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Office of Health and Ecological
Effects
Washington DC 20460
EPA-600/9-78-009
June 1978
Carbon Disulfide,
Carbonyl Sulfide
Literature Review
and Environmental
Assessment
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development U S Environmental
Protection Agency, have been grouped into nine series These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields
The nine series are
1 Environmental Health Effects Research
2 Environmental Protection Technology
3 Ecological Research
4 Environmental Monitoring
5 Socioeconomic Environmental Studies
6 Scientific and Technical Assessment Reports (STAR)
7 Interagency Energy-Environment Research and Development
8 'Special Reports
9 Miscellaneous Reports
This document is available to the public through the National Technical Informa-
tion Service. Springfield, Virginia 22161
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Final Report
Do not remove. This document
should be retained in the EPA
Region 5 Library Collection.
January 1976
CARBON DISULFIDE, CARBONYL SULFIDE
Literature Review and Environmental Assessment
By:
THOMAS O. PEYTON
ROBERT V. STEELE
OPERATIONS EVALUATION DEPARTMENT
WILLIAM R. MABEY
PHYSICAL ORGANIC CHEMISTRY
TECHNICAL MONITOR
ALAN CARLIN
PROJECT OFFICER
ALBERT PINES
Contract No. 68-01-2940, Task 023
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DISCLAIMER
This report has been reviewed by the Office of Research and Development, EPA, and
approved for publication. Approval does not signify that the contents necessarily reflect
the views and policies of the Environmental Protection Agency, nor does mention of
trade names or commercial products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Information
Service, Springfield, VA. 22151.
-------
Final Report
Do not remove. This document
should be retained in the EPA
Region 5 Library Collection.
January 1976
CARBON DISULFIDE, CARBONYL SULFIDE
Literature Review and Environmental Assessment
By:
THOMAS 0 PEYTON
ROBERT V. STEELE
OPERATIONS EVALUATION DEPARTMENT
WILLIAM R. MABEY
PHYSICAL ORGANIC CHEMISTRY
TECHNICAL MONITOR
ALAN CARLIN
PROJECT OFFICER
ALBERT PINES
Contract No. 68-01-2940, Task 023
Prepared for:
ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
OLrl t-. $ & v. ^s
-------
DISCLAIMER
This report has been reviewed by the Office of Research and Development, EPA, and
approved for publication. Approval does not signify that the contents necessarily reflect
the views and policies of the Environmental Protection Agency, nor does mention of
trade names or commercial products constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Information
Service, Springfield, VA. 22151.
-------
CONTENTS
LIST OF TABLES -jv
I INTRODUCTION 1
II SUMMARY 2
III LITERATURE REVIEW AND ASSESSMENT 3
Chemical and Physical Properties 3
Environmental Exposure Factors 12
Estimates of Ambient Air Concentrations 23
Health and Welfare Effects 35
Environmental Quality Aspects 50
REFERENCES 51
m
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TABLES
1 Physical and Chemical Properties of C$2 3
2 Physical and Chemical Properties of COS 4
3 Estimated One-Hour Ambient Inversion Concentrations of CS2
and COS at Various Distances from a Hypothetical Array of
Sulfur Recovery Plants 26
4 California Total Primary Energy Supply: 1971 29
5 California Sales of Heating Oils 29
6 California Sales of Distillate-Type Fuel Oils and Average
Sulfur Content: 1973 31
7 California Sales of Residual-Type Fuel Oils and Average
Sulfur Content: 1974 31
8 Los Angeles SMSA Sales of Gasoline and Average Sulfur
Content: 1974 32
9 Total Sulfur Consumption and Emission and Estimated Conversion
to COS and CS2 33
10 Summary of Source Contribution to Estimated Ambient
Stagnation Levels 34
11 Lethal Doses of CS2 and COS (Inhalation) 41
IV
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I INTRODUCTION
This report, prepared for the Environmental Protection Agency under
Contract No. 68-01-2940, Task 023, is subsidiary to the primary task of
ranking ten hazardous substances/agents for the EPA by the STAR Ranking
Objective Subsystem. The purpose of this supplemental report is to
provide information that will allow the EPA to know the tolerable con-
centrations of carbon disulfide and carbonyl sulfide in the ambient air.
-------
II SUMMARY
Carbon disulfide (€82) and carbonyl sulfide (COS) are volatile sub-
stances of moderate toxicity, odor, and environmental lifetimes (days).
Vapors emitted from sources are expected to follow normal atmospheric
dispersion principles. Each compound is produced from anthropogenic as
well as natural sources. The most significant anthropogenic emission
for CS2 is from commercial usages where the atmosphere serves as the
natural sink. The use of nonselective reducing catalysts may emit sig-
nificant quantities of COS. Little is known of the toxic thresholds for
COS; however, the significant industrial usage of CSo has provided ap-
preciable industrial hygiene records on effects. Based on industrial
effects records, and until better data on chronic exposures become avail-
able, we tentatively recommend that limiting long-term averaged concen-
trations to 300 (J:g/m^ CS2 should be sufficient for protection against
adverse health effects. By chemical and biological analogy to CS-, the
corresponding level for COS would be 400
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Ill LITERATURE REVIEW AND ASSESSMENT
Chemical and Physical Properties
General Characteristics
Carbon Disulfide
Carbon disulfide (CS~) is a colorless volatile liquid of mod-
erate solubility in water, with a partition coefficient of about 100
(octanol/water) (CRC, 1971 ;* Leo et al., 1971^). Using the rate of evapora-
tion approximation and assigned parameters as developed by Mackay and
Wolkoff (1973), the half-life for evaporation from a saturated water
solution is 11 minutes. Some of the physical and chemical properties of
CSo are given in Table 1.
Table 1
PHYSICAL AND CHEMICAL PROPERTIES OF CS2
Molecular weight: 76.13
Specific gravity: 1.26 (20°C)
Melting point: -108.6°C
Boiling point: 46.3 C
Vapor density: 2.63 (air = 1)
Vapor pressure: 360 mm Hg (25^C)
Solubility: 2.2 g/liter of water
1 mg/m3 =0.32 ppm
1 ppm = 3.12 mg/m3
*
CRC (1971), Handbook of Chemistry and Physics (Chemical Rubber Company,
Cleveland, Ohio).
Leo, A., C. Hansch, and D. Elkins (1971), "Partition Coefficients and
Their Uses," Chem. Rev., Vol. 71, No. 6.
Mackay, D., and A. W. Wolkoff (1973), "Rate of Evaporation of Low Solubility
Contaminants from Water Bodies to Atmosphere," Environ. Sci. Tech. , Vol. 7,
p. 611.
-------
CS„ is a linear molecule and has the structural representation
S = C = S (1)
Carbonyl Sulfide
Carbonyl sulfide (COS) is a colorless flammable gas of moderate
solubility in water. It is 16 times more soluble in alcohol and 30 times
j*
more soluble in toluene than in water (Patty, 1963)/ The chemistry of
COS has been reviewed by Perm (1957). Some of the physical and chemical
properties of COS are given in Table 2.
Table 2
PHYSICAL AND CHEMICAL PROPERTIES OF COS
Molecular weight: 60.07
Specific gravity, Gas: 2.1 (air = 1)
Density, liquid (-87°C): 1.24 g/ml
Vapor pressure (21°C): 9032 mm Hg
Melting point (1 atm): -139°C
Boiling point (1 atm): -50.2°C
1 mg/m3 =0.41 ppm (1 atm, 25°C)
1 ppm =2.5 mg/m3 (1 atm, 25°C)
COS is a linear molecule and has the structural representation
0 = C = S (2)
Chemical Reactions
Carbon Disulfide
Synthesis—CSp is an industrially important organic chemical
(Austin, 1974). Its production is limited to a vapor-phase reaction
from methane and sulfur:
Patty, F. A. (1963), Industrial Hygiene and Toxicology, 2nd ed., Vol. 2
(Wiley Interscience, New York, New York).
Ferm, R. J. (1957), "The Chemistry of Carbonyl Sulfide, Chem. Rev..
Vol. 57, p. 621.
-------
activated A1.203,
CH4 + 4S 700°C, 25 psi
Hydrogen (HoS) sulfide is reconverted to sulfur by the Glaus process and
recycled. An older process reacted surfur with wood charcoal in either
a retort or an electric furnace.
In the reaction furnace of Glaus plants for sulfur recovery
systems, CS2 is produced from COS and H2S:
COS + H S — 2H S + CS (4)
and from methane and sulfur:
CH + 4S — 2H S + CS (5)
4 22
Levels as high as 5000 ppm for both COS and CS2 have been encountered in
the tail gas of Glaus plants; values ranging from 700-1500 ppm are more
common.
An old process for the production of carbon tetrachloride used
CS2 and chlorine with an iron catalyst at ambient temperatures. Dithio-
carbamates can result from reacting CS2 with ammonia (Austin, 1974):
CS,, + 2NH,, — H NCSSNH, . (6)
23 24
CS has been detected in the magtnatic gas over volcanoes
t
(Nordlie, 1971), during the aging of roasted coffee (Radtke et al., 1963),
Austin, G. T. (1974), "The Industrially Significant Organic Chemicals--
Part 2," Chem. Eng., p. 127 (February 18, 1974).
Nordlie, B. E. (1971), "The Composition of the Magmatic Gas of Kilauea
and Its Behavior in the Near Surface Environment," Am. J. Sci., Vol. 271,
p. 417.
*
Radtke, R.. et al., (1963) The Chemical Processes During the Aging of
Roasted Coffee," Z. Lebensn. Untersuch. Forsch., Vol. 119, p. 293.
5
-------
•
during the pressure cooking of grain-water mixtures (Ronkainen, 1973), as
a volatile constituent in the vapor of burning cigarettes (ORNL, 1975),
and in the vapor space above liquid sulfur (Pickren and Matson, 1964).
Decomposition—CSp is stable to hydrolysis in the pH region of
environmental concern (pH = 4 to 10). Hydrolysis of carbon disulfide to
carbon dioxide and hydrogen sulfide is a two-step process with carbonyl
sulfide as an intermediate product:
CS2 + H20 — COS + H2S (7)
COS + H20 — C02 + H2S (8)
C02 + 2H2S (9)
At pH = 13 (0.1 N NaOH) CS2 has a half-life of about 1 hour at 25°C.
Extrapolation of this value to pH = 9 gives a half-life of 1.1 years.
In basic solution, the carbon dioxide is converted to bicarbonate
(COn + OH" - »-HCOo~), which precludes reversibility of the reaction.
The electrophilic character of CS? does, however, provide for scrubbing
and analytical techniques utilizing more nucleophilic reagents (amines
and heterogeneous catalysts).
The flammability limits of CS2 are 1 percent to 50 percent by
volume in air, posing an acute fire and explosion hazard at high concen-
trations (flash point is -30°C). The oxidation has been studied
"Ronkainen, P. (1973), "Formation of Volatile Sulfur Compounds During Pres-
sure Cooking of Grain-Water Mixtures," J. Inst. Brew., London, Vol. 79,
No. 3, p. 200.
ORNL (1975), "ORNL Tobacco Smoke Research Program Summary Report," Oak
Ridge National Laboratory, March 1975.
Pickren, R.A., and R. F. Matson (1964), "Chromatograph Aboard a Liquid
Sulfur Ship," Chem. Eng. Progr., Vol. 62, No. 2, p. 95.
-------
for these as well as for theoretical purposes concerning the intermediate
species in these reactions (Wood and Heicklen, 1971a)." Reports on the
reaction with ozone and on photooxidation have also been made. The
rate constant for the reaction of CS2 with an oxygen atom is 5.6 X 10"
(M-sec) at 25°C as calculated from the Arrhenius expression as obtained
by Westenberg and DeHaas (1969).
j.
Olszyna and Heicklen (1970) have reported on the reaction of
ozone with CSo. The yields of products (normalized to initial ozone
concentration) are 0.85 02, 0.36 S02, 0.16 OCS, 0.10 CO, and 0.03 C02-
Wood and Heicklen (1971b, 1973/74) have reported photooxidation
studies of CS2 at 2139 A and 3130 A. DeSorgo and coworkers (1965) have
also investigated this process. Photolysis at wavelengths less than
o
2300 A proceeds in part by dissociation of the photoexcited species
(CS2*) to CS and a sulfur atom:
CS2 -CS2* (10)
CS2* — DS + S (11)
"Wood, W. P., and J. Heicklen (1971a), "Kinetics and Mechanism of the Carbon
Disulfide Oxygen Explosion," J. Phys. Chem., Vol. 75, p. 861.
Westenberg, A. A., and N. DeHaas (1969), "Atom-Molecule Kinetics Using
ESR Detection, V Results for 0 + OCS, 0 + CS2, 0 + N02 and H + C2H4,"
J. Chem. Phys., Vol 50, p. 707.
Olszyna, K. J., and J. Heicklen (1970), The Reaction of Ozone with Carbon
Disulfide," J. Phys. Chem., Vol. 74, p. 4188.
6
Wood, W. P., and J. Heicklen (1971b), "The Photooxidation of Carbon Disul-
sulfide," J. Phys. Chem., Vol. 75, p. 85.
Wood,oW. P., and J. Heicklen (1973/74), The Photooxidation of CS2 at
2139 1," J. Photochem., Vol. 2, p. 173.
ft
DeSorgo, M., et al., (1965), "The Photolysis of Carbon Disulfide and
Carbon-Oxygen Mixtures," Can. J. Chem., Vol. 43, p. 1886.
7
-------
In the presence of oxygen the products are CO, COS, SC>2, $20, and possibly
SO-j. No carbon dioxide is found. At wavelengths greater than 2300 A
(lower energy) photodissociation does not occur. The mechanism is then
the reaction of the photoexcited CS2 with oxygen or itself:
cs2" + o2 — cs + soo (-so2) (12)
CS2" + CS2 - 2CS + S2 . (13)
An excited-state quenching process with 02 was also in evidence:
CS2* + 02 - CS2 + 02 . (14)
The photooxidation study at 3130 A is relevant to environmental
conditions as this wavelength is within the solar spectrum. The products
of the reaction were CO, COS, S0~, and polymer [see Eqs. (15) and (16)]
(Wood and Heicklen, 1971b). Carbon dioxide and SO-, were not found as
products. Quantum yields of products were small and ranged from 3 X 10
to 10" l.
CS2 + °2 "" CS2 + °2
CS + SOO (-SO ) (15)
CS + 0 — COS + 0
CO + SO (-SO ) . (16)
The product ratio COS/CO was found to be approximately 1:2 with a good
carbon-sulfur mass balance for the gaseous products.
The information available indicates that CS2 is relatively per-
sistent in the atmosphere. Atmospheric oxidation of CS will produce SO ,
-------
COS, and CO. In the absence of a direct measure of an environmental half-
life for CS , we make the following estimates:
• Oxygen atom reaction. Modeling for atmospheric
chemistry suggests that the oxygen atom is an
important species which results from the photolysis
of ozone and/or nitrogen dioxide among other sources
(Demerjian et al., 1974)." If we assume an ambient
steady-state concentration of oxygen atoms as
4 x 10"9 ppm (1.2 x 1CT16 M), the half-life for
CS2 at 25°C is approximately 12 days.
• Ozone reaction. The data of Olszyna and Heicklen
(1970) are not amenable to an environmental predic-
tion. The unusual kinetic expression, as reported
in the cited paper, has been explained as being due
to aerosol formation in the experimental work
(J. Heicklen, personal communication, 1975). Since
the CS2 concentrations in the experiment were in
excess of 1300 ppm and the ozone concentration, the
potential for aerosol formation under environmental
conditions is not certain.
• Photooxidation of CSn. To approximate the photo-
oxidation of CS^ some evaluation of the specific
absorption rate constant at 3130 A is needed
(Leighton, 1961). Correcting the value for the
S02 photooxidation study of Allen, McQuigg and
Cadle (1972)* to that for CS2 at this wavelength
(extinction coefficient ~ 50 M sec ) (Trieber
et al., 1957),3 a specific absorption rate con-
stant of 0.93 day"^ is obtained. Taking the
maximum quantum yield of 10 from the work of
Wood and Heicklen (1971b), a mean lifetime of
130 hours is calculated, corresponding to 11 days
when assuming 12 hours of sunlight per day.
*
Demerjian, K. L•, J- A. Kerr. and J. G. Calver (1974). "The Mechanism of
Photochemical Smog Formation," Adv. Environ. Sci. Tech.. Vol. 4, p. 1.
t
Leighton, P. A. (1961), Photochemistry of Air Pollution (Academic Press,
New York, New York).
Allen, E. R., R. D. McQuigg and R. D. Cadle (1972), "The Photooxidation
of Sulfur Dioxide in Air, Chemosphere. Vol. 1. p. 25.
fi
'Treiber, E. et al., (1957). "UV and IR-Absorption von Kohlenstoffdise-
lenid," Acta Chem. Scand.. Vol. 11, p. 752.
-------
Taking the minimum quantum yield value (3 x 10 ),
the mean lifetime is 10 years for 12 hours of sun-
light per day.
Thus photooxidation may be a contributing or insignificant
process in the degradation of 082 in the atmosphere. The uncertainty
arises from both the limits of the experimental work reported (quantum
yields, reactant concentrations, quenching effects, and the like) as well
as the climatological conditions of any subject area.
Carbonyl Sulfide
Synthesis--COS is prepared by the action of oxidizing agents
on CS? and as a by-product during the preparation of C$2 from carbonaceous
matter and SC^. It may be formed by heating oxides of carbon with sulfur,
or by the action of carbonyl chloride on sulfides. Ferm (1957) reviews
the various methods of synthesis. In the Glaus reaction furnace, CC>2
reacts with IS:
CO + H S — HO + COS . (17)
Equations (7) and (16) indicate that COS is a natural decomposition prod-
uct of CS_ in the environment.
In a similar manner to CS2, COS is produced in a variety of
natural environs. It emanates from cattle manure at concentrations up
to 3 ppm for several days (Elliot and Travis, 1973),* from volcanic fuma-
4-
roles at temperatures exceeding 400° C (Momot, 1964), during the cooking
Elliot, L. F., and T. A. Travis (1973), "Detection of Carbonyl Sulfide
and Other Gases Emanating from Beef Cattle Manure," Soil Sci. Soc, Am.
Proc., Vol. 37, p. 700
Momot, J. (1964), "Carbonyl Sulfide, a Product of the Activity of Vol-
canic Fumaroles," Bull. Mens. Soc. Linneenne Lyon, Vol. 33, No. 8, p. 326,
10
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of grain-water mixtures (Ronkainen, 1973), and as a volatile component
in tobacco combustion (ORNL, 1975). It is probable that most carbonaceous
combustion processes involving sulfur compounds emit COS directly, as well
as indirectly from biological production of l^S, which further reacts with
CO and C02 to produce COS.
Decomposition--COS is an intermediate in the hydrolysis of CS2
as previously discussed. The half-life at pH = 12 (0.01 N KOH) is about
JU
three minutes at 22°C (Galivets et al., 1972)." Extrapolation to pH = 9
gives a half-life of about 2 days. At pH = 8 the half-life would be ap-
proximately 20 days. Its decomposition rate is more rapid than the hydro-
lysis of CS2 under similar conditions. In 19 percent ethanol solvent,
COS reacts some 1000 times faster than CS£ in alkaline hydrolysis (Philipp
and Dautzenberg, 1966). A more detailed study on the alkaline hydrolysis
of COS has also been reported by these authors (Philipp and Dauzenberg,
1965).
We found no photooxidation studies on COS or reports on reaction
with ozone in the chemical literature. The rate of oxygen atom reaction
with COS at 25°C as calculated from the work of Westenberg and DeHaas (1969)
Q _ ^
is 6.9 x 10 (M - sec) . Calculation at the same temperature based on the
expression of Wood and Heicklen (1971b; 1973/1974) gives a rate constant
of 3.6 x 108 (M - sec)"1:
COS + 0 — CO + SO . (18)
Galivets, L. S., Yu. I. Usatenko, and D. V. Galivets (1972), "Investiga-
tion of Kinetics of Alkaline Hydrolysis of Carbon Bisulfide," Soviet
Chem. Ind., Vol. 48, No. 12, p. 730.
Philipp, B., and H. Dautzenberg (1965), "Untersuchungen zur Bildung und
Zersetzung von Monothiocarbonat in wassriger Losung," Z. Physik. Chem.
(Leipzig), Vol. 229, p. 210.
11
-------
The volatility of COS and slow hydrolysis at relevant environmental pH
values suggest that COS will be present and gradually degraded in the
atmosphere. In the absence of other data, an environmental lifetime must
be based on the oxygen atom reaction as previously discussed for CSo.
Again, if we assume a steady-state oxygen atom concentration of 1.2xlO^M
and use the rate constant of Wood and Heicklen (1971b: 1973/1974), we cal-
culate a half-life of 0.5 years. The value of Westenberg and deHaas
(1969) would predict 0.3 years.
It has been suggested that COS elicits a toxic response due to
partial decomposition in the lungs and blood stream to H?S via hydrolysis
(Patty, 1963). According to the above rate constants and chemical reviews
by Perm (1957) this appears to be a relatively slow reaction at physio-
logical pH. However, as indicated by Philipp and Dautzenberg (1966),"^
the hydrolysis of COS is 1000 times faster than CS~ in an ethanol solvent.
Thus, the production of t^S in biochemical metabolism seems reasonable.
It is significant that in coke oven gas stored for five years
a total disappearance of the 0 , COS, and CS2 occurred. However, initial
traces of iron and nickel carbonyl rose to 1000 mg/m3 and 10 rng/m ,
respectively (Degent et al., 1962).
Environmental Exposure Factors
Sources and Emissions
Commercial Production and Emissions
Carbon Disulfide--In 1974 approximately 350 million kilograms
of CS2 were produced by five U.S. manufacturers. Over 8070 of the produc-
tion of CS2 is used to make regenerated cellulose rayon and cellophane.
Degent, C.. C. Rouse, and C. Lebras (1962). "Modification in Properties
of Coke-Oven Gas During Underground Storage," Rev. Combust., Vol. 16,
No. 1, p. 11.
t
Philipp, B., and H. Dautzenberg (1966), "Zur Bildungsgeschwindigkeit von
Na-Athylmonothiocarbonat in Vergleich zu Na-Athylxanthogenat," Z. Physik.
Chem. (Leipzig). Vol. 231, p. 270.
12
-------
In the rayon process CS? is employed as a solvent carrier to form xanthate
crumb from alkali cellulose; tLS and CS are liberated upon immersion into
acid spinning baths, where the viscose is coagulated and filaments ex-
tracted (Austin, 1974;Davidson and Feinleib, 1972"). The minor inter-
v
mediate uses of 082 are numerous and include the manufacture of many in-
dustrial chemicals such as thiocarbamates, xanthates, mercaptans. thioureas.
and carbon tetrachloride. Among the many dispersive uses, CS^ is used as
a solvent for oils, waxes, and the flushing of oil casings, and as a
fumigant in pesticide applications (CEH, 1973).
It is estimated that 100 million kilograms of industrially
produced CS2 were emitted in the U.S. to the atmosphere and approximately
35 million kilograms reached the water and land in 1973 (SRI, 1975).* It
is probable that the 35 million kilograms deposited to land and water
found an eventual sink in the atmosphere due to the high volatility of
the compound.
Carbonyl Sulfide--Less than one thousand pounds of COS were
commercially produced in the United States in 1973 (Directory of Chemical
Producers, 1975).^ No dispersive uses are known, and the intermediate uses
are in the synthesis of thioacids, S-trisubstituted carbinols, and sub-
stituted thiazoles. The fraction of COS emitted to the environment by
commercial sources is insignificant compared with that emitted by non-
commercial sources (SRI, 1975); however, significant quantities are gen-
erated in the atmospheric decomposition of CS,-,. COS was recently presented
Davidson, M., and M. Feinleib (1972). "Carbon Disulfide Poisoning: A
Review," Am. Heart J.. Vol. 83, No. 1, p. 100.
t
CEH (1973), Chemical Economics Handbook (Stanford Research Institute.
Menlo Park, California).
SRI (1975), "STAR Ranking Objective Subsystem." Draft Report, EPA Con-
tract 68-01-2940, Task 023, Stanford Research Institute. Menlo Park.
California.
§
Directory of Chemical Producers (1975). Stanford Research Institute.
Menlo Park, California.
13
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as a chemical building block (Field and Sawhon, 1974) and may find wide-
spread use in the future.
Natural and Anthropogenic Emissions
The quantity of CS~ and COS emitted from such natural sources
as volcanic and geothermal activity is not known; however, previously
cited reports indicate these natural sources may be significant con-
tributors. As previously indicated, COS has been produced in large
quantities (=-3 ppm air) from cattle feedlots. It also has been found in
horseradish plant tissue up to 12 ppm (Rauch, 1962). Combustion of fossil
fuels and other carbonaceous material in the presence of sulfur compounds
probably generates significant quantities and contributes to atmospheric
emissions; however, the combustion contribution is probably disperse
rather than concentrated. Various industrial gases have reported concen-
trations ranging from 30 ppm to 90 ppm COS and hydrogen produced from
coal gas contains both COS and CS2 (Perm, 1957). Some NOX reducing cata-
lytic systems have been reported emitting COS from input S02 (Koutsoukos
et al., 1975).*
Of primary significance to the health and welfare of man are
the sources where emissions of COS and CS™ are most concentrated and
controllable. Such emissions are found in sulfur recovery plants and
potentially from mobile and stationary sources where reducing catalysts
are used.
Field, E., and E. A. Sawhon (1974), "Carbonyl Sulfide as a Chemical Build-
ing Block," paper presented at the Symposium on New Sulfur Chemistry,
167th ACS National Meeting, Los Angeles, California, 1974.
Rauch, G. (1962), "The Defensive Substances of Plants, III: Horse
Radish Gas," Z. Naturforsch., Vol. 17, p. 800.
Koutsoukos, E. P., et al. (1975), "Assessment of Catalysts for Control
of N0x from Stationary Power Plants," Report No. EPA-650/2 75 001-a,
Environmental Protection Agency, Washington, D.C.
14
-------
The process of removing sulfur-containing compounds (primarily
HoS) from gaseous fuels and recovering elemental sulfur as a by-product
is a widespread activity in the United States. Sulfur recovery occurs
mainly in conjunction with refinery operations and natural gas processing
facilities and may also take place in certain types of chemical plants.
Future expansion in all these areas may be expected to occur. In addi-
tion, the deployment during the next few decades of fossil fuel conversion
facilities, such as coal liquefaction and gasification plants and oil
shale processing plants, will greatly increase sulfur recovery activities.
The most common method of removing and recovering sulfur from
hydrocarbon gas streams is to scrub the gas with amine compounds (e.g.,
monoethanolamine, di-isopropanolamine) to absorb the F^S, after which the
solution is stripped and the concentrated H2S stream is directed to a
Glaus sulfur recovery unit where it is oxidized to elemental sulfur.
The Glaus process carries out catalytic oxidation of H2S to sulfur in
the presence of air at elevated temperatures. The important reactions
in the Glaus process are the direct oxidation reaction
- 02 - H20 + S (19)
and the two-step process
3
H2S + - 02 — SO + H20 (20)
2H2S + SO •- 3S + 2H 0 (21)
As many as three stages of Glaus conversion may be used to remove up to
96 percent of the l^S from the feed stream.
The formation of COS and CS,., during the Glaus process is due
to the presence of carbon compounds. The amine scrubbing system removes
15
-------
some CO- as well as hydrocarbons from Che fuel gas and H^S. The reactions
which are thought to be important in the formation of €82 and COS during
Glaus conversion are:
CO + H S —H 0 -+ COS (22)
COS + H2S •-H 0 + CS (23)
CH + 3S — H S + CS (24)
4 12
The levels of COS and CS present in the Glaus tail gas stream
thus depend on the quantities of CO and hydrocarbons present in the
feed stream. Typically, COS and CS levels are on the order of 1000 ppm,
although much higher levels may be attained (Beavon and Vaell, 1972)."
Typical practice in refineries and natural gas fields has been
to incinerate the Glaus tail gas, thus converting all reduced sulfur
compounds to SO,-, and eliminating odor problems caused by H S and CS
emissions. However, the enactment of state and local laws regulating the
emission of sulfur compounds (usually expressed as total sulfur) from
sulfur recovery plants has brought about the increased use of tail gas
cleanup procedures.
Tail gas treatment technologies generaly fall into two cate-
gories: those that oxidize the sulfur compounds in the tail gas to SO
and then apply SO removal techniques, and those that reduce sulfur com-
pounds to l^S and then apply f^S removal techniques. Examples of the
former are the Wellman-Lord and IFP-2 processes. Examples of the latter
'Beavon, D. K., and P. P. Vaell (1972), "The Beavon Sulfur Removal Process
for Purifying Glaus Plant Tail Gas," paoer presented at the 37th Midyear
Meeting, American Petroleum Institute Division of Refining, May 1972.
16
-------
are the Cleanair, Beavon, and SCOT processes. Two other processes, IFP-1
and Sulfreen, are basically extensions of the Claus process and treat SO
and H S together.
Since incineration of the Claus tail gas leaves only trace
amounts of COS and CS , the emission of these compounds becomes a problem
only when tail gas treatment which deals with reduced sulfur compounds is
applied. Only the Cleanair and Beavon processes emit any significant
amounts of COS and CSo (tail gas of the SCOT process is incinerated).
Both of these processes are effective in achieving greater than 99.9 per-
cent sulfur removal in conjunction with an efficient Claus plant (Beavon
and Vaell, 1972; Landrum et al., 1973)."' However, emissions as high as
1000 ppm could occur with Beavon catalyst degradation.
As of January 1, 1974 there were 108 Claus sulfur recovery plants
with an average capacity of 78.3 metric tons/day installed in the U.S.
4-
refineries (OGJ, 1974). As of March 1, 1974, approximately 30 of these
plants had installed or announced plans for tail gas treatment units.
Based on the total number (169) of Claus plants operating in
the United States in early 1973 we estimate that approximately 60 Claus
plants were associated with natural gas processing. The average capacity
was approximately 127 metric tons/day (Beers, 1973). There are also a
few small sulfur recovery units operating in chemical plants.
The total level of sulfur recovery from all operations (refin-
eries, natural gas processing, and chemical plants) was 16,053 metric
tons/day in 1973 (Beers, 1973). Incinerations of tail gas resulting
Landrum, L. H., et al. (1973), "The Cleanair Sulfur Process." paoer pre-
sented at the 74th AICLE Meeting, New Orleans, Louisiana, March 1973.
t
OGJ (1974), Oil and Gas Journal, pp. 84-103 (April 1, 1974).'
Beers, W. D. (1973),"Characterization of Claus Plant Emissions." EPA
Report No. EPA-72-73-188. Environmental Protection Agency, Washington,
D.C. (April 1973).
17
-------
from these operations would result in very small total emissions of COS
and CS . Total emissions of SO have been estimated at 135,000 metric tons
per year, assuming no tail gas treatment (Beers, 1973).
Of the 30 Glaus sulfur plants in refineries for which tail gas
treatment units had been installed or planned in 1974, 16 were of the
Cleanair or Beavon type (EPA, 1975)," both of which release CS and COS.
The total sulfur plant capacity for which these tail gas units were in-
tended was approximately 1,828.8 metric tons/day, or 71 percent of the
total sulfur recovery capacity for which tail gas cleanup units were
installed.
As a basis for making a quantitative estimate of total emissions
of CS and COS we assumed first that emissions result only from Beavon
or Cleanair units installed or planned for as of 1974 and that the propor-
tion of these units installed in natural gas processing facilities is the
same as the proportion installed in refineries. On this basis the total
sulfur plant capacity of units having these tail gas treatment processes
would be 3,487.4 metric tons/day. Assuming, on the average, that 2.0 kg/h
CS2 and 1.5 kg/h COS are emitted per 101.7 metric tons/day sulfur plant
capacity with Cleanair or Beavon tail gas treatment (EPA, 1975), we cal-
culate that 599.1 metric/tons CS and 463.0 metric tons COS could have been
emitted yearly from this source. Worst case conditions would assume Beavon
catalyst degradation for all plants and would correspond to 20 kg/h CS
and 15.4 kg/h COS per 101.7 metric tons/day sulfur plant capacity.
If we assume that 71 percent of the entire 16,063.9 metric
tons/day of U.S. sulfur plant capacity is equipped with Beavon or Clean-
air units, then 1,997.2 metric tons CS and 1,543.3 metric tons COS
could be emitted yearly. Again, worst case conditions would correspond
to 19,971.6 metric tons CS and 15,432.6 metric tons COS emitted yearly.
*
EPA (1975), Environmental Protection Agency, unpublished data.
18
-------
These figures do not take into account the anticipated expansion of
sulfur plant capacity.
In coal conversion processes (gasification and liquefaction)
the sulfur compounds in the coal are subjected to a reducing atmosphere
so that H S, COS, and CS are the primary sulfur compounds present in the
product and by-product gas streams. In coal gasification processes, the
first step is the reaction of coal with steam and oxygen at elevated tem-
peratures and pressures. The resulting synthesis gas (mainly CO and H )
is then quenched to remove particulates and oils subjected to the CO shift
reaction
CO + H20 »- CO + H (25)
to achieve the appropriate H /CO molecular ratio, and finally reacted
catalytically to form methane or substitute natural gas (SNG) as follows:
CO + 3H *~CH, + H2° • (26)
The raw synthesis gas contains on the order of 3000-5000 ppm of H S,
100-1000 ppm of COS, and smaller amounts of CS (< 10 ppm) (EPA, 1974).*
During the CO shift stage, much of the COS and CS is hydrolyzed as
follows:
(27)
COS + HO —H S + CO . (28)
The remaining gas is then scrubbed to remove the acid gases CO and H S
as well as COS and CS . After stripping the scrubber solution, the result-
ing gas stream is dilute in H S compared with the concentrated streams
*
EPA (1974), "Symposium Proceedings: Environmental Aspects of Fuel Con-
version Technology (May 1974, St. Louis, Missouri)," Report No. EPA-650/
2-73-118, Environmental Protection Agency, Washington, D.C. (October 1974)
19
-------
(90 percent l^S) derived from refinery gases. If the stream is too dilute,
the Glaus process will have low efficiency in converting H S to sulfur.
An alternative process which may be used is the Stretford process, where
the H S is absorbed by a solution of sodium carbonate, sodium vanadate,
and anthraquinone disulfonic acid. Through a series of steps, the over-
all oxidation reaction [Eq. (20)] is carried out. The Stretford process
does not appreciably affect the COS and CS present in the feed stream.
El Paso Natural Gas Company has proposed to build a coal gasi-
fication plant in northwestern New Mexico for the production of 76.2 mil-
lion cubic meters (250 million cubic feet) per day of SNG. The Stretford
process will be used to treat the H S resulting from scrubbing of the syn-
thesis gas by the Rectisol (cold methanol) process. Both lean and rich
t^S streams will be generated and treated for sulfur recovery. The tail
gas from the rich stream treatment will be incinerated, thus converting
all sulfur compounds to SO.,. The tail gas from the lean stream treatment
(containing mostly C02 and N2) will be vented to the atmosphere. The con-
centrations of CS,-, and COS in this stream have been estimated at approxi-
mately 2 ppm and 65 ppm, respectively (El Paso, 1974) * The total level
of emissions from the plant will be 2.7 kg/h CS2 and 78 kg/h COS. These
emission levels correspond to the release of 0.031 percent of the sulfur
in the coal entering the plant as CS~ and 0.57 percent of the sulfur as
COS. The expected emission levels are based on thermodynamic calculations
but are not well defined at this time, however.
In general, the release of COS and CS from coal gasification
plants will depend on the sulfur content of the coal being gasified, the
methods chosen for gas purification and sulfur recovery, and the treatment
(if any) applied to the sulfur recovery plant tail gas. The numbers pre-
sented above are based on the best current estimates according to El Paso's
*
El Paso (1974), "Revised Report on Environmental Factors, Burnham Coal
Gasification Project," El Paso Natural Gas Company, El Paso, Texas.
20
-------
engineering design of a proposed commercial-size plant. Unfavorable re-
action kinetics could result in emission several times the expected levels.
The generation of reduced sulfur compounds in coal liquefaction
can occur in the following two processes: (1) the gasification of coal or
by-product carbonaceous material to generate hydrogen for use in the
hydrogenation step of coal liquefaction, and (2) the hydrogenation step
itself, wherein finely divided coal, which has been slurried in a coal-
derived solvent, is reacted with hydrogen to carry out dissolution of the
organic matter in the coal.
The production of hydrogen from coal or other carbonaceous
material proceeds much as in the production of SNG. The coal is gasi-
fied with steam and oxygen, the synthesis gas is quenched, and the CO
shift reaction [Eq. (25)] is carried out. Of course, the extent of the
CO shift reaction is much greater than it is when methane is the desired
end product. Thus the degree of hydrolysis of CS and COS may be expected
to be greater. The subsequent purification of the H stream to remove
H S and CO , followed by sulfur recovery, will undoubtedly result in the
release of lower quantities of CS and COS per unit volume of gas produced,
for the reasons cited above.
The hydrogenation of the coal slurry will generate primarily
H S if pure hydrogen is employed. This H S will enter the by-product
hydrocarbon gas stream, where purification and sulfur recovery will be
carried out much as in refinery operations. CS and COS will be formed
primarily via reactions with hydrocarbons and CO in the Glaus plant.
An alternate route to coal hydrogenation has been considered
in which synthesis gas would be used instead of hydrogen as the reducing
medium (Exxon, 1975). In this case, the level of CS and COS generated
*
Exxon (1975), "Evaluation of Pollution Control in Fossil Fuel Conversion
Processes—Liquefaction: Section 2, SRC Process," Report No. EPA-650/2-
74-009-f, Exxon Research and Engineering Company (March 1975).
21
-------
would be significantly higher, due to both the omission of the CO shift
reaction (7), in which CS and COS tend to be hydrolyzed, and the presence
of CO and CO in the hydrogenation medium, which leads to the formation of
COS and CS .
The treatment of sulfur-containing by-product gases in oil
shale retorting and upgrading plants will be similar to treatment carried
out in refineries. A more dilute H S stream resulting from amine scrubbing
of these gases will result, because of the high CO content of the gases
and the preferential absorption of C02 along with the H^S. The dilute
H^S stream entering the Glaus plant results in a lower overall sulfur
recovery and possibly higher COS and CS emissions in the tail gas after
treatment. The Beavon or Cleanair processes are anticipated for the first
commercial oil shale plants.
Colony Development Operation estimates that for a 50.000 bbl
(5960 m-*) per day oil shale plant, 29 kg/h of sulfur compounds (such as
502) will be emitted in the 175 metric tons/day sulfur recovery plant
tail gas (Colony, 1974)." This corresponds to a sulfur removal efficiency
of 99.8 percent. Assuming that, on a volume basis, the tail gas sulfur
is equally divided between COS and CS2, we calculate that 11.8 kg/h CS2
and 9.5 kg/h COS could be emitted as an upper limit from a 50,000 bbl per
day oil shale plant.
Certain reducing catalysts for the control of NO also reduce
X
S02 to S, l^S, and COS. This is generally considered to be nonselective
NO reduction and implies that sufficient reductant is present in the
flue or exhaust gas streams to reduce all the oxidant constituents of the
stream. An assessment of nonselective catalytic reduction as applied to
stationary power plants is made by EPA (Koutsoukos et al.. 1975). Some
i,.
~Colony (1974), "An Environmental Impact Analysis for a Shale Oil Complex
at Parachute Creek, Colorado," Colony Development Operation, Atlantic
Richfield Company.
22
-------
reducing catalysts do not produce H S or COS while efficiently reducing
NO and SO . No data were given for CS^ production for any of the non-
selective catalysts evaluated. It is probable that the residence times
under the operating conditions in the catalytic processes reviewed were
not sufficient for CS2 generation. In some reported instances successful
attempts were made to maximize simultaneous S02 reduction by increasing
residence times; however, COS production dramatically increased together
with noncollectable sulfur species other than elemental S or HoS. A
significant fraction was probably CS2«
Of the nonselective reducing catalysts (that emit COS) reviewed
in the EPA report, the most applicable to power plants appear to be TRW's
NOX - SO catalytic reduction process. In this process approximately
six percent of input sulfur is reported emitted as COS. The remaining
sulfur is emitted as elemental sulfur and H S.
An important reaction in Glaus plant CSo production [Eq. (4)]
combines COS and H S to form CS and H20. Considering this reaction it
is probable that some CS2 is produced in nonselective reducing catalysts.
Estimates of Ambient Air Concentrations
Downwind ground-level concentrations can be estimated by a plume
dispersion model (Perkins, 1974):*
X = e
TTCJ a U
y z
where
X = M-g COS and CS /m
Q = source strength in |ag/sec
1/2
\ rr_ / I
(29)
Perkins, H. C. (1974), Air Pollution. Chap. 8, "Plume Dispersion" (McGraw-
Hill Book Company, New York, New York).
23
-------
U = average wind speed in m/sec
a ,a = vertical and horizontal diffusion coefficients
y z
in meters
H = effective height of source emission in meters.
Using a nomograph of Turner's (Perkins, 1974), the maximum ground-level
concentration downwind from a 50-m stack under thinly overcast conditions
and moderate windspeed (2-3 m/sec) would be approximately 2.5 km from the
source. The value
o a
v z
reduces to 3.1 • 10 . Using U = 3 m/sec and Beavon catalyst degradation
(20 kg/h 082 and 15.4 kg/h COS per 101.6 metric tons/day sulfur recovery
plant: Q = 5.5 ' 10 p,g CS2/sec and 4.3 ' 106 |ig COS/sec)
v (3.1 • 10'5)[(5.5 • 106) or (4.3 • 1Q6 >]
X = „
= 57 |_ig CS2/m3 and 44 (ig COS/m3
This would be the maximum ambient ground-level concentration occurring
in any 1-h period. Average annual concentrations would be considerably
lower .
It is of interest to consider what 1-h maximal ambient concentra-
tions would be expected for an array of oil refinery sulfur recovery plants
under inversion conditions. Perkins (1974) presents the following inver-
sion model which can be adapted to summing refinery arrays:
x =
1/2
(2rr) UH.a
1 y
24
(30)
-------
where
H = upper level inversion layer
i
y = distance from horizontal plume axis.
Thus for a hypothetical array of nine sulfur recovery plants in rows of
three at 3-ktn intervals,
performed to calculate X:
three at 3-km intervals, the sum of Eq. (31) for given values of y. is
X =
(2n)1/2UH a
1 yi
2-,
-1/2
1 + 2e
(31)
where
a . = f(d)
yi
a = f(d + 3 km)
a = f(d . 6 km)
X =
3 km
^ *)
I
y = 3 km
Table 3 presents the results for distances of 1, 5, 10, 20, and 100 km
at an H. of 400 meters, a U of 3 m/sec, and a Q of 20 kg/h CS (5.6 • 106
lag/sec) and 15.4 kg/h COS (4.3 • 10 (ig/sec), corresponding to emissions
from a 101.7 metric tons/day sulfur recovery plant with Beavon catalyst
degradation.
The predicted ambient values are directly related to emission rates
with this model.
25
-------
Table 3
ESTIMATED ONE-HOUR AMBIENT INVERSION CONCENTRATIONS
:OS AT VARIOUS DISTANCES FROM A I
ARRAY OF SULFUR RECOVERY PLANTS
OF CS2 AND COS AT VARIOUS DISTANCES FROM A HYPOTHETICAL
22
24
12
9
7
5
4
3
2
1
1 km 5 km 10 km 20 km 100 km
Ug/m3 CS2
ug/m3 COS
It is also of interest to compute what ambient levels of CS,-, or COS
could exist within a defined basin during a period of stagnation. The
following simple model can be used to calculate the potential ambient
levels from sulfur recovery plants:
X . (32,
where
X = ng/m3
T = hours of stagnation
P = total sulfur recovery capacity (metric tons/day)
F = fraction emitting CS and COS
Q' = emission rate (ug/h 102 metric tons/day)
L = fraction lost from basin
2
A = area of basin (m )
H. = height of inversion (m).
Substituting the following values, we can approximate for the Los Angeles
Basin the input from sulfur recovery plants under worst operating condi-
tions (Beavon catalyst degradation):
26
-------
T = 120 hours
P = 2033.4 metric tons/day
F = 0.7
Q' = 2.0 • 10 ng CS2/h (20 kg/h) or 1.5 • 10 ng COS/h
(34 ng/h)
L = 0.1
A = 1.55 • 109 m2 (15 miles by 40 miles)
H. = 300 m
i
Y
(,1^1); (/(JJj.q.,) ((j . 1) \
• 1010\
J
(0.9)
(1.55 • 109)(3 • 102)
= 65 |j.g CS2/m3 or 48 |ig COS/m3
From 1973 data, we estimate 136 million kg (1.4 x 10 metric tons)
of CS2 are emitted to the atmosphere annually from industrial production
for intermediate and dispersive commercial use. Assuming that this com-
mercial emission is evenly distributed with respect to the population,
the stagnation level for the Los Angeles Basin can be calculated in a
manner as for sulfur recovery plant emissions:
ED F (1 - L)
X = —£ (33)
i
where
X = ng/m3
E = daily national emission rate (p.g/day)
D = days of stagnation
F = fraction of population
P
L = loss during inversion
A = area of basin
H. = height of inversion.
27
-------
Substituting the following values:
(1.4
365 days x 9.08 • 1011/ton)
E = 3.73 • 1014 M.g/day (1.4 • 105 metric tons/
D = 5 days
F = 0.036 (7.5 million)
P
L = 0.1
AH. =4.65 ' 1011 m3
i
v (3.73 -IP14)(5)(0.036)(0.9)
X —
4.65 • 1011
6.04 • 103
4.65 • 1011
= 129 n/m3 CS
2
Emissions of COS and CS to the Los Angeles Basin from other sources
are difficult to estimate; a preliminary appraisal of the quantity of
sulfur flowing through the different fuel processes is required before
such emissions can be estimated. Table 4 presents the sources of Cali-
fornia's primary energy supply.
We do not consider gas, wood, hydroele^ ;. _cr primary
energy supplies because they are not a source of sulfur emissions . Nor
do we consider coal, because it is not a significant part of California's
(and Los Angeles') energy supply or sulfur emissions.
Table 5 presents data concerning the sales of heating oils and sul-
fur content in California.
28
-------
Table 4
CALIFORNIA TOTAL PRIMARY ENERGY SUPPLY: 1971
Petroleum
Coal
Gas
Wood
Hydroelectric
Nuclear
10 Joules
(Trillion BTU)
3120.0 (2971.4)
50.7 (48.3)
2480.0 (2361.9)
15.6 (14.9)
422.3 (402.2)
38.0 (36.2)
6126.6 (5834.9)
Percentage
of Total
50.927o
0.83
40.48
0.26
6.89
0.62
100.00%
Source: SRI (1973)"
Table 5
CALIFORNIA SALES OF HEATING OILS
Type
#1 Distillate
#2 Distillate
#4 Distillate
#5 Distillate
#6 Distillate
3
10 Barrels
497
3059
730
296
2873
7455
Product kg/
Barrel
129.7
135.2
149.7
153.8
156.5
Wt Percent S
0.088
0.230
090
i ", .">.
-i - ^, .J j
1.640
Metric Tons
of Sulfur
5.
951,
1,191,
605,
7,378.
10,133,
7
,6
.8
.8
,3
i 2
Sources: NPN (1975) ; Bureau of Mines (1974) for average sulfur content
SRI (1973), "Meeting California's Energy Requirements. 1975-2000," SRI
Project ECC-2355, Stanford Research Institute, Menlo Park, California.
NPN (1975), National Petroleum News Factbook (May 1975).
f:
Bureau of Mines (1974), Burner Fuel Oils, 1974," Mineral Industrial Sur-
veys, Bureau of Mines, Petroleum Products Survey, Nos. 82, 86, and 88.
29
-------
These petroleum products are consumed in residential and commercial
space heating. The most recent census data assign 33 percent of Cali-
fornia's total population to the Los Angeles-Long Beach metropolitan
area." Southern California has only half the degree-day heating require-
ment of northern California (SRI, 1973). Lt is reasonable, then, to
estimate the sulfur burden in the Los Angeles SMSA from heating oils at
10.133.2 x 0.33 x 0.5 = 1672-° ™tric tons of sulfur
year
The sales of distillate and residual fuel oils in all applications
other than space heating in California are summarized in Tables 6 and 7,
along with their sulfur burden. We assigned the grades of product used
by each listed user, since the Bureau of Mines data do not so differentiate
Some users in California do not burden the Los Angeles area atmosphere
with all of their sulfur (e.g., vessel bunkering). Other users have in-
tegrated capability to some degree to remove the sulfur from the combus-
tion products (e.g.. oil company uses). Selection of users was not in the
scope of work for this study, so the aggregate sulfur burden is not esti-
mated. The applicable fractions for the Los Angeles SMSA for any of the
user categories that might be selected are the population fraction (Los
Angeles' population in relation to southern California's population) and
the activity fraction (southern California's fraction of California's
industrial activity as measured by value added in manufacture)(SRI, 1973).
Thus, 0.55 (population fraction) x 0.64 (activity fraction) = 0.35.
0.35 x sulfur content for selected user = sulfur burden.
Table 8 presents the Los Angeles SMSA sales and average sulfur con-
tent of gasoline.
12/27 data from Sales Management. July 27, 1975.
30
-------
Table 6
CALIFORNIA SALES OF DISTILLATE-TYPE FUEL OILS AND
AVERAGE SULFUR CONTENT: 1973
Use
Industrial
Oil company
Railroads
Vessel bunkering
Military
Electric utilities
On highway
Off highway
Other
Sources: Bureau of
103 Barre
5.570
903
8.530
2,210
5.605
888
18,415
4,278
480
.j.
Mines (1973,'
P roduc t
Is kg/Barrel
133
133
134
133
133
133
133
133
133
' 1974)
Table 7
CALIFORNIA SALES OF RESIDUAL-TYPE
AVERAGE SULFUR CONTENT:
Use
Industrial
Oil company use
Railroads
Vessel bunkering
Military
Electric utilities
Other
Sources: Bureau of
103 Barre
6.466
5,495
54
19,356
1, 134
84,183
202
Mines (1973,
Product
Is kg/Barrel
154
156
154
156
154
156
154
1974)
Wt.
Percent S
0.32
0.32
0.315
0.32
0.32
0.32
0.265
0.32
0.32
FUEL OILS AND
1974
Wt.
Percent S
1.33
1.64
1.33
1.64
1.33
1.64
1.33
Metric Tons
of Sulfur
2370.4
384.3
3597.9
940.4
2385.3
377.9
6490.0
1820.6
204.3
Metric Tons
of Sulfur
13,232.6
14,112.0
110.5
49,709.4
2,318.0
216, 195.9
413.4
Bureau of Mines (1973), "Fuel Oil Sales, Annual, 1973.'
31
-------
Table 8
LOS ANGELES SMSA SALES OF GASOLINE AND
AVERAGE SULFUR CONTENT: 1974
Grade
Premium price
Regular price
103 Barrels
44,310
39,770
Product
kg/Barrel
117.9
118.3
Wt.
Percent S
0.033
0.057
Metric Tons
of Sulfur
1725.6
2685.5
4411.1
Source: NPN (1975); Bureau of Mines (1974)
The sulfur burden for Los Angeles from motor gasoline is therefore
4411.1 metric tons of sulfur.
Table 9 summarizes the estimated daily emissions of sulfur and poten-
tial COS and CS2 emissions if mobile and stationary nonselective reducing
catalysts are used in the Los Angeles area. Using the sum of the esti-
mated emission rates for COS and CS^, we can calculate the stagnation
level in a similar manner as in Eqs. (32) and (33):
X =
ED (1 - L)
AH.
(34)
Substituting the following values for electric utilies and automobile
sources:
13 11
E = 1.4 ' 10 p.g COS/day, and 6.7 ' 10 )ag CS /day
D = 5 days
L = 0.1
11 3
AH. = 4.65 • 10 m
i
32
-------
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-------
_ (1.4 • 10 ug COS/day and/or 6.7 x 10 qg CS/day)(5)(0.9)
4.65 • 10U m3
3 , , , „„ , 3
3
= 135 ug COS/m and 6.5 ug CS /m
Table 10 summarizes all the contributing sources to the Los Angeles
stagnation levels of COS and CS9 under the assumptions previously given.
It should be noted that the values used in the above cases approxi-
mate near worst case conditions. Actual averages over longer time
periods (e.g., one year) would be considerably lower.
Table 10
SUMMARY OF SOURCE CONTRIBUTION TO ESTIMATED
AMBIENT STAGNATION LEVELS
Estimated Ambient
Stagnation Levels
(Ug/tn3)
CS
Source 2 COS
Refinery sulfur recovery plants 65 48
Electric utilities"' 6 128
/v
Automotive gasoline" 0.3 7
Commercial applications 129 --
Total 200 183
Nonselective reducing catalyst
34
-------
Health and Welfare Effects
As previously noted, 082 is used as an industrial chemical primarily
in the cold vulcanization of rubber and the manufacture of viscose rayon.
Acute and chronic human exposures have occurred in the industrial workplace,
providing a broad range of health effect documentations and encouraging
continuing research programs to establish threshold limits. Conversely,
COS has received little application as an industrial chemical; thus
records of human exposures are few, and health effects studies are all
but absent from the literature. However, because of the similarity in
chemical and physical properties, as well as some reports that COS is a
potentially toxic biological metabolite of CS2, some analogies may be
inferred between the two substances.
As mentioned above, extensive documentation on the health and wel-
fare effects of CS2 are present in the literature. These include a number
of review articles and three international symposia. The World Health
Organization (WHO) will soon be issuing a final report on CS2 following
review by appropriate government and industrial health organizations.
Aside from the WHO document, reviews to note are those by Brieger and
Teisinger (1967)*on the First International Symposium; a review of the
Third International Symposium (Lieben, 1974), a Yant Memorial Lecture
(Teisinger, 1974); and general literature reviews by Patty (1963),
*
Brieger, H., and J. Teisinger (1967), Toxicology of Carbon Bisulfide
(Excerpta Medica Foundation, New York, New York).
Lieben, J. (1974), "Third International Symposium on Toxicology of
Carbon Bisulphide," Arch. Environ. Health, Vol 29, p. 173.
*
Teisinger, J. (1974), "1972 Yant Memorial Lecture—New Advances in Toxi-
cology of Carbon Disulfide," Am. Ind. Hyg. Assoc. J.. Vol. 35, No. 2, p. 55.
35
-------
Browning (1965)/f Hamilton and Hardy (1974), and Davidson and Feinleib
(1972). The following paragraphs are syntheses of the above reviews with
current research findings.
Absorption, Excretion, Metabolism
CS« in inspired air enters the blood by way of the alveoli. It is
quite solubel in fat, miscible with alcohol, ether, and benzene, and
relatively insoluble in water. An equilibrium (total body saturation) can
be achieved within two hours upon inhalation of levels from 17 to 30 ppm
Eighty percent of inhaled CS^ is sorbed within the first 15 minutes and
*
45 percent in two hours (Teisinger and Soucek, 1949). Red blood cells
o
take up twice as much CS2 as the plasma (McKee, et al, 1943)/ and the
fat-soluble property allows distribution to all tissues (Brieger, 1961) .**
Blood levels of CS , following exposure, fall 75 percent in one hour
tt
and almost to zero in two (Teisinger and Soucek, 1949). McKee (1941)
found that complete desaturation requires about three to eight hours and
is directly related to the level of exposure. Metabolic degradation
accounts for approximately 95 percent of the loss of free C§2> while
Browning, E. (1965), Toxicity and Metabolism of Industrial Solvents
(Elsevier Publishing Company, New York, New York).
Hamilton, A., and H. L. Hardy (1974), Industrial Toxicology, 3rd ed.
(Publishing Sciences Group Inc., Acton, Massachusetts).
•t
Teisinger, J., and B. Soucek (1949), "Absorption and Elimination of
Carbon Disulfide in Man," J. Ind. Hyg., Vol. 31, p. 67.
8
McKee, R., et al.(1943), "A Solvent Vapor: Carbon Disulfide--Absorp-
tion, Elimination, Metabolism and Mode of Action," J. Am. Med. Assoc.,
Vol. 122, p. 217.
**
Brieger, H. (1961), "Chronic Carbon Disulfide Poisoning," J. Occup.
Med., Vol. 3, p. 302.
McKee, R. (1941), "Solubility of Carbon Disulfide Vapor in Body Fluids
and Tissues," J. Ind. Hyg., Vol. 23, p. 151.
36
-------
excretion via the lungs and kidney account for 5 and 0.05 percent, respec-
tively (Teisinger and Soucek. 1949). Other research indicates that from
10 percent to 30 percent is exhaled, and 1 percent is excreted in urine
(Brieger, 1961).
The metabolic products of CS? in human metabolism are not thoroughly
known. Dithiocarbamates are the products of the reaction of CS, with
amino acids (Brieger, 1961) and have been found in the blood (Scheel.
-I-
1967);' thiocarbamide has been found in the urine of exposed workers.
Thiourea and 2-mercapto-2-thiazolinone-5 have also been identified in the
urine (Pergal et al . . 1972)^
From comprehensive studies on the metabolism of CS,-, by Soucek and
Zahradnik, Davidson and Feinleib (1972) proposed that sorbed CS., com-
bines with materials containing a free amine group or basic nitrogen
atom. Thus products of the reaction of CS2 with proteins contain an in-
creased number of sulfhydryl groups.
There are several mechanisms regarding the toxic action of CS .
These involve the interaction of CS, or its metabolites with proteins.
+
fats, and coenzymes. Simon (1961) has suggested that CS, is a universal
enzyme inhibitor that disturbs oxidative phosphorylation and fat metabolism.
Scheel, L. (1967), "Experimental CS2 Poisoning in Rabbits, Its Mechanism
and Similarities with Human Case Reports," in Toxicology of Carbon Disul-
fide, H. Brieger and J. Teisinger. eds., pp. 107-114 (Excerpta Medica
Foundation, New York, New York).
+
Pergal, M., et al. (1972), "Carbon Disulfide Metabolites Excreted in the
Urine of Exposed Workers," Arch. Environ. Health. Vol. 25, p. 38.
*
Simon, K. (1961), "Chronische Vergiftung durch Schwefelkohlenstoff,"
Med. Monatschr., Vol. 16, p. 810, cited in Toxicity and Metabolism of
Industrial Solvents, E. Browning, ed., p. 704 (Elsevier Publishing Com-
oany, New York, New York).
37
-------
Cohen et al. (1959)" propose that the thiocarbamates and other metabolites
with sulfhydryl groups chelate metal ions and interfere with the energy
metabolism of cells. The stress incurred promotes a mobilization of fat
stores and leads to a disturbance of cellular metabolism and cell injury
or death. Disturbances in zinc metabolism following 089 exposure have
been observed by Scheel (1967), and decreases in serum zinc and increases
in urinary zinc in exposed workers have been observed by El Gazzar and
associates (1973). Many enzymes require metal ions as activators (e.g.,
Zn and Mg for alkaline phosphatase); thus the chelating effect of
su1fhydryl-bearing metabolites of CS9 to metal ions would inhibit the
enzymes from performing their normal function. Scheel (1967) has noted
decreased toxic effects of CS9 in animals fed highly mineralized diets.
Mack et al. (1974) found inhibition of oxidatixe N-demethylation
in man at doses as low as 10 ppm CS7 for six hours. The inhibition was
reversible and the deficit in metabolism was gradually compensated after
exposure ceased. The inhibitory mechanism is not known. However, as in
the above studies, the CS.-, metabolites, which are proposed to have similar
structures as dithiocarbamates, become active in enzymes due to chelation
of catalytically active metals. Mack et al. state, however, that a
reverse route is conceivable, in which the metabolites (e.g., dithio-
carbamates) release CS?, providing an indirect reaction with mixed-
function oxidases and other enzymes.
Cohen, et al. (1959), "Biochemical Mechanisms in Chronic Carbon Disul-
fide Poisoning," Am. Ind. Hyg. Assoc. J.. Vol. 20, p. 303.
t
El Gazzar, et al. (1973). "Changes in Zinc and Serum Proteins Due to
Carbon Disulfide Poisoning," Brit. J Ind. Med.. Vol. 30. p. 284.
*
Mack, T., K. Freundt, and D. Henschler (1974). "inhibition of Oxidative
N-Demethylation in Man by Low Doses of Inhaled Carbon Disulfide." Biochem.
Pharmac.. Vol. 23, p. 607.
38
-------
»l-
Vigliani (1954)" reports that under chronic exposures to €82, a
persistent presence of lipoproteinic macromolecules leads to hyaliniza-
tion and carbon disulfide arteriosclerosis. Vigliani implicated a dis-
turbance of the lipaemia clearing factor. In his exposed subjects, he
noted greater incidences of hypertension and vascular spasms, which were
correlated with an increase in the ratio of beta to alpha lipoproteins.
Cohen et al. (1959) also noted the same increases in beta to alpha lipo-
proteins but attributed the results to stress rather than to an inhibi-
tion of the lipaemia clearing factor.
A study of 120 viscose rayon workers cited a 34 percent increase over
normal of serum cholesterol, and the results were confirmed using dogs
as experimental animals (Davidson and Feinleib, 1972).
The effects of CSo on Vitamin B6 metabolism have been studied exten-
sively and there is a significant similarity in the neurological symptoms
of B6 deficiency and C&2 poisoning (Davidson and Feinleib, 1972). In-
creased diets of Vitamin B6 have been shown to inhibit toxic effects of
CS« in animals (Teisinger, 1974). Teisinger feels that nervous system
lesions due to C$2 poisoning are associated with the inhibition of mono-
amine oxidase activity and the accumulation of serotonin in the brain.
This mechanism is not widely supported, however, because there is con-
tradictory evidence in the literature. Browning (1965) suggests another
mechanism involving chelation of copper by thiocarbatnates in nerve cells,
resulting in inhibition of the functions of cytochrome oxidases and
coenzyme-A dehydrogenase.
*
Vigliani, E. C. (1954), "Carbon Disulfide Poisoning in Viscose Rayon
Factories," Brit. J. Ind. Med.. Vol. 11, p. 235.
39
-------
The liver is an important organ in the metabolism of CSo. Dalvi et
al. (1974," 1975'), using radio labeled CS2, have revealed that COS is
formed from 082 when incubated with rat liver microsomes in the presence
of NADPH. Furthermore, the COS is metabolized to yield sulfur radicals and
C02- Each step appears analogous to a mixed-function oxidase catalysis
and leads to formations of highly reactive sulfur radicals that covalently
bind to microsomal membranes and decrease the concentration of cytochrome
P-450. This highly reactive sulfur leads to a decrease in the concentra-
tion of cytochrome P-450 and hepatic damage seen on liver examinations
following CS2 administration to rats. Thus, if oxidative metabolism
plays a significant role in the toxicity of CS (forming reactive sulfur
atoms), COS would likewise be expected to be toxic.
Unfortunately, we have not uncovered in the literature any research
describing the mechanism of toxicity of COS, other than the formation of
a reactive sulfur species in liver microsomes. However, assuming oxida-
tive metabolism is the eventual cause of toxicity for CS~ and COS (due
to the formation of highly reactive sulfur atoms), then on a molecular
level one molecule of CS2 would be twice as toxic as one molecule of COS.
This is an oversimplification of the toxicity problem for the whole
organism, due to the confounding of probable differences in tissue dis-
tribution, metabolism, and the formation of toxic metabolites. However,
because of the lack of data concerning chronic COS toxicity, we hypo-
thesize the 2:1 (CS2:COS) toxicity ratio.
Dalvi, R. R., et al. (1974), "Studies of the Metabolism of Carbon Bi-
sulfide by Rat Liver Microsomes," Life Sci., Vol. 14, p. 1785.
t
Dalvi, R R., et al. (1975), "Toxicological Implications of the Mixed-
Function Oxidase Catalyzed Metabolism of Carbon Bisulfide," Chem.
Biol. Int., Vol. 10, p. 347.
40
-------
Toxic Effects
Although CS2 is highly volatile, a case of acute poisoning by in-
gestion, followed by death within four hours, occurred in a victim who
swallowed a glass of CS2 (Foreman. 1886) ." Physical examination prior
to death showed normal pupils, abnormal respiration, and a rapid pulse
(150-160/minute). Some studies on the acute toxicity of COS in animals
have been reported and are presented in Table 11 along with CS data.
Table 11
LETHAL DOSES OF CS2 AND COS (INHALATION)
cs2
Species (ppm)
Man (Patty, 1963) 4,815
Cats (Browning, 1965) 1,260
Rabbits (Patty, 1963)
Mice
Mice
Mice
Rats
Rats
(Patty,
(Patty,
(Patty,
(Hayashi
(Hayashi
1963)
1963)
1963)
et al., 1971)"
et al., 1971)
Death COS
(Time) (ppm)
30 min
180 min
3,
8,
2,
1,
5,
20,
200
900
900
200
000
000
Death
(Time)
60
0.
1.
35
10
45
min
75 min
5 min
min
h
min
Hayashi,, E., et al. (1971), "Acute Toxicity of Carbonyl Sulfide
Towards Animals," Oyo Yakuri, Vol. 5, No. 3, p. 435.
In acute exposures, COS and CS2 act upon the central nervous system
and result in death by respiratory paralysis. Chronic toxicity studies
with animals for COS have not been found in the literature and exposure
of humans has not been recorded.
Foreman, W. (1886), "Notes of a Fatal Case of Poisoning by Bisulphide
of Carbon," Lancet, Vol. 2, p. 118.
41
-------
Experimental studies of C5>2 on animals reveal a wide variety of
changes involving the nervous, reproductive, and cardiovascular systems.
and the liver, kidney, and blood.
Chronic exposure in man, likewise, has caused a variety of effects.
Most noticeable are those on the nervous system; potentially the most
dangerous effects are those on the heart, which have led to an increased
incidence of coronary heart disease.
In the 1850s the French were aware of the public health aspects of
respired 082 and diagnosed over 80 cases of "carbon disulfide neurosis"
(a wide variety of nervous and mental disorders with an early stage of
excitation followed by a second stage of depression) in the rubber indus-
try, where CS^, was used. These findings were confirmed with animal studies
Other symptoms of CS,-, intoxication reported in the early literature were
classified as "CS? insanity," "mental morbidity," "chronic neuritis." and
"acute mania." Among rubber workers in 1898, "mental morbidity" was
reported to have decreased by 86 percent ten years after improvements
in ventilation that decreased CSo concentrations from several hundred
to less than 30 ppm (Davidson and Feinleib. 1972).
The effect of 082 on the central nervous system is now generally
considered as polyneuritic (affecting a large number of spinal nerves).
Recent neurophysiological studies of chronically poisoned workers (ex-
posed to 20-40 ppm in the 1950s and 10-30 ppm in the 1960s) indicate im-
pairments at several levels of the central and peripheral nervous system
(Seppalainen et al., 1972)."' The exact locus of the polyneuropathic type
of lesion varies. Of 9, 17, and 10 subjects exposed (from 0.5 to 2 years.
Seppalainen, A. M., et al. (1972), "Neurophysiological Findings in
Chronic Carbon Disulfide Poisoning, A Descriptive Study," Work-Environ.
Health. Vol. 9, p. 71.
42
-------
3 to 10 years, and greater than 10 years, respectively); 0, 3, and 1 sub-
jects were neurophysiologically normal compared with a control group of
120 normal adults. The reported observations show that the effect of CS2
on the nervous system cannot be considered specific.
•Jt"
Tiller and coworkers (1968) found that in men with more than 10
years employ in the viscose rayon industry, the death rate from coronary
heart disease (CHD) was 2.5 times greater in exposed workers than in
nonexposed workers. Nearly half of the air-monitoring samples over a
period of 16 years reported levels greater than 20 ppm. It is interest-
ing to note that the nonexposed rayon workers had a significantly higher
observed death rate than expected for CHD, as had other local men who were
not employed in the viscose rayon industry. The male death rate from
cardiovascular diseases in those areas of England and Wales where viscose
rayon factories are situated is somewhat higher than the national rates
but is thought to be due to soft drinking water. (Soft drinking water
frequently acquires high concentrations of heavy metals, which have been
cited as contributors to CHD.)
+
Hernberg and coworkers (1970) reported an excess of coronary deaths
among 48 men who had been exposed to CS2 for at least five years and had
died under the age of 65. The expected number of deaths from CHD was 15;
however, 25 were observed. Examination of 343 viscose rayon workers, who
were matched with 343 control subjects from a paper mill revealed that
the subjects exposed to CS« had higher blood pressure and a slightly
*
Tiller, J. R., R. Schilling, and J. Morris (1968), "Occupational Toxic
Factor in Mortality from Coronary Heart Disease," Brit. Med. J., Vol. 4,
p. 407.
t
Hernberg, S., et al. (1970), "Coronary Heart Disease Among Workers Ex-
posed to Carbon Disulphide," Brit. J. Ind. Med.. Vol. 27, p. 313.
43
-------
higher prevalence of electrocardiogram abnormalities. Exposures to CS^
were from 20 ppm to 40 ppm in the 1950s and about 10 ppm to 30 ppm in
the 1960s.
A follow-up study by Hernberg and coworkers (1973)"'on the 343 exposed
workers showed that 16 men had died from CHD compared with 3 in the con-
trol cohort over a five-and-one-half year period. Other causes of death
were evenly distributed (7 and 6) among both groups. The control cohort
had an incidence of CHD that was less than the national death statistics
(Finland), and this was attributed to the occupational status. The inci-
dence of CHD mortality was 6.7 percent and 2.6 percent for the two groups.
A further analysis of the data of Hernberg and coworkers indicated that
11 nonfatal first cardiac infarctions had occurred in the exposed group
as compared with 4 in the control (Tolonen et al., 1975). The exposed
group also had a greater prevalence of angina (chest pains).
Lieben and coworkers (1974)* evaluated the effects of the CS2 °n the
cardiovascular system of 1498 presently employed U.S. rayon workers com-
pared with 481 acetate workers. An electrocardiogram, blood pressure,
total cholesterol, and occupational exposure history were obtained for
each worker. The only statistically significant finding was a higher
blood pressure (140/87) in workers in the rayon plants than in workers
in the acetate plant (135/83) .
The question of whether the association between CHD and CS9 is
causal is still addressed, although the circumstances favor such an
association. Some biochemical mechanisms that add credence to the cau-
sality are decreases in fibrinolytic activity (Brieger and Teisinger, 1967),
•/v
Hernberg, S., et al. (1973), "Excess Mortality from Coronary Heart Disease
in Viscose Rayon Workers Exposed to Carbon Disulfide7" Work-Environ.-
Health, Vol. 10, p. 93.
t
Tolonen, M., et al. (1975), "A Follow-up Study of Coronary Heart Disease
in Viscose Rayon Workers Exposed to Carbon Disulfide," Brit. J. Ind. Med.,
Vol. 32, p. 1.
$
Lieben, J., et al . (1974), "Cardiovascular Effects of CS2 Exposure," J_._
Occ. Med., Vol. 16, No. 7, p. 449.
44
-------
changes in lipid metabolism, elevation of blood pressure, and myocardial
effects through interference with catecholamine metabolism (Magos, 1974).
Another notable toxic effect of CSo is on the reproductive system.
The estrous cycle of rats was found distorted (Vasileva. 1973). Follow-
up studies on women workers exposed to greater than 10 ppm and 4 ppm CS,-,
indicated greater disruption of the menstrual cycle and more pathological
changes in the cellular composition of vaginal smears than in the control
groups. Humans (Lancranjan. 1972) and rats have been shown to have changes
in spermatogenesis (Rozewichi et al, 1973).:
A synergism between 082 (20-25 pm) and H^S (20-25 ppm) has been
noted in rabbits exposed for four hours per day for 150 consecutive days
(Kuwai, I960)."" In the mixed gases group, reticulocyte count and globulin
increased, and total cholesterol rose on the 110th day and continued to
rise for the remainder of the experiment. No abnormality was detected in
the separate groups except for a slight elevation of total cholesterol in
the H2S group, which eventually returned to normal.
CSn was detected in the urine of children in a study of persons
living near a Czechoslovakian industrial plant emitting 32 kg/h H9S and
Magos, L.. et al. (1974). "Half-Life of CS9 in Rats in Relation to Its
Effect on Brain Catecholamines," Int. Arch. Arbeitsmed.. Vol. 32, p. 289.
Vasileva. I. A. (1973). "Effect of Small Concentrations of CS > and H2S on
the Menstrual Function of Women and the Estryl Cycle of Experimental
Animals," Gigiena i Sanitaria. Vol. 7. p. 24 (transl. from Russian).
Lancranian. I. (1972). "Alteration of Spermatic Liquid in Patients Chron-
ically Poisoned by Carbon Disulphide." Med. Lavoro. Vol. 63, No. 12. p. 29.
'^Rozewichi, S., et al . (1973). "Effect of Chronic Poisoning with Carbon
Disulfide on the Hormone Activities of Rat Ovaries," Med. Pr.. Vol. 24 ,
p. 133.
Kuwai, S. (1960), "Experimental Studies on Gas Inhalation of Respective
and Combined CS2 and H0S ." Shikoku Igaku Zasshi . Vol. 16. Suppl. 144. p. 64.
45
-------
and 55.5 kg/h C$2• The incidence of upper respiratory passage disease
was noted to be 10 percent higher in this industrial group than in a rural
V"
control group (Holasova, 1969).'
Threshold Levels
It is apparent that 20 ppm CS£ allows little if any margin of safety
for chronic C&2 exposure. Current allowable concentrations for occupa-
tional exposures are 20 ppm in the United States, (ACGIH, 1971), 3 ppm
in the USSR, and 10 ppm in Czechoslovakia (Brieger and Teisinger, 1967).
The 20-ppm level has received considerable critisicm; Finnish authorities
reduced the level to 10 ppm in 1972 (Tolonen et al., 1975).
In estimating the allowable concentration in the ambient atmosphere
from epidemiological studies of industrial exposures, one must consider
that the workers are (aside from exposure effects) normal, healthy males
performing manual operations, and that they are exposed less than eight
hours per day for five days per week. In these groups, cardiovascular
and neurological effects have been noted from chronic (intermittent)
exposures approaching 10 ppm. Disruption of the estrous cycle of working
women was also noted at exposures to 4 ppm. Continual exposure (i.e.,
24 hours/day) does not occur for the worker (i.e., 8 hours/working day);
thus reversible effects would tend to be restored on a diurnal basis until
an equilibrium has been established. Using the 35 minute half-life for
CS2 in man established by Magos (1974), the chronic damage must either
be irreversible or caused by a long-lived metabolite. Tolonen et al. (1975)
*
Holasova, P. (1969), "Pathology of Children in an Area Polluted with CS2
and H2S in Comparison with a Control Group," Cesk. Hyg., Vol. 14, p. 7;
Vol. 8, p. 260.
ACGIH (1971), "Documentation of Threshold Limit Values," 3rd edition
(American Council of Governmental and Industrial Hygienists).
46
-------
noted that 40 percent of his historically exposed group had not been
exposed for the f ive-and-one-hal f-year period in which the elevated CHD
mortality rate was significantly greater. Thus the CHD effects appear
irreversible. In contrast, some studies have noted reversible occurrences
at the biochemical level (i.e., mixed-function oxidase inhibition). Re-
versible impairments would be continuous under constant exposure and thus,
in general, indistinguishable from irreversible alterations.. In rats
o
continuously exposed to levels of 100 |_ig CS2/m (0.03 ppm) the rate of
body weight increase and content of coproporphyrin in urine was decreased
(Misiakiewicz et al., 1971)* Baikov (1974)"'' found eye sensitivity to
light reflexes affected at 10 ng/m^ (3 ppb) in humans.
For continual exposure to CS,-,, the morbidity threshold effect for
humans is presumably lower than 10 ppm. A certain fraction of the popula-
tion is predisposed to symptoms that continuous levels of CS2 may further
aggravate (e.g., hypertension, elevated cholesterol). It appears that
persons on mineral-deficient diets may also be more susceptible to toxic
effects (ACGIH, 1971). To establish a critical margin of safety for the
general population, further research on threshold effects to critical
subgroups needs to be carried out. In light of the above, an ambient
standard should be developed that allows a magnitude of difference for
chronic-intermittent versus chronic-continuous exposure, as well as
another magnitude for critical subgroups that may be further impaired.
We recommend a level equal to or less than 300 p,g CS2/m^- Such a level
should provide an adequate health effects margin of safety for the general
population until further studies on continual exposure thresholds are
performed.
Vf
Misiakiewicz, A., et al. (1971), "Effect on Animals of Prolonged Exposure
to Low Concentration of CS2 in the Air," Roc. Pansstw. Zakl. Hig.,
Vol. 22, No. 1, p. 7.
Baikov, B. K. (1974), "Hygienic Effect of Carbon Bisulfide and Hydrogen
Sulfide Simultaneously Present in Atmospheric Air," microfiche, transl.
from Russian, Information Systems Inc., Omaha, Nebraska.
47
-------
Because of the lack of data on chronic COS health effects, a margin
of safety should be established by analogy to CS2- The basis for this
analogy is the similarity in chemical and physical properties, the possible
relationship in biochemical metabolism and mechanism of toxic effect
(reactive sulfur atom), and the similarity in acute exposure thresholds
and symptomatology. Using a ratio (CS?/COS) of molecular weights of 1.25
and a ratio of toxicity of 2 (reactive sulfur atoms), we recommend an am-
bient level of 0.16 ppm COS (400 |_ig/nr) until further studies are performed.
It should be noted that the maximum allowable concentration for CS~
o
in the workplace in the USSR is 10 mg/m (3.3 ppm) and in the ambient air
10 p.g/m (3.3 ppb) (Baikov, 1974). These concentrations are considered as
goals rather than as regulatory ceilings and are frequently exceeded.
Welfare Effects
CS~ has received wide application as a fumigant pesticide in the con-
trol of mosquito larvae, wax moths, nematodes, ants, fungi, and flour
beetles. The concentrations employed are quite high; generally greater
than 5000 ppm is required to produce the desired effect. CS2 is controlled
as a food additive for the fumigation of processed grains in the produc-
tion of fermented malt beverages under the Federal Food, Drug, and Cos-
metic Act (Federal Register, 1964)." Residues must be absent in the fin-
ished beverages.
€82 increases the efficiency of seed germination for Zea mays (corn)
(Popescu et al., 1971). Concentrations of C&2 up to 10 percent stimulate
Federal Register (1964), "Fumigants for Processed Grains Used in the
Production of Fermented Malt Beverages," Fed. Reg., Vol. 29, p. 7462.
Popescu, V., et al. (1971), "Influence of the Treatment with Some Chem-
icals on the Seed Germination of Several Cultivated Plants," Ser. Biol.
Vol. 16, p. 101.
48
-------
C09 fixation in alfalfa leaves and higher concentrations stimulate the
formation of 1-alanine (Lehman et al.. 1972)."" Low seedling weight and
reduced glucose content were observed in wheat seeds that were treated
with high concentrations of CS 9 and stored for six months (Zaki and Nada,
+
1964). These studies indicate that there would be little impact of CS2
on plants at expected ambient concentrations.
Rauch (1962) found 12 ppm COS in horseradish tissue and suggests the
substance as a defensive compound for plants. In a study to characterize
odor-producing substances from cattle feedlots. Elliott and Travis (1973)
found COS produced in significant quantities. COS is reported to have an
unpleasant odor similar to that of rotten eggs; however, no threshold data
are reported in the literature.
Pure COS has a foul etheral odor; however, according to Patty (1963).
it does not offer adequate warning at harmful concentrations. A solution
of 1 mg CS2/per liter of water is said to be the threshold for detection
by smell (Vinogradov, 1966). Baikov (1974) found an odor threshold of
0.08 mg/m^ in air.
There are reports in the literature concerning the corrosive prop-
erties of CS2 on metallic coatings during its manufacture; however, at
emission concentrations (100 ppm) this effect would not be a problem.
Lehman, J., et al. (1972), "Effect of Some Vaporized Lipophilic Sol-
vents on Carbon Dioxide Fixation by Alfalfa," Experientia. Vol. 28,
No. 12, p. 1415.
Zaki, M., and M. Nada (1964), "Effect of CS9 on the Total Carbohydrate
Content of Treated Wheat Seeds," Ann. Agr. Sci. (Cairo). Vol. 6. No. 1.
p. 1350.
Vinogradov, P. B. (1966). "New Experimental Data for Substantiating the
Maximum Permissible Concentration of Carbon Disulfide in Water Basins,"
Gigiena i. Sanitaria, Vol. 31. p. 13.
49
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Environmental Quality Aspects
It appears that the primary anthropogenic controllable source for
CS,-, emissions is from viscose rayon manufacturing. Emissions from re-
finery sulfur recovery plants, assuming Beavon catalyst degradation,
would contribute approximately 30 percent of the anthropogenic emissions
in the Los Angeles basin. For the five-day stagnation conditions pre-
viously given for the Los Angeles Basin (Estimates of Ambient Air Concen-
o
trations), the threshold odor concentration (80 ^ig/mj) would be exceeded.
Contributions from other sources do not appear to be significant, and
under the assumed conditions cf stagnation, our 300 p.g/m-' recommended
health effects threshold would not be exceeded.
Little is known about the health effects of COS. Because of its
significant emission from some nonselective reducing catalyst systems,
however, establishing the threshold effect is worthy of immediate con-
sideration. Based on analogy to CS2- a 400 ug/rrr health effects level is
recommended until more data are available. Under the worst case condi-
tions (as above) this level will not be exceeded. The odor threshold is
not known, but, if similar to CS2? it will frequently be exceeded.
Coal gasification plants may emit significant quantities of COS and
CS2 and may pose aesthetic problems (odor) in the vicinity of the source
along the plume. This will depend on the sulfur content of the coal being
gasified. Oil shale retorting and upgrading plants will also emit sig-
nificant quantities of CS? and COS, and likewise may pose aesthetic prob-
lems in the near vicinity. In these plants, however, annual time-weighted
ambient air concentrations above 300 ug CS2/m and 400 ug COS/nr should
not be exceeded.
Due to the generally long environmental half-lives for each compound,
the transformations to l^S and S02 would occur, but after appreciable
dilution of the vapors in the atmosphere.
50
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54
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55
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57
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NOL
EPA-600/9-78-009
3. RECIPIENT'S ACCESSION NO.
PB 257 947/2BA
4. TITLE AND SUBTITLE
Carbon Disulfide, Carbonyl Sulfide:
Literature Review and Environmental Assessment
5. REPORT DATE
June 1978 issuing date
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Thomas 0. Peyton, Robert V. Steele, and
William R. Mabey
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Stanford Research "Institute
Menlo Park, California 94025
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-01-2940, Task 023.
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Protection Agency
401 M. Street, S.W
Washington, D.C. 20460
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
t6. ABSTRACT
Carbon disulfide (CS2) and carbonyl sulfide (COS) are volatile substances of mod-
erate toxicity, odor, and environmental lifetimes (days). Vapors emitted from sources
are expected to follow normal atmospheric dispersion principles. Each compound is
produced from anthropogenic as well as natural sources. The most significant anthropo
genie emission for CS2 is from commercial usages where the atmosphere serves as the
natural sink. The use of nonselective reducing catalysts may emit significant quanti-
ties of COS. Little is known of the toxic thresholds for COS; however, the signifi-
cant industrial usage of CS2 has provided appreciable industrial hygiene records on
effects. Based on industrial effects records, and until better data on chronic ex-
posures become available, we tentatively recommend that limiting long-term averaged
concentrations to 300 p-g/m-^ CS2 should be sufficient for protection against adverse
health effects. By chemical and biological analogy to CS2, the corresponding level
for COS would be 400
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COS AT I Held/Group
Ecology
Organic Compound
Assessments
Criteria
Standards
Carbon Disulfide
Carbonyl Sulfide
CS2
COS
Energy systems
6F
7C
10A
18. DISTRIBUTION STATEMENT
Document is available to the public through
the National Technical Information Services
Springfield, VA 22151
19. SECURITY CLASS (This Report)
unclassified
21 NO. OF PAGES
63 -
20. SECURITY CLASS (This page)
unclassified
22. PRICE
EPA Form 2220-1 (9-73)
*U.<
260-880/76
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