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Cryogenic Brine and Its Impact On Diagenesis of Glaciomarine Deposits,

McMurdo Sound, Antarctica

Article in Journal of Sedimentary Research · August 2018

DOI: 10.2110/jsr.2018.48

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 Journal of Sedimentary Research, 2018, v. 88, 898–916
Research Article
DOI: http://dx.doi.org/10.2110/jsr.2018.48

CRYOGENIC BRINE AND ITS IMPACT ON DIAGENESIS OF GLACIOMARINE DEPOSITS, McMURDO

SOUND, ANTARCTICA

MINGYU YANG, TRACY D. FRANK, AND CHRISTOPHER R. FIELDING

1
Department of Earth and Atmospheric Sciences, 126 Bessey Hall, University of Nebraska-Lincoln, Lincoln, Nebraska 68588-0340, U.S.A.
e-mail: mingyu.yang@huskers.unl.edu

ABSTRACT: Pervasive 18O-depleted carbonate cements in sediment cores acquired by the Cape Roberts Project (CRP)
in McMurdo Sound, Antarctica, were previously attributed to mixing of glacial meltwater and seawater in the
subsurface. However, a more recent discovery of 18O-depleted, connate brine formed by seawater freezing in a nearby
sediment core (AND-2A core) called this interpretation into question. This core contains widespread carbonate
cements in the glaciomarine sediments, which have been demonstrated to precipitate from the brine by conventional
(d18O) and clumped (D47) isotopic data. Building on findings from the AND-2A core, this study investigates the
geochemical nature, origin, and distribution of diagenetic fluids, and re-evaluates their impact on diagenetic patterns
in glaciomarine deposits of the composite Oligocene to lower Miocene succession from the CRP cores. Sandstones
were characterized in the context of a well-established chronostratigraphic and sequence stratigraphic framework by
systematic point counting and modal analysis using optical microscopy. Diagenetic carbonate phases and mineralogies
were assessed by cathodoluminescence microscopy and energy-dispersive X-ray spectrometry. Low-Mg calcite cement
is the most widespread diagenetic phase and was selected for analyses of stable carbon and oxygen isotopes. Similar to
the AND-2A core, the cement increases in crystal size and decreases in d18O value (–4.8 to –19.5% VPDB) with
increasing depth to ~ 700–800 m. These patterns indicate calcite precipitation from interstitial brine along local
geothermal gradients. When considered in the context of Neogene climate, tectonic, and burial history, timing of
calcite cementation is linked to a period of extensive formation of cryogenic brine during c. 13 to 10 Ma when the
region transitioned into a cold, polar climate regime and McMurdo Sound was periodically glaciated by expanded,
cold-based Antarctic ice sheets. Beyond McMurdo Sound, the propensity for formation of cryogenic brine exists in
most glaciomarine settings. As such, the potential for diagenetic alteration by such fluids should be considered in
studies of the deposits of ancient glaciated continental margins.

INTRODUCTION subsurface migration of brines over long time intervals during repeated
Neogene continent-scale glaciations in Antarctica (Frank et al. 2010;
Progressive freezing of seawater is known to produce hypersaline, Mikucki et al. 2015).
carbonate-saturated cryogenic brine (Herut et al. 1990). Glaciation and
Cryogenic brine, present as interstitial fluid, in the glaciomarine
attendant sea-level fluctuation on continental margins can promote
sediments of the core (AND-2A core) recovered by the ANDRILL-SMS
production of brines from bodies of seawater that are isolated in marginal
Project has isotopic signatures that distinguish it from other surface fluids
troughs (Starinsky and Katz 2003; Grasby et al. 2013). Cryogenic brines in
in the polar regions. The fluid has been linked to distinctive diagenetic
coastal areas of the polar regions have been well documented via direct
patterns in the sediments (Dunham et al., in press). The d18O values of the
analyses of water chemistry. In the Arctic region, brines form by annual
freezing of isolated seawater masses in two thermokarst lake basins on brine vary between –11 and –6% VSMOW (Frank et al. 2010). The 18O
Banks Island, Canadian Arctic Archipelago (Grasby et al. 2013). Brines are depletion results from preferential removal of 18O during sea-ice formation
also documented from seasonally ice-gouged seabed depressions in (Craig and Gordon 1965), mirabilite precipitation (Stewart 1974), and
Resolute Bay, NW Territories, Canada (Kvitek et al. 1998). In the subsequent rock–fluid interaction during burial, for example through
Antarctic region, especially the McMurdo Sound region, a dense brine alteration of volcanic materials and feldspars (Garlick and Dymond 1970).
body of cryogenic origin was discovered in the subsurface of McMurdo Further investigation, including stable (d13C and d18O) and clumped (D47)
Sound by the ANDRILL Southern McMurdo Sound (SMS) Project (Frank isotope analyses of the diagenetic carbonate, indicates that the brine is a
et al. 2010). In addition, brines associated with an ancient marine intrusion long-term feature of McMurdo Sound, and is responsible for much of the
exist beneath glaciers, lakes, and permafrost along the onshore Taylor carbonate precipitation in the Neogene sediments of the AND-2A core
Valley, which connects to McMurdo Sound (Matsubaya et al. 1979; (Fielding et al. 2012; Staudigel et al. 2018). The stratigraphic distribution
Cartwright and Harris 1981; Carlson et al. 1990; Takamatsu et al. 1998; of the carbonate cements is strongly correlated with paleoclimate regimes
Lyons et al. 1999; Higgins et al. 2000; Lyons et al. 2005; Mikucki et al. and sequence stratigraphic systems tracts (Dunham et al., in press).
2015). The studies from the McMurdo Sound region point to widespread Carbonate cements are more prominent in sandstones deposited in the

Published Online: August 2018

Copyright Ó 2018, SEPM (Society for Sedimentary Geology) 1527-1404/18/088-898/
JSR IMPACT OF CRYOGENIC BRINE ON DIAGENESIS OF GLACIOMARINE DEPOSITS 899

FIG. 1.—A) Satellite image of the southern Victoria Land Basin in McMurdo Sound in the Antarctic continent (Part C), showing drill sites and key geographic features.
Cryogenic brine is present in pore water at the AND-2A drill site. B) Tectonic context of area in image (Part A).

coldest (polar and subpolar) regimes, related to a high propensity for may have formed during ancient ice ages of the Phanerozoic, but their
infiltration of cryogenic brine into open pore space (Dunham et al., in presence may be recorded only in diagenetic phases.
press). By contrast, higher porosity is maintained in sand bodies formed
during temperate climate intervals because the sandstones were protected BACKGROUND
from brine infiltration by enclosing mudrock units that acted as
permeability barriers (Dunham et al., in press). The observations from Geological Setting
the AND-2A core highlight the control of the brine on diagenetic patterns McMurdo Sound forms part of the southern Victoria Land Basin (VLB)
in the glaciomarine deposits. of Antarctica (Fig. 1), a trough at least 400 km long and c. 150 km wide
To broaden current understanding of the origin, nature, and distribution with a Cenozoic sedimentary fill up to 4 km thick. The VLB is the
of cryogenic brine and its impact on diagenetic patterns in glaciogenic westernmost, north–south-trending subbasin of the West Antarctic failed-
deposits, the present study examines drillcores from the Cape Roberts rift complex, which extends from the East Antarctic Craton to West
Project (CRP), acquired a short distance away from the ANDRILL drill site Antarctica (Fig. 1B; Cooper et al. 1987; Behrendt et al. 1991). The western
and within the same basin. Unlike the ANDRILL project, however, no margin of the West Antarctic Rift System is defined by the Transantarctic
pore-water samples were acquired during drilling. 18O-depleted cement Mountain Front, an extensional basement fault zone between the rising
phases similar to those encountered in the AND-2A core were interpreted Transantarctic Mountains to the west and the VLB to the east (Cooper et al.
by previous workers as recording the influence of mixtures of glacial 1987; Cape Roberts Science Team 1999). The Cape Roberts drill sites lie
meltwater and seawater (Baker and Fielding 1998; Aghib et al. 2003; immediately seaward of the mountain front (Fig. 1A; Cape Roberts Science
Bellanca et al. 2005). In light of the discovery of brine and associated Team 1999).
diagenetic phases in the AND-2A core, the diagenetic history in the CRP Tectonic evolution of the VLB has been extensively studied via seismic
cores is reassessed herein. surveys and stratigraphic drilling (Cooper et al. 1987; Brancolini et al.
This paper provides systematic documentation of the stratigraphic 1995a, 1995b; Bartek et al. 1996; Henrys et al. 2000, 2001; Hamilton et al.
distribution of diagenetic phases in the composite Oligocene–lower 2001; Barrett 2007). A seismic stratigraphic analysis of the Cenozoic
Miocene succession from CRP-1, -2/2A, and -3 cores. A robust succession integrating all available data and previously proposed schemes
paragenetic framework is developed in the context of this region’s tectonic, was reported by Fielding et al. (2008), who recognized five main phases of
paleoclimate and glacial, and burial history. Controls on diagenetic patterns VLB evolution: (1) exhumation and erosional denudation of the
related to the nature, origin, and spatiotemporal distribution of diagenetic Transantarctic Mountains to form the initial rift topography (pre–34 Ma),
fluids are assessed within the paragenetic framework. Finally, the paper (2) early rifting, in which sedimentation in rapidly subsiding subbasins
presents implications of the potential presence of the unusual diagenetic (34–29 Ma), (3) a main rift phase, in which the subbasins merged to form
fluid for comparable polar settings throughout Earth history. Similar brines one basin-centered depocenter, characteristic of a sediment wedge
900 M. YANG ET AL. JSR

FIG. 2.—Geological cross section based on

seismic surveys, showing the seaward-dipping
strata in CRP drillholes, McMurdo Sound,
Antarctica (after Naish et al. 2001).

symmetrically thickening toward the basin center (29–23 Ma), (4) a fragmented Pliocene to Quaternary sections in the cores are omitted from
subsequent phase of passive thermal-subsidence in which basin subsidence this paper when each core is described. With an overlap between the base
rate was slowed, leading to sheet-like strata that blanketed over the infilled of CRP-1 and the top of CRP-2/2A, CRP-1 and -2/2A are combined as the
rift topography (23–13 Ma), and (5) a renewed extensional phase with CRP-1/2/2A section in this study with a total penetration depth of 669.57
extensive volcanism since 13 Ma, known as the Terror Rift phase (Cooper m in cumulative depth (mcd; Florindo et al. 2005). A minor gap exists
et al. 1987; Henrys et al. 2007). between the base of CRP-1/2/2A and the top of CRP-3 (Henrys et al. 2000;
Florindo et al. 2005). An unconformity associated with the Mi-1 glacial
Stratigraphy expansion event of the East Antarctic Ice Sheet (EAIS) was noted at ~ 352
mcd (c. 24 Ma) of the CRP-1/2/2A section (Fig. 3; Fielding et al. 2000;
In the late 1990s, the CRP recovered a nearly complete stratigraphic Naish et al. 2001, 2008a; Fielding 2018). The whole composite CRP
transect (CRP-1, -2/2A, and -3 cores) through seaward-dipping, shallow succession also captures VLB basin evolution phases from the early and
marine Cenozoic strata that unconformably overlie probable Devonian main rift phases to the passive thermal-subsidence phase (Fielding et al.
sedimentary basement (Fig. 2; Cape Roberts Science Team 1998, 1999, 2008).
2000; Davey et al. 2001). The Cenozoic section in CRP-3, bounded by a
basal depositional breccia and conglomerate interval, spans from c. 34 to c. Sedimentology
31 Ma (790 to 0 m below sea floor: mbsf; Florindo et al. 2005; Galeotti et
al. 2016). CRP-2/2A penetrated a total depth of 624 mbsf, with a Based on sedimentological studies of previously acquired cores over the
continuous lower Oligocene to lower Miocene (c. 31–18 Ma) record from past four decades in the McMurdo Sound area, Fielding (2018) synthesized
624 to 27 mbsf truncated by 27 m of a fragmented Pliocene to Quaternary existing facies schemes and sequence stratigraphic models, and presented
record at the top (Wilson et al. 2000; Naish et al. 2001, 2008a; Florindo et the facies architecture and sequence stratigraphy for all cores recovered in
al. 2005). CRP-1 was drilled to only 148 mbsf, with a major hiatus McMurdo Sound. The recognized lithofacies represent an array of
separating the lower Miocene section (148–43 mbsf; c. 21–17 Ma) from a nearshore to shelfal depositional environments affected by varying degrees
fragmented Pliocene to Quaternary section (43–0 mbsf; Roberts et al. of glacial influence across the basin, ranging from open shallow marine,
1998). glaciomarine, to proglacial and subglacial deposition. Vertical stacking
The Oligocene through lower Miocene sections in CRP-1, -2/2A, and -3 patterns of the lithofacies through the Oligocene and Miocene progres-
together comprise a continuous stratigraphic record spanning from c. 34 to sively change upward from a random pattern (1456–1146 mcd) through a
c. 17 Ma with a total cumulative thickness of 1456 m (Fig. 3; Florindo et better-defined cyclic fining-upward stacking pattern (1146–996 mcd)
al. 2005), named the composite CRP succession in this study. The dominated by abundant sandstone with subordinate conglomerate, to a

!
FIG. 3.—Graphic sedimentological log of the composite CRP succession (after Florindo et al. 2005; Fielding 2018). Interpreted depositional sequences, stratigraphic
motifs, paleoenvironmental step change periods, and basin evolution phases are shown on the left side of the log (after Fielding 2018). Point-counting results showing the
percentages of porosity, cement, and detrital mud of the sandstones are shown on the right side of the log. Lithological colors correspond to mud in gray, sand in yellow,
diamictite in desert blue, and conglomerate in orange.
JSR IMPACT OF CRYOGENIC BRINE ON DIAGENESIS OF GLACIOMARINE DEPOSITS 901
902 M. YANG ET AL. JSR

TABLE 1.—Summary of stratigraphic motifs recognized in McMurdo SAMPLING AND ANALYTICAL PROCEDURE
Sound drillcores (after Fielding 2018).
To broadly capture the full range of diagenetic phases across the entire
stratigraphic record, 100 sandstone samples were selected from 41 (fourth-
Stratigraphic Motif Interpretation and fifth-order) depositional sequences, which represent the full range of
stratigraphic motifs and sequence stratigraphic systems tracts in the
1 Cold, polar glacial regime with minor meltwater
involvement in sediment dispersal (absent in the CRP composite CRP succession. Diagenetic phases were systematically
succession in this study) documented using a combination of petrographic and geochemical
2 Subpolar glacial regime with significant meltwater methods.
involvement in sediment dispersal Each sandstone sample was thin-sectioned for standard petrographic
3 High-latitude temperate glacial regimes with substantial examination, including polarized-light and cathodoluminescence (CL)
meltwater discharge by wet-based glaciers microscopy. The samples were impregnated with blue epoxy under vacuum
4 High-latitude temperate glacial regimes with more distant to facilitate determination of porosity and identification of preserved
wet-based glacier influence
texture. A combined stain of alizarin red-S and potassium ferricyanide was
5 Minimal (distal) glacial influence on sediment dispersal
6 Indirect glacial influence from ice-rafting
applied to thin sections to distinguish calcite and dolomite and to highlight
7 No glacial influence iron-rich carbonate phases (Friedman 1959). Point counting was performed
manually on all the thin sections using a Vernier scale mounted in the
mechanical stage of a standard polarization petrographic microscope.
more fully developed cyclic stacking pattern with increasing lithofacies Counts were taken at 103, 203, or 403 magnification for 300 points per
diversity and abundance of diamictite and muddy lithofacies (996–0 mcd; thin section using an evenly spaced grid that encompassed the entire thin
Fig. 3). This progressive change in stratal stacking patterns indicates section under plane-polarized (PPL) and cross-polarized (XPL) light.
successively more pronounced glacial influence following the onset of Because quartz (Q), feldspar (F), and rock fragments (R) constitute the
Antarctic glacial ice growth at c. 34 Ma (Fielding et al. 1997, 2001; Barrett major framework grains, and other detrital constituents are negligible in the
2007; Galeotti et al. 2016). Cyclical stratigraphic stacking patterns were samples, the abundance of the three major constituents (QFR) was
interpreted as a succession of depositional sequences that reflect cycles of considered to determine the modal grain composition (Folk 1980). In
glacial advance and retreat with attendant relative sea-level changes addition to describing the texture of the framework grains, the percentages
(Fielding et al. 1998, 2000, 2001). Over fifty depositional sequences were of cement, detrital mud, and porosity were also documented in each
identified throughout the composite CRP succession (summarized in sample. The CL microscopy was used to examine cement growth patterns
Fielding 2018). However, these sequences are thin (often , 10 m), severely in the thin sections and to assess qualitative variations in Mn2þ and Fe2þ.
top-truncated, and incomplete in terms of systems tracts (Catuneanu et al. An energy-dispersive X-ray spectrometer (EDX) with silicon drift detector,
2009), particularly highstand systems tracts (HSTs), owing to erosion at which is mounted on the CL stage, also aided in discrimination of
the sequence boundary associated with glacial advance, characteristic in carbonate mineralogies associated with major-element and trace-element
proximal glaciogenic settings. variations in diagenetic carbonate phases. Carbonate cement size and
Patterns in the variation of the diversity of lithofacies, completeness of morphology is described using the terminology of Folk (1959).
systems tracts, and proportion of diamictite noted in the high-frequency A full spectrum of diagenetic carbonate phases characterized via
(fourth- and fifth-order) sequences can be readily arranged into longer- petrographic methods was selected for analyses of stable carbon and
term stratigraphic styles, termed stratigraphic ‘‘motifs’’ (Fielding 2018). oxygen isotopes. Microsamples (n ¼ 34, weight ~ 30 lg) were drilled from
The seven motifs reflect fluctuations in paleoclimate regimes, ranging from polished thin-section blanks using a microscope-mounted microdrilling
cold polar to no glacial influence (Table 1; Fielding 2018). Although absent assembly. The microsamples were analyzed using a Kiel III Device in line
in the composite CRP succession, Motif 1 occurs in successions of mid- with a Finnigan MAT 253 isotope-ratio mass spectrometer at the W.M.
Miocene and younger age, recording cold, polar climate regimes similar to Keck Paleoenvironmental and Environmental Stable Isotope Laboratory of
today with minimal sediment dispersal by cold-based ice sheets. Apart the University of Kansas. Isotope values are reported in the conventional d
from Motif 7, which characterizes the basal Oligocene section without notation relative to Vienna Pee Dee Belemnite (VPDB) and Vienna
cyclicity, the other motifs recur throughout the succession (Fig. 3). The Standard Mean Ocean Water (VSMOW) for carbonate minerals and
distribution pattern of the stratigraphic motifs not only reflects highly diagenetic fluids, respectively. Analytical precision is better than 0.10%
dynamic climate and glacial conditions, but also provides the basis for and was monitored by daily analyses of National Bureau of Standards –18
understanding paleoenvironmental step change (PSC) periods during the and –19. The low-temperature calcite–water fractionation equation by Kim
Oligocene through lower Miocene (Table 2; Fig. 3; Fielding 2018). and O’Neil (1997) was used for calculation. Results were considered in a

TABLE 2.—Interpreted paleoenvironmental step change (PSC) periods with respect to basin and paleoclimate evolution in the CRP drillcores (after
Fielding 2018).

PSC Period Depth Range Interpretation

I. prior to 33.15 Ma 1456–1084 mcd High-altitude glaciation began in Antarctica associated the Oi-1 glaciation event (Miller et al. 1991), while the VLB started
rifting and was unaffected by glacial ice
II. 33.15–32.3 Ma 1084–871 mcd Early glacial ice began to grow on coastal regions adjacent to McMurdo Sound, but was unable to extend across the
Transantarctic Mountain Front into the basin
III. 32.3–24 Ma 871–352 mcd The EAIS was established and extended into the VLB in a cyclic fashion
IV. ~ 24–22.5 Ma 352–176 mcd The Antarctic climate regime shifted into a more austere state associated with the Mi-1 EAIS expansion, resulting in major
uniformities and three fragmented but unusually thick sequences
V. 22.5–17 Ma 176–0 mcd A period of cyclic growth and decay of the EAIS when the climate transitioned toward sub-polar and polar conditions and
the VLB rifting phase switched to the passive thermal-subsidence phase
JSR IMPACT OF CRYOGENIC BRINE ON DIAGENESIS OF GLACIOMARINE DEPOSITS 903

FIG. 4.—Ternary QFR plots for A) sandstone classification (Folk 1980) and B) provenance analysis (Dickinson 1985) for sandstones in the CRP succession, with data
derived from point counting. Data are plotted with respect to interpreted PSC periods of the VLB (Fielding 2018): blue squares, PSC Period I; yellow diamonds, PSC Period
II; red triangles, PSC Period III; green circles, PSC Period IV; and black crosses, PSC Period V.

context of well-established sedimentological, stratigraphic, and tectonic cement, and detrital mud contents exist with respect to systems tracts (Fig.
frameworks to yield information about the nature, origin, and spatiotem- 6).
poral history of diagenetic fluids.
Diagenetic Features
RESULTS
Compaction-Related Features.—Evidence for physical compaction
Sandstone Petrography varies down-hole with mostly point intergranular contacts at shallower
depths transitioning to noticeably more long intergranular contacts toward
Point-counting results show that while monocrystalline quartz domi-
the bottom of the composite CRP succession. No interlocking or sutured
nates framework grains across the entire succession, variations in both
grain contacts were noted, indicating minimal chemical compaction.
texture and composition of sandstones occur across the Mi-1 unconformity
Abundant grain fracturing noted on framework grain surfaces was
at ~ 352 mcd (c. 24 Ma; Figs. 3, 4). The proportion of quartz decreases
artificially introduced during thin-section preparation, which has over-
and the relative abundances of detrital feldspar and rock fragments become
printed compaction-related grain fracturing by sediment and/or glacial
more variable above the Mi-1 unconformity. Feldspars include mainly K-
loading.
feldspar and plagioclase. Rock fragments are mainly igneous in origin
(igneous rock fragments: IRF), with trace (, 1%) amounts of sedimentary
and metamorphic rock fragments. The IRF include plutonic and volcanic Low-Mg Calcite Cement.—Non-ferroan, low-Mg calcite is volumet-
rock fragments. Plutonic rock fragments disappear above the Mi-1 rically the most abundant cement throughout the succession. The calcite
unconformity (c. 24 Ma; ~ 352 mcd), such that all IRF are volcanic in occurs as equant crystals, which can be divided into three main types in
origin. Other minor detrital constituents include muscovite, zircon, and terms of size: (a) microcrystalline calcite with crystal size less than 20 lm
ferromagnesian minerals, e.g., orthopyroxene. (Fig. 7A), (b) finely crystalline calcite with crystal size ranging from 20 to
Sandstone compositions plotted on a provenance ternary diagram 100 lm (Fig. 7B), and (c) coarsely crystalline calcite with crystal size
(Dickinson 1985) indicate mainly a recycled orogenic source (Fig. 4B). generally greater than 100 lm and often exhibiting poikilotopic texture
Sandstone compositions shift with time, from predominantly sublithar- (Fig. 7C). These three types of calcite cement do not coexist and show
enites below the Mi-1 unconformity during PSC periods I through III (c. uniformly moderate to moderately dull luminescence in individual
34–24 Ma; 352–1456 mcd), to a wider range in composition from arkose samples.
to litharenite above the Mi-1 unconformity during PSC periods IV and V The microcrystalline calcite cement is common in sandstones that lack
(c. 24–17 Ma; 352–0 mcd; Fig. 4A). Sandstone texture varies with the intergranular contacts. The crystal size typically increases toward pore
stratigraphic motifs of Fielding (2018). In Motifs 5–7, the sandstones are centers, from aphanocrystalline on grain surfaces to microcrystalline at
mostly texturally submature with variable proportions of porosity (~ 0– pore centers. This cement is also present in intragranular pores of
45%) and cement (~ 0–39%) but less than ~ 2% detrital mud (Fig. 5A). skeletal grains (Fig. 7D). The finely crystalline calcite cement mainly
By contrast, the sandstones in Motifs 2–4 are texturally immature, showing occurs in mud-free sandstones with dominantly point intergranular
more detrital mud in the matrix (mostly more than 50%), and less porosity contacts. The coarsely crystalline calcite cement occurs in mud-free
(mostly less than 10%) and cement (mostly less than 10%) (Fig. 5B). sandstones with point and minor long intergranular contacts. Both the
Porosity is dominantly intergranular, with minor (less than approximately microcrystalline and finely crystalline calcite cements almost fully
equal to 10%) fracture and intraparticle porosity in framework grains occlude intergranular pore space, whereas the coarsely crystalline calcite
(altered IRF and feldspars) and in carbonate cement crystals that have cement significantly reduces both intergranular and intragranular
undergone secondary dissolution. No clear relationships between porosity, porosity to near 0%.
904 M. YANG ET AL. JSR

FIG. 5.—Photomicrographs showing textural maturity of sandstone relative to FIG. 6.—Photomicrographs of closely spaced sandstones from the same systems
stratigraphic motif (PPL). A) Texturally submature, mud-free HST sandstone with tract of a depositional sequence (lowstand/transgressive systems tract [LST/TST],
porosity of ~ 41% in Motif 6 (621.52 mcd, PSC Period III). B) Texturally immature, Motif 6, PSC Period II) illustrating spatial heterogeneity of cement distribution
mud-rich HST sandstone with porosity of ~ 1% in Motif 4 (272.81 mcd, PSC Period (PPL). A) Fully calcite-cemented (pink) sandstone with porosity of ~ 0% (1000.25
IV) mcd). B) Sandstone with porosity of ~ 33% (1001.27 mcd).

The stratigraphic distribution of the three types of calcite cement is a small to negligible part of the total cement volume in the sandstones
similar in both CRP-1/2/2A and CRP-3 sections (Fig. 8), and is correlated because of its relatively low abundance.
with burial depth. The microcrystalline calcite is limited to shallowest The ferroan dolomite cement is notably more abundant (accounting for
depths, in the upper ~ 300 mbsf of CRP-1/2/2A (0–345.42 mcd) and the ~ 20% of the cement volume) in intervals near the Mi-1 unconformity at c.
upper ~ 200 mbsf of CRP-3 (669.57–866.77 mcd). The finely crystalline 352 mcd (c. 24 Ma). This cement phase becomes less abundant (~ 0–5%)
calcite is distributed in discrete intervals of intermediate depths, ranging down-core and rarely occurs near the base of CRP-1/2/2A at 669.57 mcd.
from 295.42–655.42 mcd in CRP-1/2/2A and ~ 240–470 mbsf (906.77– The finely crystalline ferroan dolomite develops fluid inclusion-rich
1136.77 mcd) in CRP-3. The coarsely crystalline calcite is distributed rhombohedral crystals (Fig. 9A). Strong mineral color distinctions are
respectively in the deepest part of CRP-1/2/2A, ranging from ~ 545.42 to easily visible between the cloudy, sometimes rusty, fluid-inclusion-rich
core and clear layers in individual crystals, but some inclusion-rich layers
622.42 mcd, and in nearly the entire CRP-3 section, ranging from ~ 250 to
have undergone secondary dissolution, creating minor intracrystalline
690 mbsf (916.77–1356.77 mcd).
porosity (Fig. 9B).
The microcrystalline ferroan dolomite phase occurs as aggregates at
Ferroan Dolomite.—Ferroan dolomite occurs in various intervals of shallow depths (~ 23 to 68 mcd) in CRP-1/2/2A (Figs. 8, 9C) and is
sandstones that lack compaction as finely crystalline (16–62 lm) or associated with pyrite. Individual crystals have a brownish core and a
microcrystalline (, ~ 20 lm) cement. Determination of ferroan dolomite colorless thin rim. Their petrographic characteristics are consistent with the
is aided by EDX analyses of finely crystalline crystals, which show carbonate cement described from the upper ~ 100 mcd of CRP-1/2/2A by
elevated (albeit variable) Mg and Fe concentrations compared to non- Baker and Fielding (1998). Thin brownish rims of microcrystalline ferroan
ferroan, low-Mg calcite. In thin section, the ferroan dolomite has dull to dolomite around framework grains are also present in several intervals near
non-luminescence under CL. Overall, ferroan dolomite cement constitutes the bottom of CRP-3 between 1000 mcd to 1456 mcd (Fig. 9D).
JSR IMPACT OF CRYOGENIC BRINE ON DIAGENESIS OF GLACIOMARINE DEPOSITS 905

FIG. 7.—Photomicrographs of non-ferroan low-Mg calcite cement phases. A) Microcrystalline calcite cement (stained pink) developed in between floating sand grains
(PPL, 335.33 mcd, LST/TST, Motif 4, PSC Period IV). B) Finely crystalline calcite mosaic cement (stained pink) completely filling the pore space (PPL, 469.27 mcd, LST/
TST, Motif 4, PSC Period III). C) Coarsely crystalline calcite cement displaying poikilotopic texture (XPL, 662.89 mcd, HST, Motif 6, PSC Period III). D) Microcrystalline
calcite filling foraminifer chambers (XPL, 255.42 mcd, HST, Motif 3, PSC Period IV).

Other Cement Phases.—Zeolite is present in low abundances (less mineralogy of the clay-mineral rims has been extensively demonstrated by
than 5%) as pore-lining cement in sandstone samples from two parts of the previous workers as authigenic smectite (Ehrmann 2001; Wise et al. 2001;
succession (Fig. 8), ranging from 525 to 669 mcd in CRP-1/2/2A, and Setti et al. 2001, 2004; Ehrmann et al. 2005; Priestas and Wise 2007).
from 218 to 285 mbsf (884–951 mcd) in CRP-3, respectively. The depths In addition, very minor amounts of pyrite cement are present throughout
of the first down-core occurrence of zeolite cement roughly coincide with the succession as aggregates of cubic or spherical crystals (up to ~ 10 lm)
the first occurrence of the coarsely crystalline calcite cement in both CRP- fringing single or multiple framework grains (Fig. 10C), but the pyrite
1/2/2A and -3 sections. Zeolite crystals range from tabular to cubic forms becomes rarer down-core.
(Fig. 10A) with very low birefringence to almost isotropic under crossed
polarizers. Previous X-ray diffraction analyses have revealed that the Altered Framework Grains.—Feldspars and volcanic rock fragments
zeolite minerals are of the heulandite–clinoptilolite group (Neumann and generally show increasing degrees of diagenetic alteration in terms of
Ehrmann 2000, 2001). The distinctive ‘‘coffin-shaped’’ crystals were also dissolution and replacement with depth. Dissolution created moldic
imaged via scanning electron microscope by Priestas and Wise (2007). The porosity that is sometimes occluded by calcite cement. Some feldspars
cement appears to preferentially surround grains in mud-free, porous are replaced by minerals such as albite (Fig. 11A), pyrite (Fig. 11B), or
sequences of Motif 6. calcite (Fig. 11C). Volcanic rock fragments above the Mi-1 unconformity
Clay-mineral rims are prevalent only below ~ 350 mbsf of the CRP-3 (c. 24 Ma; c. 352 mcd) show less devitrification and/or no alteration (Fig.
section (below 1019 mcd of the composite CRP succession; Fig. 8). They 11D) compared to those in deeper parts of the succession.
occur as fibrous coatings around detrital grains (Fig. 10B). Coatings
noticeably increase in abundance and thickness (up to ~ 10 lm) down- Summary of Stratigraphic Distribution of Diagenetic Features.—
core. They are most common in mud-free sandstones with high primary Overall, no clear pattern of the stratigraphic distribution of carbonate
porosities, notably in all systems tracts of sequences in Motifs 6 and 7. The phases can be identified in high-frequency depositional sequences (Fig. 6).
906 M. YANG ET AL. JSR

FIG. 8.—Stratigraphic distribution of diagenetic

phases in the composite CRP succession in a
chronostratigraphic, paleoclimate, and tectonic
framework (after Florindo et al. 2005; Fielding
2018).
JSR IMPACT OF CRYOGENIC BRINE ON DIAGENESIS OF GLACIOMARINE DEPOSITS 907

FIG. 9.—Photomicrographs of ferroan dolomite (Do) cement phases (PPL). A) Fluid-inclusion-rich, finely crystalline ferroan dolomite cement (unstained) (450.51 mcd,
LST/TST, Motif 3, PSC Period III), showing an inclusion-rich core and a limpid rim. B) Ferroan dolomite rhombs showing partially dissolved layers and creating minor
secondary porosity (563.05 mcd, LST/TST, Motif 6, PSC Period III). C) Microcrystalline ferroan dolomite aggregates occurring with pyrite (Py) (42.04 mcd, LST/TST, Motif
3, PSC Period V). D) Thin overgrowth of microcrystalline ferroan dolomite on detrital grains (1116.62 mcd, HST, Motif 7, PSC Period I).

Instead, most relationships correspond to depth. Low-Mg calcite cement Stable-Isotope Compositions of Calcite Cements
shows distinct trends in both CRP-1/2/2A and -3 sections, with crystal size
Selection of the 34 microsamples for analyses of stable carbon and
and abundance increasing with increasing depth (Fig. 8). Generally,
oxygen isotopes was based on the morphologies of the calcite cement, four
microcrystalline calcite (, 20 lm) in the upper part of both sections microcrystalline, six finely crystalline, and 23 coarsely crystalline cement
(, ~ 300 mcd in CRP-1/2/2A and , ~ 200 mbsf in CRP-3) gives way to samples. A bivalve shell was also analyzed. Fibrous aragonite and/or
finely (20–100 lm) and coarsely (. 100 lm) crystalline calcite (. ~ 250 bladed calcite cements may have been mixed with the bivalve shell calcite
mcd in CRP-1/2/2A and . ~ 240 mbsf in CRP-3) with increasing depth. during sampling. Two of the microsamples, one from the microcrystalline
Ferroan dolomite cement is best developed near significant unconformities, calcite at 238.07 mcd in CRP-1/2/2A (Fig. 12A) and the other from the
near the truncated top and around the Mi-1 unconformity at ~ 352 mcd (c. coarsely crystalline calcite at 590.86 mbsf in CRP-3 (1257.63 mcd; Fig.
24 Ma) in CRP-1/2/2A. Except for a trace amount in several intervals of 12B), were drilled from fracture fills.
intermediate depths, ferroan dolomite is absent in CRP-3, which lacks Oxygen isotope compositions range from –19.5% to –4.8%, whereas
major unconformities. carbon isotope compositions range from –30.2% to –1.3%. A cross-plot
of d18O and d13C values (Fig. 13) shows that isotope composition varies
By contrast, a recognizable pattern is evident with regard to the
with cement morphology. Microcrystalline and finely crystalline calcite
distribution of non-carbonate phases, namely smectite rims and zeolite cements show a wide range of d18O values (–14.8% to –4.8%) and lower
cement (Fig. 8). Clay rims are restricted in sequences of Motifs 6 and 7 d13C values (, –10.0%). The d18O values of coarsely crystalline calcite
near the base of CRP-3 only, whereas zeolite cement occurs exclusively in cement are less variable, ranging from –19.5 to –11.6%. The majority of
Motif 6 sequences in CRP-1/2/2A and -3. Clay rims and zeolite occur in the d13C values of coarsely crystalline calcite cement are higher than
mud-free sandstones with abundant intergranular porosity. –10.0%, ranging from –8.5 to –1.3%, except for four samples with low
908 M. YANG ET AL. JSR

d13C values (as low as –30.2%). The bivalve shell has a composition
distinct from cements, d18O ¼ –4.9% and d13C ¼ –5.1%. The d18O values
plotted against the cumulative depth show trends that decrease down-core
in CRP-1/2/2A and -3, respectively indicated by linear regression (Fig.
14A). In contrast, the d13C values are scattered throughout the CRP-1/2/2A
and -3 sections (Fig. 14B).

PARAGENESIS

Evidence used to reconstruct paragenesis includes the degree of physical

compaction during precipitation of the diagenetic phases as indicated by
intergranular contacts and crosscutting relationships of the array of the
diagenetic features.
Ferroan dolomite and minor pyrite are the earliest diagenetic minerals,
formed before physical compaction, as they appear to surround framework
grains lacking intergranular contacts. These phases are associated with
significant erosional (hiatal) surfaces, because they are prominent near the
truncated section top and around the Mi-1 uniformity at 352 mcd (c. 24
Ma). Deeper in the section, where evidence for physical compaction is
apparent, ferroan dolomite (or pyrite) is overlain by either smectite rims,
zeolite, or low-Mg calcite cements, depending on stratigraphic positions.
Smectite rims that are present only in the basal part (lowermost Oligocene)
of CRP-3 are overlain by zeolite cement that evidently formed at a later
stage (Fig. 15). Where smectite rims are absent, zeolite cement directly
overgrows detrital grains (Fig. 10A).
The final and most widespread process is related to emplacement of
low-Mg calcite cement phases. These calcite cements grow atop the phases
described above where they are present. Where ferroan dolomite, pyrite,
zeolite, and smectite phases are absent, microcrystalline or finely
crystalline phases of low-Mg calcite cement grow directly atop detrital
grains. As described above, the microcrystalline and finely crystalline
calcite phases are generally distributed in discrete intervals from shallow to
intermediate depths of CRP-1/2/2A (0–610 mbsf; 0–655.42 mcd) and
CRP-3 (0–470 mbsf; 906.77–1136.77 mcd). Smectite rims and/or zeolite
cements, present in the lower parts of both CRP-1/2/2A and -3, are
overgrown by coarsely crystalline calcite cement (Fig. 15).
Altered labile framework grains are noted throughout the entire
succession. In some cases, all the cements have been observed to develop
around ghost detrital grains that have been partially to fully dissolved,
indicating that dissolution occurred during or after the formation of the
cements. By contrast, growth of coarsely crystalline calcite as poikilotopic
texture into moldic porosity left by grain dissolution suggests that
cementation of calcite continued after grain dissolution (Fig. 16).

DISCUSSION

Diagenetic History

The paragenetic sequence provides the basis for discussion of the

diagenetic history and associated diagenetic fluids during the deposition of
the composite CRP succession (Fig. 17). The burial history of the CRP
sections indicates that diagenesis occurred at depths , 1.5 km and
temperatures , 608C, possibly even , 408C (Wise et al. 2001). If the
burial temperature exceeded 608C, then the authigenic smectite rims would
have begun to convert to illite (Bjørlykke and Aagaard 1992). Higher
burial temperatures would have also favored development of quartz
overgrowths (Bjørlykke and Egeberg 1993) and transformation of
FIG. 10.—Photomicrographs (PPL) showing A) pore-lining, microcrystalline
zeolite cement (662.89 mcd, HST, Motif 5, PSC Period III), B) smectite rims clinoptilolite (Iijima 1988), but none of these features are present.
(1222.69 mcd, Motif 7, PSC Period I), and C) pyrite cement fringing quartz grain Moreover, chemical compaction is minimal and no thermal alteration of
(573.34 mcd, HST, Motif 5, PSC Period III). organic matter has been observed (Wise et al. 2001). Chemically unstable
constituent framework grains in the Miocene section have undergone only
modest diagenetic modification compared to more extensive modification
in deeper parts of the succession, allowing preservation of grains as
reactive as volcanic glass. This preservation is consistent with slow
JSR IMPACT OF CRYOGENIC BRINE ON DIAGENESIS OF GLACIOMARINE DEPOSITS 909

FIG. 11.—Photomicrographs showing feldspar grains replaced by A) albite (arrow; PPL, 563.05 mcd, LST/TST, Motif 6, PSC Period III), B) pyrite (arrow; PPL, 563.05
mcd, LST/TST, Motif 6, PSC Period III), and C) calcite (arrow; XPL, 892.58 mcd, LST/TST, Motif 6, PSC Period II). D) Variably altered volcanic glass (PPL, 272.81 mcd,
HST, Motif 4, PSC Period IV).

diagenetic reaction rates in a low-temperature environment (Fielding et al. brine. The early ferroan dolomite and pyrite phases, prominent around
2012; Dunham et al., in press). Recorded seafloor temperatures at CRP-2/ hiatal surfaces, may have formed in the shallow-burial environment as a
2A and CRP-3 are near the seawater freezing point, and bottomhole consequence of prolonged slow deposition and bacterially mediated sulfate
temperatures were 17.28C at 624 mbsf in CRP-2/2A and 23.78C at 870 reduction (Berner 1984; Mortimer et al. 1997). Zeolite cement, prominent
mbsf in CRP-3, giving average present-day geothermal gradients of in mud-free, porous sandstones in Motif 6 of both CRP-1/2/2A and -3, is a
24.08C/km in CRP-2/2A, and 28.58C/km in CRP-3 (Bücker et al. 2000, common burial phase that forms from the interaction of alkaline fluids
2001). These relationships indicate a maximum burial temperature for the (e.g., seawater or brine) and volcaniclastic sediment (Passaglia et al. 1990;
succession of c. 408C. Dickinson and Grapes 1997; Hall 1998). Zeolite cement immediately
One exception to the above that should be noted is the smectite rims that overlain by calcite cement in Antarctic soils has been suggested as an
are present only in the lowermost Oligocene of the CRP-3 section. The indicator of brine formation under freezing conditions (Dickinson and
authigenic smectite was interpreted to be of low-temperature (less than Grapes 1997). In the both CRP-1/2/2A and -3 sections, the intervals of co-
608C) hydrothermal origin and related to initial basin rifting (34–29 Ma), occurring zeolite and coarsely crystalline calcite cements could indicate a
because this phase is absent in other nearby cores of similar burial depths diagenetic front of progressive precipitation from brine (Fig. 8).
and/or ages in the VLB (Setti et al. 2001, 2004, 2009). The CRP Previous workers called upon glacial meltwater to account for the low
succession is located near the Transantarctic Mountains Front faults and d18O values of low-Mg calcite cements in the CRP cores (Baker and
overlies the depositional breccia. During the early rifting phase, rapidly Fielding 1998; Aghib et al. 2003; Bellanca et al. 2005). Numerous glacial
accumulating lowermost Oligocene sediments are interpreted to have been advance–retreat cycles recorded in the high-frequency depositional
influenced locally by hydrothermal fluids, resulting in smectite formation sequences generally imply batches of 18O-depleted glacial meltwater
and development of moldic porosity in labile framework grains. production. Glacial meltwater would presumably have highly variable d18O
The most likely sources of diagenetic fluids responsible for the other compositions assuming formation under different climate regimes and
cement phases in this setting are glacial meltwater, seawater, and cryogenic subsequent mixing with varying proportions of local seawater. In any case,
910 M. YANG ET AL. JSR

FIG. 12.—Photomicrographs showing calcite-filled fractures. A) A fracture

(arrow) partially filled by microcrystalline calcite (PPL, 238.07 mcd, HST, Motif 4,
FIG. 13.—Cross-plot diagram of d18O and d13C values of the bivalve calcite and
PSC Period IV). B) A fracture completely filled with coarsely crystalline calcite
calcite cements through the composite CRP succession. Empty symbols denote data
(arrow) (XPL, 1257.63 mcd, Motif 7, PSC Period I).
from CRP-1/2/2A, and solid symbols denote data from CRP-3.

effective mixing and infiltration into the subsurface is unlikely due to which the calcite precipitated follow the geothermal gradients of both
density differences. If glacial meltwater were added gradually and cement sections. If a seafloor temperature of –1.958C is assumed (Bücker et al.
precipitation occurred continuously, the resultant stratigraphic distribution 2000, 2001) and the low-temperature calcite–water fractionation equation
of d18O values of the calcite cements would be more random, not strongly of Kim and O’Neil (1997) is applied, results indicate that the d18O values
correlated with depth (Fig. 18). Furthermore, glacial meltwater is of pore water (d18Ow) from which the diagenetic calcite precipitated fall
undersaturated with respect to CaCO3, calling into question the drive for between approximately –19% and –11% VSMOW through both sections
carbonate precipitation at cold temperatures. Such complications make (Fig. 18). These modeled d18Ow values are significantly lower than those
glacial meltwater involvement difficult to justify in the context of determined from pore-water measurements in the AND-2A core. Lower
similarities to the AND-2A core, in which the cements have been modeled d18Ow values of the brine compared to those at the AND-2A site
demonstrated to have precipitated from cryogenically formed brine may reflect a number of factors, including local variation in the cryogenic-
(Fielding et al. 2012; Staudigel et al. 2018). Not only are the calcite brine formation process or increased levels of isotopic exchange with
cements identical petrographically, but they show similar down-core trends volcanogenic materials at CRP sites.
in morphology and 18O-depleted isotope compositions (Figs. 8, 18). Given that these modeled values are tied to assumptions regarding
Therefore, the most parsimonious explanation suggests that carbonate precipitation temperature, precipitation temperatures were modeled using
cement in the CRP cores precipitated from 18O-depleted, cryogenically AND-2A brine d18Ow values (–11 to –6% VSMOW; Fig. 18). The
formed brine. modeled temperature profiles show higher geothermal gradients, 468C/km
As observed in AND-2A, calcite-cement data show linear trends of and 408C/km at CRP-1/2/2A and -3 sites respectively, than current-day
decreasing d18O value with increasing depth in both CRP-1/2/2A and -3, geothermal gradients. Elevated geothermal gradients are possible (Bücker
which lie parallel to the local geothermal gradient (Fig. 18). Precipitation et al. 2000, 2001), and may be related to the exhumation and tilting of the
temperatures can therefore be estimated by assuming that temperatures at CRP strata during the inception of the renewed rift phase beginning in the
JSR IMPACT OF CRYOGENIC BRINE ON DIAGENESIS OF GLACIOMARINE DEPOSITS 911

FIG. 14.—Depth profiles of A) d18O and B) d13C values of calcite through the CRP succession. Negative correlation between d18O of the cements and depth in both CRP-1/
2/2A and -3 sections is indicated by Pearson’s r values and low probabilities (p) of the pattern being random. The d13C values, in contrast, are randomly distributed along
depth in both sections.

mid-Miocene (c. 13 Ma; Cooper et al. 1987; Henrys et al. 2007). However, calcite cements in the CRP succession to the presence of cryogenic brine is
both temperature profiles lie at temperatures 20 to 408C higher, indicating the most parsimonious explanation, as it removes the need to invoke fluid
additional burial of hundreds of meters of sediments on top of both sources and processes that were not present at AND-2A to explain a nearly
sections. This scenario is unlikely in this shallow marine setting which has identical suite of petrographic phases.
been affected by numerous Neogene glacial advance–retreat cycles (Wise
et al. 2001). Therefore, the isotope modeling results indicate that calcite Timing of Brine Formation
cements precipitated from low d18Ow values of brine along the local As discussed above, the two stratigraphic trends of decreasing d18O
geothermal gradient, and/or at slightly higher temperatures at CRP sites. value of calcite cements with depth strongly argue for calcite precipitation
Whatever the explanation, attributing the low d18O values of low-Mg from cryogenic brine at temperatures closely parallel to the geothermal
912 M. YANG ET AL. JSR

FIG. 15.—Crosscutting relationship showing a sequence of diagenetic phases, FIG. 16.—Photomicrograph showing that coarsely crystalline calcite postdates
with smectite rims overgrown by zeolite cement. Remaining pore space is filled by smectite rims and dissolution of framework grains as intergranular and intragranular
coarsely crystalline calcite cement (pink) (PPL, 1018.85 mcd, HST, Motif 5, PSC cement, resulting in complete occlusion of pore space (XPL, 1056.07 mcd, HST,
Period II). Motif 5, PSC Period II).

gradient in both CRP-1/2/2A and -3 sections (Fig. 18). Both sections show clumped-isotope data from AND-2A indicated that the bulk of the calcite
similar trends in cement morphology and increases in crystal size with cements formed over a discrete period of time, likely during a period of
depth (Figs. 8, 18). The preservation of these trends in sections that were pronounced formation of cryogenic brine (Staudigel et al. 2018). When
once stacked atop one another suggests that the calcite precipitated after considered in a chronostratigraphic context, the clumped-isotope temper-
tectonic exhumation and tilting during the renewed rifting phase beginning atures suggested that brine formation may have been linked to a period of
at c. 13 Ma, namely when the tops of CRP-1/2/2A and -3 sections were at pronounced cooling that is represented by an unconformable surface in
or near their present locations on the seafloor. The degree of erosion of the AND-2A after the MMCO (Staudigel et al. 2018).
section tops is unknown. The exhumation process along with subsequent Based on regional climate reconstructions and data from drillcores, we
cycles of glacial erosion eventually led to the major amalgamated hiatus at infer that a large amount of brine was formed during the interval c. 13–10
the tops of both sections. Ma when the southern VLB was periodically glaciated by expanded, cold-
Over the last 13 Ma, climate regimes and ice-sheet behavior have been based Antarctic ice sheets. During this period, ice shelves extended across
highly dynamic with numerous glacial advance–retreat cycles in the marine the southern VLB, providing the requisite conditions for brine formation
realm of the southern VLB (Naish et al. 2008b; McKay et al. 2009). over a large region. The brine eventually sank and infiltrated into the
Following the mid-Miocene Climatic Optimum (MMCO) at c. 17–15 Ma, subsurface, leading to widespread carbonate cementation. A period of
a gradual cooling began at c. 14–13 Ma, known as the Miocene Climatic brine formation is in line with the timing of climate deterioration
Transition (MCT; e.g., Flower and Kennett 1994; Holbourn et al. 2014). associated with the MCT as recorded by the stratigraphy of McMurdo
The MCT led to the establishment of cold-based EAIS at least at high Sound (Naish et al. 2008b; McKay et al. 2009), seismic profiles of the
altitudes in the Transantarctic Mountains (Lewis et al. 2007). However, it Ross Sea shelf (De Santis et al. 1995; Bart 2003), and the far-field marine
was at c. 13 Ma that substantial cooling triggered periodic expansions of d18O record (e.g., Mi glaciations; Miller et al. 1991). Although the cold
both cold-based EAIS and West Antarctic Ice Sheet (WAIS) into the polar climate regime during the brine formation at c. 13–10 Ma may not
southern VLB (Naish et al. 2008b; McKay et al. 2009), which persisted have been as austere as the Quaternary, it provides a time slice when the
through c. 13–10 Ma (Wilson et al. 2012). The austere period was then Antarctic ice sheets were sufficiently cold to expand and produce
ameliorated by extended warmer climate dominated by ice-shelf and open- cryogenic brines along the continental shelf. In short, cryogenic brine is
water conditions throughout the rest of the late Miocene (Naish et al. a longstanding feature of the McMurdo Sound region.
2008b). The warmth peaked in the early and middle Pliocene (5–3 Ma),
during which the VLB was mostly ice free (e.g., Crowley et al. 1996). The
CONCLUSIONS
late Pliocene cooling and Pleistocene glaciations ultimately established the
current ‘‘deep freeze’’ regime of Antarctica (Webb et al. 1984). The Cenozoic succession from the CRP drillcores in McMurdo Sound,
Requisite climate conditions for potential timing of widespread brine Antarctica, serves as an excellent example that demonstrates the
formation may have been in place during two periods dominated by complexity of diagenetic impact on siliciclastic deposits from glaciomarine
repeated expansions of cold-based EAIS and WAIS across the southern settings:
VLB. The brine that currently resides beneath the eastern end of the Taylor
Valley is suggested to result from changes in sea level and subsequent (1) Textural maturity and primary porosity of glaciomarine sandstones
marine intrusion linked to climate variation since the Last Glacial are strongly correlated to paleoclimatic regimes, known as
Maximum (Mikucki et al. 2015), when the cold polar regime prevailed stratigraphic motifs in this study. Sandstones deposited during
in the Pleistocene. As the cold-based Antarctic ice sheets expanded over periods of minimal to distal glacial influence, such as the
the Antarctic continental shelf, seawater that was trapped in continental- stratigraphic Motifs 5–7 in the composite CRP succession, are
margin troughs (e.g., the VLB) became highly concentrated as brine due to expected to be texturally more mature and maintain high primary
progressive freezing and limited sub–ice-shelf melting. Stable- and porosity. By contrast, sandstones tend to be texturally immature with
JSR IMPACT OF CRYOGENIC BRINE ON DIAGENESIS OF GLACIOMARINE DEPOSITS 913

FIG. 17.—Diagenetic history of the composite CRP succession. A) Initial rifting of the VLB caused local hydrothermal activity and the growth of smectite rims that are
exclusively concentrated in the bottom half of the CRP-3 section. B) Continuous deposition in CRP-3 with few major breaks in sedimentation. Only minor amounts of ferroan
dolomite and pyrite formed by sulfate reduction of buried seawater around unconformities. C) During the deposition of sediments in CRP-1/2/2A, the Mi-1 glaciation (c. 24
Ma) caused a major unconformity, around which ferroan dolomite (and minor pyrite) is concentrated due to prolonged slow sedimentation and sulfate reduction of buried
seawater. D) Significant cooling of Antarctica led to widespread brine formation in the southern VLB. This event took place after exhumation of the CRP strata, and resulted
in minor zeolite cement and abundant calcite cement which increases in crystal size with depth in CRP-1/2/2A and -3 sections.

low primary porosity because of more intense glacial erosion and is negatively correlated with burial depth, indicative of widespread
clay infiltration, such as the stratigraphic Motifs 2–4 in the CRP brine formation over a short time interval.
succession. (3) When considered in a chronostratigraphic context, brine and the
(2) However, glaciomarine sandstones are subject to diagenetic resultant diagenetic patterns contribute to better understanding of
modification by carbonate-saturated brine, cryogenically formed paleoclimate evolution and glacial processes. In the southern VLB,
during significant cooling and ice-sheet expansion, leading to the timing of brine formation is linked to a major climate
unique diagenetic patterns. Not only does zeolite cement precipitate deterioration of Antarctica at c. 13–10 Ma after the exhumation of
from the brine under freezing conditions, but pervasive calcite the CRP strata associated with the initiation of renewed basin rifting.
cement also forms as the brine infiltrated, resulting in strong Overall, diagenetic patterns studied in the context of sequence
porosity heterogeneity in the glaciomarine sandstones. The calcite stratigraphy help evaluate diagenetic controls on glaciomarine deposits
cement increases in crystal size with increasing depth. Geochem- and provide a fuller understanding of a region’s paleoclimate and glacial
ically, the calcite cement has an 18O-depleted isotopic signature that history. Potential presence of brine can be fingerprinted by strongly 18O-
914 M. YANG ET AL. JSR

FIG. 18.—Isotope modeling using d18O values of diagenetic calcite and modern-day geothermal gradients (Bücker et al. 2000, 2001) from CRP-1/2/2A and -3 sections.
Solid symbols for d18O plots denote data derived from this study. Additional data are bulk-rock values compiled from Aghib et al. (2003) in open diamonds and Bellanca et al.
(2005) in open circles. The blue-filled trends define the range of diagenetic calcite compositions showing two decreasing slopes along both sections. Modeled pore-water
values assuming precipitating temperatures along local geothermal gradients show a relatively constant trend (blue dashed lines) in both sections. Modeled precipitation
temperature profiles assuming AND-2A brine d18Ow values (–11 to –6% VSMOW; Frank et al. 2010) show steeper geothermal gradients and higher temperatures in both
sections.

depleted diagenetic carbonates, and should be considered in diagenetic BART, P.J., 2003, Were West Antarctic Ice Sheet grounding events in the Ross Sea a
evaluation of ancient glaciogenic deposits of similar settings. consequence of East Antarctic Ice Sheet expansion during the middle Miocene?: Earth
and Planetary Science Letters, v. 216, p. 93–107.
BARTEK, L.R., HENRYS, S.A., ANDERSEN, J.B., AND BARRETT, P.J., 1996, Seismic stratigraphy
ACKNOWLEDGMENTS of McMurdo Sound, Antarctica: implications for glacially influenced early Cenozoic
eustatic change?: Marine Geology, v. 130, p. 79–98.
This research was supported by National Science Foundation (NSF) Grant BEHRENDT, J.C., LEMASURIER, W.E., COOPER, A.K., TESSENSOHN, F., TREHU, A., AND
PLR-1341390 to T.D. Frank and C.R. Fielding. The Department of Earth and DAMASKE, D., 1991, The West Antarctic rift system: a review of geophysical
Atmospheric Sciences at the University of Nebraska-Lincoln is thanked for investigations: Antarctic Research Series, v. 53, p. 67–112.
providing facility support. We are grateful to the Alfred Wegener Institute for BELLANCA, A., AGHIB, F., NERI, R., AND SABATINO, N., 2005, Bulk carbonate isotope
stratigraphy from CRP-3 core (Victoria Land Basin, Antarctica): evidence for Eocene–
Polar and Marine Research (AWI) for supporting sample collection. Justin
Oligocene palaeoclimatic evolution: Global and Planetary Change, v. 45, p. 237–247.
Ahern assisted with drafting the lithostratigraphic column. We thank Brenda BERNER, R.A., 1984, Sedimentary pyrite formation: an update: Geochimica et
Bowen, Kitty Milliken, and Sadoon Morad, whose thoughtful reviews helped to Cosmochimica Acta, v. 48, p. 605–615.
improve the manuscript. BJØRLYKKE, K., AND AAGAARD, P., 1992, Clay minerals in North Sea sandstones, in
Houseknecht, D.W., and Pittman, E.D., eds., Origin, Diagenesis, and Petrophysics of
Clay Minerals in Sandstones: SEPM, Special Publication 47, p. 65–80.
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