Document XOojQRXXDbNvDOoXMqdN6GZ9J

Threshold Limit Values For 1967 RECOMMENDED AND INTENDED VALUES Adopted at the 29th Annual Meeting of the American Conference of Governmental Industrial Hygienists, Chicago, Illinois, May 1-2, 1967. EC- 2038 f f THRESHOLD LIMIT VALUES FOR 1967 fr rr (c Copyright 1967, by American Conference of Governmental Industrial Hygienists. The American Conference of Governmental Industrial Hygienists will welcome requests for permission to republish or reprint these Thresh old Limit Values. Requests for such permission should be directed to the Secretary-Treasurer, 1014 Broadway, Cincinnati, Ohio 45202- Price: 1 -- 49 Copies............................. 50c 50 - 999 Copies........................ 40c 1000 or more Copies............. 30c The 2nd edition of the Documentation of Threshold Limit Values, rewritten and greatly enlarged to include the approximately 400 sub stances in the list, is available and may be pur chased from the Secretary-Treasurer. The Docu mentation should be consulted when using the Threshold Limit Values herein (Price -- $4.50 -- see order blank in back of this booklet). c <" ! (c Reprinted by permission of The American Conference of Governmental Industrial Hygienists The Threshold Limit Values refer to air-bome concentrations of substances and represent con ditions under which it is believed that nearly all workers may be repeatedly exposed, day after day, without adverse effect. Because of wide variation in individual susceptibility, exposure of an occasional individual at or even below the threshold limit may not prevent discomfort, ag gravation of a pre-existing condition, or occupa tional illness. Clinical tests are becoming available that per mit detection of those individuals who will hyperreact upon exposure to certain industrial sub stances. Being predictive in character, they may be applied as screening tests in the preplacement job examination. Requests for further details of these tests should be directed to the Chairman of the Committee. Threshold limits should be used as guides in the control of health hazards and should not be regarded as fine lines between safe and dan gerous concentrations. Exceptions are the sub stances given in Appendix A and certain of the substances given a "C" listing. The values not given a "C" listing refer to time-weighted aver age concentrations for a conventional 7 or 8 hour workday. Time-weighted average concentrations permit excursions above the limit, provided they are compensated by equivalent excursions below the limit during the work day. The degree of permis sible excursion is pegged to the threshold limit value of the particular substance as given in table in Appendix C under "Test TLV Factor." Hence, it is not considered appropriate to inter pret air concentration values as exceeding timeweighted average limits, if such values lie within the permissible excursions. (See section on Legislative Code.) The amount by which these concentrations may be exceeded for short periods without injury to health depends upon a number of factors such as the nature of the contaminant, whether very high concentrations even for short periods produce acute poisoning, whether the effects are cumula tive, the frequency with which high concentra tions occur, and the duration of such periods. 1 EC- 2039 All must be taken into consideration in arriving at a decision as to whether a hazardous situa tion exists. Enlightened industrial hygiene prac tice inclines toward controlling exposures below the limit rather than maintenance at the limit. c r Threshold limits are based on the best avail able information from industrial experience, from experimental human and animal studies, and when possible, from a combination of the three. The basis on which the values are established may differ from substance to substance; protec tion against impairment of health may be the guiding factor for some, whereas reasonable free dom from irritation, narcosis, nuisance or other forms of stress may dominate the basis for others. The Committee holds to the opinion that limits based on physical irritation should be considered no less binding than those based on physical impairment; growing bodies of evidence indicate that physical irritation may promote and accelerate physical impairment. These limits are intended for use in the field of industrial hygiene and should be interpreted and applied only by persons trained in this field. They are not intended for Use, or for modifica tion for use, (1) as a relative index of toxicity, by making a ratio of two limits, (2) in the evalu ation or control of community air pollution or air pollution nuisances, (3) in estimating the toxic potential of continuous uninterrupted exposures, (4) as proof or disproof of an existing disease or physical condition, or (5) for adoption by coun tries whose working conditions differ from those in the United States of America and where sub stances and processes differ. Documentation of Threshold Limit Values. A separate companion piece to the TLVs is is sued by ACGIH under this title. This publication gives the pertinent scientific information and da ta with reference to literature sources that were used to base each limit. Each documentation al so contains a statement defining the type of response against which the limit is safeguarding the worker. For a better understanding of the TLVs it is essential that the Documentation be consulted when the TLVs are being used. Ceiling vs Time-Weighted Average Limits. Although the time-weighted average concentra r rv (f tC c c* c* 2 tion provides the most satisfactory, practical way of monitoring air-bome agents for compli ance with the limits, there are certain substan ces for which it is inappropriate. In the latter group are substances which are predominantly fast acting and whose threshold limit is more appropriately based on this particular response. Substances with this type of response are best controlled by a ceiling "C" limit that should not be exceeded. It is implicit in these defini tions that the manner of sampling to determine compliance with the limits for each group must differ, a single brief sample, that is applicable to a "C" limit, is not appropriate to the timeweighted limit: here, a sufficient number of sam ples are needed to permit a time-weighted average concentration throughout a complete cycle of operations or throughout the work shift. Whereas the celling limit places a definite boundary which concentrations should not be permitted to exceed, the time-weighted average limit requires an explicit limit to the excursions that are permissible above the listed values. The magnitude of these excursions may be peg ged to the magnitude of the threshold limit by an appropriate , factor shown in Appendix C. It should be noted that the same factors are used by the Committee in making a judgment whether to include or exclude a substance for a "C" listing. "Skin11 Notation. Listed substances followed by the designation "Skin" refer to the potential contribution to the over-all exposure by the cu taneous route including mucous membranes and eye, either by air-bome, or more particularly, by direct contact with the substance. Vehicles can alter skin absorption. This attention-calling de signation is intended to suggest appropriate measures for the prevention of cutaneous absorp tion so that the threshold limit is not invalidat ed. These values are reviewed annually by the Committee on Threshold Limits for revision or additions, as further information becomes avail able. Mixtures. Special consideration should be given also to the application of these values in assessing the health hazards which may be as- 3 EC- 2040 sociated with exposure to mixtures of two or more substances. A brief discussion of basic rconsiderations involved in developing threshold limit values for mixtures, and methods for their development, amplified by specific examples are given in Appendix B, r ``Inert1* or Nuisance Particulates. A number of dusts or particulates that occur in the working environment ordinarily produce no specific ef fects upon prolonged inhalation. Some insoluble substances are classed as inert (e.g. iron and steel dusts, cement, silicon carbide, titanium dioxide, cellulose); others may be solu c ble (starch, soluble oils, calcium carbonate) but are of such a low order of activity that in con r centrations ordinarily encountered do not cause *{ (physiologic impairment; still others may be rap- idly eliminated or destroyed by the body (veg <( etable oils, glycerine, sucrose). In the case of Cthe insoluble substances, there may be some ac < cumulation in the respiratory passages. In the case of the soluble substances, this accumula tion will ordinarily be temporary but may inter fere to some extent with respiratory processes. Hence, it is desirable to control the concentra tions of such particulates in the air breathed by any individual, in keeping with good industrial hygiene practice. 3 A threshold limit of ISmg/m , or SO mppcf, whichever is less, is recommended for substan ces in these categories and for which no specif ic threshold limits have been assigned. This limit, for a normal work day, does not apply to brief exposures at higher concentrations. Neither ( does it apply to those substances which may cause physiologic impairment at lower concen trations but for which a threshold limit has not c yet been adopted. Some ``inert'' particulates are given in Appendix D. Simple Asphyxiants-"Inert*' Gases or Vapors. c K A number of gases and vapors, when present in high concentrations in air, act primarily as sim ple asphyxiants without other significant phys iologic effects. A TLV may not be recommend ed for each simple asphyxiant because the limit ing factor is the available oxygen. The minimal oxygen content should be 18 percent by volume under normal atmospheric pressure (equivalent to a partial pressure, pOJt of 135 mm Hg). Atmos pheres deficient in 0; do not provide adequate warning and most simple asphyxiants are odor less. Several simple asphyxiants are listed in Appendix E. Some asphyxiants present an ex plosion hazard. Account should be taken of this factor in limiting the concentration of the asphyx iant. Physical Factors. It is recognized that such physical factors as heat, ultraviolet and ioniz ing radiation, humidity, abnormal pressure and the like may place added stress on the body so that the effects from exposure at a threshold limit may be altered. Most of these stresses act adversely to increase the toxic response of a substance. Although most threshold limits have built-in safety factors to guard against adverse effects of moderate deviations from normal en vironments, the safety factors of most substan ces are not of such a magnitude as to take care of gross deviations. For example, continuous work at temperatures above 90*F or over-time, extending the work-week more than 50%, might be considered gross deviations. In such instan ces judgment must be exercised in the proper adjustments of the threshold limit values. ``Notice of Intent" At the beginning of each year, proposed actions of the Committee for the forthcoming year are issued in the form of a "Notice of Intent." This Notice provides not only an opportunity for comment, but solicits suggestions of substances to be added to the list. The suggestions should be accompanied by substantiating evidence. As Legislative Code. The Conference does not consider the Threshold Limit Values appro priate matter for adoption in legislative codes and regulations and recommends against such use. If, however, the list is so used,the intent of the concepts contained in the preface should be maintained and provisions should be made to keep the list current. Reprint Permission. This publication may be reprinted provided that written permission is ob tained from the Secretary-Treasurer of the Con ference and that it be published in its entirety. 4 5 EC- 2041 RECOMMENDED VALUES (In Alphabetical Order) c r $ub*toriee Butanethiol, see Butyl mercaptan ............ $ubtanc* ppm* MVM* 2-Butanone................................................... 2-Butoxy ethanol (Butyl Cel!osolve)-Skin .. Acetaldehyde.......................................... Acetic acid............................................. Acetic anhydnde................................... Acetone.................................................. Acetonitnie............................................. Acetylene dichloride, see 1,2 Dicloro- ethylene .............................................. Acetylene tetrabromide....................... Actolein................................................... Acrylamide- Skin.................................... Acrylonitrile-Skin.................................... Aldrin-Skin ............................................. Ally I alcohol-Skin.................................. Allyl chloride.......................................... Allyl glyeidyl ether (AGE)....................... Allyl propyl disulfide................................ 2-Aminoethanol, see Ethanol amine............ 2-Aminopyridine........................................... Ammonia .................................................... Ammonium sulfamate (Animate).................. n-Amyl acetate............................................. sec-Amyl acetate......................................... Aniline-Skin ................................................ Anisidine (o, p-isomers)-SkinAntimony & compounds(as Sb)_ ANTU (alpha naphthyl thiourea).. Atsenic & Compounds (as As)..... Arsine .......................................... Azinphos-methyl Skin................ Barium (soluble compounds)........ Benzene (benzol)-Skin................. Benzidine - Skin........................... p-Benzoquinone. see Quinone.... Benzoyl peroxide.......................... Benzyl chloride .......................... Beryllium.................... ......... ......... . Biphenyl, see Diphenyl .............. Boron oxide....... ....... ........ --....... Boron tnfluoride .................... Bromine ...................................... Btomoform-Skin............................ Butadiene (1,3-butadiene) ........ 200 10 S 1,000 40 360 25 20 2,400 70 + Butyl acetate (n-butyl acetate)................... + n-Butyl acetate ......................................... + see-&ityl acetate ....................................... + tett-Butyl acetate ................................... . Butyl alcohol ............................................... tett. Butyl alcohol ....................................... C Butylamine-Skin.......................................... 1 14 0.1 0.25 0.3 20 45 0.25 5 c10 45 2 12 (0.5 2 50 35 - 15 100 525 125 650 5 19 0.5 0.5 0.3 0.S 0.05 0.2 0.2 0.5 25 80 A1 C tett Butyl chromate (as Cr03)-Skin........... n-Butyl glycidyl ether (BGE)...................... Butyl mercaptan............................................ p-tert Butyltoluene .................................. r a <r + Cadmium (Metal dust and soluble salts)..... Cadmium oxide fume.................................... Calcium atsenate........................... .............. Calcium oxide................................. .............. c t Camphor............................................. --...... Carbary! (Sevin) (R)......................-.............. + Carbon black.................................................. Carbon dioxide............................................. Carbon disulfide-Skin ................................ + Carbon monoxide........................................ . Carbon tetrachloride-Skm........................... Chlordane-Skin.............................................. Chlorinated camphene, -Skin ..................... Chlorinated diphenyl oxide ....................... c Chlorine.......................................................... Chlorine dioxide ......................................... c Chlorine tri fluoride................................... c Chloroacetaldehyde.................................... Chlorobenzene (monochloiobenzene) .... + o-Chlorobenzylidene malononitrile (OCBM)...................................................... Chlorobtomomethane................................ ( 0.002 2-Chloto-l, 3 butadiene, see Chlotoptene . Chlorodiphenyl (424. chlorine)-Skin ......... Chlorodiphenyl (54% chlorine)-Skin ..... l'Chloro, 2, 3 epoxypropane, see c15 13 EpiChloihydnn..................... ...................... 2, Chloroethanol, see Ethylene 0.1 0. 7 Chlorohydrin................................................ 0.5 5 1,000 2.200 C Chloroethylene, see Vinyl chloride.......... ( c Chloroform (trichloromethane) .................. 1-Chloro-l-nitropropane ............................ Chloropicrin.............................................. * Part* of vapor or 90* por million part* of eontaminatod air by volvmo at 25 C and 76Q mm. Hg pressure. ** Approximate milligrams of partieulote per cubic meter of air. A Numbers, See Appendix A Chloroprene (2-chloio-l, 3-butadiene)-Skm Chromic acid and chromates (as Cr03) .... + Coal tar pitch volatiles (benzene soluble fraction) (anthracene, BaP, phenanthrene , acridine, chrysene, pyrene) t Cobalt........................................................ ppm* MMJ 200 590 50 240 150 710 150. 710. 200 950 200. 950. 100 300 100 300 5 15 -- 0.1 50 270 10 35 10 60 -- 0.2 -- 0.1 -1 --S -2 -5 -- 3.5 5,000 9,000 20 60 SO. 55. 10 6S -- 0.5 -* 0.5 0.5 1. 3. 0.1 0.3 0.1 0.4 13 75 350 0.05 0.4 200 1,,050 _1 - 0. 5 50 20 0.1 25 - 240 100 0.7 90 0.1 0.2. -_ 1967 Addition See Intended Values t See Intended Values 6 7 EC- 2042 ppm* My Mj!* _ 0. Substance e. 1.1 _1 15 5 22 2. 6. 50. 245. -5 300 1.050 50 200 50 200 300 1,015 75 200 _ 10 f _ _ c0.05 C u- 1 1 0.: 0. > t50 240 o.:! 0. C 0.1 0. Dimethyl 1, 2-dlbromo-2, 2-dichloroethyl phosphate, (Dibtom) (R>........................... Dimethylformamide-Skin.............................. 2,6 Dimethylheptanone, see Diisobutyl ketone .......................................................... 1,1 -Dimethylhydrazme-Skin......................... Dimethylsulfate - Skin ................................ Dimtrobenzene (all isomers)-$kin ............. Dinitto-o-cresoi-Skin........ ............................ Dinitrotoluene-Skin...................................... Dioxane (Oiethylene dioxide)-Skin ............ Diphenylmethane diisocyanate (See Methylene bisphenyl isocyanate (MDI)..... Diptopylene glycol methyl ether-Skin......... Di-sec, ectyl phthalate (Di-2-ethylhexylphthalate............................. ......................... Endrin-Skin.................................................... Epichlothydrin-Skin...................................... EPN-Skin ...................................................... 1.2-Epoxypropane, see Propyleneoxide .... 2.3-Epoxy-l-propanol see Glycido! ........... Ethanethiol, see Ethylmercaptan............... 2S 50 75 000 _ 100 50 200 15 190 300 450 4,950 o.; 400 200 790 90 Ethanolamine............................................... 2 Ethoxyethanol-Skin .................................. 2 Ethexyethylacetate (Cellosolve acetate) -Skin ............................................................ Ethyl acetate................................................ Ethyl acrylate-Skin ...................................... Ethyl alcohol (ethanol) ................................ + Ethylamine.................................................... + Ethyl sec-amyl ketone (5-methyl-3-heptan- one) ............................................................ 000 4, 200 10 60 + Ethyl benzene ............................................. Ethyl bfomlde................................. .... ... + Ethyl butyl ketone (3-Heptanone).............. 000 7,000 c Ethyl chloride ............................................. Ethyl ether.................................................... Ethyl formate ............................................ - o.; + C Ethyl mercaptan............................................ 25 75 Ethyl silicate................................................ 10. 50. Ethylene chlorohydrin-Skin .................... 100 0.5 50 10 10 860 2.1 c290 35 18 Ethylenediamine ................... ................ Ethylene dibromide, see 1,2-Dibromoethane........................................................ *c. Ethylene dichloride, see 1,2-0ichloroethane......................................................... Ethylene glycol dtmtrate-Sktn..................... Ethylene glycol monomethyl ether acetate, see Methyl cellosolve acetate................. 5 25 + Ethylene imine-Skin .................................. Ethylene oxide.............................................. Ethylidine chloride, see 1,1-Dichloro- ethane ....................................................... + N-Ethylmorphohne-Skin .............................. t See Intended Values ppm* My/M' * 3 10 30 0.5 1 100 1 5 1 0.2 1.5 360 100 600 5 0.1 19 0.5 36 200 740 100 400 25 ,1,000 10 540 1.400 100 1,900 18. 25. 100. 200 50. 1,000 400 100 10. 100 5 10 130. 435. 890 230. 2,600 1,200 300 25. 850 16 25 0.2 1.2 0.5 1. 50 90 20. 94. Ujllj.l'J Ut<' EC- 2043 Substance Fetbam......................................................... Ferrovanadrum dust...................................... Fluoride (as F) ........................................... Fluorine ..................................................... Fluorotnchloromethane ........................... C Formaldehyde............................................... + Formic acid ................................................ Furfural-Skin .............................................. Futfuryl alcohol............................................ Gasoline................................................ - Glyerdol (2, 3-Epoxy-l-propanol)................ Glycol monoethyl ether, see 2-Ethoxy- ethanol ....................................................... Guthion, see Azmphosmethyl------------- ---- Hafnium......................................................... Heptachlor-Skin............................................ t Heptane (n-heptane) .................................... Hexaehloroethane-Skin .................... -- Hexane (n*hexane)........................................ 2-Hexanone.................................. ................ Hexone ......................................................... + seC-Hexyl acetate Hydrazine-Skin.............................................. Hydrogen bromide ........................................ C Hydrogen chloride ...................................... Hydrogen eyanide-Skm................................ Hydrogen fluoride ..................................... Hydrogen peroxide, 90%.............................. Hydrogen selenide........................................ Hydrogen sulfide......................................... Hydroqumone................................................ C Iodine ....................................................... -y Iron oxide fume ........................................... Isoamyl alcohol ........................................ + Isoamyl acetate .......................................... + tsobutyl acetate........................................... ISOphorone .................................................. + Isopropyl acetate ..................................... Isopropyl alcohol ........................................ Isopropylamme.............................................. Isopropylether ............................................. Isopropyl glycrdyl ether (IGE).................... Ketene........................................................... Lead ............................................................. Lead arsenate ............................................. Lindane-Skin ........................................ Lithium hydride ....................................... L. P. G. (Liquified petroleum gas)............ Magnesium oxide fume ...................... Malathion-Skin ..................................... C Manganese ................................................ Mercury-Skin................................................ Mercuty (oigamc compounds)-Skin Mesityl oxide ........................................ + 1967 Addition 10 ppm* Mg' Mij Substance _ 15 _1 - 2.! 0.1 o.; 000 5.600 56 s. 9. 5 20 SO 200 - A6 50 150 Methanethiol, see Methyl mercaptan . Methoxyehlor ............................................ 2-Methoxyethanol, see Methyl cellosolve Methyl acetate .......................................... Methyl acetylene (propyne) ......................... Methyl acetylene-propadiene mixture (MAPP)....................................................... Methyl acrylate-Skin.................................... Methylal (dimethoxymethane)...................... Methyl alcohol (methanol) .......................... r + Methylamme.................................................. Methyl amyl alcohol, see Methyl isobutyl carbinol......... ..................................... 0. - 0. rr500 2,000 1 10 c <f500 1,800 + Methyl (n-amyl) ketone (2-Heptanone) ...... C Methyl bromide-Skin.................................... Methyl butyl ketone, see 2-Hexanone......... Methyl cellosolve-Skin................................ Methyl cellosolve acetate-Skin ................. (100 410 100 410 50. 300. (( C Methyl chloride ............................................ Methyl chloroform ....................................... Methylcyclohexane ...................................... 1 1. Methylcyclohexanol ..................................... 3 10 o-Methylcyclohexanone-Skin..................... . 57 Methyl ethyl ketone (MEK), see 2-Butan- 10 11 one................................................. .............. 32 Methyl formate....... ....................................... 1 1. + Methyl iodide Skin .................................. 0.05 0. Methyl isobutyl carbinol-Skin ................... 10 15 Methyl isobutyl ketone, see Hexone ........ -2 + Methyl isocyanate - Skin ........................... 0.1 1 C Methyl mercaptan.......................................... - 10. Methyl methacrylate...................................... 100 3S0 Methyl propyl ketone, see 2-Pentanone..... 100. 525. C aMethyl styrene............................................ 150. 700. C Methylene bisphenyl isocyanate (MDl) ..... 25 140 250. 950. 400 980 f Methylene chloride (dichloromethane) ....... Molybdenum (soluble compounds) .............. (insoluble compounds) ........... 5 12 Monomethyl aniline-Skin............................. 500 2,100 C Monomethyl hydiazme-Skin......................... 50 240 Morpholine-Skm............................................ 0.5 0.9 t Naphtha (coal tar) ...................................... 0.2 Napthalene.................................................... 0.15 0. 0, "( jl-Naphthylamine......................................... Nickel carbonyl .......................................... Nickel, metal and soluble compounds ........ 1,000 1 800 Nicotine-Skin............................................... 15 Nitric acid..... .................................... ........ .... IS p-Nitroamline-Skin ..................................... 5 Nitrobenzene-Skin .................................... 0.1 p-Nittochloro-benezene-Skin........................ 0.01 Nitroethane.................................................... 25 100 C Nitrogen dioxide .......................................... Nitrogen trifluoride..................... ................ t See Intended Values 11 ppm* Mp/MJ 15 200 610 1,000 1,650 1,000 10 1,000 200 10. 1,800 35 3,100 260 12. 100. 465, 20 80 25 80 25 120 100 210 350 1.900 500 2,000 100 470 100 460 100 250 5. 28. 25 100 0.02 0. 10 20 100 410 100 480 0. 02 0. 500 1. 740 -5 - 15 29 0.2 0. 20 70 200 800 10 50 _ AJ 0.001 - - 0. 1 0. 25 16 15 -1 100 310 59 10 29 EC- 2044 Substance C Nitroglycerin-Skin..................................-.... Nitiomethane.............. ...................... ........... 1-Nitrepropane.............................................. 2-Nitrepropane.............................. ............... N-NitrosOdimethyl-amine (Di-methylnitrosoamine)*Skin------------------------------ Nitiotpluene-Skin.............................. ........... Nitrotrichloromethane, see Chloropicnn .... t Octane............................... -.......................... Oil mist (mineral) ........................................ Osmium tetroxide.......................................... + Oxalic acid.................................................... Oxygen difluotide-...................................... Ozone ........................................................... Patathion-Skin............................... .............. Pentaborane................................ ....... ......... Pentachleronaphthal ene-Skin.... .................. Pentachlorophenol-Skin .............................. Pentane.......................................................... 2-Pentanone.................................................. Perchloroethylene........................................ Perchloiomethyl mercaptan......................... Perchloryl fluoride ...................................... Petroleum Distillates (naphtha)--.............. Phenol-Skin .................................................. p-Phenylene diamine-Skin............ -.............. + Phenyl ether (vapor)..................................... + Phenyl ether-Biphenyl mixture (vapor)....... Phenylethylene, see Styrene. ..................... Phenyl glycidyl ether (PGE) ..... ................ Phenylhydrazine-Skin.................................. Phosdrin (MevinphOS) (R)-Skm ................. Phosgene (carbonyl chloride) .................... Phosphine...................................................... Phosphoric acid............................................ Phosphorus (yellow)......... ........................... Phosphorus pentachlonde .......................... Phosphorus pentasulfide ............................ Phosphorus trichloride............................... Phthalic anhydride........................................ Picric acid-Skin............................................ + Pival (2-Pivaiyl-l, 3-indandione) ............... Platinum (Soluble Salts)............................. Polytetrafluotaethylene decomposition products ......................... ............................ Propane................................... -..... ...... ........ |3Propiolactone........................................... n-Propyl acetate .......................................... n-Propyl nitrate............................................ Propylene dichloride.................................... + Propylene imine - Skin................................ Propylene oxide............................................ Propyne, see Methylacetylene ................... Pyrethrum...................................................... + 1967 Addition ppm* Mp/k 0.2 100 25 25 2 250 90 90 A5 30 500 2,350 5 0.002 1. 0.05 0.1 0.1 0.2 0.1 0.005 0.01 0.5 0.5>| ( 1,000 2,950 200 700 100 670 c 0.1 0.8 3 13.5 500 2,000 5 19 0.1 i. 7. i. 7. 50 5 0.1 0.3 0.5 2 310 22 0.1 0.4 0.4 1 0.1 1 1 3 12 0.1 0.1 0.002 -- 1,000 200 25 75 2. 100 A* 1,800 A 840 no 350 5. 240 { V. 5 f K $u betone* Pyridine ....................................................... Quinone......................................................... Rhodium, Metal fume and dusts ................ Soluble salts.............................................. Rotenone (commercial)................................ Selenium compounds (as Se)........_....... ..... Selenium hexafluoride................................ Silver, metal and soluble compounds......... Sodium fluoroacetate (1080) - Skin............. Sodium hydroxide.......................................... Stibine .......................... .............................. Stoddard solvent.......................................... Strychnine...................................................... t c Styrene monomer (phenylethylene)........ ..... Sulfur dioxide...... ......................................... Sulfur hexafluoride ...................................... Sulfuric acid......... ........................................ Sulfur monochlonde...................................... Sulfur pentafluoride...................................... Sulfuryl fluoride-.......................................... Systox, see Demeton.................................. 2,4,5 T ....................................................... Tantalum..................................................... . TDP Skin.................................................. Teflon (R) decomposition products............. Tellurium...................................................... Tellurium hexafluoride................................ TEPP - Skin.................................................. 1,1,1. 2-Tettachloro-2, 2-difluoroethane..... 1.1.2.2-Tetrachloro-l. 2-difluoroethane .... 1.1.2.2-Tetrachloroethane-Skin................ Tetrachloroethylene, see Petchloroethy lene ............................................................. Tetrachloromethane, see Carbon tetra chloride................................ ....................... Tetraethyl lead (as Pb)- Skin ................... Tetrahydrofuran............................................ Tetramethyl lead (TML) (as lead) - Skin ... Tetramethyl succinonitrile - Skin............... TeBanitromethane........................................ Tetryl (2,4,6-trimtrophenylmethylni tra mmel - Skin ................................................ Thallium (soluble compounds) - Skin......... Thiram........................................................... Tin (inorganic cmpds, except oxide)........ Tin (organic cmpds) ........... ......................... Titanium dioxide.......................................... Toluene (toluol) .......................................... Toluene-2,4-diisocyanate .......................... o-Tolutdine - Skin ...................................... Toxaphene, see Chlorinated camphene..... 1,1,1-Tnchloroethane, see Methyl chloro form ............................................................. t See Intended Values ppm* M ft' M1 * 5 15 0.1 0.4 0.1 0.001 5 0.2 0.05 0.4 0.01 0.05 2 0.1 0.5 500 2,900 0.15 100 420 5 13 1,000 6,000 1 16 0.025 0.25 5 20 10 5 0.2 A4 0.1 0.02 0.2 0.05 500 4,170 500 4,170 5 35 200 0.5 1 0.075 590 0,075 3. 8 1.5 0.1 5 2 0.1 IS 200 750 0.02 0.14 5 22 12 13 EC- 2045 Subatoncp 1,1,2-Trichloroethane Skin...................... Trichloroethylene ........................................ Trichloromethane, see Chloroform............ Tiiehloronaphthalene - Skin...................... 1,2, 3-Trichloropropane ............................ 1,1,2*Ttiehloro 1, 2.2-trifluoroethane Tnettiylamine................................................ T rifluoiomonobromomethane........................ 2, 4,6-Trinitrophenol See Picric acid......... 2,4,6-Trinitrophenylmethylmtramine, see Tetryl ......................................................... Trinitrotoluene Skin.................................. Triorthocresyl phosphate............................ Triphenyl phosphate .................................. Turpentine .................................................. Uranium (soluble compounds) .................... (insoluble compounds)................ Vanadium (VjOs dust).............................. (ViOa fume)................................ Vinyl benzene, see Styrene Vinyl chloride ............................... -.......... Vinyleyanide, see Acrylonitrile ............... Vinyl toluene ............................................. Warfarin.............................. ........................... Xylene (xylol) .............................................. Xyiidine - Skin.............................................. Yttrium........................................................... Zinc oxide fume....................................... Zirconium compounds (as Zr) .................... ppm* 10. 100 45. 535 50 1,000 25 1,000 5 300 7.600 100 6,100 r11.5 0.1 3 100 S60 0.05 f0.25 0.5 0.1 (500 1,300 100 480 -- 0.1 100. 435. s 25 -1 -5 -5 < Radioactivity: For permissible concentrations of radio* isotopes in air, see U. S. Department of Commerce, National Bureau of Standards, Handbook 69, "Maximum Permissible Body Burdens and Maximum Permissible Concentrations of Radionuclides in Air and in Water for Occupational Exposure, " June 5, 1959. Also, see U. S. Department of Commerce National Bureau of Standards, Handbook 59, "Permissible Dose from External Sources of Ionizing Radiation, M September 24, 1954, and adden dum of April 15, 1958. {( ( i( + 1967 Addition 14 RESPIRABLE DUSTS EVALUATED BY COUNT SubfMncP m- P- P- p- f- * SILICA Crystalline Quartz, Threshold Limit calculated from the formula.......................... 250 ** %SiOz+ 5 Cnstobalite " " " Amorphous, including natural diatomaceous earth....................... + Tremolite...................................... 20 SILICATES (less than 146 crystalline silica) Asbestos........................................... 5 Mica.................................................. JO Soapstone......................................... JO Talc.................................................. 20 Portland Cement............................... 50 GRAPHITE (natural).......................... IS "Inert" or Nuisance Particulates 50 (or 15 mg/ms whichever is the see Appendix D smaller) Conversion factors mppcf x 35,3 = million particles per cubic meter = particles per c. c. Millions of particles per cubic foot of oir, based on impinger samples counted by light-field technics. The percentage of crystalline silica in the formula is the amount determined from oir*bome samples, except m those instances in which other methods hove boon shown to be applicable. 15 EC- 2046 NOT!a of INTENDED CHANGES The?it* with their corresponding values. v'OTWfN"'** th*M*e for which either a limit has been tnwvtfvd ** the first time, or for which a change m :*"< *K**'*^mnle^ded,, listing has been proposed, tr. >\dh s'wjtea, the proposed limits should he trial limits that will remain in this Haim* v * **nod of at least two years. During this the previously Recommended Limit wtlt tetMM? n effect* If, after two years no evidence ,vme* to light that questions the approprialene*? ot the values herein, die values will be pUi-ec the ''Recommended" list. Docu mentation vs atetlehJe for each of these substan ces. SubvHmc* ppm* M t)' M -H- Abate___ . H- 0oron tntMOfw.tt .............. -.............. ................-.... . ++ Btorowe ppntM'iuiv* .......................... sec*0utvi 4ii\wv .............................. + Camptwr,. --*...... -.......... . t Chlorine. ........ ................ . a-Chloio.'H-ehviww U'henocylchloride).. Chromium, *>.. duomous salts, as Ci Metal Ik* A Cobalt, Mel;* tivmr H- Cyanogen Dbutyl phns.ivwf ..................... ..................... dust.......... ............ . ................ *............ ............................ DibutylpMh.-***!* H-C Diethylavp ................ ........... .............. ............ 10 Onsoptopviam-if^*`i ................ ........... OimethviphtMi as Diphenyl ................. .......... ............. .......... . -H Diphen\l .vm^r ........... ............. + Ethylwipfiii*'*'' ,i * ^ jwami or NitTOgh* * ............................ - 15 i.o 0,1 ISO 450 2 1 0.05 0.3 _ 10 \m -- 5, 0.2 0.5 1. 0.1 5. 5. 20. 5. 1. 10 0.2* r T i f Sub. tone. ++ Indium and compounds, as Id.................... H- lion salts, soluble, as Fe.... ..... -........ . Isobutyl alcohol-....................... ............... Maleic anhydride......................... -............ H-C Methyl silicate............................... ........... Naphtha (coal tar)...... -............-............... Nitric oxide.................................. -............ Octachlornnaphthalene-Skin...................... + Octane......................................................... Parquat-Skin........................................... . Phenyl glycidyl ethei (PGE).................... ++ Propargyl alcohol-Skin............................ Piopyl alcohol.... ................. ..................... ++ RDX-Skin................................. ................ Ronnel................ -.... ............ -................... + Stoddard solvent.-................................... -- " + Stytene--.......... -........-............................. I C Tetphenyis........................................... .... c Tetiachloronaphthalene-Skin.................... Tributyl phosphate.................-................. -+ Tungsten & compounds, as W Soluble....... ................... ....................... . Insoluble................................................... + Uranium, sol. & insol. compounds as U. Zinc chlotide (fume)................ -................ Fibrous Gasoline + Hept.me *........... --........... HexachlwnnA'***-SKm........ ................ -- A6 200 _ * Pori* of * *** *fc*r mill1" parts of air pigs vaper by v*-***^ ** vml 760 mm. Hg prciiurt. ** Appro*tn*0* * *e'**** 't tMfticulot* par cubic 800 0.2 C ( * mAnotoartm*>of yp>hf -* *'******* of not moto than 0. 02 ppm a. v#cioh may b ft<ssorv *t> + 1967 Revision ppm* Mg/Md ** - 0.1 -1 100. 300. 0.25 1. 5100. 400. 25 30. _ 0.1 200 930 - 0.5 10. 62. 1200. 510. - 1.5 - 15. 200 50 _ 1. 9.4 - 2. - 5. _1 -5 - 0.2 - 1. Appendix A c be considered as additive. That is, if the sum of the following ,Tact ions. a' Bemidin* Because of high incidence of bladdei tumors in man, any exposure, including skin, is extremely hazardous. C t Cz T, + Tg + Cn Tn A* jJ.Nophthylnmine. Because of the extremely high incidence of bladder tumors in workers handling this compound and the in ability to control exposures^ naphthylamine has been piohibited by the State of Pennsylvania fmm manufactuie, use and ether activities that involve human contact. exceeds unity, then the threshold limit of the mixture should be considered as being exceeded. Ci indicates the observed atmospheric concentration, and Tt the corresponding thres hold limit, (See Example lA.a.). a'N-Nirrosodimethylomine Because of extremely high toxicity and presumed carcinogenic potential of this compound, con r tact by any route should not be permitted. A4 PQlytetrafluoroerhylenv* decomposition products. r'r Thermal decomposition of the fluorocarbon chain in an leads fto the formation of oxidized products containing carbon,fluor i ine and oxygen. Because these pioducts decompose in part by hydrolysis in alkaline solution, they can be quantita (tively determined in air as fluoride to provide an index of f exposuie No TLV is recommended pending determination of the toxicity of the pioducts, but an concentrations should be minimal. A5p PropioloetoneBecause of high acute toxicity and demonstra ted skin tumor production in animals, contact by any route should be avoided. A Gasoline. The composition of gasoline vanes greatly and thus a single TLV for all types of gasoline is no longer ap plicable. In general, the aromatic hydrocarbon content will determine what TLV applies. Consequently the content of benzene, other aromatics and additives should be determined to artive at the appropriate TLV (Elkins, et al. A.I.H.A.J. 24, 99, 1963). Trade Names: Algoflon, Fluon, Halon, Teflon, Tetran Exceptions to the above rule may be made when there is good reason to believe that the chief effects of the different harmful substances are not In fact additive, but independent as when purely local effects on different organs of the body are produced by the various components of the mixture. In such cases the threshold limit ordinarily is exceeded only when at least one member of the series (C_t or_Cz etc.) itself T i Tz has a value exceeding unity, (See Example lA.b.) Antagonistic action or potentiation may occur with some combinations of atmospheric contaminants. Such cases at present must be determined individually. Potentiating or an tagonistic agents are not necessarily harmful by themselves. Potentiating effects of exposure to such agents by routes other than that of inhalation is also possible, e.g. imbibed al cohol and inhaled narcotic (trichloroethylene). Potentiation is characteristically exhibited at high concentrations, less probably at low. When a given operation or process characteristically emits a number of harmful dusts, fumes, vapors or gases, it will frequently be only feasible to attempt to evaluate the hazard by measurement of a single substance. In such cases, the threshold limit used for this substance should be reduced by a suitable factor, the magnitude of which will depend on the number, toxicity and relative quantity of the other contami nants ordinarily present. Appendix B B.l THRESHOLD LIMIT VALUES FOR MIXTURES Examples of processes which are typically associated with two or more harmful atmospheric contaminants are welding, automobile repair, blasting, painting, lacquering, certain foundry operations, diesel exhausts, etc. (Example 2.) When two or more hazardous substances are present, their combined effect, rathei than that of either individually, should be given primary consideration. In the absence of informa tion to the contrary, the effects of the different hazaids should 18 19 EC- 204B threshold limit values for MIXTURES EXAMPLES 1A. General case, where air Is analyzed far each componenL o. ADDITIVE EFFECTS Ci . _Cz_ . Cj Ti Tz Ts Tv Air contains 5 ppm of carbon tetrachloride (TLV, 10), 20 ppm of ethylene dichloride (TLV, 50) and 10 ppm of ethylene dibromide, (TLV, 25). _5 10 +. 20 T, 10 "25" = 65 _ in Threshold limit is exceeded. rr r c cc h. INDEPENDENT EFFECTS Air contains 0.15 mg/m3 of lead (TLV, 0. 2) and 0. 7 mg/m 3 of sulfuric acid (TLV, 1). JLiL = o.2o 0.75; _2zl_ = o.7 Threshold limit is not exceeded. IB. Special case when source of contaminant is a mixture and atmospheric composition is assumed similai to that of original material, i.e. vapor pressure of each component is the same at the oOserved temperature. a. additive effects, approximate solution. 1. A mixture of edual parts (1) trichloroethylene (TLV, 100), and (2) methyl chloroform (TLV, 350). -L + -i = Cm 100 350 Tm Solution applicable to "spot" solvent mixture usage, where all or nearly all, solvent evap orates. C) = Cj -- Cm 2 Ci C; _ 2Ci 100 3 50 Tm f v f 7 a ^ (. 7C. , 2c _ ;ci 700 700 Tm Tm = 700 * -L = 155 ppm IB. b. General Exact Solution for Mixtures of N Components With Additive Effects and Different Vapor Pressures. (4L+ CL + T i Tz 1; T (2) Ci + Ci + . + Cv = T; (2.1) _Cj_ + Ci T C> 1. T By the Law of Partial Pressures, (3) C i = ap i, And by PaoulPs Law, (4) p i = F i p i". Combine (3) and (4) to obtain (5) C i = aF ip i'. Combming(l), (2, l)and(S), we obtain (6) _Fjpi T + Fzpz" T .. _F'g' , Fzpiy, . . Fvpv T i T z +- Tv and solving tor T, (6.1| y __ F I P I* + Fzpz` Fipi , Fzpz Ti + Tz y --1 " 11 _ or Z Fipi" (6.2) Z F i p i* i--l Ti T 3= Threshold Limit Value in ppm. C = Vapor concentration m ppm, p = Vapor pressure of component m solution. EC- 2049 p" = Vapor pressure of pure component F = Mol fraction of component in solution. a = A constant of proportionality. Subscripts 1,2, .. . n relate the above quantities to components 1,2, . . . n, respectively. Subscript i refers to an arbitrary component from 1 to n. Absence of subscript telates the quantity to the mixture. Solution to be applied when there is a reservoir of the solvent mixtuie whose composition does not change appreciably by evaporation. Exact Arithmetic Solution of Specific Mixture Mol. wt. Oensity T p*at Mol frac2S,'C tion in half-and half solu tion by volume Trichloro ethylene (1) 131.4 1,46 g 'ml 100 73mm Hg 0. 527 Methylchlorofoim (2) 133,42 1. 33 g'ml 350 125mm Hg 0.473 F ip i = (0. 527) (73) = 38.2 Fips" = (0. 47 3) (125) = 59. 2 , _ 38.2 + 59.2 ,, 197 . 4) (350) __ i97.4) '3501 ,, ,77 38. 2 59.2 133.8 - 59. 2 193.0 100 350 T = 177 ppm (Note difference in T.L.V. when account is taken of vapor piessure and mol fraction in comparison with above example where sucn account is not taken). 2. A mixture of one part of fl> paiathion (TLV, 0.1) and two parts of (2) EPN (TLV, 0. 5r. rr C1 . Cl 0. 1 0, 3 Cm: C 2 Tie Cm s= 3C i Ct , 2C 1 _ 3C i 0. 1 0. S Tie 7Ci -- 3Ci 0, S Tie 30 r rr'r . (c TIB = . -- 0.21 mj/ml 1C. T. L. V. for Mixtures of Mineral Ousts. For mixtures of biologically active mineral dusts the general formula for mixtures may be used. With the exception of asbestos, pure minerals are assigned TLV of 2.5, 20 or 50. For a mixtuie containing 80% talc and 20% quartz, the TLV for 100% of the mixture "C" is given by: ff (, %' (( TLV= oxhn = 8-4mppcf 20 1 4.5 Essentially the same result will be obtained if the limit of the mote (most) toxic component is used provided the effects aie additive. In the above example the limit for 20% quartz is 10 mppcf. For another mixture of 25% quartz 25% amorphous silica and 50% talc: TLV= O.M,1 0.25, o,5 = 7.3 mppcf T20 ^ 20 The limit for 25% quartz approximates 8 mppcf. 22 23 EC- Appendix C BASES FOR ASSIGNING LIMITING "C" VALUES By definition in the Preface, a listed value bear ing a "C" designation refers to `ceiling* value that should not be exceeded; all values should fluctuate below the listed value. In general the bases for assigning or not assigning a "C" value rest on whether excursions of concentration above a proposed limit for periods up to 15 minutes may result in a) intolerable irritation, b) chronic, or irreversible tissue change, or c) narcosis of sufficient degree to increase accident ptoneness. impair self rescue or materially reduce work efficiency. In order for the Committee to decide whether a sub stance is a candidate for a "C" listing, some guidelines must be formulated on the permissive fluctuation above the limit in terms of the seriousness of the response in the categories a, b, c, given above. For this the factors given in the table below have been used by the Committee. For both technical and practical reasons, the factors have been pegged to the concentration in an inverse manner. It will be noted that as the magnitude of the T. L. V. increases a correspondingly decreased range of fluctuation is permitted; not to decrease the factor for T. L. V. s of increasing magnitude would permit exposures to large absolute quantities, an undesirable condition, a condition that is minimized at low T. L. V. s. More over, larger factors at the lower T. L. V. s are con sistent with the difficulties in analyzing and con trolling trace quantities. T.L.V. RANGE ppm" or mf/m3 Examples 0 to 1 1 + to 10 Toluene diisocyanate-T. L. V., 0.02 ppm, if permitted to rise above 0.06 ppm may result ; sensitization in a single sue. sequent exposure.1 "C" listing recommended on category b. Manganese -T.L.V., 5mg/m\ contains little or no safety factor. All values should fluct uate below 5mg/mJ. "C" listing recommended on category b. 24 T.L.V. T**t f RANGE T.I.V. n* r mi/mi Factor Eiamplai 10+ to 100 1.5 Methyl styrene-T. L. V. 100 if encountered at levels of 150 ppm will prove intense ly irritating, **C" listing recommended on category a. c 'r 100 +to 1000 1.25 Methyl chloroform-T. L. V. 35Qppm, at 438 ppm for per iods not exceeding 15 min utes is not expected to re sult in untoward effects relating to category c. No "C" listing recommended. < * Whichever unit is applicable PERMISSIBLE EXCURSIONS FOR TIMEWEIGHTED AVERAGE (TWA) LIMITS c As stated in the preface, the same factors may be used as guides for reasonable excursions above the limit for substan ces to which the time-weighted average applies. The timeweighted average implies that each excursion above the limit is compensated by a comparable excursion below the limit. Thus, a value of 6 -ppm HF is permissible for periods not ex ceeding 15 minutes, provided an equivalent decrease below the limit of 3 -ppm obtains. Appendix D Some "Inert" or Nuisance Particulates* Aiundum (AijOs) Calcium carbonate Limestone Magnesite Cellulose Marble Poittand Cement ^ Corundum (Alitb) Plaster of Paris Rouge Glycerine Mist Graphite (synthetic) Gypsum Silicon Carbide Starch Sucrose Tin Oxide Vegetable oil mists (except castor, cashew nut, or similar irritant oils) Titanium Dioxide *When toxic impurities are not present. 25 EC- 2051 Appendix E Some Simple Asphyxiants - "Ineft" Gases and Vapors. Acetylene Argon Ethane Ethylene Helium Hydrogen Methane Neon Nitrogen Nitrous Oxide f r r r< E.J. Baler Hervey B. Elkins, Ph.D. W. W. Fredrick, Ph.D. Bernard Grabois, P.E. Paul Gross, M.D. Wayland J. Hayes, Jr., M.D. Harold N. MacFarland, Ph.D. Consultant Fredrick T. McDermott E. Mastromatteo, M.D. Walter W. Melvin, M.D. Ralph G. Smith, Ph. D. Mitchell R. Zavon, M.D. i Herbert E. Stokinger, Ph.D., Chairman EC- 2052