Chemical Appendix 6
Appendix 6 - Handling Procedures for Some Common Particularly Hazardous Substances
This section outlines special handling procedures for some specific particularly hazardous substances that may be used in Chemistry Department laboratories. The information presented in this section is not meant to be complete, and faculty should consult the appropriate literature and their laboratory supervisor before working with these particularly hazardous substances.
Acrylonitrile is regulated as a human carcinogen by OSHA and also is listed as a substance with a high degree of acute toxicity. The PEL (permissible exposure limit) is 2 ppm as an 8-hour time-weighted average or 10 ppm as averaged over any 15-min period. Dermal or eye contact with liquid acrylonitrile is also prohibited. Work involving significant quantities of acrylonitrile should be conducted using the general procedures outlined in both Parts VI-C and VI-D. Laboratory hoods that have been demonstrated to provide sufficient protection should be used, and closed systems are recommended for laboratory operation.
In humans, acute inhalation exposure to benzene can produce a picture of acute delirium, characterized by excitement, euphoria, and restlessness and, if the exposure is significantly high, the symptoms may progress to depression, drowsiness, stupor, and even unconsciousness. The concentration required to produce this symptom complex is 1000 ppm or higher. These concentrations will also produce irritation of the eye, nose, and respiratory tract. Chronic inhalation exposure to 25-50 ppm of benzene can produce changes in the blood picture that include macrocytosis, decrease in the total red blood count, decrease in platelets, decrease in the hemoglobin concentration, or decrease in leukocytes. Any or all of these hematologic effects may be seen in any individual. Usually, the worker will be asymptomatic while these effects are observed in the blood picture. Continued exposure at somewhat higher concentrations (probably more than 100 ppm) can insidiously result in more severe blood disorders that include leukopenia or even aplastic anemia, with symptoms of headaches, dizziness, loss of appetite, nervousness, irritability, and perhaps bleeding manifestations, i.e., nosebleeds, easy bruisability, or hematuria. Severe cases may have fatal outcomes. Recently, a number or reports have been published that describe leukemia in workers who have had aplastic anemia. These cases have been reported in Italy and Turkey in workers exposed to grossly high concentrations of benzene. In addition, there is some indication that an excess of leukemia may occur without a preceding picture of aplastic anemia in workers who have been repeatedly exposed to benzene at concentrations of more than 100 ppm.
The current OSHA PEL for benzene is 1 ppm as an 8-hour time-weighted average (TWA), 25 ppm for a ceiling concentration for time period such that the 8-hour TWA is not exceeded, and a peak above the ceiling at 50 ppm for no more than 10 min. Benzene is a flammable liquid and should not be exposed to heat or flame. An explosion hazard also exists when its vapors are exposed to flame. Benzene may react vigorously with oxidizing agents such as bromine pentafluoride, chlorine, chromic acid, nitryl perchlorate, oxygen, ozone, perchlorates, aluminum chloride plus fluorine perchlorate, sulfuric acid plus permanganates, potassium peroxide, silver perchlorate plus acetic acid, and sodium peroxide.
Experiments involving the use of benzene should be conducted employing the general procedures outlined in Part VI-C; all operations in which there is the possibility of the accidental release of harmful quantities of benzene should be carried out in a designated area.
(3) Bis(chloromethyl)ether (BCME), Chloromethyl Methyl Ether, and Other Chloromethyl Ether Derivatives
Because of the high volatility of bis(chloromethyl)ether (BCME), inhalation is the route of exposure that presents the greatest hazard to humans. BCME vapor is severely irritating to the skin and mucous membranes and can cause corneal damage that heals slowly. The substance has caused lung cancer in humans. BCME is highly toxic to animals via inhalation: LD50 (rats, 7-hour inhalation) = 7 ppm. It is moderately toxic via the oral and skin routes:LD50 (rats, oral) =280 mg/kg; LD50 (rabbits, skin) =368 mg/kg. Its vapors are strongly irritant to the eyes of rats. Rats and hamsters subjected to 10 or 30, 6-hour exposures of 1 ppm BCME showed evidence of tracheal and bronchial hyperplasia, as well as effects on the central nervous system. BCME is carcinogenic to mice following inhalation, skin application, or subcutaneous administration. In mice, it is carcinogenic by inhalation and subcutaneous administration. BCME is a lung carcinogen in humans.
The TLV for BCME is 0.001 ppm (1 ppb; 5 mg/m3). The substance is classified by ACGIH as a human carcinogen. OSHA has classified BCME as a cancer-suspect agent and has stringent regulations (29 CFR 1910.1008) for its use if its concentration in a material exceeds 0.1%. Work involving chloromethyl ether derivatives must be carried out using the general procedures outlined in Parts VI-C and VI-D.
(4) Carbon Monoxide
Carbon Monoxide is a direct and cumulative poison. It combines with the hemoglobin of the blood to form a relatively stable compound, carboxyhemoglobin, and renders if useless as an oxygen carrier. When about one-third of the hemoglobin has entered into such combination, the victim dies. The gas is a treacherous poison because of its odorless character and insidious action. Exposure to 1500-2000 ppm CO in air for 1 hour is dangerous, and exposure to 4000 ppm is fatal in less than 1 hour. Headache and dizziness are the usual symptoms of CO poisoning, but occasionally the first evidence of poisoning is the collapse of the patient.
Carbon monoxide should be used only in areas that have adequate ventilation employing the general procedures outlined in Part VI-C. A trap or vacuum break should always be used to prevent impurities from being sucked back into a CO cylinder.
(5) Carbon Tetrachloride
The current OSHA PEL for carbon tetrachloride is 2 ppm as an 8-hour time-weighted average. The current TLV for carbon tetrachloride is 5 ppm. Carbon tetrachloride is suspected to have carcinogenic potential in humans. ACGIH also states that skin contact may account for a substantial part of toxic responses.
The carcinogenic potency of carbon tetrachloride is low and in most of its uses in Chemistry Department laboratories it need not be treated as a particularly hazardous substance. In cases where large quantities of carbon tetrachloride are in frequent use, then the general procedures outlined in Part VI-C should provide adequate protection. All operations should be carried out in a hood, not only because of the carcinogenicity of the substance, but also because of its other toxic effects and its volatility. Nitrile rubber is the recommended material for gloves and other protective clothing.
Chlorine is classified as a substance with a high degree of acute toxicity. Humans can generally detect the odor of chlorine at about 0.3 ppm. Minimal irritation of the throat and nose are noticed at about 2.6 ppm and painful irritation at about 3.0 ppm; at a range of 2.6-41.0 ppm, a group of "trained industrial hygienists" noted "strong irritation." The subjective response to chlorine is less pronounced with prolonged exposure. Experimentally determined responses to chlorine by humans are not very consistent. Throat irritation occurs at about 6.6-15 ppm. However, an exposure for medical purposes of a large number of humans to 5-7 ppm for 1 hour did not result in serious or long-term consequences. Exposure to about 17 ppm causes coughing, and levels as low as 10 ppm may cause lung edema. Chronic effects on humans from long-term low-level exposures have been well documented. Animal exposures have indicated that prolonged exposure to approximately 1.7 ppm for 1 hour per day may cause deterioration in the nutritional state, blood alteration, and decreased resistance to disease. The TLV and the OSHA PEL are 0.5 ppm (1.5 mg/m) TWA over eight hours. NIOSH has recommended a ceiling limit of 0.5 ppm over any 15-min period. The ACGIH 15-min exposure limit is 3 ppm.
Chlorine should be kept away from easily oxidized materials. Chlorine reacts readily with many organic chemicals, sometimes with explosive violence. Because of the high toxicity of chlorine, laboratory operations using it must be carried out in a hood employing the general procedures outlined in Part VI-C.
Inhalation exposure to chloroform at concentrations greater than 1000 ppm can produce dizziness, nausea, and headaches. At higher concentrations, there can be disorientation and delirium progressing to unconsciousness. Such high exposure can also produce liver and possibly kidney damage. It is believed that chloroform can sensitize the heart to adrenaline, causing cardiac arrhythmias and possibly death. High concentrations of the vapor can produce conjunctivitis. Liquid chloroform in the eyes will produce a painful corneal injury that usually heals in several days. Chronic exposure to chloroform at concentrations of 100-200 ppm has been reported to produce large livers. Continued contact with the skin can produce drying , fissuring, and inflammation. In experimental studies, prolonged ingestion of high levels of chloroform by mice resulted in liver cancers and by rats, kidney tumors.
Although the fire hazard of chloroform is slight, exposure to heat or flame can result in generation of phosgene gas. Chloroform reacts violently with acetone plus a base, aluminum, disilane, lithium, magnesium, nitrogen tetroxide, potassium, perchloric acid plus phosphorus pentoxide, potassium hydroxide plus methanol, potassium tert-butoxide, sodium, sodium hydroxide plus methanol, sodium methylate, or sodium hydride.
The current OSHA PEL for chloroform is 2 ppm as an 8-hour time-weighted average. The ACGIH currently recommends that chloroform be treated as a suspect human carcinogen and recommends an 8-hour time-weighted average exposure of 10 ppm. Although chloroform has caused tumors in animals, its potency is low. In most of its uses in the Chemistry Department it need not be treated as a particularly hazardous substance. In cases where significant quantities of chloroform are in frequent use, the general procedures outlined in Part VI-C should provide adequate protection. The high volatility of chloroform emphasizes the importance of a hood for such operations. Polyvinyl alcohol gloves provide the best hand protection.
(8) Dimethyl and Diethyl Sulfate
Many cases of dimethyl sulfate poisoning have been reported. The common initial symptoms are headache and giddiness, with burning of the eyes. The patient's condition may worsen, with painful eyes, nose and throat irritation, loss of voice, coughing, difficult in breathing and swallowing, vomiting, and diarrhea possible. The onset of the symptoms may be delayed up to 10 hours. Skin contact causes blistering and necrosis, and DMS can be absorbed through the skin in sufficient quantity to cause systemic intoxication. In the worst cases, there is severe inflammation of the mucous membranes and pulmonary injury that may be fatal; several deaths have occurred. For example, exposure to 97 ppm for 10 min was fatal. DMS is moderately toxic to animals via the oral route: LD50 (rats) = 440 mg/kg. Undiluted DMS produced moderate to severe irritation when applied to the skin of guinea pigs; 1% DMS produced mild irritation. DMS does not cause skin sensitization in animals. Undiluted DMS applied to rabbit eyes produced severe injury. Even a 1-hour exposure to 58 ppm has resulted in permanent eye damage in rats. During a 4-hour exposure, 30 ppm DMS killed five out of six rats, but 15 ppm was not lethal.
DMS has been shown to be carcinogenic in the rat by inhalation, subcutaneous injection, and following 1 hour per day exposures to 10 ppm DMS for 130 days. The TLV for DMS is 0.1 ppm (0.5 mg/m3) as an 8-hour time-weighted average. DMS is classified as being suspected of carcinogenic potential in humans by the ACGIH. The OSHA PEL for DMS is 0.5 ppm. These limits include a warning of the potential contribution of skin absorption to the overall exposure.
The general procedures outlined in Part VI-D should be used when handling more than a few grams of DMS in view of its fairly high carcinogenic potency in rats by inhalation and its ability to penetrate the skin. It is particularly important to avoid skin contact by appropriate use of rubber gloves, a rubber apron, and other protective apparel, and to avoid inhalation of even low concentrations of vapor by working in a hood. Operations involving smaller quantities of DMS can be conducted using the general procedures presented in Part VI-C.
(9) Ethylene Dibromide (1,2-Dibromoethane)
Ethylene dibromide (EDB) is classified as a compound with a high degree of acute toxicity; the approximate oral lethal dose of EDB for humans is 5 ml. Skin absorption of EDB can also cause death, and inhalation of the vapor can produce pulmonary edema. EDB can cause severe irritation to all exposed tissues, respiratory tract, skin, and eye. Systemic effects include central nervous system depression, kidney injury, and severe liver necrosis. Ethylene dibromide is highly toxic to animals via inhalation.
The maximum survival exposure of rats to EDB vapors in air are 3000 ppm for 6 min, 400 ppm for 30 min, and 200 ppm for 2 hours. It is moderately toxic via the oral and skin routes: LD50 (rats, oral) = 140 mg/kg; LD50 (rabbits, skin) = 300 mg/kg. EDB is markedly irritating to skin, and a 10% solution has caused serious but reversible corneal injury in rabbit eyes. Rats were repeatedly exposed to 50 ppm EDB for 6 months. Half died from pneumonia and upper respiratory tract tumors (squamous-cell carcinomas of the forestomach) in mice and rats following oral administration. The 1979 TLV for EDB was 20 ppm (155 mg/m3) as an 8-hour time-weighted average. The exposure limit is 30 ppm over any 15-min period. These limits include a warning about the potential contribution of skin absorption to the overall exposure. In 1980, the ACGIH put EDB in category A 1b (human carcinogen). For this category, there is no assigned TLV, but the ACGIH recommends that those working with A 1b carcinogens should be properly equipped to ensure maximum peak is 50 ppm for 5 min in any 8-hour time period.
On the basis of the carcinogenicity data for EDB, the procedures described in Part VI-D should be followed when handling more than a few grams in the laboratory. Operations involving smaller quantities should be carried out using the procedures outlined in Part VI-C. Serious skin injury can occur from direct exposure to EDB. The substance can penetrate neoprene and several other types of plastic; therefore, gloves and other protective apparel of these materials provide only temporary protection if EDB spills on them.
Hydrazine is classified as a compound with a high degree of acute toxicity; exposure to its vapors can cause respiratory tract irritation, excitement, convulsion, cyanosis, and decrease in blood pressure. The liquid can severely burn the eyes and skin. Hydrazine can cause fatty degeneration of the liver, nephritis, and hemolysis. Hydrazine is moderately toxic to animals via the inhalation, oral, and skin routes: LC50 (rats, 4-hour inhalation) = 570 ppm; LD50 (rats, oral) = 60 mg/kg; LD50 (rabbits, skin) = 283 mg/kg (hydrazine hydrate). It is a strong skin and mucous membrane irritant and a strong skin sensitizer. Hydrazine hydrate produced moderately severe irritation when applied to rabbit eyes. After repeated oral, skin, or injection exposure, the effects noted include weight loss, weakness, vomiting, and convulsions. The chief histological finding is fatty degeneration of the liver.
Among guinea pigs and dogs exposed to hydrazine in the air 5-47 times, the dogs showed liver damage, with lesser damage to the kidneys and lungs, while the guinea pigs had pneumonitis and partial lung collapse.
Hydrazine and hydrazine salts have been shown to be carcinogenic in mice after oral and intraperitoneal administration and in rats following oral dosing. By the oral route, effects were found at doses of 24-36 (mg/kg)/day in mice and 20 (mg/kg)/day in rats. No tumors were observed in Syrian golden hamsters after oral administration. The ACGIH has classified hydrazine as suspected of carcinogenic potential in humans. The TLV for hydrazine is 0.1 ppm (0.1 mg/m3) and the OSHA PEL is 0.1 ppm (0.1 mg/m3) as 8-hour time-weighted averages. These limits include a warning about the potential contribution of skin absorption to the overall exposure. The NIOSH has (1978) recommended a ceiling limit of 0.03 ppm in any 2-hour period.
When more than a few grams of hydrazine are to be used in the laboratory, the general procedures outlined in both Parts VI-C and VI-D should be used because hydrazine is carcinogenic in animal tests, quite volatile, and readily absorbed through the skin. Nitrile rubber is recommended for gloves and other protective apparel. Prompt washing with water effectively removes hydrazine from skin that it has splashed on. Hydrazine should not be used in the vicinity of a flame or under conditions where sparks can occur, as an explosion or fire can result.
(11) Hydrogen Bromide and Hydrogen Chloride
Both hydrogen bromide (HBr) and hydrogen chloride (HCL) are toxic gases which are severely irritating to the upper respiratory tract. The acids formed neutralize the alkali of the tissues and can cause death as a result of edema or spasm of the larynx and inflammation of the upper respiratory system. Concentrations of 0.13-0.2% are lethal for human beings in exposures lasting a few minutes. However, because of their odor, usually these gases provide adequate warning for prompt voluntary withdrawal from contaminated atmospheres. These gases are also corrosive to the skin and mucous membranes and can cause severe burns. Exposure to high concentrations may also result in dermatitis. Contact with the eyes rapidly causes severe irritation of the eyes and eyelids.
Hydrogen bromide and hydrogen chloride are corrosive gases that have pungent, irritating odors. Although both are colorless, they fume in moist air because of their high solubility in water. In a cylinder under pressure, both exist in the form of a gas over a liquid (under such conditions, the cylinder pressure is equal to the vapor pressure of the substance contained; at 25o C, this is 4.22 MPa (613 lb/in.2 for HCL and 2.20 MPa (320 lb/in.2 for HBr). As long as liquid is present in the cylinder, the pressure will remain fairly constant. Although neither HBr nor HCl is combustible, both react with common metals to form hydrogen, which may form explosive mixtures with air.
Operations involving significant quantities of hydrogen bromide and hydrogen chloride should be conducted using the general procedures outlined in Part VI-C. Laboratory workers should wear protective apparel, including rubber gloves, suitable gas-tight chemical safety goggles, and clothing such as a rubber or plastic apron. Proper respiratory equipment should be available. These gases should be handled only in adequately ventilated areas. A check valve, vacuum break, or trap should always be used to prevent foreign materials from being sucked back into the cylinder because this can cause the development of dangerous pressures. Leaks of HBr and HCl will be evident by the formation of dense white fumes on contact with the atmosphere. Small leaks of HCl can be detected by holding an open bottle of concentrated ammonium hydroxide near the site of the suspected leak; the formation of dense white fumes confirms the existence of a leak. Cylinder-valve leaks can usually be corrected by tightening the valve packing nut (by turning it clockwise as viewed from above).
(12) Hydrogen Cyanide
Prior approval from the Chemical Hygiene Committee is required before using hydrogen cyanide (see Part VII).
(13) Hydrofluoric Acid
The use of anhydrous hydrogen fluoride requires prior approval from the Chemical Hygiene Committee. All forms - dilute or concentrated solutions or the vapor - of hydrofluoric acid (HF) cause severe burns. Inhalation of anhydrous HF or HF mist or vapors can cause severe respiratory tract irritation that may be fatal. Death from pulmonary edema occurred within 2 hours in three of six workers splashed with 70% HF solution despite prompt showering with water. Anhydrous HF is a clear, colorless liquid that boils at 19.5o C. Because of its low boiling point and high vapor pressure, anhydrous HF must be stored in pressure containers. A 70% aqueous solution is a common form of HF. Hydrofluoric acid is miscible with water in all proportions and forms an azeotrope (38.3% HF) that boils at 112o C. Anhydrous or concentrated aqueous HF causes immediate and serious burns to any part of the body. Dilute solutions (<30%) and gaseous HF are also harmful, although several hours may pass before redness or a burning sensation is noticed. These burns may still by quite severe and progressively damaging to the skin and deeper tissues. "Undissociated HF readily penetrates skin and deep tissue where the corrosive fluoride ion can cause necrosis of soft tissues and decalcification of bone; the destruction produced is excruciatingly painful. Fluoride ion also attacks enzymes (e.g. of glycolysis) and cell membranes. The process of tissue destruction and neutralization of the hydrofluoric acid is prolonged for days, unlike other acids that are rapidly neutralized. Because of the insidious manner of penetration, a relatively mild or minor exposure can cause a serious burn" [Proctor, N. H.; Hughes, J. P.; Fischman, M. L. Chemical Hazards of the Workplace, J. B. Lippincott Co., Philadelphia, 1988, p.279]. Occasionally workers fail to recognize the importance of seeking medical attention for HF before pain commences. By the time the victim is affected with progressively deep and more painful throbbing and burning, serious damage may have taken place. Exposures under fingernails can be a particularly painful problem if ignored. Wearing clothing (including leather shoes and gloves) that has absorbed small amounts of HF can result in serious delayed effects such as painful slow-healing skin ulcers.
When handling HF, it is crucial to ensure adequate ventilation by working only in a hood so that safe levels (3 ppm) are not exceeded. All contact of the vapor of the liquid with eyes, skin, respiratory system, or digestive system must be avoided by using protective equipment such as a face shield and neoprene or polyvinyl chloride gloves. The protective equipment should be washed after each use to remove any HF on it. Safety showers and eyewash fountains should be nearby. Anyone working with HF should have received prior instructions about its hazards and in proper protective measures and should know the recommended procedure for treatment in the event of exposure (Reinhardt, C.F> et al.; Am. Ind. Hyg. Assn. J., 1966, 27, 166.)
Spills and leaks - The vapors of both anhydrous HF and aqueous 70% HF produce visible fumes if they contact moist air. This characteristic can be useful in detecting leaks but cannot be relied on because of atmospheric variations. Spills of HF must be treated immediately to minimize the dangers of vapor inhalation, body contact, corrosion of equipment, and possible generation of hazardous gases. Spills should be contained and diluted with water. The resulting solution should be neutralized with lime before disposal.
Waste disposal - Waste HF should be slowly added to a larger volume of a stirred solution of slaked lime to precipitate calcium fluoride, which is chemically inert and poses little toxic hazard (sodium fluoride is highly soluble and toxic). Alternatively, hydrofluoric acid can be diluted to about 2% concentration with cold water in a polyethylene vessel, neutralized with aqueous sodium hydroxide, and treated with excess calcium chloride solution to precipitate calcium fluoride.
In the event of exposure - Anyone who knows or even suspects that he or she has come into direct contact with HF should immediately flush the exposed area with large quantities of cool water. Exposed clothing should be removed as quickly as possible while flushing. Medical attention should be obtained promptly, even if the injury appears slight. On the way to the physician, the burned area should be immersed in a mixture of ice and water. If immersion is impractical, a compress made by inserting ice cubes between layers of gauze should be used. Make sure that the physician understands that the injury was cause by HF and requires treatment very different from other acid burns. Even in the case of very small exposure, washing alone may not be sufficient to completely prevent injury. For minor exposures such as small hole in glove, application of a calcium glutaconate antidote gel can bind free fluoride ion not removed by washing.
If HF liquid or vapor has contacted the eyes, these organs should be flushed with large quantities of clean water while the eyelids are held apart. This flushing should be continued for 15 minutes. Medical attention should be obtained promptly.
Anyone who has inhaled HF vapor should be removed immediately to an uncontaminated atmosphere and kept warm. Medical help should be obtained promptly. Anyone who has ingested HF should drink a large quantity of water as quickly as possible. Do not induce vomiting. Again, medical help should be obtained promptly. After the acid has been thoroughly diluted with water, if medical attention is delayed, the person should be given milk or two fluid ounces of milk of magnesia to drink to sooth the burning effect.
(14) Hydrogen Sulfide
Hydrogen sulfide is extremely dangerous. Human exposure to relatively low concentrations of H2S has caused corneal damage, headache, sleep disturbances, nausea, weight loss, and other symptoms suggestive of brain damage. Higher concentrations can cause irritation of the lungs and respiratory passages and even pulmonary edema. Exposure to 210 ppm for 20 min has caused unconsciousness, arm cramps, and low blood pressure. Coma may occur within seconds after one or two breaths at high concentrations and be followed rapidly by death. For example, workers exposed to 930 ppm H2S for less than 1 min died. Hydrogen sulfide is moderately toxic to animals via the inhalation route: LC50 (mice, 1 hour) = 673 ppm; LC50 (mice, 7.5 hours) = 140 ppm. Exposure to 10-13 ppm for 4-7 hours has caused eye irritation. Skin absorption of H2S is slight and not
considered significant. However, prolonged or repeated skin contact might cause mild irritation. Guinea pigs that had 0.78 in2 of their skin exposed to 100% H2S vapors for 1 hour experienced slight swelling. The TLV and PEL for H2S is 10 ppm (14 mg/m3) as an 8-hour time-weighted average and 15 ppm as a short-term exposure limit. NIOSH (1977) has recommended a 10-min ceiling of 10 ppm.
Partly because of the disagreeable odor of H2S, but also because of its toxicity, laboratory operations with it should be carried out in a hood. Use the general procedures outlined in Part VI-C when working with hydrogen sulfide. Cylinders of it should not be stored in small, unventilated rooms, as deaths have resulted from people entering such rooms containing a leaking cylinder.
(15) Nickel Carbonyl
The use of nickel carbonyl requires prior approval from the Chemistry Department Chemical Hygiene Committee (see part VII).
(16) Nitrogen Dioxide
Nitrogen dioxide (NO2) is classified as a highly acute toxin; it is a primary irritant, acting primarily on the lungs and to a lesser extent on the upper respiratory tract. It is certainly one of the most insidious of the gases. The inflammation of the lungs may cause only slight pain, but the edema that results may easily cause death. One hundred ppm of NO2 in air is a dangerous concentration for even a short exposure, and 200 ppm may be fatal in a short time. Nitrogen dioxide is reddish brown, has an irritating odor, and must be avoided by the use of an air-purifying respirator equipped with an acid-gas cartridge or canister; at concentrations greater than 50 times the TLV, a positive-pressure atmosphere-supplying respirator must be used and, in IDLH atmospheres, a pressure-demand self-contained breathing apparatus or a positive-pressure air-line respirator that has escape-cylinder provisions is required.
Nitrogen dioxide should be handled using the general procedures outlined in Part VI-C. Nitrogen dioxide is a deadly poison, and no one should work with a cylinder of this substance unless they are fully familiar with its handling and its toxic effect. Ventilation is extremely important, and respiratory protective equipment should always be available. Only stainless steel fittings should be used.
The element of mercury is a liquid metal with a vapor pressure of 0.00185 mm at 25o C. This corresponds to a saturation concentration of 20 mg of mercury per cubic meter of air or 2.4 ppm of air. The American Conference of Governmental Industrial Hygienists has established a threshold limit for mercury vapor of 0.05 mg of mercury per cubic meter of air for continuous 40-hour per week exposure. Long term chronic exposure to mercury vapor in excess of 0.05 mg of mercury per cubic meter of air may result in cumulative poisoning. The use of mercury in laboratory amounts in well-ventilated areas is fairly safe; however special precautions must be followed when working with large quantities of mercury.
Mercury poisoning from exposure by chronic inhalation produces a variety of symptoms. The characteristic effects are emotional disturbances, unsteadiness, inflammation of the mouth and gums, general fatigue, memory loss, and headaches. Kidney damage may result from poisoning by mercurial salts. In most cases of exposure by chronic inhalation, the symptoms of poisoning gradually disappear when the source of exposure is removed. However, improvement may be slow and complete recovery may take years. Skin contact with mercury compounds produces irritation and various degrees of corrosion. Soluble mercury salts can be absorbed through the intact skin and produce poisoning.
The general procedures outlined in Part VI-C should be followed when working with large quantities of liquid mercury. Every effort should be made to prevent spills of metallic mercury because the substance is extremely difficult and time consuming to pick up. Droplets get into cracks and crevices, under table legs, and under and into equipment. If spills are frequent and Hg is added to the general air level, the combined concentration may exceed the allowable limits.
Storage - Containers of large quantities of mercury should be kept closed and stored in secondary containers in a well-ventilated area. When breakage of instruments or apparatus containing mercury is a possibility, the equipment should be placed in an enameled or plastic tray or pan that can be cleaned easily and is large enough to contain the Hg. Transfers of Hg from one container to another should be carried out in a hood and over a catch tray or pan to confine any spills.
Cleanup of spills - Pools of metallic Hg can be collected by suction by using an aspirator bulb or a vacuum device made from a filtering flask, a rubber stopper, and several pieces of flexible and glass tubing. Alternatively, mercury-spill cleanup kits are available commercially. When a large spill, pressure system rupture, or heating of mercury is involved, the College Safety Officer (356-2457) will survey the area and advise on the degree of hazard which may exist and necessary preventive measures to be undertaken. If Hg has spilled on the floor, the workers involved in cleanup and decontamination activities should wear shoe covers. When the cleanup is complete, the shoe covers should be disposed of and the workers should thoroughly wash their hands, arms, and face several times.
Waste Disposal - Significant quantities of metallic Hg from spills or broken thermometers or other equipment, and contaminated Hg from laboratory activities should be collected in thick-walled high-density polyethylene bottles for reclamation. Rags, sponges, shoe covers, and such used in cleanup activities, and broken thermometers containing small amounts of residual mercury, should be placed in a sealed plastic bag, labeled, and disposed of in a safe manner.
(18) N-Nitrosodialkylamines and Certain Other N-Nitroso Compounds
N-Nitrosodimethylamine is strongly hepatotoxic and can cause death from liver insufficiency in experimental animals. It is carcinogenic in at least 10 animal species, including subprimates. The main targets for its carcinogenic activity are the liver, lung, esophagus, trachea, and nasal cavity. Although data are not available on the toxicity of N-nitrosodiethylamine in humans, the closely related compound N-nitrosodimethylamine has caused extensive liver damage as a consequence of ingestion, inhalation, or topical application to the skin.
The general procedures outlined in Parts VI-C and Part VI-D should be followed when working with N-nitrosodialkylamines. All work with N-nitrosodialkylamines should be carried out in a well-ventilated hood or in a glove box equipped with HEPA filter. To the extent possible, all vessels that contain N-nitrosodialkylamines should be kept closed. All work should be carried out in an apparatus that is contained in or mounted above unbreakable pans that will contain any spill. All containers should bear a label such as the following: CANCER-SUSPECT AGENT. All personnel who handle the material should wear plastic, latex, or neoprene gloves and a fully buttoned laboratory coat.
Storage - All bottles of N-nitrosodialkylamines should be stored and transported within an unbreakable outer container; storage should be in a ventilated storage cabinet (or in a hood).
Cleanup of spills and waste disposal - Because N-nitrosodialkylamines are chemically stable under usual conditions, disposal is best carried out by incineration. Contact the Safety Office to arrange for the disposal of waste and contaminated materials. For incineration of liquid wastes, solutions should be neutralized if necessary, filtered to remove solids, and put in closed polyethylene containers for transport. All equipment should be thoroughly rinsed with solvent, which should then be added to the liquid waste for incineration. Great care should be exercised to prevent contamination of the outside of the solvent container. If possible, solid wastes should be incinerated; if this is not possible, solid wastes from reaction mixtures that may contain N-nitrosodialkylamines should be extracted and the extracts added to the liquid waste. Similarly, any rags, paper and such that may be contaminated should be incinerated. Contaminated solid material should be enclosed in sealed plastic bags that are labeled CANCER-SUSPECT AGENT and with the name and amount of the carcinogen. The bags should be stored in a well-ventilated area until they are incinerated. Spills of N-nitrosodialkylamines can be absorbed by Celite R or commercial spill absorbent. After the absorbent containing the major share of the nitrosamine has been picked up (avoid dusts; do not sweep), the surface should be thoroughly cleaned with a strong detergent solution. If a major spill occurs outside of a ventilated area, the room should be evacuated, the Campus Police (911) should be contacted, and the cleanup operation should be carried out by trained persons equipped with self-contained respirators. Those involved in this operation should wear rubber gloves, laboratory coats, and plastic aprons or equivalent protective apparel.
Phosgene is classified as a substance with a high degree of acute toxicity. In humans, the symptoms of overexposure to phosgene are dryness or a burning sensation in the throat, numbness, vomiting, and bronchitis. An airborne concentration of 5 ppm may cause eye irritation and coughing in a few minutes. The substance can cause severe lung injury in 1-2 min at a level of 20 ppm. Exposure to concentrations above 50 ppm is likely to be fatal. Phosgene is extremely toxic to animals via inhalation. Thus 74% of a group of rats died from exposure to 55-100 ppm for only 10 min. Liquid phosgene is likely to cause severe skin burns and eye irritation. Pulmonary edema, bronchiolitis, and emphysema were found in cats and guinea pigs exposed to 2.5-6.25 ppm of phosgene/day for 2-41 days. A variety of animals exposed to 0.2 or 1.1 ppm for 5 hours per day also had pulmonary edema. The TLV and the OSHA PEL for phosgene are 0.1 ppm (0.4 mg/m3) as an 8-hour TWA. NIOSH has recommended a limit of 0.2 ppm over any 15-min period.
Laboratory operations involving phosgene require the use of the general procedures outlined in Part VI-C. Work with phosgene should always be carried out with water or dilute alkali. Note that for many applications phosgene can be replaced by the less hazardous diphosgene and triphosgene.
(20) Sodium Cyanide (and other cyanide salts)
Inorganic cyanide salts are classified as substances with a high degree of acute toxicity. Sodium cyanide is among the fastest acting of all known poisons. The lethal oral dose for humans is 200 mg. The symptoms of cyanide overdose include weakness, headache, confusion, and, occasionally, nausea and vomiting. Higher doses may be followed by almost instantaneous death. Solutions are irritating to the skin, nose, eyes, and cyanide is absorbed through the skin. Sodium cyanide is highly toxic to animals via the oral route: LD50 (rats) = 6.4 mg/kg. It can be corrosive to the skin and the eyes, for it is highly alkaline. Sodium cyanide can also produce toxic symptoms via skin absorption and inhalation. The TLV and OSHA PEL for cyanide are both 5 mg/m3 as an 8-hour TWA. These limits include a warning of the potential contribution of skin absorption to the overall exposure. In 1976, NIOSH recommended that the 5 mg/m3 limit be retained but that its basis be changed from an 8-hour TWA to a 10-min ceiling.
Proper gloves should be worn when handling dry sodium cyanide. Rubber gloves and splash proof goggles should be worn when substantial amounts of sodium cyanide solution are used. Hydrolysis of sodium cyanide (and other cyanide salts) by water or acid generates HCN which is extremely hazardous. Consequently, cyanide salts should always be handled using the general procedures outlined in Part VI-C. All reaction equipment in which cyanides are used or produced should be placed in or over shallow pans so that spills or leaks will be contained. In the event of spills of HCN or cyanide solutions, the contaminated area should be evacuated promptly and it should be determined immediately whether anyone had been exposed to cyanide vapors or liquid splash. Consideration should be given to the need for evacuating other parts of the building or notifying other occupants that the spill has occurred. In general, it is usually best not to attempt to dilute or absorb such spills if they occur in well-ventilated areas.
Detection - Hydrogen cyanide has a characteristic odor that resembles that of bitter almonds, however, many people cannot smell it in low concentrations, and this method of detection should not be relied on. Vapor-detector tubes sensitive to 1 ppm of HCN are available commercially. The presence of free cyanide ion in aqueous solution may be detected by treating an aliquot of the sample with ferrous sulfate and an excess of sulfuric acid. A precipitate of Prussian blue indicates that free cyanide ion is present.
Storage - Sodium cyanide and acids should not be stored or transported together. An open bottle of NaCN can generate HCN in humid air, and HCN may be liberated from spills of sodium cyanide solutions.
Waste disposal - Waste solutions containing cyanides should be sealed in clearly marked bottles. Contact the Safety Office to arrange disposal of these containers.
In the event of exposure - Anyone who has been exposed to HCN should be removed from the contaminated atmosphere immediately. Any contaminated clothing should be removed and the affected area deluged with water. Emergency medical attention should be obtained immediately.