Intermedia Priority Pollutant Guidance Documents
Prepared and Edited by.
Robert Kayser, Ph.D.
Doreen Sterling, Ph.D.
Donn Viviani, Ph.D.
Chemical Coordination Staff
Office of Toxic Substances
U.S. Environmental Protection Agency
July 1982
(Revised October 1984)
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Introduction
The Intermedia Priority Pollutant (IPP) Guidance Documents are
designed to provide an overview of current regulatory and tech-
nical information on a group of toxic chemicals of intermedia
concern. Topics covered include: physical/chemical properties;
health and environmental effects; producton, use, release, and
exposure; regulatory status; recommended criteria and standards;
spill clean-up/disposal; and analytical methodologies. Key pro-
gram office contacts are also provided.
The original IPP chemicals were selected in December 1980 by a
work group composed of a representative from each regulatory
program office and the regions using a composite candidate list
of all chemicals that each program office considered a "priority".
Each chemical was considered in terms of its intermedia transport
properties, health effects, exposure patterns, and other factors
that would indicate that the chemical was an intermedia and, there-
fore, inter-office problem.
These documents were prepared using published technical documents
submitted by involved program offices, which CCS abstracted. All
of the documents were reviewed in draft by both the program offices
and the regions, and appropriate revisions have been made.
Tne IPP documents have been formatted so that they can be updated
as needed and new chemicals suggested by 'the Regional Offices added.
We hope you find this document useful. Your comments or suggestions
are welcome.
Steven D. Newburg-Rinn
Acting Director
Chemical Coordination Staff
Office of Toxic Substances
October, 1984
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MARCH 1984
Intermedia Priority Pollutant (IPP) Chemicals
Acrylonitrile
Arsenic
* Asbestos
Benzene
* Cadmium
Chlorinated Organic Solvents
Trichloroethene (TCE)
Tetrachloroethene (PCE)
1,1,1-Trichloroethane (methylchloroform)
Carbonte trachloride
Methylen-e Chloride
Chloroform
Chlorophenols
Chromium
Dichlorobenzenes
1,2-Dichloroethane (Ethylene dichloride or EDO
* Formaldehyde
* Lead
Mercury
PCBs
Phthalnte Esters
2,3,7, 8-Tetrachlorodibenzo-p-Dio::in (TCDD)
Toluene
* Selected sections have been updated.
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Acrylonitrile
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ACRYLONITRILE
Table of Contents Page
Physical/Chemical Properties and Chemistry 1-1
Properties 1-1
Chemistry and Environmental Fate/Transport 1-1
Effects Information 2-1
Health Effects 2-1
Environmental Effects 2-3
Environmental Release 3-1
Air Releases 3-1
Water Releases 3-1
Land Releases 3-1
Exposure Routes 4-1
Air Exposure 4-1
Water Exposure 4-1
Other Exposure Routes 4-1
Data Bases 5-1
Chemicals in Commerce Information System (CICIS) 5-1
EPA Chemical Activities Status Report (EPACASR) 5-1
NIH/EPA Chemical Information System (CIS) 5-1
Chemical Regulations and Guidelines System (CRGS) 5-1
Chemical Substances Information Network (CSIN) 5-1
EPA Information Clearinghouse 5-2
Regulatory Status 6-1
Promulgated Regulations 6-1
Proposed Regulations 6-2
Other Actions 6-2
July, 1982
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Standards and Recommended Criteria 7-1
Air 7-1
Water 7-1
Spill or Other Incident Clean-Up/Disposal 8-1
Hazards and Safety Precautions 8-1
First Aid 8-1
Emergency Action 8-1
Notification and Technical Assistance 8-1
Disposal 8-2
Sampling, Acceptable Analytical Techniques, and Quality Assurance 9-1
Air 9-1
Water 9-1
Solid Waste 9-3
Other Samples 9-3
Quality Assurance 9-3
References and Office Contacts R-l
July, 1982
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ACRYLONITRILE
1. PHYSICAL/CHEMICAL PROPERTIES AND CHEMISTRY
1.1 Properties
Acrylonitrile Is a chemical intermediate used in the production of
synthetic fibers, plastics, and elastomers. Synthetic acrylic and
modacrylic fibers are widely used in apparel and home furnishings,
while high-impact acrylonltrile resins are used in appliances, auto-
mobiles and housewares. Acrylonitrile ranked forty-second in overall
domestic production in 1980 with a production volume of 830,000
metric tons (1.8 billion Ib).
Some of the important properties of acrylonitrile are listed in
Table 1. Acrylonitrile is a toxic, volatile liquid which is moder-
ately soluble in water. Acrylonitrile is highly flammable (flash
point -4.4°C) and the vapors are explosive. The characteristic odor
of this reactive chemical is unpleasant and irritating (ECAO, 1981).
1.2 Chemistry and Environmental Fate/Transport
All acrylonitrile is currently produced using propylene as the raw
material. Most processes utilize a mixture of propylene, ammonia,
and air in the presence of a catalyst; acetonitrile and hydrogen
cyanide are by-products of this process. Commercial acrylonitrile is
a highly pure product and is stabilized against self-polymerization
with water and methylhydroquinone (35-50 ppm) (ECAO, 1981).
Polymerization, the most important commercial reaction of acrylo-
nitrile, may be initiated by free radicals or light; oxygen is a
powerful inhibitor of this process. Acrylonitrile is used commer-
cially to produce acrylamide (CH2=CHCONH2) and adiponitrile, a raw
material for nylon production. The double bond in acrylonitrile is
also susceptible to attack at the terminal carbon atom in the double
bond (i.e., CH2=CH-CN + YH • CH2Y-CH2-CN); this addition reaction
is called cyanoethylation (ECAO, 1981; OWRS, 1979).
Acrylonitrile is thought to be primarily an airborne hazard due to
its volatility. Acrylonitrile contains a carbon-carbon double bond
which should enhance its reactivity toward atmospheric photo-oxida-
tion by hydroxyl radicals or other oxidants. Expected products in-
clude hydrogen cyanide (HCN), carbon monoxide (CO), formaldehyde
(HCHO), and formic acid (HCOOH). Laboratory studies suggest that
acrylonitrile vapor has an estimated atmospheric half-life of 9-10
hours (OAQPS, 1979).
There is limited information on the fate of acrylonitrile in the
aquatic environment. However, the volatility of this pollutant
indicates that transport to the atmosphere is likely. Hydrolysis and
photolysis reactions of acrylonitrile are probably not relevant in
natural surface waters. On the basis of the octanol/water partition
coefficient, acrylonitrile is not expected to undergo significant
1-1 July, 1982
-------
adsorption on organic sediment or bioaccumulation in aquatic organ-
isms. However, the reaction of acrylonitrile with nucleophiles in
proteins (amino and sulfhydryl groups) may lead to accumulation of
the cyanoethylated form. Acrylonitrile is degraded by sewage sludge
and is susceptible towards biodegradation in natural waters at low
concentrations «50 ppm) (OAQPS, 1979; OWRS, 1979).
The volatile products produced from combustion of acrylonitrile and
acrylonitrile resins are toxic. Thermal degradation of acryloni-
trile, polyacrylonitrile, acrylonitrile-styrene resins (AS), and
acrylonitrile-butadiene-styrene plastics (ABS) result in the release
of hydrogen cyanide as the predominant volatile product. Acryloni-
trile contained in acrylic fibers and in non-food contact ABS/SAN
will not migrate under normal use. However, acrylonitrile monomer is
reported by FDA to migrate from nitrile resins used in beverage con-
tainers (OAQPS, 1979).
1-2 July, 1982
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TABLE 1; PROPERTIES OF ACRYLONITRILE*
Synonyms ; Cyanoethylene, 2-propenenitrile
vinyl cyanide , AN
CAS Number; 107-13-1
Molecular Formula:
Structure; ^
CSN
Physical Properties;
Melting point: -83.5°C
Boiling point: 77.5 - 79°C
Vapor pressure (25°C): 110 - 115 torr
Flash point (closed cup): -4.4°C
Density (20°C): 0.806 g/ml ; vapor: 1.83 (air = 1)
Solubility in water (20°C): 73.5 g/1
Partition coefficient
(octanol/water) : log P = -0.92 (calculated)
•j
Conversion Factor: 1 ppm in air = 2.17 mg/mj
*Source: (ECAO, 1981).
1-3 July, 1982
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2. EFFECTS INFORMATION
2.1 Health Effects (CONTACT: Bob McGaughy, FTS 755-3968)
2.1.1 Acute Toxlcity
The acute toxic effects of acrylonitrile are reported to be similar
to those from cyanide poisoning. Worker exposure to 16-100 ppm for
20-45 min. was reported to lead to headache, vertigo, vomiting, trem-
ors, and convulsions. Other symptoms may Include mild jaundice,
nasal and respiratory oppression, and diarrhea.
Acrylonitrile acute toxiclty varies widely among animal species.
Acute oral (LDjo) for laboratory animals ranges from 27 to 113 mg/kg;
mice appear to be the most sensitive with LDjQ values of 25 to 48
mg/kg. With respect to Inhalation exposure, fatalities in experimen-
tal animals occurred after four hours exposure to levels ranging from
100 ppm (dogs, 7 out of 7 died) to 576 ppm (guinea pigs, 10 out of 16
died) (ECAO, 1981; OTS, 1978).
2.1.2 Chronic Toxicity
Long-term occupational exposure to acrylonitrile may affect the cen-
tral nervous system, the liver, and blood. Exposed workers have
exhibited hematological effects, including low hemoglobin, leucoyte,
and erythrocyte counts, at exposure levels of 1.2 to 2.3 ppm. Dermal
exposure produces diffuse erythema, blistering, and swelling. In
animals, long-term administration may affect growth, food and water
intake, adrenal function, and the central nervous system. However,
of more concern is recent evidence concerning the carcinogenic poten-
tial of acrylonitrile.
Carcinogenicity, Mutagenicity, and Teratogenicity - Based on evidence
from animal experiments, epidemloLogic Investigations, and
mutagenicity assays, both IARC (the International Agency for Research
on Cancer) and EPA (Office of Health and Environmental Assessment)
consider acrylonitrile an animal carcinogen and a potential human
carcinogen. Animal studies have involved exposure by ingestion and
inhalation.
All four animal studies in which rats received acrylonitrile in
drinking water showed Increased incidences of tumors In the brain
(astrocytomas) and ear canal (zymbal gland); excess tumors in various
other organs were noted in some of the studies. In three studies
tumors were observed at doses as low as 10 to 100 ppm (equivalent to
daily dosages of approximately 1.2 to 12 mg/kg body weight, respec-
tively) over treatment schedules of 19 to 26 months. The other
drinking water study was actually a three-generation reproductive
study in which tumors were observed in the second generation. Expo-
sure of rats by inhalation Is also reported to increase tumor inci-
dence. In one study, rats exposed to 5 to 40 ppm acrylonitrile in
air (4 hrs/day, 5 days a week, for 12 months) showed marginal in-
creases In tumors of the mammary region and stomach. A study by Dow
2-1
July, 1982
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Chemical Company confirmed the increase in tumor incidence in rats
exposed to acrylonitrile by inhalation (20 to 80 ppm in air for 6
hrs/day, 5 days/week, for 24 months) (ECAO, 1981; IARC, 1979).
An occupational epidemiology study that involved workers exposed to
acrylonitrile at a DuPont textile fibers plant indicates an excess
risk of cancer (most notably, lung and colon cancer). However, lack
of monitoring data prevents the calculation of a reliable quantita-
tive estimate of worker exposure or risk (ECAO, 1981).
Based on the brain tumor incidence (astrocytomas) in female rats in-
duced by acrylonitrile in drinking water, EPA (Office of Health Re-
search) has calculated a risk factor for cancer in humans. Based on
the above data, ingestion of about 1.3 ug/day is estimated to result
in an increase in cancer risk of 10~5 (l in 100,000). Using this
risk factor, OWRS has calculated the following human Water Quality
Criteria for acrylonitrile: for ingestion of contaminated water and
aquatic organisms, 0.58 ug/1 corresponds to an increased cancer risk
of 10~5; for consumption of aquatic organisms only, the level would
be 6.5 ug/1 (OWRS, 1980).
The mutagenicity of acrylonitrile has been examined in various bac-
terial and mammalian systems (ECAO, 1981). Mutagenic reponses were
observed in the Ames Salmonella test in the presence of a mammalian
activation system. Base-pair substitution may result from a possible
carcinogenic metabolite of acrylonitrile. One of the proposed meta-
bolic pathways for acrylonitrile postulates an epoxide as a transient
metabolite; epoxides as a group are regarded as being potential car-
cinogens. Also, acrylonitrile itself has been shown to react (cyano-
ethylation) with ring nitrogen atoms of certain tRNA nucleosides and
this suggests that acrylonitrile may react with base residues in
DNA. However, it is not known if these nucleotide reactions occur
under physiological conditions.
Adverse maternal and fetal effects, including teratogenic effects,
were reported after pregnant rats were given oral doses of
acrylonitrile at 65 mg/kg/day during gestation. Lower doses (10 to
25 mg/kg/day) caused no significant adverse effects. Acrylonitrile
has also been described as embryotoxic to pregnant mice by other
workers. (ECAO, 1981; OWRS, 1980).
2.1.3 Absorption, Distribution, and Metabolism
Acrylonitrile is readily absorbed by inhalation or ingestion; dermal
absorption is comparatively poor. Acrylonitrile or its metabolites
are distributed to all tissues, with high levels found in red blood
cells, skin, and stomach, regardless of route or dose. Acrylonitrile
is metabolized in animals to cyanide ion (CN-) which is then
converted to thiocyanate (SCN-). However, blood protein binding and
other reactions with tissue nucleophiles via cyanoethylation compete
with conversion to cyanide. The oxidative pathway which leads to
2-2 July, 1982
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cyanide is thought to involve conversion by mixed function oxidases.
For example, oxidation of acrylonitrile may lead to an epoxide which
could be hydrated, rearrange, or react with nucleophiles; in any
case, cyanide would be produced (ECAO, 1981).
There has been considerable disagreement about the mechanism of
acrylonitrile toxicity. While the liberation of cyanide was
originally thought to produce all toxic reactions, the prevalent
opinion now is that toxicity results largely from direct effects of
the acrylonitrile itself or other organic metabolites (such as an
epoxide). The blocking of important sulfhydryl group containing
enzymes by cyanoethylation has been suggested as a possible mechanism
for acrylonitrile toxicity (ECAO, 1981).
2.2 Environmental Effects (CONTACT: Richard Carlson, FTS 783-9511)
2.2.1 Aquatic Effects
The data base for acrylonitrile is deficient in several important
aspects. Acute toxicity data are lacking for planktonic or benthlc
crustaceans, benthic insects, detritivores, and salmonid fishes. Of
the data available, only one of the 96-hour LCso values for the fat-
head minnow was generated in a flow-through test, the rest being
static tests; all acute tests used unmeasured concentrations. The
range of EC50 and LCso values is from 7,550 to 33,500 ug/1. The
chronic data are limited to one inconclusive test with Daphnia magna
and a 30-day LCjQ value for the fathead minnow of 2,600 ug/1.
Despite these limitations, there is enough information available to
indicate that acrylonitrile merits some consideration of its possible
toxicological effects on freshwater aquatic life. In particular,
these data suggest that acrylonitrile has a definite chronic or cumu-
lative effect and that adverse effects can be expected to occur at
concentrations below 2,600 ug/1 in fish exposed to this compound for
more than 30 days. The only datum on saltwater species is a 24-hour
LC50 value of 24,500 ug/1 for the pinfish (OWRS, 1980).
2-3
July, 1982
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3. ENVIRONMENTAL RELEASE
Acrylonitrile is manufactured for use as feedstock in the synthesis
of a variety of materials and chemicals. During 1978 the industry
produced 800,000 metric tons of acrylonitrile. The major use for
acrylonitrile is in the production of acrylic and modacrylic fibers
and acrylonitrile-butadiene-styrene (ABS) and styrene-acrylonitrile
(SAN) resins. Acrylonitrile is also used as a raw material in the
manufacture of nitrile elastomers and barrier resins and as an inter-
mediate in the production of adiponitrile and acrylamide. Approxi-
mately 17% of the domestic production was exported during 1978.
The total discharge of acrylonitrile to the environment is estimated
to be about 2% of the total annual production. Acrylonitrile, a vol-
atile compound, is released primarily through air emissions from pro-
duction facilities and acrylic fiber and ABS/SAN resin manufacturing
operations. Air releases account for about 87% of the total re-
leases, while water releases account for nearly all of the other
13%. Releases in solid waste are considered to be relatively small.
Current release estimates are based on limited data and are subject
to a high degree of uncertainty.
A summary of acrylonitrile production, consumption, and environmental
release for 1978 is presented in Table 2. The major sources of envi-
ronmental release of acrylonitrile to air and water are listed be-
low. Accidental spills are also considered a potential source of re-
lease because acrylonitrile is liquid, volatile, and highly soluble
in water, and therefore readily released to the environment if
spilled.
3.1 Air Releases (CONTACT: Nancy Pate, FTS 629-5502)
Significant Sources
Acrylonitrile production plants (SIC 2869)
Acrylic and modacrylic fiber manufacturing plants (SIC 2824)
ABS/SAN resin manufacturing plants (SIC 2821)
Adiponitrile production (SIC 2869)
Acrylamide plants (SIC 2869)
3.2 Water Releases
Significant Sources
• Acrylic and modacrylic fiber manufacturing plants (SIC 2824)
• ABS/SAN resin manufacturing plants (SIC 2824)
3.3 Land Releases
No significant sources. Wastes from acrylonitrile production plants
and facilities using acrylonitrile, and accidental spills are possi-
ble sources of minor releases.
3-1 July, 1982
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TABLE 2: ACRYLONITRILE SUPPLY, CONSUMPTION, AND RELEASES (1978)*
I. Production and Emissions
Acrylonitrile production
Supply
(kkg)
800,000
Consumption
(kkg)
Airborne
Emissions
(kkg/yr)
5,300
Water
Releases
(kkg/yr)
LJ
I
ro
II. Uses and Emissions
Acrylic and modacrylic fiber
ABS/SAN resins
Adiponitrlle
Nitrile elastomers
Latex Production
Acrylamide
Nitrile barrier resins
Minor miscellaneous uses
Exports
Totals
326,000
167,000
87,500
24,000
7,760
25,700
10,200
11,800
135,000
3,300
800
40
10
400
100
NA
140
850
90
20
NEC
NEC
20
NA
40
794,960
11,790
1,830
I-1
*<
00
ts>
*Source: (OTS, 1980).
NA = not available NEC = negligible
Total land/solid waste releases are considered negligible (less than 1 kkg/yr).
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4. EXPOSURE ROUTES
The National Institute of Occupational Safety and Health (NIOSH) has
estimated that 125,000 people are potentially exposed to acryloni-
trile in the workplace. EPA has estimated that 2.6 million people
are exposed to an annual average concentration of acrylonitrile rang-
ing up to 20 ug/m3 (OAQPS, 1979).
Acrylonitrile is readily absorbed in humans by inhalation and oral
routes. The principal route of exposure for acrylonitrile is ambient
air. Exposure may also occur to a limited extent via drinking water,
dermal absorption, and food.
4.1 Air Exposure
Exposure estimates for air were calculated by SRI for EPA using
dispersion modeling. Annual average atmospheric concentrations of
acrylonitrile ranged up to 20.0 ug/m3- Estimates are presented in
Tables 3 and 4 of the number of people exposed to various increments
of acrylonitrile concentrations (OAQPS, 1979).
4.2 Water Exposure
No exposure estimates for drinking water were available. However,
since less than 2000 metric tons of acrylonitrile are released to the
water (roughly 15% of the amount released to the air), it is probable
that exposure via drinking water is not great. The volatility of
acrylonitrile also aids in intermedia transfer to the air.
4.3 Other Exposure Routes
Dermal Absorption
Acrylonitrile is not readily absorbed through the skin. Studies of
dermal absorption of acrylonitrile vapor found the penetration rate
of the vapor through the skin to be about one percent relative to the
quantity absorbed by the lungs (ECAO, 1981).
Food
The U.S. Food and Drug Administration banned the use of acrylonitrile
resin in the production of soft drink bottles; however, this Is
currently under revision. The use of this resin is allowed in other
food packaging. Although no exposure estimates are available, food
contaminated with acrylonitrile resin is a potential, albeit minor,
exposure route.
4-1 July, 1982
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TABLE 3: ESTIMATED HUMAN EXPOSURES TO ATMOSPHERIC
ACRYLONITRILE FROM PRODUCERS
Annual Average
Atmospheric AN
Concentration (ug/m3)
10.0-14.9
5.0-9.99
1.0-4.99
0.500-0.999
100-0.499
0
0.050-0.099
Number of
People Exposed
50
240
64,000
140,000
1,800,000
600,000*
Total People 2,600,000
(approx.)
Source: (OAQPS, 1979).
^Exposures in these ranges are underestimated because calculations were made
only for exposures within 30 km of each plant.
TABLE 4: ESTIMATED HUMAN EXPOSURE TO ATMOSPHERIC ACRYLONITRILE
FROM PLANTS THAT USE ACRYLONITRILE
Chemical Product
Annual Average
AN Concentration
ug/m3
15.0-19.9
10.0-14.9
5.00-9.99
1.00-4.99
0.500-0.999
0.100-0.499
0.050-0.099
0.010-0.049
0.005-0.009
0.001-0.004
Total People
(approx. )
ABS/SAN
Resin
2,700
850
73,000
79,000
680,000
1,200,000
1,400,000+
510,000+
790,000+
4,700,000
Acrylic and
Modacrylic
Fibers
4,700
52,000
70,000
370,000
190,000
260,000+
0+
0+
950,000
Nitrile
Elastomers
1,800
22,000
81,000
650,000
690,000
2,700,000
5,100+
93,000+
4,200,000
Adiponitrile
22,000
32,000
65,000+
0+
0+
120,000
Source: (OAQPS, 1979).
+Exposures in these ranges may be underestimated because calculations were
made only for exposures within 30 km of each plant.
4-2
July, 1982
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5. DATA BASES
5.1 Chemicals in Commerce Information System (CICIS)
The Inventory was compiled under the authority of Section 8 of TSCA,
which requires manufacturers to report to EPA the chemicals imported
and manufactured during calendar year 1977. The Inventory lists the
Chemical Abstract Service (CAS) preferred name for the chemicals,
their respective CAS numbers (often used for identification pur-
poses), production site, company name, and volume(s) of production
and import. There is also a Confidential Inventory in which many of
these characteristics are claimed confidential by the manufacturer.
In these instances, the confidential information will not be avail-
able on the public inventory. CICIS can now be accessed through the
NIH/EPA Chemical Information System (CIS - see 5.3). For further
information, contact Gerri Nowack at FTS 382-3568.
5.2 EPA Chemical Activities Status Report (EPACASR)
EPACASR is an on-line system containing information on EPA's interest
in chemicals. This system includes data on the Agency's regulations,
research, and assessments directed toward specific chemicals.
EPACASR is published annually and the data base is updated as
information is received. A searchable subset itemizes NTP/NCI
studies and results, as well as chemicals discussed in the IARC
monograph series. (Other sources are added as appropriate.) Entries
identify the statutory authority, the nature of the activity, its
status, the reason for and/or purpose of the effort, and a source of
additional information. Searches may be made by CAS Number or coded
text. For further information contact Eleanor Merrick at FTS
382-3415.
5.3 NIH/EPA Chemical Information System (CIS)
This is a collection of various scientific data bases available
through an interactive computer program. The linking system between
these data files is the Structure and Nomenclature Search System
(SANSS). CIS can also provide a list of non-CIS sources of informa-
tion on a chemical of interest. However, these files have to be
accessed individually by either separate on-line systems or in hard-
copy. For further information, contact Delores Evans at FTS 382-3546
or Irv Weiss at FTS 382-3524.
5.4 Chemical Regulations and Guidelines System (CRGS)
CRGS is an on-line data base that is being developed to provide
information on chemical regulatory material found in statutes, regu-
lations, and guidelines at the Federal, State, and international
levels. Currently, only the first phase of CRGS, which encompasses
source material only at the Federal level, is operational. Nation-
wide access to CRGS is available through Dialog. For further infor-
mation, contact Delores Evans at FTS 382-3546 or Ingrid Meyer at FTS
382-3773.
5-1 July, 1982
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5.5 Chemical Substances Information Network (CSIN)
The prototype CSIN, operational since November 1981, has been devel-
oped by merging the technologies of computer networking and distrib-
uted data base management. CSIN is not another data base, but a
library of systems. Through the CSIN front-end intermediary manage-
ment computer, the user may access and use independent and autonomous
information resources that are geographically scattered, disparate
for data and information content, and employ a variety of types of
computer hardware, software, and protocols. Users may converse in
and among multiple systems through a single connection point, without
knowledge of or training on these independent systems.
Currently, six independent information resources are accessible
through CSIN. They are: National Library of Medicine (NLM), CIS,
EPA-CICIS, CAS-On-Line, SDC-orbit, and two files of Dialog: CRGS and
TSCA Inventory. The CSIN management computer allows the user to cre-
ate, retrieve, store, manipulate data and queries. This eliminates
the need for re-entering long lists of chemical identifiers or other
information elements that are part of the original query or that have
been identified and acquired from one or more of the CSIN resources.
For further information contact Dr. Sid Siegal at FTS 382-2256.
5.6 EPA Information Clearinghouse
The EPA Information Clearinghouse is a bibliographic data base com-
posed of over 475 individual data bases and models which contain mon-
itoring information and statistics on a variety of chemicals. The
individual data bases are maintained for offices within EPA. For
further information, contact Charlene Sayers at FTS 755-9112.
The following data bases contain information on acrylonitrile:
BAT Review Study for the Timber Products Processing, Gum and Wood,
Chemicals, and the Printing and Publishing Industries
Best Management Practices, Timber Industry Effluent Guidelines -
Runoff
Best Management Practices, Timber Industry Effluent Guidelines -
Sludge
Chemicals in Commerce Information System
Compliance Sampling Toxicant Surveys
Consolidated Permits Program-Application Form l,2b,2c
Data Collection Portfolio for Industrial Waste Discharges
Distribution Register Organic Pollutants in Water
Energy and Mining Point Source Category Data Base
Federal Facilities Information System
Fine Particle Emissions Information System
Food Industry Group
Fugitive Emissions Information System
Gaseous Emissions Data System
Hazardous Waste Site Tracking System
Hazardous Waste Data Management System
Hemlock, Michigan Environmental Samples
5-2 July, 1982
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Humacao Ambient Data Base
IFB Organics Data Base
Indicatory Fate Study
Industrial Process Evaluations
Innovative Technology, Timber Industry Effluent Guidelines
Inorganic Chemicals Industry Regulation Record
LiPar1 Landfill
Liquid Effluents Data System
Listing of Organic Compounds Identified in Region IV
Love Canal Data Handling System
Method Validation Studies of Priority Pollutants
National Electronic Injury Surveillance System
National Pollutant Discharge Elimination System (NPDES) Discharge
Permit Compliance
Nationwide Urban Runoff Program
Needs Survey
New York Bight Ocean Monitoring Program
Organic Chemicals/Plastics Industry
Paint and Ink Analytical Data
Permit Compliance System
Pesticide Incident Monitoring System
Pesticide Product Information System
Pharmaceutical Screening/Verification Data Base
Precision and Accuracy for Screening Protocols
Priority Pollutants-Region I
Priority Pollutants-Region III
Publicly Owned Treatment Works (POTW) Analytical Data
Publicly Owned Treatment Works (POTW) Quality Control
Puerto Rico Reservoirs
Regional Toxics Monitoring Program
Resource Conservation and Recovery Act (RCRA)-Hazardous Waste Site
Inspections
Screening Sampling Program
Sources of Toxic Pollutants Found in Influents to Sewage Treatment
Plants
Spill Prevention Control and Countermeasure
System for Consolidated Permitting and Enforcement Data Base
Textile Industry BAT Study-Toxic Sampling Data
Toxics Monitoring
U.S. Virgin Islands-St. Thomas, St. Croix
Verification Data Base
Waste Characterization Data Base
Water Quality Information System
5-3 July, 1982
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6. REGULATORY STATUS (Current as of 4/16/82)
6.1 Promulgated Regulations
6.1.1 EPA Programs
Clean Water Act (CWA)
• Section 311 - Acrylonitrile is classified as a hazardous sub-
stance (40CFR116.4) and discharges are subject to reporting re-
quirements (40CFR117.3).
• Sections 301, 304, 306, and 307 - Acrylonitrile is listed as a
toxic pollutant (40CFR401.15) and is subject to effluent limita-
tions. Effluent guidelines or standards have not yet been pro-
mulgated, however, NPDES permit applicants in specified indus-
trial categories are required to report quantitative data for
several organic pollutants including acrylonltrile; analytical
methods are specified (40CFR122.53(d)(7)).
Resource Conservation and Recovery Act (RCRA)
• Section 3001 - Acrylonitrile is listed as hazardous waste number
U009 (40CFR261.33). The following solid wastes are designated
hazardous wastes due, in part, to the presence of acrylonltrile
(40CFR261.32).
Organic Chemicals Industry:
- (K011) - bottom stream from stripper in acrylonitrile produc-
tion
- (K013) - bottom stream from acetonitrile column in production
of acrylonitrile
- (K014) - bottoms from acetonitrile purification during acry-
lonitrile production
• Sections 3002 to 3006 - Regulations for generators and trans-
porters of hazardous waste and standards for treatment, storage
and disposal are applicable (40CFR262 to 265).
Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA)
• Sections 3 and 25(a) - Pesticide products containing acryloni-
trile in combination with carbon tetrachloride are classified
for restricted use (40CFR162.31).
6-1 July, 1982
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6.1.2 Programs of Other Agencies
OSHA - Occupational Safety and Health Act
• Sections 6 and 8 - Permissible exposure level as an 8-hr. TWA
concentration, is 2 ppm, with a ceiling of 10 ppm for any 15-
minute period. Exemptions and other safeguards are described
(29CFR1910.1045).
DOT - Hazardous Materials Transportation Act
• Acrylonltrile is classified as a flammable liquid and a poison.
Complete regulation is required regardless of amounts shipped;
it is forbidden on passenger-carrying aircraft or railcar (40-
CFR172.101); other regulations exist for transporting and pack-
aging (40CFR171-177).
FDA - Food, Drug, and Cosmetic Act
• FDA regulates the use of acrylonitrile in a variety of polymer
and copolymer products if the use involves contact with food;
such materials may be used under certain conditions (21CFR173 to
181). Use in fabrication of beverage containers is prohibited
(21CFR177).
6.2 Proposed Regulations
6.2.1 EPA Programs
CAA
• A New Source Performance Standard (NSPS) has been proposed to
control fugitive emissions from the manufacture of volatile or-
ganic chemicals (VOCs) from new process units within the syn-
thetic organic chemical manufacture industry (46FR1136).
CWA
Self-monitoring for acrylonitrile is proposed for various pro-
cesses used to produce ABS and SAN polymers and acrylic fibers
(44FR47113).
Proposal to add 40CFR125 establishing ocean discharge criteria
including toxic pollutants listed in 40CFR401.15; includes acry-
lonitrile (45FR9549).
6.3 Other Actions
Comprehensive Environmental Response, Compensation, and
Liability Act (CERCLA or Superfund) - CERCLA provides for the
liability,compensation,clean-up,and emergency response for
the release of hazardous substances into the environment. This
Act also deals with the cleanup of hazardous waste disposal
sites. (42USC9601; PL96-510). EPA is developing regulations
concerning the designation of hazardous
6-2 July, 1982
-------
substances, the development of reportable quantities, claims proce-
dures, and the confidentiality of business records (46FR54032). Re-
visions to the National Contingency Plan (NCP) as required by CERCLA
have been issued in a proposed rule (47FR10972). Hazardous sub-
stances as defined by Section 101(14) of CERCLA include: hazardous
wastes designated under Section 3001 of the RCRA; hazardous air pol-
lutants regulated under Section 112 of the CAA; and water pollutants
listed under Sections 307 and 311 of the CWA (and also any substances
regulated in the future under Section 7 of TSCA and Section 102 of
CERCLA). Therefore, acrylonitrile is a hazardous substance under
CERCLA and will be subject to regulations developed under Superfund.
• Acrylonitrile is under consideration for listing under Section
112 of the CAA, which would authorize NESHAPS to control release
from specific sources (46FR54025).
• Human health-based Water Quality Criteria for acrylonitrile have
been calculated on the basis of carcinogenic potential
(45FR79324).
• After a preregulatory assessment, the Office of Drinking Water
has decided that national drinking water regulations under SDWA
will not be developed at this time. In the event of drinking
water contamination problems, the Office of Drinking Water, Cri-
teria and Standards Division should be contacted for assistance
(Contact: William Lappenbusch, FTS 472-6820).
6-3 July, 1982
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7. STANDARDS AND RECOMMENDED CRITERIA*
7.1 AJT
• OSHA Standards (29CFR1910.1045)
8-hr TWA: 2 ppm
Ceiling (15 min): 10 ppm
• NIOSH Recommended Limit: 4 ppm
7.2 Hater
• Ambient Water Quality Criteria (FR4579318)
Human health (10-5 risk): 0.58 ug/1
• Hazardous spill rules require
notification of discharge equal to
or greater than the reportable
quantity (40CFR117.3). 100 Ibs.
* See Appendix A for a discussion of the derivation, uses, and limitations of
these Criteria and Standards.
7-1 July, 1982
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8. SPILL OR OTHER INCIDENT CLEAN-UP/DISPOSAL
(CONTACT: National Response Center, 800-424-8802; 426-2675 in the
Washington, D.C. area)
8.1 Hazards and Safety Precautions
Acrylonitrile readily volatilizes to a poisonous vapor. Symptoms in-
clude headache, vertigo, nausea, tremors, and nasal and respiratory
oppression. The chemical has an irritating odor.
Acrylonitrile is extremely flammable and may be ignited by heat,
sparks, or flames; vapor is explosive. Fire produces toxic combus-
tion products (Hydrogen cyanide).
Pure acrylonitrile may polymerize violently with evolution of heat in
the presence of light or at elevated temperature.
8.2 First Aid
Move victim to fresh air; give artificial respiration if not breath-
ing and oxygen if breathing is difficult. In case of contact, flush
with running water; remove and isolate contaminated clothing. Ef-
fects may be delayed.
8.3 Emergency Action
Spill or Leak - Stay upwind, isolate area, and wear breathing appara-
tus, eye protection, and protective clothing. Remove all ignition
sources. Use water spray to reduce vapors.
Fire - For small fires use dry chemical, C02, water spray, or foam.
For large fires use water spray or foam. Cool containers with water
until well after fire is out.
Isolate for 1/2 mile in all directions if tank or tankcar is involved
in a fire.
8.4 Notification and Technical Assistance
Section 103(a) of the Comprehensive Environmental Response, Compensa-
tion, and Liability Act (CERCLA or Superfund) requires notification
of the National Response Center (NRC) 800-424-8802 (in Washington,
D.C. area, 426-2675) if releases exceed reportable quantities (100 Ib
in the case of acrylonitrile).
For emergency assistance call:
CHEM TREC: 800-424-9300.
For information call EPA, Division of Oil and Special Materials
(1-202-245-3045).
8-1 July, 1982
-------
8.5 Disposal
Generators of more than 1,000 kg of hazardous waste (or residues from
spill clean-up) per month are subject to RCRA regulations. Specific
waste streams subject to Subpart D regulations are listed in Section
6.1.1 of this document.
Small quantities can be poured on sand and ignited. Protective appa-
ratus should be worn due to toxic combustion products. Chlorine so-
lutions will convert acrylonitrile to less toxic cyanates.
8-2 July, 1982
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9. SAMPLING, ACCEPTABLE ANALYTICAL TECHNIQUES, AND QUALITY ASSURANCE
9.1 Air (CONTACT: Robert H. Jungers, FTS 629-2331)
Acrylonitrile is not a regulated air pollutant*; therefore, no Agency
approved or reference procedure is available. However, a sampling
and analysis procedure using charcoal for sampling, gas chromatogra-
phy for separation, and flame ionlzation detection for analysis has
been used for monitoring around production and user facilities (NIOSH
Method S-156, NIOSH Manual of Analytical Methods, No. 77-157-C; Re-
covery of Acrylonitrile from Charcoal Tubes at Low Levels; American
Industrial Hygiene Association Journal (40) October 1979, p.
923-925).
The sampling method is currently being evaluated using 1000 rag char-
coal tubes sampled for 24 hours at a rate of 500 cc/min and 150 mg
charcoal tubes sampled for 24 hours at a rate of 150 cc/min. The de-
sorbing solvent is carbon dlsulfide with 2% by volume acetone. A gas
chromatographic column of 80/100 mesh Durapak OPN/Porosil C is
utilized to achieve the best peak separation with the flame
ionization detector.
9.2 Water (CONTACT: Thomas Bellar, FTS 684-7311
James Lichtenberg, FTS 684-7308)
Acrylonitrile (CAS No. 107-13-1) is a proposed parameter under Sec-
tion 304(h) of the Clean Water Act. It is listed as one of the pri-
ority pollutants.
There are three proposed procedures for the analysis of acrylonltrile
in natural, waste, and drinking waters. Two of the methods call for
direct aqueous injection; the third uses the purge and trap proce-
dure. For all proposed methods, detection and quantitative analysis
are made using a gas chromatograph equipped with a flame ionization
detector.
Direct Aqueous Injection;
EPA Method #626
ASTM // D3371-79
Major Equipment: Gas Chromatograph
Three to five ul of the sample is injected directly into the gas
chromatograph. The detection limit is approximately 1 mg/1 when a
flame ionization detector is used.
Purge and Trap: EPA Method //603
Major Equipment: Gas chromatograph equipped with a purge and
trap apparatus.
* Although acrylonitrile is indirectly regulated as a volatile organic com-
pound (VOC), no specific analytical procedure is approved for acryloni-
trile.
9-1 July, 1982
-------
An inert gas is bubbled through a 5 ml water sample contained in a
heated purging chamber. Acrylonitrile is transferred from the aque-
ous to the vapor phase. The vapor is swept through a sorbent trap
where the acrylonitrile is retained. After the purge is completed,
the trap is heated and backflushed with inert gas to desorb the com-
pound onto a gas chromatographic column. Detection is made with a
flame ionization detector, the method detection limit is 0.5 ug/1.
Sampling
The samples are collected in narrow-mouth bottles filled to overflow-
ing in such a manner that no air bubbles pass through the liquid.
The samples must be stored headspace free and iced or refrigerated at
4°C from the time of collection until analysis. If the sample con-
tains free or combined chlorine, add sodium thiosulfate preservative
to the sample bottles before filling (10 mg/40 ml is sufficient for
up to 5 ppm Cl2.) All samples must be analyzed within 14 days of
collection.
List of Procedures for Acrylonitrile
Method3
EPA 603
EPA 626
ASTM #03771-79
Typeb
P&T
DAI
DAI
MDL
0.5 ug/1
1 mg/1
1 mg/1
% Standard
Recovery0 Deviation
107 5.6
Status
(March 1981)
Proposed
Proposed
Proposed
(a) See references below.
(b) p&x = Purge and Trap; DAI = Direct Aqueous Injection.
(C) Single laboratory recovery from spiked reagent water or wastewater.
References for Water Analysis
"Acrolein and Acrylonitrile" Method #626, October 1980, USEPA, Environmental
Monitoring and Support Laboratory, Cincinnati, Ohio 45268. Also see
44FR69532.
"Standard Test Method for Nitriles in Aqueous Solution by Gas-Liquid Chroma-
tography," Annual Book of ASTM Standards, 1980, Part 31, Water, ASTM D
3371-79.
"Methods for Organic Chemical Analysis of Water and Wastes by GC, HPLC, and
GC/MS," Method 603: Acrolein and Acrylonitrile, USEPA, Environmental Moni-
toring and Support Laboratory, Cincinnati, Ohio 45268. Also see 44FR69479.
9-2 July, 1982
-------
9.3 Solid Waste (CONTACTS: M. Hiatt, FTS 545-2118;
W. Beckert, FTS 545-2137)
Method 8.03 (Test Methods for Evaluating Solid Wastes - Physical/
Chemical Methods; EPA/SW-846 (1980)) is approved for analyses of
acrylonitrile in solid wastes.
Commonly used techniques include GC/MS for the determination of
acrylonitrile in wastes. Sample preparation may be by extraction,
purge-trap, or vacuum extraction. For extraction techniques see I.
R. DeLeon, et al., Journal of Chromatographic Science, 18, 85-88
(1980).
Purge and trap methods are described by David Speis in "Determination
of Purgeable Organics in Sediment Using a Modified Purge and Trap
Technique." Protocol, USEPA, Region II, Edison, N.J., October 10,
1980. The Love Canal Study also required purge-trap methods (see
CONTACTS).
Vacuum extraction of volatiles and collection in a liquid-nitrogen
trap permits analysis at 100 ppb with a precision of 8% and 89%
recovery. Total sample preparation takes about 36 minutes. See
above CONTACT (M. Hiatt) for details.
9.4 Other Samples
No approved method for the analyses of acrylonitrile in soil or sedi-
ment has been published. However, a recent EPA document contains
procedures for monitoring industrial sites for soil contamination
(Environmental Monitoring Near Industrial Sites; EPA-560/6-79-003;
OTS (1979)).The desorption methods used were ultrasonic agitation
of water extracts and the purge-trap technique.
9.5 Quality Assurance
Water
Single laboratory test data on simple spiked matrices have been
collected by EPA. Quality control and performance evaluation samples
are available from the Environmental Monitoring and Support Labora-
tory, Quality Assurance Branch, USEPA, Cincinnati, Ohio 45268 (See
Water CONTACTS).
Solid Waste
Standards can be obtained from Radian Corporation or EMSL-Las Vegas.
Supelco supplies diluted standards but the concentrations are not
verified. Standard solutions may also be prepared in the laboratory
from reagent-grade acrylonitrile to the appropriate dilution using
methanol. (See Solid Waste CONTACTS).
9-3 July, 1982
-------
REFERENCES
The major references used in preparation of this document are listed below.
EPA documents are listed by the EPA office of origin and the year of publica-
tion. For further information refer to the contacts given throughout this
document or contact the relevant EPA Program Offices given at the end of this
section.
(IARC, 1979)
(ECAO, 1981)
(OAQPS, 1979)
(OTS, 1978)
(OTS, 1980)
(OWRS, 1979)
IARC Monographs on the Evaluation of the Carcinogenic Risk of
Chemicals to Humans, Vol. 19, pp. 73-113; International
Agency for Research on Cancer, World Health Organization
(1979).
Health Assessment Document for Acrylonitrile; EPA-Contract
No. 68-02-3277, Environmental Criteria and Assessment Office,
(1981).
Assessment of Human Exposure to Atmospheric Acrylonitrile;
EPA-Contract No. 68-02-2835, Office of Air Quality Planning
and Standards, (1979).
Investigation of Selected Environmental Contaminants; Acry-
lonitrile; EPA-560/2-78-003, Office of Toxic Substances,
(1978).
Level I Materials Balance; Acrylonitrile; Draft Final Inter-
im Report, EPA-Contract No. 68-01-5793, Office of Toxic Sub-
stances, (1980).
Water-Related Environmental Fate of 129 Priority Pollutants;
Vol II, Chapter 105; EPA-440/4-79-029b, Office of Water
Regulations and Standards, (1979).
(OWRS, 1980) Ambient Water Quality Criteria for Acrylonitrile;
EPA-440/5-80-017, Office of Water Regulations and Standards,
(1980).
R-l
July, 1982
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OFFICE CONTACTS
The EPA offices and divisions that are listed below may be contacted for more
information relating to the indicated sections of this document. While these
offices are, in many cases, the offices of origin for the data included in
this paper, the personal contacts given throughout this document should be
contacted first. Unless otherwise noted, the offices listed are situated in
Headquarters, Washington, D.C., and the telephone numbers given are FTS
(Federal Telecommunications System) numbers. For commercial telephone calls
to Headquarters which are not placed on FTS, area code 202 must be used.
Other commercial numbers are noted for the office contacts located outside
Washington, D.C.
HEALTH AND ENVIRONMENTAL EFFECTS (Section 2)
Office of Health and Environmental Assessment (OHEA)
Environmental Criteria and Assessment Office:
Cincinnati, OH 684-7531 (513-684-7531)
Research Triangle Park, NC 629-2266 (919-541-2266)
Carcinogen Assessment Group 755-3968
Office of Drinking Water (ODW)
Health Effects Branch 472-6820
Office of Toxic Substances (OTS)
Health and Environmental Review Division 382-4241
Environmental Research Laboratory
Duluth, MN, Region V 783-9550 (218-727-6692)
ENVIRONMENTAL RELEASES AND EXPOSURE (Sections 3 and 4)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Water Regulations and Standards (OWRS)
Monitoring and Data Support Division 426-2503
R-2 July, 1982
-------
Office of Toxic Substances (OTS)
Exposure Evaluation Division 382-3873
Assessment Division 382-3442
DATA BASES (Section 5)
Office of Toxic Substances (OTS)
Management Support Division 382-3546
REGULATORY STATUS, STANDARDS, AND CRITERIA (Sections 6 and 7)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Drinking Water (ODW)
Criteria and Standards Division 472-5016
Office of Water Regulations and Standards (OWSR)
Criteria and Standards Division 755-0100
Effluent Guidelines Division 426-2571
Office of Solid Waste (OSW)
State Programs and Resources
Recovery Division 755-9107
SPILL CLEAN-UP AND DISPOSAL (Section 8)
NOTE: For Emergenices call the National Response Center at 1-800-424-8802
(1-800-426-2675 from the Baltimore/Washington area).
Office of Emergency and Remedial Response (OERR)
Emergency Response Division 245-3045
Oil and Hazardous Materials Spills Branch
Edison, NJ, Region II 340-6634 (201-321-6634)
R-3 July, 1982
-------
Office of Solid Haste (OSW)
Hazardous and Industrial Waste Division 755-9187
ANALYTICAL TECHNIQUES (Section 9)
Environmental Monitoring Systems Lab (EMSL)
Air Analysis
Research Triangle Park, NC 629-2454 (919-541-2454)
Water Analysis
Cincinnati, OH 684-7311 (513-684-7311)
Waste Analysis
Las Vegas, NV 545-2137 (702-798-2137)
GENERAL IPP COMMENTS, CORRECTIONS, OR QUESTIONS
Office of Toxic Integration
Chemical Information and Analysis Program 382-2249
R-4 July, 1982
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Arsenic
-------
ARSENIC
Table of Contents
Page
Physical/Chemical Properties and Chemistry 1-1
Properties 1-1
Chemistry and Environmental Fate/Transport 1-1
Effects Information 2-1
Health Effects 2-1
Environmental Effects 2-3
Environmental Release 3-1
Air Releases 3-1
Water Releases 3-1
Exposure 4-1
Air Exposure 4-1
Water Exposure 4-1
Other Exposure Routes 4-3
Data Bases 5-1
Chemicals In Commerce Information System (CICIS) 5-1
EPA Chemical Activities Status Report (EPA CASR) 5-1
NIH/EPA Chemical Information System (CIS) 5-1
Chemical Regulations and Guidelines System (CRGS) 5-1
Chemical Substances Information Network (CSIN) 5-1
EPA Information Clearinghouse 5-2
Regulatory Status 6-1
Promulgated Regulations 6-1
Proposed Regulations 6-2
Other Actions 6-3
July, 1982
-------
Standards and Recommended Criteria 7-1
Air 7-1
Water 7-1
Hazardous Waste 7-1
Other 7-2
Spill or Other Incident Clean-up/Disposal 8-1
Hazards and Safety Precautions 8—1
First Aid 8-1
Emergency Action 8-1
Notification and Technical Assistance 8-2
Disposal 8-2
Sampling, Acceptable Analytical Techniques and Quality Assurance 9-1
Air 9-1
Water 9-1
Solid Wastes 9-3
Other Samples 9-3
Quality Assurance 9-3
References and Office Contacts R-l
July, 1982
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ARSENIC
1. PHYSICAL/CHEMICAL PROPERTIES AND CHEMISTRY
1.1 Properties
Arsenic, which is a naturally occuring element, is produced commer-
cially as a byproduct during the processing of nonferrous metal
ores. Although most of the arsenic produced is in the form of arse-
nic trloxide, there are approximately 50 other arsenic compounds pro-
duced in the United States. Table 1 lists the physical/chemical
properties of arsenic compounds with environmental significance (OTS,
1979).
1.2 Chemistry and Environmental Fate/Transport
The chemistry of arsenic is complex due to the stability of three
oxidation states (+5, +3, -3) and also because of the propensity of
arsenic compounds to undergo complexation, precipitation, adsorption,
and biotransformation. Inorganic arsenic is generally in ionic form
as trlvalent arsenlte (+3 state, As03~3) or pentavalent arsenate (+5
state, As0^-3) salts. Cacodylic acid and methylarsonic acid and its
salts are the only widely used organic derivatives (NRG, 1977; OWRS,
1979).
Arsenic compounds are generally nonvolatile, except for the gaseous
arslnes (e.g., As 113) which are rare, and arsenic trioxide (As203>.
Due to the relatively low sublimation temperature (193°C) of arsenic
trioxide, nonferrous smelting results in significant release of this
arsenic compound to the atmosphere. The use of arsenical pesticides
and coal combustion are other major emission sources (NRC, 1977).
Arsenic is extremely mobile in the aquatic environment and may cycle
through several components, i.e., the water column, the sediments,
and the biota. Inorganic arsenate salts are very soluble in water
and are usually the predominant forms of arsenic in natural waters.
However, the reducing action of aquatic microorganisms metabolizes
arsenate to form arsenite and a variety of methylated organoarsenl-
cals (i.e., methylarsonic acid and dimethylarslnic acid). Inorganic
arsenic is removed from waters primarily by adsorption onto clays,
iron oxides, aluminum hydroxides, and organic material; coprecipita-
tlon with various metal ions is also effective in removing arsenic
from water. In most cases the sediment is the major sink for arse-
nic, but the mobilzation by underwater microorganisms returns much of
this arsenic to the water column (OWRS, 1979).
The predominant fate of arsenic applied to soil is the formation of
inorganic arsenate bound as Insoluble salts. Soluble arsenical spe-
cies are converted to insoluble forms by metal cations in the soil or
by adsorption. The equilibrium between insoluble and soluble species
can require from several days to months depending on amounts applied
and soil variables. Soluble arsenicals may be leached deeper into
the soil or be carried away as runoff into groundwater or streams.
1-1 July, 1982
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TABLE I: PROPERTIES OF ARSENIC COMPOUNDS3
Chemical Name
and Formula
Arsenic pentoxlde
AS205
Arsenic acid
H3As04.1/2 H20
Calcium arsenate
Ca3(As04>2
Lead arsenate
PbHAs04
Sodium arsenate
Na3As04
Arsenic trioxlde
As203
CAS Number Oxidation
and Synonyms State
1303-28-2 +5
Arsenic oxide
[AS205J; arsenic
acid; arsenic
anhydride
7778-39-4 +5
Orthoarsenic
acid
7778-44-1 +5
Arsenic acid,
[H3As04],
calcium salt (2:3)
7784-40-9 +5
Arsenic acid,
[l^AsO^], lead
(+2) salt (1:1);
schultenite
7631-89-2 +5
Arsenic acid,
[H3AS04J, sodium
salt
1327-53-3 +3
Arsenic [As 203]
oxide; araenous
acid; white
arsenic
Water
Transitions Solubility
Points (per liter)
Decomposes 1.5 kg (16°C)
at 315°C to
AS203 vapor
bp 160°C 170g (208C)
0.13g (25°C)
Decomposes v. si. soluble
at 720°C
389 (16°C)
Begins to 21 (25°)b
sublime at Rate of dis-
193°C. solution Is
very slowb
Specific
Properties
Forms arsenic acid,
H3As04, in water, the
salts of which are
known as arsenates.
Trlprotic acid with
pKa values of 2.2,
7.0, and 11. 5. b
Occurs in mineral
form as schultenite.
Also available as the
the potassium salt,
KH2As04. The name
"sodium arsenate" is
applied to both the
dlsodium and tri-
sodlum salts.
Forms arse nous acid
As(OH)3 in water,b
the salts of which
are known as arse-
nltes.
c
•^
GO
ro
-------
TABLE 1: PROPERTIES OF ARSENIC COMPOUNDS (cont.)
Chemical Name
and Formula
CAS Number
and Synonyms
Water
Oxidation Transitions Solubility
State Points (per liter)
Specific
Properties
Sodium Arsenite
Arsenic sulflde
Arsenic
As
Arsine
AsH3
Monosodium
methylarsonate
CH3As03HNa
Cacodylic acid
(CH3)2As02li
Arsanilic acid
7784-46-5 +3
Arsenenous acid,
sodium salt
1303-33-9 +3
Arsenic sulfide
[As2S3]; arsenic
yellow; orpiment
7440-38-2 0
Arsenic black;
metallic arsenic
7784-42-1 -3
Arsenic hydride;
hydrogen arsenide
2163-80-6
Methane arsonic
acid, monosodium
salt; arsonic acid,
methyl-, monosodium
salt; MSMA
75-60-5 Organo-
Dimethyl- metallic
arsinic acid;
Arsine oxide,
hyd roxyd imethy1-.
98-50-0 Organo-
Arsonic acid, metallic
(4-aminophenyl)-
v.sol.
mp 320°C 0.5 rag (18°C)
bp 707°C
Sublimes insoluble
at 613°C
bp -55°C 200 ml (20°C)
Organo- mp 115-
metallic 119°C
mp 200°C
570g
(25°C)
830g
(22°C)
mp 232°C sol. (Hot)
Available as the
potassium salt
KH(As02)2.
Burns in air forming
A&203+S02. Occurs
naturally as
orpiment".
When heated in air
sublimes and is
oxidized to
Faint garlic odor.
Vapor density is 2.7
times that of air.
Also available as
disodium salt,
disodlum methyl-
arsonate (DSMA).
Available as the
sodium salt
(sodium cacodylate),
Available as the
sodium salt, sodium
arsanllate.
a Source: (IARC, 1980) unless otherwise noted. b (NRC, 1977)
-------
In soils, microbiological oxidation and reduction processes act
chiefly on organic arsenicals (methylarsonic and cacodylic acids).
Eventually the organic arsenicals and inorganic arsenites are
oxidized, either chemically or biologically, to carbon dioxide and
arsenate. Arsenic removal by volatilization is reported to occur by
bacterial formation of arsines, e.g., dimethylarsine (NRG, 1977; OTS,
1976).
An important concept with respect to the distribution of arsenic in
the environment is the dynamic nature of the ecological cycling of
this element. Arsenic is ubiquitous in nature and is released from
natural sources such as weathering of minerals, volcanic action, and
decay of plant matter. Man may modify the arsenic cycle by causing
localized high concentrations through inadvertent contamination from
industrial activity, or through the widespread use of arsenic com-
pounds such as arsenical pesticides. Arsenic exists in a variety of
chemical forms which are subject to numerous chemical and biological
transformations in the environment. Because the chemical speciation
of arsenic is important in determining its adverse health and
ecological effects, transformations may significantly alter the
mobility and toxicity of arsenic (NAS, 1977).
1-4 July, 1982
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2. EFFECTS INFORMATION
2.1 Health Effects (CONTACTS: Jerry Stara, FTS 684-7531; Les Grant, FTS
629-2266; Ed Ohanian, FTS 472-6820)
Chemical species of arsenical compounds differ greatly in their tox-
icity. For example, trivalent species (e.g., arsenites) of inorganic
arsenic are generally considered more toxic than pentavalent species
(e.g., arsenates). Organic arsenic species (e.g., cacodylic acid)
are much less toxic than the inorganic species; organoarsenicals
found in seafood are essentially nontoxic. Arslne and its methyl de-
rivatives are the most acutely toxic of all the arsenical compounds.
2.1.1 Acute Toxicity
Acute arsenic toxicity can cause severe intestinal injury, accompa-
nied by shock, pain, vomiting, diarrhea, muscle cramps, and cardio-
vascular disturbances. In some cases, these can progress to convul-
sions, paralysis, and death from circulatory failure. Delayed-onset
injury to the motor and sensory nerves, congestive heart failure, and
skin lesions are also seen, as well as severe red blood cell breakage
and kidney failure. The acute lethal dose for humans appears to
range from 70 to 180 mg for trivalent arsenic. Subacute doses in
the range of 50 mg over a 2-week period may produce demonstrable
clinical effects such as anorexia, fainting, nausea and some vomit-
ing, dry throat, shooting pains, diarrhea, nervous weakness, tingling
of the hands and feet, jaundice, erythema, and peripheral neuropa-
thy. Longer exposure can result in dry, falling hair; brittle, loose
nails; eczema; darker skin; exfoliation; and hyperkeratoses of the
palms and soles (OWRS, 1980; ECAO, 1980).
Exposures to arsine concentrations of 25 ppm for 30 minutes can be
fatal, and 3 to 10 ppm can cause symptoms within a few hours. Animal
studies indicate that "blood changes" occur within a period of sever-
al weeks following exposures to concentrations between .5 and 2 ppm
for 3 hours a day. Arsine exposure results in hemolytlc anemia, and
clinical signs characterized by nausea, headache, anemia, coppery
skin coloration, and shock within 2-24 hours after exposure (OTS,
1976; IARC, 1980).
2.1.2 Chronic Toxicity
The effects of extended, lower-level exposure to inorganic arsenic
can include heart and blood vessel injury, damage to the peripheral
(motor and sensory) nervous system (accompanied by motor weakness,
muscle soreness and in extreme cases, paralysis), liver damage (such
as cirrhosis), and various skin lesions, such as patch scaling and
hyperpigmentation (OWRS, 1980).
Carclnogenlcity, Teratogenicity, and Mutagenicity
•Based on clinical, occupational, and epidemiologlcal studies, inor-
ganic arsenic is generally considered to be a human carcinogen. Both
the EPA's Office of Health and Environmental Assessment and IARC have
concluded that there is sufficient evidence that inorganic arsenic is
2-1 July, 1982
-------
a lung carcinogen when Inhaled and a skin carcinogen when ingested.
In general, however, animal studies have not shown carcinogenicity
for arsenic compounds even when administered near the maximum toler-
ated dosage for long periods (ECAO, 1980; IARC, 1980; Pershagen,
1981).
Occupational lung cancers have been associated with inorganic arsenic
exposure for: miners of gold-bearing ores, workers exposed to arse-
nical insecticides or sheep dip, and copper smelter workers exposed
to arsenic trioxide. It must be recognized however, that these occu-
pational environments are usually complex and the interaction of
arsenic with other pollutants (e.g., sulfur dioxide) as well as with
tobacco smoking is not well understood (NAS, 1977).
Skin cancers have been reported in several groups exposed to arsenic
via drugs or drinking water. The best documented case is in Taiwan
where the arsenic levels in drinking water ranged from 0.01 to 1.8
mg/1 with a median of about 0.5 mg/1. The prevalence of skin cancer,
hyperpigmentation, and kerotosis correlated with the arsenic content
of the water; for skin cancer, the rate was 10.6 per 1,000. EPA has
used this study to estimate risk factors for consumption of arsenic
in drinking water (OURS, 1980).
However, several aspects of the Taiwan study noted above have result-
ed in some controversy concerning the carcinogenic potency of inges-
ted arsenic. In general, these uncertainties arise from the presence
of other bioactive organic chemicals in the water supply, and the
nutritionally deficient diet of the exposed population (OWRS, 1980).
Other difficulties in assessing the carcinogenic potency of arsenic
include the lack of a satisfactory animal model for arsenic carcino-
genicity and the observed nutritional necessity of arsenic in some
nonhuman mammals (NAS, 1977; NAS, 1980).
Teratogenic effects of arsenic compounds have been demonstrated at
relatively high single dose levels (15 to 45 mg/kg) in hamsters,
rats, and mice. Effects included reduced fetal and birth weights,
Increased fetal resorption, skeletal defects, and other malforma-
tions. However, studies of chronic oral exposure to low levels of
arsenic (e.g., 5 ppm in drinking water during pregnancy) have not
shown significant effects on fetal development. Thus, extrapolation
of the results in experimental animals to man is especially difficult
in light of the failure to demonstrate effects at low exposure
levels. Human epidemiology data is not sufficient to demonstrate
specific associations between arsenic exposure and teratogenic or
embryotoxic effects (ECAO, 1980).
Studies performed on the mutagenic activity of arsenic have yielded
conflicting results. An increased frequency of chromosome aberra-
tions has been found in lymphocytes of wine growers, in psoriatic
patients treated with arsenic, and in arsenic-exposed copper smelter
workers (OWRS, 1980). However, arsenite and arsenate were both inac-
tive in the Ames assay (S. typhimurium). Evidence for arsenicals
causing DNA damage in other bacterial systems (i.e., IS. subtilis) is
contradictory. Arsenic is reported to interfere with enzymatic DNA
repair processes in E. Coll (Sirover, 1981).
2-2 July, 1982
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2.2 Environmental Effects (CONTACTS: Charles E. Stephan, 783-9510 and
John Gentile, FTS 838-4843)
2.2.1 Aquatic Effects (OURS, 1980)
The chemistry of arsenic In water Is complex and the form present In
solution Is dependent on such environmental conditions as Eh, pH,
organic content, presence of suspended solids, and sediment charac-
teristics. Based on freshwater data, trivalent inorganic arsenic
(with the exception of arsenic trisulfide) and the pentavalent form
appear to be similarly toxic to aquatic organisms. Organic arsenic
compounds and arsenic trisulfide were much less toxic but additional
data are needed to adequately determine their effect on aquatic life.
Acute data for 14 freshwater species show that differences in toxic-
ity were not related to the type of exposure (i.e., static or flow-
through tests). Acute values for trivalent inorganic arsenic ranged
from 812 to 41,760 ug/1. A life cycle test was conducted with Daph-
nla magna which gave a chronic value of 912 ug/1. No chronic tests
with freshwater fish species were reported.
The freshwater residue data indicate that arsenic is not bioconcen-
trated to a high degree and that lower forms of aquatic life may
accumulate higher arsenic residues than fishes. Arsenic accumulation
In freshwater aquatic organisms does not appear to be greatly af-
fected by the form of arsenic present, although the highest residues
were seen in exposures with the trivalent inorganic form. The high-
est arsenic bioconcentration factor was found in one test with a
saltwater bivalve mollusc which indicates that these organisms may
accumulate more arsenic than freshwater organisms.
The other toxicological data revealed a wide range of toxic!ty based
on tests with 16 freshwater species and several endpoints of effect.
Comparisons of these data with acute tests showed that arsenic toxic-
ity was increased with increased exposure time. Higher temperatures
also appeared to increase arsenic toxicity whereas water hardness had
no significant effect. Effects of other parameters such as pH, sus-
pended solids, and organic content In the water were not found in the
literature.
Early life stages of freshwater aquatic organisms appear to be the
most sensitive indicator of arsenic toxicity and should be used as
the basis for formulating criteria for arsenic in water. The lowest
effect concentration for arsenic and freshwater organisms is 40 ug/1.
Trivalent Inorganic arsenic acute values for saltwater fish species
were 16,000 ug/1 for Atlantic silverside and 15,000 ug/1 for the
fourspine stickleback; and, among three invertebrate species, acute
values ranged from 508 ug/1 for a copepod and 7,500 ug/1 for the
American oyster. No chronic, plant, or equilibrium residue data are
available for any saltwater species and arsenic.
2-3 July, 1982
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2.2.2 Other Effects
Arsenic is a natural element which can be found in various forms in.
nearly all living organisms and soils. Arsenic accumulates in soils
and can interact with several plant nutrients. Phosphate, for
example, can increase or decrease absorption of arsenic by plants
depending on conditions. If soils have a high fixation for arsenic,
the addition of phosphate can increase the amount of soluble arsenate
and quicken the leaching of the arsenic from top soil into deeper
soil. The phytotoxicity of organic arsenical herbicides is
characterized by a relatively slow kill; chlorosis, cessation of
growth, and browning are followed by dehydration and death (NAS,
1977; OTS, 1976).
Poisoning of forage-eating livestock by inorganic and methylated
arsenical compounds, especially those used as herbicides and
defoliants, has been reported. Most cases result from accidental or
careless contamination of forage. The use of phenylarsonic animal
feed additives as recommended is beneficial and does not constitute a
health hazard. The mechanism of action of these feed additives
remains obscure; these additives are absorbed and excreted without
significant metabolic change (NAS, 1977).
2-4 July, 1982
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3. ENVIRONMENTAL RELEASE (CONTACT: Michael Slimak, FTS 426-2503)
Several EPA program offices have evaluated and ranked source catego-
ries of arsenic release. Even though the reported quantities emitted
to the environment differ, there is general agreement as to the major
sources of arsenic release. Table 2 lists both the uses of arsenic
and its releases to the environment by media. The release data are
only crude estimates and have not been verified in most cases by
sampling and analysis.
Estimates of the relative importance of natural releases of arsenic
into the environment vary widely, from a value of about 7,000 kkg per
year (OWRS, 1981) to a range of 45,000 to 120,000 kkg per year (OTS,
1979). Natural releases occur primarily into water by weathering of
minerals in soils and continental rock. The major anthropogenic
sources of arsenic release are pesticide use/production, copper
smelting, and fossil fuel combustion. About 81% of the total anthro-
pogenic release of arsenic occurs to land, 16% is emitted to air, and
only 3% is discharged to water.
3.1 Air Releases (CONTACT: Warren Peters, FTS 629-5645)
Significant sources
• Primary copper smelters (SIC 3331)
Other sources
Lead smelters (SIC 3332)
Primary zinc smelters (SIC 3333)
Glass manufacturing, using arsenic in production processes (SIC
332)
Pesticide manufacturing (SIC 2679)
Cotton gins processing arsenic desiccated cotton (SIC 0724)
3.2 Water Releases (CONTACT: Michael Slimak, FTS 426-2503)
Significant sources
• Zinc smelters (SIC 3333)
Other sources
• Phosphate rock mining (SIC 1475)
• Copper smelters (SIC 3331)
• Iron and steel foundries (SIC 332)
3-1 July, 1982
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TABLE 2: ANTHROPOGENIC SOURCES OF ARSENIC TO THE ENVIRONMENT (kkg/yr and %)a
I. USES OF ARSENIC
A. Pesticides
B. Wood preservatives
C. Glass manufacture
D. Nonferrous alloys
E. Small volume (feed
additives, veterinary
chemicals, electronics,
catalysts)
Estimated
Rate
(kkg/yr)
10,250
2,930
730
440
290
% of
Total Uses
70.0
20.0
5.0
3.0
2.0
II.
RELEASES TO ENVIRONMENT
A. Land
1.
2.
3.
4.
5.
6.
7.
Discharges
Energy production^
Pesticide prod./usec
Copper production
Iron & steel prod.
Arsenic prod.
Lead & zinc prod.
Phosphorus prod.
Land Total
B. Airborne Emissions^
1.
2.
3.
4.
5.
6.
7.
8.
Pesticide prod. /used
Copper prod.
Lead & zinc prod.
Glass manufacture
Energy productions
Iron & steel prod.
Arsenic production
Phosphorus production
Estimated
Rate
(kkg/yr)
14,000
8,680
8,100
5,700
1,200
1,100
640
43,000
Estimated
Rate
(kkg/yr)
3,150
2,450
1,600
580
540
88
3
<1
Estimated
Rate
(kkg/yr)
14,000
8,680
8,100
5,700
1,200
1,100
640
% of
Discharges
to Land
32.5
20.2
18.8
13.2
2.8
2.6
1.5
% of
Total
Releases
26.3
16.3
15.2
10.7
2.3
2.1
1.2
80.9
Estimated
Rate
(kkg/yr)
3,150
2,450
1,600
580
540
88
3
% of
Emissions
to Air
37.4
29.1
19.1
6.9
6.4
1.0
<0.1
% of
Total
Emissions
5.9
4.6
3.0
1.1
1.0
0.2
<0. 1
Air Total
8,410
15.9
3-2
July, 1982
-------
TABLE 2: ANTHROPOGENIC SOURCES OF ARSENIC TO THE ENVIRONMENT
(kkg/yr and %) (cont.)
Estimated % of % of
Rate Discharges Total
C. Aquatic Discharges (kkg/yr) Direct Emissions
1. Industrial discharges
a. Pesticide use 720 42.3 1.3
b. Lead & zinc prod. 560 33.0 1.0
c. Phosphorus prod. 160 9.4 0.3
d. Energy prod.c 150 8.8 0.3
e. Copper prod. 38 2.2 <0.1
f. Iron & steel prod. 9 <0.1 <0.1
g. Nonferrous metals 7 <0.1 <0.1
2. POTW's <57 <0.7 <0.1
Water Total 1,700 3.1
Total Releases 53,100
a Source, unless otherwise noted: (OWRS, 1981).
k Energy production = combustion of fossil fuels.
c Includes cotton ginning.
d From (OAQPS, 1980).
3-3 July, 1982
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4. EXPOSURE ROUTES
Human exposure to Che various forms of arsenic occurs primarily
through ingestion and inhalation. While ingestion is the most sig-
nificant pathway for exposure in the general population, airborne
arsenic poses more of a problem in occupational settings and to popu-
lations in the vicinity of smelters. Furthermore, much of the arse-
nic in food is probably in the form of less toxic organoarsinicals
and average levels are not considered hazardous (ECAO, 1980).
Table 3 summarizes estimated average daily intake of arsenic from the
major exposure routes. The procedures used in arriving at these
estimates are discussed in detail below.
4.1 Air Exposure (CONTACT: Warren Peters, FTS 629-5645)
Air exposure to arsenic occurs primarily at locations with major
arsenic emission sources (copper, lead, and zinc smelters; glass and
pesticide manufacturing plants; secondary smelters; and cotton gins)
and arises from stack and/or fugitive emissions.
Atmospheric arsenic concentration data for 1974 in 267 locations in
the United States are available from the National Air Sampling Net-
work conducted by EPA. The annual average concentrations for all
sites ranged from below the detection limit (.001 ug/tn3) to 0.083
ug/n»3; the mean arsenic level was 0.003 g. For eight locations near
nonferrous smelters the average was 0.03 ug/m3, and the average for
eight remote rural areas was 0.0004 ug/m3 (assuming a concentration
of zero for samples reported to be below the detection limit) (OAQPS,
1980).
The extent of respiratory absorption of arsenic In humans depends on
a number of variables such as particle size and the chemical form of
arsenic. Experiments with human subjects Indicate an overall absorp-
tion efficiency of about 30% for inhaled arsenic. The average daily
exposure to airborne arsenic may be estimated from the average arse-
nic levels by assuming a daily ventilation rate of 20 m3/day. There-
fore, the estimates for arsenic absorbed via Inhalation shown in
Table 3 are obtained from the daily exposures using an absorption
efficiency of 30% (ECAO, 1980).
Limited data suggests that the predominate form of airborne arsenic
is inorganic. Both trivalent and pentavalent arsenic have been de-
tected in air samples of mixed origin; arsenic from smelters, how-
ever, is thought to be primarily in the trivalent form (A&203).
While the presence of inorganic arsenic in the air is of concern due
to its association with lung cancer, ambient levels are normally far
below the excessive arsenic levels observed in the occupational
exposures associated with cancer (ECAO, 1980).
4.2 Water Exposure (CONTACT: Michael Slimak, FTS 426-2503)
In an EPA national study of residential tap water, two-thirds of the
samples (from 3,834 residences) had arsenic levels above 0.1 ug/1.
4-1 July, 1982
-------
TABLE 3: AVERAGE ARSENIC EXPOSURE LEVELS AND DAILY ABSORBANCE8
Exposure
Route
Air
All sites
Near smelters
Remote sites
Drinking Water
Food
Cigarettes
Average
Arsenic
Levels
0.003 ug/m3
0.03 ug/m3
0.0004 ug/m3
2.4 ug/l»>
13 ppb (fruits)
44 ppb (meat,
fish)
<1 ppb (other
foods)
1.5 ppm
(1.5 ug/cigarette)
Daily
Exposure
(ug)
0.06
0.6
0.008
4.8
15
from
average
diet
6 ug/pack
Estimated
Dally
Absorbance (ug)
0.018
0.18
0.002
4.8
15
from
average
diet
2 ug/pack
Major
Chemical
Species
inorganic trioxide
and pentoxide
probably arsenates
organo-
arsenlcals
unknown
PO
c
l<
a Estimates were calculated as described in the text; most of the data is summarized in (ECAO,
1980) except where otherwise noted.
V0
00
PO
b (OWRS, 1981)
-------
The average, minimum, and maximum arsenic levels detected were 2.37,
0.50 and 214 ug/1, respectively. There have been a number of reports
of isolated instances of high concentrations of arsenic in well
water sources associated with geochemical enrichment in arsenic.
These wells are mainly found in the western U.S. and Alaska. Arsenic
is widely distributed in low concentrations in U.S. surface waters.
A survey of a large number of community water supplies revealed that
only 0.4% exceeded 10 ug/1. Since arsenic in drinking water is pre-
dominately in soluble form (probably arsenates) virtually all of it
is absorbed from the GI tract (OURS, 1980; ECAO, 1980).
Using an average arsenic level in drinking water of about 2.4 ug/1,
it can be estimated that approximately 4.8 ug of mostly inorganic
arsenic is absorbed from an average daily consumption of 2 liters of
drinking water.
Concentrations of arsenic for the entire U.S. in various media are
reported in the STORE! Water Quality data base. The median levels
for total recoverable arsenic are: water, 3 ppb; fish, 100 ppb; sed-
iment, 5,000 ppb. Sediment concentrations are generally 3 orders of
magnitude greater than ambient waters (OWRS, 1981).
4.3 Other Exposure Routes
Food
There is a wide diversity in estimates of daily intake of arsenic in
foods. While older estimates suggested that the average diet could
provide arsenic intake near 1 mg/day (OWRS, 1980), more recent analy-
sis by FDA indicates the level is probably much less In recent
years. For 1974, FDA has calculated that the total daily dietary
intake for a standard diet was about 15 ug; this represents a marked
drop from the FDA estimate of about 75 ug/day for 1967-1969. This
decrease was ascribed to decreasing use of arsenical pesticides and
changes in analytical methods. Approximately 80% of the 15 ug/day
intake is attributed to meats, poultry and seafood; levels in seafood
can be exceedingly high (ECAO, 1980; OWRS, 1981).
Assuming arsenic in food is all absorbed, the estimated daily absorb-
ance from food is 15 ug. However, the chemical forms of arsenic in
various types of foodstuffs are crucial for assessment of risk since
most of arsenic Intake is from this source. Based on available data,
arsenic in marine life is present in complex organoarsenical forms of
limited toxlcity. Also, part of the arsenic in terrestrial food ani-
mals is present as cacodyllc acid, a form much less toxic than inor-
ganic arsenic (ECAO, 1980).
Tobacco
Tobacco-borne arsenic will also contribute to the respiratory burden
of cigarette smokers. Recent data indicates an average level of
about 1.5 ppm of arsenic in tobacco. Assuming a cigarette has a mass
of one gram, and that only 20% of the arsenic is released in main-
stream smoke, the inhaled amount would be approximately 6 ug/pack of
4-3 July, 1982
-------
20 cigarettes. Of the 6 ug inhaled, approximately 30% would be
absorbed by the lungs; therefore 2 ug/pack. of cigarettes is the esti-
mate for daily absorbaace from cigarette smoke (ECAO, 1980).
4-4 July, 1982
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5. DATA BASES
5.1 Chemicals in Commerce Information System (CICIS)
The Inventory was compiled under the authority of Section 8 of TSCA
which requires manufacturers to report to EPA the chemicals imported
and manufactured during calendar year 1977. The Inventory lists the
Chemical Abstract Service (CAS) preferred name for the chemicals,
their respective CAS number (often used for identification purposes),
production site, company name, and volume(s) of production and im-
port. There is also a Confidential Inventory in which many of these
characteristics are claimed confidential by the manufacturer. In
these instances, the confidential information will not be available
on the public inventory. CICIS can now be accessed through the
NIH/EPA Chemical Information System (CIS - see 5.3). For further
information, contact Gerri Nowack at FTS 382-3568.
5.2 EPA Chemical Activities Status Report (EPACASR)
EPACASR is an on-line system containing information on EPA's interest
in chemicals. This system includes data on the Agency's regulations,
research, and assessments directed toward specific chemicals.
EPACASR is published annually and the data base is updated as infor-
mation is received. A searchable subset itemizes NTP/NCI studies and
results, as well as chemicals discussed in the IARC monograph
series. (Other sources are added as appropriate.) Entries identify
the statutory authority, the nature of the activity, its status, the
reason for and/or purpose of the effort, and a source of additional
information. Searches may be made by CAS Number of coded text. For
further information contact Eleanor Merrick at FTS 382-3415.
5.3 NIH/EPA Chemical Information System (CIS)
This is a collection of various scientific data bases available
through an interactive computer program. The linking system between
these data files Is the Structure and Nomenclature Search System
(SANSS). CIS can also provide a list of non-CIS sources of informa-
tion on a chemical of interest. However, these files have to be
accessed individually by either separate on-line systems or in hard-
copy. For further information contact Delores Evans at FTS 382-3546
or Irv Weiss at FTS 382-3524.
5.4 Chemical Regulations and Guidelines System (CRGS)
CRGS is an on-line data base that is being developed to provide in-
formation on chemical regulatory material found in statutes, regula-
tions, and guidelines at the Federal, State, and international
levels. Currently, only the first phase of CRGS, which encompasses
only source material at the Federal level, is operational. Nation-
wide access to CRGS is available through Dialog. For further infor-
mation, contact Delores Evans at FTS 382-3546 or Ingrid Meyer at FTS
382-3773.
5-1 July, 1982
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5.5 Chemical Substances Information Network (CSIN)
The prototype CSIN, operational since November 1981, has been devel-
oped by merging the technologies of computer networking and distrib-
uted data base management. CSIN is not another data base, but a li-
brary of systems. Through the CSIN front-end intermediary management
computer, the user may access and use independent and autonomous In-
formation resources that are geographically scattered, disparate for
data and information content, and employ a variety of types of compu-
ter heardware, software, and protocols. Users may converse in and
among multiple systems through a single connection point, without
knowledge of or training on these independent systems.
Currently, six independent Information resources are accessible
through CSIN. They are: National Library of Medicine (NLM), CIS,
EPA-CICIS, CAS-On-Line, SDC-orbit, and two files of Dialog: CRGS and
TSCA Inventory. The CSIN management computer allows the user to cre-
ate, retrieve, store, manipulate data and queries. This eliminates
the need for reentering long lists of chemical identifiers or other
information elements that are part of the original query or which
have been identified and acquired from one or more of the CSIN re-
sources. For further information contact Dr. Sid Slegal at FTS
382-2256.
5.6 EPA Information Clearinghouse
The EPA Information Clearinghouse is a bibliographic data base com-
posed of over 475 Individual data bases and models that contain mon-
itoring information and statistics on a variety of chemicals. The
individual data bases are maintained by offices within EPA. For fur-
ther information, contact Charlene Sayers at FTS 755-9112.
The following data bases contain information on arsenic compounds.
Baseline* Survey of Public Water Supplies on Indian Lands
BAT Review Study for the Timber Products Processing, Gum and Wood,
Chemicals, and the Printing and Publishing Industries
Best Management Practices, Timber Industry Effluent Guidelines -
Runoff
Best Management Practices, Timber Industry Effluent Guidelines -
Sludge
Boone County Field Site
Chemicals in Commerce Information System
Compatibility Studies to Determine Effectiveness of Treatment
Alternatives for Selected Industrial Wastewaters
Compliance Data System
Compliance Sampling Toxicant Surveys
Consolidated Permits Program-Application Form l,2b,2c
Continuous Monitoring Subset
Contrary Creek Project-803801
Crete, Illinois Metals Environmental Samples
Data Collection Portfolio for Industrial Haste Discharges
Discharge Monitoring Report
Discharge Monitoring Report Files
5-2 July, 1982
-------
Drinking Water
Drinking Water Special Study
Energy and Mining Point Source Category Data Base
EPA, Region X, Point Source File
Federal Facilities Information System
Federal Reporting Data System
Federal Reporting Data System-Regional
Fine Particle Emissions Information System
Fish Kills
Food Industry Group
Fugitive Emissions Information System
Hazardous Waste Site Tracking System
Heavy Metals, Minerals, and Nutrient Data Base
Hemlock, Michigan Environmental Samples
Hewlett-Packard
Humacao Ambient Data Base
IFB Organlcs Data Base
Indicatory Fate Study
Industrial Process Evaluations
Inhalable Particulate Analysis Bank
Inhalable Particulate Network
Innovative Technology, Timber Industry Effluent Guidelines
Inorganic Chemicals Industry Regulation Record
Inventory (Regional National Pollutant Discharge Elimination System)
LiPari Landfill
Liquid Effluents Data System
Love Canal Data Handling System
Metals Data Base-New Mexico
Method Validation Studies of Priority Pollutants
Model State Information System
Multimedia Assessment of the Inorganic Chemicals Industry
National Electronic Injury Surveillance System
National Pollutant Discharge Elimination System (NPDES) Permit
Compliance-Region III
National Pollutant Discharge Elimination System (NPDES) Discharge
Monitoring Reports-Region VII
National Pollutant Discharge Elimination System (NPDES) Discharge
Monitoring Reports-Region I
National Water Quality Surveillance System
Nationwide Urban Runoff Program
Needs Survey
New York Bight Ocean Monitoring Program
Organic Chemicals/Plastics Industry
Paint and Ink Analytical Data
Permit Compliance System
Pesticide Incident Monitoring System
Pesticide Product Information System
Pharmaceutical Screening/Verification Data Base
Priority Pollutants-Region I
Priority Pollutants-Region III
Priority Pollutants Data Base
Publicly Owned Treatment Works (POTW) Analytical Data
Publicly Owned Treatment Works (POTW) Quality Control
Puerto Rico Reservoirs
5-3 July, 1982
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Regional Air Pollution Study-Ambient
Regional Air Pollution Study-Point and Area Source
Regional Toxics Monitoring Program
Resource Conservation and Recovery Act (RCRA)-Hazardous Waste Site
Inspections
Salsbury Laboratories
Screening Sampling Program
Sludge Distribution and Marketing Regulations-Community Impact Survey
Soil, Water, Estuarine Monitoring System
Solid Discharge Data System
Sources of Toxic Pollutants Found in Influents to Sewage Treatment
Plants
Southeast Ohio Exposure-Assessment
Spill Prevention Control and Countermeasure
Storage and Retrieval of Aerometric Data
System for Consolidated Permitting and Enforcement Data Base
Textile Industry BAT Study-Toxic Sampling Data
Toxic Metals
Toxics Monitoring
U.S. Virgin Islands-St. Thomas, St. Crolx
United Nuclear Corporation (UNC) Spill-Rio Puerco Monitoring
UPGRADE
Utility Simulation Model Data Base
Verification Data Base
Wasteload Allocation File
Water Enforcement Regional System
Water Quality Information System
Wisconsin Power Plant Impact Study Data System
5-4 July, 1982
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6. REGULATORY STATUS (Curretit as of 4/23/82)
6.1 Promulgated Regulations
6.1.1 EPA Programs
Clean Air Act (CAA)
• Section 112 - Inorganic arsenic is listed as a hazardous air
pollutant based on the chemical's potential carcinogenic!ty and
significant public exposure (45FR37886). However, emission
standards (NESHAP) have not been promulgated. New Stationary
Source Performance Standards (NSSPS) for primary copper smelters
require monitoring of arsenic levels present in copper ore
processed (40CFR60.165(a)).
Clean Water Act (CWA)
• Section 311 - The following arsenic compounds have been
designated as hazardous materials and are subject to reportable
quantities of 5,000 Ibs: arsenic disulfide, arsenic pentoxide,
arsenic trichloride, arsenic trioxide, and arsenic trisulfide
(40CFR116.4 and 117.3).
• Sections 301, 304, 306 and 307 - Arsenic and its compounds are
listed as priority pollutants (toxic pollutants, 40CFR401.15).
Effluent limitations and/or pretreatment standards for arsenic
have been issued for sections of the following industries:
Inorganic chemicals (40CFR415)
Nonferrous metals (40CFR421)
Timber products (40CFR429)
Ore mining and dressing (40CFR440)
Pesticides (40CFR455)
Safe Drinking Water Act (SDWA)
• Section 1412 - Establishes a maximum contaminant level (MCL) for
arsenic in drinking water supplies (40CFR141.il).
• Sections 1421 to 1424 - Requirements are set forth for state
programs to protect underground drinking water. The regulations
cover operators of wells which inject hazardous wastes, such as
arsenic, (40CFR146).
Resource Conservation and Recovery Act (RCRA)
• Section 3001 - A number of arsenic compounds are designated as
acute hazardous or toxic wastes (40CFR261.33). These chemicals
are hazardous/toxic wastes when they are discarded or intended
to be discarded as commercial products, or off-specification
species. Container residues and spill residues are also includ-
ed. Total extractable arsenic may also characterize wastes as
6-1 July, 1982
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hazardous (EP toxicity, 40CFR261.24). Specific sources of haz-
ardous waste which contain arsenic and the hazardous waste
numbers are: pesticides (K031), coking (K060), veterinary
Pharmaceuticals (K084, K101, K102) (40CFR261.32 and App. VII).
Arsenic compounds are also listed as hazardous constituents
(40CFR261, App. VIII).
• Sections 3002 to 3006 - Hazardous wastes containing arsenic are
subject to further control under RCRA. Regulations cover gener-
ators (40CFR262), and transporters (40CFR263) of such waste; and
treatment, storage, and disposal are subject to interim stand-
ards (40CFR264 and 265).
Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA)
• Labeling requirements for arsenical pesticides include a state-
ment of ingredients and the percentage of water soluble arsenic
(40CFR162.10(g)).
• Tolerance levels are established for arsenic residues on a vari-
ety of agricultural commodities (40CFR180.3(d)(4), and .192 to
.196).
• Procedures are recommended for the disposal of arsenic-contain-
ing pesticides and containers of such pesticides (40CFR165.7 to
.11).
6.1.2 Programs of Other Agencies
OSHA - Occupational Safety and Health Act
• For inorganic arsenic the permissible exposure limit (PEL) is 10
ug/m3 (8-hour time-weighted average); workers in some occupa-
tions are excluded. Inorganic arsenic is regulated as a carcin-
ogen (29CFR1910.1018). For organic arsenic compounds the PEL is
0.5 mg/m3 and for arsine the PEL is 0.2 mg/m3 (29CFR1910.1000).
DOT - Hazardous Material Transportation Act
• Regulations cover the packaging, labeling, and shipping of
hazardous materials such as arsenic compounds (49CFR171 to 177,
parts).
FDA - Food, Drug, and Cosmetic Act
There are numerous regulations which control the amount of arsenic
which may be contained as an ingredient or as a "specification" in
certain food, drugs, and cosmetics; a large number of these regula-
tions involve food coloring additives. The regulations include the
following:
• Tolerances are established for residues of arsenic In food-
producing animals (21CFR556.60).
6-2 July, 1982
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• The maximum contaminant level for arsenic in bottled water is
0.05 mg/1 (21CFR103.35(d)).
• Warning labels are required for over-the-counter drugs which
contain arsenic (21CFR369.20); more stringent labeling, contain-
er and testing requirements exist for trivalent organic arseni-
cals (21CFR680, Subpart B).
MSHA - Mine Safety and Health Act
• Reporting requirements (30CFR50.20-6(b)(7)) and respirator use
are established for mines (30CFR11.130).
Atomic Energy Act
• Where discharges of licensed material containing arsenic exceed
certain radioactive limits, waste disposal and reporting re-
quirements take effect (10CFR20, App. B). Packaging and opera-
ting standards exist for transporting radioactive materials con-
taining arsenic (10CFR71).
6.2 Proposed Regulations
6.2.1 EPA Programs
CWA
• Proposed ocean discharge criteria for issuing and reviewing
NPDES permits for discharges into seas, contiguous zones, and
oceans (45FR9549).
6.2.2 Other Programs
FDA
• Proposals have been issued to revise regulations concerning the
use of arsenic drugs in food-producing animals (46FR2456).
• New or revised standards have been proposed for arsenic impuri-
ties in sugar, Juices and other foods (43FR14679, 19866, 58576;
44FR10729, 10742, 10748; 46FR2456).
6.3 Other Actions
Comprehensive Environmental Response, Compensation, and Liability Act
(CERCLA or Superfund) - CERCLA provides for the liability, compensa-
tion, clean-up, and emergency response for the release of hazardous
substances into the environment. This Act also deals with the clean-
up of hazardous waste disposal sites. (42USC9601; PL 96-510). EPA
is developing regulations concerning the designation of hazardous
substances, the development of reportable quantities, claims proce-
dures, and the confidentiality of business records (46FR54032). Re-
visions to the National Contingency Plan (NCP) as required by CERCLA
6-3 July, 1982
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have been issued in a proposed rule (47FR10972). Hazardous sub-
stances as defined by Section 101(14) of CERCLA include: hazardous
wastes designated under Section 3001 of the R.CRA; hazardous air pol-
lutants regulated under Section 112 of the CAA; water pollutants
listed under Sections 307 and 311 of the CWA (and also any substances
regulated in the future under Section 7 of TSCA and Section 102 of
CERCLA). Therefore, arsenic compounds are hazardous substances under
CERCLA and will be subject to regulations Issued under Superfund.
• CWA - Water quality criteria for arsenic have been issued for
aquatic life and human health (45FR79318).
• OAQPS is evaluating the need for regulations under Section 112
of the CAA for several source categories of inorganic arsenic.
The first priority for development is copper smelters processing
high arsenic-containing ore.
6-4 July, 1982
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7. STANDARDS AND RECOMMENDED CRITERIAa
7.1 Air
• OSHA Standards (8-hr TWA)
Inorganic Arsenic (29CFR1910.1018) 10 ug/m3
Organic Arsenic (29CFR1910.1000) 500 ug/m3
Arsine (29CFR1910.1000) 200 ug/m3
• NIOSH Recommended Limit (15 minute
ceiling for inorganic arsenic) 2 ug/m
7.2 Water
• Drinking Water Standard (MCL)b
(40CFR141.il) 50 ug/1
• Water Quality Criteria (45FR79318)
Human Health (10-5 ri3k) b Q.022 ug/1
Freshwater Aquatic Life
(trivalent arsenic) 440 ug/1
Saltwater Aquatic Life
(trivalent arsenic) 508 ug/1
• The following arsenic compounds are designated as hazardous
substances under Section 311 of the CWA and have reportable
quantities for spills defined as over 5,000 Ibs; arsenic disul-
fide, arsenic pentoxide, arsenic trioxide, and arsenic trisul-
fide (40CFR117.3).
7.3 Hazardous Waste
• Wastes which contain in excess of 5.0 mg/1 of total extractable
arsenic are classified as hazardous ("EP" toxicity, 40CFR261-
.24).
a" See Appendix A for a discussion of the derivation, uses, and limitations of
these criteria and standards.
b EPA recognizes the widely differing values for arsenic for drinking water
(50 ug/1) and WQC (0.02 ug/1 at the 10~5 risk level). Health effects in-
formation and other available data pertinent to this issue (i.e., the car-
cinogenicity of ingested arsenic) are not sufficient or definitive
enough to allow a clear decision. ORD has been directed to develop an
epidemiologic study which might resolve the issue of the carcinogenic
potential ofarsenic in U.S. drinking water supplies. (Contact Charles
Mitchell, FTS 426-2317 for information on how this is progressing).
7-1 July, 1982
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7.4 Other
Tolerance levels for arsenical pesticides in food are listed in
40CFR180.3(d)(4), and .192 to .196. Numerous other tolerances
and standards exist for arsenic in a variety of foods, drugs and
additives (see FDA citations in Section 6.1.2 of this document).
7-2 July, 1982
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8. SPILL OR OTHER INCIDENT CLEAN-UP DISPOSAL (CONTACT: National
Response Center, 800-424-8802 or 426-2675 in the Washington, D.C.
area)
8.1 Hazards and Safety Precautions
Many inorganic arsenic compounds are poisonous materials which may be
fatal if inhaled or ingested. Contact may cause burns to skin or
eyes. Fire may produce irritating or poisonous gases. Runoff from
fire control or dilution water may cause pollution.
Arsine is an extremely flammable gas and may be ignited by sparks and
flame. Flammable vapor may spread from spill area. Container may
explode in heat of fire. Vapor explosion and poison hazard exists
indoors, outdoors, and in sewers.
Store arsenic compounds in tightly closed containers in well venti-
lated areas away from heat and water and from exposure to food.
Arsenic trisulfide and arsenic should be kept away from exposure to
oxidizing agents and acids. Avoid ingestion, contact with skin and
eyes, and Inhalation. Wear protective clothing including safety
glasses, gloves, and a NIOSH-approved self-contained breathing appa-
ratus. For workplace requirements see 29CFR1910.1018. In case of
arsine spill, wear positive pressure breathing apparatus plus full
protective clothing.
8.2 First Aid
Move victim to fresh air; call emergency medical care. If not
breathing, give artificial respiration. If breathing is difficult,
give oxygen. Remove and isolate contaminated clothing and shoes. In
case of contact with material, immediately flush skin or eyes with
running water for at least 15 minutes.
8.3 Emergency Action
Spill or Leak
Avoid contact and inhalation of the spilled cargo. Stay upwind;
notify local fire, air, and water authorities of the accident. Evac-
uate all people to a distance of 200 feet upwind and 1,000 feet down-
wind of the spill. Wear full protective clothing Including
NIOSH-approved rubber gloves and boots, safety goggles or face mask,
hooded suit, and either a respirator whose cannlster is specifically
approved for this material, or a self-contained breathing apparatus.
Care must be exercised to decontaminate fully or dispose of all
equipment after use.
The Department of Transportation's "Hazardous Materials 1980 Emergen-
cy Guidebook" recommends the following general procedures for con-
tainment and clean-up for arsenic spills (excluding arsine). Small
spills, take up with sand, or other noncombustible absorbent materi-
al, then flush area with water. For small dry spills, shovel into
8-1 July, 1982
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dry containers and cover; move containers; then flush area with
water. Large spills, dike far ahead of spill for later disposal.
Arsine concentration in air can be reduced by the use of water spray.
Fire
Fire can be extinguished with water in flooding quantitites as fog,
"alcohol" foam, dry chemical, or carbon dioxide. If water or foam is
used, contain flow to prevent spread of pollution, keep from drains
and sewers. Remove container from fire area if you can do it without
risk.
In case of arsine fire, let burn unless leak can be stopped immedi-
ately. Otherwise, extinguish by method mentioned above; stay away
from ends of tank. Cool containers that are exposed to flames with
water from side until well after fire is out. For massive fire In
cargo area, use unmanned hose holder or monitor nozzles. If this is
impossible, withdraw from area and let fire burn. Withdraw immedi-
ately in case of rising sound from venting safety device or discolor-
ation of tank.
8.4 Notification and Technical Assistance
Section 103(a) of the Comprehensive Environmental Response, Compensa-
tion, and Liability Act (CERCLA or Superfund) requires notification
of the National Response Center if releases exceed reportable quanti-
ties (NRC: 800-424-8802; in Washington, D.C., 426-2675). Under Sec-
tion 311 of the CWA, the reportable quantities for spills are 5,000
Ibs. for arsenic disulfide, arsenic pentoxide, arsenic trichloride,
arsenic trioxide, and arsenic trisulfide. Reportable quantities for
hazardous arsenic compounds are being finalized under CERCLA (see
Section 6.3 of this document).
For emergency assistance call:
CHEM TREC: 800-424-9300
For information, call EPA, Division of Oil and Special Materials
(1-202-245-3045).
8.5 Disposal
The following arsenic compounds are designated as acutely hazardous
wastes under Section 261.33(e) of RCRA: arsenic acid (P010), arsenic
pentoxide (P011), arsenic trioxide (P012), and diethylarsine (P038).
Generators of greater than 1 kg of any commercial or off-specifica-
tion material, or greater than 100 kg of any spill residue resulting
from clean-up, are subject to regulations under 40CFR262 to 265.
Cacodylic acid is designated as a toxic waste (U136) under Section
261.33(f) of RCRA; in this case a small quantity generator which pro-
duces less than 1,000 kg per month of total hazardous waste is not
subject to RCRA regulations. Finally, wastes that fail the HP
toxicity test for arsenic under Section 261.24 are also subject to
RCRA regulations.
8-2 July, 1982
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The following wastestreams are subject to RCRA regulations and
contain arsenic compounds. Hazardous wastes are listed by industry
and hazardous waste number (see 40CFR261.32):
Pesticides (K031) - By-product salts generated in the production
of MSMA and cacodylic acid.
Coking (K060) - Ammonia still lime sludge from coking opera-
tions.
Veterinary Pharamaceuticals - In the production of veterinary pharma-
ceuticals from arsenic or organo-arsenic compounds, the following are
designated as hazardous wastes:
(K084) - Wastewater treatment sludge.
(K101) - Distillation tar residues from the distillation of
aniline-based compounds.
(K102) - Residue from the use of activated carbon for
decolorization.
8-3 July, 1982
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9. SAMPLING. ACCEPTABLE ANALYTICAL TECHNIQUES, AND QUALITY ASSURANCE
9.1 Air (CONTACTS: Larry Purdue, FTS 629-2665,
Robert Stevens, FTS 629-3156 or
Robert Shaw, FTS 629-3148)
Since arsenic is not yet a regulated air pollutant, EPA has not
promulgated an analysis methodology; but arsenic measurements have
been made for a number of years on selected samples from the National
Air Monitoring Stations (NAMS) and its predecessor, the National Air
Surveillance Network (NASN). Data from these networks are stored In
the National Aerometrlc Data Bank under the jurisdiction of OAQPS.
The procedure used most recently is based on the collection of air-
borne particulate matter on glass fiber filters using the high volume
sampling technique and the measurement of arsenic in the particulate
matter using neutron activation analysis. The limit of detection is
approximately 5 mg/m3, although this will vary with the composition
of the glass fiber filters used for sampling. The relative standard
deviation of the analytical measurement is approximately 20 percent.
Both internal and external quality control procedures are available.
The Environmental Sciences Research Laboratory at Research Triangle
Park has measured arsenic concentrations between 10 and 1,800 ng/m
by X-ray flourescence (X-RF). Despite possible complications due to
the presence of lead, X-RF measurements are within +20 percent where
arsenic concentrations exceed 0.5 ug/m3. A dlchotomous sampler modi-
fied to collect volatile forms of arsenic has been developed for sam-
pling near high temperature sources (e.g., smelters).
9.2 Water (CONTACTS: Gerald D. McKee, FTS 684-7372 or
Ted Marten, FTS 684-7312)
Arsenic is a Clean Water Act 304(h) parameter and is listed as an in-
organic priority pollutant. It is also a drinking water parameter,
with a maximum contaminant level of total arsenic set at 0.05 mg/1.
The term "total arsenic" is defined as the sum of the concentrations
of all forms of arsenic in both the dissolved and suspended fractions
of the sample. When a sample containing suspended material is to be
used for analysis of total arsenic, a sample digestion step is re-
quired. For the total analysis of dissolved arsenic by a colorime-
tric or gaseous hydride procedure, sample digestion is also required
to ensure that the arsenic is in the proper chemical state and avail-
able for reaction.
There are a variety of approved methods for arsenic analysis ("Meth-
ods for Chemical Analysis of Water and Wastes, 1979", EPA-600/
4-79-020). The spectrophotometric measurement at 535 run of the com-
plex formed by the reaction of silver diethyldithiocarbamate (SDDC)
with arsine is a well-known procedure. This colorimetric method,
however, is limited to the analysis of arsenic concentrations at or
above 0.01 mg/1.
9-1 July, 1982
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The gaseous hydride method Is an atomic absorption procedure. After
an acid digestion the arsenic Is reduced to the trlvalent form and
converted to arslne using either zinc metal or sodium borohydride.
Using an inert gas, the arsine is then swept into a hydrogen fueled
flame or heated quartz tube for dissociation and atomic absorption
measurement. The normal analytical working range for hydride methods
is from 0.002 to 0.020 mg/1.
The graphite furnace method is also an atomic absorption method. For
this analysis, the sample is digested with nitric acid and hydrogen
peroxide and then stabilized with nickel nitrate. For every matrix
analyzed, verification is necessary to determine that the method of
standard addition (MSA) is not required. The optimum range for
graphite furnace methods (for 20 ul injection) is 0.005 to 0.100
mg/1.
In response to the improved state-of-the-art of multi-element analy-
sis, a water/wastewater related method which includes arsenic has
been promulgated by EPA (Federal Register, 44, p. 69559, December 3,
1979). The revised method (200.7) uses Inductively coupled plasma-
atomic emission spectroscopy (ICP-AES). The atomic-line emission
spectra is processed by computer to subtract background and to
correct for any spectral interference. While the estimated detection
limit is 0.05 mg/1 (at 193.7 nm), the optimum working range for arse-
nic by the 1CP technique is considered to be from 0.25 mg/1 to well
above 100 mg/1.
The following table summarizes the approved methods with appropriate
references:
LIST OF APPROVED TEST PROCEDURES FOR TOTAL ARSENIC
Reference Method No.
Standard
EPA1 Methods 2 ASTM3 USGS*
Sample DigestionS 206.5
Spectrophotometric (SDDC) 206.3 303E D2972-78(B) 1-3062-78
AA-Gaseous Hydride 206.4 307B D2972-78(A) 1-3060-78
AA-Furnace 206.2 304
ICP-AES6 200.7
1. "Methods for Chemical Analysis of Water and Wastes, 1979,"
EPA-600/4-79-020.
2. "Standard Methods for the Examination of Water and Wastewater,"
15th Edition, American Public Health Association, Washington,
D.C.
9-2 July, 1982
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J. "Annual Book of ASTM Standards, Part 31, Water," American Soci-
ety for Testing and Materials.
4. "Methods for Analysis of Inorganic Substances in Water and
Fluvial Sediments" U.S. Department of the Interior, Geological
Survey, Open-file Report 78-679.
5. Sample digestion for total arsenic may be omitted for AA graph-
ite furnace and ICP analyses provided the sample has a low COD
and the filtrate meets the following criteria: (a) visibly
transparent, (b) no odor, (c) free of particulate matter follow-
ing acidification.
6. Inductively Coupled Plasma Optical Emission Spectrometric Method
(ICP) for Trace Element Analysis of Water and Wastes; Method
200.7 published by U.S. EPA, EMSL-Cincinnati.
9.3 Solid Wastes
Two approved methods for arsenic analysis in solid wastes are given
in "Test Methods for Evaluating Solid Wastes - Physical/Chemical
Methods," (US EPA/SW-846/May 1980), Method No. 8.51. The graphite
furnace method uses atomic absorption to analyze samples digested
with HN03/H202* The gaseous hydride method also uses atomic absorp-
tion to measure arsenic levels in wastes which are digested with
HN03/H2S°4* Both procedures are nearly identical to the atomic ad-
sorption methods approved for arsenic determination in water.
9.4 Other Samples
Typical methods of analysis for arsenic levels in a wide variety of
biological and other environmental matrices are listed in a monograph
published by the International Agency for Research on Cancer, World
Health Organization (IARC, 1980). In most cases, however, these
methods are not "approved" procedures.
Recently, several procedures for species-specific analysis of arsenic
have been published. Procedures have been developed for determina-
tion of nanogram amounts of methylarsonic acid and cacodylic acid, in
addition to inorganic arsenic. (Andreae, M.O. (1977), Anal. Chem.
49, 820 and Braman, R.S., et al., (1977), Anal. Chem., 49_, 621).
NIOSH has developed an automated ion-exchange method for species-
specific arsenic analyses which is capable of detecting as little as
3 ppb. A draft report has been published by the Health Effects Re-
search Laboratory, Cincinnati ("Speciation of Arsenic Compounds in
Water Supplies," HERL, Cinn. 1981) which summarizes the state-of-the-
art for arsenic analyses.
A procedure is given for the determination of total arsenic in sedi-
ments and other solids in "Chemical Laboratory Manual for Bottom Sed-
iments and Elutriate Testing," (EPA-905/4-79-014). The dried sedi-
ment is digested (HN03/H202) and heated in HN03~HC1 to solubilize the
metal. Analysis is obtained by atomic absorption using the graphite
9-3 July, 1982
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furnace method and standard addition techniques. A similar procedure
for arsenic determination In sediment can be found In "Interim
Methods for the Sampling and Analysis of Priority Pollutants In
Sediments and Fish Tissue," (EPA/EMSL-Cinn./Aug., 1977, revised
October 1980). This publication also contains a procedure for the
analysis of fish for arsenic by a gaseous hydride-atomic absorption
method.
9.5 Quality Assurance
ORD has a full range of Quality Assurance support available which
includes the following Items:
• unknown performance evaluation samples
• known quality control check samples
• recommended procedures for verification of results
These are available to the regions through the Quality Assurance
Branch of EMSL-Cincinnati. (Quality Assurance Contact: John Winter,
FTS 684-7325).
9-4 July, 1982
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REFERENCES
The major references used in preparation of this document are listed below.
EPA references are listed by EPA office of origin and the year of
publication. For further information refer to contacts given throughout this
document or contact the relevant EPA offices listed at the end of this
section.
(ECAO, 1980)
(IARC, 1980)
(NAS, 1977)
(NAS, 1980)
(NRC, 1977)
(OAQPS, 1980)
(OTS, 1976)
(OTS, 1979)
(OWRS, 1979)
(OWRS, 1980)
(OWRS, 1981)
(Pershagen, 1981)
(Sirover, 1981)
Health Assessment Document for Arsenic, Environmental
Criteria and Assessment Office, EPA - Draft, Research
Triangle Park, N.C. (1980).
IARC Monographs on the Evaluation of the Carcinogenic
Risk of Chemicals, Vol. 23, International Agency for
Research on Cancer, World Health Organization (1980).
Drinking Water and Health, Vol. 1, pp. 316-344, National
Academy of Sciences, Wash., D.C. (1977).
Drinking Water and Health, Vol. 3, pp. 337-345, National
Academy of Sciences, Wash., D.C. (1980).
Arsenic, National Research Council, Wash., D.C. (1977).
Human Exposure to Atmospheric Arsenic, EPA contracts
68-01-4314 and 68-02-2835, Office of Air Quality Planning
and Standards, Research Triangle Park, N.C. (1980).
Technical and Microeconomic Analysis. Task III - Arsenic
and Its Compounds, EPA-560/6-76-016, Office of Toxic
Substances (1976).
Status Assessment of Toxic Chemicals - Arsenic,
EPA-660/2-79-210b, Office of Toxic Substances (1979).
Water-Related Environmental Fate of 129 Priority
Pollutants, Vol. L, Ch. 6, EPA-4AO/A-79-029a» Office of
Water Regulations and Standards (1979).
Ambient Water Quality Criteria for Arsenic, EPA
440/5-80-012, Office of Water Regulations and Standards
(1980).
Strategy for Controlling Environmental Exposure to
Arsenic, EPA-Draft, Office of Water Regulations and
Standards (1981).
"The Carcinogenicity of Arsenic," G. Pershagen,
Environmental Health Perspectives, 40_*. 93-100 (1981).
"Effects of Metals in in Vitro Bioassays," M.A. Sirover,
Environmental Health Perspectives, 40: 163-172 (1981).
R-l
July, 1982
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OFFICE CONTACTS
The EPA offices and divisions that are listed below may be contacted for more
Information relating to the Indicated sections of this document. While these
offices are, in many cases, the offices of origin for the data included in
this paper, the personal contacts given throughout this document should be
contacted first. Unless otherwise noted, the offices listed are situated in
Headquarters, Washington, D.C., and the telephone numbers given are FTS
(Federal Telecommunications System) numbers. For commercial telephone calls
to Headquarters which are not placed on FTS, area code 202 must be used.
Other commercial numbers are noted for the office contacts located outside
Washington, D.C.
HEALTH AND ENVIRONMENTAL EFFECTS (Section 2)
Office of Health and Environmental Assessment (OHEA)
Environmental Criteria and Assessment Office:
Cincinnati, OH 684-7531 (513-684-7531)
Research Triangle Park, NC 629-2266 (919-541-2266)
Carcinogen Assessment Group 755-3968
Office of Drinking Water (ODW)
Health Effects Branch 472-6820
Office of Toxic Substances (OTS)
Health and Environmental Review Division 382-4241
Environmental Research Laboratory
Duluth, MN, Region V 783-9550 (218-727-6692)
ENVIRONMENTAL RELEASES AND EXPOSURE (Sections 3 and 4)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Water Regulations and Standards (OWRS)
Monitoring and Data Support Division 426-2503
R-2 July, 1982
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Office of Toxic Substances (OTS)
Exposure Evaluation Division 382-3873
Assessment Division 382-3442
DATA BASES (Section 5)
Office of Toxic Substances (OTS)
Management Support Division 382-3546
REGULATORY STATUS, STANDARDS, AND CRITERIA (Sections 6 and 7)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Drinking Water (ODW)
Criteria and Standards Division 472-5016
Office of Water Regulations and Standards (OWRS)
Criteria and Standards Division 755-0100
Effluent Guidelines Division 426-2571
Office of Solid Waste (OSW)
State Programs and Resources
Recovery Division 755-9107
SPILL CLEAN-UP AND DISPOSAL (Section 8)
NOTE: For Emergenices call the National Response Center at 1-800-424-8802
(1-800-426-2675 from the Baltimore/Washington area).
Office of Emergency and Remedial Response (OERR)
Emergency Response Division 245-3045
Oil and Hazardous Materials Spills Branch
Edison, NJ; Region II 340-6634 (201-321-6634)
R-3 July, 1982
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Office of Solid Waste (OSW)
Hazardous and Industrial Waste Division 755-9187
ANALYTICAL TECHNIQUES (Section 9)
Environmental Monitoring Systems Lab (EMSL)
Air Analysis
Research Triangle Park, NC 629-2454 (919-541-2454)
Water Analysis
Cincinnati, OH 684-7311 (513-684-7311)
Waste Analysis
Las Vegas, NV 545-2137 (702-798-2137)
GENERAL IPP COMMENTS, CORRECTIONS, OR QUESTIONS
Office of Toxic Integration
Chemical Information and Analysis Program 382-2249
R-4 July, 1982
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Asbestos
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ASBESTOS
Table of Contents
Page
Physical/Chemical Properties and Chemistry 1-1
Properties 1-1
Chemistry and Environmental Transport 1-1
Effects Information 2-1
Health Effects 2-1
Environmental Effects 2-3
Environmental Release 3-1
Air Releases 3-1
Exposure Routes 4-1
Air Exposure 4-1
Water Exposure 4-2
Other Exposure Routes 4-2
Data Bases 5-1
Chemicals in Commerce Information System (CICIS) 5-1
EPA Chemical Activities Status Report (EPACASR) 5-1
NIH/EPA Chemical Information System (CIS) 5-1
Chemical Regulations and Guidelines System (CRGS) 5-1
Chemical Substances Information Network (CSIN) 5-2
EPA Information Clearinghouse 5-2
Regulatory Status 6-1
Promulgated Regulations 6-1
Proposed Regulations 6-3
Other Actions 6-3
Standards and Recommended Criteria 7-1
Air 7-1
Water 7-1
July, 1982
-------
Spill or Other Incident Clean-Up/Disposal 8-1
Sampling, Acceptable Analytical Techniques, and Quality Assurance 9-1
Air 9-1
Water 9-1
Solid Wastes 9-2
Other Samples 9-2
Quality Assurance 9-4
References and Office Contacts K-l
July, 1982
-------
ASBESTOS
1. PHYSICAL/CHEMICAL PROPERTIES AND CHEMISTRY
1.1 Properties
Fibrous asbestos minerals have found wide use because of a unique
combination of resistance to heat and chemical attack, high tensile
strength, and flexibility. Asbestos is found in thousands of commer-
cial products including heat-resistant textiles, reinforced cement,
filters, thermal insulation, and brake linings. As a consequence of
the natural occurrence and wide use of this mineral, asbestos fibers
are widely dispersed in the environment. Asbestos constitutes a
health hazard for asbestos workers and is a potential threat unless
it is completely sealed into a product (NIH, 1978; IARC, 1977).
Asbestos is a common name for a group of natural silicate minerals
that separate into thin but strong fibers. Current usage of the term
asbestos is usually reserved for the serpentine mineral chrysotile,
and five fibrous minerals in the amphibole class (see Table 1).
Identification of asbestos fibers is relatively simple with bulk sam-
ples due to the unique characteristics of these minerals; however,
positive identification is difficult for submicroscopic samples. For
regulatory purposes, asbestos has been defined as having a length to
diameter (aspect) ratio of 3:1 or greater. Chrysotile is the major
mineral form of asbestos and accounts for more than 95% of the fiber
presently used in the United States (NIOSH, 1980).
1.2 Chemistry and Environmental Fate/Transport
Asbestos minerals are composed of silicon, oxygen, hydrogen, and var-
ious metal cations (sodium, magnesium, iron, calcium). Typical for-
mulas for asbestos are given in Table 1 along with important proper-
ties and uses. Asbestos minerals are resistant to chemical attack;
chrysotile, however, is susceptible to degradation by acids. All
forms of asbestos will decompose to simpler components (i.e., pyrox-
enes and silica) when heated to temperatures in the range 600-1000°C
(OWRS, 1979; Michaels, 1979).
Dry asbestos easily separates and forms dust which consists of fibers
varying from several inches to microscopic in size. These microscop-
ic fibers are hazardous and may remain in the atmosphere long enough
to travel great distances. Because asbestos persists in the environ-
ment it can be widely redistributed by natural and human means.
While not water soluble, asbestos may remain in suspension and travel
great distances. The surface of asbestos fibers in water may carry
either a net positive (chrysotile) or negative (amphiboles) charge.
These charged surfaces permit the formation of stable suspensions in
water. Some materials, notably trace metals and organic compounds,
may be adsorbed onto or react with asbestos surfaces. Bioaccumula-
tion and biotransformation processes are not significant in aquatic
organisms. Suspended asbestos fibers eventually undergo physical
1-1 July, 1982
-------
TABLE 1: PROPERTIES Of ASBESTOS FIBERS3
Name
CAS Number
and
General Formula'5
Decomposition0
Temperature (°C)
Properties
Uses
i
ro
c
_-J
*<
VO
00
ro
Chrysotlle
12001-29-5
Mg3Si205(OH)4
Crocldollte
Amosite
12001-28-4
12172-73-5
(Mg,Fe)7Si8022(OH)2
Anthophyllite 17068-78-9
(fibrous) (Fe,Mg)7Sl8022(OH)2
Actlnolite 13768-00-8
(fibrous) Ca2(Mg,Fe)5Si8022(OH)2
Tremolite 14567-73-8
(fibrous) Ca2(Mg)5Si8022(OH)2
800-850 Usually white or
pale in color; flex-
ible, silky, and
tough; high tensile
strength.
800 Blue color, flexible,
brittle and tough;
high tensile strength.
600-900 Usually pale brown
and brittle.
950 White in color and
brittle; talc-like
form.
1040 Pale to dark green
in color.
1040 White to grey;
usually brittle.
Widely used in ce-
ment sheets & pipes,
floor and ceiling
materials, and fric-
tion products.
Sparingly used for
asbestos cement
pipe.
Some use in asbestos
cement sheet and as
thermal insulation.
Limited use in com-
posite materials
(plastic resins).
Fibrous actinolite
is of no commercial
significance.
Fibrous form has no
significant uses,
but is an impurity
in talcs.
a Source: (Michaels, 1979) unless otherwise noted.
b (OWRS, 1979).
c Typical temperature peak or range observed during differential thermal analysis (DTA) of the
thermal breakdown to simpler products in an inert atmosphere.
-------
degradation or chemical coagulation which allows them to settle into
the sediment. Environmental release of asbestos occurs primarily
through disposal of consumer wastes to land. Disposal to the land is
also an important source of atmospheric asbestos (N1H, 1978; OWRS,
1979).
1-3 July, 1982
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2. EFFECTS INFORMATION
2.1 Health Effects (CONTACT: Jerry Stara, FES 684-7531; Les Grant,
FTS 629-2266; Bob McGaughy, FTS 755-3968;
Ed Ohanlan, FTS 472-6820)
Disposition of Fibers in the Body
The disposition of inhaled asbestos fibers depends primarily on fiber
size. Certainly some fibers are ultimately deposited In the airways
and lung tissue. Some could also be expectorated or conveyed to the
gastrointestinal tract by airway clearance mechanisms and possibly
some to the pleural and peritoneal cavities via lymphatic drainage.
Of asbestos fibers found in human lungs, a majority are less than 5
urn in length and seldom do they exceed lengths of 200 urn or diameters
of 3.3 urn. One autopsy study of persons with occupational exposure
demonstrated that all asbestos fibers examined in the lung were less
than 0.5 urn in diameter. This preponderance of small fibers in part
reflects their ability to remain suspended in air for longer periods
than larger fibers, but it is also a function of their deposition and
clearance characteristics once they enter the respiratory tract.
Studies with mammalian cells in culture indicate that these shorter
fibers (usually less than 5 urn) may be engulfed by alveolar macro-
phages and transported to lymphatic channels or the mucociliary blan-
ket for excretion. Longer fibers may be only partially engulfed or
may be engulfed by several macrophages at once (NIH, 197B).
Asbestos fibers may enter the gastrointestinal tract via the diet, or
by ingestion of inhaled fibers cleared from the respiratory tract.
While most of the swallowed asbestos is probably excreted in the fe-
ces, microscopic fibers can migrate through the gastrointestinal mu-
cosa. Recent studies show significant asbestos levels In tissue sam-
ples (liver, jejunum, lung) of humans due to transmucosal uptake of
fibers Ingested by drinking asbestos contaminated water. Ingestion
of asbestos by humans has been shown to lead to asbestos fibers in
urine; this result also provides evidence for transmucosal passage of
mineral fibers. Animal studies of gastrointestinal tract penetration
by asbestos fibers have yielded conflicting results (OWRS, 1980).
2.1.1 Acute Toxicity
Acute effects are of little consequence in inhalation exposure to
high asbestos concentrations. Temporary breathing difficulty due to
air-flow abnormalities may result from short-term exposure to high
levels.
2-1 July, 1982
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2.1.2 Chronic Toxicity
Nearly all the positive evidence linking asbestos to human disease
has come from occupational studies. Asbestosis requires the greatest
degree of exposure, followed by bronchial carcinoma and mesothelioma,
in that order. However, development of these diseases follows the
opposite trend, so that heavy exposure to asbestos may lead to death
by asbestosls or bronchial carcinoma long before mesothelioma arises
(OWRS, 1980).
Asbestosls - Asbestosls Is a long-term disease resulting from inhala-
tion of asbestos fibers. Fibrous tissue is generated around the
alveoli of the lungs and the thickened membranes impede the inter-
change of carbon dioxide and oxygen. Severely affected people devel-
op shortness of breath and may eventually die of heart failure. All
varieties of asbestos appear capable of producing asbestosis (NIH,
1978).
Carcinogenicity Mutageniclty and Teratogenicity - Exposure to air-
borne asbestos fibers has been conclusively shown to cause bronchial
carcinoma (lung cancer), mesothelioma (a rare cancer of the membranes
lining the chest and abdomen), and gastrointestinal tract cancers
(IARC, 1977; NIH, 1978; OWRS, 1980).
Bronchial cancer is the major exposure-related cancer affecting as-
bestos workers. All commercially available asbestos forms are linked
with increased incidences of lung cancer to varying degrees. Evi-
dence indicates that combined exposure to both asbestos and cigarette
smoke greatly increases the risk of lung cancer. Almost all reported
cases of mesothelioma have been associated with exposure to asbes-
tos. Epidemiological studies suggest that all commercial forms of
asbestos (except possibly anthophyllite) may cause mesothelioma.
There does not appear to be a synergistic effect between asbestos and
cigarette smoking regarding mesothelioma (OURS, 1980; IARC, 1977).
Epidemiological studies have shown that workers exposed to airborne
asbestos also incur increased risks of developing cancers of the gas-
trointestinal tract (throat, stomach, colon, rectum). In the one
study in which synergism has been investigated, esophagus cancers
were increased in incidence only among smoking asbestos workers, not
in their non-smoking co-workers. Stomach and colon-rectum cancer
showed no smoking relationship. Cancers of the oropharynx and larynx
were also concentrated among the smoking asbestos workers (OWRS,
1980; NIH, 1978).
For asbestos-related GI cancers discussed above, such exposure occurs
principally via inhalation and by swallowing asbestos fibers cleared
from the lung ( in Che sputum), and by ingestion of fibers trapped in
the nose or mouth. However, no definitive study exists which estab-
lishes risk levels for ingested asbestos alone. To date, the studies
which have examined the effects of asbestos in drinking water are not
2-2 July, 1982
-------
conclusive. Also, two forms of asbestos (chrysotile and amosite)
were recently found not to be carcinogenic in large-scale feeding
experiments using hamsters (National Toxicology Program).
Chromosal aberrations in hamster cells due to asbestos have been
observed. However, mutagenicity in several bacterial systems was not
observed in testing with various forms of asbestos. No data exist
that link teratogenic effects with exposure to asbestos fibers,
although transplacental transfer of asbestos has been reported (OURS,
1980).
2.2 Environmental Effects
2.2.1 Aquatic Effects
No freshwater or saltwater organisms have been tested with asbestos
minerals. The only available data result from field studies in which
chrysotile and amphibole fibers were found in fish samples taken from
freshwater with known concentrations of these fibers. While muscle
tissue does not appear to accumulate asbestos, bioconcentration may
occur in fish liver and kidney (OWRS, 1980).
2-3 July, 1982
-------
3. ENVIRONMENTAL RELEASE (CONTACT: Phillip Cook, FTS 783-9523;
William Brungs, FTS 838-4843)
Chrysotile is the major type of asbestos used in the manufacture of
asbestos products. These products include asbestos cement pipe,
flooring products, brake linings and clutch facings, roofing prod-
ucts, and coating and patching compounds (see Table 2). Most of the
asbestos used in the United States is imported; in 1980, for example,
80 kkg were produced in this country while 328 kkg were imported.
Domestic use of asbestos has decreased significantly in recent years
due, in part, to the well publicized undesirable health effects;
e.g., 1980 consumption was less than one-half of 1972 consumption
(SRI, 1982).
Total releases of asbestos to the U.S. environment have been estimat-
ed to be about 240,000 kkg (for 1980). Major sources include asbes-
tos mining and milling; manufacturing and use of asbestos products;
and disposal of asbestos wastes. Although these estimates are uncer-
tain, several important conclusions are indicated (NIH, 1978).
• Land discharge accounts for nearly all releases; air emissions may
total about 1% of asbestos released to the environment and water
discharges are on the order of 0.2%.
• Solid waste disposal by consumers is by far the major discharge of
asbestos.
• The potential for intermedia transfer of asbestos is significant
due to its widespread use and persistence in the environment. For
example, solid wastes produced from the manufacture and use of as-
bestos products, and from demolition can be emission sources of
atmospheric asbestos. Water may become contaminated with asbestos
due to: erosion from natural deposits; runoff from sites of as-
bestos disposal; and release of asbestos fibers from asbestos ce-
ment pipes used in water distribution systems.
3.1 Air Releases (CONTACT: Gilbert Wood or John Copeland
FTS 629-5595)
Significant Sources
• Asbestos mining operations; ore and tailings dumps (SIC 1499)
• Surfacing of roadways with asbestos tailings (SIC 1499 and 1611)
• Asbestos milling (SIC 1499)
• Manufacturing of
- asbestos cloth, cord, or other textiles (SIC 2200 and 3292)
- asbestos cement (SIC 3292)
- asbestos fireproofing and insulation materials (SIC 3292)
- asbestos friction products (SIC 3292)
- asbestos paper, millboard and felt (SIC 2661)
- asbestos floor tile (SIC 3292)
- paints, coatings, and caulks which contain asbestos (SIC 2850)
- plastics and rubbers which contain asbestos (SIC 2821 and 2822)
3-1 July, 1982
-------
Chlorine production (SIC 2812)
Demolition operations (SIC 1795)
Use of spray-on asbestos materials (SIC 174)
Open storage of asbestos materials (SIC 4221)
Fabrication of asbestos products (SIC 3292)
Other Sources
• Transportation (consumption of asbestos brake linings)
• Mining of minerals containing trace amounts of asbestos
• Disturbance of asbestos-bearing overburden by off-road vehicles
during mining and road-building or for recreation.
3-2 July, 1982
-------
TABLE 2: DOMESTIC CONSUMPTION OF ASBESTOS (1980)
Uses of Asbestos
Asbestos cement pipe
Flooring products
Friction products
Roofing products
Packing and gaskets
Surface coats/sealants
Insulation
Asbestos cement sheet
Others
(kkg/yr
kkg/yr
144,000
90,000
44,000
26,000
13,000
11,000
9,000
8,000
14,000
Total 359,000
and %)
% of Total
Uses
40
25
12
7
4
3
3
2
4
Source: (SRI, 1982)
3-3
July, 1982
-------
4. EXPOSURE ROUTES
There is little data available in the published literature on non-
occupational exposures to asbestos. Occupational exposures are com-
monly reported as optical-microscope-visible fibers/cm-* (or f/ml)
greater than 5 urn in length. However ambient levels are normally de-
termined by transmission electron microscopy without a minimum length
criterion. It is not known whether differences in fiber counts actu-
ally reflect differences in concentrations. In addition, techniques
used to prepare samples for electron microscopic observation may
cause alteration in fiber size.
4.1 Air Exposure (CONTACT: Gilbert Wood, FTS 629-5595)
Asbestos of the chrysotile variety is a ubiquitous contaminant of am-
bient urban air. Over 98 percent of the 24-hour samples monitored
and analyzed had chrysotile asbestos concentrations of less than 20
^ and most samples were less than 2 ng/m^ (OWRS, 1980).
As one would expect, airborne asbestos can be found in the vicinity
of asbestos mines, mills, manufacturing facilities, and waste dumps.
But elevated levels of fibers also may be found near concentrations
of braking vehicles, in buildings in which asbestos spray products
have been used, and in cars and homes of asbestos workers who have
con.tanLin.ated them with dusc brought from the work area on clothing,
body, or equipment. Asbestos may be inhaled by persons who install
their own asbestos roofing or flooring, or who repair such items as
automobile brakes and clutches, home heating and plumbing systems,
wires for toasters and waffle irons, or the walls of their homes
(NIH, 1978).
Asbestos contamination has also been found in office buildings and
schools where loose asbestos fireproofing material was applied to the
structural steel surfaces. Current average exposure to asbestos in
buildings containing accessible friable asbestos materials (i.e.,
materials not enclosed and easily crumbled or pulverized) has been
estimated to be between 58 and 270 ng/m3 (OPTS, 1980).
Most asbestos is incorporated into finished products where the fibers
are bound in a matrix (e.g., asbestos-cement pipe and sheet, flooring
and roofing products, and friction products), and this reduces the
possibilities for air contamination. Yet, by the application of suf-
ficient energy, fibers may be dislodged from even tightly bound mate-
rials; automobile brake linings are an example.
Clearly, there are opportunities for human non-occupational atmo-
spheric exposure during installation, use, and repair of asbestos
products. However, since there are so many products that use asbes-
tos or materials that may be contaminated with asbestos, it would be
next to impossible to estimate human exposure for each product type.
4-1 July, 1982
-------
4.2 Water Exposure (CONTACT: Phillip Cook, FTS 783-9523; William
Brungs, FTS 838-4843; Ed Ohanian, FTS 472-
6820)
Asbestos, usually chrysotile, is commonly found in domestic water
supplies. Generally asbestos of all sizes in water is expressed as
fiber concentrations using electron microscope techniques. Some
estimates relate chrysotile fiber concentrations to mass concentra-
tions. It has been concluded that the majority (about 95 percent) of
water consumers in the United States are exposed to asbestos fiber
concentrations of less than 106 f/1. This is equivalent to the range
of 2 x 10"^ to 2 x 10" 3 ug/1 in water supplies. The mass concentra-
tion of chrysotile asbestos in city water with less than 106 f/1 are
likely to be less than 0.01 ug/1, which is equivalent to a daily in-
take of less than 0.02 ug. However, in areas with significant con-
tamination from natural sources, man's activities, or erosion from
asbestos cement water pipes by aggressive water, the intake of asbes-
tos from water can exceed 2 ug/day (OURS, 1980).
Although the fate of the asbestos in inspired air is only approxi-
mately known, it appears that eventually more than half the asbestos
inhaled will be swallowed. Assuming that an individual breathes 10
m3 in 24 hours, most ambient air levels of chrysotile (1 to 10 ng/m3)
result in exposures to the gastrointestinal tract of from 0.01 to
0.05 ug/day of asbestos, although, in some circumstances, inhalation
could produce gastrointestinal exposures exceeding 0.1 ug/day. These
exposures are to be compared with those from water ingestion which
lead to daily intakes of less than 0.02 ug. It would appear that in-
halation can give rise to exposures at least equal to that of direct
ingestion for most of the population of the United States (OWRS,
1980).
4.3 Other Exposure Routes
Food - There is little information on the contribution of food pro-
ducts to human asbestos exposure. Beers and wines could contain
quantities of asbestos fibers similar to those found in water systems
(106 to 107 f/1). This contamination could be from natural water
sources or from the erosion of asbestos fibers from purifying fil-
ters. Contamination of drinking water by fibrous glass and other
synthetic fibers used in cartridge filters has been measured at con-
centrations in excess of 109 f/1 (OWRS, 1980).
Erosion of chrysotile from asbestos filters, used to purify parenter-
al drugs, up to 1 mg/dose have been noted in about one-third of drugs
tested. Therefore, the Food and Drug Administration has prohibited
the use of asbestos filters for drug purification, without subsequent
cleanup (41FR16933).
4-2 July, 1982
-------
Occupational - Only after 1966 has occupational monitoring attempted
to quantify asbestos exposures by fiber counting techniques. Since
then, considerable data have accumulated on occupational exposure of
workers to asbestos. A large compilation of such data is included in
the 1972 Asbestos Criteria Document (NIOSH, 1972). Levels during the
period from 1966 through 1971 were generally under lOf (f>5um)/cm3,
although concentrations exceeding 100 f/cm3 were observed, particu-
larly in two plants producing amosite insulation materials and in un-
controlled textile mills. Data on earlier exposures are lacking al-
though some estimates have been made of insulation-workers' exposure
and factory environments (OWRS, 1980).
4-3 July, 1982
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5. DATA BASES
5.1 Chemicals in Commerce Information System (CICIS)
The Inventory was compiled under the authority of Section 8 of TSCA
which requires manufacturers to report to EPA the chemicals imported
and manufactured during calendar year 1977. The Inventory lists the
Chemical Abstract Service (CAS) preferred name for the chemicals,
their respective CAS number (often used for identification purposes),
production site, company name, and volume(s) of production and
import. There is also a Confidential Inventory in which many of these
characteristics are claimed confidential by the manufacturer. In
these instances, the confidential information will not be available in
the public inventory. CICIS can now be accessed through the NIH/EPA
Chemical Information System (CIS - see 5,3). For further information,
contact Gerri Nowack at FTS 382-3568 or Robin Heisler at FTS 382-3557.
5.2 EPA Chemical Activities Status Report (EPACASR)
EPACASR is an on-line system containing information on EPA's interest
in chemicals. This system includes data on the Agency's regulations
research, and assessments directed toward specific chemicals. EPACASR
is published annually and the data base is updated as information is
received. A searchable subset itemizes NTP/NCI studies and results,
as well as chemicals discussed in the IARC monograph series. (Other
sources are added as appropriate.) Entries identify the statutory
authority, the nature of the activity, its status, the reason for
and/or purposes of the effort, and a source of additional
information. Searches may be made by CAS Number or coded text.
(EPACASR is scheduled to be added to CIS in early 1984.) For further
information, contact Eleanor Herrick at FTS 382-3415.
5.3 NIH/EPA Chemical Information System (CIS)
This is a collection of various scientific data bases available
through an interactive computer program. The linking system between
these data files is the Structure and Nomenclature Search System
(SANSS). CIS can also provide a list of non-CIS sources of
information on a chemical of interest. However, these files have to
be accessed individually by either separate on-line systems or in
hard-copy. For further information, contact Dr. Steve Heller at FTS
382-2424.
5.4 Chemical Regulations and Guidelines System (CRG5)
CRGS is an on-line data base which is being developed to provide
information on chemical regulatory material found in statutes,
regulations, and guidelines at the Federal, State, and international
levels. Currently, only the first phase of CRGS, which encompasses
only source material at the Federal level/ is operational. Nation-
wide access to CRGS is available through Dialog. For further
information, contact Doug Sellers at FTS 382-2320.
5-1 October, 1983
-------
5.5 Chemical Substances Information Network (CSIN)
The Chemical Substances Information Network (CSIN) is a
sophisticated switching network based on heterogeneous distributed
data base management and networking concepts. CSIN offers efficient
access to on-line information resources containing data and
information relevant to chemical substances, as well as information
covering other scientific disciplines and subject matters. The
purposes of CSIN are two-fold: first to meet the growing chemical
data and information requirements of industry, academe, government
(Federal and State), public interest groups, and others; and secondly
to reduce the burden on the private and public sector communities when
responding to complex Federal legislation oriented to chemical
substances.
CSIN is not another data base. CSIN links many independent and
autonomous data and bibliographic computer systems oriented to
chemical substances, establishing a "library of systems". Users may
converse with any or all systems interfaced by CSIN without prior
knowledge of or training on these independent systems, regardless of
the hardware, software, data, formats, or protocols of these
information resources.
Information accessible through CSIN provides data on chemical
nomenclature, composition, structure, properties, toxicity, production
uses, health and environmental effects, regulations, disposal, and
other aspects of the life cycle of materials as they move through
society. Currently, seven independent information resources are
accessible through CSIN. They are: National Library of Medicine
(NLM), Chemical Information System (CIS), CAS-On-Line, SDC's ORBIT,
Lockheeds's DIALOG, Bibliographic Retrieval Service (BRS), and the US
Coast Guard's Hazard Assessment Chemical System (HACS). For further
information contact Dr. Sid Siegel at 202-395-7285.
5.6 EPA Information Clearinghouse
The EPA Information Clearinghouse is a bibliographic data base
composed of over 500 individual data bases and models which contain
monitoring information and statistics on a variety of chemicals. The
individual data bases are maintained for offices within EPA. The
clearinghouse listed 71 citations for asbestos. For further
information, contact Irvin Weiss at FTS 382-5918.
5_2 October, 1983
-------
6. REGULATORY STATUS {Current as of 9/83)
6.1 Promulgated Regulations
6.1.1 EPA Programs
Clean Air Act (CAA)
o Section 112 - Asbestos is listed as a hazardous air pollutant
and EPA has issued National Emission Standards (NESHAP). The
standards prohibit any visible emissions of asbestos from milling,
manufacturing, demolition, renovation, and spraying operations.
Use of specified air cleaning procedures may be used in lieu of
the no visible emission standard. These emission standards apply
to the following product manufacturing operations (40CFR61):
textile materials
cement products
fireproofing and insulation material
friction products
paper, millboard, and felt products
floor tile
paints, coatings, caulks, adhesives, sealants
plastics and rubber materials
chlorine
shotgun shells
asphalt concrete
For spray-on materials used for insulation or fireproofing, the
standard limits asbestos content to no more than 1 percent. The
use of friable asbestos in molded pipe insulation is prohibited.
Also, waste management operations for manufacturing, demolition,
renovation, and spraying processes are regulated.
Clean Water Act (CWA)
o Sections 301, 304, 306 and 307 - Asbestos is listed as a
Toxic Pollutant (40CFR401.15), also known as a priority pollutant,
and is subject to effluent limitation guidelines. Guidelines have
been promulgated for subcategories A through K of the asbestos
manufacturing point source category. In addition, new point
performance standards and pretreatment standards are also included
in the regulations (40CFR427, Subparts A to K).
Toxic Substances Control Act (TSCA)
o Section 8(a) - Naturally occurring chemical substances are
included in the inventory reporting regulations. Asbestos is
included under the definition of a naturally occurring chemical
substance which is (1) unprocessed or (2) processed only by
manual, mechanical or gravitational means; by dissolution in
water; by flotation; or by heating solely to remove water
(40CFR710).
6-1 October, 1983
-------
o Section 6 - School Program - This rule requires public and private
elementary and secondary schools in the United States to identify
friable asbestos-containing building materials, maintain records
and notify employees, and notify the PTA of the inspection results
(40CFR763, Subpart F)
o Section 12 (b) - This regulation requires exporters of asbestos to
notify the agency. This requirement applies to raw asbestos,
although expansion to include asbestos-containing products is
under consideration (40CFR707; 45FR82S44).
o Reporting and recordkeeping requirements have been issued for
manufacturers, importers, and processors of asbestos (40CFR763
Subpart D).
Resource Conservation and Recovery Act (RCRA)
o Although asbestos was originally listed as a hazardous waste
(4SFR33066), it has been deleted because disposal of asbestos
wastes is already regulated under the Clean Air Act (NESHAP).
Consideration is being given to regulating asbestos wastes under
RCRA and deleting waste disposal regulations under CAA in order to
concentrate all waste regulations in one program office.
6.1.2 Programs of Other Agencies
CPSC Consumer Product Safety Act
o Section 8 and 9 - Consumer patching compounds and artificial
emberizing materials (used in fireplaces to simulate live embers
and ash) which contain asbestos are banned (16CFR1304 and 1305).
General use garments containing asbestos are also banned
{16CFR1500.17).
FDA - Federal Food, Drug, and Cosmetic Act
o Sections 501, 502, and 701 - The content of asbestos
particles in parenteral (injectable) drugs is restricted
(21CFR133).
o Sections 201 (s), 409, and 701 (a) - The use of the electrolytic
diaphragm process in the production of salt for human consumption
is prohibited due to asbestos impurities (21CFR121).
o FDA also regulates asbestos as a component in packing material
(21CFR175.105) and food contact surfaces (21CFR177).
MSHA - Federal Metal and Nonmetallic Mine Safety Act
o Section 6 - Health and safety regulations exist for workers in
mines concerning exposure to asbestos dust (3OCFR55.5).
6-2 October, 1983
-------
OSHA - Occupational Safety and Health Act
o Sections 6 and 8 - These regulations list definitions of asbestos,
set permissible exposure limits, and describe methods for
compliance, measurement, monitoring and recordkeeping
(29CFR1910.1001 and 1910.1002).
DOT - Hazardous Material Transport Act (HMTA)
o These regulations cover the packaging and shipping of asbestos
materials (49CFR172 to 177).
6.2 Proposed Regulations
6.2.1 EPA Programs
CAA
o Amendments to the existing NESHAP have been proposed that would
reinstate work practice and equipment provisions. These
provisions had been disallowed by the Supreme Court in 1978
(48FR32126).
Comprehensive Environmental Response, Compensation, and Liability
Act (CERCLA or Superfund)
o CERCLA provides for the liability, compensation, cleanup, and
emergency response for the release of hazardous substances into
the environment. The Act also deals with the cleanup of hazardous
waste disposal sites (42USC9601; PL-96-510). EPA is developing
regulations concerning the designation of hazardous substances,
the development of reportable quantities (RQ), claims procedures,
and the confidentiality of business records (46FR54032).
o Revisions to the National Contingency Plan (NCP) as required by
CERCLA have been issued in a proposed rule (47FR10972).
Adjustments to the statutory reportable quantities have been
proposed; however, until an Agency assessment of the
carcinogenicity and other effects is complete, the statutory RQ of
one pound is applicable for asbestos (48FR23552)
6.3 Other Actions
SDWA - The possible development of a drinking water standard for
asbestos depends upon ongoing health hazard assessments for
ingested asbestos by epidemiological and animal studies.
TSCA - EPA is evaluating the need for further regulation
of remaining asbestos uses. Alternatives under consideration
include labeling requirements and prohibition or otherwise
restricting certain uses (44FR60056;CONTACT: Edward Klein, FTS
382-3938). EPA will coordinate its asbestos activities with those
of the Federal Asbestos Task Force.
6-3 October, 1983
-------
o CPSC - The Commission has issued an ANPRM on asbestos in consumer
products and convened a Chronic Hazards Advisory Panel (CHAP).
Based on the findings of the Panel, CPSC will decide what
regulatory actions, if any, are appropriate. The final report of
the CHAP is available on request {301-492-6800; 48FR39486).
o OS HA - An emergency temporary standard of 0.5 fibers/cm^ has been
issued for asbestos. Emergency temporary standards are effective
for six months or until superseded by a permanent standard or
stayed judicially.
6-4 October, 1983
-------
7.
7.1
STANDARDS AND RECOMMENDED CRITERIA^
Air
•
OSHA permissible exposure limit
(29CFR1910):
8 hr. TWA
ceiling concentration
NIOSH recommended limits:
8 hr. TWA
ceiling concentration
7.2
Water
Water Quality Criteria for human
health. This is a gastrointes-
tinal cancer risk projected from
occupational inhalation exposure
and extrapolated to consumption
of asbestos in drinking water
(OWRS, 1980).
2 f/cm3b
10f/cm3
0.1 f/cm3b
0.5 f/cm3
3 x 103 f/1
for 10~5 risk
a See Appendix A for a discussion of the derivation, use, and limitations of
these criteria and standards.
b Fibers (f) longer than 5 micrometers per cm3 of air using optical
microscopy. Note that 1 f/cm3 = 10^ f/m3.
7-1
July, 1982
-------
8. SPILL OR OTHER INCIDENT CLEANUP/DISPOSAL (CONTACT: National
Response Center 800-424-8802; in Washington 426-2675)
General Information
Very little information was available on the cleanup and disposal
of asbestos spills. It is recommended that asbestos-containing
wastes be packaged in sealed bags or containers prior to transport
or disposal in an approved landfill. Section 103(a) and (b) of
the Comprehensive Environmental Response, Compensation, and
Liability Act of 1980 requires persons who release hazardous
substances into the environment in reportable quantities
determined pursuant to Section 102 of the Act to notify the
National Response Center (NRC): 800-424-8802 (Washington, D.C.,
426-2675). The CERCLA statutory reportable quantity of one pound
applies until the Agency assesses asbestos for carcinogenicity and
other toxic effects (48FR23552).
An example of ongoing remedial action concerning asbestos is the
current Agency activity in Globe, Arizona. Asbestos contamination
of the soil at a residential subdivision was discovered in Arizona
in 1979. The development had been constructed at the site of a
defunct asbestos mill. The site was given a six inch soil cap by
the state of Arizona in 1980; however, the soil cap deteriorated
due to natural erosion and human activity, once again exposing
asbestos fibers. The site was eventually put on the Superfund
list of hazardous waste dumps and the families relocated. The
soil at the site will be sealed by fabric and fresh soil and re-
vegetated. For further information concerning this incident and
related Agency cleanup actions, contact the Office of Emergency
and Remedial Response (Deborah Dalton, FTS 382-7788).
8-1 October, 1983
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9« SAMPLING. ACCEPTABLE ANALYTICAL TECHNIQUES AND QUALITY ASSURANCE
9.1 Air (CONTACT: Michael E. Beard, FTS 629-2623)
EPA has not promulgated an analysis methodology for asbestos. A
method for measurement of airborne asbestos by transmission electron
microscopy (TEM) has been developed and is in provisional use as
evaluation of the technique continues. Airborne asbestos is
collected by drawing air through a polycarboaate or cellulose ester
filter and the fibers are then examined by TEM at a magnification of
20.000X. Fibers with an aspect ratio of 3:1 (length to width) or
greater are counted and identified as possible asbestos by
morphology. The fiber identity is confirmed as amphibole or
serpentine (chrysotile) asbestos by determining crystal structure
with selected area electron dlffratlon (SAED) patterns and by
determining chemical composition with x-ray fluorescence spectroscopy
(XRF). Fiber concentration as fiber number and mass per cubic meter
of air is reported. Detailed Instructions for accomplishing the
analysis are given in EPA-600/2-77-178 (Revised June, 1978),
"Electron Microscope Measurement of Airborne Asbestos Concentrations,
A Provisional Methodology Manual." Evaluation of this method is
continuing (EPA Contract No. 68-02-3266) and further revision of the
manual is anticipated.
A test of the provisional method by six laboratories gave a precision
of 0.49 (ratio of spread between 95% confidence Interval and mean
value) for fiber number concentration and 1.57 for mass concentration
on real samples containing chrysotile. A comparison of mass concen-
trations of laboratory prepared samples measured by the provisional
method and by x-ray spectroscopy showed agreement within 10%.
(EPA-600/2-78-038, June 1978).
9.2 Water (CONTACT: J. M. Long, FTS 250-3525)
More detailed information than that given below can be found in the
"Interim Method for Determining Asbestos in Water" (EPA-600/4-80-005,
January 1980). This method, although considered to be state-of-the-
art, has not been designated as the approved procedure for determin-
ing asbestos in water.
Samples collected are treated with ultrasound for 15 minutes, and a
known volume (generally 50-500 ml, depending on solids and asbestos
concentration) of water sample is filtered through a 0.1 urn Nuclepore
filter to trap asbestos fibers. The filter is then carbon coated, a
small portion of this filter with deposited fibers is placed on an
electron microscope grid, and the filter material is removed by
gentle solution in chloroform. The grids are then examined in a
transmission electron microscope at a magnification of about
20.000X. The asbestos fibers are identified by their morphology and
electron diffraction patterns and their lengths and widths are mea-
sured. The electron diffraction pattern obtained from the suspect
fiber is compared with diffraction patterns from UICC standard mate-
rial for confirmation as asbestos. The fiber must have an aspect ra-
tio (length/width) greater than or equal to 3 to 1. The total area
9-1 July, 1982
-------
of the grid examined in the electron microscope is determined and the
number of asbestos fibers in this area is counted. The concentration
in million fibers per liter (MFL) is calculated from the number of
fibers counted, the volume of sample filtered, and the ratio of the
total filter area/sampled filter area. The mass per liter is calcu-
lated from the assumed density and the volume of the fibers.
Under favorable circumstances the detection limit is around 0.01 MFL
(fiber concentration) corresponding to the order of 0.1 nanogram per
liter (mass concentration). The common range of concentrations over
which this procedure is applicable is from the limit of detection
(0.01 MFL) up to about 900 MFL. Intra- and inter-laboratory
precision for chrysotile analysis over this range is about 35%. For
amphibole analysis intra-laboratory precision over the range is also
about 35%; however, inter-laboratory precision for amphibole analysis
is about 60%.
Mineral fibers that are occasionally misidentified as chrysotile as-
bestos are halloysite, palygorskite, and vermiculite. If the sample
contains copious amounts of organic matter, this material can be re-
moved by using Low Temperature Plasma Ashing. The ash is resuspended
in water, refiltered on fresh nuclepore filter, and the particles are
then counted.
Other methods for chrysotile (not amphibole) asbestos in water have
been reported in "Development of a Rapid Analytical Method for Deter-
mining Asbestos in Water" (EPA-600/4-78-066). Chrysotile fibers are
separated (75% recovery) from the bulk of other fibrous material by
extraction into isooctane from water samples containing added anionic
surfactant. The filtered isooctane fraction is then examined by
microscope or by a visual color spot test. The reported detection
limits are 100 nanogram per liter ( 10 MFL) for the color test and 1
nanogram (0.1 MFL) for the optical microscopy method.
9.3 Solid Waste (CONTACT: W. Beckert, FTS 595-2137;
T. Hinners, FTS 595-2140)
Asbestos is no longer listed as a hazardous waste, and no pollutant
measurements are required or specified for waste management proce-
dures. If analysis of a waste for asbestos is desired the "Interim
Method for Determining Asbestos in Water" (EPA-600/4-80-005) could be
applied. If organic matter is collected in the filter and obscures
the fibers, a specified low-temperature ashing procedure followed by
refiltration is applicable.
9.4 Other Samples (CONTACT: Michael E. Beard, FTS 629-2623)
Bulk - While EPA has not promulgated an analysis methodology, an
interim method for bulk sample analysis has been developed and is
currently being evaluated.
9-2 July, 1982
-------
The interim method has been developed primarily for the analysis of
friable, sprayed-on insulation materials which may contain asbestos
fibers. Core samples of the suspect material are taken with a clean
container such as a 35mm film canister. Caution should be exercised
during sampling to avoid generating dust; it is recommended that the
material be lightly sprayed with water before sampling. At least
three samples should be taken from each area homogeneous in appear-
ance. Detailed instructions on sampling and survey program design
are reported in EPA 560/13-80-017A, December 1980 (Asbestos-Contain-
ing Materials in School Buildings; Guidance for Asbestos Analytical
Programs).
Samples are analyzed by polarized light microscopy (PLM). Samples
may be treated to remove interferences such as binders and organic
matrix material. Indentification of asbestos requires the observa-
tion of diagnostic optical properties for each fiber type in the
sample. The relative area occupied by asbestos fiber within micro-
scope fields of view is determined by a point counting technique.
The relationship between relative area and weight percent of asbestos
in a sample is currently being investigated. Multiple laboratory
analysis of replicate samples containing a known weight percent of
asbestos in a predominately gypsum matrix has provided some informa-
tion on the performance of the iterim method. The bias of the method
varies with asbestos type and weight percentage: for samples con-
taining 10% chrysotile by weight, bias is 18.5%; for 50% chrysotile,
bias is -24.2%; for 10% amosite, bias is 118.5%; for 50% amosite,
bias is 12.1%. The coefficient of variation (CV) varies with the re-
ported area percent value: at a mean reported value of 10% asbestos,
CV = 79%; for 50% asbestos, CV = 41%. The rate of false negatives is
such that the analysis of three samples of a suspect material, if
each contained at least 5% asbestos by weight, would result in three
false negatives with a probability less than 0.03 and possibly as low
as 0.001.
The interim method includes procedures for x-ray powder diffraction
(XRD) analysis should further information on a sample be required.
It should be emphasized that XRD affords information only on crystal
lattice structure and not on gross crystal morphology. Therefore,
XRD cannot distinguish between the asbestos minerals and their non-
asbestiform varieties. Particle morphologies must be determined by
an optical technique such as PLM. It is therefore imperative that
XRD be used only as a corroborative procedure with PLM and not as an
independent analytical method. Although electron microscopy can be
used for bulk samples, it is not recommended because only small quan-
tities of sample can be analyzed at one time and multi-sample analy-
sis becomes prohibitively expensive.
Procedures for Occupational Exposure
The "tJIOSH Manual of Analytic Methods" contains several procedures
for determining asbestos levels in air. A thermal analysis procedure
9-3 July, 1982
-------
and a microscopic counting method «450-x magnification) are de-
scribed in Volume I (1977, Procedures 245 and 239, respectively).
Volume V (1977, Procedure 309) contains an x-ray diffraction proce-
dure for chrysotile.
Note that data currently relating concentrations of fibers (>5 urn)
counted by optical microscopy to concentrations measured by electron
microscopy are limited (estimates of the ratio of >5 urn fibers count-
ed by electron to optical methods range from 15:1 to 1000:1).
9.5 Quality Assurance (CONTACT: M. E. Beard, FTS 629-2623)
Asbestos reference materials are currently being developed by the
National Bureau of Standards (NBS) through an interagency agreement
with EPA. The materials will consist of filters deposited with chry-
sotile and various species of amphibole asbestos in an urban air par-
ticulate matrix and will be available in 1982. Prototypes of these
devices are available on a limited basis.
An external quality assurance program for PLM analysis of bulk sam-
ples is currently available through the EPA Asbestos-in-Schools Pro-
gram. Presently there are no QC samples for asbestos in water.
9-4 July, 1982
-------
REFERENCES
The major references used in preparation of this document are listed below.
EPA references are listed by EPA office of origin and the year of publica-
tion. For further information refer to contacts given throughout this docu-
ment or contact the relevant EPA offices listed at the end of this section.
(IARC, 1977)
(Michaels, 1979)
(NIH, 1978)
(NIOSH, 1972)
(NIOSH, 1980)
(OPTS, 1980)
(OWRS, 1979)
(OWRS, 1980)
(SRI, 1982)
IARC Monographs on the Evidence of the Carcinogenic Risk
of Chemicals to Humans, Vol. 14, International Agency for
Research on Cancer, WHO (1977).
Asbestos - Properties, Applications, and Hazards, Vol. 1,
L. Michaels and S. Chissick, Eds., Wiley (1979).
Asbestos - An Information Resource, National Institutes
of Health, DHHS pub. no. (NIH) 79-1681 (1978).
Criteria For a Recommended Standard - Occupational Expo-
sure to Asbestos, National Institute for Occupational
Safety and Health, DHH pub. no. (NIOSH) 72-169 (1972).
Workplace Exposure to Asbestos, National Institute for
Occupational Safety and Health, DHHS pub. no. (NIOSH)
81-103 (1980).
Support Document: Asbestos-Containing Materials in
Schools, EPA-560/12-80-003, Office of Pesticides and
Toxic Substances (1980).
Water-Related Environmental Fate of 129 Priority Pollut-
ants, Vol. 1, Ch. 7, EPA-440/4-79-029a, Office of Water
Regulations and Standards (1979).
Ambient Water Quality Criteria for Asbestos, EPA 440/5-
80-022, Office of Water Regulations and Standards (1980).
Chemical Economics Handbook, "Asbestos-Salient Statis-
tics", SRI International (1982).
R-l
July, 1982
-------
OFFICE CONTACTS
The EPA offices and divisions that are listed below may be contacted for more
information relating to the indicated sections of this document. While these
offices are, in many cases, the offices of origin for the data included in
this paper, the personal contacts given throughout this document should be
contacted first. Unless otherwise noted, the offices listed are situated in
Headquarters, Washington, D.C., and the telephone numbers given are FTS
(Federal Telecommunications System) numbers. For commercial telephone calls
to Headquarters which are not placed on FTS, area code 202 must be used.
Other commercial numbers are noted for the office contacts located outside
Washington, D.C.
HEALTH AND ENVIRONMENTAL EFFECTS (Section 2)
Office of Health and Environmental Assessment (OHEA)
Environmental Criteria and Assessment Office:
Cincinnati, OH 684-7531 (513-684-7531)
Research Triangle Park, NC 629-2266 (919-541-2266)
Carcinogen Assessment Group 755-3968
Office of Drinking Water (ODW)
Health Effects Branch 472-6820
Office of Toxic Substances (OTS)
Health and Environmental Review Division 382-4241
Environmental Research Laboratory
Duluth, MN, Region V 783-9550 (218-727-6692)
ENVIRONMENTAL RELEASES AND EXPOSURE (Sections 3 and 4)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504
Office of Water Regulations and Standards (OWRS)
Monitoring and Data Support Division 426-2503
R-2 July, 1982
-------
Office of Toxic Substances (OTS)
Exposure Evaluation Division 382-3873
Assessment Division 382-3442
DATA BASES (Section 5)
Office of Toxic Substances (OTS)
Management Support Division 382-3546
REGULATORY STATUS, STANDARDS, AND CRITERIA (Sections 6 and 7)
Office of Mr Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Drinking Water (ODW)
Criteria and Standards Division 472-5016
Office of Water Regulations and Standards (OWRS)
Criteria and Standards Division 755-0100
Effluent Guidelines Division 426-2571
Office of Solid Waste (OSW)
State Programs and Resource
Recovery Division 755-9107
SPILL CLEAN-UP AND DISPOSAL (Section 8)
NOTE: For Emergenices call the National Response Center at 1-800-424-8802
(1-800-426-2675 from the Baltimore/Washington area).
Office of Emergency and Remedial Response (OERR)
Emergency Response Division 245-3045
Oil and Hazardous Materials Spills Branch
Edison, NJ; Region II 340-6634 (201-321-6634)
R-3 July, 1982
-------
Office of Solid Waste (OSW)
Hazardous and Industrial Waste Division 755-9187
ANALYTICAL TECHNIQUES (Section 9)
Environmental Monitoring Systems Lab (EMSL)
Air Analysis
Research Triangle Park, NC 629-2454 (919-541-2454)
Water Analysis
Cincinnati, OH 684-7311 (513-684-7311)
Waste Analysis
Las Vegas, NV 545-2137 (702-798-2137)
GENERAL IFF COMMENTS. CORRECTIONS, OR QUESTIONS
Office of Toxic Integration
Chemical Information
and Analysis Program 382-2249
R-4 July, 1982
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Benzene
-------
BENZENE
Table of Contents Page
Physical/Chemical Properties and Chemistry 1-1
Properties 1-1
Chemistry and Environmental Pate/Transport 1-2
Effects Information 2-1
Health Effects 2-1
Environmental Effects 2-2
Environmental Release 3-1
Air Releases 3-1
Water Releases 3-2
Land Releases 3-2
Exposure 4-1
Air Exposure 4-1
Water Exposure 4-1
Other Exposure Routes 4-1
Data Bases 5-1
NIH/EPA Chemical Information System (CIS) 5-1
Chemical in Commerce Information System (CICIS) 5-2
Chemical Substances Information Network (CSIN) 5-2
Graphic Exposure Modeling System IGEMS) 5-3
Regulatory Status 6-1
Promulagated Regulations 6-1
Proposed Regulations 6-3
Other Actions 6-5
Standards and Recommended Criteria 7-1
Air 7-1
Water 7-1
July, 1984
-------
Spill or Other Incident Clean-Up/Disposal 8-1
Hazards and Safety Precautions 8-1
First Aid 8-1
Emergency Action 8-1
Notification and Technical Assistance 8-2
Disposal 8-2
Sampling, Acceptable Analytical Techniques, and Quality Assurance 9-1
Air 9-1
Water 9-1
Solid Waste 9-2
Other Samples 9-3
Quality Assurance 9-3
References and Office Contacts R-1
July, 1984
-------
BENZENE
1. PHYSICAL/CHEMICAL PROPERTIES AND CHEMISTRY
1.1 Properties
Benzene is a volatile, flammable aromatic hydrocarbon which is pro-
duced domestically in large volume (14.8 billion Ibs in 1980). A
number of physical properties of benzene are listed in Table 1. The
relatively high water solubility and volatility illustrate the high
potential of benzene for intermedia transfer.
TABLE 1: PROPERTIES OF BENZENE3
Synonyms:
CAS Number:
Molecular Formula:
Structure:
Physical Properties:
Melting point
Boiling point
Vapor pressure (25°C)
Flashpoint (closed cup)
Density (25°C, g/ml)
Water solubility (25CC)
Octanol/water partition
coefficient (log P)
Benzol, cyclohexatriene
71-43-2
C6H6
5.55°C
80.18C
95.2 torr
-ll.l'C
0.874
1.8 g/1
2.13
a Source: Data as summarized in (OTS, 1975),
1-1
July, 1982
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1.2 Chemistry and Environmental Fate/Transport
Benzene can undergo a wide variety of chemical transformations
(substitution, oxidation, reduction) to yield many chemicals of com-
mercial importance. In all cases these reactions are carried out
with catalysts, strong acids, elevated temperatures, or high pres-
sures and, therefore, are not likely environmental processes. Fur-
thermore, the direct photolysis in the environment is unlikely be-
cause benzene does not absorb natural sunlight appreciably (OTS,
1975; OWRS, 1979).
Due to its high volatility, most of the benzene released to the envi-
ronment is emitted to the atmosphere. The atmospheric photooxidation
of benzene probably subordinates all other fate processes. The half-
life (t 1/2) for benzene In the atmosphere has been estimated to be
from 2.4 to 24 hours; benzene depletion is thought to arise primarily
from attack of photochemically generated hydroxyl radicals. Because
of its fairly high solubility in water, benzene is washed out of the
atmosphere by precipitation (OTS, 1975; OWRS, 1979).
The predominate fate for benzene in water is volatilization to the
atmosphere. However, due to the relatively high water solubility,
persistence of some benzene in the water column Is expected. Benzene
which persists in the water is expected to biodegrade at a slow
rate. The partition coefficient for benzene indicates a low bioaccu-
mulation potential for benzene (OWRS, 1979).
1-2 July, 1982
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2. EFFECTS INFORMATION
2.1 Health Effects (CONTACTS: Jerry Stara, FTS 684-7531; Bob McGaughy,
FTS 755-3968; Penny Fenner-Crisp, FTS 472-
4944)
2.1.1 Acute Toxicity
In humans acute benzene poisoning is characterized by nausea, vomit-
ing, ataxia (a loss of the power of muscular coordination) and ex-
citement followed by depression and coma. Death is usually the re-
sult of respiratory or cardiac failure. Benzene exposure causes
acute toxic effects on the central nervous system (CNS). Single
exposures of benzene in the air at a concentration of 20,000 ppm have
proved to be fatal within 5 to 10 minutes. Effects include headache,
nausea, staggering gait, paralysis, convulsions, and eventual uncon-
sciousness and death, usually following cardiovascular collapse.
Giddiness and euphoria have also been reported. Severe nonfatal
cases have exhibited similar symptoms but recovered after a period of
unconsciousness. Accidentally ingested benzene may result in ulcer-
ation of the gastrointestinal mucosa (OWRS, 1980).
2.1.2 Chronic Toxicity
Although CNS and gastrointestinal effects may result from chronic
benzene exposure, the important toxic manifestations are related to
Injury of the blood-forming (hematopoietic) system. Benzene damages
the bone marrow and may be unique among aromatic hydrocarbons sol-
vents in this respect. Alkyl substitution of the benzene ring (e.g.,
toluene) markedly alters the metabolism and apparently largely re-
moves the potential for bone marrow toxicity. Benzene is causally
related to pancytopenia (reduced levels of red and white blood cells
and platelets in the blood) which may be manifested by anemia, in-
creased susceptibility to infections and/or a reduction in the
blood's ability to clot. Aplastic anemia (reduced hematopoietic sys-
tem cells in the bone marrow) is also linked closely to benzene expo-
sure in occupational settings. Benzene exposure studies on numerous
nonhuman animals have produced similar blood disorders (OWRS, 1980;
Cheremisinoff, 1979).
Carclnogenlclty, Mutagenicity and Teratogenicity - Studies linking
benzene exposure to human leukemia are quite prevalent and have pro-
duced evidence that is considered conclusive (OWRS, 1980; NAS, 1976;
IARC, 1980). The most common benzene-associated leukemia is myeloge-
nous leukemia, also known as acute myeloblastic leukemia. These epl-
demlological studies have been performed on groups of workers which
showed a rise in leukemia cases with the usage of benzene. However,
the available literature is not considered adequate by EPA for calcu-
lation of accurate dose-response curves for the relationship of ben-
zene exposure to the development of acute leukemia. In those studies
of acute leukemia where benzene exposure levels have been reported,
concentrations have generally been above 100 ppra, or 325 rag/m^ (OWRS,
1980).
2-1 July, 1982
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Thus far, animal experiments have not yielded conclusive evidence
that benzene is leukemogenic. However, recent studies have yielded
some carcinogenic response. Rats have shown an increased incidence
of Zymbal gland (inner ear) tumors, mammary gland carcinomas, and
leukemia; in this study benzene was introduced by gavage (SO and 250
rag/kg» 4-5 times per week for 52 weeks). A recent inhalation study
reported an increased incidence of thymic lymphoma in mice exposed to
300 ppm of benzene (OURS, 1980).
While benzene has not shown mutagenic activity in the Salmonell-
microsome ^n vitro assay, it has shown such activity in animals and
man. Chromosomal abnormalities in bone marrow cells have been re-
ported as a result of experimental benzene exposure in rats, rabbits,
mice, and amphibians. Benzene is a mitotic poison, producing a de-
crease in DNA synthesis in animal bone marrow cells jji vitro and in
cultured human cells. Cytogenetic abnormalities in benzene-exposed
humans have been observed and such abnormalities may persist for
years after cessation of exposure. Studies on workers clearly indi-
cate a causal relationship between benzene exposure and persistent
chromosomal abnormalities. However, no direct evidence supports the
linkage between chromosomal aberrations and the induction of leukemia
in humans (OURS, 1980).
From available data, it is unlikely that benzene administered by
inhalation during the principal period of organogenesis constitutes a
teratogenic hazard. However, the data is not sufficient for other
stages of the reproductive cycle (OWRS, 1980).
2.2 Environmental Effects (CONTACTS: Bill Brungs - Freshwater; and John
Gentile - Saltwater: FTS 838-4843)
2.2.1 Aquatic Effects (OWRS, 1980)
The acute toxicity of benzene to freshwater species has been measured
with eight species and the species acute values range from 5,300 ug/1
to 386,000 ug/1. No data are available for benthic crustaceans,
benthic insects, or detritivores. However, the most important defi-
ciency may be that only with the rainbow trout were the results ob-
tained from a flow-through test and based on measured concentra-
tions. Results based on unmeasured concentrations in static tests
are likely to underestimate toxicity for compounds like benzene that
are relatively volatile.
A life cycle test was conducted with one freshwater species, Daphnia
magna, but no concentration up to 98,000 ug/1 caused an adverse
effect. On the other hand, concentrations which apparently did not
adversely affect Daphnia magna in a life cycle test did affect other
species in acute tests.
For saltwater species, species acute values are available for one
fish species and five invertebrate species and range from 10,900 to
924,000 ug/1. These values suggest that saltwater species are about
as sensitive as freshwater species. The one acute value from a flow-
through test in which toxicant concentrations were measured was not
2-2 July, 1982
-------
the lowest value, as was the case with the freshwater acute data.
Saltwater plants seem to be about as sensitive as saltwater animals.
Other data indicate that herring may have suffered stress and some
mortality at 700 ug/1.
The available data for benzene indicate that acute toxicity to fresh-
water aquatic life occurs at concentrations as low as 5,300 ug/1 and
would occur at lower concentrations among species that are more sen-
sitive than those tested. No data are available concerning the
chronic toxicity of benzene to sensitive freshwater aquatic life.
The available data for benzene indicate that acute toxicity to salt-
water aquatic life occurs at concentrations as low as 5,100 ug/1 and
would occur at lower concentrations among species that are more sen-
sitive than those tested. No definitive data are available concern-
ing the chronic toxicity of benzene to sensitive saltwater aquatic
life but adverse effects occur at concentrations as low as 700 ug/1
with a fish species exposed for 168 days.
2-3 July, 1982
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3. ENVIRONMENTAL RELEASE
In recent years nearly all (96% In 1978) of the benzene produced do-
mestically is obtained during the fractionation and enrichment of
petroleum; the balance is produced from coke oven sources. Benzene
is also a constituent of motor fuels. While present in low concen-
trations in crude oil, the benzene content of the crude increases
during catalytic reformation. BTX (a mixture of benzene, toluene,
and xylene) is separated from the refined oil and, if a higher con-
tent of aromatlcs is desired in the gasoline (to raise octane rat-
ings), BTX may be blended back into the gasoline pool. Thus, benzene
would not be counted in reports of total benzene production if it was
not separated from the BTX mixture. Gasoline production and market-
ing contributes to the amount of benzene released to the environment
even though this benzene is not included in reported production fig-
ures. Approximately one-half of the benzene in reformats is isolated
for use, the remainder is left in the reformate and stays in gasoline
at levels of 0.5% to 2% (OPTS, 1980).
The predominant use of benzene is as a feedstock for the synthesis of
a wide variety of organic compounds. Most of these compounds are
eventually incorporated into polymers (synthetic rubbers, plastics,
resins, and fibers). Based on 1980 data, the largest use for benzene
is in the production of ethylbenzene (51%), a precursor for styrene.
Cumene (20%) and cyclohexane (14%) are other major products of ben-
zene. Direct uses of benzene (e.g., as a solvent) are now negligible
(SRI, 1982; OPTS, 1980).
Table 2 summarizes estimated annual releases (for 1978) from the pro-
duction and use of isolated benzene; also included are releases aris-
ing from the presence of benzene in fuels. It is obvious from the
data in the table that nearly all of the benzene released is emitted
to the air.
3.1 Air Releases (CONTACT: Dave Patrick, FTS 629-5345)
Significant sources:
• Ethylbenzene/Styrene manufacturing (SIC 2869)
• Coke by-product plants (SIC 3312)
• Benzene storage vessels in refining and chemical plants (SIC
286, 2911)
• Chemical plant petroleum refinery fugitive emissions
(SIC 286, 2911)
• Maleic anhydride plants (SIC 2869)
Although benzene release is heaviest from the marketing and use of
fuels, the Agency has ranked this as low priority because: the rela-
tively low individual risk to the exposed population; the projected
decrease in benzene tailpipe emissions by 1985 to one-quarter of 1978
levels due to increased prevalence of catalytic converters and die-
sels; and the reduction of benzene evaporative emissions due to SIPs
and other actions.
3-1 July, 1982
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3.2 Water Releases (CONTACT: Charles Delos, FTS 426-2503)
• Solvent use
• Petroleum refinery
• Chemical plants
3.3 Land Releases
• Gasoline refinery
• Petroleum refinery
3-2 July, 1982
-------
TABLE 2: ESTIMATED RELEASES OF BENZENE FDR 1978 a
(Metric tons/year)
OJ
1
GO
c_.
QT
M
Category
Pure Sources of Production
From Petroleum
From Coal Light Oil
From Coal Coking
Import
Inventory Reduction
Pure Uses
Chanlcal Feedstock
Solvent
Export
Transport /Storage
Sources & Uses of Mixtures
Gasoline Refining
- Imports
- Transport/Storage
- Consumption
Other Fuel ProJ.
- Use
Coal Coklngh
Impure Solvent Production
- Use
Oil Spills
Other Industry
POTW
Natural Sources
TOTALS
Production Use
4,709,900
65,400
178,786
225,000
272,000
5,251,000
9,600
151,000
1,400,000
3,288,000
4,440 ,000
959,410
959,410
107,000
107,000
30
148
?
11,205,644 10,918,040
Destruction
0
0
0
0
0
5,107,300
6,590
150,983
0
2,000
0
0
4,254,000
0
923,850
^
0
7
0
0
10,444,723
Air
3,139
?
768
13
0
10,681
1,505
?
7,200
20,000
0
21,000
165,000
?
35,560
30,000
?
?
0
?
90
?
294,956
Water
620
?
10
13
0
235
1,505
2
72
1
0
0
0
9
0
?
?
?
30
148
30
?
2,666
Land
141
?
8
0
0
?
0
15
?
228
0
?
0
?
0
?
?
?
0
?
5
?
337
Unaccounted
10,865b
107,000
117^65
CO
INJ
a Most of the data are from a Level II Materials Balance (OPTS, 1980); some release estimates were revised by OIKS and Q4QPS based on
more recent data.
b Carry over Into products.
c Facilities not recovering benzene.
-------
4. EXPOSURE
4.1 Air Exposure (CONTACT: Dave Patrick, FTS 629-5645)
The major route of human exposure to benzene is via inhalation. The
annual average exposure for the general public to ambient benzene
from all air sources is estimated to be about 1 ppb or 3.2 ug/ra^
(OAQPS, 1978). The geographical distribution of benzene emission due
to gasoline marketing and use probably approximates population densi-
ty distribution. Concentrations of benzene around gas stations range
from 0.3 to 3 ppm (OTS, 1975). The rural background levels for ben-
zene are estimated to be 0.017 ppb (OWRS, 1980).
Specific sources likely to be exposure routes are:
• Continuous or semi-continuous emissions from benzene-contain-
ing process vents
• Fugitive leaks from valves, pumps, and compressors carrying
benzene
• Evaporative emissions from improper disposal of benzene-
containing storage tanks and handling systems
• Automobile tailpipe emissions; gasoline storage and marketing
• Accidental spills
4.2 Water Exposure (CONTACTS: Charles Delos, FTS 426-2503; Bill
Coniglio, FTS 382-3035)
Four of ten water supplies surveyed by EPA contained benzene at con-
centrations of 0.1 to 0.3 ug/1; the highest level ever reported in
finished drinking water was 10 ug/1. Based on the limited data,
water intake is not a major route of exposure for benzene (OWRS,
1980).
Specific sources of aquatic benzene of most concern are:
Accidental spills to water supplies
Leaks of storage tanks to ground water
Drinking water contamination from atmospheric wash out
Waste water discharge downstream from chemical plant
Food fish contamination
4.3 Other Exposure Routes
Although ingestion of benzene is not considered to be a problem for
the general population, relatively high levels of benzene have been
found in some foods such as eggs (500-1900 ppb) and rum (120 ppb).
Certain occupational groups have the potential for exposure to ben-
zene levels above ambient levels. The industrial activities of con-
4-1 July, 1982
-------
cern include chemical manufacturing, coking operations, gasoline
service stations, refineries, and solvent operations (OWRS, 1980).
Benzene has also been reported in cigarette smoke. The presence of
benzene is suspected to result from pyrolytic reformation of tobacco
constituents during combustion.
4-2 July, 1982
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5. DATA BASES
5.1 NIH/EPA Chemical Information System (CIS)
This is a collection of various scientific data bases available
through an interactive computer program. The linking system between
these data files is the Structure and Nomenclature Search System
(SANSS). CIS can also provide a list of non-CIS sources of
information on a chemical of interest. For further information,
contact Jim Cottrell at FTS 382-3546.
CIS contains numeric, textual, and bibliographic information in the
areas of toxicology, environment, regulations, and physical/chemical
properties. Several of these data bases are described below.
5.1.1 EPA Chemical Activities Status Report (EPACASR)
EPACASR is an on-line system containing information on EPA's interest
in chemicals. This system includes data on the Agency's regulations,
research, and assessments directed toward specific chemicals.
EPACASR is published annually and tN» data base is updated as
information is received. A searchable subset itemizes NTP/NCI
studies and results, as well as chemicals disc"""**! in the IARC
monograph series. (Other sources are added as appropriate.) Entries
identify the statutory authority, the nature of the activity, its
status, the reason for and/or purposes of the effort, and a source of
additional information.
EPACASR is now available on CIS for internal use by EPA personnel and
is expected to be accessible from a public CIS account in the ne-r
future. The publication and computer tapes are also available
through the National Technical Information Service (NTIS). For
further information on EPACASR, contact Eleanor Merrick at
FTS-382-3626.
5.1.2 Indus try File Indexi ng Sys tern (IFIS)
IFIS is an on-line system which contains information relating to the
regulation of chemicals by EPA through industry-specific
legislation. IFIS enables the user to determine, for any particular
industry, which chemicals are used and produced and how these
chemicals are regulated. IFIS is currently available on CIS for
internal use by some EPA personnel and is expected to be accessible
from a public CIS account soon. For more information on IFIS,
contact Daryl Kaufman at FTS 382-3626.
5.1.3 Scientific Parameters in Health and the Environment,
Retrieva1 and Estimation (SPHERE)
SPHERE is being developed by the EPA Office of Toxic Substances as a
system of integrated data bases, each representing a compilation of
extracted scientific data. The system is being released to the
public in stages as part of CIS, and the accessibility of component
data bases should be confirmed with the contact given below. The
5-1 July, 1984
-------
components currently available {either through public CIS accounts or
the internal EPA system) include: DERMAL, which provides
quantitative and qualitative health effects data on substances
admitted to humans and test animals via the dermal route; AQUIRE, a
component containing aquatic toxicity data for about 2,000 chemicals;
GENETOX, a mutagenicity data base; ISHOW, and ENVIROFATE, both of
which are compilations of physical/chemical parameters useful in
assessing environmental fate and transport. For more information
contact Paula Miles, FTS 382-3760.
5.1.4 Oil and Hazardous Materials Technical Assistance Data System
(OHMTADS)
OHMTADS is a data base created by EPA to aid spill response teams in
the retrieval of chemical-specific response information. The file
currently contains data for approximately 1,200 chemicals including
physical/chemical, biological, toxicological, and commercial
information. The emphasis is on harmful effects to water quality.
OHMTADS is available to the public through CIS.
5.1.5 Chemical Eyaluation Search and Retrieval Sys tern (CESARS)
CESARS provides detailed information and evaluations on a group of
chemicals of particular importance in the Great Lakes Basin. CESARS
was developed by the State of Michigan with support from EPA's Region
V. Presently, CESARS contains information on 180 chemicals including
physical-chemical properties, toxicology, carcinogenicity, and some
aspects of environmental fate. Information for most chemicals is
extensive and consists of up to 185 data fields. CESARS is
accessible through public CIS accounts.
5.2 Chemicals in Commerce Information System (CICIS)
CICIS is an on-line, version of the inventory compiled under the
authority of TSCA. This law required manufacturers of certain
chemicals (excluding food products, drugs, pesticides, and several
other categories) to report production and import data to EPA. CICIS
contains production volume ranges and plant site locations (for 1977)
for over 58,000 chemical substances. There is also a Confidential
Inventory in which data for some chemicals are claimed confidential
and are not available in the public inventory. A version of CICIS
(TSCA Plant and Production, or TSCAPP) is now accessible through
CIS. For more information contact Gen Nowak at FTS 382-3568.
5.3 Chemical Substances Information Network (CSIN)
The Chemical Substances Information Network (CSIN) is not another
data base, but rather a sophisticated switching network. CSIN links
may independent and autonomous data and bibliographic computer
systems oriented to chemical substances, establishing a "library of
systems." Users may converse with any or all systems interfaced by
CSIN without training on these inde^ndent systems, regardless of the
hardware, software, data formats, or protocols of these information
resources.
5-2 JUly, 1984
-------
Information accessible through CSIN includes data on chemical
nomenclature, composition, structure, properties, toxicity,
production uses, environmental effects, regulations, disposal, and
other aspects of the life cycle of materials as they move through
society. Currently, twelve independent information resources are
accessible through CSIN, including: National Library of Medicine
(NLM); Chemical Information System (CIS); CAS-On-Line; Snc's ORBIT;
Lockheeds's DIALOG, and the Bibliographic Retrieval Service (BRS).
For further information contact Dr. Sid Siege1 at FTS 395-7285.
5.4 Graphical Exposure Modeling System (GEMS)
EPA has developed GEMS, an interactive computer system, to provide a
simple interface to environmental modeling, physiochemical property
estimation, statistical analysis, and graphical display
capabilities. GEMS is being developed for use by the Office of Toxic
Substances to support integrated exposure/risk analyses. The system
provides environmental analysts who are unfamiliar with computer
programming with a set of sophisticated tools to undertake exposure
assessments. For information about the system and the current
accessibility of GEMS, contact Bill Wood at FTS 382-3928.
5-3 July, 1984
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6. REGULATORY STATUS (Current as of 6/84)
6.1 Promulgated Regulations
6.1*1 EPA Programs
Clean Air Act (CAA)
o Section 112 - Benzene is designated as a hazardous air pollutant
(42 FR 29332). National emission standards for hazardous air
pollutants (NESHAP's) for benzene fugitive emission sources
(equipment leaks), were promulgated on June 6, 1984, 49 PR 23498
(40 CFR 61, Subparts J and V).
o Sections 202, 203, 205-208, 212 and 301 (a) - Standards to
control the release of air pollutants from motor vehicle exhaust
emissions by limiting hydrocarbon emissions are established (40
CFR 85 and 40-CFR 86).
o Section 111 - New source performance standards have been
promulgated to control fugitive emissions from the manufacture
of volatile organic chemicals (VOC's) from new process units
within the synthetic organic chemicals manufacturing industry.
Benzene is listed as a VOC (40 CFR 60.480-.482).
Clean Water Act (.CWA)
o Section 301 / 304^ 306( and 307 - Benzene is designated as a
toxic pollutant (40 CFR 401.15). Accordingly, effluent
limitations, pretreatment standards, new source performance
standards, and standards of performance for new and existing
sources have- been issued for sections of the following
industries:
Electroplating-1 (40 CFR 413, Subpart A, B, D-H),
- Iron and s*teel manufacturing (40 CFR 420, Subpart A),
- Stream electric power generating (40 CFR 423),
Metal finishing1 (40 CFR 433), and
Copper forming' (40 CFR 468, Subpart A).
o Section 311_(b_) (2) (A) - Benzene is designated a hazardous
substance (40 CFR 116.4); discharges are subject to reporting
requirements (40 CFR 117).
o Section 318, 402, 405(a) - National Pollutant Discharge
Elimination System (NPDES) permit testing requirements. Benzene
is listed as an organic toxic pollutant based on gas
chromatographic and mass spectroscopic analyses (40 CFR 122,
Benzene is controlled b.y limiting the total toxic organics
(TTO), which is the summation of all quantifiable value-s greater
than 0.1 milligrams per liter.
6-1 July, 1984
-------
Appendix D). Other permitting requirements are covered in the
consolidated permit programs (40 CFR 123 and 124).
Safe Drinking Hater Act (SDWA)
o Sections 1421, 1423, 1424, 1431 and 1450 - Benzene is designated
as a hazardous waste (40 CFR 144) on the basis of 40 CFR 261.3
and is subject to the requirements prescribed in the Underground
Injection Control Program (UIC) (40 CFR 144) and to the criteria
and standards developed under 40 CFR 146 to protect underground
sources of water. State program requirements are covered by 40
CFR 145.
Resources Conservation and Recovery Act (RCRA)
o Section 3001 - Commercial chemical products, off-specification
products, residues, and intermediates containing benzene are
classified as toxic hazardous wastes when discarded (40 CFR 261 .
33(f)).
Benzene is also identified as a toxic constituent of the
following waste streams designated hazardous under 40 CFR
261.31-.32:
- Distillation or fractionation column bottoms from the
production of chlorobenzenes (KO85),
combined wastewater streams generated from
nitrobenzene/aniline production (K104),
separated aqueous stream from the reactor product washing
step in the production of chlorobenzenes (K105), and
wastes including but not limited to: distillation
residues, heavy ends, tars, and reactor clean-out wastes
from the production of chlorinated hydrocarbons having a
carbon content from one to five, utilizing free radical
catalyzed processes (FO24), Interim final rule, 49 FR 5312.
o Sections 3002 to 3006 - Wastes identified as hazardous under
Section 3001 are subject to a "cradle to grave" management
system. Standards are established for generators of hazardous
waste for hazardous waste determination (40 CFR 262.11);
packaging, labeling, and marking (40 CFR 262.30-.34);
recordkeeping and reporting (40 CFR 262.40-.43). Standards for
transporters of hazardous waste are covered under 40 CFR 263.
Additional control standards covering treatment, storage, and
disposal facilities (40 CFR 264 and 265). Permit procedures are
included in the consolidated permit regulations covered in 40
CFR 122 to 124.
6.1.2 Programs of Other Agencies
OS HA - Occupational Safety and Health Act
o Section 6(a) - Benzene is designated as an air contaminant (29
pFR 1910.1000(b)(1-3)) in workplaces. Exposure of employees to
6-2 July, 1984
-------
benzene is limited by 8-hour time weighted averages (29 CFR
1910.1000, Table Z-2).
o Sections 4(b), 6(b), 8(a), and 8(c) - Benzene is designated as a
potential occupational carcinogen, and procedures are prescribed
for the identification, classification, and regulation of
potential occupational carcinogens (20 CFR 1990).
CPSC - Federal Hazardous Substances Act
o Section 30(a) - Under Section 3(b) of the FHSA, products
containing 5 percent or more by weight of benzene require
special labeling (16 CFR 1500.14). Poison prevention packaging
requirements as prescribed by Section 30(a) of the Consumer
Product Safety Act and Sections 1-9 of the Poison Prevention
Packaging Act of 1970 are covered in 16 CFR 1700'. 1.
Department of Transportation (DOT) - Hazardous Materials Transporta-
tion Act
o For purposes of transportation, DOT has designated benzene as a
hazardous material, of the flammable liquid hazard class (I.D.
No: UN 1114) (40 CFR 172.101). Additional parts of Title 49
applicable to benzene are reportable quantities (RQ's), and
labeling requirements (49 CFR 172.101 and 172.102); packaging
exceptions (49 CFR 173.118); specific requirements (49 CFR
173.119); carriage by rail (49 CFR 174, Subpart G); carriage by
aircraft (49 CFR 175); carriage by vessel (49 CFR 176, Subpart
I); and carriage by public highway (49 CFR 177, Subparts A-D).
Department of Transportation Act (DOTA)
Coast Guard, DOT (46 U.S.C. 391a)
o Identification of incompatible hazardous materials and
procedures for transporting those wastes (46 CFR 150).
o Regulations for benzene and benzene-hydrocarbon mixtures
prescribing transportation requirements (46 CFR 151.01-.10);
permissible airborne concentrations (46 CFR 151.50-.60).
o Requirements for self-propelled vessels transporting hazardous
materials (46 CFR 153).
6.2 Proposed Regulations
6.2.1 EPA Programs
CAA
0 Section 112 - EPA has proposed to limit benzene emissions from
new and existing coke oven byproduct recovery plants (49 FR
23522) through a combination of emission standards, equipment,
work practices, and operational requirements. Standards that
6-3 July, 1984
-------
were proposed for benzene emissions from maleic anhydride pro-
cess vents (45 FR 26660}; Ethylbenzene-styrene process vents <45
FR 83448); and benzene storage vessels {45 FR 83952) were with-
drawn from proposal (49 FR 23558, June 6, 1984).
Section 111 - Standards of performance for new sources of VOC
emissions from the synthetic organic chemical manufacturing
industry distilling operations proposed on December 30, 1933.
Benzene is listed as a VOC (48 FR 57538).
CWA
o Sections 301, 304, 306, and 3O7 - Proposed effluent limitations,
pretreatment standards, and new source performance standards
have been proposed to limit benzene discharges from facilities
engaged in the manufacture of organic chemicals and plastics (40
CFR 414), and synthetic fibers (40 CFR 416) (48 FR 11852, March
21, 1983).
EPA has proposed to regulate benzene by establishing effluent
limitations, pretreatment standards, and new source performance
standards for facilities engaged in the manufacture of pesticide
chemicals (47 FR 54010, November 30, 1982}.
Comprehensive Environmental Response, Compensation, and Liability Act
(CERCLA or Superfund).
o Sections 102(b), 103(a)(b) - CERCLA provides for the liability,
compensation, clean-up, and emergency response for the release
of hazardous substances into the environment. This Act also
deals with the clean-up of hazardous waste disposal sites (42
USC 9601; PL 96-510). EPA is developing regulations concerning
the designation of hazardous substances, the development of
report able quantity requirements (RQ's), claims procedures, and
the confidentiality of business records (46 FR 54032).
Revisions to the National Contingency Plan (NCP) as required by
CERCLA have been issued (47 FR 10972).
Benzene is a hazardous substance under CERCLA and will be
subject to regulations developed under Superfund. EPA has
proposed adjustments to the RQ's established under CERCLA and
the CWA (48 FR 23552).
RCRA
o Section 3001 - Regulations proposed to list as hazardous a group
of wastes of generic category generated during the manufacture
of chlorinated aliphatic hydrocarbons utilizing free radical
catalyzed processes, having a carbon content ranging from one to
five, and with varying amounts and positions of chlorine
substitution; benzene is designated as a hazardous constituent
(49 FR 5313).
6-4 July, 1984
-------
6.3 Other Actions
Public Health Service (PHS) - National Toxicology Plan (NTP)
o Benzene is cited as a substance known to be carcinogenic (Third
Annual Report on Carcinogens, September 1983) (48 FR 17259).
o Selected for mutagenicity testing FY 1984.
o Carcinogenesis toxicity testing to be completed in FY 1984.
6-5 July, 1984
-------
7. STANDARDS AND RECOMMENDED CRITERIA*
7.1 Air
o OSHA
8-hour time-weighted average (TWA) 10 ppm
Acceptable ceiling concentration 25 ppm
Acceptable maximum peak concentration 50 ppm
(Maximum Duration 10 minutes)
29 CFR 1910.1000, Table 2-2.
o American Conference of Government S Industrial Hygienists
(ACGIH)
8-hour TWA 10 ppm
Short Term Exposure Limit 30 ppm
(Maximum Duration 15 minutes)
7.2 Water
Water Quality Criteria for Human Health for ingestion of
contaminated water and aquatic organisms; the criterion
corresponding to an estimated lifetime cancer risk of 10~ is
6.6 ug/1. For ingestion of contaminated aquatic organisms only
the 10~5 risk level corresponds to a concentration of 400 ug/1.
Designated a hazardous substance under Section 311 of the CWA,
notification is required if discharges of benzene are equal to
or greater than 1,000 pounds (454 kg) (40 CFR 117.3). The
reportable quantity proposed under CERCLA is the same (48 FR
23552).
*See Appendix A for a discussion of the derivation, use, and
limitations of these Criteria and Standards.
7-1 July, 1984
-------
8. SPILL OR OTHER INCIDENT CLEAN-UP/DISPOSAL (CONTACT: National Response
Center, 800-424-8802; in the Washington area, 426-2675)
8.1 Hazards and Safety Precautions
Benzene is a flammable liquid which may be ignited by heat, sparks, and
flames. Vapors may '• travel -a considerable distance -to -a source of
ignition and iflash back,. Vapors may cause drzzrness "or suffoca'tion.
Contact may irrita-te or .burn skin and -eyes. Liquid as harmful if
swallowed. Fires ma.y 'produce irritating or poisonous gases. Runoff
from fire control or dilution water 'may cause pollution.
Outdoor or detached storage preferable. Indoor storage should -be in
standard flammable liquid storage -rooms. Store in well-closed, non-
glass containers --in >cool area. Spark resistant tools should be 'used.
Wear chemical safety goggles, face shield, s'elf-contained breathing
apparatus and rubber protective 'Clothing.
8.2 First Aid
Move victim to 'fresh air; call emergency and •medical care. If not
breathing, give artificial respiration. If breathing is difficult,
give oxygen. No adrenaline should be used as a respiratory
stimulant. In 'case of contact with benzene, immediately flush skin or
eyes with running water for at least 15 minutes. Remove and isolate
contaminated clothing .and shoes. If swallowed and victim is conscious,
have victim drink water or milk.
8.3 Emergency Action
Spills or Leak
Avoid contact with liquid and vapor. Stay upwind; notify local fire,
air, and water authorities of the accident. Evacuate unnecessary
people immediately and isolate hazard area. Explosion hazard is great
if ignition has not already occurred, hence civil defense authorities
should be alerted. Water intakes are threatened and should be
closed. Attempts should be made to contain slicks. Full protective
clothing including self-contained breathing apparatus should be worn.
Small spills of benzene can be taken up by sorption on carbon or
synthetic sorbent resins. The "Hazardous Materials 1980 Emergency
Response Guidebook" recommends take-up with sand or other non-
combustible material and then flushing the area with water. For large
quantities, if response is rapid, benzene can be skimmed off the
surface. Straw may be used to mop slicks. The following steps should
be taken for spills occurring at manufacturing facilities: (1) inspect
for malfunctioning control devices and leaks in major equipment, (2) if
malfunction cannot be repaired within 72 hours, process shutdown should
be considered, and (3) major leaks should be repaired within 15 days.
8-1 August, 1984
-------
Fire
Use dry chemical, foam, or carbon dioxide. Water spray may be
ineffective as an extinguishing agent, but water should be used to keep
fire-exposed containers cool until well after the fire is out. Move
containers from fire area if this can be done without risk. Stay away
from ends of tanks. For massive fire in cargo area, use unmanned hose
holder or monitor nozzles. If this is impossible, withdraw from area
and let fire burn. Withdraw immediately in case of rising sound from
venting safety device or discoloration of tank.
8.4 Notification and Technical Assistance
Section 103 (a) and (b) of the Comprehensive Environmental Response,
Compensation, and Liability Act (CERCLA) of 1980 requires persons who
release hazardous substances into the environment in reportable
quantities determined pursuant to Section 102 of the Act to notify the
National Response Center (NRC): 800-424-8802 (in Washington, D.C. 426-
2675).
Benzene is designated as a hazardous substance under CWA Section 311.
Its reportable quantity is 10OO pounds.
For technical assistance, call CHEMTREC (Chemical Transportation
Emergency Center): 800-424-9300. Other sources of technical
information are (1) the EPA's Oil and Hazardous Materials - Technical
Assistance Data System (OHM-TADS) contained in the NIH-EPA Chemical
Information System (CIS) which provides information pertinent to
emergency spill response efforts and (2) the CHRIS system which
provides information on first aid, physical/chemical properties, hazard
assessments, and response methods. Both systems can be accessed
through NRC.
8.5 Disposal
Benzene is designated as a "toxic" waste under 40 CPR 261.33{f) of RCRA
and generators of greater than 7,OOO kg of waste are subject to the
provisions of subpart D (Section 30O4), Standards for Owners and
Operators of Hazardous Waste Treatment, Storage, and Disposal Facili-
ties.
The following wastestrearns are classified as hazardous wastes due, in
part, to the presence of benzene (40 CFR 261.32):
o Distillation or fractionation column bottoms from chlorobenzene
production (K085).
o Separated aqueous stream from the reactor product washing step in
chlorobenzene production (K105).
o Combined wastewater streams generated from nitrobenzene/aniline
production (K104).
8-2 August, 1984
-------
o Wastes including but not limited to, distillation residues, ho.ivy
ends, tars, and reactor clean-out wastes from the production ot
chlorinated hydrocarbons having a carbon content from one to
utilizing free radical catalysed processes (KO.J41, interim
rule, 49 FR 5312.
8-3 August, 1984
-------
9. SAMPLING, ACCEPTABLE ANAL ĄT 1CAL TECHNIQUES AND fflJALITY ASSURAHCE
9.1 Air (CONTACT: Larry Perdue, FTS 629-2665)
Since benzene is not yet a regulated criteria pollutant, ORD has not
promulgated a criteria analysis methodology; but a monitoring approach
has been developed. The methodology is reported in EPA-600/4-80-027 -
May 1980 (Ambient Air Monitoring of Benzene). The method involves
adsorption of benzene from ambient air onto a Tenax polymer resin. The
benzene is then desorbed by heating the resin, cryogenically trapped on
silanized glass beads in liquid nitrogen, and analyzed by gas
chromatography using a flame lonization detector (FID).
The method described is applicable for measuring benzene in ambient air
using a 24-hour sampling period.
The limit of detection is approximately 0.1 iig/m . The relative
standard deviation of replicate gas chromatographic analyses of
standard gas mixtures is within 26%. The accuracy of the method is
approximately 44%. Both internal and external quality control
procedures are available.
It should be noted that monitoring data were collected before full
development of satisfactory sampling and analytical techniques so that
certain technical problems were in evidence. The major problems
encountered were with the use of Tenax adsorbent. These problems
included: (1) large residual benzene concentration in the Tenax
compared to that of a field sample, (2) this concentration was highly
variable, and (3) it could not be completely removed from the Tenax.
Materials other than Tenax need to be considered. A solvent desorption
technique would be preferable to thermal desorption.
9.2 Water (CONTACT: Jim Lichtenberg, FTS 684-7326}
Benzene is a contaminant regulated by the Clean Water Act 304(h) and
therefore a water and wastewater related method has been promulgated by
EPA (Federal Register, December 3, 1979, p. 69474). The revised
analysis method is entitled "The Analysis of Aromatic Chemical
Indicators of Industrial Contamination in Water by the Purge and Trap
Method; Method 503.1" published by U.S. EPA, EMSL-Cincinnati, May 1980.
The method is applicable to the determination of various purgeable
aromatics, including benzene, found in finished drinking water, raw
source water, or drinking water in any stage of treatment.
The method incorporates an extraction/concentration technique which
enhances the quantities of certain compounds by a factor of greater
than 1,000 over direct gc injection. The method involves bubbling an
inert gas through a 5 ml water sample contained in a specially designed
purging chamber. The aromatics are transferred to the vapor phase
which is then swept through a short solver.*- tube on which the aromatics
are trapped. After the purge is completed, the trap is heated and
backflushed with gas to desorb the aromatics into a gas chromatographic
system. Temperature programming is used to separate aromatics before
detection with a photoionization detector.
9-1 August, 1984
-------
This method is recommended for use only by experienced residue analysts
or under close supervision of such qualified persons.
The lower limit of detection is 0.02 ug/1. Analytical quality control
procedures require organic quality control samples to be within 20% of
the true value and the precision of replicate analyses should have an
average relative standard deviation of 6%.
9.3 Solid Waste (CONTACT: D. Friedman, FTS 755-9187)
Benzene in waste solids may be determined as described by Method 8020
in Test Methods for Evaluating Solid Waste, Physical/Chemical Methqds
(Office of Solid Waste and Emergency Response, July 1982, SW-846,
Second Edition). Method 8020 is used to determine the concentration of
various aromatic volatile organic compounds in groundwater, liquid, and
solid matrices.
Specifically, Method 8020 provides cleanup and GC conditions for the
detection of aromatic volatile organic compounds including benzene.
Waste samples can be analyzed using direct injection, the headspace
method (Method 5020) or the purge-and-trap method (Method 5030).
Groundwater samples should be determined using Method 5030. A temper-
ature program is used in the gas chromatograph to separate the organic
compounds. Detection is achieved by a photo-ionization detector
(PID). The detection limit of this method for benzene using purge-and-
trap procedure is 0.2 Jig/1. The average recovery is 91 percent for
benzene and the standard deviation is 10.0 percent.
9.4 Other Samples (CONTACT: Jim Lichtenberg, FTS 684-7308)
Sediments - -"Interim Methods for the Sampling and Analysis of Priority
Pollutants in Sediments and Fish Tissue" (EPA; EMSL-Cin.; August 1977,
revised October 1980) is a collection of draft methods for the analyses
of fish and sediment samples for the priority pollutants. Prepared
originally as guidance to the Regional Laboratories, two methods are
applicable to benzene analysis:
(1) determination of purgeable organics in sediments - the procedure
applies a modified purge/trap technique in a direct analysis of an
undiluted sediment sample. The method relies on the use of a mass
spectrometer detection system, although other selective detectors
may be used. Under ideal conditions, the minimum detectable limit
has been determined to be 0.5 ppb.
(2) analysis of fish for volatile organics by purge and trap analysis
- a purge and trap analysis using GC/MS intended for both
qualitative and semi-quantitative determinations.
9.5 Quality Assurance (CONTACT: John Winter, FTS 684-7325)
ORD has a full range of Quality Assurance support available which
includes the following items:
9-2 August, 1984
-------
o Unknown performance evaluation samples
o Known calibration check samples
o A "dgBenzene" surrogate compound
These are available to the Regions through the Quality Assurance
Branch of EMSL-Cincinnati (see Contact).
9-3 August, 1984
-------
REFERENCES
The ma]or references used in the preparation of this document are listed
below. EPA references are listed by the EPA office of origin and the year of
publication. For further information refer to the contacts gien throughout
this document or contact the relevant EPA offices given at the end of this
section.
(Cheremisinoff, 1979)
{DOT, 1980)
(IARC, 1980}
(MAS, 1980)
(OAQPS, 1978)
(OPTS, 1980)
(OTS, 1975)
(OWRS, 1979}
(OWRS, 1980)
(SRI/ 1982)
Benzene, P. Cheremisinoff and A, Morresi, Dekker,
1980 Emergency Response
New York (1979).
Hazardous Materials:
Guidebook, U.S. Department of Transportation
Tl980).
Cancer Research, 4„•; 1-12; report of IARC work
group (1980).
Health Effects of Benzene:
A Review, National
Academy of Sciences, EPA-560/5-76-003 (1976).
Assessment of Human Exposures to Atmospheric
Benzene, EPA-450/3-78-031, Office of Air Quality
Planning and Standards (1978).
Level II Materials Balance for Benzene, EPA-
Draft, Contract No. 68-01-5~793, Office of
Pesticides and Toxic Substances (1980).
Benzene: Environmental Sources of Contamination,
Ambient Levels, and Fate, EPA-560/5-75-005,
Office of Toxic Substances (1975).
Wa te r— Re la .ted Envi ronme ntal Fa te of_JJ29 Priority
~~
Polutants, Vol.
Ch. 71 , EPA-440/4-79-029b,
Office of Water Regulations and Standards (1979).
Ambi en t Ha te r Qua 1 1 ty Cr i te r la for Benzene, EPA-
440/5-80-018, Office of Water Regulations and
Standards (1980) .
Chemical Economics Handbook , Manual of Current
Indicators-Supplemental Data/ SRI (1982).
R-1
July, 1984
-------
OFFICE CONTACTS
The EPA offices and divisions that are listed below may be contacted for more
information relating to the indicated sections of this document. While these
offices are, in many cases, the offices of origin for the data included in
this paper, the personal contacts given throughout this document should be
contacted first. Unless otherwise noted, the offices listed are situated in
Headquarters, Washington, D.C., and the telephone numbers given are FTS
(Federal Telecommunications System) numbers. For commercial telephone calls
to Headquarters which are not placed on FTS, area code 202 must be used.
Other commercial numbers are noted for the office contacts located outside
Washington, D.C.
HEALTH AND ENyiROlMENTAL EFFECTS (Section 2)
Office of Health and Environmental Assessment (OHEA)
Environmental Criteria and Assessment Office:
Cincinnati, OH 684-7531 (513-684-7531)
Research Triangle Park, NC 629-4173 (919-541-4173)
Carcinogen Assessment Group 382-7341
Office of Drinking Water (ODW)
Health Effects Branch 382-7571
Office of Toxic Substances (OTS)
Health and Environmental Review Division 382-4241
Environmental Research Laboratory
Duluth, MM, Region V 783-9550 (218-727-6692)
ENVIRONMENTAL RELEASES AND EXPOSURE (Sections 3 and 4)
Office of Air Quality and Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Water Regulations and Standards (OWRS)
Monitoring and Data Support Division 382-7051
Office of Toxic Substances (OTS)
Exposure Evaluation Division 382-3873
R-2 July, 1984
-------
DATA BASES (Section 5)
Office of Toxic Substances (OTS)
Information Management Division 382-3749
REGULATORY STATUS, STANDARDS, AND CRITERIA (Sections 6 and 7)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 62975504 (919r541T5504)
Office of Drinking Water (ODW)
Criteria and Standards Division 382-7575
Office of Hater Regulations and Standards (OWRS)
Criteria and Standards Division 755-0100
Effluent Guidelines Division 382-7120
Office of Solid Waste (OSW)
Permits and State Programs Division 382-4746
SPILL CLEAN-UP AND DISPOSAL (Section 8}
NOTE: For Emergencies call the National Response Center at 1-800r424-8802
(1-800-426-2675 from the Baltimore/Washington area).
Office of Emergency and Remedial Response (OERR)
Emergency Response Division 382r2;182
Hazardous Site Control 382-2443
Oil and Hazardous Materials Spills Branch
Edison, NJ; Region II 340-6635 (201-321-6635)
ANALYTICAL TECHNIQUES (Section 9)
Environmental Monitoring Systems Lab (EMSL)
Air Analysis
Research Triangle Park, NC 629-2454 (919-541-2454)
Water Analysis
Cincinnati, OH 684-7311 (513-684-7311)
R-3 July, 198.4
-------
Waste Analysis
Las Vegas, NV 545-2137 (702-798-2137)
Office of Monitoring Systems
and Quality Assurance 382-5767
GENERAL IFF COMMENTS, CORRECTIONS, OR QUESTIONS
Chemical Coordination Staff
Chemical Information
and Analysis 382-3375
R-4 July, 1984
-------
Cadmium
-------
CADMIUM
Table of Contents Page
Physical/Chemical Properties and Chemistry 1-1
Properties 1-1
Chemistry and Environmental Fate/Transport 1-1
Effects Information 2-1
Health Effects 2-1
Environmental Effects 2-3
Environmental Release 3-1
Air Releases 3-1
Water Releases 3-1
Land Releases 3-1
Exposure 4-1
Air Exposure 4-1
Water Exposure 4-1
Other Exposure 4-3
Data Bases 5-1
Chemicals in Commerce Information System (CICIS) 5-1
EPA Chemical Activities Status Report (EPACASR) 5-1
NIH/EPA Chemical Information System (CIS) 5-1
Chemical Regulations and Guidelines System (CRGS) 5-1
Chemical Substances Information Network (CSIN) 5-1
EPA Information Clearinghouse 5-2
Regulatory Status 6-1
Promulgated Regulations 6-1
Proposed Regulations 6-2
July, 1982
-------
Standards and Recommended Criteria 7-1
Air 7-1
Water 7-1
Hazardous Waste 7-1
Other 7-2
Spill or Other Incident Clean-up/Disposal 8-1
Hazards and Safety Precautions 8-1
First Aid 8-1
Emergency Action 8-1
Notification and Technical Assistance 8-2
Disposal 8-2
Sampling, Acceptable Analytical Techniques and Quality Assurance 9-1
Air 9-1
Water 9-1
Solid Wastes 9-3
Other Samples 9-3
Quality Assurance 9-3
References and Office Contacts R-l
July, 1982
-------
CADMIUM
1. PHYSICAL/CHEMICAL PROPERTIES AND CHEMISTRY
1.1 Properties
Cadmium is a relatively rare element which is produced commercially
as a byproduct of primary metal industries, principally from the
refining of zinc. Cadmium is a soft ductile metal with relatively
low melting and boiling points. Due to the superior corrosion
resistance of the metal, the largest use for cadmium is in electro-
plating. Other significant uses are in pigments, plastic stabil-
izers, alloys, and batteries. Properties and uses of various cad-
mium compounds are listed in Table 1. Although of limited commer-
cial significance, cadmium is a toxic pollutant which is widely
dispersed by the mining and production of metals and combustion of
fossil fuels (Nriagu, 1980; IARC, 1976).
1.2 Chemistry and Environmental Fate/Transport
Cadmium is a member of Group lib in the periodic table, below zinc
and above mercury. In fact, cadmium is chemically similar to zinc
and will be found wherever zinc occurs in nature. The only stable
oxidized state of cadmium is the divalent cation, Cd+2. Although
organocadmium compounds are useful synthetic intermediates, they are
unstable and rapidly decompose upon exposure to water or air.
Divalent cadmium forms complexes with various inorganic ligands in
solution, notably cyanide, ammonia, hydroxide, and chloride. Cad-
mium can also bind a variety of organic ligands, including sulfides
(OWRS, 1979; ORNL, 1973).
The relatively low volatility of the metal permits the release of
cadmium vapors during various thermal processes such as ore roasting
and smelting, and incineration of wastes or combustion of fossil
fuels. Cadmium vapors rapidly react with other gases to form
finely divided and hazardous products. In the presence of carbon
dioxide, oxygen, or water vapor, the products should be the carbon-
ate, oxide, or hydroxide salt respectively. Cadmium-containing
particles emitted settle out on the soil or water, the fallout rate
being dependent on particle size, density and wind patterns (ORNL,
1973; OAQPS, 1979a).
Compared to other heavy metals, cadmium is relatively mobile in
water and may be transported in solution as hydrated cations or as
organic and inorganic complexes. The formation of complexes with
organic matter (i.e., humic acids) facilitates sorption by sedi-
ments. In unpolluted waters sorption onto clay minerals, co-precip-
itation with hydrous metal oxides and substitution of Cd+2 for Ca+-
in carbonate minerals are also important factors. Although toxic,
cadmium is strongly accumulated by aquatic organisms, especially in
soft water. Biomethylation of cadmium has not been observed.
Cadmium is less mobile in alkaline than in acidic waters (OWRS,
1979).
1-1 July, 1982
-------
Because a major route of human cadmium exposure is through food,
understanding the movement of cadmium through the food chains is
important. Cadmium is distributed to soil through the addition of
phosphate fertilizers or municipal sewage sludge containing cadmium
to cropland and by deposition from air. Cadmium tends to concen-
trate in soil/sediment sinks due to the insolubility of carbonate,
oxide, sulfide, and phosphate salts; the affinity of cadmium for
organic matter also impedes transport. However, leaching and runoff
of cadmium can occur, especially from sandy, acidic soil. In addi-
tion, cadmium concentrates in various food crops (potatoes, root
crops, and leafy vegatables), especially when the soil is acidic.
The availability of cadmium to plants is reduced in the presence of
phosphates (OWRS, 1980; MERL, 1981).
1-2 July, 1982
-------
TABLE 1: PROPERTIES OF CADMIUM COMPOUNDS3
Chemical Name
and Formula
Cadmium
Cd
Cadmium
chloride
CdCl2
Cadmium
nitrate
Cd(N03)2
Cadmium
oxide
CdO
Cadmium
sulflde
CdS
CAS Number Mp
and Synonyms (°C)
7440-43-9 321
10108-64-2 568
Cadmium
dichlorlde
10325-94-7 350
Nitric acid,
cadmium (2+)
salt (1:2)
1306-19-0 900
(dec)
1306-23-6
Aurora yellow,
Capsebon
Up Water Solubility
(°C) (per liter)
765 insol.
1.4 kg
(20°C)
1.1 kg
(O'C)
1560 insol.
(sublimes)
980 1.3 mg
(sublimes) (18°C)
Other Properties
and Uses
d25 8.65; oxidized
slowly in air to CdO.
Used In electroplat-
ing, alloys, solder,
batteries.
Hygroscopic; used
in photography and
phosphors.
Tetrahydrate is major
commercial form.
Used in manufacture
of nickel-cadmium
batteries.
Used in electroplating
and in electrodes for
storage batteries.
Used in heat stable
pigments, and in
phosphors. A major
mineral form of
cadmium (greenockite).
I
U)
t_
c
VO
oo
NJ
a From (IARC, 1976).
-------
2. EFFECTS INFORMATION
2.1 Health Effects (CONTACTS: Jerry Stara, FTS 684-7531; Les Grant, FTS
629-4173; Bob McGaughy, FTS 755-7315; Ed Ohanian, 382-7586)
2.1.1 Acute Toxicity
Symptoms of acute poisoning by ingesting as little as 15-30 mg of
cadmium in food or drink appear within 15 to 30 minutes and include
persistent vomiting, increased salivation, choking sensation,
abdominal pain, and diarrhea. Acute poisoning symptoms by inhalation
of cadmium oxide fumes appear within 4-6 hours after exposure and
include cough, shortness of breath and tightness of the chest.
Pulmonary edema may ensue within 24 hours, often to be followed by
bronchopneumonia. Fifteen to 20 percent of cases result in
fatality. Later effects from acute poisoning include pulmonary
fibrosis, permanently impaired lung function and disturbed liver
function. It is calculated that inhalation of 2,900 mg/m^ for one
minute is fatal. From this figure it may be estimated that
inhalation of 5 mg/m3 over an 8-hour period would result in death
(OWRS, 1980; Friberg, 1974).
2.1.2 Chronic Toxicity
Two cardinal pathological lesions associated with chronic effects of
cadmium are pulmonary emphysema and kidney damage. Cadmium-induced
emphysema is apparently related only to the inhalation route of
exposure. Regardless of exposure route, cadmium is a cumulative
poison and is primarily stored in the liver and kidney. Pathological
changes occur in the kidney (renal cortex) when cadmium
concentrations reach 200-300 mg/kg net weight. Renal tubular damage
is characterized by the urinary excretion of protein
(Bjmicroglobulin), glucose, phosphate, amino acids and calcium. The
renal dysfunction rarely progresses to kidney failure. The most
severe occurrence of such effects and their most extreme consequences
can be found in itai-itai disease patients. On occasion, the renal
lesion may be severe enough to produce osteomalacia and multiple
fractures due to a negative calcium balance caused by excessive
calcium excretion. Chronic cadmium toxic effects seem to be more
prevalent in individuals suffering from multiple dietary deficiencies
of protein, vitamin C or vitamin D. Since renal, bone, and body
fluid cadmium levels are apparently higher in some hypertension
patients, cadmium has been suggested as a factor in the etiology of
essential hypertension. However, epidemiologic studies have failed
to support this concept (OWRS, 1980; Frieberg, 1974).
Carcinogenicity, Mutagenicity, and Teratogenicity - While cadmium has
been associated with the etiology of prostate cancer and, to a lesser
extent, kidney and respiratory tract cancer (IARC, 1976), the
available epidemiological evidence is not conclusive. The human
evidence for the carcinogenicity of cadmium is conjectural, based on
small-scale studies, and confounded by exposure to other chemicals,
e.g., arsenic (OWRS, 1980; OHEA, 1983).
2-1 October, 1983
-------
Cadmium and various cadmium salts have produced injection site
sarcomas in rats and interstitial cell testicular tumors in mice and
rats after subcutaneous injection. Specifically, injection site
sarcomas were produced by cadmium powder, cadmium sulfide, cadmium
oxide, cadmium sulfate, and cadmium chloride, and interstitial cell
tumors were produced by cadmium chloride, cadmium sulfate, and
ferritin containing cadmium. However, three drinking water, two
gavage, and two dietary studies using cadmium acetate, cadmium
sulfate, or cadmium chloride have shown no excessive risk of cadmium
carcinogenicity in rats and mice. A lifetime rat inhalation study
has been completed which shows a dose-related induction of lung
carcinomas by cadmium chloride aerosol. Estimates of carcinogenic
risk from epidemiological studies of worker exposure via inhalation
are about 100 times lower than the risk calculated from the animal
study. No carcinogenic response has been observed in rats with
ingested cadmium, thus the potency via the oral route is at least 200
times less than via inhalation in rats (OHEA, 1983).
There is no doubt that cadmium is a teratogen in several rodent
species when given in large parenteral doses. Doses of this
magnitude (4-12 mg/kg) would produce severe, if not fatal, toxic
symptoms in humans. Furthermore, in humans only small amounts of
cadmium cross the placental barrier. Experiments suggest that
congenital abnormalities observed in exposed mice could be due to a
cadmium-induced zinc deficiency (OWRS, 1980).
A definitive conclusion on the mutagenicity of cadmium is difficult
to reach because of conflicting results and inadequate test
protocols. Gene mutation studies in Salmonella, E.coli, yeast, and
Drosophila are conflicting or inconclusive. However, gene mutation
studies in mammalian cell cultures, rec-assays (DNA repair test) in
bacteria, chromosomal nondisjunction studies in intact mammals, and
other indirect evidence suggest that cadmium is weakly mutagenic
{OHEA, 1983).
2.2 Environmental Effects (CONTACTS: John Eaton FTS 783-9557,
John Gentile, FTS 838-4843)
2.2.1 Aquatic Effects (OWRS, 1980)
The forms of cadmium which are commonly found in bodies of water that
are most toxic to aquatic life (or can be converted to the more toxic
forms under natural conditions) are the free cadmium ion, the
hydroxide, carbonate, and sulfate. Factors which affect cadmium
toxicity to aquatic life include: the chemical form of cadmium,
water hardness (toxicity decreases as hardness increases), water
temperature, oxygen content, life stage of exposed species, salinity
and water pH.
Freshwater - The results of acute toxicity tests on cadmium with 29
freshwater species range from 1 to 73,500 ug/1 with both fish and
invertebrates distributed throughout the range. The antagonistic
effect of hardness on acute toxicity has been demonstrated with seven
species. The seven available acute-chronic ratios are all between 66
and 431.
2-2 October, 1983
-------
Freshwater aquatic plants are affected by cadmium at concentrations
ranging from 2 to 7,400 ug/1. These values are in the same range as
the acute toxicity values for fish and invertebrate species, and are
considerably above the chronic values. Bioconcentration factors for
cadmium reach 3,000 for some invertebrates and may be as high as
12,000 for some fish species.
Saltwater - The saltwater acute values for cadmium in five species of
fishes ranged from 577 ug/1 for larval Atlantic silversides to
114,000 ug/1 for juvenile mummichog. Acute values for 26 species of
invertebrates ranged from 15.5 ug/1 for the mysid shrimp to 46,600
ug/1 for the fiddler crab. The acute toxicity of cadmium seems to
increase as salinity decreases and as temperature increases, although
the magnitudes of the effects seem to vary with species. Two life
cycle tests on Mysidopsis bahia under different test conditions
resulted in similar chronic values of 5.5 and 8.0 ug/1, but the
acute-chronic ratios were 2.8 and 14, respectively. These acute
values appear to reflect the effects of salinity and temperature,
whereas the chronic values apparently do not. Plant studies with
microalgae report growth inhibition at 160 ug/1.
Tissue residues were reported for 1 species of algae, 10 species of
invertebrates, and 1 species of fish. Bioconcentration factors for
fish and crustaceans were generally less than 400, whereas those for
bivalve mollusks were above 2,500 in long exposures, with no
indication that steady-state was reached. Cadmium mortality is
cumulative for exposure periods beyond four days. Chronic cadmium
exposure resulted in significant effects on the growth of bay
scallops at 78 ug/1 and on reproduction of a copepod at 44 ug/1.
Water Quality Criteria - At water hardness of 50, 100 and 200 ug/1 as
CaCO3, the criteria to protect freshwater aquatic life are 0.012,
0.025 and 0.051 ug/1 respectively, and the concentration of total
recoverable cadmium should not exceed 1.5, 3.0 and 6.3 ug/1,
respectively, at any time. For total recoverable cadmium, the
criterion to protect saltwater aquatic life is 4.5 ug/1 as a 24-hour
average, and the concentration should not exceed 59 ug/1 at any time.
2.2.2 Other Effects
Because food is one of the main sources of cadmium intake in non-
occupationally exposed individuals, knowledge of its concentration
levels in the soil is extremely important. The mobility and persis-
tence of cadmium in the soil depends on the physical/chemical proper-
ties of the soil plus the cadmium speciation. However, the majority
of applied cadmium is thought to remain in the soil at the zone of
incorporation under normal conditions in agriculture systems. There
is insufficient evidence documenting the half-life of cadmium in the
soil. Cadmium uptake by plants depends upon the plant species. In
particular, potatoes, root crops, leafy vegetables, rice and wheat
tend to take up cadmium in. considerable quantities in polluted
areas. Soil pH is a critical factor determining cadmium uptake in
plants: the lower the pH (more acidic), the higher the cadmium
concentration (OWRS, 1980; Nriagu, 1980).
2-3 October, 1983
-------
3. ENVIRONMENTAL RELEASE
Cadmium is a naturally occurring element in the earth's crust and
ranks in abundance between silver and mercury. It is produced as a
by-product in the recovery of primary zinc and from residuals of
primary lead and copper production. In recent years, U.S. production
has been decreasing so that inports now exceed domestic production.
Cadmium is also present as an impurity in coal, petroleum, phosphate
rock, and limestone. Cadmium enters the environment primarily from
combustion of coal and fuel oil, mining and metals production, direct
land application of POTW sludge, effluent from POTWs, incineration of
PUTW sludge, production and disposal of cadmium-containing products,
phosphate production, and the use of phosphate fertilizers.
Its domestic uses were as follows for 1979:*
% of
Uses of Cadmium kkg/yr Total Uses
Electroplating 2510 51
Batteries 1080 22
Paints and Pigments 640 13
Plastics 540 11
Other 155 3
TOTAL 4925
Table 2 summarizes attempts to estimate cadmium releases to the
environment. While numerous mass balances have been completed for
cadmium, the estimates for various sources vary widely. The release
data are only crude estimates and have not been verified by sampling
or analysis.
3.1 Mr Releases (CONTACT: Rayburn Morrison, FTS 629-5519)
Prioritization of industrial sources for cadmium emissions is cur-
rently being studied by EPA in order to determine whether or how cad-
mium will be regulated as an air pollutant. Cadmium releases are
greatest from fossil fuel combustion in terms of total tonnages
released; the impact of these sources, however, is generally small
because fossil fuel cadmium emissions are distributed over thousands
of widely scattered sources, the largest of these generally having
taller stacks. (See Table 2 for itemized releases.)
Significant Sources
• Primary zinc smelting (SIC 3333)
• Primary cadmium smelting (SIC 3339)
* Mineral Facts and Problems, U.S. Department of Interior, Bureau of Mines,
Bulletin 671 (1980). Numbers refer to a 100% cadmium basis.
3-1 July, 1982
-------
• Primary copper smelting (SIC 3331)
• Primary lead smelting (SIC 3332)
• Sludge incineration
Other Sources
• Fuel oil combustion
• Coal combustion
• Municipal refuse incineration (SIC 4953)
• Iron and steel manufacturing (SIC 3312)
• Secondary lead smelting (SIC 3340)
3.2 Water Releases (CONTACT: Michael Slimak, FTS 426-2503)
Significant Sources
• Electroplating operations
• POTW pass-through water
3.3 Land Releases
Significant Sources
• Phosphate fertilizer application
• POTW sludge application
3-2 July, 1982
-------
TABLE 2: CADMIUM MATERIALS BALANCE (kkg/yr)
MUNICIPAL
Zn/Pb Mining and Beneficiation
Zn/Cd Smelting
Electroplating e
Batteries Ł
Pigment
Plastic
Pesticide
Other Cd Products
Iron and Steel
Primary Non-Ferrous/Non-Zn
Secondary Non-Ferrous
Zn Products h
Printing/Photography
Laundry & Car Wash
Coal Combustion
Coal Mining
Oil Combustion
Gasoline Combustion
Lubricating Oil
Tire Wear
Phosphate Detergent
Phosphate Fertilizer
Urban Runoff a
Potable Water Supply t
Combustable Refuse k
POTW Effluent
POTW Sludge n
Municipal Kefuse
Totals
N = No Data
- = Negligible
AIR
0 (V)
7(G)b
-
1 (V)
10 (V)
3 (V)
-
N
H (G)
218 (G)
2 (V)
-
-
-
202 (G)
-
363 (G)
13 (E)
1 (V)
5 (V,E)
-
-
-
-
-
-
14 (G)
38 (G)
890
WATER
8 (W)a
5 (V)c
163 (W)
1 (V)q
1 (V)
-
-
N
8 (W)
1 (V)
- (v)
N
-
-
152 (V)
45 (W)j
-
-
N
-
-
-
115
-
-
308 m
89
—
893 p
LANDFILL LANDSPREAD
250 (V)
- (v)
42 (W)
9 (V)
17 (V)
-
9 (A,S)
N N
400 (Y)
-
1 (W)
N
N
-
429 (V)
N
-
-
N
-
-
400 (W)
-
-
-
-
239 143
3434 d
4821 552
POTW
-
310 (W)
2 (V)
2 (V)
5 (V)
-
N
-
-
-
g
<80 (W)i
10 (W)
-
-
-
-
-
-
10 (V,W)
-
11
41
-
-
-
—
475/800 r
REFUSE
-
1225 d
827 d
519 d
456 d
-
118 d
-
-
-
N
N
-
-
-
-
-
N
N
-
-
-
-
420 k
-
-
—
3565
U)
I
U)
c_
c
CO
to
-------
TABLE 2: CADMIUM MATERIALS BALANCE (kkg/yr) (cont.)
Footnotes:
a. Alternative estimate: 114+90 kkg/yr active + inactive mines (Y)
b. Alternative estimates: 127 to air (V); 0.5 to water (W)
c. Alternative estimate: 0.5 (W)
d. By difference = Production less other identified releases
e. Cycled to iron & steel or other industry = 216 (Y)
f. Recycled = 89 (Y & V)
g. Water pipe corrosion accounted for underwater supply
h. Total Cd in Zn metal - 173 (Y), disposition unknown
i. Alternative estimate = 11 (V)
j. Alternative estimate = 0 (W)
k. Excluding Cd pigments and plastics;
100 million kkg/yr combustible refuse X 14 ppm Cd (Campbell, 1976), less
pigments and stabilizers contribution.
m. Influent 800 - sludge 492
n. To air - 21% of sludge, 20% escapes emission controls
To water (ocean dump) =» 18% of sludge
Landfill = 32% + captured emissions
Landspread = 29% (from EPA, OSW, 1979)
Total sludge quantity from Cook (1979)
p. Excluding unknown quantity in rural runoff
q. Scanty EGD data suggests a higher value
r. Sum of known contributions, independently estimated POTW total influent
(derived from Sverdrup and Parcel (1977) data)
s. Derived from Sullivan (1977): 6 ppb X 21 trillion liters/yr.
t. Concentration from Battalia (1977)
Sources;
(A) Arthur D. Little (1979)
(S) SRI, Inc. (1979)
(V) Versar (1979a)
(W) Versar (1979b)
(Y) Yost (1978)
(E) EEA (1978)
(G) GCA (1981)
Note; This table is a summary of the numerous cadmium mass balances
assembled by OWRS, except for the air emissions which are more recent
estimates from OAQPS (OAQPS, 1981).
3-4 July, 1982
-------
4. EXPOSURE ROUTES
The major route of cadmium exposure in nonsmokers occurs through the
food chain by soil contamination. The primary source of this con-
tamination can be attributed to natural cadmium in the soil, phos-
phate fertilizers, cadmium contaminated sludge application, and air
releases. Irrigation water, when taken from contaminated sources
may also be a source of topsoil contamination. Although the contam-
ination appears to be moderate in this country, the ability to
create hotspots which result in substantial human risk has been
observed in Japan where several routes combined to cause adverse
human health effects (OWRS, 1980).
EPA has estimated that retention of 10 ug of cadmium in the body
each day for 50 years would result in the critical concentration of
200 ppm in the kidney cortex. The 10 ug per day figure assumes a 38
year half-time of cadmium in the human body. For evaluating the
health significance of cadmium exposures, EPA used 10 ug per day as
a critical daily retention level. The total combined exposure from
average levels in air, drinking water, and food result in a total
daily retention of approximately 1 to 2 ug. Cigarette smoking can
add about 1.5 ug/pack to this total. Thus, the general population
is not expected to approach the critical retention level of 10
ug/day (ECAO, 1981). The various exposure routes are discussed in
more detail below.
4.1 Air Exposure Routes (CONTACT: Rayburn Morrison, FTS 629-5519)
Analysis indicates that retention levels resulting from present and
predicted future concentrations of cadmium in the ambient air are
well below a kidney dysfunction level. Compared with the 10 ug
critical level, average urban air results in a daily cadmium reten-
tion of less than 0.1 ug; the highest measured concentration (at a
monitoring site near a currently out-of-compliance smelter) results
in a daily retention of 2.4 ug; and the highest concentration pre-
dicted around any type of in-compliance cadmium source equates to a
daily retention of less than 0.6 ug (OAQPS, 1981). Estimates of
maximum anticipated annual average ambient cadmium concentrations
around the primary sources indicate that very low concentrations
should result if the sources, both existing and new, comply with
current ambient air standards for particulate matter. These annual
average concentrations were estimated to range from a high of about
0.13 ug/m3 for sewage sludge incinerators to as little as 0.002
ug/m3 for municipal incinerators. These levels are well below the
ambient concentration of 2 ug/m3 which equates to a critical daily
retention level of 10 ug (OAQPS, 1981).
Currently, regulation in State Implementation Plans and Federal
regulations for new sources control the emissions of particulate
matter from virtually all cadmium source categories, including sew-
age sludge incinerators, primary lead smelters, primary copper
smelters, and municipal incinerators. In addition, state require-
ments for controlling emissions of lead are expected to be developed
for some of the sources, and these requirements are expected to
result in additional control of cadmium emissions.
4-1 July, 1982
-------
4.2 Water Exposure
Drinking water contributes little to the average daily intake of
cadmium. Community water supplies in the United States average
about 1.3 ug/1. Sea waters have an average cadmium level of 0.1-
0.15 ug/1. This is less than freshwater entering the sea and below
the levels expected from solubility factors. Cadmium may be effec-
tively removed by co-precipitation with or adsorption on clays,
hydrous manganese oxide or phosphorites. Assuming a retention
factor of about 6% for Ingested cadmium, consumption of 2 liters of
water containing 1.3 ug/1 would result in retention of less than 0.2
ug per day (OWRS, 1980).
4.3 Other Exposure
Food
The major nonoccupational routes of human cadmium exposure are
through food and tobacco smoke. Recent studies indicate that the
average daily intake of cadmium is about 20 ug for teenage males.
Other studies indicate that the daily intake of cadmium via food for
individuals in the United States is comparable to that in other
parts of the world. Daily retention of cadmium from an average
intake of 20 ug/day would be about 1 ug/day, assuming a 6% retention
factor (OWRS, 1980).
Balanced diets generally contain about 0.05 mg/kg of cadmium.
Aquatic food species, (fish, crabs, oysters, and shrimps) bioconcen-
trate cadmium, as do visceral meats (liver, kidney and pancreas).
Older animals generally have higher cadmium levels due to the
cumulative nature of cadmium.
Tobacco
Tobacco in all forms contains appreciable amounts of cadmium.
Smoking contributes to relatively high total body levels since the
absorption of cadmium from the lung Is greater than that from the
gastrointestinal tract. Smoking 20 cigarettes per day results in
the inhalation of about 3 ug of cadmium per day. Assuming a
retention factor of 50%, smoking one pack of cigarettes a day
results in the retention of about 1.5 ug of cadmium per day (OWRS,
1980; ECAO, 1981).
4-2 July, 1982
-------
5. DATA BASES
5.1 Chemicals in Commerce Information System (CICIS)
The Inventory was compiled under the authority of Section 8 of TSCA
which requires manufacturers to report to EPA the chemicals imported
and manufactured during calendar year 1977. The Inventory lists the
Chemical Abstract Service (CAS) preferred name for the chemicals,
their respective CAS number {often used for identification purposes),
production site, company name, and volume(s) of production and
import. There is also a Confidential Inventory in which many of these
characteristics are claimed confidential by the manufacturer. In
these instances, the confidential information will not be available in
the public inventory. CICIS can now be accessed through the NIH/EPA
Chemical Information System (CIS - see 5.3). For further information,
contact Gerri Nowack at PTS 382-3568 or Robin Heisler at FTS 382-3557.
5.2 EPA Chemical Activities Status Report (EPACASR)
EPACASR is an on-line system containing information on EPA's interest
in chemicals. This system includes data on the Agency's regulations
research, and assessments directed toward specific chemicals. EPACASR
is published annually and the data base is updated as information is
received. A searchable subset itemizes NTP/NCI studies and results,
as well as chemicals discussed in the I ARC monograph series. (Other
sources are added as appropriate.) Entries identify the statutory
authority, the nature of the activity, its status, the reason for
and/or purposes of the effort, and a source of additional
information. Searches may be made by CAS Number or coded text.
(EPACASR is scheduled to be added to CIS in early 1984.) For further
information, contact Eleanor Merrick at FTS 332-3415.
5.3 NIH/EPA Chemical Information System (CIS)
This is a collection of various scientific data bases available
through an interactive computer program. The linking system between
these data files is the Structure and Nomenclature Search System
(SANSS). CIS can also provide a list of non-CIS sources of
information on a chemical of interest. However, these files have to
be accessed individually by either separate on-line systems or in
hard-copy. For further information, contact Dr. Steve Heller at FTS
382-2424.
5.4 Chemical Regulations and Guidelines System (CRGS)
CRGS is an on-line data base which is being developed to provide
information on chemical regulatory material found in statutes,
regulations, and guidelines at the Federal, State, and international
levels. Currently, only the first phase of CRGS, which encompasses
only source material at the Federal level, is operational. Nation-
wide access to CRGS is available through Dialog. For further
information, contact Doug Sellers at FTS 382-2320.
5-1 October, 1983
-------
5.5 Chemical Substances Information Network (CSIN}
The Chemical Substances Information Network (CSIN) is a
sophisticated switching network based on heterogeneous distributed
data base management and networking concepts. CSIN offers efficient
access to on-line information resources containing data and
information relevant to chemical substances, as well as information
covering other scientific disciplines and subject matters. The
purposes of CSIN are two-fold: first to meet the growing chemical
data and information requirements of industry, academe, government
(Federal and State), public interest groups, and others; and secondly
to reduce the burden on the private and public sector communities when
responding to complex Federal legislation oriented to chemical
substances.
CSIN is not another data base. CSIN links many independent and
autonomous data and bibliographic computer systems oriented to
chemical substances, establishing a "library of systems". Users may
converse with any or all systems interfaced by CSIN without prior
knowledge of or training on these independent systems, regardless of
the hardware, software, data, formats, or protocols of these
information resources.
Information accessible through CSIN provides data on chemical
nomenclature, composition, structure, properties, toxicity, production
uses, health and environmental effects, regulations, disposal, and
other aspects of the life cycle of materials as they move through
society. Currently, seven independent information resources are
accessible through CSIN. They are: National Library of Medicine
(NLM), Chemical Information System (CIS}, CAS-On-Line, SDC's ORBIT,
Lockheeds's DIALOG, Bibliographic Retrieval Service (BRS), and the US
Coast Guard's Hazard Assessment Chemical System (HACS). For further
information contact Dr. Sid Siegel at 202-395-7285.
5.6 EPA Information Clearinghouse
The EPA Information Clearinghouse is a bibliographic data base
composed of over 500 individual data bases and models which contain
monitoring information and statistics on a variety of chemicals. The
individual data bases are maintained for offices within EPA. The
clearinghouse listed 1 33 citations for cadmium. For further
information, contact Irvin Weiss at FTS 382-5918.
5-2 October, 1983
-------
6. REGULATORY STATUS (Current as of 9/83)
6.1 Promulgated Regulations
6.1.1 EPA Programs
Clean Water Act (CWA)
o Section 311 - Cadmium acetate, cadmium bromide and cadmium chloride
are designated as hazardous substances (40CFR116.4) and are subject
to reporting requirements (40CFR117.3).
o Sections 301, 304, 306/ and 307 - Cadmium and its compounds are
listedasprioritypollutants{toxic pollutants, 40CPR401.15).
Effluent limitations and/or pretreatment standards for cadmium have
been issued for the following industries:
Electroplating and 40CFR413,430
metal finishing
Inorganic chemicals 40CFR415
(19 subcategories)
Nonferrous metals 40CFR421
(copper; lead; zinc)
Ore mining and dressing 40CFR440
(base and precious metals;
ferroalloys)
Porcelain enameling 40CFR466
(steel; iron;
aluminum; copper)
Electrical and electronic 40CFR469
components
o Section 403 - Ocean dumping of materials containing cadmium (except
as a "trace" contaminant) is restricted (40CFR227.6 [a][3]).
o Section 402 and 404 - Discharged toxic pollutants, such as cadmium,
are controlled by permits under the National Pollutant Discharge
Elimination System (NPDES). The Army Corps of Engineers issues
permits for discharge of dredged or fill materials (40CFR122 to
125) .
Safe Drinking Water Act (SDWA)
o Section 1412 - A maximum contaminant level (MCL) of 0.01 mg/1 for
cadmium is in effect for community drinking water (40CFR141.11[b]).
o Sections 1421 and 121 - An underground injection control (UIC)
program protects underground sources of drinking water (40CFR146).
6-1 October, 1983
-------
Requirements and criteria used by states incorporate hazardous
wastes as defined by RCRA (40CFR261), including cadmium and its
compounds. Permit procedures are given in consolidated permit
regulations (40CFR122 to 124).
Resource Conservation and Recovery Act (RCRA)
o Sections 1008
-------
FDA - Federal Food, Drug and Cosmetic Act
o Quality standards for bottled water include a maximum cadmium
concentration of 0.01 mg/1 <21CFR103.35[dJ[1]}.
o Cadmium is a regulated impurity in zinc methionine sulfate
(21CFR172.399).
6.2 Proposed Regulations
6.2.1 EPA Programs
CWA
o Effluent guidelines concerning cadmium have been proposed for the
following industry point sources:
Inorganic chemicals 45FR49450
Porcelain enameling 46FR8S60
Nonferrous metals 48FR7032
(13 subcategories)
Pesticide Chemicals 47FR53394
Pharmaceuticals 47FR53584
Battery manufacturing 47FR51052
Comprehensive Environmental Response, Compensation/ and Liability Act
(CERCLA or Superfund)
o CERCLA provides for the liability, compensation, cleanup, and
emergency response for the release of hazardous substances into the
environment. This Act also deals with cleanup of hazardous waste
disposal sites (42USC9601; PL-96-510). EPA is developing
regulations concerning the designation of hazardous substances, the
development of reportable quantities (RQ), claims procedures, and
the confidentiality of business records (46FR54032).
o Revisions to the National Contingency Plan (NCP) as required by
CERCLA have been issued in a proposed rule (47FR10972). Adjustments
to the statutory reportable quantities have been proposed; however,
until an Agency assessment of the carcinogenicity and other effects
is complete, a statutory RQ of one pound is applicable except for
those cadmium compounds listed previously under Section 311 of the
CWA (48FR23552).
6-3 October, 1983
-------
7.
7.1
STANDARDS AND RECOMMENDED CRITERIA*
7.2
7.3
7.4
Air
Current OSHA occupational standards
(29CFR1910.1000):
Cadmium fume
Cadmium dust
100 ug/m3 (8-hr. TWA)
300 ug/m3 (ceiling)
200 ug/m3 (8-hr. TWA)
600 ug/m3 (ceiling)
• NIOSH recommendation for occupational 40 ug/m3 (8-hr. TWA)
cadmium exposure limit.
200 ug/m3 (ceiling)
Water
Hazardous spill rules specify the same reportable quantity for
several cadmium compounds (40CFR117.3):
Cadmium acetate, cadmium
bromide, cadmium chloride
Effluent limitations for various
industries:
• Maximum concentration level of
total cadmium in drinking water
(40CFR141.11[b]).
• Water Quality Criteria (45FR79318)
Human Health
Freshwater aquatic life
Saltwater aquatic life
Hazardous Waste
• Waste is hazardous if an extract
exceeds the maximum EP toxicity
level (40CFR261.24).
Other Media
• FDA maximum for the level of
cadmium in bottled water
(21CFR103.35).
100 Ibs.
See Section 6.1.1 of this
document for CFR cita-
tions.
10 ug/1
10 ug/1
Varies with hardness
4.5 ug/1 (24 hr. avg.)
59 ug/1 (max.)
1.0 mg/1
10 ug/1
*See Appendix A for a discussion of the derivation, uses, and limitations of
these criteria and standards.
7-1
July, 1982
-------
8. SPILL OR OTHER INCIDENT CLEAN-UP/DISPOSAL
(CONTACT: National Response Center, 800-424-8802 in Washington area
426-2675)
8.1 Hazards and Safety Precautions
Cadmium is a toxic material which may be fatal when inhaled or
ingested. Fire will produce toxic combustion products. Runoff from
fire control or dilution water may cause pollution. Some of these
materials may burn but do not ignite readily.
Store in tightly closed containers in well-ventilated areas.
Cadmium nitrate should be kept away from easily oxidized substances,
sparks, flames, and highly heated surfaces.
8.2 First Aid
Move victim to fresh air; call emergency medical care. In case of
contact with material, immediately flush skin or eyes with running
water for 15 minutes.
8.3 Emergency Action^
Spills
Avoid contact and inhalation of the spilled cargo. Stay upwind;
notify local fire, air, and water authorities of the accident. Keep
unnecessary people away. Use full protective clothing Including
NIOSH-approved rubber gloves and boots, safety goggles or face mask,
hooded suit, and either a respirator whose canister is specifically
approved for this material, or a self-contained breathing apparatus.
Care must be exercised to decontaminate fully or dispose of all
equipment after use.
OHM-TADS recommends the following action: dam the stream to reduce
the flow and to retard dissipation by water movement. Dredging or
bottom vacuum may be effective. Information on a specific cadmium
compound can be found in the OHM-TADS data base of the Envirex
Manual EPA 600/2-77-227.
Fire
Fire can be extinguished with water in flooding quantities or as a
spray, foam, dry chemical, or carbon dioxide. If water or foam is
used, contain flow to prevent spread of pollution, keep from drains
and sewers. Remove container from fire area if you can do it without
risk. Cool containers that are exposed to flames with water until
well after the fire is out. For massive fire in cargo area, use
unmanned hose holder or monitor nozzles. If this is impossible,
withdraw from area and let fire burn.
8.4 Notification
Section 103(a) and (b) of the Comprehensive Environmental Response,
Compensation, and Liability Act of 1980 requires persons who release
8-1 July, 1982
-------
hazardous substances into the environment in reportable quantities
determined pursuant to Section 102 of the Act to notify the National
Response Center (NRG): 800-424-8802 (Washington, D.C. 426-2675).
The following cadmium compounds are designated as hazardous under
the CWA Section 311; all have reportable quantities of 100 Ib. :
cadmium, cadmium acetate, cadmium bromide, and cadmium chloride.
For technical assistance, call CHEMTREX (Chemical Transportation
Emergency Center): 800-424-9300. Other sources of technical infor-
mation are (1) the EPA's Oil and Hazardous Materials - Technical
Assistance Data System (OHM-TADS) contained in the NIH-EPA Chemical
Information System (CIS) which provides information pertinent to
emergency spill response efforts, and (2) the CHRIS System which
provides information on first aid, physical/chemical properties,
hazard assessments, and response methods. Both systems can be
accessed through NRC.
8.5 Disposal
Wastes that fail the EP toxicity test, 40 CFR (261.24), (EP extract
cadmium concentration is greater than 1.0 mg/1), are subject to
provisions of Subtitle C, the hazardous waste management standard.
The following waste streams are subject to subpart D regulations:
F006 - Generic wastewater treatment sludges from electroplating
operations.
K061 - Emission control dust/sludge from electric furnace production
of steel.
K069 - Emission control dust/sludge from secondary lead smelting.
K100 - Wastewater leaching solution from acid leaching of emission
control dust/sludge from secondary lead smelting.
8-2 July, 1982
-------
9. SAiMPLING, ACCEPTABLE ANALYTICAL TECHNIQUES, AND QUALITY ASSURANCE
9.1 Air (CONTACT: J. Walling, FTS 629-7954)
Cadmium in air is not a regulated pollutant. Therefore, no approved
or reference procedure has been promulgated. Analyses for cadmium
have been performed for a number of years, however, on particulate
matter collected in the National Air Monitoring Stations (NAMS) net-
work and its predecessor, the National Air Surveillance Network
(NASN). More recently, analyses have been done for size fractioned
particulates.
Hi-vol sampling is used for NAMS. Usual reference method sample
handling precautions are needed. Filters are cut, extracted ultra-
sonlcally in a hot aqua regia, which after dilution is analyzed by
optical emission spectrometry using plasma excitation. The discrim-
ination limit is dependent on the particular filter and spectrometer
used but is typically on the order of 10~3 ug Cd/m3 and reproducibil-
ity is usually within 15%. Accuracy is unknown, and interferences
are a function of the specific instrument (wavelength monitored).
Dichotomous samplers can be used to obtain size fractionated atmos-
pheric samples. Particulate loss from particulate coarse fraction
samples is a problem. Using energy dispersive x-ray fluorescence
for elemental analysis, the discrimination limit is on the order of
10~2 Ug Cd/m3, while reproducibility is typically smaller than 10%;
accuracy is not known.
9.2 Water (CONTACT: Theodore D. Martin, FTS 684-7312 or
Gerald D. McKee, FTS 684-7372)
Cadmium is a Clean Water Act 304(h) parameter and is listed as an
inorganic priority pollutant. It is also a drinking water parameter
with a maximum contaminant level of total cadmium set at 0.01 mg/1.
The term "total cadmium" is defined as the sum of the concentrations
of cadmium in both the dissolved and suspended fractions of the
sample. Samples collected for the analyses of total cadmium are not
filtered and must be preserved with nitric acid to pH < 2 as soon as
possible, preferably at the time of collection. When a sample con-
tains suspended material and is to be analyzed for total cadmium, a
sample digestion step is required. When a colorimetric, stripping
voltammetry, or chelation/extraction method is to be used, a sample
digestion step is also required to ensure that the cadmium is in the
proper chemical state and available for reaction.
There are a variety of approved methods for cadmium analysis. The
most commonly used method is atomic absorption spectroscopy (AA).
The analysis may be conducted using one of three different tech-
niques: direct aspiration, chelation/extraction, or graphite fur-
nace. For direct aspiration, a processed sample solution is aspi-
rated into an air/acetylene flame for dissociation and absorption.
The optimum concentration range for the 228.8 nm wavelength is 0.05
to 2 mg/1 with an estimated detection limit of 0.005 mg/1. Chela-
tion/extraction is used to concentrate and/or separate cadmium from
9-1 July, 1982
-------
an interfering matrix. Either the PDCA/CHC131,2* or APDC/MIBK3,4
methods can be used. Although cadmium can be extracted over a wide
pH range, with the APDC/MIBK system the extracting time is critical
(1 min.) and must be well controlled. Calibration standards must be
treated in the same manner as the samples. Chelatlon/extraction can
extend the direct aspiration working range downward from 0.05 mg/1 to
less than 0.005 mg/1. Intel-laboratory precision and accuracy studies
on 4 water samples containing 0.002 to 0.325 mg Cd/1 analyzed by
flame atomic absorption, gave relative standard deviations of ±34%,
to ±4.7%. Recoveries at these levels were ranged from 78% to 98%.
The graphite furnace technique is also used for analyzing low concen-
trations of cadmium. To prevent volatilization before atomization,
ammonium phosphate is added as a matrix modifier and the ashing
temperature is limited to 500°C. For every matrix analyzed, verifi-
cation is necessary to determine that method of standard additions is
not required. The optimum range for graphite furnace methods (for 20
ul injection) is 0.5 to 10.0 ug/1 with an estimated detection limit
of 0.1 ug/1. In an interlaboratory precision and accuracy study,
where 31 laboratories participated and 2 water samples containing 1.7
and 17 ug Cd/1 were analyzed by AA-graphite furnace, the standard
deviations were ±0.41 and ±3.0, respectively. Recoveries at these
levels were 108% and 99% respectively. In a single laboratory with
concentrations of 2.5, 5.0, and 10.5 ug Cd/1 spiked in tap water, the
standard deviations were ±0.10, ±0.16, and ±0.33, with recoveries of
95%, 99%, and 98%, respectively.
In the colorimetric method, cadmium reacts with dithizone in chloro-
form to form cadmium dithizonate. Cadmium is extracted at pH 2.8
and the absorbance of the pink dithizonate complex in chloroform is
measured spectrophotometrically at 518 nm. No interference problems
are reported. The analytical range for this method is 1 to 10 ug Cd
in the sample aliquot used for extraction. If 25 ml of sample is
extracted, the minimum detectable concentration is 0.02 mg/1. In an
interlaboratory precision and accuracy study with 44 participating
laboratories using a synthetic sample with a concentration of 0.05
mg Cd/1, the reported relative standard deviation was ±24.6% with a
recovery of 106%.
In the differential pulse anodic stripping voltammetry method (DPAS-
voltammetry), the sample is first digested with nitric acid. The
solution is then buffered with ammonium citrate to pH 3 and hydroxy-
lamine is added to eliminate interference from ferric iron. After
deposition onto a hanging mercury drop electrode at a constant
potential, the cadmium is stripped back into solution using the dif-
ferential pulse scanning mode. The current is measured and the
cadmium concentration determined using the standard addition
*Numbers refer to references contained in the table at the end of
this section.
9-2 July, 1982
-------
technique. This method is applicable up to 0.1 mg/1 cadmium, while
the limit of detection is 0.001 mg/1. In an interlaboratory preci-
sion and accuracy study, where 7 laboratories participated and 3
water samples containing 0.01, 0.03, and 0.07 mg Cd/1 were analyzed
by DPAS-voltammetry, the standard deviations were ±0.002, ±0.003,
and ±0.01, respectively. Recoveries at these levels were 103%, 91%,
and 98%, respectively. In a single laboratory, the reported stan-
dard deviations for the same levels of concentration were ±0.003,
±0.004, and ±0.01, respectively.
In response to the improved state-of-the-art of multi-element analy-
sis, a water/wastewater related method which includes cadmium has
been promulgated by EPA (Federal Register, 44, p. 69559, December 3,
1979). The revised method (200.7) uses inductively coupled plasma-
atomic emission spectroscopy (ICP-AES). The atomic-line emission
spectra is processed by computer to subtract background and to
correct for any spectral interference. While the estimated instru-
ment detection limit is 0.004 mg/1 (at 226.5 nm), the optimum work-
ing range for cadmium by the ICP technique is considered to be from
0.01 mg/1 to well above 100 mg/1. In an interlaboratory precision
and accuracy study, where 7 laboratories participated and 2 quality
control check samples containing 0.014 and 0.05 mg Cd/1 were ana-
lyzed by ICP-AES, the relative standard deviations were ±16% and
±12%, respectively. Recoveries at these levels were 93% and 96%,
respectively. In a single laboratory at concentrations of 0.07 and
0.59 mg Cd/1, the relative standard deviations were ±1.9% and ±1.8%
with recoveries of 100% and 98%, respectively.
The fallowing table summarizes the approved method with appropriate
references:
LIST OF APPROVED TEST PROCEDURES FOR TOTAL CADMIUM
Reference Method No.
Digestion^ followed by
AA-direct aspiration
AA-graphite furnace
ICP-AES6
D PAS-Vo11 ammet ry
Colorimetrtc (Dithizone)
EPAl
213.1
213.2
200.7
Std
Methods3
303A or
303B
304
ASTM2
D3557-78
(A or B)
uses4
1-3135-78 or
1-3136-78
D3557-78C
310B
1. "Methods for Chemical Analysis of Water and Wastes, 1979"
EPA-600/4-79-020.
2. "Annual Book of Standards," Amer. Society for Testing and
Materials, Part 31, Water.
9-3
July, 1982
-------
List of Approved Test Procedures for Total Cadmium (continued)
3. "Standard Methods for the Examination of Water and Wastewater,"
15th Edition.
4. "Methods for Analysis of Inorganic Substances in Water and
Fluval Sediments," U.S. Department of the Interior, Geological
Survey, Open-file Report 78-679.
5. Sample digestion of the filtrate for dissolved metals, or diges-
tion of the original sample solution for total metals may be
omitted for AA (direct aspiration or graphite furnace) or ICP
analyses provided the sample has a low COD and meets the follow-
ing criteria: (a) visibly transparent, (b) no odor, (c) free of
particulate matter following acidification.
Note: If the sample digestion procedure included in one of the
other approved references is different than an EPA procedure,
the EPA procedure must be used.
6. Inductively Coupled Plasma Optical Emission Spectrometric Method
(ICP) for Trace Element Analysis of Water and Wastes; Method
200.7 published by U.S. EPA, EMSL-Clncinnati.
9.3 Solid Wastes (CONTACTS: T. Hlnners, FTS 545-2140,
W. Beckert, FTS 545-2137)
EPA regulations define a waste as hazardous if the concentration of
cadmium in a specified extract of the waste, equals or exceeds 1.0
mg/1. The procedure is explained in detail in "Test Methods for
Evaluating Solid Waste, Physical/Chemical Methods" (EPA, SW-846,
1980). The aqueous extract is analyzed by AA.
At present, no approved methods are available for determination of
total cadmium content of wastes. Digestion procedures, similar to
that described for soil analysis have been used for waste materi-
als. Soil and sediment samples are prepared as outlined in "Interim
Methods for Analysis of Elemental Priority Pollutants in Sludge,"
EPA-EMSL. Cinn. (1978). The sample Is digested (HN03/H202) and
analyzed for cadmium according to the AA methods detailed in Section
9.2 above.
9.4 Other Samples
The "NIOSH Manual of Analytic Methods" (2nd edition, Vol. I, 1977)
contains procedures for the analysis of cadmium in blood (Method
223) and urine (Method 224). Both procedures consist of digestion
with an acid mixture followed by analysis using anodic stripping
voltammetry. Volume 3 of the same NIOSH manual also provides
procedures for analysis of cadmium dusts (Method S312) and fumes
(Method S313) in air. These procedures use HN03 digestion of
collection filters followed by AA analysis.
9-4 July, 1982
-------
9.5 Quality Assurance (CONTACT: John Winter, FTS 684-7325)
ORD has a full range of quality assurance support available which
includes the following items:
• Unknown performance evaluation samples
• Known quality control check samples
These are available to the Regions through the Quality Assurance
Branch of EMSL-Cincinnati.
Quality control standards for air analysis for cadmium are under
development. (CONTACT: J. Puzak, FTS 629-2188)
For hazardous waste analysis, quality assurance and certified sam-
ples are available from the National Bureau of Standards (telephone:
309-921-2045); samples include cadmium in coal fly ash (SRM 1633) and
river sediment (SRM 1645).
9-5 July, L982
-------
REFERENCES
The major references used in the preparation of this document are listed
below. EPA references are listed by EPA office of origin and the year of
publication. For further information, refer to contacts qiven throughout this
document or .contact the relevant EPA offices listed at the end of this section.
(ECAO, 1981)
Health Assessment Document for Cadmium, EPA-600/8-81 -.023
Environmental Criteria and Assessment Office (1980).
(Friberg, 1974) Cadmium in the Environment, L. Friberg M. Piscator, G.
Nordberg, and T. Kjellstrom; 2nd edition, CRC Press (.1974).
(IARC, 1976)
(MERL, 1981)
(Nriagu, 1980)
(OAQPS, 1981)
(OHEA, 1983)
(ORNL, 1973)
(OWRS, 1979)
(OWRS, 198(3)
IARC Monograph, 'Vol. II, pp 39-74, World Health Organiza-
tion (1976).
Effects of Sewage Sludge on the Cadmium and Zinc Content of
Crops,EPA-600/8-81-003,Municipal Environmental Research Lab,
Cincinnati, OH (1981).
Cadmium in the Environment, J.O. Nriagu, Ed., Wiley (1980).
Survey of Cadmium Emission Sources, EPA-450/3-81-013, Office
of Air Quality Planning and Standards, (1981).
Updated Mutagenicity and Carcinogenicity Assessment of
Cadmium,EPA600/8-83-025A,Draft,OfficeofHealth and
Environmental Assessment (1983).
Cadmium the Dissipated Element, ORNL/NSF-EP-21 , Oak Ridge
National Laboratory (1973).
Water-Related Environmental Fate of 129 Priority Pollu-
tants, Vol. I, Ch. 9, EPA-440/4-79-029a, Office of Water
Regulations and Standards (1979).
Ambient Water Quality Criteria for Cadmium, EPA-440/5-
80-025, Office of Water Regulations and Standards (1980) .
R-1
October, 1983
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OFFICE CONTACTS
The EPA' offices and divisions that are listed below may be contacted for more
information relating to the indicated sections of this document. While these
offices are, in many cases, the offices of origin for the data included in
this paper, the personal contacts given throughout this document should be
contacted first. Unless otherwise noted, the offices listed are situated in
Headquarters, Washington, D.C., and the telephone numbers given are FTS
(Federal Telecommunications System) numbers. For commercial telephone calls
to Headquarters which are not placed on FTS, area code 202 must be used.
Other commercial numbers are noted for the office contacts located outside
Washington, D.C.
HEALTH AND ENVIRONMENTAL EFFECTS (Section 2)
Office of Health and Environmental Assessment (OHEA)
Environmental Criteria and Assessment Office:
Cincinnati, OH 684-7531 (513-684-7531)
Research Triangle Park, NC 629-2266 (919-541-2266)
Carcinogen Assessment Group 755-3968
Office of Drinking Water (ODW)
Health Effects Branch 472-6820
Office of Toxic Substances' (OTS)
Health and Environmental Review Division 382-4241
Environmental Research Laboratory
Duluth, MN, Region V 783-9550 (218-^727-6692)
ENVIRONMENTAL RELEASES AND EXPOSURE (Sections 3 and 4)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Water Regulations and Standards (OWRS)
Monitoring and Data Support Division 426-2503
R-2 July, 1982
-------
Office of Toxic Substances (OTS)
Exposure Evaluation Division 382-3873
Assessment Division 382-3442
DATA BASES (Section 5)
Office of Toxic Substances (OTS)
Management Support Division 382-3546
REGULATORY STATUS. STANDARDS, AND CRITERIA (Sections 6 and 7)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Drinking Water (ODW)
Criteria and Standards Division 472-5016
Office of Water Regulations and Standards (OWRS)
Criteria and Standards Division 755-0100
Effluent Guidelines Division 426-2571
Office of Solid Waste (OSW)
State Programs and Resources
Recovery Division 755-9107
SPILL CLEAN-UP AND DISPOSAL (Section 8)
NOTE: For Emergenices call the National Response Center at 1-800-424-8802
(1-800-426-2675 from the Baltimore/Washington area).
Office of Emergency and Remedial Response (OERR)
Emergency Response Division 245-3045
Oil and Hazardous Materials Spills Branch
Edison, NJ; Region II 340-6634 (201-321-6634)
R-3 July, 1982
-------
Office of Solid Waste (OSW)
Hazardous and Industrial Waste Division 755-9187
ANALYTICAL TECHNIQUES (Section 9)
Environmental Monitoring Systems Lab (EMSL)
Air Analysis
Research Triangle Park, NC 629-2454 (919-541-2454)
Water Analysis
Cincinnati, OH 684-7311 (513-684-7311)
Waste Analysis
Las Vegas, NV 545-2137 (702-798-2137)
GENERAL IPP COMMENTS, CORRECTIONS, OR QUESTIONS
Office of Toxic Integration
Chemical Information and Analysis Program 382-2249
R-4 July, 1982
-------
Chlorinated Org. Solvents
-------
CHLORINATED ORGAMTC SOLVENTS: TRICHLOROETHAHE, TETRACHLOROETHE«E,
1,1,1-TRICHLOROETHAHE, DICHLOROMETHANE, ANH TETRACHLOROHETHANE
Table of Contents Page
Physical/Chemical Properties and Chemistry 1-1
Properties 1-1
Chemistry and Environmental Fate/Transport 1-1
Effects Information 2-1
Health Effects 2-1
Environmental Effects 2-7
Environmental Release 3-1
Air Releases 3-1
Water Releases 3-3
Exposure 4-1
Air Exposure 4-1
Water Exposure 4-2
Data Bases 5-1
NIH/EPA Chemical Information System (CIS) 5-1
Chemical in Commerce Information System (CICIS) 5-2
Chemical Substances Information Network (CSIN) 5-2
Graphic Exposure Modeling System (GEMS) 5-3
Regulatory Status 6-1
Promulagated Regulations 6-1
Proposed Regulations 6-9
Other Actions 6-11
Standards and Recommended Criteria 7-1
Air 7-1
Water 7-1
Hazardous Waste 7-3
Other 7-3
July, 1984
-------
Spill or Other Incident Clean-Up/Disposal 8-1
Hazards and Safety Precautions 8-1
First Aid 8-1
Emergency Action 8-1
Notification and Technical Assistance 8-2
Disposal 8-3
Sampling, Acceptable Analytical Techniques, and Quality Assurance 9-1
Air 9-1
Water 9-2
Solid Wastes 9-6
Other Samples 9-6
References and Office Contacts R-1
July, 1984
-------
CHLORINATED ORGANIC SOLVENTS; TRICHLOROETHENE, TETRACHLOROETHENE,
1,1,1-TRICHLOROETHANE, DICHLOROMETHANE, AND TETRACHLOROMETHANE
Table of Contents Page
Physical/Chemical Properties and Chemistry 1-1
Properties 1-1
Chemistry and Environmental Fate/Transport 1-1
Effects Information 2-1
Health Effects 2-1
Environmental Effects 2-7
Environmental Release 3-1
Air Releases 3-1
Water Releases 3-3
Exposure 4-1
Air Exposure 4-1
Water Exposure 4-2
Data Bases 5-1
Chemicals in Commerce Information System (CICIS) 5-1
EPA Chemical Activities Status Report (EPACASR) 5-1
NIH/EPA Chemical Information System (CIS) 5-1
Chemical Regulations and Guidelines System (CRGS) 5-1
Chemical Substances Information Network (CSIN) 5-1
EPA Information Clearinghouse 5-2
Regulatory Status 6-1
Promulgated Regulations 6-1
Proposed Regulations 6-5
Other Actions 6-8
Standards and Recommended Criteria 7-1
Air 7-1
Water 7-1
Hazardous Waste 7-2
Other 7-2
July, 1982
-------
Spill or Other Incident Clean-Up/Disposal 8-1
Hazards and Safety Precautions 8-1
First Aid 8-1
Emergency Action 8-1
Notification and Technical Assistance 8-2
Disposal 8-2
Sampling, Acceptable Analytical Techniques, and Quality Assurance 9-1
Air 9-1
Water 9-2
References and Office Contacts R-l
July, 1982
-------
CHLORINATED ORGANIC SOLVENTS: TRICHLOROETHENE, TETRACHLOROETHENEt
1,1,1-TRICHLOROETHANE, DICHLOROMETHANE, AND TETRACHLOROMETHANE
Five chlorinated organic solvents are being extensively studied by
several Agency program offices. These solvents Include: trichloro-
ethene (79-01-6), tetrachloroethene (56-23-5), 1,1,1-trichloroethane
(71-55-6), dichloromethane (75-09-2), and tetrachloromethane (56-23-
5). The information contained within is excerpted from the work-
group's findings. General information pertaining to the chlorinated
organic solvents is presented first, followed by specific information
on the individual chemical where applicable. Further information can
be obtained from Mr. Arnie Edelman, FTS 382-2249.
1. PHYSICAL/CHEMICAL PROPERTIES AND CHEMISTRY
1.1 Properties
Trichloroethene (TCE), tetrachloroethene (PCE), 1,1,1-trichlorothane,
dichloromethane, and tetrachloromethane are all short-chain chlorina-
ted aliphatic hydrocarbons. Physical/chemical properties character-
istic of this class include: high volatility, non-flammability, good
thermal stability, and in general low acute toxicity. Additionally,
they are miscible with a wide variety of organic compounds. Relevant
physical/chemical properties are listed in Table 1.
Because of their physical/chemical properties, these chemicals, with
the exception of tetrachloromethane,* have found widespread use in a
variety of industrial and consumer solvent applications. As a conse-
quence of their use, these solvents are widely distributed throughout
the environment.
1.2 Chemistry and Environmental Fate/Transport
As a consequence of use, approximately 90 percent of the chlorinated
organic solvents are released directly to the atmosphere. Once in
the troposphere, TCE and PCE react with hydroxyl radicals, via attack
on the carbon-carbon double bond to yield phosgene and either
dichloroacetyl chloride (from TCE) or trichloroacetyl chloride (from
PCE). Dichloromethane and 1,1,1-trichloroethane also undergo
photooxidation in the troposphere by hydroxyl radicals (OWRS, 1979).
The photochemical oxidants which are produced in these reactions
contribute to the formation of photochemical smog (NAS, 1977).
Approximately 1 percent of the dichloromethane and 15 percent of the
1,1,1-trichloroethane in the troposphere will be transported to the
stratosphere where they will either undergo photodissociation by
* The use of tetrachloromethane as an industrial solvent has been on the
decline because of the availability of more suitable and presumably safer
substitutes.
1-1 July, 1982
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\o
CO
TABLE 1. PROPERTIES OF THE CHLORINATED ORGANIC SOLVENTS
Chemical Name
and Formula
CAS Number
and Synonyms
Melting Boiling
Point Point
Water
Density Vapor
(20°/ Pressure
40°) (torr)
Water Flash-
Solubility point
(mg/1) (°C)
Log Octanol/
Water Parti-
tion Coeffi-
cient
Trichloroethene 79-01-6
trichloroethylene
-73 87-90 1.46 58 (20°C) 1100 (20°C) None 2.29
Tetrachloroethene 127-18-4
tetrachloroethylene
perchloroethylene
-19 121
1.62 14 (20°C) 150-200 (20°C) None 2.88
i
to
1,1,1-Trichloro- 71-55-6
ethane methyl chloroform
-30 74-76 1.34 96 (20°C) 480-4400 (20°C) None 2.17
Oiciiloroinethaue 75-09-2
CH2C1-2 methylene chloride
-95 40 1.33 362 (20°C) 13,200-20,000 None
(25°C)
1.25
c
i-'
*<
Tetrachloromuthane 56-23-5
carbon tetrachloride
-23 77
1.59 90 (20°C) 785 (20°C) None 2.64
-------
higher energy ultraviolet light or be carried back to earth during
the precipitation process. Tetrachloromethane is stable in the
troposphere; the rate of photooxidation is extremely slow. As a
consequence, it also ditfuses into the stratosphere where it is
photolytically degraded by high energy ultraviolet light or is
carried back to the earth during the precipitation process. The
resultant photodissociation products (chlorine atoms and other
chlorine-containing free radicals) from these reactions are theorized
to be involved in the series of reactions that contribute to the
destruction of the ozone layer (OWRS, 1979; NAS, 1979).
Volatilization is the major transport process for the removal of the
chlorinated organic solvents from surface water. The evaporative
half-life for these chemicals from stirred water ranged from 15-30
minutes. Neither hydrolysis, oxidation, nor microbial degradation
are important fate processes. These processes are slow compared to
volatilization (OWRS, 1979).
All the chlorinated organic solvents have been measured in ground
water and in ambient air*. If these chemicals are released into the
soil, they are expected to move through the soil column to ground
water. Sorbtion to soil is not a significant fate process (OWRS,
1979).
* Information received from OAQPS.
1-3 July, 1982
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2. EFFECTS INFORMATION
2.1 Health Effects (CONTACTS: Jerry Stara, FTS 684-7531;
Bill Lappenbush, FTS 472-6820)
2.1.1 Acute Toxicity
Dichloromethane; The primary health effects associated with acute
exposure to dichloromethane are central nervous system (CNS) depres-
sion, cardiotoxic effects; and increased levels of carboxyhemoglobin
(CoHb), which are a consequence of the metabolic transformation of
dichloromethane to carbon monoxide (CO). The increased levels of
CoHb in the blood interferes with oxygen transfer and transport.
CNS effects are related to the anesthetic properties of dichloro-
methane. The onset of these effects is generally rapid and tempor-
ary, normally subsiding within hours after cessation of exposure.
However, in cases of acute human exposure, CNS effects have included
death, unconsciousness, labored breathing, headache, lassitude, and
nausea.
The observed cardiotoxic properties of dichloromethane include car-
diodepresslon and cardiacsensitization. Several human studies have
reported fatalities resulting from, or closely associated with, ex-
posure to dichloromethane, in which myocardial infarction was diag-
nosed.
Hepatotoxicity has not been reported in any human case report, even
those following fatal exposures.
The only evidence of human nephrotoxicity resulting from dichloro-
methane exposure was the finding of congested kidneys following a
fatal exposure (OHEA, 1982a).
Tetrachloromethane; Tetrachloromethane is toxic to humans and
animals following inhalation, ingestion or dermal administration.
Exposure to tetrachloromethane primarily affects the CNS, liver, and
kidneys. Tetrachloromethane has anesthetic properties.
Acute exposure to tetrachloromethane by Ingestion or inhalation may
result in fatal poisoning. Following ingestion, the patient experi-
ences a burning sensation in the mouth, esophagus, and stomach. Soon
the patient starts feeling dizzy, may suffer headache and become con-
fused, semiconscious and delirious. Finally, consciousness is lost
and the patient passes into a coma.
Ingestion of lesser amounts results in abdominal pain, nausea, and
vomiting. Some patients develop hiccoughs. The tongue becomes
coated. These symptoms are soon followed by diarrhea, which later
may be followed by constipation and occasionally by gastric and
Intestinal hemorrhages which, in some cases, may also be seen in the
mouth and pharynx. The patient can develop jaundice, the liver gets
enlarged and tender, and this may be associated with ascites and
generalized edema. Injury to kidney is also common. Some patients
2-1 July, 1982
-------
complain of visual disturbances, and edema of Che eyelids and develop
hemorrhages of the sclerae.
Inhalation of low concentrations of tetrachloromethane may be re-
stricted to such symptoms as moderate irritation of the eyes, moder-
ate dizziness and headache, which disappear promptly upon discontinu-
ation of exposure. In addition to the symptoms described above,
effects from higher concentrations include nausea, loss of appetite,
mental confusion, agitation, and the feeling of suffocation. At
higher concentrations the patient may lose consciousness and develop
fever and chills.
Dermal exposure causes a burning or stinging sensation followed by
erythema, hyperend a, wheal formation and vesication (OHEA, 1982b).
TCE; Exposure to TCE is associated with neurological disorders,
cardiovascular effects, and morphological damage to the liver and
kidney.
Acute exposure to high concentrations (>1,000 ppm) of TCE
via inhalation narcotizes the CNS, progressively depressing all func-
tions of the brain from cortex to medulla. Short exposures (few
minutes) result in headache, dizziness, nausea, vomiting, and uncoor-
dination; longer exposures cause CNS depression and unconsciousness,
in some cases death.
Exposure to low levels of TCE vapor can result in irritation of
mucous membranes and impairment of psychophysiological functions.
Exposures of 100 to 200 ppm TCE have caused eye and throat irrita-
tion. Inhibition of normal performance has been observed at concen-
trations as low as 100 ppm (8-hr, exposure) and is increasingly
pronounced at 300-500 ppm.
Virtually no dose-response data for oral exposure of humans to TCE is
available. Cases of poisoning from ingestion Involved adverse
effects on the heart or liver. However, liver damage was attributed
to contamination of TCE with other substances since no damage occured
when pure TCE was ingested. The oral LD5Q for humans has been
reported to be 7,000 mg/kg body weight (OHEA, 1982c).
PCE; The immediate effect of acute exposure of humans to PCE is
depression of the CNS. Acute exposure to high levels (approximately
4,000 ppm) may be fatal. Individuals, in controlled human studies,
exposed to 100 ppm for up to seven hours have shown gross signs
(decrements in task performance and coordination) of CNS depression
and behavioral alterations.
While there are insufficient data to estimate the lowest level of PCE
that would cause liver damage in humans upon acute or prolonged
exposure, the evidence suggests that adverse effects upon the liver
can occur at exposure levels that would cause only slight CNS depres-
sion. In animals, intermittent or prolonged exposure to PCE has been
observed to result in both liver and kidney damage at levels
exceeding 200 ppm.
2-2 July, 1982
-------
The LDjQ values in rats and mice were determined to be 4,000 and
8,000 mg/kg respectively. Although PCE can be absorbed through un-
broken skin, absorption through this route was estimated to be minor
(OHEA, 1982d).
1,1,1-Trichloroethane; 1,1,1-Trichloroethane affects both the CNS
and cardiovascular system (CVS). At levels of 1000 ppm, 1,1,1-tri-
chloroethane produces cardiovascular effects in humans that include
sensitization of the heart to spontaneous or catecholamine-provoked
arrhythmias and hypotension. It is highly likely that myocardial
depression occurs to some degree at much lower inhalation concentra-
tions than has been previously thought.
Concentrations at levels as low as 350 ppm also produce adverse
health effects. These effects include subjective symptoms of light-
headedness, syncope, stuffiness, mild headache, nausea, and mild
irritation of eye, nose, and throat. No significant abnormal blood
chemistry or organ function tests have been noted. The most adverse
effects are neurological symptoms, which have been diagnosed by sub-
jects' impaired performance of cognitive and manual tasks (OHEA,-
1982e).
2.1.2 Chronic Toxicity
Dichloromethane: The effects of low-level, long-term exposure are
not well characterized. Experimental animal studies and evidence in
humans provide limited information on the correlation between chronic
exposure to dichloromethane and subsequent toxic effects. Interpre-
tation of these data are further complicated by the fact that dichlo-
romethane contains chemical impurities. Exposure to dichloromethane
levels close to its threshold limit value (TLV) of 200 ppm have
resulted in behavioral and psychological effects such as decrements
in manual and mental performance. Decrements in eye-hand coordina-
tion and task-related response time have been associated with CoHb
levels of 3 to 5 percent.
It has been reported that CoHb levels of 2.5 percent or greater can
adversely affect individuals with angina pectoris or cardiovascular
disease.
Dichloromethane has been shown to pass through the placenta and into
the fetus. No clinical reports to date have shown an association be-
tween maternal exposure and congenital malformations; however, no
epidemiology studies have been performed. There is some preliminary
evidence to suggest behavioral teratogenic effects at low levels.
[-lore follow-up studies would be needed to clarify or confirm this
evidence.
Dichloromethane has shown positive responses in both bacterial and
yeast mutagenicity assays; information on the purity of the test
compound is not as yet available.
There are no well-designed animal bioassays available that positively
support the suggestive evidence of carcinogenic potential indicated
by Che bacterial inutagenic test results. The Dow Chemical Company
2-3 July, 1982
-------
recently completed a two-year chronic toxicity and oncogenicity
inhalation study of dichloromethane in rats and hamsters. A dose-
response increase in salivary gland sarcomas in the male rats became
statistically significant at the highest dose (3,500 ppm). There
were also increases in benign mammary tumors in female rats at all
dose levels (500, 1,500, and 3,500 ppra) and in male rats at the
highest dose levels (3,500 ppm).
Two long-term animal bioassay studies are currently in progress at
NTP (OHEA, 1982a).
Tetrachloromethane; Patients suffering from chronic inhalation poi-
soning by continued low exposures may complain of fatigue, lassitude,
giddiness, anxiety, and headache. These patients suffer from pares-
thesias and muscular twitchings and show increased reflex excitabil-
ity. They may be moderately jaundiced, have a tendency to hypogly-
cemia, and the liver may show fatty infiltration. Patients may com-
plain of loss of appetite, nausea, and occasionally of diarrhea. In
some cases, the blood pressure is lowered which is accompanied by
pain in the kidney region, dysuria, slight nocturia, and has urine
containing small amounts of albumin and a few red blood cells.
Burning of the eyes and, in a few instances, blurred vision are
frequent complaints of those exposed. If these symptoms are not
pronounced or of long standing, recovery usually takes place upon
discontinuation of the exposure and if the proper treatment is
received.
Tetrachloromethane has not been shown to be teratogenic; however,
the potential exists for embryotoxicity, especially in males. Tetra-
chloromethane has produced distinct degenerative changes in testicu-
lar histology in male rats, eventually resulting in aspermatogenesis
and functional male infertility. These effects occurred following
intraperitoneal injection at relatively high doses. Unfortunately,
low doses were not tested.
Studies on experimental animals indicate that this chemical is a
carcinogen in three species: hamsters, mice, and rats. The Inter-
national Agency for Research on Cancer (IARC) concluded that there is
sufficient evidence that tetrachloromethane is carcinogenic in exper-
imental mammals. There are suggestive case reports of liver cancer
in humans. IARC states that "in the absence of adequate data on
humans, it is reasonable, for practical purposes to regard tetra-
chloromethane as if it presented a carcinogenic risk to humans"
(IAKC, 1979).
TCE; The effects of low-level (50-500 ppm), long-term exposure are
not well characterized. Reports of the toxicological consequences of
industrial exposures are often sketchy, and there are few well-
controlled epidemiological studies. Difficulties in delineating the
toxic effects of trichloroethene are further compounded by chemical
impurities and toxic decomposition products of trichloroethene.
However, experimental studies in human volunteers provide some infor-
mation about the relationship between chronic low-level exposure to
2~4 July, 1982
-------
trichloroethene and toxic effects. Signs and symptoms of toxicity
include dizziness, headache, fatigue, nausea, fainting spells, and
other subjective responses that suggest a CNS origin. Dermal and eye
irritation and intolerance to alcohol are among the better defined
manifestations of exposure to trichloroethene. Behavioral and psy-
chological effects, particularly as they affect manual and mental
performance, have been reported at levels of LOO ppm (current
TWA-TLV) in some, but not all, experimental and epidemiological
studies. It is highly likely that the direct myocardial depressant
effect, which is a serious health hazard for those with compromised
or reduced cardiac reserve occurs at lower exposure concentrations
than has been previously thought.
TCE has been associated with fetotoxcity in humans. However, these
reports are not conclusive in establishing this association.
There is evidence that technical grade trichloroethylene (epoxide-
stabilized) has carcinogenic activity, based on the increased inci-
dence of hepatocellular carcinomas in exposed B6C3F1 mice, the posi-
tive mutagenic responses in bacteria and yeast, and the positive
mutagenic response of bacteria to chloral hydrate, a metabolite found
in both rats and man. Applying the International Agency for Research
on Cancer criteria for animal studies, this level of evidence would
be regarded as limited and not sufficient to provide a firm
conclusion on its carcinogenic potential in humans (OHEA, 1982c).
However, the National Toxicology Program (NTP) recently completed a
carcinogenesis bioassay of pure TCE by gavage in rats and mice. The
preliminary draft report supports the carcinogenic!ty of pure TCE.
(Carcinogenic!ty occurred in two species, which would cause it to be
categorized as having sufficient evidence of carcinogenicity by the
IARC criteria.) (OHEA, 1982c, NTP, 1982)
PCE; The data available from both human and animal exposures to PCE
indicate that the CNS, liver and kidneys are adversely affected.
Subjective complaints such as headache, fatigue, dizziness, and
general intoxication have been reported after exposure to 100 ppm.
Both acute and chronic exposure situations have the potential to
cause liver damage in humans. While there are insufficient data to
estimate the lowest level of PCE that would cause liver damage upon
acute or prolonged exposure, the evidence suggests that adverse
effects upon the liver can occur at exposure levels that would cause
only slight CNS depression. Since PCE has the potential to
accumulate in lipid-rich body tissues and is only completely
eliminated from the body several weeks after cessation of exposure,
prolonged exposure may result in a greater body burden, subjecting
the liver to a chronic insult at a given exposure concentration.
PCL has not been clearly demonstrated to cause point mutations in
bacteria. There is suggestive information that PCE may be
genetically active in yeast.
2-5 July, 1982
-------
Two long-term animal bioassays have been performed to assess the
carcinogenic potential of PCE. In one involving exposure of rats and
mice to PCE by gavage, the National Cancer Institute (NCI) reported
the induction of hepatocellular carcinomas in male and female mice.
However, the dose levels used in the NCI study are levels that have
been observed in other experiments to result in hepatotoxicity.
Also, the PCE used contained epoxide stabilizers. In rats the
resulting high mortality precluded any conclusions with regard to
carcinogenic potential. In the second study, rats were exposed to
PCE by inhalation. No evidence for carcinogenicity was reported,
however, limitations in this study make it difficult to assess PCE's
carcinogenic potential (OHEA, 1982d). NIP is currently completing a
lifetime animal bioassay on purified PCE.
1,1,1-Trichloroethane; Very little information is available on
low-level, long-term exposure to 1,1,1-trichloroethane.
Technical grade 1,1,1-trichloroethane has tested positive in several
mutagenicity tests; however, this chemical contained small amounts of
dioxane, a stabilizer, that may have contributed to the positive
results.
NCI animal bioassays have not provided definitive evidence of carcin-
ogenicity. An NTP lifetime animal bioassay using both rats and mice
is currently nearing completion (OHEA, 1982e).
2.1.3 Absorption, Distribution, and Metabolism
The chlorinated organic solvents are readily absorbed through the
lungs and gastrointestinal cract. Absorption through the skin occurs
but at a much slower rate. Because of their physical/chemical pro-
perties, the chlorinated solvents are distributed to the fatty tis-
sues. Tetrachloromethane is also found in high concentrations within
the bone marrow. Dichloromethane, on account of its solubility in
water, tends to distribute throughout all body fluids and tissues.
These solvents readily cross the blood-brain barrier as witnessed by
their narcotic effects. They can also cross the placenta and dis-
tribute within the developing fetus.
These chemicals are all metabolized to some extent before elimination
from the body. The extent of metabolism varies among these chemicals
and among species. The primary route of elimination is through the
lungs. Dichloromethane is metabolized to carbon monoxide by the
liver microsomes. Tetrachloromethane metabolism is thought to
involve short-lived free radicals which either alkylate protein sulf-
hydryl groups or initiate peroxidative decomposition of lipids.
Metabolites include chloroform, hexachloroethane, and carbon
dioxide. These metabolites are thought to play a major role in the
overall toxicity of tetrachloromethane.
The metabolism of both TCE and PCE probably involve an epoxide
intermediate. The trichloroethylene oxide intermediate, an
unsymmetrical epoxide, is less stable and more reactive toward
cellular nucleophiles than the symmetrical tetrachloroethylene oxide
2-6 July, 1982
-------
intermediate. The principal products of ICE metabolism are tri-
chloroacetaldehyde, trichloroacetic acid, trichloroethanol, and
trichloroethanol-glucuronide. PCE is metabolized to trichloroacetic
acid as well as oxalic acid and trichloroacetyl chloride.
1,1,1,-Trichloroethane is metabolized to only a small degree by mam-
mals. The postulated metabolic pathway involves hydroxylation of
1,1,1-trichloroethane to trichloroethanol by cytochrome P-450 mixed
function oxidase system. Other metabolites are trichloroacetic acid
and trichloroethanol-glucuronide (OHEA, 1982a-e).
2.2 Environmental Effects
2.2.1 Aquatic Effects
Dichloromethane: The 48-hour LC5Q for Oaphnia magna is 224,000
ug/1.Thereis little difference in sensitivity between Uaphnia
magna and bluegill towards dichloromethane. The 96-hour LCso^or
mysid shrimp is 256,000 ug/1. No information is available concerning
the chronic toxicity of dichloromethane to freshwater aquatic life.
(OWRS, 190a)
Tetrachloromethane: The available data for tetrachloromethane indi-
cate that acute toxicity to freshwater aquatic life occurs at concen-
trations as low as 35,200 ug/1 and would occur at lower concentra-
tions among species that are more sensitive than those tested. No
data are available concerning its chronic toxicity to sensitive
freshwater aquatic life.
The available data for tetrachloromethane indicate that acute toxici-
ty to saltwater aquatic life occurs at concentrations as low as
50,000 ug/1 and would occur at lower concentrations among species
that are more sensitive than those tested. No data are available
concerning the chronic toxicity of tetrachloromethane to sensitive
saltwater aquatic life (OWRS, 1980b).
TCE; No data on the effects of TCE on freshwater aquatic life were
published prior to 1978, and consequently the data base is quite
limited. The available data for TCE indicate that acute toxicity to
freshwater aquatic life occurs at concentrations as low as 45,000
ug/1 and would occur at lower concentrations among species that are
more sensitive than those tested. No data are available concerning
the chronic toxicity of TCE to sensitive freshwater aquatic life but
adverse behavioral effects occur to one species at concentrations as
low as 21.9UO ug/1.
The available data for TCE indicate that acute toxicity to saltwater
aquatic life occurs at concentrations as low as 2,000 ug/1 and would
occur at lower concentrations among species that are more sensitive
than those tested.
There was a 50 percent decrease in i$C uptake by the alga Phaeodacty-
lum tricornutum at a concentration of 8,000 ug/1. Erratic swimming,
2~7 July, 1982
-------
uncontrolled movement, and loss of equilibrium have been observed in
sheepshead minnows and grass shrimp after several minutes' exposure
to 20,000 and 2,000 ug/1, respectively. No other data for saltwater
organisms were found.
No data are available concerning the chronic toxicity of ICE to sens-
itive saltwater aquatic life (OWRS, 1980c).
PCE; The available data for PCE indicate that acute and chronic tox-
icity to freshwater aquatic life occur at concentrations as low as
5,280 and 840 ug/1, respectively, and would occur at lower concentra-
tions among species that are more sensitive than those tested.
The data base for freshwater organisms exposed to PCE indicates that
the rainbow trout is most sensitive and the blueglll and fathead min-
now are about as sensitive as Daphnia magna. An embryo-larval test
has been conducted with the fathead minnow and the ratio between the
acute and chronic values for this species is 16. The data for an
alga indicate that it is much more resistant than the fishes and
cladoceran. Compared to the dichloroethenes and trichloroethene
(TCE), tetrachloroethene (PCE) is more acutely toxic to fish and
invertebrate species.
The available data for PCE indicate that acute and chronic toxicity
to saltwater aquatic life occurs at concentrations as low as 10,200
and 450 ug/1, respectively, and would occur at lower concentrations
among species that are more sensitive than those tested.
Acute and chronic tests have been conducted with the mysid shrimp and
the acute value is 23 times the chronic value which result suggests a
substantial accumulative chronic toxicity. The saltwater alga, Skel-
etonema costatum, is much more resistant than the mysid shrimp, and
the alga, Phaeodactylum tricornutum, has a resistance comparable to
that for the mysid shrimp (OWRS, 1980d).
1,1,1-Trichloroethane; The 48-hour LC5Q value for DaPhnia ma8na was
greaterthanthe highest exposure concentration, 530,000 ug/1. The
96-hour LC5Q value for bluegill was 69,700 ug/1. No freshwater in-
vertebrate species or saltwater organisms have been tested under
chronic exposure conditions (OWRS, 1980e).
2.2.2 Other Effects
The available data indicate that the bluegill can bioconcentrate the
chlorinated solvents to a limited extent. The highest factor
obtained, 49, was for PCE. However, the biological half-life was
less than one day. These results suggest that no residue problem
will occur at concentrations that are not directly toxic to aquatic
life (OWRS, 1980a-e).
2-8
July, 1982
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3. ENVIRONMENTAL RELEASE
The uses of the chlorinated organic solvents and their releases to
the environment are summarized in Tables 2 and 3. As shown in Table
2, these chlorinated organic chemicals, with the exception of tetra-
chloromethane, have found widespread use for a variety of solvent
applications, most notable metal cleaning/degreasing. As a conse-
quence of their use and as a function of their physical/chemical
properties, these chemicals eventually reach the atmosphere. Table 3
quantifies these environmental releases. The figures in this table
refer to initial release, not to their short-term or long-term envi-
ronmental sink. Media transfer is expected to occur over time.
3.1 Mr Releases* (CONTACT: Karen Blanchard, FTS 629-5519)
(It should be noted that the largest environmental releases do not
necessarily contribute to the highest concentrations found in ambient
air around a particular stationary source.)
Uichloromethane:
Significant Sources
The following are the sources contributing the highest concentrations
of dichloromethane to the ambient air:
• Metal cleaning operations (widely scattered industries, SIC
groups 25 and 33-39), and paint stripping operations.
• Chemical industries producing dichloromethane or using it as an
intermediate (SIC 2869). Dichloromethane is produced at 7
plants located in West Virginia, Texas, Louisiana, Kentucky, and
Kansas.
Other Sources
• Widely scattered industries or households using paint or varnish
removers containing dichloromethane solvent.
• It is used as a chemical intermediate in the manufacture of var-
ious drugs, dyes, and perfumes, and in the dewaxing of oils. It
is also used as a decaffelnating agent for coffee and as a foam-
ing agent for flexible polyurethane foams. In 1978 approximate-
ly 5 percent of production was used as a solvent in plastics
processing. About 17 percent was used as a vapor depressant in
aerosols and represents the third largest end use. In these
applications the chemical is eventually released to the atmos-
phere.
Information supplied by OAQPS.
3-1 July, 1982
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TABLE 2. USES OF THE CHLORINATED ORGANIC SOLVENTS, 1978 (kkg/yr)
Non-
Consumptive
Uses and Percent
Adhesives
Aerosols
Dry Cleaning
Solvent
Foam Blowing Agent
Grain Fumigaut
Identified Solvent
Uses
Intermediate
Metal, Cleaning/
Degreasing
Miscellaneous
Solvent Uses and
Other Applications
Miscellaneous/
Other Uses
Paint Kemoverb
Phdniidceutical
Solvent
Textile Processing
Tetrachloro- 1, 1, 1-Trichloro- Dichloro-
me thane ethane methane PCC TCE TOTALS
19,800 (8%) -- — — 19,800
20,000 (8%) 40,500 (17%) — — 60,500
168,000 (61%) — 168,000
11,900 (5%) — — 11,900
13,300 (4%) -- — 9,500 (3%) -- 22,800
2,500 (1%) — — — — 2,500
293,000 (87%) — — — — 293,000
187,000 (76%) 52,000 (22%) 53,900 (20%) 110,000 (89%) 402,900
28,800 (8%) — 49,400 (21%) — 13,600 (11%) 91,800
100 «1%) 20,700 (8%) — 22,200 (8%) — 43,000
71,400 (30%) — — 71,400
10,000 (5%) — — 10,000
22,200 (8%) — 22,200
Source: Compiled by the Agency-wide Solvents Workgroup //2.
-------
TABLE 3. RELEASE OF THE CHLORINATED ORGANIC SOLVENTS
TO THE
Dichlororaethane
Production
Paint removers
Metal degreasing
Aerosols
Foam blowing agent
Pharmaceutical solvent
Miscellaneous solvent uses
Total
Tetrachloromethane
Production
Grain fumigant
Intermediate
Identified solvent uses
Miscellaneous
Total
Trichloroethene
Production
Metal degreasing
Other solvent uses
PVC chain cerminater
Total
Tetrachloroethene
Production
Dry cleaning
Metal degreasing
Grain fumigant
Textile processing
Miscellaneous
Total
1,1, 1-Trichloroethane
Production
Metal degreasing
Aerosols
Adhesives
Miscellaneous
Total
M973
Source: Compiled by the Agencj
ENVIRONMENT (kkg/yr)*
AIR
280
61,200
43,600
36,700
10,700
5,300
41,900
199,680 (41%)
1,300-1,900
12,000
480
1,400
24,400
39,880 (99%)
300
92,400
11,400
130
104,230 (86%)
420-1,030
143,000
45,300
9,500
14,300
18,300-18,50
231,275 (84%)
830
157,000
18,100
17,400
17,600
210,930 (87%)
r-wide Solvents
LAND
10
8,800
6,100
3,800
1,200
2,200
5,900
28,010 (58%)
110
5
5
no" «i%)
12,800
1,600
14,400 (12%)
25,200
6,300
6,000
iO 3,200-3,300
40,750 (15%)
21,800
1,900
920
2,300
26,920 (11%)
Workgroup #2.
WATER
30-60
1,400
1,000
460
760
3,665
50
110
200
35TT
40
2,200
270
2,510
(1%)
(1Z)
(2%)
30
1,100
290
120-380
1,680 (1%)
3,700
330
370
4,400
(2%)
3-3
July, 1982
-------
Tetrachloromethane;
Significant Sources
The following are the sources which contribute the highest concentra-
tions of tetrachloromethane to the ambient air. They are located in
West Virginia, Texas, Georgia, Louisiana, Kentucky, Kansas, Alabama,
Illinois, New Jersey, California and Michigan.
• Tetrachloromethane production (SIC 2869)
• Fluorocarbon production (SIC 2869)
Other Sources
Scattered industrial users of end products containing tetrachlo-
romethane solvents such as oil, wax and fat extractants, inks,
stains, paints, and lacquers. Few end products will be used in
sufficient volume to contribute significant pollution to the
ambient air. Tetrachloromethane is being phased out of most of
these applications.
TCE:
Significant Sources
The following are the sources contributing the highest concentrations
of TCE to the ambient air:
• Chemical industries producing TCE or using it as an intermediate
(SIC 2869). The three plants producing this chemical are lo-
cated in Texas and Louisiana.
• Metal cleaning operations (various widely scattered industries,
SIC groups 25 and 33-39). In 1978, 89 percent of the TCE
produced was used for metal cleaning, but there is a trend
toward substituting other chemicals (such as
1,1,1-trichloroethane) which contribute less to ozone formation.
Other Sources
TCE is used in dry cleaning establishments for removing grease
spots. It is also used as a solvent base for adhesives, seal-
ants, lubricants, and dip-painting processes, but these applica-
tions account for only 4 percent of total production.
PCE;
Significant Sources
The following are the sources contributing the highest concentrations
to the ambient air.
3~4 July, 1982
-------
• Dry cleaning establishments (SIC 7215, 7216, and 7218)
• Chemical industries producing PCE or using PCE as an intermedi-
ate (SIC 2869). PCE is produced at ten facilities located in
California, Kansas, Kentucky, Louisiana, and Texas.
• Metal cleaning operations (various industries, SIC groups 25 and
33-39).
Other Sources
PCE is used for processing in some of the 2,500 textile process-
ing facilities across the United States, accounting for less
than 7 percent of total PCE consumption.
1,1,1-Trichloroethane;
Significant Sources
The following are the sources contributing the highest concentrations
of 1,1,1-trichloroethane to the ambient air.
• Metal cleaning operations (widely scattered industries, SIC
groups 25 and 33-39). This application constituted 63 percent
of the 1978 total production.
• Chemical industries producing 1,1,1-trichloroethane (SIC 2869).
The four plants producing this chemical are located in Texas and
Louisiana.
Other Sources
1,1,1-Trichloroethane is used as a formulation and vehicle sol-
vent in a wide variety of consumer products, such as adhesives,
nonflammable paints, urethane coatings, and other sealants. It
is also used as an extraction solvent in nonfood and drug formu-
lations, as a fabric and drain cleaner, and as a lubricant and
coolant in cutting oils. Aerosol formulations represented 8
percent of production in 1978.
3.2 Water Releases;
• Metal degreasing operations
3-5 July, 1982
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4. EXPOSURE ROUTES (CONTACT: Mike Callahan, FTS 382-3873)
For all solvents, consumption of drinking water, inhalation of
ambient air and air in certain occupational settings can result in
the highest exposures. Food consumption may also be an important
exposure route. Preliminary U.S. data suggest the highest solvent
levels in foods appear to be trichloroethene in beverages (especially
colas) and oils and fats (such as margarine). The activities
responsible for inhalation exposures are primarily production, metal
degreasing, and dry cleaning. The most severe drinking water
exposures can be attributed to ground water contamination from dispo-
sal activities. At this time, the source of TCE in food has not been
determined.
4.1 Air Exposure* (CONTACT: Karen Blanchard, FTS 629-5519)
Pichloromethane;
In addition to occupational exposure, persons living near chemical
plants using dichloromethane may be exposed to it. Exposure may also
occur at industrial degreasing operations or in plastics processing.
Other exposures may be due to the use of paint remover or aerosols.
Tetrachloromethane;
Besides exposure in the workplace, persons living near tetrachloro-
methane or fluorocarbon production facilities are estimated to be the
most exposed.
TCE:
Persons living near chemical plants using or producing this chemical-
may be exposed to TCE in the ambient air. Also the general popula-
tion living near degreasing operations may be exposed to low concen-
trations.
PCE:
In addition to occupational exposures, persons living near dry
cleaning establishments, metal cleaning operations, or certain
chemical plants may be exposed to this chemical.
1,1,1-Trichloroethane:
Unnecessary exposure may occur at metal cleaning facilities, if
improperly operated. Perons living near chemical plants producing
this chemical or near degreasing operations may be exposed to
1,1,1-trichloroethane in the ambient air.
* Supplied by OAQPS.
4-1 July, 1982
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4.2 Water Exposure (CONTACT: Bill Coniglio, FTS 382-3035
Michael Slimak, FTS 426-2503)
The chlorinated organic solvents have been found In both surface and
ground water. The levels found In contaminated surface water are
usually In the low ppb range. However, a small percentage of ground
water supplies have been found to be contaminated by these chemicals
at much higher concentrations (i.e., 100-1,000 ppb). Contamination
of ground water to some degree has been detected in about 10 percent
of the sites examined. This contamination is most likely the result
of improper disposal of hazardous waste, industrial activities and/or
sub-surface disposal system discharges.
» 1982
-------
5. DATA BASES
5.1 NIH/EPA Chemical Information System (CIS)
This is a collection of various scientific data bases available
through an interactive computer program. The linking system between
these data files is the Structure and Nomenclature Search System
(SANSS). CIS can also provide a list of non-CIS sources of
information on a chemical of interest. For further information,
contact -Tim Cottrell at FTS 382-3546.
CIS contains numeric, textual, and bibliographic information in the
areas of toxicology, environment, regulations, and physical/chemical
properties. Several of these data bases are described below.
5.1.1 EPA Chemical Activities Status Report (EPACASR)
EPACASR is an on-line system containing information on EPA's interest
in chemicals. This system includes data on the Agency's regulations,
research, and assessments directed toward specific chemicals.
EPACASR is published annually and the data base is updated as
information is received. A searchable subset itemizes NTP/NCI
studies and results, as well as chemicals discussed in the IARC
monograph series. (Other sources are added as appropriate.) Entries
identify the statutory authority, the nature of the activity, its
status, the reason for and/or purposes of the effort, and a source of
additional information.
EPACASR is now available on CIS for internal use by EPA personnel and
is expected to be accessible from a public CIS account in the near
future. The publication and computer tapes are also available
through the National Technical Information Service (NTIS). For
FTS-3S2-3626.
5.1.2 Industry File Indexing System (IFIS)
IFIS is an on-line system which contains information relating to the
regulation of chemicals by EPA through industry-specific
legislation. IFIS enables the user to determine, for any particular
industry, which chemicals are used and produced and how these
chemicals are regulated. IFTS is currently available on CIS for
internal use by some EPA personnel and is expected to be accessible
from a public CIS account soon. For more information on IFIS,
contact Daryl Kaufman at FTS 382-3626.
5.1.3 Scientific Parameters in Health and the Environment,
Retrieval and Estimation (SPHERE)
SPHERE is being developed by the EPA Office of Toxic Substances as -a
system of integrated data bases, each representing a compilation of
extracted scientific data. The system is being released to the
public in stages as part of CIS, and the accessibility of component
data bases should be confirmed with the contact given below. The
components currently available (either through public CIS accounts or
5-1 July, 1984
-------
the internal EPA system) include: DERMAL, which provides
quantitative and qualitative health effects data on substances
admitted to humans and test animals via the dermal route; AQUIRE, a
component containing aquatic toxicity data for about 2,000 chemicals;
GENETOX, a mutagenicity data base; ISHOW, and ENVIROFATE, both of
which are compilations of physical/chemical parameters useful in
assessing environmental fate and transport. For more information
contact Paula Miles, FTS 382-3760.
5.1.4 Oil and Hazardous Materials Technical Assistance Data System
(OHMTADS)'
OHMTADS is a data base created by EPA to aid spill response teams in
the retrieval of chemical-specific response information. The file
currently contains data for approximately 1,200 chemicals including
physical/chemical, biological, toxicological, and commercial
information. The emphasis is on harmful effects to water quality.
OHMTADS is available to the public through CIS.
5.1.5 Chemical Evaluation Search and Retrieval System (CESARS)
CESARS provides detailed information and evaluations on a group of
chemicals of particular importance in the Great Lakes Basin. CESARS
was developed by the State of Michigan with support from EPA's Region
V. Presently, CESARS contains information on 180 chemicals including
physical-chemical properties, toxicology, carcinogenicity, and some
aspects of environmental fate. Information for most chemicals is
extensive and consists of up to 185 data fields. CESARS is
accessible through public CIS accounts.
5.2 Chemicals in Commerce Information System (CICIS)
CICIS is an on-line version of the inventory compiled under the
authority of TSCA. This law required manufacturers of certain
chemicals (excluding food products, drugs, pesticides, and several
other categories) to report production and import data to EPA. CICIS
contains production volume ranges and plant site locations (for 1977)
for over 58,000 chemical substances. There is also a Confidential
Inventory in which data for some chemicals are claimed confidential
and are not available in the public inventory. A version of CICIS
(TSCA Plant and Production, or TSCAPP) is now accessible through
CIS. For more information contact Geri Nowak at FTS 332-3568.
5.3 Chemical Substances Information Network (CSIN)
The Chemical Substances Information Network (CSIN) is not another
data base, but rather a sophisticated switching network. CSIN links
many independent and autonomous data and bibliographic computer
systems oriented to chemical substances, establishing a "library of
systems." Users may converse with any or all systems interfaced by
CSIN without training on these independent systems, regardless of the
hardware, software, data formats, or protocols of these information
resources.
5-2 July, 1984
-------
Information accessible through CSIN includes data on chemical
nomenclature, composition, structure, properties, toxicity,
production uses, environmental effects, regulations, disposal, and
other aspects of the life cycle of materials as they move through
society. Currently, twelve independent information resources are
accessible through CSIN, including: National Library of Medicine
(NLM); Chemical Information System (CIS); CAS-On-Line; SDC's ORBIT;
Lockheeds's DIALOG, and the Bibliographic Retrieval Service (BRS).
For further information contact Dr. Sid Siege 1 at FTS 395-7285.
5.4 Graphical Exposure Modeling System (GEMS)
EPA has developed GEMS, an interactive computer system, to provide a
simple interface to environmental modeling, physiochemical property
estimation, statistical analysis, and graphical display
capabilities. GEMS is being developed for use by the Office of Toxic
Substances to support integrated exposure/risk analyses. The system
provides environmental analysts who are unfamiliar with computer
programming with a set of sophisticated tools to undertake exposure
assessments. For information about the system and the current
accessibility of GEMS, contact Bill Wood at FTS 382-3928.
5-3 July, 1984
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6. REGULATORY STATUS (Current as oŁ 5/84)
6.1 Promulgated Regulations
6.1.1 EPA Programs
Clean Air Act (CAA)
o Section 111 - New source performance standards have been
promulgated to control fugitive emissions from the manufacture
of volatile organic chemicals (VOC's) from new process units
within the synthetic organic chemicals manufacturing industry.
Chemicals listed as VOC's include the following: (40 CFR
60.489(a)).
Carbon tetrachloride,
Di ch Lorome thane,
Perchloroethylene/
1,1,1-trichloroethane, and
Trichloroethylene (40 CFR 60.480-.489).
Clean Water Act (CWA)
o Section 311(b)(2)(A) - Carbon tetrachloride and
trichloroethylene are designated hazardous substances (40 CFR
116, Table 116.4A). General provisions, reportable quantities,
and notification requirements for discharges of hazardous
substances to navigable waters (40 CFR 117).
o Sections 318, 402, and 405(a) - National Pollutant Discharge
Elimination System (NPDES) permitting requirements (40 CFR
122). Permit applicants must report quantitative data for toxic
pollutants based on gas chromatographic and mass spectroscopic
analyses for the following:
Carbon tetrachloride,
Methylene chloride,
Perchloroethylene,
1,1,1-trichloroethane, and
Trichloroethylen-(40 CFR 122, App, D).
Other permitting requirements are covered in 40 CFR 123 and 40
CFR 124; NPDES standards and criteria are covered in 40 CFR 12 .
o Sections 301, 304, 306, 307, and 316 - Designated as toxic
pollutants {40 CFR 401.15):
Carbon tetrachloride,
1,1,1-trichloroethane,
Dichlorotne thane,
Tetrachloroethylene, and
Trichloroethylene.
6-1 July, 1984
-------
Accordingly, effluent limitations, new source performance
standards, or standards of performance for new and existing
sources have been promulgated for sections of the following
industries:
Electroplating1 (40 CPR 413.02U)),
Iron and steel manufacturing2 (40 CFR 420.02(p)) Subpart J,
Steam electric power generating (40 CFR 423, App. A),
Metal finishing' (40 CFR 433.11(e)),
Coil coating3 (40 CFR 465.02(j)),
Aluminum forming4 (40 CFR 467.02(p)),
Copper forming5 (40 CFR 468.02(r», and
Electrical and electronic components1 (40 CFR 469.12(a)).
Safe Drinking Water Act (SDWA)
o Part C, Sections 1421, 1423, 1424, 1431, and 1450 - Chlorinated
solventsaredesignated ashazardous wastesf40 CFR 144) as
defined in 40 CFR 261.3 and are subject to requirements covered
in the Underground Injection Control Program (UIC) (40 CFR 144)
to protect underground sources of water.
Resource Conservation and Recovery Act (RCRA)
o Sections 1006, 2002, 3001-3007, 3010, and 7004 - General
provisionsoF the hazardous waste management system (40 CFR
260).
o Sections 1006, 2Q02(a), 3001, and 3002 - Procedures for the
identification and listing of hazardous wastes:
Designated as hazardous waste from nonspecific sources are
wastes F001,- spent halogenated solvents used in degreasing:
perchloroethylene, trichloroethylene, dichloromethane,
1,1,1-trichloroethane, carbon tetrachloride, and sludges
from the recovery of these solvents; F002; spent halo-
Controls carbon tetrachloride, 1,1,1-trichloroethane,
dichloromethane, tetrachloroethylene, and trichloroethylene by
limiting total toxic organics (TTO's).
2Controls perchloroethylene only.
3Controls 1,1,1-trichlocoethane, dichloromethane, and
perchloroethylene by limiting TTO's.
4Controls perchloroethylene and trichloroethylene by limiting
TTO's.
5Controls 1,1,1-trichloroethane, dichloromethane, and
trichloroethylene by limiting TTO's.
6-2 July, 1984
-------
genated solvents: perchloroethylene, dichloromethane,
trichloroethylene, 1,1,1-trichloroethane, and the still
bottoms from the recovery of these solvents, and F024;
wastes including, but not limited to, distillation
residues, heavy ends, tars and reactor cleanout wastes from
the production of chlorinated aliphatic hydrocarbons,
having carbon content from one to five, utilizing free
radical catalyzed processes (40 CFR 261.31).
Designated as hazardous wastes from specific sources are:
K009 and K010: Distillation bottoms and side cuts
from the production of acetaldehyde from ethylene (40
CFR 261.32); Basis for listing K009, K010:
dichloromethane (App. VII),
K016: Heavy ends or distillation residues from the
production of carbon tetrachloride (40 CFR 261.32);
Basis for listing K016: carbon tetraehloride and
perchloroethylene (App. VII),
K019: Heavy ends from the distillation of ethylene
dichloride in EDC production (40 CFR 261.32); Basis
for listing K019; 1,1,1-trichloroethane, perchloro-
ethylene, carbon tetrachloride, and trichloroethylene
(App. VII),
K020: Heavy ends from the distillation of vinyl
chloride in VC monomer production (40 CFR 261.32);
Basis for listing K020: same as K019 (App.. VII),
K021: Aqueous spent antimony catalyst waste from
fluoromethanes production (40 CFR 261.32); Basis for
listing K021: carbon tetrachloride (App. VII),
K018: Heavy ends from the fractionation column in
ethyl chloride production (40 CF 261.32); Basis for
listing K018: trichloroethylene (App. VII),
K028: Spent catalyst from the hydrochlorinator
reactor iri the production of 1,1 ,1-trichloroethane
(40 CFR 261.32); Basis for listing K028: 1,1,1-
trichloroethane (App. VII),
K029: Waste from the product steam stripper in the
production of 1,1,1-trichloroethane (40 CFR 261.32);
Basis for listing K029: same as K028,
K073: Chlorinated hydrocarbon waste from the
purification step of the diaphragm cell process using
graphite anodes in cl.lo-ine production (40 CFR
261.32); Basis for listing K096: 1,1,1-
trichloroethane (App. VII).
6-3 July, 1984
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Commercial chemical products, manufacturing chemical
intermediates, or off specification commercial chemical
products, when discarded, are identified as hazardous toxic
wastes unless otherwise designated and are subject to the
small quantity exclusion (for generators) defined in 40 CFR
261.5(a) and (f) are:
U211: Carbon tetrachloride,
U080: Dichloromethane,
U226: 1,1,1-trichloroethane (methyl
chloroform),
U210: Perchloroethylene, and
U228: Trichloroethylene.
The above chlorinated solvents are listed in 40 CFR
261.33(f).
Listed as hazardous constituents
{40 CFR 261, App. VIII):
1,1,1-Trichloroethane,
Dichloromethanet
Carbon tetrachloride,
Trichloethylene, and
Perchloroethylene.
o Sections 3002 to 3006 - Wastes identified as hazardous
under Section 3001 are subject to a "cradle to grave"
management system. Standards are established for
generators of hazardous waste for hazardous waste
determination (40 CFR 262.11)? packaging, labeling, and
marking (40 CFR 262.30-.34); recordkeeping and reporting
{40 CFR 262.40-.43). Standards for transporters of
hazardous waste are covered under 40 CFR 263. Additional
control standards covering treatment, storage, and disposal
facilities (40 CFR 264 and 265). Permit procedures are
included in the consolidated permit regulations covered in
40 CFR 122 to 124.
Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA)
o Sections 2-12, 19, 21, and 25 - 1,1,1-Trichloroethane is
designated as an inert ingredient when used as a diluent in
antimicrobial products unless determined to be otherwise by the
Agency (40 CFR 162.60(d)).
Toxic Substances Control Act (TSCA)
o Section 8(a) - Requirements for the submittal of preliminary
assessment reporting apply to:
Carbon tetrachloride and
1,1,1-trichloroethane
6-4 July, 1984
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(40 CFR 712.30(d)).
o Section 8(d) - Requirements for the submission of lists and
copies of health and safety studies apply to:
Carbon tetrachlonde,
1,1,1-trichloroethane
(40 CFR 716).
Federal Food, Drug, and Cosmetic Act (FFDCA) - Administered by EPA
o Section 409 - Carbon tetrachloride may be used as a fumigant in
or on grain-mill machinery.
(21 CFR 193.225(a)J
o Section 409 - The use of carbon tetrachloride with carbon
disulfide or ethylene dichloride with or without pentane as a
pesticide. (21 CFR 193.230(a)(1))
o Section 408(d)(2) - 21 U.S.C. 346a(d)(2)
The following are exempted from the requirement of a
pesticide tolerance: tetrachloroethylene; when used as a
solvent or cosolvent at a level of not more than 0.6
percent of the pesticide formulation and 1,1,1-
trichloroethane; when used as a solvent or cosolvent, and
when applied to growing crops or to raw agricultural
commodities after harvest (40 CFR 180.1001(c)):
dichloromethane; when used as a solvent or cosolvent in
pesticide formulations applied to growing crops only (40
CFR 180.1001(d)): dichloromethane, tetrachloroethylene,
and 1,1,1-trichloroethane, (not more than 25 percent), when
used as solvents or cosolvents in pesticide formulations
applied to animals (40 CFR 180.1001(e)).
The following are exempted from the requirement of a
tolerance for residues, when used as a fumigant after
harvest on the grains, barley, corn, oats, popcorn, rice
sorghum (milo), wheat; and when used in the post-harvest
fumigation of citrus fruits:
Carbon tetrachloride (40 CFR 180.1005),
Dichloromethane (40 CFR 180.1010),
1,1,1-trichloroethane (40 CFR 180.1012).
'Dichloromethane and 1,1,1-trichloroethane only.
6-5 July, 1984
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6.1 .2 Programs of Other Agencies
OS HA - Occupational Safety and Health Act
o General industry standards for employee exposure to air
contaminants in the workplace (29 CFR 1910.1000).
1,1 ,1-tr ic hloroe thane (methyl chloroform), Table Z-1,
Carbon tetrachloride (Table Z-2),
Dichlorome thane (Table Z-2),
Tetrachloroethylene, (Table Z-2),
Trichloroethylene (Table Z-2).
o Regulations establishing employee access to exposure and medical
records which contain any information concerning that employee's
exposure to any harmful physical agents or toxic substances; the
latter of which are listed in the latest printed edition of
RTECS or are regulated by any Federal law or rule due to a
hazard to health (29 CFR 1910.20).
FDA - Federal Food, Drug, and Cosmetic Act
o The use of dichlorome thane as a diluent in color additive inks
for marking fruit and vegetables (21 CFR 73.1 (b) (1 ) (ii) ) .
o Solvents permitted to be used as food-grade extractants in the
preparation of the exempt color additive annatto extract (21 CFR
Dichloromethane and
Trichloroethylene .
Solvents permitted to be used as extractants in the preparation
of the exemp^ color additive paprik oleoresin (21 CFR
73.345(a)(D), and turmeric oleoresin (21 CFR 73.6l5(a) ( 1 ) ) :
Dichloromethane and
Trichloroethylene .
Solvents permitted to be used as extractants in the manufacture
of modified hops extract for beer (21 CFR 172.560(b) (3-6) ) :
Dichloromethane and
Trichloroethylene.
Sections 409, 701 (21 U.S.C. 348, 371) - Tetrachlorome thane
(carbon tetrachloride) is permitted as a substance from which
anti-offset powders for use as components of paper and paper-
board intended for use in food manufacturing process (21 CFR
176.130(cJ), and as a component of uncoated and coated
paperboard that contacts dry food (21 CFR 176.180(b) (2) ) .
6-6 July, 1984
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o Sections 201(s), 409 (21 U.S.S 321(s), 348) - Dichloromethane
(methylenechloride)Isacceptedasan" optional adjuvant
substance which may be used in the production of polycarbonate
resins intended for use in food manufacturing processes
{21 CFR 177.1580(b)).
o Trichloroethylene is permitted to be used as a chain transfer
agent in the production of vinyl chloride-hexene-1 copolymers as
components of articles intended for use in contact with food (21
CFR 177.1960(a)}.
o Tetrachloroethylene is approved for use as an adjuvant in the
manufacture of foamed plastics intended for use in contact with
food? when it is used as a blowing agent adjuvant in polystyrene
at a level not exceeding 0.3 percent by weight
(21 CFR 178.3010).
o Sections 201-902 - Guidelines for aerosol drug products for
human use that contain 1,1,1-trichloroethane (21 CFR 310.507).
o Sections 409 and 701 - Approves for the jse as components of
adhesives, the following:
Carbon tetrachloride,
Dichloroiaethane,
Tetrachloroethylene,
Trichloroethylene, and
1,1,1-trichloroethane (21 CFR 175.105).
o Tolerances for residues of trichloroethylene resulting from its
use as a solvent in the manufacture of certain foods (21 CFR
173.290). The foods and tolerances are presented in Section
7.4.
o Section 409 - Approves dichloromethane (methylene chloride) for
use as a secondary food additive in foods for human consumption
(21 CFR 173.255). The permissible levels and foods are
presented in Section 7.4.
o Section 409 and 701 - Approves the use of tetrachloroethylene as
an indirect food additive, adjuvant, production aid or sanitizer
(21 CFR 178.3010).
CPSC - Federal Hazardous Substances Act
o Section (2)(g)(1)(B) - Tetrachloromethane (carbon tetra-
chloride) and mixtures containing it (including CC14 and
mixtures containing it in fire extinguishers) declared banned
from interstate commerce (16 CFR 1500.17(2)).
o Section (2){F)(2) - Visual novelty devices containing no more
than 105 ml of tetrachloroethylene are exempt from the labeling
requirements of Title 21 Part 1500.121U). (21 CFR 1500.83(31)
(i-ii)).
6-7 July, 1984
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DOT - Hazardous Materials Transportation Act
o Regulations and procedures for the packaging requirements for
transportation of hazardous materials via rail, air, vessel, and
over public highways (49 CFR 172.101 and .102, 173, 174, 175,
176, and 177). Chemicals subject to these provisions are:
Carbon tetrachloride,
Dichloromethane,
1,1,1-trichloroethane,
Perchloroethylene, and
Trichloroethylene.
DOT/Coast Guard - Port and Tanker Safety Act
o Regulation pertaining to compatibility of bulk liquid hazardous
materials on tank vessels (46 CFR 150, Subpart A).
Carbon tetrachloride,
Dichloromethane,
Trichloroethylene, and
Perchloroethylene.
o Interim regulations governing foreign flag vessels carrying
certain hazardous cargoes in U.S. waters (46 CFR 154a).
Carbon tetrachloride,
Dichloromethane.
DOT/Coast -Guard - Port and Tanker Safety Act/Dangerous Cargoes Act
o Regulations and standards for unmanned barges carrying certain
bulk dangerous cargoes (46 CFR 151).
Carbon tetrachloride,
Dichloromethane,
Tetrachloroethylene, and
Trichloroethylene.
o Regulations and standards for self-propelled shipping vessels
carrying hazardous liquids (46 CFR 153, Table 1).
Carbon tetrachloride,
Dichloromethane,
Tetrachloroethylene, and
Trichloroethylene.
6-8 July, 1984
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6.2 Proposed Regulations
6.2.1 EPA Programs
CAA
CWA
Section 111 - EPA has proposed new source performance standards
to limit emissions of volatile organic carbons (VOC's) from new,
modified, and reconstructed air oxidation facilities within the
synthetic organic chemicals manufacturing industry (48 FR 43932,
October 21, 1983); and for VOC emissions from the synthetic
organic chemicals manufacturing industry distilling operations
(48 FR 57538, December 30, 1983).
EPA has also proposed new source performance standards to limit
emissions of VOC's from new, modified, and reconstructed
petroleum solvent dry cleaning facilities installed at any
petroleum dry cleaning plant which consumes more than "',800
liters (4,700 gallons) of petroleum solvent annually (47 FR
56118, December 14, 1982).
o Sections 301, 304, 306, 307, and 501 - EPA has proposed to
establish effluent guidelines, new source performance standards
(NSPS) and performance standards for new and existing sources
(PSNS and PSES) for the organic chemicals and plastics and
synthetic fibers point source category (40 CFR 414 and 416) by
regulating the following: (48 FR 11852, March 21, 1983).
Carbon tetrachloride,
1,1,l-trichloroethane,
Dichloromethane, and
Trichloroethylene.
o Proposed effluent guidelines, NSPS, PSNS. and PSES for pesticide
chemicals manufacturing (40 CFR 465) by regulating the
following:
Carbon tetrachloride,
Dichloromethane.
(47 FR 54010, November 30, 1982).
SDWA
o Section 14T2 - EPA has proposed regulations establishing
Recommended Maximum Contaminant Levels (RMCLs) for the following
volatile synthetic organic chemicals (VOCs) in drinking water:
(49 FR 24330, June 12, 1984).
Carbon tetrachloride,
1,1,1-trichLoroethane,
6-9 July, 1984
-------
Tetrachloroethylene, and
Trichloroethylene.
RCRA
0 Section 3001 - EPA is proposing to establish as a toxic
hazardous waste stream, F025; light ends, spent filters and
filter aids, and spent dessicant wastes from the production of
chlorinated aliphatic hydrocarbons having carbon content from
one to five, utilizing free radical catalyzed processes. The
hazardous constituents for which the waste stream is listed
include:
Carbon tetrachloride,
Dichloromethane,
1,1,1-trichloroethane,
Tetrachloroethylene, and
Trichloroethylene.
(49 FR 5315, February 10, 1984)
TSCA
o Section 4(a) - EPA has withdrawn the proposed health and
environmental effects testing requirements for the following:
Methylene chloride and
1,1,1-trichloroethane
(49 FR 25009 and 25013, June 19, 1984).
Comprehensive Environmenta1 Response, Compensation and Liability
Act (CERCLA)
CERCIA provides for the liability, compensation, clean-up and
emergency response for the release of hazardous substances into
the environment. This Act also deals with the cleanup of
hazardous waste disposal sites (42 USC 9601; PL 96-510). EPA is
developing regulations concerning the designation of hazardous
substances, the development of reportable quantities (RQ),
claims procedures, and the confidentiality of business records
(46 FR 54032). Revisions to the National Contingency Plan (NCP)
as required by CERCLA have been issued in a proposed rule (47 FR
10972).
The chemicals listed below are designated hazardous substances
under CERCLA and will be subject to regulations developed under
Superfund. EPA has proposed adjustments to many of the RQ's
established under CERCLA and the CWA (48 FR 23552):
Carbon tetrachloride,
Perchloroethylene,
Dichloromethane,
6-10 July, 1984
-------
1,1,1-trichloroethane, and
Trichloroethylene.
6.3 Other Actions
Public Health Service (PHS) - National Toxicology Program (NTP)
o Published FY '84 plans for the testing of tetrachloroethylene to
determine mutagenicity in L5178Y mouse lymphoma cells (Chemical
Regulation Reporter, May 4, 1984, page 170).
o Carbon tetrachlonde is cited as a substance that may reasonably
be anticipated to be a carcinogen (Biird Annual Report on
Carcinogens, Summary, September 1983, page 38).
o Published FY '83 plans for testing 1,1,1-trichloroethane for
cytogenetic effects in Chinese Hamster ovary cells (48 FR 17246,
April 21, 1983); and for testing perchloroethylene for heritable
genetic effects in Drgspphilia in FY '82 (48 FR 17247).
EPA
Announced availability of Draft Health Assessment Document for
perchloroethylene (49 FR 10575, March 21, 1984).
EPA - CWA
Section 3Q4(g) - Standard analytical test procedures are
established for chlorinated organics (40 CFR 136} as defined in
Sections 401 and 403 of Title 40.
Section 311(c)(2) - A methodology for rating uncontrolled
hazardous waste sites by establishing quantity and waste
characteristics determination parameters is set (40 CFR 300,
Subpart H, Appendix A and Tables 4-5).
6-11 July, 1984
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7. STANDARDS AND RECOMMENDED CRITERIA*
7.1 Air
OSHA Standard for workplace exposure to the solvents in air (29
CFR 1910.1000, Tables Z-1 and Z-2).
TWA Acceptable
8-hr. avg. ceiling
Di ch lorome thane
Carbon tetrachloride
Perch loroe thylene
Tr i ch lor oe thy 1 ene
1,1,1 -Trichloroethane
500 ppm
10 ppm
100 ppm
100 ppm
350 ppm
American Conference of Governmental and
(ACGIH)
Recommended threshold limit values
Di ch lorome thane
Carbon tetrachloride
Perch loroe thylene
Trichloroe thylene
1,1,1 -Trichloroethane
1 ,000 ppm
25 ppm
200 ppm
200 ppm
N/A
Industrial Hygienists
for 1980:
TWA
200 ppm
10 ppm
100 ppm
100 ppm
350 ppm
STEL
(tentative)
250 ppm
20 ppm
150 ppm
150 ppm
450 ppm
7.2 Water
Water Quality Criteria (45 PR 79318)
Freshwater aquatic life (acute exept where indicated):
Dichloromethane 11,000 jug/1
Carbon tetrachloride 35,200 pg/1
Trichloroethylene 45,000 ug/1
Tetrachloroethylene 5,280 pg/1
840 pg/1 (chronic)
1,1,1-Trichloroethane 18,000 pg/1
Saltwater aquatic life (acute except where indicated)
Dichloromethane 12,000 pg/1
Carbon tetrachloride 6,400 pg/1 (chronic)
50,000 pg/1
Trichloroethylene 2,000 pg/1
See Appendix A for a discussion of the derivation, uses, and
limitations of these criteria and standards.
7~1 JUly, 1984
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Tetrachloroethylene 10,200 «g/l
450 ug/1 (chronic)
1,1,1-Trichloroethane 31,200 ug/1
Water Quality Criteria for the Protection of Human Health
corresponding to a 10~5 lifetime cancer risk by ingestion of
contaminated water and contaminated aquatic organisms3 and
contaminated aquatic organisms only:
Criteria Limits
Dichloromethane 1.9 ug/la 157 ug/lb
Carbon tetrachloride 4.0 ug/la 69.4 ug/lb
Perchloroethylene 8 ug/la 88.5 ug/lb
Trichloroethylene 27 ug/la 807 ug/lb
Water Quality criteria for the protection of human health by
ingestion of water and contaminated aquatic organisms
(noncarcinogenic risk)
1,1,1-Trichloroethane 18,400 y g/1
Designated as hazardous substances under Section 311 of the OTA,
notification is required if discharges exceed the following:
Carbon tetrachloride 5,000 Ibs
Trichloroethylene 1,000 Ibs
{40 CFR 117.3) the proposed regulation is the same (43 PR 23577
and 23595).
the Office of Drinking Water has issued Health Advisories; the
Suggested Ho Adverse Response Levels (SNARLs) are:
Dichloromethane 13,000 ug/1 (one day)
1,300 ug/1 (ten days)
150 ug/1 (chronic)
Carbon tetrachloride 200 ug/1 (one day)
20 ug/1 (ten days)
Trichloroethylene 2,000 jig/1 (one day)
200 ug/1 (ten days)
75 ug/1 (chronic)
7~2 July, 1984
-------
Tetrachloroethylene 2,300 ug/1 (one day)
175 ug/1 (ten days)
20 ug/1 (chronic)
1,1,1-Trichloroethane 1,000 ug/1 (chronic)
Draft - Office of Drinking Water ANPRM Potential Maximum
Contaminant Levels (PMCLs), (47 FR 9351).
Carbon tetrachloride 5-500 ug/1
Trichloroethylene 5-500 ug/1
Perchloroethylene 5-500 ug/1
1,1,1-Trichloroethane 1,000 ug/1
Proposed RMCLS (49 FR 24352) are zero for the following VOGs:
Carbon tetrachloride,
Tetrachloroethylene, and
Trichloroethylene.
The proposed RMCL for 1,1,1 -tnchloroethane is
0.2 mg/1 (49 FR 24352).
7.3 Hazardous Waste
The chlorinated organic solvents are listed as toxic waste and are
subject to the small quantity exclusion; any disposal of more than
1,000 kg per month of hazardous waste is subject to RCRA
regulations (40 CFR 261-33(f)).
7.4 Other
FDA tolerance levels of solvents in food.
Dichloromethane (21 CFR 173.255)
Extractant for spice
oleoresins (if other
chlorinated solvents
are present, total
residue must be less
than 30 ppm) 30 ppm
7-3 ' July, 1984
-------
Hops extractant; the
limit is 2.2% provided
than the hops extractant
is added before the beer
production process
Extractant for removal
of caffeine from coffee
ground coffee
instant coffee
Trichloroethylene [21 CFR 173.290)
Extractant for spice
oleoresins (if other
chlorinated solvents
are present, total
residue must be less
than 30 ppm)
Extractant for removal
of caffeine from coffee
Decaffinated ground coffee
Decaffinated soluble
(instant) coffee
10 ppm (residue)
10 ppm (residue)
30 ppm
10 ppm (residue)
10 ppm (residue)
7-4
July, 1984
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8. SPILL OR OTHER INCIDENT CLEAN-UP/DISPOSAL
(CONTACT: National Response Center, 800-424-8802; in Washington area,
426-2675)
8.1 Hazards and Safety Precautions
The combustion products of these chlorinated organic solvents are
highly toxic and may be fatal if inhaled, swallowed or absorbed through
the skin. Contact may cause burns to skin and eyes. Runoff from fire
control or dilution water may cause pollution.
Store in cool, dry, well-ventilated area.
8.2 First Aid
Move victim to fresh air; call emergency medical care. If not
breathing, give artificial respiration. If breathing is difficult,
give oxygen. In case of contact with material, immediately flush skin
or eyes with running water for 15 minutes. Speed in removing material
from skin is of extreme importance. Remove and isolate contaminated
clothing and shoes. Keep victim quiet and maintain normal body
temperature. Effects may be delayed; keep victim under observation.
8.3 Emergency Action
Avoid contact and inhalation of the spilled cargo. Stay upwind; notify
local fire, air, and water authorities of the accident. Keep
unnecessary people away. Wear "acid" goggles and use self-contained
(positive pressure) breathing apparatus and special protective
clothing.
It should be noted that PVC and natural rubber should not be used. Use
Neoprene for protective clothing. Do not use closed-circuit
rebreathing system employing soda lime or other carbon dioxide absorber
because of formation of toxic compounds capable of producing cranial
nerve paralysis. Equipment should not be iron or metal, susceptible to
hydrogen chloride.
OHM-TADS recommends the following action: seek professional
environmental engineering assistance through EPA's Environmental
Response Team (ERT), Edison, NJ, 24-H at 201-321-6660. Contain and
isolate spill by using clay/bentonite dams, interceptor trenches, or
impoundments. Construct swale to divert uncontaminated portion of
watershed around contaminated portion. Seek professional help to
evaluate problem; implement containment measures and conduct bench
scale and pilot scale tests prior to full scale decontamination program
implementation. Density stratification and impoundment—remove product
from bottom layer by pumping through manifold or polyethylene rope mop
collection or remove clarified upper portion by skimmers or siphon.
Treatment is required for both clarified and concentrated product
fractions. Treatment alternatives include powdered activated carbon,
granular activated carbon, and biodegradation. Treatment alternatives
for contaminated soils include well point collection and treatment of
leachates as for contaminated waters, bentonite/cement injection to
8-1 July, 1984
-------
immobilize spill. Contaminated soil residues may be packaged for
disposal.
Although these chemicals are not flammable, high temperature can cause
decomposition which can produce very toxic decomposition products
(i.e., phosgene, hydrogen chloride, etc.).
Remove container from fire area if it can be done without risk. Cool
containers that are exposed to flames with water from side until well
after the fire is out. Fight fire from maximum distance.
8.4 Notification and Technical assistance
Section 103(a) and (b) of the Comprehensive Environmental Response,
Compensation, and Liability Act (CERCLA) of 1980 require persons who
release hazardous substances into the environment in reportable
quantities determined pursuant to Section 102 of the Act to notify the
National Response Center (NRC): 800-424-8802 (Washington, D.C. 426-
2675).
All the chlorinated organic solvents are designated as hazardous under
CERCLA. Their reportable quantities are as follows: dichloromethane
(100 Ibs.), tetrachloromethane (5000 Ibs.), TCE (1000 Ibs.), PCE (100
Ibs.), and 1,1,1-trichloroethane (100 Ibs.). EPA has proposed an
adjustment of the RQ to 1 Ib. for dichloromethane, PCE, and 1,1,1-
trichloroethane (Federal Register, May 25, 1983, p. 23587, 23594, and
23595).
For technical assistance, call CHEMTREX (Chemical Transporation
Emergency Center): 800-424-9300. Other sources of technical
information are: (1) the EPA's Oil and Hazardous Materials Technical
Assistance Data System (OHMTADS) contained within the NIH-EPA Chemical
Information System (CIS) which provides information pertinent to emer-
gency spill response efforts, and (2) the CHRIS System which provides
information on first aid, physical/chemical properties, hazard
assessments, and response methods. Both systems can be accessed
through NRC.
8.5 Disposal
The chlorinated organic solvents are subject to Subpart D regulation
under RCRA only if 1000 kg of the commercial product is disposed of in
one month (40 CFR 261.33).
The following nonspecific and specific wastestreams, which contain one
or more of the solvents, are also subject to RCRA regulations (40 CPR
261.31 and 261.32).
(1) The spent halogenated solvents used in degreasing; PCE, TCE,
methylene chloride, 1,1,1-trichloroethane, carbon tetrachloride,
and sludges from the recovery of these solvents (FOOD.
(2) The spent halogenated solvents; PCE, TCE, methylene chloride,
1,1,1-trichloroethane and the still bottoms from the recovery of
these solvents (F002).
8-2 July, 1984
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(3) Wastes including, but not limited to, distillation residues,
heavy ends, tars, and reactor cleanout wastes from the
production of chlorinated aliphatic hydrocarbons, having carbon
content from one to five, utilizing free radical catalyzed pro-
cesses (F024).
(4) Distillation bottoms from the production of acetaldehyde from
ethylene (K009).
(5) Distillation side cuts from the production of acetaldehyde from
ethylene (K010).
(6) Heavy ends or distillation residues from the production of
carbon tetrachloride (K016).
(7) Heavy ends from the fractionation column in ethyl chloride
production (K018).
(8) Heavy ends from the distillation of ethylene dichloride in EDO
production (K019).
(9) Heavy ends from the distillation of vinyl chloride in VC monomer
production (K020).
(10) Aqueous spent antimony catalyst waste from fluoromethanes
production (K021).
(11) Spent catalyst from the hydrochlorinator reactor in the
Production of 1,1,1-trichloroethane (K028).
(12) Waste from the product steam stripper in the production of
1,1,1-trichloroethane (K029).
(13) Chlorinated hydrocarbon waste from the purification step of the
diaphragm cell process using graphite anodes in chlorine
production (K073).
8-3 July, 1984
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9. SAMPLING, ACCEPTABLE ANALYTICAL TECHNIQUES, AND QUALITY ASSURANCE
9.1. Air (CONTACT: Robert Jungers for PCE, FTS 629-2331;
Joseph F. Walling for the other solvents, FTS 629-7954).
PCE is not a criteria air pollutant; therefore, no Agency-approved or
reference procedure is available. A procedure using charcoal for
sampling and gas chromatography with flame ionization detectors (FID)
and/or electron capture detectors (BCD) for analysis has been used for
ambient monitoring around metal degreasing and commercial dry cleaning
facilities ("Development of a Measurement Method for Perchloroethylene
in Ambient Air," RTI/V507/1Q-01F, March 1979). Confirmation analysis
is made using gas chromatography for component separation and mass
spectrometry for analysis.
The method was evaluated in coin-operated1 dry cleaning establishments
and in the peripheral ambient atmosphere-. Indoor concentrations of PCE
ranging from 100 ppb to 10,000 ppb, were collected for eight hours at a
sampling rate of 60 cm^/rnin. Outdoor (ambient) concentrations' of PCE
ranging from less than 1 ppb to 30 ppb, were collected for 24 hours at
a sampling rate of 230 cnr/inin.
The total method precision determined by analysis of replicate field
samples ranged from 1-2.2 percent to 18.1 percent relative standard
deviation. The laboratory method precision determined by replicate
analyses of samples ranged from 1.43 percent to 6.57 percent relative
standard deviation. The average percent PCE recovery efficiency, at
the 95 percent confidence interval, of quality control spiked sample
analyses ranged on inside samples from 86.4 ±' 10.2 to 98.5 ± 2.9 and on
outside samples from 60.1 ±< 1.9> to 84.6 ± 8.9.
The quality assurance program for this evaluation consisted of the
following:
o Triplicate samples were collected at selected sites to determine
field method precision.
o Samples were distributed to three laboratories to detect possible
bias.
o External QA spiked samples were distributed to determine accuracy of
analysis.
Like PCE, dichloromethane, tetrachloromethane, TCE, and 1,1,1-
trichloroethane are not criteria air pollutants; therefore, no Agency-
approved or reference' procedure is available.
A procedure using Tenax adsorbent for sampling and gas
chromatography/mass spectroraetry (GC/MS) for analysis has been used but
little is known about the precision and accuracy of the procedure.
GC/MS requires special- expertise and expensive, sophisticated
equipment. For these reasons, monitoring for one compound alone using
the Tenax GC/MS procedure is rarely cost-effective and the approach is
most suitable when monitoring for an array of volatile compounds is
des ired.
9-1 July, 1984
-------
The preparation of Tenax suitable for sampling is demanding. Tenax
background is a problem that must be addressed. Precautions about
permissible maximum air volumes, sampling rates and ambient
temperatures during sampling must be observed and these, in turn,
govern allowable sampling times.
Detection limits and accuracy are not known; reproducibility is
estimated to be 50-100 percent. Quality assurance materials composed
of blank Tenax sampling cartridges spiked with known amounts of solvent
can be prepared and must be used in any monitoring program.
9.2 Water (CONTACT: Thomas Bellar, FTS 684-7311 or
James Lichtenberg, FTS 684-7308)
The chlorinated organic solvents are all parameters under Section
304{h) of the Clean Water Act. Information has been supplied on all
the chlorinated solvents except 1,1,1-trichloroethane. However, the
analytical procedures should be analogous.
There are several approved and proposed gas chromatographic procedures
for the analysis of the chlorinated solvents in natural, waste, and
drinking waters.
The primary differences between the methods are the extraction
procedure and the means of injecting the extracts into the gas
chromatograph. Mass spectrometry and halogen specific detectors are
normally used to improve qualitative accuracy.
Direct Aqueous Injection EPA ft Method 8 t1)
ASTM # D 2908-74 12)
Major Equipment Required: Gas chromatograph
One to 5 ul of the neat sample is injected directly into the gas
chromatograph. The method detection limit is approximately 1 mg/1 when
mass spectrometry, flame ionization or halogen specific detectors are
used. For nickel-63 electron capture detectors the method detection
limit is approximately 1 ;ig/1.
Liquid-Liquid Extraction EPA # 501.2(3)
ASTM - To be included in the 1981
Annual Book of ASTM standards
Major Equipment Required: Gas chromatograph
A small volume of sample is extracted once with a low boiling water
insoluble solvent, such as pentane. Sample/solvent ratios of 5:1 are
commonly used. One to five ul of the extract is then injected into a
gas chromatograph equipped with an elecron capture detector. The
method detection limit is approximately 1.0 ug/1.
Purge and Trap EPA ft 601,(4)625,(4)502.1,(5)
ASOM # D-3871-79(6)
Standard Methods - included in the 15th Edition
9-2 JUlyi 1984
-------
Major Equipment: Gas chromatograph and purge and trap apparatus.
Five ml of the aqueous sample is placed into a purging device. The
solvent and other volatile water insoluble organic compounds are
transferred from the aqueous phase to the gas phase. The volatilized
compounds are swept from the purging device by the purge gas and are
trapped in a short column containing a suitable sorbant. After a
predetermined period of time the trapped compounds are thermally
desorbed and backflushed into a gas chromatograph equipped 'With a mass
spectrometer, flame ionization or a halogen specific detector.
The method detection limit for the mass spectrometer (full scan) and
for the flame ionization detector is approximately 1 pg/1. For a
carefully optimized halogen specific detector method, detection limits
as low as 20 ng/1 have been achieved.
Samples are collected in narrow-mouth screen-cap bottles with TFE
fluorocarbon seals. Samples are stored head-space free at 4°C in the
dark. Sodium thiosulfate is normally used to remove free residue
chlorine. Spiked river water samples have been stored for up to 27
days under'these conditions with no apparent losses.
Single laboratory test data on simple spiked matrices have been
collected by EPA. Intralaboratory accuracy and precision and method
detection limit data are currently being collected. Quality control
and performance evaluation samples (methanolic concentrates containing
solvent to be spiked into water) are available from the Environmental
Monitoring and Support Laboratory, Quality Assurance Branch, USEPA,
Cincinnati, Ohio 45268.
References for Water Analysis
1. "A Method for Organochlorine Solvents in Industrial
Effluents." National Pollutant Discharge Elimination System
Appendix A, Federal Register 38, No. 7S Pt. II.
2. "Standard Test Method for Measuring Volatile Organic
Matter in Water by Aqueous - Injection Gas Chromatography," Annual
Book of ASOM Standards, 1980, Part 31, Water, ASTM D-2908-74.
3. Federal Register, Thursday, November 29, 1979, Volume 44. No. 231,
40 CFR, Appendix C - Parts I and II.
4. Federal Register, Monday, December 3, 1979, Volume 44, No. 233, 40
CFR Part 136, Guidelines Establishing Test Procedures for the
Analysis of Pollutants.
5. "The Determination of Halogenated Chemical Indicators of Industrial
Contamination in Water by the Purge and Trap Method." Method 502.1,
September 1980, USEPA, Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio 45268.
6. "Standard Test Methods for Measuring Purgeabie Organic Compounds in
Water Using Headspace Sampling," ASTM D-3871-79, Part 31, Water,
Annual Book of ASTM Standards, 1980.
9-3 July, 1984
-------
LIST OF PROCEDURES FOR DICHLOROMETHANE
Method
EPA 624
EPA 601
EPA 502.1
EPA 501 .2
EPA 8
Standard Methods
ASTM D-2098-74
ASTM-D-3871-79
Type
P&T
P&T
P&T
LLE
DAI
P&T
DAI
P&T
MDL
2.8
0.25 ug/1
ND
ND
1 mg/1
ND
ND
ND
Recovery3
(%)
66-82
90.7
84
ND
ND
ND
ND
ND
Standard
Deviation
(%)
46-66
4.6
12
ND
ND
ND
ND
ND
Status
Proposed
Proposed
Proposed
Untested
Official13
Untested
Untested
Untested
P&T = Purge and Trap
LLE = Liquid/Liquid Extraction
DAI = Direct Aqueous Injection
Status - As of March 1981.
a Single laboratory recovery from spiked reagent water or wastewater.
b Official for the analysis of organohalides in wastewater.
Method
EPA 624
EPA 601
EPA 502.1
EPA 501.2
EPA 8
Standard Methods
ASTM D-2098-74
ASTM-D-3871-79
LIST OF
Type
P&T
P&T
P&T
LLE
DAI
P&T
DAI
P&T
PROCEDURES FOR TETRACHLOROMETHANE
MDL
2.8 ug/1
0.12 ug/1
<0.1 ug/1
<1 ug/1
1 mg/1
ND
ND
ND
Recovery*
(%)
91
88
90
ND
ND
ND
ND
ND
Standard
Deviation
(%)
23
26
7
ND
ND
ND
ND
ND
Status
Proposed
Proposed
Proposed
Untested
Official13
Untested
Untested
Untested
P&T = Purge and Trap
LLE = Liquid/Liquid Extraction
DAI = Direct Aqueous Injection
Status - As of March 1981.
a
b
Single laboratory recovery from spiked reagent water or spiked wastewater.
Official for the analysis of organohalides in wastewater.
9-4
July, 1984
-------
LIST OF PROCEDURES FOR TRICHLOROETHENE
Method
EPA 624
EPA 601
EPA 502.1
EPA 501 .2
EPA 8
Standard Methods
ASTM D-2098-74
ASOM-D-3871-79
Type
P&T
P&T
P&T
LLE
DAI
PST
DAI
PST
MDL
1 .9 ug/1
0.1
ND
ND
1 mg/1
ND
ND
ND
Recovery3
(%)
106-110
96
94
ND
ND
ND
ND
ND
Standard
Deviation
(%)
14-22
14
6.0
ND
ND
ND
ND
ND
Status
Proposed
Proposed
Proposed
Untested
Official1*
Untested
Untested
Untested
P&T = Purge and Trap
LLE = Liquid/Liquid Extraction
DAI = Direct Aqueous Injection
Status - As of March 1981.
a
b
Single laboratory recovery from spiked reagent water or wastewater.
Official for the analysis of organohalides in wastewater.
LIST OF PROCEDURES FOR TETRACHLOHOETHENE
Method
EPA 624
EPA 601
EPA 502.1
EPA 501.2
EPA 8
Standard Methods
ASTM D-2098-74
ASTM-D-3871-79
Type
P&T
P&T
P&T
LLE
DAI
P&T
DAI
P&T
MDL
4 ug/1
.03 ug/1
ND
ND
1 mg/1
ND
ND
ND
Recovery3
<%>
97-99
97
90
ND
ND
ND
ND
ND
Standard
Deviation
.1%)
13-26
16
10
ND
ND
ND
ND
ND
Status
Proposed
Proposed
Proposed
Untested
Official15
Untested
Untested
Untested
P&T = Purge and Trap
LLE = Liquid/Liquid Extraction
DAI = Direct Aqueous Injection
Status - As of March 1981.
a
b
Single laboratory recove-ry from spiked reagent water or wastewater.
Official for the analysis of organohalides in wastewater.
9-5
July, 1984
-------
9.3 Solid Waste
The chlorinated organic solvents being discussed may be determined as
described by Method 8010 in Test Methods for Evaluating Solid Waste,
Physical/Chemical Methods (Office of Solid Waste and Emergency
Response, July 1982, SW-846, Second Edition). Method 8010 is used to
determine the concentration of various halogenated volatile organic
compounds in groundwater, liquid, and solid matrices.
Specifically, Method 8010 provides cleanup and GC conditions for the
detection of halogenated volatile organic compounds including the
compounds under discussion. Haste samples can be analyzed using direct
injection, the headspace method (Method 5020) or the purge-and-trap
method (Method 5030). Groundwater samples should be determined using
Method 5030. A temperature program is used in the gas chromotograph to
separate the organic compounds. Detection is achieved by a halide-
specific detector (HSD). The estimated method detection limits using
the purge-and-trap procedure for the various chlorinated organic
solvents being discussed are as follows: 0.12 ug/1 for
trichloroethene and tetrachloromethane, .03 ug/1 for tetrachloroethene
and 1,1,1-trichloroethane, and .10 pg/1 for dichloromethane.
9.4 Other Samples
The methods used for the analysis of these chlorinated organic solvents
in environmental and other samples are summarized in an IARC Monograph
(IARC, 1979). The determination is made most frequently by using GC in
conjunction with one of several available detectors.
9-6 JUly, 1984
-------
REFERENCES
The major references used in the preparation of this document are listed
below. EPA documents are referenced by the EPA office of origin and the year
of publication. For further information refer to the contacts given
throughout this document or contact the EPA Program Offices listed in the next
section•
(IARC, 1979)
("AS, 1977)
(HAS, 1979)
(NTP, 1982)
(OHEA, 1982a)
(OHEA, 1982b)
(OHEA, 1982c)
(OHEA, 1982d)
(OHEA, 1982e)
(OWRS, 1979)
(OWRS, 1980a)
(OWRS, 1980b)
IARC Monographs on the Evaluation of the Carcinogenic Risk
of Chemicals to Humans, Vol. 20, International Agency 'for
Research on Cancer, World Health Organization, Tyon (1979).
Ozone and Other Photochemical Oxidants, National Academy of
Science, Washington, D.C. (1977).
Stratospheric Ozone Depletion by Hydrocarbons; Chemistry
and Transport, National Academy of Sciences, Washington,
'D.C. (1979).
NTP Technical Report on the Carcinogenesis Bioassay of
Trichloroethylene in F344/N Rats and B6C3F1/N Mice (Gavage
Study) National Toxicology Program (1982).
Health Assessment Document for Dichloromethane (Methylene
Chloride), Draft, EPA-600/8-82-004, Office of Health and
Environmental Assessment (1982).
Health Assessment Document for Carbon Tetrachloride, draft.
EPA-600/8-82-001, Office
Assessment (1982).
of Health and Environmental
Health Assessment Document for Trichloroethylene, Dra f t,
Ei>A-600/8-82-006, Office of Health and Environmental
Assessment.(1982).
Health Assessment Document for Tetrachloroethylene (Per-
chloroethylene), Draft, EPA 600/8-82-003, Office of Health
and Environmental Assessment (1982).
Health Assessment Document for 1,1,1-Trichloroethane (Methyl
Chloroform), Draft, EPA 600/8-82-003, Office of Health and
Environmental Assessment (1982).
Water-Related Fate of 129 Priority °ollutants, Vol. II, EPA-
440/4-79-029b, Office of Water Regulations and Standards
(1979).
Ambient Water Quality Criteria for Halomethanes, EPA 440/5-
80-051, Office of Water Regulations and Standards (1980).
Ambient Water Quality Criteria for Carbon Tetrachloride, EPA
440/5-80-026, Office of Water Regulations and Standards
(1980).
R-1
July, 1984
-------
(OWRS, 1980c)
(OWRS, 1980d)
(OWRS, 1980e)
Ambient Water Quality Criteria for Trichloroethylene,
EPA 440/5-80-077, office of Water Regulations and Standards
(1980).
Ambient Water Quality Criteria for Tetrachloroethylene, EPA
440/5-80-073,OfficeofWaterRegulationsandStandards
(1980).
Ambient Water Quality Criteria for Chloroethanes, EPA
440/5-80-029,Officeof Water Regulationsand Standards
(1980).
R-2
July, 1984
-------
OFFICE CONTACTS
The EPA offices and divisions that are listed below nay be contacted for more
information relating to the indicated sections of this document. While these
offices are, in many cases, the offices of origin for the data included in
this paper, the personal contacts given throughout this document should be
contacted first. Unless otherwise noted, the offices listed are situated in
Headquarters, Washington, D.C., and the telephone numbers given are FTS
(Federal Telecommunications System) numbers. For commercial telephone calls
to Headquarters which are not placed on PTS, area code 202 must be used.
Other commercial numbers are noted for the office contacts located outside
Washington, D.C.
HEALTH AND ENVIRONMENTAL EFFECTS (Section 2}
Office of Health and Environmental Assessment (OHEA)
Environmental Criteria and Assessment Office:
Cincinnati, OH 684-7531 (513-684-753U
Research Triangle Park, NC 629-4173 (919-541-4173)
Carcinogen Assessment Group 382-7341
Office of Drinking Water (ODH)
Health Effects Branch 382-7571
Office of Toxic Substances (OTS)
Health and Environmental Review Division 382-4241
Environmental Research Laboratory
Duluth, MM, Region V 783-9550 (218-727-6692)
ENVIRONMENTAL RELEASES AND EXPOSURE (Sections 3 and 4)
Office of Air Quality and Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Water Regulations and Standards (OWRS)
Monitoring and Data Support Division 382-7051
Office of Toxic Substances (OTS)
Exposure Evaluation Division 382-3873
R_3 July, 1984
-------
DATA BASES (Section 5)
Office of Toxic Substances (OTS)
Information Management Division 382-3149
REGULATORY STATUS, STANDARDS, AND CRITERIA (Sections 6 and 7)
Office of kit Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Drinking Water (ODW)
Criteria and Standards Division 382-7575
Office of Water Regulations and Standards (OWRS)
Criteria and Standards Division 755-0100
Effluent Guidelines Division 382-7120
Office of Solid Waste (OSW)
Permits and State' Programs Division 382-4746
SPILL CLEAN-UP AND DISPOSAL (Section 8)
NOTE: For Emergencies call the National Response Center at 1-800-424-8802
(1-800-426-2675 from the Baltimore/Washington area).
Office of Emergency and Remedial Response (OERR)
Emergency Response Division 382-2182
Hazardous Site Control 382-2443
Oil and Hazardous Materials Spills Branch
Edison, NJ; Region II 340-6635 (201-321-6635)
ANALYTICAL TECHNIQUES (Section 9)
Environmental Monitoring Systems Lab (EMSL)
Air Analysis
Research Triangle Park, NC 629-2454 (919-541-2454)
Hater Analysis
Cincinnati, OH 684-7311 (513-684-7311)
R-4 July, 1984
-------
Waste Analysis
Las Vegas, NV 545-2137 (702-798-2137)
Office of Monitoring Systems
and Quality assurance 382-5767
GENERAL IPP COMMENTS, CORRECTIONS, OR QUESTIONS
Chemical Coordination Staff
Chemical Infornation
and Analysis 332-3375
R-5 July, 1984
-------
Chloroform
-------
CHLOROFORM
Table of Contents Page
Physical/Chemical Properties and Chemistry 1-1
Properties 1-1
Chemistry and Environmental Fate/Transport 1-1
Effects Information 2-1
Health Effects 2-1
Environmental Effects 2-3
Environmental Release 3-1
Air Releases 3-1
Water Releases 3-1
Land Releases 3-1
Exposure 4-1
Data Bases 5-1
Chemicals in Commerce Information System (CICIS) 5-1
EPA Chemical Activities Status Report (EPACASR) 5-1
NIH/EPA Chemical Information System (CIS) 5-1
Chemical Regulations and Guidelines System (CRGS) 5-1
Chemical Substances Information Network (CSIN) 5-1
EPA Information Clearinghouse 5-2
Regulatory Status 6-1
Promulgated Regulations 6-1
Proposed Regulations 6-2
Other Actions 6-3
Standards and Recommended Criteria 7-1
Air 7-1
Water 7-1
Hazardous Waste 7-1
Other 7-2
July, 1982
-------
Spill or Other Incident Clean-up/Disposal 8-1
Hazards and Safety Precautions 8-1
First Aid 8-1
Emergency Action 8-1
Notification and Technical Assistance 8-2
Disposal 8-2
Sampling and Acceptable Analytical Techniques 9-1
Air 9-1
Water 9-1
Solid Waste 9-3
References and Office Contacts R-l
July, 1982
-------
CHLOROFORM
1. PHYSICAL/CHEMICAL PROPERTIES AND CHEMISTRY
1.1 Properties (OWRS, 1980)
At standard temperatures and pressures, chloroform is a clear,
colorless, volatile liquid with a pleasant, etheric, non-irritating
odor and sweet taste.
Synonyms: formyl trichloride; methane trichloride; methenyl chlo-
ride; methenyl trichloride; methyl trichloride; trichloroform.
CAS Number 67-66-3
Formula CHCl*
H
C1-C-C1
Cl
Molecular Weight 119.4
Melting Point (°C) -63.5
Boiling Point (°C) 61.2
Vapor Pressure (25°C) 190 torr
Water Solubility (258C) 7800 mg/1
Log Octanol-Water Partition
Coefficient 1.95
1.2 Chemistry and Environmental Fate/Transport
Chloroform is released to the atmosphere directly and by volatiliza-
tion from the aquatic environment and soil surfaces. Once it is in
the troposphere, its estimated lifetime is reported to be 2-3
months. Reaction with hydroxyl radicals appears to be the primary
degradation mechanism. Photochemical degradation is not expected to
be an important pathway. Removal from the atmosphere by rainout is
also considered unlikely because the high vapor pressure of chloro-
form indicates that an insignificant fraction will be associated
with water droplets or dust particles.
Volatilization is the predominant pathway for removal of chloroform
from the aquatic environment. One study reported that the half-life
1-1 July, 1982
-------
for evaporation of chlorine from a stirred aqueous solution was
approximately 20 minutes. Hydrolysis does not appear to be rapid
enough to compete with volatilization as a removal mechanism. Bio-
degradation and bioaccumulation in the aquatic environment are prob-
ably not important fate pathways. The extent to which adsorption
competes with volatilization is uncertain due to a lack of data in
this area, although volatilization is likely to predominate.
Little information is available on the Eate of chloroform in soils
and sediment. Volatilization is probably the dominant pathway from
surface soils. Evidence does suggest, however, that migration to
ground water might also occur (OURS, I960).
1-2 July, 1982
-------
2. EFFECTS INFORMATION
2.1 Health Effects (CONTACT: Jerry Stara, FTS 684-7531)
2.1.1 Acute Toxicity (OWRS, 1980)
The acute toxicity of chloroform in experimental animals is spe-
cies-, strain-, sex-, and age-dependent. Oral LDjQ values range
from 119 mg/kg to 2,000 mg/kg with indications of renal and hepatic
necrosis.
Most human toxicologic observations on chloroform have been made as
a result of its use as a general anesthetic, a practice which has
been discontinued. There are many documented fatalities from chlor-
oform-induced anesthesia. Ingestion of 120 ml of chloroform has been
survived, but serious illness occurred in another individual after
ingestion of only 5 ml.
Signs of chloroform poisoning in humans include a characteristic
sweetish odor on the breath, dilated pupils, cold and clammy skin,
initial excitation alternating with apathy, loss of sensation, abo-
lition of motor functions, prostration, unconsciousness and eventual
death. Liver and renal damage have been found.
Acute dermal exposure to chloroform may result in hyperemia, erythe-
ma, irritation and destruction of the epithelium. Eye contact pro-
duces burning, redness of conjunctival tissue and possible damage to
the corneal epithelium.
2.1.2 Chronic Toxicity
Worker exposure to concentrations of chloroform of over 112 mg/m^
have been reported to result in depression, ataxia, flatulence,
irritability, and liver and kidney damage (ORNL, 1978; OWRS,
1980a). Based on evidence that chloroform is carcinogenic in mice
and rats, IARC states that it is reasonable to regard the substance
as though it presents a carcinogenic risk to humans (IARC, 1979).
2.1.3 Absorption, Distribution and Metabolism (OWRS, 1980)
Chloroform is rapidly absorbed through the lungs if inhaled, through
the gastrointestinal tract if ingested, and, to a lesser extent,
through intact skin. With some species variation, chloroform is
partially excreted unchanged and partially metabolized to carbon
dioxide and unidentified urinary metabolites in mice, rats, monkeys
and humans.
An average chloroform concentration of 51 ug/kg was detected in
samples of body fat taken from eight subjects between 48 and 82
years of age. Concentrations of 1.0 ug/kg to 10 ug/kg were present
in kidney, liver, and brain tissues.
2-1 July, 1982
-------
2.2 Environmental Effects (Contacts: John Gentile, FTS 838-4843)
2.2.1 Aquatic Effects
Freshwater - Available data for chloroform indicate that acute tox-
icity to freshwater life occurs at concentrations as low as 28.9
mg/ral. Twenty-seven-day LC5Q values indicate that chronic toxicity
occurs at concentrations as low as 1.2 mg/1 and could occur at lower
concentrations among species or other life stages that are more sen-
sitive than the earliest life cycle stage of the rainbow trout
(ORNL, 1978).
Saltwater - The lowest reported 96-hour LC5Q value for a marine
organism is 28 mg/1 for the dab (Limanda sp). The 96-hour LC$Q for
the pink shrimp is 81.5 mg/1 (OWRS, 1980).
2.2.2 Other Effects
Plants - Studies show that abnormal mitosis has occurred in cells
exposed to chloroform concentrations of 0.025%. Toxic effects also
occur at this level. Concentrations greater than 0.25% have been
shown to be lethal (ORNL, 1978).
Microorganisms - Chloroform is not particularly susceptible to
degradation by microorganisms. It is a powerful inhibitor and has
been used for sterilization purposes. One study indicates that
extremely low concentrations of chloroform can severely limit diges-
tion of sewage sludge (ORNL, 1978).
2-2 July, 1982
-------
3.
ENVIRONMENTAL RELEASE
Information on sources and amounts of chloroform released to the
environment varies. For Instance, a comparison of two studies
reveals air emissions estimates in 1978 of 19,200 kkg (OWRS, 1980)
and 11,100 kkg (OAQPS, 1980). In general, present knowledge of
releases due to the activities of man is sketchy. There is also some
question about the relative importance of natural versus
anthropogenic sources. Materials balances, therefore, are
tentative. The releases listed in the table below are taken from a
report prepared by the Office of Water Regulations and Standards
(OWRS, 1980).
3.1
Air Releases
Source of Release
Pulp and Paper Bleaching
Chlorination of Water
Pharmaceutical Extractions
Automobile Exhausts
Atmospheric Decomposition
of Trichloroethylene
Chloroform Production
Production of Vinyl
Chloride Monomer
Transportation & Storage Loss
Production of F-22
Use of Chloroform as a Fumigant
3.2.
Water Releases
Source of Release
Pulp and Paper Bleaching
Pharmaceutical Extractions
Chlorination of Water
Chloroform Production
Production of Vinyl
Chloride Monomer
3.3
Land Releases
Source of Release
Pharmaceutical Extractions
Production of Vinyl
Chloride Monomer
Amount (kkg)
12,100
3,245
1,525
965
450
370
187
177
150
38
Amount (kkg)
400
275
221
14
Amount (kkg)
290
200
3-1
July, 1982
-------
4. EXPOSURE (CONTACT: Mike Slimak, FTS 426-2503)
The chlorlnation of drinking water represents the largest source of
human exposure to chloroform in the United States, generally ranging
from 0.02 - 0.2 rag/day. Although data are scarce, maximum exposure
due to ingestion of food has been estimated at 0.04 mg/day. In
general, inhalation exposure is thought to be low; however, somewhat
higher exposures are expected in industrialized and urban areas.
Another exposure route that may be of significance is absorption of
chloroform through the skin. Swimmers may receive up to 1.1 mg/day
via this route (OWRS, 1980).
4-1 July, 1982
-------
5. DATA BASES
5.1 Chemicals in Commerce Information System (CICIS)
The Inventory was compiled under the authority of Section 8 of TSCA
which requires manufacturers to report to EPA the chemicals imported
and manufactured during calendar year 1977. The Inventory lists the
Chemical Abstract Service (CAS) preferred name for the chemicals,
their respective CAS number (often used for identification purposes),
production site, company name, and volume(s) of production and im-
port. There is also a Confidential Inventory in which many of these
characteristics are claimed confidential by the manufacturer. In
these instances, the confidential information will not be available
on the public inventory. CICIS can now be accessed through the
NIH/EPA Chemical Information System (CIS - see 5.3). For further
information, contact Gerri Nowack at FTS 382-3568.
5.2 EPA Chemical Activities Status Report (EPACASR)
EPACASR is an on-line system containing information on EPA's interest
in chemicals. This system includes data on the Agency's regulations,
research, and assessments directed toward specific chemicals.
EPACASR is published annually and the data base is updated as
information is received. A searchable subset itemizes NTP/NCI
studies and results, as well as chemicals discussed in the IARC
monograph series. (Other sources are added as appropriate.) Entries
identify the statutory authority, the nature of the activity, its
status, the reason for and/or purpose of the effort, and a source of
additional information. Searches may be made by CAS Number or coded
text. For further information contact Eleanor Merrick at FTS
382-3415.
5.3 NIH/EPA Chemical Information System (CIS)
This is a collection of various scientific data bases available
through an interactive computer program. The linking system between
these data files is the Structure and Nomenclature Search System
(SANSS). CIS can also provide a list of non-CIS sources of informa-
tion on a chemical of interest. However, these files have to be
accessed individually by either separate on-line systems or in hard-
copy. For further information contact Delores Evans at FTS 382-3546
or Irv Weiss at FTS 382-3524.
5.4 Chemical Regulations and Guidelines System (CRGS)
CRGS is an on-line data base which is being developed to provide
information on chemical regulatory material found in statutes, regu-
lations, and guidelines at the Federal, State, and international
levels. Currently, only the first phase of CRGS, which encompasses
only source material at the Federal level, is operational. Nation-
wide access to CRGS is available through Dialog. For further infor-
mation, contact Delores Evans at FTS 382-3546 or Ingrid Meyer at FTS
382-3773.
5-1 July, 1982
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5.5 Chemical Substances Information Network (CSIN)
The prototype CSIN, operational since November 1981, has been devel-
oped by merging the technologies of computer networking and distrib-
uted data base management. CSIN is not another data base, but a
library of systems. Through the CSIN front-end intermediary manage-
ment computer, the user may access and use independent and autonomous
information resources which are geographically scattered, disparate
for data and information content, and employ a variety of types of
computer hardware, software, and protocols. Users may converse in
and among multiple systems through a single connection point, without
knowledge of or training on these independent systems.
Presently, six independent information resources are accessible
through CSIN. They are: National Library of Medicine (NLM), CIS,
EPA-CICIS, CAS-On-Line, SDC-orbit, and two files of Dialog: CRGS and
TSCA Inventory. The CSIN management computer allows the user to
create, retrieve, store, or manipulate data and queries. This elimi-
nates the need for re-entering long lists of chemical identifiers or
other information elements which are part of the original query or
which have been identified and acquired from one or more of the CSIN
resources. For further information contact Dr. Sid Siegal at FTS
382-2256.
5.6 EPA Information Clearinghouse
The EPA Information Clearinghouse is a bibliographic data base com-
posed of over 475 individual data bases and models which contain
monitoring information and statistics on a variety of chemicals. The
Individual data bases are maintained by offices within EPA. For
further information, contact Charlene Sayers at FTS 755-9112.
The following data bases contain information on chloroform:
Consolidated Permits Program-Application Form l,2b,2c
Data Collection Portfolio for Industrial Waste Discharges
Distribution Register of Organic Pollutants in Water
Drinking Water
Effluent Guidelines GC/MS Screening Analysis Data Base
Energy and Mining Point Source Category Data Base
Federal Facilities Information System
Fine Particle Emissions Information System
Food Industry Group
Fugitive Emissions Information System
Gaseous Emissions Data System
Hazardous Waste Data Management System
Hazardous Waste Site Tracking System
Hemlock, Michigan Environmental Samples
Hewlett-Packard
Humacao Ambient Data Base
IFB Organics Data Base
Indicatory Fate Study
Industrial Process Evaluations
Innovative Technology, Timber Industry Effluent Guidelines
5-2 July, 1982
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Inorganic Chemicals Industry Regulation Record
LiPari Landfill
Liquid Effluents Data System
Listing of Organic Compounds Identified in Region IV
Love Canal Data Handling System
Method Validation Studies of Priority Pollutants
National Electronic Injury Surveillance System
National Pollutant Discharge Elimination System (NPDES) Discharge
Permit Compliance
Nationwide Urban Runoff Program
Needs Survey
New York Bight Ocean Monitoring Program
Organic Chemicals/Plastics Industry
Organic Transport thru Soil
Ozone and its Precursors Data Base—Houston/Los Angeles
Ozone and its Precursors Data Base—Midwest/Boston
Paint and Ink Analytical Data
Permit Compliance System
Pesticide Incident Monitoring System
Pesticide Product Information System
Pharmaceutical Screening/Verification Data Base
Precision and Accuracy for Screening Protocols
Priority Pollutants-Region I
Priority Pollutants-Region III
Publicly Owned Treatment Works (POTW) Analytical Data
Publicly Owned Treatment Works (POTW) Quality Control
Puerto Rico Reservoirs
Regional Toxics Monitoring Program
Resource Conservation and Recovery Act (RCRA)-Hazardous Waste Site
Inspections
Screening Sampling Program
Select Hazardous Chemicals-Ambient
Sources of Toxic Pollutants Found in Influents to Sewage Treatment
Plants
Spill Prevention Control and Counter-measure
System for Consolidated Permitting and Enforcement Data Base
Textile Industry BAT Study-Toxic Sampling Data
Toxics Monitoring
U.S. Virgin Islands-St. Thomas, St. Croix
Verification Data Base
Verification Sampling Program
Waste Characterization Data Base
Water Enforcement Regional System
Water Quality Information System
Wisconsin Power Plant Impact Study Data Center
5-3 July, 1982
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6. REGULATORY STATUS (Current as of 4/15/82)
6.1 Promulgated Regulations
6.1.1 EPA Programs
Clean Air Act (CAA)
Chloroform is not regulated directly as an air pollutant.
Clean Water Act (CWA)
• Toxic Pollutant Effluent Standards - Pursuant to Section
307(a)(l) of the Federal Water Pollution Control Act (FWPCA),
chloroform is listed as a toxic pollutant (40CFR401.15). As
such, It is subject to effluent limitations reflecting the
"best technology economically achievable" (BAT). Effluent limi-
tations for chloroform have not been promulgated, however.
• Designation of Hazardous Substances and Reportable Quantities -
Chloroform has been designated as a hazardous substance under
Section 311(b)(2)(A) of the FWPCA (40CFR116.4). A reportable
quantity has been established; any discharge into navigable
waters in excess of the reportable quantity must be brought to
the attention of the Coast Guard (40CFR117.21), and the dis-
charger is subject to clean-up liability and civil penalties
(40CFR117.22-23).
Safe Drinking Water Act (SDWA)
• Maximum Contaminant Levels - National Interim Primary Drinking
Water regulations for total trihalomethanes (TTHMs; a combina-
tion of chloroform and three other trihalogenated methanes)
apply to community water systems which serve 10,000 individuals
or more and which add a disinfectant as part of their treatment
process. For such systems, the maximum contaminant level (MCL)
for TTHMs is 0.10 mg/1 (40CFR141.12). This restriction takes
effect for large water systems (greater than 75,000 customers)
on November 29, 1981, and for all regulated systems by November
29, 1983.
• Underground Injection Control - The Safe Drinking Water Act
requires EPA to promulgate minimum requirements for State pro-
grams to protect underground drinking water sources from con-
tamination due to pollutants Injected into wells. Technical
requirements and criteria can be found at 40CFR part 146. In a
State with an approved UIC program, underground injection of
chloroform-containing wastes designated as hazardous wastes
under RCRA cannot occur without a permit.
6-1 July, 1982
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Resource Conservation and Recovery Act (RCRA)
Wastes Identified as hazardous under Section 3001 of RCRA are sub-
ject to a "cradle-to-grave" management system which encompasses gen-
eration, transportation and treatment, storage or disposal. Chloro-
form is identified as a hazardous toxic waste under 40CFR261.33(f)
if it is a discarded commercial chemical product or manufacturing
intermediate, off-specification commercial product or manufacturing
intermediate, or contained in clean-up residue resulting from a
spill of chloroform in the form of a commercial product or
manufacturing intermediate. An exclusion for those who generate
less than 1,000 kg/month of these wastes is available.
Chloroform is also identified as a toxic constituent of the follow-
ing wastes listed as hazardous under 40CFR261.32:
(1) Distillation bottoms from the production of acetaldehyde from
ethylene;
(2) Distillation side cuts from the production of acetaldehyde from
ethylene;
(3) Heavy ends from the distillation of ethylene dichloride in
ethylene dichloride production;
(4) Heavy ends from the distillation of vinyl chloride in vinyl
chloride monomer production;
(5) Aqueous spent antimony catalyst waste from fluoromethanes
production;
(6) Waste from the product stream stripper in the production of
1,1,1-trichloroethane; and
(7) Chlorinated hydrocarbon wastes from the purification step of
the diaphragm cell process using graphite anodes in the produc-
tion of chlorine.
Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA)
On April 6, 1976, (41FR14588), pursuant to the procedures set forth-
in 40CFR162.11, a Notice of Rebuttable Presumption Against Registra-
tion (RPAR) was issued for pesticide products containing chloroform.
Under 4XFR162.ll the RPAR was triggered when chloroform was found
to meet or exceed EPA's oncogenic risk criterion.
The RPAR on chloroform may be rebutted by showing that it "will not
concentrate, persist or accrue to levels in man or the environment
likely to result in any significant chronic adverse effects" or that
the risk criteria determination was in error (40CFR162.il). In
addition, the registrant may submit evidence that the benefits of
the pesticide outweigh the risk (40CFR162.il).
6-2 Julyi 1982
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Marine Protection, Research and Sanctuaries Act (MPRSA)
Section 102(a) of the Marine Protection, Research and Sanctuaries
Act authorizes the Administrator of EPA to issue ocean dumping per-
mits if such dumping will not degrade or endanger human health, wel-
fare, or amenities, or the marine environment, or economic poten-
tial. The Agency has promulgated criteria to which permitted dump-
ing operations must adhere. Major provisions which affect the dis-
posal of chloroform are:
• A prohibition on dumping organohalogens, mercury,
and cadmium compounds except as "trace contami-
nants" (40CFR227.6).
• A prohibition on dumping known or suspected carcin-
ogens, mutagens, and teratogens (40CFR227.6).
However, chloroform is not mentioned in the regulations, and it
appears that if any control over its disposals exists, it is exer-
cised on a case-by-case basis when disposers apply for ocean dumping
permits.
6.1.2 Programs of Other Agencies
Occupational Safety and Health Administration (OSHA)
Section 6(a) of OSH Act requires the Secretary of Labor to adopt as
mandatory any national consensus standard or established Federal
standard relating to employee health and safety. OSHA has adopted
the Threshold Limit Value established by the American Conference of
Government Industrial Hygienists. OSHA limits the concentration of
chloroform In workplace air to a celling value of 50 ppm, or 240
mg/m3 (29CFR1910.1000)
Food and Drug Administration (FDA)
FDA has banned chloroform as an ingredient (active or inactive) in
any human or animal drug or any cosmetic product, except in residual
amounts resulting from the manufacturing process (21CFR310.513,
510.413 and 700.18 respectively).
Department of Transportation (DOT)
Pursuant to the Hazardous Materials Transportation Act, the Depart-
ment of Transportation has promulgated rules governing the trans-
porters of hazardous materials. The rules require that shippers and
transporters of hazardous materials (as defined in 49CFR172.101) ad-
here to standards for containing, packaging and labeling such mate-
rials and for maintaining manifests and documentation (49CFR171-
177). Amendments to the rules were promulgated on May 22, 1980,
(45FR34560), which add to the Hazardous Materials Table the hazard-
ous substances and hazardous wastes regulated by EPA (40CFR116 and
262, respectively). Further provisions were added requiring trans-
porters to notify the appropriate Federal agency of any discharges
6-3 July, 1982
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of hazardous wastes and hazardous substances (49CFR171.16, 171.17).
The revised Hazardous Materials Table, published as 49CFR172.101,
includes chloroform.
6.2 Proposed Regulations
6.2.1 EPA Programs
Clean Air Act
• No proposed regulations address chloroform directly. Proposed New
Source Performance Standards for the Synthetic Organic Chemicals
Manufacturing Industry (46FR1136) would regulate volatile organic
compounds (VOC), however. If promulgated, this regulation could
affect emission of chloroform (OTI, 1981).
Clean Water Act
• Best Available Technology (BAT) and New Source Performance
Standards (NSPS) would impose effluent limitations on concen-
trations of chloroform in waste water for 10 subcategories of the
Pulp, Paper and Paperboard and Builder's Paper and Board Mills
point source categories (46FR1430).
6.2.2 Programs of Other Agencies
FDA - Food and Drug Administration
• FOA has proposed a ban on the use of chloroform as a component of
food-contact articles and the listing of chloroform as a substance
prohibited from use in human food under Section 409(c)(3)(A) of
the Federal Food Drug and Cosmetic Act (Food Additives - the
Delaney Clause) 41FR1S029.
6.3 Other Actions
Clean Water Act - Water Control Criteria - While Water Quality
Criteria published pursuant to Section 304(a)(l) of the FWPCA do not
have regulatory force, they are used in establishing individual
effluent limitations for point source discharge permits under Section
402 (NPDES permits) and best management practices for non-point
sources under Section 208. Water Quality Criteria for chloroform are
based on protection of human health and are calculated parametrically
on the basis of various expected levels of incremental cancer risk
resulting from ingestion of a) aquatic organisms only and b) aquatic
organisms plus water (OWRS, 1980a).
Comprehensive Environmental Response, Compensation, and Liability Act
(CERCLA or Superfund) - CERCLA provides for the liability, compensa-
tion, clean-up, and emergency response for the release of hazardous
substances into the environment. This Act also deals with the clean-
up of hazardous waste disposal sites (42USC9601; PL 96-510). EPA is
6_4 July, 1982
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developing regulations concerning the designation of hazardous
substances, the development of reportable quantities, claims
procedures, and the confidentiality of business records (46FR54032).
Revisions to the National Contingency Plan (NCP) as required by
CERCLA have been issued in a proposed rule (47FR10972). Hazardous
substances as defined by Section 101(14) of CERCLA include:
hazardous wastes designated under Section 300L of the RCRA; hazardous
air pollutants regulated under Section 112 of the CAA; water
pollutants listed under Sections 307 and 311 of the CWA (and also any
substances regulated in the future under Section 7 of TSCA and
Section 102 of CERCLA). Therefore, chloroform is a hazardous
substance under CERCLA and will be subject to regulations developed
under Superfund.
6-5 July, 1982
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7. STANDARDS AND RECOMMENDED CRITERIA*
7.1 Air - None
7.2 Water
• Water Quality Criteria (OWRS, 1980a)
Aquatic Life
• Freshwater Species
Acute Toxicity: 28,900 ug/ml
Chronic Toxicity: 1,240 ug/ml
• Saltwater Species - None
Human Health
For the maximum protection of human health from the potential
carcinogenic effects due to exposure of chloroform through
ingestion of contaminated water and contaminated aquatic organisms,
the ambient water concentrations should be zero based on the
non-threshold assumption for this chemical. However, zero level
may not be attainable at the present time. Therefore, the levels
which may result in incremental increase of cancer risk over the
lifetime are estimated at 10~5, 10~6, and 10~7. The corresponding
recommended criteria are 1.90 ug/1, 0.19 ug/1, and 0.019 ug/1,
respectively. If the above estimates are made for consumption of
aquatic organisms only, excluding consumption of water, the levels
are 157 ug/1, 15.7 ug/1, and 1.57 ug/1, respectively.
• Reportable Quantity Under Section 311 of the Clean Water Act
(40CFR117)
The reportable quantity for spilled chloroform has been set
at 5,000 pounds. EPA has proposed to lower this amount to
100 pounds (45FR46097). Discharge of chloroform into the
navigable waters of the United States or adjoining shorelines
in excess of the reportable quantity must be brought to the
attention of the Coast Guard.
• Maximum Contaminant Level Under the Safe Drinking Water Act
(40CFR141.12)
Restrictions on total trihalomethanes (TTHMs); a combination
of chloroform and three other trihalogenated methanes apply
to community water systems which serve 10,000 individuals or
more and which add a disinfectant as part of the treatment
process. For such systems, the maximum contaminant level
(MCL) for TTHMs is 0.10 mg/1.
* See Appendix A for a discussion of the derivation, uses, and limitations of
these Criteria and Standards.
7-1 July, 1982
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7.3 Hazardous Waste
Generation as waste in one month of 1,000 kilograms or more of chlo-
roform in the form of a commercial chemical product, manufacturing
chemical intermediate, off-specification product or clean-up residue
resulting from a spill of the above, is subject to the hazardous
was.te regulations promulgated under RCRA,
7.4 Others
• Transportation - Reportable Quantities
Under regulations promulgated pursuant to the Hazardous Mater-
ials Transportation Act, 5,000 pounds or more of chloroform is
a reportable quantity. If a quantity of chloroform equaling or
exceeding that amount is offered for transportation in one
package, or transport vehicle when the material is not pack-
aged, that fact must be noted on shipping papers and displayed
on packages.
• Workplace
- OSHA limits the concentration of chloroform in workplace air
to a ceiling value of 50 ppm or 240 mg/m3 (29CFR1910.1000).
- The American Conference of Government Industrial Hygienists
has revised their TLV to 10 ppm (approximately 50 mg/m3) on
an 8-hour time-weighted average basis.
- NIOSH recommended a standard that limited workplace concen-
trations to 10 ppm on a 10-hour time-weighted average basis,
with a 10-minute maximum of 50 ppm. NIOSH also recommended
. that chloroform, when used as an anesthetic, be limited to an
airborne concentration of 2 ppm.
7-2 July, 1982
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8. SPILL OR OTHER INCIDENT CLEAN-UP/DISPOSAL
(CONTACT: National Response Center, 800-424-8802; in the Washington
area, 426-2675)
8.1 Hazards and Safety Precautions (SAX, 1979; ITU, 1980)
Highly toxic by inhalation. Slightly flammable but will burn on
prolonged exposure to flame or high temperature (combusion products
are highly toxic). Reacts violently with (acetone + a base), Al,
disilane, Li, Mg, nitrogen tetroxide, K, (perchloric acid + phospho-
rus pentoxide), (KOH + methanol), K-tert-butoxide, Na, (NaOH + meth-
anol), sodium methylate.
Protect containers from damage. Store in a dark place away from
direct sunlight and moisture. When handling, use safety glasses,
self-contained breathing apparatus, protective clothing. Note: PVC
and rubber are unsuitable materials for protective clothing.
8.2 First Aid (SAX, 1979; ITII, 1980)
If chloroform has been ingested, or there has been substantial over-
exposure, the following antidotes may be applied: emetics, stomach
syphon, friction, cold douche, fresh air, strychnine (hypodermical-
ly—from 1/120 to 1/60 grain), rubefacients, artificial respira-
tion. Wash eyes with abundant water. Contaminated areas of the
body should be washed clean with soap and water.
8.3 Emergency Action (DOT, 1980)
Do not touch spilled material. Use water spray to reduce vapors.
For small spills, take up with absorbent material then flush area
with water. For large spills, dike far ahead.
8.4 Notification and Technical Assistance
Section 103 of the "Superfund" Act requires persons who release
hazardous substances into the environment in reportable quantities
to notify the National Response Center at 800-424-8802 (in the
Baltimore-Washington, D.C. area, call 800-426-2675). The reportable
quantity for chloroform is 5,000 pounds.
For technical assistance, call CHEMTREC (Chemical Transportation
Emergency Center) at 800-424-9300. Another source of information is
the Oil and Hazardous Materials Technical Assistance Data System
(OHM-TADS) contained in the NIH/EPA Chemical Information System
(CIS) (See Section 5.3).
8.5 Disposal
A person who generates 1,000 kg or more per month of chloroform
defined as a hazardous waste (discarded commercial product, off-spec
product, manufacturing intermediate and clean-up residues of same) is
subject to the RCRA hazardous waste regulations on treatment, storage
and disposal.
8-1 July, 1982
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The following specific waste screams, which contain chloroform, are
also subject to the hazardous waste regulations.
(1) Distillation bottoms from the production of acetaldehyde from
ethylene;
(2) Distillation side cuts from the production of acetaldehyde from
ethylene;
(3) Heavy ends from the distillation of ethylene dichloride in
ethylene dichloride production;
(4) Heavy ends from the distillation of vinyl chloride in vinyl
chloride monomer production;
(5) Aqueous spent antimony catalyst waste from fluoromethanes
production;
(6) Waste from the product stream stripper in the production of
1,1,1-trichloroethane; and
(7) Chlorinated hydrocarbon wastes from the purification step of
the diaphragm cell process using graphite anodes in the
production of chlorine.
8-2 July, 1982
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9. SAMPLING AND ACCEPTABLE ANALYTICAL TECHNIQUES
9.1 Air (CONTACT: Joseph F. Walling, FTS 629-7954)
Chloroform is not regulated as an air pollutant. Therefore, no
Agency or reference procedures exist. Although measurements of this
pollutant have been made and reported, there are no well-documented
method descriptions available for quantitative measurements in
ambient air. Therefore, monitoring for this pollutant must be
approached with great caution.
A procedure using Tenax adsorbent for sampling and gas chromato-
graphy/mass spectrometry (GC/HS) for analysis has been used but
little is known about the precision and accuracy of the procedure.
GC/MS requires special expertise and expensive, sophisticated equip-
ment. For these reasons, monitoring for one compound alone using
the Tenax GC/MS procedure is rarely cost effective and the approach
is most suitable when monitoring for an array of volatile compounds
is desired.
The preparation of Tenax suitable for sampling is demanding. Tenax
background is a problem that must be addressed. Precautions about
permissible maximum air volumes, sampling rates and ambient tempera-
tures during sampling must be observed and these, in turn, govern
allowable sampling times.
Detection limits and accuracy are not known; reproducibility is esti-
mated to be 50-100 percent. Quality assurance materials composed of
blank Tenax sampling cartridges spiked with known amounts of chloro-
form can be prepared and must be used in any monitoring program.
9.2 Water (CONTACT: Thomas Bellar, FTS 684-7311 or
James Lichtenberg, FTS 684-7308)
There are several approved and proposed gas chromatographic proce-
dures for the analyses of chloroform in natural, waste and drinking
waters. The primary difference between the methods is the extrac-
tion procedure and the means of injecting the extracts into the gas
chromatograph. Mass spectrometry and halogen-specific detectors are
normally used to improve qualitative accuracy.
• Direct Aqueous Injection for Wastewater EPA # Method 8 (la)*
ASTM 9 D-2908-74 (2*)
Major Equipment Required: Gas chromatograph
One to 5 ul of the neat sample is injected directly into the gas
chromatograph. The method detection limit is approximately 1 mg/1
when mass spectrometry, flame ionization or halogen-specific detec-
tors are used. For nieke1-63 electron capture detectors the method
detection limit is approximately 1 ug/1. Direct aqueous injection
techniques are not acceptable for the analysis of chloroform in
drinking water.
*Superscripts refer to references at the end of this subsection.
9-1 July, 1982
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• Liquid-Liquid Extraction EPA 9 501.2(3a)
ASTM - To be included in the 1981
Annual Book of ASTM Standards
Major Equipment Required: Gas chromatograph
A small volume of sample is extracted once with a low boiling, water
insoluble solvent such as pentane. Sample/solvent ratios of 5:1 are
commonly used. One to 5 ul of the extract is then injected into a
gas chromatograph equipped with an electron capture detector• The
method detection limit is approximately 0.5 ug/1.
• Purge and Trap EPA I 601,(4a) 625,(*a) 502.1,(5a) 501.1 (3a)
ASTM I 0-3871-79(6*)
Standard Methods - To be included in the
15th Edition
Major Equipment: Gas chromatograph and purge and trap apparatus.
Five ml of the aqueous sample is placed into a purging device.
Chloroform and other volatile, water insoluble organic compounds are
transferred from the aqueous phase to the gas phase. The volatilized
compounds are swept from the purging device by the purge gas and are
trapped in a short column containing a suitable sorbent. After a
predetermined period of time, the trapped compounds are thermally
desorbed and backflushed into a gas chromatograph equipped with a
mass spectrometer, flame ionlzation or a halogen-specific detector.
The method detection limit for the mass spectrometer (full scan) and
the flame ionization detector is approximately 1 ug/1. For a care-
fully optimized halogen-specific detector method, detection limits
as low as 20 ng/1 have been achieved.
Samples are collected in narrow-mouth screen-cap bottles with TFE
fluorocarbon seals. Samples are stored head-space free at 4°C in
the dark. Sodium thiosulfate must be used to remove free residue
chlorine. Spiked water samples have been stored for up to 14 days
under these conditions with no apparent losses.
Single laboratory test data on simple spiked matrices have been
collected by EPA. Intralaboratory accuracy and precision and method
detection limit data are currently being collected. Quality control
and performance evaluation samples (methanolic concentrates contain-
ing chloroform to be spiked into water) are available from the
Environmental Monitoring and Support Laboratory, Quality Assurance
Branch, USEPA, Cincinnati, Ohio 45268.
9-2 July, 1982
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References
la. "A Method for Organochlorlne Solvents in Industrial Effluents."
National Pollutant Discharge Elimination System Appendix A,
Federal Register 38, No. 7S Ft. II.
2a. "Standard Test Method for Measuring Volatile Organic Matter in
Water by Aqueous - Injection Gas Chromatography," Annual Book
of ASTM Standards, 1980, Part 31, Water, ASTM D-2908-74.
3a. Federal Register, Thursday, November 29, 1979, Volume 44.
231, 40CFR, Appendix C - Parts I and II.
No.
4*. Federal Register, Monday, December 3, 1979, Volume 44, No. 233,
40CFR Part 136, Guidelines Establishing Test Procedures for the
Analysis of Pollutants.
52. "The Determination of Halogenated Chemical Indicators of Indus-
trial Contamination in Water by the Purge and Trap Method,"
Method 502.1, September 1980, USEPA, Environmental Monitoring
and Support Laboratory, Cincinnati, Ohio 45263.
6a. "Standard Test Method for Measuring Purgeable Organic Compounds
in Water Using Headspace Sampling," ASTM D-3871-79, Part 31,
Water, Annual Book of ASTM Standards, 1980.
LIST OF PROCEDURES FOR CHLOROFORM
Standard
Recovery^ Deviation
Method
Type
MDL
Status
EPA 624
EPA 601
EPA 502.1
EPA 501.2
EPA 8
Standard Methods
ASTM D-2098-74
ASTM D-3871-79
EPA 501.1
P&T
P&T
P&T
LLE
DAI
P&T
DAI
P&T
P&T
1.6
0.05 ug/1
<1 ug/1
<1 ug/1
1 mg/1
ND
ND
ND
<1 ug/1
90
98
ND
106-110
ND
ND
ND
99-121
88-100
18
7.5
ND
5.3-9.8
ND
ND
ND
ND
0.14-7.9
Proposed
Proposed
Proposed
Official
Official0
Untested
Untested
Untested
Official5
P&T = Purge and Trap
LLE = Liquid/Liquid Extraction
DAI = Direct Aqueous Injection
Status - As of March 1981.
a Single laboratory recovery from spiked reagent water or wastewater.
b Official for the analysis of chloroform in drinking water.
c Official for the analysis of organohalides in wastewater.
9-3
July 1982
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9.3 Solid Waste (CONTACT: Michael Hiatt, FTS 545-2118 or
Werner F. Beckert, FTS 545-2118)
Chloroform is a volatile priority pollutant that is determined in
water according to Method 601 (44FR69468, gas chromatography with
electron capture detector - GC/EC) or Method 624 (44FR69532, gas-
chroraatography/mass spectrescopy - GC/MS). No approved method for
the determination of chloroform in soil, sediment or hazardous waste
has been published. The commonly used analytical technique for the
determination of volatile priority pollutants is GC/MS.
Sediments may be stored as long as 60 days when kept at 4°C and
tightly sealed (lb).* The container should be a glass septum vial
with an unpierced teflon-lined septum. However, it is desirable to
analyze samples as soon as possible, preferably within seven days
since the septum vial seals are difficult to insure. When
improperly sealed, the samples are easily cross-contaminated during
storage by other stored samples or solvents used in laboratory
operations. It has been found that 10 g blank sediment sealed in a
septum vial and stored for several days in a freezer, which was
situated in a sample preparation laboratory, has been contaminated
with methylene chloride to a level of 200 ppb.
GC/MS quantitation is done using bromochloromethane as the Internal
standard for both capillary and packed columns. Chloroform is com-
pletely separated in the GC column from the other volatile priority
pollutants. Quantitation is done by peak height or using the area
of mass 83 m/e. The recommended reverse library identification
masses are 47, 48, 49, 83, 85, and 87 m/e. Identification should be
confirmed by a NBS forward library search.
Four sample preparation techniques that are applicable to GC/MS are:
head space analysis, solvent extraction (2b), modified purge and trap
(3b & 4b), and vacuum extraction (5b).
Head space analysis is not recommended since the precision is very
poor for spike recoveries and is suspected to be analyst-dependent.
The solvent extraction is done by shaking 1 ml n-hexadecane with 1 g
of sample in a 1-ml septum vial. The injection aliquot is removed
directly from the vial after 30 seconds of mixing and injected
splitless into a capillary column. The solvent extraction technique
is recommended only for ppra or greater concentrations. A standard
deviation of 1.4% at 10 ppm has been reported for this method.
One modified purge and trap technique (3b) desorbs the volatile com-
pounds from the sample by heating the sample to 110°C while sweeping
with helium carrier gas that is subsequently passed through 5 ml of
water. The carrier gas then passes through a Tenax-silica gel trap
which absorbs the volatile organics. The volatiles are desorbed from
the trap by heating and passed through a GC column. Sample
*Superscripts refer to references at the end of this subsection.
9-4 July, 1982
-------
preparation generally takes less than 30 minutes. Recoveries are
reported to be 77% at 26 ppb with a 35% precision. This method has
been tested for the ppb range.
In another modified purge and trap technique (4b), which was used in
the Love Canal Study, the sample is diluted with water and the
resultant slurry is purged. A standard deviation of 19% has been
reported for this method at the 20 ppb range with a recovery of 88%.
With the vacuum extraction technique (5b), the volatiles are
extracted from the sample using a vacuum. The extracted volatiles
are collected in a liquid-nitrogen-cooled trap. After extraction, 5
ml of water are added to the extract and the sample analyzed as a
5-ml water sample using Method 624. The precision at 25 ppb is 11%
with a 102% recovery. The total sample preparation takes approxi-
mately 36 minutes.
Standards can be obtained from Radian Corporation or EMSL-Las
Vegas (see Contact). Supelco supplies diluted standards but the
concentrations are not verified. Standard solutions may also be
prepared in the laboratory from reagent-grade chloroform to the
appropriate dilution using methanol.
Periodic performance evaluations with samples that include chloro-
form are carried out by EMSL/CIN (Water Supply and Water Pollution
Studies).
lb. Memorandum Report, March 12, 1981, entitled "Holding Time for
Purgeable Love Canal Soil and Sediment Samples," Dennis L.
Forest to William L. Budde, EMSL-CIN.
2b. I. R. DeLeon, et al., "Rapid Gas Chromatographic Method for the
Determination of Volatile and Semivolatile Organochlorine Com-
pounds in Soil and Chemical Waste Disposal Site Samples,"
Journal of Chromatographic Science, 18:85-88 (1980).
3b. David N. Spels, "Determination of Purgeable Organics in Sedi-
ment Using a Modified Purge and Trap Technique," Protocol,
U.S. EPA, Region II, Edison, New Jersey, October 10, 1980.
4b. Quality Assurance Plan, Love Canal Study (unpublished).
5b. Michael H. Hiatt, "Analysis of Fish and Sediment for Volatile
Priority Pollutants." Submitted for publication to Analytical
Chemistry.
9-5 July, 1982
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REFERENCES
The major refernces used in preparation of this document are listed below.
EPA references are listed below. EPA references are listed by the EPA office
of origin and the year of publication. For additional information, refer to
contacts given throughout this document or contact the EPA offices listed
below.
(DOT, 1980)
(IARC, 1979)
(ITII, 1980)
(OAQPS, 1980)
(ORNL, L978)
(OTI, 1981)
(OWRS, 1980)
(OWRS, 1980a)
(SAX, 1979)
Hazardous Materials: 1980 Emergency Response Guidebook.
U.S. Department of Transportation, 1980.
IARC Monographs on the Evaluation of the Carcinogenic
Risk of Chemicals to Humans, Vol. 20, International
Agency for Research on Cancer, World Health Organization,
October 1979.
Toxic and Hazardous Industrial Chemicals Safety Manual.
International Technical Information Institute, 1980.
Human Exposure to Atmospheric Concentrations of Selected
Chemicals"! Prepared for the Office of Air Quality
Planning and Standards by Systems Applications, Inc.,
March 1980.
Environmental and Health Aspects of Selected Organohallde
Compounds; An Information Overview. Oak Ridge National
Laboratory, July 1978.
Integrated Multimedia Control Alternatives: Phase I Case
Study - Chloroform. Draft report prepared by Abt Assoc.
for the Office of Toxics Integration, June 1981.
An Exposure and Risk Assessment for Trihalomethanes.
Final Draft Report, Office of Water' Regulations and
Standards, November 1980.
Ambient Water Quality Criteria for Chloroform, Office of
Water Regulations and Standards, EPA 440/5-80-033,
October 1980.
Dangerous Properties of Industrial Chemicals, N. Irving
Sax, 5th ed., 1979.
R-l
July, 1982
-------
OFFICE CONTACTS
The EPA offices and divisions that ace listed below may be contacted for more
information relating to the indicated sections of this document. While these
offices are, in many cases, the offices of origin for the data included in
this paper, the personal contacts given throughout this document should be
contacted first. Unless otherwise noted, the offices listed are situated in
Headquarters, Washington, B.C., and the telephone numbers given are FTS
(Federal Telecommunications System) numbers. For commercial telephone calls
to Headquarters which are not placed on FTS, area code 202 must be used.
Other commercial numbers are noted for the office contacts located outside
Washington, D.C.
HEALTH AND ENVIRONMENTAL EFFECTS (Section 2)
Office of Health and Environmental Assessment (OHEA)
Environmental Criteria and Assessment Office:
Cincinnati, OH 684-7531 (513-684-7531)
Research Triangle Park, NC 629-2266 (919-541-2266)
Carcinogen Assessment Group 755-3968
Office of Drinking Water (ODW)
Health Effects Branch 472-6820
Office of Toxic Substances (OTS)
Health and Environmental Review Division 382-4241
Environmental Research Laboratory
Duluth, UN, Region V 783-9550 (218-727-6692)
ENVIRONMENTAL RELEASES AND EXPOSURE (Sections 3 and 4)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Water Regulations and Standards (OWRS)
Monitoring and Data Support Division 426-2503
R-2 July, 1932
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Office of Toxic Substances (OTS)
Exposure Evaluation Division 382*3873
Assessment Division 382-3442
DATA BASES (Section 5)
Office of Toxic Substances (OTS)
Management Support Division 382-3546
REGULATORY STATUS, STANDARDS, AND CRITERIA (Sections 6 and 7)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Drinking Water (ODW)
Criteria and Standards Division 472-5016
Office of Water Regulations and Standards (OWRS)
Criteria and Standards Division 755-0100
Effluent Guidelines Division 426-2571
Office of Solid Waste (OSW)
State Programs and Resources
Recovery Division 755-9107
SPILL CLEAN-UP AND DISPOSAL (Section 8)
NOTE: For Emergenices call the National Response Center at 1-800-424-8802
(1-800-426-2675 from the Baltimore/Washington area).
Office of Emergency and Remedial Response (OERR)
Emergency Response Division 245-3045
Oil and Hazardous Materials Spills Branch
Edison, NJ; Region II 340-6634 (201-321-6634)
R-3 July, 1982
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Office of Solid Waste (OSW)
Hazardous and Industrial Waste Division 755-9187
ANALYTICAL TECHNIQUES (Section 9)
Environmental Monitoring Systems Lab (EMSL)
Air Analysis
Research Triangle Park, NC 629-2454 (919-541-2454)
Water Analysis
Cincinnati, OH 684-7311 (513-684-7311)
Waste Analysis
Las Vegas, NV 545-2137 (702-798-2137)
GENERAL IFF COMMENTS. CORRECTIONS. OR QUESTIONS
Office of Toxic Integration
Chemical Information and Analysis Program 382-2249
R-4 July, 1982
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CHROMIUM
Table of Contents Page
Physical/Chemical Properties and Chemistry 1-1
Properties 1-1
Chemistry and Environmental Transport 1-1
Effects Information 2-1
Health Effects 2-1
Environmental Effects 2-4
Environmental Release 3-1
Exposure Routes 4-1
Air Exposure 4-1
Water Exposure 4-1
Other Exposure Routes 4-1
Data Bases 5-1
Chemicals in Commerce Information System (CICIS) 5-1
EPA Chemical Activities Status Report (EPACASR) 5-1
NIH/EPA Chemical Information System (CIS) 5-1
Chemical Regulations and Guidelines System (CRGS) 5-1
Chemical Substances Information Network (CSIN) 5-2
EPA Information Clearinghouse 5-2
Regulatory Status 6-1
Promulgated Regulations 6-1
Proposed Regulations 6-4
Other Actions 6-5
Standards and Recommended Criteria 7-1
Air 7-1
Water 7-2
Other 7-2
July, 1983
-------
Spill and Other Incident Cleanup/Disposal 8-1
Hazards and Safety Precautions 8-1
First Aid 8-1
Emergency Action 8-1
Notification and Technical Assistance 8-1
Disposal '8-2
Sampling, Acceptable Analytical Techniques, and Quality Assurance 9-1
Air 9-1
Water 9-1
Solid Wastes 9-3
Other Samples 9-3
References and Office Contacts R-1
July, 1983
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CHROMIUM
1. PHYSICAL/CHEMICAL PROPERTIES AND CHEMISTRY
1.1 Properties
Chromium is a common metallic element present in low concentrations
throughout the environment. While there is no significant domestic
mining of chromite ore (the predominant chromium-bearing mineral), about
1.2 billion Ibs. (540 x 103 metric tons) of chromite ore and 320 million
Ibs. (145 x 10 metric tons) of chromium ferroalloy were imported for
consumption in 1982. Chromium is widely used as an alloying element in
stainless steel and heat-resistant materials; chromium compounds are
also used in pigments/ metal finishing, and leather tanning. Very
little chromite ore is processed to chromium metal, but rather most is
used in intermediate forms such as ferrochrome, sodium dichrornate, and
chromium trioxide. Table 1 summarizes the properties and uses of a
variety of chromium compounds (IARC, 1980).
1.2 Chemistry and Environmental Fate/Transport
Although chromium can exist in a variety of oxidation states, the
hexavalent (+6) and trivalent (+3) forms are the most significant.
Hexavalent chromium, such as dichrornate, is a strong oxidizing agent and
readily reacts with reducing agents and organic matter to produce the
more stable trivalent form. The foremost characteristic of trivalent
chromium is the tendency to form relatively inert complexes and insolu-
ble compounds. Chromium has its greatest industrial applications in the
+6 state due to its oxidizing properties and its ability to form soluble
colored salts (OWRS, 1980; ORNL, 1978).
Chromium is released into the atmosphere mainly from processes in the
chromium industry, such as ore refining, and from inadvertent sources,
such as coal combustion. Chromium is emitted and transported primarily
in particulate form and removal occurs by fallout and precipitation.
The chemical form of chromium in air depends on its source. While
chromium from metallurgical production is usually in the trivalent or
metallic state, hexavalent chromium may be released in dusts during
chroma te production and in the form of chromic acid aerosols from
plating processes (ORNL, 1978).
Most aqueous chromium in excess of background levels originates from
direct and indirect industrial discharges. Chromium is one of the most
commonly detected priority pollutants in sewage and industrial waste-
water. Trivalent chromium is very insoluble and tends to accumulate in
the sediments in the form of oxides or hydroxides. The hexavalent form
(i.e., chromates) tends to remain in solution due to its high water
solubility and resistance to adsorption. interconversion between the
two oxidation states does not occur under most environmental condi-
tions. Apparently, hexavalent chromium must diffuse into anaerobic
sediments in order to undergo reduction to the trivalent form and thus
accumulate in the sediment. Photolysis and volatilization are not
1 -i July, 1983
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TABLE 1: PROPERTIES OF CHROMIUM COMPOUNDS
Chemical Name
and Formula
CAS Number
and Synonyms
Oxidation
State
Transition
Points (°C)
Water
Solubility
(per liter)
Uses
Chromium
Cr
7440-47-3
chrome.
0 mp: 1857
bp: 2672
insol. In alloys for
strength, hardness
and corrosion
resistance.
Ferrochromium
11114-46-8
Chromium alloy,
Cr,C,Fe,N,Si;
ferrochrome.
insol. In stainless and
heat resistant
steels and alloys,
Chromite ore
Cr2°3*Fe°
1308-31-2
Chromite mineral
[Cr2Fe04l;
chrome ore;
chromite.
+3
Common mineral
forms also contain
Al, Mg, and other
metals.
Chromic oxide
Cr203
Chromic chloride
CrCl,
Chromium trioxide
CrO,
I-1
><
1308-38-9
Chromium oxide
[Cr203l;
chromium trioxide.
10025-73-7 +3
chromium chloride
[CrCl3l.
1333-82-0 +6
Chromic acid;
chromium oxide
[Cr03l.
mp: 2435
bp: 4000
mp: 1150
bp: decomposes
at 1300
mp: 196
bp: decomposes
insol. In pigments in
glass, ceramic
polymers, and
paints; also a
brick component.
585g
(hydrated)
625g
(20°)
Limited use in
dyes.
Corrosion inhibitor
in chrome plating
and an oxidizing
agent.
vo
00
-------
TABLE 1:
PROPER!^
.F CHROMIUM COMPOUNDS (cont.)
Chemical Name
and Formula
CAS Number
and Synonyms
Oxidation
State
Transition
Points (°C)
water
Solubility
(per liter)
Uses
Lead Chrornate
34
7758-97-6
Chromic acid
[H2CrO4l, lead
(2+) salt (1:1),
+6 mp: 844 0.58mg
bp: decomposes (25°)
Yellow orange
pigments for
paints, inks, and
resins.
Sodium Chromate
Na2Cr04
7775-11-3
Chromic acid,
[H2Cr04l, di-
sodium salt.
+6 mp: 792
bp: decomposes
873g
(30°)
In tanning and as
a preservative; an
intermediate for
other chromium
compounds.
Sodium Dichromate
10588-01-9
Chromic acid
[H2Cr207l
disodium salt.
+6 mp: 357
bp: decomposes
at 400°
2380g
(0°)
An intermediate for
many chromium
compounds; used in
tanning and as
corrosion inhibitor.
Source: (IARC, 1980).
Cj
e
03
CJ
-------
important transformation processes for chromium in water (OWRS, 1979;
OWRS, 1981).
Most chromium naturally present in soils is in an insoluble state in
adsorbed, mineral, or precipitated forms. In most cases, chromium in
soil is relatively immobile and is unavailable for uptake by plants.
Wind action and weathering can transport chromium-bearing soils to the
atmosphere. The chromium content of soils may be increased by applica-
tion of phosphate fertilizers and sludges. Chromium precipitated from
wastewaters and municipal wastes is often disposed of in landfills, and
leaching could potentially result in contamination of groundwater.
However, leachate is not expected to contain significant amounts of
chromium unless the landfill is subject to acidic conditions which would
solubilize and mobilize a portion of the chromium (ORNL, 1978).
1_4 July, 1983
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2. EFFECTS INFORMATION
2.1 Health Effects (Contacts: Lester Grant, FTS 629-4172; Si Duk Lee,
FTS 629-4159)
2.1.1 Acute Toxicity
Chromium is generally accepted to be an essential element in humans.
The amount of chromium needed to produce toxic effects is several
orders of magnitude higher than the dose needed to relieve symptoms of
chromium deficiency. Because of their insolubility, trivalent
chromium compounds are relatively nontoxic when qiven orally.
Hexavalent chromium compounds are strong oxidizing agents and are
highly irritating to tissues (ORNL, 1978).
The lethal oral dose in humans from the various forms of hexavalent
chromium has been estimated to be in the range of 1.5 to 16g. High
oral doses of hexavalent chromium can lead to kidney damage; tubular
necrosis has often been observed in humans following massive
accidental or deliberate exposures. Renal lesions have also been
reported in animals; a single subcutaneous dose (15mg/kg) of potassium
dichromate led to changes in renal tubules and increases in chemical
levels in the urine that were indicative of renal damage (IARC, 1980).
Acute human exposure to high concentrations of chromic acid via
inhalation results in severe damage to deep pulmonary structures.
Similar damage including bronchitis and pneumonia developed in cats
acutely exposed to dichromate (11-23 rag/kg). Acute skin exposure to
chromate dusts or solutions may result in the development of ulcers,
especially if a break in the skin is present. Acute systemic effects
of hexavalent chromium compounds are rare in humans and generally
result from deliberate exposure (ECAO, 1983).
2.1.2 Chronic Toxicity
Long-term exposures to relatively high dietary levels of chromium have
been studied extensively in animals. Although increases in chromium
concentrations were reported in the liver, spleen, and kidneys, few
adverse effects were noted in most cases. Thus, few systemic changes
are expected from moderately elevated oral exposure to chromium
(OWRS, 1980).
After a review of the toxicity data, EPA used a one-year feeding study
in rats to estimate an acceptable daily intake (ADI) for hexavalent
chromium. A well-defined, no-observable-effect-level (NOEL) of 2.5
rag/kg per day in rats was divided by a safety factor of 1000 to give
an ADI for a 70kg man of 0.18 mg/day. Several studies are also
available that give dose levels for trivalent chromium in animals with
no evidence of toxicity (NOEL). No effects were noted in a two-year
study with rats fed up to 5% trivalent chromium in their diet. This
translates into a NOEL of about 5.1 gAg per day and, using a safety
factor of 1000, EPA calculated an ADI of 357 mg of trivalent chromium
for a 70 kg adult (OWRS, 1980). Note that these ADI calculations
refer only to oral routes of exposure.
2-1 July, 1983
-------
Occupational exposures to airborne hexavalent chromium compounds give
rise to severe nasal irritation and to corrosive action in the nasal
passage (septum perforation). Bronchitis, bronchial asthma, and an
obstructive respiratory syndrome have all been reported in workers
exposed to hexavalent chromium compounds at concentrations as low as
0.12 mg/m . In animal studies, lifetime inhalation exposure to
calcium chromate (13 mg/m ) resulted in lung damage and ulceration of
the stomach and intestinal membranes. Dermal contact with chromic
acid, chromate dusts, or chromate solutions results in development of
primary dermatosis in workers. An eczmoid dermatitis, which is
considered an allergic reaction to chromate, may develop from skin
contact to much lower concentrations of hexavalent chromium
compounds. Sensitization may take place in a few days or over the
course of several years (ECAO, 1983).
Carcinogenicity, Hutagenicity, and Teratogenicity - The carcinogen-
icity of various chromium compounds has been well documented in
humans. Several studies of the chromate production industry have
demonstrated a large excess risk of lung cancer. Studies of the
chromate pigment industry also suggest a similar risk of lung
cancer. Although the available epidemiological evidence does not
permit a clear distinction between the relative carcinogenicity of
different chromium compounds, exposure to a mixture of hexavalent
compounds apparently carries the greatest risk (IARC, 1980).
Except for experiments showing sarcoma production at implantation or
injection sites, the evidence for cancer production by chromium in
experimental animals is not convincing. Attempts to produce lung can-
cers in animals by feeding or inhalation exposure to chromium have not
been very successful. Positive results were obtained, however, by
intrabronchial, intrapleural, intramuscular, or -subcutaneous injection
of hexavalent chromium compounds. These studies provide sufficient
evidence for the carcinogenicity of several chromium compounds in
animals. This work also indicates that all hexavalent forms of
chromium are likely to be carcinogenic, but that the degree is
modified by the solubility of the specific compounds. Thus, the
animal studies suggest that hexavalent chromium is the etiologic agent
in chromium-related cancer in humans (ECAO, 1983; IARC, 1980).
Most occupational epidemiological studies do not show an excess risk
of cancer at sites other than the respiratory tract; some studies
suggest that exposure to chromium compounds may lead to an increased
risk of gastrointestinal cancer, but this has not been firmly
established. Attention must be drawn to the fact that most
occupational exposures involve airborne chromium concentrations which
are quite high. In addition, the specific carcinogens responsible for
the increased incidences of cancer in various industries have not been
fully identified. It is also possible that chromium may possess
cocarcinogenic properties, especially at high levels of exposure
(OWRS, 1980).
2-2 July, 1983
-------
Evidence has accumulated in recent years to show that chromium
compounds possess the ability to cause cell transformations and
mutations. Hexavalent chromates are mutagenic in E. eoli and
Salmonella and also affect DNA repair in bacteria. Chromates appear
to be direct-acting mutagens and do not require activation by
microsomal fraction. In fact, several studies indicate that sodium
dichromate is deactivated as a mutagen in the Salmonella system in the
presence of liver microsomes. Trivalent chromium salts appear to be
either nonmutagenic or very weakly mutagenic in bacterial systems.
Hexavalent chromium is mutagenic in yeast, and soluble hexavalent
salts induce in vitro morphological transformations and chromosomal
aberrations in mammalian cells. Chromosomal aberrations are also
found in exposed workers (ECAO, 1983).
Little evidence exists for fetal damage that is directly attributable
to chromium. While trivalent chromium in the form of natural
complexes obtained from yeast can readily cross the placental barrier,
simple inorganic chromium compounds do not. Although embryonic
abnormalities were observed in the chick when hexavalent chromium was
injected directly into the yolks of eggs, the significance to normal
routes of exposure to chromium is questionable (OWRS, 1980).
Teratogenic effects were detected in hamsters following single
intravenous doses of 5 mg/kg Cr03 and in mice following a single
intraperitoneal injection of 15 mgAg CrCl3 during the critical period
of gestation. The most common findings were cleft palate and
hydrocephaly. Note that these teratogenic effects were observed at
doses that were toxic to the mother (ECAO, 1983).
2.1.3 Absorption, Distribution, and Metabolism
Less than 1% of trivalent chromium is absorbed from the
gastrointestinal (GI) tract of animals, whereas chromates are absorbed
at a rate of 3-6% in rats. In humans, hexavalent chromium is absorbed
from the GI tract at a'rate of about 2% (IARC, 1980). The ability of
GI juices to reduce hexavalent chromium to the trivalent form may
decrease any differences between the two valence states in absorption
efficiency or toxic effects after ingestion. Compounds of chromium
also penetrate the skin fairly readily in the hexavalent form, while
trivalent chromium reacts directly with epithelial and dermal
tissues. In animal studies, water-soluble chromates disappeared
rapidly from the lungs into circulation, whereas trivalent chromium
did not. Workers exposed to primarily hexavalent chromium also
absorbed chromium rapidly via the respiratory tract (IARC, 1980;
OWRS, 1980).
Normally in humans the highest concentration of chromium is found in
the lungs, and pulmonary levels tend to rise with age while the
chromium content in other tissues falls. Apparently, the lung obtains
most of the chromium from the air, not from oral exposure, and
pulmonary chromium is not in complete equilibrium with other body
pools of chromium. Once absorbed, the three major accumulation and
clearance organs are the liver, spleen, and bone marrow (OWRS, 1980).
2-3 July, 1983
-------
Chromium circulates in the blood bound primarily to plasma proteins.
The half-life of chromium in plasma is relatively short, and cells
tend to accumulate the metal. Chromium penetrates the cells in the
hexavalent state and reacts with cell constituents (such as hemoglobin
in red blood cells). Thus, within the cell, hexavalent chromium is
reduced to the trivalent form which cannot exit the cell. This lack
of chromium equilibrium between plasma and cells renders invalid the
use of blood levels as exposure indicators. In general, the reduction
of hexavalent chromium to the trivalent form and the subsequent
reaction of Cr+3 with organic molecules of biochemical importance
explain, in large part, the biological reactivity of chromium (OWRS,
1980). In rats, three main components of elimination have half-lives
of 0.5, 5.9, and 83 days. Urinary excretion is the major route of
elimination (ORNL, 1978).
Chromium is necessary for glucose and lipid metabolism and for
utilization of araino acids in several mammalian systems. It is also
important in the prevention of chronic diseases such as mild diabetes
and atherosclerosis in humans. In addition, nucleic acids normally
contain high chromium concentrations and the trivalent form may play a
role in maintaining the configuration of the RNA molecule (ORNL,
1978).
2.2 Environmental Effects
2.2.1 Aquatic Effects
Chromium toxicity to aquatic organisms varies with pH, hardness,
temperature, species, and the chemical form of chromium. Although
hexavalent chromium is often considered the greater hazard, the
bioassay data as a whole indicate no substantial overall differences
in the aquatic toxicity of the two forms. Trivalent chromium appears
to be more toxic in fish, while the hexavalent compounds are more
toxic for invertebrates (OWRS, 1981; OWRS, 1980).
The lowest observed acute or chronic values in fish and invertebrates
are 44 to 66 ug/L for trivalent and 47 ug/L for hexavalent chromium.
For hexavalent chromium, Water Quality Criteria have been set for
freshwater life. The acute criterion (21 ug/L) was determined
primarily from effects on the invertebrate Gammarus which is nearly
50-fold more sensitive than the next most sensitive species. The
chronic criterion for hexavalent chromium (0.29 ug/L) is almost 500-
fold lower than the chronic value for rainbow trout, the most
sensitive of three species tested for chronic effects (OWRS,1981).
2-4 July, 1983
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3. ENVIRONMENTAL RELEASE
In 1979 total domestic consumption of chromium was 540 x 10 metric
tons; metallurgical usage constituted 61% of consumption, while
chemical and refractory uses totaled 21% and 18%, respectively. The
greatest use by far of chromium is in the production of wrought
stainless and heat resistant steels. Major chemical uses are in the
production of pigments, metal finishing, and leather tanning (ECAO,
1983).
Table 2 summarizes the major sources of emissions of chromium to the
atmosphere; approximately 16,500 metric tons/yr are estimated to be
emitted after controls (for the year 1970). Hie major sources are
from different aspects of the chromium industry (ore refining,
chemical processing, refractory processing, and metallurgical
processing) and inadvertent sources (coal and oil combustion,
incineration, and asbestos mining) . Ferrochromium production during
refining is apparently the major source of atmospheric emissions
(68%). The more populated, industrial areas of the United States
receive the most emissions, especially the Great Lakes area and the
East Coast regions (Contact: Dave Patrick, FTS 629-5645).
POTWs discharge about 1,000 metric tons of chromium a year to water,
nearly all of which originates from indirect industrial discharge.
POTW influent is estimated to be approximately 8,000 metric tons/yr.
Based on limited data, the Metal Finishing and Leather Tanning
industries appear to contribute the most to POTW influents. Industry
also discharges about 850 metric tons/yr directly to surface waters,
most of which is generated by Coal Mining, Metal Finishing, Nonferrous
Metals, Organic Chemicals, Pulp and Paper, and Iron and Steel.
Chromium is one of the three or four most commonly detected priority
pollutants in sewage and industrial wastewater (OWRS, 1981)
(Contact: Mike Slimak, FTS 382-7051).
Although chromium in urban runoff is significant (perhaps up to 1000
metric tons/yr), most chromium in excess of rural background levels
appears likely to originate from industrial releases. The amount of
chromium disposed of on land is probably a large portion of total use,
but the quantity has not been estimated (OWRS, 1981).
3-1 July, 1983
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TABLE 2. SOURCES AND ESTIMATES OF UNITED STATES
ATMOSPHERIC CHROMIUM EMISSIONS IH 1970°
Source Chromium Emissions, metric tons/year
Industrial Sources:
ferrochromium refining 11,200
steel and alloy 595
material handling 750
chemical processing 106
refractory 1,650
Inadvertent Sources:
coal combustion 1,420
oil combustion 336
cement production 254
incineration 143
Total 16,500
aSource: (ORNL, 1978); controlled emissions.
3-2
July, 1983
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4. EXPOSURE
Food is apparently the major route of exposure to chromium for the
general population. The oral routes of exposure are not expected to
lead to harmful levels of chromium in the body when exposure involves
the low levels normally present in food and water. In fact, the
average American may actually suffer from mild chromium deficiency.
However, exposure to airborne chromium may pose special risks both
because the lungs tend to retain the element, and also because of the
carcinogenic hazard posed by inhaled hexavalent chromium (OWES, 1980).
4.1 Air Exposure
The majority of chromium in the atmosphere is probably in the
trivalent or metallic state. However, chromium released during chrome
production, chrome plating, and cooling tower drifts (chromate salts
are often used in cooling towers as a corrosion inhibitor) may be in
the more toxic hexavalent form. Air levels near a cooling tower were
measured to be about 50 ng/m3 up to 660 ft. from the tower. (ECAO,
1983).
Data concerning levels of total chromium in ambient air are available
from the EPA's National Aerometric Data Bank. According to the
available data obtained during the 1977 to 1980 period, the mean
chromium concentration for urban areas ranged from 0.0052 ug/m3 (i.e.,
background) to 0.16 ug/m ; the highest level (24 hour average) was 2.5
ug/m . Specific industrial sources such as power plants, incinera-
tors, and iron and steel plants may significantly increase atmospheric
levels in certain areas (ECAO, 1983).
4.2 Water Exposure
Although chromium is a widely distributed element, high levels are not
naturally found in surface or groundwater. The amounts of chromium
found in these waters are usually related to anthropogenic sources.
The chromium concentration in various United States drinking water
supplies has been measured in several studies. In a recent survey
(1974 to 1975} of 3834 tap waters from 35 representative locations
only 28% of the areas monitored had chromium levels above the
detection limit (0.1 ug/L). The range in this study was 0.4 to 8 ug/L
and the average value was 1.8 ug/L (ECAO, 1983). Assuming a typical
concentration of 2 ug/L, ingestion of 2 liters per day of water would
lead to the uptake of only 0.2 ug/day based on an absorption factor of
5% (OURS, 1981).
4.3 Other Exposure Routes
The chromium content of a variety of foods has been determined. Foods
with the highest mean concentrations are canned fruits (0.51 ppm),
seafoods (0.47 ppm), meats and fish (0.23 ppm}, frozen or fresh
vegetables (0.23 ppm), and grains and cereals (0.22 ppm). The most
recent (1979) diet study conducted by FDA-USDA indicated that the
chromium intake from the typical American diet was 62 ± 28 ug/day and
89 ± 56 ug/day respectively, for diets with high (43%) and low (25%)
4-1 July, 1983
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fat content (ECAO, 1983). Older estimates for dietary intake of
chromium ranged from 50 to 280 ug/day (OWES, 1980). Assuming 5%
absorption of ingested chromium, uptake from food containing 90 ug of
chromium would be 4 to 5 ug/day-(OWRS, 1981).
Chromium has been determined to be a component of cigarette tobacco.
Tobaccos grown in the United States have been found to have a chromium
content of 0.24 to 6.3 pptn. However, the amount actually inhaled
during smoking has not been determined (IARC, 1980).
NIOSH estimated that 175,000 workers in 104 occupations are
potentially exposed to hexavalent chromium. Chromium and its
compounds are found in several types of industrial activity
including: (1) the metallurgical industry, particularly chromium
extraction, ferro-alloy production, and chromium plating; (2) the
manufacture of refractory materials, such as bricks, glass, ceramics,
and certain metals; and (3) the pigment, paint, dyeing, and tanning
industries (IARC, 1980).
4-2 July, 1983
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5. DATA BASES
5.1 Chemicals in Commerce Information System (CICIS)
The Inventory was compiled under the authority of Section 8 of TSCA
which requires manufacturers to report to EPA the chemicals imported
and manufactured during calendar year 1977. The Inventory lists the
Chemical Abstract Service (CAS) preferred name for the chemicals,
their respective CAS number (often used for identification purposes),
production site, company name, and volume(s) of production and
import. There is also a Confidential Inventory in which many of these
characteristics are claimed confidential by the manufacturer. In
these instances, the confidential information will not be available on
the public inventory. CICIS can now be accessed through the NIH/EPA
Chemical Information System (CIS - see 5.3). For further information,
contact Gerri Nowack at FTS 382-3568 or Robin Heisler at FTS 382-3557.
5.2 EPA Chemical Activities status Report (EPACASR)
EPACASR is an on-line system containing information on EPA's interest
in chemicals. This system includes data on the Agency's regulations
research, and assessments directed toward specific chemicals. EPACASR
is published annually and the data base is updated as information is
received. A searchable subset itemized MTP/NCI studies and results,
as well as chemicals discussed in the IARC monograph series. (Other
sources are added as appropriate.) Entries identify the statutory
authority, the nature of the activity, its status, the reason for
and/or purposes of the effort, and a source of additional
information. Searches may be made by CAS Number or coded text.
(EPACASR is scheduled to be added to CIS in 1984.) For further
information contact Eleanor Merrick at FTS 382-3415.
5.3 NIH/EPA Chemical Information System (CIS)
This is a collection of various scientific data bases available
through an interactive computer program. The linking system between
these data files is the Structure and Nomenclature Search System
(SANSS). CIS can also provide a list of non-CIS sources of
information on a chemical of interest. However, these files have to
be accessed individually by either separate on-line systems or in
hard-copy. For further information contact Dr. Steve Heller at FTS
382-2424.
5.4 Chemical Regulations and Guidelines System (CRGS)
CRGS is an on-line data base which is being developed to provide
information on chemical regulatory material found in statutes,
regulations, and guidelines at the Federal, State, and international
levels. Currently, only the first phase of CRGS, which encompasses
only source material at the Federal level, is operational. Nation-
wide access to CRGS is available through Dialog. For further
information, contact (Doug Sellers) at FTS 382-2320.
5-1 July, 1983
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5.5 Chemical Substances Information Network (CSIN)
The Chemical Substances Information Network (CSIN) is a
sophisticated switching network based on heterogeneous distributed
data base management and networking concepts which were only theory
less than a decade ago. CSIN offers efficient and effective access to
on-line information resources (systems) containing data and
information relevant to chemical substances, as well as information
covering other scientific disciplines and subject matters, the
purposes of CSIN are two-fold; first to meet the growing chemical data
and information requirements of industry, academe, government (Federal
and State), public interest groups, others, and secondly to reduce the
burden on the private and public sector communities when responding to
complex Federal legislation oriented to chemical substances.
CSIN is not another data base. CSIN links many independent and
antonomous data and bibliographic computer systems oriented to
chemical substances, establishing a "library of systems". Users may
converse with any or all systems interfaced by CSIN (see Table 1)
without prior knowledge of or training on these independent systems,
regardless of the hardware, software, data, formats, or protocols of
these information resources.
Information accessible through CSIN provides data on chemical
nomenclature, composition, structure, properties, toxicity, production
uses, health and environmental effects, regulations, disposal, and
other aspects of the life cycle of materials as they move through
society. CSIN provides more data, information, and processing
capabilities than could practicably or cost effectively be included in
as single centralized data base. Users may now converse in and among
multiple systems through a single connection point — CSIN.
Currently, seven (7) independent information resources are
accessible through CSIN. They are: National Library of Medicine
(NLM), Chemical information System (CIS), CAS-On-Line, SDC's ORBIT,
Lockheeds's DIALOG, Bibliographic Retrieval Service (BRS), and the US
Coast Guard's Hazard Assessment Chemical System (HACS). Since
November of 1961 the CSIN support contractor has trained over 400
users from the public and private sectors, representing over 100
different organizations.
5.6 EPA Information Clearinghouse
The EPA information Clearinghouse is a bibliographic data base
composed of over 500 individual data bases and models which contain
monitoring information and statistics on a variety of chemicals. THe
individual data bases are maintained for offices within EPA. The
clearinghouse listed 120 citations for chromium. For further
information, contact Irvin Weiss at FTS 382-5918.
5-2 J\ily, 1983
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6. REGULATORY STATUS (Current as of 7/83)
6.1 Promulgated Regulations
6.1.1 EPA Programs
Clean Air Act (CAA)
o Section 111 - New Source Performance Standards have been issued
covering particulate emissions from ferroalloy production
facilities (40 CFR 60.260-.262). Although chromium emissions are
not directly controlled, particulate chromium is indirectly limited
by this NSPS. Most other source categories are also controlled to
some extent by existing State or Federal requirements for
particulate matter.
Clean Water Act (CWA)
o Sections 301, 304, 306, and 307 - Chromium and its compounds are
listed as priority pollutants (toxic pollutants, 40 CFR 401.15).
Effluent limitations, pretreatment standards, and new source
performance standards have been issued for sections of the
following industries:
o Textile (40 CFR 410, Subparts A-B and D-G)
o Electroplating (40 CFR 413, Subparts A-B and D-H)
o Inorganic chemicals (40 CFR 415, Subparts L, Q, V, W, AH, AL,
and BB)
o Petroleum refining (40 CFR 419, Subparts A-E)
o Iron and steel manufacturing (40 CFR 420, Subparts T and W-Z)
o Non-ferrous metals (40 CFR 421)
o Steam electric power generating (40 CFR 423, Subparts
A-C)
o Ferroalloy manufacturing (40 CFR 424, Subparts A-C and G)
o Leather tanning and finishing (40 CFR 425, Subparts A-F)
o Rubber manufacturing (40 CFR 428, Subpart J)
o Timber products (40 CFR 429, Subparts G and H)
o Pulp, paper, and paperboard mills (40 CFR 430 and 431)
o Electroplating and metal finishing (40 CFR 433)
o Ore mining and dressing (40 CFR 440)
o Paint formulation (40 CFR 446)
o Ink formulation (40 CFR 447)
o Battery manufacturing (40 CFR 461)
o Metal molding and casting (40 CFR 464)
o Aluminum forming (40 CFR 467)
o Copper forming (40 CFR 468)
o Section 311 - The following chromium compounds have been designated
as hazardous materials and are subject to reportable quantity rules
for discharges exceeding 1,000 Ibs (40 CFR 116.4 and 117.3):
o Ammonium chrornate
o Calcium chromate
o Chromic acetate
6-1 July, 1983
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o Chromic acid
o Chromic sulfate
o Chromous chloride
o Lithium chromate
o Potassium bichromate
o Potassium chromate
o Sodium chromate
o Sodium bichromate
o Strontium chromate
o Sections 402 and 404 - Discharge of toxic pollutants such as
chromium are controlled by permits required under the National
Pollutant Discharge Elimination System (NPDES). Permits for
discharge of dredged or fill materials are issued by the Army Corps
of Engineers (40 CFR 122 to 125).
Safe Drinking Water Act (SDWA)
o Section 1412 - Establishes a maximum contaminant level (MCL) for
chromium in drinking water supplies (40 CFR 141.11).
o Sections 1421 to 1424 - Establishes an underground injection
control (UIC) program to protect underground sources of drinking
water (40 CFR 146).
Resource Conservation and Recovery Act (RCRA)
o Sections 1008(a)(3) and 4004(a) - Establishes a safe level for
chromium in ground water (40 CFR 257, App. I).
o Section 3001 - Chromium and its compounds are designated as
hazardous constituents (40 CFR 261, App. VIII). Extractable
chromium also characterizes waste as hazardous (40 CFR 261.24).
Non-specific sources of chromium-containing hazardous wastes
include electroplating operations (40 CFR 261.31, App. VII). Haste
streams containing chromium from the following industries are
listed as specific sources of hazardous waste: pigment production,
ink formulation, production of iron and steel, and petroleum
refining (40 CFR 261.32, App. VII). Calcium chromate is designated
as a toxic waste (U032) when it is discarded or intended to be
discarded as a commercial product or off-specification species.
Container residues and spill residues are also included.
o Sections 3002 to 3006 - Hazardous wastes containing chromium are
subjecttofurthercontrol under RCRA. Regulations cover
generators (40 CFR 262) and transporters (40 CFR 263) of such
waste; and treatment, storage, and disposal facilities are subject
to interim standards (40 CFR 264 and 265). Hazardous waste-
permitting procedures are included in the consolidated permit
regulations (40 CFR 122 to 124).
6-2 July, 1983
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6.1.2 Programs of Other Agencies
QSHA - Occupational Safety and Health Act
o General industry standards for workplace exposure to air
contaminants (29 CFR 1910.1000):
o Chromic acid and chromates
o Soluble chromic and chromous salts
o Metal and insoluble salts
o Regulations also cover respiratory protection from chrominum dust
(29 CFR 1915.152) and ventilation requirements for welding,
cutting, or heating chromium-bearing metals (29 CFR 1915.51 and
1926.353).
FDA - Food, Drug, and Cosmetic Act
o Maximum quantity of chromium-cobalt-aluminum oxide as coloring
agent in surgical sutures (21 CFR 73.1015).
o Minimum amount of chromium oxide in chromium hydroxide green
coloring agent used in externally applied drugs (21 CFR 73.1326)
and cosmetics (21 CFR 73.2326).
o Minimum amount of chromium oxide in chromium oxide coloring agent
used in externally applied drugs (21 CFR 73.1327) and cosmetics (21
CFR 73.2327).
o Maximum level of chromium as an impurity in food coloring FDSC Blue
No. 1 (21 CFR 74.101), FD&C Green No. 3 (21 CFR 74.203), drug
coloring DSC Blue No. 4 (21 CFR 74.1104) and cosmetic coloring DSC
Blue NO. 4 (21 CFR 74.2104).
o Standard for bottled water (21 CFR 103.35).
o Regulated under 21 CFR 175.105 for packaging adhesives; 21 CFR
176.160 and 21 CFR 176.180 for packaging; 21 CFR 177.2600 for
rubber products; 21 CFR 178.3120 in paper and paperboard
manufacture; 21 CFR 178.3290 for release agents in food packaging;
21 CFR 181.30 for use in waxed paper and paperboard.
MSHA - Mine Safety and Health Act
o Performance requirements for respirators (30 CFR 11.130-140):
o Chromium
o Chromic acid
6-3 July, 1983
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6.2
6.2.1
DOT - Hazardous Materials Transportation Ret
o Listed as a hazardous material (49 CFR 172.101):
o Chromic acid
o Chromic fluoride
o Chromium oxychloride
o Chromic anhydride
o Chromic sulfate
o Chromic acetate
o Chromium
o Chromous chloride
o Specifications for packaging (49 CFR 173.164 and 49 CFR 173.247):
o Chromic acid
o Chromium oxychloride
Proposed Regulations
EPA Programs
CWA
o Sections 54, 204, 208,
301, 304, 307, 308, 309, 402, 405, and 501
General pretreatment regulations for a wide variety of existing and
new sources (47 FR 42698).
o Section 403 - Ocean discharge criteria (45 FR 9549).
o Comprehensive Environmental Response, Compensation, and Liability
Act (CERCLA or Superfund)
o CERCLA provides for the liability, compensation, clean-up, and
emergency response for the release of hazardous substances into the
environment. ttiis Act also deals with the cleanup of hazardous
waste disposal sites. (42 USC 9601; PL 96-510). EPA is developing
regulations concerning the designation of hazardous substances, the
development of reportable quantities (RQ), claims procedures, and
the confidentiality of business records (46 FR 54032).
o Chromium compounds are hazardous substances under CERCLA and will
be subject to regulations developed under Superfund. Although EPA
has proposed adjustments to many of the RQs established under
CERCLA and the CWA, RQs for chromium compounds are still under
development (48 FR 23552).
Atomic Energy Act
o Section 206(a) - Proposed disposal standards for uranium mill
tailings; limit on chromium leakage (46 FR 2556).
6-4 July, 1983
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6.2.2 Other Programs
OSHA
o Sections 6(b) and 8(g)(2) - Proposed standard requires employers to
identify hazardous materials in the workplace (46 FR 4412).
6.3 Other Actions
CAA
o Although OAQPS has not yet proposed regulations, chromium is
considered a high assessment priority. An exposure assessment has
been completed and a source assessment is undergoing revision. A
regulatory decision is currently scheduled for early FY 1985
(Contact: Dave Patrick, FTS 629-5645).
NIOSH - Occupational Safety and Health Act
o Request for information on data pursuant to the development of a
criteria document for chromic acid.
6-5 July, 1983
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7. STANDARDS AND RECOMMENDED CRITERIA*
7.1 Air
o Current OSHA occupational standards (29 CFR 1910.1000):
Soluble chromic and chromous salts 500 ug/m3 (8-hr. TWA)
Chromium and insoluble salts 1,000 ug/m3 (8-hr. TWA)
Chromic acid and chromates 100 ug/m3 (ceiling)
o NIOSH recommendations for occupational exposure limits:
Chromic acid 50 ug Cr03/m3 (8-hr. TWA)
100 ug Cr03/m (ceiling)
Carcinogenic chromium** 1 ug/m
(VI)
Chromium (VI) 25 ug/m3 (8-hr. TWA)
50 ug/m (ceiling)
o American Conference of Government Industrial Hygienists (ACGIH)
threshold limit values (TLV) based on an 8-hour time-weighted
average:
Chromium metal, 0.5 mg/m
Chromium II compounds, and
Chromium III compounds
Chromium VI compounds 0.05 mg/m
and
Chromite ore processing
Tert-Butyl Chromate, 0.1 mg/m
as Cr03 (skin)
7.2 Water
o Various chromium compounds are designated as hazardous substances
under Section 311 of the CWA and have reportable quantities for
spills defined as over 1,000 Ibs (40 CFR 117.3). See Section 6.1.1
of this document for compounds listed.
*See Appendix A for a discussion of derivation, uses, and limitations of these
criteria and standards.
••Certain forms of chromium (VI) have been found to cause increased
respiratory cancer among workers; other forms are currently labeled non-
carcinogenic by NIOSH.
7-1 July, 1983
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o Maximum Contaminant Level (HCL)
for total chromium in drinking
water (40 CFR 141.11) and ground
water (40 CFR 257, App. I).
o Water Quality Criteria (45 PR 79318)
50 ug/1
Freshwater aquatic life:
Chromium III
Chromium VI
Saltwater aquatic life:
Chromium III
Chromium VI
44 ug/1 (chronic)
0.29 ug/1 (24-hr, average)
21 ug/1 (ceiling)
10,300 ug/1
18 ug/1
1,260 ug/1
(acute)
(24-hr, average)
(ceiling)
Human health (values refer to non-carcinogenic criteria
levels associated with ingestion of contaminated aquatic
organisms and drinking water except where indicated):
Chromium III
Chromium VI
170 mg/1
3,433 mg/1 (ingestion of
aquatic organisms
only)
50 ug/1
7.3 Other
o Solid waste is considered 5.0 mg/1
hazardous if the concentration
of chromium equals or exceeds
this maximum for extractable
chromium (40 CFR 261.24).
o Numerous FDA regulations set limits on levels of chromium permitted
in coloring agents. See Section 6.1.2 for CFR citations.
o FDA maximum concentration level of 0.05 mg/1 total chromium in
bottled water (21 CFR 103.35).
7-2
July, 1983
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8. SPILL OR OTHER INCIDENT CLEANUP/DISPOSAL
8.1 Hazards
The toxicity and hazardous properties of chromium compounds vary
widely. In general, the hexavalent chromate salts and chromic acid
are the most hazardous due to their irritative and corrosive action on
skin, mucous membranes, GI tract, and the respiratory tract. In
addition, hexavalent chromium compounds are recognized as having
carcinogenic potential when inhaled. Chromate salts are strong
oxidizing agents and may react violently with other chemicals and
organic matter. Chromic acid (CrO^) reacts so vigorously that it may
ignite on contact with compounds such as acetic acid and alcohol, and
organic materials such as cloth or wood.
Protective clothing should be worn during clean-up to prevent skin
contact with solids or liquids containing chromic acid or chromates.
Areas in which exposure to carcinogenic hexavalent chromium may occur
should be identified and access should be limited.
8.2 First Aid
Acute poisoning by ingestion of chromates is manifested by dizziness,
thirst, abdominal pain, vomiting, and shock. Use of dimercaprol has
been suggested as treatment. Emergency treatment includes the
immediate administration of large amounts of water; afterwards try to
induce vomiting. Skin or eye exposure should be followed by thorough
washing with water. Contaminated clothing must be removed
immediately. In case of inhalation exposure, move the victim to fresh
air and perform articial respiration if necessary.
8.3 Emergency Action
Unnecessary people and people not wearing protective equipment and
clothing should be restricted from spill areas. If chromic acid or
chromates are spilled, the area should be ventilated, and the material
collected for disposal. Solutions should be absorbed with
vermiculite, sand, or similar material. Fires can be extinguished
with water, spray, or foam. Note that a few chromium compounds
(chromium oxychloride, chromosulfuric acid) may react violently with
water. Fire may also produce toxic gases from the decomposition of
chromium compounds.
8.4 Notification and Technical Assistance
Section 103(a) of CERCLA {Superfund) requires notification of the
National Response Center (NEC; 800-424-8802; in Washington, D.C.,
426-2675) if releases exceed reportable quantities (RQ). At present,
Section 102 of CERCLA sets a statutory RQ of 1 pound for hazardous
substances except those for which RQs have been established previously
under Section 311 of the CWA. Thus, until and unless adjustments of
the RQs are promulgated, the CWA RQs of 1000 Ibs. are in effect for a
number of chromium compounds (see section 6.1.1 of this document).
8-1 July, 1983
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For technical assistance call CHEMTRBC (800-424-9300) or EPA's
Environmental Response Team (ERT), Edison, NJ (201) 321-6660. Farther
information may be obtained from the Division of Oil and Special
Materials (1-202-245-3045).
The Center for Disease Control (CDC) has developed a manual ("A System
for Prevention, Assessment, and Control of Exposure and Health Effects
from Hazardous Sites") in order to help State health departments in
efforts related to hazardous wastes and substances. The manual
includes procedures for inspection of hazardous waste sites,
monitoring and analysis of hazardous substances (including chromium),
assigning priorities to various sites, and conducting health
studies. Sources of information and assistance related to these tasks
are also given (Contact: Kathy Deck, FTS 236-4100).
8.5 Disposal
Generators of more than 1,000 kg of hazardous waste per month, or
spill clean-up residues or debris resulting from clean-up are subject
to regulation under RCRA. Such wastes include wastes that fail the EP
(extraction procedure) toxicity test for chromium (40 CFR 261.24).
A variety of industrial wastestreams which contain chromium are also
listed as hazardous (40 CFR 261.31 and 261.32), including sludges from
electroplating (F006) and from chemical conversion of aluminum
(F019). Specific source wastestreams which contain chromium are
listed below by industry:
Inorganic Pigments Wastewater treatment sludges and oven
residue from the production of inorganic
pigments.
Petroleum Refining Dissolved air flotation (DAF) float, stop
oil emulsion solids, heat exchanger bundle
cleaning sludge, and API separator sludge
from the petroleum refining industry.
Iron and Steel Emission control dust/sludge from the
primary production of steel in electric
furnaces and spent pickle liquor from
steel finishing.
Secondary Lead Emission control dust/sludge and waste
leaching solution from secondary lead
smelting.
Ink Formulation Washes and sludges from equipment used
in the formulation of ink from pigments,
driers, soaps, and stabilizers containing
chromium and lead.
8-2 July, 1983
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9. SAMPLING, ACCEPTABLE ANALYTICAL TECHNIQUES, AND QUALITY ASSURANCE
9.1 Air
Although no EPA approved procedures have been issued for the analysis
of chromium in air, a variety of procedures have been published. The
NIOSH Manual of Analytical Methods contains several procedures which
may be useful in analytical situations outside of the occupational
environment. Method 351 in the NIOSH Manual (Volume 7) describes a
general method for the analysis of trace elements, including chromium,
by inductively coupled plasma-atomic emission spectroscopy (ICP-AES)
in airborne material. A known volume of air is drawn through a mixed
cellulose ester filter and the filters are treated (HNCK/HCIO.) to ash
the organic matrix and dissolve the elements. Analysis is
accomplished by nebulization into an inductively coupled argon plasma
and monitoring the emission spectra of the various elements. The
working range in 5 to 2000 ug/m in a 500 L sample (i.e., 2.5 to 1000
ug dissolved in a 10 mL sample solution). The instrumental detection
limit for chromium is quite low (1.3 ng/mL of solution) which
translates into a detection limit of about 0.03 ug/m3 for a 500 L air
sample. Multi-element spiked filters at 2.5 ug element/filler ashed
and analyzed by this procedure yielded a relative standard deviation
of approximately 5% for chromium and recoveries of chromium were
essentially quantitative.
The NIOSH Manual also contains procedures for analysis of chromium in
air by atomic absorption AA spectrosopy (Method 152, Vol. 1),
colorimetry (Method 319, Vol. 6), a kinetic procedure (Method 182,
Vol. 1), and methods to analyze for insoluble or soluble chromium
compounds (Methods 8323 and S352, Vol. 3). Among other techniques
commonly used in the analysis of air particulates (collected on
filters) is X-ray fluorescence (XRF). This method is particularly
well suited to samples which have more-or-less homogeneous surfaces,
such as filtered air particulates. XRF can distinguish between the
oxidation states of chromium without pretreatment of the samples.
Neutron activation analysis is also widely used to determine chromium
levels due to its high sensitivity, ability for multi-element
analyses, and the need for a minimum of processing prior to
analysis. In ambient air, dusts and fumes of chromium compounds are
usually collected by high volume samplers. Typical filter media have
included cellulose, polyethylene, PVC, and glass fibers (ECAO, 1983).
9.2 Water
Chromium is listed under the Clean Water Act 304(h) as an inorganic
priority pollutant. A drinking water standard has also been
promulgated which lists a Maximum Contaminant Level (MCL) of 0.05
mg/L. The Agency-approved methods described below may be used for
measuring both total and dissolved chromium; if dissolved chromium is
to be measured, the sample must be filtered (0.45 micron membrane
filter) prior to analysis. The sample (or filtrate) may be preserved
with HN03 (pH 2); however if hexavalent chromium is to be determined
(Method 218.4), the sample should not be preserved with acid, but
rather filtered and a portion of the filtrate analyzed as soon as
possible for hexavalent chromium.
9-1 July, 1983
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The approved methods for chromium (Methods for Chemical Analysis, of
Water and Wastes, 1979, EPA-600/4-79-020, Environmental Monitoring and
Support Laboratory) all utilize atomic absorption (AA) techniques for
analysis. The direct aspiration procedure (Method 218.1) has an
optimum working range of 0.5 to 10 mg/L and a detection limit of 0.05
mg/L.
For increased sensitivity, the sample may be concentrated by chelation
of hexavalent chromium prior to analysis. To determine total chromium
present (Method 218.3) the sample must first be treated with an
oxidizing agent in order to convert trivalent chromium to the
hexavalent form. Method 218.4 covers the determination of dissolved
hexavalent chromium only, and thus, the sample is not oxidized prior
to extraction. Both chelation methods utilize direct aspiration AA
and have a working range of 1.0 to 25 ug/L.
When direct aspiration AA techniques do not provide adequate
sensitivity, furnace techniques may be used (Method 218.2). In this
procedure, hydrogen peroxide is added to convert all chromium to the
trivalent state. The optimum concentration range is 5 to 100 ug/L and
the detection limit is 1 ug/L. To insure valid data with furnace
techniques, the sample matrix should be examined for interference
effects.
EPA has also issued a method for multi-element analysis which can be
used to determine chromium concentration in solution. (Federal
Register 44, 69559, December 3, 1979). The method (200.7) uses
inductively coupled plasma-atomic emission spectroscopy (ICP-AES).
The atomic-line emission spectra are processed by computer to correct
for background and spectral interference. The estimated instrumental
detection limit for chromium is 7 ug/L (at 267.7 nm).
Several methods for chromium analysis are also included in Standard
Methods for the Examination of Water and Wastewater, 15th Edition,
American Public Health Association (1980). Direct aspiration AA
procedures (Methods 303A and 303B) are quite similar to EPA methods
(218.1 and 218.3). A colorimetric method (Method 312B) based on the
reaction of hexavalent chromium with diphenyl carbazide in acid
solution is also included. (To determine total chromium, potassium
chrornate is used to convert all chromium to the hexavalent form.) The
intense red violet color produced is monitored at 540 nm. This method
may be used to analyze samples containing 0.5 to 50 mg of chromium per
liter.
9-2 July, 1983
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9.3 Solid Waste
Five approved methods for chromium analysis in wastes are given in
Test Methods for Evaluating Solid Wastes - Physical Chemical Methods,
EPA/SW-846, Office of Solid Waste (1982). Methods 7190, 7191 and 7197
are AA methods similar to water methods 218.1, 218.2, and 218.4
respectively. Method 7195 is a specific procedure for determining the
level of hexavalent chromium in solution. This method is based on the
separation of hexavalent chromium from solution by coprecipitation of
lead chromate with lead sulfate. The hexavalent chromium is then
reduced to the trivalent state and quantified by either flame or
furnace AA. Method 7196 is a colorimetric procedure analogous to the
procedure described in Standard Methods referenced in the water
section (9.2) of this document.
Acid digestion procedures for the preparation of samples for analysis
by flame and furnace AA are given in the solid waste document noted
above (methods 3010 and 3020). These methods are applicable for
aqueous samples, EP extracts, and certain nonaqueous wastes containing
chromium. A method (3050) is also included to prepare sludge-type and
soil samples for analyses by AA or ICP methods. A special method
(3060) describes the alkaline digestion of waste samples for analysis
for hexavalent chromium; the digestion is done under basic conditions
to protect the chromium from reduction to the trivalent form.
9.4 Other Samples
Analytical methods for the detection of chromium have been summarized
in an IARC monograph (IARC, 1980) and in several EPA publications
(ECAO, 1983; ORNL, 1978). Sampling and analytical methods used to
monitor air, water, and soil near industrial sites have been
summarized in Environmental Monitoring Near Industrial Sites, Chromium
(PB-271 881; 1977). Numerous references exist for the analyses of
biological samples (IARC, 1980) and NBS has recently issued chromium
certified materials for biological media (yeast, liver, plants).
9-3 July, 1983
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REFERENCES
The major references used in preparation of this document are listed below.
EPA references are listed by EPA office of origin and the year of
publication. For further information refer to contacts given throughout this
document or contact the relevant EPA offices listed at the end of this
section.
(ECAO, 1983) Health Assessment Document for Chromium, EPA-600/8-83-014A,
External Review Draft, Environmental Criteria and Assessment
Office (1983).
(IARC, 1980) IARC Monographs on the Evaluation of the Carcinogenic Risk of
Chemicals to Humans, Vol. 23, p. 205, International Agency for
Research on Cancer, World Health Organization (1980).
(ORNL, 1978) Reviews of the Environmental Effects of Pollutants;III.
Chromium,
(1978).
EPA-600/1-78-023, Oak Ridge National Laboratory
(OWRS, 1979)
(OWRS, 1980)
(OWRS, 1981)
Water Related Environmental Fate of 129 Priority Pollutants,
Vol. I, Chapter 10, EPA 440/4-79-029a, Office of Water
Regulations and Standards (1979).
Ambient Water Quality Criteria for Chromium, EPA-
440/5-80-035, Office of Water Regulations and Standards (1980).
Recommendations for Control of Environmental Hazards of
Chromium, draft document,
Standards (1981).
Office of Water Regulations and
R-1
July, 1983
-------
OFFICE CONTACTS
The EPA offices and divisions that are listed below may be contacted for more
information relating to the indicated sections of this document. While these
offices are, in many cases, the offices of origin for the data included in
this paper, the personal contacts given throughout this document should be
contacted first. Unless otherwise noted, the offices listed are situated in
Headquarters, Washington, D.C., and the telephone numbers given are FTS
(Federal Telecommunications System) numbers. For commercial telephone calls
to Headquarters which are not placed on FTS, area code 202 must be used.
Other commercial numbers are noted for the office contacts located outside
Washington, D.C.
HEALTH AMD ENVIRONMENTAL EFFECTS (Section 2)
Office of Health and Environmental Assessment (OHEA)
Environmental Criteria and Assessment Office:
Cincinnati, OH 684-7531 (513-684-7531)
Research Triangle Park, NC 629-4173 (919-541-4173)
Carcinogen Assessment Group 382-7341
Office of Drinking Water (ODW)
Health Effects Branch 382-7571
Office of Toxic Substances (OTS)
Health and Environmental Review Division 382-4241
Environmental Research Laboratory
Duluth, MM, Region V 783-9550 (218-727-6692)
ENVIRONMENTAL RELEASES AND EXPOSURE (Sections 3 and 4)
Office of Air Quality and Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Water Regulations and Standards (OWRS)
Monitoring and Data Support Division 382-7051
Office of Toxic Substances (OTS)
Exposure Evaluation Division 382-3873
R-2 July, 1983
-------
DATA BASES (Section 5)
Office of Toxic Substances (OTS)
Information Management Division 382-3749
REGULATORY STATUS, STANDARDS, AND CRITERIA (Sections 6 and 7)
Office of Mr Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Drinking water (ODW)
Criteria and Standards Division 382-7575
Office of Water Regulations and Standards (OWRS)
Criteria and Standards Division 755-0100
Effluent Guidelines Division 382-7120
Office of Solid Waste (OSW)
Permits and State Programs Division 382-4746
SPILL CLEAN-UP AND DISPOSAL (Section 8)
NOTE: For Emergencies call the National Response Center at 1-800-424-8802
(1-800-426-2675 from the Baltimore/Washington area).
Office of Emergency and Remedial Response (OERR)
Emergency Response Division 382-2182
Hazardous Site Control Division 382-2443
Oil and Hazardous Materials Spills Branch
Edison, NJ; Region II 340-6635 (201-321-6635)
ANALYTICAL TECHNIQUES (Section 9)
Environmental Monitoring Systems Lab (EMSL)
Air Analysis
Research Triangle Park, NC 629-2454 (919-541-2454)
Water Analysis
Cincinnati, OH 684-7311 (513-684-7311)
Waste Analysis
Las Vegas, NV 545-2137 (702-798-2137)
R-3 July, 1983
-------
Office of Monitoring Systems
and Quality Assurance 382-5767
GENERAL IPP COMMENTS, CORRECTIONS, OR QUESTIONS
Chemical Coordination Staff
Chemical Information
and Analysis Group 382-3375
R-4 July, 1983
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CHLORINATED PHENOLS
-------
CHLOROPHENOLS
Table of Contents
Page
Physical/Chemical Properties and Chemistry 1-1
Properties 1-1
Chemistry and Environmental Transport 1-1
Effects Information 2-1
Health Effects 2-1
Environmental Effects 2-5
Environmental Release 3-1
Exposure Routes 4-1
Air Exposure 4-1
Hater Exposure 4-2
Other Exposure Routes 4-2
Data Bases 5-1
Chemicals in Commerce Information System (CICIS) 5-1
EPA Chemicals Activities Status Report (EPACASR) 5-1
NIH/EPA Chemical Information System (CIS) 5-1
Chemical Regulations and Guidelines System (CRGS) 5-1
Chemical Substances Information Network (CSIN) 5-2
EPA Information Clearinghouse 5-2
Regulatory Status 6-1
Promulgated Regulations 6-1
Proposed Regulations 6-2
Other Actions 6-3
Standards and Recommended Criteria 7-1
Air 7-1
Water 7-1
Other 7-2
July, 1983
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Spill or Other Incident Cleanup/Disposal 8-1
Hazards and Safety Precautions 8-1
First Aid 8-1
Emergency Action 8-1
Notification and Technical Assistance 8-1
Disposal 8-2
Sampling, Acceptable Analytical Techniques, and Quality Assurance 9-1
Air 9-1
Water 9-1
Solid Waste 9-2
Other Samples 9-3
References and Office Contacts R-1
July, 1983
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CHLOROPHENOLS
1. PHYSICAL/CHEMICAL PROPERTIES AND CHEMISTRY
1.1 Properties
Chlorophenols are a family of compounds consisting of the phenol ring
structure substituted with from one to five chlorine atoms.
Chlorophenols are used as intermediates in the manufacture of dyes,
herbicides, pesticides, pigments, and phenolic resins. Certain
Chlorophenols are also used directly as antimicrobial agents and
preservatives. There are 19 different Chlorophenols which differ in
the degree or site of chlorination of the aromatic ring.
Commercially, the most important compounds are: 2-chlorophenol
(2-CP), 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-CP),
2,4,5-trichlorophenol (2,4,5-TCP), and pentachlorophenol (PCP)
(ECT, 1979; OWRS 1980a).
As shown in Table 1, the physical/chemical properties of
Chlorophenols vary according to chlorine content. The less
chlorinated isomers are moderately volatile and water soluble while
the highly chlorinated phenols are relatively nonvolatile and only
sparingly soluble in water. The dissociation constants in Table 1
illustrate that increased chlorination also increases the acidity of
the chlorophenol (ORNL, 1979).
1.2 Chemistry and Environmental Fate/Transport
Most Chlorophenols are commercially synthesized by the chlorination
of phenol. Other Chlorophenols which have no commercial applications
are produced to some extent as by-products during the synthesis of
commercially important Chlorophenols. Chlorinated dibenzo-p-dioxins
may also be formed during the synthesis of Chlorophenols. The highly
toxic 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) has been
reported in commercial samples of 2,4,5-TCP and is carried as a trace
contaminant in derived herbicides. While other chlorinated dioxins
have been found in samples of tetra- and pentachlorophenol, the
2,3,7,8-TCDD isomer has not been reported. Chlorodibenzofurans have
also been found as contaminants in various chlorophenol samples
(ORNL, 197'9).
Only a small fraction of environmental releases of Chlorophenols is
emitted to the atmosphere, primarily in the form of vapor from
production processes. Little air monitoring has been done for these
substances and the fate and persistence of Chlorophenols in the
atmosphere are not known. The detection of FCP in precipitation,
however, indicates that this relatively non-volatile chlorophenol is
present in the atmosphere and that it is removed by washout. While
little or no evidence exists regarding degradation of Chlorophenols
in the atmosphere by photolysis or free radical oxidation, these are
probably not significant removal pathways (OWRS, 1980e; OWRS, 1980f).
1-1 July, 1983
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TABLE 1. PHYSICAL PROPERTIES OF CHLOROPHENOLSa
to
Chemical Name
2-Chlorophenol
4-Chlorophenol
2, 4-Dichlorophenol
2,4,5-Trichlorophenol
2,4, 6-Tr ichlorophenol
2, 3,4,6-Tetra-
chlorophenol
Pentachlorophenol
0 Data as summarized
Melting
Point
CAS Number (°C)
95-57-8
106-48-9
120-83-2
95-95-4
88-06-2
58-90-2
87-86-5
in (ORNL,
Log octanol-water partition
c pK = - log K, , where K is
C| el el el
c
M
ID
00
U>
d Prom (OWRS, 1979).
8.7
40-41
43-33
68
68
69-70
190
1979) or (OTS,
coefficients are
the dissociation
Boiling
Point
175
220
210
245-246
246
150
(15 torr)
310
1980) unless
the highest
constant.
Water
Solubility
(q/100g)
2.85 (20°C)
2.71 (25°C)
0.45 (20°C)
si. sol.
0.08 (25°C)
0.01 (25°C)
0.0014
(20°C)
otherwise
and lowest
Vapor
Pressure
(torr)
1 (12°C)
1 (53°C)
1 (72°C)
d 1 (76°C)
1 (1OO°C)
0.12
(100°C)
noted.
values reported
Log Pb pKac
2.12-2.19 8.50
2.35-2.53 9.18
3.06-3.30 7.68
3.72 7.43
3.62-4.05 7.42
4.10 5.38
5.01-5.86 4.92
in (Hansch, 1979).
-------
Chlorophenols enter the environment by discharge to water primarily
by chemical producers. Chlorophenols may also be inadvertently
produced during treatment of drinking water by chlorination of phenol
and lower Chlorophenols already present. Chlorophenols are removed
from environmental waters by volatilization, sorption to sediments,
biodegradation, or photodegradation. ' The relative importance of
these processes is unclear due to a lack of experimental data (OWRS,
1980e).
The high vapor pressure of the lower Chlorophenols suggests that
volatilization plays a role in their dissipation from water.
However, definitive data are not available and the relatively high
water solubility of the less chlorinated phenols should inhibit
volatilization. Biodegradation is probably the major route of
removal of most Chlorophenols from aquatic environments. However,
due to the microbial toxicity of these compounds, ready degradation
probably requires acclimated microorganisms. Based on octanol/water
partition coefficients, adsorption onto organic matter appears to be
important for the higher Chlorophenols. For example, PCP and its
metabolites are known to concentrate in sediment and to bioaccumulate
in fish. While the anionic forms of the chlorinated phenols may
undergo photochemical reactions in surface waters, other chemical
reactions in water, such as hydrolysis and oxidation, are unlikely
(OWRS, 1980f; ORNL, 1979).
The primary source of soil contamination by many Chlorophenols is
through application of herbicides; other Chlorophenols enter the soil
as impurities or breakdown products of several pesticides. Based on
limited data, the mono-, di-r and trichlorophenols seem to be
absorbed only weakly by soil particles, and the potential for seepage
into groundwater exists. As in water, biodegradation plays a crucial
role in the dissipation of Chlorophenols from soil. Microbial
degradation in soils is inhibited by the presence of a chlorine atom
in the meta-position (ring position 3 or 5); limited data indicate
that 2,4,5-TCP, 2,3,4,6-tetrachlorophenol, and PCP are more
persistent. Even the most resistant isomers appear to biodegrade
under appropriate conditions; however, the rate of removal depends on
a variety of soil parameters and on the presence of acclimated
microorganisms (ORNL, 1979).
1-3 July, 1983
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2. EFFECTS INFORMATION
2.1 Health Effects
Various impurities have been found in commercial samples of
chlorophenols which may have important toxicological implications. Of
most concern are the polychlorodibenzodioxins (PCDD) and
chlorodibenzofurans found in technical grade trichlorophenols and
PCP. The highly toxic 2,3,7,8-tetrachlorodibenzodioxin (2,3,7,8-TCDD)
has been found in 2,4,5-TCP samples at levels of 0.07 to 6.2 mg/kg;
2,3,7,8-TCDD has not been found in PCP or most other samples of
chlorophenols sampled. Other PCDDs have also been found in
chlorophenols, especially technical PCP; commercial PCP is reported to
contain on the order of 1,000 ppm octachlorodibenzodioxin and 100 ppm
hexachlorodibenzodioxin. Chlorinated dibenzofurans have also been
reported in samples of trichlorophenols and PCP (IARC, 1979; OWRS,
1980f).*
2.1.1 Acute Toxicity
Except for PCP, most toxicological information on chlorophenols is
derived from experiments with animals. Chlorophenols may be separated
into two categories based on their acute toxic effects: (1) convulsive
chlorophenols, including 2-CP and 2,4,6-TCP, and (2) nonconvulsive
chlorophenols. Poisoning by chlorophenols in general is characterized
by a marked rise in temperature and, in most cases, an initial increase
in respiratory rate followed by a decreased rate and onset of coma.
Poisoning by the convulsive chlorophenols can lead to convulsions,
tremors and eventually coma. The most common symptoms in humans
poisoned by acute (or chronic high-level) doses of PCP are general
weakness, profuse perspiration, and weight loss. Chlorophenols are
also irritating to the nose, throat, skin, and eyes (ORNL, 1979; OWRS,
1980e).
The toxic action of chlorophenols appears to involve the uncoupling of
oxidative phosphorylation leading to serious metabolic disturbances.
increased chlorine content increases the potency of the chlorophenols
in producing this effect and the acute toxicity of the higher
chlorinated phenols (PCP, and tetrachlorophenols) is greater. In
general, increased chlorination of phenol leads to a reduction of the
convulsant action but an increase in the inhibition of oxidative
phosphorylation (ORNL, 1979).
Oral LD5Q values for chlorophenols in rats range from 50 mg/kg for PCP
to the gram-per-kilogram levels for the trichlorophenol isomers; the
lowest reported oral lethal dose in humans is 29 mg/kg for PCP and 500
mg/kg for 2,4,6-TCP. Chlorophenols are also toxic when inhaled or
absorbed through the skin. in the case of PCP, for example, the LD5Q
information concerning the toxic effects of PCDDs may be found in the IARC
monographs (Vol. 15, 1977), the Intermedia Priority Pollutant document on
2,3,7,8-TCDD, and references cited therein.
2-1 July, 1983
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in rats for inhaled aerosol (11.7 rag/kg) and the dermal LD5Q (105
rag/kg) are both comparable to the oral LD50 for rats (50 mg/kg) (OWRS,
1980e; OWRS, 1980f).
2.1.2 Chronic Toxicity
Symptoms of chronic toxicity are, in general, similar to those seen in
acute poisonings. Chlorophenols do not accumulate in body tissues to
the extent of more lipophilic chlorinated organics; consequently,
chronic effects usually require relatively high levels of continuous
exposure. While the long term effects of many of the chlorophenols
have not been extensively studied, the limited information available
suggests that most chlorophenols are of low-to-moderate toxicity (ORNL,
1979; OWRS, 1980e). More specific information on the chronic effects
of individual chlorophenols is summarized below.
Monochlorophenols
Monochlorophenols have not been adequately tested for long term
effects. Short term (3-week) feeding studies with 2-CP in rats (65
mg/kg every other day) showed altered function and histological
degeneration of the liver. Rats exposed to 4-CP aerosols at levels of
2 mg/m3 for 6 hrs/day showed reversible weight loss and increased
myoneural excitability, but temperature and blood parameters were not
affected. Workers exposed to 4-CP are reported to have a significantly
higher incidence of neurological disorders, including increased
myoneural excitability (OWRS, 1980a; OWRS, 1980e).
The carcinogenic potential of raonochlorophenols has not been tested by
the oral route; 2-CP was found to be a promoter in the DMBA-induction
of tumors on the skin of mice. Both 2-CP and 4-CP have shown some
mutagenic potential; 4-CP was positive in a microorganism test and 2-CP
caused increased chromosomal damage and deletions in mammalian cells.
Adequate tests have not been done with 2-CP and 4-CP for teratogenic or
reproductive effects (OWRS, 1980a,- OWRS, 1980b).
2,4-Dichlorophenol
A chronic feeding study showed that mice fed 2,4-DCP at the level of
230 mg/kg/day for 6 months had a slight increase in histological
abnormalities of the liver and a significantly depressed growth rate.
in the same study, animals dosed with 100 mg/kg showed no apparent
adverse effect. Based on this no-observable-effect-level (NOEL) of 100
mg/kg/day and a 1000-fold safety factor, EPA has estimated the
Acceptable Daily Intake (ADI) for 2,4-DCP to be about 7 mg/day for a 70
kg human (OWRS, 1980c; OWRS, 1980e).
As part of the National Toxicology Program (NTP), 2,4-DCP is currently
undergoing testing by NCI for possible carcinogenicity. The chemical
has been found to be a promoter of DHBA-induced skin tumors on mice but
was negative when examined for mutagenicity by the Ames Salmonella
microsomal test. While the teratogenicity of 2,4-DCP has not been
adequately examined, effects have been reported in rats following oral
doses as low as 20 mg/kg (OWRS, 1980e).
2-2 July. 1983
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2,4,5-Trichlorophenol
High chronic doses of 2,4,5-TCP have produced relatively minor damage
to kidneys and liver in animals. Rats fed 2,4,5-TCP (99% pure) for 98
days at levels of 100 mg/kg/day had no apparent adverse effects. At
1000 mg/kg growth was slowed in females and at 3000 mg/kg reversible
histopathologic changes in the liver and kidneys were observed. Using
a NOEL of 100 mg/kg and an uncertainty factor of 1000, the ADI is
estimated to be about 7 rag/day for a 70 kg human (OWRS, 1980a).
The carcinogenic potential of 2,4,5-TCP has not been demonstrated
except as a promoter on the skin of mice. The Ames Salmonella
mutagenicity test proved negative both with and without microsomal
activation. No teratogenic effects of 2,4,5-TCP were observed at doses
of 0.9 or 9 mg/kg/day {at 6-15 days gestation) in pregnant mice (OWRS,
1980a).
Adverse health effects have been seen in workers exposed to
trichlorophenols contaminated with 2,3,7,8-TCDD. These effects
(persistent chloracne, liver dysfunction, neuromuscular weakness, and
porphyria) have been attributed to the 2,3,7,8-TCDD contaminant (IARC,
1979).
2,4,6-Triochlorophenol
The National Cancer Institute (NCI) has completed an assessment of the
carcinogenicity of 2,4,6-TCP in rats and mice. Male rats showed a
significant increase in the incidences of lymphoma or leukemia when fed
approximately 250 mg/kg/day (5000 ppm in diet) over two years.
Statistically significant incidences of liver carcinomas or adenomas
were observed in mice (both sexes) fed 2,4,6-TCP at a similar dietary
level (equivalent to about 600 mg/kg/day). EPA has extrapolated the
animal data using four dose-response models to estimate human dose
response; the predicted excess lifetime cancer risk was estimated to be
between about 10~7 and 30 x 10~5 for exposure to 20 ug of 2,4,6-TCP per
day (OWRS, 1980e).
While 2,4,6-TCP gave a negative result in Ames Salmonella test for
mutagenicity, a weak, but significant, mutagenic response was reported
in yeast cultures. No evidence is available to judge the
teratogenicity of 2,4,6-TCP (OWRS, 1980e). NTP testing for cytogenic
effects (hamster ovary cells) yielded negative results in chromosome
abberation and sister chomatid exchange tests.
2,3,4,6-Tetrachlorophenol
No long term toxicity studies are available for 2,3,4,6-TCP.
Commercial tetrachlorophenol reportedly contains PCP (27%) and toxic
impurities (chlorodibenzofurans and chlorodioxins) that may be of more
concern. No other data pertinent to the carcinogenicity of 2,3,4,6-TCP
is currently available. Tetrachlorophenol is reported to be
nonmutagenic in the Ames test, both with and without microsomal
activation. The chemical also did not induce teratogenic effects in
rats at doses of 10 or 30 mg/kg given on days 6 through 15 of
2-3 July, 1983
-------
gestation. However, tetrachlorophenol produced fetotoxic effects
(subcutaneous edema and delayed ossification) in pregnant rats at doses
of 10 and 30 mg/kg (OWES, 1980a).
Pentachlorophenol
A long term (2-year) feeding study with purified POP in rats showed
some toxic effects (decreased weight gain, increased activity of
selective serum enzymes, pigmentation accumulation in the liver and
kidneys) at levels of 30 mg/kg PCP per day. The apparent NOEL from
this study was 3 mg/kg/day for females and 10 mg/kg/day for male
rats. No increases in tumor incidence were evident in this study.
Using a NOEL of 3 mg/kg and applying a 100-fold uncertainty factor, EPA
has calculated an ADI of about 2.1 mg for a 70 kg human. Another
feeding study in rats over 8 months yielded an NOEL of 6 mg/kg/day
based on clinical changes in enzymatic activities. Liver changes
observed in other feeding studies with technical grade PCP have been
attributed to toxic contaminants rather than PCP itself; long term
dietary exposure to 20 mg/kg of technical grade PCP produced liver
lesions, porphyria, and enhanced hepatic enzyme activity. (OWRS,
1980d).
The most serious effects of PCP may be its embryotoxicity and fetotoxic
effects. PCP of both commercial and purified grades produced fetal
anomalies in rats. Fetotoxic and teratogenic effects have been
produced in rats following oral doses of 30 mg/kg/day of PCP during
gestation. Purified PCP was somewhat more toxic than commercial grade
PCP with respect to the incidence of fetal resorptions, growth retarded
fetuses, and skeletal and soft tissue anomalies; these effects were
more apparent when pregnant rats were dosed during early
organogenesis. Comparable effects were not observed following a single
but higher oral dose of PCP (OWRS, 1980f).
PCP has been shown to be mutagenic in a few test systems. Purified PCP
was mutagenic in yeast cells; in mice, single high doses of PCP during
gestation reportedly yielded significant changes in the hair coat color
of mice offspring. PCP has produced negative mutagenic responses in
tests with Drosophila fruit flies, and tests in microorganisms
(bacteria and yeast) have yielded conflicting results. FCP was not
found to be carcinogenic in long term studies in rats and mice. PCP
also did not act as a promoter in skin tumor promotion studies with
mice. PCP is currently undergoing further testing by the National
Cancer Institute (OWRS, 1980f).
2.1.3 Absorption, Distribution and Metabolism
Information on the uptake and metabolism is derived mainly from studies
on experimental animals. In general, absorption can occur via oral or
dermal routes; respiratory absorption has also been confirmed for
PCP. Chlorophenols given orally appear to be readily absorbed,
metabolized, and excreted. Absorption efficiency by the dermal route
varies widely; 2,3,4,6-TCP and PCP are readily absorbed through the
skin, 2,4-DCP less readily, and the tricholorophenols are apparently
not absorbed in toxic amounts. Based on the available data for PCP,
2-4 July, 1983
-------
chlorophenols are transported in the blood. Analyses of human cases of
fatal PCP poisoning show high PCF residues in the liver, kidney, and
stomach, as well as in the blood (ORNL, 1979).
Little information is available on the metabolism of lower
chlorophenols in mammals. Conjugation to form the sulfate or
glucuronide salts is thought to be the major metabolic route for the
less chlorinated phenols. The more extensive data on the fate of PCP
in mammals indicates that conjugation with glucuronic acid is also the
major pathway for PCP. PCP is also oxidized in mammals to produce
tetrachlorohydroquinone and chloranil (tetrachloroquinone). Because
urine levels of PCP are used to estimate PCP exposure in humans,
analysis of urine should encompass these oxidation products (and
conjugates) as well as PCP itself. In mammals the bulk of PCP
administered appears to be excreted relatively rapidly, e.g., about 50%
is excreted in 24 hours. However, excretion of residual PCP may take
longer (OWRS, 1980f).
Note that exposure to other chlorinated organics can result in exposure
to chlorophenols via metabolic degradation. For example, 2,4,6-TCP is
the major metabolite of 1,3,5-trichlorobenzene in rabbits and 2,4-DCP
is produced in mice from hexachlorocyclohexanes (OWRS, 1980e).
2.2 Environmental Effects
2.2.1 Aquatic Effects
The toxicity of chlorinated phenols to aquatic life varies widely and
appears to be a function of the ring position and number of chlorine
substitutents. In general, the toxicity increases with increasing
substitution, and in most cases, aquatic plants appear to be less
sensitive than aquatic animals. Chlorinated phenols have also been
shown to impair the flavor of fish at concentrations lower than levels
which are toxic to aquatic organisms (OWRS, 1980a).
The limited information on the effects of chlorophenols on aquatic
organisms indicates acute toxicity for fish at concentrations on the
order of 0.1 to 10 mg/L. Reported LC50's for bluegill were 6.6, 2.02,
and 0.32 mg/L, respectively, for 2-CP, 2,4-DCP, and 2,4,6-TCP. Daphnia
were affected by these three chlorophenols at levels ranging from 2 to
11 mg/L. Chronic values for minnows were >3.9 mg/L, 0.37 mg/L and 0.72
mg/L for 2-CP, 2,4-DCP, and 2,4,6-TCP respectively. Toxicity tended to
increase with the degree of chlorination (OWRS, 1980e).
The lowest effect level for freshwater aquatic organisms for PCP was 1
mg/L in algae. Salmon exhibited sublethal effects at 1.74 mg/L and
rainbow trout had the lowest acute level (LCso of 15.5 ug/L). LCso'8
for freshwater fish and invertebrate species ranged over two orders of
magnitude. Marine organisms exhibited effects and levels as low as 38
mg/L for fish. For PCP, the toxicity increases with decreasing pH and,
to a lesser degree, with decreasing hardness (OWRS, 1980f).
2-5 July, 1983
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Few bioconcentration experiments have been undertaken for
chlorophenols. Steady state bioconcentration factors (BCFs) for PGP in
most aquatic organisms are reportedly low (390 or less}. PCP is
rapidly absorbed by fish but bioconcentration is low Ol) because PCP
is rapidly conjugated and excreted (OWRS, 1980d). A BCF of 214 has
been measured for 2-CP and theoretical BCFs were calculated from
octanol/water partition coefficients for 4-CP (41), 2,4-DCP (130),
2,4,6-TCP (380), 2,4,5-TCP (440), and 2,3,4,6-TCP (1100). These
theoretical BCFs probably represent upper limits for uptake? the
limited data available indicate that fish rapidly metabolize and
excrete chlorophenols (OWRS, 1980a; OWRS, 1980e).
2.2.2 Other Effects
PCP has documented toxic effects of domestic animals and wildlife;
toxic effects have been noted in swine, cattle, sheep, cats, and
rabbits. Food animals can come into contact with wood treated with
PCP; residues in food products of animal origin are the principle
problem rather than overt toxicity to exposed animals. Problems
related to poultry occur when sawdust or wood chips (from treated wood)
containing PCP are used for bedding (litter). Fungi in the litter
convert PCP and tetrachlorophenols to the corresponding anisole by
methylation. The chicken absorbs the anisoles, resulting in a musty
taint to meat and eggs. (ORNL, 1979).
2-6 July, 1983
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3. ENVIRONMENTAL RELEASE (CONTACT: Mike Slimak, FTS 426-2503)
The production volume, uses, and releases of the individual
chlorophenols are discussed below. Recent production data on most of
these chemicals are proprietary and unpublished. In addition,
releases could not be estimated in some cases due to insufficient
information. More monitoring data are needed to properly assess the
source and quantity of releases. In Table 2 the environmental
compartments (air, land, or water) initially receiving and
transmitting the compounds are identified. These annual release
estimates were drawn from several sources (OWRS, 1980e; OWRS, 1980f;
OTS, 1980) for different chlorophenols and may not be strictly
comparable due to the use of differing assumptions and production
data.
Quantification of indirect sources of chlorophenols in the
environment is also quite difficult. Prime examples of indirect
releases are chlorination of phenols present in water during
industrial, POIW, and drinking water treatment processes and the
environmental degradation of complex chlorinated organics (i.e.,
2,4-D; 2,4,5-T, pesticides, and higher chlorophenols} into
chlorophenols (OWRS, 1980e).
Monochlorophenols
The 2- and 4-chlorophenols are produced in low volume primarily
through the chlorination of phenol. Production estimates are 8150
kkg for 2-CP in 1977 (OWES, 1980e) and 9800 kkg for 4-CP in 1976
(OTS, 1980). Both 2-CP and 4-CP are used primarily as intermediates
for production of higher chlorinated phenols. The 4-CP is also used
in the production of other chemicals (quinizarin, dye intermediates,
germicides) and as a denaturant for ethanol (OTS, 1980). While the
data in Table 2 show that releases to water are by far the most
important route of entry of the monochlorophenols into the
environment, the amounts released are limited.
2,4-Dichlorophenol
2,4-Dichlorophenol is produced by chlorination of phenol or
monochlorophenols. The major use of 2,4-DCP is in the manufacture of
2,4-dichlorophenoxyacetic acid (2,4-D) and related herbicides. For
the purpose of a mass balance analysis, the production volume of
2,4-DCP was estimated to be about 14,000 kkg in 1977 (OWRS, 1980e).
As shown in Table 2, direct emissions of 2,4-DCP are predominantly
aqueous and arise from the manufacture of 2,4-DCP and consumption via
the production of 2,4-D. Use of the herbicide 2,4-D will result in
the direct release to the land of 1-70 kkg of 2,4-DCP present as an
impurity in commercial 2,4-D formulations (OWRS, 1980e). Of greater
3-1 July, 1983
-------
potential significance, however, is the degradation of 2,4-D to
2,4-DCP in soils, which would result in a major source of land
emissions. However, 2,4-DCP is expected also to degrade readily
under conditions favorable to 2,4-D breakdown. Therefore, further
information is needed to evaluate this point (OTS, 1980).
Trichlorophenols
The commercial synthesis of 2,4,6-TCP is readily accomplished by the
direct chlorination of phenol. Production volume is difficult to
estimate; a value of 0-16,000 kkg has been reported for 1977 (OWRS,
1980e). While 2,4,6-TCP has numerous potential direct uses
{germicide, glue and wood preservative, anti-mildew treatment), the
majority produced is used as feedstock for higher chlorophenols.
Limited sampling data indicate that 2,4,6-TCP (as well as 2,4-DCP)
has been detected in effluents from various industrial operations.
For example, 2,4,6-TCP has been measured in effluents from pulp and
paper mills, the timber industry (notably barking), the manufacture
of paints and ink, and pesticide manufacturing. However, lack of
sufficient data makes it virtually impossible to assess environmental
emissions of 2,4,6-TCP (OWRS, 1980e).
2,4,5-TCP is synthesized by the hydrolysis of 1,2,4,5-
tetrachlorobenzene. In the absence of direct data, production was
estimated at 6500 kkg in 1976. Emissions due to production were
estimated to be 94 kkg to water, 7 kkg to air, and 6 kkg to land in
1976. In several consumption processes total emissions were
estimated to be significant but allocation to an environmental medium
was not possible. 2,4,5-TCP or its sodium salt was used directly as
a fungicide, preservative, or antimildew treatment. In 1976 it was
estimated that a majority of the 2,4,5-TCP available was consumed in
the production of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) and
derived herbicides. Subsequent restrictions on the use of these
herbicides may have resulted in decreased production of 2,4,5-TCP,
and therefore the potential for releases of 2,4,5-TCP should also be
significantly reduced (OTS, 1980).
Tetrachlorophenols
Although the direct production of tetrachlorophenols in 1976 has been
reported to be insignificant (OTS, 1980), production volume in 1977
for 2,3,4,6-tetrachlorophenol has been estimated to be from 0 to
19,000 kkg (OWRS, 1980e). Production quantities of 2,4,6-TCP and
2,3,4,6-TCP are interdependent; both are probably produced, and
therefore the production of each is less than the maximum estimates
given above. In the past, 2,3,4,6-TCP was used directly as a
preservative. The compound is also found as a by-product in
commercial PCP in concentrations ranging from 4 to 10% by weight.
For this reason, releases of 2,3,4,6-TCP are expected to be similar
3-2 July, 1983
-------
to those described for PCP below. Thus, releases have been estimated
to be approximately 8 percent of those estimated for PCP (OTS, 1980).
Pentachlorophenol
Annual production of PCP has remained constant at approximately
20,000 kkg for over a decade; production in 1978 totaled 21,300 kkg
(OWES, 1980f). Most of the PCP consumed in the United States is
produced domestically and only a small portion of domestic production
is exported. Pentachlorophenol is manufacturerd via the complete
chlorination of phenol using various catalysts. Over 80 percent of
the PCP (and its salt, sodium pentachlorophenate) produced is
consumed in the timber and plywood industry as a wood preservative
for poles, lumber, fence posts, etc. Other significant uses of PCP
or its salt are as an antimicrobial agent in paints and cooling tower
waters, tanning, and textiles. In the past, PCP has also been used
as a herbicide, both commercially and in home and garden
applications.
Table 2 summarizes the releases of PCP to the environment for the
year 1978. Although PCP is only moderately volatile, widespread use
as a wood preservative and in cooling tower waters may result in
significant release to the atmosphere. Home/garden use and
herbicidal applications of PCP are thought to result in significant
land releases. However, the estimates in Table 2 are based on
limited information and other sources of PCP release are probably
important. For example, the amount of PCP lost from treated wood
(e.g., utility poles) through leaching and runoff could be quite
large (OTS, 1980; OWRS, 1980f).
3-3 July, 1983
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TABLE 2. ESTIMATED RELEASES OF CHLOROPHENOLS TO THE ENVIRONMENT
2-Chlorophenol (8,150 kkg, 1977)c
Production
Intermediate for higher
chlorophenols
Total
4-Chlorophenol (9,900 kkg, 1976)d
Production
Intermediate for higher
chlorophenols
Denatured Alcohol
Miscellaneous
Total
2,4-Dichlorophenol (14, 000 kkg, 1977)c
Production
2,4-D production
Miscellaneous
Total
Pentachlorophenol (18,140 kkg, 1978)°
Production
Wood Preserving Industry
Preserved Wood6
Cooling Towers
Textiles /Rayons
Pulp and Paper Hills
Tanning Industry
Home and Garden6
Herbicide6
POTW
Total
Air
9
—
9
11
9
—
1
21
14.0
2.1
--
TeTT
50
—
340
230
— —
—
—
—
—
—
620
Water
170
81
25T
210
180
96
182
668
294
42
—
336
__
neg
—
2.0
3.0
5.0
2.0
—
—
—
HT
Land
neg
neg
neg
._
—
—
—
— —
neg
neg
1-70
1-70
—
74
—
neg
9.0
—
6.0
600
200
18
"907
a Sources for the data are given for each chemical. Numbers in parentheses
show estimated production volume in the year for which the mass balance was
calculated.
b Blanks indicate insufficient data.
c (OWRS, 1980e).
d (OTS, 1980).
e Portions of these releases may enter other media other than those noted;
however, insufficient data exist to properly apportion the estimated
releases.
3-4 July, 1983
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4. EXPOSURE
Except for PCP, little or no monitoring information exists for most
chlorinated phenols. Crude estimates concerning the exposure of the
general population to the lower chlorophenols (mono-, di-f and
trichlorophenols) suggest human exposure is most likely due to food
consumption, especially fish (OWRS, 1980e). Monitoring data showing
the presence of PCP in various foods indicates that the major route of
PCP exposure is also probably through food consumption. In the case
of PCP, widespread use as a wood preservative can result in
significant exposure via inhalation and dermal routes in both
occupational settings and during home use (OWRS, I980f; OPP, 1981).
PCP has been detected in human urine and tissue of occupational and
non-occupational populations. In one study, 85 percent of the urine
samples analyzed for the general population showed the presence of PCP
(6.3 ug/L mean). Using reported urine PCP levels, exposure estimates
(representing total body exposure from all routes) were calculated to
be in the range of 10 to 17 ug/day per person for the general
population and 1.5 to 4.4 mg/day for certain occupational settings
(OWRS, 1980d).
The contaminants of chlorophenols may also influence the environmental
impact of releases. The presence of polychlorinated dibenzo-p-dioxins
(PCDDs) in these chemicals has been well established. The highly
toxic 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) is apparently
formed during the synthesis of 2,4,5-TCP and was detected in the past
at levels of up to 10 mg/kg in the derived herbicide 2,4,5-T; levels
of 2,3,7,8-TCDD in more recent samples of 2,4,5-T were reported to be
below 0.1 ppm. Samples of trichlorophenols have also contained other
PCCDs with 2 to 8 chlorine substituents. Only those dioxins with 6 to
8 chlorine atoms have been found in tetrachlorophenols and PCP.
Numerous analyses have confirmed that 2,3,7,8-TCDD is not a
contaminant in PCP (OWRS, 1980a).
More detailed information concerning human exposure to chlorophenols
via specific exposure routes are given below.
4.1 Air Exposure
While the potential exists for exposure to airborne chlorophenols,
especially during the use of products containing these compounds,
little or no monitoring data exist on ambient atmospheric levels. Di-
and trichlorophenols have been identified in gas condensates from
municipal incinerators, but levels were not quantified.
Simple modeling techniques were used to estimate PCP concentrations in
ambient air resulting from evaporation ponds, volatilization from
treated wood, evaporation from cooling towers, and open burning of
PCP-treated wood. The maximum level expected from these sources
totals 140 ug/m3 and, assuming a breathing rate of 20 m3/day, total
exposure to the general population via inhalation is between 2 and 3
ug PCP per day. Certain subpopulations may be exposed to higher local
levels of PCP (1 km) downwind from cooling towers (maximum 2 mg/day)
4_1 July, 1983
-------
and from waste evaporation ponds (2 ug/day). Inhalation of airborne
POP from freshly treated wood indoors and during application may also
result in high exposures (OWRS, 1980f).
4.2 Water Exposure
PCP has been found in drinking water in the United States at low
concentrations. In 1976, PCP was found in 86 out of 108 samples with
a median of less than 0.01 ug/L and a maximum of 0.7 ug/L. In a more
recent survey, PCP was detected (in concentrations ranging from 1.3 to
12 ug/L) in only 8 out of 135 systems sampled. Assuming an intake of
2 liters a day, exposure to the general population would be less than
0.02 ug/day, while the maximum would be 24 ug/day (OWRS, 1980s).
The only other monitoring information available on chlorophenols in
finished drinking water is for 2,4-DCP. This compound was detected in
56 out of 108 samples at a mean level of 0.18 ug/L (for positive
values). Assuming a 2 liter daily consumption of drinking water, a
daily exposure of about 0.4 ug of 2,4-DCP can be estimated (OWRS,
1980e}.
According to the limited ambient water data for several chlorophenols
(2-CP, 2,4-DCP, and 2,4,6-TCP), concentrations are usually less than
50 ug/L. Therefore, daily exposure through drinking water has been
estimated to be 60 to 100 ug/day as a maximum value. Such an estimate
is an upper limit which assumes consumption of untreated water and is
probably not applicable to the general population. The exposure level
of 0.4 ug/day for 2,4-DCP is probably more indicative of normal
exposure levels (OWRS, 1980e).
A characteristic which would tend to decrease the likelihood of human
exposure to chlorophenols in general is the low odor thresholds of the
compounds in water. The EPA Water Quality Criteria proposed for
various chlorophenols reflect this property (OWRS, I980a).
Chlorination of water containing phenol, a common water impurity, is
reported to result in the formation of chlorophenols. However, the
monitoring data needed to address this potential source have not been
collected (OWRS, 1980e).
4.3 Other Exposure Routes
Food
in the case of PCP, recent FDA surveys reported PCP in 13 out of 240
composite samples. PCP residues were found in the following
commodities (average values, ug/kg): dairy products (0.5), grains and
cereals (1.0), root vegetables (1.0), and sugars and adjuncts (6.0).
Based on FDA data, EPA estimated an average PCP intake of 1.5 ug/day
and a maximum of 18 ug/day (43 FR 48446). High levels of PCP have
also been reported in some samples of other foods, especially fish (1-
5 rag/kg) and peanut butter; however, the significance of these
measurements is not clear (OWRS, 1980f).
4-2 July, 1983
-------
While the source of PCP in most foods is not known, the presence of
PCP in grain and sugar products has been attributed to storage of
these products in PCP-treated wooden containers (ORNL, 1979). PCP in
peanut butter may be due to the breakdown of pentachloronitrobenzene
which was also found in peanut butter (OWRS, 1980f).
As part of its compliance program, FDA collected milk samples for
analysis in 1979. Of 198 samples analyzed, 39 contained PCP at or
above 5 ppb (231 ppb maximum). Liver samples have also been collected
by USDA from beef, swine, and poultry throughout the United States.
This survey showed that in all instances the percentage of positive
findings of PCP residues exceeded 85% (OPP, 1981). Based on the past
two years of surveys, USDA has concluded that PCP is virtually
ubiquitous in U.S. meat and poultry supplies. The highest levels of
PCP were found in swine and turkeys. In 12% of the swine samples PCP
levels exceeded 0.5 ppb; nearly 1* of cattle sampled showed levels of
250 to 500 ppb. This nationwide survey showed that levels of PCP in
chickens were below 50 ppb.
Recent FDA analysis has also revealed PCP, heptachlorodioxin, and
octachlorodioxin residues in eggs and poultry in Texas. Maximum
levels of PCP in eggs were about 300 ppb; the levels of dioxins were
much lower (up to 0.19 ppb). The source of contamination appears to
have been the use of PCP in curing hides. Flesh scraped from PCP-
treated hides was used by rendering plants in Texas to produce poultry
feed products. FDA has also reported that PCP residues in eggs may
arise from the use of PCP-treated wood chips for litter in hatcheries.
A possible source of exposure to 2,4-DCP and 2,4,5-TCP may result from
the metabolism of ingested herbicides (2,4-D and 2,4,5-T) by grazing
animals. Conversion of herbicides to 2,4-DCP and 2,4,5-TCP occurs in
animals such as cows and sheep. Consumption of contaminated liver
from cattle fed 2,4-D-treated fodder may lead to significant ingestion
of 2,4-DCP. However, dairy cattle dosed with high levels of 2,4-DCP
did not accumulate the compound in their milk (OWRS, 1980e).
Based on theoretical bioconcentration factors for chlorophenols in
fish, EPA has estimated levels expected to be found in fish. Assuming
ambient water levels of 10 ug/L of the chlorophenol, fish residues
were predicted for 2-CP (4 mg/kg), 2,4-DCP (1.2 mg/kg), and 2,4,6-TCP
(4.5 mg/kg). Actual residues of these compounds in fish are limited,
and the theoretical bioconcentration factors (derived from
octanol/water partition coefficients) provide an upper limit for
uptake. Furthermore, metabolic data indicate that fish rapidly
metabolize and excrete these chlorophenols so that significant
bioaccumulation probably does not occur (OWRS, 1980e).
Occupational
The greatest occupational exposure to PCP occurs in wood treatment
plants. Air level data for pressure treatment plants indicate that
inhalation exposure can be significant for general operations (up to
240 ug/day) and even higher exposures are likely for some
4-3 July, 1983
-------
operations. Occupational end-users (carpenters, construction workers)
are also likely to incur inhalation exposure to PCP from the use of
FCF treated lumber (OFF, 1981).
4-4 July, 1983
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5. DATA BASES
5.1 Chemical in Commerce Information System (CICIS)
The inventory was compiled under the authority of Section 8 of TSCA
which requires manufacturers to report to EPA the chemicals imported
and manufactured during calendar year 1977. The Inventory lists the
Chemical Abstract Service (CAS) preferred name for the chemicals,
their respective CAS number (often used for identification purposes),
production site, company name, and volume(s) of production and
import. There is also a Confidential Inventory in which many of these
characteristics are claimed confidential by the manufacturer. In
these instances, the confidential information will not be available in
the public inventory. CICIS can now be accessed through the NIH/EPA
Chemical Information System (CIS - see 5.3). For further information,
contact Geri Nowack at FTS 382-3568 or Robin Heisler at FTS 382-3557.
5.2 EPA Chemical Activities Status Report (EPACASR)
EPACASR is an on-line system containing information on EPA's interest
in chemicals. This system includes data on the Agency's regulations,
research, and assessments directed toward specific chemicals. EPACASR
is published annually and the data base is updated as information is
received. A searchable subset itemizes NTP/NCI studies and results,
as well as chemicals discussed in the IARC monograph series. (Other
sources are added as appropriate.) Entries identify the statutory
authority, the nature of the activity, its status, the reason for
and/or purposes of the effort, and a source of additional
information. Searches may be made by CAS Number or coded text.
(EPACASR is scheduled to be added to CIS in 1984.) For further
information, contact Eleanor Merrick at FTS 382-3415.
5.3 NIH/EPA Chemical Information System (CIS)
This is a collection of various scientific data bases available
through an interactive computer program. The linking system between
these data files is the Structure and Nomenclature Search System
(SANSS). CIS can also provide a list of non-CIS sources of
information on a chemical of interest. However, these files have to
be accessed individually by either separate on-line systems or in
hard-copy. For further information, contact Dr. Steve Heller at FTS
382-2424.
5.4 Chemical Regulations and Guidelines System (CRGS)
CRGS is an on-line data base which is being developed to provide
information on chemical regulatory material found in statutes,
regulations, and guidelines at the Federal, State, and international
levels. Currently, only the first phase of CRGS, which encompasses
only source material at the Federal level, is operational. Nationwide
access to CRGS is available through Dialog. For further information,
contact Doug Sellers at FTS 382-2320.
5-1 July, 1983
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5.5 Chemical Substances Information Network (CSIN)
The Chemical Substances Information Network (CSIN) is a sophisticated
switching network based on heterogeneous distributed data base
management and networking concepts. CSIN offers efficient access to
on-line information resources containing data and information relevant
to chemical substances, as well as information covering other
scientific disciplines and subject matters. The purposes of CSIN are
two-fold: first to meet the growing chemical data and information
requirements of industry, academe, government (Federal and State),
public interest groups, and others; and secondly to reduce the burden
on the private and public sector communities when responding to
complex Federal legislation oriented to chemical substances.
CSIN is not another data base. CSIN links many independent and
autonomous data and bibliographic computer systems oriented to
chemical substances, establishing a "library of systems." Users may
converse with any or all systems interfaced by CSIN without prior
knowledge of or training on these independent systems, regardless of
the hardware, software, data formats, or protocols of these
information resources.
Information accessible through CSIN includes data on chemical
nomenclature, composition, structure, properties, toxicity, production
uses, health and environmental effects, regulations, disposal, and
other aspects of the life cycle of materials as they move through
society. Currently, seven independent information resources are
accessible through CSIN. They are: National Library of Medicine
(NLM), Chemical Information System (CIS), CAS-On-Line, SDC's ORBIT,
Lockheeds's DIALOG , Bibliographic Retrieval Service (BRS), and the US
Coast Guard's Hazard Assessment Chemical System (HAGS). For further
information contact Dr. Sid Siegel at 202-395-7285.
5.6 EPA Information Clearinghouse
The EPA Information Clearinghouse is a bibliographic data base
composed of over 500 individual data bases and models which contain
monitoring information and statistics on a variety of chemicals. The
individual data bases are maintained for offices within EPA. The
clearinghouse listed a total of 453 citations for the chlorophenols.
For further information, contact Irvin Weiss at FTS 382-5918.
5-2 July, 1983
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6. REGULATORY STATUS (Current as of 1/B3)
6.1 Promulgated Regulations
6.1.1 EPA Programs
Clean Water Act (CWA)
o Sections 301,-304, 306, and 307 - Chlorinated phenols are listed
as toxic pollutants (40 CFR 401.15) and are subject to effluent
limitations. However, no effluent guidelines specifically limit
the release of chlorinated phenols at this time.
o Section 311 - Pentachlorophenol and trichlorophenols are
classified as hazardous substances (40 CFR 116.4) and discharges
are subject to reporting requirements (40 CFR 117.3).
o Sections 318, 402, and 405 - National Pollution Discharge
Elimination System (NPDES) permit testing requirements; the
following are listed as organic toxic pollutants based on gas
chromatographic and mass spectroscopic analyses and are part of
the consolidated permit program (40 CFR 122, App. D):
o 2-Chlorophenol
o 2,4-Dichlorophenol
o 2,4,6-Trichlorophenol
o Pentachlorophenol
Resource Conservation and Recovery Act (RCRA)
o Section 3001 - The following chlorinated phenols have been
identified as toxic hazardous wastes if and when they are
discarded as commercial products or off-specification species (40
CFR 261.33):
o 2-Chlorophenol (U048)
o 2,4-Dichlorophenol (U081)
o 2,4,5-Trichlorophenol (U230)
o 2,4,6-Trichlorophenol (U231)
o 2,3,4,6-Tetrachlorophenol (U212)
o Pentachlorophenol (U242)
Chlorinated phenols are listed as hazardous constituents (40 CFR
261, App. VIII).
o Sections 3002 to 3006 - Hazardous wastes are subject to further
controls concerning generators, transporters, and treatment,
storage and disposal facilities (40 CFR 262 to 265). Permit
procedures are also included in consolidated permit regulations
(40 CFR 122 to 124).
6-1 July, 1983
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Federal Food, Drug, and Cosmetic Act (Administered by EPA)
o Establishment of tolerance levels of 2 ppm and 0.05 ppm for 4-
chlorophenol on mung bean sprouts and tomatoes, respectively (40
CFR 180.202).
o Establishment of tolerance levels for residues of 2,4-
dichlorophenol in food products of various animals (40 CFR
180.142).
6.1.2 Programs of Other Agencies
OSHA - Occupational Safety and Health Act
o General industry standards for workplace exposure to air
contaminants (29 CFR 1910.1000):
o Pentachlorophenol
FDA - Federal Food, Drug, and Cosmetic Act
o Use of pentachlorophenol (and/or its potassium or sodium salt) in
numerous food contact situations is regulated (21 CFR 175.105;
176.200; 176.210s 176.300? 177.1210? 177.2600; 178.3120; 178.3800;
178.3900; 181.30). The uses of potassium salts of trichlorophenol
are also permitted in some cases (21 CFR 176.200; 181.30).
DOT - Hazardous Materials Transportation Act
o fhe following chlorophenols are listed as hazardous materials (49
CFR 172.101) and have general packaging requirements (49 CFR
173.510):
o Pentachlorophenol
o Sodium Pentachlorophenate
6.2 Proposed Regulations
6.2.1 EPA Programs
TSCA
o Section 8 - Proposed requirement that chemical manufacturers
report production and other data to EPA for 2-chlorophenol, 4-
chlorophenol, 2,4,5-trichlorophenol, pentachlorophenol
(44 FR 77477, 12/31/79), and 2,4-dichlorophenol
(45 FR 13646, 2/29/80).
6-2 July, 1983
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Comprehensive Environmental Response, Compensation and Liability Act
(CERCLA or Superfund)
o CERCLA provides for the liability, compensation, cleanup, and
emergency response for the release of hazardous substances into
the environment. This Act also deals with the cleanup of
hazardous waste disposal -sites (42 USC 96-01; PL 96-510). EPA is
developing regulations concerning the designation of hazardous
substances, the development of reportable quantities (RQ), claims
procedures, and the confidentiality of business records (46 FR
54032). Revisions to the National Contingency Plan (NCP) as
required by CERCLA have been issued in a proposed rule (47 FR
10972).
o Seven chlorophenols are hazardous substances under CERCLA and will
be subject to regulations developed under Superfund. EPA has
proposed adjustments to many of the RQs established under CERCLA
and the CHA for chlorophenols (48 FR 23552).
6.3 Other Actions
EPA - Federal Insecticide, Fungicide, and Rodenticide Act
o A Rebuttable Presumption Against Registration (RPAR) was issued
against the use of pentachlorophenol as a wood preservative
(43 FR 48154). A risk/benefit analysis was issued (46 FR 13020)
and regulations were proposed concerning the use of PCP to reduce
risks. The Agency has modified some proposals (48 FR 13257).
NIOSH - Occupational Safety and Health Act
o Request for information for the preparation of information
profiles on industrial chemicals. The information will be used in
the evaluation of exposure and potential safety or health hazards
in the workplace (47 FR 55736):
o 2,4,5-Trichlorophenol
o Pentachlorophenol
PHS - National Toxicology Program
Toxicological testing is scheduled or underway for several
chlorophenols; 2,4-DCP and PCP are in the chronic phase of
carcinogenicity bioassays.
FDA
FDA is examining nationwide samples of animal feed for PCP; these
results, coupled with studies of PCP residues in cattle, poultry,
and swine, may lead to FDA limits for PCP.
6-3 July, 1983
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7. STANDARDS AND RECOMMENDED CRITERIA*
7.1 Air
o OSHA standard for workplace exposure (29 CFR 1910.1000):
Pentachlorophenol (skin) 0.5 mg/m3 (8-hr. TWA)
o American Conference of Government Industrial Hygienists (ACGIH)
threshold limit values (TLV):
Pentachlorophenol (skin) 0.5 mg/m3 (8-hr. TWA)
1.5 mg/m3 (short term
exposure limit)
7.2 Water
PCP and trichlorophenols are designated as hazardous substances
under Section 311 of the CWA and require notification of discharge
equal to or greater than a reportable quantity of 10 Ibs. (40 CFR
117.3). Reportable quantities proposed under CERCLA are: 100
Ibs. for 2-CP and 2,4-DCP; 10 Ibs. for 2,3,4,6-TCP; and 1 Ib. for
PCP (48 PR 23552).
water Quality Criteria (45 FR 79318)
Freshwater aquatic life (in ug/L; acute except where indicated):
2-Chlorophenol 4,380
2,4-Dichlorophenol 2,020
365 (chronic)
2,4,6-Trichlorophenol 970 (chronic)
Pentachlorophenol 55
3.2 (chronic)
Saltwater aquatic life (in ug/L; acute except where indicated):
4-Chlorophenol 29,700
Pentachlorophenol 53
34 (chronic)
Human health
Since chlorophenols can cause taste and odor problems, criteria
have been calculated based on organoleptic effects. Criteria
based on organoleptic effects as well as toxic effects were
calculated because: (1) sufficient toxicological data were not
available for some chlorophenols; and (2) where toxicity-based
*See Appendix A for a discussion of the derivation, use, and limitations of
these Criteria and Standards.
7-1 July, 1983
-------
criteria could be calculated, the criteria based on organoleptic
effects are lower. (Note that organoleptic problems have no
demonstrated relationship to adverse human health effects):
2-Chlorophenol
4-Chlorophenol
2,4-Dichlorophenol
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
2,3,4,6-Tetrachlorophenol
Pentachlorophenol
Organoleptic
Criteria (ug/L)
0.1
0.1
0.3
1.0
2.0
1.0
30
Toxicological
Criteria (ug/L)
None
None
3.09
2600
12 (10"5
Cancer risk)*
None
1010
7.3
Other
FDA permits the limited use of chlorophenols in food contact
situations. See Section 6.1.2 of this document for CFR citations.
•Increased lifetime risk calculated from NCI bioassays (See
Health Effects Section).
7-2
July, 1983
-------
8. SPILL OR OTHER INCIDENT CLEANUP/DISPOSAL
8.1 Hazards and Safety Precautions
The toxic effects of chlorophenols are described in detail in Section
2 of this document. Most chlorophenols are readily absorbed via
Inhalation or through the skin. All are irritating to both the skin
and the eyes, and dusts are irritating to the respiratory tract. Most
chlorophenols are moderately toxic, and the presence of highly toxic
impurities in many commercial samples is also of concern.
Only the lower chlorophenols (2-CP, 4-CP, and 2,4-DCP) are moderately
or slightly flammable. However, all chlorophenols will emit toxic
fumes (hydrochloric acid) at high temperatures.
8.2 First Aid
Move victim to fresh air; give oxygen if breathing is difficult. In
case of contact, flush skin or eyes with running water for at least 15
minutes; remove contaminated clothing and shoes. Effects of contact
or inhalation may be delayed.
8.3 Emergency Action
Spill or Leak - Keep upwind, isolate hazard area, and wear self-
contained breathing apparatus and protective clothing. No flares or
smoking in hazard area. In the case of small spills of
monochlorophenols, flush area with water; large spills of
monochlorophenols can be diluted with water and diked for later
disposal. Small spills of other chlorophenols may be taken up with
sand, earth, or other noncombustible absorbents; large spills may be
diked for later disposal.
Fire - For small fires involving chlorophenols dry chemical or C02
extinguishers may be used. For large fires use foam or water. Stay
away from ends of tanks and cool containers with water.
8.4 Notification and Technical Assistance
Section 103(a) of the Comprehensive Environmental Response,
Compensation, and Liability Act (CERCLA or Superfund) requires
notification of the National Response Center (NRC) at 800-424-8802 (or
426-2675 in the Washington, D.C. area) if releases of chlorophenols
exceed reportable quanitites (RQs). At present, the RQs for PCP,
2,4,5-TCP, and 2,4,6-TCP are all 10 Ibs., as established under section
311 of the CWA. Regulations listing RQs under CERCLA have not been
finalized, and until that time, a statutory RQ of 1 Ib. is applicable
for other chlorophenols (2-CP; 2,4-DCP; and 2,3,4,6-TCP).
For emergency assistance call:
CHEM TREC: 800-424-9300.
8-1 July, 1983
-------
For further information call EPA Environmental Response Team (24-hour
number: 201-321-6660) or the Division of Oil and Special Materials
(1-202-245-3045). Confirm any treatment procedures with a responsible
environmental engineer and regulatory officials.
8.5 Disposal
A generator of 1000 kg or more of hazardous waste is subject to the
RCRA hazardous waste regulations concerning treateraent, storage, and
disposal. A number of chlorophenols (2-CP; 2,4-DCP; 2,4,5-TCP; 2,4,6-
TCP; 2,3,4,6-TCP; and PCP) have been identified as toxic hazardous
wastes when discarded as commercial product or off-specification
species.
The following specific waste streams, which contain one or more
chlorophenols, are also subject to hazardous waste regulations under
RCRA. Hazardous wastes below are listed by industry and hazardous
waste number; the specific chlorophenols contained in each waste
stream are also noted in parenthesis:
Wood Preservation
K001 — Bottom sediment sludge from treatment of wastewaters from wood
preserving processes that use creosote and/or pentachlorophenol
(2-CP, trichlorophenols, tetrachlorophenols, and PCP).
Pesticides
K043 - 2,6-Dichlorophenol waste from the production of 2,4-D (2,4-DCP
and 2,4,6-TCP).
K099 - Untreated wastewater from 2,4-D production (2,4-DCP and 2,4,6-
TCP).
Organic Chemicals
K105 - Separated aqueous stream from the reactor product washing step
in the production of chlorobenzenes (2,4,6-TCP).
8-2 July, 1983
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9. SAMPLING AND ACCEPTABLE ANALYTICAL TECHNIQUES
9.1 Air
The chlorophenols are not regulated air pollutants; therefore, no
Agency-approved procedure for air analysis is available. However,
sampling and analysis procedures have been issued by NIOSH for
monitoring around production and user facilities (NIOSH Manual of
Analytical Methods, Volume 4, NIOSH Pub. No. 78-175 and Volume 7, NIOSH
Pub. No. 82-100). The published procedures specifically designed for
the analysis of 4-CP and PCP are described below; however, these
procedures can easily be adapted to collect and monitor for other
chlorophenols.
In the NIOSH analytical method for 4-CP (Method 337, Volume 7), a known
volume of air is drawn through a silica gel tube to absorb 4-CP vapor
present; the chlorophenol is desorbed with acetonitrile and a sample is
analyzed by high performance liquid chromatography (hplc). The hplc
analysis employs a reverse phase column (C18-silica) and a UV
detector. For a 3 liter air sample the working analytical range was
0.91-23 mg/m3, and the lowest level quantifiable for this method was 2.5
ug 4-CP per sorbent sample. For the overall sampling and analytical
method in this range, the pooled relative standard deviation (RSD) for
replicate measurements was 6.1%. For a 150 mg bed of silical gel, the
maximum allowable sampling volume was about 40 L; this would permit
analysis in the range of 0.064-1.6 mg/m3. Samples of 4-CP on silica gel
were stable at 25° for seven days and 29 days at 0°. In addition to
separating 4-CP, the chromatographic conditions specified in this method
(gradient elution) will permit the separation of: 2-CP; all the
dichlorophenol isomers; 2,4,5-TCP; PCP; and various other phenols.
A method specifically for PCP analysis in air (Method S297, Volume 4}
has also been issued by NIOSH. A known volume of air is drawn through a
filter connected in sequence to a bubbler with 15 mL of ethylene
glycol. The filter is added to the glycol solution and, just before
analysis, 10 mL of methanol is added. Hplc analysis of the sample uses
a reverse phase column (C18-silica) and a UV detector. The procedure is
validated over the range 0.265 to 1.13 mg/m3 using 180 L samples. The
Coefficient of Variation for the combined sampling and analytical
methods was 0.0721 in this range.
9.2 Water
A number of chlorophenols are listed as priority pollutants under
Section 304 of the Clean Water Act. The suggested analytical method
(Method 604 in "Guidelines Establishing Test Procedures for the Analysis
of Pollutants," Fed. Regist. 44, 69484; 1979} may be used to determine
levels of a variety of phenolic compounds, including: 2-CP; 2,4-DCP;
2,4,6-TCP; and PCP. The method given below is applicable to municipal
and industrial discharge samples.
A 1 liter sample of wastewater is acidified (to pH 2 with H2S04) and may
be preserved with sodium thiosulfate (35 mg per ppm of free chlorine per
liter) to retard subsequent chlorination. Samples should be extracted
9-1 July, 1983
-------
within 7 days and analysis completed within 30 days of collection. The
water sample is extracted (CH2C12) and t*16 concentrated organic extract
may be analyzed directly by gas chromatography (GC) using flame-
ionization detection (FID). The method also provides for the
preparation of pentafluorobenzylbromide (PFB) derivatives for GC
analysis using electron-capture detection (BCD). An extraction
procedure for cleanup which takes advantage of the acidic nature of
phenols is also given. Assuming a 10 mL volume of extract from a 1
liter water sample and injection of 5 uL of the extract, the GC analysis
using FID yields detection limits of 2-10 ug of chlorophenol per liter
of water sample.
Standard quality assurance practices should be used with this method.
Field replicates should be collected to validate the precision of
sampling, and laboratory replicates should be analyzed to validate the
accuracy of analysis. If doubt exists over the identification of a peak
on the GC, confirmatory techniques such as mass spectroscopy (MS) should
be used.
Similar procedures designed for the analysis of phenolic compounds have
also been published. Method 510 in Standard Methods for the Examination
of Water and Wastewater, 15th Edition {American Public Health
Association, 1981} and Method D 2580-80 in the 1982 Annual Book of ASTM
Standards, Part 31 (ASTM, 1982) both describe the GC analysis using FID
of various phenolic compounds including mono-and dichlorophenols. A
supplement (1981) to the 15th edition of Standard Methods also includes
a technique for PCP which involves the formation of the methyl ether
derivative (via diazomethane) and analysis by GC with ECD.
Colorimetric procedures for total recoverable phenolic compounds are
also available (e.g.. Methods 510B and 510C in Standard Methods).
However, these techniques do not allow the different phenols to be
differentiated, and they are of limited utility in the analysis of
chlorophenols.
9.3 Solid Haste
Chlorophenols in waste materials may be determined by two methods
described in detail in Test Methods for Evaluating Solid Waste,
Physical/Chemical Methods (Office of Solid Waste and Emergency Response,
July 1982, SW-B46, Second Edition). Method 8.04 may be used to separate
2-CP; 2,4-DCP; trichlorophenols; tetrachlorophenols; and PCP, as well as
numerous other phenolic compounds. Water samples are acidified (pH <_ 2)
and extracted with CH2C12. Solid samples are also acidified and
extracted with CH2C12, using soxhlet extraction or sonication
procedures. Extracts are analyzed by GC using FID. This method also
provides for preparation of PFB derivatives and cleanup procedures.
Therefore, after extraction this method is similar to the GC method 604
for water described above.
Method 8.25 utilizes an extensive extraction procedure which permits the
analysis of complex samples; the chlorophenols are concentrated in the
extract from the acidified sample. GC analysis using MS separates and
identifies the chlorophenols present. The detection limit for Method
9-2 July, 1983
-------
8.25 for individual compounds is about 1 ug/g (wet weight) in waste
samples. This technique is listed as being applicable to nearly all
types of samples (water, sludges, acidic and basic liquors, oily wastes,
tars, soils, sediments, etc.).
9.4 Other Samples
Bibliographic reviews of methods used to determine chlorophenol levels
in a variety of matrices are available (ORNL, 1979; IARC, 1979). While
extraction/cleanup procedures vary widely, nearly all methods use GC for
separation and FID, BCD, or MS for detection. For example, a NIOSH
procedure (Method 230 in the NIOSH Manual of analytical Methods, Vol.1;
NIOSH Pub. No. 77-157A) for the analysis of PCP in urine involves
acidification, extraction, and analysis via GC equipped with a 6 Ni
BCD. An important point to stress, however, is that such analytical
methods for use with samples of biological origin may not measure the
conjugated forms of the chlorophenols (e.g., glucuronide salts).
9-3 July, 1983
-------
REFERENCES
The major references used in preparation of this document are listed below.
EPA references are listed by EPA office of origin and year of publication.
For further information refer to the contacts given throughout this document
or contact the relevant EPA offices listed at the end of this section.
(ECT, 1979)
(Hansch, 1979)
(OPP, 1981)
(ORNL, 1979)
(OTS, 1980)
(OWRS, 1979)
(OWRS, 1980a)
(OWRS, 1980b)
(OWRS, 1980c)
(OWRS, 1980d)
(OWRS, 1980e)
(OWRS, 1980f)
Encyclopedia of Chemical Technology, 3rd Ed., Kirk-Othmer,
"Chlorophenols11, pp. 864-872,- Wiley (1979).
Substituent Constants for Correlation Analysis in Chemistry
and Biology, C. Hansch and A. Leo, Wiley (1979).
Creosote, Inorganic Arsenicals, and Pentachlorophenol.
Position Document No. 2/3, EPA-540/9-82-004, Office of
Pesticide Programs (1981).
Reviews of the Environmental Effects of Pollutants.
XI Chlorophenols, EPA-600/1-79-012, Oak Ridge National
Laboratory (1979).
Materials Balance for Chlorophenols, Level I, EPA-56,0/
13-80-004, Office of Toxic Substances- (1980).
Water-Related Environmental Fate of 129 Priority
Pollutants, EPA-440/4-79-029b, Office of Water Regulations
and Standards (1979).
Ambient Water Quality Criteria for Chlorinated Phenols,
EPA-440/5-80-032, Office of Water Regulations and
Standards (1980).
Ambient Water Quality Criteria for 2-Chlorophenol, EPA-
440/5-80-034, Office of Water Regulations and Standards
(1980).
Ambient Water Quality Criteria for 2,4-Dichlorophenol,
EPA-440/5-80-042, Office of Water Regulations and Standards
(1980).
Ambient Water Quality Criteria for Pentachlorophenol, EPA-
440/5-80-065, Office of Water Regulations and Standards
(1980).
An Exposure and Risk Assessment for Chlorinated Phenols,
EPA-Final Draft Report, Office of Water Regulations and
Standards (1980).
An Exposure and Risk Assessment for Pentrachlorophenol,
EPA-Final Draft Report, Office of Water Regulations and
Standards (1980).
R-1
July, 1983
-------
OFFICE CONTACTS
The EPA offices and divisions that are listed below may be contacted for more
information relating to the indicated sections of this document. While these
offices are, in many cases, the offices of origin for the data included in
this paper, the personal contacts given throughout this document should be
contacted first. Unless otherwise noted, the offices listed are situated in
Headquarters, Washington, D.C., and the telephone numbers given are FTS
(Federal Telecommunications System) numbers. For commercial telephone calls
to Headquarters which are not placed on FTS, area code 202 must be used.
Other commercial numbers are noted for the office contacts located outside
Washington, D.C.
HEALTH AND ENVIRONMENTAL EFFECTS (Section 2)
Office of Health and Environmental Assessment (OHEA)
Environmental Criteria and Assessment Office:
Cincinnati, OH 684-7531 (513-684-7531)
Research Triangle Park, NC 629-4173 (919-541-4173)
Carcinogen Assessment Group 3B2-7341
Office of Drinking Water (ODW)
Health Effects Branch 382-7571
Office of Toxic Substances (OTS)
Health and Environmental Review Division 382-4241
Environmental Research Laboratory
Duluth, MM, Region V 783-9550 (218-727-6692)
ENVIRONMENTAL RELEASES AND EXPOSURE (Sections 3 and 4)
Office of Air Quality and Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Water Regulations and Standards (OWRS)
Monitoring and Data Support Division 382-7051
Office of Toxic Substances (OTS)
Exposure Evaluation Division 382-3873
R-2 July, 1983
-------
DATA BASES (Section 5)
Office of Toxic Substances (OTS)
Information Management Division 382-3749
REGULATORY STATUS, STANDARDS, AMD CRITERIA (Sections 6 and 7)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Drinking Hater (ODW)
Criteria and Standards Division 382-7575
Office of Hater Regulations and Standards (OWRS)
Criteria and Standards Division 755-0100
Effluent Guidelines Division 382-7120
Office of Solid Haste (OSH)
Permits and State Programs Division 382-4746
SPILL CLEAN-OP AND DISPOSAL (Section 8)
NOTE: For Emergencies call the National Response Center at 1-800-424-8802
(1-800-426-2675 from the Baltimore/Washington area).
Office of Emergency and Remedial Response (OERR)
Emergency Response Division 382-2182
Hazardous Site Control 382-2443
Oil and Hazardous Materials Spills Branch
Edison, NJ; Region II 340-6635 (201-321-6635)
ANALYTICAL TECHNIQUES (Section 9)
Environmental Monitoring Systems Lab (EMSL)
Air Analysis
Research Triangle Park, NC 629-2454 (919-541-2454)
Hater Analysis
Cincinnati, OH 684-7311 (513-684-7311)
R-3 July, 1983
-------
Waste Analysis
Las Vegas, NV 545-2137 (702-798-2137)
Office of Monitoring Systems
and Quality Assurance 382-5767
GENERAL IPP COMMENTS, CORRECTIONS, OR QUESTIONS
Chemical Coordination Staff
Chemical Information
and Analysis 382-3375
R_4 July, 1983
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1,4-Dichlorobenzene
-------
1,4-DICHLOROBENZENE
Table of Contents ^ Page
Physical/Chemical Properties and Chemistry 1-1
Properties l-l
Chemistry and Environmental Fate/Transport 1-1
Effects Information 2-1
Health Effects 2-1
Environmental Effects 2-2
Environmental Release 3-1
Air Releases 3-1
Water Releases 3-1
Land Releases 3-1
Exposure 4-1
Air Exposure 4-1
Water Exposure 4-1
Other Exposure Routes 4-1
Data Bases . 5-1
Chemicals in Commerce Information System (CICIS) 5-1
EPA Chemical Activities Status Report (EPACASR) 5-1
NIH/EPA Chemical Information System (CIS) 5-1
Chemical Regulations and Guidelines System (CRGS) 5-1
Chemical Substances Information Network (CSIN) 5-2
EPA Information Clearinghouse 5-2
Regulatory Status 6-1
Promulgated Regulations 6-1
Proposed Regulations 6-2
Other Actions 6-2
July, 1982
-------
Spill or Other Incident Clean-up/Disposal 8-1
Hazards and Safety Precautions 8-1
First Aid 8-1
Emergency Action 8-1
Notification and Technical Assistance 8-1
Disposal 8-1
Sampling, Acceptable Analytical Techniques, and Quality Assurance 9-1
Air 9-1
Water 9-1
Hazardous Waste 9-4
References and Office Contacts
July, 1982
-------
1,4-DICHLOROBENZENE
1. PHYSICAL/CHEMICAL PROPERTIES AND CHEMISTRY
This document will focus on 1,4-dichlorobenzene; however, since
Agency assessments and regulations often consider the 1,2- and the
1,3-isomer together with 1,4-dichlorobenzene, and because of the
similar chemistry of the isomers, some information on all three will
be presented.
Isomers; (synonyms) 1,2-dichlorobenzene (1,2-DCB, o-dichloroben-
zene,ortho-dichlorobenzene), 1,3-dichlorobenzene (1,3-DCB, m-di-
chlorobenzene, meta-dichlorobenzene), 1,4-dichlorobenzene (1,4-DCB,
p-dichlorobenzene, para-dichlorobenzene, PDB).
Chemical Abstract Service (CAS) Numbers;
1,2-DCB: 95-50-1
1,3-DCB: 541-73-1
1,4-DCB: 106-46-7
Mixed Isomers: 25321-22-6
1.1 Properties
1,2-DCB and 1,3-DCB are colorless liquids at room temperature. 1,4-
DCB is a white crystalline solid. All three isomers have a strong
aromatic odor. DCBs are not naturally occurring compounds. 1,4-DCB
and 1,2-DCB have varied and widespread uses and are produced in
approximately equal amounts. 1,3-DCB has no commercial uses at
present. The kinetics of current synthetic pathways favor overwhelm-
ingly the formation of the 1,2- and 1,4-isomers (although 1,3-DCB is
favored thermodynamically). Relevant physical/chemical properties
are listed in Table 1.
1.2 Chemistry and Environmental Fate/Transport
Because of the lack of environmentally significant information, it is
not possible to determine the predominant transport and aquatic fate
of DCB. DCB has a high affinity for lipophilic materials, a rela-
tively low aqueous solubility, and a low vapor pressure at ambient
temperatures. Consequently, sorption, bloaccumulation, and volatili-
zation are expected to be competing transport processes. The rate at
which these competing processes occur will determine which fate is
predominant in the aquatic environment (OWRS, 1979).
Ninety-six percent of the DCBs, not converted to other products, are
released to the air (OWRS, 1981b). Once in the atmosphere DCB is
reported to be reactive toward hydroxyl radicals in air with a half
life of approximately three days. The 1,2- and 1,4-isomer were also
reported to be resistant to autooxidation by ozone in air (OWRS,
1979).
1-1 July, 1982
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TABLE 1: PHYSICAL/CHEMICAL PROPERTIES
CAS number:
Molecular formula:
Structure:
Molecular weight:
Melting point, "C:
Boiling point, °C:
Flashpoint, °C:
Density (20)
C 4):
Vapor pressure at
25°C, totr:
Solubility at 25°C,
mg/1:
Log octanol/water
partition coefficient:
1,2-DCB
95-50-1
C6H4C12
Cl
Cl
>Av s
Of
^Sx^
147.01
-17.0
180.5
66.1
1.31
1.5
145.0
1,3-DCB
541-73-1
C6H4C12
Cl
&
a
147.01
-24.7
173.
1.29
2.28
123.0
1,4-DCB
106-46-7
a
O
||
147.01
53.1
174.
65.6
1.25
1.18
79.0
3.38
3.38
3.39
1-2
July, 1982
-------
Because of their high lipid/low water solubility, DCBs can cross
barrier membranes and be widely distributed to various tissues.
(Blood, blood chemistry, neuromuscular function, liver and kidney
structure and function have been shown to be affected in man and
animal.) DCBs are detoxified in the liver by microsomal enzymes:
DCBs are oxidized to isomers of dichlorophenols, (the major metabo-
lites) depending on the DCB isomer, and excreted as conjugates of
glucuronic and sulfurlc acids. Excretion of all three isomers
through the urine is slow, requiring about six days. (Presence of
dichlorophenol levels in the urine can be used in assessing expo-
sure. XOWRS, 1980).
1-3 July, 1982
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2. EFFECTS INFORMATION
2.1 Health Effects (CONTACT: Jerry Stara, FTS 684-7531;
Penny Fenner-Crisp, FTS 472-4944)
2.1.1 Acute Toxiclty
Acute dermal exposure of human subjects to 1,2-DCB resulted in
burning sensation within 15 minutes. The response intensified with
continued exposure and abated when the liquid was removed from the
skin. However, hyperemla and blisters developed afterward at the
site of application and were followed by a brown pigmentation that
persisted at least three months. Inhalation of the vapor (>300
mg/m3) may result in eye and nose irritation (OURS, 1980).
Acute dermal exposure to solid 1,4-DCB produces a burning sensation
when held in contact with the skin, but the resulting irritation is
slight. However, warm fumes or strong solutions may irritate the
skin slightly on prolonged or repeated contact. Inhalation of solid
particles of 1,4-DCB or heavy vapors or fumes (such as when heated
and volatilized in poorly ventilated spaces) are painful to the eyes
and nose. The painful effect of vapor is evident to most people at
300 to 480 mg/m3 (OWRS, 1980).
2.1.2 Chronic Toxlcity
Most reported cases of human poisoning by DCBs have resulted primari-
ly from long-term exposure by inhalation of vapors, but some have
also resulted from oral or skin exposure. Most episodes were occupa-
tional; however, several involved the use of DCBs in the home (in
toilet deodorant blocks, moth balls and cleaning products) (OWRS,
1980).
The principle target system or tissues are one or more of the
following: liver, blood, CNS, respiratory tract, and integument.
Clinical findings of chronic exposure to DCB include weakness,
fatigue, dizziness, malaise, nausea, vomiting, headache; profuse
rhinitis and periorbital swelling; upper respiratory tract irritation
such as chronic progressive cough and dyspnea with mucoid sputum,
wheezing, diminished breath sounds and rales resulting from pulmonary
granulomatosls; esophageal verices; decreased appetite; weight loss
and exhaustion. Hepatocellular derangement such as hepatomegaly,
proteinuria, and bilirubinuria are common. Often DCB exposures
result in severe acute hemolytic anemia, peripheral lymphadenopathy,
leukocytosis, polynucleosis, and splenomegaly. Several cases of
chronic lymphoid leukemia and acute myelobiastic leukemia have
resulted after chronic exposure to 1,4-DCB (OWRS, 1980).
Evidence as to the mutagenicity of DCBs is inconclusive. The
teratogenicity of any of the DCBs has not been studied and reported.
Published studies of tests for carcinogenic!ty fall very short of
establishing a cause-effect relationship and do not permit a
quantitative risk assessment applicable to the general population.
Although strong direct evidence of carcinogenicity for DCB is not
available, there seems to be a sufficient collection of varied data
2-1 July, 1982
-------
to suggest a prudent regard of the DCBs as suspected carcinogens,
pending the availability of better data (OURS, 1980). NT? Is
currently conducting large-scale carcinogenicity bioassays on both
the 1,2- and 1,4-DCB isomers. These results are expected in 1982.
2.2 Environmental Effects (CONTACT: Charles E. Stephen FTS 783-9510;
John Gentile, FTS 838-4843;
Virginia M. Snarski, FTS 783-9584)
2.2.1 Aquatic Effects (OWRS, 1980)
DCBs in water result from anthropogenic sources: i.e., industrial and
consumer discharges and water chlorinatioa. There appears to be
little difference (and no consistent difference) in aquatic toxic
effects among the three DCB isomers.
Freshwater - The 48-hour EC50 values for Paphnia magna and a midge
for 1,2-, 1,3-, and 1,4-dichlorobenzene ranged from 2,440 to 28,100
tig/I with no consistent difference due to location of the chlorine
atoms or sensitivity of the two species. The range of LC$Q values
for three fish species and the same dichlorobenzenes was 1,120 to
27,000 ug/1, and the rainbow trout appears to be a little more
sensitive than the two warmwater fish species.
Embryo-larval tests with the fathead minnow and 1,2-, 1,3-, and 1,4-
dichlorobenzene have been conducted; the chronic values ranged from
763 to 2,000 ug/1. The acute-chronic ratio for both 1,3- and
1,4-dichlorobenzene was 5.2.
The freshwater alga, Selenastrum capricornutum, is less sensitive to
the dichlorobenzenes with EC5Q values that range from 91,600 to
179,000 ug/1.
Saltwater - The saltwater mysid shrimp has been exposed to 1,2-,
1,3-, and 1,4-dichlorobenzene and the 96-hour LC^g values were 1,970,
2,850, and 1,990 ug/1, respectively. For the sheepshead minnow and
the same chemicals, the 96-hour ŁŁ50 values were in the range of
7,400 to 9,660 ug/1. Ho chronic toxicity data are available for any
saltwater species.
The 96-hour EC50 for a saltwater alga and 1,2-, 1,3-, and
1,4-dichlorobenzene ranged from 44,100 to 59,100 ug/1.
2.2.2 Other Effects (OWRS, 1980)
The measured steady state bioconcentration factors for the three DCBs
are in the range of 60 to 89 for the bluegill.
2-2 July, 1982
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3. ENVIRONMENTAL RELEASE
Several Agency program offices have evaluated and ranked sources of
DCS release. Even though the reported quantities emitted to the
environment differ, there is general agreement as to the major
sources of DCS releases. Table 2 lists both the use of DCB isomers
and their release to the environment by media. The release data are
only crude estimates and have not been verified by sampling and
analyses.
3.1 Air Releases, 1,4-DCB (CONTACT: Dave Patrick, FTS 629-5645)
Significant Source:
• Manufacturing and processing, occupational exposure
Other Sources:
Spills
Domestic use (indoor air)
Land disposal
Vapor release from contaminated surface waters
Ambient air in vicinity of solvent use and chemical intermediate
plant
3.2 Water Releases, 1,4-DCB (CONTACT: Michael Slimak, FTS 426-2503)
Significant Source:
• Contamination of surface and groundwater from unconflned
landfills
Other Sources:
• Water washdown of spills
• POTU effluents
3.3 Land Releases, 1,4-DCB (CONTACT: Ken Schuster, FTS 382-4654)
Significant Source:
• Release from unconfined landfills
3-1 July, 1982
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TABLE 2: ENVIRONMENTAL RELEASES, 1978 (kkg/yr)
Amount
Isomer Category Used/Produced Air Hater Land
1 , 2-DCB Production
3 , 4-Dichloroaniline
production
Toluene diiso-
cyanate manufacture
Misc. solvents
Dye synthesis
Other*
Exports
1,4-DCB Production
Space deodorant
Moth control
Other-H-
Exports
27,000
17,000
3,600
1,900
960
720
3,200
33,000
15,000
9,500
2,700
6,300
96 230 6
24 —
3,600 — neg.
1,900 10 20
neg.
70
240 290 8
14,000 500 500
9,500 1 1
5
—
1,3-DCB Negligible
"*" Including: odor control in sewage, pesticide manufacturing, laboratory
supply.
•H- Primarily pesticide manufacturing, abrasives, and textiles.
Source: OWRS (1981a).
3-2 July, 1982
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4. EXPOSURE
DCB primarily enters the body through ingestion or inhalation.
Respiratory absorption is rapid after inhalation; however, there are
no data on the percentages absorbed. Absorption through ingestion is
rapid, and under at least some circumstances can be complete (OWRS,
1980).
4.1 Air Exposure (CONTACT: Karen Blanchard, FTS 629-5519)
The seven DCB production facilities are a source of occupational and
surrounding residential low-level chronic exposure. The frequent use
of end products containing DCBs, especially moth balls, diaper pail
deodorizers and toilet bowl deodorizers, can provide a low-level
exposure route.
4.2 Water Exposure (CONTACT: Michael Slimak, FTS 426-2503;
Bill Coniglio, FTS 382-3035)
Accidental spills into drinking water supplies or contamination of
groundwater from land disposal could result in high-level short-term
or low-level long-term exposure, respectively.
4.3 Other Exposure Routes (CONTACT: Ken Schuster, FTS 382-4654)
Land disposal could result in exposure through either groundwater
contamination or elevated ambient air levels near disposal sites.
4-1 July, 1982
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TABLE 3: DCS EXPOSURE ESTIMATES
10
fer
CO
to
1 , 2-DCB 1 , 3-DCB
Concentration Exposure Concentration Exposure
(ug/D (rag/day) (ug/1) (mg/day)
Drinking Water
Maximum observed 9.1 .018 — —
Mean observed 1.5 3xlO~3 .01 2xlO~4
Medium concentration <.005 <10~5 <.005 <10~5
(ug/m3) (mg/day) (ug/m3) (mg/day)
Ambient Air (24 hrs.)
Range (11 sites) 0-.106 0-.002 0-.382 0-.009
Urban — — .1 .02
Rural — — <1 <.02
Air at Industrial Sites .002-1.3 — .001-1.2
Air at Disposal Sites <. 03-12 -- <. 03-34
Occupational (1 site)
Maximum observed — — —
Residential (space deoderizer or moth repellant)
in Bedroom — — — —
in Closet
in Wardrobe — — — —
1,
Concentration
(ug/1)
2.0
.07
<.005
(ug/m3)
0-.062
2.7-4.2
1.5-2.4
.001-1.2
4.21xl05
105
315
1700
4-DCB
Exposure
(mg/day)
4x1 0~3
<10~5
(mg/day)
0-.001
.06-. 09
.03-. 05
4,042 mg/8 hr.
.6 mg/10 hr.
.2 mg/.5 hr.
.2 mg/. 1 hr.
Source: OWRS (I981a).
-------
5. DATA BASES
5.1 Chemicals in Commerce Information System (CICIS)
The Inventory was compiled under the authority of Section 8 of TSCA,
which requires manufacturers to report to EPA the chemicals Imported
and manufactured during calendar year 1977. The Inventory lists the
Chemical Abstract Service (CAS) preferred name for the chemicals,
their respective CAS number (often used for Identification purposes),
and production site, company name, and volume(s) of production and
import. There is also a Confidential Inventory in which many of
these characteristics are claimed confidential by the manufacturer.
In these instances, the confidential information will not be
available on the public inventory. CICIS can now be accessed through
the NIH/EPA Chemical Information System (CIS - see 5.3). For further
information, contact Gerri Nowack at FTS 382-3568.
5.2 EPA Chemical Activities Status Report (EPACASR)
EPACASR is an on-line system containing information on EPA's Interest
in chemicals. This system Includes data on the Agency's regulations,
research, and assessments directed toward specific chemicals.
EPACASR is published annually and the data base is updated as Infor-
mation is received. A searchable subset itemizes NTP/NCI studies and
results, as well as chemicals discussed in the IARC monograph
series. (Other sources are added as appropriate.) Entries identify
the statutory authority, the nature of the activity, its status, the
reason for and/or purpose of the effort, and a source of additional
information. Searches may be made by CAS Number or coded text. For
further information contact Eleanor Merrick at FTS 382-3415.
5.3 NIH/EPA Chemical Information System (CIS)
This is a collection of various scientific data bases available
through an interactive computer program. The linking system between
these data files is the Structure and Nomenclature Search System
(SANSS). CIS can also provide a list of non-CIS sources of informa-
tion on a chemical of Interest. However, these files have to be
accessed Individually by either separate on-line systems or in hard-
copy. For further information contact Delores Evans at FTS 382-3546
or Irv Weiss at FTS 382-3524.
5.4 Chemical Regulations and Guidelines System (CRGS)
CRGS is an on-line data base that is being developed to provide
information on chemical regulatory material found in statutes, regu-
lations, and guidelines at the Federal, State, and international
levels. Currently, only the first phase of CRGS, which encompasses
source material at the Federal level only, is operational. Nation-
wide access to CRGS is available through Dialog. For further Infor-
mation, contact Delores Evans at FTS 382-3546 or Ingrid Meyer at FTS
382-3773.
5-1 July, 1982
-------
5.5 Chemical Substances Information Network (CSIN)
The prototype CSIN, operational since November 1981, has been
developed by merging the technologies of computer networking and
distributed data base management. CSIN is not another data base, but
a library of systems. Through the CSIN front-end intermediary
management computer, the user may access and use independent and
autonomous information resources that are geographically scattered,
disparate for data and information content, and employ a variety of
types of computer hardware, software, and protocols. Users may
converse in and among multiple systems through a single connection
point, without knowledge of or training on these independent systems.
Currently, six independent information resources are accessible
through CSIN. They are: National Library of Medicine (NLM), CIS,
EPA-CICIS, CAS-On-Line, SDC-orbit, and two files of Dialog: CRGS and
TSCA Inventory. The CSIN management computer allows the user to
create, retrieve, store, and manipulate data and queries. This
eliminates the need for reenterlng long lists of chemical identifiers
or other information elements that are part of the original query or
that have been identified and acquired from one or more of the CSIN
resources. For further information contact Sid Siegal at FTS
382-2256.
5.6 EPA Information Clearinghouse
The EPA Information Clearinghouse is a bibliographic data base com-
posed of over 475 individual data bases and models that contain
monitoring information and statistics on a variety of chemicals. The
individual data bases are maintained by offices within EPA. For
further Information, contact Charlene Sayers at FTS 755-9112.
The following data bases contain information on 1,4-DCB:
BAT Review Study for the Timber Products Processing, Gum and Wood,
Chemicals, and the Printing and Publishing Industries
Best Management Practices, Timber Industry Effluent Guidelines -
Runoff
Best Management Practices, Timber Industry Effluent Guidelines -
Sludge
Chemicals in Commerce Information System
Compliance Sampling Toxicant Surveys
Consolidated Permits Program-Application Form l,2b,2c
Data Collection Portfolio for Industrial Waste Discharges
Distribution Register Organic Pollutants in Water
Drinking Water
Effluent Guidelines GC/MS Screening Analysis Data Base
Energy and Mining Point Source Category Data Base
Federal Facilities Information System
Fine Particle Emissions Information System
Food Industry Group
Fugitive Emissions Information System
Gaseous Emissions Data System
Hazardous Waste Data Management System
5-2 July, 1982
-------
Hazardous Waste Site Tracking System
Hemlock, Michigan Environmental Samples
Humacao Ambient Data Base
IFB Organics Data Base
Indicatory Fate Study
Industrial Process Evaluations
Infrared Spectra of Pollutants
Innovative Technology, Timber Industry Effluent Guidelines
Inorganic Chemicals Industry Regulation Record
LiPari Landfill
Liquid Effluents Data System
Listing of Organic Compounds Identified in Region IV
Love Canal Data Handling System
Method Validation Studies of Priority Pollutants
National Pollutant Discharge Elimination System (NPDES) Discharge
Permit Compliance
Nationwide Urban Runoff Program
Needs Survey
New York Bight Ocean Monitoring Program
Organic Chemicals/Plastics Industry
Organic Transport thru Soil
Paint and Ink Analytical Data
Permit Compliance System
Pesticide Incident Monitoring System
Pharmaceutical Screening/Verification Data Base
Precision and Accuracy for Screening Protocols
Priority Pollutants-Region I
Priority Pollutants-Region III
Publicly Owned Treatment Works (POTW) Analytical Data
Publicly Owned Treatment Works (POTW) Quality Control
Puerto Rico Reservoirs
Regional Toxics Monitoring Program
Resource Conservation and Recovery Act (RCRA)-Hazardous Waste Site
Inspections
Screening Sampling Program
Select Hazardous Chemicals-Ambient
Sources of Toxic Pollutants Found in Influents to Sewage Treatment
Plants
Spill Prevention Control and Countermeasure
System for Consolidated Permitting and Enforcement Data Base
Textile Industry BAT Study-Toxic Sampling Data
Toxics Monitoring
U.S. Virgin Islands-St. Thomas, St. Croix
Verification Data Base
Verification Sampling Program
Waste Characterization Data Base
Water Enforcement Regional System
Water Quality Information System
5-3 July, 1982
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6. REGULATORY STATUS (current as of 4/23/82)
6.1 Promulgated Regulations
6.1.1 EPA Programs
Clean Water Act (CWA)
o Sections 301, 304. 306, and 307 - All isomers of DCB are listed
as priority pollutants (toxic pollutants, 40CFR401.15). No
standards specific for DCBs have been issued.
• Section 311 - DCB is designated as a hazardous substance
(40CFR116.4) and is subject to reporting requirements
(40CFR117.3).
Resource Conservation and Recovery Act (RCRA)
• Section 3001 - All three isomers of DCB have been designated as
toxic hazardous wastes (T) if and when they are discarded as a
commercial product or an off-specification species: U070
(1,2-DCB), U071 (1,3-DCB), and U072 (1,4-DCB). Contaminated and
spill residues are also considered hazardous wastes
(40CFR261.33). '
The following wastestreams are designated as toxic hazardous
wastes (T), due in part to the presence of DCB (40CFR261.31,
40CFR261.32).
-F002- The following spent halogenated solvents: tetrachloro-
ethylene, methylene chloride, trichloroethylene, 1,1,1-trichlor-
oethane, chlorobenzene, 1,l,2-trichloro-l,2,2-trifluroethane,
ortho-dichlorobenzene, and trichlorofluoromethane; and the still
bottoms from the recovery of these solvents.
-K042- Heavy ends or distillation residues from the distilla-
tion of tetrachlorobenzene in the production of 2,4,5-T.
-K085- Distillation or fractionation column bottoms from the
production of chlorobenzenes.
-K105- Separated aqueous stream from the reactor product wash-
Ing step in the production of chlorobenzenes.
• Sections 3002 to 3006 - Regulations for generators and
transportersof hazardous waste and standards for treatment,
storage, and disposal facilities are applicable for the above
hazardous wastes (40CFR262 to 265). Permitting procedures are
included in the Consolidated Permit Regulations (40CFR122 to
124).
6-1 July, 1982
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6.1.2 Programs of Other Agencies
OSHA - Occupational Safety and Health Act
• Employee exposure to 1,2-DCB is limited by an acceptable ceiling
concentration. Employee exposure to 1,4-DCB is limited by an
8-hour time weighted average (TWA) (29CFR1910.1000).
DOT - Hazardous Materials Transportation Act
• Regulations concern the listing, labeling, and shipping of haz-
ardous materials including 1,2-DCB and 1,4-DCB (40CFR171 and
172.101).
FDA - Federal Food, Drug, and Cosmetic Act
• Regulations setting maximum levels in food-contacting material
(21CFR121.614).
6.2 Proposed Regulations
6.2.1 EPA Programs
TSCA
• Section 4 - Proposed health effects test rule for chloroben-
zenes; specific structural teratogenicity, reproductive effects,
and subchronic/chronic effects testing (45FR48524, 7/18/80;
45FR68411, 10/15/80),
CAA
New Stationary Source Performance Standards proposed which would
limit VOC from fugitive emission sources in the synthetic organ-
ic chemical manufacturing industry. All three DCB isomers are
among a number of VOC included in the proposal (46FR1136,
1/5/81).
6.3 Other Actions
Comprehensive Environmental Response, Compensation, and Liability Act
(CERCLA or Superfund)
• CERCLA provides for the liability, compensation, clean-up, and
emergency response for the release of hazardous substances into
the environment. This Act also deals with the cleanup of
hazardous waste disposal sites (42USC9601; PL 96-510).
• EPA is developing regulations concerning the designation of
hazardous substances, the development of reportable quantities,
claims procedures, and the confidentiality of business records
(46FR54032). Revisions to the National Contingency Plan (NCP)
as required by CERCLA have been issued in a proposed rule
(47FR10972).
6-2 July, 1982
-------
• Hazardous substances as defined by Section 101(14) of CERCLA
include: hazardous wastes designated under Section 3001 of the
RCRA; hazardous air pollutants regulated under Section 112 of
the CAA; water pollutants listed under Sections 307 and 311 of
the CWA (and also any substances regulated in the future under
Section 7 of TSCA and Section 102 of CERCLA). Therefore, DCBs
are hazardous substances under CERCLA and will be subject to
regulations issued under Superfund.
Safe Drinking Water Act (SDWA) - DCBs are among a number of
substances discussed in an Advance Notice of Proposed Rulemaking
(ANPR) for possible inclusion in revised National Primary Drinking
Water Regulations for volatile synthetic organic chemicals (47FR9350,
3/4/82).
6-3 July, 1982
-------
7. STANDARDS AND RECOMMENDED CRITERIA*
7.1 Air
o Current OSHA standard for 1,2-DCB
(29CFR1910.1000): 300 mg/m3 (ceiling)
o Current OSHA standard for 1,4-DCB
(29CFR1910.1000): 450 mg/m3 (8-hr TWA)
7.2 Water (CONTACT: Penny Fenner-Crisp, FTS 472-4944)
• The Agency expects to develop Health Advisories (HA) for both
1,2-DCB and 1,4-DCB in 1982.
• Water Quality Criteria (for DCB):
Human health 400 ug/1
(ingestion of both
water and contam-
inated organisms)
Freshwater aquatic life (acute) 1,120 ug/1
(chronic) 763 ug/1
Saltwater aquatic life (acute) 1,970 ug/1
• Hazardous spill rules require notification of discharges equal
to or greater than 100 Ib (40CFR117.3).
7.3 Other
FDA food contact maximum level .8 mg/kg in polyphenylene sulfide
resins (21CFR121.614).
* See Appendix A for a discussion of the derivation, uses, and limitations of
these criteria and standards.
7-1 July, 1982
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8. SPILL OR OTHER INCIDENT CLEAN-UP/DISPOSAL
(CONTACT: National Response Center, 800-424-8802, in Washington,
D.C., 426-2675)
8.1 Hazards and Safety Precautions
DCBs readily volatilize to a moderately toxic vapor that may irritate
the eyes and upper respiratory tract. DCB can be absorbed through
the skin and is a skin irritant.
DCBs are combustible and when handled at elevated temperatures the
isomers present a flammable hazard in the presence of an ignition
source (sparks or flames). Fire produces extremely toxic combustion
products.
8.2 First Aid
Move victim to fresh air, and call medical help. Give artificial
respiration if victim is not breathing, or oxygen if breathing is
difficult. In case of contact, immediately flush skin with running
water, followed by washing with soap and water. Remove contaminated
clothing. In case of contact with eyes, flush eyes with flowing
water for 15 minutes. If taken internally, vomiting should be
induced. An emetic such as soapy water should be taken followed by
drinking as much water as possible. Call a physician.
8.3 Emergency Action
Spill or Leak - Stay upwind, isolate hazardous area, and wear self-
contained breathing apparatus and full protective clothing (including
eye protection such as full-face mask). Remove Ignition sources and
use carbon or peat on soluble portion. Pump or vacuum from bottom.
For dissolved portions, use carbon or peat.
Fire - For small fires use dry chemical, C02, water spray, or foam.
For large fires, use water spray or foam. Move containers from fire
area if possible; cool containers exposed to fire with water until
well after fire is out. Isolate for one-half mile in all directions
if tank or tankcar is involved in a fire.
8.4 Notification and Technical Assistance
Section 103 of the Comprehensive Environmental Response, Compensa-
tion, and Liability Act (CERCLA) or "Superfund" requires notification
of the National Response Center (NRG, 800-424-8802 or in the
Washington, D.C. area, 426-2675) if releases exceed reportable
quantities (100 Ibs. in the case of DCB). For emergency assistance
call CHEMTREC: 800-424-9300. For information call the Division of
Oil and Special Materials at 1-202-245-3045.
8-1 July, 1982
-------
8.5 Disposal
Generators of more than 1,000 kg/month of commercial product (or
residues from spill cleanup) are subject to RCRA regulations.
The following specific wastestream is subject to Subpart D
regulations:
• dichlorobenzene solvents or solvent-recovery still bottoms.
8-2 July, 1982
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9. SAMPLING, ACCEPTABLE ANALYTICAL TECHNIQUES, AND QUALITY ASSURANCE
9.1 Air (CONTACT: Joseph F. Walling, FTS 629-7954)
1,4-dichlorobenzene is not a criteria pollutant; therefore, no Agency
or reference procedures exist. Although measurements of this pollut-
ant have been made and reported, there are no well-documented method
descriptions available for quantitative measurements in ambient air.
Therefore, monitoring for this pollutant must be approached with
great caution.
A procedure using Tenax adsorbent for sampling and gas chromato-
graphy/mass spectrometry (GC/MS) for analysis has been used (EPA
Method //601, 40CFR136) but little is known about the precision and
accuracy of the procedure. GC/MS requires special expertise and
expensive, sophisticated equipment. For these reasons, monitoring
for one compound alone using the Tenax GC/MS procedure is rarely cost
effective and the approach is most suitable when monitoring for an
array of volatile compounds is desired.
The preparation of Tenax suitable for sampling is demanding. Tenax
background is a problem that must be addressed (e.g., by using a
blank). Precautions about permissible maximum air volumes, sampling
rates, and ambient temperatures during sampling must be observed and
these, in turn, govern allowable sampling times.
Detection limits and accuracy are not known; reproducibility is esti-
mated to be 50-100 percent. Quality assurance materials composed of
blank Tenax sampling cartridges spiked with known amounts of
1,4-dichlorobenzene can be prepared and must be used in any monitor-
ing program.
NIOSH - NIOSH certifies detector tubes calibrated for direct-reading
of 1,2-DCB and 1,4-DCB. These are listed under 42CFR84. Also,
analytical methods for 1,2-DCB and 1,4-DCB are available in the NIOSH
Manual of Analytical Methods, Volumes 2 and 3, respectively, 1977
(GPO Nos. 017-033-00260-6 and 017-033-00261-4, respectively).
9.2 Water (CONTACT: Thomas Bellar, FTS 684-7311 or
James Llchtenberg, FTS 684-7308)
There are several approved and proposed gas chromatographic proce-
dures for the analyses of 1,2-DCB and 1,4-DCB in natural, waste, and
drinking waters. The primary difference between the methods is the
extraction procedure and the means of injecting the extracts into the
gas chromatograph. Mass spectrometry and halogen specific detectors
are normally used to improve qualitative accuracy.
Direct Aqueous Injection EPA # Method 8 (1)
ASTM f D 2908-74 (2)
Major Equipment Required: Gas chromatograph
9-1 July, 1982
-------
One Co 5 ul of Che neat sample is injected directly into the gas
chromatograph. The method detection limit is approximately 1 mg/1
when mass spectrometry, flame ionization, or halogen specific detec-
tors are used. For nickel-63 electron capture detectors the method
detection limit is approximately 1 ug/1.
Liquid-Liquid Extraction EPA // 612(3) 625 (4)
Major Equipment Required: Gas chromatograph
A measured volume of sample, approximately 1 liter, is solvent ex-
tracted with methylene chloride using separatory funnel techniques.
The methylene chloride is dried and solvent exchanged to hexane
during concentration Co a volume of 10 ml or less. One to five ul of
Che extract is Chen injected into a gas chromatograph equipped with
an electron capture detector. The method detection limit is approxi-
mately 1.0 ug/1 (4.4 ug/1 for 625 Base/Neutral Extractions).
Purge and Trap EPA f 601,(4) 624,(*) 502.1,(5) 503.1 (?)
ASTM 9 D-3871-79(6)
Standard Methods - To be included in the 15th Edition
Major Equipment: Gas chromatograph and purge and trap apparatus
Five ml of the aqueous sample is placed into a purging device.
1,4-dichlorobenzene and other volatile water Insoluble organic com-
pounds are transferred from the aqueous phase to the gas phase. The
volatilized compounds are swept from the purging device by the purge
gas and are trapped in a short column containing a suitable sorbent.
After a predetermined period of time the trapped compounds are
thermally desorbed and backflushed into a gas chromatograph equipped
with a mass spectrometer, flame ionization, or a halogen specific
detector.
The method detection limit for the mass spectrometer (full scan) and
the flame ionization detector is approximately 1 ug/1. For a care-
fully optimized halogen specific detector method, detection limits as
low as 20 ng/1 have been achieved.
Samples are collected In narrow-mouth screen-cap bottles with TFE
fluorocarbon seals. Samples are stored head-space free at 4°C in the
dark. Sodium thiosulfate is normally used to remove free residue
chlorine. Spiked river water samples have been stored for up to 7
days under these conditions with no apparent losses.
Single laboratory test data on simple spiked matrices have been
collected by EPA. Intralaboratory accuracy and precision and method
detection limit data are currently being collected (see Table 4).
Quality control and performance evaluation samples (methanolic con-
centrates containing the isomer to be spiked into water) are avail-
able from the Environmental Monitoring and Support Laboratory,
Quality Assurance Branch, USEPA, Cincinnati, Ohio 45268.
9-2 July, 1982
-------
References for Water Analysis
1. "A Method for Organochlorine Solvents in Industrial Effluents,"
National Pollutant Discharge Elimination System Appendix A,
Federal Register 38, No. 7S Pt. II.
2. "Standard Test Method for Measuring Volatile Organic Matter in
Water by Aqueous - Injection Gas Chromatography," Annual Book of
ASTM Standards, 1980, Part 31, Water, ASTM D-2908-74.
3. Federal Register, Thursday, November 29, 1979, Volume 44. No.
231, 40CFR, Appendix C - Parts I and II.
4. Federal Register, Monday, December 3, 1979, Volume 44, No. 233,
40CFR Part 136, Guidelines Establishing Test Procedures for the
Analysis of Pollutants.
5. "The Determination of Halogenated Chemical Indicators of
Industrial Contamination in Water by the Purge and Trap Method,"
Method 502.1, September 1980, USEPA, Environmental Monitoring
and Support Laboratory, Cincinnati, Ohio 45268.
6. "Standard Test Method for Measuring Purgeable Organic Compounds
in Water Using Headspace Sampling," ASTM D-3871-79, Part 31,
Water, Annual Book of ASTM Standards, 1980.
7. "The Analysis of Aromatic Chemical Indicators of Industrial
Contamination in Water by the Purge and Trap Method," Method
503.1, May 1980, USEPA, Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio 45268.
9-3 July, 1982
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TABLE 4: LIST OF WATER PROCEDURES FOR 1,4-DICHLOROBENZENE
Standard
Recovery* Deviation
Method
Type
MDL
Status
EPA 625
EPA 624
EPA 601
EPA 502.1
EPA 503.1
EPA 8
Standard Methods
ASTM D- 209 8- 7 4
ASTM D-3871-79
EPA 612
LLE
P&T
P&T
P&T
P&T
DAI
P&T
DAI
P&T
LLE
4.4 ug/1
ND
.24 ug/1
<0.1 ug/1
<0.1 ug/1
1 ag/1
ND
ND
ND
1.34 ug/1
67
ND
ND
90
106
ND
ND
ND
ND
89
22
ND
ND
7
9
ND
ND
ND
ND
20
Proposed
Proposed
Proposed
Proposed
Untested
Official*
Untested
Untested
Untested
Proposed
P&T = Purge and Trap
LLE = Liquid/Liquid Extraction
DAI = Direct Aqueous Injection
Status - As of March 1981.
* Single laboratory recovery from spiked reagent water or spiked wastewater.
+ Official for the analysis of organohalides in wastewater.
9.3
Hazardous Waste (CONTACT:
Donald F. Gurka, FTS 545-2113 or
Werner F. Beckert, FTS 545-2137)
The RCRA regulations, Part 261, Appendix III, refer to tests 8.25,
8.01, 8.02, and 8.12 in "Test Methods for Evaluating Solid Waste,"
SW-846 as suitable for the analyses of dichlorobenzenes.
9-4
July, 1982
-------
REFERENCES
The major references used In preparation of this document are listed below.
EPA documents are referenced by EPA Office of origin and the year of
publication. For further information refer to contacts given throughout this
document or contact the relevant EPA Program Offices listed in the next
section.
(OWRS, 1979) Water-Related Environmental Fate of 129 Priority Pollut-
ants, Vol. II, EPA-440/4-79-029b, Office of Water Regula-
tions and Standards (1979).
(OWRS, 1980) Ambient Water Quality Criteria for Dichlorobenzenes, EPA
440/5-80-039, Office of Water Regulations and Standards
(1980).
(OWRS, 1981a) An Exposure and Risk Assessment for DJchlorobenzenes,
Office of Water Regulations and Standards (1981).
(OWRS, 1981b) Strategy for Controlling Environmental Exposure to
1,2-DCB. 1,3-DCB, and 1,4-DCB, Office of Water
Regulations and Standards (1981).
R-l July, 1982
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OFFICE CONTACTS
The EPA Offices and Divisions that ace listed below may be contacted for more
Information relating to the indicated sections of this document. While these
offices are, in many cases, the offices of origin for the data Included in
this paper, the personal contacts given throughout this document should be
contacted first. Unless otherwise noted, the offices listed are situated in
Headquarters, Washington, D.C., and the telephone numbers given are FTS
(Federal Telecommunications System) numbers. For commercial telephone calls
to Headquarters not placed on FTS, area code 202 must be used. Other
commercial numbers are noted for the office contacts located outside
Washington, D.C.
HEALTH AND ENVIRONMENTAL EFFECTS (Section 2)
Office of Health and Environmental Assessment (OHEA)
Environmental Criteria and Assessment Office:
Cincinnati, OH 684-7531 (513-684-7531)
Research Triangle Park, NC 629-2266 (919-541-2266)
Carcinogen Assessment Group 755-3968
Office of Drinking Water (ODW)
Health Effects Branch 472-6820
Office of Toxic Substances (OTS)
Health and Environmental Review Division 382-4241
Environmental Research Laboratory
Duluth, MN, Region V 783-9550 (218-727-6692)
ENVIRONMENTAL RELEASES AND EXPOSURE (Sections 3 and 4)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Water Regulations and Standards (OWRS)
Monitoring and Data Support Division 426-2503
R-2 July, 1982
-------
Office of Toxic Substances (OTS)
Exposure Evaluation Division 382-3873
Assessment Division 382-3442
DATA BASES (Section 5)
Office of Toxic Substances (OTS)
Management Support Division 382-3546
REGULATORY STATUS, STANDARDS, AND CRITERIA (Sections 6 and 7)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Drinking Water (ODW)
Criteria and Standards Division 472-5016
Office of Water Regulations and Standards (OWRS)
Criteria and Standards Division 755-0100
Effluent Guidelines Division 426-2571
Office of Solid Waste (OSW)
State Programs and Resources
Recovery Division 755-9107
SPILL CLEAN-UP AND DISPOSAL (Section 8)
NOTE: For Emergenices call the National Response Center at 1-800-424-8802
(1-800-426-2675 from the Baltimore/Washington area).
Office of Emergency and Remedial Response (OERR)
Emergency Response Division 245-3045
Oil and Hazardous Materials Spills Branch
Edison, NJ, Region II 340-6634 (201-321-6634)
R-3 July, 1982
-------
Office of Solid Waste (OSW)
Hazardous and Industrial Waste Division 755-9187
ANALYTICAL TECHNIQUES (Section 9)
Environmental Monitoring Systems Lab (EMSL)
Air Analysis
Research Triangle Park, NC 629-2454 (919-541-2454)
Water Analysis
Cincinnati, OH 684-7311 (513-684-7311)
Waste Analysis
Las Vegas, NV 545-2137 (702-798-2137)
GENERAL IPP COMMENTS, CORRECTIONS, OR QUESTIONS
Office of Toxic Integration
Chemical Information and Analysis Program 382-2249
R-4 July, 1982
-------
1,2-Dichloroethane
-------
1,2-DICHLOROETHANE
Table of Contents
Page
Physical/Chemical Properties and Chemistry 1-1
Properties 1~1
Chemistry and Environmental Fate/Transport 1-1
Effects Information 2-1
Health Effects 2-1
Environmental Effects 2-2
Environmental Release 3-1
Air Releases 3-1
Water Releases 3-1
Exposure 4-1
Air Exposure 4-1
Water Exposure 4-1
Data Bases 5-1
Chemicals in Commerce Information System (CICIS) 5-1
EPA Chemical Activities Status Report (EPACASR) 5-1
NIH/EPA Chemical Information System (CIS) 5-1
Chemical Regulations and Guidelines System (CRGS) 5-1
Chemical Substances Information Network (CSIN) 5-2
EPA Information Clearinghouse 5-2
Regulatory Status 6-1
Promulgated Regulations 6-1
Proposed Regulations 6-2
Other Actions 6-3
July, 1982
-------
Standards and Recommended Criteria 7-1
Air 7-1
Hater 7-1
Spill or Other Incident Clean-up/Disposal 8-1
Hazards and Safety Precautions 8-1
First Aid 8-1
Emergency Action 8-1
Notification and Technical Assistance 8-1
Disposal 8-2
Sampling, Acceptable Analytical Techniques and Quality Assurance 9-1
Air 9-1
Water 9-1
References and Office Contacts R-l
July, 1982
-------
1,2-DICHLOROETHANE
1. PHYSICAL/CHEMICAL PROPERTIES AND CHEMISTRY
1.1 Properties
1,2-Dichloroethane (also known as ethylene dichloride or EDC) is a
short-chain chlorinated aliphatic hydrocarbon. It is the largest
volume chlorinated organic chemical currently produced in the United
States. EDC is consumed almost exclusively as a chemical feedstock
in the production of vinyl chloride and other chlorinated organic
chemicals. Only a very small percentage (0.1%) has been used in
solvent applications. Unlike most chlorinated solvents, EDC is flam-
mable. It is also slightly soluble in water. Relevant physical/
chemical properties are listed in Table 1.
1.2 Chemistry and Environmental Fate/Transport
EDC is released to the environment largely through its manufacture
and the manufacture of its end products. Greater than 95% is re-
leased directly to the atmosphere. Once in the troposphere, EDC is
attacked by hydroxyl radicals to yield chloroacetyl chloride as the
initial product. The half-life for this photooxidation reaction is
reported to be approximately 0.3 months. Less than 1% will be trans-
ported to the stratosphere where it will either undergo photodissoci-
ation by high energy ultraviolet light or be carried back to earth
during the precipitation process (OWRS, 1979).
Volatilization Is the major transport process for the removal of EDC
from surface water. The evaporative half-life is approximately 30
minutes. Other processes such as hydrolysis, oxidation, or microbial
degradation do not appear to be significant (OWRS, 1979).
EDC released to land would be expected to volatilize and percolate
down through the soil column. There does not appear to be any effi-
cient mechanism to remove EDC from ground water (OWRS, 1981).
Like most chlorinated hydrocarbons, EDC is not readily biodegraded.
Living matter finds it difficult to metabolize carbon-chlorine bonds;
however, some manufacturers do employ aerobic oxidation (with accli-
mated sludge) to treat some EDC wastes (OSW, 1980).
EDC has been detected in urban air, near industrial vinyl chloride
monomer (VCM) production sites, in industrial water and waste water
samples in finished and raw drinking waters, and in (expired) human
air (IARC, 1979).
1-1 July, 1982
-------
TABLE 1: PHYSICAL/CHEMICAL PROPERTIES OF 1, 2-DICHLOROETHANE
Synonyms: Ethylene dichloride, EDC
CAS number: 107-06-2
Molecular formula:
r i
Structure: H—C C—H
Cl Cl
Molecular weight: 98.96
Melting point: -35'C
Boiling point: 83°C
Flashpoint: 15°C
Density: 1.2 (20°C)
Vapor pressure: 61 torr (20°C)
Solubility: 8,690 mg/1 (20°C)
Log octanol/water partition
coefficient: 1.48
1-2 July, 1982
-------
2. EFFECTS INFORMATION
2.1 Health Effects (CONTACTS: William Lappenbusch, FTS 472-6820 or
Bob McGaughy, FTS 755-3968)
2.1.1 Acute Toxicity
Ingestion of 1 or 2 ounces, about 400 to 800 mg/kg body weight, of
EDC by an adult male is fatal. Clinical symptoms of acute 1,2-di-
chloroethane poisoning by ingestion usually appear within 2 hours
after exposure. Typically, they include headache, dizziness, general
weakness, nausea, vomiting of blood and bile, dilated pupils, heart
pains and constriction, pain in the epigastric region, diarrhea, and
unconsciousness. Pulmonary edema and increasing cyanosis are often
observed. Deaths are usually attributed to circulatory or respira-
tory failure (ODW, 1980).
Exposure to 4,000 ppm of EDC vapor for 1 hour produces serious ill-
ness in humans. The effects of acute exposure by inhalation are sim-
ilar to those described for ingestion, but the primary target appears
to be the central nervous system. Neural depression increases with
the amount of 1,2-dichloroethane absorbed. Damage to the liver, kid-
neys, and lungs also occurs, and reports of leukocytosis and elevated
serum bilirubin are common (ODW, 1980).
The absorption of 1,2-dichloroethane through skin produces effects
similar to those reported for inhalation, but large doses are requir-
ed to cause serious systemic poisoning. Brief contact of 1,2-di-
chloroethane with skin seldom causes serious difficulties; however,
repeated or prolonged contact results in extraction of normal skin
oils and can cause cracking. Although pain, irritation and lacrima-
tion normally occur when 1,2-dichloroethane contacts eye tissue, sig-
nificant damage usually occurs only if the compound is not promptly
removed by washing (ODW, 1980).
2.1.2. Chronic Toxicity
Chronic exposures in humans to EDC by inhalation or absorption usual-
ly result in progressive effects that closely resemble the symptoms
described for acute exposure, especially neurological changes, loss
of appetite, gastrointestinal problems, irritation of the mucous mem-
branes, and liver and kidney impairment. The literature indicates
chronic symptoms may appear after 8-hour exposures to 10 to 100 ppm
for durations of a few weeks to a few months. Odor is not a depend-
able guide for avoiding dangerous chronic exposures to EDC. The odor
may be thought pleasant until well above 180 ppm, and may be missed
completely below 100 ppm (ODW, 1980).
Animal ingestion tests (mouse and rat) indicate that EDC is a carci-
nogen when ingested. Animal inhalation tests have been negative
(ingestion tests used technical grade EDC while inhalation tests used
pure EDC. Different strains of the test animals were used for each)
(OHEA, 1978; ODW, 1980).
2-1 July, 1982
-------
IARC (1979) states that in the absence of adequate data in humans, it
is reasonable, for practical purposes, to regard EDC as if it
presented a carcinogenic risk to humans.
EDC is mutagenic in Salmonella typhimurium (Ames test), Drosophilia
melanogaster, Hordeum vulgare and E^. Coli. (IARC, 1979).
2.2 Environmental Effects (CONTACTS: John Eaton, FTS 783-9557 or
John Gentile, FTS 838-4843)
2.2.1 Aquatic Effects (OWRS, 1980).
Freshwater - Freshwater acute toxicity for bluegill ranged from
431,000 to 550,000 ug/1 (96 hr. LC$Q). The 48-hour LCso for Paphnia
magna is 218,000 ug/1.
The available freshwater data for EDC indicate that acute toxicity
occurs at concentrations as low as 118,000 ug/1 and chronic toxicity
occurs at concentrations as low as 20,000 ug/1.
Saltwater - The measured LC50 (96-hour) for mysid shrimp is 113,000
ug/1. Acute toxicity to fish and invertebrate species occurs at con-
centrations as low as 113,000 ug/1.
2.2.2 Other Effects (OWRS, 1980).
The steady state bioconcentration factor (BCF) for bluegill is 2 (14
days).
2-2 July, 1982
-------
3. ENVIRONMENTAL RELEASE (CONTACTS: Michael Slimak, FTS 426-2503 or
~ Bill Coniglio, FTS 382-3035)
U.S. production of EDC is almost 6,000,000 kkg/yr. Excluding a small
quantity exported, almost 99% of production is consumed as a feed-
stock in the production of vinyl chloride and other chemicals. About
1 percent is used as a leaded gasoline additive, nearly all of which
is destroyed during combustion. A remaining 0.1% (4,700 kkg/yr) is
dissipated to the environment following various solvent related
uses. Overall, of the 29,000 kkg/yr environmental release, 96% is
estimated to go to air, 3% to land, and less than 1% to water, as
shown in Table 2 (OURS, 1981).
3.1 Air Releases (CONTACT: Karen Blanchard, FTS 629-5519)
Significant Sources
• Chemical industries producing EDC or using it as feedstock (SIC
2869) are the sources contributing the greatest emissions to the
ambient air. EDC is one of the highest volume chemicals used in
the U.S. In 1977 about 80% of production was used for the syn-
thesis of vinyl chloride monomer, a hazardous chemical. Domes-
tic production emission sources are located in Louisiana, Texas,
Kentucky, California and Puerto Rico.
Other Sources
• EDC is used as a leaded gasoline additive. It has been esti-
mated that 30 million people are exposed to an EDC concentration
of 1.5 ppb for 2.2 hr/yr while refueling their automobiles
(OAQPS, 1979). Exposures to EDC may occur through its
dispersive uses, including grain fumigants, paints, coatings,
adhesives, cleaning, and the preparation of polysulfide.
However, these uses represent only 1/10 of 1% of production.
3.2 Water Releases (CONTACT: Michael Slimak, FTS 426-2503)
Based on the above production and use considerations, most releases
of EDC would be expected to occur at centralized production facili-
ties rather than at widely dispersed solvent-using facilities, in
sharp contrast to other chlorinated solvents. Although Effluent
Guidelines Division detected dichloroethanes less frequently and in
fewer industrial categories than the widely used solvents, EDC was
still found in over 10% of the samples in the Mechanical Products,
Pharmaceuticals, Pesticides, Organics and Plastics, Photographic, and
Auto and Other Laundries industries (OWRS, 1981).
3-1 July, 1982
-------
TABLE 2: EDC PRODUCTION, USE, AND DISPOSAL (kkg/yr)
i
to
Category Production
Production
Balanced process 5,400,000
Direct Chlorination 380,000
Oxy chlorination 110,000
Use
Vinyl chloride monomer
1,1, 1-trichloroethane
Ethylene amines
Trichloroethene
Tetrachloroethene
Vinylidene chloride
Dispersive Uses
Lead scavenger
Paints coating adheslves
Extraction solvent
Cleaning solvent
Polysulfide rubber
Grain fumigant
Diluent for pesticides
Film manufacture
Exports
Total:
Use
4,800,000
200,000
230,000
110,000
110,000
100,000
72,000
1,300
1,300
1,000
15
500
400
150
310,000
Air
20,000
1,100
1,300
included
1
360
63
75
Neg
800
1,300
1,300
600
Neg
500
200
8
27,607
(96%)
Release to
Water
1
1
1
in balanced
Neg
1
29
35
Neg
Neg
Neg
Neg
100
Neg
Neg
Neg
Neg
169
«1%)
Land
83
95
280
process
Neg
20
Neg
Neg
Neg
Neg
Neg
Neg
300
Neg
Neg
200
Neg
978
(3%)
00
tvi
Source: Recommendations for Control of Dichlorothanes, Draft Report, OWRS, Oct. 81.
Neg. = Negligible
-------
4. EXPOSURE (CONTACTS: Michael Slimak, FTS 426-2503 or
Bill Coniglio, FTS 382-3035)
The general population may be exposed to EDC through drinking water,
urban air, and food products which have been treated with EDC.
The level of human exposure to EDC is difficult to identify with
certainty due to sparse and conflicting measurements. Ambient air
concentrations of both dichloroethane isomers are elevated by emis-
sions from dichloroethane producers and to a lesser extent by EDC
feedstock users. Concentrations are also somewhat elevated in all
urban areas due to emissions as a leaded gasoline additive or solvent
(OURS, 1981).
Annual inhalation exposure to EDC in areas where it is produced may
attain 800 ug/day (40 ug/m3)- Because EDC is seldom detected in
drinking water, the estimate for average exposure via this route is
also broad, 0.03 - 3 ug/day, depending on the concentration assumed
for undetectables in either the National Organics Monitoring Survey
(NOMS) or Stanford Research Institute (SRI) nationwide surveys. The
highest waterborne exposure yet observed is 800 ug/day, via contami-
nated groundwater. Exposure to EDC via food cannot be estimated, due
to lack of data; however, it is known that dichloroethanes are so
weakly bioconcentrated that exposure via contaminated fish should be
minor (OWRS, 1981).
Overall, it can be concluded that:
• Despite the massive combined production volume of dichloro-
ethanes, very little is relased to the environment. Troublesome
ambient levels appear to be associated with production and
feedstock consumption facilities.
• Dichloroethanes are primarily air pollutants. Population aggre-
gated exposure is substantially greater via air than via surface
or groundwater. Highest individual exposures appear to result
from air or groundwater contamination.
• Ambient levels of EDC may contribute very slightly to cancer
risks.
4.1 Air Exposure (CONTACT: Karen Blanchard, FTS 629-5519)
• In addition to exposure in the workplace, the human population
near certain chemical manufacturing facilities may be exposed to
EDC in the ambient air. It has been estimated that as many as
14 million people were exposed to concentrations of EDC ranging
from .01-10 ppb (OAQPS, 1979).
4.2 Water Exposure
High level exposures may result via severely contaminated goundwater.
4-1 July, 1982
-------
5. DATA BASES
5.1 Chemicals in Commerce Information System (CICIS)
The Inventory was compiled under the authority of Section 8 of TSCA
which requires manufacturers to report to EPA the chemicals imported
and manufactured during calendar year 1977. The Inventory lists the
Chemical Abstract Service (CAS) preferred name for the chemicals,
their respective CAS number (often used for identification purposes),
production site, company name, and volume(s) of production and im-
port. There is also a Confidential Inventory in which many of these
characteristics are claimed confidential by the manufacturer. In
these instances, the confidential information will not be available
on the public inventory. CICIS can now be accessed through the
NIH/EPA Chemical Information System (CIS - see 5.3). For further
information, contact Gerri Nowack at FTS 382-3568.
5.2 EPA Chemical Activities Status Report (EPACASR)
EPACASR is an on-line system containing information on EPA's interest
in chemicals. This system includes data on the Agency's regulations,
research, and assessments directed toward specific chemicals.
EPACASR is published annually and the data base is updated as
information is received. A searchable subset itemizes NTP/NCI
studies and results, as well as chemicals discussed in the IARC
monograph series. (Other sources are added as appropriate.) Entries
identify the statutory authority, the nature of the activity, its
status, the reason for and/or purpose of the effort, and a source of
additional information. Searches may be made by CAS Number or coded
text. For further information contact Eleanor Merrick at FTS
382-3415.
5.3 NIH/EPA Chemical Information System (CIS)
This is a collection of various scientific data bases available
through an Interactive computer program. The linking system between
these data files is the Structure and Nomenclature Search System
(SANSS). CIS can also provide a list of non-CIS sources of informa-
tion on a chemical of interest. However, these files have to be
accessed individually by either separate on-line systems or in hard-
copy. For further information contact Delores Evans at FTS 382-3546
or Irv Weiss at FTS 382-3524.
5.4 Chemical Regulations and Guidelines System (CRGS)
CRGS is an on-line data base which is being developed to provide
information on chemical regulatory material found in statutes, regu-
lations, and guidelines at the Federal, State, and International
levels. Currently, only the first phase of CRGS, which encompasses
only source material at the Federal level, is operational. Nation-
wide access to CRGS is available through Dialog. For further infor-
mation, contact Delores Evans'at FTS 382-3546 or Ingrid Meyer at FTS
382-3773.
5-1 ' July, 1982
-------
5.5 Chemical Substances Information Network (CSIN)
The prototype CSIN,. operational since November 1981, has been
developed by merging the technologies of computer networking and
distributed data base management. CSIN is not another data base, but
a library of systems. Through the CSIN front-end intermediary
management computer, the user may access and use independent and
autonomous information resources which are geographically scattered,
disparate for data and information content, and employ a variety of
types of computer hardware, software, and protocols. Users may
converse in and among multiple systems through a single connection
point, without knowledge of or training on these independent systems.
Presently, six independent information resources are accessible
through CSIN. They are: National Library of Medicine (NLM), CIS,
EPA-CICIS, CAS-On-Line, SDC-orbit, and two files of Dialog: CRGS and
TSCA Inventory. The CSIN management computer allows the user to
create, retrieve, store, or manipulate data and queries. This elimi-
nates the need for re-entering long lists of chemical identifiers or
other information elements which are part of the original query or
which have been identified and acquired from one or more of the CSIN
resources. For further information contact Dr. Sid Siegal at FTS
382-2256.
5.6 EPA Information Clearinghouse
The EPA Information Clearinghouse is a bibliographic data base com-
posed of over 475 individual data bases and models which contain
monitoring information and statistics on a variety of chemicals. The
individual data bases are maintained by offices within EPA. For
further information, contact Charlene Sayers at FTS 755-9112.
The following data bases contain information on EDC compounds.
BAT Review Study for the Timber Products Processing, Gum and Wood,
Chemicals, and the Printing and Publishing Industries
Best Management Practices, Timber Industry Effluent Guidelines -
Runoff
Chemicals in Commerce Information System
Compliance Sampling Toxicant Surveys
Consolidated Permits Program-Application Form l,2b,2c
Data Collection Portfolio for Industrial Waste Discharges
Distribution Register of Organic Pollutants in Drinking Water
Effluent Guidelines GC/MS Screening Analysis Data Base
Energy and Mining Point Source Category Data Base
Federal Facilities Information System
Federal Reporting Data System
Fine Particle Emissions Information System
Food Industry Group
Fugitive Emissions Information System
Gaseous Emissions Data System
Hazardous Waste Data Management System
Hazardous Waste Site Tracking System
Hemlock, Michigan Environmental Samples
5-2 July, 1982
-------
Humacao Ambient Data Base
IFB Organics Data Base
Indicatory Fate Study
Industrial Process Evaluations
Infrared Spectra of Pollutants
Innovative Technology, Timber Industry Effluent Guidelines
Inorganic Chemicals Industry Regulation Record
LiPari Landfill
Liquid Effluents Data System
Listing of Organic Compounds Identified in Region IV
Love Canal Data Handling System
Method Validation Studies of Priority Pollutants
National Pollutant Discharge Elimination System (NPDES) Discharge
Monitoring Reports
Nationwide Urban Runoff Program
Needs Survey
New York Bight Ocean Monitoring Program
Organic Chemicals/Plastics Industry
Organic Transport thru Soil
Paint and Ink Analytical Data
Permit Compliance System
Pesticide Incident Monitoring System
Pharmaceutical Screening/Verification Data Base
Precision and Accuracy for Screening Protocols
Priority Pollutants-Region I
Priority Pollutants-Region III
Publicly Owned Treatment Works (POTW) Analytical Data
Publicly Owned Treatment Works (POTW) Quality Control
Puerto Rico Reservoirs
Regional Toxics Monitoring Program
Resource Conservation and Recovery Act (RCRA)-Hazardous Waste Site
Inspections
Screening Sampling Program
Select Hazardous Chemicals-Ambient
Sources of Toxic Pollutants Found in Influents to Sewage Treatment
Plants
Spill Prevention Control and Countemeasure
System for Consolidated Permitting and Enforcement Data Base
Textile Industry BAT Study-Toxic Sampling Data
Toxics Monitoring
U.S. Virgin Islands-St. Thomas, St. Croix
Verification Data Base
Verification Sampling Program
Waste Characterization Data Base
Water Enforcement Regional System
Water Quality Information System
5-3 July, 1982
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6. REGULATORY STATUS (Current as of 4/16/82)
6.1 Promulgated Regulations
6.1.1 EPA Programs
Clean Water Act (CWA)
• Sections 301, 304, 306, 307 - 1,2-Dichloroethane is classified
as a toxic pollutant (40CFR401.15). As such, it is subject to
effluent limitations reflecting "the best available technology
economically achievable (BAT)." No standards specific for
1,2-dichloroethane have been issued.
Resource Conservation and Recovery Act (RCRA)
• Section 3001 - 1,2-Dichloroethane (U077) has been identified as
a toxic hazardous waste (T) if and when it is discarded as a
commercial product or an off-specification species. Contami-
nated soil and spill residues are also considered hazardous
wastes. (40CFR261.33)
The following wastestreams are designated as toxic hazardous (T)
wastes, due in part to the presence of EDC (40CFR261.32):
-KOI8 - Heavy ends from the fractionation column in ethyl chloride
production.
-K019 - Heavy ends from the distillation of ethylene dichloride in
ethylene dichloride production.
-K020 - Heavy ends from the distillation of vinyl chloride in vinyl
chloride monomer production.
-K029 - Wastes from the product steam stripper in the production of
1,1,1-trichloroethane.
-K030 - Column bottoms or heavy ends from the combined production of
trichloroethylene and perchloroethylene.
-K096 - Heavy ends from the heavy ends column from the production of
1,1,1-trichloroethane.
• Sections 3002-3006 - Regulations for generators, and trans-
porters of hazardous waste and standards for treatment, storage
and disposal facilities are applicable (40CFR262 to 265).
Permitting procedures are included in the consolidated permit
regulations (40CFR122 to 124).
Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA)
• Tolerance exemptions for 1,2-dichloroethane residues (40CFR180).
6-1 July, 1982
-------
6.1.2 Programs of Other Agencies
OSHA - Occupational Safety and Health Act
• An employee's exposure to 1,2-dichloroethane Is limited in any
eight-hour shift of a 40-hour work week by eight-hour time-
weighted averages (TWA) and acceptable ceiling concentrations
(29CFR1910.1000).
• Safety and health regulations for construction under Federal
service contracts (29CFR1925).
DOT
• EDO is listed as a flammable liquid and must comply with the
appropriate labeling and transportation regulations (49CFR172.-
101).
6.2 Proposed Regulations
6.2.1 EPA Programs
TSCA - Toxic Substances Control Act
• Section 8(a) - Proposed requirements requesting records, reports
andotherdata possessed by manufacturers and processors of
1,2-dichloroethane.
CAA - Clean Air Act
• New Stationary Source Performance Standards proposed for Organic
Solvent Cleaners. EDC covered under the volatile organic com-
pounds (VOC) category (45FR39766, 6/11/80).
• New Stationary Source Performance Standards proposed which would
limit VOC from fugitive emission sources in the Synthetic Organ-
ic Chemicals Manufacturing Industry. EDC is one of a number of
VOC included in this proposal (46FR1136, 1/5/81).
6.2.2 Programs of Other Agencies
OSHA - Occupational Safety and Health Act
• Regulation of 1,2-dichloroethane as a mutagen under OSHA's
general policy for the identification and regulation of physical
and chemical substances posing potential carcinogenic risks to
humans (29CFR1990).
DOT
• Coast Guard lists appropriate measures to prevent storage of EDC
with incompatible materials during transport by boat
(45FR48058).
6-2 July, 1982
-------
6.3 Other Actions
• Comprehensive Environmental Response, Compensation, and
Liability Act (CERCLA or Superfund) - CERCLA provides for the
liability, compensation, clean-up, and emergency response for
the release of hazardous substances into the environment. This
Act also deals with the cleanup of hazardous waste disposal
sites. (42USC9601; PL 96-510). EPA is developing regulations
concerning the designation of hazardous substances, the
development of reportable quantities, claims procedures, and the
confidentiality of business records (46FR54032). Revisions to
the National Contingency Plan (NCP) as required by CERCLA have
been issued in a proposed rule (47FR10972). Hazardous
substances as defined by Section 101(14) of CERCLA include:
hazardous wastes designated under Section 3001 of the RCRA;
hazardous air pollutants regulated under Section 112 of the CAA;
water pollutants listed under Sections 307 and 311 of the CWA
(and also any substances regulated in the future under Section 7
of TSCA and Section 102 of CERCLA). Therefore, EDC is a
hazardous substance under CERCLA and will be subject to
regulations developed under Superfund.
Safe Drinking Water Act (SDWA)
• One of a number of substances discussed in an Advance Notice of
Proposed Rulemaking (ANPR) for possible inclusion in revised
National Primary Drinking Water Regulations for volatile
synthetic organic chemicals (47FR9350, 3/4/82).
6-3 July, 1982
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7.
7.1
STANDARDS AND RECOMMENDED CRITERIA*
7.2
Air
OSHA standard for workplace exposure (29CFR1910.1000),
TWA 50 ppm (8-hr, work day)
Water
Hazardous spill rules require notification of discharge equal to
or greater than 5,000 Ib (40CFR116, 117).
Water Quality Criteria (44FR60641)
Freshwater Aquatic Life
Saltwater Aquatic Life
Human Health
3,900 ug/1 (24-hr, avg.)
8,800 ug/1 (maximum)
880 ug/1 (24-hr, avg.)
2,000 ug/1 (maximum)
To protect human health
zero risk at zero concen-
tration. One additional
case of cancer per 100,000
population (10~5) at 9.4
ug/1.
* See Appendix A for a discussion of the derivation, uses, and limitations of
these criteria and standards.
7-1
July, 1982
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8. SPILL OR OTHER INCIDENT CLEAN-UP/DISPOSAL
(CONTACT: National Response Center, 800-424-8802, in Washington,
426-2675)
8.1 Hazards and Safety Precautions
EDC may be fatal if inhaled, swallowed or absorbed through the skin.
Contact may cause burns to skin and eyes. Runoff from fire control
or dilution water may cause pollution.
EDC will burn and may be ignited by heat, sparks and flames. Flam-
mable vapor may spread away from spill. Container may explode in
heat of fire.
Protect against physical damage. Outside or detached storage is pre-
ferable. Inside storage should be in a standard flammable liquids
storage room or cabinet.
8.2 First Aid
Move victim to fresh air; call emergency medical care. If not
breathing, give artificial respiration. If breathing is difficult,
give oxygen. Remove and isolate contaminated clothing and shoes. In
case of contact with material, immediately flush skin or eyes with
running water for at least 15 minutes.
8.3 Emergency Action
Keep unnecessary people away; isolate hazard area and deny entry.
Stay upwind; keep out of low areas. Wear positive pressure breathing
apparatus and special protective clothing. Isolate for 1/2 mile in
all directions if tank or tank car is involved in fire.
In case of spill or leak, no flares, smoking or flames in hazard
area. Do not touch spilled material. Stop leak if you can do it
without risk. Use water spray to reduce vapors. Small spills: take
up with sand, or other noncombustible absorbent material, then flush
area with water. Large spills: dike far ahead of spill.
In case of small fire use dry chemical, C02, water spray or foam.
And in case of large fire use water spray, fog or foam. (Note:
water may be ineffective on fire.) Wear goggles, self-contained
breathing apparatus, and rubber overclothing (including gloves).
Move container from fire area if you can do so without risk. Stay
away from ends of tanks. Cool containers that are exposed to flames
with water from the side until well after fire is out. Withdraw
immediately in case of rising sound from venting safety device or
discoloration of tank.
8.4 Notification and Technical Assistance
Section 103(a) and (b) of the Comprehensive Environmental Response,
Compensation, and Liability Act of 1980 requires persons who release
hazardous substances in reportable quantities determined pursuant to
8-1 July, 1982
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Section 102 of the Act to notify the National Response Center (NRG):
800-424-8802 (Washington, D.C., 426-2675).
EDC is designated as a hazardous substance under CWA Section 311.
Its reportable quantity is 5,000 pounds.
For technical assistance call CHEMTREC (800-424-9300). Also, in case
of water pollution, call local authorities. Other sources of techni-
cal information are (1) EPA's Oil and Hazardous Material Technical
Assistance Data System (OHM-TADS) contained in the NIH/EPA Chemical
Information System (CIS), which provides information pertinent to
emergency spill reponse efforts, and (2) the CHRIS System which pro-
vides information on first aid, physical/chemical properties, hazard
assessments, and response methods. Both systems can be accessed
through NRC.
8.5 Disposal
Disposal of greater than 1,000 kg/month of commercial product is
subject to subpart D regulations under RCRA.
The following specific wastestreams, which contain EDC, are subject
to subpart D regulations:
(1) Heavy ends from the fractionation column in ethyl chloride
production.
(2) Heavy ends from the distillation of ethylene dichloride in
ethylene dichloride production.
(3) Heavy ends from the distillation of vinyl chloride in vinyl
chloride monomer production.
(4) Waste from the product steam stripper in the production of
1,1,1-trichloroethane.
(5) Column bottoms or heavy ends from the combined production of
trichloroethylene and perchloroethylene.
(6) Heavy ends from the heavy ends column from the production of
1,1,1-trichloroethane.
8-2 July, 1982
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9. SAMPLING, ACCEPTABLE ANALYTICAL TECHNIQUES, AND QUALITY ASSURANCE
9.1 Air (CONTACT: Robert H. Jungers, FTS 629-2331)
EDC is not a criteria air pollutant; therefore, no Agency or ref-
erence procedures have been promulgated. A sampling and analysis
procedure using charcoal for sampling, gas chromatography for compo-
nent separation and mass spectrometry for analysis has been used for
monitoring around production and user facilities. ("Monitoring of
Ambient Levels of Ethylene Dichloride (EDC) in the Vicinity of EDC
Production and User Facilities," EPA-600/4-79-029, April 1979).
However, mass spectrometry requires sophisticated and expensive
equipment and special expertise.
The method was evaluated over an EDC range of 2.5 to 348 ug/m3 (0.6
to 86 ppb), at temperatures of 25° and 30°C and relative humidities
of 64% and 99%. The sampling rate is 65 cm3/min for 24 hours. Samp-
ling at rates greater than 65 cm3/min and for times greater than 24
hours must be avoided, because higher sampling rates and larger total
air volumes can lower collection efficiency substantially.
The precision, as measured by the relative standard deviation from
replicate sampling and analysis by one laboratory, is reported to be
6%. Accuracy of the method is estimated to be between 72% and 97%.
Quality assurance materials composed of blank charcoal sampling cart-
ridges spiked with known amounts of EDC can be prepared and must be
used in any monitoring program.
9.2 Water (CONTACTS: Thomas Bellar, FTS 684-7311 or
James Lichtenberg, FTS 684-7308)
1,2-Dichloroethane is a proposed parameter under Section 304(h) of
the Clean Water Act. It is listed as one of the priority pollutants.
There are several approved and proposed gas chromatographic proce-
dures for the analysis of 1,2-dichloroethane in natural, waste and
drinking waters. The primary difference between the methods is the
extraction procedure and the means of injecting the extracts into the
gas chromatograph. Mass spectrometry and halogen specific detectors
are normally used to improve qualitative accuracy.
In one method, the Direct Aqueous Injection (EPA Method #8) 1 to 5
ul of the neat sample is injected directly into the gas chromato-
graph. The method detection limit is approximately 1 rag/1 when mass
spectrometry, flame ionization or halogen specific detectors are
used.
A second method is the Liquid-Liquid Extraction (EPA Method #501.2)
in which a small volume of sample is extracted with a low boiling
water insoluble solvent such as pentane. Sample/solvent ratios of
5:1 are commonly used. One to 5 ul of the extract is then injected
into a gas chromatograph equipped with an electron capture detector.
The method detection limit is approximately 20 ug/1.
9-1 July, 1982
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In the third method—Purge and Trap—(EPA Method #601) 5 ml of the
aqueous sample is placed into a purging device. 1,2-Dichloroethane
and other volatile water insoluble organic compounds are transferred
from the aqueous phase to the gas phase. The volatilized compounds
are swept from the purging device by the purge gas and are trapped in
a short column containing a suitable sorbant. After a predetermined
period of time the trapped compounds are thermally desorbed and back-
flushed into a gas chromatograph equipped with a mass spectrometer,
flame ionization or a halogen specific detector.
The method detection limit for the mass spectrometer (full scan) and
the flame ionization detector is approximately I ug/1. For a care-
fully optimized halogen specific detector method detection limits as
low as 20 ng/1 have been achieved.
Samples are collected in narrow-mouth screen-cap bottles with TFE
fluorocarbon seals. Samples are stored head-space free at 4°C in the
dark. Sodium thiosulfate is normally used to remove free residue
chlorine. Spiked river water samples have been stored for up to 27
days under these conditions with no apparent losses.
Single laboratory test data on simple spiked matrices have been
collected by EPA. Intralaboratory accuracy and precision and method
detection limit data are currently being collected. Quality control
and performance evaluation samples (methanolic concentrates contain-
ing 1,2-dichloroethane to be spiked into water) are available from
the Environmental Monitoring and Support Laboratory, Quality Assur-
ance Branch, USEPA, Cincinnati, Ohio, 45268.
The following table is a summary of methods with appropriate refer-
ences :
ANALYTIC PROCEDURES FOR 1,2-DICHLOROETHANE
Method
EPA 624
EPA 601
EPA 502.1
EPA 501.2
EPA 8
Standard Methods
ASTM D-2098-74
ASTM D-3871-79
Type
MDL
Recoverya(2)
P&T
P&T
P&T
LLE
DAI
P&T
DAI
P&T
2.8 ug/1
.03 ug/1
ND
ND
1 mg/1
ND
ND
ND
102-103
106
110
ND
ND
ND
ND
ND
Standard
Deviation (%)
12-27
8.4
7
ND
ND
ND
ND
ND
Status
Proposed
Proposed
Proposed
Untested
Official1
Untested
Untested
Untested
a Single laboratory recovery from spiked reagent water or wastewater.
b Official for the analysis of organohalides in wastewater.
P&T - Purge and Trap
LLE - Liquid/Liquid Extraction
DAI - Direct Aqueous Injection
Status - As of March 1981.
9-2
July, 1982
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References for Sampling and Analysis
1. "A Method for Organochlorine Solvents in Industrial Effluents."
National Pollutant Discharge Elimination System Appendix A,
Federal Register 38, No. 7S Ft. II.
2. "Standard Test Method for Measuring Volatile Organic Matter in
Water by Aqueous - Injection Gas Chromatography," Annual Book of
ASTM Standards, 1980, Part 31, Water, ASTM D-3908-74.
3. Federal Register, Thursday, November 29, 1979, Volume 44. No.
231, 40 CFR, Appendix C - Parts I and II.
4. Federal Register, Monday, December 3, 1979, Volume 44. No. 233,
40 CFR Part 136, Guidelines Establishing Test Procedures for the
Analysis of Pollutants.
5. "The Determination of Halogenated Chemical Indicators of
Industrial Contamination in Water by the Purge and Trap Method,"
Method 502.1, September 1980, USEPA, Environmental Monitoring
and Support Laboratory, Cincinnati, Ohio 45268.
6. "Standard Test Method for Measuring Purgeable Organic Compounds
in Water Using Headspace Sampling," ASTM D-3871-79, Part 31,
Water, Annual Book of ASTM Standards, 1980.
9-3 July, 1982
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REFERENCES
The major references used in preparation of this document are listed below.
EPA documents are referenced by the EPA office of origin and the year of
publication. For further information refer to the contacts given throughout
this document or contact the EPA Program Offices listed in the next section.
(IARC, 1979)
(OAQPS, 1979)
(ODW, 1980)
(ODW, 1981)
(OHEA, 1978)
(OWRS, 1979)
(OWRS, 1980)
(OWRS, 1981)
(OSW, 1980)
IARC Monographs on the Evaluation of the Carcinogenic
Risk of Chemicals to Humans,Vol.20^International
Agency for Research on Cancer, World Health Organization
(1979).
Assessment of Human Exposure to Atmospheric Ethylene
Dichloride, EPA Contract 68-02-2835, Office of Air
Quality Planning and Standards (1979).
Criteria Document for 1,2-Dichloroethane, Draft Report,
Office of Drinking Water (1980).
Draft SNARL Review - 1,2-Dichloroethane, Office of
Drinking Water (1981).
The Carcinogen Assessment Group's (CAG) Preliminary
Report on Ethylene Dichloride, Office of Health and
Environmental Assessment (1978).
Water-Related Environmental Fate of 129 Priority
Pollutants, Vol. II, EPA-440/4-79-029b, Office of Water
Regulations and Standards (1979).
Ambient Water Quality Criteria for Chlorinated Ethanes,
EPA440/5-80-029,OfficeofWaterRegulationsand
Standards (1980).
Recommendations for Control of Dichloroethanes, Draft
Report, Office of Water Regulations and Standards (1981).
Wastes Resulting from Chlorinated Hydrocarbon
Manufacture, Preliminary Draft Report, Office of Solid
Waste (1980).
R-l
July, 1982
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OFFICE CONTACTS
The EPA offices and divisions that are listed below may be contacted for more
information relating to the indicated sections of this document. While these
offices are, in many cases, the offices of origin for the data included in
this paper, the personal contacts given throughout this document should be
contacted first. Unless otherwise noted, the offices listed are situated in
Headquarters, Washington, D.C., and the telephone numbers given are FTS
(Federal Telecommunications System) numbers. For commercial telephone calls
to Headquarters which are not placed on FTS, area code 202 must be used.
Other commercial numbers are noted for the office contacts located outside
Washington, D.C.
HEALTH AND ENVIRONMENTAL EFFECTS (Section 2)
Office of Health and Environmental Assessment (OHEA)
Environmental Criteria and Assessment Office:
Cincinnati, OH 684-7531 (513-684-7531)
Research Triangle Park, NC 629-2266 (919-541-2266)
Carcinogen Assessment Group 755-3968
Office of Drinking Water (ODW)
Health Effects Branch 472-6820
Office of Toxic Substances (OTS)
Health and Environmental Review Division 382-4241
Environmental Research Laboratory
Duluth, MN, Region V 783-9550 (218-727-6692)
ENVIRONMENTAL RELEASES AND EXPOSURE (Sections 3 and 4)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Water Regulations and Standards (OWRS)
Monitoring and Data Support Division 426-2503
R-2 July, 1982
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Office of Toxic Substances (OTS)
Exposure Evaluation Division 382-3873
Assessment Division 382-3442
DATA BASES (Section 5)
Office of Toxic Substances (OTS)
Management Support Division 382-3546
REGULATORY STATUS, STANDARDS. AND CRITERIA (Sections 6 and 7)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Drinking Water (ODW)
Criteria and Standards Division 472-5016
Office of Water Regulations and Standards (OWRS)
Criteria and Standards Division 755-0100
Effluent Guidelines Division 426-2571
Office of Solid Waste (OSW)
State Programs and Resources
Recovery Division 755-9107
SPILL CLEAN-UP AND DISPOSAL (Section 8)
NOTE: For Emergenices call the National Response Center at 1-800-424-8802
(1-800-426-2675 from the Baltimore/Washington area).
Office of Emergency and Remedial Response (OERR)
Emergency Response Division 245-3045
Oil and Hazardous Materials Spills Branch
Edison., NJ, Region II 340-6634 (201-321-6634)
R-3 July, 1982
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Office of Solid Waste (OSW)
Hazardous and Industrial Waste Division 755-9187
ANALYTICAL TECHNIQUES (Section 9)
Environmental Monitoring Systems Lab (EHSL)
Air Analysis
Research Triangle Park, NC 629-2454 (919-541-2454)
Hater Analysis
Cincinnati, OH 684-7311 (513-684-7311)
Waste Analysis
Las Vegas, NV 545-2137 (702-798-2137)
GENERAL IPP COMMENTS. CORRECTIONS, OR QUESTIONS
Office of Toxic Integration
Chemical Information and Analysis Program 382-2249
R-4 July, 1982
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Formaldehyde
-------
FORMALDEHYDE
Table of Contents Page
Physical/Chemical Properties and Chemistry 1-1
Properties 1-1
Chemistry and Environmental Fate/Transport 1-1
Effects Information 2-1
Health Effects 2-1
Environmental Effects 2-3
Environmental Release 3-1
Exposure Routes 4-1
Data Bases 5-1
Chemicals in Commerce Information System (CICIS) 5-1
EPA Chemical Activities Status Report (EPACASR) 5-1
NIH/EPA Chemical Information System (CIS) 5-1
Chemical Regulations and Guidelines System (CRGS) 5-1
Chemical Substances Information 5-2
EPA Information Clearinghouse 5-2
Regulatory Status 6-1
Promulgated Regulations 6-1
Proposed Regulations 6-2
Other Actions 6-3
Standards and Recommended Criteria 7-1
Air 7-1
Water 7-1
Spill Clean-Up or Disposal 8-1
Hazards and Safety Precautions 8-1
First Aid 8-1
Emergency Action 8-1
Notification and Technical Assistance 8-1
Disposal 8-2
July, 1982
-------
Sampling, Acceptable Analytical Techniques, and Quality Assurance 9-1
Mr 9-1
Hater 9~1
Solid Waste 9-2
Other Procedures 9-2
References and Office Contacts
July, 1982
-------
FORMALDEHYDE
1. PHYSICAL/CHEMICAL PROPERTIES AND CHEMISTRY
1.1 Properties
Formaldehyde is a flammable gas having a pungent odor and an irritat-
ing effect on mucous membranes. Because formaldehyde polymerizes
readily, it is only available in stabilized aqueous solutions or
polymeric forms. Aqueous solutions range from 37 to 56 percent
formaldehyde. Polymeric forms include a cyclic trimer (trioxane) and
paraformaldehyde, a linear polymer of varying composition. Table 1
summarizes properties of formaldehyde in the form of gaseous monomer,
solid trimer and aqueous solution (OTS, 1976).
United States commercial production of aqueous formaldehyde (37 per-
cent by weight) in 1980 was about 2,520 metric tons, down slightly
from record levels in 1978. Formaldehyde is produced by the cataly-
tic vapor phase oxidation of methanol or by a combination oxidation-
dehydration process. The largest end uses for formaldehyde are in
the production of synthetic resins, particularly phenol-formaldehyde
and urea-formaldehyde resins. These resins are used as adhesives in
wood products, principally for particleboard, fiberboard, plywood,
and in making foam insulation. Formaldehyde also has many diverse
uses as a chemical intermediate and preservative (OTS, 1982).
1.2 Chemistry
Formaldehyde is extremely reactive and will combine chemically with
many classes of organic compounds. On reduction, formaldehyde yields
methanol, while oxidation gives formic acid or carbon dioxide and
water. The major reactions of formaldehyde with other compounds
(X-H) involve formation of hydroxymethyl derivatives (X-CH2~OH).
Many of these reactions, such as hydration, are reversible and free
formaldehyde may be regenerated under proper conditions. Formalde-
hyde is useful in the production of resins due to its dual reactiv-
ity. For example, formaldehyde initially reacts with phenol, urea,
or melamine to form the hydroxymethyl derivative. Further reaction
involves the loss of water to yield thermoset resins which are highly
cross-linked by methylene groups (-X-CH2-X-) (OTS, 1976; NRC, 1981).
The major sources of formaldehyde contamination in the environment
are combustion processes, especially automobile emissions. Formalde-
hyde vapors are released due to the incomplete combustion of hydro-
carbons. In addition, hydrocarbons from automobile exhaust are oxi-
dized to formaldehyde through photochemical processes in the atmos-
phere. Formaldehyde is a recognized component of smog and can react
photochemically in the atmosphere to form radicals which undergo a
wide variety of reactions. The half-life of formaldehyde in the
atmosphere is estimated to be less than a few hours in sunlight.
1-1 July, 1982
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Although formaldehyde itself is probably not transported far in the
atmosphere due to its reactivity, hydrocarbons which are precursors
for formaldehyde may be widely dispersed (NRG, 1981).
Biological degradation Is the primary destruction process for
formaldehyde and its hydrates in water. Formaldehyde, per se, does
not persist in water, but is rapidly converted to glycols which are
biodegradable. Thus, only very low concentrations of formaldehyde
would be expected in ambient waters, except in extreme cases such as
spills of concentrated solutions (OTS, 1982; NRG, 1981).
Due to the highly reactive nature of formaldehyde, this compound is
expected to be immobilized in clay soil by adsorption. The persis-
tence of adsorbed formaldehyde, however, is uncertain, especially in
wet soils. Formaldehyde is a natural metabolic product and does not
bioconcentrate (OTS, 1976; OTS, 1982).
1-2 July, 1982
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TABLE 1: PROPERTIES OF FORMALDEHYDE AND COMMERCIALLY AVAILABLE FORMS3
Formaldehyde
Trioxane
Formalin'5
State:
Monomer; gas
Trimer; solid
Aqueous solution
37% by wt.
Synonym:
Methanal,
oxymethane
S-trixane
Formol
CAS No.:
50-00-00
110-88-3
Molecular Formula:
CH20
C3H603
CH402 (hydrate)
Structure:
H—C—H
Melting Point (°C); -92
A
CH2 CH2
I I
0 0
V
64
OH
H—C—H (hydrate)c
OH
Boiling Point (°C); -20
115
99
Flash Point (°C);
85
Density;
1.07 (vapor)
1.17 (65°C)
1.11 g/ml (18°)
Water Solubility (25"C): 55%
210 g/1
aSource: The Merck Index, 9th edition (1976), unless otherwise noted.
bSee Chemical and Process Technology Encyclopedia, p. 517; D.M. Considine, ed.,
McGraw Hill (1974). Commercial formalin contains varying amounts of methanol as a
stabilizer; constants cited are for formalin containing 1% methanol.
cPolymeric forms dominate at high formaldehyde concentrations.
1-3
July, 1982
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2. EFFECTS INFORMATION
2.1 Health Effects (CONTACTS: Bob McGaughy, FTS 755-3968;
Yogi Patel, FTS 472-4944)
2.1.1 Acute Toxlcity
Ingestion of aqueous formaldehyde solutions causes immediate and
severe abdominal pain, collapse, loss of consciousness and anuria.
Vomiting and diarrhea may also occur and death can result from circu-
latory failure. Ingestion may also lead to necrosis and shrinkage of
mucous membranes, and degenerative effects on the liver, kidneys,
heart, and brain. A fatal human dose of formalin (37 percent aqueous
solution of CH20 by weight) is estimated to be 30-90 ml (1 to 3 oz.);
the oral U)$Q for rats is about 800 mg/kg (OTS, 1976).
Formaldehyde vapor can be quite irritating at low concentrations.
The level of irritation and resulting symptoms is a function of the
formaldehyde concentration and the sensitivity of individuals. The
variability of individual responses to gaseous formaldehyde is well
established. In general, the irritation threshold is about 1 ppm
(1200 ug/m3) which is also reported to be the odor threshold. How-
ever, odor thresholds as low as 0.06 ppm (70 ug/n>3) have been re-
ported in sensitive individuals. While most people can tolerate 2-3
ppm (2400 to 3600 ug/m3) without any apparent discomfort, above this
level discomfort becomes pronounced. Symptoms include coughing,
sneezing, lacrlmation, headache, and feelings of suffocation. Expo-
sure to high concentrations (above 5 ppm) can cause damage to the
respiratory tract; bronchitis and laryngitis may result. Exposure to
levels in the range of 50-100 ppm can cause pulmonary edema, lung
inflammation, and death (OTS, 1976).
Edema and hemorrhages of the lung and damage to the liver and kidneys
of rats have been reported after exposure by inhalation or subcutan-
eous injection. The LC50 for rats exposed for 30 minutes to formal-
dehyde vapor is 800 ppm (1 g/m3) (OTS, 1976).
2.1.2 Chronic Toxicity
Dermatitis from exposure to formaldehyde is a common problem in
workers and others who contact the chemical regularly. Formaldehyde
is known to be an allergen in sensitive individuals. Reported symp-
toms experienced by residents in some homes insulated with urea for-
maldehyde insulation include: nose and eye irritation, asthmatic
attack, headaches, coughing and respiratory irritation, dry and sore
throat, nausea, vomiting, skin irritation, and anaphylatic shock
(allergic reaction). Some individuals are reported to become hyper-
sensitive to formaldehyde resulting in allergic reactions seen as
asthma (OTS, 1976).
Carcinogenicity, Mutagenicity, and Teratogenicity—The experimental
data available indicates formaldehyde is carcinogenic in animals. A
recent chronic inhalation study by the Chemical Industry Institute of
Technology (CUT) exposed rats and mice (120 animals of each sex and
2-1 July, 1982
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species per exposure group) to 0, 2, 6, and 15 ppm formaldehyde for
up to 24 months (6 hours a day, 5 days a week). A high incidence of
nasal tumors (squamous cell carcinomas) were observed in rats (51
males and 52 females) from the 15 ppm group. The mice tested showed
a much lower incidence of nasal tumors (2 male mice in the 15 ppm
group). This type of tumor is quite rare in unexposed animals and
none were observed in the unexposed control groups. Inhalation of
formaldehyde was also associated with an exposure-related increase in
frequency, severity and distribution of nasal lesions (squamous
metaplasia) in rats from all exposure groups. In contrast to the
rat, marked irritant-induced effects in mice were observed only at
the highest exposure level (15 ppm) (CUT, 1981).
Several groups (NIOSH, IARC, IRL6, EPA) regard the animal evidence
adequate to implicate formaldehyde as a potential carcinogen in
humans. However, there are no epldemiological studies to date which
indicate that formaldehyde is carcinogenic in humans (CAG, 1979; NTP,
1980; NIOSH, 1981).
There is an extensive data base showing that formaldehyde is
mutagenic in several species, including mice, Drosophila, plants,
yeast (S. cerevisiae) and several strains of bacteria (S.
typhimurium, E. coli). Formaldehyde also produced unscheduled DNA
synthesis in a human cell line (HeLa) and sister chromatid exchanges
in Chinese hamster ovary (CHO) cell line and in cultured human
lymphocytes (CAG, 1979; OSW, 1980).
The available evidence does not indicate that formaldehyde is
teratogenic. Formaldehyde has been found negative in teratogenicity
assays in beagle dogs, rats, and mice (ODW, 1981).
2.1.3 Absorption, Distribution and Metabolism
Under normal conditions formaldehyde can enter the body through
dermal and eye contact, inhalation, and ingestion. On dermal
contact, formaldehyde reacts with proteins of the skin resulting in
cross-linking and precipitation of the proteins. Inhalation of
formaldehyde vapors produces irritation and inflammation of the
bronchi and lungs; once in the lungs, formaldehyde can be absorded
into the blood. Ingestion of formaldehyde is followed immediately by
inflammation of the mucosa of the mouth, throat, and gastrointestinal
tract. Absorption appears to occur in the intestines (OTS, 1976).
Following absorption into the blood stream, formaldehyde disappears
rapidly due to condensation reactions with tissue components and oxi-
dation to formic acid (which exists in the form of the formate anion
at physiological pH). The main metabolic pathway for formaldehyde
appears to involve initial oxidation to formic acid, followed by
further oxidation to C02 and ^0. Liver and red blood cells appear
to be the major sites for the oxidation of formaldehyde to formic
acid. Some of the formic acid metabolite is excreted in the urine as
the sodium salt; most, however, is oxidized to C02 and eliminated via
the lungs (OTS, 1976).
2-2 July, 1982
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2.2 Environmental Effects
2.2.1 Aquatic Effects
The use of formalin (aqueous formaldehyde) as a chemotherapeutant for
control of fungus on fish eggs and ectoparasites on fish is a widely
accepted and successful technique. However, unless certain criteria
are met, formalin may cause acute toxic effects in fish. Analysis of
toxicity levels indicates that a wide range of tolerances exists for
different species; striped bass appear to be the most sensitive with
an LCso of 5.6 to 13 ppm of formaldehyde. The LCso of formaldehyde
for invertebrates (Daphnia magna) is reported to range between 100 to
1,000 ppm. The 48-hour median threshold limit (TLm) for Daphnia was
about 2 ppm. Ho effects were observed in crayfish (Procambarus
blandingi) exposed to 100 ul/1 of formalin for 12 to 72 hours (OTS,
1976; OSW, 1980).
2-3 July, 1982
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3. ENVIRONMENTAL RELEASE* (CONTACT: Nancy Pate, FTS 629-5502)
The sources of formaldehyde can be grouped into two major categories:
direct (or commercial) production and indirect production. The chem-
ical is not imported in any appreciable quantities.
Commercially, formaldehyde is produced from the catalytic oxidation
of methanol, using either silver oxide or a mixed-metal oxide as the
catalyst. Processes accounting for the indirect production of
formaldehyde include the photochemical oxidation of airborne hydro-
carbons from vehicular exhausts, the incomplete combustion of hydro-
carbons in fossil fuels and refuse, and other natural processes.
Formaldehyde serves as a feedstock for many products and processes.
The chemical may enter into and leave these products and processes
essentially unaltered (non-consumptive use), altered in an irrevers-
ible manner (consumptive use) or altered in a manner that may be
reversed under certain conditions (pseudo-consumptive use). The type
of use plays a significant role in determining the release levels of
formaldehyde that are associated with secondary and subsequent appli-
cations of the primary products.
The available data on the production, uses, and release levels (with
pollution control devices) of formaldehyde indicate the following
(all data are expressed as 100 percent formaldehyde for the year
1978):
(1) Approximately 1,580,000 kkg of formaldehyde were produced in
1978: 1,070,000 kkg (68 percent) from direct production and
510,000 kkg (32 percent) from indirect production.
(2) All of the formaldehyde indirectly produced (510,000 kkg) was
released to the atmosphere; these releases accounted for 97
percent of the total airborne emissions of formaldehyde in 1978
(525,000 kkg).
(3) Of the releases from indirect production (510,000 kkg), 330,000
kkg (63 percent) were generated from the combustion of fossil
fuels and refuse, and 180,000 kkg (34 percent) were generated
from the photochemical oxidation of airborne hydrocarbons from
vehicular exhaust.
(4) Most (94 percent; approximately 1,000,000 kkg) of the
formaldehyde directly produced was consumed in subsequent
chemical reactions (consumptive and pseudo-consumptive uses).
*The data for this section was taken from the recent technical document
prepared by the Office of Toxic Substances (OTS, 1982).
3-1 July, 1982
-------
(5) Approximately 588,000 kkg (55 percent) of the commercially
produced formaldehyde were consumed in the manufacture of two
products: urea-formaldehyde and phenol-formaldehyde resins.
The urea resins (pseudo-consumptive use) consumed 300,000 kkg
(28 percent), and the phenol resins (consumptive use) consumed
288,000 kkg (27 percent).
(6) No more than 55,000 kkg (5 percent) of the direct production
levels were used in non-consumptive applications.
(7) No solid waste or waterborne releases of formaldehyde could be
quantified.
For a better perspective on the significance of the sources of re-
lease, the release levels are ranked in order of decreasing quantity
in Table 2.
In general, the emissions from indirect production are concentrated
in urban and industrial areas. Most of the facilities involved in
the manufacture and processing of formaldehyde and products contain-
ing formaldehyde are located in the Northeastern United States, along
the Gulf Coast, and in the Pacific Northwest. The plants range in
size from large, fully integrated plants that produce the raw materi-
als, resins, and end-use products to small, specialized facilities
that may produce only one product line of a particular consumer good.
Formaldehyde is potentially released from many sources that could not
be quantitatively addressed. These sources include derivative chemi-
cals containing residual levels of formaldehyde (e.g., 1,4-butane-
diol), products containing unreacted formaldehyde (e.g., embalming
fluids and deodorizing agents), and derivatives containing labile
formaldehyde bonds (e.g., urea-formaldehyde resins). Releases from
these sources may occur during their production, processing, use by
consumers, or disposal and may be emitted to air, land, or water
throughout the United States.
Note; Recent estimates from OAQPS for formaldehyde emissions from
stationary and mobile sources and from photochemical oxidation are
included in a footnote to Table 2. The value for photochemical
production differs considerably from that estimated by OPTS.
Attempts are underway to develop agreed-upon air emission estimates
for the indirect production of formaldehyde (CONTACT: Jack
McGinnity, FTS 629-5504).
3-2 July, 1982
-------
TABLE 2: SUMMARY OF AIRBORNE FORMALDEHYDE RELEASES. 1978a
Formaldehyde Releases
Source
Formaldehyde indirect production :b
Combustion of fossil fuels and refuse
Photo-oxidation of vehicular exhaust
Urea-formaldehyde resin production
Phenol-formaldehyde resin production
Miscellaneous chemical production
Pentaerythritol production
Formaldehyde production, direct
Acetal resins production
Melamine-formaldehyde resin production
1 , 4-Butanediol production
Hexamethylenetetramine production
Trimethylolpropane production
Total
Quantity
(103 kkg)
330.0
180.0
3.7
3.5
2.7
1.5
1.1
1.0
0.6
0.6
0.2
0.01
525
Percent of
total
63.0
34.0
0.7
0.7
0.5
0.3
0.2
0.2
0.1
0.1
<0.1
<0.1
100%
aSource: (OTS, 1982)
^Recent data submitted by OAQPS for indirect production as follows (10-* kkg):
mobile sources, 208; combustion of fuel oil, gas, and coal, 63; incineration
of refuse, 34; oil refineries, 42; photochemical oxidation in the atmos-
phere, 1390 (Contact: Jack McGinnity, FTS 629-5504).
3-3
July, 1982
-------
4. EXPOSURE ROUTES* (CONTACT: Nancy Pate, FTS 629-5502)
Over 97 percent of the formaldehyde releases are airborne and are
asssociated with the incomplete combustion of fossil fuels and trash,
and the photochemical oxidation of hydrocarbons from vehicular
exhaust. These processes occur primarily in urban and industrial
areas. Much lower levels of inadvertent release are expected to
occur in rural areas.
Because of the scarcity of data concerning exposure via routes other
than inhalation, only the inhalation route will be discussed in
detail. Table 3 is a summary of the available inhalation exposure
data. The table shows that three situations have the potential for
significant exposure: residences using particleboard and/or urea-
formaldehyde foam insulation; biology laboratories; and autopsy
rooms. Two other situations, mushroom farming and particleboard
veneering, also show potential for significant exposures based on
monitoring data, but these data may not be representative of general
levels for those occupations. Exposure for most other occupations
related to formaldehyde is in an order-of-magnitude range below the
high exposure situations mentioned above. Typical ambient exposures
(0.001 to 0.03 ppm) are rather low in comparison to almost all
occupational exposures. The highest levels of atmospheric formalde-
hyde have been recorded in urban areas. Typical urban levels are on
the order of 0.005 ppm while in non-urban areas levels can be assumed
to be between the background level of 0.0004 ppm and the typical
urban level of 0.005 ppm.
The reader is cautioned that most of the data used for this exposure
assessment, while useful for obtaining rough estimates of exposure,
probably are not statistically representative of the categories for
which they were used. Assessing risk based on these exposure values
should therefore be done with care.
The most significant limitations in the exposure data are that many
of the data probably are not statistically representative and that
some of the data represent levels that probably could not be
tolerated by a person for more than a brief period of time. The lack
of statistical representativeness has been confirmed for some of the
data. Because, in general, sampling sites were selected purposefully
from among those locations where a formaldehyde problem was suspected
and because time periods for air sampling appeared to be selected
arbitrarily, the data probably are not representative of the average
exposures for the studied populations. In many cases, the data are
of marginal analytical quality, generally because of insufficient
information on sampling, analytical, and quality assurance proce-
dures. Although these limitations are recognized, there are at
present no hard data on which to make more representative and more
realistic estimates of exposure. The procedures used to arrive at
these exposure estimates and their limitations are described in
detail in the source document (OTS, 1982).
* The information in this section is taken from a recent document prepared by
the Office of Toxic Substances (OTS, 1982).
4-1 July, 1982
-------
Almost half the formaldehyde produced is consumed to make resins for
adhesives. These adhesives are used by the construction industry for
manufacturing particleboard, plywood, and urea-formaldhyde foam
insulation. Release of formaldehyde from these products may be a
major source of exposure in the home. While many formaldehyde-
derived plastics release little formaldehyde during normal use,
urea-formaldehyde resins may decompose and release formaldehyde at a
faster rate.
Formaldehyde is very water soluble and may be discharged to aquatic
environments. However, there is essentially no data which would
permit water releases to be estimated. The amount of formaldehyde
present in wastes and subsequent releases associated with incinera-
tion or leachate from landfills also cannot be estimated.
Formaldehyde contamination of foods from anthropogenic sources (such
as the use of formaldehyde in packaging materials) is not apparent
from the available monitoring data. Formaldehyde has been detected
in some foods, but the sources are frequently non-anthropogenic. For
example, in some fish species, reduction of trimethylamine oxide
yields formaldehyde. Studies indicate that formaldehyde levels in
fish and shrimp increase with storage time.
4-2 July, 1982
-------
TABLE 3: SUMMARY OF INHALATION EXPOSURE ESTIMATES
00
NJ
Subpopulation
I. Occupational exposures
Direct producers
of formaldehyde
Users of formaldehyde:
Resin producers
Plywood/particle-
board manufacturing
Furniture production
(veneering)
Office trailer
occupants
Workers in U-F foam
insulated buildings
U-F foam producers/
distributors
U-F foam installers/
dealers
Molded products
producers
Textile producers
Estimated
number of
people exposed
420
2,000-6,200
21,000-30,000
unknown
unknown
unknown
30-80
2,000-15,000
unknown
360-6,000
Exposure
level (ppm)
1.1-1.6 a
0.1-1.7 a
1-2.5 r
0.008-6.4 r
0.4-2.8 a
0.02-0.10 r
0.06 a
<0. 5-3.1 r
0.06-5.4 r
0.19-1.5 a
<0.02-1.3 r
0.01-4 r
0.09-0.53 a
<0.1-1.4 r
0.25-0.7 a
Duration
(hr/wk)
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
Individual
exposure
(ppm-hr/yr)*
2,300-3,300 a
200-3,500 a
2,000-5,200 r
17-13,000 r
800-5,800 a
42-200 r
120 a
< 1,000-6, 400 r
125-11,000 r
395-3,100 a
<42-2,700 r
<20-8,300 r
190-1,100 a
<200-2,900 r
520-1,600 a
Estimated
yrs
exposed
40 x
10 a
40 x
10 a
40 x
10 a
40 x
10 x
15 x
5 a
40 x
10 a
40 x
10 a
40 x
10 a
40 x
10 a
40 x
10 a
-------
TABLE 3. SUMMARY OF INHALATION EXPOSURE ESTIMATES (Continued)
1-1
VO
00
Subpopulation
Paper and paper
products producers
Fertilizer producers,
appliers
Estimated
number of
people exposed
7,200-45,000
500-9UO
Exposure
level (ppm)
0.01-0.28 r
0.05-0.08 a
0.2-1.9 r
0.9 a
Duration
(hr/wk)
40
40
30
30
Individual
exposure
(ppm-hr/yr)*
20-580 r
100-170 a
310-3,000 r
1,400 a
Estimated
yrs
exposed
40 x
10 a
40 x
10 a
Users of formaldehyde as a
disinfectant or preservative:
Embalmers/funeral services 70,000
Pathologists
Agricultural production
(mushroom farms)
biology instructors
(college/univ. )
biology instructors
(high school)
College students
High school students
12,000
unknown
13,000
22,000
1,200,000
unknown
0.20-4.0 r
0.52-2.1 a
0.06-7.9 r
4.8 a
<0.5->10 r
2.68 a
2.75-14.8 r
8.3 a
2.75-14.8 r
8.3 a
2.75-14.8 r
8.3 a
2.75-14.8 r
8.3 a
20
20
30
30
40
40
20
5
10
1
200-4,200 r
540-2,200 a
12,000 K
7,500 a
2 0,000 x
5,600 a
2,000-11,000 r
6,000 a
500-2,700 a
1,500 a
990-5,300 r
3,000 a
99-530 r
300 a
40 x
10 a
40 x
10 a
40 x
10 a
40 x
10 a
40 x
10 a
8 x
4 a
2 x
1 a
-------
TABLE 3. SUMMARY OF INHALATION EXPOSURE ESTIMATES (Continued)
I
Ul
t-l
to
oo
10
Estimated
number of
Subpopulation people exposed
Producers of rubber 6,100-28,000
and misc. plastics
(.rubber hose production)
Glue producers unknown
Producers of paving and unknown
roofing materials
Primary metal industries 540-15,000
(includes iron and steel
foundries)
Locomotive mechanics unknown
II. Consumer use exposures
Residents, from
plywood/par ticleboard
Mobile homes 2,200,000
Conventional homes unknown
Residents, from 1,330,000-1,560,000
U-F foarn
Exposure
level (ppm)
0.02-0.04 r
0.04 a
0.09-0.17 r
0.03-0.07 r
0.05 a
<0. 02-18. 3 r
0.43
0.015-0.07 r
<0. 03-2. 54 r
0.4 a
0.04-1.8 r
0.5 a
0.05-3.4 r
0.72.a
Duration
(hr/wk)
40
40
40
40
40
30
30
40
100-150
100-150
100-150
Individual
exposure
(ppm-hr/yr)*
<42-83 r
83 a
193-350 r
60-150 x
100 a
<30-29,000 r
670 a
31-150 r
<156-20,000 r
2,000-3,100 a
200-14,000 r
2,600-3,900 a
260-27,000 r
3,700-5,600 a
Estimated
yrs
exposed
40 x
10 a
40 x
10 a
40 x
10 a
40 x
10 a
40 x
10 a
15 x
5 a
15 x
5 a
15 x
5 a
-------
TABLE 3. SUMMARY OF INHALATION EXPOSURE ESTIMATES (Continued)
Subpopulatioii
Residents from foam/
particleboard
(unspecified or both)
Estimated
number of
people exposed
unknown
Exposure
level (ppm)
0.1-2.92 r
0.22-0.99 a
Duration
(hr/wk)
100-150
Individual
exposure
(ppm-hr/yr)*
520-23,000 r
1,100-7,700 a
Estimated
yrs
exposed
5 a
III. Ambient exposures
Air (U.S. ambient) 220,000,000
Water 220,000,000
<0.001-0.03 r
negligible
168
<9-262 r
70 a
x = maximum data observed or "worst case"
r = range
a = average, median, or "typical" value
* Yearly exposures for occupations where weekly exposures are 40 hrs per week were estimated using a 2,080-hr
work year. Occupations where exposures are less than 40 hours per week were estimated as a fraction of the
2,080-hr work year (e.g., for embalmers, weekly exposure is 20 hrs/wk, and yearly exposure is based on
20/40 x 2,080, or 1,040 hrs/yr). Items which relate to school settings were calculated using a 36-week
year times the weekly exposure duration. Non-occupational exposure, such as residential exposures or
ambient exposures, were based on a 52-week year times the weekly exposure duration.
vo
00
Source: (UTS, 1982); categories for which no exposure level could be estimated have been deleted.
OTS document for other potential occupational exposure sections.
See the
-------
5. DftTA BASES
5.1 Chemicals in Commerce Information System (CICIS)
The inventory was compiled under the authority of Section 8 of TSCA
which requires manufacturers to report to EPA the chemicals imported
and manufactured during calendar year 1977. The Inventory lists the
Chemical Abstract Service (CAS) preferred name for the chemicals,
their respective CAS number (often used for identification purposes),
production site, company name, and volume(s) of production and
import. There is also a Confidential Inventory in which many of these
characteristics are claimed confidential by the manufacturer. In
these instances, the confidential information will not be available in
the public inventory. CICIS can now be accessed through the NIH/EPA
Chemical Information System (CIS - see 5.3). For further information,
contact Gerri Nowack at FTS 382-3568 or Robin Heisler at FTS 382-3557.
5.2 EPA Chemical Activities Status Report (EPACASR)
EPACASR is an on-line system containing information on EPA's interest
in chemicals. This system includes data on the Agency's regulations
research, and assessments directed toward specific chemicals. EPACASR
is published annually and the data base is updated as information is
received. A searchable subset itemizes KTP/tfCI studies and results,
as well as chemicals discussed in the IARC monograph series. (Other
sources are added as appropriate.) Entries identify the statutory
authority, the nature of the activity, its status, the reason for
and/or purposes of the effort, and a source of additional
information. Searches may be made by CAS Number or coded text.
(EPACASR is scheduled to be added to CIS in early 1984.) For further
information, contact Eleanor Merrick at FTS 382-3415.
5.3 NIH/EPA Chemical Information System (CIS)
This is a collection of various scientific data bases available
through an interactive computer program. The linking system between
these data files is the Structure and Nomenclature Search System
(SANSS). CIS can also provide a list of non-CIS sources of
information on a chemical of interest. However, these files have to
be accessed individually by either separate on-line systems or in
hard-copy. For further information, contact Dr. Steve Heller at FTS
382-2424.
5.4 Chemical Regulations and Guidelines System (CKGS)
CRGS is an on-line data base which is being developed to provide
information on chemical regulatory material found in statutes,
regulations, and guidelines at the Federal, State, and international
levels. Currently, only the first phase of CRGS, which encompasses
only source material at the Federal level, is operational. Nation-
wide access to CRGS is available through Dialog. For further
information, contact Doug Sellers at FTS 382-2320.
5-1 October, 1983
-------
5.5 Chemical Substances Information Network (CSIN)
The Chemical Substances Information Network (CSIN) is a
sophisticated switching network based on heterogeneous distributed
data base management and networking concepts. CSIN offers efficient
access to on-line information resources containing data and
information relevant to chemical substances, as well as information
covering other scientific disciplines and subject matters. The
purposes of CSIN are two-fold: first to meet the growing chemical
data and information requirements of industry, academe, government
(Federal and State), public interest groups, and others; and secondly
to reduce the burden on the private and public sector communities when
responding to complex Federal legislation oriented to chemical
substances.
CSIN is not another data base. CSIN links many independent and
autonomous data and bibliographic computer systems oriented to
chemical substances, establishing a "library of systems". Users may
converse with any or all systems interfaced by CSIN without prior
knowledge of or training on these independent systems, regardless of
the hardware, software, data, formats, or protocols of these
information resources.
Information accessible through CSIN provides data on chemical
nomenclature, composition, structure, properties, toxicity, production
uses, health and environmental effects, regulations, disposal, and
other aspects of the life cycle of materials as they move through
society. Currently, seven independent information resources are
accessible through CSIN. They are: National Library of Medicine
INLM), Chemical Information System (CIS), CAS-On-Line, SDC's ORBIT,
Lockheeds's DIALOG, Bibliographic Retrieval Service (BRS), and the US
Coast Guard's Hazard Assessment Chemical System (HACS). For further
information contact Dr. Sid Siegel at 202-395-7285.
5.6 EPA Information Clearinghouse
The EPA Information Clearinghouse is a bibliographic data base
composed of over 500 individual data bases and models which contain
monitoring infornation and statistics on a variety of chemicals. The
individual data bases are maintained for offices within EPA. The
clearinghouse listed 38 citations for formaldehyde. For further
information, contact Irvin Weiss at FTS 382-5918.
5-2 October, 1983
-------
6. REGULATORY STATUS (Current as of 9/83}
6.1 Promulgated Regulations
6.1.1 EPA Programs
Clean Water Act (CWA)
o Section 311 - Formaldehyde is classified as a hazardous substance
UOCFR116) and discharges are subject to reporting requirements
(40CFR117.3).
Resource Conservation and Recovery Act (RCRA)
o Section 3001 - Formaldehyde is listed as a toxic waste
(40CFR261.33) and as a hazardous waste constituent (40CFR261.32)
in wastes generated in the production of acetaldehyde (Waste
streams Nos. K009 and K010) and in the production of the pesticide
phorate (Nos. K038 and K040).
o section 3002 to 3006 - Standards concerning the generation,
transportation, treatment, storage and disposal of hazardous
wastes as defined above (40CFR262 to 265).
Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA)
o As an inert ingredient, formaldehyde is exempt from any tolerance
when used at less than 1 percent of pesticide ingredients
(40CFR180.1001(d)}.
6.1.2 Programs of Other Agencies
OSHA - Occupational Safety and Health Act
o Specifies permissible exposure limit for formaldehyde (3 ppm) as
an 8-hour TWA, with ceiling level (5 ppm) and peak level (10 ppm)
for 30 minutes (29CFR1910.1000). Construction industry standards
under the Contract Work Hours and Safety Standards Act are the
same (29CFR1926.55).
DOT - Hazardous Materials Transportation Act
o Regulations for transporting hazardous materials; identification
and listing of hazardous materials, including formaldehyde
(49CFR171 to 177).
o Port and Tanker Safety Act - Regulations governing shipping
vessels carrying hazardous liquids (46CFR150, 151, 153, and 154a).
FDA - Federal Food, Drug, and Cosmetic Act
o Regulations concern permissible components of the color additive
FD & C Blue No.2 (21CFR74.102); defoaming agents used in processed
foods (21CFR173.340); adhesives used in food packaging
6-1 October, 1983
-------
(21CFR175.105..300); food contacting paper and paperboard
(21CFR176.170 .180, .200, .210, .177). Also permissible use in
food additives (21CFR178, 181). These regulations apply to
formaldehyde or formaldehyde copolymers.
6.2 proposed Regulations
6.2.1 EPA Programs
Clean Air Act
o New Source Performance Standards (NSPS) have been proposed for the
Synthetic Organic Chemicals Manufacturing industry. The standards
would limit the emissions of volatile organic chemicals (VOC),
including formaldehyde (46FR1136).
Comprehensive Environmental Response, Compensation, and Liability
Act (CERCLA or Superfund)
o CERCLA provides for the liability, compensation, cleanup, and
emergency response for the release of hazardous substances into
the environment. This Act also deals with the cleanup of
hazardous waste disposal sites (42USC9601; PL-96-510). EPA is
developing regulations concerning the designation of hazardous
substances, the development of reportable quantities, claims
procedures, and the confidentiality of business records
(46FR54032).
o Revisions to the National Contingency plan (NCP) required by
CERCLA have been issued in a proposed rule (47FR10972).
Adjustments to the statutory reportable quantities have been
proposed; however, the RQ for formaldehyde is still under
assessment, and the statutory RQ based on Section 311 of the CWA
is still in effect (48FR23552).
6.2.2 Other Programs
DOT - port and Tanker Safety Act
o proposed revision of regulations for vessels carrying hazardous
liquids (45FR48058).
DHUD
o The Department of Housing and Urban Development has proposed
formaldehyde standards to control indoor air quality in
manufactured (mobile) homes. Product standards would limit
formaldehyde emissions from plywood and particle board materials
(48FR37136).
6-2 October, 1983
-------
6.3 Other Actions
EPA (Office of Drinking Water) has issued an informal guidance
level for formaldehyde (see Section 7.2).
o A rule issued by the Consumer Product Safety Commission (CPSC)
banning the use of urea-formaldehyde foam ((IFF) insulation in
households and schools (47FR14366) has been vacated by the United
States Fifth Circuit Court of Appeals. CPSC voted to establish a
Chronic Hazard Advisory Panel (CHAP) on formaldehyde and to
initiate a new program to address hazards associated with
formaldehyde in insulation and other consumer products.
o FDA's National Center for Toxicological Research (NCTR), under the
sponsorship of EPA, will convene a Consensus Workshop on
Formaldehyde to examine existing scientific data and to identify
future research needs (48FR36201; CONTACT: William McCallum, FTS
542-4513).
6-3 October, 1983
-------
7. STANDARDS AND RECOMMENDED CRITERIA*
7.1 Air
o OSHA limits (40FR1910.1000)
8-hour TWA 3 ppm
Ceiling 5 ppm
Peak 10 ppm
o NIOSH recommended ceiling: as low as practically
possible
o American Conference of 2 ppm
Governmental Hygienists
(ACGIH) threshold limit
value (TLV)
o The Department of Housing 0.4 ppm
and Urban Development
(DHUD) has proposed product
standards to regulate
formaldehyde levels in
mobile homes. DHUD estimated
that this level provides
reasonable protection
(48FR37136).
7.2 Water
Hazardous spill rules require 1000 Ibs
notification of spills equal
to or greater than the
reportable quantity
(40FR117.3)
A Health Advisory suggesting 30 ug/1
an acute exposure guidance
level for short term exposure
to formaldehyde in drinking
water has been issued by the
Office of Drinking Water (ODW).
* See Appendix A for a discussion of the derivation, use, and
limitations of these criteria and standards.
7-1 October, 1983
-------
8. SPILL OR OTHER INCIDENT CLEAN UP/DISPOSAL (CONTACT: National
Response Center
800-424-8802;
in Washington,
426-2675)
8.1 Hazards and Safety Precautions
Formaldehyde solutions emit toxic formaldehyde fumes, producing
irritation of eyes, nose, throat and skin. Formaldehyde is a
suspected human carcinogen and should be handled with caution.
Formaldehyde will burn and may be ignited by heat, sparks and flame.
Flammable vapor may spread from spill. Vapor is an explosion hazard
indoors, outdoors, or in sewers. Fire produces poisonous gases.
8.2 First Aid
Move victim to fresh air. If not breathing give artificial respira-
tion; if breathing is difficult, give oxygen. In case of contact,
flush eyes or skin with running water. If ingested, dilute, inacti-
vate, or absorb formaldehyde by giving milk, activated charcoal, or
water. Do not use gastric lavage or emetics. Treat for shock.
8.3 Emergency Action
Spill or Leak
Do not touch spilled material; use water spray to reduce vapors.
Stay upwind and wear protective clothing and breathing apparatus.
Remove all ignition sources.
Fire
For small fires, use dry chemical, C02, water spray, or foam. For
large fires, use water spray, fog, or foam. Move containers from
fire area if possible, stay away from ends of tanks, and cool con-
tainers with water from the side until well after fire is out.
Isolate for one-half mile in all directions if tank or tank car is
involved in fire.
8.4 Notification and Technical Assistance
Section 103(a) of the Comprehensive Environmental Response, Compensa-
tion, and Liability Act (CERCLA or "Superfund") requires notification
of the National Response Center (NRC; 800-424-8802; in Washington,
426-2675) if releases exceed reportable quantities (1,000 Ibs in the
case of formaldehyde).
For emergency assistance call CHEMTREC: 800-424-9300. Within EPA,
information may be obtained from the Division of Oil and Special
Materials (1-202-245-3045).
8-1 July, 1982
-------
8.5 Disposal
Generators of more than 1,000 kg (2,200 Ibs) of hazardous waste (or
residues from spill cleanup) per month are subject to RCRA
regulations. The following specific waste streams which contain
formaldehyde are subject to RCRA regulations:
• Distillation bottoms (K009) and side cuts (K010) from the
production of acetaldehyde from ethylene.
• Wastewater from washing and stripping (K038) and treatment
sludge (K040) from the production of the pesticide phorate.
8-2 July, 1982
-------
9. SAMPLING, ACCEPTABLE ANALYTICAL TECHNIQUES. AND QUALITY ASSURANCE
9.1 Air (CONTACTS: Michael E. Beard, FTS 629-2623)
Formaldehyde (CI^o) is not a regulated air pollutant,* therefore, no
Agency-approved procedure is available. However, measurements of
atmospheric CH20 using a chromotropic acid procedure have been
reported in the literature and a tentative method has been published
by the Intersociety Committee (Methods of Air Sampling and Analysis,
2nd Edition, American Public Health Association Intersociety Commit-
tee, 1015 Eighteenth St., NW, Washington, D.C. 20036).
Formaldehyde is sampled by bubbling ambient air through an absorber
containing distilled water. A sampling rate of one liter per minute
for 24 hours is recommended, but shorter sampling times may be used
where concentrations are sufficiently high. The effect of storage on
the sample is unknown.
Formaldehyde in the solution is determined by adding chromotropic
acid (4,5-dihydroxy-2,7-naphthalenedisulfonic acid disodium salt) and
sulfuric acid to form a purple solution. The absorbance of the solu-
tion at 580 nm is proportional to the formaldehyde concentration. A
range of 0.1 ug/ml to 2.0 ug/ml of formaldehyde can be measured in
the solution using this procedure. A concentration of 0.1 ppm CH2°
can be determined from a 25-liter air sample. Analyses of samples
containing 1 to 20 ug C^O by three laboratories gave a precision of
± 5 percent. There are no significant positive interferences,
including other aldehydes, but several negative interferences are
reported. An 8:1 excess of phenols over CH20 results in a negative
interference of 10 to 20 percent. A 10:1 ethylene and propylene
excess over CI^o results in a negative interference of 5 to 10
percent. A 15:1 excess of 2-methyl-l,3-butadiene showed a 15 percent
negative interference. Aromatic hydrocarbons and cyclohexanone also
produce negative interferences.
No quality assurance reference materials are currently available for
formaldehyde.
9.2 Water
Formaldehyde is not a priority pollutant and there are no Agency pro-
cedures at this time for the analysis of formaldehyde in water.
However, methods used for analysis of formaldehyde air samples may
presumably be applied to water samples because formaldehyde is
usually analyzed in water solutions in these procedures (see
Sections 9. 1 and 9.4).
* Formaldehyde is indirectly regulated as a "volatile organic compound" but
no procedure is required for the specific analysis of formaldehyde.
9-1 July, 1982
-------
9.3 Solid Waste (CONTACTS: Michael Hiatt, FTS 545-2118
Werner Beckert, FTS 545-2137)
Method 8.01 in Test Methods for Evaluating Solid Waste - Physical/
Chemical Methods (US EPA/SW-846/1980) is approved for analyses of
formaldehyde in solid wastes.
Three possible sample preparation techniques that could be applicable
to the formaldehyde determination by GC/MS are solvent extraction,
modified purge and trap, and vacuum extraction. However, no recovery
and precision data are available for any of the above methods when
applied to the quantitation of formaldehyde—most methods have
problems.
The solvent extraction technique is recommended only for concentra-
tions exceeding 1 ppm, while purge and trap methods may give low
recoveries because of the relatively high solubility of formaldehyde
in water.
With the vacuum extraction technique, the volatiles are extracted
from the sample using a vacuum. The extracted volatiles are collec-
ted in a liquid nitrogen-cooled trap. After extraction, 5 ml of
water are added to the extract and the sample is analyzed as a 5-ml
water sample using Method 624 (44FR69532, gas chromatography/mass
spectroscopy).
In a recent Japanese publication (referenced in Chem. Abstracts
94:141037v) a method is described for the determination of formalde-
hyde at the ppb level in clothes. The compound is extracted into
water, derivatized, the derivative extracted into hexane and deter-
mined by GC/EC.
Standards can be obtained from Radian Corporation or EMSL-Las Vegas
(see Contact above). Supleco supplies diluted standards but the
concentrations are not verified. Standard solutions may also be
prepared in the laboratory from reagent-grade formaldehyde (40
percent) to the appropriate dilution using methanol.
9.4 Other Procedures
The NIOSH Manual of Analytical Methods, 2nd Edition, contains proce-
dures for the collection and analysis of formaldehyde vapors.
Methods 125 and 235 (Vol. 1) employ chromotrophic acid to form a
colored derivative which is detected spectrophotometrically. Collec-
tion by drawing the air through alumina followed by desorbtion with
1 percent methanol in water (method 235) allows measurement in the
0.4 to 52 mg/m3 range (0.3 to .43 ppm).
In Method S327 (Vol. 4) air is drawn through a solution of Girad's T
reagent which traps formaldehyde in an ionic water soluble form. The
derivative is then analyzed by polarography. The working range is
reported to be 1.4 to 20 ppm.
9-2 July, 1982
-------
The most recent NIOSH procedure (318, Vol. 6) involves adsorption of
formaldehyde on impregnated charcoal, desorption with H202 to
formic acid (HCOOH), and isolation and quantification by ion exchange
chroma tography. Recoveries are excellent, precision is 9.7 percent
(16 to 320 ug/sample), and the working range is 0.03 to 2 mg/m3 for a
9.6 liter air sample (3 to 200 ug/sample).
Monitoring and analysis methods for formaldehyde have recently been
summarized in a document prepared by the Office of Toxic Substances
(OTS, 1982).
9-3 July, 1982
-------
REFERENCES
The major references used in the preparation of this document are listed
below. EPA references are listed by the EPA office of origin and the year of
publication. For further information refer to the contacts given throughout
this document or contact the relevant EPA offices given at the end of this
section.
(CAG, 1979)
(CUT, 1981)
(NIOSH, 1981)
(NRC, 1981)
(NTP, 1980)
(ODW, 1981)
(OPTS, 1980)
(OSW, 1980)
(OTS, 1976)
(OTS, 1982)
Preliminary Risk Assessment on Formaldehyde-Type I-Air
Program, Carcinogen Assessment Group, Office of Health and
Environmental Assessment (1979).
Final Report on a Chronic Inhalation Toxicology Study in
Rats and Mice Exposed to Formaldehye, by Battelle Labs for
the Chemical Industry Institute of Toxicology (1981). [For
a summary, see CUT Activities, Vol. 2, No. 3; March,
1982].
Current Intelligence Bulletin 34; Formaldehyde-Evidence of
Carcinogenicity, National Institute of Occupational Safety
and Health, April 15, (1981).
Formaldehyde and Other Aldehydes, National Research
Council, NTIS No. PB82-128075 (1981).
Report of the Federal Panel on Formaldehyde, National
Toxicology Program, RTP, November (1980).
Informal Guidance Level for Formaldehyde, EPA Draft, Office
of Drinking Water, August (1981).
Level I Materials Balance: Formaldehyde, EPA Draft,
Contract No. 68-01-5793, Office of Pesticides and Toxic
Substances (1980).
Background Document-RCRA Subtitle C, Appendix A: Health
and Environmental Effects Profile, P. 104, Office of Solid
Waste (1980).
Investigation of Selected Potential Environmental
Contaminants; Formaldehyde, EPA-560/2-76-009, Office of
Toxic Substances (1976).
Technical Document: Formaldehyde EPA-Draft Document,
Office of Toxic Substances, March (1982).
R-l
July, 1982
-------
OFFICE CONTACTS
The EPA offices and divisions that are listed below may be contacted for more
information relating to the Indicated sections of this document. While these
offices are, in many cases, the offices of origin for the data included in
this paper, the personal contacts given throughout this document should be
contacted first. Unless otherwise noted, the offices listed are situated in
Headquarters, Washington, D.C., and the telephone numbers given are FTS
(Federal Telecommunications System) numbers. For commercial telephone calls
to Headquarters which are not placed on FTS, area code 202 must be used.
Other commercial numbers are noted for the office contacts located outside
Washington, D.C.
HEALTH AND ENVIRONMENTAL EFFECTS (Section 2)
Office of Health and Environmental Assessment (OHEA)
Environmental Criteria and Assessment Office:
Cincinnati, OH 684-7531 (513-684-7531)
Research Triangle Park, NC 629-2266 (919-541-2266)
Carcinogen Assessment Group 755-3968
Office of Drinking Water (ODW)
Health Effects Branch 472-6820
Office of Toxic Substances (OTS)
Health and Environmental Review Division 382-4241
Environmental Research Laboratory
Duluth, MN, Region V 783-9550 (218-727-6692)
ENVIRONMENTAL RELEASES AND EXPOSURE (Sections 3 and 4)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Water Regulations and Standards (OWRS)
Monitoring and Data Support Division 426-2503
R-2 July, 1982
-------
Office of Toxic Substances (OTS)
Exposure Evaluation Division 382-3873
Assessment Division 382-3442
DATA BASES (Section 5)
Office of Toxic Substances (OTS)
Management Support Division 382-3546
REGULATORY STATUS, STANDARDS, AND CRITERIA (Sections 6 and 7)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Drinking Water (ODW)
Criteria and Standards Division 472-5016
Office of Water Regulations and Standards (OWRS)
Criteria and Standards Division 755-0100
Effluent Guidelines Division 426-2571
Office of Solid Waste (OSW)
State Programs and Resources
Recovery Division 755-9107
SPILL CLEAN-UP AND DISPOSAL (Section 8)
NOTE: For Emergenices call the National Response Center at 1-800-424-8802
(1-800-426-2675 from the Baltimore/Washington area).
Office of Emergency and Remedial Response (OERR)
Emergency Response Division 245-3045
Oil and Hazardous Materials Spills Branch
Edison, NJ; Region II 340-6634 (201-321-6634)
R-3 July, 1982
-------
Office of Solid Waste (OSW)
Hazardous and Industrial Waste Division 755-9187
ANALYTICAL TECHNIQUES (Section 9)
Environmental Monitoring Systems Lab (EMSL)
Air Analysis
Research Triangle Park, NC 629-2454 (919-541-2454)
Water Analysis
Cincinnati, OH 684-7311 (513-684-7311)
Waste Analysis
Las Vegas, NV 545-2137 (702-798-2137)
GENERAL IPP COMMENTS, CORRECTIONS, OR QUESTIONS
Office of Toxic Integration
Chemical Information and Analysis Program 382-2249
R-4 July, 1982
-------
Lead
-------
LEAD
Table of Contents Page
Physical/Chemical Properties and Chemistry 1-1
Properties 1-1
Chemistry and Environmental Fate/Transport 1-1
Effects Information 2-1
Health Effects 2-1
Environmental Effects 2-4
Environmental Release 3-1
Air Releases 3-1
Water Releases 3-1
Exposure 4-1
Air Exposure 4-4
Water Exposure 4-4
Other Exposure Routes 4-5
Data Bases 5-1
Chemicals in Commerce Information System (CICIS) 5-1
EPA Chemical Activities Status Report (EPACASR) 5-1
NIH/EPA Chemical Information System (CIS) 5-1
Chemical Regulations and Guidelines System (CRGS) 5-1
Chemical Substances Information Network (CSIN) 5-2
EPA Information Clearinghouse 5-2
Regulatory Status 6-1
Promulgated Regulations 6-1
Proposed Regulations 6-3
Standards and Recommended Criteria 7-1
Air 7-1
Water 7-1
Hazardous Waste 7-1
Other 7-1
July, 1982
-------
Spill or Other Incident Clean-Up/Disposal 8-1
Hazards and Safety Precautions 8-1
First Aid 8-1
Emergency Action 8-1
Notification and Technical Assistance 8-2
Disposal 8-2
Sampling, Acceptable Analytical Techniques, and Quality Assurance 9-1
Air 9-1
Water 9-1
Solid Waste 9-4
Other Samples 9-4
Quality Assurance 9-4
References and Office Contacts &*!•
July, 1982
-------
LEAD
1. PHYSICAL/CHEMICAL PROPERTIES AND CHEMISTRY
1.1 Properties
Lead has by far Che largest use in the United States of any heavy
metal due to its utility and abundance. Although widely used in
metallic form (Pb), there also are over 70 lead compounds produced
in the United States. Table 1 lists the physical/chemical proper-
ties of some lead compounds of commercial or environmental signifi-
cance. Automotive uses dominate the market for lead in the form of
lead oxides for storage batteries and as alkyl lead fuel additives
(IERL, 1979).
Some properties of metallic lead that enhance its utility are soft-
ness, malleability, high density, low melting point, and corrosion
resistance. Inorganic lead compounds are generally ionic, nonvola-
tile, and moderately or highly insoluble in water. In contrast,
organolead compounds are usually nonionic, volatile, and lipid solu-
ble. The only widely used organolead derivatives are tetraethyl lead
(TEL) and tetramethyl lead (TML) (HERL, 1978).
1.2 Chemistry and Environmental Transport
Although lead can exist in two oxidized states (+2,+4), the divalent
species (Pb+2) dominates the inorganic chemistry of lead. Divalent
lead has a strong affinity for inorganic ions containing oxygen
(e.g., carbonate) or sulfur (sulfide). Furthermore, lead can com-
plex with electron-rich ligands in many organic compounds such as
amino acids, proteins, and humic acid. In organolead compounds the
lead is tetravalent, (e.g., TEL) and the covalent Pb-carbon bond can
dissociate thermally or photolytlcally to yield free radicals (HERL,
1978; OTS, 1979).
The atmosphere is the primary medium for transport of lead (in the
form of inorganic particulates). The combustion products of fuels
containing antiknock lead compounds (TEL or TML) are the largest
source of atmospheric lead pollution. The organometallic TEL and
TML decompose during combustion and the lead is scavenged from the
engine by halogenated fuel additives. Lead is emitted in the ex-
haust as particulate matter primarily in the form of lead halides
(e.g., PbBrCl). Although much of this particulate lead settles very
closely to roadways, smaller particles are widely dispersed so that
the average residence time of lead in the atmosphere is about 10
days. Complex chemical and photochemical reactions in the atmosphere
transform lead halides to relatively insoluble salts (i.e., PbC03»
PbO, PbSO^). Atmospheric lead particles are removed by sedimenta-
tion, dry deposition, and precipitation (HERL, 1978; ORD, 1977).
1-1 July, 1982
-------
TABLE 1: PROPERTIES OF LEAD COMPOUNDS3
Chemical Name
and Formula
Lead
Lead acetate,
trihydrate
Pb(OOCCH3)2.(H20}3
Lead carbonate
PbC03
Lead chloride
PbCl2
Lead nitrate
Pb(N03)2
Lead oxide
PbO
CAS Number
and Synonyms
7439-92-1
6080-56-4
Acetic acid, lead (2+)
salt, trihydrate;
sugar of lead
598-63-0
Carbonic acid, lead
(2+) salt (1:1);
white lead
7758-95-4
Lead (2+) chloride
10099-74-8
Nitric acid, lead
(2+) salt
1317-36-8
Lead monoxide;
Melting Boiling
Point (°C) Point (°C)
328 1,740
75 200
(dec)
315
(dec)
501 950
470
(dec)
886 1,472
Water
Solubility
(per liter)
0.3 mg
456g
(15°C)
1.1 mg
(20°C)
9.9 g
(20°C)
376 g
(0°C)
17 mg
(20°C)
Specific
Properties
and Uses
High density (11.3 g/cm3).
Often used in alloy form
with tin and/or antimony
Sweet tasting. Used in
paints and textile dyeing
Used commercially in paints
and ceramics in the form of
basic lead carbonate
Automotive combustion
product. Used in paints and
manufacturing lead compounds
Used in manufacturing lead
compounds, and the match
industry
Used as oxidized powder
in batteries
vo
oo
ro
litharge
-------
TABLE 1: PROPERTIES OF LEAD COMPOUNDS (cont.)
f— '
1
CO
C-,
c
<<*
t— '
vO
CO
ro
Chemical Name
and Formula
Lead sulfideb
PbS
Lead sulfateb
PbSO^
Tetraethyl leadb
Pb(C2H5)4
Tetramethyl leadb
Pb(CH3>4
a From data summarized
h /ii~ •- ift*7a\
CAS Number Melting
and Synonyms Point (°C)
13L4-87-0 1,114
Lead monosulfide;
galena
7446-14-2 1,170
Sulfuric acid,
lead (2+) salt (1:1)
78-00-2 -137
Plumbane ,
tetraethyl
75-74-1 -28
Plumbane ,
tetramethyl
in (IARC, 1980) unless otherwise
Boiling
Point (°C)
____
200 (dec)
Flash point
85°
110
Flash point
38°
noted .
Water
Solubility
(per liter)
0.86 mg
(20°C)
42 mg
(25°C)
0.2 mg (20°C)
[soluble in
organic solvents]
20 mg (20°C)
[soluble in
organic solvents]
Specific
Properties
and Uses
Major mineral source for ,
lead production
Used in pigments and
batteries
Density, 1.65
Degraded photochemically
Antiknock agent
Density, 2.0
Degraded photochemically
Antiknock agent
-------
Lead has a low solubility in natural waters due to the limited disso-
lution of the carbonate, sulfide, and sulfate salts. In hard water,
the carbonate concentration Is sufficient to keep lead concentrations
low ( 30 ppb). However, a drop in pH in soft water can result in
alarming increases in lead solubility. Lead introduced into surface
waters is readily adsorbed onto sediments with organolead complexes
(e.g., with humic acid) facilitating sorption by clays or metal hy-
droxides. Due to the relative immobility of lead in water it tends
to accumulate wherever delivered. However, anaerobic sediment mi-
crobes can methylate several lead derivatives to form a volatile or-
ganolead compound (THL). Furthermore, any changes in water charac-
teristics caused by acid rain, urban runoff, industrial effluents or
dredging may release lead from sediments. The effectiveness of these
biological, chemical, and physical mechanisms in remobilizing lead is
unknown (OWRS, 1979; OWRS, 1980b).
Soils represent the major sink for pollutant lead. The adsorption
or precipitation of lead in soils is promoted by the presence of
organic matter, carbonates, and phosphate minerals. Lead usually
accumulates in topsoil due to complexation with organic matter and
the transformation of soluble lead compounds to relatively insoluble
sulfate or phosphate derivatives. The efficient fixation of lead by
most soils greatly limits the transfer of lead to aquatic systems and
also inhibits absorption of lead by plants. However, leaching of
lead can be relatively rapid from some soils, especially at highly
contaminated sites or landfills (HERL, 1978; OTS, 1979).
1-4 July, 1982
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2. EFFECTS INFORMATION
2.1 Health Effects (CONTACTS: Jerry Stara, FTS 684-7531;
Les Grant, FTS 629-2266; Bob McGaughy,
FTS 755-3968; Bill Marcus, 382-3037)
Lead (Pb) poisoning, often referred to as "plumbism", can result
from its inhalation, ingestion, and in some cases, absorption
through skin. The effects of lead in humans are well documented and
levels once considered acceptable have been lowered due to increas-
ing evidence of subtle effects. The principal target organs affected
by lead are the erythroid cells of bone marrow, the kidney, and the
central and peripheral nervous system. The extent of lead toxicity
varies with different lead compounds and their physical/chemical
properties (e.g., soluble lead salts are considered more toxic than
Insoluble lead salts and organic lead compounds, in general, are more
toxic than inorganic lead compounds) (HERL, 1978).
Many toxic effects of inorganic lead can be attributed to the affini-
ty of lead for thiol groups (-SH) and other organic ligands in
proteins. Low concentrations of Pb"1"2 inhibit a select group of en-
zymes including thiol-dependent enzymes involved in heme synthesis
and mitochondrial energetics. The toxicologic effects of lead may
result from the ability of Pb+2 to uncouple oxidative phosphorylation
and modify mitochondrial ion transport (especially for calcium,
Ca*2). The volatile, lipid soluble organoleads, TEL and TML, are
rapidly absorbed either by inhalation or percutaneously. The extreme
toxicity of tetraalkyl lead compounds is apparently due to their
rapid metabolism to unstable and highly toxic trialkyl and dialkyl
lead derivatives (HERL, 1978).
2.1.1 Acute Toxicity
The following symptoms may occur after acute lead exposure: anorex-
ia, vomiting, malaise, and convulsions due to increased intracranial
pressure. Severe acute exposure may lead to acute lead encephalopa-
thy. These symptoms are most common in young children with a history
of pica. Colic has also been demonstrated in cases of acute poison-
ing (HERL, 1978). The mechanism for this occurrence is not under-
stood. Short-term exposure to high lead levels (MOOPbB*) can pro-
duce severe renal (kidney) effects (e.g., aminoaciduria) due to re-
versible tubular damage (WHO, 1977).
Anemia is an early symptom of both acute and chronic lead poisoning.
Anemia due to lead poisoning is thought to result from a decrease in
red blood cell production and Increased destruction due to lead in-
terference (HERL, 1978). Because this form of anemia has many mor-
phologic features in common with iron deficiency anemia and thalasse-
mia, it is often not easily distinguished as lead poisoning (NAS,
1972).
PbB's are expressed as micrograms of lead per 100 ml of blood, ug/dl.
2-1 July, 1982
-------
2.1.2 Chronic Toxic!ty
The effects of lead on the hematopoietic system are particularly
important since current knowledge suggests that this system Is the
"critical organ." The disruption of hemoglobin synthesis is general-
ly considered the first observable adverse effect of lead exposure.
Lead inhibits d-aminolevulinic acid dehydrase (ALAD) and heme-synthe-
these (enzyaes involved in hemoglobin synthesis) both in vitro and in.
vivo at relatively low levels of chronic lead exposure. Elevation of
the concentrations of the substrates for these two enzymes in plasma
and urine (ALA) and in erythrocytes (PROTO) increase as blood lead
levels (PbBs) increase. Rises in PROTO and ALA occur at PbBs some-
what below those associated with a decrement of hemoglobin. A decre-
ment in hemoglobin first appears at PbB • 50 in adults and at PbB =•
40 in children, whereas a distinct elevation in ALA in the urine
(ALAU) first appears at PbB = 40 in men and children and somewhat
lower in women. Rises in PROTO first appear at PbB = 15 to 20 in
women and children and at PbB - 25 in men (OWRS, 1980a).
Exposures to high concentrations of lead, resulting in PbBs ranging
from 80-120 ug/dl of blood can give rise to lead encephalopathy.
The major features are dullness, irritability, ataxia, headaches,
loss of memory and restlessness. These symptoms often progress to
delirium, mania, coma, convulsions, and even death. In addition to
central nervous system damage, peripheral neuropathy (paralysis) has
been reported at somewhat lower PbBs. The same general effects are
also described in infants and young children. Encephalopathy due to
lead is probably more frequently fatal in children than adults be-
cause lead exposure is usually not suspected and because children do
not communicate signs and symptoms as readily as adults. The mortal-
ity rate among children has been variously reported as being from 5
to 40 percent (OWRS, 1980a).
Subtle neurobehavioral effects occur in children chronically exposed
to lead at levels which do not result in clinical encephalopathy.
The minimal level of lead exposure, the duration of exposure re-
quired, and the period of greatest sensitivity cannot be specified
with any degree of certainty. The blood lead levels associated with
neurobehavioral deficits (minimal brain dysfunction) In asymptomatic
children appear to be In excess of 50 to 60 ug/dl. Future research
may reveal that this cut-off point is actually lower (OWRS, 1980a;
WHO, 1977).
Chronic toxlcity resulting from exposure to organic lead compounds
is manifested in elevated blood-lead levels. Inhalation of organic
lead compounds first results in toxicity to the central nervous sys-
tem, but in order to be absorbed Into the bloodstream, It must be
retained la the lower portions of the lung long enough to be solu-
bilized. The effects of organic lead on the hematopoietic system are
not as well documented as those of inorganic lead. Organic lead com-
pounds have a greater affinity for lipid tissues—the brain, body
fat, and the liver—than the bone marrow (HERL, 1978).
2-2 July, 1982
-------
No conclusive statement can be made as to whether lead is carcino-
genic in humans. Although rodents are susceptible to a variety of
lead-induced cancers, epidemiological evidence to date indicates no
carcinogenic effect on humans. The teratogenic and mutagenlc effects
of lead in humans also need clarification. Animal studies show that
parental exposure to lead increases reproductive problems and terato-
genic effects of lead in animals are manifested by congenital skele-
tal malformations. In humans, however, embryotoxicity apparently
precedes tetratogenicity (HERL, 1978).
Lead Poisoning in Children
Children between the ages of 1-5 are most susceptible to acute and
chronic lead poisoning. Lead is prevalent in big cities, especially
where deteriorated housing exists; paint peelings from this source
can contain up to 40 percent lead by weight. (See Section A for com-
plete discussion of exposure routes). The majority of lead-poisoning
cases in children are due to ingestion of the paint chips containing
lead. This can be attributed in part to the sweet taste of leaded
chips and to the tendency of children to put foreign objects into
their mouths ("pica" - the repetitive ingestion of non-food materi-
als). A higher percentage of Ingested lead is absorbed by children
than adults (HERL, 1978).
According to a 1976 National Academy of Science (NAS) report, child-
hood lead poisoning occurs primarily in three stages:
(1) Asymptomatic lead poisoning in which no clinical symptoms are
apparent, but in which measurable metabolic changes occur.
(2) Symptomatic poisoning in which clinical symptoms such as anorex-
ia, vomiting, apathy, atoxla, drowsiness, or irritability oc-
cur.
(3) Lead encephalopathy with cerebral edema, in which coma or con-
vulsions occur.
Other manifestations of lead poisoning are learning disabilities and
hyperkinesis (OTS, 1979).
Because young children are more susceptible to lead-induced neurolog-
ic damage (the brain is still growing in a child's early years) and
because of their tendency toward pica, children are less resistant Co
lower levels of lead than adults. Diet (e.g., malnutrition, and cal-
cium and iron deficiencies) has been Implicated as a possible cause
for elevated intestinal absorption rates for lead and high calcium or
phosphate levels have been effective in decreasing lead absorption
(OTS, 1979; HERL, 1978).
The fetus is highly sensitive to the neurological effects of lead
(due to lack of a blood brain barrier, efficient absorption, and rap-
Id brain growth rate). Lead has been shown to enter the placenta in
laboratory animals as well as in humans; lead has been detected
2-3 July, 1982
-------
in 12-week-old fetuses and has been shown to Increase throughout ges-
tation. Newborns have shown a. correlation between their urinary
ALA levels with blood-lead levels indicating that heme damage must
have occurred "in utero" (OTS, 1979).
2.2 Environmental Effects (OWRS, 1980a)
(CONTACTS: Duane Benoic, FTS 783-9507; John Gentile, FTS 838-4843)
2.2.1 Aquatic Effects
In addition to the acute toxicity of lead towards aquatic life,
chronic exposure to lead can delay embryonic development, suppress
reproduction, and inhibit the growth rate of fish, crab, poly-
chaetes, ciliate protozoans, and plankton, and reduce photosynthesis
and respiration in algae and diatoms.
Freshwater - Three invertebrate freshwater species demonstrate a
wide range of susceptibility to lead. LCso values ranged from 124
tig/1 for a acud to 40,800 ug/1 for a rotifer. In exposures up to 28
days the scud has been shown to be more sensitive to lead than a
snail, cladoceran, and immature stages of the chironomid, mayfly,
stonefly, and caddlsfly. Edible fish {rainbow trout, brook trout,
bluegill) appear to be less sensitive to lead than invertebrate
species.
Acute toxicity values ranged from 1,170 ug/1 to 8,000 ug/1 for rain-
bow trout and 4,100 ug/1 for brook trout in flow-through studies. In
static tests, rainbow trout and bluegill species demonstrated acute
toxicities of 471,000 ug/1 and 442,000 ug/1, respectively, in water
of similar hardness. The acute toxicity of lead to other freshwater
fish species ranged from 2,400 ug/1 to 7,330 ug/1 for fathead min-
nows, 31,500 ug/1 for goldfish and 20,600 ug/1 for gupples in static
tests conducted in water of similar hardness. Acute toxicity de-
creases as water hardness increases.
The relative acute sensitivities of various freshwater organisms in-
dicate that benthic insects are the least sensitive to lead.
The chronic toxicity of lead has been determined for only two fresh-
water Invertebrate species, Daphnia magna and a snail Lymnea palus-
trls. The acute-chronic ratio of 8.2 was obtained for Daphnia. A
lifecycle test with snails demonstrated that lead at a concentration
of 25 ug/1 significantly decreased survival but not growth or repro-
duction. This value is lower than the chronic value, 119 ug/1, re-
ported for daphnids.
Chronic tests, in hard and soft water, have been conducted wich six
species of freshwater fish. These experiments were not lifecycle
studies but determined that lead induced apinal deformities in rain-
bow trout fry at concentrations of 850 ug/1 in hard water and as low
as 31 ug/1 in soft water. This demonstrates that lead is more chron-
ically toxic in soft water than in hard water. Spinal deformities
have also been caused by lead in lifecycle tests with brook trout and
in early life stage tests with rainbow trout, northern pike, and
2-4 July, 1982
-------
walleye. Spinal deformities have not been determined in similar
tests with lake trout, channel catfish, white sucker, and bluegill.
Based on static short exposure tests with algae and diatoms, adverse
effect concentrations of lead ranged from 500 to 28,000 ug/1. It is
assumed that any adverse effects on aquatic plants are unlikely at
concentrations below those at which chronic effects on freshwater
animals occur.
Saltwater - No standard lead acute toxicity values for saltwater
fish species are available. The most sensitive invertebrate species
is a copepod Acartia elausi with an LC$Q of 668 ug/1. The least sen-
sitive is the soft shell clam Mya arenaria with an LC5Q of 27,000
ug/1. The LCso value of 2,450 ug/1 was obtained with oyster larvae
Corassostrea virginica and a value of 2,960 ug/1 was obtained for
mysid shrimp Mysidopsis bahia.
The mysid shrimp Mysidopsia bahia is the only saltwater species for
which a chronic test has been conducted on lead. The most sensitive
observed adverse effect was reduced spawning at a lead concentration
of 25 ug/1. The acute-chronic ratio is 11.9.
No saltwater plant species have been experimentally exposed to inor-
ganic lead. One saltwater algal species has been exposed to two
organolead compounds (tetramethyl and tetraethyl). Tetraethyl lead
was at least 10 times more toxic. However, no data are available
comparing the relative toxicities of inorganic and organic lead com-
pounds .
2.2.2 Other Effects
The bioconcentratlon factors for four freshwater invertebrate spe-
cies exposed to lead ranged from 499 to 1,700. Fish do not appear to
accumulate lead as readily as the Invertebrate species they may eat,
as indicated by bioconcentratlon factors of 42 and 45 for brook trout
and bluegills, respectively.
Of concern may be the relatively high bioaccumulation by saltwater
species used for human food. The bioconcentration factors for mus-
sels and oysters were 2,570 and 1,400, respectively. Hard clams had
a relatively low factor of 17.5.
2-5 July, 1982
-------
3. ENVIRONMENTAL RELEASE (CONTACT: Michael Slimak, FTS 426-2503)
Lead is a naturally occurring element in the earth's crust; however,
natural sources of emissions are insignificant when compared to an-
thropogenic releases. Lead enters the environment primarily from
auto emissions, ore mining and smelting, and ammunition production.
However, the amount of lead released to the environment from auto
emissions has been decreasing since 1973. Fifty-six percent of the
lead emitted to the environment is released to the atmosphere.
Although some lead remains in the atmosphere, a large proportion rap-
idly settles out in the vicinity of the source. Forty-two percent of
lead emissions goes to the land, 1 percent is discharged to the
water, and less than 1 percent is indirectly discharged from POTW's.
Based on Best Practical Technology (BPT), the Iron and Steel Industry
accounts for 87 percent of the industrial point source discharge to
the aquatic environment (OURS, 1980b).
Table 2 lists both the uses of lead and its releases to the environ-
ment by media. The release data are only crude estimates and have
not been verified by sampling and analysis. Note that lead batteries
constitute a non-dissipatlve use of lead so that 80 percent (Bureau
of Mines estimate) of the lead used in storage batteries is recycled
(OWRS, 1980b).
3.1 Air Releases (CONTACT: John Copeland, FTS 629-5595)
Significant Sources
• Mobile source: automotive combustion of leaded gasoline
• Primary and secondary lead smelters (SIC 3332 and
SIC 3313-3316)
• Battery production plant
• Lead gasoline additive plants
• Primary copper smelters (SIC 3331)
Other Source
• Primary zinc smelters (SIC 3333)
3.2 Water Releases (CONTACT: Michael Slimak, FTS 426-2503)
Significant Source
• Iron and Steel Industry
3-1 July, 1982
-------
Other Sources
• Non-ferrous metal
• Pulp and paper
• Inorganic chemicals
3-2 July, 1982
-------
TABLE 2: CONSUMPTION OF LEAD AND SOURCES TO THE ENVIRONMENT
FOR 1976 (kkg/yr and %)
I. USES OF LEAD
A. Lead batteries
B. Gasoline antiknock additives
C. Red and white lead paint pigments
D. Ammunition
E. Solder
kkg/yr
% of Total Uses
764,000
217,500
77,500
66,500
57,500
64.5
18.4
6.6
5.6
4.9
II. RELEASES TO ENVIRONMENT
A. Land Discharges
1. Domestic ore (mining,
milling, smelting,
refining)
2. Ammunition
3. Weights and ballasts
4. Bearing metals
5. Solders
6. Iron and steel production
B. Airborne Emissions
1. Gasoline additives3
2. Combustion of oil
3. Copper and zinc smelting
4. Domestic ore (mining,
milling, smelting,
refining)
5. Iron and steel production
6. Ammunition
55,989
50,000
10,143
9,478
5,734
5,400
kkg/yr
175,584
2,630
1,800
1,403
1,243
1,147
% of
Discharges
to Land
40.9
36.6
7.4
6.9
4.2
3.9
% of
Emissions
to Air
95.5
1.4
1.0
0.8
0.7
0.6
% of Total
Releases
41.9
17.1
15.3
3.1
2.9
1.8
1.7
Z of Total
Releases
56.2
53.7
0.8
0.6
0.4
0.4
0.4
3-3
July, 1982
-------
TABLE 2: CONSUMPTION OF LEAD AND SOURCES TO THE ENVIRONMENT
(kkg/yr and %) (cont.)
C. Aquatic Discharges
1. Industrial discharges
a. Iron and steel
manufacture^
b. Inorganic chemical
manufacture**
c. Nonferrous metals
d. Paper and pulp
e. Pigments
f. Textiles
2. POTW's
3. Urban Runoff
Source: Strategy for Controlling the
kkg/yr
1,309
83
53
36
15
6
1,375
3,700
% of
Industrial
Discharge
to Water
87.2
5.5
3.5
2.4
1.0
0.4
Environmental Exposure
% of Total
Releases
1.9
0.4
0.4
1.1
to Lead, Di
entitled Exposure and Risk Associated With Lead, OWRS, July 1981,
revised March 1982.
a This value is decreasing because of decrease of use of leaded gasoline.
b Updated 1980 value, OWRS.
3-4
July, 1982
-------
4. EXPOSURE
The pathways of human exposure to lead are numerous and complex.
Humans are exposed to environmental lead through inhalation,
Ingescion (food and water), and in the case of organolead compounds,
through cutaneous absorption. Under normal conditions, the
concentration of organic lead present in the environment is so low
that cutaneous absorption of organic lead can be ignored, except in
cases of accidental or occupational exposure. Inhalation is the
major contributor to body burden among those occupationally exposed
to lead. For the general population, dietary lead is probably the
most significant pathway of exposure, constituting 54-90 percent of
all lead intake in adults. However, relative to dietary lead,
inhalation may provide an equal or more important route of exposure
for persons living in the immediate vicinity of major stationary
sources or heavily traveled automobile freeways (OTS, 1979; OWRS,
1980b).
Food packaged in lead-soldered cans contributes 45 percent of lead
intake. Remaining lead exposure to food occurs from consumption of
leafy crops grown near sources of lead emissions (e.g., highways and
smelters). Total individual Intake of lead via food ingestion is
estimated to be 200 ug/day in urban and rural areas and 1,000 ug/day
for those living in the vicinity of smelters (OWRS, 1980b).
Inhalation of lead from the atmosphere is negligible except in
localities in which there are ore mining and smelting operations,
where estimates of individual lead Inhalation are 200 ug/day.
Drinking water generally contributes little to dally lead intake,
approximately 20 ug/day (OWRS, 1980b).
Consumption of paint, dirt, and dust containing lead represents the
largest exposure route for children. Higher exposure occurs in urban
areas than in rural areas. Preliminary results of a recently
completed four-year study* suggests that between 1976 and 1980, there
was a 36.7 percent reduction in the overall mean blood-level in the
U.S. population. Decreases were found in all races, ages, and both
sexes. The reduction in mean blood levels parallels the reduction in
the amount of lead used in the production of gasoline. The amount of
lead added to the environment from gasoline dropped from 190,000 kkg
in 1976 to 90,000 kkg in 1980 under restrictions imposed on the use
of lead as an antiknock additive for gasoline. This means that the
high-risk young children living in environments with high doses of
lead (i.e., leaded paint, lead already deposited in dust and soil,
etc.) will have a greater margin of safety.
Exposure is probably greater in urban areas, since contact with
contaminated dirt and dust may result. Infants depending entirely on
canned formulas are exposed to significantly greater amounts of lead
*Second National Health and Nutrition Examination (NHANES II), National
Center for Health Statistics, reported in the Centers for Disease Control
Morbidity and Mortality Weekly Report, Friday, March 19, 1982.
4-1 July, 1982
-------
TABLE 3: LEAD EXPOSURE/ABSORBANCE LEVELS
vo
CO
ro
Population
Effected Pathway
Adults food
drinking
water
air
Children food
drinking
water
air
Subpopulatlon
Rural
Urban
Smelting
Rural
Urban
Smelting
Leadpipes
Rural
Urban
Smelting
Rural
Urban
Smelting
Rural
Urban
Smelting
Leadpipes
Rural
Urban
Smelting
Exposure Cone .
(ug/day)
200
200
1,000
<20
<20
<20
100-200
2-15
15-62
200
100-140
100-140
500
!io
50-TOO
.3-3.4
3-13
40
Absorbed Dose
(ug/day)
20
20
100
<2
<2
<2
10-20
1-5
5-21
60
50-70
50-70
250
<5
<5
<5
25-50
.1-1.0
1-4
13
Exposure Criteria
(ug/day)
100a
100
100
100
30b
30
30
____
5QC
50
50
50
6d
6
6
Exceed
Criteria
No
No
No
Yes
No
Yes
Yes
No
No
No
Yes
No
Yes
Yes
-------
TABLE 3: LEAD EXPOSURE/ABSORBANCE LEVELS (cont.)
Population
Effected
Pathway Subpopulation
Exposure Cone.
(ug/day)
Absorbed Dose
(ug/day)
Exposure Criteria
(ug/day)
Exceed
Criteria
10
oo
PO
Children with paint
Pica
wherever avail.
,000f
500
300e
Yes
dirt &
dust
paint ,
dust &
dirt
Urban
Smelting
Urban
Smelting
1,000
1,000
2,000
2,000
500
500
1,000
1,000
300
300
300
300
Yes
Yes
Yes
Yes
Source: Strategy for Controlling the Environmental Exposure to Lead, Draft Report, OWRS (1980)
EPA Water Quality Criteria of 50 ug/1; assuming adult consumption of 2 liters/day.
EPA Air Quality Criteria of 1.5 ug/m3; assuming adult inhalation of 20 m3/day.
EPA Mater Quality Criteria of 50 ug/1; assuming child consumption of 1 liter/day.
EPA Air Quality Criteria of 1.5 ug/m3; assuming child inhalation of A m3/day.
Calculated from 0.3 mg maximum daily permissible child intake levels (King, 1971).
Estimates vary widely - figures, however, are representative of consumption due to pica.
a
b
c
d
e
f
-------
than breast-fed infants. Table 3 provides a detailed lead exposure
summary (OWRS, 1980b).
4.1 Air Exposure (CONTACT: John Copeland, FTS 629-5595)
Inhalation of particulate lead, usually in the form of elemental lead
or lead oxide, can arise near lead and non-ferrous smelters, heavily
traveled urban roads, sand blasting (for removal of leaded paints),
and roof vents from indoor firing ranges.*
4.2 Water Exposure
In areas where water supplies are stored in lead-lined tanks or
transported to the tap by lead pipes, lead concentrations may reach
in excess of 1,000 ug/1. The concentration of lead in water trans-
ported through lead pipes is dependent upon standing time, pH, and
the concentration of dissolved salts. At acidic pH values and low
salt concentrations, the solubility of lead in the water is
Increased. Plastic pipes may release lead stearate (OURS, 1980a).
The extent of excessive lead in tap water is not known. Special
attention should be given to soft water supplies, since they are low
in dissolved salts and frequently have pH values at or below pH 6.5
(OWRS, 1980a).
A survey taken of 100 major U.S. cities in 1964 found that 95 percent
contained lead at concentrations less than 10 ug/1. A similar study
conducted 6 years later of 969 public water supply systems in the
United States showed that only 37 sites exceeded the current National
Interim Primary Drinking Water Standard of 50 ug lead/liter. This
Indicates that drinking water as a major source of lead exposure
poses a relatively small hazard except in circumstances where lead
pipe or lead service connections are in contact with corrosive wa-
ter. In these cases substantial lead extraction and high drinking
water levels occur (OWRS, 1980a).
Hazardous substances from industrial waste land disposal sites are
capable of migrating into ground water. Records of hazardous waste
incidents include high lead contamination of local ground water.
Sludges from POTW may also contain high lead levels and hazards may
result from disposal of municipal sludges.**
An analysis of STORET data for the U.S. reveals concentrations of
lead at the 50th percentile of 300 ug/1 in fish tissue, 25,000 ug/1
in sediments, and 14 ug/1 in ambient waters. STORET data also show
that the criterion for protection of human health (50 ug/1) Is ex-
ceeded in only 8.4 percent of the water samples (OWRS, 1980b).
* Supplied by OAQPS.
** Supplied by OSW.
4-4 July, 1982
-------
4.3 Other Exposure Routes
Food constitutes the major source of lead ingestion by the general
population. The nature of food processing may either lower or raise
the concentration of lead in the raw product. Washing lowers the
lead content but packing in metal cans with lead solder seams tends
to increase it. Most of the lead intake from food is attributed to
lead introduced during the canning process. The lead is thought to
be in the form of microscopic pellets of metallic lead which are not
as readily absorbed as are lead salts (OURS, 1980s).
The content of lead in milk may be another major route of exposure,
especially for children who normally consume it in large quantities.
Whole raw cow's milk averages about 9 ug/1 whereas retail milk con-
tains about 40 ug/1. Evaporated milk averages vary but values of 110
to 870 ug/1 have been reported. The higher source of lead in evapo-
rated milk is attributed to lead solder seams and lead particles in
the metal containers (OWRS, I980a).
There is no evidence of lead blomagnlficatlon in the food chain, from
aquatic vegetation to the edible portions of fish and shellfish.
Therefore, fish are not a highly significant source of lead in man's
diet. However, of concern may be the relatively high bioaccumulation
by some saltwater species used for human food (e.g., mussels and
oysters) (OWRS, 1980a).
Adults may acquire clinically significant proportions of lead from
"moonshine," or storage of acidic beverages in improperly glazed
earthenware (OWRS, 1980a).
Occupational exposure to lead may be excessive. Storage battery
plants, primary lead smelters, welding and cutting lead-painted metal
structures, automobile radiator repair, and production of lead-base
paints may lead to excessive lead exposure. Inhalation and hand-to-
mouth transfer are the principal hazards (OWRS, 1980a).
Large numbers of children are exposed to lead from miscellaneous
sources. The major source is lead-base paints in the interior of the
home and in the soil surrounding the homes. Street dust and associ-
ated soil also contain relatively high levels of lead. High levels
of lead in soil near roads can be attributed to the combustion of
gasoline with lead additives. A study conducted in 1972 of lead con-
tent in industrial, agricultural, and residential soils found that
there was approximately 2.7 times as much lead in industrial soil as
in residential soil. Residential soils were found to contain a
slightly higher lead content than agricultural soils. Soil located
alongside heavily traveled highways contain the highest concentra-
tions of lead. A sample of soil taken near an expressway in Chicago
yielded up to 7,600 ppm at distances up to 13.7 meters from the ex-
pressway and 900 ppm up to 45.7 meters (OTS, 1979). These sources
could double the daily blood levels of lead in a young child. Also
children with pica can acquire high levels of lead in the blood
(OWRS, I980a).
4-5 July, 1982
-------
5. DATA BASES
5.1 Chemicals in Commerce Information System (CICIS)
The Inventory was compiled under the authority of Section 8 of TSCA
which requires manufacturers to report to EPA the chemicals imported
and manufactured during calendar year 1977. The Inventory lists the
Chemical Abstract Service (CAS) preferred name for the chemicals,
their respective CAS number (often used for identification purposes),
production site, company name, and volume(s) of production and
import. There is also a Confidential Inventory in which many of these
characteristics are claimed confidential by the manufacturer. In
these instances, the confidential information will not be available in
the public inventory. CICIS can now be accessed through the NIH/EPA
Chemical Information System (CIS - see 5.3). For further information,
contact Gerri Nowack at PTS 382-3568 or Robin Heisler at PTS 382-3557.
5.2 EPA Chemical Activities Status Report (EPACflSR)
EPACASR is an on-line system containing information on EPA's interest
in chemicals. This system includes data on the Agency's regulations
research, and assessments directed toward specific chemicals. EPACASR
is published annually and the data base is updated as information is
received. A searchable subset itemizes NTP/NCI studies and results,
as well as chemicals discussed in the IARC monograph series. (Other
sources are added as appropriate.) Entries identify the statutory
authority, the nature of the activity, its status, the reason for
and/or purposes of the effort, and a source of additional
information. Searches may be made by CAS Number or coded text.
(EPACASR is scheduled to be added to CIS in early 1984.) For further
information, contact Eleanor derrick at FTS 382-3415.
5.3 NIH/EPA Chemical Information System (CIS)
This is a collection of various scientific data bases available
through an interactive computer program. The linking system between
these data files is the Structure and Nomenclature Search System
(SANSS). CIS can also provide a list of non-CIS sources of
information on a chemical of interest. However, these files have to
be accessed individually by either separate on-line systems or in
hard-copy. For further information, contact Dr. Steve Heller at FTS
382-2424.
5.4 Chemical Regulations and Guidelines System (CRGS)
CRGS is an on-line data base which is being developed to provide
information on chemical regulatory material found in statutes,
regulations, and guidelines at the Federal, State, and international
levels. Currently, only the first phase of CRGS/ which encompasses
only source material at the Federal level, is operational. Nation-
wide access to CRGS is available through Dialog. For further
information, contact Doug Sellers at FTS 382-2320.
5-1 October, 1983
-------
5.5 Chemical Substances Information Network (CSIN)
The Chemical Substances Information Network (CSIN) is a
sophisticated switching network based on heterogeneous distributed
data base management and networking concepts. CSIN offers efficient
access to on-line information resources containing data and
information relevant to chemical substances, as well as information
covering other scientific disciplines and subject matters. The
purposes of CSIN are two-fold: first to meet the growing chemical
data and information requirements of industry, academe, government
(Federal and State), public interest groups, and others; and secondly
to reduce the burden on the private and public sector communities when
responding to complex Federal legislation oriented to chemical
substances.
CSIN is not another data base. CSIN links many independent and
autonomous data and bibliographic computer systems oriented to
chemical substances, establishing a "library of systems". Users may
converse with any or all systems interfaced by CSIN without prior
knowledge of or training on these independent systems, regardless of
the hardware, software, data, formats, or protocols of these
information resources.
Information accessible through CSIN provides data on chemical
nomenclature, composition, structure, properties, toxicity, production
uses, health and environmental effects, regulations, disposal, and
other aspects of the life cycle of materials as they move through
society. Currently, seven independent information resources are
accessible through CSIN. They are: National Library of Medicine
(NLM), Chemical Information System (CIS), CAS-On-Line, SDC's ORBIT,
Lockheeds's DIALOG, Bibliographic Retrieval Service (BRS), and the OS
Coast Guard's Hazard Assessment Chemical System (HACS). For further
information contact Dr. Siegel at 202-395-7285.
5.6 EPA Information Clearinghouse
The EPA Information Clearinghouse is a bibliographic data base
composed of over 500 individual data bases and models which contain
monitoring information and statistics on a variety of chemicals. The
individual data bases are maintained for offices within EPA. The
clearinghouse listed 146 citations for lead. For further information,
contact Irvin Weiss at FTS 382-5918.
5_2 October, 1983
-------
6. REGULATORY STATUS (Current as of 9/83)
6.1 Promulgated Regulations
6.1.1 EPA Programs
Clean Air Act (CAA)
o Section 211 - EPA regulates the amount of lead permitted in leaded
gasoline (40CFR80.20). Revised regulations have been issued which
remove the temporary exemption for small refineries effective
July 1, 1983 (47FR49322; 48FR5724; 48FR13428); all must meet a
standard of 1.10 grams of lead per gallon of leaded gasoline. A
maximum level for lead in unleaded gasoline is also in effect
(40CFR79.31).
o Section 109 - A National Ambient Air Quality Standard (NAAQS) has
been issued for lead and its compounds (40CFR50.12).
State implementation plans (SIP) have been adopted (40CFR51,
parts).
o Section 111 - New Stationary Source Performance Standards (NSPS)
have been issued covering particulate emissions from primary lead
smelters (40CFR60.180-.181) and secondary lead smelters
(40CFR60.120-.123). Although lead emissions are not directly
controlled, particulate lead is indirectly limited by these and
other NSPS. NSPS for lead-acid battery manufacture include
explicit limits for lead emissions (40CFR60, Subpart KK) .
Clean Water Act (CWA)
o Section 311 - Twelve lead compounds designated as hazardous
substances(40CFR116.4) are subject to reporting requirements
(reportable quantities, 40CFR117.3) in case of discharge.
o sections 301, 304, 306, and 307 - Lead and its compounds are
listed asToxicPollutants,also known as priority pollutants
(40CFR401.15), and are subject to effluent limitations reflecting
"best available technology economically achievable" {BAT).
Effluent guidelines for lead, including New Source Performance
Standards (NSPS) and/or Pretreatment Standards (PS), have been
issued for all or parts of the following industrial point source
categories:
Inorganic Chemicals (40CFR415)
Iron and Steel Manufacturing (40CFR420)
Glass Manufacturing (40CFR426)
Rubber Processing (40CFR428)
Elec tropla ti ng (4 OCFR413)
Nonferrous Metals Manufacturing (40CFR421 )
Ore Mining and Dressing (40CFR440)
6-1 October, 1983
-------
Porcelain Enameling (40CFR466)
Metal Finishing (40CFR430)
Copper Forming (40CFR468)
o Sections 402 and 404 - Discharged toxic pollutants such as lead
are controlled by requiring permits under the National Pollutant
Discharge Elimination System (NPDES). The Army Corps of Engineers
issue permits for discharge of dredged or fill materials (40CFR122
to 125)
Safe Drinking water Act (SDWA)
o Section 1412 - Establishes interim primary drinking water
standards,including a maximum contaminant level (MCL) for lead
(40CFR141.11).
o Sections 1421 to 1424 - Establishes an underground injection
control (UIC) program to protect underground sources of drinking
water (40CFR146). Requirements and criteria to be used by states
incorporate all hazardous wastes as defined by RCRA (40CFR261),
including lead and its compounds.
Resource Conservation and Recovery Act (RCRA)
o Section 3001 - This section identifies specific hazardous wastes,
waste sources, and criteria for listing waste as hazardous
(40CFR261). Lead and its compounds are designated as toxic wastes
(261.33) and/or hazardous constituents (261, App VIII); total
extractable lead may also characterize waste as hazardous
(EP toxicity, 261.24). The only nonspecfic source of hazardous
waste which contains lead is industrial painting activities
(261.31, App VII). Waste streams containing lead from the
following industries are listed as specific sources of hazardous
waste: pigment production, petroleum refineries, tanning,
explosives, paint manufacturing, ink formulation, and production
of iron, steel, copper, zinc, lead and ferroalloys (261.32, App
VII). [See also "Disposal," Section 8.5 of this document.]
o Sections 3002 to 3006 - Hazardous wastes containing lead are
subjecttofurthercontrol under RCRA. Regulations cover
generators (40CFR262) and transporters (40CFR263) of such waste;
and treatment, storage, and disposal facilities are also subject
to standards (40CFR264 and 265).
Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA)
o Residue tolerances are set for lead arsenate on fruits and
vegetables (40CFR180.194).
o Requirements are given for disposal of lead-based pesticide
residues and containers (40CFR165.7 to .9).
5_2 October, 1983
-------
6.1.2 Programs of Other Agencies
OS HA - Occupational Safety and Health Act
o Section 6 - A permissible exposure limit (PEL) of 50 micrograms
per cubic meter for lead has been established (29CFR1910.1025).
The standard must be achieved through some combination of
engineering controls, work practice plans, and respiratory
protection. Lead exposure in mines is controlled under the limits
adopted by the Mine Safety and Health Administration
(29CFR1910.1000).
CPSC - Consumer Product Safety Act (CPSA)
o Lead-based paint and surfaces covered with lead paint are
regulated under CPSA. Lead-based paint exceeding 0.06 percent
lead and most surfaces coated with same are banned (16CFR1145,
1303, 1500).
HUD - Lead-based Paint Poisoning Prevention Act
o In HUD-associated housing, this Act requires the elimination of
lead-based paint hazards, prohibits use of lead-based paints, and
requires notification of tenants or purchasers of the hazards of
lead-based paints (24CFR35).
DOT - Hazardous Materials Transportation Act
o Regulations concerning the packaging, labeling, and shipping of
hazardous materials, including lead compounds (49CFR171-177,
parts). Amendments incorporate hazardous substances and wastes
regulated by EPA, including lead and its compounds (40CFR116 and
261).
FDA - Federal Food, Drug and Cosmetic Act
o Quality standards for bottled water include a maximum lead
concentration (21CFR103.5).
o Lead is a regulated impurity in a variety of color additives: DSC
Orange Nos. 5, 10, and 11; DSC Green Nos. 3,5 and 6; DSC Red Nos.
21, 22, 27, 28, and 30; DSC Blue No. 2; DSC Yellow No. 10
(21CFR73, 74, 81, and 82).
o Lead is regulated as a food additive in Natamycin (21CFR172.155)
and sucrose fatty acid esters (21CFR172.859).
6-3 October, 1983
-------
6.2 Proposed Regulations
6.2.1 EPA programs
CAA
o New source performance standards (NSPS) have been proposed which
limit particulate matter release. Lead is known to be present in
particulates released from steel plants, electric arc furnaces,
and argon-oxygen decarburization vessels (40FR37338), as well as
from plants that extract or process lead (40FR36859).
CWA
o Effluent guidelines, including NSPS and PS, or revisions to
existing guidelines concerning lead, have been proposed for
various industry point source categories.
Comprehensive Environmental Response, Compensation, and Liability Act
(CERCLA or Superfund)
o CERCLA provides for the liability, compensation, cleanup, and
emergency response for the release of hazardous substances into
the environment. This Act also deals with the cleanup of
hazardous waste disposal sites. (42USC9601}; PL 96-510). EPA is
developing regulations concerning the designation of hazardous
substances, the development of reportable quantities, claims
procedures, and the confidentiality of business records
(46FR54032]. Revisions to the National Contingency plan (NCP) as
required by CEHCLA have been issued in a proposed rule
(47FR109723.
o Lead compounds are hazardous substances under CERCLA and are
subject to regulations developed under Superfund. Although
adjustments to many of the reportable quantities (RQs) have been
proposed, the RQs for lead compounds are still under assessment
and statutory values derived from CWA Section 311 or CERCLA itself
(1 Ib.) apply U8FR23552).
6_4 October, 1983
-------
6.2.2 Programs of Other Agencies
FDA
o In an Advance Notice of Proposed Rulemaking (ANPR), FDA announced
a program to reduce lead levels in canned food. Significantly,
FDA intends to regulate lead as a food additive under section 409
of FCDA and set action levels on lead levels in food
(44CFR51233). A proposed tolerance level for lead in evaporated
milk (39FR42740) is due to be withdrawn and replaced with action
levels.
o Proposal to affirm as Generally Recognized as Safe (GRAS) in corn
sugar, syrup, invert sugar, and sucrose (48FR15270).
o Proposal to regulate lead as an impurity in a color additive for
contact lenses (48FR34946).
Department of Interior
o Under the National Environmental Policy Act, a rule has been
proposed describing areas requiring non-toxic shot for waterfowl
hunting (46FR31030).
6.3 Other Actions
o EPA has designated another equivalent method for the determination
of lead in particulate matter collected from ambient air. The new
method uses Inductively Coupled Argon Plasma Optical Emission
Spectrometry (48FR14748).
o EPA has published a draft of the Revised Air Quality Criteria
Document for Lead (EPA-600/8-83-028A).
6-5 October, 1983
-------
7. STANDARDS AND RECOMMENDED CRITERIA*
7.1 Air
o National Ambient Air Quality
Standard for lead (40CFR50.12).
1.5 ug/m^ yearly
average
7.2
Water
o Hazardous spill rules require
notification of any discharge equal
to or greater than the following
reportable quantities (40CFR117.3):
tetraethyl lead
lead fluoride
other lead compounds
o Maximum Contaminant Level (MCL) of
total lead for drinking water
(40CFR141.11).
100 Ibs
1000 Ibs
5000 Ibs
0.05 mg/1
o Human health water quality criteria 0.05 mg/1
for lead (45FR79318).
7.3
o Effluent limitations (various
industries, 40CFR413 to 440).
Hazardous Waste
see Section 6.1
of this document
7.4
o Solid waste is considered hazardous
if the concentration of lead equals
or exceeds this maximum for extractable
lead (EP toxicity, 40CFR261.24).
Other
5.0 mg/1
o Maximum lead content in gasoline
(47FR49322):
leaded gasoline (40CFR80.20)
unleaded gasoline (40CFR79.31)
o Pesticide tolerances for residues
of lead arsenate (as lead,
40CFR180.194) in:
1.1 g/gallon
0.05 g/gallon
citrus fruits
other fruits and vegetables
1 ppm
7 ppm
* See Appendix A for a discussion of the derivation, use, and limitations of these criteria
and standards.
7-1
October, 1983
-------
o FDA maximum concentration level of
total lead in bottled water
(21CFR103.35).
o CPSC maximum lead content in
consumer paint (16CFR1303).
o HUD definition of lead-based paint
(24CFR35).
o OSHA Permissible Exposure Limit
(29CFR1910.1025).
0.05 mg/1
0.06% by weight
0.5% by weight
0.05
(8-hr TWA)
7-2
October, 1983
-------
8. SPILL OR OTHER INCIDENT CLEAN-UP/DISPOSAL (CONTACT: National
Response Center: 800-424-8802; in the Washington area: 426-2675)
General information pertaining to lead compounds will be presented
first, followed by specific information applicable to the individual
chemicals for which information was available. The term "lead" will
refer to all lead compounds.
8.1 Hazards and Safety Precautions
Lead is a poisonous material which may be fatal if inhaled or ingest-
ed. Contact with some lead compounds may cause burns to skin or
eyes. Fire may produce irritating or poisonous gases. Runoff from
fire control or dilution water may cause pollution.
Tetramethyl lead and tetraethyl lead are flammable liquids which may
be ignited by sparks and flames.
Lead nitrate and lead perchlorate are strong oxidizing agents and
should be kept away from oxldizable materials.
Store in tightly closed containers in well-ventilated areas away from
food products.
Lead nitrate and lead perchlorate should be protected against physi-
cal damage. Store in cool dry place; avoid storage on wood floors.
Separate from combustible, organic or other readily oxidizable mater-
ial. Immediately remove and dispose of any spilled material.
8.2 First Aid
Move victim to fresh air; call emergency medical care. If not
breathing, give artificial respiration. If breathing is difficult,
give oxygen. Remove and isolate contaminated clothing and shoes. In
case of contact with material, immediately flush skin or eyes with
running water for at least 15 minutes.
8.3 Emergency Action
Avoid contact and Inhalation of the spilled cargo. Stay upwind; no-
tify local fire, air, and water authorities of the accident. Evacu-
ate all people to a distance of 200 feet upwind and 1,000 feet down-
wind of the spill. Dam stream to prevent additional movement. Wear
full protective clothing including NIOSH-approved rubber gloves and
boots, safety goggles or face mask, hooded suit, and either a
respirator whose cannister is specifically approved for this
material, or a self-contained breathing apparatus. Care must be
exercised to decontaminate fully or dispose of all equipment after
use.
The "Hazardous Materials 1980 Emergency Guidebook" recommends the
following general procedures for containment and clean-up for lead
spills. Small spills, take up with sand, or other noncombustible
absorbent material, then flush area with water. For small dry
8-1 July, 1982
-------
spills, shovel Into dry containers and cover, move containers, then
flush area with water. Large spills, dike far ahead of spill for
later disposal.
OHM-TADS recommends the following actions: reduce dissipation by
water movement with a physical barrier. Due to low solubility of
material, dredging or bottom vacuum may be effective. Under con-
trolled conditions, chemical treatment is as follows: pump water
into suitable container. Add calcium hydroxide to a pH of 8.5 to
precipitate lead. Filter. Use carbon as a polishing step. For more
details see Envirex Manual EPA 600/2-77-227.
Fire can be extinguished with water in flooding quantities as fog,
foam, dry chemical, or carbon dioxide. If water or foam is used,
contain flow to prevent spread of pollution, keep from drains and
sewers. Remove container from fire area if you can do it without
risk.
In case of tetramethyl lead or tetraethyl lead fire, cool containers
that are exposed to flames with water from side until well after the
fire is out. For massive fire in cargo area, use unmanned hose hold-
er or monitor nozzles. If this is impossible, withdraw from area and
let fire burn.
8.4 Notification and Technical Assistance
Section 103(a) and (b) of the Comprehensive Environmental Response,
Compensation, and Liability Act of 1980 requires persons who release
hazardous substances into the environment in reportable quantities
determined pursuant to Section 102 of the Act to notify the National
Response Center (NRC): 800-424-8802 (Washington, D.C. 426-2675).
A variety of lead compounds are designated as hazardous under the CWA
Section 311; all have reportable quantities of 5,000 Ibs with the
exception of lead flouride and tetraethyl lead which have reportable
quantities of over 1,000 and 100 Ibs respectively: lead acetate,
lead arsenate, lead chloride, lead flouroborate, lead flouride, lead
iodide, lead nitrate, lead stearate, lead sulfate, lead sulfide, and
lead thiocyanate.
For technical assistance, call CHEMTREX (Chemical Transportation
Emergency Center): 800-424-9300. Other sources of technical infor-
mation are (1) the EPA'a Oil and Hazardous Materials - Technical
Assistance Data System (OHM-TADS) contained in the NIH-EPA Chemical
Information System (CIS) which provides information pertinent to
emergency spill response efforts, and (2) the CHRIS System which pro-
vides information on first aid, physical/chemical properties, hazard
assessments, and response methods. Both systems can be accessed
through NRC.
8.5 Disposal
Persons generating more than 1,000 kg of hazardous waste per month,
or spill clean-up residue or debris resulting from the clean-up are
3-2 July, 1982
-------
subject to regulation under RCRA. Such wastes include waste lead as
well as wastes that fail the EP toxicity test, 40CFR261.24, (concen-
tration is greater than 5.0 mg/1).
The following specific waste streams are subject to Subpart D regula-
tions .
(1) Wastewater treatment sludges from the manufacturing formulation
and loading of lead-based initiating compounds.
(2) Dissolved air flotation (DAF) float from the petroleum refining
industry.
(3) Slop oil emulsion solids from the petroleum refining industry.
(4) API separator sludge from the petroleum refining industry.
(5) Tank bottoms (leaded) from the petroleum refining industry.
(6) Emission control dust/sludge from the primary production of
steel in electric furnaces.
(7) Spent pickle liquor from steel finishing operations.
(8) Acid plant blowdown slurry/sludge resulting from the thickening
of blowdown slurry from primary copper production.
(9) Surface Impoundment solids contained In and dredged from surface
impoundments at primary lead smelting facilities.
(10) Sludge from treatment of process wastewater and/or acid plant
blowdown from primary zinc production.
(11) Electrolytic anode slimes/sludges from primary zinc production.
(12) Cadmium plant leachate residue (iron oxide) from primary zinc
productloo.
(13) Emission control dust/sludge from secondary lead smelting.
(14) Solvent washes and sludges, caustic washes and sludges, or water
washes and sludges from cleaning tubs and equipment used in the
formulation of ink from pigments, driers, soaps, and stabilizers
containing chromium and lead.
(15) Waste leaching solution from acid leaching of emission control
dust/sludge from secondary lead smelting,
8-3 July, 1982
-------
9. SAMPLING, ACCEPTABLE ANALYTICAL TECHNIQUES, AND QUALITY ASSURANCE
9.1 Air (CONTACT: Lary Purdue, FTS 629-2665)
A national ambient air quality standard for lead and a reference
method for the determination of lead in suspended particulate matter
collected from ambient air have been promulgated by EPA (40CFR Part
50.12. Appendix G). The standard of 1.5 ug Pb/m3 is an arithmetric
mean averaged over a calendar quarter.
Sampling is accomplished by collecting airborne particulate matter on
a glass-fiber filter for 24-hours using a high-volume sampler. Lead
in the particulate matter is solubilized by extraction with nitric
acid facilitated by heat or by a mixture of nitric and hydrochloric
acid facilitated by ultrasonication.
The lead content of the sample extract is analyzed by atomic absorp-
tion spectrometry using an air-acetylene flame and the 283.3 or 217.0
run lead absorption line. The method has a typical range of 0.07 to
7.5 ug Pb/m3, assuming an upper linear range of analysis of 15 ng
Pb/1 and an air volume of 2,400 m3. Only minor chemical interfer-
ences are reported and no corrections are recommended. Interferences
due to light scattering are overcome instrumentally or by a chela-
cion-excraction technique. The high-volume sampling procedure used
to collect airborne particulate has an interlaboratory relative
standard deviation of 3.7 percent over the range 80 to 125 ug/m3.
The combined extraction-analysis procedure has an average inter-
laboratory relative standard deviation of 7 to 9 percent over the
range 1.5 to 15 mg/1.
9.2 Water (CONTACTS: Theodore D. Martin, FTS 684-7312; or
Gerald D. McKee, FTS 684-7372)
Lead is a Clean Water Act 304(h) parameter and is listed as an inor-
ganic priority pollutant. It is also a drinking water parameter with
a maximum contaminant level of total lead set at 0.05 mg/1. The term
"total lead" is defined as the sum of the concentrations of lead in
both the dissolved and suspended fractions of the sample. Samples
collected for the analyses of total lead are not filtered and must be
preserved with nitric acid to pH <2 as soon as possible, preferably
at the time of collection. When a sample contains suspended material
and is to be analyzed for total lead, a sample digestion step is
required. Dissolved lead is that protion of an unacidifed sample
that will pass through a 0.45 urn membrane filter. Samples to be
analyzed for dissolved lead are preserved with nitric acid to pH <2
after filtration. When a colorioetric, stripping voltammetry, or
chelation/extraction method is to be used for the analysis of dis-
solved or total lead, a sample digestion step is also required to
ensure that the lead is in the proper chemical state and available
for reaction.
There are a variety of approved methods for'lead analysis. The most
commonly used method is atomic absorption spectroscopy (AA). AA
analysis may be conducted by direct aspiration of the sample into an
9-1 July, 1982
-------
air/acetylene flame. For this method the optimum concentration range
for the 283.3 nm absorption is 1 to 20 ntg/1 with an estimated detec-
tion limit of 0.1 mg/1. Chelation/extraction is used to concentrate
and/or separate lead from an interfering matrix and can extend the
working range for direct aspiration downward to less than 0.05 mg/1.
Interlaboratory standard deviations for analysis of lead samples by
flame AA varied from 4.2 to 13.8 percent as the lead concentrations
decreased from 1.57 to 0.026 mg/1; recoveries ranged from 98 to 104
percent. A more sensitive atomic absorption method is the graphite
furnace technique which is often used for analysis of trace amounts
of lead. For every matrix analyzed, verification is necessary to
determine that the method of standard addition is not required.
Hydrochloric acid must be avoided to prevent volatilization of the
lead before atomizatlon. The optimum range for graphite furnace
methods (for 20 ul injection) is 0.005 to 0.100 mg/1 with an esti-
mated detection limit of 0.001 mg/1. Interlaboratory analysis of
samples containing 0.026 and 0.046 mg Pb/1 by the AA-graphite furnace
method yielded standard deviations of 7.7 percent and 13 percent
respectively with recoveries of 102 percent and 103 percent.
In the colorlmetric method, lead reacts with dithizone in chloroform
to form lead dithlzonate. The lead is extracted at a high pH (10 to
11.5) and the absorbance of the cherry-red dlthizonate complex is
measured spectrophotometrically at 510 nm. The analytical range for
this method is 1.0 to 30.0 ug Pb In the sample aliquot used for ex-
traction. In a single laboratory using a surface water matrix spiked
at concentrations of 0.01 mg Pb/1 and 0.026 mg Pb/1, the relative
standard deviations were +6.8 percent and +4.8 percent,
respectively. The recovery at these levels were 98.6 percent and 115
percent, respectively.
In the differential pulse anodic stripping voltammetry method (DPAS-
voltammetry) the sample is digested with nitric acid. After deposi-
tion onto a mercury electrode at constant potential, the lead is
stripped back into solution using differential pulse scanning. The
current is measured and the lead concentration determined using the
standard addition technique. The limit of detection is 0.001 mg/1
and the method is applicable up to 0.1 mg/1 of lead. Samples con-
taining 0.02 to 0.08 mg Pb/1 were analyzed by DPAS-voltammetry in an
interlaboratory study. The standard deviations varied from 20 per-
cent to 12 percent and recoveries ranged from 96 percent to 108 per-
cent.
In response to the improved state-of-the-art of multi-element analy-
sis, a water/wastewater related method which Includes lead has been
promulgated by EPA (FEDERAL REGISTER, 44, p. 69559, December 3,
1979). The revised method (200.7) uses inductively coupled plasma-
atomic emission spectroscopy (ICP-AES). The atomic-line emission
spectra is processed by computer to subtract background and to cor-
rect for any spectral interference. While the estimated instrument
detection limit is 0.04 mg/1 (at 220.3 nm), the optimum working range
for lead by the ICP technique is considered to be from 0.1 mg/1 to
near 1 g/1. In an interlaboratory study, samples containing 0.08,
9-2 July, 1982
-------
and 0.25 mg Pb/1 were analyzed by ICP-AES. The relative standard
deviations were +^14 percent, and +16 percent, respectively and
recoveries at these levels were 100 percent, and 94 percent.
The following table summarizes the approved method with appropriate
references:
LIST OF APPROVED TEST PROCEDURES FOR TOTAL LEAD
Reference Method No.
EPAl
239.1
239.2
200.7
Standard
Methods?
303A or
303B
304
—
ASTM3
D3559-78
(A or B)
— —
uses4
1-3399-78 or
1-3400-78
— -—
Digestion5 followed by
AA-dlrect aspiration
AA-graphite furnace
ICP-AES6
DPAS-Voltammetry D3559-78C
Colorimetrlc (Dithizone) 316B
1. "Methods for Chemical Analysis of Water and Wastes, 1979,"
EPA-600/4-79-020.
2. "Standard Methods for the Examination of Water and Wastewater," 15th
Edition.
3. "Annual Book of Standards," Amer. Society for Testing and Materials, Part
31, Water.
4. "Methods for Analysis of Inorganic Substances in Water and Fluval Sedi-
ments," U.S. Department of the Interior, Geological Survey, Open-file Re-
port 78-679.
5. Sample digestion of the filtrate for dissolved metals, or digestion of
the original sample solution for total metals may be omitted for AA
(direct aspiration or graphite furnace) or ICP analyses provided the sam-
ple has a low COD and meets the following criteria: a) visibly trans-
parent, b) no odor, c) free of particulate matter following acidifica-
tion.
Note: If the sample digestion procedure included in one of the other
approved references is different than an EPA procedure, the EPA procedure
must be used.
6. Inductively Coupled Plasma Optical Emission Spectrometric Method (ICP)
for Trace Element Analysis of Water Wastes; Method 200.7 published by
U.S. EPA, EMSL-Cincinnati.
9-3 July, 1982
-------
9.3 Solid Wastes
Approved methods for lead analysis in solid wastes are given in "Test
Methods for Evaluating Solid Wastes - Physical/Chemical Methods,"
(USEPA/SW-846/May 1980), Method No. 8.56. The sample is digested
with HN03 and analyzed by the flame atomic absorption or graphite
furnace method. Both procedures are similar to the AA methods ap-
proved for lead determination in water.
9.4 Other Samples
A procedure is given for the determination of lead in sediments and
other solids in "Chemistry Laboratory Manual for Bottom Sediments and
Elutriate Testing," (Region V, USEPA, CRL, Chicago; EPA-
905/4-79-014). The dry sediment is digested (HNt^/l^) and analyzed
by either ICP-AES or AA.
Typical methods for lead analysis in a variety of biological and
environmental matrices are summarized in an IARC monograph (IARC,
1980). A review of the various analytical methods used for lead ia
available (see HERL, 1978).
9.5 Quality Assurance (CONTACT: John Winter, FTS 684-7325)
OKD has a full range of Quality Assurance support available which in-
cludes the following items:
• Unknown performance evaluation samples
• Known quality control check samples
These are available to the regions through the Quality Assurance
Branch of EMSL--Cincinnati.
Quality control samples for analysis of airborne lead consisting of
lead deposited on glass-fiber filter strips are available from the
Performance Evaluation Branch, Quality Assurance Division (MD-77),
EMSL/USEPA, Research Triangle Park, North Carolina 27711 (Telephone:
FTS: 629-2188). Specific guidance for a Quality Control Program for
the TSP Reference Method and the Lead Reference Method can be found
in the Quality Assurance Handbook for Air Pollution Measurement Sys-
tem, Volume II, Section 2.09, EPA-600/4-77-027a, May 1977.
9-4 July, 1982
-------
REFERENCES
The major references used in preparation of this document are listed below.
EPA references are listed by EPA Office of origin and the year of publica-
tion. For further Information refer to contacts given throughout this docu-
ment or contact the relevant EPA offices listed at the end of this section.
(HERL, 1978)
(IARC, 1980)
(IERL, 1979)
(NAS, 1972)
(ORD, 1977)
(OTS, 1979)
(OWRS, 1979)
(OWRS, 1980a)
(OWRS, 1980b)
(Weast, 1979)
(WHO, 1977)
Reviews of the Environmental Effects of Pollutants: VII
Lead,EPA-600/1-78-0029,Health Effects Research Lab,
Cincinnati, OH (1978).
IARC Monographs on the Evaluation of the Carcinogenic
Risk of Chemicals to Humans, Vol. 23, International Agen-
cy for Research on Cancer, Lyon (1980).
Status Assessment of Toxic Chemicals; Lead, EPA-660/
2-79-210h, Industrial Environmental Research Lab, Cin-
cinnati, OH (1979).
Lead; Airborne Lead in Perspective, National Academy of
Sciences, Washington, DC (1972).
Air Quality Criteria for Lead. EPA-600/3-77-017, Office
of Research and Development (1977).
Health and Environmental Impacts of Lead - An Assessment
of a Need for Limitations, EPA-560/2-79-001. Office of
Toxic Substances (1979).
Water-Related Environmental Fate of 129 Priority Pollut-
ants, EPA-440/4-79-029a. Office of Water Regulations and
Standards (1979).
Ambient Water Quality Criteria for Lead. EPA 440/5-80-
057, Office of Water Regulations and Standards (1980).
Strategy for Controlling the Environmental Exposure to
Lead, EPA-Draft, Office of Water Regulations and Stan-
dards (1980).
Handbook of Chemistry and Physics, 59th edition, The
Chemical Rubber Co., R.C. Weast, ed. (1979).
Environmental Health Criteria 3; Lead, World Health
Organization, Geneva (1977).
R-l
July, 1982
-------
OFFICE CONTACTS
The EPA Offices and Divisions that are listed below may be contacted for more
information relating to the indicated sections of this document. While these
offices are, in many cases, the offices of origin for the data included in
this paper, the personal contacts given throughout this document should be
contacted first. Unless otherwise noted, the offices listed are situated in
Headquarters, Washington, D.C., and the telephone numbers given are FTS
(Federal Telecommunications System) numbers. For commercial telephone calls
to Headquarters which are not placed on FTS, area code 202 must be used.
Other commercial numbers are noted for the office contacts located outside
Washington, D.C.
HEALTH AND ENVIRONMENTAL EFFECTS (Section 2)
Office of Health and Environmental Assessment (OHEA)
Environmental Criteria and Assessment Office:
Cincinnati, OH 684-7531 (513-684-7531)
Research Triangle Park 629-2266 (919-541-2266)
Carcinogen Assessment Group 755-3968
Office of Drinking Water (ODW)
Health Effects Branch 472-6820
Office of Toxic Substances (OtS)
Health and Environmental Review Division 382-4241
Environmental Research Laboratory
Duluth, Minn., Region V 783-9550 (218-727-6692)
ENVIRONMENTAL RELEASES AND EXPOSURE (Sections 3 and 4)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Water Regulations and Standards (OWRS)
Monitoring and Data Support Division 426-2503
Office of Toxic Substances (OTS)
Exposure Evaluation Division 382-3873
Assessment Division 382-3442
R-2 July, 1982
-------
DATA BASES (Section 5)
Office of Toxic Substances (OTS)
Management Support Division 382-3546
REGULATORY STATUS, STANDAHDS, AND CRITERIA (Sections 6 and 7)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Drinking Water (ODW)
Criteria and Standards Division 472-5016
Office of Water Regulations and Standards (OWRS)
Criteria and Standards Division 755-0100
Effluent Guidelines Division 426-2571
Office of Solid Waste (OSW)
State Programs and Resources 755-9107
Recovery Division
SPILL CLEAN-UP AND DISPOSAL (Section 8)
NOTE: For Emergencies call the National Response Center at 1-800-424-8802
(1-800-426-2675 from the Baltimore/Washington area),
Office of Emergency and Remedial Response (OERR)
Emergency Response Division 245-3045
Oil and Hazardous Materials Spills Branch
Edison, NJ; Region II 340-6634 (201-321-6634)
Office of Solid Waste (OSW)
Hazardous and Industrial Waste Division 755-9187
R-3 July, 1982
-------
ANALYTICAL TECHNIQUES (Section 9)
Environmental Monitoring Systems Lab (EKSL)
Air Analysis
Research Triangle Park, NC 629-2454 (919-541-2454)
Water Analysis
Cincinnati, OH 684-7311 (513-684-731L)
Waste Analysis
Las Vegas, NV 545-2137 (702-798-2137)
GENERAL IPP COMMENTS, CORRECTIONS, OR QUESTIONS
Office of Toxic Integration
Chemical Information and Analysis Program 382-2249
R_4 July, 1982
-------
Mercury
-------
MERCURY
Table of Contents _ , __ Page
Physical/Chemical Properties and Chemiatry 1-1
Properties 1~1
Chemistry and Environmental Fate/Transport 1-1
Effects Information 2-1
Health Effects 2-1
Environmental Effects 2-2
Other Effects 2-3
Environmental Release 3-1
Exposure *"1
Air Exposure 4-2
Water Exposure 4-2
Other Exposure Routes 4-3
Data Bases 5-1
Chemicals in Commerce Information System (CICIS) 5-1
EPA Chemical Activities Status Report (EPACASR) 5-1
NIH/EPA Chemical Information System (CIS) 5-1
Chemical Regulations and Guidelines System (CRGS) 5-1
Chemical Substances Information Network (CSIN) 5-2
EPA Information Clearinghouse 5-2
Regulatory Status 6-1
Promulgated Regulations 6-1
Proposed Regulations 6-3
Other Actions 6-3
July, 1982
-------
Standards and Recommended Criteria 7-1
Air 7-1
Water 7-1
Hazardous Waste 7-1
Other 7-1
Spill or Other Incident Clean-up/Disposal 8-1
Hazards and Safety Precautions 8-1
First Aid 8-1
Emergency Action 8-1
Notification and Technical Assistance 8-1
Disposal 8-2
Sampling, Acceptable Analytical Techniques, and Quality Assurance 9-1
Air 9-1
Water 9-1
Solid Wastes 9-2
Other Samples 9-2
Quality Assurance 9-3
References and Office Contacts &~1
July, 1982
-------
MERCURY
1. PHYSICAL/CHEMICAL PROPERTIES AND CHEMISTRY
1.1 Properties
Mercury Is used In many industrial processes and commercial products
because of its unique physical/chemical properties. Elemental mer-
cury is a dense, silver liquid at room temperature with excellent
electrical conductivity, chemical stability, and alloying ability.
Mercury and many of its organic derivatives are relatively volatile
and most inorganic mercury compounds decompose upon heating to yield
mercury vapor. Some mercury compounds will also degrade to elemental
mercury due to the action of sunlight. Biological transformations of
mercury, coupled with its volatility, enhance both the toxicity and
environmental mobility of mercury (IERL, 1979; WHO, 1976).
Most mercury is used in metallic form in various electrical products
(e.g., alkaline batteries and fluorescent bulbs) and in the electro-
lytic production of chlorine and sodium hydroxide (chlor-alkali
industry). The cytotoxic properties of organomercurials also led to
their use as preservatives in Pharmaceuticals, paints, and other pro-
ducts, although less so in recent years. The high toxicity of mercu-
ry and its organic and Inorganic derivatives has resulted in strin-
gent regulations to control contamination. While most metallic mer-
cury used is imported, a variety of mercury compounds are produced
domestically; Table 1 lists the properties and uses of various mercu-
ry derivatives (IERL, 1979).
1.2 Chemistry and Environmental Fate/Transport
Mercury (Hg) can exist in three oxidation states: elemental, mercur-
ous (Hg+l), and mercuric (Hg+2). Most common inorganic mercurials
and essentially all organic mercury compounds contain divalent mercu-
ry. Organomercurials may contain one or two covalent carbon-mercury
bonds (e.g., CH3-Hg-Cl or CH3-Hg-CH3). An important species of envi-
ronmental significance owing to its toxicity and tendency to bioaccu-
mulate is the methylmercury ion (C^Hg"1"). Mercury compounds are
highly reactive and can form stable complexes with various organic
ligands found in proteins (e.g., sulfhydryl groups) and nucleic
acids. The old name "mercaptan" (mercury seizing) for sulfhydryl
compounds (-SH) stems from their great affinity for mercury (WHO,
1976; OWRS, 1979).
The atmosphere plays a dominant role in the transport of mercury,
usually in the form of mercury vapor. Although natural degassing is
the primary source of mercury air emissions, the use and disposal of
mercury products and fossil fuel combustion are also significant
sources. Mercury is removed from the atmosphere primarily by partic-
ulate fallout or precipitation (OWRS, 1980). According to various
estimates, the residence time for mercury in the atmosphere varies
from 6 to 90 days; a value of 11 days is currently accepted as most
authoritative (NAS, 1978).
1-1 July, 1982
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TABLE 1: PROPERTIES OF MERCURY COMPOUNDS
Chemical Name
and Formula
Mercury
Hg
Mercurous
chloride
HgCl
Mercuric
acetate
Hg(CH3COO)2
Mercuric
chloride
HgCl2
Mercuric
oxide , red
HgO
Mercuric
sulfide, red
HgS
CAS Number Mp Bp
and Synonyms (aC) (°C)
7439976 -39 356
Quicksilver v.p. 0.002mm
(25°)
7546307 400
Mercury (I) sub.
chloride;
calomel
1600277 178
Acetic acid, dec.
mercury (2+)
salt
7487947 276 302
Mercury (II)
chloride;
corrosive
sublimate
1344452 500
Red precip- dec.
itate
1344485 584
vermillion sub.
Water Solubility
(per liter)
0.08 mg (30°C)
(airfree water)
Lipid soluble
2 mg (25°C)
250 g (10°C)
69 g (20°C)
Also sol . in
org. solv.
53 mg (25°C)
0.010 mg (18°C)
Properties
and Uses
Dense (d25 13.5 g/cm^)
silver liquid. Used
in chlor-alkali in-
dustry and In elec-
trical apparatus.
Dlsproportionates
readily to Hg and
HgCl2. Used in
standard electrodes.
Used in manufacture
of mercurials,
catalyst.
Yields slightly acid
solution upon dis-
solution; used as
fungicide and insect-
icide .
Also exists in yellow
form. Decomposes
thermally or photo—
chemically to Hg +02.
Also exists as black
metas table form.
Mineral form of HgS
(cinnabar) is the
major mineral source.
Used in pigments.
-------
TABLE 1: PROPERTIES OF MERCURY COMPOUNDS (cont.)
Chemical Name
and Formula
Dime thylmer cur y
(CH3)2 Hg
EthyLmercuric
chloride
C2H5HgCl
Phenylmer curie
acetate
C6H5HgCH3COO
CAS Number Mp Bp
and Synonyms ("C) (°C)
593748 — 96
Mercury, v.p. 20mm
dimethyl (20°)
107277 193 sublimes
Mercury , at 40°
chloroethyl-
62384 149
Mercury
(acetato)
phenyl-; PMA
Water Solubility
(per liter)
2.5 g (20°)
Also sol . in
org. solv.
1 mg (18°)
Also sol . in
org . solv .
2 g (20°)
Also sol. in
org. solv.
Properties
and Uses
Flammable , volat lie ,
and toxic. Environ-
mental contaminant
produced together
with monomethyl
mercury in bottom
sediments .
Highly toxic; absorbed
through skin. Fung-
icide .
Preservative , herb-
icide , and fungicide .
Available in a var-
iety of other organic
salts .
I
OJ
Source: (Stokinger, 1962)
\o
00
ro
-------
The adsorption of mercury by sediments and subsequent biotransforma-
tion are the two most important processes determining the fate of
mercury in water. While the elemental metal is essentially insoluble
in water, the presence of oxygen and organic substances facilitates
oxidation to more soluble mercuric salts. The mild reducing condi-
tions in anaerobic sediments can cause mercury to precipitate as the
sparingly soluble sulfide (HgS). Mercury compounds are released from
sediments through methylation by bacteria to form methylmercury and,
to a lesser extent, dimethylmercury, This methylation process could
enhance the evaporative Loss of mercury as dimethylmercury from
aquatic systems. More importantly, the lipophilic nature of
methylmercurials permits them to rapidly cross body membranes.
Consequently, even low concentrations of methylmercury produce
dangerous accumulations in fish and other aquatic biota (OURS,
1980a).
Although most of the mercury released due to human activity goes to
landfills, little is known about the fate of mercury lost to land
areas. Mercuric compounds bind strongly to humic substances and the
affinity of mercury for organic matter retards leaching. However,
mercuric compounds may be biotransformed to different, more mobile
forms of mercury. Thus, methylation by soil microorganisms can
produce methylmercurials, and certain bacteria in soil can convert
Hg+2 to elemental mercury by a bioreductive process. The reduction
of ionic mercury in soils (by either chemical or microbiological
processes) may be a major mechanism for natural degassing of mercury
vapor to the atmosphere (NAS, 1978; WHO, 1976).
July, 1982
-------
2. EFFECTS INFORMATION
2.1 Health Effects (CONTACT: Jerry Stara, FTS 684-7531)
2.1.1 Acute Toxicity
Acute mercury Intoxication following oral intake of inorganic mercury
salts is characterized by paresthesla, metallic taste, abdominal
pain, nausea and vomiting, diarrhea, salivation, and upper gastroin-
testinal tract edema (Drelsbach, 1977). Large doses result in kidney
damage and may lead to death. The lethal oral dose in man for mercu-
ric chloride (HgCl2) ls estimated to be 1 to 4 grams (OWRS, 1980a).
Organic mercury compounds, particularly alkyl derivatives such as
methylmercury salts, are highly toxic and can produce ataxia, dysar-
thria, constricted visual fields, and altered plantar reflexes. Der-
matitus can also result from dermal contact with or ingest ion of
alkyl mercurials (OWRS, 1980a).
Acute mercurial pneumonitis results from exposure to high concentra-
tions of mercury vapor (above 1 mg/m3). The condition is character-
ized by symptoms similar to those observed for ingestlon of inorganic
mercury. Death'from lung edema is also possible (OWRS, 1980a).
2.1.2 Chronic Toxicity
Neurotoxicity—The critical organ system in chronic exposure appears
to be the central nervous system (CNS), although kidney damage is
also observed. The onset of chronic poisoning may be slow; the early
symptoms are usually a progressive numbness of the extremities, lips,
or tongue, and tremors. With increasing exposure, symptoms progress
to malaise, muscular weakness, ataxlc gait, clumsiness, slurred
speech, deafness, and impaired vision, as well as numerous psycholog-
ical effects. Generally, severe neurological symptoms are not re-
versible. The onset of CNS effects are noted at 200 ug Hg/day for a
70 kg human (OWRS, 1980a).
Carcinogenicity—Little Information has been published on animals and
none on humans that Indicates any significant carcinogenic potential
for mercury compounds (OWRS, 1980a).
Mutagenicity—No assessment of mutagenicity in systems such as the
Ames salmonella assay has yet been made and data concerning genetic
and reproductive effects of mercury compounds are meager. Methylmer-
cury is a weak mutagen in Drosophila and can interfere with chromo-
some segregation in plants and animals. The significance of these
and other results for human health remains unclear, and the effects
of methylmercury on human reproduction and chromosomes should be
investigated further. No evidence has been published concerning the
mutagenicity of inorganic mercury salts in humans (OWRS, 1980a).
Teratogenicity—Psychomotor retardation due to fetal exposure to
methylmercury is well documented. Although brain damage due to pre-
natal exposure occurs, no anatomical defects have been reported in
2-1 July, 1982
-------
humans. In animals prenatal exposure to methylmercury has resulted
in cleft-palates and reduced birth weights, as well as brain damage.
Teratological effects of inorganic and metallic nercury have been
reported in animals, but little is known about prenatal effects of
these mercury forms in humans (OWRS, L980a).
2.1.3 Absorption, Distribution, and Metabolism
The absorption and toxicity of mercury and its compounds varies with
the chemical species involved and the exposure route. Toxicity by
ingestion in humans increases in accordance with the extent of
absorption through the gastrointestinal tract, i.e., metallic mercury
< inorganic salts < nethylmercurials. Metallic mercury vapor and
alkylmercury compounds are absorbed in the human lung with
approximately 80% efficiency. Absorption of mercurials through the
skin is reported to occur but is not usually a significant exposure
route (OWRS, 1980a).
Methylmercury (i.e., CH3-Hg+) is of special concern because it is
readily absorbed, crosses the blood-brain barrier, and is eliminated
from the human body more slowly than other mercurials. The metabo-
lism of elemental mercury is complex and is thought to proceed as
follows. After inhalation of mercury vapor and absorption into the
bloodstream, the mercury is oxidized (to Hg+2). However, despite
this rapid oxidation, some elemental mercury reaches the blood-brain
barrier and rapidly crosses into brain tissue. Subsequent oxidation
in the tissue then traps the mercury in toxic form (Hg+2) and leads
to cumulative neurological damage (WHO, 1976).
Due to their lipid solubility, both methylmercury and elemental mer-
cury are readily transferred from mother to fetus across the placen-
ta. Thus, these forms of mercury pose special hazards to developing
embryos and fetuses (WHO, 1976).
The presence of selenium is reported to reduce the toxic effects of
methylmercury. The mechanism of the protective effect of selenium is
unclear; selenium appears to immobilize methylmercury, but does not
speed elimination. Vitamin E is also reported to provide some
protection from methylmercury toxicity (NAS, 1978).
2.2 Environmental Effects (CONTACT: Howard McCormlck, FTS 783-9548
John Gentile, FTS 838-4843)
2.2.1 Aquatic Effects (OWRS, 1980a)
Virtually any mercury compound entering water can become a bioaccum-
ulation hazard due to conversion to methylmercury. Aquatic organisms
absorb and magnify methylmercury at each trophic level of the food
chain. Therefore, mercury pollution in water can be a serious hazard
to humans through ingestion of fish or shellfish containing methyl-
mercury. Among the factors which affect aquatic toxicity are: tem-
perature, salinity, pH, water hardness, and interactions with other
chemicals.
2-2 July, 1982
-------
Acute Toxicity—In fresh water the reported 96-hour LC50 values for
inorganic mercury vary from 0.02 ug/1 to 2,000 ug/1 among aquatic
species. For rainbow trout, the most acutely sensitive fish tested,
methylmercury is 10-fold more toxic than inorganic mercury. In
general, however, data for methylmercurials are limited.
Salt water animals appear to be much less sensitive to mercury, with
LC5Q values for inorganic mercury varying from 3.5 ug/1 to 1680
ug/1. Molluscs and crustaceans are more sensitive than fishes to the
acute toxic effects of mercury.
Chronic Toxieity—Available chronic data indicate that methylmercury
is the most chronically toxic mercury compound tested. Chronic
values for Daphania magna and brook trout are 1.0 and 0.52 ug/1 re-
spectively. The acute/chronic ratios for sensitive species in fresh-
water and saltwater are both approximately 3.0 for inorganic mercury.
Cold-blooded species, such as fish, retain mercury for long periods;
i.e., elimination half-times for methylmercury for fish and crusta-
ceans are 1 to 3 years. Mercury and its compounds elicit a variety
of sublethal responses in aquatic organisms, including loss of appe-
tite, abnormal development, reduced growth and reproduction, blind-
ness or "pop-eyes," loss of nervous control, and tissue damage. Num-
erous studies claim a degree of acclimation to low levels of mercury
by various species.
Aquatic Plants—Freshwater plant toxicity values of methylmercury
vary widely; effects are observed at concentrations as low as 4.8
ug/1. In general, freshwater plants are relatively Insensitive to
inorganic mercury, and more sensitive to methylmercurials.
Reductions in saltwater algae growth were reported to occur at mer-
cury (HgCl2) levels ranging from 10 to 160 ug/1. The toxicity of
organomercurials to saltwater plant life has not been studied ade-
quately.
Water Quality Criteria*—The criteria to protect freshwater aquatic
life are 0.20 ug/1 as a 24-hour average, with a maximum limit at any
time of 4.1 ug/1. The corresponding criteria for saltwater species
are 0.10 ug/1 for the 24-hour average and a maximum level of 3.7
ug/1.
2.2.2 Other Effects (OWRS, 1980a)
The mercury burdens in terrestrial mammals usually are directly re-
lated to diets and are low compared to marine mammals. Herbivores
have the lowest mercury levels, while carnivores that prey on aquatic
organisms have the highest body burdens**. Non-fish-eating animals
* 46FR40919 (correction to 45FR79318)
** It should be recognized that carnivores other than those that prey upon
aquatic organisms may be contaminated if they consume carnivores that feed
directly on fish or other aquatic organisms.
2-3 July, 1982
-------
and birds usually concentrate less than 0.02 parts per million (ppm)
of mercury. Levels of methylmercury in plants are usually extremely
low, with the exception of plants grown on contaminated soil or from
mercury-created seed stock.
Bioconcentration—Due to the concern over dangers to human health
from eating mercury-containing fish, mercury bioaccumulation has been
well studied in aquatic environments. Methylmercury is readily
absorbed by fish both from food and through the water. Due to the
difficulty fish have in eliminating methylmercury, bioconcentration
factors (BCF) for mercury can become extremely high.
Equilibrium BCF values vary from 12,000 to 63,000 for methylmercury
in freshwater fish. A BCF value of 40,000 has been reported for
methylmercury in oysters.
2-it July, 1982
-------
3. ENVIRONMENTAL RELEASE (OWRS, 1980b, 1980c)
(CONTACT: Michael Slimak, FTS 426-2503)
Approximately 1660 kkg of mercury were used in the U.S. in 1978, down
from the 1976 level of 2230 kkg. Table 2 lists both the uses of mer-
cury and its releases to the environment by media. The year 1976 was
selected for the use/release analyses because it was the most recent
year for which a complete set of data was available. The release
data are only crude estimates and have not been verified by sampling
and analysis.
Electrical products such as dry-cell batteries, fluorescent light
bulbs, switches, and other control equipment account for 50% of mer-
cury used. Mercury is also used in substantial quantities in elec-
trolytic preparation of chlorine and caustic soda (chlor-alkali
Industry, mercury cell process; 25%), paint manufacture (12%), and
dental preparations (3%). Lesser quantities are used in industrial
catalyst manufacture (2%), pesticides manufacture (1%), general labo-
ratory use (1%), and Pharmaceuticals (0.1%).
Consumer use and disposal of products containing mercury eventually
release more mercury to the overall environment than do manufacturing
processes. Only 2% of the mercury released due to human activities
goes directly to surface waters. A large proportion (72%) of that
which is discharged goes to landfills and most of the remainder goes
to air. Only 1% goes to or through POTVs.
While over 60% of the mercury consumed in the U.S. in 1978 has been
or will be disposed of to landfills, relatively little is known about
the movement of mercury in landfills. There is general recognition
that mercury originating in other media is quite mobile in the envi-
ronment due to a cycle of deposition In sediments or soil, followed
by chemical interactions and/or revaporization.
Natural releases of mercury to the U.S. environment are substantial
although there is considerable disagreement on the reliability of
current estimates and the relative importance of natural contribu-
tions. Air emissions due to outgassing of soils and rock strata are
estimated to total approximately 1020 metric tons per year (150% of
man-made air emissions). Direct aquatic discharges due to mercury in
groundwater and non-urban runoff are estimated to total approximately
190 metric tons per year (250% of the comparable man-made contribu-
tion).
3.1 Air Releases (CONTACT: Dave Patrick, FTS 629-5645)
Significant Sources—The following stationary sources have been found
to contribute significant amounts of mercury emissions to the ambient
air.
• Mercury-cell chlor-alkali plants (SIC 2812)
• Primary mercury smelting (SIC 3339)
• Sewage sludge incineration (SIC 4953)
3-1 July, 1982
-------
TABLE 2: CONSUMPTION OF MERCURY AND ANTHROPOGENIC SOURCES TO THE ENVIRONMENT
I. Uses of Mercury
A. Electrical products
B. Chlor-alkali plants
C. Paints
D. Dental preparations
E. Industrial catalysts
F. Pesticides
G. General laboratory
H. Other
II. Releases to Environment
A. Land Discharges
1. Electrical products
2. Chlor-alkali plants
3. Fertilizer
4. From POTW
5. Paint applications
6. Industrial catalysts
7. Pesticides
8. Dental preparations*
9. Fossil fuel combustion
10. Cu, Zn, and Pb smelting
11. General laboratory
12. Other
B. Airborne Emissions
1. Paint applications
2. Fossil fuel combustion
3. Electrical products
4. Cu, Zn, and Pb smelting
5. From POTW
6. Chlor-alkali plants
7. Other
kkg/yr
1836
880
530
190
50
50
40
20
50
10
5
1
10
kkg/yr
650
200
180
150
50
40
20
10
(kkg/yr and
2
kkg/yr
1120
550
270
70
40
20
20
140
% of
Discharges
to Land
48
29
10
3
3
2
1
3
0.5
<0.5
<0.5
0.5
% of
Emissions
to Air
31
28
23
8
6
3
2
%)
I of Total
Uses
50
25
12
3
2
1
1
6
% of
Total
Releases
72
34
21
7
2
2
2
1
2
<1
<1
<1
a
% of
Total
Releases
25
8
7
6
2
1
1
-------
TABLE 2; CONSUMPTION OF MERCURY AND ANTHROPOGENIC SOURCES TO THE ENVIRONMENT
(cont.)
II. Releases to Environment (continued)
kkg/yr
C. Aquatic Discharges 75
1. Industrial Discharges 55
a. Paint applications 20
b. Electrical products 20
c. Dental preparations** <5
d. Fossil fuel combustion 5
e. Cu, Zn, and Pb smelting 5
2. POTWs** 20
% of
Industrial
Discharge
to Water
36
36
9
9
9
•••
% of
Total
Releases
3
2
1
** Although approximately two-thirds of the nation is served by POTWs, this
calculation assumes a tendency toward urban location of dental offices.
Therefore, a much higher level of treatment (>90%) is a more appropriate
assumption. Dental preparations then account for 15 kkg/yr discharged to
POTWs.
Source: Environmental Material Balance for Mercury, draft report, OWRS (1980)
with revision of dental preparations value by OWRS.
3-3
July, 1982
-------
4. EXPOSURE ROUTES
Mercury occurs naturally in many rock strata and soils at trace
levels (less than 1 ppm). Because mercury Is very volatile, a large
amount of mercury vapor enters the atmosphere from outgassing of
soils or rock, from fossil fuel combustion, and from various indus-
tries. A significant percent of this vapor is quickly adsorbed to
very fine particulates which later wash out or fall out onto soils,
pavements, or surface waters. As a consequence, virtually all sur-
face and ground water contain very low levels of mercury (less than 1
ppb average) except in cases of improper management of landfills (See
4.2) (OURS, 1980b).
Consistent with this is the pattern of increased levels of mercury in
the vicinity of large stationary emission sources which gradually
diminish to background within 10-15 kilometers. However, calcula-
tions indicate that nowhere near all of the emitted mercury has been
deposited within a 15 kilometer radius. No good estimates of the
exact percentage sorbed on particulates in air have been reported.
The average life-times reported for mercury vapor in air have ranged
from 5 to 90 days but the most authoritative recent figure appeared
to be 11 days. Concentrations of mercury in air in rural areas are
usually 1-5 ng/m3 while urban concentrations average from 12-13
ng/m3 (OWRS, 1980b).
Many mercury-containing consumer products end in landfills (along
with large amounts of chlor-alkali sludge). Since many landfills are
not well designed (e.g., acid environment, location over porous or
non-clay deposits), some further movement of mercury to the aquatic
environment may occur (OWRS, 1980b).
At present, mercury contamination of ambient air, drinking water, and
soil presents little risk to the general U.S. population. The prim-
ary route of human exposure to mercury appears to be through eating
fish or shellfish. The World Health Organization (WHO) has recom-
mended that weekly Intake be limited to less than 200 ug of methyl-
mercury and less than 300 ug total mercury based on dietary intake.
Human intake of total mercury from food in the U.S. typically ranges
from 35 to 100 ug/week, and Inhalation exposure in general ranges
from 10 to 20 ug/week. Average ingestion of total mercury from
drinking water is less than 7 ug/week, for a total of 50 to 130
ug/week. Highest exposure is very likely attained by dentists
(300-3000 ug/week, by Inhalation) and a small subpopulation who
derives most of Its diet from fish (more than 700 ug/week). Several
other occupational groups are also at somewhat higher risk than the
general population as are pregnant women and developing embryos.
(The WHO permissible levels were based on clinical observations and
should not be equated with threshold levels. Other, more subtle
effects such as behavioral or intellectual deficits might not have
been detectable by the procedures used.) (WHO, 1976).
4-1 July, 1982
-------
4.1 Air Exposure* (CONTACT: Dave Patrick, FTS 629-5645}
Elemental mercury may be inhaled as a vapor. This vapor may be the
result of evaporation of elemental mercury or as part of an indus-
trial process.
Major sources of exposure are:
• Mercury-cell chlor-alkali plants:
hydrogen and end box ventilation
gas streams; cell room floor
• Processing mercury ores: from
rotary kilns and the condenser
• Emissions from a sewage sludge
incinerator
4.2 Water Exposure
Analytical data obtained by the U.S. Geological Survey at its Nation-
al Stream Quality Accounting Network (NASQAN) stations indicate that
no significant changes have occurred in mercury concentrations In
surface waters for the U.S. in general between 1974 and early 1980,
although small variations in average concentrations have occurred
from year to year. On the other hand, 1979 STORET data indicate that
mercury levels in surface waters at a number of locations are above
the threshold for deleterious, but sublethal, effects for "most sen-
sitive" aquatic species. However, lŁ$Q values for "most sensitive"
species are generally more than 10 times the average river basin con-
centrations. Fish-eating wildlife living near contaminated waters
may be at significant risk due to bioaccumulation of mercury in fish
(OWRS, 1980b).
Results of a nationwide reconnaissance of mercury in U.S. 'Waters
(Department of Interior) show that with few exceptions the mercury
content of groundwater samples was below the level of detection (0.1
ug/1). Hazardous waste incidents, however, have resulted in signifi-
cantly higher levels in certain local situations. Major uses of
mercury, which generate mercury-containing solid waste residuals,
include use; as the cathode in the electrolytic preparation of chlo-
rine and caustic soda, In electrical apparatus, in industrial and
control instruments, in general laboratory applications, in dental
amalgams, and in anti-fouling and mildew-proofing paints.**
* Supplied by the Office of Air Quality Planning and Standards.
** Supplied by the Office of Solid Waste.
4-2 July, 1982
-------
4.3 Other Exposure Routes
The primary route of human exposure appears to be through the eating
of fish or shellfish (WHO, 1976).
In foodstuff other than fish and fish products, the concentrations of
mercury are so low as to be near or below the limit of detection by
the analytical methods used. In the United States most foodstuffs
have total mercury levels below 20 ng Hg/g. Due to the uncertainties
in these numbers, it is impossible to calculate average daily intakes
for non-fish food in the United States. These findings are
consistent with the knowledge that non-fish-eaters have the lowest
blood concentration of mercury (OWRS, 1980a).
The average concentration of mercury in most fish is less than 200
ng/g and nearly all the mercury in fish muscle is in the form of
methylmercury compounds. Large carnivores like swordfish can exceed
1,000 ng/g. Canned tuna samples Indicated an average total mercury
concentration of about 250 ng/g. In heavily polluted areas concen-
trations ranging over 20,000 ng/g have been reported. Also, the
older the fish the higher the mercury concentration. Fish that are
carnivorous and at the end of a food chain have the highest concen-
trations. Therefore, freshwater fish like the northern pike and
oceanic fish such as the shark and swordfish have elevated mercury
levels compared to other fish. Marine mammals may obtain levels in
the order of 340,000 ng/g in their livers (OWRS, 1980a).
4-3 July, 1982
-------
5. DATA BASES
5.1 Chemicals in Commerce Information System (CICIS)
The CICIS Inventory was compiled under the authority of Section 8 of
TSCA, which requires manufacturers to report to EPA the chemicals
imported and manufactured during calendar year 1977. The Inventory
lists the Chemical Abstract Service (CAS) preferred name for the
chemicals, their respective CAS number (often used for identification
purposes), production site, company name, and volume(s) of production
and Import. There is also a Confidential Inventory In which many of
these characteristics are claimed confidential by the manufacturer.
In these Instances, the confidential information will not be
available on the public inventory. CICIS can now be accessed through
the NIH/EPA Chemical Information System (CIS - see 5.3). For further
information, contact Gerri Nowack at FTS 382-3568.
5.2 EPA Chemical Activities Status Report (EPACASR)
EPACASR is an on-line system containing Information on EPA's interest
in chemicals. This system includes data on the Agency's regulations,
research, and assessments directed toward specific chemicals.
EPACASR is published annually and the data base is updated as
Information is received. A searchable subset itemizes NTP/NCI
studies and results, as well as chemicals discussed in the IARC
monograph series. (Other sources are added as appropriate.) Entries
identify the statutory authority, the nature of the activity, Its
status, the reason for and/or purpose of the effort, and a source of
additional information. Searches may be made by CAS Number or coded
text. For further information contact Eleanor Merrick at FTS
382-3415.
5.3 NIH/EPA Chemical Information System (CIS)
This Is a collection of various scientific data bases available
through an interactive computer program. The linking system between
these data files is the Structure and Nomenclature Search System
(SANSS). CIS can also provide a list of non-CIS sources of informa-
tion on a chemical of interest. However, these files have to be
accessed individually by either separate on-line systems or in hard-
copy. For further information contact Delores Evans at FTS 382-3546
or Irv Weiss at FTS 382-3524.
5.4 Chemical Regulations and Guidelines System (CRGS)
CRGS is an on-line data base that is being developed to provide
information on chemical regulatory material found in statutes, regu-
lations, and guidelines at the Federal, State, and international
levels. Currently, only the first phase of CRGS, which encompasses
source material at the Federal level only, is operational. Nation-
wide access to CRGS is available through Dialog. For further Infor-
mation, contact Delores Evans at FTS 382-3546 or Ingrid Meyer at FTS
382-3773.
5-1 July, 1982
-------
5.5 Chemical Substances Information Network (CSIN)
The prototype CSIN, operational since November 1981, has been devel-
oped by merging the technologies of computer networking and distrib-
uted data base management. CSIN is not another data base, but a
library of systems. Through the CSIN front-end intermediary manage-
ment computer, the user may access and use independent and autonomous
information resources that are geographically scattered, disparate
for data and information content, and employ a variety of types of
computer hardware, software, and protocols. Users may converse in
and among multiple systems through a single connection point, without
knowledge of or training on these independent systems.
Currently, six independent information resources are accessible
through CSIN. They are: National Library of Medicine (NLM), CIS,
EPA-CICIS, CAS-On-Line, SDC-orbit, and two files of Dialog: CRGS and
TSCA Inventory. The CSIN management computer allows the user to
create, retrieve, store, and manipulate data and queries. This
eliminates the need for reentering long lists of chemical identifiers
or other information elements that are part of the original query or
that have been identified and acquired from one or more of the CSIN
resources. For further information contact Dr. Sid Slegal at FTS
382-2256.
5.6 EPA Information Clearinghouse
The EPA Information Clearinghouse is a bibliographic data base com-
posed of over 475 individual data bases and models that contain
monitoring information and statistics on a variety of chemicals. The
Individual data bases are maintained for offices within EPA. For
further information, contact Charlene Sayers at FTS 755-9112.
The following data bases contain information on mercury:
BACT/LAER Determinations
Baseline Survey of Public Water Supplies on Indian Lands
BAT Review Study for the Timber Products Processing, Gum and Wood,
Chemicals, and the Printing and Publishing Industries
Best Management Practices, Timber Industry Effluent Guidelines -
Runoff
Best Management Practices, Timber Industry Effluent Guidelines -
Sludge
Boone County Field Site
Compatibility Studies to Determine Effectiveness of Treatment
Alternatives for Selected Industrial Wastewaters
Compliance Data System
Compliance Sampling Toxicant Surveys
Consolidated Permits Program-Application Form l,2b,2c
Continuous Monitoring Subset
Contrary Creek Project-803801
Conventional Water Pollutants
Crete, Illinois Metals Environmental Samples
Data Collection Portfolio for Industrial Waste Discharges
Discharge Monitoring Report
5-2 July, 1982
-------
Discharge Monitoring Report Files
Dredging-Special Studies Metals
Drinking Water
Drinking Water Special Study
Energy and Mining Point Source Category Data Base
EPA, Region X, Point Source File
Federal Facilities Information System
Federal Reporting Data System
Federal Reporting Data System-Regional
Fine Particle Emissions Information System
Fish Kills
Food Industry Group
Fugitive Emissions Information System
Hazardous Waste Data Management System
Hazardous Waste Site Tracking System
Hemlock, Michigan Environmental Samples
Hewlett-Packard
Humacao Ambient Data Base
IFB Organics Data Base
Indicatory Fate Study
Industrial Process Evaluations
Inhalable Particulate Analysis Bank
Inhalable Farticulate Network
Innovative Technology, Timber Industry Effluent Guidelines
Inorganic Chemicals Industry Regulation Record
Inventory (Regional National Pollutant Discharge Elimination System)
LiPari Landfill
Liquid Effluents Data System
Love Canal Data Handling System
Method Validation Studies of Priority Pollutants
Model State Information System
Multimedia Assessment of the Inorganic Chemicals Industry
National Pollutant Discharge Elimination System (NPDES) Permit
Compliance-Region III
National Pollutant Discharge Elimination System (NPDES) Discharge
Monitoring Reports-Region VII
National Pollutant Discharge Elimination System (NPDES) Discharge
Monitoring Reports-Region I
National Water Quality Surveillance System
Nationwide Urban Runoff Program
Needs Survey
New York Bight Ocean Monitoring Program
New York Harbor Survey
Ocean Dumping
Organic Chemicals/Plastics Industry
Paint and Ink Analytical Data
Permit Compliance System
Pharmaceutical Screening/Verification Data Base
Priority Pollutants-Region I
Priority Pollutants-Region III
Publicly Owned Treatment Works (POTW) Analytical Data
Publicly Owned Treatment Works (POTW) Quality Control
Puerto Rico Reservoirs
Regional Air Pollution Study-Ambient
5-3 July, 1982
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Regional Air Pollution Study-Point and Area Source
Regional Toxics Monitoring Program
Resource Conservation and Recovery Act (RCRA)-Hazardous Waste Site
Inspections
Screening Sampling Program
Sludge Distribution and Marketing Regulations-Community Impact Survey
Soil, Water, Estuarine Monitoring System
Solid Discharge Data System
Source Test Data System
Sources of Toxic Pollutants Found in Influents to Sewage Treatment
Plants
Storage and Retrieval of Aerometric Data
System for Consolidated Permitting and Enforcement Data Base
Textile Industry BAT Study-Toxic Sampling Data
Toxic Metals
Toxicant Control Fish Tissue Analyses
Toxics Monitoring
U.S. Virgin Islands-St. Thomas, St. Croix
United Nuclear Corporation (UNC) Spill-Rio Puerco Monitoring
UPGRADE
Utility Simulation Model Data Base
Verification Data Base
Verification Sampling Program
Waste Characterization Data Base
Wasteload Allocation File
Water Enforcement Regional System
Water Quality Information System
Wisconsin Power Plant Impact Study Data Center
5-4 July, 1982
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6. REGULATORY STATUS (current as of 4/23/82)
6.1 Promulgated Regulations
6.1.1 EPA Programs
Clean Air Act (CAA)
• Section 112 - Mercury is listed as a hazardous air pollutant and
EPA has issued national emissions standards (NESHAPs) for mercu-
ry smelters, chlor-alkali plants, and for sludge incineration or
drying plants (40CFR61, Subpart E).
Clean Water Act (CWA)
• Section 311 - Five mercury compounds designated as hazardous
substances (40CFR116.4) are subject to reporting requirements
(40CFR117.3).
• Sections 301, 304, 306 and 307 - Mercury and its compounds are
listed as toxic pollutants, also known as Priority Pollutants
(40CFR401.15), and are subject to effluent guideline limitations
which may Include pretreatment standards and new source
performance standards. Regulations have been issued for the
chlor-alkali industry (40CFR415, Subpart F), and for certain
subcategorles of the ore mining and dressing industry (40CFR440,
Subpart B and F) and the pesticide chemical Industry (40CFR455).
• Sections 402 and 404 - Discharge toxic pollutants such as mercu-
ry are controlled by permits required under the National Pollu-
tant Discharge Elimination System (NFDES). Permits for dis-
charge of dredged or fill materials are issued by the Army Corps
of Engineers (40CFR122 to 123}.
• Section 403 - Restricts dumping of mercury in the ocean except
as a "trace" contaminant (40CFR227.6).
Safe Drinking Water Act (SDWA)
• Section 1412 - EPA has issued a National Interim Primary
Drinking Water Standard for mercury (40CFR141.il).
• Sections 1421 to 1424 - Establishes an underground injection
control (UIC) program to protect underground sources of drinking
water (40CFR146).
Resource Conservation and Recovery Act (RCRA)
• Section 3001 - Mercury and its compounds are designated as toxic
wastes (40CFR261.33) and/or hazardous constituents (40CFR261,
App VIII). Extractable mercury also characterizes waste as haz-
ardous (40CFR261.24). Specific sources of hazardous waste that
contain mercury are from the chlor-alkali industry (K071, K106)
(40CFR261.32).
6-1 July, 1982
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• Sections 3002 to 3006 - Regulations for generators and trans-
porters of hazardous wastes and standards for treatment, stor-
age, and disposal are applicable to wastes characterized as
hazardous due to mercury levels (40CFR262 to 265).
Federal Insecticide, fungicide, and Rodenticide Act (FIFRA)
• All pesticide uses of mercury have been banned except for a
limited number of approved uses as fungicides or preservatives
(41FR 26742, 36068, and 164971).
« Procedures for disposal of organic mercury pesticides and con-
tainers (40CFR165.7 -.9).
6.1.2. Programs of Other Agencies
OSHA - Occupational Safety and Health Act
• An industry standard for airborne mercury is in effect
(29CFR1910.1000).
CPSC - Federal Hazardous Substances Act
• Among products subject to the Act are mercury switches and
batteries. However, no regulatory action is expected in the
near future.
DOT - Hazardous Materials Transportation Act
• A number of mercury compounds have been designated Class B
poisons and must be handled according to DOT regulations. Air
shipment of metallic mercury is prohibited (49CFR171-177).
FDA - Federal Food, Drug, and Cosmetic Act
• Standard for mercury content of bottled water
(21CFR103.35Id][ll).
• Regulations governing use of mercury compounds in cosmetics
(21CFR700.13) and hair coloring (21CFR73.2396).
• Administrative guideline sets action level for mercury in aquat-
ic animals (44FR4012).
• Color additives containing mercury are subject to certification-
—DSC Orange #10 and //ll and D&C Green #6 (21CFR74, 81, 82).
Note: The Bureau of Biologies at FDA has a limited control program
for mercury. Mercury levels are determined to check if the manufac-
ture complies with the product license.
6-2 July, 1982
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6.2 Proposed Regulations
6.2.1 EFA Programs
CAA
State implementation plan requirements; emission rates that
trigger need for controls (44FR51937).
CWA
• Effluent guidelines, including pretreatment standards and new
source performance standards, concerning mercury have been
proposed for subsections of the following industry point source
category:
Inorganic chemical manufacturing 45FR49450 (7/24/80)
6.2.2 Programs of Other Agencies
Atomic Energy Act
• Standards for disposal of residual radioactive materials from
uranium processing will limit resultant groundwater contamina-
tion by mercury (46FR2556).
6.3 Other Actions
Comprehensive Environmental Response, Compensation, and Liability Act
(CERCLA or Superfund)
• CERCLA provides for the liability, compensation, clean-up, and
emergency response for the release of hazardous substances into
the environment. This Act also deals with the cleanup of
hazardous waste disposal sites. (42USC9601; PL 96-510).
• EPA is developing regulations concerning the designation of
hazardous substances, the development of reportable quantities,
claims procedures, and the confidentiality of business records
(46FR54032). Revisions to the National Contingency Plan (NCP)
as required by CERCLA have been Issued in a proposed rule
(47FR10972).
• Hazardous substances as defined by Section 101(14) of CERCLA
include: hazardous wastes designated under Section 3001 of the
RCRA; hazardous air pollutants regulated under Section 112 of
the CAA; water pollutants listed under Sections 307 and 311 of
the CWA (and also any substances regulated in the future under
Section 7 of TSCA and Section 102 of CERCLA). Therefore,
mercury and compounds are hazardous substances under CERCLA and
will be subject to regulations issued under Superfund.
6-3 July, 1982
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7.
7.1
7.2
7.3
7.4
STANDARDS AND RECOMMENDED CRITERIA*
Air
• National Emission Standards (NESHAP) (40CFR61, Subpart E):
Mercury smelters and chlor-alkali plants 2.3 kg/day
Sludge incineration or drying plants 3.2 kg/day
Water
• Hazardous spill rules require notification of discharges equal
to or greater than the following reportable quantities (40
CFR117.3):
Mercuric cyanide
Mercuric nitrate; mercuric
sulfate; mercuric thiocyanate;
mecurous nitrate
• Maximum concentration level of
total mercury for drinking water
(40CFR141.il)
• Water Quality Criteria (45FR79318)
Freshwater aquatic life
Saltwater aquatic life
Human health
Hazardous Waste
• Waste is designated hazardous
if the concentration of mercury
equals or exceeds this maximum
for extractable mercury
(EP toxicity, 40CFR261.24)
Other
• FDA maximum concentration of
mercury in bottled water
(21CFR103.35[d]]l])
1.0 Ib
10 Ibs
2 ug/1
0.20 ug/1 (24-hr avg)
4.1 ug/1 (maximum)
0.10 ug/1 (24-hr avg)
3.7 ug/1 (maximum)
0.144 ug/1 (ambient)
200 ug/1
2 ug/1
* See Appendix A for a discussion of the derivation, uses, and limitations of
these criteria and standards.
7-1
July, 1982
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FDA maximum for the level of
mercury preservatives In
cosmetics (21CFR700.13):
Eye area cosmetics 65 ppm
Other cosmetics 1.0 ppm
FDA guideline action level
for mercury in aquatic animals
(44FR4012) 1.0 ppm
OSHA standard for workplace
exposure to mercury in air
(29CFR1910.1000). (A NIOSH 100 ug/m3
criteria document recommends (8-hr avg)
a 50 ug/m3 limit.)
7-2 July, 1982
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8. SPILL OR OTHER INCIDENT CLEAN-UP/DISPOSAL (CONTACT: National
Response Center, 800-424-8802, or 426-2675 if in Washington, D.C.)
General information pertaining to mercury compounds will be presented
first, followed by specific information applicable to the individual
chemicals for which information is available. The term "mercury"
will refer to all mercury compounds.
8.1. Hazards and Safety Precautions
Mercury is a highly toxic material that may be fatal when inhaled or
Ingested. Fire will produce highly toxic mercury fumes. Runoff from
fire control or dilution water may cause pollution. Some of these
materials may burn but do not ignite readily.
Store mercury in tightly closed containers in well ventilated areas
and protect from light.
8.2 First Aid
Move victim to fresh air; call emergency medical care. In case of
contact with material, immediately flush skin or eyes with running
water for 15 minutes.
8.3 Emergency Action
Avoid contact with and Inhalation of the spilled cargo. Stay upwind;
notify local fire, air, and water authorities of the accident. Keep
unnecessary people away. Use full protective clothing including
NIOSH-approved rubber gloves and boots, safety goggles or face mask,
hooded suit, and either a respirator whose cannister is specifically
approved for this material or a self-contained breathing apparatus.
Care must be exercised to decontaminate fully or dispose of all
equipment after use.
In case of spill or leak, OHM-TADS recommends the following action:
dam the stream to reduce the flow and to retard dissipation by water
movement. Dredging or bottom vacuum may be effective. Information
on a specific mercury compound can be found in the OHM-TADS data base
or the Envirex Manual (EPA 600/2-77-227).
Fire can be extinguished with water in flooding quantities as fog,
foam, dry chemical, or carbon dioxide. If water or foam Is used,
contain flow to prevent spread of pollution; keep from drains and
sewers. Remove container from fire area if you can do it without
risk. Cool containers that are exposed to flames with water from
side until well after the fire is out. For massive fire in cargo
area, use unmanned hose holder or monitor nozzles. If this is
impossible, withdraw from area and let fire burn.
8.4 Notification and Technical Assistance
Section 103(a) and (b) of the Comprehensive Environmental Response,
Compensation, and Liability Act of 1980 requires persons who release
8-1 July, 1982
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hazardous substances Into the environment in reportable quantities
determined pursuant to Section 102 of the Act to notify the National
Response Center (NRC): 800-424-8802 (Washington, D.C. 426-2675).
A variety of mercury compounds are designated as hazardous under the
CWA Section 311. These compounds (and their reportable quantities)
are: mercuric cyanide (1 Ib), mercuric nitrate (10 Ib), mercuric
sulfate (10 Ib), mercuric thiocyanate (10 Ib), mecurous nitrate (10
Ib), and phenylmercury acetate (100 Ib).
For technical assistance, call CHEMIREX (Chemical Transportation
Emergency Center): 800-424-9300. Other sources of technical infor-
mation are (1) the EPA's Oil and Hazardous Materials - Technical
Assistance Data System (OHM-TADS) contained in the NIH-EFA Chemical
Information System (CIS), which provides information pertinent to
emergency spill response efforts, and (2) the CHRIS System, which
provides information on first aid, physical/chemical properties,
hazard assessments, and response methods. Both systems can be
accessed through NRC.
8.5 Disposal
Persons generating more than 1000 kg of hazardous waste per month, or
spill clean-up residue or debris resulting from the clean-up, are
subject to regulation under RCRA. Such wastes include waste mercury
as well as wastes that fall the EP Toxic!ty test, 40 CFR 261.24,
(extractable concentration is greater than 0.2 mg/1).
The following specific waste streams are subject to Subpart D regula-
tions:
(1) Brine purification muds from the mercury cell process in
chlorine production, where separately prepurified brine is not
used.
(2) Wastewater treatment sludge from the mercury cell process
in chlorine production.
8-2 July, 1982
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9. SAMPLING. ACCEPTABLE ANALYTICAL TECHNIQUES, AND QUALITY ASSURANCE
9.1 Air (CONTACT: Sharon Harper, FTS 629-2443)
Mercury is a hazardous air pollutant; therefore reference procedures
have been promulgated (40CFR61).
Test Method 101 is applicable for the determination of particulate
and gaseous mercury emissions when the carrier gas stream is princi-
pally air. The method is for use in ducts or stacks at stationary
sources. Test Method 102 is applicable for the determination of
particulate and gaseous mercury emissions when the carrier gas stream
is principally hydrogen. The method is for use in ducts or stacks at
stationary sources.
In both methods, particulate and gaseous mercury emissions are iso-
kinetically sampled from the source and collected in acidic iodine
monochloride solution. The mercury collected (in the mercuric form)
is reduced to elemental mercury in basic solution by hydroxylamine
sulfate. Mercury is aerated from the solution and analyzed using
spectrophotometry.
9.2 Water (CONTACT: Theodore D. Martin, FTS 684-7312 or
Gerald D. McKee, FTS 684-7372)
Mercury is a Clean Water Act 304(h) parameter and is listed as an in-
organic priority pollutant. It is also a drinking water parameter
with a maximum contaminant level of total mercury set at 2 ug/1. The
term "total mercury" is defined as the sum of the concentrations of
all forms of mercury in both the dissolved and suspended fractions of
the sample. Samples collected for the analyses of total mercury are
not filtered and must be preserved with nitric acid to pH < 2 as soon
as possible, preferably at the time of collection.
The approved method for mercury analysis is a flameless cold vapor
atomic absorption procedure based on the absorption of ultraviolet
radiation at a wavelength of 253.7 nm by mercury vapor. For the
analysis of total mercury, a sample digestion step is required to
ensure the mercury is in the proper chemical state and available for
reduction to elemental mercury. After reduction with stannous sul-
fate, the solution Is aerated and the mercury is passed through an
absorption cell positioned in the light path. The absorbance of the
mercury is measured as a function of concentration. The analytical
range of the manual cold vapor method is 0.2 to 10 ug Hg/1.
In an interlaboratory precision and accuracy study, where 11 labora-
tories participated and 3 acidified distilled water samples contain-
ing 0.52, 2.2, and 8.7 ug Hg/1 were analyzed by the manual cold vapor
method, the standard deviations were ±0.052, ±0.28, and ±1.51, re-
spectively. Recoveries at these levels were 99%, 100%, and 94%,
respectively. In a single laboratory with concentrations of 1.0,
3.0, and 4.0 ug Hg/1 spiked in surface water, the standard deviations
were ±0.14, ±0.10, and +0.08 with recoveries of 89%, 87%, and 87%,
respectively.
9-1 July, 1982
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The cold vapor method can1 also be automated using a Technicon Auto
Analyzer and vapor-liquid separator. The analytical range of the
automated method is 0.2 to 20.0 ug Hg/1. Precision in a single lab-
oratory was determined using standards at concentrations of 0.5 to
10.0 ug Hg/1. The reported standard deviations varied from 8% to
4%. Recovery from surface water spiked with ten organic mercurials
at 10 ug/1 level ranged from 87% to 117%.
9.3 Solid Waste (CONTACTS: Thomas Hinners, FTS 545-2140; and
Werner Beckert, FTS 545-2137)
A waste is defined as hazardous if the extractable mercury equals or
exceeds 0.2 mg/1. The extraction procedure is explained in detail in
"Test Methods for Evaluating Solid Waste, Physical/Chemical Methods"
(EPA Publication SW-846, 1980, Method 8.5.7). After extraction and
conversion to the volatile elemental form, the extractable mercury is
measured by a cold vapor atomic absorption procedure similar to
method 245.1 for water.
At present there are no EPA approved methods available for
determining total mercury content in waste. However, the procedure
described for sediments (Section 9.4) has been applied to waste
materials.
9.4 Other Samples
A procedure for the determination of total mercury in sediments,
soils, and sludge materials is given in "Methods for Chemical
Analysis of Water and Wastes," (1979, EPA-600/4-79-020; Method
245.5). This method uses cold vapor atomic absorption, and has a
useful range of 0.2 to 5 ug/g. Samples are dried (60°C), digested
(aqua regia), and oxidized (KMn04), before analysis.
Precision and accuracy studies gave the following standard deviations
on replicate sediment samples at indicated mercury levels: 0.29 ug/g
±0.02; 0.82 ug/g ±0.03. Recoveries were 97% and 94% respectively.
Table 3 summarizes the approved method with appropriate references.
The "NIOSH Manual of Analytic Methods" (2nd ed., Vol. 1, 1977)
contains flameless atomic absorption methods for mercury detection in
several media: air (Method 175), blood (Method 167), and urine
(Method 165). The analytical technique for air uses a three-stage
collection tube which permits separate determinations of partlculate,
organic, and metallic mercury.
9-2 July, 1982
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A procedure for methylmercury determination in biological media
(e.g., fish) has been proposed by EPA (J. E. Longbottom, et al., J.
Assoc. Offie. Anal. Chem., 56:1297 [1973]). Cupric sulfate is used
to free methylmercury from inorganic and organic ligands. Addition
of excess KBr forms CHjHgBr which is separated by gas chromato-
graphy. Sensitivity is reported to be 10 ppb, with a precision of
-10% and recoveries of >95%.
TABLE 3. LIST OF APPROVED TEST PROCEDURES FOR TOTAL MERCURY
Reference Method No.
Standard
EPAl Methods 2 ASTM3 USGS4
Manual Cold Vapor 245.1 303F D3223-79 1-3462-78
Automated Cold Vapor 245.2
. "Methods for Chemical Analysis of Water and Wastes," 1979
EPA-6 00/4-79-020.
2. "Standard Methods for the Examination of Water and Wastewater,"
15th Edition.
3. "Annual Book of Standards," Amer. Society for Testing and Materi-
als, Part 31, Water.
4. "Methods for Analysis of Inorganic Substances in Water and Fluvi-
al Sediments" U.S. Department of the Interior, Geological Sur-
vey, Open-file Report 78-679.
9.5 Quality Assurance (CONTACT: John Winter, FTS 684-7325)
ORD has a full range of Quality Assurance support available which
Includes the following items:
• unknown performance evaluation samples
• known quality control check samples
These are available to the regions through the Quality Assurance
Branch of EMSL-Cincinnati.
9-3 July, 1982
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Quality assurance materials and assistance are also available for air
analysis (CONTACT: J. Puzak, FTS 629-2188).
Waste materials with certified levels of mercury are available from
the Office of Standard Reference Materials, National Bureau of
Standards (telephone: 301-921-2045).
9-4 July, 1982
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REFERENCES
The major references used in preparation of this document are listed below.
EPA documents are referenced by EPA Office of origin and the year of publica-
tion. For further information refer to contacts given throughout this docu-
ment or contact the relevant EPA Program Offices listed in the next section.
(Dreisbach, 1977)
(IERL, 1979)
(NAS, 1978)
(OWRS, 1979)
(OWRS, 1980a)
(OWRS, 1980b)
(OWRS, 1980c)
(Stokinger, 1962)
(WHO, 1976)
Handbook of Poisoning, Dreisbach, R.H., Lange Medical
Publications (1977).
Status Assessment of Toxic Chemicals: Mercury,
EPA-600/2-79-210i, IERL, Cincinnati (1979).
An Assessment of Mercury in the Environment, National
Academy of Sciences, Washington, D.C. (1978).
Water-Related Environmental Fate of 129 Priority
Pollutants, EPA-440/4-79-029a, Office of Water
Regulations and Standards (1979).
Ambient Water Quality Criteria for Mercury, EPA-
440/5-80-058, Office of Water Regulations and Standards
(1980).
Strategy for Controlling Environmental Exposure to
Mercury, draft report, Office of Water Regulations and
Standards (1980).
Environmental Material Balance for Mercury, EPA Contract
No. 68-01-3852, Office of Water Regulations and Standards
(1980).
Industrial Hygiene and Toxicology, Ch. 27, Stokinger,
H.E., Interscience, New York, N.Y. (1962).
Environmental Health Criteria 1 - Mercury, World Health
Organization (1976).
R-l
July, 1982
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OFFICE CONTACTS
The EPA Offices and Divisions that are listed below may be contacted for more
information relating to the Indicated sections of this document. While these
offices are, in many cases, the offices of origin for the data included In
this paper, the personal contacts given throughout this document should be
contacted first. Unless otherwise noted, the offices listed are situated in
Headquarters, Washington, D.C., and the telephone numbers given are FTS
(Federal Telecommunications System) numbers. For commercial telephone calls
to Headquarters which are not placed on FTS, area code 202 must be used.
Other commercial numbers are noted for the office contacts located outside
Washington, D.C.
HEALTH AND ENVIRONMENTAL EFFECTS (Section 2)
Office of Health and Environmental Assessment (OREA)
Environmental Criteria and Assessment Office:
Cincinnati, OH 684-7531 (513-684-7531)
Research Triangle Park, NC 629-2266 (919-541-2266)
Carcinogen Assessment Group 755-3968
Office of Drinking Water (ODW)
Health Effects Branch 472-6820
Office of Toxic Substances (OTS)
Health and Environmental Review Division 382-4241
Environmental Research Laboratory
Duluth, MN, Region V 783-9550 (218-727-6692)
ENVIRONMENTAL RELEASES AND EXPOSURE (Sections 3 and 4)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Water Regulations and Standards (OWRS)
Monitoring and Data Support Division 426-2503
R-2 July, 1982
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Office of Toxic Substances (OTS)
Exposure Evaluation Division 382-3873
Assessment Division 382-3442
DATA BASES (Section 5)
Office of Toxic Substances (OTS)
Management Support Division 382-3546
REGULATORY STATUS, STANDARDS. AND CRITERIA (Sections 6 and 7)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Drinking Water (ODtf)
Criteria and Standards Division 472-5016
Office of Water Regulations and Standards (OWRS)
Criteria and Standards Division 755-0100
Effluent Guidelines Division 426-2571
Office of Solid Waste (OSW)
State Programs and Resources
Recovery Division 755-9107
SPILL CLEAN-UP AND DISPOSAL (Section 8)
NOTE: For Emergenices call the National Response Center at 1-800-424-8802
(1-800-426-2675 from the Baltimore/Washington area).
Office of Emergency and Remedial Response (OERR)
Emergency Response Division 245-3045
Oil and Hazardous Materials Spills Branch
Edison, NJ, Region II 340-6634 (201-321-6634)
R-3 July, 1982
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Office of Solid Waste (OSW)
Hazardous and Industrial Waste Division 755-9187
ANALYTICAL TECHNIQUES (Section 9)
Environmental Monitoring Systems Lab (EMSL)
Air Analysis
Research Triangle Park, NC 629-2454 (919-541-2454)
Water Analysis
Cincinnati, OH 684-7311 (513-684-7311)
Waste Analysis
Las Vegas, NV 545-2137 (702-798-2137)
GENERAL IPP COMMENTS. CORRECTIONS OR QUESTIONS
Office of Toxic Integration (OTI)
Chemical Information and Analysis Program 382-2249
R-4 July, 1982
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Polychlorinated Biphenyls
-------
POLYCHLORINATED BIPHENYLS (PCBs)
Table of Contents Page
Physical/Chemical Properties and Chemistry 1-1
Properties 1-1
Chemistry and Environmental Fate/Transport 1-2
Effects Information 2-1
Health Effects 2-1
Environmental Effects 2-3
Other Effects 2-3
Environmental Release 3-1
Exposure Routes 4-1
Air Exposure 4-2
Hater Exposure 4-2
Other Exposure 4-2
Data Bases 5-1
NIH/EPA Chemical Information.System (CIS) 5-1
Chemical in Commerce Information System (CICIS) 5-2
Chemical Substances Information Network (CSIN) 5-2
Graphic Exposure Modeling System (GEMS) 5-3
Regulatory Status 6-1
Promulagated Regulations 6-1
Proposed Regulations 6-5
Other Actions 6-6
Standards and Recommended Criteria 7-1
Air 7-1
Mater 7-1
Food 1-1
July, 1984
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Spill or Other Incident Clean-Up/Disposal 8-1
Hazards 8-1
First Aid 8-1
Emergency Action 8-1
Notification and Technical Assistance 8-1
Disposal 8-2
Sampling, Acceptable Analytical Techniques, and Quality Assurance 9-1
Air 9-1
Water 9-1
Solid Waste 9-3
Other Samples 9-4
Quality Assurance 9-5
References and Office Contacts R-1
July, 1984
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POLYCHLORINATED BIPHENYLS
1. PHYSICAL/CHEMICAL PROPERTIES AND CHEMISTRY
1.1 Properties
The term polychlorlnated biphenyls (PCBs) refers to a class of chlo-
rinated aromatics which were commercially produced in this country as
a series of complex mixtures known as Aroclors (Monsanto trademark).
Individual Aroclors were identified by a set of four digits; usually
the last two digits denote the approximate chlorine content by
weight. For example, Aroclor 1242, had an average chlorine content
of 42% and consists primarily of di-, tri-, and tetrachloro-
biphenyls.
Of the total 209 compounds resulting from the partial or total chlo-
rination of blphenyl, approximately 100 individual compounds have
been detected in the various Aroclors. The structure of a typical
PCB is shown below.
2,2'-dichloro-1,1'-biphenyl
Higher chlorine content results from increased chlorination and
corresponds, in general, to greater persistence in the environment.
Most PCBs marketed in the U.S. are still in service, primarily in
electrical equipment. The remainder is believed to be primarily in
landfills and dumps across the country. No PCBs have been intention-
ally produced in the United States since 1977, and the distribution
and use of PCBs are severely limited by regulations (OTS, 1977).
While individual PCBs vary in their physical properties, all have
very low water solubility, low vapor pressure, low flammability, low
electrical conductivity, and a high degree of thermal and chemical
stability. Because of these properties PCBs have been extensively
used in "closed" or "semi-closed" systems such as electrical trans-
formers and capacitors, heat transfer systems, and hydraulic sys-
tems. PCBs used in transformers are usually present as a mixture
with trichlorobenzenes called Askarels.
Environmentally relevant physical properties of the Aroclors are
given in Table 1. It must be emphasized that the Aroclors are mix-
tures of different PCBs and the physical properties cannot be proper-
ly defined as constants. An additional problem arises because two
grades of PCB mixtures existed; for most Aroclors a darker, less pure
grade was available. No compounds other than chlorobiphenyls were
found in commercial PCBs at 0.01% or more of product weight. How-
ever, small amounts of chlorinated dibenzofurans and chlorinated
naphthalenes were detected in some batches (NAS, 1979).
l-l July, 1982
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TABLE 1: PROPERTIES OF AROCLORS*
CAS NO.
Distillation Range
Water Solubility
(mg/D
Log u/cPb
Vapor Pressure
(torr, 25°C)
Density
(g/cm3; 25°C)
1016
12674-11-2
325-356
0.42
4.38
[4xlO~4]
1.33
1221
11104-28-2
275-320
[15]
[2.8]
[6.7x10-3]
1.15
1232
11141-16-5
290-325
[1.45]
[3.2]
[4.1x10-3]
1.24
1242
53469-21-9
325-366
0.24
4.11
4.1x10-3
1.35
1248
12672-29-6
340-375
0.054
[5.75]
4.9xlO~4
1.41
1254
11097-69-2
365-390
0.012
[6.03]
7.7xlO~5
1.50
1260
11096-82-5
385-420
0.0027
[7.14]
4.0xlO~5
1.58
Bracketed data are estimated; the last two digits of the Aroclor Identity number Indicate the approximate chlorine
percentage content by weight except for Aroclor 1016 which was a more recent mixture containing 41% chlorine.
•-• b Octanol/water partition coefficient.
CD
ro
Source: From data summarized in (OWRS, 1979)
-------
1.2 Chemistry and Environmental Fate/Transport
FCBs are extremely stable compounds and nearly inert under normal
environmental conditions. Chemical oxidation, reduction, isomeriza-
tion, and hydrolysis only occur under extreme conditions. For ex-
ample, thermal conversion of PCBs to chlorinated dibenzofurans occurs
only upon heating to 500-6008C. PCBs are reported to undergo photo-
lytic loss of chlorine (MAS, 1979; OWRS, 1979).
The ubiquitous distribution of PCBs is apparently due to volatiliza-
tion and transport as an aerosol followed by fallout in dust or
rain. PCBs may exist in vapor form and attached to atmospheric par-
ticles. Vapor pressure data suggest that the more volatile (less
chlorinated) PCBs should preferentially accumulate in the atmo-
sphere. Although laboratory results indicate that PCBs undergo pho-
todegradation in the vapor state, no direct evidence exists concern-
ing the environmental relevance of such a process (NAS, 1979).
PCBs have low water solubility, high octanol/water partition coeffic-
ients, and are readily adsorbed onto suspended solids, especially
those high in organic carbon. In natural waters, adsorption to sedi-
ments is the major process for Immobilizing PCBs. The persistence of
these chemicals, however, allows resuspension of these sediments
which may cause them to be released back into the water. The biota
are another environmental compartment into which these compounds are
concentrated; measured bioconcentration factors range from 10* to
106. Biodegradation is most important for the less chlorinated com-
pounds and is the only process known to degrade PCBs under environ-
mental conditions. While evaporative half-lives of Aroclors from
water are estimated to be about 10 hours, volatilization from natural
waters is probably as much as 100-fold slower, perhaps due to absorp-
tion by suspended solids (OURS, 1979).
FCBs are adsorbed most efficiently on soils with high clay or organic
content. Transfer of PCB isomers from soil to water closely follows
their physical properties; thus, the higher chlorinated compounds are
not leached from soils, while those with lower chlorine content are
leached with difficulty. Losses do occur by volatilization and bio-
transformation. Ambient air analysis over landfills indicates that
evaporation may be the principal mode of PCB transport from land dis-
posal sites (OTS, 1976; NAS, 1979).
1-3 July, 1982
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2. EFFECTS INFORMATION
2.1 Health Effects (CONTACTS: Jerry Stara, FTS 684-7531;
Penny Fenner-Crisp 472-4944)
2.1.1 Acute Toxiclty
PCBs have low acute toxicity. Most instances of human toxicity have
resulted from long-term exposure and accumulation in the body. In a
well-known Instance of acute poisoning by PCB-contamlnated rice oil
in Japan (Yusho disease), average total ingestion of 2 g PCS was
associated initially with increased eye discharge and swelling of
upper eyelids, acneform eruptions and follicular accentuation, and
pigmentation of the skin. Other symptoms including dermatologic
problems, swelling, Jaundice, numbness of limbs, spasms, hearing and
vision problems, and gastrointestinal disturbances were prominent
among the complaints of patients seen within the first eight months
after exposure. Other changes observed during this period Included
lowered blood counts, and skin, liver and eye abnormalities. Per-
sistence of the compounds in the body resulted in long-term and
reproductive effects. However, due to the high levels of chlorinated
dibenzofurans also present in the rice oil, (average total intake was
estimated to be 10 mg), the above effects cannot conclusively be
attributed to PCB toxicity (IARC, 1978; NAS, 1979).
2.1.2 Chronic Toxicity
Occupational exposure to PCBs often results from inhalation and
dermal contact. Worker complaints after months or years of PCB
exposure include chloracne, other dermal effects, irritation of eye,
nose, or throat, and gastrointestinal disturbance. Other effects
include changes in fat metabolism and mild disturbances in liver
function. PCB levels of 5.2-6.8 mg/m3 caused severe chloracne; a
level of 0.1 mg/m3 caused mild chloracne. Lower levels not causing
overt toxicity may affect liver function. Levels of 10 mg/m3 are
reported to be unbearably irritating.
Other systemic effects of PCBs in mammals Include porphyrla, increas-
ed thyroxin metabolism, inhibition of ATPases, and interference in
oxidatlve phosphorylation. Alterations in steroid hormone metabolism
are produced by PCBs in rats; it has been suggested that effects on
reproduction may be due to induction of steroid metabolizing en-
zymes. Aroclors appear to reduce liver vitamin A levels in several
species and some authors suggest vitamin A may play a role in detoxi-
fication of PCBs. PCBs have also shown immunosuppressive effects in
various species (WHO, 1976; OURS, 1980).
Carcinogenicity, Mutagenicity and Teratogenicity
Several studies using rodents indicate that some PCB mixtures are
carcinogenic; however, other studies, including a recent study by
NCI, have been negative for some Aroclors. PCBs are classified as
carcinogenic by the International Agency for Research on Cancer
(IARC) and the EPA (IARC, 1978; OWRS, 1980).
2-1 July, 1982
-------
The only firm data exists for female rats which were given a 100 ppm
diet of Aroclor 1260 (4.3 to 11.6 mg/kg body weight per day) for 21
months. The incidence of hepatocellular carcinoma (liver cancer) was
26/184 (controls, 1/173); in addition, nonoalignant (neoplastic)
nodules were observed in liver at high frequencies (170/184) in these
FCB-treated animals. It should be noted that none of the studies on
PCBs was a lifetime study; in all cases animals were treated, killed,
and examined. Lifetime studies might help to elucidate the signifi-
cance of nonmalignant tumors induced by PCBs, i.e., whether or not
these nonmalignant tumors become malignant. Data on carcinogenicity
of PCBs in humans are inconclusive at this time (OWRS, 1980).
PCBs have also been shown to have a significant effect on carcinogen-
ic properties of other chemicals. The co-carcinogenic properties of
PCBs apparently results from induction of mixed-function oxidases,
particularly in the liver. PCBs can stimulate microsomal enzyme
activity responsible for metabolizing many xenobiotic chemicals; this
may increase the carcinogenicity of chemicals that must undergo
microsomal activation, and decrease the activity of those chemicals
which are detoxified by the microsomal enzymes (IARC, 1978).
The mutagenicity of PCB isomers has been tested in several systems.
The only marked genetic effect observed at any level was with the
single isomer 4-chlorobiphenyl, and attempts to reproduce this exper-
iment have not been successful. Despite the apparent weak mutagen-
icity of PCBs in the systems examined to date, the fact that most
animals probably metabolize PCBs through an arene oxide Intermediate,
(reactive compounds which could react with nucleic acids and cause
genetic effects), indicates that the mutagenic potential of PCBs
should not be casually dismissed (OWRS, 1980; IARC, 1978).
Evidence concerning teratogenic effects of PCBs is lacking. No fatal
abnormalities were produced in rats by daily doses of Aroclors 1242,
1254, or 1260 at 10 and 30 ppm, or Aroclors 1254 at 100 ppm in the
diet. Indications of structural malformations or genetic changes
have been rare. However, controlled experiments using nonhuman
primates have illustrated reproductive abnormalities due to low-level
PCB exposure. In addition to alterations in menstrual cycles and
births of small infants, nonhuman primates had more early abortions.
The Infants born to exposed mothers also showed some immunological
and behavioral deficiences (WHO, 1976; OWRS, 1980).
2.1.3 Absorption, Distribution, and Metabolism
Commercially prepared PCBs are a complex mixture of chlorinated bi-
phenyls and may be contaminated with other toxicants, such as chlor-
inated napthalenes and chlorinated dibenzofurans. The toxicological
properties of these mixtures vary according to their composition.
Exposure may occur through ingestlon, inhalation, or dermal contact;
absorption is efficient by all routes. Human exposure has resulted
largely from consumption of contaminated food. PCBs accumulate in
the fatty tissues and skin of man and other mammals. The amount
stored depends on the susceptibility to metabolism and, therefore, on
the degree of chlorination and availability of adjacent unsubstituted
carbons in the aromatic rings (NAS, 1979).
2-2 July, 1982
-------
Metabolism of PCBs occurs by formation of phenolic and dihydroxy
metabolites with arene oxides as probable intermediates. The rate of
metabolism and excretion slows dramatically as the number of
chlorines on the biphenyl nucleus increases. PCBs may be transferred
either transplacentally or in breast milk. Apparently, nonhuman
primates retain PCBs more efficiently than rodents (NAS, 1979).
2.2 Environmental Effects (CONTACT: Oilman Veith, FTS 783-9534)
2.2.1 Aquatic Effects
The acute toxicity of several polychlorinated biphenyls (FCBs) to
freshwater animals has been measured with three Invertebrate and four
fish species, and the species mean acute L.C5Q values for the various
compounds range from 2.0 to 283 ug/1. The data from flow-through
tests with measured concentrations are similar for fish and
invertebrate species, and probably accurately reflect the toxicity of
the compounds. The data from static tests are more variable, and
many may not reflect actual toxicity, due to volatility, solubility,
bioconcentration, and adsorption characteristics of the various PCB
compounds. Eleven life-cycle or partial life-cycle tests were com-
pleted with three Invertebrate and two fish species; the chronic no-
effect levels range from 0.2 to 15 ug/1. Species mean acute LCjQ
values for PCBs and saltwater animals range from 10.5 to 20 ug/1 In
six tests on three Invertebrate species. Two chronic tests have been
conducted on the sheepshead minnow, providing chronic no-effect lev-
els for this species of 7.14 and 0.098 ug/1 (OWRS, 1980).
The freshwater residue data show that PCBs accumulate to relatively
high levels in fish and invertebrate tissues, and that for most spe-
cies PCBs are not rapidly eliminated when exposure is discontinued.
Bioconcentration factors (BCF) for invertebrate species range from
2,700 to 108,000. Bioconcentration factors for PCB exposures of fish
species range from 3,000 to 274,000. Biocentration data for PCBs in
saltwater fish and invertebrate species show bioconcentration factors
ranging from 800 to 230,000 for Invertebrate species and from 14,400
to 670,000 for fish species (OWRS, 1980).
The Water Quality Criteria document lists criteria to protect aquatic
life that are very low. For freshwater a 24-hour average of 0.014
ug/1 Is suggested and the value for saltwater is 0.03 ug/1. Drinking
water has seldom been found to be contaminated with PCBs (OWRS,
1980).
2.3 Other Effects
Assessment of effects of PCBs on the environment Is not clear-cut.
Although many "hot spots" with high PCB levels exist, these compounds
have not been detected In agricultural soil. Average PCB concentra-
tions In vegetation are not known. Available data in birds deal with
predators, and since levels depend on diet It is difficult to derive
an average value for PCB concentration in wildlife (see Section 4).
2-3 July, 1982
-------
While PCBs are found in many places the toxic effects are subtle and
difficult to detect. Reduced reproductive capability and morpholog-
ical and functional changes in the livers of test animals have been
observed. PCBs accumulate in adipose tissues and severe effects may
arise when the animal is under sufficient stress to mobilize the PCB-
containing lipids (NAS, 1979).
2-4 July, 1982
-------
3. ENVIRONMENTAL RELEASE
There is no substantial evidence suggesting that PCBs are produced in
the environment, either from natural sources or from chemical trans-
formation of the compounds. Therefore, all environmental contamina-
tion by PCBs is Inferred to have resulted from the production and use
of materials and equipment containing PCBs. Also, no significant
degradation processes, either environmental or biological are opera-
tive for free PCBs which contain four or more chlorine atoms per mol-
ecule (NAS, 1979).
Overview of PCBs Industrial Usage in the United States
Over the four years from 1971-1975 the domestic production and use of
polychlorinated biphenyls were approximately constant with averages
of 40 million pounds per year for production and 33 million pounds
per year for domestic sales. During this period Monsanto Industrial
Chemicals Corp., the sole domestic producer, supplied approximately
99% of the domestic market. Monsanto sold several PCB mixtures under
the generic trade name Aroclor, and purchase was limited to intended
use in nominally closed electrical systems (transformers and capaci-
tors) since 1971 under voluntary restrictions imposed by Monsanto.
No PCBs have been produced in the U.S. since 1977 (OTS, 1977).
Of the domestic sales of PCBs, 65% to 70% were to manufacturers of
capacitors, and the remainder to manufacturers of transformers. An
average of 2,000 to 2,500 pounds of PCBs (in the form of a mixture
with trichlorobenzenes) are used in PCB transformers. Approximately
5% of the transformers in service in this country were estimated to
contain PCBs as of 1976 (most transformers contain mineral oil in-
stead of PCBs). Capacitors containing PCBs are of two general types;
small capacitors which are built into electrical appliances such as
flourescent lights, TV sets and small motors, and large capacitors
which are used as separate units In electrical power distribution
systems and with large industrial machinery such as electric motors
and welding machines. Most small capacitors in use in radios and
other electronic equipment are solid-state units and do not contain
PCBs (OTS, 1977).
Cumulative PCBs Production and Usage in the United States
Estimates developed for total PCBs production and utilization in the
U.S. since their introduction to industry in 1930 are presented in
Table 2. These data define the estimated proportions of PCBs used in
various applications, and an accounting, based on available data plus
estimates, of the current distribution of this material (as of
1975). Of the roughly 1.25 billion pounds purchased by U.S. indus-
try, it is estimated that only 55 million pounds, or 4.4% have been
destroyed by incineration or by degradation in the environment.
About 60% of the total domestic sales is still In service, almost all
in capacitors and transformers. The remainder, about 440 million
pounds, are in the environment; it is estimated that 290 million
pounds are in landfills or dumps and 150 million pounds are "free" in
the general environment (air, water, soil, sediments) and presumably
3-1 July, 1982
-------
available to the biota. Some of the values in Table 2 are relatively
well-established, while others are gross estimates resulting from a
lack of data in the area. The estimated reliability for each value
presented is shown in the table (OTS, 1977).
One of the more important conclusions from this work is the estima-
tion that the amount of PCBs in landfills and dumps is nearly twice
the amount of PCBs already "free" in the environment. The material
in land disposal sites may be considered a threat to become widely
dispersed over a long period of time through slow vaporization and
leaching (OTS, 1976).
Routes of entry into the environment in the past which are no longer
important are: releases from PCB production and industrial use and
losses from open-end and nominally closed systems in service. Pre-
sent and future routes of entry into the environment are (NAS, 1979):
• Land disposal of obsolete materials containing PCBs (e.g.,
capacitors).
• Leakage from electrical equipment and accidental releases due to
fires or spills.
• Disposal of PCB-containing materials through incineration.
• PCB evaporation into air from landfills containing PCB waste.
3-2 Julyi 1982
-------
TABLE 2: ESTIMATES OF CUMULATIVE PCBS PRODUCTION, USAGE, AND GROSS ENVIRONMENTAL
DISTRIBUTION IN THE UNITED STATES OVER THE PERIOD 1930-1975 IN MILLIONS OF POUNDS
CO
1
co
C-i
c.
!<
1—"
ID
oo
r\)
Commercial
Production
U.S. PCB Production 1,400
Total U.S. PCB Imports 3
Total U.S. PCB Exports
PCB by Use Category:
Petroleum Additives
Heat Transfer
Misc. Industrial
Carbonless Copy Paper
Hydraulics and Lubricants
Other Plasticlzer Uses
Capacitors
Transformers
Use Other Than Electrical
PCB Degraded or Incinerated:
Environmentally Degraded
Incinerated
Landfills and PCBs in Dumps:
Production Wastes
Obsolete Elect. Equipment
Other (paper, plastic, etc.)
Free PCBs in the Environment
(soil, water, air, sediment)
TOTAL 1,403
Industrial PCBs Currently
Purchases in Service
150
1
20
27
45
80
115
630 450
335 300
8
1,253 758
Estimated
PCBs Currently PCBs Reliability
in Environment Destroyed of Values
+ 5%, -20%
+30%
+20%
+50%
+10%
+15%
+ 5%
+10%
+ 15%
+^20%
+20%
+60%
30 +70%
25 +10%
110 +20%
80 +40%
100 +40%
150 +30%
440 55
Source: (UTS, 1976).
-------
4. EXPOSURE ROUTES
Environmental Levels
Average PCB levels for possible exposure routes are given below (NAS,
1979):
ROUTE AVERAGE PCB LEVEL
Food (see Section 4,3)
Atmosphere .
Rural and Oceanic 0.05 ng/nT
Urban and Suburban 5.0 ng/m3
Major U.S. Rivers 0.1 to 3.0 ug/1*
Soil (1 cm) 2 x 10-5 ug/kg
The North Atlantic Ocean appears to be the dominant sink for PCBs,
accounting for 50% to 80% of PCBs in the environment, and freshwater
sediment is a major continental reservoir. Environmental load esti-
mates for the United States and the Atlantic Ocean are presented for
the following compartments (NAS, 1979):
Amounts (x 10& kg)
Atmosphere 0.018
Hydrosphere
Freshwater 0.012 - 0.035
Freshwater sediment 1.400 - 7.100
Freshwater biota 0.030
Marine sediment 0.660 - 2.700
Marine water 6.000 - 66.00
Marine biota 0.300
Lithosphere 0.140 - 2.800
The estimated distribution and amount of PCBs in the lithosphere are
summarized below. The uncertainty Involved in attempting to estimate
the distribution and amount of PCBs in the biota must be noted, par-
ticularly in the two largest compartments, soil and plants (NAS,
1979).
ESTIMATED PCB LEVELS IN THE LITHOSPHERE
PCB Concentration Amount of PCBs
(mg/kg) (kg)
Compartment low high low high
Soil (1 cm) 2 x 10-7 2 x 1Q-3 2.7 x 10* 2.7 x 10s
Plants 2 x 10~3 4 x 1Q-2 1.3 x 105 2.5 x 10°
Wildlife 2 x 10-2 4 x 10~1 1.3 x 10* 2.6 x 10Z
Livestock 2 x 10~3 10~1 1.3 x Ifl2 6.3 x 10-J
Man 3.5 x 1Q-1 4.9 x 1Q3 4.9 x 103
TOTAL 1.4 x 1032.8 x
* These estimates appear to be too high, probably due to proximity to point
sources. Low and high estimates for freshwater levels of PCBs are 1 and 3
ng/1 for four geographic areas in the U.S. (NAS, 1979).
4-1 July, 1982
-------
PCBs in Humans
Studies suggest that about half the American population has PCB lev-
els of one part per million or more; levels of PCBs in human adipose
tissue have been well documented, and the mean level in the U.S. pop-
ulation is 1.2 mg/kg. The concentration detected in adipose tissue
can be converted into whole body levels, assuming that lipid consti-
tutes 30% of body weight. Accordingly, a PCB concentration of 0.35
mg/kg body weight has been suggested. No adverse effects have been
associated with PCBs at these concentrations found in adipose tissue
or at levels measured in blood, or milk of individuals whose only
exposures were from general environmental contamination (NAS, 1979).
4.1 Air Exposure (CONTACT: Dave Patrick, FTS 629-5645)
Presently there are no known sources of low-level long-term atmo-
spheric emissions of PCBs. Potential for exposure exists for popula-
tions living near incinerators and landfills used for PCB disposal.
Fires or explosions involving electrical equipment containing PCBs
can result in short-term exposures. Dally intake from air is likely
to be much less than 1 ug according to the World Health Organization
(WHO, 1976).
4.2 Water Exposure
The highest concentration of PCBs reported in tap water is 100 ng/1
(in Japan), but levels probably do not exceed about 1 ng/1. There-
fore, daily intake from water consumption should also be much less
than 1 ug (WHO, 1976).
4.3 Other Exposure Routes
Food
The primary exposure route for the general population is through food
consumption. FDA and USDA monitoring programs in the past have shown
that fish, cheese, eggs and by-products used in animal feed were the
main commodities in the U.S. contaminated with PCBs. However, the
PCB content of all food items has decreased between 1971 and 1975
except for fish; it was estimated that PCB intake from diet was about
15 ug/day in 1971 and 8.7 ug/day in 1975 (IARC, 1978).
The measures taken in the 1970's to limit releases of PCBs and to
remove them from food processing environments has reduced direct con-
tamination of food to a low level. The bioconcentration potential
and persistence of PCBs in the aquatic environment have maintained
fish as a dietary source however (OWRS, 1980).
4-2 July> 1982
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5. DATA BASES
5.1 NIH/EPA Chemical Information System (CIS)
This is a collection of various scientific data bases available
through an interactive computer program. The linking system between
these data files is the Structure and Nomenclature Search System
(SANSS). CIS can also provide a list of non-CIS sources of
information on a chemical of interest. For further information,
contact Jim Cottrell at FTS 382-3546.
CIS contains numeric, textual, and bibliographic information in the
areas of toxicology, environment, regulations, and physical/chemical
properties. Several of these data bases are described below.
5.1.1 EPA Chemical Activities Status Report (EPACASR)
EPACASR is an on-line system containing information on EPA's interest
in chemicals. This system includes data on the Agency's regulations,
research, and assessments directed toward specific chemicals.
EPACASR is published annually and the data base is updated as
information is received. A searchable subset itemizes NTP/NCI
studies and results, as well as chemicals discussed in the IARC
monograph series. (Other sources are added as appropriate.) Entries
identify the statutory authority, the nature of the activity, its
status, the reason for and/or purposes of the effort, and a source of
additional information.
EPACASR is now available on CIS for internal use by EPA personnel and
is expected'to be accessible from a public CIS account in the near
future. The publication and computer tapes are also available
through the National Technical Information Service (NTIS). For
further information on EPACASR, contact Eleanor Merrick at
FTS-382-3626.
5.1.2 Industry File Indexing System (IFIS)
IFIS is an on-line system which contains information relating to the
regulation of chemicals by EPA through industry-specific
legislation. IFIS enables the user to determine, for any particular
industry, which chemicals are used and produced and how these
chemicals are regulated. IFIS is currently available on CIS for
internal use by some EPA personnel and is expected to be accessible
from a public CIS account soon. For more information on IFIS,
contact Daryl Kaufman at FTS 382-3626.
5.1.3 Scientific Parameters in Health and the Environment,
Retrieval and Estimation (SPHERE)
SPHERE is being developed by the EPA Office of Toxic Substances as a
system of integrated data bases, each representing a compilation of
extracted scientific data. The system is being released to the
public in stages as part of CIS, and the accessibility of component
data bases should be confirmed with the contact given below. The
5-1 July, 1984
-------
components currently available (either through public CIS accounts or
the internal EPA system) include: DERMAL, which provides
quantitative and qualitative health effects data on substances
admitted to humans and test animals via the dermal route; AQUTRE, a
component containing aquatic toxicity data for about 2,000 chemicals;
GENETOX, a mutagenicity data base; ISHOW, and ENVIROFATE, both of
which are compilations of physical/chemical parameters useful in
assessing environmental fate and transport. For more information
contact Paula Miles, FTS 382-3760.
5.1.4 Oil and Hazardous Materials Technical Assistance Data System
(OHMTADS)
OHMTADS is a data base created by EPA to aid spill response teams in
the retrieval of chemical-specific response information. The file
currently contains data for approximately 1,200 chemicals including
physical/chemical, biological, toxicological, and commercial
information. The emphasis is on harmful effects to water quality.
OHMTADS is available to the public through CIS.
5.1.5 Chemical Evaluation Search and Retrieval System (CESARS)
CESARS provides detailed information and evaluations on a group of
chemicals of particular importance in the Great Lakes Basin. CESARS
was developed by the State of Michigan with support from EPA's Region
V. Presently, CESARS contains information on 180 chemicals including
physical-chemical properties, toxicology, carcinogenicity, and some
aspects of environmental fate. Information for most chemicals is
extensive and consists of up to 185 data fields. CESARS is
accessible through public CIS accounts.
5.2 Chemicals in Commerce Information System (CICIS)
CICIS is an on-line version of the inventory compiled under the
authority of TSCA. This law required manufacturers of certain
chemicals (excluding food products, drugs, pesticides, and several
other categories) to report production and import data to EPA. CICIS
contains production volume ranges and plant site locations (for 1977)
for over 58,000 chemical substances. There is also a Confidential
Inventory in which data for some chemicals are claimed confidential
and are not available in the public inventory. A version of CICIS
(TSCA Plant and Production, or TSCAPP) is now accessible through
CIS. For more information contact Geri Nowak at FTS 382-3568.
5.3 Chemical Substances Information Network (CSIN)
The Chemical Substances Tnformation Network (CSIN) is not another
data base, but rather a sophisticated switching network. CSIN links
may independent and autonomous data and bibliographic computer
systems oriented to chemical substances, establishing a "library of
systems." Users may converse with any or all systems interfaced by
CSIB without training on these independent systems, regardless of the
hardware, software, data formats, or protocols of these information
resources.
5-2 July, 1984
-------
Information accessible through CSIN includes data on chemical
nomenclature, composition, structure, properties, toxicity,
production uses, environmental effects, regulations, disposal, and
other aspects of the life cycle of materials as they move through
society. Currently, twelve independent information resources are
accessible through CSIN, including: National Library of Medicine
(NLM); Chemical Information System (CIS); CAS-On-Line; SDC's ORBIT;
Lockheeds's DIALOG, and the Bibliographic Retrieval Service (BRS).
For further information contact nr. Sid Siegel at FTS 395-7285.
5.4 Graphical Exposure Modeling System (GEMS)
EPA has developed GEMS, an interactive computer system, to provide a
simple interface to environmental modeling, physiochemical property
estimation, statistical analysis, and graphical display
capabilities. GEMS is being developed for use by the Office of Toxic
Substances to support integrated exposure/risk analyses. The system
provides environmental analysts who are unfamiliar with computer
programming with a set of sophisticated tools to undertake exposure
assessments. For information about the system and the current
accessibility of GEMS, contact Bill Wood at FTS 382-3928.
5-3 July, 1984
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6. REGULATOR* STATUS (Current as of 6/10/84)
6.1 Promulgated Regulations
6.1 .1 EPA Programs
Clean Water Act (CWA)
0 Section 311 (b)(2)(A) - Polychlorinated biphenyls (PCBs) are
designated as hazardous substances (40 CFR 116.4). Accordingly,
PCBs ate subject to the general provisions, reporting quanti-
ties, and notification requirements established in CFR 117.
o Sections 307, 308, and 501 - Effluent standards for the toxic
pollutants, PCBs, are established for the following (40 CFR
129.105):
PCB manufacturers/
Electrical capacitor manufacturers, and
Electrical transformer manufacturers.
o Sections 301, 304, 306, 307, and 316 - PCBs are designated as
toxic pollutants (40 CFR 401.15). Accordingly, effluent
limitations, pretreatment standards, new source performance
standards (NSPS), and performance standards for new (PSNS) and
existing (PSES) sources have been promulgated for various
sections of the following industries:
Electroplating (40 CFR 413),2
'Steam electric power generating (40 CFR 423),
Metal finishing {40 CFR 433),2 and
Aluminum forming <40 CFR 467).2
o Sections 318, 402, and 405 - Under the National Pollutant
Discharge Elimination System (NPDES) permit testing
requirements, PCBs are listed as organic toxic pollutants on the
basis of gas chromatographic and mass spectroscopic analyses (40
CFR 122, App. D, Table II). Other permitting requirements are
covered in 40 CFR 123 to 124.
1Applies to those manufacturers of electrical capacitors and
transformers which contain PCBs or PCB-containing compounds as
part of the dielectric.
2PCBs are controlled by limiting the total toxic organics (TTOs)
which are the summation of all quantifiable values greater than
0.01 mg/1.
6-1 July, 1984
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Resource Conservation and Recovery Act (RCRA)
o Sections 1008 and 4004 - When applied to land used for the
production of animal feeds, including pasture crops for animals
raised for milk, solid waste containing PCBs at concentrations
equal to or greater than 10 mg/kg (10 ppm; dry weight) must be
incorporated into the soil (40 CFR 257.3-5 (b)}.
Section 3001 - PCBs are listed as hazardous waste constituents (40
CFR 261, App. VIII).
Toxic Substances Control Act (TSCA)
o Section 12(b) - Requires notification to EPA of intent to import
or export PCBs for any purpose other than disposal (40 CFR
707.60 (b)-(c)).
o Section 6(e)(3)(B) - Allows manufacturers to apply for
exemptions from the PCB manufacturing ban (40 CFR 750.10 -
750.21).
o Section 6(e) - Prohibits the manufacture, processing,
distributionin commerce, and use of PCBs or PCB items
regardless of concentration, in any manner other than in a
totally enclosed manner within the United States except those
PCBs or PCB items resulting from certain excluded manufacturing
processes or recycled PCBs (40 CFR 761.20). The excluded
processes and items are those in which:
The concentration of inadvertently generated PCBs in
products manufactured in or imported into the U.S. have an
annual average of less than 25 ppm, with a 50 ppm maximum
(49 FR 28189).
The concentration of inadvertently generated PCBs in the
components of detergent bars manufactured in or imported
into the U.S. is less than 5 ppm (49 FR 28190).
The release of inadvertently generated PCBs at the point at
which emissions are vented to ambient air is less than 10
ppm; and, the amount of inadvertently generated PCBs added
to water discharged from a manufacturing site is less than
100 g per resolvable gas chroma tograpMc peak per liter of
water discharge (49 FR 28190).
Recycled PCBs in paper products at concentrations less than
25 ppm with 50 ppm maximum or asphalt materials that have
no detectable concentration and have emissions into the
atmosphere of less than 10 ppm, with other requirements for
exclusion. (40 CFR 761.3 as amended by 49 FR 28190, July
10, 1984).
6-2 July, 1984
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Manufacturing Export Exemptions
o Items containing PCBs in concentrations less than 50 ppm can be
exported or imported for disposal.
Distribution in Commerce Exemptions
o PCBs or PCB items at concentrations of 50 ppm or greater, sold
before July 1, 1979, for purpose other than resale can be
distributed in commerce only in a totally enclosed manner after
that date.
o PCBs or PCB items at concentrations of less than 50 ppm are
allowed to be processed and distributed in commerce for the
purpose of disposal, and
o PCBs or PCB items at concentrations of 50 ppm or greater may be
processed and distributed in commerce for the purpose of
disposal in accordance with 40 CFR 761*
o Section 6(e)(2)(B) - PCB use authorizations have been approved
for the following non- totally enclosed uses:
o In transformers (except transformers for railroad
locomotives and self-propelled railroad cars), including
rebuilding and servicing (40 CFR 761 .30(a) (-1 ) (i)
Use and servicing of railroad transformers, and may be
processed and distributed in commerce for the purposes of
servicing these transformers (40 CFR 761 .30(b) {1 ) (i) -
Use and servicing of mining equipment (40 CFR 761.30(c)(1)
- (5)},
Intentionally manufactured PCBs in heat transfer systems at
a concentration of less than 50 ppm (49 FR 28190, July 10,
1984),
Intentionally manufactured PCBs produced after July 1 ,
1984, may be used in hydraulic systems at a concentration
of less than 50 ppm (49 FR 28190, July 10, 1984),
In carbonless copy paper (40 CFR 761.30{f)),
In "Diarylide" and "Phthalocyanin" pigments containing 50
ppm PCBs or greater if exempted under TSCA (6) (e) (3) (B) ,
(40 CFR 761 .30(g»,
Use and servicing of electromagnets, switches, and voltage
regulators (40 CFR 761.30(h)(1> - (2)(vii)),
6-3 July, 1984
-------
o Indefinitely in the compressors and in the liquids of
natural gas pipelines at a concentration level of less than
50 ppm (49 FR 28191, July 10, 1984),
o In small quantities for research and development (49 FR
28202, July 10, 1984),
o As a permanent microscopic mounting medium (49 FR 28202),
o In capacitors (40 CFR 761.30(1)(1)(i) - (ii)),
o Use and servicing of circuit breakers, reclosers, and
cables (40 CFR 761.30(m)(1)(i) - (ii)),
o As an immersion oil in fluorescence microscopy (49 FR
28202), and
o Indefinitely as optical liquids (49 FR 28202, July 10,
1984).
On July 10, 1984, EPA granted, under Section 6(e)(3)(B) of TSCA, one
year exemptions for the manufacturing, processing, and distribution
in commerce of certain PCB items (49 FR 28171). Regulations under
TSCA also cover marking (40 CFR 761.40); disposal (40 CFR 761.60);
storage for disposal (40 CFR 761.65); incineration (40 CFR 761.70);
chemical waste landfills (40 CFR 761.75); and decontamination (40 CFR
761.79).
6.1.2 Programs of Other Agencies
Federal Food, Drug, and Comestic Act (FFDCA) Administered by the FDA
o sections 306, 402, 406, 408, 409, and 701 - Establishes
restrictions on the industrial uses of PCBs in establishments
manufacturing food-packaging materials (21 CFR 109.!5(a) - (c)).
o Tolerances for PCBs in dairy products, poultry, eggs, finished
animal feed, fish, infant foods, and paper packaging materials
(21 CFR 109.30(a) - (b)). The tolerances and foods are
presented in section 7.3; and, tolerances for unavoidable
residues of PCBs in fish and shell-fish lowered from 5 ppm to 2
ppm (49 FR 21514, May 22, 1984. Effective date August 20, 1984.
o Provisions providing for minimizing the accidental PCB
contamination of animal feed in the production, handling, and
storage of animal feed (21 CFR 500.45).
o Provisions to preclude the accidental contamination of foods by
PCBs (21 CFR 110.40(b)).
6-4 July, 1984
-------
Hazardous Materials Transportation Act (DOT)
o PCBs are classified within the other regulated materials (ORM-E)
hazard class for the purposes of transportation (49 CFR 172.101
and 49 CFR 173.1300, Subpart 0).
o PCB packaging requirements (49 CFR 173.510).
o Other transportation regulations that cover PCB hazardous
materials (49 CFR 173-177).
Occupational Health and Safety Act
o Standards for employees exposed to hazardous air contaminants
limit occupational exposure to PCBs (29 CFR 1910.1000, Table 2-
1).
6.2 Proposed Regulations
6.2.1 EPA Programs
TSCA
o EPA withdrew the proposed rule (45 FR 30989) restricting the use
of PCBs at agricultural pesticide and fertilizer facilities on
March 19, 1984 (49 FR 10133).
o EPA is proposing to incorporate into existing American Society
for Testing and Materials (ASTM) test methods for PCBs (40 CFR
761), a revised ASTM method (centrifugation of water and
sediment in crude oils and fuels) to meet particular PCB
requirements (49 FR 22836, June 1, 1984).
o In an advance notice of proposed rulemaking (ANPR) EPA announced
its interest in collecting data specific to the risks posed by
fires involving electrical transformers that contain PCBs; and
to solicit data on methods for eliminating these risks for the
purpose of determining the need for further control through
regulation (49 FR 11070, March 23, 1984).
Comprehensive Environmental Response, Compensation and Liability Act
(CERCLA or Superfund).
o Sections 102(b), 103(a)(b) - CERCLA provides for the liability,
compensation, clean-up, and emergency response for the release
of hazardous substances into the environment. This Act also
deals with the clean-up of hazardous waste disposal sites (42
USC 9601; PL 96-501). EPA is developing regulations concerning
the designation of hazardous substances, the development of
reportable quantity requirements (RQ's), claims procedures, and
the confidentiality of business records (46 FR 54032). Re-
visions to the National Contingency Plan (NCP) as required by
CERCLA have been issued (47 FR 10972).
6-5 July, 1984
-------
PCBs are hazardous substances under CERCLA and will be subject
to regulations developed under Superfund. EPA has proposed
adjustments to the RO's established under CERCLA and the CWA (48
FR 23552).
6.2.2 Other Programs
o USDA
Proposed amendnents to the meat and poultry products inspection
regulations concerning compliance with performance standards for
retaining laboratory accreditation; requires a minimum
proficiency ]evel for the identification and quantification of
PCS residues of 0.5 ppm (45 FR 73949).
6.3 Other Actions
Public Health Service (PHS) National Toxicology Plan
o PCBs are recognized as substances or groups of substances that
may reasonably be anticipated to be carcinogens (Third Annual
Report on Carcinogens, Summary, September 1983, page 111).
6-6 July, 1984
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7. STANDARDS AND RECOMMENDED CRITERIA3
7.1 Air
7.3
o OSHA workplace exposures to toxic air contaminants, 8 hour TWA
(29 CFR 1910.1000, Table Z-1 ) .
Chlorodiphenyl (42 percent chlorine) 1
Chlorodiphenyl (54 percent chlorine) 0.5 mg/m
o NIOSH recommendation of weekly average 1 ug/m
o American Conference of Governmental and Industrial Hygienists
(ACGIH) recommended in 1980 TWA'S identical to those promulgated
by OSHA.
7.2 Water
o Water Quality Criteria (WQC); 45 FR 79318.
Freshwater aquatic life: 24 hour average 0.014 u g/1
Saltwater aquatic life: 24 hour average 0.03 ug/1
An estimated lifetime cancer risk for human health of 10
corresponds to a criterion concentration of 0.79 ng/L for the
ingestion of contaminated water and contaminated aquatic
organisms. The human health criteria are based on the
consumption of fish/shellfish (6.5 grams/day) in addition to
water (2 liters/day). Because PCB bioconcentration factors
average around 30,000, nearly all (99%) of the estimated
exposure results from consumption of aquatic organisms . Because
of this, the concentration corresponding to the 10" cancer risk
for the ingestion of contaminated aquatic organisms only is also
0.79 ng/L.
o Designated as hazardous substances under Section 311 of the CWA,
notification is required if discharges of PCBs exceed 10 pounds
(4.54 kg). The RQ proposed under CERCLA is 1.0 pound (0.454
kg), 48 FR 23552.
FDA temporary tolerances for unavoidable residues of PCBs in
certain foods and animal grains (21 CFR 109.30)
Milk and dairy products (fat basis) 1.5 ppm
Poultry (fat basis) 3.0 ppm
aSee Appendix A for a discussion of the derivation, uses, and
limitations of these criteria and standards.
7-1 July, 1984
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Eggs °-3
Finished animal feed (except feed
concentrates, feed supplements, and feed
premixes) °-2 PP"»
Animal feed (originating from animals) 2.0 ppm
Fish and shellfishb 2.0 ppm
Infant and jinior foods 0.2 ppm
Paper food-packaging material (Except those
with functional barriers that prevent
PCB migration). 10 ppm
21 CFR 109.30(a)(1-9) and 509.30
FDA action levels
Red meat 3 ppm
bTolerance of 2 ppm, effectively upheld (49 FR 21514).
7-2 July, 1984
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8. SPILL OR OTHER INCIDENT CLEAN-UP/DISPOSAL (CONTACT: National
Response Center, 800-424-8802, or 426-2675 in Washington, D.C.)
8.1 Hazards
PCBs are moderately combustible and may be carcinogenic. Fire
hazards are slight, but irritating or highly toxic gases are
generated when some of these materials burn. Although PCBs pose few
immediate health hazards, contact may cause burns to the skin and^
eyes. Vapors can cause eye and lung injury and irritation of the
throat.
PCB runoff from fire control or dilution water may cause pollution.
PCBs are toxic to aquatic life in very low concentrations.
8.2 First Aid
In case of contact with PCBs, immediately flush affected areas with
plenty of water for at least 15 minutes. If in eyes, hold eyelids
open and flush with lots of water. Remove and isolate contaminated
clothing and shoes.
8.3 Emergency Action
Spill or Leak_
isolate contaminated area and wear self-contained breathing apparatus
and full protective clothing. Stop discharge if possible without
risk. Avoid contact and isolate and remove discharged material. In
the case of small spills, take up with sand or other noncombustible
absorbent material, then flush area with water. For large spills,
dike far ahead of spill for later disposal. If water is contami-
nated, contact local health and pollution control authorities.
Fire
For small fires use dry chemical, C02f water spray or foam. For
large fires use water spray, fog or foam. Move container away from
fire area if possible.
8.4 Notification and Technical Assistance
Section 103 of the Comprehensive Environmental Response, Compensation
and Liability Act (CERCLA) or "Superfund" requires notification of
the National Response Center (NRC, 800-424-8802; 426-2675 in the
Washington, D.C. area) if releases exceed repayable quantities (10
Ibs. in the case of PCBs}. For emergency assistance call CHIMTRECi
800-424-9300. For information call the Division of Oil and Special
Materials at 1-202-245-3045.
8-1 July, 1984
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8.5 Disposal
No wastestreams containing PCBs were listed under RCRA regulations.
Disposal and marketing of PCBs are regulated under TSCA Section
6{e). See Tables 3 and 4 for summary of the disposal requirements
for PCBs and related materials. EPA has concluded in general that
PCBs at levels of 50 ppm or greater must be disposed of in accordance
with the requirements of 40 CFR Part 761. Under TSCA, PCBs in
concentrations below 50 ppm (excluding dilutions of higher level
PCBs) are not required to be disposed of in any special manner. EPA
has a list of commercial landfill sites approved for PCB disposal and
the contaminated items each location can accept. (CONTACT: TSCA
Assistance Office, 800-424-9065; 382-3790 in the Washington area).
8-2 July, 1984
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TABLE 3; SUMMARY OF PERMANENT DISPOSAL REQUIREMENTS
PART A; Liquid PCBs and Contaminated Debris
TSCA Regulatory Disposal Provisions
Chemical High Municipal
Waste Efficiency EPA-Approved Solid
PCS or PCS Item Incinerator5 Landfillb Boiler0 Alternative*3 waste
1. PCB Chemical Substances x
(above 500 ppm PCBs)
2. Mineral oil dielectric x x x
fluid from PCB-contami-
nated electrical equip-
ment (50-500 ppm PCBs)
3. Liquids, other than mineral x x x
oil dielectric fluid (50-500
ppm PCBs)
4. Non-liquid PCBs in the form x x
of contaminated soil, rags,
or other debris (PCBs above
50 ppm)
5. Dredged materials and x x x
municipal sewage treatment
sludges (PCBs above 50
ppm)
a. 40 CFR 761.70
b. 40 CPR 761.75
c. 40 CFR 761.60 (a) (2) (iii) & 40 CFR 761.60 (a) (3) (iii)
d. 40 CFR 761.60 (a) (5) (iii) & 40 CFR 761.60 (c)
8-3 July, 1984
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TABLE 4:
SUMMARY OF PERMANENT DISPOSAL REQUIREMENTS
PART B: PCS ARTICLES
TSCA Regulatory Disposal Provisions
PCS or PCB Item
1. PCB Transformers (PCBs
above 500 ppm)
2. PCB-Contaminated
Transformers
(50-500 ppm PCBs)
3. PCB-Contaminated
Capacitors (50-
500 ppm PCBs)
4. PCB Small Capacitors
containing less than
1.36 kg. (3 Ibs.) die-
lectric fluid, otherwise
fluid must be drained
first and the contents
properly disposed of (ap-
plies to present and former
manufacturers of- "PCB
capacitors or^equipment)
5. PCB Small Capacitors
(applies to anyone other
than present or former
manufacturers of PCB
capacitors or equipment)
6. PCB Large Capacitor, high
or low voltage
Incinerator0
Chemical
Waste
Landfillb
High
Efficiency
Boiler0
EPA-Approved
Alternative*3
Municipal
Solid
Haste
8-4
July, 1984
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TABLE 4; SUMMARY OF PERMANENT DISPOSAL REQUIREMENTS
PART B; PCB ARTICLES
TSCfl Regulatory Disposal Provisions
PCB or PCB Item
7. PCB Hydraulic Machines
8. Other PCB Articles
9. PCB Containers (PCBs
above 50 ppm)
10. PCB Containers (PCB
concentration of less
than 500 ppm)
Incinerator3
Chemical
Waste
Landfill13
High
Efficiency
Boiler0
EPA-Approved
Alternative*1
Municipal
Solid
Waste
x
X
a. 40 CFR 761.70
b. 40 CFR 761.75
c. 40 CFR 761.60 (a) (2) (ni) & 40 CFR 761.60 (a) (3) (iii)
d. 40 CFR 761.60 (a) (5) (iii)
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9. SAMPLING, ACCEPTABLE ANALYTICAL TECHNIQUES AMD QUALITY_ASSURANCE
9.1 Air (CONTACT: Dr. Robert G. Lewis, FTS 629-3065}
PCBs are not criteria pollutants and therefore a criteria analysis
methodology has not been promulgated for them. Methodology has been
developed and used by ORD for sampling and analysis of PCBs in air.
Two EPA reports, EPA-600/4-79-022 (Sources of Emissions of
Polychlorinated Biphenyls into the Ambient Atmosphere and Indoor Air)
and EPA-600/2-80-180 (Protocol for Assessment of Human Exposure to
Airborne Pesticides), describe sampling and analysis methodology
which has been determined to be more than adequate.
The collection medium of preference is polyurethane foam (open-cell
polyether type; density 0.02 g/cm3). Air is drawn through the
cylindrical plugs of the foam for periods of 4 to 24 hours using
either low- or high-volume pumps, depending on the particular
application. After extraction from the plugs with appropriate
solvents, the samples are analyzed by electron capture GC and
confirmed if necessary by GC-MS.
The method has been used successfully in the range of 0.1 ng/m to 11
ug/m3 (30 ng to 3 mg actual PCBs collected). Replicate sampling
gives a relative standard deviation of 17%. The collection
efficiency of the method is greater than 95% for all Aroclor mixtures
tested with the low volume method and between 75% and 100%, depending
on percent chlorine, for the high-volume method.
The limits of detection depend on the background interference arising
from the foam and on the particular instrumentation being used for
the analysis. They commonly range from 15 ng for Aroclor 1242 to 500
ng for Aroclor 1260.
9.2 Water (CONTACTS: 'Thomas Bellar, FTS 684-7311 or
James Lichtenberg, FTS 684-7308)
PCS - 1016 CAS No. 12674-11-2
PCB - 1221 CAS No. 11104-28-2
PCB - 1232 CAS No. 11141-16-5
PCB - 1242 CAS No. 53469-21-9
PCB - 1248 CAS No. 12672-29-6
PCB - 1254 CAS No. 11097-69-2
PCB - 1260 CAS No. 11096-82-5
These Aroclors (PCBs) are proposed parameters under Section 304(h) of
the Clean Water Act. They are listed as priority pollutants.
The existing and proposed procedures for analysis of PCBs in natural
waste and drinking waters is liquid-liquid extraction followed by
analysis of extracts by gas chromatography.
Liquid-Liquid Extraction Methods: EPA #608, 625
ASTM #3534
Method #3 EPA
9-1 July, 1984
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Major Equipment Required: Gas Chroma tograph
A measured volume of sample, approximately 1-liter, is solvent
extracted with methylene chloride using separatory funnel
techniques. The methylene chloride extract is dried and exchanged to
hexane during concentration to a final volume of 10 ml or less.
Identification is made from gas chroma tographic patterns obtained
from injection of 1 to 4 ul of the extract through two or more unlike
columns. Detection and measurement are accomplished using electron
capture, microcoulcmetric, or electrolytic conductivity detectors.
The method detection limit is approximately 0.1 ug/1 . If EPA #625 is
followed, detection is accomplished through Mass Spectrometry with a
detection limit of approximately 35
Samples must be collected in glass bottles following conventional
sampling practices except the bottle must not be prewashed with
sample before collection. Samples must be iced or refrigerated at
4°C from the time of collection until extraction. If the sample will
not be extracted within 72 hours of collection, the sample should be
adjusted to a pH range of 5.0 to 9.0 with sodium hydroxide or
sulfuric acid. Spiked river water samples have been stored for up to
7 days under these conditions with no apparent losses.
9_2 July, 1984
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LIST OF PROCEDURES FOR PCBse
Method
Detection
Limit
(MDL)
Recovery
(%)
Standard
Deviation
(%)
Status
(As of 3/81)
EPA-3
EPA-608
EPA-625
ASTM-3534
N.D.
c
d
1 .0 ug/1
N.D.
88-96
N.D.
99
N.D.
2-5
N.D.
6.9
Official
Proposed
Proposed
Proposed
.
aAll are liquid-liquid extraction methods; N.D'. means not determined.
bSingle laboratory recovery from spiked reagent water or spiked Wa'ste'wat'e'r.
CMDL for PCB-1242 is 0.065 ug/1; all other PCB MDLs are undetermined 'for
this method.
dMDL for PCB-1221 is 30 ug/1; for PCB-1254 MDL is 36 ug/1. All other
MDLs are undetermined for this method.
References for Wa ter Analysis
"Method for Polychlorinated Biphenyls (PCBs) in Industrial
Effluents." National Pollutant Discharge Elimination System Appendix
A, Federal Register, 38, No. 75, Part II. (1973); Method, EPA-3.
"Standard Test Method for Measuring Polychlorinated Biphenyls (PCBs)
in Water," ASTM D-3534-76, Part 31, Water, Annual Book of ASTM Stand-
ards, 1980.
"Methods for Organic Chemical Analysis of Water and wastes by GC,
HPLC, and GC/MS." Method 625; Base/Neutrals and Acids. USEPA, En-
vironmental Monitoring and Support Laboratory, Cincinnati, Ohio
45268.
"Methods for Organic Chemical Analysis of Water and Wastes by GC,
HPLC, and GC/MS." Method 608, Pesticides and PCBs, USEPA, Environ-
mental Monitoring and Support Laboratory, Cincinnati, Ohio 45268.
9.3 Solid Waste (CONTACTS: Werner Beckert, FTS 545-2137 and
Donald Gurka, FTS 545-2113)
Method 8.08 and a Method for Polychlorinated Biphenyls (PC.Bs) in
Wa ter and Was tewa ter, p. 43 are approved for analyses of PCBs in
solid wastes (Test Methods for Evaluation Solid Wastes: Physical/-
Chemical Methods, USEPA/SW.846, 1980).
There is no approved method for analysis of PCBs in hazardous waste
matrices. However, methods 608 and 625 for water have been employed
9-3
July, 1984
-------
in some cases. Analyses via electron capture GC or GC/MS are gen-
erally reliable for 5 to 500 mg/kg samples, with detection limits of
1 mg/kg; certain matrices (e.g., soils, sediments, phthalate esters)
may interfere however.
Standard deviations on successive analyses typically are 1-26
percent; spike recoveries of 76-109 percent and relative standard
deviations of 2.0-11.5 percent were reported for PCBs in a motor oil
matrix.
References for Solid Waste Analysis
Criterion Document: Polychlorinated Biphenyls. Criteria and Stan-
dards Division, Office of Water Planning and Standards, U.S. EPA, PB
296803.
T.A. Bellar and J.J. Lichtenberg, The Determination of Polychlori-
nated Biphenyls in Transformer Fluid and Waste Oils. EPA-EMSL-
Cincinnati, September 17, 1980.
J.W. Eichelberger, L.E. Harris, and W.L. Budde, Anal. Chem. 46, 227
(1974).
9.4 Other Samples
A method for analysis of PCBs in soils and bottom sediments may be
found in Chemistry Laboratory Manual for Bottom Sediments and Elu-
triate Testing,(USEPA/Regionv)CentralRegionalLaboratory,
Chicago, 111., p.108).
The soil or sediment sample is dried, sieved, and extracted for 16
hours (Soxhlet) with acetone/hexane (1:1). The extract is concen-
trated and passed through Florisil or silica gel for elimination of
interferences. Sulfur is a common interfering substance. Analysis
is affected by GC and' ED or EC detection. Detection limit is about 2
mg/kg.
The NIPSH Manual of Analytic Methods contains several methods for PCS
analysis. Method 244 (Vol. 1) describes a procedure for analysis of
PCBs in air; adsorption onto Florisil and desorption with hexane is
followed by analysis by electron capture GC. The range of detection
is 0.01 to 10 mg/m^. The sample may be reacted with antimony pen-
tachloride to yield decachlorobiphenyl which is easier to selectively
quantify (method 253).
A method (329, Vol. 6) is also listed for analysis of PCBs in blood
serum. The blood serum is extracted with ether/hexane (1:1), and the
extract chromatographed, concentrated, and analyzed for PCBs by elec-
tron capture GC. The detection limit is about 0.026 mg/1 (based on 5
ml sample) with a working range up to 10 mg/1. Pesticides and their
metabolites may interfere; precision is about 14% and total recovery
exceeds 80%.
9-4 July, 1984
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Methods of analysis for PCBs in a wide variety of environmental sam-
ples have been reviewed briefly by IARC [IARC, 1978). Hutzinger, et
al. (The Chemistry of PCBs, Cleveland, Ohio, Chemical Rubber Co.,
pp. 41-70, 169-193; 1974) gives a more detailed review of analytical
techniques for PCBs.
9.5 Quality Assurance
Single laboratory test data on simple spiked matrices have been col-
lected by EPA. Interlaboratory accuracy and precision and method
detection limit data are currently being collected. Quality control
and performance evaluation samples (concentrates of PCBs in acetone
to be spiked into water) are available from the Environmental
Monitoring and Support Laboratory, Quality Assurance Branch, USEPA,
Cincinnati, Ohio 45268.
9-5 July, 1984
-------
REFERENCES
The major references used in the preparation of this document are listed
below. EPA references are listed by the EPA office of origin and the year of
publication. For further information refer to the contacts given throughout
this document or contact the relevant EPA offices given at the end of this
section.
[lARC, 1978)
(MAS, 1979)
(OTS, 1976)
(OTS, 1977)
(OWRS, 1979)
(OWRS, 1980)
(WHO, 1976)
IARC Monographs on the Evaluation of the Carcinogenic Risk
of Chemicals to Humans, Vol. 18, pp. 43-103/ International
Agency for Research on Cancer, World Health Organization
(1978).
Polychlorinated Biphenyls, National Academy of Sciences,
Washington, D.C. (1979).
PCBs in the United States. Industrial Use and Environmental
Distribution, EPA-560/6-76-005, Office of Toxic Substances
(1976).
A First Order Mass Balance Model for the Sources,
Distribution, and Fate of PCBs in the Environment, EPA-
560/6-77-006, Office of Toxic Substances (1977).
Water-Related Environmental Fate of 129 Priority Pollutants,
Vol. 1, Chapter 36, EPA-440/4-79-029a, Office of Water
Regulations and Standards (1979).
Ambient Water Quality Criteria for PCBs, EPA-440/5-80-068,
Office of Water Regulations and Standards (1980).
Polychlorinated Biphenyls and Terphenyls.
Environmental
Health Criteria 2, World Health Organization (1976)
R-1
July, 1984
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OFFICE CONTACTS
The EPA offices and divisions that are listed below may be contacted for more
information relating to the indicated sections of this document. While these
offices are, in many cases, the offices of origin for the data included in
this paper, the personal contacts given throughout this document should be
contacted first. Unless otherwise noted, the offices listed are situated in
Headquarters, Washington, D.C., and the telephone numbers given are FTS
(Federal Telecommunications System) numbers. For commercial telephone calls
to Headquarters which are not placed on FTS, area code 202 must be used.
Other commercial numbers are noted for the office contacts located outside
Washington, D.C.
HEALTH AND ENyiRObMENTAL EFFECTS (Section 2)
Office of Health and Environmental Assessment (OHEA)
Environmental Criteria and Assessment Office:
Cincinnati, OH 684-7531 (513-684-7531)
Research Triangle Park, NC 629-4173 (919-541-4173)
Carcinogen Assessment Group 382-7341
Office of Drinking Water (ODW)
Health Effects Branch 382-7571
Office of Toxic Substances (OTS)
Health and Environmental Review Division 382-4241
Environmental Research Laboratory
Duluth, MN, Region V 783-9550 (218-727-6692)
ENVIRONMENTAL RELEASES AND EXPOSURE^ (Sections 3 and 4)
Office of Air Quality and Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Water Regulations and Standards (OWRS)
Monitoring and Data Support Division 382-7051
Office of Toxic Substances (OTS)
Exposure Evaluation Division 382-3873
R-2 July, 1984
-------
DATA BASES (Section 5)
Office of Toxic Substances (OTS)
Information Management Division 382-3749
REGULATORY STATUS, STANDARDS, AND CRITERIA (Sections 6 and 7)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Drinking Water (ODW)
Criteria and Standards Division 382-7575
Office of Water Regulations and Standards (OWRS)
Criteria and Standards Division 755-0100
Effluent Guidelines Division 382-7120
Office of Solid Waste (OSW)
Permits and State Programs Division 382-4746
SPILL CLEAN-UP AND DISPOSAL (Section 8)
NOTE: For Emergencies call the National Response Center at 1-800-424-8802
(1-800-426-2675 from the Baltimore/Washington area).
Office of Emergency and Remedial Response (OERR)
Emergency Response Division 382-2182
Hazardous Site Control 382-2443
Oil and Hazardous Materials Spills Branch
Edison, NJ; Region II 340-6635 (201-321-6635)
ANALYTICAL TECHNIQUES (Section 9)
Environmental Monitoring Systems Lab (EMSL)
Air Analysis
Research Triangle Park, NC 629-2454 (919-541-2454)
Hater Analysis
Cincinnati, OH 684-7311 (513-684-7311)
R-3 July, 1984
-------
Waste Analysis
Las Vegas, NV 545-2137 (702-798-2137)
Office of Monitoring Systems
and Quality Assurance 382-5767
GENERAL IPP COMMENTS, CORRECTIONS, OR QUESTIONS
Chemical Coordination Staff
Chemical Information
and Analysis 382-3375
R-4 July, 1984
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PHTALATE ESTERS
-------
PHTHALATE ESTERS
Table of Contents
Physical/Chemical Properties and Chemistry 1-1
Properties 1-1
Chemistry and Environmental Fate/Transport 1-1
Effects Information 2-1
Health Effects 2-1
Environmental Effects 2-7
Environmental Release 3-1
Exposure Routes 4-1
Air Exposure 4-1
Hater Exposure 4-1
Other Routes 4-2
Data Bases 5-1
Chemicals in Commerce Information System (CICIS) 5-1
EPA Chemical Activities Status Report (EPACASR) 5-1
NIH/EPA Chemical Information System (CIS) 5-1
Chemical Regulations and Guidelines System (CRGS) 5-1
Chemical Substances Information Network (CSIN) 5-2
EPA Information Clearinghouse 5-2
Regulatory Status 6-1
Promulgated Regulations 6-1
Proposed Regulations 6-4
Other Actions 6-4
Standards and Recommended Criteria 7-1
Air 7-1
Water 7-1
Spill or Other Incident Clean Up/Disposal 8-1
Hazards and Safety Precautions 8-1
First Aid 8-1
Emergency Action 8-1
Notification and Technical Assistance 8-1
Disposal 8-2
July, 1983
-------
Sampling, Acceptable Analytical Techniques, and Quality Assurance 9-1
Air 9-1
Water 9-1
Solid Waste 9-2
Other Samples 9-2
References and Office Contacts R-1
July, 1983
-------
PHTHALATE ESTERS
1. PHYSICAL/CHEMICAL PROPERTIES AND CHEMISTRY
1.1 Properties
Phthalate esters are alkyl esters of 1,2-benzene dicarboxylic acid.
Most are produced commercially by the esterification of phthalic anhy-
dride with alcohols in the presence of catalyst; alkyl benzyl
phthalates also require benzyl chloride as a precursor. In recent
years, annual domestic production of all phthalate esters has exceeded
one billion pounds (OWRS, 1980a; OTS, 1980).
In general, the alkyl phthalates can be described as colorless (or
lightly colored), oily liquids with little, if any, odor. They have
relatively high boiling points and low vapor pressures; their water
solubilities range from sparingly soluble for the longer chain
alkylesters to moderately soluble for the glycol ether esters; and
they are stable to heat and light (OTS 1981; OWRS 1979). Phthalate
esters, most notably di(2-ethylhexyl) phthalate (DEHP), have found
widespread use as plasticizers because of their unique combination of
physical/chemical properties such as low volatility, resistance to
migration from polymers, low temperature flexibility, chemical
stability, freedom from odor and taste, and compatibility with polar
polymers and additives over a wide range of compositions.
Table 1 lists most of the phthalate esters discussed in this report.
Table 2 summarizes their physical/chemical properties. This report
will focus on DEHP because of its high production volume, persistence
in the environment, and potential for human exposure. Information on
the other phthalate esters will be included where available.
1.2 Chemistry and Environmental Fate/Transport
DEHP is the most studied of the phthalate esters. For several of the
phthalate esters, very little specific data were available; therefore,
the behavior of some of these compounds in the environment was infer-
red from data for the phthalate esters as a group.
Phthalate esters are widely distributed in the environment. They have
been found in wells and drinking water, oil, soil, air, plants, fish,
food, bacteria, fungi, worms, cattle pineal glands, bovine heart
muscle, and humans. The fact that they are so commonly found suggests
that some may be naturally-occurring. However, there is also a dis-
tinct possibility of sample contamination in collection and
analyses. The extent of naturally-occurring phthalate esters, if any,
is small when compared with anthropogenic sources (OWRS, 1979; OWRS,
1980a).
The two transport mechanisms that appear to be most important for the
phthalates in the aquatic environment are adsorption onto suspended
solids and particulate matter and complexation with natural organic
!_! July, 1983
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TABLE 1: STRUCTURE AND NOMENCLATURE OF THE PHTHALATE ESTERS
General Structure:
Side chain structures (R1 and R2) are given below for each phthalate.
NAME
ALTERNATE NAMES
CAS NO.
SIDE CHAIN (R1 AND
Dimethyl phthalate
Diethyl phthalate
Dibutyl phthalate
Di-n-octyl phthalate
Di(2-ethylhexyl) phthalate3
Benzyl butyl phthalate
c
M
^<
DMP; 1,2-Benzenedicarboxylic acid, 131-11-3
dimethyl ester
DEP; 1,2-Benzenedicarboxylic acid, 84-66-2
diethyl ester
DBP; 1,2-Benzenedicarboxylic acid, 84-74-2
dibutyl ester
DNOP; 1,2-Benezenedicarboxylic acid, 117-84-0
dioctyl ester
DEHP; 1,2-Benezenedicarboxylic acid, 117-81-7
bis(2-ethylhexyl) ester;
bis(2-ethylhexyl) phthalate
BBP; 1,2-Benzenedicarboxylic acid, 85-68-7
butyl phenylmethyl ester
-CH,
-(CH2)3CH3
-(CH2)7CH3
-CH2CH(C2H5)
-(CH2>3CH3 and -C
ID
* a
DEHP and DNOP are sometimes mistakenly reported as each other in the literature.
-------
TABLE 2: PROPERTIES OF PHTHALATE ESTERS3
l
UJ
Cj
c
GO
10
PROPERTY
Molecular weight
Melting point, °C
Boiling point, °C
Vapor pressure, torr (°C)
Water solubility, mg/L (25°C)
Log octanol/water partition
coefficient
Specific gravity0
Vapor density (air=1)
Flash point, open cup, °F
DMP
194
3
284
1.0 (100)
4320b
2.1
1.192
6.69
315
DEP
222
-41
298
0.05(70)
896b
3.2
1.120
7.66
322
DBP
278
-35
340
1.0(147)
13b
5.2
1.048
9.58
375
DNOP
391
-25
220(4 torr)
<0. 2(150)
3
9.2
0.978
(20°/4°C)
-
219
DEHP BBP
391 31 2b
-50 -35b
384 377b
1.21(200) <0. 01(25)
0.4 2.9b
8.7 4.8-5.8b
0.985 1.115-1.1
b
23(
(25°/25°C)
13.45
420 390d
a Source: (OTS,1981) unless otherwise noted.
b Source: (OWRS, 1979).
c The density at 20°C relative to water at 20° unless otherwise specified.
Source: Plasticizers and Resin Modifiers; Monsanto Co.; Technical Publication IC/PL-361 .
-------
substances, such as fulvic acid, to form water-soluble complexes or
emulsions. Photolysis, oxidation, and hydrolysis are too slow to be
environmentally significant. The second order rate constants from the
alkaline hydrolysis of a group of phthalate esters were measured; the
corresponding half-lives in neutral water ranged from 3.2 years for
DMP to 2,000 years for DEHP. Volatilization is not considered to be a
competitive transport process. The transport of the phthalate esters
will be dependent upon the hydrogeologic conditions of the aquatic
system (OWRS, 1979; OWRS, 1980a).
The fate of DEHP and DMP were evaluated in five simulated ecosystems
using EXAMS (Exposure Analysis Modeling System). The simulation
predicts that, for phthalates esterified with short-chain alkyl
groups, biochemical transformations will compete with export in the
ecosystems with long retention times (i.e., ponds or lakes). For
phthalates esterified with larger alkyl groups such as DEHP, trans-
formation processes are slow. Export will be the dominant process for
all phthalate esters entering a river, regardless of chain length.
Phthalate esters with alkyl chains of intermediate length exhibit
intermediate behavior. The oceans may be considered the ultimate sink
for phthalate esters introduced into unimpeded rivers (OWRS, 1979;
OWRS, 1980a).
Phthalate esters have been identified in living matter, and data
collected from field and laboratory studies indicate that they can be
taken up and accumulated by a variety of organisms. The phthalates
are degraded by microbiota and metabolized by fish and animals; they
are not expected to biomagnify. The highest concentrations would be
expected at intermediate levels of the food chain (e.g., inverte-
brates) rather than at the top as occurs with chemicals such as DDT.
Thus, bioaccumulation, biotransformation, and biodegradation are
important aquatic fate processes for phthalate esters (OWRS, 1979).
The fate of phthalate esters in air is expected to be controlled by
hydroxyl radical attack. Adsorption onto particulates and rainout are
expected to be less important fate processes (OWRS, 1980a).
Little information is available on the fate of phthalate esters in
soil, even though the primary point of entry into the environment is
the soil (via landfills). The migration of phthalate esters out of
plastics is slow. The amount available for transport or degradation
is expected to be low. However, the formation of soluble complexes
may increase their mobility. Thexphthalate esters may also be subject
to biodegradation; however, the degradation rates measured have been
highly variable (OWRS, 1979).
1-4 July, 1983
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2. EFFECTS INFORMATION
2.1 Health Effects
2.1.1 Acute Toxicity
While numerous reports document the toxic effects in animals due to
short-term, high-level exposure to phthalate esters, the information
for humans is severely limited. The meager toxicological data may be
attributed to the long use of these esters with few cases of adverse
effects noted in exposed populations. It has been suggested that
patients receiving transfusions through PVC tubing and blood bags may
have suffered "shocked-lung" syndrome due to the leaching of DEHP into
the blood. While phthalates increase platelet adhesiveness and may be
a factor in the formation of pulmonary embolt, evidence of in vivo
toxicity in recipients of blood transfusions is lacking. Evidence has
accumulated, however, to indicate that exposure to DEHP and other
plasticizers is likely to occur from the use of PVC materials in
transfusions (OWRS, 1980a; OTS, 1981).
The estimated lethal dose of DEP for humans is 0.5 g/kg and the lowest
published toxic concentration in air for humans is 1.0 g/m3. A
workman ingesting lOg DBF experienced nausea, vertigo, albuminuria,
keratitis (cornea inflammation), and lachrymation a few hours after
ingestion; these symptoms most likely resulted from the toxic effects
of the hydrolysis products of DBP (butanol). In humans, ingestion of
DMP is reported to cause irritation of the buccal mucosa (cheek),
nausea, vertigo, vomiting, coma, and a drop in blood pressure. DMP is
not irritating to the human skin, nor is dermal absorption efficient
in humans (OWRS, 1980a).
A review of the acute toxicity of phthalate esters in experimental
animals reveals that the phthalates exhibit relatively low acute
toxicity. L°50 values for various exposure routes and several
mammalian species normally exceed 1 g/kg for all phthalates
examined. Reported values range from 1 g/kg for DEP (oral LD50 in
rabbits) to 50 ml/kg for DEHP (i.p. LD50 in rats) (OWRS, I980b).
2.1.2 Chronic Toxicity
Chronic toxicity data in humans for the phthalate esters are limited.
Industrial workers exposed to ambient levels of 10 to 66 mg/m3 of
phthalate vapors or aerosols (a mixture of phthalates, primarily DBP)
for 6 months to 19 years exhibited polyneuritis (nerve inflammation);
the frequency and severity increased with length of exposure. The
most frequent worker complaint was pain in the upper and lower
extremities, often accompanied by numbness and spasms. This study,
however, must be taken with some reservation because of the presence
of other chemicals such as tricresyl phosphate, a substance known for
inducing polyneuritis (OWRS, 1980b).
2-1 July, 1983
-------
Symptoms of hepatitis have been observed in hemodialysis patients
using new PVC dialysis tubing. Experiments revealed that phthalates
were leached continuously from the tubing and that the symptoms
disappeared shortly after a change to other hemodialysis tubing (OWRS,
1980a).
The chronic adverse effects for various phthalate esters in laboratory
animals are shown in Table 3, and carcinogenic, mutagenic, and
teratogenic/reproductive effects are also discussed below. The lowest
effect levels (excluding the carcinogenic!ty of DEHP) shown are 0.4 g
DEHP/Xg f°r teratogenicity in mice (the no apparent effect level,
NOEL, was 0.07 g/kg) and 0.6 to 0.7 g DEHP/kg for testicular atrophy
in rats and mice. Most other reported effect levels for the
phthalates exceed 1 g/kg (OWRS, 1980a).
DEHP has been shown to produce changes in liver function as indicated
by increases in liver weight and morphological and biochemical
alterations in rats, mice, and rhesus monkeys. DEHP also induces the
proliferation of peroxisomes in liver cells (peroxisomes are
organelles which are functionally involved in lipid metabolism,
glyconeogenesis, and the detoxification of hydrogen peroxide).
Sustained peroxisome proliferation in liver cells has been associated
with increased appearance of liver cancer in rodents. A possible
mechanism for DEHP induced carcinogenesis in rats may involve chronic
proliferation of peroxisomes, however, supporting evidence is lacking
(EHP, 1982). Recent testing under the direction of The Chemical
Manufacturers Association (CMA) has confirmed that DEHP induces
peroxisome proliferation in the liver.
Water Quality Criteria have been established for phthalate esters
based on human health considerations. Allowable daily intakes (ADIs)
for a 70 kg person were developed (using a NOEL and a safety factor of
100) for DMP (700 mg), DEP (438 mg), and DBP (12.6 mg). Note that
these ADI values are not necessarily based on the data described
below; also, the ADI for DEHP (42 mg) is no longer applicable due to
the recently discovered carcinogenic potential (OWRS, 1980a; OWRS,
1980b).
Carcinogenicity - Adequate long term carcinogenicity testing has been
conducted for DEHP. The evidence suggests that DEHP is a liver car-
cinogen in both rats and mice. DEHP was administered to rats of each
sex at 0.0, 0.6, or 1.2% of the diet (equivalent to doses of about 300
rag/kg and 600 mg/kg per day for 300 g rats) and mice of each sex at
0.0, 0.3, or 0.6% of the diet (equivalent to doses of about 720 mg/kg
and 1440 mg/kg per day for 25 g mice) for 103 weeks. DEHP was
carcinogenic for rats and mice of either sex, inducing hepatoeellular
carcinomas or neoplastic nodules in rats and hepatoeellular carcinomas
or adenomas in mice. In rats, the neoplastic liver nodules were
significantly elevated in all treatment groups compared with controls
and the combined incidences of neoplastic nodules and hepatoeellular
carcinoma were significantly elevated in high dose male rats and in
both high and low dose females. The incidence of hepatoeellular
carcinoma alone was statistically significant only for high dose
female rats. Increased incidences of hepatoeellular carcinoma were
2-2 July, 1983
-------
observed in high dose male mice and in both low and high dose
females. the combined incidences of hepatocellular carcinoma and
hepatocellular adenoma were also elevated in these groups (OWRS,
1980a).
Other lifetime feeding studies have shown no increased incidence of
neoplasms due to ingestion of DEHP, DBF, and DMP at levels of 200 to
1400 mgAg/day. NTP test results for BBP are difficult to
interpret. While no carcinogenic effects were noted for mice fed 0.6%
and 1.2% BBP in their diet, female rats receiving 1.2% BBP showed an
increased incidence of myelomonocytic leukemia. However, due to the
variable and high background incidence of this lesion in similar
groups of historical controls, the evidence for BBP was judged to be
equivocal. In addition, excessive numbers of BBP-treated male rats
died and no evaluation of tumorigenic response in male rats could be
made. No data are available concerning the carcinogenicity of DEP and
DNOP (OWRS, 1980a).
Mutagenicity - All of the phthalate esters under consideration in this
document were examined in the Ames Salmonella test using metabolic
activation under the National Toxicology Program protocol; all
chemicals tested were judged to be nonmutagenic. However, other
experiments indicate that some phthalates (DEP, DMP} are mutagenic in
the Ames test in the absence of the activating S-9 enzymes. Conflic-
ting results are also reported -concerning the mutagenic potential of
the phthalate monoesters formed in the presence of S-9 associated
enzymes (EHP, 1982).
DEHP showed no increases in chromosomal aberrations in human fetal
lung cells, human leukocytes, or Chinese hamster cells exposed in
culture. While another study did report effects in Chinese hamster
cells, the effects were weak. Chromosomal aberrations and sister-
chromatid exchanges are also reported to show slight increases in
Chinese hamster cells exposed to DBP; however, the increases were
slight and no clear dosage effect was observed. Therefore, no
definitive conclusions concerning the genetic risk from exposure to
most phthalate esters can be drawn at this time (OWRS, 1980a).
As part of the negotiated testing program under section 4 of TSCA, CMA
has submitted results of genotoxicity studies for DEHP, and mono-2-
ethyl phthalate (MEHP). CMA reported no significant genotoxic effects
were noted for these compounds. No mutagenic activity was found in
Ames Salmonella tests (5 strains, with and without microsomal
addition). Several other genotoxic tests also indicated no mutagenic
or clastogenic activity for DEHP and MEHP (46 FR 53775). Other
results of the CMA testing program suggest that DEHP does not bind to
DNA in_ vivo (CPSC, 1983). EPA is evaluating this information for
consideration of further testing.
2-3 July, 1983
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TABLE 3: EFFECTS OF PHTHALATE ESTERS ON LABORATORY ANIMALS3
Adverse Effects
DEHP
Hepatocellular
Carcinoma plus
Neoplastic Nodules
He pa toce 1 lu la r
Carcinoma plus
Adenoma
Teratogenesis
Testicular Atrophy
Embryotoxicity
DMP
Chronic Nephritis
Embryotoxicity
PEP
Teratogenesis
DBF
Teratogenesis
Testicular injury
BBP
Periportal Hepatitis
Carcinogenicity
Species
Rat
Mouse
Mouse
Mouse
Rat
Mouse
Rat
Chick/Embryo
Rat
Mouse
Rat
Mouse
Mouse
Lowest Reported
Effect Levels
g/kg % Incidence
0.6
0.36
0.4
0.72
0.6
0.83
1.9
2.1
2.0
0.5
26
52
14
90
100
4.0
0.005/egg 100
81
No Apparent
Effect Levels
gAg
0.07
0.36
0.3
2.0
0.8
1.4
Source: (OWRS, 1980a).
2-4
July, 1983
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Teratogenicity and Reproductive Effects - Most phthalate esters are
capable of producing teratogenic and reproductive effects at high
doses by various routes. DEHP at high doses (> 5 ml/kg), induced
gross abnormalities in both rats and mice. DMP (0.3 ml/kg), DBF (0.3
mlAg)f and DEP (0.5 ml/kg) have also produced skeletal malformations
in rats. Injection of phthalate esters into developing chick eggs
produced no teratogenic effects with DBF, BBP, or DMP; there was a
single incidence with DEP. Increased embryo mortality was noted for
DMP, DEP, DBP, DNOP, and BBP (OWRS, 1980a).
Feeding studies with pregnant mice yielded no-effect levels of about
70 mg/kg/day for DEHP and 370 mg/kg/day for DBP for the mouse
fetuses. At dose levels of 410 mg/kg for DEHP and 2100 mg/kg for DBP
increases in fetal resorption and external malformations were
observed. The major malformations in this study were neural tube
defects (exencephaly and spinabifida). These authors concluded that
normal exposure to phthalate esters (<1 mg/kg/day) should not pose an
imminent threat to human fetal development (EHP, 1982).
With respect to reproductive changes, the administration of 200 mg
DEHP/kg/day to the diet of rats for two years produced no adverse
effects on reproductive functions. At high doses, DEHP produces
dominant lethal and antifertility effects in mice after a single
intraperitoneal injection (12.8 ml DEHP/kg). Damage to the testes has
been reported to occur in rodents given high doses of DEHP and DBP.
Administration of high doses (>1 g/kg/day) of DMP, DEP, or DNOP to
male rats had no effect on testicular tissues in short term experi-
ments (OWRS, 1980a).
Phthalate-induced injury to rodent testes is accompanied by adverse
effects on gonadal metabolism of zinc. Phthalates cause an increase
in urinary excretion of zinc resulting in a depletion of this vital
element in the testes. Experiments have confirmed that administration
of zinc along with phthalates offered a measure of protection against
testicular atrophy (EHP, 1982).
While there have been a number of studies in which DEHP concentrations
were measured in tissues and blood of human patients exposed to DEHP
during transfusions or hemodialysis, teratogenic or reproductive
effects have not been documented. For example, hemodialysis of men
who suffered from uremia resulted in restoration of spermatogensis;
conception and successful pregnancies in their spouses followed.
2.1.3. Absorption, Distribution, and Metabolism
The phthalate ester and/or derived metabolites are readily absorbed
from the intestinal tract and the lungs; evidence concerning absorp-
tion through the skin is conflicting. The vehicle can play an impor-
tant role in the absorption and distribution of the phthalates. From
the present data, it appears that the diester phthalates can be hydro-
lyzed to the monoester in the gut and thus be absorbed primarily as
the monoester; the efficiency of absorbance of the diester in the gut
is not clear (OWRS, 19BOb).
2-5 July, 1983
-------
Based on current information, the phthalate esters appear to be
rapidly distributed to various organs and tissues and are rapidly
cleared from the body. Earlier studies, particularly those using the
intravenous route, were complicated by poor solubility of the
phthalates and artifacts later attributed to phthalate-solubilizer
interations. The bulk of DEHP and DBF administered by oral or
parenteral routes is cleared from experimental animals within 24 hours
and little is left 3 to 5 days after exposure. There is little
evidence of tissue accumulation or prolonged retention. The major
initial repositories for phthalate esters (or metabolites) are fat,
gastrointestinal tract, liver, and kidney. Chronic administration of
DEHP to rats showed progressive increases in the level of the
phthalate (or metabolite) in the liver and abdominal fat. Rhesus
monkeys infused (i.v.) repeatedly with small amounts of DEHP (total
dose, 21 to 69 mg/kg) in blood showed some retention of DEHP in their
livers for several months after infusion was halted (EHP, 1982).
Phthalate esters are metabolized to the monoesters by enzymes present
in many tissues, but complete hydrolysis to phthalic acid apparently
occurs only in the liver. Appreciable amounts of DMP are excreted as
phthalic acid, but only small fractions of DEHP and other long-chain
alkyl phthalates are completely hydrolyzed to phthalic acid. DMP and,
to some extent, DBF are primarily excreted as the unchanged diester or
as monoester metabolites. The phthalates with longer alkyl groups,
such as DEHP, must undergo conversion to more polar metabolites for
efficient excretion. Several animal species are known to form glu-
curonide conjugates with the monoesters of DBP and DEHP; however, rats
seem unable to form glucuronide conjugates of the monoester (MEHP)
formed from DEHP (EHP, 1982).
The inability of the rat to conjugate MEHP requires extensive oxida-
tion of the remaining 2-ethylhexyl group to achieve sufficient water
solubility for excretion. Studies of the metabolism of DEHP and MEHP
in animals and humans indicate that the terminal or adjacent carbon
atom in the ester side chain is successively oxidized to an alcohol,
then to an aldehyde or ketone, and finally to a carboxylic acid;
excretion via the urine occurs in the form of glucuronide conjugates
of these oxidation products. Similar oxidation pathways have been
documented for the metabolism of the monoester derivatives of other
dialkyl phthalate esters. In light of the recent report that DEHP is
a liver carcinogen in rats and mice, the elucidation of species
differences in DEHP metabolism is crucial to understanding the
applicability of these experiments to humans (EHP, 1982).
Results submitted by CMA under the negotiated testing program for
phthalates are consistent with previous investigations on absorption
and metablism in rats; i.e., DEHP is rapidly absorbed from the GI
tract, produces an enlarged liver, and induces peroxisome formation.
The CMA reported results for marmosets which suggests that DEHP is
poorly absorbed through the GI .tract and that only a small degree of
peroxisome proliferation is induced in monkeys. However, differences
in the protocols used for the two species make it difficult to reach
definitive conclusions from these studies (CPSC, 1983).
2-6 July, 1983
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2.2 Environmental Effects
2.2.1 Aquatic Effects
Information regarding the toxicity of phthalate esters to aquatic
organisms is sparse and inconsistent. No data are available on the
toxic effects of DNOP, and only limited data exist on DEP, DMP, BBP,
and DEHP. Most of the studies presented information on DBP. The
available data focused more on aquatic invertebrates than on fish
species and were taken from OWRS documents in most cases (OWRS, 1980a;
OWRS, 1980b).
Some loss of phthalates from aqueous solution may occur in toxicity
experiments as a result of volatilization and adsorption onto glass
and plastic surfaces. Both static and flow-through systems may
experience losses. When reviewing toxicity test results, rapid re-
duction in phthalate concentration should be considered.
Acute toxic effects on fish were reported at levels ranging from 0.7
mg/L to greater than 10 mg/L DBP and DEHP. DBP was the more toxic of
the two compounds; however, the problems associated with testing DEHP
prevent drawing conclusions about its relative toxicity. The only
data available on the sublethal or chronic effects of phthalate esters
pertained to ingested DEHP on the reproductive success in two species
of fish. A level of 0.05 mg/kg in food reduced reproduction in zebra
fish. It is difficult to compare these data with LC5Q values (lethal
concentration to 50% of the population) because different exposure
routes were involved. The other phthalates had acute effects at
levels greater than 29 mg/L in water.
Limited data exist that would support any conclusions regarding the
greater sensitivity of coldwater fish species to phthalate esters.
The only LC5Q reported for a salmonid species, the rainbow trout, was
higher than those reported for warmwater species. Levels of 0.014
mg/L DEHP significantly increased sac fry (young fish) mortality but
had no effect on egg mortality or hatchability. No comparable studies
on warmwater species were available.
Acute toxic effects have been measured for the bluegill and a number
of phthalates. LC5Q (96 hr.) values have been reported for DBP (10
mg/L), BBP (43.3 mg/L), DMP (49.5 mg/L), DEP (98.2 mg/L), and DEHP
(100 mg/L).
The reported acute effects of phthalates on aquatic invertebrates had
concentration ranges similar to those of vertebrates. Acute LC^s
ranged from 1.9 mg/L to 92.3 mg/L for all phthalates. Reproductive
effects were reported at levels as low as 0.003 mg/L (DEHP) in
Daphnia, while no significant effects were observed at 1.0 mg/L (DEHP,
DMP, and DBP) in the mud crab and at 10 mg/L (DMP and DEP) in brine
shrimp.
Data from chronic studies are conflicting, particularly regarding
effects on Daphnia reproduction and early-life stage effects. In
contrast to the 3ppb reproductive effect noted above, other studies
2-7 July, 1983
-------
report that another fresh water invertebrate (midge) showed no effects
(on midge emergence) when exposed to DEHP levels up to 0.24 mg/L. In
addition, studies with BBP indicate that effects on Daphnia
reproduction are not observed until the BBP level reaches 760 mg.
Therefore, the reported effects at 0.003 mg/L should be confirmed,
since this level is relatively low compared with other observed
effects.
In every study where DBF was tested, it is reported as the most toxic
phthalate. DBF's relationship to DEHP is uncertain, however, because
of the difficulty in dissolving DGHP in water at levels greater than 1
mg/L (and possibly lower). DBF's effects, as well as those of other
phthalates, were generally observed at levels greater than 1 mg/L. It
is possible, therefore, that DGKP is toxic to some species at lower
concentrations (less than DBF) than reported data indicate. An
inverse correlation between solubility and toxicity has been suggested
for some of the phthalates although not all phthalates under consider-
ation in this assessment were represented.
Some evidence demonstrates that fish, like mammals, can rapidly
metabolize certain phthalate esters. Low biomagnification factors in
guppies (130 x) compared with those of aquatic invertebrates and
plants (21,480-107,670 x) also indicate metabolization of DEHP. In
fathead minnows, however, a lab study measured biomagnification
factors as high as 1130. The order of magnitude difference may be
attributed to species characteristics or varying experimental con-
ditions.
2-8 July, 1983
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3. ENVIRONMENTAL RELEASE
Phthalate esters are produced by reacting phthalic anhydride with
appropriate alcohols in the presence of a catalyst (sulfuric acid,
p-toluene sulfonic acid, or an amphoteric metal salt). The esters are
high volume chemicals, the total U.S. production exceeding 500 metric
tons (kkg) for the year 1981; 19 companies supplied the following
amounts of individual esters:*
Phthalate ester Amount produced (10^ kkg)
DU2-ethylhexyl) 129.0
Diisodecyl 63.5
Ditridecyl 12.7
Oibutyl 9.0
Diethyl 9.0
Butyl octyl 5.0
Dimethyl 3.2
Other 276.0
Total 507.4
*Chemical Economics Handbook, SRI International, Feb. 1983.
The major phthalates in the "other" category are ditheptyl,nonyl,
undecyl)phthalate (DHNUP), diisononyl phthalate (DINP), and BBP.
DHNUP is a mixture of dialkyl phthalates containing C-j, Cg, and C11
alkyl groups. A number of other dialkyl phthalates are produced as
mixtures because they are prepared by reaction of phthalic anhydride
with mixtures of isomeric or different alcohols (OTS, 1981).
Approximately 95% of the phthalate esters are used as plasticizers for
various resins, primarily polyvinyl chloride (PVC). DEHP has the
highest production figure because of its overall properties, i.e.,
compatibility, low vapor pressure, low solubility in water, long term
stability, and low cost. Oiisodecyl phthalate is used as a PVC
plasticizer for wires and cables. Butyl benzyl phthalate is used
primarily for vinyl flooring. DHNUP is widely used in automobile
interiors and wire coatings. Both DHNUP and BBP have appreciable
percentages of the total phthalate market (approximately 20% and 10%
respectively). DEP and DMP are used in the manufacture of cellulosic
resins; DMP is also used as an insect repellent. DBP is used as a
plasticizer for epoxy and PVC resin (OWRS, 1980a).
Plasticizers are used to aid in processing or to impart desired
characteristics to plastic (e.g., stain resistance in flooring,
flexibility and temperature resistance in wire insulation, good
adhesion in coatings and adhesives). Plasticized PVC formulations
usually contain from 20 to 40% plasticizers (by weight) in the end
product. The main uses of plasticizers in PVC applications are
flooring, upholstery in automobiles and furniture, and wire
coatings. Table 4 summarizes the recent end use pattern for the
phthalate esters (OTS, 1981).
3-1 July, 1983
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TABLE 4. PHTHALATE ESTER END-USE PATTERN FOR 1977
Flexible PVC
Apparel
Baby Pants
Footwear
Outerwear
Building Construction
Flooring
Swimming Pool Liners
Weathers tripping
Electrical Wire and Cable Coatings
Home Furnishings
Furniture
Wall Cove rings /Wood Surfacing Film
Housewares
Packaging Film
Recreation
Sporting Goods
Toys
Transportation
Upholstery
Other
Miscellaneous
Garden Hose
Medical Tubing
Other PVC Uses
Subtotal for PVC Uses
Other Polymers and Resins
Non-Plasticizer
Export
Subtotal for non-PVC Uses
Total
106kg
3.2
30.4
14.1
47.7
108.1
6.8
7.3
122.2
87.6
87.6
53.6
19.2
72.8
18.2
18.2
7.0
7.0
8.4
12.2
20.6
53.6
16.2
69.8
5.0
5.5
10.5
21.6
21.6
477.6
15.0
10.4
42.5
67.9
545.8
Percentage
8.7
22.4
16.0
13.3
3.3
1.3
3.8
12.8
5.9
87.5
2.8
1.9
7.6
12.5
100.0
SOURCE: (OTS, 1981)
3-2 July, 1983
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The environmental release occurs with synthesis and continues through
production, use and disposal. Table 5 shows the estimated amounts
released at various stages of phthalate manufacturing and consump-
tion. Losses of phthalates during production are small. During
compounding with high temperatures, appreciable losses occur to air
and water. Between 70 and 90% of the esters are disposed of in land-
fills.
The distribution of releases to the environmental compartments is
shown in Table 6. The rate of release from the landfills is not
known. It is speculated that the lipophilic phthalates partition into
the soil which then becomes the interface for transport to lakes,
rivers, and ocean via underground streams or rain runoff.
Phthalate-containing products may be grouped into four categories
according to their 'ease1 of release, based on the physical state,
intermolecular forces, and surface area. In order of decreasing
freedom of release, they are as follows (OTS, 1981):
Non-plasticizer uses
Cosmetics, lubricating oils, dielectric fluids, adhesives, etc.,
that do not physically bind or encase the phthalate. Nearly all of
the phthalates from these mixtures are estimated to be released.
Plasticizer uses
(a) Swimming pool liners, garden hoses, medical products (for
transfusions, artificial kidney tubing). In these uses
there is direct liquid contact with the phthalate-containing
surface to facilitate release through partitioning.
(b) Upholstery, flooring, food wrapping, seat covers, etc.
These materials have high surface to volume ratios from
which the phthalates can escape.
(c) Household plastics, molded furniture, construction
materials. These products are bulk materials of low surface
area and, therefore, slow in releasing to the environment.
3-3 July, 1983
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TABLE 5. RELEASES OF PHTHALATES IN THE UNITED STATES AT VARIOUS
STAGES OF MANUFACTURING AND CONSUMPTION OO6 kg)a
Production
Transportation
Processing
(Compounding)
(Manufacturing)
Product Use &
Consumption
Product Disposal
(97% to Landfill)
TOTAL
DEHP
0.9
0.2
14.9
(5.0)
(9.9)
>3.4
149.1
168.5
DBP
0.04
0.01
0.50
(0.18)
(0.32)
>0.35
6.15
7.1
DEP
0.04
0.01
0.5
(0.2)
(0.3)
>0.30
6.7
7.6
DMP
0.02
0.01
0.2
(0.1)
(0.1)
>1.0
2.9
4.1
OTHER
1.6
0.3
22.3
(9.5)
(12.9)
27.3
266.4
318.0
TOTAL
2.61
0.50
38.99
(15.52)
(23.49)
32.33
429.58
505.2
PERCENTAGE
0.5%
0.1%
7.7%
(3.1%)
(4.6%)
6.4%
85.3%
100%
aSOURCE: (OTS, 1981); data for 1977.
3-4
July, 1983
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TABLE 6. DISTRIBUTION OF PHTHAIATE RELEASES TO ENVIRONMENTAL COMPARTMENTS
IN THE UNITED STATES ( 1 O5 kg)a
Released to
Released to
Landfilled
Incinerated
TOTAL0
DEHP
air 4.3
waterb 5.2
154.1
4.9
168.5
DBF
0.3
0.3
6.3
0.2
7.1
DEF
0.2
0.4
6.8
0.2
7.6
DMP OTHER
0.5 13.6
0.6 25.4
2.9 270.6
0.1 8.4
4.1 318.0
TOTAL
18.9
31.8
440.7
13.8
505.2
PERCENTAGE
3.7%
6.3%
87.3%
2.7%
100.0%
a Source: (OTS, 1981); data for 1977.
13 Includes process loss during manufacturing, estimated at 0.5% of production,
all to water.
c Includes U.S. supply plus process loss during manufacturing.
3-5 July, 1983
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4. EXPOSURE ROUTES
In general, human exposure- to phthalates is low; DEHP exposure is
probably the most common. Food is the primary source of DEHP, with
average food exposure levels of about 0.3 ing/day and maximum levels of
about 2 rag/day. As described below, intake from drinking water,
inhalation, and dermal absorption are comparatively low, although
occupational exposures may be high. Certain subpopulations which may
receive higher exposures include people receiving large quantities of
blood, dialysis patients, and hemophiliacs. Possible exposure from
PVC consumer products, especially children's products, are also of
concern (OWRS, 1980a).
Monitoring data for phthalate esters in the environment are relatively
scarce and interpretation of much of the information is complicated by
possible phthalate contamination. Many monitoring studies reported in
the literature, especially prior to 1975, do not give procedures for
avoiding contamination during collection and analysis. The accuracy
of the data on these substances may suffer from the ubiquitous nature
of some of the phthalates (OTS, 1981).
4.1 Air Exposure
Based on the limited information available, exposure of the general
population to airborne phthalates should be low. The meager
monitoring data show mean levels of 0.011 to 0.07 ug/m3 of DEHP in
urban areas and 0.001 to 0.018 ug/m3 in nonurban locales (OTS,
1982). Based on the mean concentrations of DEHP in urban air,
inhalation of 20 m3 a day of air would result in exposures of only 0.2
to 1.4 ug DEHP per day. A single study reported higher levels of DEHP
(0.3 ug/m3) and DBP (0.7 ug/m3) in the vicinity of an incinerator
(OWRS, 1980a).
Plastics in flooring, furniture, and other materials may result in
significant levels of phthalates indoors. DEHP has been detected in
indoor air, but no levels were reported. While exposure to airborne
phthalate esters in automobiles is likely due to the extensive use of
vinyl materials, no quantitative measurements are available to
estimate exposure. Although the use of DEHP plastics in car interiors
has been discontinued in the U.S., other phthalates, such as
diisodecyl phthalate and di(heptyl,nonyl,undecyl) phthalate, are still
widely used (OTS, 1981; OWRS, 1980a).
4.2 Water Exposure
The most comprehensive study of finished drinking water for DEHP
content was undertaken in EPA Region V. The 53 cities surveyed were
selected on the basis of suspected high levels of organic
pollutants. DEHP was detected in 20 out of 53 samples. The mean of
detected values was 3 ug/L and the maximum level was 17 ug/L. In
another drinking water study, the mean detected value of DEHP was 6
ug/L (maximum 53 ug/L); in this study, DEHP was detected in 10 out of
14 cities (OTS, 1982).
4-1 July, 1983
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Other limited monitoring data suggest that several phthalate esters
may be present in finished drinking water supplies. An EPA study of
drinking water in ten cities reported DEHP, DEP, and DBF in water from
several locations. Excluding the abnormally high levels reported for
one city (Miami, Florida) the ranges reported were: DEHP, 0.04 to 0.8
ug/L; DBP, 0.01 to 5 ug/L; DEP, 0.01 to 0.05 ug/L (OWRS, 1980a).
A realistic upper limit of 10 ug/L has been suggested for DEHP in
drinking water. Assuming a consumption of 2 liters of drinking water
per day, intake from this source should not exceed 20 ug per day
(OWRS, 1980a).
Although ambient water monitoring is also limited, results suggest
that ambient levels of phthalate esters are generally less than 10
ug/L. Higher levels of these esters, primarily DEHP and DBP, are
found in industrialized areas (OWRS, 1980a).
4.3 Other Routes
Food
Contamination of food can occur from surfaces of phthalate-containing
PVC processing equipment and packaging film with which the food comes
in contact. FDA regulates phthalate esters and approves uses that
might result in migration of phthalates into foods under certain
constraints. A variety of phthalates are approved providing
conditions avoiding contamination are met. For example, DEHP, being
hydrophobic, is only approved for use in packaging of foods with high
water content (as opposed to fatty foods). Generally, regulations are
based on the rate of migration and release that do not result in
contamination. In a survey (1974) FDA found most samples contained
DEHP levels of less than 1 mg/kg. This value in conjunction with
dietary assumptions gives an estimated exposure of less than 2
mg/day/person. Information on other phthalate esters in food is
incomplete. Butyl benzyl phthalate was found in margarine; and DBP in
milk. The information is not sufficient to allow estimation of human
exposure (OWRS, 1980a).
Consumer Products
In addition to inhalation and ingestion, a consumer is likely to be
exposed dermally to phthalates used in nonplasticizer products, such
as perfumes and cosmetics, and plasticized products, such as vinyl
swimming pools, plasticized vinyl seats (on furniture and in cars),
and clothing (jackets, raincoats, boots, etc.). For a skin surface
area of 1080 cm2 (midcalf to midthigh) in contact with plasticized
vinyl fabric (i.e., boot) for 4 hours, 0.5 mg DEHP may transfer to the
skin surface (OTS, 1982). There is also exposure from children's
toys, mats, pacifiers, and teethers made of phthalate plasticized
PVC. CPSC has completed a risk/exposure assessment for DEHP in
children's products. The total potential exposure of an infant to
DEHP from both oral (mouthing) and dermal routes is estimated to be
about 100 to 800 mg over the course of one to two years of use of
DEHP-containing baby products (CPSC, 1983).
4-2 July, 1983
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Occupational
Workers in plastics manufacture in which phthalate esters are used
might have exposures of 20 to 800 ug/m3 in various areas of a DEHP
production plant. Although it is known that DEHP is used in the
fabrication of a variety of industrial products, few monitoring data
are available on the producers or on the commercial users of such
products. In every inspection, some of which monitored several
different employees within a facility, the level was found to be below
the established threshold value of 5 mg/m^ (OTS, 1982; IARC, 1982).
Intravenous
Humans may be exposed to phthalate esters through tubing and liquid
storage bags used in transfusions. Blood stored in PVC bags has been
shown to contain DEHP; an extraction rate of 0.25 mg DEHP/100 ml
blood/day has been established over a 21-day period. the estimated
exposure to patients who receive 4 to 63 units of blood is 14 to 600
mg DEHP, depending on the storage conditions (time and temperature)
for each blood unit. Also, cryoprecipitate packs may contain 0.8 to
1 .9 mg DEHP. Hemophiliacs may receive 400 bags of
cryoprecipitates/year, representing a possible exposure of 2 mg
DEHP/day (OTS, 1982).
Hemodialysis patients may also receive phthalate esters (primarily
DEHP) from the dialysis apparatus. Assuming a 5 to 7 liter blood
volume, a patient could receive 75-105 mg DEHP per treatment.
Therefore, two-to-three treatments per week would lead to an exposure
of 150 to 315 mg DEHP; this translates into a daily average dose of 21
to 45 mg DEHP/day (OWRS, 1980a). Monitoring data obtained from
dialysis patients have confirmed the addition of DEHP to the blood;
however, the amount of DEHP delivered varied widely (OTS, 1981).
4-3 July, 1983
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5. DATA BASES
5.1 Chemicals in Commerce Information System (CICIS)
The Inventory was compiled under the authority of Section 8 of TSCA
which requires manufacturers to report to EPA the chemicals imported
and manufactured during calendar year 1977. The Inventory lists the
Chemical Abstract Service (CAS) preferred name for the chemicals,
their respective CAS number (often used for identification purposes),
production site, company name, and volume(s) of production and
import. There is also a Confidential Inventory in which many of these
characteristics are claimed confidential by the manufacturer. In
these instances, the confidential information will not be available in
the public inventory. CICIS can now be accessed through the NIH/EPA
Chemical Information System (CIS - see 5.3). For further information,
contact Gerri Nowack at FTS 382-3568 or Robin Heisler at PTS 382-3557.
5.2 EPA Chemical Activities Status Report (EPACASR)
EPACASR is an on-line system containing information on EPA's interest
in chemicals. This system includes data on the Agency's regulations
research, and assessments directed toward specific chemicals. EPACASR
is published annually and the data base is updated as information is
received. A searchable subset itemizes NTP/NCI studies and results,
as well as chemicals discussed in the IARC monograph series. (Other
sources are added as appropriate.) Entries identify the statutory
authority, the nature of the activity, its status, the reason for
and/or purposes of the effort, and a source of additional
information. Searches may be made by CAS Number or coded text.
(EPACASR is scheduled to be added to CIS in 1984). For further
information, contact Eleanor Merrick at FTS 382-3415.
5.3 NIH/EPA Chemical Information System (CIS)
This is a collection of various scientific data bases available
through an interactive computer program. The linking system between
these data files is the Structure and Nomenclature Search System
(SANSS). CIS can also provide a list of non-CIS sources of
information on a chemical of interest. However, these files have to
be accessed individually by either separate on-line systems or in
hard-copy. Fur further information, contact Dr. Steve Heller at FTS
382-2424.
5.4 Chemical Regulations and Guidelines System (CRGS)
CRGS is an on-line data base which is being developed to provide
information on chemical regulatory material found in statutes,
regulations, and guidelines at the Federal, State, and international
levels. Currently, only the first phase of CRGS, which encompasses
only source material at the Federal level, is operational. Nation-
wide access to CRGS is available through Dialog. For further
information, contact Doug Sellers at FTS 382-2320.
5-1 July, 1983
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5.5 Chemical Substances Information Network (CSIN)
The Chemical Substances Information Network (CSIN) is a
sophisticated switching network based on heterogeneous distributed
data base management and networking concepts. CSIN offers efficient
access to on-line information resources containing data and
information relevant to chemical substances, as well as information
covering other scientific disciplines and subject matters. The
purposes of CSIN are two-fold: first to meet the growing chemical
data and information requirements of industry, academe, government
(Federal and State), public interest groups, and others, and secondly
to reduce the burden on the private and public sector communities when
responding to complex Federal legislation oriented to chemical
substances.
CSIN is not another data base. CSIN links many independent and
autonomous data and bibliographic computer systems oriented to
chemical substances, establishing a "library of systems." Users may
converse with any or.all systems interfaced by CSIN without prior
knowledge of or training on these independent systems, regardless of
the hardware, software, data, formats, or protocols of these
information resources.
Information accessible through CSIN provides data on chemical
nomenclature, composition, structure, properties, toxicity, production
uses, health and environmental effects, regulations, disposal, and
other aspects of the life cycle of materials as they move through
society. Currently, seven independent information resources are
accessible through CSIN. They are: National Library of Medicine
(NLM), Chemical Information System (CIS), CAS-On-Line, SDC's ORBIT,
Lockheed's DIALOG, Bibliographic Retrieval Service (BRS), and the US
Coast Guard's Hazard Assessment Chemical System (MACS). For further
information contact Dr. Sid Siegel at 202-395-7285.
5.6 EPA Information Clearinghouse
The EPA Information Clearinghouse is a bibliographic data base
composed of over 500 individual data bases and models which contain
monitoring information and statistics on a variety of chemicals. The
individual data bases are maintained for offices within EPA. The
clearinghouse listed a total of 453 citations for the phthalate
esters. For further information, contact Irvin Weiss at FTS 382-5918.
5-2 July, 1983
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6. REGULATORY STATUS (Current as of 7/83)
6.1 Promulgated Regulations
6.1.1 EPA Programs
Clean Water Act (CWA)
o Sections 301, 304, 306, and 307 - Phthalate esters are listed as
toxic pollutants (40 CFR 401.15) and are subject to effluent
limitations. However, no effluent guidelines specifically limit
the release of phthalate esters at this time.
o Sections 318, 402, and 405 - National Pollution Discharge
Elimination System (NPDES) permit testing requirements; the
following are listed as organic toxic pollutants based on gas
chromatographic and mass spectroscopic analyses and are part of the
consolidated permit program (40 CFR 122, App. D):
o Butyl benzyl phthalate
o Oi(2-ethylhexyl) phthalate
o Dibutyl phthalate
o Diethy1 phthalate
o Dimethyl phthalate
o Di-n-octyl phthalate
Resource Conservation and Recovery Act (RCRA)
o Section 3001 - The following phthalate esters have been identified
as toxic hazardous wastes if and when they are discarded as
commercial products or off-specification species (40 CFR 261.33):
o Di(2-ethylhexyl) phthalate (U028)
o Dibutyl phthalate (0069)
o Diethyl phthalate (U088)
o Dimethyl phthalate (U102)
o Di-n-octyl phthalate (U107)
Also, phthalate esters are listed as hazardous constituents (40 CFR
261, App. VIII).
o Sections 3002 to 3006 - Hazardous wastes are subject to further
controls concerning generators, transporters, and treatment,
storage, and disposal facilities (40 CFR 262 to 265). Permit
procedures are also included in consolidated permit regulations (40
CFR 122 to 124).
Toxic Substances Control Act (TSCA)
o Section 8(a) - Preliminary assessment reporting for the following
(40 CFR 712):
o Dimethyl phthalate
o Diethyl phthalate
6-1 July 1983
-------
o Dibutyl phthalate
o Di(2-ethylhexyl) phthalate
o Di-n-octyl phthalate
o Butyl benzyl phthalate
Federal Food, Drug, and Cosmetic Act (administered by EPA)
o Materials exempted from pesticide tolerance requirements under
certain conditions (40 CFR 180.1001):
o Diethyl phthalate
o Butyl benzyl phthalate
6.1.2 Programs of Other Agencies
OSHA - Occupational Safety and Health Act
o General industry standards for work place exposure to air
contaminants (29 CFR 1910.1000):
o Dibutyl phthalate
o Dimethyl phthalate
o Di(2-ethylhexyl) phthalate
FDA - Food, Drug, and Cosmetic Act
o Permissible components of adhesives used in food packaging,
storage, and transport (21 CFR 175.105):
o Dibutyl phthalate o Diisodecyl phthalate
o Diethyl phthalate o Dicyclohexyl phthalate
o Di(2-ethylhexyl) phthalate o Diphenyl phthalate
o Dimethyl phthalate o Butyl phthalyl butyl glycolate
o Di-n-octyl phthalate o Methyl phthalyl ethyl glycolate
o Butyl benzyl phthalate
o Permissible substances in paper and paperboard in contact with
aqueous and fatty foods (21 CFR 176.170):
o Butyl benzyl phthalate o Butyl phthalyl butyl glycolate
o Dibutyl phthalate o Dicyclohexyl phthalate
o Permissible components of paper or paperboard in contact with dry
food (21 CFR 176.180):
o Dibutyl phthalate
o Butyl benzyl phthalate
o Dicyclohexyl phthalate
o Permissible substances used as defoaming agents in manufacturing
paper and paperboard used in food packaging (21 CFR 176.210):
o Butyl benzyl phthalate
6-2 July 1983
-------
o Permissible substances for use in the preparation of slimicides
used in the manufacture of paper or paper board that contact food
(21 CFR 176.300):
o Dibutyl phthalate
o Limit on miscellaneous materials used in acrylic and modified
acrylic plastics in contact with food (21 CFR 177.1010):
o Di(2-ethylhexyl) phthalate
o Dimethyl phthalate
o Permissible component of cellophane used for packaging (21 CFR
177.1200):
o Di(2-ethylhexyl) phthalate
o Dibutyl phthalate
o Dicyclohexyl phthalate
o Permissible components that facilitate or are added to cross-linked
polyester resins used as articles intended for repeated contact
with food (21 CFR 177.2420):
o Dibutyl phthalate
o Butyl benzyl phthalate
o Permissible components used in the preparation of rubber articles
intended for repeated use (21 CFR 177.2600):
o Dibutyl phthalate
o Di-n-octyl phthalate
o Diisodecyl phthalate
o Permissible components used as plasticizers in polymeric substances
used in the manufacture or articles intended for food contact (21
CFR 178.3740):
o Butyl benzyl phthalate
o Diphenyl phthalate
o Dicyclohexyl phthalate
o Permissible substances used as surface lubricants in the
manufacture of metallic articles that contact food (21 CFR
178.3910):
o Diethyl phthalate
o Di(2-ethylhexyl) phthalate
MSHA - Federal Mine Safety and Health Act
o Performance requirements for respirators (30 CFR 11.183):
o Di-n-octyl phthalate
6-3 July 1983
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DOT
o Regulations for bulk transportation (46 CFR 30.25):
o Butyl benzyl phthalate
o Dibutyl phthalate
o Di-n-octyl phthalate
Port and Tanker Safety Act/Dangerous Cargos Act
o Regulations and standards for unmanned barges carrying certain bulk
dangerous cargos (46 CFR 151.01; 46 CFR 154, Annex B):
o Butyl benzyl phthalate
o Dibutyl phthalate
o Di-n-octyl phthalate
o Diethyl phthalate
o Dimethyl phthalate
o Di (2-ethylhexyl) phthalate
6.2 Proposed Regulations
6.2.1 EPA Programs
Comprehensive Environmental Response, Compensation, and Liability Act
(CERCLA or Superfund) {CERCLA or Superfund)
CERCLA provides for the liability, compensation, clean-up and
emergency response for the release of hazardous substances into the
environment. This Act also deals with the cleanup of hazardous waste
disposal sites. (42 USC 9601; PL 96-510). EPA is developing regula-
tions concerning the designation of hazardous substances, the develop-
ment of reportable quantities (RQ), claims procedures, and the confi-
dentiality of business records (46 FR 54032). Revisions to the
National Contingency Plan (NCP) as required by CERCLA have been issued
in a proposed rule (47 FR 10972).
Phthalate esters are hazardous substances under CERCLA and will be
subject to regulations developed under Superfund. EPA has proposed
adjustments to many of the RQ's established under CERCLA and the CWA
(48 FR 23552).
6.3 Other Actions
Consumer Product Safety Commission (CPSC)
CPSC has decided to convene a Chronic Hazard Advisory Panel on DEHP to
assist in determining whether regulatory action is needed. Of imme-
diate concern is the potential exposure of children to DEHP from
infant products. (CONTACT: Sandra Eberle, FTS 492-6957)
6-4 July 1983
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Public Health Service - National Toxicology Program (NTP)
o Studies are in progress with selected phthalates including the
investigation of the genotoxicity and carcinogenic mechanism of
DEHP; in addition, the reproductive toxicity and carcinogenic
potential of several other phthalates (diallyl-,diethyl-, and butyl
benzyl phthalate) are under study. A variety of phthalates will
also be analyzed for absorption, disposition, and clearance. The
NTP studies are designed to complement other studies in progress,
such as the CMA testing noted below (Contact: Dr. William Kluwe,
FTS 629-4177).
EPA - TSCA
o Under section 4(e) of TSCA, the ITC recommended the alkyl
phthalates and BBP for testing (42 FR 55026; 45 FR 78432). EPA
negotiated a comprehensive testing agreement with the Chemical
Manufacturers Association (CMA) whereby the phthalate ester
industry, through CMA, agreed to voluntarily test a variety of
phthalate esters for environmental and health effects. Therefore,
EPA decided not to propose, at that time, a section 4(a) rule to
require testing. The Agency is free to pursue the issuance of a
section 4(a) test rule in the future if more information is
required (Contact: Larry Rosenstein, FTS 475-8163).
NTP/EPA Clearinghouse on Phthalates
o The Phthalate Clearinghouse was set up by NTP and EPA to facilitate
the collection and dissemination of information on phthalates. The
clearinghouse attempts to provide up-to-date results of
experimental work on phthalate esters (Contact: Joan Chase, FTS,
496-1152).
6-5 July 1983
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7. STANDARDS AMD CRITERIA*
7.1 Air
o OSHA standards for work place exposure to phthalates in air (29 CFR
1910.1000):
Dibutyl phthalate 5 mg/m3 (8 hr. TWA)
Dimethyl phthalate 5 mg/m3 (8 hr. TWA)
Di(2-ethylhexyl) phthalate 5 mg/ra3 (8 hr. TWA)
7.2 Water
o Water Quality Criteria {45 FR 79318)
Freshwater aquatic life:
Phthalate esters 940 ug/L (acute)
3 ug/L (chonic)
Saltwater aquatic life:
Phthalate esters 2,944 ug/L (acute)
Human health criteria for the ingestion of water and contaminated
aquatic organisms:
Dimethyl phthalate 313 mg/L
Diethyl phthalate 350 mg/L
Dibutyl phthalate 34 mg/L
Di(2-ethylhexyl) phthalate 15 mg/L
Human health criteria for the ingestion of contaminated aquatic
organisms only:
Dimethyl phthalate 2,900 mg/L
Diethyl phthalate 1,800 mg/L
Dibutyl phthalate 154 mg/L
Di(2-ethylhexyl) phthalate 50 mg/L
o Based on NTP animal bioaasays for carcinogenic!ty, EPA has
calculated water concentrations for DEHP which correspond to the
10~6 risk level. For ingestion of water and aquatic organisms the
value would be 1.7 ug/L; for ingestion of aquatic organisms only,
the criteria would be 5.8 ug/L.
See Appendix A for a discussion of the derivation, use, and limitations
of these criteria and standards.
7-1 July, 1983
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8. SPILL OR OTHER INCIDENT CLEANUP/DISPOSAL
8.1 Hazards and Safety Precautions
Safety precautions when handling or cleaning up spills of phthalate
esters are necessary because of their potential toxicity as described
in Section 2. In general, phthalate esters are readily absorbed via
inhalation or thourgh the skin. Exposures to hot vapors or mists may
cause irritation of the nasal passages, the mouth, and throat. Eye
contact with the liquids causes pain. If swallowed, the esters may
cause irritation of the stomach, dizziness, and unconsciousness. Most
phthalates have slight or no odors. The various phthalates differ in
their degree of toxicity. For example, dibutyl phthalate (DBF) if
swallowed may cause light sensitivity, watering and redness of the
eyes, in addition to the above general symptoms.
Chemically, the phthalate esters are relatively stable unless contact
occurs with nitrates, strong oxidizers, strong alkalies, or strong
acids which may cause fires and explosions. DMP has a flashpoint of
146°C (295°F; closed cup), and an auto ignition temperature of 556°C
(1032°F). Flammability of the phthalate esters is generally low
except for DMP.
8.2 First Aid
Move victim to fresh air; give artificial respiration if not breathing
and oxygen if breathing is difficult. In case of eye or skin contact
flush with running water; remove clothing as necessary to assure water
flowing over the affected skin. Isolate contaminated clothing. There
may be delayed effects after exposure. If swallowed, induce vomiting
unless unconscious.
8.3 Emergency Action
Spill or Leak - Stay upwind, wear breathing apparatus, eye protection,
and protective clothing and isolate area. Remove all ignition
sources. Use water spray to control and reduce vapors.
Fire - For small fires use dry chemical, C02' water spray, or foam.
For large fires use water spray or foam. Cool containers with water
after fire is out.
8.4 Notification and Technical Assistance
Section 103 (a) of the Comprehensive Environmental Response, Compensa-
tion, and Liability Act (CERCLA or Super fund) requires notification of
the National Response Center (NRC) in the event of a spill of a listed
chemical; telephone: 800-424-8802 (in Washington D.C. area: 426-
2675). The reportable quantity in effect for DBP is 100 Ibs.
Regulations listing RQs under CERCLA have not been finalized and a
statutory RQ of 1 Ib. is applicable for other phthalates.
8-1 July, 1983
-------
For further information call EPA Environmental Response Team (24-hour
number: 201-321-6660) or the Division of Oil and Special Materials
(1-202-245-3045). Confirm any treatment procedures with a responsible
environmental engineer and regulatory officials. For emergency assis-
tance one may also call: CHEH TREC: 800-424-9300.
8.5 Disposal
General disposal procedures may be used for phthalates after confirm-
ing with a responsible environmental engineer and regulation
officials. Thus/ product residues and sorbent media may be packaged in
epoxy-lined drums and disposed of at an approved EPA disposal site.
Destruction by high temperature incineration or microwave plasma
detoxification, if available, or encapsulation by organic polyester
resin or silicate fixation may be also used.
A generator of 1000kg or more of hazardous waste is subject to RCRA
regulations concerning treatment, storage, and disposal. A number of
phthalate esters (BBP, DEHP, DBP, DEP, DMP, and DNOP) are listed as
toxic hazardous wastes if discarded as commercial products or off-
specification species.
8-2 July, 1983
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9. SAMPLING, ACCEPTABLE AHALYTICA1 TECHNIQUES, AMD QUALITY ASSURANCE
Phthalate esters contaminate many types of products commonly found in
the laboratory. The analyst must demonstrate that no phthalate
residues contaminate the sample or solvent extract under the
conditions of the analysis. Of particular importance is the avoidance
of plastics (e.g., tygon tubing) because phthalates are commonly used
as plasticizers and are easily extractable. Phthalate residues have
also been found in solvents and in chromatographic column packing
materials. Serious phthalate contamination may result at any time if
consistent quality control is not practiced (OTS, 1981).
9.1 Air
The phthalate esters are not regulated air pollutants; no EPA approved
procedure for air analysis has been adopted. Sampling and analysis
procedures for DBP and DEHP have been issued by NIOSH for monitoring
around producton and user facilities (NIOSH Manual of Analytical
Methods, Vol. 2, 1977, DHSS Pub. A77-157-B). A known volume of air is
drawn through a cellulose membrane filter to adsorb the phthalate
aerosol present. The filter is transferred into a disposable glass
pipet and eluted with carbon disulfide. The eluted sample is analyzed
by gas chromatography (GC) using flame ionization detection (FID).
The method for DEHP was validated over the range of 2.03 to 10.9 mg/m3
for a 32-liter sample; the validation range for DBP is similar. For
the conditions used with this sample size, the probable useful range
of this method is 0.5 to 15 mg phthalate/m3. The limit of the method
is dependent on the filtration efficiency of the cellulose membrane
filter. The filtration efficiency for DBP and DEHP aerosol is greater
than 95% when sampled for 30 minutes at 1 liter per minute from a test
atmosphere containing 10 mg/m . The variability corresponds to a
standard deviation of 0.29 mg/m at the OS HA standard level (5
mg/m ). The average values obtained for the overall sampling and
analytical method are 8% higher than the "true" values for DEHP and
8.6% lower for DBP.
Other procedures reported (IARC, 1982) for the analysis of airborne
phthalates include: absorbance on Florisil or glass fiber filters
followed by desorption and GC/FID analysis; and use of glass fiber
filters plus foam plugs to trap the phthalate followed by extraction
and GC/ECD analysis (detection limit given 0.1 ng/m ).
9.2 Water
A number of phthalate esters are listed as priority pollutants under
section 304 of the Clean Water Act. The suggested analytical proce-
dure (Method 606 in "Guidelines Establishing Test Procedures for the
Analysis of Pollutants," 44 PR 69491; 1979) covers the determination
of BBP, DEHP, DBP DNOP, DEP, and DMP, and is applicable to the deter-
mination of these compounds in municipal and industrial discharges.
This method is designed to meet the monitoring requirements of the
National Pollutant Discharge Elimination System (NPDES).
9-1 July, 1983
-------
If samples are not to be extracted within two days of collection, they
should be adjusted to pH 6 to 8. All samples should be extracted
within 7 days and analysis completed within 30 days. In the procedure
a 1-liter sample of water is extracted with raethylene chloride and the
extract is dried and concentrated. Separation is carried out using
gas chromatography (GC) and the phthalates are detected using electron
capture (ECD) or flame ionization detectors (FID). For ECD detection
limits range from 0.02 to 0.13 ug/L; for FID the limits are about two
orders of magnitude higher. Solvents, reagents, glassware and other
sample processing hardware may yield discrete artifacts and/or
elevated baselines causing misinterpretation of gas chromatograms.
The Chemical Manufacturers Association (CMA) has submitted analytical
characterization and interlaboratory recovery and measurement data for
fourteen phthalate esters. These submissions are part of the
negotiated testing program for phthalates accepted by EPA in lieu of a
test rule under section 4 of TSCA. These studies are available in the
public file on phthalates (47 FR 54161).
9.3 Solid Waste
Phthalate esters in waste solids may be determined as described by
methods 806 and 825 in Test Methods for Evaluating Solid Waste,
Physical/Chemical Methods (Office of Solid Waste and Emergency
Response, July 1982, SW-846, Second Edition). Method 806 is used to
determine the concentration of phthalate esters in groundwater,
liquid, and solid sample matrices.
Specifically, Method 806 may be used to detect BBP, DEHP DBF,
DNOP, DEP, and DMP. This method provides cleanup and GC conditions
for the detection of ppb levels of phthalate esters. Water samples
are extracted at a neutral pH with methylene chloride as a solvent and
solid samples are extracted using either the Soxhlet apparatus or
sonication procedures.
The extract is analyzed by gas chromatography using an electron
capture detector (ECD) or a flame ionization detector (FID). The de-
tection limits are lowest for the low molecular weight esters and
highest for the high molecular weight compounds, i.e., 0.29 ug/L for
DMP and 3.0 ug/L for DNOP using the ECD technique. In a single labo-
ratory, the average recovery varied from 80-94% for the phthalates
measured and the standard deviation ranged from 1.3 to 6.5%. Method
825 is a general procedure for analysis and separation of a wide
variety of semivolatile organics by GC/MS.
9.4 Other Samples
A review of the methods used in the analyses of environmental samples
for phthalates and possible sources of sample contamination has been
completed for EPA. A summary of this review and the monitoring data
is included in an EPA exposure assessment for DEHP (OTS, 1982). Other
reference documents also review procedures for the sampling and
analysis of phthalates in a variety of environmental matrices
including: food; human serum and stored blood; PVC products; human
and animal tissues and urine; and laboratory supplies (OTS, 1981;
IARC, 1982).
9-2 July, 1983
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REFERENCES
The major references used in the preparation of this document are listed
below. EPA references are listed by EPA office of origin and the year of
publication. For further information refer to contacts given throughout this
document or contact the relevant EPA offices listed at the end of this section.
(CPSC, 1983)
(EHP, 1982)
(IARC, 1982)
(OTS, 1980)
(OTS, 1981)
(OTS, 1982)
(OWES, 1979)
(OWRS, 1980a)
(OWRS, 1980b)
Children's Chemical Hazards - Risk Assessment on Di(2-
Ethylhexyl) Phthalate in Children's Products, Consumer Products
Safety Commission, (1983).
Environmental Health Perspectives; Vol. 45, Nov. 1982.
IRRC Monographs on the Evaluation of the Carcinogenic Risk of
Chemicals to Humans; Vol. 29, International Agency for Research
on Cancer, world Health Organization (1982).
Priority Review Level I; Pi(2-Ethylhexyl)Phthalate (DEHP);
EPA Draft Report, Office of Pesticides and Toxic Substances
(1980).
TSCA Section 4 Human Exposure Assessment-AlkyL Phthalates;
EPA Final Report, Office of Toxic Substances (1981).-
Exposure Assessment for DEHP; EPA Interim Draft Report, Office
of Toxic Substances, November (1982).
Water-related Environmental Fate of 129 Priority Pollutants;
Vol. II, Chap. 94, EPA 440/4-79-029b, Office of Hater
Regulations and Standards (1979).
An Exposure and Risk Assessment for Phthalate Esters; EPA Final
Draft Report, Office of Water Regulations and Standards (1980).
Ambient Water Quality Criteria for Phthalate Esters; EPA
440/5-80-067, Office of Water Regulations and Standards (1980).
R-1
July, 1983
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OFFICE CONTACTS
The EPA offices and divisions that are listed below may be contacted for more
information relating to the indicated sections of this document. While these
offices are, in many cases, the offices of origin for the data included in
this paper, the personal contacts given throughout this document should be
contacted first. Unless otherwise noted, the offices listed are situated in
Headquarters, Washington, D.C., and the telephone numbers given are FTS
(Federal Telecommunications System) numbers. For commercial telephone calls
to Headquarters which are not placed on FTS, area code 202 must be used.
Other commercial numbers are noted for the office contacts located outside
Washington, D.C.
HEALTH AND ENVIRONMENTAL EFFECTS (Section 2)
Office of Health and Environmental Assessment (OHEA)
Environmental Criteria and Assessment Office:
Cincinnati, OH 684-7531 (513-684-7531)
Research Triangle Park, NC 629-4173 (919-541-4173)
Carcinogen Assessment Group 382-7341
Office of Drinking Water (ODW)
Health Effects Branch 382-7571
Office of Toxic Substances (OTS)
Health and Environmental Review Division 382-4241
Environmental Research Laboratory
Duluth, MN, Region V 783-9550 (218-727-6692)
ENVIRONMENTAL RELEASES AND EXPOSURE (Sections 3 and 4)
Office of Air Quality and Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Water Regulations and Standards (OWRS)
Monitoring and Data Support Division 382-7051
Office of Toxic Substances (OTS)
Exposure Evaluation Division 382-3873
R-2 July, 1983
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DATA BASES (Section 5)
Office of Toxic Substances (OTS)
Information Management Division 382-3749
REGULATORY STATUS, STANDARDS, AND CRITERIA (Sections 6 and 7)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Drinking Water (ODW)
Criteria and Standards Division 382-7575
Office of Water Regulations and Standards (OWRS)
Criteria and Standards Division 755-0100
Effluent Guidelines Division 382-7120
Office of Solid Waste (OSW)
Permits and State Programs Division 382-4746
SPILL CLEAN-UP AND DISPOSAL (Section 8)
Note: For Emergencies call the National Response Center at 1-800-424-8802
(1-800-426-2675 from the Baltimore/Washington area).
Office of Emergency and Remedial Response (OERR)
Emergency Response Division 362-2182
Hazardous Site Control Division 382-2443
Oil and Hazardous Materials Spills Branch
Edison, NJ; Region II 340-6635 (201-321-6635)
ANALYTICAL TECHNIQUES (Section 9)
Environmental Monitoring Systems Labs (EMSL)
Air Analysis
Research Triangle Park, NC 629-2454 (919-541-2454)
Water Analysis
Cincinnati, OK 684-7311 (513-684-7311)
Waste Analysis
Las Vegas, NV 545-2137 (702-798-2137)
R-3 July, 1983
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Office of Monitoring Systems
and Quality Assurance 382-5767
GENERAL IPP COMMENTS, CORRECTIONS, OR QUESTIONS
Chemical Coordination Staff
Chemical Information
and Analysis Group 382-3375
R-4 July, 1983
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2,3,7,8-TCDD
-------
2,3,7,8-TETRACHLORODIBENZO-p-DIOXIN (2,3,7,8-TCDD)
Table of Contents Page
Physical/Chemical Properties and Chemistry 1-1
Properties 1-1
Chemistry and Environmental Bate/Transport 1-1
Effects Information 2-1
Health Effects 2-1
Environmental Effects 2-2
Environmental Release 3-1
Exposure 4-1
Air Exposure 4-1
Water Exposure 4-1
Other Exposure Routes 4-1
Data Bases 5-1
NIH/EPA Chemical Information System (CIS) 5-1
Chemicals in Commerce information System (CICIS) 5-2
Chemical Substances Information Network (CSIN) 5-3
Graphic Exposure Modeling system (GEMS) 5-3
Regulatory Status 6-1
Promulgated Regulations 6-1
Proposed Regulations 6-3
Other Actions 6-4
Standards and Recommended Criteria 7-1
Air 7-1
Water 7-1
Etood 7-2
July, 1984
-------
Spill or Other Incident Clean-up/Disposal 8-1
Sampling, Acceptable Analytical Techniques and Quality Assurance 9-1
Air 9-2
Water 9-2
Solid Waste 9-3
Other Samples 9-4
Quality Assurance 9-4
References and Office Contacts R-1
July, 1984
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2,3,7,8-TETRACHLORODIBENZO-p-DIOXIN (2,3,7,8-TCDD)
1. PHYSICAL/CHEMICAL PROPERTIES AND CHEMISTRY
1.1 Properties
There are a total of 73 different compounds classified as polychlor-
inated dibenzo-p-dioxins (PCDOs). PCODs contain from two to eight
chlorine atoms located in any of the eight positions on the two
aromatic rings of the dibenzo-p-dioxin nucleus shown below. There
are 22 isomers of tetrachlorodibenzo-p-dioxin (TCDDs), including
2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD). The Agency focus
on 2,3,7,8-TCDD reflects both its presence in commercial formulations
derived from 2,4,5-trlchlorophenol and its high toxlcity.
Some physical/chemical properties of 2,3,7,8-TCDD are presented in
Table 1. The compound is liphophilic and has a very low solubility
in water. It has a low vapor pressure and resists thermal decomposi-
tion (ASME, 1981).
1.2 Chemistry and Environmental Fate/Transport
PCDDs are formed as by-products during the synthesis of polychlori-
nated phenols and derived pesticides. Combustion of general munici-
pal, commercial, and industrial wastes also may result in release of
PCDOs. The PCDDs are chemically stable under most environmental
conditions (OWRS, 1979).
2,3,7,8-TCDD has a uv absorption at 307 nm and may be susceptible to
photochemical degradation in the atmosphere. Experiments carried out
under environmental sunlight conditions indicate that the photolytic
half-life of this compound in the gas phase is on the order of 5 to
24 days. Oxidation by hydroxyl radicals in the atmosphere may also
be significant (ASME, 1981). Atmospheric transport of PCDDs occurs
by way of airborne particulate matter which is released by combustion
of wastes. Present estimates of potential TCDD emission from
municipal waste combustors suggest that such releases do not present
a public health hazard for residents living in the vicinity of the
plants (EPA, 1981).
Data from microcosm experiments indicate that 2,3,7,8-TCDD reaching
the aquatic environment is probably strongly adsorbed onto sediment.
1-1 July, 1982
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TABLE 1; PROPERTIES OF 2.3,7,8-TCDDa
Chemical Name
and Formula:
Chemical Abstract Service
(CAS) Number
and Synonyms:
Molecular Weight:
2,3,7,8-tetrachlorodibenzo-p-dioxin
C 12^1402
1746-01-6
2,3,7,8-TCDDb
322
Molecular Structure:
Melting Point:
Decomposition Temperature:
Vapor Pressure (25°C)
Solubility: Water
Benzene
n-Octanol
Log octanol: water
partition coefficient
305°C
>700°C
10-6 to 10-7 torr (estimated)
0.2 ug/1
0.57 g/1
0.048 g/1
7.14 (calculated)
a Source: (ASME, 1981).
t> Also popularly known as "TCDD" or "Dioxin".
1-2
July, 1982
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Bloaccumulation of the compound is likely based on its lipophilic
nature, and laboratory data on uptake by biota support this
hypothesis. Photolysis of the chemical in water may be significant
if reactive organic substrates (e.g., hydrogen atom donors) are
available. While some reports suggest that volatilization and
biodegradation may also be Important processes for aquatic
2,3,7,8-TCDD, experimental verification is needed (OWRS, 1979; 1ERL,
1980).
The transport and fate of 2,3,7,8-TCDD in soil has been investigated
to a limited extent. 2,3,7,8-TCDD is not leached from most soils due
to its strong adsorption onto soil particle surfaces; mobility
increases with decreasing amounts of organic matter in the soil.
While 2,3,7,8-TCDD in soil is fairly immobile, transport with soil
particles may occur and could result in surface water contamination.
The evidence for biodegradacion of 2,3,7,8-TCDD in soil is inconclu-
sive; if biodegradation occurs, it is a slow loss mechanism from
soil. Photodegradation of 2,3,7,8-TCDD on surface soil appears to be
a possible loss mechanism. Uptake by plants does not appear to be an
important fate for 2,3,7,8-TCDD (ASME, 1981).
1-3 July, 1982
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2. EFFECTS INFORMATION
2.1 Health Effects (CONTACT: Jerry Stara, FTS 684-7531)
2.1.1 Acute Toxiclty
On a molecular basis, 2,3,7,8-TCDD is one of the most toxic synthetic
chemicals. An important consideration for understanding the poten-
tial significance of PCDD release is the widely differing toxicities
of the individual PCOD compounds. The PCDOs with chlorine substi-
tuents on the 2,3,7, and 8 positions are recognized as having high
acute toxicity; the toxicological information on 2,3,7,8-TCDD is by
far the most extensive (ASME, 1981). The LDjQ values reported for
2,3,7,8-TCDD vary widely for different animal species. Representa-
tive L05Q values for oral exposure are (ug/kg body weight): guinea
pig, 0.6-2.1; rat, 22-45; mouse, 284 (IERL, 1980). Studies with ex-
perimental animals have shown that exposure to 2,3,7,8-TCDD leads to
malfunction of liver, pancreas, CNS, and thymus; death is frequently
delayed and may occur as long as 40 days after a single exposure
(ASME, 1981).
Reports of human symptoms resulting from acute high-level exposure to
2,3,7,8-TCDD arise primarily from industrial accidents. Generally
there is no quantitative measure of dose, and exposure to multiple
chemicals often complicates interpretation. Immediate symptoms arise
from the irritant nature of 2,3,7,8-TCDD which leads to irritation of
the eyes, respiratory tract, and skin. As little as 20 ug of
2,3,7,8-TCDD on the skin is reported to lead to chloracne develop-
ment. Other symptoms of exposure include: headache, dizziness,
nausea, fatigue, Insomnia, loss of libido, and arthralgias (pains in
the joints). Other effects which may be delayed or immediate include
porphyria (a disease associated with abnormal metabolism of porphy-
rins by the liver), liver dysfunction, hyperpigmentation, and hirsut-
ism. A variety of metabolic, emotional, and neurological disorders
also appear in some cases (IERL, 1980).
2.1.2 Chronic Toxicity
In humans, chronic exposure to dioxln can cause chloracne and another
dermatologic disorder, porphyria cutanea tarda (PCT), a photosensi-
tive dermatosls caused by altered porphyrin metabolism. Hepatic
(liver) toxicity resulting from prolonged exposured to 2,3,7,8-TCDD
(common in animal models) has been observed in human workers after
industrial exposure (IERL, 1980).
In laboratory animals, dloxin has caused damage to renal (kidney)
tubular epithelium and caused alteration in levels of serum
gonadatrophln (pituitary hormones influencing reproductive organs).
A profound deficit in cell-mediated immunity is produced in
experimental animals exposed to 2,3,7,8-TCDD in the prenatal period.
Along with thymlc atrophy, exposure to 2,3,7,8-TCDD leads to
depletion of cells in the spleen, lymph nodes and bone marrow (IERL,
1980; OURS, 1981).
2-1 July, 1982
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Carcinogerticity, Mutagenicity, and Teratogenicity - Bioassays have
demonstrated that 2,3,7,8-TCDD is an animal carcinogen in rats and
mice when ingested. Multiple studies which examined the effects of
2,3,7,8-TCDD administered in combination with other carcinogens indi-
cate that 2,3,7,8-TCDD can also act as a potent cocarcinogen (OWRS,
1981).
The information with respect to human exposure is less conclusive.
Epidemiological studies of cohorts of workers engaged in chlorophenol
production and use, and their exposure to TCDDs in this country
suggest that any overall carcinogenic effect on humans is small. A
significant excess of stomach cancer, however, has been reported in a
similar cohort of German workers. In addition, recent studies indi-
cate that soft tissue sarcomas (a form of cancer) may be associated
with long-term exposure to phenoxy herbicides which contain 2,3,7,8-
TCDD. The human information available from the Seveso, Italy expo-
sure in 1976 has not indicated that the local populations have
developed any excess of cancer. However, it may be too early to
evaluate the long-term effects from this exposure in view of the
short period of time that has elapsed since the Seveso incident and
the generally longer latency period for cancer development. More
definitive work to address this question has been initiated by the
National Institute of Occupational Safety and Health (NIOSH) and the
National Cancer Institute (EPA, 1981; 1ERL, 1980).
2,3,7,8-TCDD displays an unusually high degree of reproductive toxi-
city in animals. It was found in numerous animal studies to cause
teratogenic and fetotoxlc effects and reduced fertility. In a
three-generation reproductive study in rats, a reduction in fertility
was observed after daily doses of 0.1 or 0.01 ug/kg/day. Equivocal
effects were also seen at the lowest dose (0.001 ug/kg/day). Human
epidemiological studies in this area are limited; those that have
been conducted lack the statistical power to demonstrate clear
exposure-related effects (EPA, 1981, OWRS, 1981). Related PCDDs were
relatively nontoxic and are reported to have no observed teratogenic
effects at the doses studied (IERL, 1980).
In genotoxicity tests, none of the Salmonella strains capable of de-
tecting base-pair substitutions ga"vepositive results when tested
with 2,3, 7,8-TCDD. Some investigations have indicated that this
chemical may be mutagenic in one Salmonella strain which detects
frame shift mutations. A dominant lethal study with 2,3,7,8-TCDD was
negative for male rats given daily oral doses of 4, 8, and 12 ug/kg
for seven days before mating; there was no evidence of induction of
dominant lethal mutations during postmeiotic phases of
spermatogenesis (OWRS, 1981; IERL, 1980).
2.2 Environmental Effects (CONTACT: Douglas W. Kuehl, FTS 783-9559)
2.2.1 Aquatic Effects
No data are available concerning the acute toxicity of 2,3,7,8-tetra-
chlorodibenzo-p-dioxin to freshwater fish. Delayed mortality has
been observed following acute exposures of salmon to concentrations
2-2 July, 1982
-------
as low as 0.056 ng/1. The salmon were exposed for 96 hours under
static conditions and then transferred to control water; after 60
days there was 12% mortality compared to 2% among the control fish.
Salmon exposed to a 100-fold higher concentration (0.0056 ug/1)
showed a 55% delayed mortality (OURS, 1981).
Although steady-state bioconcentration factors are not available,
sufficient studies have been completed to Indicate high bioconcen-
tration factors as predicted by the high octanol; water partition
coefficient. Data on the toxicity of 2,3,7,8-tetrachlorodibenzo-p-
dioxin to freshwater aquatic life are few, but the high mammalian
toxicity coupled with a high bioconcentration factor is strong
evidence for a concern about residues produced by concentrations in
water in the ug/1 range or lower (OWRS, 1981).
No data are available concerning the toxicity of 2,3,7,8-tetrachloro-
dlbenzo-p-dioxin to saltwater aquatic life.
2.2.2 Soil and Terrestrial Life
Several studies have examined the levels of 2,3,7,8-TCDD in animals
living in contaminated areas. Available data indicate that
2,3,7,8-TCDD accumulates in environmentally exposed wildlife. Since
the molecules are lipophilic they tend to accumulate in fatty
tissue. Exposed wildlife tend to bloaccumulate TCDD at varying
degrees, but biomagniflcation does not appear to be significant
(IERL, 1980).
Few studies are available which determine whether PCDDs are
incorporated into plants. Results available indicate that very small
amounts of 2,3,7,8-TCDD can be accumulated in plants. 2,3,7,8-TCDD
can be translocated from the soil and are usually found in newly
forming organs of the plant. Below-ground portions of exposed plants
tend to have higher concentrations than aerial portions. However,
the fact -that other studies have shown no uptake by plants emphasizes
the need for further research (IERL, 1980).
2-3 July, 1982
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3. ENVIRONMENTAL RELEASE
PCDDs are not manufactured commercially. However, they are formed
inadvertently as Impurities during the production of polychlorinated-
phenols. Various PCDOs have been reported in commercial samples of
2,4,5-trichlorophenol (2,4,5-TCP), 2,4,6-trichlorophenol, 2,3,4,6-
tetrachlorophenol, and pentachlorophenol. The 2,3,7,8-TCDD isomer is
formed primarily in the production of 2,4,5-TCP. Because the major
use of 2,4,5-TCP is in the manufacture of the herbicide 2,4,5-tri-
chlorophenoxyacetic acid (2,4,5-T) and Silvex, 2,3,7,8-TCDD is found
as a trace impurity in these pesticides. 2,3,7,8-TCDD is also con-
sidered a possible trace contaminant in the bactericide hexachloro-
phene (ASME, 1981; IERL, 1980).
Parts-per-million quantities of TCDDs have been reported in 2,4,5-T
manufactured in the past. However, 2,4,5-T with 2,3,7,8-TCDD isomer
content of less than 0.1 ppm is now commercially available. Produc-
tion and use of both Silvex and 2,4,5-T have declined in recent years
due to severe restrictions on the use of these herbicides (IERL,
1980).
Detectable quantities of PCDDS have also been identified from various
combustion sources. PCDDs have been found in collected fly ash
samples (i.e., from electrostatic precipitators) from municipal waste
incinerators in the U.S. and a number of other countries. PCDDS were
also detected in industrial and hazardous waste incinerators. In
general, levels of PCDDs from municipal Incinerators appear to be
lower than levels emitted from industrial incinerators. Levels of
TCDDs detected in municipal incinerator fly ash vary widely (2-100
ppb), but are generally less than 10 ppb (IQng/g). Where isomer-
specific data are available, the 2,3,7,8-TCDD isomer is not found to
be a major component of the TCDDs collected (ASME, 1981; EPA, 1981).
PCDDs have also been detected in the flue gas from municipal and
industrial incinerators. The PCDDs are probably adsorbed to the
sub-micron particulates emitted, although it is possible that PCDDs
exist partly in the vapor phase at stack termperatures (ASME, 1981).
A recent study (OB, 1981), reported that PCDDs were detected only in
stack gas and associated particulates from a municipal waste
combust or and not in the fly ash as has been reported in other
studies (ASME, 1981).
Because 2,3,7,8-TCDD is not commercially manufactured, limited data
are available on its (inadvertent) production and release. However,
based on its occurrence in commercial pesticide products, it was
estimated that about 1 kg was produced annually (in 1976) as an
impurity in 2,4,5-TCP and related herbicides. The decreased produc-
tion and usage of Silvex in recent years coupled with lower levels of
2,3,7,8-TCDD in commercial products suggests that the current produc-
tion volume could be significantly less than 1 kg/yr. The amount of
2,3,7,8-TCDD produced during combustion cannot be estimated at this
time due to a lack of data (ASME, 1981; IERL, 1980).
3-1 July, 1982
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A major route of entry of 2,3,7,8-TCDD into the environment appears
to be release of compounds contaminated with 2,3,7,8-TCDD to the land
through land application and land disposal of contaminated wastes.
The principal route of entry into the aquatic environment is believed
to be erosion and runoff from land. Current and past disposal of
2,3,7,8-TCDD-contaminated substances, through incineration and
landfilling, represents an unknown and potentially significant source
of entry of 2,3,7,8-TCDD into water. Probable sources of release of
2,3,7,8-TCDD to the air include contaminated particulates from
incinerators, pesticide production and formulation areas, and
undetermined quantities from combustion sources. 2,3,7,8-TCDD may
also be released accidentally from spills during transportation or
inadvertent release during the manufacture and formulation of
2,3,7,8-TCDD-contaminated pesticides.
The origin of PCDDs in particulates arising from combustion is not
clear. PCDDs may form in most combustion processes (as claimed by
Dow), or only in the presence of chlorinated phenol precursors.
Another possibility is that the PCDDs may already be present as con-
taminants of the wastes being burned (ASME, 1981).
3_2 July, 1982
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4. EXPOSURE ROUTES
2,3,7,8-TCDD may enter the body through dermal absorption, ingestion,
and inhalation. However, many exposure determinations appear to be
fraught with analytical difficulties because 2,3,7,8-TCDD is only one
of many trace contaminants found in chlorinated industrial products.
In essence, it is unclear in many cases what isomer was actually
being measured (OWRS, 1981).
The most obvious groups at risk are those employed in the manufacture
of chemicals in which 2,3,7,8-TCDD may occur as an unwanted by-pro-
duct. The spraying of herbicides containing traces of 2,3,7,8-TCDD
has become less of a problem because of restrictions on the use of
such agents. Considering the reproductive toxicity of 2,3,7,8-TCDD,
women of child-bearing age and especially the fetus may be at high
risk from exposure to 2,3,7,8-TCDD (OWRS, 1981).
4.1 Air Exposure (CONTACTS: Jack McGinnity, FTS 629-5504
Warren Peters, FTS 629-5645)
No data pertaining to the inhalation exposure of 2,3,7,8-TCDD were
found. It is clear that the spraying of 2,4,5-T could lead to a
concomitant exposure to 2,3,7,8-TCDD, but it is not possible to
estimate a typical exposure because of spray drift to nontarget
sites, and because of the intermittent exposure during spraying.
Potential airborne exposures to human populations living near chemi-
cal plants (e.g., 2,4,5-TCP, 2,4,5-T) may also occur. Human popula-
tions living in areas near incinerators could potentially be exposed
to variable concentrations of PCDDs, dependent upon the materials
consumed (OWRS, 1981).
A preliminary evaluation of the risks related to TCDDs emissions from
municipal waste combustors has been made by EPA using mathematical
dispersion models and data from five U.S. sites. This evaluation
suggests that present emission levels of TCDDs from the Incinerators
do not present a health hazard for residents in the immediate vicin-
ity. This was an interim report and EPA intends to monitor represen-
tative facilities for future TCDD emissions (EPA, 1981).
4.2 Water Exposure
Human exposure to 2,3,7,8-TCDD that can be directly attributed to
drinking water alone appears to be low. No 2,3,7,8-TCDD has ever
been detected in drinking water using methods with detection limits
in the parts per trillion (ppt) range (OWRS, 1981).
4.3 Other Exposure Routes
Dermal exposure may be significant during the spraying of 2,4,5-T.
However, accurate determinations of the amounts of 2,3,7,8TCDD
absorbed during such operations appear to be lacking (OWRS, 1981).
4-1 July, 1982
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The occurence of 2,3,7,8-TCDD in food could result from (1) acciden-
tal spraying of plant crops with 2,3,7,8-TCDD-contaminated herbi-
cides; (2) consumption by livestock of 2,3,7,8-TCDD-contaninated
forage; or (3) magnification of residues through the food chain.
Conceivably, 2,3,7,8-TCDD could also be deposited on food crops dur-
ing the combustion of 2,4,5-T treated vegetation. Contaminated beef
fat samples have been found to have concentrations varying between 3
to 6 ppt of 2,3,7,8-TCDD. 2,3,7,8-TCDD has also been reported in
fish from the North Atlantic and the Great Lakes at concentrations
ranging from below detection to 278 ppt. Because of the great analy-
tical difficulties involved in all of these 2,3,7,8-TCDD analyses,
these results must be viewed with caution (OWRS, 1981).
4-2 July, 1982
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5. DATA BASES
5.1 WIH/EPA Chemical Information System (CIS)
This is a collection of various scientific data bases available
through an interactive computer program. The linking system between
these data files is the Structure and Nomenclature Search System
(SANSS). CIS can also provide a list of non-CIS sources of
information on a chemical of interest. For further information,
contact Jim Cottrell at FTS 382-3546.
CIS contains numeric, textual, and bibliographic information in the
areas of toxicology, environment, regulations, and physical/chemical
properties. Several of these data bases are described below.
5.1.1 EPA Chemical Activities Status Report (EPACASR)
EPACASR is an on-line system containing information on EPA'.s interest
in chemicals, this system includes data on the Agency's regulations,
research, and assessments directed toward specific chemicals.
EPACASR is published annually and the data base is updated as
information is received. A searchable subset itemizes NTP/NCI
studies and results, as well as chemicals discussed in the IARC
monograph series. (Other sources are added as appropriate.) Entries
identify the statutory authority, the nature of the activity, its
status, the reason for and/or purposes of the effort, and a source of
additional information.
EPACASR is now available on CIS for internal use by EPA personnel and
is expected to be accessible from a public CIS account in the near
future. The publication and computer tapes are also available
through the National Technical information Service (NTISK For
further information on EPACASR, contact Eleanor Merrick at
FTS-382-3626.
5.1.2 Industry Pile Indexing System (IFIS)
IFIS is an on-line system which contains information relating to the
regulation of chemicals by EPA through industry-specific
legislation. IFIS enables the user to determine, for any particular
industry, which chemicals are used and produced and how these
chemicals are regulated. IFIS is currently available on CIS for
internal use by some EPA personnel and is expected to be accessible
from a public CIS account soon. For more information on IFIS,
contact Daryl Kaufman at FTS 382-3626.
5-1 July, 1984
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5.1.3 Scientific Parameters in Health and the Environment,
Retrieval and Estimation (SPHERE)
SPHERE is being developed by the EPA Office of Toxic Substances as a
system of integrated data bases, each representing a compilation of
extracted scientific data. The system is being released to the
public in stages as part of CIS, and the accessibility of component
data bases should be confirmed with the contact given below. The
components currently available (either through public CIS accounts or
the internal EPA system) include: DERMAL, which provides
quantitative and qualitative health effects data on substances
admitted to humans and test animals via the dermal route; AQUIRE, a
component containing aquatic toxicity data for about 2,000 chemicals;
GENETOX, a mutagenicity data base; ISHOW, and ENVIROFATE, both of
which are compilations of physical/chemical parameters useful in
assessing environmental fate and transport. For more information
contact Paula Miles, FTS 382-3760.
5.1.4 Oil and Hazardous Materials Technical Assistance Data System
(OHMTADS)
OHMTADS is a data base created by EPA to aid spill response teams in
the retrieval of chemical-specific response information. The file
currently contains data for approximately 1,200 chemicals including
physical/chemical, biological, toxicologies1, and commercial
information. The emphasis is on harmful effects to water quality.
OHMTADS is available to the public through CIS.
5.1.5 Chemical Evaluation Search and Retrieval System (CESARS)
CESARS provides detailed information and evaluations on a group of
chemicals of particular importance in the Great Lakes Basin. CESARS
was developed by the State of Michigan with support from EPA's Region
V. Presently, CESARS contains information on 180 chemicals including
physical-chemical properties, toxicology, carcinogenicity, and some
aspects of environmental fate. Information for most chemicals is
extensive and consists of up to 185 data fields. CESARS is
accessible through public CIS accounts.
5.2 Chemicals in Commerce Information System (CICIS)
CICIS is an on-line version of the inventory compiled under the
authority of TSCA. This law required manufacturers of certain
chemicals (excluding food products, drugs, pesticides, and several
other categories) to report production and import data to EPA. CICIS
contains production volume ranges and plant site locations (for 1977)
for over 58,000 chemical substances. There is also a Confidential
Inventory in which data for some chemicals are claimed confidential
and are not available in the public inventory. A version of CICIS
(TSCA Plant and Production, or TSCAPP) is now accessible through
CIS. For more information contact Geri Nowak at FTS 382-3568.
5~2 JUly, 1984
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5.3 Chemical Substances Information Network (CSIN)
The Chemical Substances Information Network (CSIN) is not another
data base, but rather a sophisticated switching network. CSIN links
many independent and autonomous data and bibliographic computer
systems oriented to chemical substances, establishing a "library of
systems." Users may converse with any or all systems interfaced by
CSIN without training on these independent systems, regardless of the
hardware, software, data formats, or protocols of these information
resources.
Information accessible through CSIN includes data on chemical
nomenclature, composition, structure, properties, toxicity,
production uses, environmental effects, regulations, disposal, and
other aspects of the life cycle of materials as they move through
society. Currently, twelve independent information resources are
accessible through CSIN, including: National Library of Medicine
(NLM); Chemical Information System (CIS); CAS-On-Line; SDC's ORBIT;
Lockheeds's DIALOG, and the Bibliographic Retrieval Service (BRS).
For further information contact Dr. Sid Siegel at PTS 395-7285.
5.4 Graphical Exposure Modeling System (GEMS)
EPA has developed GEMS, an interactive computer system, to provide a
simple interface to environmental modeling, physiochemical property
estimation, statistical analysis, and graphical display
capabilities. GEMS is being developed for use by the Office of Toxic
Substances to support integrated exposure/risk analyses. Tlie system
provides environmental analysts who are unfamiliar with computer
programming with a set of sophisticated tools to undertake exposure
assessments. For information about the system and the current
accessibility of GEMS, contact Bill Wood at FTS 382-3928.
5-3 July/ 1934
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6. REGULATORY STATUS1 (Current as of 7/84)
6.1 Promulgated Regulations
6.1.1 EPA Programs
Clean Water Act (CWA)
o Section 311 (b)(2)(A) - Three compounds potentially contaminated
by 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) are 2,4,5-
trichlorophenoxyacetic acid (2,4,5-T), 2,4,5-trichlorophenoxy
propionic acid (silvex), and 2,4,5-trichlorophenol (2,4,5-
TCP). These three chemicals are designated as hazardous
substances (40 CFR 116.4) and are subject to reporting
requirements (reportable quantities, 40 CFR 117.3) in case of
discharge.
o Sections 301, 304, 306, 307 and 316 - 2,3,7,8-TCDD is listed as
a toxic pollutant (40 CFR 401.15). Accordingly, effluent
limitations, pretreatment standards, new source performance
standards, and standards of performance for new and existing
sources have been issued for sections of the following
industries:
Electroplating2 (40 CFR 413),
Steam electric power generating (40 CFR 423),
Pulp, paper,, and paperboard3 (40 CFR 430),
Metal finishing2 (40 CFR 433), and
Pesticide chemicals (40 CFR 455).
Resource Conservation and Recovery Act (RCRA)
o Section 3001 - 2,3,7,8-TCDD is listed as a hazardous constituent
(40 CFR 261, App. VIII). 2,3,7,8-TCDD is not listed as a
hazardous waste under 40 CFR 261 .33, however, several compounds
which may contain TCDD as an impurity are listed, i.e., 2,4,5-
TCP (Hazardous waste number (HHN) U230), 2,4,5-
trichlorophenoxyacetic acid (HWN 232), and silvex (HWN 233)).
Extractable silvex (2,4,5-TP) also characterizes solid waste as
hazardous under the EP toxicity test (40 CFR 261.24, Table 1).
1While few regulations explicitly cover 2,3,7,8-TCDD, many regulations do
cover compounds which may be contaminated with 2,3,7,8-TCDD. Therefore
regulations concerning 2,4,5-TCP, 2,4,5-T and silvex will also be included in
this Section.
22,3,7,8-TCDD is controlled by limiting the total toxic organics (TTO), which
is the summation of all quantifiable values greater than 0.010 milligrams per
liter.
Explicitly regulates tnchlorophenol only.
6-1 July, 1984
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Sections 3002-3006 - Regulations for generators and transporters
of hazardous waste and standards for treatment, storage, and
disposal facilities are applicable (40 CFR 262 to 265).
Permitting procedures are included in the consolidated permit
regulations (40 CFR 122 to 124).
Federal Insecticide, Fungicide, and Rodenticide Act (FIFRA)
o Section 12(b) - Establishes procedures for persons who
export or intend to export 2,3,7,8-TCDD to submit
notification to EPA (40 CFR 707).
o Section 6 - Prohibits removal of TCDD-containing wastes at
the Vertac Chemical Company facilities in Jacksonville,
Arkansas. Also requires 60-day notice to EPA by any person
disposing wastes containing TCOO (40 CFR 775).
Safe Drinking Water Act (SDWA)
o Section 1412 - A National Primary Drinking Water Standard
has been issued for silvex. 2,3,7,8-TCDD is a potential
contaminant in silvex (40 CFR 141.11).
o Section 1421 and 1424 - Establishes an underground
injection control (UIC) program to protect underground
sources of drinking water (40 CFR 146). Requirements and
criteria to be used by States incorporate all hazardous
wastes as defined by RCRA (40 CFR 261). Permitting
procedures are given in the consolidated permit regulations
(40 CFR 122 to 124).
Federal Food, Drug, and Cosmetic Act (FFDCA) Administered by EPA
o Section 408 - Establishes tolerances for residues of silvex in
or on pears resulting from post harvest application (40 CFR
180.340). 2,3,7,8-TCDD is a potential contaminant in silvex.
6.1.2 Programs or Other Agencies
Occupational Safety and Health Act (OSHA)
o 2,4,5-T designated a toxic and hazardous air contaminant.
Accordingly, OSHA has set a maximum allowable ambient air
concentration in the workplace (29 CFR 1910.1000, Table Z-1).
TCDD is a potential contaminant in 2,4,5-T.
Hazardous Materials Transportation Act (DOT)
o 2,4,5-T, TCP, phenoxy-based, and benzoic-based pesticides are
designated as hazardous materials for the purposes of
transportation requirements (49 CFR 172.101). TCDD is a
potential contaminant in these compounds.
6-2 July, 1984
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6.2 Proposed Regulations
6.2.1 EPA Programs
CWA
o EPA has proposed effluent guidelines, pretreatment standards,
and new source performance standards for the pesticide chemicals
manufacturing industry (40 CFR 455). The pollutants regulated
are silvex isooctyl esters, silvex salts, silvex, and 2,4,5-T
(47 FR 54011, November 30, 1982).
RCRA
o EPA has proposed to list as acutely -hazardous, those wastes
containing certain chlorinated dioxins, and to specify certain
management standards for these wastes. In addition, EPA has
proposed to revoke regulations concerning the disposal of TCDD-
contaminated wastes under TSCA at such a time as when the
regulation becomes effective under RCRA. Parts of Title 40
affected by this proposal and the wastes involved are:
40 CFR 261.31; HWNs F020, F021, F022, and F023,
40 CFR 261.33; HWNs U212, U230, U231-U233, and U242,
40 CFR 261, App. Ill; chlorinated dibenzo-p-dioxins,
40 CFR 261, App. VII; tetra-, penta-, and hexa- chloro-
dibenzo-p-dioxins,
40 CFR 261, App. VIII; tetra-, penta-, and hexachloro-
dibenzo-p-dioxins,
40 CFR 261, App. IX; chlorinated dibenzo-p-dioxins
40 CFR 264.231, .259, .283, and .317,
40 CFR 265, and
40 CFR 775 (removed when rule is finalized).
(48 FR 14514, April 4, 1983).
Comprehensive Environmental Responses, Compensation, and Liability
Act (CERCLA or Superfund)
o CERCLA provides for the liability, compensation, clean-up, and
emergency response for the release of hazardous substances into
the environment. This Act also deals with the clean-up of
hazardous waste disposal sites (42 USC 9601; PL 96-510). EPA is
developing regulations concerning the designation of hazardous
substances, the development of reportable quantities, claims
procedures, and the confidentiality of business records (46 FR
54032). Revisions to the National Contingency Plan (NCP) as
required by CERCLA have been issued in a proposed rule (47 FR
10972).
6-3 July, 1984
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2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD), 2,4,5-T and its
acids, esters, amines, and salts, silvex, and 2,4,5-
trichlorophenol (2,4,5-TCP) are hazardous substances under
CERCLA and will be subject to regulations developed under
Superfund. EPA has proposed adjustments to the RQ's established
under CERCLA and the CWA (48 FR 23552).
6.3 Other Actions
FIFRA - EPA issues notice of intent to cancel the registrations
of all products which contain as an active ingredient 2,4,5-
trichlorophenoxyacetic acid (2,4,5-T) or silvex (2,4,5-
trichlorophenoxy propionic acid) or any salt, ester, amine, or
derivative of 2,4,5-T or silvex, and revokes notice of intent to
hold a hearing to determine if certain uses of 2,4,5-T or silvex
should be cancelled (48 FR 48434). In an additional notice, EPA
announced a policy statement concerning the legal ramifications
of transferring, sales, distribution, or importation of any
unregistered pesticide product containing 2,4,5-T or silvex (48
FR 48436, October 18, 1983).
In a February 29, 1984 notice EPA announced its intention to
suspend the registrations of certain 2,4,5-T and silvex
pesticide products because of failure to comply with an October
14, 1983 request for additional data in support of registration
(49 FR 7443).
CWA - EPA announced on February 15, 1984 the availability of a
final ambient water quality criteria (WQC) document for 2,3,7,8-
TCDD and provided a summary of that WQC (49 FR 5831).
EPA announces the availability of the external review draft of
the Health Assessment Document for polychlorinated dibenzo-p-
dioxins (49 FR 19408, May 7, 1984).
The Office of Research and Development, EPA has completed a risk
analysis of 2,3,7,8-TCDD contaminated soil. The Office of Solid
Waste plans to use this analysis in support of regulations
defining the level of TCDD which causes a soil to be
hazardous. (Contact: John Schaum, FTS 382-7353)
The National Toxicology Program (NTP) published results of
testing in the Third Annual Report on Carcinogens, September,
1983; TCDD is cited as being a substance that may reasonably be
anticipated to be a carcinogen.
KIOSH has issued a Current Intelligence Bulletin (#40) on
2,3,7,8-TCDD which summarizes findings related to the human
hazard potential (DHHS Publication No. 84-104).
6-4 July, 1984
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7. STANDARDS AND RECOMMENDED CRITERIA*
7.1 ftir
o OSHA workplace exposure to toxic air contaminants; 8-hour TWA,
(29 CFR 1910.1000, Table Z-1),
2,4,5-T 10 mg/m3
(2,4,5-trichlorophenoxyacetic acid)
o ACGIH suggested threshold limit values (1980).
2,4,5-T (8-hr TWA) 10 mg/m3
(15 minute STEL) 20 mg/m3
7.2 Water
o Water Quality Criteria (WQC); 49 FR 5831
The estimated lifetime cancer risk of 10~5 from exposure to
2,3,7,8-TCDD from the consumption of contaminated water and
aquatic organisms corresponds to a criterion of 1.3 x 10"
ug/L. For ingestion of contaminated aquatic organisms only, the
estimated lifetime cancer risk of 10~* corresponds to a
criterion concentration of 1.4 x 10 pg/L. If these estimates
are made for the consumption of water only, the risk of 10
corresponds to criterion of 2.2 x 10
Section 311 of the CWA report able quantities for discharge are:
Silvex (2,4,5-TP acid) 100 pounds
2,4,5-T and 100 pounds
2,4, 5-trichlorophenol 1.0 pounds
The RQs proposed under CERCLfl are the same; in addition the
following RQs have been proposed (48 FR 23552) .
2,3,7,8-TCDD 1 .0 pound
Unlisted hazardous wastes that have
characteristics of EP toxicity 1 .0 pound
WasteDOl?, (2,4,5-TP) 100 pounds
•See Appendix A for a discussion of the derivation, uses, and limitations of
these criteria and standards.
July, 1984
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7.3 Food
FDA has set a 50 parts per trillion (ppt) maximum level for 2,3,7,8-
TCDD in food fish from the Great Lakes. (For information on the
development of FDA action levels for 2,3,7,8-TCDD in food, contact
Dick Schmitt, FDA, FTS 557-7324). Tfe Canadian Ministry of Health
and the New York State Department of Health have set maximum levels
of 20 and 10 ppt respectively for food fish from the Great Lakes.
Agency policy on 2,3,7,8-TCDD is still evolving. There are no Agency
criteria for any media except for a final Water Quality Criteria (49
FR 5831). Problems with PCDDs are being handled by the Chlorinated
Dioxins Work Group (CDWG). Questions or requests for assistance can
be referred to this Work Group by calling Donald Barnes, OPTS (202)
382-2897.
7-2 July, 1984
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REFERENCES
The major references used in the preparation of this document are listed
below. EPA documents are referenced by the EPA office of origin and the year
of publication. For further information refer to contacts given throughout
this document or contact the relevant EPA office listed in the next section.
(ASMS, 1981)
(EPA, 1981)
(IERL, 1980)
(NCI, 1980)
(OWRS, 1981)
(OWRS, 1979)
(Reggiani, 1981)
(OTS, 1981)
Dioxin from Combustion Sources, American Society of
Mechanical Engineers (1981).
Interim Evaluation of Health Risks Associated with Emis-
sions of TCDDS from Municipal Waste Resource Recovery
Facilities, EPA - Interim Report, November (1981).
Dioxins, EPA-600/2-80-197, Industrial Environmental Re-
search Lab (1980;.
National Cancer Institute Publications No. (NIH) 80-1757
and 80-1765.
Ambient Water Quality Criteria for 2,3,7,8-Tetrachloro-
dibenzo-p-dioxin, EPA Draft 440/5-80-072, Office of Water
Regulations and Standards (1981).
Water-Belated Environmental Fate of 129 Priority Pollu-
tants, Vol. I, Chapter 34; EPA-440/4-79-029a, Office of
Water Regulations and Standards (1979).
G. Reggiani, Regulatory Toxicology and Pharmacology, _1_:
211-243 (1981).
Emissions of PCDDs and PCDFs from Combustion Sources,
Office of Toxic Substances, October (1981).
R-1
July, 1984
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OFFICE CONTACTS
The EPA offices and divisions that are listed below may be contacted for more
information relating to the indicated sections of this document. While these
offices are, in many cases, the offices of origin for the data included in
this paper, the personal contacts given throughout this document should be
contacted first. Unless otherwise noted, the offices listed are situated in
Headquarters, Washington, D.C., and the telephone numbers given are FTS
(Federal Telecommunications System) numbers. For commercial telephone calls
to Headquarters which are not placed on FTS, area code 202 must be used.
Other commercial numbers are noted for the office contacts located outside
Washington, D.C.
HEALTH AND ENVIRONMENTAL EFFECTS (Section 2)
Office of Health and Environmental Assessment (OREA)
Environmental Criteria and Assessment Office:
Cincinnati, OH 684-7531 (513-684-7531)
Research Triangle Part, NC 629-4173 (919-541-4173)
Carcinogen Assessment Group 382-7341
Office of Drinking Water (ODW)
Health Effects Branch 382-7571
Office of Toxic Substances (OTS)
Health and Environmental Review Division 382-4241
Environmental Research Laboratory
Duluth, MN, Region V 783-9550 (218-727-6692)
ENVIRONMENTAL RELEASES AND EXPOSURE (Sections 3 and 4)
Office of Air Quality and Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504}
Office of Water Regulations and Standards (OWRS)
Monitoring and Data Support Division 382-7051
Office of Toxic Substances (OTS)
Exposure Evaluation Division 382-3873
R-2 July, 1984
-------
DATA BASES (Section 5)
Office of Toxic Substances (OTS)
Information Management Division 382-3749
REGULATORY STATUS, STANDARDS, AND CRITERIA (Sections 6 and 7)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Drinking Water (ODW)
Criteria and Standards Division 382-7575
Office of Hater Regulations and Standards (OWRS)
Criteria and Standards Division 755-0100
Effluent Guidelines Division 382-7120
Office of Solid Waste (OSW)
Permits and State Programs Division 382-4746
SPILL CLEAN-UP AND DISPOSAL (Section 8)
NOTE: For Emergencies call the National Response Center at 1-800-424-8802
(1-800-426-2675 from the Baltimore/Washington area).
Office of Emergency and Remedial Response (OERR)
Emergency Response Division 382-2182
Hazardous Site Control 382-2443
Oil and Hazardous Materials Spills Branch
Edison, NJ; Region II 340-6635 (201-321-6635)
ANALYTICAL TECHNIQUES (Section 9)
Environmental Monitoring Systems Lab (EMSL)
Air Analysis
Research Triangle Park, NC 629-2454 (919-541-2454)
Water Analysis
Cincinnati, OH 684-7311 (513-684-7311)
R-3 July, 1984
-------
Waste Analysis
Las Vegas, NV 545-2137 (702-798-2137)
Office of Monitoring Systems
and Quality Assurance 382-5767
GENERAL IPP COMMENTS, CORRECTIONS, OR QUESTIONS
Chemical Coordination Staff
Chemical Information
and Analysis 382-3375
July, 1984
-------
Toluene
-------
TOLUENE
Table of Contents Page
Physical/Chemical Properties and Chemistry 1-1
Properties 1-1
Chemistry and Environmental Fate/Transport 1-1
Effects Information 2-1
Health Effects 2-1
Environmental Effects 2-3
Other Effects 2-3
Environmental Release 3-1
Air Releases 3-1
Water Releases 3-1
Land Releases 3-1
Exposure Routes 4-1
Data Bases 5-1
Chemicals in Commerce Information System (CICIS) 5-1
EPA Chemical Activities Status Report (EPACASR) 5-1
NIH/EPA Chemical Information System 5-1
Chemical Regulations and Guidelines System (CRGS) 5-1
Chemical Substance Information Network (CSIN) 5-1
EPA Information Clearinghouse 5-2
Regulatory Status 6-1
Promulgated Regulations 6-1
Proposed Regulations 6-2
Other Actions 6-2
Standards and Recommended Criteria 7-1
Air 7-1
Water 7-1
July, 1982
-------
Spill or Other Incident Clean-Up/Disposal 8-1
Hazards and Safety Precautions 8-1
First Aid 8-1
Emergency Action 8-1
Notification and Technical Assistance 8-1
Disposal 8-1
Sampling, Acceptable Analytical Techniques, and Quality Assurance 9-1
Air 9-1
Water 9-1
Solid Wastes 9-3
Other Samples 9-3
Quality Assurance 9-4
References and Office Contacts R-l
July, 1982
-------
TOLUENE
1. PHYSICAL/CHEMICAL PROPERTIES AND CHEMISTRY
1.1 Properties
Of the toluene produced in the United States, only a small fraction
(about 10%) is isolated as toluene. The remainder stays in gasoline
as a benzene-toluene-xylene mixture (BTX). Even so, isolated tolu-
ene ranks fifteenth in the top 50 chemicals produced in the United
States (5.1 million metric tons in 1980). Toluene is produced prin-
cipally during the petroleum refining process by catalytic reforma-
tion. Isolated toluene is used in benzene production, as a gasoline
additive, as a solvent, and in the synthesis of various aromatic
compounds.
Some relevant physical and chemical properties of toluene are listed
in Table 1. Toluene is a colorless liquid at ambient temperature.
It is both volatile and flammable and has a benzene-like odor. The
relatively high vapor pressure and low water solubility of toluene
indicate that most toluene is likely to be found in the vapor phase
mixed with air. Commercial toluene (isolated) may contain benzene
as an impurity.
1.2 Chemistry and Environmental Transport
Toluene is a homolog of benzene in which one hydrogen atom is re-
placed by a methyl group. Although toluene is fairly stable, the
methyl group increases the chemical reactivity of toluene over ben-
zene. Toluene undergoes substitution reactions on both the methyl
group (-CH3) and on the benzene ring. The methyl group in toluene
is susceptible to dealkylation and this process is used commercially
to produce benzene. The methyl group also undergoes oxidation,
both chemical and biochemical, to yield benzole acid.
Due to its relative stability in the atmosphere, toluene undergoes
short- and long-range transport away from urban emission sources.
The primary mode of removal is probably through photochemical reac-
tions in the troposphere. Washout from precipitation apparently is
not a significant transfer mechanism. Toluene is susceptible to
oxidation by photochemically generated hydroxyl radicals which may
result in the formation of cresols, benzaldehyde, and nitrotoluenes
as the major products. The half-life of toluene in the atmosphere
is estimated to be on the order of two days; this value is based on
laboratory data and is dependent on solar intensity, temperature,
and pollutant concentrations. Photolysis of toluene in polluted at-
mospheres (containing NOX) can also yield significant amounts of
peroxynitrates due to secondary reactions involving the initial oxi-
dation products, cresol and benzaldehyde (NRG, 1980).
The volatility and low water solubility of toluene permit rapid
transfer from water surfaces to the atmosphere; the evaporative
1-1 July, 1982
-------
half-life in water is estimated to be on the order of five hours.
Toluene does not undergo extensive chemical transformation in
natural waters. However, toluene may form traces of chlorine-
substituted products during chlorination procedures used for water
purification. To date, experimental results from sediment analysis
suggest that sorption onto sediments is not a significant pathway
for removal of toluene from water. Toluene is readily biodegraded
in aqueous media, both in surface water and during wastewater
treatment (ECAO, 1981).
Although the fate of toluene in soil has not been thoroughly inves-
tigated, intermedia transfer to air is likely; the remaining toluene
adsorbed to the soil is susceptible to biological degradation.
Therefore, volatilization and biodegradation are probably the most
important processes for toluene disposed of on land. Evaporative
losses may be significantly lower from soils with high organic con-
tent (i.e., sludge), compared to sandy soils (ECAO, 1981).
1-2 July, 1982
-------
TABLE 1; PROPERTIES OF TOLUENE*
Synonyms; Methylbenzene, phenylmethane, toluol
CAS Number; 108-88-3
Molecular Formula; C?H8
Structure:
Physical Properties;
Melting point: -95°C
Boiling point: 110.6°C
Vapor pressure (25°C): 28.7 torr
Flash point (close cup): 40°F (4.4°C)
Density (liquid, 20°C): 0.867 g/ml
Solubility in water (25°C): 0.53 g/1
Log octanol/water partition
coefficient: 2.69
Concentration in
Saturated Air (26°): 39,400 ppm
(148 g/m3)
*From data summarized in (ECAO, 1981).
1-3 July, 1982
-------
2. EFFECTS INFORMATION
2.1 Health Effects (CONTACT: Robert McGaughy, FTS 755-3968; Penny
Fenner-Crisp, FTS 472-4944)
2.1.1 Acute Toxlclty
Acute exposures of humans to toluene have almost exclusively in-
volved inhalation in experimental or occupational settings or during
episodes of intentional abuse (i.e., "glue sniffing"). The health
effect of primary concern is dysfunction of the central nervous sys-
tem (CMS). Acute experimental and occupational exposures to toluene
in the range of 200-1,500 ppm have elicited dose-related symptoms
indicative of CNS depression, as well as impairments in reaction
time and perceptual speed. Following initial CNS excitatory effects
(e.g., exhilaration, llghtheadedness), progressive development of
narcosis has characterized acute exposures to excessive concentra-
tions of toluene (i.e., levels approaching the air saturation con-
centration of approximately 30,000 ppm) (ECAO, 1981).
Single short-term exposures to moderate levels of toluene have, on
occasion, been reported to cause transitory eye and respiratory
tract irritation, but irritative effects have generally not been
observed in workers exposed repetitively to toluene. Dermal contact
with toluene may cause skin damage due to Its degreasing action
(OWRS, 1980).
The acute oral toxiclty (1.050) of toluene in rats is in the range of
6.0 to 7.5 g/kg, which indicates only slight toxicity in this spe-
cies. An acute dermal toxicity (LDso) was reported to be 12 g/kg in
the rabbit. Inhalation studies have yielded values for "LC$Q in the
range of 5,300 to 6,900 ppm (6 to 7-hr, exposure) in mice and a
value of 8,800 ppm (4-hr exposure) in rats (ECAO, 1981).
2.1.2 Chronic Toxicity
While a number of studies are available on the effects of chronic
Inhalation exposure to toluene, these studies have yielded conflict-
ing results. Repeated occupational exposures to toluene vapors over
a period of years at levels of 200-400 ppm have been reported to re-
sult in neurologic effects. However, a study of workers with at
least 10 years exposure to atmospheres containing 200-400 ppm tolu-
ene concluded that these exposure levels do not cause adverse neuro-
logical effects. Prolonged abuse (i.e., "glue sniffing") of solvent
mixtures containing toluene (at inhalation exposure levels of up to
30,000 ppm) has, on occasion, led to residual or permanent CNS ef-
fects. Chronic exposure to mixtures of organic solvent vapors con-
taining predominantly toluene has reportedly caused impairments in
visual accuracy and psychomotor performance of workers (ECAO, 1981).
Dysmenorrhea (painful menstruation) has been reported in Japanese
women exposed for over 3 years to 60-100 ppm toluene and concomi-
tantly to 20-50 ppm gasoline in a "few" working places. Distur-
2-1 July, 1982
-------
bances of menstruation have also been reported in female workers ex-
posed concurrently to toluene, benzene, and xylene, and to toluene
and other unspecified solvents (ECAO, 1981).
There is little or no evidence that toluene is -carcinogenic in ani-
mals or man. Inhalation exposure to toluene at concentrations of up
to 300 ppm for 24 months did not produce an increased incidence of
neoplastic, proliferative, inflammatory, or degenerative lesions in
various organs of rats relative to unexposed controls. However, it
should be noted that 300 ppm is not considered a maximum tolerated
dose (MID). Thus, it is unknown if higher exposure levels would
produce the same responses. Other studies indicate that toluene is
not carcinogenic when applied topically to the shaved skin of labo-
ratory animals and that it does not promote the development of skin
tumors following initiation with DMBA (ECAO, 1981).
Toluene has been shown to be non-mutagenic in a battery of micro-
blal, mammalian cell, and whole organism test systems. The Russian
literature reported chromosome aberrations in the bone marrow cells
of rats exposed subcutaneously and via inhalation to toluene, but
these findings have not been corroborated in other studies (ECAO,
1981).
Toluene has been reported to induce cleft palates in mice following
oral exposure, but it was not teratogenlc in mice or rats following
inhalation exposure. Embryotoxic effects (increased incidence of
skeletal anomalies and signs of retarded skeletal development, low
fetal weights) and Increased maternal toxicity were, however, noted
in some of the rats and mice exposed via Inhalation (OWRS, 1980;
ECAO, 1981).
2.1.3 Absorption, Distribution, and Metabolism
Toluene is readily absorbed from the respiratory and gastrointesti-
nal tracts. Studies in humans indicate approximately one-half of
the amount inhaled is retained; ingestion leads to fairly complete
absorption, based on experiments with animals. While liquid toluene
may also be absorbed through the skin, this route does not appear to
be significant for absorption of toluene vapor. Animals given tolu-
ene orally or by inhalation had high concentrations of toluene in
their adipose tissue and bone marrow, and moderately high concentra-
tions of toluene and its metabolites in their liver and kidney.
These results are reasonable, based on tissue-blood partition
coefficients and known routes of metabolism and excretion (ECAO,
1981).
The initial step in the metabolism of toluene is side-chain hydrox-
ylation by the hepatic mixed-function oxidase system, followed by
oxidation to benzole acid. Benzole acid is then conjugated with
glycine to form hippurlc acid and excreted in the urine. In both
humans and animals, 60 to 75 percent of the absorbed toluene can be
accounted for as hippuric acid in the urine, regardless of the dose
or whether the chemical was administered orally or by inhalation.
2-2 July, 1982
-------
The excretion of toluene and its metabolites is rapid; the major
portion occurs within 12 hours of oral administration or the end of
inhalation exposure (ECAO, 1981).
2.2 Environmental Effects (CONTACT: Teresa Norberg, FTS 783-9528)
2.2.1 Aquatic Effects
Lethal effects of toluene have been reported for numerous species of
freshwater and marine fish and invertebrates. The acute LC5Q f°r 22
species of freshwater and marine organisms ranged between 3 and
1,180 ppm. Very little information, however, is available concern-
ing the sublethal effects of toluene exposure on fish. Chronic tox-
icity data, for example, are only available for the sheepshead min-
now. The lowest toluene concentration shown to cause sublethal ef-
fects was 2.5 ppm, in trout and in salmon. This value is lower than
the lowest acute LCso value for any fish species, i.e., 3.08 ppm for
coho salmon. In an embryo-larval test with sheepshead minnow,
chronic effects occurred at a concentration 36 to 152 times lower
than the acute LC50 for Cnis species. This suggests that chronic
effects may occur at lower levels in more sensitive species (ECAO,
1981; OWRS, 1980).
Evaluation of the effects of toluene on aquatic organisms must take
into account several factors. A primary consideration is the high
volatility of toluene. The half-life for volatilization from a wa-
ter column one meter deep has been reported to be between 30 minutes
and 5 hours. Furthermore, the bioconcentration and biomagnification
potential of toluene is low. Toluene is metabolized by fish and the
rate of elimination is rapid (ECAO, 1981).
2.2.2 Other Effects
Except in cases of accidental spills, toluene is unlikely to be pre-
sent at levels that would cause adverse effects on the ecosystem.
Effects have been studied using aquatic organisms, bacteria, and
higher plants. Toluene can both stimulate and inhibit the growth of
algae, depending on the species and the toluene concentration. The
no-effect level for most algal species is 10 mg/1. Several salt-
water algal species and kelp have been tested and effects were ob-
served between 8 and about 433 mg/1. In both microorganisms and
higher plants toluene can disrupt cell membranes, thus causing toxic
or lethal effects. Toluene does not accumulate in plants nor is it
translocated. Ecosystem impacts of toluene spills or chronic low-
level pollution are unknown. Adverse effects may occur but probably
are limited by rapid rates of loss of toluene through evaporation
and biodegradation (ECAO, 1981).
2-3 July, 1982
-------
3. ENVIRONMENTAL RELEASE
As shown in Table 2 (based on 1978 estimates), toluene is released
to the environment from production, usage, and inadvertent sources.
It is evident from Table 2 that nearly all (99.9%) releases of tol-
uene enter the atmosphere. The largest emitters of toluene are
(1978 data): automobile exhaust, 640,000 kkg (58%); industrial use
of toluene as a solvent, 375,000 kkg (34%); and evaporative loss of
gasoline in marketing and automotive use, 37,000 kkg (3.4%). The
relatively small amount of toluene released to surface water «1,200
kkg) arises primarily from spills of gasoline, oil, and toluene.
Land releases, which are also comparatively minor (278 kkg), are
mainly due to transportation spills of gasoline (ECAO, 1981).
3.1 Air Releases
Significant Releases
• Automobile exhaust
• Industrial use as solvent
Other Releases
• Gasoline evaporation (in marketing and use)
• Catalytic reforming (toluene production)
• Ethylene-propylene rubber production
• Combustion processes
3.2 Water Releases
• Spills from transport of gasoline and toluene
3.3 Land Releases
• Spills from transport and storage of gasoline
3-1 July, 1982
-------
TABLE 2. TOLUENE SUPPLY, CONSUMPTION, AND RELEASES PER YEARa
(1978 Data)
Toluene Production
Catalytic reforming
Isolated
Non-isolated (BTX)b
Supply
(Meg)
3,110,000
27,000,000
Consumption
(kkg)
Airborne
Releases
(kkg)
3,011
Aquatic
Releases
(kkg)
Discharge
to POTWs
(kkg)
Discharges
to Land
(kkg)
Pyrolytic cracking
Isolated
Non-isolated (BTX)
324,000
197,000
469
Styrene by-product
135,000
103
u> Coke oven by-product
isj Isolated
Non-isolated (BTX)
Production totals
26,000
96.000
30,888,000
153 47
28 from waste—
water
3,764 47
36
36
31
31
Toluene Uses
i-*
•<
Non-isolated (BTX)
Isolated
Benzene production
Gasoline back-blending
Solvent for paint and coatings
Solvent for adhesives , inks ,
Pharmaceuticals, and others
Toluene diisocyanate
Xylene production
Benzole acid
Benzyl chloride
Vinyl toluene
Other uses
27,293,000
1,675,000
1,465,000
263,000
132,000
200,000
98,000
65,000
36,000
25,000
39.000
335
c
263,000
112,000
256
20
98
36
25
39
1
29
CO
ro
Use totals
31,291,000
375,809
30
NA
NA
-------
OJ
10
\o
00
to
TABLE 2.
Miscellaneous Releases
of Toluene
Gasoline marketing
Auto gasoline evaporation
Auto exhaust
TOLUENE SUPPLY, CONSUMPTION, AND RELEASES PER YEAR (Continued)
(1978 Data)
Supply
(kkg)
Consumption
(kkg)
Airborne
Releases
(kkg)
19,000
18,000
640,000
Aquatic
Releases
(kkg)
Discharge
to POTWs
(kkg)
Discharges
to Land
(kkg)
Transport spills:
Oil
Gasoline
Toluene
Propylene oxide manufacture
Polychloroprene manufacture
Ethylene-propylene terpolymer
and rubber production
Mood preserving industry
Acrylonltrlle manufacture
Combustion processes:
Coal refuse piles
Stationary fuel combustion
Forest fires
Agricultural burning
Structural fires
Cigarette smoke
Coke production (unrecovered)
Others
Miscellaneous subtotals
Combined totalsd 30,888,000
400
680
3
36
460
4,290
6
59
4,400
13,000
7,000
1,000
<1,000
53
10,560
8
718,866 1,089
31,291,000 1,098,439 1,166
6
230
11
247
36 278
a Source: (ECAO, 1981).
b BTX = Combined benzene, toluene, xylene gasoline product.
c Listed under Miscellaneous Releases.
d The discrepancy in production and consumption results from the fact that the former figure is reported by
producers but the latter figure Is a total of estimates only.
-------
4. EXPOSURE ROUTES
The general population may be exposed to toluene through the follow-
ing routes: (1) Inhalation of air; (2) ingestion of water and
foods; and (3) direct exposure through the skin. Certain segments
of the population may be exposed to toluene through occupational ex-
posure, cigarette smoking, and consumer products.
Air constitutes the most important exposure route for the general
population although concentrations are many times lower than the
vapor levels considered to be potentially harmful in occupational
settings. Atmospheric toluene in urban areas arises primarily from
automotive emissions with solvent losses as a secondary source.
Dermal exposures of significance are primarily restricted to occupa-
tional uses.
Estimates of toluene exposure levels for various routes and popula-
tion groups are given in Table 3. Inhalation exposure has been es-
timated for three areas: urban, rural/remote, and areas near manu-
facturing or user sites. The concentration of toluene in monitored
urban areas in the United States ranged from less than 0.1 ug/m3 to
about 200 ug/m3; average levels were in a range of approximately A
to 40 ug/m3.Near manufacturing/user sites, measured toluene
concentrations ranged from 0.1 to 600 ug/m3; atmospheric levels
depend strongly on distance from release sites. In remote and rural
areas, toluene levels averaged about 1 ug/m3 and ranged from a
"trace" to 3.8 ug/m3. intake estimates in Table 3 assume a daily
breathing rate of 22.4 m3/day (157 m3/wk). It should be remembered
that the amount of toluene inhaled is not the amount absorbed. Only
about one-half of the amount Inhaled is retained; also, much of the
absorbed toluene is probably rapidly excreted (ECAO, 1981).
Population exposure through ingestion of food or drinking water is
probably negligible compared to air exposure. Most (>80%) surface
waters contain levels of toluene In the range of 0 to 10 ug/1. The
range of concentrations found in drinking water was 0-19 ug/1. How-
ever, only one water supply examined had a concentration of 19 ug/1;
most other levels of toluene detected were around 1 ug/1 (ECAO,
1981).
4-1 July, 1982
-------
TABLE 3. TOLUENE EXPOSURE ESTIMATES UNDER DIFFERENT EXPOSURE CONDITIONS a b
Exposure Route
Observed
Range of
Concentration
Frequency
of
Exposure
Total Volume
Exposed or
Amount Consumed
Inhalation or
Ingestion Rate
(mg/wk)
General Population
Inhalation
Urban areas
Rural and remote areas
Areas near manufacturing
and user sites
0.1-204 ug/m3
trace-3.8 ug/m3
0.1-600 ug/m3
168 hr/wk
168 hr/wk
168 hr/wk
157 m3
157 m3
157 m3
0.02-32
trace 0.6
0.02-94
N>
Ingestion
Drinking water
Food (fish)
0-19 ug/1
0-1 mg/kg
2 I/day
6.5 g/day
14 1
45.5 g
0-0.3
0-0.45
Occupational Group
Inhalation
380 mg/m3b
40 hr/wk
48 m
18,000b
Cigarette Smokers
Inhalation
0.1 mg/clgarettec
20 cigarettes/day
140 cigarettes
14
ir
a Source: (ECAO, 1981).
b This value assumes 8-hr work day exposure to NIOSH recommended level of 100 ppm (8-hr average).
to c From mainstream smoke only.
-------
5. DATA BASES
5.1 Chemicals in Commerce Information System (CICIS)
The Inventory was compiled under Che authority of Section 8 of TSCA
which requires manufacturers to report to EPA the chemicals imported
and manufactured during calendar year 1977. The Inventory lists the
Chemical Abstract Service (CAS) preferred name for the chemicals,
their respective CAS number (often used for identification purposes),
production site, company name, and volume(s) of production and im-
port. There is also a Confidential Inventory in which many of these
characteristics are claimed confidential by the manufacturer. In
these instances, the confidential information will not be available
on the public inventory. CICIS can now be accessed through the
NIH/EPA Chemical Information System (CIS - see 5.3). For further in-
formation, contact Gerri Nowack at FTS 382-3568.
5.2 EPA Chemical Activities Status Report (EPACASR)
EPACASR is an on-line system containing information on EPA's interest
in chemicals. This system includes data on the Agency's regulations,
research, and assessments directed toward specific chemicals.
EPACASR is published annually and the data base is updated as
information is received. A searchable subset itemizes NTP/NCI
studies and results, as well as chemicals discussed in the IARC
monograph series. (Other sources are added as appropriate.) Entries
identify the statutory authority, the nature of the activity, its
status, the reason for and/or purpose of the effort, and a source of
additional information. Searches may be made by CAS Number or coded
test. For further information contact Eleanor Merrick at FTS
381-3415.
5.3 MIH/EPA Chemical Information System (CIS)
This is a collection of various scientific data bases available
through an interactive computer program. The linking system between
these data files is the Structure and Nomenclature Search System
(SANSS). CIS can also provide a list of non-CIS sources of informa-
tion on a chemical of interest. However, these files have to be
accessed individually by either separate on-line systems or in hard-
copy. For further information contact Delores Evans at FTS 382-3546
or Irv Weiss at FTS 382-3524.
5.4 Chemical Regulations and Guidelines System (CRGS)
CRGS is an on-line data base that is being developed to provide
information on chemical regulatory material found in statutes, regu-
lations, and guidelines at the Federal, State, and international lev-
els. Currently, only the first phase Of. CRGS, which encompasses only
source material at the Federal level, is operational. Nationwide ac-
cess to CRGS is available through Dialog. For further information,
contact Delores Evans at FTS 382-3546 or Ingrid Meyer at FTS 382-
3773.
5-1 July, 1982
-------
5.5 Chemical Substances Information Network (CSIN)
The prototype CSIN, operational since November 1981, has been devel-
oped by merging the technologies of computer networking and distrib-
uted data base management. CSIN is not another data base, but a
library of systems. Through the CSIN front-end intermediary manage-
ment computer, the user may access and use independent and autonomous
information resources that are geographically scattered, disparate
for data and information content, and employ a variety of types of
computer hardware, software, and protocols. Users may converse in
and among multiple systems through a single connection point, without
knowledge of or training on these independent systems.
Currently, six independent information resources are accessible
through CSIN. They are: National Library of Medicine (NLM), CIS,
EPA-CICIS, CAS-On-Une, SDC-orbit, and two files of Dialog: CRGS and
TSCA Inventory. The CSIN management computer allows the user to cre-
ate, retrieve, store, and manipulate data and queries. This elimi-
nates the need for reenterlng long lists of chemical identifiers or
other information elements that are part of the original query or
that have been identified and acquired from one or more of the CSIN
resources. For further Information contact Dr. Sid Siegal at FTS
382-2256.
5.6 EPA Information Clearinghouse
The EPA Information Clearinghouse is a bibliographic data base com-
posed of over 475 individual data bases and models that contain mon-
itoring information and statistics on a variety of chemicals. The
individual data bases are maintained for offices within EPA. For
further information, contact Charlene Sayers at FTS 755-9112.
The following data bases contain information on toluene:
BAT Review Study for the Timber Products Processing, Gum and Wood,
Chemicals, and the Printing and Publishing Industries
Best Management Practices, Timber Industry Effluent Guidelines -
Runoff
Best Management Practices, Timber Industry Effluent Guidelines -
Sludge
Chemicals in Commerce Information System
Compliance Sampling Toxicant Surveys
Consolidated Permits Program-Application Form l,2b,2c
Data Collection Portfolio for Industrial Waste Discharges
Distribution Register Organic Pollutants in Water
Effluent Guidelines GC/MS Screening Analysis Data Base
Energy and Mining Point Source Category Data Base
Federal Facilities Information System
Fine Particle Emissions Information System
Fish Kills
Food Industry Group
Fugitive Emissions Information System
Gaseous Emissions Data System
Hazardous Waste Site Tracking System
5-2 July, 1982
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Hazardous Waste Data Management System
Hemlock, Michigan Environmental Samples
Hewlett-Packard
Houston Oxidant Modeling Study
Humacao Ambient Data Base
1FB Organics Data Base
Indicatory Fate Study
Industrial Process Evaluations
Infrared Spectra of Pollutants
Innovative Technology, Timber Industry Effluent Guidelines
Inorganic Chemicals Industry Regulation Record
LiPari Landfill
Liquid Effluents Data System
Listing of Organic Compounds Identified in Region IV
Love Canal Data Handling System
Method Validation Studies of Priority Pollutants
National Pollutant Discharge Elimination System (NPDES) Discharge
Monitoring Reports
Nationwide Urban Runoff Program
Needs Survey
New York Bight Ocean Monitoring Program
Northeastern Regional Oxidant Study
Organic Chemicals/Plastics Industry
Organic Transport thru Soil
Ozone and its Precursors Data Base-Houston/Los Angeles
Ozone and its Precursors Data Base-Midwest/Boston
Ozone and its Precursors Data Base-Northeast
Paint and Ink Analytical Data
Permit Compliance System
Pharmaceutical Screening/Verification Data Base
Precision and Accuracy for Screening Protocols
Priority Pollutants-Region I
Priority Pollutants-Region III
Publicly Owned Treatment Works (POTW) Analytical Data
Publicly Owned Treatment Works (POTW) Quality Control
Puerto Rico Reservoirs
Regional Toxics Monitoring Program
Resource Conservation and Recovery Act (RCRA)-Hazardous Waste Site
Inspections
Screening Sampling Program
Select Hazardous Chemicals-Ambient
Sources of Toxic Pollutants Found in Influents to Sewage Treatment
Plants
Spill Prevention Control and Countermeasure
System for Consolidated Permitting and Enforcement Data Base
Textile Industry BAT Study-Toxic Sampling Data
Toxics Monitoring
U.S. Virgin Islands-St. Thomas, St. Crolx
Verification Data Base
Verification Sampling Program
Waste Characterization Data Base
Water Enforcement Regional System
Water Quality Information System
5-3 July, 1982
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6. REGULATORY STATUS (Current as of 4/16/82)
6.1 Promulgated Regulations
6.1.1 EPA Programs
Clean Water Act (CWA)
• Section 311 - Toluene is designated a hazardous substance (40-
CFR116.4) and is subject to reportable quantity limitations
(40CFR117.3).
• Section 307 - Toluene is listed as a toxic pollutant (40 CFR-
401.15) as applied to effluents. However, no effluent guide-
lines specifically limit toluene release at this time.
• Sections 318, 402 and 405 - National Pollution Discharge Elimi-
nation System (NPDES) permit testing requirements; toluene is
listed as a volatile organic pollutant based on gas chromato-
graphic and mass spectroscopic analyses; it is part of the
consolidated permit program (40CFR122 App. D).
Resource Conservation and Recovery Act (RCRA)
• Section 3001 - Toluene is identified as a toxic waste (U220) and
listed as a hazardous waste constituent (40CFR261.33, App.
VIII). Nonspecific sources of toluene-containing waste are sol-
vent use (or recovery) activities (40CFR261.31). Waste streams
from the following industries contain toluene and are listed as
specific sources of hazardous waste: organic chemicals (benzyl-
chloride production) and pesticides (disulfoton production)
(40CFR261.32, App. VII).
• Sections 3002 to 3006 - Hazardous wastes are subject to further
controls concerning generators, transporters, and treatment,
storage and disposal facilities (40CFR262 to 265). Permit pro-
cedures are also included in consolidated permit regulations
(40CFR122 to 124).
6.1.2 Programs of Other Agencies
OSHA - Occupational Safety and Health Act
• Sections 6(a) and 8(g) - general industry standards; specifies
permissible exposurelimit for toluene, including ceiling and
peak levels (29CFR1910.1000).
CPSC - Federal Hazardous Substance Act
• Sections 2-3, 10 and 14 - Products requiring special labeling
anHexemptions(16CFR1500.14(a)(3) and (b)(3); - .83(a)(8);
(a)(9), and (a)(13)).
6-1 July, 1982
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POT - Hazardous Materials Transportation Act
• Shipment of toluene is regulated due to its combustibility
(49CFR172.101-102).
FDA - Food, Drug, and Cosmetic Act
• Sections 409 and 701 - Toulene is a permissible component in
foo3packaging,TTeT, an allowable indirectfood additive
(21CFR175 to 178).
• Section 512(i) - New animal drug dosage forms that are not sub-
ject to certification include toluene capsules (21CFR520.580).
• Section 408 - Toluene is exempt from tolerances for use as a
solvent in pesticide formulations applied to growing crops
(40CFR180.1001(d) and 180.1045).
DOE - Emergency Petroleum Allocation Act
• Regulations apply to toluene products produced in or imported
into the United States (10CFR211.201, 212.31, 212.56, and
213.11).
6.2 Proposed Regulations
6.2.1 EPA Programs
Clean Air Act (CAA)
• New stationary source performance standards (NSPS) have been
proposed for volatile organic chemicals from the synthetic or-
ganic chemicals manufacturing industry (46FR1136) and pressure-
sensitive tape and label surface coating operations (45FR86278).
Toxic Substances Control Act (TSCA)
• Section 8(d) - Requires chemical manufacturers, processors, dis-
crlbUCors, and others who possess health and safety studies on
listed chemicals (including toluene) to submit the data to EPA
(44FR77470).
6.3 Other Actions
EPA
• A Suggested No Adverse Response Level (SNARL) for toluene is
being developed for drinking water (ODW).
• The National Ambient Air Quality Standard (NAAQS) for hydrocar-
bons Indirectly regulates toluene. The hydrocarbon standard is
for use as a guide in devising Implementation plans to achieve
photochemical oxidant (i.e., ozone) standards (40CFR50.10).
6-2 July, 1982
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7. STANDARDS AND RECOMMENDED CRITERIA*
7.1 Air
• OSHA limits (29CFR1910.1000):
8-hour time-weighted average 200 ppm
Ceiling concentration 300 ppm
Maximum peak for 10 min. 500 ppm
• NIOSU recommended exposure limits:
8-hour time-weighted average 100 ppm
Ceiling concentration 200 ppm
7.2 Water
Ambient water criterion level to
protect human health (FR4579318). 14.3 mg/1
Hazardous spill rules require
notification of discharges equal
to or greater than the reportable
quantity (40CFR117.3). 1000 Ib
*See Appendix A for a discussion of the derivation, uses, and limitations of
these criteria and standards.
7-1 July, 1982
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8. SPILL CLEAN-UP/DISPOSAL (CONTACT: National Response Center
800-424-8802; 426-2675 in
the Washington, D.C. area)
8.1 Hazards and Safety Precautions
Toluene readily volatilizes to a moderately toxic vapor that may
cause dizziness, CNS depression, and reaction time impairments at
levels of 200-1,500 ppm. Contact may irritate skin and eyes.
Toluene is extremely flammable and may be ignited by heat, sparks, or
flames. Container may explode in heat of fire; vapor explosion haz-
ard exists and runoff to sewers may create fire or explosion hazard.
Fire produces toxic combustion products.
8.2 First Aid
Move victim to fresh air and call medical help. Give artificial
respiration if not breathing or oxygen if breathing is difficult. In
case of contact, immediately flush skin or eyes with running water.
Remove contaminated clothing.
8.3 Emergency Action
Spill or leak
Stay upwind, isolate hazardous area, and wear self-contained breath-
ing apparatus and full protective clothing. Remove ignition sources
and use water spray to reduce vapors. Contain slick on waters; use
oil skimming and sorbent foams. For dissolved portions, use carbon
or peat.
Fire
For small fires use dry chemical, C02> water spray, or foam. For
large fires, use water spray or foam. Move containers from fire area
if possible; cool containers exposed to fire with water until well
after fire is out. Isolate for one-half mile in all directions if
tank or tankcar is involved in fire.
8.4 Notification and Technical Assistance
Section 103 of the Comprehensive Environmental Response, Compensa-
tion, and Liability Act (CERCLA) or "Superfund" requires notification
of the National Response Center (NRG, 800-424-8802 or 426-2675 in the
Washington, D.C. area) if releases exceed reportable quantities
(1,000 Ib in the case of toluene). For emergency assistance call
CHEMTREC: 800-424-9300. For information call the Division of Oil
and Special Materials at 1-202-245-3045.
8.5 Disposal
Toluene is classified as a toxic waste (U220) and generators of more
than 1,000 kg of hazardous waste per month (or residues from spill
8-1 July, 1982
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clean-up) are subject to RCRA regulations. The following waste
streams are subject to Subpart D regulations:
• Still bottoms from the distillation of benzylchloride.
• Still bottoms from toluene reclamation distillation in the pro-
duction of disulfoton.
• Wastewater treatment sludge from disulfoton production.
• Used solvents and wastes from recovery of solvents (generic
wastestream).
8-2 July, 1982
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9. SAMPLING, ACCEPTABLE ANALYTICAL TECHNIQUES. AND QUALITY ASSURANCE
9.1 Air (CONTACT: Joseph F. Walling, FTS 629-7954)
Toluene is not a criteria air pollutant*, therefore, no Agency or
reference procedures exist. Although measurements of this pollutant
have been made and reported, there are no well documented method de-
scriptions available for quantitative measurements in ambient air.
Therefore, monitoring for this pollutant must be approached with
great caution.
A procedure using Tenax adsorbent for sampling and gas chroma-
tography/mass spectrometry (GC/MS) for analysis has been used but
little is known about the precision and accuracy of the procedure.
GC/MS requires special expertise and expensive, sophisticated equip-
ment. For these reasons, monitoring for one compound alone using the
Tenax GC/MS procedures is rarely cost effective and the approach is
most suitable when monitoring for an array of volatile compounds is
desired.
The preparation of Tenax suitable for sampling is demanding. Tenax
background is a problem that must be addressed. Precautions about
permissible maximum air volumes, sampling rates, and ambient tempera-
tures during sampling must be observed and these, in turn, govern al-
lowable sampling times.
Detection limits and accuracy are not known; reproducibility is esti-
mated to be 50-100 percent. The generation of artifacts during ther-
mal elutlon with Tenax GC can be significantly reduced by proper
clean-up and conditioning.**
9.2 Water (CONTACT: Thomas Bellar, FTS 684-7311;
James Lichtenberg, FTS 684-7308)
Toluene is a proposed parameter under Section 304(h) of the Clean
Water Act. It is listed as one of the priority pollutants. There
are three proposed procedures for the analysis of toluene in natural,
waste, and drinking waters. All methods proposed use the purge and
trap procedure. Two of the methods use gas chromatography for
detection and quantification; the third calls for detection by a gas
chromatograph/mass spectrometer.
* Toluene is indirectly regulated as a "volatile organic compound" (VOC),
but no analytical procedure has been approved to analyze specifically for
toluene.
** See G. Holzer, et.al., J. Chromatogr. 142, 755-64 (1977).
9-1 July, 1982
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Purge and Trap Methods** EPA Method #503.1
EPA Method #602
EPA Method #624
Major Equipment: Gas Chromatograph and Purge and Trap Apparatus.
Five ml of the aqueous sample is placed into a purging device. Tol-
uene and other volatile water insoluble organic compounds are trans-
ferred from the aqueous phase to the gas phase. The volatilized com-
pounds are swept from the purging device by the purged gas and are
trapped in a short column containing a suitable sorbent. After a
predetermined period of time the trapped compounds are thermally de-
sorbed and backflushed into a gas chromatograph equipped with a mass
spectrometer or photoionizatlon detector. The method detection limit
for the mass spectrometer is approximately 6.0 ug/1. For the photo-
ionization detector method detection limits as low as 0.02 ug/1 have
been achieved.
Samples are collected in narrow-mouth screen-cap bottles with TFE
fluorocarbon seals. Adjust the pH of the sample to about two by add-
ing 50% HC1 while stirring vigorously. If the sample contains free
or combined chlorine, add sodium sulfite preservative. From time of
collection to extraction the sample is stored head-space free at 4°C
in the dark. Spiked river water samples have been stored for up to
14 days under these conditions with no apparent losses.
List of Procedures for Toluene
Recoveryc
Method
EPA 624
EPA 602
EPA 503.1
Type*
P&T
P&T
P&T
MDLb
6.0 ug/1
0.2 ug/1
0.02 ug/1
%
96
95
95
Standard
Deviation
%
25
10.1
7.6
Status
(March 1981}
Proposed
Proposed
Proposed
a) Purge and Trap; b) MDL - Minimum Detectable Level; c) Single laboratory
recovery from spiked reagent water or wastewater.
**References for Water Analysis
"The Analysis of Aromatic Chemical Indicators of Industrial Contamination in
Water by the Purge and Trap Method" Method 503.1; May 1980, USEPA, Environ-
mental Monitoring and Support Laboratory, Cincinnati, Ohio 45268.
"Methods for Organic Chemical Analysis of Water and Wastes by GC, HPLC, and
GC/MS" Method 602; Purgeable Aromatics. USEPA, Environmental Monitoring Sup-
port Laboratory, Cincinnati, Ohio 45268. See also 44FR69474-78.
"Methods for Organic Chemical Analysis in Water and Wastes by GC, HPLC, and
GC/MS" Method 624; Purgeables. USEPA, Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio 45268. See also 44FR69532.
9-2 July 1982
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9.3 Solid Waste (CONTACT: Michael Hiatt, FTS 545-2118
Werner Beckert, FTS 545-2137)
Methods 8.02 and 8.24 in "Test Methods for Evaluating Solid Waste -
Physical/Chemical Methods" (USEPA/SW-846/1980) are approved for anal-
yses of toluene in solid wastes.
In one modified purge and trap technique the volatile compounds are
removed from the sample by heating the sample to 110°C while sweeping
with helium carrier gas that is subsequently passed through 5 ml of
water. The carrier gas then passes through a tenax-silica gel trap
which absorbs the volatile organics. The volatiles are desorbed from
the trap by heating and passed through a GC column. Sample prepara-
tion generally takes less than 30 minutes. Recoveries are reported
to be 77% at 26 ppb with an 88% precision. This method has been
tested for the ppb range. See:
David N. Speis, "Determination of Purgeable Organics in
Sediment Using a Modified Purge and Trap Technique."
Protocol, U.S. EPA, Region H, Edison, New Jersey,
October 10, 1980.
In another modified purge and trap technique, which was used in the
Love Canal Study, the sample is diluted with water and the resultant
slurry is purged. A standard deviation of 24% has been reported for
this method at the 20 ppb range. Recoveries are reported to be 35%.
From: Quality Assurance Plan, Love Canal Study (unpublished).
With the vacuum extraction technique, the volatiles are extracted
from the sample using a vacuum. The extracted volatiles are collect-
ed in a liquid-nitrogen-cooled trap. After extraction, 5 ml of water
are added to the extract and the sample analyzed as a 5-ml water sam-
ple using Method 624. The precision at 25 ppb is 4% with a 102% re-
covery. The total sample preparation takes approximately 36 min-
utes. See:
Michael H. Hiatt, "Analysis of Fish and Sediment for
Volatile Priority Pollutants." Accepted for publica-
tion in Analytical Chemistry.
9.4 Other Samples
A modification of the purge and trap method has been suggested by
EPA, (1979, Chemistry Laboratory Manual for Bottom Sediments; NTIS
PB294-596) for the analysis of soil and sediment samples. The modi-
fied purge and trap apparatus used for this purpose is described.
The sample, contained in a specially designed glass vial, is heated
at 80°C and purged with helium gas. The desorbed organics are
trapped in a Tenax GC column. At the end of trapping, thermally de-
sorbed organics from the column are analyzed by GC-FID as in the case
of water and wastewater samples. The recovery of toluene was deter-
mined to vary between 32% and 44% when 0.1 ug to 3.0 ug of toluene
was spiked onto a specially prepared soil matrix. Although the
9-3 July, 1982
-------
recoveries were low, they were found to be linear and reproducible.
Data on spiked environmental samples showed much higher recoveries
(80-1005!).
With the purge-trap system described, the minimum detection limit of
O.I ppb can be attained. Thus, the method showed at least two orders
of magnitude higher sensitivity than headspace analysis.
9.5 Quality Assurance
9.5.1 Water
Single laboratory test data on simple spiked matrices have been col-
lected by EPA. Quality control and performance evaluation samples
(methanolic concentrates containing toluene to be spiked into water)
are available from the Environmental Monitoring and Support Labora-
tory, Quality Assurance Branch, USEPA, Cincinnati, Ohio 45268. (See
Water Contact).
9.5.2 Solid Waste
Standards can be obtained from Radian Corporation or EMSL-Las Vegas
(see Solid Waste Contact). Supelco supplies diluted standards but
the concentrations are not verified. Standard solutions may also be
prepared in the laboratory from reagent-grade toluene to the appro-
priate dilution using methanol.
Periodic performance evaluations with samples that include toluene
are carried out by EMSL-CM (Water Supply and Water Pollution
Studies).
9-4 July, 1982
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REFERENCES
The major references used in preparation of this document are listed below.
EPA references are listed by the EPA office of origin and the year of publi-
cation. For further information refer to the contacts given throughout this
document or contact the relevant EPA Program Offices given at the end of this
section.
(ECAO, 1981) Health Risk Assessment Document for Toluene, EPA-Contract
No. 68-02-377, Environmental Criteria and Assessment Office
(1981).
(NRC, 1980) The Alkyl Benzenes, National Research Council, Washington,
D.C. (1980).
(OWRS, 1980) Ambient Water Quality Criteria for Toluene. EPA - 440/5-80-
075; Office of Water Regulations and Standards (1980).
R-l July, 1982
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OFFICE CONTACTS
The EPA Offices and Divisions listed below may be contacted for more Informa-
tion relating to the indicated sections of this document. While these of-
fices are, in many cases, the offices of origin for the data included in this
paper, the personal contacts given throughout this document should be con-
tacted first. Unless otherwise noted, the offices listed are situated in
Headquarters, Washington, D.C., and the telephone numbers given are FTS
(Federal Telecommunications System) numbers. For commercial telephone calls
to Headquarters that are not placed on FTS, area code 202 must be used.
Other commercial numbers are noted for the office contacts located outside
Washington, D.C.
HEALTH AND ENVIRONMENTAL EFFECTS (Section 2)
Office of Health and Environmental Assessment (OREA)
Environmental Criteria and Assessment Office:
Cincinnati, OH 684-7531 (513-684-7531)
Research Triangle Park, NC 629-2266 (919-541-2266)
Carcinogen Assessment Group 755-3968
Office of Drinking Water (ODW)
Health Effects Branch 472-6820
Office of Toxic Substances (OTS)
Health and Environmental Review Division 382-4241
Environmental Research Laboratory
Duluth, MN, Region V 783-9550 (218-727-6692)
ENVIRONMENTAL RELEASES AND EXPOSURE (Sections 3 and 4)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Water Regulations and Standards (OWRS)
Monitoring and Data Support Division 426-2503
R-2 July, 1982
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Office of Toxic Substances (OTS)
Exposure Evaluation Division 382-3873
Assessment Division 382-3442
DATA BASES (Section 5)
Office of Toxic Substances (OTS)
Management Support Division 382-3546
REGULATORY STATUS, STANDARDS, AND CRITERIA (Sections 6 and 7)
Office of Air Quality Planning and Standards (OAQPS)
Strategies and Standards Division
Research Triangle Park, NC 629-5504 (919-541-5504)
Office of Drinking Water (ODW)
Criteria and Standards Division 472-5016
Office of Hater Regulations and Standards (OWRS)
Criteria and Standards Division 755-0100
Effluent Guidelines Division 426-2571
Office of Solid Waste (OSW)
State Programs and Resources
Recovery Division 755-9107
SPILL CLEAN-UP AND DISPOSAL (Section 8)
NOTE: For Emergencies call the National Response Center at 1-800-424-8802
(1-800-426-2675 from the Baltimore/Washington area).
Office of Emergency and Remedial Response (OERR)
Emergency Response Division 245-3045
Oil and Hazardous Materials Spills Branch
Edison, NJ, Region II 340-6634 (20L-321-6634)
R-3 July, 1982
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Office of Solid Waste (OSW)
Hazardous and Industrial Waste Division 755-9187
ANALYTICAL TECHNIQUES (Section 9)
Environmental Monitoring Systems Lab (EMSL)
Air Analysis
Research Triangle Park, NC 629-2454 (919-541-2454)
Water Analysis
Cincinnati, OH 684-7311 (513-684-7311)
Waste Analysis
Las Vegas, NV 545-2137 (702-798-2137)
GENERAL IPP COMMENTS, CORRECTIONS OR QUESTIONS
Office of Toxic Integration
Chemical Information and
Analysis Program 382-2249
R-4 July, 1982.
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Appendix A
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APPENDIX A
Criteria and Standards, Their Derivation, Use, and Limitations
The Agency is often required to respond to environmental emergencies or
incidents for which established protocols are not relevant. In some cases,
when no traditional regulatory health criteria or action level exist, the
Agency may fashion an approach using professional judgement, borrowing from
standards/guidelines developed for similar circumstances. If the existing
standards and criteria are to be applied correctly, the assumptions and
methods used in deriving them must be taken into account. This Appendix
contains a short description of the methods used to derive the standards and
criteria listed in the IPP documents (Section 7).
Clean Air Act (CAA)
National Ambient Air Quality Standards (NAAQS)—Sections 108 and 109 of
the CAA authorizes EPA to set levels at which air pollutants can safely
be tolerated and to establish NAAQS. Control strategies (implementation
plans) for emission sources are developed on a State-by-State basis.
NAAQS are based on air quality criteria documents which reflect the
latest knowledge concerning effects on the public health. To develop
primary NAAQS, EPA must: (1) specify the significance of health
effects; (2) identify sensitive populations, (e.g., asthmatics, heart
patients, children, etc.); (3) determine probable adverse heath effect
levels in sensitive persons; and (4) estimate the level below the
probable effect level which provides an adequate margin of safety. See
40 CFR 50 for NAAQS issued to date.
New Source Performance Standards (NSPjS)—Under Section 111 of the CAA,
EPA may issue NSPS to regulate air pollutants from new stationary
sources which endanger the public health or welfare. In many cases,
NSPS are set by EPA to facilitate the achievement of NAAQS; NSPS
regulate emissions from specific categories of pollution sources rather
than "air quality." NSPS are published in 40 CFR 60.
National Emission Standards for Hazardous Air Pollutants (NESHAPs)—
Hazardous air pollutants are defined under Section 112 of the CAA as
those that cause an increase in mortality or an increase in serious
irreversible or incapacitating reversible Illness. NESHAPs may apply to
one particular stationary source or to several categories of sources.
The basic approach used in the development of NESHAPs has been to
identify an ambient level sufficient to protect public health and then
relate emissions to this level by the use of meterological dispersion
estimates. The procedure used to determine what ambient concentrations
allow an "ample margin of safety" varies with the pollutant of concern.
For suspected carcinogens, such as vinyl chloride, EPA assumes that no
level of exposure is toxicologically insignificant (44 FR 58642).
Therefore, EPA requires emission on reduction for vinyl chloride to the
lowest achievable by use of the best available'control technology (40 FR
59534). See 40 CFR 61 for published list.
A-l July, 1982
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Clean Water Act (CWA)
Section 31 I—Report able Quantities for Hazardous Substances—Under CWA
Section 311, 297 compounds have been designated as hazardous substances
(40 CFR 116) and reportable quantities (RQs) have been assigned (40 CFR
117). The RQs assigned are all essentially based on acute aquatic
toxicity. [EPA further screened candidates for listing under Section
311 on the basis of discharge potential.] Other criteria for selection
adopted in 40 CFR 116 (acute toxicity in mammals and plants) have not
yet been employed by the Agency. To date, EPA has relied exclusively on
the 96-hour LC50 toxicity test (i.e., the concentration likely to kill
50 percent of the fish population within 96 hours) to assign reportable
quantities. Reportable quantities vary from 1.0 pound for substances
which are the most highly toxic to aquatic life (LC50 < Ippm) up to 5000
pounds for substances which are practically nontoxic 7100 ppm Ł LC50 <_
500 ppm). The reportable quantities of 10 pounds, 100 pounds, and 1000
pounds correspond to aquatic toxicity (LC50) ranges of 0.1 to 1 ppm, 1
to 10 ppm, and 10 to 100 ppm respectively (43 FR 10492).
If the reportable quantity is reached in a discharge, the regulations
under Section 311 specify requirements for notification and prescribe
penalty provisions. The regulations apply only to discharges of RQs in
any 24-hour period; thus, RQ levels are set to control short-term
nonroutine discharges of hazardous substances (44 FR 50775). No
consideration is given to water body characteristics. In addition,
discharges of mixtures and solutions are subject to the regulations only
if a component hazardous substance is discharged in a quantity equal to
or greater than its RQ (44 FR 50767).
Due to the passage of the Comprehensive Environmental Response,
Compensation, and Liability Act (CERCLA or Superfund), the Agency is in
the process of assigning RQs for newly designated hazardous substances
and adjusting the RQs previously assigned under the CWA Section 311. RQ
values set under Superfund regulations will use other criteria in
addition to aquatic toxicity. However, until EPA sets other reportable
quantities, RQs for CERCLA are the same as RQs established for Section
311 of the CWA, where applicable. For all other hazardous substances
not covered under Section 311, the statutory RQs under Section 102(b) of
CERCLA are set at 1.0 pound unless and until they are superceded by EPA
regulations.
Water Quality Criteria (45 FR 79318)— Pursuant to Section 304(a)(l) of
the CWA, EPA published water quality criteria (WQC) for the 65
pollutants that Congress, in the 1977 amendments to the Act, designated
as toxic under Section 307(a)(l). The WQC reflect the latest scientific
knowledge on the relationship between pollutant concentrations and
environmental and human health effects. Criteria values do not consider
the economic or technological feasibility of attainment; they are based
on a scientific assessment of environmental and human health effects.
WQC have no direct regulatory impact.
Two different types of WQC are calculated: one to protect aquatic life
and other to protect human health. The human health criteria are based
on three types of biological end points: carcinogenicity, toxicity
(adverse effects other than carcinogenicity), and organoleptic effects
A-2 July, 1982
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(taste and odor). Because EPA has regarded carcinogenic!ty as a
non-threshold phenomenon, "safe" or "no-effect" levels for carcinogens
could not be established. Consequently, WQC for carcinogens are
presented as a range of pollutant concentrations associated with
corresponding incremental risks of 10~4, io~5 and 10~6 (i.e., one out of
10,000, one out of 100,000, and one out of 1,000,000 respectively). The
lifetime risk assumes a person is continuously exposed to the
carcinogenic agent. In most cases, the data for a quantitative estimate
of carcinogenic response are from lifetime animal studies; human studies
were used in the few cases where the data were sufficient.
For compounds that do not exhibit a carcinogenic response, a threshold
assumption is used in deriving criteria. These criteria are based upon
Acceptable Daily Intake (ADI) levels and are generally derived using
no-observed-adverse effect-level (NOAEL) data from animal studies. The
ADI is calculated using safety factors (in accordance with the National
Research Council recommendations) of 10 to 1000 depending on the quality
and quantity of data. In instances where insufficient data are
available on a chemical's toxicological effects, criteria may be based
on its organoleptic characteristics. This type of criterion may also be
established if the level based on organoleptic effects is lower than the
level calculated from toxicological data.
The basic assumptions used for these calculations are that a 70 kilogram
male will consume two liters of water per day, plus 6.5 grams per day of
freshwater and estuarine fish and shellfish products. An average
bloconcentratlon factor for the chemical in aquatic animals is used to
estimate potential exposure due to ingestion of the fish or shellfish.
Aquatic life criteria were developed to protect most aquatic life.
These criteria specify maximum and 24 hour average values in order to
provide protection from acute and chronic toxlcity. Specific aquatic
life criteria have not been developed for some toxic pollutants due to
insufficient data. In these cases, descriptions of apparent threshold
levels are presented in order to convey an estimate of the toxlcity in
the absence of specific criteria.
An explanation of the guidelines used in developing aquatic and human
health criteria may be found in the Federal Register (45 FR 79318).
Safe Drinking Water Act (SDWA)
Drinking Water Standards*—Pursuant to Section 1412 of the SDWA,'- EPA has
promulgated National Interim Primary Drinking Water Standa'rds for
certain toxic pollutants in finished drinking water (40 CFR 141).
Maximum contaminant levels (MCLs), which specify the maximum level
permitted, are based on consideration of a range of factors including
not only health effects, but also the technological and economic
feasibility for removal of the substance from the supply (40 FR 59566).
For treated drinking water supplies serving 25 or more people, States
* See: National Interim Primary Drinking Water Regulations, EPA-570/9-76-
003, Office of Drinking Water (1976).
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must control toxics down to levels at least as stringent as MCLs. EPA
Is also required to establish revised primary drinking regulations based
on currently available information and treatment techniques.
The MCLs were based on an assumed consumption of two liters of water per
•day. Total environmental exposure was also considered in order to take
into account the fact that drinking water may be a minor source of a
contaminant in an average person's intake.
In the absence of formal drinking water standards, ODW has developed
Health Advisories (HAs) on various pollutants. The advisories are
called Suggested-No-Adverse-Response-Levels (SNARLs). EPA-SNARLs are
not legally enforceable standards, although they may lead ultimately to
the issuance of MCLs. Normally, EPA-SNARLs are issued for 1-day,
10-day, and longer-term exposure (where data exists) but do not consider
possible carcinogenic risks. EPA-SNARLs are provided on a case-by-case
basis in emergency situations such as spills and accidents.
One-day SNARLs are calculated for a 10 kg body weight child who consumes
one liter of water per day. Minimal-effect-doses or no-adverse-effect-
levels obtained from animal studies are used in conjunction with an
appropriate safety factor (10 to 1000). Ten-day SNARLs are usually
calculated by dividing one day SNARLs by 10. Longer-term SNARLs require
information on effects produced from long-term exposure.
Resource Conservation and Recovery Act (RCRA)
EP''Toxicity—A solid waste is classified as hazardous under RCRA if the
waste exhibits the- characteristics of the extraction procedure (EP)
toxicity using specified test methods. The EP tests for the presence of
any of 14 specified toxic materials at levels equal to or greater than
'the maximum level specified (40 CFR 261.24). The EP was designed in an
attempt to identify wastes likely to leach hazardous concentrations of
toxic chemicals into groundwater. The maximum levels specifled-were set
at 100 times the MCL issued under the SUWA. (See 45 FR 33066 for a
disussion of the rationale for using a 100-fold attenuation factor.)
Exclusion Limits for Acutely Hazardous Wastes—Chemicals designated as
acutely hazardous under RCRA are subject to regulations in very small
quantities. - Provisions apply only to pure chemicals and associated
containers, liners, and contaminated soils or spill residues (40 CFR
261.33(e)). EPA has set a general exclusion limit for generators of
less than a total of 1000 kg/month hazardous waste; i.e.; the disposal
of up to 1000 kg/month is not subject to RCRA Subtitle C requirements.
However, for acutely hazardous wastes, the exclusion is set at 1 kg (2.2
Ibs.) for the chemical (with other amounts specified for associated
containters, etc.).
Acutely hazardous wastes are considered so hazardous that, unlike most
wastes, they present - a substantial hazard whether or not they are
properly managed. Specifically, such a waste has been found to be fatal
to humans in low doses', or, in the absence of human toxicity data, the
chemical has been found to have a high acute toxicity in mammals (i.e.,
an oral LD50 of less than 50 mg/kg or inhalation LC50 of less than 2
mg/liter in rats, or a dermal LD50 of less than 200 mg/kg in rabbits).
A-4 July, 1982
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Also included are chemicals which are otherwise capable of causing or
contributing to serious or incapacitating adverse health effects,
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Food, Drug, and Cosmetic Act (FDCA)
Pesticide Tolerance Levels—The powers originally granted to FDA to
establish tolerance's for pesticides were transferred to EPA in 1970 (35
FK* 15623). In general, no raw agricultural commodity which bears or
contains -a pesticide 'chemical may be marketed in interstate commerce
unless EPA has set a tolerance (i.e., maximum permissible level). The
pesticide must be registered under the Federal Insecticide, Fungicide,
and Rod'enticlde Act -(FIFRA) before a tolerance may be set.
Approved pesticides are listed along with maximum levels permitted on
specific crops in 40 CFR 180.101 through 180.379. The FDCA specifically
requires that EPA1 con'sider the usefulness and necessity of the
chemical. The level of tolerance is based on a broad cost/benefit
-analysis which examines the economic, environmental, and health effects
resulting from use of the pesticide chemical'(21 U.S.C. Section 346).
Food Additives and Color Additives—Except for food additives "generally
recognized as safe" (GRAS), FDA must certify an additive and safe
conditions/concentrations for use must be issued. Generally, the
maximum permissible level of an additive must be 1 percent or less of
the concentration found to produce no effect in experimental animals.
Additives usually cannot be approved, nor safe tolerances set, if they
are carcinogenic (the Delaney clause). However, carcinogenic color
additives may still be used in external drugs and cosmetics if its use
in those products does not induce cancer. Regulations covering food
additives are published in 21 CFR 172 to 178; regulations covering color
additives are listed in 21 CFR 73 and 74.
Other Tolerance/Action Levels—In contrast to the food and color
additive regulations, FDA must first prove a cosmetic contains a
"poisonous or deleterious substance" which is hazardous under conditions
of normal use before it can be regulated. Under the FDCA, FDA may also
regulate "poisonous and deleterious substances" in foods (and food
packaging) if the substance "may render it injurious to health." FDA
may issue tolerances permitting the presence of such substances if the
substance cannot be avoided by good manufacturing practice and the
tolerance is sufficient for protecting public health, taking into
account the extent to which the presence of the substance cannot be
avoided (21 CFR 109.6).
If possible technological changes may change the appropriateness of a
tolerance level, then FDA may issue an Informal action level. Action
levels do not carry the same legal force as formal regulatory
tolerances. Thus, food is considered "adulterated" and may be barred
from interstate commerce merely if FDA demonstrates that a tolerance has
been exceeded. When proceeding against a food with residues that are
higher than an action level, however, the FDA must defend the action
level itself in court.
Bottled Drinking Water Standards—the SDWA contains a provision which
amends the FDCA by adding Section 410 to cover bottled drinking water.
Based on the MCLs issued under the SDWA, FDA has set identical limits in
bottled drinking waters (21 CFR 103.35).
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Consumer Product Safety Act (CPSA)
Under CPSA, the CPSC regulates consumer- .productsr which present an
unreasonable risk of injury (16 CFR--1201 rto -1404.). The
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