October 1977
HUMAN EXPOSURES TO ATMOSPHERIC BENZENE
By. SUSAN J.MARA
SHONH S. LEE
Prepared for:
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF RESEARCH AND DEVELOPMENT
WASHINGTON, D.C. 20460
Project Officer: ALAN P. CARLIN
Technical Monitor: RICHARD J. JOHNSON
CONTRACT 68-01-4314
CENTER FOR RESOURCE AND ENVIRONMENTAL SYSTEMS STUDIES
Report No. 30
STANFORD RESEARCH INSTITUTE
Menlo Park, California 94025 • U.S.A.
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STANFORD RESEARCH INSTITUTE
October 1977
HUMAN EXPOSURES TO ATMOSPHERIC BENZENE
By: SUSAN J. MARA
SHONH S. LEE
Prepared for:
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF RESEARCH AND DEVELOPMENT
WASHINGTON, D.C. 20460
Project Officer: ALAN P. CARLIN
Technical Monitor: RICHARD J. JOHNSON
CONTRACT 68-01-431 4
SRI Project EGU-5794
CENTER FOR RESOURCE AND ENVIRONMENTAL SYSTEMS STUDIES
Report No. 30
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NOTICE
This is a preliminary draft. It has been released by the U.S.
Environmental Protection Agency (EPA) for public review and comment and
does not necessarily reflect Agency policy. This report was provided
to EPA by SRI International, Menlo Park, CA, in fulfillment of contract
No. 68-01-4314. The contents of this report are reproduced herein as
received by SRI after comments by EPA. The opinions, findings, and
conclusions expressed are those of the authors and not necessarily those
of EPA. Mention of company or product names is not to be considered as
an endorsement by the EPA.
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CONTENTS
LIST OF ILLUSTRATIONS v
LIST OF TABLES vii
PREFACE ; ix
ACKNOWLEDGMENTS xi
I SUMMARY 1
II BENZENE IN THE ENVIRONMENT 5
A. Introduction 5
B. Chemical and Physical Properties of Benzene 8
III CHEMICAL MANUFACTURING FACILITIES 13
A. Sources 13
B. Methodology 19
C. Exposures 26
IV COKE OVENS 29
A. Sources 29
B. Methodology and Exposures 31
V GASOLINE SERVICE STATIONS 39
A. Sources 39
B. Methodology and Exposures 41
VI PETROLEUM REFINERIES 53
A. Sources 53
B. Methodology 54
C. Exposures 59
VII SOLVENT OPERATIONS 63
A. Sources 63
B. Methodology and Exposure 65
ill
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VIII STORAGE AND DISTRIBUTION OF BENZENE AND GASOLINE 77
A. Sources 77
B. Methodology and Exposures 77
IX URBAN EXPOSURES RELATED TO AUTOMOBILE EMISSIONS 85
A. Sources 85
B. Methodology and Exposures 86
BIBLIOGRAPHY 95
APPENDICES
A DIAGRAMS OF VARIOUS BENZENE-RELATED OPERATIONS . . . 101
B EMISSION RATES AND POPULATION EXPOSURES
FROM CHEMICAL MANUFACTURING FACILITIES 113
C POPULATION EXPOSURES FROM COKE OVEN OPERATIONS
BY LOCATION 121
D POPULATION EXPOSURES FROM PETROLEUM REFINERIES
BY LOCATION 127
iv
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ILLUSTRATIONS
III-l Benzene Derivatives and Their Uses 17
II1-2 Dispersion Modeling Results for Each Type
of Source Category 23
IV-1 Dispersion Modeling Results for Coke Oven
Operations 35
VI-1 Monitoring Data for Gulf Alliance Refinery,
Belle Chasse, Louisiana 55
VI-2 Dispersion Modeling Results for Three Size Categories
of Petroleum Refineries 58
VII-1 Sampling Data for Three Solvent Operations 66
VIII-1 The Gasoline Marketing Distribution System
in the United States 81
VIII-2 Vapor and Liquid Flow in a Typical Bulk Terminal .... 82
IX-1 Isopleths (m/sec) of Mean Annual Wind Speed
Through the Morning Mixing Layer 88
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TABLES
I- 1 Summary of Human Exposures to Atmospheric
Benzene from Emission Sources 3
I- 2 Comparison of Benzene Exposures Among Sources 4
II- 1 Estimated Benzene Levels in Food 8
II- 2 Properties of Benzene 10
III- 1 Locations and Capacities of Plants Using
Benzene as an Intermediary Agent in the
Manufacture of Various Chemical Compounds 14
III- 2 Emission Factors and Characterizations for
Benzene-Consumption Plants 18
III- 3 Rough Estimates of Ambient Ground-Level
Benzene Concentrations (8-hour Average) 20
III- 4 Rough Estimates of Ambient Ground-Level
Benzene Concentrations (8-hour Average) per 100 g/s
Emission Rate 21
III- 5 Estimates of 8-hour Worst Case Benzene Concentrations
Based on Average of Three Emission Source Categories . . 22
III- 6 Population Exposed to Benzene from Chemical
Manufacturing Facilities by State 27
IV- 1 Estimated Size and Productive Capacity of By--Product
Coke Plants in the United States on December 31, 1975 . . 30
IV- 2 Ambient Levels of Benzene Within a Coal-Derived
Benzene Production Plant 31
IV- 3 Atmospheric Benzene Emission from the Coking and
Recovery Plants in Czechoslovakia 32
IV- 4 Rough Estimates of 8-hour Worst Case Benzene
Concentrations per 100 g/s Emission Rate Using
the PAL Dispersion Model 34
IV- 5 Estimated Population Exposed to Benzene from
Coke Ovens 38
V- 1 Typical Liquid Volume Percent of Benzene in
Gulf U.S. Gasolines, October 1976 39
V- 2 Benzene Concentration in Different Grades and
Seasonal Blends of Gasoline 40
V- 3 Self-Service Operations 42
vii
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V- 4 Gasoline Market Share of Self-Service Stations
in Four AQCRs, Spring 1977 43
V- 5 Gasoline Market Share of Self-Service Stations
in Two Metropolitan Areas, 1976 , , . . . 44
V- 6 Sampling Data from Self-Service Gasoline Pumping . , . . 45
V- 7 Rough Dispersion Modeling Results for Gasoline
Service Station 48
V- 8 Service Station Density in Four Metropolitan Areas ... 49
V- 9 Summary of Population Exposed to Benzene from
Gasoline Service Stations 51
VI- 1 Petroleum Refineries Producing Aromatics, by State ... 54
VI- 2 Calculation of Emission Factors for
Petroleum Refineries 57
VI- 3 Estimated Population Exposed to Benzene from
Petroleum Refineries by State 61
VII- 1 Industries and Manufactured Products Possibly
Using Benzene as a Solvent 65
VII- 2 Average Number of Employees per Plant for
Selected Solvent Operations 68
VII- 3 Number of Plants and Employees for Solvent
Operations with High Potential for Benzene Emissions . . 69
VII- 4 Estimated Average Annual Benzene Concentrations
in the Vicinity of an Average Size Solvent
Operation in Rubber-Related Manufacture 71
VII- 5 States with the Highest Potential for Atmospheric
Benzene from Solvent Operations 72
VII- 6 Estimated Potential Population Exposures from
Solvent Operations in Rubber-Related Manufacturing ... 74
IX- 1 Estimates of Annual Average Benzene Concentrations
in Four Urban Areas 87
IX- 2 Estimates of Average Annual Benzene Concentrations
for Cities with Populations Exceeding 1,000,000 .... 90
IX- 3 Estimates of Average Annual Benzene Concentrations
for Selected SMSAs 92
IX- 4 Urban Exposures Related to Automotive Emissions 93
vlii
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PREFACE
There is substantial evidence that concentrations of benzene en-
countered in the workplace (both in the United States and elsewhere) have
caused blood and bone marrow diseases (e.g., blood dyscrasia, pancytopenia)
and leukemia (especially myelogenous leukemia). As current U.S. Environ-
mental Protection Agency (EPA) policy states that there is no zero risk
level for carcinogens, benzene has been listed by EPA under Section 112
of the Clean Air Act as a hazardous air pollutant. To determine what
regulatory action should be taken by EPA on atmospheric emissions of
benzene, three reports have been prepared: (1) a health effects assess-
ment, (2) a population exposure assessment, and (3) a risk assessment
document based on the data in the first two assessments. This document
is the human population exposure assessment and presents estimates of the
numbers of people in the general population of the United States exposed
to atmospheric concentrations of benzene from specific sources.
ix
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ACKNOWLEDGMENTS
It is a pleasure to acknowledge the cooperation and guidance given
by several individuals of the U.S. Environmental Protection Agency.
Dr. Alan Carlin, Office of Research and Development, was project officer.
Mr. Richard J. Johnson, Office of Air Quality Planning and Standards,
Strategies and Air Standards Division, generously provided data and
direction throughout the study. Messrs. Philip L. Youngblood and
George J. Schewe (Office of Air Quality Planning and Standards, Monitoring
and Data Analysis Division) conducted dispersion modeling, offered
guidance about the application of their results, and reviewed draft
documents.
Mr. Benjamin E. Suta, SRI project leader, gave vital support and
provided useful input throughout the study. Mr. Michael Smith patiently
edited the study. Ms. L. H. Wu and Ms. Grace Y. Tsai were responsible
for all graphics.
xi
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I SUMMARY
This report is one in a series that SRI International is conducting
on a quick-response basis for the U.S. Environmental Protection Agency
(EPA). Populations at-risk to selected pollutants are being quantified
for input to other, more inclusive studies. This study was undertaken
to quantify the environmental exposure of the general population to
atmospheric benzene emissions.
Although recent reports have identified benzene in water, food,
and soil in some locations, the available data do not indicate that
widespread exposures occur from these environmental pathways. There-
fore, the main exposure pathway considered in this report is air. The
seven primary sources of atmospheric benzene emissions are chemical
manufacturing plants, coke ovens, gasoline service stations, petroleum
refineries, solvent operations, storage and distribution of benzene
and gasoline, and urban exposures related to automobile emissions.
The quantitative nature of this study has necessitated reliance
on very limited data. When data were available, source locations were
identified and benzene emission rates were calculated. Atmospheric
environmental concentrations of benzene were then estimated by applying
approximate, dispersion modeling results developed by EPA. Population
exposed to concentrations of 0.1 ppb (the detection limit of current
sampling techniques) and greater were estimated. When data were uavail-
able, best estimates were developed to provide a reasonable basis for
comparison.
All estimates given in the report are subject to considerable
uncertainty as to: 1) the quantity of benzene emissions, (2) benzene
production and consumption levels, (3) source locations, (4) control
technologies employed, (5) deterioration of control technologies over
time and, (6) the physical parameters (e.g., stack height) of benzene
sources. As a result, the accuracy of the modeling results could not
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be assessed quantitatively. Nevertheless, the estimates, although not
precise, do provide an approximate estimate of expected conditions.
Because of averaging techniques, the summary results for each source
category are expected to be well within 1 order of magnitude.
Table 1-1 summarizes results of the study. Urban exposures
and exposures from gasoline service stations constitute the two larg-
est sources. Coke ovens are third with more than 16 million people ex-
posed over a wide range of exposure levels. Chemical manufacturing
plants and petroleum refineries are sources of benzene exposures
for more than 5 million people.
For comparative purposes, Table 1-2 lists each source. For ap-
proximate comparison of different emission sources, exposures are
calculated in similar units by multiplying the number of exposed popu-
lation by the annual average benzene concentration within each range.
These values were then summed for each emission source. Thus, the
units become ppb-person-years. For self-service gasoline exposures
the exposure time was 1.5 hr/person/year; the units became ppb-
person-hours and were then divided by the number of hours per year
to determine ppb-person-years.
The results presented in Table 1-2 show that urban exposures
and gasoline service stations have the highest weighted human expos-
ures. Next are chemical manufacturing plants, followed by coke ovens.
These results differ from Table 1-1 because they are weighted by the
number of people exposed to a particular level of atmospheric benzene.
Thus, they provide a more useful basis for comparison.
As indicated above, the estimates given in this report are sub-
ject to considerable uncertainty; they thus require further monitoring
and sampling data for a more complete assessment. Despite the insuffi-
ciency of data, however, the fact remains that the population exposed
is substantial. Potential health effects from the estimated exposures
will be addressed in another report being prepared by the EPA Cancer
Assessment Group.
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Table 1-1
SUMMARY OF HUMAN EXPOSURES TO ATMOSPHERIC BENZENE FROM EMISSION SOURCES
Chemical
Q
Population Exposed to Benzene Concentrations (ppb)
8-hour Worst Case: 1 Q _ 1Q Q
Annual Average: 0.1 - 1.0
Source
manufacturing
Coke ovens
Gasoline
service stations
1. People using self-
service
2. People living in the
vicinity
Petroleum refineries
Solvent operations6
Storage and distribution
Urban exposures
7,497,000
15,726,000
87,000,000
6,529,000
208,000
f
68, 337,00.0
10.1 - 20.0
1.1 - 2.0
970,000
521,000
31,000,000
64,000
5,000
45,353,000
20.1 - 40.0
2.1 - 4.0
453,000
50,000
4,000
2,000
40.1 - 100.0
4.1 - 10.0
644,000
2,000
d
d
>100.0
>10.0
319,000
c
Totalb
Exposed
Population
9,883,000
16,299,000
37,000,000
118,000,000
6,597,000
215,000
113,690,000
u>
Source: SRI estimates
*To convert to ug/m , multiply each exposure level by 3.2.
^Population estimates are not additive vertically, because some double-counting may exist.
Estimated at 245 ppb for 1.5 hr/yr/person.
'T.ess than 500 people exposed.
eExact determination is impossible. This represents a crude population estimate (see Chapter VII).
fEstimated at «0.1 ppb annual average. The population exposed was not determined but is assumed to be very small.
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Table 1-2
COMPARISON OF BENZENE EXPOSURES AMONG SOURCES
(10° ppb-person-years)
Source Exposure
Chemical manufacturing 15.9
Coke ovens 8.8
Gasoline service stations
1. People using self-service 1.6
2. People living in the vicinity 90.0
Petroleum refineries 3.4
Solvent operations 0.1
Storage and distribution *
Urban exposures from automobile 102.2
emissions
* Minimal
Source: SRI estimates
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II BENZENE IN THE ENVIRONMENT
A. Introduction
The primary objective of this study was to quantify the environ-
mental atmospheric exposure of the general human population to benzene
emissions.
This is one in a series of studies being conducted by SRI for the
U.S. Environmental Protection Agency (EPA) to quantify populations at-
risk to selected pollutants. These studies are generally conducted on
a quick-response basis to provide input to other, more inclusive studies.
The procedure used here was to identify sources of benzene emissions,
to estimate atmospheric environmental concentrations of benzene re-
sulting from these sources, and to estimate human populations exposed
to various levels of benzene concentrations. This study has not con-
sidered the degree of biological sorption of material. No attempt was
required or has been made in this input report to assess potential
health effects.
Atmospheric sources of benzene are widespread and include natural
sources such as forest fires and man-made sources such as automobile
emissions. Although benzene is not sampled regularly in any air qual-
ity monitoring program, some sampling data do exist. EPA has also
conducted dispersion modeling that is applicable to most of the major
sources. On the other hand, sample data of benzene concentrations in
water, food, and soil are sparse, and those measurements that have been
taken have been infrequent and inconsistent. Therefore, because infor-
mation on other environmental pathways is generally lacking, only atmos-
pheric sources are evaluated in this report.
Benzene is commercially produced mainly by petrochemical operations
(92%) and on a much smaller level as a coke-oven by-product (8%). Total
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r 6
benzene production in 1976 was approximately 7500 x 10 Ib (3400 x 10 kg)
(SRI estimates). Benzene is used primarily as an additive in gasoline,
in chemical manufacturing processes, and in solvent operations. Of all
benzene used in chemical and solvent operations, more than 97% is used
in chemical processing (SRI estimates).
For this report, seven sources of atmospheric benzene were evaluated:
chemical manufacturing plants, coke ovens, gasoline service stations,
petroleum refineries, solvent operations, storage and distribution
of benzene and gasoline, and urban exposures related to automobile
emissions. These sources have been identified as the major sources of
atmospheric benzene (PEDCo, 1977; Johnson, 1977). Although oil spills
and discharges represent a potentially significant source of benzene
in the environment, the most significant of these occur in remote loca-
tions or along coastal areas where population density is low, and the
benzene released to the atmosphere from each occurrence is very small.
Potential human exposure to atmospheric benzene from these sources
is negligible.
It is not within the scope of this study to evaluate human expos-
ures to benzene from water, food, or other environmental pathways.
However, it is useful to review the available data to provide some
basis for comparison.
Only limited data on benzene in water are available. A review of
benzene sampling data by Howard and Durkin (1974) found that the few
freshwater samples analyzed by that time showed only trace levels of
benzene. For example, a 1972 EPA study cited in the report identified
53 organic chemicals, ranging from acetone to toluene, in the finished
waters and organic waste effluents in 11 plants (of 60 sampled) dis-
charging into the Mississippi River. Benzene was not detected in the
effluents, but the trace detected in the finished waters suggested
another source than effluent discharge.
A recent sampling of five benzene production or consumption plants
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by Battelle (1977) found benzene levels in water ranging from <1.0 to
179 ppb in one plant's effluent. The concentrations at 13 upstream
and downstream sample locations in nearby receiving waters, however,
ranged from <1.0 to 13.0 ppb, with an average of 4.0 ppb.
A recent report by the National Cancer Institute (1977) noted
benzene levels of 0.1 to 0.3 ppb in four U.S. city drinking water
supplies. One measurement from a groundwater well in Jacksonville,
Florida showed levels higher than 100 ppb. No indication is given
in the report of the sampling methods or the analytical procedures.
However, study of the behavior of benzene in the groundwater system
and in the drinking water supply system is clearly warranted.
One possible source of benzene in the aquatic environment is from
cyclings between the atmosphere and water (Mitre, 1976). Benzene is
fairly volatile(high vapor pressure of 100 mmHg at 26°C) and has a rela-
*
tively high solubility (1780 mg/L at 25°C). Consequently, it is
reasonable to believe that benzene will be washed out of the atmos-
phere with rainfall and then evaporated back into the atmosphere,
causing a continuous recycling between the two media.
The distribution of benzene in the aquatic system is not well-
known. Needy et al. (1974) demonstrated a relationship between octanol-
water partition coefficients and bioaccumulation potential in fish.
The partition coefficient for benzene which is estimated to be very
low, suggests that the bioaccumulation potential in fish is minimal.
Benzene uptake by aquatic vegetation has not been studied.
Only one study of benzene levels in soil has been conducted.
Battelle (1977) sampled soils in the vicinity of five benzene consump-
tion or production facilities. Their preliminary results from 14
samples showed levels ranging from <1.0 to 191.0 ppb, with an average
of 53.0 ppb. In most cases, the highest levels of benzene were found
in samples taken closest to the plant. These results indicate that the
* L = liter.
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potential for accumulation of benzene in the soil is significant.
Human exposure to benzene in food is not addressed in this report.
We note, however, the following information: those few available data
that quantify benzene levels in food (Chinn, personal communication,
1977) indicate that it occurs naturally in fruits, fish, vegetables,
nuts, dairy products, beverages, and eggs. However, data on concen-
trations are only available for cooked meat, rum, and eggs (see
Table II-l). A report by the National Cancer Institute (1977) estimated
that an individual could ingest as many as 250 yg/day from these foods.
Table II-l
ESTIMATED BENZENE LEVELS IN- FOOD
(pg/kg)
Heat treated or canned beef 2
Jamaican rum 120
Irradiated beef 19
Eggs 2100
Source; National Cancer Institute (1977)
The quantitative nature of this study has necessitated reliance
on very limited data. All estimates given in the report are subject
to a large degree of uncertainty related to: quantity of benzene
emissions, benzene production and consumption level, source locations,
control technology employed, deterioration of control technology over
time, and dispersion modeling. Because monitoring data are insuffi-
cient, no quantitative assessment could be made of the accuracy of the
modeling results. Consequently, although the estimates are not pre-
cise, they do provide a reasonable evaluation of expected conditions.
And, because of averaging techniques, the summary results for each
source category are expected to be well within 1 order of magnitude.
B. Chemical and Physical Properties of Benzene
Benzene, CgHg, is a nonpolar, nonreactive, highly refractive cyclic
aromatic hydrocarbon. In benzene, the C-C bond is 1.39 A long and
8
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the CH bond is 1.08 A long(Ayers, 1964; MacKenzie, 1962). Under stan-
dard conditions, benzene is a clear, noncorrosive, colorless, and
highly flammable liquid. Benzene possesses a characteristic odor,
similar to that of gasoline. It is relatively soluble in water and
is miscible with acetone, alcohol, chloroform, ether, carbon disul-
phide, carbon tetrachloride, glacial acetic acid, and oils. Pertinent
physical properties of benzene are listed in Table II-2.
Benzene is quite thermodynamically stable because the resonance
energy of its unsaturated bonds is due to the interaction of the six ir
electrons that form "doughnut11 shaped electron orbitals above and
below the plane of the ring.
Benzene solubility in water at 25°C is 1800 ppm (0.18 mg/g water).
Variation of benzene solubility in water from 1730 to 1800 ppm has been
noted (McAuliffe, 1963). The difference is believed to be attributable
either to the temperature of the experiment or the precision of the
technique. Both salting-in and salting-out (increase or decrease in
solubility) phenomena have been observed for benzene in aqueous solu-
tion (Giacomelli, 1972). Benzene solubility in salt water and dis-
tilled water have been compared, and the results show that solubility
decreases as the salt content of water increases (Sutton, 1974). A
similar decrease in solubility of the water soluble fraction
(including benzene) from crude oil was observed (Lee, 1974). These
observations reveal that benzene is less soluble in salt water than
in fresh water. The vapor pressure of benzene is an important
property in assessing the benzene contamination in the gaseous phase.
The vapor pressure of 100 mmHg at 26°C indicates that benzene exists
environmentally only in the gaseous and the aqueous phases.
Benzene is highly stable. Consequently, chemical reactivity is
limited unless the reactions take place under certain extreme conditions
(and in the presence of the necessary reagents). When chemical re-
actions do take place, benzene behaves primarily as a nucleophilic
agent, usually with substitution of individual hydrogen atoms rather
than addition. The two most common substitutive reactions are
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Table II-2
PROPERTIES OF BENZENE
Constant
Freezing point, °C
Boiling point, °C
Density, at 25°C, g/mL
Vapor pressure at 26.075°C, mm Hg
Refractive index, n25
Viscosity (absolute) at 20°C, cP
Surface tension at 25°C, dyn/cm
Critical temperature °C
Critical pressure, atm
Critical density, g/mL
Flash point (closed cup), °C
Ignition temperature in air, °C
Flammability limits in air, vol%
Heat of fusion, kcal/mole
Heat of vaporization at 80.100°C, kcal/mole
Heat of combustion at constant pressure and
25°C (liquid C^ to liquid H20 and
gaseous CO-), kcal/g
Solubility in water at 25°C, g/100 g water
Solubility of water in benzene at 25C, g/100 g
benzene
Value
5.553
80.100
0.8737
100
1.49792
0.6468
28.18
289.45
48.6
0.300
-11.1
538
1.5-8.0
2.351
8.090
9.999
0.180
0.05
Source: Ayers and Muder (1964).
10
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nitration and sulfonation. In additive reactions, other reactive
chemical agents are added to the unsaturated bonds. Three types
of additive reactions are most common: oxidation, hydrogenation,
and halogenation.
The general environmental fate of benzene can be assessed by
examining the degradation processes of oxidation, hydrolysis, photolysis,
and microbial decomposition. Hydrolysis and, microbial decomposition
occur primarily in the aqueous phase, whereas oxidation and photolysis
can occur in both the aqueous and the gaseous phases.
Benzene can be oxidized to a number of different products in the
presence of catalysts or at elevated temperatures and pressures.
Under extreme conditions, benzene has been observed to oxidize com-
pletely to water and carbon dioxide. In the environment, such extreme
conditions rarely exist. Thus, it can be concluded that degradation
of benzene by oxidation is probably negligible. Oxidation in the
emission pathways from chemical plants and refineries is conceivable,
but no such observations have been reported.
The benzene ring does not undergo reaction with water or hydroxyl
ions (OH ) unless substituted with a significant number of strong
electronegative groups, or at elevated temperature and pressure.
Thus, hydrolysis in the environment is assumed to be minimal.
Several studies have investigated the wavelength absorption
properties of benzene. No appreciable amounts of light at wavelength
O
longer than 280 nm (2800A) were directly absorbed by benzene dissolved
in cyclohexane. A slight shift, however, in wavelength absorption
would be more representative of environmental media, such as dissolution
in water or absorbtion on particular matter. Chien (1965) reported the
ultraviolet absorption spectra of liquid benzene in the presence of
oxygen under 1 atmosphere. Noyes et al. (1966) found that gaseous
benzene only absorbs light at 275 nm or less. Because the atmospheric
ozone layer effectively filters out wavelengths less than 290 nm, it
appears that direct excitative photolytic reaction of benzene in
11
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the environment is unlikely, unless a substantial wavelength shift
occurs in the presence of other media. Indirect excitation of benzene
may be possible in the presence of certain sensitizers in the water
or soil.
Photolysis by light with a wavelength of less than 290 nm of ben-
zene in the vapor phase and in oxygenated aqueous solution has been
reported. Two types of products, 2-formyl-4H-pyran and cyclopentadiene-
carboxaldehyde result (Luria, 1970; Kaplan et al., 1971). Matsuura
and Omura (1974) have reviewed several investigations where atomic
oxygen that had been photochemically generated from various sources
reacted with benzene to form phenol. Atomic oxygen is generated, for
instance, from the photodecomposition with nitrogen dioxide, which is
frequently found in high concentration in heavily polluted air
(Altshuller, 1971). Laboratory results conclude that benzene is not
completely inert under smog conditions (Laity et al., 1973; Stephens,
1973).
The microbial degradation of benzene has received some attention
in recent years and it is conceivable that biodegradation of benzene
probably occurs under environmental conditions. Benzene has been
found to biodegrade in a waste treatment plant, with the rate of
degradation determined by the incubation period and acclimation of the
microorganisms. It is safe to conclude, therefore, that benzene can
be degraded—but at a very slow rate.
In summary, oxidation and hydrolysis of benzene in the environment
are unlikely. Photolysis is possible in the natural environment, but
the photolysis rate depends on wavelength adsorption and the presence
of sensitizers. In a heavily polluted atmosphere, atomic oxygen
may cause photochemical decomposition of benzene. Biodegradation of
benzene in the environment is also possible, but the degradation
rate is quite slow.
12
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Ill CHEMICAL MANUFACTURING FACILITIES
A. Sources
In this section, generation of benzene emissions from the manufacturing
of chemical compounds will be addressed. Producer companies of various com-
pounds (excluding solvents) are listed in Table III-l; their locations and
1976 capacity productions are also included in the table. The Gulf Coast
has the highest density of these benzene-consumption facilities.
Benzene is used commercially as an intermediate agent in the production
of many chemical compounds. The emissions of benzene from such industrial
uses are potentially significant sources of atmospheric benzene. Total U.S.
consumption of benzene in 1975 was 108.4 x 10 gal (4.1 x 10 m )
(Anderson, 1976). Figure III-l illustrates the benzene derivatives and their
uses. Primary use involves the manufacture of such chemicals as nitro-
benzene, ethylbenzene, maleic anhydride, cumene, phenol, chlorobenzene, cyclo-
hexane, and detergent alkylate. Appendix A contains flow diagrams for some
of these processes.
To assess the ambient benzene concentrations in the vicinity of chemical
manufacturing facilities, two factors must be estimated: benzene emission
rates at each location; and atmospheric dispersion of benzene in the vicinity
of the plants. The emission rates can be estimated if the emission factors
and total production are available. Table III-2 gives the emission factors
used in the analysis and emission characterization. The emission factors
were selected to represent averages. Because little is known about benzene
emissions from chemical manufacturing facilities, these emission factors
are considered order-of-magnitude estimates. Maleic anhydride and aniline
have the highest emission factors related to the specific manufacturing
processes and reaction kinetics of each compound.
13
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Table II1-1
LOCATIONS AND CAPACITIES OF PLANTS USING BENZENE AS AN INTERMEDIARY
AGENT IN THE MANUFACTURE OF VARIOUS CHEMICAL COMPOUNDS*
STATE
ALABAMA
CALIFORNIA
DELAWARE
GEORGIA
ILLINOIS
KANSAS
KENTUCKY
LOUISIANA
LOCATION
TUSCAIOOSA
CARSON
EL SEGUNOO
RWINOALE
RICHMOND
SANTA FE SPRINGS
DELAWARE CITY
CARTERSVILLE
BLUE ISLAND
CICERO
MORRIS
SAUGET
EL DORADO
ASHLAND
BATON ROUGE
COMPANY
REICHHOLD CHEM.. INC.
WITCO CHEM.
STO. OIL CO. OF CALIF.
SPECIALTY OHGANICS. INC.
STO. OIL CO. OF CALIF.
FERHO CORP.
STD. CHLORINE CHGM CO.. INC.
CHtM. PRODUCTS CORP
CLARK OIL ft REFINING
KOH-F-HS CO.. INC.
REICHHOLD CHEM.. INC.
MONSANTO
SKEULY OIL CO.
ASHLAND OIL. INC.
FOSTER GRANT CO.
CORVILLE COSJUAR. INC.
CHALMETTE TCNNECO. INC.
GEISMAR RUBICON CHEM.. INC.
FLAOUEMINI GECHir.lA PACIFIC CORP.
MARYLAND
WELCOME
GULF OIL COUP.
BALTIMORE CONTINENTAL OIL CO.
MASSACHUSETTS MALOEN
MICHIGAN
MISSISSIPPI
MISSOURI
NEVADA
SOLVENT CHEM. CO.. INC.
MIDLAND DOW CHEMICAL
PASCAGOULA FIRST MISSISSIPPI CORP.
ST. LOUIS MONSANTO
HENDERSON MONTROSE CHEM.CORP. OF CM..
NEW JERSEY BOUND BROOK
BOUND BROOK
AMERICAN CYANAMID
UNION CARBIDE
ELIZABETH REICHHOLO CHEM.. INC.
FORDS TENNECO. INC
GIBBSTOWN
C. 1. do PONT
KEARNY STD. CHLORINE CHEM. CO.
WESTVILLE TEXACO. INC.
CAPACITY PRODUCTION JANUARY 1. I97B ImMliont ol h?)
NITRO-
BENZENE
5
34
B1
3B
91
ANILINE
25
45
27
99
ETHVL-
9EN2ENE
440
327
12
2SO
290
STYRENE
372
272
738
IB2
MALEIC
ANHYDRATE
.5
27
4B
14
12
CUMENE
49
SO
91
ISO
4.9
119
PHENOL
SB
2S
N.A.
40
U
120
11
9B
MONO.
CHLOHO-
BENZENE
34
52
N.A.
m
u
OICHLOP.O.
BENZENE
Id- and P-l
1
IT"
101
13
CYCLO-
HEXANE
DETERGENT
ALKYLATE
lUnttr
•nd Bnnch)
IS
t«
29
f
100
99
-------
Table 111-1 (Continued}
STATE
MEW YOflK
OHIO
PENNSYLVANIA
PUERTO RICO
TEXAS
LOCATION
NIAGARA FALLS
NIAGARA FALLS
NIAGARA FALLS
SYRACUSE
HAVERHILL
BE AVER VALLEY
enmoEviLLE
CLA1KTON
FKANKFOMD
NEVILLE ISLAND
PHILADELPHIA
GUAYAM*
PENUELAS
PENUELAS
BAYTOWN
BFAUMOHT
BEAUMONT
BIG SPRING
BORDER
CHOCOL»TE BAYOU
CORPUS CHRISTI
COH?US CHniSTI
conpus CHRISTI
FREEPOHT
HOUSTON
HOUSTON
HOUSTON
HOUSTON
HOUSTON
ODESSA
OYSTER CHEEK
PHILLIPS
PORT ARTHUR
PORT ABTHUH
PORT ARTHUR
SEADRIFT
SWEENEY
COMPANY
icc INDUSTRIES. INC.
OCCIOCNTflL PtTROCEUM
SOLVENT CHEM. CO.
ALLIED CHtM. CORP.
UNITED SfATES STEEL
ARCOJPOLYMERS. INC.
KOWEHS CO.. INC.
UNITED STATES STEEL
ALLIED CHEMICAL CORP.
UNITfLD STATES STCtL
GULF OIL COHI".
PHILLIPS PHTROLEUU
COMf.W)NWIrALTH OIL
UNION CAHBIOE CORP
EXXON COHP
E. 1. du PONT
UNION OIL CO. OF CALIFORNIA
AMERICAN PETROFIHA
PHILLIPS PETROLEUM
MONSANTO
COASTAL STATES GAS
SUN OIL CO.
UNION PACITICCORP
DOW CHEMICAL
ARCO/POLYMERS. INC.
THE CHARTER CO.
JOE OIL. INC.
THE MfltlCHEM CO.
PETRO-rEX CHEM COflP.
EL PASO NATURAL CAS
OOW CHEMICAL
PHILLIPS W-TROLEUM CO.
ABCO/POIYMERS. INC.
GULF OIL conr
TEXACO
UNION CARBIDE CORP
PHILLIPS PETROLEUM CO.
CAPACITY PRODUCTION JANUARY 1. 10T6 Cmif
NITRO-
BENZENE
ANILINE
]
:
141
81
ETHYL-
BENZENE
73
20
43
i
1
1
!
1
B48
45
16
tn
300
IS5
STYfiENE
300
41
36
649
4S
«B
136
MALE 1C
ANHYORATC
IS
IB
CUMENE
PHENOt
i
90
j
1
i
».*.
290
!
205
]
29O 90
i
|
2*5
M
114
MI
;
HJk,
»
3OS
118
187
ioni of kgl
MOMO-
BEN7ENE
N.A.
' 7
N.A.
WCHiOflO-
*O- »WKf P-)
M.A.
9
HEX AWE
11 »
... -_^_
\
i
l
r
98
XB
lie
lie
too
3S
118
Gfi
xa
251
DETERGENT
ALKVLATE
-------
Table ltl-1 (Concluded)
STATE
TEXAS
WEST VIRGINIA
WASHINGTON
LOCATION
TEXAS CITY
TEXAS CITY
TEXAS CITY
CHARLESTON
FOU.ANSBEE
MOUNDSVILLE
NATRIUM
NEW MARTINSVILLE
WILLOW ISLAND
ANACURTES
KALAMA
COMPANY
MARATHON OIL CO.
WONSANTO
STANDARD OIL (INDIANA)
UNION CARBIDE CORP
HOPPERS CO.. INC.
ALLIED CHEM COP P.
PPG INDUSTRIES. INC.
MOUAY CHcM CORP.
AMERICAN CYANAMIDE
STIM3O* LUMtiFFI CO.
KALAMA CHEMICAL
TOTAL
CAPACITY PRODUCTION JANUARY 1. 1976 ImiWont ol kgt
NlTRO
BENZENE
ANN FNE
a
si
11
03
4S
12
314
ETHYL-
BENZENE
USD1
4X
3BH
STVRENE
590
387
3J11
MALEIC
ANHYDRATE1
CUWENE
86
»
"
.....
)•
17»
PHENOL
N.A.
n
12»
MONO
CMLOHO-
BENZENE
N.A.
41
313
DICHLORO-
BENZENE
4O- Bnd P-t
23
130
CYCLO-
HEXANE
770B
DETERGENT
ALKVLATE
n
303
SOURCE: SRI. 1>7Q DIRECTORY Of CHEMICAL PRODUCERS. • dnd In PEDCO. 1*77
liLA. - NOT AVAILABLE
•. PRODUCTION CAPACITY FOR O-DICHLOROBCNZENE ONLY
b. PRODUCTION CAPACITY FOR P-OICHLOROBENZENE ONLY
c. ItTB DATA SHOWED COMBINED ESTIMATES OF ETHYLBENZENE PflODUCTION AT CHOCOLATE BAYOU. TEXAS AND AT TEXAS CITV. TEXAS.
1977 SRI ESTIMATES SHOW ETHYUCNZENE PRODUCTION ONLY AT THE TEXAS CITY PLANT.
-------
^\
ETHYL \ / CYCLO-
MALEIC
ANHY-
DRIDE
CHLORO-
BENZENE
LUBE
OIL
THANES ADDITIVES
ALKLO. VPOLYESTE
RESINS A RESINS
PHENOLIC V SURFAC
MOLDINGS I FIBERS
RESINS A TANTS
LAMINATES! ADHEStVES I COATINGS I MOLDINGS 1 FIBERS I LAMINATES I ADHESIVESI MOLDINGS I COATINGS
SOURCE: MEDLEY. 1975
FIGURE IH-1. BENZENE DERIVATIVES AND THEIR USES
-------
Table II1-2
EMISSION FACTORS AND CHARACTERIZATIONS
FOR BENZENE-CONSUMPTION PLANTS
Chemical
Aniline
Cumene
a
Cyclohexane
Q
Detergent Alkylate
(linear and branched)
Dichlorobenzene
(p- and o-)b
Ethylbenzene
Maleic anhydride
Monochlorobenzene
Nitrobenzene
Phenolb
Styrene
Emission Factor
(10~3 kg Of benzene/kg
of product)
23.60
0.25
2.80
2.20
8.60
0.62
96.70
3.50
7.00
1.00
1.50
Emission
Characterization
Fugitive
Fugitive
Fugitive
Fugitive
Chlorinator, PDCD
recovery system
Scrubber-vent
Product recovery
scrubber
Unknown
Point absorber
Unknown
Collection vent,
emergency vent
a
SRI estimates
3PEDCo estimates
18
-------
A
The atmospheric dispersion of benzene is more difficult to assess.
Simply, source characteristics (e.g., stack dimensions) and meteorological
conditions greatly influence the dispersion of benzene in the vicinity
of the plants. Youngblood (1977a) made rough dispersion estimates from
very limited data on source characteristics. He classified the processes
according to three source categories: A—ground-level point source
(effective stack height, 0 m); B—building source (effective stack height,
10 m); and C—elevated point source (effective stack height, 20 m).
Emission rates were then calculated for each process by assuming a maximum
production rate. Ambient ground-level concentrations were derived manually
from Turner's workbook. One-hour worst-case concentrations were derived
with the following meteorological conditions assumed: wind speed, 4 m/s;
stability class, neutral (Pasquill Gifford "D"). For source category B,
the results from Turner's workbook were adjusted to account for the
initial dispersion of the pollutant in the building cavity. The one-hour
estimates were then converted to 8-hour worst-case estimates (by multi-
plying by 0.5). The results of the dispersion modeling by Youngblood are
given in Table III-3.
B. Methodology
Each chemical manufacturing plant has different production rates,
chemical processes, geographic locations, pollution control technology,
and meteorological conditions. Thus, detailed dispersion calculations
are impractical, given the scope of the study. A simple method of
assessment was therefore developed to allow for comparative analysis.
Variations in geographic locations and meteorological conditions were not
considered in the analysis. The results are not precise; rather, they
provide a reasonable order-of-magnitude estimate of atmospheric benzene
concentrations. A single dispersion curve was constructed and applied
to all chemical manufacturing facilities, based on their emission rates.
The derivation of this methodology is discussed below.
Battelle-Columbus has monitored benzene concentrations in the vicinity
of chemical manufacturing facilities. These data are now in draft form
and should be available in the near future.
19
-------
Table III-3
ROUGH ESTIMATES OF AMBIENT GROUND-LEVEL BENZENE CONCENTRATIONS (8-HOUR AVERAGE)'
to
O
Source
Maleic anhydride
Styrene
Phenol from cumene
Benzene
Cumene
Phenol from benzene
Nitrobenzene
Ethyl benzene
Phenol from toluene
Chlorobenzene
o- dichlorobenzene
p-dichlorobenzene
Emission
Rate
(K/s)
139.0
7.49
10.8
0.179
2.34
0.0691
31.20
16.60
2.42
15.10
3.60
6.20
Concentration (yg/m )
Source
Category
C
A
B
C
A
B
A
B
A
B
C
A
B
C
A
B
A
B
A
B
C
A
B
C
A
B
C
150 m
700
3800
850
54
90
20
1200
260
35
8
<1
16000
3500
160
8500
1900
1200
270
7700
1700
76
1800
400
18
3200
700
31
300 m
5000
1100
460
390
26
11
340
140
10
4
2
4500
1900
1100
2400
1000
350
150
2200
940
540
500
220
130
900
380
220
450 ra
5000
530
290
390
13
7
170
91
5
3
2
2200
1200
1100
1200
650
170
94
1100
590
540
250
140
130
440
240
220
at Given Distance
600 m
3900
330
210
300
8
5
100
66
3
2
2
1400
870
870
730
460
110
68
660
420
420
160
100
100
270
180
170
750 m
2900
220
160
230
5
4
70
49
2
1
1
940
650
650
500
350
73
51
453
320
320
110
75
75
190
130
130
1600 m
1100
68
55
89
2
1
21
17
1
<1
<1
280
230
250
150
120
21
17
140
110
120
32
26
28
39
46
49
This is a worst-case estimate. It may be multiplied by 0.1 to give rough estimates of annual-average concentrations.
Key to Source Categories: A—Ground-level point source; B—Building source; C—Elevated point source.
Sourqe: Youngblood, 1977a.
-------
Table III-4
ROUGH ESTIMATES OF AMBIENT GROUND-LEVEL BENZENE CONCENTRATIONS
(8-HOUR-AVERAGE)* PER 100 g/s EMISSION RATE
Source
Category
0.15
km
A 51 , 000
B 11,000
C 510
Concentrations
0.3
km
14,000
6,100
3,500
0.45
km
7,000
3,800
3,500
0.6
km
4,500
2,800
2,800
0.75
km
3,000
2,100
2,100
(yg/m )
1.6
km
900
740
800
2.5
km
440
370
410
4.0
km
220
220
220
6.0
km
120
120
120
9.0
km
62
62
62
14.0
km
34
34
34
20.0
km
20
20
20
To give rough estimates of annual-average concentration, multiply by 0.1.
Source: Youngblood (1977b).
-------
As shown in Table III-3, ambient benzene concentrations in the vicinity
of chemical manufacturing plants vary significantly in relation to the char-
acteristics of the emission sources. Exhaust gas temperature, which is
important in determining near-source concentrations, was not considered.
Because of the generally high concentrations estimated at 1.6 km,
Youngblood (1977b) extended his model calculations to a distance of 20 km
with an emission rate of 100 g/s for each source category (see Table III-4).
The results of Youngblood's analysis are shown in Figure III-2. The
ground-level (A) and building (B) sources are highest near the plant and
decrease rapidly with distance. The elevated point source (C), however,
shows low initial concentrations that increase to a peak followed by a
decline. Although the differences due to source category are considerable
at 150 m, the differences decrease rapidly with distance. Even as close
as 300 m, the differences are within the range of uncertainty normally
associated with dispersion calculations. In addition, distances less than
300 m are likely to be within the plant perimeter or to have low population
densities. A single dispersion curve (Curve M in Figure III-2) was there-
fore developed to represent all three source categories, as suggested by
Youngblood (1977b). This curve was derived by averaging the high and low
values of the three emission source categories at each calculated distance.
The resulting concentrations estimated by this method are shown in Table
III-5.
Table III-5
ESTIMATES OF 8-HOUR WORST CASE* BENZENE CONCENTRATIONS
BASED ON AVEPAGE OF THREE EMISSION SOURCE CATEGORIES
O ££
Distance (km) Concentration (yg/m )
0.30 8800
0.45 5200
0.6 3600
0.75 2600
1.6 820
2.5 400
4.0 220
6.0 120
9.0 62
14.0 34
20.0 20
To convert to annual average estimates, multiply concentrations by 0.1.
**
To convert to ppb, divide concentrations by 3.2.
Source: Youngblood (1977b).
22
-------
10'
10'
I
o
LU
O
z
L1J
I
10'
10
\ \
- I
I
I C
A . GROUND LEVEL SOURCE
B - BUILDING SOURCE
C - ELEVATED SOURCE
M • AVERAGE OF CURVES A, B, AND C
0.1 1.0 10 100
DISTANCE FROM SOURCE - km
'Based on an emission rate of 100 g/s
Source: After Youngblood, (1977b)
FIGURE III-2. DISPERSION MODELING RESULTS FOR EACH TYPE OF SOURCE CATEGORY*
23
-------
Regression analysis was used to develop an equation to characterize
the single dispersion curve (Curve M) . Equation (3.1) was derived from
that analysis:
C = 1648 D""1'48 (3.1)
3
where, C is the 8-hour worst-case benzene concentration in yg/m , and
D is the distance from the source in km. Because equation (3.1) is only
valid for an emission rate of 100 g/s, a normalized equation is given as
follows :
C = 16.48 E D'1'48 (3.2)
3.
where, E , in g/s, is the emission rate for the location of interest.
3.
The annual average concentration can be estimated by including a
multiplier of 0.1 in the equation. Thus, the equation becomes:
C = 1.648 E D'1'48 (3.3)
3
In this study, the ranges of benzene concentrations that follow and
that apply to all sources have been established for the sake of uniformity:
0.1 - 1.0 ppb
1.1 - 2.0 ppb
2.1 - 4.0 ppb
4.1 - 10.0 ppb
>10.0 ppb
A computer program was developed to estimate the people exposed to
concentrations within each range at each location. Equation (3.3) was
rearranged as follows to determine the distance at which the specified
concentrations are found:
0.6757
where, C. is the specified concentration (i.e. ,0.1, 1.0, 2.0, and so on;
1 3
input data, however, are in yg/m ); D is the distance at which the
specified concentration is found; and E is the emission rate at that
cl
location.
24
-------
The population residing within a circle of radius D. was then
estimated by the following equation:
P± = d TT DI (3.5)
where, d is the city or state population density, and P. is the population
exposed to concentration C. or greater.
The three main assumptions included in this analysis are:
The benzene source is in the center of the city
The maximum allowable radius is 20 km
When a city has more than one plant, it is assumed that
these plants are co-located and their corresponding
emission rates are summed.
To accommodate these assumptions the following steps were included in the
computer program. The radius of each city was determined by Equation
(3.6):
/ r \ ±f *-
(3.6)
where, D is the estimated radius of the city; P is the population of
the city (1970 Bureau of Census data) ; and d is the average city density
(1970 Bureau of Census data available for cities of population greater
than 25,000).
When D calculated from Equation (3.4) is greater than D , or when
no city density is available, Equation (3.7) is substituted for Equation
(3.5) to calculate the exposed population on the basis of state density.
P± = Pc + dg TT (D* - D£) (3.7)
where, d is average state population density; D. is the distance at which
S li
concentrations C. is found; D is the radius of the city calculated in
Equation (3.6); and P is the population exposed to concentration C. or
greater. P and D equal 0 when no city density is available.
Because the dispersion modeling results are unverified at distances
greater than 20 km from the source location, the computer program automat-
ically cut off calculations when a distance of 20 km was attained and
calculated the concentration (C.) at 20 km.
25
-------
The cumulative population totals resulting were then automatically
subtracted, so that the total population within each range of concentra-
tions was printed out. For example, for range 0.1 to 1.0 ppb, the program
subtracted P. n (a smaller number) from Pn .. (a larger number). In other
X * U U • -L
words, Pn .. is the population exposed to concentrations of 0.1 ppb or
\J • -L
greater. P.. _ is the total population exposed to concentrations of 1.0
X • U
ppb or greater. By subtracting the two values, the total population exposed
to concentrations between 0.1 and 1.0 ppb is determined.
Emission rates were estimated for each plant, based on the production
estimates contained in Table III-l and the emission factors in Table III-2.
Because actual production data are unobtainable, capacity production and
24-hour (365 days) operation were assumed. Appendix B, Table B-l, lists
the estimated emission rates for each chemical manufacturing facility.
C. Exposures
Ambient benzene concentrations and the exposed population for each
source location were estimated, based on the methodology described above.
Table B-2 in Appendix B presents the results of this analysis.
The population were obtained from density data derived from the 1970
census (U.S. Department of Commerce, Bureau of the Census, 1972 County
and City Data Book). When the population density for a city was unavailable,
the average statewide population density was used, even though population
density in the vicinity of chemical manufacturing plants can vary widely.
However, the methods employed here provide a reasonable overall estimate
of the exposed population. Table III-6 presents the estimated population
exposed to specified levels of atmospheric benzene for each state. More
than 9 million people are exposed to annual average benzene concentrations
of 0.1 ppb or greater.
26
-------
Table III-6
POPULATION EXPOSED TO BENZENE
FROM CHEMICAL MANUFACTURING FACILITIES BY STATE
Population Exposed to Benzene (ppb)
State
Alabama
California
Delaware
Georgia
Illinois
Kansas
Kentucky
Louisiana
Maryland
Massachusetts
Michigan
Mississippi
Missouri
Nevada
New Jersey
New York
Ohio
Pennsylvania
Puerto Rico
Texas
West Virginia
Washington
Total Exposed
Population
0.1-1.0
62,700
104,600
76,200
10,900
204,000
11,800
26,800
166,600
800,400
18,300
65,400
21,000
4,400
18,000
1,523,400
263,600
11,400
1,986,900
805,500
1,169,200
144,200
1,200
7,496,500
1.1-2.0
2,000
16,500
2,200
700
27,600
400
1,500
106,900
46,500
500
6,200
18,600
17,400
1,000
110,200
21,600
300
141,400
25,000
406,600
16,400
100
969,600
2.1-4.0
800
6,500
1,300
300
39,400
200
600
41,800
18,200
200
21,500
7,300
6,800
400
43,100
8,500
100
55,300
10,000
182,700
7,700
100
452,800
4.1-10.0
400
3,000
800
100
31,700
100
300
19,400
8,300
100
10,100
3,300
348,600
200
84,500
3,900
100
27,800
4,500
93,600
3,500
t
644,300
>10.0
100
1,200
300
100
15,500
t
100
8,400
3,400
t
4,100
1,400
190,200
100
38,700
1,600
t
12,700
1,900
38,200
1,400
t
319,400
To convert to yg/m , multiply by 3.2; to convert to
8-hour worst case, multiply by 10.
Fewer than 50 people exposed.
Source: SRI estimates.
27
-------
IV COKE-OVENS
A. Sources
In 1975, 57.2 x 10 tons of coke were produced in the United States.
The yield of coke from coal, averaging 68.4% in 1975, has remained
fairly constant during the past decade (Sheridan, 1976). Coke is pro-
duced by 65 plants in the United States (Suta, 1977). The 65 plants,
which are listed in Appendix C» consist of an estimated 231 coke-oven
batteries containing 13,324 ovens. Their theoretical maximum annual
productive capacity is 74.3 x 10 tons. Table IV-1 shows the esti-
mated size and productive capacity in each state.
Although coke-ovens producing benzene as a by-product account for
only about 5 to 8% of the total benzene production in the United
States, they are a potentially significant source of benzene emissions.
About 0.66% by volume benzene, 0.13% toluene, 0.05% xylene, and less
than 0.10% of other aromatics have been identified in the coal gas
generated from coking operations (Faith, 1966). The higher the tem-
peratures in coking operations, the larger the amounts of aromatic
hydrocarbons produced, particularly benzene. Reduction in quantities
of paraffinic naphthenic (saturated alicyclic) and unsaturated hydro-
carbons in the production is observed at high temperatures (Faith,
1966; McGannon, 1970). Carbonizing 1 ton of coal in coke-ovens to
produce blast furnace coke yields 3 to 4 gallons of light oil. The
principal constituent of this oil is benzene, which comprises about
60 to 80% of the total composition. This crude light oil is then dis-
tilled to produce benzene, toluene, and xylene. The typical amount
of benzene recovered from coke-oven gas is 1.85 gal/ton of coal
carbonized (U.S. Public Health Service, 1970).
The distillation of coal tar is one additional source of benzene
production. The amount of benzene produced varies with the coking and •
recovery processes and the grade of the raw coal. In general, the light
29
-------
Table IV-1
ESTIMATED SIZE AND PRODUCTIVE CAPACITY OF BY-PRODUCT COKE PLANTS
IN THE UNITED STATES ON DECEMBER 31, 1975
Number of Number of Number of
State Plants * Batteries Ovens
Alabama 7 28 1,401
California 1 7 315
Colorado 1 4 206
Illinois 4 9 424
Indiana 6 (7) 31 2,108
Kentucky 1 2 146
Maryland 1 12 758
Michigan 3 10 561
Minnesota 2 5 200
Missouri 1 3 93
New York 3 10 648
Ohio 12 35 1,795
Pennsylvania 12 (13) 51 3,391
Tennessee 1 2 44
Texas 2 3 140
Utah 1 4 252
West Virginia 3 (4) 13 742
Wisconsin 1 2 100
Undistributed - - -
Total 62 (65) 231 13,324
Included in Undistributed.
* 3 plants are co-located.
Source: Sheridan (1976).
Maximum Annual
Theoretical
Productive
Capacity (tons)
6,961,000
1,547,000
1,261,000
2,523,000
11,925,000
1,050,000
3,857,000
3,774,000
784,000
257,000
4,053,000
9,960,000
18,836,000
216,000
839,000
1,300,000
4,878,000
245,000
74,266,000
Coke
Production
in 1974
(tons)
5,122,000
1,912,000
9,073,000
3,259,000
!59,l
C1)
C1)
8,842,000
16,318,000
C1)
C1)
3,555,000
12.656.000
60,737,000
-------
Table IV-2
AMBIENT LEVELS OF BENZENE WITHIN A COAL-DERIVED
BENZENE PRODUCTION PLANT
Occupation
Agitator operator
Benzene loader and
loader helper
Benzene still operator
Light oil still
operator
Naphthalene operator
Analyst
Chemical observer
Foreman
8-hour
Time- weighted
averaqe
(pprO
6.0
4.0
4.0
2.5
10
10
10
1.5
Range
(ppm)
0.5
0.5
1
1
2
4
4
1
- 20
- 15
- 15
- 15
- 30
- 30
- 50
- 10
Source: Bethlehem Steel Corporation data (NIOSH, 1974).
31
-------
oil distilled from coal tar is added to the major portion of light oil
recovered from coal gas and refined for its benzene content.
The basic coke-oven sources of air pollutant emissions include
charging and topside emissions, emissions from doors during the coking
cycle, waste gas stack emissions, pushing emissions, and quenching
emissions. Appendix A contains a diagram of a typical coke-oven operation.
The only ambient benzene concentration data available are occupational
exposure data. Table IV-2 gives the typical ambient benzene concen-
tration ranges per occupation, within a coal-derived benzene recovery
plant (NIOSH, 1974). Measurements of benzene in Czechoslovakia
coke-oven plants are tabulated in Table IV-3. In the recovery plant,
3
the benzene concentration can reach as high as 145 mg/m .
Data on benzene concentration in the vicinity of coke-oven and
benzene recovery plants are unavailable. In coke-oven operations,
the charging of coal is regarded as the potentially largest source
of benzene emissions.
Table IV-3
ATMOSPHERIC BENZENE EMISSION FROM THE COKING AND
RECOVERY PLANTS IN CZECHOSLOVAKIA
Benzene Concentration
3
Areas ug/m
3
Coke-oven battery 50. - 13 x 10
3
Recovery plant 50. - 145 x 10
2
Tar processing 3 x 10
Source: Maskek (1972).
B. Methodology and Exposures
To estimate the at-risk population to benzene from coke-oven emissions,
the number of people residing around the coke-oven plants and the ambient
32
-------
benzene concentration must be determined. The general methodology
discussed in Chapter III was used as the basis for determining exposure
levels from coke-ovens. Variations in geographic locations, meteorologic
conditions and control technology were not considered in the analysis.
*
Crude dispersion modeling was conducted by Youngblood of EPA (1977c).
Coke oven operations usually cover a large area and benzene emissions are
distributed widely throughout. Consequently, the point source model
used by Youngblood to estimate downwind concentrations resulting from
chemical manufacturing emissions is not applicable. To account for the
emissions distributed over a large area, Youngblood used the PAL (Point,
Area, and Line Source) Dispersion Model (Turner et al., 1975) that results
in lower ambient impact for a given emission rate. The benzene emissions
were assumed to occur primarily from oven leaks. The model assumptions
were as follows: square plant area; uniform distribution of emissions
throughout the area; effective stack height, 10 m; wind speed, 4 m/s;
stability class, neutral (Pasquill Gifford "D"). Maximum, one-hour-average
concentrations at selected downwind distances for a given emission rate
of 100 g/s were obtained from PAL. These were divided by two to represent
maximum eight-hour-averages. These are shown Table IV-4.
The plant size most applicable to coke-oven operations is 0.25 km2
(500 m on a side). The curve corresponding to this plant size is shown
in Figure IV-1. An equation was developed through regression analysis
to characterize this curve:
-0 Ql
C = 403 D U'*-L (4.1)
where C is the 8-hour worst case benzene concentration in yg/m3; and
D is the distance from the source in km.
'{
In this report, "crude" is used to mean approximate and extrapolatable.
33
-------
Table IV-4
ROUGH ESTIMATES OF 8-HOUR WORST CASE BENZENE
CONCENTRATIONS PER 100 g/s EMISSION RATE
USING THE PAL DISPERSION MODEL
Distance
from
Source
Area
(km)
0.3
0.45
0.60
0.75
1.6
2.5
4.0
6.0
9.0
14.0
20.0
0.01 km2
5,000
3,850
2,850
2,150
800
405
205
110
60
33
20
3 *
(Concentration pg/m ) for Given Plant Area
.06 km2 0.25 km2 1 km2 4 km2 9 km2
2,000
1,700
1,450
1,250
600
360
190
110
60
32
20
900
750
650
595
390
270
165
100
55
32
19
365
325
290
260
190
150
110
80
50
29
18
145
130
120
110
85
70
50
45
34
23
16
80
75
70
65
50
43
35
29
23
18
13
25 km2
39
37
34
33
27
23
20
17
14
11
9
To give rough estimates of annual-average concentrations multiply by 0.1;
To convert to ppb, divide concentrations by 3.2.
Source: Youngblood (1977c).
-------
1000
n
4
01
u
o
u
N
Z
UJ
ffi
100
10
T 1 I I I I I |
T 1 I I I I U
i
i
i t i i i i
i
I
i i i i i i
0.1 1.0 10
DISTANCE FROM SOURCE - km
* Based on an emission rate of 100g/s
Source: After Youngbtood (1977c)
FIGURE IV-1. DISPERSION MODELING RESULTS FOR COKE OVEN OPERATIONS*
100
-------
Equation (4.1) was then normalized to annual average conditions
and to individual emission rates (the Youngblood model was based on an
emission rate of 100 g/s):
C = 0.4 E D~°'91 (4.2)
3.
To estimate the number of people exposed to benzene concentrations
within each range at each location, Equation (4.2) is rearranged as
follows to determine the distance at which the specified concentrations
are found:
x..10
E
D. = 0.36 ,
\ C±
(4.3)
where C, is the specified concentration (i.e., 0.1, 1.0, 2.0, and so
^ o
on; input data, however are in u^./m ); and D± is the distance at which
the specified concentration is found.
Detailed population estimates for as far as 15 km from each location
were available from an on-going SRI study (Suta, 1977). Consequently,
once distances (D.) were determined, the population exposed to benzene
concentrations within each range was easily determined. Geographic
coordinates for most of the coke plants were obtained from the U.S.
EPA-NEDS data system. The remainder were obtained from consulting
maps or by telephone conversation. The population residing within a
15-km radius about each coke plant was calculated by use of the Urban
Decisions Systems, Inc., Area Scan Report. This computer data system
contains the 1970 census data in the smallest area available (city
blocks and census enumeration districts).
Emission rates for each coke-oven operation were estimated by
basing them on the capacity and the emission factor of 0.09 Ib benzene/
ton of coal obtained from EPA document AP-42 (EPA, 1976). Because
actual production data are unobtainable, capacity production and 24-
* Estimated by multiplying the hydrocarbon emission factor (6.9 Ib/ton
of coal) by the fraction of benzene in the total hydrocarbon emissions
(0.0132).
36
-------
hour (365 days) operation were assumed. Appendix C lists the estimated
emission rates for each coke-oven operation. Exact plant locations
are unknown. Thus, when more than one operation is found within one
city, these plants were assumed to be co-located and their corresponding
emission rates were summed. Because no background benzene concentrations
are available, the emissions of benzene from the coke plants were assumed
to be the sole contributors of benzene to the atmosphere in the vicinity
of the oven.
Table IV-5 summarizes people exposed to various annual average
benzene concentrations by state. More than 500,000 people are exposed
to annual average concentrations greater than 1.1 ppb (8-hr worst case
concentration greater than 10.1). Pennsylvania has the highest number
of exposed population, followed by Ohio and Michigan.
37
-------
Table IV-5
ESTIMATED POPULATION EXPOSED TO
BENZENE FROM COKE OVENS
Population Exposed
State
Alabama
California
Colorado
Illinois
Indiana
Kentucky
Maryland
Michigan
Minnesota
Missouri
New York
Ohio
Pennsylvania
Tennessee
Texas
Utah
West Virginia
Wisconsin
0.1 - 1.0
822,700
222,300
0
616,300
2,074,500
50,600
579,900
2,957,000
77,900
36,600
994,100
3,378,800
3,413,600
6,700
5,900
104,100
117,100
267,400
1.1 - 2.0
23,900
1,400
800
48,600
600
36,100
20,900
116,600
251,300
21,000
2.1 - 4.0 4.1 - 10.0 >10.0
200
19,400 t
100
3,100
4,400
22,600 2,400
t
t
Total 15,725,500 521,2QQ 49,800 2,400
Total exposed population = 16,298,900
* Totals are rounded; a zero indicates that a coke oven(s) is present,
but exposure levels are below o.l ppt>.
** To convert to 8-hr worst case, multiply concentration by 10; to
convert to yg/m^, multiply by 3.2
+ Fewer than 50 people exposed.
tt Because of averaging techniques and the population data base used,
some ranges of concentation show no exposed population.
Source: SRI estimates
38
-------
V GASOLINE SERVICE STATIONS
A. Sources
Gasoline contains varying amounts of benzene depending, among other
things, on lead content and refinery source. Before 1974, the average
benzene content in U.S. gasoline was less than 1% by liquid volume (Runion,
1975). Recent data (Runion, 1976) indicate that the average benzene
content has been increased to maintain octane levels while reducing lead
content. Current estimates of average benzene content in gasoline range
from 1.24 to 2.5% by liquid volume (PEDCo, 1977). Tables V-l and V-2 show
the results of analyses of gasoline from different refinery sources that
indicate substantial variation among refineries and types of blends.
Table V-l
TYPICAL LIQUID VOLUME PERCENT OF BENZENE IN
GULF U.S. GASOLINES, OCTOBER 1976
Vol% Benzene
Refinery Source
A
B
C
D
E
F
Average
Standard Deviation
Good Gulf
0.54
1.99
1.19
1.59
1.25
0.85
1.24
0.52
Gulf Crest
0.88
1.45
1.21
1.18
1.98
0.82
1.25
0.43
No-Nox
1.16
0.85
0.81
1.49
2.39
0.88
1.26
0.61
Source: Runion, 1976 (as cited in PEDCo, 1977).
39
-------
Table V-2
BENZENE CONCENTRATION IN DIFFERENT GRADES AND
SEASONAL BLENDS OF GASOLINE
Company —
Typical
Service
Station
Tresler-Comet
Bonded
Bonded
Clark
Gasoline
Grade
Premium
Regular
Unleaded
Regular
Unleaded
Regular
Unleaded
Regular
Unleaded
Vol% Benzene in
Bulk Sample
Summer
1.11
1.21
1.41
0.88
1.19
0.88
1.20
0.97
1.09
Winter
1.10
1.00
1.60
0.88
1.60
0.88
1.60
2.00
1.10
Average
Vol%
Benzene
1.11
1.11
1.51
0.88
1.40
0.88
1.40
1.49
1.10
Source: National Institute of Occupational Safety
and Health, 1976 (as cited in PEDCo, 1977).
Because benzene is one of the more volatile gasoline constituents,
evaporation from gasoline represents a significant source of human
exposure. In this chapter, human exposure from gasoline service stations
is considered. (Chapter IX examines general urban exposures related to
automotive emissions, including gasoline evaporation from automobiles.)
Two main pathways of exposure are examined: (1) obtaining gasoline at self-
service pumps; and (2) residing in the vicinity of gasoline service stations.
Although few exposure data about gasoline service stations are avail-
able, Battelle recently obtained (1977) a few monitoring data of benzene
concentrations in the breathing zone at self-service operations. Limited
data of ambient benzene concentrations in the vicinity of gasoline stations
are also available. In addition, some rough estimates of benzene concentra-
tions within 300 m of gasoline service stations have been projected by
dispersion modeling (Youngblood, 1977d) . In the following section, the
available sample data and the estimating techniques for the two pathways
identified will be_discussed separately.
40
-------
B. Methodology and Exposures
1. Self-Service Operations
Service stations are characterized by their services and business
operations: full-service stations, split island stations, self-service
stations, and convenience store operations. In full-service stations,
attendants offer all services, including gasoline pumping and other
mechanical check-ups. If fuel is obtained at any of the last three classes
of stations, the customers may fill up their tanks themselves. In split
island stations, both self-service and full-service are offered. At the
two remaining types of stations, only self-service is available. While
pumping gasoline, an individual is exposed to high benzene levels released
*
as vapor from the gasoline tank. Although occupants in the car at both
self-service and full-service operations receive some benzene exposures,
the highest exposures are received by the individual pumping the gas.
Because it is difficult to estimate level and length of exposure for occupants,
only those individuals obtaining gasoline from self-service pumps are
considered. (It is not within the scope of this report to evaluate occupa-
tional exposures.)
Benzene content of evaporative gases increases and decreases
during evaporation, depending on the system temperature and the relative
volatilities of all the components of the fuel (Mitre, 1976). Recent
information indicates that gases released during automobile fill-ups have
little relationship to the benzene content in the gasoline. Rather, the
ambient temperature relative to the temperature of the gasoline has the
most significant effect, and most of the exposure results from the benzene
vapor trapped within the tank, not from the gasoline being pumped (Johnson,
personal communication, 1977). If the gasoline is cold relative to the
tank (as in summer), most of the benzene vapor will be absorbed into the
gasoline. On the other hand, if the gasoline is warm relative to the
Vapor recovery systems can reduce exposure levels significantly, if properly
working and operated. Such systems are required for service stations in
parts of California.
41
-------
tank (as in winter), the benzene vapor will be displaced rather than
absorbed and more significant exposures will result.
Self-service dispensing of gasoline is a relatively new marketing
method pioneered by independent operators on the West Coast and in the
southern United States. Today, it accounts for 30% of gasoline sold. The
national market-share of the major gasoline producers has decreased recently
as independents and others specializing in high-volume, low-margin sales
capture a larger percentage. Of the approximately 184,000 conventional
service stations and tie-in gasoline operations in the United States,
service stations with some self-service operations account for 39% (ADL,
1977b). Table V-3 indicates the types of service stations offering self-
service gasoline.
Table V-3
SELF-SERVICE OPERATIONS
Percent of
Outlets Offering Self-Service U.S. Total
Total self-service 9
Split island with self-service 26
Convenience stores _4_
Total Outlets with Self-Service 39
A recent ADL report (1977b) revealed that there are 71,300 out-
lets with self-service gasoline. Gasoline sold for the year ending May
9
30, 1977, equals approximately 87.4 x 10 gal in the United States. Of
Q
this amount, 27.0 x 10 gal (31%) was dispensed at self-service pumps.
The market-share of self-service stations was surveyed for four metro-
politan Air Quality Control Regions (AQCR): Boston, Dallas, Denver, and
Los Angeles. The market-share held by self-service operations varied
from 9% in Boston to 45% in Denver (see Table V-4). Another study by
Applied Urbanetics, Inc. (1976) surveyed Baltimore and Madison,
Wisconsin. The results of this study are shown in Table V-5. It appears
that about 40% of the market in urban areas is accounted for by self-
service operations.
42
-------
Table V-4
GASOLINE MARKET SHARE OF SELF-SERVICE STATIONS
IN FOUR AQCRs,
SPRING 1977
Type of Operation
Boston AQCR
Full-service
Self-service (total)
Split island
Self-service
Convenience stores
Dallas AQCR
Full-service
Self-service (total)
Split island
Self-service
Convenience stores
Denver AQCR
Full-service
Self-service (total)
Split island
Self-service
Convenience stores
Los Angeles AQCR
Full-service
Self-service (total)
Split island
Self-service
Convenience stores
Number of
Outlets
2,253
100
a
a
8
92
2,094
1,124
480
444
200
621L
656
310£
226
120
2,518
4,780
3,632*
1,022
126
Sales
Volume
(1Q6 gal/yr)
1,045.1
108.6
924.6
593.8
292.1
235.7
2,472.6
2,154.8
Market
Sharing
Percent
91%
61%
39%
55%
45%
53%
47%
aSplit island operations offering full service and self-serve islands.
bOf these 445 are split island operations that offer full service and
mini-serve (attendant-operated) islands.
Source: ADL (1977b).
43
-------
Table V-5
GASOLINE MARKET SHARE OF SELF-SERVICE
STATIONS IN TWO METROPOLITAN AREAS, 1976
Type of Operation
Baltimore SMSA
Full-service
Self-service (total)
Split island
Self-service
Madison SMSA
Full-service
Self-service (total)
Split island
Self-service
Sales
Volume
(106 gal/yr)
111.5'
90.5
25.5
65.0
56.0'
77.0
17.0
60.0
Market
Sharing
Percent
55%
45%
42%
58%
alncludes the sales from mini-serve (attendant-operated)
stations and 50% of the sales from split islands.
Source: Applied Urbanetics, Inc. (1976).
44
-------
To estimate the people exposed to benzene from this source,
several assumptions were necessary. The gasoline pumped through self-
service outlets is estimated at 27.0 x 10^ gal. The annual average fuel
consumption per vehicle is 736 gal (U.S. Federal Highway Administration,
1974). If it is assumed that on the average, a person who primarily uses
self-service gasoline makes one trip there per week, an average fill-up
amount of 14 gal is determined by dividing 736 gal/vehicle/yr by 52 wk/yr.
By dividing the average fill-up into the self-service gallons pumped, we
9
estimate trips per year to self-service operations at 1.9 x 10 . When
this number is divided by 52 trips per person per year, the people exposed
to benzene from this source is estimated at 37 x 10 . This estimate of
the population exposed assumes that the individuals using self-service
gasoline never obtain gasoline at full-service stations.
Battelle conducted a preliminary study (1977) to determine the
benzene exposure levels from self-service gasoline pumping. Three samples
of ambient air were taken in the breathing zone of persons filling their
tanks. The results, shown in Table V-6, indicate a wide range in the
benzene concentrations of the emissions. The variations seem to be related
to the subject's position in relation to the tank opening and the wind
direction. Because all measurements were taken on the same day and at
approximately the same time, ambient temperature did not cause the varia-
tion. Basically, if the subject was downwind of the tank opening, higher
levels were recorded. The time-weighted average concentration of benzene
from the three samples is 245 ppb. The average length of time taken to
fill up a gasoline tank is 1.7 min. Although 14 gal per fill-up is assumed,
the wide range in pumping speeds does not allow a precise estimate of
time required per fill-up.
Table V-6
SAMPLING DATA FROM SELF-SERVICE GASOLINE PUMPING
Sampling Rate Nozzle
Customer
1
2
3
(mL/min)
31
31
31
Time (min)
2.5
1.1
1.6
Gallons
Pumped
14
8
9
Sample
Volume
(L)
78
34
50
Benzene Level
o
Vg/m
115
324
1740
ppb
43'
121
647
Source: Battelle (1977)
45
-------
The estimated exposure levels are based on the information con-
tained in Table V-6. It is recognized that these data are quite limited
and highly variable. In states where vapor recovery systems are used, the
estimated exposure level may be much lower, these levels do allow an
order-of-magnitude estimate of expected exposure levels from self-service
gasoline pumping. It can be estimated that approximately 37 x 10 persons
use self-service stations. While filling their tanks once a week, they
are exposed to a benzene level of 245 ppb for 1.7 minutes. Their annual
exposure is estimated at 1.5 hr. (Table V-9 summarizes this information.)
2. Vicinity of Service Stations
People residing in the vicinity of service stations are exposed
to benzene from gasoline evaporation. Benzene emissions result from
gasoline pumping by attendants and customers, and from gasoline loading
by distribution trucks. The amount of benzene emitted depends on the
ambient temperature, vapor recovery controls, and the benzene content in
gasoline. The United States has approximately 184,000 service stations,
and it is expected that many people are exposed to benzene from these
sources. Because density of service stations in urban areas is high and
is expected to correlate well with urban population density, only urban
areas are considered in this analysis.
*
Available monitoring data for one location (Battelle, 1977b)
indicate that benzene concentrations are below 1.0 ppb within 300 m of a
service station. Higher benzene concentrations may be observed in the
direction of the prevailing winds. These results are generally supported
by dispersion modeling estimates developed by EPA.
Dispersion modeling for a worst case condition was conducted
by EPA (Youngblood, 1977d) using the Single Source (CRSTER) Model. Meteor-
ological data for Denver, Colorado, were used to represent a reasonable
worst-case location. The model was executed in such as way that night-time
The American Petroleum Institute and Battelle are currently conducting
monitoring studies; the data should soon be available.
46
-------
inversions were eliminated, resulting in enhanced dispersion and, for
low-level sources such as service stations, lowered ground-level concen-
trations. Table V-7 presents the results of the dispersion modeling.
Note that the operating conditions, pumping volumes, and the chosen
location all represent worst-case conditions. Consequently, extrapolation
of these results to average conditions is difficult. Nevertheless, it
is reasonable to conclude that individuals residing within 300 m of a
service station may be exposed to annual-average concentrations of 1.0 ppb
or more, whereas those residing beyond 300 m are expected to be exposed
to less than 1.0 ppb on an annual-average basis.
The number of service stations in urban areas can be estimated,
based on service station density and total U.S. population in urban areas;
service station density in urban areas can be extrapolated from the data
presented in Table V-8. The service station density shown for four
metropolitan AQCRs is somewhat variable, with no apparent regional pattern
evident. Based on these data, an average of 0.7 service station per 1000
population was estimated. It is believed that this number can be applied
generally to urban areas throughout the United States.- Urbanized areas
provide the best population base. The 1970 population residing in urbanized
areas was 118,447,000 (Bureau of the Census, 1975). Thus, service stations
in urbanized areas are estimated at 82,900, or 45% of all stations.
There are many difficulties inherent in applying the available
dispersion modeling data to urbanized areas. For example, it is impossible
to determine the distance at which the benzene levels fall below 0.1 ppb.
In the absence of this information, we developed an approach for estimating
the maximum possible radius between service stations in which none overlap.
This approach assumes (1) that service stations are uniformly distributed
throughout the urbanized area, and (2) that levels fall below 0.1 ppb at
Defined by the Bureau of Census as the central city or cities and surround-
ing closely settled territories. All sparsely settled areas in large incor-
porated cities are excluded by this definition. Densely populated suburban
areas, however, are included (U.S. Department of Commerce, Bureau of the
Census, 1972 County and City Data Book).
47
-------
Table V-7
ROUGH DISPERSION MODELING RESULTS FOR GASOLINE SERVICE STATIONS
Station
Al
A2
Bl
B2
Hours of
Operation
8 a.m. - 4 p.m.
6 days /week
8 a.m. - 4 p.m.
6 days /week
24 hours /day
7 days /week
24 hours /day
7 days /week
% Benzene
in Gasoline Calculated
Vapor Emission Rate (j»/s)
0.7 0.019
3.0 0.080
0.7 0.0053
3.0 0.023
50
8-Hour
27
117
Annual
1
2
Distance (m)
100 150 200 300
A*
Worst-Case Concentration (ppb)
13 8 5 3
57 34 23 12
&&
Average Concentration (ppb)
-------
Table V-8
SERVICE STATION DENSITY IN FOUR METROPOLITAN AQCRs
Service Station
AQCR
Boston
Dallas
Denver
Los Angeles
*
Number of
Service Stations (1977)
2,353
3,218
1,277
7,298
**
AQCR
Population (1975)
4,039,800
2,970,900
1,389,000
14,072,400
Density
(number/ 1000
population)
0.6
1.1
0.9
0.5
Source:
*ADL
U.S. Department of Commerce, Bureau of Economic Analysis, 1973.
SRI estimates.
the distance of the maximum radius. The maximum possible radius is esti-
mated as follows:
2
(TT r ) (number of service stations) = urbanized area
2 2
where, urbanized area = 90,860 km (35,081 mi ); and
service stations = 82,900.
I 90.86
"V IT 82,
r = / 90,860 km2
900
r = 0.59 km
Thus, for this analysis, the average annual benzene concentration in the
vicinity of gasoline service stations is assumed to range between 1.0 and
2.0 ppb within 300 m, and between 0.1 and 1.0 ppb from 300 to 590 m.
The population residing within 300 m of gasoline service sta-
tions is estimated by the following equation:
IT (0.3 km)2 (1318 people/km2) (82,900) - 31,000,000;
where, 1318 is the average population density in urbanized areas (1970).
49
-------
The population residing within from 300 to 590 m of a service
station is estimated as follows:
(IT [0.59 km]2 - TT [0.3 km]2) (1318 people/km2) (82,900) = 87,000,000
The summary results are presented in Table V-9. It is recog-
nized that these estimates are only rough approximations, based on assump-
tions of uniform distribution of service stations in urbanized areas,
uniform pumping volume, and average population density. In reality, more
service stations are located in commercial areas than in residential areas,
and pumping volumes vary substantially. In addition, it is likely that
several service stations are located in the same general area. If these
areas are considered to be commercial, they may have either a higher than
average population density within 600 m (because of a high percentage of
apartments nearby), or one much lower than average (because of a high
percentage of businesses and few residences of any kind). People residing
near areas with co-located service stations may be exposed to higher annual
average benzene concentrations than those estimated. It is likely from this
analysis that population exposed is overestimated, whereas the exposure levels
may be underestimated. Further study is warranted to determine a more
accurate estimate of exposure levels based on pumping volumes, co-location
of service stations, their distribution within an urban area, and emission
rates.
50
-------
Table V-9
SUMMARY OF POPULATION EXPOSED TO BENZENE
FROM GASOLINE SERVICE STATIONS
EXPOSURE TYPE
SELF-SERVICE
PUMPING
RESIDING IN
THE VICINITY
EXPOSURE
TIME
1.7 MIN.
34 HR.
ANNUAL
EXPOSURE
1.5 HR.
ANNUAL
AVERAGE**
POPULATION EXPOSED TO BENZENE CONCENTRATIONS (ppb)*
0.1 - 1.0
-
87.000,000
1.0 - 2.0
-
31,000.000
245.0
37,000,000
-
TOTAL
37.000,000
118.000,000
* To convert to /ig/m3 , multiply concentrations by 3.2.
** To convert annual average exposures to 8-hour worst case, multiply concentrations by 10.
Source: SRI estimates..
-------
VI PETROLEUM REFINERIES
A. Source
Petroleum refineries appear to be a significant source of atmos-
pheric benzene emissions. Benzene is produced as a by-product of the
refining process, used in the formulation of gasoline, and emitted
from distillation of crude oil. Benzene emissions from a refinery
include: (1) process emissions from crude unit light and heavy naphtha
streams, fluid catalytic cracking units, hydrocracking units, and
gasoline treating units; and (2) nonprocess sources such as waste-
water treatment facilities, heaters and boilers, and facilities for
storage and handling of benzene and gasoline (PEDCo., 1977).
Benzene produced from catalytic reforming extraction by petroleum
refineries accounted for 50% of the benzene supply in the United
States in 1976 (SRI estimates). Because the average distribution
of aromatics in reformate is 10% benzene, 40% toluene, and 50% xylene,
toluene dealkylation processes are being used more frequently to in-
crease the benzene fraction. (Faith et al., 1966). Toluene dealky-
lation to produce benzene currently accounts for 27% of the benzene
supply in the United States (SRI estimates). This process is most
common in petrochemical complexes, rather than in the petroleum
refineries. Table VI-1 lists the petroleum refineries in each state
that extracts aromatics from the reformate produced in catalytic
reforming. Texas and Louisiana account for 84% of the total production
of benzene, toluene, and xylene.
The composition of crude oil varies widely, but commonly contains
about 0.15% benzene by volume (Dickerman et al., 1975). Consequently,
benzene is emitted during the refining process. However, only 34 out
of a total of 266 refineries actually produce benzene as a salable
item. We have assumed that those producing benzene as a salable
by-product have larger benzene emissions than those that do not be-
cause of the processing and handling involved. This assumption is basic
53
-------
to the methodology discussed in subsection VI-B.
Sample data from one refinery producing benzene as a by-product
is shown in Figure VI-1. The extreme variability of the measurements
is evident. All samples were collected during the same day. The limited
nature of these data makes extrapolation unreliable.
Table VI-1
PETROLEUM REFINERIES PRODUCING AROMATICS,*
BY STATE
*
Number of Quantity
State Plants (bbl/stream day)
California 3 5,990
Illinois 2 6,700
Kansas 1 1,400
Kentucky 1 4,000
Louisiana 3 19,100
Mississippi 1 6,000
New York 1 3,000
Oklahoma 1 2,000
Pennsylvania 3 9,700
Texas 18 122,525
Total 34 180,415
* Total quantity of benzene, toluene, and xylene produced.
Source: Oil & Gas Journal (May 28, 1977)
Four states have 60% of the refining capacity in the United States:
California (14%), Illinois (7%), Louisiana (13%), and Texas (26%). Penn-
sylvania (5%) and New Jersey (4%) bring the total to*69%. Thus, 15% of
the states (6 out of 39 states) with petroleum refineries account for
69% of the refining capacity.
B. Methodology
The general methodology discussed in Chapter III was used as the
basis for determining exposure levels from petroleum refineries.
54
-------
100
o
CC
Z
UJ
o
I
LU
ID
N
LU
CD
10
1 I I I I |
1 I I I L
CURVE EXTRAPOLATED BY
REGRESSION ANALYSIS
AS FOLLOWS:
C - eDb
a • 8.95
b " -1.44
R 2 - 0.14
I I I I I I I J
0.1
1.0
DISTANCE FROM SOURCE - km
10
* Collected In activated charcoal tube* and analyzed by gat chromatograph with a flam* lonlzatloo detector.
Detection limit vw» approximately 0.1 ftg of benzene/100 mg charcoal.
Source: EPA, 1977
FIGURE VI-1. MONITORING DATA* FOR GULF ALLIANCE REFINERY,
BELLE CHASSE, LOUISIANA
55
-------
Youngblood of EPA conducted dispersion modeling (1977c) to characterize
benzene emissions from petroleum refineries. The results were then applied
to each refinery by computer program to estimate the exposed population.
Emissions are highly variable, depending on the size and age of the
plant and on the control technology employed; however, because specific
emission factors were unavailable, general averages were used. Because
actual production data are unobtainable, capacity production and 24-hr
(365 days) operation were assumed. Variations in geographic location
and meteorological conditions were not considered. The results are
not meant to be precise: rather, they provide a reasonable order-of-
magnitude estimate of expected exposure levels.
Estimates of refinery emission factors were based on average hydro-
carbon emissions and the percent of the total hydrocarbon emissions
attributed to benzene. Evaluations of available information and dis-
cussions with EPA (Radian Corporation, 1975; Hustvedt, personal com-
cunication, June 1977a) resulted in the selection of the following
factors:
• Total hydrocarbon emissions from petroleum refineries
= 920 lb/1,000 bbl
• Estimated percentage of hydrocarbon emissions attributed to
benzene from refineries without catalytic reforming =0.5
• Estimated percentage of hydrocarbon emission attributed to
benzene from refineries with catalytic reforming * 1.0
These emissions result from storage losses (f«50%) and from leaks
and stacks (j=a50%). Table VI-2 presents the calculations of emission
factors from the two types of petroleum refineries identified. The
listing of U.S. petroleum refineries, shown in Appendix D, was ob-
tained from the Annual Refining Survey published in the Oil & Gas
Journal (March 28, 1977). This listing includes a breakdown of re-
fineries that extract benzene, toluene and xylene from the refonnate
as well as the plant capacities. The emission rate in g/s for each
plant was estimated, based on the plant capacity and the emission
factor. The emission rate for each plant is shown in Appendix D.
56
-------
Table VI-2
CALCULATION OF EMISSION FACTORS FOR PETROLEUM REFINERIES
Refineries with catalytic reforming:
~ no -ii./1-vi ( total hydro- \ n nn /percent\ ,_3 „
0.92 Ib/hbll , J . . I x 0.01 If )x 10 g/kg o
__ V carbon emissions/ _ \ benzene/ _ _ £6 g/m
~~~~ 0.159 ra3/bbl x 2.2 Ib/kg
Refineries without catalytic reforming:
0.92 Ib/bbl (tot? hyd"- \ xO.005 fPercent> 103 g/kg
\ carbon emissions / \ benzene/ & & _
0.159 m3/bbl x 2.2 Ib/kg
o/m
Because petroleum refineries are large and benzene emissions are
distributed widely throughout the plant area, Youngblood used the PAL
(Point, Area, Line Source) Dispersion Model (Turner et al.) to esti-
mate approximate downwind concentrations. The modeling assumptions and
procedure were the same as those described for coke ovens (pages IV-5
and IV-6). Table IV-A applies to petroleum refineries as well as to
coking plants.
Three of the size categories are applicable to petroleum refiner-
ies (Hustvedt, personal communication, 1977b) :
2
Plant Area (km ) Capacity (bbl/day)
0.25 <35,000
1.00 35,000 - 200,000
A.00 >200,000
Figure VI-2 shows the curves corresponding to the three plant sizes.
Because the differences between the curves are within the range of
2
uncertainty associated with dispersion analysis, the middle curve (1.0 km )
was used to represent the dispersion characteristics of all refineries
at the suggestion of Youngblood (personal communication, August 1977).
57
-------
1000
m
00
1
O
Ui
O
IU
5
N
UJ
03
100
10
\ \ fill
PLANT AREA
(km2)
I I I TT
I
I
I I I I I I
I
I
J I I I I I
I
I I I I I I I
0.1 1.0 10 100
DISTANCE FROM SOURCE - km
* Bated on an emtaion rate of 100g/s
Source: After YoungUood (1977c)
FIGURE VI-2. DISPERSION MODELING RESULTS FOR THREE SIZE CATEGORIES OF PETROLEUM REFINERIES*
-------
The computer program discussed in Chapter III was applied to petro-
leum refineries by substituting a new equation developed through re-
2
gression analysis to characterize the.l.O-km curve. This equation can
be written as follows:
C = 200 D~°'51 (6.1)
3
where, C is the 8-hour worst-case benzene concentration in yg/m ;
and D is the distance from the source in km.
Equation (6.1) was then normalized to annual average conditions,
and individual emission rates (the Youngblood model was based on an
emission rate of 100 g/s):
C - 0.2 E D~°'51 (6.2)
3
where, E is the emission rate for the location of interest.
3
To estimate the people exposed to benzene concentrations
within each range at each location, Equation (6.2) is rearranged
as follows to determine the distance at which the specified concen-
trations are found:
0.0426
a
\
1.96
/
(6.3)
where C, is the specified concentration (i.e. 0.1, 1.0, 2.0, and so
o
on; input data, however are in yg/m ); and D. is the distance at
which the specified concentration is found. The remaining steps in
the methodology are discussed in Chapter III.
If more than one refinery was located in a particular city, we
assumed that the refineries were co-located, and we summed their emis-
sion rates. Although several cities had three or more refineries,
it is also true that few people generally live near such complexes.
Thus, with this method, the exposed population is minimized,
whereas the exposure level is maximized for a particular city.
C. Exposures
The population exposed to atmospheric benzene from petroleum
refineries by plant location is shown in Appendix D. A state summary
59
-------
of annual average benzene concentrations and exposed population is
shown in Table VI-4. Pennsylvania, which is fifth in number of
refineries, has the highest exposed population with 2,171,300; Texas
is second with 1,881,000 people exposed. Of the states with petroleum
refineries, 21 (54%) have less than 5,000 people exposed, and 9 (23%)
have more than 100,000 people exposed. More than 6 x 10 people
are exposed to benzene from petroleum refineries. More than 68,000
people are exposed to an annual average concentration of 1.0 ppb
or more (8-hr worst case level of 10 ppb or more). Although the ex-
posure levels and population estimates are rough approximations,
they can be considered to be a reasonable estimate of expected condi-
tions.
60
-------
Table VI-3
ESTIMATED POPULATION EXPOSED TO BENZENE
FROM PETROLEUM REFINERIES BY STATE
Population Exposed ~ **
State
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Delaware
Florida
Georgia
Hawaii
Illinois
Indiana
Kansas
Kentucky
Louisiana
Maryland
Michigan
Minnesota
Mississippi
Missouri
Montana
Nebraska
New Hampshire
New Mexico
New York
New Jersey
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Tennessee
Texas
Utah
Virginia
Washington
West Virginia
Wisconsin
Wyoming
Total
Total Exposed
0.1 - 1.0
100
t
0
500
555,200
AGO
6,400
0
0
100
203,000
118,400
20,100
24,600
322,700
500
12,100
800
49,500
500
22,500
0
0
t
40,500
465,400
t
537,100
127,200
t
2,137,700
700
1,854,800
10,200
100
4,800
0
t
13,200
6,529,100
Population -
1.1-2.0 2.1-4.0 4.1-10.0 >10.0
4,800 300 . t t
t
200 t t
t t
t
t
1,600 100 t
t
1,000 100 t
t
t
200 t
200 t t
t t
31,300 2,100 200 t
24,500 1,600 100 t
t
t
63,800 4,200 300 t
6,597,400
* Totals are rounded; a zero indicates that a refinery(ies) is pre-
sent in the state, but exposure levels were below 0.1 ppb.
** To convert to 8-hr worst case, multiply concentration by 10;
to convert to ug/nr* multiply by 3.2
t Fewer than 50 people exposed.
Source: SRI estimates.
61
-------
VII SOLVENT OPERATIONS
A. Sources
Little is known about benzene used in solvent operations. Recent
publications evaluating benzene in the workplace have identified in-
dustries in which benzene may be used as a solvent, but the studies
were unable to quantify actual volumes of use (Arthur D. Little, Inc.,
1977; PEDCo, 1977; Mitre, 1976). The Occupational Safety and Health
Administration (OSHA) is currently evaluating industries for benzene
hazards under their emergency temporary standards (Brinkerhoff, per-
sonal communication, 1977). Table VII-1 lists major industries that
OSHA is investigating to determine whether benzene is used as a
solvent in their operations.
Some indication of the maximum possible volume of benzene used in
solvent operations can be obtained by evaluating benzene consumption
data for the United States. More than 95% of all benzene used as a
raw material is consumed by seven chemical manufacturing processes
(see Chapter III). Only 2.8% (3.05 x 108 Ib [1.39 x 108kg]) is con-
sumed by other uses (SRI estimates, 1977). Other uses include benzene
for: anthraquinone, benzene hexachloride, benzene sulfonic acid
(primarily for phenol), diphenyl, hydroquinine, nitrobenzene (other
than that used for aniline), resorcinol, and solvent applications.
Because three of the uses (resorcinol, nitrobenzene, and benzene
sulfonic acid) account for approximately 50% of the benzene consumed
by all other uses, solvent operations must consume much less than
150 x 10 Ib/yr (68.0 x 10 kg). In fact, many operations have
switched to other solvents because of the toxicity hazard associated
with benzene. The amount of benzene used by solvent operations is con-
sumed in many, small volume markets (SRI estimates, 1977).
63
-------
Table VII-1
INDUSTRIES AND MANUFACTURED PRODUCTS
POSSIBLY USING BENZENE AS A SOLVENT
Rubber tires
Miscellaneous rubber products
Adhesives
Gravure printing inks
Printing and publishing
Trade and industrial paints
Paint removers
Miscellaneous industrial uses
Coated fabrics
Synthetic rubber
Leather and leather products
Floor covering
Source: Brinkerhoff, personal communication (1977)
64
-------
A recent study by Arthur D. Little (ADL) (1977a) identified
the manufacture of rubber tires and of miscellaneous rubber products
using synthetic rubber and adhesives as possible major sources of
occupational exposures. Although industry sources indicate that benzene
has been removed from many of the operations within the rubber industry,
the ADL study reported that substantial quantities are still being
used in the manufacture of synthetic rubbers, production of phenolic
antioxidants, polymerization of hydrophilic polymers, and manufacture
of rubber adhesives. However, these operations may take place in
locations apart from the location where the final product is produced.
Toluene has often been substituted 'as a solvent for benzene
(Brinkeroff, personal communication, 1977). However, it contains
significant quantities of benzene contamination ranging from 2 to 15%
by weight. The proposed OSHA standard will reduce this level to 1%
by the end of 1977 and to 0.1% by the end of 1978.
Limited monitoring data are available. NIOSH is currently con-
ducting a sampling program in the vicinity of solvent operations
using benzene (Hardel, personal communication, 1977). Sampling data
for three B. F. Goodrich Chemical Company solvent operations were
recently submitted to EPA. Figure VII-1 displays the measured
benzene concentrations at various sampling sites within 1 km of the
source. (The wide variability probably occurred because the wind
was gusty, averaging between 10 to 15 mph throughout the sampling
period.) Benzene concentrations as high as 700 ppb were measured
within 420 m of the source—an indication that significant potential
exists for high environmental exposure to benzene from solvent
operations.
B. Methodology and Exposure
Because of the extremely limited information on operations using
benzene as a solvent, amount used, and probable emission factors, any
exposure estimates are necessarily crude. The primary assumption is
that only the largest plants will have significant potential for high
65
-------
800
700
600
500
400
300
& 200
g
I
§
z
111
N
IU
CD
100
90
80
70
60
50
40
30
20
10
I I I IT
D ANTI-OXIDANT PLANT (3-5 hr)*
• SPECIALTY POLYMER PLANT (7 hr)
• CB-EPDM PLANT (5-7 hr)
I -I- I-
I I I
0.1
.3 .4
DISTANCE - km
.7 JB J»
The hours shown In parenthesis are approximate averaging times
for the samples taken at each plant.
FIGURE VIM. SAMPLING DATA FOR THREE SOLVENT OPERATIONS
66
-------
environmental exposure. The 1972 Census of Manufacturers (Bureau of
the Census) was used to determine those operations that have the
largest average plant size. Table VII-2 lists the major operations
and average number of employees per plant. Five operations that aver-
aged more than 100 employees per plant were selected for further
analysis. Table VII-3 lists the number of plants and average number
of employees per plant for each of the five operations by state.
Georgia and California have the largest number of plants together com-
prising 32% of the total. Based on Table VII-3 it can be assumed that
the population in those states with the most plants, have the greatest
risk of benzene exposure from the solvent operations identified.
A rough estimate of the level of risk associated with each plant
can be obtained by approximating the benzene use by each operation.
As discussed in the previous section, it is known that 150 x 10 Ib/yr
of benzene (68 x 10 kg) is used for other unidentified uses, including
solvent applications. If it is assumed that 75% of this figure repre-
sented solvent use, the total is 110 x 10 Ib/yr (50 x 10 kg/yr).
Because it is expected that the largest single solvent application
is in rubber tires and miscellaneous rubber products, it is further
assumed that 80% of the total estimated solvent use is found in rubber-
related manufacturing. Therefore, the amount allocated "to rubber
tires and miscellaneous rubber products is estimated to be 88.0 x 10 Ib/yr
(40 x 10 kg/yr). Table VII-3 shows 360 plants in rubber-related
manufacturing. Using this total, the average benzene consumption per
plant is estimated at 0.24 x 10 Ib/yr (0.11 x 10 kg/yr).
The next step is to estimate an emission factor. By careful analysis
the data in Figure VII-1 can be compared with the dispersion modeling
data presented in Chapter III (see Table III-3). At 300 m, the aver-
age benzene concentration for the three monitored solvent operations
ranges between 50 and 100 ppb. If these data are assumed to represent
annual average conditions, the concentrations approximate the annual
average concentrations of p-dichlorobenzene (56 ppb) and chlorobenzene
(137 ppb) at 300 m for ground-level sources. However, comparing the
67
-------
Table VII-2
AVERAGE NUMBER OF EMPLOYEES PER PLANT
FOR SELECTED SOLVENT OPERATIONS
Sic Number
Item
Average Number of
Employees/Plant
221
229
278
282
285
301
302
303
304
306
307
31
379
Floor covering mills
Miscellaneous textile goods
Blankbooks and bookbinding
Plastics materials, synthetics
Paints and allied products
Tires and innertubes
Rubber and plastics footwear
Reclaimed rubber
Rubber, plastic hose, and belting
Fabricated rubber products
Miscellaneous plastic products
Leather and leather products
Miscellaneous transportation equipment
113 .
60
35
351
41
522
295
45
354
89
45
84
38
Source: adapted from 1972 Census of Manufacturers.
68
-------
Table VI1-3
NUMBER OF PLANTS AND EMPLOYEES FOR SOLVENT OPERATIONS
WITH HIGH POTENTIAL FOR BENZENE EMISSIONS
Tires and Rubber, Plastic Hose
Innertubes and Belting
JL E_ » E_
Alabama
Arkansas
California
Colorado
Connecticut
Delaware
Florida
Georgia
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Missouri
Nebraska
Hew Hampshire
New Jersey
New York
North Carolina
North Dakota
Ohio
Oklahoma
Pennsylvania
Rhode Island
South Carolina
Tennessee
Texas
Utah
Virginia
West Virginia
Wisconsin
Total
10 800
5 400
22 500*
2 900
1 1800
9
10
5
5
2
3
12
11
2
180
200
500*
360
700
1750
600
1750
600
600
600
100
7 400
27 1000
7 600
14 500*
460
500*
360
1750
4
2
2
3
18
5
i
15
1
4
1
1
83
300
750
350
100
900
400
100
200
750
450
100
600
600
350*
360
900
600
300
200
300
750
150
Rubber and
Plastic Footware
* E
1 300
3 100
1 300
3 1200
4 450
3 600
2 375
3 250
5 360
3 1200
12 300
7
5
10
4
1
2
_1
97
Plastics Materials, Floor Covering
Synthetics Mills
JL JL- JL -L.
7 300
5 150
62 100*
100
250
150
180
450
50
250
900
200
150
200
ISO
750
9
SI
9
6
10
11
27
9
3
3
10
14
5
21
13
4
5
4
37
27
400
40
200
700
5BO
100
100
160
100
100
450
264
580
200
300
200
150
50
J 70
35 150
20 100
22 700
200
400
IS 1100
IS 1400
35 280
10 1800
6 1200
10 100
502
247 100
7 100
2 100
100
10 100
1 1800
2
3
17
6
27
8
30
20
4
449
ISO
100
20
38 100
200
200
25
100
80
100
600
Nuator
of
Plants
26
12
146
4
IS
8
14
270
SO
22
8
6
17
14
S
10
S3
19
6
9
14
3
12
61
52
35
38
85
14
81
10
47
53
SO
2
19
8
1311
I m Number of plants
E • Average nunber of employees per plant
* . The average plant size for the category. This was used when it was not possible to determine an average plant
sice for the Slate from the listed information.
Source: 1972 Ce"8"» of Manufacturers. Bureau of the Census; 1975 Statistical Abstract of the United States.
Bureau of the Census.
69
-------
annual production rates of 150,000 ton/yr for chlorobenzene and 30,000
ton/yr for p-dichlorobenzene to 120 ton/yr per plant of estimated
average benzene consumption for rubber and tire manufacturing, it is
evident that the emission factor for solvent operations must be much
higher than those for chemical processes to account for the measured
benzene concentrations. For this analysis, we assume an emission
_3
factor of 100 x 10 kg/kg.
With the assumed emission factor and the estimated average plant
size, the following calculations can be made:
Average benzene consumption per plant = 0.11 x 10 kg/yr
_3
Emission factor = 100 x 10 kg/kg benzene used
Total emissions = 0.011 x 10 kg benzene/yr
Estimated emission rate = 0.35 g/s
The dispersion modeling results presented in Chapter III can be
used to estimate the ambient benzene concentrations near a plant of
average size. (See Table VII-4). The results of the calculations
indicate that average annual concentrations >1 ppb can be expected
within 1 km of the average solvent operation under our previously
stated assumptions. Consequently, further analysis is required.
The states containing the most plants with high potential for
atmospheric benzene emissions are identified in Table VII-5. It is
impossible to discern with certainty whether or not benzene is
actually used at these facilities. The probability of benzene
use is high, however, and, if used, the probability of annual average
benzene concentrations of 0.1 ppb or greater is significant. In
fact, all the plants identified in Table VII-5 are at least two times
larger than the average plant size in their category (based on total
number of employees).
A crude estimate of exposed population is possible by assuming an
annual benzene consumption and a general emission factor for each
plant listed in Table VII-5. As before, the emission factor used is
_3
100 x 10 kg/kg. The total benzene use for each plant is estimated
70
-------
Table VII-4
ESTIMATED AVERAGE ANNUAL BENZENE CONCENTRATIONS
IN THE VICINITY OF AN AVERAGE SIZE SOLVENT OPERATION
IN RUBBER-RELATED MANUFACTURING
Distance
Benzene
Concentrations
Distance
Benzene
Concentrations
From Source (km)
0.15
0.30
0.45
0.60
0.75
1.6
ppb
1.2
0.7
0.4
0.3
0.2
0.08
tig An
3.8
2.2
1.3
1.0
0.6
0.3
From Source (km)
2.5
4.0
6.0
9.0
14.0
20.0
ppb
0.04
0.02
0.01
0.007
0.004
0.002
ug/m
0.1
0.06
0.03
0.02
0.01
0.006
To convert to 8-hour worst case, multiply concentrations by 10.
Source: Extrapolated from dispersion modeling results using curve
B (Building Source), (see Chapter III, Table III-4).
71
-------
Table VII-5
STATES WITH THE HIGHEST POTENTIAL FOR ATMOSPHERIC BENZENE
FROM SOLVENT OPERATIONS
Number
State Plants
Tires and innertubes
Connecticut 1
Kansas 2
Maryland 2
Ohio 27
Wisconsin 2
Rubber, plastic hose
California 8
Delaware 2
Kentucky 1
North Carolina 2
Tennessee 1
Rubber and plastics
Connecticut 3
Georgia 3
Rhode Island 2
Wisconsin 1
Average Number
of
of Employees
Per Plant
1,800
1,750
1,750
1,000
1,750
, and belting
750
900
750
900
750
footwear
1,200
600
900
750
Plant Size as
Average State Compared to
Density (1974) Estimated .
(People /km^) Average Plant
244
11
159
101
32
52
111
33
42
38
244
32
343
32
* See text for discussion of the estimated average plant
Source: 1972 Census
"of Manufacturing and
1975 Statistical
3x
3x
3x
2x
3x
2x
2.5x
2x
2.5x
2x
4x
2x
3x
2.5x
size.
Abstract
of the United States (Bureau of Census).
72
-------
by scaling up the estimated use at a plant of average size, based on
the comparative size factors shown in Table VII-5. Because plant
locations were unknown, average state densities were used to deter-
mine the exposed population. The dispersion modeling curve B (building
source) developed by Youngblood (1977b) was used as the basis for extra-
polation (see Chapter III, Table III-4). The population exposed to
five ranges of benzene concentrations were estimated for each plant
in a particular state. These estimates were then multiplied by the
total number of plants in the state (see Table VII-6). Note that, even
for large plants nearly all of the estimated exposure levels range
from 0.1 to 1.0 ppb.
Ambient benzene concentrations for the remaining rubber-related
manufacturing facilities were then estimated, based on the analysis
above. The 57 plants listed in Table VII-6 represent 16% of the
rubber-related manufacturing plants originally identified. Their
combined benzene consumption accounts for 35% of the estimated con-
sumption for this category (based on our earlier assumptions).
Assuming some benzene use as a solvent in all plants, it can be con-
cluded that the remaining 303 plants probably use amounts equal to or
less than the estimated average. Thus, the population exposed to
levels of 0.1 ppb and above live within 1 km of the plant (from
Table VII-4). Table VII-6 shows the results of this analysis. The
results were derived by using average 1974 state densities (Table VII-3)
to estimate the population residing within 1 km and then multiplying
that population by the plants in each state.
This same methodology can be used to determine potential exposures
in the remaining two categories: plastics materials, synthetics, and
floor covering mills. If it can be assumed that they account for 15%
of benzene consumed for solvents, the total use for these two manu-
facturing processes is estimated to be 17.0 x 10 Ib/yr (8 x 10 kg/yr).
The calculations follow: (on page 75)
7.3
-------
Table VII-6
ESTIMATED POTENTIAL POPULATION EXPOSURES
FROM
SOLVENT OPERATIONS IN RUBBER-RELATED MANUFACTURING
Population Exposed To ^
Annual Average Benzene Concentrations (ppb)
State 0.1 - 1.0 1.0 - 2.0 2.0 - 4.0 4.0 - 10.0 Total1"
Tires and Inner-
tubes
Connecticut 4,600 200 70 4,900
Kansas 400 18 6 400
Maryland 6,000 260 80 6,300
Ohio 57,600 1,000 800 59,400
Wisconsin 1,200 52 18 1,300
Rubber, plastic
hose, and belting
California 8,000 1,400 120 9,500
Delaware 4,200 80 62 4,300
Kentucky 600 12 9 600
North Carolina 1,600 30 24 1,700
Tennessee 700 14 11 700
Rubber and plastic
footwear
Connecticut
Georgia
Rhode Island
Wisconsin
Subtotal
Remaining 303
plants
Total11
20,600
1,800
13,000
600
120,900
87,000
207,900
900
36
600
12
4,600
4,600
420
27
192
9
1,800
1,800
51 22,000
1,900
13,800
600
100 127,400
87,000
100 214,400
* To convert to 8-hour worst case, multiply concentrations by 10.
To convert to yg/nr*, multiply concentrations by 3.2.
t All totals are rounded.
Source: SRI estimates, based on dispersion modeling of a building
source by Youngblood (1977b).
74
-------
Plants = 951
Average benzene consumption per
plant = 0.008 x 10 kg/yr
Emission factor = 100 x 10 kg/kg benzene consumed
Total emissions = 0.0008 x 10 kg benzene/year
Estimated emission rate = 0.025 g/s
8-hour worst case benzene concen-
tration within a 150 m radius
*
of emission source =0.9 ppb
Annual average benzene concen-
tration within 150 ra radius =0.09 ppb
* Extrapolated from dispersion modeling results of Youngblood (1977b)
usine curve for building source (see Chapter III, Table ""'
-------
Because it is not known how many plants use benzene as a solvent,
these estimates only roughly approximate actual population exposures.
Further study of solvent operations is thus warranted.
76
-------
VIII STORAGE AND DISTRIBUTION OF BENZENE
AND GASOLINE
A. Sources
Storage and distribution of benzene and gasoline represent poten-
tial sources of atmospheric benzene in the environment. There are
two main emission pathways: (1) evaporation and spills during loading
and unloading benzene and gasoline and (2) spills from collisons in
transportation.
Benzene transfers normally occur at petrochemical complexes and at
major transportation nodal points. The majority of benzene is trans-
ported by barge, with smaller amounts handled by rail and truck. The
operations involved in loading and unloading liquid benzene are
similar for barge, rail, and truck shipments. Emissions from these
sources would depend on the quantity of benzene being transferred,
the rate of transfer, the purity of the raw material, and the effi-
ciency of the transfer.
Gasoline transfers normally occur at petroleum refineries and at
numerous storage sites throughout the United States. Gasoline is
usually stored in closed containers located in remote locations. Al-
though evaporation loss from storage tanks has been observed, most
of the benzene released into the environment is believed to result
from the operations of loading and unloading the gasoline. Spills
from collisions involving gasoline transfer vehicles account for
negligible benzene losses.
B. Methodology and Exposures
1. Storage
Storage facilities consist of closed storage vessels, includ-
ing pressure, fixed-roof, floating-roof, and conservation tanks. Or-
dinary fixed-roof tanks store less volatile petroleum products, whereas
floating-roof tanks are most commonly used to store gasoline and ben-
zene. Diagrams of several of these tanks are shown in Appendix A.
77
-------
Emissions of benzene from storage in a floating-roof tank occur
primarily from standing and withdrawal (wetting) losses. Fixed-roof
tanks have "breathing" losses caused by expansion and contraction of
the vapors due to diurnal changes in atmospheric temperature. Because
of the low volume of gasoline and benzene stored in fixed-roof tanks,
breathing losses are not considered to be a significant source of
atmospheric benzene.
Limited data have been reported on benzene exposures adjacent
to storage facilities. A survey of industry reported an average of
375 ppm of benzene measured next to the sampling port on top of a
benzene storage tank (Young, 1976).
Standing emissions are caused by improper fit of the seal and
shoe to the vessel shell. Small losses also occur when vapor escapes
between the flexible membrane seal and the roof. Withdrawal or wetting
losses are caused by evaporation from the tank walls as the roof
descends during emptying operatings (PEDCo, 1977).
Emission factors of benzene as a result of these losses were
recently estimated by PEDCo (1977, p. 4-65) as follows:
3
Storage Emission Factor (kg/m )
Gasoline
Standing losses 3.3 x 10~
Withdrawal losses 2.6 x 10
Total 5.9 x 10"5
Benzene
Standing losses 1.3 x 10
-4
Withdrawal losses 8.6 x 10
Total 8.7 x 10~4
Benzene storage tanks are located near the producers and users
of the chemical and the exposure estimates for those locations have been
determined in Sections III, IV, and VII. The very small emissions re-
lated to storage losses are insignificant when compared with production
emissions.
78
-------
Gasoline bulk storage terminals, however, are generally near urban
demand centers, commonly in highly industrialized areas or on the city
periphery where population density is low.
Rough ambient benzene concentration estimates for the vicinity
of storage sites can be based on the emission factors, assumed storage
volumes, and the dispersion modeling results discussed in Chapter IV.
An average gasoline storage terminal is assumed to have the following
L:
2
3 3
characteristics: average tank size, 8.7 x 10 m ; 30-day retention time;
10 gasoline storage tanks of average size; and facility size, 0.25 km
The emission rate is calculated as follows:
(emission factor) x (tank volume) x (number of tanks) = (emission rate)
that is, (5.9 x 10"5 kg/m3) (8,7 x 1Q3 m3) (10) =5.13 kg/30 days
= 62 kg/yr
= 1.97 x 10~3 g/s
The ambient benzene concentrations can be estimated from the
dispersion modeling calculations of Youngblood (1977c) that assume
uniform emissions throughout the terminal area. By applying the es-
timated emission rate to the results presented in Table IV-4 (Chapter IV)
2
for the indicated terminal area of 0.25 km , the following estimate
can be made:
8-hr Worst-Case Exposure Levels at 300 m
1.97 x IP"3 g/s\ / 900 ug/m3 \ <
-------
petroleum refineries to the consumer may also be a significant source
of atmospheric benzene. The benzene distribution system, on the
other hand, involves much lower quantities and transfers at manufactur-
ing and consuming facilities. Because they have already been evaluated,
benzene distribution systems will not be considered in this chapter.
The U.S. gasoline distribution system is illustrated in
Figure VIII-1. Bulk terminals represent intermediate stations set up
to serve near-source regional markets. Gasoline at bulk terminals
is transferred directly from refinery by ships, rail tank cars, barges,
and pipelines. Bulk plants, on the other hand, are designed for
local markets and their supplies are distributed by tank trucks.
Service stations that fuel public motor vehicles are supplied by
tank trucks from either bulk terminals or bulk plants. Privately
owned commercial operations, such as those providing fuel for vehicles
of a company fleet, are generally supplied by tank trucks from an in-
termediate bulk installation.
Most of the emissions take place during transfers of the
gasoline to tanks and tank trucks. These losses occur at a rate directly
proportional to the amount of gasoline passing through the particular
location. Because many tank trucks are filled with one bulk terminal
or plant, benzene emissions from that procedure are potentially much
greater. As empty tank trucks are filled, hydrocarbons in the vapor
space are displaced to the atmosphere unless vapor collection facil-
ities have been provided. The quantity of hydrocarbons contained
in the displaced vapors depends on the vapor pressure, temperature,
method of tank filling, and conditions under which the truck was
previously loaded. Figure VIII-2 is a schematic drawing of liquid and
vapor flow through a typical bulk terminal.
All monitoring data collected to date have concerned possible
occupational exposures. Measurements at several bulk loading operations
in Britain showed ambient benzene concentrations ranging from 0.1 to
7.7 ppm (NIOSH, 1974). In the same study, NIOSH also evaluated worker
exposure during loading and weighing of rail tankers with gasoline
80
-------
SHIP, RAIL, BARGE
REFINERY STORAGE
PIPELINE
SERVICE STATIONS
BULK TERMINALS
TANK TRUCKS
AUTOMOBILES, TRUCKS
BULK PLANTS
TRUCKS
COMMERCIAL,
RURAL USERS
SOURCE: PEDCo, 1977
FIGURE VIII-1. THE GASOLINE MARKETING DISTRIBUTION SYSTEM
IN THE UNITED STATES
81
-------
CO
ro
J-1
PIPELINE GASOLINE
TO STORAGE
STORAGE TANK
r
_LOA[HNG VAPORS
"TO RECOVERY UNIT*
I
TERMINAL
TRANSPORT
VENT GAS
1
VAPOR
RECOVERY
UNIT
RECOVERED
GASOLINE TO
LOADING RACK
GASOLINE
SOURCE: PEDCo. 1977
FIGURE VUI-2. VAPOR AND LIQUID FLOW IN A TYPICAL BULK TERMINAL (Floating-Roof Tank)
-------
from storage tanks. An exposure equivalent to 14 ppm over an 8-hr
workday was estimated. Thus, environmental exposure to benzene from
gasoline distribution systems appears to require some evaluation.
Gasoline is loaded from storage tanks to transport trucks
(tank cars) by two basic methods: top loading and bottom loading (PEDCo,
1977). Top loading can be done by splash fill or submerged fill.
The former method involves free fall of gasoline droplets and thus
promotes evaporation and possibly liquid entrainment of these droplets
in the expelled vapors. In subsurface or submerged filling, the
gasoline is introduced below the liquid surface in the tank. Bottom
loading of gasoline is comparable to submerged top loading.
Vapor recovery systems are designed to reduce the overall
hydrocarbon emission losses (including benzene) for both loading and
unloading. For bottom loading, the vapor recovery system may achieve "
100% efficiency (PEDCo, 1977). Although it is difficult to quantify,
vapor collection for top loading is generally not so efficient as that for
bottom loading. An overall 95% efficiency of vapor recovery and contain-
ment can be assumed for both loading and unloading (PEDCo, 1977, p. 4-60).
Rough ambient benzene concentrations estimates related to gasoline
distribution can be based on emission factors, assumed transfer volumes,
and the dispersion modeling results discussed in Chapter III. Emission
factors related to the loading and unloading of gasoline were estimated
by PEDCo (1977, p. 4-65). A gasoline bulk storage terminal of the
same characteristics as described in the previous section is assumed.
In addition, continuous loading and unloading operations are assumed
over an 8-hr work day. Average retention time for each tank is 30 days.
The emission rate is calculated as follows:
Loading of Storage Tanks
(Emission factor) x (Volume Pumped/Day) x (// of Tanks) = Emission Rate
that is,
(1.1 x 10~\g/m3) (8,7 x 103 m3/30 days) (10) = 3.2 x lO^kg/day
- 1.1 x 10~2g/s
83
-------
Unloading of Storage Tanks
(1.1 x 10~5 kg/m3) (8.7 x 103 m3/30 days) (10) = 3.2 x 10~2kg/day
• 1.1 x 10~3g/s
_2
Total emission rate = 1.2 x 10 g/s
The ambient benzene concentration can be estimated from the dis-
persion modeling calculation of Youngblood (1977b) by assuming ground-
level point source emissions (Curve A). When the estimated emission rate
is applied to the results presented in Table III-4 (p. 111-10), the
following estimate can be made:
8-hr Worst-Case Exposure Levels at 300 m
1.2 x 10~2g/s\ /14,000ug/m3 \ _ 0.5 ppb
100 g/s ) I
' ^ 3.2
Approximate annual average concentration = 0.05 ppb
From this analysis, it appears that annual average concentrations,
which result from loading and unloading gasoline, are generally below
0.1 ppb within 300 m of a bulk storage terminal. Concentrations may be
higher in some cases if a large volume of gasoline (larger than the
3 3
average value used in this analysis—2.9 x 10 . m /day loaded and unloaded)
is loaded and unloaded during one 8-hr period. Thus, although occupa-
tional exposures may be high, exposures to the general public are
considered to be minimal.
84
-------
IX URBAN EXPOSURES RELATED TO AUTOMOBILE EMISSIONS
A. Sources
Urban exposures to benzene come from many sources, including chemical
manufacturing plants, automobile exhaust, gasoline service stations, gaso-
line evaporation, and losses through transportation and storage of benzene
and gasoline. However, benzene is not routinely monitored in the ambient
air, and few sampling data exist. A study by Altshuller (1969) estimated
normal benzene concentrations at between 10 and 50 ppb. These concentra-
tions appear to be quite high, however, when they are compared with other
benzene sources discussed previously. A study of atmospheric benzene and
toluene levels in Toronto found a maximum concentration of 98 ppb with an
average concentration of 13 ppb (Filar and Graydon, 1973). That study
concluded that benzene contamination of the air was related to automobile
emissions based on three factors: (1) the ratio of benzene to toluene,
(2) the presence of distinct peak periods for both hydrocarbons at rush
hour periods, and (3) the relative concentrations detected at various
sampling stations.
To determine average urban exposures throughout the United States it
is necessary to restrict the analysis. Although substantial variation
from one urban area to another occurs, it is nonetheless possible to
determine a reasonable order-of-magnitude estimate of exposures related
to two definitive sources: emission from tailpipes, and evaporation
from gasoline tanks. This analysis does not estimate urban exposures per
se, but does analyze possible ambient conditions related to automobile
emissions.
As previously discussed, the benzene content in gasolines varies
widely, with an average of approximately 1.24% by liquid volume. In
addition, catalytic converters on automobiles can reduce benzene in vehicle
exhaust by 30 to 80% (Johnson, personal communication 1977). Thus, evaporation
85
-------
from gasoline and emissions from vehicle exhaust will also vary substantially*
Dispersion modeling of these sources has been conducted by EPA. In the
Hanna-Gifford dispersion model used by Schewe of EPA (1977) concentration
depends on areawide emissions and wind speed. An empirical factor is also
applied. By applying generalized emission factors, areawide emissions were
estimated from vehicle miles traveled (the total number of miles traveled
in a given area in a year) and from the number of registered automobiles.
Table IX-1 presents the results of this study. In central cities, the
concentrations range from 1.0 ppb to 4.0 ppb, whereas in suburban areas
the concentrations are generally below 1.0 ppb.
B. Methodology and Exposures
Limited data are available concerning urban exposures from automobile
emissions. Consequently, it is difficult to develop accurate techniques
to predict benzene levels in urban areas. Uncertainties include: benzene
content in gasoline; control technology; deterioration of the control
technology over time; and dispersion characteristics of benzene under
variable meteorological conditions. Thus, a simplified model is employed
to provide general estimates of ambient concentrations.
The Hanna-Gifford dispersion model (Gifford and Hanna, 1973) as
applied by Schewe (1977) is used for this analysis. Inputs to the model
include: number of vehicle registrations, total number of vehicle miles
traveled (VMT) , area size, and average annual wind speed.
The tailpipe emissions are estimated by the following equation
(Schewe, 1977):
. , 2 0.22 g VMT _ 1 _
4tair8/S~m ' = mile s Area of study (m^) Q9>1'
The emission factor of 0.22 g benzene per mile is a composite emission
factor for 1976 (Schewe, 1977).
The evaporative emissions are calculated as follows:
C / 2) 0.148 g 3.3 trips #veh. 365 days year _1 _
8/s~m ' "
_ _
trip veh.-day 1 year 3.154 x 107 s area
(9.2)
86
-------
Table IX-1
ESTIMATES OF ANNUAL AVERAGE BENZENE CONCENTRATIONS
IN FOUR URBAN AREAS
oo
City
Dallas
City
Suburbs
Los Angeles
City
Suburbs
St. Louis
City
Suburbs
Chicago
City
Suburbs
10
Vehicle
Miles
Traveled
6.14
5.36
10.2
21.5
2.86
7.71
18.8
23.5
Registered
Automobiles
619,684
540,786
2,044,203
4,299,073
378,280
1,020,219
1,860,292
2,327,206
Land Area
(108 m2)
6.9
43.0
12.0
54.0
1.6
61.0
5.8
88.0
evap
(10-92
g/s m )
5.08
.719
9.63
4.53
13.5
.944
18.2
1.49
Qtail
(10-92
g/s m
62.2
8.80
59.3
28.0
126.0
8.80
227.0
18.6
QT
(10-92
g/s m )
67.3
9.52
68.9
32.5
140.0
9.74
245.0
20.1
Average
Annual Wind Benzene
Speed (m/s) (yg/tn3)
5 3.03
0.43
2 7.75
3.66
4 7.88
0.55
4 13.78
1.13
Concentration
(ppb)
.95
.13
2.4
1.1
2.5
.17
4.3
.35
1976 projections
O = Evaporative emissions from automobiles.
evap
Qtail
Tailpipe emissions from automobiles.
= Total automobile emissions
Source: Schewe, 1977
-------
By multiplying the constants in this equation we get the following:
2 5.653 x 10"6 j // veh.
(g/B-ffl ) = ^
Q
evap
veh. s
area of study
(9.3)
This technique assumes that each vehicle emits 0.148 g of benzene per trip
and that the average vehicle travels 3.3 trips per day (Schewe, 1977).
The total emissions for automobiles can be expressed as follows:
(9.4)
Equation (9.4) is essentially the summation of Equations (9.1) and (9.3).
V Qtail-
To calculate the average annual areawide benzene concentration,
Equation (9.5) is used:
= 225 QT
XA " u (ra/s)
(9.5)
The average annual wind speed, u, in the area of study was obtained from
Figure IX-1. Because wind speed (and thus dispersion) increases in the
afternoon, the morning values were used to estimate higher concentrations.
The number 225 is an empirical factor derived from several studies that
gave very good results for long-term averages; it applies to light-duty
vehicles such as passenger cars.
Source: EPA, 1971
FIGURE IX-1. ISOPLETHS (m/sec) OF MEAN ANNUAL WIND SPEED THROUGH THE
MORNING MIXING LAYER
88
-------
Because of the general unavailability of 1976 data for all urban
areas, 1973 data were used as much as possible in this estimation. Com-
parisons of 1973 with 1976 data indicated that the change was less than
3% and had a negligible effect on the final results. The following data
sources were used:
• 1973 Standard Metropolitan Statistical Area (SMSA) and
county populations—U.S. Bureau of the Census, 1976,
Series P-25, No. 618.
1973 SMSA and county automobile registrations—U.S.
Department of Transportation, Federal Highway Administration,
1974, Table MV-21.
Average annual vehicle miles traveled by size of SMSA—
Federal Highway Administration, 1972, Nationwide Personal
Transportation Study, Report No. 2, Table 9.
Average annual wind speed—EPA, 1972, Publication No. AP-101.
SMSA, county and city land areas—Bureau of the Census, 1972
County and City Data Book.
A detailed analysis was conducted for the six largest cities in the U.S.
(populations of more than 1 million). Table IX-2 presents the results.
Because input data were slightly different, the results differ somewhat
from those shown in Table IX-1. For example, the suburban area used in
this estimate may include a larger area than that used in the Schewe
estimates. Suburban areas aretdefined as those areas outside the central
city but within the SMSA. Because no VMT and registration data were
available at the city level, they were extrapolated either from SMSA data
or county data and were based on the fraction of the population residing
in each area. The results show that the estimated benzene concentrations
in city and suburban areas range from 0.7 to 2.7 ppb and 0.2 and 1.5 ppb,
respectively. The composite benzene concentrations in the six correspond-
ing SMSAs ranged from 0.5 to 2.0 ppb.
It is expected that people living in urban areas are exposed to higher
levels of benzene from automotive emissions than those living in rural
areas. Consequently, our approach was designed to maximize the urban pop-
ulation considered in the analysis. Although 43% of the total urban
population resides in central cities (as defined by the Bureau of the Census),
83% of the total urban population resides in SMSAs. Thus, a greater
89
-------
Table IX-2
ESTIMATES OP AVERAGE ANNUAL BENZENE CONCENTRATIONS
FOR CITIES WITH POPULATIONS EXCEEDING 1,000,000
VO
o
Cltv
Chicago
Detroit
Houston
Los Angeles
New York
Philadelphia
SMSA
Population
103
6,999.8
4,446.3
2,163.4
6,938.3
9,746.4
4,826.3
City
Population
103
3,173
1,387
1,320
2,747
7,647
1,862
City
Area
109»2
0.57
0.35
1.1
1.2
0.77
0.33
Automobile
Registration
1,324,171
675,065
701.766
1,490,483
1.707,891
944,660
VMT/
vehicle
103
11.5
11.5
14.0
11.5
11.5
11.5
virr
1.5
0.77
0.98
1.7
1.9
1.0
u
(m/s)
5
6
6
3
7
6
Qtall
1.8
1.5
0.63
0.98
1.7
2.0
Qevap
10~8
«/»-•*
1.3
1.0
0.36
0.67
1.2
1.5
1.9
1.6
0.66
1.0
1.8
2.1
Benzene
Central City
yg/» ppb
8.6 2.7
6.0
2.5
7.5
5.9
8.0
1.8
0.7
2.3
1.8
2.5
Concentration
Suburban
1.1
1.2
0.23
0.4
0.3
1.5
Composite
. ppb
1.9
1.5
0.5
1.3
1.0
2.0
Source: SRI estimates based on Hanna-Glfford oodel as applied by Schewe (1977);
data sources listed In text.
-------
percentage of the urban population is captured by using SMSAs as study
areas. The six largest cities are in SMSAs with more than 2 million
population. To analyze the remaining SMSAs, the following population
size categories were employed (U.S. Bureau of the Census, 1976, Series
P-25, No. 618):
SMSA Population Size Category Number of Areas
2,000,000 or more 15
1,000,000 - 2,000,000 20
500,000 - 1,000,000 37
250,000 - 500,000 63
less than 250,000 124
SMSA composite benzene concentrations were estimated for seven areas
that represent four population size categories (see Table IX-3). For SMSAs
with population exceeding 500,000, the composite average annual benzene
concentrations ranged between 0.1 and 0.4 ppb. However, SMSAs of less
than 500,000 were below 0.1 ppb. It may be assumed from this analysis
that the SMSAs with population less than 500,000 have average annual
benzene concentrations less than 0.1 ppb.
The estimates of urban exposures from automobile emissions are order-
of-magnitude estimates that are based on a simple dispersion model. Note
that, in certain locations and under certain meteorological conditions,
benzene concentrations may be a factor of 10 higher than those listed.
In addition, central city areas (as shown in Table IX-2) may have consis-
tently higher levels than surrounding areas because of traffic density,
frequency of intersections, and street density. Because the model only
includes automobile emissions, areas with substantial commercial or bus
transportation may have higher levels than estimated. Also, the model
is extremely sensitive to area size as Table IX-2 indicates. Thus, com-
posite SMSA benzene concentrations provide the most reasonable estimate
of the average annual exposures for .an urbanized area.
The total estimated urban population exposed to benzene in concen-
trations greater than 0.1 ppb from automobile emissions is shown in
Table IX-4. The 1974 SMSA populations for Chicago, Detroit, Los Angeles,
91
-------
vO
Ni
Table IX-3
ESTIMATES OF AVERAGE ANNUAL BENZENE CONCENTRATIONS FOR SELECTED SMSAs
SMSA
SMS As
Pittsburgh
San Francisco
SMS As
Columbus
Milwaukee
SMS As
Sacramento
Providence-
Warwick-
Pawtucket
SMS As
Wichita
Harrisburg
2
Population Area (m )
>2, 000, 000
2,333,600
3,135,900
1,000,000
1,055,900
1,423,200
500,000
851,300
854,400
250,000
375,600
425,500
7.8 x 109
6.2 x 109
- 2,000,000
6.2 x 109
3.7 x 109
- 1,000,000
8.7 x 109
2.4 x 109
- 500,000
6.2 x 109
4.1 x 109
VMT/
Automobile vehicle VMT
Registration 10 10
2,358
688
567
642
439
869
221
198
,600
,300
,803
,531
,803
,100
,715
,997
11.3
11.5
11.3
11.3
11.3
11.3
10.3
10.3
26.0
7.7
6.4
7.2
4.9
9.8
2.3
2.0
u
m/s
5
3
5
5
3
7
7
5
Qtail
10-9 2
g/s-m
23.0
8.5
7.2
13.0
3.9
28.0
2.5
3.4
evap
g/s-m
17.0
6.2
5.1
9.8
2.8
20.0
2.0
2.7
QT
-9
g/s-m
25.0
9.1
7.8
14.0
4.2
30.0
2.7
3.7
Benzene
Concentration
yg/m2
1.1
.68
.35
.62
0.3
0.9
.08
.16
ppb
.4
.2
.1
.2
0.1
0.3
<0 1
<0.1
Source: SRI estimates using Hanna-Gifford dispersion model
as applied by Schewe (1977).
-------
New York, and Philadelphia were summed to estimate the population exposed
to average annual benzene concentrations of 1.1 to 2.0 ppb. The 1974 SMSA
population of Houston plus the remainder residing in SMSAs with populations
greater than 500,000 were summed to estimate the total population exposed
to average annual benzene concentrations between 0.1 and 1.0 ppb. The
results indicate that 114 million people, or 73% of the total SMSA popula-
tion, are exposed to average annual benzene concentrations greater than
0.1 ppb.
Table IX-4
URBAN POPULATION EXPOSURES RELATED TO AUTOMOTIVE EMISSIONS
Annual Average
Benzene Concentration
(ppb)*
Source 0.1 - 1.0 1.1 - 2.0 Total
Automotive Emissions 68,337,000 45,353,000 113,690,000
To convert to yg/m , multiply concentrations by 3.2.
Source: SRI estimates
93
-------
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99
-------
APPENDIX A
Diagrams of Various Benzene-Related Operations
101
-------
EMISSIONS
A. C;A. P;?TS
J CO.;E.S::£ :?:-:
STA'OPIPE CAPS
COLLCCTC3 FiAIM
CAR
WASTE GAS
STACK
Source: PEDCo. 1977
FIGURE A-1. SCHEMATIC DIAGRAM OF BY-PRODUCT COKE OVEN SHOWING POSSIBLE
ATMOSPHERIC EMISSION SOURCES FOR BENZENE
-------
AMBIENT
EMISSIONS
NIXED,
ACID
'
BENZENE
1
'
DC
LU
CO
O£
O
«
j
i
i
< —
•«
NITRATOR
^ TO ANILINE
-AIR CRUDE
NITROBENZENE
i
oc
a.
PRODUCTION
WATER, DILUTE
SODIUM CARBONATE
i
Uftrurn
>* HnoncK
1
WASH-WATER
1 WASTE
SPEND ACID
TO RECOVERY
*"
1
:z>
o
0
I
NITROBENZENE
(REFINED)
r
WASTE
Source: PEOCo. 1977
FIGURE A-2. FLOW CHART FOR NITROBENZENE MANUFACTURE FROM BENZENE
AND NITRIC ACID
-------
ETHYLENE^
e
>•
L
Q
BENZENE
RECYCLE-*
AND FRESH
f
OFF-GAS
— crniinntur
* jLKUUUlnu
SYSTEM
1
1 CO"DENSEI1 1 BErmnir nccrcic
TO REACTOR ETHYLBENZENE
_L T 7 J_T
* . ^ fc WATER HASH . CAUSTIC WASH ,„ £ ±
J- fc AND SETTLER AND SETTLER " gf «z ?^z
' —i— SS 5o "*" ^m^
j ^^ ^o
ALUMINUM k "
— rmnRinp
COMPLEX J
HEAVY
(POLYETHYL) BENZENES
AND TAR
. RECYCLE (POLYETHYL JBENZENES
v*H» T C«WT""~"^^'C— "evnHe
DO £ * D9c3
Source: PEDCo, 1977
FIGURE A-3. FLOW CHART FOR ETHYLBENZENE MANUFACTURE FROM BENZENE AND ETHYLENE
-------
AIR,
BENZENE
MIXER
FUSED
Cfll T
COOLER
rnuvcoTto
uunrtKi tn
ABSOKHLRo
i
1
COOLER
v.n.
x z
5 °
1
MALE 1C
ANHYDRIDE
4 1/2
CHCO
2H20
MASTC
Source: PEDCo, 1977
FIGURE A-4. FLOW CHART FOR THE MANUFACTURE OF MALEIC ANHYDRIDE BY
CATALYTIC VAPOR-PHASE OXIDATION OF BENZENE
-------
on
o
os
UJ
tvl
o.
o
COMBINED
FEED DRUM
CONDENSER
Ixl
Ul
CO
FRESH PROPYLENE PROPANE
PROPANE
FRESH
BENZENE
CONDENSER
CUMENE
BOTTOMS
CONDENSER
CUMENE
PHOSPHORIC
CfiH, + CH,CH • CH,
663 Z
SOLID
^,K,
6 5 3
Source: PEDCo. 1977
FIGURE A-5. PROCESS FOR THE MANUFACTURE OF CUMENE
-------
o
CO
CUMENE-
HYDROGEH-
IHPURE CUHENE RECYCLE
HYDROGENATOR
-EMULSIFIERS
AtR-
SULFUR1C ACID
V
— »
f
OXIDIZER
ACIDIFIER
-*
SEPAR
RECYCLE ACID i
ATOR
CH6H5(CH3)
OOH— H:
ACETONE
PS
VI
if
O _l
««: o
I »PHENOL
OOH
) CO
ACETOPHENONE
Source: PEDCo, 1977
FIGURE A-6. FLOW DIAGRAM FOR THE MANUFACTURE OF PHENOL BY THE
CUMENE PEROXIDATION PROCESS
-------
BENZENE OR
CHLOROBENZENE
HYDROCHLORIC ACID.
WATER
BENZENE,
CHLORINE.
CHLORINATOR
o
vo
HI
CO
VENT
at
eo
SODIUM
HYDROXIDE
I
CHLOROBENZENE
i
HYDROCHLORIC
ACID ^
NEUTRALIZING
TANK
HC1
HC1
SETTLING.
TANK
o
-^DICHLORO- AND
POLYCHLOROBENZENES
TO DISTILLATION
DICHLOROBENZENE
SLUDGE TO RECOVERY
Source: PEDCo. 1977
FIGURE A-7. FLOW DIAGRAM FOR THE MANUFACTURE OF CHLOROBENZENE AND
BY-PRODUCT DICHLOROBENZENES
-------
RECOVERABLE
SOLVENT
MIXTURE
\
SETTLING
TANK
SLUDGE
pDCUCfiTFP
r nCnLM 1 Cr\
'
»,
J-
UIUJ 1
^^
tt_ ^J
ii*-
(/) O
gl
^Sg
-Jof-
fegS
2§
I
SODIUM CARBONATE n 1
STEAM
DEHYDRATING
TANK
i
CONDENSATE HA^ER
* TO
SEWER
BOTTOMS
"WATER OUT
-WATER IN
PRODUCT
Source: PEDCo, 1977
FIGURE A-8. TYPICAL SOLVENT RE-REFINING INSTALLATION
110
-------
• PRESSURE-VACUUM
VENT
GAUGE HATCH,
MANHOLE
t
LIQUID LEVEL
MANHOLE
\
tt
Source: PEDCo, 1977
FIGURE A-9. FIXED-ROOF STORAGE TANK
•EATHER SHIELD LIQUID LEVEL DRAIN
HATCHES
VENT
ROOF SEAL
(NONMETALLIC
OR
METALLIC)
HINGED CENTER SUPPORT
Source: PEDCo, 1977
FIGURE A-10. DOUBLE-DECK FLOATING-ROOF STORAGE TANK
(Nonmetallic Seal)
111
-------
ROOF CENTER SUPPORT
FLEXIBLE DIAPHRAGM ROOF
GAUGE HATCH
ROOF SEAL
(LIQUID IN TROUGH)
Source: PEDCo, 1977
FIGURE A-11. VARIABLE VAPOR SPACE STORAGE TANK
(Wet-Seal Lifter Type)
112
-------
APPENDIX B
Emission Rates and Population Exposures
from
Chemical Manufacturing Facilities
113
-------
Table B-1
EMISSION RATES FROM DIFFERENT CHEMICALS IN EACH PLANT USING BENZENE
ESTIMATED EMISSION RATE, JANUARY 1, 1976 (millions of kg per year)
STATE
ALABAMA
LOCATION COMPANY
TUSCALOOSA REICHHOLD CHEM.. INC
CALIFORNIA CARSON WITCO CHEM
EL SEGUNDO STO. OIL CO. OF CALIF.
IRWINDALE SPECIALTY ORGANICS. INC
RICHMOND STO. OIL CO. OF CALIF.
SANTA FE SPRINGS FERRO CORP.
DELAWARE DELAWARE CITY STO. CHLORINE CHEM CO.. INC.
GEORGIA CARTERSVILLE CHEM. PRODUCTS CORP
ILLINOIS BLUE ISLAND CLARK OIL » REFINING
CICERO KOPPERS CO. INC.
MORRIS REICHHOLD CHEM. INC.
SAUGET MONSANTO
KANSAS EL DORADO SKELLV OIL CO.
KENTUCKY ASHLAND ASHLAND OIL. INC.
BENZENE
ANILINE
I
1
ETHYL
BENICNE
I
1
0.031
LOUISIANA BATON ROUGE FOSTER GRANT CO. 1
CORVILLE COSJJAH. INC. 1
CHALMETTE TENNECO. INC.
GEISMAR RUBICON CHEM.. INC.
PLAOUEMINE GEORGIA PACIFIC CORP.
WELCOME GULF OIL CORP.
0.238
MARYLAND BALTIMORE CONTINENTAL OIL CO. 1
MASSACHUSETTS MALDEN SOLVENT CHEM. CO.. INC 1
MICHIGAN MIDLAND DOW CHEMICAL 1
MISSISSIPPI PASCAGOULA FIRST MISSISSIPPI CORP.
MISSOURI ST. LOUIS MONSANTO
0.427
NEVADA HENDERSON MONTROSE CHEM.CORP. OF CAL. 1
NEW JERSEY BOUND BROOK AMERICAN CYANAMID
BOUND BROOK UNION CARBIDE
ELIZABETH REICHHOLD CHEM.. INC.
FORDS TENNCCO. INC.
GIBBSTOWN E. 1. du PONT
KEARNY STO. CHLORINE CHEM. CO
WESTVILLE TEXACO. INC
0.266
0.637
0.272
0202
0.070
0.155
0.155
1
MALEIC
STYRENE UNHYDRAT
0.483
2.610
1
CUMENE
0.011
PHENOL
0.068
MONO-
CHLOHO
BENZENE
0.025
1 0.119
0.012
0.015
0.040
0.558
0.409 !
0.357
0.273
:
i
4.641
1.353
1.160
0.001
0.029
0.04O
t
0.183
0.043
0.120
0.018
0.068
DICHLORO
BENZENE
(O- and P-
O.OBO
0.232
0.066
0.111
0.476
I
0008
0.249
CYCLO
HEXANE
0.1,2 ,
(-
0.060
DETERGE
ALKYLAT
ILinM
0.055
0.220
0.215
TOTAL
EMISSION
RATE
0.066
0.055
0.011
0.060
0.24!
0.351
O.OB6
Oj052
0.4S3
2.610
0.324
O.OSB
0.040
0.830
0.611
0.070
0.238
0.120
0.512
0.215
0AM
1.172
0.427
4.B41
0.111
0.268
O.OBB
1.353
1.180
OJ37
OJOtO
0.029
-------
Table B-1 (Continued)
STATE
NEW YORK
•
OHIO
PENNSYLVANIA
PUERTO RICO
TEXAS
LOCATION
NIAGARA FALLS
NIAGARA FALLS
WAGARA FALLS
SYRACUSE
HAVERHILL
BEAVER VALLEY
BR1DCEVILLE
CLAIRTON
FRANICFORD
NEVILLE ISLAND
PHILADELPHIA
GUAYAMA
PENVELAS
PENUELAS
• AYTOHN
BEAUMONT
BEAUMONT
BIG SPRING
BORGER
CHOCOLATE BAYOU
CORPUS CHHISTI
CORPUS CHHISTI
CORPUS CHFtiSTI
FREEPOHT
HOUSTON
HOUSTON
HOUSTON
HOUSTON
HOUSTON
ODESSA
OYSTER CREEK
PHILLIPS
PORT ARTHUR
PORT ARTHUR
PORT ARTHUR
SEADRIFT
SWEENEY
COMPANY
ICC INDUSTRIES. INC.
OCCIDENTAL PETROLEUM
SOLVENT CHEM. CO.
ALLIED CHEM. CORP.
UNITED STATES STEEL
AFtCO/POLYMEHS. INC.
•COPPERS CO.. INC.
UNITED STATES STEEL
ALLIED CHEMICAL CORP.
UNITED STATES STEEL
GULF OIL CORP.
PHILLIPS PETROLEUM
COMMONWEALTH OIL
UNION CARBIDE CORP
EXXON CORP
E. 1. Chi PONT
UNION OIL CO. OF CALIFORNIA
AMERICAN PETROFINA
PHILLIPS PETROLEUM
MONSANTO
COASTAL STATES GAS
SUN OIL CO.
UNtON PACIFIC CORP
DOM CHEMICAL
AHCO/POLYMERS. INC.
THE CHARTER CO.
XX OIL. INC.
THE MERICHEM CO.
PETHO-TEX CHEM CORP.
EL PASO NATURAL GAS
DOW CHEMICAL
PHILLIPS PETROLEUM CO.
ARCOIPOLVMERS . INC.
GULF OIL COFIP
TEXACO
UNION CARIIOE CORP
PHILLIPS PETROLtUM CO.
NITRO-
BENZENE ANILINE
ETHYL
BENZENE
STYRENE
;
0.9B7
0.300
MALEIC
ANHYDRATE
1.450
CUMENE
PHENOL
0.090
;
i
1.740
0.04S
I
0.012
O.026
O.525
0.037
0.009
0.060
0.054
1.009
O.O67
1
OLO77
0.124
0098
O.1D7
0.7O4
0.250
0.051
0.072
1
2.224
0.073
0.01C
00»
O.OSI
0.090
0.237
MONO-
CHLORO-
BENZENE
Oj024
0.036
DICHLORO-
BENZENE
(O- and P.|
a077
O.077
CYCLO -
HEXANE
0.112
'•• 0.374
0.585
0.330
0.330
0,380
OJM
OJ30
0.1S2
(LDBO
0.703
DETERGENT
ALKYLATE
[|)|>|g| y^J
Branch)
0.224
TOTAL
EMISSION
HATE
0.024
0.070
0.115
0.010
OJOO
1.460
0.250
1.740
0.325
0.585
0.375
«,1«2
0^330
0.9«7
0.260
0.170
0.1»
0.524
0.016
0.108
0.1B2
1334
OXB*
ojon
2.734
0.17*
o.in
0.134
ami
ao«
OJOO
0.103
-------
Table B-1 (Concluded)
STATE
TEKAS
WEST VIRGINIA
WASHINGTON
LOCATION
TEXAS CITY
TEXAS CITY
TEXAS CITY
CHARLESTON
FOLLAKSBEE
MOUNDSVPLIE
NATRIUM
NEW MARTINSVILLE
WIILOW ISLAND
AN* CORTES
KALAMA
COMPANY
MARATHON OIL CO.
MONSANTO
STANDARD Olt IINDIANAI
UNION CARBIDE CORP
KOBPEHS CO., INC.
ALLIED CHFM CORP.
PPG INDUSTRIES. INC.
MO6AY CHEW CORP.
AMERICAN CYANAMIOE
STIMSON LUMBER CO.
KALAMA CHEMICAL
NITROGEN
ANILINE
|
f
O.ITS
o.m
0.1 88
ETHYL-
BENZENE
O.B99
0.266
STYRENE
0.885
O.S73
MALEIC
AN HYDRATE
0.361
CUMNE
D.07I
0.007
PHENOL
N.A.
O.OB
MONO
CHLORO-
BEN2ENE
0.143
DICHLORO.
BENZENE
<0- m '•>
0.197
CYCLO.
HEXANE
DETERGENT
ALKYLATE
ILMWW wid
Br«nch)
O.I 49
TOTAL
EMISSION
RATE
0.021
l.TM
0.946
0.149
0.436
OL340
0477
0.189
O.TOS
N>. - NOT AVAILABLE
SOURCE SRI ESTIMATES
-------
Table B-2
ESTIMATED ANNUM. AVERAGE EXPOSURES
FROM CHEMICAL MANUFACTURING FACILITIES
OO
State
Alabama
California
Delaware
Georgia
Illinois
Kansas
Kentucky
Louisiana
Maryland
Massachusetts
Michigan
Mississippi
Missouri
Nevada
New Jersey
New York
Ohio
Pennsylvania
Location
Tusc.iloosa
Carson
El Ser.undo
Irvlndale
Richmond
SnnLa Fe Springs
Delaware City
Cartersvllle
Blue Island
Clrcro
MorrJs
Snnr.rt
F.I Dorado
Ashland
Baton Rouge
Corvllle
Clnlmotte
Gelsmnr
Plmtucmlne
Welcome
Baltimore
Maiden
Midland
Pnsr.-lRnula
St. Louis
Henderson
Bound Rrook
Bound Brook
El I'.ihPth
Fords
Glbbstown
Ke.lrny
Uestvllle
Nl.-igara Falls'
Niagara Falls
Niagara Falls
Syracuse
H.-IVI rhlll
Beaver Valley
Bridgevllle
Cl.llrtnn
Frankford
Neville Island
Philadelphia
Total
Benzene
Emission
R.ue
Company 10f Kg/yr
Relchhold Chem., Inc.
Witco Chem.
Std. Oil Co. of Calif.
Specialty Organ Ics
Std. Oil Co. of Calif.
Ferro Corp.
Std. Chlorine Chemical
Co., Inc.
Chem. Products Corp
Clark Oil & Refining
Koppers Co., Inc.
Kelchhold Them., Inc.
Monsanto
Skelly Oil Co.
Ashland Oil, Inc.
Foster Grant Co.
Cos-Mar, Inc.
Tenneco, Inc.
Ruhlron Chen. Inc.
Georgia Pacific Corp.
Gulf Oil Corp.
Continental Oil Co.
Solvent Chen. Co., Inc.
Dow Chemical
First Mississippi Corp.
Monsanto
Mont rose Chem. Corp. of
California
American Cyanamld
Union Carbide
Relchhold Chem.
'I'unuuco. Inc.
E. I. du Pont
Std. Chlorine Chen. Co.
Texaco, Inc.
ICC Industries, Inc.
Occidental Petroleun
Solvent Chen. Co.
Allied Chem. Corp.
United States Steel
Arco/Polymers, Inc.
Koppers Co. , Inc.
United States Steel
Ailed Chemical Corp.
United States Steel
Uilf Oil Corp.
0.068
0.055
0.011
0.008
0.245
N.A.
0.351
0.086
0.052
0.4H3
2.610
0.324
0.058
0.040
0.830
0.611
0.07
0.238
0.120
0.512
0.215
0.008
1.172
0.427
4.641
0.112
0.266
0.068
1.153
1.16O
0.637
0.060
0.029
N.A.
0.024
0.07
0.115
0.09
0.300
1.450
N.A.
0.250
1.740
0.325
**
Population F.xposed to Bpiizcne (ppM •
0.1-1.0
62,700
10,700
14,900
800
78,200
76,200
10,900
12,500
84 , 300
58,000*
49,200
11,800
26,800
50,100*
37,100*
18,700
13,200
10,400
37,100
800,400
18,300
65,400*
21,000
4,400*
18,000
245,300
386.100*
400,300*
434,500
48,200
9,000
80,500
183,100
11,400
58.300
104,100*
45,600
97,700*
1,681,200
1.1-2.0
2,000
4,300
400
t
11,800
. 2,200
700
400
2,400
23,400
1,400
400
1,500
102,500
1,300
500
400
1,100
1,100
46,500
500
6,200
18,600
17,400
1,000
7,000
46,000
37,400
16,600
2,900
MO
8,400
13,200
300
1,700
13.900
1,300
17,800
106,700
2.1-4.0
BOO
1.7OO
200
t
4.600
1,300
300
100
29,600
9,200
500
200
600
40,200
500
200
100
400
400
18,200
200
21,500
7,300
6,800
400
2,700
18,000
14 , 700
6.500
1,100
100
3,300
5,200
100
600
5.400
500
7.0OO
41,800
4.1-10.0 >10.0
400
BOO
100
t
2.100
800
100
too
24,900
6.40O
300
100
300
18,400
400
100
100
200
200
8,300
100
10,100
3,300
348,600
200
1,200
73.1OO
6,700
3,000
500
It
1,500
2,400
100
300
5.000
200
3,200
19,100
100*
300
i +
*
900
300
100
**
10,200
5,200
100
tt
100
7,500
700
* +
* +
100
100
3,400
*«
4,100
1.400
190.200
100
500
34.100
2,700
1.200
200
* +
600
1,000
tt
100
2,300
100
2,400
7,800
Total
66.000
17,»00
15.600
800
97,600
80,800
12,100
13.100
151, iOO
102. 200
51,500
12,500
29,300
218,700
40.000
19,500
13,800
12,200
33.900
876,800
19,100
107, JOO
51.600
576,400
19.700
256.700
557. VK1
461,800
461,800
52,900
9.400
94.300
204.900
11.900
61,000
130.700
47.700
128, IOO
1.856.600
-------
Table B-2 (Concluded)
State
Puerto Rico
Texas
West Virginia
Washington
Location
Giayam.1
P'-rvn-lns
P. nu. las
B.iytown
Beaumont
Bc-.iumont
8 IK Spring
Bor;;t-r
Chocolate fiayou
Corpus Christl
Corpus Christl
Corpus Christl
Freeport
Huuston
Houston
Houston
Houston
Houston
Odessa
Oyster Creek
Pl.illips
Port Arthur
Port Arthur
Port Arthur
Seadrlft
Sweeney
Texas City
Texas City
Texas City
Charleston
Follunsbee
Moundsvillo
N;it r itim
New Hartlnsville
Willow Island
Anacortes
(C.il .irn.i
Conpany
Phillips Petroleum
Commonweal th Oil
Union Carbide Corp
Exxon Corp
E. 1. duPont
Union Oil Co. of Calif.
American Petroflna
Phillips Petroleum
Monsanto
Cnast.il Statos Gas
Sun Oil Co.
Union Pacific Corp
Dov Chemical
Arco/Folyners
The Charter Co.
Joe Oil, Inc.
The Merlcheia Co.
Pei.ro -Tex Chemical
El Paso Natural Cas
Dow Chemical
Phillips Petroleum Co.
Arco/Pol ymers
Gulf Oil Corp
Texaco
Union Carbide Corp
Phillips Petroleum Co.
Marathon Oil Co.
Monsanto
Standard Oil (Ind.)
Union Carbide Corp
Koppers Co. , Inc.
Allied Chemical
PPC Intliiiitrlcx, Inc.
Hobay Chemical
American Cyanamide
Stimson Lumber Co.
Kalana Chemical
Total
.Benzene
Emission
Rate
106 KE/yr
0.585
0.375
0.162
0.330
0.987
0.280
0.170
0.330
0.524
0.016
0.108
0.182
1.534
0.094
0.009
N.A.
N.A.
2.224
0.179
0.182
N.A.
0.124
0.051
0.050
0.300
0.703
0.021
1.784
0.846
0.149
N.A.
0.436
0.340
0.427
0.189
N.A.
0.025
TOTAL
Population** Exposed to Benzene (ppb)***
0.1-1.0
401,500
404,000
805,500
10,900
17,700*
22,000
17,500
19,900*
9,800
16,800*
399,500*
60,200
4,900
48,600
9,600
19,400*
12 ,400*
61,400
29,400
19,000
25,800.
8,600
1,200
7,496,500
1.1-2.0
13,000
12,000
25,000
300
69,200
6,600
4,300
600
12,500
2,500
285,600
13,400
100
5,100
300
900
5,200
6,400
6,300
500
3,000
200
100
944,600
2.1-4.0
5,300
4,700
10,000
100
28,400
2,600
1,700
200
5,200-
2,800
111,900
5,200
100
2,000
200
500
21,800
2,500
2,500
200
2,400
100
100
452, BOO
4.1-10.0
2,400
2,100
4,500
100
13.000
1,200
800
100
2,400
6,200
51,200
2,400
tt
900
700
2,100
12,500
1,200
1,100
100
1,100
tt
tt
644,800
>10.0
1,000
900
1,700
tt
5,300
500
300
tt
1,000
2,500
20,900
1,000
tt
400
300
900
5,100
500
500
tt
400
tt
tt
319,400
Total
423.200
423,700
846,700
11,400
133.600
32,900
24,600
20,800
30,900
30,800
1,369,100
82,200
5.100
57,000
11,100
23,800
57,000
72,000
39,800
19,800
32,700
8,900
1,400
9,882,600
*Socie population may be exposed to levels above 0.1 ppb beyond 20 km.
••Population and density Information vere obtained fro* the Statistical Abstract-1975
and the 1972 City and County Data Book, both published by the Bureau of Census.
***To convert to l.g/m' multiply by 3.2.
^Estimated benzene concentration at the location with more than one plant; the estimated
concentration is the turn of individual concentration estimated from each plant.
*Less than 50 people exposed.
Source: SRI estimates
-------
APPENDIX C
Population Exposures from Coke Oven Operations by Location
121
-------
COKE PLANT LOCATIONS, CAPACITIES. POPULATION, EMISSION RATE AMD
AREA AVERAGE CONCENTRATION OF BENZENE
State, City
Alabao*
1. Tarrant
2. Holt
3. Von-tward
4. Cacfsdcn
3. Thi-as
6. llrmlnghasi
7. Falrfleld
California
B. Fontansj
9. Pueblo
Illinois
10. Granite City
11. Chicago
12. Chicago
11. South Chicago
li. Chesterton
1*>. In'Ji-vMpxIls
!*• Terre Haute
17. r. '.hI-:-T*o
If. tast Chicago
19. Csry
2'). Indiana Harbor
Plant Name
Tarrant Plant
Holt Plant
Wcodvard Plant
Cadfiden Plant
Thomas Plant
Birmingham Plant
Fairfleld Plant
Fcntana Plant
Pueblo Plant*
Tranlte City Steel Dlv.
Chlc.i;o Plant
Wisconsin Steel Works
South Chicago Plant
Burns Harbor Plant
Prospt-ct Street Plant
Terre Haute Plant
Pl.int No. 2
Pl.int No. 3
Gary Plant
Indiana Harbor Pl.int
Company
Alabana By-Products Co.
Empire Coke Co.
Koppers Company. Inc.
Republic Steel Corp.
Republic Steel Corp.
U.S. Pipe and Foundry Co.
D.S. Steel Corp.
Kaiser Steel Corp.
CF&I Steel Corp.
National Steel Corp.
Interlake, Inc.
International Harvester Co.,
Wisconsin Steel- Dlv.
Republic Steel Corp.
Bethlehem Steel Corp.
Citizens Cas t Coke Utility
Indiana Gas and Chemical' Corp.
Inland Steel Co.
Inland Steel Co.
U.S. Steel Corp.
Youngstown Sheet and Tube Co.
Annual Coal
Capacity
(tons)
1,200,000
150,000
800,000
820.000
185.000
1,175,000
2,500,000
2.336.000
1,332,000
1,132.000
949,000
991.000
590.000
2,630.000
675.000
204.000
3.102.000
1,642,000
3,700.000
2.100.000
Emission
Rate
(g/sec)
1.572
0.196
1.048
1.074
0.242
1.539
3.275
3.060
1.744
1.482
1.743
1.298
0.772
3.445
0.884
0.267
4.063T
2.151
4.847
2.751
Population
0.1-1.0
130,509
101.935
56.954
2.188
153,888
377,213
222.300
79.609
313,798
2.828
220,088
89,582
287.163
3,571
572,452
388.319
733.369
Exposed to Benzene (ppb)t+
1.1-2.0 2.1-4.0 4.1-10
388
478
975
22,105
1.416
827
21,279 53
26,829 33
482 99
S-»irce: SRT ritt-wtm.
-------
Table C-l (Continued)
K>
State, City
36. Portsmouth
37. Toledo
38. Cleveland
39. Hassilon
40. Warren
41. Ycungstoun
42. Lrratn
41. Ca-pbell .
Pennsylvania
44. Swede land
45. Bethlehea
46. Johnstown
47. Jchnsiovn
48. Midland
49. Aliquippa
50. Pittsburgh
51. Erie
52. Philadelphia
53. Pittsburgh
54. Clalrton
55. Falrless Hills
56. Monessen
Tennessee
57. Chattanooga
Ttxas
58. Houston
Vt. Lone Star
•tab
60. Prove
Plant Nane
Empire
Toledo Plant*
Cleveland Plant
Hassilon Plant
Warren Plant
Youngstoun Plant
Lorain Cuyahoga Works
Campbell Plant
Alan Wood Plant
Bethlehem Plant*
Rosedale Dlv.
F rank 1 In Dlv.
Alloy & Stainless Steel
Div.
Aliqulppa Plant*
Pittsburgh Plant
Erie Plant
Philadelphia Plant
Neville Island Plant
Clalrton Plant*
Fairleas Hills Plant
Wheeling
Chattanooga Plant
Houston Plant
E. B. Germany Plant
Geneva Work**
Company
Detroit Steel Dlv. of Cyclop*
Corp.
Interlake Inc.
Republic Steel Corp.
Republic Steel Corp.
Republic Steel Corp.
Republic Steel Corp.
U.S. Steel Corp.
Youngstown Sheet and Tube Co.
Alan Wood Steel Co.
Bethlehem Steel Corp.
Bethlehem Steel Corp.
Bethlehem Steel Corp.
Crucible Inc., Div. Colt
Industries
Jones and Laughlln Steel Corp.
Jqnes and Laughlin Steel Corp.
Koppers Company, Inc.
Philadelphia Coke Division
Shenango Inc .
U.S. Steel Corp.
U.S. Steel Corp.
Pittsburgh Steel Corp.
Chattanooga Coke and Chemicals Co
Arnco Steel Corp.
Lone Star Steel Co.
U.S. Steel Corp.
Annual Coal
Capacity
(tons)
600.000
438,000
2,220,000
250,000
650,000
1,500,000
2,700,000
2,300,000
803,000
2,210,000
550,000
1,680,000
657,
2,250,
2,587,
290,
715,
1,022,
9,670,
1,800,
750
000
,633
,404
,000
,400
,000
,000
,000
,000
204,400
584,000
498,000
2,000,000
Emission
Rate
(g/sec)
0.786
0.573
2.908
0.327
1.650
1.965
3.537
3.013
1.051
2.895
0.720t
2.200
0.860
2.947
3.389
0.379
0.937
1.338
12.667
1.768
0.982
Population
0.1-1.0
39,419
25,191
1,342.409
17,734
102,288
193,005
1,238,831
280,123
136,971
336,726
89,682
12,859
198,194
1,144.922
68.912
648.240
154,473
407,475
148,277
66,820
Exposed to Benzene (j>pb) '
1.1-2.0 2.1-4.0 4.1-10
4.228 1,530
1,986
72,578 2,871
37,797
1,593 3,960
36,330 1,804
125,482
83,779 16.819 2,389
4,131
0.267
0.765
0.652
2.620
6,668
4,866
1,046
104.054
19
-------
Table C-l (Concluded)
to
UI
-lit
61.
62.
61.
«4.
St.ite. City
Vir;lnla
tfelrton
Velrton
falrnont
follonsbee
Plant "arce
Ifelrton Mainland Plant
V'elrton'c Brown'* Island
Plant
Falrnont Plant
East Steubcnville Plant
Annual Coal EnLsslon
Capacity Rate Population Exposed to Benzene (ppb}tf
Company
Uclrton Steel J>iv.. National Steel
Corp.
Ueirton Steel Dlv.. Rational Steel
Corp.
Sharon Steel Corp.
Wheeling-Pittsburgh Steel Corp.
(tons) (g/sec) 0.1-1.0 1.1-2.0 2.1-4.0 4.1-10
2,500,000 3.275+ 12,168
1,825,000 2.390
300.000 0.393
2,500,000 3.275 104,932 20,971 3
Vlscufisln
«.
•Illvaiikee
Milwaukee Solvay Coke Co.
A Division of Pleklands tether and
Co.
Total Exposed
347.000 0.656 267,400
Population 15,457,770 521,148 49,719 2,400
Cr>it« own operat Ions producing benzene as a by-product (FEDCo., 1977).
"Based on a 1973 emission inventory.
"Optrat Ions In saoe city are assumed to be co-located and their emissions are sunned.
" To convert to Kg/a3, nultlply concentrations by 3.2; to convert to 8-hour worst-case,
•ultiply concentration* by 10.
Basic Data Source: Keystone Coal Industrie* Manual (1975) and Varga (1974), as cited
In Suta (1977).
-------
APPENDIX D
Population Exposures from Petroleum Refineries by Location
127
-------
Table D-l
POPULATION EXPOSED TO BENZENE FROM PETROLEUM REFINERIES BY PLANT LOCATION
Location -*•
ALABAMA
Holt
Warrior Asphalt Co. of
Alabama, Inc.
Theodore
Marion Oil Co.
Tuscaloosa
Hunt Oil Co.
Total
ALASKA
Kenai
Chevron USA Inc.
Tesoro Petro Corp.
North Slope
At-Rich Co.
Total
ARIZONA
Fredonia
Arizona Fuels Corp.
Total
Total
Capacity
(lO^3)1
.17
1.04
1.65
2.86
1.28
2.21
.75
4.24
.23
.23
Total
Emission
(iQ6e)2
2.1
13.5
21.5
37.1
16.6
28.7
9.8
55.1
3.0
3.0
Emission
Rate
(g/sec)2
.07
.43
.68
.53a
.91
.31
.10
0.1-1
0
0
101
101
2
0
2
0
Population
.0 1.1-2.
0
0
0
0
0
0
2 *
Exposed to Benzene (ppb)
0 2.1-4.0 4.1-10.0 > 10.0
000
000
000
000
000
000
ARKANSAS
El Dorado
Lion Oil Co.
2.69
35.0
1.11
456
1. Source: Oil and Gas Journal, May 28, 1977.
2. Source: SRI estimates.
-------
Table D-l (Continued)
Locationl
Total Total Emission
Capacity Emission Rate
2 *
Population Exposed to Benzene (ppb)
ARKANSAS (Cont.)
Norphlet
MacMillan Ring-Free
Oil Co., Inc.
Smackover
Cross Oil & Refining
Co. of Arkansas
*
Stephens
Crystal Oil Co.
Total
CALIFORNIA
Bakersfield
Chevron USA Inc.
Kern Co. Refinery Co.
Lion Oil Co. (TOSCO)
Mohawk Petroleum Corp., Inc.
Road Oil Sales
Sabre Refining Co.
Sunland Refining Co.
West Coast Oil Co.
Benicia
Exxon Co.
Carson
Atlantic-Richfield*
Fletcher Oil and
Refining Co.
(10 V)1
.26
.34
.22
3.51
1.51
.92
2.21
1.28
.09
.20
.81
.87
5.12
10.16
1.11
(106g)2
3.3
4.4
2.9
45.6
19.6
12.0
28.7
16.7
1.1
2.6
10.6
11.3
66.4
264.1
14.5
(g/sec)2 0.1-1.0 1.1-2.0 2.1-4.0 4.1-10.0
.11 0 0 0 0
.14 0 0 0 0
.09 0 0 0 0
456
.62a
.38
.91
.53
.04
.08
.34
.36 52,833 600
2.11 473 0 0 0
8.39a
.46 132,936t 459 30 2
>10.0
0
0
0
0
0
0
-------
Table D-l (Continued)
Location 1
CALIFORNIA (Cont.)
El Segundo
Chevron USA Inc.**
Hanford
Beacon Oil Co.
Hercules
Pacific Refining Co.
Long Beach
Edgington Oil Co. Inc.
Los Angeles
Union Oil Co. - Calif.
Martinez
Lion Oil Co. (TOSCO)
Shell Oil Co.
Newhall
Newhall Refining Co. Inc.
Oildale
Golden Bear Div., Witco.
Chemical Corp.
San Joaquin Refining Co.
Oxnard
Oxnard Refinery
Paramount
Douglas Oil Co.
Richmond
Shell Oil Co.
San Francisco
Union Oil Co. - Calif
Total
Capacity
23.51
.71
3.09
1.71
6.27
7.31
5.80
.63
.61
1.57
.15
2.70
21.20
6.44
Total
Emission
(10 6g)2
611.2
9.3
40.2
22.3
81.5
95.1
75.4
8.2
7.9
20.4
1.9
35.1
550.8
83.8
Emission
Rate
(g/sec)2
19.40
.29
1.28
.71
2.59
3.02a
2.40
.26
.25a
.65
.06
1.11
17.49
2.66
2
Population Exposed to
0.1-1.0
4-
63,748T
0
67
369
48,447
19,080
0
17
0
0
2,226
4.
134,711
1.1-2.0
318
0
0
0
5
2
0
0
0
0
0
3,945
2.1-4.0
21
0
0
0
0
0
0
0
0
0
0
261
Benzene (ppb)
4.1-10.0
1
0
0
0
0
0
0
0
0
0
0
18
>10.0
0
0
0
0
0
0
0
0
0
0
0
1
-------
Table D-l (Continued)
•f
Location-1-
CALIFORNIA (Cont.)
Santa Fe Springs
Gulf Oil Co.
Powerline Oil Co.
Santa Maria
Douglas Oil Co.
Signal Hill
MacMilJ.an Ring-Free
Oil Co.
South Gate
Lunday-Thagard Oil Co.
Torrance
Mobile Oil Corp.
Ventura
USA Petrochem Corp.
Wilmington
Champlin Petroleum Co.
Shell Oil Co.
Texaco Inc.
Total
COLORADO
Commerce City
Asamera Oil (U.S.) Inc.
Denver
Continental Oil Co.
Fruita
Gary Western Co.
Total
Total
Capacity
(lO^rn3)!
2.99
2.56
.55
.67
.49
7.17
.87
1.78
5.22
4.35
132.63
1.31
1.89
.53
3.73
Total
Emission
(10*>g)2
38.9
33.3
7.2
8.7
6.4
93.2
11.3
23.1
67.9
56.6
2,437.3
17.0
24.5
6.94
48.44
Emission
Rate
(K/sec)2
1.23a
1.06
.23
.28
.20
2.96
.36
.73a
2.16
1.80
.54
.78
.22
Population
0.1-1.0
651
1
0
3
88,756
13
10,822
555,203
0
391
0
391
1.1-2.
0
0
0
0
10
0
1
4,746
0
0
0
o
Exposed to
0 2.1-4.0
0
0
0
0
1
0
0
267
0
0
0
Benzene (ppb)
4.1-10.0 >
0
0
0
0
0
0
0
21
0
0
0
10.0
0
0
0
0
0
0
0
1
0
0
0
-------
Table D-l (Continued)
Total Total Emission 2 ^
Capacity Emission Rate _ Population Exposed to Benzene (ppb)
Location1
DELAWARE
Delaware City
Getty Oil Co. Inc.
Total
FLORIDA
St Marks
Seminole Asphalt
Refinery Co.
Total
GEORGIA
Douglasvilie
Young Refining Co.
Savannah
Amoco Oil Co.
Total
HAWAII
Barbers Point
Chevron USA Inc.
Ewa Beach
Hawaii Independent
Refinery Inc.
Total
(lOSi3)1
8.13
8.13
.33
.33
.28
8.71
8.99
2.32
3. 42
5.74
(106g)2
105.6
105.6
4.3
4.3
3.6
11.3
14.9
30.2
44.5
74.7
(g/sec)^ 0.1-1.0 1.1-2.0 2.1-4.0 4.1-10.0 > 10.0
3.35 6,355 1 0 0 0
6,355 1
.14 0 00 0 0
0
.12 0 0 0 0 0
.36 0 0 0 0 0
0
.96 22 0 0 0 0
1.41 65 0 0 0 0
67
-------
Table D-l (Continued)
Total Total Emission
Capacity Emission Rate
Population Exposed to Benzene (ppb)
Locatiotr
ILLINOIS
Blue Island
Clark Oil and
Refining Co.
Colmar
Yetter Oil Co.
Hartford
Clark OiJ. and Refining Co.
Joliet
Mobil Oil Corp.
Lawrenceville
Texaco Inc.
Lemont
Union Oil Co. of Calif.**
Lockport
Texaco Inc.
Plymouth
Wireback Oil Co. Inc.
Robinson
Marathon Oil Co.
Wood River
Amoco Oil Co.
Shell Oil Co.**
Total
(lO^3)1
3.86
.06
3.03
10.45
4.88
8.76
4.18
.10
11.32
5.51
16.43
68.58
(106g)2
50.1
.8
39.4
135.8
63.4
227.9
54.3
1.4
147.1
71.7
427.1
1,287.58
(8/sec)2
1.59
.02
1.25
4.31
2.01
7.23
1.72
.04
4.67
2.28a
13.56
0.1-1.0
235
0
92
87,063
590
89,134
320
0
16,067
96,529t
290,020
1.1-2.0
0
0
0
32
0
10
0
0
2
217
261
2.1-4.0
0
0
0
2
0
1
0
0
0
14
T7
4.1-10.0
0
0
0
0
0
0
0
0
0
1
1
>10.0
0
0
0
0
0
0
0
0
0
0
-------
Table D-l (Continued)
Total Total Emission
Capacity Emission Rate _ Population Exposed2 to Benzene (ppb)*
u>
Ul
Location1
INDIANA
East Chicago
Energy Coop. Inc.
Fort Wayne
Gladieux Refinery Inc.
Indianapolis
Rock Island Refining Corp.
Lake ton
Lake ton Asphalt Refining Inc.
Mt Vernon
Indiana Farm Bureau
Coop. Association Inc.
Princeton
Princeton Refinery Inc.
Whiting
Amoco Oil Co.
Total
KANSAS
Arkansas City
Apco Oil Co.
Augusta
Mobil Oil Corp.
Chanute
Mid Amer Refinery Co.
Coffeyville
CRA Inc.
(10 ^nr1)-1-
7.31
.71
2.53
.47
.12
.27
21.19
33.31
2.68
2.90
.18
2.81
(106g)^
95.1
9.2
32.9
6.1
1.6
3.5
275.4
423.8
34.9
37.7
2.3
36.5
(g/sec)2
3.02
.29
1.04
.19
.05
.11
8.74
1.11
1.20
.07
1.16
0.1-1.0
46,312
5
439
0
0
0
4.
71,612f
118,368
7
10
0
9
1.1-2.0
0
0
0
0
0
0
16
16
0
0
0
0
2.1-4.0
0
0
0
0
0
0
1
1
0
0
0
0
4.1-10.0
0
0
0
0
0
0
0
0
0
0
0
>10.0
0
0
0
0
0
0
0
0
0
0
0
-------
Table D-l (Continued)
Total Total Emission
Capacity Emission Rate
2 *
Population Exposed to Benzene (ppb)
LJ
CT.
Location-*-
KANSAS (Cont.)
El Dorado
Getty Oil Co.**
Pester Refining Co.
Kansas City
Phillips Petr. Co.
McPherson
Nat. Cdop. Refinery Assoc.
Phillipsburg
CRA Inc.
Shallow Water
E-Z Serve
Wichita
Derby Refining Co.
Total
KENTUCKY
Betsy Layne
Ky Oil & Refining Co. Inc.
Catlettsburg
Ashland Petr. Co.**
Louisville
Louisville Refining Co.
Somerset
Somerset Refinery Inc.
Total
(10 6m3)1
4.57
1.31
5.22
3.14
15.32
.55
1.45
40.13
.03
7.88
1.46
.17
9.54
(106g)2
118.8
17.0
67.9
40.9
199.2
7.2
18.1
580.5
.04
204.9
19.0
2.3
226.24
(g/sec)2
3.77a
.54
2.16
1.30
6.32
.23
.60
.01
6.51
.60
.07
0.1-1.0
1,524
11,620
14
6,832
0
83
20,099
0
24,554
0
0
24,554
1.1-2.0
0
1
0
1
0
0
2
0
3
0
0
3
2.1-4.0
0
0
0
0
0
0
0
0
0
0
4.1-10.0
0
0
0
0
0
0
0
0
0
0
> 10.0
0
0
0
0
0
0
0
0
0
0
-------
Table D-l (Continued)
Total Total Emission
Capacity Emission Rate
2 *
Population Exposed to Benzene (ppb)
Location1
LOUISIANA
Baton Rouge
Exxon Co.
Belle Chasse
Gulf Oil Co., Alliance
Refinery**
Chalmette
Tenneco Oil Co.**
Church Point
Canal Refining Co.
Convent
Texaco
Cotton Valley
Kerr-McGee Refining Corp.
Garyville
Marathon Oil Co.
Ross ton
Bayou St. Oil Corp.
Jennings
Evangeline Refining Co. Inc.
Lake Charles
Cities Service Oil Co.
Continental Oil Co.
Lisbon
Claiborne Gasoline Co.
Meraux
Murphy Oil Co.
(ICPm3)1
29.60
11.4
4.93
.26
8.13
.64
11.61
.23
.29
15.56
4.82
.38
5.37
(106g)2
384.8
295.6
128.3
3.4
105.6
8.30
150.9
3.0
3.8
202.2
62.6
4.9
69.8
(g/sec)2
12.22
9.38
4.07
.11
3.35
.26
4.79
.10
.12
6.42a
1.99
.16
2.22
0.1-1.0
201,106f
40,200f
3,895
0
1,816
0
7,376
0
0
40,204f
0
362
1.1-2.0
1,613
12
0
0
0
0
1
0
0
8
0
0
2.1-4.0
107
1
0
0
0
0
0
0
0
0
0
0
4.1-10.0
7
0
0
0
0
0
0
0
0
0
0
0
>10.0
0
0
0
0
0
0
0
0
0
0
0
0
-------
Table D-l (Continued)
UJ
00
Location^-
LOUIS1ANA (Cont.)
Metairie
Good Hope Refineries Inc.
Norco
Shell Oil Co.
Port Allen
Placid Refining Co.
Princeton
Calumet Refining Co.
Shreveport
Atlas Production Co., Div.
of Pennzoil**
St. James
LaJet Inc.
Venice
Gulf Oil Co.
Total
MARYLAND
Baltimore
Amoco Oil Co.
Chevron USA Inc.
Total
Total
Capacity
3.86
13.93
1.99
.14
2.61
.83
1.67
118.25
.87
.78
1.65
Total
Emission
(106g)2
50.2
181.1
25.8
1.8
67.9
10.8
21.7
1,782.5
11.3
10.2
21.5
Emission
Rate
(g/sec)^
1.59
5.75
.82
.06
2.16
.34
.69
.36a
.32
o
Population Exposed to
0.1-1.0
98
15,093
7
0
12,555
0
4
322,716
489
489
1.1-2.0
0
2
0
0
1
0
0
1,637
0
2.1-4.0
0
0
0
0
0
0
0
108
0
Benzene (ppb)
4.1-10.0
0
0
0
0
0
0
0
7
0
> 10.0
0
0
0
0
0
0
0
0
MICHIGAN
Alma
Total Petroleum Inc.
2.32
30.2
.96
26
-------
Table D-l (Continued)
u>
VO
Location1
MICHIGAN (Cont.)
Bay City
Dow Chemical USA
Carson City
Crystal Refining Co.
Detroit
Marathon Oil Co.
Kalamazoo
Lakeside Refining Co.
West Branch
Osceola Refinery Div. ,
Texas American Petrochemicals
Inc.
Total
MINNESOTA
Rosemount
Koch Refining Co.
St. Paul Park
Northwest Refining Co., Div.
of Ashland Oil Co.
Wrenshall
Continental Oil Co.
Total
Total
Capacity
(H^m3)1
1.21
.36
3.77
.33
.72
8.71
7.39
3.83
1.36
12.58
Total
Emission
(106g)2
15.8
4.7
49.0
4.2
9.3
113.2
96.1
49.8
17.7
163.6
Emission
Rate
(g/sec)2
.50
.15
1.56
.13
.30
3.05
1.58
.56
Population
0.1-1.0
63
0
12,007
0
0
12,096
746
57
1
804
1.1-2
0
0
1
0
0
1
0
0
0
0
2
Exposed to
.0 2.1-4.0
0
0
0
0
0
0
0
0
Benzene (ppb)
4.1-10.0 >
0
0
0
0
0
0
0
0
10.0
0
0
0
0
0
0
0
0
-------
Table D-l (Continued)
Total Total Emission
Capacity Emission Rate
2 *
Population Exposed to Benzene (ppb)
Location!
MISSISSIPPI
Lumberton
Southland Oil Co.
Pascagoula
Chevron USA Inc.
Purvis
Amerada-Hess Corp.
Sandersville
Southland Oil Co.
Yazoo City
Southland Oil Co.
Total
MISSOURI
Sugar Creek
Amoco Oil Co.
Total
MONTANA
Billings
Continental Oil Co.
Exxon Co.
Cut Bank
Westco Refining Co.
Great Falls
Phillips Petroleum Co.
Kevin
Big West Oil Co.
(lO5^!3)1
.33
16.3
1.65
.60
.23
19.11
6.21
6.21
3.05
2.61
.27
.35
.30
(106g)2
4.3
422.5
21.5
7.85
3.0
459.2
80.7
80.7
39.6
34.0
3.5
4.5
3.87
(g/sec)2
.14
13.41
.68
.25
.10
2.56
_ _ f\
1.26a
1.08
.11
.14
.12
0.1-1.0
0
49,501
2
0
0
49,503
534
534
22,492
0
0
0
1.1-2.0
0
1,032
0
0
0
1,032
0
3
0
0
0
2.1-4.0
0
68
0
0
0
68
0
0
0
0
0
4.1-10.0
0
5
0
0
0
5
0
0
0
0
0
> 10.0
0
0
0
0
0
0
0
0
0
0
-------
Table D-l (Continued)
Total Total Emission
Capacity Emission Rate _ Population Exposed to Benzene (ppb)*
Location1
MONTANA (Cont.)
Laurel
Cenex
Wolf Point
Tesoro Petroleum Corp.
Total
NEBRASKA
Scottsbluff
CRA Inc.
Total
NEW HAMPSHIRE
Newington
Atlantic Terminal Corp.
Total
NEW JERSEY
Bayonne
National Oil Recovery Corp.
Linden
Exxon Co.
Paulsboro
Mobil Oil Corp.
Perth Amboy
Chevron USA Inc.
Westville
Texaco , Inc .
Total
(UPm3)1
2.35
.15
9.08
.29
.29
.75
.75
.35
16.54
'5.69
9.75
5ft2
37.45
(10 6g)^
30.5
1.9
117.87
3.8
3.8
9.8
9.8
4.5
215.0
73.9
126.8
66.4
486.6
(g/sec)z
.97
.06
.12
.31
.14
6.83
2.35
4.02
2.12
0.1-1.0
1
0
22,493
0
0
0
0
0
378,786
5,315
77,763
3,549
465,413
1.1-2.0
0
0
3
0
0
0
151
1
41
0
193
2.1-4.0
0
0
0
0
0
10
0
3
0
13
4.1-10.0
0
0
0
0
0
1
0
0
0
1
> 10.0
0
0
0
0
0
0
0
0
0
-------
Table D-l (Continued)
Total Total Emission
Capacity Emission Rate _ Population Exposed2 to Benzene (ppb)J
ro
Location1
NEW MEXICO
Artesia
Nova jo Refining Co.
Bloomfield
Plateau Inc.
Thriftway Co.
Ciniza
Shell Oil Co.
Farmington
Giant Refining Co. Inc.
Kir t land
Caribou Four Corners Inc.
Lovington
Southern Union Refining Co.
Monument
Southern Union Refining Co.
Total
NEW YORK
Buffalo
Mobil Oil Corp.
N. Tonawanda
Ashland Petroleum**
Total
(lO^3)1
1.74
.49
.44
1.04
.51
.17
2.23
.30
6.92
2.50
3.71
6.21
(106g)2
22.6
6.3
5.7
13.6
6.6
2.2
29.0
3.9
96.82
32.4
96.6
129.0
(g/sec)2 0.1-1.0
.72
.20a
.18
.43
.21
.07
.92
.12
1.03
3.07
0
0
0
0
0
1
0
1
2,412
38.107
40,519
1.1-2.0
0
0
0
0
0
0
0
0
6
6
2.1-4.0
0
0
0
0
0
0
0
0
0
4.1-10.0
0
0
0
0
0
0
0
0
0
>10.0
0
0
0
0
0
0
0
0
0
-------
Table D-l (Continued)
Total Total Emission
Capacity Emission Rate
2 *
Population Exposed to Benzene (ppb)
Location
NORTH DAKOTA
Dickson
Northland Oil & Refining Co.
Mandan
Amoco Oil Co.
Williston
Westland Oil Co.
Total
OHIO
Canton
Ashland Petroleum Co.
Cleves
Gulf Oil Co.
Findlay
Ashland Petroleum Co.
Lima
Standard Oil Co. of Ohio
Toledo
Gulf Oil Co.
Standard Oil Co. of Ohio
Sun Petroleum Prod. Co.
Total
(10 6m3)1
.29
2.84
.27
3.40
3.71
2.48
1.16
9.75
2.92
6.96
7.26
34.24
(106g)Z
3.8
37.0
3.5
44.30
48.3
32.2
15.1
126.8
38.0
90.5
94.3
445.2
(g/sec)2
.12
1.17
.11
1.53
1.02
.48
4.02
1.20a
2.87
2.99
0.1-1.0
0
4
0
4
5,877
54
34
62,124
469,013
537,102
1.1-2.0
0
0
0
1
0
0
23
216
240
2.1-4.0
0
0
0
0
0
0
2
14
16
4.1-10.0
0
0
0
0
0
0
0
1
1
> 10.0
0
0
0
0
0
0
0
0
OKLAHOMA
Ardmore
Vickers Petroleum Corp.
3.56
46.2
1.47
34
-------
Table D-l (Continued)
Total Total Emission „ ^
Capacity Emission Rate Population Exposed to Benzene (ppb)
Location
OKLAHOMA (Cont.)
Arnett
Tonkawa Refining Co.
Gushing
Hudson Refining Co. Inc.
Cyril
Apco Oil Corp.
Duncan
Sun Petroleum Products Inc.
Enid
Champlin Petroleum Co.
Okmulgee
OKC Refining Co.
Ponca City
Continental Oil Co.
Stroud
Allied Materials Corp.
Tulsa
Sun Petroleum Products Inc.
West Tulsa
Texaco Inc.
Wynnewood
Kerr-McGee Corp.
Total
(lQ6m3)l
.35
1.10
.81
2.81
3.12
1.45
7.31
.03
5.14
2.90
2.90
31.48
(106g)2
4.52
14.3
10.6
36.6
40.6
18.9
95.1
3.6
133.6
37.7
37.7
479.42
(g/sec)2
.14
.46
.33
1.16
1.29
.60
3.02
.11
4.24
1.20
1.20
0.1-1.0
0
0
0
13
992
1
20,292
0
105,882
15
15
127,244
1.1-2.0
0
0
0
0
0
0
2
0
12
0
0
14
2.1-4.0
0
0
0
0
0
0
0
0
1
0
0
1
4.1-10.0
0
0
0
0
0
0
0
0
0
> 10.0
0
0
0
0
0
0
0
0
-------
Table D-l (Continued)
Locationl
OREGON
Portland
Chevron USA Inc.
Total
PENNSYLVANIA
Bradford
Kendall-Amalie Div.,
Witco Chemical Co.
Emlenton
Quaker State Oil Refining
Corp.
Farmers Val
Quaker State Oil Refining
Corp.
Freedom
Valvoline Oil Co. Div.
of Ashland Oil Co.
Marcus Hook
BP Oil Corp.
JLJL
Sun Petroleum Products Co.
Philadelphia
Atlantic-Richfield Co.**
Gulf Oil Co.**
Reno
Pennzoil Co. - Wolf's Head
Div.
Total
Capacity
.81
.81
.52
.19
.38
.39
9.34
9.58
10:74
11.85
.12
Total
Emission
(106g)2
10.6
10.6
6.8
2.5
4.9
5.1
121.5
249.0
279.2 .
308.2
1.6
Emission
Rate
(g/sec)2
.34
.22
.98
.16
.16
3.86a
7.90
8.86a
9.78
.05
Population
0.1-1.0 1.1-2.
12 0
12
0 0
47 0
0 0
0 0
128,081t 89
2,009,462 31,189
0 0
2
Exposed to
0 2.1-4.0
0
0
0
0
0
6
2,060
0
Benzene (ppb)*
4.1-10.0 >10.0
0 0
0 0
0 0
0 0
0 0
0 0
142 4
0 0
-------
Table D-l (Continued)
Total Total Emission _
Capacity Emission Rate Population Exposed to Benzene (ppb)'
Location
PENNSYLVANIA (Cont.)
Roseville
Pennzoil Co. - Wolf's Head
Div.
Warren
United Refining Co.
Total
TENNESSEE
Memphis
Delta Refining Co.
Total
TEXAS
Abilene
Pride Refining Co.
Amarillo
Texaco Inc.
Baytown
Exxon Co.
Beaumont
Mobil Oil Corp.
Union Oil Co. of Calif.
Big Spring
Cosden Oil & Chemical Co.
Borger
Phillips Petroleum Co.
Carrizo Springs
Tesoro Petroleum Corp.
(10 6m3)1
.58
3.02
46.71
2.55
2.55
2.12
1.16
22.6
18.86
6.96
3.77
5.80
1.51
(106g)2
7.5
39.2
1,025.5
2.3
2.3
27.5
15.1
294.3
245.2
181.1
98.1
75.5
19.7
(K/sec)2
.24
1.25
1.05
.87
.48
9.34
7.78a
5.75
3.11
2.40
.63
0.1-1.0
0
121
2,137,711
665
665
133
23
65,159f
134,266
28,992
276
1
1.1-2.0
0
0
31,278
0
0
0
237
963
4
0
0
2.1-4.0
0
0
2,066
0
0
0
16
64
0
0
0
4.1-10.0
0
0
142
0
0
0
1
4
0
0
0
> 10.0
0
0
4
0
0
0
0
0
0
0
0
-------
Table D-l (Continued)
Location
TEXAS (Continued)
Corpus Chris ti
Champlin Petroleum Corp.
Coastal States Petrochemical
Co.
Howell Corp.
Qu in tana Refining Co.
Saber Refining Co.
Southwestern Refining
Co . Inc .
Sun Petroleum Products Co.
Deer Park
Shell Oil Co.**
El Paso
Chevron USA Inc.**
Texaco Inc.
Euless
Texas Asphalt Refining Co.
Ft. Worth
Winston Refining Co.
Hearne
Mid-Tex Refinery
Houston
Atlantic Richfield Co.**
Charter International
Oil Co.
Crown Central Petroleum Co.
Eddy Refining Co.
Total
Capacity
CK^m3)1
7.26
10.7
1.23
1.36
.54
6.96
3.31
17.06
4.00
.99
.35
1.16
.17
17.76
3.77
5.80
.18
Total
Emission
(106g)2
188.6
279.2
31.9
35.3
7.0
181.1
86.0
443.7
105.6
12.8
4.5
15.1
2.3
461.8
49.0
150.9
2.3
Emission
2 fc
Rate Population Exposed to Benzene (ppb)
(g/sec)2 0.1-1.0 1.1-2.0 2.1-4.0 4.1-10.0 > 10.0
5.99a
8.86
1.01
1.12
.22
5.75
2.75 216,970T 5,188 343 24 1
14.08 22,585 32 2 0 0
3.35
.41 93,949 11 1 0 0
.14 00 0 0 0
.48 21 0 0 0 0
.07 0000 0
14.66
1.56
4.79
.73 l,170,743t 131 9 1 0
-------
Table D-l (Continued)
Total Total Emission
Capacity Emission Rate Population Exposed to Benzene (ppb)*
Location
TEXAS (Cent.)
LaBlanca
Crystal Oil Co.
Longview
Crystal Oil Co.
Mt . Pleasant
American Petrofina Inc.
Nixon
Pioneer Refining
Odessa
Shell Oil Co.**
Port Arthur
American Petrofina Inc.**
Gulf Oil Co.**
Texaco Inc.
Port Heches
Texaco Inc.
Quitman
Gulf St. Oil & Refining Co.
San Antonio
Flint Chemical Co.
Howell Corp.
Silsbee
South Hampton Co.
Sunray
Diamond Shamrock Corp.
Sweeny
Phillips Petroleum Co.
(10 6m3)1
.28
.50
1.51
.15
1.86
6.38
18.11
23.56
2.73
.24
.07
.20
1.05
2.99
6.04
(106g)Z
3.6
6.5
19.6
1.9
48.3
166.0
471.0
306.3
35.5
3.1
0.9
2.6
13.7
38.9
78.5
(g/sec)2
.11
.20
.63
.06
1.53
5.27a
15.0
9.72
1.13
.10
,03a
.08
.43
1.23
2.49
0.1-1.0
0
1
1
0
4,327
60,839
14
0
0
0
20
319
1.1-2.0
0
0
0
0
0
15,798
0
0
0
0
0
0
2.1-4.0
0
0
0
0
0
1,044
0
0
0
0
0
0
4.1-10.0
0
0
0
0
0
72
0
0
0
0
0
0
>10.0
0
0
0
0
0
2
0
0
0
0
0
0
-------
Table D-l (Continued)
Total Total Bnlssion
Capacity Emission Rate Population Exposed2 to Benzene (ppb)*
Location^
TEXAS (Cont.)
Texas City
Amoco Oil Co.**
Marathon Oil Co.**
Texas City Refining Inc.
Three Rivers
Sigmor Refining Co.
Tucker
J&W Refining Inc.
Tyler
LaGloria Oil & Gas Co.
White Deer
Dorchester Gas Products Co.
Winnie
Independent Refining Co.**
Young County
Thriftway Inc.
Total
UTAH
Asphalt Ridge
Arizona Fuels Corp.
North Salt Lake
Husky Oil Co.
Roosevelt
Plateau Inc.
Salt Lake City
Amoco Oil Co.
Chevron USA
(lO^)-1
20.20
3.83
4.32
.59
.58
1.70
.06
.77
.06
243.22
.06
1.33
.46
2.26
2.61
(10 bg)^
525.2
99.6
56.2
7.7
7.5
22.1
.8
19.9
.8
4,949.8
0.8
17.4
6.0
29.4
34.0
(g/sec)^
16.67a
3.16
1.78
.24
.24
.70
.02
.63
.02
.02
.55
.19
.93a
1.08
0.1-1.0
56,049
0
0
118
0
1
0
1,854,807
0
0
0
10,212
1.1-2.0
2,139
0
0
0
0
0
0
24,503
0
0
0
1
2.1-4.0
141
0
0
0
0
0
0
1,620
0
0
0
0
4.1-10.0
10
0
0
0
0
0
0
112
0
0
0
0
> 10.0
0
0
0
0
0
0
0
3
0
0
0
0
-------
Table D-l (Continued)
Total Total Emission
Capacity Emission Rate _ Population Exposed to Benzene (ppb)
Ul
o
Location^
UTAH (Cont.)
Woods Cross
Caribou Four Corners Inc.
Morrison Petroleum Co.
Phillips Petroleum Co.
Western Refining Co. Inc.
Total
VIRGINIA
Yorktown
Amoco Oil Co.
Total
WASHINGTON
Anacortes
Shell Oil Co.
Texaco Inc.
Ferndale
Atlantic Richfield Co.
Mobil Oil Corp.
Seattle
Chevron USA
Tacoma
Sound Refining Co.
U.S. Oil and Refining Co.
Total
(10 6m3)1
.41
.15
1.33
.57
9.18
3.08
3.08
5.28
4.53
5.57
4.15
.26
.26
1.24
21.29
(106g)2
5.4
1.9
17.4
7.4
119.7
40.0
40.0
68.7
58.9
72.4
53.9
3.4
3.40
16.1
276.8
(g/sec)2
.17a
.06
.55
.23
1.27
2,18a
1.87
2.30a
1.71
.11
.lla
.51
0.1-1.0 1.1-2.0 2.1-4.0 4.1-10.0 > 10.0
3000 0
10,215 1
60 0 0 0 0
60
2,388 000 0
2,297 000 0
00 00 0
95 0 00 0
4,780
-------
Table D-l (Continued)
Total Total Emission
Capacity Emission Rate Population Exposed2 to Benzene (ppb)*
Location1
WEST VIRGINIA
Falling Rock
Pennzoil Co. , Elk Refining
Div.
Newell
Quaker State Oil Refining
Corp.
St. Marys
Quaker State Oil Refining
Corp.
Total
WISCONSIN
Superior
Murphy Oil Corp.
Total
WYOMING
Casper
Amoco Oil Co.
Little American Refining Co.
Texaco Inc.
Cheyenne
Husky Oil Co.
Cody
Husky Oil Co.
(106m3)J-
.28
.56
.28
1.12
2. 64
2.64
2.50
1.42
1.22
1.37
.63
(106g)^
3.7
7.3
3.7
14.7
34.3
34.3
32.4
18.5
15.8
i7.8
8.1
(g/sec)'
.12
.23
.12
1.09
1.03a
.59
.50
.57
.26
1 0.1-1.0 1.1-2.0 2.1-4.0 4.1-10.0
0000
0000
0000
22 0 0 0
22
13,084 100
75 0 0 0
0000
>10.0
0
0
0
0
0
0
0
-------
Table D-l (Concluded)
Location
WYOMING (Cont.)
Cowley
Sage Creek Refining Co.
LaBarge
Mountaineer Refining
Co . Inc .
Southwestern Refining Co.
Lusk
C&H Refinery Inc.
Newcastle
Tesoro Petroleum Corp.
Osage
Glacier Park Co.
Sinclair
Sinclair Oil Corp.
Total
Total
Total
Capacity Emission
(lOSi3)1 (106g)2
.07
.02
.03
.01
.61
.24
2.84
10.96
Total
.86
.23
.4
.14
7.92
3.09
37.0
142.24
Emission
Rate
(g/sec)2
.03
.007
.01
.005
.25
.10
1.17
Exposed Population
Population Exposed to Benzene (ppb)
: 0.1-1.0
0
0
0
0
0
2
13,162
6,617,134
1.1-2.0
0
0
0
0
0
0
1
63,944
2.1-4.0
0
0
0
0
0
0
4,223
4.1-10.0
0
0
0
0
0
0
291
>10.0
0
0
0
0
0
0
8
a - When more than one refinery is located in a city, it is assumed that they are in approximately
the same area and the emission levels are summed.
To convert to ug/m3, multiply concentrations by 3.2; to convert to 8-hour worst case, multiply by 10.
**Refineries having catalytic reforming of benzene. Their emission rate is assumed to be twice that
of refineries with no benzene production.
1"Some population may be exposed to annual average concentrations >0.1 ppb beyond 20 km.
------- |