United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park NC 27711
EPA-450/2-80-074
June 1980
Air
Health Impacts,
Emissions, and Emission
Factors for IMoncriteria
Pollutants Subject to
De Minimis Guidelines and
Emitted from Stationary
Conventional Combustion
Processes
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This report is issued by the Environmental Protection Agency to report technical data of
interest to a limited number of readers. Copies are available - in limited quantities - from
the Library Services Office (MD-35) , U.S. Environmental Protection Agency, Research
Triangle Park, North Carolina 27711; or, for a fee, from the National Technical Infor-
mation Service, 5285 Port Royal Road, Springfield, Virginia 22161.
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TABLE OF CONTENTS
i
Page
1. INTRODUCTION AND SUMMARY 1
2. HEALTH AND ECOLOGICAL EFFECTS 5
2.1 HEALTH AND ECOLOGICAL EFFECTS ON POPULATIONS 6
2.1.1 Mercury 6
2.1.2 Beryllium 11
2.1.3 Asbestos 14
2.1.4 Fluorides 16
2.1.5 Sulfuric Acid Mist 20
2.1.6 Vinyl Chloride 24
2.1.7 Hydrogen Sulfide 26
2.1.8 Methyl Mercaptan 29
2.1.9 Dimethyl Sulfide 30
2.1.10 Dimethyl Disulfide 31
2.1.11 Carbon Disulfide 31
2.1.12 Carbonyl Sulfide 34
2.2 ECOSYSTEM EFFECTS 35
3. NATIONAL EMISSIONS 37
3.1 TRACE ELEMENTS 37
3.2 ASBESTOS 37
3.3 SULFURIC ACID MIST 41
3.4 VINYL CHLORIDE 41
3.5 TOTAL REDUCED SULFUR AND REDUCED SULFUR COMPOUNDS 41
3.6 SUMMARY OF EMISSIONS 45
4. EMISSION FACTORS 48
4.1 TRACE ELEMENTS . 48
4.2 SULFURIC ACID MIST 55
4.3 ASBESTOS AND VINYL CHLORIDE 57
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TABLE OF CONTENTS (continued)
Page
5. DEVELOPMENT OF EMISSION FACTORS 58
5.1 TRACE ELEMENT EMISSIONS 58
5.1.1 External Combustion - Utility Boilers 58
5.1.2 External Combustion - Industrial Boilers 62
5.1.3 Internal Combustion - Industrial or 63
Electricity Generation
5.1.4 External Combustion - Commercial/Institutional 64
5.2 ASBESTOS EMISSIONS 65
5.3 SULFURIC ACID MIST EMISSIONS 71
5.4 VINYL CHLORIDE EMISSIONS 69
5.5 TOTAL REDUCED SULFUR AND REDUCED SULFUR COMPOUND EMISSIONS 70
6. SAMPLING AND ANALYSIS PROCEDURES USED TO OBTAIN EMISSIONS DATA 72
6.1 SAMPLING METHODOLOGY 72
6.2 ANALYTICAL METHODOLOGY 74
6.3 ADEQUACY OF DATA FOR EMISSION FACTOR DEVELOPMENT 75
6.4 IMPLICATIONS OF EMISSION FACTOR VARIABILITIES FOR
EMISSIONS CALCULATIONS 81
APPENDIX A: PERSONS CONTACTED FOR INFORMATION ON TOTAL REDUCED 79
SULFUR AND REDUCED SULFUR EMISSIONS
REFERENCES 80
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1. INTRODUCTION AND SUMMARY
Rules have been proposed in the September 5, 1979, Federal Register '
(Volume 44, Number 173) involving the Prevention of Significant Air Quality
Deterioration (PSD). If adopted, these would substantially modify the
existing procedures for approving the construction or modification of
sources of pollutants regulated by the Clean Air Act. A concept discussed
in these rules involves the authority of EPA to exempt some situations from
PSD review. These situations are called de minimi's. Emission cutoffs for
twenty pollutants have been published in the Supplementary Information for
these rules (44 FR 51937) and are proposed as guidelines to determine if
potential emissions from a source subject to PSD review could be considered
insignificant. These emissions levels were based on ambient air quality
levels considered protective of public health and welfare, and were derived
from these air quality levels (44 FR 51938) by means of a conservative
modeling analysis. The guideline emission rates and air quality levels for
the noncriteria pollutants in this list are shown in Table 1-1.
TRW Inc., Radian Corporation, and Battelle Columbus Laboratories are
in the process of developing an extensive information base on environmental
health effects, emissions, and pollution control technology for Stationary
Conventional Combustion Processes (SCCP) as part of the ConventionaT^om-0* .^ +
bustion Environmental Assessment (CCEA) program for EPA's Industrial
Environmental Research Laboratory. The source categories included as SCCP
are shown in Table 1-2.
This report summarizes the results of a quick-response task assignment
to TRW and Battelle under the CCEA Systems Contract to use the CCEA infor-
mation base in developing the following kinds of information for the pollu-
tants listed in Table 1-1:
Health and ecological impacts associated with de minimis air quality
levels.
0 Emission factors for SCCP source categories.
Comparison of emission levels from important source categories
for each pollutant.
Sampling and analysis methods, associated accuracies, and implica-
tions of variabilities of emission factors.
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TABLE 1-1 NONCRITERIA DE MINIMIS GUIDELINES FOR SIGNIFICANT EMISSION RATES
AND AMBIENT AIR QUALITY IMPACTS
Pollutant
Mercury
Beryllium
Asbestos
Fluorides
Sulfuric Acid Mist
Vinyl Chloride
Total Reduced Sulfur:
Hydrogen Sulfide
Methyl Mercaptan
Dimethyl Sulfide
Dimethyl Disulfide
Reduced Sulfur Compounds:
Hydrogen Sulfide
Carbon Disulfide
Carbonyl Sulfide
Significant
Emission Rate
(metric tons/year)
0.2
0.004
1
0.02
!^
1
1
1
1
1
1
10
10
Significant
Air Quality
Wm3)
0.1
0.005
1
0.01
1
1
1
0.5
0.5
2
1
200
200
Impact
(24 hr)
(24 hr)
1 hr)
(24 hr)
(24 hr)
(max. value)
( 1 hr)
( 1 hr)
( 1 hr)
( 1 hr)
( 1 hr)
( 1 hr)
( 1 hr)
Source: Federal Register - September 5, 1979, Pp 51937-8(222.)
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This information is developed in this report for all sources shown in
Table 1-2. In order to be consistent with the EPA timetable for promulga-
tion of the proposed rules, the following constraints were placed on this
assignment:
Period of performance: two months.
Resources: only the existing CCEA information base.
Emission sources considered: stationary conventional combustion
processes (SCCP) only.
Normally the Residential sector is included as a fourth emission source
category. However, it will not be considered in this study, since residen-
tial sources probably will not be subject to PSD regulation. The informa-
tion listed above and the assumptions and methods used to compile this
information are discussed in the following sections.
Although developing conclusions relative to the magnitude of the
de minimis emission and ambient levels in the proposed regulation was not
one of the objectives of this study, several observations can be made in
summary of the information accumulated in this report:
Health and ecological impacts. The results of the investigation
of the health effects of the noncriteria de minimi's pollutants
vary by pollutant (see Section 2.1). Comparisons of dose-response
TABLE 1-2. MAJOR STATIONARY CONVENTIONAL COMBUSTION
PROCESS SOURCE CATEGORIES CONSIDERED IN
THIS STUDY
ELECTRICITY GENERATION
External Combustion
Coal
Petroleum
Gas
Internal Combustion
Petroleum
Gas
INDUSTRIAL
External Combustion
Coal
Petroleum
Gas
Internal Combustion
Petroleum
Gas
COMMERCIAL/ INSTITUTIONAL
External Combustion
Coal
Petroleum
Gas
Internal Combustion
Petroleum
Gas
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information in the literature with the de minimi's ambient levels
are summarized in Section 2.1. Unfortunately, insufficient
information is available in the literature to form substantive
conclusions on ecosystem effects (as opposed to health effects)
of most of these pollutants (see Section 2.2), and necessary
research and synthesis are well beyond the scope of this effort.
t Emission source categories. Stationary Conventional Combustion
Processes (SCCP) produce nearly all of the beryllium and sulfuric
acid emissions nationally. These sources also account for 65
percent of the fluoride emissions and 25 percent of the mercury
emissions. Asbestos, vinyl-chloride and all reduced sulfur com-
pounds are emitted exclusively by other (non-SCCP) sources,
according to available data. (See Section 3).
Emission factors. Based on emission factors in the existing
information base, emissions of sulfuric acid mist from large
coal or oil-fired external combustion systems (utility and large
industrial boilers, for example) controlled to meet the New
Source Performance Standards (NSPS) will exceed the de minimi's
emission levels by orders of magnitude. Similarly, fluoride
emissions from NSPS-controlled external combustion sources burn-
ing coal will exceed the de minimis levels significantly. (See
Sections 4. and 5.). Emissions of the remaining noncriteria
pollutants from combustion sources will not normally exceed
de minimi's levels, although the uncertainty of emission levels
calculated with the beryllium emission factors is high due to
high variabilities of the influence parameters used to develop
the factors (see Section 6.).
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2. HEALTH AND ECOLOGICAL EFFECTS
Published information on the health and ecological effects of the
twelve subject pollutants was identified, assembled, and reviewed. This
section summarizes the results of that review. The biological effects
information necessary for the completion of this study was obtained in
part from a data base assembled at Battelle's Columbus Laboratories for
the EPA's Conventional Combustion Environmental Assessment Program.
This collection of published material, although small, contains useful
data for some of the substances. These data were augmented via the
results of computer bibliographic searches. Successful searches on part
of the substances were conducted in BIOSIS, AGRICOLA, NTIS, TOXLINE, and
TOXBACK for the general period 1970 to 1979. For such topics as odor
thresholds, manual searches were carried out using different keywords in
order to locate as many germane articles as possible within the scope
of work. Much of the human health effects data were obtained from occu-
pational health studies reported by the National Institute for Occupa-
tional Safety and Health (NIOSH) in Criteria Document reports for the
EPCH chemical.
Although much useful information was obtained from the above sources
these should not be considered all inclusive. Additional information
sources are available but the level of effort of this task precluded
their review. Effort was placed in reporting observed effects from in-
halation of low concentrations of the twelve pollutants. Where suffi-
cient data were available they are presented in tables. Dosages reported
range from the lowest known to cause a measurable effect to those which
generally cause a more deleterious effect. Each table and accompanying
text feature several species including plants and animals; however,
emphasis is on human responses.
Data reported in tables emphasize biological responses to low levels
of the pollutant by various target organisms. The accompanying text dis-
cusses the studies most relevant to the de minimis recommendations, thus
not all data in the tables are discussed in the text.
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Although the availability of low dosage information exceeded our
expectations, there remained a general lack of such needed data. Another
inherent limitation was the lack of rigorous dose-response curves. Ideally,
the dose-response curve would provide a continuous, quantitative relation-
ship of a given response by a given species to a given route of entry; e.g.,
inhalation. In the absence of such quantitative dose-response curves,
numerous dose-response relationships are presented. Here, the emphasis
is on the variety of responses by numerous species to various routes of
entry (although inhalation was the usual one).
The presentation of the health and ecological effects has been
divided into three sections: health and ecological effects, ecosystem
effects, and comparison of de minimis levels with the lowest identified
exposures known to cause biological effects.
2.1 HEALTH AND ECOLOGICAL EFFECTS ON POPULATIONS
Studies reviewed in this section concentrate on the effects of
substances on individual species. Effects observed include odor thresh-
olds, changes in rates of morbidity or sickness, changes in tumor incidence,
and other effects associated with humans, plants, and animals. Throughout,
the effects on humans are discussed first, followed by effects on non-
humans. Emphasis has been placed on inhalation as the primary route of
exposure. However, depending on the substance and species involved, other
routes of exposure were considered.
2.1.1 Mercury
The proposed die minimis value for mercury is 0.1 yg/m , 24-hour
average. The health effects from mercury vary depending upon the route
of exposure and form of mercury encountered.
Exposure to mercury may occur from inhalation of atmospheric mercury,
ingestion of mercury contaminated products, and percutaneous absorption of
mercury. The research reported below has concentrated on inhalation exposure.
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TABLE 2-1. HEALTH/ECOLOGICAL EFFECTS OF POPULATIONS EXPOSED TO MERCURY IN AIR
. Exposure
Concentration,
mg/m3
0.002-0.005
0.005-0.06
0.01-0.05
0.01-0.27
0.01-0.6*
0.01
0.08"
3.0
Duration of
Exposure
6.5 hr/d.6 d/Nk
19 yr
>lyr
occupational
exposure
variable
occupational
exposure
(1-20+ yrs.)
9 yr average
occupational
exposure
occupational
exposure
continuous
Species
Rat
Human
Human
Human
Human
Human
Human
Dog
Effects
Changes In conditioned reflexes
Clinical mercury poisoning - tremors erethism 1n
1 of 16 exposed workers.
'Mlcromercurlallsm1 -functional changes In cardio-
vascular, urogenltal, endocrine systems.
Hyperthyroldlsm.
Anorexia, loss of weight, Insomnia, tremors,
dose/response relationship shyness, nervousness
Dose/response relationship Identified. Tremors,
erethism, Impaired memory
Temporary disability, disturbed menstrual function,
elevated percentage of complications In pregnancy
and delivery.
Borderline symptoms of mercury poisoning.
Gingivitis, diarrhea, weight loss after 15 days
Reference
Koumossov 1962 (101), cited
In (90.)
Blstrup, et al, 1951 (84.)
Frlberq and Vostal , 1972
(90.)
Smith, et al., 1970 (103.)
TurHan, et al. , 1956
(104.)
Goncharuk, 1977 (91.)
Neal, et al., 1937, (96.)
1941 (95.)
Fraser, et al., 1934 (89.)
"Analytic methods suspect. Spot samples obtained, not breathing zone time weighted average (TWA).
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However, atmospheric mercury may be incorporated in aquatic and terres-
trial environments. Inorganic and organic mercury compounds introduced
into these environments may undergo microbial transformation to the more
toxic alky! mercury form. Aquatic organisms biomagnify the alkyl mercury
compounds. The partitioning of organic and inorganic mercury compounds
within various media and ecosystems is not reported here. A more thorough
analysis of this partitioning was not possible in this level of effort.
The health effects data in Table 2-1 are based on respiratory exposures
to inorganic mercury compounds in occupational environments. The following
narrative reviews some of these data. Bidstrup et al. (84.) reported
tremors and erethism in one individual occupationally exposed 9.5 years
3
to inorganic mercury at concentrations of 0.005 to 0.06 mg/m air. How-
ever, Friberg and Vostal (90.) question the accuracy of this value as
they note only spot samples were used to estimate worker exposure.
Friberg and Vostal (90.) described several Russian studies which
reported an asthenic vegetative syndrome diagnosed as micromercurialism.
The syndrome was reported in workers exposed to 0.01 to 0.05 mg/nr in
work room air. The syndrome itself was not clearly defined but included
neurasthenic symptoms and was diagnosed by the occurrence of any three
of the following symptoms: tremor, thyroid enlargement, increased uptake
of radioiodine in the thyroid, hematological changes, hypotension, labile
pulse, tachycardia, dermographism and gingivitis.
Smith et al. (103.) identified a dose response relationship in workers
occupationally exposed through inhalation of inorganic mercury in the
manufacture of chlorine. Anorexia, weight loss, tremors, insomnia,
shyness, frequent colds, nervousness, diarrhea, alcohol consumption and
dizziness demonstrated a significant positive correlation. The author
summarized the clinical results as exhibiting a dose-related response to
mercury exposure by evidencing higher incidences of neuropsychiatric
symptoms. The authors concluded that, with respect to most of the symptoms,
the dose-response relationship does not exhibit sufficiently high incidence
o
to warrant concern unless exposure exceeds 0.1 mg/m air. However, they
noted that there did not appear to be a threshold of effect for anorexia
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and weight loss, but in these instances uncertainties existed which
led the authors to express a reasonable doubt as to the significance
of the effect.
Skerfving and Vostal (102.) described a hypersensitive reaction in
persons orally and dermally exposed to inorganic and organic mercury
ointments and teething powders. The disease, known as acrodynia, was
characterized by coldness, swelling and irritation of the hands, feet,
cheeks and nose, loss of hair, and ulceration. Disease onset was
characterized by increasing irritability, photophobia, sleeplessness,
and general dehydration. Neurological symptoms were also observed.
Mercury exposure was postulated as the etiologic agent, but adequate
analysis and elucidation of the mechanisms of the disease was not reported.
Inorganic and organic mercury compounds have demonstrated genetic
effects in humans and nonhumans via consumption of fish contaminated
with methyl mercury (100.). Ramel (100.) concluded that mercury pollution
has reached a level at which genetic effects on human beings do take place,
noting that little is known of the medical significance of these chromo-
somal defects.
The National Research Council (94.) concluded that more subtle effects
from mercury exposure, such as behavioral or intellectual deficits, may not
be detectable at present due to limitations in clinical procedures of
diagnosis. The Council concluded that, in view of the toxicity of mercury
and the inability of researchers to specify the threshold levels of toxic
effects, on the basis of present knowledge, all such contamination must
be regarded as undesirable and potentially hazardous to humans.
For nonhuman receptors, exposure to mercury following microbial
transformation and bioaccumulation represents a more serious hazard than
inhalation of vaporized mercury. Air borne elemental mercury has an
estimated residence time of eleven days, and is removed from the atmosphere
by precipitation. It is estimated that 40 percent of the mercury emitted
from the stacks of a power generating plant would enter a typical drainage
system (99.). Once in the aquatic system, the mercury can be transformed
into methyl mercury, a neurotoxin. Jensen and Jernelev (92.) demonstrated
that biomethylation of mercury can be accomplished by the microflora in
the sediments.
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The relative amounts of mono- and dimethyl-mercury compounds
produced are a function of temperature, pH, mercury concentration,
organic pollution load, and the microbial population. Low concen-
trations of mercury tend to favor the formation of dimethyl mercury,
a relatively inert compound, while higher concentrations of mercury
favor the formation of monomethyl mercury. In neutral and alkaline
environments, dimethyl mercury transformation is favored. Dimethyl
mercury thus produced will decompose to monomethyl mercury in a slightly
acid condition (88.).
Potter et al. (99.) studied the bioaccumulation of mercury through
the food chain of Lake Powell, Utah and found that, compared to the
mercury in the water, mercury in fish in the upper trophic level had
increased by a factor of 43,000. Thus, many of the effects of mercury
cannot be related to a single direct dosage; an organism can receive
additional dosages from eating mercury contaminated prey.
The LD50* values for intertidal red algae sporelings range from
3.0 to 8.0mg/l in water (86.). Boney (85.) however found a 40 percent
inhibition of growth in the red algae Plumaria elegans 21 days after
the sporeling was immersed in a 0.12 mg/1 mercuric chloride solution
for 24 hours.
Terrestrial animals also bioaccumulate mercury. Even though concen-
trations of atmospheric mercury may be lower than what would directly
evoke a biological response, the indirect (food chain) effects can be
considerable. For example, even though the half-life of methylmercury
in mice is 3.7 days (97.), the white-footed deer mouse (Peromyscus
maniculatus) can accumulate enough mercury to impair swimming and open
field behavior (87.).
Other studies Involving ingestion of mercury by rodents demonstrated
that relatively low dosages cause little to no effects. For example, 0.22
ppm of continuous exposure in food for two years caused no ill effects to
*Lethal Dose Fifty - a calculated dose of a substance which is expected to
cause the death of 50 percent of an entire defined experimental animal
population, as determined from the exposure to the substance by a route
other than inhalation of a significant number from that population (244.)
10
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rats in either reproduction or histopathology (98.). Dosages of one mg/
kg/day of continuous feeding caused a depressed rate of body weight gain
after 70 days and mild to severe motor disturbance in five of 18 rats
after 70 days (93.).
Kournossov (101., cited in 90.) observed changes in conditioned
reflexes in rats exposed to atmospheric concentrations of mercury vapor
at 0.002 mg/m3 to 0.005 mg/m3. However, Friberg and Vostal (90.) con-
cluded that the significance of these changes is difficult to evaluate
due to inadequate descriptions of study methods.
2.1.2 Beryllium
3
The proposed de minimis level for beryllium is 0.005 yg/m , 24-hour
average. Several generalities are evident from the literature examined.
The toxicity of beryllium is dependent on its form. For example, beryllium
fluoride is more toxic than beryllium sulfate or beryllium oxide; in other
words, the more water soluble the compound, the more rapid and severe the
response. The toxicity of beryllium oxide depends on its chemical and
physical properties. When injected intratracheally, high-fired beryllium
oxide (calcinated at 1600°C) resulted in fewer adenocarcinomas and minor
cellular reaction in rats as compared to the low-fired oxide (calcined at
1100°C and 500°C) (117-, cited in 113.).
Respiratory exposure to beryllium in occupational environments was
used as the basis for evaluating the human health effects summarized in
Table 2-2. Respiratory exposures to beryllium have produced both acute
and chronic effects. These effects have been differentiated by time between
exposure and onset of disease, and by the duration, type, and severity of
health effects. Acute manifestations of beryllium disease have occurred at
o
high concentrations in excess of 100 yg/m (105.). The Beryllium Case
Registry has reported one case of chronic beryllium disease after 9.5 years
exposure to 2.0 yg/m beryllium daily weighted average (range 0.7 to 5.9
yg/m3) (113.). Further investigations have indicated that this exposure
may have been greatly underestimated (113.). The correlation of exposure
11
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TABLE 2-2. HEALTH/ECOLOGICAL EFFECTS OF POPULATION EXPOSED TO BERYLLIUM IN AIR
Exposure
Concentration,
(ug/m3)
2.0 average
Range 0.7-5.9
5-650
34 (BeS04)
35 (BeS04)
55
Duration of
Exposure
9.5 years
occupational exposure
Acute occupational
exposure -30 minutes
7 hr/d, 5 d/wk
for 72 weeks
8 hr/d, 5 d/wk
9 hr on Saturday
for 6 months
6 hr/d, 5 d/wk
Species
Human
Human
Rat
Rat
Rat
Effects
Confirmed case of beryllium disease.
Beryllium registry.
Decreased vital capacity, pneumonltis,
bronchitis
Lung tumors first occurred after
9 months exposure; 100% incidence
at 13 months exposure
Pulmonary lesions started on month 6.
Pulmonary lesions (focal and randomly
scattered) after 9 months
Reference
National Institute for
Occupational Safety and
Health, 1972 (113.)
Eisenbud, et al . , 1948
(107.)
Reeves, et al., 1967
(115.)
Schepers, et al., 1957
(116.)
Vorwald and Reeves, 1959
(121O
ro
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and effects in other chronic cases has been lacking because of inade-
quate analytical capabilities at the time of exposure. Therefore, a
dose-response relationship of beryllium exposure at low levels cannot
be developed.
Several investigators have conducted epidemiological studies of
occupational exposures to beryllium, attempting to correlate length of
employment in beryllium occupations and cause-specific mortality. Results
of these studies are inconclusive. Mancuso (112.) reported an inverse
relationship between length of employment and lung cancer as well as for
total mortality. Similar findings were reported by other investigators
(110.). Mancuso's results did not establish the carcinogenicity of
beryllium in humans, but mentioned the possibility. Reeves (114.)
summarized beryllium toxicity thus, "the sum of evidence, at least thus
far, favors the view that humans, like the guinea pig, are susceptible
to berylliosis but resistant to beryllium cancer".
Although the carcinogenicity of beryllium is suspect, the etiology
of chronic beryllium disease or "berylliosis" is well established. Sterner
and Eisenbud (118.) hypothesized that chronic beryllium disease was the
result of antigen-antibody interaction in the affected tissue. Deodhar
et al. (106.) also reported strong evidence for the existence of cellular
immune reactivity to beryllium in patients with chronic beryllium disease.
The question then arises, at what level of exposure will an individual
develop a reaction leading to chronic beryllium disease? Sensitivity
differences between sexes and host variability (114.) makes it difficult
to establish this value. Neighborhood cases of chronic beryllium disease
3
were reported at ambient air concentrations of 0.01 yg/m . Lieben et al.
(111.) questioned these cases and established exposures to beryllium in
excess of the ambient concentrations for each of these "neighborhood cases",
The National Institute for Occupational Safety and Health (113.) concluded
that "it has yet to be definitely established whether ambient air contami-
nation alone, at a distance from a manufacturing/fabricating plant, can
cause chronic beryllium disease".
Ecological effects of beryllium have been studied in a limited way,
most of the work being associated with laboratory toxicology studies.
Thus, the studies included in the immediately available literature deal
primarily with laboratory animals.
13
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Stokinger et al. (119.) pointed out that the response to relatively
3
high dosages of beryllium (1000 pg/m air) is species specific. Respira-
tory exposure to equal concentrations of beryllium in six different
animals produced a wide range of effects (120.). Beryllium concentrations
lethal to rats produced no functional changes in rabbits, although post
mortem examinations of rabbits found pulmonary lesions.
2.1.3 Asbestos
The proposed de minimis level for asbestos is 1 yg/m , 1-hour average.
The health effects from respiratory exposure to asbestos have been well
documented for occupational environments (126.) and, to a limited extent,
nonoccupational environments (125.). Health effects from asbestos exposure
have included diffuse interstitial fibrosis, mesothelial malignancies, and
cancer of the lung and gastrointestinal tract.
Dose-response curves for asbestos exposures and cancer of the lung
and digestive tract (128.) have been developed. Exposure to asbestos
concentrations of 125 mppcf-years* has been associated with excessive
cancer deaths (125.). Murphy (124.) reported asbestos exposures to 60 mppcf-
years would result in diffuse interstitial fibrosis. Individual suscep-
tibilities and other confounding factors may also play a role in disease
incidence as latency periods for lung cancer have ranged from 3.5 to 37
years.
The review of available literature revealed several methods of analyses
and reporting of asbestos exposure which are not readily interconvertible.
For example, occupational exposures to asbestos were reported as millions
of particles per cubic foot (mppcf) or fibers per cubic centimeter greater
than 5 pm in length, whereas the de minimis level is a mass concentration
3
measurement in pg/m . The National Institute for Occupational Safety and
*Mppcf-years: Millions of particles per cubic foot-years are computed by
multiplying the asbestos level (mppcf) at each job and time period by
years at the job and summed across all jobs. The total cumulative expo-
sure is thought of as mppcf-years (122.). It should be noted that such
exposures are occupational, 8 hours per day, and not continuous as in
community exposures.
14
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Health (126.) considered this conversion problem and concluded that a general
3
conversion factor for equating yg/m to mppcf could not be developed.
Inherent differences in asbestos type and operation of the plant generating
the asbestos would result in conversion factors ranging from 11 to 108,000
for estimating the number of fibers per nanogram. Furthermore, the majority
of health effects data are from occupational exposures using fiber number
concentrations. Fiber size and shape are important factors in producing
tumors, with fibers less than 0.5 ym in diameter most active (126.).
Asbestos fiber length has been considered important in initiating
fibrosis, but Selikoff and Lee (129.) pointed out that it cannot be said
with any confidence that fibrogenicity drops to negligible proportions at
fiber lengths of 5 urn or 1 ym. The authors speculated that smaller fibers may
also be responsible for fibrotic and mesotheliomatous reactions. Other
confounding factors affecting disease induction include cigarette smoking
(129.).
The available health effects data for developing dose-response curves
are available but in units of measure as particle counts and not mass con-
centrations. The dose response information is further limited in its
application since it was generated from health workers occupationally
exposed and not from continuous exposure to the general population.
Asbestos has been reported to cause pulmonary fibrosis in wild and
domesticated animals living in the vicinity of asbestos mines or factories.
High concentrations are implied but dose-response information is not avail-
able (123.).
Available information on the effects of asbestos to nonhuman organisms
is of recent origin and involves laboratory animals exposed to high dosages.
Physiological reactions in rats include formation of malignant neoplasms as
well as various gross morphological changes in the lung for chronic expo-
sures (2 years) to milled asbestos at approximately 49 mg/m3 (fiber concen-
tration of 0.08 to 1.82 percent). Mice, gerbils, and guinea pigs exhibited
similar morphological changes, but no neoplasms were observed under similar
exposures (127.).
15
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As with man, the literature generally supports the assumption that
fiber length, fiber concentration, and chemical origin or type of asbestos
mineral influences the response of an organism exposed to asbestos. In
fact, literature reporting asbestos exposure is infrequently reported in
yg/m3, but rather as fiber concentration or total "asbestos" concentration
including nonfibrous pseudomorphs and other allied chemical species.
Furthermore, the interconversion of these various types of measurements
is a technically difficult problem as explained above. No information
was found concerning field-observed effects of asbestos on plants and
animals.
2.1.4 Fluorides
The proposed de minimi's level for fluorides is 0.01 pg/m , 24-hour
average. The health effects data in Table 2-3 relate to occupational and
community respiratory exposures to fluorides in or near aluminum smelters
and phosphate fertilizer plants. The populations concerned were subject
to concomitant exposure to other compounds associated with the respective
industries.
Many community studies have monitored dental fluorosis in children
as an evaluation of respiratory fluoride exposure. Dental fluorosis, or
mottled enamel, is a result of functional changes preceding the eruption
of a tooth. Consequently, chronic fluoride exposure will result in mottled
enamel in children under the age of five to eight years, but can be tolerated
without effects in adults. Leloczky (109., cited in 136.), reported
o
fewer dental caries than expected in children exposed to 0.03 to 0.06 mg/m
fluoride particulates in air. Sadilova (185., cited in 136.) supported
this finding, but noted an increase in the incidence of mottled enamel in
children exposed to 0.03 to 0.56 mg/m3 in air. Agate et al. (131., cited
in 136.), also observed fewer dental caries in children living near an
aluminum production plant, but noted a slight increase in very mild mottling
of tooth enamel associated with respiratory exposure to 0.045 to 0.048 mg/m^
fluorides.
Elkins (132.) reported nosebleeds and sinus trouble in welders exposed
to 0.7 mg/m3 hydrogen fluoride. Midttun (108., cited in 136.), observed
an allergic asthma reaction of unknown etiology in aluminum plant workers
16
-------
TABLE 2-3. HEALTH/ECOLOGICAL EFFECTS OF POPULATIONS EXPOSED TO FLUORIDES IN AIR
Exposure
Concentration
0.54-0.66 ug/m3
0.55 i*/*3
0.64 ug/M3
0.76 ug/M3
0.98 ug/M3
1.6 ug/M3
2.0 ug/M3
4.3 ug/M3
4.7 ug/M3
5.0 ug/M3
B.2 pg/M3
Duration of
Exposure
Continuous
Continuous
Continuous
Continuous
40 days
Continuous
24 hr
Continuous
7 days
Continuous
Continuous
Continuous
Continuous
Continuous
Species
Corn (Zea mays)
Strawberry
Marshall Var.
Soybean
(Glyclne max)
Gladiolus, var.
Snow Princess
Ponderosa pine
(Plnus ponderosa)
Com (Zea mays)
Corn (Zea mays)
Oat (Avena
satlvaT
Sorghum
(Sorghum vulgare)
Wheat (Trltlcum
aestlvuil
Wheat (Trltlcum
aestlvunT)
Effects
HI Id leaf symptom; Chlorotlc streaking on tips
. and margins of leaves.
Achenes and underlying receptacle tissue at the
apical end of fruit did not develop.
Significant reduction In number of pods,
weight/seed, stem length, significant Increase
In dry weight of stems and leaves.
391 Increase In oxygen uptake over controls
(Increase In respiration). Necrosis.
Chlorosis of young needles.
A mean of 1.9S of total leaf area affected by
necrosis.
Seed production completely Inhibited.
Delay of maturation; significant Increase In
dry weight of stems and leaves.
851 reduction In seeds; 301 reduction In seed
weight (weight/seed); Increase In dry weight
of steins and leaves.
No significant difference from controls In seed
production, seed weight, dry stems and leaf
weight. Trace of leaf tip dleback noted after
10 weeks.
SOS reduction 1n number of seeds produced;
18X reduction In weight/seed; Decrease In
dry stem and leaves weight.
Reference
Pack and Sulzbach. 1976
(142.)
Pack, 1972 (141.)
Pack and Sulzbach. 1976
(1«.)
Hill, et al., 1959 (133.)
Adams, et al.. 1956 (130.)
Hitchcock, et al.. 1964
(134.)
Pack and Sulzbach. 1976
(142.)
Pack and Sulzbach. 1976
(142.)
Pack and Sulzbach. 1976
(142.)
Pack and Sulzbach, 1976
(142.)
Pack and Sulzbach. 1976
(142.)
-------
TABLE 2-3. HEALTH/ECOLOGICAL EFFECTS OF POPULATIONS EXPOSED TO FLUORIDES IN AIR (continued)
Exposure
Concentration
10.4 gg/m3
40 ug/m
0.03-0.11 mg/m3
0.045-0.048 mg/m3
0.03-0.06 mg/m3
0.03-0.56 mg/m3
0.09-0.90 mg/m3
0.14 mg/m3
0.7 mg/m3
2.5 mg/m3
1-2 mg/m3
Duration of
Exposure
Continuous
Continuous
7 days
Single exposure
Community
exposure - continuous
Community
exposure -continuous
Community
exposure -continuous
Community
exposure -continuous
Community
exposure -continuous
6h
Occupational -
Aluminum plant
workers
Occupational -
Aluminum plant
workers
Species
Strawberry
Marshall var.
Soybean
(Gljfclne max)
Human
Human
Human
Human
Human
Human
Human
Human
Human
Effects
Severely restricted fruit development. Approxi-
mately 50" decrease in weiqht/frui t. Significant
reduction in percentage of flowers that developed
into fruit. Chlorosis of leaves; Marginal
necrosis.
Average of 34.3^ increase in respiration.
Perceptible odor concentration.
Slight increase very mild mottling of tooth
enamel compared to control. Teeth of children
near plant appeared less prone to carles.
Children with slightly less carles than normal
and excreted <6.6 mg F/l in urine.
Incidence of mottled enamel: Exposed 31.0-
37. 5~. Control 2.1* Incidence of dental caries:
Exposed 10. 8-24. 5V Control 37.5"
Slight dental fluorosls -58*. Moderate dental
fluorosls - 8". Severe dental fluorosis - 1 "
No significant differences In clinical observa-
tions between exposed and control.
Welders exposure to AP-Nosebleeds .
Sinus trouble
Osteosclerosis
Nausea, headache. Irritation of conjunctiva and
respiratory passages. 54 cases allergic asthma
observed over 5 years, Mleroen unknown fluoride
compound. Concomitant exposure to organir tars,
dust t.nrne fluorides, HF . A1F . cryolit--. fll.,fl,.
502. ' _|
Reference
Pack. 107? (141.)
Yu and Miller, 1967 (149.)
National Institute for
Occupational Safety and
Health, 1976 (140.)
Haale. 1940 (131.),c1ted
in (136.)
Leloczky. 1970 (109.),
cited in (136.)
Sadllova, 1957 (185.),
cited in (136.)
Khyngln and Shamsutdfnova,
1970 (139.). cited In (136.)
Balazova, 1971 (212.. 223.)
Balazova, et al, 1970 (224.)
Hluchan, et al, 1968 (225.)
Balazova « Llpkova. 1974 (226.
Lezovic 4 Balazova, 1%9 (227.
cited in (136.)
Elkins, 1959 (132.)
Hodge and Smith, 1977 (13fi.)
Kaltreider, 197? (138.)
Midttun, I960 (108.),
cited in (136.)
CD
-------
exposed to 1 to 2 mg/m particulate fluorides. Nausea, headache, irri-
tation of conjunctiva and respiratory passages were also observed. Hodge
and Smith (136.) and Kaltreider (138.) noted osteosclerosis in aluminum
plant workers exposed to 2.5 mg/m fluoride particulates in air.
Study of the health effects of exposure to low concentrations of
atmospheric fluorides has centered on dental effects in children. The
ability of fluorides to prevent dental caries has been noted; indeed,
the addition of fluorides to drinking water is recommended to prevent
dental caries.
The primary ecological effect of fluorides is on vegetation. Gaseous
fluorides enter the leaves of vegetation primarily through the stomata, the
primary site of accumulation being leaf tips or margins (137.). The visible
symptoms of fluoride toxicity vary according to the type of plant, but seem
to be relatively consistent. The initial symptoms of most herbaceous plants
is chlorosis, starting at the leaf margins of elongating leaves; usually
this results in necrosis. In many of the grasses including corn and sorghum,
chloritic flecks appear scattered at the tips and upper margins of the middle-
aged leaves.
Ponderosa pine is very susceptible to fluoride toxicity. An atmospheric
exposure of 0.98 yg/m for 24 hours produced chlorosis of the immature
needles, which turned to a light brown or reddish brown at the tips. This
discoloration may be interrupted by dark bands, which may indicate inter-
mittent exposures (148.).
The work of Pack (141.) and Pack and Sulzbach (142.) indicated that
damage to a plant may result before visible symptoms occur. For example,
strawberry bushes grown in a continuous exposure to 5.0 yg/m air (hydrogen
fluoride) exhibited a significant decrease in fruit development and fruit
weight compared to controls, yet showed no signs of chlorosis (141.).
Animals are exposed to fluorides principally from ingesting contami-
nated forage or from feed supplements. The most frequently encountered
symptoms are dental lesions. In sheep, ingestion of 10,000 mg/m fluorides
in water caused decreased wool production and dental lesions (143.). Fluo-
rides added to feed at a concentration of 2.0 mg/kg caused slight mottling
19
-------
and wear on the fourth incisor of dairy cattle (147.). Stoddard et al.(145.)
fed dairy cattle 2.08 mg/kg of fluoride in feed (109 ppm) and found reduced
lactating ability but not a significant decrease in overall production
of milk. When fed 1.17 mg/kg fluoride in feed (55ppm), reduced feed consump-
tion and reduced lactating ability were noted. But again, there was no
significant decrease in total milk production (146.).
One problem in a literature study is to generalize the results of
experiments in which fluorides added to feed or water are compared to
results where animals forage naturally contaminated feed. Shupe et al.
(144.) fed groups of dairy heifers food supplemented with sodium fluoride
and calcium fluoride as well as the fluoride contaminated hay, and found
that the naturally contaminated hay was as toxic as the sodium fluoride
supplement. In addition, Hobbs and Merriman (135.) found that hay contami-
nated with fluoride from an aluminum smelter was somewhat less toxic than
sodium fluoride supplemented food.
There is evidence that a lag period may exist before physiological
expression of fluoride toxicity. Suttie et al. (147.) found a two to five
year latent period between the time dental lesions were noted and the
development of other physiologic effects including depression of milk
production. Thus, he suggests that fluoride toxicity is a function of
exposure (time) and amount of ingestion.
2.1.5 Sulfuric Acid Mist
o
The proposed de minimi's level for sulfuric acid^mist is 1 yg/m ,
24-hour average. A comprehensive review of the human health effects from
sulfuric acid mist published by the National Institute for Occupational
Safety and Health (NIOSH) was the source for much of the effects data
described below (162.).
The reported health effects from respiratory exposure to low concen-
trations (Table 2-4) report different effects as explained in the following
narrative.
20
-------
TABLE 2-4. HEALTH/ECOLOGICAL EFFECTS OF POPULATIONS EXPOSED TO SULFURIC ACID MIST IN AIR
ro
Concentration
(mg/m3)
0.07 0.1 um dli
0.1 0.3 \m dla I
0.12 0.7 um dial
0.07 1.0 um dial
0.22 2.5 um dla
0.35
0.4
0.5
0.6-0.85
0.8-16.6
2.9
>4.0 (0.6. 0.9. and
9.0 um dua)
8 (-1 umdla)
20
20
87-1600
(<2 um dla)
Duration
1 hr
5-15 mln
10 sec
5-14 days
Unknown
Occupational
60 m1n
18-140 days
8-72 days
7 hr/day
for 13 days
7 hr/day
for 9 days
NA
Species
Guinea pig
Human
Human
Guinea pig
Human
Human
Human
Guinea pig
Guinea pig
Rabbit (New
Zealand white)
CF-1 mice
Rabbit
Rat
House
Guinea pig
tffects
Increase pulmonary flow resistance
percentage: 32
41
43
14
18
Increased respiration rate, decreased maxi-
mum Insplratory and expiratory air flow
Conditioning of electrocortlcal reflex
Slight lung Irritation
Perception of odor and Irritation of mucosa
Etching of dental enamel
Coughing, some bronchoconstrictlon rales
Greatest pulmonary pathology occurred at
0.9 |im diameter exposure; foci of pulmonary
damage changed with varying particle size.
Increased time of exposure did not increase
mortality; suggests concentration more
Important than duration.
Slight maternal toxicity (none at 5 mg/m );
no teratoqenicity or fetal toxicity
Same as above
Species sensitivity to HjSO^ particles
compared; sensitivity increases: Rabbit
< Rat Mice < Guinea piq
Reference
Amdur, et al., 1975
(151.)
Amdur. et al., 1952
(153.)
Lewis, et al.. 1972
(158.)
Bushtueva. 1962 (155.)
Lewis, et al., 1972 (158.)
Halcolm and Paul. 1961
(159.)
Sim and Pattle. 1957
(166.)
Thomas, et al.. 1958
(168.)
Amdur, et al., 1952
(15Z.)
Hurray, et al . . 1979
(161.)
Treon, et al., 1950
(221.)
-------
TABLE 2-4. HEALTH/ECOLOGICAL EFFECTS OF POPULATIONS EXPOSED TO SULFURIC ACID MIST IN AIR (continued)
Concentration
centratl
(mg/m3)
Duration
Species
Effects
Reference
ro
r>o
OTHER MEASUREMENTS
ph 3.2, 0.9 mm drop
size
1.7 vm aerodynamic
diameter of 18 M
sulfurlc add
6 days/wk
10 hrs/day
for 14 days
Halo blight on
kidney beans
Fusiform rust on
willow oak
Kidney beans
4- to 6-wk-old
soybean seedlings
Pathogen" Inhibition (varying percent related
related to life cycle stage)
Pathogen Inhibition (86 percent)
SEM observed extensive erosion of cuticular
waxes (therefore, 3.2 pH may Inhibit host
invasion but cuticular erosion leaves plant
more susceptible to invasion post exposure).
None observed with scanning electron
microscope or human eye
Shriner, 1977 (165.)
Wedding, et al., 1979
(170.)
-------
The health effects from respiratory exposure to sulfuric acid mist
include irritant effects on mucous membranes and chemical corrosion of
dental enamel. Amdur et al. (153.) reported changes in respiratory rates
3
and respiratory flow from exposure to 0.35 mg/m . The exposure tests were
conducted on human volunteers of various ages. The authors noted that
asthmatics, cardiac patients, and other less healthy persons in the
general population may be more susceptible to sulfuric acid mist exposure.
NIOSH (162.) reported similar results by Morando (160.), but questioned
the validity of the findings at these concentrations. Sackner et al.
(164.) supported the NIOSH conclusions showing no respiratory resistance
3
at sulfuric acid concentrations of 0.01 to 1.0 mg/m . Toyama and Nakamura
(169., cited in 162.) demonstrated pulmonary airway resistance in humans
at exposures of 0.01 to 0.1 mg/m , but concluded that concomitant hydrogen
peroxide and sulfur dioxide exposure had produced a synergistic effect.
Earlier, Lewis et al. (158.) extensively reported the sensory and
central nervous system studies in the USSR and noted conditioned reflex
responses and perception and irritation thresholds in humans exposed to
3
atmospheric concentrations of 0.4 and 0.6 to 0.85 mg/m , respectively.
Malcolm and Paul (159.) reported etching of dental enamel from occupational
3
exposures to 0.8 to 16.6 mg/m sulfuric acid mist. Other studies have noted
etching of dental enamel but accurate monitoring measurements were lacking
(167., 154.).
NIOSH (162.) also noted one study by Raule (163.) which reported worker
acclimation to inhalation of sulfuric acid mist. Conversely, Sim and
Rattle (166.) noted long-lasting bronchitic symptoms in two male volunteers.
Contradictions of effects at similar concentrations may be due to variance
in relative humidity, temperature, and particle size (150., 156., 162., 166.).
On the other hand, it must be remembered that all studies described
above were either occupational or human volunteer studies of health persons.
It is possible, as noted by Amdur et al. (153.), that less healthy persons
in the general population may be more susceptible to sulfuric acid mist
exposures. Epidemiological studies to support this relationship and identify
a dose-response relationship are lacking.
23
-------
From the viewpoint of nonhuman effects, there has been extensive
testing of the effects of sulfuric acid aerosol exposure on laboratory
animals and on selected plant species; however, the lowest known value
reported in the literature as having a biological effect is 0.07 mg/m
(151.).
In Table 2-4 selected literature references for acute or chronic
biological effects of sulfuric acid aerosol are presented. Damage from
sulfuric acid aerosol is species-specific (221.). Particle size has a
major influence on both the degree of damage and the specific places of
damage in the pulmonary system (168., 151.). However, insufficient information
is available to establish a lower limit of effect. Because of the powerful
hygroscopic nature of concentrated sulfuric acid, it is likely that any
exposure results in some effect on biological tissues (157.).
Waxy coatings on many plants are somewhat protective, though erosion
of these layers begins with initial exposure to sulfuric acid (170., 171., 172.).
Increased exposures result in tissue damage from drying, heating, and
charring. On the other hand, sulfuric acid aerosol exposure appears to be
associated with a slight increase in resistance to parasite attack, probably
the result of either damage to the parasite or substrate changes which, in turn,
do not provide favorable conditions for the parasite/host relationship (165.).
2.1.6 Vinyl Chloride
The proposed de minimi's level for vinyl chloride is 1 pg/m, maximum
value. Toxicological experience with this compound came as a result of
occupational health studies which identified an excess incidence of angio-
sarcoma of the liver in vinyl chloride workers (175.). Vinyl chloride was
previously considered non-toxic and therefore exposure was not of-great
concern. Consequently, adequate personal monitoring data do not exist
to allow an accurate estimate of worker exposure and cancer risk.
Several researchers have correlated length of exposure measured as
years of work in vinyl chloride plants to occupational diseases including
angiosarcoma of the liver (174., 175., 184.), respiratory and brain cancers,
cancer of other unspecified sites, and chromosome aberrations (177.).
24
-------
Other health effects observed include nervous manifestations (euphoria),
cardiovascular manifestations (arterial hypertension), Raynaud's syndrome
(abnormal sensitivity to cold), digestive problems (hepatomegaly), respira-
tory manifestations, skin irritations, endocrine alteration, hematologic
changes, and bone changes (acroosteolysis) (179., 180., 183., 186.).
Several community epidemiological studies have been conducted to
correlate proximity to a production facility and various health effects.
For example, Infante (178.) noted an excessive number of congenital malfor-
mations in communities with polyvinyl chloride production facilities.
Ambient concentrations of vinyl chloride during the study period were
not given; therefore, no association between vinyl chloride exposure
and congenital malformations can be stated.
Edmonds et al. (176.) conducted a community case-control study of the
possible relationship between congenital central nervous system malforma-
tions and exposure to vinyl chloride monomer emissions from a local plant.
Although central nervous system malformations were significantly higher
than the United States rates, no correlation was found with occupation of
parent or residential proximity to the plant site. The authors suggest
that vinyl chloride may be one of several pollutants emitted from nearby
plants which may be responsible for the high rates.
NIOSH (181.) concluded that there is probably no threshold for car-
cinogenesis from vinyl chloride exposure, although it is possible that at
very low concentrations the latency period may be extended beyond the life
expectancy. This implies that setting a low enough exposure level for
vinyl chloride may decrease cancer incidence, but data thus far have come
from healthy workers occupationally exposed 8 hours per day. Thus, setting
a safe level for persons not occupationally exposed must consider those
most susceptible to disease.
Basuk and Nichols (173.) best summarized the vinyl chloride data by
stating that because of the extremely high vinyl chloride concentrations in
plants with little or no reliable monitoring facilities, because of personnel
turnover and lack of medical records and because of unknown effects of other
contaminants used in the process which may be carcinogenic, it is impossible
25
-------
to determine the shape of the hunan dose-response curves except in a
rough qualitative manner.
The relatively recent understanding of the hazard of vinyl chloride
to man has resulted in studies using laboratory animals to establish
dose-response relationships. Early testing at exposures assumed to be
at nontoxic levels has resulted in carcinogenesis. It is believed that
subsequent testing has been conducted at lower levels, but these findings
have apparently not reached the open literature, and, consequently, are
not accessible.
Vinyl chloride is carcinogenic in a number of laboratory species
including mice, rats, and hamsters. Mammary carcinomas can be induced
in laboratory animals by exposure to one ppm or less of vinyl chloride
(173.). Repeated daily exposures in both rats and mice at 50 ppm are
carcinogenic (187.). Also, incidence of angiosarcoma and nephroblastomas
appear to be dose related in the lower range of exposures (182.).
Information is not available on either chronic or acute effects of
exposure of vinyl chlorfde to natural populations.
2.1.7 Hydrogen Sulfide
The proposed de minimi's level for hydrogen sulfide is one yg/m3, one-hour
average. Much of the available health effects data for hydrogen sulfide were
derived from acute occupational exposure studies of concentrations greater
than five mg/m3 (see Table 2-5). Community studies of hydrogen sulfide exposure
have also been reported but exposures were much higher than the de minimis
levels. Thus, the major effects at the de minimi's concentrations are psycho-
physical responses to odors.
The odor threshold has been variably reported at one to 45 yg/m
by Miner (192.) and 0.65 yg/m by Leonardos et al. (191.). Differences in
odor thresholds can be explained by variations in the methods and statis-
tical analyses used to determine the threshold level and inherent variation
in the study population (193.). The National Research Council (193.) reviewed
the psychophysical factors of hydrogen sulfide exposure and concluded that
one cannot depend on adaptation to reduce awareness of odorous pollution.
The National Research Council noted that sociological factors (such as age,
26
-------
TABLE 2-5. HEALTH/ECOLOGICAL EFFECTS OF POPULATIONS EXPOSED TO HYDROGEN SULFIDE IN AIR
Exposure
loncentrailon,
V9/*F
1-45
18
42
400
420
420
420
5,000
10.000
15.000
15.000
28.000
28.000
Duration of
Exposure
12 hr/d
3 months
Continuous
2 months
Continuous
Continuous
Continuous
Unknown
12 hr/d
3 months
6-7 hr
5d
90d
8 hr/d
Species
Human
Rat
Sugarbeet
Lettuce
Human
Ponderosa
pine
Seedless
grape
Alfalfa
Human
Rat
Human
Mouse
Monkey
Human
Effects
Odor Threshold
Motor chronaxle abnormalities
Increased yield
Community exposure -Terre Haute. Indiana.
Nausea, loss of sleep, abrupt awakening,
breathlessness. H?S range 30-11000 yg/m3
Tip burn visible after 8 weeks
Detectable damage, lesions on leaves
Successive harvests showed yield reduction
Occupational exposure. Conjunctlval and
corneal Irritation. Concomitant CSj
expoAute. H2S range 5,000-20,000 ug/m3
M11d Irritation of tracheal, broncheal
mucosa, lower weight gain, motor
chronaxle abnormalities, abnormal
cerebral cortex dendrites.
Occupational exposure. Eye Irritation
Anorexia
Weight loss, Increased blood amylase
and alkaline phosphatase activities
Occupational exposure. Fatigue,
decreased libido, anorexia, dizziness,
eye and respiratory tract Irritation.
Reference
Miner, 1969 (192.)
Duan, 1959 (189.)
Natl. Res. Council. 1979
(193.)
Illinois Institute for Env.
Quality, 1974 (190.)
Natl. Res. Council, 1979
(193.)
As above (193.)
As above (193.)
Masure, 1950, (228.). cited In (193.)
Duan. 1959 (189.)
Nesswetha, 1969 (229^c1ted In (194.)
Hays, 1972. (230.). cited 1n (194.)
Sandage. 1961 (195), cited In (194.)
Ahlborg. 1951 (188.)
ro
-------
sex, and socioeconomic status) affect odor complaints. They concluded
there is no evidence that the experience of malodor per se produces
disease but noted that poor health may increase the displeasure or at
least the frequency of complaints about odors.
Community exposure studies in Terre Haute, Indiana conducted by
the Illinois Institute for Environmental Quality (190.), observed various
psychological disturbances from atmospheric hydrogen sulfide concentra-
tions of 400 yg/m3. Nausea, loss of sleep, abrupt awakening, breathless-
ness, headaches, abdominal cramps, diarrhea, choking, coughing, eye
irritation and acute asthma attacks were described. The Institute suggested
that low concentrations of hydrogen sulfide posed special dangers to indi-
viduals with heart or lung disease (190,, 228., cited in 193.).
Studies of occupational exposure have generally concentrated on
effects at levels greater than 5000 yg/m . Health effects from occupa-
tional exposures included eye and respiratory tract irritation and brain
damage. The existence of a discrete clinical chronic poisoning from
hydrogen sulfide has been questioned (194., 193.), with some indication
that the chronic poisonings are actually recurring acute or subacute
toxic exposures.
Acute effects have not been included in Table 2-5 since these
effects occur at concentrations greater than 700 mg/m . At such concen-
trations, respiratory distress, nervous system effects, and eventual
paralysis of breathing occur (194.).
The environmental effects of hydrogen sulfide', as assessed through
laboratory experiments, are both varied and species specific. At low
levels (4 yg/m in air) continuous exposure produced an increased yield
on sugar beets and lettuce (193.). Concentrations an order of magnitude
higher, however, caused tip burn on ponderosa pine, and lesions on the
leaves of seedless grapes (193.). Effects on animals show UD with concen-
trations in the 10,000 yg/m range and above. Symptoms range from mild
irritation of trachea and broncheal mucosa to anorexia and weight loss.
28
-------
2.1.8 Methyl Mercaptan
The proposed de minimis level for methyl mercaptan is 0.5 yg/m , one-hour
average. Toxicological data are limited to a few cases.
Shults et al. (198.) described an acute respiratory exposure to
methyl mercaptan (methanethiol) in a 53 year old black male. The worker
was engaged in salvaging metal cylinders and was instructed to empty
tanks containing methyl mercaptan. The worker was presumably exposed
to high atmospheric concentrations of the compound, although personal
monitoring was not available. Acute, severe hemolytic anemia and methe-
moglobinemia developed. Deep coma persisted and the victim died 28 days
after exposure. The authors concluded that the likely mechanism of the
hemolysis was an oxidant effect of methyl mercaptan in a person deficient
in erythrocytic glucose-6-phosphate dehydrogenase (G-6-PD), an inherited
deficiency.
Fairchild and Stokinger (196.) and Key et al. (197.) described local
and systemic effects in humans from respiratory exposure to methyl
mercaptan. Observed effects included irriation of skin, eyes, and mucous
membranes. The toxic effect of methyl mercaptan is similar to that of
hydrogen sulfide with central nervous system depression resulting in
respiratory paralysis. Although personal exposure data and ambient
measurements of methyl mercaptan were not given, the above effects probably
occur at excessive levels, several orders of magnitude higher than the pro-
posed de minimi's level.
Leonardos et al. (191.) reported an odor threshold for methyl mercap-
tan of 0.0021 ppm (4.1 ug/m3). Verschueren (199.) reported a threshold
odor concentration of 0.044 yg/m3. The differences in the two odor threshold
values reported may be explained by methods of study, sensitivity of observers
to the odor, and different types of odor thresholds reported. For example,
the study by Leonardos et al. (191.) reported an odor threshold which can be
recognized by all panel members (Population Identification Threshold 100
percent) whereas the value reported by Verschueren (199.) was an absolute
perception threshold.
29
-------
Available information on the toxic effects of methyl mercaptan on
nonhumans is limited to a few high dosage experimental animal studies.
The concentration which caused 50 percent of experimental rats to become
comatose was determined to be 0.16 percent by volume (200.). The concen-
tration of methyl mercaptan lethal to rats after 10 to 20 minutes exposure
was determined to be 1.0 percent by volume (231.).
2.1.9 Dimethyl Sulfide
3
The proposed de minimi's level for dimethyl sulfide is 0.5 yg/m ,
one-hour average. This level was established primarily to control odors.
Specific information on the human health effects of dimethyl sulfide were
not found in the available literature. The following discussion deals with
the odor properties of the compound.
Leonardos et al. (191.) reported an odor threshold of 0.001 ppm (2.6
pg/m3) for dimethyl sulfide. Verschueren (199.) reported an absolute per-
ceptible limit of 0.4 ppb (1.0 ug/m3).
Dimethyl sulfide is one of four total reduced sulfur (TRS) compounds
for which de minimi's levels were proposed. These TRS compounds are charac-
terized as highly odorous, generally considered repugnant or malodorous.
The National Research Council (218.) noted physiologic and morphologic
changes occur in animals from exposure to odorants. These effects are
different from toxic effects. Similar manifestations from exposure to
odorous pollutants are suggested in humans. The Council noted that the
impact of these changes on human health has yet to be established, but
warrant immediate study.
No information was available in the immediate literature concerning
field-observed effects of dimethyl sulfide on nonhumans. Only data on
high dosage, experimental animal studies were available. Ljunggren and
Norberg (231.) state that a 5.4 percent by volume concentration (140,000
o
mg/m ) of dimethyl sulfide is lethal to rats after a 10 to 20 minute
exposure. Zieve et al. (200.) report that the inhalation dose at which
o
50 percent of rats become comatose is 9.6 percent by volume (243,040 mg/m ),
30
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2.1.10 Dimethyl Dlsulfide
The proposed de minimi's level for dimethyl disulfide is 2 yg/m3, one-
hour average. This level was established primarily to control odors.
Toxicological information for dimethyl disulfide is sparse, with only
limited short-term studies on animals and no data for human health effects
available. Thus, the discussion will be limited to the odor properties
of the compound.
Verschueren (199.) reported two different odor thresholds for dimethyl
disulfide: a threshold odor concentration of 0.005 mg/m and a 50 percent
recognition threshold of 5.6 ppb (21.5 yg/m ). Berglund (219.) studied
the effects of sulfurous compound mixtures on odor intensity and noted
additive and interactive components of mixtures. For example, a field
investigation of a pulp mill indicated that selective elimination of
several sulfur compounds including dimethyl disulfide would not necessarily
reduce the odor strength of the effluent. Indeed, the author noted that a
slight increase in odor intensity may result from selective elimination of
hydrogen sulfide, methyl mercaptan, dimethyl disulfide, and dimethyl
sulfide.
Dimethyl disulfide is a naturally occurring compound produced from
aerobic or anaerobic activity in soils and organic matter (232., 233.,
234.). Dimethyl disulfide residues have been confirmed in human blood,
urine, and respiratory gas (235., 236., 237.). Gage (238.) reported
symptoms of lethargy, respiratory difficulties, and low weight gain in
rats exposed to 250 ppm dimethyl disulfide in air. Respiratory exposure
to 100 ppm dimethyl disulfide did not elicit a toxic reaction, after six-
hours exposure. Kadota and Ishida (234.) reported inhibition of Aphanomyces
euteiches (Pea root rot) at dimethyl disulfide concentrations as low as 20 ppm.
2.1.11 Carbon Disulfide
3
The proposed de minimis value for carbon disulfide is 200 yg/m , one-hour
average. Toxicological experience with carbon disulfide in humans has been
limited to occupational exposures in the viscose rayon industry where con-
comitant exposure to hydrogen sulfide occurs. A comprehensive review of
human health effects from respiratory exposure to carbon disulfide published
31
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TABLE 2-6. HEALTH/ECOLOGICAL EFFECTS OF POPULATION EXPOSED TO CARBON DISULFIDE IN AIR
Exposure
Concentration,
(mg/m3)
Duration of
Exposure
Species
Effects
Reference
0.08
0.09
0.65
1.0
0.1
1.5-4.2
3-10
9
9-50
10
10
15
10-15 minutes
10 minutes
160 d
Unknown
9 months
Occupational exposure
0.5-30 years
Occupational exposure
4+ years
Occupational exposure
Occupational exposure
Occupational exposure
Occupational exposure
Human
Human
Human
Carbon Disulflde Alone
Disturbed rate of execution of assigned motor
responses
CMS effects - visual center of brain
Odor threshold
Carbon Disulflde and Other Chemicals
Rat
Human
Human
Human
Human
Human
Human
Human
Inflammation of bronchi, weight changes.
Increased serum aspartate amino-transferase
and blood chollnesterase. Most severe with
concomitant exposures.
Increase In color and light sensitivity
Hypotension; nervous system excitability
Retinal degeneration; conjunctiva! inflamma-
tion; color-vision disturbances
Inmunologlc abnormalities
Adverse effects-menstruation and pregnancy
in exposed workers
Increased digestive tract diseases
Muscular power diminished, reflexes slowed
Boklna, et al., 1976 (206.)
Boklna, et al., 1979 (205.)
Leonardos, et al., 1969 (191.
M1s1ak1ew1cz, et al., 1972
(209.), cited 1n (211.).
Gabovich, et al., 1978 (210.)
Kramarenko, et al., 1971
(240.),cited In (211.)
Szymankowa, 1968, (213.),
cited In (211.)
Kashln, 1965 (241.). cited
In (211.).
Agadzhanova, 1978 (203.)
Gabovich, et al., 1975 (210.)
Vasllescu. 1972, (239.),
cited In (211.).
Concomitant exposure to hydrogen sulflde; see text for limitations of this study.
-------
by the National Institute for Occupational Safety and Health (211.) was
relied upon for much of the effects data described below. Carbon di-
sulfide exposure has produced health effects in the cardiovascular,
neurologic, and reproductive systems and in the eye (Table 2-6).
The odor threshold for carbon disulfide is 0.21 ppm (0.65
2
mg/m ) by Leonardos et al. (191.), but has been reported as low as 0.08
mg/m3 by Baikov (127) cited in (201.). Lindvall (208.) noted that a con-
comitant exposure to hydrogen sulfide, nitric oxide, and acid fumes increa-
sed the human sensitivity to carbon disulfide. Studies by Berglund (219.)
emphasized this finding, noting that exposure to a mixture of sulfur compounds
will alter the psychophysical response to the odor. The National Research
Council (218.) emphasized the adverse public response to odors of sulfurous
compounds and suggested setting acceptable odor limits for compounds other
than hydrogen sulfide at ten times the odor threshold.
The lowest concentration eliciting a response to carbon disulfide
gas was documented by Bokina et al. (206.). Human volunteers exposed to
0.08 mg/m exhibited disturbed rates of motor responses. Bokina et al.
(205.) later described central nervous system effects on the visual center
of the brain from exposure to 0.9 mg/m carbon disulfide.
Much of the remaining health effects data presented in Table 2-6
were published by Russian and Eastern European authors who have studied
protective and adaptive reactions of carbon disulfide on humans.
Kramarenko (240., cited in 211.) observed hypotension and nervous system
excitability in viscose rayon workers exposed to three to ten mg/m3 carbon
disulfide in workroom air. Kashin (241., cited in 211.) described
immunologic abnormalities in viscose rayon workers exposed to ten to 50 mg/m
carbon disulfide in air. Agadzhanova (203.) described adverse effects on
menstrual function and pregnancy in female rayon workers exposed to ten mg/m^
in workroom air. Petrov (242.) cited in (211.), noted an increased risk of
spontaneous abortions in female rayon workers exposed to atmospheric concen-
trations of 27 mg/m3 carbon disulfide for three plus years. Cardiovascular
effects were reported by Gavrilescu and Lilis (243., cited in 211.) in
rayon workers exposed for ten years to 20 to 42 mg/m3 carbon disulfide in
workroom air. Arteriosclerotic changes and arterial hypertension were also
observed.
33
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Dose response information for carbon disulfide in nonhuman
populations is difficult to elucidate, as no published studies of
this nature are immediately available.
Laboratory animal studies have been conducted because of the need
to better understand the human effects. Respiratory exposure levels
have been approximately 1000 mg/m3. The most frequently occurring effects
at this dosage are lethargy and loss of motor control. Effects on repro-
ductive success have also been noted. The relatively new technique of
behavioral toxicology has been used to help assess the effects of carbon
disulfide (207., 216., 217.). Respiratory exposure to the carbon disulfide
affected the operant behavior in pigeons and the aversive threshold in
squirrel monkeys.
Some authors (204., 209., 214., 215.) have reported a synergistic
effect from exposure to a mixture of carbon disulfide and hydrogen sulfide
at levels three orders of magnitude lower than those previously encountered.
The possibility of a toxic synergism with these gases is indicated but
this type of relationship is hard to confirm. The studies of synergistic
effects have definite weaknesses, including the lack of proper controls,
insufficient numbers of subjects, lack of statistical reliability and
lack of a sufficiently detailed explanation as to procedure and results
(211.). These results are of limited reliability.
2.1.12 Carbonyl Sulfide
The proposed de minimi's value for carbonyl sulfide is 200 yg/m3, one-hour
average. Experience with human exposures to carbonyl sulfide is lacking.
The review of available literature did not reveal any definitive studies of
biological responses to carbonyl sulfide. Therefore, human and ecological
effects data are not reported in tabular form. The information presented
below describes the available information on carbonyl sulfide. Available
information on odor properties of carbonyl sulfide is also described.
34
-------
Peyton et al. (201.) concluded that carbonyl sulfide and carbon
disulfide (see Section 2.1.11) may produce similar effects due to the
similar physical and chemical properties. The authors estimated the
relative toxicity of carbon disulfide to carbonyl sulfide is a ratio
of 2:1 based on the additional sulfur radical on carbon disulfide.
o
They recommended an ambient concentration of 400 yg/m . The National
Research Council (193.) concluded that the toxic effect of carbon
disulfide was attributed to metabolism to carbonyl sulfide and an
unknown form of sulfur. Thus the effects of carbonyl sulfide exposure
may be similar to those observed in carbon disulfide exposure. As
noted previously (Section 2.1.11), the available data on human effects
from carbon disulfide are confounded by the concomitant exposure of
hydrogen sulfide. Thus, although the compounds may react similarly in
humans, the effects are still uncertain.
The de minimi's level of 200 yg/m for carbonyl sulfide was
established primarily to control odors. An odor threshold for carbonyl
sulfide was not identified. Wostradowski et al. (202.) reported on
carbonyl sulfide research involving Kraft recovery furnaces and con-
cluded that carbonyl sulfide present in concentrations of one to 30 ppm
q
(2.4 to 74 mg/m ) in flue gas does not significantly contribute to the
odor problem. Berglund (219.) in a field investigation of a Kraft pulp
mill noted that selective elimination of all the known odorants (hydrogen
sulfide, methyl mercaptan, dimethyl sulfide, dimethyl, disulfide) would
not necessarily reduce the odor strength of the emission. The same may
also apply to carbonyl sulfide as supported by Worstradowski et al. (202.),
2.2 ECOSYSTEM EFFECTS
No studies of ecosystem effects of the twelve substances were
available in the literature consulted for this study. More exhaustive
searches and, especially, interpretation and synthesis of diverse informa-
tion would be required to elucidate this type of effect. More research
could possibly produce, for example, observations on changes in species
diversity in the presence of mercury. Other searches and interpretations
35
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would develop knowledge of the effect of fluorides on overall plant or
primary productivity.
However, it is expected that information on ecosystem effects will
be sparse. Only recently has the need been recognized for studies of this
type. Consequently, there is not a large body of published knowledge in
world literature. Ecosystem parameters, in the absolute sense, are
more difficult and costly to measure than toxicological studies using small
populations, as reported in Sections 2.1.1 through 2.1.11.
36
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3. NATIONAL EMISSIONS
For the purpose of evaluating the significance of SCCP emissions, a
nationwide emission inventory of the pollutants subject to de mini mis
guidelines for both SCCP and non-SCCP sources is presented in Tables 3-1
through 3-5. A comparison of SCCP versus non-SCCP emissions is presented
in Table 3-6. All emission data are for 1974, the most recent year for
which information is available. This information is not complete and blanks
in the tables indicate where no data were found. Values shown for column
totals represent the sums of the reported data, not estimated total emis-
sions.
s
3.1 TRACE ELEMENTS
Table 3-1 summarizes 1974 national SCCP emissions of trace elements (mer-
cury, beryllium and fluorides). Of the SCCP source categories, Electricity
Generation and Industrial Combustion Processes produce the greatest amounts
of trace element emissions. Combustion of coal for electricity generation
produces over 50 percent of the total mass of emissions for each of the
three trace elements.
Non-SCCP sources include industrial processing and waste incineration
(see Table 3-2.). Few industrial sources emit beryllium at rates of 100
kg/yr or greater. Fluorides are emitted from several industrial categories,
including those associated with ceramic manufacture, phosphorus-based
products, and primary metals. Electrolytic production of chlorine generates
the largest amount of mercury.
Overall, emissions of beryllium and fluorides from SCCP sources are
significantly higher than from non-SCCP- SCCP sources generate nearly all
of the beryllium emissions and over 40 percent of fluorides. However, non-
SCCP sources generate approximately 75 percent of mercury emissions.
3.2 ASBESTOS
Table 3-3. summarizes national emissions of asbestos, Non-SCCP sources
for asbestos emissions are reported in the available data; SCCP source
emission are not. The most important non-SCCP sources of asbestos emissions
are the production and processing of asbestos. Asbestos production accounts
for approximately 75 percent of the total asbestos emisssions nationally.
37
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TABLE 3-1. 1974 NATIONAL EMISSIONS OF TRACE ELEMENTS FROM SCCP
Source Category
Bituminous Coal
Pulverized Dry Bottom
Pulverized Het Bottom
Cyclone
Stoker
Anthracite
Stoker
Pulverized Dry Bottom
Lignite
Pulverized Dry Bottom
Pulverized Wet Bottom
Cyclone
Stoker
Residual 011
Other fired
Tangent lally fired
Electricity Generation
External Combustion
(1000 kg/yr)
Mercury Beryllium Fluorides
30.9 1*5.0 19,996.0
5.7 27.1 3.716.4
5.7 27. 1 3,716.4
0.3 1.4 190.2
0.2 0.6 90.9
0.1 0.3 50.9
0.4
0.1
0.1
0.1
0.7 3.8 0.2
0.5 2.4 0.1
Industrial
External Combustion
(1000 kg/yr)
Mercury Beryl Hum Fluorides
1.4 0.7 2,129.3
0.7 1.5 418.1
0.2 0.1 126.9
2.5 8.0 1.6Z9.6
0.1 0.1 53.5
0.1
0.5 2.3 0.1
0.1 0.4 0.0
Commercial/Institutional
External Combustion
(1000 kg/yr)
Mercury Beryllium Fluorides
0.1 1.6 53.7
0.0 0.1 1.9
0.4 39.0 90.8
0.5 0.3 308.5
0.6 2.5 0.1
0.0 0.0 0.0
Residential
External Combustion
(1000 kg/yr)
Mercury Beryllium Fluorides
0.0 0.3 13.8
0.0 0.0 0.5
-'
CO
CO
Source: Elmutls, et al., 1978(66.)
-------
TABLE 3-2. 1974 NATIONAL EMISSIONS OF TRACE ELEMENTS FROM NON-SCCP
Source Category
NON-SCCP SOURCES
Industrial Processes
Cement
Brick Tile Kilns and Dryers
Refractories
Phosphorus - Elemental
Phosphoric Acid - Wet Process
Phosphate Rock Drying, Grinding,
Calcinating
Primary Copper Smelting
Vitreous Kaolin Products
Flat Glass, Pressed and Blown Glass,
and Glass Containers
Mineral Wool
Primary Lead Smelting and Refining
Primary Zinc Smelting
Triple Superphosphates
Ammonium Phosphates
A1 iimi ntim Fl iinv*i_Hp
f\ 1 Ufri 1 1 1 till I r rwW r t-MC
Calcium Phosphate
Other Fluoride Sources
Electrolytic Production of Chlorine
Potassium Hydroxide
Carbon Black Furnace
Municipal Incineration
Incineration of Type '2' Waste
Sewage Sludge Incineration
Coal Refuse Piles, Outcrops and
abandoned mines
TOTAL NON-SCCP EMISSIONS
Emissions in 1000 kg/yr
Mercury
137.2
3.2
0.2
7.6
0.9
0.5
0.1
150.0
Beryllium
0.1
0.0
0.2
0.0
0.0
0.3
Fl uori des
239.5
5679.8
3408.8
2904.5
1734.3
748.1
542.9
448.3
340.8
204.1
181.2
180.9
162.7
120.3
94.5
80.7
271.8
17300.0
Data Source: Eimutis, et al, 1978(66.).
39
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TABLE 3-3. 1974 NATIONAL EMISSIONS OF ASBESTOS
Source Category
Asbestos (1000 kg/yr)
SCCP Sources
Non-SCCP Sources
Industrial Processes
Asbestos Products
Spinning Asbestos Fibres,Twist-
ing and Winding
Preparation of Asbestos Fibres
Carding Asbestos Fibres
Combing Asbestos Fibres
Manufacture of Asbestos Products,
Weaving
TOTAL ASBESTOS EMISSIONS
485.3
65.2
37.8
27.5
27.5
13.7
657.0
NA means no information available.
Data Source: Eimutis, et al, 1978(66.).
40
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mist for SCCP
aruL ^^SfiflLJjfflmffjfi JS^q0^*.:.^,5"1 f»**r acid emissions we re list i ma ted "By*
applying'the emission factors in Table 4-6 to a nationwide inventory of
total sulfur oxide emissions (reported as $02) from Reference 56.
SCCP sources generate approximately 96 percent of all sulfuric acid
emissions. Of the SCCP sources, coal combustion by the electric utility
sector generates the largest percentage of sulfuric acid emissions. This
is due to the large quantity of fuel consumed as well as the high sulfur
content of coal. Industrial combustion is less significant than the Elec-
tric Utility sector because of the difference in fuels, fuel consumption,
and capacity of combustion systems. The Commercial/Institutional and Resi-
dential sectors contribute approximately 26 percent of sulfuric acid emis-
sions from SCCP sources. Ninety-four percent of these emissions are from
oil combustion.
Emissions from non-SCCP sources are primarily from industrial process-
ing. The production of sulfuric acid accounts for over half of these
emissions, and brick and tile kilns and dryers contribute approximately
39 percent.
3.4 VINYL CHLORIDE
Table 3-5 presents national emissions of vinyl chloride. Only non-SCCP
sources were reported in the available data. Industrial processing accounts
for all emissions of vinyl chloride. The production of polyvinyl chloride
and vinyl chloride-ethylene dichloride account for approximately 99 percent
of all vinyl chloride emissions nationally.
3.5 TOTAL REDUCED SULFUR AND REDUCED SULFUR COMPOUNDS
Available data sources did not indicate total reduced sulfur and
reduced sulfur compound emissions for stationary conventional combustion
sources. Non-SCCP source category emissions were primarily from industrial
processes (see Table 3-6.). Pollutants are ranked as follows according to
total emissions produced by these sources per year:
41
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TABLE 3-4. 1974 NAT I ON AL ,£Mi SS&afSS&FS&Sftt- -ACID
, , --.-j^i -_" =* r fi^lWwBBIr.i'jjy ^~=sa-
SCCP Source Category
Electricity Generation
External Combustion
Coal
Oil
Internal Combustion
Oil
Turbines
Reciprocating Engines
Industrial Combustion
External Combustion
Coal
Oil
Internal Combustion
Oil
Turbines
Reciprocating Engines
Commercial /Institutional
External Combustion
Coal
Oil
Residential
Coal
Oil
Sulfuric Acid Mist (1000
144,213
49,885
190
56
22,675
33,559
169
70
2,358
43,536
2,449
39,908
TOTAL SCCP EMISSIONS 339,000
Non-SCCP Source Category
Sulfuric Acid
Production of Lead Acid
Batteries
Carbonizing Wool Fibers
Chlorosulfonic Acid
Salicylic Acid
Sal icyclates-Excluding
Aspirin
Brick and Tile Kilns &
Dryers
Chlorosulfonic Acid-
Inorganic Acids
Sul fated Ethoxylates-AEOS
MIST**.
kg/yr)
c
Sulfuric Acid Mist (1000 kg/yr)
7,105.2
405.6
5.5
14.1
0.9
0.1
4,797.5
26.1
20.0
TOTAL NON-SCCP EMISSIONS 12,400.0
TOTAL SULFURIC ACID MIST EMISSIONS 351,000.0
Source: Surprenant, et al, 1976(56.).
42
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TABLE 3-5. 1974 NATIONAL EMISSIONS OF VINYL CHLORIDE
Source Category
Vinyl Chloride (1000 kg/yr)
SCCP Sources
Non-SCCP Sources
Industrial Processes
Polyvinyl Chloride
Vinyl Chloride - Ethylene
Di chloride
Vinyl Chloride - Acetylene
Caprolactam
1,1,1 - Trichloroethane
Polyvinylvinylidene Chloride
Ethylene Dichloride -
Oxyhydrochlorination
TOTAL VINYL CHLORIDE EMISSIONS
NAa
78,639.6
10,357.0
530.7
155.1
135.2
61.9
0.0
89,900.0
aNA means no information available.
Data Source: Eimutis, et al, 1978(66.).
43
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TABLE 3-6. 1974 NATIONAL EMISSIONS OF TOTAL REDUCED SULFUR AND REDUCED SULFUR
COMPOUNDS (1000 kg/yr)
Source Category
SCCP Sources
Non-SCCP Sources
Industrial Process
Carbon Black-Furnace
Natural Gas Processing
Petroleum Refining - Sulfur
Plant
Petroleum Refining - Vacuum
Distillation
Wood Processing - Neutral
Sulfite Semi chemical
Rayon - Semi synthetic
Viscose Rayon
Sodium Hydrosulfide - Sodium
Bisulfide or Sulfhydrate
Fish & Seafood Canning
Methyl Mercaptan
Wood Processing - Kraft or
Sulfate Process
Wood Processing - Neutral
Sulfite Semi chemical
Captafal
Falpet
Mixed Olefinic Product
Carbon Tetrachloride -
Chi ori nation of Propane
Carbon Tetrachloride -
Carbon Disulfide
Coffee Roasting
Phosphoric Acid - Thermal
Process
Captan
TOTAL EMISSIONS
Hydrogen
Sulfide
NAa
44,617.9
8,572.4
57,624.4
8,515.2
4,122.6
1,327.6
22.9
20.4
4.5
179,544.3
71.2
53.5
304,000.0
Dimethyl
Sulfide
NAa
114.0
144.0
Dimethyl
Disulfide
NAa
534.2
534.0
Carbon
Disulfide
NAa
44,617.9
8,550.7
1,217.0
0.7
0.7
589.7
531.6
36.0
4.5
55,500.0
Carbonyl
Sulfide
NAa
14,872.6
8,550.7
23,400.0
Mercaptans
NAa
74,131.0
1,470.1
75,600.0
aNA means no information available.
-------
Pollutant
Hydrogen sulfide
Mercaptans
Carbon di sulfide
Carbonyl sulfide
Dimethyl di sulfide
Dimentyl sulfide
Hydrogen sulfide emissions comprise over half of all total reduced
sulfur and reduced sulfur compound emissions from non-SCCP sources. It
should be noted that, since available data sources did not provide emissions
information on methyl mercaptans separately, emissions of all mercaptans
are shown on the table. Of the industrial processes, Carbon Black-Furnace,
Petroleum Refining-Sulfur Plant and Wood Processing - Kraft of Sulfate
Processes produce the largest quantity of these pollutants.
3.6 SUMMARY OF EMISSIONS
Table 3-7 summarizes the total emissions for SCCP and non-SCCP sources
for the twelve pollutants. Of the trace elements, SCCP sources produce
nearly all of the beryllium and about 65 percent of the fluoride emissions
nationally. Non-SCCP sources generate about 75 percent of the mercury
emissions. Asbestos, vinyl chloride, and all total reduced sulfur and
reduced sulfur compounds are emitted exclusively by non-SCCP sources,
according to available data. Sulfuric acid mist is produced primarily by
SCCP sources.
Conclusions on this emissions inventory are based on information
found in available data sources. All tables except that for sulfuric acid
mist are based on data from Reference 66, Eimutis, et al, (1978). Accord-
ing to one of the authors of the document, information presented in this
source was based on 1974 NEDS data. Some of these data were updated when
new information became available. Other sources indicated that de minimi's
pollutant information had not been updated beyond 1974. Also, this docu-
ment is not all inclusive or exhaustive. Data are more complete for some
pollutants than others. If data were not included for certain source
categories, this may be due either to a lack of information on the source,
45
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TABLE 3-7. COMPARISON OF SCCP VERSUS NON-SCCP POLLUTANT
EMISSIONS (1000 kg/yr)
Pollutant
Total
SCCP Emissions
Total
Non-SCCP Emissions
Mercury
Beryllium
Asbestos
Fluorides
Sulfuric Acid Mist
Vinyl Chloride
Total Reduced Sulfur
Hydrogen Sulfide
Mercaptans
Dimethyl Sulfide
Dimethyl Disulfide
Reduced Sulfur Compounds
Hydrogen Sulfide
Carbon Disulfide
Carbonyl Sulfide
51.2
266
32,600
339,000
150
0.3
657
17,300
12,400
89,900
304,000
75,600
114
534
see above
5,500
23,400
46
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or that a certain pollutant may not be emitted from this source. Also, in
rounding*certain values may be reduced to 0.0, but this 1s not necessarily
an indication that a pollutant is not being emitted from a source.
Information on sulfuric acid emissions was derived from two sources.
Non-SCCP data were obtained from Reference 66, Eimutis, et al, (1978).
Sulfuric acid emissions from SCCP sources were estimated by applying the
emission factors in Table 4-6 to a nationwide inventory of sulfur oxides
(reported as SOg) from Reference 56, Surprenant, et al, (1976). This
document was based on a survey of data existing in literature and informa-
tion supplied through contact with industry, government and academic
laboratories.
47
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4. EMISSION FACTORS
This chapter presents pollutant emission factors for stationary con-
ventional combustion processes (SCCP). The factors are summarized from
the CCEA information base and are primarily a result of extensive data
surveys being conducted under EPA's Emissions Assessment of Conventional
Combustion Systems (EACCS) program. A discussion of the development of
these factors is presented in Section 5. Section 6 contains a discussion
of the variability of actual emission factors and the expected uncertainty
in emission values calculated with the mean factors presented here.
4.1 TRACE ELEMENTS
Tables 4-1 through 4-5 summarize trace element emission factors for
the predominant combustion source categories. The trace elements subject
to the de minimi's guidelines are mercury, beryllium, and fluorides.
Because the trace element emission factor data base was relatively undevel-
oped for industrial and commercial/institutional combustion processes,
emission factors for these combustion sources were based on similarities
to other combustion sources for which a more extensive data base was
developed. Accordingly, Tables 4-1 to 4-3 present equivalent trace element
emission factors for utility and industrial boilers, with the values of the
factors being based primarily on the more extensive emissions data base
available for utility boilers. Values of emission factors for commercial/
institutional combustion sources (Table 4-5) are also based primarily on
the data base for utility boilers. The rationale for the use of utility
boiler data for industrial and commercial/institutional emission factors is
discussed in Section 5.
All emission factors are presented in terms of weight of the pollutant
per unit heat input of fuel. In addition, most emission factors are pre-
sented in terms of the concentration of the pollutant in the fuel. Thus,
source specific emission factors may be determined if fuel composition and
fuel feed rate are known. For the case of utility (or industrial) coal-fired
boilers, a parameterized factor (see Table 4-1) is available to characterize
source specific beryllium emission factors when values of influence para-
meters (i.e., enrichment ratio, particulate control efficiency) are known.
48
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TABLE 4-1. TRACE ELEMENT EMISSION FACTORS FOR CONTROLLED COAL-FIRED UTILITY AND INDUSTRIAL BOILERS
BITUMINOUS COAL
FURNACE TYPE
Pulverized Dry Bottom
Pulverized Dry Bottom
Pulverized Dry Bottom
Pulverized Wet Bottom
Pulverized Wet Bottom
Pulverized Wet Bottom
Cyclone Boiler
Cyclone Botler
Cyclone Boiler
Stoker
Stoker
Stoker
Stoker
CONTROL DEVICE
Electrostatic Preci pita tor
Mechanical Preci pita tor
Wet Scrubber
Electrostatic Preci pita tor
Mechanical Preci pi tator
Wet Scrubber
Electrostatic Preci pi tator
Mechanical Preclpltator
Wet Scrubber
Baghouse
Mechanical Preclpltator
Wet Scrubber
Electrostatic Preclpltator
Hg
39C
39C
7.8C
39C
39C
7.8C
39C
39C
7.8C
2.0
6.2
.
-
pg/J
Be
2.3C
7.8C
0.2C
1.9C
6.3C
0.2C
0.4C
1.3C
0.03C
0.06
5.5
-
F
40C
40C
8.0C
40C
40C
8.0C
40C
40C
8.0C
10
3540
-
LIGNITE COAL
pg/J
Hg
64C
64C
13C
64C
64C
13C
64C
64C
13C
2.4
0.23
Be
0.7C
19C
0.3C
0.4C
18C
0.2C
5.9
0.11
50C
50C
IOC
50C
50C
IOC
50C
50C
IOC
423
638
General Notes: c 3
1. For Be. the emission factor may be computed from the general equation E*rr -f (I-E)ERXIO (see Section 5.1.1) Mhen
source specific values of the variables are known.
2. Most emission factors are shown In terms of C, the trace element content 1n the coal. C Is In units of ng/g, or
ppm. Typical values of C for bituminous coal are 0.2, 0.9 and 100 for Ho, Be, and F, respectively. Typical
values for lignite are 0.16, 0.8 and 37 for Hg, Be, and F, respectively. The limited data base for stoker units
did not permit the expression of emission rates In terms of C.
3. Blanks In the table Indicate that no emission factor Is reported In the existing data base. The source configur-
ations corresponding to these blanks are rarely encountered at industrial or utility boiler Installations.
4. Emission factors presented In this table are based on reference 1, (Sh1h,et al, October 1979) and reference 56
(Surorenant, 1976).
5. Emissions for anthracite coal are not reported In the existing data base. However, the amount of anthracite coal
used by combustion processes 1s very small (see Table 4-7) and expected to decrease to still lower levels of
consumption In the future.
6. To convert emission factor units to LB/1012BTU, multiply factors by 2.33.
-------
TABLE 4-2 TRACE ELEMENT EMISSION FACTORS FOR UNCONTROLLED COAL-FIRED
UTILITY AND INDUSTRIAL BOILERS
FURNACE
TYPE
Pulverized dry bottom
Pulverized wet bottom
Cyclone boiler
Stoker
BITUMINOUS COAL
pg/J
Hg
39 C
39 C
39 C
6.2
Be
26C
2 1C
4.4C
18
F
40C
40 C
40 C
3540
LIGNITE COAL
pg/o
Hg
64C
64C
64C
2.4
Be
81C
--
67C
24
F
50C
50 C
50 C ,
423
in
o
General Notes:
\
1. Emission factors presented in this table are based on Reference 1 (Shih, et al 1979).
2. Most emission factors are shown in terms of C, the trace element content (in yg/g or ppm) in
the coal. The limited data base for stoker units did not permit the expression of emission
rates in terms of C.
3. Blanks indicate that no emission factor is reported in the existing data base.
4. To convert emission factor units to LB/10^BTU, multiply factors by 2.33.
-------
TABLE 4-3 TRACE ELEMENT EMISSION FACTORS FOR OIL-FIRED
AND GAS-FIRED UTILITY AND INDUSTRIAL BOILERS
FURNACE
TYPE
UNCONTROLLED0
Tangential firing
Wall firing
RESIDUAL OIL3
P9/J
Hg Be F
23C 24C 23C
23C 24C 23C
NATURAL GASb
pg/J
Hg Be
4.9 Nil
4.9 Nil
F
Nil
Nil
(a) Emission factors for residual oil are calculated based on characterization of eleven residual oil
samples and the assumption that all trace elements in the oil feed are emitted through the stack
(Shin, et al, October 1979). C indicates the concentration of trace element in residual oil, in ppm.
(b) Based on stack test measurements for gas-fired utility boilers (i.).
(c) When boilers are equipped with wet scrubbers (used for flue gas desulfurization), the emission factor
for Be may be assumed to be 0.01 times the uncontrolled factor given above, and emissions of Hg and
F are .2 times the values given above (1.).
NOTE: To convert emission factor units to LB/1012BTU, multiply factors by 2.33.
-------
TABLE 4-4. TRACE ELEMENT EMISSION FACTORS FOR INTERNAL COMBUSTION SOURCES
SOURCE
TYPE
Gas turbine
Reciprocating engine
DISTILLATE
OIL
pg/J
Hg Be F Hg
.39 .14 -- 4.9
.13 .03 -- 4.9
NATURAL
GAS
pg/J
Be
Nil
Nil
F
Nil
Nil
en
ro
General Notes:
1. Emission factors are based on characterization of fuel samples as described in Reference 57
(Shin et al,February 1979) with the exception of emissions for Hg from natural gas-firing which
are based on stack test measurements for gas-fired utility boilers as reported in Reference 1
(Shih, et al, October 1979).
2. Blanks in the table indicate that no emission are reported in the existing data base.
3. To convert emission factor units to LB/1012BTU, multiply factors by 2.33.
-------
TABLE 4-5. TRACE ELEMENT EMISSION FACTORS FOR UNCONTROLLED COMMERCIAL/
INSTITUTIONAL EXTERNAL COMBUSTION
TYPE OF FURNACE EMISSION FACTOR , pg/J
Hg Be
Bituminous Coal:
Pulverized Dry Bottom
Pulverized Wet Bottom
Stoker
Residual Oil
Tangential or Wall firing
Natural Gas
Tangential or Wall firing
39C
39C
6.2
23C
4.9
26C
21C
0.6Cb
24C
Nil
40C
40C
3540
23C
Nil
(a) Unless otherwise noted, emission factors above are based on reference
1 (Shih, et al, October, 1979).
(b) The emission rate of Be from Stokers was determined by adjusting the
emissions factor for utility stokers. The adjustment was made by
comparing the coal ash/fly ash ratio for utility boilers versus the
coal ash/fly ash ratio for commercial/institutional boilers.
(See discussion of Section 5.1.4.)
(c) The term C in the emissions factor indicates the concentration of
trace element in the fuel, in ppm.
NOTE: To convert emission factor units to LB/1012BTU, multiply factor
by 2.33.
53
-------
Tables 4-1 through 4-5 present emission factors for the trace elements
mercury, beryllium, and fluorides. Depending on the type of emission con-
trol, fuel, and fuel composition, it is possible that emissions from some
new utility or industrial boilers would exceed the proposed de mini mis
emission rates for these pollutants. For example, a 500 MW pulverized dry
bottom boiler (operating at 60 percent capacity and 40 percent overall
efficiency) burning typical bituminous coal and controlled to meet the New
Source Performance Standards (NSPS) for criteria pollutants would be
expected to emit about 0.004 metric tons per year of beryllium, 0.04 metric
tons per year of mercury and 10 metric tons per year of fluorides. These
emission levels are nearly equivalent to the proposed de minimi's levels of
0.004 and 0.2 metric tons per year for beryllium and mercury, and greater
than the proposed level of 0.02 metric tons per year for fluorides. When
coal of high trace element composition is used, the de minimis levels may
also be exceeded for mercury and beryllium. However, for NSPS controlled
coal-fired boilers of average size (100 to 500 MW), the trace element
de minimis levels would normally be exceeded only for fluorides. These
calculated emission values are subject to some uncertainty because of
variabilities in the parameters used for the calculation, especially for
beryllium emissions from coal combustion. These uncertainties are dis-
cussed in Section 6.
Emissions from large oil fired boilers burning low sulfur fuel and
not equipped with flue gas desulfurization (FGD) units would be expected
to exceed the de minimis levels for beryllium and fluorides. For example,
a 500 MW oil fired boiler (operating at 60 percent capacity and 40 percent
overall efficiency) would emit 0.05 metric tons per year of beryllium
and 0.06 metric tons per year of fluorides (assuming a typical fuel com-
position of 0.08 and 0.12 ppm for Be and F, respectively). These emission
levels exceed the de minimis levels of 0.004 and 0.02 metric tons per year
for beryllium and fluorides. Respectively, however, when the same boiler
is equipped with an FGD unit to achieve the NSPS, the expected emission
levels would be 0.005 and 0.013 metric tons per year for beryllium and
fluorides, respectively.
54
-------
It should be noted that the relatively high stacks (e.g., 100 to 200 M)
associated with large boilers would probably preclude the possibility that
emissions from these sources would result in levels exceeding the de minimi's
ambient air guidelines, despite the expectancy that the de minimis emission
levels may be exceeded in some cases.
4.2 SULFURIC ACID MIST
Table 4-6 summarizes sulfuric acid emission factors for various un-
controlled combustion sources. Because the data base was limited, emission
factors were combined into the overall source categories shown. While in-
sufficient data exist to quantify the influence parameters affecting H2S04
emissions, it should be.noted that the values in Table 4-6 may change
significantly depending on oxygen levels in the flue gases, power level of
the process, and the concentration of trace elements vanadium, magnesium,
and sodium in the fuel.
Sulfuric acid emission levels from large coal and oil fired external
combustion sources would be expected to exceed the de minimi's level of one
metric ton per year. When a wet scrubber is used to meet the NSPS, the
expected emissions of sulfuric acid mist from a 500 MW boiler (operating
at 60 percent capacity and 40 percent overall efficiency) burning bitu-
minous coal of two percent sulfur would be 210 metric tons per year. The
expected emissions of sulfuric acid mist from a 500 MW boiler controlled
by wet scrubbing and burning two percent oil would be 420 metric tons per
year.
Emissions of sulfuric acid mist from internal combustion units are not
likely to exceed the de minimis levels. The average size of these sources
1s about 2 MW, and sulfuric acid emissions are not expected to be greater
than about one metric ton/year per unit (reciprocating engine or gas
turbine).
55
-------
TABLE 4-6. EMISSION FACTORS FOR SULFURIC ACID MIST FROM COMBUSTION SOURCES
SOURCE
Percent of
fuel Sulfur
in H2S04
Emission
Factor^
ng/J
Information
Sources
(Reference no.)
en
UNCONTROLLED D
EXTERNAL COMBUSTION
Bituminous coal- fired utility boilers
Oil-fired utility boilers
.74
2.4
8.8S
16.9S
58,22,2,14,56
59,58,56
INTERNAL COMBUSTION
Distillate oil-fueled gas turbine 3.8
Distillate oil-fueled reciprocating engine 1.4
Gas-fueled internal combustion Nil
1.5
8.9S
Nil
60,61
62,57
57
(a) Some emission factors are presented in terms of S, the percent sulfur in the fuel.
The limited data base for distillate oil-fueled gas turbines did not permit the
expression of emission rates in terms of fuel sulfur concentration.
(b) For controlled emission rates, multiply uncontrolled levels above by 0.50 when flue gas
desulfurization units are used, 1.0 when cold side ESPs or mechanical precipitators are
used, and 2.4 when hot side ESPs are used (63, 64, 65, 67, 68),
NOTE: To convert emission factor units to LB/1012BTU, multiply factor by 2.33.
-------
4.3 ASBESTOS AND VINYL CHLORIDE
An information search revealed no available emission data for asbestos
or vinyl chloride from stationary combustion sources. Potential emission
sources of asbestos from combustion systems were identified as internal
insulation materials, coal, and limestone used in flue gas desulfurization
units. Emissions of asbestos from any of these sources is expected to be
negligible. More data are needed to accurately quantify the significance
of the potential sources. Potential emissions of vinyl chloride are not
expected to exceed the de minimis emission levels. Conditions in the com-
bustion environment are extremely unfavorable for the information of vinyl
chloride, and existing emission data for hydrocarbon emissions indicate
low emissions levels for hydrocarbon groups containing vinyl chloride.
Specific emission data for vinyl chloride are needed to accurately quantify
an emission factor for this compound.
57
-------
5. DEVELOPMENT OF EMISSION FACTORS
The estimation of environmental loadings arising from combustion pro-
cesses depends on characterization of the emission rates peculiar to the
various combustion sources. The characterization of emissions of noncriteria
pollutants such as those considered for de minimi's cutoff levels is a
special problem because the data base is often inadequate. This chapter
discusses the manner in which the available data base has been used to
develop the pollutant emission factors presented in Section 4. for station-
ary conventional combustion sources.
5.1 TRACE ELEMENT EMISSIONS
Trace elements which are considered for de minimi's cutoffs are mer-
cury, beryllium, and fluorides. Mercury and fluorides are discharged
to the atmosphere primarily in the gas phase, and it is plausible to assume
that all quantities present in the coal feed are emitted to the stack.
The emission rate of beryllium, on the other hand, depends on the parti-
tioning of the element between particles in the flyash and bottom ash
fraction, and between flyash particles in the control device collector
and the control device exhaust.
5.1.1 External Combustion - Utility Boilers
Trace element emission rates depend greatly on the type of fuel.
Three principal fuels are used: coal, residual oil, and natural gas.
Coal Combustion
The existing data base for trace element emissions from coal fired
utility boilers is discussed extensively in Volume III of the Emissions
Assessment of Conventional Combustion Sources (1.). The data base was
developed from a large number of reference sources, as listed at the con-
clusion of this report. The major drawbacks in the data base concern the
limited information with respect to trace element emissions from lignite
combustion and the absence of data for trace element emissions from stoker
units. Also, the data base contained limited information for the charac-
terization of trace element emissions from sources controlled by mechanical
precipitators and wet scrubbers.
58
-------
Because trace element emissions are dependent on a number of factors,
including trace element content of coal, boiler firing configuration,
boiler size, and particulate control device efficiency, it is practical to
develop trace emission factors in a parameterized format to account for the
effect of the more important variables. In the EACCS program (l.),the equa-
tion used to calculate trace element emission factors is:
EF -jj- . F (I-E) ER X 103
where EF = emission factor for a specific trace element, ng/J
C = concentration of element in coal, vg/g
H = higher heating value of coal, kJ/kg
F = fraction of coal ash as fly ash
E = fractional particulate collection efficiency of control
device.
ER = enrichment factor for the trace element (ratio of concen-
tration of element in emitted flyash to concentration of
element in coal ash)
The use of enrichment factors enables direct comparison and compilation
of trace element emission data on a normalized basis. This normalization
scheme is appropriate because the enrichment behavior of trace elements is
generally consistent, despite differences in furnace or coal types, and
sampling or analysis procedures (1. through 13.).
Unique emission rates are associated with different sets of fuel type,
boiler type and control device type. Table 4-1 in Section 4. summarizes
the emission factors for these sets, as computed in the EACCS program using
the available data base and the equation above.
TABLE 5-1. EFFICIENCIES OF CONTROL SYSTEMS
Electrostatic predpltator
Mechanical predpltator
Wet Scrubber
Bituminous Coal
All Boilers
.98
.70
.99 ;
Lignite Coal
Pul. Dry Bottom cyclone
.99 .99
.76 .73
.99 .99
Note: Based on data base comprised of References 3., 4., 14.through 22.
59
-------
TABLE 5-2. FRACTION OF COAL ASH AS FLY ASH IN COAL FIRING
Pulverized dry bottom
Pulverized wet bottom
Cyclone
Stoker
Bituminous Coal
.80
.65
.135
.60
Lignite Coal
.35
.30
Note: Based on evaluations conducted in the EACCS program (!.)> using data
base comprised of References 3., 4., 14.through 22.
Enrichment factors used to calculate trace element emission factors were
determined in the EACCS program by averaging values reported by the various
reference sources of the existing data base. Since enrichment factors depend
on the efficiency of the emission control device, separate factors were de-
termined for three types of control devices; electrostatic precipitators,
mechanical precipitators, and wet scrubbers.
Based on evaluations conducted in the EACCS program (1.), the fraction-
al collection efficiencies for coal-fired boilers are shown in Table 5-1.
These efficiencies represent the average control observed for installations
associated with the trace element emissions data base. The control levels
for electrostatic precipitators and wet scrubbers are sufficient to attain
compliance with the New Source Performance Standards for boilers.
The average fraction of coal ash produced as fly ash varies with coal
type and boiler type as shown in Table 5-2.
Concentrations of trace elements for bituminous coal and lignite were
tabulated from published U.S. Geological Survey Data (24.) and the computer-
ized National Coal Resources Data System (23.), and supplemented by other
reference sources (25. through 54.). The average values for trace element
concentrations were determined by weighting the area specific concentra-
tions with annual production by county (55.).
The calculation of emission factors for mercury and fluorides does not
require the calculation of enrichment factors, since these elements are
discharged from coal combustion primarily in the gas phase. If mechanical
or electrostatic precipitators are used to control emissions, it is assumed
that all amounts of these elements contained in the coal are emitted
through the stack. When wet scrubbers are used, the data base indicates an
average removal efficiency of eightly percent for mercury and fluorides (1.).
60
-------
The data base compiled In the EACCS program contained no information
for trace element emissions from stoker units. Consequently, a test pro-
gram was conducted as a part of the EACCS program to obtain the necessary.
data. Because the data resulting from these tests are limited, and because
trace element analyses were performed using semi quantitative analysis tech-
niques, enrichment factors were not calculated from the data, and it is not
possible to normalize the test results with respect to trace element
composition in the fuel. Hence, for the limited stoker units tested, the
differences in trace element contents of the various fuels and control
devices result in substantial variation in the test results and the cal-
culated emission factors.
Trace element emission factors for uncontrolled utility boilers were
estimated by factoring out the effects of control devices from the exten-
sive data base compiled for controlled boilers. Control devices affect
both the enrichment factors and overall particulate collection rates.
Enrichment factors for uncontrolled boiler emissions were assumed to be
equivalent to those observed for boilers equipped with the low-efficiency
mechanical precipitators. The effect of the mechanical precipitator on
collection of particulate matter (including trace elements) was factored
out of the controlled emissions data base by applying the average collec-
tion efficiencies presented previously in this section to the emission
factors of Table 4-1. The results are shown in Table 4-2. (See Section
4.1.)
Gas and Oil-Fired Boilers
The data base compiled in the CCEA program includes analysis results
of residual oil samples from eleven separate oil-fired boiler sites. These
trace element concentrations were used to calculate mean emission factors,
assuming that all trace elements present in the oil feed are emitted through
the stack (1.). The emission factors are expressed 1n terms of the trace
element concentration in the residual oil (Table 4-3). (See Section 4.1.)
The data base for trace element emissions from gas-fired utility
boilers is extremely limited. Measurements of trace element emissions from
seven separate gas-fired boilers were conducted as part of the EACCS pro-
gram to supplement the existing data base. However, measurements were
61
-------
conducted for a limited number of trace elements, and concentrations for
only one of the pollutants of concern in this study, mercury, were deter-
mined.
5.1.2 External Combustion - Industrial Boilers
Emissions from industrial boilers are governed by the same principles
that apply to utility boilers. However, differences in combustion equip-
ment design and operating practices may result in differences in emission
factors. Generally industrial combustion equipment is smaller and less
efficiently operated than electric utility equipment, resulting in greater
emission rates from industrial boilers.
GCA is currently evaluating emission rates from industrial boilers
under the ongoing EACCS program. The evaluation includes a comprehensive
survey of the existing data base for trace element emissions, and the cal-
culation of trace element emission factors for various sets of boiler
design, fuel type, and control device. However, the results of this effort
will not be available until mid-1980. In the interim, the most comprehen-
sive synthesis of trace element emissions data and computation of trace
element emissions factors for industrial boilers is found in GCA's
Preliminary Emissions Assessment of Conventional Stationary Combustion
Systems (56.).
GCA estimates trace element emissions from coal-fired industrial boil-
ers based on fuel composition and distribution of fly ash to bottom ash for
the various external combustion categories. Because the data base was too
limited to permit characterization of trace element enrichment behavior in
the fly ash, it was assumed in this reference that trace element concentra-
tion was equally partitioned (no enrichment) between the fly ash and
bottom ash. GCA then applied the fraction of coal emitted as fly ash to
the trace element composition to calculate uncontrolled emission factors.
Controlled emission factors were determined by adjusting the uncontrolled
factors using typical particulate control efficiencies and assuming that
trace elements are partitioned equally (per unit mass) between the collected
matter and the matter escaping through the stack. However, since the
existing data base is inadequate to characterize differences in fuel com-
position and fly ash/bottom ash ratios between the Industrial and Utility
62
-------
sectors, it 1s also not possible to establish separate uncontrolled emission
factors for these two sectors. Similarly, since emission control capability
is equivalent for both utility and industrial boilers, the controlled emis-
sion factors are the same for each of these two combustion sectors.
Since there are insufficient data (based on available data base
surveys) to permit discrimination between trace element emissions from
utility boilers and industrial boilers, emission factors were assigned to
industrial boilers based on the recent investigation of utility boiler
emissions conducted under the EACCS program (1.). This work assembled an
extensive data base which permitted characterization of trace element en-
richment factors, fly ash/bottom ash ratios, fuel composition, and control
device efficiencies. (See Section 1.1.1.) Table 4-1 summarizes trace
element emission factors for coal-fired industrial boilers. (See Section
4.1.)
The available data base for trace element emissions from oil-fired and
gas-fired industrial boilers is also insufficient to permit a quantifying
distinction between the utility and industrial combustion sector. There-
fore, trace element emission factors for industrial boilers were assigned
values equivalent to those compiled for utility boilers in the EACCS pro-
gram (1.). Table 4-3 summarizes trace element emission factors for oil and
gas fired industrial boilers.
5.1.3 Internal Combustion - Industrial or Electricity Generation
The data base for trace element emissions from internal combustion
sources is discussed extensively 1n Volume II of the Emissions Assessment
of Conventional Stationary Combustion Systems (57.). The data base was
developed from various references and supplemented by additional test data
acquired 1n the EACCS program.
Measurements of trace elements emissions in the stack gases from a gas
fueled turbine revealed the presence of negligible or nondiscernlble amounts
for most of the trace elements. However, emission of mercury vapors during
gas firing were of the same magnitude as those resulting during oil-firing
and are consistent with the levels observed in tests of utility boilers
(as discussed earlier in Section 5.1.1). Table 4-4 shows trace element
emission factors for gas-fired turbines.
63
-------
Table 4-4 also presents trace element emissions data for distillate
oil-fueled gas turbines and distillate oil (diesel fuel) engines. The
emissions data were based on the trace element content of the fuel used at
various test facilities, and represent maximum potential emission rates.
The emission factors for the turbine and engine are of the same order of
magnitude, and are the result of the similarity between the trace element
content of turbine and engine fuels.
5.1.4 External Combustion - Commercial/Institutional
GCA is currently evaluating emissions from commercial/institutional
combustion systems under the ongoing EACCS program. The evaluation will
include a comprehensive survey of the existing data base for trace element
emission, and the determination of trace element emission factors for
various sets of boiler design and fuel type. Until the results of this
effort are available, the most comprehensive synthesis of trace element
emissions data for commercial/institutional combustion systems is found
in GCA's Preliminary Emissions Assessment of Conventional Stationary Com-
bustion Systems (56.). In this document, GCA estimates trace element
emissions factors from commercial/institutional combustion systems for
coal-fired boilers based on fuel composition ratio of fly ash to bottom ash
for the various combustion categories. Trace element concentration is
assumed to be equally partitioned between bottom ash and fly ash. The fly
ash/bottom ash ratio is assumed to be the same as that for industrial
boilers, with the exception of stoker units. For stoker units, the fly
ash/bottom ash ratio is assumed to be 5/95 as compared to 35/65 for indus-
trial stokers. Hence, emission factors for trace elements from commercial/
institutional stoker units are seven times less than from industrial stoker
units. This relative difference was applied to stoker emission factors for
the industrial sector to calculate emission factors for commercial/insti-
tutional stoker units. The emission rate for other combustor types is
assumed to be the same as that for industrial boilers. The emission factors
are shown in Table 4-5. (See Section 4.1.)
The available data base for trace element emissions from oil-fired and
gas-fired commercial/institutional boilers is insufficient to permit a
quantifying distinction between the various boiler sectors. Therefore,
64
-------
trace element emission factors for commercial/institutional boilers were
assigned values equivalent to those compiled for utility boilers in the
EACCS program (1.). Table 4-5 summarizes trace element emission factors '
for oil and gas fired commercial/institutional boilers.
5.2 ASBESTOS EMISSIONS
Asbestos is the generic term for any of six naturally occurring
crystalline mineral hydrated silicates. Asbestos occurs in a fibrous state,
and is formed by the metamorphosis of serpentine and amphibole minerals.
Asbestos emissions result from the mining of asbestos ores, the mil-
ling of asbestos ores for production of five fibrous asbestos materials,
and the manufacture and end use of various asbestos-containing materials.
Based on existing emission inventories, it is estimated that 90 percent of
asbestos emissions arise during mining, manufacturing or production of
asbestos, while it is estimated that five percent of the total asbestos
emissions result from end-uses of asbestos-containing products (69.).
No accurate asbestos emission factors are reported in the existing data
base. Existing emission inventories developed for asbestos are based on
engineering judgments and very limited data. The CCEA information base was
searched for data on asbestos emissions from stationary combustion systems,
fuel and fly ash composition studies were evaluated, emission inventories
for noncriteria pollutants were examined, and various cognizant individuals
of pertinent agencies were consulted.
One possible source of emissions resulting from end-use of asbestos in
combustion systems is internal insulation in boiler breechings and ducts.
The rate of erosion of internal asbestos insulation is unknown, and the
integrity of the eroded fibers as an asbestos form is not known. However,
it is not expected that the quantity of emitted insulation materials would
approach the de minimis emission levels. For example, 1f asbestos emissions
resulted only from insulation loss, a stack emission rate of one ton per
year of asbestos (the de minimls level) would be equivalent to the loss of
approximately 90 tons per year of asbestos insulation from the boiler
equipment, assuming the stack emissions are controlled for particulate
matter. As this depletion rate is several orders of magnitude greater
than the amount of internal insulation used in a large boiler installation,
it is apparent that emissions of eroded insulation are actually negligible.
65
-------
Moreover, the use of asbestos insulation is no longer commonplace, as other
insulating materials with greater resistance to high temperatures are
presently being used instead. Use of these substitute insulation materials
also avoids the hazards previously experienced from exposure to asbestos
emissions during application of the insulator to the boiler equipment.
Other potential sources of asbestos emissions are flue gas desulfur-
ization (FGD) units which use limestone as the scrubbing medium. In some
deposits, limestone is known to contain the asbestos fibers tremolite and
actinolite (72.). As combustion flue gases are treated in a limestone FGD
unit, trace amounts of asbestos may be generated and emitted out the stack.
No information is available from the existing data base to characterize the
chemistry associated with asbestos emissions from limestone scrubbers or
the quantities of asbestos which may arise.
Still another potential asbestos emission source in combustion systems
is coal itself. However, only trace amounts of minerals are usually found
in coal deposits and it is not expected that detectable amounts of asbestos
occur in coal (71.). Moreover, it is expected that the normal temperatures
produced in the combustion zone are sufficient to disintegrate any asbestos
fibers present (70,).
In the development of the present national emission standards for
asbestos, various mining, processing, manufacturing and end-use sources of
asbestos emissions were considered. However, stationary combustion systems
were not addressed as a source of concern. Preliminary investigations
should be conducted to assess the significance of asbestos emissions aris-
ing from potential sources in combustion systems.
5.3 SULFURIC ACID MIST EMISSIONS
Sulfuric acid ^$04) is a product found in the flue gases of combus-
tion systems. It is formed when S02 in the combustion gases in oxidized
to $03, followed by the combination of SOs with water vapor in the stack
gas. Sufficient water vapor exists in the stack to convert essentially all
SOa to H2$04 before it is finally emitted out the stack. As the H2S04 is
emitted and is cooled to temperatures below the acid dew point, it is
transformed to a liquid aerosol known as "sulfuric acid mist".
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Sulfuric acid may be adsorbed on solid particulate matter in the stack
or condensed on boiler surfaces. This results in the formation of metal
surfates (MS04) and corrosion products. The sulfates which are formed, the
$03, and the ^804 vapor and liquid aerosol, are all referred to as primary
sulfates. (Secondary sulfates are sulfur oxidation products formed in the
atmosphere.)
Because current analytical methods and reporting procedures for primary
sulfates vary, the resulting emissions data may be misleading. Generally,
the analytical approaches used allow a separate determination of particulate
and gaseous forms of the primary sulfates (.64.). The gaseous sulfates,
consisting of HgS04 and SOg, are collected by filter for analysis by wet
chemical techniques. Depending on the temperature of the filter and the
sampled stack gases, some fraction of the h^SCty present in the sample
stream will be collected by the filter as aerosol particulate matter. The
aerosol H2S04 on the filter is indistinguishable from the particulate
sulfates during analysis, and is included as total particulate sulfate.
In sampling systems using high temperature probes and filters, the portion
of H2S04 collected by the particulate filter is minor, while systems which
sample isokinetically from the stack may contain significant portions of
aerosol H2S04 which is collected on the filter (78.). Thus, emissions data
surveys for average emission levels tend to understate the actual level of
H2S04 to some degree, depending on the type of sampling procedures asso-
ciated with the data base. However, this understatement is mitigated to
some degree, considering that some H2S04 is adsorbed on particulate matter
between the stack sample point (typically near the base of stack) and the
stack exit.
Emissions of 863 and H2S04 depend on numerous operating parameters.
The parameter causing the most pronounced effect on $03/^504 emissions is
the amount of excess oxygen supplied to the burners. Low excess air opera-
tion is most practical in oil-fired systems, whereas the technology for
burning pulverized coal at low oxygen levels is not available. Excess air
must be less than two percent to decrease SOs formation by one half from
normal operation at twelve to 20 percent excess air. $03 concentration can
be reduced to essentially zero at 0.1 percent oxygen in the flue gas (63.).
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Sulfuric acid concentration in flue gas is also related to the boiler
load factor (i.e., the operating power level compared to the design full
power level), the sulfur content of the fuel, and the concentrations of
vanadium, magnesium, and sodium in the fuel. The latter trace elements
introduce a catalytic effect on the reaction of S02 to $03. Recently.
studies have been conducted to quantify the relationship of the various
influence factors affecting sulfuric acid and sulfate emissions (67.).
Such models are in formative stages of development, and may be useful when
plant specific data are available to characterize the influence variables
and calibrate the model.
Emissions data for f^SC^ (including SOs reported as h^SC^) are pre-
sented in Table 4-6. Because the data were very limited for some boiler
firing types, data were combined into the general source categories shown.
However, the variability of the combined emissions data base is less than
0.7, and may, under the criteria established in the EACCS program (!.)» be
considered an adequate portrayal of S03/H2S04 emissions from utility
boilers. No data for lignite-fired utility boilers were found.
In the absence of emissions data for industrial boilers, the emission
rate of S03/H2S04 from industrial boilers was assumed to be equivalent to
that of utility boilers.
The most extensive survey of the SC^/h^SCh emissions data base for
internal combustion sources was developed in the EACCS program (57.). The
SOo/^SO^ emission data base was found to be adequate for oil fueled gas
turbines; however, limited data were available to characterize S03/H2S04
emissions from reciprocating engines. Table 4-6 summarizes the emission
factors and information sources for internal combustion sources.
Conventional control equipment which is used to reduce emissions of
parti cul ate matter and S02 from flue gases may also affect emissions of
sulfuric acid. Of the controls used, flue gas desulfurization systems
exert the greatest impact on H2S04 emissions. Evaluation of data for lime
and limestone scrubbers at various coal-fired sources (63.) has shown that
desulfurization systems operating at 80 to 90 percent S02 removal also
removal about 50 percent of the SO- and HUSO^ in the flue gas. Evaluation
of test data for emissions from conventional electrostatic precipitator
(ESP) installations at coal and oil-fired sites has shown that an ESP has
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no effect on the concentration fo S03/H2$04 in the flue gases (64.). How-
ever, emissions of S03/H2S04 may increase appreciably when an ESP is
installed upstream of heat recovery equipment ("hot side" configuration).,
Electrical arcing across the ESP electrodes converts S02 to $03 rapidly
at the higher temperatures in the hot side ESP (65.). In limited tests
conducted at a coal-fired industrial boiler equipped with a hot side ESP,
flue gas concentrations of S03/H2S04 increased by 242 percent through the
ESP (65.).
5.4 VINYL CHLORIDE EMISSIONS
No emissions data for vinyl chloride were reported in the CCEA data
base. Some specific organic compounds have been identified in flue gases
of combustion systems, but quantitative data on the emissions of these
compounds is extremely limited. Generally, conditions of high temperature,
mixing, ample residence time and excess oxygen in the combustion environ-
ment have been considered unfavorable for formation of organic compounds
in quantities which could cause significant environmental concern. In
fact, a common method used to control emissions of chlorinated hydrocarbons
(i.e., vinyl chloride) from manufacturing facilities involves incineration
in steam boilers (220). This control technique has been used in existing
boilers without affecting normal operations or boiler efficiency.
Although the amount of vinyl chloride emission in flue gases cannot be
determined specifically, the quantitative emissions data base does demon-
strate that emission levels of vinyl chloride from combustion systems will
not exceed the de minimis levels. Table 5-3 shows emissions factors for
63 alkanes measured in stack gases for various utility boilers and fuel
types in the EACCS program (1.). The data were obtained by chromatograph
using a normal boiling point retention time calibration, according to EPA's
Level 1 Method. As the boiling point of vinyl chloride is -13.9 C, the
chromatograph will report this compound in the range of 3 alkanes in terms
of propane (74.). Thus, assuming that as much as ten percent of organics
reported as 63 alkanes are vinyl chloride (a conservative assumption, con-
sidering the stability and formation potential of vinyl chloride relative
to other more common alkanes), and that the greatest expected emission rate
would be 410 pg/J (see Table 5-3), the total emissions of vinyl chloride
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Table 5-3. EMISSIONS OF C3 HYDROCARBONS FROM UTILITY BOILERS
Maximum Emission Rate Reported
Combustion Source P9/J
Bituminous Coal-fired Utility Boilers
pulverized dry bottom 320
pulverized wet bottom 160
cyclone 280
stoker 320
Lignite-fired Utility Boilers
pulverized dry bottom 410
cyclone 260
stoker 370
Oil-fired Utility Boilers
tangential firing 320
wall-firing 340
Gas-fired Utility Boilers
tangential-firing 200
wall-firing 250
Source: Shih, C., et al, 1979(1.)
from a 500 MW lignite fired boiler would be 0.7 tons per year. This is
less than the de minimis level of 1 ton per year.
5.5 TOTAL REDUCED SULFUR AND REDUCED SULFUR COMPOUND EMISSIONS
Theoretically, under normal combustion process conditions all of the
sulfur, in any type of fuel, would be converted to sulfur oxides, most of
which is sulfur dioxide. Sulfur trioxide and primary sulfates are also
formed in the oxidative process. It has been observed (80.), however, that
less than the expected amount of sulfur is completely oxidized. The actual
amount is usually from 79 to 99 percent. The remaining sulfur may be found
70
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as sulfur compounds retained in coal and oil bottom ash or slag in the form
of metal sulfides. If reduced sulfur compounds exist in a combustion
(oxidation) process as a part of the flue gas, it would have to be under
reducing combustor conditions. Combustion thermodynamics, which would
govern the formation of any sulfides, are a function of the fell owing
parameters:
Fuel type: percent sulfur, percent ash and concentration of metals
Temperature and air/fuel ratio (stoichiometry)
Mode of combustion: type of firing, time in combustor, etc.
Kinetic limitations of the sulfur reactions
The CCEA information base was searched for data on emissions, analy-
tical methods of determination, fuel combustion and studies, and any mass
balance approaches to reduced sulfur evaluation. National emission inven-
tories for noncriteria pollutants were examined for historical reduced
sulfur emissions, and persons knowledgeable in the field were contacted.
Very little pertinent information is available. One report (80.)
contains information on hydrogen sulfide, carbonyl sulfide, and carbon
disulfide. This information was limited to a mole fraction computer study
of sulfur distribution in four types of coal. The other (83.) included
total sulfide and total reduced sulfur species as a percent of oil and coal
fired fly ash composition. In either case the recorded levels are always
less than 0.01 percent of the sulfur in fuel. The report states that
"although the method of determination of sulfate might measure other sulfur
species, determinations have shown the presence of other sulfur forms to
be negligible". While examination of the literature reveals that many of
these sulfur compounds have been observed at coal gasification and oil
refinery sources (81.,82.), no other combustion emissions data nor any
other analytical procedures are mentioned for the measurement of total
reduced and reduced sulfur pollutants from conventional combustion sources.
Furthermore, all persons contacted (see Appendix A) have no knowledge
of any reports or ongoing projects that measure the sulfur compounds at
conventional combustion sites. Most of them informally agreed to the
assumption, a priori, that one would not expect appreciable amounts of
these pollutants in an oxidative process.
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6. SAMPLING AND ANALYSIS PROCEDURES USED TO OBTAIN EMISSIONS DATA
This section presents a discussion of the following major areas related
to emission measurement for the pollutants subject to the de minimis guide-
lines :
Sampling and analysis methodology
Accuracy and precision of sampling and analysis methodology
Means of assessing the adequacy of emissions data for use in cal-
culating emission factors.
0 Implications of the variability of actual emission factors for
calculating source emissions.
A search of the CCEA data base for information on the emissions of
these pollutants from SCCP produced the following results:
For Mercury, Beryllium and Fluorides: a relatively large amount
of valid data.
t For Sulfuric Acid Mist (SOs): limited data.
t For Asbestos, Hydrogen Sulfide, Methyl Mercaptan, Dimethyl Sulfide,
Dimethyl Disulfide, Carbon Disulfide and Carbonyl Sulfide: no data.
The discussion in this section will therefore be limited to Mercury, Beryl-
lium, Fluorides, and Sulfuric Acid Mist ($03).
It was beyond the scope of this effort to review all pertinent litera-
ture on sampling and analysis for these four pollutants. Thus, this section
will briefly describe general, widely used sampling and analysis methodo-
logies and will then present in more detail several examples from the CCEA
information base.
6.1 SAMPLING METHODOLOGY
There are a limited number of widely used methods for sampling stacks
for particulates and volatiles. Work prior to 1971 was typically performed
with an ASTM specified train (ASTM, 1971). Since then, stack sampling
typically has been performed in accordance with EPA's method 5 specifications
(EPA-76). A stack sampling train now in wide use is the Source Assessment
Sampling System (SASS) train, which is required by EPA-IERL on its emissions
72
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assessment programs (77.)- The impinger contents of the ASTM and Method 5
trains were modified by workers who needed to trap volatile inorganic
species. The SASS train impingers were designed to trap volatile inorganics.
A typical sulfur species sampling train is the Controlled Condensation
System (CCS) (78.). This train collects particulate sulfate on a heated
filter; SOs, as HgSC^, in a coil maintained at a temperature above the dew
point of H2SC«4; and $62 in a hydrogen peroxide filled impinger. Some
chlorine and fluorine is trapped in the peroxide impinger, and the reminder
is trapped in a second, sodium carbonate filled impinger.
Recent reports from the Emissions Assessment of Conventional Combustion
Systems (EACCS) (1,57.) program have been used in the development of emission
factors discussed in Sections 4.0 and 5.0 of this report. A major task of
the EACCS program is to evaluate the existing data base. This evaluation
cited eleven sources of emissions data as being particularly useful. Three
of these reports will be used as examples of sampling methodology.
Bolton, et al. (5.) used a standard ASTM train to sample particulate
emissions from the stack and across the electrostatic precipitator of a
coal-fired utility plant. Samples were taken isokinetically across the
ducts and stack diameters. Samples of coal, slag, and other process streams
were taken by conventional methods (e.g., grade sampling) and composited >
over the test period. They also reported on laboratory tests of an impinger
system for trapping volatile mercury compounds.
Curtis (8.) summarized a number of trace element emission studies
performed by Ontario Hydro. Conventional methods were used to sample
liquid and solid process streams. Use of a special stack sampling unit for
collecting vapor phase trace elements was mentioned, but no details were
given. The stacks were traversed, and sampling was isokinetic.
Schwitzgebel, et al. (4.) used conventional methods of sampling liquid
and solid process streams. They used a wet electrostatic precipitator (WEP)
to sample particulates in the stack. The WEP was backed up by a standard
Method 5 filter to verify the collection efficiency of the WEP. Mercury was
sampled by a gold amalgamation technique. Sulfur species were trapped in
hydrogen peroxide. Sampling was isokinetic at the required number of
traverse points across the stack diameter.
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Shih, et al , (57.) reported the use of the CCS train for sampling
sulfur species at oil-fired internal combustion sources in the utility and
industrial use sectors. Sampling with this train on the EACCS program is
performed isokinetically at the point of average velocity.
6.2 ANALYTICAL METHODOLOGY
Analytical methods applied to trace pollutant emissions measurements
are also limited. Neutron activation analysis (NAA) is a multi-element
technique capable of ultratrace levels with high accuracy and precision.
Spark source mass spectrometry (SSMS) is another widely used multi-element
method. For most elements, SSMS has an accuracy and precision of +_ 50 per-
cent. Atomic absorption spectroscopy (AAS), both flame and flameless, is a
single element technique capable of high accuracy and precision at trace
and ultratrace levels. Titrimetry is commonly used for sulfur species
sampled by the Goksoyr-Ross or CCS trains. Selective ion electrodes (SIE)
are generally used for halogens. Selective ion electrodes are capable of
accuracy and precision of about five percent.
Analytical methods generally are not the limiting factor in trace
element analysis. The nature of the sample, sample handling, and parti-
cularly sample preparation can have a significant effect on the overall
accuracy of a sampling and analysis program. For example, to get reasonable
closure on a materials balance, solid samples (e.g., fly ash) have to be
totally dissolved in order to free trace elements bound in the solid matrix
for analysis. The usual method for totally dissolving inorganic solids is
with a mixture of strong acids. Coal samples are usually burned in an
oxygen filled calorimeter (e.g., Parr oxygen bomb) before trace element
analysis.
Bolton, et al, (5.) determined mercury by flameless AA, and beryllium
by NAA. Fluoride and $03 were not determined. They reported that NAA was
good to five percent for most elements.
Curtis (8.) reported that Hg and F were determined by NAA, F by selec-
tive ion electrode, and Be by flameless AA. Table 6-1 presents the
accuracies given by Curtis.
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TABLE 6-1. ACCURACIES OF TRACE ELEMENT DETERMINATIONS FROM CURTIS (7)
Element
Be
Hg
F
Coal
+10%
+15%
+ 5%
Bottom Ash
+15%
+15%
+15%
ESP Ash
+15%
+15%
+35%
Post-ESP
+35%
+85%
+55%
Ash Parti oil ate
NA
+15%
+40%
TABLE 6-2. ACCURACIES OF TRACE ELEMENT DETERMINATIONS FROM SCHWITZGEBEL (1975)
Element Coal & Coal Ash Lime Aqueous Samples
Be +12%
Hg +10%
F + 8%
+12%
+10%
+ 8%
+10%
+10%
+ 8%
WEP Liquor
+10%
+20%
+ 8%
Schwitzgebel et al, (4.) used AA for Hg and Be and a selective ion
electrode for F. Table 6-2 presents analytical accuracies reported by
Schwitzgebel.
Samples from the CCS train are the filter (particulate sulfates), the
coil rinse (SOs as H2S04), the peroxide impinger (S02 as H2S04, Cl, and F),
and the carbonate impinger (Cl and F). Fluoride is determined by selective
ion electrode. The filter is extracted to remove sulfates. The filter
extract and impinger contents are determined by turbidimetry. The accuracy
of the analyses is ten percent.
6.3 ADEQUACY OF DATA FOR EMISSION FACTOR DEVELOPMENT
One major task of the EACCS program is the identification of gaps and
inadequacies in the emissions data base for stationary conventional combus-
tion processes (SCCP). Assessment of the adequacy of emissions data is
performed by considering both the reliability and the variability of the
data. The general approach to this assessment is a three step one, which
is fully described in the literature (1.) and which is summarized below.
In Step 1, emissions data are screened for adequate definition of
process, equipment, and fuel parameters. Also, sampling and analysis
methods are assessed. If process definition is not adequate or if sampling
75
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and analysis methods are not capable of accuracy in the range +_ factor of
three, the data were rejected. This step eliminates data which would be of
little or no use.
Step 2 consists of further engineering and statistical analysis of the
emissions data to determine their internal consistency and variability-
Emission factors calculated from each pollutant-unit operation pair are
evaluated for consistency by comparison with emission factors from similar
sites. Emission factors lying outside upper and lower bounds are discarded.
The Method of Dixon, a statistical technique applicable to the rejection of
single outlying points in a small group of points, is used as the rejection
criterion.
The variability of emission factors is calculated from
v =
x
where x is the mean value of the emission factor, s(x) is the estimated
standard deviation of the mean, and t is the Student "t", the value of
which depends on the degrees of freedom of the mean and the confidence
level desired for the interval containing the true population mean. For
the EACCS program, values of t are chosen such that the confidence inter-
val is 95 percent.
Step 3 of the data evaluation process involves a quantitative treat-
ment of the variability of the emission factors to assess their adequacy.
This assessment is based on both the potential environmental risks asso-
ciated with the emission of each pollutant and the quality of the existing
emissions data.
6.4 IMPLICATIONS OF EMISSION FACTOR VARIABILITIES FOR EMISSION CALCULATIONS
Emissions from a particular combustion source are generally calculated
in the following manner:
Emissions = (EF) (F) (H)
where EF is the emission factor, F is the fuel use rate of the source, and
H is the heating value of the fuel. The expected uncertainty of the emis-
sion value calculated in this manner depends on the variabilities of all of
the terms in the equation.
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In the EACCS program, TRW calculated variabilities for the emission
factors for trace elements and SOs for many combustion source categories.
In Table 6-3 these variabilities have been grouped by fuel type. Actual '
variabilities greater than 70 percent are not shown, since,,in many cases,
they vary widely among the specific source categories, and since such a
high variability would argue against the use of the emission factor at all.
The 70 percent criterion used in the table is arbitrary; however, the same
variability criterion is used in the EACCS study to measure the adequacy of
the data base for emission factor development.
Table 6-3 indicates that the variabilities for the beryllium emission
factors are consistently greater than 70 percent for all categories of coal
and oil-burning boilers. In fact, the actual variabilities are often
several hundred percent for beryllium emissions from coal combustion (1.).
One must conclude from this that the actual emissions of beryllium from a
given coal-burning source bear little relationship to calculated emission
value for the pertinent source category, based on the existing emission
data (i.e., using one of the factors given in Section 4.1 of this report).
Emission factors for mercury, on the other hand, have variabilities less
than 70 percent for coal and oil combustion, although the variability for
the mercury emission factor for gas combustion is greater than 70 percent "
(143 percent (1.)). The emission factor variability for fluorides from
coal combustion is less than 70 percent and for fluorides from oil combus-
tion is greater than 70 percent (96 percent (1.)). Variabilities for SOs
emission factors are less than 70 percent for both coal and oil combustion.
TABLE 6-3. VARIABILITIES OF CALCULATED EMISSION FACTORS
Fuel -
Coal
Oil
Gas
Mercury
35%-40%
50%
>70%
Variabilities
Beryllium Fluorides
»70% 35%-40%
>70% >70%
NEa NEa
S03
19%
33%
NEa
Negligible emissions.
Source: Shih, et al, 1979 (1.).
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It should be noted that variability does not necessarily represent the
accuracy of sampling and analysis methods used. It more often represents
variation in the parameters used to develop the emission factors:
Concentration of element in fuel.
High heating value of fuel.
For t ace elements only:
Fraction of ash as fly ash
Collection efficiency of control device
Enrichment factor for the trace element
(See equation in Section 5.1.1). Most emission factors shown in Section 4
of this report require substitution of the concentration of the element in
the fuel for C in the case of trace elements and for S in the case of sul-
furic acid mist. The variability of this concentration appears to be
relatively low (1.), however, and, therefore, is probably not an important
influence on the high variability of the beryllium emission factors.
Instead, it is more likely the variability of the enrichment ratio which
causes high variability in the beryllium emission factors. (Enrichment
does not occur during emission of mercury, fluorides, and sulfuric acid
mist). Although enrichment ratios depend on the efficiency of the control
device and the consequent particle size distribution, the relationship
between enrichment ratio and these and other influence parameters is not
known.
The expected uncertainty of a calculated emission value depends also
on the variabilities of the remaining two terms in the equation quoted
earlier in this section: the fuel use rate and the heating value of the
fuel. If it is assumed that the variabilities of these terms are very
small compared to the variability of the emission factor, the following
recommendations can be made, based on the observations in this discussion:
Little confidence can be placed in calculated emission of beryllium
from any combustion source until more sampling data are taken and
better beryllium emission factors are developed.
Calculated emissions of mercury from gas combustion and fluorides
from oil combustion are somewhat uncertain until better emission
factors can be developed.
t Calculated emissions of mercury, fluorides, and $03 from source
categories not mentioned in the preceding statement are within the
range of uncertainty usually anticipated for this type of calcula-
tion.
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APPENDIX A: PERSONS CONTACTED FOR INFORMATION ON TOTAL REDUCED SULFUR
AND REDUCED SULFUR EMISSIONS
Name Affiliation
David Anderson TRW
Steve Cherry KVB Inc.
Dr. Delbert Eatough Brigham Young University
Dr. Ed Eimutis ' Monsanto Research Corporation
Dr. Warren Hamersma TRW
William Henry Battelle
Jim Homolya EPA/RTP
Dr. Ralph Perhac Electric Power Research Institute
Jake Sommers EPA/RTP
Jim Sutherland EPA/RTP
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99
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-450/2-80-074
5. REPORT DATE rial copy
June '80 -forwarded to EPA
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Health Impacts, Emissions, and Emission Factors for
Noncriteria Pollutants Subject to De Minimi's Guidelines
and Emitted from Stationary Conventional Combustion
6. PERFORMING ORGANIZATION CODE
Processes
7.AUTHOR(s)
g^ Ackermanj M- T. Haro> G. Richard, A. M.
Takata and P- J. Weller plus D. 0. Bean, B. W. Cornaby,
8. PERFORMING ORGANIZATION REPORT NO.
M-iHan anrl
E Ron*
. PERFORM'fN'G'OR'dANl'ZATIO'N NAME\~ffND ADDRESS
TRW
Redondo Beach, California
Batlelle
Columbus, Ohio
10. PROGRAM ELEMENT NO.
T1. CONTRACT/GRANT NO.
68-02-3138
12. SPONSORING AGENCY NAME AND ADDRESS
U. S. EPA
Industrial Environmental Research Laboratory
Research Triangle Park, N.C. 27711
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
6. ABSTRACT
Report presents a literature survey of the health and ecological effects
associated with various air quality levels of noncriteria pollutants that are
regulated under the Clean Air Act. These noncriteria pollutants include mercury,
beryllium, asbestos, sulfuric acid mist, vinyl chloride, hydrogen sulfide, methyl
mercaptan, dimethyl sulfide, dimethyl disulfide, carbon disulfide and carbony
sulfide. Nationwide emissions are estimated for each noncriteria pollutant with
particular emphasis on contributions from fossil fuel combustion at stationary
sources. Factors for quantifying emissions from fossil fuel combustion processes
are discussed for each noncriteria pollutant.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Noncriteria pollutant
8. DISTRIBUTION STATEMEN1
19. SECURITY CLASS (This Report}
Unclassified
21. NO. OF PAGES
100
20. SECURITY CLASS (This page)
22. PRICE
Unclassified
EPA Form 2220-1 (Rev. J-77) PREVIOUS EDITION is OBSOLETE
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