DEVELOPI\-iENTS

IN
SEl)IMENTOLOGY
9B
DEVELOPMENTS IN SEDIMENTOLOGY 9B

CARBONATE ROCKS
Physical and Chemical Aspects

EDITED BY

GEORGE V. CHILINGAR
Professor of Petroleum Engineering
University of Southern California, Los Angeles, Calif. (U.S.A.)

HAROLD J. BISSELL
Professor of Geology
Brigham Young University, Provo, Utah (U.S.A.)

AND

RHODES W. FAIRBRIDGE
Professor of Geology
Columbia University, New York, N.Y. (U.S.A.)

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CONTENTS

CHAPTER 1. INTRODUCTION
R. W. FAIRBRIDGE (New York, N.Y., U.S.A.), G. V. CHtLINGAR (Los Angeles, Calif.,
U.S.A.) and H. J. BISSELL (Provo, Utah, U.S.A.) . . . . . . . . . . . . . . . . . .

CHAPTER 2. ELEMENTAL COMPOSITION OF CARBONATE SKELETONS,

MINERALS, AND SEDIMENTS
K. H. WoLF (Canberra, A.C.T., Australia), G. V. CmuNGAR (Los Angeles, Calif., U.S.A.)
and F. W. BEALES (Toronto, Ont., Canada) . . . . . . . . . . . . . . . . . . 23

CHAPTER 3. PHYSICAL CHEMISTRY OF FORMATION OF CARBONATES

W. H. TAFT {Tampa, Fla., U.S.A.) . . . . . . . . . . . . . . . 151

CHAPTER 4. CHEMISTRY OF DOLOMITE FORMATION

K. J. Hsu (Riverside, Calif., U.S.A.) . . . . . . . . . . . . . . . . . . 169

CHAPTER 5. STABLE ISOTOPE DISTRIBUTION IN CARBONATES

E. T. DEGENS (Woods Hole, Mass., U.S.A.) . . 193

CHAPTER 6. INFLUENCE OF PRESSURE AND TEMPERATURE ON LIME-

STONES
B. L. MAMET (Bruxelles, Belgium) and M. o'ALBISSIN (Paris, France) . . . 209

CHAPTER 7. THE ORIGIN OF PETROLEUM IN CARBONATE ROCKS

J. M. HUNT (Woods Hole, Mass., U.S.A.) . . . . . . . . . . . . . . . . 225

CHAPTER 8. TECHNIQUES OF EXAMINING AND ANALYZING CARBONATE

SKELETONS, MINERALS, AND ROCKS .
K. H. WOLF (Canberra, A.C.T., Australia), A. J. EASTON (London, Great Britain) and
S. WARNE (Newcastle, N.S.W., Australia) . . . . . . . . . . . . . . . . . . • • . 253

CHAPTER 9. PROPERTIES AND USES OF THE CARBONATES

F. R. SIEGEL (Washington, D.C., U.S.A.) 343

REFERENCES INDEX 395

SUBJECT INDEX . . . 404

Chapter 1

INTRODUCTION

RHODES W. FAIRBRIDGE, GEORGE V. CHlLlNGAR AND HAROLD J. BISSELL

Columbia University, New York, N. Y. (U.S.A.)

University of Southern California, Los Angeles, Calif. (U.S.A.)
Brigham Young University, Provo, Utah (U.S.A.)

Carbonates constitute some 10-15 % of the sedimentary rocks of the earth’s crustl,
as well as contributing to some important igneous and metamorphic rock types.
Thus high- and low-temperature carbonate types are recognized, but in this book
the authors are considering almost exclusively the latter.
Field and laboratory investigations of ancient sedimentary carbonate rocks
must of necessity be extended beyond the realm of origin and classification only,
and should take into consideration the physical and chemical properties of these
sediments. In order for these studies to be scientific and meaningful, careful
research of such properties of modern carbonate sediments must be undertaken on
a scale ranging from world-wide field investigations to all those detailed laboratory
techniques now known to sedimentary petrologists and petrographers. Realizing
that the bulk of ancient sedimentary carbonate rocks accumulated in various
depocenters of the marine realm, researchers have directed most of their attention
to this environment in an effort to learn more of the physical processes of desic-
cation, compaction, expulsion of interstitial water, congelation, pressure-cohesion,
grain orientation, and others. Furthermore, serious study is also being made of
sedimentary structures which heretofore were thought to be present only in sand-
stones; included among these sedimentary structures are various types of cross-
bedding, ripple-marks, mud-cracks, bottom markings, slump structures, ripple-
drift lamination, and many more. Certain coarse carbonate deposits have been
identified as turbidites, and theories have been advanced to account for their
mode(s) of origin.
All in all, geologists desire to know the entire spectrum of processes, phys-
ical, chemical, biologic, and their combinations, which lead to ultimate lithification
of carbonate sediments. Factors involved include compaction, pore reduction,
expulsion of interstitial fluids and gases, pressure-cohesion, cementation, crystal-
lization and recrystallization, dolomitization, silicification, bacterial effects, and
introduction of authigenic or metasomatic substances such as iron, sulfates, and

Some estimates run as high as 25% by volume (CHILINGAR, 1956d). All calculations must be
revised, however, in the light of drilling beneath the oceans. At the present time none of the
+
estimates is likely to be correct by 10%.
2 R. W. FAIRBRIDGE, G. V. CHILINGAR A N D H. J. BISSELL

phosphates. Lime-muds of modern repositories contain as much as 80% water,

suggesting that ancient lime-muds had comparable water contents; when these
sediments dehydrate they become denser and resultant shrinkage is taken up by
physical compaction of the sediments.
According to WELLER (1959, p.298), several firmly settled, modern calcareous
sands have been observed to have porosity between 50 and 60% (or more), which
is higher than that of quartz sand (37%). Not many limestones, however, retain
more than 10% porosity; numerous limestones practically are non-porous.
According to recent research by ATWATER (1965) on sandstones, burial to 30,000 ft.
results in a reduction of porosity to 2.5% (largely through intergranular pressure
solution); the almost total loss of porosity in medium- to fine-grained limestones
under similar burial may well be predicted. Inasmuch as empty shells and porous
structures are not crushed in many coarse-grained carbonate rocks, consolidation
was probably accomplished at an early stage before being subjected to much over-
burden pressure (WELLER,1959, p.298). The time and conditions of consolidation
of many limestones by cementation are uncertain. The question of whether the
calcareous muds compact less readily than clay or not still remains to be answered.
The weight of overlying sediments, however, is obviously an important factor
in compaction. High-pressure (up to 200,000 p.s.i.) compaction studies were
conducted by RIEKEet al. (1964) on the hectorite clay from Hector, California,
containing 50-58% by weight of CaC03. The remaining moisture content versus
the logarithm of pressure curve was similar to those of pure clays. No significant
changes in the X-ray pattern have been noticed by these writers.
The chemical composition of modern sea water is approximately the same
over the very large expanse of the oceans; in the littoral zone, however, and
particularly near the mouths of rivers, there is dilution of the ocean water by fresh
water. The dissolved solids in ocean waters (volume = 1.37 * lo9 km3; specific
gravity = 1.05) amount to 5 1016 metric tons, assuming an average salinity of
35%,, (SVERDRUP et al., 1952, p.219). The composition of sea water is presented in
Table I. In addition to the ions listed, there are over 36 others elements present.
Material contained in sea water is chiefly in ionic form. Only a small part
of total solids occurs as colloids in different degrees of dispersion, these being
chiefly clay particles and some organic matter. Various organisms are present, and
ocean water contains atmospheric gases in varying amounts depending on depth
and the history of the water mass. It must also be realized that the form of some of
the elements in sea water is far from being known, and various changes of local or
regional significance, such as the COz content, influence ionic equilibrium. As
shown in Fig.1, the order of increasing solubility of various chemical compounds of
sedimentary deposits is as follows: Al, Fe, Mn, SiOz, Pz05, CaC03, CaS04, NaCl,
MgC12. The solubility depends on the following physicochemical factors: (I) pH;
(2) Eh; (3) COz content; ( 4 ) chemical composition of solution; (5) size of dissolved
particles; (6) temperature; and (7) pressure. It is obvious, therefore, that any at-
INTRODUCTION 3

TABLE I

CHEMICAL COMPOSITION OF SEA WATER (CHIEFCOMPONENTS)~

Ion Percentage of mg/kg* Percentage equiv.

dissolved solids

Na+ 30.62 (S) 10,707 (A) 38.50 (A)

K+ 1.10 (S) 387 (A) 0.82 (A)
Mg2+ 3.69 (S) 1,317 (A) 8.95 (A)
Caa+ 1.15 (S) 449 (A) 1.73 (A)
CI- 55.04 (S) 19,343 (A) 45.10 (A)
Br-
HCO3- 0.41 (S)
Co&
sod2- 7.68 (S) 2,688 (A) 4.63 (A)
Sr2+ 13 (s)
B3+ 4.7 (S)
Sr2+, H3B03, Br- 0.31 (S)

'A = After ALEKIN(1953, p.269); S = After SVERDRUP

et al. (1952, pp.214, 220).
*See also Appendix A.

tempt at understanding physical and chemical aspects of present-day marine sedi-

ments must take into account these variables; however, the extrapolation of the
data so gained to interpret the origin of ancient sediments has inherent hazards.
Still, with the full realization of all these uncertainties, tremendous and
significant advances are being made. For example, a research program into some

/
A

/
A
J
/
/
ii 1.000

/
"/
/
/ O
- 0 /b

.o
0'
d
Fig.1. Solubility(mg/l) ofvariouschemicalcomponents of sedimentary rocks in water at atmospheric
pressure. (After RUKHIN,1961, p.275, fig.10-IX.)
4 R. W. FAIRBRIDGE, G. V. CHILINGAR AND H. J. BISSELL

of the aspects of mineralogy and chemistry of modern, unconsolidated carbonate

sediments of southern Florida, the Bahama Islands region, and Espiritu Santo
Island (by TAFTand HARBAUGH, 1964) was undertaken to understand better the
relationships of different carbonate minerals in different sedimentary environments.
One significant result of the study was the lack of evidence to suggest that either
aragonite or high-magnesium calcite is being transformed to low-magnesium calcite
within the unconsolidated sediments which were investigated. It was suggested by
these workers that inversion or transformation are not taking place because the
concentration of magnesium ions in the water surrounding the mineral grains in the
sediment is high. The high concentration of magnesium ions in interstitial water
apparently prevents transformation of aragonite and high-magnesium calciie.
The role of the various trace elements, notably Mg, Sr, Mn, Pb, etc., in con-
trolling the precipitation and stability of the metastable carbonates, especially
aragonite and high-magnesium calcite, has received considerable attention in
recent years. GOTO(1961) has shown that the solvation effect of the water molecules
is critical in loosening the atomic bonds of carbonate minerals of distinct structural
densities, and is hindered at elevated temperatures. Experimental work has shown
that the crystal form is closely controlled by the ionic concentrations.
SANDERS and CRICKMAY (1945, pp.25 1-253) discussed the chemical character
of Quaternary and Tertiary limestones of Lau, Fiji, in &e Southwest Pacific.
Particular emphasis was placed on investigating dolomite content. They observed
that dolomitization seems to be unrelated to the fossils present. Coral rocks are
generally no more dolomitized than algal rocks; but, in any particular dolomitic
rock, dolomite is most abundant in corals and least abundant in Algae and echi-
noids. Furthermore, replacement by dolomite appears to be roughly dependent on
solubility of skeletal remains, being most common in the easily soluble aragonite
shells. It was also noted that dolomitization is related to original texture: permeable
reef rock and calcarenites are usually the most strongly dolomitized.
These two examples are mentioned for the single purpose of calling attention
to the benefits of field-oriented research into physical and chemical aspects of mod-
ern sedimentary carbonate materials, but can equally well apply to all carbonates
ranging from those forming today to those as old as Precambrian. Such work must
involve careful studies of elemental composition of marine organisms as well as
those of the sediments themselves. As pointed out by VINOGRADOV (1953, p.16),
". . . the fate of some chemical elements . . . is connected with their accumulation
in the sediments so that much clarification is still needed in regard to the study of the
elemental composition of marine organisms which extract a large number of ele-
ments from the sea and concentrate them a hundredfold or a thousandfold in the
sediments, silts, and so forth." The monumental study by VINOGRADOV (1953)
has contributed substantially to our knowledge of the geochemistry of the sea.
For the better understanding of physical chemistry of dolomite formation,
two figures may be consulted. Fig.2 shows the region of dolomite formation in
INTRODUCTION 5

Fig.2. Region of dolomite formation in saturated chloride and sulfate solutions. (After VALYASH-
KO, 1962, p.57, fig.14.)

Fig.3. Solubility of CaC03-MgC03-HzO system at Pco,=l atm. and Pc0~-0.0012 atm. and
temperatures ranging from 0" to 70°C. Points between ordinate and 45 "-line represent solubility
of calcite-dolomite mixtures, whereas those between 45"-line and the abscissa represent dolomite-
magnesite mixtures. The amounts of Mg(HC03)z and Ca(HC03)z are expressed in mmole/l ,OOOg
solution. (After YANAT'EVA, 1950, 1954; also see CHILINGAR, 1956a; BARONand FAVRE, 1958.)

-
saturated chloride and sulfate solutions, and Fig.3 indicates the solubility of the
CaC03-MgC03-HzO system atpcoz 1 atm. and temperatures ranging from 0 to
70°C. In Fig.3, the points of intersection between the bisectrix and dolomite
saturation curves show the composition of solutions saturated with respect to pure
dolomite, whereas the solubilities of pure CaC03 and MgC03 are shown on the
ordinate and abscissa, respectively. On the other hand, the solubilities of mixtures
of dolomite + calcite and dolomite +
magnesite (two-phase) are shown by the
junction (nodal) points. The curve connecting these junction points to the left of
bisectrix represents solubility of mixtures of dolomite and calcite, whereas the one
6 R. W. FAIRBRIDGE, G. V. CHILINGAR AND H. J. BISSELL

at the right of bisectrix represents mixtures of dolomite and magnesite. In all cases,
the magnesite had the highest solubility; dolomite was least soluble. If the solubil-
ity of carbonate rock is determined and plotted on Fig.3, the position of the point
on the diagram could indicate the presence of: ( I ) CaCOs alone; (2) CaMg(CO3)z
alone; (3) MgC03 alone; (4) mixture of CaC03 and CaMg(C03)~;and (5) mixture
of CaMg(CO3)z and MgC03. On the other hand, the solubility of carbonate rock
may be estimated if the mineralogical composition of carbonate rock is determined.
More research, however, still remains to be done in this field. YANAT’EVA (1957)
showed that the region of crystallization of dolomite at a given pcoZ reaches
maximum proportions at temperatures between 30” and 45 “C. Inasmuch as pH
in sea water tends to respond to and reflect (inversely) pcoZ in the atmosphere, one
may conclude that dolomite is stable at a lower pH than calcite; thus, some of’the
widespread dolomites of the Precambrian and early Paleozoic times may be
primary precipitates out of ancient sea water of lower pH than that of today.
Diagenesis of carbonate rocks and mechanism of dolomitization have been dis-
cussed recently in detail by CHILINCAR et al. (1967), and by various authors in a
symposium edited by PRAYand MURRAY (1965).
It is important to mention here that there are ever-increasing investigations
of the role of microorganisms in primary precipitation of certain materials in
oceans and lakes, as well as studies of diagenetic effects of these organisms. As
pointed out by Oppenheimer in the introduction to the excellent work of KUZNET-
sov et al. (1963): “It can be presumed that much of the transition or diagenesis
of inorganic elements and organic compounds in water and sedimentary environ-
ments takes place directly or indirectly through the activities of living microor-
ganisms. These microorganisms are indigenous to all environments except vol-
canic high-temperature sites, and their abundance throughout the hydrosphere
and surface of the lithosphere is evidence of their acitvity. They can withstand and
be active at pressure up to 25,000 p.s.i., pH from 1 to 10, temperatures from 0 to
75 “C, and salinities up to saturation.” Evidence has been obtained which indicates
probable existence of bacteria in sedimentary rocks in excess of 3 billion years.
Microorganisms probably have been present in all sedimentary realms throughout
all geologic eras and accordingly have affected sedimentary processes. Data on
simultaneous deposition of calcite, dolomite (or magnesium calcite) and sulfur,
and the role played by bacteria, are not abundant. It would appear that at least
two principal mechanisms by which microbiological processes can lead to formation
of sulfur in syngenetic deposits have been noted. One is the formation of molecular
sulfur by bacteria in a bioanisotropic body of water rich in hydrogen sulfide; the
sulfur sinks and is buried in bottom lime-mud. The second is that sulfides can form
by reduction of sulfates in water-rich oozes, and after diffusion to the surface layer
will be oxidized to molecular sulfur by the bacteria. Such an example seemingly
is the bioanisotropic Lake Belovod (U.S.S.R.), which has been described by DOLGOV
(1955). Microscopic studies of the surface layer of ooze proved the presence of
INTRODUCTION 7

new crystals of calcite, having been formed by oxidation of calcium sulfide and by
the photosynthetic activity of the phytobenthos. One would suppose that molecular
sulfur can be deposited in bodies of water only when hydrogen sulfide is formed
at a very high rate in the lime oozes. Here, again, is a problem requiring further
study.
The present book, Carbonate Rocks, Volume B, is an integrated effort of
many scientists to bring into sharp focus the tremendous amount of data, ideas,
and concepts of physical and chemical aspects of carbonate sediments. The chapters
by different authors are reviewed in the order of their appearance in this book.
In the opinion of the editors, the volumes (Carbonate Rocks, A and B) represent
some of the best thinking of researchers and teachers in this field today. These are
people whose lives are dedicated to the development of new ideas and concepts,
and to a rigid application of the scientific method. The latter calls for imagination,
indeed intuition, but patient testing and practical demonstration are inherent
requirements. Although it is now more than 100 years since Henry Sorby first cut
a thin-section of limestone, and even longer since Charles Darwin described the
modern carbonate environments of the tropic seas, the “loose ends” are numerous
and fundamental mysteries still persist as a constant and exciting challenge to
successive generations.

ELEMENTAL COMPOSITION OF CARBONATE SKELETONS, MINERALS, A N D SEDIMENTS

Factors determining elemental composition of sedimentary carbonate rocks fall

into three groups: (a) initial physicochemicalfacfors (nature of solutions and ions,
pH, Eh, temperature and pressure, rates of reactions, etc.); (6) organic factors
(direct and indirect metabolic effects, reworking, bacterial processes-even long
after burial); and (c) inorganic (diagenetic) factors (modifications to the sediment
during and after burial). Numerous components occur in carbonate rocks in only
trace amounts; yet in certain cases they appear to play decisive roles. Solid solution
(isomorphous) series are particularly important. Of possible importance are the
following elements: Mg, Mn, Ni, Fez+, Sr, Ba, Pb, Co, Zn, Ca, Cd. Binary series
are better known than polycomponent systems. Some research is being conducted
on the possible use of fluid inclusions as indicators of paleoenvironments (either
synsedimentary or diagenetic).
In Chapter 2, K. H. Wolf, G. V. Chilingar and F. W. Beales discuss the
elemental composition of carbonate skeletons, minerals and rocks. They also de-
scribe the factors and processes determining the elemental composition; both inor-
ganic and organic processes were covered in considerable detail.
The numerous chemical components of carbonates occur in what has been
usually termed major, minor and trace quantities. Some elements occurring as
traces under certain conditions, are present as minor or even major components
8 R. W. FAIRBRIDGE, G. V. CHILINGAR AND H. J. BISSELL

under other physicochemical or biochemical influences. On the other hand, certain

elements never occur in concentrations beyond that of minute traces in carbonate
skeletons, minerals and rocks due to numerous reasons. According to DEERet al.
(1962), the following elements have been recorded: (1) calcite-Mg, Mn, Fez+,
Sr, Ba, Co, Zn; (2) aragonite-Sr, Pb, Ba, Mg(?), Mn(?); (3) dolomite-Fe2+, Mn,
Pb, Co, Ba, Zn, Ca, replacing Mg; less commonly Mn, Fe, Pb, and Mg substituting
for Ca; ( 4 ) ankerite-Fe2+, Mn; (5) siderite-Mn, Mg, Ca, Zn, Co; (6) magnesite-
Fe2+, Ca, Mn, Ni, Co, Zn; (7) rhodochrosite-Ca, Fez+, Mg, Zn, Co, Cd; (8)
strontianite-Ca; and (9) witherite-Ca, Mg. It should be noted, however, that
many of the above minor and/or trace elements are from high-temperature carbon-
ate minerals. Probably, future research will result in the finding of other elements
in these minerals.
Elements that occur in sea water in amounts higher than (p.p.m.)
are concentrated by organisms 10-100 times that amount. Some of the elements
present in the ocean water in quantities less than lO-5% (1 part per 10 million)
are also organically utilized. Elements found in biological material and which can
be classified as structural elements include C, H, N, 0, P, S, C1, Na, K, F, Mg, Si,
and Ca; whereas Fe, Cu, B, Mn, and I are the biocatalysts.
Due attention has been given by Wolf et al. to Ca/Mg and Sr/Ca ratios in
both organic and inorganic carbonates; and their dependence on temperature,
salinity, etc., of the depositional environment was discussed. It is interesting to
note here that the maximum MgC03 content of inorganically precipitated calcium
carbonate is approximately 4% in contrast to the maximum value of about 30%
in organically formed carbonates. CHAVE(1954) demonstrated that aragonitic
organisms seldom contain over 1% magnesium carbonate. The Ca/Mg ratio,
therefore, also largely depends on the mineralogic form of the carbonate.
Non-carbonate material is often present in carbonate sediments. A distinc-
tion between primary detrital components and authigenic (diagenetic) minerals is
made. The presence of so-called “high-temperature” forms among the latter
(e.g., quartz, feldspars, sphene, rutile, tourmaline, etc.) should no longer be a
source of astonishment but rather should be used as indicator for reconstructing
diagenetic environmental chemistry. The presence of considerable primary organic
matter in a carbonate sediment is often the signal for the enrichment of the rock in
a wide range of trace elements such as Mo, V, Ni, Pb, Cu, Ag, As, Ge, I and Br.
The bacterial liberation of H2S in the syndiagenetic stage is a significant “fixing”
process. Inasmuch as some elements present in sea water in the merest traces are
selectively concentrated by certain organisms by several orders of magnitude, the
nature of the initial biota is of special significance.
Among the organisms that are involved in the precipitation of carbonates, it
is important to distinguish between (1) the higher phylogenetic groups that secrete
carbonates into skeletal material; and (2) those-notably certain primitive Algae-
that merely create a favorable microenvironment for precipitation by removal of
INTRODUCTION 9

COz and elevation of pH, and hold the fresh precipitate from dispersal by currents
by mats of fine hairs or filaments. The latter are particularly significant in the
Precambrian deposits; however, they are still observed in the living state today,
particularly in lagoons and tidal flats, i.e., partially isolated but well-illuminated
and oxygenated habitats (favoring vigorous photosynthesis).
Much attention has been given to the ratios of the various carbonate minerals
within sediments and their diagenetic roles. Aragonite/calcite, Ca/Mg, and Ca/Sr
ratios, organic components, etc., are of significant importance in skeletal compo-
sition and reflect both environments and phylogeny. Of considerable interest is the
discovery pioneered by ABELSON (1957), that proteins and amino acids in minute
amounts may be analyzed from shells of great antiquity. Some, but up till now very
little, attention has been given to the nature of invertebrate shell growth. Because
of its biomedical significance,somewhat more is known of mammalian calcification.
Isotopic analysis of skeletal material has proved to be illuminating; not only
for paleotemperature work (1*0/l60 ratios), but also for salinity determination
and for recognizing organic from inorganic microcomponents, notably carbon
isotopes. The “law of minimum in ecology and geochemistry” can be’utilized
successfully in environmental reconstruction. For developing exploration philos-
ophies (notably in petroleum search) the geochemical techniques involved can be
very helpful.
As a result of diagenesis-epigenesis, which encompasses a large number of
factors and mechanisms, there is an alteration in the content of major, minor and
trace elements, and texture and structure of individual carbonate particles and
whole rock units. Trace elements are mobilized by diagenesis-epigenesis and meta-
morphism.
In relation to a chemical alteration of carbonates, the numerous diagenetic
processes include: (I) inversion: aragonite-calcite; (2) conversion: high-Mg
calcite-low-Mg calcite; (3) pseudomorphic replacement: carbonate by carbonate;
(4) grain growth; (5) grain diminution; (processes 2-5 are commonly grouped and
referred to collectively as “recrystallization”); (6) genesis of non-carbonate compo-
nents; (7) solution, leaching and bleaching; (8) adsorption-diffusion-absorption;
and (9) precipitation of carbonate: cement and nodules.
Attention is given to ionic exchange and replacement during advanced
diagenesis; compaction of sediments within any sedimentary basin forces migration
of fluids, as stressed by NAGY(1960) in his “natural chromatography” concept.
Low-grade metamorphism is sometimes induced.
Special consideration has been given to an examination of the inorganic
physicochemical conditions of precipitation. These conditions today appear to be
of very little importance, but may have been predominant in many ancient deposits.
Of interest for the idea of a “cold Precambrian” (FAIRBRIDGE, 1964) is ANGINOet al.
(1964) recent observation of gypsum, aragonite and mirabilite precipitation in
ice-covered Lake Bonney in Antarctica. The presence of dominant Mg in contem-
10 R. W. FAIRBRIDGE, G. V. CHILINGAR AND H. J. BISSELL

porary sediments has now been traced to a large range of environments, but always
distinct from modern sea water; the implications for interpreting the nature of
Precambrian-Paleozoic sea water are forceful but incomplete.
A number of examples illustrating changes in the elemental composition
with time through the geologic column are presented by Wolf et al. Some of the
changes in contents of elements occurring from the Precambrian to the Recent are
world-wide (Fig.4). The interpretations of the causes, however, are quite hypothet-
ical and consequently are of a controversial nature. For example, the analyses of
numerous limestone samples showed that there is a general increase in the average
Ca/Mg ratio in going up the geologic column, with superimposed periodic fluc-
tuations (see CHILINGAR, 1956~).One possible explanation for the evolution of
dolomites is the selective return of calcium to the lands. There appears to be a
selective weathering of calcium over magnesium in the sediments, and a gradual
increase with time of Ca/Mg ratio in solutions contributing to the sea. Permanent
loss of muds, which have very low Ca/Mg ratios,. from lands is another reason
for the selective and permanent loss of magnesium from the continents.
A possible reason for the decrease in Ca/Mg ratio since the Cretaceous time
is the fact that pelagic Foraminifera started to extract great quantities of calcium
out of the sea water and deposit it in the oceans during and after the Cretaceous
time. This calcium is thus withdrawn from the cycle and never returned to the

5 - 50-

v)
n
z
a
v) 4- 40-
4
I-
O Z
- 0 '
* r n
m a
3u
4
30-
3 -
z
z - 0 -
o t
-
I- P
2 2- 0
20

0, - .-r"
. s
0
0
s I - - 10 CARBONATES OF
4''NORTH AUERICA

I I I 1

Pr 23 1 Pz I Mr 1Kr
950 600 225-m-0-

ABSOLUTE TIM^ IN MILLIONS OF YEARS

Fig.4. Variation of CaO/MgO ratio in clays, sands and carbonate rocks with time. (After RONOV,
1964, p.723, fig.2.)
INTRODUCTION 11

Regional factors are of great interest in considering ancient environments.

Arid shores will set up quite distinctive circulation patterns within a basin from
temperate well-watered coastlines. Depth distribution can also play a critical role.
In Paleozoic rocks dolomite was formerly often considered to be a deeper environ-
mental indicator than limestones, but the evidence from cyclic sequences showed
that in many cases the dolomite facies was near-shore (FAIRBRIDGE, 1957). On the
Russian Platform through much of the Paleozoic a distinctive nature of circulation
reversed this pattern, and phosphorites commonly mark the near-shore facies.
Wolf et al. review in some detail the works of Soviet scientists Vinogradov, Ronov,
Khain, Teodorovich and others on the changes in Ca/Mg and Ca/Sr ratios through
time based on vast numbers of analyses made on the carbonate rocks of the Rus-
sian Platform. These results were also compared with the data from North America
and the rather sparse information from elsewhere in the world. The modern Mg con-
tent drops to 1/25 of its Proterozoic value, whereas the Ca content rises 40% in
the same period. Thus there is a marked decrease in the Ca/Mg ratio going back
through time.
TEODOROVICH (1960) suggested that there has been a progressive change in
mode of carbonate genesis through time: (a) Precambrian-Early Paleozoic: direct
chemical dolomites; (b) Late Paleozoic: both diagenetic and chemical dolomites;
and (c) Mesozoic-Cenozoic: predominantly diagenetic dolomites. VINOGRADOV
and RONOV(1956) have shown that these systematic changes affect cements as
well as granular components, so that they must be a function of a secular change
in environmental fluids, which in turn reflects the progressive evolution of the
earth‘s crust. The dynamic nature of the latter, indeed, precludes any possibility
that its composition should remain static, although one may visualize perhaps
rapid, non-secular steps from one near-equilibrium condition to the next, as
successive threshold levels are surpassed (FAIRBRIDGE, 1964). In this way, the total
pco2, at or near the earth’s surface, derived basically from “juvenile” volcanic
emanations, has been progressively rising through time, but has been controlled
and in fact probably decreased sharply at certain stages by solid carbonate removal
into buried sediments.
Very large deviations of the pco2 through geologic time are ruled out by some
scientists on two counts: (a) the buffering effects related to CaC03 solubility in
sea water, and (b) the principle of biologic continuity through time, which will
not allow gross changes in the atmospheric environment without destroying the
planetary biota. Minor phylogenetic catastrophes are allowable and are believed
to have occurred. It is believed from the geochemistry of the lithologic record that
the pcoZdecreased slowly through the Paleozoic and Mesozoic times, culminating
with the vast removal of c0a2-by pelagic plankton in the Cretaceous time.
It would be interesting. for imaginative biologists to experimentally control the
metabolism of selected primitive marine organisms under conditions of higher
pco2, higher Mg2+ and lower Ca2+ concentrations.
12 R. W. FAIRBRIDGE, G. V. CHILINGAR AND H. J. BISSELL

PHYSICAL CHEMISTRY OF CARBONATES

Modern carbonates laid down in warm, shallow waters consist, for the most part,
of metastable minerals (aragonite and high-magnesium calcite) that did not as a
rule persist for long periods in the past. Ancient carbonates consist of dolomite
and low-magnesium calcite. During lithification (diagenesis) alteration occurs either
by solid-state recrystallization (thus preserving original structures as well as
Sr/Ca, W / W , and 1 6 0 / 1 8 0 ratios) or by solution and reprecipitation (destroying
original features and isotopic ratios).
Experiments described by W. H. Taft in his Chapter 3 on the “Physical Chem-
istry of Carbonates”, show that the metastable aragonite recrystallizes to calcite
within 100 days, if submersed in distilled water at room temperature. In nature,
however, Holocene shallow marine aragonites maintained constantly in sea
water for several thousand years are found to be perfectly preserved. It was found
experimentally that the presence of large amounts of magnesium ions ,inhibited
inversions; this is true also of strontium, but only in very high concentrations.
Recrystallization is accelerated by the rise in temperature, by the presence of cer-
tain trace elements, or by the introduction of any ion that tends to lower the pH.
Generally, when the natural aragonite or metastable calcite are exposed to
rainwater, they rapidly invert to the stable forms. Aragonite forms the cement in
beachrock; however, all beachrocks dating from a few thousand years have calcite
cements, because during this time they have been subjected to leaching by rain and
ground water. Occasionally, dolomite replaces the aragonite or high-magnesium
calcite in quite modern deposits.
The role of time in some carbonate reactions is just beginning to become
recognized. Some dolomite does not form immediately, but instead the disordered
form “protodolomite” forms, which only slowly becomes ordered. The protodolo-
mite may be synthetically prepared if Ca2+ and Mg2+ ions are slowly introduced
to the solutions containing CO&. For a detailed review on a synthetic formation
of dolomite, one may consult CHILINGAR (1956b) and SIEGEL (1961). In sea water,
S O P may form a complex with Ca2+ and thus raise the Mg/Ca ratio which is
favorable for the dolomite formation.
In nature, if a bed of shallow-water metastable carbonates becomes emergent
(due, for example, to brief eustatic oscillation), it is likely to be quickly inverted to
stable calcite. If, however, the platform is subsiding and the formation becomes
covered by other sediments and is subjected to rising connate waters (“anadiage-
nesis”) rich in Mg2+ and S042- ions, a favorable situation may exist for dolomiti-
zation. An alternating (cyclic) sequence of calcitic limestone and dolomite could
thus develop. On the other hand, the common association of Paleozoic dolomite
layers with higher amounts of insoluble residues suggests rather that they belonged
to shallower water environments (FAIRBRIDGE, 1957). Inasmuch as the latter are
normally richer in the high-magnesium calcites and aragonites than deeper sedi-
INTRODUCTION 13

ments, the alternation may be controlled by primary differences in carbonate sedi-

ment type, which in turn may be in a cyclic sequence of eustatic origin.

CHEMISTRY OF DOLOMITE FORMATION

In Chapter 4,Dr. K. Jinghwa Hsu sums up the present state of knowledge on the
long-puzzling problem of dolomite formation. He pointed out that not only must
one consider the geochemical conditions appropriate for the formation of the
mineral dolomite as a stable phase, i.e., simple discrete crystals, as in abyssal depths
of g e northern ocean, but also for the large masses of dolomitic rocks in the geo-
logical record which indicate that such conditions must have persisted for consid-
erable periods of time.
Experimental data on dolomite formation under surface environments still
contain much that is contradictory. For example, the solubility product of dolomite
at 25 "C and a pressure of 1 atm., as determined by various investigators, ranges from
10-17 to 10-20. Unquestionably dolomite is present in very recent sediments within
a few cm of the surface in some South Australian lagoons, in beachrocks of the
Persian Gulf, in the West Indies, and elsewhere under about 1 atm. pressure.
Equally well established is the presence of fresh dolomite rhombs in modern deep-
sea sediments under a pressure approaching 500 atm. and temperature of about
2°C. Under such contrasting conditions wide ranges of pH and Eh are observed;
and there is little agreement among the geochemists concerning their respective
roles. An increase of temperature, however, evidently increases the rate of dolomite
formation. In synthetic dolomites, an elevated pressure has always favored the
reaction. At relatively low pressure, GRAFand GOLDSMITH (1956) only obtained
what they termed a protodolomite (calcic and with a disordered lattice).
Dr. Hsu considers the free energy relations in three hypothetical reactions:
CaC03 + MgC03 + CaMg(CO3)z (A)
In this case, confusion occurs because MgC03 is found to be not stable in
water (marine or fresh) at room temperature and normal pressure, although the
free-energy calculation suggests that it is.
CaC03 + MgC03.3Hzo + CaMg(C03)~+ 3Hz0 (B)
Experiments suggest that MgC03. 3Hz0, nesquehonite, is the stable mag-
nesium carbonate in water below 80°C.
4CaCO3 + Mg4(CO&(OH)z. 3Hz0 + COz + 4CaMg(C03)~+ 4Hz0 (C)
Hydromagnesite is the stable form where the pcoZ is very low. An aragonite-
hydromagnesite mixture was found as a thin surface layer over the modern
South Australian dolomites.
14 R. W. FAIRBRIDGE, G. V. CHILINGAR AND H. J. BISSELL

It can be postulated that the rate of dolomite formation without catalysis

is very slow under normal conditions, and that metastable minerals or mineral
pairs form from supersaturated solutions. Organisms may well provide the cata-
lysts.

STABLE ISOTOPE DISTRIBUTION IN CARBONATES

Stable isotope distribution in carbonates is discussed by Egon T. Degens in Chapter

5. Calcite, aragonite, and dolomite are composed of four light elements: ( I ) carbon,
(2) oxygen, (3) magnesium, and (4) calcium, all of which contain at least two stable
isotopes. Most of the stable isotope fractionation in nature apparently is the result
of exchange reactions occurring at or near equilibrium. Consequently, knowledge
of isotope fractionation factors may reveal information on paleotemperatures,
mode of formation, etc.
Carbonates exhibit a range of about 12% in 13C/12C ratio. The heaviest
carbonates occur in meteorites, whereas the lightest ones are associated with
sulfur-evaporite domes (bacterial carbonates). As pointed out by Degens, a great
number of marine organisms secrete a carbonate that is slightly enriched in 12C
as compared to the value predicted by theory for a system in isotopic equilibrium
(CRAIG, 1953; LOWENSTAM and EPSTEIN,1957; WILLIAMS and BARGHOORN, 1963).
Thus, the fact that Recent limestones from many areas also show this slight
enrichment in 12C content from the expected equilibrium value, suggests that these
limestones are in part, at least, a product of life processes in the sea. As a result of
even more 12C-enriched C02 contributions to the continental carbon dioxide
system, the fresh-water carbonates may be distinguished from carbonates formed
in a marine environment; hydrothermal carbonates in contrast are enriched in
13C. Precambrian marine carbonates are often enriched by a few permil (parts per
mille) in 1% relative to the average S W of younger limestones, and thus are more
like modern lacustrine carbonates.
For air oxygen the ratio 1 6 0 / 1 7 0 / 1 8 0 = 99.759/0.0374/0.2039. The data,
however, are generally reported in terms of lS0/160 ratio or P O , which is the
permil deviation in 180/160 ratio relative to standard mean ocean water (SMOW).
A range of about 4% in 1 8 0 / 1 6 0 is exhibited by carbonates; carbonates associated
with certain continental evaporite deposits are the heaviest, whereas the igneous
carbonatites are the lightest.
The temperature dependence of oxygen isotopes allows paleotemperature
determinations. Unfortunately, however, the original 1 * 0 / 1 6 0 record, as laid
down during deposition, is diagenetically altered. Isotopic equilibration with the
surrounding meteoric or connate waters, often intensified by higher temperature,
results in an increase in 1 6 0 content of marine limestones and shell carbonates. The
original 1 8 0 / 1 6 0 record, even of late Paleozoic carbonates, is preserved, however,
under certain post-depositional environments.
INTRODUCTION 15

Isotope studies possibly would also contribute significantly to deciphering

the origin of sedimentary dolomite. Dolomites, which precipitated in an aqueous
environment at room temperature, should be heavier by ca. 6-10 permil in 1 8 0
over cogenetic calcite or aragonite (CLAYTON and EPSTEIN,1958; ENGELet al.,
1958; EPSTEIN et al., 1964). Inasmuch as isotope data of Recent dolomite-calcite
pairs from various localities show no significant difference between calcite and dolo-
mite (EPSTEIN et al., 1964; DEGENS and EPSTEIN,1964) one may conclude that these
dolomites did not precipitate from an aqueous solution. Thus, dolomite probably
was derived by way of metasomatism of calcite, and dolomitization must have
proceeded without significantly altering ls0/160 ratio of the precursor carbonate.
DEGENS and EPSTEIN(1964) also found this to be true in the case of Paleozoic dolo-
mites. The findings of Degens and Epstein are indeed a major step forward in our
understanding of mechanism of dolomitization. The editors of this book, however,
believe that further experimental work should be done in this field before reaching
absolutely definite conclusions.
Inasmuch as the stable isotopes of calcium differ in mass by up to 20%
(4OC vs. W a ) , studies on calcium isotopes appear to be promising. There is also 5%
variation in the 24Mg/26Mg ratios in dolomites (DAUGHTRY et al., 1962), which
warrants further investigation.

INFLUENCE OF PRESSURE AND TEMPERATURE ON LIMESTONES

The joint contribution (Chapter 6) by Bernard Mamet (of Brussels) and Micheline
d’Albissin (of Paris) bears the unmistakable stamp of the classical metamorphic
limestone studies that have been made over the last century in western Europe.
Partly as a result of Mamet’s travels in America it has been possible to blend these
data with the concepts developed in the New World by F. Adams, N. Bowen, D.
Griggs, J. Handin, F. Turner, J. Verhoogen, and others.
Several distinctive stages of alteration are recognized. First of all, simple
diagenetic lithification occurs without temperature or pressure changes. Often
there is merely a phase change with or without additional cementation and, some-
times, with recrystallization. The latter expression should be used if there are new
grain boundaries and the initial fabrics are limited to ghost or palimpsest features.
Mamet called the penecontemporaneously recrystallized rock “alpha sparite” and
the subsequently altered rock “gamma sparite”. With increased load the pore
spaces in loose calcitic mixtures disappear as a result of compaction, and there is
a gradual increase in strength and stability. Precise quantitative data on the ne-
cessary loading to achieve a certain degree of compaction are lacking, in part
because very small amounts of impurities can completely alter the crystallographic
reactions, e.g., less than 2% MgO triggers recrystallization, whereas same amounts
of clay inhibit it. Studies of microfossil walls, however, offer a fairly good yard-
stick for such pressure appraisal.
 16 R. W. FAIRBRIDGE, G. V. CHILINGAR AND H. J. BISSELL

With the onset of regional, dynamometamorphic stress, calcite crystals

become reoriented (with c-axes parallel to the principal stress). Plastic strain may
be expressed by intracrystalline gliding, intercrystalline gliding and finally by re-
crystallization.
The various methods of studying deformed fabrics are also discussed in
Chapter 6: infra-red reflection spectroscopy, dilatometry, X-ray diffraction, corro-
sion patterns, thermoluminescence, etc.
In contact metamorphism, Bowen’s thermal decarbonatization series gives
the stages of alteration. If magnesium is present, which is usually the case, the
series can be complete. In regional metamorphism, the metamorphic limestones
react ultimately in the same manner as the surrounding silicate rocks, and conse-
quently the established metamorphic facies series can be identified. An outstanding
area of needed research is the progressive reaction of all types of carbonate sedi-
ments to simple basin compaction to the equivalent overburden load of 30,000 ft.

THE ORIGIN OF PETROLEUM IN CARBONATE ROCKS

In Chapter 7, John M. Hunt discusses the origin of petroleum in carbonate rocks.

This chapter is a very important contribution, because it has been frequently
assumed that petroleum does not originate in carbonate rocks. Thorough studies of
both Recent and ancient carbonates, however, show that the amounts of hydro-
carbons present in them are comparable to those in clay sediments. Hunt pointed
out, nevertheless, that there are certain basic differences in the source and types of
organic matter deposited with carbonates as compared to shales. In addition, the
rapid lithification of carbonate rocks, as compared to the slow compaction of ar-
gillaceous sediments, leads to different conditions of migration. Migration paths
are developed through fissures, fractures, and solution channels.
Approximately 87 billion barrels of oil are now known to be present in
carbonate rocks in major oil fields outside the Soviet Union and other east Euro-
pean countries. Inasmuch as some of these reservoirs are surrounded by carbonate
rocks, a reasonable assumption is that carbonates can also be the mother rocks of
petroleum.
The close association of source and reservoir beds in carbonates, in addition
to the frequent presence of impermeable evaporite cap-rocks, probably results in
a more efficient process of oil accumulation in carbonate rocks than in sand-shale
sequences. Evidences of molecular migration within carbonate source rocks are
quite numerous and convincing.
There is a possibility for the catalytic generation of hydrocarbons in carbon-
ate rocks, because small amounts of clay are present in many of these rocks. The
conversion of organic matter to hydrocarbons in pure carbonates is a thermal
process; hydrocarbons could then migrate along the solution and fracture zones.
INTRODUCTION 17

As pointed out by Hunt, this suggests that somewhat greater depths of burial and
longer periods of time are required to generate oil in carbonates as compared to
clays.

TECHNIQUES OF EXAMINING A N D ANALYZING CARBONATE SKELETONS, MINERALS AND

ROCKS

Chapter 8 is devoted to the techniques usually employed for examining and analyz-
ing carbonate skeletons, minerals and rocks. It is the joint work of Karl H. Wolf,
A. J. Easton and S. St. J. Warne. Some of these techniques are traditional; others
are rather new. Both quick field tests and the more quantitatively precise laboratory
tests are described, but space requirements limit detailed treatment to those pro-
cedures that seemed to the authors to be the most convenient and appropriate.
The basic technique to assist hand lens and binocular examination is the
etched surface, which may be produced even under field conditions with a variety
of weak acids. This is ideal for a preliminary appraisal of the microfacies, the
texture and structure. To distinguish further, for example, between faecal, baha-
mite and algal pellets, between “open-space” sparite and recrystallization sparite,
etc., thin-sections are needed. Even these can be prepared in a field camp with a
little ingenuity.
Another helpful field procedure, that may also be used in the laboratory,
is that of staining. It is essentially limited to grain sizes larger than 0.01 mm. The
same is true of spot tests.
Both well-lithified and unconsolidated material can also be studied for tex-
tures and structures by acetate peel techniques. These are particularly helpful both
for the study and easy storage of records of microfacies. These methods also can be
applied both in the laboratory and in the field. With the accumulation of large
volumes of data, special statistical methods and graphic presentation have been
developed.
Study of the associated insoluble minerals is often helpful, but care must
be taken not to alter them seriously during the separation process (especially in the
case of clays). The carbonate minerals themselves are often difficult to distinguish
from one another in thin sections. Determination of the refractive index by oil
immersion is commonly employed, but overlaps occur in the isomorphous series
and hence staining, chromatography, etc., may be used. The universal stage micro-
scope is also helpful. In recent years the electron microscope is rapidly gaining in
popularity (with its increasing availability); surface textures of fine-grained car-
bonates, particularly the organogenic ones, are remarkably characteristic. X-ray
radiography is helpful when dealing with mixed terrigenous lithologies. Great
care must be taken with aragonite, because it tends to invert to calcite under grind-
ing or during preparation of thin-sections.
18 R. W. FAIRBRIDGE, G. V. CHILINGAR AND H. J. BISSELL

Methods of chemical analysis have also been presented in Chapter 8 in some

detail for the various carbonates as well as for some of the related trace elements.
Traditional methods of wet analysis have of late been partially replaced by the
use of the spectrophotometric instruments and by the flame photometer. Differen-
tial thermal analysis and X-ray diffraction are now standard procedures, and their
particular application to the various carbonates are treated in detail in this book.
Thermoluminescence is also a phenomenon that has been applied to carbonate
study in recent years; it has attracted considerable attention with various objec-
tives in mind, both analytical and paleoecological. Further basic studies, however,
are still required in this field.
Of invaluable use in determining the rates of sedimentation and the recent
ecologic history of carbonate rocks is Urey’s method of 1% age determinations.
Many refinements have been added over the last fifteen years, and many anomalies
and confusing aspects have been ironed out. The half life of 14C essentially limits
the method to less than 50,000 years; however, encouraging research, work on
carbonate shells has been made in recent years with uranium-helium, protoac-
tinium and thorium methods that may extend the datable ranges to several million
years.
Isotope studies have also been widely employed in determining paleotem-
peratures (1*0/160), in distinguishing organic from inorganic carbonates (13C/W),
and for a number of other purposes.

PROPERTIES AND USES OF THE CARBONATES

The economic aspects and practical uses of the carbonates, here discussed in Chapter
9 by Dr. F. R. Siegel, are numerous. Inasmuch as bulk supplies, especially of
limestone and dolomite, are often required, accessibility and short transport
routes from consumers are of the highest importance. In some parts of the world
this is no problem, but in others (notably the Precambrian shield and volcanic
regions) there may be serious deficiencies.
Annual consumption figures for limestone in a country such as the United
States are constantly rising, and indeed may be taken as an approximate index of
the gross national product. This is especially true if the year to year figures are seen
on a tonnage basis rather than on the sliding scale of a gradually inflating currency.
For example, in 1964 crushed stone used in U.S.A. exceeded 700 million tons as
compared with less than 450 million tons in 1954. Lime production in 1964 was
19 million tons against 8 million tons in 1954. Portland cement output was 360
million barrels in 1964 against 290 million barrels in 1954.
Some 100 uses are listed for limestone, dolomite and marble (Table XI11 in
Chapter 9). Some are employed directly as for building stone (known technically in
the U.S.A. as “dimension stone”); others indirectly as in the chemical industry
INTRODUCTION 19

(e.g., “whiting”, see over 70 uses listed in Table XIV in Chapter 9), glass manu-
facture, or in sugar refining.
Other carbonate minerals are not found in large rock-forming deposits as is
the calcium-magnesium group; they are mainly utilized as metal ores and in the
chemical industry. These include rhodochrosite, an ore of manganese, also used
as a pigment “manganese white”; siderite, an iron ore; smithsonite, a zinc ore and
pharmaceutical; witherite, a barium ore, also used in sugar refining, as a rat poison,
in paints, and in glass and paper industries; strontianite, a strontium ore, also used
in sugar refining, in paints, glass and in pyrotechnics; cerussite, a lead ore, also
used in paints, for putty and in “leaded” paper; malachite and azurite, copper
ores and ornamental stones such as vases and table tops; and trona, a sodium ore,
used in the glass, paper, soap and other chemical industries.
Modern research is constantly opening new areas of use for the carbonates.
The new “oxygen process” for steel smelting uses twelve times more limestone
than do conventional refractory methods. Consumption, even of the simple
crushed rock, will rise inevitably.
A natural by-product of limestone country is the geomorphic phenomenon,
the “karst” landscapes and caverns. Whereas the waterless land surface may be
poor for agriculture, it is sometimes more than offset by the valuable tourist at-
tractions of the caves, with their stalactites and stalagmites, underground streams
and speleological interests. Karst systems (if adequately sealed) also offer a poten-
tial for underground storage of gasoline, etc.
Another group of limestone geomorphic phenomena of very considerable
tourist value are the coral reefs, and the related island-life charms extending across
the tropical Pacific and Indian Oceans. The rather minor, though more accessible,
examples in the Atlantic include those in Florida, the Bahamas and West Indies.

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In reviewing various chapters in this book, in many instances the editors quoted the same authors
whose names appear in the reference lists of particular chapters; these references are not re-
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VINOGRADOV, A. P., 1953. The Elementary Chemical Composition of Marine Organisms. Sears
Foundation for Marine Research, Yale Univ., New Haven, Conn., Mem., 2: 647 pp.
WELLER, J. M., 1959. Compaction of sediments. Bull. Am. Assoc. Petrol. Geologists, 43(2): 273-310.
YANAT’EVA, 0. K., 1950. The solubility of dolomite in aqueous salt solutions. Izv. Sektora Fiz.
Khim. Analiza, Inst. Obshch. Neorgan. Khim., Akad. Nauk S.S.S.R.,20: 252-268.
YANAT’EVA, 0. K., 1954. About physical-chemical characteristic of some carbonate rocks. Dokl.
Akad. Nauk S.S.S.R.,96(4): 717-719.
YANAT’EVA, +
0.K., 1957. On the solubility polytherm of the system (CaCOs MgSO4 $ CaS04
+ MgCOs) - HzO. Proc. Acad. Sci. U.S.S.R.(Chem.Sect., English Transl.), 1957: 155-151.
INTRODUCTION 21

APPENDIX A

COEFFICIENTSFOR CONVERTING mg/l TO rng-equiv./l (rng/l - COEFFICIENT = mg-equiv./l)I

Ions Equivalent weight Coefficient

20.035 (20) 0.0499

12.16 0.0822
22.997 (23) 0.0435
18.03 0.0554
30.0 0.0333
48.03 (48) 0.0208
35.476 (35.5) 0.0282
61.0 0.0164
46.0 0.0217
62.0 0.0161
17.0 0.059

1 See also EREMENKO

(1960).
Chapter 2

ELEMENTAL COMPOSITION OF CARBONATE SKELETONS,

MINERALS, AND SEDIMENTS

K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

Department of Geology, The Australian National University, Canberra, A.C. T. (Australia)'

Department of Petroleum Engineering, University of Southern California, Los Angeles, Cal$
(U.S.A.)
Department of Geology, University of Toronto, Toronto, Ont. (Canada)

SUMMARY

Emphasis is laid upon the basic chemical, organic, and inorganic principles that
determine the composition of carbonates. Elemental compositions vary consider-
ably depending on numerous primary and secondary factors. Their significance
has been documented by selected published examples.
The practical applicability of elemental analyses of carbonates is stressed,
and some case histories provide evidence that the chemical make-up of both the
carbonates and associated non-carbonate components can be useful indicators
of the original environmental conditions.
It is hoped that data compiled here are sufficient to stimulate further research
in this interesting field of sediment geochemistry.

INTRODUCTION

Carbonate minerals and rocks form in nature over a wide range of environmental
conditions and their composition is controlled largely by their mode of genesis.
In addition to constituting approximately 10-1 5 % of the sedimentary deposits,
carbonates occur also in certain varieties of igneous and metamorphic rocks. In
general, therefore, carbonates can be divided into high- and low-temperature types.
The present contribution, however, deals almost exclusively with the low-temper-
ature and low-pressure carbonate minerals and rocks. Further, inasmuch as a
comprehensive summary of many of the aspects related to sedimentary carbonates
has been presented recently by a number of workers such as REVELLE and FAIR-
BRIDGE (1957), and GRAF (1960), the authors confined themselves to the discussion
of selected fields covering only some of the many facets of the elemental composition

Present address: Department of Geology, Oregon State University, Corvallis, Ore. (U.S.A.).
24 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

of carbonates. A summary of the absolute values of chemical elements appears to

be premature in view of the rapid advances in both compositional data and con-
cepts of genetic mechanisms. Hence, no pretense is made of completeness and much
of the information presented here is of necessity sketchy and superficial. Where a
choice has had to be made between brief citations, or more complete coverage of
fewer examples, the authors have favored the policy of reference to as many
different publications as space permitted.
Numerous gaps are only too apparent in the present state of our knowledge.
For example, RONOVand KORZINA (1960) pointed out the gap in our knowledge
between highly concentrated mineral deposits on the one hand, and the dispersed
trace minerals and trace elements on the other.

FACTORS AND PROCESSES DETERMINING THE ELEMENTAL COMPOSITION OF CARBONATES

Some details of materials, conditions, and processes that control the composition
of carbonate minerals, skeletons and rocks are given in other chapters. By way of
introduction, and to emphasize the complexity of inter-relationships, however,
some of the factors and processes that are considered in other chapters are listed
as follows:

Physicochemicalfactors

(I) Composition of solution (type of ions present).

(2) Concentration of ions present.
(3) Ionic potential (= property of ions).
(4) pH (= property of solutions).
(5) Eh (= property of both solutions and ions).
(6) Temperature and pressure.
(7) Rate of reactions.
(8) Solubility of the various possible compounds that can form.
(9) Absolving property of water medium and other fluids (GOTO,1961).

Organic influences

(I) Direct metabolic processes (e.g., processes which control composition

of both carbonate skeletons and organic matrix).
(2) Indirect influences by changing environment (e.g., metdbolic processes
of animals and plants may change pH, Eh, and ion-concentration of water medium).
(3) Biotic reworking (e.g., mud-eater may cause chemical alteration of
carbonate sediments in digestive system before excretion as fecal pellets occurs).
(4) Bacterial processes (although strictly referrable to items 1 and 2 above,
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 25

solution, deposition, and transformation of carbonates and solutions by Bacteria

is a sufficiently important topic to warrant separate mention), e.g., post-humous
decomposition of organic matter (gases, fluids, and ions are liberated to the sur-
rounding environment as a result of decomposition), sulfate reduction and so on.

Inorganic processes

( I ) Precipitation (e.g., deposition of aragonite, low-Mg calcite, etc., by

evaporation).
(2) Solution (e.g., selective removal of more soluble carbonates).
(3) Leaching (e.g., selective removal of ions from carbonate minerals and
skeletons without actual solution).
( 4 ) Oxidation and reduction.
(5) Adsorption-diffusion-absorption (e.g., differential uptake of ions by
clay minerals and both living and dead organic matrix).
(6) Replacement (e.g., replacement of carbonates by carbonates or by non-
carbonates).
(7) “Recrystallization” (a number of processes included here can change the
composition of the carbonates).
(8) Extraneous contribution (e.g., terrigenous, volcanic, and cosmogegcpus).
Two important factors have to be taken in consideration in all discussions
on the chemical composition of sediments, namely, first, the limitations of the
methods and instruments employed, and second, the “human” factors involved in
collecting samples, and others (LAMARand THOMPSON, 1956).
Numerous sensitive stability ranges and geochemical thresholds clearly
control the equilibria involved in carbonate-rock formation. Numerous examples
of complete alteration and many reversible reactions are well documented in the
literature. Probably even more serious at the present time is our lack of knowledge
of the relationships between organogenic and purely physical processes in carbonate-
rock formation. Organic processes undoubtedly predominate in providing the raw
materials from which the bulk of Phanerozoic (post-Precambrian) limestones have
formed. The course of their subsequent diagenesis has largely depended on physical
processes. Many direct and indirect inter-relationships undoubtedly occur and will
be the subject of much research in future years. It is hoped that this partial compila-
tion of ideas will assist both assessment of the present state of our knowledge and
the research that will advance our understanding further.

ELEMENTAL COMPOSITION OF CARBONATE SKELETONS, MINERALS, AND ROCKS

In a general way, the numerous chemical components of carbonates occur in what

has been usually termed, major, minor, and trace quantities. Where cations can
26 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

form a partial or complete solid solution, the ionic species can be expected to
occur in either major or minor quantities, or as minute traces. Considering particu-
lar solid solution series, it has been found that elements occurring as traces under
some conditions, will be present as minor or even major components under other
physicochemical or biochemical influences. On the other hand, certain elements
never occur in concentrations beyond that of minute traces in carbonate skeletons,
minerals, and rocks due to numerous geological and chemical reasons as illustrated
here. The writers refrained from setting precise boundaries between the major,
minor, and trace elements as they would serve no purpose in the present discussions,
especially in view of the uncertain chemical affinities of the components in many
cases.
The chemistry of sedimentary carbonates is in general divisible into the
following aspects: ( I ) isomorphism (= solid solution) of carbonate minerals, (2)
minor and trace elements in carbonate minerals, (3) “fluid inclusions” in carbon-
ates, and (4) non-carbonate components in carbonate sediments. Each aspect is
considered briefly as given below.

Isomorphism of carbonate minerals

Complete low-temperature isomorphous substitution of one cation by another is

possible in the following cases:
calcite (CaC03) - rhodochrosite (MnCOs)
dolomite (CaMg(CO3)z) - ankerite (CaFe(CO3)z)
magnesite (MgC03) - siderite (FeC03)
rhodochrosite (MnC03) - siderite (FeC03)
strontianite (SrC03) - witherite (BaC03); isomorphous only in artificial
material.

High-temperature solid solutions (not further considered here) are discussed

in the following references (among others):
ROSENBERG (1 963) for MgC03-FeCO3, and MnC03-FeC03
ROSENBERG (1 963) for CaC03-FeC03
HARKER and TUTTLE ( 1 955) for CaC03-MgC03
GOLDSMITH (1959) for CaC03-MgC03, CaC03-MnC03, and CaC03-
FeC03
GOLDSMITH et al. (1 962) for CaC03-MgC03-FeC03
CHANC(1 963) for BaC03-SrC03, SrC03-CaC03, and BaC03-
CaC03
GOLDSMITH et al.( 1955) for MgC03-CaC03
CHAVE (1 952) for CaCOs-CaMg(CO3)z (of low-temperature origin)
HOLLAND et al.( 1963) for Zn and Mn coprecipitated with calcite; and Sr
content of calcite and other carbonates.
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 27

Reference can also be made to general publications such as those by GRAF

and LAMAR (1955), GRAF(1960), GOTO(1961), and DEER et al. (1962).
Rare carbonate minerals are not discussed in this chapter although they
most certainly will be of definite interest in future petrologic studies: in particular
those concerning diagenesis. ALDERMAN (1959), for example, pointed out that
huntite (CaMg3 (C03)4), which usually forms as a weathering product of dolomite
and magnesite, may prove to be more widespread than is generally assumed.

Minor and trace elements in carbonate minerals

According to DEERet al. (1962), the following elements, in addition to the major
ones given in the formulae above, have been recorded: (1) calcite-Mg, Mn, Fez+,
Sr, Ba, Co, Zn; (2) aragonite-Sr, Pb, Ba, Mg(?), Mn (?); (3) dolomite-Fe2+,
Mn, Pb, Co, Ba, Zn, Ca, replacing Mg; less commonly Mn, FeyPb, and Mg sub-
stituting for Ca; ( 4 ) ankerite-Fez+, Mn; (5) siderite-Mn, Mg, Ca, Zn, Co; (6)
magnesite-Fez+, Ca, Mn, Ni, Co, Zn; (7) rhodochrosite-Ca, Fez+, Mg, Zn, Co,
Cd; (8) strontianite-Ca; and (9) witherite-Ca, Mg. It should be noted, however,
that many of the above minor and/or trace elements occur in high-temperature
carbonate minerals. Probably, future research will show presence of other elements
in these minerals.
According to LOGVINENKO and KOSMACHEV (1961), mainly binary series of
isomorphism are described in the literature, whereas information on polycompo-
nent systems such as (Fe, Ca, Mg, Mn)C03 are scarce or lacking. In many cases,
the minerals have been identified by optical, X-ray, thermal, staining, and other
methods as ones of simple composition, and none of the other elements were
detected in spite of their presence in comparatively large amounts. In this regard
the binary nomenclature (e.g., ferroan calcite, breunnerite) is misleading. For
example, LOGVINENKO and KOSMACHEV (1961) determined the composition of
diagenetic carbonate concretions to be ( F ~ s z . z ~ - s s . ~Ca7.39-12.96,
z, Mnz.45-3.10,
Mg0.34-5.26) CO3. (A similar occurrence has been quoted in the chapter on
techniques of analyzing carbonate skeletons, minerals, and rocks -WOLF et
al., 1967.)

Fluid inclusions in carbonates

Inter- and intra-crystalline fluid inclusions in calcite and dolomite minerals are
mentioned by LAMAR and SHRODE (1953) and SHOJIand FOLK(1964). The former
two investigators examined water-soluble .salts in carbonate rocks and concluded
that “much of the calcium and sulfate (excluding calcium dissolved from the calcite
and dolomite) probably occurs as intergranular solid calcium sulfate with mag-
nesium sulfate possibly occurring in the same manner”. As thin-section and de-
crepitation studies suggest, however, “the sodium, potassium, and chlorides,
28 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

together with some calcium, magnesium, and sulfate, are probably present primarily
in solution in intragranular fluid inclusions”.
SHOJIand FOLK(1964) found fluid inclusions in calcite during electron-
microscopic investigations of carbonates. The calcites are often spongy due to
densely crowded bubbles. The above authors suggested that the inclusion-rich
calcite formed in environments that lacked clay-sized carbonate and where the
sea water was relatively clean. The sponginess of the calcite may affect dolomitiza-
tion. Influences on other diagenetic processes by these fluid inclusions may also be
expected. As to what extent these fluids can be used in environmental reconstruc-
tions remains to be determined by future research (WEBER,1964b).

Non-carbonate components in carbonate sediments

Non-carbonate components in calcareous sediments are inorganic or organic in

composition. The sum total of organic matter from diverse sources has a consider-
able influence on the cation composition of sediments. The non-calcareous material
is either syngenetic, diagenetic or epigenetic in origin according to one consider-
ation (see CHILINGAR et al., 1967) and either detrital or authigenic from another
view-point. When attempting to separate the non-carbonate from the carbonate
fraction, it is significant to consider that not all non-carbonate fractions are
“insoluble” (see WOLFet al., 1966).
GRAF(1960) gave a list of authigenic minerals that have been reported from
carbonate sediments. This list included fluorite, celestite, zeolites, goethite, barite,
clay minerals, phosphate, pyrolusite, gypsum, feldspar, micas, quartz, sphene,
rutile, glauconite-chlorite, tourmaline, pyrite-marcasite, rare carbonate minerals,
and a host of others, that can form at the surface or within the carbonate sediments.
In general, one of the most significant and widespread contaminants of
sedimentary carbonates is the clay fraction. The adsorption and ion-exchange
ability of the clays makes them valuable as environmental indicators that may
assist in distinguishing between fresh-water and marine limestones. DEGENS et al.
(1958) showed that the clay fraction of these two types of calcareous sediments have
significant mean differences in boron and gallium contents; and that the inter-
pretations as to whether they are fresh-water or marine deposits agree in 80%
of the cases examined, where previous environmental reconstructions were based on
fossil evidence. WALKER (1964) has done some similar work on the boron content
of clays. GULYAEVA and ITKINA (1962) found that clays and argillites of fresh-water
facies differ from those of marine deposits in having lower halogen contents and
low CI/Br and Br/l ratios, as given in Table I.
To what extent the observations on the halogens apply to clays derived from
carbonate sediments remains to be seen.
Both skeletal and inorganieally formed carbonate sediments commonly
contain organic matter, in particular in the early stages of sedimentation. In both
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 29

TABLE I

RATIOS OF Br/I AND CI/Br I N SOME MARINE AND FRESH-WATER CLAYS

and ITKINA,1962)
(After GULYAEVA

Marine clays Organic-rich Fresh-wafer clays

marine clays
~- ~

Br/I 8.8- 16.3 5- 6 2.2-2.7

CI/Br 75 -170 45-64 5. I

living and post-mortem stages, the organic matter controls to a marked degree both
minor and trace elements in the bulk composition of carbonate skeletons and rocks,
as mentioned above. For example, GOLDSCHMIDT (1 937), GOLDSCHMIDT et al.
(1948), and KRAUSKOPF (1955) stated that carbonate sediments rich in organic
matter may be enriched in Mo, V, Ni, Pb, Cu, Ag, As, Ge, I, and Br (see also
GRAF,1960). KRAUSKOPF (1955) suggested that Pb, Zn, Ni, and Cu may react with
H2S liberated from decaying organic matter and precipitate as sulfides.
Similar correlations exist between inorganic components and trace elements.
For instance, sediments containing manganese oxide have been known to be
enriched in Co, Mo, and Ba; and phosphatic limestones often contain F and CI in
the structure of the phosphate minerals.
K. G. BELL(1 963) stated that carbonate rocks that are composed wholly of
carbonate minerals and contain only traces of other constituents generally have
about 0.0001 %, or less, of syngenetically precipitated uranium. The impure
carbonates, however, may contain 0.OOOX-O.OOX% of' uranium. This element is
associated with phosphatic, organic and detrital components mainly; and, accord-
ing to K. G . Bell, no appreciable amounts of uranium can be expected in the carbon-
ate fraction itself.
Both the fluid inclusions and numerous types of non-carbonate constituents
mentioned above make it extremely difficult to determine the form of occurrence of
the major, minor and trace elements present in skeletons, minerals and rocks. Thus,
in many studies elaborate techniques had to be devised to achieve a separation of
the different fractions. The chemical data given in Table I1 and 111 can, therefore,
be used only as general guides to the elemental composition of carbonates; much
more research is required before the actual distribution of all elements can be
demonstrated and predicted.
TABLE I1

TRACE-ELEMENT COMPOSITIONOF CARBONATEAND NON-CARBONATECONSTIWENISI

Ag A1 As Au B Ba Be Bi Br C Ca

Limestones P--G P--G P-G P--G P--G

4 p.p.m. 15 p.p.m. 200 p.p.m. 10,000 10 p.p.m.
p.p.m.
Dolomites PG PG P--G P--G
0.5 p.p.m. 65 p.p.m. 2,000 15 p.p.m.
p.p.m.
“Carbonates” P--G P--Gp--G F - G P--G
20 p.p.m. 0.009 6,000 8,000 3 p.p.m.
p.p.m. p.p.m. p.p.m.
“Insolubles” P--G P--G p--G
Clays p--G P--G P-G x
“Heavies” P--G
Organic matter
Bitumen
P-G 8
“Q
Algae S-FM s-V,FM 9
P--v 1.2.10-6 2.10-8 p-v P--v P-v P-v
g/g d.m. g/g d.m. 5
Phaeophyceae P--v s-v p-v 0
P--v
10 mgl 0.044% 43% 64% $
100 g d.m. 1.m. d.m. CaO of 2
ash $ger
Rhodophyceae P--v s-v p-v P-V
1.2 mg/ 0.7% 28% 89 %
5,
2
100 g d.m. 1.m. d.m. CaO tl
of ash w
Chlorophyceae P--v
0.08 mg/
s-v
0.02%
p-v
46%
P-v
60 %
2
!F
1,OOo g
d.m.
1.m. d.m. CaO
of ash ::
Corallinaceae h-V,K
99.3 %
CaC03
 ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 31
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Arthropoda
Trilobita P - G m
25 p.p.m. G
Crustacea P--v s-v s-v B
7.7 % 0.0016% 0.52 % 5
d.m. 1.m. 1.m. F
Echinodermata s-v 0
P-V 0.05 % s-v 0
d.m. 3
Echinoidea h-V
7 10-5%
E
d
8
d. wt. z
Crinoidea
Annelida s-v s-v s-v
6.73 % 0.651 % 2.22 % s-v
v)
m
d.m. d.m. KzOd.m. 8
5
2
- ~~

Mg Mn Mo N Na Nd Ni P Pb Pr Ra
ga
4
Limestones P--G
3,200
P--G
22 p.p.m.
P--G
150
P--G
70 p.p.m.
P--G
100
P--B
58 . 10-14 *
cl

p.p.rn. p.p.m. p.p.m. glg

E
2
Dolomites p--G
4,100
p--G
1.2 p.p.m.
P--G
240
P--G
14 p.p.m.
P--G
8 p.p.m. sE
p.p.m. p.p.m.
“Carbonates” P - G P--G P--G P--G
2,800 70 p.p.m. 100 200
p.p.m. p.p.m. p.p.m.
“Insolubles” P--G
190 P--G
p.p.m.
Clays
P--G P - G P--G P--G
“Heavies”
Organic matter P--G
Footnote is given on p.49 w
\o
TABLE I1 (continued)

Mg Mn Mo N Na Nd Ni P Pb Pr Ra

Bitumen P-G
120 P-G
p.p.m.
Algae p-V,FM
1.0 * 10-6 P--v P-V p-v p-v p-v
g/g d.m.
Phaeophyceae P V P--v P--v P--v P--v
15% 0.015% 4.8 % 34 % 5.9 %
MgO d.m. d.m. NazO PZo5
of ash of ash of ash
Rhodophyceae P--v P--v P--v P--v P--v
15% 0.036% 6.6 % 27 % 46.5 % F
MgO
of ash
d.m. d.m. NazO
of ash
pzos
of ash
r
Chlorophyceae P V P-V P-v P-v P--v
9.7% 0.008 "/, 5.6 22.2 % 4.8 %
MgO d.m. d.m. NazO pzos
of ash of ash of ash
Corallinaceae p-V,G p-V,G P--v h-V,G p-G
II % 0.02% 2.8 % 0.5% 0.8 p.p.m.
MgO d.m. Nan0 CadPWz
of ash of ash wt.
Rryozoa h-V,G h-G FFJ
11% P--v P--v 8.5% p-V
MgC03 CadPO&
wt. wt.
Protozoa
P --G
Foraminifera p-V,G,S, p-H,G,S P--s P-GS
BT 0.1 % <lo"/, 0.01 7;
>25 mol%
"Globigerina p-G p-G P--G P-G P-G
ooze" 2,600 3 p.p.m. 5.5 % 60 p.p.m. 360
p.p.m. Na2O p.p.m.
Porifera h-G,V p-V p-v p-v P-V p-V h-G,V PV
14.1 % 8.4 % 16.7% 9.1 %
MgC03 d. wt. NazO pZo5 E?
wt. of ash of ash
Calcarea P-v
14.1

'
MgC03

Coelenterata
of ash
h-S1 s-v p-SH p-SH p-B
8
0.31 % 13.7% d.m. .
8
0.71 0.028 105
2.2 % 1.m. p.p.m. wt. p.p.m. wt. g/g
Hexacoralla
Octocoralla h-V,G P--v
8z
16.7% 8.6 %
MgCO3 pZo5
wt. of ash
Hydrocorallina h-V,G P-v
8.5 % 1.2%
MgC03 pzo6
of ash of ash
Medusae p-v p-v p-v p-v P--v P-V p-v p-v
0.118% 0.0055% 0.0018% 0.2% 1% 0.003 % 0.33% 0.0043%
d.m. d.m. d.m. 1.m. 1.m. d.m. 1.m. d.m.
Brachiopoda
Inarticulata G-P V
G
P-, P-V,G
6.7% 0.46% 93.7 %
MgC03 Mn304 CadP04h
wt. in ash of ash
Articulata P-V,G PV,G
8.6 % 0.61 %
M&03 Caa(P04)z
wt. of ash
Mollusca s.h-V O-V s-v s-v s-v s,h-V S-V
38% 2.5% S-V 11.6% I .34% 0.004% 5.9% 0.015%
MgC03 d.m. d.m. 1.m. $m. PZOSof d.m.
of residue residue

Footnote is given on p.49 P

TABLE I1 (continued)
~

Mg Mn Mo N Nu Nd Ni P Pb Pr Ra

Pelecypoda p--GJ'G P-V,G, h-G h 4 P-B

TA0,TAI PG 0.40% 1.4 p.p.m. 78 . 10-14
2.8% 440 wt. g/g
MgC03 wt. p.p.rn. Ca3(PO&
Gastropoda pG,KB p4,KB p P G h-G
PG,TAO, PG 438 0.85 % wt.
TAI 2.4% 0.059% p.p.m. Ca3(P04)~
MgCO3wt. wt.
Cephalopoda p-G,TAI p T A I h 4 h-G
7% > 7,000 trace 1 p.p.m.
MgCOa p.p.m.
wt.
Arthropoda

Trilobita l--G
2,700
p.p.m.
Crustacea s,h-V,G
1%MgO S-V s-v s-v S-V pV,G
d.m.; 16 % 0.025 % s-V 16.9 % 0.65 % 50% s,h-V
MgC03 d.m. d.m. 1.m. CadP04h
of ash wt.
Echinodermata S,h-V S,h-V S,h-V S,h-V
15% 0.0028% s,h-V s-v s-v s,h-V 1.12% 0.0021%
MgC03 d.m. Ca3(P0& in tissue
of ash ash residue
Rhinoidea h-G h 4 h-G h-G- h-G
16% 530 -
1 10-5% 2.1 p.p.m. 5 p.p.m.
MgC03 p.p.m. d.wt. d. wt. d. wt.
wt. d. wt.
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 43
e
c;
epq$F
rn- av
>
4 a1
>
E I
0, a
>
I
rn 4
4
s
9
0,
9
>
4 I
rn
>
9 1 QI
a: a t
a
C
0
C
B
'a
.-
rn
3
0
C
c)
0
TABLE 11 (continued) k
Rb Re S Sb sc Se Si Sn1 Sn Sr Tb
~~

Rhodophyceae P-v P-v

44.2 % 16.4%
so8 Si02
of ash of ash
Chlorophyceae P--v P--v
39 % 26.7 %
SO3 SiOz
of ash of ash
Corallinaceae P--v P--v h-G h-G
6.9 % 8.4 % .0.7 p.p.m. 2,200
so3 SiOz p.p.m. A
of ash of ash
Bryozoa P--v P--v h-G
F
8.5 % 16.7 % 3,100
CaS04 Si02 p.p.m.
of ash of ash
Protozoa p
Foraminifera PVS, h-S h-S 3
94.7 % 0.01 % 10%
SiOz
of ash
“Globigerina P--G P--v P-G
ooze” 0.05 % <O.OOol% 160
RbzO p.p.m.
Porifera P--v P--v h-G U
8.6% p-V 99.2 % p-V 1,500
so3 SiOz p.p.m.
of ash of ash
Calcarea P--v
1.97 %
CaSOa
d. ash
Coelenterata P-SH PB
-G
,, P-SH
0.08 s1 0.0058
p.p.m. wt. < 1.2 % p.p.m. wt.
Hexacoralla P--v P--v P--G
0.9 % 1.25% 8,700
CaSO; SiOz p.p.m.
of ash of ash
Octocoralla P--v P-v P-G
5.4 % 1.7% 6,200
CaS04 SO:! p.p.m.
of ash of ash
Hydrocorallina P--v P--v P--G
2.14% 0.63 % 9,300
CaS04 SiOz p.p.m.
of ash of ash
Medusae P--v P--v P--v
0.19% 0.00002 % 0.003 %
1.m. d.m. d.m.
Brachiopoda
Inarticulata P--v P--v
8.37 % 0.9 % P--v
CaS04 SiOz
of ash of ash
Articulata P--v P--v h-G
2.4 % 0.6 % 1,300
CaS04 SiOz p.p.m.
of ash of ash
Mollusca s,h-V S,h-V,B s,h-V
2.82 % 0.6% 92.9%
CaS04 of of residue SiOz of
residue residue
Pelecypoda S-FM h-G p-G,PG,
4.6.10-9 0.8 p.p.m. TA0,TAI
g/g d.m. 10,Ooo
p.p.m.

Footnote is given on p.49 R

 K. H. WOLF. G. V. CHILINGAR AND F. W. BEALES
9
Ir
4
4
E
Y
E
4
G
4
>
9
Y
I
a
Y
4
0 i j >
9
Is:
18
a- 2 I
v)
40
4
0
ea
-8
m
c
*
8 u3
 Th Ti TI Tm U V W Y YtJ Zn Zr

E3
M
Limestones p--C P-G PG,B PG P--G P--G
7 p.p.m. 2,400 1,500 5,350 0.7p.p.m. 13 p.p.m. PG
700
p.p.m. p.p.m. p.p.m. p.p.m.
Dolomites P--G P-G P-G P-G PG F
10,Ooo 5 p.p.m. 160 0.0001% CI
200 0
p.p.m. p.p.m. Ye03 p.p.m. 6
“Carbonates” p--G p--G P--G P--G P - G P--G P--G
Ei
‘Tnsolubles”
7 p.p.m.

P--G
6,000
p.p.m.
P--G
I p.p.m.

P--G
3,000
p.p.m.
80 p.p.m. 500
p.p.m.
340
p.p.m.
P--G
8
8cn
1
Clays P-G PG P-G P-G
“Heavies” PG P--G P-G P--G
Organic matter
Bitumen P--G P-G
150 250
$
Algae
p-v
s-v
9.2. 10--3 p-v
p.p.m. p.p.m.
s-V,FM
2 - 10-5
s-V,FM
4.10-8 p-v
z
P-V +
CI

Phaeophyceae
%
of ash
g/g d.m. g/g d.m.
:s
Rhodophyceae 2
Chlorophyceae cn
Corallinaceae P--G P--G
0.4 p.p.m. 4 p.p.m.
Bryozoa h-TG
0.5 p.p.m. p-V P-v
Protozoa
Foraminifera P-HS h-S
0.01 % 0.01 %
“Globigerina P--G P--G P-G P-v P--G P--G
ooze” 0.15 1,500 10 p,p.m. <0.001% 180 (in insol-
p.p.m. p.p.m. p.p.m. ubles)
- _____ --___
Footnote is given on p.49 P
4
 K. H. WOLF, G. V. CHILINGAR A N D F. W. BEALES
>>
I I
aa
>
l
a
x
>
I
a
78
a0
E
.o
I
cq%
I C ? W
a m
> >
I a
l
a
x
I
>El Ej
I . a
am
 m
Echinodermata S,h-V s,h-V z
h-V h-V 0.123 % 0.018% B
d.m. d.m.
Echinoidea h-G h-G h-TG h-G h-G r
1 . lo-'% 4.8 p.p.m.
d. wt. d. wt.
0.18
p.p.m.
5 p.p.m.
d. wt.
I6 p.p.m.
d. wt.
8
Crinoidea 5
Annelida s,h-V,G 8
12 p.p.m. 3z
'Distribution of elements in carbonate skeletons, rocks and associated components as based on a literature survey. In cases where several values were
available, the maximum value has been used. Future research will result in many changes of the data in Table 11, and many of the blank spaces
~

are expected to be filled in. As only a number of selected publications were surveyed it is essential for those readers engaged in detailed studies to
E!
consult the original literature, p = present, but no other details given; s = present in soft parts of organisms; h = present in hard parts (= skeletal)
of organisms; p.p.m.= parts per million; d.m.= in dry matter; I.m.= in living matter; d. wt.= dry weight; wt.= weight; gig= gram per gram; B=
$
2
BROECKER (1963); BT= BLACKMON and TODD(1959); E = VON ENGELHARDT
of numerous publications; H = HOOPER(1964); K = KONISHI(1961); KB= KRINSLEY
(1936); F M = FUKAr and MEINKE (1962); G = G~~~(1960)+ompilation W
and BIERr (1959); P G = PILKEYand GOODELL (1963, 1964);
*
c)
P H = PILKEYand HOWER(1960); S= SAm (1951); SH= SCHOFIELD and HASKIN (1964); S1= SIEGEL(1965); TAI= TUREKIAN and ARMSTRONG(1961); >
TAO= TUREKIAN and ARMSTRONG (1960); T G = TATSUMOTO and GOLDBERG (1959); V= VINOGRADOV (1953)&compilation. 6
0
z
5
9
TABLE 111
TRACE ELEMENTS IN CARBONATE ROCKS AS GWEN IN VARIOUS PUBLlCATIONS (IN PARTS PER MILLI0N)l

Ele- RANKAMA KRAUSKOPF RUNNELSand SCHLEICHEROSTROM(1957) GRAF(1960, GRAF(1960, table 19)

ments and ( 1955) (1956) table 38)
SAHAMA - average range average
(1950) range average range average

Ag 0.2 0.2(?) 0.1-20 0.9 0.7 &0.4(?)

As 2.5 k1.q?)
Au 0.005-0.009 0.005-0.009 0.005-0.009
B 3 5-300 21 1-200 18 12+ 8(?) < 14,OOO 320
Ba 120 20-200 10-3,OOO 390 10-10,OOO 260 150f110 <5-8,OOO 220
Be 0 <1 1
Br 7
Cd 0.1-0.2(?)
C1 200 460
co 0 0.2-2 4.3 < 5-35 4.3&1.8
Cr 2 5(?) 1-200 13 3-61 11 9k4 t2-100 13
cs 4 +2
cu 20.2 5-20 0.13-500 5 4-70 18 14&9
F 250 320 200-700 320
Fe n.1. n.1. 3,200-46,OOO 11,300
Ga 3.7 3(?) 2.5+1.5 t3-10 2.2+1.2
Ge 0.09
Hg 0.03 0.03(?) 0.07
I 2.8
In 0.02(?)
K n.1. n.1. 300-7,500 1,600
La 14+11(?) <25-50 14&11
Li 26 2-20(?) 20*17 < 1-1,OOO 31
Mn 385 20-6,OOO 850 400-3,700 1,400 5W?)
Mo 0.14.5(?) 0.1-70 44 n.d.-20 1 1.1 &0.7(?)
Na n.1. n.1. tr.-3,300 700
Ni 0 3-10 0.5-100 10 n.d.-70 15 12f4 <5-60 11&1
Pb 5-10 5-10 1-200 16 6-100 26 8 < 10-80 7.2+4.2
Ra 0.42 . 10-6
Rb 0 <loo(?) 7034 < 30-800 60511
Sb 0.2 *o. I(?)
sc 0 0.3(?)
se. t0.1 0.1-1 (?) 0.1-l(?)
Sn 1-200 19 4 10,10,20,20
p.p.m.2
Sr 425-765 -800 14->2,000 470 240-8 10 490 475 f50 <10-6,000 420
Sr Analyses with < 10%Mg0 < 10-6,OOO 484
Sr Analyses with > lO%MgO 1 m 134
Th 1.1 1.910.8
Ti 10-6,OOO tr.-2,400 400 300+150(?)
U 1.3 2.1 *0.2
V < 10 2-20( ?) 5-3.000 n.d.-tr. 15f8(?) <10-150 1213
W 0.5(?)
Y 0 1318 <2&80 1318
Zn 5 50 4-20 0.5-500 35 n.d.-700 40 26*5
Zr 1714 < 10-200 16f3
-~

ln.1. = not listed; n.d. = not determined; tr. = traces

2Four samples
52 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

COMPOSITION OF ORGANIC CONSTITUENTS AND SKELETAL LIMESTONES

A definite interdependence between chemical elements on one hand and living

organisms on the other has been demonstrated; organic processes control and
manipulate elements, and conversely, elements in the surrounding media influence
both fauna and flora. Both the tissues or organic matrices and calcareous skeletons
have revealed enrichment of elements that has proved to be of considerable theoret-
ical and practical interest, or may do so in the future. Some of the elements are
essential to the life processes, whereas others are taken up, so it seems according to
our present state of knowledge, accidentally. Even post-humously, the organic
material influences diagenetic processes as discussed later in this chapter.
High concentrations of such constituents as zirconium, titanium, and thallium
have been recorded. These observations are particularly striking in view of the fact
that some of these elements have not yet been detected in sea water (GOLDBERG,
1957). According to VINOGRADOV (1953), elements that occur in sea water in

TABLE IV
DISTRIBUTION OF ELEMENTS AS PERCENTAGE OF BODY WEIGHT OF ORGANISMS

1937; with additions by MASON,1958)'

(WEBBand FEARON,
~

Invariable (%) Variable

~ _ _ ~
primary secondary micro-constituents Secondary Micro-constituents Contaminants
(60-1) (1-0.05) (<0.05)

H Na B Ti Li He
C Mi3 Fe V Be A
N S Si Br Al Se
0 c1 Mn Cr AU
P K cu F Hg
Ca I Ni Bi
co Ge TI
Mo As
Zn Rb
Sr
Ag
Cd
Sn
cs
Ba
Pb
Ra

'These authors pointed out that this classificationis by necessityarbitrary for some of the elements.
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 53

TABLE V

CONTENT (%) OF ELEMENTS I N DRY ORGANIC MATTER OF MARINE ORGANISMS (DRY MATTER APPROX-
IMATELY 10% OF THE LIVING MATTER)

(After WEDEPOHL,
1964, table 8)

9 types of KALLE Plankton Algae Plankton Plankton

organisms, (1943) VINOGRADOV BLACKand NICHOLLSFUKAI and MEINKE
Gullrnarflord (1953) MITCHELLet al. (1959, 1962)
(Southwest (1952) (1959) and others
Sweden)
NODDACK and
NODDACK
(1939)

Fe 6.9. 1 (Phyto- 5 ' 10-2-10-' 6.9 * 10-2

plankton); (Cyanophyceae) (Phyto-
4 10-2 1 (Peridiniaceae) plankton)
(Zoo- 2-10-1
plankton) (Diatomaceae)
Zn 4.5- 10-2 2 . 10-2 8 . 10-3
Mn 1.2- 2.10-3 4.10-5 9.10-3
(Cyanophyceae)
4 . 5-5-2. 10-2
(Diatomaceae)
v 8.5. 10-3 3 . 10-3 3.3. 10-2 2.10-4 10-3 2.5 . 10-4
(Cyanophyceae)
cu 3.0.10-3 5.10-3 10-3 2.8.
Ni 2.1 * 3.7. 10-4 3 .10-3
Pb 1.3. 8.4. 10-4 10-2 5 . 10-5-2 * Pb:
MALJUGA(1 939);
1.2 . 10-3 (micro-
plankton):
LAEVASTU and
THOMPSON (I 956)
AS 1.1.10-3 10-4 n.d.l 7.10-5
Sn 8.2. 1.1 . 10-4 7.7. 10-4
Ti 5* 10-1 3 . 10-3 4 10-4
Ag 3.3 * 10-4 3.10-5
MO 3.10-4 3.9. 10-5 3.9. 10-4 8 * 10-5;
(microplankton):
SUGAWARA et al.
(1961)
co -
2.1 10-4 5.10-5? .
7. I . 10-5 9.5 10-4
B 9.4. 10-3
C 30 30 (Peridiniaceae, Cyanophyceae)
11-25 (Diatomaceae)

1n.d. = not determined.

54 K. H. WOLF, G. V. CHlLlNGAR AND F. W. BEALES

amounts larger than are concentrated by organisms 10-100 times that

amount. Some of the elements present in the ocean in quantities less than
are also organically utilized. Radioactivity of lake plankton reaches 100 times the
radioactivity of the water in Quirke Lake, Ontario.
MASON(1958) discussed the work of WEBBand FEARON (1937) and gave
updated information on the elements found in biological material which can be
classified as structural elements (C, H, N, 0, P, S, C1, Na, K, F, Mg, Si, Ca) and
biocatalysts (Fe, Cu, B, Mn, I). Table IV gives some idea on the elements present
in organisms. (See also Table V.) When these data are plotted on the periodic table
(see MASON,1958, fig.37) it becomes clear that these elements (except iodine) are
invariably all of low atomic number. HUTCHINSON (1943) has shown that there is a
relationship between the elements incorporated in organisms and ionic potential of
the ions (see also MASON,1958, fig.38).
It has been most difficult to prepare a summary of representative data on
trace elements of carbonate material for various reasons. In many cases IIO clear
distinction has been given in the literature on whether the analyses were carried
out on either the calcareous skeletal parts, or the organic tissue, or both. Frequent-
ly, no indication has been offered to what extent contaminations and adsorbed
components may have contributed to the trace-element composition. In precise
studies, bulk compositions of organisms and carbonate sediments are of little use
except in giving some rough estimations. The tables given here must, therefore, be
considered only as an approximate guide. This is particularly true because only
one, two or three specimens were analyzed in a number of cases.
The manifold factors that determine the composition of carbonate skeletons
and skeletal limestones are considered further under the following headings: ( I )
indirect and direct organic influences; (2) aragonite versus calcite, and other
skeletal minerals; (3) magnesium in skeletons; ( 4 ) strontium content of skeletons;
(5) other elements in skeletal and protective structures of organisms; (6) organic
matter associated with carbonates; (7) direct bacterial influences. A number of
other factors are discussed in the section on the application of composition to
geological problems.

Indirect and direct organic influences

Although details on the direct versus the indirect influences of life processes are
given in various sections, the discrimination between them is of the utmost
importance and warrants special attention. Where recognizable calcareous skele-
tons form the major part of carbonate sediments, the direct contribut,ionof organ-
isms is readily apparent. On the other hand, it may be problematic, if not impossi-
ble, to estimate the contribution of the tissues of organisms to the trace-element
composition of carbonate sediments. Even less clear are the indirect influences of.
for example, algal and bacterial processes. It is the contention of most workers that
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 55

organisms are the major contributors to the formation of limestones. It is entirely

possible that no carbonates were deposited prior to the origin of life very early in
Precambrian time, and that subsequent to that time organic influences have domi-
nated the global COz-carbonate budget. Element extraction and utilization within
any environment of carbonate deposition will, therefore, have been subject to this
overriding control.
Among the non-calcareous Algae (i.e., those that do not form a carbonate
skeleton), some can cause chemical changes in the water medium that results in
“inorganic” precipitation of carbonates. ALDERMAN and SKINNER (1957) stated:
“Our observations have shown that carbonate precipitation can take place in

TABLE VI

DIS’I?(IBUTION OF SKELETAL MINERAL SPECIES ACCORDING TO PHYLUM

(After LOWENSTAM, 1963, fig.2; see also CHAVE, 1962, for a table on mineralogic composition of
skeletons; and for bacterial products see VINOGRADOV, 1953, and GREENFIELD, 1963)

Carbonates
Aragonite ? + + + + + + + + +
Calcite ? + + + + + + + + + +
Aragonite plus calcite ? ? + + + + +
“Amorphous” ? + + +
Silicates
“Opaline” + + + ?

Phosphates
Hydroxyapatite + -I-
Undefined
plus calcite
+ ++
Oxides
Magnetite +,
Goethite
+
T

Magnetite plus goethite

Amorphous (Fe) +
plus aragonite +
Surfates
Celestite
Barite
+
?
56 K. H. WOLF, G . V. CHILINGAR AND F. W. BEALES

waters which have only half the salinity of average sea water. Precipitation of
carbonates in such solutions could be brought about by a rise in pH. The presence of
vigorous plant life in water can have a very considerable effect on the pH of the
.
solution.. extraction of C02 from lake water by plants during photosynthesis
can raise the pH to 9.3 in strong sun-light. The pH may fall to below 8 at night as
the water absorbs C02 from the air."
Many ancient stromatolites, probably formed by Algae, are not thought to
be the product of direct inorganic and/or organic precipitation of calcium carbo-
nate, but to have been produced by the binding of fine calcareous (and other)
debris by algal filaments and cells. Whatever the derivation of the calcareous detri-
tus may be, the metabolic algal processes will result in enrichment and/or depletion
of the chemical elements in the associated debris. The originally inherited compo-
sition of the bound particles will, therefore, change. This complex picture is
further complicated by the presence of Bacteria that utilize the algal tissue as
nutrient.

'I
S
m
0
0

.-
0
I:
c
m

I I

I P

?
P

P
0
P

3
r
3

Fig. 1 . Time-stratigraphic distribution of silica (S)- and phosphate (P)-secreting organisms. Width
of bars indicates relative importance of groups. (After LOWENSTAM, 1963, fig.10; by permission of
University of Chicago Press, Chicago, Ill.)
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 57

Fig.2. Time-stratigraphic distribution of important carbonate-secreting organisms. Width of

bars indicates relative importance as contributors to sediment. C=calcite; A =aragonite. (After
LOWENSTAM, 1963, fig.12; by permission of University of Chicago Press, Chicago, Ill.)

Aragonite versus calcite, and other skeletal minerals

Calcareous skeletal parts are composed mainly of aragonite and/or calcite. As

these polymorphs reflect biological and environmental factors, and because the
crystal lattice of each determines the type of elements present and the degree of
substitution for Ca, polymorphism must be given due consideration in the study of
chemical composition. The following four major mineralogic groups can be rec-
ognized: high-Sr and low-Sr aragonite, and high-Mg and low-Mg calcite. In
recent calcareous material vaterite may also be present. (See INGERSON,1962, for
an excellent review.)
Fig.1 and Table VI, based on findings of LowENsTAM (-1963),illustrate that in
addition to the various forms of calcium carbonate some skeletons contain silica,
phosphate, iron oxide, and sulfate. These non-carbonate components are not only of
significancethemselves, but may also be important as adsorbants of trace elements.
The approximate geologic ranges of the important calcite- and/or aragonite-
secreting organisms are given in Fig.2. Most of the aragonite and high-Mg calcite
that formed part of the Paleozoic and younger limestones have inverted to calcite.
The factors determining the predominance of aragonite over calcite are numerous
and complex. LOWENSTAM (1954a, b, 1963) has paid particular attention to the
58 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

temperature-dependence of the aragonite/calcite ratio. LOWENSTAM (1954a) divided

organisms secreting calcareous shells into four types: (I) orders composed of forms
that secrete skeletons entirely of aragonite, but in which the number of species is
markedly greater in the warmer than in the colder water; (2) classes or subclasses in
which all species of a given order secrete either all calcite or all aragonite, but in
which the orders with aragonite-depositing species are confined to the warmer
waters; (3) a transitionary type from type 2, containing species which differ from
those in category 2 in that they secrete trace amounts of calcite in the colder
climates, in their marginal geographic ranges; and ( 4 ) genera with species the skele-
tons of which are composed of mixtures of both aragonite and calcite, with the
aragonite content increasing with higher temperatures and the calcite with lower
temperatures, the temperature effect depending upon the species.
The “species effect” is particularly marked in the mollusca. Their mineralogic
composition and their temperature responses differ distinctly from genus to genus,
and also within genera from species to species. In some organisms the aragonite, for
example, is confined to particular localities in the skeleton. STENZEL (1963) reported
on oysters that are mainly composed of conchilin and calcite, and have five small,
but distinct, areas composed of aragonite (the resilium and four muscle pads).
Of particular interest are the observations made by WATABE and WILBUR
(1960) who performed both in vivo and in vitro experiments with organic matter.
They demonstrated that the precipitation of aragonite versus calcite in molluscs
is determined by the protein matrix. In a subsequent study, WILBURand WATABE
(1963) found that the crystal growth and formation of organix matrix of shells
takes place from a thin layer of extrapallial fluid enclosed between the mantle and
inner shell surface. “Composition of this fluid presumably affects the submicroscop-
ic pattern of the matrix which in turn influences the polymorphic type of CaC03
crystals deposited upon it. In vitro experiments have demonstrated that aragonite
formation is favored by appropriate concentrations of inorganic ions and certain
amino acids and that vaterite is favored by amino acids and glycoprotein (Y. Kita-
no, personal communication). Temperature had a marked effect on the ratio of
CaC03 polymorphs. In regenerating Viviparus shell and in one strain of Coccolithus,
vaterite was deposited in relatively high proportion at lower temperatures, whereas
at higher temperatures vaterite decreased and aragonite increased.” Nitrogen
deficiency had two effects on Coccolithus (an alga): (I) one strain formed plates of
CaC03, although it formed no plates in normal medium, and (2) another strain
deposited very considerable amounts of vaterite, aragonite and calcite in a nitro-
gen-deficient medium, whereas under normal conditions only calcite was deposited
(see also W. D. EVANS,1964). Similar complexities have been pointed out by
SIMKISS (1964), who stated that calcite, aragonite, and vaterite have been found in
certain specimens of molluscs and marine Algae (i.e., coccolithophorids).
The foregoing examples illustrate the control of the organic matrix, both
in vivo and post-mortem, on the polymorphism of calcium carbonate. To what
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 59

extent it influences in turn the minor and trace-element contents is not known in
precise terms. CHAVE(1954a) observed that different parts of the same specimen
of an organism, despite being composed wholly of either calcite (e.g., echinoids)
or aragonite, may vary in composition. This may well be a reflection of different
composition within the organic matrix.
Magnesium in skeletons
In his monograph on the elemental chemical composition of organisms, VINO-
GRADOV (1953) pointed out that one can recognize three groups of similar calcitic
skeletons: ( 1 ) those with a small MgCOs content (Cirripedia, Mollusca); (2) those
with a labile amount (Foraminifera, Bryozoa); and (3) those with continuously
high MgC03 content (all Echinodermata, Corallinaceae, and Alcyonaria). Inas-
much as large MgC03 concentrations are found in skeletal calcium carbonate, espe-
cially in warm seas, Vinogradov suggested that the MgC03 precipitation is a second-
ary phenomenon and is more energetic when the ,Ca metabolism is more intensive.
Vinogradov also pointed out that invertebrates with calcite skeletons that
contain large quantities of MgC03 are typically marine organisms and are not
present in fresh-water environments, e.g., Echinodermata, Alcyonaria, Calcarea
and Corallinaceae. They are also absent in salt lakes such as the Caspian Sea; but
some have been reported from the Red Sea and can withstand higher salinities
than has been assumed hitherto. If organisms, such as the calcitic, Mg-containing
Foraminifera, migrate into fresh water they lose their calcareous skeletons (with
rare exceptions). Some invertebrates, upon adaptation to fresh-water conditions,
lose Mg first of all from their marine “blood”.
CHAW(1954a) found that, with the exception of a few cold-water calcitic
forms, aragonitic skeletons are lower in Mg than the calcitic types, and that in all
groups of calcitic organisms there is a linear or near linear relationship between
the Mg content and the temperature (see also CHILINGAR, 1953, 1962a). CHAVE
(1954a) also found that the total amount of Mg in skeletons decreases with an
increase in phylogenetic level of the organisms. Although other factors, like salinity,
depth of water, age or size of the individual organism, may be influential, Chave
found little evidence of this. Subsequent research, however, led to modifications of
the above generalized conclusions which are dealt with later in this chapter.
CHAW(1954a) pointed out that the mineralogy of the organic skeletonsis
complicated by the ability of some organisms to secrete both calcite and aragonite.
As aragonitic forms seldom contain more than 1 % of MgC03, whereas the calcitic
types rarely have less than 1 % MgC03 and in some cases up to 20-30%, the bulk
composition of an organic skeleton depends to a large degree on the aragonite/
calcite ratio. This can be shown, for example, in the case of gastropods and pele-
cypods in which the presence of a few percent of calcite results in a distinct increase
in Mg content. A similar relationship occurs in the annelids in which serpulid tubes
are composed of calcite, aragonite, or a mixture of the two. The aragonite content
60 K. H. WOLF, G. V. CHlLlKGAR AND F. W. BEALES

increases with increasing temperature (LOWENSTAM, 1954b). Hence, the Mg content

of the whole tube increases with higher environmental temperatures to a certain
point due to the increase of Mg content in the calcite portion of the tube. The Mg
content then decreases as the amount of aragonite becomes large, although the
Mg proportion in the calcite continues to rise with the higher water temperature.
CHAVE ( I 954a, b) cited an example of a Serpula tube composed of 70 % calcite and
30 % aragonite, with the former containing 13% of MgC03 and the latter less than
1 %. The bulk analysis showed approximately 9.4 % MgC03.
Other complicating factors can only be evaluated by future research. For
example, CHAVE (1954a, b) noticed that in the case of calcitic Algae, the correlation
between water temperature and the Mg content is less perfect than in any of the
other classes and phyla. This may be partly a reflection of the diverse taxonomic
position of the Algae. Based on his observations, Chave concluded that the total
Mg content is not characteristic of groups of organisms; however, the slopes of
the temperature versus Mg-content curves are characteristic for different groups.
Although this may be the case in some phyla, more recent studies have shown that
both the ratios of the CaC03 polymorphs and their compositions are not always
a direct function of temperature.
BLACKMON and TODD(1959) showed that no combination of aragonite with
calcite occurs in the Foraminifera, i.e., they are composed of either one or the
other. This simplifies somewhat the consideration of bulk trace-element variations.
It was also found that: (I) certain genera were aragonitic in both arctic and tropical
waters, (2) certain other genera were always calcitic irrespective of environment, and
(3) both calcitic and aragonitic genera are present in the same habitat. It seems,
therefore, that a phylogenetic control rather than physicochemical influences
determines whether either calcite or aragonite is deposited. This in turn controls
the amount of Mg that can be taken up. Competition and selection, however, will
ultimately develop a stable organic community in which this phylogenetic control
may be subordinate to the physicochemical background.
Such considerations greatly complicate the interpretation of results. The
Mg content in the calcitic shells of most Foraminifera falls into a low (0-5 mol%)
or a high (10 mol% or higher) range, with very few skeletons being in the inter-
mediate range. The results given in the tables by BLACKMON and TODD(1959)
suggest that mainly phylogenetic factors influence the proportion of Mg in the
shells. They found some evidence, however, that cold water has a noticeable effect
on Mg content. The genera from normally high-Mg families existing in arctic or
deep tropical waters show varying degrees of incorporation of Mg, but do not
exhibit a fixed rate of decrease of Mg content with decrease in temperature. The
rate varies with the different genera. Every specimen from a normally high-Mg
group indicated some decrease in Mg content where the water temperature was
below about 20°C. Significant is the fact that the converse is not true. Where
low Mg content is normal for a group, higher temperatures do not tend to increase
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 61

the Mg content above 5 mol%. Also some families of Foraminifera provide evi-
dence that there is some relationship between the thickness of the shell and the
amount of Mg.
The observations of TUREKIAN and ARMSTRONG (1960) that “molluscan
genera, which have species with some calcite in the shell structure, are generally
high in Mg, and this obtains even when a species of such a genus has no calcite in
it at all”, strongly suggests that a generic control of Mg is more important than the
aragonite/calcite ratio. They also concluded that in addition to Mg, Sr, and Ba,
trace-element contents in recent molluscs appear to be controlled by phylogenetic
factors, although this is obscured by individual differences.
Contrary to the findings of CHAVE (1954a), TUREKIAN and ARMSTRONG (1961)
reported that the snails as a group are higher in Mg content than the clams.
(For additional data on relationship between the Mg content and temperature see
the section on ecologic implications in this chapter.)
An interesting correlation between elements was given by VINOCRADOV
(1953), who stated that the greater the amount of phosphate in eunicid worms,
brachiopods, Bryozoa, and Crustacea, for example, the higher is the Mg content.
NEWELL and RIGBY(1957) reported that “it is well established that limestone
outcrops between low and high water levels show enrichment of Mg, and this
certainly is not limited to the shores of hypersaline seas . , . ; nor is there evidence
that it is an effect of differential leaching of the more soluble calcium carbonate”.
They also stated that on Andros Island of the Bahamas the oolitic limestone sur-
faces in the intertidal zone show a slight but persistent enrichment in Mg (3.9-
9.4 % MgC03). This chemical composition is comparable to the (1) intertidal muds
of Western Andros, (2) lime-muds of the fresh-water lakes (5.7-9.5 % MgCOs), (3)
deep-sea ooze from the Tongue of the Ocean (5.4-7.2 % MgCOs), ( 4 ) mud polygons
bound by blue-green algal filaments (5.2-19.4 % MgCOa), and (5) laminated
limestones (6.9-8.3 % MgC03). The relatively high Mg content of all of the above
sediments may be due to a similar cause. One common denominator of these Mg-
enriched sediments is the intimate association with blue-green Algae, which, ac-
cording to NEWELL and RIGBY(1957), seem to extract magnesium carbonate from
both fresh water and sea water.
The role of Bacteria has been investigated by CARROLL and GREENFIELD
(1963) who showed that “these organisms are capable of -concentrating calcium
and magnesium up to 10 times that of an equivalent volume of sea water. . . the
alkaline earths are partly adsorbed, partly hydrogen-bonded, and partly complexed
in or on the bacterial cell envelope”.

Strontium content of skeletons

Strontium is, next to Mg, the most important element that has attracted the atten-
tion of many research workers, and cpnsequently a considerable amount of
TABLE VII
Sr/Ca RATIOS OF ORGANISM+

REVELLETHOMPSON and CHOW ODUM(1950a, 19576) KULPet al. (1952) Culvert ODUM(1957))
and FAIR-(1955: see GRAF,1960, GRAF(1960, table 3-17) (variousformations Formation (modern
BRIDGE table 3-14) Average values as old as Proterozoic) (Miocene) specimens)
(1957)

Marine Algae calcitic Algae 3.96 0.1&1.80 0.49-13.00

aragonitic Algae 10.82 (listed as Algae) (listed as
calcitic fresh-water Algae 0.52 Algae)
Chlorophyta (green) 14-16
Phaeophyta (brown) n.d.
Rhodophyta (red)
Nemalionales n.d.
Cryptonemiales
(corallines) 2.93-3.45 2.93-3.45(3.20)
Chrysophyta
(golden brown)
Coccolithophores n.d. p
Protozoa c
Foraminifera 2.78-3.28 2.78-3.28(3.07) littoral Foraminifera 2.07 1.86-2.77
Porifera
Calcarea 2.30-3.34 2.30-3.3q2.99) calcitic marine sponges 3.82 1.1-1 2.90
Coelenterata Corals 0.12-1.62
Hydrozoa 6.83-1 1.2 2.73-1 1.2(8.69) aragonitic 11.02 (0.22) 2.0-1 1.40 k
Alcyonaria 2.64-7.57(4.04) calcitic 4.10
aragonitic 8.06
Coenothecalia
(Heliopora) 7.57
All others 2.64-3.78 aragonitic 10.80
Zoantharia m

E
m
(Madreporaria) 8.85-10.7 8.85-10.7(9.86)
Annelida 12.00
Serpulidae 3.86-8.24 3.868.24(5.87) aragonitic marine 3.10
Bryozoa 3.00-3.94 3.00-3.94(3.4 1) calcitic marine 3.96
Brachiopoda calcitic marine 1.81 0.36-0.78 (0.66)
(Articulata) 1.20-1.57 1.20-1.57(1.36) (Telotremata) Inarticulata 4.75
Echinodermata 0.21-0.22
Crinoidea 2.56 2.56 calcitic marine 3.38 0.20-0.80 (0.45)
Asteroidea 2.60-2.89 2.60-2.89(2.73) calcitic marine 3.71
Ophiuroidea 2.63-2.78 2.63-2.78(2.69) calcitic marine 3.47
Echinoidea 2.46-2.89 2.4&2.89(2.70) calcitic marine 3.06
Holothuroidea 2.72-2.78(2.74) calcitic marine 2.60
Mollusca v)
m
Amphineura 7.32-9.35 7.32-9.25 (8.06) aragonitic marine 9.01 El
Pelecypoda 1.01-2.98(1.85) aragonitic marine
aragonitic fresh-water
2.63
0.87 0.81-2.95 1.6-7.4 0.2 1-3.6 5*
-I

Pectinidae,
calcitic marine 1.65
z
Ostreidae,
Anomiidae 1.01-1.33 *
c1

All others 1.19-2.91 6

Gastropoda 1.25-2.48 Prosobranchia 1.25-2.48( 1.68)
Opisthobranchia 9-1 l(10)
aragonitic fresh-water
aragonitic marine
0.75
2.31
0.12-0.1 6 1.8-3.5 0.02-6.74 P1
Scaphopoda 2.35 2.35 aragonitic marine 2.35 3.8-3.9 2.00-2.32 E
Cephalopoda 3.74 3.74 aragonitic marine 4.86 0.7-1 .OO (Belemnires) 3.874.70
calcitic marine 4.60 1.7-2.5
Arthropoda 0.62-7.30
Cirripedia 3.77-5.28 3.77-5.28(4.45)
Crustacea marine (calcite and
(Decapoda) 6.00-6.69 6.00-6.69(6.17) amorphous CaC03) 6.03
calcitic fresh-water 0.62
Crustacea
(Ostracoda) n.d. n.d.

1Atoms Sr/1,000 atoms Ca; n.d. = not determined.

64 K. H. WOLF, G. V. CHILINGAR A N D F. W. BEALES

information is available concerning this element. Table VII, VIII and IX give the
Sr/Ca ratios as based on some selected publications. KULPet al. (1 952) and ODUM
(1957b), among others, stated that the Sr/Ca ratio in organisms primarily depends
(I) on the Sr/Ca ratio in the water medium; (2) on the salinity; (3) on the phylo-
genetic factors; (4) on the temperature and crystal lattice (polymorphism), which
are thought to be of secondary significance by some; and (5) on possible other, as
yet poorly understood, influences.
KULPet al. (1952) investigated a large number of fossil specimens from one
horizon of the Miocene Calvert Formation. The 23 species collected represent 23
genera, all of which exist today. The investigation showed that the Sr contents of a
particular Miocene genus are relatively constant.
Also, the investigations of Kulp and his co-workers suggested that, except
for certain individuals, the Sr proportion is quite constant within a class (Table
VIII) ranging from the Cretaceous to the Recent. This agrees with ODUM’S(1950a)
results on various other animal types. The results of KULPet al. (1952), however,
did not show agreement when samples as old as the Proterozoic were included
(Table VIIl). They also could not find annual trends in Sr precipitation by organ-
isms. It seems that for a given environment the fossils have the same Sr/Ca ratio.
On the other hand, other organisms are selective and some show enrichment in Sr
content. Worm tubes, for example, exhibit a very much higher Sr/Ca ratio than do
molluscs.

TABLE VIII

RANGES OF Sr/l,Oo Ca RATIOS IN SOME GASTROPODA AND PELECYPODA OF VARIOUS AGES

(After KULPet al., 1952)

Sample Cretaceous Eocene Miocene PIiocene Recent

Lower Middle Lower Upper

Gastropod
Turritella 1.67 2.01 1.60 1 .72 2.58 2.48 2.52
4.15 1.69

Variousformations (extending Calvert Formation,

back to the Proterozoic) Miocene

Various 0.12-0.16 1.8-3.5

Gastropoda
Various
Pelecypoda 0.81-2.95 1.6-7.4
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 65

TABLE IX

SUMMARY OF THE Sr ABUNDANCE DATA IN CARBONATES

(After KULPet al., 1952; and others)

Reference Sr/l,OOOCa

Average of 155 limestones KULPet a]. (1952) 0.71

Average of 40 limestones ODUM(1950a) 1.21
Range of 78 Paleozoic limestones KULPet al. (1952) 0.1 1-3.90
Average of 78 Paleozoic limestones KULPet al. (1952) 0.76
Range of 25 Paleozoic limestones ODUM(1950a) 0.3-1.4
Average of 25 Paleozoic limestones ODUM(1950a) 0.9
Average of 155 fossils from 3.10
Calvert Formation (Miocene)
Average of 103 uncrystallized fossils 2.76
(Brachiopoda, Pelecypoda, Gastropoda
Average (198) of all fossils studied 1.88
(including many recrystallized)
Deep-sea calcareous ooze TUREKIAN(1957) 2.8-ca.24.0 (Sr/Ca)
Recent carbonates of North America SIEGEL
(1961) 8.3-13.6

In contrast, BOWEN(1956) stated that the amount of Sr in recent corals is

much greater than that in fossil corals. An approximate linear relationship exists
between the Ca/Sr ratio and geological time as far back as the Devonian period; the
results obtained for the Silurian period are anomalous. Bowen suggested that Sr has
accumulated in sea water progressively. This interpretation, however, is opposed by
many others working on the geochemistry of strontium. Again it is apparent that
the interpretation of results is a complicated matter. It is reasonable to assume that
modern aragonitic corals will lose Sr when the aragonite is recrystallized to calcite.
Also, bearing in mind that numerous workers have considered that Paleozoic rugose
corals secreted calcite skeletons, the results for the Silurian period may reflect
taxonomic variations below the class level.
Comparing the Sr contents of ancient samples with those from Miocene
formations, KULPet al. (1952) obtained the distinct differences shown in Table
VIII. The analyses of Recent and Pleistocene corals by SIEGEL(1960; in press)
indicateaslightly lower value for average range of Sr content in Pleistocene specimens.
To what extent secondary changes have influenced the compositions cannot
be evaluated here and discussions on the related problems are to be found in the
section on diagenesis.
The influence on the Sr contents by the water medium, the effects of calcium
carbonate polymorphism, and the phylogenetic level of the organisms are consider-
ed next, whereas discussion of influences of salinity and temperature is deferred to
the section on paleontologic and ecologic implications.
66 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

Composition of water medium in determining Sr content

It has been demonstrated by a number of investigators, and supported by tracer

studies, that large quantities of Sr can be taken up in shells, and that the Sr/Ca
ratios in the skeletons of animals and plants are almost directly related to the Sr/Ca
ratio in the environment (see summary by ODUM,1950a, 1957b; KULPet al., 1952).
Take-up of Sr is reduced relative to Ca, however, leading to a Sr/Ca ratio that is
usually lower than the ratio determined for the environmental medium (see section
on “Phylogenetic effects”, below).
The extraction of Sr from the water medium may have a notable influence on
the chemistry of shallow-water regions. LOWENSTAM (1954a) pointed out that Sr
fixation is particularly high in aragonitic scleractinian corals and aragonite-secret-
ing Algae on tropical reefs, and suggested that this is probably the cause of the
relative Sr depletion of the waters in the vicinity of the reefs compared to temperate
and arctic waters. The removal of Sr apparently occurs at a faster rate than the
replenishment of Sr by mixing. Thus, the question comes to mind as to what
degree Sr depletion occurs, and to what extent the depletion affects other organisms
and the trace-element content of inorganic carbonates in the vicinity of the reefs.

Calcium carbonate polymorphism aflecting the Sr content

ODUM (1957b) stated that questions pertaining to the relationship between organic
carbonate polymorphs and the Sr content are largely unsettled, for in some cases
aragonite of fresh-water mollusc shells may have much less Sr than calcite skeletons
of marine species. ODUM(1957b) concluded, therefore, that although on the statisti-
cal average one finds more Sr associated with the aragonite crystal lattice than
with calcite, in any particular sample other factors are also operative. KULPet al.
(1952) also pointed out that the crystal form is only a secondary factor. Never-
theless, some very general trends are obvious as indicated in Table X.

Phylogenetic eflects which determine the Sr content

A number of observations seem to suggest that the “species”, “generic”, or “phylo-

genetic” effect, as it is variously called, is a major, if not the most important, con-
trolling factor determining the Sr content in organic calcium carbonate as pointed
out by TUREKIAN and ARMSTRONG (1960), among others. For example, in general
the Sr content varies greatly in aragonitic pelecypods. Although the Sr content in
calcitic types is lower, the latter overlap with aragonitic clams having a low Sr
content. This indicates the importance of generic control of test secretion in
molluscs. Also, clams as a group have higher Sr content than snails. Turekian and
Armstrong emphasized the “generic” effect on Sr concentration but recognized that
this is often obscured by other causes.
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 67

TABLE X

AVERAGE Sr/Ca ATOM RATIOS, TIMES 1000, CONTRASTED FOR CALCITIC AND ARAGONITIC SKELETAL
MATERIALS

(After THOMPSON
and CHOW,1955)

Calcite (excluding aragonitic Calcite-aragonite Aragonite (excluding

species) mixtures (excluding calcitic species)
completely calcitic
species)

Algae, Corallinaceae 3.20 Mollusca Coelenterata

Protozoa, Foraminifera 3.07 Pelecypoda 1.94 Hydrozoa 9.49
Porifera, Calcarea 2.99 Zoantharia 9.86
Coelenterata, Alcyonaria 3.16 Gastropoda Mollusca
Arthropoda, Cirripedia 4.45 Prosobranchia 1.68 Arnphineura 8.06
Mollusca Gastropoda
Pelecypoda Nudibranchia 10
Anomiidae 1.22 Scaphopoda 2.35
Ostreidae 1.22 Cephalopoda 3.74
Pectinidae 1.31
Bryozoa, Ectoprocta 3.41
Brachiopoda, Articulata 1.36
Echinodermata 2.71

ODUM(1957b) showed that there is a distinct difference in Sr/Ca ratio of

aragonitic pelecypods, gastropods and calcitic Algae, to name only a few, from
fresh water in contrast to those from sea water. In some cases, the marine-water
specimens have a higher value by a factor of six. The Sr/Ca ratio is not, therefore,
a taxonomic constant for large groups, but the distribution pattern may never-
theless be a distinct taxonomic property (ODUM,1957b). Only where the external
conditions are relatively constant, as in certain marine environments, are the
Sr/Ca ratios predictable from the taxonomic position alone. In general, however,
it is now established that some genera, families, orders, and phyla are characterized
by a certain range of Sr/Ca ratio values.
ODUM(l957b) suggested that in addition to tissue and mineralogical food
chain1 differences it appears that some other factors appear to be operative in
controlling, for example, the high Sr/Ca ratio in reef corals and low ratio in pelagic
Foraminifera, pelecypods and brachiopods. Odum stated in his section on Sr-
turnover and isolation of depositional surfaces, that a partial answer may be
found in the same phenomenon inside organisms that may occur in the geochemical
cycle of isolated environments. In both cases, the precipitation of Sr-poor calcium

'Different organisms use different types of food from which they extract different trace elements
to build their tissue and skeletons.
68 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

carbonate will increase the Sr/Ca ratio in the surrounding depositional medium.
In regard to organisms, ODUM(1957b, p.65) stated: “The exclusion of Sr from the
crystal deposition tends to raise the Sr/Ca ratio in the surrounding tissues. If
deposition takes place under a steady state condition which involves little free
ionic exchange with the external medium, the Sr/Ca ratio will be higher both in the
tissues immediately around the deposition and in the deposition itself. If there is
free exchange with the environment, the Sr/Ca ratio of the immediate chemical
environment of the deposition will be little altered by the deposition and a steady
state condition will result with the lower Sr/Ca ratio both in deposition and sur-
rounding tissue. Rapid deposition or slow exchange will tend to raise the Sr/Ca of
tissue as noticed by SWAN(1956). Rapid circulatory systems, efficient excretory
systems, and planktonic existences, all tend to lower the Sr/Ca ratio by this pre-
diction. On the other hand, deposition in enclosed places deep in tissues not closely
connected with exchange membranes will lead to higher Sr/Ca ratios.” The ex-
perimental graph (Fig.3) drawn by ODUM(1957a) appears to support the “ex-
change theory” that controls the Sr/Ca ratio.

E
t Sr/Ca Atoms per 1000 atoms

3
2
s
._
Kidnev
strbng

4
L
Moderate
U
:. Weak

,“
L

Flamecells
*
m Diffusion
c
t Planktonic
Currents
Sessile

None

Separation of calcification surface f r o m

exchange with thesea

Fig.3. A semi-quantitative graph relating the Sr/Ca ratio of skeletons of various groups of organ-
isms to the rate of turnover of substances in the depositional tissue. The vertical coordinate: the
strength of the excretory and circulatory systems of the organism ranging from no circulation to
a strong kidney. The horizontal axis: the thickness of the tissue separating the calcification sur-
face from the sea. An effort has been made to draw isopleths of approximately equal Sr/Ca
ratio. Species with poor exchange due to poor circulation and thick separation from the sea in the
lower left corner of the diagram seem to have higher Sr/Ca ratios. Species with exposed calcifica-
tion surfaces and good circulation provided either internally or due to planktonic existence are
presented in the upper right side of the diagram, and are characterized by lower Sr/Ca ratios.
(After ODUM, 1957a, fig.2; by permission of the Institute of Marine Sciences, Texas University.)
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 69

LIKINS et al. (1963) performed interesting experiments that demonstrated the

difference between the vital (= organic, metabolic) and non-vital (e.g., physico-
chemical surface exchange) uptake of strontium into aragonite. The experiments
were performed on the ( I ) living fresh-water snail (Australorbis glubrutus) with
aragonitic shell; both the pre-test (= preformed) shell and newly, metabolically
deposited shell material (precipitation was induced by removing some of the origi-
nal shell) were tested; (2) aragonitic shell (snail-free) of a dead snail, and powdered
shell material of the same snail; and (3)artificially precipitated aragonite and calcite.
On exposing these three groups of materials to a number of solutions with varying
concentrations of strontium and calcium, LIKINSet al. ( I 963, p.276) concluded
from the results that there is a " . . . marked discrimination against strontium
relative to calcium in new shell formation which decreases as the Sr/Ca ratio of the
solution was increased. Preformed shell also discriminated against Sr but to a
lesser extent. Conversely, snail-free shell took up Sr preferentially as did powdered
shell in an in vitro exchange study. Aragonite and calcite precipitated from calcium
solutions containing S9Sr and 45Ca removed equal proportions of these two isoto-
pes." Apparently, the discrimination against Sr relative to Ca in the living snail is
primarily the result of metabolic process with the possibility of some crystallo-
graphic differentiation; whereas in the case of dead snail there is mainly an exchange
of ions between the solution and the shell material, possibly accompanied by a
small degree of recrystallization or inversion (LIKINS et al., 1963, pp.276-277).
In his work on the relationship between Sr, Mg, and lgO/l60 ratios, LOWEN-
STAM (1961, 1963) found that the brachiopods investigated by him show a discrimi-
nation against Sr and Mg, and that the means of Sr/Ca and Mg/Ca ratios of shell
material are significantly lower in contrast to those of sea water.

Other jiuctors influencing the Sr content

In addition to the factors mentioned above, some others may also be influential.
Although they may be insignificant in general, in individual cases they can con-
tribute to cause distinct deviations from the norm. For example, KULPet al. (1952)
suggested that the high Sr content of Lingulepis is probably related to the high
proportion of phosphatic material in the shell.
Considering the bulk compositions of skeletal limestones, the amounts and
types of non-carbonate contaminations may become important factors in control-
ling the trace-element compositon. HIRST(1962) illustrated that the Sr/Ca curves of
some of the Recent sediments indicate that the Sr is more concentrated in those
containing considerable amounts of aragonitic skeletons. On relating the Sr/Ca
ratio to the percentage of Ca, additional control on Sr content was suggested:
probably, adsorption by clay minerals.
70 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

Sr content of skeletons versus sedimentary matrix of limestones

An interesting relationship was found by KULPet al. (1952) between the matrix
and the skeletons. Most striking is the higher Sr content of the fossil than that of
the carbonate matrix. The average values of Sr/l,OOO Ca ratios for the skeletons
and the matrices are 1.03 and 0.51 respectively, which gives a ratio of approximately
2/1. KULPet al. (1952) examined fossil brachiopods and matrices from a common
horizon to check on any possible relative variabilities. They found, however, that
the Sr concentration of brachiopods remained constant despite the variable con-
tents of Sr in the matrix samples. The Sr concentration of the matrix may be con-
trolled partly by the proportions of skeletal fragments and inorganic carbonate,
and partly by the type of skeletons in the organic fraction. It does not follow, how-
ever, that where the fossil and matrix show the same Sr content, the matrix is -
mainly skeletal and is composed largely of the same fossils that make up the frame-
work. Original differences may well be reduced (or completely erased) by differen-
tial solution, recrystallization, replacement, or some other process.

Other elements in skeletal and protective structures of organisms

In addition to Mg and Sr, a number of other minor and trace elements have been
found in association with calcareous skeletons. WISEMAN (1964) stated that cocco-
lithorphorids, for example, can concentrate nickel, cobalt, and copper, and do so
to a greater extent than planktonic Foraminifera.
In order to prevent contamination, utmost care should be taken in the prep-
aration of the samples. Most interesting is the observation made by GRAYSON
(1956) that while attempting to separate siliceous and calcareous material with
hydrofluoric acid, the CaC03 of various components was replaced completely by
calcium fluoride (CaF2) with preservation of all minute structural details. Changes
in concentrations of trace elements accompanied this major transformation.
EMILIANI (1955) spectrographically analyzed pelagic Foraminifera and found
the presence of small amounts of Ti, Al, Si, Fe, Mn, Mg, and Sr. He discovered
that when the analytic data was arranged in order of decreasing amounts of Al
(on the assumption that this indicates decreasing sedimentary contamination of the
samples), then Mg, Fe and A1203 reduced to zero simultaneously, whereas Si and
Mn did not. This suggests that Mg and Fe are not part of the skeletal material, and
that Si and Mn may be incorporated in the skeletons or tissues. As Emiliani pointed
out, Si does not substitute for Ca and it is not clear, therefore, how it might be
associated with the shell material. Although Mn can substitute for Ca, one has to
consider the presence of possible surficial MnO2 crusts on the organic shells that
cannot be easily removed by ordinary washing processes. According to Emiliani,
the Sr content in the Foraminifera did not change with the change in Al content but
remained constant, thus indicating that it is a part of calcium carbonate structure.
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 71

Comparing regional changes, Emiliani stated that “the abundance of elements

characteristic in terrigenous sediments (Ti, Al, Si) generally appears to be greatest
in the Caribbean and least in the Pacific samples. The Pacific samples may have
washed more cleanly, or perhaps these elements are less abundant there than in the
Caribbean and the Atlantic. In either case, analyses may be arranged in order of
decreasing amounts of A1 on the assumption that this indicates decreasing sedi-
mentary contamination.”
TUREKIAN and ARMSTRONG (1961) stated that the low Ba content in contem-
porary molluscan shells is a consequence of the low Baconcentration in theocean.
Of the three elements, Sr, Ba, and Mg, the greatest variability in concentration is
exhibited by Ba. The Ba content is on the whole higher in clams than it is in snails.
“This may be explained in terms of the environment in which these two groups are
most often associated. Snails to a large extent are epifauna while clams have a large
component of infauna. The low content of Ba in the sea contrasted with its high
content in marine muds and shales may provide the difference in environment of
shell growth of clams and snails. . . ” As ODUM(1957b) pointed out, especially
mud-eating organisms may take up elements from the sediments during digestive
processes.
Comparatively high values of uranium in corals (2.9-5.5 p.p.m.) have been
mentioned by TATSUMOTO and GOLDBERG (1959). In contrast to Sr, for example,
which is more readily accommodated in aragonite as compared to calcite in biolog-
ical specimens, uranium in the limited cases studied does not show any evident
preference apart from that noted in the case of corals.
GOREAU (1961) developed a technique of measuring growth of living corals
by introducing a radioactive 45Ca tracer into their skeletons.

Organic matter associated with carbonates

The control of organic matter and matrices on the minor and trace elements
ranges from subordinate to very considerable. W. D. EVANS(1964) stated, as have
others previous to him, that organic matter may affect diagenetic processes such
as solution, reprecipitation, recrystallization, and so forth, of both carbonate and
other minerals. LONGet al. (1963) discussed the significance of organic materials
in sediments as a possible useful indicator in paleogeographic reconstructions in oil
exploration. GEHMAN (1962) supplied the following data on the proportions of
organic matter: (I) mean organic content of limestones = 0.24%, (2) mean organic
content of shales = 1.14%, (3) mean hydrocarbon content of limestones = 98
p.p.m., and (4) mean hydrocarbon content of shales == 96 p.p.m. Gehman also
pointed out that Recent limestones have higher contents of organic matter than
ancient sediments.
Reference such as the above to organic matter in sediments is common, and
its influence on diagenetic events is probably great. For example, the decomposition
72 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

of organic matter may free associated cations. BERGER (1950) offered the following
division concerning the role of organic matter (see also OPPENHEIMER, 1960):
(A) Concentration of elements through metabolic processes: C, N?, P, S,
Fe, Si, Ca, Ba, Mn, I, (Cu, V, geochemically not active) Zn?
( B ) Post-mortem concentration:
(1) Chemical.
(a) Uptake into organic molecules: V, Ga, Ge?
(b) Sulfide precipitation: Fe, Cu, Pb, Zn, etc.
(c) Reduction: Ag.
(2) Physical adsorption: V, Ag, Th, U, etc.
The survey by ABELSON (1 957) showed the widespread presence of proteins
in Recent skeletons, which makes it likely that many, if not most, fossils originally
contained some proteins. Abelson exposed different layers in Recent shells by
removing successive laminae with dilute acid, and thus determined the location of
the protein within the skeletons. He found that many of the shells are sufficiently
dense to make the interior impervious to Bacteria, which suggests that preservation
of proteins in fossils may be possible. Many fossil specimens have been reported to
contain amino acids which may be partly adsorbed on carbonate skeletons.
ABELSON’S (1 957) experiments indicated that aspartic and glutamic acids are the
two amino acids which are readily adsorbed, whereas alanine, one of the principal
amino-acid camponents of fossils, has almost no affinity for CaC03. This suggests
that at least the latter is not merely a contaminant adsorbed to the carbonate
skeletons. ABELSON (1959a, b) also reported that porphyrins are among the most
stable organic materials and, therefore, can be expected to be found in ancient
specimens.
Very little is known on the history of various metals originally contained in or
adsorbed on the soft tissue of organisms as mentioned by GRAF(1960), who gave a
list of pertaining references. GLAGOLEVA (1961) investigated the role of bottom
organisms in contributing the trace elements and concluded that some elements
came from the calcareous skeletons, whereas others must have come from some
other source, possibly from the soft organic parts. Glagoleva did not, however,
support the latter possibility by conclusive evidence. HOODet al. (1959, in: INGER-
SON, 1962) identified carbamino-carboxylic acid complexes which are utilized, for
example, by certain marine phytoplanktons in photosynthesis. These compounds
may complex Ca, Sr, and possibly Mg into non-ionic form. According to ABELSON
(1959a,b), hemalin and chlorophyll (porphyrin pigments) readily lose their Fe
and Mg to become free of metals until V and Ni occupy the sites formerly held by
Fe and Mg. The resulting stable complexes are hydrophobic and very soluble in
petroleum; and are the types of porphyrins commonly found in sediments and
petroleum. (See GRAF,1960, parts I1 and 111 for literature survey.)
GOLDBERG (1957) pointed out that parallelism in biochemical and paleo-
biochemical paths of trace constituents is difficult to establish, inasmuch as only
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 73

very seldom analyses have been made on more than a few elements. In general,
however, it has been found that the concentration of heavy metals is greater in
marine organisms than that found in the hydrosphere. Also, it appears that organ-
isms of lower phylogenetic levels seem to take up trace metals to a greater extent
than do the vertebrates. The differences between the concentration of elements in
organisms and in sea water exist for families as well as species, and the trace
metals are retained by fairly strong chemical bonds in the organisms. GOLDBERG
(1957) stated that “in general the relative concentration factors for metals in the
marine biosphere as compared to sea water closely parallel the order of stability of
metal ions with organic ligands”. SCHUBERT (1954) showed that for a variety of
bivalent transition metals (essentially independent of whether the metals are attach-
ed to oxygen, nitrogen or sulfur atoms) the decreasing order of stability of the
complexes is: Pd> C u > Ni> Pb> Co> Zn> C d > Mg. It appears, that the
stability decreases as the basicity of the metal increases. Schubert also reported
that for alkaline earth metals the order generally i s Z n s Mg, Ca> Sr> Ba> Ra,
where position of Mg is often irregular. For certain tervalent metal ioas the se-
quence is often as follows: TI> Fe> G a > In> A12 Cr> Sc> rare earths.
For the rare earths the order is Y > Sm> N d > Pr> La, again in the order of
increasing basicity. In the case of group of divalent metal cations of the first
transition series, the stability of complexes increases to a maximum (at copper)
and then decreases: M n < Fe< C o < Ni< C u > Zn. It is of importance to re-
member that stability relationships may vary. For example, Mn2+ ions form
stronger complexes with oxygen-type ligands, and Co2+, with nitrogen-type
ligands; these differences are even more pronounced for c03+and Mn3+ ions
(SCHUBERT, 1954).
GOLDBERG (1957) mentioned that the fractionation factors (concentration in
organism/concentration in sea water ratio) for sponges, for example, are as follows:
Cu, 1,400; Ni, 420; Co, 50; Mg, 0.07; and Ca, 3.5. Biochemical fractionation can
lead to an extensive depletion of some elements in the surrounding sea water as
has been reported already for strontium in waters near coral reefs (SIEGEL,1960),
and during extensive radio-yttrium ion concentration by red Algae and diatoms.
Regarding the uptake of trace elements in connection with particulate matter
by members of the marine biosphere, GOLDBERG (1957) mentioned that “these
particles can enter the marine biosphere via the filter-feeding organisms and their
predators, as well as by direct transfer through adhesion to the outer surfaces of
plants and animals”. Because all these substances, except calcium carbonate, can
exist as colloidally dispersed particles, it may be expected that the adsorbed ions
with charges opposite to those of the colloidal particles will accompany them.
LEHNINGER (1950) stated that the biological specificity of metal ions for such
organic substances as proteins depends on: (I) the mass of the ions, (2) ionic
charge, (3) ionic radius, (4) oxidation-reduction potentials of the ions, and (5)
availability and chemical state of elements, among others.
74 K. H. WOLF, G. V. CHlLlNGAR AND F. W. BEALES

Certain enzymes have been found to contain Mn and facilitate the precipita-
tion of calcium phosphate. INGERSON (1962) suggested that similar enzymes in
lime-secreting organisms may be active in the deposition of calcium carbonate and
possibly even of dolomite. In pursuing this problem the active metal in the enzymes
should be of particular interest.
INGERSON (1962) suggested that, although the available information is
extremely scarce, the work of VINOGRADOV (1953) and others shows that certain
groups of organisms are characterized by relatively high contents of certain
elements. If high concentrations of particular elements, that are known not to
precipitate inorganically, are present in carbonate sediments, it may indicate that
the corresponding organisms were active in the formation of these sediments.
Considerable caution is necessary in the selection and preparation of ancient
sediments for analysis for traces of organic compounds. For example, during the
preparation of insoluble residues, fungal hyphae, associated with lichens growing
on the rock surface, have been observed to penetrate several inches into the rock.
Freshly quarried material and diamond drill cores can be penetrated and contam-
inated rapidly.

Direct bacterial influences

Diverse bacterial activity can hardly be overestimated in (I) the precipitation and
solution of carbonates, (2) the transformation and decomposition of both inorganic
and organic materials, (3) the control of the pH and Eh of the water medium, ( 4 )
the production of gases and disfiguration of sediments, and (5) the liberation and
concentration of minor and trace elements. VINOGRADOV (1 953), ZOBELL(1957),
OPPENHEIMER (1960), CLOUD (1962) and KUZNETSOV (1962) in numerous publica-
tions have given a list of bacterial processes and discussed their effects on the
chemical composition of sediments.
VINOGRADOV (1953) gave the following list of elements that are utilized or
transformed by Bacteria: C, H, 0, N, P, As, S , Se, Fe, Mn, Al, Ca, Si, and Mg.
Probably, future research will result in the addition of other elements to this list.
The interesting phenomenon of Mg- and Ca-concentration mentioned by
CARROLL(1963) has been presented earlier. This observation is of particular
significance as it has been suggested that Bacteria may form a nucleus for calcium
carbonate precipitation. TAFTand HARBAUGH (1 964) have suggested that the dark
matter in the interior of some dolomite crystals in Recent carbonate deposits may
be organic in composition. If one accepts the evidence given by LALOU(1957) and
NEHERand ROHRER(1958), which indicates that Bacteria may be able to form
dolomite, or at least carkact as nuclei for the inorganic precipitation of carbonates,
then one may well suppose that the dark components described by Taft and Har-
baugh could be of bacterial origin.
The problems encountered by BROECKER (1963, p.2829) in evaluating the
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 75

uranium series inequilibrium as a possible tool for absolute age determinations of

marine carbonates, indicate that further studies of diagenetic processes, that may
have been initiated and controlled by Bacteria, are of real practical importance.

Application of skeletal mineralogy and chemical composition to geological problems

A number of attempts have been made to evaluate the possible use of the mineralogy
and elemental composition of calcareous skeletons and organogenic limestones.
Some of these possible uses are implied in the paragraphs which follow, in which
brief consideration is given to skeletal growth and element uptake and retention,
under differing ecological and diagenetic conditions.

Mode and rate of shell growth and element uptake

Experiments performed on the growth of calcareous shells have furnished some
data on the mechanisms and rate of skeleton genesis, and on the role of chemical
elements and certain isotopes. Some of the publications, such as the one by LIKINS
et al. (1963), have been mentioned elsewhere in this chapter. Additional references
are to be found in the chapter on techniques of analyzing carbonates by WOLF
et al. (1967) in this book. T. F. GOREAU and N. I. GOREAU (1960) have used
radioactive tracers to study skeleton formation in corals.

Taxonomic significance
In general, little information is available on significant mineralogical and chemical
criteria in the classification of plants and animals as a whole. One exception is the
attempt by BLACKMON and TODD(1959), mentioned earlier, who have suggested
that the mineralogic composition of foraminiferan skeletons should be taken into
account when lineages are under consideration. LOWENSTAM (1961) suggested that
the discrimination of brachiopods against Sr and Mg, and the mean values of
Sr/Ca and Mg/Ca ratios, may be characteristic for the species of various genera
and orders of the articulate brachiopods.
VINOGRADOV (1953) mentioned that skeletal chemical compositions in
Algae, to name only one group, are characteristic for given species and genera and
that composition is also related to the organism’s habitat.

Mode and degree of diagenetic alterations

The tempo of study of diagenetic modifications is increasing with development of
more sophisticated techniques supporting the petrographic microscope, and
making it possible to measure minute changes. The difficulties involved are, of
course, enormous. Investigations on Recent skeletons, ooliths, pellets, various
types of lime-muds, and so on, coupled with laboratory syntheses may eventually
lead to the establishment of upper and lower limits of element concentration for
skeletal and non-skeletal materials for particular conditions. Any increase or
76 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

decrease from the “standard values” would indicate a change, and this in turn may
assist in understanding diagenetic-epigenetic alterations.

Temperature and salinity interpretations

Many factors can influence the mineralogy and chemical composition of calcareous
skeletons; however, most attention has been given t o the study of mineralogy-
temperature, magnesium-temperature, strontium-temperature, oxygen isotope-
temperature, mineralogy-salinity, and strontium-salinity relationships, with lesser
consideration of other interdependencies of elements within their environment of
formation. These are briefly considered here:

Mineralogy-temperature relationship. LOWENSTAM (1954a, b) has presented data

that leave little doubt that temperature is one of the factors influencing skeletal
mineralogy. Closer examination of small taxonomic groups, at the generic or
specific level, however, revealed numerous exceptions. Lowenstam found, for
example, that limited sensitivity to temperature of shell mineralogy and even a
lack of mineralogy-temperature interdependence for some species appears to be
linked to semi-terrestrial adaption. In some extreme cases, shell deposition was
shown to occur only at elevated temperatures. In another case, Lowenstam report-
ed on two species, occupying essentially the same environmental niche: one was
found to be temperature dependent whereas the other was not. The mode of life
may intervene as, for example, in the case of pelecypods where only the vagrant
benthos show temperature-dependence, whereas sessile or cemented types do not
seem to show it. Lowenstam also suggested that salinity may influence the aragonite
and/or calcite precipitation of skeletons in addition to temperature and other
possible controls.
DODD(1961) stated that the mineralogy of the mussel, Mytilus caftforniunus,
is not affected by temperature in small specimens, but larger ones show positive
temperature-aragonite correlation. In the case of Mytifus edulis the mineralogy is
also affected by salinity and shows a negative salinity-aragonite correlation. Dodd
concluded, therefore, that Mytifus in the region investigated by him can be useful
for paleotemperature and paleosalinity interpretations.
Subsequent work by DODD(1962) showed that the shell of Mytifus calijor-
nianus comprises four layers composed of either organic substance, calcite or
aragonite. The growth-pattern and structure of some of the layers are believed to
represent summer deposition and can be used, therefore, for age determinations of
the shell. In turn, the growth rates, which are in part a function of temperature,
can be determined; this provides additional paleotemperature data. In a more
recent publication, DODD(1963a, b) suggested that a strong phylogenetic effect
existed; different species of the same genus showed different temperature-mineral-
ogy relationships which definitely indicate additional influences to those given
above. Correlation exists between shell thickness and mineralogy in Mytifus cufifor-
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 77

nianus, whereas mineralogy and shell length correlate in Mytilus edulis diegensis.
Shell thickness itself, however, may not affect mineralogy; instead, some unknown
factor may control both mineralogy and thickness of calcareous skeletons. Some
species have an early stage in their growth that is temperature insensitive, whereas
this is not found in other species. In some instances, Mytilus californianus smaller
than 20 mm in length showed no relationship between mineralogy and temperature.
Both subspecies of Mytilus edulis show negative correlation between salinity and
aragonite content. This relationship is not determinable in the case of Mytilus
calijornianus, as it is stenohaline in nature. In this connection it should be noted
that, with one exception as reported by DODD(1 963b), all fresh-water molluscs
are aragonitic. DODD(1963a) concluded that the variations in species and sub-
species of Mytilus are not completely explained by any of the factors considered;
as yet undetermined influences may be operative in controlling the aragonite
content. It seems, however, that Mytilus californianus can be used for paleotempera-
ture reconstructions, if large, complete, unworn, qnd well-preserved shells are used.
Shell mineralogy of the two subspecies Mytilus edulis eduli and Mytilus edulis
diegensis is possibly useful for paleosalinity determinations.

Magnesium-temperature relationship. The magnesium content and the Mg/Ca

ratio of calcareous shells certainly reflect environmental temperature as shown by
CHAVE (1954a) and CHILINGAR (1953, 1962a). Deviations from the “ideal” temper-
ature-magnesium relationship have been mentioned earlier in the section on
magnesium in skeletons. Some other examples that show the degree of reliability
of using Mg contents of skeletons for paleotemperature reconstructions are present-
ed here.
CHILINCAR (1962a) plotted the Ca/Mg ratios of various organic groups and
confirmed CHAVE’S(l954a) observation that there is an inverse (hyperbolic)
relationship between the Ca/Mg ratio and the environmental temperature. Chilin-
gar found that in some cases temperature differences as small as 0.5”C are reflected
in the Ca/Mg ratios of organisms. Artificially precipitated carbonates also showed
an inverse relationship between the Ca/Mg ratios and the temperature. Chilingar,
therefore, concluded that “the similarity in shape of ‘Ca/Mg ratio versus tempera-
ture’ curves of invertebrates and direct chemical precipitates suggests that the
Ca/Mg ratios of these organisms are controlled to some extent by the effect of
temperature on solubility products of CaC03, MgC03, Mg (OH)2, etc. The differ-
ences in magnitude of Ca/Mg ratio in different organisms may be related to the
growth mechanism, and composition and pH of the body fluids.”
DODD(1963a) mentioned that the Mg content of the outer calcitic layer of
Mytilus increases with increasing environmental temperature, but not so regularly
as does the Sr concentration.
CHAVE(1954a) observed that the temperature-magnesium trend of a single
echinoid species roughly parallels the trend of the entire class. PILKEY
and HOWER
78 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

Species trend
\ /’

Class trend+
L
4-

Temperature -
Fig.4. Diagrammatic illustration of temperature-magnesium trends of individual echinoid species
as compared to temperature-magnesium trend of the whole class. (After PILKEY and HOWER,
1960; by permission of Journal of Geology.)

(1960), on the other hand, found that the trend of temperature versus MgCO3
content curve of a single echinoid species differs from the trend of the entire class:
“the MgC03 content of a single echinoid species changes at a significantly lesser
rate than the temperature-Mg trend of the entire class . . . ” They commented that
future studies may reveal a step-like succession of temperature-Mg trends as
shown in Fig.4. Based on their work, Pilkey and Hower pointed out that although
LOWENSTAM (1954a, b) showed a positive correlation with water temperature for
the articulate brachiopods at the class level, this relationship may not hold for the
specific level of the brachiopods. In conclusion, there appears to be little doubt
that in general CHAVE’S (1954a) and CHILINGAR’S (1953, 1962a) temperature-
magnesium correlation is valid but that in many particular instances the relationship
has proved to be more complex. Both purely organic-metabolic and purely physico-
chemical influences appear to be operative, and more research is required on the
species and subspecies level before paleotemperature reconstructions can be
accepted as reliable.

Strontium-temperature relationship. If one considers the observations made by

LOWENSTAM (1 954a, b) that the aragonite/calcite ratio in many organisms increases
with temperature, and that the Sr content is usually greater in aragonite, then one
should expect a relationship between Sr content and temperature. In fact, Lowen-
stam did notice an increase in Sr content with increasing temperature in the Ser-
pulidae. KULPet al. (1952) and ODUM(1950a, b) had previously reported, how-
ever, that no correlation, or at least a very poor one, exists between the Sr/Ca
ratio and temperature even for those species the crystal form of which does not
vary with temperature. Genera and species that have a wide range of temperature
tolerance have similar Sr/Ca ratios in both warm and cold environments. For
example, calcareous red Algae and aragonitic gastropods do not show a consistent
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 79

variation pattern of Sr/Ca ratio with temperature in Odum’s table. KULP et al.
(1952) and CHAVE (1954a, b) made similar observations; and the latter stated that
the incorporation of Sr is quite different from the inclusion of Mg in echinoderms,
for example.
TUREKIAN (1957) analyzed Atlantic equatorial eupelagic cores for Ca and Sr
and found that “when the Globigerina contribution to the Sr and Ca contents of the
core are subtracted, a variation in the Sr-to-Ca ratio for the fine fraction is observed
which is related to the Ericson temperature curve for the core-the high Sr/Ca
ratio corresponding to a time of high surface ocean temperature.” This is best
explained by a sympathetic variation in abundance of celestite tests secreted by
acantharian Radiolaria. “If the carbonate and lutite sedimentation rates are sensi-
bly constant, then Acantharia productivity is temperature dependent.” Subsequent
investigations, however, seem to have shown that the celestite has been depositing
at a constant rate and that the variations observed are due to varying rates of
calcium carbonate deposition.
PILKEY and HOWER (1960) found that Sr/Ca ratio is temperature dependent
at the specific level but not at the class level. In a subsequent publication (PILKEY
and HOWER,1961) they stated that Sr content of some aragonitic mollusc species
exhibits a positive correlation with annual mean temperature; the Sr content of
some calcitic molluscs shows a poor negative correlation with temperature but an
excellent negative relationship with salinity. One species correlated poorly with all
environmental factors examined.
DODD(1963a) determined the Sr content of the calcitic prismatic layer of
Mytilus and found that it is directly proportional to growth temperature, whereas
the Sr content of the aragonite nacreous layer varies inversely with temperature.

Combined study of Sr, Mg, and 0 isotope contents of skeletons. Many of the ap-
parently contradictory results obtained in the study of carbonate chemistry and
environmental reconstructions are due to the restriction of analytical investigations
to only one or two components; and this, consequently, does not permit the detec-
tion of possible secondary modifications. LOWENSTAM (1961, 1963) reported
investigations of the Sr and Mg contents and the 1 8 0 / l 6 0 ratios of Recent and
fossil brachiopods. He demonstrated that SrC03 and MgC03 contents and
1 8 0 / 1 6 0 ratios of Recent brachiopods from waters having salinities close to the
average of the oceans (33.5-36.5 %,) are all temperature-dependent. The data
presented, however, suggest that the Sr and Mg contents in brachiopods vary not
only with environmental temperatures but also with the species and other factors.
The use of SrC03 and MgC03 contents in conjunction with l 8 0 / l 6 0 ratios for
determining the presence and degree of diagenetic alterations are discussed in the
appropriate section below.

and GOODELL
Other elements-environment relationships. PILKEY ( 1963) stated that
80 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

aside from studies on Mg and Sr, only a few attempts have been made to evaluate
the environment-element relationships for other major and trace constituents.
They analyzed seven species of molluscs for Mg, Mn, Ba, Sr, and Fe contents and
shell mineralogy, and studied their relationship to both temperature and salinity.
The results indicated that no compositional variable is related to environmental
temperature in four species. The Mg/Sr, Mn+Mg+Ba+Fe/Sr, and Mn+Mg+
Ba/Sr ratios, and the percentage of calcite correlate with temperature in three
species, whereas other ratios or percentages exhibit a relationship in very few
(two or less) instances. With two exceptions (i.e., Sr and calcite contents), the
nature of the relationships between temperature and any single compositional
variable are consistent and the correlations are always inverse or always direct. In
general, however, the correlations with temperature are weak, and the differences
in salinity cause greater changes in the composition of skeletons than differences
in temperature. Thus, PILKEYand GOODELL(1963) concluded that the environ-
ment-composition relationships are too weakly defined to be of use in ecological
reconstructions in the cases investigated by them.

Relationship bet ween salinity cind skeleton composition. TUREKIAN (1955) pointed
out that the importance of salinity as a possible independent variable controlling
the Sr/Ca ratio in shells and sediments has not been stressed. KULPet al. (1952)
also stated that the primary factor controlling the composition is the Sr/Ca ratio
in the water medium, which in turn is related to salinity. The effect of temperature,
according to them, is only of very minor importance.
SAID(1951) reported on a species that was found to have a different skeleton
composition in two widely separated localities, both in respect to elements present
and the quantities thereof. Amphistegina radiata from the Red Sea has higher
contents of practically all the rare chemical elements present than those of the
Pacific Ocean specimens. The Red Sea specimens also have tin, whereas those of the
Pacific lack it. According to Said, these differences may be due to a higher salinity
of the Red Sea, among other possible reasons.
More recent investigations have shown that salinity certainly has a marked
effect on both shell mineralogy and elemental composition, but the relationships
once again are far from being simple (PILKEYand HOWER,1960), as illustrated
here by a few examples.
PILKEY and GOODELL (1962) found that of several mollusc species some show-
ed a positive correlation of Sr content with temperature, whereas others exhibited
poor negative correlation with salinity. Except for one species, an inverse relation-
ship between salinity and Sr content is present to some degree in all the molluscs
studied. In a subsequent study, PILKEY and GOODELL (1963) demonstrated that the
differences in salinity result in a greater modification of mollusc shell composition
than do temperature variations, but that salinity concentration above 25z0 do not
markedly affect the composition of the skeletons. Pilkey and Goodell showed,
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 81

however, that salinity-composition interdependence is too weak to permit reliable

paleoecological reconstructions.
RUCKER and VALENTINE (1961) measured the concentrations of Mg, Sr, Mn,
Na, Cu, and B in 71 shells of Recent Crassostrea virginica. They found that Mg+Sr
and Mn contents are statistically inversely related to salinity. The Na content
correlates directly with salinity; however, it is interpreted as not being part of the
carbonate shell, and is thought instead to be present in interstitial salts deposited
from sea water trapped in the skeleton. Contents of the other elements show no
significant relation to either salinity or temperature. Rucker and Valentine con-
cluded that the “multiple-regression technique based on the concentrations of Mn,
Na and Mg+Sr permits the prediction of the environmental salinity of shell
growth for Crassostrea virginica within a rather large standard error (5.3 %)”.
DODD(1963a) reported a marked increase of Mg content in the outer calcitic
prismatic layer of Mytilus with decreasing salinity. The Mg concentration in the
aragonitic nacreous layer was too low for accurate measurements.
Regarding the relationship of Ba and Sr to salinity, LANDERGREN and MAN-
HEIM (1963) presented arguments showing that Ba is not a useful salinity indicator
8s based on our present knowledge, except possibly in rare cases. According to
LEUTWEIN (1963), the Ba/Ca ratio increases in fresh water, whereas the Sr/Ca
ratio decreases. Many exceptions to this rule, however, have been recorded.
The excellent work by LOWENSTAM (1961, 1963), already mentioned in the
section on temperature-element correlation, indicated that Sr and Mg contents of
articulate brachiopods are partly related to temperature; however, other influences
seem to be operative. Lowenstam, therefore, examined specimens from hypersaline
and hyposaline environments and compared them with those of normal marine
localities with similar water-corrected 1 8 0 / 1 6 0 ratios. It was found that the SrC03
contents and the Sr/Ca ratios of the skeletons are sensitive to changes in Sr
concentration and Sr/Ca ratio of the water medium, and that the magnitude of
changes differ for hyper- and hyposaline waters. Lowenstam also reported that in
spite of proportional differences in Mg and Ca contents in hypo- and hypersaline
waters, the uptake of Mg into brachiopod skeletons varies. He suggested that the
absolute Mg concentration in the water medium is the important factor in determin-
ing the Mg content of the shells, but other influences are operative and complicate
the relationship.
ODUM(1957b) concluded that “ . . . it is possible to use analyses of Sr/Ca
ratios to determine whether fossil skeletons that are unreplaced are marine or
.
fresh-water . . If the Sr/Ca ratio is higher than the Sr/Ca of ocean species a non-
marine locality with a high Sr/Ca ratio can be recognized, but if the Sr/Ca ratios
are close independent evidence is required for proper interpretation . . .” Inasmuch
as closed lakes may resemble the oceans in having high Sr content, the Sr/Ca
ratio cannot always indicate the difference between inland closed basins of sedi-
mentary drainage and the ocean. In a table, ODUM(1957b, table 32) showed the
82 K. H. WOLF, G . V. CHILINGAR AND F. W. BEALES

use of Sr/Ca ratio in fossil skeletons for determining the nature of ancient environ-
ments. He recognized two groups: ( I ) fossils with high Sr/Ca ratio, which possibly
indicate marine and arid lake origin, ground-water source, or volcanic drainage;
and (2) fossils with a low Sr/Ca ratio which are indicative of origin in fresh water
having a low Sr/Ca ratio. These two groups are so all-inclusive, however, that they
are of little applicability in precise geochemical interpretations. Odum admitted
that in controversial cases independent criteria have to be used, e.g., type of fossil
assemblage.
KUBLER (1962) investigated the Sr content of two sedimentary cycles com-
posed of marine to lacustrine deposits and found a range of about 1,OOO to 5,000
p.p.m. He did not find a distinctive difference that could be attributed to the salinity
factor.
The foregoing considerations compel one to agree with ODUM(195713) that
the Sr/Ca ratio is not a complete answer in salinity reconstructions; however, in
many cases it can be helpful if used with other sources of evidence.
The present state of our knowledge permits us to support other data useful in
recognizing specific environments with information on the Sr/Ca ratios. These data
may assist in attempts to interpret ancient environments but too little is known
about Sr-Ca partition during genesis, or modification during diagenesis, to permit
definitive interpretations based on Sr/Ca ratios alone.

Skeleton-environment relationships, and “Law of Minimum in Ecology and Geo-

chemistry”. Some insight has been gained into the factors that control directly and
indirectly, separately and in combination, the mineralogic and elemental compo-
sition of the calcareous skeletons of both plants and animals: carbonate poly-
morphism, temperature, salinity, phylogenetic level, growth rate of shells, multi-
mineralogic composition, seasonal and life-span variations in composition and mode
of development, biochemistry of body fluids, adsorbed and absorbed impurities,
solubility products and other conditions in the depositional medium, non-uniform
degree of effects with changing physic0 chemical conditions (e.g., salinity effects
are absent in some cases above 25%,, but are distinct below that value), mode of
life (e.g., planktonic versus benthonic; crawlers versus borers and burrowers),
mode of food-intake, and many others.
The published results so far indicate that if the composition of skeletons is
to be used for definite paleoecological reconstructions, it can be done with confi-
dence only at the specific level. One promising approach is suggested by the work
of PILKEY and GOODELL (1962) who found that certain species of molluscs are
either temperature- or salinity-insensitive to varying degrees. By the simultaneous
use of shells of more than one of these species, it may be possible to make both
paleotemperature and paleosalinity interpretations. Wherever possible, shells
composed of either calcite or aragonite should be utilized to eliminate complex
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 83

effects due to polymorphism. More than one variable should be determined in large
samples to enhance the reliability of the interpretations made.
With an increase in the data on environment-organism and environment-
mineral relationships, the familiar Law of Minimum in Ecology may be expanded to
include minor and trace elements, and inorganically and organically formed
minerals, and be designated instead The Law of Minimum in Ecology and Geo-
chemistry (WOLF,1963b). Briefly stated, the geochemical phenomena that are
sensitive to environmental conditions can be used in conjunction with biological
data as criteria to narrow down environmental ranges. WOLF(1965a) demonstrated
the partial application of this principle to a Devonian reef study.

Environmental reconstructions of regional trends in skeletal mineralogy and

chemical composition
Regional trends in both the mineralogy and chemical composition of skeletal
carbonate sediments have been shown by CHAVE (1962) to depend not only on the
particular organisms present in the different environments, but also on the size of
the organisms, selective physical destruction, transportation, and differential
solution. In addition to these, the work of MAXWELLet al. (1964) suggested
that selective removal of various components by winnowing and differential
transportation-accumulation is significant.
CHAVE(1962) illustrated that in the recent reef complex in North America
studied by him, the highest ratio of high-Mg to low-Mg calcite is in the reef vicinity
due to coralline Algae Lithothamnion and Lithophyllum, and encrusting Foramini-
fera Homotrema. The lowest value of this ratio is found in sediments from deeper
waters because of the abundance of planktonic Foraminifera, e.g., Globigerina. The
highest percentage of aragonite is present in shallow waters due to the abundance
of the aragonitic corals and molluscs and aragonitic alga Halimeda in lagoons. This
seems to agree with the observations made previously by CHAVE (1954a, b) and
STEHLIand HOWER (1961) that only in quiet deep water is calcite the predominant
mineral phase. In other parts, aragonite and high-Mg calcite form the main compo-
nents of recent sediments.
Inorganic processes may also control the mineralogy as suggested by
CHAVE’S observations (1962) that: ( I ) near-reef sediments contain less aragonite
than the nearby lagoonal sediments; and (2) the mineralogy changes with grain
size. He concluded that inasmuch as the living reef is mainly composed of aragonitic
madreporarian corals and molluscs, and that the calcitic alcyonarian corals,
coralline Algae and Foraminifera are of minor quantitative importance (some-
times, however, they are responsible for the local high-Mg calcite concentration),
it seems probable that a non-biologic process or processes remove aragonitic
debris. Chave suggested that perhaps differences in durability of aragonitic versus
calcitic material may be the causal factor. Change of mineralogy with grain size
84 K. H. WOLA,,G . V . CHILINGAR AND F. W. BEALES

is reflected in a regular increase in mineral stability, with associated decrease in

mineral solubility, from coarse to the fine fractions of the carbonate sediments
(CHAVE,1962). According to him, there is a decrease in aragonite percentage and a
decrease in the ratio of high-Mg to low-Mg calcite from the coarse to the fine sizes.
This regular change has been found in a wide range of environments. For this
reason, and because of the fact that the sediments of deep-water environments are
largely composed of calcite, it appears that in the case of CHAVE'S(1962) study-
locality, differential removal by washing and transportation to a more favorable
site of accumulation is not applicable. Under other conditions such as those de-
scribed by MAXWELL et al. (1964),however, a differential washing process may be of
major importance. To understand his observations, Chave considered, among
other explanations, inversion from aragonite to calcite and removal by solution
as possible processes. Inversion was dismissed as an unlikely mechanism based on
his belief that it would not be controlled by grain size in contrast to solution. Chave
concluded, therefore, that solution is the most plausible cause of the regular
increase in mineral stability with decrease in size. It should be noted, however, that
in general the relationship between grain size and degree of inversion needs verifi-
cation for reasons pointed out elsewhere in this chapter. A number of other inde-
pendent investigations of Recent carbonate sediments indicated that selective
removal by solution seems to be a rare phenomenon in the warm, shallow-marine
environment.

Age determination
BARNES et al. (1956) suggested that it may be possible to date corals by the U-10
(uranium-ionium) method as far back as 300,000 years, because the 238U decay
series in recently formed marine coral is systematically out of radioactive equilib-
rium. Subsequent investigations by TATSUMOTO and GOLDBERG (1 959) revealed
the presence of substantial amounts of uranium in oolites, and studies thereof led
to the conclusion that dating of oolites based on growth of ionium (thorium-230)
from uranium also seems possible. BROECKER (1 963) furnished data, however,
which demonstrate that fossil molluscs have a higher uranium content than living
forms. Various lines of reasoning led Broecker to dismiss both the species effect and
the change in U/Ca ratio of sea water during geologic time. He concluded that the
excess uranium is secondary and of very early origin. One possible explanation for
the excess of uranium being added shortly after death, while the organism was still
in contact with the marine environment, is perhaps bacterial destruction of the
organic matrix which sets up a microenvironment favorable for U precipitation.
I t is important to note here that the origin of the uranium in organisms must be
precisely known before the reliability of these materials for dating can be evaluated.
BROECKER (1963) also found that zz6Ra in any fossil carbonate can be divided
into five types according to origin and that only two are useful for age estimates.
Thus, use of the Z26Ra/238Uratio in determining the absolute age of marine carbon-
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 85

ates results in highly misleading ages. Broecker concluded that “criteria based on
internal agreement of the isotopic data (i.e., 234U, 230Th, 226Ra, and where
possible, 231Pa), other diagnostic parameters (microscopic examination, aragonite
content, 13C/12C, 180/160, 232Th content, 238U content, 234U/238U, etc.) and
material type (for example, coral and oolite are obviously more suitable than the
average mollusk) will have to be developed”.

Correlation based on composition

K u D Y M o v ( ~in~ his
~ ~ book
) Spectral Well Logging has shown that correlation
based on the minor and trace-element contents of carbonates and non-carbonate
sediments can be most useful. CHILINGAR and BISSELL (1957) used Ca/Mg ratio
for correlation purposes in studying the Mississippian Joana Limestone of the
Cordilleran miogeosyncline. (Some discussion on this subject is presented in the
section on “Regional aspects of carbonate composition” in this chapter.

Basis for exploration philosophies

GARLICK(1964) and MALAN(1964) described the pattern of metallic mineral
distribution in reef complexes. Malan showed that copper is mainly concentrated
in the inter-reef argillites.
Various other attempts have been made, mainly by commercial companies,
to use trace elements or other geochemical gradients to assist in the search for
oil and gas deposits or metallic ore bodies. They have not been conspicuously
successful to date; or if they have, the results have been kept as well-guarded
secrets. Despite the difficulties that are bound to be encountered, the search for
such indicators should be continued unless and until it has been proven futile. The
objective is to develop criteria that are sufficiently diagnostic to reduce the number
of test bore holes necessary for reconstruction of paleoenvironments and yet to
permit conventional stratigraphic correlation. The present state of the research
seems to be one of adding interesting corroboration of results already understood
rather than one of developing an exploration tool. The authors were informed
(confidential data), however, that the use of Ca/Mg ratios (plotting lines of equal
Ca/Mg ratio and recording directions in which these ratios decrease) in locating
dolomitized (and porous) carbonate oil reservoirs proved to be of value in some
areas.

INORGANIC FACTORS AND PROCESSES RELATED TO ELEMENTAL COMPOSITION OF

CARBONATES

The problems related to the mineralogic and elemental composition of inorganical-

ly formed carbonates can conveniently be discussed under the following headings:
( 1 )inorganic physicochemical precipitation of calcium carbonates; (2) mechanical,
volcanic, and cosmogenous contaminations; (3)magnesium in inorganic carbonates;
86 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

( 4 ) strontium in inorganic carbonates; (5) other elements in inorganic carbonates,

and associated contaminants; (6) elemental composition of environment control-
ling precipitation and stability of vaterite, aragonite, calcite, and dolomite; (7)
environmental influence on the particle form of carbonate precipitates; and (8)
influence of chemical composition of depositional medium on organisms.

Inorganic physicochemical precipitation o j calcium carbonates

The numerous parameters and processes that cause inorganic enrichment, deple-
tion, and migration of chemical components cannot be considered in this chapter.
Due attention has been given to them in other chapters of this book, and additional
information is available in the publications by RANKAMA and SAHAMA (l95O),
KRAUSKOPF (1955), GARRELS (1960), GOTO(1961), and others.
Most interesting from the petrologic point of view is the recent observation
made by ANGINOet al. (1964) indicating that inorganic processes, which are
usually associated with warm and temperate climatic zones, can be expected to be
operative also in unusual localities. Angino and co-workers observed the precipita-
tion of gypsum (CaS04), aragonite (CaC03) and mirabilite (NazS04) in the per-
manently ice-covered Antarctic Lake Bonney where water temperature ranges from
-3.5 O to 7 “C. These investigators stated that “an analysis of ionic ratios suggests
that the lake waters may consist of trapped sea water highly modified by subsequent
concentration by evaporitic processes, by addition of ions from surrounding soils,
and by addition of warm spring water”.

Mechanical, volcanic and cosmogenous contaminations

Any type of discrete detrital particle that can occur in sedimentary rocks can, in
general, also be expected to be present in carbonates. Many of these mechanically
added components constitute the “insolubles”, such as clay and different types of
silt and sand grains. Under certain conditions, however, carbonate sediments can
be diluted by calcareous and dolomite detritus derived from an older source. In
precise geochemical studies these contaminations must be carefully considered,
for the older carbonate-rock fragments may have been in equilibrium with a differ-
ent physicochemical environment.
Volcanic emanations, both on the continent and in the ocean, can contribute
solid particles, as well as gases and fluids to an environment of carbonate sedi-
mentation. Some of the geochemical problems involved were discussed by STRAK-
HOV (1964) who stated that little is known about the contribution of volcanic
material to sediments in general, or about the chemical contamination arising
therefrom.
Cosmogenous contamination of shallow-water carbonates may be negligible
because of the high rate of sedimentation and the possible immediate removal by
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 87

reworking processes. In localities where the rate of accumulation is extremely slow,

however, a cosmogenous source for some of the chemical constituents should be
considered. WISEMAN (1964), for example, mentioned that the components of
Mid-Atlantic deep-sea sediments are derived from lithogenous, biogenous,
hydrogenous (= derived from the surrounding body of water) and cosmogenous
sources. In this case, however, after taking into account numerous variables,
Wiseman tentatively concluded that the presence of trace elements can be explained
without assuming an appreciable addition from a cosmogenous source.

Magnesium in inorganic carbonates

It has been mentioned earlier that the maximum MgC03 content of inorganically
precipitated calcium carbonate is approximately 4 % in contrast to the maximum
value of about 30% in organically formed carbonates. The statement of CHAVE
(1954a, b) that there is no evidence of inorganic processes forming high-Mg calcite
under surficial conditions appears to be in general true, but one has to count on
minor exceptions and, in particular, on early diagenetic alteration of precipitated
carbonates. In the study of naturally formed sediments, it is very difficult to deter-
mine whether the Mg in carbonates was coprecipitated (as MgC03, Mg ( O H ) 2 ,
x Mg CO3. y Mg ( O H ) 2 . z HzO, etc.) or whether it has been added diagenetically
by adsorption-diffusion-absorption processes, for example. In doubtful cases,
therefore, it is not possible to discuss the limits of Mg uptake meaningfully (or that
of any other element) without first precisely knowing the mechanisms involved.
The Mg in carbonates can occur as: ( I ) magnesite or hydromagnesite (e.g.,
ALDERMAN and VON DER BORCH,1961); (2) dolomite (e.g., ALDERMAN and VON
DER BORCH,1961, 1963; PETERSON et al., 1963; SKINNER 1963; TAFTand HAR-
BAUGH, 1964); (3) ankerite (e.g., USDOWSKI, 1963a; BROVKOV,1964); ( 4 ) high-Mg
calcite (e.g., KUBLER, 1962, mentioned calcite with 40 % MgC03; FUCHTBAUER
and GOLDSCHMIDT, 1964, reported on a calcite with 18% MgC03; occurrences
were also noted by STEHLIand HOWER,1961; SEIBOLD,1962; TAFTand HAR-
BAUGH, 1964); and (5) low-Mg calcite (e.g., SEIBOLD, 1962; USDOWSKI, 1962; TAFT
and HARBAUGH, 1964). SKINNER (1963) showed that the Mg of a sedimentary
deposit can be present in more than one phase; the predominantly inorganic
carbonates of South Australia investigated by her are composed of magnesian cal-
cite, calcian dolomite and dolomite, and magnesite and hydromagnesite.

Strontium in inorganic carbonates

The problems of Sr concentration in inorganically formed carbonates must be

considered from two view-points: ( I ) contemporaneous coprecipitation of Sr, and
(2) subsequent introduction of Sr into the carbonate. ODUM(1957b) stated that in
most cases it appears that the Sr/Ca ratio of a carbonate is smaller than that of the
88 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

solution from which the carbonate was precipitated. In some occurrences, however,
some very high Sr/Ca ratios were observed indicating that certain sedimentary
processes can lead to Sr/Ca values equal to or greater than those of the aquatic
medium. In one case the ratios were comparable: the Sr/Ca ratio of the oolite
sediments, Great Salt Lake, Utah, is 4.23/1,000 atoms and is nearly equal to that
of the water (4.20/1,000 atoms). Odum mentioned that if the solubility products
are much exceeded, and if the solutions have no possibility to exchange with a
large reservoir, precipitation occurs in a closed system and the Sr/Ca ratios of the
precipitates are equal to those of the solution. For example, in five experiments the
addition of sodium carbonate to sea water (Sr/Ca = 9.0/1,000 atoms) at various
rates, produced in all cases calcium carbonate precipitates with Sr/Ca ratios ranging
from 4.9 to 13.3/1,000 atoms. Similar results were described by ZELLERand WRAY
(1 956). They also found that the Sr/Ca ratio increases with successive precipitation.
WATTENBERG and TIMMERMANN (1938, in: SVERDRUP et al., 1952, p.211) reported
that the solubility product of carbonate in sea water is approximately the same for
both Sr and Ca (5 * lo-’), in contrast to distilled water where it is much smaller for
strontium carbonate (0.3 * than for calcium carbonate (5 10-9). This suggests
that the Sr/Ca ratios of directly precipitated carbonate should be higher in low-
salinity water.
On investigating the coprecipitation of Sr with calcium carbonate from
aqueous sdutions, OXBURGH et al. (1959) found, in agreement with many other
investigators, that Sr2+ ions are much more readily precipitated with aragonite
than with calcite. They also mentioned that it is possible to estimate the Sr2+/Ca2+
ratio of the solution from which the precipitation took place.
GOLDBERG (1957) stated that examination of inorganically precipitated
calcium carbonate from sea water in the laboratory, and studies of artificially
prepared oolites, show that aragonitic structures contain more Sr relative to Ca
than does the sea water. On the other hand, the Sr/Ca ratio in sea water is higher
than that of most aragonite-precipitating organisms. HOLLAND et al. (1963) dis-
cussed the chemical composition of ocean water and its bearing on the coprecipita-
tion of Sr with oolites. They stated that according to the mean value of the concen-
tration of Sr as compared to Ca, one should expect a content of about 9,060 p.p.m.
of Sr in aragonite precipitated from sea water at 25°C. Holland and co-workers
mentioned that this is within the range of values found for the Sr concentrations
in oolites from Cat Cay, Bahamas.
ODUM(1957b) made it clear that it is difficult to evaluate the applicability
of the principle that rapid or restricted inorganic precipitation gives rise to high
Sr/Ca ratios, because the exact physico chemical mechanisms are still in dispute.
For example, aragonite-needle deposits are believed by some to be derived from
calcareous Algae, whereas others have suggested a bacterial or physico chemical
origin. Future investigations of the Sr/Ca ratios may cast some light on these
problems. As Odum indicated, the situation is made somewhat difficult by the
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 89

presence of reef corals and aragonitic green Algae having Sr/Ca ratios of 9-12/
1,000 atoms and 10-13/1,000 atoms or greater, respectively. The Sr/Ca values are
high (9/1,000 atoms or greater) in three occurrences (in the Bahamas, Key West,
and fossiliferous carbonates of Miami), where direct precipitation is assumed by
some investigators: ( I ) unconsolidated and consolidated oolite (9/1,000 atoms);
(2) drewite (9.3/1,000 atoms); and (3) consolidated and cemented rocks composed
of fragments of taxonomic components originally not high in Sr content.
The high Sr/Ca ratio of the drewite is comparable to the high value of
calcareous green Algae; however, it is also similar to the Sr/Ca ratios of some types
of inorganic precipitates from sea water. The Sr/Ca ratio does not, therefore, allow
a precise evaluation of depositional environment.
The mechanism that results in the cementation of beach-rock is still problem-
atic, and the explanations vary from inorganic to organic processes, as reviewed
by CHILINGAR et al. (1967). ODUM(1957b) mentioned Cloud’s suggestion that blue-
green Algae in the upper zones cause solution and reprecipitation due to large
diurnal pH changes associated with algal metabolism. It is possible thatc)he high
Sr/Ca ratios of all reef corals are due to the fact that the skeleton-building colonies
contain symbiotic Zooxanthellae and green Algae which produce similar pH
changes. Hence, the Sr/Ca ratios of cemented beach sands, calcareous Algae, and
reef corals may all be related to the algal processes. It must be concluded, there-
fore, that studies of minor and trace elements of the beach-rock cement may be
helpful in understanding its precipitation. Textural features of Devonian and Recent
reef limestones support the concept that Algae can cement beach sands (WOLF,
1963b, 1965~).ODUM(1957b) suggested that if rapid precipitation is required for
oolite genesis, the very great vital activity of organisms (photosynthesis) in shallow
water and reef environments may be partly responsible. High Sr/Ca ratios (greater
than 9/1,000 atoms) may be a paleoecological indication of algal photosynthesis.
More research, however, is needed before this line of reasoning is substantiated.
In the above discussions it was assumed that the Sr was located in the car-
bonate lattice. Under favorable conditions, however, celestite may form as an
accessory mineral in carbonate sediments. SKINNER (1963) pointed out that in the
recently formed sediments composed mainly of calcite and dolomite, the Sr is
present as celestite, and the Sr content ranges from 0.28 to 1.12%.
The strontianite deposits discussed by HARDER (1964) have been explained
by some as being the product of lateral-secretion processes of solutions which
derived the Sr from the limestones and organic skeletons. Others have suggested
a hydrothermal origin. Harder showed that the limestones and fossils do not
indicate any depletion of Sr and that there are no lateral changes in Sr content
from the limestones to the strontianite layers; this precludes a lateral-secretion
origin. Inasmuch as hydrothermally generated strontianite usually contains Ba,
Cu, Pb, Zn, and other elements, and because Harder found that these elements are
either absent or are present in traces, he concluded that a hydrothermal origin is
90 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

also unlikely. He proposed, therefore, that ascending solutions from the lower
Zechsteinsalzen rocks (evaporite-rich deposits) precipitated the strontianite. The
fact that the calcite was deposited prior to strontianite indicates that NaCl solutions
carried the Sr, because fresh water would have precipitated strontianite first. This
supports the viewpoint that the Sr was derived from the lower evaporites.

Other elements in inorganic carbonates, and associated contaminants

A number of trace elements, other than Sr and Mg, have been reported from in-
organically formed carbonate fractions of limestones. Considering the bulk
composition of carbonates, it is frequently very difficult to make a distinction
between the carbonate portion and the non-carbonate “impurities”. For example,
DEGENS et al. (1962) determined the concentration of the following trace elements
(in p.p.m.) in petroleum-bearing fresh-water carbonate concretions: B(290-420),
Mn(35400), Ni( <2-8.9), Ti(65-1,040), Cu(4.8-25.0), Zr( < 10-92), Cr(3.7-9.2),
V( 11-38), Ba(90-850), and Sr( 110-> 3,000). It is not quite clear to what extent some
of the elements in the concretions may have been adsorbed-absorbed from the
petroleum.
OSTROM (1957) stated that “the average content of barium, manganese, and
strontium, and the average range of Ba and Mn in the limestone samples, are
higher than the averages and ranges of these elements in the shale samples. This
suggests that these elements commonly are more closely associated with the minerals
composing limestone than those of the shales”. The average amounts and ranges
of the other twelve trace elements studied by Ostrom (ByCr, Cu, FeyPb, Mo, Ni,
K, Na, Ti, V, Zn) are highest in the shales.
The data on Ba given by Ostrom differ from those furnished by LANDERGREN
and MANHEIM (1963). As shown in Table XI, there is no enrichment in the case

TABLE XI

DISTRIBUTTONOF Ba AND Sr IN SEDIMENTSOF THE PACIFIC (glton)

(After LANDERGREN
and MANHEIM,
1963, table 6)

Clay sediments Calcareous sediments

Ba content (average) 1,170 1,070

Ba content (range) 300-2,500 800-1,350
Ba/Ca ratio 0.12 0.0035
Ca content (average) 9,600 306,000
Sr content (average) 200 1,480
Sr content (range) 85-580 940-2,000
Sr/Ca ratio 0.021 0.0048
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 91

of Ba. On the other hand, Sr content is higher in calcareous sediments than in clay
deposits by a factor of 7; this, in general, agrees with the observations of Ostrom.
In this connection, it is interesting to note that in the algal bioherms studied
by MALAN(1964) the copper is concentrated not in the carbonate deposits but in
the inter-reef argillites. Malan concluded that this type of occurrence supports a
syngenetic origin of the metalliferous deposits, because secondary processes would
most likely concentrate the copper within the carbonates. The latter have greater
susceptibility to solution, and replacement, than the argillites.
This leads one to the controversies of syngenetic versus diagenetic and epige-
netic origins of chemical components in carbonate skeletons, minerals, and rocks
that are considered in some detail later in this chapter. K. G. BELL(1963) mentioned
that the average content of syngenetically formed uranium of carbonates is
<0.00014.021%, whereas that of uranium of epigenetic origin is 0.0005-1.19 %.
The syngenetic uranium contents (in parts per million) of inorganic and
organic carbonates are as follows (TATSUMOTO and GOLDBERG, 1959): (1) oolites-
0.83-5.8; (2) calcareous skeletons-up to 3.2; (3) aragonite (precipitated in the
laboratory from sea water)-2.64.6; and ( 4 ) manganese nodules-3.6-5.0. The
thorium content of oolites is up to 2.0 p.p.m.
GOLDBERG (1957) stated that uranium contents of oolites compare favorably
with those of chemical precipitates in the laboratory, but differ distinctly from
those of organic material.
In regard to the doubly charged ions cadmium, tin, and manganese, GOLD-
BERG (1957) pointed out that they may show a similar substitution pattern to that
of Sr. They may be useful in characterizing environments inasmuch as contents
of these ions differ markedly in, for example, fresh and marine waters.
Investigations on chemical genesis and diagenesis, for instance, require
precise chemical analyses of particular components of the sediments rather than
of the bulk sample. This has been illustrated by USDOWSKI (1962) who presented
the chemical data on the ooids and matrix of a carbonate rock (Table XII).

TABLE XI1
COMPARISON OF CHEMICAL COMPOSITION OF MATRIX AND OOIDS

(After USDOWSKI,
1962)

Matrix 1.43-2.02 0.39-2.20 1,726-3,675 380-676 110-120

(2,600)
Ooids 0.46-0.79 0.16-0.18 744-1,314 189-381 276-383
(3,210)
92 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

Future studies may lead to the application of non-carbonate minerals present

in carbonate sediments for paleoenvironmental interpretations. RUCKERand
VALENTINE (1961), for example, suggested that the Na content of some shells, in
spite of being trapped in interstitial salts rather than forming part of the carbonate
crystal lattice, may be useful in determining paleosalinity.

Elemental composition of environment controlling precipitation and stability of

vaterite, aragonite, calcite, and dolomite

A large proportion of the Pleistocene and Recent calcareous sediments are com-
posed of aragonite and high-Mg and low-Mg calcite, of which the former two are
considered to be unstable. It is believed by many scientists that they either convert
to low-Mg calcite or are replaced by dolomite. Although general theories have
been available for some time, precise information has been lacking on (I) the
numerous factors that cause the genesis of all these minerals, and (2) the relative
stability of the carbonate minerals once formed. The following is a brief review of
some of the relevant literature.
In his experiments on the deposition of calcium carbonate in caves, MURRAY
(1954) found that:
(I) Those waters from which aragonite precipitates tend to have a higher
Mg/Ca ratio than do those depositing calcite.
(2) The addition of Mg(HC03)z to a solution of Ca(HCO&, or the replace-
ment of Ca by Mg ions, increases the proportion of aragonite in the calcium
carbonate precipitated. When concentration of Mg is approximately equal to that
of Ca, aragonite seems to predominate over calcite.
(3)Aragonite appears to be less abundant among the first crystals that appear
than among those precipitating later.
(4) The presence of Sr and Pb is effective in much lower concentrations than
is required of Mg in causing aragonite precipitation.
(5) Ba, Mn, and SO4 ions considerably in excess of the other ions used were
ineffective in causing the precipitation of aragonite in the test-tube experiments
performed. (The fact that Ba did not cause the formation of aragonite contradicts
the work of others, as discussed below.)
(6) A slight increase in temperature increases the proportion of aragonite.
The results of ZELLER and WRAY(1956) indicated that the form of calcium
carbonate precipitation is strongly controlled by the content of impurities in the
crystals. This impurity content, in turn, is greatly affected by impurity ion concen-
tration and the type of ions in the original solution, the pH, temperature, the
solubility of the polymorphs, crystal size, and the time of exposure of the crystals
to the solutions. The above authors pointed out that a close interrelationship
exists between these factors, and showed that high p H and temperature, low Mn2f
and high Sr2+, Ba2+, and Pb2f concentrations favor the precipitation of aragonite
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 93

from a solution of Ca(N03)~on the addition of N a ~ C 0 3 .Calcite formation is

favored by lower p H and temperature, and by high concentration of Mn2+ and
low concentrations of Sr2+, Ba2+, and Pb2+.
The observations made by WRAYand DANIELS (1957) showed that:
( I ) It is relatively easy by controlling temperature, pH and duration of
experiments to get either calcite or aragonite, or both.
(2) The temperature range is small and very critical.
(3) Aragonite may change rather rapidly to more stable calcite when in
contact with certain solutions and that this rate of change is indefinitely slow in
the dry state.
( 4 ) The aragonite lattice structure favors inclusion of cations (e.g., Sr, Ba,
Pb,) larger than the Ca ion.
(5) The formation of aragonite is induced by the presence of Sr, Ba, and Pb
under high p H and other conditions that favor their co-precipitation with calcium
carbonate; consequently, these ions are incorporated into the lattice of the aragonite.
(6) At low pH, the Sr, Ba and Pb carbonates do not precipitate and the initial
colloidal calcium carbonate particles do not contain these larger ions; this favors
calcite deposition.
(7) Under favorable conditions, Sr having small concentration in solution
is brought into the small volume of the first colloidal grains; this gives rise to a
high concentration of Sr in these particles.
(8)The colloid aggregates undergo subsequent orientation leading to crystal-
lization.
(9) Decrease in time available for the Sr, Ba, and Pb ions to diffuse out of the
colloidal particles back into the solution, and those factors that shorten this time
of escape, tend to produce aragonite. Conversely, factors that tend to lengthen
this time before crystallization, enhance the genesis of calcite.
(10) Higher temperatures accelerate the rate of crystallization and the ions
have little chance to escape; this promotes the formation of aragonite.
( 1 1 ) The greater the concentration of precipitating ions, the greater is the
tendency for the formation of colloidal deposition and thus the longer is the time
available before crystallization occurs. Hence, greater concentration of ions leads
to calcite if all other conditions remain constant.
(12) Aragonite in contact with water goes into solution and the carbonate is
reprecipitated as calcite because of loss of Sr to the Sr-deficient water.
(13) After minimum concentrations of Sr and other critical impurities are
obtained, further additions have little or no effect.
GOTO(1961) conducted extensive experiments that led him to conclude that:
( I ) The most important effect on the preferential or selective genesis of
aragonite and calcite is the solvation of water molecules. These molecules act upon
the surface ions of the particles and cause a marked loosening of the atomic binding
throughout the particles. Inasmuch as the denser structure of aragonite is less stable
94 K. H. WOLF. G. V. CHILINGAR AND F. W. BEALES

than that of the open structure of calcite under the influence of solvation by the
water molecules, the genesis of aragonite is favored in solutions with a diminished
solvation effect of water. This can be brought about by mixing the water with some
polar liquids having low dielectric constants, such as alcohols. Goto pointed out
that the secretion fluids of most organisms are believed to be composed of such
polar liquids, and the aragonite formation by organisms may be thus explained.
(See also discussions and references in the earlier section on organic aragonite
versus calcite genesis.) Future research on solvation effect of fluids of different
organisms and natural environments, such as lakes, lagoons, and so on, may be
valuable.
(2) Inasmuch as the solvation effect of water is considerably hindered by
thermal agitation of the water molecules, the formation of aragonite is favored by
higher temperatures from 60°C to the boiling point in contrast to lower tempera-
tures.
(3) Because of the low entropy structure of aragonite, it seems that oqtheoret-
ical grounds a high velocity of reaction does not favor the precipitation of arago-
nite. GOTO(1961) stated that although the slow reaction is of primary importance
in the formation of aragonite, it is by no means enough, as a slow reaction also
favors the genesis of the high entropical structure of calcite to the same extent.
From the viewpoint of reaction velocity alone, however, it is always more difficult
to form aragonite than calcite, and the difficulty of formation of aragonite in-
creases with increasing velocity of the reaction. This leads to the considerations
more directly related to the elemental composition of the solutions.
( 4 ) Both a comparatively larger pH value of the solution and a balanced
proportion of Ca2+ and C032- contents may be favorable for the precipitation of
aragonite according to GOTO(1961). In contrast, high concentrations of H+ ions
appear to favor the formation of the more open structures of calcite and vaterite.
Goto stated that the unbalance of Ca2+ and C032- contents seems to cause the
absorption of foreign ions in the growing nuclei of each CaC03 variety, and this is
usually unfavorable for the genesis of aragonite.
(5) The experimental results of Goto indicate that Mg2+, Sr2+, and Ba2+ ions
do not enhance the formation of aragonite. Mg2+ favors the genesis of calcite,
whereas Ba2+ causes the formation of vaterite (p-CaC03). Goto stated “it may be
confidently said regarding these facts that the diadochic substitution of Ca by Mg
makes calcite more stable relative to aragonite and p-form, and the substitution
by Ba makes the p-form more stable than the other two. It is a very interesting
fact that, in the present experiments, no aragonite was found even in the presence
of Sr2+, while calcite, in which an appreciable amount of Ca is replaced by Sr,
could form under the same conditions. These facts prove the chemically non-
negotiable nature of aragonite, and this nature may be attributed to the low entropy
structure of aragonite.” (See chapter on techniques of analyzing and examining
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 95

carbonates, WOLFet al., 1966, for possible misidentifications of vaterite, Ca-bearing

strontianite and aragonite as suggested by GOTO,1961.)
CLOUD(1962) pointed out that “WRAY and DANIELS directly (1957, p.2033),
and ZELLER and WRAYobliquely (1956, pp.145-147, fig.2), relate the effect of the
supposedly controlling ions to pH; but . . . the same relation of aragonite to higher
and calcite to lower pH seems more consistently interpreted in terms of carbonate-
ion concentrations and free energy of reaction”. Cloud was not able to demon-
strate that the mere presence of Sr or Ba, even in high concentration, causes the
formation of aragonite (see also INCERSON, 1962).
KITANO(1956a, b) has also determined the effect of numerous inorganic ions
on the proportions of aragonite precipitated.
TAFT(1962) pointed out that because aragonite is thermodynamically less
stable than calcite under pressure and temperature conditions prevailing at the
earth’s surface, some other factors must be responsible to cause the stability of
aragonite and high-Mg calcite present in carbonates as old as the Late Paleozoic.
Taft found experimentally that “inorganically precipitated aragonite in contact with
distilled water and with solutions of Ca and Sr ions changed slowly to calcite at
rates dependent on cation concentration and the temperature. If more than 5
p.p.m. of magnesium were present, however, the recrystallization did not take
place. High-Mg calcite and vaterite in contact with solutions containing 1,300 and
240 p.p.m. of Mg, respectively, did not recrystallize. In another series of experi-
ments, calcite was placed in a solution containing 1,330 p.p.m. of Mg (equal to its
concentration in sea water), and C02 was added to dissolve some of the calcite.
When the C02 was allowed to escape, aragonite and high-Mg calcite precipitated
even though some of the undissolved calcite was still present. Mg ion is evidently
an important factor in causing the precipitation and persistence of aragonite and
high-Mg calcite rather than calcite in marine environments.” As long as there is at
least one Mg ion for each unit cell of aragonite in direct contact with the inter-
stitial water, transformation of the aragonite to low-Mg calcite, according to
Taft, will not occur. This “critical concentration ratio” is approximately 1.0 for
aragonite but remains to be determined for high-Mg calcite. It is interesting to
compare Taft’s conclusions with those of GOTO(1961) mentioned above.
The recently completed investigations by TAFTand HARBAUCH (1964) also
appear to substantiate that the presence of enough Mg ions in interstitial waters
prevents the transformation of metastable carbonates to more stable forms.
(See also TAFT, 1967.)
SIMKISS(1964) prepared artificial sea water (without trace elements) and
added various solutions to examine the influence of particular ions on the mineral-
ogy of calcium carbonate precipitation. He stated that if C02 is removed from
natural sea water, aragonite is precipitated. Simkiss’ experimental results can be
summarized as follows: ( I ) solution with only NaCl and CaC12 formed pure
96 K . H. WOLF, G. V. CHILINGAR A N D F. W. BEALES

calcite; (2) solution with CaC12, MgCb plus NaCl precipitated aragonite; (3) in the
absence of Mg but in the presence of NaCI, KCI, N a ~ S 0 4plus CaC12, the precipi-
tate was found to be composed of calcite plus vaterite, and in some cases traces
of aragonite were recorded as well. The genesis of vaterite was an unexpected
result. Simkiss stated that the Japanese investigator KITANO(1962a, b) found that
vaterite formation was favored by high temperature and a large concentration of
Ba ions. Simkiss concluded that the p H in his experiments did not seem to have
had any marked effect on the genesis of vaterite. Perhaps an increase in the speed of
precipitation may assist in the formation of vaterite. This, however, requires
experimental confirmation as Simkiss pointed out.
JOHNSTON et al. (1916) believed that the presence of SO& ions in sea water
causes the precipitation of calcium carbonate in the form of aragonite. DUNBAR
and RODGERS (1957) stated that meteoric waters, being normally very low in salts,
tend to destroy aragonite; and that if connate fluids rich in S O P content are
trapped with aragonite in sediments, the aragonite may be preserved for millions
of years. MONAGHAN and LYTLE (1956), on the other hand, reported that the sul-
fate in a prepared solution of calcium chloride and sodium carbonate induces the
deposition of calcite, whereas Mg2+ ions cause the formation of aragonite.
SIEGEL (1965) could not come to a conclusion regarding the effect of stron-
tium on the formation of aragonite versus calcite in limestone caves, for even the
calcite investigated by him contained measurable quantities of Sr. Siegel, how-
ever, did note a preferred association of Sr with the aragonite. The Mg concentra-
tions determined by Siegel are notably higher in aragonite-calcite mixtures than
in calcite alone. The data did not permit evaluation of whether Mg promotes
aragonite formation as suggested by MURRAY (1954) in his cave studies. (For
additional information on the significance of Mg see the work by USDOWSKI,
1963a; also a summary of his findings is given in the next section.) Siegel concluded
that temperature is of primary importance in carbonate formation (in caves),
but further research is required to definitely substantiate this.
In studying the effects of the chemistry of environmental fluids on the
formation of various calcium carbonate polymorphs, it is most important to give
consideration to the influence of organic matter both in vivo and post-mortem in
addition to inorganic ions, as has been illustrated in the section on organic carbon-
ates above. Contradictory results obtained so far may well be associated withthe
influences of organic matter, superimposed on those brought about by inorganic
factors.
Aside from the numerous publications available on the parameters that
determine the origin of vaterite, aragonite and calcite, not much has, been reported
on similar relationships related to other carbonate minerals. SHEARMAN et al.
(1 961) concluded from their study of ancient carbonate rocks that gypsiferous
solutions could bring about dedolomitization. TEODOROVICH (1955, 1960)
showed on theoretical grounds that as a result of increasing NaCl concentration
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 97

to a certain limit, the solubilities of calcite and dolomite approach each other; and
this gives rise to dolomite formation. According to MEDLIN(1959), the presence of
NaCl in solution also extends the range of temperature at which dolomite can be
precipitated. HARDER (1964) mentioned that NaC1-containing solutions precipitate
CaC03 first and then SrC03, whereas in pure water the converse would be the case.

Environmental influence on the particle form of carbonate precipitates

Varying the numerous parameters has been shown to cause the formation of
different mineralogic precipitates within the carbonate system. Similarly, the
genesis of gel-like carbonate, aragonite needles, spherulites and oolites, for example,
appears to be a reflection of a range of physicochemical and biochemical factors.
Although much more experimental work is required, the two examples presented
here illustrate some of the results obtained so far.
MONAGHAN and LYTLE(1 956) stated that a carbonate-ion concentration of
more than 0.002 mol/l in solution causes precipitation of spherulites, and concen-
trations of less than 0.002 mol/l induce the formation of needle-like crystals. That
is to say, when the solubility products are much exceeded, as in the case of rapid
precipitation, the formation of calcium carbonate occurs in the form of spherulites.

1 6 4 3 2 1 6 8 4 2 1 1 1 1 1 1 1 1 1 1 1 1 1 0
0 1 1 1 1 1 1 1 2 4 8 16 3 2 6 4 1 2 5 2 5 0 5 0 ~ 1

-
16.5%
.-
0

c
P- R M Nd*P - mi
1 64 3216 8 4 2 1 1 1 1 1 1 1 1 1 1 1 1 1 0
0 1 1 1 1 1 1 1 2 4 8 16 32'64 1252505W#w)1

MgICa weight ratio of the solution

F i g 5 CaC03 precipitation from solutions having different salt content and varying Mg/Ca
ratios. Every dot represents a precipitation experiment. Mg/Ca ratio of sea water = 2.11, G =
amorphous gel as determined by X-rays; A =aragonite; K=calcite; V=vaterite; Sph I =ooid-like,
optically negative spherulites with visible radial-fibrous structure (30-40 mp in diameter);
Sph 2=optically negative spherulite, without visible fibrous structure (5-10 mp in diameter);
P = prismatic crystals (approximately 15 mp in diameter); Nd 1 =granular precipitate, partly
rhombohedra1 (approximately 10 mp in diameter); Nd 2 =finely granular precipitate (approxi-
mately 1 mp in diameter). Two identical sets of figures at the lower and upper parts of the diagram
represent Mg/Ca ratios; e.g., Mg/Ca ratio of 1/0, 64/1, 32/1, 16/1, etc. (After USDOWSKI. 1963b;
fig.1; by permission.)
98 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

Slower precipitation, on the other hand, favors the genesis of needles. They also
discovered that sulfate-reducing Bacteria can cause the precipitation of “ooliths”.
Monaghan and Lytle found that rhombic crystals of calcite formed from solutions
having Ca2+ alone, Ca2+ plus Na2+ ,Ca2+plus K+, and Ca2+ plus S O P . On the
other hand, solutions with Ca2+ plus Mg2+ gave rise to amorphous gel, which
transformed upon standing into spherulitic crystals of aragonite and calcium
carbonate monohydrate (CaC03.HzO).
The investigation by USDOWSKI (l963b) demonstrated that the origin of
amorphous calcium carbonate, vaterite, calcite and aragonite minerals, and their
form (as spherulites, radial-fibrous and concentric oolites, and prismatic and granu-
lar crystals) are dependent on the Mg/Ca ratio and the salinity, among other
factors. As shown in Fig.5, the experiments indicated that vaterite, calcite, aragonite
and finally amorphous calcium carbonate gel (in that order, with stages where
two occur simultaneously) were precipitated with an increase of Mg/Ca ratio from
solutions having a salt content of 16.5 %and 3.6 %. The vaterite formed as,a finely
granular or crystalline precipitate, the calcite deposited in the form of spherulites
without recognizable radial-fibrous structure, and the aragonite gave rise to optical-
ly negative spherulites with distinct radial-fibrous appearance. Calcium carbonate
precipitation occurred in the form of calcite, aragonite and gel from the solution
having salinity of 0.5 % and with an increase in Mg content; however, no spherulites
formed. The calcite occurred as finely granular or crystalline particles among which
some rhombohedra were present. The aragonite precipitated as crystals with pris-
matic and pyramidal faces. No vaterite formation took place in this case.
Thus, the experiments performed by Usdowski suggest that the Mg/Ca
ratio determines the CaC03 polymorph, and the salinity controls the habit or
structural form of the carbonate precipitate. Ooids or spherulites are formed when
the Mg/Ca ratio lies between 2/1 and 8/1. The lowest limit of salt content necessary
for ooid-genesis lies somewhere between 3.6 % and 0.5 %.

Influence of chemical composition of depositional medium on organisms

It has been said earlier that chemical elements in environmental medium influence
organic life, and that on the other hand organisms control elements either directly
or indirectly. Up to now no consideration has been given to the possibility that
specific types of elements, or certain concentrations of elements can be harmful to
organic existence, and may result in dwarfed faunas and floras and, possibly, mass-
mortality. Little information is available on these aspects as related to the geo-
chemistry of carbonate sediments and most of the data are based on inferences
and hypotheses.
TASCH(1957) pointed out that the presence of dwarfed fauna in black shales
may possibly be due to the prolific growth of Algae. Catastrophic death of organ-
isms that normally live in upper water horizons can result from recirculation of
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 99

poisonous waters from the bottom, and noxious red water caused by the presence
of certain phytoplankton.
Selective toxicity of waters as far as animals and plants are concerned will
change the ecological equilibrium and hence the composition of any carbonate
deposits formed. Similarly, such important ecological controls as the salinity,
nutrient concentrations and so on, will influence the living community. Because of
the selective concentration of certain ions exhibited by different life processes, the
elemental composition of any carbonate formed will, in turn, be influenced by
faunal and floral variation.
It is interesting to note here that CHILINGARand BISSELL (1963) on theoretical
and experimental grounds showed that possibly the high Mg/Ca ratio of Precam-
brian sea waters prevented the formation of hard protective and skeletal structures
of organisms, or largely hindered their formation. FAIRBRIDGE (1964) pointed
out that though the alkalinity in the Precambrian has been high, a high pcoZ
could have kept all carbonates in solution, except in partly isolated lagoon or
intertidal environments. Almost aN Precambrian carbonates show traces of Colleniu
type (intertidal) Algae.
It appears feasible to assume that not all organisms respond equally to the
same elements and to the same ranges of concentrations. Whereas some organ-
isms prefer specific elements, others find them harmful. Certain concentrations
of chemical elements may exclude one group of organisms, whereas other types of
life may even prefer high concentration of the particular elements. It would be most
helpful in environmental interpretations to continue experiments on the factors
(involving elements) that stimulate and factors that hinder the growth of various
organisms.

DIAGENESIS-EPIGENESIS RELATED TO CARBONATE COMPOSITION

The field of carbonate diagenesis-epigenesis encompasses a large number of factors

and mechanisms that alter the content of major, minor and trace elements, and text-
ure and structure of individual carbonate particles and whole rock units. Partly to
avoid controversy and mainly because one is concerned here with all “secondary”
changes irrespective of when they have occurred, the term “diagenesis” and “diage-
nesis-epigenesis” must be considered here in its widest sense in contrast to the very
restricted application used by CHILINGAR et al. ( 1967). “Diagenesis-epigenesis”
includes all secondary processes except metamorphism. In this respect, it must be
emphasized that present-day weathering of. ancient sediments results in changes
that can easily be attributed by mistake to diagenetic or epigenetic phenomena.
No extensive discussion of the numerous secondary processes is given here,
inasmuch as they are covered in the various sections of this and other chapters of
this book, and by CHILINGAR et al. (1967) elsewhere. In general, one has to admit
100 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

that little is known about each of the mechanisms listed in the next paragraph; this
particularly applies to grain diminution (WOLF,1965b), as practically no data on its
influence on chemical changes is available. In many investigations one resorts to
more than one process to explain the field and laboratory observations. For
example, loss of trace elements is explained loosely by either “leaching or recrystal-
lization”, a gain of elements by either “adsorption, diffusion, or uptake in solid
solution”. None of these terms mean much, unless the causes and processes they
represent are precisely understood and given a solid geochemical foundation.
Much remains to be done in applying chemical and metallurgical principles and
concepts to geological problems, and in determining to what extent they are
applicable to natural occurrences of minerals and rocks. For example, similar
features observable in both synthetic metals and ancient carbonate sediments may
not necessarily be the product of the same or similar causes, as has been pointed
out by FOLK(1964).
In relation to a chemical alteration of carbonates, the numerous diagenetic
processes include: ( 1 ) inversion: aragonite to calcite; (2) conversion: high-Mg
calcite to low-Mg calcite; (3) pseudomorphic replacement: carbonate by carbonate;
(4) grain growth; (5) grain diminution; (processes I through 5 are commonly
grouped and referred to collectively as “recrystallization”); (6) genesis of non-
carbonate components; (7) solution, leaching and bleaching; (8) adsorption-
diffusion-absorption; and (9) precipitation of carbonate: cement and nodules.

Inversion: aragonite to calcite

Some of the factors that cause or prevent inversion have already been mentioned.
It is also important to note here that FUCHTBAUER and GOLDSCHMIDT (1964)
described skeletons in which inversion was prevented by the clayey and oily
matrix in which they were embedded.
One problem that requires the full attention of researchers is the enigma of
expulsion versus uptake of elements in relation to “recrystallization”, i.e., are
they a cause or an effect of secondary changes. For instance, SIEGEL (1960) con-
cluded that Sr has to be leached out of the calcium carbonate before inversion can
take place, whereas others maintain that recrystallization (see next section) leads
to the expulsion of trace elements. It seems possible that, depending on the cir-
cumstances and the types of elements concerned, either one or the other, or both,
explanations may be true. On the other hand, SPOTTS(1952) believed that during
recrystallization there is a possibility of Mg uptake from the connate fluids.
KRAUSKOPF (1 955) mentioned that during inversion of aragonite to calcite,
the liberated Pb, Zn, Ni, and Co may combine with traces of S from organic matter
to form small grains of galena, sphalerite, millerite and linnaeite.
LOWENSTAM (1954a) found that Serpulidae tubes with an initial aragonite
content ranging from 53 to 96 %, after 1 year of exposure had an aragonite content
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 101

between 45 and 78 %. Extreme care should be exercised, therefore, if old museum

specimens are used for carrying out mineralogic and trace-element studies.
It has been suggested that grinding of aragonite specimens may cause an
inversion to calcite. KRINSLEY(1960), however, stated that no such alteration was
observed in his work.

Conversion, pseudomorphic replacement, grain growth and grain diminution

As has been mentioned earlier in the discussion on inorganic carbonates, TAFT

(1962) and TAFTand HARBAUGH (1964) found that a high concentration of Mg in
sea water or interstitial fluids prevents transformation of aragonite and high-Mg
calcite to the more stable low-Mg and Mg-deficient calcites. On the other hand,
STEHLI and HOWER(1961) mentioned that although it is known that high-Mg
calcite is the least stable among the carbonates present in the Recent sediments
investigated by them, the ultimate disposition of the Mg released is still far from
clear. Do the certain ions in interstitial fluids reach a critical concentration, at
which further transformation of unstable to stable carbonate cannot take place
until the fluids are diluted? It has been shown that recrystallization rates are con-
trolled by the concentration of particular cations, e.g., recrystallization in solutions
containing Ca2+ and Sr2f ions, and in distilled water occurs a t different rates.
Consequently, one of the principal factors controlling recrystallization is clearly the
degree of saturation and rate of migration of the sea water and interstitial fluids.
There seems little doubt that recrystallization causes migration of elements
but the processes are complex. For example, USDOWSKI (1962) showed that con-
tents of Mg, Fe, Mn, Sr, and C1 in an oolitic limestone are comparable to those of
an average limestone. The distribution of these elements, however, is particularly
significant. Mg, Fe, Mn, and Sr are concentrated in the calcitic matrix (inter-
granular debris plus sparry calcite cement), whereas ooliths are enriched in C1.
Usdowski explained the higher contents of elements in the matrix by assuming that
recrystallization of the ooliths expelled these elements. The CI is thought to be
present in inclusions in the ooliths. Circulating solutions were able to remove CI
selectively from the intergranular matrix due to its high porosity and permeability,
whereas they were not able to reach the inclusions in the ooliths. It seems that
recrystallization did not affect these CI-containing inclusions. Clearly, more re-
search is needed before the behavior of different elements is clearly understood.
ODUM (1957b) found a noticeable difference in the Sr content of recrystallized
in contrast to unaltered fossil specimens. He plotted the percent deviation of the
Sr/Ca ratio of the skeleton from the matrix as a function of the percent deviation
of Sr/Ca ratio of the fossil from its modern counter-part (ODUM,1957b, fig.lO).
The distribution pattern of the points suggests that fossils and the matrix tend to
have similar Sr/Ca values when the Sr/Ca ratios are low. On the other hand, when
the Sr/Ca ratios of fossils are as high as those of unrecrystallized recent skeletons,
102 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

the Sr/Ca values of the shells are usually greater than those of the matrix. Odum
pointed out that echinoderms and corals appear to be much more readily altered
than brachiopods and molluscs. He concluded that it is doubtful whether many
fossil echinoderms exist that have not undergone transformation, however well
preserved they appear on the outside. Odum cited an example of three very well
preserved Pennsylvanian urchins that have a Sr/Ca ratio of 0.89/1,000 atoms in
comparison to 3.06/1,000 atoms in three recent urchins. In contrast, Odum found
no such discrepancy between Pennsylvanian and Recent mollusca. He suggested
that a very low Sr/Ca value of the order of less than 1/1,OOO atoms in certain
skeletons may be a useful indicator of alteration. As pointed out by CHILINGAR
(1962b) in the case of Mg content, however, there is a possibility of change in the
chemistry of the oceans with time.
KULP et al. (1952) made similar investigations on skeletons and found a
definite relationship between recrystallized and unaffected fossil specimens: the
former always had lower Sr/Ca ratios. These investigators suggested that the release
of Sr during recrystallization may have given rise to the celestite (SrS04) that has
been encountered in the same sediments. USDOWSKI (1963a) also presented evidence
that cone-in-cone structures may have been formed by recrystallization of a marl
and that this process was accompanied by a loss of both Sr and Mg ions.
It has been shown by BANNERand WOOD(1964), among others, that re-
crystallization of calcareous skeletons takes place differentially and in a predictable
sequence. The loss of trace elements by these skeletons, therefore, should be equally
predictable.
In addition to the effects of recrystallization on inorganic elements, it has
been suggested by ABELSON (1959a) that this process leads to the expulsion and
loss of amino acids and other soluble organic compounds. These, previously
isolated from interstitial fluids, become mobilized upon recrystallization.

Genesis of non-carbonate components (e.g., celestite)

ODUM(1957b, partly quoting NOLL,1934) mentioned that percolating waters are

enriched and carbonate sediments are depleted in Sr content. Celestite (SrS04)
forms when the Sr-rich fluids come in contact with sulfate either in solution or as a
mineral. Inasmuch as the solubility product of SrC03 in sea water (5.10-') is
smaller than that of SrSO, (lO-5), strontianite will tend to replace celestite and
celestite, in turn, will replace gypsum. That this has occurred is indicated by studies
of crystal pseudomorphs. Odum also pointed out that a number of investigators
suggested that the celestite associated with dolomite deposits contains the Sr that
was released by inversion of aragonite and/or by the dolomitization of the lime-
stone. On the other hand, the possibility must be considered that the aragonite
precipitation and/or dolomite genesis took place in a saline environment and that
the celestite was formed directly from the sea water.
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 103

Solution. leaching and bleaching

Removal of elements from carbonate minerals and rocks may be conveniently

divided into processes that (1)result in the removal of bulk material by uptake into
solution, and (2) leach the elements selectively from the material under attack.
Bleaching of the carbonates can be due to either removal of components and/or by
alteration in situ. Conversion of high-Mg calcite and high-Sr aragonite to calcite
and aragonite devoid (or having only a trace) of Mg and Sr, respectively, has been
explained as the result of “leaching”, for example.
In a number of cases contradictory information is given on whether an
element can be removed from a crystal that is in contact with a fluid, or whether
complete solution and recrystallization are required to remove it from the crystal
lattice. ZELLERand WRAY(1956) stated that Sr cannot be selectively removed
without complete solution or recrystallization of the carbonate. On the other hand,
SIEGEL(1960) mentioned that Sr can be leached from the carbonate lattice prior to
recrystallization. In the case of magnesium, under suitable conditions (pH, etc.)
it would go into solution and, therefore, would be selectively extracted from the
carbonate rock.
CHILINGAR (1962b) also pointed out the existence of disagreement among
investigators as to the possible loss of Mg from calcareous skeletons to the sea
water during and shortly after sedimentation. He exposed skeletons to sea water,
which was changed periodically, for 4 months and found no detectable change in
the Ca/Mg ratio.
CHAVE(1954a, b) mentioned that the removal of Mg by circulating waters
can be observed in the Pleistocene formations of southern Florida. The extensively
leached oolitic limestone studied by him now has only 0.37 % MgC03, although it
contains 15% of echinoids, Foraminifera and Bryozoa that originally were prob-
ably rich in Mg content. Here again, however, solution and reprecipitation could
be involved.
PILKEY (1964) in his study of Recent carbonate sediments restricted his
examination to the <62, <31, and < 4 p size fractions “on the assumption that
any post-depositional changes would be most obvious in the finer size fractions”.
He found that the < 4 p fraction is usually more unstable (aragonite plus high-Mg
calcite) than the < 64 p fraction. Pilkey concluded that selective mineralogical
alterations due to solution and recrystallization play a secondary role, if at all,
during early diagenesis of material near the depositional surface. Some objections,
however, can be raised against Pilkey’s reasoning for general application. It has
been pointed out earlier in this chapter that ,the degrees of stagnancy and satura-
tion of interstitial fluids significantly control the stability of the so-called unstable
carbonate minerals (aragonite and high-Mg calcite). As the movement of inter-
stitial fluids is very slow (or practically nil in some instances) in the finer grained
sediments, Mg-rich waters may prevent transformation of the fine-grained unstable
104 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

minerals. In contrast, the coarser sediments without a fine matrix permit rapid
renewal of interstitial fluids and have a better chance to come in contact with
waters that do not enhance the stability of aragonite and Mg-rich calcite. Never-
theless, under favorable conditions selective alterations affecting the finer fractions
are possible.
Inasmuch as different size-grades of carbonate sediments may contain
specific minor and trace elements, it follows that if selective removal of certain
size fractions is possible by solution, a selective extraction of chemical elements is a
consequential possibility.

A dsorption-diffusion-absorption

Adsorption takes place when some foreign ion or molecule is fixed to the surface
of a solid. As pointed out by FYFE(1964; see also RITCHIE, 1964), absorption involves
the preliminary surface adsorption followed by diffusion into the interior of the
solid. Molecules adsorbed on a surface are frequently deformed and chemical
reactions occur on the surface. KRAUSKOPF (1955) stated that the adsorption of
ions on the grains of a growing precipitate occurs as a result of coprecipitation,
occlusion, ion exchange, and isomorphic substitution. He referred to the original
literature and discussed some of the difficulties encountered in setting up general
rules to predict the behavior of ions.
TEICHERT (1930) discussed some of the problems of adsorption; and a num-
ber of papers contain descriptions of experiments performed on the adsorption
of ions on carbonate minerals. In general, however, as GRAF (1960) pointed out
after summarizing the literature, there is meager knowledge on the subject, and
some of the results appear to be contradictory and inconclusive. BISSELL and CHI-
LINGAR (1958), for example, discussed diagenetic dolomitization and migration of
Ca and Mg ions by diffusion. GARRELS et al. (1949) and GARRELS and DREYER
(1 952) reported experimental data on the subject.
The investigations of TUREKIAN and ARMSTRONG (1961) showed that cal-
careous molluscan skeletons are slightly enriched in Ba relative to Ca, as compared
to sea water. On the other hand, molluscs discriminate slightly against Sr and much
more so against Mg. According to Turekian and Armstrong, these phenomena
suggest that the “adsorption properties of ions on the surface of the growing shell
front or during complexing in the blood of the organisms has a strong effect on the
ultimate trace-element content of a molluscan test. If it were a matter of simple
substitution in the lattice, then Goldschmidt’s commonly quoted rules would be
operative and Ba should be excluded relative to both Ca and Sr because of its
much larger ionic radius. However, if adsorption and complexing are important
controls, one might expect a greater enrichment of Ba than Sr in a growing shell.”
GOLDBERG (1954, 1957) referred to surface adsorption or “scavenging” of
minor and trace elements. This process depends on the size and charge of the
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 105

adsorbed ion and the topographical character and charge of the adsorbing surface.
For example, Mn-, Al-, and Fes+-hydroxides are very efficient in scavenging.
GOLDBERG (1954) proposed that an electro-chemical process is responsible for
giving either a negative or positive charge to the sea floor. When the latter is
positive, negatively charged manganese micelles will be attracted; and when
negative, positively charged iron will accumulate. The manganese hydroxide will
scavenge nickel and copper; and the iron hydroxide supposedly will scavenge cobalt.
Goldberg also suggested that “the concentration of minor elements by
members of the marine biosphere is explained either by the direct uptake of the
element or by the uptake of iron or manganese oxides with the accompanying
scavenged element”. LOWENSTAM (1963) pointed out that certain calcareous shells
contain minute proportions of phosphate, iron oxide and sulfate that appear to be
of organic origin; and that trace elements may be expected to be adsorbed on these
non-calcareous specks.
GOLDSCHMIDT (1937) and MASON (1958), among others, pointed out that clay
minerals, particularly montmorillonite, have a marked adsorptive capacity for
ions (mainly positive) in solutions. The amounts of elements (e.g., c o h e r , lead,
arsenic, mercury, selenium), which have been supplied from the primary rocks to
the oceans during the past geological periods, would have been sufficient to have
caused serious poisoning of the ocean unless some mechanism had removed these
elements. Goldschmidt stated that a number of the poisonous elements such as
selenium, arsenic, lead, antimony, and bismuth, have been removed by adsorption
on iron hydroxides. It would be equally valid to assume that even if the poisonous
elements had not been removed, the organisms most probably would have devel-
oped a tolerance during evolution.

Precipitation of carbonate cement and nodules

Investigations of both elemental and isotopic compositions in conjunction with

textural studies of carbonate-cement types may prove to be useful in determining
the time of formation of the cement relative to the sediment-framework and the
mode of cement genesis. Consequently, this may show what types of cement are
useful as paleoenvironmental indicators (WOLF,1963a, b; 1965a). The influence of
living and dead organic matter on the precipitation of carbonate cement must also
be given its due consideration (WATABE and WILBUR,1960). Further studies may
lead to information that will solve the contradictory theories on beach-rock genesis.
For example, if cryptocrystalline cement described by CHILINGAR et al. (1966) and
WOLF(1965~)is indeed of algal origin, the Sr,and Mg contents of the cement should
(as long as diagenesis did not cause secondary changes) correlate favorably with
contents of these elements in products resulting from algal metabolism.
Distribution patterns of elements in carbonate concretions have been shown
to furnish valuable data on the relative mobility of certain elements during diage-
106 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

nesis-epigenesis. For instance, LOGVINENKO and KOSMACHEV (1 961) examined

carbonate (Mg, Ca, Fe, Mn) concretions and found that the Co, Sr, Ba, V, Ni,
Cr, and Ti contents of the concretions and adjacent rocks indicate that the partici-
pation of different elements in the formation of the concretions varies distinctly.
There is a direct correlation between the Co and Mn occurrences, for example, but
in general the interdependency among the elements is more complex. Two groups
of elements were recognized by these authors: (I) elements migrating in the stage of
diagenetic redistribution of the material in the deposits (Co and Sr); and (2) ele-
ments that do not appear to undergo redistribution (Ba, V, Ni, Cr, Ti).
A most interesting example of regional distribution of various types of
carbonate cement and concretions described by BROVKOV (1964), is presented in the
section on regional aspects related to carbonate chemistry.

Chemical and physical changes brought about by diagenesis-epigenesis

In general, chemical and physical changes brought about by diagenesis-epigenesis

can give irise to the following modifications and alterations:
(I) Chemical changes or absence thereof: (a) no change; (6)change in mineral-
ogy (e.g., aragonite to calcite); (c) removal of trace elements; ( d ) addition of trace
elements; (e) change in content of isotopes; and (f)decomposition of organic
matrix and matter, which in itself may lead to alterations of a chemical and/or
physical nature.
(2) Physical changes or absence thereof: (a)no change in texture and structure,
and (b) change of texture and structure.
In general, many of the earlier sections have included discussions on the
numerous diagenetic-epigenetic alteration mechanisms, and only a few supple-
mental case histories that illustrate the above list of possible modifications are
reviewed here.
Some of the complexities to be expected in diagenetic changes are discussed
by TUREKIAN and ARMSTRONG (1961) who set up a quantitative model to “en-
courage the viewing of a fossil shell of any age as a complex of alteration products”.
In the case of the molluscs investigated by them, three “end-members” were
considered: (I) original unaltered shell material composed of pure aragonite;
(2) completely recrystallized material, either replacing the original shell or filling
interstices; and (3) a “reaction layer” in which trace elements have been adsorbed
on otherwise unaltered aragonite shell material.
The reaction layer may be a consequence of the approximately 3 % of organic
matter which is present as a network within the hard skeletons. Upon decomposition
of the organic material, vacant interstices may be left and thus furnish a reactive
environment for adsorption processes. Turekian and Armstrong pointed out that
because alterations giving rise to phases 2 and 3 proceed at different rates in differ-
ent environments, the ratios of these three phases are not simply predictable from
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 107

the calcite concentration. Assuming that each one of the phases has a distinctive
trace-element composition, concentration of a particular element in a mollusc
skeleton is equal to:
Cim = amxi + bmyi + CmZi
where C i m = measured concentration of element rn in shell chip i; xt = fraction of
original aragonitic unaltered material in shell chip i ; y t = fraction of calcite in
shell chip i; zi = fraction of “reaction layer” aragonitic in composition in
shell chip i; xi+ + yi zi = 1; and a,, b m , Cm = the concentrations of the trace
element in the phases x i , y i , and zt, respectively. Analogous models can be set up
for other skeletal types, i.e., for those originally composed of calcite only, or of
both high-Mg and low-Mg calcite, and so forth.
TUREKIAN and Armstrong (1961) found that similar molluscan fossil shells
contain l-lO% calcite in contrast to the complete absence of calcite in similar
modern types, which are composed of aragonite only. They assumed that secondary
effects gave rise to calcite, and used the percentage of calcite of the sampled skele-
tons as an indication of the degree of diagenetic change. Turekian and Armstrong
also found that the aragonite crystals of the fossil specimens are somewhat larger
than those in the modern representatives; this could be due either to the species or
diagenetic effect.
The trace element versus calcite-content curves of Turekian and Armstrong
indicate a general increase for Mg, Fe, Mn, and Ba with increasing calcite content.
The curve for Sr is the most difficult to interpret. The highest Sr contents occur
when calcite content lies between 2 and 10%; and these Sr concentrations are
considerably higher than those of modern molluscan shells (average 1,600 p.p.m.).
Upon reaching a maximum, the Sr content decreases with increasing calcite content
toward the 100% calcite value.
The Mg content shows a hundred-fold increase between the aragonitic and calcitic
end members. The Mn content also exhibits a marked increase with increasing
calcite content as indicated by a concentration of 500 p.p.m. of Mn for low-calcite
shells. This is about 100 times higher than the Mn content of contemporary mollusc
shells (KRINSLEY, 1959). The trend of the curve for Ba shows a slight increase in
Ba content with increasing percentage of calcite. Three very high values recorded
by TUREKIAN and ARMSTRONG (1961) may be due to the presence of barite. On the
other hand, even where the shells are almost totally composed of aragonite, an
average content of Ba is about 130 p.p.m., which is more than 10 times the average
for modern molluscs. The Fe content also increases with increasing amount of
calcite, but the spread of values is larger. In addition, aragonite specimens are much
higher in Fe content than their contemporary equivalents.
After considering the possibility that either (I) the shells having lowest
calGite content are the closest approximation to the original shell, or (2) the
composition reflects the multiple effects of diagenesis and weathering, Turekian
and Armstrong subscribed to the second alternative. Because of the unusually high
108 K. H. WOLF, G. V. CHlLINGAR AND F. W. BEALES

Fe and Mn concentrations and the increase of Sr and Ba contents by factors of

two and ten, respectively, an interpretation based on diagenetic changes is more
plausible.
Important for future research are two further conclusions reached by TURE-
KIAN and ARMSTRONG (1961): ( I ) that visual appearance of shell material is not
necessarily a valid indicator of degree of alteration, and (2) that even where there
is no apparent alteration in mineralogy, there may be an alteration of the original
chemical composition of the shell. In addition, they doubt if the composition of
molluscan external hard parts are useful for paleoecological reconstructions.
The loss of Sr from the carbonate particles during fossilization and diagenesis
has been reported by KULPet al. (1952), ODUM(1957b), and SIEGEL(1960), for
example; whereas KRINSLEY (1959) found that Sr and Cu contents (with one excep-
tion) in his samples remained constant. Krinsley also reported that Al, Mn, and
Mg contents are higher in pteropod shells from cores in contrast to the shells of
plankton samples. Krinsley suggested that the higher concentrations are the result
of uptake of these elements from the ocean bottom sediments. As Sr and Cu con-
tents did not change, he suggested that they may be used as standards in the study of
post-depositional changes. In view of the contradictory results obtained for Sr by
different investigators, however, this may not be possible. TUREKIAN (1959) found
a notable enrichment in Ba, whereas Sr content appears to undergo the least change.
PILKEYand GOODELL (1964), comparing the composition of fossil and recent
mollusc shells, determined that the aragonitic shells of older specimens usually
have higher Ba, Sr, and Fe contents, and lower contents of Mn and Mg than their
modern representatives. In one calcitic species, the average Sr and Mg concentra-
tions were lower in the fossil, whereas the other elements did not show statistical
differences between the Recent and fossil specimens. Of particular interest are the
“inter-specific variation” and the “element-element correlation” illustrated by
Pilkey and Goodell. Curves illustrating the former concept indicate that inter-
specific variations in composition of fossil and contemporary aragonitic skeletons
are similar only for Mg and Sr, whereas Ba, Fe, Mn and calcite contents in the older
skeletons illustrate inter-specific variations different from those of the Recent
shells.
In examining the element-element correlations, PILKEY and GOODELL (1964)
found that in some cases Ba and Mn contents of fossil, but not of Recent, shells are
directly related; whereas in other instances Fe and Mn contents show a strong
correlation. Again these changes are explained as being due to diagenesis and
possibly to weathering. Pilkey and Goodell concluded that the available evidence
favors post-depositional alterations which have occurred mainly within the crystal
lattice, and that the nature and properties of the bonds formed or broken are more
important than the similarity of ionic radii to Ca. The changes are such that they
increase the stability of the crystal lattice. Hence, the contents of elements that
enhance the stability will increase and contents of those that decrease the stability
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 109

of the crystal lattice will diminish during secondary processes. Based on this con-
cept, Pilkey and Goodell listed the elements in order of increasing “desirability” in
the aragonite lattice under post-depositional conditions as Mn <Mg <Sr <Fe
<Ba. It is significant to note that the compositional changes occurred in aragonitic
and calcitic specimens examined by them without apparent “recrystallization”.
The contradictions of trace-element depletion versus enrichment may be
partly due to chemical changes caused by physicochemical differences between
the environment in which the organisms lived and those conditions that existed
within the sediments. For example, there may be an increase or decrease of element
concentration in the diagenetic interstitial fluids as compared to the original sea
water. Both Mg-depletion and Mg-enrichment can occur in littoral gastropods
(KRINSLEY, 1959, 1960); and most likely are due to local variations in environ-
mental conditions. ODUM(1951, 1957b) pointed out the possibility of loss of Sr
during recrystallization when the carbonate is in contact with fresh water.
The technique employed by LOWENSTAM (1961) in determining the absence or
presence, and in the latter case the degree, of diagenetic alterations, is of particular
interest. As pointed out in the previous sections, several properties of calcareous
shells can be affected by a singre factor: aragonite/calcite ratios, Sr contents, Mg
contents, and 1 8 0 / 1 6 0 ratios are sensitive to environmental temperatures. On the
other hand, diagenetic modifications affect the 1 8 0 / 1 6 0 ratio and the Mg and Sr
concentrations somewhat differently. LOWENSTAM (1961,1963), therefore, concluded
that a comparative investigation of these three parameters will permit a more
reliable interpretation of diagenesis in contrast to an independent study of each of
these without relating them to each other. Diagenetic alteration by fresh water, for
example, would result in 1 8 0 / 1 6 0 values corresponding to spuriously high tempera-
tures, and in Sr and Mg concentrations giving spuriously low temperatures. If, on
the other hand, the temperature of formation as determined by 1 8 0 / l 6 0 ratio
agrees with that determined from Sr and/or Mg contents, then it is possible that no
changes took place. Lowenstam demonstrated that in diagnetically altered fossil
brachiopods the relationships of the 1 8 0 / 1 6 0 ratios to the SrC03 and MgC03
concentrations are different from the relations existing in modern specimens from
both the average ocean water and from isolated water. It should be possible,
therefore, to discriminate between unaltered fossil skeletons from average and
isolated waters on one hand, and diagenetically affected shells on the other.
Lowenstam illustrated SrC03 versus 1 8 0 / 1 6 0 and MgC03 versus 1 8 0 / 1 6 0
curves of the fossil brachiopods that match similar curves based on analyses of
Recent brachiopods from similar depositional environments; in these cases it is
assumed that no alteration occurred. Some .others give values that, on superficial
examination, resemble those of recent hyposaline environments. The proportionate
relationships of their SrC03 and MgC03 contents as related to the 180/’60 ratios,
however, are not compatible with those of recent specimens from hyposaline
waters. They harmonize with diagenetic modifications in the presence of fresh
110 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

TABLE XI11

DIAGENETICCHANGES IN lSO/lsO RATIO AND SrC03 AND MgC03 CONTENTS OF BRACHIOPODA

(After LOWENSTAM,
1961, p.255)

Initial stage of diagenetic alteration no change no change 45

Intermediate stage of - 0.8 15 50
diagenetic alteration
Most advanced diagenetic alteration - 1.2 20 50

water low in Sr, Mg, and 1 8 0 contents. It is interesting to note the progressive and
selective diagenetic alterations as illustrated in Table XI11 (based on the data given
by LOWENSTAM, 1961).The values are compared to those of unaltered brachiopod
specimens.
The study conducted by Lowenstam illustrated that of fourteen fossil speci-
mens, 1 8 0 / 1 6 0 ratio was preserved in nine samples; SrC03 content, in eight samples;
and MgC03 content, in two specimens. The results indicated that the oxygen-
isotope ratios are the most stable and the Mg content, the least stable. By compar-
ing the 1 8 0 / 1 6 0 ratios and SrC03 concentrations in fossil and in Recent skeletons,
it is possible to distinguish original from diagenetically depleted MgC03 contents.
With an increase in diagenetic alteration and the formation of secondary calcite,
the fossils usually have lower 180/160 ratios and are significantly depleted in
MgC03 and SrC03 contents.
Relationships between the Ca/Mg ratios, on one hand, and silicification and
dolomitization (and porosity) on the other, have been described by CHILINGAR and
TERRY(1954) and CHILINGAR (1956b, c).
In the section on skeletal carbonates it has been mentioned that once the
chemical composition of Recent shells has been determined to a reasonably
reliable degree, they can be used as “standards” or “norms” for the study of fossil
specimens. Similar extrapolations in the study of inorganic carbonates may be
possible, but most likely will prove to be difficult. For example, SKINNER (1963)
found that the recently precipitated carbonates in the Coorong lagoon, South
Australia, range in composition from Ca0.77 Mgo.23(C03)2 to Cao.gsMgo.oz(C03)2.
Investigating older carbonate sediments in the district of the Coorong, Skinner
found evidence suggesting that they formed under similar conditions; however,
these carbonates have compositions ranging from C ~ O . W ~ M ~ O . I Zto ( CCao.98-
O~)Z
Mgo.oz(CO3)2. If they had the same original composition as the carbonates of the
Coorong lagoon, then recrystallization and/or leaching possibly changed the
composition.
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 111

REGIONAL ASPECTS OF CARBONATE COMPOSITION

In the preceding sections no consideration has been given to possible regional or

facies changes in the composition of carbonate sediments, and the chemistry was
discussed in view of more local factors and processes. The significance of regional
aspects goes far beyond mere academic considerations and is of interest to both
metalliferous and non-metalliferous exploration geologists alike.
Surveying the literature on regional chemical changes in carbonate rocks,
one will find that the amount of available information is meager. This seems
to be predominantly a reflection on the lack of methods that would permit a
rapid, and yet reliable, analysis of many specimens. On the other hand, literature
(in particular Russian publications) furnishes sufficient analytical data for case
history studies of which some are considered below.
As in many other branches of geology, it may be relatively easy to make
reliable determinations of a number of parameters, in this case of chemical ele-
ments, but any interpretations based upon them are at present largely speculative
and frequently contradictory. The problems of reconstructing past events on the
basis of chemical composition have been pointed out by CLAYTON and DEGENS
(1959) as follows: “DEGENS et al. (1957, 1958) have demonstrated that trace-element
data for a complete rock sample are less conclusive and sometimes not interpretable
with reference to their environmental grouping than analyses of certain mineral
fractions. Analytical data on separated detrital or chemical end members, i.e.,
clays, carbonates, sulphides, organics, allow more conclusive interpretation of the
environmental conditions during sedimentation than trace-element analyses on the
total rock sample. In addition, correlation between two or more variables was
found to be more useful for the environmental classification of sediments than the
absolute values of one element.”
According to CLAYTONand DEGENS(1959), “the great defect in trace-
element investigations is the lack of a world-wide absolute environmental standard
both marine and fresh water. This is mainly caused by the local variation in trace-
element supply (i.e., source effects). Although certain elements are found to be
generally useful as fresh-water or marine indicators, each geological or geographical
area has to be evaluated separately by establishing new correlation standards.”

Sr, Mg, and CalMg ratio distribution

Strontium variations in reef complexes have been studied by FLUGEL and FLUGEL-
KAHLER(1962; Sauwand limestones) and .STERNBERG et al. (1959; Steinplatte
limestones), among others. These investigators found a gradual increase of SrC03
content from the back-reef to the basin limestones (Fig.6). STERNBERG et al. (1959)
reported values of 60-1 50 p.p.m., 150-420 p.p.m., and 3804,570 p.p.m. SrCO3
for the back-reef, fore-reef and basin sediments, respectively. Their investigations
112 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

1 reef fore-reef basin

back-reef

, ,
-
\ \ '.
'
?, ?' ,
---? --____
Fig.6. A. Distribution of SrC03 in the Sauwand and Steinplatte Reef Complexes. (After FLUGEL
and FLUGEL-KAHLER, 1962, fig.11; by permission.) B. Approximate (very diagrammatic as
precise numerical values are not given) trend of the Sr content reconstructed from descriptions
by SIEGEL (1961) illustrating the decrease of Sr from the reef to the fore-reef facies in contrast to
the occurrence shown in Fig.6A.

indicated that carbonates which have undergone recrystallization have low Sr

contents due to depletion. This interpretation is supported by the high Sr values of
unrecrystallized reef samples. The relatively high Sr content and the well-preserved
organisms in the basin sediments indicated that diagenetic to epigenetic depletion
due to recrystallization has been less intense here.
FLUGEL and FLUGEL-KAHLER(1962) concluded that recrystallization lowered
the Sr content of the Sauwand limestones. They postulated that depletion of Sr
took place in more or less equal proportions in both the back-reef and reef facies
so that the present Sr,content still gives some idea as to the d a t i v e proportions of
the original Sr contents. In general, however, one has to expect differential recrys-
tallization according to the mineralogically different types of carbonates (e.g.,
aragonite, high-Mg calcite, low-Mg calcite) and different environments of forma-
tion (e.g., fresh water, lagoon, reef, basin). The final trace-element composition
after diagenetic-epigenetic recrystallization, therefore, may be very complex and
difficult to interpret.
FLUGEL and FLUGEL-KAHLER(1962) reported that there are no systematic
changes in the amounts of MgC03 with changes in the SrC03 content in the ancient
rocks they studied. On the other hand, SIEGEL (1961) found that in Recent car-
bonate sediments the Mg concentration decreases as the Sr content increases and
reaches a maximum where Sr content is at a minimum. The iso-strontium/calcium
atom ratio lines plotted by Siege1 showed that Sr/Ca ratio of the sediments increases
with distance offshore from the Pleistocene reef and as the living reef is approached.
The highest value for Sr content is reached about 1 nautical mile on the leeward
side of the living reef and decreases at the reef and seaward from it (Fig.6). As the
reef organisms consist mainly of aragonite with a high Sr content, these results
suggested that most of the reef-debris is deposited about 1 mile on the leeward side
of the reef, thus causing the shift of the maximum of the curve.
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 113

So many different factors control the distribution of both Mg and Sr within

a reef-complex, that it is most difficult to, first, make generalizations, and, second,
use findings on Recent carbonates in the interpretation of ancient reef-complexes.
If carbonate differentiation as reported by MAXWELL et al. (1964), which is due to
differential breakup of aragonitic and calcitic skeletons, is extensive, a number of
other factors will determine whether the fine, Sr-rich detritus will be transported
to lagoons or to the deep-sea basin. Hence, a Sr maximum may be found either on
the leeward or seaward side of the reef. Many ancient reefs are composed mainly
of calcareous Algae and it is most difficult to predict both Sr and Mg maxima in
this case. CHILINGAR (1960) found that the Ca/Mg ratio of carbonate sediments
increases on going away from shore, which can be attributed to the abundance
of Mg-rich coralline Algae in the near-shore waters. The Devonian Nubrigyn
Reef Complex of New South Wales (WOLF,1965a) has been shown to comprise
many algal bioherms, some lagoonal deposits, and algal debris washed in the
opposite direction to form the “turbidite” facies of the adjacent basin. Where all
facies are composed of algal components, Sr- and Mg-differentiation of skeletal
origin may be poor to absent, unless physicochemical processes independent of the
mineralogy of the organisms caused secondary differentiation of the trace elements
at the site of accumulation.
ODUM(1957a) pointed out that knowledge of the geochemical cycle of Sr is
most important for the understanding of the regional and local distribution of
strontium. Variations in Sr/Ca ratios during sedimentary cycle are presented in Fig. 7.
ODUM(1957b) stated that the Sr content is higher in sediments of isolated
lakes than in those of open lakes, for cases in which the chemical natures of drainage
are similar. Generally, sediments of closed basins have a high Ca content; how-
ever, open basins also can have a wide range of Ca values. Isolated or closed lakes
should have Sr/Ca ratios comparable with the ratios of the inflowing tributary
waters. In open water bodies the rate of Ca extraction due to precipitation may
be less than the rate of Ca inflow. In addition, if Sr is excluded relative to Ca during
SrlCa
Rain

1
Attered Surface
Limestone Waters
uplift
Intermediate
1.2- 2.5
Water 3.8
Unconsotidated

Fig.7. The variation of the Sr/Ca ratio during the sedimentary cycle. Values for various phases
are means of data from the study of ODUM(1957a). Strontium is more readily removed into solu-
tion during consolidation than calcium. This behavior accounts in part for low values in limestones
and high values in ground waters. (After ODUM,1957a, fig.5; by permission of the Institute of
Marine Sciences, Texas University.)
114 K. H. WOLF, G. V. CHlLlNGAR AND F. W. BEALES

carbonate deposition in such lakes, the Sr/Ca values of the sediments will be less
compared to those of the inflowing waters. In closed basins, then, the Sr remaining
in the waters will build up to a higher concentration, whereas in open lakes an
exchange with other water bodies is possible. It was found that the sediments of the
Great Salt Lake (Utah), East Twin Lake (Connecticut), and Lake Mendola
(Wisconsin) have lower Sr/Ca values than the lake waters. This substantiates the
concept of Sr being excluded during deposition of calcareous sediments. Although
the above explanation and data may be applicable in some cases, numerous other
factors have to be taken into account that will cause deviations from any “norm”.
TUREKIAN (1955) stated, for example, that his work points to the fact that there
will not be very large increases in Sr/Ca ratio in evaporating arms of the sea.
H. A. Lowenstam (personal communication to ODUM,1957b), however, gave data
indicating that high Sr/Ca ratios exist in parts of the sea having high salinity.
In general, according to Odum, the Sr/Ca ratios of marine carbonate sedi-
ments are higher than those of the calcareous deposits of open fresh-water basins.
Because of the size and diversity of the ocean, however, a wide range in Sr/Ca
values can be expected. Odum concluded that the Sr/Ca ratio varies partly with
depth because of differential sedimentary accumulation of the calcareous deposits;
this has been borne out by the work of others mentioned above. In some localities,
the Sr/Ca ratio may be controlled largely by the variation in content of insoluble
components. In areas where there is no chemical precipitation of carbonate sedi-
ment, the Sr/Ca ratio is determined by the taxonomic composition of the calcareous
skeletons. In marine, as well as in lake sediments, as the Ca concentration diminish-
es, the Sr/Ca ratio approaches the value characteristic of the acid insolubles; and
when the Ca content increases, the Sr/Ca ratio approaches that of the carbonates
present.
As mentioned previously, diagenesis-epigenesis can mobilize chemical
elements. FOLK( I 962) postulated that brackish-water micrites recrystallize more
readily than either normal marine or lacustrine fresh-water micrites. Geochemical
profiles through a carbonate formation, that accumulated in a variety of environ-
ments, may offer the original or slightly altered composition in one area, whereas in
other parts the chemistry has been markedly changed. This has been brought to
attention in discussing the work of FLUGEL and FLUGEL-KAHLER (1962) and
STERNBERG et al. (1959). KUBLER (1962) also found that both fresh-water and
marine limestones contain the same amount of Sr and concluded that the Sr
content may be independent of salinity. On the other hand, DEGENS’ (1959) studies
showed that recent fresh-water limestones have a lower content of Sr than marine
carbonate sediments; this is caused presumably by the lower amounts of Sr in
fresh water. With an increase in age of limestones, however, the difference in
Ca/Sr ratio between the fresh-water and marine sediments afipears to diminish;
and the Sr contents of Paleozoic carbonates, independent of facies, do not deviate
much from the average value of 500 p.p.m. Hence, fresh-water limestones must
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 1I5

have gained and marine limestones lost Sr (relatively speaking) during the geologic
history as a result of diagenesis-epigenesis.
A hopeful note was sounded by KUBLER(1962) who concluded that the Sr
content is a useful parameter in environmental interpretations. In general, Kiibler
found in his studies that the maximum content of Sr occurs in sediments containing
aragonite; and that light-colored carbonates are poor in Sr in both Mg-calcite and
dolomite in contrast to the darker carbonate rocks. During diagenesis the Sr
appears to have been mobilized in some cases to form celestite.
KULPet al. (1952) reported that Sr contents of the Mississippian sediments
differ from those of the older limestones, and suggested that this may be due to
difference in salinity. On the other hand, various samples collected 144 miles along
the strike of one formation, the Harrodsburg Limestone (Indiana, U.S.A.),
exhibited a constant Sr/Ca ratio which indicates homogeneous conditions of
sedimentation. Only values collected from the southernmost part of the formation
fall appreciably outside the range of experimental errors.
In his studies of Recent carbonates, CLOUD(1962) found that the magne-
sium content of the calcite fraction is either high (1 1-19 mol%) or low (0.5 molx).
The low-Mg calcite is particularly abundant in near-shore localities and in bottom
core samples that reached bed rock. The abundance of high-Mg calcite increases
offshore, and Cloud stated that it is probably all skeletal.
Comparative investigations of carbonate provenance may show that each
sedimentary region may have a characteristic range of mineralogic and/or chemical
composition. Table XIV is based on the work of TAFTand HARBAUGH (1964)

TABLE XIV

RANGES OF MINERALOGIC ELEMENTAL COMPOSITION OF SOME MODERN CARBONATE SEDIMENTS

(Data after TAFTand HARBAUGH,

1964)

Locality Aragonite Low-Mg High-Mg CalMg SrlCa Mol %

( %) calcite calcite ratio (x MgCO3
( %) ( %) ratio in high-Mg
calcite

Southern 0-89 1-100 0-54 6-1.51' 1.7-15.1'

Florida
Bahaman 2-91 0-6 8-98 16.8-93.0' 5.0-16.0
Islands2
Andros 45-99 0-1 3 1-51 22.1-212.3 13.5-16.0
Island
Baja 38-90 I4 2 3-58 16.0-37.0' 8.2-1 1.2
California

'The values were not determined for all samples. (See original publication for details.)
Andros Island and Yellow Bank.
116 K. H . WOLF, G. V. CHILINGAR A N D F. W. BEALES

giving the ranges of aragonite, low-Mg calcite and high-Mg calcite contents, and
Ca/Mg and Sr/Ca ratios.
E. T. Degens reported on a detailed study of fossiliferous and unfossiliferous
beds in Mesozoic and Tertiary limestones. E. T. Degens and his co-workers
(personal communication to INGERSON,1962) concluded that (I) the Ca/Mg ratio
decreases as salinity increases, and (2) fossils occur only in formations where the
Ca/Mg ratio is greater than 50. The absence of fossils is believed to reflect hyper-
saline conditions.
KUBLER (1962) described regional facies changes of two cycles of sedimentary
units rich in carbonate sediments of lacustrine (fresh-water), brackish, and marine
environments. In addition to numerous differences not considered here, each cycle
exhibits a different carbonate phase. Calcite is the dominant mineral in the whole
profile. In the fresh-water limestone of cycle one, the Mg present occurs as detrital
dolomite. In cycle two, however, the Mg is present in the calcite lattice to form Mg-
calcite of various compositional ranges. The interbedded carbonates associated
with coal deposits contain the maximum amount of Mg-rich calcite having the
highest Mg content. In any one hand-specimen, there are often two types of
Mg-rich calcite: one with a MgCOs content of about 20 %, and an other with as high
as 40% MgC03.
The formation of Mg-rich carbonate sediments in Recent saline lagoons has
been described by SKINNER (1 963) and ALDERMAN and VONDER BORCH(1 963), and
in a number of other publications. Skinner reported on the saline Coorong lagoon
which is an elongated finger of the ocean and is connected to the sea at the northern
extremity. He also described a string of isolated, shallow, saline lakes which are
isolated remnants of the Coorong lagoon. The amount of Mg being precipitated
from the saline water in the form of carbonates appears to increase southward,
away from the mouth of the Coorong lagoon, and reaches a maximum in the
isolated lakes. The calcite/dolomite ratio seems to be distinctive for a particular
lake or a particular position in the Coorong lagoon. As the amount of dolomite
increases in the sediment, the content of Mg in associated calcite decreases.
Conditions in the enclosed lakes appear to be the most favorable for the formation
of dolomite relative to calcite. When the deposition of carbonate ceases, halide and
sulfate minerals may subsequently precipitate. The precipitation of carbonates
appears to be related to the activities of plants that control the chemical composition
of the water by photosynthesis.
ALDERMAN and VON DER BORCH(1963) visualized a definite pattern in the
sedimentation history of the Coorong lagoon and the lakes. Inasmuch as the lakes
became isolated from the Coorong lagoon by marine regression, it is possible to
assign relative ages to the lakes or groups of lakes. This age in turn seems to delimit
the type of sediment and carbonate petrology. The assemblages of minerals that
have been recognized by the above two investigators are given in Table XV. This
list of assemblages is thought to be in the order of increasing age of the environ-
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 117

TABLE XV

SEQUENCE OF MINERAL ASSEMBLAGE IN COORONG LAGOON AND ASSOCIATED LAKES, SOUTH AUSTRALIA

(After ALDERMAN
and VON DER BORCH,1963)
~~

Age of lake Mineral assemblage Approximate Mg/Ca raiio in

water ai time of maximum p H

111
( I ) Aragonite plus magnesian calcite 5
3 (2) Magnesian calcite 6

g
.-
(3) Magnesian calcite plus calcian
dolomite 8

I
(4) “Ordered” dolomite 10
(5) Dolomite plus magnesite 16
.1 (6) Aragonite plus hydromagnesite 20

ment: type I occurs in the Coorong lagoon; type 2 is forming in the most recently
isolated lakes in which the absence of aragonite is striking; type 3 occurs in the
somewhat older isolated lakes where the amount of calcian dolomite progressively
increases with increasing age (in the southern older lakes); and types 4, 5, and 6
occur in the oldest groups of lakes.
Considering various geochemical factors, ALDERMAN and VON DER BORCH
(1963) found that the relative amounts of Mg and Ca are important in understand-
ing the genesis of the above-described carbonates. They found that a high Mg/Ca
ratio of these carbonates is associated with increasing age. The approximate values
of the Mg/Ca ratio of water for each group of lakes at the time of maximum pH
are shown in Table XV. The above authors suggested that as the waters of each
lake approach the saturation level at which NaCl begins to crystallize, the Mg
concentration in the water becomes unusually high and calcareous material reacts
so as to increase its Mg content. The following reaction series was proposed by
Alderman and Von der Borch: aragonite-tmagnesian calcite-tcalcian dolomite+
“ordered” dolomite. (The relationships of dolomite plus magnesite, and aragonite
plus hydromagnesite to the above series is not quite clear as yet.)
WEBER(1964a) presented the elemental composition of a large group of
dolostones and dolomites. It is significant that his more finely grained so-called
“primary” dolostones are consistently higher in alumina and some trace elements
that would likely be associated with clay minerals. As Weber noted, the so-called
“primary” dolostones are in fact probably secondary. One might suspect that the
most obvious chemical differences between his so-called “primary” and “secondary”
groups are possibly largely due to the differences in energy of the original environ-
ment and the relative amounts of carbonate and clay mineral muds that accumulat-
ed in the original calcareous sediment. Apart from the significant differences noted
by Weber there is a remarkable similarity in trace-element associations for dolo-
118 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

mites and dolostones which tends to confirm the similarity of origin of most
dolostones. The latter probably owe their origin to secondary replacement of
original calcium carbonate material.

Mn, Sr, P, and Cu distribution in sediments of the Russian platform (STRAKHOV

et al., 1956)

Most of the following information is based on the work of Russian investigators

who accumulated interesting data for the preparation of lithochemical facies
maps. In dealing with facies changes, it is not possible to divorce entirely carbonate
from terrigenous sediments. On the contrary, it is more illuminating to treat
chemical aspects on a comparative basis, showing synchronous variations as well
as those reflecting changes through geologic time within the same basin of depo-
sition.
In an absence of comparative analytical data illustrating possible regular
changes in content of elements with the environment of accumulation, STRAKHOV
et al. (1956) used an indirect method by employing the familiar “ideal facies
section” to solve the problem. They postulated that the lithologic sequence sands-
silts-clays-marls-limestones reproduces the whole range of gradual transition
from the near-shore to the basin or pelagic facies. Some objections to this idealiza-
tion have been raised by RONOVand ERMISHKINA (1959) which are discussed in the
next section.
In studying ancient sediments that were formed under humid conditions in
the geologic past, STRAKHOV et al. (1956) found that in the “ideal facies” section
the concentrations of most elements increase on going from sandstones to siltstones
to argillites and then diminish toward the pure calcareous deposits. The concen-
trations of Mn, P, and Sr, however, continue to grow to a maximum in the mads
or the argillaceous limestones, and occasionally in the pure carbonates (Fig.8).
These investigators mentioned that ten other elements also show a somewhat
higher concentration in the carbonate sediments. Hence, it seems that in the plat-
form type of environment many elements preferentially to almost entirely bypass the
near-shore zone. Strakhov and co-workers stated that the distribution of elements
depends mainly on the mode of transportation and the physicogeographic
conditions, and to a lesser extent on the properties of the element.
The ratio of amounts of an element in suspension and in solution varies
considerably for different elements. For example, Strakhov and his co-workers
mentioned that Fe, Mn, P, and a number of minor elements such as V, Cr, Ni, Co,
Cu, Pb, Zn, Ga, and others, remain mainly in suspension during transportation
by river waters and enter true solution only to a minor extent. Also, within the size
range of a suspension, some elements may occur in coarser portions, whereas
others may constitute part of the finer components. These differences in mode of
element migration in streams are partly responsible for the differentiation of
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 119

3.0

2.o

I .o

Fig.8. Distribution of elements in Pashiysk marine sediments of Second Baku. ss=sands; sf =silts;
arg=argillaceous sediments; murl=marls; arg Is = argillaceous limestones; Is =limestones.
(After STRAKHOV et al., 1956.) The ordinate was not marked in the original article, and the values
presented here (%, are assigned by the authors of this chapter. lO-*O,< probably
also applies to the lower graph.

elements during sedimentation. The migration of matter in solution tends to favor

transportation to the pelagic zones of a basin inasmuch as the maximum contents of
significant elements which migrate mainly in solution are found in clay-rich and
calcareous basin sediments. When suspensions dominate the mode of transporta-
tion, then association of elements with particular size grades becomes more signifi-
cant, and the maxima on the distribution curves shift toward the coarser near-
shore sediments. Elements adsorbed on colloidal matter tend to accumulate in the
clay zone, whereas detrital minerals and elements present in their lattices are de-
120 K. H. WOLF. G. V. CHILINGAR AND F. W. BEALES

posited in the silts and sands. In cases where an element migrates both in a lattice
of coarser particles and adsorbed on colloidal matter, the curve may have two
maxima: one for sand and one for clay deposits.
In addition to the suspension/solution ratio and the distribution of elements
in the different size grades, geographic factors of element availability are important.
Thus, the ultimate element-distribution is affected by the type and intensity of
weathering in the source area and degree of sorting during transportation and
deposition.
Intensive chemical weathering of the source rocks breaks down the complex
silicates, alumino-silicates, and sulfides of igneous and metamorphic rocks. The
elements thus obtained (Fe, Mn, P, V, Cr, Co, Cu, Pb, Zn, Be, etc.) migrate partly
in solution and partly in suspension as adsorbed cations on colloidal particles such
as clay minerals, as mentioned above. The more intensive the chemical weathering
on the continent, the more impoverished in elements will be the sand- and silt-
sized sediments. Consequently, there will be a higher concentration of the elements
in fine-grained argillaceous-calcareous deep-water sediments.
The better sorted sediments usually show a clear maximum on the distribu-
tion curve. Poor sorting gives rise to spreading and more uniform element distri-
bution in the various environments. An intensification of chemical weathering in
the source area, accompanied by a high degree of sorting, results in an increase of
contrast in the distribution of the elements in different lithologies, and in an in-
crease in similarities between the distribution curves of the various elements in
lithologically different types of sediments. In other words, the variability in curve
shape becomes less and the curves become more comparable and concordant under
intense weathering and better sorting conditions (STRAKHOV et al., 1956).
“Dilution” of sediments faraway from shore with carbonates results in a
decrease in the proportion of elements in marls and carbonate rocks as compared
to argillaceous sediments. The content of Sr, however, which is associated largely
with carbonates, should increase with increasing carbonate content.

Mn distribution in sediments of the Russian platform (RONOV

and ERMISHKINA,
1959)

Some objections raised against the use of “ideal facies concept” by STRAKHOV
et al. (1956) come from RONOVand ERMISHKINA (1959). As shown in previous
sections, STRAKHOV et al. (1956) found that the Mn content of the Lower Frasnian
and the Lower Carboniferous rocks of the Second Baku sediments increases from
the sands to the limestones. Thus, they concluded that Mn content increases with
increasing distance from the shore; that is, it increases with distance from the
Mn ore deposits, which Ronov and Ermishkina reported as having been situated
along the shores of the ancient shallow seas.
Strakhov and co-workers, of course, were well aware that local variations
from their “ideal section” could occur. RONOVand ERMISHKINA (1959), however,
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 121

demonstrated more than a local variation and developed the concept further.
They analyzed 10,389 samples and obtained the following results: 0.063 % Mn
in sands and silts, 0.075 % Mn in clays, and 0.068 % Mn in carbonates. These data
are in direct contradiction of the assumption that Mn content increases gradually
from the sandstones to the clays and then to the carbonates.
It was suggested that this discrepancy was mainly due to the differences of
rock types studied by STRAKHOV et al. (1956) and by RONOVand ERMISHKINA
(1959). The latter two scientists divided all the types of sediments that had been
analyzed into two genetic groups according to the paleoclimatic conditions: first,
sediments formed in an arid, hot and dry climate; and second, deposits accumulat-
ed in a humid and warm climate. On considering this division, two completely
different types of Mn distributions became apparent. In humid zones, such as those
studied by STRAKHOV et al. (1956), the Mn concentrations increase continuously
from the sands to the clays and further to the calcareous sediments. On the other
hand, in arid zone accumulations the Mn content increases from the sands and
silts to the clays and then decreases rapidly to a minimum in the carborpte sedi-
ments (Fig.9).
The changes of the Mn concentration through the stratigraphic column of
the Russian platform are given in Fig.10. The sediments of some periods show
relative enrichment, whereas others indicate impoverishment in Mn content. The
direction of these changes through time are more or less the same for all rock types,
but for some intervals the displacement of the maxima and minima reflects the
lithology of the sediments. (In this connection it should be remembered that the
Mn contents of the Russian platform sediments are considerably smaller than those
of geosynclinal sediments. In modern oceanic sediments the Mn content is about
4 times higher than the Mn contents of the Russian platform sediments.)
If the lithology and Mn variations are compared, it becomes evident that

Mn0

!
in *I.
Humid
0.100
~

,0 zone
0

0’0201 Sands ;nd

siltstones
1
Clays
’ Carbonate rocks ’
Fig.9. Variation in MnO content of sedimentary rocks of the Russian platform according to the
climatic conditions of their formation. (After RONOVand ERMISHKINA, 1959, fig.1.)
122 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

greater uniformity in Mn contents prevails in the sandstones and siltstones,

whereas the fluctuation is a feature of the carbonate rocks.
As shown in Fig.11, MnO follows FeO closely in its distribution through
the stratigraphic column, indicating that Fe and Mn are genetically related;
this has also been noticed by KUDYMOV (1962). The ratio of Mn to Fe remains more
or less constant in clays and sands, whereas in carbonate rocks there is generally
an increase in the Mn/Fe ratio relative to the associated sands and shales. This
suggests that in zones of carbonate formation some regional geochemical processes
are operative that lead to some differential separation of Mn and Fe. Local favorable
pH and Eh conditions in both the transportation and deposition mediums (KRAUS-
KOPF, 1957) may cause a nearly complete geochemical differentiation of Mn and

MnO
in%
Carbonates
0.26-
f
0.24. I
022- I
0.20 I
018. I
0.16 I I
0.14 . A I
0.12 -
0.10 .
OD8 -
0.06 .
004 -
0.02 -
0 -

690 510 430 30 225 150 m 0

Absolute time in millions of years

Fig.10. Variation in MnO content in sands and silts, clays, and carbonate rocks of the Russian
platform. (After RONOVand ERMISHKINA, 1959, fig.2.) Explanation of symbols:
snz = Sinian PZ = Upper Permian
Cm = Cambrian TI = Lower Triassic
o = Ordovician Tz = Middle Triassic
s = Silurian T3 = Upper Triassic
SI = Upper Silurian JI = Lower Jurassic
sz = Lower Silurian Jz = Middle Jurassic
DI = Lower Devonian J3 = Upper Jurassic
Dz = Middle Devonian Cri = Lower Cretaceous
Di = Frasnian Crz = Upper Cretaceous
D: = Famennian Ce = Cenozoic
c 1 = Lower Carboniferous Tr = Tertiary
cz = Middle Carboniferous Pg = Paleogene
c 3 = Upper Carboniferous Ng = Neogene
PI = Lower Permian Q = Quaternary
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 123

690 510 L30 310 225 150 70

Absolute time in millions of years
Fig.11. Variation in the MnO, FeO, and insoluble residue (I.R.) contents in carbonate rocks of
the Russian platform. (After RONOVand ERMISHKINA, 1959, fig.5.) For explanation of the symbols
see Fig. 10.
Mn 0 Carbonates
in % -f A
0.130 / \
I \
0.110 / \
\
Clays
"'":
RWO-
,,, '-.
\
.A
0.050- 'f

Fig.12. Variation in the MnO content in sedimentary rocks according to the facies conditions of
their formation. (After RONOVand ERMISHKINA, 1959, fig.6.)

Fe that would favor the formation of sedimentary manganese deposits.

The maximum Mn concentration, independent of lithology, is associated
with coastal facies deposits; and Mn content decreases both toward the continental
and basinal sediments, as illustrated in Fig.12. On the other hand, if the climatic
conditions are taken into consideration, their influence on the facies profile
becomes quite clear (Fig.13). Coastal sediments of a humid environment have
124 K. H. WOLF, G. V. CHlLlNGAR AND F. W. BEALES

0.09 -
0.08 .
0.07 . Humid
zone
0.06 . e---

0.05-
0.04- \

\,Arid
zone
'Continental '
ao3.
0.02 I 1
lagoonal
and
Pelagic

Fig.13. Variation in the MnO content in Russian platform deposits according to the facies and
climatic conditions of their sedimentation. (After RONOV
and ERMISHKINA, 1959, fig.7.)

a higher Mn content than those of similar facies formed under arid conditions.
The decrease of Mn concentration toward the continental facies occurs more
rapidly in a humid than in an arid zone deposit. On the other hand, the decrease
of Mn content toward the pelagic or basin sediments takes place more rapidly
in an arid environment as compared to humid ones. These differences are due
to different intensities of physicochemical mechanisms that are indicative of
various climatic conditions. Deep weathering in the source area results in large
amounts of bivalent Mn, which is completely oxidized. The transportation medium
is rich in organic acids and permits the Mn to stay in solution for a long time and
to migrate beyond the limits of the continental facies. Thus, only small amounts of
Mn are precipitated in the latter. The major deposition occurs as soon as the alka-
line sea water is encountered. As powerful currents can freshen the sea water to a
great distance from the shore, a very gradual gradient from acidic to alkaline
conditions can prevail. Thus, the precipitation of the Mn does not occur all at
once, but instead may gradually diminish with distance from shore.
In arid localities the conditions are quite different. In cases of slight vegeta-
tion cover, chemical weathering is slow and shallow, and as a result of absence of
organic acids the surface waters are slightly alkaline or neutral. Hence, the small
amounts of totally oxidized bivalent Mn ions are not readily transported in solu-
tion. Because of smaller amounts of fresh-water run-off in arid regions, the sea
water is not diluted to a great extent; and any Mn that reaches the sea in solution is
rapidly precipitated in coastal and near-shore alkaline environments.
RONOVand ERMISHKINA (1959) further pointed out that the rate and degree
of upheaval of the continent controls the amount and rate of fresh-water run-off,
which in turn is changing the width of the zone of Mn deposition along the coast-
line.
For regional changes in contents of the elements Fe, Mn and P from silt-
stones to clays and marls, see also the publication of TIKHOMIROVA (1964).
 ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 125

Phosphate distribution in sediments of the Russian platform (RONOVand KORZINA,

1960)

The phosphate content of the Russian platform sediments was investigated by

RONOVand KORZINA(1960), who found that geosynclinal phosphorites have a
higher content of both PzO5 and carbonates than those of the platforms. In con-
trast, the phosphorites of the platform deposits are richer in terrigenous detritus.
The average PzO5 content of sandstones, clays, and carbonates of the Russian
platform is 0.104 %, 0.102 %, and 0.068 %, respectively. Significant for determining
the mode of origin of phosphorites is the fact that the distribution of dispersed P
in carbonate rocks follows the pattern of organic carbon. The curves in Fig.14
show an enrichment in PzO5 and Corgduring 0,D3, and J3 and an impoverishment
during Snz, S,C, P, and Cr2 times.
Most of the living organisms are concentrators of phosphorus; the PzO5
content in marine plankton, for example, is a thousand times greater than that in
sea water. After death, diagenetic processes, such as those caused by bacterial
decomposition, break down the P-bearing organic material and the phosphate
formed goes into solution (RONOVand KORZINA,1960). As a result of diagenetic
redistribution of PzO5 in the sediments, the phosphorus is precipitated around
minute nuclei such as skeletons to form nodules of phosphorite. It seems that the
larger the amount of organic matter present, the more phosphorus will accumulate
in the calcareous ooze. It is not clear, however, if this phosphorus is released as a
result of decay of the organic matter or precipitated by organic reagents formed
during decay processes, or both.

5'2' Corg
inoh in %
0.22 0.33

0.18

0.16

0.10

0.06

on2
0

Absolute time in millions of years

Fig.14. Variations in the average content of PZOSand Corg.in the carbonate rocks of the Russian
platform. For explanation of the symbols see Fig.10. (After RONOVand KORZINA,1960, fig.5.)
126 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

in% mela
1.4 . 0.26 '

A
1.2 0.22-

1.0 0.19 -
'

0 8 . 0.16 .

0.6 . 0.12 -
Humid zone 5%
0 . 4 . 0.08.
Humid zone Cog.

- _- $05
'
0.2- 0.04-
/
/----
\.Arid zone

1
*------ -*Arid zone cots.
'SandstoAes and
si It st on es
I Claystbnes
rocks
' CarboAate '
Fig.15. Variation in the average PZOSand Corg.contents in sandstones, claystones and carbonate
rocks of the Russian platform deposited in humid and arid climatic zones. (After RONOVand
KORZINA, 1960, fig.9.)
con
inel
5in%s
1.3

1.2 024

1.1 0.22-

1.0 0.20-

09 0.18 .

08 0.16 ~

0.7 014 .

0.12 . Humid zone cog,

0.E
Humid ZOMP205
0.5 0.10 .
0.4 0.08 -
./
\
\
0.3

0.2
0.06-

0.04 - c/--
_ / - _
em-----
----. \
\.Arid zone
Arid zone coq.
5%

0.1 0.02

0
Continental and
lagoonal
I Nearshoic -
marine
I Pelagic
I

Fig.16. Variation in the average PZOSand Corg.contents in the sedimentary rocks of the Russian
platform according to the facies and the climatic conditions of deposition. (After RONOVand
KORZINA,1960, fig.11.)
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 127

Ronov and Korzina divided the sandstones, shales and carbonates according
to their mode of formation into arid and humid zone deposits; and as to their
environment of deposition, into continental, nearshore and pelagic facies (Fig. 15
and 16).
It is interesting to note that in sandstones and siltstones there is no obvious
correlation between dispersed phosphorus and organic carbon. The occurrence of
P is determined by different factors which include: (I) accumulation of detrital
“terrigenous” apatite derived from igneous rocks in the source area; (2) cementa-
tion of porous arenaceous sediment with phosphate, brought to the site of pre-
cipitation by the upwelling of water from deeper parts of the basin; and (3) ad-
mixture of phosphatic shells, such as those of inarticulate brachiopods.

A1 and Ti distribution in Russian platform sediments (MIGDISOV,

1960)

The A1 and Ti distribution in the sediments of the Russian platform have been
examined by MIGDISOV (1960). The variation of the Ti02 concentration in the
carbonate rocks in the geologic column parallels those of the A1203, SiOz, and
the content of insoluble residue in carbonates (Fig.17). As pointed out by Migdisov,

Fig.17. Variation of the average contents of insoluble residue (I.R.), SiOz, A1~03,and Ti02 in
the carbonate rocks of the Russian platform with time. For explanation of the symbols see Fig.10.
(After MIGDISOV,1960, fig.5.)
128 K. H. WOLF, G . V. CHILINGAR AND F. W. BEALES

the clays of humid epochs in general have higher average A1 and Ti contents. The
maxima of the TiOz/A1203 ratios correspond to humid periods, during which
intensive chemical weathering occurred with the formation of a thick weathered
overburden and the deposition of large amounts of kaolinite, bauxite and clean
quartz sand. The Ti and A1 are associated with the insoluble residue in the carbonate
rocks and their content is determined by the tectonism of the platform. The maxi-
mum Ti02 concentration occurs in sediments formed at the beginning and the end
of each tectonic cycle; this corresponds to both transgression and regression and an
associated intensive supply of detritus.

Element distribution as revealed by KUDYMOV

(1962)

The distributions of minor elements on a regional scale and through the geologic
column of the Russian platform (KUDYMOV, 1962) are of particular interest
because of their application to both correlation and environmental reconstructions.
As most of the findings are in close harmony with the geochemical findings discus-
sed in the previous sections, there is no need to review them in detail here. It is
sufficient to state that the spectral curves of Ca, Mg, Al, and Si, taken together,
reflect the basic lithologies; and one can quite readily discriminate between lime-
stones, dolomites, sandstones, shales, marls, argillaceous limestones, calcian
dolomites, dolomitic marls, and calcareous or dolomitic shales. In general, a
change from shales and sandstones into calcareous rocks is indicated by a decrease
of Na, B, Fe, Mn, Ti, Cr, and P contents; Ca, Mg, and Cu contents, however,
do not decrease. In addition, V, Ni, and Cu are usually associated with argillaceous
sediments. It is believed that some of the Cu has been derived from organisms that
are capable of concentrating this element. Cu and Ni are genetically related,
especially in sandstones and shales. The Mn content relative to Cu is on the average
higher in carbonates than it is in siltstones and shales. This suggests that there is
no genetic relation between these two elements.
Based on extensive research, KUDYMOV (1962) found that, as a rule, litholog-
ically uniform sedimentary bodies are not geochemically homogeneous. In fact,
some of the upper parts of formations are spectrographically similar to the lower
parts of overlying deposits. Hence, the accepted lithologic boundaries are often
transgressed by geochemical boundaries.

Environmentally induced niineralogic and chemical changes of cement and concretions

BROVKOV (1 964) described diagenetically formed carbonate cement types and

concretions as a product of different environments in the Jurassic coal measures.
These are predominantly composed of terrigenous siltstones, sandstones, conglom-
erates and coals, and rare small lenses of pelecypod-rich limestones.
The trends of the p H and Eh changes during diagenesis at any one locality, as
I
1
I
Siderite

Silica

Pyrite

An ke r i t e

Calcite
-
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES

m
3
R D L LG T SS DS
129

.\.
Res. org. C N

Fig.18. Occurrence of the various phases in the various types of facies. R = river beds; D = deltas;
L = lagoons; LG= lagoon-gulfs; T= talus sands; SS= shallow sea deposits; DS= deep-sea
clays. (After BROVKOV,1964, fig.7.)

'18
50 *\
\
\
\
\
LO \
\
\
\

30
\
'.
/=
/' \ alcite IC)
20 / \
\
/
/
/ _-------,
\ /

10 d'
/
--- -- -
/
K-
. -0

'' 0
0
Siderlte IS)
Quartz IQ)

Zones of
Q A Q A with A wirh Q A C with diagenetic
si deri t e and siderite siderite formation

Fig.19. Authigenic zones and relative proportions of quartz and carbonates in the cement of
sandstones-siltstones of various facies. Q = quartz; A = ankerite; C = calcite, (After BROVKOV,
1964, fig.9.)
130 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

Fig.20. Occurrence of different types of concretions in the various facies. R = river beds;
D = deltas; M = marshy lakes; LG= lagoon-gulfs; L= lagoons; T= talus sands; SS = shallow
sea deposits; DS= deep-sea clays. (After BROVKOV, 1964, fig.9;sideroplesite = Mg-rich siderite.)

well as from facies to facies, have been suggested through the study of calcite,
siderite, sideroplesite, ankerite, dolomite, authigenic quartz, pyrite, and glauconite.
The distribution of the numerous phases is given in Fig.18; authigenic zones and
relative amounts of diagenetic quartz and carbonate cement of the sandstones and
siltstones of various facies are presented in Fig. 19; and the distribution of different
mineralogic types of concretions in the various facies is shown in Fig.20.

Metamorphically mobilized elements

An interesting use of trace elements in connection with low-grade metamorphosed

sediments was suggested by GORLITSKIY and KALYAEV (1962), and others prior
to them. As soon as more information is available on the distribution pattern of
syngenetic elements in sediments, it should be possible, even if only indirectly, to
follow the migration of trace elements during metamorphism. Gorlitskiy and
Kalyaev observed: (I) a distinct increase in trace-element content in the schists,
which they considered as having been formed from argillaceous sediments; (2) a
reduction in trace-element content in quartzites and sandstones; and (3) a still
greater reduction in content of trace elements in the dolomites. Ba and Sr are
noteworthy in this respect. They were probably originally deposited with the
carbonate sediments, but appear to have migrated with some of the carbonates
to form cement in the sandstones and quartzites.
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 131

WORLD-WIDE CHANGES IN COMPOSITION OF CARBONATES THROUGHOUT GEOLOGIC TIME

In the previous section a number of examples have been given that illustrate changes
in elemental composition both in synchronous sediments and through the geologic
column within the Russian platform. No consideration was given to the fact that
some of the changes in contents of elements occurring from the Precambrian to
the Recent may be world-wide. The interpretations of the causes are quite hypo-
thetical and consequently are of a controversial nature.
VINOGRADOV and RONOV(1956) mentioned that the composition of the
carbonate sediments of the Russian platform show a periodicity and a definite
trend through geologic time, which are comparable to those observed on the North
American continent. As shown in Fig.21, with a decrease in geologic age the Mg
content diminishes twenty-five fold from 12.63 % in the Proterozoic to 0.51 % in the
Quaternary. This is accompanied by a conspicuous increase in Ca content of
carbonate rocks from the Proterozoic (20.35 %) to the Quaternary (35.9 %).
Fig.22 demonstrates similar trends in North America as based on the Ca/Mg ratio.
According to VINOGRADOV and RONOV(1956), the dolomites of the Russian
platform are syngenetic and/or early diagenetic, and the Ca and Mg contents
consequently reflect the geochemical processes occurring at or close to the sea
floor. It is important to note here the conclusions of TEODOROVITCH (1960, p.76)
that: ( I ) during the Precambrian and Early Paleozoic times most of the dolomites
resulted from direct chemical precipitation out of sea water; (2) dolomites of the
Late Paleozoic time are of chemical (primary dolomites in salinified lagoons or
brackish-water large bays) as well as of diagenetic origin; and (3)during the Meso-

Absolute time in millions of years

Fig.21. Variation with time of the average percentages of Ca and Mg in the carbonate rocks of
the Russian platform. For explanation of the symbols see Fig. 10. (After VINOGRADOV
and RONOV,
1956, fig.3.)
132 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

Cahg
+Caledonian --MHercynian ---w A t p i c e 4

'O0I
90

70

501

40 1 /

30 platform

20

101

0
Sn2 ' C m ' S, ' 5 $ D ' C ' P ' T ' J ' C r Ce'
5x) 433 310 225 150 70 0
Absolute time in millions of years

Fig.22. Variation of the Ca/Mg ratio with time in the carbonate rocks of the Russian platform
and North America (N.A.). For explanation of the symbols see Fig.10. (After VINOGRADOV and
RONOV,1956, fig.4.)

zoic and Cenozoic periods predominantly diagenetic dolomites were formed.

The distribution of Sr is also quite distinct. As has been shown earlier, Sr
can enter the aragonite of organisms, and thus the skeletal carbonate sediments are
enriched in Sr content. Sr can also precipitate with marine salts together with
CaC03, either independently or together with CaS04. The data on the Sr con-

0.18- 18
0.16:
0.14. 14
161
0.12-

0.10.
0.08

0.06
0.04,
0.02.

0-

Absolute time in millions of years ,

Fig.23. Variation with time of the average percentages of CaS04 and Sr. For explanation of the
symbols see Fig.10. (After VINOGRADOV and RONOV,1956, fig.5.)
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 133

centration in the carbonate rocks indicate certain maxima that coincide with
maxima of CaS04 contents. Lower Paleozoic deposits have a small CaS04
content, and the Sr concentration is also correspondingly small. In Middle and
Upper Paleozoic times the amounts of both CaS04 and Sr increase (Fig.23). This
parallelism in composition, however, is not present from the beginning of the
Mesozoic: CaS04 in the carbonate rocks is practically zero, whereas the Sr content
increases rapidly. This trend is well demonstrated by the change in Ca/Sr ratio with
time as shown in Fig.24. The superimposed curve for the North American carbonate
rocks illustrates a similar increase in Sr content. There is an almost fifty-fold
enrichment of Sr from the Proterozoic to the Tertiary. (See FAIRBRIDGE, 1964, for
further discussion.)
Complementary to the observed changes in Ca and Mg contents in carbonate
sediments from the Proterozoic to the Tertiary, there are similar trends in the
argillaceous sediments and sandstones. There is a distinct increase in the Ca/Mg
ratio with decreasing age. The Ca and Mg contents in both sandstones and clays
are probably largely associated with carbonate admixture. A similar tendency
toward an increase in the Ca/Mg ratio with decreasing age has been reported from
the carbonate fraction of phosphorites (RONOVand KORZINA,1960). VINOGRADOV
and RONOV(1956) pointed out that although there is a distinct relationship
between the lithology and the content of certain essential elements (e.g., Mg in
dolomite), the changes in content of elements through the geologic column are
also quite distinct in cases where the elements are only of secondary importance,
as in the cements of sediments. This suggests that the initial material of the sedi-
mentary rocks had a common source and that their composition reflects changes
in geologic times. They concluded that the general increase in Ca/Mg ratio with

510 L30 310 225 M) 70 0

Absolute time in millions of years

Fig.24. Variation with time of the Ca/Sr ratio in the carbonate rocks of the Russian platform and
North America (N.A.). For explanation of the symbols see Fig.10. (After VINOORADOV and RONOV,
1956, fig.6 and 7.)
134 K. H. WOLF, G. V. CHILINGAR AND F. W. BEALES

time in clays, sandstones, and carbonates, and possibly the Sr content in the latter,
in Russia and North America appears to reflect the evolution of the chemical
composition of the sedimentary crust. (For additional curves based on the work
of VINOGRADOV et al., 1952, see summary of CHILINGAR, 1957.)
Additional concepts that attempt to explain the trend of Ca/Mg ratio through
geologic times are given by CHILINGAR (1953, 1956a), CHAVE(1954a, b), and
FAIRBRIDGE (1957, 1964). Fairbridge discussed some of the problems of inter-
preting this geochemical trend.
RONOV(1959) pointed out that the principal cations in sea water (Na, K,
Mg, Ca, Sr, etc.) and the elements of sedimentary rocks (Si, Al, Fe, Ca, Mg, Na, K,
Mn, etc.) were derived in the past from the erosion of ancient rocks. Although the
water of the oceans contains the principal anions (CI, S 0 4 , F, B, etc.) and COZ,the
same components in the sedimentary rocks and a considerable part of the at-
mospheric gases (Nz,COz, etc.) must have been derived from an additional source,
most likely from volcanism (RONOV,1959).
According to RONOV(1959), if RUBEY'Sview (1955) is maintained that the
amounts of COz in the atmosphere and ocean remained relatively constant and that
the excess volatiles supplied through volcanism accumulated gradually, "then the
conclusion is inevitable that, in order for these conditions to persist, in the system
atmosphere-ocean there must have been a continuously active mechanism of
.
removal and fixation of COz . ." Ronov proceeded to compare the evidence of
volcanism during the geologic epochs and periods with the amount of COz
locked in the sediments as carbonates.
A possible relationship between the volumes of volcanic emanations and the

9.75

825

6.75

=
m
x 5.25

E 3.75 t \
al I \ C%of the
E P carbonates
225
3
0.75 s
1 , I I , I

'
I I ,

D I ' D Z ' D '~ c1 c2+3 ' PI

I
p2 '
T1 I T 2 ' T 3 ' J1 ' J21J3'
310 275 225 185 150 110
Absolute time in millions of years

Fig.25. Relation between the volumes of subaqueous and subaerial volcanic extrusions, and the
volumes of COZlocked in the carbonate rocks of the present-day continents. For explanation
of the symbols see Fig.10. (After RONOV,1959, fig.1.)
ELEMENTAL COMPOSITION OF SEDIMENTARY CARBONATES 135

Absolute time in millions of years

Fig.26. Relation between volumes of volcanic extrusions and areas covered by seas (percentage
of the total of the present-day continents). For explanations of the symbols see Fig.10. (After
RONOV,1959, fig.2.)

amounts of COZ locked in carbonate sediments is illustrated in Fig.25. The

volcanic COZ added to the atmosphere and sea water was apparently almost
immediately incorporated in the carbonate sediments deposited. Deviations from
this pattern must have been rare and of short duration, as an increase in the amount
of COZ would have dissolved carbonates. RONOV(1959) also mentioned that the
epochs of intensive volcanism and great accumulation of carbonates alternated
with periods having less intense volcanic activity. The fluctuations correspond
well to marine transgressions and regressions (Fig.26). Ronov concluded that ". . .
the periodic fluctuations in the amount of carbonate sediments were governed by
the corresponding periodic changes in the intensity of the interrelated volcanic and
tectonic (epeirogenic) processes. The former provided the quantity of C02 needed
for the accumulation of the carbonates; the latter determined the area of the inland
seas. . ."
The question whether or not the absolute amount of COZin the atmosphere
and oceans changed during post-Precambrian (Phanerozoic) time can be approach-
ed indirectly by investigating the lithology and chemical composition of the sedi-
mentary deposits. In particular the Ca/Mg ratios in carbonate rocks may serve as a
kind of COZ indicator in the system atmosphere-ocean (CHILINGAR, 1956a;
RONOV,1959). This is possible if, first of all, the much higher Mg concentration
and the high COZcontent in the water, in addition to climatic conditions and salini-
ty, govern dolomite formation. Ronov concluded that during Paleozoic time the
pcoZ decreased very slowly. At the end of the Mesozoic, however, it diminished
136 K. H. WOLF, G . V. CHILINGAR AND F. W. BEALES

more rapidly because of the precipitation of carbonates associated with the vast
accumulation of Globigerina ooze during the Upper Cretaceous and Paleocene
times, and because of photosynthetic fixation by plants.
In addition to the control of the C02 budget by volcanism, one has to con-
sider the effect of organic life processes. Apart from possible minor catastrophies
of individual taxonomic groups, it is reasonable to assume that animals and plants
have been establishing a progressively greater control on-their environment. It is
not likely, for instance, that carbon dioxide concentrations in the atmosphere
have fluctuated greatly for any considerable period. Simple mutational probability
demands that plants must have become progressively more efficient in such a basic
activity as the utilization of carbon dioxide. Furthermore, it is likely that the vast
mass of the slowly evolving oceanic plankton has controlled the C02 budget more
than their more flamboyant and variable terrestrial relatives. Ultimately it should
be possible to relate the composition of sediments to organic evolution and its
interplay with the earth’s and cosmic evolution.

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Chapter 3

PHYSICAL CHEMISTRY O F FORMATION O F CARBONATES

WILLIAM H. TAFT

Department of Geology, University of South Florida, Tampa, Fla. (U.S.A.)

SUMMARY

Modern, unconsolidated, carbonate sediments are composed predominantly of

metastable carbonate minerals, whereas ancient carbonate rocks are made up of
calcite and dolomite. If ancient carbonates were predominantly metastable prior
to lithification, then in order to preserve the original textures solid-state recrys-
tallization must have been operative instead of solution-reprecipitation of ara-
gonite to calcite.
Aragonite in contact with distilled water completely recrystallizes to calcite
in approximately 100 days at 23°C. Recrystallization rate of aragonite to calcite
increases with increasing concentration of calcium ions and increasing temperature.
Magnesium, on the other hand, retards recrystallization of aragonite to calcite
if the weight ratio of aragonite to magnesium is 804 or less.

INTRODUCTION

One of the more important aspects of carbonate rock formation is that dealing
with their chemical origin. Although physical characteristics of carbonate rocks
have been extensively studied (BATHURST,1959; HARBAUGH, 1960; MURRAY,
1960; CAROZZI, 1961;and many others), seemingly little progress has been made in
deciphering their chemical history.
The sites of modern carbonate sediments that are forming and accumulating
in many warm, shallow, tropical and subtropical seas, such as the Bahama Banks,
Florida Bay, Persian Gulf, and the Great Barrier Reef of Australia, are not unlike
those in which sediments of ancient limestones were deposited.
One critical aspect of unconsolidated modern carbonate sediments that should
be kept constantly in mind, when one considers the origin of carbonate rocks, is
their mineralogy. Modern, shallow warm-water carbonate sediments are composed
predominantly of metastable carbonate minerals, aragonite and high-magnesium
calcite, and contain only minor amounts of low-magnesium calcite (STEHLIand
HOWER,1961; Blackman, in CLOUD,1962; TAFTand HARBAUGH, 1964). Carbonate
rocks are composed essentially of two stable minerals, calcite and dolomite. One
152 W. H. TAFT

of the problems facing chemists and geologists alike is the abundance of metastable
carbonate minerals in modern sediments and their absence in carbonate rocks.
Only in rare instances, however, one can demonstrate recrystallization of meta-
stable carbonate minerals to either calcite or dolomite. These exceptions include
beach rock exposed to fresh water in the form of ground water or rainfall (DEBOO,
1961; RUSSELL, 1961) and dolomite replacing aragonite (ILLING, 1964; LUCIAet al.,
1964; SHINNand GINSBURG, 1964).One notable exception to the apparent rule of
lack of persistence of exposed metastable carbonate minerals can be found in a
report by DURHAM (1950), in which he described metastable high-magnesium cal-
cite surviving at the expense of calcite in uplifted Pleistocene carbonate sediments
along the Peninsula of Lower California (Baja California, Mexico).
One may summarize this introduction to the problem as follows:
( I ) Most modern, unconsolidated, shallow warm-water carbonate sediments
are composed of metastable minerals.
(2) Metastable carbonate minerals are generally absent in Pliocene and.older
carbonate rocks.
(3) If one can assume that Pliocene and older limestones were chiefly meta-
stable carbonate minerals originally, virtually all limestones have undergone
recrystallization.
( 4 ) Recrystallization can be either a solid-state recrystallization or can be
achieved through the solution of metastable carbonate minerals and reprecipita-
tion as stable carbonate forms.
(5) Many older limestones show preservation of very delicate structures,
which is probably due to the early lithification that prevented compaction from
destroying these textures.
(6) Modern carbonate sediments, for the most part, tend to be unconsoli-
dated. This possibly suggests that either rates of lithification have changed since
older limestones formed, or chemical environments at present are not conducive
to lithification.
The origin of carbonate rocks is extremely complex, and it is necessary to
subdivide each and every effect and understand it thoroughly. Although this chap-
ter purports to explain the physical chemistry associated with the origin of carbo-
nate rocks, this problem is far from being solved. Many new approaches will be
required, such as studies of surface energies (SCHMALZ, 1963), before one truly
begins to understand the physical and chemical changes accompanying recrystal-
lization of unconsolidated metastable carbonate minerals to stable carbonate
minerals in carbonate rocks.
One fruitful avenue of approach would appear to be study of the effect of
Mg/Ca ratios of solutions from which carbonate minerals precipitate. ERENBURG
(1961) reported precipitation of protodolomite (GRAFand GOLDSMITH, 1956)
below 100°C from CaClz and MgClz solutions. One might suspect that, given
sufficient time, protodolomite would recrystallize to ordered dolomite.
PHYSICAL CHEMISTRY OF FORMATION OF CARBONATES 153

CHILINGAR and BISSELL (1 963b) presented some physical-chemical evidence

which suggests that possible high Mg/Ca ratio of Precambrian sea waters prevented
the formation of hard protective and skeletal structures of organisms, or largely
hindered their formation. This could explain the scarcity of calcareous skeletons
of invertebrates in Precambrian formations.
Another interesting avenue of approach is that dealing with the influence of
time, concentration, and pH. SIEGEL (1961) demonstrated that protodolomite can
be produced at 25 "C if Ca2+ and Mg2+ ions were temporarily tied up in activated
charcoal and could only come in contact with c 0 s 2 - ions very slowly. In
addition, he found that somehow the sulfate radical plays an important role
in dolomite formation, although admittedly at present its importance is not under-
stood. Possibly S O P complexes with Ca2+ to form a CaS04O complex,which
increases the Mg/Ca ratio to the critical point at which dolomite forms. Certainly,
it comes as no surprise to see the so& radical somehow involved in this reaction
because of the abundance of S O P in evaporite sequences where dolomite is so
common (cf. CHILINGAR, 1956a,b). CHILINGAR and BISSELL(1963a) discussed the
formation of dolomite in sulphate-chloride solutions and presented adiagram
showing the region of dolomite formation in saturated chloride and sulphate
solutions.
The purpose of this chapter is to emphasize that (1) the formation of carbon-
ate rocks (i.e., lithification and recrystallization) is a chemical problem; and (2)
the chemical composition of water in which carbonate sediments were deposited,
and that of interstitial water, during lithification, cannot be overlooked in studying
their origin and subsequent history. In addition, experimental data are presented
that suggest a major role played by magnesium ions of sea water in controlling
the form of carbonate minerals precipitated and their persistence. Finally, an
attempt is made to demonstrate the importance of these data in interpreting the
origin of carbonate rocks.

Experimental procedures

Aragonite was prepared at 70°C by the procedure described previously by WRAY

and DANIELS (1957). This technique consists of adding 20 ml of a 1.O M Ca(N03)~
solution to 200 ml of a 0.1 M N a ~ C 0 3solution in a 500-ml beaker. Each solution
was preheated and mixed in a water bath at 70°C. The resulting precipitate was
allowed to equilibrate for approximately 2 min, filtered, washed with distilled water
at 70"C, dried, ground with a mortar and pestle to minus 0.062 mrn, and then iden-
tified by X-ray diffraction.
A calibration curve for aragonite and calcite was prepared following the
procedure of LOWENSTAM (1954) and is described in detail elsewhere (TAFTand
HARBAUGH, 1964).
All chemicals used in the preparation of test solutions were Reagent Grade
154 W. H. TAFT

Baker-analyzed. Test solutions were added to a weighed quantity of aragonite

precipitate in 50-ml and 250-ml beakers, mixed, covered with Parafilm, and stored
in the laboratory at specific temperatures.

INFLUENCE OF CHEMISTRY AND TEMPERATURE ON RECRYSTALLIZATION RATES

Recrystallization of aragonite to calcite would appear possible by either solution

of aragonite and reprecipitation as calcite or by solid-state recrystallization. So-
lution of aragonite and subsequent reprecipitation as calcite obliterates original
texture, whereas textures may be preserved by solid-state recrystallization. In
view of perfect texture preservation in many ancient limestones, one must con-
clude that in these instances, if the original sedimentary particles were metastable
carbonates, solid-state recrystallization had taken place. All experiments, listed
in this chapter which show evidence of recrystallization, involved solution and
reprecipitation.

Aragonite in distilled water

Recrystallization rate of aragonite to calcite in contact with distilled water is direct-

ly affected by temperature of the solution (Table I). Recrystallization rate at 3 "C
is very slow averaging about 0.1 %/day. With increasing temperature, recrystalli-
zation speeds up, until at 70°C only 3 days are needed to convert a sample of

100

80
eP,
0 I
m \A
g
236
60
.#
C
\A
8
40
n
70' A\ A
20

0 - I

Fig.1. Recrystallization of aragonite to calcite in distilled water (D.W.) as a function of tempera-

ture. At 70°C recrystallizationwas complete within 3 days; whereas at 3 "C, and after 236 days,
only 22 % of the aragonite recrystallized to calcite.
TABLE I z
ARAGONITE IN CONTACT WITH DISTILLED WATER AT VARIOUS TEMPERATURES SHOWING INCREASED RATE OF RECRYSTALLIZATION OF ARAGONITE TO CALCITE
2>
WITH TEMPERATURE RISE r
~~
0

Experiment Chemistry of solution Volume Weight of precipitate Temp. Duration of Mineralogy B

01
(mi) (g) ( "C) experiment 4
(days) Aragonite
(weight %)
Calcite
(wei.pht %) *
ga

8
g
~~

11-H distilled water 40 0.1074 3*1 0

77
99
91
+ trace
9
236 77 23 2;
az
11-F distilled water 50 0.1996 23*2 0 99 + trace
18 95 5
cl
36 85 15 >
49 74 26 6
0
64 58 42 z
75 43 58
86 27 63
2;
100 trace 99+
43 distilled water 50 0.1998 70' 1 0 99 + trace
3 0 100
TABLE111
ARAGONITE IN CONTACT WITH MAGNESIUM SOLUTIONS OF VARIOUS CONCENTRATIONS1

Experiment Chemistry of solution Volume Weight of precipitate Temp. Duration OJ Mineralogy

(nil! (g) ("C! experiment
Aragonite Calcite
(days)
(weight %) (weight %)

+
~~

3 2 p.p.m. Mg 50 0.2011 23'2 0 99 1

28 I0 30
54 45 55
70 15 85
86 0 100
4 2 p.p.m. Mg 50 0.1921 70+1 0 99 t 1
40 65 35
I0 30 I0
90 10 90
110 0 100
5 5 p.p.m. Mg 50 0.2010 23*2 0 99 + 1
8 99 1
15 99 1
33 99 1
I0 99 . 1
86 99 I
100 99 1
130 5 p.p.m. Mg 50 0.2000 IO-tl 0 99 + 1
4 80 20
19 30 I0
29 0 100
11 5 p.p.m. Mg 40 0.2188 23*2 0 100 0
108 14 26
246 trace 99 -I
 10 10 p.p.m. Mg 40 0.331 1 23*2 0 100 0
108 74 26
246 0 100
55 26 p.p.m. Mg 40 0.1 140 23'2 0 91 9
3 90 10
13
24
91
90
. 9
10
141 87 13
115 49 p.p.m. Mg 40 0.1008 23+2 0 99 + trace
66 99 + trace
180 99 + trace
300 99 + trace
365 99 J- trace
131 10 p.p.m. Mg 50 0.2003 23*2 0
121
99 + trace

133 10 p.p.m. Mg 50 0.2004 70-t1 0 99 + trace

12 45 55
29 trace 99 + i
136 50 p.p.m. Mg 50 0.1998 70*1 0 99 + trace
$3
38 99 + trace
I 42 250 p.p.m. Mg 50 0.1997 70*1 0 99 + trace
38 99 + trace
11-G 1,330 p.p.m. Mg 50 0.1Ooo 23'2 0 64 36
120 63 37
200 64 36
320 61 39
400 64 36
470 64 36
L
1 Mineralogy is presented in weight :L and appears to be dependent upon temperature and quantity of magnesium ions relative to weight of precipitate. 5
158 W. H. TAFT

essentially 100% aragonite to calcite (Fig. 1). Of particular interest is the curve at
23 "C (Fig. 1) (close to standard temperature), which suggests that aragonite in
contact with distilled water would recrystallize to calcite in less than 6 months in
the natural environment.

Magnesium effect

Because of the metastable nature of aragonite (JAMIESON, 1953; MACDONALD,

1956), any condition that slows down or prevents solution of aragonite and its
reprecipitation as calcite may be a controlling factor that enables solid-state
recrystallization to be the dominant process. KITANO and HOOD(1961) described
the influence of organic material on the polymorphic form of CaC03 precipitated.
In addition, organic matter secreted by carbonate shell-secreting organisms
prevents chemical reaction between interstitial water and calcium carbonate of the
shell until chemical or biological activity removes this layer.
Magnesium ions in contact with aragonite appear to be capable of prevent-
ing recrystallization to calcite for an indefinite period by the process of solution
and reprecipitation. Temperature and concentration of magnesium ions relative
to quantity of aragonite appear to be important factors (Table 11,111).The empir-
ical weight ratio of aragonite to magnesium in solution was termed the critical
concentration ratio (TAFTand HARBAUGH, 1964). This ratio (Table 111) is critical
to long-term aragonite preservation at laboratory temperature (23*2 "C), but
changes with increasing temperature. At 2312 "C, 50 ml of a 5 p.p.m. solution of
magnesium in contact with 0.2010 g of aragonite prevents aragonite solution and
reprecipitation as calcite (Fig.2). If the temperature is increased to 70 "C,

TABLE 111

EFFECT OF MAGNESIUM ION CONCENTRATION ON RE CRYSTALLIZATION^

Experiment2 Critical Recrystallized

concentration
ratio3 Yes no

3 2,011 +
11 1,394 +
10 827 +
5 804 +
131 400 +
55 109 +
115 51 +
Based on empirical results from Table 11; temperature 23 f 2°C.
Taken from Table 11.
Grams of precipitate (in contact with solution)/grams of magnesium in solution.
PHYSICAL CHEMISTRY OF FORMATION OF CARBONATES 159

40 80 100
Tome (days1

Fig.2. Recrystallization of aragonite to calcite as a function of weight ratio of aragonite to mag-

nesium ions available in the solution. This ratio in experiment 3 (Table 11) is 2,011 ;recrystalliza-
tion is complete within 87 days. The same ratio for experiment 5 (Table 11) is equal to 804; no
detectable recrystallization occurs within 100 days.

1
49.4 p.p.m.Mg2’(115)
100 0 0 0 0
26 pp.m.Mg2+(55)

c
L -
u
n
k 40-

20 -
0- I I

Fig.3. Lack of recrystallization to calcite of aragonite in contact with solutions having 49.4, 26
and 1,330 p.p.m. of Mgz+. Numbers in parentheses refer to experiment numbersfrom Table 11.

solutions containing 5 and 10 p.p.m. of magnesium are ineffective, but 50 p.p.m.

of Mg at this temperature prevents recrystallization (Table 11). Sea water contains
1,330 p.p.m. of Mg2+ which is sufficient to prevent recrystallization (Fig.3). In
some instances, the magnesium concentration in interstitial water of fine-grained
modern carbonate sediments tends to increase during compaction. Therefore,
as interstitial water is squeezed from these sediments, magnesium ions remain
160 W. H. TAFT

in sufficient quantity to prevent recrystallization. If magnesium ions are flushed

before lithification, however, recrystallization by solution and reprecipitation
appears possible.

Calcium effect

Increasing the quantity of magnesium ions relative to the amount of aragonite tends
to prevent recrystallization if the critical concentration ratio is 804 or less (Table
IV). Calcium ions, on the other hand, react in just the opposite manner. If the
concentration of calcium ions relative to quantity of aragonite is increased, the
rate of aragonite recrystallization to calcite also increases (Table IV, Fig.4). In
addition to calcium ion concentration, temperature, and pH of the solution affects
the recrystallization rate (Table IV). At 3 "C, recrystallization is sluggish, but with
less calcium at 70°C recrystallization is complete within three days (Table IV).
In order to investigate the effect of pH on recrystallization rates, 10 ml of
an ethanolamine buffer solution (pH= 10.4) was added to 30 ml of a 400 p.p.m.
solution of calcium in contact with 0.2006 g of aragonite at 70°C. Based on pre-
vious experiments of aragonite in distilled water (Fig. I), and aragonite in
contact with 400 p.p.m. of Ca2+(Fig.4) that recrystallized to calcite within 3 days,
this mixture at adjusted pH should have recrystallized similarly. This, however,
was not the case (Table IV). During the 20 days duration of this experiment, no
recrystallization to calcite was detected. Although this relationship indicates that
pH may play a role in affecting recrystallization, it would be unusual to find pH
values this high (10.4) in the natural environment.

01.000 p.p.m. Ca2+

A2.500p.p.m. Ca2+
400pp.m. Ca2+

C
P,
L
U

20 -

0
0
I
5 Ib 115 2b ;
5 do i5 do d5
- 20
Time (days)

Fig.4. Dependence of recrystallization rate of aragonite to calcite upon Ca2+ concentration.

Recrystallization rate increases with increasing Ca2+ion concentration.
TABLE IV
ARAGONITE IN CONTACT WITH SOLUTIONS CONTAINING VARIOUS CONCENTRATIONS OF CALCIUM IONS AND AT DIFFERENT TEMPERATURES
zcl
Experiment Chemistry of solution Volume Weight of precipitate Temp. Duration of Mineralogy F
experiment cl

zi?!
(mil (gl ("C)
(days) Aragonite Calcite
(weight %) (weight %)

Calcium 400 p.p.m. Ca 50 0.2008 23*2 0 99 trace

8
g
15 90 10
22 17 23
32 55 45
40 30 70
7 93 5
44
46 trace 99 + az
Calcium 1,OOO p.p.m. Ca 50 0.2008 23'2 0 99 + trace
8
10 80 20
13 70 30 c,
>
15
21
60
25
40
75 tiz
24 95
Calcium 2,500 p.p.m. Ca 50 0.1996 23'2 0 99
5
+ trace
5
6 80 20
E
9 50 50
12 1 99
13 0 100
Calcium 400 p.p.m. Ca 50 70*1 0 99 + trace
1,OOO p.p.m. Ca 0.1998 1 0 100
2,500 p.p.m. Ca 0.2002
Calcium 720 p.p.m. Ca 40 0.1940 3*1 0 99 + trace
9 99 + trace
81 97 3
115 97 3
237 89 11
Calcium 300 p.p.m. Ca solution 40 0.2006 70*1 0 99 + trace
adjusted to pH 10.4 2 99 + trace
with ethanolamine 6 99 + trace
buffer 14 99 + trace
20 99 + trace
162 W. H. TAFT

Effect of other ions

Potassium and sodium chlorides increase the recrystallization rate of aragonite

to calcite (Table V). The recrystallization rate also increases with increasing con-
centration of chlorides (Fig.5).
Strontium has a retarding effect (Table V), similar to that of magnesium,
and prevents recrystallization. The quantity of strontium necessary to preserve
aragonite (> 100 p.p.m.), however, exceeds that present in sea water (8 p.p.m.).
During precipitation of aragonite, in one instance the writer obtained vate-
rite with a trace of aragonite and a trace of calcite. In order to test whether or not
vaterite could possibly be preserved in marine sediments, vaterite was placed in
contact with distilled water and solutions containing magnesium and calcium ions
(Table VI).
No attempt was made to construct a calibration curve for the three carbonate
minerals aragonite, calcite, and vaterite. By comparing the relative intensities of the
more intense reflections of these minerals, however, one can obtain a general idea
concerning their relative abundance. The second most intense peak of vaterite
(intensity= 75; d=3.29) correspondsvery closely to the third most intense peak of
aragonite (intensity= 52; d=3.273); and, therefore, as vaterite recrystallizes to
aragonite, this peak does not diminish as rapidly as it should. Nevertheless, from
the results presented in Table VI, one can conclude that vaterite, if formed in
the marine environment, would recrystallize and be preserved as aragonite.
If vaterite comes into contact with distilled water, or water containing calcium ions
alone, recrystallization to calcite will be rapid.

100 3,000 P.pm CI- AS KCI

\ -
8.0. 0 30.000 D.D.m.CI-AS NaCl

”
k 40

20

0 b 10 2‘0 2‘5
Tlme(day5)

Fig.5. Dependence of recrystallizationrate of aragonite to calcite upon concentration of potassium

and sodium chloride solutions. The recrystallizationrate increases with increasing concentration
of chloride solutions.
PHYSICAL CHEMISTRY OF FORMATION OF CARBONATES 163
?
W
N

N
W
N

-
ti
m
I- m
-
tl
I-
-
0
2 0 0 0
2: 2: 2:
6
Y
mul 3
G 6
E:
2
N
W I-
d
I
TABLE VI

VATERITE IN CONTACT WITH 150 DISTILLED WATER CONTAINING VARIOUS CONCENTRATIONS OF MAGNESIUM IONS AND CALCIUM IONS1

Experiment Chemistry of solution Volume WeiRht of precipitate Temp. Duration of Mineralogy, intensities
experiment
(mu (g) ("C)
(days)
Aragonite Calcite Aragonite +
Vaterite

Vaterite Distilled water 150 2.5 23+2 0 42 8 78

1 4 32 59
9 0 loo+ 0

Vateritc 420 p.p.rn. Ca 150 2.5 2312 0 4 8 78

5 0 lOOt 0

Vaterite 30 p.p.m. Mg I50 2.5 2312 0 4 8 78

1 5 8 65
71 29 7 22
80 71 9 0
32 1 72 8 0

Vaterite 60 p.p.rn. Mg 150 2.5 23*2 0 4 8 78

1 4 10 67
71 17 8 40
90 36 12 66
32 1 72 9 0

Vaterite 240 p.p.rn. Mg 150 2.5 23*2 0 4 8 78

1 4 9 72
71 5 9 70
I05 13 8 60 3
321 68 8 0 X
1
1 Intensities are used as a measure of relative abundance of aragonite, calcite, and coincident peak vaterite-aragonite. %1
PHYSICAL CHEMISTRY OF FORMATION OF CARBONATES 165

SUMMARY OF PHYSICAL CHEMISTRY

Some of the reactions between aragonite and test solutions, described in this chap-
ter, can be summarized as follows:
( I ) Addition of a common ion, calcium in this instance, increases the recrys-
tallization rate of aragonite to calcite.
(2) Recrystallization rate of aragonite to calcite is markedly affected by
temperature. Increasing the temperature of test solutions speeds up the recrys-
tallization rate, whereas lowering the temperature reduces the recrystallization
rate of aragonite to calcite.
(3) Addition of a high pH solution to a mixture of aragonite and calcium,
that would normally recrystallize rapidly, retards recrystallization. This pH value
(10.4), however, is much higher than that normally found in modern carbonate
sediments.
(4) If the weight ratio of aragonite to magnesium ions in solution is less than
804, recrystallization of aragonite to calcite by solution and reprecipitation does
not take place.
(5) Strontium ions are effective in preventing recrystallization of aragonite
to calcite, but the Sr2+ concentration necessary is much greater than that which
occurs in marine waters.
(6) Potassium and sodium-chloride solutions increase the recrystallization
rate of aragonite to calcite over that of aragonite in distilled water.

CONCLUSIONS

Lack of detectible recrystallization of metastable carbonate minerals in uncon-

solidated modern carbonate sediments may be attributed to the high concentra-
tion of magnesium ions in interstitial waters. If magnesium-ion concentration
persists, the preserved metastable carbonate particles should be cemented by
aragonite. This cementation by aragonite will preserve original textures and pre-
vent large-scale recrystallization by aragonite solution and reprecipitation as
calcite.
Solid-state recrystallization of aragonite to calcite should preserve original
chemistry such as Sr2+/Ca2+,12C/13C, and 1 6 0 / 1 * 0 ratios. These ratios should be
useful in interpreting ancient depositional environments. In the case of aragonite
solution and calcite precipitation, however, the resulting chemical ratios can be
significantly altered as a result of changes of ion ratios in the interstitial waters.
Preservation of aragonite in carbonate sediments for long periods favors
formation of dolomite. This is particularly true in those environments where brines
are concentrated at the surface by evaporation, the Mg/Ca ratio increases as a
result of calcium carbonate precipitation, and brines percolate through aragonite-
rich sediment.
 166 W. H. TAFT

ACKNOWLEDGEMENTS

Financial support for this work was provided principally by National Science
Foundation Grants G- 19772 and GP-2527. Assistance of Catheryn MacDonald
who did much of the laboratory work is gratefully acknowledged.

REFERENCES

BATHURST, R. G. C., 1959. Diagenesis in Mississippian calcilutites and pseudobreccias. J. Sedi-

ment. Petrol., 29: 365-376.
CAROZZI,A. V., 1961. Reef petrography in the Beaverhill Lake Formation, Upper Devonian,
Swan Hills area, Alberta, Canada. J. Sediment. Petrol., 3 1 :497-5 13.
CHILINGAR, G. V., 1956a. Solubility of calcite, dolomite, and magnesite and mixtures of these
carbonates. Bull. Am. Assoc. Petrol. Geologists, 40:2770-2773.
CHILINGAR, G. V., 1956b. Note on direct precipitation of dolomite out of sea water. Compass,
34: 29-34.
CHILINGAR, G. V . and BISSELL, H. J., 1963a. Formation of dolomite in sulfate-chloride solutions.
J. Sediment. Petrol., 33: 801-803.
CHILINGAR, G. V. and BISSELL, H. J., 1963b. Note on possible reason for scarcity of calcareous
skeletons of invertebrates in Precambrian formations. J. Paleontol., 37: 942-943.
CLOUDJR., P. E., 1962. Environment of calcium carbonate deposition west of Andros Island,
Bahamas. U.S.,Geol. Surv., Profess. Papers, 350: 1-1 38.
DEBOO,P. B., 1961. A preliminary petrographic study of beach rock. Proc. Natl. Coastal Shallow
Water Res. Conf:, Ist, 1961, pp.456458.
DURHAM, J. W., 1950. 1940 E. W. Scripps Cruise to the Gulf of California. Part 2: Megascopic
paleontology and marine stratigraphy. Geol. SOC.Am., Mem., 43: 216 pp.
ERENBURG, B. G., 1961. Artificial mixed carbonates in the CaC03-MgC03 series. J. Struct.
Chem. (U.S.S.R.) (Eng. Transl.), 2: 178-182.
GRAF,D. L. and GOLDSMITH, J. R., 1956. Some hydrothermal syntheses of dolomite and proto-
dolomite. J. Geol., 64: 173-186.
HARBAUGH, J. W., 1960. Petrology of marine bank limestones of Lansing Group (Pennsylvanian),
southeast Kansas. Geol. Surv. Kansas, Bull., 142: 189-234.
ILLING,L. V., 1964. Penecontemporary dolomite in the Persian Gulf. Bull. Am. Assoc. Petrol.
Geologists, 48: 532-533.
JAMIESON,J. C., 1953. Phase equilibrium in the system calcite-aragonite. J. Chem. Phys., 21:
1385-1 390.
KITANO,Y .and HOOD,W. H., 1961.Effect of organic material on the polymorphic forms ofCaCO3.
Geol. SOC.Am., Spec. Papers, 72: 86-87.
LOWENSTAM, H. A., 1954. Factors affecting the aragonite/calcite ratios in carbonate-secreting
organisms. J. Geol., 62: 284-322.
LUCIA,F. J., WEYL,P. K. and DEFFEYES, K. S., 1964. Dolomitization of Recent and Plio-Pleis-
tocene sediments by marine evaporite waters on Bonaire, Netherlands Antilles. Bull.
Am. Assoc. Petrol. Geologists, 48: 535-536.
MACDONALD, G. J. F., 1956. Experimental determination of calcite-aragonit? equilibrium re-
lations at elevated temperature and pressures. Am. Mineralogist, 91 : 744-736.
MURRAY,R. C., 1960. Origin of porosity in carbonate rocks. J. Sediment. Petrol., 30: 59-84.
RUSSELL,R. J., 1961. Origin of beach rock. Proc. Natl. Coastal Shallow Water Res. Con$, Ist, 1961,
pp.454-456.
SCHMALZ, R. F., 1963. Role of surface energy in carbonate precipitation. Geol. SOC.Am., Spec.
Papers, 76: 144.
SHINN,E. A. and GINSBURG, R. N., 1964. Formation of Recent dolomite in Florida and the Baha-
mas. Bull. Am. Assoc. Petrol. Geologists, 48: 547.
PHYSICAL CHEMISTRY OF FORMATION OF CARBONATES 167

F. R., 1961. Factors influencing the precipitation of dolomitic carbonates. Geol. Surv.
SIEGEL,
Kansas, Bull., 152: 127-158.
F. G. and HOWER,
STEHLI, J., 1961. Mineralogy and early diagenesis of carbonate sediments.
J . Sediment. Petrol., 31: 358-371.
TAFT,W. H. and HARBAUGH, J. W., 1964. Modern carbonate sediments of southern Florida,
Bahamas, and Espiritu Santo Island, Baja California: a comparison of their mineralogy
and chemistry. Stanford Univ.Publ., Univ. Ser., Geol. Sci.,8: 1-133.
WRAY,J. L. and DANIELS,F., 1957. Precipitation of calcite and aragonite. J . Am. Chem. SOC.,79:
203 1-2034.
Chapter 4

CHEMISTRY OF DOLOMITE FORMATION

K. JINGHWA HSU

University of California, Riverside, Calif. (U.S.A.)

SUMMARY

Chemical experiments under atmospheric conditions so far have not yielded any
unequivocal answers on the stability of dolomite. The possibility that nesque-
honite or hydromagnesite might be the stable magnesium carbonate at 25 "C and
1 atm. in the system MgC03-COz-HzO has added further complications. Unless
further experimentation proves the contrary, the possibility exists that the stability
of dolomite in the system C~CO~-M~CO~-COZ-HZOat 25°C and'l atm. is
related not only to temperature and pressure, but also to the partial pressure of
coz.
The geologic occurrence of magnesium-bearing carbonates in Recent
sediments is somewhat puzzling. The common occurrence of dolomite in ancient
carbonate rocks, however, indicates that dolomite, rather than a mineral pair,
is the stable phase under the low temperature and pressure conditions of carbo-
nate diagenesis.
The possibility that the calcite-hydromagnesite pair might represent a stable
assemblage at 25°C and 1 atm. and extremely low pcoZ in the system CaCO3-
MgCO,-COz-HzO has been suggested-by the theoretical considerations and by
experimental data. This tentative conclusion is not ruled out by the field evidence.
Experimental evidence on the solubility of dolomite is controversial. The
composition of the ground waters in dolomites is such that the writer believes the
highest reported values (Kdr 1O-l') are more nearly correct than the lower values.
This interpretation is not accepted by those who question whether equilibrium has
been established or even approximated between a ground water and the solid
carbonate phases of its host rocks. The controversy on the solubility of dolomite
will probably not be resolved until dolomite is synthesized under controlled atmos-
pheric conditions. Inasmuch as the solubility of dolomite is not known, the ques-
tion whether any natural water (such as normal marine sea water) is saturated with
dolomite cannot be satisfactorily answered. Experimental results on the composi-
tion of solution at dolomite-calcite-solution equilibrium differ radically, and
deductions from such results have led to controversies. Nevertheless, all experi-
mental results as well as deductions on the basis of ground water composition
studies suggest that the Kdz value is less than 1 at room temperatures and atmos-
170 K. J. HSU

pheric or near-surface pressures. Paradoxically, sea water with a magnesium/

calcium-concentration ratio of 5.3 is apparently not dolomitizing. The reason is
not clear, although alternative explanatidns have been suggested.

INTRODUCTION

The origin of dolomite involves two different problems. First of all, the chemical
condition must have been such that the mineral dolomite could be formed as a
stable phase. Secondly, the geologic history of a region must have permitted the
chemical condition for the formation of dolomite mineral to persist long enough
for sufficient quantity of the mineral dolomite to be formed in order to constitute
a dolomite rock, or “dolostone”. This chapter is only concerned with the chemical
problem of dolomite formation.
Chemical experimental results are required to define specifically the con-
ditions (temperature, pressure, chemical potentials of the various components in
solution, etc.) under which the dolomite mineral can be formed. Unfortunately,
experimental studies pertaining to dolomite formation under room temperatures
and atmospheric pressures have not been very successful. Those who attempted
to determine the solubility by dissolving dolomite in aqueous solutions have given
widely divergent results; the solubility product of dolomite at 25°C and 1 atm.,
for example, as determined by the various experiments, ranges from 10-17 to
10-20, or a difference of three orders of magnitude! Deductions on the basis of
controversial experimental data led, at times, to conflicting opinion. Further
confusion arose because the occurrence of dolomite is not always what might be
predicted on the basis of experimentation.
This chapter is a review of the present status of our knowledge of the chemis-
try of dolomite formation under the relatively low temperatures and pressures of
sedimentary and diagenetic conditions. The theoretical discussions begin with a
consideration of the conditions of equilibrium as given by GIBBS(1875-1878) in
his collected works, which form a basis for further theoretical deductions. A re-

-
view of experimental work follows next. Finally, the geologic evidence pertaining
to the chemistry of dolomite formation is presented.

A THREE-FOLD PROBLEM

-
Three questions may be asked regarding the chemistry of formation of the mineral
dolomite.
(I) Whether the double salt dolomite rather than a pair of single salts,
calcite-magnesite, calcite-nesquehonite, or calcite-hydromagnesite, is the stable
phase under a given temperature and pressure condition?
CHEMISTRY OF DOLOMITE FORMATION 171

(2) Whether the mineral dolomite could be precipitated from a solution of

a given composition under a given temperature and pressure condition?
(3) Whether the mineral dolomite should replace the mineral calcite (or
aragonite) when a solution of a given composition at a given temperature and pres-
sure is in contact with a solid phase of calcium carbonate?
These three questions should be answered separately. The often-repeated
phrase in geologic literature “conditions favorable for the formation of dolomite”
is not meaningful unless one specifies the mode of formation.

STABILITY OF DOLOMITE

Theoretical discussions of conditions of equilibrium

GIBBS(1875-1878, p.63) stated that the variation of energy of any homogeneous

part of variable chemical composition of a given mass is:
dE = TdS - pdV + pldml -k pzdmz + . . . + pndmn (1)
Where E denotes the total energy of the homogeneous part; T=its absolute
temperature; S=its entropy; p=its pressure; V=its volume; ml, mz, . . mn are .
the quantities of the various substances; and pi, pz, . . . pn denote the chemical
potentials of the various substances or the differential coefficients of E taken
with respect to ml, mz, . . . md.
If, for example, the whole mass consists of three homogeneous parts each
consisting of the same two components, the variation of the energy of the system
+ +
is expressed by dE’ d E ’ dE“’, if one distinguishes the letters referring to the
different parts by accents. GIBBS(1875-1878, p.64) stated that the general condi-
tion of equilibrium requires that:

dE‘ + dE” + dE”’ b 0 (2)

or:

To satisfy equation 3, the necessary and sufficient conditions of equilibrium

are:

1 The chemical potentials are intensive quantities: they can be expressed in J/g, or J/mole. Gibbs
used the chemical potentials in terms of J/g; consequently, molecular-weight terms are involved
in many of his equations. The chemical potentials are expressed here in terms of J/mole.
172 K . J. HSU

If the whole mass consists of three homogeneous parts (the first part
consists of a substance s1, the second part of s2, and the third part of a
substance s3 which is composed of s1 and s2 combined in the ratio l / l ) , then
conditions of equilibrium are (GIBBS,1875-1 878, p.67):

On considering the reaction:

CaC03 (calcite) + MgC03 (magnesite) CaMg(CO3)z (dolomite) (A)
at relatively low temperatures and pressures, when dolomite ideally does not
contain CaC03 and MgC03 as separately variable components, the conditions of
equilibrium are as follows:
T' = T'= T"
P' = P" = P"'
Y'CaCO, i-
p"MgC03 p"'CaMg(C03)2

where ~'caco3.,U"MgC03 and ,U"'CaMg(C03)2 are the chemical potentials of the

CaC03 in calcite, MgC03 in magnesite, and CaMg(CO& in dolomite, respec-
tively.
If calcite and magnesite are to form dolomite spontaneously, under a given
T and p:
Y'CaCO3 + p"MgC03 > p"'CltMg(C03)2 (7)
Inasmuch as chemical potentials of those solid phases are a function of
temperature and pressure only, and are independent of other variables, the stability
of dolomite in the system CaCOs-MgCO3 depends thus upon temperature and
pressure only.
A complication arises, however, because of the uncertainties regarding the
stability of magnesite.
Free-energy calculations suggested that magnesite rather than nesquehonite
is the stable magnesium carbonate phase at a temperature of 25 "C and a pressure
of 1 atm in the system MgC03-H20 (GARRELS et al., 1960). Evidence on the basis
of synthesis experiments suggested the contrary. KAZAKOVet al. (1957) repeatedly
synthesized nesquehonite or hydromagnesite at room temperatures (1 5-24 "C)
and atmospheric pressures, but failed to obtain magnesite under such conditions.
Hydrothermal experiments by SCHLOEMER (1 952) also suggested that nesquehonite
is the stable phase at temperatures below 80°C, above which, depending upon the
 40001-
CHEMISTRY OF DOLOMITE FORMATION 173

0 Brucite
350° A
0

:250° M

Moqnesite
\
..
I
w

N e s q u e honite
--
500 1,000 1,500 2,000 2,500 3,000 3,500 4,000
PRES'URE (ATM)

Fig.1. Stability of magnesite. (Modified after SCHLOEMER, 1952.). Hydrothermal experiments by

Schloemer suggested that nesquehonite is the stable phase containing MgCO3 at room tempera-
tures and atmospheric pressures. The univariant curve defining the equilibrium MgCOq8) +
3Hz0 = M ~ C O ~ . ~ H ZisOdetermined
(~) by experimentally determining the hydration temperature
of nesquehonite at various pressures. The possibility of errors introduced by sluggishness of
the reaction at low temperatures cannot be ruled out. That nesquehonite is the stable magnesium-
carbonate phase at room temperatures and atmospheric pressures is also indicated by the synthe-
sis experiments of KAZAKOV et al. (1957). Free-energy calculations by GARRELS et al. (1960),
however, suggested that magnesite rather than nesquehonite is the stable phase in the system
MgC03-H20 at 25 "C and 1 atm. total pressure. Crosses indicate runs in which the stable solid
phase is nesquehonite; triangles, magnesite; and spheres, brucite.

confining pressure effect, nesquehonite may dehydrate to form magnesite and

water (Fig. 1).
If nesquehonite, rather than magnesite, is the stable carbonate in the pre-
sence of water, the following reaction must be considered:
CaC03 (calcite) +
MgC03.3HzO (nesquehonite) CaMg(CO3)z
(dolomite) + 3Hz0 (B)
The conditions of equilibrium are:

where and , U H ~ O represent the chemical potentials of MgC03.

$'MgC03.3H20
3Hz0 in nesquehonite and that of water, respectively. In such a case, the stability
of dolomite at room temperatures would be not only a function of T and p, but
also that of the chemical potential of the water.
174 K. J. HSU

A still further complication arises because hydromagnesite could be the

stable magnesium carbonate phase of the system MgC03-COz-HzO at room
temperatures and very low pco, (KAZAKOV et al., 1957; GARRELS
et al., 1960). If
so, the following reaction must be considered:
4CaC03 (calcite) +
M ~ ~ ( C O ~ ) ~ ( O H ) Z .(hydromagnesite)
~HZO +
C02 e 4CaMg(CO& (dolomite) 4H20 + (C)
The condition of equilibrium at any given T and p , would then be:
T = T' = T" = T"'
p = p' = p" = P"' (9)
4p'CaC03 + p"Mgp(C03)3(OH)2.3H20 + pC02*4p"'CaMg(C03)2 + ~ P H , o
where ~ " M ~ ~ ( C O ~ ) ~ ( O H ) Zand
. ~ H pcoZ
~ O represent the chemical potential of
M ~ ~ ( C O ~ ) Z ( O H )in~ .hydromagnesite
~HZ~ and that of the C02, respectively.
The question whether calcite-hydromagnesite pair or dolomite represents a stable
phase at room temperatures is related, therefore, not only to T and p , but also to
the chemical potential of water and to the partial pressure of COZ.

Deductions on the basis of solubility experiments

The chemical potential of a one-component pure substance, expressed in J/mole

is equal to its molar Gibbs Free energy, F. The change of free energy of the reac-
tion A can thus be expressed by AFA, which is:
AFA = F"' - (F' + F") (10)
where F', F", and F"' represent molar free energies of calcite, magnesite, and
dolomite, respectively. Equations 7 and 10 show that AFA must be negative if dolo-
mite is to be formed from calcite and magnesite spontaneously at any given
T and p .
The AFA is related to solubility constants through a consideration of the
following equilibria of calcite, magnesite, and dolomite with their saturated
solutions:
CaC03 (calcite) s Ca2+ + CO& (D)
MgC03 (magnesite) zMgz+ + cos2- (E)
CaMg(CO3)z (dolomite) Caz+ + Mgz+ + 2C0s2- (F)
The free energy of a solution, F, at any given T and p , is related to,the activity of
the ions, a, in solution by the relation (LEWISand RANDALL,1923, p.291):
F = F" -l- R T l n a (1 1)
where F" is the free energy of a solution at an arbitrarily chosen standard state.
CHEMISTRY OF DOLOMITE FORMATION 175

Inasmuch as the free energies of the solids are equal to the free energies of their
saturated solutions (FCa2+C0:-, FMg2+co:-, Fca2+Mg2+(co:-)2) at any given
T and p, then:
F' = FCa'+Co:- = F"ca2+ + Poco:- f R T In Kc (12)
F" = FMg2+co,2- = F0Mg2+-/ F"c0:- $- R T In Km (13)
F"' = Fca2+Mg2+(c0:-), = FoMg2++ F"Ca'+ + 2F"co:- -/ RTln Kd (14)
where Foca2+,FoMg2+and F"CO:- represent the free energies of Ca2+, Mg2+, and
C032- ions of a solution at an arbitrarily chosen standard state, and K,, Km,
and Kd represent the equilibrium activity products (or solubility constants) of
calcite, magnesite, and dolomite, respectively, at any given T and p.
Thus, on substituting equations 12, 13, and 14 into equation 10, one obtains
the condition of stability of dolomite, i f
Kd
AFA = RTln- <O
KcKm
Inasmuch as solubility constants can be determined by solubility measure-
ments, AFA at any given T and p can thus be calculated from such experimental
data. HALLA(1935), GARRELS et al. (1960), and HALLAet al. (1962), proceeded
from such a theoretical consideration to determine the stability of dolomite on the
basis of solubility measurements. Unfortunately, as discussed later (p. 179), dif-
ferent workers experimenting at the same T and p conditions have obtained
different values of Kd; none of the results are universally accepted because equi-
librium has not been ascertained during any of the experiments. Calculations
based upon such debatable results are thus subjected to the same degree of uncer-
tainty as the experimental results themselves. Nevertheless, calculated AFA values
based on those widely divergent results are all negative, ranging from about -0.5
to -4 kcal. for the reaction A at 25 "C and 1 atm. (HALLA,1935; GARRELS et al.,
HALLA et al., 1962). Halla used the maximum reported Kd value in his calculations,
which is three orders of magnitude larger than the minimum reported value used
by Garrels in his calculations. The available experimental evidence is thus favoring
the idea that dolomite, rather than calcite-magnesite, is the stable phase at 25 "C
and a pressure of 1 atm.
The change in Gibbs free energy involved in reaction B at room tempera-
tures (25-38°C) and 1 atm. have also been calculated from solubility data (HALLA,
1935, p.79). The results also indicated a negative free energy change for such a
reaction under atmospheric conditions. The same criticism concerning the estab-
lishment of equilibrium, however, must be'applied, and the calculated results have
thus been viewed with skepticism.
The stability field of dolomite and of the calcite-hydromagnesite pair at
25"Cand 1 atm. has been tentatively defined by GARRELS et al. (1960, p.416, f i g 3
176 K. J. HSU

on the basis of their solubility studies and free energy calculations. Their postulate
contains also an element of uncertainty because of the difficulty of ascertaining
equilibrium during solubility measurements of magnesium-bearing carbonates.

Deductions on the basis of synthesis experiments

Early claims of having succeeded in synthesizing dolomite under atmospheric

conditions (e.g., RIVIZRE,1939) were not supported by positive identification of the
dolomite phase. GRAFand GOLDSMITH (1956, p. 178) have synthesized, at tempera-
tures less than 100"C and unknown pressures, a calcium-magnesium carbonate
phase with a calcium content somewhat greater than that of dolomite. Such a
carbonate, termed protodolomite, has a composition ranging from Ca55Mg45 to
Ca,,Mg4, and was formed at a temperature as low as 25 "C. These workers failed,
however, to obtain dolomite with an ordered arrangement of Ca and Mg ions
under low temperatures, although such dolomite could be easily synthesized at
higher temperatures of 200-500 "C. Graf and Goldsmith accepted Halla's'tentative
conclusion that dolomite, rather than the pair calcite-magnesite, is the stable
mineral at room temperatures. They explained their failures in synthesizing or-
dered dolomite in terms of the kinetics of dolomite formation; they believed that
crystallization under the low-temperature experimental conditions could not
attain the ordered Ca-Mg configuration in dolomite.
Recently, OPPENHEIMER and MASTER(1963) synthesized dolomite at 22-
25°C and 1 atm. in an experimental aquarium. The carbonate phase was iden-
tified by X-ray diffraction method. Whether an ordered dolomite or proto-
dolomite was synthesized was not mentioned in the published preliminary report.
Except for this one reported success, the repeated failures to synthesize dolomite
under atmospheric conditions are well known to students of the dolomite problem.
Commonly a hydrous magnesium carbonate, nesquehonite or hydromagnesite,
co-precipitates with a calcium carbonate phase under atmospheric temperatures
and pressures (e.g., KAZAKOV et al., 1957). The interpretation of the experimental
evidence is very difficult. One might postulate that calcite and nesquehonite, or
calcite and hydromagnesite, but not dolomite, represent the stable assemblage
under atmospheric conditions, and that the dolomite synthesized in the aquarium
represents a metastable biochemical precipitate. Alternatively, one might conclude
that the rate ofthe dolomite formation without catalysis is so slow under atmospheric
conditions that the metastable mineral pair tend to be formed from supersaturated
solutions; the organisms in the experimental aquarium assumed the role of the
catalyst which promotes the formation of the stable dolomite phase.

Deductions from j e l d occurrences

Recent dolomite has been repeatedly discovered during the last few years (e.g.,
CHEMISTRY OF DOLOMITE FORMATION 177

ALDERMAN and SKINNER, 1957; JONES,1961; WELLS,1962; DEFFEYES et al., 1964).

The Recent dolomite of Australia is calcium-rich, having a constant composition
of Ca56Mg44; it was considered a protodolomite because of its structural resem-
blance to those synthesized (SKINNER, 1960). The Recent dolomite of the Antilles,
ranging in composition from Ca56Mg44 to Ca54Mg46 has an ordered structure
(DEFFEYES et al., 1964). These discoveries have dispelled much of the doubt that
dolomite can be a stable phase under room temperatures and atmospheric pres-
sure. On the other hand, the assemblage aragonite-hydromagnesite has also been
reported from the Recent or Pleistocene sediments (ALDERMAN and VON DER
BORCH,1960; GRAFet al., 1961). Aragonite is not the stable calcium carbonate
phase under atmospheric conditions (MACDONALD, 1956). Also the surficial de-
posits of aragonite and hydromagnesite of Australia are replaced by dolomite at
a few inches below the surface (ALDERMAN and VON DER BORCH,1960). These
facts suggest that the aragonite-hydromagnesite pair might represent metastable
phases precipitated from supersaturated solutions at atmospheric temperatures
and pressures. An alternative explanation that hydromagnesite is the stable phase
under very low atmospheric pcoZ,however, cannot be ruled out.
Dolomite rather than the single-salt mineral pairs is found in ancient sedi-
mentary formations containing calcium and magnesium carbonates. This fact
alone strongly indicates that the double carbonate is the stable phase under the
low temperatures and pressures of carbonate diagenesis.

PRECIPITATION OF DOLOMITE

In the heterogeneous equilibrium dolomite-solution:

CaMg(CO3)z (dolomite) Ca2+ + Mg2+ + 2CO$- (F)
at equilibrium under any given T and p (GIBBS,1875-1878, p.426):
/&a2+ + PMg2+ + 2pCO,2- = p”’CaMg(C03)2 (16)
where pca2+, p M g 2 + and pc0,2- represent the chemical potentials of calcium,
magnesium, and carbonate ions in the solution phase. The additional condition
that dolomite represents a stable phase is expressed by equation 7:
P‘CaC03 + P”MgC03 > p”’CaMg(CO.&
Today activity and related quantities rather than chemical potential serve as the
usual medium for expressing the results of thermodynamic measurements on solu-
178 K. J. HSU

tions. Equation 16 is expressed in terms of activities in the better known form of

mass-action lawl:
(aca2+)(aMg2+)(aco:->2 = Kd (17)
where (ma2+), (aMg2+),and (ace:-) represent the activities of calcium, magnesium
and carbonate ions in the saturated solution, and Kd is the equilibrium activity pro-
duct, or the solubility product, of dolomite and is a constant at any given T and p.

Solubility experiments

Several attempts have been made to determine the solubility of dolomite under
room temperatures and 1 atm (HALLA,1935; YANAT'EVA, 1950, 1955a, 1955b,
1956, 1957; KRAMER,1959; GARRELS et al., 1960; Von Tassel in HALLAet al.,
1962). So far all solubility experiments consisted of dissolving dolomite in aque-
. ous solutions. Different analytical techniques in determining the composition of
the solutions have been used: for example, GARRELS et al. (1960) determined the
carbonate concentration indirectly by measuring the pH of the solutions. Common-
ly after an initial increase, the concentration of a solution dissolving dolomite be-
came practically constant within the errors of measurements. Inasmuch as the
solubility experiments cannot be continued forever, the final apparently constant
concentration of the solution is assumed as the equilibrium concentration. The
equilibrium constant Kd has been calculated from the relation:
Kd = (mCa2+)(7Ca2+) (mMg2+)(yMg2+)(mCO:-)2 (yCO:-)2 (18)
where (mca2+),(mMg2+)and (rnco:-) are the molar concentrations, and (yca2+),
(yMg2+),and ( y ~ 0 , 2 -are
) the activity coefficients of the ions in solution, which are
usually calculated through the use of the Debye-Hiickel relations for very dilute
solutions (KLOTZ,1950, p.239).
Inasmuch as attempts to precipitate dolomite under controlled atmospheric
conditions have not been successful, the usual procedure of checking equilibrium
by precipitating a solid phase from its supersaturated solution has not been under-

The mass-action law expressed in terms of concentration of solute (in a very dilute solution)
has been derived by GIBBS(1 875-1 878, p.424426) through the relation, which is approximately
valid for very dilute solutions under ordinary pressures:
+
p = function ( t ) RT In rn
The term activity was introduced by Lewis and was defined by the equations (LEWISand
RANDALL,1923):
+
p = function ( t ) RT In a
p(+) = 1

On substituting activity terms for concentration terms in very dilute solutions, the mass-action
law is expressed in terms of activity. ADAMS
(1936) gives a thorough discussion of the definitions
of activity.
CHEMISTRY OF DOLOMITE FORMATION 179

TABLE I
COMPARISON OF EXPERIMENTALLY DETERMINED AND ESTIMATED VALUES OF DOLOMITE SOLUBILITY

Investigators Kd

Values determined experimentaNy

Von Tassel in HALLA et al. (1962)

KRAMER(1959)
YANAT'EVA(1955a)

GARRELS
et al. (1960)

Values estimated from composition of subsurface waters

HOLLAND et al. (1964)
Hsu (1963)
BARNES and BACK(1964)

taken in those experiments. All published data on the solubility of dolomite under
atmospheric conditions, therefore, contain an uncertainty. This uncertainty left
geochemists in doubt as to which of the widely divergent results obtained by dif-
ferent experimenters is more nearly correct. The value of Kd at any given temper-
ature and pressure should be a constant. The reported values of & for 25 "C and
1 atm., calculated from solubility measurements, however, range from 10-17 to
10-20, a difference of three orders of magnitude (Table I).
Two alternative explanations have been advanced to explain the discrepancy
of Kd values calculated from laboratory experiments. One school of thought sug-
gested that the highest reported values (Kd z 10-17) should more nearly approxi-
mate the equilibrium value than the lower values, because the equilibrium has al-
ways been approached from the undersaturation side (Hsu, 1963). Another school
of thought suggested that the lowest reported values (Kd z 10-20) should represent
the equilibrium value; higher values resulted from grinding of dolomite, which
caused disordering of the surface of dolomite crystals, either during sample prep-
aration or from the stirring or tumbling during the measurement itself (GARRELS
et al., 1960, p.417). This controversy cannot be entirely resolved until dolomite
can be synthesized under controlled atmospheric conditions. It can be pointed
out, however, that the high estimates of dolomite solubility in ground water can
not be explained in terms of disordering by grinding.

Synthesis experiments

The composition of the solution phase in the dolomite-synthesis experiments of

Graf and Goldsmith is unknown. The dolomite synthesized by Oppenheimer was
180 K. I. HSU

precipitated from a solution similar to sea water in composition; he reported (per-

sonal communication, 1964):
“The solution was 1 1 of artificial sea water, composition of Lyman and
Fleming (In: SVERDRUP et al., 1942, p.186), plus 0.1 g peptone, 0.01 g FeP04,
0.1 g KN03 and 50 ml of soil extract prepared from mangrove peat. To the liter
of solution were added 50 g each of quartz and Mg-calcite (7%) with a particle
size of approximately 100p and an inoculum consisting of a mixture of micro-
organisms from an algal mat from the shore line near The Marine Laboratory,
Miami. Sterile controls were maintained by adding 0.5 % mercuric chloride to the
above solutions without inoculum. The solutions were then subjected to 12 h of
light and dark, at a temperature of approximately 20°C for 30 days. During alter-
nate dark and light periods, the pH of the solution had a diurnal fluctuation be-
tween 7.6 and 9.2 and the carbonates were both dissolved and precipitated and
quartz dissolved. After 1 month of diurnal pH fluctuation, X-ray analyses of the
residual carbonate material showed the presence of dolomite.”
The temperature of Oppenheimer’s synthesis experiments varied ‘between
22 O and 25 “C. Oppenheimer believed that the magnesian calcite was dissolved,
and both calcite and dolomite precipitated during the pH change caused by the
biologic activities of the living organisms. Inasmuch as the pH and the carbonate-
ion concentration of the solution at the time when dolomite was precipitating are
unknown, solubility constant K d cannot be obtained from the data of this experi-
ment. One is left with the uncertainty whether K d is more nearly equal to 10-17
or to 10-20.
ROSENBERG and HOLLAND (1 964) studied the stability relations of calcite,
dolomite, and magnesite in 2 M chloride solutions at temperatures ranging from
275°C to 420°C and pressures of a few hundred atmospheres. They have been
able to synthesize dolomite and to analyze the calcium and magnesium ion
concentrations of the solution phase. Their data are, however, insufficient to per-
mit a calculation of the & value. If one is so bold as ( I ) to assume that the activity
coefficient ratio, ( Y M ~ ~ + ) / ( Y Cfor
~ ~such
+ ) , concentrated solutions is not much
different from unity, and (2) to make an extrapolation from such high temperatures
to room temperatures, then one could obtain, by using the relation which is
expressed by equation 19, that K d at 25 “C is of the order of 10-17 (Fig.2). Such a
long range extrapolate with a very uncertain assumption is, of course, extremely
speculative.

Composition of subsurface waters in dolomite

Studies of the chemical composition of the natural waters have served as an inde-
pendent check of the validity of the various experimental data. Namely, the solu-
bility of dolomite can be computed from the analysis of a subsurface water which
CHEMISTRY OF DOLOMITE FORMATION 181

3 4-

\
33-A\m

:::
30-
29- \
2 8 - \
2 7-
?\
26-
- 2 5 -
\

\
0- 24-
w 23- \
-
x
22'
2 1 -
\
\
+ 20-
1 19-
18-
17-
I 6 -
15-
14-

6 02 04 06 08 10 12 14 16 18 210

Fig.2. Variation of the calcium-magnesium concentration ratio of a solution at calcite-dolomite-

solution equilibrium as a function of temperature. (Modified after ROSENBERG and HOLLAND,
1964.). Data at lower right corner are taken from the hydrothermal experiments of ROSENBERG
and HOLLAND (1964)at high temperatures and some unspecified high pressures. Data at upper
left corner are taken from a ground-water study by Hsu (1963). Oil-field brine data have not yet
been systematically studied. The question mark on the diagram indicates the range of tempera-
ture and concentrations of oil-field brines possibly in equilibrium with both calcite and dolomite
(CHAVE, 1960). Such an extrapolate from the high-temperature data at high pressures to low tem-
peratures at a much lower pressure is very speculative. The relation of the concentration ratio
to the activity ratio at equilibrium depends upon the activity coefficient ratio of the calcium
and magnesium ions in solution. For the very dilute solutions studied by Hsw (1963), the con-
centration ratio is approximately the same as the activity ratio. Squares indicate the temperature-
concentration ranges in which the stable carbonate phase is dolomite, and triangles, calcite.

has equilibrated with dolomite. The difficulty of such an approach is two-fold:

(1) sampling problems, and (2) difficulty of ascertaining equilibrium.
A most serious sampling problem arises from the tendency of the bicarbon-
ate ion in water samples to equilibrate with atmospheric COZ before an analysis
could be made. Consequently, subsurface waters from carbonate terranes are often
apparently supersaturated with respect to the carbonate phases when calculations
involve pH and (mco,2-) terms (e.g., BACK,1960; HOLLANDet al., 1964). To cir-
cumvent the difficulty, one could utilize the relation that at any given T and p:

Kd = (aMg2')/(aca2') ' Kc2 (19)

where ( u M ~ ~and
+ ) (aca2+) represent the activities of magnesium and calcium ions
of a solution in equilibrium with both calcite and dolomite. Using this method,
Hsu (1963) obtained a figure of 2 * 10-17, and HOLLANDet al. (1964) obtained a
182 K. J. HSU

figure of the about same order of magnitude (IO-l7). Those results led to the
belief (Hsu, 1963; BARNESand BACK,1964) that the experiments which yielded the
highest published figures on the solubility of dolomite most likely have approxima-
ted equilibrium.
The question whether ground waters in dolomites have equilibrated with
the carbonate phases in the host rocks has not been resolved. Due to its slow flow
rate a ground water might maintain a prolonged contact with its host rock under
similar temperature and pressure conditions; the opportunity of achieving equilib-
rium in nature is thus far greater than that afforded by laboratory experiments of
limited durations. That calcite-dolomite-solution equilibrium might actually
be established during the flow of ground waters through dolomitic limestones is
indicated by the relatively constant activity ratio of such waters (Fig.3). Such a
constant ratio constitutes a necessary, but not sufficient, proof of equilibrium.

2.01
DOLOMITE STABLE

. . :. , .
........
.... . . . . . -
. ~

- 0.5-
A
A

-
",- 0.4-

0.3-
A .

CALCITE STABLE
0.2- A A

<O.l A A A
2 3 4 5 6 7 0 9
[caZ'] rnMal/l

Fig.3. Magnesium/calcium molar concentration ratio of shallow ground waters, and the pos-
tulated stability fields of calcite and of dolomite at about 25°C and at near-surface confining
pressures of a few atmospheres. (After Hsu, 1963.). Data on the chemical composition of dolo-
mitic limestones are taken from Hsu (1963). Data on the chemical composition of waters from lime-
stones and from dolomites are taken from WHITE et al. (1963). Note that the limestone waters all
have magnesium/calcium ratio equal to or less than the postulated ratio at dolomite-calcite-
solution equilibrium, and that the dolomite waters all have magnesium/calcium ratio equal to or
greater than the postulated equilibrium ratio.
CHEMISTRY OF DOLOMITE FORMATION 183

Composition of surface waters related to Recent dolomite precipitation

Solubility of dolomite could be estimated if a natural water which is precipitating

dolomite could be analyzed. ALDERMAN and SKINNER (1957, p.566) believed that
the Recent dolomite of Australia was precipitated from waters which are similar
to sea water in composition, but which have a high pH of about 9.2 and a salinity
half of that of an average sea water. No attempts were made to calculate the solu-
bility constant of dolomite. JONES(1961, 1963) made a detailed study of the chem-
ical composition of the surface waters in the Deep Spring Playa region, Cali-
fornia, where Recent dolomite has been found. He reported that “dolomite ooze
coats the bottoms of all surface inflow channels (to the Deep Spring Playa) from
springs” implying that the precipitation of dolomite might be related to the evap-
oration of such spring waters. The spring waters contain very little dissolved solids
and have a magnesium/calcium concentration ratio similar to that of the ground
waters in dolomitic limestones (cf. HSU, 1963, and JONES,1963). This fact would
support the postulate of for the value of K d . An uncertainty remains, how-
ever, because the composition of the evaporated spring water which deposited
dolomite might have been significantly different from that of the fresh spring
waters.

REPLACEMENT OF CALCIUM CARBONATE BY DOLOMITE

On considering the heterogeneous equilibria:

CaMg(C03)~ Ca2+ + Mg2+ + 2Coa2-
CaC03 zCa2+ + C032-
the conditions of calcitedolomite-solution three-phase equilibrium are:
T = T’ = T’”
p = p’ = p”’
PCa2+ + + 2PC032-
+
PMg2+ = P”‘CaMg(C03)e
pca2+ P C O , ~ - = P’CaCO3

Expressed in terms of ion activity, at equilibrium under any given T and p :

(aca2+)(am2+)(ace:-)' = Kd
(aca2+)(aco,2-) = KC
At the three-phase equilibrium, therefore, the following relation would hold true:
(aMg2+)/(aca2+)
= Kd/Kc2 = Kdz (22)
The magnesium/calcium activity ratio of a solution in equilibrium with both
calcite and dolomite is a constant at any given temperature and pressure, and is
184 K. J. HSU

represented by the abbreviation Kdz. Dolomitization of a calcium carbonate could

occur if the magnesium/calcium activity ratio of a solution in contact with a
calcium carbonate would exceed the value of Kdz.
On letting the ion activity terms be substituted by terms of ion concentrations,
one gets:
(mMg2+) (yMg2+)/(mca2+)(yCa2+)= Kdz (23)
Equation 23 can be written as:
(mMg2+)/(mCa2+) = Kdz * (yCa2+)/(rMg2+) (24)
The activity coefficients, YMg2+ and yca2+, are not only a function of T
and p , but also a function of the concentrations of the various ions in solution.
Thus, the ion-concentration ratio at dolomite-calcite-solution three-phase equi-
librium is not necessarily a constant at any given T and p.

Solubility experiments

Several experiments have been attempted by different investigators to obtain the

magnesium and calcium ion concentrations of a solution in equilibrium with
both calcite and dolomite at room temperatures and atmospheric pressure. Time-
concentration plots have indicated that to achieve calcite-dolomite-solution
equilibrium is even more difficult than to obtain the simpler dolomite-solution two-
phase equilibrium (YANAT'EVA,1950, fig. 1). The results of different experiments
do not agree.
The wide discrepancies in reported values are clearly indicated in Table 11.
The magnesium/calcium concentration ratio at the calcite-dolomite-solution
three-phase equilibrium for the MgC03-CaC03-C02-H20 system should be a
constant at a given temperature, pressure, and a constant partial pressure of C02.
The reported values range from 0.017 (at 17 "C) to 0.146 and 0.352 (at 25 "C).Nene
of the experimenters have demonstrated establishment of equilibrium through the

TABLE I1

SOLUBILITY DATA OBTAINED BY DIFFERENT INVESTIGATORS

Experimenter Temperature Composition at presumed equilibrium Duration of

("C) mca2+ mMg2+
experimenr
in mll solution mMgZ+'
mcaz+ (days)

BAR (1932) 17 6.339 0.110 0.017 30

HALLA (1935) 25 8.21 2.67 0.325 28
8.67 3.05 0.352 28
YANAT'EVA
(1950) 25 8.10 1.18 0.146 100
CHEMISTRY OF DOLOMITE FORMATION 185

precipitation of the solid phases from a supersaturated solution. One cannot be

certain which, if any, of the reported values is more nearly correct.
Solubility studies of the system C~CO~-M~CO~--COZ--HZOhave also
been conducted at different temperatures (0-70°C) and partial pressures of COZ
(0.0012-1 atm) by YANAT’EVA (1955a), who also evaluated the effect of addition
of sulphate and chloride on the solubility relation of the system (YANAT’EVA, 1956;
1957). These results serve to renew the controversy of the effect ofpco, on the val-
ue of magnesium/calcium concentration ratio at calcite-dolomite-solution three-
phase equilibrium. BAR (1932) postulated that the ratio is a function of pco,.
HALLA(1935) stated that the ratio is constant under any given temperature and
pressure, and cannot be a function of any other factors such as pco,. Halla’s
statement, however, was based upon an assumption that the ratio of the activity
coefficients of calcium and magnesium ions in solution is unity; an assumption which
is probably valid only for very dilute solutions. Yanat’eva’s results supported
Bar’s postulate. Equilibrium, however, has not been ascertained during solubility
measurements; and the reported results are controversial. Thus the question re-
mains unsettled whether the magnesium/calcium concentration ratio of a solution
at the three-phase equilibrium does decrease as a result of increasing ~ c o , .

Deductions on the basis of subsurface waters

The tendency for well-recognized mineral associations to recur in rocks of widely

different age and locality is the single most important indirect evidence that approx-
imate chemical equilibrium has been established in many metamorphic rocks.
In a heterogeneous system of fluid-bearing rock, the solution in equilibrium with
the solid phases of the enclosing rock should be characterized by an equilibrium
composition. Thus, if ground water in a dolomitic limestone has equilibrated with
the dolomite and calcite phases in a rock, the magnesium/calcium activity ratio
of the fluid should be a constant under a given temperature and confining pressure
(equation 22).
A study of the chemical composition of ground waters in dolomitic lime-
stone has been undertaken (Hsu, 1963). The values of the magnesium/calcium
concentration ratio of such waters fall within a very narrow range with an average
of about 0.8, even though the calcium or magnesium concentration varies from
1 to more than 10 mmoles/l (Fig.2). The activity ratio, (aMg2+)/(acaz+),should be
approximately the same as the concentration ratio, because the magnesium/calcium
activity coefficient ratio is approximately equal to unity for these waters which
contain less than 1 part per thousand of dissolved salts. The relatively constant
activity ratio suggests that calcite-dolomite-solution equilibrium might be
approximated during the flow of ground waters through dolomitic limestone. The
value of K d z at 25°C and a pressure of a few atmospheres is thus estimated to be
about 0.8 (Hsu, 1963), which corresponds to a K d value of about 2 * 1O-l’.
186 K. J. HSU

This result is consistent with that extrapolated from the data of high-temperature
experiments (Fig.2).
Oil field brines of higher temperatures from deeply buried dolomitic lime-
stones contain much dissolved salts. The Debye-Huckel relation can hardly be
applied and Kdz for such waters cannot be ascertained. It is interesting to note,
however, that such waters tend to have a magnesium/calcium concentration ratio
of about 1/2 or 1/3 (e.g., CHAVE,1960, fig.5): such a ratio is what might have
been postulated on the basis of very speculative extrapolate shown in Fig.2.

Deductions on the basis of composition of sea water

A normal marine sea water contains 53.57 mg-atoms of Mg2+ and 10.24 mg-atoms
of Ca2+/1 (SVERDRUP et al., 1942, p.173). It thus has a magnesium/calcium con-
centration ratio of about 5.3. If the ratio of the activity coefficient of these ions is
unity, the magnesium/calcium ion activity ratio of sea water should also be 5.3,
and thus considerably greater than the various values of Kdz reported by the
various experimenters and by the students of ground water geochemistry. There
is no geologic evidence, however, that dolomitization of Recent carbonate sedi-
ments by normal marine sea water is taking place anywhere. One could accept
one of the following alternatives:
( I ) The sea water has magnesium/calcium activity ratio greater than K d z ,
but the kinetics of dolomite formation under room temperatures is so slow that
dolomitization of lime sediments cannot take place, or
(2) The sea water has a magnesium/calcium activity ratio smaller than K d z .
Dolomitization of lime sediments by sea water under surface conditions is not
possible until the chemical composition of the sea water is so modified by natural
processes that its activity ratio becomes greater than the equilibrium ratio. Such
an increased activity ratio might be related to an increase of the magnesium/
calcium concentration ratio, or to an increase of the magnesium/calcium activity
coefficient ratio, or to both.
No agreement can be reached at the present time. The numerous discoveries
of Recent dolomite in places where the chemical composition of the sea water has
been sufficiently altered seem to argue in favor of the second alternative.
Still another possibility exists that hydromagnesite rather than dolomite is
the stable phase containing MgC03 (in equilibrium with sea water) under the
atmospheric partial pressures of C02. Such a hypothesis would postulate that the
formation of dolomite under atmospheric temperatures and pressures is not pos-
sible unless P C O , of a solution is sufficiently different from that of the atmospheric
pco,, so that dolomite becomes the stable phase containing MgC03. The discovery
of Recent dolomites in high pH and presumably low pco, environment by ALDER-
MAN and SKINNER (1 957) seems to argue against such an idea.
CHEMISTRY OF DOLOMITE FORMATION 187

Deduction on the basis of synthesis experiments

As discussed on p. 176 magnesian calcite has been converted to calcite and dolomite
in artificial sea water in an aquarium experiment by OPPENHEIMER and MASTER
(1963). One might postulate that the presence of other substances, such as KNO3,
soil extract, etc., sufficiently influenced the activity coefficients of the solution so
that the magnesium/calcium activity ratio of the artificial sea water became greater
than the K d z value at the given T and p. Or, alternatively, one might postulate
that the activity ratio of some sea water is always greater than that at calcite-
dolomite-solution equilibrium; the living organisms served as a catalyst and pro-
moted a reaction which has otherwise too slow a rate without a catalytic agent.
Oppenheimer's experiment is interesting, but does not help resolve the question
whether theoretically dolomite should form spontaneously in normal marine
sea water at room temperatures and atmospheric pressures.
ROSENBERGand HOLLAND(1 964) determined the magnesium/calcium
concentration ratio of the solution at dolomite-calcite-solution equilibrium at high
temperatures of 275-420 "C and pressure of a few hundred atmospheres. Their
results show an exceedingly small magnesium/calcium concentration ratio at the
three-phase equilibrium at such high temperatures (Fig.2,4). The solutions are
too concentrated to permit a meaningful calculation of the activity ratio. An
extrapolation of such results to room temperatures, however, is interesting be-
cause such a speculative extrapolate seems to confirm the deductions from other
lines of evidence (Fig.2).

450-

-
-2!!400-
Magnesite

2 350- so Iu t io n Dolomite
z +
0 solution
n
E 300
0
-
c
250 - 't
Calcite + solution
0.6 0.7 0.8 0.9 1.0
mCa2+ /(mCa2+ + mMg*+ ) i n solution

+
Fig.4. The ratio in solutions in equilibrium with calcite, with calcite dolomite, and with mag-
nesite at temperatures between 275°C and 420°C. (After ROSENBERG and HOLLAND, 1964.)
Squares indicate runs in which dolomite was replaced by calcite; and triangles, calcite or
magnesite replaced by dolomite. The presence of the vapor phase and the possible intervention
of critical phenomena have been ignored. Circles indicate runs in which magnesite is stable.
188 K. J. HSU

CONCLUSION

Preceding discussions demonstrated clearly the unsatisfactory state of our know-

ledge on the chemistry of dolomite formation. One does not even know for certain
that dolomite, rather than a mineral pair (calcite-magnesite, or calcite-nesque-
honite), is the stable phase under room temperatures and atmospheric pressures.
The published results of the solubility of dolomite at 25 "C and a pressure of 1 atm.
differ by as much as three orders of magnitude. No two persons seem to agree on
the value of magnesium/calcium activity ratio of a solution equilibrated with
both calcite and dolomite.
Under the circumstances of our present imperfect knowledge, postulates
of the conditions that are favorable for the precipitation of dolomite, or for the
replacement of calcite by dolomite have been speculative. Much has been written
that the dolomite genesis is related to the pH, Eh, or pco, of the sedimentary or
diagenetic environments. Preceding analysis of our present knowledge has fur-
nished very little basis for such postulates.
The carbonate ion activity of a solution is related to pH by the relation:
(a
'
)'
H (aCO:-)/(a H2C03) = K H2CO3 (25)
where KH,CO~ is a constant at any given temperature and pressure. An increase of
carbonate ion activity resulting from an increased pH should favor the precipita-
tion of a carbonate phase, but there is no theoretical basis and little experimental
evidence to suppose that the rise of pH favors the precipitation of dolomite in
place of calcite. Nor is there any apparent reason why dolomitization should be
directly related to changes in pH of a solution; the conditions for replacement of
calcite by dolomite at any T and p are determined by the magnesium/calcium
ion activity ratio (equation 22) and apparently are unrelated to hydrogen ion
activity. A theoretical possibility cannot be ruled out, however, that the formation
of dolomite migth be related to changes in pH under certain circumstances, be-
cause the pH of a solution is related to the pco, of a solution, which in turn might
have some influence on the relative stability of dolomite and hydromagnesite.
The relation between'Ehand dolomite genesis is even more remote as neither
the precipitation of dolomite nor dolomitization of lime sediments involves an
oxidation-reduction process.
The relation of the partial pressure of CO, of a system to the genesis of
dolomite is controversial. The possibility that hydromagnesite might be the stable
phase containing MgC03 in the CaC03-MgC03-C02-H20 system permits a
working hypothesis that the precipitation of dolomite (in place of two single salts)
might be related to pco,. It has been shown that K d z , or the equilibrium magne-
sium/calcium activity ratio, is not a function of pco,. Whether the equilibrium
concentration ratio is related to pco, cannot be ascertained; there is no obvious
reason for such a supposition unless the activity coefficient ratio ( ~ M ~ ~ + ) / ( Yisc ~ ~ + ) ,
significantly altered by variations in pco,.
a

The effect of T and p on dolomite genesis is also not very clear. An increase
in temperature obviously increases the rate of dolomite formation. An influence
of changing temperature on the stability relations of the dolomite in the system
CaC03-MgC03-C02-H20 is shown in Fig.2, but this relation is not certain
because of the present uncertainties on experimental results.
An eventual understanding of the dolomite genesis is not completely unlikely,
despite the existence of many controversies at the present moment. The discoveries
of Recent dolomites permit field studies of the geochemistry of dolomite formation.
Ground water studies and hydrothermal experiments provide some evidence to
confirm the higher reported values of dolomite solubility at 25 "C and a pressure
of 1 atm. The reported success of synthesizing dolomite under atmospheric
conditions also points to the possibility that the equilibrium condition might
eventually be ascertained during solubility measurements, and thus many of the
present uncertainties might be resolved.

ADDENDUM

Recently LANGMUIR (1964), using the Garrels technique but giving the system
more encouragement to reach equilibrium, obtained a solubility product 1.O * 10-17
for dolomite at 25°C and 1 atm. This work gave further credence to the view
that the true value of the dolomite solubility product at 25°C and 1 atm. is not
far from 2 10-17 as suggested by the works of many.

ACKNOWLEDGMENTS

The writer is indebted to Drs. Heinrich D. Holland of Princeton University,

Princeton, N.J., Abraham Lerman of John Hopkins University, Baltimore, Md.,
and Frank Dickson of University of California at Riverside, Calif., who critically
read and improved the manuscript. My late wife, Ruth, helped in many ways
during the preparation of the manuscript.

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190 K. J. HSU

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KAZAKOV, A. V., TIKHOMIROVA, M. M. and PLOTNIKOVA, V. I., 1957. The system of carbonate
equilibria (dolomite, magnesite). Tr. Inst. Geol. Nauk, Akad. Nauk S.S.S.R.,Geol. Ser.,
64: 13-58.
KLOTZ,M., 1950. Chemical Thermodynamics. Prentice-Hall, Englewood Cliffs, N.J., 369 pp.
KRAMER, J. R., 1959. Correction of some earlier data on calcite and dolomite in sea water.
J. Sediment. Petrol., 29: 465467.
LANGMUIR, D., 1964. Thermodynamic properties of phases in the system Ca0-Mg0-COz-Hz0.
Geol. SOC.Am., Progr. 1964 Ann. Meeting, 120 (abstract).
LEWIS,G. N. and RANDALL, M., 1923. Thermodynamics and the Free Energy of Chemical Sub-
stances. McGraw-Hill, New York, N.Y., 653 pp.
MACDONALD, G. J. F., 1956. Experimental determination of calcite-aragonite equilibrium
relation at elevated temperatures and pressures. Am. Mineralogist, 41 : 744-756.
OPPENHEIMER, C. H. and MASTER, I. M., 1963. Transition of silicate and carbonate crystal struc-
ture by photosynthesis and metabolism. Geol. SOC.Am., Progr. 1963 Ann. Meeting,
125A (abstract).
RIVI$RE,A., 1939. Sur la dolomitisation des sediments calcaires. Compt. Rend., 209: 597-
599.
ROSENBERG, P. E. and HOLLAND, H. D., 1964. Stability relations of calcite, dolomite, and magne-
site between 275°C and 420°C in the presence of aqueous solutions of CaCh, MgClzand
COZ. Science, 145: 700-701.
SCHLOEMER, H., 1952. Hydrothermale Untersuchungen iiber das System Ca0-Mg0-COz-Hz0.
Neues Jahrb. Mineral., Abhandl., 1952: 129-133.
SKINNER, H. C. W., 1960. Formation of modern dolomitic sediments in south Australian lagoons.
Bull. Geol. SOC.Am., 71: 1976. Abstract. .
SVERDRUP, H. U., JOHNSON, M. W. and FLEMING, R. H., 1942. The Oceans. Prentice-Hall, New
York, N.Y., 1089 pp.
WELLS,A. J., 1962. Recent dolomite in the Persian Gulf. Nature, 194: 274-275.
CHEMISTRY OF DOLOMITE FORMATION 191

WHITE,D. E., HEM,J. D. and WARING, G. D., 1963. Chemical composition of subsurface waters.
US.,Geol. Surv., Profess. Papers, 440-F: 67 pp.
YANAT’EVA,0. K., 1950. The solubility of dolomite in aqueous salt soiutions. Zzv. Sektora
Fiz.Khim. Analiza, Znst. Obshch. Neorgan. Khim., Akad. Nauk S.S.S. R., 20: 252-268.
YANAT’EVA,0. K., 1954. Solubility of dolomite in water in the presence of carbon dioxide. Zzv.
Akad. Nauk S.S.S.R.,Otd. Khim. Nauk, 6: 1119-1 120.
YANAT’EVA,0. K., 1955a. Solubility in the system CaC03-MgC03-HzO at different temperatures
and pressures of COz. J. Gen. Chem. U.S.S.R. (English Transl.), 25: 217-234.
YANAT’EVA,O.K., 1955b. Solubility isothermsat0” and 55’ in the system Ca, Mg//C03, so4-Hzo.
Zzv. Sektora Fiz.Khim. Analiza, Znst. Obshch. Neorgan. Khim., Akad. Nauk S.S.S.R., 26:
266-269.
YANAT’EVA,0. K., 1956. The nature of the solubility of dolomite in water and in calcium sulphate
solutions at different partial pressures of C02. Zh. Neorgan. Khim., 1: 1473-1478.
YANAT’EVA,0. K., 1957. On the solubility polytherm of the system CaC03+MgS04 = CaS04
+MgC03-H20. Proc. Acad. Sci. U.S.S.R.(Chem. Sect., English Transl.), 1957: 155-157.
Chapter 5

STABLE ISOTOPE DISTRIBUTION I N CARBONATES

EGON T. DEGENS

Division of Chemistry, Woods Hole Oceanographic Institution, Woods Hole, Mass. (U.S.A.)

SUMMARY

A brief survey has been presented on the stable isotope geochemistry of carbonates.
Emphasis was placed on sedimentary carbonates in view of the fact that most of
the other chapters of this book are almost exclusively concerned with sediments.
The principal goal of this chapter was to demonstrate in what way stable
isotope studies may contribute to a better understanding of certain problems in
the area of classical geology and petrography; the data were selected accordingly.

INTRODUCTION

The stable isotope geochemistry of carbonates has been thoroughly investigated

for a number of reasons. In the first place, the common pure end-member car-
bonates (calcite, aragonite, and dolomite) are composed of only four light elements:
(I) carbon, (2) oxygen, (3) magnesium, and ( 4 ) calcium, all of which contain at
least two stable isotopes in sufficient relative abundance. In the second place,
the methods of extracting carbon and oxygen from carbonates are relatively
simple and straightforward, whereas isotope extraction techniques for other
mineral groups are more time-consuming and cumbersome. Thirdly, carbonates
are equally well at home in magmatic and metamorphic rocks (e.g., carbonatites,
nepheline-syenites, marbles), hydrothermal ore deposits (e.g., siderite veins,
accessory minerals), and in sediments (e.g., limestones, shell materials, dolomites).
It is also noteworthy that carbonates can be a product of both inorganic and
organic processes.
Factors that determine isotope fractionation in nature have been extensively
discussed by UREY(1947), CRAIG(1953, 1963), EPSTEINet al. (1953), EPSTEIN
(1959), CLAYTON and EPSTEIN(1958), and others. Principally, most of the stable
isotope fractionation in nature appears to be the result of exchange reactions
occurring at or near equilibrium. Thus, knowledge of the isotope fractionation
factors in natural systems may reveal detailed information on, for instance,
paleotemperatures, mode of mineral formation, photosynthesis, and many other
natural phenomena.
194 E. T. DEGENS

CARBON ISOTOPES

In nature, the distribution of the two stable carbon isotopes 12C and 13C (12C/13C
terrestrial ratio is about 90/1) is predominantly determined by (I) kinetic effects,
and (2) equilibrium processes. For instance, the enrichment in 12C in land plants
over that of atmospheric COZby about 2 %can be partly attributed to the more
frequent collision of 1zC160~with the photosynthesizing leaf, as compared to
13C160z.
In general, carbon isotope data are reported as per mil deviation relative
to the PDBI Chicago Belemnite Standard (CRAIG, 1953, 1957):
R
613C = (- - 1) * 1,Ooo
Rstandard
where R = 13C/12Cratio in the sample, and Rstandard = 13C/12Cratio in the
standard.
d l 8 0 is defined similarly in terms of l8O/16O ratio. The 'data for oxygen 6
values will differ by about 29.5 when reported as per mil deviation relative to
Standard Mean Ocean Water (S.M.O.W.). The relationship between 6 1 8 0 ~ ~ ~ 1
and ~ ~ ~ O S . M .can
O.W be. expressed as:
= (POPDBI* 1.03)
G1~0s.~.o.w. + 29.5
In the present chapter, all carbon isotope data are reported relative to PDBI,
whereas the oxygen isotope data are reported relative to mean ocean water
standard (the most commonly used oxygen isotope scale).
Since publication of a detailed study on the distribution of stable carbon
isotopes in nature by CRAIG(1953), many papers have appeared on this subject.
With regard to carbonates, a few pertinent studies on 13C/12C ratios include
WICKMAN (1952), LANDERGREN (1954), JEFFREY et al. (1955), CRAIG(1957),
SILVERMAN and EPSTEIN (1939, VOGEL(1959), COMPSTON (1960), KREJCI-GRAF
and WICKMAN (1960), DEGENS and EPSTEIN (1962,1964), ECKELMANN et al. (1962),
and MUNNICH and VOGEL(1963).
The distribution of carbon isotopes in the carbonate system is plotted in
Fig.1. Carbonates exhibit a range of about 12% in 13C/12C ratio. The lightest
carbonates are those associated with sulfur-evaporite domes (bacterial carbonates),
and the heaviest ones occur in meteorites. In order to illustrate the pathway of
stable isotope fractionation in the carbonate system, the precipitation and disso-
lution mechanisms of fresh-water and marine carbonates are briefly discussed here.
It is well established that due to the low COz content (0.03% by volume)
in the atmosphere (KEELING, 1958), only small amounts of C02 can be picked up
by precipitates. Rain water, therefore, will merely yield carbonate concentrations
up to about 1.2 mMol/l. Inasmuch as the usual content of dissolved carbonates
in ground waters of humid regions falls in the range of 3-10 mMol/l, most of it
STABLE ISOTOPE DISTRIBUTION IN CARBONATES 195

averaae
values

b-yI ~* carbonates
marine carbonates

hydrothermally altered limestone

ot spring gases (COZ)
atites (soevites and alvikites)

fresh-water carbonates

---
well gases ( C o p )

L
-60 -40 ” -20 -15 -10 -5 0 t5 t10 t50 t70
8 ’3c
Fig.1. Distribution of carbon isotopes in carbonates and related materials. (Largely obtained
from BAERTSCHI 1951; UREYet al., 1951; CRAIG,1953; THODEet al., 1954; JEFFREYet al.,
1955; CLAYTON and DEGENS, 1959; VOGEL, 1959; COMPSTON, 1960; ZARTMAN et al., 1961; DEGENS
and EPSTEIN, 1962, 1964; CLAYTON, 1963; KEITH and ANDERSON, 1963; G. D. Garlick, personal
communication, 1964; TAYLOR et al., 1964; and others.)

has to come from sources other than atmospheric C02.

As shown by VOGEL(1959) and MUNNICHand VOGEL(1963), the over-
whelming portion of bicarbonate ions found in fresh waters is derived from
biogenic sources in the soil. Namely, soil air, enriched in COz relative to the
atmosphere by a factor of about 10-100, will equilibrate with percolating fresh
waters and thus increase the carbonate content in the moving waters. Limestones
in contact with these COz-enriched fresh waters will react in the following manner:
CaC03 + C02 + HzO s Cazf + 2HC03l-
This reaction actually involves a number of separate equilibria (WEYL,
1958), i.e., the dissociation of calcite into calcium and carbonate ions and the
subsequent formation of the bicarbonate ions from the various carbonate species
present in the aqueous and gaseous phases (c0s2-, HzC03, and CoZ(Hz0)).
In equilibrium, the amount of calcium bicarbonate that can go into solution,
therefore, depends on the partial pressure of COZ or the quantities of dissolved
C02 in the system.
Data’on the solubility product ofCqCO3 in saline waters are more difficult
to obtain, inasmuch as-aside from temperature and hydrostatic pressure-the
solubility product is a function of type and amount of the various solutes present.
In addition, kinetics considerations are also very important. As shown by PYT-
KOWICZ (1964) and P. K. Weyl (personal communication, 1964), Mg ions in the
196 E. T. DEGENS

sea seem to interfere with the spontaneous nucleation of calcium carbonate upon
supersaturation of sea water. The power dependence of the rate of nucleation
increases from a second to a sixth order in the presence of magnesium. The in-
ference is that CaC03 deposition in the oceans is largely a result of biogenic
extraction.
In summary, under normal fresh-water conditions, where the water is
saturated with respect to CaC03 and the Mg content is negligible, dissolution and
precipitation can only take place as the solubility changes due to changes in
pressure, temperature, or chemical composition of the moving water. CaC03
deposition can be brought about, for instance, when fresh waters move into open
spaces having a lower partial pressure of COZthan that which existed at the place
of origin of bicarbonates. CaC03 deposition under marine conditions, however,
appears to be largely governed by the activities of organisms that extract both
calcite and aragonite during their life cycle.
It is important to study the fractionation characteristics of the stable carbon
isotopes that are established between the various molecular species of the natural
carbonate cycle. In Fig.2, a model is presented that illustrates the fractionation

I I
I I
I
I

t - t - -LEGEND
L-

,
I
(therrnol decomposiflbn) blcorbonote

I corbonotes

I lond plonts
(travertine) I
t10 0 -10 -20 -30
heovier L -+lighter

Fig.2. 13C/12Cfractionation in the carbonate system under different environmental conditions.

(After CRAIG,1953; MUNNICHand VOGEL,1962; and others.)
STABLE ISOTOPE DISTRIBUTION IN CARBONATES 197

steps of the 13C/W ratios. As mentioned before, soil COZ is predominantly

derived from biogenic sources, e.g., respiration of plants, or decay of organic
matter. According to CRAIG(1953) and others, the average land plant has a
613C of -25 as compared to -8 for atmospheric COz. Thus, biogenic COZin
the soil is expected to be enriched in I2C by about 2 %. This is based on the findings
of CRAIG(1954), WICKMAN ( 1 952), BAERTSCHI(1953), and others, that apparently
no significant isotope fractionation is involved, at least during decay and respira-
tion of common land plants. Direct studies on the carbon isotopic composition
of soil air, however, are still lacking.
Biogenic COZwhich is incorporated in the moving meteoric water is eventu-
ally instrumental in dissolving ancient carbonates which, in most instances, are of
marine origin. The 13C/W ratio of the bicarbonate ion in the water is, therefore,
determined by the isotopic composition of the biogenic COz and the marine
limestone. Carbonates precipitated in a marine environment under equilibrium
conditions are about 7-8%, heavier in I3C than atmospheric COz. The isotope
relationship between COz(atm),dissolved carbonate ions, and marine limestones
is presented in Fig.2.
Assuming that the biogenic COz in the soil air has a 613C of -24, and the
limestone source one of 0, the resulting bicarbonate will have a 613C of -12.
Inasmuch as this bicarbonate may still stay in contact with biogenic COz, carbon
isotope exchange will take place until equilibrium is attained. This will result in a
lowering of the d13C value in the bicarbonate by as much as 5-6%, (Fig.2). In
contact with atmospheric COz, on the other hand, equilibrium processes work in
the opposite direction, i.e., fresh waters preferentially lose 12C. In the final stage,
the bicarbonate in fresh waters exposed to the atmosphere will be isotopically
similar to the dissolved carbonates in the sea. The speed of equilibration under
various natural condition!; has been determined by 14C analysis. A review on this
subject has been prepared by CRAIG(1963) and MUNNICH (1963). Fresh-water
carbonates, therefore, may yield a wide range of 613C values from as low as about
-20 to as high as $2 to +3. Most of the fresh-water carbonate deposits, however,
fall in the range of approximately -5 to -15%, (BAERTSCHI, 1951; CLAYTON and
DEGENS, 1959; KEITHand ANDERSON, 1963).
Thermal decomposition of marine limestones will produce a COz having 613C
identical to that of the carbonate precursor (Fig.2). In analogy to the marine and
fresh-water carbon-dioxide system, the resulting bicarbonate will be enriched in
1% by about 7 % , and a carbonate forming from this source at room temperature
will have a 613C of about +7-+8 %,.
In summary, equilibrium processes predominantly govern the distribution
of stable carbon isotopes in the natural carbonate system. Carbonates deposited
in equilibrium with their surrounding water and gas phases should yield identical
613C values, independent of whether they are of organic or inorganic origin. It
appears, however, that a great number of marine organisms secrete a carbonate
198 E. T. DEGENS

that is slightly enriched in 12C relative to the value predicted by theory for a
system in isotopic equilibrium (CRAIG,1953; LOWENSTAM and EPSTEIN,1957;
WILLIAMS and BARGHOORN, 1963). Inasmuch as Recent limestones from many areas
also reflect this slight deviation in “X content from the expected equilibrium value,
the previously proposed hypothesis that marine limestones are largely a product
of life processes in the sea receives further support.
Fresh-water carbonates, in general, are significantly different from marine
carbonates. This is a result of 12C-enriched CO2 contributions to the continental
carbon-dioxide system. Thus, isotope data may reveal information regarding the
nature of ancient environments.
Aquatic marine and fresh-water organisms thriving on the dissolved car-
bonates will indirectly affect the carbon isotope distribution of marine and
lacustrine carbonates. During assimilation and respiration, the C02 content in
the dissolved carbonate fraction will decrease or increase, respectively. The
magnitude of organic activity and the available bicarbonate resources in the
environment where the plants live will, therefore, determine the fluctuations in the
613C of the bicarbonate from water samples taken during daytime (assimilation) or
nighttime (respiration). Diurnal and seasonal fluctuations in the isotope distri-
bution of bicarbonate may account for some of the apparent “disequilibrium”
613C values recorded in marine carbonates. UREYet al. (1951) presented evidence
for internal 613C variations as high as about 2x0 within the shell structure of a
single belemnite.
The carbon isotope distribution once fixed in the carbonates is apparently
not significantly altered during diagenesis and metasomatism (CRAIG, 1953;
DEGENSand EPSTEIN,1962, 1964). But it is noteworthy that the few Precambrian
marine carbonates analyzed so far are often enriched by a few per mil in 12C
relative to the average 613C of geologically younger limestones. In this context,
carbon isotope data of organic materials reported by S. R. Silverman and W. R.
Eckelmann (personal communication, 1964) are of interest. Based on hundreds
of analyses, these two investigators showed that organic extracts of rocks older
than about 400-500 million years are systematically enriched in l2C by a few
per mil. The number of data on Precambrian carbonates, however, is too small
to justify further elaboration on this subject.
Little is known on the carbon isotope distribution in high-temperature
carbonates. The 613C of marbles (CRAIG,1953) and hydrothermally altered lime-
stones (ENGELet al., 1958) fall in the range of normal marine limestones. This
adds further support to the contention that the 613C of sedimentary carbonates
is not drastically affected during the post-depositional history. Carbonatites
(BAERTSCHI, 1951; VON ECKERMANN et al., 1952; TAYLORet al., 1964) and hydro-
thermal vein carbonates (G. D. Garlick, personal communication, 1964; TAYLOR
et al., 1964), however, are enriched in 12C relative to normal marine carbonates.
Inasmuch as the fractionation characteristids in the carbonate system are reason-
STABLE ISOTOPE DISTRIBUTION I N CARBONATES 199

ably well established, these isotope data may reveal important details on the
isotopic composition of the primordial terrestrial carbon source and its subsequent
history of fractionation.
CLAYTON (1963) reported 613C values for carbonate minerals of two car-
bonaceous chondrites which are about 5-6 % greater than the ratio of any known
terrestrial carbon. According to CLAYTON (1963), the isotopic differences observed
may be a result of chemical isotope fractionation involving processes not common
to earth, or it may be the result of incomplete homogenization of substances with
different histories of nucleosynthesis. On the other hand, data by ABELSON and
HOERING (1961) indicate that decarboxylation of amino acids-which are known
to be present in meteorites-results in a significant l2C enrichment of the re-
maining amine by as much as 1-2%. Consequently, a COZ gas can be obtained
which will be enriched in 13C by the same amount. So far, dolomites are only
known from carbonaceous chondrites high in organic matter, and a cause and
effect relationship between organic matter and carbonates may be anticipated.

OXYGEN ISOTOPES

UREY(1947), in his classical paper on the thermodynamic properties of isotopic

substances, laid the foundation of modern isotope geochemistry. One of the first
elements studied in detail during the early fifties for its isotope abundance in
geological materials was oxygen (MCCREA,1950; UREYet al., 1951; BAERTSCHI
and SILVERMAN, 1951;SILVERMAN, 1951;DANSGAARD, 1953; EPSTEIN and MAYEDA,
1953; EPSTEIN et al., 1953). In later work, in particular that by E P S T E I N (1959)
~~~~,
and his associates (CLAYTON and EPSTEIN,1958, 1961; TAYLOR and EPSTEIN,1962),
the principal laws that govern oxygen isotope fractionations in natural systems
were outlined. Based on their findings and those of the earlier workers, a number
of geological problems in the field of carbonate geochemistry can be solved.
Oxygen has three stable isotopes: 160,170,and l80in a ratio of 99.759/0.0374/
0.2039 for air oxygen. In dealing with natural variations of oxygen isotopes, the
data are generally reported in terms of 1 8 0 / 1 6 0 ratios or P O , which is the per mil
deviation in 1 8 0 / 1 6 0 ratio relative to Standard Mean Ocean Water (S.M.O.W.).
Carbonates exhibit a range of about 4 % in 1 8 0 / 1 6 0 ratio, with carbonatites
being the lightest and carbonates associated with certain continental evaporite
deposits being the heaviest ones. A representative collection of data is included
in Fig.3.
The temperature dependence of oxygen isotopes present in the various
molecular species of the C02-bicarbonate-carbonate-water system allowed paleo-
temperature determinations such as those by UREYet al. (1951), EPSTEIN et al.
(1953), LOWENSTAM and EPSTEIN (1954,1956), EMILIANI (1955,1956, 1958), H. J. H.
BOWEN(1960), COMPSTON (1960), and others. Their data indicate that it is possible
 200 E. T. DEGENS

marine carbonates (syngenetic)

marine carbonates (recrystallize

f re s h-water carbonates
hydrothermally altered
hydrothermal veins

-20
-10 -5 0 +5 +10 +15 +20 +25 +30 +35

8 1%
Fig.3. Distribution of oxygen isotopes in carbonates and related materials. (Largely obtained
from BAERTSCHI, 1951; DANSGAARD, 1953; EPSTEINand MAYEDA, 1953; LOWENSTAM’ and EP-
STEIN, 1954,1956,1957; CLAY TON^^^ EPSTEIN, 1958; EMILIANI, 1958; EN GEL^^ al., 1958; CLAYTON
and DEGENS,1959; UREYet al., 1961; DEGENS and EPSTEIN,1962, 1964; CLAYTON, 1963; G. D.
Garlick, personal communication, 1964; TAYLOR et al., 1964).

to use the 1*0/160 ratio of preserved marine carbonates for the determination of
water temperature fluctuations in the ancient sea. The results of the comprehensive
isotope study by EMILIANI (1 958) are of particular geological significance because
they can be checked by different geological methods and observations. First of all,
paleotemperatures inferred from the 180/le0 data of carbonates (“Globigerina
ooze” facies) in Pleistocene deep-sea cores from the middle and equatorial Atlantic,
the Caribbean, and the Mediterranean areas, show similar patterns. Furthermore,
a generalized curve of temperature variations of tropical surface oceanic waters

I I
N o r t h America
Wisconsin(Proirie) ,&,Songomon lllinoion Yormouih Konson Aftonion Nebroskon

E u rope
Wurm
WurmP Loufen I Riss/Wurm Riss MindeVRlss Mindel Gunz/Mindel Gunz
c
0
L 30-1 2 3 4 5 6 7 8 9 10 11 12 13 14-stoqes
STABLE ISOTOPE DISTRIBUTION IN CARBONATES 201

I I I , 1 I I I

?Ye
f r e s h water
J\,S 1 0 2
0 - CoCO3 CoCO3 502
*---I c----l
12 6 14 2

ZI
c
.-0
I 300-
.-
E

400 -

v
500 I I I

Fig.5. Variations in 180/160

ratio of carbonates and cherts with geologic age. (After DEGENS
and EPSTEIN, 1962.)

t32 -

t30 -
W
.-
c

5 +28 -
-0

0
z6 0 t 2 6 -

+24 -

8 "0 calcite
Fig.6. The W O relationship between coexisting dolomites and calcites of Recent age. +=
marine environment; o = continental salt lake environment. (After EPSTEIN
et al., 1964.)
202 E. T. DEGENS

during the last 300,000 years correlates well with continental temperature varia-
tions inferred from loess profiles, pollen profiles, and with eustatic changes of sea
level (Fig.4).
Uncertainties in the reliability of paleotemperatures are introduced, how-
ever, as marine carbonates of older geologic periods are studied for their 1 8 0 / 1 6 0
ratios. In most instances, 6180 values of limestones and shell materials, unfortu-
nately, do not indefinitely remain constant with geologic time; isotopic equilibration
with the surrounding meteoric or connate waters, which is often stimulated by a
general increase in temperature (geothermal gradient), makes the marine limestones
or shell carbonates progressively lighter (increase in l 6 0 content). Thus, the original
1 8 0 / 1 6 0 record, as laid down during deposition, is diagenetically altered. The
6180 variation of a number of carbonates and coexisting cherts with geologic
age is presented in F i g 5 There are, however, certain diagenetic environments
known which apparently have preserved the original l 8 0 / 1 6 0 record even of late
Paleozoic carbonates. This can be inferred either from the presence of internal
isotope variations, the occurrence of metastable aragonite, or the perfect structural
preservation of the calcite material (STEHLI,1956; COMPSTON, 1960; H. A. Lowen-
stam and S . Epstein, personal communication, 1964).
Stable isotope investigations have also proven to be rather significant in
studies concerning the origin of sedimentary dolomites. The isotope data of
high-temperature mineral phases reported by CLAYTONand EPSTEIN(1958),
ENGELet al. (1958), and EPSTEINet al. (1964) suggest that dolomites, which
precipitated in an aqueous environment at room temperature, should be heavier
by about &lo%, in 6180 over cogenetic calcite or aragonite. In view of the con-
siderable isotope fractionation between calcite and dolomite, it might, therefore,
be expected that sedimentary dolomites and calcites which precipitated under the
same environmental conditions should be different in 6180 values by about 6-10 x0.
Isotope data of recent dolomite-calcite pairs from various localities, how-
ever, show no significant difference between calcite and dolomite (DEGENSand
EPSTEIN,1964; EPSTEIN et al., 1964). The lack of such a relationship in the investi-
gated sedimentary dolomite-calcite pairs and the consistent A-dolomite-calcite
values1 of about zero suggest that the dolomite did not precipitate from an
aqueous solution (Fig.6). Dolomite, even in recent samples, must have been
derived by way of metasomatism of calcite, and dolomitization must have pro-
ceeded without significantly altering the 1 8 0 / 1 6 0 record of the precursor carbonate.
Namely, the transformation of the original calcareous ooze must have taken
place without chemically affecting the CO32- unit. Consequently, it can be inferred
that the growth of dolomite did take place under solid state conditions from
crystalline calcium carbonate.

1 A-dolomitexalcite is the difference between P O of dolomite and 6 1 8 0 of calcite, and thus is

a measure of the magnitude of oxygen isotope fractionation between these two carbonate species.
STABLE ISOTOPE DISTRIBUTION IN CARBONATES 203

The same characteristics also hold true in the case of late diagenetic-
epigenetic dolomitization, which does not introduce a major isotope fractionation
between coexisting dolomites and calcites. Namely, the isotope ratio of the calcite
precursor is inherited by the dolomite without any changes. Thus, isotope data
suggest that all sedimentary dolomites, independent of age, environment, and
mode of formation (syngenetic, diagenetic, or epigenetic), are products of calcite
metasomatism. Aragonites, however, first have to become inverted to calcite,
before dolomitization may proceed.
In contrast to calcite and aragonite, dolomite does not easily adjust isotopi-
cally to changes in temperature, and l80/16O ratio of formation waters (EPSTEIN
et al., 1964). This makes penecontemporaneous dolomites of marine origin a
potential tool for the evaluation of paleotemperatures in the ancient sea. The
d l 8 0 and d13C relationships that are established between coexisting dolomites
and calcites of various origins are presented in Fig.7 and 8. The data illustrated
in Fig.7 indicate that dolomites are either about equal or heavier in cY80relative

OC

0 .='/
/

marine pairs

-201
early diagenetic
/
(penecontemporaneous
/+ A late diagenetic-epigenetic
/
te r r est r ia I pairs
recent and ancient early dlagenl
hydrothermal pairs
naturally occuring deposits
+ bomb experiments
-3OV I I I I I
-30 -25 -20 -15 -10 -5 0 t5
8 I8O calcite
Fig.7. The 6180 relationship between coexisting dolomites and calcites. Black line: A-dolomite-
calcite equals zero; dashed line: the dolomite-calcite relationship obtained by CLAYTON and
EPSTEIN, 1958 (the assumed equilibrium curve between dolomite and calcite and a large reservoir
of hydrothermal fluids). (After CLAYTON and EPSTEIN, 1958; DEGENS and EPSTEIN, 1964: and
EPSTEIN et al., 1964.)
204 E. T. DEGENS

recent, early diagenetic

ancient, early diagenetic
+ late diagenetic-epigenetic

terrestrial pairs
recent, early diagenetic
-4
ancient, early diagenetic

-% -4
I-
-3 -2 -1 0 +I +2
'
t3 +4 t6 t5
813c calcite
Fig.8. The 613Crelationshipbetween coexistingdolomites and calcites.Diagonal line: Sdolomite-
calcite equals zero. (After DEGENS
and EPSTEIN, 1964.)

to their coexisting calcites. That the majority of the calcites tend to approach the
assumed equilibrium curve constructed by CLAYTON and EPSTEIN(1958) can
probably be linked to the faster equilibration rate of calcite when compared to
that of dolomite.
Studies on high-temperature carbonates include those of BAERTSCHI ( 195l),
CLAYTON and EPSTEIN (1958), ENGEL et al. (1958), CLAYTON (1961), G. D. Garlick
(personal communication, 1964), O'NEILL and CLAYTON (1964), and TAYLOR et al.
(1964). Most crucial for any future work in the area of high-temperature carbonate
geochemistry appears to be the knowledge of the equilibrium constants for the
various carbonate-water systems. CLAYTON (1 96 I), for instance, has experimentally
determined the equilibrium constants for CaC03(,)-H20(1) at elevated temper-
atures. By including data of the paleotemperature scale of EPSTEIN et al. (1953),
an equilibrium curve over a temperature range of about 1,000"C can be construct-
ed. In Fig.9, In K is plotted versus the reciprocal of the square of the absolute
temperature. An empirical equation which fits the experimental data over the
0"-750" C range is as follows:
In K = 2,730 T-2 - 0.000256
In case the equilibrium constants in two or more cogenetic mineral systems
STABLE lSOTOPE DISTRIBUTION IN CARBONATES 205

temperature ("C)

1 I I I
0 2 4 6 8 I0 12
lo6/ T 2
Fig.9. Experimental equilibrium constants for CaC03(,,-H~0(~,. et al., 1953;
(After EPSTEIN
and CLAYTON, 1961.)

are sufficiently different, the 6 1 8 0 values of mineral pairs may allow, for instance,
the evaluation of the temperature of mineral formation and the determination
of the isotopic composition of the participating water phase. The usefulness of
this type of approach has been shown, for instance, by CLAYTON and EPSTEIN
(1958), ENGELet al. (1958), TAYLOR and EPSTEIN (1962), O'NEILL and CLAYTON
(1964), and others. Geologically potential mineral pairs include: ( I ) calcite-
apatite, (2) siderite-magnetite, (3) calcite-dolomite, and (4) calcite-quartz. In
case carbonate-containing magmatic and metamorphic rocks are studied (e.g.,
carbonatitesj, the various silicates coexisting with the carbonate can be used as
proper mineral partners (TAYLOR et al., 1964).

CALCIUM A N D MAGNESIUM ISOTOPES

Stable isotopes of calcium differ in mass by up to 20% (40Ca versus 48Ca). Inas-
much as this is the largest relative mass difference of all the elements except
hydrogen, a priori, studies on calcium isotopes appear promising.
Mass-spectrometrical studies by HIRTand EPSTEIN (1964), however, indicate .
that there is a lack of large calcium isotope variations in nature in contrast to
206 E. T. DEGENS

oxygen, carbon, nitrogen, and sulfur. Namely, samples of different origins, i.e.,
meteorites, crystalline rocks, limestones, shell materials, ocean waters, bones and
teeth, have about the same calcium isotope distribution. This may mean that
elements in natural products which are bonded by ionic bonds show small isotopic
variations when compared to those light elements that are bonded by covalent
bonds.
In the light of these results, a re-examination of magnesium isotopes would be
relevant, because DAUGHTRY et al. (1962) reported 5 % variation in the 24Mg/26Mg
ratios in dolomites. Similarly, the isotope data of CORLESS (1963) and CORLESS
et al. (1963) have to be re-evaluated in view of the results by HIRTand EPSTEIN
(1964).

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BAERTSCHI, P., 1953. Die Fraktionierung der natiirlichen Kohlenstoff-isotopen im Kohlendioxyd-
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BAERTSCHI, P. and SILVERMAN, S.R.,1951. The determination of relative abundances of the
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BOWEN,R.,1963. Oxygen isotope paleotemperature measurements on Mesozoic Belemnoidae
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CLAYTON, R.N., 196l.Oxygen-isotope fractionation between 180/1e0 ratios in calcium carbonate
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COMPSTON, W., 1960. The carbon isotopic compositions of certain marine invertebrates and
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CRAIG,H., 1954. Geochemical implications of the isotopic composition of carbon in ancient
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208 E. T. DEGENS

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Chapter 6

INFLUENCE O F PRESSURE AND TEMPERATURE ON LIMESTONES

BERNARD L. MAMET AND MICHELINE D'ALBISSIN

Fonds National de la Recherche Scientifque. Laboratoire de Gkologie, UniversitC Libre de Bruxelles,

Bruxelles (Belgium)
Centre National de la Recherche Scientifque, Laboratoire de Gkologie dynamique, Facultt des
Sciences, Paris (France)

SUMMARY

Some of the petrographic and physical characteristics of limestones which have

been exposed to increasing temperatures and pressures are reviewed in this chapter.
They are first considered under burial load on a moderate scale, with conditions
being of the order of magnitude of slightly deformed rocks usually encountered
in stable cratons or parageosynclines. Then, the behavior of the carbonate rocks
is examined under oriented stress at low temperature; such conditions are well
exemplified in alpine-type orogenies. Finally, contact and general metamorphism
are studied; they deal with pressures reaching 5,000 atm. and temperatures of
150-700"C.

SEDIMENTATION AND DIAGENETIC FABRICS

Before reviewing the influence of physical variables on limestones, it is important

to review a few basic facts concerning limestone formation, because calcite aggre-
gates display properties somewhat different from those of the ideal Iceland spar
crystal.1
Limestones are indurated or lithified rocks containing more than 50%
calcium carbonate. This induration suggests that the fabric of the assemblage
differs from the original fabric; lithification implies diagenesis (the different stages
through which aragonite and calcite muds reach equilibrium) but not necessarily
recrystallization.
It should be noted that petrographers and metallographers often use re-
crystallization in different senses. If the original dimensions of the crystals remain
unmodified and if no nucleation centers appear, one may hardly speak of recry-
1 Dolomites are not included in this chapter; although their behavior is rather similar to that of
limestones, quantitative data are still inadequate to reach definite conclusions. The influence of
small amounts of magnesium on calcite assemblages is considered whenever possible.
210 B. L. MAMET AND M. D’ALBISSIN

stallization but only of phase transformation. The term recrystallization should

really be reserved to designate obliteration of original fabric, through displace-
ment of grain boundaries. In such a case the pre-existing texture may still be
recognizable as “phantom” or “palimpsest”, or may be totally destroyed. The
newly formed assemblage has a lower free energy than the original one.
The original matrix in numerous limestones is made up of fine-grained
aragonite crystals of micron dimensions. It encloses discrete elements which can be
divided into three main groups: fossils, oolites and intraclasts.
Diagenesis usually converts the matrix to a stable aggregate. Depending
on pcoZ,nucleation, and accretion speed, a microcrystalline mud may remain of
the micron size and form an interlocking mosaic of crystals (micrite). In contrast,
recrystallization leads to much bigger crystals; it may occur simultaneously with
sedimentation (“alpha sparite” parrim) or at a later time (“gamma sparite”)
(MAMET,1961).
Another possibility is that the closely-packed discrete elements lack micrite
matrix at the time of deposition; however, they form a mechanically stable assem-
blage which may, or may not, be cemented by percolating solutions. The latter
product is referred to as void-filled sparite.
A first conclusion may be drawn from this brief outline: from purely chemi-
cal causes, without external pressure or temperature changes, limestones may vary
from those having homogeneous fabrics, with mosaic texture of the micron size
(e.g., “Marbre Noir”, MAMET,1964), to those with completely heterogeneous tex-
tures where grain-size differences may be of the order of 1-105.

INFLUENCE OF LOAD PRESSURE

Load pressure applied on a calcite assemblage increases its strength and stability1
(GOGUEL, 1943; HANDINand HAGER,1957-1958). The primary effects of deforma-
tion are compaction, pore reduction, and development of contact surfaces between
the grains. These grains become completely xenomorphic2 and the order of magni-
tude of their size differences decreases to an average of 1-103.
It is hard to find a direct and simple quantitative relationship between
petrography and burial depth, at such low pressures. The great heterogeneity of the
original material, inherited from sedimentation conditions, has already been stres-
sed. Moreover, minute differences in chemical composition lead to extremely var-
iable petrographic “landscapes” (i.e. microfacies). The presence of less than
2 % MgO in the latter is sufficient to induce extensive recrystallization. In contrast,
a small percentage of clay readily prevents such a modification. These chemical
and sedimentation characteristics often carry through the entire formation. Hence,

This pressure may be considered as hydrostatic.

Anhedral.
INFLUENCE OF PRESSURE AND TEMPERATURE ON LIMESTONES 21 1

by examining Lower Carboniferous carbonate sequences of northern France and

Belgium, the writers were able to recognize a number of persistent crystalline cal-
cite assemblages, which persisted almost independently of tectonic conditions;
these latter ranged from burial under about 1,OOO m of sediment to dynamic
modification under small load. However, for thrust faults under load, persistent
recrystallization patterns (e.g., recrystallization “fibrous sparite”) were detected.
Increasing pressure diminishes the depositional differences; unfortunately
petrographic recrystallization fabrics are of questionable value at the present time,
because there is considerable difference of opinion as to their quantitative signi-
ficance (BATHURST,1959; ORMEand BROWN,1963). Precise examination of micro-
fossil walls, however, may lead to a fair recrystallization appraisal; these walls
exhibit different calcite fabrics, the reactivity of which varies greatly in response to
external conditions. Moreover, through morphological and paleontological ex-
amination, one can determine exactly from which material the actual assemblage
is derived; and thus the approximate amount of recrystallization may be ascer-
tained. The writers have found, for instance, in European Carboniferous limestones:
(1) fine-grained, dense, “isotropic” micrite of the pre-Fusulinid wall type (Eos-
tafella); (2) micrite (Endothyra, Bradyana) or agglutinated calcite grains in such
material (Forschia);and (3) radially oriented clear microspar on a microcrystalline
basal layer (Archaediscus) (W.W. Brown, personal communication, 1964).
Careful investigation of such assemblages in similar petrographic environ-
ments reveals the same order of texture obliteration, the radially oriented micro-
spar being the last to recrystallize. By comparing the total assemblage of such
microfossils in similar facies (same magnesium and clay content, in the same mi-
crospar range) and eliminating the otherwise dominant sedimentation factor, one
may obtain a clue to the influence of increasing pressure.
The same line of thought may be applied to the study of other microfossil-
bearing sequences. Inasmuch as this type of investigation is long and painstaking
one may conclude that a method based on selective oxidation (TEICHMULLER et
al., 1960) of the ubiquitous kerogen may be a more convenient geological tool in
evaluating burial depth.

INFLUENCE OF STRESS

If pressure increases further, with dynamic modification, calcite crystals respond

to the stress by acquiring a preferred orientation (SANDER,1930; TURNER and WEISS,
1963).

Mechanism of the deformation

Plastic strain may be related to the concurrent effects of ( I ) intracrystalline gliding

212 B. L. MAMET AND M. D’ALBISSIN

by twinning or translation; (2) intercrystalline gliding along intergranular boun-

daries; and (3) recrystallization.

Intracrystalline gliding
Intracrystalline gliding occurs by a step-by-step process, which induces defects or
dislocations between the glided parts. Whereas creation of such defects in pure crys-
tals requires high energies, natural carbonate lattices show many defects which can
be displaced and grouped. This process, leading to a distortion of the lattice, raises
its potential energy.

Twin-gliding. Twin-gliding is the most obvious, but not necessarily the most ef-
ficient mechanism for orienting crystals (positive e gliding on 0112) (TURNER
and WEISS,1963). Twin-gliding results in petrographic modifications which can be
studied under the microscope; this induced early workers to attach paramount
importance to the mechanism.1 Further experiments, however, have shown that
translation gliding is as likely to induce permanent deformation.

Translation gliding on r (0111)2. Extensive gliding on r leaves no visible traces

except random orientation of twin lamellae, which usually does not survive minor
post-tectonic adjustments (TURNER and WEISS,1963).

In tercrystalline gliding
Experiments of ADAMSand NICHOLSON (1901) have shown that intercrystalline
gliding occurs during plastic deformation; it is an intergranular rupture followed
by immediate “healing”. Moreover, the contact of “mosaic calcite” crystals is
not planar, but is along an S dislocation family3. In spite of their small volume
(HABRAKEN and GREDAY,1956), boundaries act as barriers for dislocation pro-
pagation.

Recrystallization
Recrystallization occurs by (I) solution and precipitation linked to pressure, or (2)
formation of new crystal nuclei within the aggregate.

Solution and precipitation linked to pressure. The sometimes misquoted “Riecke’s

principle” effects are often observed by petrographers. The outlines of a crystal

1 The “mean spacing index” is the number of lamellae encountered per millimeter, in a direction
perpendicular to the lamellae plane. It can not be related to the effectiveness of the stress orien-
tation.
2 Another translation off1 has been described for artificially deformed limestones, but it would
be effective only in the deepest catazone.
Some authors ( L m m , 1957) have proposed the presence of a fluid phase between the mosaic
boundaries.
INFLUENCE OF PRESSURE AND TEMPERATURE ON LIMESTONES 213

surrounded by a saturated solution of its own composition change; under pressure,

strained faces are dissolved, whereas epitaxial growth occurs on the faces under
minimal stress.l There is, therefore, a competition among coexistent grains, and
the original orientation determines their increase or decrease in size.

Formation of new crystal nuclei within the aggregate. Syntectonic recrystallization

from a nucleus leads to more or less lenticular grains, with rather regular outlines
and no cataclastic effects. The order of magnitude of grain-size differences range
from 1-10 to 1-102. Few to no original micrite grains areencountered, but palimp-
sest textures are still conspicuous. Experimental data have shown that this recrys-
tallization can lead to the formation of rocks similar to natural “marbles” at
temperatures as low as 300°C (GRIGGS et al., 1960).
Post-tectonic recrystallization of calcite assemblages will first affect the
most deformed zones. Grains having many faces with concave boundaries show
a tendency to grow, while grains with few boundaries tend to disappear. The limits
of grains often coincide with lamellae or twin-glides, which have acted as barriers
during the process.

Conclusion on the mechanism of the deformation

Whatever the proposed mechanism, gliding or recrystallization, the result from
a geological point of view is quite similar; the optical axes of the reoriented
crystals are in a direction roughly parallel to the maximum stress and plastic
deformation increases the stored energy within the lattice.

Experimental analysis of the deformation

The oldest method for the evaluation of crystal orientation is that of the universal
stage developed by SCHMIDT (1925) and SANDER (1930). It has proved invaluable
in many cases of macrocrystalline aggregates. TURNERand WEISS(1963) have
shown, however, the difficulties of relating petrography to the probable stress
action. Moreover, petrographical approach is hard to apply to microspar, where
the grains have sizes comparable or inferior to the thickness of a thin-section.
Attempts have been made, therefore, to overcome the difficulties of Sander’s
method by investigation of other characteristics. linked to the anisotropy of cal-
cite rhombohedra. Such methods are either vectorial and deal with crystalline
orientation-(I) infra-red spectroscopy, (2) dilatometry and (3) X-ray diffraction
-or are linked to a direct evaluation of lattice disorder-(l) etching figures and
(5) thermoluminescence.

Poynting’s law has been proposed as appropriate here (BARTH,

1962); however, the thermody-
namic treatment is still inadequate (MACDONALD, 1960; KAMB,1959, 1961).
214 B. L. MAMET AND M. D’ALBISSIN

B
650 900 vcm-

Fig.1. Stress-oriented Guillestre marble. A. Gamier River, Guil Valley, near Guillestre, Hautes-
Alpes, France. B. South of La Chapelue, Hautes-Alpes, France.

Infra-red reflection spectroscopy

HAAS(1956) has shown that the reflection spectrum of the extraordinary p r a y at
875 cm-l varies in intensity according to its orientation with respect to the calcite
crystal. When the light is parallel to the optical axis, reflection is minimum;
whereas when the light is at 90°, reflection is maximum.
This method may be applied to calcitic aggregates, and differences in inten-
sities allow rapid determination of the mean orientation (D’ALBISSIN,1963).
Some results dealing with strongly oriented microcrystalline aggregates (obtained
in the “Zone BrianConnaise” of the Alps) are presented in Fig. 1.

Dilatometry
The linear thermal expansion coefficient is a property of the lattice (Mitscherlich)
and varies according to the orientation of the crystalline structure. The expansion
coefficient along the optical axis of calcite is 31.6 whereas that perpendicular
to the same axis is -4.2 *lo-6 (D’ALBISSIN et al., 1960). Dilatometers or micro-
strain gauges readily enable a quantitative measurement of the expansion ellipsoid
and, therefore, reconstruction of the deformation ellipsoid. The method is simple,
reproducible and most adequate for routine examination.

X-ray diflraction
As early as 1930, SANDER and SACHSshowed that the X-ray diffraction planes
were more important in some directions than in others for aggregates showing
preferred orientation. Whereas the Debye-Scherrer method was not accurate
enough for detection of such small variations, diffractometry is readily applicable
to the variations in intensities observed for a given reflection (HIGGSet al., 1960;
D’ALBISSIN and ROBERT,1962).
INFLUENCE OF PRESSURE AND TEMPERATURE ON LIMESTONES 215

Etching figures
If it is assumed that a direct relation exists between the number of dislocations and
the etching figures (FRIEDEL,1956; D'ALBISSIN,1963), their density per grain can
be related to intracrystalline gliding. Although the number of performed experi-
ments is insufficient to prove this, the limited results obtained are in agreement
with the proposed scheme. One finds an abnormally high number of corrosion
pits in highly laminated microspars (up to 13 patterns per square p as compared
to less than 0.01 per square ,n for Iceland spar crystals).

Thermoluminescence
The energy absorbed during dynamic metamorphism can be dissipated as heat,
it may be used to displace the dislocations, or it can be stored within the crystal
by distortion of its lattice. Furthermore, it may also be used for recrystallization or
solution. A very small amount is used by the electrons which are kept in an excited
state, in the highest parts of the forbidden band, through lattice defects.
By thermal stimulation, it is possible to liberate such captive electrons and
to drive them to a lower energy state with light emission. This phenomenon, called
thermoluminescence, is extremely sensitive to the lattice defects and may, therefore,
help in the evaluation of stress deformation by intracrystalline gliding. Experiments
have shown that thermoluminescence of limestones is restricted to threemain peaks,
viz., A peak-235-270 "C, B peak-280-330 "C, and C peak-350-380°C.
All undeformed rocks show obvious A and C peaks. Moderate artificial
pressure (ZELLER,1954; DEBENEDETTI, 1958) applied to carbonates increases the
C peak and decreases the A peak intensity. When pressure reaches 2,000 atm, a new
B peak appears (HANDIN et al., 1957). Thermoluminescence of field specimens has
shown reasonably good agreement with experimental data. For instance, the
patterns presented in Fig.2 are those of Upper Cretaceous sediments from the

zoo IOO LOO sm

Temperature

Fig.2. I. Undeformed Guillestre marble. 2. Laminated Guillestre marble. 3. Laminated and

recrystallized Guillestre marble.
216 B. L. MAMET AND M. D’ALBISSIN

“Sub-Brianconnais” of the Alps. Such curves have been observed in numerous

analogous tectonic zones (D’ALBISSIN, 1963) and one may infer that thermolumi-
nescence can be applied to stress evaluation.

Geological results

The writers have reviewed the different physical approaches which allow appraisal
of calcite orientation and hence may lead to estimation of stress pressures. The
objection of GOGUEL (1952), who felt that pre-tectonic petrofabrics could be super-
imposed by stress re-orientation, should be kept in mind, however. This approach
is theoretically exact; and investigations should be limited to former homogeneous
micrites as described in the introduction. In dynamic metamorphism, palimpsest
textures are readily distinguishable and such discrimination is feasible. But when
it is no longer possible to recognize the original nature of the rocks, Goguel’s
objection must be considered.
Stress action can be synthesized in the study of the Alpine orogenic belt.
Results are in close agreement with paleo-tectonic history of this chain (Fig.3).
Rocks subjected to a feeble load (Sub-Alpine) grade into rocks which have undergone
severe thrust action under loads of approximately 2,500 m (Sub-BrianGonnais).
In the latter case, the effects of regional metamorphism (epizone) are superimposed
on the effects of oriented stress pressure.
It is obvious that stress-oriented rocks grade into formations subjected to
contact or regional metamorphism, which also display preferred orientation of
various intensities. Lack of sufficient data concerning the environment of such
metamorphism makes difficult the appraisal of plastic deformation. Attention is,
therefore, directed to the formation of new mineral phases in the carbonate assem-
blages at higher temperatures.

CONTACT METAMORPHISM

Bowen’s progressive thermal decarbonatization series is widely used (STRUVE,

Dynamic metamorphism

?!
Sub-Brianconnais I Ultra-Brianconnais
Ultra-Hclv6tiC I
Fig.3. Degree of re-orientation of calcite with increasing dynamic metamorphism.
INFLUENCE OF PRESSURE AND TEMPERATURE ON LIMESTONES 217

1958; CALLEGARI, 1962), and can now be found in any textbook of metamorphic
petrography. Dolomite, quartz and water lead to the formation of talcl; talc and
calcite form tremolite; and the latter with dolomite yields forsterite. These are
followed by diopside, brucite, and wollastonite (DANIELSON, 1950; HARKER and
TUTTLE,1955, 1956). Higher members have been described by BOWEN(1940) and
TILLEY (1951) as shown in Table 1. Successive authigenic minerals occur at given
temperatures but an increase of as little as 200 bars in the COZpressure raises the
required temperatures by 2OO0C2.
Magnesium present in many natural limestones leads to the completion of
the series. Bowen’s stages can be observed, therefore, not only in dolomites, but
also in the great majority of carbonates. The first steps of Bowen’s series can
successfully be checked in contact metamorphism where the system can be regar-
ded as “open”. For higher temperatures, however, the monticellite-larnite series
can be contracted. BURNHAM (1959) has shown that spurrite may be derived directly
from calcite and silicate without passing through the “low-temperature” steps.
From a petrographic point of view, calcite twin gliding on e is conspicuous,
and the lamellae are often bent; undulatory extinction or crystal clouding is wide-
spread.

REGIONAL METAMORPHISM

The lower boundary of the regional metamorphism is difficult to draw,

because stress-oriented rocks grade into it with increasing temperature; however,
authigenesis of minerals such as chlorite, epidote or albite is considered as indica-
tion of greenschist facies or epizone according to other schools of thought.
The last remnants of original carbonate textures may extend rather deep
into regional metamorphism. Pentelikon marble’s Macroporella is one example
(MARINOS and PETRASCHEK, 1956). One should also note the exceptional and puz-
zling case of the Cretaceous “Marbres chloriteux” (RAGUIN,1925; ELLENBERGER,
1958), where limestones associated with glaucophane schists3 show such clear
palimpsest texture that specific determination of the enclosed microfossils is possi-
bie4.
Normally the last phantoms disappear in the epizone; lepidoblastic grains
are still encountered, whereas e twin glides are rarely distorted. In m&sozone,
the granoblastic texture is dominant and size variations of the order of 1-10 are

The presence of talc is often misleading because it is often derived through hydrothermal alter-
ation.
2 Theoretical calculations based on the Clapeyron formula (WEEKS, 1954; LAFFIITE,1957) differ
from experimentalcurves; the discrepancy is probably due to the slow equilibriumspeed.
Aragonite is the stable form of carbonate in glaucophanite schists facies (JAMIESON, 1953).
Another striking example of palimpsest texture is found in pneumatolysis. The case of the
datolite-bearing Lower Carboniferous limestones may be noted (PHEMISTER and MACGREGOR,
1942).
218 B. L. MAMET AND M. D’ALBISSIN

TABLE I

APPLICATION OF BOWEN’S SERIES TO OPEN AND CLOSED CARBONATE SYSTEMS

Contact metamorphism

open system mineral facies

(“C)

talc
tremolite 200 albite tremolite contact
epidote limestone
forsterite 250-(330)2 forsterite contact G E
limestone 2
* .Y
*
cdd
diopside 300 hornblende diopside contact T 8
hornfels limestone $ 8
pencatite-predazite
$5
brucite 315
wollastonite 450
pyroxene
hornfels wollastonite contact sg
limestone 58
~~

periclase 560 periclase tactite

monticellite 600-800 sanidinite monticellite. . . tactite
or xenolith
akermanite
ti1 leyite
spurrite
hankinite
merwinite
larnite

1 Italian term for regionally metamorphosed limestones.

2 Calculated value.

normal. Mortar texture (GRUBENMAN, 1910) and wandering or undulatory ex-

tinctions are conspicuous. Cataclasis occurs, while distorted e lamellae are devel-
oped.
Granoblastic textures are encountered in the deepest part of the almandine-
amphibole facies and probably in granulite facies. Characteristics of such “cata-
marbles” are poorly known. Some have been confused with carbonatites (Kaiser-
stuhl), and the confusion is still to be found in the literature.
It is often said that metamorphic limestones react quite differently from the
surrounding silicate-bearing rocks (“selective metamorphism”). Whereas this is
probably true for extensive metasomatism, careful review of literature shows that
this is not so for regional metamorphism. Pure calcium carbonate is indeed one of
the minerals most stable with respect to pressure and temperature modifications,
but rocks are never devoid of impurities. As little as 1 % of such impurities gives
rise to a mineral facies similar in all respects to that of the surrounding silicate
INFLUENCE OF PRESSURE AND TEMPERATURE ON LIMESTONES 219

Regional metamorphism

closed system (“C) mineral facies

200 1,000 2,000
atm. atm. arm.

“epi-marble” epi
greenschists
cipolinl
tremolite cipolin 500 almandine
or “marble”
forsterite cipolin 550
or “marble”
diopside cipolin 620
or “marble”
scapolite 700
“cata-marble”?

rocks. Should this have not been the case, the whole concept of metamorphic
facies would have required revision.
Bowen’s decarbonatization series is of little use in regional metamorphism,
because one is rarely certain of the validity of the “closed system” assumption.
Formation of tremolite in such a “closed system” with a burial depth of as little
as 2,000 m requires mesozone conditions, and for deeper burial postulates catazone
environment. If Bowen’s series is of little value in the case of slight metamorphism,
it is still a good indicator of the temperatures occurring in the most severe conditions,
The most advanced mineral of the series encountered with certitude is diopside, and
one may, therefore, reasonably assume a maximum temperature of 600-700 “C for
the deepest-seated regional metamorphism affecting carbonates.
Oriented stress in regional metamorphism is hard to decipher. Limestones
of epi- and mesozone show quite variable preferential orientation ranging from
fully oriented to nearly isotropic fabrics. Moreover, dislocations are still abundant.
220 B. L. MAMET AND M. D'ALBISSIN

CONCLUSIONS

Influences of pressure and temperature are hard to estimate because they may have
affected rocks at different intervals; each time, they modified the crystal size and
shape, preferred orientation, intensity of dislocation, and hence, the mechanical
properties of the aggregate. Moreover, these stages may be obscured by post-
tectonic recrystallization. Recent developments, however, have indicated a series
of different approaches which allow a valid appraisal of the geological history of
the carbonates.

ACKNOWLEDGEMENTS

The authors are indebted to Prof. J. Michot for careful review and constructive
criticism of the manuscript.

REFERENCES~

ADAMS,E. and NICHOLSON, J., 1901. An experimental investigation into the flow of marble.
Phil. Trans. Roy. SOC.London, Ser. A, 195.
BARTH,T., 1962. Theoretical Petrology. Wiley, New York, N.Y., 416 pp.
BATHURST, R., 1959. Diagenesis in Mississippian calcilutites and pseudobreccias. J. Sediment.
Petrol., 29: 365-376.
BOWEN,N., 1940. Progressive metamorphism of siliceous limestones and dolomites. J. Geof.,
48: 225-275.
BURNHAM, C., 1959. Contact metamorphism of magnesian limestones at Crestmore, California.
Bull. Ceol, SOC. Am., 70: 879-920.
CALLEGARI, E.. 1962-1963. La Cima Uzza. Consiglio Nazionale delle Ricerce, Centro per le studio
delle Alpi, Padova, I : 116 pp.; 2: 127 pp.
CORDIER,P., 1868. Description des Roches Constituant I'l?corce Terreslre. Dunod, Paris, 553 pp.
D'ALBISSIN,M., 1963. Les traces de la dtformation dans les roches calcaires. Rev. Giograph.
Phys. Giol. Dyn. Sir. 2, 5 : 1-174.
D'ALBISSIN,M. et DE RANGO,C., 1962. etude de la microstructure des roches calcaires par
I'observation au microscope klectronique. Bull. SOC.Franc. MinPral. Crist., 85: 170-1 76.
D'ALBISSIN,M. et ROBERT,M., 1962. Apprkiation du degre de deformation naturelle au moyen
d'un diffractometre. Compt. Rend., 254: 1123-1 125.
DALBISSIN, M., FORNACA-RINALDI, G. et TONGIORGI, E., 1962. Modifications apportks aux
courbes de thermoluminescence des roches calcaires par une pression orogknique. Compt.
Rend., 254: 2804-2806.
D'ALBISSIN,M., SAPLEVITCH, A. et SAUCIER, H., 1960. etude par la mkthode dilatomktrique de
la dkformation des roches calcaires. Compt. Rend., 251: 2995-2997.
DANIELSON, A., 1950. Das Calcit-Wollastonitgleichgewkht.Geochim. Cosmochim. Acta, 1 : 55.
DEBENEDETTI, A., 1958. O r mechanical activation of thermoluminescence in calcite. Nuovo
Cimento, 7: 251-254.
ELLENBERGER, F., 1958. etude geologique du pays de la Vanoise. Mim. Carte Giol.France, 1958:
561 pp.
FRIEDEL,J., 1956. Dtformation plastique et dislocations. Cahier Groupe Franc. dudes Rhiof.,
3: 17-22.

1 For Russian publications see SMOLIN

(1959).
INFLUENCE OF PRESSURE AND TEMPERATURE ON LIMESTONES 22 1

GOGUEL, J., 1953. Importance des facteurs physico-chimiques dans la deformation des roches.
Congr. Gdol. Intern.,Compt. Rend.,l9e., Algiers, 1952, 3: 133-142.
GRIGGS,D., TURNER, F. and HEARD, H., 1960. Deformation of rocks at 5W800”C. Geol. SOC.
Am., Mem., 79: 39-104.
GRUBENMAN, U., 1910. Die Kristallinen Schiefer. Borntraeger, Berlin, 298 pp.
HAAS,C., 1956. Vibration Spectra of Crystals. Thesis Univ. of Amsterdam, Amsterdam. Un-
published.
HABRAKEN, L. and GREDAY, T., 1956. Sur les modes de deformation dans les metaux. Rev.
Universelle Mines, 12: 38-55; 209-227.
HANDIN, J., HIGGS,D., LEWIS.D. and WEYL,P., 1957. Effects of gamma radiation on the expe-
rimental deformation of calcite and certain rocks. Bull. Geol. SOC.Am., 88: 1203-1224.
HANDIN, J. and HAGER,R., 1957-1958. Experimental deformation of sedimentary rocks under
confining pressure. Bull. Ceol. SOC.Am., 41: 1-50; 42: 2897-2934.
HARKER, A., 1952. Metamorphism. Methuen, London, 380 pp.
HARKER, R. and TUITLE,O., 1955. Studies in the system CaO-MgO-Cot. Am. J . Sci., 25:3
209, 274.
HARKER, R. and TUI-TLE,O., 1956. Experimental data on the p C 0 ~ - Tcurve for the reaction
calcite+quartz. Am. J . Sci., 254: 239.
HIGGS,D., FRIEDMAN, M. and GEBHART, J., 1960. Petrographic analysis by means of X-ray
diffractometer. Geol. Soc. Am., Mem., 79: 275-292.
HOLMES, A., 1920. The Nomenclature of Petrology. Murby, London, 284 pp.
JAMIESON, J., 1953. Phase equilibrium in the system calcite-aragonite. J. Chem. Phys., 21:
1385.
JUNG,J., 1958. Prdcis de PPtrographie. Masson, Paris. 314 pp.
KAMB,W., 1959. Theory of preferred crystal orientation developed by crystallization under stress.
J. Geol., 67: 153-170.
KAME,W., 1961. The thermodynamic theory of non-hydrostatically stressed solids. J . Geophys
Res., 66: 259-271.
LAPFITTE, P., 1957. Introduction a I’gtude des Roches mdtamorphiques et des Gites mdtallifPres.
Masson, Paris, 358 pp.
LUCAS,G., 1955. Caracteres petrographiques des calcaires noduleux, A facies ammonitico rosso
de la region mediterraneenne. Compt. Rend., 240: 1909.
MACDONALD, G., 1960. Orientation of anisotropic minerals in a stress field. Geol. SOC.Am., Mem.,
79: 1-18.
MAMET,B., 1961. Reflexions sur la classification des calcaires. Bull. SOC.Belge Gdol. Palkontof.,
Hydrol., 70: 48-64.
MAMET, B., 1964. Skdimentologie des facies “marbres noirs” du Paleozolque franco-belge. Mdm.
Inst. Roy. Sci. Natl. Belg., 151: 131 pp.
MARINOS, G. and PETRASCHEK, W., 1956. Laurium. 4. Geological and Geophysical Research
Institute, Athens, 246 pp.
MICHEL,R., 1953. Les schistes cristallins du Massif du Grand Paradis et de Sesia-Lanzo. Sci.
Terre, I : 1-287.
ORME,G. and BROWN,W., 1963. Diagenetic fabrics in the Avonian limestones of Derbyshire and
North Wales. Proc. Yorkshire Geol. Soc., 34: 51-66.
PHEMISTER, J. and MACGREGOR, A., 1942. Note on a datolite and other minerals in a contact
altered limestone at Chappel Quarry. Mineral Mag., 26: 275-282.
RAGUIN, E., 1925. Decouverte d’une faune de foraminifkres dans les calcaires hautement meta-
morphises du Vallon de Paquiers, pres de la Grande Motte. Compt. Rend., 181: 726-728.
SANDER, B., 1930. Gefugekunde der Gesteine. Springer, Berlin, 352 pp.
SANDER, B. and SACHS,G., 1930. Zur rontgenoptischen Gefugeanalyse von Gesteine. Z. Krist.
Mineral. Petrog., Abt. A., Z . Krist., 75: 550-571.
SCHMIDT, W., 1925. Gefugestatistik. Mineral. Petrog. Mitt., 38: 392-423.
SMOLIN,P. P., 1959. Principes d’une classification ration+e des roches carbonatks metamor-
phiques. Izv. Akad. Nauk S.S.S.R., Ser. Geol., 12: 14 pp.
STRUVE,S., 1958. Data on the mineralogy and petrology of the dolomite-bearing northern
contact zone of the Qukrigut granite. Leidse Geol. Mededel., 22: 235-349.
222 B. L. MAMET AND M. D’ALBISSIN

TEICHMULLER, M., KALIFEH, Y. and Lows, M., 1960. Transformation de la matiere organique.
Rev. Inst. Franc. Pitrole Ann. Combust. Liquides, 15: 1567.
TILLEY,
C., 1951. A note on the progressive metamorphism of siliceous limestones and dolomites.
Geol. Mag., 38: 175-178.
TURNER,F. and VERHCKIGEN, J., 1962. Igneous and Metamorphic Petrology. McGraw-Hill, New
York, N.Y., 694 pp.
TURNER,F. and WENS,L., 1963. Structural Analysis of Metamorphic Tectonites. McGraw-Hill,
New York, N.Y., 545 pp.
WEEKS,W., 1954. Equilibria relations during thermal metamorphism of carbonate rocks. Am.
Mineralogist, 39: 349.
E., 1954. Thermoluminescence of carbonate sediments. In: H. FAUL
ZELLER, (Editor), Nuclear
Geology. Wiley, New York, N.Y., pp.180-188.

APPENDIX ON NOMENCLATURE

Although the writers are fully aware of the inadequacies of taxonomic treatments
in petrography, they feel that it is not inappropriate to recommend care in the
use of the word “marble”. Not only does the word have different meanings for the
layman, the field geologist, and the petrographer, but these meanings also widely
differ from one country to another.
Most European geologists accept the Harker’s definition of marble as “crys-
talline limestone”, independently of whether it is of sedimentary or metamorphic
origin; this definition was used as early as the 18th century. Moreover, “marble”
is often used as a formation name for sedimentary carbonate rocks (e.g., “Marbre
Noir” of Dinant, MAMET,1964; “Marbre de Guillestre”, LUCAS,1955).
The above usage has also prevailed in the United States; but one generation
ago, petrographers began to restrict its meaning. According to TURNERand
VERHOOGEN (1962) “marbles are metamorphic rocks composed principally of
calcite and dolomite”. This definition is also found in some recent European text-
books (JUNG,1958).
Replacement of “marble” by a more precise petrographic term is somewhat
difficult and is not really desirable. The literature abounds in obsolete forms
which should remain in obscurity, even if some of them are rather self-explanatory.1
The authors feel that the term “metamorphic limestone” used by most English
petrographers is by no means lengthy and leads to no confusion. If, however,
the petrographic use of “marble” is to be applied to metamorphosed carbonates,
composite descriptive names are recommended (HOLMES,1920), e.g., epi-, meso-,
or cata-marble (GRUBENMAN, 19lo); or forsterite-marble, diopside-marble, etc.
The use of “cipolin”2 for muscovite to diopside limestones formed by regional

1 Thermocalcite for contact metamorphic limestones (CORDIER, 1868); or calciphyre for ‘crystalline
limestones containing conspicuous calc-silicate minerals such as forsterite, pyroxene and garnet’
(Brongniart in HOLMES, 1920).
a A crystalline limestone rich in silicate minerals and characterized by micaceous layers; ser-
pentinization of the forsterite leads to ophicalcite.
INFLUENCE OF PRESSURE AND TEMPERATURE ON LIMESTONES 223

metamorphism might also partiaIIy meet our needs; it is, however, rarely if ever
used in American literature.
Chapter 7

THE ORIGIN OF PETROLEUM I N CARBONATE R O C K S

JOHN. M. HUNT

Department of Chemistry and Geology, Woods Hole Oceanographic Institution, Woods Hole,
Mass. (US. A.)

SUMMARY

The hydrocarbons in petroleum appear to owe their origin to different sources and
mechanisms. The light hydrocarbons and gases generally containing less than nine
carbon atoms are formed in sediments over geologic time from the decomposition
of heavier organic materials. The heavier hydrocarbons are synthesized by living
organisms and are formed in the sediments. Formation of hydrocarbons
appears to continue until the sediments are so metamorphosed that only methane is
obtained. Carbonate sediments appear to be as effective source beds as clay sedi-
ments although there are differences in the time and conditions of generation,
migration, and accumulation of oil. As a result of early lithification of carbonates,
hydrocarbons tend to be retained until migration paths are developed through frac-
tures, fissures, and solution channels. The close juxtaposition of source and reservoir
beds in carbonates plus the frequent presence of impermeable evaporite caprocks
results in a more efficient process of oil accumulation in carbonates than in sand-
shale sequences.
Carbonates, however, have very little catalytic activity compared to clays
and they do not continue to expel fluids to reservoirs over long geologic periods as
do the clays. The fact that 40 % of the petroleum in major oil fields is in carbonate
reservoirs, many of which are completely surrounded by carbonate rocks, indicates
that carbonates can be oil source beds.

INTRODUCTION

It has frequently been assumed that petroleum does not originate in carbonate
rocks. Present day concepts on the origin and migration of oil, however, do not
preclude the possibility of carbonates being source rocks. One of the more impor-
tant findings of the past decade is that finely disseminated petroleum constituents
are indigenous to nearly all types of sedimentary rocks: VASSOEVICH (1955),

Woods Hole Oceanographic Institution Contribution No.1577.

226 J. M. HUNT

HUNTand JAMIESON (1956) and PHILIPPI (1956). This was predicted some years ago
by PRATT (1942), who stated: “Petroleum is an inevitable result of fundamental
earth processes, so typical that they have been repeated in each successive cycle
of earth history. It is a normal constituent of unmetamorphosed rocks of near-
shore origin.”
There are certain basic differences in the source and types of organic matter
deposited with carbonates as compared to shales. Also, the early lithification of
carbonate rocks as compared to the slow compaction of shales would infer differ-
ent conditions of migration. These factors might alter the composition of oil and
its time of migration, but they would not prevent it. The wide range of environments
of deposition of carbonate rocks would allow adequate quantities of organic matter
to be retained for the generation of oil. Many studies of both Recent and ancient
fine-grained carbonates have shown them to contain hydrocarbons in amounts
comparable to clay sediments.
Approximately 40% of the estimated 217 billion barrels of oil from major
fields outside the Soviet Union and related Socialist republics are in carbonate
reservoirs (KNEBEL and RODRIGUEZ-ERASO, 1956). In view of the fact that some of
these reservoirs are completely surrounded by carbonate rocks, one must assume
that carbonates can generate petroleum.

ORIGIN OF PETROLEUM

Petroleum is a complex mixture of hydrocarbons with molecular size ranges

from 1 to over 40 carbon atoms, the predominant molecular types being paraf-
fins, naphthenes (cycloparaffins), and aromatics. In addition, petroleum contains
small amounts of oxygen, nitrogen and sulfur compounds called asphaltics plus
traces of metallic salts. Table I shows the composition of what might be regarded
a typical crude oil, although it should be emphasized that crude oils vary tremen-
dously in composition. Some oils show large variations in composition within the
same reservoir.
Nearly all petroleum is believed to have an organic source, that is, it was
formed from organic matter that was once part of a living organism. The different
fractions of petroleum, however, may have been formed by different processes.
As postulated by HUNTand JAMIESON (1956), the origin of petroleum appears to
be a dual process: part of the oil originally being deposited with’ the sediments as
a product of living organisms, and part being formed in the sediments after burial
from the reduction of non-hydrocarbon organic material.

Hydrocarbons.from living organisms

Many hydrocarbons and related organic structures have been identified in both
THE ORIGIN OF PETROLEUM IN CARBONATE ROCKS 227

TABLE I

COMPOSITION OF A TYPICAL CRUDE OIL

Fraction (molecular size)

gasoline (C4x10) 31
kerosene (C11-C12) 10
gas oil (Cls-Czo) 15
lubricating oil ( c 2 1 - c 4 0 ) 20
residuum (> c40) 24
100
Molecular type
parafins 30
naphthenes 49
aromatics 15
asphaltics - 6
100

living things and petroleum. These substances have also been found in Recent
and ancient sediments, suggesting that they find their way into petroleum purely
by an accumulation process with only minor changes in chemical composition. The
first structures from living things identified in crude oils were porphyrin derivatives
of chlorophyll and hemin, which are the green plant and animal blood pigments,
respectively. These were found by TREIBS in 1934. He found the chlorophyll-derived
porphyrins to be about 20 times more numerous than those from the hemins. This
suggestedthat crude oil originated primarily from plant life. Later, OAKWOOD et al.
(1952) concentrated the optically active fraction of crude oils and found it to be a
crystalline hydrocarbon with several naphthene rings. Optically active compounds
have never been formed except by living things. This was an added evidence that
a life process was involved. More recently, BENDORAITIS et al. (1963) isolated
from petroleum a whole series of isoprenoid hydrocarbons, and MAIRand MAR-
TINEZ-PICO (1962) isolated a hydrocarbon with the steroid nucleus. Both the iso-
prenoid and steroid structure are common in living things.
The presence of hydrocarbons in living things has been known for some time.
CHIBNALL and PIPER(1934) made the most detailed studies of paraffin hydrocar-
bons in insects and plant waxes. They were the first to discover a predominance of
alkanes with odd carbon number chain lengths in the c 2 5 - c 3 7 range. WHITMORE
(1945) postulated from his studies of the hydrocarbons in kelp that the quantities
of hydrocarbons formed by life processes were sufficient to account for all the pe-
troleum in the world. More recently, GERARDE and GERARDE (1961) published
a detailed summary of all the hydrocarbons known to be in living organisms.
Among the paraffin hydrocarbons, methane is the most common and is produced
228 J. M. HUNT

primarily in marshes where bacteria are metabolizing organic matter. No hydro-

carbons from ethane through octane (CZ-CS)are known to be formed biologically,
except possibly heptane. Paraffin hydrocarbons containing nine or more carbon
atoms, particularly the waxes in the molecular weight range c23-c37, are quite
common in nature.
Naphthenes with less than ten carbon atoms do not occur in living organisms.
Most of the cycloparaffins occur as unsaturated terpenes ( C ~ Hl6).
O
The naturally occurring aromatic hydrocarbons start with ten carbon atoms
and go up into the higher molecular weight ranges. The most common is para-
cymene which is widely distributed in spices. The presence of high molecular weight
hydrocarbons in marine organisms has been studied by BERGMANN (1 949, 1963),
who first observed that the unsaponifiable fraction of invertebrate lipids was higher
in the more primitive animal forms. This suggested that waxes, sterols, and hy-
drocarbons are most prominent in the lowest and most primitive forms of life.
BLUMER et al. (1964), BLUMER and THOMAS (1964), and BLUMER and OMAN(1965)
have isolated pristane and a whole series of hydrocarbons related to phytol from
marine zooplankton.
The first isolation of liquid hydrocarbons from Recent sediments was by
SMITH(1954) who found a series of paraffin, naphthene, and aromatic hydrocar-
bons heavier than c14 in Gulf Coast muds. He was able to date them by radio-
carbon methods at about 10,000 years. A more detailed study by MEINSCHEIN
(1961) showed a large number of hydrocarbons having more than 14 carbon
atoms to be present in Recent sediments.
It should be emphasized that the hydrocarbons identified by the aforemen-
tioned workers in living things and in Recent sediments represent only a very
small fraction of petroleum in the higher molecular weight range (above c14).
SOKOLOV (1957) and VEBERand TURKELTAUB (1958) stated that their studies of
hydrocarbons from the sediments of the Caspian Sea and Black Sea, which are
rich in organic matter, showed no hydrocarbons in the CZ-c14 range. They
pointed out that the hydrocarbons in Recent sediments cannot represent petroleum
because the missing fractions up to c14 constitute up to 50% or more of many
crude oils. EMERY and HOGGAN (€958) had previously reported finding a total of
less than 1 p.p.m. of these hydrocarbons in sediments of the basins off the Califor-
nia coast. J. G. Erdman (personal communication, 1962) found only methane
and heptane in the Cl-C, range of Recent sediments, whereas in ancient sediments
he found all the saturated hydrocarbons including pentanes: hexanes, heptanes,
etc. ERDMAN et al. (1958) had previously reported that the low molecular weight
aromatic hydrocarbons, benzene and the xylenes, also are absent from Recent
sediments. DUNTONand HUNT(1962) found the C4-cS hydrocarbons to be absent
from 21 Recent sediment samples from Venezuela, Texas, Cuba, California, and
Norway. Twenty-nine ancient sediment samples ranging in age from Precambrian
to Miocene, however, yielded c 4 - c S hydrocarbons in amounts ranging from 1 to
THE ORIGIN OF PETROLEUM IN CARBONATE ROCKS 229

over 800 p.p.m. These studies show that hydrocarbons lighter than nonane (Cg)
are generally absent in Recent sediments.
It has also been found that there are fewer heavy hydrocarbons in Recent
sediments than in ancient sediments. HUNT(1961) analyzed 55 Recent sediment
samples from six different areas and found only one of them to contain as many
hydrocarbons above C14 as the average of 1,000 ancient sediments. Most of the
Recent sediments contain only about 1/5 as many hydrocarbons as the ancient
sediments.
In summary, it appears likely that some of the hydrocarbons in the high
molecular weight range of petroleum are synthesized by living organisms and even-
tually become crude-oil accumulations with only minor changes. All paraffin,
naphthene and aromatic hydrocarbons containing less than nine carbon atoms
(except methane and heptane), however, are not synthesized by living organisms,
and are not found in Recent sediments. Consequently, these must be generated in
the sediments. Also, the fact that Recent sediments contain fewer hydrocarbons
above Cg than ancient sediments suggests that part of the whole molecular weight
range of hydrocarbons is formed from organic matter in the sediments.

Generation of hydrocarbons from organic matter

The basic substances of plant and animal material are the proteins, carbohydrates,
and lipids. Higher plants also contain lignin, a high molecular weight aromatic
compound. Lignin comprises about 15-20 % of the total terrestrial plant substance
on a dry weight basis and would be the major contributor of aromatic structures
to petroleum. The proteins, which are the chief source of nitrogen in organic
sediments, are complex polymers of amino acids, Cellulose, the most important
carbohydrate, is a fundamental constituent of cell walls. Lipid is a general term
which includes waxes, fats, essential oils and pigments. Many of the pigments
are pure hydrocarbons and can be incorporated in crude oils with only minor
chemical changes. SILVERMAN (1962) pointed out that the 13C/12C isotope ratios
of petroleum and various organic materials point to the lipids as the primary
source of petroleum. In chemical composition the lipids are closest to petroleum
as can be seen from Table 11. Any of these constituents may be potential sources
of hydrocarbons until proven otherwise.
Bacteria, which are common in the first few feet of most sediments, bring
about the initial decomposition 6f organic matter. From 10-50% of the organic
matter is converted into bacterial cell material. Under aerobic conditions the free
products are water, carbon dioxide, and sulfate, phosphate and ammonium ions.
Products formed are similar under anaerobic conditions except that sulfur is
eliminated as hydrogen sulfide and methane and hydrogen are formed (ZOBELL,
1959). One significant difference between carbonate and clay sediments concerns
the depth at which bacterial activity may occur. LINDBLOOM and LUPTON(1961)
230 J. M. HUNT

TABLE I1
AVERAGE CHEMICAL COMPOSITION OF NATURAL SUBSTANCES

Elemental composition in weight %

C H S N 0

carbohydrates 44 6 50
lignin 63 5 0.1 0.3 31
proteins 53 7 2 16 22
lipids 80 10 10
petroleum 82-87 12-15 0.1-5 0.1-0.5 0.1-2

found that bacteria living on the organic matter in carbonate muds from Florida
and Cuba practically died out within the first five feet of sediments. Clay muds
from areas such as the Orinoco Delta and the Gulf of California, however, con-
tained active bacteria at much greater depths. In the former case viable bacteria
were found to a depth of about 150 ft. Lindbloom and Lupton suggested that the
extreme reducing conditions and the high H2S content associated with carbonate
muds such as those from Florida Bay may limit bacterial growth. The average
Eh of eleven shallow cores from carbonate muds of Florida Bay and the Gulf of
Batabano was -200 mV, whereas some Orinoco Delta clay sediment had a positive
Eh even at great depth. The iron associated with clay sediments utilizes H2S to
form sulfides, but in pure carbonates relatively free of iron, there is a build-up in
H2S content which remains in the sediments even at great depths. This H2S has
been found in ancient carbonates which may have little or no organic matter. It
may also be a factor in the high suifur content of many oils associated with carbo-
nates. KREJCI-GRAF (1963) stated that the commonly asphaltic nature and high
sulfur content (several percent) of oils ,associated with calcareous rocks implies
a different mode of origin than that of low (usually under 1 %) sulfur oils from
clay sediments. As the organic matter is buried deeper in sediments, the bacterial
activity becomes less important and the conversion of organic matter to hydro-
carbons proceeds through thermal or catalytic degradation. Catalytic activity
requires intimate contact between the organic matter and the mineral surface.
Here there appears to be significant differences between carbonate and clay muds.
GORSKAYA (1950) noted that as the particle size of Recent clastic sediments de-
creased, the percent of organic carbon, the total bitumens and the hydrocarbons all
increased (Table III).
In a study of the Viking Shale, HUNT(1962) found a three-fold increase in the
organic content in going from siltstone to clays having particles less then 2 p in
diameter as shown in Table IV. The organic matter in clays, associated with
the finest particle size, is, therefore, in intimate contact with the mineral surfaces.
THE ORIGIN OF PETROLEUM IN CARBONATE ROCKS 23 1

TABLE I11

ORGANIC MA'ITER OF RECENT CLASTIC SEDIMENTS

(After GORSKAYA,
1 950)

Sediment organic matter Weight % in organic matter

(weight %) total bitumens' hydrocarbons

sands 0.77 1.5 0.043

silts 1.15 2.1 0.096
clay muds 1.80 2.8 0.141

1 Organic matter soluble in organic solvents.

On the other hand GEHMAN (1962), in a study of 346 ancient limestone

samples, found the carbonate muds to contain 0.18 % organic matter compared
to 0.23 % for skeletal grains and 0.10 % for non-skeletal grains. Gehman also found
that the organic compound, quinoline, in aqueous concentrations up to 200 p.p.m.
was readily adsorbed by the three principal clay minerals, namely, kaolinite, illite,
and montmorillonite; whereas no adsorption occurred with lime-mud. Clays have
been known for decades to be excellent catalysts in causing rearrangements of car-
bon groups in organic compounds. FROST(1945) was able to convert alcohols,
ketones, and other non-hydrocarbon compounds to hydrocarbons at relatively low
temperatures, such as 150-180 "C,in the presence of clays. He found that the mont-
morillonite- and illite-type clays were quite active, whereas the kaolinites were
relatively inactive. More recently, WEISS(1963) reported the formation of cyclic
and aromatic hydrocarbons from heating organic complexes of montmorillonites.
A particularly interesting study is that of JURG and EISMA (1964), who found that
heating behenic acid (C21H4sCOOH) at 200°C in the presence of bentonite with
or without water yielded a series of paraffin and olefin hydrocarbons. It is signi-
ficant that hydrocarbons were obtained in the presence of water, which would be

TABLE IV

VARIATION IN ORGANIC CONTENT WITH PARTICLE-SIZE IN VIKING SHALE

(After HUNT,1962)

Particle size Organic matter

(average weight %)
232 J. M. HUNT

the natural state for oil generation. No hydrocarbons were obtained by heating
without the clay. Although more studies of this type are needed, particularly with
carbonate muds, it does appear that the clay shales have a distinct advantage over
carbonates in generating hydrocarbons by catalytic processes.
There is still the possibility for the catalytic generation of hydrocarbons be-
cause the small amount of clays is dispersed in many carbonate rocks. USPENSKIY et al.
(1949) noted that the organic carbon in carbonate rocks is primarily associated with
the clay minerals frequently present in such rocks. The author treated a sample of
mud from Florida Bay with dilute hydrochloric acid to isolate the non-carbonate
fraction. The latter was then analyzed for organic matter content and compared
with the original mud. One sample containing about 15% of clay minerals was
found to have 75 % of its organic matter attached to the small clay fraction and only
25 % to the large carbonate fraction.
USPENSKIY and CHERNYSHEVA (1 95 1) noted a very clear relationship between
the insoluble residue, presumably clays, in carbonate'rocks and the organic matter
as shown in Table V. The total organic matter and the bitumen content, which in-
cludes hydrocarbons, increased with increasing insoluble residue content.
In pure carbonates, where no clays are present, the possibility of catalytic for-
mation of hydrocarbons is remote. The conversion of organic matter to hydro-
carbons in pure carbonates is a thermal process. This suggests that somewhat
greater depths of burial and longer periods of time are required to generate oil
in carbonates than in clays. Consequently, carbonate source beds might not yield
oil to reservoirs as early in the history of a sedimentary basin as would the clays.

TABLE V

RELATIONSHIP BETWEEN ORGANIC MATTER AND INSOLUBLE RESIDUE OF CARBONATE ROCKS

(After USPENSKIY
and CHERNHYSHEVA,
1951)

Insoluble residue Organic matter Bitumen'

(weight %) (weight %) (weight %)

4.3 0.06 0.015

10.2 0.15 0.021
15.5 0.28 0.034
24.5 0.49 0.034
57.9 0.70 0.046
66.1 0.93 0.05 1
72.8 2.36 0.052

1 Organic matter soluble in organic solvents. It contains the hydrocarbons.

THE ORIGIN OF PETROLEUM IN CARBONATE ROCKS 233

MIGRATION OF PETROLEUM

The primary migration of petroleum involves the movement of oil and gas from
the dense, low permeability source sediment into the porous, permeable reservoir
rock. Secondary migration is concerned with the movement of petroleum within
the reservoir rock. In considering carbonates as possible source rocks, it is impor-
tant to compare the processes of primary migration as they might occur in car-
bonates and clays. The most plausible hypothesis is that as the sediments are
deposited, the more deeply buried sediments lose their interstitial water under
the forces of overburden pressure and compaction. WEEKS(1961) has estimated
that from 15-20 billion barrels of fluid is expelled from each cubic mile of mud
during compaction of a sedimentary basin. As the fluid passes out of the consoli-
dating sediment it carries with it minute quantities of oil. On entering a porous re-
servoir rock, the physical and chemical conditions are believed to change suffi-
ciently to cause release of the oil. As the oil droplets increase in size, they are
unable to re-enter the fine, water-wet pores of the surrounding dense rock. This
is purely a hypothesis and it does not explain how the oil migrates in the water,
what portion of it moves with the water, or at what stage most of the oil leaves the
source bed.
The oil may travel in the form of droplets, as a colloidal dispersion, in
solution, or in a gaseous form. HOBSON(1954) has discussed a mechanism by
which oil globules may be squeezed between small pore openings, eventually
making their way into the reservoir. E. G. BAKER(1962) has presented evidence
on petroleum composition, which, according to him, supports the concept of the
migration of oil as a dilute colloidal dispersion stabilized by natural soaps.
MCAULIFFE ( I 964) made detailed studies on the solubility of hydrocarbons in
water. His data suggested that hydrocarbon solubilities are sufficient to account
for known oil accumulations. In most sedimentary basins calculations of the total
quantity of water moved compared to the oil in place indicate that solubilities
of hydrocarbons in water of 2-5 p.p.m. are sufficient to account for the oil fields.
There are arguments against all of the proposed mechanisms. Migration
of oil as globules would require distortion of the globule in order to move through
the very fine pores of the source bed, and such distortion is resisted by the high
interfacial tensions. About 50 times more soap or solubilizing material than
hydrocarbon is needed for the formation of a colloid, and it is well known that
such surface-active agents tend to be adsorbed by the host rock. For example,
attempts to use soap solutions for the secondary recovery of oil have largely
failed because the soap is adsorbed on the mineral surfaces before travelling very
far. Migration either as a colloid or in pure solution does not explain why the oil
separates out on entering a porous reservoir. Undoubtedly there are differences
in the physical and chemical environment of the reservoir compared to the source
bed, but just what these are and how they cause separation of the oil is not known.
234 J. M. HUNT

If oil migrates as fine globules or as colloids it would encounter more difficulty in

moving through fine-grained carbonate source beds than through clays. Carbonate
particles would not have the mechanical ability of clay particles to cause distor-
tion of the globules and consequent squeezing through the sediment pores. Migra-
tion as a soap-stabilized colloid would be stopped by the presence of calcium and
magnesium ions in the water. It is generally known that calcium ions in sand
columns will tie up surface-active agents, and there is no reason why this would
not happen in muds. Migration in solution without the aid of solubilizing
organic material would probably occur as readily in carbonates as in clays.
GINSBURG (1957) has pointed out that most of the water in carbonatemuds is
lost in the first foot or two. WELLER(1959) agrees that very little compaction
occurs in lime-muds. HOLLMANN (1962) showed evidence for the underwater
consolidation of limestones, and observed that in relatively deep water off northern
Italy the undersides of ammonites have impressions of irregularities of the under-
lying limestone beds. This indicates that the limestone beds were hardened and
partly dissolved before the ammonites were laid down. The limestones consolidate
mainly by cementation and recrystallization. It would seem from this that the mi-
gration of fluids from limestones would occur too early and over too short a
depth interval to be an effective mechanism in carrying appreciable quantities of oil
to a reservoir. Consequently, most of the oil in a carbonate rock would be locked
in and would have to find its way out at some later stage of lithification. This
could occur with fluid migration along fractures, solution paths and joints which
are much more common in carbonates than in shales. GEHMAN (1962) observed
that the ratio of hydrocarbons to organic matter in limestones was much higher
than that in shales. This is consistent with the idea that limestones tend to lock in
their hydrocarbons and release them with much more difficulty than do the shales.
There are other explanations for this, however, which will be considered later.
CHAYKOVSKAYA (1960) stated that according to some investigators the early
lithification of carbonate muds makes them incapable of giving up bitumens to
surrounding formations. Nevertheless, there are evidences of molecular migration
within carbonate source beds which are quite numerous and convincing. Chaykovs-
kaya pointed out that bitumens move into the numerous fractures and caverns
that are formed by the circulation of underground water through the carbonate
rocks, which also increases primary porosity. She concluded that several of the
carbonate formations in the Turukhansk and Noril’sk district of the Soviet Union
are characterized by high bitumen content. These’bitumens were formed within
the carbonate source beds and redistributed themselves in minor caverns, pores
and fractures. Chaykovskaya also agreed with Gehman that pure carbonate for-
mations contain a relatively small quantity of organic matter, a large part of which
consists of hydrocarbons.
It should be emphasized that there are many argillaceous limestones and
calcareous shales having mineral compositions between those of the clays and
THE ORIGIN OF PETROLEUM IN CARBONATE ROCKS 235

carbonates. These are even less understood with respect to their compaction
characteristics and ability to release fluids to the reservoirs. Many of these hybrid
sediments have very high organic contents (HUNT,1961; BITTERLI, 1963). Some of
these, such as the Duvernary Formation of Canada and the LaLuna Formation
of Venezuela, appear both chemically and geologically to be source rocks.

EXAMPLES OF CARBONATE SOURCE ROCKS

Recently, OWEN(1964) reviewed the geological concepts favoring carbonates as

being source rocks. He stated that the stratigraphic and structural habitats of many
oil and gas pools in carbonate rocks indicate indigenous origin of their hydrocar-
bons. There are many oil-producing areas where carbonate rocks are by far the
dominant lithology. Some of the important oil occurrences are discussed in this
chapter.

The Williston Basin, U.S.A.

This basin covers an area of more than 100 sq. miles and contains a Devonian
marine carbonate section more than 1,000 ft. thick (BAILLIE,1955). The strata
consist of an assemblage of limestones, dolomites, evaporites and minor amounts
of shale. Commercial oil is found in the predominantly carbonate strata of the
Saskatchewan group, although both oil shales and asphalt stains are present through-
out many parts of the Middle and Upper Devonian. For example, at the base of
the Elk point group in northwestern North Dakota and eastern Montana, there
is a dark colored, dense limestone that was deposited under euxinic conditions that
favored preservation of organic matter. Oil shows and staining are common on
fractured surfaces, suggesting that the oil is indigenous, and that the dark lime-
stone can be considered a source rock. Here again, however, it could be argued
that clays are contributing some oil, because argillaceous limestones and dolomites
are common to both the Middle and Upper Devonian sections. Nevertheless, this
does represent an oil-generating area of predominantly carbonate facies. Many of
the carbonates of both the Elk Point and Saskatchewan groups are pale to dark
brown limestones and dolomites with dark grey carbonaceous shale laminae in
places, and oil staining and bitumens are common throughout the section.

Abqaiq-Ghawar oil j e l d , Saudi Arabia

The largest oil field in the world, Abqaiq-Ghawar, is on a structural accumulation

more than 140 miles long and produces from an oil column reaching a maximum
vertical thickness of 1,300 ft. (ARABIAN-AMERICAN OIL COMPANY STAFF,1959).
The main producing interval is the Arab-D member in the upper part of the Juras-
236 J. M. HUNT

sic Jubaila formation. The Jubaila consists of 1,200ft. of fine-grained limestone with
subordinate calcarenite, limestones and dolomite. The Arab-D formation con-
sists of calcarenite, fine-grained limestone and dolomite with interbedded anhydrite
members (560 ft.). This is overlain by another 500 ft. of limestone and dolomite
with an anhydrite cover. Above the anhydrite at the base of the Arab-D member
the sediments contain only oil shales and minor staining. Most of the oil production
found in the first 240 ft. of the Upper Jubaila Formation is below the anhydrite.
The Arabian-American Oil Company staff, who have probably studied this field
more intensively than any other group of individuals, believe that the Ghawar oil
originated in the Upper Jubaila and Arab-D sediments. This is based partly on the
apparently capricious distribution of oil and water in porous units of the Middle
and Lower Jubaila. The volume of these porous units is roughly proportional to
the amount of calcarenite in the formations. This is probably one of the most
clear-cut geological examples of carbonate source rocks.

Other Middle East ,fields

Other possible carbonate source beds in the Middle East include the Middle
Cretaceous to Oligocene limestones and chalk of Iraq, Iran and southeast Turkey
with oil in associated reef complexes and fractured limestones (BAKERand HAN-
SON, 1952). Also, the oil fields of southwest Iran produce from the Upper Asmari
Limestone which is believed to contain indigenous oil. The Asmari Limestone is
700-1,500 ft. thick and has reef characteristics in places. Both the Miocene and
Oligocene components of the Asmari are richly organic. The 60-mile long Kirkuk,
a billion barrel oil field in northern Iraq, is another good example of a Middle
Eastern oil field with carbonate source rocks (DUNNINGTON, 1958). The producing
reservoir is made up of reef and globigerinal limestones of Middle Eocene to
Lower Miocene age. Limestone and a salt bed overly it, and thick limestones and
marlstones underly it.

Miscellaneous examples

There are other examples of oil occurrence in carbonate rocks but in many of
these an overlying or underlying shale is a more likely source. One of the most
common examples of this is oil occurring at unconformities where shales overly
carbonates. Porosity in such carbonates is frequently due to erosion and solution
weathering. This provides an excellent reservoir for oil migration from overlying
clay muds. Typical examples are the Rogers City, Traverse, and Dundee Lime-
stones of the Michigan Basin and the Trenton Limestone of Michigan and western
Ohio. Another is the Simpson Shale acting as a source for the Ellenburger Lime-
stone of the Permian Basin of Texas and New Mexico.
MILLERet al. (1958), in a detailed study of the oil in the Maracaibo Basin of
Venezuela, concluded that the highly bituminous LaLuna Limestone was a
THE ORIGIN OF PETROLEUM IN CARBONATE ROCKS 237

probable source for some of the oil in western Venezuela. The effective reservoir
section of the Cogollo and La Luna'Limestones is about 1,800 ft. thick. BODUNOV-
SKVORTSOV (1 958) believed that the bitumens found in the lower Cambrian dolo-
mitic limestones of eastern Siberia were indigenous. There are three carbonate
suites, the Angar, Bulay and Bel, which represent about 800 m of limestones inter-
bedded with anhydrite. The whole section is underlain by a thick dolomite se-
quence. BROD(1959) believed that the asphalts and bitumens found in inclusions
of thick Paleozoic limestones and dolomites of the western part of the East
Siberian platform are indigenous. There are probably many other examples of
carbonate sediments believed to be source beds of oil. Those given here are sufi-
cient, however, to attest to the widespread distribution of carbonate sources. As
previously mentioned, carbonate rocks contain at least 40 % of the world's oil,
although they represent only 16 % of the sediments of the basins of continents and
continental shelves compared to 50% for clay shales (WEEKS,1958).
Some of the factors which favor formation of carbonate source rocks
include the following:
(I) It has been stated that the carbonates would lithify quickly and tend to
hold in their hydrocarbons during the early stages of fluid migration from a basin.
Many hydrocarbons are undoubtedly lost from clay muds during this period
due to the lack of a sufficiently impermeable caprock.
(2) Limestones are frequently associated with evaporites under conditions
that are highly favorable to oil generation and accumulation. WEEKS(1961) cited
a typical sedimentary sequence as beginning with a deep stagnant limy mud facies
with limestones or dolomites around the flanking shelves. Cherts may occur in the
deeper parts, followed by purer, partly recrystallized and dolomitized limestone
facies. Isolated reefs facing the deep basin as well as patch reefs higher on the
shelf are common. The sequence continues up with spreading evaporites-primary
dolomites, anhydrites, and/or salt. Eventually evaporites spread over the entire
central area of the basin. In such a cycle the organic matter which accumulated
from the beginning eventually generates hydrocarbons on a vast scale. These are
then trapped because of the presence of impermeable cover of evaporite deposits.
Weeks cited about 20 examples of oil-producing basin sequences that go through
some or all of these stages.
(3) The hydrocarbons moving with the aqueous phase through fractures,
fissures and primary.pores enlarged by solution would tend to be released to
form oil globules on contact with the highly saline waters typical of carbonate-
evaporite sequences. This is speculative, of course, but the great variations in
salinities could be a favorable factor in the oil-accumulation process.
In summary, it appears that most carbonate source rocks associated with
major oil accumulations, such as the huge Tertiary and Jurassic oil pools of the
Middle East, are of this carbonate-evaporite sequence type favorable for the or-
igin, migration and accumulation of oil.
238 J. M. HUNT

DISTRIBUTION OF ORGANIC MATTER IN CARBONATE SOURCE ROCKS

Geochemists have approached the identification of source rocks by making

detailed studies of the various organic constituents in ancient sediments and
finding out differences between oil-producing and non-producing regions. If
one accepts the concept that petroleum originates from organic matter deposited
with the non-reservoir sediments (dense carbonates) and migrates into reservoirs
(reefs, oolites), then it is important to understand the distribution of the organic
matter and hydrocarbons in the non-reservoir sediments. The distribution of or-
ganic matter in sediments varies widely and is significant in drawing conclusions
about the probabilities of finding oil in a particular part of a sedimentary basin.
Unfortunately, few studies of this type have been made in carbonate sequences.
Much more common are studies of clays with minor amounts of carbonates.
For example, RONOV (1958) made a detailed study of the organic carbon distribu-
tion in the Devonian sediments of the Russian platform. He found that, in general,
the clays contained more organic carbon than the carbonates. His data are
shown in Table VI with the organic carbon converted to organic matter by multi-
plying by a factor of 1.22 (see FORSMAN and HUNT,1958, for conversion factor).
As might be expected, the coastal and open-sea environments contained most of
the organic matter and the continental the least. Ronov also noted an interesting
correlation between the occurrence of petroleum in Devonian reservoirs and the
concentration of organic matter in associated non-reservoir rock. He found that
all the petroleum was located in regions where the associated shales contained the
higher organic contents, generally at least 1 % organic matter. In regions where
the organic content of the shales was low (generally less than 0.5 %), no oil or gas
was found. Inasmuch as the carbonates were intermixed with the clays, no con-
clusions can be drawn as to their effect on the oil accumulations. Also, Ronov did
not make hydrocarbon analyses which are important in evaluating carbonate
source rocks.

TABLE VI
WANIC
MATTER AND ENVIRONMENT (DEVONIAN OF THE u.s.s.R.)

(After RONOV,1958)

Environment Weight % of organic matter1

days carbonstes

continental, lagoonal 0.43 0.18

coastal-marine 0.95 ' 0.25
open sea 1.10 0.39

1 Organic carbon times 1.22.

THE ORIGIN OF PETROLEUM IN CARBONATE ROCKS 239

TABLE VII
DISTRIBUTION OF HYDROCARBONS AND ORGANIC MATTER IN NON-RESERVOIR ROCKS

(After HUNT,1961)

Rock type Hydrocarbons Organic matter

fP,p.rnJ (weight %)

Shales
Wilcox, La. 180 1 .o
Frontier, Wyo. 300 1.5
Springer, Okla. 400 1.7
Monterey, Calif. 500 2.2
Woodford, Okla. 3,000 5.4

Limestones and dolomites

Mission Canyon Limestone, Mont. 67 0.11
Ireton Limestone, Alta. 106 0.28
Madison Dolomite, Mont. 243 0.13
Charles Limestone, Mont. 271 0.32
Zechstein Dolomite, Denmark 310 0.47
Banff Limestone, N.D. 530 0.47

Calcareous shales
Niobrara, Wyo. 1,100 3.6
Antrim, Mich. 2,400 6.7
Duvernay, Alta. 3,300 7.9
Nordegg, Aka. 3,800 12.6

The hydrocarbon analysis can be obtained by pulverizing the sediment

sample and extracting the soluble organic matter with various organic solvents,
such as ether or benzene. The soluble organic matter can be separated into two
fractions, the hydrocarbons and the non-hydrocarbons (asphalts), by column
chromatography (HUNT,1956; PHILIPPI,1956). Light hydrocarbons are lost in
removing the solvent so that the molecular weight range starts a t about c14 and
continues on to c40-c50. The asphalts are compounds containing nitrogen, sulfur
and oxygen as well as carbon and hydrogen. The residual organic matter, which
has sometimes been referred to as kerogen, has been described in some detail by
FORSMAN and HUN? (1958).
The distribution of the hydrocarbons and residual organic matter in some
typical shales and carbonates is shown in Table VII. The hydrocarbon fraction
represents petroleum that is disseminated in the source bed. In most sedimentary
basins there is 20-100 times as much of this petroleum in the source beds than in
the reservoirs.
The high concentration of hydrocarbons and organic matter in rocks such
as the Woodford, Duvernay and Nordegg Shales does not automatically make
240 J. M. H U N T

them good source rocks. It is possible that the organic content of this type of
sediment is so high that it tends to act as a blotter, that is, it adsorbs hydro-
carbons instead of releasing them to the reservoirs. The fact that some rocks such
as the Mission Canyon limestones have a very low hydrocarbon content does not
necessarily mean that they have released a considerable amount of hydrocarbons
to reservoirs. The quantities of hydrocarbons that were originally present or have
been gathered from any of these sediments is not known. Some estimates could
be made by adding up the hydrocarbons in both reservoir and non-reservoir rocks
of an entire sedimentary basin, but this figure would not include losses over geologic
time. It is interesting to note that most of the limestones and dolomites have
hydrocarbon contents comparable to those of the shales even though the organic
contents are lower by a factor of 10. This emphasizes the aforementioned impor-
tance of hydrocarbon analyses.
The low organic content of carbonates compared to shales in Table VII
agrees with Ronov's data in Table VI. Recent carbonate sediments, however,
have organic contents very similar to those of Recent clays (Table VIII). GEHMAN
(1962) suggested that most carbonates lose organic matter faster than shales due
to repeated exposure to meteoric waters. An alternative hypothesis by E. T. Degens
(personal communication, 1964) is that the carbonates contain primarily protein-
aceous organic matter which is hydrolyzed during recrystallization, whereas the
clays contain primarily humic and lignitic organic matter which survives the
period of compaction and diagenesis. This is summarized in Fig. 1 and 2. If a large
part of the organic matter is lost in carbonate sediments early in their diagenesis,
it still does not explain why the remaining organic matter is such an efficient
generator of hydrocarbons. The ratio of hydrocarbons to organic matter as shown
in Table VIII is far higher in ancient carbonates than in ancient shales. Unfor-
tunately, the proportion of hydrocarbons lost from these two types of rocks is

TABLE VIII

DISTRIBUTION OF HYDROCARBONS AND ASSOCIATED ORGANIC MATTER IN RECENT AND ANCIENT

SEDIMENTS

(After HUNT, 1961)

Sediments fiydrocarbons Organic matter

(p.p.m.) (weight %)

clays (Recent)2 50 1.5

clays (ancient)2 300 2.0
carbonates (Recent)l 40 1.7 '

carbonates (ancient)2 340 0.2

1 Gulf of Batabano, Cuba.

2 Average of samples from several areas.
THE ORIGIN OF PETROLEUM IN CARBONATE ROCKS 24 1

[7 Amino compounds
Carbohydrotes
Organic solvent extract
Organic residue( humicl

Ancient shole
(mean total
organic matter 1

-Ancient limestone -
(mean total organic matter)
Shell Carbonate Limestone Clay
(Mylilus (Florida Bay) (Son Diego Tmughl
Cali fornianusl

Fig.1. Organic maaer content of Recent marine sediments. (After E.T. Degens, personal commu-
nication, 1964.)

WEIGHT PERCENT IN CLAYS CONSTITUENTS WEIGHT PERCENT IN CARBONATES

85 Humus and lignin 5
10 Proteins 90
Sugars and lipids

=\>y.dorv!si Compaction of proteins\Recrystallization

Only 5-10% 6;ganic matter lost About 75%organic matter lost

Fig.2. Loss of organic matter in sediments.

not known. As previously mentioned, it may be that most of the hydrocarbons

generated in carbonates are trapped in them by early lithification, whereas those
in shales represent a remnant of a much greater amount that was generated and
partially lost.
One of the most detailed studies of the distribution of hydrocarbons in the
source-reservoir facies of a geological section was made by D. R. BAKER(1962).
He found a wide Yariation between the hydrocarbon and organic carbon contents
of sediments of different lithologies from the Cherokee group of Kansas and
Oklahoma. His data for the principal lithologies are summarized in Table IX. The
range in hydrocarbon content from these different lithologies, which are in very
close stratigraphic proximity, is nearly as large as for samples from all over the
world as shown in Table VII.
All of the lithologies presented in Table IX could have contributed some hy-
drocarbons to the Cherokee reservoirs. The most probable sources would be the
limestones and gray shales. The underclays and greenish-gray shales have too
242 J. M. HUNT

TABLE IX

MEAN ORGANIC COMPOSITION OF PRINCIPAL ROCK TYPES OF CHEROKEE GROUP OF KANSAS AND
OKLAHOMA

(After D. R. BAKER,1962)

Rock type Number of Hydrocarbons Organic carbons Hydrocarbons

samples (p.p.m.) (weight %) organic c * 10-2

underclay and
related rocks 9 19 0.34 1.06
greenish-grayshales
and related rocks 43 31 0.31 1.26
limestone 11 91 0.19 4.12
gray shale 31 129 1.52 0.92
black phosphatic shale 19 2,920 7.94 3.88

low a hydrocarbon content to be effective contributors, whereas the phosphatic

shale is so rich in hydrocarbons that it might not release them. Baker’s data verify
the results obtained by other investigators previously mentioned by showing a
very high ratio of hydrocarbons to organic carbon in carbonates.
In discussing his results, Baker mentioned the problem of differentiating
hydrocarbons which have migrated vertically into a presumed source bed from
those which are indigenous. This is a knotty problem which clouds any inter-
pretation of hydrocarbon distribution in sediments. Most comparisons of crude
oil in reservoirs, however, show that there are chemical similarities over several miles
horizontally within a formation, but marked differences can be observed in only
a few hundred feet vertically. The data of BASS(1963) are typical in showing the
composition of crude oil in the Rangely, Ashley Valley and Elk Springs pools in the
Weber sandstone to be similar even though they span a horizontal distance of 50
miles. On the other hand, the oils in the Weber, Shinarump and Mancos Sands are
entirely different even though they span a vertical distance of only 4,000 ft. (less
than 1 mile). This suggests that the migration of most crude oils occurs within
neighboring stratigraphic units and does not span the entire vertical section of the
basin. NERUCHEV (1962) also has geochemical data, to be shown later, which
indicate that most hydrocarbons in the source beds are indigenous.

GEOCHEMICAL TECHNIQUES FOR RECOGNIZING CARBONATE SOURCE ROCKS

The studies reported above have provided much valuable information on how
hydrocarbons are distributed in sedimentary basins relative to oil and gas accu-
mulations. Many petroleum companies have also developed empirical methods of
THE ORIGIN OF PETROLEUM IN CARBONATE ROCKS 243

source-rock identification which are based partly on experience and partly on

faith. The first of these empirical methods was developed by PHILIPPI (1956) and
associates of the Shell Oil Company. They considered fine-grained sediments
with indigenous oils to be oil-source beds, the source-rock quality being defined
as the amount of hydrocarbons present per unit weight of dry rock. Rocks with
less than 50 parts of indigenous hydrocarbons per million parts ofdry sediment were
considered very poor sources, whereas those with over 5,000p.p.m. were considered
excellent sources. The LaLuna Limestone of western Venezuela was regarded as
an important oil source by this method.
The hypothesis on which this technique is based is simply that if a fine-
grained sediment contains indigenous hydrocarbons, it means that the sediment
was capable of generating hydrocarbons and, therefore, is a source rock. One
cannot really define the sediment as an oil source, however, unless oil from it has
accumulated in commercial quantities. This requires not only generation but also
release of the hydrocarbons and their accumulation in a suitable porous trap.
Assuming that the hydrocarbons extracted by the Shell technique are indigenous,
the method does fulfill the first requirement of a source rock but not the others.
In effect, it gives a picture of the distribution of hydrocarbons in a sedimentary
basin, and one must assume that the sediments with highest concentration of
hydrocarbons will be associated with reservoirs containing the highest amount of
oil. This is probably true for rocks with intermediate-range hydrocarbon contents,
but it may not be true for rocks with very high hydrocarbon contents. As previous-
ly mentioned, if the rocks are oil wet, they would tend to adsorb the oil instead of
releasing it.
Another system for identifying source rocks has been reported by BRAY
and EVANS (1961). They pointed out that the normal paraffins of Recent sediments,
which eventually become part of crude oil, have predominantly odd-numbered
chain lengths. The ratio of the amounts of odd to even chain lengths of hydrocar-
bons is 3-5/1. The reason for this was first discovered by CHIBNALL and PIPER(1934).
They found that insect and plant waxes contain primarily the odd-numbered
paraffin chain lengths. As these waxes from living organisms find their way into
the sediments they would maintain this ratio. In contrast, it was found by Bray and
Evans that the normal paraffins in crude oil contain practically equal quantities
of odd- and evenhumbered chain lengths of hydrocarbons. The ancient sediments
that might be considered as possible sources of the crude oils contained normal
paraffins that have a greater preference for the odd chain lengths than the crude
oil accumulations. This is generally less pronounced for the hydrocarbons in Re-
cent sediments. These results are summarized in Table x. Bray and Evans reasoned
that the initial difference in odd and even chain lengths of paraffins in living
organisms and in Recent sediments was gradually reduced as the hydrocarbons
that were generated in the sediments were added to the original hydrocarbons from
the living organisms. Generated hydrocarbons would have equal amounts of odd
244 J. M. HUNT

TABLE X

RATIO OF ODD- TO EVEN-NUMBERED I2-PARAFFINS IN SEDIMENTS AND CRUDE OILS

Source Ratio of odd- to even-numbered

n-parafins chain length

Recent sediments 2.5-5.5

ancient sediments 0.9-2.4
crude oils 0.9-1.2

and even chain lengths. Consequently, if enough of these were formed in compar-
ison with the amount originally present, they would tend to obscure the odd chain-
length preference observed in hydrocarbons from Recent sediments. Bray and
Evans concluded that a sediment could be considered a source rock if it generated
enough hydrocarbons to reduce the odd-even carbon ratio to 1.20 or less.'This is
about the maximum value observed in crude oils. By this technique, both the Can-
yon Limestone of Texas and the Heath Limestone of Montana could be defined
as source rocks because their odd-even ratios averaged 1 .O and 1.1, respectively.
Of course, any of these source-rock techniques require examination of several
samples within a formation, because a formation may not be uniform in its capa-
bility of generating hydrocarbons.
KHALIFEH and LOUIS(1961) developed an oxidation method for determining
source rocks. Briefly, their method consists of measuring the reducing power of the
insoluble organic matter in the rock by adding a strong oxidizing agent such as
potassium permanganate. The ratio of reducing power to total organic carbon
is then plotted against the weight percent carbon remaining after oxidation. This
indicates the state of reduction at various stages in the oxidation process. Khalifeh
and Louis obtained three types of curves:
(1) A rising curve, indicating that the more resistant organic matter consumes
more oxygen and, therefore, is more reduced. This is characteristic of a good source
rock.
(2) A descending curve, indicating that the more resistant organic material
consumes very little oxygen, that is, it has already been oxidized to some extent.
This is characteristic of a poor source rock, or more continental-type organic
matter.
(3) In some instances, a straight line is obtained indicating that the organic
matter is similar to that found in Recent muds, that is, it is in a state .of evolution,
or still in the process of being reduced. By this technique, the LaLuna Limestone
of Venezuela appears to be a good source rock and the Kimmeridgien limestone
of France appears to have not yet generated any oil.
VEBERand GORSKAYA (1963) studied the chemical composition of dispersed
THE ORIGIN OF PETROLEUM IN CARBONATE ROCKS 245

bitumens as a means of recognizing source rocks. They cited the bituminous

limestones of Carboniferous age in the Donets Basin as an example of carbonate
source rock. They found that the dispersed bitumen in the limestones is a true pe-
troleum, and, according to Veber, it was clearly indigenous. In one section of the
Viscan Limestone, the asphalt found in a fracture was generally similar in compo-
sition to the dispersed bitumen in the limestone matrix.
Any method for distinguishing migrating (allochthonous) hydrocarbons from
native (autochthonous) hydrocarbons would be a method of recognizing source
rocks. The presence of large quantities of migrating hydrocarbons would imply
good source characteristics. USPENSKIY et al. (1958) first proposed that changes in
the degree of bituminosity (percentage of hydrocarbons) in the total organic
matter could be used to recognize traces of oil which migrated. The idea is that if
oil is migrating, being redistributed within the mother rock, there will be sections
of high concentrations of hydrocarbons which will stand out over and above
the levels due to indigenous hydrocarbons. These would be considered migrated
hydrocarbons. VASSOEVICH (1958) defined this more precisely by showing that
the percentage of hydrocarbons in the total organic matter increased as the
content of organic matter decreased. NERUCHEV (1962) demonstrated these con-
cepts by logarithmically plotting the percent of soluble bitumens in total carbon
against the total organic carbon content as shown in Fig.3. The line in this figure
separates the anomalously high values of soluble bitumens from the background
values. Points above this line represent migrated bitumens, whereas those below
the line represent native bitumens. It can be seen that the percent of native
bitumens increases with decreasing organic carbon. Vassoevich, who edited
Neruchev’s book, pointed out that each different type of rock would have its
autochthonous hydrocarbons on a different part of the diagram. The line in Fig.3
would shift with lithology. For example, carbonate rocks are known to have high
native bitumen content in their organic matter, so that the line separating migrated
bitumens would be higher than that for clays. Unfortunately, Neruchev does not
state just how he decides where to draw the line. Neruchev also distinguished
native and migrated bitumens by plotting frequency distribution curves of the
bitumen content of samples from individual formations. Anomalous values be-
lieved to be caused by migrating bitumens stand out very clearly on these graphs.
Generally the native bitumens represent more than 75 % of the total. This is also
evident in Fig.3.
At the end of his book, Neruchev presented equations for calculating the
quantities of native and migrated oils in a sediment. The calculations are based on
the idea that when a source rock gives up oil, there is a reduction in the contents of
carbon and hydrogen and a proportionate increase in the contents of oxygen,
nitrogen and sulfur in the organic matter of the rock. Also, there is a decrease
in the amounts of oily fraction and hydrocarbons in the rock. According to
Neruchev, by determining the amounts of carbon, hydrogen, oxygen, nitrogen
246 J. M. HUNT

I
Mlgrated
bitumens i

.iT
50- i l

10

11
51

i
tumens
I 0 5
I
0 I
0.5
0 OO0 I

1
0.1
0.1 0.5
Total organic carbon (weight percent)

Fig.3. Relationship between the total organic carbon content and the ratio of soluble bitumens in
total carbon. (After NERUCHEV, 1962.)

and sulfur in various fractions of the organic matter, one can calculate the
quantity of oil that has migrated from oil-generating deposits and thereby esti-
mate the amount of total undiscovered reserves in the basin under study. Although
he recognized the difficulty in estimating the amount of oil lost due to the lack
of reservoir cover, he still felt that this technique could be used in oil exploration.

CONCLUSIONS

Table XI attempts to summarize the various concepts relating to source rocks.

It is recognized in any comparison of lithologies, such as carbonates and clays,
that the entire spectrum of conditions may be present in both groups. The state-
ments made are designed to highlight the more significant differences rather than
describing a typical carbonate or shale source rock.
Carbonate deposition in open shelf areas occurs in shallow, well-aerated
waters. The slow rate of deposition allows adequate time for destruction of the
fleshy material of marine organisms, leaving the organic matter, which is largely
THE ORIGIN OF PETROLEUM IN CARBONATE ROCKS 247

proteinaceous, in the shells. Somewhat greater quantities of organic matter would

be preserved in the less common evaporite basins.
Clay particles, in contrast, come from the continents with adsorbed humic
and lignitic organic matter, and are deposited in the deeper, rapidly subsiding
parts of the basin. More organic matter is preserved due to the rapid deposition,
but there is also more mineral matter. Thus, the percentage of organic matter
in the sediment is about the same for clays and carbonates. Carbonates lose their
water in the first few feet of burial and undergo early lithification and recrystalli-

TABLE XI
COMPARISON OF CARBONATES AND SHALES AS SOURCE ROCKS OF PETROLEUM

Limestones and dolomites Clay shales

environment of deposition: shallow, aerated on open deep, often reducing

shelf but reducing in eva-
porite basins
rate of deposition: slow rapid
source of organic matter: primarily marine primarily terrestrial
type of organic matter: proteinaceous, some humic humic and lignitic
compaction and lithifi- early loss of water, rapid slow and continuous loss
cation: lithification and recrys- of water
tallization
process of hydrocarbon thermal catalytic and thermal
generation from organic
matter:
probable time of hydro- late early and continuous
carbon generation:
probable time of HC late, after lithification early during major
migration: and fracturing of the movement of fluids
rock and development of
solution permeability
probable mechanism of HC in solution or as globules in solution with the
migration: moving along fractures expelled fluid
and solution paths
proximity of reservoir very near; oolites and variable; many thick
porosity to source: reefs; fracture complexes; source beds have no
frequently porosity is interbedded porous rocks
developed in or close to
the source (solution and
dolomitization)
effectiveness of reservoir good, due to frequent average, considerable
traps: proximity of impermeable amount of oil is lost
anhydrite covers through sands, silts and
continental sediments
248 J. M. HUNT

zation. Clay sediments have a slow and continuous loss of water from 80 % porosity
a t the surface to about 8 % at a depth of 10,000 ft. (HEDBERG,1936). Experimental
laboratory results obtained at the Petroleum Engineering Department of the
University of Southern California show that the remaining moisture content
(percent dry basis), at an overburden pressure of 10,000 lb./sq.inch varies from
6-32 %, depending on the type of clay (G. V. Chilingar, personal communication,
1965). Due to the catalytic effect of clays, even in the presence of water, hydro-
carbons can be generated quite early in this process and migrate within the first
500 ft. of sediment. Many of these hydrocarbons will be lost because of the lack
of adequate rock cover; therefore, it is important that suitable reservoirs and
traps form early enough to catch the hydrocarbons while the major fluid movement
is still going on in the basin. At depths beyond 5,000 ft. hydrocarbons are prob-
ably still being generated, but, due to the great decrease in permeability .and the
minor amount of fluid movement, the hydrocarbons would have difficulty in-
migrating out of the shales.
In carbonates, on the other hand, the early cementation and recrystallization
to form a lithified rock would be accompanied by hydrolysis and solution of
much of the organic matter and probably some of the initially deposited hydro-
carbons. Later in its history, as the carbonate rock became buried deeper, hydro-
carbons would be generated thermally from the remaining organic matter and would
migrate along the solution or fracture zones. The solution zones could be formed
by infiltrating meteoric waters, or by fluids moving up from the deeper parts of
the basin.
One advantage of carbonate source beds over shales is the frequent close
proximity of porous reservoir beds. Studies of the hydrocarbon contents of source
beds generally show them to be most effectively drained in the presence of inter-
bedded porous sediments. In carbonates the source and reservoir rocks are fre-
quently in juxtaposition. Reservoir porosity (oolite, solution and dolomite poros-
ity) may be scattered capriciouslj throughout a carbonate rock, whereas in a shale
bed the associated sand development is more clearly delineated. Many thick shale
sections contain vast amounts of hydrocarbons which could have made oil pools
had there been interbedded porous zones. Carbonates deposited in evaporite
basins also have the advantage of impermeable anhydrite covers which retain the
oil much better than do shales in typical sand-shale sequences.

ACKNOWLEDGEMENTS

The author is indebted to Dr. K. 0. Emery, Dr. F. Manheim and Dr.'E. T. Degens
for reviewing the manuscript, and to Mrs. T. Perras for typing it. This work was
partially supported by the National Science Foundation Grant No.1599 and
Contract Nonr-2196(00) with the Office of Naval Research.
 THE ORIGIN OF PETROLEUM IN CARBONATE ROCKS 249

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TREIBS,
A., 1934. Chlorophyll and hemin derivate in bitumens, rocks, oil, waxes and asphalts.
Ann. Chem., 510: 42-62.
USPENSKIY, V. A. and CHERNYSHEVA, A. S., 1951. Material composition of organic material from
the Lower Silurian limestones in the region of the town of Chudovo. Tr. Vses. Nauchn.
Issled. Geologorazvcd. Neft. Inst., 57.
THE ORIGIN OF PETROLEUM IN CARBONATE ROCKS 25 1

USPENSKIY, V. A., CHERNYSHEVA, A. S. and MANDRYKINA, Yu. A., 1949. About dispersed form
of hydrocarbon Occurrence in different sedimentary rocks. Izv. Akad. Nauk S.S.S.R.,
Ser. Geol., 5 : 83.
USPENSKIY, V. A., INDENBOM, F. B., CHERNYSHEVA, A. S. and SENNIKOVA, V. N., 1958. On the
development of a genetic classification of dispersed organic matter. In: N. B. VASSOEVICH
(Editor), Questions of Formation of Petroleum (Symposium)-Tr. Vses. Nauchn. Issled.
Geologorazved. Neft. Inst., 128: 22 1-3 14.
VASSOEVICH, N. B., 1955. The Origin of Petroleum (Symposium). Gostoptekhizdat, Leningrad.
VASSOEVICH, N. B., 1958. Formation of oil in terrigenous deposits (especially the Chokrak-
Karagansk deposits of the Tersk anterior basin). In: N. B. VASSOEVICH(Editor), Questions
of Formation of Petroleum (Symposium)-Tr. Vses. Nauchn. Issled. Geologorazved. Neft.
Inst., 128: 9-220.
VEBER,V. V. and GORSKAYA, A. I., 1963. Bitumen formation in carbonate facies of sediments.
Sov. Geol., 8: 51-63.
VEBER,V. V. and TURKELTAUB, N. M., 1958. Gaseous hydrocarbons in Recent sediments. Geol.
Nefti, 2: 3944, English translation in Petrol. Geol., 2: 737-742.
WEEKS,L.G. (Editor), 1958. Habitat of Oil. Am. Assoc. Petrol. Geologists, Tulsa, Okla., 1384 pp.
WEEKS,L. G., 1961. Origin, migration and occurrence of petroleum. In: G. R. MOODY (Editor),
Petroleum Exploration Handbook, p.24.
WEISS,A., 1963. Organic derivates of mica-type layer silicates. Angew. Chem. Intern. Ed. Engl.,
2: 143.
WELLER, J . M., 1959. Compaction of sediments. Bull. Am. Assoc. Petrol. Geologists, 43: 273-310.
WHITMORE, E. C., 1945. A. P. I. Research Project 43B. Proc. Am. Petrol. Inst., Sect. IV, 25:
100-101.
ZOBELL,C. E., 1959. Introduction to marine microbiology. In: C. D. OPPENHEIMER (Editor),
Marine Microbiology-New Zealand Oceanog. Inst., Mem., 3: 1-23.
Chapter 8

TECHNIQUES OF EXAMINING AND ANALYZING CARBONATE SKEL-

ETONS, MINERALS, AND ROCKS

K. H. WOLF^, A. J . EASTON AND s. WARNE

Department of Geology, The Australian National University, Canberra, A.C.T. (Australia)

British Museum, London (Great Britain)
Newcastle University, Newcastle, N.S. W . (Australia)

SUMMARY

The increasing emphasis on detailed study of the petrology of carbonate rocks has
led to the adoption of a multitude of techniques that are described in a series of
widely scattered publications. A selection of these techniques, of proven value in
specific studies, has been brought together in this chapter in the hope that they will
contribute to carbonate studies in general. In many cases, refinements and an in-
crease in reliability of a particular technique will rest on a simultaneous use of
associated methods and modifications to suit specific cases. The interpretation of
the analytical results must be based on sound genetic concepts, which in some
instances also require new approaches as discussed in other chapters in this book.

INTRODUCTION

The impetus given to carbonate sediment research in the past few years has led
to the application of numerous techniques, some old and others rather new. They
range from simple quick field tests to highly specialized, time-consuming, and
elaborate instrument-requiring approaches. The existence of a large variety of
techniques necessitates a rather superficial treatment of a number of them in this
chapter. In some cases only a short discussion and a few pertinent references are
given, but for the more important procedures details of both methods and results
are outlined. In no case, however, is it possible to treat the methods adequately
enough to make the reader independent of the original publications. Fig.1 gives
a general scheme that includes most of the usual methods employed in carbonate
investigations.
Owing to limitations of space there can be no complete coverage of the liter-
ature, and some omissions of pertinent references are unavoidable. Much credit
is due to the various research workers from whose publications much of the infor-
mation has been extracted.

Present address: Department of Geology, Oregon State University, Corvallis, Ore. (U.S.A.).
254 K . H. WOLF, A. J. EASTON AND S. WARNE

Fig.1. Flow chart of examining carbonate sediments. (Modified after SHORT,

1962, by permission
of Am. Assoc. Petrol. Geologists, Tulsa, Okla.)

FIELD STUDIES OF CARBONATE SEDIMENTS

In most geological studies, field work and collecting of samples form the basis for
more precise investigations in the laboratory. Therefore, the importance of ob-
taining as exact and detailed information as circumstances permit during field
work, or on the well site, cannot be too overemphasized.
In large-scale regional reconnaissance work one usually is not concerned
with the precise petrographic make-up of sediments. Just as it has become routine
to divide terrigenous sediments into arkose, greywacke, and so forth, an attempt
should be made to give as detailed a description of carbonate rocks as the par-
ticular conditions allow. The carbonates will reveal many textures, and struc-
tures when etched with dilute (1 :lo) HCl acid and then wetted with water and exa-
mined with a hand lens. At least the grain size and the presence of dolomite and
terrigenous impurities can be determined. In addition, the rock can be described
as calcilutite (= micrite), calcisiltite, calcarenite, calcirudite, dololutite, dolarenite
EXAMINATION AND ANALYSIS OF SEDIMENTARY CARBONATES 255

or dolorudite; or where crystalline, as microsparite, sparite or dolosparite (see

CHILINGAR et al., 1966, for an outline in describing carbonates both descriptively
and genetically). For fine sediments, thin-section studies are absolutely necessary
to check field interpretations. In the coarser rocks the percentage of grains, matrix,
and sparite cement is also determinable by hand lens and many of the fossil types
can be recognized. In particular, if a binocular microscope is available, e.g., on the
well site or in the base camp, descriptive classification of the specimens is possible.
This facilitates the collecting of samples for detailed thin-section examination
that may permit a precise genetic classification. For example, calcareous rocks
thought to be lithographic or micritic limestones, and described as unfossiliferous
and massive when examined with a binocular microscope, have been shown
in thin-section studies to be composed of blue-green algal filaments, cells, etc.
(WOLF,1963a, 1965a; CHILINGAR et al., 1967). Some of the Algae are useful in
dating such limestones (JOHNSON, 1964). Thus, in the case of apparently unfossil-
iferous, massive micritic limestones thin-section studies are most pertinent for a
precise paleontological and petrographic interpretation.
If paleontological studies are to be made predominantly on one particular
phylum, e.g., corals, brachiopods, stromatoporoids or Bryozoa, a quick check on
the associated “micrite” matrix components may assist paleoecological and en-
vironmental reconstructions. In addition, if the micrite proves to be of algal
origin, it may be possible to observe symbiotic relations between the organisms.
In strongly folded areas, it is useful to examine hand specimens for geopetal
(top-and-bottom) criteria, which help in structural and stratigraphic reconstruc-
tions. For example, large brachiopods or primary reef cavities may be partly filled
with sediments at the bottom and have an upper sparite growth, thus providing
useful top-and-bottom criteria where limestones are vertical or overturned.
For detailed studies on textures and structures, it is important to collect
oriented hand specimens in order to understand the diagenesis and paleoenviron-
ments; qnd it is necessary to investigate internal sediments, replacement patterns
of hematite and dolomite, orientation of stromatactis, and so forth.
In studying terrigenous rocks it is desirable to test for carbonate components.
The carbonate may be present either as cement, or as carbonate detritals, or both.
The importance of this distinction has already been stressed (WOLFand CONOLLY,
1965).
The foregoing indicates that in spite of limitations, a field geologist should
endeavor to collect all possible information from HC1-etched and water-wetted
hand specimens to assist in stratigraphic work and to facilitate the selection of
samples for subsequent laboratory studies. In remote areas where field camps may
be set up for lengthy periods, it is advisable to have available binocular micro-
scopes, diluted hydrochloric acid, staining material, and other equipment for more
detailed examinations. More precise analyses may help in solving stratigraphic pro-
blems, in particular where a number of similar-looking carbonate formations outcrop.
256 K. H. WOLF, A. J. EASTON AND S. WARNE

ACID-ETCHING OF CARBONATE SEDIMENTS

Even in reconnaissance studies, it is desirable to carry out acid-etching as pointed

out above. The acid-etched surface reveals textural and structural features and
assists in the identification of dolomite. Etching is also used ( I ) as a preliminary
step to staining; (2) in the preparation of peels; (3) for electron-microscope
studies; ( 4 ) in the determination of percentages of mixtures of calcite and dolomite
using, for example, comparative charts (TERRYand CHILINGAR, 1955); and (5) in
extreme cases of etching, this procedure grades into the separation of insolubles
by acid-digestion (to be described below). Etching is employed on relatively
smooth broken surfaces, on polished surfaces, and on drilling chips. Depending on
the information required, etching may be the only method applied, but for ac-
curate studies it has to be supplemented by thin-section, staining, chemical, and
other techniques. Carbonates composed of particles less than 0.5 mm in diameter
require thin-section studies.
In general, only calcitic, dolomitic and the non-carbonate materials are
identified in routine work. The examination of well cuttings will not allow a very
precise determination of percentages, and it is sufficient to subdivide them into
four lithologic groups. The following procedure is recommended (Low, 1958).
Use chips about 1 /4inch in diameter and 1/8 inch thick and immerse them in cold
dilute HCI (I :7-10). Observe reactions under the microscope, in particular, if
effervescence is slow (clean microscope afterwards to prevent damage by fumes).
In straightforward cases the reaction will be approximately as follows.
Limestone: violent effervescence; frothy audible reaction; specimen bobs
about and tends to float to the surface.
Dolomitic limestone: brisk, quiet effervescence; specimen skids about on the
bottom of the container, rises slightly off bottom; there is a continuous flow of
COZ beads through the acid.
Calcitic dolomite: mild emission of COZ beads; specimen may vibrate, but
tends to remain in one place.
Dolomite: no effervescence; no immediate reaction; slow formation of COz
beads on the surface of the rock; reaction slowly accelerates until a thin stream of
fine beads rises to the surface.
A number of factors will modify these reactions, e.g., presence of non-
carbonate constituents such as clay, anhydrite, and bituminous material, and may
drastically reduce the rate of effervescence of calcitic rocks. The rate of reaction is
also dependent on the size of the chips, presence of adhering powdered carbonate
material, film of water adhering to the surface or present in pores, degree of poro-
sity and permeability, and other factors. With some experience, however, the mod-
ifying conditions are relatively easy to establish. Argillaceous limestone 0.r marl,
for example, will effervesce fast at the beginning, but the reaction will progres-
sively slow down. If a rock chip is crushed with the blunt end of a pair of tweezers
EXAMINATION AND ANALYSIS OF SEDIMENTARY CARBONATES 257

or a probe, a rejuvenation of the acid reaction will occur. On the other hand, dolo-
mite will react very slowly at first and reaction will gradually become more vigor-
ous especially if the acid is heated.
Very porous and permeable dolomite cuttings may react with acid in a manner
rather similar to limestone or argillaceous limestone because of the larger surface
area available to the acid and the greater buoyancy of the dolomite. IRELAND
(1950) mentioned the advantage of examining “curved surface sections” of carbo-
nate chips digested in acid.
Whenever polishing equipment is available, thecarbonatespecimens should be
cut, polished and etched with dilute hydrochloric, acetic, or other acids, or mixtures
thereof, before binocular-microscope examination is undertaken. (Note: aragonite
may invert to calcite if too energetically ground.) The size of the samples depends,
of course, upon the material available and the information desired. LAMAR (1950)
and IVES(1955) used specimens approximately 6 inches long, 2 inches wide and
4-3 inch thick. WOLF(1963a) used slabs up to 10 x 10 inches and larger in the
study of stromatactis, surge-channel and algal colonial structures. Large drilling
chips can be polished quite simply (without a lap) on abrasive paper, for instance,
before acid etching.
After polishing and cleaning thoroughly to remove all abrasive, the spec-
imen to be etched is placed in a dish with the polished surface up. Modelling clay
is useful to hold the specimen in position. The polished surface should be horizon-
tal, for an inclined surface may be channeled by rising streams of bubbles, and the
grooves may be confused with genuine sedimentary features.
The acids employed in etching carbonates as recommended by LAMAR (1950)
are: 23 ml C.P. glacial acetic acid in 100 ml water, or 8 ml concentrated HCI
acid in 100 ml water. The etching times required vary and experiments are ne-
cessary until the best result for the particular rock is obtained. Lamar suggested
20 min etching with acetic acid and 5 min in hydrochloric acid for limestones, but
shorter times may suffice. Dolomites require a longer reaction period, mild heating
of the acid, or both. In general, a slow reaction is necessary to prevent the destruc-
tion of delicate features. To initiate a very slow reaction, the specimen may be
covered with about ++ inch of water, and sufficient acid is then added to commence
mild effervescence. A deep etch is required in some cases, and about 0.5 mm of
rock may be dissolved from the flat surface. After the specimen has been etched for
a period of time as determined by trial-and-error, the acid may be siphoned off
using an eye-dropper, and replaced by water. In this fashion the specimen will not
be moved and none of the minute surface features, e.g., adhering insoluble specks,
will be destroyed or removed. If the specimen is taken from the dish, it is pref-
erable to immerse it twice or three times into a beaker of water instead of washing
it under a stream of water. Under no circumstance should the sample be brushed.
The surfaces of limestones etched with acetic or citric acid are occasionally
covered with a fine powder that precipitates when the specimen is dried. To remove
258 K. H. WOLF, A. J. EASTON AND S. WARNE

the absorbed salt, the specimen is soaked for a few hours in several changes of
water, or is rinsed quickly in a very dilute hydrochloric acid.
The results of acid etching differ somewhat for acetic and hydrochloric
acid (see excellent photos by LAMAR,1950). The latter develops a so-called
“acid polish” due to the absence of strong differential solution; exceptions, however,
have been noted. Coarsely crystalline calcite often appears “glassy”, i.e., it has
the sparry appearance. Internal fossil structures and differences in grain size of
calcite particles are usually well shown, and textures and structures are distinctly
brought out. Dolomite, clay, silt, sand, chert, and other insoluble or less soluble
components project above the etched surface.
Acetic acid reacts less uniformly with the carbonates and usually produces
a rough surface in contrast to the smooth HC1-etched surface. The action of acetic
acid is considerably influenced by porosity, incipient fractures, grain contacts, size
and relative purity of calcite grains, and so forth. Due to local micro-variations,
the core and concentric rings of oolites exhibit differential etching, and so do fos-
sils and calcite grains, for example. Because of the rough surface produced, in-
soluble material is not readily seen on the etched surface, especially if the carbonate
is coarse-grained or coarsely crystalline.
In general, both acids should be used in order to determine which gives the
best result, especially if peels are to be prepared from the polished and etched sur-
faces. One should try different acids at various concentrations applied for selected
periods of time. In a combination treatment a mixture of acetic and hydrochloric
acids produces etched surfaces combining the characteristic effects of the individ-
ual two acids, namely, a semi-polished and subdued differentially‘etched surface.
Dolomite etching is done best with dilute HCl than with acetic acid because
of greater speed of reaction. In the case of pure dolomite, there is little difference
between HCI and acetic acid etching results.
LAMAR (1950) mentioned that the etching results with citric acid are similar
to those of acetic acid, as are those of organic and carbonic acids. Oxalic, sulfuric,
and other acids that produce relatively insoluble reaction products with calcite or
dolomite, are usually undesirable for etching. PERCIVAL et al. (1963) have described
a technique for cleaning and etching the surface of carbonate rocks with hydrogen-
ion exchange resin which reveals details in texture and fossil morphology.
It cannot be emphasized too much that in many cases etched polished car-
bonate specimens are not sufficient to give genetic connotations to the components
present. To distinguish between faecal, bahamite and algal pellets, between autoch-
thonous and allochthonous micrite, and between genuine open-space sparite
cement and recrystallization sparite, to name only a few examples, thin-section
studies are a prerequisite.
EXAMINATION A N D ANALYSIS OF SEDIMENTARY CARBONATES 259

STAINING OF CARBONATE ROCKS A N D MINERALS

Staining has been used in carbonate petrography for the following six purposes.
( I ) Identification of minerals (e.g., FRIEDMAN, 1959; GRASENICK and GEY-
MEYER, 1962; WARNE, 1962).
(2) Identification of isomorphous series in combination with refractive-
index determinations (e.g., WALGER, 1961).
(3) Textural and structural studies of recent and ancient calcareous fossils,
carbonate rocks and soils (e.g., HEEGER, 1913; SABINS,1962; EVAMY, 1963).
(4) Petrogenetic investigations, e.g., diagenesis, paragenesis (e.g., SABINS,
1962; EVAMY,1963).
(5) Percentage determination (visual estimates or with point-counter).
(6) For illustration purposes, because stained grains are more distinct from
surrounding non-stained material in photomicrographs (e.g., SABINS, 1962;
EVAMY, 1963).
The staining procedures are applicable to 'the study of thin-sections with re-
moved cover-slides (as long as heating is not required), smoothly broken hand-
specimens, drilling chips, polished surfaces, and uncemented loose carbonate
material in the field, on well site, and in the laboratory. Certain methods have
advantages over others, and it is often left to the individual investigator to select
a technique most suitable for his purposes. In general, little skill and only a few
utensils are necessary to obtain satisfactory results.
Table I (WOLF,1963b) gives a number of staining reagents, procedures of
application, and results. The more pertinent references have been given which
should be consulted for details on staining of carbonates. A number of staining
methods have not been included in the table, e.g., techniques using malachite green
(HENBEST, 1931; HEDBERG, 1963) and methyl red (RAMSDEN,1954). One of the
tests for dolomite is based on the fact that this mineral usually contains some iron
in contrast to the calcite.
Inasmuch as most carbonate minerals can contain traces of iron, this test
may not be a safe one to employ in precise work. EVAMY (1963) proposed a scheme
which enables the discrimination between iron-free and iron-containing calcite
and dolomite on a semi-quantitative basis (Table 11).
Results of staining are most reliable in the case of mineralogic end-members.
As indicated in Fig.5, however, a number of isomorphous (solid-solution) replace-
ments are possible and caution is in order in the interpretation of staining results.
LEITMEIER and FEIGL(1 934) and GOTO(196 I , p.6 14) observed that minerals from
different localities react differently to staining probably because of varying degrees
of purity. Results also change with the optical orientation of the crystals. The reac-
tions, however, occur between certain limits and are still useful for gross identifi-
cations.
One of the major limitations of staining is its application to granular and
TABLE I

OUTLINE OF STAINING METHODS FOR CARBONATE MINERALS

(After WOLF,196313)

Chemicals Preparation and method Results Remarks

FeC13, (NH4)zS RODGERS (1940): use 1 part of Calcite = brown-black. The dolomite grains when smaller than
FeC13.6HzO and 10 parts of water Aragonite = brown-black. 0.01 mm become nearly black. Ankerite,
and immerse specimen not more than Dolomite = nearly colorless- magnesite, breunnerite, and siderite
1 min, then wash specimen gently pale green. when below 0.01 mm in size and
and dip it into (NH4)zS. slightly green (STRAKHOV, 1957).
STRAKHOV (1957) stated: in a Ankerite = nearly colorless-pale The disadvantage of this stain is
solution of 1 0 4 5 % of FeC13 moisten green. its tendency to spread over adjacent
the carbonate specimen 1-2 min, or Magnesite = colorless. grains; and it oxidizes, turning brown,
put a drop of the solution on the Breunnerite = greenish. cracks and crumbles. Also, the film is
specimen. Wash specimen with distilled (STRAKHOV, 1957.) easily washed off.
water and then treat it with a solution Brucite = pale green. (Somewhat If limonitic material is present
of (NH&S for a few seconds. Wash darker than dolomite; LEMBERG, in the rock, it will be changed to black
again with caution. 1888.) FeS by the (NH4)zS and will make
FRIEDMAN (1959): use 2.5% of Siderite = colorless. carbonate estimation difficult. If other
a FeCh solution (=2.5 g in 97.5 ml of black materials, e.g., carbonaceous
water); apply to the specimen for a components and magnetite, are present
few seconds. as impurities the stained carbonate is
difficult to estimate.
According to LEMBERG (1 888),
dolomite and calcite cannot be distin-
guished if they are very fine grained.
.~

AIzCls FAIRBANKS (1925): use 0.24 g of Calcite = violet or purple. LEMBERG (1888): use 4 parts of &CIs,
hematoxyline haematoxyline, 1.6 g of AlzCk and 24 Aragonite = violet or purple. 6 parts of logwood and 60 parts of
HZOZ ml of water. This solution is boiled Dolomite = colorless. water, and boil it under constant stirring
and then cooled. A small amount of Ankerite = colorless. for 20-30 min. The dark violet mixture
HZOZis then added to oxidize the Magnesite = colorless. is filtered and used as staining fluid.
haematoxyline to hematein. Immerse Breunnerite = colorless. STRAKHOV (1957), using the above
 carbonate specimen in solution. Siderite = colorless. method, diluted the solution with 1,OOO-
Brucite = colorless. 2,000 ml of water. He boiled the car-
bonate specimen for 5-10 min. On the
other hand, Lemberg did not dilute the
solution and did not boil the specimen.
Different logwood contain dif-
s2
?-

ferent amounts of haematoxyline and 5

hematein, and the stains formed ac- E;
cording to Lemberg’s method are not 2:
?-
uniform. Hence, Fairbanks’ preparation 2
method is preferable. U
?-
Disadvantages: (I) solution is 2:
unstable, (2) stain contracts and spalls
off, (3) stain rubs off easily, and (4) due
F*
to spalling it is not useful if carbonates
are very small.
~~
e
m
HENBEST (1931): use 2 parts of HCI, Dolomite = blue-dark blue The solution is unstable and gives m
88 parts of water and 10 parts of K3 if Fez+ is present (it is colorless off HCN (poisonous). E!
Fe(CN)e solution and immerse the if it lacks Fe). For relation between Fe content E
specimen for 30-70 sec. Better effects
are obtained by using more dilute
and rate of reaction and intensity of 2P
HCI and treating the specimen longer. Fe-dolomite = dark blue.
stain see HEEGER (1913) and EVAMY
(1963) (see below and Table 11).
*
0
HEDBERG (1963) in the study of Ankerite = dark blue. Certain clays also stain relatively easy- >
cores used the same solution, but
treated the samples for 5-60 min
Siderite = dark blue.
Calcite and magnesite stain if
sometimes easier than the carbonates.
Warne reported that ankerite and 6z
depending on composition. they contain Fez+. ferroan dolomite stain well in cold ?-
WARNE(1962): use solution of solutions, whereas dolomite generally ;;I
m
equal parts of 2 % HCI and 2 % K3 and siderite always require heating.
Fe(CN)6. Heating may be required On using cold and hot reagents, this
according to Warne in the case of test seems useful for the differentiation
siderite and dolomite. The former of ankerite and Fe-dolomite from
reacts rapidly, whereas it may take siderite and possibly dolomite.
5 min for the dolomite to stain.

ordinary According to STRAKHOV (1957), STRAKHOV’S (1957) results with The intensity of blue is related to the
photographic the above solution is best applied with photographic paper: amount of Fez+ present.
paper ordinary photographic paper. This calcite and dolomite gave no
TABLE I (continued)

Chemicals Preparation and method Results Remarks

ordinary paper is washed in hyposulphite color impression.

photographic causing it to turn dark. Then it is Ankerite = blue.
Paper soaked in 1 % 1 :20 HCI for a few Breunnerite = deep blue.
(continued) seconds to a minute. The paper is Siderite = deep blue.
pressed against the carbonate specimen
for 1-10 min. Then the paper is
soaked in a solution of KaFe(CN)g
followed by washing in water and
drying.

KaFe(CN)a EVAMY (1963): use the staining For results see Table 11. EVAMY’S (1963) method permits a rough
alizarin red S solution in combination with alizarin estimation of the amounts of Fe con-
HCI red S as shown in Table 11. The reagents tent in calcite and dolomite and the
can be employed independently or the recognition of ankerite.
alizarin red S and K3Fe(CN)e can be
combined in a single solution. The
solution is then acidified by 0.2 % HCI.

LEMLIERG (I 892): required are Calcite = red-orange-red-brown. The rate of staining of the less reactive
neutralsolutionsof 10”/.AgN03and20% carbonates, e.g., dolomite, depends on
. drops of former solution Aragonite = spotted red or un-
K ~ C r 0 4Put the grain size. STRAKHOV (1957) found
on the specimen, heat it to 60-70°C stained (see remarks). that large grains of dolomite remain
(others boil it), and maintain it for unstained, whereas those smaller than
2-5 min. Then wash the sample care- Dolomite = nearly colorless. 0.01 mm become brown.
.
fully and treat the specimen with Ankerite = nearly colorless. Aragonite from different locali-
K2CI-04 solution for a few seconds. Magnesite = nearly colorless. ties reacts differently according to
Wash again and let it dry. Breunnerite = nearly colorless. LEMBERC ( I 892). If the AgN03
FRIEDMAN (1959): immerse the Siderite = colorless. solution is too strong (greater than 273,
specimen for 2-3 min and use a According to Friedman: the reaction between aragonite and the
saturated K2CI-04 solution. Magnesite = brown. solution is too vigorous and no stain
THUGETT (1910) and STRAKHOVGypsum = brown. adheres to the surface; hence, apparent
(1957) suggest a 0.1 % AgN03 solu- Dolomite = colorless. unstained appearance. The reaction of
tion. According to LEMBERG aragonite is 1,800 times that of calcite
 If a very weak AgN03 (I .7 % = ( 1892) and THUGETT ( I9 10). (THUGETT,1910).
0.1 N)solution is used for 1 sec, strontianite, magnesite and dolo- LEMBERG (I 892) gives staining
aragonite stains red, witherite mite react only very slowly (see procedures for some non-carbonate RP
slightly red, and strontianite column to the left). minerals as well. 3
I

remains unaffected. z
~~ ~ ~~
______ . >
MnS04.7HzO In 100 ml of water dissolve Aragonite = grey. LEITMEIER and FEIGL (1934) give a
AgzS04 11.8 g of MnS04.7HzO. Add to the Strontianite = grey. table showing the reactions of numerous 2
NaOH solution solid AgzSO4 and boil. Witherite = grey. carbonates in time. Sequence of >
2
(Feigl’s solution) After cooling, filter the insol- Calcite, dolomite, reaction is as follows: U
uble material. Then add 1-2 magnesite, ankerite, (I) aragonite, strontianite, wither- >
z
drops of dilute NaOH solution, siderite, smithsonite, ite, (2) smithsonite; (3) cerussite, >
ankerite, (4) dolomite; (5) calcite; r
and filter off the precipitate and cerussite need
much longer time than the
$
after 1-2 h. Keep reagent (6) siderite; (7)crystalline E
in a brown bottle. Put specimen above three to stain. magnesite; and (8) pure gel magnesite.
into solution (powder, for Minerals from different localities r
A
3-5 min; sections, for 30-50 often react somewhat differently but
always within certain limits.
B
min). Instead of placing
the specimen into the solution,
it can be dabbed gently with 5>
some material soaked in the XI
Feigl’s solution.
<
c1
>
diphenylcarbazide A test-tube or some other container Magnesite = lilac. STRAKHOV (1 957) recommended a
procedure for the preparation of
E
0
alcohol is filled with about 15 cm3 of alcohol Breunnerite = rose. z
NaOH or KOH and 1-2 g of diphenylcarbazide is (STRAKHOV, 1957) stained thin-sections. >
dissolved by heating. Then add 3-5 mg = colorless (FEEL, 1958). Note slight apparent discrepancy 3
of NaOH or KOH (25 %). Add the Siderite = dark grey between the results of STRAKHOV (1957)
grain of carbonate to be examined and (STRAKHOV, 1957). and F E E L (1958). The latter stated
boil for 2-3 min. The solution is All other carbonates that magnesite can be distinguished
poured out and the specimen boiled remain unstained from both dolomite and breunnerite
with some water. The water is changed according to by this test. The reaction does not
until it remains uncolored. STRAKHOV (1957). take place “when the magnesium
FErGL (1958) recommended to According to FElGL carbonate is in the form of dolomite
place drops of hot solution on a spot (1958), magnesite be- which is usually regarded as a double
plate before adding the rock. After 5 comes red-violet. .
carbonate CaMg(CO3). .regarded as the
min the solution is pipetted out and When Mg is in dolomite complex CaMg(C0a)z. The magnesium h)
Q\
w
 h,
TABLE 1 (continued) m
P

Chemicals Preparation and method Results Remarks

diphenylcarbazide replaced by hot water. The washing combination (or in is thus a constituent of a complex
alcohol continues until the water remains breunnerite). no color anion, and therefore has lost its
NaOH or KOH clear. results. The Mg can normal reactivity. . .” Breunnerite
(continued) then be detected by is isomorphous with dolomite and
taking a fresh sample also gives no reaction for magnesium.
and igniting it on If dolomite and breunnerite are
platinum. The resulting ignited, the dolomitic linking is
sample can be stained as destroyed and Mg can be detected
described above. (See test with diphenylcarbazide, in the
using magneson.) resulting mixture of oxides. (See
magneson test.)

The powder of the carbonate is boiled Calcite = bright green. Large dolomite grains remain unstained,
for 2-3 min. in a solution of 5 % Aragonite = bright green. whereas those smaller than 0.01 mm
of Cu(N03)~.Thenthe solution is Dolomite = unstained or become pale green.
decanted and the specimen washed in pale green. See recommended procedure using
water (RODGERS, 1940; STRAKHOV, Ankerite = pale green. C~(N03)zPIUS NH40H.
1Y57.) Magnesite = pale blue.
Breunnerite = unstained.
Siderite = unstained.

The specimen is put for 5-6 h in a Calcite = blue-green.

solution of 5 % Cu(N03)~.The Aragonite = blue-green.
solution is removed and the According to Ross (1935):
specimen treated for a few seconds Mn-rich calcite = unstained.
with a solution of concentrated Siderite = unstained.
ammonia. Ankerite = unstained.
RODGERS (1 940) and Rhodochrosite = unstained.
FRIEDMAN (1959) recommended a Pure calcite = blue-green.
molar solution of Cu(NO3)z (= 188
of Cu(N03)z ,225 g of Cu(N03)z.
3Hz0 or 332 g of Cu(N0&.6HzO
 to 1,OOO g of water) into which
the carbonate specimen is immersed
for 2.5-6 hours depending on
intensity of stain desired, and then
treated with NHIOH (without
washing and before drying) for a
few seconds. (See also Ross, 1935;
and STRAKHOV, 1957.)

The carbonate specimen is boiled Calcite = unstained, or lilac- Coarsely crystalline calcite remains
for 5 4 min in a concentrated solution rose, or faint blue. unstained. Microcrystalline
Of cO(N03)z. Aragonite = dark violet. calcite becomes lilac-rose.
FRIEDMAN (1959): use 2 cm3 Dolomite, ankerite, After boiling for 10 min, the calcite
of 0.1 N Co(N03)~solution to which magnesite, breunnerite, and becomes light blue. LEITMEIER and
0.2 g of the sample is added, boil siderite remain unstained. FEEL(1934) stated that calcite stains
and filter. grey, green, yellow, or blue, but
LEITMEIER and FEIGL (1934, never violet when boiled for some time.
following Meigen): use a 5-10% Some contradictions have been
Co(N03)~solution and boil reported. (See FRIEDMAN, 1959.)
specimen 1-5 min depending on Boiling time may be critical.
grain size. Not useful for staining thin-
sections as boiling is required.
LEITMEIER and FEIGL (1934)
reported spreading of stain over
adjacent grains.
~~ ~ .~

eosin Fill test tube half full with alcohol Calcite = unstained.
KOH (about 15 ml) and dissolve 1-2 g Aragonite = unstained.
of eosin by heating. Add about 3 mg Dolomite = unstained.
of 25 % KOH. The carbonate speci- Ankerite = unstained.
men is placed into the solution and Magnesite = faint rose.
boiled for about 2 min. Then the Breunnerite = pale rose.
solution is decanted and the specimen Siderite = faint rose.+
washed with water (STRAKHOV, 1957).
(Eosin = red tetrabromofluorescein)
TABLE I (continued)

Chemicals Preparation and method Results Remarks

magneson WARNE(1962): prepare the reagent Magnesite = blue. The stain is unstable and disappears
NaOH and HCI by using 0.5 g of magneson (= para- Smithsonite = unstained rapidly.
nitrobenzene-azoresorcinal) added to or shows faint tint to blue after Dolomite and breunnerite
100 ml of 0.25 N (= 1 %) NaOH. 5 min. do not stain in the alkaline solution
The HCl-etched and washed specimen Calcite may stain if because the Mg forms a complex ion
is covered with equal amounts of immersed too long. and is not available for the reaction
reagent and 30 % cold NaOH Dolomite = unstained with the dye (FEIGL,1958, p.465).
solution. Breunnerite = unstained. If dolomite is ignited in a platinum
MANN(1955): suggested to According to MANN(1959, crucible, the dolomite linking is
drop some dilute HCl on the MgO is present if the drop destroyed and MgO is formed.
specimen; and when all efferves- turns blue in about 30 sec. MgO reacts with the dye. If HCI acid
cence has ceased, a drop of the is put on the dolomite prior to adding
alkaline magneson solhtion is intro- the alkaline magneson solution, the Mg
duced into the earlier drop. (See is precipitated and allows the
a h 0 STRAKHOV, 1957.) magneson to become attached to it
and color it. This latter test does not
show whether the Mg comes from a
dolomite or magnesite, for example.
methylviolet Two possible procedures are
(violet writing ink) proposed by STRAKHOV(1957):
(I) To an ordinary violet (1) The spot on the calcite m
writing ink (methylviolet) add a small.
amount of HCl, causing a change to
turns immediately violet; on the
dolomite the spot remains green
5
0
2:
green color. If one drop of that solution for some time.
is put on calcite or dolomite, the
acid is more rapidly neutralized by
calcite than dolomite.
(2) Oxidize the methylviolet (2) Calcite = violet. The dolomite crystals less than
with 5 % HCl until an intense blue Aragonite = violet. 0.01 mm in size become pale violet.
color is obtained. Soak the carbonate Dolomite = unstained or pale
specimen in the solution (or put a violet.
 layer of the solution on the specimen)
and leave it there for 1.5-2 min. z
Apply carefully a blotting paper. 2
2;
alizarin red S Dissolve 0.1 g of alizarin red S in Calcite, aragonite, high-Mg WARNE(1962) reported that no staining
5
2
2 % HCI 100 cm3 0.2 % cold HCl(0.2 % HCl = calcite, and witherite = deep red. occurred when reagent was applied for +
2 cm3 of concentrated HCI plus 998 ml Ankerite, strontianite, 5 min. Prolonged staining produced z
U
of water). The specimen to be tested Fe-dolomite, and cerussite = slightly purplish surface on the >
is first etched in 8-10 % HCI (see purple. dolomite. z
WARNE,1962, p.34) and then covered
with the cold alizarin red S solution
Anhydrite, siderite,
dolomite, rhodochrosite,
According to SCHWARTZ (1929)
staining is successful with carbonates EE
and allowed to react for about 2-5 magnesite, gypsum, and with grain-size of 0.5-1.5 mm.
mill. SCHWARTZ (1929), FEIGL smithsonite = no color. Below this size distinction becomes 8
(1958), FRIEDMAN (1959), and difficult due to spreading of the stain. vl

WARNE(1962). F;
alizarin red S
30% NaOH
Use equal volumes of alizarin red S
and 30 % NaOH solutions (30 %
Calcite = no stain.
High-Mg calcite = purple.
Etch the specimen first in 10% HCl
(WARNE,1962, p.34).
3
>
NaOH = 30 g of NaOH plus 70 ml of Dolomite = purple. HENBEST (1931): use KOH *
w
water). Add specimens to be tested Magnesite = purple. instead of NaOH (1 part KOH to 119 0
and boil for 5 min. Gypsum = purple. parts of water in which the maximum >
Alizarin red S solution is pre-
pared by dissolving 0.2 g of the dye in
Anhydrite = no stain.
Witherite = no stain.
amount of alizarin red S is dissolved).
Alizarin red S at 26°C has a
ti2
25 ml methanol, by heating if Siderite = dark brown-black. solubility of 7.6 % in water. 2
necessary (FRIEDMAN, 1959). Replenish Rhodochrosite = purple. vl

any methanol lost by evaporation. Smithsonite = purple.

Aokerite = dark purple.
Cerussite = dark red-brown.
Strontianite = no stain.

alizarin red S Use equal volumes of alizarin red S Dolomite = unstained or faint
5 % NaOH and 5 % NaOH solution and boil color.
therein for about 5 min. Etch specimen Rhodochrosite = unstained or
first in 10% HCI. (See WARNE, faint color.
1962, p.34; and FRIEDMAN, 1959.) Magnesite = purple.
Gypsum = purple.
Smithsonite = purple.
-
 s
h,
TABLE I (continued)

Chemicals Preparaiion and method Results Remarks

titan yellow Boil carbonate s w i m e n to be Calcite = unstained.

30% NaOH tested in solution of titan yellow Aragonite = unstained.
and 30% NaOH (FRIEDMAN, 1959). Anhydrite = unstained.
High-Mg calcite = orange-red.
Dolomite = orange-red.
Gypsum = orange-red.
Magnesite = orangered.

titan yellow Boil specimen in solution of titan High-Mg calcite = orange-red. High-Mg calcite studied by Friedman
5 % NaOH yellow and 5 % NaOH (FRIEDMAN, Gypsum = orange-red. (1959) was very fine grained. Degree of
1959). Magnesite = orangered. coloration of the high-Mg calcite
Dolomite = unstained. apparently depends on the amount of
Mg present (FRIEDMAN, 1959).
.. --- - -- - x
sl
T
x
Hams’ Harris’ hematoxylin can be purchased Calcite = purple. The more frequently the solution i s
hematoxylin commercially or can be. prepared as
described by FRIEDMAN (1959).
High-Mg calcite = purple.
Aragonite = purple.
used, the quicker the stain takes effect.
A fresh solution will often require 3
Solution is made up of 50 ml commer- Magnesite = no stain. 9-10 min to stain, whereas a frequently &!.
cia1 grade Harris’hematoxylin and 3 ml Gypsum = no stain. used solution may need only 3 min or ?
10% HCI. 3-10 min are required Anhydrite = no stain or less (FRIEDMAN, 1959). 2
to stain specimen. faintly orange. m
Dolomite = no stain. %
4

5
rhodizonic Dissolve 2 g of disodium Witherite = orange-red. T h e spot test proposed (FEIGL,1958,
acid rhodizonate in 100 ml of distilled Calcite = no stain. p.220) utilizing sodium rhodizonatc, can
water. The specimen to be tested is detcct strontium in very small v1
etched in dilute HCI and washed quantities.
several times in distilled water. The I
>
a
specimen is then submerged in the
reagent for 5 min (FEIGL,1958; z
WARNE,1962).
benzidine Dissolve 2 g of pure benzidine Rhodochrosite = blue stain See FEEL(1958, pp. 175 and 416)
in 100 ml of water which contains (almost immediately). for spot test using benzidine. (The rn
1 ml of 10 N HCI. The HC1-etched Dolomite = not stained. production of benzidine has been x
specimen is washed several times, after discontinued by some companies $
which the specimen is immersed in a because of the cancer risks involved 2
dilute solution (1-3 %) of NaOH for
about 1.5 min. Then it is covered
in the preparation of the pure material.)
$z
with cold benzidine solution
(WARNE.1962). 5U
270 K. H. WOLF, A. J. EASTON AND S. WARNE

crystalline carbonates of which the individual particles are larger than about 0.01
mm. STRAKHOV (1957) found that below this grain size some staining procedures
lead to results that differ from those obtained on using coarser material.
Some staining methods depend on the rate of solution of the carbonate in
acid, e.g., difference between aragonite and calcite (FRIEDMAN, 1959), and between
calcite and dolomite. In the latter case, very finely powdered dolomite forms
C02 rapidly and, therefore, may be confused with calcite (HEEGER, 1913).
A few of the staining reagents spread readily over neighboring particles and
make identification and percentage determinations difficult. Hence, it may be
necessary to modify the manner of application of the reagents. For example,
gentle dabbing of the specimen with a cloth soaked in the reagent, or pressing the
specimen against a reagent-wetted blotting paper may give satisfactory results. A
similar approach may be required to prevent staining fluids from penetrating into
openings in the case of porous carbonate rocks.
As has been illustrated by FRIEDMAN (1 959) and WARNE (1962), a few of the
staining techniques listed in Table I can be used to identify most of the major
carbonate minerals by a progressive elimination scheme shown in Fig.2 and 3.
The other methods are given for those who wish to experiment with different
techniques and for the purpose of double-checking a mineral identification.
Further research on the applicability of staining for semi-quantitative deter-
minations of isomorphous minerals and minor element-containing carbonate
minerals, possibly in combination with spot tests, may improve and expand the
methods available at present.

I
Alizorln red S
t3OXNoOH boll

ANHYORITE SIDERITE ANKERITE STRONTNNITE CERUSSITE

HIGH-Mg
CALCITE

[ree=,
CALCITE WITTHERITE DOLOMITE RHOOO- MAGNESITE WITHSONITE
CHRO- or
SITE GYPSUM

Fig.2. Staining scheme for the identification of carbonate minerals employing alizarin red S;
(After WARNE,1962b, by permission of the Journal of Sedimentary Petrology.) I = or faint stain.
TABLE I1 m
x

STAINING METHOD OF CALCITE, DOLQMITE AND ANKERITE, CONSIDERING Fe-CONTENT

(After EVAMY,
1963)
_
Staining reagents Calcite Dolomite gU
__

Compositions are given Fez+ Fez+ Fez+ Fez+

5
Fez+ Fez+
in weight percent. MT+<' Mg2+'1
Critical solution strengths are underlined. free. poor rich free
--
E
calcite ferroan ferroan dolomite ferroan ankerite
s. str. calcite calcite s. str. dolomite

0.2 % hydrochloric acid

_ ~ . ~ _ _ _
red red red not not not
stained stained stained
~

0.2% alizarin.red S

0.2 % hydrochloric acid

-~
not light dark not light dark
0.5-1 .O % potassium ferricyanide stained blue blue stained blue blue

0.2 % hydrochloric acid red mauve purple not light dark

0.2% alizarin red S stained blue blue
0.5-1 .O% potassium ferricyanide
272 K. H. WOLF, A. J. EASTON AND S. WARNE

mrellow’l
30% Na?H + boic

ANHYDRITE
Fei I’J solution

HIGH-Mg GYZ$JM
CALCITE ARAGONITE
CALCITE MAGNESITE

Fig.3. Staining scheme using titan yellow. (After FRIEDMAN, 1959, by permission of the Journal qf
Sedimentary Petrology). I = see FRIEDMAN (1959) for other excellent stains; 2 = or faint stain
(light orange); 3 = high-magnesiumcalcite used in this study was very fine grained. The behavior
of coarse-grained high-magnesium calcite was not studied.

PEEL TECHNIQUES

Peel prints have been used to facilitate the examination of both well-lithified
and unconsolidated carbonate and terrigenous sediments with or without
additional staining. Peels may be useful also in the study of metamorphic and
igneous rock fabrics as mentioned by BISSELL(1 957). It seems that peels have not
been applied to the best advantage in structural analyses. As Bissell and HEEZEN
and JOHNSON(1 962) pointed out, peels can be made even from outcrops.
The following procedure is based essentially on that described by MCCRONE
(1963) with minor alterations and additions.
(I) Prepare a polished flat rock section; polish with fine abrasive on a flat
glass plate in the final stage. Different grades of abrasive have been suggested
ranging from 400-1,000. Abrasive 600 seems to give satisfactory results.
(2) Etch the polished surface with dilute hydrochloric or acetic acid, or a
mixture of the two, to obtain optimum results as suggested in the section on
etching. Experiments soon will reveal the best combinations of acid types, strength
and application time. McCrone suggested dilute (1 %) hydrochloric acid applied
for 10 sec. This time may be too short, in particular in the case of dolomites,
and the time may be prolonged accordingly. McCrone stated that dilute acetic
acid precipitates “faint films of indefinite composition” which tend to cloud the
peel-prints, and that this precipitate is difficult to remove without obliterating some
of the fine details of the textures. It has been shown in the section on etching,
however, that the precipitated salt (e.g., calcium chloride) can be easily dissolved
EXAMINATION A N D ANALYSIS OF SEDIMENTARY CARBONATES 273

by immersing the specimen for a few hours in several changes of water or by a

quick rinse in very dilute HCI (LAMAR,1950).
BEALES(1960) suggested a “standard” of 5 % v/v hydrochloric or 5 % v/v
acetic acid applied to limestones for I5 sec or 5 min, respectiveIy. The time should
be changed according to needs. For immersion over-night, 0.5% acetic acid or
very dilute HCI give good results.
(3) After etching, wash the specimen with water and then with alcohol or
acetone without touching and leaving “finger prints” on the etched surface. If
acetic acid has been used, remove any precipitate as mentioned in 2 above (see
also the section on etching).
( 4 ) Place the rock specimen, with polished surface up, horizontally into a
tray, pan or dish filled with coarse sand. The latter will hold the specimen in place
and absorb the spilled acetone.
(5) Have ready a piece of single-matte commercial acetate film (0.005-inch
thick) slightly larger than the polished rock surface. (D. W. LANE,1962, used film
0.002-0.003-inch thick.)
(6) Wet the polished surface with acetone by pouring a small amount from
the bottle without flooding the specimen. (For other peel solutions see BUEHLER,
1948; and BISSELL,1957.)
(7) Hold the acetate film between thumb and forefinger so that it forms a
U-shape. Apply the dull side of the film to the rock so that the base of the “U” is
first to touch the acetone-wet surface near the center. By letting the film unroll onto
the polished section, no bubbles will be trapped. Do not press the film against the
rock to prevent smearing and breaking of delicate textural features. BEALES(1960)
and others suggested to place the turned-over specimen on a smooth surface. An
alternative method is to place the acetate film on a glass plate, adding a little
acetone near the center of the film and lowering the specimen onto it. In any case,
one should avoid sliding the specimen on the film.
(8) Allow the film to dry for 15 min or longer. Then, starting at one corner,
gently peel it from the rock.
(9) Mount the peel between two pieces of lantern-slide glass and bind them
with tape. The mounted peel can then be used in a photographic enlarger to make
enlarged peel prints on high-contrast paper. Mounted peels can be used also as
lantern slides for projection on a screen, or for direct examination under a micro-
scope (MCCRONE, 1963).
To obtain photomicrographs, HARBAUGH (1959) projected the “peels in a
standard photographic enlarger onto high-contrast photographic printing paper,
such as Kodabromide F-5. The enlarger lens aperture was stopped down to about
f / l l to give sufficient depth of field to insure sharp focus. Negative peel prints
produced in this way have proved more convenient to use than peels themselves
because the prints provide several magnifications and several prints may be easily
viewed and compared simultaneously.” Equally well this technique may be used
274 K. H. WOLF, A. J. EASTON AND S. WARNE

with thin-sections. To obtain positive prints, one may project onto a cut film or
negative glass slide (e.g., quarter plate size) and then contact print.
As the peel picks up minute specks of the rock surface, some peels accurately
record color as well as the texture. In some cases it may be desirable to emphasize
certain textures, minerals or fossils by staining before the peel is taken. BISSELL
(1957) stated that it may be profitable to make stained peels of varying thickness,
depth of color, and intensity of fabric.
It is evident that minerals cannot be identified in peels by optical means.
Euhedral minerals, however, are recognizable in some cases by their crystal habit.
In one instance (WOLF,1963a), peels showed clear hexagonal features of minute
authigenic quartz crystals in algal limestones, and cubic outlines of pyrite.
A peel technique for unconsolidated sediments has been described by
HEEZEN and JOHNSON(1961), which has to be applied soon after the sediments have
been obtained and prior to dessication and shrinkage obliterates many features.
Experiments with a number of glues and plastics indicate that polyvinyl emulsion
is the best suited, in particular because it can be diluted with water to decrease its
viscosity, and inasmuch as it dries clear. Depending on the type of sediments,
different proportions of plastic and solvent are necessary.
The advantages of peels are numerous: (I) little skill, time, equipment and
expense is required in their preparation with easily available material; (2) they can
be easily filed and projected onto a screen; (3) peels are easier to photograph than
polished sections as transmitted light is utilized; (4) peels can be made under
circumstances where equipment necessary for the preparation of thin sections is
unavailable; (5) examination of peels helps in selecting critical areas that demand
thin-section studies; and (6) peels can be made of very large polished sections, in
contrast to the limited size of thin sections,.which makes them particularly advan-
tageous in textural and structural studies.

SEPARATION OF INSOLUBLES

The reasons for separating non-carbonate and carbonate components include the
following.
(I) To determine the two- or three-dimensional distribution of the non-
carbonate fraction in the carbonate rock, thus permitting the petrographic and
petrologic examination of syngenetic and authigenetic as well as diagenetic mineral
distribution.
(2) To investigate the different minerals of the non-carbonate fraction
(e.g., clays, organic matter, glauconite, heavy minerals, and so forth).
(3) To investigate more easily the remaining carbonate fraction.
One of the most difficult tasks is to achieve separation without causing com-
positional alterations of the so-called “insoluble” residue. Progress in some
EXAMINATION AND ANALYSIS OF SEDIMENTARY CARBONATES 275

fields of carbonate petrology may well depend on the development of new separation
techniques. This is particularly the case in trace-element and isotope studies of the
carbonate versus the non-carbonate constituents. Certain techniques have been
proposed that allow separation of the “insolubles” with a minimum destruction
and which were sufficiently satisfactory in the particular types of investigations.
Acetic acid, for example, is thought to be useful in clay-mineral separation without
destroying the mineral structure (as determined by X-ray diffraction analysis).
Little published information, however, is available on the effects of the organic
and other inorganic acids and ion-exchange resins on the trace elements. In gener-
al, the term “insoluble” residue is somewhat misleading as most substances are
soluble, however small the solubility may be.
A useful technique that has the advantage in that non-carbonate components
can be observed in their original position and may be removed for further study
has been mentioned by LEE(1958) and HEDBERG (1963). The procedure is given
below.
( I ) Prepare a thin rock slice. Orientation depends on the information de-
sired, of course. Usually sections vertical to the bedding are used. In three-dimen-
sional investigations, however, sections parallel to the bedding are often required.
(2) The rock slice is ground and polished smooth on the side to be mounted.
(3) The slice is immersed in 20% acetic acid for approximately 5 min and
subsequently thoroughly washed and dried.
( 4 ) The prepared side is mounted with a resin as mountant on a glass slide.
Lakeside No.70C, for example, is useful, whereas Canada Balsam mounts are less
successful.
(5) The rock.slice is ground down to approximately 0.030 mm, and the final
stage is done with the finest abrasive.
(6) The whole section is then placed in 20% acetic acid and the carbonate
completely dissolved away.
The non-calcitic carbonates can be easily examined or removed for refrac-
tive-index determinations. Non-carbonate minerals can be examined by normal
means after the surface has been moistened with water. If all carbonate minerals
are to be removed, the above procedure is performed with dilute or concentrated
hydrochloric acid.
Etching prior to mounting has been done with acetic acid to produce differ-
ential etching. The “acid-polish”, or smooth surface produced by hydrochloric
acid, is undesirable. The differentially attacked limestone surface permits the resin
to penetrate into the slice when mounted. Thus, after complete digestion of the
carbonate material, the texture of the original rock is preserved on the resin. This
replica is best examined on a dry mount using reflected light or transmitted light
and crossed nicols. Minute details, down to the size of calcisiltite, are observable
in the replica.
HEDBERG (1963) used a slightly modified version of Lee’s technique. In-
276 K. H. WOLF, A. J. EASTON AND S. WARNE

stead of etching the sample prior to mounting, the rock slice is highly polished as in
the preparation of thin-sections and mounted with Lakeside 70 on a glass slide.
Heat is then applied to the mountant with a Bunsen burner to a temperature just
below the point at which the Lakeside becomes very fluid. If this is done for
about 1 min, the fluid will penetrate and bind the clay and other minerals but will
affect only slightly the calcareous material. If heating is prolonged to 5 min, much
of the calcareous constituents will be bonded, in addition to bonding of the non-
carbonate components. After mounting, the carbonate material is dissolved in 20 %
acetic acid, or dilute to concentrated hydrochloric acid (depending on factors men-
tioned above). By using this procedure, i.e., mounting an unetched surface, the
calcareous features are subdued and mainly the textures and structures due to
clay and other insolubles are visible.
TheLee-Hedberg technique has been used with success in the study of traces
of insoluble material in stromatolites, irregular algal Spongiostromata, and in the
investigation of non-carbonate components within internal sediments versus those
of the reef-limestone framework (WOLF,1963a).
In the methods advocated above, the acid reactions with clay may alter the
latter and one should be circumspect in the interpretation of the exact clay mineral-
ogy. Techniques for the separation of clays with a minimum destruction or altera-
tion are given below.
It has been customary to separate clay minerals from the carbonate rocks by
acid digestion. Acids react with clays, however, and a number of methods have
been proposed to minimize destruction. According to GRIM(1953, p.296), the
reaction of clay minerals with acids varies with: (I) nature of acid $2) concentration
of acids; (3) acid/clay ratio; ( 4 ) temperature; (5) duration of treatment; (6) group
of clay minerals (e.g., montmorillonite is more sensitive than illite or kaolinite);
(7) type of clay mineral within a group (e.g., Mg-rich montmorillonite is more
soluble in acid than Al-rich ones, whereas Fe-containing types are intermediate in
sensitivity to acids); (8) degree of crystallinity; and (9) particle size.
ROBBINS and KELLER (1952) made experiments on montmorillonite to check
the effects of HCl acid on that mineral. They reported that 57.1 % of the original
montmorillonite sample dissolved in 6 N HCI in 96 h. LLOYD(1954) used a cation
exchange resin and I /10 N HCI for the separation of clay minerals from limestones.
The use of the resin resulted in three times as much clay in contrast to the samples
that were digested in hydrochloric acid.
RAYet a]. (1957) stated that strong acids dissolved also some of the hydrated
micas, and ferri-ferrous chlorites, in addition to some members of the mont-
morillonite family such as hectorite. Their experiments on hectorite indicated that
the use of both HCI and formic acids for extracting acid-sensitive clay minerals
from carbonate rocks is restricted to room temperature and a p H no lower than
2. The reactions are slow under these conditions, especially for dolomite. The resin
Amberlite IRC-50, however, can be employed at higher temperatures and the
EXAMINATION A N D ANALYSIS OF SEDIMENTARY CARBONATES 277

reaction times are favorable as far as limestones are concerned and are even faster
for dolomite. Acetic acid seems to be as effective as the resin for calcitic material
but less so for dolomite, because of the very slow rate of dissolving of this mineral.
The cation exchange resins cause solution of the carbonate in a very weakly
acidic solution of relatively high pH. Amberlite IRC-50 when ionized is in the
form of COO-, and when non-ionized is in the form of COOH, and derives its
exchange activity from carboxylic acid. The Amberlite’s hydrogen form in dis-
tilled water gives rise to a pH of 6 or a H3O+ concentration of about 10-6 molar.
This is equivalent to a Haof concentration of about 9 * 10-3 molar for a 4.4
molar solution of acetic acid (1:3 by volume); about 3.3 * 10-2 molar for a 6
molar solution of formic acid (1 :3 by volume); and about 3 molar for a 1 :3 solution
of HCl, all at room temperature (RAYet al., 1957). As the H30+ concentration is
the major parameter controlling the rate of reaction of the various acid solutions
with the clay minerals, it is significant to note the low hydronium concentration on
using the resin. It is a million times smaller than that of hydrochloric acid solutions.
OSTROM (1961) found that “. . . expansible minerals, or those with expansible
constituents, are the most susceptible to acid reaction. No reaction was apparent
from X-ray diffraction curves between nonexpansible clay minerals and acetic
acid solutions of 16.6 A4 and HCI solutions of 10 M concentrations for 72 h.”
(For precise data of the experiments see Ostrom’s original paper.) Ostrom recom-
mended the following method for the separation of clay minerals from carbonate
rocks utilizing weak HC1 or acetic acid.
(I) Remove possible adhering foreign particles by washing and scrubbing
(or using an ultrasonic vibrator) approximately 150 g in distilled water.
(2) The sample is allowed to dry.
(3) Crush the sample to pass a 60-mesh sieve.
( 4 ) Place a small amount of the crushed material (less than 10 g) in a 100ml
of 0.5 Macetic acid. If a reaction is noticeable, the sample consists of calcite with
or without an admixture of dolomite and the procedure given below is followed.
If no reaction is apparent, the sample probably consists of dolomite (or some other
carbonate). The same procedure is used except that a HCI solution of less than 0.1 1
M concentration is utilized.
(5) The unused minus 60-mesh material is mixed with 100 ml of distilled
water in a 1,500-ml beaker.
(6) Add 1,000 ml of acetlc acid of less than 0.3 M concentration.
(7) Stir periodically until reaction ceases; reaction may last up to several days.
(8) Separate impotent liquid from solid residue by filtering or decanting.
(9) Additional acid is added and the process repeated until &#inch very
fine material covers the undissolved limestone after settling. This material consists
of clays and other insolubles. N.B. During the foregoing steps undissolved lime-
stone should be present at all times to minimize clay alteration.
(10) Separate clay by mixing the solids with 300 ml of distilled water. After
278 K. H. WOLF, A. J. EASTON AND S . WARNE

2 min settling period, decant the mixture into a 1,500-ml collecting beaker.
(11) Repeat process until liquid decanted is essentially clear.
(12) The solids in the 1,500-ml beaker are washed by decanting or filtering
off the supernatant liquid until the fine-grained solids are thoroughly dispersed.
(13) Permit the suspension to settle for 2 h before preparing oriented ag-
gregates of the less than 2 mp clay mineral fraction.
(14) Use eye dropper to transfer dispersed clay to glass slides.
It seems that if precise investigations are to be made, e.g., on trace elements.
a slight modification of the above procedure may be advantageous. Instead of
waiting until the reaction ceases (7), the insoluble material could be removed from
the beaker every few hours to minimize the time of exposure of the clays to the
acid.
BISQUEand LEMISH (1958) used the following approach to minimize damage
of the clay structure as determined by X-ray diffraction: “50 g of finely powdered
rock (passing No.100 sieve), 50 ml of dispersing agent (prepared by dissolving 40
g of sodium metasilicate-NazSiOa.9H~O and 7 g of sodium carbonate-NazCOa
in water and diluting the solution to 1 I), and several hundred milliliters of dis-
tilled water were agitated for 5 min in a mechanical laboratory stirrer. This sus-
pension was then transferred into a 1,000-mlgraduated cylinder and more water was
added. The system was again tlioroughly agitated with a mixing plunger and allowed
to stand for 7 h at room temperature. A 50-ml aliquot was centrifuged for 15 min
at 2,500 r.p.m. and the supernatant decanted, leaving a heavy slurry clinging to the
bottom of the bottle. Of distilled water 10 ml were added and the slurry stirred
into suspension. Exactly 4 ml of the resulting suspension were drained onto a 25
x 46 mm glass slide which was previously placed in an oven pre-heated to 60 “C.
After several hours the dry slide is found to be covered with a uniform coating
suitable for X-ray diffractometer investigation”. J. Lemish stated (personal
communication, 1964) that “the method is effective and sensitive to detection of
clay in carbonate rock. In experiments on mixtures of clay and pulverized lime-
stone, the method has proven to be sensitive to 0.1 % clay. On natural rocks the
flotation method is at best roughly semi-quantitative or relatively comparative if
care is taken to standardize the method; the method is effective for the qualitative
determination of clays in the carbonate fraction”.
PETERSON (1961) extracted clays from carbonates “. . . by leaching the finely
ground specimen. at room temperature in a solution of acetic acid buffered at
pH of 4.5 with lithium acetate.” Dolomite takes up to 1 day to dissolve at this pH,
whereas calcite leaches much faster. “Li+ was chosen because it would be one of the
ions least likely to replace other ions already in the clay structure (GEDROIZ, 1922:
GRIM,1953, p.147). During the leaching process, Ca2+ and Mg2+ ions are also
produced. To keep the concentration of these ions low, a large excess of leaching
solution was used. The solution was well buffered and change in acidity was less
than 0.5 p H unit during the digestion of a specimen.”
EXAMINATION AND ANALYSIS OF SEDIMENTARY CARBONATES 279

Investigations of trace elements of both the carbonate and non-carbonate

fractions depend, as in the case of clay minerals, on separation procedures that
permit a minimum of contamination. HIRSTand NICHOLLS (1958) carried out
experiments which showed, in agreement with the results of others quoted above,
that HCI attacks the clay minerals considerably whereas the effects of acetic acid
are less severe. The amounts of trace elements determined from the carbonate
fraction were constantly less when acetic acid was employed in the digestion as
contrasted to HCI. Although it is clear that the acetic acid is more effective than
HCI acid in separating procedures, the possibility still exists that minor changes
in trace elements are caused by acetic acid.
MCCREA(1950) presented a method of preparing carbonate rocks crushed
to 200 mesh for l*O/l60 isotope analysis by using phosphoric acid. DEGENSand
EPSTEIN(1962) in their study of isotopes in coexisting carbonates, cherts, and
diatomites, used phosphoric acid to obtain a separation of the carbonate from the
non-carbonate constituents. Where small amounts of carbonate still adhered to the
chert, they were removed by treatment with 2ni HCI for approximately 5-10 min.
This HCI treatment did not affect the 1 8 0 / 1 6 0 ratio of the chert as demonstrated
experimentally.
HUNTand JAMIESON (1956) described a method for the extraction of organic
matter from samples that have been crushed to a particle size of about 15 p.
MCIVER(1962) increased the efficiency of this extraction method by using an ultra-
sonic processing tank.

OPTICAL IDENTIFICATION OF CARBONATE MINERALS

Information on the optical and physical properties of the carbonate minerals

are to be found in numerous text and reference books such as those by WINCHELL
(1956), STRAKHOV (1957), BERRYand MASON(1959), MOOREHOUSE (1959), and
DEERet al. (1962). No duplication of this readily available material is required
here, therefore, except for some data on the relationship between the refractive
index and chemical composition.
The carbonate minerals are notoriously difficult to identify in thin-sections
with a petrographic microscope. A number of methods have been proposed, how-
ever, that facilitate the determination of the approximate chemical composition
of these minerals. They are mainly based on the determination of the refractive
index from mineral grains by the oil-immersion method or in thin-section with the
use of the universal stage. As the refractive index of different isomorphous carbon-
ate series overlap, staining, spot tests, or chromatographic methods (RITCHIE,
1964) may be required to determine the particular mineral.
When a powder of rhombohedral carbonate minerals is examined, most of
the crystal fragments will rest on the prominent rhombohedral cleavage (1011).
The no can be measured from any grain. The cleavage fragments resting on (loil),
280 K. H. WOLF, A. J. EASTON A N D S. WARNE

1.56 1.58 1.60 1.62 1.64

-na'(ioii) - 1.66 1.68 1.70 1.72 1.74 1.76

Fig.4. Chart for determining nc for the trigonal (rhombohedral)carbonates, provided no and ne'
are known. (After LOUPEKINE, 1947, by permission of The American Mineralogist. See also BLOSS,
1961.)

however, will only give ne' (symbolized ne'cloil,). Once no and ne' have been meas-
ured, n e can be determined from Fig.4 (LOUPEKINE, 1947; BLOSS, 1961, p.140).
The values obtainable from this figure are reported to be accurate to within f
0.004. If a correction factor is applied, as discussed by LOUPEKINE(1947), this error
is theoretically reduced to k 0.001. Knowing the refractive indices, and establish-
ing the isomorphous series present, the approximate composition of the crystal-
line carbonate minerals can be determined from Fig.5, which in this case utilizes
EXAMINATION AND ANALYSIS OF SEDIMENTARY CARBONATES 28 1

Mol. per c e n t

Fig.5. Variation of no with composition in the trigonal carbonates. (Mainly after DEER
et al., 1962,
and TR&ER,1959. Modified after KENNEDY, 1947, by permission of The American Mineralogist.)

no. In the publications listed above other tables and diagrams using both ne and no
are available.
USDOWSKI (1963, p. 100) used the immersion method for the determination
of ankerite and obtained no values of 1.717-1.726. From this he concluded that the
composition should be C ~ M ~ O . ~ ~ F ~ O . ~ toZ CaMg0.52(C03)~.
(CO~)Z Chemical
analysis of some of the ankerite indicated satisfactory agreement with the optically
determined compositions.
282 K. H. WOLF, A. J. EASTON AND S. WARNE

GRUSS(1958) used the immersion method successfully in establishing various

compositions of Mn-, Fe-, Ca-, and Mg-carbonate minerals (GRUSS,1958, fig.8, 12,
23) formed by the replacement of limestones. Gruss showed, for example, that
echinoid and mollusk fragments have ne values ranging from 1.658 (=calcite)
to 1.78 (=rhodochrosite and possibly siderite). To determine the mode and rate
of replacement, he performed experiments in which he succeeded in replacing
the Ca in calcite by Mn. Determining the refractive indices, Gruss found a meas-
urable progressive increase of Mn content until no further change occurred at
70% MnC03.
BURGER (1963) also used the immersion method in determining the refractive
indices and from them the composition of the carbonate minerals. He was able
to plot, for instance, changes of Mn content related to the location of ore deposits.
He found, however, that the compositions determined by this method are only
approximate.
The recognition of the carbonate minerals in thin-sections is considerably
facilitated by utilizing a universal stage. WALGER(1961) used the so-called
Schumann method (SCHUMANN, 1948), or a modification thereof. This method is
based on the size and shape of the indicatrices of the trigonal (rhombohedra])
carbonates. Measurements are taken of the angle between the optical axis and
the normal of the direction within the indicatrix where ne’ = nr (no> nr > ne,
where ni is the refractive index of the mounting medium; Fig.6). This angle of
rotation is measured with the universal stage in the following manner: (I) A4 is in
E-W position; Az=OZ; A3=0”. (2) Polarizer is in N-S position. (3) Analyzer and
Bertrand lens inserted. (4) Turn about A1 until N-S isogyre coincides with N-S
line of cross-hair. A principal section is parallel to A4. ( 5 ) Tilt about A4 until
melatop coincides with center of cross-hair. Read [*. (6) Remove analyzer and
Bertrand-lens. (7) Tilt about A4 in opposite direction until the Becke line and
relief disappears, then ne’ = na. Read i*.(8) [* and *; are corrected according to
Snell’s law to obtain [ and 2.(The correction of S* is not required if the segment
measured is close to na.) (9) 5 and 2 = Po. (10) Use Fig.6 to determine composition.
WALGER (1961) mentioned that staining is required to determine the partic-
ular isomorphous series before a final determination is possible. Walger stated that
based on FRIEDMAN’S (1959) staining techniques not all series can be identified.
This limitation, however, has been eliminated by the staining scheme of WARNE
(1962) given here in the appropriate section.
The use of Canada Balsam or Lakeside cement 70C as mounting medium
(nt = 1.537 or 1.54) limits the application of the method described above. Walger
pointed out, however, that mounting media with nr = 1.57 and 1.665 are available,
and permit the examination of the whole range of carbonates under consideration
here (nr = 1.57 for Phthalopal G, many polyester-resins such as Standofix, Palatal,
Legural KR25; nr = 1.665 for Aroclor No.4465 manufactured by Monsanto Chem-
EXAMINATION AND ANALYSIS OF SEDIMENTARY CARBONATES 283

ical Co., St. Louis, Mont., U. S. A.). As Aroclor has a strong dispersion ( n ~ - n ~ =
0.019), it is advisable to use Na-light.
GILBERT and TURNER (1949) described a universal stage method to distin-
guish between calcite, dolomite, Fe-dolomite and ankerite; and HOWELLand
DAWSON(1958) use a similar technique as described above for iron-bearing
dolomite.
WINCHELLand MEEK(1947) suggested that the diagnostic birefringence/
dispersion ratio is useful in discrimination between various carbonates in thin-
section. Both SCHUMANN (1948) and WALGER (1961), however, discussed the limi-
tations of this method. During Walger’s investigations he met unexpected diffi-
culties which have not been solved as yet and it is impossible, therefore, to make
a final decision regarding the applicability of the method advocated by Winchell
and his co-workers.

Fig.6. Variation of eo with composition in the minerals of the calcite group. (After WALGER,
1961, by permission of the Neues Jahrbuch fur Mineralogie, Monatshefte.)
 284 K. H. WOLF, A. J. EASTON AND S. WARNE

PLATE I

A
EXAMINATION AND ANALYSIS OF SEDIMENTARY CARBONATES 285

B
286 K . H. WOLF, A. J. EASTON A N D S. WARNE

The limitations of using the methods mentioned above in determining the

composition of carbonate minerals have been mentioned by WAYLAND (1942) and
Burger (1963), for example. In the cases of simple solid solution substitutions, e.g.,
MgC03--MgFe(CO3)~-FeC03, the figures by KENNEDY(1947) and WALGER
(1961) can provide a sufficiently accurate means for rough estimates. Substitutions
are often more complicated, however, and instead of one cation two or more take
the place of Ca, for instance. Particularly illuminating are the discussions and data
by LOGVINENKO et al. (1961). They pointed out that most information on the iso-
morphism of carbonates is related to binary series, whereas in fact many are poly-
component systems, such as (Fe, Ca, Mg, Mn) C03. One of the examples of sed-
imentary (i.e., low-temperature) monomineralogic carbonates determined by them
had the composition (Fe49.67-85.04 Ca3.54-38.80 Mg3.99-20.47 Mno.ol-9.1z)COa.
Presently available optical methods alone, of course, cannot reveal such complicated
compositions.

ELECTRON-MICROSCOPE EXAMINATION OF CARBONATES

The electron microscope has already been used for some time to reveal micro-
features of fossils, but it has not yet been employed everywhere to its fullest
advantage in carbonate petrology. WATABE et al. (1958), GRUNAU (1959), GRB-
GOIRE (1961, 1962), WATABE and WILBUR(1961), HAY and TOWE(1962), and
ROSTOKER and CORNISH (1964), for example, studied micro-organisms. ALBISSIN
and RANGO(1962) investigated corrosion features, and GRBGOIRE and MONTY
(1962) examined the cryptocrystalline nature of stromatolites.
M. I. Whitecross (personal communication, 1964) has shown that the
Renalcis unicellular Algae in certain limestones (WOLF,1963a, 1965a) are crys-
talline in nature (Plate IA,B).
The presence or absence of crystals as well as their size and shape may be
investigated with the electron microscope using a surface-replica method. Since
the carbon-replica technique was first reported (BRADLEY,1954), it has been used
in examining the surfaces of a wide variety of materials. Though there have been

PLATE I (813.284-285)

A. The central part shows an electron-microscope enlargement of a section of a Lower Devonian

unicellular Alga Renalcis (WOLF, 1965a).Note the gradation into larger crystals of the surrounding
somewhat coarser, matrix. The Renalcis cells cannot be resolved by an ordinag petrographic
microscope and are seen as dense, cryptocrystalline specks. (Photo by Dr. M. I. Whitecross,
Australian National University.)

B. Electron-microscope enlargement of the coarser crystalline matrix surrounding the Renalcis

cells featured in Plate IA. (Photo by Dr. M. I. Whitecross, Australian National University.)
EXAMINATION AND ANALYSIS OF SEDIMENTARY CARBONATES 287

many modifications, it consists essentially in transferring an impression of the

surface in question through some intermediate steps to a thin layer of carbon
which can be examined in the electron microscope. Carbon replicas are commonly
shadowed in vacuo with a heavy metal to enhance their contrast and three-dimen-
sional appearance in the electron beam (BRADLEY, 1906). Plates IA,B were taken
from replicas using the following procedure, employed by Dr. M. I. Whitecross
of the Australian National University.
The rock surface was polished with carborundum powder (grade 500),
washed and etched with saturated disodium E.D.T.A. solution for 1 min. The
surface was washed again, dried thoroughly and the chosen area flooded with a
20 % solution of Bedacryl 122X(I.C.I.). When the solvent had dispersed, a plastic
film was left forming a negative replica of the rock surface on its lower face.
Stripping the plastic film from the rock surface (to which it had become firmly
“keyed”) was simplified if the rock plus film was immersed for a couple of minutes
in water. The stripped film, with its replica surface uppermost, was then bonded
to a microscope slide, given a layer of carbon and shadowed with gold palladium
in the usual way. The final carbon replicas were obtained by dissolving the Bedacryl
with acetone and picking up pieces of the carbon film on electron-microscope
grids.
SHOJIand FOLK(1964) recently investigated fractured limestone surfaces
with an electron microscope and were able to correlate the features observed with
those obtained with an optical microscope. Significant for trace element and dia-
genetic studies and environmental interpretations are the liquid inclusions observed
in calcitic material by the above two investigators.
Solution to the problems of genesis of the numerous cryptocrystalline
micrite types listed by CHILINGAR et al. (1967) and WOLF(1963b, 1965b) may well
rest on detailed electron-microscope examinations.

STATISTICAL AND RELATED MICRO-FACIES STUDIES

A number of diverse techniques have been employed in carbonate petrology that

rely heavily on a statistical basis for genetic and stratigraphic interpretations.
FAIRBRIDGE (1954) discussed the advantages, limitations, and applications of
micro-facies investigations. Fairbridge quoted CUVILLIER (1951b) as stating that
an oil survey of Aquitaine (France) “. . . required the application of a system of
stratigraphic correlation in which the micro-facies played a much more important
part than the microfauna. In fact, among the formations encountered both in
outcrop and borehole, especially those consisting of hard rocks, calcareous,
marno-calcareous, siliceous, etc., correlations by microfaunas of Foraminifera
from washings are hardly practicable. Thousands of thin sections of these rocks,
systematically sampled, have permitted, on the other hand, the realization of a
288 K. H. WOLF, A. J. EASTON AND S. WARNE

detailed stratigraphic subdivision which embodies all the most characteristic micro-
facies.”
The more pertinent micro-facies features of carbonate rocks are morphologic
grain types; matrix types; morphologic types of sparry calcite cement and recrys-
tallization sparite; grainlmatrixlcement ratios; degree and amount of replace-
ment and recrystallization; fossils and fragments thereof without a need for pre-
cise identification (FAIRBRIDGE, 1954); certain diagenetic products; and other
textures, structures and morphologic characteristics. CUVILLIER (195 1a), HAGN
(1955), REY and NOUET (1958), GRUNAU (1959), HANZAWA (1961) and SACAL
(1963) have published books on micro-facies, some containing over 100 photomi-
crographs, that illustrate the method discussed by FAIRBRIDGE (1954), among
others.
Micro-facies studies have been much improved by the handling of the in-
formation in a statistical manner as done with success by CAROZZI (1950, 1958) and
STAUFFER (1962), for example. BANKS(1950) described a log for recording the types
of individual constituents as well as the gross rock lithology. This kind of log, with
modifications, is very useful in the description of carbonate sediments. Very
detailed logs may resemble those prepared by BOUMA(1962), and MENNING and
VITTIMBERCA (1962) for terrigenous sediments. To complement the various sym-
bols and verbal descriptions of logs, a number of exploration companies have
resorted to adding photomicrographs that greatly enhance the visualization of
sediment lithology.
CAROZZI (1950, 1958) developed a technique which consists of preparing thin
sections of carbonate rock specimens that have been collected at an interval of
about 1 ft. The spacing is usually adjusted to suit the particular requirements.
In precise investigations, thin-sections prepared of samples taken every 4-6
inches approaches the ideal of continuous sampling. Carozzi measured the follow-
ing parameters in thin-sections: ( I ) maximum diameter of detrital grains (clas-
ticity-index), which gives an idea of the power of transportation, and the number
of detrital grains (frequency index), which furnishes information about the load of
the current; (2) microfaunas (frequency and maximum apparent diameter);
(3) matrix (amount, texture and composition); and ( 4 ) authigenic minerals (fre-
quency and maximum apparent diameter). The curves based on these parameters
are valuable in particular as they not only assist in correlation but permit detailed
paleoenvironmental reconstructions as has been illustrated by Carozzi and his
co-workers in their numerous well-known publications.
In addition to presenting frequency curves that give the vertical distribution
of numerous components in the sedimentary column, STAUFFER (1962) prepared
contour maps of these parameters, thus illustrating the regional paleoenvironmental
pattern of distribution. The parameters he used for the contours are as follows:
composition and percentages of allochemical grains, sparry calcite cement, and
recrystallized calcite; individual allochemical grain types such as Bryozoa, cri-
EXAMINATION AND ANALYSIS OF SEDIMENTARY CARBONATES 289

noids, intraclasts, algal fragments, fusulinids; the largest diameter of different

grain types; and others.
SLOSSand COOKE (1946) proposed spectrochemical sample logging of lime-
stones; and KUDYMOV(1962) presented ample evidence of the usefulness of
analyzing for major and minor elements in both practical and research geology.
In the investigation of Recent carbonate sediments, FOLK(1962), FOLKet al.
(l962), and FOLKand ROBLES(1964) have used a statistical approach in recording
grain size, sorting, and skewness that resulted in some interesting information
regarding similarities and dissimilarities between carbonate and terrigenous sedi-
ments. For an example of grain-size, frequency, rounding and sphericity studies
applied to ancient limestones, the publication by FLUGEL and FLUGEL-KAHLER
(1962) is recommended by the writers. HARBAUGH and DEMIRMEN (1964) gave an
example of factor analysis in stratigraphic work (see also IMBRIEand PURDY,1962;
and IMBRIE, 1964).

X-RAY RADIOGRAPHY

A number of recent publications recommended the application of X-ray radio-

graphy for bringing out the sedimentary structures in terrigenous rocks (CALVERT
and VEEVERS, 1962; HAMBLIN, 1962; RIOULTand RIBY, 1963). The senior writer
has attempted without success to apply the same method to a few homogeneous
limestone samples. Acid-digestion of these specimens indicated that they were too
pure to have caused differential passage of the X-rays. Better results are expected
with carbonate rocks containing non-carbonate impurities which reflect the primary
depositional pattern.

SPOT TESTS FOR CATIONS IN CARBONATES

It has been mentioned in an earlier section that staining and spot tests may be
made on carbonate minerals to help in identifying the isomorphous series as well
as possible minor elements present. Spot tests for some of the cations usually
associated with carbonate minerals, and a short description of the techniques,
results, and limitations are presented in Table 111. For more information on spot
tests the reader may wish to consult a more comprehensive work on the subject
such as that of FEIGL (1958). The following aspects should be noted:
(1) The quantities of acid used are only approximate and should be added
dropwise to approximately 100 mg of the sample.
( 2 ) The neutrality or acidity should be tested by the use of Universal indica-
tor paper. The adjustment may be made either by the addition of more sample or
acid.
TABLE I11 h,
\o
0
SPOT TESTS FOR CATIONS IN CARBONATES
~~

Element Solvent Solution Reagents Procedure Reaction Notes

Fe3+ lO%v/v HC1 Slightly acid. lO%w/v Place 1 ml of test Red coloration Limit of identification
(2 ml) potassium solution in a test due to ferric (30 p.p.m.).
thiocyanate tube, add 3 drops thiocyanate.
solution. of reagent.
Ca lO%v/v HCI Slightly acid. (I) 300 mg Place 2 ml of test White crystalline (I)In case of ferrodolomite:
(2 ml) ammonium solution in a test precipitate: after reagent I, add 1 ml of
chloride tube, add reagent calcium oxalate. Brz water, boil for 1 min, and
(2) S%w/v I. Then add 1 ml then add ammonium hydroxide
ammonium- of reagent 2. until neutral. Centrifuge off the
oxalate Heat to boiling, precipitate and discard; then
solution. add excess ammonium add reagent 2, and boil for
hydroxide, and con- several minutes.
tinue boiling for (2) In rhodochrosite:
several minutes. after reagent I, add 1 ml of
bromine water, boil for 1 min,
and then add 3 ml ammonium
hydroxide. Centrifuge off pre-
d
"G
cipitate and discard; then add
reagent 2 and boil for several
minutes. (Limit of identification
is 600 p.p.m.)

Sr lO%v/v HC1 Neutral. 0.2%w/v Place 1 drop of Brown-red fleck In case of rhodochrosite:
(2 ml) sodium- test solution on on circle dissolve sample, add 1 ml of
rhodizonate a filter paper (strontium bromine water, boil for 1 min,
solution. impregnated with rhodizonate). and then neutralize with am-
saturated potassium monium hydroxide. Centrifuge
chromate and then off the precipitate and discard.
dried. After 1 min add Then continue as under
1 drop of reagent. procedure. (Limit of iden-
tification is 100 p.p.m.)
Mg lO%v/v HCl Slightly acid. (1)0.1 %w/v Place 5 ml of Supernatant In case of siderite or rhodo-
(2 ml) titan yellow reagent I in a test liquid and precipitate chrosite: dissolve sample, make
solution tube. Add 10 drops of are red (magnesium volume to 5 ml, add 300 mg
(2) lO%w/v
sodium
test solution; then
add reagent 2
dye complex). of ammonium chloride, and then
add 1 ml of bromine water. 5*z
hydroxide
solution.
dropwise until
precipitate forms.
Boil for 1 min and neutralize 5
with ammonium hydroxide. 8
Centrifuge off precipitate, make
centrifugate just acid with HCI. *
2
2
Then add 5 ml of reagent I U
followed by reagent 2 dropwise *
until a precipitate forms; allow
to settle. The precipitate alone
%.e
is colored red due to inter- E
ference of ammonium salts.
%
(Limit of identification is v1
150 p.p.m.) 6
Fez+ lO%v/v HCI Neutral. (I) 0.2%w/v Place 2 drops of Pink coloration (ferrous When testing for Fez+ in Z
(2 ml) 2,2-dipyridyl test solution dipyridyl complex). rhodochrosite: increase volume 4
or (in 1.5 %v/v in a test tube, of test solution to 5 ml, >
P
3 %V/V HzS04 HCI solution). add 2 drops of reagent I to 1 ml, and 4
0
(3 ml) (2) 25 %w/v reagent I, and then reagent 2 to 5 ml. (Limit of >
sodium acetate 5 drops of reagent 2. identification is 20 p.p.m.). P
solution. 8
5
Mn 3 %v/v HzS04 Acid. (I) 1 %w/v Place 5 ml of test Pink coloration in When testing for Mn in a
(5 ml) silver nitrate solution in a test tube.
v)
supernatant liquid siderite: increase phosphoric
solution. Add 2 drops of phos- (KMn04). acid to I ml and reagent 2 to
(2) 20U mg phoric acid, then add 500 mg. (Limit of identification
ammonium drop of reagent 1. is 15 p.p.m.)
persulphate. This is followed by
reagent 2.
Boil for 1-2 min.
292 K. H. WOLF, A. J. EASTON AND S. WARNE

(3) The reagents should in the case of organic compounds be freshly prepared
(daily).
To increase the sensitivity of spot tests on filter paper, a circle (a
inch) is
pencilled on both sides of the filter paper with a white grease pencil and warmed over
a low Bunsen flame to congeal the grease. The test drops are applied within the
circle in order to concentrate the reaction. Where precipitates are formed, the solu-
tion may be drawn from the drop by blotting the under side of the test circle. Thus
the color of the precipitate can be seen more easily.

CHEMICAL ANALYSIS OF CARBONATE MINERALS AND ROCKS

Methods for the determination of the major and some minor components of car-
bonates by either wet or dry, o r a combination of both techniques are presented
here in some detail. It is not possible to present data on analytical techniques of
most of the trace elements and only a table is given to indicate the method usually
employed (Table IV,V). The techniques described here have been utilized on the
analysis of ten samples and the results are shown in Table VI.
The basis of the earlier schemes for the wet chemical analysis of limestones
was mainly formulated in relation to the industrial application of the material.
Often the analysis was restricted to the determination of acid insoluble residue,
iron, calcium and magnesium. The carbon dioxide was either calculated from the
calcium and magnesium contents or determined by loss on ignition. This simplified
analysis satisfied the industrial requirements and was not expanded until geological
investigations required a more detailed knowledge of the carbonate material.
The work by NORTH (1930) shows this expansion of limestone analyses in detail.
Since that time, however, the accuracy of some of the analytical methods
for the determination of minor elements, e.g., Fey Mn, P, Ti, Cr, and Al,

TABLE IV

MAJOR AND MINOR ELEMENT ANALYSIS'

Element Percentage
0.1-1 1-10 > 10

Ca b (*Is%) b,c (f2%) b,c ( 4 2 % )

Mg b(55%) b,c ( M %) b,c (52%)
Fe a (52%) a,b (*2%) b (32%)
Mn a (52%) a,b ( 5 2 % ) b (&2%)
Ti a (f2%) - -

a = spectrophotometricanalysis; b= E.D.T.A. titration; c = gravimetric analysis.

EXAMINATION AND ANALYSIS OF SEDIMENTARY CARBONATES 293

TABLE V

TRACE ELEMENTS ANALYSIS~

U U b C d
_____

Na + Ga + P + -
K + Ge
Li + Au - P + -

Rb + Pb + + + +
Sr + Mn +- + P +-
cs +- Hg + +
Sb Mo - P + -
As - Ni + P + +
Ba + + + + +
+- + +-
U2
Be - Th2 +
B + Se - +
Br -
Ag +- - P -
CI - Sn -
+ +
1 - Ti + + P +
Cd - W - P + -

Cr + V +- P + +
co + Zn + P +
cu + Zr -
+ + +-
F - Ra2 - + -

Neutron activarion. With the exception of the halogens, Li and Be, most other elements, including
the rare earths, can be determined by this technique. Although this method has the advantage
of sensitivity, the equipment involved is costly. This is the only technique available for certain
elements at the concentrations in which they occur.
(a) Flame-photometry. Although a number of elements have been indicated in the table as being
determinable by flame-photometry, with the exception of the alkalies Na and K, complex separa-
tions are often necessary to remove major elements that would otherwise interfere in the deter-
mination. Separation of organic complexes containing the element to be determined increases the
sensitivity, and allows the determination of elements which otherwise would not be practical.
(b) Spectrometry (copper electrodes). Extra sensitivity is obtained by the use of copper-spark
emission techniques. The great advantage of spectrographic equipment is that a large range of
elements may be determined at the same time.
(c) Spectrophotornetry. This technique enables the determination of a large number of elements,
although the time involved is sometimes greater than that required by other techniques. Ion-
exchange separations have assisted in the removal of interfering elements.
(d) X-ray spectrograph (X-ray fluorescence). Similar to spectrographic techniques, the same sample
may be used for the determination of a number of elements, particularly those with high atomic
numbers. The sample may also be stored for future reference.

Explanation of symbols: + = determination possible; - = determination impossible; P =

determination by this technique preferred.
Neutron activation is the technique preferred for these elements.
TABLE VI
CHEMICAL ANALYSIS OF SOME RECENT AND ANCIENT CARBONATES ROCKS

(Determined by A. J. EASTON)
Sample No. I 2 3 4 5 6 7 8 9 10

Moisture (%) 0.58 0.42 2.09 0.10 0.11 0.05 0.09 0.01 0.11 0.07
Loss on ignition (%) 44.80 44.79 48.18 42.91 42.68 39.91 46.80 45.51 44.58 40.05’
Acid insoluble residue (%) 0.17 0.05 0.06 1.79 2.05 8.14 0.82 2.90 11.85 0.06
CaO 50.60 49.27 39.78 53.61 53.06 49.50 30.44 32.45 7.85 0.22
MgO 2.54 2.99 8.29 0.51 0.80 0.76 21.40 18.62 34.90 6.07
Fez03 0.01 1 0.017 0.017 0.02 0.055 0.16 0.09 0.018 0.08 n.d.2
FeO 0.005 0.003 0.003 0.14 0.16 0.65 0.19 0.047 0.28 50.62
MnO 0.003 <0.001 <0.001 0.022 0.056 0.046 0.01 1 0.002 <0.001 2.66
Ti02 <0.001 0.002 0.001 0.03 0.005 0.008 0.004 0.013 0.013 n.d.2
Crz03 0.002 <0.001 <0.001 0.003 0.002 0.002 0.003 0.003 0.001 n.d.2
Pzos 0.06 0.03 0.01 0.17 0.30 0.33 0.07 0.10 0.13 <0.01
AhOs 0.08 0.04 0.11 <0.01 <0.01 0.27 <0.01 0.13 0.05 n.d.%
Na 0.59 0.58 0.67 0.01 0.006 0.02 0.03 0.04 0.03 0.06
K 0.03 0.02 0.04 0.02 0.01 0.02 0.01 0.02 0.04 0.02
Sr 0.40 0.56 0.40 <0.01 0.04 0.20 <0.01 0.06 0.04 n.d.z
S (total) 0.18 0.11 0.07 <0.01 0.04 0.20 <0.01 <0.01 <0.01 n.d.2
c1 0.53 0.39 0.16 0.33 0.09 0.06 0.16 0.14 0.14 n.d.2
Total (%) 100.57 99.26 99.87 99.66 99.43 100.31 100.11 100.04 100.09 99.83

Sample No.1. Recent lagoon sample of Heron Island, Great Barrier Reef, composed of unconsolidated fine-grained calcarenite with constituents of
aragonite, and low-Mg and high-Mg calcite (WOLF,1963a.)
Sample No.2. Heron Island beach rock composed of aragonite-cemented skeletal calcarenite. Constituents: aragonite, low-Mg and high-Mg calcitic
organic debris. (WOLF,1963a.)
Sample No.3. Lithothamnion (algal) colony of Heron Island. Note high Mg content. (WOLF,1963a.)
Sample No.4. Algal biolithite from the Lower Devonian Red Hill limestone @lo) near Wellington, N.S.W. (WOLF,1965a.)
Sample No.5. Algal micrite from a Lower Devonian Nubrigyn bioherm (Nub. 716) near Stuart Town, N.S.W. (WOLF,1965a.)
Sample No.6. Algal calcarenite from a “turbidite” facies of the Tolga Formation, near Stuart Town, N.S.W. (WOLF,1965a.)
Sample No.7. Dolomite from the G.R.G. 14 well, Georgina Basin, N.T. (Sample No.141, courtesy Bureau of Mineral Resources, Canberra, A.C.T.)
Sample No.8. Dolomite in Kaibab limestone, west of Blue Diamond Hill, Blue Diamond, Nev. (Courtesy H. J. Bissell.)
Sample No.9. Pellet magnesite, Lower Adelaide System, S. Austr. (Specimen from Australian National University collection, courtesy Department of
Mines, Adelaide, S. Austr.)
SampleNo.10. Sideritefrom Mammoth Black Ridge, Martin’s Well Station, S.Austr. DDH2,476 ft. 1 inch. (Courtesy Broken Hill Proprietary Co. Ltd.,
Whyalla, S. Austr.)

1 Corrected for oxidation of Rz03 group.

2 n.d. = not determined.
EXAMINATION AND ANALYSIS OF SEDIMENTARY CARBONATES 295

has been improved by the introduction of spectrophotometric instruments. In

a similar way the introduction of the flame-photometer has increased the accu-
racy of the determination of sodium and potassium.
The use of E.D.T.A. titrations for the determination of calcium, magnesium,
iron and manganese now offers an alternative method to the gravimetric proce-
dures.
The methods given in this section include: ( I ) moisture and loss on ignition;
(2) carbon dioxide; (3) main analysis: 3a-acid insoluble, 36-silica in the acid
insoluble, 3c-Rz03, 3d-iron, 3e-manganese, 3f-titanium, jlg-chrornium,
3h--phosphorus, 3i-aluminum, 3j-calcium-gravimetric, 3k-calcium-E.D.T.A.,
31-magnesium-gravimetric, 3m-magnesium-E.D.T.A.; ( 4 ) ferrous iron; (5)
alkalies-Na, K and Sr; (6) total sulphur and sulphur trioxide; and (7) chlorine.
A general scheme combining some of these methods is shown in Fig.7. The details
of the analysis largely depend upon the particular interest in the sample, i.e.,
industrial or geological investigation.

Spectrophotometric measurements

In a number of the following procedures the element is measured by forming a

soluble colored complex. The absorbance (ie., intensity of color) of the test
solution is measured using a spectrophotometer and compared with a curve
obtained by treating aliquots of a standard solution of the same element in a simi-
lar manner (A. I. VOGEL,1951).
In all of the spectrophotometric methods it is possible to prepare a standard
curve by taking various size aliquots and plot the absorbances obtained against
the quantity of the element in solution. In this way the absorbance of the test
solution may be quickly converted to the quantity of the element (in milligrams)
present in the solution.

SAMPLE
'
Dissolve in acid
I
SAMPLE
I
Dissolve in ocld
I

I
Acid insoluble I I
Acid insoluble
residue

30
residue ;"
Ignite coo Adjust

I
Weigh
Fuse
I
I
I
MgO
&
P Cr Mn
V
Ti,,Co Mg
*
A1 Fe,

Sqlutlon
E.D.T.A.
Spectrophotometricolly titratbn
Fe Ti Mn Cr P Al

Fig.7. Scheme of chemical analysis of carbonates.

296 K. H. WOLF, A. J. EASTON AND S. WARNE

The water reference sample and solutions were held either in special glass
tubes or flat-sided glass containers known as cells. Whichever type of container
is used, the light path is of a fixed length, e.g., 1 or 4 cm.

Determirlation of moisture and loss on ignition

The moisture and loss on ignition are determined on the same portion of the sample.
Weigh 1 g of sample into a clean weighed platinum crucible and dry for 2 h in
an oven set a t 105°C. At the end of this period remove the crucible and cool in a
desiccator for 15 min before reweighing. Repeat the heating for 30 min more,
cooling as before.
The loss in weight of the crucible and sample is due to loss of moisture
(HzO) and is recorded as a percentage of the sample weight.
Then transfer the crucible to either a Bunsen burner or an electric furnace
and raise the temperature slowly to red heat (600°C). Finally, heat the crucible at
1,000-1,lOO"C for 1 h, then allow the crucible to cool in a desiccator for '30 min
and weigh. Repeat the ignition for 30-min periods at the higher temperature until
a constant weight is obtained.
The loss on ignition is the difference in weight of the crucible and sample
after drying at 105"C, and the final weight after ignition. This is then calculated
as a percentage of the sample weight. Loss on ignition will be the combined loss
of carbon dioxide plus any other constituents present that are evolved at tempera-
tures above 105"C (e.g., hydrocarbon compounds and organic materials as those
in Lithothamnion in sample No. 3 in Table VI).
Note: Where a large proportion of the sample is siderite, the loss on ignition
must be corrected for the increase in weight due to the oxidation of the Rz03
group [i.e., FeO (from FeC03) + Fez03; and MnO (from MnC03) -+Mnz031.

Determination of carbon dioxide

Two alternative methods are available for this determination, the first is usually
reserved for samples high in carbon dioxide, whereas the second may be used
regardless of the carbon dioxide content.

Schotter flask (CLOWESand COLEMAN, 1944)

In this method the carbon dioxide is liberated from a weighed portion of the sam-
ple by the action of phosphoric acid. The sample, separated from the 10 ml of
50% v/v phosphoric acid is placed in the flask and weighed. The acid is allowed
to come into contact with the sample and the liberated gas leaves the flask through
a trap containing sulphuric acid. After the reaction is complete, the flask is re-
weighed; the difference in weight is a measure of the carbon dioxide content of
the sample.
EXAMINATION AND ANALYSIS OF SEDIMENTARY CARBONATES 297

Absorption train (A. I. VOGEL,1951)

This method uses the increase in weight of U-tubes containing soda-lime and
calcium chloride to measure the carbon dioxide liberated by the action of phos-
phoric acid on a weighed portion of the sample.

Main analysis

Acid insoluble residue

Weigh 1.0 g of .the sample into a 250-ml beaker and cover it with a watch glass.
Add 150 ml of 25% v/v hydrochloric acid and warm the beaker and contents
to 50-60°C for 30 min (BISQUE and LEMISH, 1959). After this period wash the cover
glass into the beaker and filter off the insoluble residue through a 541 Whatman
filter paper. Wash the paper three or four times with warm water and set the
filtrate aside for the determination of the other elements.
Ignite the paper containing the insoluble residue in a previously weighed plat-
inum crucible. The heating should initially only be sufficient to dry the contents
of the crucible, then increased slightly so that the paper is charred, a& finally
increased to just red heat to ignite the paper completely. After the paper has been
ignited, the heat is increased to about 1,OOO"C for 10-15 min. The crucible is
allowed to cool in a desiccator for 30 min before weighing. Repeat the ignition
until a constant weight is obtained.
The weight of the ignited residue is reported as a percentage together with
the strength of the acid (25 % v/v HCI) and the temperature to which it was ini-
tially heated (50-60°C).
It should be appreciated that some clay minerals will also pass into solution
with the carbonate portion of the sample, because certain clay minerals are slightly
soluble.
Organic insoluble matter will be destroyed on using the ignition method
given above; and, therefore, if the acid insoluble residue including the organic
matter is required, the filtration must be made through a weighed glass-sintered
crucible. This is then reweighed after drying to a constant weight at 105°C in
an oven.

Complete analysis of acid insoluble residue (silica)

Upon recording the weight of the platinum crucible plus the acid insoluble residue
after ignition, the residue is then treated with one or two drops of sulphuric acid
and 5 ml of hydrofluoric acid. The silica is then volatilized off by heating the
crucible first on a water bath and then, when only sulphuric acid remains, by
heating over a low Bunsen burner flame until all of the acid is fumed off. The heat-
ing is continued for approximately 10 min after which the crucible is allowed to
cool in a desiccator for 30 min and then reweighed. The loss in weight is the
weight of the silica present in the acid insoluble residue.
298 K. H. WOLF, A. J. EASTON AND S. WARNB

Where a complete analysis of the other constituents of the acid insoluble

residue is required, the residue from the treatment with HF-HzS04 is fused in
the platinum crucible with 0.5 g of sodium carbonate.
The fusion cake is dissolved from the platinum crucible with a minimum of
10% v/v hydrochloric acid and the solution is transferred to a beaker. This solution
is then analyzed by the methods given in the sections on iron, manganese, titanium,
chromium, phosphorus, and aluminium for the R203 group constituents; and the
calcium and magnesium are determined on using the filtrate from the R203 group
precipitation by the methods given in the sections on calcium-gravimetric, cal-
cium-E.D.T.A., magnesium-gravimetric, and magnesium-E.D.T.A. determina-
tion.

R203 group (Fe, Mn, Ti,Cr, P,AI)

(If the limestone analysis is required to include the acid insoluble residue with the
carbonate portion, i.e., total analysis, the residue left after treatment with HF-
HzS04 is fused with sodium carbonate (0.5 g). Then the fusion cake is dissolved in
a minimum of 10% v/v hydrochloric acid and the solution is added to the filtrate
from the acid insoluble separation.)
Add 1-2 ml of bromine water to the filtrate from the acid insoluble separation
and boil for several minutes to oxidize any ferrous iron to the ferric state. Remove
from the heater and add a few drops of universal indicator; then add ammonium
hydroxide dropwise until the p H is raised to 7, i.e., neutral. (All members of the
R2O3 group are precipitated after oxidation as hydroxides by the addition of
ammonium hydroxide solution.) Replace the solution on the heater for 1-2 min,
avoiding boiling, to coagulate the precipitate. Allow the precipitate to settle and
filter through a 541 Whatman filter paper.
Wash the precipitate in the filter paper three or four times with warm 1 %
w/v ammonium nitrate solution. Set aside the filtrate.
Dissolve the precipitate into a 250-ml beaker with warm 10% v/v hydrochlo-
ric acid, washing the dissolved salts through the filter paper with hot water. In-
crease the volume to 150 ml and reprecipitate as before. Filter off the precipitate
and wash with warm 1 % w/v ammonium nitrate solution. Combine both filtrates
and set aside for the determination of calcium and magnesium.
Ignite the precipitate in a previously weighed platinum crucible. Heat slowly
at first, increasing the temperature finally to approximately 1,lOO"C for 10-15
min. The crucible is allowed to cool in a desiccator for 30 min before weighing.
Ignite again until a constant weight is obtained. The weight of the ignited precipi-
tate is a sum of the weights of Fe, Mn, Ti, Cr, P, and A1 as oxides, depending on
which are present in the sample.
These are now determined separately by adding 1-2 g of potassium bisul-
phate to the crucible and fusing the ignited precipitate over a Bunsen burner
flame in a fume cupboard. The crucible should only be heated at first sufficiently
EXAMINATION AND ANALYSIS OF SEDIMENTARY CARBONATES 299

to cause the potassium bisulphate to just melt. The heat is gradually increased
to avoid loss from the fusion due to “spitting”. Most of the fusion action is obtain-
ed below red heat; but it may be necessary to heat to red heat to obtain complete
fusion of the ignited precipitate as the constituents are present as oxides.
After fusion allow the crucible to cool to room temperature: this is most
important for safety.
Half fill the crucible with 3 % v/v sulphuric acid and place on a water bath
or heater to dissolve the fusion cake. This may require several additions of the
sulphuric acid before complete solution is effected. Allow the solution to cool,
then transfer it to a 100-ml volumetric flask and adjust the volume with water.
Shake the contents well to ensure thorough mixing. Then determine the constit-
uents of the RzO3 group as given in the section below.

Determination of total iron

Two methods are available for the determination of iron depending upon the com-
position of the sample. The spectrophotometric method using the ferrous di-
pyridyl complex is suitable for samples containing < 5 % FenO3, but where this
figure is exceeded an E.D.T.A. titration is more suitable (CHENGet al., 1952).

Spectrophotometric method (RILEYand WILLIAMS, 1959). The iron present in the

aliquot is reduced to the ferrous state as described below, then 2,2’-dipyridyl solu-
tion is added and the pH adjusted by the addition of a sodium acetate buffer.
This results in a pink coloration. The absorbance of the solution is measured and
compared with a standard iron curve.
Place an aliquot containing 0.05-0.5 mg of iron as Fez03 in a 100-ml
volumetric flask. If the iron content is totally unknown then initially use a 5 ml
aliquot. Add 10 ml of 10% w/v hydroxylamine hydrochloride solution and set
aside for 10 min to allow the iron in the solution to be reduced to the ferrous
state. Add 5 ml of 0.2% w/v 2,2’-dipyridyl solution (prepared in 1.5 % v/v HCI),
followed by 25 ml of sodium acetate buffer (272 g CH3COONa.3H20 per liter).
Adjust the volume of the solution in the flask to 100 ml with water and mix.
Measure the absorbance of the solution against water in a 1-cm cell using a spec-
trophotometer with the wave-length set at 522 mp. Compare the absorbance of the
sample solution against a standard curve prepared by treating aliquots of a stand-
ard iron solution in a similar manner.

Preparation of standard curve (Fig.8). A standard iron solution may be prepared

by dissolving 0.1398 g of “specpure” iron sponge in about 2 ml of hydrochlo-
ric acid and diluting to 2 1 with water. Further, this solution should be diluted ten-
fold so that 1 ml will contain 0.01 mg of iron as FezOs.
Place at least six aliquots of the standard iron solution, ranging from 0.05-
0.5 mg, in 100-ml volumetric flasks and make the same additions of hydroxylamine
hydrochloride, 2,2’-dipyridyl and sodium acetate buffer as before. After measuring
300 K. H. WOLF, A. J. EASTON AND S. WARNE

0.6 1

Fig.8. Hypothetical “standardcurve” of absorbanceversus Fez03 content used in spectrophotom-

etry. Wave length 522 mp; volume 100 ml; 1 cm cell.

the absorbances, construct a curve relating absorbance against milligrams of iron

per 100 ml of solution.

Determination of manganese
The spectrophotometric method described below is used where MnO is < 5 %;
but where the sample contains a high proportion of rhodochrosite, an E.D.T.A.
titration is used (FLASCKA, 1953).
The manganese in an aliquot is oxidized by the addition of ammonium
persulphate and silver nitrate (catalyst) in an acid solution to form the pink per-
manganate color (WILLARD and GREATHOUSE, 1917). The phosphoric acid is added
to prevent the interference of iron by forming iron phosphate, whereas the mer-
curic salt is added to prevent any trace of chloride from forming a turbidity with
the silver ions in the solution. The absorbance of the solution is measured and
compared with a standard manganese curve.
An aliquot containing 0.05-0.5 mg of manganese as MnO is placed in a 100-ml
beaker. If the manganese content is totally unknown, then initially use a 10-ml
aliquot. On the other hand, if only a faint pink coloration is developed after oxida-
tion, increase the size of the aliquot.
Add 2 ml of the following solution to the beaker from a measuring cylinder.
The solution is prepared as follows: dissolve 37.5 g of mercuric sulphate in 200 ml
of concentrated nitric acid, then add 100 ml of phosphoric acid (85% strength)
and 0.017 g of silver nitrate. Allow the solution to cool and dilute to 500 ml.
Add 0.5 g of ammonium persulphate and adjust the volume to approximately 30
ml with water. Oxidize by boiling for 10 min. Allow the solution to cool to room
temperature; if manganese is present then a pink coloration (KMn04) will develop.
Transfer the solution to a 50-ml volumetric flask and adjust to volume with freshly
boiled and cooled water. Shake well to ensure complete mixing.
Measure the absorbance of the solution as soon as possible against water in a
EXAMINATION AND ANALYSIS OF SEDIMENTARY CARBONATES 30 1

Fig.9. Hypothetical “standard curve” of absorbanceversus MnO content used in spectrophotom-

etry. Wave length 525 mp; volume 50 ml; 1 cm cell.

I-cm cell usinga spectrophotometerwith thewave-length set at 525 mp. Compare the
absorbance of the sample solution with a standa’rd curve prepared by treating ali-
quots of a standard manganese solution in a similar manner.

Preparation of standard curve (Fig.9). A standard manganese solution may be

prepared by dissolving 0.11 14 g of potassium permanganate in 1 1 of water con-
taining 5 ml of 10% w/v hydroxylamine hydrochloride solution. Of this solution
1 ml will then contain 0.05 mg of manganese as MnO.
Place at least six aliquots of the standard manganese solution ranging from
0.05-0.5 mg in beakers, adjust the volume to approximately 30 ml with water, and
oxidize as described above using the same additions of reagents. Allow the so-
lutions to cool to room temperature, transfer to 50-ml volumetric flasks, and adjust
to volume. Construct a curve relating absorbance against milligrams of manganese
per 50 ml of solution.
Note: Inasmuch as the precipitation of manganese as a hydroxide is not
always completed in the Rz03 precipitation, the residual must be measured at a
later stage, i.e., in the magnesium pyrophosphate precipitate; see the section on
the magnesium-gravimetric method. Where E.D.T.A. titrations are to be used for
the determination of calcium and magnesium, an aliquot of the filtrate from the
Rz03 separation must be evaporated to dryness with 1 ml of sulphuric acid to
expel chlorides before applying the above method.

Determination of titanium
Titanium forms a yellow complex with tiron (1 ,Zdihydroxy-benzene 3,5-disul-
phonic acid) (YOEand ARMSTRONG, 1947), which is more sensitive than the yellow
titanium peroxide complex commonly used in rock analysis. A buffer is added to
adjust the p H of the solution, as the maximum absorbance is obtained at pH 5.0.
Any ferric iron present in the solution forms a purple complex with the reagent;
302 K. H. WOLF, A. J. EASTON AND S. WARNE

and for this reason a few milligrams of sodium dithionite are added to reduce the
iron to the ferrous state, in which the iron-tiron complex is colorless. Inasmuch as
sodium dithionite decomposes fairly rapidly liberating colloidal sulphur, the absorb-
ance of the solution is measured within 15 min of being prepared and compared
with a standard titanium curve.
An aliquot containing 0.01-0.1 mg of titanium as Ti02 is placed in a 50-ml
beaker and the volume adjusted accurately to 5 ml with water. It is usually con-
venient initially to use a 5-ml aliquot. Add approximately 100 mg of tiron followed
by 25 ml of buffer solution. The buffer solution is prepared by dissolving 40 g of
ammonium acetate in about 500 ml of water, adding 15 ml of glacial acetic acid and
adjusting the volume to 1 1 with water. If a purple color is present, add 10-20 mg
of sodium dithionite to reduce the iron present in the solution to the colorless
ferrous state.
Where the iron content of the sample is high (> lo%), e.g., in siderite, the
iron may interfere by the mechanism of air-reoxidation of the iron-tiron complex.
In this case the iron present in the aliquot may be held as the colorless ferrous
E.D.T.A. complex which does not undergo air-reoxidation (EASTON and GREEN-
LAND,1963).
Measure the absorbance of the solution against water in a 1-cm cell using
a spectrophotometer with the wave-length set at 430 mp. Compare the absorbance
of the sample solution with a standard curve prepared by treating aliquots of a
standard titanium solution in a similar manner.

Preparation of standard curve (Fig.10). A standard titanium solution may be pre-

pared by fusing 0.02 g of pure titanium dioxide with 2 g of potassium bisulphate
in a platinum crucible. After allowing the crucible to cool, the fusion cake is dis-
solved from the platinum crucible with 3% v/v sulphuric acid by heating until
a clear solution is obtained. The volume is then adjusted to 1 1 with 1 % v/v
sulphuric acid; thus 1 ml will contain 0.02 mg of titanium as TiO2.
Place at least six aliquots of the standard titanium solution ranging from
0.02-0.1 mg in 100-ml beakers, and buffer solutions as before. After measuring the
absorbances, construct a curve relating absorbance against milligrams of titanium
in each beaker.

Determination of chromium
The chromium (0.02-0.1 mg Crz03) in an aliquot is oxidized by the addition of
ammonium persulphate and silver nitrate (catalyst). The iron is separated by
neutralizing the solution with solid sodium carbonate, the precipitate is centri-
fuged off and discarded. The solution is acidified with sulphuric acid and an excess
of 1 ml is added. Then 10 ml of 0.1 % w/v diphenylcarbazide solution (in acetone)
is added forming a pink complex with the chromate (VANDER WALTand VANDER
MERWE, 1938).The absorbance is measured at a wave-length of 540mp andcompared
EXAMINATION AND ANALYSIS OF SEDIMENTARY CARBONATES 303

0.6

Ti02 (mg)

Fig. 10. Hypothetical “standard curve” of absorbanceversus Ti02 content used in spectrophotom-
etry. Wave length 430 mp; volume as given; 1 cm cell.
Fig.11. Hypothetical “standard curve”ofabsorbance versus Crz03 content used in spectrophotom-
etry. Wave length 540 mp; volume 50 ml; 1 cm cell.

with a standard chromium curve prepared from potassium dichromate (Fig.11).

Note: Manganese present as permanganate interferes with the reaction be-
tween chromium and diphenylcarbazide (A. J. EASTON, 1964); and if present, it may
be reduced by the addition of E.D.T.A. solution before the chromium-diphenyl-
carbazide complex is formed. A 0.1 % w/v E.D.T.A. solution is added dropwise
into the flask until the permanganate color is almost discharged in the sample
solution. If no permanganate color is present in the solution, this addition is
omitted.

Determination of phosphorus
The phosphorus in the aliquot combines with the vanadomolybdate reagent to
form yellow vanadomolybdic phosphoric acid (KITSONand MELLON,1944).
Inasmuch as the reagent solution itself has an absorbance at 430 mp, the absorbance
of the sample solution is measured against a reagent blank so that the difference in
absorbance is due only to the complex formed by the phosphorus. This difference
in absorbance is then compared with a standard phosphorus curve.
An aliquot containing 0.01-0.3 mg of phosphorus as Pz05 is placed in a
50-ml volumetric flask and the vohme adjusted with water to approximately 15 ml.
Where the phosphorus content is low, a 15-ml aliquot may be taken initially.
Add 10 ml of vanadomolybdate solution. Prepare the reagent solution by
dissolving 1.25 g of ammonium metavanadate (NH4V03) in 400 ml of cool 50%
v/v nitric acid. Separately dissolve 50 g of ammonium molybdate in 400 ml of
water and filter off any solid particles that may remain. Add the ammonium molyb-
date solution to the ammonium metavanadate solution and adjust the volume to
1 1.
Adjust the volume to 50 ml with water and shake well to ensure complete
mixing. Measure the absorbance of the solution after 5 min against the reagent
[!L
304 K. H. WOLF, A. J. EASTON AND S. WARNE

0.15

a 0.05
a 0 0.15 0.3

P205 (mg)
Fig.12. Hypothetical “standard curve” of absorbanceversus PZOScontent used in spectrophotom-
etry. Wave length 430 my; volume 50 ml; 1 cm cell.

blank in a 1-cm cell, using a spectrophotometer with the wave-length set at 430 mp.
The reagent blank is prepared by adding 10 ml of vanadomolybdate solution to
a 50-ml volumetric flask and then adjusting the volume with water.
Compare the absorbance of the sample solution with a standard curve pre-
pared by treating aliquots of a standard phosphorus solution in a similar manner.

Preparation of standard curve (Fig.12). A standard phosphorus solution may be

prepared by dissolving a quantity of a standard phosphate rock (e.g., National
Bureau of Standards phosphate rock 56) by adding 25 ml of 50% v/v nitric acid
to the weighed material in a 150-ml beaker. The beaker is covered with a watch
glass and the contents allowed to digest for several hours on a steam bath until the
material is dissolved. A suitable concentration of the standard solution is 0.02 mg
of phosphorus as PzO5 per 1 ml. Dilute solutions of phosphorus should not be
stored in polyethylene bottles due to absorption of phosphorus by the walls of the
container.
Note: If the phosphorus content of the sample is sufficiently high so that it
will not be completely precipitated with the Rz03 group, then it will remain in the
filtrate. In this case it will be necessary to add a small quantity of aluminum
chloride to the acidified filtrate, and then precipitate the aluminum phosphate by
the addition of ammonium hydroxide as in the normal precipitation of the
Rz03 group described above. The precipitate is washed free of calcium and
magnesium salts by 1 % w/v ammonium nitrate solution, and then dissolved in
warm 3 % v/v sulphuric acid. The solution is next transferred to a volumetric
flask (e.g., 50-ml). An aliquot is then taken and the phosphorus determined with
vanadomolybdate solution as given above.

Determination of alurninum
For the determination of aluminum two main methods are available: ( I ) gravi-
and LEMISH,1959). Other methods
metric, and (2) titration with E.D.T.A. (BISQUE
EXAMINATION AND ANALYSIS OF SEDIMENTARY CARBONATES 305

include a spectrophotometric measurement after extraction of aluminum oxinate

(RILEYand WILLIAMS, 1959b).
If a scheme of analysis has been used that requires the separation of the
Rz03 group (i.e., Fig.7 left), then the aluminum may be determined by subtraction
of the other constituents from the total Rs03 content. This method is usually
referred to as “by difference”. An alternative method is that of titration with
E.D.T.A., which may be used when the scheme shown in Fig.7 (right) has been
applied to the sample.

Gravimetric method “by difference”. When using this method certain consider-
ations must be taken into account. First, the oxides are present in the ignited
Rz03 group in the following form: Fez03, TiOs, Mns03, Cr203, phosphorus
chiefly as AlP04, and excess aluminum as A1203. MnsOa is calculated from manga-
nese determined as MnO by multiplying by a factor of 1.11; whereas P04. by
multiplying the PzO5 found by a factor of 1.35.
The second consideration is that where aluminum is a minor constituent of
the RzO3 group, the magnitude of the errors involved in the determination of the
other constituents may impair the accuracy of the determination of aluminum.
Where this is the case and iron is the major constituent, e.g., siderite-bearing sam-
ples, the iron may be separated by an ion-exchange technique which leaves the
iron retained on the column whereas the other constituents are elutriated (EASTON
and LOVERING, 1963).
The advantage of this separation is that the aluminum is then obtained
as a relatively major constituent, and, therefore, is determined with increased
accuracy.

Determination of calcium
Two wet chemical methods are available for the determination of calcium: (I)
gravimetric precipitation as calcium oxalate followed by ignition to calcium oxide;
and (2) titration with E.D.T.A. The latter method has the advantage of being a
rapid procedure.
A third useful physicochemical method for the determination of the MgO
and CaO has been described by CHILINGAR and TERRY(1954). The sample is
heated in a micro-crucible at a constant rate in a current of COz and the temperature
-weight relationship is determined; from this the MgO and CaO contents can be
calculated.

Calcium gravimetric method (GROVES,1951). Add sufficient water to the filtrate

obtained earlier from the Rz03 group precipitation (p.298) so that the volume
is approximately 250 ml, contained in a 600-ml beaker, and heat to boiling after
acidifying with a few drops of hydrochloric acid. While boiling add 10 ml of
5 % w/v ammonium oxalate solution and one or two drops of universal indicator.
Add ammonium hydroxide dropwise until the indicator changes from red to blue;
306 K. H. WOLF, A. J. EASTON AND S. WARNE

continue boiling for 10-20 min. The presence of a boiling stick assists in the
prevention of bumping.
Set the beaker aside on a water bath for 1-2 h, and then allow to remain cold
for 4-5 h to ensure complete precipitation of the calcium oxalate.
Filter off the precipitate through a 540 Whatman filter paper and wash the
precipitate with 1 % w/v ammonium oxalate solution three or four times.
Dissolve the precipitate back into the original beaker with hydrochloric acid
and wash the filter paper with hot water. Reprecipitate the calcium oxalate after
adjusting the volume again to 250 ml and adding 5 ml of the ammonium oxalate,
by the addition of ammonium hydroxide as before. (The second precipitation being
made in a nearly salt-free solution avoids the coprecipitation of other ions, e.g.,
Mg.) After boiling for 10 min, the precipitate is again set aside as before. The
precipitate is filtered through a 540 Whatman filter paper and washed with 1 %
w/v ammonium oxalate solution.
The precipitate is ignited in a weighed platinum crucible, initially at a low
temperature and finally at 1,100"C. After cooling in a desiccator for 30 min,
the calcium is weighed as the oxide. The ignition is repeated until a constant
weight is obtained.
Note: The precipitate also contains SrO; thus an adjustment is made after
measurement of strontium by the flame photometry method.

Calcium titration method (PATTONand REEDER,1956)

Transfer the combined filtrate obtained earlier from the Rz03 group precipitation
(p.298) to a volumetric flask, e.g., 250 ml, and adjust to volume with water. Shake
well to ensure complete mixing.
Place an aliquot containing approximately 25 mg of calcium as CaO in
a 250-ml beaker. Add 10 ml of concentrated nitric acid and evaporate to dryness
on a steam bath to remove the ammonium salts. Rinse down the sides of the beaker,
add 2 ml of nitric acid, and evaporate again. Take up the residue with approx-
imately 50 ml of water and transfer to a 250-ml conical flask. Add 10 ml of a 10%
w/v sodium hydroxide solution (pH should be ~ 1 2 )and , a few milligrams of
both sodium cyanide and hydroxylamine hydrochloride. Stopper the flask and set
aside for 1 h. Any magnesium present will precipitate as magnesium hydroxide.
After the period of standing, add a few milligrams of Patton and Reeders
reagent [2-hydroxy-1 (-2 hydroxy-4-sulpho-l-naphthylazo)-3-naphthoic acid]. This
reagent is usually diluted: 0.0375 g with 20 g of sodium chloride. Then titrate with
1 % w/v E.D.T.A. (disodium salt) until the indicator changes from red to a clear
sky blue color.
The E.D.T.A. solution is standardized against a standard calcium solution
prepared from calcium oxide obtained by heating A.R. calcium carbonate to
1,OOO"C for 1 h and then cooling in a desiccator for 30 min. Dissolve 1 g of the
freshly ignited CaO in 100 ml of 5 % v/v hydrochloric acid and dilute to 1 1 with
EXAMINATION AND ANALYSIS OF SEDIMENTARY CARBONATES 307

water; then each 1 ml will contain 1 mg of calcium as CaO. Use 25-ml portions
of the standard calcium solution to standardize the E.D.T.A. solution.

Determination of magnesium
Two methods are available for the determination of magnesium: (I) gravimetric
precipitation as magnesium pyrophosphatel, and (2) titration with E.D.T.A.
Where magnesium carbonate is only a minor constituent, e.g., a fraction of
1 % as in some limestones, the titration method is preferred.

Magnesium gravimetric method (GROVES, 1951). Adjust the volume of the two
filtrates obtained earlier from the calcium precipitation (see the section on the
calcium titration method) to approximately 800 ml in a 1-1 beaker. Make the
solution just acid with a few drops of hydrochloric acid and add several drops
of universal indicator. Add 10 ml 10% w/v ammonium phosphate solution and
stir to mix. Add ammonium hydroxide dropwise stirring vigorously until the
magnesium pyrophosphate precipitate just appears. Cease the addition of ammo-
nium hydroxide and stir vigorously for several minutes. The slow precipitation
ensures a coarse crystalline precipitate. Continue the addition of ammonium
hydroxide until the indicator turns purple (pH 11), then add excess ammonium
hydroxide, 5 ml for each 100 ml of solution, and set aside overnight.
Filter through a 540 Whatman filter paper and wash the precipitate with
5 % v/v ammonium hydroxide solution three or four times. Dissolve the precipi-
tate into the original beaker with 25% v/v hydrochloric acid, washing the filter
paper well with 200-300 ml of water. Add 5 ml more of 10% w/v ammonium-
phosphate solution and several drops of universal indicator. Reprecipitate as be-
fore after adjusting the volume to approximately 800 ml. Filter and wash the pre-
cipitate as before and ignite in a weighed platinum crucible. Care should be taken
during the filtration of the magnesium pyrophosphate that the surface of the glass
funnel above the filter paper remains dry. If this is not the case, the precipitate
will tend to creep up the glass. This may be counteracted by washing particles
down into the filter paper with ethyl alcohol.
The precipitate should be ignited at a minimum temperature with free access
of air to avoid reduction of the phosphate. Then the temperature should be raised
slowly until it reaches approximately 1,OOO"C. The crucible is allowed to cool in
a desiccator for 30 min before weighing. It is ignited again until a constant weight
is obtained.
Inasmuch as there is a possibility that manganese will not completely
precipitate with the R203 group, the magnesium pyrophosphate precipitate is
examined for manganese.

Actually magnesium ammonium phosphate is the precipitate, and magnesium pyrophosphate

is the result of ignition.
308 K. H. WOLF, A. J. EASTON AND S. WARNE

Examination of precipitate for manganese. The ignited precipitate is dissolved in

5 ml 15 % v/v sulphuric acid and the solution transferred to a volumetric flask
(e.g., 50 ml). Either the whole solution or an aliquot is taken and the manganese
is determined as permanganate by the procedure given under the analysis of the
R2O3 group. The weight of this manganese is added to that previously found in the
R203 group.
The weight of manganese determined as MnO is converted to Mn2P207;
on using a factor of 2 before deduction from the weight of the magnesium as
MgzPz07; 0.3621 * MgzPz07 = MgO.

Magnesium titration method (CHENGet al., 1952). Transfer the two filtrates from
the RzO3 group precipitation to a volumetric flask (e.g., 250-ml) and adjust to
volume with water. Shake well to ensure complete mixing.
Place an aliquot containing approximately 25 mg of magnesium as MgO in a
250-ml beaker and acidify with hydrochloric acid. Then add 5 ml of 5 % w/v
ammonium oxalate solution to precipitate the calcium present, and while the so-
lution is gently boiling neutralize with ammonium hydroxide solution and add
2-3 ml in excess. After boiling for 10 min, allow the beaker to cool and stand for
2 h; then filter off the precipitated calcium oxalate through a 540 Whatman filter
paper into a 250-ml conical flask.
Test the filtrate for completeness of precipitation of the calcium by adding
one or two drops of 5 % w/v ammonium oxalate to the solution. Upon warming,
no turbidity should develop if the precipitation is complete. If a turbidity does
develop, add 5 ml more of the ammonium oxalate solution and boil, allow to
stand and filter as before.
Heat the solution almost to boiling and add one or two drops of 10% w/v
hydroxylamine hydrochloride solution to reduce any manganese present. Then add
10 ml of ammonium hydroxide buffer (to 60 g of NH4CI dissolved in 200 ml of
water, add 570 ml of ammonium hydroxide and dilute to 1 I).
Add 1-2 ml of solochrome black (eriochrome black) solution (0.2 g of reagent
dissolved in 50 ml of ethyl alcohol) and titrate with 1 % w/v E.D.T.A. (disodium-
salt) solution until the indicator changes from red to clear sky blue color.
The E.D.T.A. solution is standardized against a standard magnesium
solution prepared from magnesium oxide. The latter is obtained by heating A.R.
magnesium carbonate to 1,OOO"C for 1 h and then cooling in a desiccator for 30
min. Dissolve 1 g of the freshly ignited MgO in 5 ml of hydrochloric acid and dilute
to 1 1 with water; then each 1 ml will contain 1 mg of magnesium as MgO. Use
25-ml portions of the standard magnesium solution to standardize the E.D.T.A.
solution.
EXAMINATION A N D ANALYSIS OF SEDIMENTARY CARBONATES 309

Determination of ferrous iron

Apparatus. Fit a 250-ml conical flask with a tight-fitting rubber stopper in which
three holes have been bored. To two holes fit a piece of glass tubing bent at right
angles. One is for the entry of an oxygen-free inert gas, e.g., COz, Nz. To the second
attach a Bunsen valve to allow exit of the gas. Place a thistle funnel with a stopcock
capable of holding 20 ml of acid in the third hole.

Method. The sample is dissolved in hydrochloric acid in the absence of oxygen so

that the ferrous iron present in the sample remains in the reduced state. 2,2'-
dipyridyl solution is added and forms a sufficiently strong complex with the ferrous
iron to avoid oxidation during the removal of the insoluble material by filtration.
Weigh out a quantity of the sample which will contain 0.05-0.5 mg of iron
calculated from the total iron determination (see above). If the iron content is
high, the quantity to be taken should be such that a ten-fold dilution after solution
of the sample will bring it to within this range.
Transfer the weighed material to the conical flask and add 20 ml of water;
then swirl the contents carefully to wet the sample. Connect the inert gas supply
and allow it to pass through the flask for 5-10 min to expel the air.
Add 10 ml of 10% v/v hydrochloric acid to the thistle funnel, depress the
Bunsen valve and slowly add the acid to the contents of the flask. After the vigor-
ous reaction has finished, release the Bunsen valve to its normal position and
warm on a water bath to 50-60°C for 30 min to complete the reaction. After this
period, allow the flask to cool to room temperature either naturally or by cooling
in a trough of cold water.
Disconnect the gas supply and immediately add 10 ml of 0.2% w/v 2,2'-
dipyridyl solution (prepared in 1.5 % v/v hydrochloric acid). Filter the solution
through a previously water-washed 541 Whatman filter paper into a 100-ml
volumetric flask, washing the sides of the conical flask with small portions of
water. Wash the residue several times with small portions of water.
If a maximum of 0.5 mg of iron has been calculated to be present, add 25 ml
of sodium acetate buffer (272 g CHsCOONa.3HzO per liter) and adjust the volume
to 100 ml with water.
If 5.0 mg of iron has been calculated to be present in the solution, adjust the
volume to 100 ml, mix well and pipette a 10-ml aliquot of this solution into another
100-ml volumetric flask. To this flask add 5 ml of 0.2 % w/v 2,2'-dipyridyl solution
and 25 ml of sodium acetate buffer, and adjust to 100 ml with water.
Measure the absorbance of the solution against water in a 1-cm cell using a
spectrophotometer with the wave-length set at 522 mp.Compare the absorbance of
the sample solution with a standard curve (Fig.l3), which may be calculated from
the curve prepared for the determination of total iron (see above).
The ferric iron is calculated by converting the FeO value to Fez03 and sub-
3 10 K . H. WOLF, A. J. EASTON AND S. WARNE

0.6

“c
01

0.3
0
n
u)

Fig. 13. Hypothetical “standard curve” of absorbanceversus FeO content used in spectrophotom-
etry. Wave length 522 mp; volume 100 ml; I cm cell.

tracting this from the total iron taken as Fez03; the difference is the amount of
ferric iron, i.e., Fez03 (0.9 * Fez03 = FeO).

Determination of sodium, potassium and strontium

The determination of these elements by flame-photometry requires the measure-

ment of the radiation emitted by these elements from a solution excited by a
flame (DEAN,1960). The sample solution is drawn up in a finely divided state into
a flame, and the resulting radiation compared with that given by standard solutions
under the same conditions. A number of combinations of flame condition and
instrument are available. The details given here are for a Beckman flame-photo-
metric attachment, but the procedures for measurement of background and
elimination of interferences are generally applicable.

Interferences. The main interfering ions in the determination of sodium and po-
tassium are the members of the RzO3 group, i.e., Fe, Al, and the elements Ca and
Mg. The interfering elements emit their own characteristic radiation which inter-
feres with that of the alkalies, e.g., Fe and Ca. The other type of interference is a
depression ofthe radiation, and this is exhibited by A1 and Mg. It is for this reason
that the Rz03 group and calcium are separated before the measurement of the
alkalies in the flame.
In the case of strontium only, the Rz03 group is removed (DIAMOND, 1955);
the precipitation of calcium would also precipitate the strontium as oxalate. The
interference caused by magnesium is eliminated by the use of standard addition
technique, provided the background radiation is first deducted.

Background. When small quantities ( < O . 1 %) of sodium and potassium (also

strontium) are measured (EASTONand LOVERING, 1964), a large slit width is re-
quired which will allow extraneous radiation also to be measured. This radiation,
EXAMINATION A N D ANALYSIS OF SEDIMENTARY CARBONATES 31 1

72 5 768 825
Potassium
Fig.14. Curve constructed to determine both the background and peak heights of each sample
and standard; examplified here by potassium. The relevant wave lengths for each element are
given in Table VII. In all subsequent measurements, used for obtaining either an approximate
value (Fig.15) or for the standard addition technique (Fig.l6), the background is deducted
leaving only the peak height to be plotted. (Wave lengths in mp.)

which is not associated with the radiation from the elements to be measured, is
known as background (Fig.14). In the case of potassium it is necessary to take
readings of the background at both 725 and 825 mp and calculate graphically the
background at 768 mp. The wave lengths for the measurement of the peak and
background radiation are given in Table VII.

Preparation of the sample solution for sodium and potassium. Weigh 0.5 g of the
sample into a 250-ml beaker, add 25 ml of water followed by 10 ml of 50% v/v
hydrochloric acid, and place the beaker on a water bath for 30 min to allow com-
plete solution of the carbonate portion of the sample. Wash the cover glass into the
beaker and add 1 g of A.R. oxalic acid; heat gently at first to dissolve the sample
and then heat almost to boiling. Pass ammonia vapor through the solution until
the solution is neutral to Universal indicator paper. This will precipitate the RzO3
group components as hydroxides and the calcium as calcium oxalate. The passage
of compressed air through a wash bottle containing ammonium hydroxide
(s.g. = 0.88) is a convenient method of obtaining the ammonia vapor for the neu-
tralization. After neutralizing the solution, stand the beaker on a steam bath for
10 min to complete precipitation.

TABLE VII

WAVE LENGTHS FOR THE MEASUREMENT OF RADIATION (mp)

Na K Sr

peak 588 768 46 1

background 580 or 600 125 and 825 466
312 K. H. WOLF, A. J. EASTON AND S. WARNE

The precipitated hydroxides and calcium oxalate are centrifuged off using
clean glass tubes. The supernatant liquid is collected in a 50-ml volumetric flask,
I .5 ml of hydrochloric acid is added and the solution is allowed to cool before being
adjusted to volume with water. This solution is set aside for measurement of the
amounts of sodium and potassium. A blank is prepared by using the same quan-
tity of reagents as above.

Preparation of sample solutionfor strontium. Weigh 0.5 g of the sample into a 250-ml
beaker, add 25 ml of water followed by 10 ml of 50% v/v hydrochloric acid, and
place the beaker on a water bath for 30 min to allow complete solution of the car-
bonate portion of the sample. Wash the cover glass into the beaker. Pass ammonia
vapor through the solution until the solution is neutral to universal indicator paper.
After neutralizing the solution, stand the beaker on a steam bath for 10 min to
complete precipitation. The precipitated hydroxides are centrifuged off using
clean glass tubes. The supernatant liquid is collected in a 50-ml volumetric flask,
1.5 ml of hydrochloric acid is added and the solution is allowed to cool before
being adjusted to volume with water. This solution is set aside for the measurement
of strontium.

Preparation of standard solutions. Weigh 2.54 g of dried A.R. sodium chloride

(for Na standard), 1.91 g of dried A.R. potassium chloride (for K standard), and
1.685 g of dried A.R. strontium carbonate (for Sr standard) into three separate
100-ml beakers. Dissolve the material in 20-50 ml of water (add a minimum of
HCI for the SrC03) and transfer the solutions to three 1-1flasks; then make up to
volume with 1 % v/v hydrochloric acid. The concentration of Na, K and Sr in
these solutions is 1,OOO p.p.m. These solutions are then diluted with 1 % v/v
hydrochloric acid to the required range of concentrations: this will usually be
1-10 and 10-100 p.p.m; (0.1-1.0 for the blank).

Concentration
(ppm. Na, K or S r )

Fig.15. Curve constructed from four standards such that the radiation given by the sample lies
within the range covered by that of the standards. The background has been deducted in each case
prior to plotting. The approximate concentration (in p.p.m.) of the element in the solution is
obtained by reference to the horizontal axis. This approximate value is used as a guide to the
strength of the standard solutions required when using the “standard addition” technique (see
Fig. 16).
EXAMINATION AND ANALYSIS OF SEDIMENTARY CARBONATES 313

Measurement of approximate value. First, an approximate value is obtained by

direct comparison with standards both above and below the transmission given by
the sample. Turn the wave-length dial to the peak transmission for the element and
adjust the slit width so that the highest standard selected gives a high transmission
reading, e.g., 80-90 %.
Now place the standards and sample solution alternately in the flame,
repeating the operation until constant readings are obtained and the sample solu-
tion has been bracketed by standards. Record these readings and repeat the opera-
tion for the same solutions, with the dial turned to the background wave-lengths to
obtain readings on any background present. Subtract the background from the
readings and use the peak heights to obtain an approximate value (Fig.15).
Deduct the appropriate blanks.

Measurement by standard addition. Having obtained an approximate value of the

content by the procedure given above, place 5-ml aliquots of the sample solution
in four 25-ml beakers.
To the first beaker add 5 ml of water and to the other three add 5 ml of
standard solutions, so that the first addition is equal in parts per million to the
previously found approximate value. The others are of higher concentrations.
Swirl to mix the four solutions and then place them in succession in the flame with
the wave-length dial turned to the peak wave-length. Record the transmission.
Repeat the operation with the wave-length dial turned to the background wave-
length to obtain readings of any background present. If a background is present,
subtract this from the former readings.
These results are now plotted graphically as shown in Fig.16, and the line
joining the points is projected back to the base line from which the concentration
of the unknown sample solution is read.

Determination of total sulphur (A. I. VOGEL,1951)

Weigh up to 25 g of the sample into a 400-ml beaker and add 100 ml of saturated
bromine water; stir to ensure complete wetting of the sample. Add nitric acid
dropwise until the sample is dissolved. A violent reaction should be avoided be-
cause loss of HzS will cause a low result. After solution of the sample, gently heat
the solution to discharge the excess bromine.
After the bulk of the bromine has been discharged, filter off any insoluble
residue through a 541 Whatman filter paper. Wash the residue three or four times
with hot water. Add 10 ml of hydrochloric acid to the filtrate and evaporate to
dryness on a water bath to discharge the nitric acid. Take up the residue in 250
ml of hot water and heat to boiling.
Remove the beaker from the heater and add 10 ml of hydrochloric acid to
make the solution acid (0.5 N). Slowly add 10 ml of hot 5 % w/v barium chloride
314 K. H. WOLF, A. J. EASTON AND S. WARNE

Content 0 Addition
(ppm. Na,K or Sr)

Fig.16. Curve constructed to determine the exact concentration by “standard addition”. Point I,
indicating the lowest percentage of transmission, represents 5 ml of the unknown sample (whose
concentration has been determined approximately) plus 5 ml of water. Point 2: 5 ml of the
unknown sample plus 5 ml of a standard of about the same concentration as the approximate
value of the unknown sample. Point 3: 5 ml of unknown sample plus 5 ml of a standard having
50% higher concentration than that used for point 2. Point 4, indicating the highest percentage
of transmission, represents 5 ml of unknown sample plus 5 ml of a standard having 100% higher
concentration than that used for point 2. In all cases the background has been deducted and the
peak heights plotted. Point 0 indicates zero addition only and is not to be confused with “zero
content” which lies farther to the left on the horizontal axis. p.p.m. x 50 = weight in micro-
grams of the element; weight of the element in grams x 100 divided by the weight of the
sample gives the percentage.

solution, stirring continuously. Allow the beaker to stand on a water bath for 2 h,
filter precipitate through a 540 Whatman filter paper, and wash with small portions
of cold water. Continue the washings until the filtrate is free from chloride, as
shown by allowing a few drops of the filtrate to collect in a test tube containing
1-2 ml of 1 % w/v silver-nitrate solution.
Ignite the precipitate in a previously weighed platinum crucible, allowing
free access of air to avoid reduction of the barium sulphate. Continue ignition
until a constant weight is obtained.
Calculate the sulphur content of the sample from the weight of the ignited
BaS04: 0.13735 * Bas04 = S

Determination of sukhur trioxide (NATIONAL BUREAUOF STANDARD METHODS,

1928). Weigh up to 25 g of the sample into a 400-mlbeaker and add dilute 50 % v/v
hydrochloric acid until the sample is dissolved. Then add additional 10 ml of acid
and evaporate the solution nearly to dryness. This will discharge any sulphide
present in the sample, leaving sulphate ions in the residue. Increase the volume to
250 ml with hot water and filter off any insoluble residue through a 541 Whatman
filter paper; wash the residue three or four times with hot water. Heat the solution
to boiling.
Precipitate the sulphate, filter and ignite the precipitate as described above
for the determination of total sulphur.
EXAMINATION A N D ANALYSIS OF SEDIMENTARY CARBONATES 315

Chlorine (A. I. VOGEL,1951)

The chloride ions present in the neutral sample solution are titrated with silver-
nitrate solution. In the presence of a slight excess of silver ions, a red coloration,
(i.e., silver chromate) is formed indicating the end point of the titration. The
surface of the sample should be cleaned with dilute 5 % v/v nitric acid.
Weigh 2-5 g of the sample into a 250-ml beaker and add sufficient nitric
acid under a cover glass to dissolve the sample. Warm until the reaction has
ceased, then filter through a 541 Whatman filter paper. Evaporate the filtrate to
dryness on a water bath and bake for 1 h to expel any excess nitric acid present.
Dissolve the residue in 100 ml of water and transfer the solution to a 250-ml
conical flask. Check by the use of Universal indicator paper that the solution is
neutral and add a small excess of A.R. ammonium acetate in the solid form.
Add 1 ml of 2.5% v/v potassium-chromate solution as indicator and
titrate with silver nitrate solution (1.699 g AgN03/1). The end point is indicated
by the formation of deep-red silver chromate. 1 ml of silver nitrate solution =
0.0003546 g CI.

DIFFERENTIAL THERMAL ANALYSIS

The use of differential thermal analysis (D.T.A.) equipment is now routine in

petrological and mineralogical laboratories. This technique is widely used for
carbonate minerals and rock studies. The latest equipment, once loaded with the
test sample and switched on, will continuously record the endothermic and exo-
thermic data as a thermogram at preset heating rate, sensitivity and furnace
atmosphere conditions.
Carbonate minerals considered here are classified in Table VIII.
For reference, thermograms characteristic of these carbonates, obtained
from specimens of known chemical composition, are given in Table IX. These
were determined from material crushed to -150 mesh (B.S.S.), heated at lSoC/
min, while the furnace atmospheres other than air were maintained by a 2 I/min

TABLE VIII

CLASSIFICATION OF SOME CARBONATE MINERALS

Calcite group Aragonite group Dolomite group

siderite aragonite dolomite

magnesite witherite ankerite
calcite strontianite
316 K. H. WOLF, A. J. EASTON AND S. WARNE

TABLE IX

CHEMICAL ANALYSIS OF SOME CARBONATE MINERALS'

Mineral CaCO3 Mgc03 FeCO3 MnCO3 BaCO3 SrCO3 Bas04 SiOz Fez03 Total
f %I

ankerite 51.63 19.05 28.23 1.09 - - - 0.07 - 100.07

calcite 98.70 trace 0.48 - - - - - - 99.18
dolomite 50.82 39.33 5.52 trace - - - 4.33 - 100.00
magnesite - 99.40 0.96 - - - - - - 100.36
siderite 1.46 9.50 81.86 6.38 - - - 0.48 0.10 99.78
witherite 0.70 - - - 95.57 2.16 1.61 - - 100.04
strontianite 7.60 - - - - 92.42 - - - 100.02

1 The D.T.A. and T.G.A. curves of the listed minerals are given in this chapter. These analyses
were generously provided by the Western Australian Government Chemical Laboratories, the
New South Wales Department of Mines, and the School of Applied Geology, University of New
South Wales.

of a particular gas flow. This, together with the apparatus used, has been described
elsewhere (WARNE,1964).
BECK (1950), WEBBand HEYSTEK(1957) and SMYKATZ-KLOSS (1964) pro-
vided D.T.A. data on less common carbonates; whereas the marked influence on
thermogram configuration of controllable variables, and specifically crystallinity,
has been described respectively by BAYLISSand WARNE (1 962) and BAYLISS(1964).

Calcite group1

Siderite (FeCO3)
The thermogram of siderite determined in air is characterized by a single endother-
mic peak Ed./ (sometimes preceded by a small exothermic peak: Ex.I), which is
followed by two exothermic peaks Ex.2 and Ex.3 (Fig. 17, curve 13). The peak
temperatures occur at approximately 520", 590", 675 " and 850°C.
The conflicting published decomposition mechanisms of siderite were re-
viewed by WARNE(1961), from which it would appear that the decomposition
mechanism described by KULPet al. (1951) is the most acceptable. It involves three
reactions:
(I) FeCOa-tFeO COz?+ endothermic (Ed./)
(2) 2Fe0 +
O+a-Fez03 y-Fez03 + exothermic (Ex.2)
(3) y-Fez03-ta-Fez03 exothermic (Ex..?)

For the D.T.A. of rhodochrosite (MnC03) and smithsonite (ZnCOa), see KissiNGER et al.
(1956) and WEBBand HEYSTEK
(1957), respectively.
EXAMINATION AND ANALYSIS OF SEDIMENTARY CARBONATES 317

The small exothermic peak, Ex.1, has been attributed (PAPAILHAU, 1958)
to the immediate oxidation of the FeO released during the initial slow decomposi-
tion of FeC03. After a small increase in temperature, however, the endothermic
decomposition rate rapidly increases and becomes dominant (Ed.I). The major
exothermic peak, Ex.2, is generally partially superimposed on the preceding
endothermic peak, Ed.1, which consequently shows some size reduction.
When determined in COz or inert gases, the thermogram is composed solely
of the fully developed endothermic peak, Ed.1, caused by the reaction I given
above (Fig.17, curve 12). In Nz and COz the thermograms are similar, except that
the commencement of the reaction and its peak temperature occur at slightly
higher temperatures in COe. The second reaction probably occurs because the
end product is magnetite (Fe304) (cf. KISSINGER et al., 1956). The reaction rate
must be slow and uniform as no additional recognizable peak is recorded:
3Fe0 + COz+Fe304 + CO f
SCHWOB(1950) indicated that such a reaction was possible, and the slow
oxidation of FeO, liberated by the D.T.A. of siderite in nitrogen, has been attrib-
uted to the same reaction (CAILL~RE, 1962).
Under closely reproducible conditions, the detection limits and the effects
on thermogram configuration of many carbonate minerals, caused by progressive
artificial dilution with alundum, have been determined (WARNE,1963). The de-
tection limits for siderite were between 2 5 5 % and 1-2% when determined in
air and Nz, respectively.
When determined in air, the thermogram shows a major modification for
siderite contents between 30 and 40 % (by weight). Here, the increasing diminution
of the endothermic peak, Ed.Z, becomes very marked; this gradually occurs with
decreasing siderite content due to the progressive superposition of the stronger
exothermic peak, Ex.2 (Fig. 17). At about 30 % siderite content, the resultant ther-
mogram contains only a relatively small exothermic peak, because the exothermic
peak, Ex.3, has become too weak to be recorded. With further decreases in siderite
content, this single exothermic peak is so rapidly reduced in size that below 20 % it
is recorded as a relatively insignificant feature. This confirms in detail the results of
ROWLAND and JONAS (1949). In 0 2 this process is accelerated. Thus, the endother-
mic peak is completely suppressed even when 100 % siderite is present (ROWLAND
and JONAS,1949; PAPAILHAU, 1958, 1959). The same effect was obtained by finely
grinding the sample before D.T.A. analysis (ROWLAND and JONAS,1949).

Magnesite ( M g c o 3 )
The available literature on magnesite D.T.A. is listed by SCHWOB (1950), WARNE
(1962) SMYKATZ-KLOSS (1964). The D.T.A. and decomposition mechanisms of
rhodochrosite have been described in detail by KULPet al. (1949) and KISSINCER
318 K . H. WOLF, A. J. EASTON AND S. WARNE

et al. (1956), and those of breunnerite and pistomesite by BECK(1950) and SCHWOB
(1 950).
The thermogram of magnesite, determined in air, is composed of a single large
asymmetrical endothermic peak, due to the simple irreversible reaction: MgC03
+MgO +C02 .T (SCHWOB, 1950). The peak temperature usually occurs between
660 and 700°C (Fig. 17). The additional small peaks sometimes recorded at higher
temperatures (Fig.17, curve 19) have been attributed to the presence of small
amounts of Ca, Feyand/or Mn. The formation of intermediate oxycarbonates as
suggested by BRILL(1905) was not supported by X-ray and optical studies (BECK,
1950).
The thermogram configuration is little affected by furnace atmosphere con-
ditions (SCHWOB,1950; HAUL and HEYSTEK,1952; and WARNE,1963). The
presence of only 1.xNaCl, however, lowers the peak temperature 50°C (BERG,
1943), and sharpens the initial inflection point (WEBBand HEYSTEK, 1957). The
effects of progressive dilution are a gradual reduction in peak height, area, and
temperature, whereas the detection limit is approximately 1% (Fig.17; WARNE,
1963).

Calcite (CaCO3)
WEBBand HEYSTEK (1957) and WARNE (1963) have reviewed the literature on cal-
cite D.T.A. In air or N2 the thermograms are similar, being composed of a single
large asymmetrical endothermic peak caused by the reaction CaCOasCaO +
C02 t . The peak temperature generally occurs between 960 and 990°C.
Evidence ranging from distortions to marked bifurcation of the calcite and
aragonite endothermic peak, as figured by FAUST(1950), GRUVER (1950b), and
WEBBand HEYSTEK (1957) has been attributed to the decomposition of two “types”
of CaCO3 present: (1) primary calcite; (2) calcite formed by the inversion of arago-
nite. Thus, thermograms from samples containing mixtures of two calcites having
markedly different crystallinity might be expected to show similar modifications.
Determination in static or dynamic C02 atmospheres (ROWLAND and LEWIS,
1951; and WARNE,1963, respectively) displaces the endothermic peak up scale,
thus increasing the peak temperature by about 60°C (Fig.18, curves 5 and 6).
From a mixture of calcite and quartz, LIPPMAN (1952) recorded a small
exothermic fluctuation due to wollastonite (CaSi03) formation, immediately
following the “calcite” endothermic peak. This reaction was confirmed only when

Fig.17. D.T.A. curves of the major carbonates (siderite and magnesite) illustrating thermogram
configuration and the effects of dilution and furnace atmosphere.

Fig.18. D.T.A. curves of the major carbonates (calcite, aragonite, witherite, strontianite and
dolomite) illustrating thermogram configuration and the effects of dilution and furnace atmos-
phere, and the difference between dolomite and a comparable mixture of magnesite plus calcite.
 319
I , '
mo roo 600 mo roi~c
5k5
'
-2
%8
SIDERITE

30170

WLDMITE

2ibl

MAGNESITE
,9

_-------DETERMNED IN N
................. DETERMINED IN 0; K

U
200 rpo 600 800 , lppopo'c
320 K. H. WOLF, A. J. EASTON AND S. WARNE

the constituents were very fine grained and intimately mixed (WARNE,1963).
Thermograms from mixtures containing siderite or magnesite instead of calcite,
contained no peaks attributable to Fe- or Mg-silicate formation.
A gradual reduction in peak height, area and temperature results from pro-
gressive dilution; the detection limit is about 1 % (Fig.18; WARNE,1963).

Aragonite group1

Aragonite (CaCO3)
The thermograms of aragonite and calcite are similar, having a large endothermic
+
peak caused by the same reaction: CaCOasCaO COZf . In addition, aragon-
ite has a small endothermic peak between about 400 and 500°C due to the inversion
of orthorhombic aragonite to trigonal calcite (Fig.18, curve 8). The latter small
characteristic inversion peak is not detected when aragonite content is much below
35 %. This may vary considerably with the sensitivity of the D.T.A. unit used.

Witherite2 (BaCO3) and strontianite (SrCO3)

The witherite and strontianite thermograms of CUTHBERT and ROWLAND(1947),
GRUVER(1 950a), KAUFFMAN and DILLING (1 950), BARONet al. (1959), WARNE
(1963), and SMYKATZ-KLOSS (1964) are in good agreement. The witherite thermo-
gram is composed of two small sharp endothermic peaks (peak temperatures at
about 820 and 980"C), due to reversible inversions from a to /l to y forms; whereas
the cooling curve shows two similar exothermic peaks at somewhat lower tempera-
tures due to y to /l to a inversions (Fig.18, curve 9). No decomposition takes place
below 1,350"C.
The thermogram of strontianite below 1,OOO"C is composed of a small
sharp endothermic peak (approximate peak temperature is 930 "C) caused by an
orthorhombic to trigonal inversion. Inasmuch as the latter is reversible, it shows
as an exothermic peak on the cooling curve at about 850°C (Fig.18, curve 20). At
temperatures above 1,000"C, endothermic decomposition starts, giving a peak
temperature at about 1,200"C (WEBBand HEYSTEK, 1957).
The presence of strontianite with calcite, endothermic peaks of which are
usually superimposed, may be detected by the exothermic strontianite inversion
peak on the cooling curve. If cooled in COz, however, this peak will be obscured by
the recarbonation peak of calcite.

1 Cerussite has been studied in detail by WARNE

and BAYLISS
(1962).
* Thermograms of bromlite, BaCa(CO&, and baryto-calcitehave been published by BECK(1950).
EXAMINATION A N D ANALYSIS OF SEDIMENTARY CARBONATES 32 1

Dolomite group'

Dolomite, C a M g ( C 0 3 ) ~
The available literature on dolomite D.T.A. is listed by SCHWOB ( I 950), GABINET
(1959), WARNE (1962), and SMYKATZ-KLOSS (1964).
Thermograms of dolomite determined in air or nitrogen are similar, being
composed of two large endothermic peaks (Fig. 18, curve 18). The peak tempera-
tures occur at approximately 800 and 950°C. It is generally accepted that the first
and second endothermic peaks are caused by the dissociation of C02 from the
ions in the Mg and Ca lattice positions, respectively.
The first and second dolomite peaks occur at considerably higher and slightly
lower temperatures than the corresponding peaks of magnesite and calcite (BECK,
1950). This enables one to differentiate dolomite from magnesite, calcite, or their
mixture (Fig.18, curve 19). For dolomite+alcite mixtures, the CaC03 decom-
position peaks of both minerals are usually superimposed, but the presence of
considerable proportions of calcite may be inferred from the disproportionate
enlargement of the resulting peak (Fig.18, curves 16 and 17; WARNE,1964).
Occasionally, incomplete superposition results in a doubly terminating feature
(SMYKATZ-KLOSS, 1964).The presence of salts, although greatly affecting the initial
decomposition temperature, leaves the second peak unaltered (MURRAYet al.,
1951).
The D.T.A. of dolomite in C02 results in lowering and raising the first and
second peak temperatures, respectively; whereas the cooling curve (in C02)
shows only the exothermic recarbonation peak of calcite (Fig.18, curve 15).
With progressive dilution, the peak sizes, areas and temperatures gradually de-
crease, but the second peak temperature falls more rapidly than the first. Thus, for
dolomite contents below 20 % these peaks slowly coalesce to form a single peak.
This is observable down to the detection limit of about 1 X(Fig.18; WARNE,1963).

Ankerite, Ca(Mg,Fe) (CO3)z

Ankerite thermograms (in air) contain three endothermic peaks, with peak
temperatures generally occurring between 700-800 "C, 830-870 "C, and 930-950 "C,
respectively. The first peak is sometimes followed by an exothermic reaction, which
suppresses the immediately preceding and following peaks to a variable degree
(cf. the published thermograms by GABINET, 1959; WARNE, 1962; and SMYKATZ-
KLOSS, 1964).
The increase in size of the second endothermic peak (not the first) with in-
creasing Fez+content, and the production of a similar peak from a calcite-hematite

1For thermograms of huntite, MgCa(CO&, see FAUST and NEMECZ

(1953), KOBLENCZ (1953), and
BARON et al. (1959).
322 K. H. WOLF, A. J. EASTON AND S. WARNE

mixture (KULPet a]., 1951), apparently invalidates the mechanism of BECK(1951)

and SMYKATZ-KLOSS (1964).
According to KULP et al. (1951), dissociation at Mg positions in the lattice
causes the first peak; MgO and FeO are released, the latter oxidizing immediately
to y-FezO3 (exothermic). The Fez03.CaC03 formation produces the second en-
dothermic peak (hence the dependence of the size of this peak on Fez+ content),
whereas the dissociation of C02 from the Fe203.CaC03 and residual CaC03
produces the third endothermic peak. The end products were confirmed to be
MgO and CaO.FezO3.
Peak temperature differences enable one to distinguish ankerite from mix-
tures of siderite, magnesite and calcite (the presence o f a superimposed peak of cal-
cite may be detected as described under dolomite) (Fig.20, curves I, 2 and 3). As
previously described, siderite contents below 30% are best detected by using N2
atmosphere.
Progressive dilution effects are similar to those of dolomite, except that all
three peaks coalesce for ankerite contents much below 20% (Fig.19). The deter-
mination in COz results in greater peak separation than shown by dolomite
(Fig.19, curve 5).

ANKERITE +CALCITE (I :I)

--
ANKERlTE +OOLOMITE +AI2O3
(2:1:1)
-
-DETERMINED IN AIR

200 400 SO0

Fig.19. Fig.20.

Fig.19. Thermograms (D.T.A.) of ankerite showing the effects of dilution and futnace atmosphere.

Fig.20. Thermograms (D.T.A.) of mixtures of carbonates minerals.

EXAMINATION AND ANALYSIS OF SEDIMENTARY CARBONATES 323

Mixtures of carbonates
Thermograms (in air) of bimineralic (1 : I ) artificial mixtures of the above described
nine carbonates show no evidence of interaction. The effects of all carbonate
peaks can be recognized even for dolomite-ankerite mixtures (Fig.20, curve 4),
although superposition of some peaks does occur (WARNE,1963).
Even though no detailed study of mixtures of all these carbonates in various
proportions was made, it is concluded that they are detectable in mixtures by
D.T.A. Detection limits should be similar to those established for the individual
mineral-dilution sequences. Due to peak coalescence, the detection limits of dolo-
mite or ankerite in mixtures may be somewhat higher. With the exception of si-
derite-rhodochrosite mixtures, this conclusion is supported by the limited number
of studies on carbonate mixtures (KULPet al., 1949, 1951; FAUST,1953; KOBLENCZ
and NEMECZ,1953; CAPDECOMME and PWLOU,1954; WEBBand HEYSTEK, 1957;
and WARNE,1964). Problems arising from the confusing multiplicity of peaks
exhibited by samples containing several minerals are greatly reduced by using the
double D.T.A. method Of GR~MSHAW et al. (1945) or D.T.A. of artificial mixtures.
Further D.T.A. data on the minerals which may occur in relatively minor
amounts in carbonate rocks are presented by MACKENZIE (1957).

THERMOGRAVIMETRIC ANALYSIS

Thermogravimetric analysis (T.G.A.), the continuous record of weight changes

produced by heating a sample at a constant rate, is complementary to D.T.A. as
it provides continuous weight variation data relatable to the D.T.A. peaks. The
variations in the rate of weight change are often recorded only as lines having
slightly different slopes on T.G.A. curves, also called thermobalance curves,
although considerable improvement is indicated by determination in self-generating
atmospheres (GARNand KESSLER,1960; GARN,1961). Simultaneous determina-
tions of T.G.A. and D.T.A. curves are described by KISSINGER et al. (1956) and
PAPAILHAU (1959).
SCHWOB (1950) studied the Fe, Mg, and Ca carbonates covering the effects
of NaCl, flux, and atmospheres of air, COZ and water vapor. PAPAILHAU (1959),
CAILLI~RE and POBEGUIN (1960), CAILL~RE (1962), and WARNE(1963) presented
additional curves. (See KISSINGER et al., 1956, and WARNEand BAYLISS,1962,
for data on rhodochrosite and cerussite.)
For reference, T.G.A. curves of the carbonate minerals used for D.T.A.,
except strontianite and witherite (the T.G.A. curve of aragonite is identical with
that of calcite), are included here in Fig. 21. They were determined on using a
continuously weighing Stanton thermobalance reading to 1 mg, and 1.00 g
samples at - 100 mesh (B.S.S.). The heating rate was 5.5 "C/min. Diagnostically
different curves are presented for: ( I ) magnesite, (2) siderite, (3) dolomite and
ankerite, and (4) calcite. Although thermogravimetric studies of carbonate
324 K. H. WOLF, A. J. EASTON AND S. WARNE

i " " " " " " " " " 1

TEMPERATVRE(~C)

Fig.21. Curves illustrating the T.G.A. of siderite, rnagnesite, calcite, dolomite and ankerite, the
D.T.A. curves of which are shown in Fig.17-20.

mixtures have not been made, the detection of reasonable proportions of these
minerals in bimineralic mixtures, with the exception of dolomite and ankerite
or calcite with dolomite or ankerite, appears likely. The anticipated detection
limits by T.G.A. would be considerably higher than those by D.T.A.

X-RAY DIFFRACTION

Amongst the many descriptions of the experimental methods and techniques for
X-ray diffraction those of AZAROFF and BUERGER (1958), BRINDLEY (1961), and
GRAFand GOLDSMITH (1963) provide a good coverage.
The diffraction patterns of the carbonate and associated minerals in car-
bonate rocks are diagnostically different and their identification is made by refer-
ence to suitable collations of X-ray diffraction data, such as the A.S.T.M. X-ray
powder data index (BROWN,1961). Data for the rhombohedra1 carbonates speci-
fically was presented by GRAF(1961). Despite the multiplicity of diffraction lines
or peaks, the constituents of mixed carbonates may be identified by various X-ray
diffraction techniques.
From the relative intensities of the strongest diffraction lines of dolomite and
calcite (determined by diffractometer examination of fine powders in a cell type
holder), their percentage contents may be read off from the calibration curve of
TENNANT and BERGER (1957). This is considered to apply equally well to dolomite-
EXAMINATION AND ANALYSIS OF SEDIMENTARY CARBONATES 325

magnesite mixtures. The adaptations to polished rock slices and plastic bonded
grain mounts were described by HUGHES et al. (1960) and WEBER and SMITH(1961).
The detection limit of 5 % suggested by these workers also applies to magnesite,
siderite, rhodochrosite and minerals commonly associated with them which they
listed; whereas albite, gypsum and polyhalite may produce interfering reflections.
The description of a wet chemical X-ray method by HILTROP and LEMISH (1960)
has been followed by a detailed appraisal of this and other X-ray methods pre-
viously applied to the determination of the calcite, dolomite, quartz and clay
contents of carbonate rocks by DIEBOLD et al. (1963). For the quantitative deter-
mination of calcite, dolomite and quartz, the quantitative and qualitative eval-
uation of the clay mineral fraction, and the composition of calcite and dolomite,
they recommended the following four procedures: ( I ) an internal standard method
modelled after ALEXANDER and KLUG (1 959); (2) a subtraction method described
by them; (3) clay separation and X-ray diffraction; and (4) a modified method after
HARKER and TUTTLE (1955). Furthermore, the merits of both the “Tennant and
Berger” and “Hiltrop and Lemish” methods were evaluated.
By measuring integrated line intensity in place of peak intensity, DAVIES
and HOOPER(1963) achieved a detection limit of 1 % for calcite or aragonite in
mixtures of the two.
The composition of individual members of the dolomite, ferroan dolomite,
ankerite series can be obtained from the diffraction data of H o W l E and BROADHURST
(1958) and GOLDSMITH et al. (1 962). ROSENBERG (1963) established the relationship
of variation in 2 0 with composition for the systems MgC03-FeC03 and MnC03-
FeC03.
GRAFand GOLDSMITH (1955) established the relationship between the com-
position of magnesian calcites and calcian dolomites and their unit-cell edges. This
led to its detailed application by SKINNER (1963) and to an improved method of
measurement of small changes in the lattice spacings of calcites, with particular
reference to Mg2+substitution (WAITE,1963).
By employing the techniques of CHAVE (1 954) and GOLDSMITH et al. (1955),
TAFTand HARBAUGH (1964) constructed calibration curves from which the propor-
tions of aragonite, low-Mg calcite and high-Mg calcite may be determined from the
ratio of the intensity of their diffraction peaks.
X-ray diffraction studies thus provide, within the limits described by the
various authors, suitable methods for the rapid evaluation of the minerals present
in carbonate rocks. Interesting to note in this regard is the observation made by GOTO
(1961, p.614) that vaterite and Ca-bearing strontianite have properties that may
cause them to be confused with aragonite; and, in addition, their sensitivity to
chemical tests, such as Meigen’s reaction, resemble that of aragonite.
HOOPER (1964) described the method of electron probe X-ray microanalysis
for the determination of trace elements, as exemplified on Foraminifera, and dis-
cussed its advantages as compared to other techniques.
326 K. H. WOLF, A. J. EASTON AND S. WARNE

THERMOLUMINESCENCE OF CARBONATES

Certain minerals such as calcite, dolomite, fluorite, and potash feldspar, for exam-
ple, emit light when heated to temperatures below that of incandescence. A spe-
cimen emits this light (“thermoluminescence”) only once, and it has to be exposed
to X-rays or y-rays before a second heating will produce thermoluminescence.
According to DANIELS et al. (1953), natural carbonates previously exposed to 6OCo
radiation show four temperature peaks: a t 120-140°, 150-190”, 210-250”, and
290-310°C. The two lower peaks are often not observed because ambient temper-
atures are usually high enough to cause a shift of electrons from their traps.
ZELLER and PEARN(1960), however, were able to observe the 125°C peak in refrig-
erated Antarctic limestone specimens.
For the theory that explains thermoluminescence and the experimental pro-
cedures, the reader may consult the numerous readily available publications by
DANIELS et al. (1953), PARKS(1953), SAUNDERS (1 953), ZELLER (1954), BERGSTROM
(1956), LEWIS(1956b), PITRAT(1956), ZELLERet al. (1957), DANIELS (1958),
ANGINO and SIEGEL (1959), JOHNSON (1960), and SIEGEL (1963).
In numerous instances the various investigators have suggested that thermo-
luminescence may be a useful tool in practical and research geology. It has been
found, however, that the glow curves of carbonate sediments “represent an alge-
braic total of diverse physical and chemical influences” (BERGSTROM, 1956)such as:
mineralogy (OCKERMAN and DANIELS, 1954; LEWIS,1956b; ZELLER and WRAY,
1956; MOORE,1957; RIEKE,1957; DANIELS, 1958; and JOHNSON, 1960), polymor-
phism (ZELLER and WRAY,1956; and JOHNSON, 1960), ratio of minerals present
(LEWIS,1956b; PITRAT, 1956; JOHNSON, 1960; and INGERSON, 1962), trace elements
or “impurities” (PITRAT,1956; ZELLERand WRAY,1956; ZELLERet al., 1957;
DANIELS, 1958;and JOHNSON, 1960),exposure to radioactive material (DANIELS et al.,
1953;PARKS, 1953;SAUNDERS, 1953; LEWIS,1956b; PITRAT, 1956;ZELLERetal., 1957;
and DANIELS, 1999, heating (MOORE,1957; INGERSON, 1962; and MCDIARMID,
1963), pressure (ZELLERet al., 1955, 1957; DANIELS, 1958; BARNES, 1959; and
INGERSON, 1962), recrystallization and inversion (MOORE,1957; ZELLERet al.,
1957; DANIELS, 1958; JOHNSON, 1960; and INGERSON, 1962), and geologic history
and diagenesis in general (SIEGEL,1963).
As some of these factors increase and others reduce the type and degree of
luminescence, and because more than one factor can be influential at the same time
or be effective in successive stages, it is not surprising that seemingly contradictory
results have been obtained. Nevertheless limited success has been achieved: (I)
in age determination (ZELLER,1954; ZELLER et al., 1955, 1957); (2) in correlating
and zoning carbonate sediments (PARKS,1953; SAUNDERS, 1953; BERGSTROM, 1956,
LEWIS,1956; PITRAT,1956; DANIELS, 1958); (3) for measuring calcite-dolomite
contents (LEWIS,1956; PITRAT,1956); (4) in determining origin of dolomites
(SIEGEL,1963); (5) in the study of biogenic calcium carbonate (JOHNSON, 1960);
EXAMINATION AND ANALYSIS OF SEDIMENTARY CARBONATES 327

and (6) in the investigation of temperature and pressure histories (HANDINet al.,
1957; ANGINO,1959). On the other hand, many similar studies have indicated that
despite the occasional successful application of thermoluminescence, it is not a
reliable tool as yet and more basic research is required as has been pointed out by
most of the investigators. (See also Hsu, 1967.)

RADIOCARBON DATING OF CARBONATE SEDIMENTS

The dating of sediments by the 14C method has been described, for example, by
LIBBY(1955), RANKAMA (1956), EMERYand BRAY(1962) and ~ S T L U N Det al.
(1962). This is an invaluable tool for determining the approximate absolute age
of recent carbonate deposits; it is particularly useful, therefore, in measuring the
rates of sedimentation. A number of modifying influences exist, however, that
cause either an increase or decrease of apparent ages because of dilution and alter-
ation effects. Charcoal, well-preserved wood, and peat sometimes prove to be
more reliable for 14C dating. In any case, there are cosmic controls that lead to
variations in 14C productivity by as much as 2 %.
TAFTand HARBAUGH (1964, p. 113) recently discussed the discrepancies be-
tween radiocarbon ages of different components in carbonate sediments. Both
carbonate carbon and organic carbon were analyzed. “Of ten samples, six yielded
greater ages for carbonate carbon in respect to organic carbon, three yielded
smaller ages for carbonate carbon in respect to organic carbon, and one yielded
the same age for carbonate carbon in respect to organic carbon.” The reasons for
the differences in radiocarbon ages of carbonates and organic carbons are poorly
understood, but they suggested four possible reasons (see also FAIRBRIDGE, 1961).
(I) In analyzing carbonate sediments it is possible that the material consists
of particles derived from different geographic sources and rocks that vary in age.
TAFTand HARBAUGH (1964, p.113) gave an example of this. A similar case has
been pointed out by EMERY and BRAY(1962), and WOLF(1965a,c).
(2) Another possibility is that the organisms used carbon deficient in 14C
in comparison to the proportion of 14C in the atmosphere. For example, “old”
carbonate carbon may reach the environment in which the organisms live via
rivers that drain land areas with ancient carbonate rocks. Thus, 14C deficiency
causes the skeleton to appear older than it is in reality.
(3) Burrowing organisms such as burrowing clams and worms may contribute
younger organic material to buried sediments.
(4) Many animals take in finely divided carbonate particles with their food,
and if the organisms absorb some of the carbonate particles that may have “older”
carbonate carbon (see I) and secrete skeletal carbonate, the 14Cdates of the latter
may be anomalous.
EMERY(1960) and EMERY and BRAY(1962) have dated different fractions
328 K. H. WOLF, A. J. EASTON AND S. WARNE

of the samples collected, namely, Foraminifera, fine-grained carbonate, total

carbonate, and extracted carbon. These two investigators concluded “. . . after
..
considering the various pieces of evidence . that the total organic carbon is the
most reliable dating medium for the basins off Southern California.”
Other possible modifying factors that increase or decrease the apparent ages
determined by 14C method are discussed by KEITHand ANDERSON (1963) and
RUBINet al. (1963). The former concluded that the errors in determining radiocar-
bon dates of shell material may be as large as several thousand years. BERGER et al.
(1964), however, indicated that conchiolin of shells, similar to collagen in bones,
can be prepared for dating; this may give more reliable results than dating of the
calcium-carbonate shell material, because secondary changes are less likely to
occur in conchiolin than in the carbonate skeleton.
The published results indicate that the interpretation of radiocarbon age
dates, in particular in the case of the 14Cmethod, is still marked by many uncer-
tainties. Aside from determining the precise half-life of 14C, which was assumed
as being 5,568 f 30 years by LIBBY(1955), but now raised to 5,730 f 40’years
(see GODWIN,1962), many primary and secondary factors that control the radio-
carbon content are poorly understood. Continued emphasis on research con-
cerning the basic problems, no doubt, will increase the reliability of 14C dating
of carbonate sediments.
It should also be mentioned that research is in progress on the use of traces
of uranium, helium, protactinium, and thorium in carbonates for absolute age
determination (TATSUMOTO and GOLDBERG, 1959; BROECKER, 1963; THURBER et al.,
1963; FANALE and SCHAEFFER, 1964).

ISOTOPE INVESTIGATIONS OF CARBONATE SEDIMENTS

Isotope investigations are being made at an ever-increasing rate in solving prob-

lems in carbonate rock petrology. Most of the work has been conducted on the
ratios of 1 8 0 / 1 6 0 and 13C/W, and in isolated cases on 24Mg/26Mg(and also
48Ca/Wa/ (total Ca) ratios). Some of the more recent papers that describe the
theory of isotope fractionation and analytical procedures, and provide references
to earlier publications, are those by MCCREA(1 950), CRAIG(1953), JEFFERY et al.
(1959, RANKAMA (1956), CLAYTON and EPSTEIN(1958), and DAUGHTRY et al.
( 1962).
Although considerable information is available on the elemental distribution
of Sr (WOLFet al., 1967), only a few investigations appear to have been made on
its isotopes. WICKMAN (1948), KULP(1950), and KULPet al. (1952) suggested a
possible use of Sr isotopes for age determination. On the other hand, HERZOG
et al. (1953) indicated that it would be difficult to use strontium for that purpose
(see RANKAMA, 1956, p.337).
EXAMINATION AND ANALYSIS OF SEDIMENTARY CARBONATES 329

Investigations of 13C/"T ratio have been used: (I) to distinguish between

marine and fresh-water or terrestrial calcareous material (CRAIG,1953; CLAYTON
and DEGENS, 1959; J. C. VOGEL,1959; LOWENSTAM, 1961; DEGENS and EPSTEIN,
1962b, 1964; KEITHand ANDERSON, 1962;LLOYD,1964; WEBER,1964; WEBER et al.,
1964); (2) in studies of dolomite genesis and limestone petrology (DEGENS and EP-
STEIN, 1962a, 1964; Ross and OANA,1961;WILLIAMS and BARGHOORN, 1963); (3) to
study calcareous varves (WEBER,1964); and (4) in investigating diagenetically
altered carbonates (WICKMAN and VONUBISCH,1951; JEFFERYet al., 1955; COMP-
STON, 1960; Ross and OANA,1961; WEBER and ROCQIJE, 1963; DEGENS and EP-
STEIN, 1964; GROSS, 1964; LLOYD,1964). A number of the isotope studies revealed
phylogenetic differences of faunal and floral calcium carbonate (CRAIG, 1953, 1954;
REVELLE and FAIRBRIDGE, 1957; LOWENSTAM, 1961; KEITHand ANDERSON, 1962;
GROSS,1964; LLOYD,1964; TAFTand HARBAUGH, 1964). The isotope studies under-
taken by LOWENSTAM and EPSTEIN(1957) suggested that many of the Recent
aragonite needle deposits may have been formed,by the disintegration of calcare-
ous Algae. Similar approaches may assist in discriminating for example between
algal, bahamite, and faecal pellets.
The ratio 1 8 0 / 1 6 0 has been utilized: (I) in establishing paleotemperatures
(UREYet al., 1951; EPSTEIN et al., 1953; CLAYTON and EPSTEIN, 1958; FLUGEL and
FLUGEL-KAHLER, 1963; EMILIANI, 1964; LLOYD,1964); (2) in distinguishing between
syngenetic, diagenetic, hydrothermal and metamorphic carbonates (ENGELet al.,
1958; DEGENS and EPSTEIN, 1964); (3) in ore investigations (ENGELet al., 1958);
(4) in dolomite studies (DEGENS and EPSTEIN, 1962a, 1964); (5) in general petrogene-
sis and diagenesis of carbonate sediments (CLAYTON and EPSTEIN, 1958; DEGENS
and EPSTEIN,1962a, 1964; FLUGELand FLUGEL-KAHLER, 1963; GROSS,1964;
WEBER,1964); and (6) in the discrimination between marine and fresh-water
sediments (DEGENS and EPSTEIN, 1962a, 1964). Differences in oxygen-isotope com-
position of some right- and left-coiled Foraminifera and their influence on the
accuracy of isotope data are discussed by LONGINELLI and TONGIORGI (1964).
DAUGHTRY et al. (1962) have shown that future work on magnesium iso-
topes may prove to be a valuable approach in solving genetic problems of dolomites
and possibly other Mg-containing carbonates.
Finally, 45Ca has been used in determining the mode, location, rate, and
amount of calcium carbonate deposition by a number of shell-forming organisms
(BEVELANDER, 1952; WILBURand JODREY, 1952; JODREY, 1953).
More detailed information on isotope studies related to carbonate mineralogy
and petrology is given by DEGENS (1967).
330 K. H. WOLF, A. J. EASTON AND S. WARNE

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EXAMINATION A N D ANALYSIS OF SEDIMENTARY CARBONATES 34 1

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Chapter 9

PROPERTIES AND USES OF THE CARBONATES

FREDERIC R. SIEGEL

Department of Geology, The George Washington University, Washington, D.C. (U.S.A.)

SUMMARY

Carbonate rocks are raw materials indispensable to industrial development.

In recent years, limestone, dolomite, and marble constituted more than 70% of all
rocks quarried in the United States. Statistics on production and dollar value for
1961, 1962, and 1963 are presented, by uses. The uses to which carbonate rocks
and minerals can be put is a function of their physical and/or chemical properties.
This chapter contains listings of selected chemical analyses and important physical
properties of carbonate rocks. More than one hundred uses for carbonate rocks and
minerals are given together with the users’ general chemical and physical require-
ments. Because of space limitations, only three of the many areas of active re-
search on carbonate properties are discussed: solid solution and subsolidus
relations, thermoluminescence, and infrared absorption.

SOME ASPECTS AND STATISTICS OF CARBONATE ECONOMICS

A myriad of uses exist for carbonate minerals and rocks or products derived from
them. Indeed, industrial development in the United States and other areas of the
world is often reflected in the number of tons of carbonate raw material produced
and sold each year. If, for example, there were a cut-back in steel production or a
lag in building construction, there would generally be a concomitant drop-off in
the quarrying of carbonate rock. Similarly, a reduction in funds for state and fed-
eral highway development programs would cause a great drop in carbonate quar-
rying. During 1962, more than 70% of all rock quarried in the United States was
limestone, dolomite, and marble. Crushed and broken stone comprised a major
part of the carbonate rock production, and 93 % of almost 500 million short tons
(representing about U.S.$ 600 million) was used for concrete and road stone,
cement (Portland and natural), flux, agriculture, and lime and dead-burned dolo-
mite. In Table I there is a categorization of statistics on production and dollar value

~-
l Former address: The University of Kansas, State Geological Survey, Lawrence, Kans. (U.S.A.).
TABLE I

CARBONATE ROCKS SOLD OR USED BY PRODUCERS IN THE UNITED STATES, BY USES]

1961 1962 1963

- -
Quantity Value Quantity Value Quantity Value
(x 1,000 (x US.$ ( x 1,ooo (x US.$ ( x 1,m (x US.$
short tons) 1,000) short tons) 1,m) short tons) 1,000)
~~

Limestone and dolomite (crushed and broken stone)

concrete and roadstone 258,997 338,798 276,878 365,098 292,976 380,893
flu 27,198 39,725 26,081 36,821 27,185 39,322
agriculture 22,196 38,478 23,029 39,348 25,956 44,195
railroad ballast 4,260 5,376 5,065 6,578 4,923 6,4 10
riprap 9,138 10,440 10,016 12,253 10,690 13,229
alkali manufacture 2,560 2,878 2,840 3,188 2,955 3,282
calcium-carbide manufacture 764 785 *2 *2 *2 *2

cement (Portland and natural) 79,779 85,883 83,318 92,886 86,842 92,646
coal-mine dusting 372 1,527 400 1,667 539 2,268
fill material 266 277 440 330 383 296
filler (not whiting substitute):
asphalt 2,130 5,408 3.208 6,955 1,994 5,012
fertilizer 438 1,080 448 1,132 457 1,133
other 219 873 35 1 1,567 419 1,921
filtration 148 22 1 79 141 62 117
glass manufacture 1,211 3,736 1,337 4,294 1,492 4,781
lime and dead-burned dolomite 18,124 28,283 19,356 32,959 21,450 36,024
limestone sand 1,693 2,596 1,706 3,103 1,759 3,234
limestone whiting3 802 9,242 838 9,639 785 9,298
mineral food 695 3,723 692 3,847 618 3,793
paper manufacture 400 1,129 27 1 82I 358 1,099
poultry grit I53 1,185 161 1,333 160 1,342
 w
ga
refractory (dolomite) 235 465 322 563 769 1,297 0
suger refining 882 2,215 623 1,506 646 1,580
8w
other uses4
uses unspecified
2,838
1,900
4,603
2,475
1,741
1,753
4,253
2,518
2,125
2,805
5,472
3,282
-
i*
subtotal 2:
437,398 591,401 460,953 632,800 488,348 661,926 U

Marble (crushed and broken stone)

terazzo 397 4,535 3 80 4,866 367 4,768 8
e
other uses5 1,038 7,859 1,243 9,512 1,385 8,797
i2
subtotal 1,435 12,394 1,673 14,378 1,752 13,565 *
c1

Limestone (dimension stone)

2
building 4
v1
rough: construction 61 323 82 326 52 289
architectural 223 3,455 197 3,000 196 3,091
dressed: sawed and cut 330 12,066 318 12,476 347 13,498
rubble 219 725 284 928 282 1,104
curbing and flagging 22 169 15 117 18 152
~

subtotal 855 16,738 896 16,847 895 18,134

Marble (dimension stone)

buildings
rough; architectural 37 1,168 34 1,330 28 1,334
dressed: sawed and cut 106 14,670 95 14,269 80 12,574
monumental: rough and finished 14 2,728 17 3,140 42 7,294

subtotal 157 18,566 146 18,739 150 2 1,002 w

.~ R
TABLE I (continued)

1961 1962 1963

Quantity Value Quantity Value Quantity Value
( x 1,000 ( x U.S.$ (x 1,OOo ( x U.S.% ( x 1,000 ( x U.S.b
short tons) 1,000) short tons) 1,000) .rhort tons) 1,000)
~

Shell
concrete and road material 1 1,499 18,256 12,792 18,611 11,821 17,277
cement 4,406 4,881 5,117 5,531 5,278 5,847
lime 1,420 1,782 1,441 1,876 1,169 1,663
poultry grit 598 5,004 581 4,635 552 3,874
mineral food 3 14 4 22 *2 *2

other uses7 78 438 113 566 I99 759

subtotal 18,004 30,375 20,054 31,241 19,019 29,420

Calcareous marl
agriculture 223 168 226 156 260 178
cement 876 819 956 855 904 811
subtotal 1,099 987 1,182 1,Ol I 1,164 989
grand total 458,948 670,461 485,042 715,016 511,328 745,036

Data for 1961 and 1962were given by ANONYMOUS (1963), those for 1963by ANONYMOUS (1964a).
Included with “other uses”.
3 Includes stone for filler, abrasives, calcimine, calking compounds, ceramics, chewing gum, fabrics, floor coverings, insecticides, leather good, paint,
paper, phonographic records, plastics, pottery, putty, roofing, rubber, Wire coating, and unspecified uses. Excludes limestone whiting made by
companies from purchased stone.
4 Includes stone for acid neutralization, calcium carbide (1962), cast stone, chemicals (unspecified), concrete products, disinfectant and animal sanitation,
electrical products, magnesia, magnesite, magnesium, mineral wool, oil-well drilling, patching plaster, rice milling, road base, roofing granules,
stucco, terrazo, and water treatment.
Stone for agriculture, asphalt filler, flux, poultry grit, roofing, stone sand, stucco, whiting and unspecified uses.
1961: US.$ 8,934,000 for exterior use, U.S.$ 6,904,000 for interior use; 1962: US.$ 9,575,000 for exterior use; U.S.$ 6,024,000 for interior use;
1963: US.$ 7,351,000 for exterior use; U.S. $ 6,357,000 for interior use.
’Agriculture, asphalt filler to whiting.
PROPERTIES A N D USES OF THE CARBONATES 347

TABLE I1

CEMENT PRODUCTION OF SELECTED COUNTRIES WHICH ACCOUNT FOR ABOUT 90% OF THE TOTAL
WORLD PUODUCTlON

(After ANONYMOUS,
1964c)

Country 1961 I962

(long tons) (long tons)

Argentina 2,856,900 2,857,000

Austria 3,035,450 3,008,830
Australia 2,813,000 2,887,000
Brazil 4,636,341 4,992,000
Belgium 4,678,792 4,817,296
Canada 5,541,025 6,059,133
China 9,800,000* 8,900,000*
Czechoslovakia 5,259,000 5,620,000
Denmark 2,879,140 2,937,900
Egypt 2,107,000 2,260,000
France 15,138,469 16,433,000
Germany (eastern) 5,192,000 5,346,000
Germany (western) 26,714,000 28,141,000
India 8,114,000 8,450,000
Italy 17,698,986 19,838,415
Japan 24,243,000 28,33 1,000
Korea (North) 2,226,000 2,338,000
Mexico 2,987,149 3,299,000
Pakistan 1,223,000 1,373,000
Poland 7,248,000 7,422,000
Roumania 3,255,538 3,434,129
South Africa 2,557,420 2,616,870
Spain 6,408,005 6,342,000
Sweden 2,964,000 3,006,000
Switzerland 3,544,292 3,667,018
Turkey 1,995,971 2,279,961
U.S.S.R. 50,194,000 56,394,000
United Kingdom 14,149,000 14,030,000
United States 56,841,100 59,074,300
Yugoslavia 2,299,000 2,478,000
World total 33I ,000,000 353,000,000

* Estimate made by the U.S. Bureau of Mines.

for most of the carbonate rock sold or used by producers in the United States in
1961, 1962, and 1963, by uses. No such detailed data are available on a world-
wide basis. Cement production figures, however, have been published and are
presented in Table 11. They show that in 1962, 30 countries accounted for about
90% of the world production of 353 million long tons of cement. During 1962,
seven countries (China, France, Germany, Japan, the United Kingdom, the
U.S.S.R., and the United States) produced over 75 % of the world total of 618 mil-
348 F. R. SIEGEL

lion long tons of steel ingots and castings, pig iron, and ferro-alloys. Ifone can
extrapolate from this to the amount of carbonate rocks (or derivatives) used in the
siderurgical industry, an extremely conservative estimate would be well over
1,000 million long tons.
In addition to their direct and indirect applications in many industrial
processes, limestones and dolomites are reservoir rocks for more than one-half
of the known petroleum reserves of the world (IMBT, 1950), and act as host rock
for numerous important metalliferous ore deposits. Equally impressive is the
fact that in many areas, the major source of water is from limestone aquifers.
Although the practical (economic) value of the carbonates is emphasized
in the later paragraphs of this chapter, one must not forget their meaning to the
academician. In his study of fossils and other features commonly associated with
the carbonate rocks, the geoscientist can often find clues for solving economic
problems by delving into the geologic past, reconstructing environments that
existed at the time of their formation, developing fundamental concepts, and es-
tablishing parameters which could show trends important to successful exploitation.

PROPERTIES

Introduction

The physical, chemical, optical, and other properties of carbonate rocks influence
(within certain limits) their economic potential, that is, the maximum number
of uses they might serve. Because these properties are in great part determined by
those of the carbonate mineral(s) in the rock and because the carbonate minerals
themselves can be very valuable, selected physical, optical, and crystallographic
properties of the economically important carbonate minerals are presented here
(Tables 111-V). These properties can be significantly altered by cationic substi-
tution, especially in calcite and dolomite. In fact, much recent research has been
devoted to the solid solution and subsolidus relations within the calcite group
minerals. This aspect is discussed in another part of the chapter.

Physical proper ties

Factors which most affect carbonate economics are the physical properties of the
quarried material. For example, to be suitable for building stone, limestone, dolo-
mite, or marble must be strong, durable, and reasonably workable; in addition,
stone which has these qualities and is aesthetically pleasant to view, will have
greater dollar value.
Basic properties are given in Table VI. These are generally sufficient for the
builders’ (architectural and engineering) needs, but there are many other physical
TABLE 111 w

PHYSICAL PROPERTIES OF SOME ECONOMICALLY IMPORTANT CARBONATE MINERALS E

(After LANGE,1956;DANA, et al., 1962)
1959;KRAUSet al., 1959;and DEER i+?i
Mineral Chemical formula Hardness Specific Colour Common impurities Cleavage
(pure) gravity

calcite caco3 3 on (1011) 2.72 colourless or white Mn, Fe, Mg for Ca (1011)perfect
2.5 on base
dolomite CaMg(CO3)n 3.54 2.85 pink, white, or colourless Fe, Mn, Co, Zn for Mg, (1011)perfect
Pb for Ca
magnesite MgC03 3.5-5 3.0-3.2 white, gray, yellow, or brown Fe, Ca, Mn for Mg (1011)perfect
rhodochrosite MnCOs 3.54 3.5-3.7 rose-red or light pink Fe, Ca, Mg, Zn for Mn (1011) perfect
siderite FeCO3 3.54 3.96 brown Mn, Mg, Ca for Fe (lOT1) perfect
smithsonite ZnCOa 4-4.5 4.3M.45 brown or green Fe, Mn, Ca, Mg, Cd, (1011)perfect
Cu, Co, Pb for Zn
aragonite CaC03 3.54 2.95 colourless, white, or pale Sr, Pb,Zn for Ca (010) and (110)
yellow imperfect
witherite BaC03 3.5 4.3 colourless, white, or gray Sr, Ca for Ba (010)and (110)
poor
strontianite SrC03 3.54 3.7 white, gray, yellow, or green Ca for Sr (1 10) good
cerussite PbC03 3-3.5 6.55 colourless, white, or gray (1 10) good and
(021)fair
malachite CuzCOa(0H)z 3.54 3.9403 bright green (001) perfect
azurite Cu3(OH)z(C03)2 3.54 3.77 intense azure blue (021)imperfect
TABLE I V
w
OPTICAL DATA ON THE ECONOMICALLY IMPORTANT CARBONATE MINERALS VI
0
(After LARSENand BERMAN,
1934; WINCHELL
and WINCHELL,
1951; MOOREHOUSE,
1959; and DEER
et al., 1962)

Mineral System Optic sign Indices of refraction Birefringence Optic axial 2V Dispersion Colour in
plane section

calcite hexagonal uniaxial ne=1.486-1.550 0.172-0.190 - very high co1our1ess

(-1 no=1.658-1.740
dolomite hexagonal uniaxial ne= 1.5W1.520 0.181-0.196 - high colourless
(-1 no = 1.681-1.716
magnesite hexagonal uniaxial ne=1.509-1.563 0.191-0.219 - very high colourless
(3 no=1.700-1.782
rhodochrosite hexagonal uniaxial ne=1.597-1.605 0.220-0.221 - high co1our1ess
(-1 no= 1.817-1.826 to pink
siderite hexagonal uniaxial ne=1.575-1.633 0.207-0.242 - high colourless
(-1 no=1.782-1.875 to brown
smithsonite hexagonal uniaxial ne= 1.621-1.625 0.228-0.225 - high colourless
(-) no= 1.849-1.850
aragonite orthorhombic biaxial nz= 1.53G1.531 0.155 18-18.5' low colourless
(-1 nu=1.680-1.682
nz= 1.685-1.686
witherite orthorhombic biaxial nz =1.529 0.148 16" very low colourless
(-1 nu=1.676
nz=1.677
strontianite orthorhombic biaxial nz =1.516-1 520 0.1 50-0.149 7-10" low colourless
4 (-) nv= 1.664-1.667
nc= 1.666-1.669
cerussite orthorhombic biaxial nz=1.803-1.804 0.273-0.214 8-8.5" high colourless
(-1 nu=2.0742.076
nz =2.076-2.078
malachite monoclinic biaxial nz =1.655 0.254 43 high green
(4 nu=1.875
n2=1.909
azurite monoclinic biaxial nz= 1.730 0.108 68 O low blue
(+I nu= 1.758
n2=1.838
PROPERTIES AND USES OF THE CARBONATES 35 1

properties which have been measured and reported, and which must be known
before a carbonate rock may be considered for a specializeduse. A classic compila-
tion of quantities important for the physics and physical chemistry of geological
materials was published by BIRCHet al. (1942) in the Handbook of Physical Con-
stants. Selected data from this publication are presented in Tables VII-XIX.
Methods of testing rock materials for several of their physical properties
have been fairly well standardized by the American Society for Testing and Mate-
rials (A.S.T.M.). Many of these tests, however, were not directly applicable to
samples obtained, for example, by diamond drilling techniques. Therefore, in a
program designed to determine the petrographic and physical properties of mine
rock and establish correlations between these properties and the costs of various
mining operations, U.S. Bureau of Mines scientists began by developing or adap-
ting methods for measuring the physical properties of rock from core specimens ob-
tained by diamond drilling (OBERTet al., 1946). The standardization of testing
methods was necessary first to demonstrate that the size of the sample or the testing
conditions did not affect the results; second, to establish a correlation factor so
that values obtained, which were influenced by size or testing methods, could be
made to correspond to values obtained by a recognized standard technique. The
physical properties treated were the following: apparent specific gravity, apparent
porosity, compressive strength, tensile strength, modulus of rupture (flexural
strength), impact toughness, abrasive hardness, scleroscope hardness, Young’s
modulus (modulus of elasticity), modulus of rigidity, specific damping capacity,
longitudinal bar velocity, apparent Poisson’s ratio, and grindability.
This initial phase of the U.S. Bureau of Mines program was followed by a
systematic investigation of the physical properties of mine rock from all parts of
the United States. Results were published in a series of four papers (WINDES,
1949, 1950; BLAIR,1955, 1956), the last of which contains a complete index of all
the rocks examined. These papers, titled: “Physical properties of mine rock,
parts I, 11,111, and IV”, probably present the most complete data on the important
physical properties of the carbonate (and other) rocks. Selected information from
these papers are shown in Table XX where they can be compared with values given
by other authors.
GILLISON (1 960a,b) briefly reviewed testing methods and physical properties
given by KESSLER and SLIGH(1927) and WOOLF(1953). Woolf‘s paper is especially
interesting because in it are described physical tests crushed stone must undergo
before it can be evaluated for use as road building aggregate for state and federai
highway development programs. A test treated by Woolf but often omitted
by other authors is that of soundness, that is, response of the rock to alternate
freezing and thawing. One manne: of determining whether material is “sound”,
“questionable”, or “unsound” is by immersing several fragments or blocks of the
material in a saturated solution of Na2S04 for 16-18 h, drying them in an oven,
repeating the test five times, and noting the damage to the fragments or blocks.
TABLE V
CRYSTALLOGRAPHIC DATA ON SOME ECONOMICALLY IMPORTANT CARBONATE MINERALS

et al., 1962; and A.S.T.M., 1963a)

(After GRAF,1961; DEER

Mineral Space group Unit cell (A) Rhombohedra1 Z # of for- Cleavage Twinning
cell edge ( A ) mula unitslunit
cell

calcite R3c a =b =4.990 6.31 2 (lOT1) perfect (01T2) very common

c =17.061 (OOO1) common
(loil) not common
dolomite R5 a=b=4.807 6.01 5 2 (1OTl) perfect (OOO1) common
c=16.01 (10T1) common
(1120) common
(loT1) rare
(0221) glide twinning
magnesite R3c a=b=4.633 5.615 2 (loT1) perfect (OOO1) translation gliding to [loll]
C = 15.016
rhodochrosite R3c a = b =4.111 5.91 2 (loT1) perfect (01T2) rare (lamellar twins)
~=15.66
siderite R3c a=b=4.69 5.77 2 (10T1) perfect (01T2) rare (lamellar twins)
c=15.30 (OOO1) rare
smithsonite RJc a= b =4.653 4.432 2 (loll) perfect
c=15.028
aragonite Pmcn a = 4.95 - 4 (010) imperfect (110) common (lamellar and repeated)
b= 1.95 (1 10) poor
C = 5.13
wi therite Pmcn a = 5.26 - 4 (010) good (1 10) always present, repeated
b= 8.84 (1 10) poor
C = 6.56
-
(012) poor .a
strontianite Pmcn a = 5.13 4 (1 10) good (110) common (single, repeated, and lamellar)
b= 8.42 (021) poor v1

cerussite Pmcn
C = 6.09
a = 5.195 - 4
(010) poor
(1 10) good (1 10) common (repeated)
B
b= 8.436 (021) fair
P
C = 6.152
malachite P21/A a = 9.502 - 4 (001) perfect (100) common
b= 11.974
c= 3.240
azurite P21IC a = 5.008 - 2 (021) imperfect
b= 5.884
c=10.336

TABLE VI

SOME PROPERTIES OF LIMESTONE USED IN KANSAS AS BUILDING STONE^

(After KANSSSBUILDING ASSOCIATION,

STONE 1964)

Name Texture Colour Absorption Specific Weight Compressive strength Temperature-

( %) gravity (Wcubicft.) normal parallel Weak salt
to bed to bed efect
(IbJsq. inch) (Ib./sq. inch)

Onaga fine grain light buff 7.6 1.956 122 9,629 9,775 none
Chestnut Shell coquinoid chestnut 5.4 2.118 132 4,806 5,625 none
Neva dense, fine grain white 3.1 2.440 I52 22,600 18,800 no data
Cottonwood medium to fine grain gray 6.2 2.21 8 139 11,292 11,525 none
Silverdale medium to fine grain light buff 9.4 2.109 137 6,189 8,505 none
Benton fine grain buff 4.9 2.259 141 11,589 10,650 none
Kansas Cream fine grain creamy 9.0 1.674 I05 4,520 4,710 none

1The Kansas Building Stone Association prepared a pamphlet which serves as a guide for architects and engineers who need a rapid reference to the
most important properties of Kansas building stone.
Compression test (A.S.T.M. C170-50) determined by C. Crosier of Kansas University Civil Engineering Department. Absorption and specific gravity w
(A.S.T.M. C97-47) and temperature-weak salt (A.S.T.M. C218-48T) tests were made by the State Geological Survey of Kansas. VI
w
354 F. R. SIEGEL

TABLE VII

SELECTED PHYSICAL CONSTANTS OF CARBONATE ROCKS. POROSITY AND BULK DENSITY (DRY AND
SATURATED)

(After BIRCHet al., 1942, table 2-6)

Lithology Location Porosity Bulk density

and age ( %) dry saturated
w1hz0

limestone Buxton' 14.1 2.31 2.45

limestone, Carboniferous 2.2-9.4 2.342.59 2.43-2.61
limestone, Silurian -1 1.4-6.3 2.53-2.64 2.59-2.65
limestone. Dundee, Mich. 0.9 2.63 2.64
Caddo Lime, Pennsylvanian Ranger, Texas 4.4 2.57 2.61
Greenhorn Limestone, Crook Co., Wyo. 37.6 1.74 2.12
Upper Cretaceous
limestone, sugary, quartz-free 25.6 2.14 2.40
oolitic limestone Monk's Park' 20.3 2.16 2.36
chalk -1 17.642.8 1.53-2.22 1.962.40
dolomite Mitcheldeanl 8.6 2.54 2.63
marble -1 1.1 2.65 2.66
marble, 34 samples from 12 states 0.4-2.1 2.66-2.86 2.68-2.86
in U.S.A.

Known or unknown location in Great Britain.

TABLE VIII

SELECTED PHYSICAL CONSTANTS OF CARBONATE ROCKS. THERMAL EXPANSION OF ROCKS, TEMPERATURE

INTERVAL OF 20-100"c

(After BIRCHet al., 1942, table 3-4)

Lithology Number of determinations Average linear expansion coefficient

*
limestones 20
marbles 9
 PROPERTIES A N D USES OF THE CARBONATES 355

TABLE IX

SELECTED PHYSICAL CONSTANTS OF CARBONATE ROCKS. COMPRESSIBILITY OF ROCKS AT LOW PRES-

SURES

(After BIRCHet al., 1942, table 4-13)

Lithology Pressure 107p

(kglcm2) enclosed unenclosed

dolomite 0 37.1 11.9

120 25.4 11.9
600 14.8 11.9
marble (Vermont) 0 180.0 13.9
120 33.1 13.8
600 15.0 12.6
limestone, Pennsylvanian 0 29.2 24.7
(carbonaceous) 120 27.5 24.5
600 23.5 24.1

' p = compressibility, in reciprocal bars, at the pressures given.

TABLE X

SELECTED PHYSICAL CONSTANTS OF CARBONATE ROCKS. COMPRESSIBILITY OF ROCKS AT HIGH PRES-

SURES

(After BIRCHet al., 1942, table 4-14)

Lithology Location Pressure (bars) lO7/?1

marble (enclosed) Colorado 7,000 13.8 (18°C)

limestone (unenclosed,
linear method) Solnhofen, Bavaria 6,000 13.6 (30°C)
Solnhofen, Bavaria 6,000 14.2 (75 "C)
Solnhofen, Bavaria 5,000 12.9 (6°C)
Solnhpfen, Bavaria 5,000 14.2 (100°C)
Solnhofen, Bavaria 5.000 16.3 (270°C)
Solnhofen, Bavaria 5,000 17.1 (476°C)

lp= compressibility, in reciprocal bars, at the pressures given.

 F. R. SIEGEL

TABLE XI

SELECTED PHYSICAL CONSTANTS OF CARBONATE ROCKS. ELASTIC CONSTANTS OF ROCKS AT ORDINARY

PRESSURE AND TEMPERATURE^

(After BIRCHet al., 1942, table 5-4)

Lithology Location E2 G3 a4 Stress

(dynes/cm2) (dyneslcm2) (kglcm2)

limestone Knoxville, Tenn. 6.2 I (2.48) 0.25 1 70-600

Montreal, Que. 6.35 (2.50) 0.252 70-600
Solnhofen, Bavaria 5.77 2.31 (0.25)

dolomite Pennsylvania-I 7.10 3.23

Pennsylvania-2 9.30 3.62

marble Dinant, Belgium 7.24 (2.98) 0.278 70-600

Rutland, Vt. 5.24 (2.07) 0.263 70400

1Values of G or u in parentheses have been derived from the measurements by the use of the
connecting equations for isotropic materials..
?E= Young's modulus.
3G= modulus of rigidity.
4u= Poisson's ratio (dimensionless).

TABLE XI1

SELECTED PHYSICAL CONSTANTS OF CARBONATE ROCKS. EFFECT OF STRESS ON YOUNG'S MODULUS

OF ROCKS, BY THE METHOD OF FLEXURAL VIBRATIONS OF LOADED BARS

(After BIRCHet al., 1942, table 5-5)

Lithology Location Orientation Density EO2 Ea3

of axis' (glcm3) (dynes/cm2) (dyneslcm2)
_ _ _ ~

limestone Bedford, Ind. I 2.23 2.86 * 10" 2.97 * 10"

Bedford, Ind. /I 2.35 3.48 * lo1' 4.07. 10"

marble Danby, Vt. /I 2.70 6.01 . 10" 6.99 . 10"

Danby, Vt. lI 2.70 6.48 . 10" 7.24 . loll
Danby, Vt. I 2.70 4.36. 10" 6.94. 10"
Danby, Vt. I 2.70 3.66. 1011 5.81 . 10"

marble Cockeysville, Md. 2.86 7.10 * 10" 8.84 * lo1'

1 Orientation of the axis of the bar with respect to the bedding plane.
2Eo= Young's modulus at zero stress.
3Ea= Young's modulus at a strsss not quite great enough to cause failure (500-1,OOO kglcm2).
PROPERTIES AND USES OF THE CARBONATES 351

TABLE XI11

SELECTED PHYSICAL CONSTANTS OF CARBONATE ROCKS. ELASTIC PARAMETERS OF CERTAIN ROCKS AT

4,000 kg/cm2 AND 30°C'

(After BIRCHet al., 1942, table 5-8)

Lithology Locat ion E2 G3 P4 u5 VP6 V87

(dynes/ (dynes/ (cmz/ (kmlsec) (kmlsec)
cm2) cm2) dyne)

limestone Solnhofen, Bavaria 6.3 2.47 21.4 0.276 5.54 3.08

marble Vermont 8.7 3.33 13.9 0.299 6.51 3.49

1 Values computed for the measured G and u by the use of equations for isotropic materials.
The rocks were enclosed.
2E= Young's modulus.
3G= modulus of rigidity.
4 8 = volume compressibility
5u= Poisson's ratio (dimensionless).
6Vp= velocity of propagation of compressional waves in an infinite medium.
7 V8= velocity of propagation of distortional waves in an infinite medium.

TABLE XIV

SELECTED PHYSICAL CONSTANTS OF CARBONATE ROCKS. RIGIDITY AND VELOCITY OF SHEAR WAVES AS
A FUNCTION OF PRESSURE^

(After BIRCHet al., 1942, table 5-9)

Lithology Location G2 vs3

P=I P=500 P=4,000 P = l P=500 P=4,000

limestone Solnhofen, Bavaria 1.96 2.20 2.47 2.75 2.91 2.47

Pennsylvania 2.67 2.88 3.00 3.15 3.27 3.34

dolomite Pennsylvania 3.49 4.20 - 3.5 3.87 -

marble Proctor, Vt. 1.57 3.18 3.33 2.4 3.42 3.49

1All measurements made 30°C. These results were obtained by a dynamical method, with
enclosed specimens.
2G= modulus of rigidity, in units of 10" dynes/cm2.
3Vs= velocity of shear or distortional waves, in km/sec.
4P= hydrostatic pressure, in kg/cm2.
358 F. R. SIEGEL

TABLE XV

SELECTED PHYSICAL CONSTANTS OF CARBONATE ROCKS. STANDARD CRUSHING STRENGTHS OF ROCKS

(After BIRCHet al., 1942, table 9-1)

Lithology Number of Average strength Range

localities (kglcm2) (kg/cm2)

limestone 216 960 60-3,600

marble 76 1,020 3 1 O-2,620

TABLE XVI

SELECTED PHYSICAL CONSTANTS OF CARBONATE ROCKS. SHORT TIME COMPRESSIVE STRENGTH OF

UNJACKETED MATERIALS WITH CONFINING PRESSURE OF KEROSENE~

(After BIRCHet al., 1942, table 9-6)

Lithology Location Confining pressure Strength

(kglcm2) (kglcm2)

limestone Solnhofen, Bavaria 2,560

Solnhofen, Bavaria 2,600
Solnhofen, Bavaria 3,260
Solnhofen, Bavaria 4,000
Solnhofen, Bavaria 5,970
Solnhofen, Bavaria > 13,000
marble location not given 810
location not given 860
location not given 1,650
location not given > 5J00
location not given > 11,400

Strength = p1-p2 at failure, where pi = axial compressive strength and p2 = lateral confining
pressure.
PROPERTIES AND USES OF THE CARBONATES 359

TABLE XVII
SELECTED PHYSICAL CONSTANTS OF CARBONATE ROCKS. THERMAL CONDUCTTVITY (AT1 atm PRESSURE)

(After BIRCHet al., 1942, table 17-4)

Lithology Location Temperature Conductivity K

( "C) cal.lsec cm degree Wlcm degree

limestone Solnhofen, Bavaria 0 7.2 . 10-3 30.1 .lo-3

Solnhofen, Bavaria 100 5.5.10-3 23.1 .
Solnhofen, Bavaria 200 4.8.10-3 20 10-3
limestone, (carbona- Pennsylvania 0 8.2 . 10-3 34.5.10-3
ceous), parallel to Pennsylvania 100 7.0.10-3 29.5.10-3
bed Pennsylvania 200 .
6.5 10-3 -
27.4 10-3
limestone, (carbona- Pennsylvania 0 6.1 . 10-3 25.5 .10-3
ceous), perpendicular Pennsylvania 100 5.4 . 10-3 22.6.10-3
to bed
limestone, dolomitic Longford Mills, Ont. 130 3.9. 10-3 -
16 10-3
Longford Mills, Ont. 181 3.8.10-3 -
16 10-3
Longford Mills, Ont. 268 3.7.10-3 15 .10-3
Longford Mills, Ont. 377 3.2.10-3 13 . 10-3
Queenston, Ont. 123 -
3.4 10-3 14 .10-3
Queenston, Ont. 177 3.4.10-3 14 .10-3
Queenston, Ont. 254 -
3.3 10-3 14 .10-3
Queenston, Ont. 332 3.2. 10-3 13 -
10-3
chalk 2.2.10-3 9.2.10-3
0 -
11.9 10-3 49.8 .10-3
dolomite 100 9.3 10-3 38.9.10-3
200 8.0 . 10-3 -
33.3 10-3
marble (17 varieties) 30 5.~7.7.10-3 21-32 .10-3
marble (black) St. Albert, Ont. 124 -
3.7 10-3 -
16 10-3
St. Albert, Ont. 210 3.6. 10-3 -
15 10-3
St. Albert, Ont. 334 3.3 10-3 14 .10-3

TABLE XVIII
SELECTED PHYSICAL CONSTANTS OF CARBONATE ROCKS. ELECTRICAL RESISTIVITY

(After BIRCHet al., 1942, table 21-1)

Lithology Location Resistivity (Q em)

limestone 3.105
Spain 104
Missouri 104-105
Kentucky 105
marble 10'0
France 4 * 108
France 109
France 10'0
360 F. R. SIEGEL

TABLE XIX
SELECTED PHYSICAL CONSTANTS OF CARBONATE ROCKS. DIELECTRIC CONSTANT

(After BIRCHet al., 1942, table 21-7)

Lithology Dielectric constant (range)

chalk 8.0-9.0
coral dolomite 8.0-9.0
dolomite 7.3
limestone 8.0-12.0
marble 8.3
marmorized limestone 15.2

Research on newer testing methods is continuously in progiess. CROW(1963)

presented an easy and precise optical method for determining Poisson’s ratio.
DURELLI and FERRER (1963) have developed a simple and somewhat novel way
of determining Young’s modulus and Poisson’s ratio, which could be practical
when speed is required or when measurements have to be made inside furnaces.
These authors expect the method to be especially useful for materials used in three
dimensional photoelastic studies.

Chemical composition

The chemical property of the carbonates which most influences their potential
usefulness is the chemical composition. Iron content, for example, is undesirable
in limestones to be used as dimension stone, because with weathering, the iron will
alter to the oxide, and stain the stone surface a reddish or brownish color. The
American Society for Testing and Materials, the U.S. Bureau of Standards, the
British Standards Institution, and similar organizations publish results of the inves-
tigations and give recommendations as to the limits of impurities that can be toler-
ated in carbonates for industrial use.
Stringent control must be maintained on the chemical composition of the
limestone used in the manufacture of many economically important products.
Thus, for the production of the better grades of glass, a maximum of only 0.2 %
iron oxide is allowable in the limestone used in the manufacturing process, and
for flint glass this impurity must not exceed 0.03 % (JOHNSTONEand JOHNSTONE,
1961). It must be remembered, however, that the economics of industrial operations
often dictates that a raw material, less pure than that recommended, be used so that
the end product is obtained at a maximum profit. This is true in the metallurgical
industry in which both the economics and the processes affect the acceptibility
of a carbonate rock considered as a fluxing agent for the removal of silica, alumina,
PROPERTIES A N D USES OF THE CARBONATES 361

and other undesirable impurities from the ore rock. For the production of pig
iron from iron ore in the blast furnace process, the limestone flux should contain
less than 1.5% silica, and less than 0.1 % each of sulphur and phosphorus; but
because of the logistics of individual operations, more silica and up to 0.5 %percent
sulphur might be tolerated. Several large companies use a limestone with 4-15 %
magnesia as a flux, although a purer limestone, if it were available at thesame
cost as that being used, would contribute to a more efficient process. Similarly,
for basic open-hearth smelting, the flux should be ideally at least 98% CaC03
with only 2 % of impurities such as alumina, silica and magnesium carbonate and
but a trace of phosphorus; however, in areas where the purer material is not avail-
able, the flux might contain 5-10% magnesium carbonate, 1.5 % alumina and
1 % silica. The capacity for phosphorus removal is lessened by the higher magnesia
content, and more flux must be used. Transportation costs involved in bringing
a purer fluxing agent from a distant area, however, would cut profit margins so
that the less efficient material is employed in many cases.
Table XXI contains individual and composite analyses of selected carbonate
rocks. There does not exist a standard list of components that should be determined
in the chemical analysis of a carbonate rock. The analyses that are made are de-
pendent, in some cases, upon the needs of the person requesting them and, in
others, by the availability of facilities and equipment. Some of the differences in
the type of compounds reported as part of a carbonate analyses are demonstrated
in Table XXI. An obvious difference can be found in the method of reporting
the loss on ignition in weight percent. Some laboratories equate this percentage
with the COZ content of a carbonate rock, but investigations made by GALLE
and RUNNELS (1960) and WAUGHand HILL(1960) demonstrate that this is not so.
By accurately controlling the temperature of a muffle furnace at 550°C and l,OOO"C,
values of the loss on ignition were obtained for carbonate and non-carbonate
portions. In samples which contain small amounts of pyrite, the loss on ignition
is complicated by the oxidation of the pyrite. Upon oxidation, the pyrite forms
Fez03 and oxides of sulphur, which in turn react with CaC03 below the inter-
mediate temperature to form CaS04, and thus cause a premature evolution of
COZ. It is possible to obtain a true COa value by applying corrective measures as
outlined by WAUGHand HILL(1960). It is evident that the results of a chemical
analysis, however technically perfect, are representative of a carbonate rock only
in so far as the sample supplied to the analyst is representative of the unit being
studied. GALLE (1964) has shown that on samples taken along an outcrop, channel
samples give more reliable and consistent analytical results than spot
samples, and indicated that analyses of carbonate rock to be presented to a possible
user should be made on channel samples.
CLARKE (1924) gave an extensive listing of chemical analyses of carbonate
rocks. GRAF(1 960a) presented tables of isotopic compositions and chemical
analyses of carbonate rocks and sediments and of minor element distribution in
TABLE XX
SOME PHYSICAL PROPERTIESOF SELECTED CARBONATE ROCKS~

Rock type Location ASG AP CS TS MRupIT AH SH Y M MRig SDC L B V P R Reference

limestone Ind. 2.37 11- 10.9 1.6 1.9 3 27 4.84 2.06 3 12.4 WINDES(1949)
(fossiliferous)
limestone Ohio 2.69 0.7 28.5 2.9 8.6 10 58 7.97 3.64 4 15.4 WINDES (1949)
limestone Ala. 2.83 0.9 24.0 6.6 7 66 7.64 3.51 4 14.2 WINDES(1949)
(coarse white)
limestone Colo. 2.25 16.6 0.4 3.7 10 56 1.8 1.0 22 7.8 WINDES
(1949)
(kerogenaceous)
limestone Utah 2.78 0.26 28.0 2.2 2.5 9.3 52 9.43 3.93 2 15.9-0.12 WINDES (1950)
limestone w. v. 2.68 6 23.0 1.9 2.5 9.6 61 9.56 3.96 3 16.4 0.21 WINDES(1950)
limestone Ohio 2.6 2.7 8.0 13 1.5 2.6 33 4.2 2.0 4 11 0.06 WINDES (1950)
limestone Ill. 2.68 0.8 22.3 2.6 3.0 7.4 52 9.87 3.84 3 16.5 0.28 BLAIR(1955)
limestone S. D. 1.71 26.0 2.4 0.3 13 0.65 0.37 10 5.7 0.13 BLAIR(1955)
(chalky-smokey
Hill-dry
limestone (chaky- S. D. 2.0 2.0 0.3 10 0.75 0.5 5.0 DWALLand
Smokey Hill) ATCHINSON (1957)
limestone (chalky- S.D. 1.81 8.3 3.7 0.6 1.2 16 0.98 0.57 13 6.3-0.13 BLAIR(1955)
Fort Hays-dry)
limestone Calif. 2.80 15.3 0.6 3.2 42 4.51 2.15 7 10.9 0.05 BLAIR(1955)
(metamorphic)
limestone Okla. 2.67 1.2 18.9 2.0 3.1 8 59 6.49 2.66 6 13.5 0.24 BLAIR(1956)
limestone (fossiliferous, Mo. 2.56 16.8 58 2.3 2.9 41 7.45 0.20 BLAIR(1956)
oolitic)
dolomitic limestone Ohio 2.5 6.4 13 17 2.1 3.7 30 6.1 2.6 7 14 0.19 WINDES(1950)
dolomitic limestone Ohio 2.5 5.2 12 22 2.0 4.0 36 6.8 2.8 10 14 0.23 WINDES (1950) 7
dolomitic limestone Ohio 2.8 1.3 26 28 4.0 7.2 55 9.5 4.1 4 16 0.16 WINDES(1950) P
dolomitic limestone Mo. 2.69 2.6 28.8 2.7 4.8 8.0 33 11.1 4.55 3 17.6 0.22 B~~m(1955)
dolomitic limestone, Mo. 2.67 3.6 21.2 1.5 4.2 7.2 48 5.61 3.05 >11 12.4-0.07 BLAIR(1955)
glauconitic
dolomite Tenn. 2.84 0.7 46.7 3.8 5.9 14 74 12.3 5.1 2 17.9 WINDES (1949)
dolomite (gray) Tenn. 2.76 2.3 52.0 3.8 7.1 13 69 11.3 4.6 3 17.4 WINDES (1 949)
dolomite (siliceous) Tenn. 2.77 1.2 35.6 2.5 4.6 11 66 10.9 4.62 2 17.0 WINDES (1949)
dolomite Ohio 2.4 8.6 13 11 1.8 3.4 42 2.8 1.55 5 9.0 -0.09 WINDES (1950)
dolomite Ohio 2.6 3.4 23 19 2.7 7.3 56 6.7 3.2 5 14 0.05 WINDES (1950)
dolomite Ohio 2.6 4.0 15 14 1.9 6.4 53 4.1 2.0 6 11 0.03 WINDES(1950) *z
dolomite Ohio 2.6 3.0 19 14 2.3 7.8 58 6.9 2.9 3 14 0.18 WINDES (1950) U
dolomite Ohio 2.4 11 14 2.1 4.2 39 3.2 1.5 4 10 0.07 WINDES(~~~O)
marble Md. 2.87
8.5
0.6 30.8 2.8 2.7 8 56 7.15 3.78 4 13.7 WINDES(1 949) c,m
m
marble (white) Nev. 3.2 2.3 34.5 2.4 11.9 5.02 4 16.6 WINDES (1949)
marble N. Y. 2.72 1.8 18.4 1.7 3.0 7 49 7.84 3.35 3 14.5 WINDES (1949)
limestone and marble Nev. 2.79 0.4 22.3 2.6 3.9 9 54 11.4 4.54 1 17.4 WINDES (1949)
marlstone (calcareous Colo. 2.31 4.9 21.9 1.8 4.3 6.7 56 3.61 1.61 14 10.5 0.11 WINDES(1950)
and dolomitic)
limestone 1.87-2.80 1.1-31.0 2.6- 427- 0.5-2 7ea 1-24 4.35- 0.8-3.6 TREFETHEN
(1959)
2.8 853 8.7
marble 2.64-2.87 0.4-2.1 8-27 427- 0.6-4 6ea 8 4 2 7.25- 1.3-6.5 TREFETHEN
(1959)
1280 10.15
limestone 2.66 8 26 WCOLF(1953)
dolomite 2.70 9 25 WCOLF(1953)
marble 2.63 6 47 WOOLF(1953)
limestone 2.34 2.5-28.4 3-6 1.2-3 KESSLERand SLIGH(1927)
limestone 2.56 16.5 700 7.6 15 ATCHISONet al. (1962)
marble (dolomitic) 2.80 22 950 12 18 ATCHISONet al. (1962)

Legend: ASG= apparent specific gravity; AP= apparent porosity (%); CS= compressive strength (1,OOO Ib./sq. inch); TS= tensile strength (1,OOO
lb./sq. inch); MRup= modulus of rupture (1,OOO Ib./sq. inch); IT= impact toughness (inch/sq. inch); AH = abrasive hardness (10-3 resistivity x sq.
inch/lb.); SH= scleroscope hardness (scleroscope units); YM= Young’s modulus? (106 Ib./sq. inch); MRig = modulus of rigidity (106 Ib./sq.
inch); SDC= specific damping capacity ( x lod2);LBV= longitudinal bar velocity (1,OOO ft./sec); PR= Poisson’s ratio (dimensionless).

W
m
w
TABLE XXI

SELECTED COMPOSITE AND INDIVIDUAL CHEMICAL ANALYSES OF CARBONATE ROCKS

I 2 3 4 5 6 7 8 9 10

talc. CaC03 80.83 89.78 86.39 79.86 70.10

calc. MgC03 2.26 1.33 1.94 1.39 3.96
CaO 42.61 41.32 45.44 50.40 48.49 43.01 42.92 54.84 53.81
MgO 7.90 2.19 1.68 1.09 1.29 1.03 0.42 0.26 0.56
coz 41.58 33.53 35.36 43.26 42.69
1.o.i. (34.55)
d.1.o.i. (lO5/55OyC) 1.34 0.75 0.89 1.12
d.1.o.i. (550/1,OOO"C) 36.73 40.17 38.93 34.44
SiOz 5.19 14.11 8.47 4.67 7.08 14.45 1.36 1.14 15.05 1.15
A1 2 0 3 0.81 4.16 1.91 0.81 1.22 2.32 0.18 9.02 0.45
Fez03
FeO } 0.54 1.63 3.71 1.16 1.55 2.46 0.20 ),.I' 1.27
0.26
acid. insol. Fe 0.14 0.29 0.13 0.14
MnO 0.05 0.038
MnOz
Ti02 0.06 0.16 0.08 0.05 0.07 0.18
KzO
NazO
0.33
0.05
0.71
0.39
0.25
0.07
0.07
0.02
0.12
0.04
0.39
0.10 } 0.07
Liz0 trace
sos 0.05 0.04 0.03 0.10 0.04 0.03 trace 0.09
S 0.09 0.25 0.02 0.26 0.06 0.04
FeSz 0.49
Pzos 0.04 0.15 0.09 0.03 0.05 0.08
HzO (-) 0.21(110"C) 0.23
HzO (+) 0.56l )19.03 0.69
carbonaceous material 0.61
SrO 0.12
F 4

Hz
vzos
total 100.09 99.40 99.96 99.87 99.96 99.79 99.47 100.00 99.40 99.91

I Composite analysis of 345 limestones (CLARKE,1924).

2 Argillaceous limestone standard sample la, U.S. Natl. Bur. Std., dried at 105°C (NATIONAL BUREAU
OF STANDARDS, 1954).
3 Composite analysis of 32 channel samples of the Toronto Limestone member of the Oread Limestone
Formation, Pennsylvanian age, eastern Kansas, taken along the strike of the outcrop from the Nebraska
border on the north to the Oklahoma border on the south (0.K. Galle, W. N. Waugh and W. E. Hill Jr.,
personal communication, 1964). Used for riprap, rubble.
4 Composite analysis of 32 channel samples of the Leavenworth Limestone member of the Oread
Limestone Formation, Pennsylvanian age, eastern Kansas, taken along the strike of the outcrop from the
Nebraska border on the north to the Oklahoma border on the south (0. K. Galle, W. N. Waugh and
W. E. Hill Jr., personal communication, 1964).
5 Composite analysis of 32 channel samples of the Plattsmouth Limestone member of the Oread Lime-
stone Formation, Pennsylvanian age, eastern Kansas, taken along the strike of the outcrop from the
Nebraska border on the north to the Oklahoma border on the south. Used for aggregate, road metal,
agricultural limestone (0.K. Galle, W. N. Waugh and W. E. Hill Jr., personal communication, 1964).
6 Composite analysis for 25 channel samples of the Kereford Limestone member of the Oread Limestone
Formation, Pennsylvanian age, eastern Kansas, taken along the strike of the outcrop from the Nebraska
border on the north to the Oklahoma border on the south (0.K. Galle, W. N. Waugh and W. E. Hill Jr.,
personal communication, 1964). Used for flagging.
7 Medway white chalk, Great Britain (JOHNSTONE and JOHNSTONE, 1961). Used for Portland cement
manufacture.
8 North Wales limestone, Great Britain (JOHNSTONE and JOHNSTONE, 1961). Used for Portland cement
manufacture.
 PROPERTIES AND USES OF THE CARBONATES 365

I1 12 13 14 15 16 17 18 19

55.41 94.39 calc. CaC03

43.00 0.61 calc. MgCo3
54.70 30.49 31.20 53.54 29.9 51.09 42.75 53.03 CaO
0.60 21.48 20.45 1.02 9.9 0.93 1.46 0.29 MgO
41.70 47.25 47.87 30.3 34.62 coz
(43.00) (47.52) 7.57 41.56 1.o.i.
d.1.o.i. (l05/55O0C)
43.27 33.8 43.92 d.1.o.i. (55O/1,OOO0C)
0.40 0.31 0.11 1.57 17.7 0.10 9.07 4.43 SiOz
0.52 0.067 0.63 0.30 0.40 2.5 0.14 0.85 1 A1203
0.08 0.084 0.70 0.19 0.24 1.1 0.08 0.93 (0'54 Fez03
FeO
acid. insol. Fe
0.006 0.18 MnO
0.02 MnOz
0.005 0.1 0.04 0.05 Ti02
0.03 0.9 0.16 KzO
016 0.08 0.06 0.8 0.14 NazO
Liz0
0.05 0.035 I .O 0.69 so3
0.27 0.013 0.007 S
FeSz
0.003 0.007 2.6 0.09 PZOS
0.006(105"C) )o.6 1.39 HzO (-)
J HzO (+I
trace 0.08 2.9 carbonaceous material
<0.01 SrO
0.3 F
0.008 Hz
0.1 vzos
99.78 99.94 99.95 100.18 100.08 100.7 96.30 99.95 99.85 total
~ -

9 Typical cement rock, Bethlehem, Penn. (ECKEL,1913).

10 Lithographic limestone, Solnhofen, Bavaria (CLARKE, 1924).
I1 Spergen Formation (oolitic Salem Limestone), Mississippian age, Indiana (LOUGHLIN, 1930). Used
for building stone.
12 Dolomite standard sample 88, U.S. Natl. Bur. Std., dried at 105"C (NATIONAL BUREAU OF STANDARDS,
I#954).
13 Ketona Dolomite, Cambrian age, Alabama (BALLand BECK,1938). Used for fluxstone and a source
for magnesia.
14 Niagara Dolomite, Silurian age, Illinois (LAMAR, 1960). Used as a refractory and for dead-burned
dolomite.
I5 Composite analysis of 10 channel samples of the Baum member of the Paluxy Formation, Lower
Cretaceous age, Oklahoma (WAYLAND and HAM,1955).
16 Composite of 15 analyses of the Meade Peak member of the Phosphoria Formation, Permian age,
Wyoming (GULBRANDSEN, 1958, compiled from MCKELVEY et al., 1953).
17 Composite of 8 analyses of the Marble Falls Formation, Pennsylvanian age, Texas (BARNES, 1952).
18 Composite analysis of 9 mark from Minnesota lakes (GOLDICH et al., 1959). Total loss on ignition
less COZand HzO (-)
19 Limestone from Maquijata, Province of Santiago del Estreo, Argentina (GAMKOSIAN et al., 1961).

Includes organic matter.

366 P. R. SIEGEL

these materials (GRAF,1960b). Several analyses have also been presented by

GILLISON (1960a,b). INCERSON (1962) noted that compilations of carbonate rock
analyses were being made at least at two places: H. R. Gault began such a com-
pilation at Lehigh University and his program is being continued by K. Chave. The
collection of analyses of all types of sedimentary rocks was begun by W. W. Rubey
of the U.S. Geological Survey and continued by H. A. Tourtelot, who reports
(personal communication, 1964) that for Kansas, Nebraska, North Dakota,
South Dakota, Montana, Wyoming, and Colorado, it had already been completed.

Other properties

The number of measurable properties of carbonate minerals is great (see GRAFand

LAMAR,1955) and is increasing as systematic advances in theory and instrument
technology are made (e.g., electron-spin resonance, nuclear magnetic resonance,
Mossbauer effect, microwave, and exo-electron emission studies). Some of the
properties of a physical-chemical nature are summarized in Tables XXII-XXIV.
For the most part, the data given are for pure compounds, and as noted previously,
properties will vary with the presence of impurities. Among the properties most
affected by the presence of foreign ions in the crystal lattice are thermolumines-
cence, infrared absorption, and those properties related to solid solution.

Solid solution and subsolidus relations

Much of the initial impetus for these studies was provided by GRAFand GOLD-
SMITH (1955) and HARKER and TUTTLE (1955) who investigated the solid solution
and subsolidus relations in the system CaC03-MgC03. It was found that the per-
centage of Mg in calcite could be determined from various cell parameters (e.g.,
dioia, a or c). Similar results were given by CHAVE(1952), who found a linear
variation in the dloia spacing with varying percentages (2-1 6 %) of MgC03 in shell
material from living organisms. At the elevated temperatures and pressures used
by HARKER and TUTTLE (1955), the solubility of MgC03 in CaC03 increased from
5 mol: % at 500°C to 27 mol. % at 900°C. Corroborating figures were given by
GRAFand GOLDSMITH (1955). Because of these and similar relations, it was sug-
gested that when a rock contains dolomite in equilibrium with magnesian calcite,
the amount of solid Solution can be used as a geologic thermometer. Harker and
Tuttle also found that at 900"C, dolomite will take only 1 % excess MgC03 in
solid solution indicating that the miscibility gap in the system CaC03-MgC03
is almost complete and that at this same temperature magnesite would take only
about 2 % (by weight) CaC03 into solid solution. GRAF(1960c), citingunpublished
data of Goldsmith, wrote that at 800°C dolomite will hold 2 mol. %excess CaC03
in solid solution and that this would increase to 4 % at 900°C. GOLDSMITH and
GRAF(1958a) were able to determine the mole percentage of CaC03 in dolo-
mites from various rocks by X-ray diffraction techniques.
TABLE XXII
MELTING AND TRANSFORMATION TEMPERATURES AND SOLUBILITIES OF SOME ECONOMICALLY IMPORTANT CARBONATE MINERALS

(Melting and transformation temperatures after KRACEK,

1963; solubilities after PERRY
et al., 1963)
*2:
v1

Solubility in 100 g
'
Mineral Melting point Dissociation temperature Transition point H20

m
s
b5
calcite 1,339"C(at 1,038 898.6"C 970 "C 0.0014 (25°C) %
bars C02 pressure) 1
dolomite at 500°C and 1 atm COZ
pressure,
0.032 (1 8 "C) 8
n
dolomite+CaCOs+ MgOSCOZ z-
at 89OoC,
+
dolomite-tCaO Mg0+2C02
0
2:
magnesite 404°C (at 1 atm COz pressure) 0.0106 5
rhodochrosite 369 "C (at 1 atm C02 pressure) 0.0065 (25°C) E
siderite 450°C (at 1 atm C02 pressure)
smithsonite 3oO-400"C (at 1 atm C02 pressure) 0.001 (15°C)
aragonite to calcite at about 0.0012 (20°C)
425°C and 1 atm
pressure
witherite 1,740"C (at 90 atm 1,204"C (at 0.068 atm C02 pressure) 806"C, 968 "C 0.0022 (1 8 "C)
C02 pressure) 1,352"C (at 1 atm CO2 pressure)
strontianite 1,497"C (at 60 atm 1,091"C (at 0.152 atm COZpressure) 925°C 0.0011 (18°C)
C02 pressure) 1,289"C (at 1 atm CO2 pressure)
cerussite 293°C (at I atm COZpressure) o.oO011 (20°C)
malachite 200 "C
azurite 200 "C
trona 195°C
TABLE XXIII

HEATS OF FORMATION, FREE ENERGIES OF FORMATION AND HEAT CAPACITIES OF SOME ECONOMICALLY IMPORTANT CARBONATE MINERALS'

Heat of formation Fret' energy Of formation Heat capacity at constant Range of temp. Uncertainty
at 25"C, kcallmole at 2jaC9kcallmole pressure (T='K; O"C=273.1 OK), ( O K ) ( %)
AH (I)@ (2) A F (calldegree mol)

calcite -289.5 -270.8 -269.78 19.68+O.O I 189T-307600/Tz 273-1 033

dolomite -558.8 -520.0 40.1 299-372
magnesite -261.7 -241.7 -246.0 16.9 290
rhodochrosi te -21 1 -192.5 -195.4 7.79 +OM2 1T +0.0000090T2 273-773
siderite -172.4 -154.8 -161.06 22.7 293-368
smithsonite -192.9 -173.5 -174.8
aragonite -289.54 -270.57 -269.53
witherite -284.2 -271.4 -272.2 a 17.26+0.0131T 273-1083 5
30.0 1,083-1 255 15
strontianite -290.9 -271.9 -271.9 21.8 281-371 ?
cerussite -167.6 -150.0 -149.7 21.1 286-320 ?
malachite -216.44
azurite -373.73

1 Heats of formation, free energies of formation (I)and heat capacities, compiled from LILEY
et al. (1963); free energies of formation (2) compiled from
CARRELS et al. (1960).

crl
P
PROPERTIES A N D USES OF THE CARBONATES 369

TABLE XXIV

MAGNETIC SUSCEPTIBILITIES OF CERTAIN CARBONATE MINERALS

(Compiled from POWELL

and MILLER,1963)

Mineral Location

calcite Joplin, Mo. 12

calcite not given - 0.384
dolomite Cumberland, Great Britain 156
dolomite Guanajuato, Mexico 73
dolomite Westchester Co., N.Y. 51
dolomite Berkshire Co., Mass. 42
dolomite not given 42
dolomite not given 0.993
magnesite Regla, Cuba 83
magnesite Lancaster Co., Texas 17
siderite Roxbury, Conn. 499
siderite Allevand, France 492
siderite not given 103.8
siderite not given 103.7
siderite Kellogg, Idaho 91.5
siderite Saline Co., Ark 90.8
siderite Rhine Province, Germany 87.3
siderite Saline Co., Ark. 85.8
siderite Saline Co., Ark. 84.2
siderite Los Angeles Co., Calif. 83.2
siderite Leadville, Colo. 81.5
siderite Cass Co., Texas 77.2
siderite Pulaski Co., Ark. 75.4
siderite Clairborne Parish, La. 12.5
siderite Pulaski Co., Ark. 72.1
siderite Rogers Co., Okla. 66.6
siderite Bates Co., Mo. 66.2
siderite Roxbury, Conn. 66.1
rhodochrosite not given no value given
smithsonite Mineral Point, Wisc. 17
smithsonite Kelly, N.M. 14
aragonite not given - 0.408
witherite Cumberland, Great Britain 4
strontianite not given no value given
cerussite New South Wales, Australia 65
cerussite New South Wales, Australia 23
limestone not given 6

1x= 1 * 10-6 cgs electromagnetic units.

370 F. R. SIEGEL

The most comprehensive study on the properties of the calcium and magne-
sium carbonates was presented by GRAFand LAMAR(1955), with a bibliography
of 524 references. Further advances in understanding this CaC03-MgC03 system
were made by GOLDSMITH and GRAF(1958a) who published data on structural and
compositional variations in some natural dolomites, as well as on the relation be-
tween lattice constants and composition in the Ca-Mg carbonates (GOLDSMITH
and GRAF, 1958b). More recently, ROSENBERG and HOLLAND(1963) gave a
preliminary report on the stability of calcite, dolomite, and magnesite in chloride
solutions at elevated temperatures and COa pressures.
The solid solution relations existing between calcite and rhodochrosite
were reported on by GOLDSMITH and GRAF(1957). They have shown experimentally
that a complete series exists above 550°C at COZpressure sufficient to prevent de-
composition, but that there is a solubility gap at lower temperatures in the man-
ganese half of the system. BODINE and HOLLAND (1963) have provided additional
data on the coprecipitation of manganese with calcite at elevated temperatures to
complement data presented by GOLDSMITH and GRAF(1957), who were able to
precipitate the complete Ca-Mn carbonate solution series at room temperature.
ROSENBERG and HARKER (1956) worked on the subsolidus phase relations
in the CaC03-FeC03 system and found a miscibility gap between calcite and si-
derite at temperatures from 350-550°C. Experiments run at COZpressure high
enough to prevent dissociation showed that a solid solution of 5 mo1.X siderite
in calcite is stable at 400°C and that at 5OO0C, about 14 mo1.x siderite can be
taken into solid solution by calcite. Under similar COZpressure conditions, GOLD-
SMITH (1959) reported that a solid solution of up to 8 mol. % siderite in calcite is
stable at 400°C and at 700°C this increases to 37 mol. %. In a more recent study at
elevated temperatures (ROSENBERG, 1963) (using small CO partial pressure to
maintain iron as Fez+), a solvus between CaC03 and FeC03 was determined
between 300 and 550°C. With COe pressures sufficient to prevent dissociation of
the carbonates, solid solutions containing up to 9 mo1.x siderite in calcite and
7 mo1.X calcite in siderite were stable at 400°C. At 500°C the solvus passed
through a point at 17 mol. % siderite in calcite.
Related studies on ternary systems have been made. GOLDSMITH and GRAF
(1960) investigated the subsolidus relations in the system CaC03-MgC03-MnC03
in the temperature range of 5O0-80O0C, with special emphasis being given to the
CaMg(C03)2-CaMn(C03)~ join; above 650 "C, a complete solid solution series
extends between the two members.
In his work on the system CaC03-MgC03-FeC03, particularly on the join
CaMg(C03)2-CaFe(C03)2, ROSENBERG (1959) found that at 450°C this join is
binary from CaMg(C03)~to 75 mo1.X CaFe(CO3)z. GOLDSMITH et al. (1962)
studied the phase relations in this same system at temperatures ranging from 600
to 800°C and 15 kbars total pressure.
More recently GOLDSMITH and NORTHROP (1 964) have reported the results of
 PROPERTIES AND USES OF THE CARBONATES 371

their research on the subsolidus phase relations in the ternary systems CaC03-
MgC03-CoC03 and CaC03-MgC03-NiC03.
Although emphasis has been on the minerals of the calcite or dolomite
groups, CHANG(1964a) worked on the subsolidus phase relations in the binary
systems BaC03-CaC03, SrC03-CaC03, and BaC03-SrC03 between 400 and
1,OOO”C and at C02 pressures high enough to prevent decomposition of the
carbonates. He observed that for the system BaC03-CaCO3, there is a complete
solid solution above 850°C; at 400”C, CaC03 was 3.5 mol. % soluble in BaCOs;
and at 700”C, 5 mol. % soluble. The maximum amount of calcium taken up by
SrC03 is about 47 mol. % at 550°C.

Thermoluminescence
Certain minerals possess the ability to store energy in the form of electron energy.
An electron, displaced by some external source of energy such as natural a radia-
tion, can be moved from its normal lattice position and become “trapped” by
some type of imperfection in the crystal lattice structure. Some of the common
types of possible electron traps are described by DANIELS et al. (1953): ( I ) imper-
fections and vacancies in the crystal lattice produced at the time of crystal forma-
tion, or later by mechanical stress or thermal agitation; (2) lattice vacancies
(Schottky defects); (3) distortions produced by impurity ions of larger or smaller
radius than is normal in a given crystal lattice; and (4) dislocations produced by
radioactive bombardment. In addition, Frenkel defects, which are produced when
an atom is transferred from a lattice site to an interstitial position, can serve as
electron traps (KITTEL,1956, chapter 17); and color centers (F, F’, R and N
centers) may act as traps for electrons, whereas V centers may act as traps for
holes (KITTEL,1956, chapter 18). Any excess energy associated with the electron
becomes “frozen” in the trap; when released by the application of heat, the excess
- energy is dissipated in the form of heat and light. The light thus produced is termed
thermoluminescence.
The frontispiece (p.VI) shows calcite crystals that were photographed by
their own thermoluminescence. These crystals were subjected to approximately
-
2 106 Roentgens of y-radiation from 6OCo. They were then heated on a standard
laboratory electric hot plate to 300°C in a completely dark room and the photo-
graphic exposures were made. Both the rhombohedra1 and scalenohedral crystal
forms give the orange luminescence characteristic of calcite. The photographs were
prepared by H. K. W. Bowers, using Ektachrome Daylight film and an
exposure time of 1+ min. This technique for obtaining excellent representations of
mineral thermoluminescence was developed by Mr. Bowers as part of a radiation
damage research project supported by the U. S. Atomic Energy Commission
(contract no.AT( 11-1)-1057), with Dr. E. J. Zeller being the principal investigator.
The thermoluminescence of calcite, aragonite, dolomite, and magnesite
has been studied by many workers and attempts have been made to use observed
372 F. R. SIEGEL

effects in solving certain geologic problems involving carbonate rocks. For example,
limited success was achieved in correlation and zonation of carbonate sediments by
PARKS(1953), SAUNDERS (1953), BERGSTROM (1956), LEWIS(1956), and BROOKS
and CLARK(1961), whereas SIEGEL(1963) was able to relate artificially induced
thermoluminescence of sedimentary dolomites to their probable environment of
deposition. ZELLER(1957), PEARN(1959), D’ALBISSIN et al. (1962), and ZELLER
and RONCA(1963) have applied thermoluminescence techniques to direct age
determinations and the dating of tectonic and thermal events. Temperature
(including paleoclimatology) and pressure histories of carbonate rocks have been
revealed by thermoluminescence investigation (ZELLER,1957; ANGINO,1961 ;
Ronca, 1964). HANDINet al. (1957) have used thermoluminescence in deformation
studies of calcite and dolomite, as have ROACHet al. (1961) in their investigation
of the effects of impact on marble. Geochemical prospecting using thermolumines-
cence has been reported by MACDIARMID (1960a, b). The above represent only a
fraction of the studies made using thermoluminescence. ANGINOand GROGLER
(1 962) have compiled an extensive bibliography of thermoluminescence regearch
containing more than 600 entries. This is an excellent reference work for scientists
intending to do thermoluminescence research on carbonates and other rocks.

Infrared absorption spectra

HUANGand KERR(1960) described the infrared spectra of 27 common and rare
carbonates and found that each one shows characteristic absorption bands, some
of which differ from published curves. In the calcite and the aragonite groups
there was a noteworthy shift of absorption bands with longer wave lengths,
which corresponds to an increase in cation radius or mass, a phenomenon also
observed by KELLER et al. (1 952). HUANGand KERR(1960) believed that the spec-
tral difference between the more common groups may be related to crystal struc-
ture and that infrared-active groups (CO32-, HCOs-, HzO, OH-, and so42-)
dominate the absorption characteristics.
Although the emphasis of infrared studies has been on mineral identification
(Table XXV), ADLERand KERR(1962) began applying the method to geologic
problems. In a detailed study on aragonite and calcite, they found that in artificial
mixtures, the intensity ratio of the bands at 11.41,~(specific for calcite) and 11.65,~
(specific for aragonite) is approximately proportional to the ratio of concentration
of aragonite and calcite in a given sample. This relation held for recent and fossil
invertebrates and suggested application of the method to the study of the composi-
tion of calcareous shells. Later empirical studies of infrared absorption spectra of
isomorphous, anhydrous carbonate minerals (ADLER and KERR,1963)demonstrated
that shifts in the frequencies of carbonate-ion vibrations are primarily related to
differences in the radius of cations in the external lattice positions. They believed
that this relationship may be conditioned by the electronic periodicity of the cations;
and although mass effects are suggested, they are not definitely shown. In addition,
PROPERTIES AND USES OF THE CARBONATES 373

they interpreted spectral differences among the calcite group and aragonite group
minerals in terms of co-ordination change between the two groups and the mineral
composition within each group. ADLER(1963) presented some basic considerations
in the application of infrared spectroscopy to mineral analysis. He affirmed that
the infrared absorption spectra may be used in various ways to gain information
on minerals and mineral aggregates, such as composition, structure, and mode of
combination of molecular ions (anionic radicals) in unidentified materials.

USES

The most recent compilation of uses in which the carbonate rocks are employed
directly (e.g., dimension stone) or indirectly in a manufacturing process (e.g., glass
manufacture or sugar refining) was made by LAMAR (1961). In this paper, Lamar
gave more than 70 uses for limestone and dolomite, and general physical and/or
chemical specifications for each use; he also included an excellent bibliography of
156 entries. Similar presentations have been made by other authors. JOHNSTONE
and JOHNSTONE (196 1) wrote about minerals for the chemical and allied industries,
with a chapter devoted to limestone, chalk, and whiting; carbonates are also con-
sidered in separate chapters on iron ores, lead, magnesium, manganese, sodium
carbonate, and strontium. These authors included many British and Canadian
specifications in addition to the American Society for Testing and Materials
requirements. In the American Institute of Mining, Metallurgical, and Petroleum
Engineers (1960) edition of Industrial Minerals and Rocks (Nonmetallics other than
Fuels), GILLISON (1960a,b) treated physical and chemical properties of the car-
bonate rocks and discussed some of the uses for limestone and dolomite. This
fine symposium also contains chapters on specific carbonate products (e.g.,
cement materials, chalk and whiting, crushed stone, dimension stone, lime, mag-
nesite and related materials, mineral fillers, refractories, sodium carbonate from
natural sources in the United States, and strontium minerals). GAMKOSIAN et al.
(1961) listed the chemical specifications of carbonate rocks to be used for specific
industries of Argentina; it was noted that Gamkosian is preparing a publication
entitled Technologia Mineral, in which he will present various physical and chem-
ical requirements followed not only in the Argentine Republic, but probably
also in other republics of Central and South America.
Previous to this surge of publications in 1960 and 1961, BOWLES (1956) sum-
marized many uses for limestone and dolomite, bringing up to date earlier publi-
cgions of the U. S. Bureau of Mines by BOWLES (1952) on the lime industry, by
BOWLESand JENSEN (1947) on the industrial uses for limestone and dolomite, by
BOWLESand JENSEN (1941) on limestone and dolomite in the chemical and pro-
cessing industries, and by COLBY(1941) on the occurrence and uses of dolomite
in the United States.
TABLE XXV w
2
INFRARED ABSORPTION BANDS OF SOME ECONOMICALLY IMPORTANT CARBONATE MINERUS

(Compiled from HUANG

and KERR,1960, and ADLERand KERR,1963)

Mineral Position of absorption bands; wavelength ( p ) Reference

calcite 3.93 5.52 6.97 11.42 14.03 HUANGand KERR(1960)

3.92 5.50 6.97 11.40 14.02
7.02 11.40 14.02 ADLERand KERR(1963)
7%5 ir.41 14.03
dolomite 3.95 5.50 6.90 11.35 13.70 HUANGand KERR(1960)
6.95 11.35 13.72 ADLERand KERR(1963)
6.97 11.35 13.71
magnesite 5.50 6.90 11.28 13.36 HUANGand KERR(1960)
6.86 11.28 13.35 ADLERand KERR(1963)
6.94 11.29 13.35
rhodochrosite 3.95 5.52 6.98 11.53 13.76 HUANGand KERR(1960)
7.07 11.54 13.75 ADLERand KERR(1963)
7.09 11.55 13.77
siderite 3.95 5.50 7.03 11.55 13.58 HUANGand KERR(1960)
7.06 11.53 13.54 ADLERand KERR(1963)
7.08 11.55 13.58 .
smithsonite 3.95 5.47 6.95 11S O 13.45 HUANG and KERR (1960)
7.04 11.48 13.42 ADLERand KERR(1963)
7.06 11.50 13.45
aragonite 3.95 5.55 6.70-7.00 9.22 11.42 14.03
11.63 14.30
3.95 5.55 6.72 9.22 11.40 14.03 HUANGand KERR(1960)
11.63 14.30 I"
3.93 5.53 6.70-7.00 9.22 11.42 14.03 0
11.63 14.30 Y
6.80 11.65 14.02 ADLERand KERR (1963)
8P
 v

6.79 11.64
14.31
14.04 E
witherite 4.00 5.65 6.92 9.40 11.63
14.31
14.43
14.41
HUANGand KERR(1960)
ADLERand KERR(1963)
b!$
6.97 11.63
6.99 11.62 14.41 a.
strontianite 3.97 5.57 6.80 9.30 11.63 14.15 HUANGand KERR(1960)
14.30 12
6.88 11.65 14.16 ADLERand KERR(1963)
14.31 d
6.86 11.65 14.14
14.29
E
c,
cerussite 5.75 6.95 7.13 9.48 11.90 14.77 HUANGand KERR(1960) $
7.17
7.18
11.90
11.92
14.75
14.75
ADLERand KERR(1963)
82.
malachite 2.85 6.62 7.00 9.10 11.45 12.17 13.33 14.05 HUANGand KERR(1960) 5
7.17 9.52 12.90 12
azurite 2.84 5.40 6.63 7.03 9.15 10.47 11.97 12.23 13.00 13.45 HUANGand KERR(1960)
6.78
trona 2.83 5.92 6.80 9.45 11.75 14.70 HUANGand K E R(1960)
~
9.65
376 F. R. SIEGEL

The US.Bureau of Mines annual publication, Minerals Yearbook, Volume

I , (Metals and Minerals except Fuels) gives an excellent review of carbonate rocks
and materials derived from them (e.g., calcium and calcium compounds, cement,
lime, magnesium, magnesium compounds, manganese, sodium and sodium
compounds, stone, and strontium). Major uses are also listed along with pertinent
production and dollar statistics. This volume also includes data on production
increases (or decreases) for given uses, and makes note of the development of
technological advances or new products which affect carbonate (and other) rock
economics. The Bureau of Mines has a materials survey project under way; and
in 1963, COMSTOCK treated magnesium and magnesium compounds in great detail
and listed the principal uses for magnesium compounds (derived in part from dolo-
mite and magnesite), as given in Table XXVI.
Table XXVII gives more than 100 uses for limestone, dolomite, marble,
precipitated calcium carbonate, or products derived from them (e.g., lime). The
table is constructed on a base of LAMAR’S (1961) paper and is supplemented by the

TABLE XXVI

PRINCIPAL USES FOR MAGNESIUM COMPOUNDS

(After COMSTOCK,1963)

Magnesium oxide Precipitated magnesium carbonate

Refractory grades: insulation

basic refractories rubber, pigments, and paint
Caustic-calcined: glass
cement ink
rayon ceramics
fertilizer chemicals
insulation fertilizers
magnesium metal Magnesium hydroxide
rubber sugar refining
fluxes magnesium oxide
refractories pharmaceuticals
chemical processing and manufacture Magnesium chloride
uranium processing magnesium metal
paper processing cement
U.S.P. and technical grades: ceramics
rayon textiles
rubber (filler and catalyst) Paper
refractories chemicals
medicines
uranium processing
fertilizer
electrical insulation
neoprene compounds and other chemicals
cement
 PROPERTIES AND USES OF THE CARBONATES 377

20

18

I6

14
600
12

550
10

u
8

6
450 1954 '55 '56 '57 '58 '59 '60 '61 '62 '63 '64
1955 '56 '58 '59 '60 '61 '62 '63 '64
Fig. 1 . Fig.2.
Fig.1, U.S. crushed stone production (in millions of tons). Printed by permission of Rock Products
(Mining and Processing), January, 1964.
Fig.2. U.S. lime production (in millions of tons). Printed by permission of Rock Products (Mining
and Processing), January, 1964.

400
390
380
370
360
350
340
330
320
310
3m
1955 '56 5 7 '58 '59 '60 '61 '62 '63 '64
Fig.3. U.S. Portland cement production (in millions of barrels). Printed by permission of Rock
Products (Mining and Processing), Januaiy, 1964.

sources already mentioned as well as trade magazines such as Rock Products or

Rock Products (Mining and Processing) (name changed with the January, 1964,
number). Several of the derivatives of the carbonate rocks (such as whiting or lime)
have multiple uses; to give the reader an idea of the magnitude of applications a
single derivative can have, the various uses in which and for which whiting is used
are presented in Table XXVIII. In some reviews of carbonate economics, the uses
of carbonate minerals are neglected. Such data are readily available in most mi-
neralogy and economic geology textbooks and other not so widely known reference
works such as those by STECHER (1 960) and LANGE (1 956). In Table XXIX, some
of the more important uses for natural or artificially prepared carbonate minerals
are summarized.
The future looks good for the continued development of the major industries
in which carbonate rocks are a primary raw product. Trends in the U.S.production
of crushed stone, lime, and Portland cement (Fig.1, 2, and 3, respectively) are all
TABLE XXVII w
4
00
PURPOSES FOR WHICH LIMESTONE AND DOLOMITE (OR LIME DERIVED FROM THEM) ARE USED (WITH SOME GENERALSPECIFICATIONS)

(Constructed on a base of the report by LAMAR,1961, and supplemented by data from BOWLES
and JENSEN,1941, 1947; COLBY,1941; BOWLES,
1952,
1956; BOWEN,1957; JOHNSTONE and JOHNSTONE,1961; and ANONYMOUS, 1963)

Use Physical requirements Chemical requirements

abrasive (scouring and polishing finely pulverized; free of grit

preparations)
acetic acid manufacture high-calcium limestone
acid neutralization size varies for each job and for equipment > 95 % CaC03
being used; particles 1-3 mm and 1-3 inch
in diameter have been used
aggregates and road stone resistant to abrasion; sound; size varies, but free of deleterious substances such as chert,
coarse (>0.187 inch) to fine (<0.187 inch) is shale, or clay
common
agricultural limestone and dolomite ground to specification for each job or high calcium-carbonate equivalent,
according to state law at least 80%
alcohol and phenol highcalcium limestone, free of
deleterious substances
alkali stone 1 or 2 to 6 inches in diameter high-salcium limestone with < 1 % silica
aluminium oxide (Bayer process) > 97 % CaC03 and < 1 % silica
aluminium production high-calcium limestone, low in silica
ammonia
asphalt filler size varies according to process; generally 80%
should pass through a 200-mesh sieve
athletic-field marking light in colour
barnstone stone should pass through an 8-mesh sieve reasonably high purity
bleaching powder and liquid open-textured limestone or chalk preferred high-calcium limestone with only traces of
. Mn, Fe, MgO, or clay
brick glazing finely ground
brick making (silica refractory brick and workable impure argillaceous limestone
sand-lime and slag brick
bulb growing (in planters) in small chips and of an attractive colour
calcium acetate
calcium carbide and calcium cyanamide limestone should not decrepitate during burning > 97 % CaC03, < 0.01 % P, <2 %MgO,
but should give a tough strong lump maximum of 3 % SiOz, c 0.05 - 0.75 %

calcium carbonate (precipitated)

Fez03 +A1 2 0 3 , trace of S sm
111
calcium hydride

calcium nitrate high-calcium limestone

carbolic acid and carbonic acid
carbon dioxide high-purity limestone or dolomite,
which gives > 30 % COZ b
ceramics > 97 % total carbonates, < 0.3 % FezO3, 0
z
<2 % si02, <o. 1 % SO3 5
chromate and bichromate dolomite B
citric acid free of deleterious substances
coke and gas (gas purification high calcium limestone which gives
and plant by-products) > 95 % CaO
creameries and dairies
dimension stone good weathering resistance; free minimum amount of iron or iron-bearing
of deleterious substances minerals (pyrite and marcasite)
cut stone, exterior use good weathering resistance; free from minimum amount of iron or iron-bearing
fractures or joints; pleasing aspect minerals (pyrite and marcasite)
cut stone, interior use free from defects; pleasing appearance; minimum amount of iron or iron-bearing
resistant to abrasion if used for minerals (pyrite and marcasite)
flooring or steps
ashlar, rubble good weathering resistance; free from defects, minimum amount of iron or iron-bearing
one good face; resistant to abrasion minerals (pyrite and marcasite)
if to be walked on
veneering, flagging, and curbing good weathering resistance; one good minimum amount of iron or iron-bearing
face; resistant to abrasion if to be minerals (pyrite and marcasite)
walked on w
 w
TABLE XXVII (continued) 00
0

Use Physical requirements Chemical requirements

monumental stone superior weathering resistance; free from minimum amount of iron or iron-bearing
defects; uniform; pleasing appearance minerals (pyrite and marcasite)
disinfectants reasonably high purity
dyes stone should all pass a 20-mesh sieve high-calcium limestone
and 97% should pass a 100-mesh sieve
electrical products
Epsom salts stone should pass a 60-mesh sieve , dolomite with > 99 % calcium and
magnesium carbonates combined
explosives pure carbonate rock with as much
magnesium as calcium
fertilizer filler usually stone should pass an 8-mesh sieve reasonably pure limestone or dolomite
but be retained on a 20-mesh sieve
fill material (other than riprap)
filter stone 3.5-2.5 or 3.5-1.5 inch sizes are used; minimum amount (if any) of pyrite,
rough surface; should withstand 20 cycles marcasite, and clay
of the N a ~ S 0 4soundness test;
minimum of fines
flux
blast furnace size varies from about 0.5-6 inches depending vary according to the user and economics
on the user and the economics of the of the operation
operation; minimum amount of decrepitation
open-hearth furnace is necessary
size varies from about 4-1 1 inches depending on vary with user; generally > 98% CaC03
the user and the economics of the trace of P
operation; minimum amount of decrepitation
is necessary cr!
foods ga
fungicides and insecticides high-calcium limestone, low in Fez03 and
AIzo3; composition should be uniform
glass stone should pass a 16-20-mesh sieve but > 98 % total carbonates, < 0.05 % iron
should be retained on a oxide, low in S and P, minimal amount
100-140 mesh sieve possible of C
gelatin free of deleterious substances
glue free of deleterious substances
grease 98 % should pass a 200-mesh sieve and high-calcium limestone with < 1.5 % MgO,
95 % should pass a 325-mesh sieve < I % silica, < 0.5 % Fez03 sm
leather dressing (tanning) high-calcium limestone, low in Fe or other
metallic impurities; MgO and clay are
injurious
lime vary with production techniques; stone > 90% CaC03 (preferably 97-98 %) and
should be hard and should not decrepitate < 5 % MgC03, < 3 % other impurities
upon burning; fines are undesirable for high-calcium lime; > 40% MgC03
and < 3 % other impurities for high-
magnesium lime
lithographic limestone even texture; free of defects, grit or granular
impurities
magnesia recovery from sea water dolomitic limestone
magnesium and magnesium compounds size stone used varies with dolomite of high purity
individual operations
magnesium chloride 42 % MgC03,55 % CaC03, and -=3 % SiOz +
Rz03
masonry cement
membrane waterproofing stone should be sound; size varies
with operation
mineral feeds for livestock stone should pass a 200-mesh sieve > 95 % CaC03; low (if any) F
mineral-treatment processes high-purity limestone, low in Mg
(e.g., flotation)
monocalcium phosphate pure, high-calcium limestone
natural cement finely pulverized limestone or dolomite with 13-35 %
clayey material (of which SiOz is 10-22 %)
and 4 1 6 % A 1 ~ 0 3 S F e z 0 3
oil-well drilling
W
m
 w
TABLE XXVII (continued) 00
h,

Use Physical requirements Chemical requirements

ore concentration and refining high-calcium limestone

(e.g., flotation)
paints
paper stone > 3 inches in diameter highcalcium limestone, low in Mg, < 2 %
AlzOs+Fez03+ acid insoluble material;
acid insoluble material should be light in
colour and should settle rapidly
petrochemicals (glycol)
petroleum refining
pharmaceuticals high-purity limestone (artificially
prepared usually)
Portland cement hard impurities are undesirable > 75 % CaCO3, < 3 %MgO, < 0.5 % Pz05;
for white Portland cement, limestone
should be low in Fe ( <0.01% FezO3);
low Mn content is desirable
poultry grit stone should pass a @-mesh sieve but should high-calcium limestone with < 0.1 % F
be retained on a 10-mesh sieve
pozzolana cements
railroad ballast various sizes of stone are used; should have a
good abrasion hardness and a minimum
amount of deleterious substances
rayons
refractory dolomite and dolomite
refractories: raw dolomite stone should pass a 0.75-inch sieve; >20% MgO,<O.O5%S,<2%SiOz
fines are removed; should not
disintegrate when heated
calcined dolomite stone should pass a 0.75-inch sieve; > 20% MgO, < 0.05% S, < 2 % SiOz
fines are removed; should not
disintegrate when heated
 dead-burned dolomite size of stone used varies but is
usually <0.5 inch in diameter
retarder
rice milling
riprap weather resistant; free from defects that
cause spalling and splitting
2U
rock dusting (mines) 100% should pass a 20-mesh sieve and <5 % combustible matter; < 5 % free
70 % should pass a 200-mesh sieve; and combined silica
should not cake if wetted and dried
rock or mineral wool size of stone used varies with plant 4 5 4 6 % CaC03 or CaC03 + MgCO3
operation but 2-5 inches is common
roofing granules
sewage and trade-waste treatment 3.5-2.5 or 3.5-1.5 inch sizes are used; rough high-calcium limestone
surface should withstand 20 cycles of the
Na2S04 soundness test; minimum of fines
silica brick manufacture high-calcium limestone
silicones
soap free of deleterious substances high-calcium limestone
soil and structure stabilization highcalcium hydrated lime
stone chips uniform, attractive colour;
hard, durable, and tough;
low absorption; free from dust; ability to
take a polish; size used varies
stucco
studio snow finely pulverized; light colour
sugar refining (cane and beet) size varies with plant operation; stone should high purity, >9697% CaC03, < I % SiO2,
retain shape during burning < 1 4 % MgO, <0.5% iron oxide
sulfuric acid purification
table salt
target sheets
terazzo uniform, attractive colour; hard, durable,
and tough; low absorption; free from dust;
ability to take a polish; size used varies
w
00
w
TABLE XXVII (continued) w
E
Use Physical requirements Chemical requirements

textiles high-calcium limestone with < 3 %MgO,

+
(2 % Fez03 AlzOa, < 2.5 % sioz +
insoluble residues
tobacco
varnish manufacture high-calcium limestone, low in Mg and Fe
whiting should pass a 200-mesh sieve; no grit; specifications vary with user
specifications vary with user
wire drawing
wood pullers
wood distillation
PROPERTIES AND USES OF THE CARBONATES 385

TABLE XXVIII

USES IN WHICH AND FOR WHICH WHITING (MANUFACTURED AND ARTIFICIALLY PREPARED) IS USED

(After LAMAR,1961; supplemented by data from BOWLES

and JENSEN, 1947; KEY,1960; and JOHN-
STONE and JOHNSTONE,1961)

acoustic tile locomotive works

antibiotics magazine and book papers
asbestos products filler making buff brick from
asphalt red-burning clay
calcimine and cold water paints manufacture of citric acid
caulking compounds medicines (pharmaceutical products)
ceramic glazes, enamels, and bodies metal polish
chemical manufacture neutralizing in fermentation processes
chewing gum oil cloth
cigarette papers oil paints
coating on glazed paper paints
confectionery paper
cosmetics parting compounds
crayons petroleum refining
disinfectants phonograph records
dolls picture frame moldings
dressing for white shoes plastics
dusting and polishing agents pottery
dusting unburned brick to prevent printing ink
sticking to kiln printing and engraving
dusting printing rollers Putty
dyes roofing cement
explosives rubber
fabric filler rubber goods (footwear, heels, hard
facing for molds and cores in rubber objects, white rubber stock,
brass casting molded rubber goods, sponge rubber,
file manufacture hose, belts, mats and electric
fireworks cable insulation)
flat wall paint and enamel undercoats sealing wax
flavoring extracts ship building
floor coverings shoe manufacturing
food shoe polishes
foundry compounds soap
fungicides structural iron making
glue toiletries
graphite filler toothpaste (dentifrices)
grease welding electrode coatings
gypsum plaster white ink
insecticides whitewash
leather goods window shades
linoleum wire insulation
linseed oil putty
 F. R. SIEGEL

TABLE XXIX

USES FOR WHICH AND IN WHICH CARBONATE MINERALS (NATUREL AND ARTIFICIALLY PREPARED)
ARE USED

(After DANA,
1959; KRAUSet al., 1959; and STECHER,
1960)

Mineral Uses

calcite As limestone, see Table XXVII; or as whiting, see Table XXVlII; variety
Iceland spar used for the Nicol prism in polarizing microscopes to obtain
plane polarized light; in tooth powders, white polishes, and whitewash
(paint); in removing acidity from wines; as a gastric antacid and for
mild diarrhea; ore of calcium.
dolomite As dolostone, see Table XXVII; ore of metallic magnesium.
magnesite Dead-burned (MgO with less than 1 % COZ) used in the manufacture of
refractory brick linings, furnace hearths, and Sore1 cement; source of
magnesia used for the manufacture of many industrial chemicals; mixed
with asbestos, serves as a fireproof and heat insulating covering for boilers
and steam pipes; calcined magnesite used in flooring, tiling, wainscoting,
and sanitary finishes; in tooth and face powders and in polishing com-
pounds; as a filler for rubber; in the manufacture of mineral waters,
pigments and paper; used to clarify liquids by filtration; as an antacid and
laxative; ore of metallic magnesium.
rhodochrosite Ore of manganese; used in feeds and as a drier for varnishes; as the pig-
ment “manganese white”; has been used in treating anemia.
siderite Ore of iron.
smithsonite Ore of zinc; used polished as a gem or for ornamental purposes; used as a
pigment and in the manufacture of porcelain and pottery; has been used
topically as a mild antiseptic and astringent in inflammatory skin diseases.
aragonite No economically important use except as a gem (pearl).
wi therite Ore of barium; used in the extraction of sugar from sugar beets; as a
drilling mud, as an adulterant in white lead, and as a rat poison; in paints,
enamels, marble substitutes, and in rubber; used in the ceramics, glass
(especially optical glass), vacuum-tube, and paper industries; used for
the preparation of many barium compounds.
strontianite Ore of strontium; used in pyrotechnics and military rockets; in the se-
paration of sugar from molasses; as a lead replacement in certain enamels;
in the manufacture of irridescent glass; used in the preparation of many
strontium compounds.
cerrussite Ore of lead; as a pigment in oil paints and water colors; used in certain
cements and for making putty and lead-carbonate paper.
malachite Ore of copper; as jewelry and for ornamental purposes such as vases and
veneer for table tops.
azurite Ore of copper.
trona Ore of sodium; used in the manufacture of glass, pulp and paper, and in
the preparation of sodium compounds; used for water treatment and in
the production of nonferrous metals, cleaners, soap, textiles, and dyes.
PROPERTIES AND USES OF THE CARBONATES 387

moving upward. The effect of some technological advances have not been felt
yet to any great degree in the United States. Development of the oxygen process
for making steel is most encouraging to the carbonate rock and lime producer,
because in this process about twelve times more lime is used per day than in the
conventional steel production processes. Although European and Japanese steel
manufacturers produce large quantities of their steel by the oxygen process (Japan
produces about 38 % this way as compared to 10% in the United States), the major
steel producers in the United States have been somewhat conservative and slow
to convert to this speedy and more efficient technique. Because of domestic and
foreign competition and lower prices, however, established companies such as
U. S. Steel have been stimulated into constructing oxygen furnaces in an effort to
maintain traditional markets and to establish new ones.
In other fields, research is leading to new uses for the carbonates. The
Texas Crushed Stone Company of Austin, Texas, is experimenting with crushed
limestone base in livestock areas on farms in an effort to prevent livestock bogging
(KENNERLY, 1963). This company is also interested in other applications on farms
and may experiment: ( I ) with limestone floors in poultry houses; (2) with crushed
limestone as a base for self-feeding hay to cattle from stacks in pastures; and (3)
with its potentially most important use as a base for the hundreds of beef-cattle
feeding lots, currently appearing in many of beef-producing states in U.S.A. HEDIN
(1963), head of the Chemical Department of the Swedish Cement and Concrete
Institute, Stockholm, Sweden, pointed out that lime consumption can be increased
if the lime is manufactured for specific uses by selecting starting carbonate rock
of known chemical composition and crystal size, and then controlling the burning
process. FALKE (1963) described a new method for recovering manganese from
manganiferous limestones and slimes, and found that 50-75 % of the total man-
ganese in manganiferous limestones can be recovered as manganese carbonate
containing 45 % manganese. Considering that only about 3 % of the manganese used
in the United States is of domestic origin this advance is extremely important.
Although one may review Tables XXVII-XXIX, trends in production,
technological advances or product development, and fully appreciate the impor-
tance of carbonate rocks to the development and advancement of our civilization,
limestones and dolomites serve other purposes in which they are not actually “used”
but for which they are esteemed or have actual economic meaning. For example,
caverns and unique speleothem formations that have formed in them (Fig.4)
serve as a constant source of education and wonder to those visiting them. In
the United States, thousands of visitors each year take guided tours through the
Carlsbad Caverns, New Mexico, and the many caves of the Mammoth Cave
National Park, Kentucky. The actual dollar ‘value represented by payment for
these tours is difficult to assess, but it no doubt exceeds that derived from many of
the products listed in the tables of uses (Tables XXVII-XXIX). Similar exhibitions
of natural beauty are found in the coral reefs of the Pacific and off the east coast of
388 F. R. SIEGEL

Fig.4. Speleothem formations (stalactites, stalagmites, straws, and flowstone) in the Great
Onyx Cave, Mammoth Cave National Park, Kentucky.

the Florida Keys and the Bahamas; and the number of people who visit these
features each year represents a good portion of the tourist trade. Unfortunately,
in areas where conservation is not practiced or dictated by law, these non-replacea-
ble features (stalactites, stalagmites, or flowstone) or coral specimens are sold at
local souvenir stands for ornamental purposes.
In several areas where underground quarries have been worked out or where
caves are present, the land owner can make substantial profit by renting the empty
space for storage. Because of the low (and constant) temperature and humidity
of these underground facilities, they are ideal for raising mushrooms, and for the
storage of records, frozen foods, medicinals, bonded whiskey, military equipment,
and other products. The U. S. Government has set up specificationsfor theseunder-
ground areas, which if they are followed,can lead to the eventual rental of the stor-
age facilities to the government at favorable fees. STEARN(1963) has summarized
these for mined-out limestone caves (or quarries) to be used as storage areas of
high security and unrivalled material preservation: (I) the minimum size should be
at least 200,000 sq. ft. and there should be a geometrical pillar arrangement,
spaced at least 30 ft. apart, and a minimum ceiling height of 14 ft.; (2) only drift-
type entryways are allowed and the exits and entrances must be serviced by paved
roadways; (3) proximity to a railroad spur is desirable; (4) there must be at least
PROPERTIES AND USES OF THE CARBONATES 389

50 ft. of overburden; ( 5 ) a 4-h fire rating is necessary for the installed doors and
reinforced concrete walls separating the different areas, and there should be a
complete automatic sprinkler system throughout the facility; and (6) proper
equipment for temperature maintenance (between 55 and 70 O F ) and for relative
humidity maintenance (30-50 %) must be installed. It is most probable that in the
future, such rigidly constructed underground areas will house power plants or
nuclear reactors.
The magnitude of the importance of carbonate rock to man can be further
emphasized by the previously cited fact that more than one-half of the known
petroleum and natural gas reserves are in carbonates, as well as a great percentage
of our past and existing metalliferous reserves. Also, that precious commodity
water comes from limestone aquifers in many parts of the world, and porous and
permeable carbonate rock units have been developed for storage of natural gas and
liquefied petroleum products. On adding to this the secrets of the earth’s history that
have been, are being, and will be revealed by detailed, systematic studies of the car-
bonate rocks and their fossils and other than carbonate mineral content, one may see
that “use” although considered mainly from an economic aspect, can be extended
to include academic studies which can and many times do lead to economic devel-
opment and successful exploitation.

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PROPERTIES A N D USES OF THE CARBONATES 393

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REFERENCES INDEX

ABELSON, P. H., 9, 72, 102, 136 K. G., 136

ABELSON, P. H. and HOERING, T. C., 199, 206BARGHOORN, E. S., MEINSHEIN, W. G. and
ADAMS, E. and NICHOLSON, J., 212, 220 SCHOPF, J: W., 136
ADAMS, J. E. and RHODES, M. L., 136 BARLETT, H. H., 230
ADAMS,L. H., 178, 189 BARNES, I., 137
ADLER,H. H., 373, 389 BARNES, I. and BLACK,W., 179, 182, 190
ADLER,H. H. and KERR,P. F., 372, 374, 375, BARNES, J. W., LANG,E. J. and POTRATZ, H. A..
389 84, 137
ALDERMAN, A. R.,27, 136 BARNES, V. E., 326, 330, 365, 390
ALDERMAN, A. R. and SKINNER, H. C. W., 55,BARON,G. and FAVRE,J., 5,20
136, 177, 183, 186, 189 BARON,G., CAILL~RE, S., LAGRANGE, R. and
ALDERMAN, A. R. and VONDER BORCH,C. C., POBEGUIN, TH., 320, 321, 330
87, 116, 117, 136, 177, 189 BARTH,T., 213, 220
ALEKIN, 0. A., 3, 20 BASS,N. W., 242, 249
ALEXANDER, L. E. and KLUG,P. H., 325, 330 BATHURST, R. G. C., 151, 166,211, 220
ANGINO,E. E., 9, 327, 330, 372, 389 BAXTER, J. W., 137
ANGINO,E. E. and GR ~ GL EN., R , 372,389 BAYLISS, P., 316, 330
ANGINO,E. E. and SIEGEL, F. R.,325, 330 BAYLISS,P. and WARNE,S., 316,330
ANGINO,E. E., ARMTAGE, K. B. and TASH,J. C., BEALES, F. W., 273, 330
86, 136 BECK,C. W., 316, 318, 322, 330
ANONYMOUS, 346, 347, 378, 389 BELL,K. G., 29, 91, 137
ARABIAN-AMERICAN OIL Co. STAFF,235, 236, BELL,P. M., ENGLAND, J. L. and SIMMONS,
249 M. G., 137
ARPER,W. B., 136 BENDORAITIS, J. G., BROWN,B. L. and HEPNER,
ARRHENIUS, G., KJELLBERG, G. and LIBBY, L. S., 227, 249
W. F., 330 BERG,L. G., 330
A. S. T. M., 351, 352, 353, 389 BERGER, R.,HORNEY, A. G. and LIBBY,W. F.,
ATCHISON, T. C., DUVALL, W. I. and PETKOF, 328, 330
B., 363, 389 BERGER, W., 72, 137
ATWATER, G. I., 2, 20 BERGMANN, W., 228, 249
AUDLEY-CHARLES, M. G., 136 BERGSTROM, R. E., 326, 330, 372, 390
AZAROFF, L. V. and BUERGER, M. J., 324, 331BERNER, R. A., 137
BERRY,L. G. and MASON,B., 279,330
BAAS-BECKING, A. V. and GALLIHER, G., 136 BEVELANDER, G., 329,330
BAERTSCHI, P., 195,197,198,200,204,206 BIRCH,F., SCHAIRER, J. F. and SPICER,H. C.,
BAEKTSCHI, P. and SILVERMAN, S. R.,199, 206 351, 354, 355, 356, 357, 358, 359, 360, 390
BAKER, D. R., 241, 242, 249 BISQUE,R. E., 330
BAKER, E. G., 233, 249 BISQUE,R. E. and LEMISH, J., 278,297,304,330
BAKER, N. E. and HANSON, F. R. S., 236, 249 BISSELL,H. J., 272, 273, 274, 330
BALL,S. M. and BECK,A. W., 365, 390 BISSELL, H. J. and CkILINGAR, G. V., 104, 137
BALLIE,A. D., 235, 249 BITTERLI, P., 137, 235, 249
BANKS,J. E., 288, 330 BLAIR,B. E., 351, 390
BANNER, F. T. and WOOD,G. V., 102, 136 BLACK,W., 181, 189
BAR, O., 184, 185, 190 BLACK,W. A. P. and MITCHELL, R.L., 53, 137
BARANOV, V. I., RONOV, A. B. and KUNASHOVA, BLACKMON, P. D. and TODD,R., 49,60,75,137
396 REFERENCES INDEX

BLOSS,F. D., 280, 330 CHILINGAR, G. V., 1, 5, 6, 10, 12, 20, 59, 77,
BLUMER, M. and OMAN,G. S., 228,249 78, 102, 103, 105, 110, 113, 134, 135, 138,
BLUMER, M. and THOMAS, D. W., 228, 249 153, 166
BLUMER, M., MULLIN,M. M. and THOMAS, CHILINGAR, G. V. and BISSELL, H. J., 20, 85,
D. W., 228,249 99, 138, 153, 166
BODINE JR., M. W. and HOLLAND, H. D., 370, CHILINGAR, G. V. and TERRY, R. D., 110, 138,
390 305, 331
BODUNOV-SKVORIXOV, E. I., 237, 249 CHILINGAR, G. V., BISSELL, H. J. and WOLF,
BOUMA, A. H., 288, 330 K. H., 28, 89, 99, 138, 255, 287, 331
BOWEN,H. J. M., 65, 137, 199, 206 CLARKE, F. W., 361, 364, 365, 390
BOWEN,N., 217, 220 CLAYTON, R. N., 195, 198, 200, 204, 205, 206,
BOWENJR., 0. E., 378, 390 331
BOWEN,R., 199, 206 CLAYTON, R. N. and DEGENS, E. T., 111, 138,
BOWLES, O., 373, 378, 390 195, 197, 200, 206, 329, 331
BOWLS, 0. and JENSEN,N. C., 373, 378, 385, CLAYTON, R. N. and EPSTEIN, S., 15, 193, 199,
390 200, 202, 203, 204, 205, 206, 328, 329, 331
BRADLEY, D. E., 286, 287, 330 CLOUDJR., P. E., 74, 95, 115, 138, 151, 166
BRADLEY, W. F., BURST,J. F. and GRAF,D. L., CLOWES, F. and COLEMAN, J. B., 296, 331
137, 330 COLBY,S. F., 373, 378, 390
BRAY,E. E. and EVANS,E. D., 243, 249 COMPSTON, W., 194,195,199,202,206,329,331
BRENDA, B. J. and BRUNFELT, A. O., 137 COMSTOCK, H. B., 376, 390
BRILL,O., 318, 331 CORDIER, P., 220, 222
BRINDLEY, G. W., 324, 331 CORLESS, J. T., 206
BROD,I. O., 237, 249 CORLESS,J. T., RAHN,K. A., and WINCHESTER,
BROECKER, W. S., 49, 84, 137, 328, 331 J. W., 206
BROECKER, W. S. and ORR,P. C., 74, 137,231 CRAIG,H.,14,193,194,195,196,197,198,206,
BROOKS, D. B., 137 328, 329, 331
BROOKS, J. E. and CLARK,D. L., 372, 390 CRICKMAY, G. W., 20
BROOKS, R. R. and RUMBSBY, M. G., 137 CROW,S. C., 360, 390
BROVKOV, G. N., 87, 106, 128, 129, 130, 137 CURL,R. L., 138
BROWN,G., 324, 331 CUTHBERT, F. L. and ROWLAND, R. A., 320,
BROWN,W. W., 211,220 331
BUEHLER, E. J., 273; 331 CUVILLIER, J., 287, 288, 331
BURGER, D., 282, 331
BURNHAM, G., 217, 220 D’ALBISSIN, M., 214, 215, 216, 220
D’ALBISSIN, M. and DE RANGO,C., 286, 332
CAILL~RE, S., 317, 323, 331 DALBISSIN,M. and ROBERT,M., 214, 220
CAILL~RE, S. and POBEGWIN, TH., 323, 331 DALEISSIN,M., FORNACA-RINALDI, G. and
CALLEGARI, E., 217,220 TONGIORGT, E., 220, 372, 390
CALVERT, S. E. and VEEVERS, J. J., 289, 331 DALEISSIN, M., SAPLEVITCH, A. and SAUCIER,
CAMPBELL, F. A. and LERBEKMO, J. F., 137 H., 214, 220
CAPDECOMME, L. and P m u , R., 323, 331 DANA,J. D., 349, 386, 390
CAROZZI, A. V., 151, 166, 286, 331 DANIELS, F., 326, 332
CARROLL, J. J. and GREENFIELD, L. J., 61, 74, DANIELS, F., BOYD,C. A. and SAUNDERS, D. F..
137 326. 332, 371, 390
GANG, L. L., 137, 371, 390 DANIELSON, A., 217, 220
GAVE, K. E., 8, 26, 55, 59, 60, 61, 77, 78, 79, DANSGAARD, W., 199, 200,207
83,84,103, 134,137,181, 186,190,325,331, DAUGHTRY, A. C., PERRY,D. and WILLIAMS,
366,390 M., 15, 206, 207, 328, 329, 332
CHAVE,K. E., DEFFEYES, K. S., WEYL,P. K., DAVIES,T. T. and HOOPER,P. R., 325, 332
GARRELS, R. M. and THOMPSON, M. E., 138, DEAN,J. A., 310, 332
390 DEBENEDETIT, A., 215, 220
CHAYKOVSKAYA, E. V., 234, 249 DEBOO,P. B., 152, 160
CHENG, K. L., KURTZ,T. and BRAY,R. H., 299, DEER,W. A., HOWIE,R. A. and ZUSSMAN, J.,
308, 331 8, 27, 138, 279, 281, 332, 349, 350, 352, 390
CHIBNALL, A. C. and PIPER,S. H., 227,243,249 DEFFEYES, K. S. and MARTIN,E. L., 332
REFERENCES INDEX 397

DEFFEYES, K. S., LUCIA,F. J. and WEYL,P. K., ERENBURG, B. G., 152, 166
177, 190 ERICSON, D. B. and WOLLIN,G., 333
DEGENS,E.T., 111,114,116,138,240,241,329, EVAMY, B. D., 259, 261, 262,271, 333
332 EVANS,R. C., 139
DEGENS, E. T. and EPSTEIN, S., 15, 194, 195, EVANS,W. D., 58, 71, 139
198, 200, 201, 202, 203, 204, 207, 279, 329,
332 FAIRBANKS, E. E., 260, 333
DEGENS, E. T., HUNT,J. M., REUTER, J. H. and FAIRBRIDGE, R. W., 9, 11, 12, 20, 99, 133, 134,
REED,W. E., 138 139, 287,288, 327, 333
DEGENS, E. T., PIERCE, W. D. and CHILINGAR, FALKE,W. L., 387, 390
G. V., 90, 138 FANALE, E. P. and SCHAEFFER, 0. A., 328, 333
DEGENS, E. T., WILLIAMS, E. G. and KEITH, FAUST,G. T., 318, 321, 323, 333
M. L., 28, 138, 332 FEIGL, F., 263, 267, 268, 269, 289, 333
DE VRIES,H., 332 FLASCKA, H., 300, 333
DIAMOND, J. J., 310, 332 FLUGEL, E. and FLUGEL-KAHLER, E., 111, 112,
DIEBOLD, F. E., LEMISH, J. and HILTROP, C. L., 114, 139, 289, 329, 333
325, 332 FOLK,R. L., 100, 114, 139, 289, 333
DODD,J. R., 76, 77, 79, 81, 139 FOLK,R. L. and ROBLES,R., 289, 333
DOLGOV, G. I., 6, 20 FOLK,R. L., HAYES, M. 0. and SHOJI,R., 289,
DUNBAR, C. 0. and RODGERS, J., 96, 139 333
DUNNINGTON, H. V., 236, 249 FORSMA J.~P., and HUNT,J. M., 238,239,249
DUNTON, M. L. and HUNT,J. M., 228, 249 FRETTER, V., 139
DURELLI, A. J. and FENER, L., 360, 390 FRIEDEL,J., 215, 220
DURHAM, J. W., 152, 166 FRIEDMAN, G. M., 139,259,260,262,264,265,
DUVALL, W. I. and ATCHISON, T. C., 362, 390 267, 268, 270,272, 282, 333
FROST,A. V., 231, 249
EASTON, A. J., 294, 303, 332 FUCHTBAUER, H., 139
EASTON, A. J. and GREENLAND, L., 302, 332 FUCHTBAUER, H. and GOLDSCHMIDT, H., 87,
EASTON, A. J. and LOVERING, J. F., 305, 310, 100, 139
332 FUKAI,R. and MEINKE, W. W., 49, 53, 139
EASTON, W. H., 332 FYFE,W.S., 104, 139
ECKEL,E. C., 365, 390 FYFE, W. S. and BISCHOFF, J. L., 139
ECKELMANN, W. R., 198
ECKELMANN, W. R., BROECKER, W. s., WHIT- GABINET, M. P., 321, 333
LOCK,D. W. and ALLSUP,J. R., 194,207 GALLE,0. K., 361, 364, 390
ELLENBERGER, F., 217, 220 GALLE,0. K. and RUNNELS, R. T., 361, 390
ELLING~OE, J. and WILSON,J., 332 GAMKOSIAN, A., JANSSON, A. C. and UMLANDT,
EL WAKEEL, S. K. and RILEY,J. P., 139 R. M., 365, 373, 390
EMERY, K. O., 327, 332 GARLICK, G. D., 195, 198, 200, 204, 207
EMERY, K. 0. and BRAY,E. E., 327, 332 GARLTCK, W.G., 85, 140
EMERY,K. 0. and HOGOAN,D., 228, 249 GARN,P.D., 323, 333
EMILIANI,C., 70, 139, 199, 200, 207, 329, 332 GARN,P. D. and KESSLER, J. E., 323, 333
EMILIANI, C. and EDWARDS, G., 332 GARRELS, R. M., 86, 104, 140
ENGEL,A. E. J. and ENGEL,C. 139 GARRELS, R. M. and DREYER, R. M., 104,140,
ENGEL,A. E. J., CLAYTON, R. N. and EPSTEIN, GARRELS, R. M.,DREYER, R. M. and HOWLAND
S., 15, 198,200, 202,204,205,207, 329, 332 A. L., 140
EPSTEIN,S., 15. 193, 207, 333 GARRELS, R. M., THOMPSON, M. E. and SIEVER,
EPSTEIN, S. and MAYEDA, T., 199, 200, 207 R., 140, 172, 173, 174, 175, 178, 179, 190,
EPSTEIN,S.,BUCHSBAUM, R., LOWENSTAM, H. A. 368, 391
and UREY,H. C., 193, 199, 204, 205, 207, GAULT,H. R. and WELLER, K. A., 333
329, 333 GEDROIZ, K., 278, 333
EPSTEIN, S., GRAF,D. L. and DEGENS, E. T., GEHMAN JR., H. M., 71,140,231,234,240,250
199, 201, 202, 203,207, 333 GERARDE, H. W. and GERARDE, D. F., 227,249
ERDMAN, J. G., M A R L EE. ~ ,M. and HANSON, GERMAN, K., 140
W. E., 228, 249 GIBBS,J. W., 170, 171, 172, 177, 178, 190
EREMENKO, N. A., 20,21 GILBERT, C. M. and TURNER, F. J., 283, 333
398 REFERENCES INDEX

GILLISON, J. L., 351, 366, 373, 391 GRWER,R. M., 318, 320, 334
GINSBURG, R. N., 234,249 GULBRANDSEN, R. A., 365, 391
GLAGOLEVA, M. A., 72, 140 GULYAEVA, L. A.gnd ITKINA, E. S., 28,29,141
GLOVER, E. D., 333
GODWIN,F. R. S., 328, 333 HAAS,C., 214,221
GOGUEL, J., 210, 216, 221 HAGN,H., 288, 334
GOLDBERG, E. D., 52, 72, 73, 88, 91, 105, 140 HAGUI,R. D. and SAADALLAH, A. A., 141
GOLDBERG, E. D. and ARRHENIUS, G. 0. S., HALLA, F., CHILINGAR, G. V. and BISSELL,H. J.,
104,140 175, 178, 184, 185, 190
GOLDICH, S. S., INGAMELLS, C. 0. and THAEM- HAMBLIN, W. K., 289, 330
LITZ, D., 365, 391 HANDIN, J. and HAGAR,R., 210, 221
GOLDMAN, M, 140 HANDIN, J., HIGGS,D., LEWIS,D. and WEYL,
GOLDSCHMIDT, V. M., 29, 105, 140 P., 215, 221, 327, 334, 372, 391
GOLDSCHMIDT, V. M., KREJCI-GRAF, K. and HANZAWA, S., 288, 334
WITTE,H., 29, 140 HARBAUGH, J. W., 151, 166, 273, 334
GOLDSMITH, J. R., 26, 140, 370, 391 HARBAUGH, J. W. and DEMIRMEN, F., 289, 334
GOLDSMITH, J. R. and GRAF, D. L., 366, HARBAKEN, L. and GREDAY, T., 212, 221
370, 391 HARDER, H., 89, 97, 141
GOLDSMITH, J. R. and HEARD, H. C.,391 HARKER, A., 221
GOLDSMITH, J. R. and NORTHROP, D. A., HARKER, R. I., 141
370, 391 HARKER, R. I. and TUTTLE,0.F.,26,141,217,
GOLDSMITH, J. R., GRAF,D. L. and HEARD, 221, 325, 334, 366, 391
H. C.,391 HARRIS,R. C., 141
GOLDSMITH, J. R., GRAF,D. L. and JOENSUU, HARVEY, R. D., 391
0. I., 26, 140, 325, 333 HAUL,R. A. W. and HEYSTEK, H., 318, 335
GOLDSMITH, J. R., GRAF,D. L., WITTERS, J. HAUN,J. D. and LEROY,L. W., 335
and NORTHROP, D. A., 26,140,325,334,391 HAY,W. W. and TOWE,K. M., 286, 335
GOREAU, T. F., 71, 140 HAYES, J. R., 335
GOREAU, T. F. and GOREAU, N. I., 75,140 HEDBERG, H. D., 248, 250
GORLITSKIY, B. A. and KALYAEV, G. I., 130,140 HEDBERG, R. M., 259, 261, 275, 335
GORSKAYA, A. I., 230, 231, 250 HEDGPETH, J. W., 141
GOTO,M., 4, 27, 86, 93, 94, 95, 140, 259, 325, HEDIN,R., 387, 391
334 HEEGER, J. E., 259, 270, 335
GRAF,D. L., 23,27,28,29,49, 50,62, 72, 104, HEEZEN, B. C. and JOHNSON 111, G. L., 272,274,
140, 324, 334, 352, 361, 391 335
GRAF,D. L. and GOLDSMITH, J. R., 13, 152, HEIDE,F. and CHRIST,W., 141
166, 176, 190, 324, 325, 334, 366, 391 HENBEST, L. G., 259, 261, 267, 335
GRAF,D. L. and LAMAR, J. E., 141,366,370, HERZOO, L. F., ALDRICH, L. T., HOLYK, W. K.,
391 WHITING, F. B. and AHRENS, L. H., 328, 335
GRAF,D. L., EARDLEY, A. J. and SHIMP,N. F., HIGGS,D., FRIEDMAN, M. and GEBHART, J.,
177, 190 214, 221
GRASENICK, F. and GEYMEYER, W., 259, 334 HILTROP,C. L. and LEMISH, J., 325, 335
GRAYSON, J. F., 141, 334 HIRST,D. M., 69, 141
GREENFIELD, L. J., 55, 141 HIRST,D. M. and NICHOLLS, G. D., 279, 335
GR~GOIRE, C.,286, 334 HIRT,B. and EPSTEIN, S., 205, 206, 207
GR~GOIRE, C.and MONTY,C., 286, 334 HOBSON, G. D., 233, 250
GRIGGS, D., TURNER, F. and HEARD, H. C., 21 3, HOLLAND, H. D., BODTNE, M. W., BORCSIK, M.,
22 1 COLLINS,P., KIRSIPU,T. V., ROSENBERG,
GRIM,R. E., 276, 278, 334 P. E., SAWKINS, F. J. and TSUSUE, A., 26,88,
GRIMSHAW, R. W.,HEATON, E. and ROBERTS, 141
A. L..323. 334 HOLLAND, H. D., BORCSIK, M. and GOLDMAN,
GROSS,M. G., 141, 329. 334 E., 141
GROVES. A. W. 305, 306, 334 HOLLAND, H. D., KIRSIPU,T. V., HUEBNER,
GRUBENMAN, U., 218, 221, 222 J. S. and OXBOUGH, V. M., 179,181,190,391
GRUNAU,H. R., 286,288, 334 HOLLMANN, R., 234,250
GRUS, H., 282, 334 HOLMES, A., 221, 222
REFERENCES I N D E X 399

HONJO,S., FISCHER, A. G. and GARRISON, R., KAYCHENKOV, S. M., 142

141 KAZAKOV, A. V., TIKHOMIROVA, M. M. and
HOOD,D. W., 72, 141 PLOTNIKOVA, V. I., 172, 173, 114, 176, 190
HOOD,D. W., PARK,K. and SMITH,J. B., 141 KEELING,C. D., 194,207
HOOPER, K., 49, 141, 325, 335 KEITH,M. L., 336
HOWELL, J. E. and DAWSON, K. R., 283, 335 KEITH,M. L. and ANDERSON, G. M., 195,197,
HOWIE,R. A. and BROADHURST, F. M., 325, 201, 328, 329, 336
335 KEITH,M. L. and DEGENS, E. T., 142,336
Hsu, K. J., 141, 179, 181, 182, 183, 185, 190, KEITH,M. L., ANDERSON, G. M. and EICHLER,
327, 335, 392 R., 336
HUANG, C. K. and KERR,P. F., 312, 374, 375, KELLER, W. D., SPOTTS, J. H. and BIGGS,D. L.,
392 372, 392
HUEGL,TH., 335 KENNEDY, G. C., 281, 286, 336
HUGHES, P. W., BRADLEY, W. F. and GLASS, KENNERLY, A. B., 387, 392
H. D., 325, 335 KESSLER, D. W. and SLIGH,W. H., 351, 363,
HUNT,J. M., 229,230,231, 235,239, 240,250 392
HUNT,J. M. and JAMIESON, G. W., 226, 250 KEY,W. W., 385, 392
279, 335 KHALIFEH, Y. and LOUIS,M., 244, 250
HUTCHINSON, G. E., 54, 141 KING,R. J., 142
KINSMAN, D. J. J., 142
ILLING, L. V., 152, 166 KISSINGER, H. E., MCMURDE, H. F. and S ~ P -
ILLING, L. V., WELLS,A. I. and TAYLOR, sow, B. S., 316, 317, 323, 336
J. C. M., 141 KITANO, Y., 58, 95, 96, 142
IMBRIE, J., 141, 289, 335 KITANO,Y. and HOOD,W. H., 158, 166
IMBRIE, J. and PURDY, E. G., 289, 335 KITSON,R. R. and MELLON, M. G., 303, 336
IMBT, W. C., 348, 392 KITEL, C., 371, 392
INGERSON, E., 57,72,74,95,116,141,326,335, KLOTZ,M., 178, 190
366, 392 KNEBEL, G. M. and RODRIQUEZ-ERASO, G.,
IRELAND, H. A., 257, 335 226, 250
ISENBERG, H. D., LAVINE, L. S., WEISFELLNER,KOBLENCZ, V. and NEMECZ, E., 321, 323, 336
H. and SPOTNIZ,A., 141 K o c ~ zF.
, F. and TITZE,H., 142
Ims JR., W., 257, 335 KONISHI,K., 49, 142
KRACEK,F. C., 367, 392
JAMIESON, J. C., 142, 158, 166, 217, 221 KRAMER, J. R., 142, 178, 179, 190
JAMIESON, J. C. and GOLDSMITH, J. R., 142 b u s , E. H., HUNT,W. F. and RAMSDELL,
JEFFERY, P. M., COMPSTON, W., GREENHALGH, L. S., 349, 386, 392
D. and DE LAETER, J., 195, 207, 328, 329, KRAUSKOPF, K. B., 29, 50, 86, 100, 104, 122,
335 142
JODREY, L. H., 142, 329, 335 KREJCI-GRAF,K., 230,250
JOHNSON, N. M., 255, 272, 326, 335 KREJCI-GRAF, K. and WICKMAN, F. E., 194,207
JOHNSTON, J. H., 335 KRINSLEY, D., 101, 107, 108, 109, 142
JOHNSTON, J., MERWIN,H. E. and WILLIAMSON,KRINSLEY, D. and BIERI,R., 49, 142
E. D., 96, 142 KRUGER, P., 142, 143
JOHNSTONE, S. J. and JOHNSTONE, M. G., 360, KUBLER,B.,82, 87, 114, 115, 116, 143, 336
364, 373, 378, 385, 392 KUDYMOV, B. Y.,85, 122, 128, 143, 289, 336
JONES, B. F., 177, 183, 190 KULP,J. L., 316, 328,336
JUNG,J., 221, 222 KULP,J. L., KENT,P. and KERR,P. F., 322,336
JURG,J. W. and EISMA, E., 250 KULP,J. L., TUREKIAN, K. K. and BOYD,D. W.,
JURIK,P., 336 62, 64, 65, 66, 69, 70, 78, 79, 80, 102, 108,
115, 143, 328, 336
KAHLE,C. F., 142 KULP,J. L., WRIGHT,H. D. and HOLMES,R. J.,
KALLE,K., 53, 142 322, 336
KAMB,W., 213, 221 KUZNETSOV, S. I., 74, 143
KANSAS BUILDINGSTONE ASSOCIATION, 352, KUZNETSOV, S. I., IVANOV, M. V. and LYALI-
392 KOVA, N. M., 6, 20, 143
KAUFFMAN, A. J. and DILLING,E. E., 320,336 KVENVOLDEN, K. A., 143
400 REFERENCES INDEX

LADD, H. S., 143 MACDIMID, R. A., 326,337,372,392

LAFFITE, P., 212, 217, 221 MACDONALD, G., 213, 221
LALOU,C., 74, 143 MACDONALD, G. J. F., 158, 166, 177, 190
LAMAR,J. E., 257,258, 273, 336, 365, 373,376, MACHATSCHKI, F., 144
378,385, 392 MACKENZIE, R. C., 323, 337
LAMAR,J. E. and SHRODE,R. S., 27, 143 MAGDEFRAU, F., 144
LAMAR,J. E. and THOMPSON, K.B., 25,143,336 MALAN,S. P., 85, 91, 144
LANDERGREN, S., 194,207 MAWUGA, D. P., 53, 144
LANDERGREN, S. and MANHEIM, F. T., 81, 90, MAIR,B. J. and MARTINEZ-PICO, J. L., 227,250
143 MAMET, B., 210, 221, 222
LANE,D. W., 273, 336 MANHEIM, F. T., 144
LANE,N. G., 336 MANN,V. I., 266, 337
LANGE,N. A., 349,377, 392 MANSON, V. and IMBRIE,J., 337
LANGMUIR, D., 143, 189, 190 MARINOS,G. and PETRASCHEK, W., 217, 221
LARSEN,E. S. and BERMAN, H., 350, 392 MASON,B., 52, 54, 105, 144
LARSEN,G. and CHILINGAR, G. V., 20 MAXWELL, W. G. H., JELL,J. S. and MCKEL-
LEAVASTU, T. and THOMPSON, T. G., 53, 143 LAR, R. G., 83, 84, 113, 144, 337
LEE,P. J., 275, 336 MCAULIFFE, C., 233, 250
LEES, A., 336 MCCREA,J. M., 199, 207, 279, 337
LEHNINGER, A. L., 73, 143 MCCRONE, A. W., 272, 273, 337
LEITMEIER, H. and FEIGL, F., 259,263,265,336 MCIVER,R. D., 279, 337
LEMBERG, J., 260, 262, 263, 336 MCKELVEY, V. E., SWANSON, R. W. and SHEL-
LEMISH,J., 278, 341 DON, R. P., 365. 392
LE RIcm, H. H., 143 MEDLIN,W. L., 97, 144
LERMAN, A., 143 MEINSCHEIN, W. G., 228, 250
LEUTWEIN, F., 81, 143 MENNING, J. J. and VITTIMBERGA, P., 288, 337
LEWIS,D. R., 326, 336, 372, 392 MEYER,R. and TAYLOR, D. W., 337
LEWIS,D. R., WEYL,P. K., HANDIN, J. W. and MICHEL,R., 221
HIGGS. D. V., 336 MIGDISOV, A. A., 127, 144
LEWIS,G. N. and RANDALL, M., 178, 190 MILLER,J. B., EDWARDS, K. L., WOLCOTT,
LIBBY, w. F., 327, 328, 337 P. P., ANISGARD, H. W., MARTIN,R. and
LILEY,P. E., TOULOUKIAN, V. S. and GAMBILL, ANDEREGG, H., 236, 250
W. R., 368, 392 MOORE,L. E., 326, 337
LWNS, R. C., BERGY, E. G. and POSNER, A. S., MONAGHAN, P. H. and LYTLE,M. L., 96, 97,
69,75, 143 144
LINDBLOOM, G. P. and LUPTON, M. D., 229,250 MOORHOUSE, W. W., 279, 337, 350, 392
LIPPMANN,N. F., 318, 337 MULLER,G., 337
LLOYD,R. M., 276, 329, 337 MULLER,W., 144
LOGVINENKO, N. V. and KOSMACHEV, V. G., MUNNICH,K. O., 197, 207
27, 106, 143 MUNNICH,K. 0. and VOGEL,J. C., 194, 195,
LOGVINENKO, N. V., KARPOVA,G. V. and 196, 207, 337
KOSMACHEV, V. G., 286, 337 MURRAY,J. A., FISHER,H. C. and SHADE,
LONG,G., NEGLIA,S. and FAVRETTO, L., 71, R. W., 321, 337
143 MURRAY, J. W., 92, 96, 144
LONGINELLI, A. and TONGIORGI, E., 329, 337 MURRAY, R. C., 151, 166
LOUGWN,G. F., 365, 392 Muzn, E. 0. and SKINNER, H. C. W., 144
MUPEKINE, I. S., 280, 337
Low, J. W., 337 NAGY,B., 9, 20
LOWENSTAM, H. A., 55, 56, 57, 58, 60, 66, 75, NATIONAL BUREAUof STANDARDS, 314, 337,
76, 78, 79, 81, 100, 105, 109, 114, 143, 153, 364, 365, 392
166, 329, 337 NAYUDU, Y. R., 337
LOWENSTAM, H. A. and EPSTEIN,A., 14, 198, NEHER,J. and ROHRER, E., 74, 144
199,200, 202, 207, 329, 337 NERUCHEV, S. G., 242, 245, 246, 250
LUCAS,G., 221, 222 NEWELL,N. D. and RIGBY,J. K., 61, 144
LUCIA,F. J., WEYL,P. K. and DEFFEYES,K. S., NICHOLLS,G. D. O., CIIRL,H. and BOWEN,
152, 166 V. T., 53, 144
REFERENCES INDEX 40 1

NODDACK, I. and NODDACK,

W., 53, 144 RAY,S., GAULT,H. R. and DODD,C. G., 276,
NOLL,W., 102, 144 277, 278, 338
NORTH,F. J., 292. 338 REVELLE, R. and FAIRBRIDGE, R., 23, 62, 145,
338
OAKWOOD, T.S., SHRIVER, D. S., FALL,H. H., REY,M. and NOUET,G., 288, 338
MCALEER, W. J. and WLJNZ,P. R., 227,250 REYNOLDS, R. C., 145
OBERT,L., WINDES,S. L. and DUVALL, W. I., RICE,T. R., 145
351, 392 RIEKE111, H. H., CHILINGAR, G. V. and Ro-
OBORN,E. T., 144 BERTSON JR., J. o., 2, 20
OCKERMAN, J. B. and DANIELS,F., 326, 338 RIEKE,J. K., 326, 338
ODUM,H. T., 62, 64, 66, 67, 68, 78, 81, 82, 87, RILEY,J. P. and WILLIAMS, H. P., 289, 305,338
88, 89, 101, 102, 108, 109, 113, 114, 144 RIOULT,M. and RIBY,R., 289, 338
O’NEILL,J. R. and CLAYTON, R. N., 204,205, RITCHIE,A. S., 104, 145, 279, 341
207 RIVIERE,A., 176, 190
OPPENHEIMER, C. H., 72, 74, 144 RIVI~RE, A. and VERNHET, S., 145
OPPENHEIMER, C. H. and MASTER, I. M., 176, ROACH,C. H., JOHNSON, G. R., MCGRATH,
187, 190 J. G. and SPENCE, F. H., 393
ORME,G. and BROWN,W., 211, 221 ROBBINS, C. R. and KELLER,W. E., 276, 338
~ S T L U N D ,H. G., BOWMAN, A. L. and RUSNAK, RODGERS, J., 260, 264, 338
G. A., 327, 338 RONCA,L. B., 312, 393
OSTROM, M. E., 50, 90, 144, 277, 338 RONOV~ A. B., 10, 11, 20, 134, 135, 145, 238,
OWEN,E. W. 235,250 250 ..
OXBURGH, V. M., SEGNIT, R. E. and HOLLAND, RONOV,A. B. and ERMISHKINA, A. I., 118, 120,
H. D., 88, 144 121, 122, 123, 124, 145,
RONOV,A. B. and KORZINA, G. A., 24, 125,
PANTIN,H. M., 144 126, 133, 145
PAPILHAU, J., 317, 323, 338 ROSENBERG, P. E., 26, 145, 325, 338, 370, 393
PARKSJR., J. M., 326, 338, 372, 392 ROSENBERG, P. E. and HOLLAND, H. D., 180,
PATTON, J. and REEDER, W., 306, 338 181, 187, 190, 370, 393
PEARN,W. C., 372, 393 Ross, C. A., 265, 338
PERCIVAL, S. F., GLOVER,E. D. and GIBSON, Ross, C. A. and OANA,S., 329, 338
L. B., 258, 338 ROSTOKER, D. and CORNISH, R., 338
PERRY,R. H., CHILTON,C. H. and KIRK- ROWLAND, R. A. and JONES, E. C., 317,338
PATRICK, J. D., 367, 393 ROWLAND, R. A. and LEWIS,D. R., 318, 339
PETERSON, M. N. A., 278, 338 RUBEY, W. W., 134, 145
PETERSON, M. N. A., BIEN,G. S. and BERNER, RUBIN,M., LIKINS,R. C. and BERRY,E. G.,
R. A., 144 328, 339
PFLUG,H. D., 145 RUCKER, J. and VALENTINE, J. W., 81, 92, 145
PHEMISTER, J. and MACGREGOR, A., 217, 221 RUDDIGER, G., 145
PHILPPI,G. T., 226, 239, 243, 250 RUKHIN,L. B., 3, 20
PILKEY,0. H., 103, 145 RUNNELS, R. T. and DUBINS,I. M., 145
PILKEY,0. H. and GOODELL, H. G., 49,79,80, RUNNELS, R. T. and SCHLEICHER, J. A., 50,145
82, 108, 115 RUOTSALA, A. P., 339
PILKEY,0. H. and HOWER,J., 49, 77, 78, 79, RUSSELL, R. J., 152, 166
80, 145
PITRAT,C. W., 326, 338, 393 SABINS, F. F., 259, 339
POWELL, H. E. and MILLER,C. K., 369, 393 SACAL,V., 288, 339
PRATT,W. E., 226, 250 SACKETT, W. M., 145
PRAY,L. C. and MURRAY, R. C., 6, 20, 145 SAID,R., 49, 145
PYTKOWICZ, R. M., 145, 195, 207 SANDER, R., 211, 213, 214, 221
SANDER, B. and SACHS,G., 214, 221
RAMSDEN, R. M., 259, 338 SANDERS JR., J. W. and CRICKMAY, G. W., 4,
RANKAMA, K., 327, 328, 336 20
RANKAMA, K. and SAHAMA, T. G., 50, 86, 145 SASS,E., 145
RAO,M. S. and YOGANARASIMHAN, S. R., 145 SAUNDERS, D. F., 326, 339. 372, 393
RAQUIN.E., 217, 221 SCHARRER, K., 145
402 REFERENCES I N D E X

SCHLOEMER, H., 172,173, 190 SVERDRUP, H. U., JOHNSON, M. W. and FLE-

SCHMALZ, R. F., 152, 166 MING, R. H., 2, 3, 20, 88, 147, 180, 186, 190
SCHMIDT, V., 146 SWAN,E. F., 68, 147
SCHMIDT, W., 213,221 SWETT,K., 147
SCHOFIELD, A. and HASKIN,L., 49, 146
SCHOLL, D. W., 146 TAFT,W. H., 95, 147
SCHUBERT, J., 73, 146 TAFT,W. H. and HARBAUGH, J. W., 4, 20, 74,
SCHUMANN, H., 282,283,339 87, 95, 101, 115, 147, 151, 153, 158, 167,
SCHWARTZ, F., 267, 339 325, 327, 329, 339
SCHWOB, Y.,317, 321, 323, 339 TASCH,P., 98, 147
SEIBOLD, E., 87, 146 TATSUMOTO, M. and GOLDBERG, E. D., 49, 71,
SHARMA, G. D., 146 84, 91, 147, 328, 339
SHEARMAN, D. J., KHOURI,J. and TAHA,S., TAYLOR JR., H. P. and EPSTEIN,S., 199, 200,
96, 146 205, 207
SHOJI,R. and FOLK,R. L., 27,28,146,287,339 TAYLOR JR., H. P., FRECHEN, J. and DEGENS,
SHORT,N. M., 254, 339 E. T., 195, 198, 204, 205, 207
SHINN,E. A. and GINSBURG, R. N., 152, 166 TAYLOR, J. H., 147
SIEGEL, F. R., 12, 20, 49, 65, 73, 96, 100, 103, TEICHERT, C., 147
108, 112, 146, 153, 167, 326, 339, 372, 393 TEICHM~LLER, M., KALIFEH, Y.and LOUIS,M.,
SILVERMAN, S. R., 198, 199, 207, 229, 250 211,222
SILVERMAN, S. R. and EPSTEIN,S., 194, 207 TENNANT, C. B. and BERGER, R. W., 324,339
SIMKISS, K., 58, 95, 146 TEODOROVICH, G. I., 11, 131, 147
SIPPEL,R. F. and GLOVER, E. D., 146 TEODOROVICH, G. I., SOKOLOVA, N. N.,
SKINNER, H. C. W., 87, 89, 110, 116, 146, 177, ROSSONOVA, E. D. and BAGDASSAROVA,
190, 325, 339 M. V., 96, 147
SKINNER, H. C. W., SKINNER, B. J. and RUBIN, TERRY,R. D. and CHILINGAR, G. V., 256, 339
M., 339 THODE, H. G., WANLESS, R. K. and WALLOUCH,
SLOSS, L. L., 339 R., 195, 207
SLOSS,L. L. and COOKE,S. R. B., 289, 339 THOMPSON, T. G. and CHOW,T. J., 62,67, 147
SMITH JR., P. V., 228, 250 THUGETT, ST. J., 262, 263, 339
SMOLIN, P. P., 220, 221 THURBER, D., BROECKER, W. and KAUFMAN,
SMYKATZ-KLOSS, W.,316,317,320,321,322,339 A., 328, 339
SOKOLOV, V. A., 228,250 TIKHOMIROVA, E. S., 124, 147
SPEARS, D. A., 146 TILLEY,C., 217, 222
SPOONER, G. M., 146 TISCHENDORF, G. and UNGETHUM, H., 147
SPOITS,J. H., 100, 146 TOURTELOT, H. A., 366, 393
STAUFFER, K. W., 288, 339 TREIBS,A., 227, 250
STEARN, G. W., 388, 393 TREFETHEN, J. M., 363, 393
STECHER, P. G., 377, 386, 393 TR~ER W., E., 281, 340
STEHLI,F. G., 202, 207 TUREKIAN, K. K., 79, 80, 108, 114, 147
STEHLI,F. G. and HOWER,J., 83, 87, 101, 146, TUREKIAN, K. K. and ARMSTRONG, R. L., 49,
151, 167 61, 71, 104, 106, 107, 108, 147
STENZEL, H. H., 58, 146 TUREKIAN, K. K. and KULP,J. L., 148
STERNBERG, E. T., FISHER, A. G. and HOLLAND, TUREKIAN, K. K. and WEDEPOHL, K. H., 148
H. D., 111, 146 TURNER, F. and VERHOOGEN, J., 222
STERNBERG, R. M. and BELDING,H. F., 339 TURNER, F. and WEISS,L., 211, 212, 213, 222
STEVENS, R. E. and CARRON,M. K., 339
STOWELL, F. R., 393 UREY,H. C., 199, 207
STRAKHOV, N. M., 146,260,261,262,263,264, UREY,H. C., LOWENSTAM, H. A., EPSTEIN,S.
265, 266, 270, 279, 339 and MCKINNEY, C. R., 195, 198,207, 340
STRAKHOV, N. M., ZALMANZON, E. S. and USDOWSKI, H. E., 87, 91, 96, 97, 98, 101, 102,
GLAGOLEVA, M. A., 118, 119, 120, 121, 147 148, 281, 340
STRIJVE, S., 216, 221 USPENSKIY, V. A. and CHERNYSHEVA, A. S., 232,
STUIVER, M., 339 250
SUGAWARA, K., OKABE,S. and TANAKA, M., USPENSKIY, V. A., INDENBOM, F. B., CHERNYS-
53, 147 HEVA, A. S. and SENNIKOVA, V. N.. 245,251
 REFERENCES INDEX 403

VALENTINE, J. W. and MEADE,R., 148 WHITE,D. E., HEM,J. D. and WARING,G. D.,
VALYASHKO, M. G., 5, 20 182, 190
VANDER WALT,c. F. J. and VANDER MERWE, WHITECROSS, M. I., 286
A. J., 302, 340 WHITMORE, E. C., 227, 251
VANNEY, J.-R., 148 WICKMAN, F. E., 148, 197, 207, 328, 340
VASSOEVICH, N. B., 225, 245, 251 WICKMAN, F. E. and VONUBISCH,H., 329,341
VEBER,V. V. and GORSKAYA, A. I., 244,251 WICKMAN,F. E., BLIX, R. and VON UBISCH,
VEBER,V. V. and TURKELTAUB, N. M., 228, H., 341
251 WILBUR,K. M., 149
VINOGRADOV, A. P., 4, 20, 49, 52, 53, 55, 59, WILBUR,K. M. and JODREY,L. H., 329, 341
61, 74, 75, 148 WILBUR,K. M. and WATABE,N., 58, 149
VINOGRADOV, A. P. and BOROVIK-ROMANOVA, WILLARD, H. H. and GREATHOUSE, L. H., 300,
T. F., 148 341
VINOGRADOV, A. P. and RONOV,A. B., 11, WILLIAMS, M. and BARGHOORN, E. S., 14, 198,
131, 132, 133, 148 207, 329 341
VINOGRADOV, A. P., RONOV,A. B. and RATYN- WILLIAMS, R. P., 149
SKIY, V. M., 134, 148 WILSON,R. L. and BERGENBACK, R. E., 149
VOGEL,A. I., 295, 297, 313, 315, 342 WINCHELL, A. N., 276, 341
VOGEL,J. C., 194, 195, 207, 329, 340 WINCHELL, A. N. and MEEK,W. B., 283, 341
VONDER BORCH,C., 148 WINCHELL, A. N. and WINCHELL, H., 350, 393
VON ECKERMANN, H., VON UBISCH,H. and WINDES,S. L., 351, 362, 363, 393
WICKMAN, F. E., 198, 207 WISMAN, J. D. H., 70, 87, 149
VON ENGELHARDT, W. 49, 148 WOBBER,F. J., 149
WOLF,K.H., 10,28,83,89, 100, 105,113, 149,
WAITE,J. M., 325, 340 255, 257, 259, 260, 274, 276, 286, 287, 294,
WALGER, E., 259, 282, 283, 286, 340 327, 341
WALKER, C. T., 28, 148 WOLF,K. H. and CONOLLY, J. R., 149,255,341
WANGERSKY, P. J. and GORDON, D. C., 148 WOLF,K. H., CHILINGAR, G. V. and BEALES,
WANGERSKY, P. J. and JOENSUU, O., 148 F. W., 328, 341
WARNE,S., 259, 261, 266, 267, 268, 269, 270, WOLF, K. H., EASTON,A. J. and WARNE,S.,
316, 317, 318, 320, 321, 323, 340 27, 75, 149
WARNE,S. and BAYLISS,P., 320, 323, 340 WOODRING, W. R., 149
WATABE, N. and WILBUR,K. M., 58, 105, 148, WOOLF,D. O., 351, 363, 393
286, 340 WRAY,J. L., 341
WATABE, N., SHARP, D. G. and WILBUR, K. M., WRAY,J. L. and DANIELS, F., 93, 95, 149, 153,
286, 340 167, 341
WATTENBERG, H. and TIMMERMANN, E., 88, 148 WYLLIE, P. J. and TUTTLE, 0. F., 149
WAUGH,W. N. and HILLJR., W. E., 361,364,
393 YANAT’EVA, 0. K., 5, 6, 20, 21, 178, 179, 184,
WAYLAND, J. R. and HAM,W. E., 393 185, 191
WAYLAND, R. G., 286, 340 YOE,J. H. and ARMSTRONG, A. R., 301, 341
WEBB,D. A. and FEARON, W. R., 52,54,148 YUSHKIN, N. P., 149
WEBB,T. L. and HEYSTEK,. 316, 318, 340
WEBER,J. N., 28, 117, 149,329,340 ZARTMAN,R. E., WASSERBURG, G. J. and
WEBER,J. N. and KEITH,M. L., 340 REYNOLDS. J. H., 195,207
WEBER,J. N. and LAROCQUE, A., 148,329,340 ZARITSKIY, P. V., 149
WEBER,J. N. and SMITH,F. G., 325, 340 ZELLER. E. J., 215,222,326, 341, 372, 393
WEBER,J. N., WILLIAMS,E. G. and KEITH, ZELLER,E. J. and PERN,W. C.,326,341
M. L., 329, 340 ZELLER,E. J. and RONCA,L. B., 372, 393
WEDEPOHL, K. H., 53, 148 ZELLER,E. J. and WRAY,J. L., 88, 92, 95, 103,
WEEKS,L. G., 233, 237, 251 149, 326, 341
WEEKS,W., 217, 222 ZELLER,E. J., WRAY,J. L. and DANIELS,F.,
WEISS,A., 231, 251 326, 341
WELLER,J. M., 2, 20, 234, 251 ZEN,E-AN, 149, 341
WELLS,A. J., 177, 191 ZOBELL,C. E., 74, 149, 229, 251
WEYL,P. K., 195, 207 ZUMPE,H. M., 341
SUBJECT INDEX1

Abqaiq-Ghawar oil field, 235 - inversion, 57, 100, 101, 203

Abrasive hardness of carbonate rocks, 362,363 -, Lake Bonney, 86
Absorption of elements, 104, 105 - needles, 97
- train, 297 - precipitation, 92-98
Acid-etching, 256-258 - preparation, 153
Adsorption, 104, 105 - recrystallization, 154-165
Age dating, 14, 18, 84, 327, 328 - thermodynamic stability, 95
- _ ,carbonates, zzsRa/238Umethod, 84 Argon, 52
_ _,- U-10 method, 84 Arsenic, 30-33, 50, 52, 53, 293
_ - , -, 234U/238Umethod, 85
~

Arthropoda, 32, 36, 39, 42, 46, 48, 55, 56, 63,
_ _ , -, uranium-helium, 18, 328 67,68
_ _ , -,carbon-14, 327, 328 Asmari Limestone, 236
_ _,corals, 84 Atmospheric COz, 134, 135, 194-197
Algae, 30, 33, 37, 40, 43, 44, 47, 55-58, 60,62, AustraIorbis glabratus, 69
67, 68, 73, 78, 83, 88, 89, 98, 99, 105, 113, Authigenic minerals, 28, 129
255, 286 Azurite, 349, 350, 353, 375, 386
-, Chlorophyceae, 30, 34, 37, 40,44
-, Corallinaceae, 30, 34, 37, 40, 44, 47, 59, 67 Bacteria, 24, 55, 56, 61, 72, 74.75, 88, 98, 229,
_ ,- ,Sr/Ca ratio, 67 230
-, Phaeophyceae, 30, 34, 37, 40,43 -, concentration of Ca and Mg, 61
-, Rhodophyceae, 30, 34, 37,40,44 -, decomposition of organic matter, 229, 230
Alteration, due to diagenesis-epigenesis, 9, -, direct influences on carbonates, 74
100-1 10 -, elements utilized by, 74
Ammonites, 234 -, ooliths precipitation, 98
Amphistegina radiafa, rare elements in, 80 Banff Limestone, 239
Anhydrite, 237, 248, 267, 268 Barite, 55
Ankerite, 260-265,281, 283, 315,321-324 Barium, 30-33, 50, 52, 71, 81, 90, 92-94, 104,
-, DTA analysis, 321-323 106, 108, 130, 293
Annelida, 33, 36, 38, 43, 46, 49, 55, 63 - content in molluscan shells, 71
Antimony, 43-46, 51, 293 _ _ _ Pacific sediments, 90
Antrim Shale, 239 Barium/calcium ratio, 81
Apparent specific gravity of carbonate rocks, Beryllium, 30-33, 50, 52, 293
362, 363 Biochemical fractionation in organisms, 73
Arab-D-Formation, 236 Biogenic versus inorganic extraction of ac03
Aragonite, 4,9, 12, 14,27,54,55,57,83,86,88, in sea water, 196, 197
92-95, 97, 98, 100, 101, 117, 153-165, 177, Biological specificity of metal ions, 73
203, 260, 262-266, 268, 315, 320, 321, 323, Bismuth, 30-33, 52
325, 349, 350, 352, 374, 386 Bitumen, 33, 40,47, 232, 234, 245,246
-, DTA analysis, 319, 320 Boron, 3, 30-33, 50, 52, 53, 81, 90, 128, 293
-, entropy structure, 94 Brachiopoda, 32, 35, 38, 41, 45, 48? 55-57, 63,
65, 67,68, 70, 75, 78, 79, 81, 109, 110, 255
Breunnerite, 27, 260, 262, 263, 265, 266
I The help extended by Herman H. Rieke, 111, Bromine, 3, 30-33, 50, 52, 293
in preparing the index is greatly appreciated Brucite, 173, 217, 218
by the editors. - stability range, 173
SUBJECT INDEX 405

Bryozoa, 31, 34, 37, 40,44,55, 57, 59, 61, 63, _ _,skeletal materials, 197, 198
67, 68, 103,255,288 _ - ,soil gases, 195-197
Building stone, 353 _ _ ,uses, 329
_ _ properties of limestone used in Kansas, Carbonate minerals, 7-13, 24-28, 83, 98, 102,
353 103, 115, 117, 151, 152, 165, 171-176, 280,
Bulk density of carbonate rocks, 354 281, 292-315, 350, 352, 353, 362, 363, 368-
375,386
Caddo Lime, 354 _ _ ,amorphous origin, 98
Cadmium, 33-36, 50, 52, 293 _ _ ,chart for determining ne, trigonal car-
Calcite, 14, 27, 55, 59, 76, 83, 96-98, 100, 107, bonates, 280
116, 153, 155-157, 161-164, 174, 183, 185, _ _ ,chemical analysis, 292-31 6
205,211,26&268,283,315,316,318 324-326, _ _ , classification, 315
349,350,352,371,374,386 _ _,composition of modern carbonate sedi-
-, DTA analysis, 315-320 ments, 115
-, thermoluminescence, 326, 371 - _ ,crystallographic data, 352, 353
-, variation of Po with composition, 283 _ _,fluid inclusions, 27
Calcium, 30-33,52,90,131, 161, 164,205,290, _ _, free energy, 368
305, 306, 328 _ _ , heat capacity, 368
-, changes with geologic time, 131 - -, - of formation, 368
- isotopes, 205, 328 - _ , infrared absorption spectra, 372-375
Calcium/magnesium ratios (also Mg/Ca ratio), _ _ , isomorphism, 26
10, 11, 77, 85, 99, 111, 113, 116, 117, 132, _ - ,magnetic susceptibility, 369
133, 135, 165, 186, 187, _ - , melting and transformation tempera-
_ _ _ , activity ratio, 180-188 tures, 367
_ _ _ , carbon dioxide indicator, 135 - _ , metastable, 151, 152, 165
_ _ _ , changes with time, 11, 133 _ _,mineral assemblage in Coorong lagoon,
- _ - , Coorong lagoon, 117 117
- - -, distribution, 111, 117 _ _ ,mineralogy control by inorganic proces-
_ _ _ , increase from shore, 113 ses, 83, 84
- - _ , iso-Ca/Mg ratio lines, 85 _ _ , minor elements, 27
_ _ _ , Precambrian sea water, 99 _ _ , modulus of rigidity, 362, 363
_ _ _ ,salinity effect, 116 _ _ ,-- rupture, 362, 363
_ _ _ , sea water, 186 _ _ ,non-carbonate components, 28
Calvert Formation, 62, 64, 65 _ _ ,optical data, 350
Canyon Limestone, 244 _ _ , physical properties, 349
Carbon, 30-33, 52, 53, 246 _ _ , physicochemical factors controlling
- -14, 327, 328 composition, 24
- dioxide, 134-136, 194-197, 296, 297, 317- _ _ , solubilities, 179, 367
322 - _ , solution, 103
_ - ,atmospheric, 134, 135, 194-197 - _ , stability, 171-176
_ _, biogenic, 197, 197 _ _ , ternary systems, 370
_ _ , determination of, 296, 297 _ - ,thermoluminescence, 326, 371, 372
_ _ , DTA analysis, 317-322 _ _ , trace elements, 27
_ _ effect on Ca/Mg ratio of carbonate rocks, _ _ , uses, 386
134-136 _ _ , variation of no with composition, trigo-
- isotopes (13C/12C), 14, 165, 194-199, 229, nal carbonates, 281
328, 329 Carbonate rocks, aspects and statistics of
- _ ,atmospheric COZ, 195-197 economics, 343-348
_ _ , bicarbonates, 195-197 _ _ ,bacterial carbonates, 194
_ _ , carbonate rocks, 195-197 - _ , calcium oxide/magnesium oxide ratio, 10
_ _ ,fractionation in the carbonate system, -- ,chemical alteration, 9, 100-110
_' _,- analysis, 292-3 15
196, 197, 329
_ _ , organic matter, 229 _ _,- composition, 294, 360, 361, 364,
_ _ , recrystallization of aragonite to calcite, 365
165 - _ , compressibilities, 355
- _ , sediments, 328 - _ , compressive strength, 358, 362, 363
406 SUBJECT INDEX

Carbonate rocks (continued) _ _,composite analysis of limestones, 364,365

- _ , crushing strength, 358 _ _ , determination of moisture and loss on
- _ , deformation, 211-216 ignition, 296
- _ ,dielectric constant, 360 _ _, ferrous iron, 309, 310
- _ , economics, 343-348 _ _ , magnesium, 307, 308
- -, formation of source rocks, 237 _ _ , main analysis of carbonates, 297-315
_ _ , high temperature studies, 198, 204 _ _ , major and minor element analysis, 292
_ _ , impact toughness, 362, 363 _ - , manganese, 300, 301, 308
- -, isotopes, 13, 14, 15, 193-206 _ _ , phosphorus, 303, 304
_ _ ,longitudinal bar velocity, 362, 363 _ _ , potassium, 310-313
--, magmatic and metamorphic rocks, 193 _ _ , Recent and ancient carbonate rocks, 294
- -,physical chemistry of formation, 12, _ _ , Rz03 group, 298-300
15 1-167 _ _ ,scheme for carbonate rocks, 295
- _ , physical properties, 348-360, 362, 363 _ _ , silica, 297, 298
- _ , Poisson's ratio, 362, 363 _ - ,sodium, 31G313
- _ , polycomponent systems, 286 _ _ , some carbonate minerals, 316
- _ , porosity, 2, 354 _ _ , strontium, 310-313
- _ , relationship between organic matter and _ _ , sulfur trioxide, 314, 315
insoluble residue in, 232 _ _ , titanium, 301, 302
- _ , reservoir, 348 _ - , total sulfur, 313, 314
- _ ,resistivity, 359 _ - , trace element analysis, 293
- _ ,rigidity, 357 - composition of various carbonates, 294,
- _ ,scleroscope hardness, 362, 363 360, 361, 364-366
- _ , shear waves, 357 Cherokee Reservoir, 241, 242
- _ , solid solution and subsolidus relations, Cherts, 201, 202, 258
366-371 -, 1 * 0 / 1 6 0 ratio, 201, 202
- _ ,source rocks for oil, 235-248 Chlorine, 3, 21, 33-36, 50, 52, 293
- _ ,specific damping capacity, 362, 363 Chondrites, 199
- _ ,spot tests for cations, 289-292 Chordata, 55, 56, 68
- _ , tensile strength, 362, 363 Chromium, 33-36, 50, 52, 90, 118, 128, 293,
- _ , thermal conductivity, 359 298, 302
- _ , - expansion, 354 Cipolin, 219, 222
- _ , uses, 18, 19, 373, 376-389 Classification of carbonate minerals, 3 I5
- _ , Young's modulus, 356, 362, 363 Clay, 2, 29, 90, 229-231, 240, 248, 258, 274
Carbonatites, 14, 195, 198-200 (see also shale)
Caspian Sea, 228 -, Br/CI ratio, 29
Caves, 19, 92, 96, 387 -, CI/Br ratio, 29
Celestite, 79, 102 -, organic matter of, 231
Cement, 105, 128-130, 344, 346, 347, 377 -, overburden pressure, 2, 248
-, cryptocrystalline, 105, 287 - separation from carbonates, 276-279
-, environmentally induced changes, 128-130 Cobalt, 33-36, 50, 52, 53, 100, 106, 118, 293
-, production of, 377 Coccoliths, 58
-, world production, 347 Coelenterata, 31, 35, 38, 41, 45, 48, 55, 56, 62,
Cephalopoda, 32, 36, 38, 42, 46, 48, 57, 63, 68 67
Cerium, 33-36 Collenia, 99
Cerussite, 19, 267, 349, 350, 352, 375, 386 Compressibility of carbonate rocks, 355
Cesium, 33-36, 50, 52, 293 _ _ _ _ , at high pressures, 355
Charles Limestone, 239 _ _ _ _ , at low pressures, 355
Chemical alteration of carbonates, 9, 100-1 10 Compressive strength, 358, 362, 363
- analysis, 289-3 15, 364, 365 Concretions, 105, 106, 128-130
_ _ , absorption train, 297 Cone-in-cone structures, 102
- _ , acid insoluble residue, 297 Contamination, 74, 86
- _ , aluminum, 304, 305 -, cosmogenous, 86
- _ , calcium, 305, 306 -, drill cores, 74
-- , carbon dioxide, 296 -, mechanical, 86
- -, chromium, 302, 303 -, volcanic, 86
 SUBJECT INDEX 407

Conversion, 101 -, uses, 378-384

Coorong lagoon, 110, 116, 117 Dolomitization, 11, 15, 110, 183, 184, 186, 198,
Copper, 33-36, 50, 52, 53, 81, 85, 90, 118, 128, 202-204
293 Drewite, 89
Corals, 62, 65, 68, 71, 83 Dundee Limestone, 236
Correlation, based on composition, 85, 128 Duvernay Shale, 235, 239
Crassostrea virginica, 8 1
Critical concentration ratio (aragonite/magne- East Twin Lake, 114
sium), 151, 158 Echinodermata, 33, 36, 39, 42, 46, 49, 5 5 , 59,
Crushed stone, 377 63, 67, 68
Crushing strength, 358 Echinoidea, 33, 36, 39, 42,46, 49, 57, 63, 78
Crustacea, 32, 36, 39,42,46,48, 61, 63,68 Economics of carbonate rocks, 343-348
Cyanophyceae, 53 Elastic parameters of carbonates, 356, 357
_ - _ _ , ordinary pressure and tempera-
Deep Spring Playa, California, 183 ture, 356
Deformation of carbonate rocks, 15, 16, 211- _ _ _ _ ,4,000 kg/cm2 and 30°C, 357
21 6 Elemental composition of carbonates, 7-10,
_ _ _ _ , mechanism of, 211-213 23-149
_ _ _ _, experimental analysis of, 213-216 _ _ _ _ ,carbonate skeletons, 25, 3049,
Diagenesis (or diagenesissepigenesis), 1 I, 15, 57-71, 76-84, 98, 99
75, 99-110, 183, 184, 186, 198, 202-204 _ _ _ _,concentration through metabolic
-, alteration, 75 processes, 72
-, - by fresh water, 109 _ _ _ _ , diagenetic alterations, 75, 76,
-, chemical and physical changes, 106-110 106-1 10
-, conversion, 101, 102 _ _ _ _ ,direct bacterial influences, 74, 75
-, diagenetic dolomitization, 11, 15, 110, 183, _ _ _ _ , inorganic processes determining,
184, 186, 202-204 25, 85-98
-, grain growth and diminution, 101-102 -__- , metamorphically mobilized ele-
-, inversion, 100 rnents, 130
-, 1 8 0 / ' 6 0 alteration during, 202 _ _ _ _ , organic matter of organisms, 52-
-, 1sO/160change in brachiopods, 109, 110 54, 71-74
Dielectric constant, 360 _ _ _ _, physicochemical factors deter-
Differentiation of carbonates and trace ele- mining, 24
ments, 113 _ _ _ _, poisonous elements, 105
Dilatometry, 214 _ _ _ _ , uptake of elements by shells, 75-
Dolomite, 5, 13, 169-191, 199-204, 378-384 82
-, chemical requirements, 378-384 Ellenburger Limestone, 236
-, chemistry of formation, 13, 14, 169-191 Environment, 76-85, 97-99, 109
-, COZeffect on formation, 169, 185, 186 -, hypersaline and hyposaline effect on skele-
-, DTA analysis, 321, 322 ton composition, 81, 109
-, Eh effect on formation, 188 -, influence on particle form of carbonate
-, equilibrium conditions, 171-174 precipitates. 97, 98
-, metasomatism of calcite, 202, 203 -, inorganic precipitation, control of, 92-97
-, origin of, 202-204 -, regional trends in skeletal mineralogy,
-, 180/1e0 ratio of, 199-203 dependence on, 83, 84
-, pH effect on formation, 188 -, salinity and temperature influences on
-, physical requirements, 378-384 composition, 76-82
-, precipitation, 177-178 Epigenesis, see diagenesis-epigenesis
-, pressure effect on formation, 169, 187, 189 Equilibrium constants, 169, 178-181, 183, 185,
-, solubility, 170, 174-176, 178, 179, 184, 189, 205
185 Erbium, 33-36
-, stability, 171-174 Espiritu Santo Island, 4, 167
-, stable isotope distribution, 193-206 Etching figures, 213, 215
-, synthesis experiments, 176, 177, 187 Europeum, 33-36
-, temperature effect on formation, 169, 181, Experiments, 2, 69, 75, 88, 92-98, 153-164,
187, 189 176-181, 184, 185, 187, 248
408 SUBJECT INDEX

Experiments (continued) Greenhorn Limestone, 354

-, aragonite preparation, 153 Guil Valley, France (Guillestre Marble), 214,
-, - shell uptake of strontium, 69 215
-, calcium carbonate deposition in caves, 92, Gulf of Batabano, 230
96 Gypsum, 86, 262, 267, 268
-, - -precipitation controlled by impuiities,
92-96 Hankinite, 218
-, dolomite synthesis, 176180 Harrodsburg Limestone, 115
-, inorganic precipitation of calcium carbon- Heat capacity of carbonate minerals, 368
ate, 88, 92-98 - of formation of carbonate minerals, 368
-, overburden pressure effect on porosity, 2, Heath Limestone, 244
248 Helium, 52
-, particle form of carbonate precipitates, 97, Hematite, 255
98 Hemichordata, 55
-, recrystallization of aragonite to calcite, Holmium, 3639
153-164 Hydrocarbons, 225-248
-, shell growth, 75 -, allochthonous, 245
-, solubility, 178-181, 184, 185, 187 -, analysis of, 239
-, *%r and 45Ca isotopes in aragonite and -, autochthonous, 245
calcite precipitates, 69 -, catalytic generation, 232, 247
-, Sr/Ca ratios in precipitates, 88 - derived from living organisms, 226229
-, vaterite precipitation, 94-96 - distribution in non-reservoir rocks, 238,239
Exploration philosophies, 85 - - in Recent and ancient sediments, 240
- _ - source-reservoir facies, 241
Feigl’s solution, 270, 272 - generation from organic matter, 229-232
Florida Bay, 230, 232 -, liquid hydrocarbons in Recent sediments,
Florine, 33-36, 50, 52, 293 228
Fluid inclusions, 27 -, ratio of odd- to even-numbered n-paraffins
Flux, 361 in sediments and crude oils, 244
Foraminifera, 31, 34, 37, 40, 44,57, 5941, 67, Hydrogen, 36-39, 52
68, 70, 71, 83, 103, 211,287, 325, 328, 329 Hydromagnesite, 13, 87, 117, 172, 174-177,
Forsterite, 217, 218 186, 188
Fractionation in organisms, biochemical, 73
-, isotope, 193-205 Impact toughness, 362, 363
Free energy calculations: dolomite, calcite, Inclusions, fluid, 27
magnesite, 171-175, 177, 178 Indium, 37-39, 50
- _ of formation of carbonate minerals, 368 Infrared absorption spectra of carbonate
Frontier Shale, 239 minerals, 372-375
- reflection spectroscopy, 214
Gadolinium 3639 Inorganic precipitation of calcium carbonate,
Galena, 100 86, 92-98
Gallium, 36-39, 50, 118, 293 Insoluble residue, 123, 127, 232
Garnier River, 214 - -, relationship with organic matter and
Carrels technique, 189 bitumen contents, 232
Gastropoda, 32,36,38,42,46,48,57,63,67,78 _ _ , variation with time in carbonate rocks,
Germanium, 36-39, 50, 52, 293 123, 127
Gibbs conditions of equilibriumand freeenergy Intercrystalline gliding, 212
calculations, 171-178 Intracrystalline gliding, 212
Glauconite, 274 Inversion, aragonite to calcite, 57, 84, 100,
GlobiKerina, 31, 34, 37,40,44,47, 79, 83, 136 101
Goethite, 55 Iodine, 36-39, 50, 52, 293
Gold, 3C33, 50, 52, 293 Ions. interference in determinations of, 310
Grain deformation, 21 1-213 Ireton Limestone, 239
- diminution, 101-102 Iron, 33-36,50,52,53, 101,105,124, 128. 290-
- growth, 101-102 292, 298, 299, 309, 310
Great Salt Lake, Utah, 88, 114 Isomorphism, 26
SUBJECT INDEX 409
Isotope geochemistry, 14, 15, 193-208, 279, Macroporella, 217
328, 329 Madison Limestone, 239
_ _ , calcium and magnesium, 205, 206, 328, Magnesite, 5 , 87, 172-176, 180, 187, 188, 260-
329 268, 315, 317-320, 323, 349, 350, 352, 374,
_ _ ,carbon, 194199,204 386
_ - , carbonate sediments, 328, 329 -, DTA analysis of, 317-320
--, distribution of carbon in carbonates, - stability range, 173, 187
194199,204 -, thermogravimetric analysis, 323, 324
_ _ ,- - oxygen in carbonates, 199-203 Magnesium, 3, 15, 39-43, 52, 59, 77, 79, 87,
--,fractionation, 193-205 90, 95, 101-103, 107, 111, 115, 131, 158,
--, magnesium, 206, 328 186,205, 206, 217,291, 307, 308
- -,high-temperature carbonates, 196, 198, - compounds, uses of, 376
200,203,204 - concentration in sea water, 3, 186
--,oxygen, 199-205, 279, 328, 329 -, determination of, 307, 308
_ - , W C relationship between coexisting - in inorganic carbonates, 87
dolomites and calcites, 204 -, isotopes of, 205, 206
_ _,613Cvalues in carbonaceous chondrites, - relationship to temperature, 77, 78
199 -, spot test for, 291
--, P O relationship between coexisting Mg/Ca ratio, see Ca/Mg ratio
dolomites and calcites, 201-203 Magnetite, 55
Joana Limestone, 85 Malachite, 19, 349, 350, 353
Jubaila Formation, 236 Mammoth Cave, Kentucky, 387
Manganese, 39-43, 50, 52, 53, 81, 90,101,I105,
Ketona Dolomite, 365 108, 118-124,291-295, 300, 301, 308, 387
Kimmeridgien Limestone, 244 Maracaibo Basin, 236
Marble, 18, 193, 210,222, 345, 354360
La Luna Limestone, 236, 243 -, defined, 222
Lake, Sr/Ca ratio in, 114 - Falls Formation, 365
- Beloved, U.S.S.R., 6 Medway White Chalk, 364
- Mendola, 114 Melting and transformation temperatures of
Lanthanum, 36-39, 50 carbonate minerals, 367
Larnite, 218 Mercury, 36-39, 50, 52,293
Lau, Fiji, 4 Menvinite, 218
Law of minimum in ecology and geochemistry, Metabolic processes,concentration of elements,
82, 83 72
Lead, 39-43, 51-53, 92, 93, 100, 118, 293 Metal ions, concentration, stability of com-
Leavenworth Limestone, 364 plexes, and biological specificity, 73
Lee-Hedberg technique, 276 Metamorphism, 216-220
Lime, production of, 377 (see limestone and --,Bowen’s series, open and closed systems,
dolomite) 218,219
Limestone, 209, 210, 361, 364, 365, 378-384, -, contact, 216, 217
387 -, regional, 217-220
-, chemical composition of, 364, 365 -, reorientation of calcite, 216
-, chemicalrequirements in their use, 378-384 -, selective, 218
- flux, 361 Metastable carbonate minerals, 151, 152, 165
-, formation of, 209, 210 Michigan Basin, 236
-, organic matter in, 71, 72, 238-242 Micrite, 114, 210, 211
-, physical requirements in their use, 378- -, recrystallization, 114
384 Microorganisms, 6
-, uses of, 378-384, 387 Migration of petroleum, 233-235
Lingulepsis, 69 Millerite, 100
Linnaeite, 100 Minerals, see individual names
Lithium, 37-39, SO, 51, 293 -, authigenic, 28
Lithothamnion, 83, 294 Mirabilite, 86
Longitudinal bar velocity in carbonate rocks, Mission Canyon Limestone, 239
362, 363 Modulus of rigidity, 362, 363
 410 SUBJECT INDEX

Modulus of (continued) - isotopes (180/le0 ratio), 69, 79, 109, 110,

_ _ rupture, 362, 363 165, 194, 199-205, 328, 329
Mollusca, 32, 36, 38, 42, 45, 46, 48, 55-57, 59, _ _, diagenetic changes, 109, 110
61, 63, 67, 68, 71, 82, 102 _ _ , Globigerina ooze, 200
Molybdenum, 3943, 52, 53, 293 _ _ in brachiopods, 79
Mytilus califomianus, 76, 77 _ _ _ carbonates, 199-203
-, edulis, 76, 77 --- carbonate sediments, 328, 329
_ _ _ dolomitexalcite pairs, 201-205
Neodymium, 3 9 4 3 _ _ _ formation waters, 203
Nesquehonite, 172-174 _ _ , paleotemperature curve, 200
-, stability range, 173 _ _ , recrystallization of aragonite to calcite,
Neutron activation, 293 165
Niagara Dolomite, 365 _ _ , uses of, 329
Nickel, 39-43, 51-53, 90, 100, 118, 128, 293 _ _ , variation with age, 201, 202
Niobrara Shale, 239
Nitrogen, 3943, 52, 58 Paluxy Formation, 365
Nodules, 91. 105 (see also concretions) Peel techniques, 272-274
Nordegg Shale, 239 Pelecypods, 32, 36, 38, 42, 45, 48, 67, 68
North Wales Limestone, 364 Peridiniaceae, 53
Nubrigyn Reef Complex, 113 Permian Basin, 236
Persian Gulf, 151
Oil, crude, composition of, 227 Petroleum, 16, 17, 225-248

-.
Ooid, 91, 97, 98
chemical composition of, 91
Oolite, 84, 88, 89, 91, 97, 98, 101, 210, 247, 258
-, migration of, 233-235, 245
-, origin of, 16, 17, 225-248
-, source rocks of, 235-248
-, environmental influences, 97, 98 Phanerozoic, 25
Oolith, 75, 98 Phosphate, in Russian platform sediments,
-, bacteria causing precipitation of, 98 125-1 27
Optical data on carbonate minerals, 279-283, Phosphatic material in shells, 55, 56, 69
350 Phosphoria Formation, 365
Oread Limestone, 364 Phosphorite, 125
Organic influences on elemental composition, Phosphorus, 3943, 52, 118, 124, 162,298, 303,
24, 25 304
- matter, 71-74, 229-231, 238-242, 246 -, chemical analysis for, 303, 304
- _ , bacterial decomposition, 229, 230 - in Russian platform sediments, 118-120,
- _ , composition, Cherokee Group of Kan- 125-127, 128
sas and Oklahoma, 242 Physical properties, 348-360, 362, 363
- _ ,environment, effect on amount of, 238 _ _ of carbonate minerals, 349
_ _, generation of hydrocarbons from, 229- _ - _ carbonate rocks, 348-360, 362, 363
232 Physicochemical factors determining elemental
- _ , in carbonate source rocks, 238-242 composition, 24
_ _ _ limestones, 71 Plankton, 53
_ _ _ non-reservoir rocks, 239 Plattsmouth Limestone, 364
_ _ _ Recent and ancient sediments, 240 Poisson’s ratio, 360, 362, 363
_ - _ _ clastic sediments, 231 Polymorphism, 57, 66, 82, 83, 98, 99
_ _ _ _ marine sediments, 240 Porifera, 31, 35, 38, 41, 44, 47, 5 5 , 56, 62, 65,
_ _ _ shales, 71 67, 68, 255
_ _ , relationship between total Corg and Porosity, 2, 248, 354
soluble bitumens, 246 Porphyrins, 72, 227
- _ , - to insoluble residue, 232 Portland cement, production of, 377
- _ variation in content with particle size, Potassium, 3, 37-39, 50, 52, 98, 162, 293, 310-
Viking Shale, 231 312
Organism, shell secretion, 58 -, chemical analysis for, 31C312
Orinoco Delta, 230 Post-mortem concentration of elements, 72
Overburden pressure, effect of, 2,210,211,248 Praseodymium, 3 9 4 3
Oxygen, % weight of organisms, 52 Precipitation, 86,92-98, 105, 106, 153,177-180
 SUBJECT INDEX 41 1

- of aragonite, 92-98, 153 Sauwand Limestone, 111, 112

_ - calcite, 92-98 Scandium, 4346, 51
_ - carbonate cement and nodules, 105, 106 Scapolite, 219
_ _ dolomite, 92, 177-180 Schist, 217
_ - vaterite, 92, 94, 97, 98 Schotter flask, 296
-, physicochemical inorganic, 86 Schumann method, 282
Pressure, influence, 2, 169, 187, 189, 209-222, Scleroscope hardness of carbonate rocks, 362,
248 363
-, - of load, overburden, 2, 210, 21I , 248 Sea water, composition of, 2, 3, 186
-, - on dolomite genesis, 169, 187, 189 Selenium, 4346, 51, 52, 293
Proteins, 9, 72, 229, 230, 241 Serpula tubes, 59, 60,63
Protodolomite, 13, 152, 153, 176, 177 Shale, 90, 234, 239, 242, 247
Protozoa, 31, 34, 37, 40, 44, 55, 56, 61, 67 Shear waves in carbonate rocks, 357
Pteropod shells, 68, 108 Siderite, 27, 129, 205, 260-265, 267, 281-283,
Pyrite, 129, 130, 361 294, 315, 316, 317, 322, 324, 349, 350, 352,
Pyroxene, 218 367, 369, 374, 386
-, DTA analysis, 3 16, 3 17, 3 19, 322
Quirke Lake, Ont., 54 -, staining, 260-265, 267
Quarries, 388 Sideroplesite, I30
Quartz, 2, 129, 130, 205, 207 (see silica) Silica (SiOz), 127, 129, 297, 298
-, chemical analysis for, 297, 298
Radiolaria, 79 - in carbonate rocks of Russian platform, 127
Radium, 39-43, 51, 84, 293 Silicon, 4346, 52, 72
- isotopes, 84, 85 Silver, 30-33, 50, 52, 53, 293
Recrystallization, 100, 109, 112, 151, 152, 1 5 4 Simpson Shale, 236
165, 212, 213 Skeletal mineralogy, 8,9,24,54,55,57-63, 65-
- effect of calcium ion, 160, 161 67, 69, 75-84, 106-109
_ - - magnesium ion, 156160 _ _ , aragonite, 57-59
_ _ - other ions, 162, 163 _ _,calcite, 57-59
-, influence of chemistry and temperature, _ _ , distribution according to phylum, 55
154, 155 _ _ , environment, influence of, 82, 83
- of aragonite to calcite, 100, 154-165 _ _ ,factors determining, 54
- _ vaterite, 162, 164 _ _ , geological problems, application of, 75
-, post-tectonic, 213 _ - , regional trends in, 83, 84
-, rate of, in distilled water, 154, 155, 158 - _ , taxonomic significance, 75
-, Riecke’s principle, 212 _ - , temperature indicator, 76, 77
-, solid state, 151, 152, 165 Skeleton composition, 25, 3 M 9 , 57-71, 76-
-, syntectonic, 213 84, 98, 99
Reorientation of calcite, with dynamic meta- _ _ , magnesium content, 59-61, 77, 78
morphism, 216 - -,strontium content, 61-70, 78, 79
Replacement, dolomite, 183, 184, 202, 203 Smithsonite, 19, 266, 267, 349, 350, 352, 375,
Reservoir rocks, carbonate, 348 386
Resistivity, 359 Sodium, 3, 21, 3943, 51, 52, 92, 98, 128, 162,
Rhenium, 43-46 293, 310
Rhodochrosite, 19, 27,264,267,269, 281-283, Solnhofen Limestone, 355-359, 365
349, 350, 352, 374, 386 Solid solution and subsolidus relations, 366-371
Riecke’s principle, 212 Solubility, 2.3, 174-176, 179-185, 187,367
Rigidity of carbonate rocks, 357 -, calcite-dolomite equilibrium, 181
Rogers City Limestone, 236 +
-, calcite dolomite and magnesite dolo- +
Rubidium, 4346, 51, 52, 293 mite, 187
Russian platform, 120-128, 131-133 -, CaC03-MgC03-HzO system, 5
-, dolomite, 174-176, 178, 179, 183-185, 187
Salinity, relation to skeletoncomposition, 80-82 -, Mg/Ca ratio in ground waters, 182
Samarium, 4 3 4 6 -, various components in sedimentary rocks,
Sand, 2, 10, 119, 123, 130, 213, 231, 258 2, 3
Sandstone, 126, 130, 133, 242 Solution, leaching and bleaching, 103, 104
412 SUBJECT INDEX

Source rocks, 235-248 ----corals, 62, 67, 68

--,comparison of carbonates and shales, ---- fossil shells, 81, 82
247 _ _ - _ fossils and rock matrix, 70, 101
_ _ , distribution of organic matter in, 238- _ _ _ _ gastropods, 63, 64,67
242 _ _ _ _ organisms, 62-70, 78-82, 101,102
_ _ , examples of, 235-237 _ _ _ _ pelecypods, 63,64,67
- -, geochemical techniques for recognition _ _ _ _ precipitates, 87-89
Of, 242-246 _ _ _ - sea water, 88
Sparite, 15, 210, 21I , 288 _ _ - _ sediments, 90, 112-115
Species effect, in composition of skeletons, 58 -,- - - tissue, 68
Specific damping capacity of carbonate rocks, _ _ _ , iso-strontium/calcium ratio lines, 112
362, 363 ---, marine versus fresh-water sediments,
- gravity, apparent, 362, 363 114
Spectral well logging, 128 __- , recrystallization, effect on, 101, 165
Spectrometry, 293 -__ ,sedimentary cycle, 113
Spectrophotometry, 293, 295, 299-304, 309- _-- , temperature effect on, 78, 79
315 __- , salinity effect on, 8&82
Spergen Formation, 365 _-- , variation with geologic time, 133
Sphalerite, 100 Sulphur, 43-46, 52, 313, 314
Spherulite, formation, 97, 98 -, chemical analysis for, 313, 314
Spongiostromata, 276
Spot tests for cations, 289-292 Talc, 217, 218
Springer Shale, 239 Techniques in analyzing carbonates, 17, 18,
Spurrite, 218 214,215, 242-246, 253-329
Stability of carbonate minerals, 171-174, 187 _ _ _ - , acid etching, 256258
Staining, 259-272 _ - _ - , - insoluble residue, 297, 298
-, alizarin red, 262, 267, 270, 271 _ _ _ _ , differential thermal analysis, 315-
-, determination of isomorphous series, 282 323
-, Feigl's solution, 263, 272 _ _ _ _,diolatometry, 214
-, Harris' hematoxylin, 268, 272 _ _ _ - , electron microscope, 286, 287
-, iron content in calcite, dolomite and anke- _ _ - - ,etching figures, 215
rite, 271 _ _ _ - , field studies, 254, 255
- solutions, 260-269 _ _ - - , geochemical, for recognizing-
-, titan yellow, 268, 272 source rocks, 242-246
Stalactites, 388 _ _ _ - ,infrared reflection spectroscopy,
Stalagmites, 388 214
Steinplatte Limestone, 111, 112 _ _ - - , introduction, 17, 18
Stone, production of, 343, 351, 353, 373, 377 _ _ - - , isotopes, 328
Stress, influence on carbonate rocks, 21 1-216 _ _ _ _, moisture and loss on ignition, 296
Stromatactis, 255 _ - _ _ , peel, 272-274
Stromatolites, 56 _ - - - ,optical identification,279-283,286
Strontianite, 19,27,89, 102, 263,267,315,320, _ _ _ _, oxidation method for determining
323, 325, 349, 350, 352, 375, 386 source rocks, 244
Strontium, 3, 43-46, 51, 52, 65-67, 69, 78-82, _ _ _ _,radiocarbon dating, 327, 328
87-97, 100-115,118,119,130,132,133,162, _ _ _ - , separation of insolubles, 274-279
163, 165,290, 293,294, 310, 311 _ _ _ _,- _ clay, 276279
-, chemical analysis for, 310, 311 - _ _ _ ,spectrophotometricmeasurements,
- in inorganic carbonates, 87-97 295, 296, 299-305, 309-314
- in skeletons, 61-70, 78,79 _ _ _ _, spot tests for cations, 289-292
-/calcium ratio (also Ca/Sr ratio), 8,9, 11, 12, - _ _ _ , staining, 259-272
62-70,78-82,87-90, 101,102,112-116, 133, ----, statistical and microfacies studies,
165 287-289
- - _ ,factors affecting, in organisms, 64 _ _ _ - ,thermogravimetric analysis, 323,
- - _ in Algae, 62, 89 324
- - _ _ carbonates, 65 _ _ _ _ , thermoluminescence, 215, 216,
- - _ _ cemented beach sands, 89 326, 327
SUBJECT INDEX 413

Techniques in analyzing carbonates (continued) -/calcium ratio, 84

---_ ,trace-element analysis, 293 --helium, age determination, 18, 328
- _ _ _ , universal stage, 213 Uses of carbonate minerals, 386
- - _ _ , X-ray diffraction, 214, 324, 325 - _ _ rocks, 18, 19, 373-389
- - _ _ , - radiography, 289
Temperature, 76-79, 154-161, 163-165, 169, Vanadium, 47-49, 51-53, 90,106, 118, 293
181, 187, 189, 204, 205 Vaterite, 94, 96, 98, 162, 164, 325
-effect on dolomite formation, 169, 181, 187, -, recrystallization, 162, 164
189 Viking Shale, 230
- _ - equilibrium constant, 204, 205 Viscan Limestone, 245
- - _ recrystallization rate, 154-161, 163- Viviparus, 58
165
- -magnesium relationship, 77, 78 Water, 2, 3, 180-186, 200
- -mineralogy relationship, 76, 77 -, sea, 2, 3, 186, 200
- -strontium relationship, 78, 79 -, subsurface, 180-182, 185, 186
Tensile strength, 362, 363 -, surface, 183, 184
Terbium, 43-46 Weber Sandstone, 242
Ternary systems, 370 Wilcox Shale, 239
Thallium, 47-49, 52 Williston Basin, 235
Thermal conductivity, 359 Whiting, uses of, 385
- expansion, 354 Witherite, 19, 27, 263, 267, 268, 315, 320, 323,
Thermogravimetric analysis, 323, 324 349, 350, 352, 375, 386
Thermoluminescence, 215, 326, 327, 371, 372 -, DTA analysis of, 320
Thorium, 47-49, 51, 293 Woliastonite, 217, 218
Thulium, 4 7 4 9 Woodford Shale, 239
Tilleyite, 218
Time, importance in reactions, 12, 153 X-ray, 2, 17, 18, 153, 176, 180, 213, 214, 275,
Tin, 43-46, 51-53,293 277, 278,289, 318, 324-327, 366
Titanium, 47-49,52, 53,90, 127, 128,292,293, -, crystal deformation, 213
298, 301, 302 - diffraction, 324-327
- determination of, 301, 302 -, overburden pressure, 2
Toronto Limestone, 364 - radiography, 289
Traverse Limestone, 236 - spectrograph, 293
Tremolite, 218, 219 Xenomorphic, 210
Trenton Limestone, 236
Trilobita, 36, 39, 42, 46, 57 Young's modulus, 356, 362, 363
Trona, 19, 375, 386 Ytterbium, 4749, 51
Tungsten, 4749, 51, 293 Yttrium, 47-49, 73

Universal stage, 213 Zechstein Dolomite, 239

Uranium, 18,29,4749, 51, 71, 84, 85,91, 293, Zechsteinsalzen rocks, 90
328 Zinc, 4749, 51-53, 100, 118, 293
-, syngenetic, 91 Zirconium, 47-49, 51, 90,293