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Threshold Limit Values of Airborne Contaminants Adopted By ACGIH For 1969 AND INTENDED CHANGES I r1 ~ I i i SGP 0006415 I i Copyright 1969, by American Conference of Governmen tal Industrial Hygienists. The American Conference of Governmental Industrial Hygienists will welcome requests for permission to re publish or reprint these Threshold Limit Values. Requests for such permission should be directed to the SecretaryTreasurer, 1014 Broadway, Cincinnati, Ohio 45202. Price Each 1 -- 49 Copies.................................................... 50$ 50 -- 999 Copies............................................... 40$ 1000 - 4999 ...................................................... 30$ 5000 or more Copies....................................... 15$ Documentation of Threshold Limit Values. A separate companion piece to the TLVs is issued by 4CG1H under this title. This publication gives the pertinent scientific information and data with reference to literature sources that were used to base each limit. Each documentation also 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. Information concerning the availability of Xerox copies of the 2nd edition of the Documentation of Threshold Limit Values shculd be directed to the Secretary-Treasurer. feprtlted fey Persrtsslo* of TtespifteaaT Prograi Pabllc fteslth Servto* ) ^ 1 ! ` I | PREFACE THRESHOLD LIMIT VALUES FOR 1969 Threshold limit values refer to airborne concentrations of substances and represent conditions under which it is be lieved that nearly all workers may be repeatedly exposed day after day without adverse effect. Because of wide varia tion in individual susceptibility, however, a small percentage of workers may experience discomfort from some substances at concentrations at or below the threshold limit, a smaller percentage may be affected more seriously by aggravation of a pre-existing condition or by development of an occupa tional illness. Simple tests are now available (J. Occup. Med. 9, 537, 1967; Ann. N.Y. Acad. Sci. 151 Art. 2, p. 968, 1968) that may be used to detect those individuals hypersusceptible to a variety of industrial chemicals (respiratory irritants, hemolytic chemicals, organic isocyanates, carbon disul fide). These tests may be used to screen out by appropriate Job placement the hyperreactive worker and thus in effect Improve this "coverage" of the TLVe. Threshold limit values refer to time-weighted concentra tions for a 7 or 8-hour workday and 40-hour workweek. They should be used as guides in the control of health hazarda and should not be used as fine lines between safe and dangerous concentrations. (Exceptions are the substances listed in Appendices A and Bandthose substances designated with a "C" or Celling value, Appendix C.) Time-weighted averages permit excursions above the limit provided they are compensated by equivalent excur sions below the limit during the workday. In some instances it may be permissible to calculate the average concentration for a workweek rather than (or a workday. The degree of permissible excursion is related to the magnitude of the threshold limit value of a particular substance as given in Appendix C. The relationship between threshold limit and permissible excursion is a rule of thumb and in certain cases may not apply. Tbs amount by which threshold limits may be exceeded tor 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 effeet* are cumulative, the frequency with which high concentratione occur, and the duration of such periods. Ail (actors must be takes into consideration in arriving at deciaion as to whether a hazardous condition exists. Threshold limits are baaed on the best available informa tion from Industrial experience, from experimental human and animal studies, and, when possible, from a combination t 1 I SGP 0006416 of the three. The basis on which the values are established may differ from substance to substance; protection against impairment of health may be a guiding factor tor some, whereas reasonable freedom from irritation, narcosis, nuisance or other forms of stress may form 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. There is increasing evidence that physical irritation may initiate, promote or accelerate physical impairment through Interaction with other chemical or biologic agents. In spite of the fact that serious injury is not believed likely as a result of exposure to the threshold limit con centrations, the best practice Is to maintain concentrations of all atmospheric contaminants as low as is practical. These limits are Intended for use in the practice of In dustrial hygiene andshouldbe interpreted and applied only by a person trained in this discipline. They are not Intended for use, or for modification for use, (1) as a relative index of hazard or toxicity (2) in the evaluation 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 conditions, or(S) for adoption by countries whose working conditions differ from those in the United States of America and where substances and processes differ. Ceiling vs Time-Weighted Average Limits. Although the time-weighted average concentration provides the most satisfactory, practical way of monitoring airborne agents for compliance with the limits, there are certain substances for which it is inappropriate. In the latter group are sub stances which are predominantly fast acting and whose threshold limit is more appropriately based on this particu lar response. Substances with this type of response are best controlled by a ceiling "C" limit that should not bs exceeded. It is implicit in these definitions that the manner of sampling to determine compliance with the limits for each 4Praip auat-diffasje-aingleJ)Ptet.jaiapUy. Untie applicable to a "C" limit, is not appropriate to the time-weighted limit: here, a sufficient number of samples 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 timeweighted average limit requires an explicit limit to the ex cursions that are permissible above the listed values. Tbs j magnitude of these excursions may be pegged to tbs magniI hide of the threshold limit by an appropriate factor shown in . Appendix C. tt should be noted that the same factors are used : by the Committee in nwetug a judgment whether to include ! or exclude a substance for a "C" listing. j "Skin" Notation. Listed substances followed by the de I slgnation "Skin" refer to the potential contribution to the j over-all exposure by the cutaneous route including mucous I membranes and eye, either by air-borne, or more particu larly, by direct contact with the substance. Vehicles can alter skin absorption. This attention-calling designation is j intended to suggest appropriate measures for the prevenI tion of cutaneous absorption so that the threshold limit is : not invalidated. I I Mixtures. Special consideration should be given also to the | application of the TLVs In assessing the health hazards I which may be associated with exposure to mixtures of two or ' more substances. A brief discussion of basic considerations involved in developing threshold limit values for mixtures, and methods for their development, amplified by specific examples are given in Appendix B. "Inert" or Nuisance Particulates. A number of dusts or particulates that occur in the working environment ordinar ily produce no specific effects 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 soluble (starch, soluble oils, calcium carbonate) but are of such a low order of activity that In concentrations ordinarily encountered do not cause physiologic Impairment; still others may be rapidly eli minated or destroyed by the body (vegetable oils, glycerine, sucrose). In the case of the insoluble substances, there may be some accumulation In the respiratory passages. In the case of the soluble substances, this accumulation will or dinarily be temporary but may Interfere to some extent with respiratory processes. Bence, It le desirable to control the concentrations of such particulates tn the air breathed by any indtvlihial, In keeping with good industrial hygiene - practice. , "A thrMMM"ttnt of' Iflnig/wVor SO mppcf, of total dust i <1% Sj02, whichever is less. Is recommended for substances . In these categories and for which no specific threshold limits have been assigned. This limit, for a normal work day, does not apply to brief exposures at higher concen trations. Neither does it apply to those substances which may cause physiologic impairmentat lower concentrations but for which a threshold limit has not yet been adopted. Some "inert" particulates are given in Appendix D. 3 i SGP 0006417 Simple Asphyxiants - "Inert" Gases or Vapor**. A number of gases and vapors, when present in high concentration* in air, act primarily an simple asphyxiants without other signi ficant physiologic effects. A TLV may not be recommended for each simple asphyxiant because the limitingfactor is the available oxygen. The minimal oxgyen content should be 18 percent by volume under normal atmospheric pressure (equivalent to a partial pressure, p02 of 135 mm Hg). Atmos pheres deficient in 02 do not provide adequate warning and most simple asphyxiants are ordorless. Several simple asphyxiants present an explosion hazard. Account should be taken of this factor in limiting the concentration of the asphyxiant. Specific examples are listed in Appendix E. Physical Factors. It is recognized that such physical factors as heat, ultraviolet and ionizing radiation, humidity, abnormal pressure (altitude) 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 to moderate deviations from normal environments, the safety factors of most substances are not of such a magnitude as to take care of gross devia tions. For example, continuous work at temperatures above 90op or over-time extending the workweek more than 25%, might be considered gross deviations. In such instances Judgment must be exercised In the proper adjustments of the threshold limit values. "Notice of Intent" At the beginning of eachyear, 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. Although the Conference does not consider the TLVs appropriate matter tor adoption Into legislative codes and regulations, it recognises that the values may be so used. If so used, the intent of the concepts contained In the Preface should be maintained and provisions should be made to keep the list current. These values are reviewed annually hy .the .Committee .on Threshold .Limits for revision or additions, as further information becomes available. Reprint Permission. This publication may be reprinted provided that written permission U obtained from the Secre tary-Treasurer of the Conference and that it be piblished in its entirety. A AOOPTED VALUES (In Alphcbetlcol Order) $wbttnc Abate ................................................ Acetaldehyde.................................... Acetic acid........................................ Acetic anhydride .............................. Acetone ............................................ Acetonitrile...................................... Acetylene dichloride, see 1, 2 Dlcloroethylene .......................... Acetylene tetrabromide.................. Acrolein............................................ Acrylamide-skin ............................ Acrylonitrile-Skin............................ Aldrin-Skin........................................ Allyl alcohol-Skin............................ Allyl chloride.................................... Allyl gtycidyl ether (AGE).............. Allyl propyl disulfide....................... 2-Amlno .nanol, see Sthanolamtne 2-Amlnopyridlne.............................. Ammonia ............................ ............. Ammonium sulfamate (Animate)... n-Amyl acetate................................ sec-Amyl acetate.............................. Aniline Skin...................................... Anisid e (o,p-isomers)-Skin......... Antimo y fc compounds (aa Sb).... ANTU (dpha naphthyl thiourea) ... Araeni b Compounds (aa Aa)........ Arable .............................................. Azinphii-methyl-Skin.................... Barlur (soluble compounds)........... 1 Benzene (benzol)-SUn..................... Benzidine-Skin................................... p-Benzoqulnone, see Quinone......... Benzoyl peroxide.............................. Benzyl chloride................................. Beryllium.......................................... Biphenyl, see Diphenyl.................. Boron oxide........................................ ' Boron trlbromlde............................. fV-*> m 200 10 5 1,000 40 1 0.1 20 2 1 10 2 0.5 SO 100 125 5 0.0$ - 25 . . 1 - 1 -/*J k) 15 380 25 20 2,400 70 14 0.25 0.3 45 0.25 5 3 4$ 12 2 35 15 525 550 19 0.5 0.5 0.5 0.5 0.2 0.2 0.5 80 A> 5 5 0.002 15 a) Puts of vapor or gu per erilllne puts of eootamiaated tlr by volume at iiC ud TOO mm. Sg praeeure. t) Approximate mUllerame of pantealaw per eubie meter of air. A Wumbara. Sea tppumhe A IMS ASdtttae S ! SGP 0006418 5vbtanc% C Boron trifluorlde............................... Bromine............................................ * Bromine pentafluorlde.................... Broraoform-Skin.............................. Butadiene (1, 3-butadlene) Butanethiol, see Butyl mercaptan . 2-Butanone........................................ 2-Butoxy ethanol (Butyl Celloaolye) Skin................................................ Butyl acetate (n-butyl acetate) .... n-Butyl acetate................................ sec-Butyl acetate............................ tert-Butyl acetate............................ Butyl alcohol.................................... sec-Butyl alcohol.............................. tert. Butyl alcohol.......................... C Butylamine-Skin.............................. C tert. Butyl chromate (as Cr03) - Skin................................................ -Butyl glycldyl ether (BGE).......... ** Butyl mercaptan.............................. p-tert. Butyltoluene........................ Cadmium (Metal dust and soluble salts)............ ................................. ** Cadmium oxide fume...................... Calcium arsenate............................ Calcium oxide..................................... ' Camphor............................................ Carbaryl (Serin ) ...................... Carbon black.................................... Carbon dioxide.................................. Carbon dlsulIlde-SUn....................... Carbon monoxide.............................. Carbon tetrachlorlde-SUn.............. Chlordane-Skln................................ Chlorinated camphene, - Skin .... Chlorinated diphenyl oxide............... Chlorine.............................................. Chlorine dioxide................................ C Chlorine trifluoride........................ C Chloroacetaldehyde.......................... "d-Chloroacetophenone (pbenacyl- chloride)........................................ -jChlacnfeaasena, (monochloroben- sene)................................................. o-Chlorobenxylidene malooonltrile (OCBM).......................................... Chlorobromomethane...................... 2-Chloro-l, 3 butadiene, see Chloroprene................................ .. Chlorodlphenyl (42% Chlorine) - Skin................................................ 1 0.1 0.1 0. s 1,000 200 50 150 150 200 200 100 150 100 5 50 10 10 - - - 2 5,000 20 50 10 1 0.1 0.1 1 0.05 75 0.05 200 m )n Notice ^ IMaadM rtmr*f e ef/t3 1 2 O.T $ 2,200 590 240 710 710 950 950 300 450 300 15 0.1 270 35 60 0.2 0.1 1 5 5 3.5 9,000 60 55 65 0.5 0.5 0.5 0.3 0.4 3 0.3 ~350 0.4 1,050 1 fablMCt Chlorodiphenyl (54% Chlorine) - Skin................................................. 1, Chloro, 2, 3 epoxypropane, see Epichlorhydrin............................... 2, Chloroethanol, see Ethylene chlorohydrin................................... Chloroethylene, see Vinyl chorlde. C Chloroform (trlchloromethane).... 1-Chloro-l-nitropropane................. Chloropierin....................................... Chloroprene (2-chloro-l, 3-twta- diene)-Skin..................................... Chromic acid and chromates (as Cr03).............................................. Chromium, sol. chromic, chrom- ous salts as Cr............................. Metal & insol. salts.................... Coal tar pitch volatiles (benzene soluble fraction) anthracene, BaP, phenanthrene, acridine. chrysene, pyrene)........................ Cobalt, metal fume 6 dust............... Copper futpe...................................... Dusts and Mists............................. Cotton dust (raw)............................... Crag herbicide........................... Cresol (all isomers) - Skin............. Crotonaldehyde................................... Cumene-Skin.................................... Cyanide (as CN)-Skin....................... * Cyanogen........................................ .... Cyclohexane...................................... Cyclohexane!..................................... Cyclohexanone............................ Cyclohexene....................................... Cyclopentadtene................ ............... 2, 4-D................................................ DDT-Skln.......................................... DDVP-Skln................................... Decaborane-Skln .......................... Demeton -Skin.......................... Discclone alcohol (4-metbyi-2- pentanone)................................. 1, 2 Dlamtnoethane, see Ethy- tenediamfne Dtaeomdthane....... Dlborane ...................................... C 1, 2-Dlbromoethane (ethylene dlbromide)-SUn........................ Dtbutyl phosphate........................ Dibutylphthalate............................ C o-Dlchlorobentene....................... p-Dichlorobenzene....................... * fftt Wrr*frr V Tntiitiil Hay sen** 50 20 0.1 25 " - 5 2 50 10 300 50 so 300 75 0.05 ** so 0.3 0.1 25 1 - 50 75 T 0. 240 100 0. 90 0. 0. 1 0. 0. 0. 1 1 15 22 6 245 5 " 1,050 200 200 1,015 200 10 l 1 0. 0. 240 0. 0. 190 5 5 300 450 > SGP 0006419 Inhumes Dichlorodiflooromethane................. 1,000 1, 3-Dichloro-5, dimethyl hy- dantoln............................................. 1, 1-Dichloroethane........................ too 1, 2-Dichloroethane........................ 50 1, 2-Diehloroethylene...................... 200 C Dlchloroethyl ether-Skin................ 15 Dichloromethane, see Methylene- chloride.......................................... . Dichloromonofluoromethane........... 1,000 C 1,1-Dichloro-l-nitroethane........... 10 1,2-Dichloropropane, see Pro- pylenedichlortde.......................... Dichlorotetrafluoroethane ... r.... 1,000 Dleldrln-SUn..................................... - Dlethylamine.................................... 25 Diethylamino ethanol-Skin............... 10 *C Diethylene triamine-Skln................. 10 Dlethylether, see Ethyl ether........ Dilluorodibromomethane................. 100 C Dlgtycldy' tther (DCE).................... 0.5 DlbydraxyteueRe, see Hydroqufta- one .................................... ........... Dlisobutyl ketone ............................ 50 Dlisopropylamlne-Skln.................... 5 * Diphenyl amine.................................. - DDnetho-ymethane, see Methylal.. Dimethj acetamlde-Skln .............. 10 Dimethy amine................................... 10 Dimethyl aminobenzene, see Xyli- dene ............................................ Dimethy utUlne(N-dlmethyUnlline)- Skin................................................ 5 Dimethyl benzene, see Xylene .... Dimethyl 1, 2-dlbromo-2, 2-dichloroetbyl phosphate, (Dtbrom). - Dimethylformamide-Skin................. 10 1,6 Dlmethylheptanone, see Dlleobutyl ketone ......................... 1,1-Dimethylbydrazine-SUn........... 0.5 Dimethytphthalate............................ - Dimethylsulfate-Skin....................... 1 Dinitrobenzene (all isomers)-Skln. Dinitro-o-cresol-Skin.................... TOnltioHl--in ..................... - Dioxane (Diethylene dioxide)-Skin . 100 Diphenyl ............................................. 0.2 Diphenyl Amine.......................... Dlpheoylmethane dllsocyanate (see - Methylene Mapbenyl isocyanate (MD0............................................... iMAiUUka * n/h3 k> 4,950 0.2 400 200 790 90 4,200 60 7,000 0. 25 75 50 - 860 2.8 290 20 10 35 18 25 3 SO 1 5 5 1 0.2 1* 360 1 10 Dipropylene glycol methyl ether- SUn ................................................ 100 01-sec, octyl phthalate (Dt-2- ethylhexylphthalate....................... Endrln-Skin...................................... Epichlorhydrln-SUn......................... S EPN-SUn.......................................... 1.2-Epoxypropane, see Propylene- oxide .............................................. 2.3-Epoxy-1-propanol, see Glycldol Ethanethiol, see EthylmercapUn.. Ethanolamtna.................................... 3 2 Ethoxyethanol-Skin...................... 200 2 Ethoxyethylacetate (Cellosolre acetate)-Skin................................ Ethyl acetate...................................... Ethyl acrylate-Sktn........................... Ethyl alcohol (ethanol)..................... 100 400 25 1,000 Ethylamine.............................. .. 10 Ethyl sec-amyl ketone (5-metbyI3-heptanone) ................................. Ethyl bensene..................................... Ethyl bromide................................... 25 100 200 Ethyl butyl ketone (3-Heptaaone) .. 50 Ethyl chloride................................... 1,000 Ethyl ether........................................ Ethyl formate..................................... ** Ethyl mercaptan.............................. Ethyl silicate..................................... Ethylene chlorohydrin-SUn............. 400 100 10 100 5 Ethylenedlamlne.............................. 10 Ethylene dlbromide, see 1,1 Dibromoethaae ............................. Ethylene dtehtorlde, see 1,2- Dlchloroethaae ............................. C Ethylene glycol dlnltrnte and/or Nltroflycerln-SUn ..................... 0.2*> Ethylene glycol monomethyl ether acetate, see Methyl cslloeolTS acetate ........................................... Ethylene Unine-SUa......................... EtltrlWM TTTHf .............................. 0.5 50 Ethylidlne chloride, see 1,1-D1- N-EtbylmorptaUne-Skla................. Ferfaam ............................................ FerrorsnmUnm duet......................... Fluoride (ae F)................................. Fluorine............................................ Flnorotrichloromathane ................. C Formaldehyde........ ........... 20 0.1 1,000 5 00 5 0.1 19 0.5 T40 540 1,400 100 1,900 18 130 435 890 230 2,500 1,200 300 25 850 16 25 1 1 90 84 IS 1 2.5 0.2 5,500 ri i SGP 0006420 SvbMM (-> Formic acid....................................... Furfural-Skin .................. ................ Furfuryl alcohol.............................. Gasoline............................................ Glycldol (2,3-Epoxy-1-propanol).. Glycol monoethyl ether, see 2- Ethoxyethanol .............................. Guthlon,* see Azlnpbosmethyl ... Hafnium ............................................ Heptachlor-Skin .............................. * Heptane (n-heptane) ........................ Hexachloroethane-Skin .................. Hexachloronaphthalene-Skin.......... Hexane (n-hexane) .......................... 2-Hexanone ...................................... Hexone .............................................. sec-Hexyl acetate............................ Hydrazine-Skin................................ Hydrogen bromide .......................... C Hydrogen chloride .......................... Hydrogen cyanide-SUn.................... Hydrogen fluoride............................ ** Hydrogen peroxide, 90%................ Hydrogen selenide............................ Hydrogen sulfide.............................. Hydroquinone .................................... * Indium and compounds, as In......... C Iodine ................................................ Iron oxide fume................................ * Iron salts, soluble, as Fe ............ Isoamyl acetate................................ Isoamyl alcohol.............................. .. lsobutyl acetate................................ lsobutyl alcohol................................ Iaopborone.................... ................... Isopropyl acetate ............................ Isopropyl alcohol ............................ Isoprupylamlne................................ Isopropylether.................................. Isopropyl glycidyl ether (ICE) .... Ketene ................................................. Lead ................................................ Lead araenate.................................. '-MMmtt'OMn.................................... Lithium hydride................................ L. P. G. (Liquified petroleum gas). Magnesium oxide fume .................. MalathKm-Skln ................................ Maleic anhydride ............................ C Manganese......................................... ** Mercury-Skin ................................... 5 5 50 50 500 1 500 100 100 so 1 3 5 10 3 1 0.05 10 0.1 100 100 150 100 25 250 400 5 500 50 0.5 1,000 0.25 See Notice at Mended 10 y/k1 k> 9 20 200 A3 150 0.5 O.S 2,000 10 0.2 1,800 410 410 300 1.3 10 7 11 3 1.4 0.2 15 2 0.1 1 10 1 525 360 700 300 140 9SO 980 12 2,100 240 0.9 0.2 0.15 Vfi 0.025 1,800 IS 15 1 5 0.1 r Sofatone* * Mercury (organic compounda)-Skin -- Mesityl oxide.................................... 25 Methanethlol, see Methyl mercaptan Methoxychlor..................................... -- 2-Methoxyethanol, see Methyl cellosoiye........ .............................. Methyl acetate.................................. 200 Methyl acetylene (propyne)............. 1,000 Methyl acetylene-propodiene mix ture (MAPP)................................... 1,000 Methyl acrylale-Skln......................... 10 Methylal (dimethoxymethane)........ 1,000 Methyl alcohol (methanol)................ 200 Methylamine ..................................... 10 Methyl amyl alcohol, see Methyl lsobutyl carblnol........................... Methyl (n-amyl) Icetone (2- Heptanone)..................................... 100 C Methyl bromide-Skin....................... 20 Methyl butyl ketone, see 2- Hexanone ............................. Methyl ceUosolve-SUn ................... 25 Methyl cellosolve acetate-Skln.... 25 C Methyl chloride................................. 100 Methyl chloroform........................... 350 Methylcyclobexane........................... 500 Methytcyclohexanol........................... 100 o-Metbylcydohexanone-Skin ......... 100 Methyl ethyl ketone (MEK), see 2-Butanone ................................... Methyl formate................................. 100 Methyl iodide - Skin......................... 5 Methyl lsobutyl carhlnol-Skln......... 25 Methyl lsobutyl ketone, see Hexone Methyl isocyanate - Skin................. 0.02 **C Methyl mercaptan............................. 10 Methyl methacrylate......................... 100 Methyl propyl ketone, see 2-Pen- eeeeeeeeeeeeeeeeeeeeeee *C Methyl silicate................................... C cc Methyl styrena............................. C Methylene bisphenyl Isocyanate (MDQ .......................................... . Methylene .ehlorids .(dlehlnromethane)......................................... Molybdenum (soluble compounds).. (Insoluble compounds) Monomethyl anlllne-SUn................. C Monomethyl hydrazine-Skin........... Morpholine-Skin............................... Naphtha (coal tar)............................. 5 100 0.02 500 2 0.2 20 100 0.01 100 15 610 1,650 1,800 35 3,100 260 12 465 80 80 120 210 1,900 2,000 470 460 250 28 100 0.05 20 410 480 0.2 1,740 5 15 9 0.35 70 400 * IMS Addition 11 ji L SGP 0006421 Vikiim Naphthalene.................... .............. t -Naphtbylamlne.......................... Nickel carbonyl.............................. Nickel, metal and aoluble cmpda. Nlcottne-SUn.................................. Nitric acid......................................... Nitric odds....................................... p-Nltroanlline-SUn........................ Nitrobenzene -Skin........................... p-Nltrochloro-benzene-SUn......... Nitroethane...................................... C Nitrogen dioxide.............................. Nitrogen Trifluorlde...................... C Nitroglycerin-Skin.......................... Nitromethane................................... 1-Nitropropnne................................ 2-Nitropropane................................ N-Nltroeodlmethyl-amlne (Dl- . methyi-aitroeoamlnel-Skin.... Nltrotoluene-Skln............................ Nltrotrlchloromethane, see Chloroplcrin................................. Octachlorooapbthalene-Skln......... * Octane.............................................. Oil mist (mineral).......................... Osmium tetraxida............................ Oxalic acid....................................... Oxygen difluoride............................. Ozone .............................................. Paraquat-Skin................................ Parathian-Skla................................ Pentaborane.................................... Pentachlorcnaphthalene-SUn .... Pentachlorophenol-Skla................ Pentane .......................................... 2-Pentanone..................................... Perchloroethylene.......................... Perchloromethyt mercaptan......... Ferchloryt fluoride........................ ** Petroleum Distillates (naphtha)... Phenol-SUa..................................... p-Phenytene dlamine-SUa............ Phenyl ether (vapor)....................... . Phcoirl.ether^Blphnnyi mlTtuee .. (vapor).......................................... Pbenylethylene, see Styrene......... Phenyl dycidyl ether (PGE)......... Phenylhydrazlne-Skin.................. .. Pbosdrln (Mevlnphoa)* -Skin... Phosgene (carbonyl chloride) .... Phosphine........................................ 10 0.001 - 2 25 1 1 - 100 5 10 0.2 100 25 25 . 5 500 0.05 0.1 0.005 - 1,000 200 100 0.1 3 500 3 1 1 10 3 0.1 0.3 v/a3 M , A 0.007 1 0.5 5 30 5 5 1 310 29 2 250 90 90 Al 30 0.1 2,350 5 0.002 1 0.1 0.2 0.5 0.1 0.01 0.5 0.5 2,950 700 570 0.5 13.5 2,000 19 0.1 7 7 SO 23 0.1 0.4 0.4 -- -- Motto* at htisiU* Hungs 11 Vfbsttc Phosphoric acid................................ Phosphorus (yellow)........................ Phosphorus pentachlorlde.............. Phosphorus pentasullide.......... . Phosphorus trichloride.................. Phthalic anhydride.......................... Picric acid-SIda.............................. Plval* (2-Plvalyl-l,3- indandlone).................................... f Platinum (Soluble Saits).................. Polytetrafluoroethylene decomposition products .............. Propane.............................................. 0 Propiolactone................................ * Propargyl alcohol-Skln................... o-Propyl acetate.............................. Propyl alcohol............................ ... n-Propyl nitrate.............................. Propylene dicblortde....................... Propylene 1mine-SUa....................... Propylene oxide................................. Propyne, see Methylacetylene.... Pyrethrum.......................................... Pyridine............................................ Quinooe............................................... RDX-Skln.......................................... Rhodium, Metal (urns and dusts... Soluble salts................................... Ronnsl................................................. Rotenone (commercial)................... Selenium compounds (ss 8s)........... Selenium hexafluoride..................... Silver, metal end soluble compounde..................................... Sodium fluroscetsts (lOSO)-SUn... Sodium hydroxide.............................. Stlbine................................................. * Stoddsrd solvent............................... Strychnine........................................... **C Styrene monomer (pbenylethylene). Sulfur dioxide..................................... Sulfur hexafluoride........................... Sulfuric add....................................... Sulfur monochlorids........ ................ -flulfnr.peaUJluovide......................... Sulfuryl fluoride............................... Systox, eee Demetou* 3,4,5 T.............................................. Tantalum............................................. TEDP-SUn......................................... Teflon * decomposition products.. Tellurium.......................................... * * 0.5 2 - , - 1,000 1 200 200 25 75 2 100 5 0.1 0. 35 . * 0.1 500 100 5 1,000 1 0.025 5 - lMMdtta 1 0.1 1 t 3 U 0.1 . 0.1 0.002 A* 1,800 A1 840 500 110 350 5 240 5 15 0.4 1. 5 0.1 0.001 15 5 0. 2 0.4 0.01 0.05 2 0.5 2,900 0.15 420 13 6,000 1 3 0.035 20 10 5 0.3 A* 0.1 13 SGP 0006422 Tellurium hexafluoride.................. TEPP - Skin .................................... ! Terpbenyls........................................ 1, 1, 1, 2-Tetrachloro-2, 2-dlfluoroethane.................................. I, 1, 2, 2-Tetrachloro-l, 2-difluoroethane.................................. t, 1, 2, 2-Tetrachloroethane-Stdn Tetrachloroethylene, see Per- chlorocthylene.............................. Tetrachtoromethane, see Carbon tetrachloride.............. '................ Tetrachloronaphthalene - Skin___ 1 Tetraethyl lead (as Pb) - Skin___ Tetrahydrofuran.............................. ' Tetramethyl lead (TML) (as Pb) - Skin................................................ Tetramethyl succloonitrile - Skin. Tetranitromethane.......................... Tetryl (2, 4, 6-trlnitrophenyl- methylnitramlne) - Skin............... ThalUum (soluble compounds) - Skin................................................ Thiram.............................................. Tin (inorganic cmpds, except S11H4 and Sn02>...................................... Tin (organic cmpds)......................... Titanium dioxide.............................. Toluene (toluol)................................ 1 Toluene-2, 4-diisocyanate............ o-Toluidine - Skin .......................... Taxaphene, see Chlorinated cam- phene .............................................. Trtbutyl phosphate........................... 1, 1, l-Trlchloroethane, see Methyl chloroform....................... 1, 1, 2-Trlchloroethane - Skin ... Trichloroethylene .......................... Triehloromethaae, see Chloro form................................................ Trichloronaphthalene - SUn........... 1, 2, 3-Trichloropropaae............... 1, 1, 2-Trichloro 1, 2, 2-tri- fluoroethane.................................. TMetaytamlne.................................. Trtfluoromonobromomethane........ 2, 4, 8-Trlnltrophenol see Picric acid................................................ 1, 4, 6-TrlnUropheaylmethylnl- tramine, see Tetryl.................. Trinitrotoluene - Skin................ . Triorthocresyl phosphate............ 0.02 1 500 500 5 - - 200 - 0.5 1 * . 200 0.02 5 10 100 - so 1,000 25 1,000 * Sea Nonce of 14 t/J 0.2 0.05 9 4,170 4,170 35 2 0.075 590 0.075 3 8 1.5 0.1 5 2 0.1 IS 750 0.14 22 5 laktlaaca ^ Triphenyl phosphate......................... - * Tungsten b Compounds, as W Soluble .......................................... - Insoluble........................................ - Turpentine........................................ 100 * Uranium (natural) soL & insoL compounds at U..................... - C Vanadium (V2O5 dust)..................... - (V2O5 fume)..................... - Vinyl benzene, see Styrene............ C Vinyl chloride................................... 500 t Vinylcyanlde, see Acrylonitrile.... Vinyl toluene................ ................... 100 Warfarin .......................................... - Xylene (xylol).................................... 100 t XyUdine - Skin.................................. 5 Yttrium.............................................. - Zinc chloride fume........................... - Zinc oxide fume................................. - Zirconium compounds (as Zr)........ - -,/B* s 1 5 560 0.2 0.5 0.1 1,300 480 0. 1 435 25 1 1 5 5 Radioactivity: For permissible concentrations of radioisotopes in air, see U.S. Department of Commerce, National Bureau of Standards, Handbook 69, "Maximum Permissible Body Burdens and Maximum Permlaaibis Concentrations of RadionucUdas la Air and in Watsr for Occupational Exposurs," June 5,1859. Also, see U.S. Department of Commerce National Bureau of Standards, 59, "Permissible Doss from External Sources of Ionis ing Radiation," September 24, 1954, and addendum of April 15, 1958. 45 535 5 300 7,600 too 6,100 il t V L5 0.1 1991 Adtfttlaa IS 1r~ Li SGP 0006423 MINERAL OUSTS SILICA Crystalline Quartz, Threshold Limit calculated _ from the formula.............................. 250 *' %S162 + T * Cristobalite " " " Amorphous, Including natural dlatomaceous earth............................ 20 SILICATES (less than 1% crystalline silica) * Asbestos.............................................. Mica...................................................... Soapstone.............................................. Talc...................................................... Tremolite............................................ Portland Cement................................. 5 20 20 20 5 50 GRAPHITE (natural).................................. 15 'Inert" or Nuisance Particulates 50 (or 15 mg/M3 whichever Is the see Appendix D smaller)of total dust < 1% SIOj Conversion factors mppcf x 35.3 * million particles per cubic meter 9 particles per c. c. ) ftUilloM of pirtdw pir coble toot at air, bmd ao Uapteger mmpli counted by Ugttf-Oeld tedMdea* t) The ptreaab|t at cryatelliae lilieo la tot toraaila la tea aaaat determined from alr*baroc --flee except la ttooee * la vttcti other meteeda bore beta abowm to be eppUcabte. ie NOTICE OF INTENDED CHANCES These substances, with their corresponding values, com* prise those for which either a limit has been proposed for the first time, or for which a change In the "Adopted" listing has been proposed. In both cases, the proposed limits should be considered trial limits that will remain la the listing for a period of at least two years. During this time, the previously Adopted Limit will remain in effect. If, after two years no evidence comes to light that questions tbs appropriateness of the values herein, the values will be placed In the "Adopted" list. Documentation Is available for each of these substances. Substance -e/1 * + C Ammonia............................................ 2-Acetylaminofluorens .................. f 4-Aminodiphenyl.............................. Ammonium chloride fume.............. Asphalt (Petroleum) fumes............ Butyl mercaptan.............................. C Cadmium oxido turn* (as Cd)......... c Dlchloraacetylene............................ f 4* Dlchlorobenzldlne............................ 4- 4- 4-Dimethylaminoaxobenzene.......... Endosulfan (Thiodan ) - Skin ... Ethyl mercaptan.............................. 4- Fibrous glass .............................. Heptane.............................................. Hydrogen peroxide.......................... Indene ................................................ f Mercury vapor, inorganic and or ganic empds, excluding alkyl Mercury - Skin............................ Methyl 2-cyanoacrylate................... Methyl demeton - Skin .................. Methyl Uoamyl ketone*.................. Methyl mercaptan............................ Methyl pnrmthion Skin................... 4 4 4-Dtmethytamlnaaaobeenene........... Octane................................................. % Oil mist (particulate)....................... Oil vapors.......................................... 50 0.5 0. 1 0.5 s) 500 1 10 2 100 0.5 400 . AJ 35 Al A* 1 2 0.1 A1 A* 0.1 Appendix D 2,000 1 0.05 0.5 475 " 0.1 Al thane) ............................................ - 0 Pentane.............................................. 500 15 1,500 to Ptto at vapor or pa per million parte ot anateaitaated air bp fokoa at ttC and HO aa, Bg preeeure. b) Appradaoh llllgrema at particulate per euMe aaeter at air. tMtRcvtetoa 1M AddLttaa rr SGP 0006424 SvkstOAC* Petroleum distillates....................... + Phenothiazine - Skin ...................... Stoddard Solvent............................... + Styrene.............................................. Tetraethyl lead (as Pb) - Skin .... Tetramethyl lead (as Pb) - Skin... Trimethyl benzene........................... * + vinyl acetate.................................... + + Wood Dust (total dust).................... pp-*> ^ A3 200 100 25 10 - mg/M*! M 5' 0.1001} 0. ISOJI 10 g) < S-7 e Dtametar. No TLV for coarse fibrous (lam baa yet been set. h) As sampled by method that doss sot collect enpors. I) According to analytically determined composition. 1) For control or general room air: biologic monitoring Is essentia! for personnel control. * UtSRsvtaioa It NOTICE OF INTENDED CHANCES (Continued) MINERAL DUST Substance Asbestos + + Coal Dust (bituminous) Crtstobalite Quartz 12 fibers/ml * 5 in length*', or 2 mppcf 3.5 mg/M3 (respirable dust) n) Use one-hall the value calculated from the count or mass formulae (or quartz. (1) TLV (or respirable dust la mg/M3: p) 10 aut/M3 % Respirable Quartz * 2 (2) "Total dust" respirable and nonresplrabie: . 30 mg/M3 % Quartz i ++ Fused SUlca Trldymlte Use quartz formulae. Use one-half the value calculated from formulae lor quartz. ) As determined by the membrane alter method at 430 i phase eonbast mscnllicaaoo. ) As counted by tbs ataretard taaptafer, llgbt-fleld count technique. a) 1 Tteeptrable" dust ss defined by the British Medical Research Council Criteria U) and as sampledby adevice prodicleg equivalent results (*). (1) Batch, T.B. and Gross, P,, Pulmonary DsposMcn tad Retention of Inhaled Aerosols, p. 14*. Academic Preen, NS* York, New York, 1964. (Z) hderim Glide for Resstrabls Mam Sampling, ABA Aerosol Tsebnalngy Commtttm. In draft form, to bn published la late IMP. p) Both concentration and per cent quarts tor the eppUcsttoo of tain limit are to be determined humme traction passim > aiss-mlector with the toUowtng cberacterlatice: Aerodynamic Diameter (s) (unit density sphere) <2 t 2.5 3.5 5.0 10 % penning selector __________________ 90 75 50 35 0 I960 Revision 1949 Addition 19 SGP 0006425 APPENDIX A \1 Because of the high incidence of cancer, either In man or in animal*, no exposure or contact by any route, respiratory, oral or skin should be permitted for the compounds: 2-Acetylaminofluorene 4-Aminodiphenyl Benzidine b its salts Dichlorobenzidine 4-Dimethylaminoazobenzene beta-Naphthylamine 4-Nitrodipbeoyl N-Nitrodimethylamine beta-Propiolactone Because of the extremely high Incidence of bladder tumors in workers handling beta-naphthylamine and the potential carcinogenic activity of the other compounds, the State of Pennsylvania prohibits the manufacture, use and other activities that involve >" exposure without express approval by the Department of Health. A2 Polytetrafluoroethylsne* decomposition product*. Thermal decomposition of the fluorocarbon chain in air leads to the formation of oxidized products carbon, fluorine and oxygen. Because these products decompose in part by hydrolysis in alkaline solution, they can be quantitatively determined In air as fluoride to provide an Index of exposure. No TLV is recom mended pending determination of the toxicity of the products, but air concentrations should be minimal. A2 Gasoline <rtd/or Petroleum OfstlIlate*.The composi tion of these materials varies greatly and thus a single TLV for all types of these material* is no longer applicable. In general, the aromatic hydrocarbon con tent will determine what TLV applies. Consequently the content of benzene, other aromatics andadditives should be determined to arrive at the appropriate TLV (Elkina, et aL A.LH.A.J. 24, M, 1963). ......APMMWX'*! B.1 THRESHOLD LIMIT VALUES FOR MIXTURES When two or more hazardous substances are present, their combined .effect, rather than that of either Indi vidually, should be given primary consideration, in the shsanrt of information to the contrary, the effects of the different hazards should be considered as additive. That Is, U the sum of the following fractions. 20 Cn TI exceeds unity, then the threshold limit of the mixture should be considered as being exceeded. Cj Indicates the observed atmospheric concentration, and Tj the corresponding thres hold limit, (See Example IAju). V 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 ^Ci, or^Ct2c,, .) itself 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 oust be determined individually. Potentiating or antagonistic agents are not necessarily harmful by them selves. Potentiating effects of exposure to such agents by rou a other than that of inhalation is also possible, e.g. lml led alcohol and Inhaled narcotic (trichloroethylene). Pot itlatlon is characteristically exhibited at high con cent atioaa, leas probably at low. 4 m a given operation or process characteristically emits a cumber of harmful dusts, fumes, vapors or gases. It will frequently be only feasible to attempt to evaluate the haiard by measurement of a single substance. In such cases, the threshold limit used for this substance should be reduced by a eultahle factor, the magnitude of which will depend on the number, toxicity and relative quantity of the other contaminants ordinarily present. rumples at processes which are typically associated with two or more harmful atmospheric contaminants are welding, automobile repair, blasting, pointing, lacquering, certain foundry operations, diesel exhausts, etc. (Ex ample 24 1 Lj SGP 0006426 THRESHOLD LIMIT VALUES FOR MIXTURES EXAMPLES 1A. General case, where air Is analyzed {or each component. a. ADDITIVE EFFECTS *. L, Si* T{ T2 T3 1 Air contains 5 pprr of carbon tetrachloride (TLV, 10), 20 ppm of ethylene dichlorlde (TLV, 50) and 10 ppm of ethylene dibromide, (TLV, 25). 5 , 20 ^ 10 . 65 TIT TiT * TT HT 1.3 Threshold limit is exceeded. b. INDEPENDENT EFFECTS Air contains 0.15 mg/M3 of lead (TLV, 0. 2) and 0.7 mg/M3 of sulfuric acid (TLV, 1). 0.15 0.20 0.75; 0.7 1 Threshold limit is not exceeded. 0.7 IB. Special ease when source of contaminant is a mixture and atmospheric composition is assumed similar to that of original material, i. e. vapor pressure of each component is the same at the ob served temperature. a. ADDITIVE EFFECTS, approximate solution. 1. A mixture of equal parts (1) trichloro ethylene (TLV, 100), and (2) methyl chloroform (TLV, 350). Cl ,, C2 100 -350 cm im Cl * c2 ' I Cm Solution applicable to "spot" solvent Diiztwevn{v,,vitors all or nearly all, sol vent evaporates. Cl + Cj 2Ct 100 350 23 7Cj 2Ci 2Cj 766 * 706 * To Tm 700 x | * 155 ppm IB. b. General Exact Solution for Mixtures of N Components With Additive Effects and Different Vapor Pressures. (1) Ci C2 Cn TT+ Tp- -+tT* (2) Cx C2 . . . CB T; (2.1) C! C2 T* T + l. By the Law of Partial Pressures, (3) Ct - apj, I and by Raoult's Law, (4) Pi * FiPl. i Combine (3) and (4) to obtain (5) Ci aFiPi. Combining (1), (2,1) and (5), we obtain (8) FiPi0 F2pj FnPn FlPl F2P2 + . . FnPn and solving for T, T.p* FjPjO* (6.1,T-pJpJ0 F2pjtr-- . . Fnprn l p-- *T" Fnnpn7" I rl t2 a or *i F,lP'l t (8-T -rfr 0 * fipi i - i ---- Ti 23 r~ 1 1i SGP 0006427 T > Threshold Limit Value In ppm. C Vapor concentration In ppm. p Vapor pressure of component in solution. 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 1 refers to an arbitrary com ponent from 1 to n. Absence of subscript relates the quantity to the mixture. Solution to be applied when there is a reservoir of the solvent mixture whose composition does not change appreciably by evaporation. Exact Arithmetic Solution of Specific Mixture Mol. Density T pat Mol fraction wt. 25C in half-andhalf solution by volume Trlchlo oethylem (1) 131.4 1.48g/ml 100 73mm Hg 0.527 Methyl Uoroform (2) 133.42 1.33g/ml 350 125mm Bg 0.473 Vi (0.527) (73) 38.2 Va (0.473) (125) - 58.2 38.2+ 59.2 (97.4) (J50 sff.ar. a " issJ : w* tst 177 T 177 ppm (Note difference In TLV when account is taken of vapor pressure ' -snd-meb traction. in rnmpsstsin with above example where such account Is not taken.)2 2. A mixture of one part of (1) parathion (TLV, 0.1) and two parts of ( EPN (TLV, 0. S). m' CV O' 2C, 24 t C-SC1 C1 *C1 JC. inurr 7C, sc. 5T = Tm z . o.21 mg/M3 1C. TLV for Mixtures of Mineral Dusts. 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 SO. For a mixture containing 80% talc and 20% quarts, the TLV for 100% of the mixture "C" is given by: 1 TLV* a.g a.T * 8-4mppcl ~3r*rs Essentially the sane result will be obtained If the limit of the more (moat) toxic component Is used provided t v effects are additive. In the above example be limit for 20% quarts is 10 mppef. For another mixture of 25% quarts 25% amor phous silica and 50% talc: TLym fl.H O.K '6.T 13 "W* TT V TT Tbs limit for 29% quarts approximates 8 mppef. 29 1 J SGP 0006428 APPENDIX C BASES FOR ASSIGNING LIMITING "C" VALUES By definition in the Preface, a listed value bearing 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 asssigning or not assigning a "C" value rest on whether excursions of concentration above a proposed limit for periods up to IS minutes may result in a) intolerable irritation, b) chronic, or irreversi ble tissue change, or c) narcosis of sufficient degree to Increase accident proneness, impair self rescue or ma terially reduce work efficiency. T.L.V. Test RANGE T.L.V. ppm or mg/M13 * Factor Examples 0 to I 1 * to 10 10 to 100 100 + to 1000 3 J 1.5 1.2S Toluene diisocyanate-T.L.V., 0.02 ppm, if permitted to rise above 0.06 ppm may result in sensitization in a single sub sequent exposure. "C" listing recommended on category b. Manganese - T.L.V., 5mg/M3, contains little or no safety factor. All values should fluc tuate below Smg/M3. "C" lut ing recommended on category b. Methyl styrene - T.L.V. 100, if encountered at leveU of ISO ppm will prove intensely irritating. "C" Listing recom mended on category a. Methyl chloroform - T.L.V. 350 ppm, at 438 ppm for per iods not exceeding 15 minutes U not expected to result in untoward effects relating to category c. No "C" listing recommended. 28 PERMISSIBLE EXCURSIONS FOR TIME. WEIGHTED AVERAGE (TWA) LIMITS The test TLV Factor in the Table serves also as a guide to the magnitude of the permissible excursion above the limit for those substances not given a "C" designation i.e. the TWA limits. Thus for HF, with a TWA limit of 3 ppm, a concentration of 6 ppm is permissible for periods not exceeding 15 minutes, provided an equivalent exposure below the limit is experienced. APPENDIX D Some "Inert" or Nuisance Particulates R| Alundum (AI2O3) Calcium carbonate Cellulose Portland Cement Corundum (AI2O3) Emery Glycerine Mist Graphite (synthetic) Gypsum Vegetable oil mists (except castor, cashew nut, or similar irritant oils) Limestone Magnesite Marble Pentaerythritol Plaster of Parts Rouge Silicon Carbide Starch Sucrose Tin Oxide Titanium Dioxide ^ When toxic impurities are not present, e. g. quartz < 1%. APPENDIX E Some Simple Asphyxiants - "Inert" Gases aid V<g>ors Acetylene i Argon , Ethans Ethylene j Helium Hydrogen Methane Neon Nitrogen Nitrous Oxide Propane 1 i 21 r~ Li SGP 0006429 RECEIVED NOV 2 ' 1971 GEORGIA-PACIFIC CORPORATION A~.C`MICE, TEXAS SGP 0006430