Document X88dnEj2BkKEoa66kwdj5oX7w
Copyright 1966, by American C onference of Governmental Industrial H ygienists.
The A merican Conference of Governmental Industrial H y g ien ists w ill welcome requests for perm ission to republish or reprint these T hresh old Lim it V alues. R equests for such perm ission should be directed to the Secretary-Treasurer, 1014 Broadway', C incinnati, Ohio 4S202.
Single C opies -- 30 cents
The 2nd edition of the Documentation of T hreshold L im it V alues, rew ritten and greatly enlarged to include the approxim ately 400 sub sta n c e s in th e lis t, i s a v ailab le and may he pur ch ased from th e S ecretary-T reasurer. The Docu m entation should be consulted when using the Threshold Lim it V alues herein.
THRESHOLD LIMIT VALUES FOR 1966
The Threshold Lim it V alues refer to air-borne concentrations of substances and represent con d itio n s under w hich if is b e lie v e d that nearly all workers may be repeatedly exposed, day after day. w ithout adverse effect. B ecause of wide variation in individual susceptibility, exposure of an o ccasional individual at or even below the threshold lim it may not prevent discomfort, ag gravation of a pre-existing condition, or occupa tional illn ess.
Threshold lim its should be used as guides in the control of health hazards and should not be regarded as fine lines betw een safe and dan gerous concentrations. E xceptions are the sub stan ces given in Appendix A and certain of the substances given a " C " listing. The values not given a " C" listin g refer to time-weighied aver age concentrations for a normal workday.
The amount by w hich th ese concentrations may be ex ceeded for sh o rt periods w ithout injury to health depends upon a number of factors such as the nature of th e contam inant, whether very high concentrations even for short periods produce acute poisoning, w hether the effects are cumula tive, th e frequency w ith w hich high concentra tions occur, and the duration of such periods. All must be taken into consideration in arriving at a decision a s to w hether a hazardous situa tion e x ists. E nlightened industrial hygiene prac tice in clin es toward controlling exposures below the lim it rather than m aintenance at the limit.
Threshold lim its are based on the best avail ab le inform ation from in d u s tria l e x p e rie n c e , from experim ental human and anim al studies, and when p o ssib le , from a com bination of the three. The b a sis on w hich the values are established may d iffer from su b stan ce to substance; protec tion ag ain st Impairment of health may be the guiding factor for some, w hereas reasonable free dom from irritation, n arco sis, nuisance or other forms of stre ss may dominate the b a sis f o r others. T he Com m ittee holds to th e opinion that
1
^ ' lim its bused on physical irritation should be considered no le s s binding than those based on physical impairment; growing bodies of evidence indicate that ph y sical irritation may promote and accelerate physical impairment.
D ocumentation of T hreshold Lim it V alues. A sep arate companion p iece to the TLV s is is* sued by ACGIH under th is title. T h is publication gives the pertinent scien tific information and da ta with reference to literature sources, that were used to base each lim it. Each docum entation al so contains a statem ent defining the type of response against which the lim it is safeguarding the worker. F a r a better understanding of the TLV s it is essen tial that the Documentation be consulted when the T LV s are being used.
C eiling vs Time-W eighted Average Lim its. Although the time-weighted average concentra tion provides the m ost satisfactory, practical way of monitoring air-bom e agents for compli ance with the lim its, there are certain substan ces for which it is inappropriate. In the latter group are su b stan ces which are predominantly fast acting and whose threshold lim it is more appropriately based on this particular response. Substances with this type of response are b est c o n tro lle d by a c e ilin g **C*' lim it th a t should not be exceeded. It is im plicit in these defini tions that the manner o f sam pling to determ ine com pliance with the lim its for each group m ust differ; a single brief sam ple, th at is applicable to a " C " lim it, is not appropriate to th e lime* w eighted limit: here, a sufficient number of sam p les are needed to perm it a tim e-w eighted average concentration throughout a com plete cycle of operations- or throughout the work shift.
W hereas the ceiling lim it p laces a definite boundary which concentrations should not be perm itted to exceed, the time-weighted average lim it req u ires an ex p licit lim it to the excursions that are perm issible above the listed values. The m agnitude of th ese excursions may be peg ged to the m agnitude o f the threshold lim it by an appropriate . factor shown in Appendix C. It should be noted that the same factors are used
2
by the .Committee in making a judgment whether to include or ex clu d e a su b sta n c e for a " C" listing.
" Skin1* N otation. L is te d s u b s ta n c e s follow ed by the designation "S kin'1 refer to the potential contribution to the over-all exposure by the cu taneous route including mucous membranes and eye, either by air-bom e, or more particularly, by direct contact with the substance. V ehicles can alter skin absorption. T his attention-calling de signation is intended to su g g est appropriate m easures for the prevention of cutaneous absorp tion so that the threshold limit is not invalidat ed.
Mixtures. S pecial consideration should be given also to the application of th ese values in a sse ssin g the h ealth hazards w hich may be a s so c ia te d w ith exposure to m ixtures of two or more su b stan ces. A brief d isc u ssio n of basic considerations involved in developing threshold lim it values for m ixtures, and m ethods for their development, am plified by sp ecific exam ples are given in Appendix B.
" Inert" or N uisance P articulates. A number of d u sts or p a rtic u la te s th at occur in the working environment ordinarily produce no specific ef fects upon prolonged inhalation. Some insoluble substances are c la sse d as inert (e.g. iron and ste e l dusts, cement, silico n carbide, titanium dioxide, cellulose); others may be solu ble (starch, soluble o ils, calcium carbonate) but are of such a low order of activ ity th at in con centrations ordinarily encountered do not cause physiologic Impairment; still others may be rap idly elim inated or destroyed by th e body (veg etable o ils, glycerine;, sucrose). In the c ase of the insoluble su b sta n c e s, there may be some a c cum ulation in the respiratory p a ssa g e s. In the c a se of the soluble substances, this accum ula tion w ill ordinarily be temporary but may inter fere to some extent with respiratory processes. Hence, it is desirable to control the concentra tions of such p articu lates in the air breathed by any individual, in keeping with good industrial hygiene practice.
a A th resh o ld lim it o f 15m g/m , or SO mppcf, whichever is le s s, is recommended for substan-
V
1
c e s in th ese c ate g o ries and for w hich no sp e c )' fic threshold lim its have been assigned. This lim it, for a norm al work day, does not apply to brief exposures at higher concentrations. N either Jo e s it apply to those su b stan ces which may c a u se physiologic im pairm ent a t lower concen trations but for which a threshold lim it has not y et been adopted. Some " in e rt" particulates are given in Appendix D.
Simple A sp h y x ia n ts-" In e rt" G ases or V apors. A number of g a s e s and vapors, when present in high concentrations in air, act primarily as sim ple asphyxiants without other significant phys io lo g ic effe c ts. A TL.V may not be recommend ed for each sim ple asphyxiant because the lim it ing factor is th e av ailab le oxygen. T he minimal oxygen co n ten t should be 18 percent by volume under norm al atm o sp h e ric p re ssu re (e q u iv a le n t to a p a rtia l p re s s u re , pOz, o f 135 mm Hg). A tm os pheres deficient in Oz do not provide adequate warning and m ost sim ple asphyxiants are odor le ss. S everal sim ple asphyxiants are listed in Appendix E . Some asphyxiants present an ex plosion hazard. Account should be taken of this factor in lim itin g the concentration of the asphyx iant.
T h ese lim its are intended for use in the field of industrial hygiene and should be interpreted and applied only by persons trained in this field. T h ey are not in te n d e d /Or u s e , or for m odifica tion for u se, (1) a s a relative index of toxicity, by making a ra tio of two lim its, (2) in the evalu ation or control of community air pollution or air pollution n u isa n c e s, (3) in estim ating the toxic potential of continuous uninterrupted exposures, (4) a s proof or d isproof of an ex istin g d is e a se or physical condition, or (5) for adoption by coun trie s w hose w orking co n d itio n s differ from those in the U.S,
P h y sical F a c to rs. It ia recognized that such physical factors as heat, ultraviolet and ioniz ing radiation, humidity, abnormal pressure and th e like may p lace added stre s s on the body so th a t th e e ffe c ts from exposure a t a threshold lim it may b e a lte re d . Most of these s tre s s e s act
4
adversely to Increase the toxic response of a substance. Although m ost threshold lim its have built-in safety factors to guard against adverse e ffe c ts of m oderate d e v ia tio n s from norm al en vironments, the safety factors of most substan ces are not of such a magnitude as to take care of gross deviations. For example, continuous work at tem peratures above 90"F of over-tim e, extending the w ork-w eek more than S0%, might be co n sid ered g ro ss d ev iatio n s. In su ch in sta n c e s judgment m ust be exercised in the proper adjustm ents of the threshold limit values.
T hese values a re review ed annually by the Committee on Threshold L im its for revision or additions, a s further information becom es a v ail able.
" N otice of In ten t" A t the beginning of each year, proposed actio n s of the Committee for the forthcoming y ear are is su e d in the form of a " N o tic e of In te n t.'* T h is N o tic e p ro v id es n o t only an opportunity for comment, but so lic its suggestions of substances to be added to the list. The suggestions should be accom panied by substantiating evidence for a tentative limit.
As L egislative Code. The Conference does not consider the T hreshold L im it V alues appro priate m atter tor adoption in leg islativ e codes and regulations and recommends ag ain st such u se. If, however, th e lis t is so u sed ,th e intent of the concepts contained in the P reface should be m aintained and p ro v isio n s should be made to keep the list current.
Reprint P erm ission. T h is publication may be reprinted provided th at w ritten perm ission is ob tain ed from the S ecretary-T reasurer of the Con ference and that it be published in its entirety.
5
RECOMMENDED VELUES (In Alphabetical Order)
Subatacic*
PPTM' H i/H "
Acetaldehyde................... ........................ Acetic acid................................................ Acetic anhydiide.......................................
Acetone......................................................
Acetonitrile................................................. Acetylene dichtorida, see 1,2 Dicloro-
ethylene ................................................... Acetylene tetrabromide.............................. Actolein................................................ ..... Acrylonitrile-Skin.......................................
Aldijn-Skin ................................................ Ally1 atcohol'Skin..................................... Allyl chloride............................................. C Allyl giycidyl ethei (AGE)....................... Allyl propyl disulfide................................ 2 Aminoethanol, see Ethanolamrne.......... Ammonia .................................................... Ammonium sulfamate Animate)................. n-Amyi acetate........................................... Aniline-Skin .............................................. + Antsidine (o, p-isameis)-Skin................... Antimony & compounds (as Sb)............... ANTU (alpha'naphthyl thiourea) .............. Arsenic & Compounds (as As)................. Aisine ................................................... .
Barium (soluble compounds).......................
C Benzene (benzol)-Skin................................ Benzidine-Skin........................................... p-Benzoquinone, seeQuinone...................
+ Benzoyl peroxide....................................... Benzyl chloride......................................... Beryllium ..................................................
| Biphenyl, see Diphenyl..................... ..... Boron oxide...............................................
C Boron ttifluoiide ....................................... Bromine...................................................... Butadiene (1,3-butadiene)......................... Butanethiol, see Butyl mercaptan ............ 2-Bulanone................................................ 2-Butoxy ethanol (Butyl Cellosolve)-Skin ..
f Butyl acetate (n-butyl acetate) ................
Butyl alcohol............................................. ten. Butyl alcohol.................................... C Butylamine-Skin.........................................
C tert. Butyl chromate (as Ci03)-Skin.......... n-Butyl giycidyl ethei (BGE)..................... Butyl mercaptan........ .................................
200 360 10 25 5 20
1.000 2.400 40 70
1 14 0.1 0.25 20 45 - 0.25 25 13 10 45 2 12
SO 35 - 15 100 525 5 19 - 0.5 0.5 - 0.3 - 0.5 n ns 0 2 - 0.5 25 80 -- A1
-5 15 - 0.002
- 15 13 0.1 0.7 1,000 2.200
200 590 50 240 -100 300 100 300 5 IS - 0.1 50 270 10 35
* P rl 1 v d p r at g d i p r m illio n p a r i* a ir p lw * v a p o r bjr v o lu m * a t 25*C and 7A m m. H g p r tt fiu r *
* A p p ro ilm a ta m llh g tfta i o f fa r iU u lo ir par co b le a la r af olr,
A NumUri, $ Apptnfix A
+ 1966 Addition t See T entative Lim its
6
SuWhnca
p-tert. SutyUotueM.................... Cadmium oxide fume....... .......................... Calcium m ate....................................... Calcium oxide ........................................... Camphor .................................................... + Carbaryl (Sevin) (Ft) ................ ................ Cai bon dioxide........................................... Carbon disulflde-Skin..... .......................... f Carbon monoxide...................................... Carbon tetrachloride-Skin.......................... Chlordane-Skin.......................................... Chlorinated camphene, -Skin ..................... Chlorinated diphenyl oxide....................... f Chlorine........................ ,.......................... Chlorine dioxide ....................................... C Chlorine trifluoiide................................... C Chloroacetaldehyde................................... Chlorobenzene (monochlorobenzene) ........ ChloiobromomeUrane.................................. 2-Chloio-l,3 butadiene, see Chloroprene .. Chlorodiphenyl [42% chloilne)-Skin.......... Chlorodlphenyl [54% chtartne)-Skln.......... 1 . Chloto, 2,3 epoxypropane, see
Eplchlorhydrin......................................... 2, Chloroethanol, see Ethylene
chlocohydrin............................................. Chloroethylene, see Vinyl chloride.......... C Chloroform (trichloramelhane)........... 1-ChlOro-l-nltiopiopane ............................ Chloropiciin........................................ ...... Chloroprene [2-chloro-1,3'buladiene)-Skin Chromic acid and chromates (as Cr03) ..... t Cobalt.............. .................. ..................... Coppet fume........................:..................... Ousts and Mists....................................... + Cotton dust (raw)....................................... Ciag(R) herbicide..................................... Cresol (all lsomets)-Skin.......................... Cyanide (as CN)-Skin................................ t Cyclohexane............................................... Cyclohexanol............................................. 1Cyclohexanone........................................... t Cyclohexane..............................................
+ Cyclopentadiene....................................... 2.4 -0......................................................... DDT-Skin .................................................. DDVP-Skin................................................ Decabotane-Skin ....................................... Demeton (R)-Skin....................................... Diacetone alcohol (4-hydioxy-4-methyl-2pentanone) ............................................... 1,2 Diamlnoethane, see EthylenedUmlne Dlborane....................................................
t 1,2'Dlbromoethane (ethylene dibromide)Sk in ................................... ......................
t See T entative Lim its
WW'* Ht f U 1
10 60 - 0.1 -1 -5 -2 -S 5,000 9,000 20 60 -10 65 - 0.5 - 0.5 - 0.5 -0.1 0.3 0.1 0.4 13 75 350 200 1.050
-1 - 0.5
50 240 20 100 0.1 0.7 25 90 - 0.1 -- 0.1 - 1.0 -1 - 15
5 22 -5
50 200 50 200 75 200 - 10 -1 -I 0.05 0.3
- 0.1
50 240
0.1 0.1
7
f
Substance
ppm* H a /M 1
C `o-Drchloiobenzene......................................
p-DIchlorobenzene...................................... Diehl oradifluoiomethane.............................
+ 1,3-Dichloio-5,5-dlmethyl hydantoin........ 1,1, -Dichloroethane.................................. 1.2- Olchloioethane............. ...........
1.2- Oich!oroethylene..................... C Dlchloroethyl etttei-Skin.............................
Ojchloramethane, see Methytenechloride "
50 300 75 450 1.000 4,950
- 0.2 100 400
50 200 200 790 15 90
Dlchloromonofluoiomethane....................... 1, 000 4, 200
C 1 ,1-Dichlarg-L-nltioethane.........................
10 60
1.2- Dlchloropropane, sea Propylenedi-
chlorlde.....................................................
Dichtoiotetraftuoioeihane........................... Oleldrln-Skin........................................ Diethytamine................................. ...... """ Dlethylethet, see Ethyl ether...................
1,000 7,000
- 0.25 25 75
Dlftuoiodibomomethane............................
Z..!ZZZC Diglycidyl ether (DGE)............ Dlhydroxybenzene, see Hydraquinone......
100 860 0.5 2.8
Oil in butyl ketone ..................................... Dimethoxymethane, see Methyla l ..............
50 290
Dimethyl acetamide-Skin ........................... + Dlmethylamine............................................
10 35 10 18
Dimathylaminobenzene, see Xylidene......
Dlmethylanlline (N-dimethylaniline)-Skln .. Dimethyl benzene, see Xylene...................
5 25
+ Dimethyl 1, 2-dibomc-2,2-dichloroethyl
phosphate, (Oibrom) (R)........................... + Dimethyl formamide-Skln............................'
2, 6 Dlmethylheptanone, see Dilsobutyl
-3 10 30
k e t o n e ......................................................
1,1 -Dhnethylhydrazlne-Skln....................... Dlmethylsulfate - Skin...............................
Dlnltrobenzene (all lsomers)-Skln.............. Dinftro-o-cresol-Skin..................................
Dlnltrotoluene-Skin.................................... Dioxane {Diethylene dlaxlde)-Skin............ Dipropylene glycol methyl ether-Skln........ + Di-sec, octyl phthalate (Ol-2-ethylhexy!-
0.5
1 -
-
100 100
1
5 1
0.2
1.5 360 600
phthalate.................................................. Endrln-Skln................................................ Epichlorhydrln-Skln................................. EPN-Skln..................................................
1.2- Epoxyptopane, see Propyleneoxide ....
-
5 -
5
0.1 19 0,5
2.3- Epoxy-l-propanol see Gtycidol ...
Ethanethiol, see Ethylmercaptan ..T...........
Eihanol amine.............................................
2 Ethoxyethanol-Skln................................ 2 Ethoxyethy Iacetate (CellOSolve acetate)
36 200 740
-Skin ........................................................
Z'.'ZEthyl acetate.....................................
Ethyl acrylate-Skin................................ Ethyl alcohol (ethanol)........................... t Ethyl amine.................................................
100 540
400 1,400
25 100 1,000 1,900
+ 1966 Addition
S
Subitonci
{C Ethylbenzene....................................... Ethyl bromide................................ ........... Ethyl chloride .............................. ........... Ethyl ethei............................ . ......... Ethyl foimate.................. ........................
1C Ethyl mercaptan..............Z Z Z ! ............. Ethyl silicate...................... .....................
Ethylene chlorohydtln-Skiii`Z Z Z 'Z 'Z '...... Ethylenedfamtne......... ................ ' ........ Ethylene dltxomide, s e e l, 2-Dlbron-..... ethane..........................................
Ethylene dichloride, see 1,2-oiehioro-..... ethane............................................... C Ethylene glycol dlnltrate-Skin...... Ethylene glycol monomethyl ether acetate" see Methyl cellosolve acetate.......... ' t Ethylene imine-Skfn.................. .......... Ethylene oxide....................... '..... ............ Ethylldln# chloride, see 1 ,1-Qlchloro-...... ethane........................................ F e rb a m ..................................................... Ferrovanadium dust......... ............... ..... Fluoride (as F) ....... ......... ........................
Fluorine.........................Z 'Z Z !!Z Z 'Z '"" Fluorotrichloromethane......... Z Z Z !! ... C Formaldehyde.............................. ..............
Freon 11, see Fluorotrichloromethane....... Fieon 12, sea Dlchlotodifluoromethane..... Freon 13Bl, see Tiifluoromonobromomethane...............................
Freon 21, See Dlchloromonofluwomethane.............................................
Freon 112, see 1, l,2,2'Tetrachioto-l,2 difluoroethane........................... Freon 113, see 1 ,1 ,2-Trichloro, 1 2 2trilluoroethane........................................ Freon 114, see Dlchlorotetrafluoio- ....... ethane....................................... Fuifural-Skin.............. Z Z Z .............. Fuilutyl alcohol........Z . . . Z Z Z ! .............. Gasoline..........................Z . Z . Z .............. Glycldol (2,3-Epoxy-l-propanol)................ Glycol monoethyl ethei, see 2-Ethoxyethanol................. .................... t Guthion, see Azlnohosmethvi ............... Hafnium.......................................................
Heptachlar-Skln...... ."ZZZ".'.'".'.'.'.............. Heptane (n-heptane) ................... + Hexachloioethane-Skln........ Z Z Z Z Z ! Hexane (n-hexane)...................... ........ 2-Hexanone.................. Z ................... Hexone........ ..........'Z'Z 'Z 'Z Z '.'Z ............ sec-Hexyl acetate.....!...!.... Z!"!!............... Hydrazine-Skin......... ......Z Z Z ,'..... ......... Hydrogen bromide........ ' .....................
t See T entative Lim ite
PP" 4 M g/H " '
200 690 1,000 2,600
400 1,200 100 300 100 850
5 IS 10 25
0.2 1.2
50 90
- 15 -1 - 2.5 0.1 0.2 1,000 5,600 56
5 20 50 200 - AS 50 150
- 0.5 - 0.5 500 2.000 1 10 500 1,800 100 410 100 410 50 295 1 1.3 3 10
9
Subrronca
C Hydrogen chloride.....................................
Hydrogen cyanide-Skin.............................. Hydrogen fluoride ........ ............................. Hydiogen peroxide, 90$............................ Hydiogen selenide...................................... + Hydiogen sulfide....................................... Hydroquinone................................ ............ C iodine........................................................ t iron oxide fume ......................................... Isoamyl alcohol......................................... Isophorone................................................ Isopropyl alcohol.............. ................
isoptopyfamine.......... ................................
Isopropylettier........................................... Isopiopyl glycidyl ether (ICE)................... Helene..................................................... .
L ead......................................................... Lead arsenate........................................... Lindane-Skin.................... ...................... Lithium hydride......................................... + L.P.G. (Liquitied petroleum g as)............
Magnesium oxide fume ..............................
Malathion-Sktn............................. C Manganese................................................
Mercury-Skin.............................................. Mercury (organic compounds)-Skin............ Mesityl oxide......................... Metltanethiol, see Methyl meicaptan ........ Methoxyehlor ............................................ 2-Melhoxyethanol, see Methyl cellosolve .. Methyl acetate........................................... Methyl acetylene (propyne) ....................... -i- Methyl acetylene-propadlene mixture
(MAPP).................................................... Methyl acrylate-Skin.......... ....................... Methylal (dimeUioxymethane)..................... Methyl alcohol (methanol) .......... Methyl amyl alcohol, see Methyl iso
butyl carhinol........................................... C Methyl bromide-Skin ..................................
Methyl butyl ketone, see 2-Hexanone........ Methyl cellosolve-Skin.............................. Methyl celiospive acetate-Skin................ C Methyl chloride ............................... Methyl chlotofoim..................................... Methylcyclohexane.................................... Methylcyclohexanol.................................... o-Methyicydohexanone-SKm......................
Methyl ethyl ketone (MEK), see 2-Butanone........................................................... Methyl formate........................................... Methyl isobutyi carblnol-Skin ................... Methyl Isobutyt ketone, seeHexone ........ +C Methyl mercaptan.......................................
ppa"
57 10 11 32 1 1.4 0.05 0.2 10 15 -2 0.1 1 -100 360 25 140 400 980
5 12 500 2,100 50 240
0,5 0.9 - ' 0.2 - 0.15 - 0.5 - 0.025 1,000 1,8DD -- 15 - 15 -5 - 0.1 - 0.01 25 100
- 15
200 610 1,000 1,650
1,000 1,800 10 35
1,000 3,100 200 260
20 80
25 80 25 120 100 210 350 1,900 500 2,000 100 470 100 460
100 250 25 100
10 20
+ 1966 Addition
10
Subatoftc*
+ Methyl methaciytate .............................
Methyl propyl ketone, see 2-Pentanone..... C aMethyl styrene............... ......................... C Methylene bisphenyl isocyanate (MOI)......
Methylene chloride (dichloromethane) ...... Molybdenum [soluble compounds)..............
(insoluble compounds).......... Monomethyl aniline-Skin............................ + Morpholine-Skin......................................... Naphtha [coal U r)..................................... Haphtha (pettoleum) .................................. + Naphthalene............................................... fl-Naphthylamlne....................................... Nickel carbonyl......................................... + Nickel, metal and soluble compounds...... Nicotine-Skin............................................. + Nitric a c id .......... ...................................... p-Nitroaniline-Skin.................................... Nitrobenzene-Skin...................................... + p-Nitrochloro-benzene-Skin....................... Nltroethane................................................ C Nitrogen dioxide....................................... + Nitrogen tritluorlde.................................... C Nitroglycerin- + EGDN-5kin....................... Nitromethane..................... ....................... 1- Nitropiopane...................................... 2- Nitropropane...................................... N-Nitrosodimethy1-amine (Di-methyinitfosoamine)-Skin ...........--................. Nitratoluene-Skin...................... ................. Nitrotrichloromethane, see Chioroplcrin....
Octane............................. -........................ Oil mist (mineral) ..................................... Osmium tetroxlde....................................... + Oxygen dilluoride -,.,,................................ Ozone ........................................................ Parathion-Skin ........................................... Pentaborane............................................... Pentachloronaphthatene-Skin..................... Pentachlotophenol-Skin............................ Pentane............... ...................................... 2-Pentanone.................. ............................
Perchloroethylene...................................... Peichloromethyl mercaptan....................... Petchlotyl fluoride.................................... Phenol-Skin............................................... + p-Phenylene diamlne-Skin........................ Phenyjitiylene. see Styrene..................... Phenyl glycidyl ether (PGE)..................... Phenyihydtazine-Skin................................ Phosdiln (Mevinphos) (R)-Skin .................. + Phosgene (carbonyl chloride) ................... Phosphine.................................................. Phosphoric acid.........................................
apm*
100 410
100 460 0.02 0.2
500 1.740 5 IS
2S 20 70 200 BOO 500 2.000 10 50
A1 0.001 0.007
1 0.5 25 16 15 1 100 310 59 10 29 0.2 2 100 250 25 90 25 90
A5 5 30
500 2,350 5 0.002
0.05 0.1 0.1 0.2
0.1 0.005 0.01
0.5 0.5 11,000 2.950 200 700 100 670 o .i o.a 3 13.5 5 19 0.1
50 310 S 22
0.1 0.1 0.4 0.3 0.4
1
| See T entative L im its
n
' su b n
ff"-
Phosphorus (yellow)..................................
- 0.1
Phosphorus pentachtoride ............. ..........
--1
Phosphorus pentasulfide ..........................
-1
Phosphorus trichloride..............................
0-5 3
+ Phthalic anhydride...................................
2 12
Picric acid-Sit in................................................
- 0-1
Platinum (Soluble Salts)...................................
- 0.002
Polyletrafluoroethylene decomposition
products .................................................. * Propane..............................
--A 1.000 1,800
Propyite, see Methylacelylene.................
ppropiolactone...........................................
- A
n-Propyl acetate .......................................
200 840
n-Propyl nitrate....................................
25 110
Propylene dichloride..... ................
25 350
f Propylene imine-Skin...............................
Propylene oxide...................... -..................
100 240
Pyrethium..................................................
-5
Pyridine ..........
5 15
Quinone.................................... ................
0.1 0.4
Rotenone (commercial).....................
-5
+ Selenium compounds (as Se) ...................
- 0.2
-t Silver, metal and soluble compounds...
-- 0.01
Sodium fluoroaceiate (1080) -Skin.............
-- 0.05
Sodium hydroxide.......................................
-2
Stibine ......................................................
0,1 0.5
Stoddard solvent.......................................
500 2,900
Strychnine...................... ...........................
" 0-15
C Styrene monomer (phenylethylene)............
100 420
Sulfur dioxide............................................
5 13
Sulfur hexatluoiide ................................... 1.0Q0 6,000
Sulfuric actd..............................................
--1
Sulfur monochtorIde...................................
16
Sulfur pentafluoride...................................
0.02 5 0.25
Sulfuryl fluoiide.........................................
5 20
Systox, see Demeton................................
2 .4 ,5T ....................................................
- 10
Tantalum...............
-5
T E O P -S k in ...............................................
- 0.2
Teflon (R) decomposition piDducts............
- A4
Tellurium.................................................. T EPP-Skin..............................................
- 0-1 - 0-05
+ l,l,l,2-Tetrachloro-2,2-diflnoroethane ....
500 4,170
1, l^.Z-Teuachloro-l^-dlfluoroethane ....
500 4,170
1 ,1 ,2 ,2-Telrachloroetfiane-Skin......... ......
5 35
Tetrachloroethylene, see Perchloroethy-
le n e ......................................................... Telrachlororoethane, see Carbon tetra
chloride........... ........................................
Tetraethyl lead (as Pb) Skin...................
- 0.075
Tetrahydrofuran.........................................
200 590
Telranitromelhane.....................................
18
Tetryl (2,4,6-trinitiophenylmelhylnitra-
mine) - Skin ............................................
-- 1-5
t 1966 Addilion
12
SubiTanca
Ppm" Mft/H1*"
Thallium (soluble compounds) - Skin........
Thiram....................................................... Tin (inorganic cmpds, except oxide)........ Tin (organic cmpds) .................................. Titanium dioxide................ Toluene (toluol) ........................................
C Toluene-2,4-diisocyanate.........................
o-Toluidtne - Skin...................... Toxaphene, see Chlorinated camphene..... 1.1.1- Trichloroethane, see Methyl chloro
form Trichloroethylene ........................
Trichloromethane, see Chloroform............ Trichloronaphthalene - Skin....................... 1,2'3-Trtchloiopropane ............................
1.1.2- Trichlotol,2.2-trifluoroelhane..
Triethylamine............................................. Ttifluoromonobiomomethane....................... 2 .4.6- Tiinittophenol see Picric acid.... 2.4.6- Tiinttrophenylmethylnitramine, see
Tetryl ......................... ............................ Trinitrotoluene - Skin................................ Trioithocresyl phosphate..........................
Triphenyl phosphate.................... Turpentine................................................ Uranium (soluble compounds) ...................
(insoluble compounds)................
C Vanadium [VaOe dust).............................. (VzOs fume)..............................
Vinyl benzene, see Styrene....................... C Vinyl chloride...........................................
Vlnylcyanide, see Acrylonitrile................
Vinyl toluene............................................. Warfarin...................................................... t Xylene (xylol) ........................................... Xylidine-Skin........................................... + Yttrium......................................................
Zinc oxide fume....................................... Zirconium compounds (as Z t ) ...................
- 0.1
-5 -2 - 0.1 - 15 200 750 0.02 0.14 5 22
100 535
50
1,000
25 1,000
5 300
7,600
10D 6,100
- 1.5 - 0.1 -3 100 560 - 0.05 - 0.25 - 0.5 - 0.1
500 1,300
100 480 - 0.1
5 25 -1 -5 -5
Radioactivity: For permissible concentrations of radio isotopes in sir, see U. S. Department of Commerce, National Bureau of Standards, Handbook 69, " Maximum Perm issible Body Burdens and Maximum Permissible Concentrations of Radionuclides in Air and in Water for Occupational Exposure, " June 5, 1959, Also, see U, S. Department of Commerce National Bureau of Standards, Handbook 59, ""Permissible Dose from External Sources of Ionizing Radiation, " September 24, 1954, and adden
dum of April 15, 19S8.
* Parla of vapor or ga**par mllllan peris al air plus vapar fay vatunva al 35*C and 740 aim. tig pressure,
** Appiaximata milligram* of porticalala par cubic mater af air.
A Humbert, Srr Appandirt A
t See Tentative Limits
13
RESPIRABLE DUSTS EVALUATES BY COUNT
Subllanc*
n . p. p. c. I.
SILICA
Crystalline
Quaili, Threshold Limit calculated
flora the formula................
250
Cristobalite " ' " *SiOa + 5
Amorphous, Including natural
diatomaceous earth-........ -.............
20
SILICATES (less than 1%crystalline silica)
Asbestos........................................
5
Mica.......................................
20
Soapstone......................................
20
T a lc .........................................
20
Portland Cement............................
50
GRAPHITE (natural)............................
15
"Inert" or Nuisance Particulates 50 (or 15 mg/m1
whichever is the
see Appendix D
smaller)
Cm w iiIui factor*
mppcf x 35.3 = million particles per cubic meter = panicles pet c.c.
* M illion* a t p a rtlc U * par cubic loot a t air, baled on Imping*? tam pla* cavnlad by llg h t.lla ld tachnic*.
* T h* p arcan tag a o ( cry atetlln * tlic a In tK* IbiovId 1* dia amount d*t*rmln*d tram ali-b*m * lam p U i, *ncpt in rhet* Inatanc* In which atbar marhadi hav* baarr *bawn to b* appllcabl*.
14
TENTATIVE VALUES
These substances, with their corresponding tentative limits, comprise those for which a limit has been assigned for the first time or for which a change in the 'Recommended' listing has been made. In both cases, the assigned limits should be considered trial values that wit) remain in the ten tative listing for a period of at least two years, during which time difinitive evidence and experience is sought. If accept able a t the end of two years, these substances and values will be moved to the RECOMMENDED list. Documentation for tentative values are available for each of these substan ces.
Svbatonca
ppm*
Acrylamide - Skin....................................
2-Aminopyridine.........................................
sec-Amyl acetate.......................................
Azinphos-methyl-Skin...............
-
Brorootorm-Skin.....................
0.5
n-Butyl acetate.........................................
sec>8utyl acetate.....................................
tert-Butyl acetate.....................................
++ sec-Butyl alcohol .....................................
Cadmium (Metal dust and soluble salts) ....
Catbon M ack............................................
Carbon monoxide.......................................
++ a'Chloioacetopheflone (phenacyIchloride)..
o-Cblorobenzyildcne maicnonitiile (QCBM)
C Chlorine...................................................
++ Chiomlum, sot. chromic,' chromous salts,
as Cr .....................................................
Metallic & insoi. salts............................
Coal tar pitch volatiles (benzene soluble
fraction) (anthracene, BaP, phenanthrene,
acridine, chrysene, pyrene)...................
.++ Cobalt, Metal fume 1 dust.......................
Crotonaldehyde.........................................
Cumene - Skin ..........................................
Cyclohexane.......................................
Cydohexcne..............................................
Di azomethane............................................
C 1,2-Oibromo-ethane-Skin ............... -- .....
+ Dibutyi phosphate.....................................
+ Dibutylphthalate.......................................
Diethylamino ethanol-Skin........................
++ Diisopiopylamine-Skin..............................
- 0.3 0.5 2 125 650
0.2 5 150. 710. 200 350 200. 950. 150. 450. - 0.2 - 3.5 50. 55. 0.05 0.3 .05 0.4 1. 3.
-- 0.5 - 1.
- 0.2 - 0.1 2. 6. 50, 245. 300. 1,050. 300. 1,015. 0.2 0.4 25. 190. 1. 5. - 5. 10, 50. 5. 20.
* Poll* of vapor or gaa par million porta of air plus vapor by voluaio al 25C and 740 aim. Hg prossura.
** Approximato milligram, of particular* par cubic
malar oi air.
Hr 1966 Revision H-+ 1966 Additions
IS
I
Sulrstanca
t+ Dlmethylphthalate...................................... ++ Diphenyl....................................................
Ethyl amine................................................
Ethyl sec-amyl ketone (S-niethyI-3-heptano n t) .......................................................... Ethyl benzene........................................... Ethyl butyl ketone (3-Heptanaae).............. + C Ethylene glycol Initiate &/01 nitrogtyceilnS kln.......................................................... Ethylene imlne-Skln .................................. C Ethyl metcaptan............ .............................
N-Ethylmorpholine-Skin............................. Fibrous glass............................................. Formic a c id ............................................... ++ Gasoline................ .................................. sec-Hexyi acetate t+ Hexachlofonaphthalene - Skin.................... lion oxide fume.......................................... Isoamyl acetate.............................. ........... Isobutyl acetate.......................................... ++ Isobutyl alcohol.......................................... isopropyl acetate........................................ + Maleic anhydride........................................ Methylamlne............................................... Methyl (n-amy!) ketone (2-Heptanone) ....... Methyl iodide S kin.................................. Methyl Isocyanate Skin ........................... C Monomethyl hydrazine - Skin...................... k Naphtha (coal ta t)...................................... k k Nitric oxide...............................................
++ Oclachlotonaphthalene - Skin................... ' Oxalic acid.................................................
k+ Paiquat - Skin-................. ,,........................ Phenyl ethet (vapor).................................. Phenyl ether-Biphenyl mixture (vapoi).......
+ Phenyl glycldyl ethet (PGE)...................... Pival (2-Plvalyl-l,3-lndandione) ..............
++ Piopyl alcohol........................................... Propylene mine - Skin.............................. Rhodium, Metal fume and dusts ................ Soluble s a lts ...........................................
++ Ronnet........................................................ Selenium hexafluoride................................. Tellurium hexafluoride...............................
k-tC Tetphenyls....... .........................................
++ Tetiachloionaphthalene - Skin.................... Tetramethyl lead(TML) (as lead) - Skin .... Tetiamethyl succinonltiile - Skin.............. Tremo1ite ...................................................
k + Trlbutyl phosphate.................................... 1 ,1 ,2-Tilchloroethane - Skin...................... Xylene........................................................
k k Zinc chloiide.............................................
+ 1966 R evision
++ 1966 A dditions
t F at interm ittent exposure only
ppm' H W
- 5. 0.2 1. 10. 13.
25. 130. 100. 435. 50. 230.
0.D2+ O .tt 0.5 1. 10. 25. 20. 94. - 5. 5. 9. A SO. 300. - 0.2 -- 10. 100. 525. 150. 700, 100. 300. 250, 950. 0.25 1. 10. 12. 100. 465. 5- 28. 0.02 0.05 0.2 0.35 100. too. 25. 30. - 0.1 - 1. -- 0.5 1. 7. 1. 7. 10. 52. -- 0.1 200. 450 2. 5. - 0.1 - 0.001 -- 15. 0.05 0.4 a. 02 0.2 l. 9.4 - 2. - 0.075 0.5 3. 5 (upper- 5. 10. 45. 100* 435. - 1.
m16
Appendix A
a ' B enzidine Because ot high incidence of bladdei tumots in man, any exposure, including skin, Is extremely hazaidous.
A2 ^N ophthylom lne, Because of the extremely high Incidence of bladder tumors in workers handling this compound and the inability to control exposures,^ -naphthylamine has bean pro hibited from manufacture, use and other activities that in volve human contact by the Stale of Pennsylvania.
A1 N-NItrosodlmethylomlns Because of extremely high toxicity and presumed carcinogenic potential ol this compound, con tact by any route should not be permitted,
A4 P o ly te tro flu o ro e fh y le n e * decom position products. Thermal decomposition of the fluorocarbon chain in air leads to the formation of oxidized products containing carbon, fluor ine and oxygen. Because these products decompose by hydro lysis in alkaline solution, they can be quantitatively deter mined in air as fluoride to provide an index of exposure. No TLV is recommended pending determination of the toxicity of the pioducts, but air concentrations should be minimal,
A*(S Propiolucton* Because of high acute toxicity and demonstra ted skin tumot production in animals, contact by any route should be avoided,
A* G asoline. The composition of gasoline vafies greatly and thus a single TLV for all types ol gasoline Is no longei applicabla. in geneial, the aromatic hydrocarbon content will determine what TLV applies. Consequently the content of benzene, other aromatics and additives should be deteimined to arrive at the appropriate TLV (Elkins, el at, A.LH.A.J. 24, 99, 1963).
* T tade Names: Algoflon, Fluon, Halon, Teflon, Tetran
' Appendix B
B.1 THRESHOLD LIMIT YALUES FOR
MIXTURES
. When two or more hazaidous substances are present, their combined effect, rather than that of either individually, should be given primary consideration. In the obscnce of informa tion to the contrary, the effects of the different hazards should
17
7C 1- +_2C ; = tc 1
700 700
Tm
Tm ' 700 x 2 -- J55 ppm 9
IB. b. General Exact Solution for Mixtures of N Components With Additive Effects and Different Vapor Pressures.
(1) C- V Ca + , ,. a + Cm = 1;
Ti Ta
Tm
(2) Ci + C2 + . .
C = T,
(2.1) _Ci_ + Ca + . ,. * + Cm = L
TT
T
By the Law of Paitial Pressures,
13) Ci = apt,
And by RaouIPs Law,
(A) p i = p l p 1".
Combine (3) and (4) to obtain
(5) Cr = aFipi,
Combining!]), (2,1) and(5), we obtain
(6) Pipi* + Papa* t . . . + FnPk*=
TT
T
FioI + Fzpa* + . . . + FhPm*
T\ Ti
T
and solving for T,
(6.1) T = F ipi* + Fap2' -t- . . . + FhPk
F ip 1" F2Pa*
FmP*
T i + Ta + . . . t- Tm
i= n
,or 1
Fipi"
(6.2) T -- i = 1 1= n 2 F ip i*
I -- l Ti
T = Threshold Limit Value in ppm. C = Vapor concentration in ppm. p -- Vapor pressure of component
in solution.
20
p* = Vapor pressure of pure component
F -- Mol fraction of component in solution.
a = A constant of proportionality. Subscripts 1,2, . . . n relate We above quantities to components 1,2, . . . n, respectively. Subscript i tefets to an arbitrary component from 1 to n. Absence of subscript relates We quantity to the mixture.
Solution to be applied when there is a reservoir of the solvent mixture whose composition does not chance appreciably by evaporation.
Exact Arithmetic Solution of Specific Mixture
Mol. wt,
Density T p*at Mol 1iac 25*C tion in half-and
half solu
tion by volume
TrichlotoeWylene'(t) 131.4 1.46 g/ml 100 73mm He 0.527
Methy(chlo roform (2) 133.42 1.33 g/ml 350 125mm Hg 0.43
F i j i * = (0. 527) (73) = 3. I F ip S * = (0, 473) (125) = 59. 2
T -- 33.2 4 59.2 = (97,4) (350)= 197.4) <3501 -- 177
3H.2 + 59.iT 133.8 + 58.2
133.0
10Q 350
T = 177 ppm (Note difference in T. L. V. when account is taken of vapor pressure and mol fraction in comparison with above example where such account is not taken).
2. A mixtuie of one part of (1) paiathion (TLV, 0.1) and two parts of (2) EPN (TLV, 0.5).
21
Cl +
:-- .C m ;
0. 1 0 .5
Tm
Cm -- 1C i
Cl + 2 0 = 3 0
0.1 0. 5
Tm
7 0 = 1C l 0 .5 Tm
Tm = 1 .5 = 0,21 7
1C. T. L. V. tot Mtxtuies of Mineral Oust*.
Foi mixturax of biologically active mineiai dusts the geneial formula lor mixtures may be used. With the exception of asbestos, pure minerals are assigned TLV of 2.5, 20 or 50.
Foi a mixture containing 80% talc and 20% quartz, the TLV foi 100% of the mixture " C" is given by:
TLV =
1 0.8-1- 0.2
" SET T T
8.4 mppcf
Essentially the same result will be obtained If the limit of the mote (most) toxic component is used provided the effects are additive. In the above example the limit foi 20% quartz is 10 mppcl.
Foi another mixture of 25% quartz 25% amoiphous silica and 50% talc:
TLVa3 0.25 j 0.25 + 0.5 = 7-a 2.5 20 20
The limit fer 25% quartz approximates 8 mppcf.
22
Appendix C
BASES FOR ASSIGNING LIMITING
"C" VALUES
By definition In the Preface, a listed value bear ing a " C " designation refers to 'ceiling ' value that should not be exceeded; all values should fluctuate below Ote listed value. In geneial the bases for assigning or not assigning a " C " value rest on whether excursions of concentration above a proposed lim it 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,impaii self rescue or materially reduce work efficiency.
In order for the Committee to decide whether a sub stance is a candidate for a **C " listing, some guidelines must be formulated on the permissive fluctuation above the limit in terms of the seriousness of the response In the categories a, b, c, given above. For this the factors given In the table below have been used by the Committee. For both technical and practical reasons, the factors have been pegged to the concentration in an inverse manner. It w ill be noted that as the magnitude of the T. L. V. increases a correspondingly decreased range of fluctuation is permitted; not to decrease the factor for T . L. V. s of increasing magnitude would permit exposures to large absolute quantities, an undesirable condition, a condition that is minimized, at tow T . L. V. s. More over, larger factors at the lowei T. L . V. s are con sistent with the difficulties in analyzing and con trolling tiace quantities.
i.L.y.
DANCE ppm* m / i
T*r
T.l.V. fa clir
,,, E x x m p lii
0 to 1
3 Toluene diisocyanate-T. L. V ., 0.0 2 ppm, if permitted to rise above 0.06 ppm may lesuit In sensitization in a single sub sequent exposuieJ " C " listing
recommended on category b.
1+tolO
'2 M a n g a n e s e -T .L .V ., 5mg/m , contains little ot no safety factor. A ll values should fluct uate below 5mg/m*. "C " listing recommended on
category b.
23
, T.L.Y.
T .ii
AWE
T.I.V.
/m ` * r rn f/iru fictu
10 + to 100
1.5
100+ to 1000
1.25
EiimiMt
Methyl styiene-T, L , V. 100 if encountered at levels of 150 ppm w ill prove Intense ly irritating, " C " listing recommended on category a.
Methyl chlorofotm-T, L. V. 350ppm, at 438 ppm for per iods not exceeding 15 min utes is not expected to re sult in untoward effects relating to category c. No " C " listing recommended.
* Whichever unit is applicable
PERMISSIBLE EXCURSIONS FOR TIMEWEIGHTED AVERAGE (TWA) LIMITS
As stated in the preface, the same factors may be used as jides for reasonable excursions above the lim it for substan ce to w hich the time-weighted average applies. The Unw eighted average implies that each excursion above the limit . compensated by a comparable excursion below the limit, hus, a value of 6 -ppm H F is permissible for periods not exceding 15 minutes, provided an equivalent decrease below e limit of 3 -ppm obtains.
Appendix D
Some " in e rt" or Nuisance Particulates*
Alundum (AlaOs) Calcium carbonate
Cellulose Portland Cement Corundum (AlaOa) Emeiy Glycerine Mist Graphite (synthetic) Gypsum
Limestone Magnesite Marble Plaster of Paris Rouge Silicon Carbide Starch Sucrose T in Oxide
Vegetable oil mists (except castor, cashew nut, or similar irritant oils)
Titanium Dioxide
When toxic impurities are not present,
24
Appendix E
Some Simple Asphyxiants -- Inert" Gases and Vapors.
Acetylene Argon Ethane Ethylene Helium
Hydrogen Methane Neon Nitrogen Nitrous Oxide
E . J. Baler
Allan L Coleman Hetvey B. Elkins, Ph.D. W .G. Fredrick, Ph.D. Bernard Grabois, P .E . Paul Gross, M-D. Wayland J. Hayes, Jr. M.D.
Harold N. MacFarland, Ph.D., Consultant
E. Mastromatteo, M.D. Russel G. Scovill
Ralph G. Smith, Ph.D. George W. Wright, M .D .
Consultant Mitchell R. Zavon, M.D.
Herbert E . Stokinger P h .D ., Chairman
25