Information on Hazardous Chemicals by Class
INTRODUCTION This Appendix contains a description of the physical and/or toxic hazards commonly encountered in laboratory chemicals. For each class some examples are provided. The examples provided is not a complete list of chemicals that fall within that hazard class. To use this section, obtain information on specific chemicals of interest (using MSDS's, compendia of information, etc.) to determine which hazard classes apply; then refer to this Appendix for a description of that hazard class. A. FLAMMABILITY Certain physical characteristics are used to describe the flammability characteristics of chemicals. The flash point is the temperature at which there is enough vapor above the liquid to ignite in the presence of a spark, and the auto ignition temperature is the temperature which the material will ignite without a spark source. The boiling point is the temperature at which the vapor pressure above liquid is equal to atmospheric pressure and the vapor pressure is the partial pressure of chemical vapor at a stated temperature, often 25 C. The lower the flash point, lower the autoignition temperature, lower the boiling point, and higher the vapor pressure, the greater the flammability hazard. Lower and upper explosion or flammability limits are also used to characterize the flammability of chemicals. The LEL (or LFL), lower explosive (flammable) limit, and UEL (or UFL), upper explosive (flammable) limit defines the lower and upper ends of the explosive or flammable range. Air and solvent mixtures (expressed as percent solvent vapor) within the flammable range will burn; below the LEL or above the UEL the mixture is too lean (not enough fuel) or too rich (too much fuel), respectively, to burn. A table of highly flammable materials follows, and after that a table which includes the flash point, boiling point, auto ignition temperature, and the upper and lower explosive (flammable) limits for a selection of common solvents. B. FLAMMABILITY DATA FOR COMMON SOLVENTS SOLVENT FLASH BOILING AUTO POINT POINT IGN oC oC oC acetone -16.7 57 604 n-amyl acetate 25 149 379 n-amyl alcohol 57 138 327 anthracine 121 340 540 benzene -11 80 580 n-butyl acetate 39 127 431 n-butyl alcohol 47 117 367 butyl cellosolve 61 171 244 isobutyl alcohol 22 107 441 carbon disulfide -22 40 125 cellosolve 40 135 238 cellosolve acetate 51 156 379 chlorobenzene 32 132 640 cyclohexane 3 80 245 dibutylphthalate 157 366 403 1,2-dichloroethylene 17 84 413 diethyl ether -41 35 186 ethyl acetate -4 77 486 ethyl alcohol 14 78 426 ethyl chloride -50 12 966 ethylene glycol 111 119 7413 ethyl formate -19 54 455 n-heptane -4 98 233 n-hexane -14 69 247 kerosene 73* 301* 210 methyl acetate -13 60 502 methyl alcohol 0 64 475 methyl n-butyl ketone 23 128 533 methyl cellosolve 47 124 288 methyl cellosolve acet. 56 143 ---- methyl cyclohexanone 55 163 595 methyl ethyl ketone -7 80 516 naphtha (VMP) 6* 161* 232 naphthalene 79 218 527 octane 13 125 220 isopropyl acetate 8 90 460 n-propyl acetate 14 102 842 n-propyl alcohol 22 97 433 toluene 4 111 552 o-xylene 30 144 493 * The composition of this material varies; what is given is the maximum of a range. C. TABLE OF HIGHLY FLAMMABLE SOLVENTS Acetaldehyde Diethylcarbonate Methyl-n-propyl ketone Acetone Diethyl ketone 1-Methylpyrrole Acetonitrile 3,4-Dihydro-2H-pyran Acetyl chloride Diisopropyl amine Naphtha (50o) (Reg) Acrolein Diisopropyl ether Nitroethane Acrylonitrile Dimethoxymethane Allyl acetate Dimethoxypropane Octane Allyl alcohol Dimethylcarbonate Allyl amine Dimethyl sulphide Phosgene solutions in benzene Allyl bromide 1,4-Dioxane Piperidine Allyl chloride 1,3-Propanediamine Allyl chloroformate Endrin Propargyl bromide Amyl acetate Ethanethiol iso-Propenyl acetate t-Amyl alcohol Ethanol Propionaldehyde Amyl amine Ethoxy acetylene Propionitrile Amylene Ethyl acetate Propionyl chloride iso-Amyl formate Ethyl acrylate iso-Propyl acetate Amyl mercaptan Ethyl benzene n-Propyl acetate Amyl nitrite Ethyl butyrate Propyl alcohol Aziridine Ethyl chloroformate Propyl amine Ethyl crotonate Propyl benzene Benzene Ethylene dichloride Propyl chloride Benzotrifluoride Ethyl formate iso-Propyl ether Butyl acetate N-ethyl morpholine n-Propyl formate Butyl alcohol Ethyl vinyl ether iso-Propyl formate Butyl amine Propyl nitrate Butyl bromide Furan Pyridine Butyl chloride Pyrrolidine Butyl formate Gasoline Pyruvic acid Butyl hydroperoxide Butyl mercaptan Heptane Styrene Isobutyl methyl ketone Hexane tert-Butyl peracetate Hexyl amine Tetrahydrofuran Butyl vinyl ether Hydrocyanic acid Thiophene n-Butyraldehyde Toluene n-Butyronitrile Kerosene Triethyl o-formate Butyryl-chloride Triisobutyl aluminium Ligroin Trimethyl borate Carbon disulphide 2,2,4-Trimethyl pentane Cellulose nitrate Mesityl oxide 2,4,4-Trimethyl-2-pentane Chlorobenzene Methyl acetate p-Chloro-m-cresol Methyl acrylate Unsymmetrical dimethyl hydrazine Chloroprene Methyl alcohol Collodion 2-Methyl-1-butene Valeraldehyde Crotonaldehyde 2-Methyl-2-butene Vinyl acetate Cyclohexane N-Methyl butyl amine Vinyl ether Cyclohexene Methyl butyrate Vinylidene chloride Cyclopentanone Methyl chloroformate Methyl cyclohexane Xylene Di-n-butyl ether 4-Methyl cyclohexene Dibutyl peroxide Methyl ethyl ketone 1,3-Dichloro-2-butene Methyl formate 1,1-Dichloroethane 2-Methyl furan 1,2-Dichloroethylene Methyl hydrazine 1,2-Dichloropropane Methyl isobutyl ketone 1,1-Diethoxyethane Methyl isobutyrate Diethylamine Methyl methacrylate C. PYROPHORIC MATERIALS Pyrophoric materials react with air, or with moisture in air. Typical reactions which occur are oxidation and hydrolysis, and the heat generated by the reactions may ignite the chemical. In some cases, these reactions liberate flammable gases which makes ignition a certainty and explosion a real possibility. Examples of pyrophoric materials are shown below. (a) Pyrophoric alkyl metals and derivatives Groups Dodecacarbonyltetracobalt Silver sulphide Dialkytzincs Dodecacarbonyltriiron Sodium disulphide Diplumbanes Hexacarbonylchromium Sodium polysulphide Trialkylaluminiums Hexacarbonylmolybdenum Sodium sulphide Trialkylbismuths Hexacarbonyltungsten Tin (II) sulphide Nonacarbonyldiiron Tin (IV) sulphide Compounds Octacarbonyldicobalt Titanium (IV) sulphide Bis-dimethylstibinyl oxide Pentacarbonyliron Uranium (IV) sulphide Bis(dimethylthallium) acetylide Tetracarbonylnickel Butyllithium (e) Pyrophoric alkyl non-metals Diethylberyllium (c)Pyrophoric metals(finely divied state) Bis-(dibutylborino) acetylene Bis-dimethylarsinyl oxide Diethylcadmium Caesium Rubidium Bis-dimethylarsinyl sulphide Diethylmagnesium Calcium Sodium Bis-trimethylsilyl oxide Diethylzinc Cerium Tantalum Dibutyl-3-methyl-3-buten-1-Yniborane Diisopropylberyllium Chromium Thorium Diethoxydimethylsilane Dimethylberyllium Cobalt Titanium Diethylmethylphosphine Dimethylbismuth chloride Hafnium Uranium Ethyldimthylphosphine Dimethylcadmium Iridium Zirconium Tetraethyldiarsine Dimethylmagnesium Iron Tetramethyldiarsine Dimethylmercury Lead Alloys Tetramethylsilane Dimethyl-phenylethynylthallium Lithium Aluminium-Mercury Tribenzylarsine Dimethyl-1-propynylthallium Manganese Bismuth-Plutonium mixo-Tributylborane Dimethylzinc Nickel Copper-Zirconium Tributylphosphine Ethoxydiethylaluminium Palladium Nickel-Titanium Triethylarsine Methylbismuth oxide Platinum Triethylborane Methylcopper Plutonium Triethylphosphine Methyllithium Potassium Triisopropylphosphine Methylpotassium Trimethylarsine Methylsilver (d) Pyrophoric metal sulphides Trimethylborane Methylsodium (Ammonium sulphide) Trimethylphosphine Poly (methylenemagnesium) Barium sulphide Propylcopper Calcium sulphide (f) Pyrophoric alkyl non-metal halides Tetramethyldistibine Chriomium (II) sulphide Butyldichloroborane Tetramethyllead Copper (II) sulphide Dichlorodiethylsilane Triethylantimony Diantimony trisulphide Dichlorodimethylsilane Triethyl bismuth Dibismuth trisulphide Dichloro(ethyl)silane Triethylgallium Dicaesium selenide Dichloro(methyl)silane Trimethylantimony Dicerium trisulphide Iododimethylarsine Trimethylgallium Digold trisulphide Trichloro(ethyl)silane Trimethylthallium Europium (II) sulphide Trichloro(methyl)silane Trivinylbismuth Germanium (II) sulphide Trichloro(vinyl)silane Vinyllithium Iron disulphide Iron (II) sulphide (g) Pyrophoric alkyl non-metal hydrides (b) Pyrophoric carbonyl metals Manganese (II) sulphide Diethylarsine Carbonyllithium Mercury (II) sulphide Diethylphosphine Carbonylpotassium Molybdenum (IV) sulphide Dimethylarsine Carboylsodium Potassium sulphide 1,1-Dimethyldiborane Dodecacarbonyldivanadium Rhenium (VII) sulphide 1,2-Dimethyldiborane Dimethylphosphine Ethylphosphine Methylphosphine Methylsilane D. ODOR THRESHOLD AND WARNING PROPERTIES (TOXICOLOGY BACKGROUND INFORMATION) Warning properties include odor, irritation, and color--chemical properties that warn you the chemical is in the area. Chemicals with good warning properties don't sneak up on you; you can smell, see or feel them, so you know to look for the source or leave the area. Chemicals with poor warning properties don't warn you of their presence, so are potentially more dangerous. People often link "strong smell" with "dangerous," and ignore the fact that some dangerous chemicals lack odor (carbon monoxide). Chemicals with good warning properties can be smelled, felt or seen at safe exposure levels; this table compares a selection of "odor thresholds" with safe 8 hour exposure levels, TLVs. TLV's are developed by the American Committee of Governmental Industrial Hygienists (ACGIH), a standard setting organization. COMPARISON OF TLV AND ODOR THRESHOLDS FOR A SELECTION OF CHEMICALS ________________________________________________________ CHEMICAL TLV ODOR THRESHOLD NAME ppm ppm acrolein 0.10 0.61 acrylic acid 10.00 110.00 arsine 0.05 0.10 diborane 0.10 2.50 ethylene dichloride 10.00 88.00 formic acid 5.00 49.00 methyl acrylonitrile 1.00 7.00 methyl formate 100.00 600.00 methyl isocyanate 0.02 2.10 phosgene 0.10 0.90 Note: these are not 100 percent odor recognition values; such values would be much higher, for instance for methyl formate 100 percent recognition = 2,000 ppm. __________________________________________________________ A table of odor thresholds published in "The Safe Handling of Chemicals In Industry" by P. A. Carson and C. J. Mumford, Volume 1, 1988, is shown on the next two pages. ODOR THRESHOLDS ODOR THRESHOLDS (CON'T) E. IRRITATING OR CORROSIVE GASES AND VAPORS LUNG IRRITATION AND DAMAGE: intense exposure (prolonged exposure to irritants or brief exposure to corrosives) causes lung tissue to swell and seep fluid, a condition called chemical pneumonitis; lungs may be damaged enough to cause death. Methyl isocyanate caused chemical pneumonitis in the Bhopol India tragedy. Chemical pneumonitis survivors may have permanent lung damage with symptoms similar to emphysema and a form of asthma in which airways constrict when exposed to quite low levels of irritating chemicals. EYE IRRITATION AND DAMAGE: irritating and corrosive gases may cause intense pain and temporary eye damage which can take several weeks to heal. During exposure the eyes are usually tightly shut--which opens the victim up to the hazards of temporary blindness. Direct eye contact with irritants and corrosive liquids or powders can cause (at best) short term irritation and swelling to (worst case) permanent blindness. Quick and correct actions can reduce symptoms and prevent blindness. Prevention is the best approach to prevent eye damage; wear goggles and face shields when handling corrosive materials. However, if contact does occur, wash chemical out of eyes immediately and continue rinsing with a gentle stream of water for 15 minutes. SKIN IRRITATION AND DAMAGE: Corrosive chemicals cause severe burns which will form scars unless treated properly. Wash contaminated skin with soap and water (or special solvent in several notable cases--bromine, phenol, hydrogen fluoride) immediately. Irritating chemicals cause a wide range of skin effects including burns, blisters, redness, itching, dryness, cracks (i.e., between fingers), roughness and a variety of skin problems termed dermatitis (skin inflammation). In general irritant effects are not severe, but are at least, annoying and at worst, temporarily or permanently debilitating (i.e., when an irritant effect turns into an allergy). F. EXAMPLES OF IRRITATING AND CORROSIVE CHEMICALS: Gases such as ammonia, chlorine, bromine, ozone, cyanogen chloride, phosgene, arsenic trichloride, nitrogen oxides, sulfur oxides, hydrogen chloride, acrolein, formaldehyde, fluorine, Liquids and solids such as strong acids, bases, chlorinated solvents (dichloroacetone, methylene chloride), organic bases, organic solvents, detergents, metal salts (chromates, nickel sulfate). See list below. Acids and anhydrides Acetic acid, acetic anhydride, acid mixtures, battery fluids, chlorosulphonic acid, chromic acid, chloroacetic acid, dichloroacetic acid, fluoroboric acid, fluorsilicic acid, hydrobromic, hydrochloric, hydrofluoric and hydriodic acids, methacrylic acid, nitric acid, nitrohydrochloric acid, perchloric acid, phenolsulphonic acid, phosphorus pentoxide, propionic acid, selenic acid, spent acids, sulphamic acid, sulphuric acid and oleum (fuming sulphuic acid), sulphurous acid, thioglycolic acid, trichloroacetic acid. Alkalis Ammonium hydroxide, potassium hydroxide (caustic potash), quaternary ammonium hydroxides, sodium hydroxide (caustic soda). Halogens and halogen salts Aluminum bromide and chloride, ammonium bifluoride and other bifluorides, antimony trichloride, pentachloride and pentafluoride, beryllium chloride, boron trichloride, bromine, chlorine, calcium fluoride, chromic fluoride, chromous fluoride, iron chlorides (ferric chloride, ferrous chloride), fluorine, iodine, lithium chloride, phosphorus oxybromide and oxychloride (phosphoryl bromide and chloride), phosphorus trichloride and pentachloride, phosphorus sulphochloride (thisphosphoryl chloride), potassium fluroide and bifluoride, potassium hypochlorite, pyrosulphuryl chloride, sodium chlorite, sodium fluoride, sodium hypochlorite, stannic chloride, sulphur chloride, sulphuryl chloride, thionyl chloride, titanium tetrachloride, vanadium dichloride, zinc chloride. Interhalogen compounds Bromine trifluoride and pentafluoride, chlorine trifluoride, iodine monochloride. Organic halides, organic acid halides, esters and salts Acetyl bromide, allyl chloride and allyl iodide, acrylonitrile monomer, allyl chloroformate, allyl iodide, ammonium thiocyanate, anisoyl chloride, benzyl chloride, benzhydryl bromide (diphenyl methyl bromide), benzoyl chloride, benzyl bromide, butyl acid phosphate, benzyl chloroformate (benzyl chlorocarbonate), chloroacetyl chloride, ethyl chloroformate (ethyl chlorocarbonate), dibromoethane (ethylene bromide). 1,2- dichloroethane (ethylene chloride), ethylene oxide, fumaryl chloride, ethyl chloroformate (methyl chlorocarbonate), propionyl chloride, iso-propylchloroformate, diisooctyl acid phosphate, p-chlororbenzyl chloride, chloropropionyl chloride, sodium tluorosilicate. Chlorosilanes Allyl trichlorosilane, amyl trichlorosilane, butyl trichlorophenltrichlorosilane, cyclohexyl trichlorosilane, dichlorophenyl trichlorosilane, diethyl trichlorosilane, diphenyl dichlorosilane, dodecyl trichlorosilane, hexadecyl trichlorosilane, hexyl trichlorosilane, methyl trichlorosilane, nonyl trichlorosilane, octadecyl trichlorosilane, octyl trichlorosilane, phenyl trichlorosilane, trimethyl trichlorosilane, vinyl trichlorosilane. Miscellaneous corrosive substances The following corrosive substances are widely used but do not fall into any of the above classes: ammonium sulphide, benzene sulphonyl chloride, benzyl dimethylamine, beryllium nitrate, catechol, chlorinated benzenes and toluenes, chlorobenzaldehyde, chlorocresols, cresols, cyclohexylamine, dibenzylamine, dichlorophenol, diethyl sulphate, diketene, dimethyl sulphate, hexamethylenediamine, hydrazine, hydrogen peroxide, organic peroxides, phenols, soda lime, sodium aluminate, sodium amide, sodium bisulphate, sodium bisulphite, sodium chromate and dichromate, sodium pyrosulphate, sodium hydride, triethyltertramine, tritolyl borate, silver nitrate. Proprietary mixtures, i.e., cleaning, disinfecting, bleaching, degreasing solids or solutions based on these chemicals are corrosive to a degree dependent upon dilution. G. SENSITIZERS (ALLERGENS) Some chemicals cause allergies; an allergy (or sensitivity) is an abnormal response to low exposure levels of chemicals which don't elicit a similar response in the majority of people. The allergic response can be quite serious. Once an allergy develops it usually does not go away. If the symptoms are serious, the person must not be allowed to work where the chemical is used or generated. Allergic responses vary from life threatening (anaphylactic "bee sting" type reactions which can cause death by asphyxiation within minutes of exposure); to moderate (dermatitis, severe headache, head or chest cold or flu symptoms); to slight (rash, dry skin, itching nose or eyes). Chemicals which cause skin sensitivities (by class and several examples of each): coal tar and its derivatives (cresol, pyridine, acridine); dyes (including auramine, amido-azo-benzene, aniline black); dye intermediates (acridine and compounds; aniline and compounds); benzidine and compounds (naphthalene and compounds); explosives (fulminate of mercury, picric acid, sodium nitrate); insecticides (many); natural resins (i.e., dammar, japanese lacquer, pine rosin, copal); natural oils (cashew, coconut, cutting, linseed, mustard, tung); photographic developers (hydroquinone, bichromates, pyrogallol); plasticizers (stearic acid, butyl cellosolve stearate, etc.); rubber accelerators and antioxidants (p-toluidine, guanidine); synthetic resins (acrylic, alkyd, epoxy, chlorophenyls); enzymes (proteolytic enzymes, B. subtilis) H. ASPHYXIANT GASES AND VAPORS Animals require a constant supply of oxygen to survive, and asphyxiants reduce or eliminate this supply. Low levels of exposure to asphyxiants (or chronic exposure to less powerful ones) generally cause headaches, fatigue and confusion. High levels (or low levels of very toxic ones) will cause comas and, if the victim is not rescued, death. Asphyxiants can act quickly. One breath of pure nitrogen causes immediate collapse and unconsciousness--leaving no time to recognize and respond to the danger. TYPES OF ASPHYXIANTS: CHEMICAL AND SIMPLE Chemical asphyxiants cause asphyxiation by reacting inside the body; generally small amounts can cause illness or death. For example, hydrogen sulfide interferes with nerve cell function, putting certain nerves to sleep, including olfactory (smell) nerves and the ones necessary for breathing. Moderate exposure levels eliminate our ability to smell--so right at the beginning of exposure we smell the characteristic rotten egg odor--and then it appears to go away. The odor is not gone; the ability to perceive it is gone. At higher concentrations or after prolonged breathing this chemical causes loss of consciousness and loss of the breathing mechanism. Several minutes in this state result in death. ppm H2S SYMPTOMS 0.2 detectible odor 20-150 eye irritation 150 loss of smell (olfactory paralysis) 250 severe lung irritation 500 severe systemic effects *1000 collapse, respiration may stop soon 5000 fatal *1000 ppm = 0.1% contaminants in air. ASPHYXIANT GASES AND VAPORS (CON'T) Certain amines, nitrites and carbon monoxide produce asphyxia by reacting with blood hemoglobin, reducing its capacity to carry oxygen. This table shows the correlation of symptoms with the percent of hemoglobin carrying carbon monoxide (which is normally less than 1% in nonsmokers, and less than 5% in smokers). % HbCO in blood SYMPTOMS 00-10% no symptoms (PEL=10 ppm) 10-20% yawning, flushed skin, headache 20-30% headache, dizziness 30-40% severe headache, weakness, dizziness, nausea,possibly collapse. 40-50% Ditto, increased respiration, probable collapse. 60-70% fainting, coma. 70-80% respiratory failure and death. 90% prompt cardiac arrest Simple asphyxiants are not toxic, but can cause serious problems in confined spaces. Simple asphyxiants reduce oxygen levels from the usual 21% to lower levels by simple displacement. For example methane may seep into an underground electrical vault and displace most of the air dropping the oxygen concentration to 5%, not enough to survive in. Physiological effects become more severe as the oxygen level decreases, as shown below: % OXYGEN in air SYMPTOMS 16-21% No noticeable effect. 19.50% OSHA standard 12-16% Possible headache; reduced coordination and ability to think clearly. 10-12% Loss of ability to think clearly. 6-10% Loss of consciousness, death. ASPHYXIANT GASES AND VAPORS (CON'T) Asphyxiating conditions can be set up in confined spaces when vessels or pipes are flushed with nitrogen; when CO2 fire extinguishers are used in confined areas; due to generation or leakage of gas from cryogenic or welding processes; due to the formation of rust in closed (or very large) pipes or vessels; and in tanks, in the presence of high levels of microorganisms which use oxygen in metabolic reactions. CHEMICAL ASPHYXIANTS INCLUDE: carbon monoxide, hydrogen cyanide, hydrogen sulfide, cyanogen, arsine, nitrites, amines, dimethyl amine, toluidine, nitrobenzene. SIMPLE ASPHYXIANTS INCLUDE: argon, methane, helium, nitrogen, carbon dioxide. CORROSIVE CHEMICAL ASPHYXIATION: breathing certain chemicals can cause severe lung burns resulting in lung damage, swelling and loss of function--thereby affecting the amount of oxygen available to the body (thus meeting the definition of asphyxiation). However this type of "asphyxia" is generally viewed as a corrosive effect rather than true asphyxia. I. CENTRAL NERVOUS SYSTEM (CNS) DEPRESSANTS ANESTHETIC AND NARCOTIC GASES, VAPORS AND LIQUIDS (MOSTLY SOLVENTS) Anesthetic or narcotic materials depress the central nervous system (CNS, the brain and spinal cord) causing sleepiness, dizziness, drunk behavior, headache and often nausea and vomiting. Many organic solvents, alcohols, ethers, ketones, esters, etc. are CNS depressants. CNS effects generally occur within a few minutes of overexposure and may last quite awhile, until the chemical has been detoxified by the liver. Chlorinated hydrocarbon solvents (methylene chloride, methyl chloroform, carbon tetrachloride, etc.) have a peculiar and dangerous effect at high exposure levels (inhalation or direct skin contact): they cause changes in heart function (similar to a heart attack) which can cause death in minutes. The exposure situation is usually use of these materials in a confined area, where extremely high exposure levels can rapidly develop. Deaths in "glue sniffing" may also be due to this type of heart effect. One of the most dangerous symptoms of overexposure to CNS depressants is inebriation (drunk behavior) because victims are more likely to make mistakes, to fall or trip, and are less likely to follow or hear instructions or see imminent danger. They are dangerous to themselves and others. Watch for signs of inebriation due to overexposure to chemicals, both in your co-workers and yourself. Many chemicals (especially solvents) can enter the body through the skin, and entry by this route is often more toxic than by oral or inhalation routes. (Propylamine is ten times as toxic via skin than via mouth). Some areas of skin are more easily penetrated by chemicals than others: the scrotum is very easily penetrated (which makes contaminated slacks particularly hazardous); the scalp and forehead are quite easily penetrated, and the palm of the hand is the least easily penetrated. OSHA and ACGIH workplace standards regulate permissible air levels of chemicals; if chemicals can also get into the body via skin, then these organizations give them an "S" or "skin" notation, which means that skin contact must be controlled as well. Chemicals denoted "skin" by ACGIH and OSHA are listed in the following table. J. MATERIALS THAT PENETRATE THE SKIN IN TOXIC QUANTITIES Compound Compound Compound Acrylamide Glycerol trinitrate Trichloroethylene Acrylonitrile Heptachlor Xylene Aldrin Hexachloroethane Xylidine Allyl alcohol Hexahydro-1,3,5-trinitro Allyl 2,3-epoxypropyl ether Hexahydro-1,3,5-triazine Aniline Hexan-2-one Anisidines, o- and p-isomers Hydrazine Azinphos-methyl Hydrogen cyanide Aziridine 2-Hydroxypropylacrylate Butan-1-ol 2,2-Iminodi(ethylamine) 2-Butoxyethanol Iodomethane Butylamine Malathion BHC Mercury alkyls Bromoform Methanol Bromomethane Methomyl Captafol 2-Methoxyethanol Carbon disulphide 2-Methoxyethyl acetate Carbon tetrachloride Methyl acrylate Chlordane 2-Methylcyclohexanone Chlorinated biphenyls 2-Methyl-4,6-dinitrophenol 2-Chlorobuta-1,3-diene 4-Methylpentan-2-ol 1-Chloro-2,3-epoxy propane 4-Methylpentan-2-one 2-Chloroethanol N-Methyl-N,2,4,6-tetranitroaniline 1-Chloro-4-nitrobenzene Mevinphos Chlorpyrifos Morpholine Cresols, all isomers Nicotine Cumene 4-Nitroaniline Cyanides Nitrobenzene Diazinon Nitrotoluene 2,2-Dichloro-4,4-methylene dianiline Octachloronaphthalene 1,3-Dichloropropene Parathion Dichlorvos Parathion-methyl Dieldrin Pentachlorophenol 2-Diethylaminoethanol Phenol Di-isopropylamine p-Phenylenediamine N,N-Dimethylacetamide Phenylhydrazine N,N-Dimethylaniline Phorate Dimethyl formamide Picric acid Dimethyl sulphate Propan-2-ol 2,4-Dinitrotoluene Propylene dinitrate 1,4-Dioxane Prop-2-yn-1-ol Dioxathion Sodium fluoroacetate Endosulfan Sulfotep Endrin Tetraethylpyrophosphate 2-Ethoxyethanol Tetramethyl succinonitrile 2-Ethoxyethyl acetate hallium, soluble compounds Ethyl acrylate Tin compounds, organic Ethylene dinitrate Toluene 4-Ethylmorpholine Tricarbonyl (eta-cyclopentadienyl) manganese 2-Furaldehyde Tricarbonyl (methylcyclopentadienyl) manganese Furfuryl alcohol 1,1,2-Trichloroethane K. POISONS Certain chemicals are acutely toxic at very low levels and can cause serious, life-threatening damage in amounts readily ingested, inhaled or absorbed through the skin. Examples of poisons by class, with examples, are: alkaloids and derivatives amino alcohols esterified with benzoic acid, phenylacetic acid, phenylpropionic acid, cinnamic acid or the derivatives of these acids or their salts. antimonial poisons arsenical poisons barbituric acids, salts or derivatives. barium salts bromomethane chloroform chloropicrin dinitrocresols (DNOC) and compounds with a base or metal dinitronaphthols dinitrophenols dinitrothymols ethylmorphine, salts, esters, ethers hydrocyanic acid, cyanide salts other than ferro- or ferricyanide hydroxyurea lead compounds mercury compounds monofluoroacetic acid and salts m-, o-, p-nitrophenol organo-tin compounds paraldehyde paraquat salts phosphorous compounds (mostly pesticides), i.e., azinphos-ethyl, dichlorovos, demeton, disulfoton, ethion, phorate, TEPP thallium salts tetamine and salts zinc phosphide L. SYSTEMIC TOXINS Systemic toxins damage tissues at sites other than the point of contact. They enter the body through the skin, mouth or lungs, spread via blood, and damage one or more internal organs such as the liver, kidneys, blood forming tissue, reproductive system, brain or nerves. Systemic damage is usually caused by long term exposure (years) to relatively low levels of chemicals, an exposure pattern often found in industry. Short term exposure to high levels of chemicals (acute exposure) is less likely to cause systemic toxic effects. We learn about systemic toxicity from human experience (e.g., occupational overexposure) and animal research. Some chemicals have many target organs, some just one. The target organ depends on the material and route and pattern of exposure. It is best to treat systemic toxins as possibly harmful to all organs, since the complete toxicity profile is usually not known. Examples: CHEMICALS THAT AFFECT SEVERAL ORGANS: halogenated hydrocarbons (many); benzene, phenols (brain and bone marrow/blood forming tissue); ionizing radiation (skin, gut, bone marrow, reproductive organs); carbon disulfide (nervous system, heart); methanol, n- hexane, methyl n-butyl ketone (nerves, brain); organophosphorus compounds, tetra-alkyl lead (brain); lead (bone marrow, brain, conceptus); manganese (lungs); cadmium (lungs, testes); beryllium (lungs); mercury (kidneys, brain); arsenic (many organs including blood); phosphorous (bones); selenium (liver); fluorides (many organs); dichloromethane (kidney, liver, brain); 2- ethoxyethanol (kidney, liver, brain, reproductive system). CHEMICALS THAT PRIMARILY AFFECT THE BLOOD: acetonitrile, aniline, antimony, arsenic, benzene, carbon disulfide, carbon tetrachloride, cobalt, DDT, ethyl silicate, EGMME, ethylene oxide, fluorides, lead, manganese, mercury, methylchloride, nitrobenzene (nitrophenol), phenylhydrazine, radium, selenium, tetrachloromethane, thallium, thorium, toluene, toluene diamine, toluidine, trichloroethylene, trinitrotoluene, uranium, vanadium, xylene. CHEMICALS THAT PRIMARILY AFFECT THE LIVER: acrylonitrile, aflatoxin, allylalcohol, antimony, arsenic, beryllium, bromobenzene, cadmium, carbon disulfide, carbon tetrachloride, cerium, chlorinated diphenyls, chlorinated naphthalenes, chloroform, cobalt, cycloheximide, cycloparaffin, DDT, dioxane, dimethyl formate, dimethyl nitrosamine, dinitrophenol, diphenyl, ethanol, ethylene chlorohydrin, ethylene dichloride, hydrazine, methyl bromide, methyl chloride, methyl formate, methylene chloride, nitrobenzol, phenol, phenylhydrazine, phosphorous, pyrolizidine alkaloids, tannic acid, tetrachloroethane, thioacetamide, trichloroethylene, triflurochloroethylene, trinitrotoluene, uranium, urethane. M. CARCINOGENS (CANCER CAUSING MATERIALS) A number of chemicals are known or suspected as causing or helping to cause cancer. A few chemicals are known human carcinogens (such as asbestos and cigarette smoke). Most are known or suspected animal carcinogens. Chemicals known to cause cancer in animals are considered potential human carcinogens. Current evidence (i.e., for cigarette smoke and asbestos) indicates a 10 to 20 year delay between onset of exposure and onset of cancer; and, for most known human carcinogens, there was a high level, long term exposure pattern. Can long or short term exposures to low levels of asbestos or side stream smoke (or other carcinogens) cause cancer? No one knows. However for regulatory purposes human carcinogens are considered carcinogenic whatever the exposure amount or pattern--thus exposure must by law be kept to a minimum. Mutagens are chemicals which damage DNA, and DNA damage is believed to play an important role in initiating cancer. Thus mutagens are viewed as "potential suspected animal carcinogens" even in the light of evidence to the contrary. Examples of known human carcinogens: 4-aminodiphenyl (skin), arsenic and certain compounds, asbestos, benzene, benzidine and related compounds (skin), beta- (or 2-) naphthylamine, bis- chloromethyl ether, chlornaphazine, chromium VI compounds, coal-tar pitch volatiles, diethylstilbestrol, melphalan, mustard gas, nickel sulfide roasting (fume and dust), 4-nitrodiphenyl (skin), soots/tars/non refined mineral oils, vinyl chloride. CANCER CAUSING CHEMICALS Probable human carcinogens (good animal and equivocal human data) A: acrylamide (skin), acrylonitrile (skin), aflatoxin, amitrole, auramine B: benzo(a)pyrene, beryllium and certain compounds, 1,3 butadiene C: cadmium and certain Cd compounds, carbon tetrachloride (skin), chlorambucil, chloramphenicol, chlordane/heptachlor, chlormethyl methyl ether, chloroprene, chromates of lead and zinc, chrysene, cyclophosphamide D: 3,3-dichlorobenzidine (skin), 1,1-dimethyl hydrazine (skin), dichloroidphenyltrichloroethane, dieldrin, dimethylcarbomyl chloride, dimethyl sulfate E: epichlorhydrin, ethylene dibromide (skin), ethylene oxide F: formaldehyde H: hematite, hexachlorobutadiene, hexachlorocyclohexane (lindane), hexamethyl phosphoramide (skin), hydrazine (skin) I: iron dextran, isoniazide, isopropyl oils L: lead and lead compounds M: 4,4'-methylene bis(2-chloroaniline) (skin), methylene chloride, methylene dianiline, methyl hydrazine (skin), methyl iodide (skin) N: nickel and certain Ni compounds, 2-nitropropane, n-nitrosodimethylamine (skin) O: oxymetholone P: phenacetin, phenobarbital, N-phenyl-2-naphthylamine, phenytoin (diphenylhydantoin), phenylhydrazine (skin), propane sultone, beta-propiolactone, propylene imine (skin), polychlorinated biphenyls R: reserpine S: styrene T: thiotepa, o-tolidine (skin), o-toluidine (skin), p-toluidine (skin), trichloroethylene, tris(aziridinyl)-p-benzoquinone V: vinyl bromide, vinyl cyclohexene dioxide (skin) N. REPRODUCTIVE TOXINS Chemicals which are linked to reproductive damage of various types include: abnormal sperm and/or low sperm count infertility reduced libido and/or impotence altered menstrual cycles or no ovulation spontaneous abortions damaged eggs DNA changes in egg or sperm (mutations) Reproductive effects are, by definition, damaging to parents and not the conceptus (fetus or embryo); fetal and embryonic damage is called TERATOGENESIS. Examples of teratogens: acrylonitrile monomethylformamide alcohol (i.e., beer, wine) ethylene dichloride arsenic ethylene oxide some antibiotics lead anticoagulants (i.e., coumarin, wafarin) inorganic mercury benzo(a)pyrene nitrogen dioxide chlorofluoromethane PBBs chloroform selenium chloroprene tellurium methyl ethyl ketone tetrachloroethylene methylene chloride thallium nitrogen dioxide trichloroethylene PBBs vinyl chloride selenium vinylidine chloride tellurium xylene cigarette smoking Examples of reproductive toxins (effects not specified): Anesthetic gases, aniline, arsenic, carbon monoxide, benzene, beryllium, boron, cadmium, chlordecone (kepone), dibromochloropropane (DBCP), epichlorhydrin, formaldehyde, manganese, PCBs, styrene, toluene, toluene diisocyanate (TDI). O. CHEMICALS THAT DAMAGE THE LUNGS The damaging effects of inhaled corrosive materials have already been presented, and are not included in this section. There are other chemicals, less obviously corrosive, but still irritating and damaging to delicate lung tissues. In general lung damage is caused by the long term moderate exposure level pattern found in the workplace, though short term high exposure levels have caused severe, permanent damage. Again, in the usual case, the damage occurs over an extended period of time and is not discovered until the victim is debilitated by the damage. Examples of lung damaging chemicals are listed below; add to this list materials which are obviously corrosive, such as strong acids and bases. asbestos aluminum dust and fume ammonia arsenic beryllium boron cadmium oxide fume and dust cotton dust bract carbides of tungsten, titanium and tantalum chlorine chromium IV coal dust coke oven emissions hydrogen fluoride iron oxide dust and fume kaolin manganese nickel dust and fume osmium tetroxide oxides of nitrogen ozone phosgene perchlorethylene silica sulfur dioxide talc tin toluene 2,4-diisocyanide (TDI) vanadium xylene

Manual Section 1 Section 2 Section 3 Section 4 Section 5 Section 6 Section 7 Section 8 Section 9 Section 10 Section 11