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 ------- 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: ------- 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 ------- 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 ------- 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 ------- 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 ------- 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 ------- 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 ------- 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 ------- 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 ix ------- 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 ------- 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 ------- 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 ------- 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. ------- 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. ------- 3 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. ------- 4 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 ------- 5 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. ------- 6 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 ------- 7 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 ------- 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 ------- 9 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. ------- 10 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). ------- 11 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 ------- 12 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 ------- 13 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 . ------- 14 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 ------- 15 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 ------- 16 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- . ’ ------- 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 ------- 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 ------- 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. ------- 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 ------- 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. ------- 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 ------- 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 ------- 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 . 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Zimmerman, W., Impurities in Air and Their Influence on Plant Life, Proceedings of the First National Air Pollution Symposium (1949). ------- 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 ------- 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 . ------- 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 ------- 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. ------- 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 ------- 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 ------- |