PRELIMINARY
AIR POLLUTION SURVEY
OF
HYDROGEN SULFIDE
A LITERATURE REVIEW
U. S. DEPARTMENT OF HEALTH, EDUCATION, AND WELFARE
Public Health Service
Consumer Protection and Environmental Health Service
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PREFACE
This document represents a preliminary literature review which is being used as a basis for
further evaluation, both internally by the National Air Pollution Control Administration
(NAPCA) and by contractors. This document further delineates present knowledge of the
subject pollutant, excluding any specific conclusions based on this knowledge.
This series of reports was made available through a NAPCA contractual agreement with
Litton Industries. Preliminary surveys include all material reported by Litton Industries as
a result of the subject literature review. Except for section 7 (Summary and Conclusions),
which is undergoing further evaluation, the survey contains all information as reported by
Litton Industries. The complete survey, including section 7 (Summary and Conclusions)
is available from:
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PRELIMINARY
AIR POLLUTION SURVEY
OF
HYDROGEN SULFIDE
A LITERATURE REVIEW
Sydney Miner
Litton Systems, Incorporated
Environmental Systems Division
Prepared under Contract No. PH 22-68-25
U.S. DEPARTMENT OF HEALTH, EDUCATION, AND WELFARE
Public Health Service
Consumer Protection and Environmental Health Service
National Air Pollution Control Administration
Raleigh, North Carolina
October 1969
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The APTD series of reports is issued by the National Air Pollution Control
Administration to report technical data of interest to a limited reader-
ship. Copies of APTD reports may be obtained upon request, as supplies
permit, from the Office of Technical Information and Publications, National
Air Pollution Control Administration, U.S. Department of Health, Education,
and Welfare, 1033 Wade Avenue, Raleigh, North Carolina 27605.
National Air Pollution Control Administration Publication No. APTD 69-37
11
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FOREWORD
As the concern for air quality grows, so does the con-
cern over the less ubiquitous but potentially harmful contami-
nants that are in our atmosphere. Thirty such pollutants have
been identified, and available information has been summarized
in a series of reports describing their sources, distribution,
effects, and control technology for their abatement.
A total of 27 reports have been prepared covering the
30 pollutants. These reports were developed under contract
for the National Air Pollution Control Administration (NAPCA) by
Litton Systems, Inc. The complete listing is as follows:
Aeroallergens (pollens)
Aldehydes (includes acrolein
and formaldehyde)
Ainmon ia
Arsenic and Its Compounds
Asbestos
Barium and Its Compounds
Beryllium and Its Compounds
Biological Aerosols
(microorganisms)
Boron and Its Compounds
Cadmium and Its Compounds
Chlorine Gas
Chromium and Its Compounds
(includes chromic acid)
Ethylene
Hydrochloric Acid
Hydrogen Sulfide
Iron and Its Compounds
Manganese and Its Compounds
Mercury and Its Compounds
Nickel and Its Compounds
Odorous Compounds
Organic Carcinogens
Pesticides
Phosphorus and Its Compounds
Radioactive Substances
Selenium and Its Compounds
Vanadium and Its Compounds
Zinc and Its Compounds
These reports represent current state—of—the—art
literature reviews supplemented by discussions with selected
knowledgeable individuals both within and outside the Federal
Government. They do not however presume to be a synthesis of
available information but rather a summary without an attempt
to interpret or reconcile conflicting data. The reports are
111
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necessarily limited in their discussion of health effects for
some pollutants to descriptions of occupational health expo-
sures and animal laboratory studies since only a few epidemio-
logic studies were available.
Initially these reports were generally intended as
internal documents within NAPCA to provide a basis for sound
decision—making on program guidance for future research
activities and to allow ranking of future activities relating
to the development of criteria and control technology docu-
ments. However, it is apparent that these reports may also
be of significant value to many others in air pollution control,
such as State or local air pollution control officials, as a
library of information on which to base informed decisions on
pollutants to be controlled in their geographic areas. Addi-
tionally, these reports may stimulate scientific investigators
to pursue research in needed areas. They also provide for the
interested citizen readily available information about a given
pollutant. Therefore, they are being given wide distribution
with the assumption that they will be used with full knowledge
of their value and limitations.
This series of reports was compiled and prepared by the
Litton personnel listed below:
Ralph J. Sullivan
Quade R. Stahl, Ph.D.
Norman L. Durocher
Yanis C. Athanassiadis
Sydney Miner
Harold Finkelstein, Ph.D.
Douglas A. Olsen, Ph . .D.
James L. Haynes
iv
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The NAPCA project officer for the contract was Ronald C.
Campbell, assisted by Dr. Emanuel Landau and Gerald Chapman.
Appreciation is expressed to the many individuals both
outside and within NAPCA who provided information and reviewed
draft copies of these reports. Appreciation is also expressed
to the NAPCA Office of Technical Information and Publications
for their support in providing a significant portion of the
technical literature.
V
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ABSTRACT
Hydrogen sulfide gas is very toxic to humans and at
concentrations over 1,000,000 ig/m 3 quickly causes death by
paralysis of the respiratory tract. At lower concentrations
it causes conjunctivitis with reddening and lachrymal secre-
tion, respiratory tract irritation, pulmonary edema, damage
to heart muscle, psychic changes, disturbed equilibrium,
nerve paralysis, spasms, unconsciousness, and circulatory
collapse. One outstanding episode in Mexico involving acci-
dental release of hydrogen sulfide killed 22 people and 50
percent of the exposed animals and hospitalized 320 persons.
The gas has a very obnoxious odor at low concentrations
(1 to 45 ig/m 3 ). At concentrations below 60,000 ig/m 3 it
has very little effect on plants. Hydrogen sulfide also
tarnishes silver and copper and combines with heavy metals
in paints to discolor or darken the paint surface.
The primary natural source of hydrogen sulfide is
biological decay of protein material in stagnant water. In-
dustrially, hydrogen sulfide is a by—product of many processes.
Main industrial producers are kraft paper mills, oil ref in—
eries, natural gas plants, and chemical plants manufacturing
sulfur—containing compounds. Hydrogen sulfide is also pro-
duced in sewers and sewage disposal plants. Average concen-
trations of hydrogen sulfide in urban atmospheres are reported
to range from 1 to 92 ig/m 3 , with most urban averages reported
at less than 10 g/m 2 .
v ii
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The installation of black liquor oxidation systems
and scrubbers has substantially reduced emissions from kraft
paper mills. Wet scrubbers using various absorbents and
iron oxide are used in refineries, natural gas plants, coke
ovens, and chemical plants to remove hydrogen sulfide from
gas streams. Incineration is also used to reduce emissions
of the gas.
Hydrogen sulfide corrosion of silver has required
substitution of gold contacts in electrical appliances at
an estimated increased cost of $14.8 million during 1963.
Abatement of air pollution resulting from the pulp and
paper industry, in which hydrogen sulfide is a major factor,
has cost approximately $10 million per year and is predicted
to increase to $15 million per year in the immediate future.
Major expenditures have been made by refineries and natural
gas plants to remove hydrogen sulfide from sour gases and to
recover sulfur as a valuable by—product.
Analytical techniques based on the methylene blue
and molybdenum blue methods are available for laboratory
analysis of hydrogen sulfide. The spot method for measuring
hydrogen sulfide, based on tiles or paper impregnated with
lead acetate, is also widely used.
vi i 1
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LIST OF TABLES
1. Odor Detection Threshold of Hydrogen Sulfide . . . . 5
2. The Protection Index of Sodium Nitrite and Papp
Pretreated Mice Exposed to Hydrogen Sulfide . . . . 11
3. Time in Minutes Until 50% Injury to Exposed Plant
Surfaces at 1,500,000 ig/rn 3 Hydrogen Sulfide . . . . 14
4. Ambient Air Quality Standards 21
5. Sulfur Production from Hydrogen Sulfide in the
United States . . . . . . • . . . . . 24
6. Hydrogen Sulfide Emissions from Kraft Mill
Processors. 30
7. Estimated Hydrogen Sulfide Emissions from 650 ton/day
Kraft Mill in Lewiston, Idaho . . . . . . . . . . 31
8. Frequency Distribution of Hydrogen Sulfide Concentra-
t ions, 1961—62 . . . . . . . 32
9. Hydrogen Sulfide Content of Coke-Oven Gas 33
10. Sources of Hydrogen Sulfide Emissions in Coke Plants 34
11. Hydrogen Sulfide Concentrations at Various Distances
from Plant s . . . . . . . 39
12. Atmospheric Air Pollution by Hydrogen Sulfide at
Different Distances from Source of Pollution . . . . 39
13. Hydrogen Sulfide Emission Factors . . . . 41
14. Atmospheric Hydrogen Sulfide Concentrations 45
15. Effects of Hydrogen Sulfide on Humans 83
16. Time Required for 50% Mortality of Subjects Treated
With Hydrogen Sulfide 84
17. 2ypica1 Gross Findings at Autopsy of Rats arid Mice
Which Died During Exposure to Hydrogen Sulfide . . . 85
18. Percentage of Leaf Area Marked by Hydrogen Sulfide . 87
19. Relative Sensitivity of Plants to Hydrogen Sulfide * 88
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LIST OF TABLES (Continued)
20. Crude Oil Capacity in the U.S. .s of Jan. 1969 . . . 89
21. Kraft Pulp Production in the United States 90
22. United States Coke Production . . . . . 91
LIST OF FIGURES
1. Time—Mortality Toxicity Curve for Houseflies Exposed
to 1,500,000 p g/m 3 Hydrogen Sulfide . . . . . . . . . 8
2. Exposure Time Versus Concentration for Hydrogen
Sulfide Effects 18
3. Crude Capacity of United States Refineries . . . . . 25
4. Natural Gas Production and Plant Production of Ethane
and Liquid Propane Gas (LPG) for Fuel and Chemical
Use . . . . . . . . . . . , . . . . . . . . • . . • . 27
5. Relation Between Hydrogen Sulfide Production and
FurnaceLoading. . . . . . . . . . . . . . . . . . . 31
6. Approximate Cost of Gas Desulfurization Plants in
1967 . . . . . . . . . 57
7. Sulfur—Recovery Plant Investment . . . . 58
8. Location of Kraft Mills in the U.S. in 1957 . . . . . 82
x
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CONT ENTS
FOREWORD
ABSTRACT
1. INTRODUCTION 1
2. EFFECTS 2
2.1 Effects on Humans 2
2.1.1 Odor Threshold 3
2.1.2 Pollution Occurrences 4
2.2 Effects on Animals 6
2.2.1 Commercial and Domestic Animals . . . . 6
2.2.2 Experimental Animals 7
2.3 Effects on Plants 12
2.4 Effects on Materials 16
2.4.1 Effects on Paint 16
2.4.2 Effects on Metals . 19
2.5 Environmental Air Standards 20
3. SOURCES 22
3.1 Natural Occurrence 22
3.2 Production Sources . 22
3.2.1 Petroleum Industry 23
3.2.2 Petrochemical Plant Complexes 26
3.2.3 Kraft Mills 28
3.2.4 Coke Ovens 32
3 * 2 . 5 I’ti. fling 35
3.2.6 Iron—Steel Industry and Foundries . . . 36
3.2.7 Chemical Industry 36
3.2.8 Animal Processing Plants and
Tanneries 38
3.3 Product Sources . . 40
3.4 Other Sources 40
3.4.1 Combustion Processes . 40
3.4.2 Polluted Water . . . . . . . 42
3.4.3 Well Water . . 43
3.4.4 Sewage Plants and Sewers . 43
3.5 Environmental Air Concentrations 44
xi
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CONTENTS (Continu )
4 . A B.TE kENT .
4.1 Kraft Paper Mills . .
4.2 Petroleum Industry and Petrochemical
4..3 Coke—Oven Plants and Chemical Plants
4.4 Coal Piles . . .
4 . 5 T arm er i_ es .
4.6 Sewers and Sewage Plants . . .
4.7 Gen a1 Abatement Systems . . .
5. ECONOMICS
6. METHODSOFANALYSIS . . .
APPENDIX
81
46
Plants
• . . .
— . • .
• — . .
• . 46
• • 50
51
- • 52
• - 52
• • 53
• • 54
55
R EFERENCES •
• 59
67
xii
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1
1. INTRODUCTION
Hydrogen sulfide (H 2 s) is a colorless gas that has
an obnoxious odor at low concentrations. The odor threshold
is in the ig/m 3 range. In higher concentrations, the gas is
toxic to humans and animals and corrosive to many metals.
It will tarnish silver and react with heavy metals in paints
to discolor the paint. In humans, it will cause headache,
conjunctivitis, sleeplessness, pain in the eyes, and similar
symptoms at low air concentrations and death at high air
concentrations. However, the majority of the complaints
arising from hydrogen sulfide air pollution are due to its
obnoxious odor in extremely low air concentrations.
Air pollution by hydrogen sulfide is not a widespread
urban problem but is generally localized in the vicinity of
an emitter such as kraft paper mills, industrial waste dis-
posal ponds, sewage plants, refineries, and coke oven plants.
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2
2. EFFECTS
2.1 Effects on Humans
Hydrogen sulfide, which is very toxic to humans,
generally enters the human body through the respiratory tract,
from which it is carried by the blood stream to various body
organs. The hydrogen sulfide that enters the blood can lead
to blocking of oxygen transfer, especially at high concentra-
tions. 102 In general, the hydrogen sulfide acts as a cell
and enzyme poison and can cause irreversible changes in
nerve tissue . 34 ’ 10 ’
At high concentrations (over 1,000,000 ig/m 3 ), hy-
drogen sulfide frequently causes death quickly by paralysis
of the respiratory center. - 01 However, if the victim is
moved quickly to uncontaminated air and respiration initiated
before heart action stops, rapid recovery can be expected. 99
At lower concentration, hydrogen sulfide causes conjuncti-
vitis, lachrymal secretion, respiratory tract irritation,
pulmonary edema, damage to the heart muscle, psychic changes,
disturbed equilibrium, nerve paralysis, spasms, unconscious-
ness, and circulatory collapse. 101 ’ 102 Some common symptoms
are metallic taste, fatigue, diarrhea, blurred vision, in-
tense aching of the eyes, insomnia, and vertigo. 49 ’ 101
Some of the effects of hydrogen sulfide and the air concen-
trations at which they occur are shown in Table 15 in the
Appendix.
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Hydrogen sulfide may produce synergistic effects in
mixtures with carbon disulfide hydrocarbons and carbon mon-
oxide. 101 In Russia, an increased effect was attained with
a mixture of hydrogen sulfide and naphtha gas)° 2 In addi-
tion, mixtures of carbon monoxide and hydrogen sulfide in
concentrations* that individually would not be dangerous
were harmful to animals after only 10 minutes’ exposure. 102
2.1.1 Odor Threshold
Hydrogen sulfide has a characteristic smell of
rotten eggs, 114 and this odor is the most sensitive indica-
tor of its presence in low concentrations. However, the
odor perception threshold varies considerably among indivi-
duals and apparently depends on the age and sex of the in—
dividuals, the size of the town they live in, and whether
they smoke. 3 The reported odor threshold varies between 1
and 45 .ig/m 3 (see Table 1). At 500 ug/m 3 , the odor is
distinct; at 4,000 to 8,000 ig/m , the odor is offensive and
moderately intense; and at 30,000 to 50,000 .ig/m 3 , the odor
is strong but not intolerable . At 320,000 g/m 3 , the
smell is not as pungent, probably due to the paralysis of
the olfactory nerves. 102 The perception concentrations are
based on initial inhalations since continuous inhalation
causes rapid olfactory sense fatigue. 99 At concentrations
*Values not stated.
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over 1,120,000 Lg/m 3 , there is practically no sensation of
odor and death can occur rapidly. 101 Loss of sense of smell
has even been reported at 150,000 ig/m 3 after exposures of
from 2 to 15 minutes. 132 Therefore, dulling of the olfactory
nerves constitutes a major danger to people who are exposed
to moderate and high concentrations of hydrogen sulfide
for extended periods. 102
2.1.2 Pollution Occurrences
The most serious episode reported involving hydro-
gen sulfide air pollution occurred in Poza Rica in Mexico
on Noverriber 24, 1950. There was an accidental release of
gas from a hydrogen sulfide absorption unit in a natural
gas refining plant. 65 This resulted in the release of con-
siderable amounts of hydrogen sulfide, which quickly spread
to the residential areas where most people were asleep. The
situation was aggravated by an atmospheric temperature in-
version with patches of haze and fog. The gas was shut off
within 20 to 25 minutes, yet 22 persons died and 320 persons
were hospitalized as a result of this brief exposure. 5 ’ 5 °
The effects were characteristic of hydrogen sulfide gas
poisoning: loss of sense of smell, cough, dyspnea, conjunc-
tival irritation, nausea, vomiting, severe headache, and
50
vertigo. The incident was over before any atmospheric
measurements were made.
In the Terre Haute, md., episodes in Nay and June
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TABLE 1
ODOR DETECTION THRESHOLD FOR HYDROG T SULFIDE
Odor Threshold
( ig/m 3 ) Reference
9—45 3
78
78
15 75
142
12—30 41
aHydrogen sulfide from sodium
sulfide.
bHydrogen sulfide gas.
CMean value ratio of highest to
lowest odor threshold concentra-
tion detected by all observers
in successive tests is 3.18.
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1964, hydrogen sulfide concentrations were sufficient to
cause foul odor, resulting in 81 public complaints of dis-
comfort and paint—blackening. Of the complaints, 40 re-
ferred to property damage, and 41 referred to health effects.
The main symptoms reported were nausea, loss of sleep and
abrupt awakening, shortness of breath, and headaches. How-
ever, almost none of those affected sought medical attention.
The source of the hydrogen sulfide was a 36—acre lagoon used
for biodegradation of industrial wastes. Hydrogen sulfide
concentrations in the atmosphere during the episodes ranged
between 34 and 450 .tg/m . 7
A major pollution problem of ]craft mills is the
emission of hydrogen sulfide and organic sulfide, causing
a disagreeable odor in the surrounding areas. At times
atmospheric concentration of these gases adjacent to the
kraft mills have reached levels which are capable of pro-
ducing nausea, vomiting, headache, loss of appetite, dis-
turbed sleep, upset stomach, and hampered breathing.
2.2 Effects on Animals
2.2.1 Coitunercial and Domestic Animals
Hydrogen sulfide produces about the same health
effects in domestic animals as in man at approximately the
same air concentrations. 101 The Air Pollution Control
Association Committee on Ambient Air Standards 76 stated
(1964) that spontaneous injury to animals occurs at 150,000
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to 450,000 pg/rn 3 of hydrogen sulfide. In the Poza Rica
incident, it was reported that all the canaries in the area
were killed and about 50 percent of the other animals died.
An ng these were chicken, cattle, pigs, geese, dogs, and
cats. 33 ’ 66
2.2.2 Experimental Animals
Fyn—Djui 41 exposed 10 rats to 1,000 pg/rn 3 of hydro-
gen sulfide in chronic experimental conditions for 12 hours
per day for three months. The exposure produced changes in
the functional state of the central nervous system, irrita-
tions in the mucosa of the trachea, and morphologic changes
in the brain cortex. At concentrations of 20 pg/rn 3 , only
slight to negligible changes occurred in the functional
state of the nervous system, and there was barely perceptible
irritation to the mucosa of trachea and bronchi. 4 - Weedon
exposed houseflies to hydrogen sulfide concentra-
tions of 1,500,000 pg/rn 3 . The percent of kill versus time
of exposure is shown in Figure 1. They also exposed groups
of eight rats and four mice to hydrogen sulfide concentra-
tions of 1,500,000 pg/rn 3 , 380,000 pg/rn 3 , 96,000 pg/rn 3 , and
24,000 pg/rn 3 for periods up to 16 hours. At 1,500,000 pg/rn 3
all the rats were active during the first 5 minutes. At
the end of 5 minutes they lost their muscular coordination,
and by 11 minutes they were prostrate. They all died in
29 to 37 minutes. Similarly, the mice were active during
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8
99
90
50
10
1
0.25 1 4 15 60 240 960
Minutes of Exposure
FIGURE 1
Time—Mortality Toxicity Curve for Houseflies Exposed
to 1,500,000 ig/m 3 Hydrogen Sulfide 139
I I I I I
4 - I
C
C.)
a,
0
0
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the first few minutes. Marked lachrymation followed and
all died within 20 minutes.
At exposures of 380,000 ig/m 3 all the rats were
active, sniffing and rubbing their noses for the first 25
minutes, and then they became quiet. Three rats were dead
when the experiment was discontinued at 22.9 hours. The
mice exposed to the same concentrations exhibited the same
symptoms for the first hour of exposure. At the end of 2
hours they were gasping and their abdomens were distended.
They all died at the end of 7 hours.
The rats were not affected during the first hour of
exposure to 96,000 .ig/m 3 . Even after 16 hours, the surviving
rats seemed to be in fair condition, even though they were
lethargic and gasping. The mice exposed to the same con-
centrations showed similar but more marked signs. Only
one mouse survived after 16 hours’ exposure, and it died 23
hours later.
No abnormal symptoms were noticed at 24,000 ig/m 3 .
A mouse exposed to the 24,000 ig/m 3 concentration for 16
hours was sacrificed, and at autopsy all organs proved normal
throughout. The time required to reach a 50 percent mor-
tality (TL 5 ,) rate in these experiments for the rats, mice,
and flies is shown in Table 16 in the Appendix. Typical
gross findings at autopsy for exposed rats and mice are
shown in Table 17 in the Appendix.
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Patty 99 reported an experiment in which a dog was
exposed to 1,500,000 .ig/m 3 of hydrogen sulfide. When first
placed in the atmosphere, the dog was frisky for a short
time; he then stopped, breathed laboriously for a moment,
fell, gasped, and remained motionless with legs extended.
At the end of 1 minute he was removed and given artificial
respiration, and he recovered fully in 1 to 2 minutes.
Smith and Goss1en - 2 ° found that pretreatment of
mice with sodium nitrate and p—aminopropinphenone (P PP)
significantly prolonged their survival during continuous
exposure to hydrogen sulfide. The mice were exposed to
1,100,000 ig/m 3 , 1,500,000 .Lg/m 3 , and 2,840,000 ig/m 3 ;
the greatest protection occurred at the intermediate concen-
tration as shown in Table 2. Propylene glycol also prolonged
the life of the mice. For the propylene glycol to be
effective at the middle concentration (1,100,000 p g/m 3 ),
exposure to hydrogen sulfide has to be delayed for 30
minutes after treatment. At the highest concentration
(2,840,000 ig/m 3 ), propylene glycol did not have any effect,
even when exposure to the hydrogen sulfide was delayed 30
minutes.
Baikov 17 found that there were no noticeable adverse
effects to rats after exposure for 70 days, 24 hours per day,
to air containing 8 jj g/m 3 of hydrogen sulfide and 10 ug/m 3
carbon disulfide (the Russian environmental standard).
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TABLE 2
THE PROTECTION INDEX* OF SODIUM NITRITE AND PAPP
PRETREATED MICE EXPOSED TO HYDROGEN SULFIDE 12 °
(Total Number of Mice = 107)
Pretreatment
Hydrogen
Sulfide
(ppm)
722
985
1,872
Nitrite
2.3
3.8
1.4
PAPP (no delay)
1.6
3.5
2.4
PAPP (30—minute delay)
1.3
2.2
*protectjon index mean survival time of protected mice
mean survival time of control mice
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2.3 Effects on Plants
There is little evidence that hydrogen sulfide
causes significant injury to field crops at environmental
air concentrations 66,123
McCallan 84 observed that little or no injury occurred
to 29 species of plants when they were fumigated with less
than 60,000 ig/m 3 of hydrogen sulfide for 5 hours. After
5 hours at 600,000 ig/m 3 , some species were injured, but
not all. Boston fern, apple, cherry, peach and coleus
showed no appreciable injury at concentrations below 600,000
tg/m 3 . At concentrations between 60,000 and 600,000 ..ig/m 3 ,
gladiolus, rose, castor bean, sunflower, and buckwheat
showed moderate injury. Slightly more sensitive were tobacco,
cucumber, salvia, and tomato. 84 ’ 148
In general, hydrogen sulfide injures the youngest
plant leaves rather than the middle—aged or older ones.
Young, rapidly elongating tissues are the most severely in—
jured. Typical exterior symptoms are wilting without typical
discoloration (which starts at the tip of the leaf), with
the scorching of the youngest leaves of the plant occurring
first. 134 ’ 135
Thornton and Setterstrom 136 exposed tomato plants,
buckwheat, and tobacco to air concentrations of ammonia,
chlorine, sulfur dioxide, hydrogen cyanide, and hydrogen
sulfide of 1,500, 6,000, 24,000, 96,000, 380,000, and
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1,500,000 ig/m 3 for periods of 1, 4, 15, 60, 240, and 960
minutes. They found that hydrogen sulfide was only mildly
toxic to plant tissue. They also made measurements of pH
changes in leaf and stem tissue of tomato plants. At low
hydrogen sulfide concentrations, they found no significant
changes in pH. At high hydrogen sulfide concentrations
(1,500,000 .ig/m 3 ) the whole plant showed only a slight drop
in pH. Once the pH changed, there was no recovery. They
found very little correlation between the hydrogen sulfide-
caused pH change and plant damage.
The time in minutes until 50 percent of the exposed
plant surfaces were injured at 1,500,000 ig/m 3 of hydrogen
sulfide is shown in Table 3.
Earton 19 exposed dry and soaked radish and rye
seeds to hydrogen sulfide in concentrations of 380,000 p.g/m 3
and 1,500,000 ug/m 3 for periods of 1, 4, 15, 60, 240, and
960 minutes. He found that the gas is relatively nontoxic
to the seeds. The germination percentages for both rye and
radish were similar to the control lots, and there was no
delay in germination for the dry seeds. Germination for
the soaked seeds of both rye and radish was delayed 4 to 6
hours after 240 minutes’ exposure and 21 to 24 hours after
960 minutes’ exposure to 1,500,000 ig/m 3 . At 380,000 ig/m 3 ,
soaked radish seed had no delay in germination, but a 28-hour
delay in germination of soaked rye seed resulted from a 960—
hour exposure at 1,500,000 ig/m 3 .
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TABLE 3
TIME IN MINUTES UNT]L 50 PERCENT INJURY TO EXPOSED PLANT
SURFACES AT 1,500,000 ig/m 3 HYDROGEN SULFIDE ’ 36
Plant Surface
Plant
Time in
Minutes
Leaves
Tomato
30
Buckwheat
60
Tobacco
100
Stems
Tomato
45
Buckwheat
120
Tobacco
480
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Benedict and Breen 2 ° fumigated 10 weeds which occur
widely throughout the United States with hydrogen sulfide
and other pollutant gases in an effort to develop a method
for identifying the pollutants causing damage in an area.
These plants included annual bluegrass, cheeseweed, chick-
weed, dandelion, Kentucky bluegrass, laith’s—quarters, mustard,
nettle—leaf goosefoot, pigweed, and sunflower, which they
fumigated with 150,000 g/m 3 and 750,000 xg/m 3 of hydrogen
sulfide for about 4 hours. The hydrogen sulfide always
produced the greatest amount of marking on the youngest
leaves. Very often the growing point was killed. The
marking occurred between the veining network on the broad—
leaved plants.
The narrow—leaved plants developed a general powdery
appearance between the tip and the bend of the leaf, except
in extreme cases where the entire leaf was killed.
The color of the marking was usually white to tan,
except for sunflowers, where the leaves in the bud stage
took on an orange—brown cast. The percentage of the leaf
marked by hydrogen sulfide is shown in Table 18 in the
Appendix.
The six—week—old plants in dry soil showed more mark-
ing at the higher hydrogen sulfide concentration than the
plants in wet soil, while the reverse effect occurred at
the lower concentration, indicating that drought conditions
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may increase the plant’s sensitivity to concentrations of
750,000 ig/m 3 hydrogen sulfide and decrease it to concentra-
tions of 150,000 ig/m 3 . The relative sensitivity of the 10
species to hydrogen sulfide is shown in Table 19 in the
Appendix.
2.4 Effects on Materials
2.4.1 Effects on Paint
Hydrogen sulfide in the atmosphere reacts with paints
containing heavy metal salts in the pigment and the drier to
form a precipitate which darkens or discolors the surface.
Lead, mercury, cobalt, iron, and tin salts cause a gray or
black discoloration; cadmium salts cause a yellowish—orange
discoloration. Lead is probably the most common metal to
exhibit discoloration caused by the formation of black lead
suif ides. 54 ’ 145 The most commonly used white pigment in
the past was basic lead carbonate. Recently, titanium dioxide
pigments have been replacing the use of lead carbonate by
the paint industry. However, lead pigments continue to be
used because of the added durability they impart to paint
films.
Wohlers and Feldstein 145 reported that experiments
in the Bay Area of California showed that old lead-base
paints are more susceptible to hydrogen sulfide damage than
are new ones. They also reported that darkening is dependent
on both duration of exposure and concentration and can occur
-------
17
after exposure to hydrogen sulfide concentrations as low as
75 p g/m 3 for two hours. The time-concentration relationship
for paint—blackening is shown in Figure 2. These authors
suggested that paint darkening by hydrogen sulfide may vary
depending on (1) heavy metal content in paint, (2) temper-
ature and moisture, (3) hydrogen sulfide concentration, (4)
age and condition of paint, and (5) presence of other con-
taminants in the air.
Manganelli and Gregory 8 ’ found that the extent of
darkening of basic lead carbonate films by hydrogen sulfide
increased as the relative humidity increased from 30 to 90
percent. They also showed that the darkening for lead car-
bonate films on wood was less than on tile. 81
White lead paints darkened by hydrogen sulfide often
revert to their original color by oxidation of the sulfide
to white sulfate. 147 Manganelli arid Gregory 81 found that
darkened films of basic carbonate faded in the presence of
light and oxygen and that the fastest rates of fading were
obtained in sunlight or under a tungsten lamp. They also
found that the fading capacity of fresh paint was not depen-
dent on the presence of atmospheric oxygen, indicating that
an oxidizing substance such as a peroxide was formed during
the drying of the film.
Paint-darkening by hydrogen sulfide occurred in the
Jacksonville area of Florida in 1961 due to hydrogen sulfide
-------
18
100
\
‘ c Metal tarnishing
\
\
\
10
\
\
U)
1.1
Paint blackening
\
\
1.0 — California Standard of
Ambient Air Quality at
“Adverse Level” \
\
\
o.i I
1 10 100 1,000
Hydrogen Sulfide Concentration, ppm vol
(ppm = 1,500 . .tg/m 3 )
FIGURE 2
Exposure Time Versus Concentration for Hydrogen Sulfide Effects 145
-------
19
emitted from the city water aeration plant. 117 Paint-darken-.
ing also occurred in 1963 in New York City and in South
Brunswick, N.J. in the New York incident, the hydrogen
sulfide was released from a polluted salt water channel.
An industrial dump was responsible for the incident in New
Jersey. In Terre Haute, md ., paint on houses close to the
7
industrial waste disposal lagoon was darkened, and in the
communities of Lewiston, Idaho, and Clarkston, Wash., damage
to house paint was caused by hydrogen sulfide emissions from
127
a kraft paper mill.
2.4.2 Effects on Metals
In the presence of hydrogen sulfide, copper and
silver tarnish rapidly.’ 47 Copper that has been exposed to
unpolluted air for some time resists attack by hydrogen
sulfide.’ 23 Hydrogen sulfide tarnishes silver at room
temperature; however, both moisture and oxygen must be present
for tarnishing to occur. 46 ’ 123 The sulfide coating formed
on copper and silver electrical contacts can increase con-
tact resistance when the contacts are closed. In some
cases, this can result in the contacts becoming welded shut. 147
Wohiers and Fe1dstein - 45 indicated that hydrogen sulfide-
sensitive metals, like silver or copper, will tarnish when
exposed to hydrogen sulfide concentrations above 4 ig/m 3
for 40 hours (Figure 2).
Some alloys of gold--even such a high—carat alloy
-------
20
as 69 percent gold, 25 percent silver, and 6 percent plati-
num--will tarnish when exposed to hydrogen sulfide. However,
in general, gold (14—carat and above) and gold leaf (95 per-
cent gold and above) will have adequate resistance to at-
mospheric hydrogen sulfide. 67
Hydrogen sulfide will attack zinc at room temperature,
forming a zinc sulfide film which prevents further corrosion.
At high temperatures the attack is quite vigorous. 70 At
concentrations normally found in the atmosphere and at am-
bient temperatures, hydrogen sulfide is not corrosive to
ferrous metals. 118
2.5 Environmental Air Standards
The American Conference of Governmental Industrial
Hygienists (ACGIH), at their 29th Annual Meeting in 1967, set
the threshold limit value for hydrogen sulfide in air for an
eight—hour—day, 40-hour week, at 15,000 pg/m ) 37 The hydrogen
sulfide ajr ient air quality standards for various States and
governments are shown in Table 4.
-------
TABLE 4
AMBIENT AIR QUALITY STANDARDS
Country or State
Basic Standard
Permissible
Standard
Maximum single
Measurement
ig/m 3
.
Reference
ig/m ”
Avg Time
.i .g/m 3
Avg Time
California
150
1 hr
67, 125, 132
Missouri
45
30 mm
75
30 mm
9, 67. 125
Montana
45
30 miri
75
30 mm
125
New York
150
1 hr
125
Pennsylvania
7.5
24 hr
150
1 hr
12, 22, 125
Texas
120
30 mm
180
30 mm
125
Czechoslovakia
8
24 hr
8
30 mm
8
67, 125
Canada (Ontario)
45
30 mm
125
Poland
20
24 hr
62, 100, 125
U.S.S.R.
8
24 hr
8
20 mm
8
93, 125
Federal Republic of
Germany
150
30 mm
300
30 mm
103, 125
I- . ’
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22
3. SOURCES
3.1 Natural Occurrence
Hydrogen sulfide is produced in nature primarily
through decomposition of proteinaceous material (vegetable
and animal) by bacteria. 81 ’ 101 It develops principally in
stagnant and insufficiently aerated water such as found in
swamps and polluted water. 34 ’ 35 ’ 101 Hydrogen sulfide also
occurs naturally as a constituent of natural gas, petroleum,
sulfur deposits, and numerous volcanic gases and sulfur
springs. 70 ’ 81 ’ 101
Robinson and Robbins 108 have estimated that the
annual worldwide production of hydrogen sulfide is around
90 to 100 million tons, with 60 to 80 million tons coming
from land sources and 30 million tons coming from ocean
areas. Other estimates range as high as 202 million tons
from ocean areas and 82 million tons from land areas. 108
Data on background air concentrations of hydrogen sulfide
due to the natural sources are scarce. However, it has
been estimated to be between 0.15 and 0.46 ..ig/m 3 , which is
well below the odor threshold or the concentrations at which
deleterious effects are known to occur.
3.2 Production Sources
Hydrogen sulfide is produced as a by—product in
many industrial processes. Production sources include the
petroleum industry (refineries and natural gas plants),
-------
23
petrochemical plant complexes, coke oven plants, kraft paper
mills, chemical processing industries, dye manufacture,
viscose rayon manufacture, sulfur production, manufacture of
sulfur—containing chemicals, iron and metal smelters, food
processing plants, and tanneries.
3.2.1 Petroleum Industry
Sulfur enters the refinery as a constituent of
crude oil and is usually found in coiribination with hydrogen
as hydrogen sulfide and with hydrocarbons as various organic
suif ides. Since removal of sulfur from both product and in-
termediate stocks is necessary to meet low sulfur requirements
for fuel oil and to prevent sulfur poisoning of catalysts,
processes such as hydrogen treating are employed. During
the various steps employed in processing the crude oil, the
sulfur compounds are generally converted to hydrogen sulfide
and lower molecular weight mercaptans. 15 ’ 57 From each
20,000 barrels of crude oil with high sulfur content pro-
cessed, approximately 50 tons of hydrogen sulfide are formed. 8 ’
The main sources of air pollution in refineries are
untreated gas stream leaks, vapors from crude oil and raw
distillates, and process and condensate sewers. 104 Typical
refinery processing systems that have hydrogen sulfide emis—
88
sions are crackthg units, catalytic reforming units, and
sulfur recovery units)- 38 The cracking process tends to
convert sulfur contained in crude oil into hydrogen sulfide
-------
24
in the heavier materials and into mercaptans in the gasoline
fractions. 14 ° Measurements were macie in the El Paso, Tex.,
area of the atmospheric hydrogen sulfide concentration adjacent
to an oil refinery. The mean hydrogen sulfide concentration
was 6 ig/m 3 . This varied from undetectable amounts to a
maximum of 91 g/m . 55
In 1960 there were about 300 oil refineries distrib-
uted throughout the United States with a crude oil capacity
of approximately 10 million barrels per day. 132 By 1969
there were approximately 263 refineries in the United States
with a crude oil capacity of approximately 12 million barrels
per day ) 30 The States in which the refineries are located
and their crude charge capacity in January 1969 are shown in
Table 20 in the Appendix. The crude capacity of refineries
in the United States from 1964 projected to 1972 is shown in
Figure 3.
A number of refineries and natural gas plants have
installed units to recover sulfur from hydrogen sulfide.
The plant capacities and yearly production rate for this
process are shown in Table 5.
TABLE 5
SULFUR PRO DUCF ION FROM HYDROGEN SULF IDE
IN THE UNITED STATES 48 ’ 94
Long Tons/Year
Year Plant Capacity Actual Production
1961 1,659,000 858,000
1967 2,737,000 1,244,000
1968 3,036,000 1,400,000
-------
25
Million barrels per
calendar day
12.0
11.5
11.0
10.5
10.0
9.5
9.0
8.5
1964 1965 1966 1967 1968 1969 1970 1971 1972
FIGURE 3
,
Year
ruae Lapacity of United States Refineries 95
-------
26
Hydrogen sulfide occurs naturally in many areas in
association with natural gas. 101 In some areas, such as
Alberta, Canada, the sour natural gas can consist of over
50 percent hydrogen sulfide. In processing, the natural
gas stream is treated to remove the hydrogen sulfide, which
is generally converted to sulfur. Distributing companies
which sell the natural gas for heating and power generation
generally require that its hydrogen sulfide content be less
than 23,000 g/m ) 15 The amount of natural gas produced in
the United States in 1955 (projected through 1985) is shown
in Figure 4.
Another possible source of hydrogen sulfide air
pollution in the petroleum industry is the production of
asphalt. Mel’ ster j 7 have reported that during the
distillation and oxidation of petroleum for the production
of asphalt, hydrogen sulfide is produced, but they gave no
production or emission data.
3.2.2 Petro hemical Plant Complexes
Hydrogen sulfide is produced in petrochemical plants
during cracking and other desulfurization reactions. 88
Krasovitskaya et al. 7 ] - reported on atmospheric hydrogen
sulfide concentrations around a petrochemical industrial
complex in Russia. The complex consisted of three oil re-
fineries, a synthetic alcohol plant, a chemical plant, and
three power plants. Measurements made of air concentrations
-------
27
28
24
0
20
F-
80 ’
.216
1955 1960 1965 1970 1975 1980 1985
* mcf: million cubic feet
FIGURE 4
Natural Gas Production and Plant Production of Ethane and
• . . 56
Liquid Propane Gas (LPG) for Fuel and Chemical Use
-------
28
of hydrogen sulfide owed 17 to 150 .ig/m 3 inside the indus-
trial cOmplex, 8 to 70 g/m 3 at 2.5 km from the complex, and
1 to 50 j..ig at 20 km from the complex. 71
3.2.3 Kraft Mills
Hydrogen sulfide and organic sulfide are produced
and released to the atmosphere in kraft mills in a number of
locations. This emission imparts the characteristic odor
in the vicinity of kraft paper mills and has been the cause
of major air pollution problems. Over 50 percent of the
pulp produced in the United States comes from the kraft or
68 108
sulfate process. Robinson and Robbins estimated that
in 1960 about 64,000 tons of hydrogen sulfide were emitted
from kraft paper mills throughout the world.
In the Icraft process, wood chips and a solution of
sodium sulfide and sodium hydroxide (white liquor) are cooked
in a digester for about 3 hours at elevated temperatures and
pressures. The solution dissolves the liquor from the wood.
The spent liquor (black liquor) is then separated from the
cellulose fiber in the blow tank. The fiber is then washec and
processed into paper. The remainder of the process in o1ves
the recovery and regeneration of the cooking chemicals from
the black liquor. The recovery process is initiated by
concentrating the black liquor by evaporation. The concen-
trated black liquor is then burned in the recovery furnace,
and the inorganic chemicals collect on the floor of the
-------
29
furnace in a molten state (smelt). Hot conibustion gases
from the recovery furnace are used in the direct contact
evaporation to concentrate the black liquor. 68 ’ 125
The major sources of hydrogen sulfide emission in
kraft mills are the stack gases from the recovery furnace,
including the direct contact evaporator; the stack gases from
the lime kilns; 29 and the noncondensibles from the digester
relief, the blow tank, and the multi-effect evaporator. 23 -’ - 27
The quantities of emissions from each source are given in
Table 6. The amount of these emissions actually reaching
the environment depends upon the efficiency of each of the
abatement systems that are installed and operating at each
mill. Table 7 shows the emissions from a kraft mill in
Lewiston, Idaho. The mill produces 450 tons per day of
bleached paper board and 200 tons per day of market pulp. 127
The single largest source of hydrogen sulfide in a
kraft mill is the recovery furnace, and the amount produced
is very sensitive to furnace loading. The hydrogen sulfide
produced in the furnace rises very rapidly when the furnace
is operated above design conditions. The relationship
between hydrogen sulfide production in the recovery furnace
and the furnace loading is shown in Figure 5.
Measurements were made during a six—month period in
1961 and 1962 of ambient hydrogen sulfide concentration in
the Lewiston, Idaho area, where the paper mill is the major
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30
TABLE 6
HYDROGEL SULFIDE E 1ISSIONS FROM KRAF MILL PROCESSORS
Pounds/Dry
Tori Produced
(cooking
temp 172°C,
0—0.45
ig/m 3
E nitted Ref.
0—600,000 68
and blow
conditions) 0.43
208,000
141
(no data on
0.9
106
and blow
3.45 hr,
sulfidity 22.5%) 0.66
127
(no data on
0.01—0.05
116
3.6—28
198,00C—
1,500,000
68,116
stack gases
750,000—
1,150,000
141
9.0
106
evaporators
1.2
68
evaporators
0—0.06
68
evaporators 1.2
106
-rw
0-900,000
125
-------
31
TABLE 7
ESTIMATED HYDROGEN SULFIDE EMISSIONS* FROM
650 TON/DAY KRAFT MILL IN LEWISTON, IDAHO 127
Process or Equipm& t
Source
lb/day
Digester gases
9
Evaporators
390
Recovery furnaces
3,120
Lime kilns
737
Total
4,256
*Includes oxidation towers for black liquor and
chlorination for digester gases (see Abatement, Section 4).
In Thousands
1,500
750
0
a,
V
ol
V
:i:
Design Limits
Furnace Loading
FIGURE 5
Relation Between Hydrogen Sulfide
Production and Furnace Loading 125
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32
contributor of gaseous pollutants. The measurements are
summarized in Table 8. During an incident in November 1961,
29
peak 2—hour concentrations of 77 .tg/m 3 were measured.
TABLE 8
FREQUENCY D ISTR IBUT ION OF HYDROG Zj SULF IDE
CO! CENTRATIONS, l961—1962
Hydrogen Sulfide _ %Frequency at Sampling Station
Concentration Lewi ston Lewistcin
( Lg/m 3 ) Lewiston Residential Commercial
Orchards District District
0—3 92.2 89.1 68.1
4—14 7.3 8.6 28.2
> 15 0.5 2.3 3.7
In 1957, about 12.8 million tons of pulp were made
by the kraft process in mills located as shown in Figure 8
in the Appendix. The United States production of pulp by
the kraft process from the year 1957 to 1967 is shown in
Table 21 in the Appendix.
3.2.4 Coke Ovens
Hydrogen sulfide is produced in the coking operation
70
at the rate of about 6.7 pounds per ton of coal charged.
The effluent gas from coke ovens contains about 6,000 to
107
13,000 xg/m 3 of hydrogen sulfide. During cooling and
scrubbing, approximately 50 percent of the hydrogen sulfide
-------
33
is removed. The remaining gas is either used as is for
firing the coke ovens; purified further (partial desulfuri—
zation) and then used for firing of coke ovens; or completely
desulfurized and used for municipal gas. The hydrogen
sulfide content of nonpurified, partially purified, and
municipal gas is mown in Table 9.
TABLE 9
107
HYDROGEN SULFIDE CONTENT OF COKE-OVEN GAS
Type of Gas p.g/m 3
Nonpurified 5,000—13,000
Partially desulfurized 1,500—5,000
Municipal gas or
pipeline gas None
Hydrogen sulfide emissions can occur throughout the
complete coking cycle from coke—oven charging to hydrogen
64
sulfide removal (desulfurization). The sources of these
emissions, other than charging and discharging emissions,
and their causes are shown in Table 10. No data were found
on the magnitude of hydrogen sulfide concentration in the
atmosphere in or around coke ovens. However, one reference
indicated that it is rarely of sufficient magnitude to
create problems or evoke complaints from nearby residents.
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34
TABLE 10
DURCES OF HYDR0GEL T SULFIDE EMISSIONS IN COKE PLANTS 107
Source of Emission
Condensation
Unburnt gases escaping from the
gas torches
In normal operation with
torch shut off
With torch open during
operational failures
Gases escaping from water seals
Outflow collectors on coolers;
collector and separator
tanks
Ammonia Scrubber
Outflow collectors and collec-
tor tanks
Secondary coolers for primary—
cooler outflow (in semi—
direct process)
Benzol Scrubber and Plant
Outflow receivers of scrubbers
and washing oil tanks
Cooler—ventilating lines
Leakage at stop valves
Failure of ignition device
Defective seals
Gas escape from liquids
Cause of Emission
Gas escape from washing of
fluid
Escape of hydrogen sulfide
with the cooling-tower
vapors
Gas escape from washing
fluid
Escape of sulfur—containing
compounds with low boiling
point, together with ven-
tilating gases
Desulfurization of Gas
Outflow receivers and tanks for Gas escape from washing
scrubbing fluid fluid
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35
In 1966 about 66 million tons of coke were produced
in the United States in 66 coke oven plants. The value of
the coke at the coke oven was estimated to be $1,144 million.
The production rate of coke from 1957 to 1968 is shown in
Table 22 in the Appendix.
3.2 .5 Mining
Burning coal refuse piles have been a continual
cause of air pollution, and one of the combustion products
131
emitted to the atmosphere is hydrogen sulfide. Approxi-
mately 20 percent to 50 percent of the raw anthracite
processed in cleaning plants is rejected as refuse. At
many operations the refuse discarded amounts to about 33
percent of the tonnage produced. This refuse over the years
has accumulated in coal refuse piles, some of iich contain
125
millions of tons.. The piles ignite either through
spontaneous con ustion, carelessness, or deliberate action.
A recent survey indicated that there are approximately
125
500 burning piles in 15 States.
The hydrogen sulfide generated during combustion
disperses into the atmosphere. Significant concentrations
of hydrogen sulfide gas have been measured in communities
131
adjacent to burning coal piles. Sussman and Muihern
reported that measurements made in July 1960 adjacent to a
large burning anthracite refuse pile showed an hourly
-------
36
maximum average of 600 hg/rn 3 . The minimum hourly average
was 140 1g/m 3 .
Other possible sources of hydrogen sulfide from
mines include underground mine fires and sulfide ore mines.
However, no information was found on these sources.
3.2.6 Iron—Steel Industry and Foundries
Small amounts of hydrogen sulfide are given off
6
when blast furnace slag is granulated. Woehlbier and
143
Rengstorff showed experimentally that the amount of
hydrogen sulfide formed is proportional to the amount of
hydrogen formed during the quenching process. No information
was given on the amount of hydrogen sulfide released to the
atmosphere by plant granulation operations. Typical hydrogen
sulfide exhaust emissions from foundries are 0.002 tons per
non—ferrous foundry producing 50 tons of castings per day,
and 0.023 tons per gray iron foundry producing 200 tons of
69
castings per day.
3.2.7 Chemical Industry
Hydrogen sulfide is a by-product of many chemical
operations. In general, it is formed when sulfur or ulfur
compounds are associated with organic materials at a high
temperature. For example, it is a by—product in the manufac-
ture of carbon disulfide. The process of producing thiophene
by the reaction of sulfur with butane at elevated temperatures
107
also produces hydrogen sulfide.
-------
37
Other sources of hydrogen sulfide in the chemical
industry are the manufacture of sulfur dyes 83 and the
production of viscose rayon, ethyl and methyl parathion
(pesticides), 128 organic thiophosphate, 86 and many other
organic sulfur chemicals. In addition, hydrogen sulfide
is evolved from some grease and fatty acid—making processes.
Approximately 6 tons of hydrogen sulfide are formed for every
100 tons of viscose rayon produced. 81 Inorganic processes
thich evolve hydrogen sulfide are zinc smelting and refining, 122
manufacture of barium chloride from barium sulfide, and
production of phosphorus compounds, pigments, lithopone,
and sodium sulfide. 101 Hydrogen sulfide is also emitted
during the manufacture of stove clay and glass. 69 ’ 101
The only data found on the magnitude of hydrogen sulfide
emissions were 0.024 tons reported per chemical and allied
products plant consuming i0 9 BTU per day, and 0.17 tons per
cement plant producing 4,830 barrels per day. 69
Yanysheva - 46 measured the hydrogen sulfide concen-
tration in the atmosphere at distances of 200 to 2,500
meters from an electric power plant and chemical combine
and up to 800 meters from a phenol production plant. The
chemical combine produced sulfuric acid, nitric acid,
chlorine, and chlorinated lime. The atmospheric hydrogen
sulfide concentration measured varied between 600 and
-------
38
28
1,600 ig/m . Buraithovich reported on hydrogen sulfide
measurements made in the vicinity of Lisichansk and Rubezhnoe
chemical plants in Russia. The Lisichansk plant manufactures
mineral fertilizers, synthetic monomers, ammonia, alcohols,
and plastics. The Rubezhnoe plant produces high quality
dyes, dye intermediates, and various poisonous chemicals.
The atmospheric hydrogen sulfide measurements are shown
in Table 11.
44
Glebova measured the concentration of hydrogen
sulfide in the atmosphere at 1 1cm from a viscose rayon plant.
The maximum single concentration was 50 .tg/m 3 . Measurements
were also made in the vicinity of the Dorogomelovsk Chemical
Manufacture Plant, which produces sulfur dyes and mercapto—
benzothiazole rubber accelerators. The hydrogen sulfide
concentrations at various distances from the plant are shown
in Table 12.
3.2.8 Animal Processing Plants and Tanneries
Hydrogen sulfide is generated in animal processing
125
plants during the decomposition of protein material.
129
Summer reported that hydrogen sulfide and organic sulfur
compounds are produced in an offal cooking plant when hooves
and horns of cattle and other animals are treated with
high—pressure live steam. Hydrogen sulfide is also produced
during the cooking of meat. In stale meat, approximately
-------
39
TABLE 11
HYDROGEN
SULFIDE CONCENTRATIONS AT VARIOUS
DISTANCES FROM PLANTS 28
(One-Time Maximum in .1g/m 3 )
Lisichansk Plant Rubezhnoe Plant
Year 2,000m
4,000m 500rn 1,000m 2,000m 4,000m
1963 40
21
1964 50
35 64 >8 >8
1965
17 18 15 9
TABLE 12
ATMOSPHERIC
DIFFERENT
AIR POLLUTION BY HYDROGEN SULFIDE AT
DISTANCES FROM SOURCE OF POLLUTION 41
Distance
in
Meters
Maximum Minimum
Concentration Concentration
( ig/m 3 ) (p g/ma)
100
66 16
200
58 35
300
59 39
400
40 26
500
35 20
750
26 15
1,000
22 14
1,250
11 05
-------
40
0.15 pounds of hydrogen sulfide is formed per ton of raw
meat at 100°C. Only a trace is formed during the cooking
129
of fresh meat.
During the 1920’s and the early thirties, there
were many cases of poisoning among tanners (some fatal)
119
mainly caused by hydrogen sulfide. The air concentrations
119
at those times varied from 1,000 to 540,000 ig/m 3 .
However, recent results of a nine—year—study on tanneries
in Russia showed that the hydrogen sulfide has been almost
119
eliminated in modern tanneries. No information was
found on United States tanneries, but it can be assumed that
the hydrogen sulfide problem has been largely eliminated.
Other sources of hydrogen sulfide are stockyards,
101
cheese and dairy plants, and wool scrubbing plants. No
information was available on emissions from these sources.
3.3 Product Sources
This category is not applicable since hydrogen
sulfide is produced only as a by-product.
3.4 Other Sources
3.4.1 Combustion Processes
Hydrogen sulfide is released when coal, oil, or gas
is burned. The amount of hydrogen sulfide depends upon the
amount of sulfur in the fuel and the efficiency of the
combustion process. In an efficient combustion system, the
-------
41
hydrogen sulfide is oxidized to sulfur dioxide. In a study
of sulfur released from domestic boilers, it was found that
hydrogen sulfide was given off from open fires during heavy
noke emission, mainly just after refueling. The emission
factors for fuel combustion are given in Table 13.
TABLE 13
HYDROGEN SULFIDE v1ISSION FACTORS
Combustion
Source
Emission Factor
Reference
Coal
—
.0045*/lb coal
110
Fuel oil
1 lb/l,000 lb
oil
8,121
Natural gas
0.13 ib/i,000
lb
gas
8
(density
0.0475)
*lb/sulfur/lb coal.
Hydrogen sulfide is also given off by apartment incinerators
37
and sanitary land fills. Eliassen reported in 1959 on
estimates of hydrogen sulfide discharged daily from domestic
and municipal sources in a metropolitan area of 100,000
persons. According to this estimate, domestic heating would
produce 1,000 pounds of hydrogen sulfide daily from coal
combustion, 500 pounds from oil, and 0.1 pounds from gas;
apartment incineration would produce 24 pounds daily, and
sanitary land fill would produce trace amounts.
-------
42
3.4.2 Polluted Water
In some localized situatiOns, air pollution due to
natural biological processes in polluted waters includes
hydrogen sulfide air concentrations that can produce black-
ening of paint as well as odors above the hydrogen sulfide
34
odor threshold. Deniuead reported on the hydrogen sulfide
emissions from a shallow tidal inlet in Auckland, New Zealand.
This inlet was polluted by untreated domestic sewage and
food processing sewage. Surveys conducted during 1957
showed that the average daily concentration of hydrogen
sulfide in the air was 380 g/m 3 . This was computed to
represent about 1,500 i g/in 3 during night hours, a concen-
tration high ough to produce paint-blackening and the
foul odor. The problem cleared up when the domestic and
food processing wastes were treated in a new sewage treatment
plant prior to discharge into the tidal inlet.
A similar incident occurred on the island of Oahu
in March 1958 when rainwater filled a natural basin and
remained there due to inadequate drainage. The water in the
basin destroyed 80 acres of Akulikuli grass growth. The
stagnant water caused the plant life to decompose, producing
a strong fecal stench. Two weeks later, hydrogen sulfide
was quantitatively measured in the air. The hydrogen sulfide
was never present in levels dangerous to health, but did
-------
43
cause tarnishing of copper and silver. House paint also
was visibly affected. Measurements made at the drainage
ditch where water was pumped into a concrete culvert showed
hydrogen sulfide concentrations as high as 30,000 g/m 3 .
The hydrogen sulfide phase of the pollution lasted for a
45
period of about 10 days.
In Terre Haute, md ., during late May and early
June 1964, the concentrations of hydrogen sulfide in the
atmosphere were sufficient to cause public complaints
because of paint—blackening and physical discomfort.
Atmospheric concentrations exceeding 460 Ig/m were measured.
The main source of the pollution was found to be a 36—acre
industrial lagoon used for biodegradation of organic
7,123
industrial wastes.
3.4.3 Well Water
Another hydrogen sulfide source is municipal plants
for removing hydrogen sulfide from well waters. heeley
117
aj . reported that water aeration plants in the city
of Jacksonville, Fla., emit about 0.15 tons per day of
hydrogen sulfide. They state that the plants are a particu-
larly troublesome cause of nuisance complaints.
3.4.4 Sewage Plants and Sewers
Hydrogen sulfide is produced biologically in sewers
from organic compounds formed by hydrolysis of materials like
-------
44
cystine and methionine and by reduction of sulfates. Sewage
usually contains 1 to 5 ppm of organic sulfur compounds,
while some industrial wastes, such as from wool, contain
90
as high as 50 to 100 ppm. Sulfates are present in sewage
almost entirely as inorganic sulfates and enter the system
in waste water, saline ground water, or through industry
discharge of tidal or sea water to sewers. The factors that
influence hydrogen sulfide generation in sewers include
sewage temperature, content of sewage, velocity of flow,
age of sewage, pH value of sewage, sulfate concentration,
and ventilation of the sewer. Hydrogen sulfide is also
77
generated and released from sewage treatment plants. The
hydrogen sulfide is formed in digesters during anaerobic
90
digestion of the sewage sludge and industrial wastes.
Atmospheric measurements made at a sewage treatment plant
in El Paso, Te ., in 1958 showed that the hydrogen sulfide
concentration varied between 24 i Lg/m 3 and 2,120 ig/m 3 ,
with the average concentration 610 g/m 3 . At a sampling
station 100 yards from the sewage plant, the maximum
55
hydrogen sulfide concentration was 205 g/m 3 .
3.5 Environmental Air Concentrations
Routine measurements of the concentration of hydrogen
sulfide in the environmental air are not made by the National
Air Sampling Network. Data from selected areas for various
time periods indicate average levels of hydrogen sulfide in
the atmosphere of 1 to 92 .ig/m 3 , as indicated in Table 14.
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45
TABLE 14
ATMOSPHERIC HYDROGEN SULFIDE CONCENTRATIONS
(p.g/m 3 )
Location Average Maximum Ref.
New York City
1956—61 1 13 81
1962 1 6 13
Elizabeth, N. J.
Aug.—Oct. 1963 1 247 81
Hamilton Township, N. J.
May—Oct. 1962 1 49 81
Woodbridge Township, N. J.
April—May 1961 1 305 81
Greater Johnstown Area, Pa.
1963 3 210 47
Winston-Salem, N. C.
Nov..—Dec. 1962 3 011 85
Lewiston—Clarkston Area,
North Lewiston, Idaho, near
pulp mill, 1962 37 1
Great Kanawha-River Vall2y
Industrial Area
Feb. 1950—Aug. 1951 3—92 410 16
Camas, Wash.
1962 0—1 6 8
Santa Barbara, Calif.
1949—1954 1,400 58
St. Louis, Mo.
1964 2—6 94 39
Terre Haute, md.
May—June 1964 >460 7
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46
4. ABAT 4 T
A. number of systems and types of equipment have been
developed for removal of hydrogen sulfide from gas streams.
Many of these systems are designed to recover the hydrogen
sulfide for subsequent conversion to valuable by—products,
such as sulfur and sulfuric acid. Many of the removal systems
are based on scrubbing the gas streams with a suitable absor-
bent ar then r uoving the absorbed gas from the absorbent
for disposal by burning or conversion to a valuable by—product.
Some of the absorbents convert the hydrogen sulfide to an
innocuous compound ‘c ftiich may be useful in some cases as a
fertilizer. Such chemicals as aqueous solutions of diethano —
amine and mtrnoethanolamine, sodium hydroxide , tn—potassium
phosphate, and aqueous solutions of chlorine and sodium
carbonate have been used as absorbents. Different types of
contacting devices (wet scrubbers) have been used, including
conventional and novel design spray towers, plate towers,
and venturi scrubbers.
4.1 Kraft Pa r Mills
In kraft paper mills, the greatest reduction of
hydrogen sulfide emissions was achieved by the black liquor
oxidation process. This process consists of oxidizing the
sulf ides in the weak black liquor (before the multiple—effect
evaporation) or strong black liquor (after the multiple—
effect evaporation) by contacting it with air in a packed—
tower, thin—film, or porous—plate black liquor oxidizing unit.
-------
47
The oxidation converts the suif ides to less volatile compounds
68
which are also less odorous and have less t dency to escape.
This conversion has the effect of reducing the hydrogen
sulfide emissions from the direct—contact evaporator and the
51,68,74
recovery—furnace stack by 80 to 95 percent. Since
these evaporators and furnace stacks are the principal emitters
101
of hydrogen sulfide in kraft mills, the net result is a
substantial reduction of hydrogen sulfide emission. The weak
black liquor oxidizing process also reduces emission from the
multiple—effect evaporators.
The majority of the black liquor oxidizing systems
installed in the United States are based on oxidation of weak
liquor, and are located in the Western part of the country.
In the Southern part of the country, the woods used in kraft
processes cause excessive foaming problems in the weak black
74,96
liquor oxidizing process. To alleviate this, a few
Southern mills have installed a process based on oxidizing
96,97
the strong black liquor.
The key to minimizing hydrogen sulfide emissions from
the recovery furnace, even in those systems employing black
liquor oxidizing systems, is proper furnace—operating condi—
51
tions. From Figure 5 in Section 3.2.3, it can be seen
that at furnace loading greater than design capacity, hydrogen
sulfide emissions rise substantially. For minimum emissions
fz m the recovery furnace, the furnace should not be operated
above design conditions. There should be 2 to 4 percent
excess oxygen leaving the secondary burning zone (i.e., leaving
-------
48
the furnace), and there should be adequate mixing (turbulence)
in the secondary combustion zone.
In the direct—contact evaporator, where the flue
gases from the recovery furnace are used to concentrate the
black liquor, the carbon dioxide in the flue gases reacts
with the sulfite in the black liquor to release hydrogen
sulfide. 96 Even where the black liquor oxidizing process is
employed, some sulfite remains after oxidation. This releases
some hydrogen sulfide when contacted with flue gases. There-
fore, rei oval of the direct—contact evaporator from the stream
further reduces sulfide emissions.
In the Scandinavian countries the recovery furnaces
are designed and operated in such a manner that black liquor
can be fed directly to them from the multiple-effect evapora-
tors. These fdrnaces efficiently burn all malodorous compounds;
the necessity c or oxidizing black liquor prior to burning is
therefore eliminated. Approximately 45 mills in Sweden use
additional multi—effect evaporators to replace the direct—
contact evaporator and burn unoxidized black liquor. 32
Three such installations are being installed in North Anierica. 32
The exact location of these units was not specified.
Another approach to burning unoxidized black liquor
while still minimizing the emission of malodorous compounds
53
was described by Hochmutch. In this system, the cornbusta on
gases from the recovery furnace are used to preheat air in a
recuperative air preheater. The hot air is then used to
-------
49
concentrate the black liquor in the direct—contact evaporator.
The air from the direct—contact evaporator is then used as
primary and secondary air in the recovery furnace, where
malodorous compounds in the air are incinerated in the
high—temperature combustion zones.
To reduce recovery—furnace particulate emissions,
some mills have installed a secondary wet scrubber to follow
the primary scrubber (direct—contact evaporator). Secondary
scrubbing does not remove hydrogen sulfide unless a basic
solution such as weak caustic is used. Limited pilot plant
studies and some plant experience have shown that weak wash
(ide., weak caustic solution) has removed hydrogen sulfide
from the stack gases. In other instances, no hydrogen
sulfide removal has been obtained under such a system. In
general, the removal of hydrogen sulfide from flue gases
containing 11 to 14 percent carbon dioxide with a caustic
solution has not been developed. 23 ’ 24 ’ 26 ’ 74
Other sources of hydrogen sulfide emissions from
kraft mills are the noncondensible gases released from
digesters and multiple—effect evaporators. Various systems
developed and installed for minimizing these emissions are
generally based on collecting the noncondensible gases in a
gas holder, then oxidizing or burning them at a constant
flow rate. The various methods used are the following:
-------
50
(1) Burning the gases in the recovery furnace or
lime lciln. 116
(2) Oxidizing the gases in a separate catalytic
74, 114
oxidizing furnace or a direct—flame incinerator.
(3) Oxidizing the gases in an absorption tower
with aqueous chlorine solutions, such as chlorine bleach
water from the bleach plant, waste chlorine, hypochiorite,
etc. Sometimes this is followed by processing in another
absorption tower, where the absorbent is either a weak
chlorine solution or a caustic solution. 61 ’ 116, 141
(4) Absorbing the gases with a caustic solution in
61
a scrubber.
In the lime kiln, the use of wet scrubbers with an
alkaithe—absorbent, efficient control of combustion, and
proper washing of lime mud will substantially reduce hydrogen
sulfide emissions. Scrubbing smelt tank gaseous emissions
with weak wash or green liquor in an absorption tower will
116
reduce hydrogen sulfide emissions from this source.
Around 1951, masking of odors by adding aromatic
compounds to the digester, the black liquor, and the stack
gases was tried in the United States. This strictly makeshift
approach did not solve the basic pollution problem and is not
141
used at the present time.
4.2 Petroleum Industry and Petrochemical Plants
In refineries and petrochemical plants, small
quantities of hydrogen sulfide associated with gas streams
-------
51
can be burned in the plant full system or in a flare. 88 In
refineries and natural gas plants where larger quantities of
hydrogen sulfide are associated with gas streams (sour gas),
the hydrogen sulfide is generally extracted in an absorption
tower using a number of different absorbents, such as
aqueous amines (Girbatol process); sulfalone (Shell process);
alkaline arsenites and arsenates (Giammarco—Vetrocoke process);
organic solvents such as propylene carbonate, glyceral
triacetate, lutoxy—dethylene-glycol acetate, methoxy—triethy—
lene glycol acetate (Fluor solvent process): and many others.
These processes are regenerative——that is, the absorbent is
regenerated by rencving the hydrogen sulfide and reused.
In the case of the Giammarco—Vetrocoke process, sulfur is
recovered directly as part of the absorbent regeneration
process. In the other processes the hydrogen sulfide from
the regeneration process is converted to sulfur by the
Claus process. 38 ’ 79 ’ 91 The sulfur can be further processed
into sulfuric acid if this is the end product desired.
4.3 coke—Oven Plants and Chemical Plants
In coke—oven plants, the coke—oven gases are often
purified of hydrogen sulfide by passing the gases through
11,38,126
iron—oxide—impregnated wood shavings. This process
is generally nonregenerative, although methods for regenerat-
ing the iron oxide have recently been developed. 80 Regener-
ative liquid absorption systems using such absorbents as
-------
52
annuonium carbonate, sodium thioarsenate, and sodium arsenate
38,42
solutions have also been used. Similarly, various liquid
absorbents have been used in the chemical industry for removal
of hydrogen sulfide in gas streams. For example, hydrogen
sulfide liberated in the production of sulfur dyes in
aniline plants is effectively absorbed by alkali in scrub—
83
bers. Another commonly used method for preventing release
of hydrogen sulfide to the atmosphere in the chemical
industry is to collect the various gaseous vents and destroy
128
them by incineration.
4.4 Coal Piles
The pollution of the atmosphere in the vicinity of
burning coal refuse piles an be minimized by constructing
the refuse piles in such a manner that ignition is minimized
131
and it is possible to easily extinguish a fire.
4.5 Tanneries
In the tanning industry, practices adopted in modern
tanneries in Russia have essentially eliminated the hydrogen
sulfide problem. These cxnsist of more rapid processing of
raw material, use of lime solutions to destroy hide .proteins
and alkalize a dium sulfide, and neutralization of the
semimanufactured products to eliminate residual sodium sulfide
119
which previously cxntaminated acid—tanning solutions.
-------
53
4.6 Sewers and Sewage Plants
In sewage plants, the most comprehensive elimination
of hydrogen sulfide is accomplished by enclosing the process
77
and venting the gases to an incinerator. Other methods of
removing hydrogen sulfide are absorbing or chemically
oxidizing the gas. The oxidation process is utilized in New
77
York City and Sarasota, Fla. Other methods consist of
odor—masking with sc&ited mint, catalytic combustion, and
77
odor counteraction.
In sewers, the production and release to the atmo-
sphere of hydrogen sulfide can be minimized by maintaining
sufficient velocities of sewage to avoid sulfide buildup
and minimizing lines of pressure and points of high
turbulence. Atmospheric pollutions may also be controlled
by adequate ventilation, injection of air to maintain aeration
conditions, cleaning of sewers to remove slime and silt,
use of chemicals such as chlorine and ozone for suppressing
90
biological activity, and addition of specific biological
life to suppress the development of organisms producing
114
the hydrogen sulfide. A method of preventing release
of hydrogen sulfide to the atmosphere which has had some
degree of success is trapping the gas in laterals, branches,
114
and mains by use of specially designed junctions. A
method utilized by the County Sanitation District of
-------
54
Los Angeles to control hydrogen sulfide is to add lime
114
slurry to sewage periodically in relatively large quantities.
4e 7 General Abatement Systems
63
Kalyuzhnyi et al. reported that reduction of hydro-
gen sulfide and other pollutants in air was achieved by
placing a green vegetation belt between the industrial emitter
and the residential areas. They observed that hydrogen
sulfide concentrations outside the green belt then decreased
from 70 g/m 3 to 30 Lg/m 3 at 500 meters, while inside the
green belt the hydrogen sulfide concentrations decreased
from 70 .ig/m 3 to 25 i.ig/m 3 ; this difference was considered
significant by the author.
-------
55
5. ECONOMICS
Incidents in which hydrogen sulfide caused metal-
tarnishing and paint blackening have been reported in areas
adjacent to kraft paper mills, industrial waste lagoons,
and water aeration plants, as outlined in the section on
Effects. In one instance in Terre Haute, md ., effects
on health were reported. However, few persons ught
medical attention. The economic inpact of the losses was
not reported. The major economic effect of hydrogen sulfide
pollution on the general public is the nuisance effect (due
to the foul smell), with the resultant decrease in property
values in areas adjacent to emitters. No information was
available on the value of property in a hydrogen sulfide—
polluted area in relation to an area not polluted by
hydrogen sulfide.
Tarnishing of metals has necessitated the use of
gold in electrical contacts instead of silver, which is
sensitive to hydrogen sulfide corrosion. It has been
estimated that if silver could be used instead, in 1963
a savings of approximately $14.8 million could have been
67
realized.
In cases of severe hydrogen sulfide pollution, the
economic inpact is substantial. For instance, in Poza Rica,
Mexico, 22 people died, 320 persons were hospitalized, and
100 percent of the canaries and 50 percent of the livestock
-------
56
and domestic animals died. However, no information was
found on the magnitude of the cost to residents of the
area.
Major expenditures have been made in kraft plants,
natural gas plants, coke—oven plants, and chemical plants
to minimize the release of hydrogen sulfide and other odor-
producing sulfur czmpounds to the atmosphere. However, no
studies were found on the total dollar value of abatement
equipment or systems or their operation. The pulp and
paper industry has spent $75 million to date to control air
emissions. This includes $40 mi].],ion spent over the last
four years. In the next four years the industry expects
to spend $60 million. The cost includes the amounts spent
for all phases of air pollution, including process changes
40
in kraft mills. The percent of the total expenditure
associated with hydrogen sulfide abatement is not known.
Major expenditures have been made by refineries and
natural gas plants to remove hydrogen sulfide from sour
gases and to recover the sulfur. The cost of desulfuriza—
tion plants and sulfur—recovery plants is shown in Figure 6
and Figure 7. However, the value of the sulfur recovered
generally exceeds the cost of construction and operation of
the facilities required to recover it. Data on the produc-
tion of hydrogen sulfide are presented in Section 3.
-------
700
500
400
300
200
150
100
70
50
40
30
20
Co
0
0
C
Co
cn
0
-c
H
C l )
0
C.)
(0
0)
a,
( ‘3
E
x
0
0.
0.
Approximate Cost of Gas DesulfUriZatiofl Plants
-o
Co
U,
C
0
F-
0)
C
0
-J
> .
a,
>
0
C .,
a,
4 - I
C
Co
0
4-
In
‘U (j
2,500
1,500
1,000
700
500
400
300
200
100
20 30 5070100
Mil’ion Standard Cubic Feet Per Day
Capacity )
Key
Approximate 1967 cost.
b Sulfur plant recovery, based on 96% recovery of hydrogen sulfide,
and 90% recovery of sulfur in sulfur plant.
1 - 20 a Hydrogen sulfide in gas, %.
FIGURE 6
in 196792
1 2 3 5 7 10
(amine or other types)
-------
In Thousands
of Dollars
10,000
U
1,000
100
10
Long Tons / Day
* Product capacity based on:
Hydrogen Sulfide in Sour Gas, %
10
20
50
100
% Hydrogen Sulfide n gas.
FIGURE 7
% Sulfur Recovery in Sulfur Plant
89
91
93
95
58
1 10 100
1,000
Sulfur—Recovery Plant Investment 48
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59
6. MET1 DDS OF P NALYSIS
The methods used in air pollution studies for
hydrogen sulfide analysis are mainly based on iodometrjc
methods such as titrating with iodine, methylene blue methods,
molybdenum blue methods, and various modifications of the
lead acetate paper and tile methods. The methylene blue
method is based on precipitating cadmium sulfide from
alkaline suspension of cadmium hydroxide by hydrogen sulfide
in a known air sample. The alkaline suspension of cadmium
hydroxide is contained in a standard impinger (0—i CFM),
through which is drawn the sample of air to be analyzed.
The sulfide ion is then reacted with a mixture of p-amino-
dimethyl—aniijne, ferric ion, and chloride ion (ferric
chloride) to yield methylene blue. The concentration of
hydrogen sulfide is then determined optically by a colon—
meter or spect.rophotometer. 59 ’ 60 ’ 124 This method is good
for hydrogen sulfide determinations down to the ig/m 3
range. Lahinann and Prescher 73 found that the cadmium
sulfide suspensions are unstable at low concentrations and
are decomposed by light. From tests run on samples of air
ntaining from 7 to 170 IJg/m 3 , they concluded that the
method of sampling (i.e, , amount of light which penetrates
the sample) will affect the analytical results. Recently
Ban berger and Adams 18 claimed to have minimized these
-------
60
problems by adding arabinogalactan, avoiding exposure to
light, and analyzing the samples as soon as possible after
collection. By this procedure they claim a sensitivity of
a few ppb of hydrogen sulfide in a 240 liter sample taken
over a 2—hour period. This improvement gives about an 80
percent recovery of hydrogen sulfide.
Variations on the methylene blue method include the
absc rpt ion of the hydrogen sulfide in zinc acetate instead
of the cadmium salts. However, this variation is not as
accurate as the cadmium salt method because zinc acetate
loses hydrogen sulfide during sampling by air stripping and
aging if allowed to stand for more than 2 hours. In addition,
the collection efficiency for cadmium hydroxide is reported
52
to be higher than for zinc acetate.
The molybdenum blue method is based on absorbing
the hydrogen sulfide from the air sample in an acid solution
of aniuoniuxn molybdate. The color developed in the ainmonium
molybdate by the hydrogen sulfide is determined optically by
27,112
a colorimeter.
The cadmium sulfide method is an example of the
iodornetric methods for deterxnining hydrogen sulfide concen-
tration in air. A known quantity of air is passed through
two bubblers in series containing ammoniacal cadmium chloride
solution. The collected samples are then stripped of any
-------
61
trapped sulfur dioxide, and the cadmium sulfide precipitate
is dissolved in concentrated hydrochloric acid. The solution
is then titrated with iodine using starch as the indicator.
The hydrogen sulfide concentration in the air can be
calculated from the amount f iodine added. Other cadmium
solutions——cadmium acetate, for example——can be used as the
59
absorbing solution. This method is accurate to about 700
59
ig/m 3 for a 30-liter air sample.
The spot method using paper or tiles impregnated with
lead acetate has been widely used to measure low concentra-
tions of hydrogen sulfide in the atmosphere. The tiles are
preferred in air pollution work. The unglazed tiles are
impregnated with lead acetate and exposed in a place where
they will be protected from rain. After exposure, the shade
of the tiles is compared with kr1own standards to estimate
the concentration of hydrogen sulfide. In general, this
method does not give accurate quantitative results, but
rather, an indication of relative exposures of various
59,124
localities to hydrogen sulfide. Gilardi and
43
Manganelli did experimental studies on the light absorbence
of lead acetate—impregnated tile surfaces after exposure to
various concentrations of hydrogen sulfide to develop an
accurate quantitative measurement technique. From their
experiments they concluded the following:
-------
62
(1) Exposure unit ( ) is a useful parameter in
representing hydrogen sulfide exposure.
(2) Average concentrations of hydrogen sulfide
between 150 and 1,500 1g/m 3 can be determined by the measure—
merit of surface absorbency of lead acetate.
(3) Fading of darkened tiles is accelerated by
air turbulence and light.
Chiarenzelli and Joba 3 ° also found that the tiles
faded on standing and that oxidation products formed. From
these facts they concluded that the lead acetate tile method
is unsatisfactory for periods greater than a day or two.
Automatic tape samplers based on lead acetate—
impregnated filter paper have been developed for field air
pollution application which continuously measure the
hydrogen sulfide content of the atmosphere. The AISI or
Hemeon tape sampler draws a known quantity of air through
lead acetate-impregnated filter paper. If hydrogen sulfide
is present in the atmosphere, a dark spot is formed which
is measured by determining the optical density of the spots
as compared to a standard. 36 Sanderson, Thomas, and Katz 113
reported that field experience has shown that large measure-
ment errors can occur due to fading of the color of the
precipitated lead sulfide spots by action of light, sulfur
dioxide, ozone, or any other substance capable of oxidizing
-------
63
lead sulfide. This fading may even occur during the
sampling period. The fading can occur in a short time and
a negative result is therefore not indicative of the absence
113
of hydrogen sulfide. Other factors that affect the
accuracy of the AISI tape sampler are relative humidity of
the air and the consistency of absorbence of the blank
113 52
paper. On the positive side, High and Horstman
reported obtaining results with the AISI tape sampler that
were in reasonably good agreement with results obtained by
the methylerie blue method. They stated that the lead sulfide
stains produced on the lead acetate filter paper did not
fade significantly during an 8-week storage period when
stored in vapor— and moistureproof bags.
98
Pare suggested that mercuric chloride—impregnated
filter paper be used in tape sampler paper as an improvement
over the lead acetate—impregnated paper. He reported that
the mercuric chloride paper tape is sensitive and reliable
for determination of hydrogen sulfide in air and the spots
are stable even in the presence of high levels of ozone,
nitrogen oxides, and sulfur dioxide. He stated that it
provided an adequate sensitivity on the order of 700 14g/m 3 .
36
Dubois and Monlcman reported that although the spots formed
by hydrogen sulfide on the mercuric chloride tape are
resistant to fading effects, sulfur dioxide in the air
-------
64
results in a substantial change in hydrogen sulfide threshold
of the tape.
38
Falgout and Harding reported a method based on
drawing air through a silver membrane filter. The hydrogen
sulfide reacts to form silver sulfide, which results in a
decrease in the reflectance of the silver surface. The
reflectance of the membrane is measured before and after
exposure, and the decrease in reflectance is proportional
to the nydrogen sulfide exposure. This method is also
sensitive to mercaptans in the air. Other methods have been
used whereby silver coupons or coupons coated with lead—
base paint are exposed to air. The sulfide formed is removed
and analyzed by the methylene blue method. Silver tarnishing
of coupons as measured by light reflectance has also been
used as a tool for measuring relative concentrations of
52
hydrogen sulfide at various locations. Detector tubes
containing inert particles coated with silver cyanide or
lead acetate have been developed for testing for hydrogen
11].
sulfide. The sensitivity of this method is 0.04 .ig
with a detection limit of 140 g/m 3 .
Gas chromatographs with minimum detection threshold
for hydrogen sulfide of 150 i-’g/m 3 have been used in air
14,82 2
pollution and industrial rk. Adams and Koppe
determined that with a gas chromatograph, the bromine
-------
65
microcoulometric titration cell had the greatest potential
for fulfur—specific analysis at a sensitivity required for
direct analysis of small—volume samples. Hydrogen sulfide
concentrations in the range of 15 p.g/m 3 to 1,200,000 ..ig/m 3
can be measured by an electrolytic titrator which is
preceded by a gas scruNer train to remove interfering sulfur
133 72
compounds. Lahrriann reported that a sensitive new
instrument based on galvanic measuring cells ha been
developed in Germany for measuring the hydrogen sulfide
content of air.
-------
66
7. JNMARY AND (X)NCLUSI0I S
Hydrogen sulfide is highly toxic to humans, and at
concentrations over 1,000,000 g/m 3 quickly causes death
by paralysis of the respiratory system.. At lower concen-
trations, hydrogen sulfide may cause conjunctivitis with
reddening and lachrymal secretion, respiratory tract
irritation, psychic changes, pulmonary edema, damaged heart
muscle, disturbed equilibrium, nerve paralysis, spasms,
unconsciousness, and circulatory collapse.
The odor threshold for hydrogen sulfide lies between
1 and 45 .ig/m 3 . Above this threshold value, the gas gives
off an obnoxious odor of rotten eggs, which acts as a
sensitive indicator of its presence. At these concentrations,
no serious health effects are known to occur. At 500 iig/m 3 ,
the odor is distinct; at 30,000 to 50,000 1g/m 3 the odor
is strong, but not intolerable; at 320,000 i.ig/m 3 , the odor
loses some of its pungency, probably due to paralysis of
the olfactory nerves. At concentrations over 1,120,000 g/tn 3 ,
there is little sensation of odor and death can occur
rapidly. Therefore, this dulling of the sense of smell
constitutes a major danger to persons exposed to high
concentrations of hydrogen sulfide.
Hydrogen sulfide produces the same health effects on
domestic animals as on man, and at approximately the same
concentrations.
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67
REFER ENCES
1. Adams, D. F., and R. K. Koppe, An Air Quality Study in the
Vicinity of Lewiston, Idaho and Clarkston, Washington, J. Air
Pollution Control Assoc . 16(6) (1966).
2. Adams, D. F., and R. K. Koppe, Direct GLC Coulometric Analysis
of Kraft Mill Gases, J. Air Pollition Control Assoc . 17(3) (1967).
3. Adams, D. F., and. F. A. Young, Kraft Odor Detection and. Objec-
tionability Thresholds, Washington State University Progress
Report on U. S. Public Health Service Grant (1965).
4. Air Pollution, Factory (Oct. 1965).
5. Air Pollution and Health—A Statement by the American Tobacco
Society Committee on Air Pollution, Am. Rev. Respirat. Diseases
93(2) (1966).
6. Air Pollution in the Iron and Steel Industry, Organization for
Economic Cooperation and Development, No. 15985 (1963).
7. The Air Pollution Situation in Terre Haute, Indiana, with Special
Reference to the Hydrogen Sulfide Incident May—June 1964, A Joint
Report to the City of Terre Haute by U. S. Public Health Service,
Division of Air Pollution, and Indiana Air Pollution Control
Board, Division of Sanitary Engineering (June 1964).
8. Air Quality in Clark County, Washington, Air Sanitation and
Radiation Control Section, washington Department of Health (1965).
9. Air Quality Standards and Air Pollution Control Regulations for
the St. Louis Metropolitan Area, Preprint. Missouri Air Conser-
vation Commission, Jefferson City, Mo. (Peb. 22, 1967).
10. Alkire, G. J., and C. R. Wyss, Air Quality Survey at Selected
Sites on the Hanford Project, Pacific Northwest Laboratory BNWL-
564, Richiand, Washington (Nov. 1967).
11. Altybaev, M., and V. V. Streltsov, Removal of Sulfur Compounds
from Gaseous Fuels, Coke Chem. (USSRJ 8 43 (1966).
12. Ambient Air Quality Criteria, Adopted by the Commonwealth of
Pennsylvania, Department of Health, Air Pollution Commission
(April, 1967).
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68
13. Annual Report, Department of Air Pollution Control, City of New
York (1962).
14. Applebury, T. E., and M. J. Shaer, Analysis of Kraft Pulp Mill
Gases by Process Gas Chromatography, Preprint. Montana State
University, Department of Chemical Engineering (1968).
15. Atmospheric Emissions from Petroleum Refineries—A Guide for
Measurement and Control, U. S. Public Health Serv. Publ. 763
(1960).
16. Atmospheric Pollution in the Great Kanawha River Valley Indus—
trial Area, The West Virginia Department of Health and the
Kettering Laboratory, University of Cincinnati (1952).
17. Baikov, B. K., Basic Experimental Data for the Determination of
Maximum Permissible Concentrations of Carbon Disulfide and
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-------
APPENDIX
-------
‘I ‘ ,-----
L ‘ -‘ ‘ .-L , ) I )
4 I a
,\ I
I I I ‘ —
r—x. ‘ L :
‘ a —— I
I I_ • ___ ‘ .4, , . I •
I 4. S
5 d
—
FIGURE 8
APPENDIX
82
—
---4 --..
r
S
Location of Kraft Mills in United States (1957)68
-------
APPENDIX 83
TABLE 15
41,49,101,102,140
EFFECTS OF HYDROGEN SULFIDE ON HUMANS
Concentr t ion
( ig/m ) Effects
1—45 Odor threshold. No reported injury
to health
10 Threshold of reflex effect on eye
sensitivity to light
150 Smell slightly perceptible
500 Smell definitely perceptible
15,000 Minimum concentration causing eye
irritation
30,000 Maximum allowable occupational
exposure for 8 hours (ACGIH
Tolerance Limit)
30,000—60,000 Strongly perceptible but not in-
tolerable smell. Minimum con-
centration causing lung irritation
150,000 Olfactory fatigue in 2—15 minutes;
irritation of eyes and respira-
tory tract after 1 hour; death
in 8 to 48 hrs
270,000-480,000 No serious damage for 1 hour but
intense local irritation; eye
irritation in 6 to 8 minutes
640,000—1,120,000 Dangerous concentration after 30
minutes or less
900,000 Fatal in 30 minutes
1,160,000—1,370,000 Rapid unconsciousness, respiration
arrest, and death, possibly
without odor sensation
1,500,000+ Immediate unconsciousness and rapid
death
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APPENDIX 84
TABLE 16
TINE REQUIRED FOR 50 PERCENT MORTALITY OF SUBJECTS TREATED
WITH HYDROGEN SULFIDE 66
(In Minutes)
Subject
Number
Studied
H 2 S C
oncentration
(in .‘g/m 3 )
1,500,000 380,000
96,000
24,000
Flies
250
7
>960
Mice
4
18
410
804
>960
Rats
8
14
>960
>960
>960
-------
APPENDIX
TABLE 17
TYPICAL GROSS FINDINGS AT AUTOPSY OF RATS AND MICE
WHICH DIED DURING E) ’OSURE TO HYDROGEN SULFIDE 139
Concentration of Hydrogen Sulfide Gas (in
96,000
-— 1,500 O0
Rats (8) Mice(4)
Very slightly
congested
Natural Same as
rats
Well coll 1 psed, Same as
dark pink, cut rats
surface wet,
rare small
hemorrhages
380,000
Rats (8) Mice (4)
Congested Slightly
congested
Natural Natural
Partly distended, Massive
extremely hemDrrhages
hemorrhagic of all lobes
Rats (8) Mice (4)
Congested Congested
Natural Natural
One-half col— Deep red,
lapsed, many apparently
small hemor— massive hemor—
rhages rhage
In systole,
atria dilated,
blooc fluid
Much congested
Not distended
bladder
Same as
rats
Same as
rats
Same as
rats
Distended
Congested
Not distended
Moderate dila—
tation of
right side
Moderately en—
larged, very
pale, lobules
not exaggerated
Definitely but
moderately
distended
Moderate dila—
tation of
right side
Medium
dark red
Not distended
Moderately
dilated
Pale, nutmeg
color, large
Not distended
to moderately
distended
-------
APPENDIX
TABLE 17 (Continued)
TYPICAL GROSS FINDINGS AT AUTOPSY OF RATS AND MICE
WHICH DIED DURING EXPOSURE TO HYDROGEN SULFIDE
Organ
Concentration of Hydrogen Sulfide Gas (in p g/m ’)
1,500,000 380 000 96,000
-—
Rats (8)
Mice(4)
- Rats (8)
Mice f4)
Rats (8)
Mice (41
Stomach
Moderately to
greatly distended,
few small
hemorrhages
Same as
rats
Distended, few
small hemorrhages
Definitely but
moderately
distended, rare
minute hernor—
rhages
Defthitely but
moderately
distended, mod-
erate number of
small hemor-
rhages
Moderately di
tended, few
hemorrhages o
moderate size
Intew-
Natural or with
Same as
Large, partly
Small intestine
Cecum moderately
Duodenum
tines
a few small
hemorrhages
rats
distended
slightly dis—
tonded
distended
dilated
Adrenals
Natural, pink
Same as
rats
Pink
Pale
Natural
Natural
Kidneys
Much congested
Moder-
ately
conges-
ted
Congested
Pale
Medium dark
red
Pale
-------
APPENDIX 87
TABLE 18
PERCENTAGE OF LEAF AREA MARKED BY HYDROGEN SULFIDE 2 °
(Four-Hour Fumigations)
- Concentration of
Hydrogen
Sulfide
-
750,000 ig/m’
150,000 1g/m
3wka 6w]ca 6wka
3wka
6wka
6wka
Plant
Moistb Moistb Dryb
Noistb
Noistb
Dryb
Lamb’s—quarters
100 69 100
53
100
28
Nettle—leaf goosefoot
91 54 83
64
88
24
Chickweed
100 55 88
41
34
29
Dandelion
75 45 76
16
26
13
Sunflower
53 45 78
28
26
17
Kentucky bluegrass
70 28 77
21
18
16
Pigweed
52 31 53
12
23
32
Annual bluegrass
66 18 64
17
9
7
Mustard
52 20 65
16
13
11
Cheeseweed
32 34 53
10
10
3
aAge of plants.
bSojl cnndition .
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APPENDIX
TABLE 19
RELATIVE SENSITIVITY OF PLANTS TO HYDROGEN SULFIDE 2 °
Sensitive
Intermediate
Resistant
Lau b’s—quarters
Dandelion
Annual bluegrass
Nettle—leaf goosefoot
Sunflower
Mustard
Chickweed
Kentucky bluegrass
P igweed
Cheeseweed
88
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89
APPENDIX
TABLE 20
CRUDE OIL CAPACITY IN THE UNITED STATES AS OF JANUARY 1969130
Alabama
Alaska
Arkansas
California
Colorado
Delawae
Florida
Georgia
Hawa ii
Illinois
Indiana
Kansas
Kentucky
Louisiana
Maryland
Michigan
Minnesota
Mississippi
Missouri
Montana
Nebraska
New Jersey
New Mexico
New York
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Rhode Island
Tennessee
Texas
Utah
Virginia
Washington
West Virginia
Wisconsin
Wyoming
Total
6
1
6
32
4
1
1
2
1
11
10
12
3
16
2
8
3
4
1
9
1
6
6
2
2
11
14
1
13
1
1
47
5
1
6
2
2
9
263
34,620
20,000
93,500
1,529,075
42,900
140,000
3,100
9,500
35,000
704,100
565,700
389 ,300
128,500
1,190,850
19,400
146,050
138,300
168,700
83,000
128,200
4,000
523,500
42,610
76,900
55,000
491,600
449,367
11,000
628,920
7,500
28,500
3,118,250
11,950
43,600
219,000
8,570
29,500
132,900
11,522,512
36,820
21,000
94,985
1,606,985
46,235
150,000
3,150
11,000
NR
732,300
588,800
407,300
132,600
1,230,000
20,500
152,000
144,000
181,500
84, 700
137,500
4,500
555,000
44, 400
81,000
57,000
525,900
464, 250
12,000
659,100
10,000
29, 750
3,244,300
116,400
45,000
226,000
9,100
30,600
146,686
12,079,201
State
No.
Plants
Crude Capacitya
b/cdb b/ 5d
aState totals include figures converted to calendar—day
or stream—day basis.
bb/cd = barrels per calendar day.
cb/sd barrels per stream—day.
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90
APPENDIX
TABLE 21
KRAF PULP PRODUCTION IN THE UNITED STATES’ 05
Mill ion
Year Tons/Year
1957 12.8
1958 13.1
1959 14.9
1960 15.3
1961 16.1
1962 17.4
1963 18.7
1964 20.4
1965 22.3
1966 24.4
1967 23.9
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91
APPENDIX
TABLE 22
UNITED STAT ES COKE PRODUCTION 89
Year
19 57—59
1964
1965
1966
Ton s/Year
60.5 x io 6
60.9 x io6
65.2 x io 6
66.0 x io6
Nuiriber of
Oven Slots
15,993
14,639
14,357
14,720
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