------- AIR POLLUTION ASPECTS OF MERCURY AND ITS COMPOUNDS Prepared for the National Air Pollution Control Administration Consumer Protection & Environmental Health Services Department of Health, Education, and Welfare (Contract No. PH-22-68-25) Compiled by Quade R. Stahl, Ph.D, Litton Systems, Inc. Environmental Systems Division 7300 Pearl Street Bethesda, Maryland 20014 September 1969 ------- 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 ------- 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, Ph0D. James L. Haynes ------- 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 Elemental mercury and most of its derivatives are proto- plasmic poisons which can be lethal to man, animals, and plants. Russian experiments with animals indicate continuous exposure to mercury vapor above 0.3 1-ig/m3 of air may present a health hazard. Some organic mercury compounds, particularly the alkyl derivatives, are much more toxic than elemental mercury or the inorganic com- pounds. Recent air measurements of particulates in New York in- dicate that the mercury concentration of indoor samples is as high as 40 l-ig/m3 , or several times higher than that found safe in animal experiments using mercury vapor. The mild symptoms of mercury intoxication are psychopathological in nature and thus can present serious problems in diagnosing the cause. Animals and plants appear to have a lower threshold to the toxicity of mercury vapors and compounds than humans. The mining and refining of mercury and the use of mer- cury in industrial and scientific laboratory applications appear to be significant sources of air pollution. Very little data are available on concentrations of mercury in the atmosphere. Methods for the control of mercury air pollution are available but may not be adequately employed. No information has been found on the economic costs of mercury air pollution or the costs of its abatement. Several methods are known for the determin- ation of measurement of mercury in the atmosphere. ------- CONTENTS FOREWORD ABSTRACT 1. INTRODUCTION 0 ...<».• 1 2. EFFECTS „ 4 2.1 Effects on Humans 4 2.1.1 Absorption, Distribution and Excretion 2.1.2 Inhibition of Enzymes 7 2.1.3 Toxicity 8 2.1.3.1 Mercury and the Inorganic Compounds 9 2.1.3.1.1 Acute Toxicity ... 9 2.1.3.1.2 Chronic Toxicity . . 10 2.1.3.2 Organic Mercury Compounds ... 12 2.1.302.1 Alky! Mercury Compounds .... 12 2.1.3.2.2 Other Organic Mercury Compounds. 13 202 Effects on Animals <, 14 2.2.1 Commercial and Domestic Animals .... 14 2.2.2 Experimental Animals ° . „ 15 2.3 Effects on Plants 19 2.4 Effects on Materials =, . . . o . . 23 2.5 Environmental Air Standards 24 2.5.1 Mercury and Its Inorganic Compounds . . 24 2.5.2 Mercury Organic Compounds 25 3. SOURCES 3.1 Natural Occurrence 28 3.2 Production Sources 28 3.3 Product Sources 32 304 Environmental Air Concentrations 39 4. ABATEMENT „ . 42 5. ECONOMICS 45 6. METHODS OF ANALYSIS 46 7. SUMMARY AND CONCLUSIONS 51 REFERENCES APPENDIX ------- LIST OF FIGURES 1. U.S. Consumption and Production of Mercury, 1935-66 . 29 2. Mercury Consumption by Uses, 1947-66 34 3. Saturation Concentration of Mercury in Air Versus Temperature 38 ------- LIST OF TABLES 1. Summary of Mercury Toxicity Data Via Inhalation ... 75 2. Properties and Uses of Mercury 76 3. Saturation Concentration of Mercury in Air at Various Temperatures 77 4. Mercury Consumed in the U.S. by Uses, 1947-1966 ... 78 5. Properties and Uses of Some Mercury Compounds .... 80 6. U.S.A. Production of Mercury by States (1936-56) . . 86 7. Major Mercury Mines in 1963 and Their Locations ... 87 8. List of Major Mercury-Producing Mines in 1966 .... 88 9. Directory of Selected Producers, Consumers, and Dealers of Mercury 89 10. List of Some Companies Producing Mercury Chemicals (1968) 92 11. Mercury-Containing Pesticides 93 ------- 1. INTRODUCTION Elemental mercury (Hg), although it is a metal, is unique in that it is a liquid at normal temperatures. This property plus its high specific gravity and electrical conduc- tivity has brought about its widespread use in industry and various types of laboratory equipment and instruments. When mercury is spilled or splashed, either in transference or by breakage of an apparatus, the mercury tends to separate into very tiny droplets that become entrapped in small cracks and crevices, rugs, etc. Moreover,- even when an attempt is made to pick up the spilled mercury, some mercury still remains. This exposed mercury, because of its high vapor pressure at room temperature, constantly emits vapors into the environmental air. In addition, any source which heats mercury (or mercury com- pounds)—such as mining and refining operations, mercury-arc rectifiers, mercury precision casting, etc.,—presents potential air pollutant hazards if not carefully controlled.. Therefore, mercury vapor is always present in the atmosphere. In ad.dition to mercury vapor, mercury compound.s may also result in air pollution. These compounds normally exist in the ambient air as aerosols. For the purposes of this report, the compounds will be d.ivided. into two main categories: inorganic mercury compound.s and. organic mercury compound.s. The inorganic ------- compounds include the ionically bonded tnercurous and mercuric salts, such as mercurous chloride and mercuric chloride. The organic compounds include those compounds in which mercury is covalently bonded to a carbon atom, as in the case of dimethyl mercury and phenylmercuric acetate. The major sources of pollution by mercury compounds are the industrial manufacturers and users of these compounds. Agricultural use of organic mercury compounds as pesticides may also be a source of air pollution. However, there has been a general decrease in the use of mercury-containing pesticides in the past years (see Section 3.3). The fact that presently no mercury residue is allowed in foodstuffs in the United States should cause this declining trend to continue. A list of pesticide formulations containing mercury is given in Table 11 in the Appendix. Further information on mercury pesticides can be found in the review by Smart 1°^ an(3 references therein. Elemental mercury and most compounds of mercury are protoplasmic poisons and therefore may be lethal to all forms of living matter. In general, the organic mercury compounds are more toxic than mercury vapor or the inorganic compounds. Even small amounts of mercury vapor or many mercury compounds can produce mercury intoxication when inhaled by man. Acute mercury poisoning, which can be fatal or cause permanent ------- damage to the nervous system, has resulted from inhalation of from 1,200 to 8,500 |_ig/m3 of mercury- -*--^9 The more common chronic poisoning (mercurialism) which also affects the ner- vous system is an insidious form in which the patient may exhibit no well-defined symptoms for months or sometimes years after exposure. The symptoms usually associated with mercuri- alism are erethism (exaggerated emotional response), gingivitis, and muscular tremors. A person suffering from a mild case of mercury poisoning is usually unaware of the cause of the ill- ness because the symptoms are psychopathological in nature. Likewise, these ambiguous symptoms may result in an incorrect diagnosis by a physician. In addition, animals and plants also exhibit a low tolerance to mercury and its compounds. ------- 2. EFFECTS 2.1 Effects on Humans It has been well documented that inhalation of air contaminated, with mercury vapor or certain mercury compounds may result in intoxication or poisoning by the absorption of toxic amounts of mercury via the respiratory tract. Neal et_ al^. ' demonstrated a correlation between the mercury concentration in the atmosphere and the prevalence of chronic mercurialism. Furthermore, inhaling mercury vapors or mercury com- pound.s may be more detrimental to the body than the other means of entry such as ingestion. For example, there are d.ata which suggest that absorption via the respiratory tract leads to a higher rate of accumulation of mercury in the brain than via the other routes of absorption. ' ' Once mercury passes the blood-brain barrier, it becomes more strongly bound in the brain 60 144 than in any other organ of the body- 2.1.1 Absorption, Distribution and. Excretion Several studies have been conducted, to determine the extent to which mercury vapor is absorbed from the human respira- tory tract. Gerstner found, that inhalation of air containing from 10 to 100 |J.g/m3 of mercury vapor resulted in absorption of 34 to 77 percent of the mercury. However, Gothlin found almost ------- complete absorption when the concentration of mercury vapor was less than 250 ng/m3 , and Shepherd et aj... found no d.etectable exhaled mercury vapor with a concentration of 60 |~ig/m3 and about 10 Hg/m3 of exhaled, mercury vapor with an initial concentration of 200,000 !~ig/m3 . Kud.sk98 found, that 67 to 88 percent of the mercury vapor was absorbed in the range of 50 to 350 The latter concluded, that when the physiological d.ead. space is considered., then for the range of concentrations studied there is also complete absorption of mercury vapor from the alveoli 99 of the lungs in normal ind.ivid.uals. He also noted that inges- tion of ethyl alcohol had. an inhibitory influence on the absorp- tion of mercury vapor by inhalation. 34 Browning reported, that organic mercury compounds are absorbed, .to a lesser extent than the inorganic compounds when ingested.. Upon passing through the alveolar and. capillary walls, elemental mercury and. mercurous compound.s appear to be readily oxidized to mercuric salts. ' The mercuric salts form solu- ble compound.s with blood, tissue, fluid.s, and proteins. Another conjunctive route for metallic mercury was suggested, by 64 Hughes. The solubility of elemental mercury in lipids allows rapid, d.iffusion through the lipid.-containing cell membranes (the alveolar walls) followed, by transport by the blood lipid.s to sensitive tissues, such as the brain. The metallic mercury is ------- then oxidized to the mercuric ion, which then reacts with the thiol groups of the proteins. In contrast, some of the organic- bound mercury compounds are not readily converted to inorganic mercurial compound.s by the blood, but by the kidneys and liver fil 64. fi R 1 9 R instead. ' ' ' Furthermore, some organic mercury compounds are retained, in the blood, for longer period.s, penetrate blood- cell barriers more easily, and. become more firmly bound, to tis- sues than the inorganic mercury compound.s. b'->a'-l-"-:> When ingested., mercury compound.s, whether organic or inorganic, become widely distributed, in all tissues. ' ' ' ' The highest accumulation occurs normally in the kidneys, with the next high- est in the liver; these compounds also accumulate in the brain, spleen, and. alimentary tract. The organic compounds appear to concentrate to a greater extent in the brain and liver than the inorganic compounds, however. Inhaled, mercury vapor and. mercury compound.s are normally excreted, as inorganic mercury in the urine and feces, with lesser amounts excreted in the bile, sweat, saliva, and. milk. '34'157 49 Mercury can also be transferred, to a fetus through the placenta 127 and to the newborn through the mother's milk. For example, 39 Butt and. Simons en reported, that in a 7-week-old, infant who died. with moist gangrene of the extremities, mercury was found in the kidneys and liver. The infant's only known contact with mercury ------- 7 was through the mother, who was exposed to mercury vapors during TOO pregnancy. Smith et a.l_. °° recently reported a strong correla- tion between mercury vapor exposure levels (time-weighted) and the mercury content of the blood and urine of workers in chlo- rine plants. Although mercury is excreted from the body as mentioned above, sometimes excretion continues for several months after exposure to mercury.^3,1^1,159 ^he rate of excretion depends on individual differences, type and duration of exposure, and the mercury derivative. In general, the excretion rate de- creases logarithmically with time after exposure has ceased. 2.1.2 Inhibition of Enzymes The ultimate effect of mercury and related compounds is the inhibition of enzyme action. It is not clearly understood which enzymes are inhibited, and to what degree, in the produc- tion of mercury intoxication symptoms. Nonetheless, it is known that both inorganic and organic mercury compounds exhibit affinity for thiol or mercaptan groups (SH groups) in enzymes, and to a lesser degree the organic ligands of enzyme systems, such as amino, carboxyl, and hydroxyl substituents. 0/44 passow et al.- also found that mercury ions can react with phosphoryl groups in cell membranes. There is some evidence that mercury ions can inhibit certain enzyme systems in vitro, including phenolsul- fate conjugation, citrulline, phosphorolysis, oxidative ------- 8 mitochondria! phosphorylation, serins biosynthesis, and cyto- chrome C oxidase. ' At low concentrations in the system, the mercury ions become bound primarily to the mercaptan groups, while at higher concentrations other types of substituents be- 27 come involved. 2.1.3 Toxicity The major factors that determine the effect of mercury poisoning on humans are (1) amount and rate of absorption, (2) physicochemical properties of the compounds inhaled, and (3) individual susceptibility. ' The first factor is illus- trated by the fact that although acute poisoning produces pri- marily nephrogastrointestinal effects, with more severe exposures, pulmonary changes predominate. On the other hand, chronic poi- soning is usually indicated by neurological effects. Several authors have noted a wide range of individual susceptibility. Although these differences are not fully understood, they have been explained in part by the varying capacity of an organ for 2 112 179 binding and. releasing mercury. ' ' Variations in the toxi- city of mercury compounds are indicated by their diverse uses, ranging from diuretics and antiseptics to highly toxic fungicides and herbicides. Inhalation of mercury vapor or mercury-containing sub- stances can lead to insidious chronic poisoning and even an acute ------- form of poisoning. Acute poisoning is not as prevalent as the chronic type but can arise from exposure to high concentrations (usually from environments where mercury is near to or in con- tact with a heated surface), or from exposure to the more toxic compounds/ particularly the alkyl-mercury derivatives. In some cases, the patient suffering from chronic poisoning exhibits no well-defined symptoms until years after exposure. The toxicity of elementary mercury and its compounds has been reviewed by Battigelli, ' Brown and Kulkarni, and Stokinger; also a 142 review by an international committee is forthcoming. A sum- mary of the symptoms of acute and chronic mercury poisoning by means of inhalation is given in Table 1 in the Appendix. 2.1.3.1 Mercury and the Inorganic Compounds 2.1.3.1.1 Acute Toxicity In some instances, inhalation of mercury in concentra- tions of 1,200 to 8,500 |-ig/m3 results in acute intoxication, affecting primarily the digestive system and. kidneys. Acute in- toxication is characterized by a metallic taste, nausea, abdomi- 159 nal pain, vomiting, diarrhea, headache, and. sometimes albuminuria. After a few d.ays, the salivary glands swell, stomatitis and gin- givitis d.evelop, and. a dark line of mercuric sulfide forms on the inflamed gums. Furthermore, teeth may loosen and ulcers may ap- g pear on the lips and cheeks. Axelsson and Friberg cite as ------- 10 symptoms gastroenteritis, anuria (with uremia), stomatitis, and ulcerohemorrhagic colitis. Severe exposure to mercury vapor pro- duces tightness and pain in the chest, difficulty in breathing, 28 and coughing. Severe cases of acute poisoning are character- ized in later stages by hemolysis, sleeplessness, headache, facial tics, digital tremors, delirium and hallucinations. Death as a result of extreme exhaustion frequently occurs with poisoning of this d.egree of severity. In mild.er cases of acute mercury poisoning, some patients recover within 10 to 14 d.ays, but others may d.evelop the chronic symptoms, such as muscular tremors or erethism. 2.1.3.1.2 Chronic Toxicity The symptoms observed, in poisoning by mercury vapor and inorganic mercury compound.s are the same. However, the inorganic compound.s, which normally occur in air as aerosols, should, be less toxic than mercury vapor because of their differences in up- 142 take and. deposition. Chronic poisoning is more common than the acute form and primarily affects the nervous system. The usual symptoms of chronic poisoning are erethism, gingivitis, and muscular tremors. ' Any of these symptoms may be present without the others and. in varying degrees, thus frequently complicating the diagnosis. Moreover, the mildest symptoms are psychopathological in nature ------- 11 and. may be exhibited by persons who have had no known exposure to mercury. Thus, as a result of exposure to mercury, a person may develop nervous anxiety, insomnia, or loss of appetite, yet his case may never be diagnosed as mercurialism. Erethism is characterized by exhibition of undue em- barrassment, timidity, depression, discouragement, irritability, resentfulness, or excitability.11'53'131'159 Other aspects are loss of the abilities to concentrate and remember, fear, and. in- decision. Thus, erethism consists of exaggerated emotional re- sponses in general. Tremors are the most frequently reported physical symptom. They can vary from a slight movement of the hands, eyelid.s, or tongue to a disabling, intense trembling which affects the whole body- 1'15 Early stages consist of tremors of the lips and tongue, followed by the fingers and. hand. Ataxia follows, first expressed, as stammering (d.ysarthria) and difficulty in swallowing (dysphagia), and. later as increasing coordination in_arms and. legs. Severe cases may intensify to en- tirely uncoordinated, movements, impaired, hearing, and. inability to communicate by writing or speaking. Gingivitis leading to recession of gums and. loss of teeth has been questioned, as a reliable indicator of mercuri- alism. Nonetheless, gingivitis, which results from poor oral hygiene, is probably aggravated by mercury exposure. ------- 12 Other symptoms noted, include such neurological d.istur- bances as paresthesia, impairment of taste or smell, neuralgia, and. d.ermographism. Stomatitis—sometimes severe—and exces- sive salivation are also common. Chronic nasal catarrh and. epistaxis, as well as renal disease and ocular lesions, are of- ten found.. 2.1.3.2 Organic Mercury Compound.s The organic mercury compounds cover a wide range in toxicity, but may generally be d.ivid.ed. into two categories on the basis of toxicity: (1) the alkyl mercury compound.s, which are stable compound.s and appear to act on the nervous system; and. (2) the other organic mercury compound.s, which are less sta- ble, d.egrading to inorganic mercury, and. are similar in toxicity to inorganic mercuric salts. 2.1.3.2.1 Alky! Mercury Compound.s The symptoms of acute and chronic poisoning for the alky! organomercury compound.s are similar. Furthermore, the symptoms, even in acute poisoning, may not be noticeable until weeks or months after exposure. Poisoning d.ue to alkyl mercury compound.s is indicated by some major neurological symptoms and. lead.s to permanent dam- age or d.eath. Cases of severe exposure have prod.uced. perman- ent impairment of the nervous system, such as gross ataxia, ------- 13 aphasia, sensory loss in the limbs, impaired vision and hearing, 11 flfi 8Q personality changes, and loss of intellectual capacity. x'00'° In severe cases the symptoms are irreversible. In an example 88 related by Hunter, a 16-year-old boy exposed to methyl mercury compounds for only a few months who had sustained severe damage to his nervous system was still unable to work after 20 years because of persistent ataxia, tremors, and inability to recognize objects by touch. Inhalation of alkyl mercury derivatives can produce sen- sations of dryness and irritation in the nasopharynx and mouth and even lead to blistering. In general, alkyl mercury cotn- pound.s affect predominantly the motor and sensory nerves, while the inorganics are more likely to prod.uce symptoms of excessive 33 salivation, stomatitis, and erethism. Cases of mental retardation with convulsive cerebral palsy have been reported in infants born to mothers who were exposed, to large amounts of methyl mercury during preg- nancy-57'117 2.1.3.2.2 Other Organic Mercury Compounds Organic mercury compounds other than the dialkyl deriva- tives are in general rapidly converted in the body to inorganic mercury compounds.1'" Thus, these organic compounds show toxi- cities and. symptoms similar to those of the inorganic mercury ------- 14 compounds (see section 2.1.3.1)- Information on the toxicity of these compounds is very limited. Methoxyethyl mercury, a fungicide, has been reported to cause symptoms associated with inorganic mercury compounds, in- cluding loss of appetite and weight, diarrhea, and fatigue.142 Goldwater ,et_ a.1.. ^ reported evidence of kidney damage from heavy exposure to phenylmercuric acetate; however/ the dam- age may have been related to a simultaneous acid burn of the skin. No conclusive evidence of toxic effects in humans from long-term exposure to phenyl mercury salts has been reported. Massman reported on 26 human subjects with up to 6 years' exposure to phenylmercuric pyrocatechin (240 to 3,200 |J.g/m3 ) with no clini- cal evidence of injury. Goldwater £t_ al_. '4,103 studied more than 100 workers exposed to phenyl mercury compounds in the air (usu- ally with some inorganic salts also present). Thirty-five of the workers had been exposed, to mercury concentrations up to 5,100 iag/m3 , with the air concentrations generally exceeding 290 fig/m3 . No cases of poisoning were record,ed. in either study. 2 .2 Effects on Animals 2.2.1 Commercial and Domestic A/iimals No qualitative or quantitative data were found con- cerning mercury poisoning for animals exposed to typical environ- mental conditions. Farm animals have been poisoned, as a result ------- 15 of eating plants treated with mercury-containing pesticides. An incident of mercury poisoning in cattle stabled overnight with a horse that had been treated with a mercury skin ointment was QO also described. Heimann0-6 reported on an incident described by R4. Henderson and. Haggard0^ in which symptoms of mercury poisoning developed in cows and other domestic animals after a fire in a nearby mercury mine. 2.2.2 Experimental Animals Papers describing the toxic effects of mercury and its compounds on animals are too numerous to be reviewed in detail in this report. However, important papers relating to inhalation of mercury-containing substances and air pollution will be summar- ized. More detailed, summaries can be found in the reviews of Battigelli,10'11 Brown and Kulkarni, and Stokinger, and in the references mentioned, therein. Kurnosov conducted, experiments in which white rats were continuously exposed, to a low concentration of mercury vapor for 9.5 months. Rats that inhaled the vapor in the concentration ranges of 20 to 30, 8 to 10, and. 2 to 5 |-ig/m3 of air showed an accumulation of mercury in the kidneys, liver, and to a lesser extent in the brain and. heart. They also exhibited pathomor- phological changes and. disturbances of the functional activity of the higher nerve centers. The degree of neurological and ------- 16 pathomorphological changes appeared to be proportional to the mercury concentration. The author also cited reports which showed that inhalation of 100 to 7,000 |ag/m3 of mercury resulted in the death of laboratory animals. Ashe .et. Jil..^ studied, the responses of animals exposed to mercury vapor at concentration levels of from 100 to 6,000 M,g/m3 for as long as 83 weeks. In rabbits exposed, to mercury vapors at 6,000 ng/m3 for 6 weeks there was severe d.amage to the kidneys, heart, lungs, and. brain. In d.ogs he found no damage af- ter 83 weeks of exposure to a mercury vapor concentration of 100 l-ig/m3 . At a concentration of approximately 860 |jg/m3 , signifi- cant d.amage to the brain and. kidneys was noted after 6 weeks, although the damage disappeared when the animal was no longer exposed.. The authors pointed, out that the animals have a greater susceptibility to renal tissue d.amage by mercury vapors than do humans, and that this type of data cannot therefore be applied quantitatively to man. These authors also d.etermined. the U/A ratio (amount of mercury in urine to amount being inhaled) at 100 |_Lg/m3 of mer- cury vapor. After several weeks, a steady-state ratio of 0.14 for rabbits and 0.4 for dogs was attained. In contrast, in hu- mans exposed to the same concentration of combined mercury vapor and dusts for months to years, the U/A ratio was 7. Some factors ------- 17 responsible for the higher U/A ratio in humans than in animals may be a higher rate of pulmonary deposition, absorption, or urinary excretion of mercury. The U/A ratio decreases as the concentration of mercury increases for both humans and animals, although the decrease is greater for humans. Frazer _et_ _al_. ° found that dogs exposed to mercury va- por of 3,000 l-ig/m3 of air or less for 40 days showed no signs of intoxication. However, an increase to 3,000 to 6,000 t-ig/m3 for the same length of time produced effects on the central ner- vous system and digestive tract. In addition, death resulted after eight days at 6,000 to 20,000 |-ig/m3 or a few hours at 20,000 |ag/m3 . Gage^4 has shown that rats inhaling 100 |~ig/m3 of mer- cury vapor for short periods had a rapid turnover of mercury in all tissues except the brain, and that the mercury was elimina- ted within one week after the exposure was discontinued.. How- ever, after prolonged, exposure the mercury was converted, by the kidneys to a derivative which was excreted, very slowly- Several authors have stud.ied. the effects of inorganic and. organic derivatives on animals .18-20,60-62,138,167 These studies are based, mainly on injection of the compound, rather than inhalation. Clarkson et al. and Berlin1^ consider that the mode of administration is irrelevant, since they believe that ------- 18 mercury entering the body by inhalation does not behave differ- ently from mercury compound.s injected, into the system. In gen- eral, their results suggest that mercury, in animals as in humans, is wid.ely distributed in the body but mainly concentrated in the kidneys and liver and to a lesser extent in the brain, and that the organic mercury compounds are more toxic to animals than in- organic mercury by a factor of 5 to 20. Moreover, the organic mercurials—especially the alky! derivatives—appear to concen- trate more rapid.ly in the brain tissues and. are also more tightly bound to most tissues. Bellies _e_t a.l_. exposed pigeons to an average mercury vapor concentration of 80 M-g/m3 for 6 hours a d.ay for 20 weeks and found no behavioral, histological, or gross signs of mercuri- alism. However, Armstrong et. ail_.-> found notable changes in the behavior of pigeons after 14 weeks at 17,000 M-g/m3 . It was noted, in the previous section that humans absorb nearly all of the mercury vapor inhaled, in the concentration range of 50 to 350 |ag/m3 . However, in dogs exposed to concentra- tions of from 3,000 to 26,000 [ag/m3 , the amount of inhaled, mer- cury absorbed, varied, from 21 to 23 percent. Gage-* also found. that rats absorbed only about 50 percent of the mercury vapor when exposed, to 1,000 ^g/m3 . It is not known whether this is due to the difference in the absorption ability of human and ------- 19 animal lungs, the higher concentration of mercury vapor, or other factors. In summary, it appears that animals exhibit toxicity symptoms similar to man but are more susceptible to lower concen- trations of mercury. 2.3 Effects on Plants Evidence has been published that clearly demonstrates the phytotoxicity of vapor from metallic mercury and. its com- pounds in a certain variety of roses and other species of plants. Although injury to plants has been noticed only when the plants are located, in a confined, atmosphere containing a source of mer- cury, examples are given where the mercury content of the air was less than 10 (Jg/m3 and yet severe damage to roses resulted.. Various species and. varieties of plants d.iffer widely in their susceptibility to mercury poisoning. The extent of damage to a particular species of plant d.epend.s mainly on factors which "in- fluence the vaporization of mercury, such as source of mercury, temperature, air-flow rate, and. initial concentration. It is generally believed, that the phytotoxicity of mercury compounds is primarily d.ue to the mercury vapors arising from thermal de- composition or catalytic red.uction of the compound to metallic vapor.^ Lesions caused, by both organic and inorganic mercury compounds are indistinguishable from those caused by metallic mercury. ------- 20 The damage to certain species of roses from mercury poisoning consists of brown or black discoloration of the leaves, petals, peduncles, and corollas of the young buds. Further expo- sure results in stronger discoloration, followed by abscission of the leaves and the young bud.s. Injured plants may recover from the mercury poisoning if removed from the contaminating source. Slightly injured, plants prod.uce normal shoots from various parts of the plant in one to two months. However, badly injured roses may not initiate normal growth or flowering for several months, and then only from the lower part of the plant. Another important aspect of mercury poisoning in plants is their tend.ency to accumulate large amounts of mercury in leaves and various other parts. One experiment is reported in which approximately 4,000 ppm of mercury was found, in tobacco leaves after the soil was moistened, with a 1 percent solution of mercuric chlorid.e for one week. Even though the leaves contained a high concentration of mercury, the tobacco plant itself exhib- ited only slight damage. Only a few papers exist which d.escribe the effect of mercury on plants. Some early experiments with mercury are re- ported, by Boussingault,2^' in which mint, petunias, peach twigs, and bean plants were exposed, to metallic mercury vapors. These plants developed, dark spots and. blackening of the leaves and stems, ------- 21 with eventual collapse and premature falling of the leaves. During 90-hour experiments, it was noticed that damage increased with the duration of the mercury exposure. Interest in the phytotoxicity of mercury was stimulated again in 1933 when some Briarcliff roses were accidentally in- jured, in a commercial greenhouse: the mature roses had faded, while the petals on the buds of the younger plants had turned brown. Other species of roses in the same greenhouse did not exhibit any sign of damage. Zimmerman and Crocker-'-"-'- experi- mentally verified the fact that the injury to the roses resulted from an application of mercuric chloride for earthworm control. Further investigation suggested that in the presence of Tank- age—a fertilizer having a high organic matter content—mercuric chloride had a much greater effect than the mercury compound a- lone. Ratsek found in similar experiments with both mercury and mercuric chloride that the leaves of the roses accumulate mercury. He also found that the amount recovered in the leaves was dependent upon the surface area exposed to mercury. Zimmerman and. Crocker182 further studied the effect of Tankage fertilizer on the apparent increase in phytotoxicity of mercuric chlorid.e. The results of these experiments showed that the injury to roses from mercuric chloride was caused by the me- tallic mercury vapor produced from the decomposition of the ------- 22 mercuric chloride, which was found to be catalyzed in the pre- sence of organic matter (such as that used in Tankage). These investigators then conducted additional experiments with mercury using other species of plants. Some of the plants which they found particularly susceptible were the broad bean, butterfly weed, oxalis, and sunflower, as well as nine varieties of roses. Some plants relatively resistant to the vapor were aloe, croton, English ivy, oak, and pachysandra. Peach, privet, tomato, gera- nium, and Boston fern exhibited intermediate susceptibility. Zimmerman and Crocker ^ analyzed the leaves of differ- ent species after about one week's exposure to mercuric chloride. Some of the results were Briarcliff rose 317, Coolidge rose 808, and Turkish tobacco 2,405 to 3,747 ppm of mercury (by dry weight). It is interesting that the Briarcliff is more susceptible to dam- age by mercury than the Coolid.ge rose, and both are more suscepti- ble than the tobacco, which showed only slight d.amage. Recent reports ind.icate that certain plants are injured. when exposed, to mercury fumes resulting from decomposition of paints containing mercuric fungicid.es. Butterfield4 reported two cases of mercury poisoning in Better Times roses caused, by emanations from a fungicid.e paint on the walls of the greenhouse. A greenhouse freshly painted, with the same fungicid.e paint showed. only a slight reading on a mercury vapor d.etector (about 10 |-ig/m3 ) ------- 23 after 24 hours. After 20 days in this greenhouse, however, Peter's Briarcliff roses exhibited minor lesions, and after an additional week of exposure severe injury was apparent. Diamond, and Stod.d.ard.^3 reported a similar case of dam- age to roses arising from the use of mercury fungicide paint in- side a greenhouse. The paint contained, about 0.08 percent mer- cury by weight in the form of the fungicid.e di-(phenylmercuric) dodecenyl succinate (DPMDS). Analysis of the air surrounding the injured, roses showed no detectable mercury vapors (the lower limit of the detector was 10 |~ig/m3 ). However, analysis of the roses showed, that the petals contained 1.3 ppm of mercury (fresh weight) and the leaves 3.3 ppm. Roses not exposed, to mercury contained 0.2 ppm of mercury in the petals and 0.07 in the leaves. When tested, the fungicide DPMDS slowly decomposed, at room temperature, releasing mercury vapor into the atmosphere. Hitchcock and. Zimmerman"^ have reviewed in detail the reports of mercury poisoning of plants up to 1957. Thomas16 also has reviewed, air pollutants (including mercury) which are harmful to plants. 2.4 Effects on Materials No information on d.amage to materials by mercury was found. However, it may be possible that even at low concentra- tions, mercury will slowly collect on certain metallic surfaces ------- 24 and penetrate the material by amalgamation. If the concentration of mercury becomes too high, the strength of the material may be weakened. 2.5 Environmental Air Standards 2.5.1 Mercury and Its Inorganic Compound.s The American Conference of Governmental Industrial Hygienists165 has ad.opted. the threshold limit value (TLV) of 100 iag/m3 for mercury vapor and. inorganic compounds of mercury for an 8-hour work day. The TLV^ is based on studies of human ex- posure in the felt hat ind.ustry by Neal et aJ^.129 and. on unpub- lished, results by Fahy5^ in the electronics and lamp industries. However, there are several examples which suggest that this level should be changed. Gold.water et a.l_.73 cited the studies of Smith _e_t _§_!. ,155'156 Bidstrup,22 and Neal et al.. on the exposure of workers to a concentration of less than 100 |-ig/m3 of mercury va- por and. inorganic compounds which resulted, in mercury poisoning in 5 to 12 percent of those exposed. However, a study by Klein- field, et^ a_l_.95 on workers exposed, to inorganic mercury compound.s in the range of 80 to 400 |ag/m3 (an average exposure of approxi- mately 200 i-ig/m3 ) for more than two years found that these work- ers exhibited no evidence of mercury intoxication. Stokinger1^9 in a review on mercury feels that with the current TLV, a relatively small margin of safety for mercury vapor ------- 25 exists, although with the mercury inorganic salts there is a greater safety factor. Several authors have shown concern that this TLV may be too high, especially in the case of mercury va- por. The ACGIH Threshold Limit Values Committee is considering lowering the TLV for "inorganic" mercury to 50 ng/m3 air, on the AQ basis of unpublished studies by the chlorine industry. In 1968 an International Symposium recommended 8-hour Maximum Allowable Concentrations (MAC) of 50 f-ig/m3 for mercury vapor and 100 |J.g/m3 for the inorganic salts. No studies have been found that suggest or set a 24-hour exposure limit for mercury in the United States. However, in AQ a discussion with B. F. Craft, ° Dr. H. E. Stokinger suggested that a 24-hour limit for mercury be no higher than 10 p.g/m (based on a limit of 50 |J.g/m3 for 8 hours). In 1963, a maximum allowable concentration of metallic mercury of 0.3 ng/m3 of environmental air for a 24-hour expo- sure was established in Russia (the U.S.S.R.'s maximum occupa- tional 8-hour exposure limit to inorganic mercury is 10 M.g/m3 ). This Russian 24-hour limit was based on animal experiments .-1-43 Long-term experiments with rats at a level of 2 to 5 (ag/m3 of mercury vapor in air affected the functional activity of higher nervous centers, caused mercury deposition in the brain and other organs, and produced pathomorphological changes.100 ------- 26 2.5.2 Mercury Organic Compounds Because of the higher toxicity of many of the organic- bound mercury compounds, the ACGIH165 has established a TLV for organic mercury of 10 [J.g/m3 for an 8-hour exposure, a factor of 10 less than that for inorganic mercury. This TLV is based mainly on the studies of Ahlmark, Lundgren and Swensson,1 Trakhtenberg,166 and Dinman et_ etl.54 The former two studies1'109 are occupational studies in which alkyl mercury compounds were being used. The data provided in these two studies do not in- clude the atmospheric concentrations of the mercury compounds nor the methods of analysis. Ahlmark1 concluded that the limit should be 10 |J.g/m3 . On the basis of the finding that mice died upon being exposed for 3 to 5 hours at 10,000 to 30,000 Mg/m3 of organic mercury (ethyl mercuric phosphate and chloride) in air, Trakhtenberg,166 in 1951, concluded that humans could not tolerate exposures of 0.01 [ag/m3 on a continuing basis. In the more recent study by Dinman et aJ^., ^4 in 1958, 20 workers were exposed to organic mercury (ethyl mercuric phosphate and chloride adsorbed on inert clay and solvent solutions of ethyl or phenyl mercuric acetate) in the range of 10 to 100 |J.g/m3 for almost 6 years, yet did not show any symptoms suggestive of mercury in- toxication. In fact, several other studies strongly suggest that some organic mercurials, especially the aryl-mercury salts, ------- 27 are no more toxic than the inorganic mercury salts.66/103,113,162 This has led several authors to question the TLV of 10 |ag/m3 for all organic mercury compounds.'3,103,175 In Russia, an 8-hour MAC of 5 ng/m3 was established for alkyl mercury compounds (methyl and ethyl mercury chlorides). An International Symposium recommended 100 k^g/m3 as the 8-hour MAC for phenyl and methoxyethyl mercury salts. Therefore, if a 24-hour maximum exposure limit is to be established for organic mercury compounds, it may be necessary to establish different tolerance levels for particular types of organic mercury compounds, such as alkyl and aryl compounds. ------- 28 3. SOURCES 3.1 Natural Occurrence Mercury is neither abundantly nor widely distributed in the earth's crust.122'12^ The percentage of mercury in ig- neous rocks is approximately 10~7. Although less abundant than platinum, uranium, silver, cesium, and other common metals, mer- cury exists in highly concentrated ores and thus is readily at- tainable. Most mercury d.eposits are found near the surface of the earth, and in the United. States are confined, mainly to the West Coast in a belt of late tertiary orogeny and volcanism. There are only a few ores of mercury, and. only one ore of economic importance—cinnabar, or mercuric sulfide (see Sec- tion 3.2). Elemental mercury occurs in small quantities, mixed with its ores. 3.2 Production Sources The production of mercury in the United. States has not kept pace with the consumption since 1918, except for the years 1931, and 1940 through 1942. The total production has fluctu- ated since 1935 (see Figure 3). In 1950, the domestic production was the lowest ever recorded, supplying only 9 percent of the national requirements. In succeeding years, prod.uction gradually increased—reaching a maximum of 83 percent of the consumption— before again declining. Approximately 5.5 million pounds of ------- 29 FLASKS (000) 80 70 60 50 40 30 20 10 CONSUMPTION PRODUCTION 1935 1940 1945 1950 1955 1960 1965 FIGURE 1 U.S. Consumption and Production of Mercury, 1935-66126 ------- 30 mercury were consumed in the United States in 1966.126 Of this amount, about 1.67 million pounds or 30.6 percent were prod.uced by domestic mines. California (with 73.1 percent) and Nevada (with 15.2 percent) are the principal mercury-prod.ucing states, with lesser quantities prod.uced. in Alaska, Arizona, Arkansas, Idaho, Oregon, Texas, Utah, and. Washington. (See Table 6 in Appendix for United States production of mercury by states since 1936.) In 1963, eight mines furnished 97 percent of the domestic primary production. (See Table 7 in Append.ix for the list of these mines and their location.) The number of producing mines has increased, from 48 in 1963 to 130 in 1966, while 149 mines produced mercury in 1965.126 Table 8 in the Appendix lists the mines with a production of 100 flasks or more in 1966. Forty other mines-'--''-' supplied the remainder. The principal ore mined for mercury is cinnabar (red mercuric sulfide, alpha-HgS), which is mined by both underground and surface or open-pit mining. Several studies have been con- ducted, to d.etermine the concentration and. hazard, of atmospheric mercury in mines all over the world.4'50'87'104'172'174 Al- though no data are given on the amount of mercury emitted into the surrounding atmosphere, these studies showed, that the working environment contained, dangerous amounts of mercury (as high as about 5,000 |-ig/m3 ) in the form of vapor and aerosols, as well as ------- 31 in mine dusts. A number of the miners studied exhibited signs of mercury intoxication especially before proper methods of con- trol were used. Ore refining, which is usually done near the mine site, is another source of atmospheric mercury contamination, as well as an industrial hazard. The ore is heated in retorts or fur- naces in the presence of oxygen or lime to liberate mercury as a vapor, which is collected in condensers. ^ These gases are then passed through washers and into the open air through a stack. According to Schuette146 as cited by Stokinger, stack losses should not exceed 2 or 3 percent, although very much higher losses have occurred. A stack loss of only 3 percent would mean that over 50,000 pounds of mercury were emitted into the atmosphere in the United States in 1966 from smelting alone. Mercury can also be found in small amounts in associa- ted sulfides of other metals, although it may not be economical- ly feasible to recover the mercury. Hence, in refining the ore to recover other metals, the mercury vapor produced in the pro- cess may escape into the atmosphere. In special cases, signifi- cant amounts of mercury have been recovered as a by-product of zinc, copper, and gold production. Due to the large demand and. low cost of production rates, the production of secondary mercury has been high. Sources of secondary mercury are reclaimed dental amalgams, oxide and ------- 32 acetate sludges, battery scrap, and dismantled mercury boilers. About 23 percent of the mercury consumed in 1966 was secondary mercury. In 1964 and 1965 secondary mercury was very high (about 30 and 63 percent respectively of the total mercury pro- duction) as a result of the release of surplus mercury by the Atomic Energy Commission. 3 . 3 Product Sources In 1963, a total of about 300 companies used the virgin mercury supplied by the mines; 96 percent of this virgin mercury was consumed by 80 companies located in the Eastern States. ^ A list of the large producers, consumers, and dealers in mer- cury is given in Table 9 in the Appendix. About 400 companies throughout the United States consumed approximately 20 percent of the redistilled mercury in 1963. Consumption appears to be generally increasing and is expected to maintain this trend for the next 5 years or more. Table 10 in the Appendix lists some of the companies producing mercury compounds. The two major uses of the mercury consumed in the United States in 1966 were in electrical apparatus and electro- lytic preparation of chlorine and caustic soda, corresponding 1 O C^. to about 19 to 16 percent of the total consumption, respectively. Other uses include paints (11 percent), industrial and control instruments (6 percent), Pharmaceuticals (5 percent), agriculture ------- 33 (3 percent), and catalysts (3 percent). The data for, the uses for the past 20 years are given in Table 4 in the Appendix. The trend for consumption by uses can be seen in Figure 2. The use of mercury in agriculture and for industrial and. control instruments has declined. However, there is a strong increase in the use of mercury for the electrolytic preparation of chlo- rine and caustic soda that is further reflected in "other uses," which includes mercury used for installation of new chlorine and caustic soda plants. Mercury is also increasingly used in electrical apparatus, paints, and laboratory products. Mercury's high specific gravity, electrical cond.uc- tivity, and boiling temperature, plus the fact that it is a liquid at normal temperatures, make it suitable for application in mercury-arc lamps, neon and fluorescent lamps, mercury boilers, electrodes in electrolysis, arc rectifiers, batteries, switches, thermometers, barometers, manometers, hydrometers, pyrometers, and related equipment.10'107'121'1^0 A relatively new applica- tion is in amalgam metallurgy and. precision casting, such as jewelry and molding processes.46'93 (See Table 2 in the Appen- dix for a summary of the properties and uses of mercury.) The chemical properties of mercury compounds give rise to such applications as catalysts in preparing organic compounds, fungicides, spermicidal jellies, herbicides, insecticides, ------- 34 FLASKS (000) 70 60 _ 50 _ 40 _ 30 _ 20- 10- Other Uses Electrical Apparatuses Redistillation Electrolytic Preparation Of Chlorine and Caustic Soda Paints Laboratories Industrial and Control Instruments Pharmaceuticals Agriculture Dental Preparations Catalysts Amalgamation —I 1 1957 61 1961 66 1 1947 - 51 1952-56 FIGURE 2 Mercury Consumption by Uses, 1947-66 ------- 35 explosives, antiseptics and disinfectants, pigments, preserva- tives, embalming preparations, antibiotics, diuretics, fire- works, and. many other uses. Some of the more common compounds and. their uses, along with their physical properties and toxi- city, are listed, in Table 5 in the Appendix. Only one example of community-wid.e mercury poisoning QO has been reported. Heimann0'' mentioned the incident described. 84 by Henderson and Haggard following a fire in a mercury mine in Idrija, Austria (now in Yugoslavia). The community of 900 inhabitants developed, the muscular tremors symptomatic of mer- cury poisoning; moreover, cows and. other domestic animals also exhibited, the symptoms of intoxication. Numerous examples in the literature d.escribe the haz- ards of merc.ury poisoning resulting from industrial exposure. These hazards are present in a variety of industries, including the manufacture of felt hats (rare),1 technical instruments, 34'54 chlorine and. caustic soda, ' carbon for electrical motors, 5 fluorescent lamps, ' neon signs, mercury compound.s, jewelry,46'93 tungsten rods,161 textiles,96 pesticides,86'88'109 and dry batteries.176 They also exist in seed-treating, 5 re- o o fi Q pair of electrical apparatus, ^ mercury catalysis, and occur in rectifier shops and breweries.3^ Broadhurst3^ anca Bid- strup^1 have summarized some of the cases of industrial mercury poisoning. ------- 36 Mercury poisoning is also a problem for the general public. It has been demonstrated that a mercury hazard exists in scientific laboratories, schools,12'72'101'168 hospitals,177 medical laboratories,131 and dental offices.94'153 Organic mer- cury compounds used, in house paints yield detectable concentra- tions of mercury (over 100 p.g/m3 for short periods of time). However, Goldberg and Shapero and Jacobs et_ al.. concluded from their studies that these paints do not constitute a direct hazard to the painters or occupants of the room which was painted. Other than mercury-containing paints, the only other com- mon household, source of poisoning appears to be the breakage of thermometers and. possible d.amage to mercury-filled, switches, nei- ther of which apparently constitute a known hazard.. There are, however, several exceptional examples of mercury poisoning in the home. Burke and Quagliana37 reported, mercury poisoning re- sulting from an attempt to recover mercury from hearing-aid mer- cury batteries. Mathes et .al_.116 cited an example where a homemade mercury paint was used, on a gas heater. The heater was turned, on before the paint was completely d.ry, resulting in the deaths from mercury vapor inhalation of three childxen sleeping in an adjacent room. Bucher36 mentions an incident in which a bottle of mercury was spilled, and although it was "cleaned up" left enough remaining mercury to be harmful. ------- 37 Mercury vapors are probably the major source of envi- ronmental pollution. The hazard from mercury vapor occurs chiefly from spillage in and around the areas where it is used. .^9 • 9 "•? Biram^J points out that it is impossible to clear mercury away completely once it has been spilled or splashed. When this hap- pens, the mercury tends to break up into exceedingly small drop- lets which can become entrapped in cracks and crevices; the amount of vapor produced is thus increased because of the greatly in- creased surface area of the mercury. The rate of vaporization for mercury increases very rapidly with increase in temperature. Figure 3 shows that the atmospheric concentration will approximately double for every 10°C increase. It should be noted that at room temperature (20 to 24°C or 68.0 to 75.2°F) the saturation concentration of mer- cury in air (see Table 3 in the Append.ix) is 130 to 180 times greater than the accepted. Threshold. Limit Value for 8-hour ex- posure. Hence, it is conceivable that mercury vapor in the environmental air could, reach a concentration that would, be harmful to the surrounding population and. even fatal. Giese68 found, that at 25°C a stream of air flowing at a rate of one liter per minute over a 10 cm2 area of mercury be- comes about 15 percent saturated, (i.e., contains about 3,000 ug/m3 of mercury), which is well above the human toxicity level. ------- 38 (000) 110 - 100 90 - 68.0 75.2 82.4 46.4 53.6 60.8 104.0 111.2 FIGURE 3 Saturation Concentration of Mercury in Air Versus Temperature ------- 39 The amount of mercury (approximately 10 g) in 10 thermometers used in the home could easily produce a 10 cm2 area if the mer- cury from each thermometer formed about 10 or more droplets or globules of mercury- More cases of mercury poisoning probably would occur were it not for the fact (in part) that in still air the heavy vapors (approximately eight to nine times more heavy than air) tend to collect near the surface of the mercury and thus tend to prevent rapid evaporation. Dirt, grease, and. other impurities also collect on the surface of the drops, re- tarding the normal rate of evaporation. Several foreign countries have problems with mercury pollution today, especially Japan and Sweden. In Japan, large amounts of organic mercury fungicides are being used in the pre- vention of "rice blast disease." A high concentration of mer- cury in the air has resulted, and an even higher one in food and water. Air measurements have shown that the concentration of mercury is as high as 10,000 |ag/m3 in some areas.^3 jn Sweden,^ the mercury comes from such industrial sources as pulp and pa- per and chloralkali plants. 3.4 Environmental Air Concentrations Only one paper giving data on the concentration of mer- cury in the air has been found. Cholak reported the mercury content of suspended particulate matter for two cities: ------- 40 Concentration in ug/ma_ Average Range Cincinnati (1946-1951) 0.10 0.03-0.21 Charleston (1950-1951) 0.17 These data pose this important question: how hazardous is the mercury contained in particulates? The question is yet to be answered- All studies found concerning the inhalation of either mercury vapor or its compounds deal with the pure sub- stance and not mercury-containing particulates. Furthermore, not only do the data represent an inadequate sampling of the United States, they also fail to give the current concentrations or illustrate trends for the future. Dr. L. J. Goldwater in 1968 kindly provided the fol- lowing unpublished data on some recent surveys of mercury con- centration : Concentration of Mercury ( Palo Alto, Calif. (Hg vapor) 0.001 - 0.01 New York, N.Y. (Hg in particulates) Outdoor: 1-14 Indoor: 1-41 [ ,"•' > - .^ ^. The New York data are from 25 to 30 samples taken about 1960 over a three month period in the Queens section of New York City, primarily from the residential district, although some of the indoor samples were taken in business offices and the laboratories and offices of Columbia University. As far ------- 41 as could be determined, there were no unusual sources of mer- cury near the sampling areas.'''-'- The Palo Alto data are from representative samples collected over several years. ------- 42 4. ABATEMENT Industries using mercury and. mercury-related compounds have developed control methods as a result of two principal fac- tors: the high toxicity of most mercury sources and the high cost of mercury. Industries that use mercury are divided into two main categories: those that use mercury at ambient tempera- tures and those that use mercury at elevated temperatures. For the former, control methods consist largely of protection of the employees by maintaining proper ventilation in work areas, cleaning up spilled mercury, and using non-porous material for floors, working surfaces, and protective clothing. Low con- centrations of mercury vapor are directly vented to the open atmosphere with no attempt to trap the mercury vapors. When mercury is used at elevated temperatures in such uses or processes as metallurgy of mercury and other metals (via amalgamation with mercury), mercury boilers, and mercury-arc rectifiers, better control of the effluent mercury vapors is necessary. In general practice, vapors are condensed by means of cold-water-jacketed condensers.70 In one instance, impreg- nated charcoal was used to remove mercury from the hydrogen gas stream originating from mercury cells used in the production of hydrogen.10^ More effective removal can be accomplished by use of water scrubbers in the final section of the condensers and by ------- 43 subsequent use of a pyrolusite adsorber.137 Spilled mercury presents another possible pollutant problem. This problem occurs not only in industry, but also in schools and hospitals, laboratories, and. even homes (from the breakage of thermometers, etc.). The ambient atmosphere as well as the working environment are continually being contaminated. by these sources. Because of lack of knowled.ge or lack of con- cern about the toxicity of mercury, the mercury is often not re- moved, effectively, if at all. Several removal methods are available, ranging from sweeping with special vacuum cleaners to chemical treatment of the mercury. Sweeping can effectively remove large droplets but is not ad.equate for removing mercury i ft n trapped in small crevices of the walls and floors. yavorovskayaxo developed, a method, which although more effective, can only be used on surfaces covered, with thermostable materials. The ap- paratus consists of an electric heating chamber (which heats the surface to be cleaned.), a blower, and. a collector-filter con- taining iod.id.e-activated. charcoal. Heating the surface to be cleaned to about 200°C vaporizes the mercury, which is then car- ried by the air stream into the collection filters. In chemical removal methods, a substance is applied which will react readily with mercury at ambient temperatures to form a nearly nonvolatile mercury compound, which can then ------- 44 be swept up. The substances generally used are inorganic poly- sulfides1^/176 or powdered sulfur. 5 A study conducted by Cop- plestone and McArthur^S On various such substances and mixtures noted that two of the most effective treatment mixtures were (1) sulfur, calcium oxide and water, or (2) commercial aerosol hair spray. Thus, effective methods have been developed to control mercury vapors, although they are not always applied because of ignorance or lack of concern about the toxicity of mercury. Other mercury compounds which may cause air pollution are those used in pesticid.es, especially those used to spray crops or weed.s. No particular methods of control are used, other than those for the normal control of pesticides. ------- 45 5. ECONOMICS No information has been found on the economic costs of mercury vapor or mercury compound air pollution or on the costs of its abatement. Data on the production and consumption of mercury and its compounds are presented in Section 3. ------- 46 6. METHODS OF ANALYSIS Various methods have been developed to measure mercury vapor and mercury particles in the atmosphere. Portable con- tinuous monitoring detectors for mercury vapor are available from several companies (Beckman Instruments, Inc.; General Elec- tric Co.; Sunshine Scientific Instruments, Inc.; etc.). These detectors are based on the principle that ultraviolet light at 2537 A is strongly absorbed by mercury vapor-160'178 Thus, any o other vapor which also absorbs light at 2537 A or affects the accuracy of the measurement of the light intensity (such as fogs, dust, and smoke) can cause interference and produce unreliable results. Many compounds d.o absorb light in this range (ozone, carbon dioxid.e, and. aromatic hydrocarbons, for example). Since their sensitivity is much less, however, a high concentration is necessary to interfere with mercury vapor detection (generally a concentration about 100 to 100,000 times greater than that of mercury). The lower sensitivity of these instruments is in the range of 5 to 10 |-ig/m3 with about 2 percent full-scale accuracy- Battery-operated vapor detectors have been described by McMurry and Red.mond1^0 and also by Jacobs and Jacobs.91 Use of these detectors at concentrations of mercury above 1,000 |ag/m3 of air requires recalibration. An apparatus was designed by Nelson jst .al.. to facilitate the calibration of these detectors. ------- 47 Systems have also been developed for use when other vapors which o absorb at 2537 A are present in concentrations high enough to cause serious interference. A specific system for mercury was reported recently by Hawkes and Williston,81 and also by James and Webb.92 Their approaches are basically similar: the air sample is split into two portions and each air stream is passed through identical absorption cells. One of the cells is pre- ceded by a material which removes the mercury vapor from the air stream, and. the difference in absorption values between the two cells is a measure of the mercury vapor. Barringer^ developed a method to measure mercury vapor in free-stand.ing air which is based on absorption of light at 2537 A. By taking advantage of the pressure-broadening of the mercury emission lines, the interference due to other compounds is minimized.. Techniques have been developed which can detect lower concentrations of mercury vapor than those mentioned although they do not continuously monitor. The basic approach is to collect the vapor on absorbing materials such as gold., silver, ft o or paper impregnated with potassium iodide, J and then release it into an ultraviolet detector system. A portable instrument is being developed—using the initial absorption of mercury on gold— which will be able to detect mercury vapor in the picogram range (10~12g) in the atmosphere.71 ------- 48 Mercury vapor can be detected by using indicator papers (such as copper iodide paper,51 selenium sulfide paper,13'132 or selenium paper158), gold chloride on silica gel,78 or commercially available gas-detecting tubes.102 All of these methods are quick and simple but not very sensitive (they can generally detect about 500 to 1,000 |ag/m3 of mercury with approximately ±5% accuracy). They could be useful for detecting vapor leaks, however. Recently a radiochemical method was developed for the detection of mercury vapor. This method is based on isotope ex- change that takes place when the vapors are passed through a solution of 203Hg-mercuric acetate.110 Several methods are available for the determination of mercury in biological materials, such as photometric,171 neutron activation,133 spectrographic'*7 and chemical techniques. Numerous chemical methods have been described for the determination of mercury vapor, mercury in dust, and both or- ganic and inorganic mercury compounds. The chemical procedures consist of collecting the mercury-containing material in im- pingers containing water,38'111 alcohol,38'111 potassium perman- ganate-sulfuric acid, 97' 108» 1J-4,141 potassium permanganate-nitric acid,^ or iodine-potassium iodide solution.111 Trapping is pos- 148 sible with iodide-activated charcoal and mineral wool. ------- 49 The final determination is usually made colorimetrically with dithizone,38'141 di-beta-naphthyl-thiocarbazone,108 or Reyneke salt. The final determination can also be done by means of electrolysis38 or the use of selenium sulfide paper.148 If 100 liters of air are passed through the collection media, the limit of detection is about 1 to 10 [Jg/m3 of mercury, with ±5% accuracy. The final mercury determination is usually d.one in a laboratory. Kud.sk, ' however, has developed an on-site method of determination with a sensitivity of about 1 |ag of mercury. By careful control of the acidity of the solutions, interference from other metals is greatly minimized and causes no problems in most cases. However, problems do arise with certain organo- mercury compounds, especially the dialkyl derivatives .1(^6,139 Linch et.al..1^ found that a collection medium of iodine mono- chloride in acid gave excellent recovery of dimethyl and diethyl mercury. Quino13^ found, isopropyl alcohol to be an effective med.ium for collection of dibutyl mercury. The latter has also developed a simple, rapid method, for the determination of dialkyl mercury compound.s (by reaction with bromine followed by reaction with ditolyl mercury and. dithizone) that can be used in the field. with a sensitivity of about 500 |ag/m3 of mercury—or if determined in the laboratory, about 2 to 12 (ag of the mercury compound. ------- 50 Hamilton and Ruthven^ reported a technique which pro- vides a continuous monitoring of combined mercury vapor and organo-mercury compounds. The technique consists of pyrolyzing the compounds to free mercury vapor, which is then detected by a spectrophotometer. By determining the mercury vapor content of the air, the amount of organic mercury can then be found by difference. ------- 51 7. SUMMARY AND CONCLUSIONS The toxicity of mercury and most of its compounds has been well established. These protoplasmic poisons can be lethal to man, animals, and plants. The high vapor pressure of mercury (resulting in mercury concentrations of 13,000 and 18,000 |ag/m3 at ambient temperatures), and the large quantities used by in- dustries and laboratories result in continual contamination of the environmental air by its vapor. Mercury poisoning has occurred in most major industries which use mercury, sometimes affecting all the employees; many fatalities have been reported as a result of mercury inhalation. Russian animal experiments have shown that the conditioned re- flex is affected, when animals are exposed to mercury vapors in the range of 0.2 to 5 |~ig/m3 for only 9.5 months. Cattle have been poisoned when stabled overnight with a horse that had re- ceived a mercury ointment application. Plants have been damaged when kept in a greenhouse that was painted with a paint con- taining mercury fungicide. Inhalation of only small amounts of mercury or its de- rivatives can result in insidious chronic poisoning, which is manifested by erethism (exaggerated emotional response), muscu- lar tremors, and gingivitis. Mild symptoms are psychopathologi- cal in nature (such as irritability, depression, etc.) and thus ------- 52 may never be diagnosed as resulting from mercury intoxication. The major sources of mercury in the atmosphere are mining and refining processes, electrical manufacturing, chlorine and caustic soda processing plants, and scientific laboratories. Many other minor sources are known. However, little is known about the concentration levels in the ambient air. Some air quality measurements in Cincinnati and Charleston before 1952 have found that particulates contained mercury equivalent to about 0.1 to 0.2 |ag/m3 . However, some recent unpublished data from New York reported particulates collected indoors containing mercury concentrations as high as 40 |ag/m3 . Method.s have been developed, for the control of air pol- lution by mercury; however it is doubtful that these measures are implemented throughout the wide and diverse potential sources of emission that exist. Several good analytical methods for determining atmos- pheric concentrations of mercury are available that provide con- tinuous records and. adequate sensitivity. No information has been found on the economic costs of mercury air pollution or on the costs of its abatement. Based on the material presented, in this report, further studies are suggested in the following areas: ------- 53 (1) Determination of the concentration of mercury in the environmental air, particularly in highly populated areas. (2) Determination of the long-time exposure effects on man, animals, and plants of mercury vapor, its organic and in- organic compounds, and especially particulates containing mer- cury. (3) Evaluation of the contribution to mercury pollution by mines, refineries, and. industrial sources, particularly those in which mercury is heated. (4) Evaluation of the possible health hazards in schools, hospitals, dental offices, and. laboratories caused by mercury pol- lution. (5) Investigation of the possible synergistic effects of mercury with other pollutants, especially with other thiol poisons- lead, cadmium, and arsenic, for example. (6) Investigation of the possible catalytic effect of mercury substances on other materials found in the atmosphere. ------- 54 REFERENCES 1. Ahlmark, A., Poisoning by Methyl Mercury Compounds, Brit. J. Ind. Med. 5;117 (1948). 903 2. Aika, J. K., and R. H. Fitz, The Distribution of Hg Labeled Mercaptomerin in Human Tissues, J. Clin. Invest. 35_:775 (1956). 3. Air and Water News 2(26) (1968). 4. Al'terman, N. A., and S. F. Sorokina, Disease Incidence in Underground Workers in Mercury Mines, Gigiena i Sanit. 31;7 (1966). 5. 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Governor's Conf. and Exhibit on Atmosphere Pollution, Trenton, N.J., pp. 23-31 (1952). ------- 74 APPENDIX ------- APPENDIX TABLE 1 SUMMARY OF MERCURY TOXICITY DATA VIA INHALATION" 159 SYMPTOMS AND EFFECTS COMMENTS ACUTE POISONING Metallic taste, nausea, abdominal pain, vomiting, diarrhea, headache, and sometimes albuminuria; after a few days the salivary glands swell, stomatitis and gingivitis develop, teeth may loosen, and ulcers may form on lips and cheeks. In addition, organic mercury derivatives irritate mucous membranes, pro- ducing sensation of dryness and irritation in the nasopharynx and. mouth. Very high exposures result in tightness and pain in the chest, difficulty in breathing, and coughing. Later stages characterized by hemolysis, sleeplessness, headache, facial tics, tremor of the digits, deliriousness, and hallucina- tions CHRONIC POISONING Psychic and emotional disturbances (irritable, irascible especially when criticized, unable to concentrate, fearful, indecisive, or depressed). Headache, fatigue, weakness, loss of memory, and either drowsiness or insomnia. Tremors affecting hand, head, lips, tongue,or jaw; writing affected. Other neurological disturbances include paresthesia, affections of taste or smell, neuralgia, and dermo- graphism. Renal disease. Chronic nasal catarrh and epistaxis. Salivation, gingivitis, and digestive disturbances. Ocular lesions, amblyopia, and narrowing of vision, the latter particularly from organic compounds Relatively infrequent; in milder cases recovery occurs in 10-14 days, although chronic poisoning symptoms may ensue, accompanied by muscular tremors and psychic disturbances. In severe poison- ing the physical defects and mental deterioration may continue. Death is frequent in very severe cases as a result of extreme exhaustion. 1,200 to 8,500 ng Hg/m^ of air have resulted in acute poisoning May appear after a few weeks of exposure, or delayed much longer. Organic mercury symptoms are con- fined more specifically to the nervous system. Slow recovery on removal from exposure. Organic mercury compounds mainly affect the motor and. sensory nerves; symptoms of salivation, stomati- tis, and erethism are more pronounced in exposure to the inorganics ------- 76 APPENDIX TABLE 2 172 PROPERTIES AND USES OF MERCURY Atomic Symbol; Hg Molecular Weight; 200.59 Isotopes; 202 (29.6%), 200 (2003%), 199 (17.0%), 201 (13.2%), 198 (10.1%), 204 (6.7%), 196 (0.15%). Physical Properties; Silver white liquid at normal ambient temperatures; high density (13.5939 at 20 C); high surface tension (480.3 dyn/cm); slightly volatile at ordinary tempera- ture (see Table 3 and Figure 2); heat of fusion 2.82 cal/g; heat of vaporization 65 cal/g; solidifies at -39°C to a tin- white, ductile, malleable mass; boiling point 356.9°0 Toxicitv, Human; Readily absorbed via respiratory tract (ele- mental mercury vapor, mercury compound dusts), intact skin, and gastrointestinal tract, although occasional incidental swallowing of metallic mercury is without harm. Spilled and heated elemental mercury is particularly hazardous. Acute: soluble salts have violent corrosive effects on skin and mucous membranes; severe nausea, vomiting, abdominal pain, bloody diarrhea; kidney damage; death usually within 10 days. Chronic: inflammation of mouth and gums; excessive salivation, loosening of teeth; kidney damage; muscle tremors, jerky gait, spasms of extremities; personality changes, depression, irri- tability, nervousness. Phenyl and alkyl mercurials can cause skin burns and be absorbed by the skin. Burning sensation is delayed several hours and thus gives no warning. Alkyls have affinity for brain tissue and may cause permanent damage„ Phenyls are no more toxic than inorganic mercury. Uses: In barometers, thermometers, hydrometers, pyrometers; in mercury-arc lamps producing ultraviolet rays; in switches, fluorescent lamps; in mercury boilers; in manufacture of all mercury salts, mirrors; as catalyst in oxidation of organic compounds; for extracting gold and silver from ores, for making amalgams, electric rectifiers, mercury fulminate; also in dentistry; in determining nitrogen by Kjeldahl method, for Millon's reagent; as cathode in electrolysis, and many other uses., Also in Pharmaceuticals, agricultural chemicals, anti- fouling paints. ------- 77 APPENDIX TABLE 3 SATURATION CONCENTRATION OF MERCURY IN AIR AT VARIOUS TEMPERATURES* Mercury Temperature Concentration °C °F Pressure (nun) (|ag/m3) -28 -10 0 4 8 10 12 16 20 24 28 30 32 36 40 44 48 50 70 100 200 300 400 -18.4 14.0 32.0 39.2 46.4 50.0 53.6 60.8 68.0 75.2 82.4 86.0 89.6 96.8 104.0 111.2 118.4 122.0 158.0 212.0 372.0 572.0 752.0 .0000063 .0000606 .000185 .000276 .000406 .000490 .000588 .000846 .001201 .001691 .002359 .002777 .003261 .004471 .006079 .008200 .01098 .01267 .04825 .2729 17.287 246.80 1,574.1 80 740 2,180 3,210 4,650 . 5,880 6,640 9,430 13,200 18,300 25,200 29,500 34,400 46,600 62,600 83,300 110,000 126,000 453,000 2,360,000 118,000,000 1,390,000,000 7,530,000,000 The saturation concentration of mercury in air given in the table was calculated from the mercury vapor pressure data. Two assumptions were necessary to make the calculation: (1) that the atmospheric pressure is equal to 760 mm, and (2) that mercury vapor behaves as an ideal gas or that it obeys the ideal gas equation: PV = nRT where P = pressure V = volume n = moles of mercury vapor T = temperature R = gas constant = 0.06236 (mm) (m3) (°K) (mole). The concentration of mercury can be calculated by: S= (moles Hg in air) (mol wt Kg) (106) volume or air in m-> = "Hq X 200.6 X 1Q6 = PHq X 200.6 X 1Q6 V RT = PHq X 3.216 X 109 T p where Hg is vapor pressure of mercury in mm and T is in °K or 273+°C. ------- APPENDIX TABLE 4 MERCURY CONSUMED IN THE UNITED STATES BY USES, 1947-1966 a (Flasks in thousands) 126 Uses Agriculture (includes fungicides and bactericides ) Ama 1 gama t i on Catalysts Dental preparations Electrical apparatuses Electrolytic preparation of chlorine and caustic soda General laboratory use , commercial General laboratory use , government General laboratory use, total Industrial and control instruments Paint, antifouling Paint, mildew-proofing Paper and pulp manufacture Pharmaceuticals Fulminate for munitions and blasting caps Redistilled Other 1947 5. 0. 5. 0. 6. 0. b b 0. 5. 0. 3. 0. 4. 1. 6 1 1 8 8 7 3 4 8 1 5 7 8. 1948 7.1 0.1 3.3 1.0 6.5 0.8 b b 0.4 5.7 1.0 3.4 0.4 6.5 10.2 1949 4.7 0.2 2.5 1.0 7.3 0.8 b b 0.3 5.0 1.7 3.4 0.2 6.6 6.2 1950 4.5 0.2 2.7 1.5 12.1 1.3 b b 0.7 5.4 3.1 6.0 0.3 7.6 3.9 1951 7.7 0.2 2.6 0.8 10.3 1.5 b b 0.5 6.2 2.5 2.8 0.5 8.8 12.5 1952 5.9 0.2 1.1 1.3 8.0 2.5 b b 0.6 6.4 1.2 1.4 0.3 7.6 6.4 1953 6.9 0.2 0.8 1.1 9.6 2.4 b b 1.2 5.6 0.7 1.9 0.0 7.8 14.1 1954 7.7 0.2 0.6 1.4 10.8 2.1 b b 1.1 5.2 0.5 b c 1.8 0.1 9.3 1.9 1955 7.4 0.2 0.7 1.2 9.3 3.1 b b 1.1 5.6 0.7 b c 1.6 0.1 9.6 16.7 1956 9.9 0.2 0.9 1.3 9.8 3.4 b b 1.0 6.1 0.5 b c 1.6 9.5 10.0 Total 35.6 46.3 39.9 49.2 56.9 42.6 52.3 42.8 57.2 54.1 (continued) ------- APPENDIX TABLE 4 (Continued) MERCURY CONSUMED IN THE UNITED STATES BY USES, 1947-1966 (Flasks in thousands) 126 Uses Agriculture (includes fungicides and bacter icides ) Amalgamation Catalysts Dental preparations Electrical apparatuses Electrolytic preparation of chlorine and caustic soda General laboratory use, commercial General laboratory use, government General laboratory use, total Industrial and control instruments Paint, antifouling Paint, mildew-proofing Paper and pulp manufacture Pharmaceuticals Fulminate for munitions and blasting caps Redistilled Other Total 1957 6.3 0.2 0.9 1.4 9.2 4.0 b b 0.9 6.0 0.6 b c 1.8 9.7 11.0 52.9 1958 6.3 0.3 0.8 1.7 9.3 4.6 b b 1.0 6.1 0.8 b c 1.4 9.5 11.0 52.6 1959 3. 0. 1. 1. 8. 5. b b 1. 6. 1. 2. 4. 1. 9. 7. 54. 2 3 0 8 9 8 1 2 0 5 4 7 3 7_ 9 1960 3.0 0.3 1.0 1.8 9.3 6.2 b b 103 6.5 1.4 2.9 3.5 1.7 9.7 207 51.2 1961 10.1 0.3 0.7 1.1 10.3 6.0 1.2 1.2 5.6 3.1 b 2.5 9.0 6.0 55.8 1962 4.3 0.3 0.9 2.0 11.6 7.3 1.8 1.8 5.2 0.1 4.6 2.6 2.4 9.0 12o4 65.3 1963 2.5 0.3 0.6 2.4 11.1 8.0 1.2 3.8 5.1 4.9 0.3 6.4 2.8 4.1 9.2 20.3 78.0 1964 3.1 0.7 0.7 2.6 10.7 9.6 1.5 17.0 18.5 5.0 0.6 4.9 2.2 5.1 1104 7.7 82.6 1965 3.1 0.5 0.9 1.6 13.9 8.8 1.1 1,1 4.6 0.3 7.5 0.6 3.3 12.0 15.4 73.6 1966 2.4 0.5 1.9 1.4 13.6 11.5 1.6 1.6 4.3 0.1 7.8 0.6 3.7 7.0 15.6 72.0 al Flask = 76 Ibo •'-'Data not available. clncluded with acrriculture. ------- APPENDIX TABLE 5. PROPERTIES AND USES OF SOME MERCURY COMPOUNDS Q(~) 0^' Compound Mol. Wt. % Wt. Hq mp°C bp°C Toxicity Uses Ammoniated .mercuric chloride (mercuric ammonium 1 chloride) HgNH Cl 252.09 79.58 Infusible See mercury As topical anti-infectiva Mercuric bromide HgBr0 360.44 55.66 237 See mercury As laboratory reagent Mercuric chloride (Corrosive sublimate) HgCi 271.52 73.88 282 (3) LD for rats, orally 37 mg/kg For preserving wood, embalming, disinfecting, etching metals, tanning leather, as ink for mercurography, in treating seed potatoes, as topical antiseptic Mercuric cyanide Hg(CN) 252.65 79.40 Decomposes Violent poison As topical antiseptic, antisyphilitic Mercuric fluoride 2 238.61 84.07 645 (650) See mercury and fluorine In fluorination of organic compounds Mercuric fulminate Hg(NCO) 284.65 Explosive In detonators Mercuric iodide HgI0 454.45 (44.14) 259 (350) See mercury As Nessler's Reagent, topical antiseptic, local counter- irritant and vesicant for horses (continued) ------- APPENDIX TABLE 5. PROPERTIES AND USES OF SOME MERCURY COMPOUNDS Compound Mol. Wt. % Wt. Hg mp°C bp°C Toxicity Uses Mercuric nitrate Hg(NO ) 'H.,0 J 2 z 342.64 70 Sae mercury In manufacture of felt, mercury fulminate, destruction of phylloxera Mercuric oxide (red) HgO 216.61 92.61 Decomposes at 500 See mercury As topical antiseptic, paints for ships' bottoms; for diluting pigments; in batteries; as reagent in quality determinations Mercuric sulfate HgS04 296.68 (67.62) Decomposes As electrolyte for primary batteries, in metallurgy of gold and silver Mercuric sulfide (cinnabar) HgS 232.68 Sublimes at 583.5 See mercury As pigment for horn, rubber, plastics, sealing wax, colored papers, linen marking Mercuric thiocyanate Hg(SCN) 2 316.79 63.33% Decomposes See mercury In fireworks; as intensifier in photography Mercurous chloride 472.09 84.98% Sublimes at 400-500 Low mammalian toxicity; 210 mg/kg (in rats) caused mercurial symptoms For dark-green Bengal lights, calomel paper, when mixed with gold in painting on porcelain, calomel electrodes, as fungicide, in agriculture to control root maggots. Med. use: as cathartic, diuretic, antiseptic Mercurous sulfate i SO 2 4 497.29 80.68% Decomposes In making electric batteries (continued) ------- APPENDIX TABLE 5. PROPERTIES AND USES OF SOME MERCURY COMPOUNDS80'121 Compound Mol. Wt. % Wt. Ha bp C Toxicity Uses Die thy 1 mercury 258.73 159 As fungicide, herbicide Dimethyl mercury 230.68 (95) As fungicide, herbicide Ethyl mercuric chloride 265.13 75.66% 192 Highly toxic; see mercury As fungicide for treating seeds Mercuric acetate 318.70 62.95 Decomposes See mercury In mercuration of organic compounds, absorption of ethylene Mercuric benzoate 460.85 43.53 In treatment of syphilis and gonorrhea Mercuric lactate (CH CHOHCOO) Hg •J £ Acute oral LD for rats 200 mgAg As fungicide Mercuric oleate 763.53 26.29 As topical parasiticide Mercuric sodium p-phenosulf onate 590.92 33.95 See mercury As germicide in soaps and lotions (1:100), local antiseptic 00 to (continued) ------- APPENDIX TABLE 5. PROPERTIES AND USES OF SOME MERCURY COMPOUNDS80'121 Compound Me r cur in Ci4H25HgN05 Mercurophen C6H4Hg NNa04 Mercurous acetate Hg2(CH3coo)2 Methyl mercuric chloride CH HgCl Methyl mercuric propionate CH3Hg02CC2H5 Methyl mercuric dicyaniamide CH3HgC2H3N4 Methyl mercuric nitrile CH HgCN Mol. Wt. % Wt. Hq 487.97 41.11% 377.70 53.11% 519.31 77.26% 251.10 mp C bp°C 170 Volatile at 100 156-157 95 Toxicity See mercury High mammalian toxicity (internal and on skin contact) High mammalian toxicity; vesicant Uses As diuret j c Med. and vet. use: As local antiseptic, surgical instrument disinfectant Med. use: formerly in syphilis treatment As fungicide As fungicide, antibiotic; in seed treatment As fungicide, in seed treatment As fungicide, in seed treatment (continued) oo u> ------- APPENDIX TABLE 5. PROPERTIES AND USES OF SOME MERCURY COMPOUNDS80'121 Compound Mol. Wt. % Wt. Hq mp°C bp C Toxicity Uses Methyl mercuric pentachlorophenate CH HgOC Cl 3 65 192 Acute oral LD for rats 56 mg/kg 50 As fungicide, in seed treatment Methyl mercuric quinolinolate 133-137 Acute oral LD for rats 72 mgAg 50 As fungicide, in seed treatment Phenylmercuric acetate 336.75 59.57% 149 High mammalian toxicity; oral LD_ for rats 40 As herbicide, fungicide Phenylmercuric benzoate 95-99 High mammalian toxicity As fungicide Phenylmercuric chloride C H HgCl 65 313.18 64.06% 250-252 See mercury; high mammalian toxicity As antiseptic, fungicide. Med. use: as external local antiseptic Phenylmercur ic hydroxide C H HgOH 6 5 Decomposes at 200 High mammalian toxicity As fungicide Phenylmercuric nitrate, basic C6H5HgOH•C6H5HgN03 634.45 63.24% Decomposes at 187-190 See mercury; subcutaneous I»E> for rats 63 rng/j,™ As fungicide oo (continued) ------- APPENDIX TABLE 5. PROPERTIES AND USES OF SOME MERCURY COMPOUNDS80'121 Compound Mol. Wt. % Wt. Hg. mp C bp°C Toxicity Uses Phenylmercuric salicylate - C6H4OH 155-161 High mammalian toxicity As fungicide Phenylmer curie borate 338.56 59.25% 112-113 See mercury; Much less toxic than most mercurial compounds As local external antiseptic CD ------- 86 APPENDIX TABLE 6 U.S.A. PRODUCTION OF MERCURY BY STATES (1936-1956) Flasks (1 Flask = 76 Ib) 124,126 Year 1966 1965 1964 1963 1962 1961 1960 1959 1958 1957 1956 1955 1954 1953 1952 1951 1950 1949 1948 1947 1946 1945 1944 1943 1942 1941 1940 1939 1938 1937 1936 Alaska * * 303 400 3,719 3,743 4,459 3,743 3,380 5,461 3,280 (1,000) 1,046 40 28 100 100 127 699 * * 786 * * 162 Calif. 16,070 13,404 10,291 13,592 15,951 18,688 18,764 17,100 22,365 16,511 9,017 9,875 11,262 9,290 7,241 4,282 3,850 4,493 11,188 17,165 17,782 21,199 28,052 33,812 29,906 25,714 18,629 11,127 12,277 9,743 8,693 Idaho 1,134 1,119 83 * * * * * it 2,260 3,394 1,107 609 * 887 357 543 886 868 62 * 4,261 * * * * Nevada 3,355 3,333 3,262 4,944 6,573 7,486 7,821 7,156 7,336 6,313 5,859 5,750 4,974 3,254 3,523 1,400 680 4,170 1,206 3,881 4,567 4,338 2,460 4,577 5,201 4,238 5,924 828 336 198 211 Oregon 700 1,364 126 * * * 513 1,224 2,276 3,993 1,893 1,056 489 648 868 1,177 5 1,167 1,351 1,185 1,326 2,500 3,159 4,651 6,935 9,032 9,043 4,592 4,610 4,264 4,126 All Other 749 362 77 181 34 1,745 1,666 2,033 2,710 87 734 167 163 1,105 77 106 2,664 4,017 3,842 8,804 5,937 4,019 2,086 768 2,303 3,539 U.S.A. 22,008 19,582 14,142 19,117 26,277 31,662 33,223 31,256 38,067 34,625 24,177 18,955 18,543 14,337 12,547 7,293 4,535 9,930 14,388 23,244 25,348 30,763 37,688 51,929 50,846 44,921 37,777 18,633 17,991 16,508 16,569 *Included in All Other. ------- 87 APPENDIX TABLE 7 MAJOR MERCURY MINES* IN 1963 AND THEIR LOCATIONS150 Mine County State Red Devil Aniak District Alaska National Maricopa Arizona New Idria San Benito California Buena Vista San Luis Obispo California New Almad.en Santa Clara California Culver-Baer Sonoma California Cordero Humboldt Nevada lone Nye Nevada *These eight mines accounted for 97% of the domestic primary production in 1963. ------- 88 APPENDIX TABLE 8 LIST OF MAJOR MERCURY-PRODUCING MINES IN 1966126 Mines Producing More Than 1,000 Flasks* Mine County Cordero Little King New Idria Buena Vista Mt. Jackson Idaho-Almaden Humboldt Kings San Benito San Luis Obispo Sonoma Washington State Nevada California California California California Idaho Mines Producing 500 to 1.000 Flasks Mines County Gibraltar (Sunbird) New Almaden Socrates Black Butte Santa Barbara Santa Clara Sonoma Lane State California California California Oregon Mines Producing 100 to 500 Flasks Mine B & B Brinkerhoff (Loretta) Kitten Springs Mt. Diablo Tehachapi (Walabu) Knoxville North Star Guadalupe Altoona White Mountain Big Sam Pine Mountain Fresno Bretz County Esmeralda Pershing Pershing Contra Costa Kern Napa San Benito Santa Clara Trinity Aniak Maricopa Maricopa Presidio Malheur State Nevada Nevada Nevada California California California California California California Alaska Arizona Arizona Texas Oregon *Flask = 76 Ib. ------- 89 APPENDIX TABLE 9 DIRECTORY OF SELECTED PRODUCERS, CONSUMERS, AND DEALERS OF MERCURY136 LARGE PRODUCERS Alaska: Decoursey Mountain Mining Co., P.O. Box 442, Anchorage. California: Harold Biaggini, Atascadero. COG Minerals Corp., Denver Club B, Denver, Colo. New Idria Mining & Chemical Co., P.O. Box 87, Idria. Sonoma Quicksilver Mines, Inc., Guerneville. Idaho : Holly Minerals Corp., 340 Third St., N.W., Albuquerque, N. Mex. Rare Metals Corp. of America, 10th Floor, First Security Bldg., Salt Lake City, Utah. Nevada: Cordero Mining Co., 131 University Ave., Palo Alto, Calif. Oregon: Arentz-Comstock Mining Venture, 870 First Security Bldg., Salt Lake City, Utah. Bonanza Oil & Mine Corp., Sutherlin. LARGE CONSUMERS The Adams & Westlake Co., Elkhart, Ind. Allied Chemical Corp., National Aniline Div., 40 Rector St., New York, N.Y. Allied Chemical Corp., Solvay Process Div., P.O. Box 271, Syracuse, N.Y. American Cyanamid Co., 30 Rockefeller Plaza, New York, N.Y. American Meter Co., Erie, Pa. American Meter Co., 1300 Industrial Blvd., Dallas, Tex. B I F Industries, Inc., P.O. Box 1342, Providence, R.I. Bailey Meter Co., 1052 Ivanhoe Road, Cleveland, Ohio. J.T. Baker Chemical Co., Phillipsburg, N.J. F.W. Berk & Co., Inc., Park Place East, Wood Ridge, N.J. Buckman Laboratories, Inc., Memphis, Tenn. Carbide & Carbon Chemicals Co., A Div. of Union Carbide & Carbon Co., 300 Madison Ave., New York, N.Y. Carbide & Carbon Chemicals Co., A Div. of Union Carbide & Carbon Co., Niagara Falls, N.Y. L.D. Caulk Co., Milford, Del. Cooper-Hewitt Electric Co., 410 8th St., Hoboken, N.J. E.I. du Pont de Nemours & Co., Inc., 1007 Market St., Wilmington, Del, Eastern Smelting & Refining Co., 107-109 W. Brookline St., Boston, Mass. Thomas A. Edison, Inc., Primary Battery Div., Bloomfield, N.J. Foxboro Co., Foxboro, Mass. General Aniline & Film Corp., Dyestuff & Chem. Div., P.O. Box 12, T.i nflon NT .T (continued) ------- APPENDIX 9° TABLE 9 (Continued) DIRECTORY OF SELECTED PRODUCERS, CONSUMERS, AND DEALERS OF MERCURY136 LARQE CONSUMERS General Color Co., Inc., 24 Avenue B, Newark, N.J. General Electric Co., Purchasing Dept., 1 River Rd., Schenectady, N.Y. Gulf Oil Corp., Gulf Bldg., Pittsburgh, Pa. Homestake Mining Co., Lead, S. Dak. Mallinckrodt Chemical Works, Jersey City, N.J. Mathieson Chemical Corp., Mathieson Bldg., Baltimore, Md. The Mercoid Corp., 200 Wagaraw Rd., Hawthorne, N.J. Minneapolis-Honeywell Regulator Co., Micro Switch Div., Freeport, 111. Minneapolis-Honeywell Regulator Co., Brown Instruments Div., Pur- chasing Dept., 4331 Wayne Ave., Philadelphia, Pa. Monsanto Chemical Co., 918 16th St., N.W., Washington, D.C. Pennsylvania Salt Mfg. Co., 1000 Widener Bldg., Philadelphia, Pa. Public Service Electric & Gas Co., 80 Park Place, Newark, N.J. Quicksilver Products, Inc., 407 Sansome St., San Francisco, Calif. Standard Oil Co. of Indiana, 910 S. Michigan Ave., Chicago, 111. Taylor Instrument Companies, P.O. Box 110,, Rochester, N.Y. Westinghouse Electric Corp., 306 4th Ave., Pittsburgh, Pa. Wyandotte Chemical Corp., Wyandotte, Mich. LARGE DEALERS Associated Metals & Minerals Corp., 75 West St., New York, N.Y. Ayrton Metal & Ore Corp., 30 Rockefeller Plaza, New York, N.Y. Bache & Co., 36 Wall St., New York, N.Y. Barada & Page, Inc., Guinotte Ave. & Michigan Ave., Kansas City, Mo. Earth Metals Co., Inc., 99-129 Chapel St., Newark, N.J. F.W. Berk & Co., Inc., Park Place East, Wood Ridge, N.J. Braun Corp., 1363 S. Bonnie Beach Place, Los Angeles, Calif. Chemical Mfg. Co., Inc., of Calif., 714 W. Olympic Blvd., Los Angeles, Calif. Derby & Company, Inc., 10 Cedar St., New York, N.Y. Stanley Doggett, Inc., 99 Hudson St., New York, N.Y. Fleischman Burd & Co., 22 W. 48th St., New York, N.Y. Geotrade Industrial Corp., 141 E. 44th St., New York, N.Y. Goldsmith Bros., Smelting & Refining Co., 1300 W. 59th St., Chicago, 111. Gordon I. Gould & Co., 58 Sutter St., San Francisco, Calif. W.R. Grace & Co., P.O. Box 286, Church St. Annex, New York, N.Y. Haesler Metal & Ore Corp., 11 W. 42d St., New York, N.Y. Chas. P. Hull Co., Inc., 50 Church St., New York, N.Y. Interchange Commercial Corp., 46 W. 55th St., New York, N.Y. International Bartering Co., 52 Broadway, New York, N.Y. International Minerals & Metals Corp., 11 Broadway, New York, N.Y. International Selling Corp., 122 E. 42d St., New York, N.Y. L.H. Keller Co., 50 E. 42d St., New York, N.Y. Leghorn Trading Co., Inc., 141 E. 44th St., New York, N.Y. Lentex Metal & Chemical Co., 500 Fifth Ave., New York, N.Y. (continued) ------- 91 APPENDIX TABLE 9 (Continued) DIRECTORY OF SELECTED PRODUCERS, CONSUMERS, AND DEALERS OF MERCURY .136 LARGE DEALERS Fred H. Lenway & Co., Inc. 112 Market St., San Francisco, Calif. Mefford Chemical Co., Sub. McKesson & Robbins, Inc., 5353 Jillson St., Los Angeles, Calif. Mercantile Metal & Ore Corp., 595 Madison Ave. New York, N.Y. Mercer Chemical Corp., 11 Mercer St., New York, N.Y. Merchants Chemical Co., Inc., 60 E. 42d St., New York, N.Y. Metal Traders, Inc., 26 Broadway, New York, N.Y. Metallurg, Inc., 99 Park Ave. New York, N.Y. Metalsalts Corp., 200 Wagaraw Rd., Hawthorne, N.J. Pacific Vegetable Oil Co., 62 Townsend St., San Francisco, Calif. Philipp Bros., Inc., 70 Pine St., New York, N.Y. C. L. Pratt, Jr., 10210 Second Blvd., Detroit, Mich. Quicksilver Products, Inc., 407 Sansome St., San Francisco, Calif, Frank Samuel & Co., 2200 Lincoln-Liberty Bldg., Philadelphia, Pa. The Schmitz-Schoenewaldt-Turner Co., 20 Vesey St., New York, N.Y. Seaforth Mineral & Ore Co., 3537 Lee Rd., Cleveland, Ohio William M. Stieh & Co., Inc., 721 River Rd., Teaneck, N.J. Swiss Bank Corp., N.Y. Agency, 15 Nassau St., New York, N.Y. ------- 92 APPENDIX TABLE 10 LIST OF SOME COMPANIES PRODUCING MERCURY CHEMICALS (1968) Allied Chemical Corp. Industrial Chemicals Div- J. T. Baker Chemical Co. City Chemical Corp. W. A. Cleary Corp. Kewanee Oil Co. Harshaw Chemical Co. Div. H. Kohnstamm and Co., Inc. General Color Co. Div- Mallinckrodt Chemical Works Industrial Chemical Div. Merck & Co., Inc. Metalsalts Precision Chemical Corp. R.S.A. Corp. Tenneco Chemicals, Inc. Nuodex Div. Troy Chemical Corp. Velsicol Chemical Corp. Marcus Hook, Pa. Phillipsburg, N.J. Jersey City, N.J. New Brunswick, N.J. Cleveland, Ohio Newark, N.J. Jersey City, N.J. Hawthorne, N.J. Richmond, Calif. Ardsley, N.Y. Elizabeth, N.J. Newark, N.J. Wood Ridge, N.J. ------- APPENDIX TABLE 11 MERCURY-CONTAINING PESTICIDES 185 Product Compound Producer Acme Panogen Ad vacide PMA Advacide PMO Advacide 60 Agrosol Agrox C Agrox Calo-clor Calo-gran Calocure Calogreen Centerchem Ceresan L Ceresan M Ceresan M-DB "Ceresan" Red Chipcote 25 Methyl mercury dicyandiamide Phenylmercuric acetate Phenylmercuric oleate Phenylmercuric oleate Methyl mercury dicyandiamide Ethyl mercury chloride and phenyl- mercuric acetate Phenyl mercury urea Mercuric chloride, mercurous chlo- ride Mercuric chloride, mercurous chlo- ride Mercury Mercurous chloride Mercuric chloride Methyl mercuric acetate Methyl mercury 2,3-dihydroxy propyl- mercaptide Ethylmercuric p-toluene sulfon- anilide Ethylmercuric p-toluene sulfon- anilide Ethylmercuric chloride Methyl mercury nitrile Acme Advance Division Advance Division Advance Division Chipman Chipman Chipman Mallinckrodt Mallinckrodt Mallinckrodt Mallinckrodt Center Chemical, Incorporated Du Pont Du Pont Du Pont Du Pont Chipman (continued) ------- APPENDIX TABLE 11 (Continued) MERCURY-CONTAINING PESTICIDES Product Compound Producer Chipcote 75 Coromerc C Coromerc Liquid Doggett Fison Dap Cal Doggett Fison Dap Cal Doggett Fison Turf Tox MC Emrni E-Z Flo Puratized Fung Chex Gallotox Gallotox 51 Green Cross Erad Green Cross Liquid Merlane Green Cross Liquid San Green Cross Merlane Dust Green Cross San Dust Methyl mercury nitrile Phenyl mercury Phenyl mercury Mercuric chloride, mercurous chlo- ride Phenylmercuric acetate Mercuric chloride, mercurous chlo- ride N-Ethylmercuri-1,2,3,6,-tetrahydro- 3,6-endo-methanol-3,4,5-677 Hexa- chlorphthalimid e Phenylmercuric monoethanolammonium 1actate Murcuric chloride, mercurous chlo- ride Phenylmercuric acetate Volatile mercury compounds Phenylmercuric acetate Methyl mercury-8-hydroxyquinolinate Methylmercuric acetate Methyl mercury 2,3-dihydroxy propyl- mercaptide Methyl mercury pentachlorophenolate Methyl mercury pentachlorophenolate Chipman Davison Davison Doggett Fiser Doggett Fiser Doggett Fiser Velsicol E. ;. Flo Wood Ridge Guard Guard Green Cross Green Cross Green Cross Green Cross Green Cross ' continued ) ------- APPENDIX TABLE 11 (Continued) MERCURY-CONTAINING PESTICIDES Product Compound Produc er GSCI GSCI Kroma-Clor Liquiphene Apple Scab Fungicide Liquiphene Turf Fungicide Mema Metnmi Merbam Mercuram Mergamma Mergamma C Mergamma Liquid Mersolite 88 Mersolite 88 W Mersolite 810 Mersolite 830 Mercurous chloride Mercuric chloride Mercury dimethyl dithiocarbamate Phenylmercuric acetate Phenylmercuric acetate Methoxyethyl mercury acetate N-methylmercuri-1,2,3,6-tetrahydro 3,6-endomethano-3,4,5,6,7,7- hexachlorophthalimide Phenylmercuric dimethyldithiocar- bamate Phenylmercuric dimethyld ithiocar- bamate Phenyl mercury urea Ethylmercuric chloride and phenyl- mercuric acetate Methyl mercury dicyandiamide Phenylmercuric acetate Phenylmercuric acetate Phenylmercuric acetate Phenylmercuric acetate Gallard- Schlesinger Gallard- Schlesinger Mallinckrodt Vine land Vineland Chipman Velsicol Chipman Vineland Chipman Chipman Chipman Wood Ridge Wood Ridge Wood Ridge Wood Ridge (continued) ------- APPENDIX TABLE 11 (Continued) MERCURY-CONTAINING PESTICIDES Product Compound Producer Metasol 10 Metasol Bi-Cal Metasol EMCL Metasol MMH Concentrate Metasol MMH Dual purpose Metasol MMH Liquid-dual purpose Metasol MMH Liquid seed treatment Metasol MMH mercury drill box formulation Metasol MMH powder Metasol MMH regular Metasol Thiram Mercury Miller (Puratized) Apple Spray Millers Puraspra Morsodren N5 DS New York Science Supply Phenylmercuric acetate Mercuric chloride, mercurous chlo- ride Ethylmercuric chloride Methyl mercury-8-hydroxy quinolinate Methyl mercury-8-hydroxy quinolinate Methyl mercury-8-hydroxy quinolinate Methyl mercury-8-hydroxy quinolinate Methyl mercury-8-hydroxy quinolinate Methyl mercury-8-hydroxy quinolinate Methyl mercury-8-hydroxy quinolinate Mercuric chloride and mercurous chlo- ride Phenylmercuri monoethanolammonium ac et at e- Phenylmercuric triethanolammonium lactate Methylmercury dicyandiamide Phenylmercuric triethanolammonium lactate Mercuric chloride Metal Salts Metal Salts Metal Salts Metal Salts Metal Salts Metal Salts Metal Salts Metal Salts Metal Salts Metal Salts Metal Salts Miller Chemical & Fertilizer Miller Products Morton Guard New York Science Supply (continued) ------- APPENDIX TABLE 11 (Continued) MERCURY-CONTAINING PESTICIDES Product Compound Producer Niagara Puratized agri- cultural spray Nuodex PMA-18 Nuodex PMO-10 Ortho-LM Apple Spray Ortho-LM Seed Protectant Panogen 15 Panogen 42 Panterra Parson's Ready Mix seed treatment Parson's Slurry Concentrate Pearson's Merc-O-Dust Phelam Phenmad Phenyl mercury fungicide PM 2,4-D PM ACETATE PMAS PMB Proturf fertilizer and fungicide Proturf fungicide Phenylmercuric triethanolammonium lactate Phenylmercuric acetate Phenylmercuric oleate Methylmercury-8-hydroxyquinolinate Methylmercury-8-hydroxyquinolinate Methylmercury dicyandiamide Methylmercury dicyandiamide Methylmercury dicyandiamide Chloromethoxypropyl mercuric acetate Chloromethoxypropyl mercuric acetate Mercurypentanedion Phenylmercuric dimethyldithiocar- bamate Phenylmercuric acetate Phenylmercuric acetate Phenylmercuric acetate Phenylmercuric acetate Phenylmercuric acetate Phenylmercuric borate Phenylmercuric acetate Phenylmercuric acetate Niagara Nuod ex Nuodex Chevron Chevron Morton Morton Morton Parsons Parsons Pearsons Wood Ridge Mallinokrodt Agway Cleary Guard Cleary Guard Scott Scott (continued) ------- APPENDIX TABLE 11 (Continued) MERCURY-CONTAINING PESTICIDES Product Compound Producer Purasan PMA Puraseed Puratized Apple Spray Puratol Puraturf No. 10 Puraturf 10 Quicksan Quicksan 20 Quicksan C20 Quicksan CMA Real-Kill Moth Proofer Satnin Corp. Samin Corp. Mercuric Chlo- ride Samin Corp. Mercury Oxide Scutl Semesan Bel Semesan Seed Disinfectant Semesan Turf Fungicide Setrete Phenylmercuric acetate Mercury compound Phenylmercuric monoethanol Ammonium acetate Phenyl mercury Phenylmercuric acetate Phenylmercuric monoethanolammonium lactate Phenylmercuric acetate Phenylmercuric acetate Chloromethoxypropylmercurie acetate Chloromethoxypropylmercuric acetate Phenylmercuric lactate Ethylmercuric chloride Mercuric chloride Mercuric oxide Phenylmercuric acetate Hydroxymercurichlorophenol Hydroxymercurichlorophenol Hydroxymercurichlorophenol Phenylmercuric ammonium acetate Guard Guard Metasol Canada, Limited Guard Metasol Canada, Limited Guard Stecker Stecker Stecker Stecker Cook Chemical Company Samin Corporation Samin Corporation Samin Corporation Scott Du Pont Du Pont Du Pont Cleary VD 03 (continued) ------- APPENDIX TABLE 11 (Continued) MERCURY-CONTAINING PESTICIDES Product Compound Producer Setrete-Fortifled Setrete Mist Shepard Chemical EMA Shepard Chemical EMC Shepard Chemical BMP Stauffer Mer-CAD Stauffer Mer-Sol 7 Stauffer Mer-Sol 48 Stauffer Mer-Sol 51 Tersan OM Troysan CMP Acetate Troysan PMA Troysan PMB Troysan PMO Ultraclor Wood Ridge Calomel Wood Ridge Corrosive Sublimate Wood Ridge Mixture 21 Ethylmercuric acetate and phenyl- mercuric acetate Ethylmercuric acetate and phenyl- mercuric acetate Ethylmercuric acetate Ethylmercuric chloride Ethylmercuric phosphate Phenylmercuric formamide Phenylmercuric ammonium acetate Phenylmercuric acetate and ethyl- mercuric acetate Phenylmercuric acetate and ethyl- mercuric acetate Hydroxymercurichlorophenol Chloromethoxypropylmercurie acetate Phenylmercuric acetate Phenylmercuric borate Phenylmercuric oleate Mercuric dimethyldithiocarbamate Mercurous chloride Mercuric chloride Mercuric chloride and mercurous chlo- ride Cleary Cleary Shepard Shepard Shepard Stauffer Stauffer Stauffer Stauffer Du Pont Troy Troy Troy Troy Mallinckrodt Wood Ridge Wood Ridge Wood Ridge ------- |