EPA
United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park, NC 27711
EPA-450/4-84-022a
October 1987
Air
APPENDIX E AND F TO
NETWORK DESIGN
AND SITE EXPOSURE
CRITERIA FOR
SELECTED
NONCRITERIA AIR
POLLUTANTS
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INTRODUCTION
This report contains Appendices E and F to the previously published
"Network Design and Site Exposure Criteria for Selected Noncriteria Air
Pollutants," EPA-450/4-84-022 (September 1984). Appendix E contains the
chemical profiles for 20 new chemicals and Appendix F contains guidance on
the monitoring frequency for noncriteria air pollutants.
U.S. Environmental Protection Agency
Region 5, Library (PL-12J)
77 West Jackson Boulevard, 12tn Moor
Chicago, IL 60604-3590
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DISCLAIMER
The development of this document has been funded by the United States
Environmental Protection Agency under contracts 68-02-3898 and 68-02-3848.
It has been subject to the Agency's peer and administrative review, and it
has been approved for publication as an EPA document.
Mention of trade names or commercial products does not constitute
endorsement or recommendation for use.
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APPENDIX E
NETWORK DESIGN AND SITE
EXPOSURE CRITERIA FOR SELECTED
NONCRITERIA AIR POLLUTANTS
Prepared by
PEI Associates, Inc.
11499 Chester Road
Cincinnati, Ohio 45246
Contract No. 68-02-3898
Task Assignment No. 3
Pn 3649-3
U.S. Environmental Protection Agency
Monitoring and Data Analysis Division
Research Triangle Park, North Carolina 27711
August 1986
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CONTENTS
Page
1. benzo(a)pyrene 2
2. 1,3-butadiene 8
3. o-, m-, p-cresol 19
4. p-dichlorobenzene 35
5. dimethylnitrosamine 45
6. ethylene dichloride 49
7. ethylene dibromide 61
8. ethylene oxide 70
9. formaldehyde 82
10. hexachlorocyclopentadiene 97
11. maleic anhydride 108
12. manganese 114
13. mercury 125
14. methylene chloride 132
15. 4,4'-methylenedianiline 141
16. perchloroethylene 147
17. phenol 156
18. phosgene 174
19. propylene oxide 186
20. o-, m-, p-xylene 204
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APPENDIX E
This appendix to the EPA report "Network Design and Site Exposure Crite-
ria for Selected Noncriteria Air Pollutants" (EPA-450/4-84-022) dated
September 1984 completes the chemical profiles begun in Appendix D; four
completely new chemicals have been added. Sixteen chemicals were included in
the body of the report for which no chemical profiles were included in Appendix
D. Chemical profiles are included in this appendix for these chemicals and
four additional pollutants: benzo(a)pyrene, 1,3-butadiene, ethylene dibromide,
and 4,4'-methylenedianiline. The 20 chemicals included in this appendix are:
0 benzo(a)pyrene
0 1,3-butadiene
0 o-, m-, p-cresol
0 p-dichlorobenzene
0 dimethylnitrosamine
0 ethylene dichloride
0 ethylene dibromide
0 ethylene oxide
0 formaldehyde
0 hexachlorocyclopentadiene
0 maleic anhydride
0 manganese
0 mercury
° methylene chloride
0 4,4'~methylenedianiline
0 perchloroethylene
0 phenol
0 phosgene
0 propylene oxide
0 o-, m-, p-xylene
The information in this appendix has been reviewed by industry groups
and reflects their comments.
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Chemical Name
Benzo(a)pyrene
CAS Number
50-32-8
Chemical Classification
Polynuclear aromatic hydrocarbon
Synonyms
Benzo(d,e,f)chrysene, 3,4-benzopirene, 3,4-benzopyrene,
6,7-benzopyrene, 3,4 benzpyren, benz(a)pyrene, 3,4-benzpyrene,
3,4-benz(a)pyrene, 3,4-benzypyrene, BP, B(a)P, 3,4-BP
Physical/Chemical Properties
Description:
Yellowish crystals
Boiling Point:
310° to 312°C (10mm)
Melting Point:
179°C
Molecular Weight:
252.3
Chemical Formula:
C12H2c
Vapor Pressure:
5.49 x 10"9 mm Hg
Vapor Density:
Not available
Refractive Index:
Not available
Solubility:
Insoluble in water; slightly soluble in alcohol; soluble in
benzene, toluene, xylene.
-------
Log Partition Coefficient (octanol/water):
6.04
Photochemical Reactivity:
Not available
Chemical Reactivity:
Hydrogenation with platinum oxide gives 4,5-dihydrobenzo(a)
pyrene, 7, 8, 9, 10-tetrahydro(a)pyrene and perhydrobenzo(a)
pyrene. On oxidation with chromic acid or ozone, B(a)P yields
benzo(a)pyrene-l,6-quinone and benzo(a)pyrene-3,6-quineon; and
on further oxidation, benzanthrone dicarboxylic anhydride.
Electrophilic substitution occurs mainly in position 6. B(a)P
oxidizes in benzene under the influence of light and air.
When heated to decomposition, emits acrid smoke and irritating
fumes.
Environmental Fate
Very strong adsorption onto suspended solids is the dominant
transport process.
Bioaccumulation is short-term; metabolism and microbial degradation
are principal fates.
Source of Emissions
Production:
Produced in the United States by one company and distributed
by several specialty companies in quantities from 100 mg to 5
g for research purposes. Although not produced in great
quantities, it is a byproduct of combustion, and an estimated
1.8 million Ib per year is released from stationary sources—96
percent from coal refuse piles, outcrops, and abandoned coal
mines; residential external combustion of bituminous coal;
coke manufacture; and residential external combustion of
anthracite coal. Has been detected in cigarette smoke at
levels ranging from 0.2 to 12.2 yg/100 cigarettes. Has been
detected in foods at levels ranging from 0.1 to 50 ppb.
Uses:
Research purposes only
Tables E-l and E-2 present emission factors and ambient
concentrations of benzo(a)pyrene.
Storage:
In laboratory only
Transportation:
Shipped only in small (less than 5 g) quantities
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TABLE E-l. EMISSION FACTORS FOR BENZO(A)PYRENE
Cigarettes
Automobile exhaust
Fuel oil combustion (large furnace)
Fuel oil combustion (small furnace)
Space heaters (coal)
Space heaters (gas)
Refuse burning
Power station (coal)
Power station (gas)
Automotive diesel
Coke oven volatiles
Water spray-tower, asphaltic concrete
Outlet of asphalt air-blowing process
2.5 yg/100 cigarettes
0.05-0.08 mg/liter gasoline consumed
0.13 mg/ton fuel
10.6 mg/ton fuel
10 mg/106 Btu input
0.2 mg/106 Btu input
11.0 g/m3 of emitted gas
0.3 g/m3 of emitted gas
0.1 g/m3 of emitted gas
5.0 g/m3 of emitted gas
35.0 g/m3 of emitted gas
<100 ng/m3
<4,000 ng/m3
Source: Verschueren, K. 1983.
TABLE E-2. BENZO(A)PYRENE CONTENT OF URBAN AIR
City
New York -Commercial
-Freeway
-Residential
Detroit -Commercial
-Freeway
-Residential
Atlanta
Birmingham
Cincinnati
Detroit
Los Angeles
Nashville
New Orleans
Philadelphia
San Francisco
Pittsburgh
Benzo(a)pyrene, ng/m3
Spring
0.5-8.1
0.1-0.8
0.1-0.6
7.2
2.1-3.6
6.3-18
2.0-2.1
3.4-12
0.4-0.8
2.1-9.0
2.6-5.6
2.5-3.4
0.8-0.9
-
Summer
0.7-3.9
0.1-0.7
0.1-0.3
4.0-6.0
0.2
1.6-4.0
6.1-10
1.3-3.9
4.1-6.0
0.4-1.2
1.4-6.6
2.0-4.1
3.5-19
0.2-1.1
0-23
Fall
1.5-6.0
3.3-3.5
0.6-0.8
3.4-7.3
12-15
20-74
14-18
18-20
1.2-13
30-55
3.6-3.9
7.1-12
3.0-7.5
2.9-37
Winter
0.5-9.4
0.7-1.3
0.5-0.7
5.0-17.0
9.2-13.7
0.9-1.8
2.1-9.9
23-34
18-26
16-31
1.1-6.6
26
2.6-6.0
6.4-8.8
1.3-2.4
8.2
Source: Verschueren K. 1983.
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Disposition:
Benzo(a)Pyrene may be disposed of in an incinerator controlled
by an afterburner and an alkaline scrubber. A flammable
solvent must be added.
Sampling and Analytical Methods
1. NIOSH Method 186
a. Collection on a membrane filter.
b. Thin layer chromatographic separation.
c. Fluorometry.
Detection limit:
0.02 vg/m3
Possible interferences:
This method is highly selective for B(a)P, but is
sensitive to variations in technique.
2. NIOSH Method 184
a. Collection on a filter.
b. Extraction.
c. Column chromatography.
d. Spectrophotometric measurement.
Detection limit:
4 mg/m3
Possible interferences:
Any substance that hinders the gas chromatographic
separation or that absorbs radiation at the same wave-
length as the sample compounds may interfere.
3. NIOSH Method 183
a. Collection on a membrane filter.
b. Extraction.
c. GC separation.
d. Spectrophotometric separation.
Detection limit:
0.4 mg/m3 per 500-liter sample.
Possible interferences:
Any compound that has about the same GC retention time
will interfere.
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4. NIOSH Method 206
a. Sampling with glass-fiber filter.
b. Extract ultrasonically.
c. Enrich and measure with high pressure chromatography.
Detection limit:
3.3 ng/m3
Possible interferences:
Any compound that is not retained in the silica column
and absorbs light at 254 nm is measured in this procedure
(eg. Fluorene + derivatives; polychloro-derivatives; di +
tricyclic hydrocarbons). Most interfering compounds have
low peak area/yg values.
Permissible Exposure Limits
OSHA ACGIH
TWA Not established Not established
OSHA indirectly limits exposure by requiring that occupational
exposure to coal tar pitch volatiles not exceed 0.2 mg/m3 8 hr TWA.
The ACGIH lists benzo(a)pyrene as an industrial substance suspected
of carcinogenic potential for man.
Human Toxicity
Acute Toxicity:
High acute subcutaneous toxicity in rats only.
Chronic Toxicity:
Carcinogenesis—The activity of benzo(a)pyrene was first
recognized decades ago, and since that time it has become a
laboratory standard for the production of experimental tumors
in animals that resemble human carcinomas. It ranks among the
most potent animal carcinogens known and can produce tumors by
single exposures to microgram quantities. It acts both at the
site of application and at organs distant to the site of
absorption. Its carcinogenicity has been demonstrated in
nearly every tissue and species tested, regardless of the
route of administration.
Mutagenicity--Benzo(a)pyrene gives positive results in nearly all
mutagenicity test systems, including the Ames Salmonella assay,
cultured Chinese hamster cells, the sister-chromated exchange test,
and the induction of DNA repair synthesis.
Teratogenicity—Limited data available.
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Bibliography
American Conference of Governmental Industrial Hygienists. 1984. TLVs,
Threshold Limit Values for Chemical Substances and Physical Agents in the
Work Environment and Biological Exposure Indices with Intended Changes for
1984-1985.ISB N:0 - 936712-54-6.Cincinnati, OH.
Hawley, G. G. 1981. The Condensed Chemical Dictionary. 10th Edition. Van
Nostrand Reinhold Company, New York.
International Agency for Research on Cancer. 1973. IARC Monographs on the
Evaluation of Carcinogenic Risk of Chemicals to Man". Volume 3,
Benzo(a)pyrene.Lyon, France.pp. 91-136.
Sax, I. N. 1981. Dangerous Properties of Industrial Materials.
Sixth Edition. Van Nostrand Reinhold Company, New Yrok.
Sittig, M. 1981. Handbook of Toxic and Hazardous Chemicals. Noyes
Publications, Park Ridge, NJ.
U.S. Department of Health and Human Services. 1983. Chemical Registry of
Toxic Effects of Chemical Substances 1981 to 1982. National Institute for
Occupational Safety and Health. Cincinnati, OH.
U.S. Department of Health and Human Services. 1984. Manual of Analytical
Methods. Third Edition. National Institute for Occupational Safety and
Health. Cincinnati, OH.
U.S. Department of Health and Human Services. 1981. Second Annual Report on
Carcinogens. Public Health Service. Washington, D.C.
U.S. Environmental Protection Agency. 1980. Benzo(a)pyrene: Health and
Environmental Effects. Washington, D.C.
U.S. Environmental Protection Agency. 1980. Treatability Manual: Volume 1,
Treatability Data. EPA 600-8-80-042a.
Verschueren, K. 1983. Handbook of Environmental Data on Organic Chemicals.
Second Edition. Department of Public Health and Tropical Hygiene,
Agricultural University of Wageningen, Netherlands. Van Nostrand Reinhold
Company, New York.
Weast, R. T. 1981. CRC Handbook of Chemistry and Physics. 61st Edition.
CRC Press, Inc., Boca Raton, FL.
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Chemical Name
1,3-Butadiene
CAS Number
106-99-0
Chemical Classification
Aliphatic hydrocarbon (unsaturated), alkadiene, olefin
Synonyms
Biethylene, biuinyl, butadieen, buta-l,3-dieen butadien,
1,3-butadien, butadiene, buta-l,3-diene, alpha-gamma-butadiene,
divinyl, crythrene, NCI-C5602, pyrrolylene, vinylethylene
Physical/Chemical Properties
Description:
Colorless gas with mild aromatic odor; easily liquified.
Boiling Point:
-4.41°C
Melting Point:
-108.9°C
Molecular weight:
54.1
Chemical Formula:
H2C:CHHC:CH2
Vapor Pressure:
17.65 psia at 0°C 1840 mm at 21°C
Vapor Density:
1.87 (air = 1)
Refractive Index:
ND~25 = 1.4292
Solubility:
Soluble in alcohol emd ether; insoluble in water.
Log Partition Coefficient (octanol/water):
1.99
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Photochemical Reactivity:
Estimated lifetime under photochemical smog conditions is less
than one hour. Half-life for reaction (at 26.8°C) with HO- is
0.1 day and with 03, 0.95 day.
Chemical Reactivity:
Very reactive. Dangerous when exposed to heat, flame, or
powerful oxidizers. Reacts violently with phenol.
Environmental Fate
The most probable environmental fate is photooxidation in the
troposphere. The high vapor pressure of 1,3-butadiene precludes
transport from the troposphere although it is sufficiently soluble
in water to be washed out of a polluted atmosphere in rainwater.
However, rapid volatilization to the atmosphere from surface water
is likely. There is no information indicating 1,3-butadiene
bioaccumulations.
Source of Emissions
Production:
Ethylene coproduct (only method currently being used)
Catalytic dehydrogenation of n-butene and n-butane (Houdry
process)
Oxidative dehydrogenation of n-butene
Uses:
Styrene-butadiene rubber and latex
Polybutadiene
Adiponitrile
Chioroprene/neoprene
ABS rubber
Nitrile rubber
Numerous polymers with styrene/acrylonitrile/vinylpyridine
Other chemicals including captan; sulfolenejtetrahydrophthalic
anhydride; 1-4-hexadiene; 1-5-hexadiene; 1,4-dichlorobutene;
butadiene furfural cotriemer; and R-ll pesticide
Tables E-3 through E-8 present 1,3-butadiene production,
consumption, and emission data.
Storage and Transportation:
Although butadiene is a gas at ambient temperatures, it is
stored and shipped as a pressurized liquid. It is shipped by
pipeline, rail tank car, tank truck, and marine vessel. There
is an extensive butadiene pipeline network between petrochemi-
cal plants on the Texas Gulf; a substantial portion of the
chemical is shipped by this method. Butadiene is a flammable
gas and must be handled as such. It must be isolated from any
oxidizing material. Electrical equipment with spark-resistant
construction must be provided.
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TABLE E-3. COMPANIES PRODUCING 1,3-BUTADIENE
Company
Atlantic Richfield Co.
ARCO Chemical Co.
Dow Chemical U.S.A.
E.I. Du Pont de Nemours
& Co. , Inc.
Conoco Chemicals Co.
El Paso Products Co.
Exxon Chemical Americas
Mobil Chemical Co.
Shell Chemical Co.
Standard Oil Co. (Indiana)
Amoco Chemicals Corp.
Tenneco, Inc.
Texas Petrochemical Corp.
Texaco Chemical Co.
Union Carbide Corp.
Location
Channelview, TX
Freeport, TX
Chocolate Bayou, TX
Corpus Christi , TX
Baton Rouge, LA
Bay town, TX
Beaumont, TX
Deer Park, TX
Norcc , LA
Chocolate Bayou, TX
Houston, TX
Port Neches, TX
Pensulas, PR
Seadrift, TX
Taft, LA
Texas City, TX
Annual capacity, 106 Ib
450
85
135
220
310
240
80
500
500
180
600
500
75
33
75
55
Total 4,038
Source: PEI Associates, Inc., 1985.
10
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TABLE E-4. USE PATTERN FOR 1,3-BD
Product
Styrene-butadiene rubber (SBR)
Polybutadiene rubber (PBR)
Adiponitrile
Styrene-butadiene copolymer latexes
Neoprene
Acrylonitrile-butadiene-styrene (ABS) resins
Nitrile rubber (NBR)
Miscellaneous (pesticides, solvents, etc.)
Total
Percentage of
total consumption
44
19
11
8
7
6
3
2
100
Source: Versar, Inc., 1984.
11
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TABLE E-5. UNCONTROLLED AND CONTROLLED VOC EMISSIONS FROM BUTADIENE
PRODUCTION BY DEHYDROGENATION OF n-BUTANE (HOUDRY PROCESS)
Source
Flue gas
Reactor vent
(regeneration
air)
Intermittent
process
emissions
Storage and
handling
Secondary
Fugitive
Total
Uncontrolled
emission
ratio,
kg/Mga
0.06
5.50
0.50
0.10
0.15
5.20
11.51
Control device
or technique
None
Catalytic or thermal
oxidation
Elevated flare
Noneb
None
Detection and repair
of major leaks plus
mechanical seals
Emission
reduction,
%
0
92
95
90
Controlled
emission
ratio,
kg/Mga
0.06
0.44
0.03
0.1
0.15
0.52
1.30
kg of VOC per Mg of butadiene produced.
Pressurized storage tanks vented to the process are considered to be normal
conditions, not a separate emission control.
Source: Adapted from Standifer, 1980.
12
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TABLE E-6. UNCONTROLLED AND CONTROLLED VOC EMISSINS FROM BUTADIENE
PRODUCTION BY OXIDATIVE DEHYDROGENATION OF n-BUTENES
Source
Flue gas
Absorption
column vent
Intermittent
process
emissions
Storage and
handling
Secondary
Fugitive
Total
Uncontrolled
emission
ratio,
kg/Mga
0.06
5.00
0.50
0.10
0.75
5.20
11.61
Control device
or technique
None
Catalytic or thermal
oxidation
Elevated flare
None
Reactor wastewater
stripper-flare
vented vapor
Detection and repair
of major leaks plus
mechanical seals
Emission
reduction,
%
0
95
95
70
90
Controlled
emission
ratio,
kg/Mga
0.06
0.25
0.03
0.10
0.23
0.52
1.19
kg of VOC per Mg of butadiene produced.
Pressurized storage tanks vented to the process are considered to be normal
conditions, not a separate emission control.
Source: Adapted from Standifer, 1980.
13
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TABLE E-7. UNCONTROLLED AND CONTROLLED VOC EMISSIONS FROM BUTADIENE
PRODUCTION BY EXTRACTION FROM ETHYLENE PLANT BY-PRODUCT STREAMS
Source
Flue gas
Hydrogenation
catalyst
regeneration
vent
Methylacetylene
column vent
Intermittent
process
emissions
Storage and
handling
Secondary
Fugitive
Total
Uncontrolled
emission
ratio,
kg/Mga
0.002
0.024
2.100
0.250
0.100
0.150
2.500
5.1
Control device
or technique
None
None
Incineration or
flare
Elevated flare
Noneb
None
Detection and repair
of major leaks plus
mechanical seals
Emission
reduction,
%
95
95
90
Controlled
emission
ratio,
kg/Mga
0.002
0.024
0.105
0.013
0.100
0.150
0.250
0.644
kg of VOC per Mg of butadiene produced.
Pressurized storage tanks vented to the process are considered to be normal
conditions, not a separate emission control.
Source: Adapted from Standifer, 1980.
14
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TABLE E-8. 1,3-BUTADIENE MONITORING DATA
Location
Houston, TX area
Los Angeles, CA
Riverside, CA
Atlanta, GA
Lincoln Tunnel , NY
Columbus, OH
Denver, CO
Jones State Forest, TX
Average mean
value
5.22
2.81
24.23
3.98
5.57
20.11
1.64
0.77
1.7
0.67
Maximum
value
88.61
33.76
88.39
6.19
24.09
2.71
5.47
7.6
2.41
Comments
incl. tunnels
excl. tunnels
in tunnel
outside air
only one sample
set
non-urban setting
38 miles north of Houston, Texas
Source: Versar, Inc., 1984.
15
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Disposition:
1,3-Butadiene may be disposed of by incineration.
Sampling and Analytical Methods
1. NIOSH Method S91
a. Adsorption on charcoal.
b. Desorption with carbon disulfide,
c. Gas chromatography with flame ionization detection.
Detection limit:
200 to 6600 mg/m3 (91-3000 ppm) with 1-liter sample.
Possible interferences:
High humidity can lower vapor trapping efficiency.
Compounds that have the same retention time at the oper-
ating parameters mentioned above may interfere.
Permissible Exposure Limits
OSHA ACGIH
TWA 1,000 ppm (2,200 mg/m3) 1,000 ppm (2,200 mg/m3)
STEL 1,250 ppm (2,750 mg/m3)
The ACGIH has listed 1,3-Butadiene for intended changes to delete
the STEL, to change the TWA to 10 ppm (22 mg/m3) and add a notation
that 1,3-Butadiene is an industrial substance suspected of carcino-
genic potential for man.
Human Toxicity
Acute Toxicity:
Vapors are irritating to eyes and mucous membranes. Inhala-
tion of high concentrations can cause unconsciousness and
death. If spilled on skin, can cause burns or frostbite (due
to rapid vaporization). Human subjects tolerated 4,000 ppm
for 6 hours with no apparent effects other than a slight
irritation of the eyes. Tolerances to high exposures appear
to develop following a single exposure. Human exposure of
volunteers to 8,000 ppm for 8 hours caused eye and upper
respiratory irritation.
Chronic Toxicity:
Chronic oncology studies completed for the National Toxicology
Program have indicated that 1,3-butadiene is carcinogenic in
both sexes of mice and rats at levels as low as 625 ppm.
16
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Bibliography
American Conference of Governmental Industrial Hygienists. 1984. TLVs,
Threshold Limit Values for Chemical Substances and Physical Agents in the
Work Environment and Biological Exposure Indices With Intended Changes for
1984-1985. 1$B N:0 - 936712-54-6. Cincinnati. OH.
Environ Corporation. 1983. Production and Utilization of 1.3-Butadiene:
Potential Exposure to Workers and the General Population. Prepared for the
U.S. Environmental Protection Agency, Office of Toxic Substances,
Washington, D.C.
Hawley, G. G. 1981. The Condensed Chemical Dictionary. 10th Edition. Van
Nostrand Reinhold Company. New York.
Kirk-Othmer. Encyclopedia of Chemical Technology, 3rd Edition, Volume 4.
1980. Butadiene.John Wiley and Sons, New York.
National Institute for Occupational Safety and Health. February 9, 1984.
Current Intelligence bulletin No. 41 - 1,3-Butadiene. DHHS (NIOSH)
Publication No. 84-105.
National Toxicology Program. 1983. Toxicology and Carcinogenesis Studies of
1,3-Butadiene (CAS A 106-99-0) in B6C3F1 Mice (Inhalation Studies).
PEI Associates, Inc., 1985, Control of Occupational Exposure to 1,3-Butadiene
at Monomer Production Facilities.Prepared for U.S. Environmental
Protection Agency, Office of Toxic Substances, Washington, D.C.
PEI Associates, Inc., 1984. Worker Exposure to 1.3-Butadiene in the Plastics
and Rubber Industry. Prepared for the U.S. "~ ^^ »—-----•--
Office of Toxic Substances, Washington, D.C.
Standifer, R. L. Butadiene, Organic Chemicals Manufacturing, Volume 10:
Selected Processes, Report 7. 198(hPrepared for the U.S. Environmental
Protection Agency, Office of Air Quality Planning and Standards, Research
Triangle Park, North Carolina.
Sax, I. N. 1981. Dangerous Properties of Industrial Materials. Sixth
Edition. Van Nostrand Reinhold Company, New York.
Sittig, M. 1981. Handbook of Toxic and Hazardous Chemicals. Noyes
Publications. Park Ridge, NJ.
U.S. Department of Health and Human Services. 1983. Chemical Registry of
Toxic Effects of Chemical Substances 1981 to 1982. National Institute for
Occupational Safety and Health. Cincinnati, OH.
U.S. Department of Health and Human Services. 1984. Manual of Analytical
Methods. National Institute for Occupational Safety and Health.
Cincinnati, OH.
17
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Versar, Inc., Springfield, Virginia. 1984. Exposure Assessment of
1,3-Butadiene. Draft. Prepared for U.S. Environmental Protection Agency,
Office of Toxic Substances, Washington, D.C.
Weast, R. T. 1981. CRC Handbook of Chemistry and Physics. 61st Edition.
CRC Press, Inc., Boca Raton, FL.
18
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Chemical Name
o-, m-, p-Cresol
CAS Number
95-48-7; 108-39-4; 106-44-5
Chemical Classification
Phenol
Synonyms
(2-, 3-, 4-,) cresol; (o-,m-,p-) cresylic acid; l-hydroxy-(2-,3-,4-)
methyl benzene; (o-,m-,p-) hydroxy toluene; (2-, 3- ,4-) hydroxy toluene;
(0-,m-,p-) methylphenol; (o-,m-,p-) oxytoluene; phenol, 2-methyl-(9Cl )
Physical /Chemical Properties
Description:
White crystals; phenol-like odor.
Colorless to yellowish liquid; phenol-like odor.
Crystalline mass; phenol -like odor
Boiling Point:
C; 203°C; 202°C
Melting Point:
30.9°C; 12°C; 35.3°C
Molecular Weight:
108.1
Chemical Formula:
CH3C6HltOH
Vapor Pressure:
1 mm at 38.2°C; 1 mm at 52°C; 1 mm at 53°C
Vapor Density:
3.72; 3.72; 3.72 (air = 1.0)
Refractive Index:
ND20 = 1.536; ND20 = 1.544; Np20 = 1.531
Solubility:
Soluble in alcohol, ether, chloroform, and hot water
Log Partition Coefficient (octanol/water):
3.40; 2.37; 2.35
19
-------
Photochemical Reactivity:
Reactivity toward OH- from 10 to 12 times butane. Reactivity
toward 03 is 10 percent of propylene. Major atmospheric
precursor is toluene; less than 10 percent of cresols from
toluene decay. o-Cresol reacts with oxidizing materials to
yield quinones and benzenes; reacts in less than one day in
air.
Chemical Reactivity:
Reacts violently with HN03, oleum, and chlorosulfonic acid.
Dangerous when heated to decomposition; emits highly toxic
fumes. Can react vigorously with oxidizing materials.
Environmental Fate
Decomposes in a soil microflora in 1 day. An aqueous solution of
cresol is destroyed by photooxidation.
Source of Emissions
Production:
Coal tar (from coke and gas works)
From toluene by sulfonation or oxidation
Uses:
Disinfectant
Phenolic resins
Tricresyl phosphate
Ore flotation
Textile scouring agent
Organic intermediate, mfg. of salicylaldehyde
Coumarin and herbicides
Surfactant
Synthetic food flavors (para isomer only)
Tables E-9 through E-20 present data on o-, m-, p-cresol pro-
duction, consumption, and emissions.
Storage:
Should be stored in cool, "dry, well-ventilated location, away
from any area where the fire hazard may be acute. Should be
protected against physical damage. Outside or detached
storage is preferred; should be separated from oxidizing
materials.
Transportation:
Shipped in glass bottles, 10- and 55-gallon metal drums, 55-
gallon metal barrels, tank trucks, tank cars, and tank barges,
Disposition:
Cresols may be disposed of by incineration.
20
-------
TABLE E-9. CRESOLS ISOMER PRODUCERS
Company
o-Cresol Producers
Continental Oil
Fallek
Ferro
Koppers
Merichem
Stimson
Location
Newark, NJ
Tuscaloosa, AL
Sante Fe Springs, CA
Oil City, PA
Houston, TX
Anacartes, WA
Total
p-Cresol Producer
Sherwln Williams
m-Cresol Producers
Koppers
Merichem
Chicago, IL
Oil City, PA
Houston, TX
Cresol isomer
capacity,
106 Ib/yr
7.7
9.6
4.5
5.4
15.1
4.5
46.8
N/Aa
N/A
N/A
Total
Cresol isomer
produced,
106 Ib/yr
5.0
6.0
3.0
3.0
10.0
3.0
30.0
21.0
0.75
0.75
1.50
Geographic coordinates,
1 ati tude/1 ongi tude
40 43 34/74 07 26
33 11 00/87 34 50
33 56 30/118 04 18
41 29 30/79 43 20
29 45 36/95 10 48
48 28 31/122 32 48
41 43 04/87 36 30
41 29 30/79 43 20
29 45 36/95 10 48
ro
Not available
Source: Systems Applications, Inc., 1982.
-------
TABLE E-10. MIXED CRESOLS AND CRESYLIC ACID PRODUCERS
Company
Mixed Cresol Producers
Continental Oil
Fallek
Ferro
Koppers
Merichem
Stimson
Location
Newark, NJ
Tuscaloosa, AL
Sante Fe Springs, CA
Oil City, PA
Houston, TX
Anacartes, WA
Total
Cresylic Acid Producers
Continental Oil
Crowley Tar Products
Fallek
Ferro
Koppers
Merichem
Mobile, Oil
Stimson
Newark, NJ
Houston, TX
Tuscaloosa, AL
Santa Fe Springs, CA
Follansbee, WV
Houston, TX
Beaumont, TX
Anacortes, WA
Total
Tar
acids capacity,
106 Ib/yr
50
20
30
35
100
30
265
50
30
20
30
35
100
10
30
305
Cresol s
or cresylic
acid produced,
106 Ib/yr
6
2
4
4
12
4
32
9
5
3
5
6
17
2
5
52
Geographic coordinates,
1 ati tude/1 ongi tude
40 43 34/74 07 26
33 11 00/87 34 50
33 56 30/118 04 18
41 29 30/79 43 20
29 45 36/95 10 48
48 28 31/122 32 48
40 43 34/74 07 26
29 43 50/95 14/20
33 11 00/87 34 50
33 56 30/118 04 18
40 23 10/80 35 07
29 45 36/95 10 48
34 04 14/94 03 40
48 28 31/122 32 48
l\3
Source: Systems Applications, Inc., 1980.
-------
TABLE E-11, 1978 END USE DISTRIBUTION OF CRESOL ISOMERS, CRESOLS,
AND CRESYLIC ACID
o-Cresol Isomer
2,6-ditert butyl -p-cresol (BHT)
Antioxidants
Export
Total
p-Cresol Isomer
Phenolic resins
Pesticides
Export
Total
m-Cresol Isomer
Pyrethroid pesticides
Mixed Cresols/Cresylic Acids Combined
Tricresyl phosphate (TCP)
Cresyl diphenol phosphate (CDF)j-
Phenolic resins
Wire enamel solvent
Pesticides
Disinfectants/cleaning compound
Ore flotation
Miscellaneous other
Export
Total
Isomers, Cresols,
or cresylic acid used
106 Ib/yr
15.0
10.0
5.0
30.0
5.5
5.0
10.5
21.0
1.5
31.0
20.0
20.0
8.0
3.0
3.0
7.0
5.0
97.0
%
50
33
17
100
26
24
50
100
100
32
21
21
8
3
3
7
5
100
Source: Systems Applications, Inc., 1980.
23
-------
TABLE E-12. IDENTIFIED SOURCE LOCATIONS OF CRESOLS END-USERS
Company
2,6 di-tert-buty-p-cresol
(BHT) Products
Ashland
Koppers
Shell
Uni royal
Location
Fords, NJ
Oil City, PA
Martinez, CA
Geismar, LA
Total
Pyrethroid Pesticide
Producers
CPC International
FMC
Vertac
Lyndhurst, NJ
Baltimore, MD
West Helena, AR
Total
Tricresyl Phosphate/Cresol
Di phenol phosphate Producers
FMC
Stauffer
Nitro, WV
Gal li polls Ferry, WV
Total
Production
capacity,
million Ib/yr
o-cresol Isomer
12
9
10
5
36
m-cresol Isomer
NAa
NA
NA
Mixed cresols/
cresylic Acid
60
50
110
Cresol
usage,
million Ib/yr
5
4
4
2
15
0.5
0.5
0.5
1.5
20
11
31
Geographic coordinates,
latitude/longitude
40 31 20/74 20 50
41 29 30/79 43 20
38 00 05/122 05 40
30 13 30/91 00 15
40 47 30/74 04 34
39 14 50/76 35 30
34 36 10/90 33 45
38 25 33/81 50 05
38 46 40/82 10 54
aNot available.
Source: Systems Applications, Inc., 1982.
-------
TABLE E-13. 1978 NATIONWIDE o-, m-, p-CRESOL EMISSIONS
Source
o-m-p-Cresol production
Mixed cresol production
Cresylic acid production
Phenolic resins production (isomer)
BHT production
Pyrethroid pesticide
Antioxidants production
Pesticides production
Tricresyl phosphate production
Phenolic resins
Wire enamel solvent
Pesticides
Disinfectants/cleaning compounds
Ore flotation agent
Miscellaneous, other
Coke ovens
Total
Nationwide emissions Ib/yr
o-cresol
75,000
24,800
3,525
0
15,000
0
10,000
0
2,120
13,700
2,740,000
550
411,000
411,000
1,000
796,080
4,503,775
m-cresol
3,750
34,400
39,950
0
0
750
0
0
5,800
37,400
7,480,000
2,185
1,122,000
1,122,000
2,600
1,104,240
10,995,075
1 1
p-cresol
105,000
20,800
41,125
27,500
0
0
0
2,500
4,900
31,600
6,320,000
1,265
948,000
948,000
2,200
667,680
9,120,570
Source: Systems Applications, Inc., 1982.
25
-------
TABLE E-14. CRESOLS PRODUCTION AND END-USE EMISSION FACTORS
Source
Mixed cresol production
Cresylic acid production
p-Cresol production
BHT/antioxidants
Phenolic resins
Pesticides
Pyrethroid pesticides
TCP production
Miscellaneous, other
Ib lost per Ib produced (used)
Process
0.00190
0.00190
0.0039
0.0008
0.00400
0.00040
0.00040
0.00035
Storage
0.00020
0.00020
0.00030
0.0001
0.0005
0.00005
0.00005
0.00005
Fugitive
0.00040
0.00040
0.00080
0.0001
0.0005
0.00005
0.00005
0.00010
Total
0.00250
0.00250
0.00500
0.001
0.00500
0.00050
0.00050
0.0005
0.001b
Deriva-
tion3
B
B
D
D
D
C
D
C
Basis: A - site visit data, B - state files, C - published data, D -
Hydroscience estimate
Based on a weighted average all of cresol uses.
Source: Systems Applications, Inc., 1982
26
-------
TABLE E-15. CRESOL ISOMER EMISSIONS FROM CRESOL, ISOMER PRODUCERS
Company
Location
Emissions Ib/yr
Process
Storage
Fugitive
Total
cresol emissions
,lb/yr
g/sec
o-Cresols Producers
Continental Oil
Fallek
Ferro
Koppers
Merichem
Stimson
Newark, NJ
Tuscaloosa, AL
Santa Fe Springs, CA
Oil City, PA
Houston, TX
Anacortes, WA
Total
9,500
11,400
5,700
5,700
19,000
5,700
57,000
1,000
1,200
600
600
2,000
600
6,000
2,000
2,400
1,200
1,200
4,000
1,200
12,000
12,500
15,000
7,500
7,500
25,000
7,500
75,000
0.18
0.22
0.11
0.11
0.36
0.11
ro
p-Cresol Producer
Sherwin Williams
Chicago, IL
81 ,900
6,300
16,800
105,000
1.51
m-Cresol Producers
Koppers
Merichem
Oil City, PA
Houston, TX
Total
1,425
1,425
2,850
150
150
300
300
300
600
1,875
1,875
3,750
0.03
0.03
Source: Systems Applications, Inc., 1982.
-------
TABLE E-16. CRESOL EMISSIONS FROM MIXED, CRESOL, CRESYLIC ACID PRODUCERS
Company
Continental Oil
Fallek
Ferro
Koppers
Merichem
Stimson
Location
Newark, NJ
Tuscaloosa, AL
Santa Fe Springs, CA
Oil City, PA
Houston, TX
Anacortes, WA
Total
Emission Ib/yr
Process
11,400
3,800
7,600
7,600
22 ,800
7,600
60,800
Storage
1,200
400
800
800
2,400
800
6,400
Fugitive
2,400
800
1,600
1,600
4,800
1,600
12,800
Total
cresol emissions
Ib/yr
15,000
5,000
10,000
10,000
30,000
10,000
80,000
g/sec
0.22
0.07
0.14
0.14
0.43
0.14
ro
00
Cresylic Acid Producers
Continental Oil
Fallek
Ferro
Koppers
Merichem
Mobil Oil
Stimson Lumber
Newark, NJ
Tuscaloosa, AL
Santa Fe Springs, CA
Follansbee, WV
Houston, TX
Beachmont, TX
Anacortes, WA
Total
17,100
5,700
9,500
11,400
32,300
3,800
9,500
89,300
1,800
600
1,000
1,200
3,400
400
1,000
9,400
3,600
1,200
2,000
2,400
6,800
800
2,000
18,800
22,500
7,500
12,500
15,000
42,500
5,000
12,500
117,500
0.32
0.11
0.18
0.22
0.61
0.07
0.18
Source: System Applications, Inc., 1982.
-------
TABLE £-17. CRESOL EMISSIONS FROM CRESOL USERS
Company
Location
Emissions Ib/yr
Process
Storage
Fugitive
Total
cresol emissions
Ib/yr
g/sec
o-Cresols Producers
2-6-Di -tert-buty-p-cresol
(BHT) producers
Ashland
Koppers
Shell
Un i roya 1
Fords, NO
Oil City, PA
Martinez, CA
Geismar, LA
Total
4,000
3,300
3,200
1,600
12,000
500
400
400
200
1,500
500
400
400
200
1,500
5,000
4,000
4,000
2,000
15,000
0.07
0.06
0.06
0.03
m-Cresol Producer
Pyrethroid Pesticide
Producers
CPC International
FMC
Vertac
Lyndhurst, NJ
Baltimore, MD
West Helena, AR
Total
200
200
200
600
25
25
25
75
25
25
25
75
250
250
250
750
0.004
0.004
0.004
ro
Mixed Cresols/Cresylic Acid
Tricresyl phosphate/cresyl
diphenyl phosphate producers
FMC
Stauffer
Nitro, WV
Gal li polis Ferry, WV
Total
7,000
3,850
10,850
1,000
550
1,550
2,000
1,100
3,100
10,000
5,500
15,500
0.14
0.08
Source: Systems Applications, Inc., 1982
-------
TABLE E-18. CRESOL ISOMER EMISSIONS FROM COKE OVEN OPERATION3
Region
New England
Middle Atlantic
East North Central
West North Central
South Atlantic
East South Central
West South Central
Mountain
Pacific
Total
Number
of sites
0
15
25
3
4
9
2
2
1
61
o-Cresol
emissions
Ib/yr
0
195,750
326,250
39,150
52,200
117,450
26,100
26,100
13,050
796,050
m-Cresol
emissions
Ib/yr
0
271,500
452,500
54,300
72,400
162,900
36,200
36,200
18,100
1,104,100
p-Cresol
emissions
Ib/yr
0
164,175
273,625
32,835
43,780
98,505
21,890
21,890
10,945
667,645
Total
cresol
emissions
Ib/yr
0
631,425
1,052,375
126,285
168,380
378,855
84,190
84,190
42,095
2,567,795
Basis: 107 billion Ib coke produced; 0.000024 Ib cresols emitted/lb coke
produced; cresol composition - 25 percent p-cresol, 31 percent o-cresol, and
43 percent m-cresol in mixed cresols emitted.
Source: Systems Applications, Inc.,, 1982.
30
-------
TABLE E-19. CRESOL ISOMER EMISSIONS FROM MIXED CRESOLS/CRESYLIC
ACID USED AS WIRE ENAMEL SOLVENT
Region
New England
Middle Atlantic
East North Central
West North Central
South Atlantic
East South Central
West South Central
Mountain
Pacific
Total
Number
of sites
46
339
370
84
174
44
87
25B
174
1,576
o-Cresol
emissions
Ib/yr
79,975
589,380
643,275
146,040
302,510
76,500
151,255
448,555
302,510
2,740,000
p-Cresol
emissions
Ib/yr
184,465
1,359,440
1,483,755
336,855
697,765
176,445
348,885
1,034,620
697,765
6,319,995
m-Cresol
emissions
Ib/yr
218,325
1,608,960
1,756,090
398,680
825,835
208,830
412,920
1,224,520
825,840
7,480,000
Source: Systems Applications, Inc., 1982.
31
-------
TABLE E-20. CRESOL ISOMER EMISSIONS FROM MIXED CRESOLS/CRESYLIC
ACID USED AS AN ORE FLOTATION AGENT
Region
New England
Middle Atlantic
East North Central
West North Central
South Atlantic
East South Central
West South Central
Mountain
Pacific
Total
Number
of sites
6
38
85
145
62
40
21
144
22
563
o-Cresol
emissions
Ib/yr
4,382
27,750
62,075
105,890
45,275
29,211
15,336
105,161
16,066
411,000
p-Cresol
emissions
Ib/yr
11,957
75,729
169,392
288,964
123,557
79,714
41,850
286,971
43,843
1,122,000
m-Cresol
emissions
Ib/yr
10,103
63,987
143,128
244,159
104,399
67,354
35,361
242,475
37,045
984,000
Source: Systems Applications, Inc., 1982.
32
-------
Sampling and Analytical Methods
1. NIOSH Method 2001
a. Absorption on silica gel.
b. Desorption with acetone.
c. Gas chromatography.
Detection limit:
5 to 60 mg/m3 in a 20-liter sample
Possible interferences:
High humidity can cause lower vapor trapping efficiency.
Compounds with the same retention time may cause interference.
Permissible Exposure Limits
OSHA (skin) AC6IH (skin) NIOSH (skin)
TWA 5 ppm (22 mg/m3) 5 ppm (22 mg/m3) 2.3 ppm (10 mg/m3)
Odor perception 0.022 mg/m3
Human Toxicity
Acute Toxicity:
Cresol vapors or liquids are readily absorbed through the skin
or any mucous membrane, which may cause acute and chronic
poisoning. Skin contact with concentrated solutions can
result in severe burns. Cresols are not sufficiently volatile
to constitute a respiratory hazard under normal conditions.
Systematic poisoning has rarely been reported, but it is
possible that adsorption may result in damage to the kidneys,
liver, and nervous systems.
Chronic Toxicity:
No reports of epidemiologic studies of worker exposures to
cresol were found. No investigations of the mutagenic or
teratogenic potential of cresol were found. The cresol isomers
promoted DMBA-induced papillomas in mice, but no carcinomas
were produced.
Bibliography
American Conference of Governmental Industrial Hygienists. 1984. TLVs,
Threshold Limit Values for Chemical Substances and Physical Agents in the
Work Environment and 6101001031 Exposure Indices with Intended Changes for
1984-1985.ISB N:0 - 936712-54-6. Cincinnati, OH.
Hawley, G. G. 1981. The Condensed Chemical Dictionary. 10th Edition. Van
Nostrand Reinhold Company, New York.
National Fire Protection Association. 1983. National Fire Codes, A Comp-
liance of NFPA Codes, Standards, Recommended Practices, and Manuals.
Volume 13.NFPA, Quincy, MA.
33
-------
Sax, I. N. 1981. Dangerous Properties of Indutrial Materials. Sixth
Edition. Van Nostrand Reinhold Company, New York.
Sittig, M. 1981. Handbook of Toxic and Hazardous Chemicals. Hoyes
Publications. Park Ridge, NJ.
Systems Applications, Inc. 1980. Human Exposure to Atmospheric Concentra-
tions of Selected Chemicals. Volume 1"PB 81-193252.Systems Applied-
tions, Inc., San Rafael, CA.
Systems Applications, Inc. 1982. Human Exposure to Atmospheric Concentrations
of Selected Chemicals, Volume IITAppendix A-10.Cresol.EPA Contract
No. 68-02-3066.SAI 58-EF81-156R2. Systems Applications, Inc., San Rafael, CA.
U.S. Department of Health and Human Services. 1983. Chemistry Registry of
Toxic Effects of Chemical Substances 1981 to j-982. National Institute for
Occupational Safety and Health.Cincinnati, OH.
U.S. Department of Health and Human Services. 1984. Manual of Analytical
Methods. National Institute for Occupational Safety and Health.
Cincinnati, OH.
U.S. Environmental Protection Agency. 1978. Human Exposure to Atmospheric
Concentrations of Selected Chemicals. Office of Air Quality Planning and
Standards.Research Triangle Park, NC.
U.S. Environmental Protection Agency. 1980. Treatability Manual: Volume 1
Treatability Data. EPA 600-8-80-042a.
Verschueren, K. Department of Public Health and Tropical Hygiene,
Agricultural University of Wageninzen, Netherlands. 1983. Handbook of
Environmental Data on Organic Chemicals, Second Edition. Van Nostrand
Reinhold Company, New York.
Weast, R. T. 1981. CRC Handbook of Chemistry and Physics. 61st Edition.
CRC Press, Inc., Boca Raton, FL.
34
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Chemical Name
p-Di chl orobenzene
CAS Number
106-46-7
Chemical Classification
Chlorinated aromatic hydrocarbon.
Synonyms
P-chlorophenyl chloride; P-dichlorobenzeen; 1,4-dichloorbenzeen;
P-dichlorbenzol; 1,4-dichlorbenzol; Di-chloricide;
P-dichlorobenzene; 1,4-dichlorobenzene; p-dichlorobenzol ;
dichlorobenzene, para, solid; 1,4-dichlorobenzene;
p-dichlorobenzene; evola; NCL-C54955; paracide; paracrystals;
paradi; paradichlorobenzene; paradichlorobenzol ; paradon; paramoth;
paranuggets; parazene; PDB; PDCB; persia-perazol ; santochlor.
Physical/Chemical Properties
Description:
White crystals; volatile (sublimes readily); penetrating odor.
Boiling Point:
173. 7°C
Melting Point:
53°C
Molecular weight:
147.0
Chemical Formula:
Vapor Pressure:
10 mm at 54.8°C
Vapor Density:
5.08 (air = 1)
Refractive Index:
N2° = 1.5285
Solubility:
Soluble in alcohol, benzene, and ether. Insoluble in water.
35
-------
Log Partition Coefficient (octanol/water):
3.39
Photochemical Reactivity:
Reactivity toward H0» is 50 percent of butane. Reactivity
toward 03 is 5 percent of propylene. No major atmospheric
precursors.
Chemical Reactivity:
Can react vigorously with oxidizing materials. When heated to
decomposition or on contact with acid or acid fumes, will
evolve toxic chloride fumes.
Environmental Fate
Volatilizes at a relatively rapid rate; half-life less than 12
hours. Bioaccumulates more than chlorobenzene; too resistant to
biodegradation to compete with volatilization. Oxidized by hydroxy
radicals in atmosphere.
Source of Emissions
Production/processing:
Chlorination of monochlorobenzene
Uses:
Moth repellent
General insecticide
Germicide
Space odorant
Manufacture of 2,5-dichloroaniline
Dyes
Intermediates
Pharmaceuticals
Agriculture (fumigating soil)
Tables E-21 through E-25 and Figure E-l present
p-dichlorobenzene production, consumption, and emission data.
Storage:
Should be protected against physical damage and stored in
cool, dry, well-ventilated place, away from any area where the
fire hazard may be acute (outside or detached storage is pre-
ferred), separate from oxidizing materials.
Transportation:
Should be shipped in 5-, 10-, 55-, and 110-gallon drums or
tank cars.
Disposition:
P-dichlorobenzene may be disposed of by incineration, prefera-
bly after mixing with another combustible fuel. Care must be
exercised to assure complete consumption to prevent the forma-
tion of phosgene. An acid scrubber is necessary to remove the
halo acids produced.
36
-------
TABLE E-21. p-DICHLOROBENZENE PRODUCERS
Source
Dow
Monsanto
PPG
Standard Chlorine
Specialty Organ ics
Montrose
ICC
Location
Midland, MI
Sauget, IL
New Martinsville, WV
Delaware City, DE
Irwindale, CA
Henderson, NV
Niagara Falls, NY
Total
1978
Estimated
production,
106 Ib/yr
9
4
13
24
1
2
2
55
1978
Estimated
capacity,
106 Ib/yr
30
12
40
75
2
7
8
174
Geographic coordinates
latitude/longitude
43 35 28/84 13 08
38 35 31/90 10 11
39 47 22/80 51 27
33 33 54/75 38 47
34 06 30/117 55 48
36 03 32/114 58 34
43 03 33/79 00 55
Total production was distributed per site based on capacity.
Processes dichlorobenzenes from Montrose.
Source: Systems Applications, Inc. 1980.
-------
TABLE E-22. p-DICHLOROBENZENE END-USE DISTRIBUTION 1978
End-Use
Space deodorant
Moth control
Pesticide intermediate
TOTAL
Volume,
million Ib/yr
27.5
22
5.5
55
Usage, %
50
40
10
100
Source: Systems Applications, Inc., 1980.
TABLE E-23. 1978 NATIONWIDE EMISSIONS OF p-DICHLOROBENZENE
Source
Nationwide
emissions,
Ib/year
Production
Space deodorant
Moth control
Pesticide intermediate
398,200
27,500,000
22,000,000
2,750
TOTAL
49,900,950
Source: Systems Applications, Inc., 1980.
38
-------
TABLE E-24. P-DICHLOROBENZEME EMISSIONS FROM PRODUCTION SITES
Source
Dow
Monsanto
PPG
Standard Chlorine
Specialty Organics
Montrose
ICC
Location
Midland, MI
Sauget, IL
New Martinsville, WV
Delaware City, DE
Irwindale, CA
Henderson, NV
Niagara Falls, NY
Total
Emissions, Ib/yr
Process
52,290
23,240
75,530
139,440
5,810
11,620
11,620
319,550
Storage
3,690
1,640
5,330
9,840
410
820
820
22,550
Fugitive
9,180
4,080
13,260
24 ,480
1,020
2,040
2,040
56,100
Total emissions
Ib/year
65,160
28,960
94,120
173,760
7,240
14,480
14,480
398,200
9/s
0.94
0.42
1.35
2.50
0.10
0,21
0.21
co
UD
Source: Systems Applications, Inc. 1980.
-------
TABLE E-25. EMISSIONS AND METEROLOGICAL STATIONS OF SPECIFIC POINT SOURCES OF p-DICHLOROBENZENE
Company
Dow
Monsanto
PPG
Standard Chlorine
Specialty Organics
Montrose
ICC
Site
Midland, MI
Sauget, IL
New Martinsville, WV
Delaware City, DE
Irwindale, CA
Henderson, NV
Niagara Falls, NY
Latitude/ longitude
43 35 28/084 13 08
38 35 31/090 10 11
39 47 22/080 51 27
39 33 54/075 38 47
36 06 30/117 55 48
36 03 32/114 58 34
43 03 33/079 00 55
Star
station
14845
13994
13736
94741
23215
23112
14747
Emissions, gm/s
Process
0.752976
0.334656
1.087632
2.007936
0.083664
0.167328
0.167328
Storage
0.053136
0.023616
0.076752
0.141696
0.005904
0.011808
0.011828
Fugitive
0.132192
0.058752
0.190944
0.352512
0.014688
0.029376
0.029376
Source: Systems Applications, Inc. 1982.
-------
VI
c
o
•r—
CO
CO
0)
OJ
C •!->
•i- tO
O >>
O. GO
U
O
OJ
Q.
o;
3
O)
o
41
-------
Sampling and Analytical Methods
1. NIOSH Method S281
a. Adsorption on charcoal.
b. Desorption with carbon disulfide.
c. Gas chromatography.
Detection limit:
75 to 1350 mg/m3 (17.5-300 ppm); 170-liter sample.
Possible interferences:
None identified.
2. Method B (Appendix A): C2-Cis hydrocarbons and other
nonpolar organics with a boiling point of 100° to 175°C
a. Whole air collection in canister.
b. Cryogenic concentration.
c. Gas chromatography/flame ionization detection.
Detection limit:
0.1 ppb per IOC-ml sample.
Possible interferences:
Storage times greater than a week are not recommended.
3. Method C (Appendix A): C6-Ci2 hydrocarbons and other
nonpolar organics with a boiling point between 60° and 200°C
a. Adsorption on Tenax (resin adsorption/solvent desorption
may be used).
b. Thermal desorption.
c. Gas chromatography/mass spectrometry analysis (gas chroma-
tography/electron capture detection or photoionization
detection may also be used).
Detection limit:
1 to 200 ppt per 20-liter sample.
Possible interferences:
Blank levels usually limit sensitivity artifacts due to
reactive components (03, NO ). Sample can be analyzed
only once.
4. Method D (Appendix A): Cg-C^ hydrocarbons and other
nonpolar organics with a boiling point of 60° to 200°C
a. Adsorption on Tenax (resin adsorption/solvent desorption
may be used).
b. Thermal desorption into canisters.
c. Gas chromatography/flame ionization detection or gas
chromatography/mass spectrometry analysis. (Gas
chromatography/electron capture detection or
photoionization detection also may be used.)
42
-------
Detection limit:
0.01 to 1 ppb per 20-liter sample.
Possible interferences:
Blanks and artifact problems, as in Method C.
Permissible Exposure Limits
OSHA ACGIH
TWA 75 ppm (450 mg/m3) 75 ppm (450 mg/m3)
STEL 110 ppm (675 mg/m3)
Human Toxicity
Acute Toxocity:
Toxicity is high orally; moderate via intraperitoneal or
inhalation. Has been reported to cause liver injury in
humans.
Chronic Toxicity:
Carcinogenic determination in both animals and humans is indefi-
nite. Currently tested by the National Toxicology Program for
carcinogenesis bioassay as of January 1983.
Bibliography
American Conference of Governmental Industrial Hygienists. 1984. TLVs,
Threshold Limit Values for Chemical Substances and Physical Agents in the
Work Environment and Biological Exposure Indices Hith Intended Changes for
gical bx
12-54-6.
1984-1985. ISB N:0 - 936712-54-6. Cincinnati, OH.
Hawley, G. G. 1981. The Condensed Chemical Dictionary. 10th Edition. Van
Nostrand Reinhold Company, New York.
International Agency for Research on Cancer. 1974. IARC Monographs on the
Evaluation of Carcinogenic Risk of Chemicals to Man"! Volume 7, Ortho- and
Para-Pichlorobenzene. Lyon, France.pp. 231-244.
National Fire Protection Association. 1983. National Fire Codes, A Comp-
liance of NFPA Codes, Standards, Recommended Practices, and Manuals.
Volume 13.NFPA, Quincy, MA.
Sax, I.N. 1981. Dangerous Properties of Industrial Materials.
Sixth Edition. Van Nostrand Reinhold Company, New York.
Sittig, M. 1981. Handbook of Toxic and Hazardous Chemicals. Noyes
Publications, Park Ridge, NO.
Systems Applications, Inc. 1980. Human Exposure to Atmospheric Concentra-
tions of Selected Chemicals, Volume 1.PB 81-193252.Systems Applica-
tions, Inc., San Rafael, CA.
43
-------
Systems Applications, Inc. 1982. Human Exposure to Atmospheric Concentrations
of Selected Chemicals, Volume II.Appendix A-7, Chlorobenzene.EPA Contract
No. 68-02-3066. SAI 58-EF81-156R2. Systems Applications, Inc., San Rafael, CA.
U.S. Department of Health and Human Services. 1983. Chemical Registry of
Toxic Effects of Chemical Substances 1981 to 1982. National Institute for
Occupational Safety and Health.Cincinnati, OH.
U.S. Department of Health and Human Services. 1984. Manual of Analytical
Methods. National Institute for Occupational Safety and Health.
Cincinnati, OH.
U.S. Environmental Protection Agency. 1980. Treatability Manual: Volume 1,
Treatability Data. EPA 600-8-80-042a.
Verschueren, K. 1983. Handbook of Environmental Data on Organic Chemicals,
Second Edition. Department of Public Health and Tropical Hygiene,
Agricultural university of Wageningen, Netherlands. Van Nostrand Reinhold
Company, New York.
Weast, R. T. 1981. CRC Handbook of Chemistry and Physics. 61st Edition.
CRC Press, Inc., Boca Raton, PL.
44
-------
Chemical Name
Dimethyl nitrosamine
CAS Number
62-75-9
Chemical Classification
Nitrosamine
Synonyms
Di methyl nitrosamin; dimethyl nitrosamine; N,N-dimethyl -nitrosamine;
dimethylnitrosoamine; DMN; DMNA; Ni-methyl-N-nitrosomethanamine;
NDMA; nitrosodimethylamine; N-nitrosodimethylamine.
Physical /Chemical Properties
Description:
Yellow liquid
Boiling Point:
152°C
Melting Point:
Not available
Molecular Weight:
74.1
Chemical Formula:
Vapor Pressure:
Not available
Vapor Density:
2.56 (air = 1)
Refractive Index:
ND20 = 1.4358
Solubility:
Soluble in water, alcohol and ether.
Log Partition Coefficient (octanol /water)
Not available
Photochemical Reactivity:
Photochemically reactive
45
-------
Chemical Reactivity:
Strong oxidants (peracids) oxidize it to the corresponding
nitrosamine; can be reduced to the corresponding hydrazine
and/or amine. Relatively resistant to hydrolysis but can be
easily split by hydrogen bromide in acetic acid. When heated,
it dampens to emit NO .
A
Environmental Fate
Biodegradation of 0.01 mg/liter is 100 percent in 15 days in both
freshwater and seawater.
Source of Emissions
Producti on/process i ng:
From sodium nitrile and dimethyl amine hyperchloride.
Uses:
Prior to April 1, 1976, NDMA was used in the United States as
an intermediate in the production of 1,1-dimethyl hydrazine, a
storable liquid rocket fuel. No evidence of present use
except for research purposes.
Storage:
Mixture containing 1 percent or more NDMA must be maintained
in isolated or closed systems. Entrance to regulated area
posted "Cancer-Suspect Agent Exposed in This Area. Impervious
Suit Including Gloves, Boots, and Air-Supplied Hood Required
at All Times. Authorized Personnel Only."
Transportation:
Certain procedures must be followed in movement of material
and in case of accidental spills and emergencies. OSHA
Standards, Subpart Z, Section 1910.1016.
Disposition:
Dimethyl nitrosamine may be disposed of by pouring over soda
ash, neutralizing with HC1.
Sampling and Analytical Methods
1. NIOSH Method 252
a. Tenax GC absorption.
b. Thermal desorption with the purge.
c. Capillary gas-liquid chromatography.
d. Mass spectrometry.
Detection limit:
0.5 ppt to 10 ppb per 150-liter sample.
46
-------
Possible interferences:
Materials having background ions of m/e 74 (C2H8N3>
C2M02, C6H6N20, C3H3C1, C3H6S, C3H602, or C3H10N2) if
at the same retention time as DMN.
2. NIOSH Method 299
a. Adsorption on Tenax-GC.
b. Thermal adsorption.
c. GC-NPD.
Detection limit:
2-1000 gm/m3 per 5-liter sample.
Possible interferences:
Any compound that has the same retention time as the
analyte is a potential interferent. Process is most
selective for nitrogen or phosphorous containing
compounds.
3. Method M (Appendix A)
a. Adsorption on Thermosorb N.
b. Thermal desorption.
c. Gas chromatography/mass spectrometry or thermal energy
detectors (in relatively "clear" environments, a gas
chromatography/nitrogen phosphorus detection approach may
be used).
Detection limit:
25 mg/m3 per 200-liter sample.
Possible interferences:
Thermal energy analyzer is a nitrosamine-specific detector
and is rather expensive. Gas chromatography/nitrogen
phosphorus detection may be a less expensive alternative
in many situations.
Permissible Exposure Limits
OSHA ACGIH
TWA Not established Not established
Specific regulations regarding use of a regulated area and labeling
requirements, are presented in Section 1910.1016 of Subpart Z of
the Occupational Safety and Health Standards. The ACGIH has listed
dimethyl nitrosamine as an industrial substance suspected of
carcinogenic potential for man (skin).
Human Toxicity
Acute Toxicity:
High oral, inhalation, intraperitoneal, and subcutaneous
toxicity. Has caused fatal liver disease in humans.
47
-------
Chronic Toxicity:
There is sufficient evidence to substantiate a carcinogenic
effect in many experimental animal species. Similarities in
its metabolism by human and rodent tissues have been demon-
strated. Although no epidemiological data are available,
dimethylnitrosamine should be regarded (for practical pur-
poses) as if it were carcinogenic to humans.
Bibliography
American Conference of Governmental Industrial Hygienists. 1984. TLVs,
Threshold Limit Values for Chemical Substances and Physical Agents in the
Work Environment and Biological Exposure Indices With Intended Changes for
gical l>
12-54-6.,
1984-1985. ISB N:0 - 936712-54-6., Cincinnati, (5H.
Hawley, G. G. 1981. The Condensed Chemical Dictionary. 10th Edition.
Van Nostrand Reinhold Company, New York.
International Agency for Research on Cancer. 1978. IARC Monographs on the
Evaluation of Carcinogenic Risk of Chemicals to ManTVol. 17
N-nitrosodmethylamine. Lyon, France, pp 125-152.
National Fire Protection Association. 1983. National Fire Codes, A Comp-
liance of NFPA Codes, Standards, Recommended Practices, and Manuals.
Vol. 13.NFPA, Quincy, MA.
Sax, I. N. 1981. Dangerous Properties of Industrial Materials.
Sixth Edition. Van Nostrand Reinhold Company, New York.
Sittig, M. 1981. Handbook of Toxjc and Hazardous Chemicals. Noyes
Publications, Park Ridge, NJ.
Systems Applications Inc. 1980. Human Exposure to Atmospheric Concentra-
tions of Selected Chemicals. VoTTTPB 81-193252. Systems Applica-
tions, Inc., San Rafael, CA.
U.S. Department of Health and Human Services. 1983. Chemical Registry of
Toxic Effects of Chemical Substances 1981 to 1982. National Institute for
Occupational Safety and Health.Cincinnati, OH.
U.S. Department of Health and Human Services. 1984. Manual of Analytical
Methods. National Institute for Occupational Safety and Health.
Cincinnati, OH.
Verschueren, K. 1983. Handbook of Environmental Data on Organic Chemicals.
Second Edition. Department of Public Health and Tropical Hygiene,
Agricultural University of Wageningen, Netherlands. Van Nostrand Reinhold
Company, New York.
Weast, R. T. 1981. CRC Handbook of Chemistry and Physics. 61st Edition.
CRC Press, Inc., Boca Raton, FL.
48
-------
Chemical Name
Ethylene dichloride
CAS Number
107-06-2
Chemical Classification
Chlorinated hydrocarbon (unsaturated)
Synonyms
Aethylenchlorid; 1,2-bichloroethane; bichorure d'ethylene; berer
sol; brocide; chlorure d'ethylene; cloruro di ethene; destruxol
borer-sol; 1,2-dichloroethaan; 1,2-dichlor-aethan; dichloremulsion;
1,2-dichlorethane; dichlor-mulsion; dichloro-l,2-ethane; alpha-
beta-dichloroethane; sym-dichloroethane; 1,2-dichloroethane; di-
chloroethylene; 1,2-dichloroetano; Dutch liquid; Dutch oil; EDC;
Ent 1,656; ethane dichloride; ethyleendichloride; ethylene
chloride; ethylene dichloride; ethylene dichloride (DOT);
1,2-ethylene dichloride; freon 150; glycol dichloride; NCI-00511.
Physical/Chemical Properties
Description:
Colorless oily liquid; chloroform-like odor; sweet taste
Boiling Point:
83.5°C
Melting Point:
-35.5°C
Molecular Weight:
100.0
Chemical Formula:
C1CH2CH2C1
Vapor Pressure:
100 mm at 29.4°C
Vapor Density:
3.35 (air = 1)
Refractive Index:
ND20 = 1.445
Solubility:
Miscible with most common solvents; slightly soluble in water.
49
-------
Log Partition Coefficient (octanol/water):
1.48
Photochemical Reactivity:
Evaporates rapidly from water to the atmosphere, where it is
destroyed by photooxidation.
Chemical Reactivity:
Stable to water, acids, and bases, and also resists oxidation.
Incompatible with dinitrogen tetroxide, metals.
Environmental Fate
Due to a high vapor pressure, volatilization to the atmosphere is
rapid and is the major transport process. Photooxidation in the
troposphere may be a predominant fate. Photooxidation in the
aquatic environment occurs at a slow rate.
Source of Emissions
Producti on/processi ng:
Action of chlorine on ethylene with subsequent distillation,
with metalic catalyst.
Reaction of acetylene and HC1.
Uses:
Vinyl chloride solvent
Lead scavenger in antiknock gasoline
Paint, varnish, and finish remover
Metal degreasing
Soaps and scouring compounds
Wetting and penetrating agents
Organic synthesis
Ore flotation
Tables E-26 through E-30 present ethylene dichloride produc-
tion, consumption, and emission data.
Storage and Transportation:
Protect against physical damage. Outside or detached storage
is preferable. Inside storage should be in a standard flam-
mable-liquids storage room or cabinet, separate from oxidizing
materials. Shipped by 1-gallon cans, 5- to 55-gallon metal
drums, tank cars, and tank barges.
Disposition:
Ethylene dichloride may be disposed of by incineration, pre-
ferably after mixing with another combustible fuel. Care must
be exercised to assure complete combustion to prevent forma-
tion of phosgene. An acid scrubber is necessary to remove the
halo acids produced. Alternatively, ethylene dichloride may
be recovered from process off-gases.
50
-------
TABLE E-26. ETHYLENE DICHLORIDE PRODUCERS AND MAJOR CONSUMERS
(January 1, 1979, production capacities in thousands of metric tons)
Producer
Borden Chemical
Conoco Chemical
Diamond Shamrock
Diamond Shamrock
Dow Chemical
Dow Chemical
Dow Chemical
Dow Chemical
Du Pont
Du Pont
Du Pont
Ethyl Corporation
Ethyl Corporation
B. F. Goodrich
Houston Chemical
ICI America3
Monochem
Location
Geismar, LA
Lake Charles, LA
Deer Park, TX
La Porte, TX
Freeport, TX
Oyster Creek, TX
Pittsburg, CA
Plaquemine, LA
Antioch, CA
Corpus Christi, TX
Deepwater, NJ
Baton Rouge, LA
Houston, TX
Calvert City, KY
Beaumont, TX
Baton Rouge, LA
Geismar, LA
Capacity
524
145
719
726
499
953
318
118
454
318
VCM
224
525
749
150
525
936
248
749
224
Ob
1.1,1-
TCE
167
112
TCE
17
51
Ob
15
PCE
45
Ob
Ob
Ob
14
EA
60
VDCM
45C
45C
20C
Scavenger
20C
20C
20C
15C
en
(continued)
-------
TABLE E-26 (continued)
Producer
Mai co Chemical
PPG Industries
PPG Industries
Shell Chemical
Shell Chemical
Stauffer Chemical
Stauffer Chemical
Union Carbide
Union Carbide
Vulcan Chemical
Vulcan Chemical
Location
Freeport, TX
Lake Charles, TX
Guayanilla, PR
Deer Park, TX
Morco, LA
Carson, CA
Louisville, KY
Taft, LA
Texas City, TX
Geismar, LA
Wichita, KS
Total
Capacity
544
379
635
544
154
68
68
150
7,316
VCM
229
375
629
525
130
6,218
1,1,1-
TCE
130
ob
409
TCE
68
151
PCE
54
Ob
41
Ob
154
EA
70
60
190
VDCM
30C
140
Scavenger
5C
80
en
ro
Plant was purchased from Allied Chemical in September 1978.
Process does not use EDC as a feedstock
cRough order estimates.
Source: SRI International, 1979.
-------
TABLE E-27. ESTIMATED ATMOSPHERIC EMISSIONS OF ETHYLENE
DICHLORIDE FOR 1977
EDC production
Fugitive
Storage
Direct chlorination
Oxychlori nation
Subtotal
Production in using EDC as Feedstock
VCM
1,1,1-TCE
TCE
PCE
EA
VDCM
Lead scavenger
Subtotal
Automobile Gasoline
Service stations
Auto emissions
Subtotal
Other
Dispersive uses
Transportation
Waste disposal
Total
Emissions,
1,000 mt/yr
5.2
14.5
6.3
17.9
43.9
1.1
0.4
0.2
0.3
0.3
0.2
0.2
2.7
0.1
1.2
1.3
5.0
0.0
0.0
52.9
Not included. Rough order estimates place these emissions at much less
than 2,400 mt/yr for transportation and much less than 29,000 mt/yr for
waste disposal.
Source: SRI International, 1979.
53
-------
TABLE E-28. ESTIMATED ATMOSPHERIC EMISSIONS FROM ETHYLENE DICHLORIDE PRODUCTION FACILITIES
Plant
Conoco
Diamond
Diamond
Dow
Dow
Dow
Ethyl
Ethyl
Goodrich
ICI America
PPG
PPG
Shell
Shell
Stauffer
Union Carbide
Union Carbide
Vulcan
Location
Lake Charles, LA
Deer Park, TX
La Porte, TX
Freeport, TX
Oyster Creek, TX
Plaquemine, LA
Baton Rouge, LA
Houston, TX
Calvert City, KY
Baton Rouge, LA
Lake Charles, LA
Guayanilla, PR
Deer Park, TX
Morco, LA
Carson, CA
Taft, LA
Texas City, TX
Geistnar, LA
Total
Production3
103 mt/yr
372
103
510
515
354
678
226
84
322
226
386
269
451
386
109
48
48
107
5,194
Emissions, g/s
Fugitive
11.8
3.3
16.2
16.3
11.2
21.5
7.2
2.7
10.2
7.2
12.3
8.5
14.3
12.3
3.5
1.5
1.5
3.4
164.9
Storage
33.0
9.1
45.3
45.7
31.4
60.1
20.1
7.5
28.6
20.1
34.3
23.9
40.0
34.3
9.7
4.3
4.3
9.5
461.2
Direct
12.8
2.6
17.8
20.5
12.4
24.4
8.3
5.9
7.5
10.5
20.8
9.4
20.8
13.5
5.3
3.4
3.4
0.0
199.3
Oxychlori
nation
12.6
1.9
15.8
67.3
0.0
99.5
43.7
0.0
26.6
70.6
0.0
41.4
27.1
59.4
19.6
0.0
0.0
80.8
566.3
Total
70.2
16.9
95.1
149.8
55.0
205.5
79.3
16.1
72.9
108.4
67.4
83.2
102.2
119.5
38.1
9.2
9.2
93.7
1,391.7
en
-£>
aAssumed to be 71 percent of production capacity.
Souce: SRI International, 1979.
-------
TABLE E-29. ESTIMATED EDC ATMOSPHERIC EMISSIONS FOR PLANTS THAT USE ETHYLENE OICHLORIDE
AS A FEEDSTOCK
(g/s)
Producer
Borden Chemical
Conoco Chemical
Diamond Shamrock
Diamond Shamrock
Dow Chemical
Dow Chemical
Dow Chemical
Du Pont
Du Pont
Ethyl Corporation
Ethyl Corporation
B. F. Goodrich
Houston Chemical
ICI America
Mai co Chemical
PPG Industries
PPG Industries
Location
Geismar, LA
Lake Charles, LA
Deer Park, TX
La Porte, TX
Freeport, TX
Oyster Creek, TX
Plaquemine, LA
Antioch, CA
Deepwater, NJ
Baton Rouge, LA
Houston, TX
Calvert City, KY
Beaumont, TX
Baton Rouge, LA
Freeport, TX
Lake Charles, TX
Guayanilla, PR
VCM
1.2
2.9
4.1
0.8
2.9
5.1
1.4
4.1
1.2
1.3
2.1
1,1,1-
TCE
5.6
3.7
4.3
TCE
0.7
2.0
0.6
2.7
PCE
1.6
0.5
1.9
EA
2.7
VDCM
2.3
2.3
1.5
Lead
scavenger
1.1
1.1
1.1
1.1
0.9
0.3
Total
1.2
2.9
2.3
4.1
13.4
2.9
8.8
3.4
1.1
3.6
1.1
4.1
0.9
1.2
0.3
11.7
2.1
in
en
(continued)
-------
TABLE E-29 (continued)
Producer
Shell Chemical
Shell Chemical
Stauffer Chemical
Union Carbide
Union Carbide
Vulcan Chemical
Location
Deer Park, TX
Morco, LA
Carson, CA
Taft, LA
Texas City, TX
Geismar, LA
Total
VCM
3.4
2.9
0.7
34.1
1,1,1-
TCE
13.6
TCE
6.0
PCE
1.5
5.5
EA
3.2
2.7
8.6
VDCM
6.1
Lead
scavenger
5.6
Total
3.4
2.9
0.7
3.2
2.7
1.5
79.5
en
en
Source: SRI International, 1979.
-------
Detection limit:
0.01 to 1 ppb per 20-liter sample
Possible interferences:
Blanks and artifact problems as in Method C.
Permissible Exposure Limits
OSHA ACGIH NIOSH
TWA 50 ppm 10 ppm (40 mg/m3) T ppm (4 mg/m3)
STEL 15 ppm (60 mg/m3)
Ceiling 100 ppm 2 ppm (8 mg/m3)
Peak 200 ppm
(5 min in 3 h)
The ACGIH has listed ethylene dichloride for intended changes to
delete the STEL.
Human Toxicity
Acute Toxicity:
Most injurious exposures are acute episodes occurring because
of accidental or industrial exposure. Ingestion of 20 to
50 ml is often fatal within a few days. Blood disorders
appear characteristic of injection, and clotting difficulties
are the most common. Death most often is attributed to circu-
latory and respiratory failure with varying degrees of liver
and kidney damage. The effect of acute exposure to DCE by
skin absorption and inhalation is similar to those following
ingestion, although blood disorders are less prominent.
Headache, weakness, eye irritation, cyanosis, nausea, and
vomiting appear first, followed by loss of consciousness and
respiratory and circulatory failure. Postmortem findings
often include damage to the liver, kidneys, and lungs.
Chronic Toxicity:
In tests by the National Cancer Institute ethylene dichloride
has been shown to be carcinogenic in both rats and mice and
therefore should be considered as a suspected human
carcinogen.
Bibliography
American Conference of Governmental Industrial Hygienists. 1984. TLVs,
Threshold Limit Values for Chemical Substances and Physical Agents in the
Work Environment and Biological Exposure Indices With Intended Changes for
1984-1985.ISB N:0 - 936712-54-6.Cincinnati, OH.
Hawley, G. G. 1981. The Condensed Chemical Dictionary. 10th Edition.
Van Nostrand Reinhold Company, New York.
57
-------
Sampling and Analytical Methods
1. NIOSH Method 1003
a. Charcoal absorption.
b. Carbon disulfide desorption.
c. Gas chromatography.
d. Flame ionization detector.
Detection limit:
0.7 ppm for ethylene dichloride per 3-liter sample
0.6 ppm for p-dichlorobenzene per 3-liter sample
Possible interferences:
None identified.
2. Method B (Appendix A): C2-C18 hydrocarbons and other
nonpolar organics with a boiling point of 100° to 175°C.
a. Whole air collection in canister.
b. Cryogenic concentration.
c. Gas chromatography/flame ionization detection (gas
chromatography/electron capture detection may also be
used).
Detection limit:
0.1 ppb per 100-ml sample
Possible interferences:
Storage times greater than a week are not recommended.
3. Method C (Appendix A): C6-C12 hydrocarbons and other
nonpolar organics with boiling point between 60° and 200°C.
a. Adsorption on Tenax.
b. Thermal desorption.
c. Gas chromatography/mass spectrometry analysis (gas
chromatography/electron capture detection also may be
used).
Detection limit:
1 to 200 ppt per 20-liter sample
Possible interferences:
Blank levels usually limit sensitivity; artifacts due to
reactive components (03, NO ) can be a problem. Sample
can be analyzed only once.
4. Method D (Appendix A): C6-C12 hydrocarbons and other
nonpolar organics with boiling point of 60° to 200°C.
a. Adsorption on Tenax.
b. Thermal desorption into canisters.
c. Gas chromatography/flame ionization detection, or gas
chromatography/mass spectrometry analysis (gas chromato-
graphy/electron capture detection also may be used.)
58
-------
TABLE E-30. ESTIMATED 1977 EDO EMISSIONS AS SOLID WASTE
AND TO WATER FROM ETHYLENE DICHLORIDE PRODUCTION
Emission factor, kg/rut
Direct chlorination
Oxychlorination
Emissions ,a 1000 mt/yr
Direct chlorination
Oxychlorination
Total emissions
Solid waste
1.5
2.8
4.5
6.1
10.6
Water
2.9
4.6
8.5
10.0
18.5
Assumes 58 percent direct chlorination and 42 percent Oxychlorination
and an EDC production of 5,194,000 mt/yr.
Source: SRI International, 1979.
59
-------
International Agency for Research on Cancer. 1979. IARC Monographs on the
Evaluation of Carcinogenic Risk of Chemicals to Man"Volume Zv,
1,2-Dlchloroethane"!Lyon, France, pp. 429-448.
National Fire Protection Association. 1983. National Fire Codes, A Comp-
liance of NFPA Codes, Standards, Recommended Practices, and Manuals.
Volume 13.NFPA, Quincy, MA.
Sax, I. N. 1981. Dangerous Properties of Industrial Materials.
Sixth Edition. Van Nostrand Reinhold Company, New York.
Sittig, M. 1981. Handbook of Toxic and Hazardous Chemicals. Noyes
Publications, Park Ridge, NJ.
SRI International. 1979. Assessment of Human Exposures to Atmospheric
Ethylene Pi chloride. Prepared for the U.S. Environmental Protection
Agency, Office of Air Quality Planning and Standards, Research Triangle
Park, NC.
U.S. Department of Health and Human Services. 1983. Chemical Registry of
Toxic Effects of Chemical Substances 1981 to 1982. National Institute for
Occupational Safety and Health.Cincinnati, OH.
U.S. Department of Health and Human Services. 1984. Manual of Analytical
Methods. Third Edition. National Institute for Occupational Safety and
Health. Cincinnati, OH.
U.S. Environmental Protection Agency. 1977. Chemical Hazard Information
Profile (CHIP) - 1,2-Dichloroethane. Office of Toxic Substances.
Washington, D.C.
U.S. Environmental Protection Agency. 1980. Treatability Manual: Volume 1,
Treatebility Data. EPA 600-8-80--042a.
Weast, R. T. 1981. CRC Handbook of Chemistry and Physics. 61st Edition.
CRC Press, Inc., Boca Raton, FL.
60
-------
Chemical Name
Ethylene dibromide
CAS Number
106-93-4
Chemical Classification
Halogenated hydrocarbon (unsaturated)
Synonyms
Aethylenbromid; bromofume; bromuro di etile; celmide; DBE; 1,2-
dibromaethan; 1,2-dibromoethano; dibromoethane; alpha-beta-dibromo-
ethane; sym-dibromoethane; 1,2-dibromoethane; 1,2-dibromoethane
(DOT); dibromure d1ethylene; 1,2-dibromethaan; dow fume 40; dowfume
EBD; dowfume W-8; dowfume W-85; dwubrometan; EDB; EDB-85; E-D-Bee;
ENT 15,349; ethylene bromide; ethylene dibromide; ethylene
dibromide (DOT); 1,2-ethylene dibromide; fumo-gas; glycol bromide;
glycol dibromide; iscobrome-D; kopfume; NCI-C00522; nephis;
pestmaster; pestmaster EDB-85; soilbrom-40; soilbrom-85;
soilbrome-85; soilbrom-90EC; soil fume; unifume.
Physical/Chemical Properties
Description:
Colorless, nonflammable liquid, sweet odor, emulsifiable.
Boiling Point:
131°C
Melting Point:
9°C
Molecular Weight:
187.9
Chemical Formula:
BrCH2CH2Br
Vapor Pressure:
17.4 mm at 30°C
Vapor Density:
6.48 (air = 1)
Refractive Index:
ND20 = 1.5387
61
-------
Solubility:
Miscible with most solvents and thinners; slightly soluble in
water.
Log Partition Coefficient (octanol/water):
Not available
Photochemical Reactivity:
Ethylene dibromide resists atmospheric oxidation by peroxides
and ozone, typically showing half-lives in excess of 100 days
in those reactions. Generally less reactive in the atmosphere
than corresponding alkanes or olefins.
Chemical Reactivity:
Reacts as alkylating agent and liberates bromide. The
chemical has a half-life of 5 to 10 days toward hydrolysis
under neutral conditions at ambient temperature in an aquatic
environment. Generally inert at normal temperatures, although
slight decomposition may result from exposure to light. It is
hydro!ized to ethylene glycol and bromothanol at elevated
temperatures. When heated to 340° to 370°C, ethylene
dibrodmide decomposes to vinyl bromide and hydrobromic acid.
The terminal halogen atoms are reactive, which makes the
compound a useful synthetic intermediate. It is the least
expensive organic bromine compound available.
Environmental Fate
C-Br bond can photolyze in atmosphere. Photooxidation is probably
important in the atmosphere. Volatilization is the major transport
mechanism. It is not known whether rates of atmospheric degrada-
tion are sufficient to handle the environmental burden adequately.
In about 2 months, EDB is converted almost completely and quantita-
tively to ethylene in soil culture.
Source of Emissions
Production:
Action of bromine on ethylene.
Uses:
Scavenger for lead in gasoline (over 85 percent, used for this
purpose. This use will be phased out as leaded gasoline is
phased out.)
Grain fumigant
General solvent
Waterproofing preparations
Organic synthesis, including vinyl bromide
Fumigant for tree crops
Tables E-31 through E-35 present ethylene dibromide
production, consumption, and emission data.
62
-------
TABLE E-31. CAPACITIES OF ETHYLENE DIBROMIDE MANUFACTURING AND FORMULATING FACILITIES
Location
Arkansas
El Dorado
Great Lakes Chemical Corp.
Magnolia
Dow Chemical Co
Ethyl Corp. (Bromet Co.)
Total
California
Antioch
E. I. Du Pont de Nemours & Co., Inc.
Louisiana
Baton Rouge
Ethyl Corporation
Michigan
Midland
Dow Chemical Company
New Jersey
Deepwater
E. I. Du Pont de Nemours & Co., Inc.
Texas
Beaumont
Houston Chemical Company
(PPG Industries)
Freeport
Nalco Chemical Company
Pasadena
Ethyl Corporation
EDB
capacity,
106 kg
23
14
68
82
39
16
Production
of vinyl
bromide
X
X
Production
of fumigant
X
X
X
X
X
TELa
capacity,
106 kg
79
79
79
54
18
79
Estimated
EDBD use for
TEL, 106 kg
14
14
14
10
3
14
CO
Source: SRI International, 1978.
aTetraethyl lead.
Ethylene dibromide.
-------
TABLE E-32. ESTIMATES OF ANNUAL
CONCENTRATIONS FOR
AVERAGE ETHYLENE DIBROMIDE
SELECTED SMSAs
SMSA
SMSAs >2, 000 ,000
Pittsburgh
San Francisco
SMSAs 1,000,000 - 2,000,000
Columbus, OH
Milwaukee
SMSAs 500,000 - 1,000,000
Sacramento
Providence - Warwick -
Pawtucket
SMSAs 250,000 - 500,000
Wichita
Harris burg
Population
2,333,600
3,135,900
1,055,900
1,423,000
851,300
854,400
375,600
425,500
Area
10V
7.8
6.2
6.2
3.7
8.7
2.4
6.2
4.1
Automobile
registration
2,358,600
688,300
567,803
642,531
439,803
869,100
221,715
198,997
Emission
rate/
lO'1*
g/s-m2
4.8
1.8
1.7
2.8
0.80
5.8
0.57
0.77
Wind
speed
m/s
5
3
5
5
3
7
7
5
EDB concentration
10"3 yg/m3
2.1
1.4
0.66
1.2
0.60
1.9
0.18
0.35
PPt
0.3
0.2
0.90
0.2
0.08
0.2
0.02
0.05
aAssumes 80 percent of vehicles use leaded gasoline.
Ethylene dibromide.
Source: SRI International, 1978.
-------
TABLE E-33. ESTIMATES OF AVERAGE ANNUAL ETHYLENE DIBROMIDE CONCENTRATIONS
FOR CITIES WITH POPULATIONS EXCEEDING 1,000,000
City
Chicago
Detroit
Houston
Los Angeles
New York
Philadelphia
SMSA
population,
103
6,998.8
4,446.3
2,163.4
6,938.3
9,746.4
4,826.3
City
population,
103
3,173
1,387
1,320
2,747
7,647
1,862
City
area,
10V
0.57
0.35
1.1
1.2
0.77
0.33
Automobile
registration
1,324,171
675,065
701,766
1,490,483
1,707,891
944,660
Emission
rate,
10" 10
g/s-m2
3.71
3.08
1.01
1.98
3.54
4.57
Wind
speed,
m/s
5
6
6
3
7
6
EDB concentration
Central city
10" 3
yg/m3
16
11
4
14
11
17
PPt
2.1
1.4
0.5
1.8
1.4
2.2
Suburban
10" 3
yg/m3
6.6
7.7
0.74
3.0
1.8
1.0
PPt
0.9
1.0
0.1
0.4
0.2
0.1
CTl
Assumes 80 percent of vehicles use leaded gasoline.
Ethylene dibromide.
Source: SRI International, 1978.
-------
TABLE E-34. RESULTS OF ETHYLENE DIBROMIDE MONITORING IN THE
VICINITY OF MANUFACTURING FACILITIES
Company
Dow
Ethyl Corp.
Location
Magnolia, Ark.
Magnolia, Ark.
Number
of a
sites9
1
1
Total
sampling
time, h
4
8
Concen-
tration,
ppb
13.2
3.1
Standard
deviation
0.9
4.3
All sites were within 100 m of the plant.
Samples were discontinuous; two were taken near the Dow facility and five
near the Ethyl Corporation facility.
cTo convert to yg/m3, divide by 0.13.
Source: SRI International, 1978.
TABLE E-35. ESTIMATES OF ETHYLENE DIBROMIDE EXPOSURES FROM
SELF-SERVICE GASOLINE PUMPS
Customer
1
2
3
Nozzle
time, min
2.5
1.1
1.6
Gallons
pumped
14
8
9
Estimated
EDBa level
ug/m3
0.345
0.972
5.220
ppt
45
126
679
Average Nozzle Time = 1.7 min.
Time-weighted average exposure = 260 ppt.
aEthylene dibromide.
Source: SRI International, 1978. The conversion is based on differences in
vapor pressure and concentration between benzene and ethylene
dibromide in gasoline.
66
-------
Storage and Transportation:
Protection against physical damage is required. Should be
stored in cool, dry, well-ventilated location, away from any
area where the fire hazard may be acute. Shipped in glass
bottles, metal drums, and tank cars.
Disposition:
Ethylene dibromide may be disposed of by controlled
incineration with adequate scrubbing and ash disposal
facilities.
Sampling and Analytical Methods
1. NIOSH Method 1008
a. Solid Sorbent Tube (coconut shell charcoal, 100 mg/50 nig).
b. Gas chromatography, electron capture detector.
Detection limit:
0.04 mg/m3 per 25-liter sample
Possible interferences:
None idnetified.
2. NIOSH Method S104
a. Adsorption with charcoal.
b. Desorption with carbon disulfide.
c. Gas chromatography.
Detection limit:
22 to 660 mg/m3 per 1-liter sample
Possible interferences:
Any compound that has the same retention time may inter-
fere. High humidity.
Permissible Exposure Limits
OSHA ACGIH NIOSH
TWA 20 ppm
Ceiling 30 ppm none 1 mg/m3 (15 min)
Peak 50 ppm (5 min)
The ACGIH lists ethylene dibromide as an industrial substance
suspected of carcinogenic potential for man (skin).
Human Toxicity
Acute Toxicity:
Severe skin irritant. Serious toxic interaction between
inhaled ethylene dibromide and ingested disulfiram. One case
of fatal poisoning reported after ingestion of 4.5 ml.
67
-------
Patient vomited recurrently, had watery diarrahea, became
anuric, and died 2 days later. Massive damage of the kidneys
noted at autopsy.
Chronic Toxicity:
Both the National Cancer Institute and the National Toxicology
Program have found ethylene dibromide to be carcinogenic in
both mice and rats; therefore, it can be considered a
suspected human carcinogen.
Bibliography
American Conference of Governmental Industrial Hygienists. 1984. TLVs,
Threshold Limit Values for Chemical Substances and Physical Agents in the
Work Environment and Biological Exposure Indices With Intended Changes for
1984-1985. ISB N:0 - 936712-54-6., Cincinnati, OH.
Hawley, G. G. 1981. The Condensed Chemical Dictionary. 10th Edition. Van
Nostrand keinhold Company, New York.
International Agency for Research on Cancer. 1977. IARC Monographs on the
Evaluation of Carcinogenic Risk of Chemicals to Man" Volume 15, Ethyle"ne
Dibromide. Lyon, France, p. 195.
National Fire Protection Association. 1983. National Fire Codes, A Comp-
liance of NFPA Codes, Standards, Recommended Practices, and Manuals.
Volume 13.NFPA, Quincy, MA.
Sax, I. N. 1981. Dangerous Properties of Industrial Materials. Sixth
Edition. Van Nostrand Reinhold Company, New York.
Sittig, M. 1981. Handbook of Toxic and Hazardous Chemicals. Noyes
Publications, Park Ridge, NJ.
SRI International. 1978. Atmospheric Ethylene Dibromide: A Source Specific
Assessment. Prepared for the U.S. Environmental Protection Agency, Office
of Toxic Substances, Washington, D.C.
U.S. Department of Health and Human Services. 1983. Chemical Registry of
Toxic Effects of Chemical Substances 1981 to 1982. National Institute for
Occupational Safety and Health.Cincinnati, OH.
U.S. Department of Health and Human Services. 1984. Manual of Analytical
Methods. Third Edition. National Institute for Occupational Safety and
Health. Cincinnati, OH.
68
-------
U.S. Environmental Protection Agency. 1980. TreatabJiity Manual: Volume 1,
Treatability Data. EPA 600-8-80-042a.
Weast, R. T. 1981. CRC Handbook of Chemistry and Physics. 61st Edition.
CRC Press, Inc., Boca Raton, FL.
69
-------
Chemical Name
Ethylene oxide
CAS Number
65-21-8
Chemical Classification
Epoxide
Synonyms
Aethylenoxid; anprolene; benvicide; carboxide; cry-oxide; di-
hydroxirene; dimethylene oxide; E.O.; 1,2-epoxyacthan; epoxyethane;
1,2-epoxyethane; ethyleen oxide; ethylene oxide (DOT); ethylene
(oxide'd); etilene (ossido di); ETO; eto; etylenutlener;
NCI-C50088; oxacyclopropane; oxane; oxidoethane;
alpha-beta-oxidoethane; oxiraan; oxiran; oxirane; oxirene,
dihydro-; oxyfume 12; oxyfume sterilant 20; pennoxide, steroxide
12; steroxide 20; t-gas;
Physical/Chemical Properties
Description:
Colorless gas at room temperature. Ether-like odor over 700
ppm.
Boiling Point:
10.73°C
Melting Point:
Molecular Weight:
44.1
Chemical Formula:
CH2CH20
Vapor Pressure:
1095 mm at 20°C
Vapor Density:
1.52 (air = 1)
Refractive Index:
Np7 = 1.3597
Solubility:
Soluble in organic solvents; miscible with water in all pro
portions.
70
-------
Log Partition Coefficient (octanol/water):
-0.3
Photochemical Reactivity:
Reactivity toward OH- is the same as butane. No reaction
toward photolysis.
Chemical Reactivity:
Reacts readily with proton donors such as alcohols, amines and
thiols. Decomposes violently at temperatures above 800°C.
Ethylene oxide will polymerize violently if contaminated with
aqueous alkalies, amines, mineral acids, metal chlorides, or
metal oxides. Incompatible with alkalines and acids. Reacts
with active hydrogen compounds (e.g., alcohols, amines, and
sulphydryl compounds) and with inorganic chloride in food to
form ethylene chlorohydrin. Also reacts with 4-4'-nitrobenzyl
pyridine.
Environmental Fate
In connection with the treatment of foods with ethylene oxide, the
compound reacts with inorganic chloride to form ethylene
chlorohydrin.
Source of Emissions
Production:
From oxidation of ethylene in air or oxygen with silver cata-
lyst.
From the reaction of ethylene with hypochlorous acid followed
by dehydrochlorination of the resulting chlorohydrin with lime
(chlorohydrin process).
Uses:
Manufacture of ethylene glycol and higher glycols
Surfactants
Acrylonitrile
Ethanolamines
Petroleum demulsifier
Fumigant
Rocket propellent
Industrial sterilant, e.g., medical plastic tubing
Fungicide
Tables E-36 through E-41 and Figure E-2 present data on ethyl-
ene oxide production, consumption, and emissions.
Storage:
Should be protected against physical damage. Should be kept
cool, below 86°F. Should be stored outside, away from build-
ings and other materials, in insulated tanks or containers,
shielded from sun and heat or provided with cooling facilities
and protected by a properly designed water-spray system.
71
-------
TABLE E-36. ETHYLENE OXIDE PRODUCERS
Source
BASF Wayandotte
Celanese
Dow
Jefferson Chemical
Northern Petrochemical
01 in
PPG
Shell Chemical
Sunolin Chemical
Texas Eastman
Union Carbide
Location
Geismar, LA
Clear Lake, TX
Freeport, TX
Plaquemine, LA
Port Neches, TX
East Morris, IL
Brandenburg, KY
Beaumont, TX
Geismar, LA
Claymont, DE
Longview, TX
Seadrift, TX
Taft, LA
Type of
process
B
B
A
A
A
B
B
B
B
B
B
A
A
Total
1978
estimated .
production,
106 Ib/yr
222
340
322
351
340
165
75
107
193
72
136
594
723
3640
1978
estimated
capacity,
106 Ib/yr
310
475
450
490
475
230
105
150
270
100
190
830
1010
5085
Geographic
coordinates
30 11 34/91 00 42
29 37 17/95 03 51
28 59 15/95 24 45
30 19 00/91 15 32
29 57 45/93 56 00
41 24 08/88 17 18
38 00 27/86 06 50
30 03 40/94 02 30
30 11 00/90 59 00
39 48 20/75 25 40
32 25 55/94 41 06
28 30 31/96 46 18
29 58 00/97 27 00
rv>
A = air oxidation process.
B = oxygen oxidation process.
The distribution of production for each producer is determined by the ratio of total U.S. production/
total capacity times individual site capacity.
Source: Systems Applications, Inc. 1980.
-------
TABLE E-37. ETHYLENE OXIDE PRODUCERS AND USERS
Source
BASF Wayandotte
Celanese
Dow
Jefferson
Northern Petrochemical
Olin
PPG
Shell Chemical
Sunolin Chemical
Texas Eastman
Union Carbide
ICI Americas
Location
Geismar, LA
Clear Lake, TX
Freeport, TX
Plaquemine, LA
Port Neches, TX
East Morris, IL
Brandenburg, KY
Beaumont, TX
Geismar, LA
Claymont, DE
Longview, TX
Seadrift, TX
Taft, LA
Hopewell, VA
-
1978 capacity (Ib x 106)
Ethylene
oxide
310
475
450
490
475
230
105
150
270
100
190
830
1010
Ethylene
glycol
330
550
360
350
50
200
200
180
870
1200
33
Diethylene
glycol
20
50
25
50
35
35
5
20
20
20
80
100
Triethylene
glycol
10
50
20
2
5
75a
Glycol
ethers
230
40
70
20
50
25
490a
Ethanol-
amines
40
100
80
25
230
OO
Includes a plant in Penuelas, Puerto Rico.
Source: Systems Applications, Inc. 1982.
-------
TABLE E-38. END-USE DISTRIBUTION OF ETHYLENE OXIDE IN 1978
Ethylene glycol polyester
Ethylene glycol antifreeze
Ethylene glycol (other uses)
Surface active agents
Ethanol amines
Glycol ethers
Other
Total
Usage
106 Ib/yr
910
837
364
546
255
255
473
3640
%
25
23
10
15
7
7
13
100
Source: Systems Applications, Inc., 1980.
74
-------
TABLE E-39. ESTIMATED 1978 NATIONWIDE EMISSIONS OF ETHYLENE OXIDE
Source
Producers3
Air oxidation
Oxygen oxidation
Users
EG polyester
EG antifreeze
EG (other uses)
Surface active agents
Ethanolamines
Glycol ethers
Other
Production/
usage
106 Ib/yr
2330
1310
910
837
364
546
255
255
473
Usage
%
25
23
10
15
7
1
13
Total
Total emissions
Ib/yr
1,277,000
410,900
1,687,900
9/s
18.4
5.9
24.3
Total emissions from producers also include total emissions from users
since ethylene oxide is produced and used at the same site.
EG = ethylene glycol.
Source: Systems Applications, Inc., 1982.
75
-------
TABLE E-40. ETHYLENE OXIDE EMISSIONS FROM PRODUCERS
(Air Oxidation Process)
Company
Dow
Jefferson
Union Carbide
Location
Freeport, TX
Plaquemine, LA
Port Neches, TX
Seadrift, TX
Taft, LA
Total
Process
emissions,
Ib
169,000
184,000
179,000
312,000
380,000
1,224,000
Storage
emissions,
Ib
6,880
7,500
7,270
12,700
15,500
49,850
Fugitive
emissions,
Ib
529
577
559
977
1,190
3,832
Total emissions
Ib
176,000
192,000
187,000
326,000
397,000
1,278,000
9/s
2.5
2.8
2.7
4.7
5.7
18.4
en
Source: Systems Applications, Inc. 1982.
-------
TABLE E-41. ETHYLENE OXIDE EMISSIONS FROM PRODUCERS
(Oxygen Oxidation Process)
Company
BASF
Celanese
Northern Petrochemical
Olin
PPG
Shell Chemical
Stmolin Chemical
Texas Eastman
Location
Geismar, LA
Clear Lake, TX
Port Neches, TX
Brandenburg, KY
Beaumont, TX
Geismar, LA
Claymont, DE
Longview, TX
Total
Process
emissions,
Ib
1,032
135
77,340
35,150
50,150
90,460
33,750
63,740
351,667
Storage
emissions,
Ib
156
12
11,690
5,314
7,581
13,670
5,101
9,636
53,158
Fugitive
emissions,
Ib
12
1,853
899
409
583
1,052
392
741
5,942
Total emissions
Ib
1,200
2,000
89,930
40,880
58,320
105,200
39,240
74,120
410,900
g/s
.02
.03
1.3
0.6
0.8
1.5
0.6
1.1
5.9
Source: Systems Applications, Inc. 1982.
-------
—I
00
NOTE: NUMERALS DENOTE NUMBER OF PLANTS.
Figure E-2. Specific point sources of ethylene oxide emissions
Source: Systems Applications, Inc. 1980.
-------
Adequate diking and drainage should be provided in tank area
to confine and dispose of liquid in case of a tank rupture.
Pits and depressions should be avoided. Inside storage should
be held at a minimum and confined to a standard fire-resistant
flammable liquids storage room, provided with continuous
ventilation and free of sources of ignition.
Transportation:
Shipped in steel cylinders, drums, insulated tank cars, and
tank barges. The U.S. Bureau of Explosives requires a red
label on all shipments. Not acceptable on passenger planes.
Disposition:
Ethylene oxide may be disposed of as a concentrated waste
containing no peroxide by discharging liquid at a controlled
rate near a pilot flame or as a concentrated waste containing
peroxides by perforation of a container of the waste from a
safe distance followed by open burning. Ethylene oxide is a
hazardous waste with a hazardous waste number of U 115 as-
signed by EPA.
Sampling and Analytical Methods
1. NIOSH Method S286
a. Adsorption on charcoal.
b. Desorption with carbon disulfide.
c. Gas chromatography.
Detection limit:
20 to 270 mg/m3 for a 5-liter sample.
Possible interferences:
High humidity. Any compound with the same retention time
may cause an interference.
2. Method A (Appendix A)
a. Direct gas injection into gas chromatograph/flame.
b. lonization detector.
Detection limit:
0.01 ppm
Possible interferences:
Losses from surface adsorption may occur in some cases.
3. Method B (Appendix A) C2-C18 hydrocarbons and other nonpolar
organics with a boiling point of 100° to 175°C
a. Whole air collection in canister.
b. Cryogenic concentration.
c. Gas chromatography/flame ionization detection.
Detection limit:
0.1 ppb per 100-ml sample
79
-------
Possible interferences:
Water soluble compounds are not readily analyzed. Stor-
age times greater than a week are not recommended.
4. Method E (Appendix A)
a. Adsorption on charcoal.
b. Desorption with CS2.
c. Analysis by gas chromatography/flame ionization detection.
Detection limit:
0.1 to 1 ppm per 10-liter sample
Possible interferences:
Sensitivity much poorer than for thermal desorption.
Permissible Exposure Limits
OSHA AC6IH
TWA 1 ppm 1 ppm (2 mg/m3)
The ACGIH lists ethylene oxide as an industrial substance
suspected of carcinogenic potential for man.
Human Toxicity
Acute Toxicity:
Powerful irritant (systemic). High toxicity effect
through oral, inhalation, intraperitoneal, and intrave-
nous means. An irritant to skin, eyes, and mucous mem-
branes of respiratory tract. High concentrations can
cause pulmonary edema.
Chronic Toxicity:
Tests on rats found ethylene oxide to be an equivocal
tumorigenic agent. Currently tested by the National
Toxicology Program for carcinogenesis bioassay.
Bibliography
American Conference of Governmental Industrial Hygienists. 1984. TLVs,
Threshold Limit Values for Chemical Substances and Physical Agents in the
Work Environment and Biological Exposure Indices With Intended Changes for
gical tx
12-54-6.
1984^198b. ISB N:0 - 936712-54-6. Cincinnati, OH.
Hawley, G. G. 1981. The Condensed Chemical Dictionary. 10th Edition. Van
Nostrand Reinhold Company, New York.
International Agency for Research on Cancer. 1976. IARC Monographs on the
Evaluation of Carcinogenic Risk of Chemicals to Man. Volume II - Ethylene
Oxide.Lyon, France, p. 157 to 167
80
-------
Kirk-Othmer. 1980. Encyclopedia of Chemical Technology Third Edition.
Volume 9. Ethylene"Oxide, John Wiley and Sons, New York.
National Fire Protection Association. 1983. National Fire Codes. A Com-
pliance of NFPA Codes, Standards. Recommended Practices, and Manuals.
Volume 13.NFPA, Quincy, MA.
Sax, I. N. 1981. Dangerous Properties of Industrial Materials. Sixth
Edition. Van Nostrand Reinhold Company, Mew York.
Sittig, M. 1981. Handbook of Toxic and Hazardous Chemicals. Noyes
Publications. Park Ridge, NJ.
Systems Applications, Inc. 1980. Human Exposure to Atmospheric Concentra-
tions of Selected Chemicals. Volume 1. PB 81-1932!>Z.Systems Applica-
tions, Inc., San Rafael, CA.
Systems Applications, Inc. 1982. Human Exposure to Atmospheric Concentra
tipns of Selected Chemicals. Volume II.Appendix A-14. Ethylene Oxide.
EPA Contract No. 68-02-3066.SAI 58-EF81-156R2. Systems Applications,
Inc., San Rafael, CA.
U.S. Department of Health and Human Services. 1983. Chemical Registry of
Toxic Effects of Chemical Substances 1981 to 1982. National Institute for
Occupational Safety ana Health.Cincinnati, OH.
U.S. Department of Health and Human Services. 1984. Manual of Analytical
Methods. National Institute for Occupational Safety and Health.
Cincinnati, OH.
Weast, R. T. 1981. CRC Handbook of Chemistry and Physics. 61st Edition.
CRC Press, Inc., Boca Raton, FL.
81
-------
Chemical Name
Formaldehyde
CAS Number
50-00-0
Chemical Classification
Aldehyde
Synonyms
Aldehyde formique; aldehyde formica; BFV; FA; fannoform; formalde-
hyd; formaldehyde, as formalin solution (DOT); formalin-loesungen;
formalith; formicaldehyde; forme!; FYDE; hoch; ivalon; karsan;
cysoform; methanal; methyl aldehyde; methylene glycol; methylene
oxide; morbicide; NCI-C02799; opplossingen; oxomethane; oxymeth-
ylene; paraform; polyoxymethylene glycols; superlysoform; tetra-
oxynethylene; trioxane
Physical/Chemical Properties
Description:
Gas; strong pungent odor.
Boiling Point:
-19°C
Melting Point:
Molecular Weight:
30.0
Chemical Formula:
HCHO
Vapor Pressure:
760 mm at -19.5°C
Vapor Density:
1.067 (air = 1)
Refractive Index:
Not available
Solubility:
Soluble in water and alcohol.
32
-------
Log Partition Coefficient (octanol/water):
-0.96
Photochemical Reactivity:
Reactivity toward OH- is 2 to 4 times butane. Photolysis is 9
percent per hour at full sunlight. Major atmospheric
precursors are hydrocarbons (photooxidation). Formed by
incomplete combustion of many organic substances. Equilibrium
is approximately 5 percent for methane hydrocarbons.
Chemical Reactivity:
Reacts with NO at about 180°F, when the reaction becomes
explosive. Also reacts violently with HlO.-aniline and
performic acid, nitromethane, magnesium carbonate, and
hydrogen peroxide. Can react with hydrogen chloride and
inorganic chlorides to yield bis-chloromethyl ether (BCME)
which is a potent carcinogen. This reaction occurs only at
high (500 to 3,000 ppm) concentrations.
Environmental Fate
Bioaccumulation of formaldehyde is unlikely due to its high
chemical reactivity. Degradation in the atmosphere is by
photochemical process, and it biodegrades to formic acid, methyl
alcohol, carbon dioxide, and water.
Source of Emissions
Production:
Oxidation of synthetic methanol or low boiling petroleum gases
such as propane and butane. The most common catalysts are
silver, copper, or iron-molybdenum.
Uses:
Urea and melamine resins
Polyacetal resins
Phenolic resins
Ethylene glycol
Pentaerythritol
Hexamethylenetetramine
Fertilizer
Dyes, medicine (disinfectant, germicide)
Embalming fluids
Preservative
Hardening agent
Reducing, agent, as in recovery of gold and silver
Corrosion inhibitor in oil wells
Durable-press treatment of textile
Industrial sterilant
Treatment grain
Tables E-42 through 4-46 and Figure E-3 present formaldehyde
production, consumption and emission data.
83
-------
TABLE E-42. PRODUCTION OF FORMALDEHYDE
Source
Allied Chemical
Borden, Inc.
Celanese Chemical
Chembond Corp.
Du Pont
GAF Corp.
Location
South Point, OH
Demopolis, AL
Diboll, TX
Fayetteville, NC
Geismar, LA
Louisville, KY
Sheboygan, WI
Fremont, CA
Kent, WA
LaGrande, OK
Missoula, MT
Springfield, OR
Bishop, TX
Newark, NO
Rock Hill, SC
Springfield, OR
Winnifield, LA
Belle, WV
LaPorte, TX
Healing Springs, NC
Linden, NJ
Toledo, OH
Calvert City, KY
1978
Estimated
production,,
10r> Ib/yr
222
72
57
168
179
57
93
161
57
46
64
172
1075
84
84
107
50
358
229
158
115
193
72
1978
Estimated
capacity,
10fe Ib/yr
310
100
80
235
250
80
130
225
80
65
90
240
1500
117
117
150
70
500
320
220
160
270
100
Geographic coordinates,
Latitude/longitude
38 25 43/82 36 00
32 30 48/27 50 06
31 11 52/94 46 50
35 01 43/78 51 41
30 13 00/91 01 00
38 12 09/85 51 49
43 45 26/87 46 17
37 32 06/121 57 24
47 23 12/122 13 15
45 20 31/100 02 02
46 54 10/114 40 00
44 02 60/122 59 06
27 34 06/97 49 27
40 43 30/74 07 25
34 57 25/80 57 32
44 02 60/122 59 06
31 54 49/92 40 35
38 12 13/81 28 34
29 42 04/95 02 05
35 01 56/80 10 30
40 36 02/74 12 08
41 39 22/83 33 20
37 02 50/88 21 12
CO
(continued)
-------
TABLE E-42 (continued)
Source
Georgia-Pacific Corp.
Gulf Oil Corp.
Hercules Inc.
Hooker Chemicals &
Plastics
IMC Chemical Group
Monsanto Corp.
Pacific Resins and
Chemicals
Location
Albany, OR
Columbus, OH
Coosbay, OR
Crossett, AR
Russelville, SC
Taylorsville, MS
Vienna, GA
Lufkin, TX
Vicksburg, MS
Louisiana, MO
Wilmington, NC
Tonawanda, NY
Seiple, PA
Sterling ton, LA
Addyston, OH
Chocolate Bayou, TX
Eugene, OR
Springfield, MA
Eugene, OR
1978
Estimated
production,
106 lb/yra
86
72
65
115
143
86
72
72
43
122
72
97
47
22
72
140
72
211
68
1978
Estimated
capacity,
10& Ib/yr
120
100
90
160
200
120
100
100
60
170
100
135
65
30
100
195
100
295
95
Geographic coordinates,
Latitude/longitude
44 37 07/123 05 13
39 53 07/82 56 45
42 27 26/124 10 47
33 08 36/93 02 11
33 20 52/79 58 00
39 51 00/89 25 00
37 07 30/83 49 00
31 21 00/94 47 00
32 17 00/90 54 00
39 26 24/91 03 37
34 19 09/77 59 23
43 02 47/78 51 44
40 38 12/75 31 58
32 43 25/92 08 56
39 07 30/84 42 58
29 14 55/95 12 45
44 02 59/123 08 19
42 09 33/72 29 09
44 01 00/123 05 05
(continued)
-------
TABLE E-42 (continued)
Source
Reichhold Chemicals, Inc.
Tenneco, Inc
Wright Chemical Corp.
Location
Hampton, SC
Houston, TX
Kansas City, KA
Malvern, AR
Moncure, NC
Tacoma, WA
Tuscaloosa, AL
White City, OR
Fords, NJ
Garfield, NJ
Riegelwood, NC
1978
Estimated
production,
106 lb/yra
36
86
36
79
86
36
50
179
133
72
57
6,400
1978
Estimated
capacity,
106 Ib/yr
50
120
50
110
120
50
70
250
185
100
80
8,929
Geographic coordinates,
Latitude/longitude
32 53 33/81 06 10
29 44 50/95 10 00
39 09 28/94 37 41
34 24 09/92 48 45
35 31 18/79 04 52
47 16 11/122 22 57
33 12 03/87 34 00
42 26 18/122 07 07
40 30 50/74 19 17
40 52 28/74 06 49
34 19 22/78 12 09
00
en
The distribution of production for each producer is determied by the ratio of total U.S. production
to total U.S. capacity as compared to individual plant opacity.
Source: System Applications, Inc. 1982.
-------
TABLE E-43. FORMALDEHYDE CONSUMPTION BY END USE
End-Use
Urea resins
Phenolic resins
Butanediol
Acetal resins
Pentaerythritol
Hexamethyl enetetrami ne
Melamine resins
Urea formaldehyde concentrates
Chelating agents
Trimethyl ol propane
Other Chemical intermediate uses
Export
Total
Percent
of total
consumption
25.4
24.3
7.7
7.0
6.0
4.5
4.2
3.6
3.6
1.3
11.9
0.5
100.0
End-use
consumption
106 Ib/yr
1630
1560
490
450
380
290
270
230
230
80
760
30
6400
87
-------
TABLE E-44. FORMALDEHYDE CHEMICAL INTERMEDIATE USERS
Source
Butanediol Production
Du Pont Company
GAP Corporation
Location
Houston, TX
Calvert City, KY
Texas City, TX
Total
Acetal Resins Production
Celanese Corporation
Du Pont Company
Bishop, TX
Parkersburg, WV
Total
Pentacrythritol Production
Celanese Corporation
Hercules, Inc.
IMC (CSC)
Perstop AB
Bishop, TX
Louisiana, MO
Seiple, PA
Toledo, OH
Total
Hexamethy 1 enetetrami ne Producti on
Borden, Inc.
W. R. Grace & Company
Occidental Petroleum Co.
Plastics Engineering Co.
Tenneco, Inc.
Wright Chemical Corp.
Fayetteville, NC
Nashua, NH
North Tonawanda, NY
Sheboygan, VII
Fords, NJ
Acme, NC
Total
Trimethylol propane Production
Celanese Corp.
Bishop, TX
1978
Estimated
formaldehyde
consumption, 106 Ib
240
80
80
400
310
140
450
160
100
50
70
380
60
60
50
20
40
60
290
80
Geographic coordinates,
La t i tude/ 1 ong i tude
29 42 04/95 02 05
37 02 50/88 21 12
29 25 29/94 58 07
27 34 06/97 49 27
39 15 27/81 32 52
27 34 06/97 49 27
39 26 24/91 03 37
40 38 12/75 31 58
41 42 33/83 30 00
35 01 43/78 51 41
42 46 00/71 27 52
43 02 47/78 51 44
43 45 00/87 47 00
40 30 50/74 19 17
34 19 22/78 12 09
27 34 06/97 49 27
oo
CO
Source: System Applications, Inc. 1982.
-------
TABLE E-45. 1978 FORMALDEHYDE PRODUCTION EMISSIONS
00
<£>
Company
Allied Chemical
Borden, Inc.
Celanese Chemical
Chembond Corp.
Du Pont
GAF Corp.
Georgia-Pacific Corp.
Gulf 011 Corp.
Hercules Inc.
Hooker Chemicals &
Plastics
IMC Chemical Group
location
South Point, OH
Demopolls, AL
01 boll. TX
Fayettevllle, NC
Geismar, LA
Louisville. KY
Sheboygan, VII
Fremont, CA
Kent, HA
LeGrande, OR
Missoula, MT
Springfield, OR
Bishop, TX
Newark, NJ
Rock Hill, SC
Springfield. OR
Winnlfleld. LA
Belle. WV
LaPorte. TX
Healing Springs, NC
Linden. NJ
Toledo, OH
Calvert City, KY
Albany, OR
Columbus, OH
Coos Bay, OR
Crossett, AR
Russelvllle, SC
Taylorsvllle, HS
Vienna, GA
Lufkln, TX
Vicksburg, MS
Louisiana, MO
Wilmington, NC
Tonawanda, NY
Selple. PA
Sterllngton, LA
1978
production,
106 Ib
222
72
57
168
179
57
93
161
57
46
64
172
1075
84
84
107
50
358
229
158
115
193
72
86
72
65
72
43
143
86
72
72
43
122
72
97
47
22
Type of
process
A
A
A
A
A
A
A
A
A
A
A
A
A
B
B
B
B
A
A
A
A
A
B
B
B
B
A
B
B
B
A
B
B
A
A
A
A
A
Process
emissions,
10" Ib
5.81
.89
.49
.40
.69
.49
.44
.22
.49
.21
.68
4.51
8.84
3.30
3.30
4.20
1.96
9.38
6.00
4.14
3.01
5.06
2.83
3.38
2.83
2.55
0.00
0.00
5.61
3.38
0.00
0.00
1.69
3.20
1.89
2.54
1.23
0.58
Storage
emissions,
10" Ib
0.46
0.15
0.12
0.35
0.37
0.12
0.19
0.33
0.12
0.09
0.13
0.35
0.70
0.43
0.43
0.55
0.26
0.74
0.47
0.33
0.24
0.40
0.37
0.44
0.37
0.34
0.15
0.22
0.74
0.44
0.15
0.37
0.22
0.25
0.15
0.20
0.10
0.05
Fugitive
emissions.
10" Ib
0.91
0.30
0.23
0.69
0.74
0.23
0.38
0.66
0.23
0.19
0.26
0.71
1.36
0.68
0.68
0.86
0.40
1.47
0.94
0.65
0.47
0.79
0.58
0.69
0.58
0.52
0.30
0.35
1.15
0.69
0.30
0.58
0.35
0.50
0.30
0.40
0.19
0.09
Total emissions
10* Ib
7.19
2.33
1.85
5.44
5.79
1.85
3.01
5.21
1.85
1.49
2.07
5.57
10.98
4.41
4.41
5.62
2.62
11.59
7.41
5.11
3.72
6.25
3.78
4.51
3.78
3.41
0.45
0.57
7.51
4.51
0.45
0.95
2.26
3.95
2.33
3.14
1.52
0.71
g/s
1.04
0.34
0.27
0.78
0.83
0.27
0.43
0.75
0.27
0.21
0.30
0.80
1.58
0.63
0.63
0.81
0.38
1.67
1.07
0.74
0.54
0.90
0.54
0.6S
0.54
0.06
0.08
0.33
1.08
0.65
0.06
0.14
0.33
0.57
0.34
0.45
0.22
0.10
(continued)
-------
TABLE E-45 (continued)
10
o
Company
Monsanto Corp.
Pacific Resins and
Chemicals
Relchhold Chemicals, Inc.
Tenneco, Inc
Wright Chemical Corp.
Location
Addyston, OH
Chocolate Bayou, TX
Eugene, OR
Springfield, HA
Eugene, OR
Hampton, SC
Houston, TX
Kansas City, KA
Malvern, AR
Moncure, NC
Tacoma, WA
Tuscaloose, AL
White City, OR
Fords, NO
Garfteld, NJ
Rfegelwood, NC
Total
1978
production ,
106 Ib
72
140
72
211
68
36
86
36
79
86
36
50
179
71
62
72
57
6400
Type of
process
A
A
A
A
A
A
B
A
B
B
B
A
B
A
B
A
B
Process
emissions ,
10" Ib
0.34
0.66
0.34
1.00
1.78
0.94
3.38
0.94
3.10
3.38
1.41
1.31
7.03
1.86
2.43
1.89
2.24
150.24
Storage
emissions ,
10" Ib
0.03
0.05
0.03
0.08
0.14
0.07
0.44
0.07
0.41
0.44
0.19
0.10
0.93
0.15
0.32
0.15
0.29
15.76
Fugitive
emissions,
10" Ib
0.05
0.11
0.05
0.16
0.28
0.15
0.69
0.15
0.64
0.69
0.29
0.21
1.44
0.29
0.50
0.30
0.46
30.86
Total emissions
10" Ib
0.42
0.82
0.42
1.23
2.20
.17
.51
.17
.15
.51
1.89
1.62
9.40
2.30
3.25
2.33
2.99
193.97
9/s
0.06
0.12
0.06
0.18
0.32
0.17
0.65
0.17
0.60
0.65
0.27
0.23
1.35
0.33
0.45
0.34
0.43
27.92
Source: Systems Applications, Inc., 1982.
-------
TABLE E-46. FORMALDEHYDE EMISSIONS FROM CHEMICAL INTERMEDIATE USERS
Source
Butanediol Producers
Du Pont Company
GAF Corporation
Location
Houston, TX
Calvert City, KY
Texas City, TX
Total
Acetal Resins Producers
Celanese Corporation
Du Pont Company
Bishop, TX
Parkersburg, WV
Total
Pentacrythritol Producers
Celanese Corporation
Hercules, Incorporated
IMC (CSC)
Perstorp AB
Bishop, TX
Louisiana, MO
Seiple, PA
Toledo, OH
Total
Hexamethylenetetramine Producers
Borden, Inc.
W. R. Grace & Company
Occidental Petroleum Company
Plastics Engineering Company
Tenneco, Inc.
Wright Chemical Corporation
Fayetteville, NC
Nashua, NH
North Tonawanda, NY
Sheboygan, WI
Fords, NO
Acme, NC
Total
Trimethylol propane Producers
Celanese Corporation
Bishop, TX
Process
emissions,
Ib/yr
480,000
160,000
160,000
800 ,000
391,409
560,000
951,409
369,208
731,000
365,500
511,700
1,977,408
63,000
63,000
52,500
21 ,000
42,000
63,000
304,500
5,050
Storage
emissions,
Ib/yr
120,000
40,000
40,000
200,000
48,927
70,000
118,927
44,445
88,000
44,000
61,600
238,045
9,000
9,000
7,500
3,000
6,000
9,000
43,500
757
Fugitive
emissions,
Ib/yr
120,000
40,000
40,000
200,000
48,927
70,000
118,927
20,708
41,000
20,500
28,700
110,908
18,000
18,000
15,000
6,000
12,000
18,000
87,000
757
Total emissions
Ib/yr
720,000
240,000
240,000
1,200,000
489,263
700 ,000
1,189,263
434,361
860,000
430,000
602,000
2,326,361
90,000
90,000
75,000
30 ,000
60,000
90,000
435,000
6,565
g/s
10.37
3.46
3.46
7.04
10.08
6.25
12.38
6.19
8.67
1.30
1.30
1.08
0.43
0.86
1.30
0.09
Source: Systems Applications, Inc. 1982.
-------
NOTE: NUMERALS DENOTE NUMBER OF PLANTS.
Figure E-3. Specific point sources of formaldehyde emissions.
Source: Systems Applications, Inc., 1980.
-------
Storage and Transportation:
Pure formaldehyde is not available commercially because of its
tendency to polymerize. It is sold as aqueous solutions
containing from 37 to 50 percent formaldehyde by weight and
varying amounts of methanol.
Should be protected against physical damage. Keep separate
from oxidizing and alkaline materials. Indoor storage should
be in storage areas having floors pitched toward a trapped
drain or in curbed retention areas. Minimum storage
temperatures to prevent polymerization range from 83°F for 37
percent formaldehyde containing 0.05 methyalcohol to 29°F for
formaldehyde containing 15 percent methylalcohol. Shipped in
insulated tank cars and tank trucks; 5- to 55-gallon metal
drums, carboys, bottles, and tank barges.
Disposition:
Formaldehyde may be disposed of by incineration. Also, formal-
dehyde may be recovered from waste waters.
Sampling and Analytical Methods
1. NIOSH Method 3501
a. Liquid in bubbler (midget bubbler, 15-ml Girard T
reagent).
b. Polarography.
Detection limit:
4.6 to 19.8 ppm for 18-liter samples.
Possible interferences:
Other volatile aldehydes such as acrylein, crotonaldehyde,
benzaldehyde, and products diffusing out of polyvinyl
chloride tubing may cause significant interference.
2. NIOSH Method 2502
a. Solid Sorbent Tube [2-(benzylamino) ethanol or Chromasorb
102 or XAD-2 120 mg/60 ing].
b. Gas chromatography.
c. Flame ionization detectors.
Detection limit:
0.25 to 4 ppm with 12-liter sample.
Possible interferences:
Phenol has almost the same retention time. Acid mists
may inactivate the sorbent, leading to inefficient
collection of formaldehyde.
3. NIOSH Method 3500
a. Filter and impingers, lym PTFE membrane and two impingers,
each with 20 ml 1 percent sodium bisulfite solution.
b. Visible absorption spectrophotometry.
93
-------
Detection limit:
0.02 to 0.4 ppm for 80-liter sample
Possible interferences:
Phenols in 8:1 excess produce 10 to 20 percent bias.
Ethanol and higher M.W. alcohols, olefins, aromatic
hydrocarbons, and cyclohexanone produce small negative
interferences. Little interference is seen from other
aldehydes.
4. NIOSH Method 235
a. Alumina collection.
b. Methanol-water elution.
c. Spectrophotometric measurement.
Detection limit:
0.3 to 0.7 ppm in 6-liter sample
Possible interferences:
Saturated aldehydes give less than 0.01 percent positive
interference. Phenols cause 10 to 20 percent negative
interference when present in an 8:1 ratio over formalde-
hyde ethylene and propylene present in a 10:1 excess over
formaldehyde give 5 to 10 percent negative interference,
while 2-methyl-l,3-butadiene in a 15:1 excess over formal-
dehyde causes a 15 percent negative interference. Cyclo-
hexanone causes a bleaching of the final color.
5. Method J (Appendix A)
a. Collection in dinitrophenyl hydrazine (DNPH).
b. Solvent extraction of DNPH derivitives.
c. Reversed phase high pressure liquid chromatography
6. Method K (Appendix A)
a. Collection in 1 percent sodium bisulfate impinger.
b. Determination of formaldehyde using chromotropic acid,
acrolein, and mercuric chloride hexylrecorcinol with gas
chromatography/flame ionization detection
Detection limit:
10 to 30 ppb 120-liter sample
Possible interferences:
High levels of phenols, ethylene, and propylene cause
negative interferences with formaldehyde.
94
-------
Permissible Exposure Limits
OSHA ACGIH NIOSH
TWA 3 ppm
Ceiling 5 ppm 2 ppm(3 mg/m3) 1.2 mg/m3(30 min)
Peak 10 ppm(30 min.)
Odor per-
ception 1 ppm
The ACGIH has listed formaldehyde for intended changes to delete
the ceiling, to add 1 ppm (1.5 mg/m3) for a TWA, to add 2 ppm (3
mg/m3) as an STEL, and to add a notation that formaldehyde is an
industrial substance suspected of carcinogenic potential for man.
Human Toxicity
Acute Toxicity:
Irritant to skin, eyes, and mucous membrane. If swallowed,
causes violent vomiting and diarrhea, which can lead to
collapse. Frequent or prolonged exposure can cause
hypersensitivity leading to contact dermatitis. Irritant to
eyes at 20 ppm.
Chronic Toxicity:
After reviewing scientific data and public comments relevant
to formaldehyde, EPA has determined there may be a reasonable
basis to conclude that certain exposures to formaldehyde
present or will present a significant risk of widespread harm
to human beings from cancer.
Bibliography
American Conference of Governmental Industrial Hygienists. 1984. TLVs,
Threshold Limit Values for Chemical Substances and Physical Agents in the
Work Environment and Biological Exposure Indices With Intended Changes for
1984-1985. I SB N:0 - 936712^54-6. Cincinnati, OH.
gica Lx
12-54-6.
Hawley, G. G. 1981. The Condensed Chemical Dictionary. 10th Edition. Van
Nostrand Reinhold Company, New York.
National Fire Protection Association. 1983. National Fire Codes, A Comp-
liance of NFPA Codes, Standards, Recommended Practices, and Manuals.
Volume 13. NFPA, Qui-ncy, MA.
Sax, I. N. 1981. Dangerous Properties of Industrial Materials. Sixth
Edition. Van Nostrand Reinhold Company, New York.
Sitting, M. 1981. Handbook of Toxic and Hazardous Chemicals. Noyes
Publications. Park Ridge, NJ.
95
-------
Systems Applications, Inc. 1980. Human Exposure to Atmospheric Concentra-
tions of Selected Chemicals, Volume 1, Appendix A-15-Forrnaldehyde.PE
81-193252.Systems Applications, Inc., San Rafael, CA.
U.S. Department of Health and Human Services. 1983. Chemical Registry of
Toxic Effects of Chemical Substances 1981 to 1982. National Institute for
Occupational Safety and Health.Cincinnati, OH.
U.S. Department of Health and Human Services. 1984. Manual of Analytical
Methods. Third Edition. National Institute for Occupational Safety and
Health. Cincinnati, OH.
U.S. Department of Health and Human Services. 1984. Manual of Analytical
Methods. National Institute for Occupational Safety and Health.
Cincinnati, OH.
U.S. Environmental Protection Agency, Office of Toxic Substances. 1979.
Chemical Hazard Information Profile (CHIP) - Formaldehyde. Washington,
D.C.
Weast, R. T. 1981. CRC Handbook of Chemistry and Physics. 61st Edition.
CRC Press, Inc., Boca Raton, FL.
96
-------
Chemical Name
Hexachl orocycl opentadi ene
CAS Number
77-47-4
Chemical Classification
Chlorinated aromatic
Synonyms
C-56; 1,3-cyclopentadiene, 1,2,3,4,5,5 hexachloro-HCCPD;
hexachlorcyklopentadien; hexachlorocyclopentadiene; NCI-C55607.
perch! orocycl opentadi ene.
Physical/Chemical Properties
Description:
Pale yellow liquid; pungent odor.
Boiling Point:
239°C
Melting Point:
-9.6°C
Molecular Weight:
272.8
Chemical Formula:
Vapor Pressure:
0.4 mm Hg at 50°C; 7.5 mm Hg at 100°C
Vapor Density:
9.42 (air = 1)
Refractive Index:
ND*5 = 1.563
Solubility:
Not available
Log Partition Coefficient (Octanol/water):
3.99
Photochemical Reactivity:
Not available
97
-------
Chemical Reactivity:
When heated to decomposition, emits toxic fumes of chloride.
Incompatible with sodium.
Environmental Fate
Important processes for the fate of HCCPD are near-surface photoly-
sis, adsorption onto organic matter, and possible acid-catalyzed,
hydrolysis to tetrachlorocyclopentadiene if HCCPD is adsorbed onto
a clay surface. HCCPD bioaccumulated in many organisms with weak
biodegradation to tetrachlorocyclopentadienone hydrate occurring.
Source of Emissions
Production:
Mixed pentanes are chlorinated to polychlorinated pentanes in
the liquid phase followed by vapor phase chlorinalysis and
ring closure over a surface-active catalyst.
Uses:
Intermediate for resins, dyes, pesticides, fungicides, pharma-
ceutical s, and flame retardants.
Tables E-47 through E-51 and Figure E-4 present data on
hexachlorocyclopantadiene production, consumption, and emis-
sions.
Storage:
Sold as a distilled liquid of high purity in 55-gallon lined
drums and in tank cars. Not corrosive to most materials of
construction if moisture is rigorously excluded. To avoid
possibility of iron contamination and corrosion, glass, nickel,
or baked phenolic coatings are recommended.
Transportation:
Transported in lined 55-gallon drums or by tank car.
Disposition:
Hexachlorocyclopentadiene may be disposed of by incineration
after it is mixed with another combustible fuel. Care must be
taken to assure complete combustion to prevent the formation
of phosgene. An acid scrubber is required to remove the
halo-acids produced.
Sampling and Analytical Methods
1. NIOSH Method 308
a. Adsorption on Propak T.
b. Desorption with hexane.
c. Gas chromatography.
d. Electron capture detector.
98
-------
TABLE E-47. PRODUCTION OF HEXACHLOROCYCLOPENTADIENE
Source
Hooker Chemical &
Plastics Corp.
Velsicol Chemical
Corporation
Location
Montague, MI
Niagara Falls, NY
Memphis, TN
Total
1978
Esti-
mated
produc-
tion
(106
Wyr)
1.75
3.50
1.75
7
1978
Esti-
mated
capacity
(106
lb/yr)
NAb
NA
NA
NA
Geographic
coordinates
latitude/longitude
43 24 45/86 22 30
43 04 52/79 00 34
35 09 50/90 57 45
Individual site production allocated by the ratio of the total number of
employees at each site compared with the total number of employees at all
three sites.
Not available.
Source: Systems Applications, Inc. 1980.
99
-------
TABLE E-48. HEXACHLOROCYCLOPENTADIENE DERIVATIVES
Compound
Aldrin
Chlorodane
Dieldrin
Endosulfan
Endrin
Heptachlor
PentacR
Het-acid
Mivex
Het-anhydn'de
Dichlorane plus
Chlorendic diesters
End-
use category
Pesticides
Pesticide
Pesticide
Pesticide
Pesticide
Pesticide
Pesticide
Flame retardant
Pesticide
Flame retardant
Flame retardant
Resins
1974
production,
106 Ib
6.5
21.2
1.0
1.5
1.2
2.0
N/A
N/A
N/A
7.0
N/A
N/A
1978 Status
No longer made
N/Aa
No longer made
N/A
No longer made
N/A
No longer made
N/A
No longer made
N/A
N/A
N/A
Known
producer
Velsicol
FMC & Hooker
Velsicol
Hooker
Hooker
Hooker
Velsicol
Location
Marshall, IL
New York, NY
Memphis, TN
Niagara Falls, NY
Niagara Falls, NY
Niagara Falls, NY
Memphis, TN
o
o
aNot available.
Source: Systems Applications Inc. 1980.
-------
TABLE E-49. 1978 HEXACHLOROCYCLOPENTADIENE PRODUCTION EMISSIONS
Company
Hooker
Velsicol
Location
Montague, MI
Niagara Falls, NY
Memphis, TN
Total
Process
emissions
Ib/yr
9,100
18,200
9,100
36,400
g/s
0.131
0.262
0.131
Storage
emissions
Ib/yr
1,400
2,800
1,400
5,600
g/s
0.020
0.040
0.020
Fugitive
emissions
Ib/yr
3,500
7,000
3,500
14,000
9/s
0.050
0.101
0.050
Total
emissions
Ib/yr
14,000
28,000
14,000
56,000
g/s
0.202
0.404
0.202
Source: Systems Applications, Inc. 1980.
-------
TABLE E-50. 1978 HEXACHLOROCYCLOPENTADIENE END-USE EMISSIONS
Company
Hooker
Velsicol
FMC
Location
Montague, MI
Niagara Falls, NY
Memphis, TN
Marshall, IL
Middleport, NY
End-use3
A
A, B
B, C
A
A
Geographic
coordinates
1 ati tude/ 1 ongi tude
43 24 45/86 22 30
43 04 52/79 00 34
35 09 50/90 57 45
39 23 00/87 42 30
43 12 21/78 29 23
Total
Process
emissions
lb/yr
570
810
390
180
325
2,275
Storage
emissions
lb/yr
90
125
60
25
50
350
Fugitive
emissions
lb/yr
215
315
150
70
125
875
Total emissions
lb/yr
875
1,250
600
275
500
3,500
g/s
0.013
0.018
0.009
0.004
0.007
o
ro
End-use code: A - pesticide, B - flame retardant, C - resin.
Source: Systems Applications, Inc. 1982.
-------
TABLE E-51. EMISSIONS AND METEOROLOGICAL STATIONS OF SPECIFIC POINT
SOURCES OF HEXACHLOROPENTADIENE
No.
1
2
3
4
5
Company
Hooker
Hooker
Velsicol
Velsicol
FMC
Site
Montague, MI
Niagara Falls, NY
Memphis, TN
Marshall, IL
Middleport, NY
Lati tude/Longi tude
43 24 45 086 22 30
43 03 02 079 00 27
35 09 50 089 57 45
39 23 00 087 42 30
43 12 21 078 29 23
Star
station
14840
14747
13963
93819
14747
Plant3
type
1
1
1
2
2
Source
type
1
2
1
2
1
2
2
2
Emissions g/s
Process
.131040
.008208
.262080
.011664
.131040
.005616
.002592
.004680
Storage
.020160
.001296
.040320
.001800
.020160
.000864
.000360
.000720
Fugitive
.050400
.003096
. 100800
.004536
.050400
.002160
.001008
.001800
o
CO
aPlant types. 1: Plant produces and consumes hexachlorocyclopentadiene; 2: Plant consumes
hexachlorocyclopentadiene.
Source types: 1: Hexachlorocyclopentadiene production; 2: Hexachlorocyclopentadiene consumption.
Source: Systems Applications, Inc. 1982.
-------
Figure E-4. Specific point sources of hexachlorocyclopentadiene emissions,
Source: Systems Applications, Inc. 1980.
-------
Detection limit:
25 ppt
Possible interferences:
Any compound with the same retention time as
hexachlorocyclopentadiene at the operating conditions is
an interferent.
Method C (Appendix A): C6C12 hydrocarbons and other nonpolar
organics with boiling point between 60° and 200°C.
a. Adsorption on Tenax.
b. Thermal desorption.
c. Gas chromatography/mass spectrometry analysis.
Detection limit:
1 to 200 ppt for a 20-liter sample
Possible interferences:
Blank levels usually limit sensitivity artifacts due to
reactive components (03, NO ). Sample can be analyzed
only once.
Method D (Appendix A): C6-C12 hydrocarbons and other nonpolar
organics with boiling point of 60° to 200°C.
a. Adsorption on Tenax.
b. Thermal desorption into canister.
c. Gas chromatography/flame ionization detection, or gas
chromatography/mass spectrometry analysis.
Detection limit:
0.01 to 1 ppb for a 20-liter sample
Possible interferences:
Blanks and artifact problems in Method C, above.
Method H (Appendix A)
a. Adsorption on solid adsorbent such as polyurethane foam,
XAD-2, or Chromasorb 102.
b. Solvent desorption.
c. Gas chromatography/electron capture detection, gas chro-
matography/mass spectrometry, or gas chromatography/flame
ionization detection analysis.
Detection limit:
3 mg/m3 (1500 m3 sample)
Possible interferences:
None.
105
-------
Permissible Exposure Limits
OSHA ACGIH
TWA 0.01 ppm (0.1 mg/m3)
STEL 0.03 ppm (0.3 mg/m3)
The ACGIH has listed hexachlorocyclopentadiene for intended
changes to delete the STEL.
Human Toxicity
Acute Toxicity:
A skin and eye irritant. High oral toxicity. Moderate skin
irritant.
Chronic Toxicity:
Selected by the National Toxicology Program for carcinogenesis
bioassay as of January 1983.
Bibliography
American Conference of Governmental Industrial Hygienists. 1984. TLVs,
Threshold Limit Values for Chemical Substances and Physical Agents in the
Work Environment and Biological Exposure Indices With Intended Changes for
1984-1985. ISB N:0 - 936712-54-6. Cincinnati, OH.
Hawley, G. G. 1981. The Condensed Chemical Dictionary. 10th Edition. Van
Nostrand Reinhold Company, New York.
Kirk-Othmer. 1979. Encyclopedia of Chemical Technology. 3rd Edition.
Volume 5. Chlorinated Derivitives of Cyclopentadiene. John Wiley and
Sons, New York.
National Fire Protection Association. 1983. National Fire Codes, A Com-
pliance of NFPA Codes, Standards, Recommended Practices, and Manuals.
Volume 13.NFPA, Quincy, MA.
Sax, I. N. 1981. Dangerous Properties of Industrial Materials. Sixth
Edition. Van Nostrand Reinhold Company, New York.
Sittig, M. 1981. Handbook of Toxic and Hazardous Chemicals. Noyes
Publications, Park Ridge, NJ.
Systems Applications, Inc. 1980. Human Exposure to Atmospheric Concentra-
tions of Selected Chemicals, Volume 1. Appendix A-16
Hexachlorocyclopentadiene.PB 81-193252. Systems Applications, Inc., San
Rafael, CA.
Systems Applications, Inc. 1982. Human Exposure to Atmospheric Concentrations
of Selected Chemicals, Volume II. Appendix A-16. Hexacnlorocylopentadiene.
EPA Contract No. 68-02-3066.SAT 58-EF81-156R2. Systems Applications,
Inc., San Rafael, CA.
106
-------
U.S. Department of Health and Human Services. 1983. Chemical Registry of
Toxic Effects of Chemical Substances 1981 to 1982. National Institute for
Occupational Safety and Health. Cincinnati, OH.
U.S. Department of Health and Human Services. 1984. Manual of Analytical
Methods. National Institute for Occupational Safety and Health.
Cincinnati, OH.
U.S. Environmental Protection Agency. 1980. Treatability Manual: Volume 1
Treatability Data. EPA 600-8-80-042a.
Weast, R. T. 1981. CRC Handbook of Chemistry and Physics. 61st Edition.
CRC Press, Inc., Boca Raton, FL.
107
-------
Chemical Name
Maleic anhydride
CAS Number
108-31-6
Chemical Classification
Anhydride (unsaturated)
Synonyms
Cis-butenedioic anhydride; 2,5-furandione; maleic acid anhydride;
toxilic anhydride
Physical/Chemical Properties
Description:
Colorless needles
Boiling Point:
200°C
Melting Point:
53°C
Molecular Weight:
98.1
Chemical Formula:
HC:CH C(0)OC(0)
Vapor Pressure:
1 mm at 44°C
Vapor Density:
3.4 (air = 1)
Refractive Index:
Not available
Solubility:
Soluble in water, acetone, alcohol, and dioxane; partially
soluble in chloroform and benzene.
Log Partition Coefficient (octanol/water):
Not available
Photochemical Reactivity:
Not available
108
-------
Chemical Reactivity:
Dust and vapors are very flammable in air. Reacts violently
with alkali metals, amines, and other strong oxidizing agents.
Incompatable with cations or bases. Will react with water or
steam to produce heat.
Environmental Fate
Because of its high boiling point and solid state at ambient tem-
peratures, most maleic anhydride emitted to the air is expected to
precipitate and be solubilized in water. Conversion to maleic acid
and subsequent biodegradation is likely to be a major pathway.
Maleic anhydride in wastewater is easily decomposed by test-acti-
vated sludge.
Source of Emissions
Production:
Vapor phase oxidation of benzene in the presence of vanadium
oxide catalyst
Vapor phase oxidation of n-butane in the presence of a
phosphorous-vanadium catalyst
Recovery from phthalic anhydride production
Uses:
Used exclusively as an intermediate to make:
Unsaturated polyester resins
Agricultural chemicals
Lubricating oil additives
Copolymers
Fumaric acid
Malic acid
Chlorendic acid and anhydride
Alkyd resins
Tables E-52 and E-53 present maleic anhydride production and
consumption data.
Storage:
Should be protected from physical damage and stored in a cool,
dry, well-ventilated area away from ignition sources; outside
or detached storage is preferred. Should be protected from
moisture and stored separately from alkali metals, amines, and
other strong oxidizing agents. Keep away from flame or spark
as dust and vapor for molten product are very flammable.
Transportation:
Shipped in fiber drums (rod, flake, and lump); iron drums
(fused); and tank cars (molten).
109
-------
TABLE E-52. PRODUCTION OF MALEIC ANHYDRIDE
Company
Ashland Oil , Inc.
Ashland Chem. Co. , Div.
Petrochems. Div.
Denka Chem. Corp.
Monsanto Co.
Monsanto Indust.
Chems. Co.
Standard Oil Co. (Indiana)
Amoco Chems. Corp. ,
subsid.
United States Steel
Corp.
USS Chems. , div.
Location
Neal, W.Va.
Houston, Tex.
Pensacola, Fla.
St. Louis, Mo.
Joliet, 111.
Neville Island,
Pa.
TOTAL
Annual
Capacity,
106 Ib
50
50
130
110
60
70
470
Raw material
and remarks
n-Butane
n-Butane
n-Butane
n-Butane (40%);
benzene (60%);
plant will be con-
verted to 100% bu-
tane raw material .
n-Butane
n-Butane (45%);
benzene (55%);
plant is being con-
verted to 100% bu-
tane based feed-
stock; benzene
based capacity is
on standby.
Source: SRI International. 1985.
110
-------
TABLE E-53. USES OF MALEIC ANHYDRIDE
Use
Unsaturated polyester resins
Agricultural chemicals
Lubricating oil additives
Copolymers
Fumaric acid
Malic acid
Chlorendic acid and anhydride
Alkyd resins
All other
TOTAL
Millions of
pounds (1978)
180
31
30
20
20
15
6
5
24
331
Percent of
total
consumption
54
9
9
6
6
5
2
2
7
100
Source: U.S. EPA 1981 (CHIP)
111
-------
Disposition:
Maleic anhydride may be disposed of by controlled incinera-
tion. Care must be taken to assure complete oxidation to
non-toxic products.
Sampling and Analytical Methods
1. NIOSH Method 302
a. Bubbler collection.
b. High-pressure liquid chromatography.
Detection limit:
10 ppb with a 360-liter sample
Possible interferences:
Any compound that has the same retention time as maleic
acid at the process conditions is an interferent. Maleic
anhydride is immediately hydro!ized to maleic acid upon
collection. This method will not differentiate between
maleic acid and maleic anhydride.
Permissible Exposure Limits
OSHA ACGIH
TWA 0.25 ppm (1 mg/m3) 0.25 ppm (1 mg/m3)
Human Toxicity
Acute Toxicity:
An eye irritant. Irritation to skin, eyes, and mucous
membranes. Inhalation of vapor can cause pulmonary
edema. Causes burns to skin and eyes.
Chronic Toxicity:
Has been found to be an equivocal tumorigenic agent in
rats. In one study one rat developed two fibrosarcomas
at the site of injection. A mutagenicity test on Chinese
hamster cells was positive for chromosomal aberrations.
Bibliography
American Conference of Governmental Industrial Hygienists. 1984. TLVs,
Threshold Limit Values for Chemical Substances and Physical Agents in the
Work Environment and Biological Exposure Indices With Intended Changes for
1984-1985.ISB N:0 - 936712-54-6. Cincinnati, OH.
Hawley, G. G. 1981. The Condensed Chemical Dictionary. 10th Edition. Van
Nostrand Reinhold Company, New York.
112
-------
Sax, I. N. 1981. Dangerous Properties of Inaustrial Materials.
Sixth Edition. Van Nostrand Reinhold Company, New York.
Sittig, M. 1981. Handbook of Toxic and Hazardous Chemicals. Noyes
Publications. Park Ridge, NO.
SRI International. 1985. Directory of Chemical Producers United States
1985. Menlo Park, California.
U.S. Department of Health and Human Services. 1983. Chemical Registry of
Toxic Effects of Chemical Substances 1981 to 1982. National Institute for
Occupational Safety and Health. Cincinnati, OH.
U.S. Department of Health and Human Services. 1984. Manual of Analytical
Methods. National Institute for Occupational Safety and Health.
Cincinnati, OH.
U.S. Environmental Protection Agency. 1981. Chemical Hazard Information
Profile (CHIP) - Maleic Anhydride. Office of Toxic Substances, Washington DC.
U.S. Environmental Protection Agency, 1978. Human Exposure to Atmospheric
Concentrations of Selected Chemicals. Office of Air Quality Planning and
Standards.Research Triangle Park, NC.
U.S. Environmental Protection Agency. 1980. Treatability Manual: Volume 1
Treatability Data. EPA 600-8-80-042a.
113
-------
Chemical Name
Manganese
CAS Number
7439-96-5
Chemical Classification
Metallic element
Synonyms
Colloidal manganese; mangan
Physical/Chemical Properties
Description:
Of the four allotropic forms, alpha is the most important.
Brittle reddish-gray, silvery metal.
Boiling Point:
2097°C
Melting Point:
1245°C
Molecular Weight:
54.9
Chemical Formula:
Mn
Vapor Pressure:
1 mm at 1292°C
Density:
7.20
Refractive Index:
Not available
Solubility:
Decomposes in water; readily dissolves in dilute mineral acid.
Log Partition Coefficient (octanol/water):
Not available
Photochemical Reactivity:
No atmospheric transformation (aerosol and particle
deposition). Reacts with all mineral acids with evolution of
hydrogen and formation of divalent manganous salts.
114
-------
Chemical Reactivity:
Will react with water or steam to produce hydrogen. Can react
with oxidizing materials. Superficially oxidizes on exposure
to air. Burns with an intense white light when heated in air.
Environmental Fate
Manganese in the ecosystem has well-established lines of movement
from rocks to soils to plants to animals, from soils to water to
organisms, and back to water and soils. Marine organisms can
concentrate manganese in their bodies, and man retains manganese at
a concentration 3 to 4 times that in his food.
Source of Emissions
Production:
Reduction of the oxide with aluminum or carbon.
Obtained electrolytically from sulfate or chloride solution.
Uses:
Ferroalloys (steel manufacture)
Nonferrous alloys (improved corrosion resistance and hardness)
High purity salt for various chemical uses
Purifying and scavenging agent in metal production
Manufacture of aluminum by Toth process
Tables E-54 through E-60 present manganese consumption and
emission data.
Storage:
Protect containers against physical damage. Food and drinks
should be kept out of work area.
Transportation:
Shipped in drums and in car lots in pure, electrolytic, or
powdered grades
Disposition:
Manganese may be disposed of by sanitary landfill.
Sampling and Analytical Methods
1. NIOSH Method 173
a. Filter collection.
b. Acid digestion.
c. AAS (atomic absorption spectrophotometry),
Detection limit:
0.2 mg/m3 with a 3-liter sample
115
-------
TABLE E-54. UNITED STATES MANGANESE ORE CONSUMPTION
Use
Manganese alloys/metals
Pig iron and steel
Dry cells, chemicals, misc.
Total
Usage, %
79
9
12
100
Manganese ore
consumed,
tons/yr
1,263,581
143,761
193,581
1,600,923
Source: Systems Applications, Inc. 1980.
116
-------
TABLE E-55. 1978 NATIONWIDE MANGANESE EMISSIONS
Source
Mining
Iron and steel
Gray iron foundry
Ferro alloy, ferro manganese, silico manganese
Chemical applications
Battery production
Welding rod manufacture
Power plants
Coal
Oil
Industrial Boilers
Coal
Oil
Residential /commercial
Coal
Oil
Coke ovens
Total
Nationwide
emissions,
Ib/yr
Negligible
9,212,000
5,540,000
12,632,000
644,000
276,000
48,000
5,280,000
13,566
352,000
14,091
16,000
4,454
1,950,000
35,982,111
Source: Systems Applications, Inc.. 1980.
117
-------
TABLE E-56. MANGANESE EMISSIONS FROM IRON AND STEEL PRODUCTION
Region
New England
Middle Atlantic
East North Central
West North Central
South Atlantic
East South Central
West South Central
Mountain
Pacific
Total
Number
of sites
10
65
84
5
22
25
12
2
32
257
Manganese
emissions,
Ib/yr
55,045
2,846,685
3,859,795
101,260
819,940
626,250
211,865
221,210
469,950
9,212,000
Average
emissions per site
Ib/yr
5,505
43,795
45,950
20,250
37,270
25,050
17,655
110,605
14,685
35,844
9/s
0.079
0.630
0.661
0.292
0.537
0.361
0.254
1.592
0.211
Source: Systems Applications, Inc. 1980.
118
-------
TABLE E-57. MANGANESE EMISSIONS FROM GRAY IRON FOUNDRY OPERATIONS
Region
New England
Middle Atlantic
East North Central
West North Central
South Atlantic
East South Central
West South Central
Mountain
Pacific
Total
Number
of sites
13
42
129
29
22
37
19
5
28
324
Manganese
emissions,
Ib/yr
138,500
508,985
2,887,725
315,085
408,575
654,410
277,000
65,785
283,925
5,540,000
Average
emissions per site
Ib/yr
10,655
12,120
22,385
10,865
18,570
17,685
14,580
13,157
10,140
17,100
g/s
0.15
0.17
0.32
0.16
0.27
0.25
0.21
0.19
0.15
Source: Systems Applications, Inc. 1980.
119
-------
TABLE E-58. MANGANESE EMISSIONS FROM FERROALLOY, FERRO MANGANESE,
AND SILICA MANGANESE PRODUCTION
Region
New England
Middle Atlantic
East North Central
West North Central
South Atlantic
East South Central
West South Central
Mountain
Pacific
Total
Number
of sites
0
12
8
1
8
13
1
4
4
51
Manganese
emissions,
Ib/yr
0
2,972,220
1,981,480
247,685
1,981,480
3,219,905
247,685
990,740
990,740
12,632,000
Source: Systems Applications, Inc. 1980.
120
-------
TABLE E-59. MANGANESE EMISSIONS FROM ELECTRICAL UTILITY POWER PLANTS
(coal-fired)
Region
New England
Middle Atlantic
East North Central
West North Central
South Atlantic
East South Central
West South Central
Mountain
Pacific
Total
Number
of sites
9
51
156
111
61
44
3
38
1
474
Manganese
emissions,
Ib/yr
36,960
596,640
1,789,920
496,320
1,034,880
860,640
68,640
359,040
36,960
5,280,000
Average
emissions per site
Ib/yr
4,105
11,700
11,475
4,470
16,965
19,560
22,880
9,450
36,960
11,140
9/s
0.06
0.17
0.17
0.07
0.25
0.29
0.33
0.14
0.54
Source: Systems Applications, Inc. 1980.
121
-------
TABLE E-60. MANGANESE EMISSIONS FROM COKE OVEN OPERATIONS
Region
New England
Middle Atlantic
East North Central
West North Central
South Atlantic
East South Central
West South Central
Mountain
Pacific
Total
Number
of sites
0
15
25
3
4
9
2
2
1
61
Manganese
emissions,
Ib/yr
0
479,505
799,185
95,900
127,870
287,705
63,935
63,935
31,965
1,950,000
Source: Systems Applications, Inc. 1980.
122
-------
Possible interferences:
Spectral interferences; background or nonspecific absorp-
tion; ionization interferences, chemical interferences;
and physical interferences.
2. NIOSH Method 351
a. Filter collection.
b. Acid digestion.
c. Inductively coupled plasma-atomic emission spectroscopy
analysis.
Detection limit:
5 to 2:000 yg/m3 with a 5-liter sample.
Possible interferences:
Physical interferences; chemical interferences; spectral
interferences.
3. NIOSH Method S5
a. Filter collection.
b. Acid digestion.
c. Atomic absorption.
Detection limit:
0.2 to 20 mg/m3 with a 22.5-liter sample.
Possible interferences:
No known interferences.
Permissible Exposure Limits
OSHA ACGIH
TWA 1 mg/m3 (fume)
STEL 3 mg/m3 (fume)
Ceiling 5 mg/m3 5 mg/m3 (dust and com-
pounds)
Human Toxicity
Acute Toxicity:
Occurs by inhalation of the dust or fumes. Symptoms are
languor, sleepiness, weakness, emotional disturbances,
spastic gait, and paralysis.
Chronic Toxicity:
Chronic manganese poisoning is a clearly characterized
disease that results from the inhalation of fumes or
dusts of manganese. Exposure to heavy concentrations for
as little as three months may produce the condition, but
it usually develops after 1 to 3 years of exposure. The
central nervous system is the chief site of damage.
Manganese has also been found to be an equivocal tumori-
genic agent in rats.
123
-------
bibliography
American Conference of Governmental Industrial Hygienists. 1984. TLVs,
Threshold Limit Values for Chemical Substances and Physical Agents in the
Work Environment and Biological Exposure Indices With Intended Changes for
1984-1985.ISB N:0 - 936712-54-6.Cincinnati, OH.
Hawley, G. G. 1981. The Condensed Chemical Dictionary. 10th Edition. Van
Nostrand Reinhold Company, New York.
National Academy of Sciences. 1973. Medical and Biologic Effects of
Environmental Pollutants-Manganese. Washington, D.C.
National Fire Protection Association. 1983. National Fire Codes, A Comp-
liance of NFPA Codes, Standards, Recommended Practices, and Manuals.
Volume 13.NFPA, Quincy, MA.
Sax, I. N. 1981. Dangerous Properties of Industrial Materials. Sixth
Edition. Van Nostrand Reinhold Company, New York.
Sittig, M. 1981. Handbook of Toxic and Hazardous Chemicals. Noyes
Publications, Park Ridge, NO.
System Applications, Inc., 1980. Human Exposure to Atmospheric
Concentrations of Selected Chemicals.Appendix A-17 Manganese. Office of
Air Quality Planning and Standards. Research Triangle Park, NC.
U.S. Department of Health and Human Services. 1983. Chemical Registry of
Toxic Effects of Chemical Substances 1981 to 1982. National Institute for
Occupational Safety and Health.Cincinnati, OH.
U.S. Department of Health and Human Services. 1984. Manual of Analytical
Methods. National Institute for Occupational Safety and Health.
Cincinnati, OH.
Weast, R. T. 1981. CRC Handbook of Chemistry and Physics. 61st Edition.
CRC Press, Inc., Boca Raton, FL.
124
-------
Chemical Name
Mercury
CAS Number
7439-97-6
Chemical Classification
Metallic element
Synonyms
Colloidal mercury; kwik; mercure; mercuric; mercury-metallic (DOT);
metallic mercury; NCI-C60399; quecksilber; quicksilver; RTEC
Physical/Chemical Properties
Description:
Silvery, extremely heavy liquid, sometimes found native.
Boiling Point:
356.6°C
Melting Point:
-38.85°C
Molecular Weight:
200.6
Chemical Formula:
Hg
Vapor Pressure:
1 mm at 126.2°C; 2 x 10"3 mm at 25°C
Density:
13.54 g/ml (20°C)
Refractive Index:
Not available
Solubility:
Insoluble in HC1; soluble in sulfuric acid upon boiling;
readily soluble in nitric acid; insoluble in water, alcohol,
and ether; soluble in lipids.
Log Partition Coefficient (octanol/water):
Not available
125
-------
Photochemical Reactivity:
Not photochemical1y reactive
Chemical Reactivity:
Incompatible with acetylenic compounds, ammonia, boron diiodo-
phosphide, ethylene oxide, metals, methyl azide, methyl si lane,
oxygen, oxidants, and tetracarbonylnickel.
Environmental Fate
Breakdown of atmospheric dimethyl mercury is of slight importance.
Oxidation of metallic mercury forms ionic mercury; reduction forms
an HgS precipitate. Metallic Hg, methylated Hg, and adsorbed Hg
all volatilize. Mercury is adsorbed by most particles, buried in
sediment, and reduced to HgS. It is bioaccumulated by all orga-
nisms and readily methylated metabolically.
Source of Emissions
Production:
By heating cinnabar in air, or with lime, and condensing the
vapor. Purified by distillation. In 1982 and 1983, Nevada
was the only mercury-producing State. Producers were the
Carl in gold mine, the Pinson gold mine, and the McDermitt
mercury mine. During 1983, four companies specialized in
processing primary or scrap mercury: Bethlehem Apparatus Co.,
Hellertown, PA; D.F. Goldsmith Chemical & Metal Corp.,
Evanston, IL; Mercury Refining Co., Inc., Albany, NY; and Troy
Chemical Corp., Newark, NJ.
Uses:
Manufacturing of all mercury salts
Mercury cells
Electric switches
Propellent
Mercury vapor lamps
Barometers
Thermometers
Medicine
Amalgams
Mercury boilers
Tables E-61 and E-62 present mercury production and consump-
tion data.
Storage:
Containers should be kept closed. Preferably, small quanti-
ties should be stored in a polyethylene bottle, and the mercu-
ry surface should be covered with water to prevent evaporation
as much as possible.
126
-------
TABLE E-61. MERCURY PRODUCTION
(flasks)
Producing mines
Mine production
Secondary production
Industry
Government
Industry stocks, year end
Shipments from the Nation-
al Defense Stockpile
Imports for consumption
Consumption, reported
Consumption, apparent
1979
3
29,519
4,287
11,300
27,582
196
26,448
62,205
82,721
1980
4
30,657
6,793
10,013
33,069
-
9,416
58,983
51,392
1981
3
27,904
4,244
7,000
27,339
-
12,408
59,244
57,286
1982
3
25,760
4,473
29,327
7,088
8,916
48,943
44,249
1983
3
25,070
13,474
31,518
6,000
12,786
49,138
55,252
Source: Minerals Yearbook.
127
-------
TABLE 1-62. MERCURY CONSUMED IN THE UNITED STATES, BY USE
(flasks)
SIC
code
28
2812
2816
2819
2821
2819
2851
2879
-
36
3641
3643
3692
-
38
382
3843
-
-
Use
Chemical and allied products:
Chlorine and caustic soda
manufacture
Pigments
Catalysts, miscellaneous
Catalysts for plastics
Laboratory uses
Paints
Agricultural chemicals
Other chemicals and allied
products
Electrical and electronic uses:
Electric lighting
Wiring devices and switches
Batteries
Other electrical and elec-
tronic uses
Instruments and related
products:
Measuring and control in-
struments
Dental equipment and sup-
plies
Other instruments and re-
lated products
Other
Total
1979
12,180
Wa
1,257
•W
410
9,979
W
82
511
3,213
25,299
106
3,603
1,422
192
556
62,205
1980
9,470
W
765
W
363
8,621
W
W
1,036
3,062
27,829
144
3,049
1,779
190
790
58,983
1981
7,323
W
815
W
328
7,049
79
W
1,043
2,641
29,441
W
5,671
1,613
253
242
59,244
1982
6,243
W
499
W
281
6,794
36
W
826
2,004
24 ,880
W
3,064
1,019
194
984
48,943
1983
8,054
W
484
W
280
6,047
W
W
1,273
2,316
23,350
W
2,465
1,597
W
1,356
49,138
W = Withheld to avoid disclosing company proprietary data; included in
"Total".
Source: Minerals Yearbook,
128
-------
Transportation:
Transported in 1-, 5-, and 10-pound bottles and 76-pound
flasks.
Disposition:
Elemental mercury may be accumulated for sale or for puri-
fication and reuse. Inorganic mercury (mercuric chloride,
mercuric nitrate, mercuric sulfate) may be disposed of by
incineration followed by recovery/removal of mercury from the
gas stream. Alternatively, mercury compounds may be recovered
from brines, sludges, and spent catalysts. Mercury in
inaccessible locations (cracks, etc.) can be treated with
calcium polysulfide and excess sulfur.
Sampling and Analytical Methods
1. NIOSH Method
a. Solid Sorbent Tube (30 mg silvered chromosorb P, with
glass-fiber prefilter.
b. Automatic absorption, flameless.
Detection limit:
0.3 ppb per 3-liter sample
Possible interferences:
Chlorine, along with other oxidizing gasess, will attack
silver. Methyl mercuric chloride is a potential inter-
ferent.
Permissible Exposure Limits
OSHA ACGIH (skin) NJOSH.
TWA 0.05 mg/m3 air (all forms ex- 0.05 mg/m3
cept alky! vapor)
0.1 mg/m3 (aryl and inorganic
compounds)
0.01 mg/m3 (alky! compounds)
Ceiling 1 mg/10m3 0.03 mg/m3 (alkyl compounds)
Human Toxicity
Acute Toxicity:
Gastrointestinal tract effects, central nervous system
effects.. High toxicity inhalation. A general protoplasmic
poison after absorption, it circulates in the blood and is
stored in the liver, kidneys, spleen, and bone. Solution
salts have violent corrosive effects on skin and mucous
membranes, severe nausea, vomiting, abdominal pain, bloody
diarrhea, kidney damage; death usually occurs within 10 days.
129
-------
Chronic Toxicity:
hercury has a cumulative effect and has a tendency to deposit
in certain organs; most notably the brain, liver, and kidneys,
although it can be found in nearly all tissues. The TLV is
set at a point to prevent chronic poisoning. The onset of
symptoms of mercury toxicity from chronic exposure may be
ignored by the individual or attributed to other causes. This
is particularly true with erethism, which is characterized by
irritability, outbursts of temper, excitability, shyness,
resentment of criticism, headache, fatigue, and indecision.
Bibliography
American Conference of Governmental Industrial Hygienists. 1984. TLVs,
Threshold Limit Values for Chemical Substances and Physical Agents in the
Uorfr Environment and Biological Exposure Indices With Intended Changes for
1984-1985.ISB N:0 - 936712-54-6.Cincinnati, OH.
Hawley, G. G. 1981. The Condensed Chemical Dictionary. 10th Edition. Van
Nostrand Reinhold Company, New York.
The International Technical Information Institute. 1979. Toxic and haz-
ardous Industrial Chemicals Safety Manual. The International Technical
Information Institute, Tokyo, Japan.
Sax, I. N. 1981. Dangerous Properties of Industrial Materials. Sixth
Edition. Van Nostrand Reinhold Company, New York.
Sittig, M. 1981. Handbook of Toxic and Hazardous Chemicals. Noyes
Publications, Park Ridge, NJ.
U.S. Department of Health, Education, and Welfare, Public Health Service.
1973. Criteria for a Recommended Standard^..Occupational Exposure to Inor-
ganic Mercury.National Institute for Occupational Safety and Health.
Cincinnati, OH.
U.S. Department of Health and Human Services. 1983. Chemical Registry of
Toxic Effects of Chemical Substances 1981 to 1982. National Institute for
Occupational Safety and Health. Cincinnati, OH.
U.S. Department of Health and Human Services. 1984. Manual of Analytical
Methods. Third Edition. National Institute for Occupational Safety and
Health. Cincinnati, OH.
U.S. Department of the Interior. 1984. 1983 Minerals Yearbook. Volume 1.
Metals and Minerals. Bureau of Mines. Washington, D.C.
130
-------
U.S. Environmental Protection Agency. 1980. Treatability Manual: Volume 1
Treatability Data. EPA 600-8-80-042a.
Weast, R. T. 1981. CRC Handbook of Chemistry and Physics. 61st Edition.
CRC Press, Inc., Boca Raton, FL.
131
-------
Chemical Name
Methylene chloride
CAS Number
75-09-2
Chemical Classification
Chlorinated hydrocarbon
Synonyms
Aerothene MM; chlorure de methylene; DCM; dichloromethane;
dichloromethane (DOT); freon 30; methane dichloride; methylene
bichloride; methylne chloride; methylene chloride (DOT); methylene
dichloride; metylenu chlorek; narkotil; NCI-C50102; solaesthin;
solmethine
Physical/Chemical Properties
Description:
Colorless volatile liquid; penetrating ether-like odor.
Boiling Point:
40.1°C
Melting Point:
-97°C
Molecular Weight:
84.9
Chemical Formula:
CH2C12
Vapor Pressure:
380 mm at 22°C
Vapor Density:
2.93 (air = 1)
Refractive Index:
ND20 = 1..4242
Solubility:
Soluble in alcohol and ether; slightly soluble in water.
Log Partition Coefficient (octanol/water):
1.25
132
-------
Photochemical Reactivity:
Reactivity toward OH- is a half-life of approximately 1 year,
less than methane. No reaction toward 03.
Chemical Reactivity:
When heated to decomposition, emits highly toxic fumes of
phosgene. Not explosive under ordinary conditions, but will
form explosive mixtures in atmosphere having high oxygen
content or in liquid 02, N20i,, K, Na, NaK. Reacts violently
with Li, NaK, potassium-tert-butoxide, and (KOH+n-methyl-n-
nitrosourea).
Environmental Fate
Because of high vapor pressure, volatilization to the atmosphere is
rapid and is a major transport process. In tetrosphere, oxidation
by hydroxyl radicals to carbon dioxide, carbon monoxide, and phos-
gene is important fate mechanism.
Source of Emissions
Production/processing:
Chlorination of methyl chloride and subsequent distillation.
Chlorination of methane and subsequent distillation.
Uses:
Aerosol products Solvent for triacetate extrusion
Paint removers Solvent in the pharmaceutical and
Solvent degreasing electronics industry
Plastics processing Photographic film
Blowing agent in foams Polycarbonate resins
Solvent in inks, Cleaning uses
adhesives
Tables E-63 through E-67 present methylene chloride produc-
tion, consumption, and emission data.
Storage:
Should be protected against physical damage and stored in a
cool, dry, well-ventilated location, away from any area where
the fire hazard may be acute.
Transport:
Should be shipped in glass bottles, 5- and 55-gallon drums,
tank cars, and tank trucks.
Disposition:
Methylene chloride may be disposed of by incineration after
mixing with another combustible fuel; care must be exercised
to assure complete combustion to prevent the formation of
phosgene. An acid scrubber is necessary to remove the halo
acids produced.
133
-------
TABLE E-63. PRODUCTION OF METHYLENE CHLORIDE
Company
Allied Chemical Corp.
Diamond Shamrock
Dow Chemical
Stauffer
Vulcan Materials Co.
Location
Moundsville, WV
Belle, WV
Freeport, TX
Plaquemine, LA
Louisville, KY
Geismar, LA
Wichita, KS
Total
1978
estimated
production,
106 Ib/yr
31
63
125
112
38
50
106
525
Process
A,BC
A
B
A
A
A A
A,Bd
1978
estimated
capacity,
10fe Ib/yr
50
100
200
180
60
80
170
840
Geographical location,
1 ati tude/ 1 ongi tude
39 54 24/80 47 51
38 14 09/81 32 38
28 59 15/95 24 45
30 19 00/91 15 00
38 12 09/85 51 49
30 10 00/90 59 00
37 36 55/97 18 30
00
-p.
Distribution of the 525 million pounds per year for each producing location has been made as a direct
ratio of total production/total capacity x individual plant capacity.
(A) - Methanol hydrochlorination process or methyl chloride chlorination process.
(B) - Methane chlorination process.
c 5% methane chlorination, 95% methyl chloride chlorination.
10% methane chlorination, 90% methyl chloride chlorination.
Source: Systems Applications, Inc. 1980.
-------
TABLE E-64. 1978 METHYLENE CHLORIDE CONSUMPTION BY END USE
End use
Paint and varnish remover
Metal degreasing
Aerosols
Plastics processing
Export
Miscellaneous
Total
Percent of
total consumption
30
22
17
5
21
5
100
End use
consumption,
106 Ib/yr
157.5
115.5
89.25
26.25
110.25
26.25
525
Source: Systems Applications, Inc. 1980.
TABLE E-65. 1978 METHYLENE CHLORIDE NATIONWIDE EMISSION LOSSES
End use
Estimated national
emission, 106 Ib/yr
Production
Paint and varnish remover
Metal degreasing
Aerosols
Plastics processing
Miscellaneous
Export
Total
0.65
157.5
107.1
89.25
26.25
26.25
0
407.00
Source: Systems Applications, Inc. 1982.
135
-------
TABLE E-66. 1978 METHYLENE CHLORIDE PRODUCTION EMISSIONS
Company
Allied Chemical
Diamond Shamrock
Dow Chemical
Stauffer
Vulcan
Location
Moundsville, WV
Belle, WV
Freeport, TX
Plaquemine, LA
Louisville, KY
Geismar, LA
Wichita, KA
Total
Process
vent emissions
Ib/yr
980
164
16,353
234
990
1,300
3,960
23,981
g/s
0.014
0.002
0.235
0.003
0.014
0.019
0.057
Storage
vent emissions
Ib/yr
74,030
15,498
119,566
22,178
93,480
123,000
24,553
472,305
g/s
1.066
0.223
1.720
0.319
1.346
1.771
0.353
Fugitive
emissions
Ib/yr
14,430
2,980
37,780
4,268
17,970
23,650
48,550
149,628
9/s
0.208
0.043
0.543
0.061
0.259
0.340
0.699
Total emissions
Ib/yr
89,440
18,642
173,699
26,680
112,440
147,950
77,063
645,914
g/s
1.288
0.268
2.498
0.383
1.619
2.130
1.109
OJ
CTl
Source: Systems Applications, Inc. 1980.
-------
TABLE E-67. EMISSIONS RATES AND NUMBER OF GENERAL POINT SOURCES OF METHYLENE CHLORIDE
Region
New England
Middle Atlantic
East North Central
West North Central
South Atlantic
East South Central
West South Central
Mountain
Pacific
Cold cleaning
Emissions/site,
gm/s
0.00952
0.00952
0.00952
0.00952
0.00952
0.00952
0.00952
0.00952
0.00952
Number
of sites
7,284
18,892
32 ,084
10,624
14,620
7,168
11,764
4,397
14,347
Open-top vapor degreasing
Emissions/site,
gm/s
0.288
0.288
0.288
0.288
0.288
0.288
0.288
0.288
0.288
Number
of sites
82
170
257
66
69
39
59
26
132
Conveyorized '
vapor degreasing
Emissions/site,
gm/s
0.857
0.857
0.857
0.857
0.857
0.857
0.857
0.857
0.857
Number j
of siteq
14
30
50
10
10
6
8
3
20
GJ
Source: Systems Applications, Inc. 1980.
-------
Sampling and Analytical Methods
1. NIOSH Method S329
a. Adsorption on charcoal.
b. Desorption with carbon disulfide.
c. Gas chromatography.
Detection limit:
350 to 10,400 mg/m3 (100-3000 ppm) per 1-liter sample
Possible interferences:
High humidity will lower vapor trapping efficiency. Any
compound with the same retention time as methylene
chloride may be an interferent.
2. NIOSH Method P&CAM 127
a. Adsorption on charcoal.
b. Desorption with carbon disulfide.
c. Gas chromatography.
Detection limit:
0.05 nig/sample (0.01 ppm); minimum 0.5-liter sample
Possible interferences:
High humidity will lower vapor trapping efficiency. Any
compound with the same retention time as methylene
chloride may be an interferent.
3. NIOSH Method 1005 (replaces NIOSH Methods S329 and P&CAM 127)
a. Solid sorbent tube (two coconut shell charcoal tubes; 100
mg/50 mg).
b. Gas chromatography.
c. Flame ionization detector.
Detection limit:
3.0 ppm per 1-liter sample
Possible interferences:
None identified.
4. Method B (Appendix A) C2-C16 hydrocarbons and other nonpolar
organics with a boiling point of 100° to 175°C.
a. Whole air collection in canister.
b. Cryogenic concentration.
c. Gas chromatography/flame ionization detection.
Detection limit:
0.1 ppb per 100-ml sample
Possible interferences:
Storage times greater than a week are not recommended.
Laboratory contamination with methylene chloride is a
common problem.
138
-------
5. Method F (Appendix A) nonpolar volatile* with a boiling
point 0° to 100°C.
a. Adsorption on carbon molecular sieves.
b. Thermal desorption into canister.
c. Analysis by gas chromatography/flame ionization detection
or gas chromatography/mass spectrometry analysis.
Detection limit:
0.01-1 ppb per 20-liter sample
Possible interferences:
High temperature (350°C) required for desorption may
decompose compounds. Laboratory contamination with
methylene chloride is a common problem.
Permissible Exposure Limits
OSHA ACGIH
TWA 500 ppm 100 ppm (350 mg/m3)
STEL 500 ppm (1740 mg/m3)
Ceiling 1000 ppm
Peak 2000 ppm (5 min. in 2 h)
The ACGIH has listed methylene chloride for intended changes to
delete the STEL.
Odor perception 25 to 50 ppm.
Human Toxicity
Acute toxicity:
Very dangerous to the eyes. Except for its property of induc-
ing narcosis, it has very few other acute toxicity effects.
Can be decomposed by contact with hot surfaces or open flame,
which yields toxic fumes that are irritating. Can cause
dermatitis upon prolonged skin contact.
Chronic Toxicity:
EPA is awaiting the results of a National Toxicology Program
peer review of a methylene chloride bioassay (February 1985).
Preliminary findings of the bioassay are that methylene chlo-
ride is carcinogenic to laboratory animals.
Bibliography
American Conference of Governmental Industrial Hygienists. 1984. TLVs,
Threshold Limit Values for Chemical Substances and Physical Agent's in the
Work Environment and Biological Exposure Indices With Intended Changes for
1984-1985.ISB N:0 - 936712-54-6. Cincinnati, OH.
139
-------
GCA Corporation. 1983. Methylene Chloride: A Preliminary Source
Assessment. Prepared for tine U.S. Environmental Protection Agency, Office
of Policy and Resource Management. Washington, D.C.
Hawley, G. G. 1981. The Condensed Chemical Dictionary. 10th Edition.
Van Nostrand Reinhold Company, New York.
National Fire Protection Association. 1983. National Fire Codes, A Comp-
liance of NFPA Codes, Standards, Recommended Practices, and Manuals.
Volume 13. NFPA, Quincy, MA.
PEI Associates, Inc. 1985. Occupational Exposure and Environmental Release
Assessment of Methylene Chloride (Draft). Prepared for the U.S.
Environmental Protection Agency, Office of Toxic Substances, Washington,
D.C.
Sax, I. N. 1981. Dangerous Properties of Industrial Materials.
Sixth Edition. Van Nostrand Reinhold Company, New York.
Sittig, M. 1981. Handbook of Toxic and Hazardous Chemicals. Noyes
Publications, Park Ridge, NJ.
Systems Applications Inc. 1980. Human Exposure to Atmospheric Concentra-
tions of Selected Chemicals. Volume 1. Appendix A-19, Methylene Chloride.
PB 81-193252.Systems Applications, Inc., San Rafael, CA.
Systems Applications, Inc. 1982. Human Exposure to Atmospheric Concentrations
of Selected Chemicals. Volume IlTAppendix A-19.Methylene Chloride.
EPA Contract No. 68-02-3066. SAT58-EF81-156R2. Systems Applications,
Inc., San Rafael, CA.
U.S. Department of Health and Human Services. 1983. Chemical Registry of
Toxic Effects of Chemical Substances 1981 to 1982. National Institute for
Occupational Safety ana Health. Cincinnati, OH.
U.S. Department of Health and Human Services. 1984. Manual of Analytical
Methods. Thiro Edition. National Institute for Occupational Safety and
Health. Cincinnati, OH.
U.S. Environmental Protection Agency. 1980. Treatability Manual: Volume 1,
Treatability Data. EPA 600-8-80-042a.
Weast, R. T. 1981. CRC Handbook of Chemistry and Physics. 61st Edition.
CRC Press, Inc., Boca Raton, FL.
140
-------
Chemical Name
4 ,4-Methylenediani 1 ine
CAS Number
101-77-9
Chemical Classification
Aromatic Amine
Synonyms
4-(4-aminobenzyl) aniline; bis-p-aminofenylmethan; bis(p-aminophenyl)
methane; bis(4-aminopheny1) methan; DADPM; DAPM; DDM; P,P'-diamino-
f enylmethan ; 4,4' -di ami nodi phenylmethan ; di ami nodi phenylmethane ;
P,P'-di ami nodi phenylmethane; 4, 4 '-di ami nodi phenylmethane; di-(4-
aminophenyl) methane; dianalinemethane, dianilinomethane, 4,4'-
diphenylmethanediamire; EPICURE DDM; HT 972; MDA; methylenebis
(aniline); 4,4'-methylenebisaniline; methylenedianiline; p,p'-
methylenedi aniline; 4,4'-methylenedianiline; TONOX.
Physical/Chemical Properties
Description:
Crystals from water or benzene; tan flakes or lumps, faint
amine-like odor.
Boiling Point:
398° to 399°C
Melting Point:
92° to 93°C
Molecular Weight:
198.3
Chemical Formula:
Vapor Pressure:
Negligible (0.2 mm Hg for one form)
Density:
1.056 g/m3 (liquid at 100°C)
Refractive Index:
Not available
Solubility:
Slightly soluble in cold water. Very soluble in alcohol,
benzene, ether.
141
-------
Log Partition Coefficient (octanol/water):
Estimated between 1.8 and 2.5
Photochemical Reactivity:
No primary information is available, but the known photochemi-
cal reactivity of both toluene and aniline suggests that MDA
may also be reactive.
Chemical Reactivity:
Weak base; has the general characteristics of primary aromatic
amines. Most reactions involve substitution of the amine
hydrogens or aromatic hydrogens. In some cases, the function-
al groups are totally altered. Polymers are formed when the
amine is condensed with multifunctional reactants. Decomposes
to highly toxic fumes of aniline and NO .
Environmental Fate
Only limited information is available on the chemical and biologi-
cal transformation of MDA in the environment. MDA appears to
undergo reactions typical of both aromatic amines and aromatic
compounds in general. The low vapor pressure of MDA crystals make
it improbable that MDA molecules evaporate readily to the atmo-
sphere. No information was found to indicate bioaccumulation of
MDA.
Source of Emissions
Production:
Acid catalyzed reaction of aniline with formaldehyde.
Uses:
Ninety-nine percent is consumed to manufacture methylene
phenyl diisocyanate (MDI).
Other uses include epoxy and urethane curing, production of
ketamines, wire coatings, circuit board coatings, dye inter-
mediates, rubber processing chemicals, Pharmaceuticals, and
herbicides.
Tables E-68 and E-69 present MDA production and consumption
data.
Storage:
Sold as a viscous liquid or lump in the crude form or as
flakes or granules in the pure form. Stored in tanks, 55-
gallon drums, bags, or kegs. Generally, containers consist of
fibrous material.
142
-------
TABLE E-68. PRESENT AND PROPOSED MDA MANUFACTURING PLANTS
Company
Plant location
Comments
CO
BASF Wyandotte Corp.
E.I. du Pont de Nemours
Mobay Chemical Corp.
01 in Corp.
Rubicon Chemicals Inc.
Uniroyal, Inc.
Upjohn Co.
Parsippany, NJ
Geismar, LA
Belle, WV
New Martinsville, WV
Baytown, TX
Moundsville, wV
(formerly Allied)
Geismar, LA
Naugatuck, CT
La Porte, TX
Presently imports MDA. Had a 1977 capacity of
less than 100,000 pounds/year. New plant
scheduled for operation by 1985 with a capacity
of 120 million pounds/year.
Between 10 and 15 million pounds of MDA produc-
tion in 1977. All production used to prepare
Du Pont Spandex fibers and Quiana resins.
Qiana resins no longer produced using MDA.
All MDA consumed onsite to produce MDI. The
1980 production capacities were 79 million
pounds/year at each facility. The Baytown plant
is scheduled to double its capacity by 1985.
01 in does not produce MDI and is the only sup-
plier of pure MDA. The 1972-73 production was
approximately 2 million pounds.
Most MDA is used to produce MDI. Present MDA capac-
ity is approximately 79 million pounds/year. Expan-
sion is planned to increase MDA capacity to 200 mil-
lion pounds/year by 1985.
Polymeric MDA available as Tonox.
unknown.
MDA capacity
Most MDA is used to produce MDI. MDA capacity in
1980 was 213 million pounds/year.
Note: ARCO chemical has a plant scheduled for operation in 1985 to produce MDI by a process that does not
use MDA as an intermediate. MDI capacity 150 million pounds/year.
Source: PEI Associates, Inc. 1983.
-------
TABLE E-69. ESTIMATED CONSUMPTION OF MDA FOR NON-MDI USES
End-use application
Estimated pounds/
year of pure MDA
Estimated pounds/
year of polymeric MDA
Epoxy curing
Urethane curing
Ketamine production
Wire coating production
Production of coatings for printed
circuit boards and aircraft parts
Dye intermediates
Rubber processing chemical
Corrosion inhibitor
Antioxidant for lubricating oil
Intermediate for Pharmaceuticals,
herbicides, etc.
200,000-450,000
50,000
40,000
220,000
50,000
50,000
10,000
0
0
140,000
1,500,000
a
a
a
a
a
b
a
200,000
No information found.
Although no estimate was reported, it is believed that some polymeric MDA
is used for this purpose.
Source: PEI Associates, Inc. 1983.
144
-------
Transportation:
Shipped in bulk by tank car or in packaged container by truck.
No special handling procedures.
Disposition:
Ninety-nine plus percent is consumed in chemical reactions.
Any unreacted or spilled material is probably disposed of in a
sanitary landfill.
Sampling and Analytical Methods
Limited information regarding sampling and analytical methods for
MDA was reported by JRB Associates (1981). Adsorption onto activa-
ted charcoal, XAD-2, and XAD-4 was reported for aqueous solutions.
No references were found for vapor monitoring of MDA. Analyses by
liquid chromatography, visible spectrometry, and wet chemical
methods have been reported. No data on any monitoring of MDA in
the environment could be found.
Permissible Exposure Limits
OSHA ACGIH (skin)
TWA Not established 0.1 ppm (0.8 mg/m3)
STEL 0.5 ppm (4 mg/m3)
The ACGIH has listed MDA for intended changes to delete the STEL
and add notation that MDA is an industrial substance suspected of
carcinogenic potential in man.
Human Toxicity
Acute Toxicity:
An eye irritant. Human systemic effects. High toxicity via
oral, subcutaneous, and intraperitoneal routes. Does not seem
to be readily absorbed through the skin.
Chronic Toxicity:
MDA has been shown to be carcinogenic in both sexes of rats
and mice in bioassays conducted by the National Toxicology
Program and is considered a potential carcinogen in humans.
Bibliography
American Conference of Governmental Industrial Hygienists. 1984. TLVs,
Threshold Limit Values for Chemical Substances and Physical Agents in the
Work Environment and Biological Ixposure Indices With Intended Changes for
1984-1985. ISB N:0 - 936712-54-6. Cincinnati, OH.
Pica Ex
12-54-6.
145
-------
Hawley, G. G. 1981. The Condensed Chemical Dictionary. 10th Edition. Van
Nostrand Reinhold Company, New York, NY.
International Agency for Research on Cancer. 1974. IARC Monographs on the
Evaluation of Carcinogenic Risk of Chemicals to Man - 4,4'-Methylenediani-
line.Lyon, France, p. 79-85.
JRB Associates. 1981. TSCA Section 4 Human Exposure Assessment: 4,4'-
Methylenediam'line. Prepared for the U.S. Environmental Protection Agency,
Washington, D.C.
Kirk-Othmer. 1980. Encyclopedia of Chemical Technology, 3rd Edition -
Methylenedianiline.John Wiley and Sons.New York. p. 338.
PEI Associates, Inc. Cincinnati, Ohio. 1983. Exposure to and Control of
4,4'-Methylenediani1ine. Prepared for U.S. Environmental Protection
Agency, Office of Toxic Substances, Washington, D.C.
Sax, I. N. 1981. Dangerous Properties of Industrial Materials. Sixth
Edition. Van Nostrand ReinhoTd Company, New York.
Sittig, M. 1981. Handbook of Toxic and Hazardous Chemicals. Noyes
Publications, Park Ridge, NO.
Springborn Regulatory Services, Inc. 1983. Non-Isocyanate Uses of4,4'-
Methy1 en e d i a n i 1 i n e. Prepared for the U.S. Environmental Protection Agency,
Office of Toxic Substances, Washington, D.C.
Systems Applications, Inc. 1980. Human Exposure to Atmospheric Concentra-
tions of Selected Chemicals, Volume 1.PB 81-193252.Systems Applica-
tions, Inc., San Rafael, CA.
U.S. Department of Health and Human Services. 1983. Chemical Registry of
Toxic Effects of Chemical Substances 1981 to 1982. National Institute for
Occupational Safety and Health.Cincinnati, OH.
U.S. Environmental Protection Agency, 1978. Human Exposure to Atmospheric
Concentrations of Selected Chemicals. Office of Air Quality Planning and
Standards.Research Triangle Park, NC.
146
-------
Chemical Name
Perch!oroethylene
CAS Number
127-18-4
Chemical Classification
Chlorinated hydrocarbon (unsaturated)
Synonyms
Ankilostin; antisol 1; carbon bichloride; carbon dichloride; cztero-
chloroetylen; didakene; dow-per; ENT-1860; ethene, tetrachloro-;
ethylene tetrachloride; fedal-UN; NCI-C04580; NEMA; PER; perawin;
PERC; perch!oerethyleen, per; perch!oroethylene; perclene; percloro-
etilene; percosolve; perk; perklore; persec; tetlen; teracap;
tetrachlooretheen; tetrachloraethen; tetrachlorethylene; tetra-
chloroethene; tetrachloroethylene; 1,1,2,2-tetrachloroethylene;
tetrachloroethylene (DOT); tetradoroefeen; tetraleno; tetralex;
tetravec; tetrogner; tetropil.
Physical/Chemical Properties
Description:
Colorless liquid; ether-like odor
Boiling Point:
121°C
Melting Point:
-22.4°C
Molecular Weight:
165.8
Chemical Formula:
C12C:CC12
Vapor Pressure:
15.8 mm at 22°C
Vapor Density:
5.83 (air = 1)
Refractive Index:
ND25 = 1.5029
Solubility:
Miscible with alcohol, ether, and oils in all proportions;
insoluble in water.
147
-------
Log Partition Coefficient (octanol/water):
2 Op
.00
Photochemical Reactivity:
Photochemically reactive
Chemical Reactivity:
When heated to decomposition, emits toxic chloride fumes.
Material is extremely stable and resists hydrolyzers. Reacts
violently with Ba, Be, Li, NgO^, and NaOH. May be handled in
the presence or absence of air, water, and light with any of
the common construction materials at a temperature up to
140°C.
Environmental Fate
The predominant fate of perch!oroethylene is tropospheric photo-
oxidation by hydroxyl radicals, which yields trichloroacetyl-chlo-
ride and phosgene. Rapid volatilization is the primary transport
process. There is a moderate potential for bioaccumulation and
possible biodegradation by higher organisms.
Source of Emissions
Production:
Made by chlorination of hydrocarbons, and pyrolysis of the
carbon tetrachloride also formed.
From acetylene and chloride via trichloroethylene.
Uses:
Dry cleaning solvent
Manufacture of fluorocarbons
Vapor-degreasing solvent
Drying agent for metals and certain other solids
Textile processing
Vermifuge
Heat transfer medium
Tables E-70 through E-74 present perchloroethylene production,
consumption, and emission data.
Storage:
Store in, a cool, dry, well-ventilated location, away from any
area where the fire hazard may be acute.
Transportation:
Shipped in 5- and 55-gallon steel drums, tank cars, and tank
trucks.
148
-------
TABLE E-70. LOCATIONS OF AND PRODUCTION FIGURES FOR
PERCHLOROETHYLENE FACILITIES
Location
California
Pittsburg
Kansas
Wichita
Kentucky
Louisville
Louisiana
Baton Rouge
Geismar
Lake Charles
Plaquemine
Texas
Corpus Christi
Deer Park
Freeport
Company3
Dow Chemical USA
Vulcan Materials Co.
Stauffer Chemical Co.
Ethyl Corporation
Vulcan Materials Co.
PPG Industries, Inc.
Dow Chemical
DuPont0
Diamond Shamrock
Dow Chemical
Manufac-
turing.
process
Cl-HC
Cl-HC
Cl-HC
Cl-EDC
Cl-HC
Ox-EDC
Cl-HC
Cl-HC
Cl-EDC
Cl-EDC
Total
1978
capacity,
106 kg
20
20
30
20
70
90
50
70
75
70
515
1978
estimated
pro-
duction,
106 kg
10
10
20
10
40
50
30
40
40
40
290
An August 1978 article in Chemical Marketing Reporter stated that the Hooker
Chemical Corporation facility at Taft, Louisiana stopped producing perc in
March 1978.
Key to symbols: Cl-HC = Chlorination of C\ to C3 hydrocarbons or their
partially chlorinated derivatives; Cl-EDC = chlorination of ethylene
dichloride; Ox-EDC = oxychlorination of ethylene dichloride.
cCaptive use only.
SRI International, 1979.
149
-------
TABLE E-71. ESTIMATED CONSUMPTION OF PERCHLOROETHYLENE BY TYPE OF USE
1978
Type of use
Dry cleaning
Metal cleaning
Chemical intermediate
Textile processing
•
Miscellaneous
Total
Consumption,
106 kg
160
50
40
20
30
300
Percent
of total
53
17
13
7
10
100
Source: SRI International, 1979.
TABLE E-72. ESTIMATED NUMBER OF URBAN DRY CLEANERS USING
PERCHLOROETHYLENE BY SIZE OF OPERATION
Type
of operation
Commercial
Coin-operated
Industrial
Number of operations
1 to 4
4,200
3,700
20
5 to 9
1,900
500
10
10 to 19
850
120
20
By number
of employees
20 to 49
700
60
100
>50
120
10
110
Total
7,770
4,390
260
Source: SRI International, 1979.
150
-------
TABLE E-73. ESTIMATED PERCHLOROETHYLENE USED FOR DECREASING
IN THE MANUFACTURING INDUSTRY
SIC
Code3
331
336
339
342
343
344
345
347
349
352
361
362
364
366
367
371
372
Fraction using
perch! oroethylene
Number of employees
0 to 20
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.08
0.00
0.00
0.00
0.17
0.00
0.00
0.06
0.00
0.10
>20
0.11
0.06
0.14
0.09
0.14
0.08
0.18
0.11
0.14
0.11
0.07
0.00
0.07
0.11
0.00
0.05
0.22
Amount of perch! oroethylene
used per plant, gal /year
Number of employees
0 to 20
_
-
-
-
-
-
-
330
_
_
-
219
_
-
700
-
10
20 to 100
l,800a
45a
12,000
2,655a
2,750
350
863a
5,262
1,310
90a
149a
_
73a
176a
-
110
490
>100
10,000
250
67,200a
14,752
15,400a
l,960a
4,795
17,044a
7,336a
500
825
_
403
980
-
616a
25,703
These amounts have been extrapolated on the basis of the number of employees
in the plant.
•*
Source: SRI International, 1979.
151
-------
TABLE E-74. ESTIMATED EMISSIONS FROM PERCHLOROETHYLENE FACILITIES
Location
California
Pittsburg
Kansas
Wichita
Kentucky
Louisville
Louisiana
Baton Rouge
Geismar
Lake Charles
Plaquemine
Texas
Corpus Christi
Deer Park
Freeport
Company
Dow Chemical USA
Vulcan Materials Co.
Stauffer Chemical Co.
Ethyl Corporation
Vulcan Materials Co.
PPG Industries, Inc.
Dow Chemical
DuPont3
Diamond Shamrock
Dow Chemical
Estimated
annual
emissions
103 kg
20
20
40
20
80
250
60
80
80
80
Estimated
emission
rate
9/s
0.63
0.63
1.27
0.63
2.54
7.90
1.90
2.54
2.54
2.54
Captive use for C. fluorocarbons; emission factor is unchanged.
Source: SRI International, 1979.
152
-------
Disposition:
Perchloroethylene may be disposed of by incineration, prefer-
ably after mixing with another combustible fuel. Care must be
exercised to assure complete combustion to prevent the forma-
tion of phosgene. An acid scrubber is required to remove the
halo acids produced. Alternatively, perchloroethylene may be
recovered from waste gases and reused.
Sampling and Analytical Methods
1. NIOSH Method S335
a. Adsorption on charcoal.
b. Desorption with carbon disulfide.
c. Gas chromatography.
Detection limit:
136 to 4065 ng/m3 (20 to 600 ppm) for 3-liter sample
Possible interferences:
High humidity will lower vapor trapping efficiency. Any
compound with the same retention time as perchloroethylene
may be an interferent.
2. NIOSH Method P&CAM 127
a. Adsorption on charcoal.
b. Desorption with carbon disulfide.
c. Gas chromatography.
Detection limit:
0.6 mg/m3 (0.01 ppm) with a 1-liter minimum sample size
Possible interferences:
High humidity will lower vapor trapping efficiency. Any
compound with the same retention time as perchloroethylene
may be an interferent.
3. Method B (Appendix A): C2-C18 hydrocarbons and other nonpolar
organics with a boiling point - 100° to 175°C.
a. Whole air collection in canister.
b. Cryogenic concentration.
c. Gas chromatography/flame ionization detection (gas
chromatography/electron capture detection may also be
used).
Detection limit:
0.1 ppb per 100-ml sample
Possible interferences:
Storage time greater than a week is not recommended.
153
-------
Method C (Appendix A): C6-C12 hydrocarbons and other nonpolar
organics with a boiling point between 60° and 200°C.
a. Adsorption on Tenax.
b. Thermal desorption.
c. Gas chromatography/mass spectrometry analysis (gas
chromatography/electron capture detection may also be
used).
Detection limit:
1 to 200 ppt for a 20-liter sample
Possible interferences:
Blank levels usually limit sensitivity artifacts due to
reactive components (03, NOX). Sample can be analyzed
only once.
Method D (Appendix A): C6-C12 hydrocarbons and other nonpolar
organics with a boiling point of 60° to 200°C.
a. Adsorption on Tenax.
b. Thermal desorption into canisters.
c. Gas chromatography/flame ionization detection, or gas
chromatography/mass spectrometry analysis (gas chromato-
graphy/electron capture detection may also be used).
Detection limit:
0.01 to 1 ppb for a 20-liter sample
Possible interferences:
Blanks and artifact problems in Method C, above.
Permissible Exposure Limits
OSHA AC6IH
TWA 100 ppm 50 ppm (335 mg/m3)
STEL 200 ppm (1,340 mg/m2)
r^i'linn 9HO nnm
Ceiling 200 ppm
Peak 300 ppm (5 min. in 3 h)
Human Toxicity
Acute Toxicity:
Moderate irritation effects via inhalation, oral, subcutane-
ous, intraperitoneal, and dermal routes. High toxicity via
intravenous route. Not corrosive or dangerously acutely
reactive, but toxic by inhalation, by prolonged or repeated
contact with skin or mucous membrane, or when ingested by
mouth. The liquid can cause injuries to the eyes. Exposures
to higher than 200 ppm causes irritation, lachrymation, burn-
ing of the eyes, and irritation of the nose and throat. There
may be vomiting, nausea, drowsiness, an attitude of
154
-------
irresponsibility, and even the appearance of alcholic intoxi-
cation. Also acts as an anesthetic. Can cause dermatitis,
particularly after repeated or prolonged contact with skin,
preceded by reddening and burning and more rarely, a blister-
ing of the skin.
Chronic Toxicity:
Perchloroethylene caused hepatocellular carcinomas in mice of
both sexes; however, a carcinogenesis bioassay was negative in
rats. Therefore, perch!oroethylene can be considered a sus-
pected animal carcinogen.
Bibliography
American Conference of Governmental Industrial Hygienists. 1984. TLVs,
Threshold Limit Values for Chemical Substances and Physical Agents in the
Work Environment and Biological Exposure Indices with Intended Changes for
1984-1985.ISB N:0 - 936712-54-6.Cincinnati, OH.
Hawley, G. G. 1981. The Condensed Chemical Dictionary. 10th Edition. Van
Nostrand Reinhold Company, New York.
National Fire Protection Association. 1983. National Fire Codes, A Com-
pliance of NFPA Codes, Standards, Recommended Practices, and Manuals.~
Volume 13.NFPA, Quincy, MA.
Sax, I. N. 1981. Dangerous Properties of Industrial Materials.
Sixth Edition. Van Nostrand Reinhold Company, New York.
Sittig, M. 1981. Handbook of Toxic and Hazardous Chemicals. Noyes
Publications, Park Ridge, NJ.
SRI International. 1979. Assessment of Human Exposures to Atmospheric
Perch!orqethylene. Prepared for the U.S. Environmental Protection Agency,
Office of Air Quality Planning and Standards, Research Triangle Park, NC.
U.S. Department of Health and Human Services. 1983. Chemical Registry of
Toxic Effects of Chemical Substances 1981 to 1982. National Institute for
Occupational Safety and Health.Cincinnati, OH.
U.S. Department of Health and Human Services. 1984. Manual of Analytical
Methods. Third Edition. National Institute for Occupational Safety and
Wealth. Cincinnati, OH.
U.S. Environmental Protection Agency. 1980. Treatability Manual: Volume 1
Treatability Data. EPA 600-8-80-042a.
Weast, R. T. 1981. CRC Handbook of Chemistry and Physics. 61st Edition.
CRC Press, Inc., Boca Raton, FL.
155
-------
Chemical Name
Phenol
CAS Number
108-95-2
Chemical Classification
Phenol (aromatic alcohol)
Synonyms
Acide carbolique; Bakers P and S liquid and ointment; carbolic
acid; carbolic acid (DOT); carbolsaure; fenol; fenolo; hydroxy-
benzene; monohydroxybenzene, NCI-50124; oxybenzene; phenic acid;
phenole; phenyl hydrate; phenyl hydroxide; phenylic acid; phenylic
alcohol.
Physical/Chemical Properties
Description:
White crystalline mass that turns pink or red if not perfectly
pure or if under influence of light; absorbs water from the
air and liquifies; distinctive odor; sharp burning taste.
When in very weak solution, has a sweetish taste.
Boiling Point:
182°C
Melting Point:
42.5° to 43°C
Molecular Weight:
94.1
Chemical Formula:
C6H5OH
Vapor Pressure:
1 mm at 40.1°C
Vapor Density:
3.24 (air = 1)
Refractive Index:
N"1 = 1.5408
156
-------
Solubility:
Soluble in alcohol, water, ether, chloroform, glycerol, carbon
disulfide, petrolatum, fixator volatile oils or alkalines.
Log Partition Coefficient (octanol/water):
1.46
Photochemical Reactivity:
Reactivity toward OH« is 2 times butane. Reactivity toward 03
is a 9.6-hour half-life or 15 percent of propylene.
Chemical Reactivity:
Reacts violently with (A1C13 + nitrobenzene), butadiene,
peroxydisulfuric acid, and peroxymonosulfuric acid. Moderate
fire hazard when exposed to heat, flame, or oxidizers. When
heated, emits toxic fumes, can react with oxidizing materials.
Environmental Fate
Photooxidation of volatilized phenol and photolysis of phenolic
anion may both take place at moderate rates. Metal catalyzed
oxidation may take place in highly aerated waters. No bioaccumu-
lation, but extensive biodegradation in natural waters.
Source of Emissions
Production:
Oxidation of cumene
Derivation from benzoic acid
Uses:
Phenolic resins
Epoxy resins (bisphenol-A)
Nylon 6 (caprolactam)
2,4-D
Selective solvent for refining lubricating oils
Adipic acid
Salicylic acid
Phenolphthaline
Pentachlorophenol
Acetophenetidine
Picric acid
Germicidal paints
Pharmaceuticals
Laboratory reagent
Dyes and indicators
Slimicide
General disinfectant
Tables E-75 through E-83 and Figure E-5 present phenol produc-
tion, consumption, and emission data.
157
-------
TABLE E-75. PHENOL PRODUCERS (NATURAL PHENOL)
Company
Ferro Corporation
Koppers
Merichem
Stimson Lumber
U.S. Steel Corporation
Location
Sante Fe Springs, CA
Follansbee, WV
Houston, TX
Anacortes, WA
Clairton, PA
Total
1978
capacity,
106 Ib/yr
12
12
12
12
12
60
1978
production,
106 Ib/yr
5.4
5.4
5.4
5.4
5.4
27
Geographical location,
latitude/longitude
33 56 30/118 04 18
40 23 10/80 35 07
29 45 36/95 10 48
48 28 31/122 32 48
40 18 15/79 52 43
en
oo
Total capacity and production distributed evenly over all five sites in the absence of capacity figures.
Source: Systems Applications, Inc. 1980.
-------
TABLE E-76. PHENOL PRODUCERS (SYNTHETIC PHENOL)
Company
Allied Chemical
Clark
Dow
Georgia Pacific
Getty
Kalama
Monsanto
Shell
Standard Oil of
California
Union Carbide
U.S. Steel
Location
Philadelphia, PA
Blue Island, IL
Freeport, TX
Plaquemine, LA
El Dorado, KS
Kalama, WA
Chocolate Bayou, TX
Deer Park, TX
Richmond, CA
Bound Brook, NJ
Haverhill, OH
Total
1978
capacity,
106 Ib/yr
600
88
465
265
95
75
500
500
55
180
325
3148
1978
production,
106 Ib/yr
453
66
351
200
72
57
377
377
42
135
245
2375
Geographical location,
latitude/longitude
40 00 24/75 04 07
41 39 21/87 41 56
28 59 12/95 24 05
30 15 00/91 11 00
37 47 10/96 52 00
46 00 54/122 51 05
20 14 55/95 12 45
29 42 57/95 07 28
37 56 12/122 20 48
40 33 32/74 31 18
38 34 52/82 49 36
en
Total production distributed based on individual site capacity.
Source: Systems Applications, Inc. 1982.
-------
TABLE E-77. PHENOL END-USE 1978
(SYNTHETIC AND NATURAL PHENOL)
Source
Phenolic resins
Bisphenol-A
Caprolactam
Nonyl phenol
Salicylic acid
Dodecyl phenol
Adipic acid
Miscellaneous
Exports
Total
Usage, 106 Ib/yr
1045
405
355
48
48
24
24
382
71
2402
Percent usage
44
17
15
2
2
1
1
15
3
100
Source: Systems Applications, Inc. 1980.
TABLE E-78. 1978 PHENOL NATIONWIDE EMISSIONS
Source
Nationwide
emissions,
Ib/yr
Production
Phenolic resins
Bisphenol-A
Caprolactam3
Nonylphenol
Salicylic acid
Dodecylphenol
Miscellaneous
Export
3,708,080
522,500
202,500
511,200
41,700
24,000
24,000
259,760
0
Total
5,293,740
Includes emissions from adipic acid manufacture.
Source: Systems Applications, Inc. 1982.
160
-------
TABLE £-79. PHENOL USER LOCATIONS
Company
Location
1978
capacity,
10<> Ib/yr
1978
production,
106 Ib/yr
Geographical location,
latitude/longitude
Bisphenol-A
producers
Dow
General Electric
Shell
U.S. Steel
Freeport, TX
Mount Vernon, IN
Deer Park, TX
Haverhill , OH
Total
150
220
150
120
640
95
140
95
75
405
28 59 12/95 24 05
37 56 42/87 34 25
29 42 55/95 07 34 ,
38 34 52/82 49 36
j
en
Caprolactam producer
Allied
Hopewell , VA
Total
400
400
355
355
37 22 13/77 18 08 i
i
Nonylphenol producers
Borg Warner
Exxon
GAP
Jefferson
Kalama
Monsanto
Rohm and Haas
Schenectady
Morgantown, WV
Bayway, NJ
Calvert City, KY
Linden, NJ
Port Neches, TX
Kalama, WA
Kearney, NJ
Deer Park, TX
Philadelphia, PA
Rotterdam Junction, NY
Oyster Creek, TX
Total
60
20
5
20
35
20
40
10
20
20
50
300
10
3
1
3
6
3
6
2
3
3
8
48
39 40 39/80 58 34
40 38 46/74 11 48
37 02 50/88 21 12
40 38 19/74 15 26 ;
29 57 45/93 56 00 \
46 00 54/122 51 05
40 46 12/74 09 08
29 43 30/95 06 15
39 54 50/75 11 30
42 47 22/73 43 12
29 58 21/95 20 38
(continued)
-------
TABLE E-79 (continued)
Company
Location
1978
capacity,
106 Ib/yr
1978
production,
106 Ib/yr
- . . . 1
Geographical locationj
1 ati tude/ 1 ongi tude
Salicylic acid producers
Dow
Monsanto
Sterling Drug
Tenneco
Midland, MI
St. Louis, MO
Cincinnati , OH
Garfield, NJ
Total
15
20
8
10
53
14
18
7
9
48
43 35 28/84 13 08
38 34 37/90 11 42
39 05 15/84 33 09
40 52 28/74 06 49
Dodecyl phenol producers
Borg Warner
GAP
Monsanto
Morgantown, WV
Calvert City, KY
Kearney, NJ
Total
60
5
40
105
4
1
9
14
39 40 39/80 58 34
37 02 05/88 21 12
40 46 12/74 09 08
Adipic acid producer
Allied
Hopewel 1 , VA
Total
30
30
24
24
37 22 13/77 18 08
Source: Systems Applications, Inc. 1980.
-------
TABLE E-80. PHENOL EMISSIONS FROM PHENOL PRODUCERS
Company
Allied
Clark
Dow
Georgia Pacific
Getty
Kalama
Monsanto
Shell
Standard Oil of
California
Union Carbide
U.S. Steel
Ferro
Koppers
Merichem
Stimson
U.S. Steel
Location
Philadelphia, PA
Blue Island, IL
Freeport, TX
Plaquemine, LA
El Dorado, KS
Kalama, VIA
Chocolate Bayou, TX
Deer Park, TX
Richmond, CA
Bound Brook, NJ
Haverhill, OH
Sante Fe Springs, CA
Follansbee, WV
Houston, TX
Anacortes, WA
Clairton, PA
Total
Process
emissions,
Ib/yr
23,000
117,480
624,780
356,000
128,160
101,460
8,419
671,060
74,760
240,300
436,100
9,612
9,612
9,612
9,612
9,612
2,829,579
Storage
emissions,
Ib/yr
172,000
1,980
10,530
6,000
2,160
1,710
142
11,310
1,260
4,050
7,350
162
162
162
162
162
219,302
Fugitive
emissions,
Ib/yr
12,740
27,060
143,910
82,000
29,520
23,370
1,939
154,570
17,220
55,350
100,450
2,214
2,214
2,214
2,214
2,214
659,199
Total emissions
Ib/yr
207,740
146,520
779,220
444,000
159,840
126,540
10,500
836,940
93,240
299,700
543,900
11,988
11,988
11,988
11,988
11,988
3,708,080
9/s
2.99
2.11
11.22
6.39
2.30
1.82
.15
12.05
1.34
4.31
7.83
0.17
0.17
0.17
0.17
0.17
o>
Source: Systems Applications, Inc. 1982.
-------
TABLE E-81. PHENOL PRODUCTION AND END-USE EMISSION FACTORS
Source
Phenol production
Caprolactam
Bisphenol-A
Nonyl phenol
Salicylic acid
Dodecyl phenol
Phenolic resins
Adipic acid
Miscellaneous
Emission factor, Ib phenol lost per Ib used (produced)
Process
0.00178
0.00130
0.00035
0.00080
0.00035
0.00080
0.00035
Storage
0.00003
0.00001
0.00003
0.00001
0.00001
0.00001
0.00002
Fugitive
0.00041
0.00013
0.00012
0.00019
0.00014
0.00019
0.00013
Total
0.00222
0.00144
0.00050
0.00100
0.00050
0.00100
0.00050
Derivation9
C
A
C
C
C
D
D
Phenol emissions are included with caprolactam pro-
duction losses
0.00068b
A - Site visit data, B - State files, C - Published data, D - Hydroscience
estimate
Based on a weighted average of all other phenol end-use emission factors.
Source: Systems Applications, Inc. 1980.
164
-------
TABLE E-82. PHENOL EMISSIONS FROM END USERS
Company
Location
Phenol emissions
Process
lb/yr
Storage
lb/yr
Fugitive
lb/yr
Total
lb/yr g/s
Bisphenol-A producers
Dow
General Electric
Shell
U.S. Steel
Freeport, TX
Mount Vernon, IN
Deer Park, TX
Haverhill, OH
Total
33,250
49,000
33,250
26,250
141,750
2,850
4,200
2,850
2,250
12,150
11,400
16,800
11,400
9,000
48,600
47,500
70,000
47,500
37,500
202,500
0.68
1.01
0.68
0.54
cn
Caprolactam producer
Allied
Hopewel 1 , VA
461,500
3,550
46,150
511,200
7.36
Nonyl phenol producers
Borg Warner
Exxon
GAF
Jefferson
Kalama
Monsanto
Rohm and Haas
Morgantown, WV
Bayway, NO
Calvert City, KY
Linden, NJ
Port Neches, TX
Kalama, WA
Kearny, NJ
Deer Park, TX
Philadelphia, PA
8,000
450
800
2,400
4,800
2,400
1,360
1,600
2,400
100
28
10
30
60
30
17
20
30
1,900
522
190
570
1,140
570
323
380
570
10,000
1,000
1,000
3,000
6,000
3,000
1,700
2,000
3,000
0.144
0.014-
0.014
0.043
0.086
0.043
0.024
0.029
0.043
(continued)
-------
TABLE E-82 (continued)
Company
Location
Phenol emissions
Process
lb/yr
Storage
lb/yr
Fugitive
Ib/yr
Total
lb/yr g/s
Nonylphenol producers (continued)
Schenectady
Rotterdam Junction, NY
Oyster Creek, TX
J Total
2,400
6,400
33,010
30
80
435
570
1,520
8,255
3,000
8,000
41,700
0.043
0.115
Salicylic acid producers
Dow
Monsanto
Sterling Drug
Tenneco
Midland, MI
St. Louis, MO
Cincinnati, OH
Garfield, NJ
Total
4,900
6,300
2,450
3,150
16,800
140
180
70
90
480
1,960
2,520
980
1,260
6,720
7,000
9,000
3,500
4,500
• r-
24,000
0.101
0.130
0.050
0.065
cr>
cr>
Dodecylphenol producers
Borg Warner
GAF
Monsanto
Morgantown, WV
Clavert City, KY
Kearny, NJ
Total
11,200
800
7,200
19,200
140
10
90
240
2,660
190
1,710
4,560
14 ,000
1,000
9,000
24,000
0.202
0.014
0.130
Adi pic acid producer
Allied
Hopewel1, VA
Emissions are included in caprolactam production losses
Source: Systems Applications, Inc. 1982.
-------
TABLE E-83. EMISSIONS AND METEOROLOGICAL STATIONS OF SPECIFIC POINT SOURCES OF PHENOL
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Company
Allied
Clark
Georgia
Pacific
Getty
Monsanto
Standard
Union Car-
bide
Ferro
Koppers
Merichem
Stimson
U.S. Steel
Dow
Shell
U.S. Steel
Site
Frankford, PA
Blue Island, IL
Plaquemine, LA
El Dorado, KS
Chocolate
Bayou, TX
Richmond, CA
Bound Brook,
NJ
Sante Fe
Springs, CA
Follansbee, WV
Houston, TX
Anacortes, WA
Clairton, PA
Freeport, TX
Deer Park, TX
Haverhill, OH
Latitude
40 18 15
41 39 21
30 15 00
37 47 10
29 14 55
37 56 12
40 33 32
33 56 30
40 23 10
29 45 36
48 28 31
40 18 15
28 59 30
29 43 30
38 34 53
Longitude
079 52 43
087 41 56
091 11 00
096 52 00
095 12 45
122 20 48
074 31 18
118 04 18
080 35 07
095 10 48
122 32 48
079 52 43
095 23 35
095 06 15
083 49 36
Star
station
14762
14855
13970
03920
12906
12906
94741
93106
14762
12906
24217
14762
12923
12986
13866
Plant Source
type3
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
type
1
1
1
1
1
1
1
1
1
1
1
1
1
2
1
2
1
Emissions, g/s
Process
11.611296
1.691712
5.126400
1.845504
9.663264
1.076544
3.468320
0.138413
0.138413
0.138413
0.138413
0.138413
8.996832
0.478800
9.663264
0.478800
6.279840
0.378000
Storage
0.195696
0.028512
0.086400
0.031104
0.162864
0.018144
0.058320
0.002338
0.002338
0.002338
0.002338
0.002338
0.151632
0.041040
0.162864
0.041040
0.105840
0.032400
Fugitive
2.674512
0.389664
1 . 180800
0.425088
2.225808
0.247968
0.797040
0.031882
0.031882
0.031882
0.031882
0.031882
2.072304
0.164160
2.225888
0.164160
1.446480
0.129600
cr»
(continued)
-------
TABLE E-83 (continued)
No.
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
Company
Kalama
General
Electric
Allied
Exxon
GAP
Jefferson
Rohm and
Haas
Rohm and
Haas
Schenectady
Schenectady
Borg Warner
GAP
Monsanto
Dow
Monsanto
Sterling
Tenneco
Site
Kalama, WA
Mount Vernon,
IN
Hopewell , VA
Bayway, NJ
Linden, NJ
Port Neches, TX
Deer Park, TX
Philadelphia,
PA
R Junction, NY
Oyster Creek,
TX
Morgantown, PA
Calvert City,
KY
Kearny, NJ
Midland, MI
St. Louis, MO
Cincinnati , OH
Garfield, NJ
Latitude
46 00 54
37 56 43
37 23 13
40 38 46
40 38 19
29 57 45
29 43 00
39 54 50
42 47 22
29 58 21
39 40 39
37 02 50
40 46 12
43 35 28
33 34 37
39 05 15
40 52 28
Longitude
122 51 05
087 34 25
077 18 08
074 11 48
074 15 26
093 56 00
095 06 15
075 11 30
073 43 12
095 20 38
080 58 34
088 21 12
074 09 08
084 13 08
097 11 42
084 33 09
074 06 47
Star
station
24229
93817
13740
94741
94741
12917
12906
13739
14735
12960
13736
03816
94741
14845
13994
13840
94741
Plant Source
type3
3
4
5
6
6
6
6
6
6
6
7
7
7
8
8
8
8
typeb
1
4
3
3
4
4
4
4
4
4
4
4
6
4
6
4
6
5
5
5
5
Emissions, q/s
Process
1.461024
0.034560
0.705600
6.643600
0.034560
0.034560
0.069120
0.028040
0.034560
0.034560
0.092160
0.115200
0.161288
0.011520
0.011520
0.069120
0.103680
0.070560
0.090720
0.035280
0.045360
Storage
0.024624
0.000432
0.060480
0.051120
0.000432
0.000432
0.000864
0.000288
0.000432
0.000432
0.001152
0.001440
0.002016
0.000144
0.000144
0.000864
0.001296
0.002016
0.002592
0.001008
0.001296
Fugitive
0.836528
0.008208
0.241920
0.664560
0.008208
0.008208
0.016416
0.005472
0.008208
0.008208
0.021888
0.027360
0.038304
0.002736
0.002736
0.016416
0.024624
0.028224
0.036288
0.014112
0.018144
00
(continued)
-------
cr>
vo
TABLE E-83 (continued)
a Plant types: 1 - plant produces phenol; 2 - plant produces phenol and Bisphenol-A; 3 - plant produces
phenol and nonylphenol; 4 - plant produces Bisphenol-A; 5 - plant produces caprolactam and adipic acid;
6 - plant produces nonylphenol; 7 - plant produces nonylphenol and dodecylphenol; 8 - plant produces
salicylic acid.
Source types: 1 - phenol production; 2 - Bisphenol-A production; 3 - caprolactam/adipic acid production;
4 - nonylphenol production; 5 - salicylic acid production; 6 - dodecylphenol production.
Source: Systems Applications, Inc. 1982.
-------
NOTE: NUMERALS DENOTE NUMBER OF PLANTS.
Figure E-5. Specific point sources of phenol emissions.
Source: Systems Applications, Inc. 1980.
-------
Storage:
Should be protected from physical damage, and stored in a
cool, dry, well-ventilated location, away from any areas where
the fire hazard may be acute. Outside or detached storage is
preferred, separate from other storage. Spills must be dis-
posed of immediately by properly protected personnel.
Transportation:
Should be shipped in bottles, cans, drums, tankcars, tank
barges. Must be Tabled "Poison B."
Disposition:
Phenol may be disposed of by incineration.
Sampling and Analytical Methods
1. NIOSH Method S330
a. Bubbler (0.1 ^ sodium hydroxide).
b. Gas chromatography.
c. Flame ionization detector.
Detection limit:
0.25 ppm with 100-liter sample
Possible interferences:
None identified.
2. Method C (Appendix A): C6-C12 hydrocarbons and other nonpolar
organics with boiling point between 60° and 200°C.
a. Adsorption on Tenax.
b. Thermal desorption.
c. Gas chromatography/mass spectrometry analysis.
Detection limit:
1 to 200 ppt for a 20-liter sample
Possible interferences:
Blank levels usually limit sensitivity artifacts due to
reactive components (03, NO ). Sample can be analyzed
only once.
3. Method S
Permissible Exposure Limits
OSHA (skin) ACGIH (skin) NIOSH
TWA 5 ppm (19 mg/m3) 5 ppm (19 mg/m3) 20 mg/m3
STEL 10 ppm (38 mg/m3)
Ceiling 60 mg/m3 (15 min)
Odor Perception: 0.022 mg/m3
171
-------
Human Toxicity
Acute Toxicity:
Phenol vapor or liquid is readily absorbed through the skin or
any mucous membrane, which may cause acute and chronic poison-
ing. A concentrated solution causes bad acid burns. Phenol
is not sufficiently volatile to constitute a respiratory
hazard under normal conditions. High toxicity for oral,
intraperitoneal, subcutaneous, and parenteral methods. Moder-
ate irritant to skin, subcutaneous, oral, and parenteral area.
In acute poisoning, mainly effects central nervous system.
Absorption from spilling phenolic solutions on skin may be
very rapid, and death results from colapse within 30 minutes
to several hours. Death has resulted from phenol absorption
through 64 in.2 of skin area. Where death is delayed, damage
to kidneys, liver, pancreas, and spleen; and edema of the
lungs may result. Dermatitis resulting from contact with
phenol or phenol-containing product is fairly common. As
little as 1.5 g (oral) has killed.
Chronic Toxicity:
Phenol as a nonspecific irritant may promote development of
tumors when applied repeatedly to the skin in large amounts.
Results were negative in a carcinogenesis bioassay completed
by the National Cancer Institute.
Bibliography
American Conference of Governmental Industrial Hygienists. 1984. TLVs,
Threshold Limit Values for Chemical Substances and Physical Agents in the
work Environment and Biological Exposure jndices with Intended Changes for
1984-1985. ISB N:0 - 936712-54-6. Cincinnati, OH.
Hawley, G. G. 1981. The Condensed Chemical Dictionary. 10th Edition.
Van Nostrand Reinhold Company, New York.
National Fire Protection Association. 1983. National Fire Codes, A Comp-
liance of NFPA Codes, Standards, Recommended Practices, and Manuals.
Volume 13. NFPA, Quincy, MA.
Sax, I. N. 1981. Dangerous Properties of Industrial Materials.
Sixth Edition. Van Nostrand Reinhold Company, New York.
Sittig, M. 1981. Handbook of Toxic and Hazardous Chemicals. Noyes
Publications, Park Ridge, NJ.
Systems Applications Inc. 1982. Human Exposure to Atmospheric Concentra-
tions of Selected Chemicals, Volume II. Appendix A-24 Phenol.EPA
Contract No. 68-02-0366. Systems Applications, Inc., San Rafael, CA.
172
-------
Systems Applications Inc. 1980. Human Exposure to Atmospheric Concentra-
tions of Selected Chemicals, Volume 1.Appendix A-24 Phenol.PB
81-193252. Systems Applications, Inc., San Rafael, CA.
Systems Applications, Inc. 1982. Human Exposure to Atmospheric Concentrations
of Selected Chemicals, Volume II.Appendix A-24.Phenol.EPA Contract
No. 68-02-3066.SAI 58-EF81-156R2. Systems Applications, Inc., San Rafael, CA.
U.S. Department of Health and Human Services. 1983. Chemical Registry of
Toxic Effects of Chemical Substances 1981 to 1982. National Institute for
Occupational Safety and Health.Cincinnati, OH.
U.S. Department of Health and Human Services. 1984. Manual of Analytical
Methods. National Institute for Occupational Safety and Health.
Cincinnati, OH.
U.S. Environmental Protection Agency. 1980. Treatability Manual: Volume 1
Treatability Data. EPA 600-8-80-042a.
Weast, R. T. 1981. CRC Handbook of Chemistry and Physics. 61st Edition.
CRC Press, Inc., Boca Raton, FL.
173
-------
Chemical Name
Phosgene
CAS Number
75-44-5
Chemical Classification
Chlorinated carbonyl
Synonyms
Carbone (oxychlorure de); carbon oxychloride; carbonylchlorid;
carbonyl chloride; CG; chloroformyl chloride; carbino (ossichoruro
di) diphosgene; fosgeen; fosgen; fosgene; koolstofoxychloride;
NCI-60219; phosgen; phosgene (DOT)
Physical/Chemical Properties
Description:
Liquid or easily liquified gas; colorless to light yellow;
odor varies from strong to stifling when concentrated to
hay-like or diluted form.
Boiling Point:
8.2°C
Melting Point:
-128°C
Molecular weight:
98.9
Chemical Formula:
COC12
Vapor Pressure:
1180 mm at 20°C
Vapor Density:
3.4 (air = 1)
Refractive Index:
Not available
Solubility:
Slightly soluble in water and slowly hydrolized. Soluble in
benzene and toluene.
Log Partition Coefficient (octanol/water):
Not available
174
-------
Photochemical Reactivity:
In the atmosphere, phosgene decomposes in water to form hydro-
chloric acid.
Chemical Reactivity:
Decomposes in water to form hydrochloric acid. Because of its
high degree of reactivity, phosgene interacts with many class-
es of inorganic and organic reagents. Reacts violently with
Al, tert-butyl azido formate, 2,4-hexadiyn-l,6-diol, isopropyl
alcohol, K, Na, hexafluoro isopropylidene, amino lithium,
lithium.
Environmental Fate
Rapid hydrolysis to C02 and HC1 is the principal fate. Photolysis
can occur, but cannot compete with hydrolysis.
Source of Emissions
Production:
Obtained by passing a mixture of carbon monoxide and chlorine
over activated carbon.
Uses:
Organic synthesis, especially in isocyanates, polyurethane and
polycarbonate resins, carbonates, organic carbonates, and
chloroformates.
Pesticides
Herbicides
Dye manufacture
Tables E-84 through E-92 and Figure E-6 graphically present
phosgene production, consumption, and emission data.
Storage:
Should be protected against physical damage and stored outdoors
or in a well-ventilated area of noncombustible construction.
Transportation:
Should be shipped in steel cylinders and tank cars. All
phosgene containers require "Poison A" labels.
Disposition:
Because of its low boiling point and high toxicity, phosgene
should never be allowed to enter drains or sewers. If recycl-
ing of phosgene is not feasible, phosgene waste can be handled
by caustic scrubbing in packed columns.
Sampling and Analytical Methods
1. NIOSH Method 219
a. Midget impinger.
b. Nitrobenzylpyridine.
c. Calorimetric analysis.
175
-------
TABLE E-84. PHOSGENE PRODUCERS
Company
Allied Chemical
BASF Wyandotte
Chemtron
Dow Chemical
DuPont
General Electric
Jefferson
Minerec
Mobay Chemical
Olin
PPG
Rubicon Chemicals
Stauffer Chemicals
Upjohn
Van De Mark
Location
Moundsville, WV
Geismar, LA
La Porte, TX
Freeport, TX
Deepwater, NJ
Mt. Vernon, IN
Port Neches, TX
Baltimore, MD
Bay town, TX
New Martinsville, WV
Ashtabula, OH
Lake Charles, LA
Barberton, OH
Geismar, LA
Cold Creek, AL
LaPorte, TX
Lockport, NY
Total
1978
capacity,
106 Ib/yr
100
55
80
130
135
60
30
8
250
250
50
120
5
130
25
200
8
1,636
1978
production,
106 Ib/yr
76
41.8
60.8
98.8
102.6
45.6
22.8
6.1
190
190
38
91.2
3.8
98.8
19
152
6.1
1,243.4
Geographical location,
latitude/longitude
39 54 24/80 47 51
30 11 34/91 00 42
29 39 20/95 02 18
28 59 12/95 24 05
39 41 25/75 30 35
37 56 42/87 54 25
30 18 50/95 23 06
39 14 11/76 34 41
29 45 30/94 54 25
39 43 35/80 49 43
41 53 46/80 43 22
30 13 55/93 15 57
41 00 37/81 36 29
30 12 00/91 00 30
30 58 30/88 01 16
29 42 26/95 04 29
43 11 08/78 42 40
cr>
Source: Systems Applications, Inc. 1982.
-------
TABLE E-85. PHOSGENE END-USE DISTRIBUTION
Source
Toluene diisocyanates (TDI)
Polymeric isocyanates (MDI)
Polycarbonates
Miscellaneous
Total
Usage, 106 Ib/yr
814.5
339.5
67.8
135.6
1357.4
Percent usage
60
25
5
10
100
Source: Systems Applications, Inc. 1980.
TABLE E-86. PHOSGENE USERS
(manufacturers of polymeric isocyanates)
Company
Mobay Chemical
Rubicon
Chemicals
Upjohn
Location
Bay town, TX
New Martinsville,
WV
Geismar, LA
LaPorte, TX
Total
1978 MDI
capacity,
1()5 Ib/yr
110
50
50
250
460
1978
phosgene
use,
106 Ib/yr
81.25
36.9
36.9
184.4
339.5
Geographical
location,
latitude/longitude
29 45 30/94 54 25
39 44 50/80 50 50
30 12 00/91 00 30
29 42 26/95 04 29
Source: Systems Applications, Inc. 1980.
177
-------
TABLE E-87. PHOSGENE USERS
[.manufacturers of toluene diisocyanate (TDI)]
Company
Allied Chemical
BASF Wyandotte
Dow Chemical
DuPont
Mobay Chemical
Olin
Rubicon Chemicals
Location
Moundsville, WV
Geismar, LA
Freeport, TX
Deepwater, NJ
Baytown, TX
New Martinsville, WV
Ashtabula, OH
Lake Charles, LA
Geismar, LA
Total
1978
TDI
capacity,
106 Ib/yr
80
100
100
70
130
100
30
100
40
750
1978
phosgene use,
10g Ib/yr
80.9
101.2
101.2
70.8
131.5
101.2
30.4
101.2
40.5
758.9
Geographical location,
1 ati tude/1 ongi tude
39 54 39/80 44 49
30 11 34/91 00 42
28 59 12/95 24 05
39 41 25/75 30 35
29 45 30/94 54 25
39 44 50/80 50 50
41 53 07/80 45 50
30 13 55/93 15 57
30 12 00/91 11 30
00
Source: Systems Applications, Inc. 1982.
-------
TABLE E-88. TOTAL PHOSGENE EMISSIONS FROM PRODUCERS AND USERS
Company
Allied Chemical
BASF Wyandotte
Chemtron
Dow Chemical
DuPont
General Electric
Jefferson
Minerec
Mobay Chemical
Olin
PPG
Rubicon Chemicals
Stauffer Chemicals
Union Carbide
Upjohn
Van De Mark
Location
Moundsville, WV
Geismar, LA
LaPorte, TX
Freeport, TX
Deepwater, NJ
Mt. Vernon, IN
Port Neches, TX
Baltimore, MD
Bay town, TX
New Martinsville, WV
Ashtabula, OH
Lake Charles, LA
Barberton, OH
Geismar, LA
Cold Creek, AL
S. Charleston, WV
LaPorte, TX
Lockport, NY
Total
Phosgene emissions
Ib/yr
14,214
8,190
10,964
18,450
18,934
8,208
4,104
1,098
35,548
35,086
7,020
17 ,082
684
18,270
3,420
20,086
28,580
1,098
251,036
9/S
0.204
0.118
0.158
0.264
0.273
0.118
0.059
0.016
0.511
0.505
0.101
0.246
0.01
0.263
0.049
0.30
0.412
0.016
3,624
Source: Systems Applications, Inc. 1982.
179
-------
TABLE E-89. SOURCES OF PHOSGENE EMISSIONS
Source
Producers
Users:
Toluene diisocyanate
Polymeric isocyanates
Polycarbonates
Miscellaneous
Total
Production/usage,
106 Ib/h
1357.4
746.0
310.9
62.2
124.3
2600.8
Percent usage
-
60
25
5
10
100
Total emissions
Ib/yr
190,960
4,998
2,140
447a
893a
199,438
g/s
2.749
0.078
0.031
0.006
0.012
2.876
Based on emission factor for toluene diisocyanate (TDI)
Source: Systems Applications, Inc. 1982.
TABLE E-90. PHOSGENE EMISSIONS FROM PHOSGENE USERS FOR MDI PRODUCTION
Company
Mobay Chemical
Rubicon
Chemicals
Upjohn
Location
Baytown, TX
New Martinsville,
wv
Geismar, LA
LaPorte, TX
Process vent
emissions
Ib/yr
480
220
220
1220
g/s
0.007
0.003
0.003
0.018
Fugitive
emissions
Ib/yr
Nil
Nil
Nil
Nil
g/s
Nil
Nil
Nil
Nil
Total
Total
emissions
Ib/yr
480
220
220
1220
2140
g/s
0.007
0.003
0.003
0.018
0.031
Source: Systems Applications, Inc. 1980.
180
-------
TABLE E-91. PHOSGENE EMISSIONS FROM PHOSGENE USERS FOR TDI PRODUCTION
Company
Allied Chemical
BASF Wyandotte
Dow Chemical
DuPont
Mobay Chemical
Olin
Rubicon
Chemicals
Location
Moundsville, WV
Geismar, LA
Freeport, TX
Deepwater, NJ
Bay town, TX
New Mar tinsv file,
WV
Ashtabula, OH
Lake Charles, LA
Geismar, LA
Process vent
emissions
Ib/yr
534
666
666
466
868
666
200
666
266
g/s
0.008
0.01
0.01
0.007
0.012
0.01
0.003
0.01
0.004
Fugitive
emissions
Ib/yr
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
g/s
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Total
Total
emissions
Ib/yr
534
666
666
466
868
666
200
666
266
4,998
g/s
0.008
0.01
0.01
0.007
0.012
0.01
0.003
0.01
0.004
0.074
Source: Systems Applications, Inc. 1982.
181
-------
TABLE E-92. EMISSIONS AND METEOROLOGICAL STATIONS OF SPECIFIC POINT SOURCES OF PHOSGENE
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
Company
Allied
Chemical
BASF Wyan-
dotte
Dow
DuPont
Mobay
Mobay
Olin
Olin
Rubicon
Upjohn
Chemetron
General
Electric
Jefferson
Minerec
ITC
Stauffer
Vandermark
Site
Moundsville, WV
Ceismar, LA
Freeport, TX
Deepwater, NJ
Bay town, TX
New Martins-
vine, WV
Astabula, OH
Lake Charles,
LA
Geismar, LA
LaPorte, TX
LaPorte, TX
Mt. Vernon, IN
Port Neches, TX
Baltimore, MD
Barberton, OH
Cold Creek, AL
Lockport, NY
Latitude
39 54 39
30 11 34
28 59 30
39 41 25
29 45 30
39 44 50
41 53 07
30 13 55
30 12 00
29 42 36
29 39 20
37 56 42
29 57 45
39 14 11
41 00 37
30 58 30
43 11 08
Longitude
080 44 49
091 00 42
095 23 35
075 30 35
094 54 25
080 50 50
080 45 50
093 15 57
091 11 30
095 04 29
095 02 18
087 34 25
093 56 00
076 34 41
081 36 29
088 01 16
078 42 40
Star
station
13736
13979
12923
13739
12906
13736
14843
03937
12958
12906
12906
93817
12917
13701
14095
93841
14747
Plant Source
type9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
type
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
Emissions, g/s
Process
0.002442
0.000349
0.256089
0.006722
0.019502
0.492485
0.002886
0.000095
0.007008
0.017567
0.
0.
0.
0.
0.
0.
0.
Storage
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
Fugitive
0.062437
0.003964
0.009576
0.265950
0.492485
0.012748
0.098491
0.002220
0.256088
0.393994
0.151890
0.118182
0.059107
0.015823
0.009323
0.049245
0.015823
CO
ro
Plant types: 1 - plant produces and consumes phosgene; 2 - plant produces phosgene.
Source types: 1 - phosgene production/consumption processes.
Source: Systems Applications, Inc. 1980.
-------
00
CO
NOTE: NUMERALS DENOTE NUMBER OF PLANTS.
Figure E-6. Specific point sources of phosgene emissions,
Source: Systems Applications, Inc. 1980.
-------
Detection limit:
0.005 ppm with a 250-liter sample
Possible interferences:
Other acid chlorides, alkyl and aryl derivatives that are
substituted by active halogen atoms, and sulfate esters
are known to produce color with this reagent.
Because this compound is highly unstable, a field determination
should be made. A manual colorimetric test using 4-nitrobenzyl-
pyridine appears to be the best approach for routine analysis
(detection limit approximately 0.05 ppm for 25-liter sample).
Permissible Exposure Limits
OSHA ACGIH NIOSH
TWA 0.1 ppm (0.4 mg/m3) 0.1 ppm (0.4 mg/m3) 0.1 ppm
Ceiling 0.2 ppm
Odor Perception 0.5 to 1 ppm.
Human Toxiclty
Acute Toxicity:
High toxicity via inhalation. High irritant to eyes and
mucous membrane at 4 ppm. In presence of moisture, phosgene
decomposes to form hydrochloric acid and carbon monoxide.
This action takes place within the body when the gas reaches
the bronchioles and the alevoli of the lungs. There is little
irritation effect upon the respiratory tract; therefore, the
warning properties of the gas are very slight. Concentrations
of 3 to 5 ppm of phosgene in air cause irritation of the eyes
and throat, with coughing; 25 ppm is dangerous for exposure
lasting 30 to 60 minutes; and 50 ppm is rapidly fatal even
after short exposure.
Chronic Toxicity:
Epidemiologic studies have shown no ill effects definitely
attributable to phosgene in 326 workers exposed to an average
of 0.125 ppm or less for considerable periods.
Bibliography
American Conference of Governmental Industrial Hygienists. 1984. TLVs,
Threshold Limit Values for Chemical Substances and Physical Agents in the
Work Environment and Biological Exposure Indices With Intended Changes for
1984-1985. ISB N:0 - 936712-54-6. Cincinnati, OH.
184
-------
Hawley, G. G. 1981. The Condensed Chemical Dictionary. 10th Edition. Van
Nostrand Reinhold Company, New York.
Kirk-Othmer. 1971. Encyclopedia of Chemical Technology Supplemental Vol-
ume - Phosgene. John Wiley and Sons, New York, NY. p. 674-683.
National Fire Protection Association. 1983. National Fire Codes, A Com-
pliance of NFPA Codes, Standards, Recommended Practices, and Manuals.
Volume 13.NFPA, Quincy, MA.
Sax, I. N. 1981. Dangerous Properties of Industrial Materials. Sixth
Edition. Van Nostrand Reinhold Company, New York.
Sittig, M. 1981. Handbook of Toxic and Hazardous Chemicals. Noyes
Publications, Par¥ Ridge, NO.
Systems Applications, Inc. 1980. Human Exposure to Atmospheric Concentra-
tions of Selected Chemicals, Volume 1, Appendix A-25 PhosgeneTPB
81-193252.Systems Applications, Inc., San Rafael, CA.
U.S. Department of Health and Human Services. 1983. Chemical Registry of
Toxic Effects of Chemical Substances 1981 to 1982. National Institute for
Occupational Safety and Health. Cincinnati, OH.
U.S. Department of Health and Human Services. 1984. Manual of Analytical
Methods. National Institute for Occupational Safety and Health.
Cincinnati, OH.
U.S. Environmental Protection Agency. 1980. Treatability Manual: Volume 1
Treatability Data. EPA 600-8-80-042a.
Weast, R. T. 1981. CRC Handbook of Chemistry and Physics. 61st Edition.
CRC Press, Inc., Boca Raton, FL.
185
-------
Chemical Name
Propylene oxide
CAS Number
75-56-9
Chemical Classification
Epoxide
Synonyms
Epoxypropane; 1,2-epoxypropane; ethylene oxide, methyl; methyl
ethylene oxide; methyl oxirane; NCI-50099; oxirane, methyl; oxyde
de propylene; propane, epoxy-; propene oxide; propylene oxide;
1,2-propylene oxide; propylene oxide (DOT).
Physical/Chemical Properties
Description:
Colorless liquid; ethereal odor.
Boiling Point:
33.9°C
Melting Point:
-104.4°C
Molecular Weight:
58.8
Chemical Formula:
CH2-CH-CH3
Vapor Pressure:
445 mm (20°C) 400 mm at 17.8°C
Vapor Density:
2.0 (air = 1)
Refractive Index:
ND20 = 1.3670
Solubility:
Partially soluble in water, soluble in alcohol and ether.
Log Partition Coefficient (octanol/water):
Not available
186
-------
Photochemical Reactivity:
Not available
Chemical Reactivity:
Reacts with active hydrogen compounds (e.g., alcohols, amines)
and with inorganic chloride in foods to form l-chloro-2-
propanol. Also reacts with 4-(4'-m'trobenzyl)pyridine.
Violent reaction with NH^OH, chlorosulfonic acid, HC1, HF,
HN03, oleum, and H2SCv
Environmental Fate
Propylene oxide exhibits a high degree of reactivity with a large
number of chemicals including water.
Source of Emissions
Production:
Chlorohydration of propylene, followed by saponification with
lime.
Peroxidation of propylene.
Epoxidation of propylene by a hydroperoxide complex with
molybdenum catalyst.
Uses:
Polyols for urethane foams
Propylene glycols
Surfactants and detergents
Isopropanol amines
Fumigant
Synthetic lubricants
Synthetic elastomer (homopolymer)
Solvent
Tables E-93 through E-105 and Figure E-7 present propylene
oxide production, consumption, and emission data.
Storage:
Carbon steel or stainless steel should be used. Teflon-filled
spiral-wound stainless steel or glass-filled Teflon can be
used for gaskets or seals. Should be protected against physi-
cal damage. Detached outside storage is preferred. Inside
storage should be in a standard flammable liquids storage room
or cabinet. Keep isolated from combustible materials and
oxidizing agents. Propylene oxide tanks should be insulated,
protected by sprinklers, diked, and electrically grounded. An
inert gas such as nitrogen or methane should be kept over the
oxide during storage and transfer.
187
-------
TABLE E-93. PROPYLENE OXIDE PRODUCERS
Company
BASF Wyandotte
Dow Chemical
Jefferson
Olin
Oxirane
Location
Wyandotte, MI
Freeport, TX
Plaquemine, LA
Port Neches, TX
Brandenburg, KY
Bayport, TX
Channelview, TX
Total
1978
capacity,
106 Ib/yr
175
1100
340
150
130
920
400
3215
Process3
A
A
A
A
A
B
B
1978 .
production,
106 Ib/yr
109
684
212
93
81
572
249
2000
Geographical coordinates,
latitude/ longitude
42 12 55/83 08 35
28 59 35/95 23 36
30 19 00/91 15 32
29 57 50/93 56 00
38 00 27/86 06 50
29 37 26/95 03 07
29 48 50/95 07 30
CO
oo
A = chlorohydrin
B = peroxidation
Based on 62.2% production to capacity ratio.
Source: Systems Applications, Inc. 1980.
-------
TABLE E-94. PROPYLENE OXIDE END-USES 1978
Source
Urethane polyols
Propylene glycol
Surfactant polyols
Dipropylene glycol
Glycol ethers
Miscellaneous
Exports
Total
Usage, 106 Ib/yr
1120
480
120
100
40
40
100
2000
Percent usage
56
24
6
5
2
2
5
100
Source: Systems Applications, Inc. 1980.
TABLE E-95. PROPYLENE OXIDE USERS FOR GLYCOL ETHERS PRODUCTION
Company
Dow Chemical
Olin
Location
Freeport, TX
Plaquemine, LA
Brandenburg, KY
Total
Propylene
oxide used,
106 Ib/yr
19.5
13.0
7.5
40.0
Geographic location,
1 ati tude/ 1 ongi tude
28 59 35/95 23 36
30 19 00/91 15 32
38 08 27/86 06 50
Propylene oxide use allocated over the three sites based on ethylene glycol
ethers capacity in the absence of propylene glycol ether figures.
Source: Systems Applications, Inc. 1980.
189
-------
TABLE E-96. PROPYLENE OXIDE USERS FOR URETHANE POLYOLS PRODUCTION
Company
BASF Wyandotte
E. R. Carpenter Co.
Dow Chemical
Emery Industries
Hodag Chemical Co.
Magna Corporation
Mil liken
3M
Mobay Chemical
Mai co Chemical Co.
01 in Corporation
Owens-Corning
Pelron Corporation
Petrol He Corp.
PPG Industries, Inc.
The Quaker Oats Co.
Reichold
Jefferson Chemical Co.
Location
Geismar, LA
Washington, NO
Wyandotte, MI
Bayport, TX
Freeport, TX
Midland, MI
Mauldin, SC
Santa Fe Springs, CA
Skokie, IL
Houston, TX
Inman, SC
Decatur, AL
1 Bay town, TX
New Martinsville, WV
Sugar Land, TX
Brandenburg, KY
Lake Charles, LA
Newark, OH
Lyons, IL
Brea, CA
St. Louis, MO
Circleview, OH
Memphis, TN
Carteret, NJ
Austin, TX
Conroe, TX
Port Neches, TX
1978
urethane
polyols
capacity,
10fe Ib/yr
100
40
225
150
400
20
10
10
10
12
3
15
100
80
40
220
30
10
22
15
15
30
10
20
33
33
34
1978
propylene
oxide used,
106 Ib/yr
45
18
101
68
180
9
4.5
4.5
4.5
5
1.5
7
45
36
18
100
14
4.5
10
7
7
14
4.5
9
15
15
15
Geographical coordinates,
latitude/ longitude
30 11 34/91 00 42
40 45 20/74 58 22
42 12 55/83 08 35
29 43 20/94 54 00
28 59 35/95 23 36
43 34 08/84 16 26
34 48 16/82 16 09
33 55 30/118 05 40
42 01 50/87 43 39
29 40 10/95 23 30
34 56 10/82 06 29
34 38 39/87 02 25
29 45 30/94 54 25
39 44 50/80 50 55
29 37 10/95 38 32
38 08 27/86 06 50
30 13 85/93 15 57
40 05 30/82 26 00
41 44 56/87 49 04
33 53 30/117 58 45
38 41 50/90 12 08
39 36 05/82 57 34
35 10 30/90 56 56
40 35 56/74 13 13
30 20 00/97 14 15
30 18 50/95 23 06
29 57 50/93 56 00
10
o
(continued)
-------
TABLE E-96 (continued)
Company
Union Carbide
Upjohn
Witco
Location
Institute, WV
Seadrift, TX
S. Charleston, WV
LaPorte, TX
Clearing, IL
Houston, TX
Total
1978
urethane
polyols
capacity,
106 Ib/yr
245
245
250
14
25
18
2484
1978
propylene
oxide used,
106 Ib/yr
110
110
113
6
11
8
1120
Geographical coordinates,
latitude/longitude
38 23 02/81 47 24
28 30 31/96 46 18
38 22 13/81 40 44
29 42 44/95 04 45
41 48 02/87 46 39
29 34 45/95 26 00
Source: Systems Applications, Inc. 1980.
-------
TABLE E-97. PROPYLENE OXIDE USERS FOR DIPROPYLENE AND TRIPROPYLENE GLYCOL PRODUCTION
Company
Dow Chemical
Olin
Oxirane
Jefferson
Union Carbide
Location
Freeport, TX
Plaquemine, LA
Brandenburg, KY
Bayport, TX
Port Neches, TX
Institute, WV
S. Charleston, WV
Total
Di propylene
glycol/tripropyl-
ene glycol pro-
duction capacity,
106 Ib/yr
27.5
17.6
5
18
7
5
85.1
Propylene
oxide used,
106 Ib/yr
32.3
20.7
5.9
21.1
8.2
5.9
5.9
100.0
Geographical coordinates,
latitude/ longitude
28 59 35/95 23 36
30 19 00/91 15 32
38 08 27/86 06 50
29 37 26/95 03 07
29 57 50/93 56 00
38 23 02/81 47 24
38 22 13/81 40 44
ro
Total propylene oxide used allocated per site based on the rate of dipropylene/tripropylene glycol individ-
ual site production capacity to total industry production capacity.
Capacity of 10 million Ib/yr equally distributed between the two sites.
Source: Systems Applications, Inc. 1980.
-------
TABLE E-98. PROPYLENE OXIDE USERS FOR SURFACTANT POLYOLS PRODUCTION
Company
Emery Industries
Olin
Petrol ite
Sherex
Union Carbide
Witco
Location
Sante Fe Springs, CA
Brandenburg, KY
Brea, CA
St. Louis, MO
Janesville, WI
Institute, WV
Seadrift, TX
S. Charleston, WV
Houston, TX
Total
Polyether polyols
capacity,
10b Ib/yr
10
270
15b
15b
5
100C
\OQC
100C
18
633
Propylene
oxide used,
106 Ib/yr
2
51
3
3
1
19
19
19
3
120
Geographical coordinates,
latitude/longitude
33 55 30/118 05 40
38 08 26/86 06 50
33 53 30/117 58 45
38 41 50/90 12 08
42 40 47/89 00 30
38 23 02/81 47 24
28 30 31/96 46 18
38 22 13/81 40 44
29 34 45/95 26 00
aTotal propylene oxide used distributed over each site based on polyether polyols capacity.
Total capacity of 30 million Ib equally distributed between both sites.
c Total capacity of 300 million Ib equally distributed between all three sites.
Source: Systems Applications, Inc. 1980.
-------
TABLE E-99. PROPYLENE OXIDE USERS FOR PROPYLENE 6LYCOL PRODUCTION
Company
Dow Chemical
Jefferson
Olin
Oxirane
Union Carbide
Location
Freeport, TX
Plaquemine, LA
Port Neches, TX
Brandenburg, KY
Bayport, TX
Institute, WV
S. Charleston, WV
Total
1978
propylene glycol
capacity,
10fe Ib/yr
250
160
50
45
250
50
50
855
1978
propylene
oxide used,3
106 Ib/yr
140
91
28
25
140
28
28
480
Geographical coordinates,
latitude/longitude
28 59 35/95 23 36
30 19 00/91 15 32
29 57 50/93 56 00
38 08 27/86 06 50
29 37 26/95 03 07
38 23 02/81 47 24
38 22 13/81 40 44
Source: Systems Applications, Inc. 1980.
-------
TABLE E-100. 1978 PROPYLENE OXIDE NATIONWIDE EMISSIONS
Estimated 1978
Source emissions, Ib/yr
Production
Urethane polyols
Propylene glycol
Surfactant polyols
Dipropylene/tripropylene glycol s
Glycol ethers
Miscellaneous
Exports
Total
1,160,660
147 ,840
13,920
15,840
2,900
1,160.
3,840a
0
1,346,160
Derived based on weighted average of other users
except exports.
Source: Systems Applications, Inc. 1980.
TABLE E-101. EMISSIONS FROM DIPROPYLENE GLYCOL, TRIPROPYLENE GLYCOL, AND
GLYCOL ETHER PRODUCERS
Company
Dow Chemical
Jefferson
Olin
Oxirane
Union Carbide
Location
Freeport, TX
Plaquemine, LA
Port Neches, TX
Brandenburg, KY
Bayport, TX
Institute, WV
S. Charleston, WV
Total
Process vent
emissions,
Ib/yr
1450
945
230
375
590
165
165
3920
Fugitive
emissions,
Ib/yr
50
35
10
15
20
5
5
140
Total emissions
Ib/yr
1500
980
240
390
610
170
170
4060
g/s
0.022
0.014
0.003
0.006
0.009
0.002
0.002
Source: Systems Applications, Inc. 1980.
195
-------
TABU E-102. EMISSIONS FROM SURFACTANT POLYOL PRODUCERS
Company
Emery
Olin
Petrol He
Sherex
Union Carbide
Witco
Location
Santa Fe Springs, CA
Brandenburg, KY
Brea, CA
St. Louis, MO
Janesville, WI
Institute, WV
Seadrift, TX
S. Charleston, WV
Houston TX
Total
Process
emissions,
Ib/yr
260
6,630
390
390
130
2,470
2,470
2,470
390
15,600
Storage
emissions,
Ib/yr
Nil
50
Nil
Nil
Nil
20
20
20
Nil
110
Fugitive
emissions,
Ib/yr
Nil
50
Nil
Nil
Nil
20
20
20
Nil
110
Total emissions
Ib/yr
265
6,730
395
395
130
2,510
2,510
2,510
395
15,840
9/s
0.004
0.097
0.006
0.006
0.002
0.036
0.036
0.036
0.006
vo
Source: Systems Applications, Inc. 1982.
-------
TABLE E-103. EMISSIONS FROM PROPYLENE OXIDE USERS FOR
PROPYLENE GLYCOL PRODUCTION
Company
Dow Chemical
Jefferson
Olin
Union Carbide
Location
Freeport, TX
Plaquemine, LA
Port Neches, TX
Brandenburg, KY
Institute, WV
S. Charleston, WV
Total
Process vent
emissions,
Ib/yr
3,920
2,550
785
700
785
785
9,525
Fugitive
emissions,
Ib/yr
140
90
30
25
30
30
345
Total emissions
Ib/yr
4,060
2,640
815
725
815
815
9,870
9/s
0.058
0.038
0.012
0.010
0.012
0.012
Source: Systems Applications, Inc. 1982.
197
-------
TABLE E-104. EMISSIONS FROM PROPYLENE OXIDE USERS FOR URETHANE POLYOLS PRODUCTION
vo
00
Company
BASF Wyandotte
E. R, Carpenter Co.
Dow Chemical
Emery Industries
Hodag Chemical Co.
Magna Corporation
Milliken
Minnesota Mining A
Manufacturing
Mobay Chemical
Nalco Chemical Co.
Olin
Owens -Corn ing
Pelron Corporation
Petrol ite Corp.
PPG Industries, Inc.
The Quaker Oats Co.
Reichold
Jefferson Chemical Co.
Union Carbide
Upjohn
Witco
Location
Geismar, LA
Washington, NJ
Wyandotte, MI
Bayport, TX
Freeport, TX
Midland, MI
Mauldin, SC
Santa Fe Springs, CA
Skokie, IL
Houston, TX
Inman, SC
Decatur, AL
Bay town, TX
New Martinsville, WV
Sugar Land, TX
Brandenburg, KY
Newark, OH
Lyons, IL
Brea, CA
St. Louis, MO
drcleview, OH
Memphis, TN
Carteret, NJ
Austin, TX
Conroe, TX
Port Neches, TX
Institute, WV
Seadrift, TX
S. Charleston, WV
LaPorte, TX
Clearing, IL
Houston, TX
Total
Process
vent
emissions
Ib/yr
103,703
2,400
13,200
8,800
23,400
1,200
600
600
600
600
200
1,000
5,800
4,600
2,400
12 ,800
600
1.400
1,000
1,000
1,800
600
1,200
2,000
2,000
2,000
14,300
14,300
14,600
800
1,400
1,000
241,903
9/s
1.49
0.03
0.19
0.13
0.34
0.02
0.01
0.01
0.01
0.01
0.01
0.08
0.07
0.03
0.19
0.01
0.02
0.01
0.01
0.03
0.01
0.02
0.03
0.03
0.03
0.21
0.21
0.21
0.01
0.02
0.01
Storage
vent
emissions
Ib/yr
708
20
100
80
100
40
40
20
100
20
20
20
20
20
120
120
120
20
1,688
9/s
0.10
0.002
0.001
0.002
0.001
0.001
0.002
0.002
0.002
0.002
Fugitive Total
emissions emissions
Ib/yr
40
20
80
60
140
40
20
20
80
""" "/<
(?
H
^
/v
C\
^ — \
-------
TABLE E-105. EMISSIONS FROM PROPYLENE OXIDE PRODUCERS
Company
BASF Wyandotte
Dow Chemical
Jefferson
OHn
Oxlrane
Location
Wyandotte, MI
Freeport, TX
Plaquemine, LA
Port Neches, TX
Brandenburg, KY
Bayport, TX
Channelview, TX
Total
Emissions,
Ib/yr
81,750
513,000
159,000
69,750
60,750
120,120
52,290
1,056,660
Process vents3
Stack
height,
m
10.4
10.4
10.4
7.25
10.4
9.1
14.6
Stack
diameter,
m
0.26
0.26
0.26
0.19
0.26
0.05
0.76
Stack
temperature,
°C
25
25
25
46
25
21
26
Storage
vent
emissions,
Ib/yr
3,380
21,200
6,570
2,860
2,510
17,730
7,720
61,970
Fugitive
emissions,
Ib/yr
2,290
14,360
4,450
1.950
1,700
12,010
5,230
41,990
Total emissions
Ib/yr
87 ,420
548,560
170,020
74,560
64.960
149,860
65,240
1,160,620
9/s
1.25
7.89
2.45
1.07
0.94
2.16
0.94
* Stack velocity for all plants 2 m/s.
Source: Systems Applications, Inc. 1980.
-------
ro
O
o
NOTE: NUMERALS DENOTE NUMBER OF PLANTS.
Figure E-7. Specific point sources of propylene oxide emissions,
Source: Systems Applications, Inc., 1980.
-------
Transportation:
Shipped in glass bottles, cans, metal drums, tank trucks, tank
cars, tank barges, and cargo ships, usually with nitrogen over
the propylene oxide. Must be labeled "Flammable Liquid."
Shipment by ship must be kept under an inert gas pad and
maintained at or below 40°C.
Disposition:
Propylene oxide may be disposed of as a concentrated waste
containing no peroxides by discharge of the liquid at a con-
trolled rate near a pilot flame or as a concentrated waste
containing peroxides by perforation of a container of the
waste from a safe distance followed by open burning.
Sampling and Analytical Methods
1. NIOSH Method S75
a. Adsorption with charcoal.
b. Desorption with carbon disulfide.
c. Gas chromatography.
Sampling and Analytical Methods
1. NIOSH Method S75
a. Adsorption with charcoal.
b. Desorption with carbon disulfide.
c. Gas chromatography.
Detection limit:
25 to 720 mg/m3 (10 to 288 ppm) for a 5-liter sample
Possible interferences:
High humidity may hamper vapor trapping efficiency. Any
compound with the same retention time as propylene oxide
will cause interference.
2. Method B (Appendix A): C2-C18 hydrocarbons and other nonpolar
organics with a boiling point of 100° to 175°C.
a. Whole air collection in canister.
b. Cryogenic concentration.
c. Gas chromatography/flame ionization detection.
Detection limit:
0.1 ppb per 100-ml sample
Possible interferences:
Water-soluble compounds are not readily analyzed. Stor-
age times greater than a week are not recommended.
201
-------
3. Method C (Appendix A): C6-C12 hydrocarbons and other nonpolar
organics with a boiling point between 60° and 200°C.
a. Adsorption on Tenax.
b. Thermal desorption.
c. Gas chromatography/mass spectrometry analysis.
Detection limit:
1 to 200 ppt for a 20-liter sample
Possible interferences:
Blank levels usually limit sensitivity artifacts due to
reactive components (03, NO ). Sample can be analyzed
only once. Low breakthrougn volume on Tenex adsorption.
4. Method D (Appendix A): C6-C12 hydrocarbons and other nonpolar
organics with a boiling point of 60° to 200°C.
a. Adsorption on Tenax.
b. Thermal desorption into canisters.
c. Gas chromatography/flame ionization detection, or gas
chromatography/mass spectrometry analysis.
Detection limit:
0.01 to 1 ppb for a 20-liter sample
Possible interferences:
Blanks and artifact problems in Method C, above low
breakthrough volume on Tenex adsorption.
Permissible Exposure Limits
OSHA ACGIH
TWA 100 ppm (240 mg/m3) 20 ppm (50 mg/m3)
Human Toxicity
Acute Toxicity:
Skin and eye irritant. A.food additive permitted in food for
human consumption.
Chronic Toxicity:
Propylene oxide was found to be carcinogenic in rats in a
limited study in which subcutaneous injection produced sar-
comas. ,No epidemiological studies were found.
202
-------
Bibliography
American Conference of Governmental Industrial Hygienists. 1984. TLVs.
Threshold Limit Values for Chemical Substances and Physical Agents in the
Work Environment and Biological Exposure Indices With Intended Changes for
1984-1985.ISB N:0 - 936712-54-6.Cincinnati, OH.
Hawley, G. G. 1981. The Condensed Chemical Dictionary. 10th Edition. Van
Nostrand Reinhold Company, New York.
International Agency for Research on Cancer. 1976. IARC Monographs on the
Evaluation of Carcinogenic Risk of Chemicals to Man, Volume 11 - Propylene
Oxide.Lyon, France, p. 191-196.
Kirk-Othmer. 1982. Encyclopedia of Chemical Technology, Volume 19,
Propylene Oxide. John Wiley and Sons, New York. p. 228-245.
National Fire Protection Association. 1983. National Fire Codes, A Comp-
liance of NFPA Codes, Standards, Recommended Practices, and Manuals.
Volume 13. NFPA, Quincy, MA.
Sax, I. N. 1981. Dangerous Properties of Industrial Materials. Sixth
Edition. Van Nostrand Reinhold Company, New York.
Sittig, M. 1981. Handbook of Toxic and hazardous Chemicals. Noyes
Publications. Park Ridge, NJ.
Systems Applications Inc. 1980. Human Exposure to Atmospheric Concentra-
tions of Selected Chemicals, Volume 1, Appendix A-26, Propylene Oxide.
PB 81-193252.Systems Applications, Inc., San Rafael, CA.
Systems Applications, Inc. 1982. Human Exposure to Atmospheric Concentrations
of Selected Chemicals Volume II. Appendix A-26.Propylene Oxide.EPA
Contract No. 68-02-3066.SAI 58-EF81-156R2. Systems Applications, Inc.,
San Rafael, CA.
U.S. Department of Health and Human Services. 1983. Chemical Registry of
Toxic Effects of Chemical Substances 1981 to 1982. National Institute for
Occupational Safety and Health.Cincinnati, OH.
U.S. Department of Health and Human Services. 1984. Manual of Analytical
Methods. National Institute for Occupational Safety and Health.
Cincinnati, OH.
U.S. Environmental Protection Agency. 1980. Treatability Manual: Voltime 1
Treatability Data. EPA 600-8-80-042a.
Weast, K. T. 1981. CRC Handbook of Chemistry and Physics. 6ist Edition.
CRC Press, Inc., Boca Raton, FL.
203
-------
Chemical Name
o-, m-, p-xylene (where properties differ, they are presented in
o-, m-, p- order)
CAS Number
95-47-6; 108-38-3; 106-42-3; mixed isomers 1330-20-7
Chemical Classification
Aromatic hydrocarbon, alkyl benzene
Synonyms
(o-,m-,p-) dimethyl benzene; 1, (2-,3-,4-,) dimethyl benzene;
(o-,m-,p-,) methyl toluene; 1 (2-,3-,4-) xylene; (o-,m-,p-) xylol
Physical/Chemical Properties
Description:
Clear colorless liquid; p-xylene exists as crystals at low
temperature.
Boiling Point:
144°C; 138.8°C; 138.5°C
Melting Point:
-25°C; -47.4°C; 13.2°C
Molecular Weight:
106.2
Chemical Formula:
1, (2-,3-,4-) C6MCH3)2
Vapor Pressure:
10 mm Hg at 32.1°C; 10 mm Hg at 28.3°C; 10 mm Hg at 27.3°C
Vapor Density:
3.66 (air = 1.0)
Refractive Index:
ND20 = 1.505; ND20 = 1.497; ND20 = 1.500
Solubility:
Soluble in alcohol and ether, insoluble in water.
Log Partition Coefficient (octanol/water):
2.77; 3.20; 3.15
204
-------
Photochemical Reactivity:
Transformation products are formaldehyde, acetaldehyde, PAN,
and benzaldehyde. Xylene can be easily chlorinated, sulfonat-
ed, and nitrated. Reactivity toward OH- has a half-life of 3
days (8 times butane) for m and p; o has a half-life of 6
days. Reactivity toward 03 has no reaction for o and m;
half-life 100 years for p.
Chemical Reactivity:
Contact with strong oxidizers may cause fires and explosions.
Toxic gases and vapors (such as carbon monoxide) may be re-
leased in a fire involving xylene. Elevated temperatures may
cause containers to burst, p-xylene incompatible with acetic
acid + air; HN03; and l,3-dich1oro-3,5-dimethyl-2,4-imid-
azolidindione. Xylene will attack some forms of plastics,
rubber, and coatings.
Environmental Fate
Calculated half-life in water at a depth of 1 meter at 25°C is 5.6
hours based on evaporative loss from the water. Some half-lives
for photochemical reactions in air are presented in the photochemi-
cal reactivity section. Estimated overall lifetime under photo-
chemical smog conditions in southeastern England is 2 to 6 hours.
Source of Emissions
Production:
Selective crystallization or solvent extraction from meta-para
mixtures.
Uses:
Solvent
Intermediate for dyes and organic synthesis especially for
isophthalic acid
Insecticides
Aviation fuel
Tables E-106 through E-119 and Figure E-8 present data on
xylene production, consumption, and emissions.
Storage:
Should be protected against physical damage. Outside or
detached storage is preferable. Inside storage should be in,a
standard flammable liquids storage room or cabinet, separate
from oxidizing materials.
Transportation:
Shipped in glass containers in 55- and 110-gallon metal drums;
in tank cars and tank trucks; and on tank barges.
Disposition:
Xylenes may be disposed of by incineration
205
-------
TABLE E-106. XYLENE ISOMER PRODUCERS
Company
o-xylene Producers
ARCO
Corco
Exxon
Monsanto
Phillips
Shell
Sun
Tenneco
Location
Houston, TX
Ponce, PR
Bay town, TX
Chocolate Bayou, TX
Guayama, PR
Deer Park, TX
Corpus Christi , TX
Chalmette, LA
Total
m-xylene Producer
Amoco
p-xylene Producers
Amoco
Arco
Chevron
St. Croix
Texas City, TX
Decatur, AL
Texas City, TX
Houston, TX
Pascagoula, MS
St. Croix, VI
I some r
capacity,
10fe Ib/yr
210
175
200
30
130
165
160
130
1200
175
1300
900
360
330
600
Isomer
production,
106 Ib/yr
183
153
174
26
113
144
140
113
1046
88
952
659
264
242
440
Geographic coordinates,
La t i tude/ longitude
29 42 17/95 16 01
Not in project scope
29 44 50/95 01 00
29 14 55/95 12 45
Not in project scope
29 42 55/95 07 34
27 49 53/97 31 30
30 03 30/89 58 30
29 21 40/94 55 50
34 36 12/86 58 42
29 21 40/94 55 50
29 42 17/95 16 01
30 19 04/88 28 37
Not in project scope
ro
O
(continued)
-------
TABLE E-106 (continued)
Company
Location
p-xylene Producers (cont.)
Exxon
Hercor
Phillips
Shell
Sun
Tenneco
Bay town, TX
Penuelas, PR
Cuayama , PR
Deer Park, TX
Corpus Christi , TX
Chalmette, LA
Total
Ethyl benzene Producers3
ARCO
Charter
Monsanto
Sun
Houston, TX
Houston, TX
Chocolate Bayou, TX
Corpus Christi , TX
Total
Isomer
capacity,
10fe Ib/yr
420
600
470
110
390
125
5605
136
35
59
73
303
Isomer
production,
106 Ib/yr
308
440
344
80
286
92
4107
99
25
43
53
220
Geographic coordinates,
Lati tude/1 ongi tude
29 44 50/95 01 00
Not in project scope
Not in project scope
29 42 55/95 07 34
27 49 53/97 31 30
30 03 30/89 58 30
29 42 17/95 16 01
29 42 50/95 15 12
29 14 55/95 12 45
27 49 53/97 31 30
ro
o
Ethyl benzene is considered to be a mixed xylene isomer.
Source: Systems Applications, Inc., 1980.
-------
TABLE E-107. MIXED XYLENE PRODUCTION SOURCE SUMMARY
Source
Catalytic reformate
Pyrolysis gasoline
Toluene disproportionation
Coal-derived
Total
Isolated mixed
xylene product,
106 Ib/yr
7,991
429
106
29
8,555
Nonisolated
mixed xylene
production,
106 Ib/yr
68,925
397
92
4
69,418
Total mixed
xylene
production,
106 Ib/yr
76,916
826
198
33
77,973
Source: Systems Applications, Inc., 1980.
208
-------
TABLE E-108. ISOLATED MIXED XYLENE PRODUCTION FROM CATALYTIC REFORMATE
Company
Amerada Hess
American Petrofina
Ashland Oil
ARCO
Charter Oil
Cities Service
Coastal States
Commonwealth
Crown
Exxon
Gulf
Kerr McGee
Marathon
Location
St. Croix, VI
Big Spring, TX
Beaumont, TX
Catlettsburg, KY
N. Tonawanda, NY
Houston, TX
Houston, TX
Lake Charles, LA
Corpus Christi, TX
Penuelas, PR
Pasadena, TX
Bay town, TX
Alliance, LA
Corpus Christi, TX
Texas City, TX
Mixed xylene
capacity,
metric tons/yr
457
209
49
98
46
258
36
163
55
343
46
408
196
140
36
Isolated mixed
xylene produced,
106 lb/yrD
699
306
72
143
67
378
53
239
80
502
67
597
287
205
53
Geographic coordinates,
Latitude/longitude
Not in project scope
32 17 10/101 25 17
29 57 30/93 53 20
38 22 39/82 35 58
42 59 45/78 55 27
29 42 17/95 16 01
29 42 50/95 15 12
30 10 58/93 19 01
27 48 43/97 26 28
Not in project scope
29 44 40/95 10 30
29 44 50/95 01 04
29 50 00/90 00 10
27 48 15/97 25 24
29 22 22/94 54 58
rvj
o
<£>
(continued)
-------
TABLE £-108 (continued)
Company
Monsanto
Phillips
Qui tana-Howe 11
Shell
Chevron
Amoco
Sun
Tenneco
Union Oil
Union Pacific
Location
Texas City, TX
Guayama, PR
Corpus Christi , TX
Deer Park, TX
Pascagoula, MS
Richmond, CA
Texas City, TX
Whiting, IN
Corpus Christi , TX
Marcus Hook, PA
Toledo, OH
Chalmette, LA
Chicago, IL
Corpus Christi, TX
Total
Mixed xylene
capacity,
metric tons/yr
32
326
42
245
212
196
800
588
78
65
163
130
33
10
5,460
Isolated mixed
xylene produced,
106 lb/yr°
47
477
61
359
310
287
1,171
860
114
95
239
190
48
15
8,021
Geographic coordinates,
Latitude/longitude
29 22 45/94 33 30
Not in project scope
27 48 35/97 27 30
29 42 55/95 07 33
30 19 04/80 28 37
37 56 12/122 20 48
29 21 40/94 55 50
41 41 07/87 29 02
27 49 53/97 31 30
39 48 45/75 24 51
41 36 52/83 31 40
30 03 30/89 58 30
41 38 33/88 03 02
27 48 10/97 35 29
ro
o
Source: Systems Applications, Inc., 1982.
-------
TABLE E-109.
NONISOLATED MIXED XYLENE (AS
CATALYTIC REFORMATS
BTX) PRODUCTION FROM
Region
New England
Middle Atlantic
East North Central
West North Central
South Atlantic
East South Central
West South Central
Mountain
Pacific
Total
Number
of sites
0
17
28
16
5
8
71
23
33
201
Reformate
capacity,
106 bbl/day
0
369,952
624,178
165,250
57,660
144,700
1,649,303
123,094
647,461
3,781,598
Non-
isolated
mixed
xylene
produced,
106 Ib/yr
0
6,743
11,377
3,012
1,051
2,637
30,061
2,243
11,801
68,925
Average
non isolated
mixed xylene
produced
per site,
106 Ib/yr
0
397
406
188
210
330
423
98
358
343
Source: Systems Applications, Inc., 1980.
211
-------
TABLE E-110. OTHER MIXED XYLENE PRODUCERS
Company
Pyrolysis
gasoline
ARCO
Commonwealth
Dow
Exxon
Gulf
Mobile
Monsanto
Shell
Union Carbide
Location
Channelview, TX
Penuelas, PR
Freeport, TX
Baton Rouge, LA
Cedar Bayou, TX
Beaumont, TX
Texas City, TX
Deer Park, TX
Taft, LA
Total
Coal -derived
Ashland
U.S. Steel
Catlettsburg, KY
N. Tonawanda, NY
Clairton, PA
Total
Toluene dispro-
portionation
ARCO
Sun
Houston, TX
Marcus Hook, PA
Total
Production
capacity,
106 Ib/yr
1179
454
1134
816
544
408
340
624
417
5916
13
7
13
33
196
202
398
Non-
isolated
mixed
xylene
produced,
106 Ib/yr
79
30
76
55
37
27
23
42
28
397
1.6
0.8
1.6
4.0
45
47
92
Isolated
mixed
xylene
produced,
106 Ib/yr
168
91
61
109
429
11.4
6.2
11.4
29.0
52
54
106
Total
mixed
xylene
produced,
106 Ib/yr
247
121
76
55
37
27
84
42
137
826
13
7
13
33
97
101
198
Geographic coordinates,
Latitude/longitude
29 50 04/95 06 43
NA
28 59 12/95 01 00
30 09 10/90 54 20
29 49 29/94 55 10
30 04 00/94 03 30
29 15 00/95 12 40
29 42 55/95 07 33
29 58 00/90 27 00
38 22 39/82 35 58
42 59 45/78 55 27
40 18 15/79 52 43
29 42 17/95 16 01
39 48 45/75 24 51
ro
ro
NA = Not applicable.
Source: Systems Applications, Inc. 1980.
-------
TABLE E-lll. END-USE DISTRIBUTION - 1978 MIXED XYLENE AND XYLENE ISOMERS
Mixed xylene as BTX (not isolated)
Gasoline
Isolated mixed xylene
p-xylene isomer
o-xylene isomer
m- xylene isomer
Ethyl ene benzene
Gasoline backblending
Paint and coating solvent
Adhesives solvent
Chemical manufacturing solvent
Agricultural solvent
Other miscellaneous solvents
Net export
o-xylene
Phthalic anhydride
Gasoline backblending
Exports
p-xylene
Terephthalic acid
Dimethyl terephthalate
Net exports
Gasoline backblending
m-xylene
Isophthalic acid
Usage
106 Ib/yr
69,418
69,418
8,555
4,107
1,046
88
220
2,158
496
77
77
66
55
165
1,046
670
21
355
4,107
1,430
2,040
620
17
88
98a
%
100.0
48.0
12.2
1.0
2.6
25.2
5.8
0.9
0.9
0.8
0.7
1.9
64.1
2.0
33.9
34.8
49.7
15.1
0.4
100.0
Difference between production and use supplied by imports.
Source: Systems Applications, Inc., 1980.
213
-------
TABLE E-112. XYLENE ISOMER END-USERS
Company
Location
Production
capacity,
106 Ib/yr
o-Xylene
used,
106 Ib/yr
Geographic coordinates,
latitude/ longitude
Phthalic Anhydride Producers (o-xylene)
Allied
BASF Wyandotte
Exxon
Koppers
Monsanto
Hooker
Chevron
Stepan
El Segundo, CA
Kearny, NJ
Baton Rouge, LA
Cicero,1 IL
Texas City, TX
Arecibo, PR
Richmond, CA
Millsdale, IL
Total
36
150
130
235
150
87
50
100
938
26
107
93
168
107
62
36
71
670
33 56 30/118 26 35
40 45 53/74 09 03
30 09 10/90 54 20
41 48 44/87 45 04
29 22 45/94 33 30
Not in project scope
37 56 12/122 20 48
41 26 03/88 09 48
ro
Isophthalic Acid Producer (m-xylene)
Amoco j Joliet, IL
(continued)
240
98
41 26 48/88 10 41
-------
TABLE £-112 (continued)
Company
Location
Production
capacity,
10fe Ib/yr
o-Xylene
used,
106 Ib/yr
Geographic coordinates,
Latitude/longitude
Dimethylterephthalic Acid Producers (o-xylene)
DuPont
Eastman Kodak
Hercofina
Old Hickory, TN
Wilmington, NC
Columbia, SC
Kingsport, TN
Wilmington, NC
Total
550
1250
500
500
1300
4100
273
622
249
249
647
2040
36 16 24/86 34 12
34 10 00/77 56 06
33 59 50/81 04 17
36 31 41/82 12 22
34 19 27/77 46 56
ro
tn
Terephthalic Acid Producers (p-xylene)
Amoco
Hercofina
Cooper River, SC
Decatur, AL
Wilmington, NC
Total
1000
2000
240
3240
441
883
106
1430
32 45 57/79 58 28
34 36 12/86 58 42
34 19 27/77 46 56
Source: Systems Applications, Inc., 1980.
-------
TABLE E-113. 1978 NATIONWIDE EMISSIONS OF XYLENE ISOMERS
p-xylene
Mixed xylene production
Mixed xylene solvent use
Ethyl benzene production
p-Xylene production
Terephthalic acid production
Dimethylterephthalate production
Gasoline marketing - evaporation
Gasoline automobile - evaporation
Gasoline automobile - exhaust
Total
o-xylene
Mixed xylene production
Mixed xylene solvent use
Ethyl benzene production
o-Xylene production
Phthal ic anhydride
Gasoline marketing - evaporation
Gasoline automobile - evaporation
Gasoline automobile - exhaust
Total
m-xylene
Mixed xylene production
Mixed xylene solvent use
Ethyl benzene production
m-Xylene production
Isophthalic acid
Gasoline marketing - evaporation
Gasoline automobile - evaporation
Gas,oline automobile - exhaust
Total
Nationwide
emissions,
Ib/yr
1,610,076
114,395,000
7,348
6,447,990
469,200
3,889,600
2,138,500
1,967,100
108,345,600
239,270,414
1,976,440
140,425,000
9,020
2,667,300
134,000
2,138,500
1,967,100
119,180,000
268,497,360
3,706,331
244,545,000
15,708
176,000
98,000
5,193,400
4,777,400
195,022,100
453,533,939
Source: Systems Applications, Inc., 1980.
216
-------
TABLE E-114. XYLENE ISOMER EMISSIONS FROM XYLENE ISOMER PRODUCERS
Company
o-xylene Producers
ARCO
Corco
Exxon
Monsanto
Phillips
Shell
Sun
Tenneco
Location
Houston, TX
Ponce, PR
Bay town, TX
Chocolate Bayou, TX
Guayama, PR
Deer Park, TX
Corpus Christi , TX
Chalmette, LA
Total
m-xylene Producer
Amoco
p-xylene Producers
Amoco
ARCO
Chevron
St. Croix
Exxon
Hercor
Phillips
Shell
Sun
Tenneco
Texas City, TX
Decatur, AL
Texas City, TX
Houston, TX
Pascagoula, MS
St. Croix, VI
Bay town, TX
Penuelas, PR
Guayama, PR
Deer Park, TX
Corpus Christi , TX
Chalmette, LA
Total
Emissions, Ib/yr
Process
382,470
319,770
363,660
54,340
237,170
300,960
292,600
236,170
2,187,140
139,040
1,085,280
751,260
300,960
275,880
501,600
351,120
501,600
392,160
91,200
326,040
104,880
4,681,980
Storage
14,640
12,240
13,920
2,080
9,040
11,520
11,200
9,040
83,680
10,560
180,880
125,210
50,160
45,980
83,600
58,520
83,600
65,360
15,200
54,340
17,480
780,330
Fugitive
69,540
58,140
66,120
9,880
42,940
54,720
53,200
42,940
397,480
26,400
228,480
158,160
63,360
58,080
105,600
73,920
105,600
82,560
19,200
68,640
22,080
985,680
Total emissions
Ib/yr
466,650
390,150
443,700
66,300
289,150
367,200
357,000
288,150
2,668,300
176,000
1,494,640
1,034,630
414,480
379,940
690,800
483,560
690,800
540,080
125,600
449,020
144,440
6,447,990
9/s
6.72
5.62
6.39
0.95
4.15
5.28
5.14
4.15
2.53
21.52
14.89
5.97
5.47
9.94
6.96
9.94
7.78
1.81
6.46
2.08
Source: Systems Applications, Inc., 1980.
-------
TABLE E-115. MIXED XYLENE EMISSIONS FROM OTHER MIXED XYLENE PRODUCERS
Company
Pyrolysis-Gasoline
ARCO
Commonwealth
Dow
Exxon
Gulf
Mobile
Monsanto
Shell
Union Carbide
Location
Channelview, TX
Penuelas, PR
Freeport, TX
Baton Rouge, LA
Cedar Bayou, TX
Beaumont, TX
Texas City, TX
Deer Park, TX
Taft, LA
Total
Coal-Derived
Ashland
U.S. Steel
Catlettsburg, KY
N. Tonawanda, NY
Clairton, PA
Total
Toluene
Disproportionation
ARCO
Sun
Houston, TX
Marcus Hook, PA
Total
Emissions, Ib/yr
Process
17,290
8,470
5,320
3,850
2,590
1,890
5,880
2,940
9,590
57,820
6,500
3,500
6,500
16,500
4,850
5,050
9,900
Storage
74,100
36,300
22,800
16,500
11,100
8,100
25,200
12,600
41,100
247,800
7,800
4,200
7,800
19,800
9,700
10,100
19,800
Fugitive
7,410
3,630
2,280
1,650
1,110
810
2,520
1,260
4,110
24,780
1,950
1,050
1,950
4,950
4,850
5,050
9,900
Total emissions
Ib/yr
98,800
48,400
30,400
22,000
14,800
10,800
33,600
16,800
54,800
330,400
16,250
8,750
16,250
41,250
19,400
20,200
39,600
9/s
1.42
0.70
0.44
0.32
0.21
0.16
0.48
0.24
0.79
0.23
0.13
0.23
0.29
0.30
ro
oo
-------
TABLE E-116. MIXED XYLENE EMISSIONS FROM CATALYTIC REFORMATS (ISOLATED MIXED XYLENES) PRODUCTION
Company
Amerada Hess
American Petrofina
Ashland Oil
ARCO
Charter Oil
Cities Service
Costal States
Commonwealth
Crown
Exxon
Gulf
Kerr-McGee
Marathon
Location
St. Croix, VI
Big Springs, TX
Beaumont, TX
Catlettsburg, KY
N. Tonawanda, NY
Houston, TX
Houston, TX
Lake Charles, LA
Corpus Christi , TX
Penuelas, PR
Pasadena, TX
Bay town, TX
Alliance, LA
Corpus Christi , TX
Texas City, TX
Emissions, Ib/yr
Process
20,070
9,180
2,160
4,290
2,010
11,340
1,590
7,170
2,400
15,060
2,010
17,910
8,610
6,150
1,590
Storage
40,140
18,360
4,320
8,580
4,020
22,680
3,180
14,340
4,800
30,120
4,020
35,820
17,220
12,300
3,180
Fugitive
20,070
9,180
2,160
4,290
2,010
11,340
1,590
7,170
2,400
15,060
2,010
17,910
8,610
6,150
1,590
Total emissions
Ib/yr
80,280
36,720
8,640
17,160
8,040
45,360
6,360
28,680
9,600
60,240
8,040
71,640
34,440
24,600
6,360
g/s
1.16
0.53
0.12
0.25
0.12
0.65
0.09
0.41
0.14
0.87
0.12
1.02
0.50
0.35
0.09
ro
_j
IO
(continued)
-------
TABLE £-116 (continued)
Company
Monsanto
Phillips
Quitana-Howell
Shell
Chevron
Amoco
Sun
Tenneco
Union Oil
Union Pacific
Location
Texas City, TX
Guayama, PR
Corpus Christi , TX
Deer Park, TX
Pascagoula, MS
Richmond, CA
Texas City, TX
Whiting, IN
Corpus Christi , TX
Marcus Hook, PA
Toledo, OH
Chalmette, LA
Chicago, IL
Corpus Christi, TX
Total
Emissions, Ib/yr
Process
1,410
14,310
1,830
10,770
9,300
8,610
35,130
25,800
3,420
2,850
7,170
5,700
1,440
450
239,730
Storage
2,820
28,620
3,660
21,540
18,600
17,220
70,260
51,600
6,840
5,700
14,340
11,400
2,880
900
479,460
Fugitive
1,410
14,310
1,830
10,770
9,300
8,610
35,130
25,800
3,420
2,850
7,170
5,700
1,440
450
239,730'
Total emissions
Ib/yr
5,640
57,240
7,320
43,080
37,200
34,440
140,520
103,200
13,660
11,400
28,680
22,800
5,760
1,800
958,920
g/s
0.08
0.82
0.11
0.62
0.54
0.50
2.02
1.49
0.20
0.16
0.41
0.33
0.08
0.03
ro
rv>
o
Source: Systems Applications, Inc., 1980.
-------
TABLE £-117. XYLENE ISOMER EMISSIONS FROM USERS
Company
Location
Emissions, Ib/yr
Process
Storage
Fugitive
Total emissions
Ib/yr
g/s
Phthalic Anhydride Producers (o-xylene)
Allied
BASF Wyandotte
Exxon
Koppers
Monsanto
Hooker
Chevron
Stepan
El Segundo, CA
Kearny, NJ
Baton Rouge, LA
Ciecero, IL
Texas City, TX
Arecibo, PR
Richmond, CA
Millsdale, IL
Total
3,640
14,980
13,020
23,520
14,980
8,680
5,040
9,940
93,800
520
2,140
1,860
3,360
2,140
1,240
720
1,420
13,400
1,040
4,280
3,720
6,720
4,280
2,480
1,440
2,840
26,800
5,200
21,400
18,600
33,600
21,400
12,400
7,200
14,200
134,000
0.07
0.31
0.27
0.48
0.31
0.18
0.10
0.20
ro
ro
Isophthalic Acid Producer (m-xylene)
Amoco
Joliet, IL
83,000
4,900
9,800
98,000
1.41
Dimethylterephthalate Producers (p-xylene)
DuPont
Eastman Kodak
Hereof ina
Old Hickory, TN
Wilmington, NC
Columbia, SC
Kingsport, TN
Wilmington, NC
Total
35,490
87,360
32,370
32,370
84,110
271,700
8,190
18,660
7,470
7,470
19,410
61,200
19,110
43,540
17,430
17,430
45,290
142,800
62,790
149,560
57,270
57,270
148,810
475,700
0.90
2.15
0.82
0.82
2.14
Terephthalic Acid Producers (p-xylene)
Amoco
Hereof ina
Cooper River, SC
Decatur, AL
Wilmington, NC
Total
1,120,140
2,242,820
269,240
3,632,200
48,510
97,130
11,660
157,300
30,870
61,810
7,420
100,100
1,199,520
2,401,760
288,320
3,889,600
17.27
34.58
4.15
Source: Systems Applications, Inc., 1982.
-------
TABLE E-118. XYLENE ISOMER EMISSIONS FROM MIXED XYLENE SOLVENT USES
Paints and coatings
Adhesive, rubber
Chemical, automotive
Agricultural pesticides
Household products,
printing inks
Total
Total mixed
xylene
emissions,
106 Ib/yr
422
77
65
66
55
685
p-xylene
emissions,
106 Ib/yr
70.474
12.859
10.855
11.022
9.185
114.395
o-xylene
emissions,
106 Ib/yr
86.510
15.785
13.325
13.530
11.275
140.425
m-xylene
emissions,
106 Ib/yr
150.654
27.489
23.205
23.562
19.635
244.545
Source: Systems Applications, Inc., 1980.
TABLE E-119. XYLENE ISOMER EMISSIONS FROM GASOLINE MARKETING
Region
New England
Middle Atlantic
East North Central
West North Central
South Atlantic
East South Central
West South Central
Mountain
Pacific
Total
Number
of sites
11,105
28,383
42,270
23,304
37,286
16,313
28,336
12,815
26,647
226,459
o-xylene
emissions,
Ib/yr
104,831
267,935
399,029
219,990
351,980
153,995
267,492
120,974
251,548
2,137,774
m-xylene
emissions,
Ib/yr
254,638
650,822
969,251
534,361
854,968
374,057
649,744
293,848
611,016
5,192,705
p-xylene
emissions,
Ib/yr
104,831
267,935
399,029
219,990
351,980
153,995
267,492
120,974
251,548
2,137,774
Source: Systems Applications, Inc., 1982.
222
-------
ro
INJ
CO
NOTE: NUMERALS DENOTE NUMBER OF PLANTS.
Figure E-8. Specific point sources of o,m,p-xylene emissions.
Source: Systems Applications, Inc., 1980.
-------
Sampling and Analytical Methods
1. NIOSH Method 1501
a. Solid Sorbent Tube (coconut shell charcoal, 100 mg/50 mg).
b. Gas chromatography.
c. Flame ionization detector.
Detection limit:
0.2 ppm for 10-liter sample
Possible interferences:
Alkanes less than C10 along with volatile organic sol-
vents (e.g., alcohols, keytones, ethers, and halogenated
hydrocarbons).
2. Method B (Appendix A): C2-C16 hydrocarbons and other nonpolar
organics with a boiling point of 100° to 175°C.
a. Whole air collection in canister.
b. Cryogenic concentration.
c. Gas chromatography/flame ionization detection (gas
chromatography/photoionization detection may also be
used).
Detection limit:
0.1 ppb per 100-ml sample
Possible interferences:
Reactive compounds are not readily analyzed. Storage
times greater than a week are not recommended.
3. Method C (Appendix A): C6-C12 hydrocarbons and other nonpolar
organics with a boiling point of 60° to 200°C.
a. Adsorption of Tenax (XAD-2 with solvent extraction may be
used).
b. Thermal desorption.
c. Gas chromatography/mass spectrometry analysis (gas
chromatography/photoionization detection may also be
used).
Detection limit:
1 to 200 ppt for a 20-liter sample
Possible interferences:
Blank levels usually limit sensitivity artifacts due to
reactive components (03, NO ). Sample can be analyzed
only once. *
4. Method D (Appendix A): C6-C12 hydrocarbons and other nonpolar
organics with a boiling point of 60° to 200°C.
a. Adsorption of Tenax (XAD-2 with solvent extraction may be
used).
b. Thermal desorption into canisters.
224
-------
c. Gas chromatography/flame ionization detection, or gas
chromatography/mass spectrometry analysis (gas
chromatography/photoionization detection may also be
used).
Detection limit:
0.01 to 1 ppb for a 20-liter sample
Possible interferences:
Blanks and artifact problems in Method C, above.
Permissible Exposure Limits
OSHA ACGIH NIOSH
TWA 100 ppm (435 mg/m3) 100 ppm (435 mg/m3) 100 ppm
Ceiling 200 ppm (10 min)
STEL 150 ppm (655 mg/m3)
Human Toxicity
Acute Toxicity:
Human eye and skin irritation can start at 200 ppm. Moderate
irritant through intraperitoneal, subcutaneous, and inhalation
means. Low toxicity orally. Very little dermal toxicity. At
high concentrations, xylene vapor may cause severe breathing
difficulties, which may be delayed in onset. At high concen-
tration, may also cause dizziness, staggering, drowsiness, and
unconsciousness. In addition, breathing high concentrations
may cause lack of appetite, nausea, vomiting, abdominal pain,
and reversible damage to kidneys and liver.
Chronic Toxicity:
Repeated exposure of the eyes to high concentrations of xylene
vapor may cause reversible eye damage.
Bibliography
American Conference of Governmental Industrial Hygienists. 1984. TLVs,
Threshold Limit Values for Chemical Substances and Physical Agents in the
Work Environment and Biological Exposure Indices With Intended Changes for
gicai Ex
12-54-6.
1984-1985. ISB N:0 - 936712-54-6. Cincinnati, OH.
Hawley, G. G. 1981. The Condensed Chemical Dictionary. 10th Edition. Van
Nostrand Reinhold Company, New York.
National Fire Protection Association. 1983. National Fire Codes, A Com-
pliance of NFPA Codes. Standards, Recommended Practices, and Manuals.
Volume 13.NFPA, Quincy, MA.
Sax, I. N. 1981. Dangerous Properties of Industrial Materials. Sixth
Edition. Van Nostrand Reinhold Company, New York.
225
-------
Sittig, M, 1981. Handbook of Toxic and Hazardous Chemicals. Noyes
Publications. Park Ridge, NJ.
Systems Applications Inc. 1980. Human Exposure to Atmospheric Concentra-
tions of Selected Chemicals. Volume 1. Appendix A-29 - XyleneTP~B
81-193252.Systems Applications, Inc., San Rafael, CA.
Systems Applications Inc. 1982. Human Exposure to Atmospheric Concentrations
of Selected Chemicals, Volume II. Appendix A-29, Xylene. EPA Contract No.
68-02-3066.SAI No. 58-EF81-156R2. Systems Applications, Inc., San
Rafael, CA.
U.S. Department of Health and Human Services. 1983. Chemical Registry of
Toxic Effects of Chemical Substances 1981 to 1982. National Institute for
Occupational Safety and HealtTi. Cincinnati, OH.
U.S. Department of Health and Human Services. 1984. Manual of Analytical
Methods. Third Edition. National Institute for Occupational Safety and
Health. Cincinnati, OH.
U.S. Environmental Protection Agency. 1980. Treatability Manual: Volume 1
Treatability Data. EPA 600-8-80-042a.
Weast, R. T. 1981. CRC Handbook of Chemistry and Physics. 61st Edition.
CRC Press, Inc., Boca Raton, FL.
226
-------
-------
APPENDIX F
GUIDANCE FOR THE CHOICE OF MONITORING FREQUENCY
TO BE USED IN ESTIMATING ANNUAL AVERAGE CONCENTRATIONS
OF NONCRITERIA AIR POLLUTANTS
Prepared by
Systems Applications, Inc.
101 Lucas Valley Road
San Rafael, California 94903
Monitoring Section
Monitoring and Data Analysis Division
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
April 1985
-------
ACKNOWLEDGMENT
Thanks go to the many reviewers at the U.S. Evironmental Protection
Agency, and in particular to Neil Frank, Bill Hunt, and Tom Curran of the
Monitoring and Reports Branch for their thoughtful comments and time spent
on earlier drafts of this guideline document.
-------
ABSTRACT
The reliability of the estimated annual average concentration of a
noncriteria air pollutant is considered. The increase in precision
resulting from more frequent monitoring is illustrated, and guidance on
the selection of a monitoring frequency to achieve a desired precision is
provided.
-------
DISCLAIMER
Although this report has been funded by the United States Environmental
Protection Agency through Contract No. 68-02-3848, it has not been subject
to the Agency's peer and administrative review; therefore, it does not
necessarily reflect the views of the Agency, and no official endorsement
should be inferred.
-------
CONTENTS
INTRODUCTION 1
MONITORING PROGRAMS 2
ISSUES 3
SOURCES OF INFORMATION 4
THE PRECISION RESULTING FROM COMBINATIONS OF
SAMPLING AND POLLUTANT CHARACTERISTICS 4
EXAMPLES OF TRADE-OFFS BETWEEN PRECISION
AND SAMPLING .FREQUENCY 8
SUMMARY 13
References 14
Appendix: DERIVATION OF THE RELATIONSHIP BETWEEN SAMPLING
FREQUENCY AND THE PRECISION OF THE ESTIMATED
ANNUAL AVERAGE CONCENTRATION 16
81*20^2 1
-------
-------
INTRODUCTION
There are at present no national ambient air quality standards for a num-
ber of air pollutants considered to be of possible harm to public
health. Planning is in progress, and some programs are already under-
way, by national, state, and local agencies, to monitor these so-called
noncriteria air pollutants. The monitoring data will be used for many
purposes, e.g., to estimate air quality trends, population exposure, or
the influence of emissions.
In allocating funds for these programs, it is important to determine
where and how often the pollutants must be monitored to achieve stated
objectives. In this report we restrict attention to the sampling fre-
quency required to reliably estimate annual average concentrations. Other
monitoring objectives, as well as the costs and health Benefits of various
monitoring alternatives, although very important, are not discussed
here. In particular, the monitoring of high concentrations of short dura-
tion will be addressed in a future report.
Our purpose is thus to quantify and illustrate the effect of sampling
frequency on the precision of the sample annual average concentration of a
noncriteria air pollutant. It should be noted that even within this nar-
rowly defined context we have had to set aside from our discussion certain
important aspects of the design or evalution of a monitoring program such
as measurement error, minimum detection limits, quality assurance, or the
determination of just how much precision is needed. Nevertheless the
results and examples presented should provide some useful information on
the design and evaluation of monitoring programs.
It should also be noted that the determination of monitoring objectives,
the development and understanding of alternative monitoring methods, and
the design of programs to meet these objectives are evolving in concert
through ongoing activities. Specifically, several state and local
agencies are currently monitoring noncriteria air pollutants, and the U.S.
Environmental Protection Agency has a pilot phase of the Toxic Air Moni-
toring System (TAMS) underway.
6^20
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MONITORING PROGRAMS
The Toxic Air Monitoring System (TAMS)
The U.S. Environmental Protection Agency (EPA) is currently developing
a Toxic Air Monitoring System (TAMS), a network of stations to monitor up
to 60 non.criteria air pollutants. One important goal of the TAMS is to
enable researchers to assess long-term exposures to toxic air pollutants,
hence our emphasis on the estimation of annual average concentrations.
An important limitation of the monitoring program is that precipitation
interferes with the measurement of certain volatile organic compounds
(VOC's) collected on Tenax adsorbent material. Lumpkin and Bond (1984)
state that samples of this type taken during precipitation should not be
used, however other monitoring methods less vulnerable to precipitation
are under study.
Another important aspect of the monitoring program is that samplers must
be operated at different flow rates and for different sampling periods to
effectively monitor different compounds. For some VOC's the usual 24-hour
integrated samples are not possible because the 24-hour air volume would
exceed the retention volume (Walling, 1984). Thus, shorter sampling
periods, e.g., 12-hour or 6-hour integrated samples, may be required.
This adds the dimension of time of day to the design of the monitoring"
program.
The EPA plans to conduct a pilot monitoring program in a few urban areas
(beginning with Boston, Chicago, and Houston) before the national network
is established. The current sampling plan for the TAMS pilot network is
to monitor at each site (1) certain volatile organic compounds (VOC's)
collected on Tenax, (2) formaldehyde, (3) benzo(a)pyrene (BaP), and (4)
the trace metals arsenic, cadmium, chromium, and nickel. Twelve-hour or
6-hour integrated samples of VOCs will be taken. Either 12- or 24-hour
integrated samples of formaldehyde will be taken, and 24-hour integrated
samples of BaP and the metals will be taken using high-volume ("hi-vol")
particulate samples. The experience and data gained from the pilot
program will enable the EPA to conduct the larger effort with greater
efficiency.
Toxic Air Monitoring by State and Local Agencies
In addition to the planned national system for monitoring noncriteria air
pollutants, many state and local agencies have or are planning programs to
monitor these pollutants. A practical limitation of these programs,
shared by national programs, is that only a proportion of the scheduled
samples yield valid observations. Planned observations may be missed or
-------
invalidated because of precipitation or equipment failure, for example.
The proportion of valid observations is known as the data capture rate.
ISSUES
A number of issues related to the TAMS are discussed by Thrall, Burton,
and Moezzi (1984). These issues include the estimation of diurnal or
seasonal components of variation, trade-offs between infrequent monitoring
at several sites versus more frequent monitoring at one site, and the
precision required of estimated annual concentrations given the uncer-
tainty of our knowledge of the health risks associated with different
pollutants.
In addition to the issues arising in national monitoring programs, a state
or local agency may face the issue of determining whether the annual aver-
age concentration of a noncriteria pollutant is sufficiently high at some
particular site to be of concern. If the concentration at which chronic
human health effects occur is known, then the agency may wish to monitor
the pollutant with sufficient frequency so that reliable comparisons can
be made between the estimated annual average concentration and the speci-
fied annual mean level of concern. When the concentration at which
chronic health effects occur cannot be specified, the agency may neverthe-
less wish to compare estimated annual averages to levels observed at other
sites or during previous years so that sites requiring more intensive
investigation can be identified.
Another issue is the monitoring frequency required to produce estimated
annual averages of specified reliability. In this case, the agency's
concern would be the more general one of obtaining data (i.e., estimated
averages) of good quality. The two issues we discuss may be summarized as
follows.
Reliability of Comparisons: What frequency of monitoring is required
to produce reliable comparisons between the estimated annual average
concentration and some specified level?
Reliability of Estimates: What frequency of monitoring is required
to produce reliable estimates of the average of ambient concentra-
tions over the entire course of the year, i.e., the average that
would be obtained from an uninterrupted data record?
8 <«20
-------
SOURCES OF INFORMATION
The TAMS network will provide needed information about the level and
variability of noncriteria air pollutants. Although profiles of these
pollutants have been compiled (see, e.g., Hunt, Faoro, and Duggan, 1984;
Koch et al., 1984; and Singh et al., 1977, 1979, 1983), long-term records
of ambient concentrations are rare. Our recommendations and examples are
based on one of the few such long-term records. The California Air
Resources Board (CARB) monitored trichloroethylene, carbon tetrachloride,
and chloroform in El Monte from November 1982 through September 1983 and
in three other sites in the Los Angeles area from January through Septem-
ber 1983. The data collected by the CARB are discussed by Hunt (1984) and
by Thrall, Burton, and Moezzi (1984) and are summarized here in Table 1.
The concentrations reported in Table 1 represent 24-hour integrated
samples. The data include 14 instances in which concentrations were below
the lower detection limit of the monitoring instrument but were reported
as equalling the instrument's lower limit. The data also include some
suprisingly high concentrations, notably a 3 ppb concentration of chloro-
form recorded in downtown Los Angeles on 29 March 1983. These reported
concentrations have been confirmed by both EPA and CARB technical staff,
that is, the concentrations do not appear to be the result of transcrip-
tion errors or faulty chemical analysis. For the time being we interpret
these concentrations as indicative of occasionally high values at these
sites, although the possibility remains that they are the result of either
some gross error in the measurement process or some very unusual event.
THE PRECISION-RESULTING FROM COMBINATIONS OF
SAMPLING AND POLLUTANT CHARACTERISTICS
The bias and imprecision of estimated annual average concentrations serve
as criteria to assess the need for more or less frequent monitoring of
VOC's and other noncriteria air pollutants. Within the resources avail-
able, it is also important to accurately estimate variances, that is, to
get some indication of the geographic variability of annual average con-
centrations within an urban area, and to obtain reliable estimates of the
extremes and standard deviation of concentrations at a site over the
course of a year, particularly during the initial operation of a network.
We emphasize, however, that we are restricting attention to the statisti-
cal reliability of estimated annual average concentrations, as mentioned
in the introduction. That is, there are other important issues beyond the
scope of the present discussion, such as the comparative costs of imple-
menting various monitoring strategies, alternative monitoring objectives
-------
TABLE 1. Summary statistics for three volatile organic compounds (VOCs) monitored at four
sites in the Los Angeles Area from November 1982 through September 1983 (concentrations are
expressed in parts per billion).
Pollutant
Trichloroethylene
Carbon
Tetrachloride
Chloroform
Statistic
Average
Standard Dev.
Coefficient of
Maximum
Minimum
Sample Size
Average
Standard Dev.
Coefficient of
Maximum
Minimum
Sample Size
Average
Standard Dev.
Coefficient of
Maximum
Minimum
Sample Size
El Monte
0.289
0.230
Var. 0.796
1.200
0.020
180
0.039
0.009
Var. 0.242
0.073
0.010
179
0.062
0.096
Var. 1.542
1.100
0.020
179
Downtown
Los Angeles
0.565
0.295
0.522
1.500
0.020
42
0.037
0.008
0.224
0.060
0.010
41
0.144
0.454
3.148
3.000
0.020
42
Site
Dominquez
0.283
0.158
0.560
0.680
0.100
43
0.041
0.012
0.297
0.080
0.030
43
0.051
0.024
0.471
0.140
0.020
42
Riverside
0.327
0.185
0.566
0.870
0.020
37
0.036
0.007
0.193
0.060
0.030
36
0.061
0.061
1.007
0.400
0.020
37
Combined
0.331
0.245
0.739
1.500
0.020
302
0.038
0.009
0.247
0.080
0.010
299
0.072
0.187
2.611
3.000
0.020
300
-------
(e.g., comparing the influence on air quality of different sources of
pollutant emissions, or estimating peak concentrations), or the public
health benefits of the information to be gained from monitoring.
The trade-off between precision and sampling frequency is illustrated in
Table 2 for sampling frequencies of 1/3, 1/6, 1/12. The table gives 95
percent confidence bounds on the magnitude of the error of the estimated
annual average expressed as a percentage of the actual annual average
(i.e., the relative difference, expressed as a percentage, between the
estimated and actual averages). These bounds have been obtained from a
normal distribution that approximates the sampling distribution of the
estimated annual average concentration for a data capture rate (percentage
of scheduled observations yielding valid data) ranging from 50 to 100
percent, and for a coefficient of variation (the standard deviation
divided by the average, thus the relative variation about the average)
ranging from 25 to 300 percent.
Table 2 shows, for example, that monitoring carbon tetrachloride at one of
the four sites in the Los Angeles area with a 100 percent data capture
rate will result in a relative error likely to' be no more than 4 percent
if 24-hour concentrations (or two consecutive 12-hour concentrations) are
monitored once every three days. The bound changes from 4 percent to 9
percent if monitoring is scheduled once every 12 days. At the other end
of the scale, monitoring chloroform in downtown Los Angeles with only a 50
percent data capture rate could result in a 69 percent error if monitoring
were scheduled every three days, and a 148 percent error if monitoring
were scheduled every 12 days.
Note that the table also provides precision bounds for monitoring 12-hour
concentrations alternately during the night and day. One can, of course,
effectively construct 24-hour observations by sampling uuring consecutive
12-hour periods. Alternatively, monitoring 24-hour concentrations once
every 3, 6, or 12 days corresponds to monitoring 12-hour concentrations
once every 36 hours, three days, or six days, respectively.
Similarly, the table can be interpreted for 6-hour samples. Again, 24-
hour averages can be formed if four consecutive 6-hour samples are taken
at a time. The table then applies to blocks of 4 consecutive samples
taken once every 3, 6, or 12 days. More generally, the table applies to
sampling schedules that call for monitoring a representative one-third,
one-sixth, or one-twelfth of the total number of possible sampling
periods.
An important assumption used in the construction of the table is that the
probability of data capture is independent of the probability of the
occurrence of either high or low concentrations. Entries in the table
8<*20<*r2 2 6
-------
TABLE 2. Ninety-five percent confidence bounds on the magnitude
of the error of the annual average concentration estimated from
scheduled monitoring of 24-hour concentrations once every three,
six, or 12 days, respectively, when the error is expressed as
a percentage of the actual annual average concentration.
Data
Capture
Rate (%)
100
90
80
70
60
50
Sampling
Frequency
1/3
1/6
1/12
1/3
1/6
1/12
1/3
1/6
1/12
1/3
1/6
1/12
1/3
1/6
1/12
1/3
1/6
1/12
Coefficient -of
25a
4
6
9
4
6
9
4
7
10
5
7
10
5
8
11
6
9
12
50
7
11
17
8
12
18
9
13
19
9
14
21
10
15
22
11
17
25
75b
11
17
26
12
18
27
13
20
29
14
21
31
15
23
34
17
26
37
Variation (%)
100
15
23
34
16
24
36
17
26
38
19
28
41
21
31
45
23
34
49
200
29
46
68
31
49
72
34
52
77
37
56
82
41
62
89
46
68
98
300C
44
69
1U2
47
73
108
51
78
115
56
85
124
62
92
134
69
102
148
25 percent corresponds roughly to the combined CV for carbon
tetrachloride in Table 1.
75 percent corresponds roughly to the combined CV for
trichloroethylene in Table 1.
c 300 percent corresponds roughly to the combined CV for
chloroform in Table 1.
-------
would have to be modified if it were known, for example, that daytime
concentrations tended to be higher or lower than nighttime concentrations
and that a disproportionate number of, say, nighttime observations would
fail to yield valid data.
From the table we see that for a pollutant and site for which the coeffi-
cient of variation and data capture rate are known, or can be estimated,
precision increases roughly in proportion to the square of the expected
number of valid observations. For example, the error bound for samples
taken once every 12 days is roughly twice that for samples taken once
every three days.
In designing a network consideration must be given to: (1) the expected
data capture rate (including loss of samples due to precipitation); (2)
the likely coefficients of variation of different pollutants at different
sites; and (3) the desired bounds on the percentage error of estimated
annual average concentrations. Thrall, Burton, and Moezzi (1984) discuss
these and other considerations in their review of the CARB data.
EXAMPLES OF TRADE-OFFS BETWEEN PRECISION
AND SAMPLING FREQUENCY
In choosing a monitoring frequency, one should consider not only the
desired level of precision, but also the likely data capture rate (the
proportion of scheduled monitoring days that yield valid observations),
and the number and types of sources of pollutant emissions that would
influence the level and variability of ambient concentrations from day to
day. The following examples illustrate this point.
Example 1. Suppose that the annual average concentration of trichloro-
ethylene at a new monitoring site is to be compared to the approximately
0.3 ppb recorded at three of the four sites located in the Los Angeles
area listed in Table 1. Suppose also that we are willing to assume that
the daily ambient concentrations at the new site are not much more vari-
able than those at the Los Angeles sites, i.e., that the coefficient of
variation (the standard deviation expressed as a percentage of the annual
average) at the new site is 100 percent (the maximum coefficient of varia-
tion among the four Los Angeles sites is about 80 percent), and that the
likely data capture rate will be 75 percent.
Finally, we want to be confident that the estimated average concentration
will fall below 0.3 ppb if the actual value is below 0.3 ppb, and, con-
versely, that the estimate will fall above 0.3 ppb if the actual average
is above 0.3 ppb. Of course, if the actual average concentration equals
6»»20M*2 2
-------
0.3 ppb or is very close to this level, the estimate may easily fall above
or below the 0.3 ppb level. So, to be more precise, we may require suf-
ficiently frequent monitoring such that, say, with 90 percent probability,
the estimate will fall on the same side of the 0.3 ppb level as the actual
average, provided that the magnitude of the relative difference between
the specified 0.3 ppb level and the actual annual average concentration at
the site is at least 10 percent. Under these circumstances the required
frequency of scheduled monitoring is about once every three days. The
derivation of the required monitoring frequency will be explained shortly.
Example 2. Suppose now that we plan to compare the annual average concen-
tration of chloroform to be obtained at the new site with the approxi-
mately 0.06 ppb obtained at the same three Los Angeles sites as in Example
1. Suppose, again, that the data capture rate is 75 percent, and that we
want to be 90 percent confident of a correct comparison, provided that the
magnitude of the relative difference between the specified 0.06 ppb level
and the actual average concentration is at least 10 percent. The required
sampling frequency now depends on whether the relative variability, i.e.,
the coefficient of variation, of daily ambient concentrations at the new
site resembles that of Riverside.or that of downtown Los Angeles. A site
resembling Riverside would have a coefficient of variation of about 100
percent, and the required sampling frequency would again be about once
every three days. A site resembling downtown Los Angeles would have a
coefficient of variation of about 300 percent, and everyday sampling would
be required.
The required frequency can be formulated as follows. If we let f denote
the frequency of scheduled monitoring, then f~* is the period between
scheduled samples, so that monitoring is scheduled "once every f days"
(or, more generally, once every f~* time intervals). In Examples 1 and 2,
f~* was obtained using the following formula' (derived in the appendix):
f1
•
CV
where
p = the proportion of scheduled monitoring days that yield valid
observations, also known as the data capture rate; in our
exampes p = 0.75;
Tne "relative difference" between two numbers, x and y, is (x - y)/y.
8 U2C <+r2 2 9
-------
N = the total number of time intervals in a year, e.g., N = 365
in our examples, corresponding to the number of 24-hour
intervals in a year;
PL = a lower limit on the magnitude of the relative difference
between the specified level and the new site's actual annual
average concentration; r = 0.1 in our examples; corresponding
to our objective of identifying differences as great or
greater than 10 percent;
CV = the coefficient of variation (the ratio of the standard
deviation divided by the average) at the new site, e.g., 1.0
to 3.0 in our examples;
z = the percentile of the standard normal distribution, corre-
sponding to the level of confidence desired for a correct
comparison; in our examples z = 1.282, corresponding to the
desired 90 percent level of confidence; in general, setting z
equal to the (1- a)th quantile produces a (1 •• a) level of
confidence, 90 or 95 percent being typical choices in sta-
tistical applications.
Generally, Equation 1 should be regarded as providing an initial approxi-
mation to the required monitoring frequency. If the number of valid
observations per year (f»p«N) is less than 20, then it is advisable to
override Equation 1 with the recommendation of Hunt, Faoro, and Duggan
(1984) that at least five valid observations per quarter be obtained.
Similarly, it is wise to avoid monitoring exclusively on one da'y of the
week, even if such a schedule is obtained from Equation 1, because pollu-
tant levels may differ substantially on different days of the week.
Finally, a once-per-six-day monitoring schedule is common among many
agencies, and it may be practically important to coordinate the new
schedule with existing schedules. Since Equation 1 approximates the mini-
mum amount of monitoring needed to meet specified criteria, any adjust-
ments to the derived sampling frequency should generally be in the direc-
tion of providing more frequent monitoring. The next examples illustrate
these suggestions.
Example 3. Suppose that the annual average concentration of carbon tetra-
chloride at the new monitoring site is to be compared to the approximate
0.04 ppb obtained at the four sites in the Los Angeles area listed in
Table 1. Suppose, again, that the expected data capture rate is 75 per-
cent (p = 0.75), and that we want to be 90 percent confident of a correct
comparison (z = 1.282, the 90th percentile of the standard normal distri-
bution) if the magnitude of the relative difference between the specified
0.04 ppb level and the new site's actual average concentration is at least
8420WP2 2 10
-------
10 percent (TL = 0.1). Finally, let us assume that the coefficient of
variation for the new site is only 25 percent (CV = 0.25), which is the
approximate value at the Los Angeles sites.
Due to the low coefficient of variation. Equation 1 yields an approximate
once-per-34-days sampling schedule (f~ = 34), i.e., about 11 scheduled
monitoring days per year, which, using the-75 percent data capture rate,
can be expected to yield about eight valid observations per year
(f»p«N = 8). Since this is less than the recommended 20 valid obser-
vations per year, we would adopt the suggestion of Hunt, Faoro, and Duggan
(1984) that at least five valid observations per quarter be obtained.
Based on the 75 percent data capture rate, we might therefore schedule
monitoring once every 12 days. (A straightforward calculation yields a
sampling schedule of once every 13.7 days; monitoring every 12 days thus
allows for a data capture rate in one or more quarters that is somewhat
less than 75 percent.)
When we have no specific concentration to which the calculated annual
average is to be compared, we may simply require that the average obtained
from intermittent monitoring be close to the average of ambient concentra-
tions over the entire course of the year.
One way to express this requirement is that the relative difference
between the calculated and underlying annual averages should be, say, less
than 10 percent with at least 90 percent probability. Equation 2 (derived
in the appendix) provides a formula for calculating the sampling period,
f , meeting these requirements:
(2)
where r., is the desired upper limit (e.g., 0.1) on the magnitude of the
relative difference, z^ is the percentile of the standard normal distri-
bution corresponding to the desired confidence level,* and N, p, and CV
are as given under Equation 1. Again, Equations 1 and 2 merely provide an
initial approximation to the required monitoring frequency (see the
remarks following Equation 1).
* To achieve the confidence level 1 - a, Z£ should be the 1 - (a/2)
quantile of the standard normal distribution, e.g., Zo should be the
95th percentile (1.645) to achieve 90 percent confidence.
8<+2C'*r2 2
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Example 4. Suppose that a state or local agency plans to monitor 24-hour
concentrations of carbon tetrachloride sufficiently often so that the
relative difference between the estimated and actual annual average con-
centrations will be no more than 10 percent with 90 percent probability
(PU = 0.1, z2 = 1.645). The coefficient of variation is assumed to be 25
percent ^CV = 0.25), consistent with the data from Table 1, and the data
capture rate is assumed to be 75 percent (p = 0.75). Since there are 365
24-hour intervals in the year (N = 365), Equation 2 yields an approximate
sampling schedule of once every 17 days (f = 17). However, since the
expected number of valid observations is less than 20 (f»p»N is approxi-
mately 16), a schedule of once every 12 days would be more appropriate,
consistent with the remarks in example 3.
Example 5. Suppose that the situtation is as described in example 4,
except that the measurement method is based on 12-hour samples rather than
24-hour samples. Application of the formula for the required sampling
frequency -now indicates monitoring one out of every seventeen 12-hour
intervals. This could be achieved in a number of ways, e.g., monitoring
for 12 hours every 8 1/2 days (thus alternating between nighttime and
daytime monitoring) or monitoring during two consecutive 12-hour intervals
every 17 days. There may be some statistical advantage to one scheme over
the other, depending on the pattern of daytime and nighttime concentra-
tions. Also, in order to match other monitoring schedules, it may be more
convenient to take alternate nighttime and daytime samples once every six
days, or to take two consecutive samples once every twelve days. In any
case, if the annual average is to be estimated as the simple arithmetic
average of all valid 12-hour samples collected during the year, it is
important to obtain about the same number of nighttime and daytime samples
to avoid biasing the estimated annual average.
Example 6. Again, let us suppose that the situation is as described in
example 4, this time with 6-hour samples. Equation 2 now indicates moni-
toring one out of every seventeen 6-hour intervals. This might be
accomplished most conveniently by monitoring four consecutive 6-hour
intervals once every 17 days. This frequency might be increased to moni-
toring four consecutive 6-hour intervals once every 12 days to better
coincide with other monitoring schedules. Other sampling designs are
possible, but if the annual average is to be estimated as the simple
arithmetic average of all valid 6-hour samples collected during the year,
it is important to obtain approximately the same number of valid observa-
tions for each 6-hour interval of the day.
8i*20'»r2 2 12
-------
SUMMARY
The development of a program to monitor specified noncriteria air pollu-
tants is a large undertaking with many potential objectives, constraints,
and unknowns. This guideline focuses on the monitoring frequency needed
to reduce to a specified level the effect of sampling error on the esti-
mated annual average concentration of a pollutant at one monitoring sta-
tion. "Sampling error" here refers to the fact that the annual average
must be estimated from a sample of say, days in the year, since practical
constraints limit how often monitoring can be scheduled. In principle the
problem of sampling error may be eliminated by monitoring every day or,
more generally, during every possible time interval (practically, however,
missing or invalid observations can and do occur in this case as well).
Thus the guideline addresses one aspect, solvable at least in principle,
of a larger and more difficult problem.
Within the sampling error context, a formula is derived in the appendix
for the probable error in the estimated annual average as a function of
monitoring frequency, data capture rate, and the relative variation of
pollutant concentrations over the course of the year. The formula is
illustrated in Table 2 and the concluding examples show how related formu-
las can be used to determine the monitoring frequency needed to limit the
probable error to a prescribed magnitude. In some cases where the rela-
tive variation in pollutant concentrations is low, the derived infrequent
monitoring is overridden by a longstanding EPA recommendation that at
least 5 valid observations per quarter be obtained.
13
-------
REFERENCES
Goldstein, Bernard D. 1983. Toxic substances in the atmospheric environ-
ment. J. Air Poll. Control Assoc., 33(5):454-467.
Hunt, William F., Jr. 1984. "Examination of Alternative Sampling
Frequencies for Volatile Organic Chemical Data." U.S. Environmental
Protection Agency memorandum.
Hunt, William F., Or., R. B. Faoro and G. M. Duggan. 1984. "Compilation
of Air Toxic and Trace Metal Summary Statistics". U.S. Environmental
Protection Agency, Research Triangle Park, North Carolina (EPA-450/4-
84-015).
Koch, R. C., et al. 1984. "Network Design and Site Exposure Criteria
for Selected Noncriteria Air Pollutants." GEOMET Technologies, Inc.,
Rockville, Maryland (EPA-450/4-84-022).
Langstaff, John E., and A. D. Thrall. 1984. "Consideration of
Appropriate Sampling Frequencies for the Monitoring of Noncriteria
Air Pollutants." Systems Applications, Inc., San Rafael, California
(SYSAPP-84/044).
Lumpkin, T. A. and A. E. Bond. 1984. "Standard Operating Procedure for
the Toxic Air Samplers Used in the Toxic Air Monitoring System
(TAMS)." U.S. Environmental Protection Agency (EMSL/SOP-EMD-204).
Singh, H. B., et al. 1977. Urban-nonurban relationships of halo-
carbons, SFg, N20, and other atmospheric trace constituents.
Atmos. Environ., 11:819-828.
Singh, H. B., et al. 1979. "Atmospheric Measurements of Selected Toxic
Organic Chemicals." SRI International, Menlo Park, California.
Singh, H. B., et al. 1983. Measurements of Hazardous Organic Chemicals
in the Ambient Atmosphere. U.S. Environmental Protection Agency,
Research Triangle Park, North Carolina (EPA-600/3-83-002).
8U20*»r ** 14
-------
Thrall, A. D., C. S. Burton, and M. M. Moezzi. 1984. "Consideration of
the Choice of Sampling Frequency to be Used in the Monitoring of
Noncriteria Air Pollutants." Systems Applications, Inc., San Rafael,
California (SYSAPP-84/212).
Walling, Joseph F, 1984. The utility of distributed air volume sets
when sampling ambient air using solid adsorbents. Atmos. Environ.,
18(4):855-859.
8<*20»*r *»
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Appendix
DERIVATION OF THE RELATIONSHIP BETWEEN SAMPLING
FREQUENCY AND THE PRECISION OF THE ESTIMATED
ANNUAL AVERAGE CONCENTRATION
We would like to know the annual average concentration, y of a pollutant
based on a complete set of N measurements. The number of possible
observations to be obtained from the schedule of intermittent monitoring
is some fraction (f) of N, and only a proportion, p (the so-called "data
capture rate") of the scheduled monitoring intervals will produce valid
observations. That is, environmental conditions may prohibit scheduled
monitoring in some instances; in other cases some mishap in the data
collection process may invalidate observations or cause them to be
missed. So from a total of N possible measurements we obtain only pfN
valid observations, which we regard as a random sample from a finite
population.
Letting y denote the sample average concentration, the expected value and
variance of y are
Ey = y
O
where a is the population variance of the N measurements. Moreoever, if
the number of valid and missing (or invalid) measurements is large, i.e.,
if both pfN and N - pfN are large, and if there are relatively few exteme
concentrations, then the sampling distribution of y is approximately
normal. (The conditions for asymptotic normality are formulated more
precisely by Cochran, 1963, who cites Hajek, 1960.)
The approximate normality of y may be conveniently expressed as the
approximate normality of the relative error of y:
where
~ N(0,
y
2 1 - fp CV2
TN " fp N
16
-------
CV =— is the coefficient variation.
We can use these results to obtain approximate answers to the following
two problems.
Problem 1. How frequently should monitoring be scheduled in order to
limit the probability of an erroneous comparison of y to a specified
concentration yg, i.e., of obtaining y > yg when y < yg or vice versa?
Problem 2. How frequently should monitoring be scheduled to limit the
relative error of y to a prescribed level?
We formulate problem 1 as follows. Since the chance of an erroneous
comparison is large if y is close to yg, we suppose that the magnitude of
the relative difference between yg and y is not less than some prescribed
lower bound, r. :
" y>
r
L.
We want the probability of an erroneous comparison to be no more than some
prescibed value, say a. Thus, if \i > yg, we require that
a > Pr(y < u0)
" y ~ ^
>Pr
W
Since the magnitude of the relative difference between yg and y may be as
small as r\, this implies
> Pr
where * is the standard normal cumulative distibution function,
Or, if y < yg, we require that
a > Pr(y > yQ)
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This implies that
a > Pr X-=-* > r,
y L
*(- r, /TN) from the symmetry of the normal distribution,
Thus, in either case, we require that
a > *(-rL/TN) •
or
1 - a < *(rL/TN)
so that
2 22
TN < rL/Zl-a
and hence,
• r 2
2 2
cv^- zf
1-
Here Z^_a denotes the (1 - a)th quantile of the standard normal distribu-
tion.
Problem 2 can be treated similarly. We want the magnitude of the relative
error of u to be no more than some up
probability, say 1-a. We thus have
error of u to be no more than some upper bound, say r.., with a high
Thus
1 - a/2 <
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or
so that
Zl-a/2 < rU/TN *
,2 - _2 ,,2
and hence
TN * rU
(2)
/« '
-a/
REFERENCES
Cochran, W. G. 1963. Sampling Techniques, 2nd ed. Wiley, New York.
Hajek, J. 1980. Limiting distributions in simple random sampling from a
finite population. Pub. Math. Inst. Hungarian Acad. Sci., 5:361-374,
81*20^2 5
i
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