Document 82RG8a742RmO4LjOLY2Gwbg3y

INDUSTRIAL HYGIENE OF AIRBORNE C02STTlAJ^I3SLA^rTS Oooupational Healtti Regulation No. 3 TEXAS STATE DEPARTMENT of HEALTH Division of Occupational Health i and Radiation Control ts Reprinted with permission from the American Conference of Govenanental Industrial Hygienists granted in a letter from Mr. Vernon E. Rose, _ Secretary-Treasurer, dated November 30, 1970. " .' The Texas Scete Board of Health approved on 7 March 1971 the reproduction of the recommendations on "Threshold Lisle Values of Airborne Contaminants" adopted by the American Conference of Governmental Industrial Hygienists at their 1970 annual meeting. They are promulgated In accordance with Article 4418d of the Revised Civil Statutes, State of Texas and also Article 4477, Section 19. "The Texas State Department of Health shall make available to the citizens of Texas current Information concerning minimum allowable concentrations of toxic gases and such environmental standards as may pertain to the health and safety of the employees of Industrial establlshants In this State." CONTENTS I. Scope; Purpose; Definitions; Availability of Pertinent References ............. ................ .............................................. II. Applicability of FiguresListed Herein ................................................ III. Source .................................................................................................................. IV. Documentation of Threshold Limit Values ........................................... V. Ceiling vs Time-WeightedAverage Limits .............................................. VI. "Skin" Notation .............................................................................................. VII. Mixtures ............................................................................................................. VIII. Nuisance Dusts ................................................................................................. IX. Simple Asphyxiants -"Inert" Gases orVapors ................................... X. Physical Factors ........................................................... XI. "Notice of Intent" ........................................................................................ XII. As Legislative Code ...................................................................................... 1 1 2 3 3 3 3 4 4 4 5 6 (continued) XIII. Adopted Value* (Gaaea, Vapor*, Toxic biata. Fume* and Miata) ................................................................................................... A. Mineral Dueta ....................................................................................... B. Notice of Intended Change* (for 1970) ............... ..................... XIV. Appendixa* ...................................................................................................... A. Appendix A ........................................................................................... B. Appendix B........... ........................ C. Appendix C ............................ .............. ................................................ D. Appendix D........................... E. Appendix E.......................................... 6 17 18 21 21 22 28 29 30 Reprinted with pemlaalon froa the American Conference of Governmental Induatrlal Byglenlata granted In a letter fren Mr. Vernon E. Roae, Secretary-Treaaurer, dated November 2, 1970. THRESHOLD LIMIT VALDES OF ATMOSPHERIC CONTAMINANTS IN PLACES OF EMPLOYMENT I. SCOPE; PURPOSE; AVAILABILITY OF PERTINENT REFERENCES Scop*: Thla information bulletin applies to all placaa of snrploymant in Ttxaa. It do*a not cover marlmim pcrmiaaibl* concentration* of radioactive material* or the environmental aanitatlon requirement*, nor doea it Include meaaure* required for control of canunlty external air pollution or air pollution nulaancea. Purpoae: The purpoae of thla regulation 1* to preaent to employers the racoonended maxiaum average atmoapherlc concentration of contaminant* to vhleh they are permitted to expoae employee* during an eight-hour working day in their place* of employment, including lnduatrlal eatabllahmenta. Definition*: 1. lnduatrlal Establishment la defined to mean an inatltutlon, a place, building or location related to manufacture* or to the product of industry or labor. 2. Flacea of Employment 1* defined to mean any place where two or more peraona are directly or indirectly employed by another for direct or indirect gain or profit. Pertinent Raferencea: Cople* of related lawa, regulations, opinions of the Attorney General of Texas, and Advisory Standards currently applicable will be provided to any citizen of Texas upon request. II. APPLICABILITY CP FIGURES LISTED HEREIN Threshold limit values refer to airborne concentrations of substances and represent conditions under which it la believed that nearly all workers may be repeatedly exposed day after day without adverse affect. Because of wide variation in Individual susceptibility, however, a small percentage of workers may experience discomfort from same 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 occupational lllneas. Simple tests are now available (J. Oecup. Med. 9, 537, 1967; Ann. N.T. Acad. Scl., 151 Art. 2, p. 968, 1968) that may be used to detect those individuals hypersusceptlble to a variety of Industrial chemicals (respiratory Irritants, hemolytic chemicals, organic isocyanates, carbon disulfide). These tests may be used to screen out by appropriate job piacaatent Che hyperreactive worker and thus in effect improve this "coverage" of the TLV's. Threshold limit values refer to time-weighted concentrations for a 7 or 8-hour workday and a 40-hour workweek. They should be used as guides in the control of health hazards and should not be used as fine lines between safe and dangerous concentrations. (Exceptions are the substances listed in Appendices A and E and those substances designated with a "C" or Ceiling value. Appendix C.) Time weighted averages permit excursions above the limit provided they are compensated by equivalent excursions below the limit during the workday. In some Instances it may be permissible to calculate the average concentration for a workweek rather than for 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 la a rule of thumb and in certain cases may not apply. The amount by which threshold limits 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 concentratlons--even for short periods--produce acute poisoning, whether the effects are cumul ative, the frequency with which high concentrations occur, and the duration of such periods. All factors must be taken into consideration in arriving at decision as to whether a hazardous condition exists. III. SOURCE Threshold limits are based on the best available 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; protection against Impairment of health may be a guiding factor for 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 concentrations, 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 industrial hygiene and should be 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 consunity air pollution or air pollution nuisances, (3) in estimating the toxic potential or.continuous uninter rupted exposures, (4) as proof or disproof of an existing disease.or ... physical conditions, or (5) for adoption by countries whose working conditions differ from those in the United States of America and where substances and processes differ. -2 - t i IV. DOCUMENTATION OF THRESHOLD LIMIT VALDES A separate companion place to the TLVa la Issued by ACGIH under this title. Thla publication glvea the pertinent aclentific Information and data with reference to literature aourcea, 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. V. 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 inappro priate. 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 celling "C" limit that should not be exceeded. It is implicit in thesa definitions that the manner of sampling to determine compliance with the limits for each group oust differ; a single brief sample, that is 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 concen trations 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 pegged 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 Connittee in making a judgment whether to include or exclude a substance for a "C" listing. VI. "SKIN" NOTATION Listed substances followed by the designation "Skin" refer to the potential contribution to the over-all exposure by the cutaneous route including mucous membranes and eye, either by airborne, or more part icularly, by direct contact with the substance. Vehicles can altar skin absorption. This attention-calling designation is Intended to suggest appropriate measures for the prevention of cutaneous absorption so that the threshold limit la not invalidated. VII. MIXTURES Special consideration should ba given also to the application of the TLVs in assessing the health hazards 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, mspllflad by specific examples are given in Appendix B. -3- VIII. NUISANCE OUSTS In contrast to flbrogenic dusts which causa scar tlssua to ba formed in lungs whan inhalad in excessive amounts, so-called "nuisance" dusts hava a long history of llttla adverse effect on lungs and do not produce significant organic dlsaasa or toxic affect when exposures are kept under reasonable control. The nuisance dusts have also been called (biologically) "inert" dusts, but the latter term la inappropriate to the extent that there is no dust which does not evoke some cellular response in the lung when Inhaled in sufficient amount. However, the lung-tissue reaction caused by inhalation of nuisance dusts has the following characteristics: 1) The architecture of the air spaces remains Intact. 2) Collagen (scar tissue) is not formed to a signif icant axtent. 3) The tlssua reaction is potentially reversible. Excessive concentrations of nuisanca dusts in the workroom air may seriously reduce visibility (iron oxide), may cause unpleasant deposits in the eyes, ears and nasal, passages (Portland Cement dust), or cause injury to the skin or mucous membranes by chemical or mechanical action "per se or by the rigorous skin cleansing procedures necessary for their removal. * A threshold limit of 10 mg/K , or 30 mppcf, of total dust<11 S102, whichever is less, is recoesaended for substances in these categories and for which no specific threshold limits have been assigned. This limit, for a normal workday, does not apply to brief exposures at higher concentrations. Neither does it apply to those substances which may cause physiologic impairment at lower concentrations but for which a threshold limit has not yat been adopted. Some "inert" particulates are given in Appendix D. IX. SIMPLE ASPHYXIANTS - "INERT" GASES OR VAPORS A number of gases and vapors, when present in high concentrations in air, act primarily at simple asphyxiants without other significant physiologic effects. A TLV may not be recommended for each simple asphyxiant because the limiting factor is the available oxygen. The minimal oxygen content should be 18 percent by volume under normal atmospheric pressure (equivalent to a partial pressure, p02 of 133 mm Hg). Atmospheres 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. X. 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 eltered. Most of these stresses act adversely 'to Increase the toidc 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 -4 - substances are not of such a magnitude as to take care of gross devia tions. For example, continuous work at temperatures above 90 F or over-time extending the workweek more than 25X, might be considered gross deviations. In such instances judgment must be exercised in the proper adjustments of the threshold limit values. XL. "NOTICE OF INTENT" At the beginning of each year, proposed actions of the Coomictee for the forthcoming year are Issued in the form of a "Notice of Intent." This Notice provides not only an opportunity for consent, but solicits suggestions of substances to be added to the list. The suggestions should be accompanied by substantiating evidence. The list of Intended Changes follows the Adopted Values in the TLV booklet. HI. AS LEGISLATIVE CODE The Conference recognises that ths TLVs may be adopted in legislative codes and regulations. If so ussd, 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 by the Committee on Threshold Limits for ravlslon or additions, as further information becomes available. XIII. ADOPTED VALDES (Gates, Vapora, Toxic Dusca, Pune* and Miaca) (In Alphabetical Order) Substance Abate ........................................................ Acetaldehyde ......................................... Acetic acid ........................................... Acetic anhydride ................................ Acetone ............... ................................... Acetonitrile ......................................... Acetylene ............................ .................. Acetylene dichloride, aee 1, 2- Dichloroethylene ............................ Acetylene tetrabroed.de .................... Acrolein ................................................. Acrylamide-Skin.......................... .. Acrylonitrile-Skin ............................ Aldrin-Skin ........................................... Allyl alcohol-Skin ............................ Allyl chloride ..................................... **C Allyl glycidyl ether (ACS) ........... Allyl propyl diaulflde .................... Allundum (AljOj) ................................ 2-Amlnoethanol, aee Ethanolamine 2-Aminopyridine .................................. ** Ammonia ....................................................... Ammonium aulfamate (Aanate) ......... n-Amyl acetate .................................... sec-Amyl acetate ................................ Aniline-Skin ......................................... Anisidine (o, p-isooars)-Skln ... Antimony & Compounds (aa Sb) .... ANTU (alpha naphthyl thiourea) .. Argon ....................................................... Arsenic & Compounds (ea Aa) ......... Arsine ..................................................... Azlnphos-methyl-Skin ........................ Barium (soluble compounds) ........... C Benzene (benzol)-Skin ...................... Benzidine-Skin .................................... p-Benzoqulnone, see Qulnone ..... Benzoyl peroxide ................................ Benzyl chloride .................................. Beryllium............................................... Biphenyl, aee Diphenyl ................... Blsphenol A, see Dlglycldyl ether Boron oxide ........................................... Boron trlbroailde ................................ C Boron trlfluoride .......................... B_a) 22_ 200 10 5 1,000 40 E 1 0.1 20 2 1 10 2 0.5 50 100 125 5 E 0.05 25 1 1 l ' mg/M^ 15 360 25 20 2,400 70 14 0.25 0.3 45 0.25 5 3 45 12 D 2 35 15 525 650 19 0.5 0.5 0.3 0.5 0.2 0.2 0.5 5 5 0.002 15 10 3 6 Substance a) ppm Bromine ................................................................................... * Bromine pentafluorlde ..................................................... Bromoform-Skin .................................................................... Butadiene (1, 3-butadiene) ........................................... Butanethlol, see Butyl mercaptan ............................ 2-Butanone ............................................................................ 2-Butoxy ethanol (Butyl Cellosolve)-Skin ........... Butyl acetate (n-butylacetate) .................................. sec-Butyl acetate .............................................................. tert-Butyl acetate ............................................................ Butyl alcohol ...................................................................... sec-Butyl alcohol .............................................................. tert-Butyl alcohol ............................................................ C Butylamine-Skin.................................................................. C tert-Butyl chromate (as Cr03)-Skin .......................... n-Butyl glycidyl ether (BGE) ...................................... * Butyl mercaptan .................................................................. p-tert-Butyltoluene ......................................................... Cadmium (Metal dust and solublesalts) .................... *C Cadmium oxide fume (as Cd) .......................................... Calcium carbonate .............................................................. Calcium arsenate ............................................................... Calcium oxide ...................................................................... ** Camphor (Synthetic) ......................................................... Carbary 1 (Sevin R) .............. Carbon black ........................................................................ Carbon dioxide .................................................................... Carbon dlsulfide-Skin............... ;................................... Carbon monoxide ................................................................. Carbon tetrachlorlde-Skin ............................................ Cellulose (paper fiber) ................................................. Chlordane-Skin .................................................................... Chlorinated camphene-Skin ............................................. Chlorinated diphenyl oxide .......................................... * Chlorine ................................................................................. Chlorine dioxide......................................... ...................... C Chlorine trlfluorlde ....................................................... C Chloroacetaldehyde ........................................................... c-Chloroacetophenone(phenacylchlorlde) ................ Chlorobenzene (monochlorobenzene) ............................ 0-Chlorobenzylldene melononitrile (0CBM) .............. Chlorobramoeiethane ........................................................... 2-Chloro-l, 3-butadiene, see Chloroprene ............. Chlorodlphenyl (421 Chlorine)-Skin ......................... Chlorodiphenyl (541 Chlorine)-Skin .......................... 1-Chloro, 2, 3-epoxypropane, see Epichlorhydrin ................................................................ 2-Chloroethanol, see Ethylene chlorohydrln Chlorocthylene, see Vinyl chorlde ............... 0.1 0.1 0.5 1,000 200 50 150 200 200 100 150 100 5 -50 0.5 10 --- ---2 --- 5,000 20 50 10 ----- 1 0.1 0.1 1 0.05 75 0.05 200 --- -7- 3b) mg /M 0.7 0.7 5 2,200 590 240 710 950 950 300 450 300 15 o.l 270 1.5 60 0.2 0.1 D 1 5 5 3.5 9,000 60 55 65 D 0.5 0.5 0.5 3 0.3 0.4 3 0.3 350 0.4 1,050 1 0.5 Substance PPm*^ mg/M3b> C Chloroform (trichloromethane) .................................... 1-Chloro-l-nitropropane ................................................. Chloropicrin ..................................................................... Chloroprene (2-chloro-l, 3-butadiene)-Skin ......... Chromic acid and chromaCaa (aa C1O3) ..................... Chromium, aol. chromic, chromoua aalca aa Cr ... Metal & Insol. aalca .................................... .............. Coal car picch volatiles (ban*ana aolubla frac tion) anehracana, BaP, phasanchrana, acridina, chrysene, pyrene) ......................................................... Cobale, macal fume & dust ............................................. Copper fume ............................ .............................................. Dusts and Mists .............................................................. Corundum (AI2O3) ............................ ................................... Cotton dust (raw) ............................................................. Crag* herbicide ................................................... .............. Cresol (all isamars) - Skin ........................................ Croconaldahyda ................................................... .. Cumene-Skin................................................. ........................ Cyanide (as CM)-Skin ....................................................... * Cyanogen ................................................................................. Cyclohexane .......................................................................... Cyclohexanol .................................................................... .. Cyclohexanone ...................................................................... Cyclohexane .......................... ................................................ Cyclopentadlane .................................................................. 2, 4-D ..................................................................................... DDT-Skin ................................................................................ DDVP, see Dichlorvos ....................................................... Decaborane-Skin .................................................................. Demeeon -Skin ...................................................................... Diacetone alcohol (4-bydroxy-4-mathyl-2pentanone) ................................................... .. 1, 2-Diaminoethane, see Ethylenediamine ............... Diazomethane............... ........................................................ Diborane ............................................... ................................. C 1, 2-Dibromoethane (ethylene dibromids)-Skin ... Dibutyl phosphate........... .................. ............................... Dibutylphtbalate ................................................................ *C Dichloroacetylene ............................................................. C o-Dichlorobenzene ............................................................. p-Dlchlorobenxene ............................................................. Dichlorodifluorooethane ............... ................................. 1, 3-Dichloro-S, 5-dimethyl hydantoin ................... 1, 1-Dichloroethane ......................................................... 1, 2-Dichloroethane ......................................................... 1, 2-Dlchloroethylene ..................................................... C Dlchloroetbyl ether-Skin ............................................... Dichlorooethane, see Mechylenechloride ................. Dichloromonofluoromethane ............................................ 50 20 0.1 25 -- --- -- -- -- -- -- -- -- 5 2 50 -- 10 300. 50 50 300 75 -- -- 0.05 -- 50 0.2 0.1 25 1 0.1 50 75 ..1,000 100 50 200 15 1,000 -- 240 100 0.7 90 0.1 0.5 1 0.2 0.1 0.1 1 D 1 15 22 6 245 5 -- 1,050 200 200 1,015 200 10 1 0.3 0.1 240 0.4 0.1 190 5 5 0.4 300 450 4,950 0.2 400 200 790 90 .4,200 -8- Substance Es!i C 1, 1-Dlchloro-l-nitroethane ........................................ 1, 2-Dichloropropane, Propylenedichloride .. Dichlorotetrafluoroethane ............................................. Dlcblorvot (DDVP)-Skin ................................................... Dialdrin-Skin ...................................................................... Diethylamine ........................................................................ Diethylamino ethanol-Skin ............................................. Diethylene triamine-Skin ............................................... Diethylather, ace Ethyl athar..................... .............. Dlfluorodlbrcoioaiethant ................................................... C Diglycidyl athar (DGE) ................................................... Dihydroxybenzane, aaa Hydroquinone .......................... Dlltobutyl katone .............................................................. Diiaopropylamlne-Skin............................................. Dimethoxymethane, aaa Matbylal .................................. Dimethyl acatamide-Skin ................................................. Dimethylamina ...................................................................... Dimethylaminobaazana, aaa Xylldana .......................... Dimethylanlline (N-dlmethylanillne)-Skln ............. Dimsthylbenzene, aaa Xylene ................................ .. Dimethyl 1, 2-dibramo-2, 2-dichloroethyl phos phate, (Dibrom) .............................................................. Dlmathylforaamide-Skin ................................................... 2, 6-Dimethylheptanone, aaa Dliaobutyl katone .. 1, 1-Dlmethylhydrazine-Skln .................... Dimethylphthalate ............................................................. Dimathylaulfata-Skln ....................................................... Dinitrobanzene (all laomars)-Skin ............................ Dinltro-o-creaol-Skin ..................................................... Dinitrotoluana-Skin ......................................................... Dloxane (Dlathylana dioxide)-Skin ............................ Diphenyl ................................................................................. Diphenyl amine .................................................................... Dtphenylmethane dllaocyanata (aaa Methylene blaphanyl laoeyanate (MDI) ...................................... Dipropylane glycol methyl ethar-Skin ..................... Di-aec, octyl phthalata (Di-2-ethylhexyl- phthalata) ................. ...................................................... Emery ...................................................................................... * Endoaulfan (Thiodan)-Skin .......................................... Endrin-Skln.................................. ....................................... Epichlorhydrin-Skin ......................................................... EPS-Skin ................................................................................ 1, 2-Epoxypropana, aaa Propyleneoxide ............... .. 2, 3-Epoxy-l-propenol, aaa Glycidol ....................... Ethane ............................................................................ .. Ethanethiol, aaa Ethylmarcaptan ................................ Ethanolamine ........................................................................ 2-Ethoxyethanol-Skln....................................................... 2-Ethoxyethylacetate (Calloaolva acetate)-Skin . 10 1,000 --- 25 10 10 100 0.5 50 5 10 10 5 -- 10 0.5 1 -.. 100 0.2 100 mm mm mm 5 -- -- .. E 3 200 100 9 60 7,000 1 0.25 75 50 42 860 2.8 290 20 35 18 25 3 30 1 5 5 1 0.2 1.5 360 1 10 600 5 D 0.1 0.1 19 0.5 --- -- -- 6 740 540 Substance P.m*) Ethyl acetate ...................................................................... Ethyl acrylate-Skin ......................................................... Ethyl alcohol (ethanol) ................................................. Ethylamina ............................................................................ Ethyl sec-amyl ketone (5-methyl-3-heptanone) ... Ethyl benzene ...................................................................... Ethyl bromide ...................................................................... Ethyl butyl ketone (3-Heptanone) .............................. Ethyl chloride .................................................................... Ethyl ether .......................................................................... Ethyl formate .............................................................. Ethyl mercaptan .................................................................. Ethyl silicate ................... ................................................ Ethylene ................................................................................. Ethylene chlorohydrin-Skin .......................................... Ethylenedlamine .................................................................. Ethylene dibromide, aee 1, 2-Dibromoethane ........ Ethylene dichlorlde, aee 1, 2-Diehloroethane ... C Ethylene glycol dinitrate and/or Nitroglycerin- Skin ..................................................................................... Ethylene glycol monomethyl ether acetate, aee Methyl celloaolve acetate ........................................ Ethylene imlne-Skin ......................................................... Ethylene oxide .................................................................... Ethylldine chloride, aee 1, 1-Dichloroetbane ... N-Ethylmorpholine-Skin ................................................... Ferbam........... ................................................................... Ferrovanadium dust............. ................................. ............ Fibrous glass ...................................................................... Fluoride (as F) ................................................................. Fluorine ................................................................................ Fluorotrichloromethane ................................................... **C Formaldehyde ........................................................................ Formic acid .......................................................................... Furfural-Skin ................. .............................................. Furfury1 alcohol ............................................................... Gasoline ................... ............................................................ Glycerin mist ...................................................................... Glycidol (2, 3-Epoxy-l-propanol) .............................. Glycol monoethyl ether, see 2-Ethoxyethanol .... Graphite. (Synthetic) ..................................................... Guthion, see Azinphosmethyl ...................................... Gypsum ........................................................................ .. Hafnium .................................................................................. Helium .................................................................................... Heptachlor-Skln ................................................................. Heptane (n-heptane) ........................................................ Hexachloroethane-Skin ..................................................... Hexachloronaphthalene-Skin .......................................... .Hexane (n-hexane) ............................ ................................. 2-Hexanone ........................................ ................................... 400 25 1,000 10 25 100 200 50 1,000 400 100 0.5 100 E 5 10 0.2") 0.5 50 20 --- --- 0.1 1,000 5 5 5 50 -- 50 -- -- E -- 500 1 -- 500 100 m^//1M3b> 1,400 100 1,900 18 130 435 890 230 2,600 1,200 300 1 850 -- 16 25 -- 1 90 94 15 1 D 2.: o.; 5,600 6 9 20 200, A3 0 150 D D 0. -- 0.. 2,000 10 o.: 1,800 410 10 Substance Hexone (Methyl lsobutyl ketone) ............. sec-Hexyl ecetate ........................................... Hydrazlne-Skln ................................................. Hydrogen .............................................................. Hydrogen bromide ............................................. C Hydrogen chloride ............................ .............. Hydrogen cyenlde-Skln .................................. Hydrogen fluoride ........................................... Hydrogen peroxide ........................................... . Hydrogen selenide ........................................... Hydrogen sulfide ............................................. Hydroquinone ...................................................... * Indene .................................................................. , Indium end compounds, es In ...................... C Iodine .................................................................. . Iron oxide fume ......................................... Iron salts, soluble, as Ft ........................ Isoasiyl acetate ............................................... . Isoamyl alcohol ............................................... , lsobutyl acetate .............................................. Isobutyl alcohol ............................................. . Isophorone ........................................................... Isopropyl acetate ............................................. Isopropyl alcohol ............................................ Isopropylamine ................................................... Isopropylether ................................................... Isopropyl glycldyl ether (IGE) ................. Kaolin .................................................................... Ketene .................................................................... Lead ........................................................................ Lead arsenate ..................................................... Limestone ............................................................. Lindane-Skin ....................................................... Lithium hydride ................................................ L.F.C. (Liquified petroleum gas) ............ Magnesite ............................................................. Magnesium oxide fume ...................................... Malathlon-Skin................................................. . Maleic anhydride .............................................. C Manganese and compounds, as M,^ ................. Marble .................................................................. . ** Mercury-Skin ...................................................... ** Mercury (organic compounds)-Skin ........... Mesityl oxide ................................................... Methane ................................................................ Methanethiol, see Methyl mercaptan .... Methoxychlor ..................................................... 2-Methoxyethanol, see Methyl cellosolve Methyl acetate ................................................. 11 ppm*^ 100 50 1 E 3 5 10 3 1 0.05 10 -10 -- 0.1 --- 100 100 150 100 25 250 400 5 500 50 -- 0.5 ----as. 000 --.* 0.25 -- -- .. 25 E -- .200 m*/M3b> 410 300 1.3 -* 10 7 11 2 1.4 0.2 15 2 45 0.1 1 10 1 525 360 700 300 140 950 980 12 2,100 240 D 0.9 0.2 0.15 D 0.5 0.025 1,800 D 15 15 1 5 D 0.1 0.01 100 15 610 Substance PP** Methyl acetylene (propyne) .......................................... Methyl acetylene-propadiene mixture (MAFP) ..... Methyl acrylate-Skin ....................................................... Methylal (dimethoxymethane) ........................................ Methyl alcohol (methanol) ................... ........................ Methylamine .......................................................................... Methyl amyl alcohol, see Methyl isobutyl carbinol........... ................................................................. * Methyl isoamyl ketone ..................................................... Methyl (n-emyl) ketone (2-Heptanone) ..................... C Methyl bromide*Skin ......................................................... Methyl butyl ketone, see 2*Hexanone ....................... Methyl ceilosolve-Skin ................................................... Methyl cellosolve acetate-Skin .................................. Methyl chloride .................................................................. Methyl chloroform ............................................................. Methylcyclohexane ................................................... .. Methylcyclohexanol ........................................................... o-Methylcyciohexanone-Skin .......................................... Methyl ethyl ketone (MEK), see 2*Butanone ...... Methyl formate .................................................................... Methyl iodide*Skin ........................................................... Methyl Isobutyl carbinoi*Skin .................................... Methyl isobutyl ketone, see Hexone ......................... Methyl isocyanate*Skin ................................................... * Methyl mercaptan ................................................................ Methyl methacrylate ......................................................... Methyl propyl ketone, see 2*Pentanone ................... C Methyl silicate .................................................................. C oc Methyl styrene ............................................................. C Methylene bisphenyl isocyanate (MDX) ..................... Methylene chloride (dichloromethane) ..................... Molybdenum (soluble compounds) .................................. (Insoluble compounds) .............................. Monomethyl anlline-Skin ................................................. C Monomethyl hydrazine-Skin ............................................ Morpholine-Skin .................................................................. Naphtha (coal car) ........................................................... Naphthalene ............................ .............................................. 0- Naphthylamina ............................................................... Neon ......................................................................................... Nickel carbonyl .................................................................. Nickel, metal and soluble cmpds, as N1 ................. Nicotine-Skin.................................... ............ .................... Nitric acid .......................................................................... Nitric oxide ....................................................... ................ p-Nitroanillne-Skin ............................... ...................... .. Nitrobenzene-Skin ....................................................... .. p-Nitrochlorobenzene-Skin ............................................ 1,000 1,000 10 1,000 200 10 100 100 20 25 25 100 350 500 100 100 ' 100 5 25 0.02 0.5 100 5 100 0.02 500 2 0.2 20 100 10 E 0.001 2 25 1 1 1,650 1,800 35 3,100 260 12 475 465 80 80 120 210 1,900 2,000 470 460 250 28 100 0.05 1 410 30 480 0.2 1,740 5 15 9 0.35 ` 70 400 0.007 1 0.5 5 30 6 5 1 - 12 - Substance Nitroethane ................................ ......................... Nitrogen ................................................................ Nitrogen dioxide ............................................... Nitrogen trifluoride ....................................... Nitroglycerin-Skin ........................................... Nitromethane ....................................................... 1-Nitropropane ................................................... 2-Nltropropane ................................................... N-Nitrosodimetbylamine (dimethyl- nitrosoaaine)-Skin ....................................... Nitrotoluene-Skin ............................................. Nitrotrichloromethane, aee Chloroplcrln Nitrous oxide ..................................................... Octschloronsphthalene-Skin .......................... * Octane ................... ................................................ * Oil mist, particulate ...................... * Oil mist, vapor ................................................. Osmium tetroxlde ............................................... . Oxalic acid ......................................................... . Oxygen difluoride .............................................. Ozone ........................................................................ Paraquat-Skin ....................................................... Parathion-Skin ..................................................... Pentaborana ........................................................... Pentachloronaphthalene-Skin ......................... Pentachlorophenol-Skin .................................... Pentaerythritol ................................................... * Pentane .................................................................... 2-Pentaaone ........................................................... Perchloroethylene ............................................... Perchloromethy1 mercaptan .............................. Perchloryl fluoride .......................................... * Petroleum Distillates (naphtha) ................ Phenol-Skin ........................................................... p-Phenylene diamine-Skin ................................ Phenyl ether (vapor) ........................................ Phenyl ether-Blphenyl mixture (vapor) ... Phenylethylene, see Styrene ......................... Phenyl glycidyl ether (PGE) .......................... Phenylhydraxine-Skin....................................... Phosdrln (Mevinphoa ")-Skin .......................... Phosgene (c*rhonyl chloride) ....................... Phosphine ................................................................ Phosphoric acid .................................................. Phosphorus (yellow) .......................................... Phosphorus pentaehloride ................................ Phosphorus pentssulflde .................................. Phosphorus trichloride .................................... 13 a) 2_ 100 E 5 10 0.2 100 25 25 5 E -400 i) 'I3 --- 0.05 0.1 -- -- 0.005 -- -- -500 200 100 0.1 i) i> 5 m 1 1 10 5 -- 0.1 0.3 -* --- 0.5 mx/M 33b) 310 9 29 2 250 90 90 Al 30 0.1 1,900. 5h 0.0( 1 0.1 0.2 0.5 0.1 0.01 0.5 0.5 D 1,500 700 670 0.8 13.5 19 0.1 7 7 60 22 0.1 0.4 0.4 1 0.1 1 1 3 Substance ppm*) Phehalic anhydride ........................................................... Picric aeld-Skin ................................................................ Pival R (2-Pivalyl-l, 3-indandione) ....................... Platter of Paris ............................................................... Platinum (Soluble Salta) as Pc .................................. Polytetrafluoroethylcne decomposition products . Propane ................................................................................... fi Propiolactone .................................................................. Propargyi elcohol-Skin ..................................... n-Propyl acetate ............................... Propyl alcohol .................................................................... n-Propyl nitrate ................................................................ Propylene dlchloride ....................................................... Propylene imine-Skin ....................................................... Propylene oxide ........................... Propyne, see Methylacetylene ................................ Pyre thrum............................................................................... Pyridine ..................... Qulnone ................................................................................... RDX-Skin ................................................................................. Rhodium, Metal fume and dusts, as Rh ................. Soluble salts .................................................................. Ronnel ...................................................................... .............. Rotenone (coonerclal) ..................................................... Rouge............... .................................................... .. Selenium compounds (as Se) ................... ...................... Selenium hexafluoride ..................................................... Silicon carbide .................................................................. Silver, metal and soluble compounds ....................... Sodium fluorecetate (1080)-Skin ................. .. Sodium hydroxide ............................................................... Stlbine ................. ................................................................ Starch ........................................ ........................................... * Stoddard solvent ............................................................... Strychnine............. .............................................................. **C Styrene monomer (phenylethylene) .............................. Sucrose ................................................................................ .. Sulfur dioxide ............................................................ Sulfur hexafluoride ......................................................... Sulfuric acid ...................................................................... Sulfur monochloride ..................................................... Sulfur pentafluoride ....................................................... Sulfuryl fluoride .................................. ........................... Systox, see Dematon* ................. 2,4, s t.............................. Tantalum ........................................... TEDP-Skin ........................................ Teflon* decomposition products Tellurium ........................................ 2 E 1 200 200 25 75 2 100 5 0.1 0.05 0.1 200 100 5 1,000 1 0.025 5 14 mg/M3b) 12 0.1 0.1 D 0.002 A* 840 500 110 350 5 240 5 15 0.4 1.5 0.1 0.001 10 5 D 0.2 0.4 D 0.01 0.05 2 0.5 0 1,150 0.15 420 D 13 6,000 1 6 0.25 20 10 5 0.1 Substance Pm>) Tellurium hexafluoride ................................................... TEPP-Skin ............................................................................... C Terphenyls ............................................................................ 1, 1, 1, 2-Tetrachloro-2, 2-difluoroethane ......... 1, 1, 2, 2-Tetrechloro-l, 2-difluoroethane ......... 1, 1, 2, 2-Tetrachloroethane-Skin ............................ Tetrachloroethylene, see Perchloroethylene ......... Tetrachloromethane, see Carbon tetrachloride ... Tetrachioronaphthalene-Skin ........................................ Tetraethyl lead (as Pb)-Skin ...................................... Tetrahydrofuran........... ...................................................... Tetramethyl lead (as Pb)-Skin .................................... Tetramethyl succinonitrile-Skin ................................ Tetrasitromethane ............................ ................................ Tetryl (2, 4, 6-trinitrophenylmethylnitramine)- Skin ..................................................................................... Thallium (soluble compounds)-Skin as T1 ............... Thiram ..................................................................................... Tin (inorganic cmpds, except SnH^ and Sa02> .... Tin (organic cmpds) ......................................................... Tin oxide .............................................................................. Titanium dioxide ............................................................... Toluene (tolul) .................................................................. C Toluene-2, 4-dilsocyanate ............................................ o-Toluidine-Skln ................................................................ Toxaphene, see Chlorinated camphene ....................... Tributyl phosphate ........................................................... 1, 1, 1-Trichloroethane, see Methyl chloroform . 1, 1, 2-Trichloroethane-Skin ...................................... Trichloroethylene ............................................................. Trichloromethane, see Chloroform .............................. Trichloronaphthalene-Skin ............................................. 1, 2, 3-Trichloropropane ............................................... 1, 1, 2-Trichloro 1, 2, 2-trifluoroethane ........... Trlethylamine ...................................................................... Trifluorooonobromomethane ............................................. * Trimethyl benzene ............................................................. 2, 4, 6-Trinitrophenol, see Picric acid ............... 2, 4, 6-Trinitrophenylmethylnltramine, see Tetryl ........................................................................ Trinitrotoluene-Skin ....................................................... Trlorthocresyl phosphate............... .. ............................ Trlphenyl phosphate ......................................................... Tungsten & compounds, as H Soluble .............................................................................. Insoluble .......................................................................... Turpentine ............................................................................ Uranium (natural) sol. & insol. compounds as U ................................................................ 0.02 1 500 500 5 200 0.5 1 200 0.02 5 10 100 50 1,000 25 1,000 25 100 - 15 - mg/M^ 0.2 0.05 9 4,170 4,170 35 2 O.lOQj) 590 0. 150 J ^ 3 8 1.5 0.1 5 2 0.1 0 D 750 0.14 22 45 535 5 300 7,600 100 5,100 120 1.5 0.1 3 1 5 560 0.2 Substance ppa*^ mg^ C Vanadium (V20j dust) ................... (VjOj fume) ................... Vinyl ban*ana, saa Styrene .... +*C Vinyl chloride ................................ Vlnylcyenlde, sac Acrylonitrile Vinyl toluene .................................. Warfarin ............................................. Xylene (xylol) ................................ Xylidine-Skin .................................. Yttrium ............................................... Zinc chloride fume ........................ Zinc oxide fume .............................. Zirconium compound* (as Zr) ... 0.5 0.1 500 1,300 100 480 0.1 100 435 5 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 Permissible Concentrations of Radionuclides In Air and In Water for Occupational Exposure, " June 5, 1959. Also, see U. S. Department of Cosneree National Bureau of Standards, Handbook 59, "Permissible Dose from External Sources of Ionizing Radiation," September 24, 1954, and addendum of April 15, 1958.* ** a) Parts of vapor or gas per million parts of contaminated air by volume at 25C and 760 mm. Hg pressure. b) Approximate milligrams of particulate per cubic meter of air. d) An atmospheric concentration of not more than 0.02 ppm, or personal protection may be necessary to avoid headache. h) As saa^led by method that does not collect vapor. I) According to analytically determined composition. J) For control of general room air, biologic monitoring is essential for personnel control. ** See Notice of Intended Changes * 1970 Addition Capital letters refer to Appendices. - 16 - A. KTHERAL DOSTS Substance SILICA Crystalline ** Quartz, Threshold Limit calculated from the formula ........................................... m.p.p.c.f.*) 250*' IS102 + 5 ** Crlstoballte, Threshold Limit calculated Amorphous, including natural diatoaaceous earth ....................................... 20 SILICATES (less than It crystalline silica) ** Asbestos, all types ......................................... Mica ......................................................................... Portland Cement ................................................. Soapstone .............................................................. Talc (non*asbestiform) .................................. Talc (fibrous), use asbestos limit ......... Tremolite, see asbestos ................................ 5 20 50 20 20 Graphite (natural) ..................................................... ** "Inert" or Nuisance Particulates See Appendix D 15 50 (or 15 mg/M^ whichever is the smaller) of total dust <IX sio2 Conversion factors mppcf X 35.3 million particles per cubic meter particles per c.c.* ** e) Millions of particles per cubic foot of air, based on lmplnger samples counted by light-fieId technics. f) The percentage of crystalline silica in the fowls is the amount deter* mined from elrborne samples, except in those instances in which other methods have been shown to be applicable. ** See Notice of Intended Changes for Mineral Ousts 17 B. NOTICE OF INTENDED CHANGES (FOR 1970) These substances, with their corresponding valuta, comprise thoae for which either a limit haa been proposed for Che flrae else, or for which a change in the "Adopted" Hating haa been propoaed. In both cases, the propoaed limits ehould be conaldered trial limits that will reaala in the Hating for a period of at leaat two years. During thia time, the previously Adopted Limit will remain in affect. If, after two years no evidence cornea to light that questions the appropriatenaaa of the values herein, the valuta will be placed in the "Adopted" liat. Documentation la available for each of theae substances. Substance ppm ++ 2-Acetylaminofluorene-Skin................................ ................ + Allyl glycidyl ether .............................................................. 4-Aminodiphenyl-Skln........................................ .................... + Ammonia ...................................................................................... + Ammonium chloride fume ......................................................... Asphalt (petroleum) fumes ................................................... + Butyl lactate ............................................................................ + Camphor (synthetic) ................................................................ + Diazinon-Skin ............................................................................ + 2-N Dlbutylamlno ethanol-Skln .......................................... Dichlorobenzidlne-Skln ......................................................... + Diethylene erlamine-Skin.................................................... 4-Dimethylamlnoazobenzene .......................... .. Fibrous glass ............................................................................ +C Formaldehyde ............................................................................... Iron pentacarbonyl ............ Mercury (Alkyl compounds)-Skin ........................................ Mercury (All forms except alkyl) .................................... + Methyl chloride .......................................... Methyl 2-cyanoacrylate ......................................................... + Methylcylopentadlenyl manganese tricarbonyl (as Mn) ......................................... ........................................... Methyl demecon-Skin ............................................................... Methyl parathion-Skin ........................................................... Phenothlazine-Skin .................................. ............................... + Rosin Core Solder, pyrolysis products ......................... 5 25 1 2 2 1 g)-2 0.01 100 2 0.1 '-- Styrene ......................................................... 100* * /M3 Al 22 A1 18 10 5 5 12 0.1 * i* D 3 o.oe o.oi 0.05 210 8 0.2 0.5 0.2 5 0.1 (as aide hyde) 420 + 1970 Revision or Addition Capital letters refer to Appendices g) <5-7 n Diameter. No TLV for coarse fibrous glass has yet been set. * - 18 - NOTICE OF INTENDED CHANGES (Cont'd) (FOR 1970) Substance +C Subtillsins (Proteolytic enzymes) .................................. ppm -- + Vanadium (V2O5 Fume) aa V Vinyl acetate ........................ + Vinyl chloride ...................... + Wood duet (non allergenic) 10 200 -- mg/M^ 0.0003 (as 100 0.05 30 770 pure crystal line en zyme) 5 + 1970 Revision or Addition Capital letters refer to Appendices 19 - v NOTICE OF INTENDED CHANCES (Cont'd) MINERAL DOSTS Substance + Asbestos (All types) + Cosl dust (bituminous) Crlstoballte + 'Inert' or Nulssnce Parti culates + Quartz Silica, fused Tridymite TLV 5 fibers/al> 5u in length1*) 2 mg/mJ (respirable dust)) Ose one-half the value calculated from the count or mass formulae for quartz. 10 ag/M3 or 30 appef (whichever is the smaller) of the total dust c IX Si02a) TLV in appef: 300 XS102 + 10 TLV for respirable dust in mg/m3: _________ 10 bk/M3p) X Respirable quartz + 2 TLV for "total dust", respirable and nonresplrable: 30 ag/M3 X quartz + 3 Ose quartz fonulae Ose one-half the value calculated from fonulae for quartz. + 1970 Revision or Addition k) As determined by the naabrane filter method at 430 X magnification phase contrast llluatLnation. Concentrations > 5 fibers/ml, but not to exceed 10, aay be permitted for 15-minute periods each hour up to five times daily. m) "Respirable" dust as defined by the British Medical Research Council Criteria (1) and as sampled by a device producing equivalent results (2) (1) Hatch, T. E. and Gross, P., Pulmonary Deposition and Rantcntlon of Inhaled Aerosols, p. 149. Academic Press, New York, New York, 1964 (2) Interim Guide for Respirable Mass Sampling, AIHA Aerosol Techno logy Conittee, AIHA J. 31, 2, 1970, p. 133. n) This automatically reduces all particulate substances in Adopted list with TLV of 15 ag/M3 to 10 ag/M3. p) Both concentration and per cent quartz for the application of this limit are to be determined from the fraction passing a size-selector vith the following characteristics: Aerodynamic Diameter (4) (unit density sphere) m2 2.5 3.5 5.0 10 - 20 - X passing selector 90 75 50 * 25 0 APPENDIX A A Because of the high Incidence of cancer, either in man or In animals, no exposure or coneacC by any route, respiratory, oral or akin should be permitted for Cha compounds: 2-Acatylaad.no fluorana 4-Aminodiphenyl Banzidina & its aalts Dlchlorobenzidina 4-Dlmathylaminoazobanzane bet a-Naphthy1amine 4-Nltrodiphenyl N'Nltrosodlmethylamine beta-Proplolaetone Because of ehe extremely high incidence of bladder tumors in workers handling beCa-naphchylamina and cha potential carcinogenic actlvicy of the other compounds, tha State of Pennsylvania prohibits the manufacture, oaa and other activities that involve human exposure without express approval by Cha Department of Health. 5 if A Polvtetrafluoroethvlene decomposition products. - Thermal decomposition of the fluorocarbon chain in air leads to the formation of oxidized products containing 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 recamended pending determination of the toxicity of the products, but air concentrations should be minimal. A3 Gasoline and/or Petroleum Distillates. - The composition of these materials varies greatly and thus a single TLV for all types of these materials is no longer applicable. In general, the aromatic hydrocarbon eontenc will determine whet TLV applies. Consequently the content of benzene, other aromatics and additives should be determined to arrive at the appropriate TLV (Elkins, et. al. A.I.H.A.J. 24, 99, 1963).* * Trade Names: Algoflon, Pluon, HaIon, Teflon, Tetran *' 21 APPENDIX B B.l THRESHOLD LIMIT VALUES FOR MIXTURES When two or sort hazardous aubeteacee ere present, their combined effect, rather than that of either individually, ahould be given primary consideration. In the abaence of information to the contrary, the effects of the different bazarda ahould be considered aa additive. That la, if the sum of the following fractions, C exceeds unity, than the threshold limit of the mixture ahould be considered as being exceeded. indicates the observed atmoapheric concentration, and Ti the corresponding threshold limit, (See Example LA.a.). Exceptions to the above rule may be made when there la good reason to believe that the chief effects of the different hamful 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^ + or + Cj ate.) Itself has a value exceeding unity, (See Example lA.b.). Antagonistic aetlon or potentiation may occur with some combinations of amospherlc contaminants. Such cases at present oust be determined individ ually. Potentiating or antagonistic agents are not necessarily hamful by themselves. Potentiating affects of exposure to such agents by routes other than that of inhalation is also possible, e.g. imbibed alcohol and Inhaled narcotic (trichloroethylene). Potentiation is characteristically exhibited at high concentrations, l'*s probably at low. When a given operation or process characteristically emits a number of haxmful 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 end relative quantity of the other contaminants ordin arily present. Exmples of processes which are typically associated with two or more harmful atmospheric contaminants are welding, automobile repelr, blasting, painting, lacquering, certain foundry operations, diesel exhausts, etc., (Example 2.) 22 THRESHOLD limit values for mixtures EXAMPLES 1A. General case, where air la analyzed for aach component a. Additive effects, (note: It la essential that the atmosphere be analyzed both qualltively and quantitatively for each compo nent preaent. In order to evaluate compliance or noncompliance with thla calculated TLV.) i+ fi +fi +.........-i Ti T2 I3 Example No. 1: Air contains 5 ppm of carbon tetrachloride (TLV - 10 ppm) 20 ppm of ethylene dichlorlde (TLV - SO ppm) and 10 ppm of ethylene dlbromlde (TLV - 25 ppm) Atmospheric concentration of mixture - 5 + 20 + 10 - 35 ppm of mixture A + 20 + 10 . 25 + 20 + 20 . , , 10 50 25 50 Threshold Limit Is exceeded. Furthermore, the TLV of this mixture may be calculated by reducing the total fraction to 1.0; l.e. Example No. 2: TLV of mixture - 35 27 ppm 1.3 Air contains 200 ppm of haxane (TLV - 500 ppm) 100 ppm of methylene chloride (TLV 500 ppm) and 20 ppm of perchlorethylene (TLV - 100 ppm) Atmospheric concentration of mixture - 200 + 100 + 20 * 320 ppm of mixture 200 100 20 200 + 100 + 100 400 500 + 500 + 100 " 500 0.S 500 Threshold Limit Is not exceeded. The TLV of this mixture - 320 -400 ppm - 23 - IB. Special case when the source of contaminant Is a liquid mixture and the atmospheric composition Is assumed to be similar to that of the original material; e.g. on a time weighted average exposure basis, all of the liquid (solvent) mixture eventually evaporates. a. Additive effects (approximate solution) 1. The percent composition (by weight) of the liquid mixture is known, the TVLs of the constituents must be listed In mg/M3. (NOTE: In order to evaluate compliance with this TLV. field sampling instruments should be calibrated. In the laboratory, for response to this specific quantitative end qualitative elrvapor mixture, and also to fractional concentrations of this mixture; e.g.. k the TLV; 1/10 the TLV; 2 X the TIV; 10 X the TLV; etc.) TLV of mixture 1 TLV, TLVb TLVC TLV,, Example No. 1: Liquid solvent contains (by weight) 501 heptane (TLV 2,000 mg/M3) 501 methylene chloride fTLV 1740 mg/M3) 20L perchlorethylene (TLV - 670 mg/M3) TLV of mixture 1______________________ 1 -Oil + _0J + 0J_ '.OOUZS + .U0017 +'.0UUJ 2000 1740 670 - - -.1 - 1390 mg/M3 -.00072 Of this mixture: 501 or 695 mg/M3 is heptane, 30L or 417 mg/M3 is methylene chloride and 201 or 278 mg/M3 is perchlor ethylene These values can be converted to ppm as follows: heptane: 2000 mg/M 500 ppm 1 mg/M3 0.25 ppm 695 mg/M3 - 174 ppm methylene chloride: 1740 mg/M3 1 mg/M3 417 mg/M3 500 ppm 0.287 ppm 119 ppm - 24 - perchlorethplene: 670 mg/M^ 100 ppm 1 mg/MI 0.15 ppm 278 mg/1r 42 ppm The TLV of this mixture 174 + 119 + 42 335 ppm. lB.b. Central Exact Solution for Mixtures of It Components With Additive Effects and Different Vapor Pressures. Si<l> Tli ++ T2 ++.........l*+. i. (2) Ci + C2 +......... + C,, - I; (2.1) C, Cj Cm . , Bp the Law of Partial Pressures, (3) Ci - aplt and bp Baoult's Lav, (4) Pl - PlPl. Combine (3) and (4) to obtain (5) Ci FiPl* Combining (1), (2,1) and (5), va obtain (6) Fjp^ + P^ +.........+ F,^ . IT T PlPl + P2P2 + + FnPn *1 t2 ......... Ta and solving for T, (6.1) T . FlPl + P2P2 *........." FnPn *iPl . ?2P24 . . FnPn Tl Tj Tn or - n Fjj!0 (6.2) _ 1 1 *' 1 ** i.i JpL -tt" - 25 - v T Threahold Liaiit Value la ppm. C Vapor concentration la ppm. p Vapor praaaura of eoaponent la (oluelon. p Vapor praaaura of pura coaponaac. F Mol fractloa of ccxaponent la aoludoa. a eoaacaae of proportionality. Subaerlpta 1, 2, . . .a ralata cha above quantltlea to components 1, 2, ... a, reapectively. Subacrlpt 1 rafara to aa arbitrary component from 1 to a. Abaaaca of aubacrlpt ralataa the quantity to tha alztura. lB.c. Solutioe to ba applied afaaa there la a reaervolr of tha aolvent Blxtura vfaoee coapoaltloa does aot change appreciably by evaporation. Exact Arithmetic Solutloa of Specific Mixture Mol. vt. Deaalty TLV p at 25C Mol fraction la half-andhalf aolutloa by volume Trichloro ethylene (1) 131.4 1.46 g/ml 100 73 an Hg 0.527 Methylchlorofora (2) 133.42 1.33 g/ml 350 125 an Hg 0.473 F^pj0 - (0.527) (73) 36.2 F2P2 * <*473> f125) " 59.2 38.2 59.2 . (97.4) (350) ,, (97.4) (350) . 177 TLV 38.2 59,2 133.8 + 59.2 193.0 100 350 TLV - 177 ppn (Mote difference la TLV when account la takaa of vapor praaaura and aol fraction la comparlaon with abova aample where auch aceouat la aot takaa.) 2. A Blxtura of one part of (1) parathloa (TLV, 0.1) and two parta of (2) EFH (TLV, 0.5) . C- 3CX i_ + ii - ii 0.1 0.5 Ta 0.5 \ ^ - 0.21 /mg H3 1C. TLV for Mixturea of Mineral Duata. For mixtures of biologically active mineral duaCa the general formula for mixturea may be uaed. For e mixture containing 80Z tele and 20Z quartz, the TLV for 1007. of the mixture la given by: TLV - * u oj 20 2.5 8.4 mppef Eaaentially the aame reault mill be obtained if the limit of the more (moat) toxic component la uaed provided the effecta ere additive. In the above example the limit for 20Z quartz ia 10 mppef. For another mixture of 25X quartz, 251 amorphoua ailica and 507. talc: TLV - _________ ] . 7.3 mppef 0.25 . (L25 . 0j[ 2.5 20 20 The limit for 25Z quartz epproximatea 8 mppef. - 27 v APPENDIX C PERMISSIBLE EXCURSIONS FOR TIME-WEIGHTED AVERAGE (IWA) LIMITS The Excursion TLV Factor la the Table eutoBatlcally defines the magnitude of the permissible excursion above the limit for those substances not given a "C" designation; l.e., the TWA limits. Examples In the Table show that nitrobenzene, the TLV for which is 1 ppm, should never be allowed to exceed 3 ppm. Similarly, carbon tetrachloride, TLV 10 ppm, should never be allowed to exceed 20 ppm. By contrast, those substances with a "C" designation are not subject to the excursion factor and must be kept below the TLV. These limiting excursions are to be considered to provide a 'rule-of-thumb' guidance for listed substances generally, and may not provide the most appropriate excursion for a particular substance. Efforts are being made to develop such specific excursions,`when Indicated to be significantly different from chat recommended by the present excursion factors. Substance Max. Cone, Permitted Excursion for short TLV Factor time Nitrobenzene Carbon tetrachloride Carbon monoxide Acetone Boron trlfluoride Butylamine Styrene monomer 1 ppm 10 ppm 50 ppm 1000 ppm C 1 ppm C 5 ppm C 100 ppm 3 2 1.5 1.25 -- -- -- 3 ppm 20 ppm 75 ppm 1250 ppm 1 ppm 5 ppm 100 ppm For all substances: TLV -0-1 (ppm or mg/m9), Excursion Factor 3 TLV -1-10 (ppm or mg/m9). Excursion Factor - 2 TLV - 10 - 100 (ppm or mg/m9). Excursion Factor - 1.5 TLV - 100 - 1000 (ppm or mg/m9). Excursion Factor - 1.25 BASIS FOR ASSIGNING LOOTING "C" VALUES By definition In the Freface, a listed value bearing a "C" designation refers to a 'celling' value that should not be exceeded; all values should fluctuate below the listed value. This, In effect, makes the "C" desig nation a maximal allowable concentration (MAC). In general, the bases for assigning or not assigning a "C" value rest on whether excursions of concen tration 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 proneness, Impair self- rescue or materially reduce work efficiency. v - 28 - APPEHDIX 0 Son* "Inrt" or Nuisance Particulates ^* ** Alundum (AI2O3) Calcium carbooata Calluloaa (papar fiber) Portland Camant Corundum (AI2O3) Emery Glycerine Miat Graphite (synthetic) Gyp rum Vagatabla oil mists (except castor, csshtv nut. or similar Irritant oils) Kaolin Limastone Magnasite Marble Peataerythritol Plaster of Paris Rouge Silicon Carbide Starch Sucrose Tin Oxide Titanium Dioxide q) When toxic impurities art sot praaant, e.g. quartz IX. ** 29 APPENDIX E Some Simple Asphyxiant* - "Inert" Gases and Vapors Acetylene Argon Ethane Ethylene -- Helium Hydrogen Methane Neon Nitrogen Nitrous Oxide Propane --1970 TLV COMMITTEE MEMBERS Paul E. Caplan Hervey B. Elkins, Ph.D. W. G. Fredrick, Sc.D. Bernard Grabois, P.E. Paul Gross, M.D. Wayland J. Hayes, Jr., M.D. John W. Knauber - Harold N. MacFarland, Ph.D. Frederick T. McDermott E. Mastroaatteo, M.D. Col. Walter W. Melvin, Jr., M.D. Ralph G. Smith, Ph.D. Mitchell R. Zavon, M.D. Herbert E. Stokinger, Ph.D., Chairman William D. Wagner, Recording Sec'y - 30