PRELIMINARY AIR POLLUTION SURVEY OF AMMONIA 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: U. S. Department of Commerce National Bureau of Standards Clearinghouse for Federal Scientific and Technical Information Springfield, Virginia 22151 ------- PRELIMINARY AIR POLLUTION SURVEY OF AMMONIA 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 readership. 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 69-25 ------- 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) Ethylene Aldehydes (includes acrolein Hydrochloric Acid and formaldehyde) Hydrogen Sulfide Ammonia Iron and Its Compounds Arsenic and Its Compounds Manganese and Its Compounds Asbestos Mercury and Its Compounds Barium and Its Compounds Nickel and Its Compounds Beryllium and Its Compounds Odorous Compounds Biological Aerosols Organic Carcinogens (microorganisms) Pesticides Boron and Its Compounds Phosphorus and Its Compounds Cadmium and Its Compounds Radioactive Substances Chlorine Gas Selenium and Its Compounds Chromium and Its Compounds Vanadium and Its Compounds (includes chromic acid) 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 iii ------- 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 epidemic- 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 Pinkelstein, Ph.D. Douglas A. Olsen, Ph0D. 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. ------- ABSTRACT Ammonia is a natural constituent of the atmosphere but exists in concentrations below the level which is hazardous to humans, animals, plants, or materials. High concentra- tions of ammonia gas are corrosive to mucous membranes; can cause damage to the eye, throat, and upper respiratory tract; and can produce residual damage and even death in humans and animals. High concentrations are also toxic to most plant life and have corrosive effects on materials. Almost all of the ammonia in the atmosphere is produced by natural biological processes, largely from the decomposi- tion of organic waste material. Man contributes a compara- tively small portion of ammonia to the atmosphere, mainly through combustion and industrial processes involved in the production or use of ammonia. Air quality standards for ammonia concentrations have not been established in the United States. Measurements of environmental concentrations indicate average levels of 3 approximately 20 |_ig/m • Wet scrubbers, bag filters, and charcoal filters are used to control industrial losses of ammonia to the atmosphere. The economic value of ammonia encourages its conservation in commercial processes. No economic data are available on damages caused by ammonia pollution. Adequate methods are available for the detection and measurement of ammonia in the atmosphere. vii ------- LIST OF FIGURES 1. Total Catalytic Cracking Capacity of Oil Refineries . 15 2. Trends in Electric Utility Fossil Fuel Consumption . 17 3. Motor Gasoline Demand 18 LIST OF TABLES 1. Gross Findings at Autopsy of Rat Exposed to 700,000 |-ig/m3 Ammonia 4 2. Time in Minutes Until 50% Injury to Exposed Plant Surfaces at 700,000 ug/m3 6 3. Percentage of Leaf Area Marked by Ammonia 7 4. Relative Sensitivity of Weeds to Ammonia 7 5. Ambient Air Quality Standards for Ammonia 9 6. Ammonia Production in 1968 12 7. U.S. Coke Production 13 8. Ammonia Released from Oil Refineries 13 9. Ammonia Emission from Catalytic Cracking Unit Regenerator Stacks (Los Angeles Refineries) 14 10. Ammonia Emissions from Combustion 16 11. Pounds of Ammonia Discharged Daily in Metropolitan Area of 100,000 Persons Using Each Heating System . . 17 12. Miscellaneous Ammonia Emissions 20 13. Catalytic Cracking Capacity of Oil Refineries in U.S.A. (Jan. 1968) 32- 14. Ammonia Emissions from Incineration .33 15. Pounds of Ammonia Discharged Daily in a Metropolitan Area of 100,000 Persons 34 16. U.S. National Ammonia Concentration 35 17. Concentrations of Ammonia in Air, United States ... 36 i* ------- CONTENTS FOREWORD ABSTRACT 1. INTRODUCTION „ 1 2. EFFECTS ....«, . 2 2.1 Effects on Humans <,.. 2 2.2 Effects on Animals 3 2.2.1 Commercial and Domestic Animals .... 3 2.2.2 Experimental Animals 3 2.3 Effects on Plants ....» 5 2.4 Effects on Materials 8 2.5 Environmental Air Standards 8 3. SOURCES 10 3.1 Natural Occurrence 10 3.2 Production Sources 11 3.2.1 Haber-Bosch Process 11 3.2.2 Coke Plants 12 3.2.3 Oil Refineries . . . „ 13 3.2.4 Metallurgical and Ceramic Plants . . . » 14 3.2o5 Combustion Processes 16 3o3 Product Sources 19 3.4 Environmental Air Concentrations 20 4. ABATEMENT 21 5. ECONOMICS 22 6. METHODS OF ANALYSIS 23 REFERENCES 25 APPENDIX 31 X1 ------- 1. INTRODUCTION The main source of atmospheric ammonia is naturally- produced ammonia which is released from land and ocean areas. In terms of total air content of ammonia, urban-produced ammonia is of lesser importance, though it may be important from the air pollution standpoint in localized situations. The primary source of ammonia air pollution in cities is the combustion process involved in the combustion of fuels, incineration of wastes, and use of the internal combustion engine. Industrial sources emitting ammonia are chemical plants, coke ovens, and refineries. Other sources are stock- yards and similar installations, where ammonia is formed by biological degradation. ------- 2. EFFECTS 2.1 Effects on Humans Ammonia gas, if inhaled, affects mainly the upper res- piratory tract, according to Jacobs.30 Only a small percen- tage of an inhaled dose reaches the lungs at the inhaled concentration. At high concentrations (1,700,000 ug/m to 4,500,000 (ag/m ), ammonia acts as an asphyxiant. At concen- 3 "3 trations of 280,000 ug/m to 490,000 |ag/m the gas can produce eye, nose, and throat irritation. 62 Silverman et al. exposed seven adult males to ammonia gas concentrations of 350,000 |jg/m . Significant effects on respiration resulted, as well as irritations of the throat and nose and hypoesthesia. 07 Kustou ran 7-to-8-hour tests to determine the effect of ammonia on certain physiological and biological indexes in man. He found that at concentrations of 13,000 |_ig/m3 the urea and ammonia content of the blood and the urine increased. In addition, he noted a lowering of the oxygen use factor and some respiratory depression. In 1955 Hemeon^ suggested that zinc ammonium sulfate aerosols were in part responsible for the irritant effects of the air during the Donora Smog Episode in 1948. Amdur 4 and Corn found that aerosols of zinc sulfate, zinc ammonium sulfate, and ammonium sulfate produced severe irritation in guinea pigs. The double salt was the most irritative. They established that the smaller the particles, the greater the ------- irritative action and that the aerosols, in conjunction with sulfur dioxide gas, produced synergistic effects. This synergistic effect was particularly enhanced when the ammo- nium sulfate and zinc ammonium sulfate were combined with sulfur dioxide gas. 2.2 Effects on Animals 2.2.1 Commercial and Domestic Animals No reports were found on effects of ammonia on livestock, although they can be expected to be negligible at the low concentration normally found in urban or rural atmospheres. High localized concentrations due to accidental releases of ammonia could cause significant effects. 2.2.2 Experimental Animals Several studies have been made on the effects on experi- mental animals both of ammonia alone and of ammonia and carbon 7fi combinations. Weedon reported that guinea pigs and rabbits exposed to 1,740,000 |jg/m of ammonia developed acute and chronic lung lesions. The rabbits were less sensitive than the guinea pigs, which tolerated around 1,000,000 |_ig/m3. When Weedon exposed house flies to ammonia concentrations 3 of 700,000 i_ig/m , 6 percent of the flies were killed in 16 •3 hours. He also exposed mice and rats to 700,000 |_ig/m of ammonia for 16 hours. Two older animals showed some evidence of slight dyspnea. At the end of the exposure, the eyes of all the rats and mice were bright, with little or no evidence of lacrimation. The gross findings at autopsy for one rat ------- (considered typical of the exposed group), which died 12 hours after exposure are shown in Table 1. TABLE 1 GROSS FINDINGS AT AUTOPSY OF RAT EXPOSED TO 700,000 |_ig/m3 AMMONIA 76 Findings Organs (Rat which died 12 hr. after exposure) Brain Slightly congested Trachea Not reddened Lungs Two-thirds distended, many large hemorrhages, cherry-red, waxy, cut surface foamy Heart Much distended Liver Congested Gall bladder Not distended Stomach Moderately distended, few hemorrhages Intestines Large intestine partly distended Adrenals Pink .Kidneys Congested Peritoneal surfaces Not remarkable 74 3 Weatherby exposed guinea pigs to 118,000 |ig/m of ammonia and found mild changes in kidneys, spleen, adrenals, and liver in 18 weeks. No change was found in 12 weeks. 13 J. Dalhamn found that low concentrations of ammonia (2,000 ) caused the cilia of the upper respiratory tract of rats pQ to stop beating in 8 to 9 minutes. Friberg found that the process of arresting the cilia was reversible until concentra- tions around 210,000 lag/m3 of inhaled air were reached. ------- 14 •} T. Dalhamn and L. Reid exposed rats to 70,000 ng/m° of ammonia and 7,000 |_ig/m of pulverized carbon in air for 6 months. The severe mucosal damage and impairment of ciliary activity observed suggested a synergistic effect. 2.3 Effects on Plants Thornton exposed tomato plants, buckwheat, and tobacco plants to air concentrations of ammonia of 700; 2,800; 1,000; 44,000; 175,000; and 700,000 |_ig/m3 in air for periods of 1, 4, 15, 60, and 240 minutes. He found that ammonia at 700,000 |ag/m3 caused changes in the pH of tomato plant leaf and stem tissue but did not cause damage at lower concentra- tions. He also found that there was some correlation between pH change and observed injury. The time required to produce injury to 50 percent of the exposed plant surfaces at 700,000 |jg/m is shown in Table 2. In general, acute injury due to ammonia is shown by a collapse of tissue without subsequent loss of chlorophyll. Definite injury was observed on buck- wheat, coleus, sunflower, and tomato after exposure to 38,000 p.g/m of ammonia for about 1 hour; slight injury was observed at 11,500 |_ig/m3 after 4 hours; and at 5,600 lag/m3, the plants were either uninjured or slightly marked after 5 hours. Nearly all parts of the leaf had a cooked green appearance which became brown upon drying.^7*64,69-71 73 Treshaw indicated that ammonia can induce glazing and silvering, particularly of lower leaf surfaces of vegetables. ------- TABLE 2 TIME IN MINUTES UNTIL 50% INJURY , 71 TO EXPOSED PLANT SURFACES AT 700,000 Part of Plant Plant Time (min) Leaves Tomato 3 Buckwheat 5 Tobacco 8 Stems Tomato 60 Buckwheat 30 Tobacco 240 9 Benedict and Breen fumigated 10 species of common weeds which occur throughout the United States in an effort to develop a method for identifying pollutants causing damage. The ammonia produced spots of cell collapse and death, primar- ily along the margins of the leaves. With grasses, small spots developed over the area where the leaf bends, giving a powdery appearance. The powdery marking increased in the region be- tween the bend and the tip as the intensity of fumigation was increased. Table 3 shows the percentage of leaf area marked <3 o by ammonia at concentrations of 8,400 (jg/mj and 2,100 ug/m . Table 4 shows the relative sensitivity of the weeds to ammonia. g Barton exposed radish seeds and spring rye seed to •j q 700,000 ng/m and 175,000 ug/m of ammonia in air. Both dry and soaked seeds were used in each case. The germination of soaked radish seeds exposed for as long as 240 minutes to 700,000 ng/m3 of this gas was not only delayed but actually ------- TABLE 3 PERCENTAGE OF LEAF AREA MARKED BY AMMONIA" (Four-hour fumigations) Plant Concentration of Ammonia 8,400 uq/m3 2,100 uq/m3 3 wk£6 wka6 wka Moist" Moistb Dry13 3 Moist 6 wkf 6 wkc Moist: Dry ,b Mustard 33 48 8 Sunflower 32 32 2 Lamb' s-quarters 5 20 11 Cheeseweed 5 19 3 Annual bluegrass 6 11 1 Kentucky bluegrass 4 13 1 Dandelion 382 Chickweed 191 Pigweed 242 Nettle-leaf goosefoot 111 15 4 2 1 2 0 0 0 1 0 10 2 2 1 1 0 0 0 2 0 8 2 1 1 1 0 0 0 1 0 Age of plants. "Soil condition. TABLE 4 RELATIVE SENSITIVITY OF WEEDS TO AMMONIA9 Sensitive Intermediate Resistant Mustard Sunflower Lamb's-quarters Cheeseweed Annual bluegrass Kentucky bluegrass Dandelion Chickweed Pigweed Nettle-leaf Goosefoot ------- 8 reduced. An extension of the treatment period to 960 minutes killed all of the seeds. A 1-minute exposure had no retarding effect. The germination of seeds treated in the dry state was delayed by 240 minutes' exposure. Rye seeds were more sensitive to ammonia than those of radish. Exposures of soaked seeds to 700,000 |_ig/m for as long as 240 minutes resulted in 100-percent kill, while those o exposed to 175,000 |_ig/m for 960 minutes had a germination rate of only 48 percent. Classes of organisms differ in their sensitivity to ammonia gas. Leaves are the most sensitive, followed by stems, fungi, and bacteria, which are intermediately sensitive. 44 Seeds are least sensitive of all to the gas. 2.4 Effects on Materials Ammonia associated with sulfur dioxide and moisture can cause crystalline bloom defects on the surface of varnish and 25 1:7 paints, according to Holbrow. In another study, Preston exposed various metallic surfaces to fine powders in atmospheres of varying humidities. The character of the resulting corro- sion was filiform, typical of highly reactive particles in the atmosphere. Ammonia can also discolor some fabric dyes. 2.5 Environmental Air Standards The American Conference of Governmental Industrial Hygienists at their 29th Annual Meeting in 1967 recommended an occupational threshold limit for ammonia in air of 35,000 |j.g/m . The Bureau of Medicine and Surgery, Department of the ------- Navy, has recommended an ammonia threshold limit for 1 hour of 280,000 |J.g/m . The permissible limit for ammonia in a submarine during a 60-day dive is around 18,000 i_ig/m . No ambient air quality standards for ammonia exist for the United States. However, such ambient air standards exist for Czechoslovakia, the U.S.S.R., and Ontario, Canada, as shown in Table 5. TABLE 5 66 AMBIENT AIR QUALITY STANDARDS FOR AMMONIA T. Basic Standard5 Permissible Location Czechoslovakia U.S.S.R. Ontario, Canada uq/m3 100 200 3,500 Averaging Time 24 hr 24 hr 30 rain ug/m3 300 200 Averaging Time 30 min 20 min a Basic standard for long-term exposure. Permissible standard not to be exceeded more than once in any 4 hours. ------- 10 3. SOURCES The major portion of atmospheric ammonia is produced by biological processes in land and sea masses, and the gas then escapes into the atmosphere. Ammonia produced by industry and as a result of urban activities, though of lesser impor- tance, may nevertheless be a factor in air pollution in localized areas. The major source of urban-produced ammonia is the combustion process which occurs in operation of the internal combustion engine, combustion of fuels for heating, and the incineration of wastes. Industrial sources of ammonia are refineries, fertilizer plants, and organic chemical process plants. Other minor sources of ammonia arise from biological degradation in areas where animals are kept, such as stoclc- yards, and from miscellaneous uses of ammonia in cleaning both in industry and in the home. 3.1 Natural Occurrence 9! 9 According to Frost and Sullivan, 3.7 x 10 tons of ammonia are released into the atmosphere annually. Of this fi amount, only 4.2 x 10 tons are emitted to the atmosphere as a result of industrial and urban processes; therefore, roughly 99.9 percent of the atmosphere's ammonia concentration 32 is produced by natural biological processes. Junge indicates that the main biological source of ammonia is the decomposition of organic waste material. Approximately 1.0 g of ammonia per man per day is produced metabolically. Ammonia is given off from manure in piggeries and other installations where ------- 11 animals are kept. Ammonia is also generated during treat- ment of waste water in sewage plants. No information was found on the quantity of these emissions. Ammonia is also found in sea water and in volcanic gases. 3.2 Production Sources Ammonia is produced commercially in chemical process plants, as a by-product in the manufacture of other chemicals, mainly in making coke from coal, and as a product of combus- tion, refining of oils, and other processes. 3.2.1 Haber-Bosch Process The Haber-Bosch process for the production of ammonia accounts for over 85 percent of the total commercial yield. This process involves the combining of hydrogen and nitrogen gases in the presence of a catalyst. The hydrogen is usually obtained from water gas (a mixture of carbon monoxide and hydrogen), and the nitrogen is obtained from the air. Hydro- gen and nitrogen are combined with the catalyst in the ammonia generator to form ammonia when heated to temperatures of 450 to 600°C under pressure of 200-1,000 atmospheres. The world's production of ammonia in 1965 was 26.8 million tons, and this is expected to reach 70 million tons by 1970.77 In the U.S.A., 7.8 million tons of ammonia were produced in 1964. By 1968 this had increased to 17.25 fift million tons. The 1968 ammonia production rates by States are shown in Table 6. ------- 12 In 1962, there were 64 synthetic ammonia plants in this country, while in 1964 there were 95. By 1966 this number had increased to 109. TABLE 6 AMMONIA PRODUCTION IN 1968 68 State Texas Louisiana California Mississippi Arkansas Iowa Pennsylvania Nebraska Illinois Ohio All Other States Total Thousand Short Tons/Yr 3,150 3,150 1,300 1,250 850 800 625 600 525 450 4,550 17,250 .,34 3.2.2 Coke Plants In a report on Russian coke ovens, Kapitulskii"'^ states that the usual ammonia concentration in air samples at the top of a coke oven during charging was 6,300 to 8,000 tag/in . This was reduced to 3,500 to 4,400 |ag/m3 by smokeless charging- that is, diverting the coke-oven gas by vacuum to the gas- collection main. No data were found on ammonia emissions from coke-oven plants in the United States. ------- 13 In 1966 about 66 million tons of coke were produced per year in this country 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 7. TABLE 7 U.S. COKE PRODUCTION47 Year 1957-1959 1964 1965 1966 Tons/Year 60.5 x 106 60.9 x 106 65.2 x lof 66.0 x 10 No. of Oven Slots 15,993 14,639 14,357 14,720 3.2.3 Oil Refineries The main source of ammonia in oil refineries is from the catalyst regenerators in the catalytic cracking plants. The ammonia releases from oil refineries are given in Table 8. TABLE 8 g AMMONIA RELEASED FROM OIL REFINERIES Lb/100 Bl Source of Fresh Feed Compressor-Internal Combustion 0.2 Fluid-Bed Catalytic Cracking Units 54.0 Thermofor Catalytic Cracking Units 5.0 Table 9 gives the ammonia emissions from regenerator stacks in catalytic cracking units of the Los Angeles area refineries. ------- 14 At the time the data were compiled, there were 18 refineries in the Los Angeles area with a combined capacity of 700,000 barrels of crude oil per day. TABLE 9 AMMONIA EMISSION FROM CATALYTIC CRACKING UNIT REGENERATOR STACKS® (Los Angeles Refineries) Unit Type ug/ni^ Tons/Day Fluid bed 47,000-470,000 4.2 Thermofor 20,000-72,000 0.2 In 1960 there were approximately 300 oil refineries dis- tributed throughout the U.S.A. The catalytic cracking capa- city of these refineries was 3.7 million barrels per day of fresh feed plus 1.1 million barrels per day of recycle. By 1968 there were around 270 refineries in the U.S.A., with a catalytic cracking capacity of 4.1 million barrels per day 0 0 fi7 of fresh feed and 1.6 million barrels per day of recycle. The total catalytic cracking capacity from 1960 as projected to 1969 is shown in Figure 1. The cracking charge capacity and the States in which the units were located in January 1968! are shown in Table 13 in the Appendix. 3.2.4 Metallurgical and Ceramic Plants 28 Typical exhaust emissions f and ceramic plants are as follows: 28 Typical exhaust emissions from some metallurgical ------- 15 From nonferrous foundries: per plant producing 50 tons of castings per day From gray iron foundries: per plant producing 200 tons of castings per day From stone, clay, and glass plants per cement plant producing 4,830 barrels per day 0.002 tons of ammonia 0.023 tons of ammonia 0.17 manufacturing tons 6.0 5 5.5 1 d 5.0 5 4.5 < 4.0 1960 1961 1962 1963 * BARRELS PER STANDARD DAY 1964 1965 1966 1967 1968 1969 FIGURE 1 Total Catalytic Cracking Capacity of Oil Refineries 61 ------- 16 3.2.5 Combustion Processes Ammonia is produced as a result of combustion, mainly from the use of fossil fuels and incineration of waste materi- als. These sources generally result in direct emission of the ammonia into the atmosphere. The emission of ammonia from internal combustion engines has been estimated at 2.0 lb/1,000 gallons burned for gasoline O £^ enginesH/26/43 an(j for aiesei engines. The total ammonia emitted daily into the atmosphere of Los Angeles from the combustion of gasoline in 1953 was estimated at 5.0 tons a day. The rates of emissions of ammonia from various categories of fossil fuels is presented in Table 10. TABLE 10 AMMONIA EMISSIONS FROM COMBUSTION11'26/59 Combustion Source Amount of Emission Coal 2 Ib/ton Fuel oil 1 lb/1,000 gal Natural gas 0.3 - 0.56 lb/106 ft3 Bottled gas (butane) 1.7 lb/106 ft3 6 3 Propane 1.3 lb/10 ft Wood 2.4 Ib/ton Forest fires 0.3 Ib/ton The amounts of ammonia discharged daily from domestic heating sources using each fuel in a metropolitan area of 100,000 persons are given in Table 11. ------- 17 TABLE 11 POUNDS OF AMMONIA DISCHARGED DAILY IN METROPOLITAN AREA OF 100,000 PERSONS USING EACH HEATING SYSTEM18 Domestic Heating Fuel Total Pounds Coal Oil Gas 2,000 800 0.3 In 1967 the total consumption of fossil fuel in the U.S.A. comprised almost 5 million barrels of oil, around 19 18 trillion cubic feet of natural gas, and 550 tons of coal. The trends of fossil-fuel consumptions in the utility industry alone are shown in Figure 2. DC £ 10.000 g ED 1.000 *• 100 z 0 -1 10 1- 1 ^ V x==^ — "* ,--*" * **^S**~~r _, — » • w- -*^^ ^^ ^ — " ^^^ p— — = K^ — •••• — ^-- f*OAI GAS 1950 1960 1970 1980 1990 2000 FIGURE 2 Trends in Electric Utility Fossil Fuel Consumption 18 ------- 18 The demand in the United States for gasoline topped 5 million barrels per day in 1968 and is expected to reach 5.5 million barrels per day in 1969. The trend in gasoline demand between 1959 and 1968 is shown in Figure 3. 6 g _i _j 5 4 I I I I I J I 1959 60 61 62 63 64 65 66 67 68 * BARRELS PER STANDARD DAY FIGURE 3 Motor Gasoline Demand19 The emission of ammonia from incineration of solid wastes is shown in Table 14 in the Appendix. The total ammonia emitted from domestic and industrial solid waste disposal that might be expected from a metropolitan area of 100,000 population, using several methods of disposal, is shown in Table 15 in the Appendix. The United States produces at the present time about 170 million tons of refuse per year, of which about 15 percent is incinerated. In 1980, about 260 million tons per year of refuse will be produced, and the percentage to be incinerated is expected to increase about 50 percent. The ------- 19 expenditure for incinerators in 1966 was 50 million dollars. This figure is expected to rise to 100 million dollars by 1980.21 3.3 Product Sources Ammonia is used as a raw material in the production of nitric acid, fertilizers, and the syntheses of hundreds of organic compounds, including many drugs, plastics, and dyes. Approximately 85 percent of the ammonia is used as anhydrous ammonia fertilizer or as a raw material for other fertilizer production. Very little information is available on ammonia emissions from these plants. It has been reported that 2,600 tons of ammonia per year are released from a fertilizer plant in South Point, Ohio.28 Another reference reported that 0.078 tons of ammonia are released for each plant consuming 109 58 BTU/day in the chemical and allied products industry. 79 Burakhovitch made air pollution surveys in the vicinities of chemical plant complexes in Russia. The plants involved produced mineral fertilizers, synthetic monomers, ammonia alcohols, plastics, and nitric acid. Sampling sites were situated at 2,000 and 4,000 meters from the principal dis- charge sources. The ammonia concentrations measured showed a significant reduction of ammonia pollution between 1963 and 1964, attributable to the construction of waste-gas absorbers in the nitric acid plant and improvement in ammonia manufac- turing technology by the changeover to natural gas. ------- 20 In dilute solutions ammonia is used domestically, com- mercially, and industrially as a cleansing agent. Ammonia is also used in developing drawing reproductions. Table 12 shows the emissions of ammonia when used for cleaning machinery and developing reproductions of drawings. TABLE 12 MISCELLANEOUS AMMDNIA EMISSIONS 58 Remarks Manufacturing of machinery- cleaning with ammonia Developing plans and repro- ductions with ammonia 10,500 Sporadic task (one timers hours per week) 5,600 Sporadic Little information was found on the ammonia concentration 25 xn the air in the home. Holbrow observed that the ammonia concentration inside houses in England may rise to several times that in the outside air and may even approach that of sulfur dioxide. 3.4 Environmental Air Concentrations The average concentration of ammonium compounds in the air in urban areas is approximately 20 |jg/m3. ' ' The back- ground concentration of ammonium in the lower troposphere is 3 3 about 6 |ag/m in the mid-latitudes and 140 ng/m near the 59 equator. Data on atmospheric concentrations of ammonium for various cities of the United States are presented in Tables 16 and 17 in the Appendix. ------- 21 4. ABATEMENT No information has been found on the abatement of ammonia as such in air pollution; however, methods used to abate other pollutants with which it is associated also reduce the quan- tity of ammonia that reaches the atmosphere. For example, in smokeless charging of coke ovens (that is, collecting the bulk of escaping coke-oven gas, coal dust, and tar by vacuum during coke-oven charging), the ammonia emissions to the 34 atmosphere are cut in half. In incineration systems where wet scrubbers are used to remove fly ash, the ammonia in the gas stream leaving the incinerator should also be reduced. However, no information was found on this subject. In the chemical industry, where ammonia is used as a raw material, its recovery is a matter of fundamental economic importance; methods have .therefore been designed to minimize its loss. For high concentrations of ammonia, gas wet scrub- bers can be used. For ammonia concentrations in air between approximately 16 to 27 percent (flammable range)->° the gas can be flared. Impregnated activated charcoal has been used to remove ammonia from the air in laboratories that use animals in research and in other places where animals are 40 kept in large numbers. Where the ammonia occurs as a solid—as ammonium sulfate in the fertilizer industry for instance—conventional methods for solids removal can be used such as bag filters, electrostatic precipitators, and wet scrubbers. ------- 22 5. ECONOMICS In the future, greater emissions of ammonia to the atmosphere may be expected as a result of increases in incin- eration, fuel oil usage, catalytic cracking, and gasoline consumption. These added emissions should be offset by the growing number of improved abatement systems installed prin- cipally to reduce emission of other substances, such as particulates, hydrocarbons, and sulfur dioxide. However, no information has been found on the effectiveness of these sys- tems in removing ammonia, or on the number of abatement systems to be installed. The economic impact of ammonia pollution on humans, plants, and animals is expected to be minimal since at normal atmo- spheric concentrations the ammonia will have little or no deleterious effect. Localized accidental emissions of ammonia in high concentrations could have serious economic impact resulting from death or sickness of animals or humans and damage to plants. No information has been found on the eco- nomic costs of ammonia air pollution or on the costs of its abatement. Data on production and consumption of ammonia are pre- sented in Section 3. ------- 23 6. METHODS OF ANALYSIS The primary method used in air pollution for analyzing for ammonia in air is the Nessler colorimetric method. '2/ The sample is collected by passing the air through a standard impinger containing 0.1N sulfuric acid. The collected sample is then contacted with Nessler's reagent and examined in a colorimeter. If a cloudy solution forms after the addition of Nessler's reagent, alkaline Rochelle salt is added to clear 9Q it up.^y To obtain more accurate results prior to Nesslerization, the acidic sample may be made alkaline and the ammonia dis- 7 txlled into a receiver containing .02N sulfuric acid. Nessler1s reagent is then added, and the sample is analyzed colorimetrically. The Nessler colorimetric method of analysis gives the total ammonia content of the air: i.e., both gaseous and particulate components. Equipment based on Nessler's 2 method has been developed for automatic analysis. Another method utilized for analyzing for ammonia is the indophenol blue technique. The sample is collected as out- lined above. It is then contacted with alkaline phenol and sodium hypochlorite, which turns it blue-green. The sample \ color is then read on a colorimeter. The ammonia determined is the total ammonia and ammonium in the sample. This method was developed for controlled atmosphere applications but can be applied to air pollution work. The indophenol blue tech- nique has also been adapted for use in automatic ammonia 35 analyzers. ------- 24 63 Smolczyk showed that paper impregnated with phenol- phthalein will change color in air in the presence of 10 to Q ^fi 100 ppm (7,000-70,000 |jg/mj) of ammonia gas. Korenman used impregnated diazotized alpha or beta-naphthylamine to test for ammonia. Canibi indicated that ammonia samples with as little o as 0.01 ppm (7 |_ig/m ) ammonia can be analyzed by titrating directly with standard solutions of sodium hydroxide and sulfuric acid. In addition, industrial methods based on 42 infrared analysis and colorimetric techniques are used for ammonia analysis. ------- 25 REFERENCES 1. Air Pollution Manual, U.S. Dept. of Health, Education, and Welfare, Public Health Service Publication No. 99 AP-40, U.S. Government Printing Office, Washington, D.C. (1967). 2. Air Quality Data from the National Air Sampling Networks and Contributing State and Local Networks, 1964-1965, U.S. Dept. of Health, Education, and Welfare, Public Health Service, Division of Air Pollution, Cincinnati, Ohio (1966). 3. Air Resources of Utah, Prepared by the Utah Legislative Council Air Pollution Advisory Committee (June 1962). 4. Amdur, M. O., and M. Corn, The Irritant Potency of Zinc Ammonium Sulfate of Different Particle Sizes, Am. Ind. Hyq. Assoc. 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Joint District, Federal and State Project for Evaluation of Refinery Emissions, Manual on Emission to the Atmo- sphere from Petroleum Refineries, Los Angeles County Air Pollution District (1955). 32. Junge, C. E., Air Chemistry and Radioactivity (New York: Academic Press, 1963). 33. Kaiser, E. R., et al., Performance of a Flue-Fed Incin- erator, J. of Air Pollution Control Assoc. 9:2 (1959). 34. Kapitulskii, E. H., A Comparison of the Hygiene Char- acteristics of the Smokeless and Ordinary Methods of Charging Coke Ovens, Coke Chem. USSR, No. 8 (1966). 35. Kawasaki, E. H., et al., Application of the Autoanalyzer for Atmospheric Trace Contamination Analysis in Close Environmental Systems, Presented at the Technician Symposium, Automation in Analytical Chemistry, New York (Oct. 1967). 36. Korenman, I. M., Detection of Ammonia in the Air, Z. Analv. Chem. 20:115 (1932). 37. Kustou, U. U., Means of Measuring the Maximum Allowable Concentrations of Toxic Products of Natural Human Metabolism, NASA Technical Translation, National Aero- nautics and Space Administration, Washington, D.C. (Oct. 1967). 38. Landsberg, H. E., Session 1, City Air - Better or Worse, Symposium, Air Over Cities, Second Report A62-5, Public Health Service, Cincinnati, Ohio (1961). 39. Ledbetter, J. O., Air Pollution from Waste Water Treat- ment, Water Sewage Works 113(2) (1966). ------- 28 40. Lee, D., Removal of Reactive Light Gases with Impreg- nated Activated Charcoal, Fourth Annual Technical Meeting and Exhibit of the American Association for Contamination Control, Miami Beach, Florida (May 1965). 41. Lodge, J. P., and J. B. Pate, Atmospheric Gases and Particles in Panama, Science 153:408 (1966). 42. Louw, C. W., Atmospheric Pollutants and Chemical Analysis, CIR Special Report SM 062, UDC 614.71: 543.27, Pretoria, South Africa (1966). 43. Mayer, M., A Compilation of Air Pollution Emission Fac- tors for Combustion Processes, Gasoline Evaporation and Selected Industrial Processes, Public Health Service, Division of Air Pollution, Cincinnati, Ohio (May 1965). 44. McCallan, S. E. A., and C. Setterstrom, Toxicity of Ammonia, Chlorine, Hydrogen Cyanide, Hydrogen Sulfide, and Sulfur Dioxide Gases. I. General Methods and Correlations, Contrib. Boyce Thompson Inst. 11(5):325 (1940). 45. McGill, P. L., Techniques Employed in the Analysis of Los Angeles Smog, Proceedings of the First National Air Pollution Symposium (1949). 46. McGill, P. L. et al., Air Pollution Handbook (New York: McGraw-Hill, 1956). 47. Minerals Yearbook, vol. 1-11, Metals, Minerals and Fuels, Bureau of Mines, U.S. Govt. Printing Office, Washington, D.C. (1966). 48. Morgan, G. B., et al., Automated Laboratory Procedures for the Analysis of Air Pollutants, Presented at the 59th Annual Meeting of the Air Pollution Control Associ- ation, San Francisco, California (June 1966). 49. Morgan, G. B., An Evaluation of an Automated Laboratory Program for Air Pollution Analysis, Presented at the 1967 Technician Symposium on Automation in Analytical Chemistry, New York, (Oct. 1967). 50. Morgan, G. B., New and Improved Procedures for Gas Sampling and Analysis in the National Air Sampling Network, J, of Air Pollution Control Assoc. 17:5 (1967). 51. MP & E's Guide to Air Pollution Control Methods, Modern Power and Engineering 6^:6 (1966). ------- 29 52. National Air Surveillance Report - Mid-Year Report, Public Health Service, National Center for Air Pollution Control, Cincinnati, Ohio (1967). 53. Overview 1969 - A Special.Report, Oil Gas J. 66_:47 (1968). 54. Pate, J. B., et al., Atmospheric Trace Constituents in Humid Tropics. IV. Environmental Measurement of Ammonia, Preprint. Presented at 9th Conference on Methods in Air Pollution and Industrial Hygiene Studies, Pasadena, Calif. (Feb. 1968). 55. Patt, R. E., and R. E. Collumbine, Toxicity of Some Atmospheric Pollutants, Brit. Med. J. 4998:913 (1958). 56. Perry, J. H., Chemical Engineers Handbook (New York: McGraw-Hill, 1950). 57. Preston, J., Atmospheric Corrosion in Nuclei, J. Appl. Chem. 6.:26 (1956). 58. Rispoli, J. A., Fight Against Air Pollution in Argentina - Education, Legal and Technological Aspects, Paper 68-175, Presented at the 61st Annual Meeting of the Air Pollu- tion Control Association, St. Paul, Minn. (June 1968). 59. Robinson, E., and R. C. Bobbins, Sources, Abundance and Fate of Gaseous Atmospheric Pollutants, Stanford Research Institute (Feb. 1968). 60. Sawicki, E., Airborne Carcinogens and Allied Compounds, Arch. Environ. Health 14 (1967). 61. Sharmont, D. H., What is Cat Crackings Role in U.S. Today, Oil Gas J. 66:2 (1968). 62. Silverman, L., et al., Physiological Response of Man to Ammonia in Low Concentration, J. Ind. Hyg. Toxicology 31 (1949). I 63. Smolczyk, E., and H. Cabler, Chemical Detection of Respiratory Poisons, Wasser Abwasser 28:95 (1930). 64. Stern, A. C., Air Pollution, Vol. I - Air Pollution and Its Effects (New York:Academic Press, 1968). 65. Stern, A. C., Air Pollution, Vol. II - Analysis, Moni- toring, and Surveying (New York: Academic Press, 1968). ------- 30 66. Stern, A. C., Air Pollution, Vol. Ill (New York: Academic Press, 1968). 67. Survey of Operating Refineries in the U.S.A., Oil gas J. 66;2 (1968). 68. Sweaney, N., Here's What 0sers Pay for Ammonia, Hydro- carbon Process. Petrol. Refiner 47:9 (1968). 69. Thomas, N. D., Gas Damage to Plants, Ann. Rev. Plant Phvsiol. 2. (1951). 70. Thomas, N. D., Effects of Air Pollution on Plants, World Health Organization Monograph Series No. 46, Geneva (1961). 71. Thornton, N. C., and C. Setterstrom, Toxicity of Ammonia, Chlorine, Hydrogen Cyanide, Hydrogen Sulfide and Sulfur Dioxide Gases. III. Green Plants, Contrib. Boyce Thompson Inst. 1^:343 (1940). 72. Threshold Limit Values for 1967, Adopted at the 29th Annual Meeting of the American Conference of Govern- mental Industrial Hygienists, Chicago, 111. (May 1967). 73. Treshaw, M., Evaluation of Vegetable Injury as an Air Pollution Criterion, J. Air Pollution Control Assoc. 15:6 (1965). 74. Weatherby, J. H., Chronic Toxicity of Ammonia Fumes by Inhalation, Proc. Soc. Explt. Biol. Med. 81 (1952). 75. Webb, P., Bioastronautics Data Book, rev. ed. (Washington, D.C.: National Aeronautics and Space Administration, 1954). 76. Weedon, F. R., et al., Toxicity of Ammonia, Chlorine, Hydrogen Cyanide, Hydrogen Sulfide and Sulfur Dioxide Gases. V. Animals, Contrib. Boyce Thompson Inst. 11 ;365 (1940). 77. Yearbook of Science and Technology (New York: McGraw- Hill, 1967). 78. Yocom, J. E., The Deterioration of Materials in Polluted Atmospheres, J. Air Pollution Control Assoc. 8.:203 (1958). 79. Burakovich, M. S., Atmospheric Pollution by Discharges from Chemical Plants, Hva. and Sanit. 31 (1966) ------- APPENDIX ------- 32 APPENDIX TABLE 13 68 CATALYTIC CRACKING CAPACITY OF OIL REFINERIES IN U.S.A. (January 1968) State Arkansas California Colorado Delaware Hawaii Illinois Indiana Kansas Kentucky Louisiana Michigan Minnesota Mississippi Missouri Montana New Jersey New Mexico New York North Dakota Ohio Oklahoma Pennsylvania Tennessee Texas Utah Virginia Washington Wisconsin Wyoming Barrels Fresh Feed 28,500 431,800 15,500 62,000 13,000 287,780 211,700 139,550 47,500 472,710 54,000 40,000 55,500 36,000 40,800 245,445 11,200 33,000 20,500 182,200 178,650 229,200 11,000 1,138,065 42,200 25,000 80,775 5,000 42,025 per day Recycle 10,200 173,570 8,500 44 , 000 108,315 70,900 82,250 5,500 133,845 31,150 14,500 33,500 18,000 36,900 93,780 7,000 9,000 10,300 91,800 84,025 79,460 4,000 356,965 19,250 15,000 30,600 5,000 16,610 Total 4,180,600 1,599,120 ------- 33 APPENDIX TABLE 14 18,24,25,27,59 AMMONIA EMISSIONS FROM INCINERATION 3 Ib/ton of Combustion Source ug/m material burned Gas-fired domestic incinerators shredded paper and domestic wastes <4,000 Older units shredded paper 4,000 Municipal incinerators spray chamber (Alhambra, Calif.) 20,000 0.3 multiple chamber 0.4 Other incinerators Single chamber 400 0.3-0.5 Wood waste 800 Backyard paper and trimmings 45,000 1.8 Backyard 6 ft| paper 3,000 0.1 Backyard 6 ft3 trimmings 100,000 4.4 Open dump burning 2. 3 Large gas-fired industrial units 400 Flue-fed apartment incinerators 0.4 ------- 34 APPENDIX TABLE 15 POUNDS OF AMMONIA DISCHARGED DAILY FROM INCINERATION IN A METROPOLITAN AREA OF 100,000 PERSONS22 Source , Total Pounds Domestic disposal Backyard burning 345 Apartment incinerator 24 Municipal disposal Incineration 45 Burning dumps 345 Sanitary land fill Trace ------- 35 APPENDIX TABLE 16 40 41 42 U.S. NATIONAL AMMONIUM CONCENTRATION ' ' Measurements Average Maximum Location Year uq/m3 uq/m3 National Average (National Air Surveil- lance Measurements) 1964-65 New York City 1955-57 1955-60 1955-62 1 20 30 20 75 260 110 70 ------- APPENDIX TABLE 17 CONCENTRATIONS OP AMMONIUM IN AIR, UNITED STATES 42 Location Alabama Mobile Alaska Anchorage Arizona Phoenix Tucson Arkansas Little Rock California Bakersfield Bur bank Los Angeles Oakland Pasadena Sacramento San Diego Santa Ana Santa Barbara Dist. of Col. Washington Georgia Atlanta Year 1964 1964 1964 1964 1964 1964 1964 1963 1964 1964 1964 1964 1964 1964 1964 1964 No. of Samp. 26 24 25 25 25 25 24 25 25 26 26 25 25 25 26 26 Min .1 .1 .1 .1 .2 .2 .2 .1 .2 .2 .1 .1 .1 .2 .1 Microcrrams Per Cubic Meter Frequency Distribution-Percent I'D .2 .3 .3 .1 .2 .4 .1 .1 .1 .3 .1 20 .1 .1 .1 .4 .4 .6 .2 .2 .6 .1 .1 .1 .3 .1 .1 30 .1 .1 .1 .1 .5 .7 .9 .2 .3 .7 .2 .2 .2 .4 .2 .1 40 .2 .1 .1 .1 .5 .7 1.8 .3 .3 1.3 .2 .2 .2 .4 .3 .1 50 .2 .1 .2 .2 .6 .8 2.1 .4 .3 1.8 .3 .3 .3 .5 .5 .1 60 .3 .1 .2 .2 .8 1.4 3.1 .5 .3 3.2 .4 .3 .3 .7 1.1 .2 70 .4 .2' .3 .2 1.0 2.0 3.7 .9 .4 3.9 .5 .4 .8 1.2 1.5 .2 80 .9 .2 1.3 .3 1.1 2.4 4.6 1.5 .4 5.4 .8 .8 1.5 2.1 2.0 .2 90 1.5 .3 3.9 .6 1.3 5.4 7.5 2.9 .9 6.1 1.1 2.4 3.9 3.4 2.9 .3 Max 2.2 .4 4.7 2.0 2.8 13.5 10.5 8.9 5.4 17.9 2.5 2.8 8.4 5.0 6.2 .6 Arith Mean .5 .2 .8 .3 .8 2.0 3.0 1.1 .7 3.3 .5 .7 1.3 1.1 1.3 .2 Geom Mean .3 .2 .3 .2 .7 1.1 1.9 .5 .4 1.8 .4 .4 .5 .7 .6 .2 (conti Std Geom Dev 2.74 1.59 3.64 2.18 1.95 2.79 3.01 3.16 2.16 3.20 2.34 2.73 3.82 2.52 3.85 1.80 nued) ------- APPENDIX TABLE 17 CONCENTRATIONS OP AMMONIUM IN AIR, UNITED STATES (Continued) Location Hawaii Honolulu Illinois Mo line Peoria Rock Island Indiana liHrsafl Q\7l 1 1 P> CftVdiio ¥••• dciLcs Fort Wayne Muncie South Bend Terre Haute Iowa Dubuque Kansas Kansas City Kentucky Ashland Covington Louisville Louisiana Baton Rouge Maryland Cumberland Year 1964 1964 1964 1964 1 Qfid X yv*t 1964 1963 1963 1963 1964 1964 1964 1964 1964 1964 1963 No. of Samp. 26 24 23 25 n-a zo 25 -25 26 24 26 25 24 24 21 26 26 Min .1 .4. .1 .1 .1 ,1 .1 .1 .1 .2 .2 .1 .1 1 Microarams Per Cubic Meter Free 10 .4 .2 .2 .1 1 .1 .2 .2 .1 .1 1 20 .1 .6 .3 .2 .1 .1 .2 .2 .1 1.1 .2 .2 .1 uencv Distribute 30 .1 .7 .3 .3 .2 .3 .3 .1 i 2.4 .2 .3 .1 .1 40 .1 .8 .3 .3 .2 .4 .3 .1 3.2 .4 .5 .1 2 50 .1 .2 1.0 .4 .4 .3 .3 .9 .5 .2 5.0 .8 .6 .1 i .2 60 .1 .2 1.2 .5 .5 .7 .7 1.1 .6 .2 6.4 1.0 .8 .2 .3 on-Percent 70 .1 .2 1.4 .7 .7 .0 1.3 1.8 .7 .3 11.2 1.3 1.5 .2 .5 1 80 .1 .2 1.5 .8 2-7 . / 1.1 1.1 3.4 3.4 1.1 .3 19.4 1.8 2.4 .3 .7 i 90 .1 .3 3.4 .9 4n • U 1.0 2.3 7.5 7.5 1.5 .5 43.2 2.4 3.9 .4 1.8 Max .2 1.3 5.8 1.5 1 •> "7 12. / 3.4 6.5 10.8 9.6 6.4 1.7 75.5 4.8 7.9 .7 6.1 Arith Mean .1 .2 1.4 .5 1Q «y .7 .9 2.0 2.3 .9 .3 12.7 1.1 1.5 .2 .8 Geom Mean .1 .2 1.1 .5 .5 .5 .6 1.0 .6 .2 4.5 .7 .8 .2 .3 Std Geom Dev 1.48 1.80 2.02 1.79 3C O .32 2.30 3.06 6.99 4.02 2.42 2.09 5.70 2.77 3.32 1.87 3.21 co (continued) ------- APPENDIX TABLE 17 CONCENTRATIONS OF AMMONIUM IN AIR, UNITED STATES (Continued) Location Michigan Flint Grand Rapids Muslcegon Minnesota Minneapolis St . Paul Missouri Kansas City Nevada Reno New Jersey Bayonne Camden Jersey City New Mexico Albuquerque North Carolina Charlotte Year 1963 1963 1963 1964 1964 1964 1963 1963 1964 1963 1964 1964 No. of Samp. 23 24 26 26 26 25 24 24 26 25 26 25 Min .1 .1 .1 .1 .3 .1 .1 .1 .2 .1 .2 Microcjrams Per Cubic Meter Frequency Distribution-Percent 10 .1 .1 .3 .1 .2 .2 .1 .2 20 .1 .1 , 1 .1 .3 .1 .2 .5 .5 .1 .2 30 .1 .1 .1 .1 .2 .4 .1 .6 .8 1.1 .2 .3 40 .1 .1 ,1 .1 .2 .4 .2 1.4 2.0 1.8 .2 .3 50 .2 .2 .2 .1 .3 .5 .3 2.1 3.4 3.4 .2 .3 60 .2 .2 .2 .2 .4 .5 .5 2.7 5.4 4.9 .4 .4 70 . .2 .2 .2 .2 .7 .6 .6 4.9 6.4 5.3 .5 .5 80 .3 .3 .3 .3 .8 .6 .9 5.4 7.5 6.4 .5 1.4 90 .4 .4 .6 .3 1.4 .6 1.8 8.8 10.9 7.5 .6 2.4 Max .5 1.1 1.2 1.0 4.7 .9 4.7 12.4 17.5 13.4 2.6 3.8 Arith Mean .2 .2 .3 .2 .7 .5 .7 3.4 4.7 3.8 .4 .8 Geoir Mean .2 .2 .2 .2 .4 .5 .4 1.6 2.2 2.1 .3 .5 Std Geom Dev 1.61 1.84 1.94 1.91 2.93 1.35 2.94 4.49 4.56 3.65 2.21 2.46 (continued) CO to ------- APPENDIX TABLE 17 CONCENTRATIONS OF AMMONIUM IN AIR, UNITED STATES (Continued) Location Ohio Columbus Dayton Lorain Stuebenville Youngstown Pennsylvania Altoona Puerto Rico Guayanilla Texas Houston Utah Salt Lake City West Virginia Huntington Wisconsin Milwaukee Wyoming Cheyenne Year 1964 1964 1964 1964 1964 1963 1964 1964 1964 1964 1964 1964 No. of Samp. 26 26 25 24 25 22 26 24 24 24 26 23 Min .1 .1 .1 .1 .1 .1 .1 .2 .1 .1 .1 .1 Microcrrams Per Cubic Meter Freauencv Distribut 10 .1 .1 .1 .1 .1 .1 .1 .1 20 .1 .1 .1 .6 .2 .2 .2 .2 30 .2 .2 .2 .9 .3 .3 .1 .2 .1 .2 .1 40 .2 .2 .2 1.5 .4 .4 .1 .2 .1 .3 .1 50 .4 .2 .3 1.8 .5 .6 .1 .3 .1 .4 .1 .1 60 .5 .3 .3 2.0 .6 1.1 .1 .3 .2 .5 .1 .1 .on-Percent 70 .6 .5 .5 2.7 1.0 1.8 .2 .3 .3 .8 .2 .1 80 .7 .7 .8 3.4 1.5 5.9 .2 .4 .5 1.3 .3 .1 90 .9 1.3 2.9 6.4 2.1 6.4 .2 .4 1.5 5.4 .5 .1 Max 1.4 4.1 10.0 10.2 8.8 13.7 .3 .5 1.9 11.5 .9 .1 Arith Mean .5 .6 1.1 2.5 1.2 2.5 .2 .3 .4 1.5 .2 .1 Geom Mean .4 .4 .4 1.5 .6 .9 .2 .3 .2 .6 .2 .1 Std Geom Dev 2.07 2.42 3.31 3.38 3.19 4.35 1.53 1.41 2.78 3.41 2.06 1.02 CO ------- |