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ST 085272'! The chemistry of industrial toxicology ST0852722 nd adMon industrial toxicology HERVEY B. ELKINS Director Division of Occupational Hygiene Massachusetts Department of Labor and Industries ST0852723 Copyright, 1950 1959 by John Wlloy A Sons, Inc. All Rights Reserved. This book or any part thereof must not be reproduced In any form without the written permission of the publisher. library o( Congress Catalog Card Number: 59--9764 Printed In the United States of America ST 0852124 Preface to the second edition Since the first edition of this book was published, the number of substances which potentially menace the health of the industrial worker has materially increased. These substances include some in organic materials and many organic compounds, especially pesticides. Very likely the most important, and certainly the best publicized, have been the radioactive isotopes. During the past few years the control of the commoner hazards has improved to such an extent that occupational illness is now rarely en countered in this country from substances such as benzene and carbon disulfide. Moreover, industrial hygiene has developed rapidly in many countries outside the U.S.A., and the findings in these countries have confirmed broadly the earlier experience of America and Western Europe with the familiar industrial poisons. Standards of permissible concentrations of toxic substances have found increasing acceptance and become increasingly severe. Also, many new analytical methods have been developed over the past decade, with particular emphasis on the analysis of body fluids. In the second edition an attempt has been made to include the more important of these new developments in the field of industrial toxicology. December, 1958 Hervey B. Elkins ST0852725 Preface to the first edition Although the literature of industrial toxicology contains many papers dealing adequately with the chemistry of various industrial poisons, nearly all books on the subject are written primarily from the medical point of view. Although the vital role played by the physician in controlling oc cupational disease is duly recognized, it is not amiss to point out that the most important single step in the prevention of many occupational illnesses is control of fumes or dust. Measurement of the effectiveness of such control, in the long run a medical problem, can best be made initially by chemical methods. Furthermore, responsibility for the protection of workers rests primarily with industry; and those most intimately acquainted with the industrial processes and materials in volved are industry's own chemists and engineers. In this book an attempt is made to treat industrial poisons primarily from the point of view of the chemist and engineer. This means that the harmful substances themselves will be emphasized, and the in dustrial processes in which they are used, rather than the symptom atology and pathology of their effects on the human being. Some mention of the nature of the injuries caused is essential; but emphasis is placed on the probable seriousness of such effects, rather than on their complete physiological characterization. It is hoped that this volume will provide a convenient source of information on the basic properties of the common industrial poisons; ST0852726 viil PREFACE TO THE FIRST EDITION that it will stimulate the interest of the industrial chemist in problems of occupational illnesses of toxic origin; and that it will encourage employers to utilize the knowledge and training of their chemists and chemical engineers in protecting their workers from harmful sub stances to which they are exposed. January 3, 1950 Hervey B. Elkins ST 0852127 Acknowledgements It would be impossible to acknowledge properly the contribu tions, direct and indirect, of my associates and friends who are active in industrial hygiene. Especial credit is due my fellow workers, past and present, in the Massachusetts Division of Occupational Hygiene. Of these, individual mention should be made of the following mem bers and former members of the chemical staff of the Division: John P. Fahy, who collaborated in preparation of Chapter 17; and John F. Ege, Jr., James E. Fuller, Robert P. Gleason, James W. Hammond, Leo Levine, Leonard D. Pagnotto, Louis Press, Benjamin P. W. Ruotolo, Emani Storlazzi, and Harland A. Wade. Without the invaluable assistance of my wife, Frances T. Elkins, who typed and edited several drafts of the manuscript, this volume would never have been completed. Ix ST0852728 Contents 1. Fundamentals 1 2. Evaluation of hazards Introduction to Chapters 3--10 13 25 3. The elements: Part I 27 4. The elements: Part II 45 5. The elements: Part III 59 6. Inorganic compounds 79 7. Orcanic compounds, part i: Hydrocarbons 98 8. Organic compounds, part ii : Oxygen compounds 112 9. Organic compounds, part iii: Halogen compounds 131 10. Orcanic compounds, part rv: Organic nitrogen, sulfur, phosphorus, and silicon compounds 158 11. Natural and industrial products 185 12. Radioactive isotopes 195 13. Preventive measures 210 14. Industrial operations and processes 219 15. Maximum allowable concentrations 241 16. Am SAMPLING DEVICES 259 1o 17. Analytical methods and 289 Bibliography 417 Index 441 xl ST0852729 I. Fundamentals INTRODUCTION Poisons have long been of interest to mankind. Primitive man encountered toxic substances in plants, insects, and reptiles. In time he learned to prepare poisonous brews of organic origin. As the arts of mining and metallurgy were developed, inorganic poisons such as compounds of arsenic and mercury became known. The effects of toxic gases, such as carbon dioxide, found in caves and wells, and carbon monoxide and sulfur dioxide, from fire, were no doubt known long before the existence of gases was discovered. With the development of the science of chemistry dozens of new elements, hundreds of inorganic substances, and thousands of organic compounds were discovered and studied. The effects of many of these substances when ingested or inhaled by animals, and even by man, were investigated. Medical science, in quest of new drugs, has sponsored the largest part of these investigations. Most effective medicines are somewhat toxic, and the importance of knowing the limiting safe dosage and physiological effects of substances which are to be swallowed by or injected into sick persons is obvious. The use of such toxic materials as mercury compounds and morphine in the treatment of disease is based on a thorough knowledge of their toxicology. The need for control of insect pests, which consume vast quantities of foodstuffs and spread many infectious diseases, has resulted in fur ther study of the properties of toxic compounds. Insecticides and fumigants, which can be effective without greatly endangering human ST 0852730 2 THE CHEMISTRY OF INDUSTRIAL TOXICOLOGY lives, have been developed; but the need for new and improved agents and methods is still great. Some of these materials, such as the pyrethrum extracts, are relatively non-toxic to man; but others, such as many of the organic phosphates, are very poisonous to humans. The occurrence of poison gases in warfare has been highly sporadic, the most important being in World War I. Their employment at that time, and the ever-present possibility of later use, have stimulated fur ther exhaustive researches on toxic materials. Thus far we have considered poisons which have been deliberately used for their effects upon some form of life. There is another host of substances which are employed for other purposes entirely but which may constitute an incidental poisoning hazard. Thus lead water pipes, cadmium-plated ice trays, and arsenic-pigmented wall paper have all been responsible for numerous poisonings. Accidental poisonings from carbon monoxide gas occur almost daily; and children have contracted lead poisoning by sucking lead-painted toys. Industrial toxicology deals with still another phase of poisoning-- that suffered by workers in the course of their employment in mining, manufacturing, and mercantile establishments. Although the funda mental principles of toxicology apply whenever poisonous substances are absorbed, in practice there is a great difference in emphasis be tween the study of industrial poisons and the study of war gases, or general public health hazards. Thus drugs are usually taken through the mouth or by injection into the blood stream, the dosage is carefully controlled, and medi cal supervision is close. Most industrial poisonings, except for derma toses, result from inhalation of the toxic agent, medical supervision, if any, is at best remote, and dosage is determined with difficulty. War gases are often inhaled, but they are intended to give immediate ef fects, whereas most industrial poisonings are typically gradual in their development. In spite of the long history of mercurial drugs, the maximum safe dosage of mercury vapor was not known until determined by the United States Public Health Service and the Connecticut Department of Health in a study of felt-hat plant workers. The limiting safe con centration of lead dust was similarly determined by investigations of storage-battery workers and bears little relationship to allowable lead concentrations in drinking water. In spite of the hundreds of soldiers exposed to chlorine gas in World War I, the effects of long-continued inhalation of small concentrations of chlorine are still unknown. In short, industrial toxicology has properly been developed to a large extent independently of other branches of toxicology. Although ST085273 I fundamentals 3 its medical aspects are obviously of great importance, the chemical and industrial phases are equally significant. This book seeks to out line those aspects of industrial toxicology which are the primary con cern of the chemist, engineer, and factory manager. AVENUES OF ABSORPTION Systemic industrial poisonings usually result from inhalation of the toxic agent. This fact is fairly obvious as far as gases, like carbon monoxide, and dusts which attack the respiratory system, such as silica, are concerned. With volatile liquids there is a possibility of absorption through the skin, and occasionally this is important. As a rule, however, skin absorption is secondary to absorption by inhalation when systemic effects are considered. Local injury to the skin, due to direct contact with a liquid or solid, is, of course, common. With solid substances, inhalation and ingestion are the most im portant avenues of intake. Industrially, inhalation is again the most important, and toxic solids are most dangerous when dispersed in the air as dusts or smokes. This fact is frequently not recognized in the trades affected. Evidence of the major importance of inhalation as a source of metal poisoning is conclusive, however. Ingestion of toxic substances along with food, in workrooms where the housekeeping is not good, or where workers are careless about washing, no doubt occurs to some extent. As a general rule, however, there is also a considerable dust inhalation where such conditions exist. The classical cases of industrial poisoning via ingestion were those of radium dial painters, who absorbed radium mainly from the prac tice of using their mouths to point the brushes wet with radiumbearing paint.1 Another group involved shinglers, who contracted lead poisoning from lead-coated nails, owing to their habit of holding extra nails in their mouths.2 These, of course, are isolated instances of exceptional practices. In the majority of situations the toxic dust carried into the body is suspended in the air breathed by the worker. Absorption through the skin is still less common with solids but may occur with certain liquids, especially those of low volatility. Phenol, cresol, nitrobenzene, aniline, lead tetraethyl, and many of the organic phosphate insecticides, such as parathion and TEPP, are liquids that present an equal or greater hazard through skin absorp tion than through inhalation. Other liquids and vapors, however, have been shown to pass through the skin to such a degree that gas masks or respirators do not give complete protection against high con- ST0852732 4 THE CHEMISTRY OF INDUSTRIAL TOXICOLOGY centrations. Hydrogen cyanide, for instance, passes through the un broken skin if enough is present in the air. Animals have been poisoned experimentally through the skin by certain of the chlorinated hydrocarbons. This fact should be borne in mind where very high concentrations of vapors or gases are present and individual respiratory protection is provided. ELEMENTS OF RESPIRATION An excellent discussion of respiratory processes is given in Hen derson and Haggard's Noxious Gases.* Only a few fundamental prin ciples will be outlined in this volume. The respiratory system is divided into two main parts: the upper respiratory tract, consisting of the nose and throat; and the lower respiratory tract, or lungs. The nose, throat, bronchi, and bronchioles are essentially air passages leading to the alveoli, the minute cell struc ture of the lungs. In the alveoli die gases in the lungs are separated from blood capillaries by very thin walls, and, since die total surface is very great (90 square meters), diffusion of the lung gases into the blood stream is rapid. Ordinarily the blood receives oxygen and gives up carbon dioxide, which is discharged to the air upon exhalation. If the air inhaled contains other gases or vapors, they ordinarily reach the blood in a similar fashion. However, if the gas is watersoluble, much of it may be deposited on the moist walls of the throat, bronchioles, and other passages of the upper respiratory system, and very little may enter the alveoli. Nevertheless, it finds its way into the blood stream, although less rapidly than via the alveoli. Since the latter cells are the most sensitive portion of the respiratory system, a corrosive gas may vary greatly in its effects, depending on where it is absorbed. Thus the water solubility of a gas or vapor, especially one whose action is primarily irritation, is an important property from the toxicological standpoint With a dust, smoke, or mist, the particle size may determine whether it is absorbed mainly in the upper or lower respiratory tract. As a general rule, the smaller the particle size, the greater the proportion which reaches the alveoli of the lungs, and the faster and more severe the action. Rate of Breathing Unless voluntarily controlled, the rate of respiration is determined primarily by the concentration of carbon dioxide in the blood, and I g ` j ( f | ST0852733 FUNDAMENTALS 5 secondarily by the blood-oxygen concentration. Since both values are affected by the rate of oxygen consumption, it follows that physi cal exertion, which creates an immediate demand for oxygen, stimu lates breathing. The degree of this effect is very great, as shown in 1 Table 1 (from Noxious Gases).* TABLE 1 > IUTE OF BREATHING FOR AN AVERAGE MAN Air Inhaled Activity (1/min) Resting in bed Sitting Standing 6 7 8 Walking--2 miles per hour 14 Walking--4 miles per hour Slow run 28 43 Maximum exertion 65-100 j Thus the volume of air breathed per minute varies nearly fourfold ' when one changes from a light sedentary occupation to moderately severe exertion (walking 4 miles per hour). The rate of inhalation of any toxic impurity in the air increases by the same ratio. It is apparent that this factor must be considered in interpreting data re garding the effects of toxic fumes in the air. CIRCULATION I The blood, which has approached equilibrium with the lung gases, ' passes through the arteries and eventually deposits its load of oxygen l in the body tissues, at the same time picking up carbon dioxide resultI ing from the combustion of carbohydrates. If the blood contains disj solved gases or other substances not normally present, these also are ! deposited to some extent in appropriate tissues, according to the fun- damental laws of physical chemistry. I The rate of circulation is increased by physical effort, although to a somewhat lesser extent than is respiration. RATE OF ABSORPTION 1. Non-Reactive Gases and Vapors Gases and vapors which do not react immediately with the body fluids or tissues to form non-volatile compounds are progressively ST0852731. 6 THE CHEMISTRY OF INDUSTRIAL TOXICOLOGY dissolved in the blood until equilibrium is reached. With a gas that is relatively insoluble in blood and body tissues, such as helium, equi librium is approached rapidly. With highly soluble vapors, like methanol, equilibrium is approached very slowly, and in practice it is probably never even approximately attained. Thus any immediately apparent toxic effects, such as narcosis, result more rapidly from a gas of low solubility in blood and tissue than from one that is readily soluble. 2. Reactive Gases and Vapors If the gas reacts irreversibly in the body to form a non-volatile product, equilibrium is not reached, and the amount of gas absorbed is proportional to the total amount inhaled. 3. Dusts and Smokes Similarly, {ill the dust of a non-volatile compound which is trapped by the respiratory system is retained. Not all the particulate matter retained by the respiratory passages is absorbed directly into the blood stream, however. According to some estimates more than half is deposited in the upper respiratory passages and subsequently swal lowed. If the particles which reach the lungs are insoluble, many of them may be eliminated from the lungs, raised by ciliary action, and finally swallowed.4 ELIMINATION Removal of waste matter from the body takes place mainly through the respiratory tract, the intestinal tract, and the bladder and urinary tract Toxic substances are eliminated through these same channels. Gases, such as carbon monoxide and radon, are removed mainly through the lungs. Vapors of lower volatility, especially water-soluble compounds such as methanol, may be eliminated mainly through the urine. Other vapors, such as those of benzene and toluene, are converted to non volatile oxidation products, which in turn are excreted in the urine. Many metals, such as lead, manganese, and radium, are excreted chiefly through the intestines in the feces. Relatively large propor tions of certain metals, however, notably mercury, uranium, and ar senic, are found in the urine. Reactive compounds of elements commonly found in the body in large amounts, like hydrochloric acid or hydrogen sulfide, may be ST0852735 FUNDAMENTALS 7 neutralized or destroyed, and the resulting products enter into regular metabolic processes. Ingested material usually passes directly into the intestines from the stomach and is often eliminated without being taken into the blood stream. For this reason many substances, e.g., lead compounds, are more toxic when inhaled than when ingested. Minor avenues of elimination of toxic compounds include perspira tion, hair, and nails. The excretion of most toxic organic compounds, and of gases, is usually a matter of hours, or at most of days. Many of the poisonous elements, however, can be stored for long periods of time in the body. Metals with chemical properties similar to those of calcium (radium, lead, and plutonium, for example) may be deposited in the bones. Mercury is also stored in various parts of the body for long periods. Fluorine, too, is stored in the bones. If further absorption of the toxic element is discontinued, excretion of the stored portion is begun and continues until it is virtually eliminated from the system. Conversely, if there is a long continued intake of some toxic ele ment, excretion may increase until it balances absorption. This is a condition frequently found in chronic poisoning. HARMFUL EFFECTS The pathological changes induced by toxic materials will not be discussed in detail in this volume, since such a discussion belongs properly to the medical consideration of toxicology. Some appre ciation of the organs and processes injured by various poisons is de sirable, however, even in a purely chemical approach. There are three types of acute effect which may result from the inhalation of any toxic fume, but particularly from gases and vapors. These are asphyxiation, irritation of respiratory organs, and narcosis. In addition there are other responses which may be acute but are more typically chronic. These include damage to blood, nervous sys tem, liver, kidneys, bones, etc. Many of these effects are exerted independently of one another, but sometimes one predominates, often to the virtual exclusion of all others. Asphyxiation Oxygen is necessary to sustain life, and, as we have already seen, an increased amount is needed if work is being done. Table 2 indi cates the result of reduction in the oxygen content of the air.5 S TO 852 736 THE CHEMISTRY OF INDUSTRIAL TOXICOLOGY Partial Prerure of Oxygen (mm mercury) 120-160 90-120 76- 90 i5~ 76 TABLE 2 BFHSCT OF REDUCED OXYGEN Oxygen in Atmosphere at Sea Level ( %) 16-21 12-16 10-12 6-10 Response No notable effect Increased respiration, slight diminu tion of coordination Loss of ability to think clearly Loss of consciousness, death Asphyxiation may be brought about by mechanical obstructions, by reduction of air pressure, by dilution of air with another gas until the concentration of oxygen is reduced by reduction of the oxygen content of the air, or by chemical action which prevents access of oxygen to, or inhibits use of oxygen by, the tissues. The simple asphyxiants, gases which act only by diluting the air, include most of the inert gases, also hydrogen, methane, ethylene, nitrogen, and carbon dioxide. In order to reduce the oxygen content to a fatal degree, a vapor concentration of about 50 per cent must be attained. This is possible only with a gas or a very volatile liquid; and in such concentrations the direct effects of most gases are in themselves fatal. Chemical asphyxiants are relatively few in number. They include carbon monoxide, the cyanides, and possibly hydrogen sulfide. Asphyxiation may also result from the inhalation of irritant gases, which injure the respiratory system so that it is no longer able to convey oxygen from the air to the blood stream. Irritation Direct irritation of the respiratory tract, the eyes, and the skin is frequently produced by toxic materials, characteristically by strong acids, alkalies, and oxidizing agents. Some degree of irritation is also caused by many solvent vapors. The most pronounced irritation is produced by substances readily soluble in water, such as ammonia and hydrochloric acid. Such gases, however, affect mainly the upper respiratory passages. Injury to these organs is less serious than damage to the lungs, which is likely to occur when gases with similar chemical properties but only slightly soluble in water are inhaled. The influence of water solubility, which in general parallels solu bility in body fluids, is shown in Table 3. i ST0852737 FUNDAMENTALS 9 TABLE 3 WATER SOLUBILITY AND TOXICITY OP CORROSIVE GASfcS Oas Ammonia Hydrogen chloride Sulfur dioxide Chlorine Phosgene Toxicity, Solubility in Water Concentration Hydrolysis at 0 C Dangerous in 1 Hour* Product (moles/1) (ppm) Weak base 53 3000 Strong acid 23 1000 Weak acid 3.6 00 Strong acid 0.2 50 Strong acid Very slight 25 The soluble gases, hydrogen chloride and ammonia, act mainly on the nose and throat, being absorbed by the moist linings of those pas sages. Sulfur dioxide, chlorine, and phosgene, being less soluble in water, pass through the upper respiratory tract to a greater extent and damage the lungs. The identity of the tissues affected, rather than the chemical reaction causing the damage, is largely responsible for the wide difference in toxicity. It is probable that differences in physical rather than chemical prop erties are responsible for other anomalies noted in the toxicides of related compounds. Another important feature of the irritant gases and vapors is that the soluble ones are more immediately irritating in low concentrations and therefore act as warning agents. No one can unconsciously in hale more than a single breath of air containing a lethal concentration of ammonia, for example. Fatal inhalation of such gases occurs only when the victim is trapped and unable to escape, whereas with less soluble gases the immediate effects of breathing a dangerous amount may be almost unnoticeable. In addition to corrosive substances that owe their irritant properties to their chemical activity, there are some relatively inert substances, especially organic compounds, that have a pronounced irritating action upon the respiratory system. The reason for this is not clear; but, as a rule, with chemically similar compounds the less volatile are the more-irritant. The lachrymators, which are as a group highly irritant, are in general moderately reactive esters of low volatility. Narcosis The symptoms of narcosis, or anesthesia, include impairment of mental facilities, muscular incoordination, lightheadedness, and laugh ing jags. If exposure is continued, the ability of the mind to function ST085273f' 10 THE CHEMISTRY OF INDUSTRIAL TOXICOLOGY clearly decreases until unconsciousness occurs. Death eventually re sults, usually from respiratory failure. Narcosis is caused by the direct action of the toxic substance on the nervous system. Apparently all organic solvents and many solids that are soluble in fats are capable of producing some degree of anes thesia. The greater the fat solubility, in comparison with the water solubility, the more potent the narcotic properties of the compound. Thus the alcohols are weak anesthetics, and the hydrocarbons and chlorohydrocarbons are relatively strong. This relationship is the basis of the Meyer-Overton theory of nar cosis: that the narcotics act on the lipoids in the membranes of nerve cells, and alter their permeability and electrical polarization. In the past, toxicity has, on occasion, been mistakenly identified with anesthetic power. Thus trichloroethylene is a more powerful anesthetic than carbon tetrachloride, and animal experiments with these vapors in high concentrations led to the conclusion that tri chloroethylene was the more toxic of the two. Actually carbon tetrachloride is also a powerful liver and kidney poison, and in low concentrations this effect is more important than anesthesia. The result is that contrary to the earlier interpretation carbon tetrachloride is in reality the more hazardous of the two compounds. Many symptoms of asphyxiation and anesthesia are quite similar. This is apparently due to the fact that in both conditions the primary effect is to impair the functioning of the brain--in asphyxiation by denying it sufficient oxygen, and in anesthesia by direct action. Damage to Nervous System Asphyxiation and anesthesia, if not carried to a fatal conclusion, are usually transitory. In other words, there are no permanent ill effects. Severe carbon monoxide poisoning, however, sometimes does result in permanent damage to the nervous system. Injury to the nervous system resulting from long-continued absorption of a toxic agent is apparently not related to either asphyxiant or anesthetic prop erties, however. Thus, of the solvents, methanol, one of the weakest anesthetics, is one of the worst offenders in producing permanent damage to the nervous system. The optic nerve is damaged in typical methanol poisoning. Other alcohols and many ethers, carbon disul fide, and some of the halogenated hydrocarbons are also reported to have a cumulative effect upon the nervous system. Of the elements, chronic mercury and manganese poisonings usually involve the nervous system, ST 0852739 FUNDAMENTALS Liver and Kidney Damage 11 Injury to the liver and kidneys is noted from a majority of the sub stances discussed in this book. Fatal industrial poisonings involving these organs have been reported from carbon tetrachloride, tetrachloroethane, hexachloronaphthalene, trinitrotoluene, and dioxane. Many other organic vapors have been shown to cause liver and kidney injury in animal experiments. Certain of the heavy metals, especially uranium, are primarily kidney poisons. Blood Changes Many toxic substances cause blood changes, either transitory or permanent. Benzene is one of the worst of this class. Its primary effect is apparently on the bone marrow, where blood cells are formed. Arsine and lead have been found to produce blood changes. The nitro compounds, such as TNT, also act upon the blood. Organic phosphates destroy the enzyme, cholinesterase, which is present in red blood cells. Bon* Damage Under some conditions, usually involving long exposure to relatively low concentrations, certain agents cause serious injury to bone struc ture. Fluorine, which is deposited in the bones, is one such poison. Chronic poisoning from yellow phosphorus usually involves necrosis of the jaw bone. Cancers frequently develop in bones in which radium is deposited. No doubt plutonium, strontium90, and other radioactive bone-seekers will have a similar effect. However, non radioactive heavy metals apparently do not injure bone structure ma terially, even though many such metals are deposited in the bones. Cancers Skin cancer is caused by long-continued contact with certain con stituents of coal tar and shale oil. Beta-naphthylamine and some re lated amines cause bladder tumors when inhaled over long periods. Radioactive substances also produce tumors, cancer of the lung being attributed to the inhalation of radon, and bone tumors to radium stored in the bones. Undoubtedly, prolonged absorption of artificially radioactive ele ments will produce cancers under suitable conditions. Radioactive ST08527l0 12 THE CHEMISTRY OF INDUSTRIAL TOXICOLOGY elements are of a higher order of toxicity than elements th&t owe their harmful effects solely to chemical reaction. Other Effects Damage to other organs predominates with a few substances. For instance, direct injury to die heart is reportedly caused by barium compounds. Strong acids damage the teeth. Hydrogen sulfide causes conjunctivitis, an eye affliction quite different bom the lachrymation caused by many irritant vapors. Ability to cause sterility is often popularly attributed to new and unknown substances or conditions of environment. In some cases the reproductive organs of animals have been damaged by heavy dosages of toxic materials.* To the authors knowledge, however, industrial use of toxic substances rarely if ever causes sterility in workers unless the exposure is great enough to cause other more typical symptoms. I ST085271*! 2. Evaluation of hazards The hazardous conditions produced by certain industrial processes are well and accurately known. Usually, however, there is a need for more precise methods of determining whether or not a hazard exists. In a chemical investigation of the potential dangers from toxic substances there are several steps. PRELIMINARY INFORMATION A preliminary estimation of the condition can be made on the basis of relatively meager data. The following points should be considered: 1. Toxicity of substances handled or present. 2. Physical properties of such substances. 3. Possibilities of absorption by workers. 4. Quantities involved. 5. Continuity of exposure. 6. Complaints or evidence of injury. Frequently, harmful effects, other than skin irritation, occur only if the air is contaminated with the toxic material. No process in volving poisonous substances can be considered safe until all possible sources of serious atmospheric contamination have been eliminated. Gases, unless confined in a completely enclosed system, auto matically escape and diffuse throughout the workroom air. Leaks ST0852742 14 THE CHEMISTRY OF INDUSTRIAL TOXICOLOGY in illuminating gas systems may produce a dangerous concentration of carbon monoxide. Methyl chloride poisoning has resulted from leaky mechanical refrigeration. Harmful concentrations of gases are more often released from chemical reactions, however. Thus carbon monoxide is produced in many combustion processes, nitrogen dioxide by various reactions of nitric acid, and arsine from the action of nas cent hydrogen on arsenic compounds. Under such conditions the toxic gas is not ordinarily included in any list of substances employed in the plant processes, and its presence must be either deduced from the operations carried out or detected by suitable tests. When volatile liquids are used at room temperature, harmful vapor concentrations are theoretically possible if the vapor pressure of the liquid exceeds the maximum safe vapor concentration. This condi tion occurs with virtually all liquids boiling below approximately 170 C and with many of substantially lower volatility. As a general rule, however, a harmful condition does not exist unless the vapor concentration at saturation exceeds the maximum allowable value by a factor of 20 or more. An atmosphere saturated with benzene vapor, for example, contains about 102 by volume, or 4000 times the maximum allowable concentration of 0.00252. With the less toxic and less volatile toluene the corresponding ratio is 200, with tetrachloroethylene 200, and with mercury 190. Liquids boiling above 150 C do not usually present a vapor hazard unless they are highly toxic or unless their evaporation is hastened by heat, if a spray or mist is produced, of course, the volatility of the liquid assumes a posi tion of minor importance. Only a few solid substances (e.g., p-dichlorobenzene) are suffi ciently volatile to produce a vapor hazard when handled cold. Others, such as the chloronaphthalenes, are commonly safe at room tempera ture but become dangerous when heated. Certain of the metals, like cadmium and zinc, vaporize readily at temperatures slightly above their melting points. Their vapors condense in the air, however, and are inhaled as a smoke of finely divided solid particles, and not as a vapor. The great majority of the toxic metals, including lead, do not volatilize appreciably much below a red heat. Nevertheless, a dust hazard may result from handling a dry powder or from grinding, cutting, pulverizing, and similar operations. If conditions are favorable for contamination of the atmosphere by a toxic material, the quantity of gas, vapor, dust, or smoke being dis persed should be ascertained. As a rule a benzene hazard, for example, is improbable if less than a quart daily is consumed in a relatively small area. With more toxic substances (i.e., maximum ST08527U3 EVALUATION OP HAZARDS 15 allowable concentration below 25 ppm) smaller amounts will produce a harmful concentration of vapor, and vice versa. Frequently much of the preliminary information can be obtained without even seeing the process in question. It is best, however, to make an actual inspection of the operation, in order to verify any statements of existing conditions, to secure additional data, some of which have invariably been overlooked, and to obtain a firsthand picture of the situation. When the inspection is made by an outsider, such as a government or insurance company representative, it serves a twofold purpose. The first is to observe the operation itself; the second is to confirm the preliminary report received, ordinarily based on statements of company representatives. Although few employers deliberately fal sify facts, their opinions on matters concerning the health of their workers are often unavoidably subject to prejudice. Similarly the state ments of employees on details of their work are, for the most part, accurate, but they are prone to magnify ills attributable to their jobs. Frequently when a process involving dust or fume is being examined, the employer comments that conditions are much worse than usual, whereas workers state that the visitor selected a poor time to observe the operation because the fumes are not nearly so thick as on most days. Some idea of the degree of atmospheric contamination may be obtained by direct observation. Thus most gases and vapors are de tectable by odor. Absence of a harmful concentration of trichloro ethylene or ammonia, for example, can be assumed if the odors of these substances cannot be detected. With some volatile compounds, however, the sense of smell cannot be relied upon to pick up a dangerous concentration. Carbon monoxide, of course, is virtually odorless. With carbon tetrachloride and benzene the odor threshold for most people approximates the maximum allowable concentration, so that any detection by odor perception is indicative of a probable hazard. Hydrogen sulfide, on the other hand, can be detected in concentrations so far below the harmful level that objectionable odors may be present in the absence of even a borderline hazard. Dusts and smokes can be seen when present in high concentrations. Harmful concentrations of smokes of low toxicity, such as zinc oxide, are readily visible under favorable conditions. Concentrations of dust of the order of 1 mg per cubic meter of air, which are well above the safe limit for many metals (such as cadmium and lead), are not easily seen. Smokes, which have a very small particle size, show up more readily than the coarser dusts. ST0852744 1* THE CHEMISTRY OF INDUSTRIAL TOXICOLOGY It should be emphasized that estimates of atmospheric contamina tion based on sensory perception are reliable only when made by highly trained observers who have had wide experience in evaluating such impurities. THE ENGINEERING APPROACH If the data available include the amount of gas or vapor released to the workroom air, it may be possible to calculate the approximate concentrations which probably exist. Suppose, for example, an opera tion requires 1 qt of carbon tetrachloride per hour, all of which evap orates into the air of the room. A quart (about 3 lb) of carbon tetrachloride forms approximately 8 cu ft of vapor. If the room is ventilated at a rate of 80,000 cu ft per hour, the average concentration of carbon tetrachloride vapor in the room should be 100 ppm (0.01J). Only under ideal conditions does this method of calculation yield highly accurate results. One reason for this is that workers are often exposed to local concentrations of the gas or vapor which may differ widely from the average room concentration. Unfortunately this method has often been improperly applied. Thus in one instance the toluene exposures of a number of workers were calculated from monthly records of consumption of solvent and the capacities of the fans ventilating the rooms where the work was done. The results obtained were of questionable value. In another situation the maxi mum concentration of benzene vapor was calculated from the amount of vapor evaporated per day and the volume of the room, with zero ventilation assumed for the room. According to the calculation, these workers were exposed to over 4500 ppm of benzene vapor. In determining the amount of ventilation needed for a given process, calculations similar to the above have been very helpful. The results should be checked by direct tests, however, if a potentially serious hazard is involved. Whenever processes are controlled by local exhaust ventilation, engineering tests of air velocities often tell whether or not the control is adequate. Sometimes, where the process is more or less standard, data on the performance and capacity of the exhaust system are more valuable than air tests, unless the latter cover a much wider range of conditions than is usually practicable. The granite industry furnishes a good example of such processes, where the requirements for control by local exhaust of certain dusty operations have been worked out with a high degree of precision.7 : ST0852745 evaluation of hazards CHEMICAL TESTS 17 The most precise method of evaluating the worker's environment, from the standpoint of its effect on his health, is a chemical analysis of the workroom air. This does not mean a complete analysis for all components, since the oxygen, nitrogen, and carbon dioxide contents are usually within normal limits. But the quantity of harmful im purity, be it dust, smoke, mist, vapor, or gas, is the important factor whenever the main source of possible hazard is respiratory tract absorption. Air analysis has many advantages over other methods of estimating exposure. It is the only method that actually tests the environment. It determines which are the important sources of contamination and whether or not ventilating systems are effective. A minimum of cooperation from the employee is required. Although special apparatus is necessary, the technique of determin ing most atmospheric impurities is not particularly difficult since few interfering substances are usually present. Direct-reading indicators are available to determine numerous gases and vapors. These are very convenient and most useful for ferreting out sources of con tamination. Most such devices are not too satisfactory for sampling over long periods of time, however. For determining the average concentration an absorbing unit that removes the impurity as the air is drawn through is commonly employed. Sometimes grab samples of the air are taken in suitable flasks or bottles for analysis in the laboratory. As a general rule the most important value is the average concen tration of impurity to which the worker is exposed over a complete job cycle. This often involves not only a long sampling period, but also an easily portable sampling device which can be moved about with the worker, at least in a limited area. Only when the source of contamination is not directly affected by the worker's activities can the sampling device be set up on a table in the middle of the room and allowed to operate without supervision. It is desirable to obtain at least one set of check samples. Not only are checks a good practice in any sampling procedure, but, when tests are made in a factory, conditions are likely to be abnormal during the first hour or so. After the novelty of the test situation has worn off, the workers usually resume their normal tempo, and more representa tive data are obtainable. A recommended practice is to take three sets of samples--one representing the operator's exposure, one of the general air, and one ST 0852746 18 THE CHEMISTRY OF INDUSTRIAL TOXICOLOGY near the probable source of contamination. This is a good procedure, but it must not be forgotten that the concentration of dust or fume actually breathed by the workers is of paramount importance. In lieu of direct analysis of the air, various indirect methods may be employed. The most common of these is analysis of filters of respirators which have been worn by workers on the process in ques tion. This gives a measure of the impurity which would have been inhaled if the respirator had not been worn, minus what, if any, passed through or around the respirator. It is a useful check, but it can be employed only for a limited group of toxic elements. Sampling devices actuated by the breathing of a worker have been successful in a few cases, but they require more cooperation from the individual worker than usually can be expected. Concentrations of vapors and gases are ordinarily expressed as parts per million by volume, or as percentage by volume. Smokes, dusts, and mists, however, are computed as milligrams per cubic meter, or 10 cubic meters, of air. The maximum concentration of dusts or smokes encountered seldom exceeds 100 mg per cubic meter of air. This corresponds to less than 50 ppm of a vapor or gas in the molecular weight range of 50 to 150, in which most industrial vapors and gases fall. Although air analyses are much more precise than indirect methods of estimating atmospheric concentrations of poisons, they are often not ideal measures of the existing degree of hazard. It is frequently very difficult to obtain a representative sample, especially since most processes change more or less from day to day, and conditions vary, owing to weather changes, even if the process remains the same. The exposure of the worker depends not only on the concentration of fume in the air but also on his rate of breathing. We have already seen that this can vary several fold, depending chiefly on the degree of exertion of the individual and undoubtedly on other factors as well. Air analysis, of course, tells nothing of absorption through the skin or of ingestion of toxic substances. Finally, when personal protective devices such as respirators and gas masks are worn, the exposure of the worker cannot be determined from the concentration of fume or dust in the air. BIOCHEMICAL TESTS The concentration of toxic agent in body tissues or excreta often gives a more accurate measure of the worker's exposure than can be obtained by any tests on his environment. Determinations of this sort are considered here as biochemical tests, | j . I | j 3 i * : ST0852747 EVALUATION OF HAZARDS 19 It has been shown that inhaled fumes may be destroyed in the re spiratory tract or dissolved in the blood and carried through the body and made available to the tissues. The further fate of these fumes depends on their physical and chemical properties. Volatile and un reactive substances are eliminated as they entered, via the lungs; less volatile substances are excreted in the urine, feces, or perspiration, or in some cases deposited in the hair and nails. Storage for long periods in the bones or other tissues is not uncommon with the toxic elements, but it does not often occur with organic compounds. The presence of toxic material in the blood, urine, or breath does i not necessarily imply poisoning. Analysis of the excreta of apparently | healthy workers for toxic ingredients is primarily for the purpose of detecting excessive exposure to the poison and is not intended other wise. On the other hand, if an individual shows symptoms of lead poisoning, for example, presence of an abnormally high lead conceni tration in the urine confirms the diagnosis by proving an exposure to j lead. Analysis of urine or blood for volatile poisons in suspected chronic poisoning cases, however, is often futile since the poison is usually eliminated rapidly. Thus the urine sulfate test, extremely valuable as an index of benzene exposure, has often been mistakenly applied to patients with benzene poisoning long after their contact with benzene has ceased. Expired Air Analysis of expired air may help to detect recent exposure to carbon monoxide and has been employed as a test for alcoholic intoxication. It is most successful, however, in the measurement of radium exposure. Radium disintegrates at a constant rate, giving off the radioactive gas radon. The radon given off by radium deposited in the bones finds its way into the blood, whence it is carried to the lungs and exhaled. Determination of the radioactivity of the expired air gives a measure of the quantity of radium stored in the body, which is an index of past exposure to radium.* Blood Analysis Examination of blood for carboxyhemoglobin is a common method of determining recent carbon monoxide exposure. The lead content of blood is preferred by some authorities to other indices of lead ex posure, especially in suspected cases of active plumbism. The bromide content of blood has been shown to rise after inhalation of sublethal amounts of methyl bromide.9 ST0852748 20 THE CHEMISTRY OF INDUSTRIAL TOXICOLOGY Most analyses for toxic substances require several grams of blood, however, and samples of this size are not often taken except under direct medical supervision. When other methods of evaluation are available, they are therefore usually preferred to analysis of blood samples. Urine Analysis Analysis of urine for toxic elements, compounds, or reaction products is the most widely applicable of the biochemical tests. The author prefers urine analysis to other tests in the evaluation of lead, mercury, fluoride, arsenic, and uranium exposures. It is useful for determining absorption of selenium, tellurium, toluene, methanol, trichloroethylene, trinitrotoluene, and benzene, as well as plutonium, tritium, strontium90 and many other radioisotopes. More work needs to be done on the excretion of these compounds and of cadmium. Analysis of urine for numerous other toxic compounds or their degradation products has been suggested, but most of such tests are still in the experimental stage. The metals, as a rule, are excreted rather slowly, over a relatively long period of time, especially when they have been absorbed in small quantities daily for several weeks or months. Samples can be collected after a lapse of several days following the last exposure without great loss in the content of mercury or lead, and probably of other toxic elements. If there has been a single short exposure, how ever, elimination falls off rapidly. Thus the urinary excretion of mercury, at a fairly high level immediately after a tooth is filled, com monly diminishes to a trace after a few days.10 With many organic compounds the presence of the toxic agent is transient. Benzene and toluene are converted , into non-volatile com pounds which are largely found in the urine but are eliminated rather rapidly. The urines of persons with substantial benzene exposure have been found normal 16 hours after the end of exposure, and a change toward normal (increase in sulfate ratio) has been noted 4 hours after exposure ceased. The urine sulfate test for benzene ab sorption is, therefore, reliable only if the urine specimen is obtained during, or within a few hours after, exposure. Other organic sub stances, such as methanol and trichloroethylene, are excreted more slowly, and a few, such as DDT, are stored in the body for consider able periods of time. Contamination is a problem in securing urine specimens for certain tests, such as lead content. The author has found the extreme pre- ST 0852749 EVALUATION OF HAZARDS 21 cautions recommended by some authorities unnecessary in the majority of cases, however. The variations in the amounts of toxic elements in the urine of different individuals with the same exposure, and of the same indi viduals at different times, have led to several proposals for alternate methods of calculating results. One suggestion, made for lead but presumably applicable to other elements, is to determine the hourly excretion by obtaining the time required for secretion of the urine sample analyzed.11 A more convenient method is to make a correc tion for specific gravity. Thus, if the normal specific gravity is 1.024 and the specimen in question has a gravity of 1.012, the corrected lead (or other toxic substance) content is obtained by multiplying the measured value by 0.024/0.012, or 2. Urinary lead values corrected in this manner have been more consistent than uncorrected values.11 Fecal Analysis Many of the toxic metals, notably lead, radium, and manganese, are excreted primarily in the feces. The difficulties of analysis, as well as of obtaining samples, discourage the average investigator from this test. Analysis of feces for toxic substances is confined largely to clinical and experimental studies. Analysis of Hair and Nails Arsenic is deposited in the hair and nails, and analyses of these materials are useful in determining a past arsenic exposure. PHYSIOLOGICAL METHODS The methods of evaluating hazards so far considered have been primarily physical or chemical; that is, they have consisted of directly determining or calculating the quantity of toxic agent being absorbed or excreted. There usually is a definite relationship between rate of absorption and rate of excretion, and the same result is achieved by either method. A further type of test consists of determining not the amount of toxic material but the degree of its effects on the persons exposed. Although some such tests can be interpreted by a layman, the majority can be dealt with intelligently only by a physician. Determination of lead in urine is primarily a chemical problem. ST0852750 27 THE CHEMISTRY OF INDUSTRIAL TOXICOLOGY In fact, only a well-equipped and well-staffed chemistry laboratory can carry out such a test properly. Interpretation of the results is comparatively simple. The body cannot transmute other elements into lead; therefore an abnormally high content of urinary lead means an abnormal absorption of lead. If a group of lead workers all show highly leaded urines, it is reasonable to assume that they are acquiring the lead on their jobs. It does not mean, however, at least to the chemist, that these individuals have lead poisoning. Very likely the majority of them are perfectly healthy. In fact it would be abnormal if, after large amounts of lead were absorbed, it failed to show up in their urines. The effects of toxic substances on the body tissues are another matter altogether, however. Such effects may be very simple and obvious--for example, the irritation of the nose or throat caused by gases like ammonia or hydrogen chloride, or by solvent vapors such as butanol and amyl acetate. Again, they may be more subtle and delayed, like the headaches resulting from continued carbon mon oxide exposure. They may consist of dizziness and lack of coordina tion, as from inhalation of high concentrations of gasoline vapor. Nausea, such as is caused by carbon tetrachloride, may be the pre dominating effect These are all subjective symptoms, indicating an early stage of poisoning. In certain cases, as with irritation caused by certain gases and vapors, especially lachrymation, some degree of immunity is apparently established. If the exposure is continued, other effects may develop. The nausea caused by carbon tetrachloride vapor may be followed by serious liver damage. Continued inhalation of various irritating sub stances may cause ulceration of the nasal passages. Repeated lowgrade narcosis by some solvents may result in damage to the nervous system. With other toxic agents the warning symptoms come too late. Long-continued exposure to benzene frequently produces no symptoms until the prognosis is unfavorable. Lead and mercury poisoning, when detected, may be so far advanced that complete recovery is doubtful. The same is true, to an even greater degree, with silicosis. Physiological Tests There are, however, tests to detect early stages of poisoning before clinical symptoms ordinarily appear. Thus chest x-rays often detect silicosis long before it becomes disabling. Blood changes caused by * ; ; { > J ST085275I EVALUATION OF HAZARDS 23 benzene poisoning are detectable before subjective symptoms are in evidence. Blood changes also occur in early stages of TNT poison ing. A reduction in the cholinesterase activity of the blood is a re liable indication of organic phosphate poisoning. A rise in the coproporphyrin content of the urine ordinarily precedes other signs of lead poisoning. Tests for tremor may disclose chronic mercurialism before it becomes obvious. It is apparent that such tests should be carried out under medical supervision and interpreted by a competent physician. It must be further emphasized that all these tests depend on measuring damage already done to the body tissues. Such injury may, of course, be trivial, but often it is not; and the chemical or biochemical test, which can determine the hazard before injury is done, is preferable from the worker's standpoint. The physiological tests are most valuable where no suitable bio chemical tests are available. They also tend to differentiate between susceptible and resistant individuals. SIGNIFICANCE OF TESTS When the amount of toxic substance has been determined by suit able means, it is necessary to know whether a harmful condition exists. Ordinarily the concentration of poisonous agent found is compared with the maximum allowable concentration--a concentration judged to be without serious effects even for long-continued exposure. A concentration below the maximum allowable level is considered satis factory, and a higher concentration is unsatisfactory for other than brief periods. In the discussion of harmful substances in Chapter 3 through 10, suitable methods of evaluation are listed. In general, chemical or biochemical tests are preferred, and physiological tests are recom mended as a second choice, if at all. This does not mean that medical examinations, including such tests, are undesirable for workers ex posed to the agent in question. On the contrary, the author believes that all workers exposed to injurious substances should periodically undergo complete medical examinations. These are primarily to de tect any possible ill effects of the environment upon the worker, how ever, and to note any changes in the worker that would make him more susceptible to an unfavorable environment. These examinations should not replace tests of the environment itself, for which purpose the evaluation tests are recommended. ST0852752 24 THE CHEMISTRY OF INDUSTRIAL TOXICOLOGY Frequently the tests or calculations indicate a hazardous condition, but .no adversei effects upon the health of workers are apparent. It is often possiblgjor a group of persons to be exposed without injury to dosages of toxie materials above the maximum allowable value, for these limits are sufficiently low to protect the more susceptible section of the population as well as the more resistant and the average individual. Often, however, the absence of evidence of harmful action is mis leading, and the workers suffer from non-spectacular and usually minor ailments which are caused or aggravated in part by their work ing environment. In other workers there is a long latent period dur ing which no symptoms appear, followed eventually by illness, in capacitation, and sometimes death. The author has seen enough serious cases of poisoning develop in groups of apparently healthy employees to put his trust in measurements of fume concentrations rather than lay opinions of the physical condition of the workers. / ST0852753 Bibliography 1. Hamilton, Alice, Industrial Toxicology, Harper & Brothers, 1934. 2. Magnuson, H. J., and Raulston, B. O., "Lead Poisoning in Roofers," J. Am. Med. Assoc., 114, 1528 (1940). 3. Henderson, Y., and Haggard, H. W., Noxious Gases, Reinhold Publishing Corp., 2nd Edition, 1943. 4. Hatch, T. F., and Kindsvatter, V. H., "Lung Retention of Quartz Dust Smaller than One-Half Micron," /. 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Toxicol, 29, 286 (1947). 37. Sabine, J. C., and Hayes, F. N., "Anticholinesterase Activity of Tributyl Phosphate," Arch. Ind. Hyg. Occupational Med., 6, 174 (1952). 38. Prodan, L., "Cadmium Poisoning: II," /. Ind. Hyg., 14, 174 (1932). 39. Leschke, E., Clinical Toxicology, William Wood & Co., 1934. S T 0852755 IlftllOGRAPHY 419 40. Spedini, F., and Valdini, P. L., "Study of Barite Pneumoconiosis," Radiol, med., 26, 1 (1939). Abstracted In }. Ind. Hyg. Toxicol, 23, 95 (1941). 41. Gumey, S. W., Private Communication, 1948. 42. Randal], M., and Humphrey, H. B., "New Process for Controlling Mercury Vapor," U.S. Bur. Mines, Inform. Circ. 7206 1942). 43. Markwith, R. H., et al., "Industrial Mercurialism," Ohio Department of Health, 1940. 44. Neal, P. A., et al., "Mercurialism and Its Control in the Felt-Hat Industry," U.S. Public Health Serv., Public Health Bull. 263 (1941). 45. Hunter, D., Industrial Toxicology, Oxford at the Clarendon Press, 1944. 46. Hill, W. H., "A Report on Two Deaths from Exposure to the Fumes of a Di-Ethyl Mercury," Can. J. Public Health, 34, 158 (1943). 47. Schulte, H. F., "Mercury Hazards in Seed Treating," J. Ind. Hyg. Toxicol., 28, 159 (1946). 48. Shepherd, M., et al., "Hazard of Mercury Vapor in Scientific Laboratories," Nat. Bur. Standards (U.S.) Research Paper 1383 (1941). 49. Morris, G. E., et al., "Protection of Radium Dial Painters," /. Ind. Hyg. Toxicol, 25, 270 (1943). 50. Tabershaw, L R., and Tebbens, B. D., "The Use of Aluminum in Silicosis Control," Ind. Med., 14, 709 (1945). 51. Jephcott, C. M., Johnston, J. H., and Finlay, G. R., "Fume Exposure in the Manufacture of Alumina Abrasives from Bauxite," J. Ind. Hyg. Toxicol., 30, 145 (1948). 52. Meek, S. F., et al., "Toxicity of Gallium--An Exploratory Investigation," Ind. Med., 12, 7 (1943). 53. McCord, C. P., Harrold, G. C., et al., "The Physiologic Properties of Indium and Its Compounds: I," /. Ind. Hyg. Toxicol, 24, 243 (1942); II, ibid., 25, 233 (1943). 54. Denny, J. J., Robson, W. D., and Irwin, D. A., "The Prevention of Silicosis by Metallic Aluminum," Can. Med. Assoc. J., 40, 213 (1939). 55. Blina, L. V., "Experiments with Titanium Oxide," Riforma med., 44, 1516 (1922). Abstracted in ]. Ind. Hyg. Toxicol., 12, 96 (1930). 56. Lenzi, L., "Pneumoconiosis Caused by Titanium," Rass. med. appl. laooro ind., 7, 301 (1936). Abstracted in /. Ind. Hyg. Toxicol, 19, 87 (1937). 57. Erhardt, W., "Todliche Subakute Gewerbliche Bleivergiftung," Arch. Gewerbepathol. Gewerbehy., 9, 407 (1939). 58. Harrold, G. C., et al., "Toxicity of Lead Chromate," J. Ind. Hyg. Toxicol, 26, 47 (1944). 59. "Progress Reported in Control of Lead Poisoning in the Automobile In dustry," Survey of Labor Law Administration, I, 6 (1936). 60. Halley, J. W., and Martin, E. D., "Lead-Bearing Steels: Control of Possible Health Hazards During Fabrication," Metal Progr., 37, 412 (1940). 61. Fassett, D. W., Private Communication, 1950. 62. Neal, P. A., et al., "A Study of the Effect of Lead Arsenate Exposure on Orchardists and Consumers of Sprayed Fruit," U.S. Public Health Serv., Public Health Bull. 267 (1941). 63. Dreessen, W. C., et al., "The Control of the Lead Hazard in the Storage Battery Industry," U.S. Public Health Serv., Public Health Bull. 262 (1941). 64. Russell, A. E., et al., "Lead Poisoning in a Storage Battery Plant," U.S. Public Health Serv., Public Health Bull. 205 (1933). ST0852756 420 THE CHEMISTRY OF INDUSTRIAL TOXICOLOGY 65. Heimann, H., "Chronic Phosphorus Poisoning," J. Ind. Hyg. Toxicol, 28, 142 (1946). 66. Fleming, R. B. L., Miller, J. W., and Swayne, V. R., Jr., "Some Recent Ob servations on Phosphorus Toxicology," J. Ind. Hyg. Toxicol., 24, 154 (1942). 67. Symanski, A., "Gewerbliche Vanadinschadigungen, Ihre Entstehung und Symptomatology," Arch. Gewerbepathol. Gewerbehy., 9, 295 (1939). 68. Wyers, H., "Some Toxic Effects of Vanadium Pentoxide," Brit. J. Ind. Med., 3, 177 (1946). 69. Hill, A. B., Perry, K., et al., "Studies in the Incidence of Cancer in a Factory Handling Inorganic Compounds of Arsenic," Brit. ]. Ind. Med., 5, 1 (1948). 70. Hamilton, A., Industrial Poisons in the United States, The Macmillan Com pany, 1929. 71. Watrous, R. M., and McCaughey, M. B., "Occupational Exposure to Arsenic in the Manufacture of Arsphenamine and Related Compounds," Ind. Med., 14, 639 (1945). 72. Bulmer, F. M. R., et al., "Chronic Arsine Poisoning among Workers Em ployed in the Cyanide Extraction of Gold," /. Ind. Hyg. Toxicol., 22, 111 (1940). 73. Metcalf, R. L., "Control of Hazards in Use of Agricultural Chemicals: Cal ifornia Experience," A.M.A. Arch. Ind. Health, 16, 337 (1957). 74. Fairhall, L. T., and Hyslop, F., "The Toxicology of Antimony," Public Health Repts. (U.S.) Suppl. 195 (1947). 75. Greenburg, L., et al., "The Effects of Exposure to Toluene in Industry," /. Am. Med. Assoc., 118, 573 (1942). 76. Dudley, H. C., and Miller, J. 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Occupa tional Med., 7, 99 (1953). 436. Brieger, H., et al., "Industrial Antimony Poisoning," Ind. Med. and Surg., 23, 521 (1954). 437. Baetjer, A. M., "Pulmonary Carcinoma in Chromate Workers," Arch. Ind. Hyg. Occupational Med., 2, 487 (1950). 438. Mancuso, T. F., and Hueper, W. C., "Occupational Cancer and Other Health Hazards in a Chromate Plant: I," Ind. Med. and Surg., 20, 358 (1951). 439. Mancuso, T. F., "Occupational Cancer and Other Health Hazards in a Chromate Plant: II," Ind. Med. and Surg., 20, 393 (1951). 440. Morris, G. E., Private Communication, 1956. ST0852772 436 THE CHEMISTRY OF INDUSTRIAL TOXICOLOGY 441. Maloof, C. C., "Use of Edathamil Calcium in Treatment of Chrome Ulcers of the Skin," A.M.A. Arch. Ind. Health, 11, 123 (1953). 442. Hall, R. H., et al., "Preliminary Observations on Toxicity of Elemental Se lenium," Arch. Ind. Hyg. Occupational Med., 4, 458 (1951). 443. Hodge, H. C., "Mechanism of Uranium Poisoning," A.M.A. Arch. Ind. Health, 14, 43 (1956). 444. 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Z., Private Communication, 1958. S T 0852777 Index Abrasives, 186 Absorbing devices, 275-288 Absorption of vapors, theoretical fac tors, 284-288 Acetaldehyde, 248 Acetic acid, 117, 248 Acetic anhydride, 117, 248 Acetone, 119, 248, 286 determination of, 290 Acetone cyanohydrin, 248 Acetonyl acetone, 248 Acetophenone, 248 Acetyl chloride, 248 Acetylene, 102 Acetylene tetrabromide, 248 Acid dipping, 84, 223, 235 Acrolein, 118-119, 220, 248 determination of, 290-291 Acrylates, 130 Acrylonitrile, 94, 175, 190, 248, 256, 400 determination of, 292 Actinium"8, 198 Activated charcoal apparatus, 279, 280* Adhesives, 191-192 Aeration constants, 286, 287 Air analysis, 17-18 Air and hose masks, 215 Air pollution, 82, 83, 88 Air-sampling methods, 267-288 choice of, 288 Alcohols, 112-117 Aldehydes, 118-119, 236 Aldrin, 155, 194, 254 Alkali cleaners, 224 Allyl alcohol, 115, 248 Ally! chloride, 148, 248 Allyl glycidyl ether, 248 Allyl isothiocyanate, 177 Allyl propyl disulfide, 177, 248 determination of, 292 Aluminum, 46, 220, 221, 226, 254 Aluminum dust, 48, 218 Aluminum oxide, 46, 222, 256 Aluminum refining, 71 Americium*41, 200, 246 Aminodiphenyl, 166, 173 2-Aminopyridine, 174 Aminothiazole, 172 Animate, 254 Ammonia, 8, 9, 15, 22, 86, 190, 225, 236, 239. 248 determination of, 292-293 Ammonium chloroplatinate, 78 Amyl acetate, 22, 129, 239, 248, 287 determination of, 293 Amyl alcohol, 115, 248 Amyl formate, 248 Amyl nitrate, 167 Amyl nitrite, 167 Aniline, 3, 170, 222, 235, 249 determination of, 293-294 2-Anilinoethanol, 173-174 Anthracene, 110, 186 Antimony, 65-66, 220, 254, 256 determination of, 294--295 Antimony1*4. 201 Antimony tnsulfide, 66, 190 ANTU, 254 Argon, 28, 222 * Italic numbers indicate pages on which illustrations appear. 441 ST0852778 442 Argon41, 200, 203-204 Argyrosis, 30 Aroclor, 152, 153 Aromatic hydrocarbons, 103-111, 265 detector kit, 264 Arsenic, 6, 20, 21, 62-63, 254, 256, 295, 298 in urine, 63, 256 determination of, 295-297 poisoning, symptoms of, 62-63 Arsenic1*, 200 Arsenic77, 201 Arsenic plating, 224 Arsenic trichloride, 63, 64 Arsenic trioxide, 62 Arsine, 14, 63-65, 237, 239, 249, 256, 265 determination of, 297-298 Arsphenamine, S3 Asbestos dust, 256 Asbestosis, 185 Asphyxiation, 7, 8, 91, 92, 93, 94, 95, 97, 170, 175 Astatine111, 200 Atropine, 179 Automobile exhaust gas, 91 Automobile repairing, 235 Azobenzene, 175 Bagassosis, 189 BAL, 75, 77 Barium, 12, 39, 254 determination of, 298 Barium1*71", 205 Barium140, 200 Barium chromate, 38, 67 Barium oxide, 38, 87 Barium sulfate, 38, 192 Battery-manufacturing operations, 36, 37, 52, 235 Bends, 88, 96 Benzene, 6, 11, 14, 15, 16, 19, 22, 23, 25, 99, 100, 103-108, 249 determination of, 298-303 industrial exposures to, 104, 105, 192, 193, 210-211, 217, 227, 228, 229, 231, 234, 235-240 in urine, 19, 20, 105-106, 256 determination of, 303 MAC, discussion of, 107 Benzene absorber, 278 Benzene hexachloride, 150-151 Benzidine, 173, 254 Benzine, 99 Benzol indicator, 288 Benzyl acetate, 249 Benzyl chloride, 249 Berylliosis, 31, 32 Beryllium, 30-32, 220, 221. 237, 238, 254 determination of, 303-305 by lung biopsy, 32 Beryllium7, 200 INDEX Beryllium fluoride, 31 Beryllium oxide, 31 Beryllium sulfate, 31 Beryllium zinc silicate, 30 Biochemical tests, 18-19, 54 Bismuth, 66-67, 254 determination of, 305 Bismuth110, 198 Bismuth111, 198, 206 Bismuth114, 198 Bladder tumors, 11, 173 Blast-furnace and producer gas, 91 Blasting (rock), 239 Bleaching, paper, textile. 239 Blood analysis, 19, 54, 55, 56, 58 Blood changes, 11, 22, 23, 54, 63, 66, 74, 96, 104, 109, 114, 125, 130, 142, 161, 162, 166, 170 Bone damage, 11, 37, 60, 71, 72, 197, 203, 204, 207, 208, 209 Boric acid, 45 Boron, 45 Boron hydrides, 45 Boron trifluoride, 249 Brain damage, 77, 155 Brass plating, 224 Brazing, 35, 37, 72, 222, 235 Breathing, rate of, 4, 5 Broaching, 136 Bromine, 75, 89, 249 determination of, 305-306 p-Bromoaniline, 172 Bromofonn, 138-139 Bronze, 33, 50, 52, 220 Bronze cutting, 54 Bronze grinding, 52, 53 Bronze pouring, 52, 53, 54 Butadiene, 102, 249 Butanol, 22, 114-115, 193, 234, 235, 237, 249, 286 determination of, 306-308 Butanone (see Methyl ethyl ketone) Butyl acetate, 128-129, 246, 249 Butyl acrylate, 130 Butylamine, 249 Butylbenzyl phthalate, 191 Butyl Cellosolve, 126, 249 2-sec-Butyl-6-4-dinitrophenol, 166 Butyl formate, 127, 249 Butyl glycidyl ether, 249 Butyl mercaptan, 249 Butyl methacrylate, 130, 249 n-Butyraldoxime, 176 Byssinosis, 189 Cable impregnating, 235 Cadmium, 14, 34-39, 254 determination of, 308-309 industrial exposure to, 35, 36, 37, 219, 220, 221, 222, 226, 235, 238, 239 in urine, 20, 256 determination of, 309-310 I ST0852779 INDEX Cadmium109, 200 Cadmium carbonate, 35 Cadmium catting, 36, 37 Cadmium-copper melting, 36, 37 Cadmium oxide, 35, 36, 38 Cadmium plating, 221, 224 Cadmium selenide, 193 Cadmium smelting, 36, 37 Cadmium spraying, 35, 36, 37 Cadmium sulfide, 36, 38, 193 Calcium, 33, 223 Calcium45, 197, 200 Calcium arsenate, 254 Calcium carbide, 87 Calcium cyanamide, 87 Calcium fluoride, 73 Calcium hydride, 64 Calcium oxide, 87 Camphor, 122, 191, 254 Cancer, 62, 68, 111, 207 bone, 11 lung, 11, 68, 77, 207 skin, 11, 186-187 Carbon, 47, 84 Carbon14, 200, 202 Carbon dioxide, 8, 26, 93, 222, 249 determination of, 310--311 Carbon disulfide, 10, 176-177, 192, 235, 249, 257, 258 determination of, 311-312 Carbon monoxide, 6, 8, 10, 14, 15, 19, 22, 91-93, 249, 257, 265 determination of, 312-313 industrial exposure to, 220, 222, 235, 236, 237, 238, 239 Carbon monoxide indicator, 260, 267, 288 Carbon tetrachloride, 10, 11, 15, 16, 22, 131, 135-137, 192, 211, 217, 246, 249, 257, 286, 287, 317 determination of, 313-315 industrial exposure to, 136, 228-234, 235-240 Carbonyl bromide, 81, 132 Carboxyhemoglobin, 19, 257 Cascade impactor, 274-275 Cashew-nut oil, 188 Cellosolve, 125, 235, 249 determination of, 315 Cellosolve acetate, 249 Celluloid, 84, 191 Cellulose nitrating, 235 Cellulose xanthating, 235 Cementing operations, 136, 228, 230, 235-236 Cerium144, 200 Cesium, 29 Cesium137, 200, 205 Chemicals mixing, 236 Chemical tests, 17 Chloracne, 152 Chlordane, 154, 194, 254, 317 Chlorinated camphene, 254 443 Chlorinated diphenyl oxide, 254 Chlorinated diphenyls, 152-153, 157, 222, 236, 254 determination of, 319-321 Chlorinated hydrocarbons, determina tion of, 317-319 Chlorinated naphthalenes, 151-152, 222, 258 determination of, 319-321 Chlorinated triphenyl, 153 Chlorine, 9, 73, 88-89, 239, 249 determination of, 315 Chlorine35, 200 Chlorine dioxide, 89-90, 239, 249 determination of, 315-316 Chlorine trifluoride, 90, 249 Chloroacetaldehyde, 249 Chloroaniline, 172, 249 Chlorobenzene, 149-150, 235, 249 Chlorobromopropene, 149 Chlorobutadiene (see Chloroprene) 2-Chlorobutene-2, 149 Chlorodifluoroethane, 144 2,1,4-Chlorodinitrobenzene, 166 Chlorodiphenyl (see Chlorinated di phenyls) bis (0-Chloroethyl) 0-chloroethyl phos phorate, 184 bis (/9-Chloroethyl) vinyl phosphonate, 184 Chloroform, 134, 249, 286, 287, 317 Chloronaphthalene, 14, 151-152, 235, 236 Chloronitrobenzene, 166, 249 1-Chloro-l-nitroethane, 161 1- Chloro-l-nitropropane, 161, 249 2- Chloro-2-nitropropane, 161 Chloropicrin, 160, 249 Chloroprene, 148-149, 190, 249 Chlorosulfonic add, 83 Chlorothion, 182, 194 Chlorotoluene, 249 Chlorotoluidine, 172 Cholinesterase activity, 11, 23, 257 determination of, 321-323 inhibition of, 179, 180, 181, 183 Chromates, 68, 265 determination of, 323-325 Chrome plating, 224--225 Chromic add, 67, 235, 237, 239, 254 determination of, 323-325 Chromium, 67-68, 220, 221 in urine, 68, 257 Chromium51, 200 Cleaning operations, 136, 236, 237 Coal products, 186 Cobalt, 75-76, 238, 254 determination of, 325-326 Cobalt50, 200, 203 Cobalt acetate, 76 Colored-flame tests, 267 Combustible-gas indicators, 259, 260 Combustion apparatus, 283 J 444 Condenser impregnating, 236 Container filling, 236 Copper, 29, 220 Copper**, 200 Copper plating, 225 Coproporphynn, 23, 54, 55, 56, 57, 257 m urine, determination of, 326-329 Crag herbicide, 254 Creatinine in urine, determination of, 329 Cresol, 3, 116, 249 Cristobalite, 48 Cryolite, 72, 73, 185 Cumene, 249 Curium*** 200 Cutting oils, 187 Cyanides, 8, 236, 237, 238, 254 alkali, 94-95, 224, 226 Cyanogen, 95, 249 Cyanogen bromide, 96 Cyanogen chloride, 95, 249 Cyclohexane. 102, 103, 131, 192, 249 CyclohexanOl, 116, 249 Cyclohexanone, 121, 249 determination of, 329-330 Cyclohexene, 249 Cyclohexylamine, 169, 249 2-Cyclohexyl-4,6-dinitrophenol, 166 Cyclopentane, 103 Cyclopropane, 102, 249 2,4-D, 254 DDA, 154, 194 DDT, 20, 153-154,194, 237, 254, 257, 317 determination of, 330-333 Decaborane, 45, 46, 250 Degreasing operations, 145, 233 Dermatitis, cutting-oil, 187-188 Deuterium, 28 Diacetone alcohol, 115, 250 Dianisidine, 173 Diazinon, 182, 194 Diazomethane, 80, 174 Diborane, 45, 250 Dichlorobenzene, 14, 150, 234, 236, 237, 240, 250 _ Dichlorobenzidine, 173 Dichlorobutane, 148, 317 Dichlorodiethyl sulfide, 178 Dichlorodifluoromethane, 250 1,1 -Dichloroethane, 250 1,2-Dichloroethane (see Ethylene di chloride) Dichloroethyl acetate, 156 Dichloroethylene, 144, 250 Dichloroethyl ether, 156, 234, 250 Dichlorohyarin, 156, 317 Dichloromethane (see Methylene chlo ride) Dichloromonofluoromethane, 132, 250 1,1-Dichloro-l-nitroethane, 161, 250 Dichlorotetrafluoroethane, 139, 250 ST 0852780 INDEX Dicyclohexylamine, 250 Dieldrin, 154-155, 194, 254 Diesel-engine operations, 84, 91, 236 Dietary enrichment, 217-218 Diethyiamine, 250 Diethylaniline, 172 Diethyl carbonate, 129, 250 Diethyl Cellosolve, 126 Diethyl /S-chloroethylamine, 169 Diethylene oxide, 124 Diethyl ether, 123 Diethyl mercury, 42, 43 Difluorodibromoethane, 144 Difluorodibromomethane, 250 Difluorodichloromethane, 133 Difluoroethane, 144 Difluoromonochloromethane, 132, 250 Difiuorotetrachloroethane, 317 Diglycidyl ether, 250 Dihydroxyoctachlorodiphenyl, 166 Diisobutylketone, 121, 250 Diisopropylamine, 168-169, 250 Diisopropylfluorophosphonate, 183 Dimethylaniline, 171, 250 Dimethylarsine, 63 Dimethyl 8-chloroethylamine, 169 Dimethyl dioxane, 250 Dimethyl formamide, 175, 250 Dimethylhydrogen phosphite, 184 Dimethylnitrosamine, 175 Dimethyl p-phenylenediamine, 171 Dimethyl sulfate, 178, 250 Dinitrobenzene, 162, 254 Dinitrocresol, 164-165, 254, 257 Dinitrodichlorobenzene, 166 Dinitronaphthalene, 166 2,4-Dinitro-l -naphthol, 166 Dinitrophenol, 163-164, 254 Dinitroresorcinol, 254 Dinitrotoluene, 162, 254 Dioctyl phthalate, 191 Dioxane. 11, 124-125, 250 Diphenols, 117 Diphenyl, 111, 254 Diphenylaminechloroarsine, 63 Diphenylchloroarsine, 63 Diphenylcyanoarsine, 63 Dipropylene glycol methyl ether, 250 Dipterex, 182, 194 Direct-reading instruments, 17, 259-265 Dope mixing, 231, 237 Dry powders, handling of, 223 Dust counters, 274 Dye mixing, 237 Dyes, 193-194 Dykanol, 152 Dynamite blasting, 84 EDTA, 57-58, 68, 75, 209, 218, 356358 Electric precipitators, 272 Electroplating, 94, 223, 237 Emanation, 198 ST085278I INDEX Emphysema, pulmonary, 36, 37, 60, 61 Enameling operations, 227-228, 238 Enamels, 193 Encephalopathy (sea Lead, poisoning) Endrm, 155 Epichlorohydrin, 156 EPN, 182, 194, 254 Esters, 126-130, 227, 238 determination of, 333-334 Etching, 72 Ethers, 123-125, 236 /J-Ethoxyethyl methacrylate, 250 Ethyl acetate, 128, 228, 229, 231, 235, 246, 250 Ethyl acetoacetate, 250 Ethyl acrylate, 130, 250 Ethyl alcohol, 113, 250 determination of, 334 Ethylamine, 250 Ethyl benzene, 250 Ethyl benzoate, 250 Ethyl bromide, 143, 250 determination of, 334 Ethyl chloride, 140, 250 determination of, 334 Ethylene, 8, 101,131 Ethylene chlorohydrin, 155, 250 Ethylene diamine, 168, 169, 250 Ethylene dibromide, 143, 250, 317 Ethylene dichloride, 140-141, 149, 155, 192, 228, 229, 231, 232, 235, 238, 239, 250, 257 determination of, 317, 334-335 Ethylene dinitrate, 167 Ethylene glycol, 116 Ethylene glycol dinitrate, 167, 250 Ethyleneimine, 168, 250 Ethylene oxide, 123-124, 250 Ethyl ether, 250 determination of, 334 Ethyl formate, 127, 251 2-Ethyl hexyldiphenyl phosphate, 191 Ethylidine chloride, 141 Ethyl mercaptan, 177, 251 Ethyl methacrylate, 130, 251 Ethyl oxalate, 130 Ethyl propionate, 129 Ethyl silicate, 178, 251 Europium154, 200 Expired air, analysis of, 19, 208, 257 Eye damage, 12, 61, 71, 81, 83, 86, 87, 95, 110, 112, 114, 115, 117, 118, 122, 123, 140, 151, 159, 160, 168, 169, 174, 179 Fabric cleaning, 136, 233-234, 237 Fabric coating, 136, 229, 237 Fatal poisonings, 11, 31, 34, 35, 37, 43, 46, 64, 66, 67, 83, 84, 90, 95, 103. 107, 113, 124, 133, 134, 137, 139, 142, 145, 151, 154, 155, 156, 157, 161, 163, 164, 171, 174, 181, 194, 207, 233 445 Fecal analysis, 21 Felt-hat operations, 237 Ferbam, 254 Ferrovanadium, 254 Field titration methods, 267 Filtering devices, 270-271 Filter-paper holder, 271 Fire extinguishers, 135, 137, 138 Fission products, 199, 204 Fluorescent-lamp manufacture, 31, 237, 238 Fluorides, 7, 11, 71-73, 220, 221, 222, 235, 238, 239, 240, 254 determination of, 335-337 in fluxes, determination of, 338-339 in urine, 20, 257 determination of, 337-338 Fluorine, 71-73, 251 in urine, 72-73 Fluorine1*, 200 Fluoroform, 132 Fluorotrichioromelhane, 251 Formaldehyde, 118, 190, 236, 238, 239, 251 determination of, 339-343 Formic acid, 117, 251 Fritted bubbler, 277 Fritted petri bubbler, 278 Fur blowing, 237 Fur cleaning, 136 Furfural, 119, 251 Furfuryl alcohol, 251 Gallium, 46 Gallium1*, 200 Galvanizing, 33, 237 Gas masks, 214 Gasoline, 22 100, 108, 251, 257 Gasoline-tanx cleaning, 52 Gast pump, 268 Germanium, 49 Germanium11, 197, 200 Glass, 186 Glass-bead columns, 277-279 Glass blowing, 237 Glycerin, 116 Glvcidol. 251 Gold, 30 Gold1**, 200 Gold1**, 200 Gold plating, 225 Grab samples, 17, 284 Haber's law, 242-243 Hafnium, 49 Half-life, definition of, 196-197 Halide meter, 263, 264-265, 288 Halogen compounds, 131-157 Halowax, 151-152 Harmful effects, definition of, 25 Hazard, evaluation of, 13, 26 Heart damage, 12, 39, 65, 133, 134, 147, 156 446 Heaters, unvented, 91-92 Helium, 6, 27-28, 96, 222 Helium3, 196 Heptachlor, 194 Heptane, 99, 103, 131, 251 Heptene, 103 HETP, 254 Hexachlorobenzene, 150 Hexachlorocyclopentadiene, 149 Hexachloroethane, 142-143 Hexachloronaphthalene, 11, 98, 151- 152, 217 254 Hexamethyldisiloxane, 179 Hexamethylene tetramine, 169, 190 Hexamethyl phosphoramide, 184 Hexane, 99, 103, 251 Hexanone (see Methyl butyl ketone) Hexene, 103 Hexane (see Methyl isobutyl ketone) Hippuric acid in urine, 109, 257 Holmium1**, 200 Hopcalite, 93, 260 Hydrazine, 86, 251 Hydraxoic acid, 251 Hydrocarbons, 10, 98-111 Hydrochloric acid, 6, 8, 223 Hydrofluoric acid, 85, 224 Hydrogen, 8, 28 Hydrogen*. 200, 202 Hydrogen oromide, 80, 251 Hydrogen chloride, 9, 22, 79-80, 223, 235, 236, 251 determination of, 343-345 Hydrogen cyanide, 4, 26, 94, 235, 251, 265 determination of, 345-347 in urine, determination of, 347, 400 Hydrogen fluoride, 251 Hydrogen peroxide, 90, 251 Hydrogen selenide, 69, 243, 251 Hydrogen sulfide, 6, 8, 12, 15, 97, 237, 251, 265 determination of, 347-348 Hydroquinone, 117, 123, 254 Illuminating gas, 91 Impingement devices, 272-275 Impinger, standard, 273 Indium, 46 Indium114, 201 Insecticide mixing, 237 Insecticides, 53, 63, 150, 154, 155, 166, 179-184, 194 Instrument filling, 237 Interferometer, 261-262 Iodine, 75, 89, 251 Iodine1*1, 200, 205 Ionium, 198 Iridium, 78 Iridium140, 200 Iridium192, 200, 205 Iron, 34, 75, 220, 221 Iron**, 200 ST 0852782 Iron*9, 200 Iron carbonyl, 75 Iron oxide fumes, 220, 255, 265 determination of, 348-349 Isoamyl alcohol, 115, 248 Isoamyl formate, 127, 248 Isophorone, 122, 251 Isoprene, 102 Isopropyl alcohol, 114, 253 Isopropylamine, 251 Isopropyl ether, 123 Isopropyl glycidyl ether, 251 INDEX Jute mill fever, 189 Kerosene, 100, 287 Ketene, 80, 121, 151 Ketones, 119-123 determination of, 349-351 Kidney damage, 11, 37, 40, 47, 58, 70, 111,115,116,117, 121, 122, 123, 124, 125, 126, 133, 135, 137, 140, 148, 149, 155, 158, 159, 164, 168, 170, 178, 197, 205, 209 Krypton, 28 Krypton85, 204 Lachrymators, 9, 160 Lacquering operations, 109, 193, 227- 228, 238 Lacquer mixing, 230, 231 Lanthanum140, 200 Latex, 190 Lauryl mercaptan, 251 Lead, 6, 7, 14, 21, 22, 49-58, 193, 211, 255 determination of, 351-353 in blood, 19, 54, 55-56, 58, 257 industrial exposures to, 3, 51-56, 192, 220, 222, 226, 227, 229, 230, 235-239 in urine, 20, 22, 51, 53, 54-58, 257 determination of, 353-358 MAC, discussion of, 56-57 poisoning, 53-56 evaluation of, 55 symptoms of exposure, 54 treatment of, 57-58 Lead20*, 200, 206 Lead209, 198 Lead20*, 197, 198 Lead210, 198, 206 Lead212, 198, 206 Lead214, 198, 206 Lead acetate, 50 Lead alloys, 50 Lead arsenate, 50, 53, 63, 255 Lead borate, 50 Lead burning, 52, 238 Lead carbonate. 50, 192 Lead casting, 52 S T 08 52783 INDEX Lead chloride, 50 Lead chromate, 50, 53, 67, 192, 193, 255 Lead dioxide, 50 Lead droning, 54, 238 Leaded iron pouring, 52, 54 Lead grinding, 52, 54, 216, 223 Lead oxide, 51, 190, 192, 216, 223, 238 Lead-painted rteel burning, 52 oxy-gas cutting, 52 Lead powder mixing, 52 Lead sanding, 52, 54, 223 Lead silicate, 50 Lead smelting, 52 Lead sulfate, 50, 192 Lead sulfide, 50, 255 Lead tetraethyl, 3, 50, 53, 54, 55, 56, 255, 257 Lead titanate, 50 Leather, 188 Leather operations, 101, 105, 107, 109, 238 Leiman pump, 269, 270 Lethane, 194 Lewisite, 62-63 Lindane, 150, 194, 255 Linotyping, 52 Litharge, 50 Lithium, 29 Lithium hydride, 255 Liver damage, 11, 22, 37, 63, 66, 69, 114, 116, 121, 122, 124, 133, 134, 135, 138, 140, 141, 142, 143, 145, 147, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 162, 163, 164, 165, 166, 170, 171, 175, 178, 197, 204, 257 Lung damage, 31, 34, 35, 46, 47, 60, 76, 80, 83, 87, 88, 89, 118, 121, 137, 148, 149, 156, 160, 164, 168, 169, 186, 189, 206, 207, 208 Lutetium1TT, 200 Magnesium, 32-33, 220 Magnesium melting, 72 Magnesium oxide, 33, 255 Magnesium tumors, 32 Malathion, 194, 255 Maleic anhydride, 117 Manganese, 6, 10, 21, 26, 73-74, 220, 221, 240, 255, 257, 258 determination of, 358-359 in urine, determination of, 360 Manganese52, 201 Manganese50, 200 Maximum allowable concentrations, 14, 23, 241-258 criteria for, 246-247 history of, 247-248 Medical examinations, 23, 108, 217 Melamine, 191 447 Mercury, 6, 7, 10, 14, 22, 23, 39-44, 255, 258, 265 determination of, 360 industrial exposure to, 192, 211, 227, 235--238 in urine, 20, 40, 41, 42, 43, 257 determination of, 360-364 Mercury-distillation apparatus, 362 Mercury-electrolysis cell, 362 Mercury vapor detector, 262, 263, 264 Mesityl oxide, 122, 251 Mesothorium, 198, 208 Metacide, 181 Metal annealing, 238 Metal degreasing, 231, 238 Metal-fume fever, 33, 45, 191, 221 Metal grinding, 238 Metal hardening, 238 Metalizing, 52, 226 Metal machining, 238 Metal melting and casting, 219-221, 238 Metal pouring, 238-239 Metal purifying, 239 Methacrolein, 251 Methacrylates, 130 Methacrylic acid, 251 Methallyl alcohol, 251 Methallyl chloride, 251 Methane, 8, 131 Methanol, 6, 10, 112-113, 235, 236, 240, 251, 286 determination of, 354--366 in urine, 20, 113, 257 determination of, 366 Methoxychlor, 194, 255 Methyl acetate, 127-128, 251, 257 Methyl acetylene, 251 Methyl acrylate, 130, 252 Methylal, 125, 252 Methyl allyl chloride, 148 MethylaniHne, 172 Methyl benzene (see Toluene) Methyl bromide, 19, 26, 98, 137-138, 252, 258 determination of, 367 Methyl butyl ketone, 120-121, 193, 252 determination of, 369 Methyl Cellosolve, 125, 228, 231, 235, 252 determination of, 367-369 Methyl Cellosolve acetate, 252 Methyl chloride, 14, 133-134, 252 determination of, 367 Methyl chloroacrylate, 252 Methyl chloroform, 211, 252, 286, 287, 317 Methyl cyclohexane, 252 Methyl cyclohexanol, 116, 252 Methyl cyclohexanone, 121, 252 Methylene chloride, 107, 131, 134, 211, 252 44S Methylene chlorobromide, 138, 252, 286, 287, 317 Methyl ethyl ketone, 120, 192, 228, 229, 235, 236, 237, 239( 252, 286 determination of, 369 Methyl formate, 126-127, 252 2-Methyl hexane, 103 Methyl hydrazine, 169 Methyl iodide, 139, 252 Methyl isobutyl carbinol, 252 Methyl isobutyl ketone, 369 Methyl mercaptan, 252 Methyl mercury iodide, 42 Methyl methacrylate, 130, 252 determination of, 369-370 Methyl propyl ketone, 120, 252 Methyl silicate, 178 Methyl styrene, 252 Meyer-Overton theory, 10, 103 Mica, 185, 256 Midget impinger, 273, 274, 276 Minimum lethal dose, 242 Mipafox, 182-183 Mixtures, toxicity of, 257-258 Molybdenum, 69, 220, 221, 235, 255 Molybdenum**, 200 Monochlorobenzene, 149-150 Monochlorobromomethane (see Meth ylene chlorobromide) Monochloronaphthalcne, 150 Monofluorotrichljromethane, 133, 252 Monomethyl aniline, 252 Multigraphing, 136, 239 Naphtha, 192, 227, 228, 229, 231, 236239 252 coal tar, 110, 192, 234, 252 vapors, determination of, 370-372 Naphthalene, 110, 192 Napthenes, 102-103, 192 Naphthol, 117 Naphthylamine, 11, 173, 255 Narcosis, 6, 9-10, 25, 93, 96, 102, 108, 110, 111, 113, 114,115, 119, 123, 125, 126, 127, 128, 129, 132, 133, 134, 139, 140, 141, 142, 144, 145, 146, 147, 257 Neon, 28 Neon-sign manufacturing, 53 Neoprene, 105, 149 Nervous system, damage to, 10, 39, 43, 45, 47, 49, 74, 112, 117, 125, 127, 133, 137, 139, 145, 150, 153, 154, 158, 160, 169, 174, 183, 250 Nickel, 76-77, 221, 255 Nickel8*, 200 Nickel88, 201 Nickel carbonyl, 76-77, 252, 257 Nickel plating, 225 Nicotine, 194, 255 Niobium, 65 Niobium*5, 200 Nitric acid, 85, 224, 252 ST085278U INDEX Nitric oxide, 96-97, 221, 252 determination of, 372 Nitroaniline, 172, 252 Nitrobenzene, 3, 161-162, 252 determination of, 372 Nitrobutane, 160 Nitrocellulose, 191, 193 Nitrodiphenyl, 165, 255 Nitroetnane, 159, 252 determination of, 372 Nitrogen, 8, 59, 96 Nitrogen dioxide, 14, 83-84, 222, 224, 235, 236, 239, 240, 252 determination of, 372-374 Nitrogen mustards, 169 Nitrogen oxides (total), determination of, 378 Nitrogen peroxide, 85 Nitroglycerin, 166-167, 217, 252 determination of, 374 Nitromethane, 158, 252 Nitronaphthalene, 166 Nitropropane, 159-160, 227, 228, 229, 231, 237, 252 determination of, 374-377 n-Nitrosodimethylamine, 175 p-Nitrosodimethylaniline, 172 Nitrosomethylurethane, 174 Nitrosyl chloride, 85. 225 Nitrotoluene, 162, 252 Nitrous oxide, 96 Octamethyl pyrophosphoramide, 181-- 182 Octane, 252 Olefins, 101-102 OMPA, 181-182, 255 Optical instruments, 261-265 Osmium, 77-78 determination of, 377 Osmium tetroxide, 78, 255 Oxalic acid, 85 Oxyacetylene welding, 84,192, 216, 221, 222 Oxygen, 67, 87-88 Oxygen apparatus, self-contained, 215 Ozone, 88, 221, 222, 252 determination of, 378-379 Paint, 192 Painting operations, 53, 54, 216, 226- 227, 239 Paint mixing, 52, 53, 54, 230 Paint sanding, 52, 53 Palladium, 77 Palladium103, 200 Palladium109, 201 Paper coating, 229, 239 Paper impregnating, 239 Paraffins, 99-101 chlorinated, 148 Paraldehyde, 119 ST 0852185 INDEX Paranitrophenol in urine, determina tion of, 381-383 Paraoxon, 181 Parathion, 3, 180-181, 194, 236, 237, 255 determination of, 379-381 in urine (tee Paranitrophenol in urine) Particle *ize, 4, 50 Pentaborane, 45, 252 Pentachloroaiphenyl, 153 Pentachloroethane, 156, 157, 255 Pentachloronaphthalene, 151-152, 255 PentachlorophenoL, 156, 157, 255 determination of, 383-384 Pentaerythritol tetranitrate, 167 Pentane, 103, 252 Perchloric acid, 85 Perchloroethylene (see Tetrachloro- ethylene) Perchlorometnyl mercaptan, 253 Petri bubbler. 275, 276, 277, 288 Petroleum etner, 99 Petroleum products, 187 Phenol, 3, 116, 253 determination of, 384-385 Phenol-formaldehyde compounds, 191, 193, 223 p-Phenylenediamine, 170, 193 Phenyl glycidyl ether, 253 Phenvlhydrarine, 253 Phoadrin, 184 Phosgene, 9, 80, 132, 222, 253 Phosphates (organic), 179-184, 257 poisoning, symptoms of, 179 Phosphine, 60, 220, 236, 253, 265 determination of, 385-387 Phosphoric acid, 60, 85 Phosphorus, 11, 59-60, 255 determination of, 387 halides, 60, 194 Phosphorus**, 200, 203 Phosphorus oxychloride, 60 Phosphorus pentachloride, 254 Phosphorus pentasulfide, 254 Phosphorus trichloride, 60, 253 Photoengraving, 239 Phthalic acid, 117, 118 Phthalic anhydride, 117, 118 Physiological tests, 22-23 Picric acid, 164, 255 Plastics, 176, 190-191 Plastics operations, 239 Platinum, 78, 255 Platinum metals plating, 225 Plutonium, 7, 11, 20, 71 Plutonium** 197, 199, 200, 209, 257 determination of, 387-388 Pneumonitis, 31, 69 Polonium*10, 198, 200, 257 Polonium*1*, 196, 198 Polonium*14, 198, 207 Polonium11*, 198 449 Polonium*1*, 198, 207 Portland cement, 256 Potassium, 29 Potassium40, 196, 201, 203 Potassium4*, 196, 200, 203 Potassium permanganate, 255 Praseodymium14*, 200 Printing operations, 52, 229-230, 235, 239 Promethium141, 200 l-Propiolactone, 253 Propyl acetate, 128, 246, 253 n-Propyl alcohol, 113-114, 253, 287 Propyl bromide, 147-148 Propyl chloride, 147 Propylene, 101 Propylene dichloride, 147, 192, 237, 253, 286, 287, 317 determination of, 388 Propylene glycol monoethyl ether, 126 Propyleneimine, 168, 253 Propylene oxide, 124, 253 Propyl ether (iso), 253 Protactinium**4, 198 Protective clothing, 215 Protective creams, 215 Pyrethrine, 194 Pyrethrum, 194, 255 Pyridine, 174, 253 Pyrocatechol, 117 Pyrogallol, 117 Pyrolusite, 185 Pyrophosphates, alkyl, 180 Pyroxylin cementing, 105, 192, 228 Quartz, 185 Quinone, 123, 253 Radiation, effects of, 195-196 type of, 196 Radioactive elements, naturally occur ring, 197 Radioactive isotopes, 195-209 artificial, 199 chemical properties of, 197 Radioactivity, 11, 19, 28, 58, 70, 207 Radiolead, 198 Radium, 3, 6, 7, 11, 19, 21, 44, 197, 257, 258 in urine, determination of, 388-390 Radium*14, 198, 206, 207-208 Radium***, 198, 199, 200, 202, 207208 Radium1**, 198, 207-208 Radon, 6, 11, 19, 28 Radon110, 198, 200, 206 Radon1*1, 198, 200, 202, 206-207 Resorcinol, 117 Respiration, elements of, 4 Respirators, 18, 214 S T 0 852786 450 INDEX Respiratory tract, damage to, 8, 9, 31, 32, 35, 61, 65, 68, 71, 72, 77, 78, 79, 81, 82, 83, 85, 86, 89, 90, 95, 97, 111, 115, 118, 124, .148, 149, 150, 151, 159, 165, 174, 189 Rhenium, 75 Rhenium1*, 200 Rhenium1**, 201 Rhodium, 77 Rhodium108, 200 Rhodium108, 205 Ricin, 188 Rodenticides, 47, 73 Rotameter, 269, 270 Rotenone, 194, 255 Rotogravure printing, 230 Rubber, 189-190, 192 Rubber cementing, 105, 140, 211, 239 Rubber operations, 54, 101, 140, 239 Rubidium, 29 Rubidium**, 200 Ruthenium, 77 . Ruthenium10*, 200, 205 Samarium181, 197, 200 Samarium188, 201 Scandium, 46 Scandium48, 200 Selenium, 20, 68-69, 190, 255, 257 in urine, determination of, 390-392 Selenium oxide. 68 Selenium oxychloride, 69 Shaver's disease, 46 Siderosis, 75, 221 Silica dust, 219, 220, 223, 256 Silica (free), determination of, 392- 394 Silica gel adsorber, 280, 281, 282, 288 Silicon, 47. 211, 221, 222 Silicon carbide, 186, 256 Silicon tetrafluoride, 73 Silicosis, 22. 46, 47, 48, 186, 223 Silver, 29-30 Silver105, 197, 200 Silver111, 197, 200 Silver plating, 225 Silver soldering, 36, 72, 222 Soapstone, 256 Sodium, 29 Sodium**, 201, 202-203 Sodium*4, 196, 200, 202-203 Sodium carbonate, 86, 224 Sodium chlorite, 90 Sodium cyanide, 95 Sodium fluoroacetate, 73, 255 Sodium hydroxide, 86, 224, 255 Sodium peroxide, 87 Soldering, 52, 222, 235 Spray coating, 226-227 Steel tempering, 52 Stereotyping, 52, 230 Sterility, 12, 196 Stibine, 66, 253 Stoddard solvent, 253 Storage-battery manufacture (see Bat tery-manufacturing operations) Strontium, 20, 34 Strontium**, 197, 201, 202, 204 in urine, determination of, 394 Strontium*0, 11, 197, 201, 202, 204, 205, 257 in urine, determination of, 394 Strychnine, 255 Styrene, 110, 236, 239, 253 determination of, 394-396 Sulfur, 67 Sulfur55, 201, 203 Sulfur chloride, 81, 253 determination of, 396 Sulfur dioxide, 9, 81-82, 220, 236, 237, 238, 253 determination of, 396-397 Sulfur hexafluoride, 253 Sulfuric acid, 82-83, 223, 235, 236, 240, 255 determination of, 397 Sulfur-lamp apparatus, 332 Sulfur pentafluoride. 83, 253 Sulfuryl chloride, 253 Susceptibility, individual, 243-244 Systox, 181, 194, 255 Talc dust, 256 Tantalum, 66 Tantalum18*. 201 Technetium9*, 201 Technetium**, 201 TEDP, 255 Teflon, 191 Tellurium, 20, 69, 220. 255, 257 determination of, 397 Tellurium1**, 201 Tellurium1*9, 201 TEPP, 3, 180, 194, 256 Terpenes, 111 Test-paper determinations, 265-266 Test-paper holder, 266 Tetrabromoethane, 143, 317 Tetrachlorodifluoroethane, 144 Tetrachloroethane, 11, 141-142, 217, 234, 237, 246. 253. 257, 317 determination of, 397-398 Tetrachloroethylene, 14, 15, 131, 146, 211, 231, 232, 233, 236, 237, 238, 253 determination of, 398 Tetrachloronaphthalene, 151-152 Tetrahydrofuran, 253 Tetramethyl succinonitrile, 190 Tetranitromethane, 159, 253 determination of, 398 Tetryl, 165, 256 determination of, 398-399 Textile printing, 230 ST0852787 INDEX 451 Thallium, 47, 256 Thallium*04, 201 Thallium*0*, 198 Thanite. 194 Thermal indicators, 259-261 Thermal precipitators, 275 Thimet, 184 Thiocyanates, 94, 194 in urine, determination of, 400-401 Thiokol, 192 Thionyl chloride, 81, 255 Thiophosphenyl chloride, 253 Thiram, 256 Thorium, 58 Thorium***, 198, 208 Thorium**0, 198, 199 Thorium***, 196, 198, 199, 201, 208 Thorium**4, 198, 201, 208 Thoron, 28, 206 Thorotrast, 208 Thulium170, 201 Tin, 49, 220 Tin11*, 201 Tinning, 52, 53 Titanium, 48, 221, 223 Titanium dioxide, 48, 192, 256 Titanium tetrachloride, 48 TNT, 11, 20, 23, 162-163, 217, 256, 258 determination of, 408-409 in urine, determination of, 409-410 o-Tolidine, 173 Toluene, 6, 14, 16, 25, 99, 108-109, 253 determination of, 302-303, 401-403 industrial exposure to, 192, 211, 227, 228, 229, 231, 236-240 in urine, 20, 257 determination of, 403--404 Toluene diisocyanate, 176, 253 determination of, 404 Toluidine, 171, 253 Tolyldiphenyl phosphate, 191 Tolylenediamine, 171 Toxaphene, 194 Tributyl phosphate, 183 Trichloroacetic acid, 146, 232 in mine, 257 determination of, 405-406 Trichlorobenzene, 150 Trichlorobutane, 148 Trichloroethane, 141, 317 Trichloroethylene, 10, 80, 108, 131, 137, 145-146, 253, 258, 286, 287, de3te1r7mination of, 406 industrial exposure to, 192, 211, 222, 231, 232, 233, 234, 236, 237, 238 in urine, 20, 146, 257 Trichlorofluoromethane, 317 Trichloronaphthalene, 151-152, 256 Trichloropropane, 147 Tricresyl phosphate, 183, 191 determination of, 406-408 Tridymite, 48 Triethylamine, 168, 253 Triethyl phosphate, 183 Trifluorobremomethane, 253 Trifluorochloroethylene, 147 Trifluorotrichloroethane, 139-140, 253, 286, 287, 317 Trimethylenetrinitroamine, 160 Trimethylphosphite, 184 Trinitroanisol, 165 Trig (heta-chloroethyl) phosphite, 184 Trisodium phosphate, 224 Trithion, 184 Tritium, 20, 202, 257 Trucking operations, 237, 239 Tungsten, 70, 220 Tungsten1**, 201 Tungsten carbide, 76 Turpentine, 111, 192, 253 Ultraviolet photometer, 262, 263, 288 Uranium, 6, 11, 20, 70-71, 220, 221, 256, 257 in urine, determination of, 410 Uranium***, 199, 201, 202, 209 Uranium**4, 198, 199, 202, 209 Uranium***, 197, 199, 201, 202, 209 Uranium***, 196, 197, 198, 199, 201, 202, 209 Uranium hexafluoride, 70 Uranium oxide, 70 Urine analyst 20-21 specific-gravity adjustment, 21 Urine sulfate test, 19, 20, 105-106, 288, 410-411 Vanadium, 61-62, 220, 257 in urine, determination of, 411--413 poisoning, symptoms of, 61-62 Vanadium4*, 201 Vanadium pentoxide, 61, 256 Vapor condensation methods, 282 Varnishes, 192 Ventilation, 213 closed system, 212 local exhaust, 213 Versene (see EDTA) Vinyl carbazole, 191 Vinyl chloride, 144, 253 Vinyl toluene, 253 Vitreous-enamel spraying, 227 Warfarin, 256 Welding, 35, 36, 72, 221-222, 239, 240 Welding fumes, 240, 265 Wood dusts, toxic, 188 Wood-heel covering, 240 Woods and plants, 188 Wool fulling, 233-234, 240 Xenon, 28 Xenon133, 201 452 Xenon1**, 201 Xylene, 109, 229, 239, 240,253, 287 determination of, 413-414 Xylidine, 171, 253 Xylol, 192 Yttrium, 46, 256 Yttrium*0, 204, 394 Yttrium*1, 201 ST0852788 INDEX Zinc, 14, 33-34, 220, 226, 237, 238, 239, 240 determination of, 414--416 Zinc**, 201 Zinc chloride, 34, 222 Zinc chromate, 33, 67, 192, 227 Zinc-fume fever (see Metal-fume fever) Zinc oxide, 15, 33, 192, 256 Zone plating, 226 Zirconium, 49, 256 ST0852719