ASTM E848-94(2006)
(Guide)Standard Guide for Safety and Health Requirements Relating to Occupational Exposure to Water-Insoluble Chromates
Standard Guide for Safety and Health Requirements Relating to Occupational Exposure to Water-Insoluble Chromates
SIGNIFICANCE AND USE
This guide includes chromates that are not readily soluble in water and that have water solubilities (Chromate ION) within the range of the more soluble calcium chromate and the much less soluble lead chromate. The major occupations involving potential exposure to insoluble chromates are in roasting of chromite ore, the manufacture of chromate pigments, the manufacture of coatings containing chromate pigments, and spray painting with these coatings. There is insufficient evidence to conclude that trivalent chromium compounds are carcinogenic.
SCOPE
1.1 This guide covers control procedures for the safe production, storage, transportation, and handling of only the hexavalent chromium compounds found in and their various hydrates, and mixtures of coprecipitates of the same regardless of crystalline form.
1.2 This guide is not intended to cover ( a) such "soluble" chromates as chromates of sodium, potassium, magnesium, or ammonium; (b) soluble bichromates; (c) chromic acid; (d) volatile chromyl compounds; (e) any trivalent chromium compound; or (f) elemental chromium. Omission of said compounds or classes of compounds should not be construed to mean that they may be handled without due regard to their particular physical, chemical, and toxicological hazards (, , ).
1.3 The chromate ion, CrO42, depending upon the acidity, complexes to form di-, tri-, and higher polychromates; hence, the chromates listed in may contain mixtures of polychromates, depending on the method of isolation and end use.
This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of whoever uses this standard to consult and establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. (For more specific precautionary information see Section 5.)
General Information
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Standards Content (Sample)
Designation: E848 − 94 (Reapproved 2006)
Standard Guide for
Safety and Health Requirements Relating to Occupational
Exposure to Water-Insoluble Chromates
This standard is issued under the fixed designation E848; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
INTRODUCTION
Thisguideisintendedtoprovideguidanceinthesafehandlingofcertainchromatecompoundsthat
are suspected to be carcinogenic in man (1-8). 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,
recognizingthatthepotentialforexposurewillvarywidelyfromindustrytoindustryandbetweenone
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 PELis 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
compound; or (f) elemental chromium. Omission of said
1.1 This guide covers control procedures for the safe pro-
compoundsorclassesofcompoundsshouldnotbeconstruedto
duction, storage, transportation, and handling of only the
mean that they may be handled without due regard to their
hexavalent chromium compounds found in Table 1 and their
particular physical, chemical, and toxicological hazards (9, 10,
various hydrates, and mixtures of coprecipitates of the same
11).
regardless of crystalline form.
−2
1.3 The chromate ion, CrO , depending upon the acidity,
1.2 This guide is not intended to cover (a) such “soluble”
complexes to form di-, tri-, and higher polychromates; hence,
chromates as chromates of sodium, potassium, magnesium, or
the chromates listed in Table 1 may contain mixtures of
ammonium; (b) soluble bichromates; (c) chromic acid; (d)
polychromates, depending on the method of isolation and end
use.
This guide is under the jurisdiction of ASTM Committee D01 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 D01.21 on Chemical Analysis of Paints and Paint Materials.
Current edition approved June 1, 2006. Published June 2006. Originally
responsibility of whoever uses this standard to consult and
approved in 1982. Last previous edition approved in 2000 as E848–94(2000).
establish appropriate safety and health practices and deter-
DOI: 10.1520/E0848-94R06.
mine the applicability of regulatory limitations prior to use.
The boldface numbers in parentheses refer to the references at the end of this
guide. (For more specific precautionary information see Section 5.)
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
E848 − 94 (Reapproved 2006)
TABLE 1 Examples of Some Hexavalent Chromium Compounds
4. Significance and Use
A
Chemical Name Formula Color Index Name
4.1 This guide includes chromates that are not readily
Barium chromate BaCrO Pigment Yellow 31
soluble in water and that have water solubilities (Chromate
Barium potassium chromate BaK (CrO ) Pigment Yellow 31
3 4 2
ION) within the range of the more soluble calcium chromate
Basic copper chromate CuCrO Not listed
xCu(OH)
2 and the much less soluble lead chromate. The major occupa-
Basic cadmium chromate Cd (OH) CrO Pigment Yellow 44
2 2 4
tionsinvolvingpotentialexposuretoinsolublechromatesarein
Basic lead chromate PbCrO PbO Pigment Orange 21
roasting of chromite ore, the manufacture of chromate pig-
Bismuth basic dichromate Bi O CrO Pigment Red 103
2 3 3
Calcium chromate CaCrO None assigned
4 ments, the manufacture of coatings containing chromate pig-
“Chromic chromate” xCaO yCr O Pigment Yellow 33
2 3
ments, and spray painting with these coatings. There is
(calcium chromate sinter) zCrO Not listed
insufficient evidence to conclude that trivalent chromium
Ferric chromate Fe (CrO ) Pigment Yellow 45
2 4 3
Basic ferric chromate Fe(OH)CrO Pigment Yellow 45
4 compounds are carcinogenic.
Lead chromate PbCrO Pigment Yellow 34
Lead molybdochromate PbCrO PbMoO Pigment Red 104
4 4
5. General Requirements
Potassium zinc chromate K O 4ano·4Cr4O Pigment Yellow 36
2 3
Strontium chromate SrCrO Pigment Yellow 32
5.1 Environmental Levels:
Zinc chromate ZnCrO Pigment Yellow 36
5.1.1 The following guide is designed to protect the health
A
For Classification, not Toxicology.
and safety of workers for an 8 to 10-h workday, 40-h
workweek, over a working lifetime. The PEL can be met by
techniques and controls that reduce employee exposure below
the applicable safe limit. These controls must be reliable.
2. Referenced Documents
Permissible exposure limits are based on the 1985 ACGIH
recommended Threshold Limit Values (TLV) for chromates of
2.1 ANSI Standards:
lead and zinc and for chromite-ore processing (12).
Z87.1Practice for Occupational and Educational Eye and
5.1.2 PEL—Occupational exposure to any of the com-
Face Protection
pounds listed in Table 1 shall be controlled to a TWA of 0.05
Z88.2Practices for Respiratory Protection
mg/m (as Chromium) for an 8-h workday.
Z129.1Precautionary Labeling for Hazardous Industrial
5.1.3 At least one full-shift (80% of the shift length)
Chemicals
4 personalsampleshouldbetakenforeachjobclassificationand
2.2 OSHA Standards:
each work area involving insoluble chromates. These samples
29 CFR 1910.20Access to Records
shallberepresentativeofamonitoredemployee’sregulardaily
29 CFR 1910.1200 Hazard Communication
exposure to insoluble chromates, and may be used to represent
29 CFR 1910.134 Respiratory Protection
the exposure of all employees in that job assignment. One
29 CFR 1910.1025 Lead
sample may not be sufficient for an adequate characterization.
2.3 NIOSH Publications:
Forfurtherguidanceandappropriatecontrolobjectivessee5.6,
“Certified Equipment,” HEW Publication No. 76-145
6.2, and 7.3.
“Recommended Industrial Ventilation Guidelines,” January
5.2 Medical Surveillance:
1976,HEW Publication No. 76-162
5.2.1 Examinations—Individuals who are currently, or who
“Criteria for a Recommended Standard Chromium (VI),”
are expected to be employed in exposure areas (see 3.1) shall
HEW Publication No. 76-129
be given preplacement and annual medical examinations that
shall include, but not necessarily be limited to the following:
3. Terminology
5.2.1.1 Work History, to elicit information on all past
3.1 Definitions of Terms Specific to This Standard:
exposures to any hexavalent chromium compounds or other
3.1.1 exposure area, n—buildings and exterior locations
toxic substances, particularly those affecting lung function.
where insoluble chromates may be present as airborne particu-
5.2.1.2 Periodic Medical Examination , consisting of at
latesinexcessoftheconcentrationsspecifiedin5.1.2,orwhere
least the following: Completion of a health history question-
there is a likelihood of skin contact with chromate containing
nairewithattentiongiventosmokinghistory,posterior-anterior
dust.
chest X-ray, complete blood count or red cell count and
3.1.2 insoluble, n—a relative term to distinguish the low-
hemoglobin, and pulmonary function studies (FVC, FEV 1.0
water solubility of the chromates listed in Table 1 from the
and FEV 1.0/FVC).
muchmorewater-solublechromatesofsodium,potassium,and
5.2.2 Medical examinations shall be made available to
ammonia. The solubilities of lead chromates and calcium
workers with symptoms of skin or upper respiratory tract
chromate are typical of the lower and upper solubilities of the
irritation at the time the symptoms are first observed or
class (see Section 6).
reported.
5.2.3 Management—Proper medical management shall be
provided promptly for workers adversely affected by exposure
Available fromAmerican National Standards Institute (ANSI), 25 W. 43rd St.,
4th Floor, New York, NY 10036, http://www.ansi.org.
AvailablefromU.S.GovernmentPrintingOfficeSuperintendentofDocuments,
732 N. Capitol St., NW, Mail Stop: SDE, Washington, DC 20401, http:// Committee on Industrial Ventilation, Documentation of TLVs, American Con-
www.access.gpo.gov. ference of Governmental Industrial Hygienist, 1985.
E848 − 94 (Reapproved 2006)
to insoluble chromates. The cause of any excessive exposure augmented as necessary by personal protective equipment or
shallbesoughtwithoutdelay,andcorrectiveactioninitiated.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 EyeIrritation—Flushthoroughlywithcopiousquan-
likelihoodofexceedingthePEL.Brushorrollerapplicationof
tities 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 OSHA29 CFR 1910.134 and
standard, appropriate warning signs, barricades, or work prac-
inANSI 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
tivetestissatisfactory (14, 15).Thetypeofrespiratorrequired
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
labeled. 5.4.4 Clothing—Any employee exposed to airborne levels
5.3.3 Material Safety Data Sheet (MSDS)—The MSDS or of chromium above the PELor when the possibility of skin or
equivalent is the primary source of the safety and health eye irritation exists, should be supplied with appropriate
information. The chemical identification and MSDS for all protective work clothing such as coveralls or similar full-body
insoluble chromates used in the workplace must be made
work clothes. See for example, ANSI Z87.1 for eye and face
readily accessible to all employees. The MSDS in conjunction
protection guidelines. Clean work clothing should be supplied
with the identity on the label and employee training will
at least weekly to employees in these cases. All protective
convey the hazard(s) (both physical and health) determination
clothingmustberemovedatthecompletionofeachworkshift
for the chromate compounds. Information on the MSDS must
in the change room provided for this purpose. Employees
include:
exposed to chromium above the PELshould shower at the end
5.3.3.1 The OSHA PEL and the ACGIH TLV.
of the work shift. Employees must not wear or take any of the
5.3.3.2 A statement to that effect if the chromate has been
protective equipment off the work site. Care must be taken to
identified as a suspect carcinogen by the National Toxicology
prevent any cross contamination of street clothes.
Program (NTP), the International Agency for Research on
5.4.5 Hand Protection—Suitable gloves to minimize skin
Cancer (IARC), OSHA, or the employer.
contact shall be worn during operations where chromates are
5.3.4 Finished Product Labels, are the responsibility of the
handled and may contact skin. Hands shoul
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