Designation: E 848 – 94 (Reapproved 2000)

Standard Guide for

Safety and Health Requirements Relating to Occupational
Exposure to Water-Insoluble Chromates1
This standard is issued under the fixed designation E 848; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.

INTRODUCTION

This guide is intended to provide guidance in the safe handling of certain chromate compounds that
are suspected to be carxcinogenic in man (1-8).2 Precautions contained herein are believed to protect
against possible carcinogenicity, and will also be sufficient to obviate any acute health hazards except
where skin hypersensitivity is a factor. Other hazards are considered and discussed.
The time-weighted average (TWA) permissible exposure limit (PEL) specified in this guide are
based on studies evaluated by the American Conference of Government Industrial Hygienists
(ACGIH) (9). Epidemiological studies of the chromate producing industry have indicated that
observed adverse health effects were associated with environmental levels and hygiene procedures
considerably less exacting than those recommended here (see Appendix X1).
Hygiene controls and medical surveillance measures have been chosen to protect workers,recog-
nizing that the potential for exposure will vary widely from industry to industry and between one
location and another, depending on the compounds handled, scale of operations, kind of process, and
physical conditions.
The key to maintaining chromate levels below the PEL is through implementation of cost effective
engineering controls augmented as necessary by personal protective equipment, or work practice
controls, or both. The choice of methods should depend upon the factors involved in each specific
situation.
Biological monitoring is also recommended for lead chromate (see 7.4).
All applicable federal, state, county and local regulations must be complied with when this guide
is used.

1. Scope volatile chromyl compounds; (e) any trivalent chromium

1.1 This guide covers control procedures for the safe pro- compound; or (f) elemental chromium. Omission of said
duction, storage, transportation, and handling of only the compounds or classes of compounds should not be construed to
hexavalent chromium compounds found in Table 1 and their mean that they may be handled without due regard to their
various hydrates, and mixtures of coprecipitates of the same particular physical, chemical, and toxicological hazards (9, 10,
regardless of crystalline form. 11).
1.2 This guide is not intended to cover ( a) such “soluble” 1.3 The chromate ion, CrO4−2, depending upon the acidity,
chromates as chromates of sodium, potassium, magnesium, or complexes to form di-, tri-, and higher polychromates; hence,
ammonium; (b) soluble bichromates; (c) chromic acid; (d) the chromates listed in Table 1 may contain mixtures of
polychromates, depending on the method of isolation and end
use.
1
This guide is under the jurisdiction of ASTM Committee D1 on Paint and 1.4 This standard does not purport to address all of the
Related Coatings, Materials, and Applications and is the direct responsibility of safety concerns, if any, associated with its use. It is the
Subcommittee D01.22 on Health and Safety.
Current edition approved Aug. 15, 1994. Published October 1994. Originally responsibility of whoever uses this standard to consult and
published as E 848 – 82. Last previous edition E 848 – 85 (1993).
2
The boldface numbers in parentheses refer to the references at the end of this
guide.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

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 E 848 – 94 (2000)
establish appropriate safety and health practices and deter- 4. Significance and Use
mine the applicability of regulatory limitations prior to use. 4.1 This guide includes chromates that are not readily
(For more specific precautionary information see Section 5.) soluble in water and that have water solubilities (Chromate
ION) within the range of the more soluble calcium chromate
2. Referenced Documents
and the much less soluble lead chromate. The major occupa-
2.1 ANSI Standards: tions involving potential exposure to insoluble chromates are in
Z87.1 Practice for Occupational and Educational Eye and roasting of chromite ore, the manufacture of chromate pig-
Face Protection3 ments, the manufacture of coatings containing chromate pig-
Z88.2 Practices for Respiratory Protection3 ments, and spray painting with these coatings. There is
Z129.1 Precautionary Labeling for Hazardous Industrial insufficient evidence to conclude that trivalent chromium
Chemicals3 compounds are carcinogenic.
2.2 OSHA Standards:
29 CFR 1910.20 Access to Records4 5. General Requirements
29 CFR 1910.1200 Hazard Communication4 5.1 Environmental Levels:
29 CFR 1910.134 Respiratory Protection4 5.1.1 The following guide is designed to protect the health
29 CFR 1910.1025 Lead4 and safety of workers for an 8 to 10-h workday, 40-h
2.3 NIOSH Publications: workweek, over a working lifetime. The PEL can be met by
“Certified Equipment,” HEW Publication No. 76-1454 techniques and controls that reduce employee exposure below
“Recommended Industrial Ventilation Guidelines,” January the applicable safe limit. These controls must be reliable.
1976, HEW Publication No. 76-1624 Permissible exposure limits are based on the 1985 ACGIH
“Criteria for a Recommended Standard Chromium (VI),” recommended Threshold Limit Values (TLV) for chromates of
HEW Publication No. 76-1294 lead and zinc and for chromite-ore processing (12).5
5.1.2 PEL—Occupational exposure to any of the com-
3. Terminology
pounds listed in Table 1 shall be controlled to a TWA of 0.05
3.1 Definitions of Terms Specific to This Standard: mg/m3 (as Chromium) for an 8-h workday.
3.1.1 exposure area—buildings and exterior locations 5.1.3 At least one full-shift (80 % of the shift length)
where insoluble chromates may be present as airborne particu- personal sample should be taken for each job classification and
lates in excess of the concentrations specified in 5.1.2, or where each work area involving insoluble chromates. These samples
there is a likelihood of skin contact with chromate containing shall be representative of a monitored employee’s regular daily
dust. exposure to insoluble chromates, and may be used to represent
3.1.2 insoluble—a relative term to distinguish the low-water the exposure of all employees in that job assignment. One
solubility of the chromates listed in Table 1 from the much sample may not be sufficient for an adequate characterization.
more water-soluble chromates of sodium, potassium, and For further guidance and appropriate control objectives see 5.6,
ammonia. The solubilities of lead chromates and calcium 6.2, and 7.3.
chromate are typical of the lower and upper solubilities of the 5.2 Medical Surveillance:
class (see Section 6). 5.2.1 Examinations—Individuals who are currently, or who
are expected to be employed in exposure areas (see 3.1) shall
be given preplacement and annual medical examinations that
3
Available from American National Standards Institute, 1430 Broadway, New shall include, but not necessarily be limited to the following:
York, NY 10018. 5.2.1.1 Work History, to elicit information on all past
4
Available from Superintendent of Documents, U.S. Government Printing
Office, Washington, DC 20402. exposures to any hexavalent chromium compounds or other
toxic substances, particularly those affecting lung function.
TABLE 1 Examples of Some Hexavalent Chromium Compounds 5.2.1.2 Periodic Medical Examination, consisting of at least
Chemical Name Formula Color Index NameA
the following: Completion of a health history questionnaire
with attention given to smoking history, posterior-anterior
Barium chromate BaCrO4 Pigment Yellow 31
Barium potassium chromate BaK3(CrO4)2 Pigment Yellow 31
chest X-ray, complete blood count or red cell count and
Basic copper chromate CuCrO4 Not listed hemoglobin, and pulmonary function studies (FVC, FEV 1.0
xCu(OH)2 and FEV 1.0/FVC).
Basic cadmium chromate Cd2(OH)2CrO4 Pigment Yellow 44
Basic lead chromate PbCrO4PbO Pigment Orange 21 5.2.2 Medical examinations shall be made available to
Bismuth basic dichromate Bi2O3CrO3 Pigment Red 103 workers with symptoms of skin or upper respiratory tract
Calcium chromate CaCrO4 None assigned irritation at the time the symptoms are first observed or
“Chromic chromate” xCaO yCr2O3 Pigment Yellow 33
(calcium chromate sinter) zCrO3 Not listed reported.
Ferric chromate Fe2(CrO4)3 Pigment Yellow 45 5.2.3 Management—Proper medical management shall be
Basic ferric chromate Fe(OH)CrO4 Pigment Yellow 45 provided promptly for workers adversely affected by exposure
Lead chromate PbCrO4 Pigment Yellow 34
Lead molybdochromate PbCrO4PbMoO4 Pigment Red 104 to insoluble chromates. The cause of any excessive exposure
Potassium zinc chromate K2O 4ano·4Cr4O3 Pigment Yellow 36
Strontium chromate SrCrO4 Pigment Yellow 32
Zinc chromate ZnCrO4 Pigment Yellow 36 5
Committee on Industrial Ventilation, Documentation of TLVs, American Con-
A
For Classification, not Toxicology. ference of Governmental Industrial Hygienist, 1985.

2
 E 848 – 94 (2000)
shall be sought without delay, and corrective action initiated. A work practice controls, or both. The choice of method should
physician shall determine if sensitized individuals should be depend on the factors involved in each specific situation. Two
excluded from jobs with a risk of exposure. criteria should be used to guide the choice of the control
5.2.4 First Aid: measures. The measure chosen must reduce employee expo-
5.2.4.1 Ingestion—Induce vomiting promptly and obtain sure below the applicable safe limit and the control method
prompt medical attention. “Advice to physicians: Administer must be reliable (14, 15). With these two factors met, other
500 to 1000 mg ascorbic acid IV as promptly as possible, factors such as logistics, product quality, economics, morale,
followed by oral Vitamin C, 5 to 10 g/day until risk of kidney housekeeping, and efficiency can then be incorporated into the
failure has ceased,” (13). decision logic for choosing appropriate control measures.
5.2.4.2 Chromium Contamination of Open Wounds—Flush Respirators are also required for emergencies and for the
thoroughly for 15 min with water and seek medical attention. performance of nonroutine tests and duties that have the
5.2.4.3 Eye Irritation—Flush thoroughly with copious likelihood of exceeding the PEL. Brush or roller application of
quantities of water for 15 min and seek medical attention. paints does not normally require respiratory protective equip-
5.3 Labeling and Posting: ment for protection from airborne chromates.
5.3.1 Warning Signs—In areas where insoluble chromate 5.4.2 The Respiratory Protection Program must meet the
concentrations in the atmosphere are likely to exceed the general requirements outlined in OSHA 29 CFR 1910.134 and
standard, appropriate warning signs, barricades, or work prac- in ANSI Z88.2-1980, see Ref (16). This program shall include
tices should be used to restrict access to unauthorized persons. instructions on the proper selection and use, including fit
The sign must alert anyone entering the area as to what action testing, cleaning and maintenance of respirators and air supply
should be taken. devices. The fit test should be performed annually on all
5.3.2 Container Labels—All containers (bag, barrel, box, negative pressure respirators. Either a quantitative or qualita-
can, drum, reaction vessel, storage tanks, but not pipe or pipe tive test is satisfactory (14, 15). The type of respirator required
lines) should be labeled, tagged, or marked with the following for protection against known or expected concentration of
information: airborne chromate to be encountered is outlined in Table 2.
5.3.2.1 The Identity of the Material(s)— Identity means any 5.4.3 Foot Protection—Industrial type leather shoes with
chemical or common name(s), code name or number, or brand synthetic soles will provide ample protection under normal
name, that is indicated on the material safety data sheet for the operating and good housekeeping conditions. For wet opera-
chemical. tions during cleanup of spills or when conducting decontami-
5.3.2.2 Batch process sheets, batch tickets, operating proce- nation procedures, rubber or synthetic booties or pullover shoe
dures, or other such written materials are acceptable alterna- protection shall be worn, and thoroughly rinsed and dried
tives to individual labels as long as the appropriate identity is before reuse. Shoes that are torn or show evidence of inside
readily accessible to employees. contamination with chromate shall be disposed of properly.
5.3.2.3 Portable containers for immediate use need not be 5.4.4 Clothing—Any employee exposed to airborne levels
labeled. of chromium above the PEL or when the possibility of skin or
5.3.3 Material Safety Data Sheet (MSDS)—The MSDS or eye irritation exists, should be supplied with appropriate
equivalent is the primary source of the safety and health protective work clothing such as coveralls or similar full-body
information. The chemical identification and MSDS for all work clothes. See for example, ANSI Z87.1 for eye and face
insoluble chromates used in the workplace must be made protection guidelines. Clean work clothing should be supplied
readily accessible to all employees. The MSDS in conjunction at least weekly to employees in these cases. All protective
with the identity on the label and employee training will clothing must be removed at the completion of each work shift
convey the hazard(s) (both physical and health) determination in the change room provided for this purpose. Employees
for the chromate compounds. Information on the MSDS must exposed to chromium above the PEL should shower at the end
include: of the work shift. Employees must not wear or take any of the
5.3.3.1 The OSHA PEL and the ACGIH TLV. protective equipment off the work site. Care must be taken to
5.3.3.2 A statement to that effect if the chromate has been prevent any cross contamination of street clothes.
identified as a suspect carcinogen by the National Toxicology 5.4.5 Hand Protection—Suitable gloves to minimize skin
Program (NTP), the International Agency for Research on contact shall be worn during operations where chromates are
Cancer (IARC), OSHA, or the employer. handled and may contact skin. Hands should be cleaned after
5.3.4 Finished Product Labels, are the responsibility of the removal of gloves. Gloves showing evidence of internal
manufacturer based on his knowledge of the end use of his contamination shall be disposed of or thoroughly cleaned
unique products. However, the label should be in agreement before reuse.
with the recommendations of ANSI Z129. Any applicable 5.4.6 Inspection—All personal protective devices shall be
governmental regulation must be followed. inspected regularly and shall be maintained in clean and
5.4 Personal Protective Equipment: satisfactory working condition.
5.4.1 Respiratory Protection—Each employee’s personal 5.5 Appraisal of Employees of Hazards ( Communications):
work environment shall be maintained at a safe exposure level 5.5.1 Education and Training—All employees who are
through implementation of cost effective engineering controls, employed in an exposure area shall be advised of the following
augmented as necessary by personal protective equipment or according to OSHA 29 CFR 1910.1200:

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 E 848 – 94 (2000)
TABLE 2 Protection Factors for Particulate Filter Respirators 5.5.1.8 Exposure monitoring programs,
NOTE 1—This table is based on Refs (17, 18, 19) and ANSI Z88.2. 5.5.1.9 Employee responsibility for following procedures
Concentrations in
and using protective equipment, and
Face-
Multiples of
Piece Permissible Respirators
5.5.1.10 Emergency procedures.
Permissible
Exposure LimitsA
Pressure 5.5.1.11 This information may be communicated and train-
ing achieved by any combination of oral or written individual
53 − Single-use dust
− Quarter-mask dust
or group methods which achieve understanding. Training
103 − Half-mask dustB should be repeated annually.
− Half of quarter mask, fume 5.5.2 Exposure Records—Employees have the right to their
− Half or quarter mask, high
efficiency exposure records and medical records under OSHA 29 CFR
− Half mask, supplied air de- 1910.20.
mand mode
503 − Full-face piece, high effi-
5.6 Work Practices and Engineering Controls:
ciency or dust, fume, mist 5.6.1 Housekeeping—Spills shall be cleaned up promptly
− Full-face piece, supplied air by vacuuming, or wet methods, or by absorption methods that
demand modeC
− Self-contained breathing ap-
will prevent airborne contamination. No dry sweeping shall be
paratus (SCBA) demand performed. Floors, equipment, stains, and other contactable
mode surfaces that may accumulate chromate particulate fallout shall
10003 + Powered, high-efficiency, all
enclosuresD be maintained free of dust that may become airborne. Contain-
+ Half mask, supplied air, ers provided for chromate solid waste shall be labeled and
pressure-demand mode or covered in accordance with 5.3.2.
continuous flow
20003 + Full-face piece, hood, hel- 5.6.2 Control of Hazards:
met, or suit; supplied air; 5.6.2.1 Engineering Design and Construction—In the plan-
pressure-demand mode or
continuous flow
ning and erection of new or modified manufacturing or
10 0003 + Full-face piece, SCBA handling facilities, the principles of industrial hygiene and
pressure-demand mode safety should be systematically applied.
+ Full-face piece supplied air
pressure-demand mode or 5.6.2.2 Ventilation—All operations that release dust, such as
continuous flow with auxiliary opening packages, sampling, taking aliquots, charging vessels,
self-contained air supply drying, sizing, mixing, discharging (packout), or cleanout shall
Emergency entry into + Full-face piece, SCBA
unknown pressure demand mode be provided with appropriately designated local ventilation in
concentrations or accordance with ACGIH recommendations and applicable
firefighting
Escape onlyE + Any SCBA
governmental regulations. Ventilation systems shall be subject
− Any self rescuer to a preventive maintenance inspection program to ensure that
A
Other chemicals, for example, lead may be the controlling factor rather than hoods, ducts, fans, absorbers, draft controls, filters, alarms, and
chromate concentration. other components are structurally sound and in good working
B
Half-mask and quarter-mask respirators should not be used if the particulate order. Periodic tests of duct pressures or flows, or both, shall be
matter causes eye irritation at the use concentration.
C
Full-face piece, supplied-air respirators should not be used in any atmosphere made to ensure that the ventilation is adequate (20).
that is immediately dangerous to life or health unless it is equipped with an 5.6.3 Solid Waste Disposal—Solid waste containing in-
auxiliary self-contained air supply that can be operated in the positive-pressure
mode.
soluble chromates that have the potential for becoming air-
D
Recent work by NIOSH would indicate a protection factor of 1000 may not be borne shall be stored in labeled and covered containers until
obtained. Consult your supplier.
E
disposal in accordance with applicable governmental agency
In an atmosphere that is immediately dangerous to life or health.
regulations.
5.6.4 Maintenance—Equipment and instruments shall be
5.5.1.1 Chemical names,6 kept in good repair. Pumps, vessels, and lines handling
5.5.1.2 Label identification system, insoluble chromates shall be drained and washed out before
5.5.1.3 Work procedures, repairs are made except where repairs can be made without
5.5.1.4 Site and government standards,7 exceeding the PEL.
5.5.1.5 Potential health effects from both acute and chronic 5.6.5 Sanitation—Washing facilities, emergency showers,
exposures,6 eye-flushing fountains, or appropriate washing facilities shall
5.5.1.6 Relevance of medical exams, be provided and be easily accessible in areas where there is
5.5.1.7 Protective control measures used and new relevant potential for skin or eye contact with insoluble hexavalent
information, chromium dust or liquids. This equipment shall be frequently
inspected, and maintained in good working condition. Con-
6
These items should also be included on the Material Safety Data Sheets
taminated clothing shall be held in containers until removed for
(MSDS). decontamination or disposal. Arrangements for laundering or
7
NIOSH Manual of Analytical Methods, 3rd ed., U.S. Department of Health and otherwise decontaminating work clothing shall ensure the
Human Services, Public Health Service, Centers for Disease Control. National protection of individuals involved in this work.
Institute for Occupational Safety and Health, Division of Physical Sciences and
Engineering; Cincinnati, Ohio, 1990. Available from the Superintendent of Docu- 5.6.6 Statistical Control—Data resulting from air and bio-
ments, U.S. Government Printing Office, Washington, DC 20402. logical monitoring can be subject to various errors such as

4
 E 848 – 94 (2000)
random sampling device errors, or random analytical errors, or maintained in a secure and confidential manner for at least 30
both. These errors can be quantified and their effects minimized years after termination of employment.
by the application of statistically based quality contol pro-
grams. Each analytical method should be consulted for appro- 6. Physical and Chemical Properties
priate details. 6.1 Selected physical and chemical properties of insoluble
5.6.6.1 Another potential source of large error is due to the chromates are given in Table 3.
random interday and intraday fluctuations in airborne contami-
nant levels. These fluctuations are generally considered to be
7. Monitoring Airborne and Biological Chromates
log-normal, and may result in erroneous conclusions unless
properly considered. 7.1 Personnel Monitoring—Breathing zone samples repre-
5.6.6.2 An appropriate objective is to control each employ- sent the most accurate measurement of employee exposure to
ee’s exposure so that the maximum probability of exposure airborne chromates. The sample is taken within a foot of the
above the exposure limit is 5 %. A number of references can be employee’s face, and represents air inhaled by the employee.
used for guidance since this detail is beyond the scope of this The sample may be obtained using a personal sampler attached
practice (21, 22, 23). to an individual or by a sampling device held within a foot of
5.6.7 Containers—All shipping, storage, or in-plant trans- the face. An analytical method should be consulted for the
port containers of insoluble chromates shall be labeled to necessary details such as collection device, flow rate, and the
identify the material. like.
5.6.8 Safety (Fire and Explosion): 7.2 Area Sampling—This is also known as fixed location
5.6.8.1 Fire—The chromates covered by this practice are sampling and is normally used to determine the maximum
nonflammable, but under favorable conditions some may have potential exposure, or to make a preliminary study of work-
sufficient solubility in the presence of combustible materials to place conditions. An example is a continuous monitor.
initiate combustion by local exothermic oxidation. 7.3 Frequency—In applying this practice, preliminary in-
5.6.8.2 Explosion—None of the chromates covered by this vestigation of all work operations should be made by an
practice are explosive even at elevated temperatures. Mixtures industrial hygienist or other qualified professional for the
of insoluble chromates with readily oxidizable materials may purposes of designating both frequency and location of air
be explosive. sampling devices and appropriate job assignments to be
5.7 Recordkeeping: monitored.
5.7.1 All test results shall be recorded showing location, 7.4 Biological Monitoring—Blood and urinalysis for certain
time and date of sample, and identity of employee in the case components have long been used for monitoring the effective-
of personal or biological sampling. This information shall be ness of programs designed to control worker exposure. Air and
retained for at least 30 years, and in the case of personal or blood lead levels should be monitored as required in OSHA 29
biological sampling, results shall be kept for 40 years or at least CFR 1910.1025. Currently, when lead chromate is used or
30 years after the termination of employment, whichever is handled in any manner such that airborne lead levels exceed 30
longer. µg/m3, it is essential that a blood-lead monitoring program be
5.7.2 Pertinent medical records, including results of clinical undertaken. Monitoring for other biochemical indicators may
examinations, biological and biochemical analysis, roentgeno- be useful in certain situations but until better correlation with
grams, and dates of treatment or hospitalization, shall be blood lead levels is established, none are recommended. It is

TABLE 3 Physical and Chemical Properties of Insoluble Chromates

Solubility Solubility Solubility
Molecular Particle Melting
Chromate in Water,A Product, in Dilute
Weight Density Point
g/100 cm3 mol2/L2 Acid
Barium potassium 563.52 4.50 (15°C)
Barium 253.37 4.50 (15°C) 0.00034 (16°C) 1.6 3 10−10(18°C) soluble
0.004 (37°C)
Basic cadmium 374.81
Basic ferric 188.85
Basic copper variable compositions
Basic lead 546.2
Bismuth basic di-chromate 665.95
Calcium 156.07 0.75 (37°C)
Chromic (sinter) variable compositions 0.13 (37°C) as Cr+6 soluble
Ferric 459.67
Lead 323.10 6.12 (15°C) 844 5.8 3 10−6(25°C) 1.77 3 10−14(18°C)
soluble
Lead molybdochromate variable compositions
Potassium zinc 819.68
Strontium 203.63 3.90 (15°C) 0.09 (37°C) soluble
Zinc 181.37 3.40 (15°C) 0.21 (37°C) soluble
A
Solubilities in water at 37°C were calculated on the basis of data given in Heuper, W. C., and Conway, W. D., Chemical Carcinogenesis and Cancers, C. C Thomas,
Springfield, IL 1964, p. 397.

5
 E 848 – 94 (2000)
noted that blood lead levels in excess of 50 µg/100 g of blood 8.2 Any analytical procedure that has been shown to possess
require worker removal from the area under the OSHA equivalent or better sensitivity, reproducibility, and accuracy
standard. may be used to determine whether environmental levels are
8. Analytical Test Methods within the recommended standards.
8.1 National Institute for Occupational Safety and Health,
9. Keywords
(NIOSH) published the following methods:7 7024; 7200; 7300;
7600; 7604; 8005; and 8310. These methods should be 9.1 chromium; chromium based pigments; chromium com-
consulted for advantages and disadvantages. (Such as separat- pounds; exposure; health; hexavalent chromium; insoluble
ing CR III from CR VI). chromium; safety

APPENDIX

(Nonmandatory Information)

X1. EPIDEMIOLOGY AND TOXICOLOGY

X1.1 General as 50 mg/kg was reported by Gleason, but Harrold found this
X1.1.1 This appendix is restricted to discussion of the compound was poorly absorbed by paint workers (29, 38).
epidemiology and toxicology of insoluble chromates as defined Gross found that rats and mice tolerate 1 % zinc chromate in
in Section 1. For a more thorough understanding, the original their feed (39). Kennedy summarized the toxicity of lead
articles should be consulted. chromates (40). The size of the dose required to produce effects
varies considerably between pigments. The most adverse
X1.2 Early Studies effects result from the availability of the lead cation.
X1.2.1 Although chrome dermatitis, skin ulcers, and nasal X1.3.3 In most studies the compounds were administered
septum perforations were reported as early as 1827 in Scotland by intravenous injection, a procedure considered irrelevant for
and in 1933 in the United States, indications that chromates of the purpose at hand. At least for the more soluble of the
some kind were a possible cause of bronchogenic carcinomas chromate pigments, it is expected that excessive oral ingestion
observed in chromate-producing plants first appeared in the will result, as with the injected soluble chromates, in acute or
German literature during the 1930s (1, 2, 24, 25, 26, 27). chronic renal damage or failure, or both. Hunder found, for
Following evidence in 1945, that a similar situation might be example, that 0.02 g/kg of potassium dichromate (as 2 %
developing in the United States, the chromates industry spon- solution) was fatal to a monkey, producing acute renal lesions
sored literature and case studies that culminated in reports by (41). Tandon reported elevated chromium levels in the urines
Machle and Gregorius, by Baetjer, and by the U.S. Public of pigment handlers in Indian paint factories (42). Toxicity by
Health Service (28, 29, 30, 31). These reports were in substan- the oral route has not been reported to be an occupational
tial agreement that the causative agents were associated with hazard.
the lime-roasting phase of the production process. By this time,
it was clear that most of the dermatitis, sensitization, and X1.4 Skin and Eye Irritation
ulceration effects were due to exposures to chromic acid and X1.4.1 The dermal irritancy and skin-sensitizing properties
the soluble chromates and causative agents. It is noted, lead of the soluble chromates are well known and fully documented
chromate compounds have not been associated with sensitiza- (43, 44). Less is known about the action of the insoluble
tion or ulceration. chromates in these regards. However, since several of the
X1.2.2 The carcinogenicity of calcium chromate and sin- chromate pigments have some limited solubility in moisture
tered and roasted ore (containing calcium chromato chromite, and therefore in perspiration, allergic skin reactions can occur
misnamed “chromic chromate”) was confirmed by animal in sensitized individuals. Walsh is of the opinion that once
studies: by Heuper in 1958 and 1959, Baetjer in 1959, and chromate sensitivity becomes established, there is apparently
Payne in 1960 (32, 33, 34, 35, 36). no “hardening” or increased tolerance to further exposures
(45). Both Fisher and Engle have observed dermatitis in
X1.3 Oral Toxicity and Metabolism workers exposed to pain containing zinc chromate (46, 47).
X1.3.1 Insoluble chromates, at rates dependent on their Calnan made a study of so called “cement dermatitis” and
solubility, are either eliminated unchanged in the feces or concluded that the presence of chromates was a possible cause
reduced to trivalent chromium that is bound to protein (37). (47). It seems likely, that any chromate present in cement
Rates of the later have three components with half-lives of 0.5, would be largely in the form of calcium salt. Similarly, as
5.9, and 83.4 days. reported by Fregert and Shelly, the chromium alleged to be a
X1.3.2 Obviously, the oral toxicity of insoluble chromates is possible causative agent in dermatitis from welding fumes may
dependent on the nature of the cation, especially in the cases of be in the hexavalent form (48, 49). In any event, there is reason
lead chromate. A lethal dose, in man, of lead chromate as low to believe that the more soluble chromate pigments may be

6
 E 848 – 94 (2000)
causative agents for contact dermatitis, particularly among chromate-producing capacity (55). These plants used the lime
sensitized or allergic individuals. process. He found a nine-fold increase in deaths from lung
X1.4.2 Insoluble chromates should be regarded as possible cancer.
eye irritants, due to their irritancy as particulates. No reports of X1.5.2.8 Enterline, in 1974, reanalyzed the data from Tay-
special studies of the effects of insoluble chromates on the eye lor’s study for 1941 to 1960 and found, again, the nine-fold
have been found. Although skin ulcers and nasal-septum increase in deaths from lung cancer (56). In addition, he also
perforations are unusually associated with excessive exposure found a slight excess in deaths from cancer of the digestive
to soluble chromates, dichromates, and chromic acid, some system.
chromate pigments are sufficiently soluble to make it unwise to
rule them out as causative agents. X1.5.2.9 In 1979, Hill and Ferguson investigated the impact
of changes in production technology at a Baltimore plant using
X1.5 Respiratory Tract Irritation “probability window analysis” (57). These authors found that
the successive decline in bronchiogenic carcinomas among the
X1.5.1 It has been shown that inhalation of soluble chro- successive cohorts of those persons entering risk in the ten year
mates can cause a variety of adverse respiratory reactions such periods, 1932 to 1941, 1942 to 1951, 1952 to 1961, and 1962
as bronchitis, laryngitis, bronchogenic asthma, rhinorrhea tra- to 1971 was highly significant. No further cases occurred in a
cheitis, pharyngitis, and emphysema (1, 44). No reports estab-
subsequent period 1972 to 1977 and there have been no
lishing airborne insoluble chromates as the cause of these
observed cases of bronchogenic carcinoma among workers
effects have been found.
entering risk during the twenty year period 1958 to 1977. The
X1.5.2 Epidemiologic Studies:
results suggest that the risk of lung cancer in chromate-
X1.5.2.1 Machle and Gregorius made the first epidemio-
production workers has been reduced by improvements in the
logic study of the U.S. chromate industry (28). They examined
process and by consequent reduction of exposure to chromium
the incidence rates of lung cancer in seven chromate producing
materials.
plants and found consistently high mortality ratios in six of
these plants. X1.5.2.10 Although the number of cases is sometimes too
X1.5.2.2 Baetjer, limiting her study to two production plants low to permit valid conclusions and most exposures have been
in Baltimore, found a similar elevation in mortality ratio (29, mixed, there is accumulating epidemiological evidence that
30). Both Machle and Baetjer studied plants that used a calcium chromate and sintered lime roast containing calcium
lime-roasting process. One plant examined by Machle did not chromato-chromite are lung cancer causative or promoting
use alkaline oxidation of chromite and had no deaths from lung (genotoxic or epigenetic) agents in chromate-producing plants
cancer in 1853 man-years of exposure. using the lime process (57).
X1.5.2.3 Mancuso and Heuper investigated an Ohio X1.5.2.11 The earliest epidemiological study of a chromate
chromate-producing plant using the lime-roasting process and pigment-producing plant was reported by Gross in 1943 (26).
found a marked increase in lung cancer cases beyond that In a German factory, there were seven deaths from lung cancer
found in control groups (50). in fewer than 50 workers. Lead, zinc, potassium, and barium
X1.5.2.4 A thorough review of the chromate-producing chromates were among the pigments produced. Potassium
industry in the United States was undertaken by the U.S. Public dichromate was used as a raw material.
Health Service in 1948 and was published in 1953 (2, 51). This X1.5.2.12 In 1975, Langaard and Norseth reported an in-
report concluded: “Some factor, not present in the comparison
crease in bronchogenic cancer in a Scandinavian chromate
group, is responsible for the greater prevalence and earlier
pigment-producing plant (3). Unfortunately, the subgroup stud-
production of bronchogenic carcinoma in chromate workers.”
ied is small. Only 24 men worked more than three years and of
X1.5.2.5 In 1951, Bidstrup reported on her study of the
these, three had bronchogenic cancer and two of these were
British chromate-producing industry where the lime process
smokers. In 1983, Langaard and Vigander reported the results
was used (52). Her results were limited in significance because
of a follow-up study on the same group of workers (21). Three
she found only one case of lung cancer in 724 workers. In
1956, Bidstrup and Case demonstrated that from 1949 to 1955 more cases of lung cancer were found. The observed/expected
in three bi-chromate producing factories in Great Britain there ratio of 44 was the same as in 1972. Five of the six lung cancer
existed a statistically significant increase in mortality due to patients smoked and all had been exposed to zinc chromate.
carcinoma of the lung (53). X1.5.2.13 Davies compared the incidence of lung cancer
X1.5.2.6 Alderson, Rappan, and Bidstrup in 1981 showed in mortality among English workers at two manufacturing sites
a follow-up study of 2715 men who had worked for at least one who were exposed to both zinc and lead chromate with another
year at the three chromate-producing factories in Britain site that only manufactured lead chromate (8, 58). There was
between 1948 and 1977, that the relative risk of lung cancer for no excess lung cancer mortality among workers with chromate
those men employed at the one factory still in operation, had exposures rated as “low” nor among those exposed only to lead
decreased from over three before plant modification to about chromates at all exposure levels. Workers with mixed expo-
1.8, in those who had worked only since plant modification sures in the “medium to high” category to both lead and zinc
(this included the elimination of lime in 1961) (54). chromate had a marked excess of lung cancer deaths. In the
X1.5.2.7 In 1966, Taylor reported on a study of 1212 author’s opinion, the results suggest that the manufacturer of
workers representing three plants and 70 % of the U.S. zinc chromate may involve a lung cancer hazard.

7
 E 848 – 94 (2000)
X1.5.2.14 In 1981, Hagauenor, and others performed a compounds as part of its monograph on the evaluation of
prospective study of mortality in a chrome-pigment manufac- carcinogenic risk of chemicals on humans (66). The conclusion
turing plant in France (59). They studied 251 workers who had is as follows:“ There is sufficient evidence of respiratory
been exposed for at least six months during 1958 and 1977 and carcinogenicity in men occupationally exposed during chro-
had been involved in the manufacture of both lead and zinc mate production. Data on lung cancer risk in other chromium
chromate. The relative standardized risk of bronchogenic associated occupations and for cancer at other sites are
cancer was 6.41. Also, it was noted that 10 of the 11 cases of insufficient. The epidemiological data do not allow an evalua-
bronchogenic carcinoma were smokers and five had previously tion of relative contributions to carcinogenic risk of metallic
had a history of lead poisoning. chromium, chromium (III), chromium (IV), or soluble versus
X1.5.2.15 In 1982, Sheffet, and others performed an epide- insoluble chromium compounds.”
miological study of mortality in a pigment plant in Newark, NJ X1.5.2.20 A recent review of the known toxic effects of lead
that utilized both lead and zinc pigments (60). The study chromate by J. Morgan concluded that “In past reviews, toxic
population comprised two cohorts, one containing 1296 white properties that are characteristic of certain lead compounds and
and the second 650 non-white male employees who worked at certain hexavalent lead chromate compounds and of processes
the plant between January 1940 and December 1969 for longer in which they occur, have been erroneously attributed to lead
than one month. A statistically significant, relative risk of 1.6 chromate pigments and the processes in which they have been
for lung cancer among white male employees was found. A manufactured and used,” (40). Past reviews did not recognize
relative risk of 1.9 was noted for individuals employed for at the dissimilar physical, chemical, and toxic properties of lead
least two years who were “moderately” exposed to chromates. chromate pigments as compared to the general classes of lead
An increased incidence of lung cancer among non-whites and compounds and hexavalent chromium compounds.
stomach and pancreatic cancers among the total cohorts was X1.5.2.21 Lung cancer has been unequivocally associated
also evident but these are not statistically significant. with the process of producing soluble chromates from chromite
X1.5.2.16 In 1976, Equitable Environmental Health, Inc. ore. This observation was made in a period of time when dust
completed a study of mortality of employees in three U.S. concentrations were exceedingly high compared to the present
chromate-pigment manufacturing plants (61). Analysis of the OSHA standard for chromic acid and chromates. In the
deaths gave inconclusive results, but the data did suggest that manufacture of lead chromate pigments, the dust composition
prolonged excess inhalation of chromate pigment could cause is different from that in chromite or processing. Even during
lung cancer. In 1983, a five year follow-up study was com- past decades when dust concentrations were high, the lung
pleted (62). The follow-up showed that in the one plant having cancer incidents have failed to reveal a clear-cut relationship
exposure only to lead chromate pigment, there was no statis- between exposure and disease. J. Morgan concluded that
tically significant excess of lung cancer deaths. The author compliance with the current OSHA chromate standard in past
concluded that “the study, therefore, did not produce evidence decades of pigment manufacture and use would have been
supporting any association between lead chromate and lung adequate to protect the health of exposed workers.
cancer.” There was a statistically significant increase in lung X1.5.2.22 A retrospective mortality study of 4215 male
cancer deaths in the plants producing both lead and zinc employees at 10 automobile factories, with special consider-
chromate and the author concluded that “although the numbers ation to spray painters, was reported by Chiazzi (67). He
are small, this updated follow-up supports the hypothesis that reported a proportionate mortality ratio (PMR) of 1.3 for 278
zinc chromate increases the risk of lung cancer.” However, the combined cancers of the upper respiratory tract and lungs
number of lung cancer deaths among persons exposed only to among all white male workers. The number of such cases was
lead chromate was too small to draw definitive conclusions. not significantly higher than the expected number. The stan-
X1.5.2.17 A study done by Frentzel-Beyme, and others, of dardized mortality ratio (SMR) for spray painters was 1.26
five factories in the Netherlands and West Germany with a total versus 1.34 for employees with no spray paint exposure. No
of 1921 employees all producing zinc and lead chromate information was given as to the exposure level or smoking
showed a moderate but consistent increased risk of lung and habits of the cohorts under study.
respiratory tract cancer at four of the five factories. A multi- X1.5.2.23 A proportionate mortality study of aircraft spray
centric European epidemiological study investigated the lung painters was reported by N. Dalager (68). The study (of
cancer mortality of workers employed in chromate pigment workers who worked at least 3 months) reported a significant
factories (63). Other studies of the occurrence of lung cancer in excess of cancer (PMR 1.36) particularly of the respiratory
workers producing chromium pigments were reported by tract (1.84) among workers who use spray paints containing
Langard in 1983 (64) and a publication by Satoh in 1981 zinc chromate. However, the study did not specify the many
described an epidemiological study of workers engaged in the other chemicals present in the paints, or smoking in the
manufacturer of chromium compounds (65). presence of the paints, or smoking histories or the fact that
X1.5.2.18 The American Conference of Government Indus- many of these workers had previously worked in other un-
trial Hygienists (ACGIH) has designated chromates of lead and known occupations.
zinc as industrial substances suspect of carcinogenic potential X1.5.2.24 A National Paint and Coatings Association
for men with a TLV of 0.05 mg/M 3. (NPCA) sponsored a mortality study in 1981 of production
X1.5.2.19 The International Agency for Research on Cancer workers in the paint and coatings manufacturing industry (69).
(IARC) has prepared a review on chromium and chromium This study showed a reduced standardized mortality ratio

8
 E 848 – 94 (2000)
(SMR) for malignant neoplasms from all causes. However, the X1.6.1.6 In 1965, Heuper and Conway concluded that the
pigment cohort group did show some elevation for certain relative carcinogenic potency of the chromium compounds
types of cancers. This could possibly be due to the small depends upon their solubility in water and is greatest for these
numbers of deaths involved. A follow-up study examined the compounds of medium solubility that are gradually dissolved
pigment cohort group and indicated that the relative risk of in the body (78). This enables them to exert a prolonged action.
having cancer in relation to the entire study cohort was not This view of the importance of solubility is supported by
elevated (70, 71). Clayson in 1962 (79).
X1.6.1.7 A study by Levy, in 1975, used the intrabronchial
X1.6 Animal Carcinogenesis pellet implantation technique with a range of chromium
X1.6.1 A large number of animal tests have been made containing materials normally found in a chromate producing
using insoluble chromates. These have for the most part industry (80). The study showed that bronchial carcinomas
involved implants, or intromuscular, intrapleural, and subcuta- could be formed in the rat lung in the presence of some
neous injections. While local sarcomas and occasional distant chromium containing materials.
tumors have been obtained by these methods in a variety of X1.6.1.8 The technique developed by Laskin (81) is re-
species, the significance of many studies is doubtful either ferred to as the intrabronchial pellet implantation in which a
because the incidence rates are low or the increase over metal pellet or basket containing the material under test is
controls is not large. surgically implanted into the left inferior bronchiole of the rat
X1.6.1.1 Heuper obtained an increase in tumors in rats with (82). The metal pellet acts as a framework in and around where
muscular implants of chromite-ore lime roast, calcium the test material is suspended. A1983 study performed by Levy
chromite, and sintered calcium chromate, but not with barium at Aston University in England has made some significant
chromate (32, 33). Payne obtained sarcomas in mice with findings from this technique (83). They are as follows: Zinc
intramuscular implants of calcium chromate and sintered chromate (low solubility) gave a significant number (5 out of
calcium chromate (35). He also implanted calcium chromate 100) of bronchial carcinomas when compared to the expected
intramuscularly and intrapleurally in rats and obtained local number. Another zinc chromate (Norge composition) gave 3
sarcomas. Subcutaneous injections into the nape of the neck of out of 100 bronchial carcinomas and this was just not statisti-
mice gave equivocal results with the same compounds (36). cally significant. No bronchial carcinomas (0 out of 100) were
Heuper made intratracheal instillation in rats using calcium seen in the control group containing only cholesterol, and
chromate, strontium chromate, and zinc chromate with nega- bronchial carcinomas were seen in the two positive control
tive results. Mice and rats were subjected by Baetjer to groups (methylcholanthrene and calcium chromate, the number
inhalation of a dust consisting of both soluble and insoluble of tumors was 22 out of 48 and 25 out of 100, respectively).
chromates with negative results (72). Intratracheal injection as Barium chromate had 0 bronchial carcinomas (1 out of 100 for
well as intravenous injections in mice of zinc potassium pure lead chromate, primrose chrome yellow, LD chrome
chromate and of barium chromate gave negative results. yellow, medium chrome yellow, and 0 out of 100 for molyb-
X1.6.1.2 Steffee and Baetjer were unsuccessful in produc- date chrome yellow). The authors conclude “These and other
ing significant tumors in rabbits, guinea pigs, rats, or mice by results suggest that lead chromate pigments are non-
intratracheal injections of lime roast, zinc potassium chromate, carcinogenic, or at most have an extremely low carcinogenic
lead chromates, or leached lime roast (73). potential.” The authors also conclude, “The results of the
X1.6.1.3 Using arachis oil as the vehicle, Roe obtained chromate pigment materials examined in this study, taken
significant numbers of local sarcomas in rats with calcium together with previous animal studies can be used to explain
chromate (74). the reported lung cancer risk to chromate pigment workers.
X1.6.1.4 In 1966, Heuper reported on the formation of a Where the workers in this industry tend to be exposed to both
high percentage of injection site cancers in rats from injection zinc and lead chromate, this present study strongly supports the
of “chromic chromate”, sintered calcium chromate, calcium hypothesis that lead chromate is non-carcinogenic, or at most
chromate, strontium chromate, and zinc yellow (75). A low has an extremely low carcinogenic potential. This is consistent
yield was obtained with barium and lead chromates. Laskin with the findings of Davies (8, 58). It is recognized that this
obtained interesting results by intrabronchial implantation of technique does not simulate human exposure in that it is an
leached lime-roast residue and calcium chromate in cholesterol extremely harsh treatment with respect to the constancy of
(76). He obtained a low yield of squamous cells in subjected contact of each test agent with target tissue, and the duration of
rats and hamsters in long-term inhalation of calcium chromate contact, the chronic irritation caused by some of the materials.
dust and obtained laryngeal hyperplasia and a few squamous X1.6.1.9 In 1981, Petrilli and De Flora concluded that
tumors, the significance of which is doubtful. chromium mutagenicity is exclusively due to the hexavalent
X1.6.1.5 In 1971, Nettesheim reported a low yield of lung ion which appears to induce errors in DNA reproduction (18).
tumors3 and no bronchiogenic tumors in mice inhaling 13 All the trivalent chromium materials tested were non-toxic and
mg/m of calcium chromate (77). The increase over controls non-mutagenic even in very high concentrations. They also
was 6/2 for 136 male mice and 8/2 for 136 female mice. showed that the mutagenicity of hexavalent chromium could be
Nettesheim also subjected hamsters to 15 weekly intratracheal decreased or eliminated by various chemicals and metabolites
injections of calcium chromate and found deterioration of the such as human gastric juice. This suggests possible detoxifi-
alveoli. cation orally, the blood through stream, or other enzyme routes.

9
 E 848 – 94 (2000)
The liver is most effective in reducing the mutagenicity of desired and do not offer definitive proof that any of the suspect
chromium (IV) compounds. Levy and coworkers reported in compounds are carcinogenic, a number of epidemiological
1986 on the investigation of the potential carcinogenicity of a reports indicate that industrial exposure during insoluble chro-
range of chromium containing materials on rat lung (84). mate manufacture at levels well in excess of the current OSHA
X1.7 Teratogenicity Endpoint PEL or TLV is associated with an increase in lung cancer. The
most likely causative agents appear to be certain chromates of
X1.7.1 Teratogenicity
limited solubility.
X1.7.1.1 No reports on the teratogenicity of insoluble chro-
mates were found.
X1.8 Summary
X1.8.1 Although both epidemiologic and animal studies of
chromate pigments and process residues leaves much to be

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