United States	Office of Air Quality	EPA-450/4-84-022
Environmental Protection Planning and Standards	September 1984
Agency	Research Triangle Park NC 27711
vvEPA Network Design
And Site Exposure
Criteria For
Selected
Noncriteria Air
Pollutants

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EPA-450/4-84-022
September 1984
Network Design and Site Exposure
Criteria For Selected
Noncriteria Air Pollutants
by
R. C. Koch. M. B. Charlton,
D. J. Peiton, and H. R. Stern
GEOMET Technologies, Inc.
1801 Research Boulevard
Rockville, Maryland 20850
Contract Number 68-02-3584
Assignment No. 4
Project Officer
David Lutz
U.S. Environmental Protection Agency
Research Triangle Park
North Carolina 2771 1
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Radiation
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 2771 1

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DISCLAIMER
TTiis report has been reviewed by the Office of Air Quality Planning and
Standards, U.S. Environmental Protection Agency, and approved for publication.
Approval does not signify that the contents necessarily reflect the views and
policies of the U.S. Environmental Protection Agency, nor does mention of
trade names or commercial products constitute endorsement or recommendation
for use.

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CONTENTS
Figures 	 iv
Tables 	 v
1.	Introduction 	 1
2.	Monitoring Needs for Noncriteria Pollutants 	 3
Monitoring objectives 		3
Data needs 		3
Principal uses of data 		4
3.	Characteristics of Noncriteria Pollutants 		8
Physical and chemical properties 		8
Sources of emissions 		8
Sampling requirements 		23
Airborne toxicity 		29
4.	Siting Procedures 		34
Representative types of monitoring sites 		34
Overview of siting procedures 		35
Siting procedures for representative spatial scales..	43
5.	References 				70
Appendixes
A.	Recommended monitoring techniques 	 72
B.	Observation of diurnal variations of selected
noncriteria air pollutants 	 89
C.	Meteorological data tabulations avail able from the
National Climatic Data Center 	100
D.	Chemical profiles 	120
¦ 11 i

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FIGURES
Number	Page
1	Site selection procedure					 3?
2	Source configuration 						 39
3	Wi nd rose 											 40
4	Steps for locating an urban scale site						44
5	Concentration as a function of stability class, computed
using HIWAY2 model 					.....50
6	Frequency of 24-hour mean wind directions for Baltimore-
Washington International Airport for 1973-197? 		 53
7	Example of high exposure area 						 54
8	Steps for locating a neighborhood scale site 		 56
9	Guideline for estimating impact distance of a point source
overlapping an area source							 62
10	Steps for locating micro or middle scale sites 			 64
11	Downwind distance to maximum concentration and maximum
relative concentration (xu/Q) as a function of Pasquill
stability class and effective plume height in rural
terrai n 										 67
12	Downwind distance to maximum concentration and maximum
relative concentration (xu/Q) as a function of stability
class and effective plume height in urban terrain 		 68
iv

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TABLES
Number	Page
1	Selected Noncriteria Pollutants That Need Monitor
Siting Guidelines 	 2
2	Common Uses of Monitoring Data 	 4
3	Volatility, Reactivity, and Physical State of 43 Selected
Noncriteria Air Pollutants 	 9
4	Sources of Emission of 43 Noncriteria Pollutants 	 10
5	Ranked Listing of Total Emissions of Selected Noncriteria
Air Pollutants 	 20
6	Classes of Pollutant Sources Applicable to Selected
Noncriteria Air Pollutants 	 24
7	Suggested Analysis Methods for Applicable Sampling Media 	 26
8	Toxicity of Noncriteria Air Pollutants 	 30
9	Representative Scales Applicable to Types of Pollutant
Sources 	 36
10	Maximum Distance for Selected Ratios of Monitored
Concentration to Source Strength 	 47
11	Ambient Concentrations and Emission Factors 	 48
12	Example of the Frequency of Occurrence of Wind Directions
for Neutral Atmospheric Stability 	 52
13	Recommended EPA Models by Source Configuration and
Averaging Time 	 58
14	Identification and Classification of Land Use Types 	 60
v

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SECTION 1
INTRODUCTION
There is a need for air monitor siting guidelines that are applicable
to the noncriteria air pollutants (NCAPs). The increasing need to consider
the effects of known or suspected hazards has led Federals State, and local
air pollution control agencies to measure a variety of hazardous NCAPs. This
has resulted in many short-term ambient air monitoring studies of NCAPs,
To increase the usefulness of NCAP studies, guidelines on network design
and siting criteria are needed. Thus, the objective of this report is to
provide monitor siting guidel 1nes for selected NCAPs. A complete list of
the pol1utants treated in this document is given in Table 1. Most of these
pollutants are toxic organic compounds that are priority substances for
consideration as primary national health hazards. Seven of the listed
pollutants have been identified as hazardous in compliance with Section 112
of the Clean Air Act (CAA).
Ambient monitoring data are needed to determine if the chemical is
present in the ambient air and at what concentration, to assess population
exposure estimates, and to determine the need for emission controls.
For many of the NCAPs, adequate methods to monitor still need to be
developed. Thus, the monitoring activities will be undergoing improvements
to the state-of-the-art methodologies initially put to use. The major
objective of the monitoring activities is to apply available state-of-the-art
techniques in data-gathering programs to observe air quality trends and to
characterize noncriteria levels around critical sources and populations.
The monitoring siting criteria cover all NCAPs with the exception of
pollutants associated with acid rain and visibility or as a criteria pol-
lutant under Section 108 of CAA. Thus, pollutants such as sulfates, nitrates,
inhalable particulates, and other "visibility" pollutants are excluded.
1

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TABLE 1. SELECTED NONCRITERIA POLLUTANTS
THAT NEED MONITOR SITING GUIDELINES
Acetaldehyde
Acrolei n
Acrylonitrile
Ally! chloride
~Arsenic
~Asbestos
~Benzene
Benzyl chloride
~Beryl 1 i um
Cadmi um
Carbon tetrachloride
Chiorobenzene
Chi orofonn
Chloroprene
Chromium
o-,m-,p-Cresol
p-D1chlorobenzene
Dimethyl nitrosamine
Dioxi n
Epichlorohydrin
Ethylene dichloride
Ethylene oxide
Formaldehyde
Hexachlorocyclopentadi ene
Maleic anhydride
Manganese
~Mercury
Methyl chloroform {1,1,1-trichloroethane)
Methylene chloride (dichloromethane)
Nickel
Ni trobenzene
Nitrosomorpholine
Perchloroethylene (tetrachloroethylene)
Phenol
Phosgene
Polychlorinated biphenyls
Propylene oxide
~Radionuclides
Toluene
Trichloroethylene
~Vinyl chloride
Vi nylidene chloride
o-,m-,p-Xylene
~ Listed as hazardous air pollutants under Section 112 of the CIean Air Act.
2

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SECTION 2
MONITORING NEEDS FOR NONCRITERIA POLLUTANTS
MONITORING OBJECTIVES
It is important when planning air monitoring activities to clearly
define the objectives to be met by the monitoring data. In general, the
objectives of ambient monitoring are the following:
® Measure or characterize urban air quality
§ Measure or assess specific source impacts.
If the NCAP data collected satisfy these two objectives, the monitoring
program will satisfy all of the needs for ambient data.
DATA NEEDS
The data needed to meet the monitoring objectives will vary in accuracy,
frequency of measurement, and spatial density, depending on the nature of
the local situation, the nature of the hazard associated with the NCAPs, and
the nature of the measurement process. With regard to the nature of the
hazard for the 43 pollutants listed in Table 1, there are two classes of
hazards, the 7 regulated pollutants already identified by EPA as hazardous
substances, and the remaining 36 pollutants that are suspected to be hazardous
and that are under consideration for regulation. However, ambient air
quality levels that are accepted as hazardous have not been established for
either class. Therefore, accuracy and frequency of measurement may be
considered secondary to spatial variation. It will be most important to
define what areas are affected by the pollutants. This is the data charac-
teristic most closely tied to siting and network design that is the subject
of this document.
The spatial variations of air quality levels may be defined by in
situ monitoring at fixed sites, by mobile monitoring, by remote monitoring
at fixed or mobile sites, or by some combination of the three. In situ
monitoring may include in situ analysis or collection of samples by a media
for subsequent laboratory analysis. The use of personal samplers to collect
samples for laboratory analysis is another way of obtaining spatially variant
data that are especially relevant to human exposure estimates. Although
there are a number of ways of including spatial variability in the monitoring
data, the use of fixed monitoring sites is most common and is the method
for which quality control procedures are best established at present. In
this document, primary emphasis is given to the use of fixed in situ monitor-
ing sites.
3

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The number of fixed monitoring sites needed to measure spatial vari-
ability of NCAPs for one or more monitoring objectives depends very much on
the number, type, and magnitude of sources of emissions. Other influencing
factors are the topography and meteorology of the local area. Methods of
taking these factors into account in pianning for the number and location of
monitoring sites are described in Section 4.
PRINCIPAL USES OF DATA
Common uses of monitoring data listed in Table 2 were recently cited by
the Ad-Hoc Work Group on Air Toxics Monitoring.* These data uses must be
borne in mi nd when planning a monitori ng network. There must be agreement
between those who will use the data and those who will collect them regarding
how many and what locations wi11 meet the data needs. Sometimes this coordi-
nation 1s needed between groups within a single agency. However, more often
there must be coordination between parties of different levels of Government
or between Government and nongovernment parties. Some concepts regarding
how data use relates to monitor siting are discussed below.
TABLE 2. COMMON USES OF MONITORING DATA
(cited by the Ad-Hoc Work Group on Air Toxics Monitoring)
®	Determine air quality status and trends
§	Develop and review air quality standards
•	Determine source-receptor relationships
§	Develop and evaluate emission control standards and
strategies
§	Initiate corrective action in emergency response
•	Characterize urban air quality
* November 1983, Second Draft. Long-Term PI an for Toxic Ambient Air Pol 1utant
Monitoring (unpublished). The group consists of representatives from
States, EPA Regions, Office of Research and Development, Office of Manage-
ment Systems and Evaluation, and Office of Air Quality Planning and Standards.
4

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Assess Human Exposure Risk
The relationship of measured ambient concentrations to human health
or welfare risks depends on a number of factors regarding time and magnitude
of exposure, which may affect how frequently samples are collected and
analyzed. However, the most crucial concern from a siting point of view is
often that the data represent or be related to the highest ambient concentra-
tion. This requires that the right location be sampled at the right time.
Another consideration is the number and sensitivity of the exposed population.
Children, elderly persons, and sick persons may be more susceptible to lower
concentrations than are other people. Therefore, the concentrations to which
highly susceptible people are exposed may be as important to health risk
assessment as the magnitude and location of the maximum concentration. Site
selections are often made to satisfy both needs, i.e., maximum concentration
and concentration to which the maximum population or the most susceptible
population is exposed.
Determine Air Quality Trends
Air quality trends are important to show whether pollution is getting
worse or better and whether regulatory controls are adequate. The single
most important si ting consideration for trend data is that transient influ-
ences not representative of the region be excluded. The shutdown of a
nearby plant or the shifts of traffic from a nearby highway are examples of
transients that may be undesirable unless they represent the major effects in
the region. Typical locations that are good locations for measuring trends
are {1) the central business district of a large metropolitan area, (2) the
edge of a metropolitan area downwind of the prevailing wind direction, and
(3) a dense residential population area. Other types of locations may also
be suitable, depending on what the local situation is regarding sources of
emissions.
Develop and/or Validate Models
The use of models can greatly increase the amount of information devel-
oped regarding air quality levels over that given by a monitoring network.
However, the model estimates are 1i mi ted by the accuracy of the model.
Monitoring data can be used to establish the validity of models and to
provide a basis for improving models. This is particularly important where
local terrain influences are present. The EPA guidance on validating
models (e.g., U.S. EPA 1978) requires that monitoring be designed to describe
the spatial variation of pollutant concentrations across the area. For each
local situation the best selection of sites will depend on meteorology,
5

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topography, arid the configuration and characteristics of sources. The
following examples are offered of four common types of local situations {U.S.
EPA 1982); however, the adequacy of a network for a specific site may be
expected to vary from these examples;
t For aerodynamic downwash, consider one or two back-
ground monitors plus two to four downwind monitors.
The number of downwind monitors should be determined
by a consideration of the frequency of the downwash
events, the expected magnitude of the impact, and the
areal extent of the impact,
•	For shoreline conditions, consider one to two back-
ground monitors and three to eight downwind monitors.
The number of downwind monitors should be determined
by considering site characteristics, the magnitude
and the areal extent of the predicted impact. It may
be necessary to complement the stationary monitoring
network with mobile sampling and plume tracking techniques.
•	For complex terrain, the air quality monitors should
assess the maximum impacts for each averaging period
for which an air quality violation is expected to occur.
Approximately three to eight monitors should be consid-
ered necessary to monitor for each such averaging time.
The exact number depends on the magnitude and extent of
expected violations. At least two monitors for each
contiguous area where violations are expected to occur
are necessary except where these areas are large. In
this case, more than two monitors could be required. As
a guide, a 22-1/2° sector should define the maximum size
of a large contiguous area. Based upon meteorological
judgment, additional monitors may be required to evaluate
the source impact, dependi ng on the complexity of the
terrai n.
•	For urban situations where the concern is particulates
and the sources of violations appear to be fugitive
and/or reentrained dust, extensive monitoring and receptor
models may be needed to accurately assess the problem.
Identify Areas of Effect or Exposure Levels
In order to estimate the area covered by a specific exposure effect,
there must be a relatively large number of sampling sites. The number
required-will depend on the complexity of the local pattern of air quality
levels, 'As a general rule it will be necessary to supplement monitoring data
6

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with modeling estimates. It is desirable that the monitoring data be adequate
to identify the shape of the air quality pattern and the areas of sharpest
gradient. Remote sampling and mobile sampling can be useful adjuncts to
fixed-site monitoring in meeting this data use.
Determine Source Impact Areas
Much of what applies to defining integrated areas of effects over
a region can be applied to defining the impact area from a single source. A
number of monitoring sites are needed, and monitoring data can be usefully
supplemented by modeling data. The monitoring sites wi11 be located in the
vicinity of the site, and will be most productive if they are sited in a
pattern that is downwind of the prevailing wind di recti on from the source.
Determine Pollutant Transport and Fate
Many air pollutants are relatively stable in the atmosphere. They
are transported out of the source area by the wind, being diluted by turbu-
lent mixing in the process. In most cases, pol1utants remain airborne until
they are taken up by dry or wet particles and washed out by rainfall.
Some pollutants undergo rapid chemical transformations, which makes them
less toxic and often more susceptible to removal. In a few cases, pollutants
fall out because they are emitted as large particles that are not easily
retained as aerosols. Detailed chemical and physical analyses of pollutant
samples are useful in defining the fate of transported air pollutants.
Moni tori ng sites can be arranged in downwi nd lines at convenient distances
from major sources or source areas to obtain data that describe pollutant
transport fates.
7

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SECTION 3
CHARACTERISTICS OF NONCRITERIA POLLUTANTS
PHYSICAL AMD CHEMICAL PROPERTIES
In planning monitoring operations for NCAPs, it is useful to keep
physical and chemical properties in mind. For this purpose, Table 3 identi-
fies the 43 pollutants listed in Table 1 in terras of three properties that
affect the Missions, transport, and fate of pollutants in the atmosphere.
The three properties are volatility, reactivity, and physical state. Standard
chemical references may be used to determine more details regarding these and
other physical and chemical properties. A number of important characteristics
of 26 compounds are listed in Appendix 0 to this report.
Volatility 1s related to the difficulty of containing a pollutant
during production, handling, transport, storage, use, and disposition.
Emission rates are likely to be higher for the more volatile compounds, and
sources that use these materials are of concern from an air monitoring point
of view. Reactivity relates to how fast the pollutant changes form in the
atmosphere due to photochemical and other atmospheric chemical processes.
Pollutants with higher reactivity will not travel far from their source
before undergoing chemical transformation. The physical state of the compound
may be of interest in selecting a sample collection technique. It may also
be of interest 1n identifying handling and storage processes that are of
concern as sources of emissions.
SOURCES OF EMISSIONS
An important step in selecting monitoring sites is identifying the nature
and location of expected emissions of the pollutants of Interest. A summary
of emissions for the 43 pollutants Identified in Table 1 is given in Table 4
for the following types of sources:
•	Production plants
•	Industrial user plants
t Sources that emit the pollutant as a byproduct or
indirect emission
•	Storage, transport, and fugitive sources.
In order to give an overview of the relative importance of these emi s-
sions, Table 5 is a ranked listing of total atmospheric emissions of
46 compounds (all from Table 1) in 1978. It may be noted that two of the
pollutants in Table 1, namely nitrosomorpholine and dimethylnitrosamine are
not commercially produced and not directiy emitted to the atmosphere. These
8

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TABLE 3. VOLATILITY, REACTIVITY. AND PHYSICAL STATE OF 43 SELECTED MONCRITER1A AIR POLLUTANTS

Low reactivity

NedliM reactlvlty


High reactivity
Volatility
Solid
Liquid
Solid
Liquid
Gas
Solid
Liquid Gas
High

Methyl
chloroform
Chloroform
Methylene
chloride

V1i\yl1dene
chloride
Chloroprene
Propylene
oxide
Ethylene
oxide
Fonaaldehyde
Vinyl
chloride

Acetaldehyde Acetaldehyde
Allyl Phosgene
chloride
Acrolein
Medlua
Dlchloro-
benzene
Benzyl
chloride
Carbon
tetrachloride
Perchloro-
ethylene
Ettyylene
dlchlorlde

Dlaethyl-
nttrosaalne
Acrylonltrllc
Chlorobenzene
Toluene
Trichloro-
e thy 1 ene
Eplchloro-
I\ydr1n
HI troso-
¦orphollne
Benzene


Xylene
LiM
ChrMluai
Manganese
Polychlor-
Inated
biphenyls
nickel
Kexachloro-
cyclopentadiene
Mercury
Polychlur-
inated
biphenyls
CaM«
Cresols
Malelc
anhydride
Arsenic
Nitro-
benzene
Cresols

Phenol

Asbestos
Beryllium
01oxln
Radionuclides
(also gas J

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TABLE 4. SI)DICES OF EMISSION OF 43 NOHCRITERIA POLIUIAHIS
Chen)cat na
Acetaldehyde
Acrolein
Production
emissions*
2.3 « H)-?t
Plants located 119781
In TX 111, PA (1).
arid LA IU
Isolated acrolein;
0.111
Unlsolated:
6.2 * ion
Industrial use
emissions*
Acetic acid production;
0.341
Other processes: 0.461
Byproduct
w»1 ssi oris*
Acryl 1c icfd:
6.7 * 10-H
Not significant
Storage, transport,
and fugitive emissions*
Production--
Storage: 2.9 x lO'-J't
Fugitive: 1.3 * 10"-'I
Fug I
industrial use-
Storage: 4.2 * I0"?t
Fugitive: 2,2 x 10"?1
Fug)
Refined acrolein and glycerin:
1,8 * io-H
Present In fuel combustion No storage emissions
products, wood fires,
smoke, ti*6 cigarette
smoke
Plants located In
I* (2| and ift (21
Methionine and other chemicals:
0.12?
Aery] on I trlle
MIyl chloride
Arsenic
Asbestos
0.031
8 plants (1900}
0.291
Plants In TX and LA
0.011
Annual production:
711 * 10® lb
5.51 from mining and
¦ 111 log
1579 production:
200 * 106 lb
93,764 tons/yr
Emitted by production of
acrylic fibers, nonacryllc
fibers, A6S and SAN resins
Approximately 35 plants
Monomer residue Is
released from auto-
mobile tires
Unknown
Fplchlorohydrtn: 0.331
799,000 lb/yr emitted by
325 glass production plants
N/A
N/A
Copper smelters (1914J:
5.9 * 10®
lb/yr
Coal burntn§ (369 plants):
1.1 * 10® lb/yr
"Percentages are amount of chemical throughput tbat Is emitted to the atmosphere.
Production--
Storage: 1.4 * 10 ?t
Fugitive: 3.0 * 10-2%
(plant equipment leaks I
Fugitive dust from refining
facilities: 0.11
1,2 x 10® lb/yr
( f row building de»ol 1 Hons
and vehicle brake 1 Inlng
wear)
Primary sources:
Nine to «1H transport
Hlufng waste disposal
Landfill areas
(Continued!

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IAKLI 4.
(con tinned I
Chemical Mae
Penierte
Benzyl chloride
Production
Missions*
0.091
Production (1980):
[)9 1
12 * 10" lb
0.051
4 plants In NJ and II
Production (1978}:
Product Ion (IS
118 x 10® lb
Industrial use
mil sslons*
Primarily from production of
ethyl benzene, cunene,
eye lohex arte: 50 x 10^ ton/yr
Benzyl alcohol: 0.0351
Quaternary Mnonftaa compounds
(PC): O.OZM
Butyl benzyl phthalate: O.Olll
15 plants In II, KC. NJ, OH,
PA, TX, and HI
Byproduct
emissions*
Motor vehicle refuel Irtg:
500 ton/yr
Coke ovens, etc.:
20 to 80 x 10* ton/yr
Gasoline consumption:
40 to 80 x 10* ton/yr
N/A
Storage, transport,
and fugitive etaisslons*
Transport and storage:
115 x Hp ton/yr
01t spllis: 11 x 10' ton/yr
Fugltlve--
Productlon: 9.3 * 10"H
Benzyl alcohol: 11.0 x 10"H
QAC: 8.0 x I0"3t
Storage: 4 x 10"3l
Beryl 1 turn
1,100 Ib/yr
Production (1978):
7.5 x 10® lb
5.500 lb/yr
primarily from alloy
production
5 plants located In PA (3),
OH, and yj
Coal consumption:
5 x 10"< lb/ton
of coal
011 consumption:
3.5 m 10~* lb/1.000 gal
of oil
Unknown
Cray Iron foundries:
4.44 x 10"4 lb/ton
of Iron
Cadmium
17 x 106 produced
(19801, Including
high cadmium content
compounds
6 x 106 Ib/yr (1975)
Steel blast furnaces:
2 x 10® lb (1975)
Copper smelting:
1.3 x 10° lb/yr
Unknown
Carbon
tetrachloride
0.311
Production (19B1):
717 x 10® lb
fluorocarbon production:
4.5 x 10-?I
Solvent applications:
approximately
60 x 10® lb
•Percentages are amount of chemical throughput that Is emitted to the atmosphere.
Production--
Storage: 0.?lt
fugitive: 4.8 x I0~*t
fluorocarbon production--
Stnrage: 4.42 x lO"?!
Fugitive: 1.78 x lO'^'l
(continued)

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TABLE 4, (continued!
Chemical m
Chlorobenzene
Production
Missions*
0.?lt
Production (19181:
335 * 10® lb
emitted from plants
1n HI, m, a, OE,
#v, rnd m
Industrial use
emissions*
DOT: 4.0 x 10*2*
Mltrochtorobenzene: 0.Ill
Otphenyl oxide: 7.0 x IQ-^i
Byproduct
calsstons*
Used as solvent In cold
cleaning operations and
In pesticide applications;
1001 enlsstons
Storage, transport,
anil fugitive emissions*
Production- •
Storage; 4.5 x 10*^J
fugitive: 6.9 * )0'i
Chemical 1ntermed1 ate--
Storage: 0.S x 1Q~?1 OUT
2.0 * 10"?t nltro-
chlorobenzene
1.0 n lO'^t dlphenyl
oxide
Fugitive: 0.5 x 10"?* DDT
3.0 x I0"2t nltro-
chlorobeniene
2,0 x 10"*l dlphenyl
oxide
Chlorofom
6.8 x 10~H
Huorocarbon if-22) production:
Solvent use:
Fluurocarbon product Ion-


OX emissions
1001 emissions fro*»
Storage: 0.371

330 pillion lb

7* of production
Fugitive: 0.08".

produced (1978)
8 plants In CA (?), Kf (2).



at ? plants
«J (2), IL. and MI

Production-



Storage: 8.2 x 10*2}
Fugitive: 2.3 x 10"<»
Chloroprene	1.40 * 10"^1 (Ou Pont) AH production Is captlvely	N/A	Production--
0.22 * 10~?1 fOunltal consumed to manufacture poly-	Storage: 0.4 x 10~-H
chloroprene (neoprene1	fugitive: 0.IX
Production (1978):
211 * 10-6 tb at
3 piants In TX and IA
Chromlua	negligible domestic Steel and alloy production:
wining emissions	1.3 *ifl1fon lb/yr (19701
Refining:
26 Billion lb/yr* (19701
750 mil 1 ion lb (1980)
of chromium and
compounds processed
in 1980
(continued)
Coal and oil combustion, Unknown
Incineration, cement
production:
4.7 Million lb/yr (19701
"Percentages are amount of cheolcal throughput that 1s emitted to the atmosphere.

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TABU 4. (continued)
Chemical na
a-,m-,p-Cresol
Production
emissions*
Mixed cresol produc-
tion and eresyllc
acid production:
0.191 (1976)
Cresol Isomer
production--
o-Cresol: 0.191
m-Cresol: 0.19t
p-Cresol: 0.391
Industrial use
ewlsslons*
Byproduct
Missions*
PhenolIc resin:
0.4t
Pesticides: 4.0 x 10"*t
BIIT/antloxIdants: B.O x I0*2l
Trfcrtsyl phosphate (TCP);
3.S k I0-2|
Miscellaneous: 0. IS
W1re enamel solvents:
16.4 Million lb/yr
(Jlslnfectant cleaning
compound:
2.5 pillion Ib/yr
Coke oven emissions:
0.04B lb/ton of coke
Ore flotation agent:
2.5 Million Ib/yr
Storage, transport,
and fugitive Missions'
Mixed cresol, cresylIc acId,
¦-eresol. and o-cresol
productions-
Storage: 2 x 10-?I
Fugitive: 4 * IQ~^t
Others--
p-Cresol
PhenolIc resin
Pesticides/TCP
Fugf t1
Storage 	
3 * lO-^X 8 x 10
5 x 10'2t 5 x 10
5 x I0"H S x 10
BKT/antloxIdants 1 x 10"2* | x 10
p-Mchlorobenzene 0.58t
7 plants
Pesticide intermediate:
4.0 x 10-2*
Space deodorant and moth
control: 100* emissions
Pesticide Intermediate--
Storage: 0.5 * 10"'J
Fugitive: 0.5 x 10'n
Production-
Storage: 4.1 x 10"zl
Fugitive: 0.10*
Dimethylnttrosantlne
Hot currently produced
fn commercial quan-
tities, but formed
from emissions of
dimethyl amine (DMA)
production: 0.131
Formed fr«* emissions of
dlaethyl amine during production
of industrial solvents, lauryl
OMA oxide, rubber chemical
accelerators, dimethyl -
hydra 2Ine/pesticIdes: 0.0651
Found as a contaminant
during rubber processing
and in rocket fuel pro-
duction and use
Contained in formulations
of the pesticide 2,3,6-
trfchlorobenzolc acid and
In dimethyl hydrazine
Production of DMA--
Storage: 0.021
Fugitive: 0.051
Users of DMA--
Storage: 0.011
Fugitive: 0.0251
Otoxln
Kot conmerc tally
produced
An Impurity resulting from the
manufacture of trlchlorophenol,
2.4,5-T, and pentachlorophenol:
2.5 x 10-2* of production
volume
10 plants In HI. KA (2), 1L (21.
PA, CA, HO. Aft, and WA
Weed control applIcattons
of 2.4,5-T: 6.5 lb/yr
(based on 1 ppb In product)
Wood preservative use:
42.3 lb/yr
From burning: 18.0 lb/yr
(based on particulate matter
content of 2 ppb)
No data avail able
•Percentages are amount of chemical throughput that 1s emitted to the atmosphere.
(continued)

-------
TABLE 4. (continued)
Chemical name
Production
ami ssfoiis*
Eplchlorohydrln
4.2 x l0-2i
Plants In TX and LA
Industrial use
emissions*
Byproduc t
an! sslons*
I poxy resin production
synthetic glycerin production
and other chemical production:
0.1 SI
From epoxy resin use:
8.0 x 10-?*
from use of glycerin and
other cheMlcals:
2.6 x 10**1
Storage, transport,
and fugltive eaissIons*
Production-
Storage: 1
fugltlye: 4.0 x 10
Storage: 1.0 x 10~3|
Ethylene dlchtorltfe
5 Mil I Ion metric tons
produced (197?)
18 facilities: 0.48t
53.2 x 10® lb/yr
Hore than BOt produced Is used
In synthesis of vinyl chloride
aonoaer and 12-151 used for
other chealcal synthesis (1977):
5.5 x lO® lb/yr
Used In gasoline as a lead
scavenger:
2.9 x 10® lb/yr
Waste disposal 1197?):
<60 x 10® lb/yr
Dispersive uses 1 1977):
11 x 106 lb/yr
Production 11977)-
Storage: 31.6 x ID6 lb/yr
Fugitive: 11.4 x 10® lb/yr
Industrial use (1977>--
Transportation: <5 x 106 lb/yr
Ethylene oxide
Air oxidation process
(5 producers):
5.25 x 10-2*
Oxygen oxidation
process (6 producers):
4.7 x 10-2*
3,640 million 1b
produced (1970) at
13 plants
Produced and used at sa
sites
N/A
Used to Make ethylene glycol
(EG) polyester, EG antifreeze,
surface active agents,
ethanolanlnes, glycol ethers,
etc.
Production enlsston estimates
Include industrial use estimates
Production	by air oxidation
process-
Storage:	0.21 x llHx
Fugitive: 0.02 x 10 *1
By oxygen	oxidation
process —
Storage:	0.71 x lQ"?t
Fugitive: 0.5 x 10*3%
Formaldehyde
For silver process:
2.6 x 10"
Urea, >ela«1ne, phenol 1c, and
acetal resins: 0.40X
For aietal oxide	Sutanedlol: 0.20t
process: 3.9 x I0*2l
Pentaerythrlto): 0.731
6.4 x 10"' lb produced
(1978) at 53 plants Host others: 0.48*
Automobile emissions:
610 Million lb/yr
Other Indirect emissions
are from power plants,
Incinerators, and petro-
leum refineries
Production by silver process-
Storage: 0.21 x 10-?t
Fugitive: 0.52 x 10"2t
By Metal oxide process-
Storage: 0.41 x I0"'l
Fugitive: 0.61 x irn
Resin and butanedlol production-
Storage: 0.5 x 10~H
Fugitive: 0.5 x 10~n
Iktxachl orocyclo-
pentadlene
0.521
7 Million lb 11970)
produced at plants
In HI. NY. and IN
Chemical Intermediate In manu-
facture of flame retardants,
pesticides:
3.25 x XO'H
Many of these uses are now
banned by EPA and OSHA
Mo data avail able
Production-
Storage: O.OB'I
Fugitive: 0.20'l
Industrial use-
Storage: 0.5 x uWt
Fugitive: 1.25 * 10
(continued)
'Percentages are aoixint of chemical ttiroiKjSijmt that ts emitted to the atmosphere.

-------
IAI1LL 4. (continued)
Chemical rt#
Malefc anhydride
Production
em)sslons*
304 ml?I Son lb/yr
produced 119811 at
7 plants
0.05 x 10® lb
emitted (1974$
Industrial use
emissions9'
1974 emissions from:
Me that 1c anhydride production
(19H): 2.96 * 10e lb
Other products: 0.85 * 10^ lb
Byproduct
Missions*
Storage, transport,
and fugitive emissions'
Unk
Packaging and storage- (1974):
0.06 x 10®
lb
Manganese
High grade ore no
longer mined In the
U.S., so raining
emissions are assumed
to be negligible
Manganese alloy and petal:
0,331 of ferro alloy product
Iron and Steel production:
0.20 x 10~2* of Iron and steel
product
Gray Iron foundries:
1.5 i 10~2% of Iron product
Electrical power utlIity
plants--
Coal fired:
II * 10* lb/ton
Mo data aval 1 able
011 fired:
1QJ lb/100 gal
0.5
Coke oven emissions;
2.6 x 10"2 lb/ton coal
Mercury
Estimated world pro-
duction (1973) of
10,000 tons, with
emissions of the
order of 300 tons/yr
Electrolytic production, of
chlorine
2M Billion lb/yr (I97B)
Local Missions froo natural
sources of mercury
Given off during electrol-
ysis of alkali metal
s»lts In line recovery
Emitted fro® coal or paper
burning, from use of elec-
trical or Measuring Instru-
ments containing Mercury
Emissions from disposal
of fluorescent tubes,
fever thermometers, etc.,
and from Incinerator sludge
estimated at about
185,500 lb/yr (1971 >
Methyl chloroform
(1,1, l-tr1chloro-
ethanej
7,1 * 10"?1
620 nllHon lb 11918}
produced at plants In
LA (3) and TX (II
Aerosol formulations and
other chemical Intermediate
uses: 0.06 million lb/yr
Hetal decreasing and
cleaning operations:
311.2 Million lb/yr
(at 276,000 units)
Solvent/cleaner use;
135 mil Hon lb/yr
Aerosol use:
30 ml 11 ion lb/yr
Production-
Storage: 0.211
fugitive: 0.101
~Percentages are amount of chemical throughput that Is emitted to the atmosphere.
(contlnuerf)

-------
IAI1LL 4.
(continued)
Chemical rsrtme
Methylene chlorlife
(dlchloraisethane)
Production
e«1sslons*
Methyl chloride
process: 2.6 x loH
Methane process:
1.4 x I0?J
525 Million ih (1978)
produced at 7 plants
In Lft (2), KS.
WV (21. TX, and KY
Industrial use
emissions*
Pa int and varnish recover foimi-
latlon, aerosol forwulatlon,
plastics processing;
eventual ly USUI
Chemical Interne til ate
Byproduc I
emissions'
Metal degreasfng sol vent:
107.1 ml 11 Ian lb/yr
(at 122.000 units)
Paint and varnish recover:
187.5 Million lb/yr
Aerosols:
89.3 mf111on lb/yr
Plastics;
26.3 nllllon lb/yr
Storage, transport.
and fugitive emissions'
Methylene chloride process--
Storage: 0.246%
Fugitive: 0.0471
Chloroaethane production:
Storage: 0.25%
Fugitive: 0.05%
He thane process--
Stordge: 0.102%
Fugitive; 0.032%
Nickel
0.81X
27.0U0 lb/yr produced
In 2 plants 1n U.S.
and IBS,100 tons.S.
imported 100 tons
Iron ami steel manufacturing:
1-1 x IO"H of 1 ron/steel
product
Ferro-allov production:
2.2 x I0~2% of ferro alloy
product
Gray-iron foundries:
5.2 x 10-n of hot metal
produe t
Honferrous alloys:
1.2 x 10-3| of product
Coal-fired boilers
(per ton)--
Power/Industry:
b.6 x 10-* lb
Resident/commerce:
3.0 x 10"* lb
Oil-fired boilers (per
1000 gali- -
Power: 0.30 lb
Resident: 0.23 lb
Resi dent/cormerce: 0.13 lb
Diesel fuel:
0.13 lb/1.000 gal
No data available
Coke ovens:
1.6 x 10 J
lb/ton coal
Ml trobenrene
Ni trnsamorpholfne
0.0 x 10-3%
795 Million lb
produced in 6 plants
(1978)
99% nitrobenzene produced is
used captively for production
of aniline: 0.8 x 1U--H
Chewical Intermedlate for
production of dfchloroanlIfnes
and dlnltrobenzenes: 0.Ill
Solvent use in cellulose
ether manufacture and in
petroleum industry: 100%
6.4 million lb (1978)
emitted From 279 refineries
Nltrolienjene and aniline
prorluc Hon- -
Storage: 0.6 x 10'^t
fuijl tlve: 3. 1 x 10"2'i
Cheflifcal
Storage: l.S x
Fugitive: 3,0 x
Intermedial
10
10"<%
Not cnsimerctally
produced; formed from
era I ssions of mnrpholIne
137,700 lb of morphol 1ne
emitted from ? IX
plants (1970S
No reported uses
Contain!nant found In	N/A
dlchloromethane, chloro-
form, morphol 1 ne, and hi
a rubber crass 1 inkpil
ai <. elerdtor
Mtirphol Ine e«issions (1978)--
Corrosion inhibitors.
7.5 * 10-6 it,
Polishes ami waxes:
?.b 10-6 lb
•Percentages are amount of chemical throuyhjiut that 1s emitted to Lie atmosphere.
(contlnu'-ill

-------
I AIM 4, {continued 1
Chemical name
Perchloroethylene
i tctrachloro-
ethylene)
Phenol
Production
euissions*
0.25%
639 mi 11 Ion lb
produced (1979)
in 10 pi ants
Industrial use
atif sslons*
Chesfcal Intermediate, dry
cleaning processes, and
equipment {19?71: 121
0. 18*
320 million lb
produced at 16 plants
(19785
Ctiealcal Intermediate:
Manufacture of phenol -
formaldehyde (phenolic! resins:
3.5 X IG-n
Caprolactam production: 0.131
Other chemical products:
7,5 x 10"2%
Byproduct
eml ssSons8
Metal cleaning operations:
104.5 x 10$ Ib/yr
estimated (19781
Miscellaneous uses:
6.B x I0-H
Storage, transport,
ami fugitive emissions"
U5-9UJ of chemical produced is
eventually lost in emissions
Production--
Storage: 0.3 x 10"^*
Fugitive: 4,1 x 10~?t
Phenolic resin production--
Storage: 0.2 * 10"2J
Fugitive: 1.3 x I0"*t
Caprolactam production:
Storage: 0.1 x 10"'J
Fugitive: 1.3 x 10~H
Phosgene
None
Toluene
0.6 x 10-
dlisocyanate (TBI):
0"31
None
Polywerlc fsocyanates:
0.6& x io-n
Production (18 sites]--
Storage: None
Fugltlve: 1.8 x 10"^l
TDI and polymer Isocyanate
production: Hone
Polychlori nateri
bI phenyls
Ho longer produced in
the U.S. after 1977
and no imports since
1979; 35 million
llj/yr produced prior
to 19?7
Approximately 1.397 bill Ion lb
produced since 1929; only an
estimated 61.5 million lb have
been destroyed
Used irs manufacture of
capacitors, transformers,
and closed electrical
systems
Disposal (Incineration)
of transformers and
capacitors containing
PCBs at I? incinerator
si tes: 30 »i 11 ion lli/yr
processed; emissions
estimated Co be
11. 1-0. IS
Spills, leaks, disposal of
hydraulic fluids:
3,960-4,950 ton/yr
Propylene oxide
Chlorohydrination
process:
7.5 x 10-Zt
Peroxidation process;
2.1 x 10-2%
{? IX sites)
J,m million lb
(197K) produced at
? plants In TX (4),
I A, HI, and KY
Urethane polyol production:
1.3 x 10"2%
Propylene glycol production:
0.28 x 10 H
Surfactant polyol production;
1.3 x 10-2*
E>1 - and trlpropyl ene glycol

-------
1AI!tC 4. (continued)
Chemical
Radlonucl Ides
Production
emissions*
Industrial use
emissions*
Byproduct
Wilts Ions'
Storage, transport,
and fug 111 we emissions*
natural sources: gases
from the earth's crust
and the Interaction of
cosmic radiation with
g«es In the atmo-
sphere. tow and
Intermediate Jewels
ire released to the
environment. High-
level wastes are not
released and require
Isolation for 600-700
years, or thousands of
years if alpha emitters
are present
Tailings fro® mining operations
are sources of radionuclide
ealsslons. Kuclear reactor
operations and nuclear spent
fuel process 1119 are principal
sources of radioactive gases
Other sources:
Processing radioactive
materials
Metallurgical plants
Chemical pi ants
Fossil fuels:
Trices of uranium 238
and thorlua 226 (1-2 ppal
are given off from coal-
ash and oll-burnlng plants
NRC specifies shipping criteria
OCT regulates shipping require-
ments
Toluene
Production processes-
Catalytic re formate:
0.2 * 10-2%
Pyrolysls gasoline:
1.5 x 10-2*
Coal derived:
5.0 * 10-2l
Styrene byproduct:
0.1 x 10"'t
Benzoic add production: 0.1*
Benzyl chloride and vinyl
toluene: 5.5 x 10~*%
Benzene production and xylene
disproportionate:
0.5 x 10-®t
Gasoline marketing:
38,5 will ion lb/yr
Coke oven operations:
25.7 million lb/yr
Paints, coatings:
1001
Trlchloroethylene 0.51 * 10-^1
3 plants (W8J
Unknown
c acid productlo
Storage: 0,4 * 10"
Itlve: 0.J * 10H
Catalytic reforwate process-
Storage: 0.6 * I0"H
fugitive: 0.2 x 10"2l
Other production processes--
Storage: 6-0 x 10**}
Fugitive: 1.5 * 10"2*
Benzoic acid productlon-
Stor*
fug1 I
Benzyl chloride and vinyl
toluene production:
Storage: 0.3 * 10"H
Fugitive: 0.15 x 10"3t
Benzene production and xylene
d1sproportlonatlon--
Storage: 0,1 1 10"H
Fugitive: 0.05 x liHi
Solvent:
]00t; 11.6 million
lb/yr 11978)
Vapor dcgreastng:
Wl; 195.6 million lb/yr
(19781
Cotrt cleaners:
32.9 million lb/yr (1978)
Production--
Storage: 0.81 x 10"H
Fugitive: 0.75 * 10
•Percentages are aiuotinl of chemical throughput that Is emitted to the atmosphere.
(corltl tilled)

-------
TABLE <1. (concluded)
Chemical name
Vinyl chlnrlde
Production
eralsslons*
0.45*
~ billion lb produced
(1975)
Industrial use
emissions*
971 of total produced Is used
1n polymer production
202.4 ml 11 Ion Ib/yr emitted
Polyvinyl chloride production:
4.51
Byproduct
emissions*
Unknown
Storage, transport,
and fugitive emissions*
2,000 Ib/yr released to sewers
In manufacturing process
discharge streams
VI nyl (dene chloride
(VDC)
4.5 x 10-?t
estimated |19771
3.3 million lb (19741
Production of 1,1,1-trlchlo-
ethMve (not Available)
Polymer synthesis of poly-
vinyl Idene chloride:
1.35 Million lb (1974)
Up to 2St used In Saran
My be In landfill refuse
areas
251
o-,ra-,p-Xylene
Mixed xylene produc-
tion front catalytic
reformats process:
0.3 x 10"2t
From pyrolysis
gasolln« process:
0.7 x 10-2%
Fro* toluene:
0.5 x 10"21
Coal derived:
5.0 x 10-2*
o-Xylene: 0.211
n-Xylene: 0.161
p-Xylene: 0.121
Ethyl benzene (»lx#d xylenes):
1.0 x 10~zt
Chthallc anhydride lo-xylene):
1.4	x 10"2X
Isophthallc acid (w-xylene):
8.5	x lO 'l
Dlaethylterephthallc acid
(p-xylene): 1.3 x 10-*t
Terephthal 1c acid (p-xylene):
0.251
Mixed xylenes In solvent
applications, agricultural
pesticides, household
products: 1001
Mlxed xylene production-
Catalytic reformate:
Storage: 0.6 x 10~2l
Fugitive: 0.3 x 10"2l
Pyrolysis gasolIne--
Storage: 3.0 x 10~2l
Fugitive: 0.3 x 10"*!
t,
Toluene process--
Storage: 1.0 x 10~2
Fugitive: 0.5 x 10
Coal derived--
Storaje: 6.0 x 10*2l
Fugitive: 1.5 x 10_2t
o-Xylene production--
Slorage: 0.8 x 10~21
Fugitive: 3.8 x 10" 21
¦-Xylene productlon--
Storage: 1.2 x IG'2X
Fugitive: 3.0 x 10_2t
p-Xylene production--
Storage: 1.9 x I0"21
Fugitive: 2.4 x 10"2%
"Percentages are amount of chemical throughput that Is emitted to the atmosphere.

-------
TABLE 5. RANKED LISTING OF TOTAL EMISSIONS
OF SELECTED NONCRITERIA AIR POLLUTANTS
Chemical
Total emissions*
(lb/yr)
Toluene
2,235,842,590
Benzene
1,300,000,000
Methyl chloroform
538,730,000
Perchloroethylene
500,000,000
m-Xylene
453,533,940
Methylene chloride
407,700,000
o-Xylene
268,497,360
Trichloroethylene
240,700,000
p-Xylene
239,270,414
Vinyl chloride
220,000,000
Acrylonitrile
190,000,000
Ethylene d1chloride
180,000,000
Chiorobenzene
175,376,130
Carbon tetrachloride
65,030,000
p-Dichlorobenzene
49,900,950
Manganese
35,000,000
Formaldehyde
33,000,000
Chloroform
24,040,000
* Actual emissions estimated as of 1978.
{continued)
20

-------
TABLE 5 (continued)
Chemical
Total emissions*
(1b/yr)
Nickel
22,573,640
Chromium
15,000,000
Nitrobenzene
13,040,000
Asbestos
12,200,000
m-Cresol
10,960,000
Morpholinet
10,028,000
Arsenic
9,500,000
p-Cresol
9,124,941
Phenol
6,924,360
Cadmi um
6,000,000
Acetaldebyde
4,853,950
Maieic anhydride
4,800,000
o-Cresol
4,504,150
Vinyl idene chloride
4,300,000
Radionucl1des
4,000,000
Chloroprene
3,523,092
Ethylene oxide
1,991,000
Mercury
1,900,000
Propylene oxide
1,346,160
(continued)
* Actual emissions estimated as of 1978.
t Precursor to atmospheric formation of nitrosoroorpholine.
21

-------
TABLE 5 (continued)
Total emissions*
Chemical	(lb/yr)
Ally! chloride
1,110,000
Epichlorohydrin
479,000
Beryl 1ium
357,035
Phosgene
253,176
Dimethyl amine^
215,400
Acrolein
102,920
Benzyl chloride
100,271
Hexachlorocyclopentadi ene
59,500
Polychlorinated biphenyls
30,020
2,3,7,8 TCDD (dioxin)
84
* Actual emissions estimated as of 1978.
t Precursor to atmospheric formation of dimethylnitrosamine.
22

-------
compounds are primarily found In the atmosphere as a result of chemical
reactions involving the precursors, morpholine and dimethyl amine, respectively,
which are listed in Table 5.
It may be noted from the description in Table 4 that the large quantities
of emissions of the highest ranked pollutants in Table 5 are from many small,
widely dispersed sources. Typical examples are the 1,3 billion pounds per
year of toluene emitted from motor vehicle exhausts, the 579 million pounds
per year of toluene emitted from paint and other coating solvents, and the
371 million pounds per year of methyl chloroform released from metal cleaning
operations.
The sources of each pollutant have been characterized into the following
four types:
•	Well-isolated plant sites having major emissions
•	. Industry-related sources that may or may not be well
isolated from one another
•	Sources identified with product use and related to popula-
tion distribution
§ Motor vehicle traffic.
Pollutants falling into each class are listed in Table 6. Some pollutants
are listed in more than one class. These groupings will help in planning
monitoring networks with respect to each pollutant- Further suggestions for
using these classes to define monitor sites are presented in Section 4,
SAMPLING REQUIREMENTS
The sample collection for NCAPs differs from that of criteria pollutants,
mainly in the fact that the sampling procedure is not specified as it is with
criteria pollutants. Therefore, the analyst must evaluate the currently
recommended and the most recently developed procedures to determine how the
sample should be collected and analyzed. A list of sampling media and
analysis methods for the pollutants addressed in this document is shown
in Table 7. The problems encountered when specifying a sampling protocol
are many; hence, a logical procedure that considers at least the following
points should be followed:
t Media. Unless very expensive equipment is dedicated to
field monitoring activities, samples wi11 normally be
collected as grab samples and brought to a laboratory for
analysis. The media selected to collect each pollutant
must have good collection efficiency for the compound}s)
of interest, and it must retain and release the compound in
23

-------
TABLE 6. CLASSES OF POLLUTANT SOURCES APPLICABLE TO
SELECTED NONCRITERIA AIR POLLUTANTS
I. Small number of well-isolated plant sites
user plants)
production pi ants)
Dimethylnitrosamine (vicinity of 13 plants emitting dimethyl ami ne, rocket
1aunches)
Ally! chloride {3 plants)
Epichlorohydrin (12 plants)
Acrolein (5 production and 3
Ethylene oxide (13 plants)
Hexachlorocyclopentadi ene (3
PCBs {12 incinerator sites)
Phenol (16 production and 16 user plants)
Phosgene (18 production plants)
Propylene oxide (7 production and 30 user plants)
Acetaldehyde (5 production and 13 user plants)
Benzyl chloride (4 production and 15 user plants)
Chioroprene (3 plants)
Acrylonitrile (5 production and 25 user plants)
Ethylene dichloride (18 production plants)
Vinyl chloride (production and chemical specialty plants)
Maieic anhydride (7 production and many specialty user plants)
II- Emissions related to specific industries and many users
Formaldehyde (wood products, chemical specialties)
Manganese (ferro and si 1ico alloys, power plants, iron and steel plants,
foundri es)
Nickel (power plant oil combustion)
Nitrobenzene (cellulose ether and petroleum plants)
Beryllium (power plant coal consumption)
Cresols (wire coating plants, coke ovens, mining sites)
Radionuclides (power plant coal consumption)
Chromium (refineries, steel pi ants, cement plants)
Mercury (power plant coal combustion, incinerators, mercury and zinc
refi neries)
Cadmium (iron and steel plants, copper and zinc smelters)
Asbestos (production plants, building demolitions)
Arsenic (copper smelters, glass plants, refining plants)
Benzene (petrochemical plants, coke ovens, gasoline refineries}
Vinylidene chloride (chemical specialty plants)
(continued)
24

-------
TABLE 6 (continued}
III.	Emissions related to population density
Dioxin (use of wood preservatives, inclnerators)
Formaldehyde (wood products in homes)
Methyl chloroform (degreasing)
Methylene chloride (paint remover, degreasing)
Ni trosomorpholi ne (vicinity of morpholi ne emi ssions, mainly boiler
corrosion inhibitors, and polishes and waxes)
Nickel (oil combustion, including diesel)
Toluene (paints and adhesives)
Trichloroethylene (degreasing and cleaning}
Xylenes (adhesives, household products, pesticides)
Carbon tetrachloride (miscellaneous household and commercial products}
Chiorobenzene (cold cleaners, pesticides)
Chloroform (solvent in pharmaceuticals and pesticides)
Cresols (disinfectant/cleaning compounds)
p-Dichlorobenzene (space deodorant, moth control)
Perchloroethylene (dry cleaning, metal cleaning)
Arsenic (coal combustion, pesticide use)
Asbestos (building demolition)
IV.	Emissions related to motor vehicle use
Toluene
Xylene
Benzene
Asbestos
25

-------
TABLE 7.
SUGGESTED ANALYSIS METHODS
FOR APPLICABLE
SAMPLING
MEDIA
Organic
pol1utant

Sample collection media
£
Tenax-GC Charcoal
Itnpi nger
PUF**
Other
Acetaldehyde

1

2 (Bubbler reagent)
Acrolein

1


Acryl onl tr11 e



3 (Canister, mole sieve!
Allyl chloride



3 (Canister, cryogenic)
Benzene
3



Benzyl chloride
4,5


4,5 (Canlstar)
Carbon tetrachloride
4,5


4,5 {Canister)
Chlorofienzene
4,5


4,5 (Canister)
Chi o reform
5,6



Chloroprene
4,5



o-,m-,p-Creso1
4,5
4,5
4,5

p-01chlorobenzene
4,6


6 (Cryogenic)
01 methyl n1 trosanti ne
7


7 (TheraosorM)
01oxln



4 (Suboicron filter)
Eplchlorohydrln
4,5


4,5 (Cryogenic)
Ethylene d1chloride



4,5 (Cryogenic)
Ethylene oxide
4,5


4 {Canlster)
Formaldehyde

1

2 (Bubbler reagent)
Hexachlorocyclopentadlene
4,5

4,5
6 (Porapak T)
Mai el c anhydride



None available
Methyl chloroform
4,5


4,5,6 (Canister)
Methylene chloride



4 (Canister, mole sieve)
Nitrobenzene
4,5


4,5 (Canister)
(continued!
* Analysis method:
1.	Spectrophotometry C
2.	Derivftization, high performance liquid chromatograph
3.	Gas chroma tograph/flame Ionization detector
4.	Gas chromatograph/photoionlzation detector
5.	Gas chromatograph/uass spectrometry
6.	Gas chroaatograph/electron capture detector
7.	Gas chromatograph/therwal emission analyzer
8.	High performance liquid chroma to graph
** Polyurethane foam.
26

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TABLE 7 (continued)
Organic
pollutant
Sample collection media*
Nitrosomorphol i ne
Perchloroethylene
Phenol
Phosgene
PCBs
Propylene oxide
Toluene
Trichloroethyl ene
Vinyl chloride
Vinyl idene chloride
o-,m-,p-Xylene
Tenax-GC Charcoal Irapinger
PUF*
Other
4,5
4,5
4,5
4,5
6
4.5
4.6
4
8 (Themosorb-N)
4,5 (Canister)
Field analysis only, due
to instability of compound
5,6 6 (rlorosil )
4,5 (Cryogenic)
4,5 (Cryogenic)
6 (Cryogenic)
4.5	(Cryogenic)
4.6	(Cryogenic)
Inorganic
pollutant
Hi-vol filter
Sample media
Other
Arsenic
Beryllium
Cadmi um
Chromium
Manganese
Mick el
Asbestos
Radionuclides
Mercury
Microscopy (rail 1 ipore filter)
a, 6, and 7 spectroscopy (mil 11 pore filter)
Atomic absorption spectrometry (silver wool)
Analysis method;
1.	Spectrophotometry
2.	Derivitization, high performance liquid chromatograph
3.	Gas chromatograph/flame ionization detector
4.	Gas chromatograph/photoionizatlcn detector
5.	Gas chromatograph/mass spectrometry
S,	Gas chromatograph/electron capture detector
7.	Gas chromatograph/thermal emission analyzer
8.	High performance liquid chromatograph
Polyurethane foam.
27

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a predictable and reliable way. Cost of the media,
sample preparation, and extraction are all necessary
considerations when designing a sampling program.
• Procedure. The procedures 1isted in Table 7 primarily
use collection on sol id media—either filters, Tenax-GC,
or charcoal. Most of the information was extracted from
the EPA "Technical Assistance Document for Sampling and
Analysis of Toxic Organic Compounds in Ambient Air1'
(Riggin 1983). A more complete description of the
sampling and analytical methods is provided in Appendix A
of this document. Table 7 shows columns headed with the
various collection media used for organic compounds.
Suggested analytical methods for each compound are indicated
by numbers that are identified in a footnote. A procedure
for each phase of the sampling program must be written out
in advance of the sampling activity in order to anticipate
how each step is to be done. Phases of the sampling
activity include preparation, field sampling, and sample
analyses. Procedures must be written to describe media
preparation, e.g., preconditioning, assembly (if necessary),
sample handling, and analytical procedures to be followed.
In addition to sample preparation and handling, a plan is
needed for how much air must be sampled to obtain the
amount of pollutant necessary to meet the minimum detectable
limits of the analytical procedure. The volume of air
necessary to sample can be determined by estimating the
concentration of the pollutant in the ambient air and
calculating what volume of air would contain the amount of
pollutant necessary to meet the minimum detectable quantity
attributed to the analytic procedure. A margin of safety
should be added for less than 100 percent capture efficiency
of the media. Consideration must be given to the possi-
bility of collecting too much of a compound in a single
sample tube, i.e., so that some of the material in the
sample passes through. Considerable study has been
directed to the breakthrough volume of Tenax. Breakthrough
volume for a variety of volatile organic compounds has
been reported by Krost et al. (1982). Estimated detection
limits are also given for most of the compounds listed by
Krost.
28

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Determination of the volume of air to sample can be shown using the
following simple example. Assume that the detection limit for a compound is
15 ng per ml and the compound is extracted into 5 ml of solvent. The sample
would need to contain 75 ng of the pollutant in order to be detectable.
Assume the concentration of the pollutant in the atmosphere typically ranges
from 5 to 25 ng/m^. The volume of air to be sampled would range from 3 nw
in areas of high concentration to 15 -jn areas where low concentrations
exist. If the sample media were only 80 percent effective in capturing the
pollutant, the volume of air to be sampled would be increased by 25 percent.
Unfortunately, the capture efficiencies of sampling media are not readily
available for many of the compounds of interest. It may be necessary to
assume collection efficiencies much lower than 80 percent,
AIRBORNE TOXICITY
Table 8 presents recent information on the toxicity of the 43 pollutants
listed in Table 1. The reason for providing these data is to assist monitor-
ing planners in setting priorities for selecting monitoring sites oriented
to certain pollutants. Sites that measure pollutants for which toxic effects
are dubious or for which the expected ambient concentration is low relative
to toxic 1evels, can be assigned a 1ow priority. When funds limit the number
of sites that can be set up and the number of samples that can be collected
and analyzed, these data may be helpful.
The toxicity effects of greatest concern relate to severe body cell
irregul arities, including carcinogencity and mutagenicity. For 13 of these
compounds, other toxic effects are of concern. Seven of the listed compounds,
including arsenic, asbestos, benzene, chromium, nickel, radionuclides, and
vinyl chloride, are known carcinogens. Two of these, radionuclides and vinyl
chloride, are also mutagens. For all of the others, the evidence on carcino-
genicity and mutagenicity varies from completely unknown to probable but
uncertain. Two of the compounds, acrolein and phosgene, are known to be not
carcinogenic but to have other toxic effects.
29

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TAIILE 8. TOXICITY OF NOHCRITEHIA AIR E'OLLUTANTS
Pollutant
Carcinogen'city*
Mutagenic!ty
Other effects
Acetaldehyde
ficrolein
AcrylonltrlTe
Allyl chloride
Arsenic
Asbestos
Benzene
Benzyl chloride
Beryl Hum
Cacfmi um
Carbon tetrachloride
Ho data
Current Information indicates
acrolein is not a carcinogen
or cocarcfnogen
Probably carcinogenic to
tinmans at though evidence
is limited; sufficient
evidence In experimental
animals
inadequate data
Sufficient evidence
In humans
Sufficient evidence
tri humans
Sufficient evidence
in humans
inadequate evidence in humans;
limited evidence in experimental
animals
Limited evidence in humans;
sufficient evidence in
experimental animals
Limited evidence in humans;
sufficient evidence in
experimental animals
inadequate evidence
in humans; sufficient
evidence In experimental
animals
Mutagenic in drosophila; no
human data
Cytotoxic in short-term
tests; mutagenic in short-
term tests
Sufficient evidence in
short-term tests
Mutagenic in E. col I;
no human data
Increased chromosomal
abtivatio.is ir.
humans
Mo data
Not mutagenic, but produces
chromosomal aberrations in
short-term tests (mammalian
cells} and in humans
Mutagenic In short-term
tests; no data on humans
Inadequate evfdence
Inadequate evidence
Inadequate evidence
Potent respiratory irritant
at 30-100 ppm
(continued)
* "Sufficient evidence" of carcinogenicity indicates a causal relationship between the agent and cancer.
"Limited evidence" Indicates that a causal Interpretatlon Is credible, but that alternative explanations such as chance, bias of review
board, or confound!n9 could not adequately he excluded.
"Inadequate evidence" indicates one or more of the following: few pertinent data; available studies showing evidence of association
df(I not exclude change, bias, or confounding; and studies were available that do not show evidence of carcinogenicity.
The classification of any chemical may change as new Information becomes available.

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TABLE 8 (continued)
1
Pollutant
Carcinogenic!ty*
Mutagenicity
Other effects
Chlorobenzene
Chloroform
Chloroprene
Chromium
o-,m-,p-Creso1
p-DIchlorobenzlne
Dime thy! illtrosamlne
Oloxln (TCDO)
Eplchlorohydrln
Ethylene dichlorlde
Ethylene oxide
Formaldehyde
Hexachlocyclo-
pentadtene
Haleic anhydride
Inadequate evidence	to assess
carcinogenic rtsk
Inadequate evidence	In humans;
sufficient evidence	In experimental
animals
Inadequate evidence	In humans
and experimental animals
Sufficient evidence In
No evidence
ns
Inadequate data 1n humans and initials
Sufficient evidence In experimental
animals
Inadequate evidence In humans;
sufficient evidence In mImIi
Inadequate evidence In humans;
sufficient evidence in experimental
animals
Carcinogenic 1r> experimental
animals; no human data
Inadequate evidence In humans
and experimental animals
Inadequate evidence In humans;
sufficient evidence 1n experimental
animals
No data
No data
No data
Inadequate evidence
Mutagenic in short-term tests;
produces chromosomal abnormal 1 ties
In humans
Cr VI mutagenic In short-tern tests;
Cr VI produces chromosomal
abnormalities In humans
No evidence
Inadequate data
No data
Inadequate evidence
Mutagenic In short-tern tests
Mutagenic In short-term tests
Mutagenic In short-term tests;
chromosomal aberrations In
exposed workers
Mutagenic in short-ten* tests
No data
Ho data
Corrosive to skin and
micous membrane
Extremely high acute
toxicity
United evidence of repro-
ductive toxic 1 ty
Potent Irritant; burns upon
contact with skin
Upper respiratory Irritant,
eye irritant; with ambient
concentrations above 2.5 ppm,
extreme acute irritation
(continued)
* "Sufficient evidence" of carcinogenicity indicates a causal relationship between the agent and cancer.
"Limited evidence" indicates that a causal Interpretation is credible, but that alternative explanations such as chance, bias of review
board, or confounding could not adequately be excluded.
"inadequate evidence" indicates one or more of the following: few pertinent data; available studies showing evidence of association
did not exclude change, bias, or confound!ng; and studies were available that do not show evidence of carcinogenicity.
The classification of any chemical may change as new Information becomes aval table.

-------
TABLE 8 (continued)
Pollutant
Carcinogenicity*
Mutagenicity
Other effects
Manganese
No data
Ho data
Manganese poisonings have
been associated with mining;
chronic disease not fatal;
reports of neurological
disorders
Mercury
No evidence 1n humans
Ho data available on humans
Associated with neurological
disorders in humans
Hethy1 chloroform
11,1,1-trlchloro-
ethane)
Methylene chloride
(dichloronethane)
Nickel
Nitrobenzene
Hitrosomorphollne
Perchloroethylene
(tetrachloro-
ethylene)
Phenol
Inadequate data
Inadequate evidence in himans
and experimental animals
Sufficient evidence In humans;
limited evidence in nickel
and certain nickel compounds
in humans, but sufficient evidence
In experimental animals
Unknown, but being tested In fiscal
year 1903
Sufficient data In experimental
animals
Inadequate evidence in humans;
United evidence in experimental
animals
Ho data
Limited data In short-term tests
Limited evidence
Inadequate evidence
Unknown, but being tested in
fiscal year 1983
Ho data
Inadequate evidence
No data
A few ml of 1fquid can be
lethal to humans; produces
cyanosis and blood disorders
Harked corrosive effect on
any tissue; can cause severe
eye damage and blindness;
skin contact causes severe
burns
Phosgene
No known carcinogenic effects
Extremely toxic gas; can
cause death by suffocation
or heart failure
Polychlorinated
biphenyl ,
Inadequate evidence in humans;
sufficient evidence 1n experimental
animals
Inadequate evidence
(continued)
"Sufficient evidence" of carcinogenicity Indicates a causal relationship between the agent and cancer.
"Limited evidence" indicates that a causal Interpretation is credible, but that alternative explanations such as chance, bias of review
board, or confounding could not adequately be excluded.
"Inadequate evidence" indicates one or more of the following: few pertinent data; aval table studies showing evidence of association
did not exclude change, bias, or confounding; and studies were available that do not show evidence of carcinogenicity.
The classification of any chemical nay change as new information becomes aval 1 able.

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TABLE 8 (continued)
Pollutant
Carcinogenic! ty*
Mutagenic! ty
Other effects
Propylene oxide
Radionuclides
Toluene (ortho)
Trlchloroethylene
Vinyl chloride
Vinyl Idene chloride
o-,»-„p-Xy1ene
Inadequate evidence In humans and
experimental anlnals
Increased risk of lung cancer,
leukemics, anil other cancers,
depending on lifetime dose rates
and biological half-llfes of
specific radionuclides
inadequate evidence	ff* humans;
sufficient evidence	fn experimental
irtltsals
Inadequate evidence	1n humans;
11m1ted evidence In	experimental
animals
Sufficient evidence	In humans
Inadequate evidence In humans;
United evidence In experimental
animals
Met evidence
No data
Genetic damage to persons directly
exposed and also their progeny,
causing genetic Impairment of live-
born offspring or fetal death
Sufficient evidence In short-ten*
tests; no human data available; no
Increase in chromosone aberrations
Inadequate evidence in short-tern
tests; no data on humans
Sufficient evidence in humans
Sufficient evidence In short-tern
tests; no data aval table fn humans
No evidence
Adverse effects to humans;
Injury to eyes and skin
Central nervous syste
Vapor causes Irritation of
eyes, nose, and throat;
exposure to high concentrations
causes reversible kidney and
liver damage
* "Sufficient evidence" of carcinogenicity Indicates a causal relationship between the agent and cancer.
"Limited evidence" Indicates that a causal Interpretation Is credible, but that alternative explanations such as chance, bias of review
board, or confounding could not adequately be excluded.
"Inadequate evidence" Indicates one or more of the fallowing: few pertinent data; available studies showing evidence of association
did not exclude change, bias, or confounding; and studies were available that do not show evidence of carcinogenicity.
The classification of any chemical nay change as new information becomes available.

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SECTION 4
SITING PROCEDURES
4
To assist in selecting monitoring sites, specific procedures have
been developed for different scales of air quality representativeness. A
description follows of what scales of representativeness may occur, how to
identify what scales of representativeness are applicable to a specific area
of monitoring responsibility, and some recommended guidelines for locating
monitors for each scale.
REPRESENTATIVE TYPES OF MONITORING SITES
Spatial Scales of Representative Air Quality Levels
Because the air quality measured at a single site is based on a sample
of air from a very small volume, it is useful to know over how 1arge an area
this value can be considered representative. The concept of representative
spatial scale is used to designate this area. The spatial scale of represen-
tativeness means the physical dimensions of the area within which a monitoring
station is located that pollutant concentrations are reasonably similar.* The
following five scales are defined in Appendix D of Part 58, Title 40 of the
Code of Federal Regulations:
• Microscale—defines the concentrations in air volumes
associated with area dimensions ranging from several
meters up to about 100 m.
§ Middle Scale—defines the concentration typical of areas
up to several city blocks in size with dimensions ranging
from about 100 m to 0.5 km.
• Neighborhood Seale—defines concentrations within
some extended areas of the city that have relatively
uniform land use with dimensions in the range of
0.5 to 4.0 km.
§ Urban Scale—defines the overal 1 citywide conditions with
dimensions on the order of 4 to 50 km. This seale
would usually require more than one site for definition.
® Regional Scale—defines usually a rural area of reasonably
homogeneous geography and extends from tens to hundreds of
kilometers.
* Similar means extreme concentrations are within 25% of the mean for the
area. If 1arger values occur, the area would need to be subdivided until
this similarity criterion is met.
34

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Relevant Representative Spatial Scales
As described above, the spatial scales of representativeness depend
on the spatial variability of air quality levels. Observable physical
properties that primarily determine air quality levels are the sources, air
movements, and atmospheric transformation and depletion processes. In
Section 3, there are data and methods to characterize data that may be used
to estimate these determinants of air quality. Experience suggests that
a good emission inventory is the most useful single factor in estimating air
quality levels. Additional needed information includes a climatological
summary of the combined influences of wind direction, wind speed, and atmo-
spheric stability and an estimate of rapid removal processes (e.g., coarse
particulate matter settles out of the air quickly, and highly reactive chemi-
cals transform to other substances quickly).
In each monitoring area, the locations and emission rates of sources
for each pollutant of concern need to be identified as well as possible.
Table 4 may provide some help in identifying sources, and Table 6 suggests
prototypes of source configurations that are most likely to be associated
with the 43 pollutants with which this report is primarily concerned. It
would be convenient to link source configurations to representative air
quality configurations. However, this requires that the meteorology of
different areas of the country be relatively consistent. A review of annual
surface wind roses in the Climatic Atlas of the United States (U.S. Depart-
ment of Commerce 1968) shows this is not the case because patterns of wind
direction are highly variable across the country. The next best alternative
is to devise a methodology for selecting monitoring sites that takes the
local air quality pattern into account. A methodology has been developed for
representative spatial scales. The air quality pattern will be related to
the source pattern. The scale of interest with respect to a source pattern
will depend on the monitoring objectives and may vary from determining the
maximum effect to determining the maximum area within which a measurable
impact can be detected. Table 9 suggests the range of representative scales
that are of interest with respect to each of four types of source configura-
tions. Because, for the pol1utants of interest in this study, we are generally
concerned with ground-level sources, there will always be a microscale area
of maximum air quality 1evel near or within the source configuration of
primary concern. The extent to which larger seale air quality effects are
also of interest will vary with the monitoring objectives.
OVERVIEW OF SITING PROCEDURES
A general method for selecting sampling sites is outlined in Figure 1.
This procedure is applicable to all the representative spatial scales. The
The monitoring agency must be able to present a strong argument that the
data collected represent the real concentration pattern or exposure
potential. Sampling locations will be selected to fulfill the monitoring
agency's information needs, such as maximum concentration, frequency distri-
bution of the typical concentrations, spatial variations of the concentration,
35

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TABLE 9. REPRESENTATIVE SCALES APPLICABLE TO
TYPES OF POLLUTANT SOURCES
Type of source	Representative scales
Isolated pi ant	Micro to neighborhood
Small area	Micro to neighborhood
Large area	Micro to urban
Traffic	Micro to urban
36

-------
Determine source types
Final site selection
Perform screening sampling, If
desired
Prioritize the sites for final
selection
Determine optimum distances for
sampling under various conditions
Determine if seasonal variations
occur with pollutant sources
Select upwind or downwind sectors
from clfmatological summary
Prioritize the candidate sample
sites with respect to information
from modeling and wind data
Determine areas impacted by
sources using dispersion model
approach (optional)
Select actual sampling sites
by visiting candidate areas and
imposing the basic site criteria
Figure 1. Site selection procedure.
37

-------
etc. The objectives of the sampling activity must be clearly stated so the
sampling strategy and locations can be selected to collect the most relevant
information.
The first step in the site selection procedure is to determine sources.
The logic that this step requires is depicted in Figure 2. The type of
sources that will be encountered and their locations are combined with
meteorological information in the next step of the procedure. A representative
climatological wind summary is needed. A wind rose (see Figure 3} readily
shows the prevalent wind directions and most frequent wind speed. From the
wind data, the logical sectors for downwind (impact) or upwind (background)
sites can be determined.
Dispersion modeling is a good way to analyze the available source
and meteorological data in an objective manner to identify areas of relatively
good and poor air quality. Model results may be used to define distances
from sources to find maximum concentrations or the most frequently impacted
areas, which is the next step in the procedure. Site selection can be narrowed
down to zones within the sectors favored by wind direction and to zones
within those sectors that will be impacted by emissions as indicated by
modeling. A prelimi nary prioritization of candidate sites can be made based
on the modeling Information. However, the candidate areas should be viewed
before final evaluation. A semifinal ranking of all locations can be finalized
after preliminary or screening sampling has been performed.
The site selection procedure described above is appropriate to all
sources in a general way but is most appropriate to sources that may be
defined as point sources or small area sources. Depending on the spatial
scale of the monitoring problem, an area source can be considered as a point
source if the monitoring location is far enough downwind (e.g., on the order
of 5 to 10 times the diameter of the area source). Monitoring area sources
may require sampling sites along the perimeter of a well-defined small area
source or sampling within the perimeter of a large area source.
The following criteria are recommended guidelines in the final site
selection step:
§ Locate the sampler in an area that has unobstructed
air flow, especially in the direction of any recognized
sources of the materials being sampled. Turbulence
and eddys from obstructions will cause nonrepresen-
tative results. The distance between the obstruction
and the sampler should not be closer than two times the
height of the obstruction.
38

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I dentify monitoring area
and pollutants of concern
Determine source types within
and near monitoring area
Pollutant use and/or generation
Captive--used as
intermediate
Large volume chemical
used by few industries
Large volume chemical
used by many industries ¦
Large volume chemical
used by industry and/or
public
Combustion product
Area {small or
large)
Large area
Isolated pi ant or
smal1 area
Point or traffic
Source type
Isolated plant
Figure 2. Source configuration.
39

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15
»CRC(*r MtQuSHcr
Figure 3. Wind rose.
40

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Avoid locations that will be unduly influenced by nearby
sources or activities.
§ Avoid locations where reactive surfaces may cause chemical
changes in the air sampled.
t Be aware of mi croneteorological influences due to nearby
hi!1s, bodies of water, valley drainage flow patterns,
etc.
§ Place the intake probe at a representative height. The
guidance given for criteria pollutants is for probe height
to be 3 to 15 m above ground level, as near to building
height as possible but not where a building is an obstruc-
tion or the equipment is easily vandalized.
§ The probe should extend at least 2 m from a supporting
structure; if located on a building, it must be mounted on
the windward side.
Monitoring site selection criteria should be the same in most regards
whether the site will be used for a fixed station or for the nonfixed
(mobile) site. Uniformity among the sites should be achieved to the greatest
degree possible. Descriptions should be prepared for all sampling sites.
The description, at a minimum, should include the type of ground surface;
the direction, distance, and approximate height to any obstruction to airflow;
and the direction and distance to any local pollutant sources (actual or
potential). Photographs of the site are valuable for analysts who will not
have firsthand knowledge of the site.
Monitoring Point and Isolated Area Sources
Once an isolated source of interest is identified, the preferred
sampling locations are selected based on climatological data and perhaps
dispersion modeling information. Representative wind data for an isolated
area is especially important for plants that are built in a coastal area.
Many of the chemical plants that are of concern for noncriteria air pollutants
are built along the Gulf Coast where sea-breeze effects will be an important
factor in sample site selection. An experienced meteorologist's advice will
be necessary to interpret available data and to select the most suitable
locations for downwind sampling. Accessibility to the desired locations may
be a determining factor for final site selection; therefore, site visits will
be necessary in order to ensure that monitoring is practical in the selected
area.
41

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For stack emissions, the sites should be selected to indicate the
locations of ground impacts of the maximum concentrations-, for area sources
normally at or near ground level and that have no buoyancy, the maximum
concentration will occur within a few meters of the downwind boundary of the
source; therefore, sampling sites should be along the perimeter of the area
source. If elevated point sources are combined with ground-level releases in
the source configuration, dispersion modeling is recommended to indicate
where the combined impact will cause the maximum concentration. A number of
samples will be necessary in order to be confident that the small plume from
a small source will impact the sampler. The dimensions of the area source
will dictate how many samplers will be necessary to represent the maximum
pollutant concentration. Judgment based on experience and knowledge of the
character of the source will provide guidance on the number of samplers to
place. If the source is not well characterized, more samples must be
obtained. A1so, if only one or a few isolated sources are present, the like-
lihood of the source impacting each sampling site is small; hence, more
samplers are required. For pollutants that are very reactive, the downwind
distance from the source should be kept to a minimum to avoid degradation of
the pollutant due to chemical reactions.
Monitoring Large Area Sources
Characterizing the air quality resulting from a large number of small
sources will be less difficult due to a higher probability of finding the
areas of maximum impact. As with all site selection activities, the first
steps are to characterize the sources of the pollutant as best as It can be
done, and identify areas with the highest likelihood of maximum impact using
climatological wind data and dispersion modeling. Special attention is
needed to select sites that offer the most potential for adverse impact,
e.g., maximum concentration or maximum population exposure. One problem is
evaluating the frequency and magnitude of the pollutant emissions. The
source with the highest emission rate and the greatest potential for adverse
impact is a good starting point. Locations that have the potential to be
affected by multiple sources, i.e., locations on the downwind edge of a large
source area, are important. Which of these two types of locations will
experience higher maximum concentrations or more frequent exposure to the
pollutants may depend on the duration of the exposure time that is of concern.
Monitoring Irregular and Widespread Smal1 Emissions
Pollutants used in small quantities by the general public or industries
will require long-term sampling programs at locations where exposure may be a
matter of special concern. Characterizing the exposure potential requires
knowledge of when and where the pollutant will be generated or emitted so
that a minimum of unnecessary sampling is done. The best judgment must be
made of where and when to sample at sites that conform to good siting criteria
with respect to the expected sources. With the probability of the pollutant
occuring in a low concentration, the sites selected should avoid areas where
high concentrations of other compounds may interfere with the analysis of the
pollutant specifically being sought.
42

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Pollutants that are frequently used in small quantities by industry
and the public will be nearly ubiquitous. Site selection will depend upon
the resources available to carry out the sampling program. Sampling sites
should be placed in as many locations as necessary to describe the population
exposure. Sampling sites selected should be within populated areas and
afford the most representative site that can be obtained over a neighborhood
or urban scale area.
SITING PROCEDURES FOR REPRESENTATIVE SPATIAL SCALES
In the preceding section, it was recommended that spatial scales of
interest to a specific area of concern be defined by considering types of
source configurations and monitoring objectives. Procedures for selecting
monitoring sites are presented for the following scales of sites:
•	Urban scale
i Neighborhood scale
« Microscale or middle scale.
Urban Scale Sites
A methodology for selecting sites that represent urban scale air-quality
levels is presented in Figure 4. In general the method consists of identi-
fying the 1argest area with which effects of interest may occur, eliminating
areas that are not representative of urban scale effects, and emphasizing
areas that are representative of high concentrations over widespread areas.
The first step is to assemble data. Seven specific types of data that
will be useful are listed in Figure 4. Because urban scale effects are of
interest, emissions are possible over a large area and from many sources.
The locations and emission rates of sources need to be identified. If a
local compilation is not available and cannot be made, information from the
following sources may be helpful:
•	EPA data bases (e.g., NEDS and NESHAPS)
•	State emission inventory
•	New source registration/application files
•	Table 4 of this report
•	EPA reports (e.g., Suta 1979).
43

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Select sites with as many good siting
characteristics as possible
Identify the area that includes most
small sources
Delete areas with low population
densities
Delete areas subject to small-scale
influences of major point and highway
sources
Identify remaining areas with the
following good siting characteristics:
•	Near sensitive population facility
•	In prevailing downwind sector
•	In low elevation terrain
•	In prevailing stable-atmosphere
downwind sector
•	Open (free of wind obstacles)
Assemble data on
•	Sources (location and emissions}
•	Population density
•	Sensitive population facilities
•	Low elevation terrain
•	Wind roses
•	Stable-atmosphere wind rose
•	Obstacles to wind flow
re 4. Steps for locating an urban scale site.
44

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Data on population density can be determined from land-use maps available
from local urban pianning agencies, zoning commissions, and similar types of
organizations. U.S. Census data of population densities in small sub-tracts
wi 11 also be helpful, but it does not reflect the daytime population distribu-
tion. The locations of sensitive population facilities (e.g., hospitals,
nursing homes, day care centers, elementary schools) can be located using
telephone yellow pages if they are not identified on local maps.
Topographical maps are valuable for showing the locations of low-lying
and elevated terrain. The information assembled can be conveniently
summarized using either topographical (e.g., U.S. Geological Survey maps) or
land-use maps.
Information on wind flow is best obtained from wind roses (i.e., a
graphical display showing the frequency of occurrence of wind directions).
If possible, wind roses for the occurrence of stable atmospheric conditions
and light wi nd speeds should be obtained in addi ti on to a local annual wind
rose for surface winds. These are available from the National Climatic Data
Center (NCDC) in Asheville, North Carolina, or they may be compiled from an
available source of local wind observations. Before wind data not obtained
from a National Weather Service (NWS) station is used, a meteorologist should
be consulted to determine whether the measured winds are representative of
pollution transport over the urban scale area. In fact, a meteorologist
should be consul ted on the representati veness of any wi nd data for the scale
or location of interest.
Because buildings, trees, and prominent terrain can obstruct air flow,
the locations of such air flow obstructions need to be noted in selecting
monitoring sites. Aerial photographs and visual inspections of areas to be
monitored are usually adequate to identify unsuitable sites.
After data relevant to characterizing the air quality pattern is assembled,
an analysis can be made of representative and nonrepresentative monitoring
locations. A characteristic of the sources when an urban seale effect is
representative is many small sources over a large area. If there are one or
more predominantly 1arge sources, there may not be a wel 1 -defined urban scale
effect. In this case, neighborhood and small-scale si ti ng are more appropriate.
The area surrounding most of the small sources that make up the 1arge
source area should be delineated as the first step of the analysis. If this
area is less than about 5 km in diameter, urban scale air-quality levels will
occur outside the source area. Otherwise, an appropriate urban scale monitor-
ing site should be sought within the source area.
Additional steps should be taken to identify locations that have
either desirable or undesirable representation characteristics. Locations
close to major sources (e.g., high-traffic roadway or relevant processing
45

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plants} are to be avoided. Locations in deserted areas and areas that are
entered infrequently day or night do not demonstrate population exposure
hazards and are to be avoided. Desirable location characteristics Include
high population density (day and/or night); sensitive populations (e.g.,
hospitals, child day care centers, retirement homes, etc.); susceptible to
air pollution episodes (e.g., low lying; downwind of the source area during
stable, light wind conditions); and free of prominent building and terrain
Influences.
A useful guide to selecting desirable sites is to mark areas for
each desirable and undesirable characteristic on a map that also shows
the source area. Areas that have the most desirable siting characteristics
and no undesirable characteristics can be easily designated. These areas
can be further reviewed by visual inspection and by mobile or temporary
monitoring.
The following guidelines are offered to help identify desirable and
undesirable monitoring areas:
Ground-Level Stationary Source Influence-
There are no absolute rules as to how far away the emissions from a
stationary source are significant. One limitation is the detection-sensing
threshold of available monitoring techniques. Another limitation is the
horizontal gradient of concentrations, because once the gradient approaches
the gradient of ambient concentrations, the effects of the source are no
longer detectable. Through the use of optimum sample col lection media and
analytical instruments, detection-sensing thresholds need not be a limitation.
Recommended monitoring techniques for many of the NCAPs of interest are
given in Appendix A, As an example, a detection threshold of 5 ng/m3 means
that a source strength of 0,1 mg/sec (about one third of an ounce per day, or
less than 10 g, per day) is detectable within a 130-m wide swath at a distance
of 1 km from the source (i.e., assuming neutral stability and a 2 m/sec wind
speed blowing from the source toward the sampler for an hour). The variations
in ambient concentrations that can be expected in urban areas are shown by
the data collected by Singh et al. (1982). For convenient reference, these
observations are presented in Appendix EL For toluene, hour-to-hour variations
are shown to be as great as 20 piq/w&. For most other pollutants, the
hour-to-hour variations are more typically 2 /xg/m3 or less. Table 10 shows
maximum distances from sources that a contribution can be measured for given
ratios of the source contribution to the source strength. In many cases the
ratio of ambient variations to source strength will not be known, but 10~4
may be a reasonable expectation. Based on the results in Table 10, locations
within 1.3 km of such stationary sources will not represent urban scale air
quality during the night. The data in Table 10 suggest that the distance to
which a source can have a significant impact on ambient concentrations is
highly variable and can be quite large. The data in Table 11 may be used to
help estimate ambient concentration variations and source strengths that need
to be considered for many of the pollutants of concern. By inspection of the
data shown in Appendix B, 1t appears 10 to 20 percent of the mean of the
46

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TABLE 10. MAXIMUM DISTANCE FOR SELECTED RATIOS OF MONITORED
CONCENTRATION TO SOURCE STRENGTH
Ratio of monitored concentration	Distance (km) for stability class1
to source strength	(s/m3) C	D	E
10-3	0,14	0.2	0.3
3x10-4	0.3	0.4	0.7
1Q-4	0.5	0.8	1.3
3xl0-5	0.9	1.8	2.8
10"5	1.7	3.7	6.1
* Assumes wind speed of 2 m/s. Based on data in Workbook of Atmospheric
Dispersion Estimates {Turner 1970).
47

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TABLE 11. AMBIENT CONCENTRATIONS AND EMISSION FACTORS
Pol 1utant
Observed urban
concentrations*
(ng/m3)
Topical emission factors1"
Benzene
Methylene chloride
Chloroform
Carbon tetrachloride
Methyl chloroform
Vinylidene chloride
Trichloroethylene
Perch!oroethylene
Chlorobenzene
p-Dichlorobenzene
Formaldehyde
Phosgene
Acrolein
Nitrobenzene
Dimethylnitrosami ne
Toluene
o-Xylene
m-,p-Xylene
Phenols
4800-15000
1400-6300
0-730
820-1700
1500-5500
11-30
250-1800
1100-4800
510-4100
0-1600
0-3300
120-130
9200-21000
0-460
25-28
17000-57000
2800-10000
6100-23000
120-120
Q.13 g/mi from motor vehicles^
1.8 Ib/yr per person
Production 0.11%; solvent use
100% {7% of product)
Production 0.22%; solvent use
100% [8% of product)
100.0% most degreasing and
solvent uses
Unknown
87 lb/day frost open top vapor
degreasing operations
1.6	Ib/yr per person for dry
cleaning, 12 lb/day from vapor
degreasing operations
0,32% production, 0,04 g/s at
cold cleaning operations
0.72% production, 0.22 Ib/yr per
person
0.48% of usage
0.018% production
0.11% production
2,8% of cellulose production,
1 lb/103 bbl crude oil capacity
0.2% of dimethyl amine production
0.38 g/mi from motor vehicles,
3.7	Ib/yr per person from solvents
0.8 lb/yr per person from sol vents,
0.035 g/mi from motor vehicles
1.6 lb/yr per person from sol vents,
0.074 g/mi from motor vehicles
0.22% production
* 25th and 75th percentiles of compiled observations (Brodzinsky 1982).
t from EPA, OAQPS compilation entitled "Human Exposures to Atmospheric
Concentrations of Selected Chemicals" (Systems App1ications, Inc. ,• 1980}.
I Assumes benzene is one-third of toluene emission rate (Bucon, Macko, and Toback 1978)
#8

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observed range is a reasonable estimate of expected hour-to-hour variations
in ambient concentrations. Data observed at urban locations for each of the
pollutants listed in Table 11 are also available (e.g., see Brodzinsky et al.
1982).
Mobile Source Influence--
Mobile source emissions are by nature less concentrated than stationary
source emissions, because they are spread over a line rather than emitted
from a single point. As a result, the concentrations of pol1utants from
mobile sources are lower and decrease less rapidly with distance. Both these
effects result in a more homogeneous effect on urban scale air quality
at distances closer to highways than to stationary sources. Figure 5 shows
how concentrations vary downwind of a typical high-traffic urban highway.
The values shown are representative effects of toluene emissions from auto-
mobiles, as computed by the EPA HIWAY2 model. These results suggest that
150 m from the highway, the gradient of concentrations from the highway
emissions has become nearly flat and thus spatially homogeneous. As a
further gui deli ne, the concentration with travel di stance from a line source
was examined for a range of typical meteorological conditions. The ratio of
the minimum concentration of interest to the estimated highway emission rate
was used to determine how far from the highway an urban scale monitor must be
located. In most cases, 0.5 km from the most dense traffic roads wi11 be an
adequate di stance for an urban scale site.
Population Density—
Data from the most recent U.S. Census can be used to identify high
density residential areas. Land-use and zoning maps prepared by metropolitan
planning commissions are good sources of nonresidential, high-population
access areas and remote areas with very low population access. The types and
forms of census data available for a specific area can be determined by
contacting the Bureau of the Census (Data User Service Division, Customer
Services (Publications), Washington, D.C. 20233).
Sensitive Population Facilities--
Sensitive population facilities can be located by consulting common
references such as 1ocal directories and public service organizations. The
number of people accommodated and the hours of operation may al so be of
interest, as well as location of each facility, because this additional
information is easily acquired.
Prevailing Oownwind Sector—
Next to an emission inventory, a climatological summary of wi nd di rec-
ti ons is the most useful information for selecting monitoring sites. The
frequency of occurrence of wi nd d1rection on an annual basis or for any
specific time period or special condition (e.g., by atmospheric stability
49

-------
15.ft
Highway Data
4-lanc, 12-m wide highway
Traffic «* 3500 vehiclef/h
Kinluioiu » 0- 2-1 g/vehlcle/km
13.5
Winds
Perpendicular to highway
Wind (peed =• 4 ni/i
?.S
un
o
a.s
tea
68
80
4®
1)1 STANCE ntOM Ml D1AN{M)
LEGEND: PASQUILI. STABILITY	+ c	-A—A-A D	&-a~™0 E
I igure S. Concentration as a function of stability class, computed using HIWAY? model.

-------
class) can be tabulated from hourly observations or obtained from the National
Climatic Data Center for National Weather Service observing stations. The
stability data from NCDC are particularly convenient for this purpose. Table 12
shows an example of the type of data that can be requested. In this example,
the relative frequency of occurrence of 16 wind direction classes are given
for six wind speed classes and Pasquil1 class D stability (i.e., as defined
by Turner 1964 for standard NWS observations)- For NWS data observations
collected since 1964, the wind direction can be tabulated by 10° intervals
instead of 16 compass point classes. If air quality observations are based
on samples collected for 24 hours, a more useful tabulation of wind data is
the frequency of occurrence of classes of 24-hour resultant wind directions
(see Figure 6). It is a good idea to limit the resultant wind tabulation to
days that the wind direction is reasonably persistent as defined by a wind
persistence indicator, calculated by taking the ratio of the resultant to the
24-hour arithmetic mean wind speed. In Figure 6 the data are limited to days
with a wind persistence indicator of 0.85 or greater.
A tabulation in the format of Table 12, including all stabilities,
is recommended to identify the prevailing downwind di recti on for 1-hour
sampling periods. Figure 7 illustrates how the prevailing wind direction
and the identified source area may be combined to define the prevailing
downwind sector of the source area. The first step is to determine by visual
inspection the longest trajectory 1ine across the source area that is parallel
to the prevaili ng wind. In thi s example, 75 percent of thi s di stance is
chosen as a high-exposure distance. All locations that have an upwind
trajectory of at least this length are identified as the high-exposure
areas.
Prevailing Stable Light Downwind Sector—
The preceding discussion places emphasis on finding a frequently
exposed monitoring site. Another area of concern is that exposed to the
highest concentrations regardless of frequency. For ground-level sources,
this will be periods of low wind speed and a stable atmosphere. Under these
conditions, the pollutant remains in the vicinity of its source or siowly
drifts with the circulation created by the thermodynamic influence of the
city on the otherwise stagnant air. The prevailing wind di recti on during a
stable atmosphere (Pasquill classes E and F) and light wind speeds {i.e.,
less than 2 m/s) can be determined using a data tabulation such as the
one shown in Table 12 for £ and F stability combined. It is interesting to
note that, for the distribution in Table 12 under the column for the totals
of all wind speeds, northwest is the prevailing wind direction. However, for
the 0 to 3 knot wind speed column, southeast is the prevailing wind direction.
51

-------
TABLE 12. EXAMPLE OF THE FREQUENCY OF OCCURRENCE OF
WIND DIRECTIONS FOR NEUTRAL ATMOSPHERIC STABILITY
AAMUMt	ICUHn 'tCttCNCf mnmtlt*	STATION:	*[Nh U'U as
5>U0 £*
0IMCT1(*
3 * 3
4 - S
7 • 10
11 - 16
17 - ?i
ustmn 7hm 11
total
H
0 001073
3.QC2U3
4.DOi>21
o.m<9U
S.002SSO
O.O0J4S&
0.0?«990
NUC
0,00364$
a.ooiaoo

a.oafOM
o.ooijso
Q.0OO72'
0,01Ut*
"C

a 002095
H.0MS44
<3 3$4?&§
0.001*21
O.QOQS71
0.019523
HI
3 000^4
0 oomi
O.XHfJ
3 010092
0.3036*
0.302431
0.0*67*2
i
0.38W3
0.502361
o.xun
0 00I9U
0.003444
0.OTI23
J.026254
CSl
O-OOIHI
isonn
«.3I«909
0 022012
Q.0041*1
0.00014?
0.0492M
sr
0.0029Z1
fl.004*32
0.017100
0,020413
O.OOSOOf
a.oootti
0.34I3SI
%%%
0 001 WO
O.pGfSIl
g.aig&ii
0.0*4107
Q-0053H
0000952
Q.Dllllf
%
o.»u;2
3,007095
OOM369
0 01*57$
0 HH951
0.000*47
o.ohim
SS*
3,000717
3 sX>!
3 SOdQH
0.3JW04
O.MJIW
0.30053:1
303JSU
s«
3 D0tS4«
S.DOS 142
o.oorsi?
0.009102
O.OCOTU
0.000724
3.0Z214?

imii
a.OTiii'
0.00464ft
O-PSWl
O.OGIW
Q.000647
0.016026
w
0.000941
a.ssiw
0.007UJ
O.0I3W2
o.oowst
0.00201*
0.031S&&

O.OOQ751
CLOOIJB
a.ouiM
0.014770
0.Q17I21
0.010473
O-0717J6
tt
Q.0C2l««
a. mm
a.0)6371
Q.ouwa
0 019270
3.306741
3,O»0>6

0.O0QBS6
Q.0ll*?S
0.01141^5
0.020HS
O-SsgW
0.30254?
0 04 7052
wai
0.020070
Q,0UO36
0.169929

O.Q*H7?
0.03301?

etunvf 'HQUtlKt OF OCCV«tt*Ci OF 3 STWilJTT • 0.621715
Ui*ni( fttgwc*CT or s&ststisuus jucnrl mi* q stmiuh • 0.002532
* Multiply by
0.51 to determine speed In m/s.

-------
WNW
WSW
Figure 6. Frequency of 24-hour mean wind directions for
Baltimore-Washington International Airport for 1973-1977
{wind persistence indicator greater than 0.85}.
53

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Prevailing
wi nd
Zone of maximum source
exposure trajectories
Boundary of
source area
75 percent of
maximum exposure
trajectory
Highest
exposure
section
Figure 7. Example of high exposure area.
54

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The procedure illustrated in	Figure 7 may be repeated for the prevailing
direction under stable light wind	conditions. However, if there is a high
frequency of reported calm winds,	it is recommended that the downwind section
be extended to include the center	of the source area.
In identifying the prevailing wind di recti on during 11ght wind conditions,
it is important that the meteorological observations be representative of the
source area. If the source area is on one side of a large metropolitan area,
wind observations from an airport on the opposite side may be misleading. If
representative wind data are not available, it would be best to consider the
center of the source as the primary exposure area for stagnant air situations,
low-lying terrain is also subject to high pollution during stagnant meteoro-
logical conditions.
Low Terrain Areas—
Just as the organization of building structures can influence the flow
of air that is stagnant, so can the shape of the terrain. This can be a
problem at night when air close to the ground cools rapidly. Cooler air is
more dense and will readily displace warmer air at a lower elevation. This
leads to nocturnal drainage flows and embedded drainage plumes. As a result,
the low point in a source area or the side of a source area to which the air
drains will be an area of relatlvely high nighttime air pollution. These
areas can be best Identified by examining a topographical map that shows low
lying areas and the locations to which air overlying the source area can be
expected to drain.
Open Areas-
Locations that are shielded from the general ambient flow by steep
bluffs, by buildings, or by trees are poor sampling locations because they
frequently are representative of a very, small local area that is cleaner or
dirtier than a more open area. Open areas that are free of obstructions can
best be identified from land-use maps and from visual inspection of the
general area to be monitored.
Neighborhood Scale Sites
A methodology for selecting neighborhood seale monitoring sites 1s
shown 1n Fi gure 8. Situations in which nei ghborhood seale air quality
effects are of interest occur for an urban area within or around which there
are well-defined sources that consist of either smal1 areas of many Industrial
or commercial operations or 1arge integrated plant sites. The methodology
consists of characterizing significant variations in the air quality pattern
and the density of population exposed to air quality. Areas of poor, medium,
and good air quality and the nature of the overall population exposure threat
can be identified by monitoring a range of different neighborhoods. The
methodology provides a systematic way of assembling and evaluating information
in order to plan a useful monitoring network.
55

-------
/ Are \
time and resources
v^avail able for alp
^xjnodel i ng?/^
Yes
Select sites
Perform modeling
analysis
Select neighborhoods
for monitoring
Perform qualitative •
air qual ity analysi s
Eliminate areas
affected by individual
sources
Assemble data on
§ sources
• population
§ terrain
Map population density and
identify sensitive population
]ocati ons
Figure 8. Steps for locating a neighborhood seale site.
56

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The first step in the analysis is to assemble data on sources, population,
wind, and terrain. Relevant data were cited in the preceding discussion of
urban scale sites.
The second step recommended in Figure 8 is to map the population
density and to identify the locations of sensitive population facilities.
U.S. Census sub-tract data for urban areas, land-use maps from urban planning
agencies, and land-use statistics (e.g., floor space, number of employees,
business volume) from tax collection and other relevant agencies are sources
of data for defining the population density. It is recommended that the
available data be used to divide the monitoring area into high, medium, and
low population areas for both day and nighttime periods. For most uses of
monitoring data, this Is an adequate spatial distinction. Of all the available
data, Census data are the most easily related to spatial distribution. It is
recommended that population densities based on Census data best represent the
nighttime population distribution. Areas of high residential population
density should be modified for daytime distribution estimates to include
locations with high employment and major shopping centers. It is a relatively
simple matter to plot the available data on residential population densities
on a map and to divide the monitoring area into zones of low, medium, and high
population density. The zones can be modified on a second map to include
areas of high employment and major shopping when these activities lie outside
the high population zone. These zones should be used as a guide in selecting
neighborhoods to include in the complete monitoring network.
The locations of sensitive population facilities should also be noted on
a map. Suggestions for identifying and locating sensitive population facili-
ties are given in the preceding section.
The next step is to determine the expected spatial distribution of
air quality levels. One way to characterize air quality levels over the
monitoring areas of concern is to perform an air quality simulation using one
of the standard mathematical models. If one is reasonably confident about
the location and emission rates of the sources, if representative meteorolog-
ical data are available for the area, and if the area is free of major
terrain complexities, computer modeling will provide a convenient and compre-
hensive analysis of the distribution of air quality levels over the area of
interest. Models recommended for different source configurations and different
averaging periods are shown in Table 13. It should be noted that when
multiple pollutants are being considered, a separate model run is needed for
each pollutant with different sources or with a di fferent distribution of
emissions from the sources. Results from a single simulation are applicable
to all pollutants that have the same sources and that have emission rates
among the sources that are equal or proportional. For guidance on the use of
models and the preparation of input data, consult the Guideline on Air
Quality Models {U.S. EPA 1978} and the Regional Workshop on Air Quality
Modeling—A Summary Report {U.S. EPA 1982).
57

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TABLE 13. RECOMMENDED EPA MODELS BY SOURCE CONFIGURATION AND AVERAGING TIME*
Averaging time
Monitoring station
Maximum i to
Annual mean 24- hour
General urban area
-	area and point sources
-	with complex sources
COM
ISC
RAM
ISC
Urban area with single or multiple major
source(s)
COM
RAM
Single source with terrain height below
stack top1" (complex source)
CRSTER
CRSTER (ISC)
Single source near terrain above stack top§
COMPLEX I
or VALLEY
YALLEY or
COMPLEX I
* Available in EPA UNAMAP System {Version 5).
t For multiple sources where it is not appropriate to consider the emissions
as located at a single point, the MPTER model is appropriate,
I COMPLEX I and VALLEY are considered screening techniques. For regulatory
purposes, COMPLEX I should be used only with onsite meteorological data as
input.
58

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These models treat inert pollutants but provide useful approximations
for reactive pollutants also. Application of models for reactive pollutants
is a special study requiring a specialist in chemically reactive models, more
sophisticated computer modeling, and special input data preparation. This
level of detail is not usually required for siting studies.
A large metropolitan area may be characterized by well over 1000 different
neighborhoods. Although mathematical modeling is the most satisfactory way to
classify the air quality potential of neighborhoods, it is also possible to
classify neighborhoods in a more qualitative fashion by examining the locations
and magnitudes of sources in relation to wind direction frequencies and
topographical influences. This approach amounts to using the data needed
in a modeling study in a more qualitative manner. Estimates of emissions
must be prepared for all areas of the city. One method is to divide the city
into homogeneous subareas, each about the size of a neighborhood (i.e., 0.5 to
4 km in diameter). A land-use map prepared by local zoning or urban planning
agencies may be suitable for this purpose. If a suitable land-use map is not
available, one may be prepared by interpreting aerial photographs and other
available sources of information. Table 14 suggests a land-use classification
scheme (after Auer 1978) that may be used to guide the preparation of a land-
use map. Of course, any large point source of each pollutant of concern
should be analyzed separately. The data presented in Section 3 may help to
identify which neighborhoods emit which pollutants, and provide a basis for
determining an emission rate. However, for many NCAPs, new and better
information on sources and emission rates is being assembled as part of EPA's
continuing review of potentially hazardous pollutants. Regional offices
should be consulted for references to the most current information on each
pollutant of interest. An extensive compilation of emission rates and
sources of emissions for most of the NCAPs listed in Table 1 was published in
a recent EPA study of human exposure estimates (Systems Applications, Inc.,
1980 and Suta 1979).
The frequency of occurrence of wind directions must also be determined.
These data are available from the National Climatic Data Center for all
metropolitan areas. It is necessary to identify only the location that is
most representative of the areas to be monitored. Appendix C contains a list
of readily available data summaries.
The locations of major topographical features must also be identified
relative to the source areas. The following topographical features are of
i nterest:
•	Central business district boundary
•	Urban development boundary
§ Undeveloped area boundaries {including parks,
wooded areas, open areas, etc.)
•	Major bodies of water
t Terrain elevation contours.
59

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TABLE 14. IQOTtPlCATION A MO CLASS1 FIXATION OF LAND USE TfTCS [ AFTER AUES 197<3]
Type
Use and structures
Vegetation
11	Heavy Industrial
Major chemical, steel, and fabrication industries;
generally 3- to 5-story buildings, flat roofs
12	Light-Moderate Industrial
Rail yards, truck depots, warehouses. Industrial
parks, minor fabrications; generally 1- to 3-story
buildings, Mat roofs
CI Commercial
Office and aoartment buildings, hotels; > 10-story
heights, flat roofs
31 Common Residential
SIngle-family dwellings with normal easements;
general 1y single-story, pitched-roof structures;
frequent driveways
R2 Compact Residential
Single- and some multiple-family dwtlings with
clost spacing; generally 7(R vegetation
Limited lawn sizes and shade
trees; «3K vegetation
Limited lawn sizes, old estab-
lished shade trees; <35% vege-
tation
Abundant grass lawns and lightly
wooded; >955 vegetation
Nearly total grass and lightly
wooded; >955 vegetation
local crops (e.g., corn, soybeans}
>95» vegetation
Mostly wild grasses and weeds,
lightly wooded; >901 vegetation
60

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The number of neighborhood scale monitoring sites to be selected will
depend on the monitoring objectives, the number of pollutants of concern,
and the resources available. However, neighborhoods can be categorized
as high, low, or medium with respect to concentrations of each pollutant,
by using the information described above. The following guidelines are
recommended:
1.	High concentration neighborhoods
§ Neighborhoods with highest emission density,
i.e., mass emitted per unit area
§ Neighborhoods downwind of prevailing wind from the
area with highest emission density, particularly
one with a relatively high emission density
•	Neighborhood at the downwind end of the longest
trajectory over areas with significant emissions.
2.	Low concentration neighborhoods
•	Neighborhoods with lowest emission density
§ Prevailing upwind side of areas with significant
emissions.
3.	Medium concentration neighborhoods
§ Between high and low concentration neighborhoods
§ Adjacent to high concentration neighborhoods
•	Neighborhoods with sensitive population, high
population density, or major projected growth.
In determining prevailing downwind and upwind directions, the available
data on wind direction frequencies should be modified to account for the
influence of topographical features. A meteorologist should be consulted on
how to estimate topographical influences.
A specific site within a selected neighborhood should be free of the
influence of individual sources, or the measurements will not represent
the neighborhood scale. Figure 9 provides an aid in determining how far
away a ground-level point source can influence a monitor. Elevated stacks
would have significantly 1 ess influence. To use the graph, an estimate
is made of the general or area source emissions from a square kilometer
in the vicinity of potential monitoring sites. The piotted lines in
Figure 9 show the distance beyond which a point source wi11 contribute less
than 10 percent of the ambient concentration due to nearby area sources that
61

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10-
*
E
Pasquil1 stability class
0.2	0.5 1
POINT SOURCE EMISSIONS AS A PERCENTAGE OF THE EMISSIONS
FROM AH AREA SOURCE EXTENDING 2KM UPWIND	)
* This is the distance from a ground-level point source beyond which the
ambient concentration contribution is less than 10% of the concentration
from a 2 km along-wind area source.
Figure 9. Guideline for estimating impact distance of a point
source overlapping an area source.
62

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extend 2 km upwind of the receptor, as a percentage of the area source
emission density. Plotted lines are presented for three Pasqui11 stability
classes in order to show how variable the estimates could be in a 1-hour
steady wind condition. It is recommended that the D stability graph be used
as a guide in determining how far to locate monitors from a nearby point
source. It may be seen that large sources wi 11 influence monitors 6 !
-------
Asseaftle data on
i Sourets
l Mtteorology
a Terrain
Is source
elevated?
Sal act si I® war
(am traffic
on prevail 1«9
dOMWind |1M of
hlojwtay



Jse distance to
¦iiIom laoact
and associated
at«iosp*«rl c
stiBl11ty and
wind d1 recti an
to select j1 te
Select site next
to source on
preva1t1nf
dowwlnd side
for most itaole
atao»(*ere



lelfct iUt next
to wurei on
prevaO 1 ng
dOMflwInd jloe
far ill
conditions
5el«Ct MC0M lit* on
opposite ltd* of source
if «u1*ub tr»ff1 c
periods and/or stable
ataospneret Have a
signlflcantly different
prevail1ng *1nd
Use prevail !ng
Mind d1 recti an
and mx1*um Ispact
distinct for
neutral ateospflere
Co select second
Ispact site
Nudlfy site selections for
topograpnlcil 1nfluences
Final l1ti selection
	_i	
Select proee location
Figure 10. Steps for locating micro or middle scale sites.
64

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The maximum impact of ground-level emissions occurs close to the source.
Site selection considerations for monitoring the influence of elevated
sources, usually well marked by stacks, are more complex. Ground level
emissions will be associated with either a plant site or a highway. To
monitor the maximum impact of a ground-level source, it is necessary to get
as close to the source as possible and still be in a zone of concern because
of the exposure hazard to the public. The major factor to take into account
is the wind direction. However, only periods in which emissions occur and
during which the emissions are least diluted due to atmospheric turbulence
need to be considered.
When considering NCAP emissions from point sources, until exposure time
standards are set, it may be necessary to consider both long-term and short-
term mean concentrations. The meteorology of the area may be such that the
maximum long-term and short-term impacts occur at different locations. An air
qual1ty simulation model may be used to Identify the locations of maximum
impact. The Impacts can be assessed using the CR5TER or the ISC models.
(See the preceding discussion for recommendations and references regarding
the use of these models.) As a quick alternative to modeling, one can use
routine meteorological data summaries to select sites. The following guide-
lines are recommended for selecting the location of the maximum short-term
impact;
1.	Determine most stable atmospheric class associated with
periods of high emissions. If emission rate has no diurnal
variations, select most stable class (Pasquill class F for
rural areas, class E for urban areas I,
2.	Determine wind direction with greatest frequency of
occurrence for selected stability.
3.	Select location close to source fence line and downwind of
source in direction of most frequent wind transport for
selected stability.
For the location of maximum long-term impact, the following guidelines are
recommended;
1.	Determine the climatologically prevailing wind direction
(highest frequency of occurrence annually). Day and night-
time summaries are available and should be used for
sources that have primarily day or nighttime emissions.
2.	Select location close to source fence line and downwind of
source in direction of prevailing wind.
65

-------
When considering NCAP emissions from highways, it is desirable to
account for possible correlations between diurnal variations in emissions and
wind direction. If two sampling sites can be allocated to the source, one
could place a site on either side of the area of maximum traffic flow. If
only one site is to be used, it is important that the site be on the side
that is downwind of the highway most frequently during periods of maximum
traffic. If peak traffic occurs from 7:00 a.m. to 8:00 a.m. and from 5:00 p.m.
to 6:00 p.m., the frequency of wind directions during very stable and very
unstable conditions should be excluded. It is recommended that the most
frequent wind direction for Pasquill stability classes C, D, and E be used to
determine on which side of the highway to locate a monitoring site. The
monitoring site should be located as close to the highway as is practical for
monitoring gaseous pollutants or pollutants collected using size selective
intakes. If standard hi-vols are to be used, the siting guidelines for
distance from roadways given in 40 CFR 58 for TSP monitoring, should be
followed.
For elevated sources, the distance to the zone of maximum impact and the
effect of meteorological conditions on its location must be taken in account
in selecting a site for monitoring the maximum impact of the source. The use
of air quality simulation models, such as CRSTER and ISC, is the recommended
way of determining the locations of maximum short-term and long-term contri-
butions to ambient concentrations. These models will take the effect of
variations in wind speed and atmospheric stability into account in estimating
the degree of plume rise, as well as the direction of travel and dilution of
the plume by turbulence. The models provide a comprehensive analysis of the
effects of hourly variations in meteorological conditions of the patterns of
air-quality effects. This provides the best estimate of where the maximum
short-term and long-term concentrations will occur. An alternative is to
take the following short-cut steps using the graphs in Figures 11 and 12 to
select the location of maximum short-term concentration:
1.	Use "Procedure for Evaluating Air Quality Impact of New
Sources" (U.S. EPA 1977, pp. 4-7 to 4-9) or other equivalent
procedures to estimate effective source height for each
stability class with significant emissions.
2.	Use Figure 11 or 12 to determine stability condition and
downwind distance that give maximum concentration.
3.	Use climatological data to determine wind di recti on with
greatest frequency of occurrence for selected stability
condition.
4.	Select site in the downwind direction of most frequent
wind for selected stability, at distance of maximum
concentration {Step 2).
66

-------
MAXIMUM xu/U. us 1
Figure 11. Downwind distance to maximum concentration and maximum relative concentration (*u/Q) as
a function of Pasquill stability class and effective plume height In rural terrain (after Turner 1970).

-------
a.i
J	L
i i i i
i i
iifi
irs
to*5
ir
MAXIMUM xu/OL m
• 1
:igure 12. Downwind distance to maximum concentration and maxintra relative
concentration Cxu/Q) as a function of stability class and effective p1jme
height in urban terrain (U.S. EPA 1977).
68

-------
The following steps are an alternative for selecting a long-term monitoring
site, if modeling cannot be performed:
1.	Determine effective source height for neutral stability
using the EPA guidelines (U.S. EPA 1977).
2.	Use Figure 11 or 12 to determine the distance to the
maximum impact for neutral stability (class D).
3.	Select a site in the downwind direction of the prevailing
wind (all stabilities combined) at the distance of maximum
neutral stability impact.
The monitoring locations selected by the above procedures should be
reviewed and possibly revised by taking topographical effects into account.
This is particularly true in areas of complex terrain and where the meteoro-
logical data were not observed in the vicinity of the source. However, a
meteorologist should be consulted before making any significant change in
site selections. The following topographical influences should be considered:
§ Complex terrain results 1n air flow being channeled by
valleys, drained near steep terrain slopes, and modified
by mountain-valley circulation effects.
§ Large water bodies induce air to flow toward land during
the day and toward water at night.
• Urban developments induce air to flow toward city centers.
Finally, in selecting specific probe locations in the vicinity of a
selected monitoring location, the guidelines presented in the preceding
section should be followed.
69

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SECTION S
REFERENCES
Auer, A.H., Jr. 1978- Correlations of Land Use and Cover with Meteorological
Anomalies. J. Appl. Meteorol. 17:636-43.
9rodzinsky, R. 1982, Volatile Organic Chemicals in the Atmosphere: An
Assessment of Available Data. EPA Contract Number 68-02-3452, SRI
International, Menlo Park, California.
Bucon, H.W., J. Macko, and H,J, Toback. 1978. Volatile Organic Compound
(YOC) Species Data, EPA 450/3-78-113. U.S. Environmental Protection
Agency, Research Triangle Park, North Carolina.
Krost, K.J., E.D, Pel 1izzari, S.G. Walburn, S.A, Hubbard. 1982. Collection
and Analysis of Hazardous Organic Emissions. Anal. Chem. 54(4-):810-17.
Riggin, R.M. 1983. Technical Assistance Document for Sampling and Analysis
of Toxic Organic Compounds in Ambient Air. EPA-600/4-83-027, U.S.
Environmental Protection Agency, Research Triangle Park, North Carolina.
Singh, H.8., L.J. Sal as, R.E. Stiles, H. Shigei shi. 1982. Measurements of
Hazardous Organic Chemicals in the Ambient Atmosphere. SRI International,
Menlo Park, California.
Suta, B.E. 1979. Human Exposure to Atmospheric Concentrations of Selected
Chemicals. PB 81-193-278, Cress Report Mo. CRU-6780, SRI International,
Menlo Park, California.
Systems Applications, Inc. 1980. Human Exposures to Atmospheric Concentra-
tions of Selected Chemicals. San Rafael, California.
Turner, D.B. 1964. A Diffusion Model for an Urban Area. J. Appl. Meteorol.
3:83-91.
Turner O.B. 1970. Workbook of Atmospheric Dispersion Estimates. Report No.
AP-26, U.S. Environmental Protection Agency, Research Triangle Park,
North Carolina.
U.S. Department of Commerce. 1968. Climatic Atlas of the United States.
U.S. Government Printing Office, Washington, D.C.
U.S. Environmental Protection Agency. 1977. Guidelines for Air Quality
Maintenance and Planning, Volume	1Q(R): Procedures for Evaluating Air
Quality Impact of New Stationary	Sources. EPA 450/4-77-011, Research
Triangle Park, North Carolina.
70

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U.S. Environmental Protection Agency. 1978. Guideline on Air Quality
Models. EPA 450/2-78-027. Research Triangle Park, North Carolina
U.S. Environmental Protection Agency. 1982. Regional Workshops on Air
Quality Modeling: A Summary Report (Revised). EPA 4-50/4-82-015,
Research Triangle Park, North Carolina.
71

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APPENDIX A
RECOMMENDED MONITORING TECHNIQUES
This appendix consists of Tables 17 and 18 extracted from EPA Technical
Assistance Document (TAD) (EPA-600/4-83-027). Table A-l lists the most
widely used sampling and analysis methods for ambient air monitoring. A
discussion of the methods (also taken from the TAD) describes a logical
grouping of compounds that can be analyzed by the suggested methods.
Table A-2 is a list of 31 toxic organic air pollutants and the recommended
sampling and analytical methods from Table A-l.
Methods A-F (Table A-l) represent sampling and analysis approaches
for volatile hydrocarbons and halogenated hydrocarbons with boiling points
less than 200® C. The simplest approach (Method A) involves direct injection
of a gas sample onto a GC/FID or other detection system and is useful for
compounds more volatile than benzene. Higher boiling compounds can be
determined in some cases, although condensation onto the container surface is
a more significant problem as volatility decreases. Use of sensitive and/or
selective detectors such as ECO for halocarbons and P1D for aromatics (19) or
certain olefins can be of great value.
Method B involves cryogenic concentration of a whole air sample.
Preferably this approach 1s used as a field method so as to avoid sample
transport and storage problems, although laboratory analysis has been used
successfully (5). This approach 1s more time consuming but also much more
sensitive than the direct GC injection approach and can be used at the part
per trillion level in favorable cases (e.g., using GC/ECD or PID). Compounds
in the C2-Cj_q volatility range can be determined using cryogenic trapping.
A limited volume of air (<500 ml) can be sampled since condensed moisture
will plug the trap if greater air volumes are collected.
Methods C and D Involve the sampling of- 20 liters of air using Tenax (a
porous polymer adsorbent), thermal desorptlon of the adsorbed components, and
GC or GC/MS analysis. Method C is more comonly used and involves direct
desorptlon of the Tenax-adsorbed components onto the GC or GC/MS system.
Method 0 involves desorption of the components into an evacuated canister and
subsequent analysis of the canister contents. Method D offers the advantage
of replicate analysis of a single sample, but is somewhat less sensitive than
the former approach. Adsorptive losses of higher boiling compounds onto the
canister surface is another potential problem. An advantage of the Tenax
approach, relative to cryogenic trapping, 1s that water and other inorganic
atmospheric components are not retained. Storage of the organic components
in the resin-adsorbed state also tends to circumvent problems with adsorption
on container surfaces.
72

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TABLE A-l. SUMMARY OF SAMPLING AND ANALYTICAL METHODS FOR
ORGANIC COMPOUNDS IN AMBIENT AIR

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-------
TABLE A-l. (Continued)
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-------
TABLE A-l. (Continued)
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-------
TABLE A-l. (Continued)
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-------
TABLE A-l. (Continued)
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-------
TABLE A-2. SUMMARY OF SAMPLING AND ANALYSIS METHODS FOR
SELECTED TOXIC ORGANIC COMPOUNDS
Most Appropriate
Methods From	Specific
Compound	Table A-l	References	Comments
Acetaldehyde
Acrolein
Acrylonitrlle
Ally! Chloride
Benzyl Chloride
J.K
J.K
B.F
B,E,F
3.6
3
1
B,C or D
Carbon Tetrachloride
B,C or D
Compound very unstable, requires
immediate analysis or deriva ti zation.
Compound very unstable, required
immediate analysis or deriva ti zation.
NIOSH Method SI56 uses methanol as
desorption solvent. GC/NPD will
give improved sensitivity.
Compound is too volatile to allow use
of Tenax/thermal desorption approach.
NIOSH Method S116 uses benzene
solvent desorption with GC/FID
analysis.
Cryogenic trapping or Tenax adsorption
appear to be the best approaches.
Adsorption on XAD-2 may also be use-
ful . GC/P1D is a useful determinative
method.
Cryogenic trapping or Tenax adsorption
appear to be the best approaches.
Storage of samples in contact with
stainless steel surfaces can result
in rapid loss of this compound.
GC/ECI) is a useful method.

-------
TABLE A-2. (Continued)
Compound
Most Appropriate
Methods From
Table A-l
Specific
References
Comments
Chlorobenzene
Chloroform
Chloroprene
o-,m-,p-Cresol
p-Dichlorobenzene
Dimethylni trosamirie
Epichlorohydrin
B,C or D
B,C or D
B,C or 0
C,S,H (low
volume)
B(C or D
M
B,C or 0
4,7,17
4,7
3,21
7,17
16
Cryogenic trapping or Tenax adsorption
appear to be the best approaches.
GC/PID is a useful method.
Cryogenic trapping or Tenax adsorption
appear to be the best approaches.
GC/ECD is a useful determinative method
Cryogenic trapping or Tenax adsorption
appear to be the best approaches,
although very little data is available.
GC/PID is a useful determinative
method.
Either collection in sodium hydroxide
impinger, Tenax adsorption, or resin
adsorption/solvent extraction can be
used. GC/PID is a useful determinative
method.
Cryogenic trapping or Tenax adsorption
appear to be the best approaches.
Resin adsorption/solvent desorption
approaches can be used. GC/ECD or
P1D are useful determinative methods.
Adsorption on Thermosorb N/thermal
desorption appears to be the best
approach. GC/NPD may provide
sufficient selectivity in many cases.
Relatively little ambient air data are
available in the literature. Cryo-
genic trapping or Tenax adsorption
appear to be viable approaches.

-------
TABLE A-2. (Continued)
Most Appropriate
Methods From Specific
Compound	Table A-l	References	Comments
Ethylene dichloride
Ethylene Oxide
Formaldehyde
Hexachlorocyclopenta-
dlene
Maleic Anhydride
Methyl Chloroform
Methylene Chloride
B,C or D	4,7
A.B.E	1
J.K	3,6
C or D,H	20
(low volume
approach)
B.C or 0
B.F
N1trobenzene
B.C or 0
Cryogenic trapping or Tenax adsorption
appear to be the best approaches.
GC/ECD Is a useful determinative
method.
Compound too volatile to use Tenax
adsorption. Cryogenic trapping is
probably the best approach.
Compound very reactive. Requires
immediate analysis or stabi1ization.
Very little data available for this
compound in ambient air.
No suitable methods could be found.
Cryogenic trapping or Tenax adsorption
appear to he the best approaches.
GC/ECD is a useful determinative
method.
Cryogenic trapping, appears to be the
most useful approach. This com-
pound is not retained well by Tenax
or other polymeric adsorbents.
Adsorption on carbon molecular sieves
in place of Tenax is a useful approach,
laboratory contamination with methylene
chloride is a coninon problem.
Tenax adsorption is probably the best
approach. GC/ECD, PID, or NPD are
useful determinative methods.

-------
TABLE A-2. (Continued)
Most Appropriate
Methods From	Specific
Compound	Table A-l	References	Comments
N1trosomorpholine
Perchloroethylene
Phenol
M
B,C or D
C or S
Phosgene
22
4,7
3,6
18
PCBs
Propylene Oxide
B,C or D
See Dimethylnitrosamine. IIPLC may be use-
ful in place of GC for this compound.
Cryogenic trapping or Tenax adsorption
appear to be the most useful approaches.
GC/ECD is a useful determinative
method.
Trapping in basic implnger solution or
Tenax adsorption appear to be the best
approaches. GC/PID is a useful
determinative method.
This compound is highly unstable and
hence field determination is desirable.
A manual colorimetric method using
4-nitrobenzyl-pyridine appears to be
the best approach for routine analysis
(detection 1 imit **.0.05 ppm for 25
1 iter sample).
Adsorption of XAD-2 or polyuretharse foam
followed by solvent extraction and GC/
ECO analysis appear to be the best
approaches. PC8 fornulat ions are com-
posed of many individual compounds
and the method of quantification
required careful consideration.
Cryogenic trapping or Tenax adsorption
appear to be the best approaches,
although the Tenax approach should be
used with caution because of the low
breakthrough volume for this compound.

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TABLE A-2. (Continued)
Most Appropriate
Methods frora Specific
Compound	Table A-l	References	Comments
Toluene	B,C or D
Trichloroethylene	B,C or D
Vinylidine Chloride	B,C or D
(1,1-dichloroethane)
o-,m-,p-Xylene	B.C or D
4,5,7,9,19 Cryogenic trapping or Tenax adsorption
appear to be the best approaches.
GC/PID is a useful determinative
technique.
4,7	Cryogenic trapping or Tenax adsorption
appear to be the best approaches.
GC/ECD is a useful determinative
technique.
4,7	Cryogenic trapping or Tenax adsorption
appear to be the best approaches,
GC/ECO is a useful determinative
technique.
4,5,7,9,19 Cryogenic trapping or Tenax adsorption
appear to be the best approaches.
Adsorption on XAD-2 and solvent
extraction is also possible. GC/PID
is a useful determinative method.

-------
Major disadvantages of the Tenax adsorption approach is the potential
for artifact formation (e.g., by interaction of ozone with the resin) and/or
contamination. These factors tend to increase the background (blank) levels
relative to cryogenic trapping, thereby adversely affecting the detection
limit. The widely varying retention volumes for organic compounds on Tenax
requires careful consideration for each monitoring situation. A recent
report describes the Tenax adsorption process and gives retention volume data
for many organic compounds of interest (25).
Methods E and F involve adsorption of volatile, nonpolar compounds on
carbon based adsorbents followed by solvent extraction or thermal desorption
and GC or GC/MS analysis. Method E, adsorption of charcoal followed by
extraction with CS2 or other solvents, is the basis for many of the NIOSH
methods. Unfortunately this approach is not sufficiently sensitive for most
ambient air monitoring programs, although the use of selective detectors can
improve sensitivity for certain compounds.
Method F has been used to some extent for ambient air monitoring of
vinyl chloride and other volatile compounds. This method is similar to
Method 0, except that carbon molecular sieves are used in pi ace of Tenax.
Direct thermal desorption/GC analysis (analogous to Method C) could be
employed for carbon molecular sieves as well. A major advantage of this
approach is the strong retention of vinyl chloride and other highly volatile
materials. However, the high temperatures required for thermal desorption
from carbon based adsorbents can lead to degradation of strongly adsorbed,
nonvolatile and/or polar materials.
Methods G, H, and I represent approaches useful for the determination of
semi volatile or nonvolatile compounds (i.e., boiling points greater than 140° C).
Method G, while referenced as a PAH analysis method, is readily adapted for
the determination of many nonvolatile materials adsorbed on atmospheric
particulate material. Method I is referenced as a separate method for
tetrachloro-dibenzodioxins (TCDOs) which are currently of great environmental
concern. Highly specific cleanup and GC/MS steps are used to gain selectivity
for TCDDs using the method.
Method H represents as useful approach for PCBs, PCNs, organo-chlorine
pesticides and other semi volatile compounds which can occur in both the
particle and vapor state. Such compounds are not retained using conventional
high volume filtration techniques hence adsorbents such as XAD-2 or poly-
urethane foam (PUF) must be used in back of the filtration device. The
semi volatile components are then recovered from the adsorbent by sol vent
extraction. Tenax is less useful than XAD-2 or PUFs in this method since
many solvents wil1 partially dissolve Tenax.
83

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The remaining methods in Table A-l represent specialized techniques for
selected groups of compounds. Methods J and K are used for determination of
volatile aldehydes (Ci to Cg)« Method J involves formation of the DNPH
derivatives of the various aldehydes followed by reversed phase HPIC analysis,
whereas Method K captures the aldehydes as bisulfite addition products and
then employs a variety of colorimetric and GC analytical procedures for the
Individual aldehydes. Method J should generally be used if a wide variety of
aldehydes are to be determined or if interferences with the colorimetrie
methods are likely to be encountered. The determination of formaldehyde
using chromatropic acid, as in Method J» is a simple procedure and is very
useful for screening purposes, although negative and positive interferences
can occur.
Detection of alcohols in ambient air has not been of widespread interest
and no sensitive methods exist. Method L refers to a group of MIOSH methods
employing carbon adsorption and solvent desorption/GC analysis. These
methods are not useful below 100 ppm. Alcohols are not retained on porous
polymer adsorbents such as Tenax and are likely to decompose if carbon
adsorption/thermal desorption approaches are attempted. An analytical method
involving silylation of alcohols followed by cryogenic trapping of the
silylated derivative (as in Method 8} has been reported (23).
Nitrosamines are of considerable environmental significance because of
the toxicological hazard and potential for formation in various combustion
sources. Method M refers to an approach involving collection of the ni tro-
sami ne on a specially treated nylon adsorbent (thermosorb/N) and subsequent
analysis using GC with MS or thermal energy (TEA) detectors. The latter
detector is relatively specific for nitrosamines (16). Since both MS and TEA
are relatively expensive detectors, the less expensive GC/NPD approach may
preferable in relatively "clean" environments in which ultimate selectivity
is not necessary. Thermosorb/N minimizes the formation of nitrosamines on
solid adsorbents during sampling, which has proven to be a problem on
Tenax under certain sampling conditions.
Methods N-Q represent the best available methods for determining
aliphatic and aromatic amines. Nitrogen heterocycles containing no other
polar functional groups can usually be determined by one or more of the
methods described earlier for hydrocarbons, using nitrogen selective detectors.
Methods N and P represent MIOSH procedures for determining aliphatic and
aromatic amines, respectively. These methods involve adsorption of the
compounds on silica gel, elution with acid and GC/FID analysis. The adsorp-
tion of water reduces the capacity of the silica gel and limits the practical
sampling volume. Therefore, these methods cannot determine low ppb levels of
amines, although use of GC/NPD should increase the sensitivity somewhat.
HPIC with fluorescence, electrochemical, or UV detection (13) can improve the
detection limit for aromatic amines.
84

-------
Method 0 involves determination of volatile aliphatic amines {C1-C4)
by adsorption on alkali-treated silica (Porasil A) followed by thermal
desorption and GC/NPD analysis. This method is reported to achieve 1-5 ppb
sensitivity 1f the GC system is carefully conditioned (11), Method Q is a
similar approach using Tenax/thermal desorption for aromatic amines. However,
the thermal instability of many aromatic amines must be considered and may
limit the usefulness of this approach.
Relatively few analytical methods are available for determining acidic
compounds (with the exception of phenols) in ambient air. Phenol itself and
possibly cresols can be determined using a Tenax adsorption approach such as
Method D. Higher boiling phenols can be determined using a resin adsorption/
solvent extraction approach such as Method H. Method S represents a standard
method for phenols wherein the compounds are collected in a dilute sodium
hydroxide impinger and then steam distilled and analyzed by GC/FID or GC/MS.
less volatile phenols can be analyzed (without steam distillation) by HPLC
with fluorescences UV or electrochemical detection.
Volatile carboxylic acids such as a formic and acetic acid can be
determined (Method R) by collection in a dilute sodium carbonate impinger
followed by ion chromatographic (ICJ analysis {10). IC is a special form of
fon exchange HPLC wherein conductance detection is employed (mobile phase
buffer 1s removed prior to detection using a stripper column).
Su1table methods for determining sulfonic acids in air have not been
reported. However, collection 1n an aqueous 1mpinger followed by HPLC
analysis (14) appears to be a viable approach.
In order to provide the reader with some useful examples of appropriate
methodology. Table A-2 lists a group of toxic organic compounds of concern in
ambient air monitoring programs. The most appropriate methods for determining
these compounds, specific literature references, and additional analytical
considerations are presented in Table A-2. This information should be used
as guidance and will not be accurate for every monitoring situation.
The majority of the compounds in Table A-2 represent hydrocarbons,
volatile halogenated hydrocarbons, or semi vol atile halogenated hydrocarbons
which can be determined using conventional cryogenic trapping„ Tenax adsorption/
thermal desorption, or resin adsorption/solvent extraction approaches. A few
compounds (e.g., acrylonitrile, ally! chloride, ethylene oxide) are too
volatile to be captured on Tenax and require use of carbon adsorbents or
cryogenic trapping. Several of the compounds can be determined using the
procedures for aldehydes (e.g., formaldehyde, acetaldehyde, acrolein).
85

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REFERENCES
1.	NIOSH Manual of Analytical Methods, Parts 1-3. 2nd Edition,
National Institute for Occupational Safety and Health, Cincinnati,
Ohio, 1977.
2.	Annual Book of Standards. Part 26, Gaseous Fuels; Coal and Coke;
Atmospheric Analysis. American Society for Testing and Materials,
Philadelphia, Pennsylvania. (Published Annually).
3.	Methods of Air Sampling and Analysis, M. Katz, ed., 2nd Edition,
American Public Health Association, Washington, D .C., 1977.
4.	Kebbekus, 8.B., and J.W. Bozzelli. Collection and Analysis of
Selected Volatile Organic Compounds In Ambient Air. Proc. Air
Pollution Control Assoc., Paper No. 82-65.2. Air Poll. Control
Association, Pittsburgh, Pennsylvania, 1982.
5.	Holdren, M., S. Humrickhouse, S. Truitt, H. Westberg, and H. Hill.
Analytical Technique to Establish the Identity and Concentration
of Vapor Phase Organic Compounds. Proc. Air Poll. Control Assoc.,
Paper No. 79-52.2, Air Pollution Control Association, Pittsburgh,
Pennsylvania, 1979.
6.	Fung, K., and 0. Grosjean. Determination of Nanogram Amounts of
Carbonyls as 2,4-Dinitrophenylhydrazones by HPLC. Anal. Chem. 53,
1981. pp. 168-171.
7.	Krost, K., E.E. Pellizzari, S.G. Walbun, and S.A. Hubbard. Collection
and Analysis of Hazardous Organic Emissions. Anal. Chem. 54, 1982.
pp. 810-818.
8.	Jackson, M.D., and R.G. Lewis. Polyurethane Foam and Selected
Sorbents as Collection Media for Airborne Pesticides and PCBs. In
Sampling and Analysis of Toxic Organics in the Atmosphere, ASTM STP
721, American Society for Testing and Materials, Philadelphia,
Pennsylvania, 1980, pp. 36-47.
9.	VanTassel, S., N. Amalfitano, and R.S. Norang. Determination of
Arenes and Volatile Haloorganic Compounds in Air at Microgram per
Cubic Meter Levels by Gas Chromatography. Anal. Chem. 53, 1981.
pp. 2130-2135.	~~
10. 8odek, I., and K.T. Menzies. Ion Chromatographic Determination
of Formic Acid in Diesel Exhaust and Mine Air. In Chemical Hazards
in the Workplace, G. Choudhary, ed., Symposium Series 149, American
Chemical Society, Washington, Q.C., 1981. pp. 599-613.

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11.	Kuwata, K., Y. Yamazaki, and M. Uebori. Determination of Traces
of low Aliphatic Amines by Gas Chromatography. Anal. Chem. 52, 1980.
pp. 1980-1982.
12.	Bowen, B.E. Determination of Aromatic Amines by an Adsorption
Technique with Flame Ionization Gas Chromatography. Anal. Chem., 48,
1976. pp. 1584-1587.
13.	Lores, E.M., D.VJ. Bristol, and R.F. Moseman. Determination of
Halogenated Anilines and Related Compounds by HPLC with Electrochemical
and UV Detection. J. Chrom. Sci., 16_t 1978. pp. 358-362.
14.	Knox, J.H., and G.R. Laird. Soap Chromatography-A New HPLC Technique
for Separation of Ionlzable Materials. J. Chrom., 122, 1976. pp. 17-34.
15.	Harvan, D.J., J.R. Hass, J.I. Schroeder, and B.J. Corbett. Detection
of Tetrachlorodlbenzodioxins in Air filter Samples. Anal. Chem., 53, 1981.
pp. 1755-1759.	~~
16.	Rounbehler, D.P., J.W. Reisch, and D.H. Fine. Nitrosomlne Air Sampling
Using a New Artifact-Resistant Solid Sorbent System. In Sampling and
Analysis of Toxic Organics In the Atmosphere, ASTM STP 721, American
Society for Testing and Materials, Philadelphia, Pennsylvania, 1980.
pp. 80-91.
17.	langhorst, M.L., and T.J. Nestrick. Determination of Chloro-benzenes
in Air and Biological Samples by Gas Chromatography with Photoionization
Detection. Anal. Chem., 251, 1979. pp. 2018-2025.
18.	Ruggl e, R.M., G.G. Esposito, T.L. Gulvan, T.L. Hess, D. Lillian, G. Podolak,
K.G. Sexton, and N.V. Smith. Field Evaluation of Selected Monitoring
Methods for Phosgene 1n Air. Amer. Ind. Hyg. Assoc. J., 40, 1979.
pp. 387-394.	"
19.	Hester, M.E., and R.A. Meyer. A Sensitive Technique for Measurement
of 8enzene and A1ky1benzenes in Air. Env. Sci. Tech., 13, 1979.
pp. 107-109.
20.	Dillon, H.K. Development of Air Sampling and Analytical Methods for
Toxic Chlorinated Organic Compounds. NTIS Report No. PB80-193279, National
Institute for Occupational Safety and Health, 1980. p. 84.
21.	Iwansiya, Y., and T. Nishishita. Determination of Phenols in the
Atmosphere by Concentration Equ11ibrium-Sampling Gas Chromatography.
Bunseki Kagaku, 28, 1979. pp. 26-31.
22.	Goff, E.U., J.R. Coombs, D.H. Fine, and T.M. Baines. Determination
of N-Nitrosamines from Diesel Engine Crackcase Emissions. Anal. Chem.,
52, 1980. pp. 1833-1836.
87

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23.	Osman, M., H.H. Hill, M.W. Holdren, and H. Westberg. Vapor-Phase
Silylation of Alcohols for Air Analysis. In Advances in Chromatography,
A. Zlatikis, ed., Chromatography Symposium - University of Houston,
Texas, 1979. pp. 301-312.
24.	Air Sampling Instruments for Evaluation of Atmospheric Contaminants,
5th Edition, American Conference of Governmental Industri al Hygi eni sts,
Cincinnati's Ohio, 1978.
25.	Cox, R.D., and R.f. Earp. Determination of Trace level Grgartics in
Ambient Air by High Resolution Gas Chromatography with Simultaneous
Photoionization and Flame Ionization Detection. Anal. Chem., 54, 1982.
pp. 2265-2270.
88

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APPENDIX B
OBSERVATION OF DIURNAL VARIATIONS OF
SELECTED NONCRITERIA AIR POLLUTANTS
Data are presented for the following NCAP:*
Figure	Pollutant
B-l	Benzene
B-2	Carbon tetrachloride
B-3	Chlorobenzene
B-4	Chlorofonii
8-5	Methyl chloroform
B-6	Methylene chloride
B-7	Perchloroethylene
B-8	Toluene
B-9	Tricholorethylene
B-10	iu-,p-Xyl ene
* Reported by: Singh, H.B., L. J. Sal as, R.E. Stiles, and H. Shigeishi.
1982. Measurements of Hazardous Organic Chemicals in the Ambient Atmosphere,
SRI International', Menlo Park, CA.
89

-------

T
i
111
TtMl —
M L« AHCiUS, CA
|
s IS
i
u»10
9
II
i1 n n
to IS
TtlH* — hour
M ODrvcn, cs
25
T
I iii
1 I
. T I X
* _
i »
M Housrew, rx
T!Mf> -™ fteur
M STATEN ISLAND. VY
Figure B-l. Mean diurnal variation of benzene.
90

-------
1
&

Figure B-2. Mean diurnal variation of carbon tetrachloride at Staten Island, NY.
91

-------
1«
III
Figure B-3. Mean diurnal variation of chlorobenzene at Denver,
92

-------
Figure 8-4. Mean diurnal variation of chloroform at Phoenix,
93

-------
L !!
T t T T
T
!
i I
I T
• *
T i i
i
| 1W3
i
|t»
I
0 soo
-1
7
t
i I J
* i i
la*
TIMS — rteur.
U U3S ANCSLES, SA
to 13
HM€ — sour
HOtJSTOW, TX
r
r
r
t
i
ii

I i.
I
1 1S0S
41
\ s
„ J 1000
8 to
a

i *
_ T
. f
Tl*«( — tKSU?
(W PMCtNIX, A2
to 15
TTMI — new
w awvsR, ca
I
5
| 
-------

-_L
10	IS
TIME — how
W NOUSTCN. TX
- I
9	m
TIMS — now
(dJ PHOENIX. A2
I	1Q	15
TIME — how

-------
TIME — ftour
W PHOENIX. A2
2DOO
I
3 TOO
!
i tooo
1
8 aoo
1 ; I
*
T
»
i
10	15
TIME — now
(U DFJJveR. CO
MN
W PITTSBURGH. PA
B-7. Mean diurnal variation of perchloroethy]ene.
96

-------

1 [_
, m U
jp
S
I
u r
«r
T ! I T
; i -
i I 1 i
I i
i t 1 i
TIMS — hour
<«i LC8? ANdSLS. CA
J I 30
«P
it ! jP 33
10
Hi
>» *
t i
i •
i i i
* *
10	IS
TIME — hour
M OSNVER. CO
20
i I I

-------
TIME — hour
(at P«0*NIX. XZ
(U HOUSTON, rx
10	15
TIME — fsoof
(el D8KVSR, CO
s
I
!•
1 I
T
i 1 T
1 ,i f I
»	A
HM« — nam
t*J PITTSBURGH,
figure B-9. Mean diurnal variation of trich!oroethylene.
98

-------
X 10
II
TO	15
TIME — taur
(a) HOUSTOH, TX
—i
>
x
a
i®	— ®
TIME — hour
lb) STATED ISLAND, SSY
Figure B-10. Mean diurnal variation of m-,p-Xylene.
99

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APPENDIX C
METEOROLOGICAL DATA TABULATIONS AVAILABLE
FROM THE NATIONAL CLIMATIC DATA CENTER
Cities for which Stability Array (STAR) data tabulations are available
are listed alphabeticaTTy by date and by city within a state.* Additional
tabulations may be available since this compilation. For assistance on
orders contact:
Director
National Climatic Data Center
Federal Building
Ashevil1e, North Carolina 28801
* From: Changery, M.J., W.J. Hodge, and J.V. Ramsdel1. 1977. Index--
Summarized Wind Data. 8NWL-2220 WIND-11 UC-60, U.S. Department of Commerce,
National CIimatic Data Center, Asheville, NC.
100

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c.-l. EXPLANATION OF ENTRIES
CITY is the city or town name for the location at which the original
observations were taken. It may also be the name of a military instal-
lation.
NAME-TYPE is usually the airport or field name and/or service which
operated the station. If these had changed during the period summarized,
the name and/or service valid for the longest portion of the summary is
used. A few stations may have no identifying information.
Under NAME, commonly used abbreviations are:
-APT -
Ai rport
ATI -
Air Terminal
BD -
Building
CAP -
County Airport
CO -
County
FID -
Field
GEN -
General
GTR -
Greater
INt -
International
MAP -
Municipal Airport
MEM -
Memorial
METRQ-
Metropolitan
MN -
Municipal
RSI -
Regional
TERM -
Terminal
Under TYPE, conntonly used abbreviations are;
AAB -	Army Ai r Base
AAf -	Army Air Field
AAFB -	Auxiliary Air Force Base
AEPG -	Army Energy Proving Ground
AF -	Air Force
AFB -	Air Force Base
AFS -	Air Force Station
ANG8 -	Air National Guard Base
ASC -	Army Signal Corp
CAA -	Civil Aeronautics Administration
FAA -	Federal Aviation Administration
FSS -	Flight Service Station
LAWR -	Limited Airways Heather Reporting (Station)
MCAF -	Marine Corps Air Facility
MCAS -	Marine Corps Air Station
NAAF -	Naval Auxiliary Air Facility
HAW -	Naval Auxiliary Air Station
NAF -	Naval Air Facility
NAS -	Naval Air Station
NAU -	Naval Air Unit
NF -	Naval Faci1ity
NS -	Naval Station
PG -	Proving Ground
SAWR -	Supplementary Airways Weather Reporting (Station)
W8AS -	Weather Bureau Airport Station
WBO -	Weather Bureau Office
101

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ST is a two-letter code identifying each of the fifty states.
WBAN # refers to the five-digit number identifying stations operated by
United States Weather Services (civilian and military) currently or in
the past, A few stations have had no number assigned.
WMQ # refers to the five-digit block and station numbers assigned to U. S.
stations as authorized by the World Meteorological Organization. Many
stations with a WBAN # will have no corresponding WMO number.
LAT, LONG are the latitude and longitude of the station in degrees and
minutes. If the station changed coordinates during the period summarized,
the location reflects the site with the longest record.
ELEV is the elevation (above sea level) of the station in meters. Reported
station elevation was used if the barometric height above sea level was not
available. If an elevation*change occurred during the period summarized,
the elevation reflects the station height for the longest period of record.
PERIOD OF RECORD is the first and last month-year of the summarized period.
As an example, 01 38 - 12 44 1s read as January 1938 through December 1944.
SO WARY TYPE identifies each s unitary according to its format. Each format
is.similar to one of the 16 types presented in detail beginning on page 1-13.
StJMM FREQ is the surrmary frequency or the time period in which the summarized
data are presented. Abbreviations used are:
M - Monthly. Data for each calendar month combined and presented on
a monthly basis.
S - Seasonal. Data for the months December through February of the period
of record are combined into a winter season, surmarized and
presented on a seasonal basis. The months March-May, June-
Augusts and September-November are similarly sunwarized.
A - Annual. All data for the period summarized together.
MA - Monthly and Annual.
SA - Seasonal and Annual.
MS - Monthly and Seasonal.
MSA - Monthly, Seasonal, and Annual.
IYM - Individual Year-Month. Data are presented for individual months
of record.
SP - Special Period. The special period presented is described further
in the given summary's Tab ^/Remarks column.
102

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TAB f/REMARKS column contains additional identifying or explanatory
information. Many of the summaries produced by the Climatic Center
and Air Weather Service for a specific project are identified by a
tabulation number. A "T" followed by a 4 or 5 digit number identifies
a summary produced by the NCC. Simi1arly, a "TCL" with a number indi-
cates an AWS stannary. Not all summaries can be so identified. This
number is provided as an aid in requesting a specific tabulation.
Numbers following or in place of a tabulation number refer to remarks
listed beginning on page 1-9. These remarks are provided if additional
information describing a summary is necessary. Examples are summaries
with data for hourly or 3-hour periods, specified hours only, combined
stations, etc.
103

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C-2. REMARKS
This is a	list of descriptive remarks coded by number in the Tab ^/Remarks
column of	the index. Numbers missing were not used.
1.	Broken period
2.	3-hourly groups
3.	Day-night
4.	0600-1800 1ST only
5.	10-12 observations per day, all daylight hours
6.	By hours 00, 03,. 06, 09, 12, 15, 18, 21 1ST
7.	See microfilm for broken periods and format
8.	Includes flying weather conditions
9.	Part "G" only
10.	Hours 0600-1200 LST only
11.	May-November only
12.	Broken period - pre-11/45 data from Point Hope (Stn #26601 )
13.	Broken period by hourly groups
14.	Less 12/59
is!	Pre-1939 data from Tin City (Stn #26634)
1$.	Less 12/70
17.	0500-1600 LST only
18.	2-13 observations daily
19.	0700-1900 LST only
20.	Combined data for Douglas AAF (Stn #23001) for 11/42-11/45
and Douglas Apt (Stn #93026) for 11/48-12/54
21.	Part "A" only by hourly groups - combined data for Kinaman CAA
(Stn #93167) for 01/34-12/4] and Kingman AAF (Stn #23108) for
03/43-06/45
22.	For hours 0800, 1400, 1700 LST only
23.	Direction and speed by visibility, relative humidity 90% and/or
precipitation, and relative humidity >_ 90% and no precipitation -
August, October, and December only
24.	Part "A" only
25.	By 2-hourly groups
26.	Daylight hours only
27.	September-December only
28.	By hourly groups
29.	For 0900-1600 and 1700-0800 LST
30.	Period 01/37-03/38 for Indio (Stn #03105)
31.	Precipitation-wind tabulation for April-October
32.	By day and night hours on microfilm
33.	Periods: July 15-31, August 1-15 for 1000 and 1400 LST
34.	No data for 27 months
35.	See Edwards AFB
36.	Some data from Paso Rabies (Stn #23231)
37.	All observations by various stability classes
38.	See Moffett Field
39.	Also contains a contact wind rose
40.	Eight directions and calm
41.	Includes a percentage graph
104

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42.	1200 1ST observations only
43.	Some missing data
44.	Contains all weather, precipitation, and visibility <_ 6 miles
wind tabulations for day and night hours
45.	Also calltd 94A
46.	See Farallon Island SE
47A.	0100-0400 1ST
478.	0700-1000 1ST
47C,	1300-1600 LST
470.	1900-2200 1ST
47E.	0600-2200 1ST
47F.	0700 LST
47G.	1600 LST
47H.	0600-0900 LST
471.	1600-1800 LST
47J.	0700-0900 LST
47K.	1900-0600 LST
47L.	1000-1500 LST
47M.	1200-2000 LST
47N.	0800-2100 LST
47P.	1100-1300 LST
48.	Also contains bimonthly summaries
49.	Located in city file
50".	Three speed groups
51.	June, July, August - daylight hours only
52.	Special tables
53.	Pre-1944 data from Boiling AAF (Stn #13710)
54.	Also known as Chantilly, VA, FAA (pre-Dulles)
55.	See Andrews AFB, MO
56.	Data for 01/74 from Hemdon Apt (Stn #12841}
57.	See also Cape Kennedy AFB
58.	Tower data - 8 levels (3-150 m)
59.	June-August only
60.	Data for 09/42-09/45 from Carlsbad AAF (Stn #23008}
61.	Data after 07/53 from Key West MAS (Stn #12850)
62.	Data thru 1945 from Marianna AAF (Stn #13851)
63.	Contains 14 months of data from Morrison Field (Stn #12865}
64.	Contains graphical wind rose
65.	Tabulated by temperature and relative humidity intervals
66.	Seasonal by day and night hours
67.	Closed and instrument weather conditions only
68.	Less 01/49
69.	24 observations daily
70.	8 observations daily
71.	1 of 3 parts
72.	Tabulation by day and night hours for May 1 - September 30 and
October 1 - April 30
73.	Tabulated for December-March and April-November
74.	Data prior to 10/42 and after 10/45 from Sioux City Apt (Stn #14943)
105

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75.	For day - clear and cloudy and night - clear and cloudy conditions
76-	Also contains a ceiling-visibility tabulation
77.	0700-1900 LST only
78.	All weather and 2 relative humidity classes
79.	Summer season only - 1957 missing
80.	May, August-November only
81.	Includes separate wind rose for WS0
82.	Four speed categories
83.	Monthly tabulation for 0400 and. 1400 LST, seasonal tabulation for
all observations
84.	Some data from Presque Isle AF8 (Stn #14604)
85.	Four observations per day
86.	Semi-monthly periods
87.	1935 data from 8oston W8AS (Stn #14739)
88.	VFR, IFR, closed conditions
89.	Pre-03/1952 data from Paso Robles (Stn #23231)
90.	August 1-15 only for hours 1000 and 1400 LST
91.	Partial SMOS
92.	June, July only for hours 2200L - 0200L
93.	April thru December only
94.	Less April -1953 and 1960
95.	January, Aprils July, and October only
96.	Winter season only
97.	Part "C1 and "£" only '
98.	36 compass points
99.	Less October-December 1945 for a 2-hour period.after sunrise
100.	November 1951 substituted for November 1955
102.	For hour groups 07-09, 10-15, 16-18, and 19-06 LST and all
hours combined
103.	For hours 0100, 0700, 1300, and 1900 LST (individual and all
hours combined)
104.	Day and night hours, clear and cloudy conditions
106.	Pre-02/33 data from Albuquerque WBO (Stn #23073)
108.	Precipitation wind rose tabulation
109.	ATI observations by 6 hourly groups
110.	For ceiling less than 600 feet and/or visibility less than 1-1/2
miles - also an annual hourly summary
111.	Also summarized by month-hour for hours 0200 and 1400 LST
112.	Summari2ed by days 1-15 and 16 to end of month for day and
night hours
USA.	1300 LST
11SB.	0400 LST
115C.	1000 LST
1150.	1600 LST
USE.	2200 LST
115F.	0700 LST
115S.	0100 LST
115H.	1900 LST
117.	See Covington, Kentucky
118.	.Pre-04/32 data from Oklahoma City WBO (Stn #93954)
119-	May to October only
106

-------
120.	. Monthly for 1961-63, individual months 1-4/64
121.	Also contains day and night summaries
124.	Summary titled Scranton
125.	See Milkes-Barre
126.	December-February for 0730 and 1930 LST only
128.	Pre-12/44 data from Galveston AAF (Stn *12905)
129.	Data for 10/62-12/63 for Greenville-Spartanburg Apt (Stn t03870)
132.	February-Apri1 and June-September only
133.	Pre-03/43 data from English Field (Stn #23047)
134.	Post-10/66 data from Fort Welters
135.	Less 6/68
136.	For hours 00-23 and 07-22 1ST
140.	Also contains annual ceiling/visibility tabulation
141.	Less 0000 and 0300 LST
142.	See Killeen
143.	See Dugway PG
144.	Data for 1943-49 for Wendover AFB (Stn #24111)
145.	0400-1800 LST
146.	See Washington, DC - Dulles International Apt WBAS
147.	See Washington, DC - National Apt WBAS
149.	0700-1200 LST
150.	Tower data, year-month-level, month-!eve!, and month-level-hour
151.	Pre-11/41 data from Paine Field CAA (Stn #24222)
152.	10 observations per day - closed on weekends
153.	10 observations per day - wind speed estimated
155.	By 5°F tauperature intervals - with and without thunderstorms
157.	One speed group - greater than 14 knots
158.	Speed classes in Beaufort Force - mean speed by direction in mph
159.	Hourly groups for 0800-1600 LST
160.	Post-05/55 data from Forest Sherman (Stn #03855)
161.	By speed classes and 5°F temperature classes
162.	for all hours combined and for hours 0030 and 1230 individually
107

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-------
APPENDIX D
CHEMICAL PROFILES
Acetaldehyde 		121
Acrolein 		133
Acrylonitrile 		144
Ally! chloride 		157
Arsenic 		161
Asbestos 				168
Benzene 		180
Benzyl chloride 			189
Beryllium 				195
Cadmium 		208
Carbon tetrachloride 		217
Chlorobenzene 			225
Chloroform 		235
Chi oroprene 				245
Chromium 		249
Dioxin 		255
Epichlorohydrln 				262
Methyl chloroform 		270
Nickel 						274
Nitrobenzene 				280
Ni trosomorpholi ne 		285
Polychlorf nated bi phenyl s 		288
Toluene 		295
Trichloroethylene 		306
Vinyl chloride 		316
Vi nylidene chloride 		323
120

-------
Chemical Name
Acetaldehyde
CAS Number
75-07-0
Chemical Classification
A1 dehyde
Synonyms
Acetic aldehyde, aldehyde, ethanol, ethyl aldehyde
Physical/Chemical Properties
Description:
1.	Colorless liquid or gas with irritant, fruity taste
2.	Exceedingly volatile (flashes back)
3.	Readily oxidized in air, forming explosive peroxides
Boiling point:
20.2° C
Melting point:
-123.5° C
Molecular weight:
44.05
Chemical formula:
C2H4O
Vapor pressure:
740.0 mm Hg (20° C)
Refractive index:
n^° = 1.33113
Log partition coefficient (Octanol/H2O):
0.43
Sol ufai 1 i ty:
Infinitely soluble in hot H^O; freely soluble in
water, alcohol, ether, benzene, gasoline, solvent
naphtha, toluene, xylene, turpentine, oil and acetone
121

-------
Photochemical reactivity:
Effective ambient air decay rate: 7.3 x 10-5 s-1 (daytime)
No reaction toward O3
Atmospheric reactivi ty:
Transformation products: peroxyacetyl nitrate; formaldehyde
Reactivity toward OH: 4x butane
Reactivity toward photolysis: 0.5x formaldehyde
Major atmospheric precursors: hydrocarbons {C3+)
Formation reactivity: equilibrium concentration 5% NMHC
Densi ty:
0.7834 at 18° C/4° C
Chemical reactivity:
Highly reactive; exhibits general reactions of aldehydes
Sources of Emissions
Production/processing:
1.	Oxidation of ethylene
2.	Vapor phase oxidat1on and dehydration of ethanol or
of propane and butane
3.	Direct conversion of ethylene
Uses:
1.	Chemical intermediate, especially for manufacture
of acetic acid and peracetic acid
2.	Used in manufacture of synthetic resins, pesticides,
and pharmaceuticals
3.	Used to make rubber processing chemicals
4.	Used 1n coating operations in manufacturing of mirrors
5.	Hardening agent in photography
6.	Used in manufacturing of gelatin, glues, casein products
7.	Used as preservative in food products and leather
Tables D-l through D-6 and Figure D-l graphically present
acetaldehyde production, consumption, and emission data
122

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TABLE D-l. ACETALDEHYDE PRODUCERS
1978	1979
Capacity Production Geographical Location
Company	 Location	do" lb/yr)	(10^ lb/yrl	Latitude /Longitude
Celaneaa
lay City, TX
300
204
28
51
45/96
01
00

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600
408
29
37
17/95
03
SI
Texas Eastman
Lon^wirw, T%
500
340
32
25
55/94
41
06
Publicise? Industries
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65
44
35
S3
30/75
IS
ia
Shall Chemical
Meres, tA
	|
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50
00
11/TO
23
42
Total

1 470
1000





Total production distributed over individual sites based an sit® capacity compared to total
Industry capacity,'
Source: Systems Applications, Inc. 1980
TABLE D-2. 1978 ACETALDEHYDE END-USE DISTRIBUTION
Usage	Acetaldehyde Use
End Use	-	(%)	(million lb/yr?
Acetic acid
69
690
Peracetic acid
10
100
Pentaerythritol
8
80
Pyridenes
4
40
Glyoxal
4
40
1,3-Butyle.ne glycol
2
20
Miscellaneous
	3
30
Total
100
1000
Source: Systems Applications, Inc. 1980
123

-------
TABLE D-3. ACETALDEHYDE EMISSIONS FROM PRODUCTION SITES


Oissions (Jti/yr)

Total
Dniisions1
Cowman y
Locution
Process
Storaqc
Fugitive
(Ib/vr)
(H/seclb
Celanesa
any city, tx
16,510
5,915
2,650
55,080
0.79

Clear Lake, TX
93.025
11,830
5.305
110.160
1.S9
Tennessee Eastaan
Longview, TS
77,520
9, 8 GO
4,420
91,800
1. 32
PublicXer Industries
Philadelphia, PA
10,030
1,275
570
11.880
0.17
Shell chemical
Norco, LA
910
115
SO
1.080
0.02
Total

228,000
29,000
13,000
270,000

*Q«sed on the following emission factors [lb acetaldahyde essitted per lb produced) .
Process 0.000228 B - (derivad from scats air emission files)
Storage 0.000029 S - (derived tram state air emission files)
fugitive 0.000013 S - (derived [ran state air emission files)
Total 9.000270
b
Based on 8760 hr/yr operation.
Source: Systems Applications, Inc. 1980
TABLE D-4. 1978 ACETALDEHYDE NATIONWIDE EMISSIONS
Nationwide
Emissions
	Source	(Ib/yr)
Production	270,000
Acetic acid	2,801,550
Peracetic acid	450,000
Pentaerythritol	688,000
Pyridenes	300,000
Glvoxal	180,000
1,3-Butylene glycol	27,000
Miscellaneous*	137,400
Total	4,853,950
~Based on a weighted average of emission
factors for other user categories.
Factor: 0.00458 lb lost/lb used.
Source: Systems Applications, Inc. 1980
124

-------
TABLE D-5. ACETALDEHYDE EMISSIONS FROM END-USERS
Eraiaalons (lb/yr)	 Total Emissions
Company
IxJCdt ion
End-Use
Process
Storage
Fugitive
llb/yrj
(f/seel
Cc! .muse
Bay City, TX
fccetlc acid
!BOfBB0
22,440
10,200
213,520
3.01

Clear Lake, TX
fccetic acid
992,100
123,090
55,950
1,171,220
16,06
Easlm.ih
Ringsport, TO
Hectic acid
1.107,690
151,000
67,2 30
1,416,010
20.40
rue
fJuffalo, NY
Perjicctic acLd
135,000
7.330
7,670
150,000
2.16
lllfjh I'oint
High Point, «C
Peracetie acid
135,000
7,330
' 1,670
150,000
2.16
Union Cat bide
Taft, I.A
Pcracetic ncid
135,000
7.330
7,670
150,000
2.16
Cl> ] anose
Bishop, TX
Pcntaerythrltol
241,2 30
29,040
13,530
203,000
4.09
licrcul cs
Louisiana, flO
VentacrythrItol
151,510
16,480
B, 610
100,600
2.60
UtC
Set file, PA
Pentaerythri tol
B0,410
9,680
4,510
94,600
1.36
I'urstorp
To 1 ctia , Oil
Pcntaerythrlto I
100, (.50
i 3,200
6,150
129,000
1.66
Hcpara
Harriman, NY
I'y ridenes
108,460
10,880
8,160
127,500
1.B4
Rel 1 1 y
Indianapolis, IN
Pyridenes
146,740
14,720
11,040
172.500
2.48
Ajncrican Cyanamide
Charlotte, NC
Glyoxa1
81,000
4,400
4,600
90,000
1.30
Union Carbiile
Taft, I.A
Glyoxai
Bl,000
4,400
4,600
90,000
1. 30
Cc liSncso
Bishop, TX
1 ,3-Butylenc glycol
8, 135
0
065
9,000
0.13
Eastman
Rochester, NY
1 , 3-Butyl«ne flycol
8,IIS
0
865
; 9,000
0.13
Mai 1incVrodt
5x:isil , IIJ
1,3-Butylene flycol
a, 135
0
BG5
9,000
0.13
Total


3.802,155
424,210
220,185
4,446,550

Source: Systems Applications, Inc. 1980

-------
TABLE 0-6. EMISSIONS AND METEOROLOGICAL STATIONS OF SPECIFIC POINT SOURCES OF ACETALDEHYOE
*	+	EMISSIONS < CM/SEC)
NO.
COMPANY
SITE
LATITUDE
LONGITUDE
STAR
STATION
PLANT
TYPE
SOURCE
TYl'li
PH0CES3
STORAGE
FUGITIVE
'
CELANESE
BAY CITY, TK
2B
31
43
96-
01
eo
1292,1
1
I
.669744
2.604672
.nnni76
.323136
.03*1160
. I46HU0
2
CELANESE
CLEAR LAKE. TX
29
37
17
95
on
Sf
12906
1
1
*1
hi
¦ 1.339360
14.2117392
. 170332
1.77,2496
.076392
.003600
3
f.ast;l\n kodak
LONGVIEW. TX
32
23
S3
94
41
06
13972
n
1
I . I (62110
. 141904
.06U64n
4
s'smi.scsrEn
PI11 LADELI'll 1 A, PA
39
S3
30
75
12
in
13739

I
. 144432
.0 IUJ60
.000200
5
SMELL
IIOIVCO.LA
ao
00
S 1
90
23
42
1293(1
rs
*•*
1
.0 13104
. 001636
.000720
6
EASTMAN KODAK
KIMGSPOIVT, TO
36
a i
41
02
12

13077
3
fed
17»246736
2. 107216
.960112
7
rrx
BUFFALO, SIY
42
59
10
7(1
SO
30
14747
4
a
1.944000
.§00352
. 1 10440
.1
¦ 11 Ct!PO S HT
fllCII POINT. NC
as
09
10
no
00
37
93007
4
a
1 .94400®
.105532
. 1 10440
9
DM ION CARD IDE
TAFT. LA
27
50
00
97
27
00
111970
0
a
&
1 .944000
1. £66400
. 103332
.063360
. 1 10440
.066240
10
CELAHESE
BISHOP, TX
27
34
06
97
49
27
12925
0
4
7
3.473712
. 1 17144
.4 10176
0.
. 194032
.012436
1 !
ISEI6CULES
LOUISIANA, m
39
26
24
9 1
03
37
93909
7
4
2.2 10544
.266 1 12
¦.123904
12
IMC
SEIPLE, PA
40
30
21
75
ni
nn
14737
7
4
1. 137964
, 139392
.064944
ia
i-eisToup
TOI.EOO, 01!
41
43
10
03
31
20
94030
7
4
t.370960
. 196000
.000360
14
FEfAHA
1IARR 1 MAN, NY
41
16
40
74
on
24
14757
0
a
I .561024
. 153320
. 1 (7304
15
!'.?¦: 1LLV TAR
INDIANAPOLIS. IN
39
42
00
06
14
00
93019
0
D
2, S 13036
.21196ft
. 130976
16
AHKI1 CYAMAfllO
C1IARLOTTG, ISC
33
12
16
00
30
32
ottos
9
6
1 . 166400
.063360
I
,066240
17
kasthan kooaic
ROCHESTER, NY
43
12
0 1
77
37
Oft
14717
to
7
. 1 17144
e.
.012456
in
T!ALL 1 NCSCPOBT
I.ODI, NJ
40
32
36
74
OS
46
9474 S
go
7
. 1 17144
0.
.012456
7
Source: Systems Applications, Inc. 1980

-------
KEY TO TABLE D-6
* Plant Types:
Type 1:
Type
2:
Type
3:
Type
4:
Type
5:
Type 6:
Type 7
Type 8
Type 9
Type 10
Plant produces acetaldehyde and
acetic add
Plant produces acetaldehyde
Plant produces	acetic add
Plant produces	peracetic add
Plant produces	peracetic acid
and glyoxal
Plant produces	pentaerythritol
and 1,3-butylene glycol
Plant produces	pentaerythritol
Plant produces	pyr1denes
PI ant produces	glyoxal
Plant produces	1,3-butylene glycol
Type 1
Type 2
Type 3
Type 4
Type 5
Type 6
Type 7
t Source Types:
Acetaldehyde production
Acetic acid production
Peracetic acid production
Pentaerythritol production
Pyridenes production
Glyoxal production
1,3-bytylene glycol

-------
t
V
Figure D-l. Specific point sources of acetaldehyde emissions.
Source: Systems ApplIcations, Inc. 1980

-------
Storage:
Bulk storage outside in detached tanks provided with
refrigeration and inert gas blanket
Small container storage in detached noncombustible
buil di ng
Inside storage in standard flammable liquids storage
room or cabinet
Transportation:
Shipped in 1-quart glass pressure bottles, 5- to 55-gallon
metal drums, insulated tank cars and trucks, tank barges
Di sposition:
Liquid acetaldehyde may be disposed of by atomizing it in
a suitable combustion chamber
Materials damage:
Liquid acetaldehyde will attack some forms of plastics,
rubbers, and coatings
Sampling and Analytical Methods
(Compound very unstable. Requires immediate analysis or deri-
vation.)
1.	NIOSH Method S345
a.	Bubbler collection
b.	Derivative from Gi rard T. reagent
c.	HPLC
Detection limit:
170-670 mg/m3 at STP with 60 1 sample
Possible interferences:
Other volatile aldehydes
2.	Tentative method of analysis for low molecular weight ali-
phatic aldehydes in the atmosphere (Method K, Appendix A}
a.	Collect in 1% NaHSC>3 solution in midget impingers
b.	C2-C5 aldehydes measured by gas chromatographic/flame
ionization procedures
Detection limits:
0.02 ppm at sampling rates of 2 1/min over a 1-hr period
129

-------
3. Method J from Appendix A
a.	Collection in dinitrophenyl hydrazine (DNPH}
b.	Solvent extraction
c.	Reversed phase HPLC analysis
Detection limits:
1-5 ppb for a 40 1 sample
Possible interferences:
Reagents must be carefully prepared to avoid significant
contamination
Material Damage
Liquid acetaldehyde will attack some forms of plastics,
rubbers, and coatings
Permissible Exposure Limits
OSHA	ACGIH
TWA 200 ppm	100 ppm (180 mg/m3)
(360 mg/m3)
Ceiling	150 ppm (270 mg/m^)
TLV (odor)	2.3 ppm
Human Toxicity
Acute toxicity:
TC[_o by inhalation is 134 ppm; produces narcosis in
humans
Chronic toxicity
Mutagenicity--Mutagenesis/genetic toxicity testing ongoing
in FY83 {U.S. DHHS 1983)
130

-------
Other chronic toxicity:
81ochemical/eel 1ular/tissue effects, pharmacokinetics/
metabolism effects, and systemic/organ toxicity testing
ongoing in FY83 (U.S. DHHS 1983)
Acetaldehyde is an eye, nose, and throat irritant and
can cause skin burns and dermatitis
Bibliography
American Conference of Governmental Industrial Hygienists. 1982. TLVS,
Threshold Limit Values for Chemical Substances and Physical Agents in the
Work Environment with Intended Changes for 1982. ISBNO 936712-39-2.
Cincinnati, OH.
Deichmann, William 8., and Horace W. Gerarde. 1969. Toxicology of Drugs
and Chemicals. Academic Press, NY.
Fuller, B., J. Hushon, M. Kornreich, R. Quel 1ette, L. Thomas, and P. Walker.
1976. Preliminary Scoring of Selected Organic Air Pollutants. EPA-450/3-77-
008b. The Mitre Corporation. McLean', VA.
Hawley, Gessner G. 1977. The Condensed Chemical Dictionary, 9th ed.
Van Mostrand Reinhold Company, NY.
Katz, Morris, ed. 1977. Methods of Air Sampling and Analysis. Alpha
Intersociety Committee, American Public Health Association, Washington, DC.
Kirk-Othmer. Encyclopedia of Chemical Technology, 3rd ed. John Wiley and
Sons, New York, NY, Vol. 1, pp. 97-109.	
Macki son, Frank W., R. Scott Stricoff, and Lawrence J. Partridge, Jr.. 1981.
NIOSH/OSHA, Occupational Health Guidelines for Chemical Hazards. U.S.
Department of Health and Human Services, DHHS (NIOSH) Publication No, 81-123.
National Institute for Occupational Safety and Health. Rockvilie, MD.
Macki son, Frank W., R. Scott Stricoff, and Lawrence J. Partridge, Jr., eds.
1978. NIOSH/OSHA Pocket Guide to Chemical Hazards. DHEW (NIOSH) Publication
No. 78-210. Washington, DC.
McGraw-Hi11, Inc. 1977. McGraw-Hill Encyclopedia of Science and Technology.
New York, NY, Vol. 1.
National Fire Protection Association. 1981. National Fire Codes, A Compila-
tion of NFPA Codes, Standards, Recommended Practices, arid Manuals. Vol. 13.
NFPA. Quincy, MA.
131

-------
Proctor, Nick W., and James P. Hughes. 1978. Chemical Hazards of the Work-
place. J.B. Lippirscott Company, Philadelphia, PA.
Riggin, R.M. 1983. Technical Assistance Document for Sampling and Analysis
of Toxic Organic Compounds in Ambient Air. EPA-60O/4-83-027. Battel 1e
Columbus Laboratories. Columbus, OH.
Systems Applications, Inc. 1980. Human Exposure to Atmospheric Concentra-
tions of Selected Chemicals, Vol ."X PB81-193252. Systems Applications,
Inc., San Raphael, CA.
U.S. Department of Health and Human Services. 1983. National Toxicology
Program: Review Qf Current DHHS, DOE, and EPA Research Relate3~tcTToxicology.
NTP-83-001. National Toxicology Program. Research Triangle Park, fclC.
U.S. Department of Health, Education and Welfare. 1977. NIOSH Manual of
Analytic Methods, Vol. 5. DHEW {NIOSH) Publ. No. 79-141, Cincinnati, OH.
U.S. Department of Labor. 1981. General Industry, OSHA Safety and Health
Standards (29CFR1910). Occupational Safety and Health Administration.
Washington, DC.
U.S. Department of Transportation. 1978. Chemical Hazards Response Infor-
mation System (CHRIS) Hazardous Chemical Data. Coast Guard, Washington, DC.
132

-------
Chemical Name
Aero lei n
CAS Number
107-02-8
Chemical Classification
Aldehyde (unsaturated)
Synonyms
Acraldehyde, acrylic aldehyde, ally! aldehyde, 2-propenal,
ethylene aldehyde, acrylaldehyde
Physical/Chemical Properties
Description:
Colorless to yellowish, watery, volatile liquid;
powerful lacrimator
Boiling point:
52.5° C
Melting point:
-86.95s C
Molecular weight:
0 6 a 06
Chemical formula:
C3H4O
Vapor pressure:
288.2 mm Hg at 25° C
215 ran Hg 20° C
Refractive index:
n*° = 1.4013
Solubility:
Very soluble in water {200 g/1 at 20° C) and many organic
liquids
133

-------
Photochemical reactivity:
Effective ambient air decay rate: 1.6 x 10"^ (daytime)
5.0 x 10~6 s~* (nighttime)
Reactivity toward: OH is 0.5x butane
O3 is 0.5x propylene
photolysis is 5x formaldehyde
Vapor density:
1.94 (air = 1)
Density:
0.84 g/cm3 at 20° C/4S C
Chemical reactivity:
Extremely reactive with oxidizing materials; can be stored
only in the presence of stabilizers (0.1% hydroquinone);
atmospheric oxygen, alkalies, mineral acids and peroxides can
trigger violent polymerization reactions
Environmental Fate
Total release rate of acrolein to the environment is not known.
Fugitive acrolein emissions come from industrial processes, and
acrolein is formed in the environment by burning tobacco, forest
fires, and by heating fats or glycerine
Sources of Emi ssions
Production:
1.	Pre-1959: vapor phase concentration of acetaldehyde
and formaldehyde
2.	Post-1959: direct catalytic vapor phase oxidation
of propylene (or allyl alcohol)
3.	Heat glycerol with magnesium sulfate
4.	Synthesized from propylene with bismuth-phosphorous-
molybdenum catalyst
Uses:
1.	Unisolated acrolein is an intermediate in the production
of acrylic acid and its derivatives
2.	Refined, or isolated acrolein end-uses:
a.	Production of synthetic glycerin
b.	Methionine and methionine hydroxy manufacture
(poultry feed supplements)
134

-------
c.	Used as fungicide to prevent slime (especially in
paper industry)
d.	Denaturant in alcohol
e.	Tissue fixative
f.	Used in leather tanning
g.	Aquatic herbicide and to control growth of
microbes in feed lines of wastewater treatment
and in liquid fuels
h.	Used to make tear gas
3. Present in:
a.	Smog
b.	Fuel combustion products
c.	Woodfire smoke
d.	Cigarette smoke
Tables D-7 through D-ll and Figure D-2 graphically present
acrolein production, consumption, and emission data
Storage:
Uninhibited acrolein 1s not to be stored under any
circumstances. Outside or detached storage preferable.
Inside storage in a standard flammable liquids storage
room or cabinet. No alkaline or oxidizing materials are
to be stored with acrolein
Di sposltion:
Acrolein wastes occur 1n both manufacturing and process-
ing plants
Nonreusable acrolein is contained in waste gases and pro-
cess water from synthesis plants or occurs in the form of
defective batches and superposed reserves
Aqueous wastes with low concentrations of acrolein are
usually neutralized with sodium hydroxide and fed to a
sewage treatment plant for biological secondary treatment
Concentrated wastes are reprocessed whenever possible or
burned in special waste incinerators
Sampling and Analytical Methods
1. NIOSH Method PSCAM 118, "Acrolein in Air"
a. Col lection in midget impingers containing the
absorbing solution or reagent
135

-------
TABLE 0-7. PRODUCTION OF ALLYL CHLORIDE, EPICHLOROHYDRIN, AND ACROLEIN
LftS rf©tiwetI "J78 csti*ac*4 rjp^cUy
	m ibi 	 	iA iu
Sourct
U>C Jtlan
Ak ly 1
CftleriHt *
rpichjor^-
by«1rtn,
Acrolein
Al lyj
CMor id*
£fj i eft loro-
Ac J"5 lei
Dm» Cfic"lCdl Co.

m
If*®

I&5
IM

Shell Co.
Prer Par*, T1
n


li*
1 tO

S*ell Cbnieil Co.
N9VCO, 1*6
71
1|
34
ill
no
IS
C»rh(dt C9r0.
T*ft* U


32


*0
Ce!#**«• Cor*«
CU*r U»k«, T7


1*


L K 7
iKi I1a«s Cd«
&Hr r»r*, ns


14*


D
U*lom C:
5,3:30
0
44S
S,96;c
0 * ZSq
itahm and Hats
Dem: Park, 7X
3,250
0
730
9,7 30"
Z ~ I 41
Onion Cariidt
Taft, LA
4,530
0
365
4.395C
3,371
Total

69,700
0
6,600
76.300

on 37SO ht/yr operation.
b
Isolated acrolein emission facto? (lb lose per lb prcducac).
'Process
Starage
Fugitive
Toea 3.
0.00110
0
o.aooi:
o.ooi::
A - Derived from si*.« visit data
A - Derived frcs* site visit data
A - 3erived	site »is;: iAza
Unxsolatad aersiai.n 
-------
TABLE 0-9. 1978 ESTIMATED ACROLEIN NATIONWIDE EMISSION LOSSES
Estimated National
Emissions
'Source (Ib/yr)
Production

Acrylic acid intermediate
20,640
Refined acrolein and glycerin
55,660
Chemical intermediate*

Methionine
24,200
Miscellaneous
2,420
Total
102,920
'Based on emission factor of 0.00121 determined for
isolated acrolein production.
Source: Systems Applications, Inc. 1980

TABLE D-10. 1978 ACROLEIN CONSUMPTION
BY END-USE
Usage
End-Use ' ¦ <%)
End-Use
Consumption
(M lb)
Acrylic acid and esters 87
30 B
Glycerin 7
24
Methionine and methionine 6
hydroxy analogue
20
Miscellaneous >1
	2
Total 100
354
Source: Systems Applications, Inc. 1980
137

-------
TABLE D-ll. EMISSIONS AND METEOROLOGICAL STATIONS OF SPECIFIC POINT SOURCES OF ACROLEIN
'	*	4.	EWIPS ions
STAn plant souncc —			
COffPAflV	SITK	LATSTUOF. LONCITUOK STATION TVTK TVTF. PROCESS RTOHACK FWtTrVE
1
F1CEIX
NORCO. LA
an
on
I §
090
23
42
i2Mn
l
I
.000160
A.
.030016
•»
union cAnnine
TAFT, LA
21
an
on
000
27
00
13970
u
S
'1
*<
.0404018
0.
0.
.034fU0
. ohti jnft
3
CELArtraE
CLRAtt LAKE. TX
2<»
37
17
A93
63
3 I
12406
a
2
¦ ¦ .A794nn
A.
.6*64*0
4
iimmAHO Haas
OEEH PATUC, TX

43
an
893
06
3»
12906
n
B*
. 130320

.1103 12
3
dccussa
¦nrcoiKm. AL
no
33
06
nnn
io
an
o.i nan
4
a
.079200
a.
.007920
6
f»APP
LOO I, NT
40
52
an
074
06
S 4
9474 1
4
si
.030400
0.
.007920
7
DIJS'OflT
ncAiirroNT. tx
30
on
31
694
oi
40
12917
4
a
.079200
o.
.007920
0
mis AH TO
TtlTltO, WV
an
24
2 ft
ant
3 1
2fs
tnn66
4
3
.079200
0.
.007920
* PI ant Types:
Type 1: Plant produces refined acrolein
Type 2: Plant produces refined acrolein and acrylic add
Type 3: Plant produces acrylic acid and acrolein Is the Intermediate
Type 4: Plant produces methionine
t Source Types:
Type 1: Refined acrolein production
Type 2: Acrylic acid production
Type 3; Methionine production
Source: Systems Applications, Inc. 1980

-------
\
(
Y-

u
* a ¦ ^ - -J j. *y ' " 11
Figure D-2. Specific point sources of acrolein emissions.
Source: Systems Applications, Inc. 1980

-------
b.	Complexation In presence of mercuric chloride
c.	Col or1metric analyses
Detection limits:
1-30 ug/10 ml
Possible interferences:
Slight interference from dienes
Samples must be analyzed soon after collec-
tion doe to 2-hour limit on color development
2.	NIOSH Method PSCAM 211, "Acrolein in Air."
a.	Collection in midget impingers with 1% aqueous NaHS03
b.	Reaction with 4-hexylresorcinol
c.	Colon'me trie analyses
Detection limits:
0.01 ppm/50 1 air sample
1-30 ug/10 ml sample
Possible interferences:
Slight interferences from dienes.
Samples should be analyzed soon after collec-
tion, unless refrigerated (for up to 48 hours)
3.	Method J from Appendix A
a.	Collection in dinitrophenylhydrazine (DNPH)
b.	Sol vent extraction of DNPH derivatives
c.	Reverse phase HPLC analysis
Detection limits:
1-5 ppb (40 1 sample)
Possible interferences:
Blank 1evels of aldehydes (usually formaldehydes)
will usually determine the detection limits
Reagents must be carefully prepared to avoid
significant contamination
Analysis within 24 hours is recommended
140

-------
Materials Damage
Contact of acrolein with oxidizing agents, acids, alkalies,
and ammonia may cause fires and explosions
Permissible Exposure Limits
OSHA
ACGIH
Ceiling
Odor Threshold
TWA
0.1 ppm
(0,25 mg/m^)
0.1 ppm (0.25 mg/m^)
0,3 ppm (0.8 mg/m3)
0.2 to 15 ppm reported
Human Toxicity
Acute toxicity:
The LC|_q for inhalation (humans) is 153 ppm/10 minutes.
Acrolein is a severe pulmonary irritant and 1acrimating
agent. As a liquid, acrolein causes severe corrosive
burns on the skin and mucous membranes
Chronic toxicity:
Carcinogenesis--Carcinogenesis testing to be completed by FY83
(U.S. DHHS 1983)
Other chronic toxicity:
Acrolein is on test in FY83 for biochemical, cellular,
and tissue effects, and for pulmonary toxicity (U.S. DHHS
1983)
Acrolein causes 1acrymation and respiratory tract irritation
and can cause CNS damage
Bib!iography
American Conference of Governmental Industrial Hygienists. 1982. TLVS.
Threshold Limit Values for Chemical Substances and Physical Agents in the
Work Environment with Intended Changes for 1982. ISfiNO. 936712-39-2.
Cincinnati, OH.
Oeichmann, William B., and Horace W. Gerarde. 1969. Toxicology of Drugs
and Chemicals. Academic Press, NY.
Federal Environmental Agency (Berlin West), Waste Management Division,
1976. Report Number NATO/CCMS Rpt. 55. ¦ EPA:PB270591.
141

-------
Fuller, B., J. Hushon, M. Kornreich, R. Quel 1ette, L. Thomas, and P. Walter.
1976. Preliminary Scoring of Selected Organic Air Pol"lutants. EPA-450/3-77-
008b. The Mitre Corporation. McLean, VA.
Hawley, Gessner G. 1977. The Condensed Chemical Dictionary, 9th ed. Van
Nostrand Reinhold Company, NY.
Katz, Morris, ed. 1977. Methods of Air Sampling and Analysis. Alpha Inter-
society Committee, American Public Health Association, Washington, DC.
Ki rk-Othmer. Encyclopedia of Chemical Technology, 3rd ed. John Wi1ey and
Sons, New York, NY, Vol. I, pp. £7?-92.
Mackison, Frank W., R. Scott Stricoff, and Lawrence J. Partridge, Jr., eds.
1981. NI0SH/0SHA Occupational Health Guidelines for Chemical Hazards.
DHHS (MlOSH") Publication No. 81-123. (J".S'." Department of Health' and' Human
Services, National Institute for Occupational Safety and Health. Rockville,
MD.
Mackison, Frank W., R. Scott Stricoff, and Lawrence J. Partridge, Jr., eds.
1978. NIOSH/OSHA Pocket Guide to Chemical Hazards. DHEW (NIOSH) Publication
No. 78-210. Washington, DC.
McGraw-Hill, Inc. 1977. McGraw-Hi11 Encyclopedia of Science and Technology.
New York, NY.
National Fire Protection Association. 1981. National Fire Codes, A Compila-
tion of NFPA Codes, Standards, Recommended Practices, Manuals. Vol. 13.
NFPA. Quincys MA.
Proctor, Nick W., and James P. Hughes. 1978. Chemical Hazards of the Work-
place. J.EL Lippincott Company, Philadelphia, PA.
Riggin, R.M. 1983. Technical Assistance Document for Sampling and Analysis
of Toxic Organic Compounds in Ambient'AiEPA-600/4-S3-027. ' Battelle
Columbus Laboratories. Columbus, OH. ~
Sittig, Marshall. 1980. Priority Toxic Pollutants. Noyes Data Corporation.
Park Ridge, NJ.
Systems Applications, Inc. 1980. Human Exposure to Atmospheric Concentrations
of Selected Chemicals Vol. I. PB81-193252. Systems Applications, Inc.,
San Raphael, CA.
U.S. Department of Health, Education, and Welfare. 1977. NIOSH Manual of
Analytic Methods, Vol 1. DHEW (NIOSH) Publ. No. 77-157-A" Cincinnati,
w.	

-------
U.S. Department of Health and Human Services. 1983. National Toxicology
Program: Review of Current DHHS, DOE, and EPA Research Related to Toxicology.
NTP-83-001. National Toxicology Program. Research Triangle Park, NC.
U.S. Department of Labor. 1981. General Industry, QSHA Safety and Health
Standards (29CFR1910). Occupational Safety and Health Administration.
Washington, DC.
U.S. Department of Transportation. 1978. Chemical Hazards Response Informa-
tion System (CHRIS) Hazardous Chemical Data. Coast Guard, Washington7~Dr7
U.S. Environmental Protection Agency. 1976. Disposal of Hazardous Wastes,
Manual on Hazardous Substances in Special Wastes. NATO/CCMS Report 5Jj.
Washington, DC.
U.S. Environmental Protection Agency. 1980. TSCA Chemical Assessment Series,
Chemical Hazard Information Profiles (CHIPS)T EPA-560/11-80-011, Office
of Pesticides and Toxic Substances, Washington, DC.
143

-------
Chemical Name
Acrylonitrlle
CAS Number
107-13-1
Chemical Classification
Substituted ally]; nitrile
Synonyms and Trade Names
ACN, aery Ion, acrylonitrlle (DOT), acrylonitrlle (8CI),
acrylonitrlle monomer, AN, carbacryl, cyanoethylene, ENT 54,
Fumi-grain, Millers Fumigrain, propenenitrile, 2-propenenitrile,
TL 314, VCN, Ventox, vinyl cyanide
Physical/Chemical Properties
Description:
Volatile, colorless liquid; explosive, flammable; charac-
teristic odor resembling peach seeds
Boiling point:
77.5° C
Melting point:
-83.5° C
Molecular weight:
53.06
Chemical formula:
C3H3N
Vapor pressure:
113.8 nm Hg at 25° C; 83 mm Hg at 20° C
Vapor density:
1.83 (air = 1.0)
Density:
0.8060 at 20° C/4° C
144

-------
Refractive index:
nf}5 = 1.3888
Solubility:
Acrylonitrile is moderately soluble in water
(50 g/1 at 20° C); it is soluble in acetone and
benzene, and is miscible with ethanol and ether
Octanol/water partition coefficient:
-0.92
Photochemical reactivity:
Olefins generally, as a class, enhance atmospheric
oxidation reactions. Acrylonitrile has been found
to be reactive, with an atmospheric half-life of
9-10 hours
Density:
806 g/1 at 20° C
Chemical reactivity:
Reacts with oxidizing materials. Cannot be stored
without the addition of polymerization inhibitors
Environmental Fate
The atmospheric half-life of acryl onitril e is sufficiently
long to allow for its atmospheric transport, especially
when coupled with its high volatility and its low solu-
bility in water
Sources of Emissions
Production:
1.	S0HI0 process: oxidation of propylene in the
presence of ammonia (ammoxidation of propylene)
using either a bismuth phosphomolybdate or
uranium-base catalyst (the only process used
commercially in the United States}
2.	Addition of hydrogen cyanide to acetylene using
cuprous chloride catalyst
3.	Catalytic reaction of propylene with nitrous
oxide
145

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4.	Reaction of ethylene oxide with hydrogen cyanide
followed by catalytic dehydrogenation of ethylene
cyanohydrln
5.	Ammoxidation of propane
Uses:
1. Acrylic and Modacrylic F1bers
More than 60% of these fibers are used in apparel.
Carpeting is the second largest use. Home furnish-
ing uses include blankets, draperies, and upholstery.
Industrial uses Include sandbags, filter cloths,
tents, and tarpaulins. The fibers are also used
in synthetic hair wigs-
2. ABS Resin
Major markets are pipes and pipe fittings, and auto
motive components. Other important markets are
large appllances, housing for business machines and
telephones, recreational vehicle components, toys,
sporting goods, sheeting material for luggage, and
food contai ners
3.	SAN Resin
Primary uses are for drinking tumblers and other
houseware items, for automobile instrument panels,
instrument lenses, and food contai ners
4.	Nitrile Elastomers
Major-uses are in rubber hose, seals, gaskets, latex,
adheslves, polyvinyl chloride blending, paper coatings,
and pigment binders
5.	Adipo nitrile
It is hydrogenated to hexamethylenediamine, which
is used to produce nylon
6.	Acrylamide
The largest use is in the production of polyacry-
lomides for waste and water treatment flocculants.
Other acrylamide products are used to aid sewage
dewaterlng, and for paper-making strengthened and
retention aids
7.	N1 trile Barrier Resins
They are used in the manufacture of non-beverage
containers for glue, nail polish, correction fluid,
air freshener, contact lenses, tooth brushes, and
combs
146

-------
The major sources of acrylonitrile emissions in the United
States are monomer and polymer production facilities. The
estimated acrylonitrile emissions from these facilities are
shown in Tables 0-12 and D-13. Table D-14 gives spill hazards
for acryl onitrile
TABLE D-1Z. ESTIMATED ACRYLONITRILE EMISSIONS FROM
MONOMER AND POLYMER PRODUCTION FACILITIES
Estimated acrylonitrile
Production facility	emissions (Mg/yr)*
Monomer	802
A8S-SAN resin	1424
Acrylic and modacrylic fiber	1276
Nitrile elastomer	295
Adiponitrile	59
3856
* Mg - millions of grams
Source: U.S. EPA 1982
TABLE D-13. MONOMER RESIDUE IN END-PRODUCTS
OF ACRYLONITRILE
Monomer
residue
Product name	Usage	(ppm)
Acrylic and
Fabric
<1
monacrylic fiber


Hycar
Rubber
0-100
Kraiastic and paracril
Resin
50
UCAR-380
Latex
250
UCAR-4358
Latex
750
Acrylamide monomer
See Figure 1
50-100
Polyacrylamide
See Figure 1
1
ABS Resin
Packaging
24
SAN Resin
Containers
3-7
SAN Resin
Containers
2-5
Source: U.S. EPA 1982
147

-------
Storage:
Outside or detached storage preferable
Inside storage in standard flammable liquids storage
room or cabinet
Uninhibited acryloni tril e not to be stored under any
condition
Outside tanks should be above-ground and surrounded by
dikes of sufficient capacity to hold entire tank con-
tents
Transport:
TABLE D-14. HAZARDS OF ACRYLONITRILE TRANSPORTATION*
Hazard parameter
Barge
Truck
Rai 1
Spill Pool radius (m)
61.0
17.1
31.7
Hazard radius (m)
122
38.4
68.3
Hazard area (m^)
46,700+
4,450#
13,400#

5,460**


Relative exposure (%)--



urban/rural
8/92
23/77
27/73
Expected number of annual



spills
0.0117
0.063
0,17
Probability of .ignition



following spill
0.30
0.25
0.40
*	Calculations are based upon the assumption that each mode
of transportation handles 100 percent of the quantity
shipped, and that a total of 73,000 Mg per year of acrylo-
nitrile is shipped between two points
+ Area affected by spills into water which ignite. Assumes
entire spi11 quantity contributes to burning pool
#	Area affected by spi11s on land which ignite. If no
ignition occurs, the exposed land area is equivalent
to the pool spill area (r2 spill)
** For spi11s into water which do not ignite. The water
toxicity hazard distance (meters) measured downstream
from spi11 location for a 152 m wide, 3.05 m deep river
flowing at 0.70 m/s. Assumes vertical dispersion rate at
0.30 m/min unti1 uniform mixing is achieved throughout the
entire depth of the river. Thereafter, plug flow is assumed
with no synergistic or antagonistic reaction between
the pollutant and the receiving body of water. For this
situation, the entire spill quantity contributes to water
Source: U.S. EPA 1982
148

-------
Disposition:
Acrylonitrile wastes are to be expected only in petro-
chemical pi ants and the frequently attached polymer
production. Due to their quantity, they require special
disposal provisions
Aqueous wastes with low contents are flushed into the
sewerage system and biologically treated in sewage
treatment plants. However, it will first have to be
determined whether other constituents are present which
could interfere with the degradation process. Undegraded
remainders can be removed by filtration through activated
charcoal
Concentrated wastes, which are mostly of a very complex
nature, are turned over to special waste disposal facil-
ities, if reproccessing appears uneconomical
Tables D-15 through D-17 give monitor!ng and analysis data
for acrylonitrile
Sampling and Analytical Methods '
1.	NIOSH method P&CAM 202 "Acrylonitrile in Air"
a.	adsorption on Carbosieve 8
b.	desorption with methanol
c.	gas chromatographic determination
Detection 1imi ts:
40-1100 mg/m3 in a 20 1 sample
Possible interferences:
High humidity decreases 1oading capacity of the
sorbent tube
Any compound that has the same retention time as
acrylonitrile
2.	NIOSH method S156 for "Acrylonitrile"
a.	adsorption on charcoal
b.	desorption with methanol
c.	gas chromatographic analysis
Detection limit:
17.5-70.0 mg/m3 with a 20 1 sample
Probable useful range is 4.5-13.5 mg/m3
149

-------
TABLE D-15. ATMOSPHERIC MONITORING DATA FOR ACRYLONITRILE
Sit*

Produot
Distance (ka)
No. of Samples
Collected

Concentration of Acrylonltrlle(m/b^)



of Collection
fro® Plant*
High
Low
HaxlMl Average
Aaarlcan Cyan*
New Orleans,
uald,
LA
Aorylonltrlla
0.6-1.8
5
13.6
<0.1
2.6
American Cyanaald,
Linden, HJ
Aorylonltrlla
0.5*1.8
6
15.9
<0.1
3.2
Konssnto,
Texas City,
TI
Aorylonltrlla
0.7-2.6
7
e.9
<0.3
3.2
Honaanto,
Decatur, AL

Aoryllo and
Nodecrylla Fibers
1.3-5.0
5
t.2
<0.1
1.2
IhiPoAt,
Logoff, SC

Aoryllo Fibers
0.7-2.2
8
1.1
<0.1
0.3
DuPont,
Wayneaboro,
U
Aoryllo and
Hodacryllo Flbera
0.3-0.9
6
7.0
<0.2
1.3
Borg-Varner,
Washington,
Iff
ABS/SAN Realns
0.5-1.3
1
329.0
<0.2
01.0
Goodrich,
Louisville,
mr
lltrlle Elaatoawra
> ABA/SAN Resin
0.^-3.0
t
«-3
<0.2
1.2
Honaanto,
Addyston, OH
ABJ/3AN Resins
0.3-1.0
5
1.1
<0.2
0.5
Unlroyal,
Pancsvllle,
OH
Mtrlla 81 as teasers
0.3-0.9
5
3.1
<0.1
1.0
Vletron,
Liu, OH

Aorylonltrlla
» Aory lsjalde
0.2-0.6
5
1*0.0
<0.2
3«.»
®Th® dlatanoea ©f aaaple collection points are obtainad fro® Suta, 1979.
^Soaetlnes replloate staples vera collected frets the aaaa stapling point.
Source: U.S. EPA 1982

-------
TABLE D-16. DIRECT ANALYSIS OF ACRYLON1TR1LE
Sample
Sample Introduction
into Detector Unit
Analysis Technique
Confirmation
Technique
Detection
Limit





Simulated occupa-
tional air
Sample probe 61 pump
IR-mlcrocomputer
None
0.2 ppm
Occupational air
Introduction of air
from gas bag into
evacuated cell
IR
Hone
0.5 ppn
Acrylonitrile in Nj
Introduction to a
vacuum cell at 8 torr
IR lasers
None
0.03 ppm
Simulated air
Pump & rotoneter
Detector tube
None
Range 1-120
PPm
Cases generated by
heating ABS plastic
Forced air
Detector tube
GC-MS
—
Occupational air
Passive diffusion
"I'M
Abeor CASBADGE
None
Range 0.8-19
PP»
Simulated air
Direct injection
GC-NPD
MS
100 ppb
Occupational air
Direct injection
GC-FID
None
0.5 ppm
GC-MS - gas chromatography-maaa spectrometry
GC-NPD - gas chromatography-nitrogen/phosphorus detectors
HS - maaa spectrometry
GC-FID ¦ gaa chromatography-flame ionization detectors
Source: U.S. EPA 1982

-------
TABLE D—17- VARIOUS SORBENTS AND TRAPPING MEDIA FOR COLLECTION OF ACRYLONITRILE IN AIR
u

S»pl Inft
Condlt lo«
Dxtlfl lo«
Ktf lio4

Anal yiU
Tichnl^M
Conlifaatipfl
Technique
Del ectIon
LUIl

—
J,0z
0.S IppT (or
K-t S
Wafer

ColorlMirle
None
	
fUitic producing
pUn(
SHochro*-! &i
-KTc
	
TtiirMt at
100'C
cc-rirtb

	
Acry1Ic fIbtr
f
Silica fcl
Pcrionml
ia«^ila( (or
\m »ln.
Hdii

oc-riB
N«n«
0.3 fpm
5 l«au)et*d »(r
Activ«t*d carbon
11 i In gat
b»S
11 aciloH
In CI,
oc-rio
fbfiG
0.11-0.1 rpm
plml
Actlvettd eAibon
0.2 Ips for
S hi.
If IC«(OM
i« at
oc-rio
fkmm
0.01-0.11 9fm
llttttn productko
fllAll
Activated eaibo«
1.0 Ipai for
¦14 hf.


nc-rio
Motl*
* 0.] Mt/a1
SlsuUivd tlr

0.1 lp«i for
3-1 1
DkihI at
100*C
oc-rio
!£&?*«
* I fph
Sla«ilatd««
¦an|< *0-710
--
fit «tKinot
1 Ip.
—

PolirntlAphk
Haeae
0.1-1 m^/iO «l
Crttn (gallant &if
Chi!S14 water
0.01-0.11 Hps
	

fol«rp|f«pkic
Shane
1.08 s I0"1 N

Water
0.01} If* (or
1.1-J I
	

Color1a*tvIc
Hont
	
—
W«t«r
	
	

ColorlMUlc

0.1
Occupfltlmil air
Chi 11 e*£ v*t*f
1 Ipa for
10-60 1 .
	


Kcms
l»|i 10-100
PI"
Ac ry lonf (r I!« plant
Chilled water
Water
l ii?™


cc-tin
Colarliactrlc

10 ppb
10 V| W

H^SO^ I | l»*a beada
0.* lp-
	

Tit rlsctrlc
g&Stt£
10-100
itabber pUnl
It M,SOt
I 4
—-
	

Color la«irlG

« 0.11 Kl/1
	
it m?so4
—
---

Colorlwetrlc
Hone
	
SAM plant
mw
)5l ncthenol at
-ivc
r>. i-o. J lr-
—

rc-rio
oc-no
None
ttksSjS
0.1 «i/«'
*lp« ¦* SllPfB p«c *f nute
b
CC-MO ¦ |«
-------
Possible Interferences:
Humidity high enough to cause condensation in the
charcoal tube will cause inefficient trapping of
vapors
Any compound present which has the same retention
time as acrylonitrile
3.	Method B from Appendix A
a.	Whole air collection in canister cryogenic concentration
b.	Gas chromatographic/flame ionization detection (GC/FID)
Detection limit:
0.1 ppb for a 100 ml sample
Possible interferences:
Storage time greater than a week not recommended
Reactive and water-soluble compounds not readily
analyzed
If possible, a fluid GC/FID should be used to
avoid sample storage problems
4.	Method F from Appendix A
a.	Adsorption on carbon molecular seives
b.	Thermal desorption into canister
c.	Analysis by gas chromatography/flame Ionization detection
or gas chromatography/mass spectrometry
Detection limits:
0.01-1.0 ppb in a 20 1 sample
Possible Interferences:
High temperature (350® C) required for desorption
may decompose labile compounds
5.	Table D-18 1ists recovery efficiency of alternate sol vents
to use of methanol
153

-------
TABLE D-18. RECOVERY OF ACRYLONITRILE
FROM VARIOUS SOLVENTS
Solvent	% Recovery
Methanol	ca. 50%
Acetone	7X5 +_ 5.3%
2% acetone in	CSg 95.5 + 7.9%
2% acetone in	CSg 94%
CS2 (2 ml)	58%
CS2 (4 ml)	75%
Source: U.S.	EPA 1982
Materials Damage
Acrylonltrile may not be stored without polymerization inhibitors
Permissible Exposure Limits
OSHA	NIOSH ACGIH
TWA	2 ppm 4 ppm/10 hr 2 ppm {4.5 mg/m^)
Ceiling 10 ppm/15 min	(human carcinogen)
Odor perception: 21.4 ppm
Human Toxicity
Acute Toxicity:
Occupational exposures of 16 to 100 ppm for 20 to 45 min-
utes produced nasal irritation, upper respiratory tract
tightness
Acrylonitrlle mixed with carbon tetrachloride caused
toxic epidermal necrolysis
Chronic Toxicity:
Carcinogenesis--0n test in FY1983 for carcinogenesis (U.S. DHHS
1981)
Occupational exposures may be associated with an excess of lung
and col on cancer
154

-------
Mutagenesis—Mutagenesis/genetic toxicity testing to be
completed in FY1983 (U.S. DHHS 1981)
Other Chronic Toxicity:
On test for pulmonary toxicity in FY1983 (U.S. DHHS 1981)
Bibliography
American Conference of Governmental Industrial Hygienists. 1982. TLVS,
Threshold Limit Values for Chemical Substances and Physical Agents in the
Work Environment with Intended Changes for 1982. ISBNO. 936712-39-2.	
Cincinnati, OH.
Clayton, George D., and Florence E. Clayton, eds. Patty's Industrial Hygiene,
3rd Revised Edition, Vol. 2. "Toxicology." pp. 2889-2890. John Wiley and
Sons, New York, NY.
Deichmann, William B., and Horace W. Gerarde. 1969. Toxicology of Drugs
and Chemicals. Academic Press, NY.
Fuller, B., J. Hushon, M. Kornreich, R. Quellette, l. Thomas, and P. Walker.
1976. Preliminary Scoring of Selected Organic Air Pollutants. EPA-450/3-77-
008b. The Mitre Corporation. McLean, VA.
Hawley, Gessner G. 1977. The Condensed Chemical Dictionary, 9th Ed. Van
Nostrand Reinhold Company, NY.
Katz, Morris, ed. 1977. Methods of Air Sampling and Analysis. Alpha Inter-
society Committee, American Public Health Association, Washington, DC.
Kirk-Othmer. Encyclopedia of Chemical Technology, 2nd ed. John Wiley and
Sons, New York, NY.
Mackison, Frank W., R. Scott Stricoff, and Lawrence J. Partridge, Jr., eds.
1978. NIOSH/OSHA Pocket Guide to Chemical Hazards. DHEW (NIOSH) Publication
No. 78-210. Washington, DC.
National Fire Protection Association. 1981. National Fire Codes, A Compila-
tion of NFPA Codes, Standards, Recommended Practices", and Manuals. Vol. 13.
NFPA. Quincy, MA.
Proctor, Nick W., and James P. Hughes. 1978. Chemical Hazards of the Work-
pi ace. J.B. Lippincott Company, Philadelphia, PA.
Riggin, R.M. 1983. Technical Assistance Document for Sampling and Analysis
of Toxic Organic Compounds in Ambient Air. EPA-600/4-83-027. Battell e
Columbus	LaWratories. Columbus, OH.
155

-------
Schwartz, W.A., F.B. Higgins, Jr., J.A. Lee; R. Newirth, and J.W. Perview.
1975. Engineering and Cost Study of Air Pollution Control for the Petro-
chemical Industry Volume 2: Acrylonitrile Manufacture. EPA-405/3-73-006b.
Air Products and Chemicals Inc., Marcus Hook, PA.
Sittig, Marshal 1 . 1980. Priority Toxic Pollutants. Noyes Data Corporation.
Park Ridge, NJ.
Suta, Benjamin E. 1979. Human Exposure to Atmospheric Concentrations of
Selected Chemicals. PB81-193-278. CRESS Report Wo. CRU-6780. SRI Inter-
national, Menlo Park, CA.
U.S. Department of Health, Education, and Welfare. 1978. National Institutes
for Occupational Safety and Health; A Recommended $ t a n da rcTTor	0 c c u'pati on a V
Exposure to Acrylonitrile. OHEW (MTOSKVPliblication No. 78-116. National
Institute for Occupational Safety and Health. Cincinnati, OH.
U.S. Department of Health, Education, and Welfare. 1977. National Institute
for Occupational Safety and Health: Manual of Analytic MetHoBs, Vol ~ 1. DVtEW
(NIOSH) Publ. No. //-15/-A. Washington, DC.	:
U.S. Department of Health, Education, and Welfare. 1977. National Institute
for Occupational Safety and Heal th: Manual of Analytic MethodsVYbT".""3". UHEW
(NIOSH) Publ.No. 77-157—C. Washington, DC.
U.S. Department of Health and Human Services. 1981. Second Annual Report on
Carcinogens. Public Health Service, National Toxicology Program. Washington,
vr.
U.S. Department of Labor. 1981. General Industry, OSHA Safety and Health
Standards (29CFR191Q). Occupational Safety and Health Administration.
Washington, DC.
U.S. Environmental Protectlon Agency. 1976. Disposal of Hazardous Wastes,
Manual on Hazardous Substances in Special Wastes. NATO/CCMS Report 55.
Washington, DC.
U.S. Environmental Protection Agency. 1982. Health Assessment Document for
Acrylonitrile (Revised Draft). EPA-600/8-82^0U7; Office" of "Health" and
Environmental Assessment, Washington, DC.
156

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Chemical Name
Ally! Chloride
CAS Number
107-05-1
Chemical Classification
Organic halide
Synonyms
3-Chloro-l-propane, 3-chloro-propylene, chlorallylene,
3-chloroprene
Physical/Chemical Properties
Description:
Colorless to strawberry-colored liquid
Boiling point:
44.6° C
Melting point;
-134.5° C
Molecular weight:
76.5
Chemical formula:
C3H5CI
Vapor pressure:
295 mm Hg 20° C
359 mm Hg 25s C
Refractive index:
1.416
Solubility:
Insoluble in water
0.36 wt % 20° C
Soluble in alcohol
157

-------
Density:
0.94 g/cm3
Vapor density:
2.64 (air = 1)
Chemical reactivity:
Very reactive and widely usable as a starting material
and intermediate in organic synthesis
Transformation products in the atmosphere include
2-chloro-acetaldehyde and formaldehyde
Sources of Emissions
Product"! on/processi ng:
Production in 1978 was estimated as 330 million lb
Process emissions
fib/year)	Producer	Location
516,000	Dow Chemical Co. Freeport, TX
226,000	Shell Chemical Co. Deer Park, TX
226,000	Base Chemicals Norco, LA
Uses:
Ally! chloride Is used as a monomer in the production
of various plastics, resins, surface coatings, and as a
chemical intermediate for glycerols epichlorohydrin, and
ally! alcohol
No emissions data were available
Storage emissions from storage operations have been
estimated as 46,200 lb/year
Di sposition:
With the exception of defective batches, no concentrated
wastes are reported
Sampling and Analytical Methods
Sampling methods:
A known volume of air is drawn through a charcoal tube
to trap the organic vapors present
NIOSH Manual of Analytical Methods number SI16
158

-------
Analytical methods:
The analyte 1s desorbed with benzene and an aliquot of
the desorbed sample 1s Injected Into a gas chromatograph;
NIOSH Manual of Analytical Methods number SI16
Detection limits:
For a 100 1 sample size, the detector sensitivity
1s 0.5 to 10 mg/m^
Possible interferences:
1.	High humidity causes inefficient trapping of organic
vapors
2.	Interference from the presence of the desorbant
3.	Compounds present with the same column retention
time
Permissible Exposure Limit
OSHA Standard
1 ppm (3 mg/m3) TWA
NIOSH recommendation
3 ppm/15 min celling (9 mg/m3)
Human Toxicity
Chronic Toxicity:
Carcinogenicity--There is inadequate evidence in humans, and in
experimental animals tumors were not induced in a 6-month
study (3 ppm, inhalation)
Mutagenic1ty--Allyl chloride was mutagenic in Salmonella TA 100
and TA 1535
Teratogenicity--Reproductive and developmental toxicity are on
test in FY83
Bibliography
Fishbein, L. 1979. Potential Industrial Carcinogens and Mutagens. Elsevier
Scientific Pulishing Co. New York, NY, pp. 194-96.
Kirk-Othmer. 1979. Encyclopedia of Chemical Technology, 3rd ed. John Wiley
and Sons, New York, NY, pp. /b3-/3.
Systems Applications, Inc. 1980. Human Exposure to Atmospheric Concentrations
of Selected Chemicals. PB81-1932"50T EPA/0AQPS, Research Triangle Park, NC,
pp. A2-"1^2tn
159

-------
U.S. Department of Health, Education, and Wei fare. 1977. NIOSH Manual of
Analytical Methods. U.S. DHEW/PHS/NIOSH, Vol. 2, S116.
U.S. Department of Health, Education, and Wei fare. 1976. NIOSH Criteria for
a Recommended Standard....Occupational Exposure to AT 1y1 Chloride. U.S.
DHEW/PHS/NIOSH, Publication No. 76-204.			
U.S. Department of Health and Human Services. 1983. Review of Current DHHS,
DOE and EPA Research Related to Toxicology. National Toxicology Program.
U.S. DHHS/PHS/NTP.					
160

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Chemical Name
Arsenic
CAS Number
7440-38-2
Chemical Classification
Elemental metal
Synonyms
Arsen; arsenic black; grey arsenic; metallic arsenic
Physical/Chemical Properties
Description:
Grey to black brittle, crystalline or amorphous solid
Boiling point:
613° C (sublimes)
Melting point:
817° C
Atomic weight:
74.92
Atomic formula:
As
Solubil ity:
Insoluble in water; soluble in nitric acid
Photochemical reactivity:
No photochemical reactivity
161

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Density:
5.727 g/cm3 20° C
Chemical reactivity:
Metallic arsenic is stable in dry air; arsenic vapor
does not combine directly with hydrogen to form hydrides.
Metallic arsenic is not readily attacked by water, alka-
line solutions or non-oxidizing acids
Sources of Emissions
Production:
Approximately 70 million lb of arsenic and inorganic
arsenic compounds are produced in the United States
annually. Table D-19 lists the location and companies
producing arsenic compounds. Table D-20 lists the esti-
mated arsenic emissions in the United States by source.
Arsenic trioxide is the source of 97 percent of arsenic
compounds
Uses:
Elemental arsenic and arsenic compounds are used in
pesticides, glass, ceramics, paints, dyes, nonferrous
al1oys, wood preservatives, etc.
Emission factors for mining, industrial sources, process-
ing and consumptive uses have been calculated as follows:
Source
Emission Factor
Mi ning
Copper smelter
Lead smelter
Zinc smelter
Cast iron
Nonferrous alloys
Pesticide production
Glass production
Others (paint, pharma-
ceutical s, semicon-
ductors, pyrotechnics,
wood preservatives,
etc.)
Cotton ginning processing
0.2 1b/ton arsenic in ore
5 1b/ton of copper
0.8 1b/ton of lead
1 1b/ton of zinc
0.01 to 0.02 1b/ton of metal
charged
1 1b/ton of arsenic processed
20 1b/ton of arsenic processed
0.2 lb/ton of glass produced
3 1b/ton of arsenic processed
4 lb/103 bales of cotton ginned
162

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TABLE D-19. PRODUCTION OF ARSENIC COMPOUNDS
Location
Company
Californta
Cucamunga
Newark
Santa Clara
South Gate
Will Ross (G. D. Searle)
II 11
Airco
Los Angeles Chemicals
Georgia .
Morrow
Fort Valley
Will Ross (G. D. Searle)
Wool folk Chemicals
Illinois
Joliet
North Chicago
Rock-ford
Will Ross (G. D. Searle)
Abbott Labs
Apache Chemicals
Massachusetts
Gloucester
Will Ross (G. D. Searle)
Missouri
St. Peters
Monsanto
New Jersey
Bayonne
Bayonne
Bound Brook
East Rutherford
Jersey City
Somerset
Vlneland
Dimensional Pigments
Rona Pearl
Slue Spruce
Will Ross (G. 0. Searle)
City Chemicals
W. A. Cleary
Vlneland Chemicals
Oklahoma
Miami
Quapaw
Tulsa
Eagle-P1cher
El
Ozark-Mahoni ng (Pannwalt)
Pennsylvania
Myerstown
Rohm and Haas
Tennessee
Memphi s
Osmose Wood Pres.
Texas
Bryan
Greens Bayou
La Parte
Pennwalt
Diamond-Shamrock
Will Ross (G. D. Searle)
Washington
Tacoma
Pennwalt
Wisconsin
Marinette
Ansul
Source: Mason et al
1979
163

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TABLE D-20. ESTIMATED ARSENIC EMISSIONS IN U.S.—1974
Source
Number of
Plants
Inorganic Arsenic
Emissions
kkq/Year
Percent
Total Emissions
Copper smelters
15
2712
61.1
Lead smelters
6
63
1.4
21 nc smelters
6
73
1.6
Production of arsenical
compounds
25
154
3.5
Application of inorganic
arsenical pesticides
N/A
399*
9.0
Glass production
325
363
3,2
Coal burning
- power plants above
25 megawatts
369
526
11.9
Other
*9
109
2.5
Misc. (cotton gins, non-
ferrous alloys,
inorganic chemicals)
EBB
36*
.8
Total

4435
100.0%
Source: Mason et al. 1979
164

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Coal-fired plants, pesticide production and use, and
copper smelting are all significant sources of atmospheric
arsenic, EPA reports that smelter emissions result in
the most arsenic exposure by air to the greatest number
of persons
Di sposition:
Arsenic-containing wastes in the form of sludge occur
during the metallurgical processing of arsenic-containing
ores. Arsenic contamination of the environment occurs
faster than it can be dissipated by natural processes.
The emission factor for sewage and sludge containing
arsenic has been calculated as 0.2 lb/ton. Airborne
waste emissions were addressed under emission factors
Sampling and Analytical Methods
Particulate Arsenicals
Sampling methods:
Particulate arsenicals are collected on a 37 mm
polytetrafluoroethylene-backed membrane filter at
1.5 1pm
Method number P&CAM 320
Analytical method:
The arsenicals are extracted ultrasonically and
the arsenical species are separated chromograph-
ically. Hydrides of each species are generated
and quantitated by AAS detection using quartz
furnace atomization
Method number P&CAM 320
Detection limits:
This method was tested over the range of 5-20 yg/m^
using a 300 1 sample
Possible interferences:
Any arsenical compound with the same column
retention time as the arsenical of interest is
an interference
Additional methods for sampling and analysis of arsenic
are:
Arsenic and compounds (as AS) in air (NI0SH Method
number S309)
165

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Inorganic arsenic in air (P&CAM 346)
Source: NIQSH Manuals of Analytical Methods
Permissible Exposure limits
OSHA Standard
0.5 mg/m^ 8-hr TWA as arsenic (organic);
10 ug/m^ 8-hr TWA (inorganic)
Human Toxicity
Acute toxicity:
Acute arsenic poisoning can occur from accidental or
intentional ingestion and can result 1n death of the
victim
Chronic toxicity:
Carcinogenicity--there is sufficient evidence that skin cancer
in humans 1s causually associated to inorganic arsenic compounds.
Case reports have suggested an association between exposure to
arsenic compounds and blood dyscrasias and liver tumors
Mutagenicity—humans who have been exposed to sodium arsenite
have shown chromosomal defects
Teratogen!"city--birth defects have been demonstrated in animals
injected with arsenic. The evidence in humans is not available
Other chronic toxicity:
Neurological effects—arsenic exposure in humans can produce
peripheral nerve damage and al tered el echocardiograms
Bibliography
International Agency for Research on Cancer. 1980. IARC Monographs on the
Evaluation of Carcinogenic Risk of Chemicals to Humans. Lyon, France,
Vol. 23, pp. 39-129.
Kirk-Othmer. Encyclopedia of Chemical Technology, 2nd ed. John Wiley and
Sons, New York, NY. Vol. 2, pp. 711-32.
166

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Mason, B., et al. 1979. Environmental Carcinogens and Human Cancer. EPA
Contract Number 68-03-2504"," USEPA/ORD Research Triangle Park, NC.
pp. 21-41.
Sittig, M. 1980. Priority Toxic Pollutants. Noyes Data Corporation, Park
Ridge, NJ. pp.		
U.S. Department of Health, Education, and Welfare. 1977. NIOSH Manual of
Analytical Methods. USDHEW/PHS/NIOSH.
Vol. 1,
p. 188.



U.S. Department of Health, Education, and
Wei fare.
1977,
NIOSH
Manual
of
Analytical Methods. USDHEW/PHS/NIOSH.
Vol. 3,
p. S309.



U.S. Department of Health, Education, and
Wei fare.
1977.
NIOSH
Manual
of
Analytical Methods. USDHEW/PHS/NIOSH.
Vol. 6,
p. 320.



U.S. Department of Health, Education, and
Wei fare.
1977.
NIOSH
Manual
of
Analytical Methods. USDHEW/PHS/NIOSH. Vol. 7, p. 346.
U.S. Environmental Protection Agency. 1978. An Assessment of the Health
Effects of Arsenic Germane to Low-Level Exposure. USEPA/OHEE/ORD.
Washington, DC.
U.S. Environmental Protection Agency. Toxics Information Series. USEPA/
OPTS. Washington, DC.
167

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Chemical Name
Asbestos
CAS Number
1332-21-4
Chemical Classification
Natural fibrous silicate
Synonyms
Asbestos fiber, asbestos fibre
Physical/Chemical Properties
Description:
Fibrous mineral that can be woven; good flexing and
tensile strengths. There are two major groups of
asbestos: serpentine (chrysotile) and amphibole.
Chrysotile is the major type of asbestos used in the
manufacture of asbestos products.
Properties of asbestos fibers:
Type Name		CAS #		Formul a	
Serpentines Chrysotile	12001-29-5	Mg3Si2O5{OH)4
Amphiboles Amosi te	12172-73-5	(MgFe)7Sis022(0H)2
Croc idolite	12001-28-4	Na2(MgFe)5SigQ22(0H)2
Anthophyllite	17068-78-9	(HgFe)7SI8^22 C OH) 2
Tremolite	14567-73-8	Ca2Mg5$ig022(0H)2
Actinolite	13768-00-8	Ca2(MgFe)5Sig022(QH)2
Other properties of asbestos fibers: See Table D-21
Synonyms:
Chrysotile: serpentine, 7-45 asbestos, Avibest C, Cassiar K,
Calidria RG 144, Calidria RG 600
Amosite: mysori te
Crocidolite: --
168

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TABLE 0-21. PROPERTIES OF ASBESTOS FIBEHS

Chrysotl le
Anthaphyl1tte
Antosl te
(ferroanttxjphyl 11 te 1
Croc 1dol1te
Irenol lte
Ac tlnol 11€
Structure
In veins of serpentine
Lamellar, fibrous
ashes U fom
lamellar, coarse to
fins fibrous and
asbestlfora
Fibrous In iron-
stones
Long, prismatic and
fibrous aggregates
Reticulated long
prismatic crys-
tals and fibers
Essential
compos 1tton
Hydrous silicates of
magnesium
M§ silicate with
Iron
Silicate of Fs and
Hg. higher Iron than
anthophyl 11 te
S11Icate of Na
and fe with some
water
Ca and Hg silicate
with some water
Ca, Hg, Fe.
silicates, water
up to SI
Crystal structure
Fibrous and asbestlforn
Prismatic, lamellar
to fubrous
Prismatic, lamellar
to fibrous
fibrous
Long and thin columnar
with some water
Long and thin
columnar to
fibrous
Color
White, gray, green,
yellowish
Grayish white, brown,
gray or green
Ash gray, greenish
or brown
Lavender, blue,
greenish
Gray-white, greenish,
yellowish, Mulsh
Green1sh
Luster
Silky
Vitreous to pearly
VItrrous, somewhat
pearly
Silky to dull
Silky
Silky
Specific gravity
2.4 - 2.6
2.85 - 3.1
3.1 - 3.25
3.2 - 3.3
2.9 - 3.2
3.0 - 3.2
Refractive intte*
1.50 - 1,55
1.61
1.64
1,1 pleochrolc
1.61
1.63 weakly
pieochrolc
Flexibility
Very flexible
Very brittle,
nonflexlble
Good, less than
chrysotlle
Fair to good
Generally brittle,
sometimes flexible
Brittle and
nonflexlble
Length
Short to long
Short
2" to 11" varies
Short to long
Short to long
Short to long
Acid resistance
Soluble up to appro*.
57%
Fairly resistant to
acids
Fairly resistant to
adds
Fairly resistant
to adds
Fairly resistant to
acids
Relatively
Insoluble In HC1
Specific heat
atu/llb *F)
Appro*. smallest
0.266
0. 01 !<¦
0.Z10
0.1 Ml
0.11?
0.1 t>m
0.201
0.08 t>m
0.212
0.1 urn
0.21?
0.08 t>ra
fiber diameter
Source: Kfrk-Othraer 1963

-------
Anthophyl1ite: Asbolen asbestos, ferroanthophyl1ite
Tremolite: Silicic acid, calcium magnesium salt (8:4)
Actinol ite:
Chemical reactivity:
Asbestos has a high fusion temperature; it is resistant
to thermal degradation and chemical attack
Envi ronmenta! Fate
Asbestos fibers are released into the environment from the natural
occurrence of asbestos in the earth
Asbestos minerals are emitted into the atmosphere and water systems
from the mixing and milling of asbestos ores
Atmospheric asbestos is limited because the mineral fibers and dust
are quickly deposited by means of precipitation, becoming bound to
soil or sediments
The general population is exposed to asbestos fibers from air,
beverages, drinking water, food, pharmaceutical and dental prepar-
ations, and asbestos-containing consumer products. Families of
asbestos workers have been exposed to high-fiber levels through
contaminated clothing that was brought home for laundering
Sources of Emissions
Production:
Naturally, from asbestos ore and counterpart rock
Asbestos mining: run-off from waste tai1ings in dry mining
run-off from wet mining
iron ore mining
Approximately 200 million pounds were produced in 1979
Uses:
Asbestos cement products, manufactured by wet processes
Electrical insulation
Thermal insulation
Asphalt and vinyl flooring, adhesives
170

-------
Papers, millboards, roofing felts
Asbestos textile industry, fireproof and acidproof
fabrics
Brake linings, clutch facings and packings
Putties, molding compounds, roof coatings, welding rods:
paints, calking compounds, fi11ers
For filtration (wines, juices, beers, whiskey)
For asphalt paving
In reinforcing plastics
Missile work--satel1ites, special packings in atomic
energy equipment
Storage:
Mi 11ed asbestos fiber is usually stored and shipped in
bags (which themselves become sources of emissions}
Transportation:
Emissions from open-truck movement of asbestos ore from
mine to mil 1 •
Emissions from shipment of milled asbestos fiber and
asbestos-containing products
Disposition:
Emissions into run-off waters from asbestos mines,
deposited in soils
Emissions from brakes lined with asbestos
Emissions from demolition of buildings with asbestos
insulation
Emissions from manufacture and use of products con-
taining asbestos
Asbestos-containing wastes occur as residues, collected
dusts and sludges, and are often disposed of in open
dump along with municipal wastes
Asbestos production, consumption, and exposure data are
given in Tables D-22 through D-28
171

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TABLE D-22. WORLD PRODUCTION OF ASBESTOS
Year
World production
(million kg)
1 Canada.
% USSR
1960
2 210
45
29
1970
3 490
44
30
1973
4 093
41
31
1974
4 115
40
33
1975
4 560
23
48
1976
5 178
29
44
Source: IARC 1980
TABLE D-23. ASBESTOS DISTRIBUTION BY END USE, GRADE, AND TYPE IN THE U.S., 1974
(million kg)

Qirysotile
Crocidolite
Arosite
Anthophyllite ]
Total
Asbestos cfsvBnt pipe
168
33
0.9
0.18
202
Asbestos cement sheet
82

3.9

96
Flooring predicts
139



139
Boofing products
66

1.5

67
Packing & gaskets
26
0.09


26
Insulation, thermal
6.6

1.6

8
Insulation, electrical
4.2



4
Friction products
72


0.18
72
Coatings arid conpaunds
34



34 j
Plastics
15
0.10

0.63
16 !
Textiles
18



18
Paper
57
0.13


57
Other
33
0.36 ¦
0.45

34
Total




763
..— . .





Source: IARC 1980
172

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TABLE 0-24. LENGTHS OF ASBESTOS FIBERS IN AIR NEAR VARIOUS U.S. INDUSTRIES
Ofjeration
Fibre
Median
% > 5 iim

type
length turn)

Textile
chrysotile


Fibre preparation & carding

1.4
4
Spinning, twisting, waving

1.0
" 2
Friction
chxysotile


Mixing

0.9
2
Finishing

0.8
2
Asbestos-cenent pipe
chrysotile


Mixing

0.9 '
2
Finishing

0.7
1
Pipe insulation
amosite


Pipe forming

4.9
51
Source: IARC 1980
TABLE D—25- ASBESTOS PRODUCERS—1976
Location
Company
Coiments
Alaska
near Eagle
Ari zona
El Dorado Mine, Gila County
Tanana Asbestos
Jacquays Mining
Dri11ing Operation in
Progress
Cal1fornia
Copperapolis
Fresno County
San Benito County
Calaveras Asbestos
Atlas Asbestos
Union Carbide
-
North Carolina
Newdale
Vermont
Lowe]1
Powhaten Mining
Vermont Asbestos
May be inactive,
Anthophyllite asbestos
Notes - All asbestos mined 1s chrysotile except at the North Carolina
location.
Source: Mason et al. 1979
173

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TABLE D—26. ASBESTOS DISTRIBUTION BY TYPE, 1974 (Short tons)




To Lai.

CrocidoliLr
AiBtniL*
AntbophyUltc

cecntaf pipe			„ , , ^
t$.$m
1.100
200'
Z3:>900
Lo« crarcflt th«t 		

4JOO
„
94,300
Flewvrins' produc*j 	„ 				 			

	

1*3.530
RiasiWa pro-duets
__
I,TOO
r —
75,500
PfcekifiGT ifid sraj.fccLa	
10 Q

OW
ZS.AGO
Iniuljihnn, t hd*T-n « | 					
mm
IMQ
_
. MOO
JBjtajAtjQfv, •]¦#»« rue a. 1						
_

	
4.700
Friction products 			

•—
zoo
TS, 500
CotttlncT *nd compounds „ « .. 	o
__


37,900
PLa«dcm 		 		 	
:oo

TOO
17.500
TestiWa 	.			.		 .....

	
_.
20,400
PaD
-------
TABLE 0-28. SELECTED ASBESTOS CONSUMERS
Locatl an
Company
Products
Alabama
ftagland
CAPCO
Asbestos-concrete pipe
Arkansas
Yan Surra
CAPCO
Asbestos-concrete pipe
California
Pitts Burg
Johns-Manv111e
Asbestos paper
Connecticut
Stratford
Saybestos-Manhatten
Textiles, friction r.aterlaIs*
Illinois "
Kankake*
Arrotrong-Cork
Roofing and Tile
Louisiana
(few Orleans
National Gypsua
Asbestos-concrete sf.ee t
M«1n«
E. Valpole
9111 erica
HolUngsxorth and Yost
Johns - Manvllle
Asbestos paper
Asbestos-concrete sheet
HI $ sourl
St. Louis
St. Louis
Certain-Teed
SAF
Asbestos-concrete pipe
Asbestos-concrete sheet
Nw Hampshire
Nashua
TUton
Johns - HanvUlt
Johns - Manvllt®
Asbestos-concrete sheet
Asbestos psper
Hew Jersey
Marwflla
Johns - Manvf 11 e
Multi-products *
New Yort
Pulton
Arsatnmg Cork
Asbestos paper
North Carolina
Marsttvlllc
N. Charleston
Raybestos - Mannatten
Ssybestos - Martha ties
Teitlles, friction materials
Textiles, friction materials
Ohio
Raverma
Hlntkote
Asbestos-concrete pipe 9
Pennsylvania
Ajnftler
Erie
Erie
WJHtehall
.Hcalet
GAP
SAF
GAF
Asbestos-concrete sheet
Asbestos pager *
Roofing and Tile
Asbestos paper *
Tejtai
0«ill son
Johns - Manvllle
Asbestos-concrete pipe *
Source: Mason et al. 1979
175

-------
Sampling and Analytical Methods
1.	NIOSH method P&CAM 239 for "Asbestos Fibers in Air"
a.	Filter col lection
b.	Microscopic count
Detection limits:
0.1 - 60 fibers/an3
Possible interferences:
In an atmosphere known to contain asbestos, all
particulates with a length to diameter ratio of
3 to 1 or greater, and a length greater than
5 micrometers should, in the absence of other
information, be considered to be asbestos fibers
and counted as such.
2.	NIOSH method P&CAM 309 for "Chrysotile"
a.	Collection on membrane filter
b.	Redisposition on silver membrane filters
c.	X-ray diffraction
Detection limits:
25 - 2500 yg/m^ for an 800 1 sample
Possible interferences:
An ti go rite, the massive form of chrysotile,
present in quantities >10%
Chlorite interferes with both primary and
secondary peaks of chrysotile unless the
instrument has good resolution
Kaolinite interferes with the primary peak of
chrysotile so the secondary peak must be used.
The presence of iron in sample results in
X-ray fluorescense which can be avoided by
using a diffracted beam monochromator
3.	For "Chrysotile in Buik Samples," see NIOSH method
P&CAM 245
176

-------
Permissible Exposure Limits
OSHA
ACGIH
TWA 2 fibers longer amosite: 0,5 fibers >5 um/cc
than 5 wm/8 hr	chrysotile: 2 fibers >5 um/cc
croc idolite: 0.2 fibers >5 um/cc
other forms: 2 fibers >5 um/cc
Ceiling 10 fibers longer
than 5 um/cc
Human Toxicity
Chronic toxicity:
Asbestosis—Asbestos dusts and asbestos-containing dusts are
among the fibrogenic dusts which, with the formation of con-
nective tissue, can simultaneously cause pneumonoconiosis.
Fibers of up to 250 urn in length can reach the alveoli.
Longer fibers are always more dangerous than short ones
Sometimes the action of asbestos can cause irritation of the
conjunctiva, gullet, and mucous membrane of the larynx. Fine
asbestos fibers .that reach the digestive tract are occasionally
capable of penetrating the stomach and intestinal walls,
reaching the blood stream and mi gating through the body with
the flow of blood. They can even pass through the placenta
Carcinogenicity—Occupational exposure to chrysotile, amosite,
anthophyl1ite, and mixtures containing crocidolite has resulted
in a high incidence of lung cancer. A predominantly tremolitic
material mixed with anthophyllite and small amounts of chrysotile
has also caused an increased incidence of lung cancer. Pleural
and peritoneal mesotheliomas have been observed after occupa-
tional exposure to crocidolite, amosite, and chrysotile asbestos.
Gastrointestinal tract cancers were increased in groups exposed
occupationally to amosite, chrysotile, or mixed fibers containing
crocidolite. An excess of cancer of the larynx was also
observed in exposed workers. Mesotheliomas have occurred in
individuals living in the neighborhood of asbestos factories
and crocidolite mines, and in persons living with asbestos
workers. Both cigarette smoking and occupational exposure to
asbestos fibers increase lung cancer incidence independently.
When present together, they act multi piicatively
177

-------
On test in FY1983 for biochemical/eel 1ular/tissue effects,
and for immunological and pulmonary toxicity, clinical
toxicology and epidemiology (U.S. DHHS 1983)
Acute/chronic toxicity, biochemical/cellular/tissue
effects, and immunological and pulmonary toxicity testing
to be started in FY1983 {U.S. DHHS 1983)
Acute/chronic toxicity testi ng to be completed in FY 1983 (U.S.
DHHS 1983)
Bibliography
American Conference of Governmental Industrial Hygienists. 1982. TLVS,
Threshold Limit Values for Chemical Substances and Physical Agents in the
Tjjork _ Environment" with	In'teh~de3~CH"a"nge s for 1982. I SB No. 936712-39-2.
Cincinnati, OH.	~~
Clayton, George D., and F1orence E. CIayton, eds. Patty's Industrial Hygiene,
3rd Revised Edition, Vol. 2B. "Toxicology." pp. 3021-3023. John Wiley and
Sons, NY.
Deichmann, William B., and Horace W. Gerarde. 1969. Toxicology of Drugs and
Chemicals. Academic Press, NY.
GEOMET Technologies, Inc. 1981. Chemical Summaries for MTP Second Annual
Report Carcinogens. Rockville, ME
Haw!ey, Gessner G. 1977. The Condensed Chemical Dictionary, 9th ed.
Van Nostrand Reinhol d Company"," NT.
International Agency for Research on Cancer. 1977. IARC Monographs on the
Evaluation of Carcinogenic Risk of Chemicals to Man" Lyons, France.
Vol. 14. "Asbestos
International Agency for Research on Cancer. 1977. IARC Monographs on the
Evaluation of Carcinogenic Risk of Chemicals to Man" Lyons, France.
Vol. 2. "Some Inorganic"and Organometal1ic Compounds."
Kirk-Othmer. Encyclopedia of Chemical Technology, 2nd ed. John Wiley and
Sons, New York, NY. Vol. I, pp. 734-47.
Mackison, Frank W., R. Scott Stricoff, and Lawrence J. Partridge, Jr., eds.
1978.	NIOSH/QSHA Pocket Guide to Chemical Hazards. DHEW (NIOSH) Pub!ication
No. 78-210^ Washington, DC".
Mason, Benjamin J., Douglas J. Pel ton, Ruth J. Petti, and David J. Schmidt.
1979.	Environmental Cardnogens and Human Cancer. GEOMET Report Number
HF-803. GEOMET, Incorporated, Gaithersburg, MD.
178

-------
McGraw-Hill, Inc. 1977. McGraw-Hill Encyclopedia of Science and Technology.
New York, NY. Vol. 1.
National Academy of Sciences. 1971. Asbestos, the Need for and Feasibility
of Air Pollution Controls. Committee on Biologic Effects of Atmospheric
Pollutants, Division of Medical Sciences, National Research Council.
Washington, DC.
Proctor, flick W., and James P. Hughes. 1978. Chemical Hazards of the Work-
place. J.8. Lippincott Company, Philadelphia, PA.
Sittig, Marshall. 1980. Priority Toxic Pollutants. Noyes Data Corporation.
Park Ridge, NJ.
U.S. Department of Health, Education and Welfare. 1977. NIOSH Manual of
Analytic Methods, Vol. 1. DHEW (NIOSH) Publ . No. 77-157^ Cincinnati, OH.
U.S. Department of Health, Education and Wei fare. 1977. NIOSH Manual of
Analytic Methods, Vol. 5. DHEW (NIOSH) Publ. No. 79-141" Cincinnati, OH.
U.S. Department of Health and Human Services. 1983. National Toxicology
Program: Review of Current DHHS, DOE, and EPA Research Related to Toxicology.
NTP-83-001. Research Triangle Park, NC.
U.S. Department of Health and Human Services. 1981. Second Annual Report on
Carcinogens. Public Health Service, National Toxicology Program, Washington,
bc:
U.S. Department of Health and Human Services. 1981. Third Annual Report on
Carcinogens. Publ1c Health Service, National Toxicology Program, Washington,
ran
U.S. Department of Labor. 1981. General Industry, OSHA Safety and Health
Standards (29CFR191). Occupational Safety and Health Administration.
Washington, DC.
U.S. Environmental Protection Agency. 1976. Disposal of Hazardous Wastes,
Manual on Hazardous Substances in Special Wastes. NATO/CRMS Report 55.
Washington, DC.
179

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Chemical Name
Benzene
CAS Number
71-43-2
Synonym
(6)Annulene, benzene (DOT), benzin, benzine, benzol, benzole,
benzolene, bicarburet of hydrogen, carbon oil, coal naphtha,
cyclohexatriene, mineral naphtha, motor benzol, NCI-C55276,
nitration benzene, phene, phenyl hydride, pyrob, pyrobenzol,
pyrobenzole
Chemical Classification
Aromatic hydrocarbon
Physical/Chemical Properties
Description:
Colorless, volatile, highly flammable liquid, with a
distinct odor, like gasoline
Boiling point:
80. T C
Melting point:
5.5° C
Molecular weight:
78.11
Chemical formula:
c6h6
Vapor pressure:
74.6 ran Hg at 20° C
Refractive index:	9Q
Highly refractive;	1.5016
180

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Solubility:
Slightly soluble in H2O (enough to be toxic to aquatic
organisms); soluble in natural fats and fat soluble
substances; miscible with acetone, alcohol, carbon
disulfide, carbon tetrachloride, chloroform, ether,
glacial acetic acid and oils
Octanol/water log partition coefficient:
2.28
Photochemical reactivity:
Not photoreactive
Density:
0.8737 g/ml at 25° C
Vapor density:
2.77 (air * 1)
Chemical reactivity:
Activity toward O2: slowly reacts with oxidizing materials
Activity toward OH: half-life ~ 3 days
Undergoes substltution, addition and cleavage of the ring
Environmental Fate
Released Into the atmosphere from both stationary and mobile sources,
Including from production, transportation, and storage of benzene
Benzene occurs in ambient air from 1-100 ppm, in drinking water
at approximately 10 ppb, and in subsurface water at 10 ppm
Benzene 1s biodegradable
Sources of Emissions
Production:
An estimated 12 bill ion lb of Isolated and non-isolated
benzene (all grades) was produced in the United States in 1980
From petroleum:
Isolated from catalytic reformate
Isolated from pyrolysis gasoline
Direct from dealkylation of toluene
Direct from disproportionation of toluene
181

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From coal:
Isolated from coke oven light oil
Isolated from further separation techniques in coke
oven operations
Distillation of coal tar
Uses:
Synthesis of other organic chemicals:
Ethyl benzene (used in production of styrene)
Cumene
Cyclohexane
Anilene
Chlorobenzenes {for DDT and mothballs)
Maleic anhydride
Detergent alkylate
Emissions of benzene from the production of other chemicals
have been estimated as 44,000-56,000 tons. Concentrations i
air near U.S. chemical manufacturing companies were reported
in the range of 2 to 109 ug/m^
Solvent in chemical and drug industries
Gasoline additive
Emissions from gasoline production have been estimated
40,000-80,000 tons annually
Benzene is used in the manufacture of styrene and phenol ,
dyes, benzene hexachloride insecticides, fumigants, paint
removers, rubber cement, anti-knock gasoline, synthetic
detergents
Storage and transport:
Emissions from motor vehicle fueling and operation
Gasoline service station emissions
Bulk terminal (rail-tank-marine) loading/storage emissions
Oil spills emissions
Most of domestically shipped benzene goes by barge (79.6%),
14,8% by rail, and 5.6% by truck
Most pipeline shipment is restricted to benzene that is
captively used by the producing plant
182

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Di sposition:
Wastes containing benzene are mainly distillation residues
from petrochemistry, spent catalysts, residues from coking
processes and spent solvents from petrochemistry, the
reprocessing of which is frequently too expensive
Benzene is biodegradable. Diluted aqueous solutions,
therefore, are drained into sewage treatment pi ants and
decomposed there by anaerobic bacteria
Solvent mixtures and sludges of higher concentration are
burnt in special waste Incinerators if a recovery process
is uneconomical
Tables D-29 through D-31 give benzene production, consumpti
and emission data
Sampling and Analytical Methods
1.	NIOSH method S311 for "Benzene"
a.	Adsorption on charcoal
b.	Desorption with carbon disulfide
c.	Gas chromatographic analyses
Detection limits:
13-51.8 ppm/2 1 sample
Possible Interferences:
High-humidity causes inefficient trapping and
decreases breakthrough volume
Any compound present which has the same reten
tion time as benzene interferes with chemical
identi fi cation
2.	NIOSH method P&CAM 127, "Organic Solvents in Air"
a.	Adsorption on charcoal
b.	De sorption with carbon disulfide
c.	Gas chromatographic analyses
Detection limits:
0.01 mg/0.5 1 to 55 1 sample
183

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TABLE D-29. ANNUAL EMISSIONS Of BENZENE
TO AIR FROM VARIOUS SOURCES
Emission
Source	(thousand tons)
Component of gasoline*	40.0 - 80.0
Production of other chemicals	44.0 - 56.0
Indirect production of benzene1"	23.0 - 79.0
Production of benzene from petroleum	1.8 - 7.3
Solvents and miscellaneous sources	1.5
Imports of benzene	0.013
* Production, storage, transport, vending and combustion
f Coke ovens, oil spills, nonferrous metals manufacturing, ore
mining» wood processings coal mining, and textile industry
Source: IARC 1982
TABLE D-30. BENZENE CONSUMPTION (1976)
Produce use	Percent
Ethylbenzene	50.0
Cumene	16.6
Cycl'ohexane	14.9
Aniline	4.3
Chlorobenzenes	3.S
Maleic anhydride	2,7
Detergent alkylate	2.6
Miscellaneous applications	3.0
Exports	2.4
Source: Ochsner, Blackwood, and Zeagler 1979
184

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TABLE D-31. BENZENE EMISSION SOURCES



1976 Estimated

Mass


benzene emis-

emi ssions


sion rate,
Number of
per source,
Emission source

1Q6 kg/yr (11)
sources
'kq/\/v
Benzene production:
t



Catalytic reforming

2,6
39
67,000
Toluene dealkylation

1.4
16
88,000
Toluene disproportionaticn

0.04
2
20,000
Pyrolysis gasoline

0.6
10
60 ,000
Coke-oven light oil

0.2
5
40,000
Coke-oven operations

0.2
6
33,000
Benzene consumption:




Ethylbenzene/styrene

9.5
12
190,000
Curaene/phenol

2.4
9
270,000
Cyclohexane

7.8
8
975,000
Aniline

0.1
7
14,000
Chlorobenzenes

2.6
7
370,000
Maleic anhydride

2.0
9
220,000
Detergent alkylate

0:01
5
a, 700
Surface coatings {paints}

3.2
8,745
370
Degreasing

73.1
1,300,000
56
Nitrobenzene

3.4
9
380,000
Fumaric acid

0. 3
6
50,000 .
Aeryloni^rile

0.2
6
33,000
Other sources;




Automobile tarJc loading

5.9
226,500
26
Service station tanks

0.2
226,500
30
Bulk terminal loading/storage
0.04
30,900
1
Motor vehicles

450
130,000,000
3
Oil spills

10
787
12,000
TOTALS

576
131,800,000


Source: Ochsner, Blackwood,
and Zeagler 1979


185

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Materials Damage
Fire hazard; explosion hazard
Permissible Exposure Limits
OSHA
ACGIH
TWA 10 ppm 8-hr
Ceiling 25 ppm
PEAK 50 ppm/10 mtn.
10 ppm (30 nig/)
25 ppm (75 mg/nP)
Human Toxici ty
Acute toxicity:
Blood effects
Aplastic anemia
Narcotic action on CNS
Chronic toxicity:
Carcinogenicity--There Is sufficient evidence that benzene is
carcinogenic to humans. Several case reports as well as
an epidemiological case control study, establish a relationship
between benzene exposure and leukemia
Mutagenicity—The evidence of mutagenicity in short-term tests
is limited. Benzene has induced chromosomal abnormalities
in occupationally exposed people
Other chronic effects;
Estrus cycle disorder
Liver, kidney and lung damage
Hormone alteration
Bone marrow hyperplasia
Bibliography
American Conference of Governmental Industrial Hygienists. 1982. TLVS,
Threshold Limit Values for Chemical Substances and Physical Agents in the
Work Environment with Intended Changes for 1982. IS8 No. $36712-39-2.
Cincinnati, OH.	"	'
186

-------
Clayton, George D., and Florence E. CIayton, eds. 1982. Patty's Industrial
Hygiene 3rd Revised Edition, Vol. 2B. "Toxicology.", pp. 3253-3273. John Wiley
and Sons, New York, NY.
Deichmann, William B., and Horace U. Gerarde. 1969. Toxicology of Drugs and
Chemicals. Academic Press, NY.
Federal Environmental Agency (Berlin West), Waste Management Division. 1976.
Report Number NATO/CCMS Rpt. 55. EPA:PB270591.
Ful1er, B. J. Hushon, M. Kornreich, R. Quellette, L. Thomas, and P. Walker.
1976.	Scoring of Selected Organic Air Pollutants.
EPA-450/3-77-008b. The Mitre Corporation, McLean, VA.
GEOMET Technologies, Inc. 1981. Chemical Summaries for NTP Second Annual
Report Carcinogens. Rockville, Wi
Hawley, Gessner G. 1977. The Condensed Chemical Dictionary, 9th ed.
Van Nostrand Reinhold Company, NY.
International Agency for Research on Cancer. 1974. IARC Monographs on the
Evaluation of Carcinogenic Risk of Chemicals to Han" Vol. 7, pp. 203-21.
International Agency for Research on Cancer. 1982, IARC Monographs on the
on the Evaluation of Carcinogenic Risk of Chemicals to Man. Vol. 29,
pp. 93-148.	
Katz, Morris, ed. 1977. Methods of Air Sampling and Analysis. Alpha Inter-
society Committee, American Public Health Association, Washington, DC.
Kirk-Othmer. Encyclopedia of Chemical Technology, 2nd ed. John Wiley and
Sons, New York, NY. Vol. 3.
Mackison, Frank W., R. Scott Stricoff, and Lawrence J. Partridge, Jr., eds.
1978.	NIOSH/OSHA Pocket Guide to Chemical Hazards. DHEW (NIOSH) Publication
No. 78-210. Washington, DC.
Mason, Benjamin J., Douglas J. Pel ton, Ruth J. Petti, and David J. Schmidt.
1979.	Environmental Carcinogens and Human Cancer. GEOMET Report Number
HF-803. GEOMET, Incorporated, Gaithersburg, MD.
McGraw-Hill, Inc. 1977. McGraw-Hill Encyclopedia of Science and Technology.
New York, NY.
National Fire Protection Association. 1981. National Fire Codes, A Compi-
lation of NFPA Codes, Standards, Recommended~Tractices.""andHManuaTsT Vol. 13.
NFPA. Quincy, MA.
187

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Ochsner, J.C., T.R. Blackwood, and L.D. Zeagler. 1979. Status Assessment
of Toxic Chemicals: Benzene. EPA-600/2-79-210d. Industrial Lnvironmental
Research Laboratory, U.S. Environmental Protection Agency, Cincinnati, OH.
Fiver, Warren T., William Jurgelski, Jr., Terri Damstra, Hans L. Falk, and
Jean Bernheim. 1978. Exposure and Metabolic Mechanisms of Four Important
Industrial Pollutants; Benzene, Toluene," Carbon Disulfide, Methylene Chloride.
Office of Health Hazard Assessment, Reseach Triangle Park, NC.
Proctor, Nick W., and James P. Hughes. 1978. Chemical Hazards of the Work-
pi ace. J.B. Lippincott Company, Philadelphi a, PA.
Riggin, R.M. 1983. Technical Assistance Document for Sampling and Analysis
of Toxic Organic Compounds in Ambient Air. EPA-600/4-83-027. Battelle
Columbus Laboratories. Columbus, OH.
Sittig, Marshall. 1980. Priority Toxic Pollutants. Noyes Data Corporation.
Park Ridge, NJ.
U.S. Department of Health, Education and Welfare. 1977. NIOSH Manual of
Analytic Methods, Vol. 1. DHEW (NIOSH) Publ. No. 77-157^ Cincinnati, OH.
U.S. Department of Health, Education and Welfare. 1977. NIOSH Manual of
Analytic Methods, Vol. 3. DHEW (NIOSH) Publ. No. 77-157^ Cincinnati, OH.
U.S. Department of Health, Education, and Wei fare. 1974. Occupational Expo-
sure to Benzene. DHEW Publication No. (NIOSH) 74-137. National Institutefor
Occupational Safety and Health, Washington, DC.
U.S. Department of Health and Human Services. 1982. Third Annual Report on
Carcinogens. Public Health Service, National Toxicology Program. Washington,
U.S. Department of Labor. 1981. General Industry, OSHA Safety and Health
Standards (29CFR1910). Occupational Safety and Health Administration.
Washington, DC.
U.S. Department of Transportation. 1978. Chemical Hazards Response Informa-
tion System (CHRIS) Hazardous Chemical Data, United StatesT Coast Guard",
Washington, DC.
U.S. Environmental Protection Agency. 1979. Measurement of Benzene Emissions
from a Floating Roof Test Tank. EPA-450/3-79-020. Office of Air Quality
Planning and Standards, Research Triangle Park, NC.
188

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Chemical Name
Benzyl chloride
CAS Number
100-44-7
Chemical Classification
Aromatic halogen
Synonyms
A1 pha-tolylchloride; chloromethyl -benzene; alpha-chloromethyl -
benzene; alpha-chlorotoluene
Physical/Chemical Properties
Description:
Benzyl chloride is a colorless to light yel1ow liquid,
moderately volatile and a strong lacrimator
Boiling point:
179° C at 760 mm Hg
Melting point:
-39° C
Molecular weight:
126.6
Chemical formula:
C7 H7 CI
Vapor pressure:
1.4 mm at 25® C
10 mm at 60.8° C
100 mm at 114.2° C
Refractive index:
n° = 1.5412
Solubility:
Slightly soluble in water (49.3 mg/100 ml); soluble in
lipids
189

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Photochemical reactivity:
No photochemical degradation
Density:
1.026 at 18° C
Vapor density:
4,36 (air « 1)
Chemical reactivity:
Benzyl chloride undergoes Friedel-Crafts condensation
reactions in the presence of such metals as iron, copper,
zincs aluminum3 magnesium and tin. The compound hydro-
lyzes slowly in boiling water. The reactions of ben2yl
chloride involve
a.	the reaction of the side chain containing the halo-
gen, and
b.	the reaction of the aromatic ring
Environmental Fate
Benzyl chloride decomposes slowly in the presence of water.
The half-Hfe for the hydrolysis of benzyl chloride at pH7
25° C is 15 hours, at 60° C hydrolysis is 45 times faster
Sources of Emissions
Production:
There are currently three producers of benzyl chloride at
four locations. An estimated 115 minion lb was produced
in 1978. Table D-32 lists the plant locations and the esti-
mated production
TABLE D-32. BENZYL CHLORIDE PRODUCERS
1978	1978
Capacity Production
Company	Location	(10° Ib/yr) (106 1b/yr)
Monsanto
Bridgeport, NJ
80
52.5

Sauget, IL
80
52.5
Stauffer
Edison, NJ
12
8.0
UOP, Inc.
E, Rutherford, NJ
3
2.0

Total
175
115.0
Source: Mannsvil1e Chemical Products 1978
190

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Total estimated missions (including process, storage,
and fugitive) were 59,000 lb/year in 1978
Uses:
The major end uses for benzyl chloride are butyl benzyl
phthalate (75%) benzyl alcohol (7%), quarternary ammonium
compounds (10%), and miscellaneous uses (8%) (1978 data)
Table D-33 lists benzyl chloride emissions from producers
and users
Transportation/storage:
Benzyl chloride is shipped in glass carboys, phenolic-
lined steel or nickel drums, tank cars and tank trucks.
The chemical has an effective storage life of 2 to 3 months
at normal temperatures. The emission factor from storage
and handling has been estimated as 0.000025 to 0.00040 lb
lost for lb produced and used
Di sposition:
No data available
Sampling and Analytical Methods
Sampling method:
A known volume of air is drawn through a charcoal tube
to trap the organic vapors present
NI0SH Manual of Analytical Methods: Method No. SI15
Analytical method:
The sample is desorbed with carbon disulfide and the
desorbed sample Is injected into a gas chromatograph
for analysis
NI0SH Manual of Analytical Methods: Method No. S115
Detection limits:
For a 10 1 sample (25° C 744 mm Hg), the detection
range is 2-8 mg/m^
191

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ms
'seel
370
378
073
010
196
196
019
006
006
007
00?
007 ;
007 j
007 |
007 |
007 '
007
00? •
007
TABLE 0-33. BENZYL CHLORIDE EMISSIONS FROM PRODUCERS AND USERS
L
Location
Source
Process
Emissions (lb/yr)
Storage
Fugitive
Bridgeport, NJ
Production
20,633
1785
3633
Sauget, IL
Production
20,633
1785
3833
Edison, NJ
Production
4 ,000
344
74 4
E. Rutherford, NJ
Production
1,000
86
186
Bridgeport,, NJ
BBP
10,178
1078
2329
Sauget, IL
BBP
10,178
1078
2329
Chattanooga, tn
Benzyl alcohol
945
108
297
Newark, HJ
Benzyl alcohol
200
32
88
Doonton, NJ
Benzyl alcohol
200
32
88
HcCook, IL
QAC
322
46
92
Morris, IL
QAC
322
46
92
Mape1 ton, IL
OAC
322
46
92
Lodi, NJ
QAC
322
46
92
Houston, TX
QAC
322
46
92
Janesville, WI
QAC
322
46
92
Jersey City, NJ
QAC
322
46
92
Philadelphia, PA
QAC
322
46
92
Cincinnati, OH
QAC
322
46
92
Salisbury, NC
QAC
322
46
92
71,347
6788
14,647

-------
Possible interferences:
1.	High humidity
2.	Compounds with the same column time retention will
interfere with analysis
Permissible Exposure Limits
1 ppm (5 mg/m3) OSHA standard
Human Toxicity
Chronic toxicity:
Carcinogenicity--There are no case reports or epidemiologic
studies available in humans; however, benzyl chloride is
carcinogenic in experimental rats. There is a long-term
animal bioassay on test in FY83 by the National Toxicology
Program
Mutagenic!ty--Benzy1 chloride was weakly mutagenic to
Salmonella typhimuiium (1975). Further microbial testing is
on test for mutagenesis and genetic toxicity in FY83 by
the National Toxicology Program
Other chronic toxicity:
Air concentrations of 32 ppm were reported to cause
severe irritation of the eyes and respiratory tract
of humans
Bibliography
Fishbein, L. 1979. Potential Industrial Carcinogens and Mutagens. Elsevier
Scientific Publishing Co. Amsterdam, pp. 278-79.
International Agency for Research on Cancer. 1976. IARC Monographs on the
Evaluation of Carcinogenic Risk of Chemicals to Man~ Vol. 11, pp. 217-23.
Kirk-Othmer. 1979. Encyclopedia of Chemical Technology, 3rd ed. John Wiley
and Sons, Mew York, NY, Vol. 5, pp. 828-38.
Mannsville Chemical Products. 1978. Chemical Product Synopsis on Benzyl
Chloride. Mannsville, NY.
Systems Applications, Inc. 1980. Human Exposure to Atmospheric Concentra-
tions of Selected Chemicals, EPA/OAQPS, Research Triangle, NC, Vol. I,
pp. A4 1-24.	
193

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U.S. Department of Health, Education, and Welfare. 1977. NIOSH Manual of
Analytical Methods, 2nd ed. U.S. DHEW/PHS/NIOSH, Vol. 2, S115.
U.S. Department of Health, Education, and Welfare. 1978. NIOSH Criteria for
a Recommended Standard	Occupational Exposure to Benzyl Chloride.
DHEW/PHS/NIOSH Publication No. 78-182.
U.S. Department of Health and Human Services. 1983. Review of Current DHHS,
DOE, and EPA Research Related to Toxicology, National Toxicology Program.
1M37PWRTP";	
194

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Chemical Name
Beryl 1i urn
CAS Number
7440-41-7
Chemical Classification
Chemical element, rare metal
Synonyms
Beryl 1ium-9, glucinium, glucinum
Physical/Chemical Properties
Description:
Hard, noncorrosible grey metal of alkaline earth family:
lightest structural metal known. .Beryllium is available
as powder, beads, electrolytic flakes, ingot, strip,
sheet, plate, foil, wire, rod, bar, tube, castings, and
fabricated parts
Boiling point;
2970° C
Melting point:
1284-1300° C
Atomic weight:
9.01
Chemical formula:
Be
Solubility:
Soluble in acids or alkalis
Atmospheric reactivity:
Two radioactive isotopes of Beryllium, Be? and BelO,
are formed in the upper atmosphere as a result of intense
cosmic-ray activity
195

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Density:
1.85 g/cm3 (20° C)
Chemical reactivity:
Reacts with hot water, alkali, and dilute
oxidation resistant; good transparency to
heat capacity and thermal conductivity
Sources of Emission
Production:
From beryl ore or from bertrandite ore: In recovering
the metal from the usual ores (beryl and bertrandite),
the sulfate process and the fluoride process produce
beryllium oxide or hydroxide. This step is followed
either by a thermal reduction or an electrolytic process.
Thermal reduction involves the magnesium reduction of a
halide, generally beryl 1ium fluoride. The electrolytic
process requires conversion to the chloride for the
fused-salt bath and produces Be of higher purity.
Approximately 74,000 lb of beryllium were produced in
1977
Uses:
To form alloys with copper, nickel, and aluminum with
emissions of approximately 55,000 lb/year
In manufacture of ceramics and vitreous enamel
To make refractory crucibles as moderator and reflecting
material in nuclear reactors
To make gas mantles
As a window material for X-ray tubes
To produce a heat sink material in low-weight, high
performance aircraft brakes, and to make mirror compo-
nents of satellite optical systems
To make electrical components
Storage and transport:
Usually stable during transport. Shipped in steel and
fiber drums. Should be stored in dry place away from
acids;
X-rays; high
19b

-------
4
acids, caustics, and chlorinated hydrocarbons. Kept
separate from oxidizing materials
Disposition:
Emission losses at production sites are kept down by
reusing beryl 1iurn occurring in production and processing
(powder, chips, beryllium compounds)
Emission dusts can be controlled by use of filters and
scrubbers at production and processing sites
Liquid or solid waste with too low a beryllium concen-
tration to warrant recovery is disposed of in special
dumps, but prior to disposal, the beryllium compound
involved must be converted to the relatively inert oxide
Beryllium emissions occur during the combustion of
fossil fuels which represents the major source of non-
occupational exposure
Some sources of beryllium emissions are given in Tables 0-34 through D-38
Sampling and Analytical Methods
1. NIOSH method P & CAM 121 for "Beryllium in Air" for use
on air, settled dust, ore, and swipe samples
a.	Air samples can be collected by using a cellulose
membrane filter, an electrostatic precipitator, or
a chemically clean impinger containing 10% HNO3
soluti on
Settled dust and ore samples can be collected
directly in chemically clean jars
Swipe samples should be collected on Whatman filter
paper
b.	Air samples are ashed with nitric acid, treated with
1:1 hydrochloric acid, and dissolved in a weak
hydrochloric acid solution
Ore and settled dust samples are ground in a mill
to pass a U.S. Standard 200-mesh sieve
-dust samples are ashed with nitric acid
-ore samples are fused without ashing
c.	The samples are analyzed by atomic absorption
spectrophotometry
Detection limits:
0.03-8,0 ug/ml
197

-------
TABLE D-34. SOURCES OF BERYLLIUM EMISSIONS
Source
Mica, feldspar mining
Gray iron foundry
Cupola
Ceramic coatings
Beryl 1ium alloys and compounds
Beryllium fabrication
Power plant boilers
Pulverized coal
Stoker coal
Cyclone coal
All oil
Industrial boilers
Pulverized coal
Stoker coal
Cyclone coal
All oil
Residential/commercial boilers
Coal
Oil
Source: Si tti g 1975
198

-------
Table D-35. SOURCES OF BERYLLIUM FROM INDUSTRIAL AND SOLID
WASTE INCINERATION EMISSIONS
Source
Mini ng
Production of beryllium metal and its
compounds
Cement pi ants
Dry process
Feed to raw mill
Wet process
Kiln
Clinker cooker
Clinker cooler
Processing or uses of beryllium and its
compounds
Beryllium alloys (stamped and drawn)
Beryllium alloys (molding)
Uncontrolled
After a baghouse
Ceramics
Rocket propel1 ants
Beryl 1iurn metal
fabrication
199

-------
TABLE D-36. SOURCES OF BERYLLIUM EMISSIONS
FROM FUEL COMBUSTION, COAL
Source
Power plants
Kansas
South Carolina
Illinois
Mi chigan
Coal beds
Maryland
Ohio
Pennsylvania
A1 abama
Georgia
Kentucky-east
Kentucky-west
Tennessee
Virginia
West Virginia
II "tinois
Indiana
Arkansas
Iowa
Mi ssouri
Oklahoma
Montana
North Dakota
Wyoming
Colorado
Utah
Source: Sittig 1975
200

-------
TABLE D—37. SOURCES OF BERYLLIUM EMISSIONS
FROM FUEL COMBUSTION, OIL
Source
Residual oil
Power plant, Connecticut
Residual No. 6
Source: Sittig 1975
TABLE D-38. SOURCES OF BERYLLIUM EMISSIONS
FROM WASTE INCINERATION
Source
Sewage sludge incinerator
Multiple hearth,
after wet scrubber
Fluidized bed,
after wet scrubber
Municipal incinerator,
uncontrolled
Municipal incinerator,
after electrostatic
precipitator
Source: Sittig 1975
201

-------
Possible Interferences:
High concentrations of aluminum, silicon, and magnesium
depress the sensitivity of beryllium determination
NIOSH method P & CAM 173 for "General Procedure for Metals"
Same as method P & CAM 121 above
NIOSH method P & CAM 288 for "Beryllium and Beryllium Compounds
(as Be)"
a.	filter collection
b.	ashing of samples with nitric acid and sulfuric
acids; sample is solubilized in 3% sulfuric
acid with 2% sodium sulfate added
c.	graphite furnace atomic absorption analyses
Detection limits:
0.5-10.0 ug/sn3
Possible interferences:
Calcium's effect 1s masked by Z% sulfuric acid
Sodiums potassium, and ammonium enhance the
¦ absorbance of beryllium
Perchloric, phosphoric, and hydrofluoric acids
produce interfering non-atomic peaks
NIOSH method P & CAM 351 for "Trace Elements"
a.	filter col lection
b.	acid digestion
c.	inductively coupled plasma atomic emission spectroscopy
fICR-AES)
Detection limits:
5-2000 yg/rt«3f in a 500 1 air sample
Possible interferences:
Changes in density and viscosity of different acids and
acid concentrations affect the sample uptake rate
Chemical interferences:
Molecular compound formation
Ionization effects
Solute volatilization effects
Spectral interferences
202

-------
5.	NIOSH method S 339 for "Beryllium and Beryllium Compounds
(as Be)"
a.	filter collection
b.	acid digestion
c.	flameless atomic absorption
Detection limits:
2.68-11.84 ug/m3
Possible interferences:
None known
6.	Tentative Method of Analysis for Beryllium Content of
Atmospheric Particulate Matter
a.	cellulose, glass fiber, or membrane filter collection
b.	ash sample
c.	measure fluorescence of an aqueous beryllium solution with
ultra violet light in the presence of morin
Detection limits:
0.01-1.0 ug Be/10 ml aqueous beryllium solution
Possible interferences:
Presence of zinc may interfere slightly
7.	Analytical Methods for Beryllium and Beryllium Compounds:
See Table D-39
Permissible Exposure Limits:
OSHA	ACGIH
TWA	2 ug/m3 1	2.0 ug/m3 (0.002 ppm)
Ceiling 5 ug/m3
Peak	25 ug/m3/3Q min
Human Toxicity:
Acute Toxicity:
Inhalation of beryl 1ium vapor causes acute "metal-fume
fever" (foundryman's fever), which can be the preliminary
stage of beryllium pneumonia
Inhalation of beryllium dust can also cause pneumonia
Beryllium slivers or dusts that penetrate the skin can
produce poorly healing sores
203

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TABLE D-39. ANALYTICAL METHODS FOR BERYLLIUM AND COMPOUNDS
Jampl® matrix
Sample preparation
Ait»y pto(«)un
$tniiti»ily <»»
limit of
dttiction
BulV chemical
Formulations
Alumina ceramics
Technological tolution
Copper-beryllium alloy
Ak
Add solutions o< urami!-,V,iV-diacstie
acid, acetate buffer and water
Add solutions of chromal felui G,
cetylt'imethyUmmonium chloride
and acetate buffer; dilute; allow
colour to develop
Add hydroxynaphihol blue solution;
allow 10 ttand 5 min
Grind; dissolve in itrong phosphoric
•cid solution
Make complex with sodium (ethyl*
enedinitrilo) tetraacetate; precipitate
beryllium at phosphate; ignite; weigh
ai pyrophosphate
Add ammonium aurintricarboxylate
to form i red lake
Dissolve collection filter matrix in hy-
drofluoric acid; add nitric acid and
water; boil ; dilute
UV 126? nm)
Spectrophotometry
(626 nm)
Spectrophotometry
AAS
Aerosol-Spark
spectrography
Grav imetry
Photometry
f AAS
AAS
2,7 «
0.02 m^Ag
0.001 mg/l
0.05 ng/m
2.S ng/m'
Dry collection filler; add nitric and
sulphuric acids and distilled, deioniied
water; reflux at 0O°C for 7 hrs ; add
EDTA-buffer solution and sodium hy-
droxide to pH 6: add irifluotoaceryl-
ecetoncbemene solution {1:1); de-
cani chelate; wash wish sodium hy-
droxide
Extract filler with sulphuric acid; add
chrome Azurol S solution, gum arabic
solution and EDTA; adjust pH to 2.0;
add cetylpyridinium bromide and
hexamine solution; adjust to pH S
Ash collection filter strips; reflux with
mixture of nitric and hydrochloric
acids containing 55.S pg/ml indium and
yttrium; concentrate extraction liquid;
add nitric acid; centrifuge; add 40%
lithium chloride solution containing ¦
20% nitric acid and 200 pg/ml indium
and yn/ium
GC/EC
Spectrophotometry
[605 nm)
Optical emission
spectroscopy
5.3 mg/m
Source: IARC 1980
204

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Chronic Toxicity:
Carclnogenesis--Suspected human carcinogen. There is suf-
ficient evidence of carcinogenicity of some beryllium compounds
in experimental animals
Other Chronic Toxicity:
On test in FY 83 for biochemical/eellular/tissue effects,
for pulmonary toxicity, and for acute/chronic toxicity {U.S.
DHHS 1983)
Industrially used beryllium metal and its compounds cause
chronic respiratory disease (beryllium disease or
berylliosis)
Bibliography
American Conference of Governmental Industrial Hygienists. 1982. TLVS,
Threshold Limit Values for Chemical Substances and Physical Agents in
the Work Environment witOntended CHanges for 1982^ ISBNO.936712-39-2.
Cincinnati, OH.
Considine, Douglas M., ed. 1974. Chemical and Process Technology
Encyclopedia. McGraw-Hill Book Company, NY.
Deichmann, William B., and Horace W. Gerarde. 1969. Toxicology of
Drugs and Chemicals. Academic Press, NY.
GEOMET Technologies, Inc., 1981. Chemical Summaries for NTP Second
Annual Report on Carcinogens. Rockville, MD.
Haw!ey, Gessner G., 1977. The Condensed Chemical Dictionary, 9th ed.
Van Klostrand Reinhold Company, NY.
International Agency for Research on Cancer. 1980. IARC Monographs on
the Evaluation of Carcinogenic Risk of Chemicals to Humans. Lyons,
France. Vol. 23. "Some Metals and Metallic Compounds."
International Agency for Research on Cancer. 1972. IARC Monographs on
the Evaluation of Carcinogenic Risk of Chemicals to Man. Lyons,
			t &> Mf" iunuuuuuuuuuuuuuuuuuuuuuuiuiuii.iuiiiiiyniMtnuuiuhHuuuijiuiutjiiuuuuyu.iiiuyuiiiuiuiiiuuuuuuL 				 iikikikikikikikikikikikik mjkikikikiki i.u 1111 iiliu uum muuuui
France.Vol. 1.
Katz, Morris, ed. 1977. Methods of Air Samp]ing and Analysis. A1 pha
Intersociety Committee, American Public Health Association, Washington, DC.
Kirk-Otbmer. Encyclopedia of Chemical Technology, 2nd ed. John Mi ley
and Sons, New York, NY. Vol. 3.
205

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Mackison, Frank W., R. Scott Stricoff, and Lawrence J, Partridge, Jr.,
eds, 1978. NIOSH/OSHA Pocket Guide to Chemical Hazards. DHEW (NIOSH)
Publication No. 78-210. Ya sfiTngton, t)C.
McGraw-HH1, Inc., 1977. McGraw-Hill Encyclopedia of Science and
Technology. New York, NY. Vol. 2.
National Fire Protection Association. 1981. National Fire Codes, A
Compilation of NFPA Codes, Standards, Recommended Practices, and Manuals,
Quincy, MA. NFPA, Vol. 13.				
Proctor, Nick W., and James P. Hughes, 1978. Chemical Hazards of the
Workplace. J.B, Uppincott Company, Philadelphia, PA.
Sittig, Marshall. 1975, Environmental Sources and Emissions Handbook.
Noyes Data Corporation. Park Ridge, NJ.
Si ttig, Marshal 1, 1980. Priority Toxic Pollutants. Noyes Data Corpo-
ration. Park Ridge, NJ.
U.S. Department of Health and Human Services. 1983. National Toxicology
Program: Review of Current DHHS, DOE, and EPA ResearchRelated to
Toxicology! NTP-83-001. National Toxicology Program. Research
Triangle Park, NC.
U.S. Department of Health and Human Services. 1981. Second Annual
Report on Carcinogens. Public Health Service, National Toxicology
Program. Washington, DC.
U.S. Department of Health and Human Services. 1982. Third Annual
Report on Carcinogens. Public Health Service, National Toxicology
Program. Washington, DC.
U.S. Department of Health, Education	and Wei fare. 1977. NIOSH Manual
of Analytic Methods, Vol. 1. DHEW	(NIOSH) Publ. No. 77-157-A.
Cincinnati, OH.
U.S. Department of Health, Education	and Welfare. 1977. NIOSH Manual
of Analytic Methods, Vol. 5. DHEW	(NIOSH) Publ. No. 79-141-A.
Cincinnati, OH.
U.S. Department of Health, Education	and Welfare. 1977. NIOSH Manual
of Analytic Methods, Vol. 7. DHEW	(NIOSH) Publ. No. 82-100-A.
Cincinnati, OH.
U.S. Department of Health, Education	and Welfare. 1977. NIOSH Manual
of Analytic Methods, Vol. 3. DHEW	(NIOSH) Publ. No. 77-1'57-C.
Cincinnati, OH.
206

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U.S. Department of Labor. 1981. General Industry, OSHA Safety and
Health Standards (29CFR1910). Occupational Safety" and" Health
Admi ni strati on. Washington, DC.
U.S. Department of Transportation. 1978. Chemical Hazards Response
Information System (CHRIS) Hazardous Chemical Data United States.
Coast Guard, Washington, DC.
U.S. Environmental Protection Agency. 1976. Disposal of Hazardous
Wastes, Manual on Hazardous Substances in Special Wastes. NATO/CCMS
Report 557 Washington, DC.
207

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Chemical Name
Cadmium
CAS Number
7440-43-9
Chemical Classification
Elemental metal
Synonyms
C.I. 77180
Physical/Chemical Properties
Description:
Soft blue-white malleable metal or grey powder
Boiling point:
767s C
Melting point:
3218 C
Atomic weight:
112.4
Atomic formula;
Cd
Vapor pressure:
0 at 20° C
Densi ty:
3.65
Refractive index:
1.13
Solubility:
Insoluble in water; soluble in dilute acids
208

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Photochemical reactivity:
Retention time in the atmosphere is dependent on parti-
cle size and meteorological parameters. Cadmium found
in the air is usually in particulate form as the oxide,
chloride or sulfate
Environmental Fate
About 85 percent of cadmium aerosols were found to be soluble.
Cadmium which is emitted to the air is ultimately deposited in
soil and water. The half-life of cadmium in humans has been
calculated to be as long as 38 years
Sources of Emission
The primary metals industry (mining and processing), waste
disposal by incinerator, fertilizer processing, and the
burning of fossil fuels are the principal man-made stationary
sources of cadmium emissions to air. Cadmium vaporization
occurs at fairly 1ow temperatures, approximately 767® to 907° C
and therefore is readily emitted by processes such as ore
roasting, pyrosmelting, steel scrap melting, incineration of
wastes and burning of fossil fuels. Total estimated emis-
sions of cadmium from stationary sources are 3,260,000 lb/
year and mobile sources add approximately 70,000 lb/year
for a total of 3,326,000 lb/year. Some estimates of cadmium
emissions by source are presented in Table D-40
Production:
The 1980 domestic production of cadmium and eight high
volume cadmium compounds was about 17 million lb and
2 million lb were imported
Uses:
Cadmium and certain cadmium compounds are widely used
commercially in electroplating, alloys, solders, plas-
tic stabilizers, batteries, fungicides, and in phosphors
and pigments for television tubes, inks, artists'
colors, glass, ceramics, textiles, paper, and fertil-
izers. Emission sources for cadmium from consumptive
uses, industrial sources, and processes are presented
in Tables D-41 to D-43
209

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TABLE D-40. CADMIUM EMISSIONS
Aftotinl	I TMs
Source	la less	Pollutant
Copper mtilng	"EC	NEC
line Mining	<1	0.01
Lead Mining	NEC	NIC
Frlsur? Copper
lutlini	229	7-59
Ktvcrbcticsry Fumae®	M	3.3.2
Converters	270	8.IS
KttcrUI Handling	59	1.96
FrlHry Sine
lai
-------
TABLE D-41. EMISSION FACTORS FOR CONSUMPTIVE USES OF CADMIUM
Source8
Emission factors
Rubber tire wear
Fungicides
Superphosphate
fertilizers
Motor oil consumption
{in vehicle)
Cigarettes
0.003 kg/10®km {0.01 lb/106 vehicle miles)
0.02 kg/103 Titers (0.05 lb/103 gal.)
of spray
0.0001 kg/103kg (0.0002 lb/ton) of fertilizer
0.0006 kg/106km (0.002 lb/100 vehicle miles)
16.0pg/20 cigarettes
"All sources are uncontrolled.
Source: Sittig 1975
211

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TABLE D-42. EMISSION FACTORS FOR CADMIUM FROM INDUSTRIAL SOURCES
Source3
Emission Factor
r
Mining of zinc-bearing or®
0,0005 kg/103kg (0.001 lb/ton) of Zn
or 0.1 kg/103kg (0-2 lb/ton) of Cd mined
Zinc smelters
150 kg/103kg (300 lb/ton) of Cd charged
or 1.0 kg/103kg (2.0 lb/ton) of Zn produced
Copper smelters
650 kg/1Q%g {1300 lb/ton) of Cd charged
or 0.4 kg/103kg (0.07 lb/ton) of Cu produced
Lead smelters
650 kg/103kg S1300 lb/ton) of Cd charged
or 0.1 kg/103kg (0.2 lb/ton) of Pb produced
Cadmium rafining unite
13 kg/103kg (25 lb/ton) of Cd produced
Secondary capper
2 kg/ltfkg {4 lb/ton] of Cu scrap
Secondary lead
p
-------
TABLE D-43. EMISSION FACTORS FOR PROCESSES
INVOLVING CADMIUM
Source 3
Emission factor,
kg/103kg {fb/ton) of
cadmium charged
Pigments
8(15)
Plastic stabilizers'
3(6)
Alloys and solders
5(101
Batteries (Ni-Cd)
1 12}
Miscellaneous (x-ray strains,
cathode ray tubes, nuclear
reactor components, etc.)
1 (2)
* Emission are uncontrolled unless otherwise specified.
Source: Sittlg 1975
Disposition:
Emission factors for cadmium from waste incineration
have been estimated in the range of 0.003 lb/103 tons
to 0.8 Ib/lO^ tons depending on source. These emis-
sion factors are presented in Table 0-44
Sampling and Analytical Methods
Cadmium dust--NIOSH Manual of Analytical Methods; Method
number S 312
Sampling method:
Sample containing filters are wet-ashed with nitric
acid and the sample is sol utilized in hydrochloric acid
Analytical method:
The sample solution is aspirated into an atomic absorp-
tion spectrophotometer. The absorbance is proportional
to the cadmium concentration
Detection limits:
This method was validated in the range of 0.12 to
0.98 mg/m^ using a 2.5 1 sample
213

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TABLE D-44. EMISSION FACTORS FOR CADMIUM
FROM WASTE INCINERATION
Source a
Emission factor
Sewage sludge incinerators

Multiple hearth c'^
0.004 kg/103kg (0.007 ib/ton) of solid
waste incinerated9
Ftuidlzed bedc
0.0002 kg/103kg {0.003 Ib/IO^tonsJof
sofid waste incinerated
Municipal incinerator

Refuse onlyc
0.4 kg/106kg 10.8 lb/103 tons) waste
indnerated
Refuse and sludge®
0.3 kg/10®kg {0.6 Ib/103tons) waste
incinerated
Overall value for
uncontrolled solid waste
incineration (municipal)*
0.0002 kg/103kg (0.003 Ib/ton) of solid
waste incinerated
Lubricating oil'
0.0002 kg/103 liters (0.002 lb/103 gal.)
of oil
¦ In this table, emissions art controlled unless otherwise specified.
Source: Sittlg 1975
214

-------
Possible interferences:
There are no known spectral line interferences for this
assay
Cadmium fume—NIOSH Manual of Analytical Methods; Method number
S313
The method is simple and specific for cadmium, but will
not distinguish between cadmium dust and cadmium fume
Permissible Exposure Limits
OSHA Standard
0.1 mg/m3	8-hr TVIA (fumes)
0.3 mg/m^	ceiling (fumes)
0.2 mg/m^	8-hr TWA (dust)
0.6 mg/m^	ceiling (dust)
Human Toxici ty
Acute Toxicity:
About 1 mg/m3 of cadmium inhaled over an 8-hour period gives
rise to clinical symptoms such as pulmonary congestion and
edema; an air level of cadmium of 5 mg/m^ inhaled over the
same period can be lethal
Chronic Toxicity:
Carcinogenicity-~The evidence of carcinogenicity in humans is
limited; studies have suggested that occupational exposure to
cadmium (possibly the oxide) increases the risk of prostate,
respiratory, and genitourinary cancers in humans. The evidence
for the carcinogenicity of cadmium and certain cadmium
compounds in experimental animals is sufficient
Mutagenic!'ty--There is conflicting evidence with regard to the
production of chromosomal aberrations in humans exposed
to cadmium
Teratogenicity--There is no evidence that cadmium is teratogenic
in humans- Teratogenic effects have been demonstrated in
animals using very high doses
215

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Bibliography
International Agency for Research on Cancer. 1976. IARC Monographs on the
Evaluation of the Carcinogenic Risk of Chemicals to Man. Vol, 11.
Lyon, France, pp. 39-/4,
International Agency for Research on Cancer. 1982. IARC Monographs on the
Evaluation of the Carcinogenic Risk of Chemicals to Humans. Supplement
T. Lyon, France I
Mason, B.J., et al. 1979. Environmental Carcinogens and Human Cancer.
GEOMET Report Number ESF-1185. GEOMET Technologies, Inc., Rockville, MD.
pp. 186-215.
U.S. Department of Health, Education, and Welfare. 1976. NIOSH Criteria
for a Recommended Standard...Occupational Exposure to Cadi urn. DHEW/PHS/NIOSH
Publication No. 76-192.
U.S. Department of Health, Education, and Wei fare. 1977. NIOSH Manual of
Analytical Methods. DHEW/PHS/NIOSH, S 312 and S 313.
U.S. Department of Health and Human Services. 1982. National Toxicology
Program, Third Annual Report on Carcinogens, pp. 76-80.
Sittig, M., 1975. Environmental Sources and Emissions Handbook.
Noyes Data Corporation. Park Ridge, NJ. pp. 32-38.
Sittig, M., 1980. Priority Toxic Pollutants. Noyes Data Corporation.
Park Ridge, NJ. pp. 102-107.	
U.S. Environmental Protection Agency. 1978. Health Assessment Document for
Cadmium. EPA Office of Research and Development. Washington, DC.
216

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Chemical Name
Carbon Tetrachloride
CAS Number
56-23-5
Chemical Classification
Halogenated hydrocarbon
Synonyms
Benzinoform; carbon chloride; carbona; flukoids; freon 10; halon
104; methane tetrachloride; methane, tetrachloro-necatorina;
perchloromethane; tetrachlorocarbon; tetrachl oromethane; tetrafi no!;
tetraform; tetrasol
Physical/Chemical Properties
Description:
Clear, colorless heavy liquid
Boiling point:
76.75° C
Melting point:
-22.8° C
Molecular weight:
153.8
Chemical formula:
CCI4
Vapor pressure:
91 mm Hg 20° C
113 mm Hg 25° C
Vapor density:
5.32 (air = 1)
Refractive index:
1.4607 20° C
217

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Solubilfty:
Miscible 1n organic liquids. Solubility in water
0.08 g/100 ml water at 25® C.
Log partition coefficient {octanol/water):
2.64
Photochemical reactivity:
CC14 is stable 1n the troposphere and there 1s appar-
ently an absence of physical or biological removal mechanisms.
Therefore, CCI4 would be expected to be a precursor of
stratospheric ozone-destroying chlorlnations
Chemical reactivity:
Chemically not reactive; not easily hydrolyzed
Environmental Fate
CC14 Is stable in air and water and tends to bioaccumulate.
It has a half life of about 10 years
Sources of Emissions
Production:
U.S. production of CC14 was estimated as over 1 billion
lb in 1974 and dropped to an estimated 717 million lb
in 1981
Production emissions for 1978 are presented in Table D-45
Uses;
The major end-use for CC14 is in the production of
fluorocarbon gases. The remaining CCI4 production is
used in solvent applications as an oil, wax and fat
extractant; in rubber cement; in polishes, paints and
lacquers; in printing inks and stains; and in pesticide
manufacturing. Estimated end use consumption; nation-
wide emissions and point sources are presented in
Tables D-46 and D-47 and Figure D-3
Storage:
Storage emission factors were reported from two site
visits as 0.000442 and 0.00374 lb per lb used
218

-------
TABLE D-45. 1978 CARBON TETRACHLORIDE PRODUCTION EMISSIONS
Company
Location
Process Vent
CMlaslona
Storage Vant
Emission*
Tuqltlv*
Dulsslons
Total D*lsalons
Ub/yO
St/seel**
(Ita/yrl
(9/acclb
(lb/yrl
(9/aoclb
Ob/yrl

-------
TABLE 0-46. 1978 CARBON TETRACHLORIDE CONSUMPTION BY END USE
End Use
Percent o£ Consumption
	End Use	Total Consumption	(H lb 7
Dichlorodifluoromethane (F-12)
Trichlorofluoromethane (F-ll)
Solvents and miscellaneous
Export
Total
Source: Systems Applications, Inc. 1980
TABLE D-47. 1978 ESTIMATED CARBON TETRACHLORIDE NATIONWIDE EMISSION LOSSES
Estimated National
- Source	 Emission (H Ib/yr)
Production	4.56
Dichlorodifluoromethane (F-12)
Trichlorofluoromethane	0•47
Solvents, miscellaneous	60.0
Export 0
Total	65.03
Source: Systems Applications, Inc. 1980
55
34
8
	3
100
412. 5
255.0
60.0
22-5
750.0
220

-------
PO
ho
-r;
\	a
Figure D-3. Specific point sources of carbon tetrachloride emissions.
Source: Systems Applications, Inc. 1980

-------
Disposition:
Emissions data from disposition were not available.
Host large-scale consumers recover impure solvents by
distillation. Residues from recovery operations are
waste dumped or burnt in special waste incinerators
Sampling and Analytical Methods
NIOSH Manual of Analytical Methods—Method Number S 314
Sampling method:
A known volume of air 1s drawn through a charcoal tube
to trap the organic vapors present
Analysis method:
An aliquot of the sample that has been desorbed with
carbon disulfide is injected into a gas chromatograph
Detection limits:
The working range of this method is 16-480 mg/tn^ for
a 15 1 sample size
Possible interferences:
1.	High humidity
2.	Compounds present in the sample with the same
column retention size
Materials Damage
Reacts sometimes exposively with aluminum and its alloys
Permissible Exposure Limits
OSHA Standard
10 ppm 8-hr TWA
25 ppm ceiling
200 ppm maximum peak for 5 min in any 4-hr period
Human Toxicity
Acute Toxicity:
Humans exposed to 14,000 ppm for 50 s were rendered unconscious.
CC14. can produce coma and death from respiratory arrest or
circulatory col 1 apse
222

-------
Chronic Toxicity:
Carcinogenesis—There are suggestive case reports of liver
cancer in humans. There is sufficient evidence that CC14
is carcinogenic in experimental animals
Mutagenicity--There is no evidence that CC14 is mutagenic
Teratogenicity—CC14 is fetotoxic in experimental animals.
There were no data available in humans. Biochemical, eel 1ular
tissue effects, and systemic organ toxicity are on study in
FY83 (U.S. DHHS 1983)
Bib!iography
Federal Environmental Agency (Berlin-West). Disposal of Hazardous
Wastes, Manual on Hazardous Wastes in Special Wastes. NATO/CCMS
Report 55.
Fishbein, L. 1979. Industrial Carcinogens and Mutagens. Elsevier
Scientific Publishing Company. Mew York, NY. pp. 217-220.
International Agency for Research on Cancer. 1979. IARC Monographs
on the Evaluation of the Carcinogenic Risk of Chemicals to Humans.
Lyon, France. Vol. 20. pp.3/1-400.
Kirk-Othmer. 1979. Encyclopedia of Chemical Technology, 3rd ed.
John Wiley and Sons, New York, NY. Vol. 5. pp. 704-714.
Mason, B., et al. 1979. Environmental Carcinogens and Human Cancer.
EPA Contract Number 68-03-2504. USEPA/ORD. Research Triangle Park,
NC. pp. 243-263.
U.S. Department of Health, Education, and Wei fare. 1977. NIOSH Manual
of Analytical Methods. HEW/PHS/NIOSH. Vol. S 314.
U.S. Department of Health, Education, and Welfare. 1975. NIOSH Criteria
for a Recommended Standard.~. Occupational Exposure to CarbonTetra-
cKTorTHeT HEW/PHS/NIOSH. Publication" number 76-133.
U.S. Department of Health and Human Services. 1983. National Toxicology
Program, Review of Current DHHS, DOE, and EPA Research Related to
Toxicology.—USOHHS/PHS/NTP.	
Systems Applications, Inc. 1980. Human Exposure to Atmospheric
Concentrations of Selected ChemicTPT PB8l-1932t>2. Vol. 1.
pp.6-1to6-21.
223

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National Library of Medicine.
Carbon Tetrachloride.
U.S. Environmental Protection
Carbon Tetrachloride.
Toxicology Data Base. Animal Carcinogens.
Agency. Chemical Hazard Information Profile.
224

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Chemical Name
Chiorobenzene
CAS Number
108-90-7
Chemical Classification
Halogenated cyclic hydrocarbon
Synonyms
Monochlorobenzene, phenyl chloride, chlorobenzol, MCB,
benzene chloride
Physical/Chemical Properties
Description:
Colorless liquid, very refractive, highly volatile
Boiling point:
131.7° C
Melting point:
-45.6° C
Molecular weight:
112.56
Chemical formula:
C6H5C1
Vapor pressure:
12.14 mm at 25° C
Density:
1.1058 at 20° C (rel. water at 4° C}
Vapor density:
3.88 {air = 1)
Refractive index:
1.5216 {25° C) highly refractive
Sol ubility:
Insoluble in water
225

-------
Log partition'coefficient (octanol/^O):
2.84
Photochemical reactivity:
No photochemical degradation
Chemical reactivity:
At ordinary temperatures and pressure, chlorobenzene
is unaffected by the presence of air, moisture or
light. At moderate temperatures, chlorobenzene is
also nonreactive
Sources of Emissions
Production/processing:
Commercially important chlorobenzenes are mono-chloro-
benzene and the two dichlorobenzenes, ortho and para.
In 1978 an estimated 355 million lb of monochlorobenzene
was produced, 59 mi 11ion lb of ortho-dichlorobenzene and
55 million lb of para-dichlorobenzene. Tables D-48 through
0-50 present the producers, location, and estimated production.
Tables D-51 through D-53 present the estimated emissions at
these sites from process, storage and fugitive (emissions from
plant leaks)
Uses:
The end-use distribution of chlorobenzenes is presented
in Table D-54
Estimated emissions from end-uses are presented in Table 0-55
Di sposition:
Chlorobenzenes should be disposed of by atomizing in a
combustion chamber equipped with appropriate effluent gas
cleaning devices, Chlorobenzenes have been detected at
hazardous waste sites. Emissions data from disposition
were not located
Sampling and Analytical Methods
NIOSH Manual of Analytical Methods: Method number S133
Sampling methods (monochlorobenzene):
A known volume of air is drawn through a charcoal tube
to trap the organic vapors present
Analysis:
Desorb sample with carbon disulfide and analyze by gas
chTomography
226

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TABLE D-48. MONOCHLOROBENZENE PRODUCERS
Source
Location
1978
Estimated
Production
(106 Ib/yr)
1978
Estimated
Capacity
{10° lb/yr)
Dow
Midland, MI
101
220
ICC
Niagara Falls, NY
5
10
Monsanto
Sauget, IL
69
150
Montrose
Hendersonj NV
32
70
PPG
New Martinsville, WV
79
172
Standard Chlorine
Delaware City, DE
69
150
Total

355
772
Source; Systems Applications, Inc. 1980
TABLE D-49. o-DICHLOROBENZENE PRODUCERS
Source
Location
1978
Estimated
Production
(10® lb/yr)
1978
Estimated
Capacity
(10® lb/yr)
Dow
Midland, MI
12
30
Monsanto
Sauget, IL
6
16
PPG
New Martinsville, WV
15
38
Standard Chlorine
Delaware City, DE
19
50
Specialty Organics
Irwindale, CA
1
2
Montrose
Henderson, NV
3
7
ICC
Niagara Fal1s, NY
3
8
Total

59
151
Source: Systems Applications, Inc. 1980
TABLE D-50. p-DICHLOROBENZENE PRODUCERS


1978
1978


Estimated
Estimated
Source
Location
Production
(106 lb/yr)
Capacity
(10° lb/yr)
Dow
Midland, MI
9
30
Monsanto
Sauget, IL
4
12
PPG
New Martinsville, WV
13
40
Standard Chlorine
Del aware City, DE
24
75
Specialty Organics
Irwindale, CA
1
2
Montrose
Henderson, NV
2
7
ICC
Niagara Falls, NY
2
8
Total

55
174
Source; Systems Applications, Inc. 1980
227

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TABLE 0-51. M0M0CHL0R0BENZENE EMISSIONS FROM PRODUCTION SITES


Emissions (lb/yr)

Total
Emiss ionsa ^
Company
Location
Process
Storage
Fugitive
(lb/yr)
(g/sec)"
Dow
Midland, MI
200,060
4 5,4 SO
69,690
32 3,200
4.65
ICC
Niagara Falls, NY
10,300
2,250
3,450
16,000
0.23
Monsanto
Saugct, IL
142,140
31,050
47,610
220.800
3.18
Montrose
Hendersons NV
65,920
14,400
22,000
10 2,400
1.47
PPG
Hew Martinsville, WV
162,740
35,550
54,510
252,000
3.64
Standard Chlorine
Delaware City, DE
142,140
31,050
47,610
220,800
3. IB
Total

731,300
159,750
244,950
1,136,000

a
Based on the following emission factors lib emitted per lb produced).
Process	0.00206	A - (derived from site visit data)
Storage	0.00045	A - {derived from site visit data)
Fugitive	0.00069	A - (derived from site visit data)
Total	0.00320
^Based on 0760 hr/yr operation.
Source: Systems Applications, Inc. 1980

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TABLE D-52. o-DICHLOROBENZENE EMISSIONS FROM PRODUCTION SITES



Emissions (Ib/vr)

Total
Emissions"
Company

Location
Process
Storage
Fuqitive
(lb/yrl
(g/sec)
Dow

HidIands Hi
27,840
5,640
9,120
4 2,600
0.61
Monsanto

Sail get* IL
13,920
2,020
4,560
21,30Q
0. 31
PPG

New Martinsville, WV
34.800
7,050
119400
5 3,2 50
0.77
Standard Chlorine
Delaware City, DE
44,080
0,930
14 ,440
67,4 50
0.97
Specialty Organ!cs
Irwindale, CA
2,320
470
760
3,550
0.05
Montrose

llend@rson8 NV
6,960
1,410
2,280
10,650
0.15
ICC

Miagara Falls, NY
6,960
1,410
2,280
10,650
0.15
Total


136,860
27,730
44,840
209,4SO

a
Qased on the
fol lowing
emission factors (lb
emitted per lb produced).



Process
0.00232
A - (derived from
site visit data)




Storage
0.0004 7
A - (derived from
site visit data)




Fugitive
0.00076
A - (derived from
site visit data)




Total 0.00355
Based on B760 hr/yr operation.
Source: Systems Applications, Inc. 1980

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TABLE D-53. p-OlCHLOROBEMZENE EMISSIONS FROM PRODUCTION SITES


Emissions (lb/yr)

Total
Emissions3
Compdny
Locat ion
Process
Storage
Fuqitive
flb/vrl
(q/scc)
Dow
Midland, Hi
52,290
3,690
9,100
65,160
0.94
Monsanto
Sauget* IL
23,240
1 ,640
4,080
20,960
0,42
PPG
New Martinsville, WV
75,5 30
5, 330
13,260
94 ,120
1. 35
Standard Chlorine
Delaware City, DE
139,440
9 i 040
24,480
173,760
2.50
Specialty Organics
Irwxndale, CA
5,810
410
1,020
7,240
0.10
Montrose
Henderson, NV
11,620
B20
2,040
14,480
0,21
ICC
Niagara Fa 1Is, NY
11,620
820
2,040
14 ,480
0.21
Total

319,550
22,550
56,100
398,200

a
Based on the following emission factors fib emitted pec lb produced).
Process O.OOS81 A - (derived from site visit data!
Storage 0,00041 A - (derived from site visit data)
Fugitive 0.00102 A - (derived from site visit data)
Total 0.00724
Based on 8760 hr/yr operation.
Source: Systems Applications, Inc. 1980

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TABLE D-54. CHLOROBENZENES END-USE DISTRIBUTION 1978
Source
Monochlorobengene
Pesticide/degreas ing solvents
Nitrochlorobenzene
DDT
Diphenyl oxide
Miscellaneous, others
o-Dichlorobenzene
3/4 dichloroar.iline
Toluene diisocyanate solvent
Miscellaneous solvents (paint
removers, engine cleaners, etc. 5
Dye manufacturing
Pesticide intermediate
p-Pichlorcber.zsr.e
Space deodorant
Moth control
Pesticide intermediate
Usage	Usage
(million Ib/yr?	(%)
355	ICO
174	49
107	30
25	7
28	8
21	6
59	100
38	6 5
9	15
6	10
3	5
3	5
55 '	100
27.5	50
22	40
5. 5	10
Source: Systems Applications, Inc. 1980
231

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TABLE D-55. 1978 NATIONWIDE EMISSIONS OF CHLOROBENZENES
Nationwide
Emissions
		Source	.	(Ib/yr)
Monochlorobenzene
Productioh	1,136,000
Pesticide/degreasing solvents	174,000,000
Nitrochlorobenzene	171,200
DDT	12,500
Diphenyl oxide	28,500
Miscellaneous, other		27 ,930
Sub-total	175,376,130
o-Dichlorobenzene
Production	209,450
3,4-Dichloroaniline	57,000
Toluene diisocynnate solvent	9,000,000
Miscellaneous solvents	6,000,000
Dye manufacturing	1,500
Pesticide intermediate		1, 500
Sub-total	15,269,450
p-Dichlorobenzene
Production	398,200
Space deodorant	27,500,000
Moth control	22,000,000
Pesticide intermediate	2,750
Sub-total	900,950
Total - all chlorobenzenes	240,546,530
Source: Systems Applications, Inc. 1980
232

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Detection limits;
This method has been validated over the range of
183-736 mg/m3 (25° C 761 mm Hg} using a 10 1 sample
Possible interferences:
1.	High humidity
2.	Compounds present with the same column retention
time.
Materials Damage
Liquid chlorobenzene may attack some forms of plastics,
rubber, and coatings
Permissible Exposure Limit
OSHA Standard
75 ppm {345 mg/m^)
The immediately dangerous to life or health (IDLH) con-
centration is 2400 ppm
Human Toxicity
Chronic Toxicity:¦
Carcinogenicity--^ adequate animal or human epidemiological
studies are available for evaluation. However, a long-term
animal carcinogenesis bioassay is being completed in FY83 by
the National Toxicology Program for monochlorobenzene; a
•long-term animal carcinogenesis bioassay for p-dichlorobenzene
is being initiated in FY83 (U.S. DHHS 1983)
Bibliography
Fishbein, L. 1979. Industrial Carcinogens and Mutagens. Elsevier Scientific
Publishing Co., New York, fclY. p. 266.
International Agency for Research on Cancer. 1974 IARC Monographs on the
Evaluation of Carcinogenic Risk of Chemicals to Man"! Lyon, France, Vol. 7,
pp. 231-44.
Kirk-Othmer. 1979. Encyclopedia of Chemical Technology, 3rd ed. John Wiley
and Sons, New York ."FTT—Vol. 5, pp. 797-808.
233

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U.S. Department of Health, Education, and Welfare. 1977. NIOSH Manual of
Analytical Methods. HEW/PHS/NIOSH, p. 133.
U.S. Department of Health and Human Services. 1983. Review of Current DHHS,
DOE and EPA Research Related to Toxicology. National Toxicology Program.
OHHS/PHS/UTP":	
Systems ApplIcations, Inc. 1980. Human Exposure to Atmospheric Concentra-
tions of Selected Chemicals, Vol ,~T EPA/OAQPS PB81-193252.
234

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Chemical Name
Chioroform
CAS Number
67-66-3
Chemical Classification
Halogenated unsaturated hydrocarbon, halogenated methane,
chlorinated aliphetic hydrocarbon, halocarbon
Synonyms
Chloroform (DOT), chloroform (BCI), formyl trichloride, freon 20,
methane trichloride, methane, trichloromethenyl chloride, methenyl
trichloride, methyl trichloride, NCI-C02686, R 20, R 20 (refrigerant),
R 20 (van), trichloroform, trichloromethane
Physical/Chemical Properties
Descripti on:
Heavy, water-white, volatile liquid with a pleasant,
non-irritant odor; nonflammable
Boiling point:
61.25° C
Melting point:
-63.5° C
Molecular weight:
119.39
Chemical formula:
CHC13
Vapor pressure:
200 mm Hg at 25.9° C; 246 mm Hg at 30° C
235

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Refractive index:
1.4467 at 20° C
Solubility:
Miscible with principal organic solvents; slightly
soluble in water (8,0 g/1)
Octanol/water log partition coefficient:
1.17
Photochemical reactivity:
Highly reactive In the troposphere and will undergo
thermal tropospheric reactions
When exposed to air and light, chloroform breaks down
to phosgene, HC1, and chlorine
half-life = <1 year (OH) atmospheric loss
0.91 loss/day (12 sun hrs)
Vapor density:
4.12
Chemical reactivity:
Reacts with strong caustics, chemically active metals
(aluminum, magnesium powder, sodium, potassium)
Environmental Fate
Degrades easily in the atmosphere to phosgene and chlorine
monoxide with a half life of-2-3 months
Found less frequently than other chlorinated hydrocarbons.
Chloroform is an ubiquitous material in the atmosphere at
trace amounts, due to industrial emissions, release from end
use applications and to formation due to reaction of chlorine
and methanol in the atmosphere
Sources of Emissions
Production:
176 million lb in 1977
chlori nation of methane
hydrochlorinati on of methanol or methyl
chl ori de chlori nation
reduction of carbon tetrachloride
236

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Uses:
In production of chlorodifluoromethane
To produce fluorocarbon 22, a refrigerant and aerosol pro-
pell ant, to make fluorocarbon resins (used 107,250 tons in
1975 or —80% of chloroform production)
As an industrial solvent; to make pharmaceuticals or pesti-
cides (leads to a population exposed to -300,000 lb/year of
chloroform)
As a laboratory solvent
Heat transfer medium
As a fire extinguisher
Storage and Transport:
Should be stored in sealed containers in a cool place;
glass containers should be dark, green or amber
Technical grade chloroform can be stored in lead lined
or mild steel containers of all welded construction
Technical grade is shipped in galvanized steel drums,
tank trucks, or tank cars
Dispostion:
Production losses to air
Emissions from bleaching of paper pulp using chlorine
Decomposition of perch!oroethylene may be a source of
chloroform in the atmosphere
Occurs in leachate of sanitary 1andfil1s
Tables D-56 through D-58 and Figure D-4 present chl oroform produc
tion, end use, and emissions data
Sampling and Analytical Methods
1. NIOSH method S 351 for chloroform
a.	adsorption on charcoal
b.	desorption with carbon disulfide
c.	gas chromatography
Detection limits:
0.10 mg/0.5 to 13 1 sample
237

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TABLE D-56. PRODUCTION OF CHLOROFORM
Source
Location
1978
Estimated
Production
(106 Ib/yr)
Process
Allied Chemical Corp.
Moundsville, WV
19
A,B
Diamond Shamrock
Belle, WV
26
A
Dow Chemical
Freeport, TX
64
B

Plaquemine( LA
64
A
Stauf fer Chemical Co,
Louisville, KY
49
A
Vulcan Materials Co.
Geismar, LA
38
A

Wichita, KS
70
A ,B
Total

330

(A) - Methanol bydrochlorination process or methyl chloride chlorination process.
(U) - Methane chlorination process.
Source: Systems Applications, Inc. 1980
TABLE D—57. 1978 CHLOROFORM CONSUMPTION BY END-USE
End Use
Percent of-
Total Cansemotion
End Use
Consumption
(« lb)
Chiorodifluoromethane {7-22)
refriger ants
61
201.3
Chlorodifluorome thane (T-22)
resin intermediates
25
82.5
Export
7
23.1
Solvent/miscellaneous
7
23.1
Total
100
330.0
Source: Systems Applications, Inc. 1980
238

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TABLE D-58. 19/8 CHLOROFORM PRODUCTION EMISSIONS



Process Vent
Emissions
Storage Vent
Dnissions
Fugi tive
Emissions
Total Emissions
, Company
Location

(lb/yr)
(y/scc)b

-------
i
Figure D-4. Specific point sources of chloroform emissions.
Source: Systems Applications, Inc. 1980

-------
Possible interferences:
High humidity (decreases breakthrough volume)
Presence of other solvents
Presence of other compounds with same retention
time as chloroform
Method B {Appendix A): C2-C18 hydrocarbons and other
nonpolar organics with a boiling point -100 to 175°
Whole air collection in canister
Cryogenic concentration
Gas chromatography/flame ionization detection
Detection limits:
0.1 ppb per 100 ml sample
Possible interferences:
Reactive and water soluble compounds are not
readily analyzed
Method C (Appendix A): Cg-Ci2 hydrocarbons and other
nonpolar organics with boiling point between 60 and
200° C
Adsorption on tenax
Thermal desorpti on
Gas chromatography/mass spectrometry analysis
Detection limits:
1-200 ppt for a 20 1 sample
Possible interferences:
B1ank 1evels usually limit sensitivity
Artifacts due to reactive components (O3, N0X)
can be a problem
Sample can be analyzed only once
Method D {Appendix A}: Cg-Ci2 hydrocarbons and other
nonpolar organics with boiling point of 60-200° C
Adsorption in Tenax
Thermal desorption into canisters
Gas chromatography/flame ionization detection, or gas
chromatography/mass spectrometry analyses
Detection limits:
0.01-1 ppb for a 20 1 sample
Possible interferences:
Blanks and artifact problems as in method C, above
241

-------
Materials Damage
Liquid chloroform will attack some forms of plastics, rubber,
and coatings
Permissible Exposure Limits
OSHA
NIOSH
ACGIH
TLV 50 ppm {240 mg/np)
Ceili ng
2 ppm/1 hour 50 ppm (225 my,)
10 ppm (50
Human Toxicity
Acute Toxicity:
Chloroform vapor is a central nervous system depressant and is
toxic to the liver and kidneys
Chronic Toxicity:
Carcinogenic!ty--There is sufficient evidence for the car-
cinogenicity of chloroform in experimental animals
Mutagenesis--Ch1oroform failed to produce mutagenetic changes
in the Chinese hamster
Teratogenesis--Chloroform appears to be somewhat teratogenic
and highly embryotoxic in animals
Bib!i ography
American Conference of Governmental Industrial Hygienists. 1982. TLVS,
Threshold Limit Values for Chemical Substances and Physical Agents in the
Work Environment with Intended Changes for 1982. ISBNO.936712-39-2.
Cincinnati, OH.
CIayton, George D., and F1orence E. CI ayton, eds. Patty's Industrial Hygiene,
3rd Revised Edition, 1981. "Toxicology." Vol. 2B pp. 3462-69. John Wi1ey
and Sons, New York, NY,
Fuller, B., J. Hushon, M, Kornreich, R. Quel 1ette, L. Thomas, and P. Walker.
1976. Preliminary Scoreing of Selected Organic Air Pollutants* EPA-450/
3-77-0082. The Mitre Corporation. McLean, VA.
GEOMET Technologies, Inc. 1981. Chemical Summaries for NTP Second Annual
Report on Carcinogens. Rockvi1le, MD.
242

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International Agency for Research on Cancer. 1972. IARC Monographs on the
Evaluation of Carcinogenic Risk of Chemicals to ManT Lyons, France. Yol. 1.
International Agency for Research on Cancer. 1979. I ARC Monographs on the
Evaluation of Carcinogenic Risk of Chemicals to ManT Lyons, France. Vol. 20.
Katz, Morris, ed. 1977. Methods of Air Sampling and Analysis. Alpha
Intersociety Committee, American Public Health Association, Washington,
DC.
Kirk-Othmer. Encyclopedia of Chemical Technology, 3rd ed. John Wiley
and Sons, New York, NY. Vol. 5. pp. 693-/03.
Mackison, Frank W., R. Scott Stricoff, and Lawrence J. Partridge, Jr.,
eds. 1978. NIOSH/OSHA Pocket Guide to Chemical Hazards. DHEW (NIOSH)
Publication No. 78-210. Washington, DC.	~
Mason, Benjamin J., Douglas J. Pel ton, Ruth J. Petti, and David J. Schmidt.
1979. Environmental Carcinogens and Human Cancer. GEOMET Report Number
HF-803. GEOMET, Incorporated, Gaithersburg, MD.
McGraw-Hi11, Inc. 1977. McGraw-Hill Encyclopedia of Science and Technology.
New York, NY.	~ ^ ^	~
National Fi re Protection Association. 1981. National Fire Codes, A
Compilation of NFPA Codes, Standards, Recommended Practices, and Manuals.
Vol. 13. WPKI Quincy, MA.
Proctor, Nick W., and James P. Hughes. 1978. Chemical Hazards of the Work-
pi ace. J.B. Lippincott Company, Philadelphia, PA. 1	~~ "" ———
Riggin, R.M. 1983. Technical Assistance Document for Sampling and Analysis
of Toxic Organic Compounds in Ambient Air. EPA-6GG/4-83-027. Battel 1e
Columbus Laboratories. Columbus, OH.
Sittig, Marshall. 1980. Priority Toxic Pol 1utants. Noyes Data Corporation.
Park Ridge, NJ.
Systems Applications, Inc. 1980. Human Exposure to Atmospheric Concentrations
of Selected Chemicals Vol. I. PB81-193252. Systems Applications, Inc.,
San Raphael, CA.
U.S. Department of Health, Education, and Welfare. 1974. Criteria for a
Recommended Standard...Occupational Exposure to Chloroform^ HEW Publication
No. (NlOSH) 75-114. National Institute for Occupational Safety and Health.
Washington, DC.
U.S. Department of Health, Education, and Welfare. 1977. NIOSH Manual of
Analytic Methods, Vol~ 1. DHEW (NIOSH) Publ. No. 77-157-A. Cincinnati, OH.
243

-------
U.S. Department of Health, Education, and Welfare. 1977. NIOSH Manual of
Analytic Methods, Vol. 3. DHEW {NIOSH) Pub!. No. 77-157-C. Cincinnati, OH.
U.S. Department of Health and Human Services. 1982. Third Annual Report on
Carcinogens. Public Health Service, National Toxicology Program.
Washington, DC.
U.S. Department of Labor. 1981. General Industry, QSHA Safety and Health
Standards (29CFR1910). Occupational Safety and Health Administration.
Washington, DC.
U.S. Department of Transportation. 1978. Chemical Hazards Response Infor-
mation System (CHRIS) Hazardous Chemical Data United States. Coast Guard,
Washington, DC.
U.S. Environmental Protection Agency. 1976. Disposal of Hazardous Wastes,
Manual on Hazardous Substances in Special Wastes" NAT07CCHS"Report 55.
Washington, DC.
U.S. Environmental Protection Agency. 1980. TSCA Chemical Assessment Series
Chemical Hazard Information Profiles (CHIPS)." Coast "Guard, Washington, DC.
244

-------
Chemical Name
Chloroprene
CAS Number
126-99-8
Chemical Classification
Halogenated hydrocarbon
Synonyms
2-chloro-1,3-butadiene; chlorobutadiene; beta-chloroprene
Physical/Chemical Properties
Description;
Colorless volatile liquid with an ether-like odor
Boiling point:
58.9° C
Melting point:
-130° C
Molecular weight;
88.5
Chemical formula:
C4H5CI
Vapor pressure:
179 mm Hg at 20° C
215.4 mm Hg at 25° C
Vapor density:
3 (air - 1)
Refractive index:
n^° 1.4583
Solubility:
Partially soluble in water; soluble in most organic
sol vents
245

-------
Photochemical reactivity:
Resistant to sunlight
Chemical reactivity;
Reacts with oxygen to form peroxides. Enters into
addition reactions with halogens. Forms high
molecular weight elastomeric polymers
Sources of Emissions
Production/processing:
EPA reports domestic production of chloroprene at
1 billion lb by four producers in one region
(public record, TSCA Inventory). EPA/OAQPS has
estimated that within 20 km of manufacturing
sites exposure to chloroprene is at median
concentrations of <0.05 to >0.025 ug/m^
Uses:
Host of the chloroprene is used in the production
of polychioroprene elastomers. Airborne concen-
trations at a chloroprene polymerization plant
ranged from 14-1400 ppm in the make-up area,
130-6800 ppm in the reactor area, and 110-250 ppm
In the latex area
Storage and transport:
Chloroprene has to be stored and transported
cooled to -10° C under an inert gas. Emissions
are probably minimal
Di sposition:
Due to high reactivity and volatility chloroprene
and chloroprene-containing wastes cannot be dumped.
Wastes have to be destroyed in special waste
incinerators
Sampling and Analytical Methods
NIOSH Manual of Analytical Methods. Method number S 112
Sampling method:
A known volume of air is drawn through a charcoal
tube containing activated coconut charcoal to
trap chloroprene vapors
246

-------
Analytical method:
Chloroprene is desorbed from the charcoal with
carbon disulfide and the sample is analyzed by
GC
Detection limits:
This method was validated over the range of
44 to 174 mg/m3 at 21° C 760 mm Hg using a
3 1 sample
Possible interferences:
Any compound having the same column retention
time under the same analytical operating
conditions could cause interference of chemical
identity
Permissible Exposure Limits
OSHA Standard:
25 ppm (90 mg/m3)
NIOSH recommendation:
1 ppm/15 min celling
Human Toxicity
Acute toxicity:
High concentrations {no exact data) lead to
collapse and death from acute pulmonary edema
Chronic toxicity:
Carcinogenici ty--Inadequate evidence
Mutagenicity—Epidemiol ogical evi dence consistent with experi-
mental evidence that chloroprene is mutagenic in humans
Other chronic toxicity:
Reproductive toxicity supported by epidemiological evidence
247

-------
Sibliography
Federal Environmental Agency (Berlin-West) Waste Management Division. 1976.
NATO Report 55.
International Agency for Research on Cancer. 1979, IARC Monographs on the
Carcinogenic Risk of Chemicals to Humans. Lyon, France. Vol. 19,	
pp. 131-56.
Kirk-Othmer. 1979. Encyclopedia of Chemical Technology. John Wiley
and Sons, New York, NY. Vol. 5, p. 773-85.
U.S. Department of Health, Education, and Welfare. 1977. NIOSH Manual of
Analytical Methods. U.S. DHEW/PHS/NIOSH. Vol. 2, S112.
U.S. Department of Health, Education, and Welfare. 1977. NIOSH Criteria for
a Recommended Standard...Occupational Exposure to Chioroprene. U.S.
DHEW/PHS/NIOSH Publication Number 77-210.	
24-8

-------
Chemical Name
Chromi imt
CAS Number
7440-47-3
Synonym
Ch rome
Chemical Classification
Elemental metal
Physical/Chemical Properties
Description:
Silver, blue-white, hard, brittle lustrous metal
Boiling point:
2672° C
Melting point:
1857 +20° C
Atomic weight:
51.9
Atomic formula:
Cr
Vapor pressure:
Essentially 0 at 210° C
Solubility:
Insoluble in water; some chromium salts are very soluble
in water
Density:
7.2 g/cnP at 28° C
249

-------
Chemical reactivity:
Not oxidized by air even in the presence of moisture;
reacts with dilute hydrochloric and sulfuric acids;
attacked by caustic alkalies and alkali carbonates
Environmental Fate
Under environmental conditions, when oxygen is present,
chromium exists as elemental, trivalent or hexavalent
chromiurn
Source of Emissions
Production/process i ng:
Chromite ore consists of varying percentages of chromium,
iron, aluminum and magnesium oxides. Current U.S. mine
production is believed negligible. In 1978, 17,705 mil-
lion lb of chromite ore were imported
The 1980 domestic production of chromium and ten important
chromium compounds was an estimated 750 million lb.
Approximately 100 million lb were imported in 1980
Uses:
Chromium metal and metal alloys are used primarily in
stainless, al1oy and heat resisting steel. Other chromium
compounds are used in chemical processing, refining, plat-
ing and a number of specialty uses. Table D-59 presents
sources and estimates of chromium emissions for 1970
Disposition:
The galvanizing and metal processing industries are a major
source of chromate waste
Chromium-containing sludges or residues cannot be disposed
of in incinerators as the trivalent chromi urn is reoxidized
to the toxic hexavalent chromium with heat. Emissions
data from disposition were not available
250

-------
TABLE D-59. SOURCES AMD ESTIMATES OF CHROMIUM-CONTAINING EMISSIONS IN 1970
UnconirulUd
Emution F»cior
rss
Sourct
Mmmg
fVutiv1 j,ti U S.A
HlMll'UJ
F«rjiOkHri>nuum
Cli:i.llt( luJ I14CC
Elut.trolyiiq i,hf ooiit-Hii
Rcis jiit-uy
tilccmc c^l
Ciicitti^jl Pj cicciting
CVctK om^K
Gll»u ctsefMaLi&ll
Sic»rS 4>iU AUuyb
Call null
Super «1
Pi f CM I Cf
in Eomiioni
(MO 830|
500'
10
QQ4B
IM
226 *
30
2b
It,
26
N A
W A
H A
14 A
N A
N A
gion 4151
2i0*
5
0 024
75
ti2
1 f>
12
38
12
N A
N A
N A
N A
N A
N A
3/S.600
3JS.5QO
9.000
60.300
6,700
61.000
1 BO ,000
6.000
12,000
N A
33 81)0 000*
IB 7.0G0d
9U.0001'
03 I OOO"
b.570
22
65
61
M
N.A.
0 026
0 13
0 03
oow
0 IS
im cimciJule vjlut!
h£
-------
Sampling and Analytical Methods
1.	Total particulate chromium sampling method
NIOSH Manual of Analytical Methods. Method number
PSCAM 152
Samp!ing:
Atmospheric samples are obtained by drawing a measured
volume of air through a 0.8 urn filter
Analysis:
The filter 1s wet-ashed and analyzed for chromium
by atomic absorption spectroscopy
Detection limit:
The working range in air is from 0.1 mg/m^ to
0.4.mg/m^	using a sample of 100 1 of air
Possible interferences:
A number of metallic elements may interfere with
the atomic absorption analysis
2,	Chromium, metal and Insoluble compounds
NIOSH Manual of Analytical Methods. Method number
S3 52
Sampling:
A known volume of air is drawn through a cellulose
ester membrane filter to collect the analyte
Analysis:
Samples are ashed to destroy the fi1ter and other
organic compounds in the sample, and the chromium
metal and other insoluble chromium compounds are
dissolved in nitric acid. The solution of sample
is aspirated into the flame of an atomic absorption
spectrophotometer for analysis
Detection limits:
A 90 1 sample has a working range of 0.08 to
2.5 mg/m3 at 26° C 761 urn Hg
Possible Interferences:
1.	Soluble chromium compounds
2.	Iron and nickel present in the sample
252

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Permissible Exposure limit
OSHA standard:
0.1 mg/m3 ceiling {chromic acid and chromates);
0.5 mg/m3 8-hr TWA (soluble chromic or chrosnous salts);
1 mg/m3 8-hr TWA (metal and insoluble salts)
Human Toxicity
Chronic toxicity:
Carcinogenicity--There is sufficient evidence for the car-
cinogenicity of chromium and certain chromium compounds both
in humans and experimental animals. There is sufficient
evidence for increased incidence of lung cancer among workers
in the chromate-producing industry, and possibly among
chromium platers and alloy workers
Mutagenicity—An increased frequency of chromosomal aberra-
tions has been observed in workers exposed to chromium (VI)
compounds
Teratogenicity—Some teratogenic effects in animals have been
reported with chromium (III) and chromium (VI) compounds
using very high doses. No human data are available
Bibliography
CI ayton, G., F. CIayton, eds. Patty's Industrial Hygiene and Toxicology, 3rd
Revised Edition. John Wiley and Sons, New York, NY. pp. 1589-1603.
Federal Environmental Agency (Berlin-West). 1976. Waste Management Division
NATO CCMS Report No. 55. P8 270591.
International Agency for Research on Cancer. 1980. IARC Monographs or the
Evaluation of the Carcinogenic Risk of Chemicals to Humans. Lyon, France,
Vol. 23, pp. 205-323.			
U.S. Department of Health, Education, and Wei fare. 1975. NI0SH Criteria for
a Recommended Standard.¦.Occupational Exposure to Chromium (VlT QHEW/PHS/NIOSH
Publication No. 76-129.
U.S. Department of Health, Education, and Welfare. 1974. NI0SH Manual of
Analytical Methods. DHEW/PHS/NIOSH. P&CAM No. 152.
U.S. Department of Health, Education, and Wei fare. 1977. NI0SH Manual of
Analytical Methods. DHEW/PHS/NIOSH. S 352.
253

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Sittig, M. 1975. Environmental Sources and Emissions Handbook. Noyes Data
Corporation, Park Kidge, NJ. pp. 44-48.	~~
Sittig, M. 1980. Priority Toxic Pollutants. Noyes Data Corporation, Park
Ridge, NJ. pp. 158-63.	" "
254

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Chemical Name
2,3,7,8-Tetrachlorodibenzo-para-dioxin {TCDD)
CAS Number
1746-01-6
Chemical Classification
Polychlorinated dioxin. There are 75 chlorinated dibenzo-para-
dioxins identified of which 2,3,7,8-TCDD is the most toxic
Synonyms
Dioxin, TCDBD, TCDD, 2,3,7,8-Tetrachlorodibenzodioxin; 2,3,7,8-
Tetrachl orodibenzo-1,4~dioxin; 2,3,7,8-Tetrachlorodibenzo(b,3)
(l,4)dioxin
Physical/Chemical Properties
Description:
Colorless needles
Melting point;
305°-306° C
Molecular weight:
322.96
Chemical formula:
C12H4CI4O 2
255

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Solubility:
Solvent
Solubility, g/1
ortho-di chlorobenzene
chlorobenzene
benzene
chloroform
acetone
n-octanol
methanol
water
1.4
0.72
0.57
0.37
0.11
0.05
0.01
2x10-7
Photochemical reactivity:
In studies exposing nanogram quantities of TCDD to sunlight,
50 percent degradation occurred in 5 to 6 hours. The chlori-
nated dibenzo-para-dioxins when dissolved in methanol are
easily degraded by strong sunlight
Chemical reactivity:
The chlorinated di oxi ns are extremely stable and persistent
compounds. TCDD is a very stable chemical that resists
breakdown by other chemicals
Atmospheric reactivity:
Some data indicate that the chemical can be photodegraded
Soil:
TCDD has been reported as Immobile in soil samples of varying
textures. In a study conducted by the U.S. Air Force, 1evels
up to 1.5 ug/kg were found in soil 10 to 12 years following
aerial spraying of herbicides containing TCDD. The microbial
degradation of TCDD is reported to be relatively rare in
nature
Production:
The chlorodibenzo-para-di oxi ns are not manufactured commercially
Byproduct sources:
TCDD forms as a hazardous byproduct during the preparation of
2,4,5-trichlorophenol, a major intermediate in the manufacture
of several herbicides, fungicides, and wood preservatives
Environmental fate
Sources of Emissions
256

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Byproduct sources:
Estimated emission rates by specific plants (SAI 1980)
Type of	Emission
Company	Site	production*	rate* (mg/sec)
Dow
Midland, MI
I
0.003298

-
2
0.018000


3
0.042480
PBI-Gordon
Kansas City, KA
1
0.003298
Riverdale
Chicago Heights, 1L
1
0.003298
Union Carbide
Ambler, PA
I
0.003298
Union Carbide
Fremont, CA "
1
0.003298
Union Carbide
St. Joseph, MO
1
0.003298
Vertac
Jacksonville, FL
1
0.003298


2
0.018000
Monsanto
Sauget, IL
3
0.042480
Reichhold
Tacoma, WA
3
0.042480
Vul can
Wichita, KA
3
0.042480
* Estimated nationwide emissions {Ib/yr) during 1978 are as follows (SAI 1980):
Type 2 Trichlorophenol production 2.5
Type 1 2,4,5-T production	1.6
Type 3 Pentachlorophenol production 11.8
These were allocated equally among the sites over 8,760 hours
Contaminant sources:
The following materials are known to contain trace amounts of
TCDO as an impurity:
1,3,4,5-tetrachlorobenzene
2,4,5-trichlorophenoxyacetic acid (2,4,5-T) and its esters
hexachlorophene
pentachlorophenol
2,4,5-trichlorophenoxypropionic acid (silvex)
2,4-dichlorophenoxyacetic acid (2,4-D)
clophen
Agent Orange: 50:50 mixture of 2,4,5-T and 2,4-D
Locust bean gum (food stabilizer)
The following emissions are estimated to result from use of
these materials in 1978 (SAI 1980):
2,4,5-T applications	6.5 1b
Pentachlorophenol as wood preservative 42.3 1b
257

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Combustion sources:
Trace levels of dioxins (including TCDD) may be present in fly
ash and flue gases from the following sources:
§ Incinerated waste material containing grass clippings
and wood previously treated with contaminated herbicides
® Particulate entisions from incinerators, powerhouse
boiler stacks, and fireplaces
•	Emissions from the combustion of chlorinated organic
chemicals such as polychlor1nated benzenes, poly-
chlorinated phenols, and polyvinyl chloride plastics
•	Emissions from fires in transformers containing chlori-
nated benzenes and polychlorinated biphenyls
•	Emissions from the combustion of gasoline, diesel fuel,
and cigarettes resulting in air levels of 0.001 to
1100 ppb
The estimated emissions of TCDD during 1978 due to combustion
processes are as follows {SAI 1980):

Particul ate
Total

Emissions
Emissi ons
Source
(tons/yr)
(lb/yr)*
Open burning
2,161,142
8.6
Agriculture
1,433,712
5.7
Forest fires
526,843
2.1
Refuse open burning
212,211
0.8
Conical burners
193,500
0.8
Coal burning—all sources
108,952
0.4
011 burning--al1 sources
72,389
0.3
Incineration, municipal
30,123
0.1
domestic


Total

18.8
* Based on a TCDD emission concentration in particulate
matter of 2 ppb
Uses:
TCDD is not used commercially. This compound has been tested
for use in flameproofing polymers, and against insects and
wood-destroying fungi, but these uses are not known to have
been exploited commercially
TCDD has no reported use other than as a test chemical in
basic research
258

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Storage:
Not applicable
Transportation:
Not applicable
Di sposition:
Abandoned dump sites which contain wastes from herbicide
manufacturings particularly 2,4,5-TCP, are major sources of
TCDD
Under the Resource Conservation and Recovery Act (RCRA), TCDD
has been designated by the EPA as a hazardous constituent of
waste, which subjects the chemical to special handling and
recordkeeping requirements. Under the Toxic Substances
Control Act, Section 6, the EPA restricts the removal of TCDD
in wastes except with EPA approval in compliance with RCRA
requirements
Sampling and Analytical Methods
1.	Commercial chlorophenols analysis for chlorodibenzo-para-dioxins
a.	Analysis on an aluminum oxide column
b.	Detection by gas chromatography with electron capture
c.	Confirmation by mass spectroscopy
Detection limits:
20 ug/kg
Possible interferences:
Presence of other compounds with the same column retention
time
2.	Analysis of samples of unknown origin
a.	Use of an ion-exchange resin column to remove chloro-
phenoxyphenols
b.	Determination of the dioxins by gas chromatography and
mass spectrometry using multiple-ion detection
Detection limits:
0.05 rag/kg for TCDD
Possible interferences:
Presence of other compounds with the same column retention
time
259

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3.	Analysis for TCDD contained in 2,4,5-T
a.	Use of gas chromatography
b.	Identification by mass fragmentography
Detection limits:
50 to ug/kg
Recovery 80 to 100 percent
Possible interferences:
Presence of other compounds with the same column retention
time
4.	Dioxins from photochemical and thermochemical decomposition
of chlorophenoxyphenols
a.	Use of gas chromatography
b.	Detection with flame ionization and mass spectometry
Possible Interferences:
Presence of other compounds with the same column retention
time
Permissible Exposure Limits/Threshold Limit Values
Under study by OSHA
Materials Damage
Chemical reactivity low, probability of materials damage low
Toxicity
Acute toxicity;
In animal tests, TCDD has been demonstrated to be the most
acutely toxic compound made
Chronic toxicity:
Carcinogenicity—TCDD caused cancer in oral and dermal studies
in animals. When the chemical was administered by gavage,
exposure caused thyroid tumors in male rats and liver tumors
in female rats. TCDD painted on the skin of mice was carcino-
genic for female mice
Mutagenic!'ty--TCD0 produced mutagenic effects in some short-
term microbial bioassays
260

-------
Teratogenicity--TCDD is embryotoxic and teratogenic in mice
and rats. No human data are available. Positive results in
these studies demonstrate that the chemical is carcinogenic
for animals and that exposure is a potential hazard to
humans
Other chronic toxicity:
Chloracne
Neurological effects
Liver toxicity
Anemia and other blood disorders
Kidney dysfunction
Impairment of the immune system
Bi'bl iography
American Conference of Governmental Industrial Hygienists. 1982, TLVS,
Threshold limit Values for Chemical Substances and Physical Agents in the
WotOjtv^	Intended Changes for I98Z. ISBN No. 936712-39-2.
Cincinnati, OH.
Environmental Health Perspectives. 1973. National Institute of Environmental
Health Sciences. DHEM Publication No. S.
International Agency for Research on Cancer, 1977. IARC Monographs on the
Evaluation of the Carcinogenic Risk of Chemicals to Humans. Vol. 15, p.
41-102, Lyon, France.	1 ~ ~ '
International Agency for Research on Cancer. 1977. IARC Monographs on the
Evaluation of the Carcinogenic Risk of Chemicals to Humans. Lyon, France.
Supplement 4.	~~ 1	~	1
National Toxicology Program. 1982. Carcinogenesis Bioassay of 2,3,7,8-
Tetrachlorodibenzo-p-dioxin {CAS No. 1746-01-6) in Osborne-Mendel Rats and
155C5FT"HTce	{^ayage^tu3lyT«	H1?cfTiTT<^	NIH Publication
No. 82-1765. Research Triangle Park, North Carolina.
National Toxicology Program. 1982. Carcinogenesis Bioassay of 2,3,7,8-
Tetrachlorodibenzo-p-dioxin (CAS NoT~I/46-01-6) in Swiss-Webster Mice
(Dermal Study). Technical Report Series No. 20T^ NIH Publication
No. 82-1757. Research Triangle Park, North Carolina, and Bethesda, Maryland.
Systems Applications, Inc. 1980, Human Exposure to Atmospheric Concentrations
of Selected Chemicals, Vol. II. PB81-19326U. Systems Applications, Inc.,
San Raphael, California.
U.S. Environmental Protection Agency. 1981. Dioxins. Toxic Information
Series. OPTS, Washington, D.C.
261

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Chemical Name
Epichlorohydrin
CAS Number
106-89-8
Chemical Classification
Epoxide fibrous silicate
Synonyms
2-{chloromethyl)	oxirane; 3-chloro-l,2-propyl ene; 3-cholro-1-
oxacyclobutane; gamma-chloropropylene oxide; alpha-epichlorohydrin;
1,2-epoxy-3-chloropropane; chloropropylene oxide; glycerol
epichlorohydrin; glycerol epichlorhydrin; 3-chlorooxetane;
3-chloro-l,2-exoxypropane;	(chloromethyl} ethylene oxide;
3-chloro-1,2-propylene oxide; 1-chloro-2,3-epoxy propane;
epichlorohydrine; ox1rane {chloromethyl); 2,3-epoxypropyl chloride;
glycidyl chloride
Physical/Chemical Properties
Descrlption:
Colorless liquid
Boiling point:
117.9° C
Melting point:
-25.6s C
Molecular weight:
92.53
Chemical formula:
C3H5C10
Vapor pressure:
16.8mm at 2.5° C
Vapor density:
3.29
262

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Physical/Chemical Properties
Refractive Index:
Njp 1.4359
Solubility:
5.48 percent soluble in water; soluble in most
organic solvents
Photochemical reactivity:
Potential for air pollution is high; however, no
data are available on photochemical reactivity
Chemical reactivity:
By suitable adjustment of reaction conditions,
epichlorohydrin can be an intermediate in the
synthesis of a wide variety of products
Epichlorohydrin emits highly toxic fumes when
heated to decomposition
The reactivity of the compound is characterized
by the terminal chlorine atom and the epoxy group
Envi ronmental Fate
Indications of accumulative effects; however, biodegradation
may occur
Sources of Emissions
Production:
Approximately 312 million lb of epichlorohydrin were produced in
1978. The total production emissions including process, storage
and fugitive was estimated as 146,600 lb/yr in 1978
lb lost/lb produced
Process	0.00042-from state files
Storage	0.00001-from state files
Fugitive	0.00004-engineering estimate
263

-------
Plants and locations:
Dow Chemical
Shell
Uses/storage/fugitive:
The ordinary end uses of epichlorohydrin are for the manufacture
of epoxy resins (53%) and synthetic glycerin (25%). Other uses
include the production of epichlorohydrin elastomers, glycidol
ethers, surfactants, etc. End use consumption is presented in
Table D-60. Epichlorohydrin emissions from epoxy resin production
including process, storage and fugitive emissions total an
estimated 250,800 lb/yr (1978 data). Table D-61 presents plant
locations and emissions. Table D-62 presents nationwide emission
losses of ally! chloride (consumed in epichlorohydrin produc-
tion) and epichlorohydrin
Di sposition:
The largest quantities of epichlorohydrin containing wastes
originate in the production of epoxy and phenolic resins. It
is expedient to destroy concentrated wastes in special incin-
erators to avoid the formation and emission of toxic fumes. No
data are available on emissions from disposition
Sampling and Analytical Mehtods
NIOSH Method Number S 118: Epichlorohydrin
Sampling method:
A known volume of air is drawn through a charcoal tube to trap
the organic vapors present
Analytical method:
The analyte is desorbed with carbon disulfide, and the desorbed
sample is injected into a gas chromatograph
Detection limits:
A sample size of 210 1 yielding a 1 mg sample has a
working range of 2-60 mg/nP
Possible interferences:
1.	High humidity
2,	Compounds with the same column retention times
Freeport, TX
Deer Park, TX
Norco, LA
264

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TABLE D-6Q. 1978 EPICHLOROHYDRIN CONSUMPTION BY END-USE
End-Use
Percent
of Total
Consumption
End-Ose
Consumption

-------
TABLE D-61. 1978 EPICHLOROHYDRIM EMISSIONS FROM EPOXY RESIN PRODUCTION


Process
Emissions
Storage
Emissions
Fugitive
Emissions
Total
a
Emissions
Company
Location
(lb/yr)
(q/sec)b
(lb/yr)
(g/sec)k
(lb/yr)
(g/sec)b
(lb/yr)
(g/sec)*
Celanese
Linden, NJ
15,960
0.2 30
1,400
0.020
3,920
0.056
21,280
0. 306

Louisville, KY
10,260
0.148
900
0.013
2,520
0.036
13,680
0. 197
Ciba-Geigy
Toms River, NJ
25,000
0. 361
2,200
0.032
6,160
0.089
33,440
0.401
Dow
Freeport, TX
69,540
1.001
6,100
0.088
17,080
0.246
92,720
1. 335
Reichhold
Andover, MA
3,420
0.049
300
0.003
840
0.012
4,560
0.066

Azusa, CA
3,420
0.049
300
0.003
040
0.012
4,560
0.066

Detroit, MI
3,420
0.049
300
0.003
840
0.012
4,560
0.066

Houston, TX
3,420
0.049
300
0.003
840
0.012
4,560
0.066
Shell
Deer Park, TX
41,040
0.591
3,600
0.052
10,080
0.145
54,720
0. 788
Union Carbide
Bound Brook, NJ
4,560
0.066
400
0.004
1,120
0.016
6,080
0.088

Taft, LA
7,980
0.115
700
0.010
1,960
0.028
10,640
0.153
Total

108,100

16,500

46,200

250,800

°Einisslon factor for epichlorohydrin emissions (lb lost per lb used) .
Process 0.00114 B - From state files
Storage 0.00010 B - From state files
Fugitive 0.000 28 B - From state files
Total	0.0015 2
Assumes 0760 hr/yr operation.
Source: Systems Applications, Inc. 1980

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TABLE D-62. 1978 ESTIMATED ALLYL CHLORIDE AND EPICHLOROHYDRIN
NATIONWIDE EMISSION LOSSES
Source
Estimated National Emissions
.Allyl Chloride Epichlorohydrin
(M lb/yr) (M Ib/yr)
Production (allyl chloride,
1.11
0.147
epichlorohydrin, and glycerin)


Unmodified epoxy resins - use

0.251
Chemical intermediate - use

0.081
Export
0
0
Total
1.11
0.479
~Based on emission factor of 0.00152 lb lost per lb used derived
for epoxy resin manufacture.
Source: Systems Applications, Inc. 1980
267

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Materials Damage
Epichlorohydrin can pit steel and attack rubber and leather.
Containers used for storage and transport require special
precautions
Permissible Exposure Limits
OSHA standard
5 ppm as an 8 hr TWA
NIOSH recommendation
0.5 ppm TWA 10 hr/40 hr week
Celling
5 ppm 15 mi n
Human Toxicity
Chronic toxicity:
Carcinogenicity—The evidence for carcinogenicity to humans is
inadequate. One epidemiological study in workers showed an
excess of respiratory cancer. The evidence of carcinogenicity
in animals is sufficient
Mutagenicity--The evidence in humans is insufficient; the
evidence in short term tests is sufficient
Bibliography
Anderson, G.E. et al. 1980. Human Exposure to Atmospheric Concentra-
tions of Selected Chemicals. Systems Applications, Inc., San Rafael, CA.
Consumer Products Safety Commission. 1980. Epichlorohydrin (CAS 106-89-8).
j
Dorigan, J. 1976. Scoring of Organic Air Pollutants. MTR-7248,
Revision 1, Appendix II. Mitre Corporation, McLean, VA.
International Agency for Research on Cancer. 1979. IARC Monographs on the
Evaluation of the Carcinogenic Risk of Chemicals to Man". Lyon, France.
Vol. 11, p. 141.	
Kirk, R.E. and D.F. Othmer. 1979. Encyclopedia of Chemical Technology,
3rd ed. John Hi ley and Sons, Inc., He w York, NY!
268

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National Institute for Occupational Safety and Health. 1976. Criteria
for a Recommended Standard.¦¦Occupational Exposure to Epichlorohydrin.
U.S. Department of Health, Education, and Welfare, Public Health Service,
Center for Disease Control, NIOSH.
National Institute for Occupational Safety and Health. 1978. Current
Intel 1igence Bulletin No. 30--Epich]orohydrin. U.S. Department of
Health, Education, and Welfare, Public Health Service, Center for
Disease Control, NIOSH.
National Institute for Occupational Safety and Health. 1978. Technical
Report, Epichlorohydrin, Manufacture and Use...Industrial Hygiene Survey.
U.S. Department of Health, Education, and Welfare, Public Health Service,
Center for Disease Control, NIOSH.
National Institutes of Health. 1980. Oil and Hazardous Materials Technical
Assistance Data System. U.S. Environmental Protection Agency, Chemical
Information System.
National Institutes of Health. 1980. Registry of Toxic Effects of Chemical
Substances. National Library of Medicine, Bethesda, MD.
Systems Applications, Inc. 1980. Human Exposure to Atmospheric
Concentrations of Selected Chemicals. Vol. II PB81-193260.
San Rafael, CA.
Toxicology Data Bank. 1980. Toxicology Information Program (TIP),
NIOSH, National Library of Medicine, Bethesda, MD.
U.S. Department of Health, Education, and Welfare. 1980. National Gccupa-
tional Hazard Survey. DHEW/PHS/NIOSH, Cincinnati, OH.
U.S. Environmental Protection Agency. 1977. Chemicals in Commerce
Information System. Office of Toxic Substances. Washington, DC.
269

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Chemical Name
Methyl chloroform
CAS Number
71-55-6
Chemical Classification
Chlorinated aliphatic hydrocarbon
Synonyms
1,1,1-Trichloroethane; alpha-Tr1chloroethane; chloroethene; methyl
trichloromethane
Physical/Chemical Proterties
Description:
Colorless mobile volatile 1iquid, chloroform-!ike odor
Boiling point:
74° C
Melting point:
-32.6° C
Molecular weight:
133.41
Chemical formula:
CH3 CC13
Vapor pressure:
100 mm Hg 20° C
127 mm Hg 25° C
Solubility:
0.44 g/lQQ g water at 25" C, soluble in ethyl ether and ethyl
alcohol
Refractive index:
1.44 at 20® C
270

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Vapor density:
4.6 (air « 1)
Chemical reactivity:
. Liquid methyl chloroform will attack some forms of plastics,
rubber and coatings. Contact with strong caustics, strong
oxidizers and chemically active metals may cause fires and
explosions
Sources of Emissions
Product!on/processi ng:
630 million lb were estimated as produced in 1976. The
release rate from production has been estimated as
284,5 million lb/year
Uses:
Methyl chloroform has been a preferred solvent for cleaning
electrical machines, electronic devices and precision instru-
ments . It is also used as a dry cleaning agent, aerosol
propel 1 ant additive, a constituent of rubber adhesives and as
an additive to metal cutting oils. The environmental level
of emissions for these industrial uses have been reported as
<1 to 400 ppm (Data from Health Hazard Evaluation Reports,
NIOSH)
Transport:
Methyl chloroform is shipped in 5 and 55 gal steel drums, tank
cars, and tank trucks. Loading and unloading operations would
be possible sources of high emission concentrations
Sampling and Analytical Methods
NIOSH Method number S328
Sampling method:
A known volume of air is drawn through a charcoal tube to trap
the methyl chloroform present
Analytical method:
The desorbed sample is analyzed by gas chromatography
271

-------
Detection limits:
Using a sample size of 3 1 the detection sensitivity
ranges from 190 to 5700 mg/m3
Possible interferences:
1.	High humidity
2.	Compounds with the same retention times will interfere
with results
Permissible Exposure Limits
The OSHA standard is 350 ppm {1900 mg/m3)
Human Toxicity
Acute toxicity:
A number of fatalities have been reported due to deliberate or
accidental exposures
Chronic toxicity:
Carcinogenicity—The available data does not permit an evalua-
tion of the carcinogenicity of methyl chloroform in humans.
A long term animal bioassay is being completed by the National
Toxicology Program in FY83
Mutagenicity—Methyl chloroform has been reported as mutagenic
in Salmonella typhimurium. Additional testing is to be
completed in FY83 by the National Toxicology Program
Bibliography
Federal Environmental Agency (Berlin West) Waste Management Division. 1976,
NATO Report 55.
International Agency for Research on Cancer. 1979. IARC Monographs on the
Carcinogenic Risk of Chemicals to Humans. Lyon, France, Vol. 20.
pp. 515-525 .	
Kirk-Othmer. 1979. Encyclopedia of Chemical Technology. John Wiley and
Sons. New York, Nr; Vol 5, pp. 154-157.
U.S. Department of Health and Human Services. 1978. Occupational Health
Guideline for Methyl Chloroform. OSHA/DHHS/PHS. pp. 1-5.
272

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U.S. Department of Health, Education, and Welfare. 1978. NIOSH Current
Intelligence Bulletin 27. Chloroethanes: Review of Toxicity. DHEW/PVlS/NIOSH.
U.S. Department of Health, Education, and Welfare. 1977. NIOSH Manual of
Analytical Methods. DHEW/PHS. Vol. 3. S328-1-8.
U.S. Department of Health, Education, and Wei fare. 1977. NIOSH Manual of
Analytical Methods. DHEW/PHS. Vol. 1. 127-1-7.
U.S. Department of Health, Education, and Welfare. 1976. NIOSH Criteria for
a Recommended Standard.. .Occupational Exposure to 1,1,1-TrTchloroethaneT-"
T3HW7PWSTD5HT~~		—					
U.S. Environmental Protection Agency. 1976. Preliminary Scoring of Selected
Organic Air Pollutants¦ EPA-450/3-77-Q08e» pp. Aiv-239.
273

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Chemical Name
Nickel
CAS Number
7440-02-0
Chemical Classification
Metal
Synonyms
Carbonyl nickel powder, nickel catalyst, nickel sponge, raney
alloy, raney nickel
Physical/Chemical Proterties
Description:
Silvery gray metallic, odorless powder
Boiling point;
2732° C
Melting point:
1453s C
Atomic weight:
58.7
Chemical formula:
Ni
Vapor pressure:
Essentially zero at 20° C
Solubility:
Insoluble in water
Density (specific gravity):
8.9
274

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Chemical reactivity;
Nickel is a divalent metal with characteristic divalent metal
chemistry, although it does not readily form chloro- or
sulfate complexes under environmental conditions
Environmental Fate
Atmospheric reactivity—nickel carbonyl decomposes readily to form
nickel oxide in dry air and/or nickel carbonate in moist air. These
products are more likely to be atmospheric pollutants than is nickel
carbonyl
Nickel subsulfide occurs in air in particulate form and is subject to
settling. Impaction, rainout and washout. It is not believed to be a
significant atmospheric or water pol1utant
The form of nickel in air and its possible reactions have not been
extensively studied, Dye to the industrial importance of nickel
carbonyl , the possibility of nickel entering the atmosphere as nickel
carbonyl does exist. Although nickel carbonyl is recognized as a
hazard in industrial hygiene, there is a scarcity of information
regarding the amount of nickel carbonyl that escapes to the atmo-
sphere. In the atmosphere nickel is unreactive toward OH and O3
Table D-63 presents average nickel concentrations at 30 urban
National Air Surveillance Network Stations from 1957-1968
Sources of Emissions
Product!on:
U.S. nickel mining operations produce about 30 million lb of
Nickel annually and imports are approximately 330 million 1b
In 1977 there were two major nickel producers in the U.S.; the
Hanna Mining Co., Riddle, Oregon, and AMAX, Inc., at Port
Nickel, Louisiana, Production emissions are estimated at
500,000 lb/year
Uses;
The principal use of nickel is as an alloying agent. Nickel
emissions from melting and alloying are in the form of nickel
oxide or complex oxides. Other than direct use sources nickel
may be released from coal and oil fired boilers, coke ovens,
275

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TABLE 0-63. AVERAGE CONCENTRATIONS OF SUSPENDED PARTICLES
AND NICKEL AT 30 URBAN AIR SURVEILLANCE NETWORKS STATIONS
1957-1960, 1961-1964, AND 1965-1968
Station
Nickel Concen(ration,
1937-1960
1961-1964
1965-!968
Act rage
Atlanta, Cjl
Baltimore, Md.
Boise. Idaho
Boston. Mju.
Chattanooga, Tenn.
ChulesioQ, W. Vjl
Oucago, ItL
Gocinnati, Ohio
Cleveland, Ohio
Columbus, Ohio
Denver, Colo.
Des Moines, Iowa
Detroit, Mich.
E»l Chicsge, Ind.
EI Paw. Tex.
Indianapolis, Ind.
Lot Angeles, Calif.
Milwaukee. Wis.
New Orleans, La.
Newark, N J.
Oklahoma City, OkJtx.
Omiha, Nebr.
Philadelphia. Penn.
Phoenix. Aril.
Pittsburgh. Perm.
Saint Louts. Mo.
San Francisco, Calif.
Seattle, Wish.
Tacoma. Wish.
Was tun {ion, D.C.
AVERAGE
0.021
0.057
0.037
0.171
0.024
0.058
0,044
0.024
0.035
0.043
0.021
0.016
8.037
0.202
0.015
0.023
0.055
0.029
0.025
0.057
0,013
0.018
0.082
0.038
0.042
0.018
0.029
0.079
0.051
0.049
0.047
0.012
0.071
0.006
0.076
0.018
0.040
0.048
0.018
0.027
0.024
0.028
0.010
0.020
0.123
0.015
0.036
0.041
0.023
0,022
0.084
0.014
0.013
0.074
0.019
0.028
0.013
0.023
0.059
0.038
0.040
0.036
0.007
0.051
0.003
0.090
0.012
0.015
0.033
0.013
0.015
0.019
0.007
0.007
0.033
0.070
0.021
0.031
0.011
0.034
0.066
0.003
0.005
0.077
0.011
0.031
0.012
0.023
0.037
0.021
0.026
0.013
0.060
0.015
0.1 12
0.018
0.038
0.042
0.018
0.026
0.029
0.19
0.011
0.030
0.031
0.015
0.027
0.042
0.021
0.027
0.069
0.0 to
0.012
0.078
0.023
0.034
0.014
0.025
0.058
0.045
0.037
0.037
Source: Sittig 1975
276

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diesel fuel burning and gray iron foundries. Emission sources
have been estimated as follows:
Source
Pounds/Year
Iron and steel industry
Ferro al1oy manufacturing
Gray iron foundries
Nonferrous alloy manufacturing
Electric utility power pi ants
Coke ovens
Diesel fuel use
Industrial boilers
Heating boilers
6,518,000
3,863,000
22,133,000
8,456,000
123,000
1,785,000
231,000
828,000
186,000
143,000
TOTAL
{0AQPS 1980}
Di sposition:
Nickel scrap is a significant source of the nickel supply.
Essentially all nickel scrap is returned to mills, smelters,
refineries and foundries. Nickel alloy scrap is usually
exported to Japan or Germany for recycling
NI0SH Method number S 206
Sampling method:
A known volume of air is drawn through a cellulose membrane
filter to collect the analyte
Analytical method:
The sample solution is aspirated into the oxidizing ai r-
acetylene flame of an atomic absorption spectrophotometer
Detection limits:
At 26.5° C 745 mm Hg the working range of an 85 1 sample
is estimated to be 0.4 to 8 mg/rn^
Interferences:
There are no known interferences for the nickel atomic
absorption spectrophotometer assay
Sampling and Analytical Methods
277

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Permissible Exposure Limit
OSHA standard:
1 mg/m3 8 hour TWA (as nickel metal and soluble nickel
compounds)
NIOSH recommended standard:
0.015 mg/m3 10 hr T>IA
Human Toxicity
Chronic toxicity:
Carcinogenic]ty— Workers in nickel refineries have increased
incidences of nasal, lung, and larynx cancer. It is not
possible to state with certainty which specific nickel
compounds are carcinogenic to humans
Other chronic toxicity:
Pharmacokinetics, metabolism and nutritional studies for
nickel are on test in FY83 sponsored by the Division of
Research Resources, NIH
Bib!iography
Bureau of Mines. 1977. Nickel: Mineral Commodity Profiles. U.S. Department
of the Interior, pp. l-HT
International Agency for Research on Cancer. 1976. IARC Monographs on the
Evaluation of Carcinogenic Risk of Chemicals to Man" Lyon, France.
Vol. 11, pp. 75-114.	
Sittig, M., 1975. Environmental Sources and Emissions Handbook~ Noyes Data
Corporation, Park Ridge, NJ.
Sittig, M., 1980. Priority Toxic Pollutants. Noyes Data Corporation. Park
Ridge, NJ, pp. 276-279.
U.S. Department of Health and Human Services. 1983. Review of Current DHHS,
DOE, and EPA Research Related to Toxicology. National Toxicology Program.
tofstphottp:	
U.S. Department of Health and Human Services. 1978. Occupational Health
Guideline for Nickel Metal and Soluble Nickel Compounds"! DHHS/^HS/NlOSH.
U.S. Department of Health, Education, and Welfare, 1977. NIOSH Criteria for
a Recommended Standard...Occupational Exposure to Inorganic Nickel.
dhew/phs/niosm:	
278

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U.S. Department of Health, Education, and Welfare. 1977. Environmental
Exposure to Airborne Contaminants in the Nickel Industry. HTubH technical
Report Number 78-178. DHEW/PHS/NIOSH. pp. 1-27.
U.S. Department of Health, Education, and Wei fare. 1977. NIOSH Manual of
Analytical Methods. DHEW/PHS/NIOSH. Vol. 3. S206.
U.S. Environmental Protection Agency. 1980. OAQPS Draft Exposure Assessment.
279

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Chemical Name
nitrobenzene
CAS number
98-95-3
Chemical Classification
N1troaromatic compound
Synonyms
Nitrobenzol, oil of mirbane, mononitrobenzene
Physical/Chemical Properties
Description:
Yellow oily liquid, yellow crystals in solid state
Boiling point:
210.8° C at 760 mm
Melting point;
5.7° C
Molecular weight:
123.11
Molecular formula
C6H5N02
Vapor pressure;
0.340 mm at 25° C
Density;
1.2037 at 20° C (water at 4° C)
Refractive index:
1.5529 - highly refractive
Sol ub i 1 i ty:
Slightly soluble in water
Octanol/water log partition coefficient:
1.88
280

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Photochemical reactivity:
Undergoes photoreduction when irradiated with UV
Chemical reactivity;
Undergoes nitration, halogenation and sulforation and is a
strong oxidizing agent. These reactions are not likely to
occur under environmental conditions
Sources of Emissions
Production/processing:
In 1978 there were 5 companies producing nitrobenzene
at 7 locations
An estimated 850 million lb were produced in 1978
The foil owing producers and processors of nitrobenzene have
been reported:
Company
American Cyanimid
Du Pont
First Chemicals
Mobay Corporation
Rubicon
BASF Wyandotte
Dow
Hercules
H. Kohnstaum
MAK Chemical
Location
Bound Brook, NJ
Willow Island, WV
Beaumont, TX
Deepwater, NJ
Gibbstown, NJ
Pascagoula, MS
Mew Martinsville, WV
Geismar, LA
Wyandotte, MI
Midland, MI
Brunswick, GA
Harbor Beach, MI
Hopewel1, VA
Pari in, NJ
Camden, NJ
Clearing, IL
Muncie, IN
281

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Company
Procter and Gamble
Location
Union Carbide
Memphis, TN
Institute, WV
Eastman Kodak
Rochester, NY
Monsanto
Toms River Chemicals
Luling, LA
Toms River, NJ
Production and process emissions:
263,500 lb (1978)
Uses:
The total number of estimated sites where nitrobenzene
is used is 279
Most of (98%) nitrobenzene is used captively to pro-
duce aniline (1978 estimate)
Nitrobenzene is used as a solvent in the petroleum
Industry and in cellulose ether manufacture
Nitrobenzene is used as a chemical intermediate
Emissions from use:
Use	Emissions
Solvent applications	12.75 million lb
Production and analine manufacture 275,000 lb
Chemical Intermediate	6,000 lb
Total nationwide emissions of nitrobenzene in 1978:
13 million lb
Emissions from storage:
Storage emissions represent total losses from surge,
final product, feed storage tanks, and loading and
handling. Emissions range from 300-18,000 lb per
year (from site visit data)
282

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Disposition:
Atmospheric concentrations of nitrobenzene adjacent
to production or processing sites are believed low.
Atmospheric nitrobenzene is not monitored by industry.
High concentrations of wastes should be incinerated.
Caution: poisonous nitrous gases can be produced
Sampling and Analytical Methods
NIQSH Method number S 217
Sampling method:
A known volume of air is drawn through a silica gel
tube
Analytical method:
An aliquot of the desorbed sample is analyzed by GC
Detection limits:
Method validation in range of 3.11-12.45 mg/m^
{23° C 765 mm) using 55 1 of sample
Possible interferences:
Vapors may not be trapped efficiently during
periods of high humidity
Compounds with the same column retention time
as nitrobenzene can interfere with the analysis
Permissible Exposure Limit
OSHA Standard
1 ppm (5 mg/rP)
Human Toxicity
Acute toxici ty:
A few ml of nitrobenzene liquid can be lethal
to humans
283

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Chronic toxicity:
Carcinogenicity—Ors test in FY83 for long term carcinogenesis
animal bioassay (National Toxicology Program)
Mutagenic!ty--0n test in FY83 for mutagenesis/genetic toxicity
testing (National Toxicology Program}
Other chronic toxicity:
On test in FY 1983 for pharmacokinetics/metabolism studies
{University of California)
Bibliography
Anderson, G.E., et al. Human Exposure to Atmospheric Concentrations of
Selected Chemicals. EPA Contract No. 65-02-30 OAQPS Research Triangle
Park, NC.	~~
Federal Environmental Agency (Berlin-West). 1976. Waste Management Division.
NATO Report 55.
Sittig, M. 1980. Priority Toxic Pollutants. Noyes Data Corporation. Park
Ridge, NJ» pp. 27^57!	^	"
U.S. Department of Health, Education, and Welfare. 1977. NIOSH Manual of
Analytical Methods. DHEW/PHS/NIQSH. Vol.3, S217-1 to S217-9.
U.S. Department of Health and Human Services. 1983. Review of Current DHHS,
DOE, and EPA Research Related to Toxicology. National Toxicology Program.
DHHS/PHS/NTP. p. 40, 50, 170.			
U.S. Department of Health and Human Services. 1978. Occupational Health
Guideline for Nitrobenzene. DHHS/PHS/NI0SH, pp. 1-5:	^
284

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Chemical Name
Mi trosomorpholi ne
CAS Number
59-89-2
Chemical Classification
N-nitroso compound
Synonyms
morpholine, 4-nitroso-, N-nitrosomorpholine, 4-ni trosomorpholi ne,
MMOiR
Physical/Chemical Proterties
Description:
Yellow crystals
Boiling point:
225° C 747 mm
Melting point:
29° C
Molecular weight:
116.1
Chemical formula:
c4h8n2°2
Solubility:
Soluble in water, and soluble in organic solvents
Photochemical reactivity:
Photochemically reactive, light sensitive, especially to
UV
Chemical reactivity:
Resistant to hydrolysis. Strong oxidants oxidize NMOR to
the corresponding nitramine
285

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Sources of Emissions
Producti on/processi ng:
NMOR is not produced commercially and there are no reports of
past commercial production
Uses:
No reported uses. NMOR has been detected as a contaminant in
analytical grade dichloromethane and chloroform, in morpholine
and in a rubber accelerator. Rubber or tire manufacturing
workers may be exposured in the range of 9-130 ug/day
Sampling and Analytical Methods
Sampling methods:
Samples should be stored in opaque containers because of the
light sensitivity of NMOR
Analytical methods:
Gas chromatography recommended for analysis of NMOR using
either an electron-capture detector or alkali flame ionization
detector. Confirmation should be made with a mass spectrometer
or thin layer chromatography
Possible interferences:
Any compound which has the same retention time as the analyte
is a potential interference. Compounds containing phosphorous
or nitrogen could be sources of interference
Human Toxicity
Chronic toxicity:
There are no case reports or epidemiologic studies available
Carcinogenicity--There is sufficient evidence for the carcino-
genic effect of NMOR in experimental animals and the chemical
should be regarded as carcinogenic to humans
Mutagenicity—There is evidence of the mutagenic effect of
NMOR in experimental animals. NMOR has been selected for
further mutagenesis/genetic toxicity testing by the National
Toxicology Program
286

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Bibliography
International Agency for Research an Cancer. 1978. IARC Monographs on the
Evaluation of the Carcinogenic Risk of Chemicals to~TTuiaWs~^ Cyan," France.
Vol. 17, pp. 263-275.
International Agency for Research on Cancer. 1972. IARC Scientific Publica-
tion No. 3, N-Nitroso Compounds: Analysis and Formation. Lyon, France,
pp. 10-14.
RTECS Data Base.
U.S. Department of Health and Human Services. 1983. Review of Current DHHS,
DOE, and EPA Research Related to Toxicology. National Toxicology Program.
BHWPfiwrp:—		
U.S. Department of Health and Human Services. 1982. Third Annual Report on
Carcinogens. National Toxicology Program. DHHS/PHS" p. Z31-232.
287

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Chemical Name
Polychlorinated biphenyl s, a generic term for 209 possible isomers
of chlorinated bi phenyls
CAS Numbers
13-36-36-3, generic
11097-69-1, Aroclor 1265
11096-82-5, Aroclor 1260
Chemical Classification
Halogenated aromatic hydrocarbon
Synonyms
PC8, chlorinated bi phenyl, chlorinated di phenyl , chlorinated
di phenylene, chloro biphenyl, polychlorinated polypheny!s
Trade Names
Akarel, Aroclor, Clophen, Chlorextol, Dykanol, Interteen, Kanechlor,
Noflanol, Phenochlor, Pyralene, Pyranol, Sovol, Therminol
Physical/Chemical Properties
Description:
Variable appearance. Lower chlorinated Aroclors are colorless
mobile oils. Increased chlorinated of the biphenyl results in
increasing yellow colorations and compound viscosity
Boiling point:
Aroclor 1254, 365° C
Aroclor 1260, 390° C
The boiling points for the PCBs increase with increased
chlorination
288

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Melting point:
2-chlorobiphenyl 5 54° C
decachlorobiphenyl, 310° C
Melting points for the PCSs increase with the chlorination of
the biphenyl. The PCBs do not crystal 1ize upon heating or
cooling, but at specific temperatures defined as pour points,
they form resinous compounds
Molecular weight:
Exact molecular weights of the PCBs are unknown
Chemical formula:
The PCBs most frequently occur as mixtures; exact chemical
formul as are unknown
General formula: Ci2ClxHx (x = 1 to 10)
Log partition coefficient {octanol/HgO):
10,000 to 20,000 for representative tri-, tetra-, and penta-
chlorobiphenyls
Refractive index:
Aroclors, 1.617-1.640 at 20° C
Kaneclors, 1.623-1.690 at 25° C
Solubility:
The PCBs are generally considered insoluble in water
Aroclor 1254, 0.1 ug/1
Chlorobiphenyls are freely soluble in nonpolar organic
solvents and lipids
Density:
1.495 to 1.505
Vapor pressure:
1 mm at 25° C
Photochemical reactivity:
Transformation products--
Reactivity toward OH: 5% butane
Reactivity toward O3: no reaction
Photolysis: free radicals can form that may result in
the formation of the contaminant chlorodibenzofurans
289

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Chemical reactivity:
PCBs are considered inert to most of the typical chemical
reactions. These compounds do not undergo oxidation, reduc-
tion , addition, or elimination except under extreme conditions
Environmental fate
Due to their chemical stability, environmental persistence, and
tendency to bioaccumulate, the PCBs have continued to present
an envi ronmental hazard despite regulatory actions
Air:
Vaporized PCBs can be adsorbed onto particulates and trans-
ported with the prevailing wind. Ultimately they will be
deposited on land or water
Water:
PCBs found in water are mainly adsorbed to particulate matter
and sediment. Because of their low aqueous solubility, PCBs
discharged into water bodies will accumulate and redissolve
very slowly. Fish can bioaccumulate 105 times more PCBs
than are found in surrounding waters
Soil:
The primary source for PCBs in soil is atmospheric fallout
Estimated half-life in soil: 5 years
Estimated residence time: 35 years
Large fractions of PCBs in soil may 1 each into adjacent water
bodies
Sources of Emissions
Production:
Except for 1imi ted research and development applications, the
PCBs are no longer produced domestically, and no importation
or exportation of the compounds has been permitted since July
1979. United States production peaked in 1970 when greater
than 80 million pounds was manufactured principally in Illinois
290

-------
Uses;
PCBs are no longer used or consumed for any kind of end use in
the United States, and end use is no longer a source of PCB
emissions
Prior common uses have been in transformer and capacitor
fluids, electrical insulations, pi asticizers, hydraulic
fluids, epoxy paints, carbonless reproduction papers, and
certain lubricants. These prior uses have continued to be
sources for environmental and human exposure
Storage:
The loss of PCBs by evaporation or leakage when stored in
closed systems such as in transformers and capacitors is not
believed to be a significant emissions source
EPA regulations specify the types of containers that can be
used for the storage of liquid containing PCBs prior to
incineration
Transportation:
Not significant
Disposition:
The only significant sources of PCB emissions to the atmo-
sphere are from the disposal of PCB-containing transformers
and capacitors. When PCBs and RGB-containing products are
disposed of, disposal must be undertaken in accordance with
EPA regulations. In 1980 there were the following existing
and proposed incineration sites:
* Designates incinerator site existing in 1980
Annual emissions of PCBs if all 12 sites are operational is
estimated to be between 3,000 and 30,000 Ib/yr
The concentration of PCBs in PCB-containing wastes determines
the disposition. Wastes that contain PCBs greater than
500 ppm require incineration. Chemical landfill disposal is
permitted for specified wastes provided all free-flowing PCBs
have been drained for incineration
~Bridgeport, NJ
*Deer Park, TX
*Baton Rouge, LA
San Francisco, CA
Los Angeles, Ca
Denver, CO
Chicago, IL
Sandusky, OH
Atlanta, GA
Richmond, VA
Waterford, NY
El Dorado, AR
291

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Sampling and Analytical Methods
1. Polychlorinated Biphenyls in	Air—Method Number PSCAM 244
a.	Adsorption of Florisil
b.	Hexane desorption
c.	Gas chromatography with	electron capture detection
Detection limits:
The estimated range of detection for this method is
0.01 to 10 wig/in^. Hie minimum detectable quantity of
PC8 from a standard curve was determined as 32 pg per
Injection. Field samples analyzed by this method ranged
from 0.1 to 1.5 mg/m3
Possible interferences:
Compounds with nearly the same retention time as the PCS
sample on the GC column. The chlorinated pesticides such
as DOT, DDEs etc., have been reported to interfere with
determinations, and sulfur-containing compounds in petroleum
products have been reported as interferences
2. Polychlorinated Biphenyls in Air—Method Number P&CAM 253
a.	Adsorption in Florisil
b.	Hexane desorpti on
c.	Perchlori nation
d.	Gas chromatography with electron capture detection
Detection limits:
The estimated useful range of this method is 0.01 to
10 mg/m^. The minimum detectable 1imit of decachloro-
biphenyl, the perchlorination product, is 10 pg per
injection
Possible interferences:
Compounds with the same column retention time or nearly
same. Chlorinated pesticides, sulfur-containing compounds
in petroleum products, and bi phenyl, if present in the PC8
mixture
Permissible Exposure Limits/Threshold Limit Values
PEL: 1 nig/m3, 8-hour Time Weighted Average {42 percent chlorine)
0.5 mg/m^, 8-hour Time Weighted Average {54 percent chlorine}
TLY: 1 mg/in3, 8-hour Time Weighted Average (42 percent chlorine)
0.5 mg/m3, 8-hour Time Weighted Average (54 percent chlorine)
292

-------
Toxicity
Acute toxicity:
Acute toxicity studies are on test in FY83 by the Division of
Research and Resources, National Institutes of Health. The
acute toxicity grams per kilogram of the PCBs increases with
chlorination, as shown in the following results:
Aroclor
1221 1232 1242 1248 IZ60 1262 1268 4465 5*42 S46D 2565
Rate, Oral	3.9*	4.5*	8.7*	U.O*	10.0$	11.jS	10.9$	16.Q§	10.6$	19.2*	6.3"
LDjq*
Rabbits, Skin	>2.0*	>1.3*	>0.8*	>7.9*	>1.35	>1.3*	-	>2.0*	>1.3*	>7.9*	>2.0*
MtO	<3.2*	<2.0*	<1.3*	<1.3*	<2.0$	<3.2$	<2.3$	<3.2$	<2.0$	--	<3.3
*	LDgo Is lethal dose to 50 percent of recipients, and MLO 1s M«n Ictftat dose
*	Undiluted
$ Administered as 50 percent In com oil ¦
*	Adn1n1stered as 33.3 percent corn of1
Chronic toxicity:
Carclnogenicity--The evidence for the carcinogenicity of PCBs
in humans is inadequate. The evidence for the carcinogenicity
of PCBs in mice and rats is sufficient for certain PCBs when
the compounds are administered in their diets
Mutagenicity--Short-term mutagenicity testing has not produced
dominant 1ethal mutations or chromosomal abberations. No data
on humans are available
Teratogenic!ty--Data available are inadequate; however,
teratogenic effects have been noted in several species of
animals, Including humans
Other Chronic effects:
Chloracne
Strong chronic irritant when inhaled, skin-absorbed, or
Ingested
Liver ailments in humans
Increased eye discharge and eyelid swelling
Jaundice
293

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Bib!iography
American Conference of Governmental Industrial Hygienists. 1982, TLVs,
Threshold Limit Values for Chemical Substances and Physical Agents in the
WorTTrfvTronielt. ISBN No. 936712-39-2. Cincinnati, OH.
Clayton, D., and E.F. Clayton, ed. Patty's Industrial Hygiene, 3d Revised
Edition, Vol. 2. Toxicology. John Wiley and Sons, New York, )fT.
Federal Register. 1979. Vol. 44, Mo. 106, pp. 31530-68.
International Agency for Research on Cancer. IARC Monographs on the
tion of the Carcinogenic Risk of Chemicals to"Humans. Vol. 7,pp." 291-31'5'.
Lyon, France.	1 "	——
International Agency for Research on Cancer. IARC Monographs on the Evalua-
tion of the Carcinogenic Risk of Chemicals to Humans"-"" Supplement 4,
pp. 217-18.					—				
National Library of Medicine. 1980. Toxicology Data Bank. Medlars II.
Sittig, Marshall. 1980. Priority Toxic Pollutants. Noyes Data Corporation,
Park Ridge, NJ.
Systems Applications, Inc. 1980. Human Exposure to Atmospheric Concentrations
of Selected Chemicals. Vol. II. PB8I-193260, San Raphael, CA.
U.S. Department of Health, Education, and Welfare. 1977. NIOSH Manual of
Analytic Methods. Vol. 5. DHEW (NIOSH) No. 77-157-A, Cincinnati, OH.
U.S. Department of Health, Education, and Welfare, Public Health Service.
1977. CDC/NIQSH. Occupational Exposure to Polychlorinated Biphenyls~
Cincinnati, OH.
U.S. Environmental Protection Agency. 1977. Polychlorinated Biphenyls.
Contract No. 68-03-2504, Research Triangle Park, NC.
294

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Chemical Name
Toluene
CAS Number
108-88-3
Chemical Classification
Aromatic hydrocarbon, alkyibenzene
Synonyms
Methacide, methyl benzene, methyl benzol, phenyl methane, toluol
Physical/Chemical Properties
Description:
Col or]ess, volatile, flammable liquid at ambient temperatures;
very refractive; noncorrosive; sweet odor, similar to benzene,
but milder
Boiling point:
110.6° C
Melting point:
-95.09 C
Molecular weight:
92.15
Chemical formula:
C7H8
Vapor pressure:
24 mm Hg at 25° C; 22 mm Hg at 20° C; 36.7 mm Hg at 30" C
log partition coefficient (Octanol/H2O):
2.80
Refractive index:
N0: 1.49693 at 30° F
1.49414 at IT F
295

-------
Solubility:
Slightly soluble (4.7 g/1 HgO); sol. in alcohol and
ether
Den s "f tv:
0.86694 g/ml at 20° C
0.86230 g/ml at 25° C
Vapor density;
3.1 (air = 1)
Photochemical reactivity:
Effective ambient air decay rate: 2.8 x 10~5 s~l (daytime)
Reactivity toward: OH is 2X butane
No reactivity toward O3 or photolysis
Chemical reactivity:
Reacts with oxidizing materials
Environmental fate
Can persist in atmosphere. Its hi gh volatility and 1ow sol -
ubi1ity in water enables it to volatilize from water surfaces
to the atmosphere
Sources of Emissions
Production:
An estimated 67,000 million lb of toluene was produced
in 1978
Several petroleum or petrochemical processes:
a.	from catalytic re formate from refineries (principal
method in U.S.) an estimated 64,875 million lb was
produced in 1978
b.	hydrocracking
c.	steam cracking
d.	catalytic cracking
296

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By-product sources:
a.	from coal carbonization, an estimated 175 million lb
of toluene was produced in 1978
b.	as BIX (Benzene, Toluene, Xylene) from petroleum-
derived pyrolysis gasoline, an estimated 1,560
million lb was produced in 1978 from this source
c.	from olefin manufacturing during cracking of hydro-
carbons
d.	from styrene manufacturing, 320 million 1b of toluene
was produced in 1978
e.	from coal-derived BTX, 175 million lb of toluene was
produced in 1978
Toluene isolated from BTX:
a.	Chemi cal intermedi ate:
benzene manufacturing (by dealkylation)
toluene dlisocyanate products
xylenes (via disproportionation)
benzoic acid manufacturing
benzl chloride
vinyl toluene
benzaldehyde
p-cresol
backblending into gasoline
b.	solvent
paints
rubber
pi astics
coati ngs
pharmaceuticals
c.	in manufacturing of artificial leather, photogravure
inks
All toluene produced as BTX and not isolated is blended into
gasoline
Tables D-64 through D-67 and Figure D-5 present toluene produc-
tion, consumption, and emission data
297

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TABLE D-64. 1978 TOLUENE PRODUCTION AND CONSUMPTION
Total
Isolated	Tolueni	Toluene
Toluene	in BTX _ Produced
Source	(M lb}	CM lb)	[M lb)
Production
Catalytic reformats 8,000
56,875
64,875
Pyrolysis gasoline 830
7 30
1,560
Coal derived 145
30
175
Styrene by-product 220
100
320
Total 9,195
57,735
66,930
Source: Systems Applications, Inc.
1980

TABLE D-65. END-USE CONSUMPTION

End Use
Isolated
Toluene
Used
C%)
Toluene
Used
(M lb/yr)
Gasoline as BTX

57,735
Gasoline isolated (back blended)
35.1
3,230
Benzene dealkylation
40.2
3,693
Paints and coating solvent
6. 3
579
Adhesives, inks, pharmaceuticals solvent
3.2
291
Toluene diisocyanate
4.8
440
Xylenes (disproportionation)
2.3
216
Benzoic acid
1.6
144
Benzyl chloride
0.8
79
Vinyl toluene
0.6
55
Benialdehyde
0.2
IB
p-Cresol
0.1
14
Miscellaneous others
0.6
53
Net export
4.2
383
Total
100.0
66,930
Source: Systems Applications, Inc. 1980
298

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TABLE D-66. TOTAL NATIONWIDE 1978 TOLUENE EMISSIONS
Toluene Emissions
Source	 (Ib/yr)	
Toluene production - catalytic reformats
6,487,500
Toluene production - pyrolysis gasoline
1,404,000
Toluene production - coal-derived
218,750
Toluene production - styrene by-product
243,200
Paint and coatings solvent ' '
579,000,000
Adhesives, inks, pharmaceutical solvent
247,000,000
Benzene production
738,600
Toluene diisocyanate production
563,200
Benzoic acid production
216,000
Benzyl chloride production
79,000
Vinyl toluene production
55,000
Benzaldehyde production
27,000
p-Cresol production
28,000
Xylene disproportionation production
43,200
Other/miscellaneous uses
20,140
Gasoline - marketing evaporative loss
38,492,000
Gasoline - automobile evaporative loss
35,400,000
Gasoline - automobile exhaust emissions
1,300,147,000
Coke ovens
25,680,000
Total
2,235,842,590
Source: Systems Applications, Inc. 1980
299

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TABLE D-67. EMISSIONS RATES AND NUMBER OF GENERAL POINT SOURCES OF TOLUENE
Toluene Production
(Catalytic Reforming)*	Gasoline Marketing 	Coke Oven	
Emissions/Site Ntjrnber	Emissions/Site Number	Emissions/Site Number
Region (gm/sec) of Sites	(qm/sec) of Sites	(gm/sec) of 'Sites
New England
0
0
0,00245
11,105
6.062
0
Middle Atlantic
0.535
17
0.00245
28,383
6.062
15
East North Central
0.510
28
0.00245
42,270
6,062
25
West North Central
0.227
16
0,00245
23,304
6.062
3
South Atlantic
0.250
5
0.00245
37,286
6.062
4
East South Central
0.422
a
0.00245
16,313
6,062
9
West South Central
0.634
71
0.00245
28,336
6.062
2
Mountain
0.116
23
0.00245
12,015
6.062
2
Pacific
0.429
33
0.00245
26,647
6.062
1
* This Includes both the nonisolated toluene (as BTX) producers and the
isolated toluene producers.
Source: Systems Applications, Inc. 1980

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Figure D-5. Specific point sources of toluene emissions.
Source: Systems Applications, Inc. 1980

-------
Storage:
Outside/detached storage or inside in standard flammable
liquids storage room/cabinet. Separate from oxidizing
materials
Transportation:
In glass bottles, cans, drums, tank cars, tank trucks, or
tank barges
Disposition:
Toluene wastes originate mainly in petrochemical plants
as well as plants which use toluene as a raw material for
synthesis of the above-mentioned compounds. Further sources
of waste are installations which blend fuels and plants which
utilize toluene as a solvent
When discharging wastes of low toluene content into the
sewer system, the local discharge regulations have to be
observed. Solvent wastes from which toluene cannot be recovered
and toluene-containing sludges are burnt. Distillation residues
and toluene-containing sludges are disposed of in special
waste incinerators
Sampling and Analytical Methods
1. EPA "Preferred Method1'
a.	Tenax GC sorbent collection (gives pre-
concentrated samples)
b.	Thermal! elution
c.	Gas chromatographic/^ ame ionization detector
determi nation
Detection limits: (depend on sample volume)
0.1 ppb with capillary column and
flame ionization detector--25 1 sample on sorbent trap
0.3 ppb with gas chromatographic/photoionization detector
directly injected—1 ml sample
Possible interferences:
High humidity
Interfering compounds possibly also present in the air
Any compound with the same column retention time
302

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2.	NIOSH Method S 343 for Toluene
a.	Adsorption on charcoal
b.	Desorption with carbon disulfide
c.	Gas chromatographic analyses
Detection Limits:
0.01 mg/0.5 1 for a 22 1 sample at 16x1 attenuation on a
gas chromatograph fitted with a 10:1 splitter
Possible interferences:
High humidity
Other sol vents in air
Presence of other compounds with same retention time
3.	See Appendix A
Cryogenic trapping or Tenax adsorption appear to be
the best approaches. GC/PID is a useful determinative
technique
Materials Damage
Toluene will attack some forms of plastics, rubber, and coatings.
Containers may burst at elevated temperatures
Permissible Exposure Li mi ts/Threshold Limit Values
ACGIH
100 ppm {375 mg/m^)
150 ppm (560 mg/m3)
Odor perception: TLV 40 ppm
OSHA	NIQSH
TWA	200 ppm	100 ppm
Ceiling 300 ppm	200 ppm/10 min
Peak	500 ppm/10 mi n
Human Toxicity
Acute tox i c i ty:
Inhal ation: 200 ppm TC[_q - central nervous system
100 ppm TC|_o - psychotrophic
Chronic toxicity:
Carcinogenic!"ty--0n test for carcinogenicity in FY83 (U.S.
DHHS 1983)
Mutagenicity--0n test for mutagenesis/genetic toxicity in FY83
(U.S. DHHS 1983)
Teratogenicity—Tests to be completed in FY83 for reproductive/
developmental toxicity (U.S. DHHS 1983)
303

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Other chronic toxicity:
Blood abnormalities
Bone marrow chromosome damage
Metabolic effects
Enzymatic effects
Increased liver microsomal enzymes
Neurological/behavioral toxicity testing to be completed
in FY83 (U.S. OHHS 1983)
Pharmacokinetics/metabolism testing to be started in FY83
{U.S. DHHS 1983)
Bibliography
American Conference of Governmental Industrial Hygienists. 1982. TLVS,
Threshold Limit Values for Chemical Substances and Physical Agents in the
Work Environment with Intended" Changes for 1982. ISBN No. 936712-39-2.
Cincinnati, OH.	~
CI ayton, George D., and Florence E. CI ayton, eds. Patty's Industrial Hygiene,
3rd Revised Edition, Vol 2. "Toxicology." John Wiley and Sons, New
York, NY.		—'—	
Fuller, B., J. Hushon, M. Kornreich, R. Quellette, L. Thomas, and P. Walter.
1976. Preliminary Scoring of Selected Organic Air Pollutants. EPA-450/3-77-
008e. The Mitre Corporation. McLean, YA.
Kutz, Morris, ed. 1977. Methods of Air Sampling and Analysis. Vol. 3. Alpha
Intersociety Committee, Ameri can Public Health Association, Wa s h ington, DC.
Kirk-Othmer. Encyclopedia of Chemical Technology, 2nd ed. John Wiley and
Sons, New York, NY. Vol. 20.	~
Mackison, Frank W., R. Scott Stricoff, and Lawrence J. Partridge, Jr., eds.
1978. NIOSH/OSHA Pocket Guide to Chemical Hazards. DHEW (NIOSH) Publication
No. 78-210. Washington, Dt":	
McGraw-Hill. 1977. McGraw-Hill Encyclopedia of Science and Technology, 4th ed.
McGraw-Hill Book Company. New York", NYT '	"
National Fire Protection Association. 1981. National Fire Codes, A Compila-
tion of MFPA Codes, Standards, Recommended PractTceTr~am3~7?anuaTsT Vol. 13.
NFPA. Quincy, MAI!
Proctor, Nick W., and James P. Hughes. 1978. Chemical Hazards of the Workplace.
J.B. Lippincott Company, Philadelphia, PA.
304

-------
Riggin, R.M. 1983. Technical Assistance Document for Sampling and Analysis
of Toxic Organic Compounds 1n Ambient Air. EPA6UU-/4-H3-U2/. Batte11e
Columbus Laboratories. Columbus, OH.
Sittig, Marshall. 1980. Priority Toxic Pollutants. Noyes Data Corporation.
Park Ridge, NJ.
Systems Applications, Inc. 1980. Human Exposure to Atmospheric Concentrations
of Selected Chemical s, Vol. 11.	Systems Applications, Inc., San
Raphael, CA.
U.S. Department of Health Education and Welfare. 1977. NIOSH Manual of Analy-
tic Methods, Vol. 1. DHEW (NIOSH) Publ. No. 77-157-A. Cincinnati, OH.
U.S. Department of Health Education and Welfare. 1977. NIOSH Manual of Analy-
tic Methods, Vol. 3. DHEW (NIOSH) Publ. No. 77-157-C. Cincinnati, OH.
U.S. Department of Health and Human Services. 1983. National Toxicology
^ev?eW-of t?u_rei?t [WHS, DOE, and EPA Research Related to Toxicology.
NTP-83-001. National Toxicology Program. Research Triangle Park, NC.
U.S. Department of Labor. 1981. General Industry, OSHA Safety and Health
Standards (29CF191Q). Occupational Safety and Health Administration.
Washington, DC.
U.S. Department of Transportation. 1978. Chemical Hazards Response Informa-
tion System (CHRIS) Hazardous Chemical Data"! United States Coast Guard,
Washington, DC.
U.S. Environmental Protection Agency. 1976. Disposal of Hazardous Wastes,
Manual on Hazardous Substances in Special Wastes. NATO/CRMS Report 55.
Washington, DC.
U.S. Environmental Protection Agency. 1982. Health Assessment Document for
Toluene—Draft. EPA-600-8-82-008. Environmental Criteria and Assessment
Office. Research Triangle Park, NC.
305

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Chemical Name
Trichloroethylene
CAS Number
79-01-6
Chemical Classification
Chlorinated Hydrocarbon
Synonyms
Acetylene trichloride; 1-chloro-2, 2-dichloroethyl ene; 1,1-dichloro-
2-chloroethylene; ethinyl trichloride; ethylene trichloride; ICE;
Tri; trichlorethylene; 1,1,2-trichloroethylene
Physical/Chemical Proterties
Description:
Colorless liquid, volatile, nonflammable
Boiling point:
87° C
Melting point:
-73° C
Molecular weight:
131.4
Chemical formula:
C2HC13
Vapor pressure:
77 mm Hg at 25° C
Solubility:
Miscible with H2O {0,1% w/v at 20° C); miscible with acetone,
ethanol, diethyl ether, chloroform arid oils.
Log Partition Coefficient (Octanol/HgO):
2.29
306

-------
Photochemical reactivity:
High photochemical reactivity; oxidative breakdown of atmo-
spheric oxygen, greatly accelerated by elevation of temperature
and exposure to light, especially UV
Chemical reactivity:
Slowly oxidized by O3 and RO2, products are phosgene,
HC1, CO, trichloroethylene oxide and dichloroacetylchloride;
unreactive toward OH
Density:
1.4642 at 20° C (4° C water)
Environmental Fate
Not expected to accumulate in atmosphere due to low solubil-
ity and reactivity. Half-life in air range from 157 minutes
to 8 hours, 1onger in water
Sources of Emissions
Product!on/processing:
From acetylene {high manufacturing cost)
By chlorination of ethylene
By oxychlorination of ethylene or dichloroethane (perch!oro-
ethyl ene is a byproduct)
Uses:
In industrial metal fabricating industry for vapor degreasing
and cleaning operations
Solvent/solvent base for adhesives, seal ants, lubricants, and
dip-painting processes
Textiles
Low temperature heat transfer fluid
Component in spot remover and cleaning fluids for rugs, etc.
Pharmaceutical grade used as general anesthetic and an analgesic
Tables D-68 to 0-72 present estimated production, end uses, and
emission losses
307

-------
TABLE D-68. PRODUCTION OF TRICHLOROETHYLENE
Source
Location -
1978 Estimated
Production
[million pounds)
1978 SstizLated
Capacity
[million sounds)
Geographic
Coordinate!
Dow CJieaical
.Ethyl Corpora-
tisn
"PPG Industries
Total
Fresport, TX
Baton Rouge, LA
"Lake Charles, LA
89.0
37.0
164.0
290
120
SO
220
2B'. 59', U
N. Latitude
9S* , 24• , 45
W, Longitudi
30* , 18' , 
-------
Figure D-6. Specific point sources of trichloroethylene emissions.
Source: Systems Applications, Inc. 1980

-------
TABLE 0-70. TRICHLOROETHYLENE
tr»i a t» 1an ^auccv
Pccxjuci loai
Ac el ytcnB*t>j«e® - Ui ¦ «<) »
Morn* (dent i M «d
Tf JmU|>uf t Al ior»i
j>o At} Imj
Ti*ut(cr
Acct denta! apiUi
Tul Al omituion	i ty*
	? u ^ lt uf
»oo w*» &i e hr oshm
Trlc'ilDfuoOiyleuc i •
A J*f lO< I I Y p»*li I i>l AlU uru1«<
F«slcr* 1 u* t»r Poll hit iurt ^ imirot
Act
I lulu^t € I A I lllitt
cr*»iij cI«|H ^ l«n* vA|«)r
( C A I»C ( A
Coiw**y»n i va^Hji
kI<*1 i «&&«r of operationa i
l«*7t5
lI,440
i,?n
69)
Pfop«r dealqu a fid op«rALton of
c^uifweiii '25*. - (.0\ ef fici *ncy 1
CaMiO^ tinrvui pi ion (9St - tQ0\
« 11 lct*r*cyI
1 ng lMcr.it lou
Liquid aI»ioi |»t Ian
Wi»t« solvent, i«c!am l ton t$0t
iff Ic les'scy 1
Has ta *atv«^t )«(««ui • i 1*i t of
100	in 8 h>r losn&i
COfk'itu*i;l u!>m ol
«n*| A liAn an
ii¦« f iii	ft r un-
rte» lc f»i »a(t| i uuiul (.of f i'f ,
a»v,i m»\ l«»* ai o, in
AU'I 1e0	< r A|k-c L I va 1 y x

-------
TABLE 0-71. ESTIMATED 1978 TRICHLOROETHYLENE
NATIONWIDE EMISSION LOSSES
Estimated National Emission
Source						 (million Ib/yr )	
Production	0.6
Cold cleaners	32.9
Vapor degreasers	195.6
Solvent	11.6
Export .	0
Total	24 0.7,
Source: Systems Applications, Inc. 1980
TABLE D-72. EMISSIONS RATES AND NUMBER OF GENERAL
POINT SOURCES OF TRICHLOROETHYLENE
Open Top	Vapor	Conveyorized Vapor
Cold Cleaning Decreasing	(QTVO)	Oegreasinq (tVO)
Emissions/Site Number Emissions/Site Number	Emissions/Site Number
Region (gm/sec) of Sites (gm/sec)	of Sites	(gw/sec} of Si tes
Mew England
0.00952
2,991
0.288
560
0.357
113
Middle Atlantic
0.00952
7,750
0.288
1,158
0.357
244
East North Central
0.00952
13,179
0.288
1 .742
0.357
405
West North Central
0.00952
4,362
0.288
452
0.357
30
South Atlantic
0.(30952
6.005
0.288
465
0.857
84
East South Central
0.00952
2,944
0.280
255
0.357
52
West South Central
0.00952
4,032
0.288
398
0.857
68
Mountain
0.00952
1,806
0.288
174
0.857
21
Pact fic
0.0095?
5,893
0.288
396
0.857
155
Source: Systems Applications, Inc. 1980
311

-------
Storage and Transport:
Stored in cool dry pi aces, well-ventilated, away from sunlight
and heat. Shipped in 5 and 55 gal steel drums, tank cars and
tank trucks, barges -
Disposition:
60^ of world's annual production is released to environment
with most to the atmosphere. Disposal methods include:
Incineration
Aqueous waste
Waste solvent reclammation
Waste solvent landfills
Sampling and Analytical Methods
1.
Sampie
Type
Extraction/Clean-Up
Detection
Limit of
Detection
Air
Ambient
Ambient
Rural
Trap in Drechsel flask fitted
with rubber septum, sample with
gas syringe
Analyze directly
Trap on porous polymer, desorb,
by heating, retrap in line on
GC column
Atmosphere Analyze directly
Ambient Analyze directly
Ambient Analyze directly
GC/ECD 1 ug/m3
GC/ECD 10 mg/m3
GC/ECD;
GC/MS
GC/MS
Carbon
di oxi de
laser
Carbon
dioxide
1 aser
160 ng/m3
(30 ppt)
27 ng/m3
(5 ppt)
1.8 Mg/m3
(0.7 ppb)
23 ug/m3
(4.2 ppb)
Source: IARC 1979
312

-------
2.	NIOSH method S 336 for trichloroethylene
a.	Adsorption on charcoal
b.	Desorption with carbon disulfide
c.	Gas chromatographic analyses
Detection limits:
0.01 mg/0,5-22 1 of sample
Possible interferences:
High humidity (decreases breakthrough volume)
Two or more solvents present of different polarities
Two or more solvents present with same retention time
as trichloroethylene
3.	Methods B, C, or D from Appendix A
Cryogenic trapping or Tenax adsorption appear to be
the best approaches. GC/PID is a useful determinative
techoi que
Materials Damage
Trichloroethylene will attack the common metals, even in the
presence of moisture
Permissible Exposure Limits
OSHA
TWA 100 ppm
Cei1i ng 200 ppm
Peak 300 ppm/5 mi
in any 2 hrs
n
NIOSH
100 ppm
150 ppm/15 min
ACGIH
50 ppm (150 mg/nP)
150 ppm (805 mg/m3)
Human Toxicity
Acute toxicity:
Inhalation of 160 ppm (83 minutes) = TClq for central nervous
system effects
Chronic toxicity:
Carcinogenesis--testing to be completed in FY83 (U.S. DHHS
1983)
Mutagenicity--mutagenesis/genetic toxicity testing ongoing in
FY83 (U.S. DHHS 1983)
Teratogenicity--selected for reproductive/developmental
toxicity testing, date not determined
313

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Other chronic toxicity:
Kidney, spleen, and liver damage
Metabolic and enzymatic effects
Hypertensi on
Decreased ATP level
Reduces antibody formation
Bibliography
Battel 1e Columbus Laboratories, 1977a. Environmental Monitoring Hear Industrial
Sites: Trichloroethylene. EPA-560/6-77-024. Battelle Columbus Laboratories.
Columbus, OH.
Battelle Columbus Laboratories. 1977b. Multimedia Levels of Trichloroethylene.
EPA 560/6-77-029. Battelle Columbus Laboratories. Columbus, OH.
Blackwood, T.R., W.C. Micheletti, and J.C. Ochsner. 1979. Status Assessment of
Toxic Chemicals: Trichloroethylene. PB80-146426. Monsanto Research Corporation,
Dayton, OH; and Radian Corporation, Austin, TX.
CIayton, George D., and F1orence E. C1ayton, eds. Patty's Industrial Hygiene,
3rd Revised Edition, Vol. 2B. "Toxicology." John Wiley and Sons, New York,
W V, pp. 3553-60.
Ful1er, B., J. Hushon, M. Kornreich, R. Quellette, L. Thomas, and P. Walker.
1976. Preliminary Scoring of Selected Organic Air Pollutants. EPA-450/
3-77-008e. The Mitre Corporation. McLean, VA.
GEOMET Technologies, Inc. 1981. Chemical Summaries for NTP Second Annual Report
Carcinogens. Rockville, MD.
Hawley, Gessner G. 1977. The Condensed Chemical Dictionary, 9th ed..
Van Nostrand Reinhold Company, NY.
International Agency for Research on Cancer. 1979. IARC Monographs on the
Evaluation of the Carcinogenic Risk of Chemicals to Humans. Lyons, France.
Vol. 20.			
Katz, Moris, ed. 1977. Methods of Air Sampling and Analysis. A1pha Inter-
society Committee, American Public Health Association, Washington, DC.
Kirk-Gthmer. 1979. Encyclopedia of Chemical Technology, 3rd ed. John Wiley
and Sons, New York, NY. Vol. 5, pp. /4b-b3.
Mackison, Frank W., R. Scott Stricoff, and Lawrence J. Partridge, Jr., eds.
1978. MIOSH/OSHA Pocket Guide to Chemical Hazards. DHEW (MIOSH) Publication
No. 78-210. Washington, DC.
314

-------
Mason, Benjamin J., Douglas J. Pel ton, Ruth J. Petti, and David J. Schmidt. 1979.
Environmental Carcinogens and Human Cancer. GEOMET Report Number HF-803.
GEOMET, Incorporated, Gaithersburg, MD.
National Fire Protection Association. 1981. National Fire Codes, A Compilation
of NFPA Codes, Standards, Recommended Practices, and Manuals. Vol. 13. NFPA.
Quincy, MA.
Proctor, Nick W., and James P. Hughes. 1979. Chemical Hazards of the Workplace.
J.B. Lippincott Company, Philadelphia, PA.
Riggin, R.M. 1983. Technical Assistance Document for Sampling and Analysis
of Toxic Organic Compounds in Ambient Air\ EPA-600/4-83-027. Battel 1e
Columbus Laboratories. Columbus, OH.
Systems Applications, Inc. 1980. Human Exposure to Atmospheric Concentrations
of Selected Chemicals Vol II. PB81-193260. San Raphael, CA.
U.S. Department of Health, Education, and Welfare. 1973. Criteria for a
Recommended Standard	Occupational Exposure to Trichloroethylene. R3M
73-11025. National Institute for Occupational Safety and Health. Rockvi11e,
MD.
U.S. Department of Health, Education, and Welfare. 1978. Current Intel 1igence
Bulletin, Reprints—Bulletins 1 through 18. National Institute for Occupa-
tional Safety and Health. Rockvilie, MD.
U.S. Department of Health, Education, and Wei fare. 1977. National Insti tute for
Occupational Safety and Health Manual of Analytic Methods, Vol 1. DHTW
(MIOSH) Publ. Ho. 77-157-A. Cincinnati, OH.
U.S. Department of Health, Education, and Welfare. 1977. National Institute for
Occupational Safety and Health Manual of Analytic Methods, Vol 3. DHEW
(NIOSH) Publ. No. 77-157-A. Cincinnati, OH.
U.S. Department of Health and Human Services. 1983. National Toxicology
Program: Review of Current DHHS, DOE, and EPA Research Related to
To>icology. NTP-83-001. National Toxicology Program. Research Triangle
Park, NC.
U.S. Department of Labor. 1981. General Industry, OSHA Safety and Health
Standards (29CFR1910). Occupational Safety and Health Administration.
Washington, DC.
U.S. Department of Transportation. 1978. Chemical Hazards Response Informa-
tion System (CHRIS) Hazardous Chemical Data"! United States Coast Guard,
Washington, DC.
315

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Chemical Name
Vinyl chloride
CAS Number
75-01-4
Chemical Classification
Synonyms
Halogenated unsaturated hydrocarbon
Chlorethene, chlorethylene, chloroethene, chloroethylene, ethylene
monochloride, monochloroethene, monochlorethylene, Trovidur, VC,
VCM, vinyl chloride C monomer, vinyl chloride monomer
Physical/Chemical Properties
Description:
Colorless gas (pure substances)
Boiling point:
-13.37° C
Melting point*.
-153.8° C
Molecular weight:
62.5
Chemical formula:
C2H3CI
Vapor pressure:
2530 mm at 20® C
Refractive index:
20
nD 1.3700
316

-------
Solubi1ity:
Slightly soluble in water, 0.11/100 g at 25° C; soluble in
ethanol; very soluble in ether, carbon tetrachloride, and
benzene
Density:
0.9106 at 20° C {water at 4° C)
Vapor density:
2.2 (air « 1)
Photochemical reactivity:
Vinyl chloride undergoes atmospheric reactions in the presence
of nitrogen oxides and solar radiation. The reaction rate is
slower than other atmospheric hydrocarbons that have been
studied. Reaction products of vinyl chloride photo-oxidation
include carbon monoxide, formaldehyde, formic acid, formyl
chloride, and hydrogen chloride. The half-life of vinyl
chloride in laboratory experiments was reported as 6 hours.
No data were available on the half-life of vinyl chloride in
the ambient atmosphere
Chemical reactivity:
On treatment with strong alkalis at high temperatures, vinyl
chloride loses hydrogen chloride. Reacts with hydrogen
peroxide, oxides of nitrogen, sulfuric acid, and ozone in
ambient air
Environmental fate
Vinyl chloride should disappear significantly in its transport over
long distances; however, in the immediate vicinity of emission
sources, it is considered a stable pollutant. Vi nyl chloride is so
volatile that it does not bioaccumulate or transfer appreciably
through food chains. Vegetational damage around manufacturing or
processing plants has not been documented. The polyvinyl chloride
products made from vinyl chloride are not readily biodegradable
Sources of Emissions
Production:
The annual production of vinyl chloride in the United States
is approximately 7 bill ion lb. The total emissions from the
10 vi nyl chloride monomer production sites operated in 1975
were estimated to be 30 million 1b/yr, based on an emission
rate of 0.45 percent of production
317

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Byproduct sources;
Polyvinyl chloride plants use an estimated 95 percent of the
vinyl chloride produced. Vinyl chloride emissions in 1975
from U.S. polyvinyl chloride polymer pi ants were approximately
240 million lb. This figure represents extrapolated figures
based on estimated emissions of 4 percent vinyl chloride
during polymer production and recovery, and full capacity
operation. The location of vinyl chloride and polyvinyl
chloride plants is presented in Figure D-7
Maximum 24-hour air concentrations around plants ranged from
0.32 to 10.6 ppm. Fabrication plants produced lower vinyl
chloride emissions than production pi ants
NESHAP addressed vinyl chloride emissions from vinyl chloride
monomer production and polymerization. The imposed engineering
controls have been shown to reduce emissions by 95 percent
over precontrol levels
Uses:
The principal use of vinyl chloride is in the production of
vi nyl chloride homopolymer and copolymer piastics. The
remainder is used in the synthesis of several chemicals
Vinyl chloride was formerly used as a component of aerosol
propel!ants. This use was banned by EPA, FDA, and CPSC in
1975
Storage:
During bulk polymerization, intermittent storage losses of
vinyl chloride were reported as high as 20 percent. Intensive
maintenance is capable of reducing these sources of fugitive
emissions 50 to 75 percent
Transportati on:
Monomer loading and unloading are potential sources of inter-
mittent vinyl chloride emissions. Special controls have been
suggested, such as vapor collection adapters with recycling,
thermal level detectors with recycling, and magnetic gauges to
limit loading area losses
318

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C	*	>4 T ~ 5
¦W	»	>5
Figure 0-7. Location of vinyl chloride and polyvinyl chloride plants. EPA Regions are delineated
Source: Systems Applications„ Inc. 1980

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Disposition:
Limited data are available on the levels of vinyl chloride
emissions from the incineration of plastics. Emissions from
incineration are expected to vary as a function of temperatures
and types of plastic incinerated. The following are repre-
sentative:
Temperature (°C) 25-280 280-350 350-430 430-510
Emissions (mg/g) 0.04 0.25 0.17	0.02
Sampling and Analytical Methods
1. Method Number P&CAM 178 Matrix Air
a.	Adsorption on activated carbon
b.	Desorption with carbon disulfide
c.	Gas chromatographic detection
Detection limits:
The detection limit of the method was determined as
0.008 mg/m3 in a 5-liter air space sample. The minimum
detectable amount of vinyl chloride was 0.2 ng per
injection (1x1 attenuation on a gas chromatograph)
Possible interferences:
a.	High humidity decreases the adsorption capacity of
activated carbon
b.	Compounds with the same column retention time as
vinyl chloride will interference in determinations
Materials Damage
Vinyl chloride is an extremely volatile gas, and appropriate
precautions must be taken in handling this human carcinogen
Permissible Exposure Limits/Threshold Limit Values
0HSA
1 ppm 8 hour Time Weighted Average
5 ppm/15 minutes Time Weighted Average Ceiling
Toxicity
Acute toxicity:
Vinyl chloride is of low order acute toxicity. Produces
anesthetic effects accompanied by cardiac irregularities and
pulmonary edema
320

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Chronic toxicity:
Carcinogenicity—There is sufficient evidence that vinyl
chloride monomer is a human carcinogen. Its target organs are
the liver, brain, lung, blood and lymphatic systems
Mutagenicity—Vinyl chloride induces mutagenicity in short-
term cellular testing. Chromosomal aberrations were induced
in workers exposed to levels of 25 ppm. No chromosomal
aberrations were induced when exposure to vinyl chloride was
reduced to 15 ppm
Teratogen!city—Studies indicate increased rates of birth
defects among children residing in communities where vinyl
chloride production and polymerization plants are located.
Further investigation of its teratogenicity is needed
Other Chronic toxicity;
Low grade liver and kidney damage
Degeneration of finger bones associted with direct
physical contact with high levels of the monomer
Hypertension following chronic exposures
Circulatory system disturbances such as fibrosis in
arteries
Bibliography
Dimmick, W.F. 1981. EPA Programs of Vinyl Chloride Monitoring in Ambient
Air. Environmental Health Perspectives. Vo~Y7 41, pp. 203-206.	"
Fishbein, L. 1979. Potential Industrial Carcinogens and Mutagens. Elsevier
Scientific Publishing Co., pp. 165-81.
International Agency for Research on Cancer. 1979. IRAC Monographs on the
Evaluation of the Carcinogenic Risk of Chemicals to"TfuiaW$. Vol. 19,
pp. 377-437, Lyon, France.
International Agency for Research on Cancer, 1982. Supplement 4.
pp. 260-62, Lyon, France.
U.S. Department of Health, Education, and Welfare. 1977. NIGSH Manual of
Analytical Methods, Vol, 1. DHEW (NIOSH) Publication No. 77-157-A.
Cincinnati, ORT
U.S. Environmental Protection Agency. 1975. Scientific and Technical Assess-
went Report on Vinyl Chloride and Polyvinyl Chloride. EPA-600/6-75-C04,
Washington, DC.
321

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Verschueren, K. 1977. Handbook of Environmental Data on Organic Chemicals.
Van Nostrand Reinhold Company, New York, NY, pp.
Wi ndholz, M., et al. 1983. The Merck Index. 10th ed. Merck £ Co., Inc.,
Rahway, NJ.
322

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Chemical Name
Vinylidene chloride
CAS Number
75-38-4
Chemical Classification
Vinyl balide
Synonyms
1,1-Dichloroethene; 1,1-dichloroethyl ene; 1,1-DCE; VDC
Physical/Chemical Proterties
Description:
Highly volatile, clear liquid
Boiling point:
32° C
Melting point:
-122.1° C
Molecular weight:
97.0
Chemical formula:
C2 H2 CI 2
Vapor pressure:
400 mm at 14.8° C
Refractive index:
Op0 1.424
Solubility:
Insoluble in water (0,4% wt/vol at 20° C)
Photochemical reactivity:
Photooxidizes rapidly
323

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Vapor density:
3.4 (air = 1)
Chemical reactivity:
Easily polymerized at temperatures above 0° C
Environmental Fate
VDC emissions to the atmosphere are estimated to be shortlived.
The half life is in the order of several hours -
Sources of Emissions
Product!on/Process:
Domestic production was reported as 386,000,000 lb by
Five producers in two regions (public record, TSCA Inventory}
The fol1owing companies reported production to EPA in 1977:
	Producer	
Dow Chemical Co,
PPG Industries, Inc.
Continental Oil Co.
Location
Freeport, TX
Plaquemine, LA
lake Charles, LA
West Lake, LA
VDC emission losses during production are in the range of
1.2 to 3.1 g/kg produced
Most of the VDC emissions are process losses. Estimated
annual emissions from processing are presented in Table D-73.
New control technologies since 1974 have probably reduced
the total emissions
Uses:
VDC has two main commercial uses: the production of
1,1,1-trichloroethane and the synthesis of various polymers
used in food packaging; coatings; resins, latexes; films
and extruded fibers. There are scant data available on
the migration of VDC monomer from products
Storage/transport:
Storage, transfer and filling operations have been esti-
mated to account for about 25% of the total environment
VDC emissions
324

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TABLE 0-73. ESTIMATED ANNUAL EMISSIONS OF VIMYLIDENE CHLORIDE (VDC)
IN THE U.S. IN MONOMER AND POLYMER SYNTHESIS AND
POLYMER PROCESSING (1974)

Annua! VDC Emissions
VCC
Conjunction
" of Total
U»S. Emissions
Process
1000 kj
1000 lbs
Monomer Synthesis
15232
33S52

82.8
Polymer Synthesis
308
679
112
16.7
- Latex for Barrier Coatings
55
120
20

- Latex for Miscellaneous Coating
683
ISO3
15

- Synthetic Fibers
733
160
16

- Coating Resin for Cellophane
82
1824
25

- SLxtnision Resin (Emulsion Process}
12
27 5
21

- Extrusion Resin {Suspension Process)
18
4Q6
15

Fabrication or Polymer Processing
13.?
30.4

0.7
- Coating Cellophane
0.7
1.6


- Coating Plastics, Paper & Glasslne
7.3
16.4


- Extrusion
0.2
0.4


- Miscellaneous Coating
5.S3
12.03


Total
1345,0
4C54.0 |
• 100.0
1 This VCC emission inventory does not Include amissions of VDC from the conversion of
Yinyl Ider.e chloride into 1,1,1 -tri cn'i or oe thane.
2	New emission-control technology will be Installed 1n one of the plants during the latter
part of 197S. On this basis, the annual VDC missions should drop to 511 ,000 lbs
(277,000 kg).
3	While all emissions listed 1n this table are estimates, the degres of certainty varies.
V These estimates are based on minimal data and are, therefore, more uncertain,
4	These products result 1n vinyl chloride missions. The annual Missions are TSCO lbs,
5	These products result in vinyl chloride emissions. The annual Missions are 105,120 lbs.
or 47,700 kg.
6	These products result In vinyl chloride missions* The annual emissions are 43,435 lbs.
or 19,700 kg.
Source: Arthur D, Little 1976
325

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Disposition:
VDC (primarily in polymerized form) is disposed of in
landfills. No data are available on emissions from this
source
Sampling and Analytical Methods
NIOSH Method number PSCAM 266
Sampl i rig:
A known volume of air is drawn through a charcoal tube
to trap the VDC present
Analysis:
An aliquot of the sample desorbed with carbon disulfide
is analyzed by gas chromatography
Detection limits:
The lowest quantifiable limit was determined as 7 ug of
VDC per sample
Possible interferences:
1.	Stability of sample
2.	Humidity
3.	Presence of other substances in the sample with
the same column retention times as VDC
Threshold limit Values
U.S. TLV 10 ppm {40 mg/m3)
Human Toxicity
Chronic Toxicity:
Carcinogenicity—The available epidemiological studies do not
permit an assessment of human carcinogenicity. VDC does
produce malignant tumors in experimental animals
Mutagenic!" ty--YPC is mutagenic in S. typhi murium and E. col i;
no data are available for humans
Teratogenicity--Fetotoxicity and embryotoxicity have been
demonstrated in animals; no adequate data for humans
326

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Other chronic toxicity:
Additional biochemical cellular, tissue effects and
pulmonary toxicity testing is to be started in FY83
(National Heart, Lung, and Blood Institute)
Bibliography
Fishbei n, L. 1979. Potential Industrial Carcinogens and Mutagens. Elsevier
Scientific Publishing Company. New York, NY. pp. 178-81.
International Agency for Research on Cancer. 1978. 1ARC Monographs on the
Carcinogenic Risk of Chemicals to Humans. Lyon, France, Vol. 19,
pp. 438-55.
Little, Arthur D. 1976. Vinylidene Chloride Monomer Emissions from Monomer,
Polymer Processing Industries. U.S. EPA, EPA 68-02-1332. Durham, NC.
Mason, B.J., et al . 1979. Environmental Carcinogens and Human Cancer.
Summary Information on Selecte"d~13Ti"emfca1 CarcinogeTisT GEOMET, Incorporated,
Gaithersburg, MD, pp. 506-24.
Neufeld, M.L., et al. 1977. Market Input/Output Studies—Task 1--Vinylidene
Chloride. U.S. EPA, EPA-560/6-77-033, Washington, DC.
U.S. Department of Heath, Education, and Welfare. 1978. 1978. Current
Intel ligenee Bulletin No. 28. Vinyl Hal ides Carcinogenicity. WCT7WS/NI0SH.
Publication No. 79-102, Cincinnati, OH.
U.S. Department of Health. Education, and Welfare. 1977. NIOSH Manual of
Analytical Methods. DHHS/PHS/NIOSH, Vol. 4, 266.
U.S. Environmental Protection Agency. 1980. Office of Pesticides and Toxic
Substances, Chemical Information Division.
327

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TECHNICAL REPORT DATA
•fPlcate rmd /ftxaziesorts on ;ke reverie before totrwietinfj
. =ie?GHT MO.
a.
3. RECIPIENT'S ACCESSiQf»NC.
t- 7tTL = ANO SU8TITLS
Network Design and Site Exposure Criteria for Selected
"loneriteria Air Pollutants
$. RETORT OATS
January 31, 1984
«. PERFORMING ORGANIZE TICN CCDS
81-01-044-04
\ AUTHORISE
R.C. Koch, M.B. Charlton, D.J. Pel ton, and H.R. Stern
S. P8KPORMING 0RGANIZA7TCN MG.
GE0MET Report No. ESF-1257
. 3£3POflMIMG ORGANIZATION NAME AMD AQOflSSS
GEOHET Technologies, Inc.
1801 Research Boulevard
Rockville, Maryland 20850
1 Ol fWOGRAM SLi.MENT NO.
11. CONTRACT, G«AN 7 NO,
Contract No. 68-02-3584
•2, SPONSORING AGENCY NAME A HQ AQCR6SS
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina
13. TYPE OF REPORT ANO PSSIOO COV8R £0
14,, SPONSORING AGENCY C006
S, SUPPLEMENTARY MOTES
6. ABSTRACT
9
Procedures for selecting air monitoring sites are provided and discussed, A significant
amount of information regarding 43 selected noncriterla pollutants is also presented.
The document is a useful guideline for systematically setting priorities, identifying
siting areas, and selecting specific sites that wi11 meet the data needs for air monitoring
responsibilities. The characteristics of each of the selected noncriteria pollutants
are presented, including physical properties, sources of emissions, emission estimates,
sampling and analysis methods, and toxicity. The siting procedures deal with a range of
representative spatial scales varying from less than 100 m to SO km.
7.	KEY WORDS AND COCSJMENT ANALYSIS
okschiptors
b.ioe.NTipiERs/opeN ended terms
c COS ATI F:eM/Group
Air Monitoring Siting Guide
Noncriteria Air Pollutants
Toxic Air Pollutants
Hazardous Air Pollutants



8. QISTRiaUTlON STATEMENT

If. SECURITY CLASS (Thu Rtportj
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5 1
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