Document 1Qp4MyL8YoZz86QnVzg4g7kzZ

I AAIH SEMINAR No. 8 ODORS: HELPFUL WARNINGS AND HARMFUL EFFECTS Tuesday* October 22, 1985 Seminar Director: John E. Amoore, Ph D. Olfacto-Labs 1414 - 4th. Street Berkeley, CA 94710 (415) 255-0205 1 130 p.JT. FUNDAMENTALS OF ODOR SCIENCE 2:15 p.m, Demonstration of olfactory threshold testing 2:30 p.m. ODOR AS AN AID TO CHHKICAL SAFETY 3*15 p.m, Intermission to visit the exhibits 3*45 p.m. EFFECTS OF CHEMICAL EXPOSURE ON THE SENSE OF SMELL 4*30 p.m. Questions, comments, and review of test results Page 6 12 17 31 00 A 039745 CONFIDENTIAL Objectives: There is a large and scattered literature on the chemistry of odorous substances and the physiology of the sense of smell. This review is designed for maximum relevance to industrial hygiene. The presentation will be in three sections: 1. Fundamentals of Odor Science: Discusses the physical chemistry of odorant*/neasurement of odor detection threshold, odor intensity and odor quality. Describes the phenomenon of specific smell-blindness, and its value in suggesting a fun damental classification of primary odors. 2. Odor as an Aid to Chemical Safety : Develops a quantitative evaluation of the warning thresholds for 214 industrial odors, in relation to their TLVs. Analyzes the potential for worker education on hazard recognition by odor, and for odorization of hazardous products that lack adequate warning properties. 3. Effects of Chemical Exposure on the Sense of Smell: Con siders the normal, and abnormal, ranges of human olfactory sensitivity. Surveys the literature on temporary and permanent loss of the sense of smell caused by chemical exposure, usually chronic, but sometimes acute Over 100 chemicals can have these effects, belonging to six major divisions of the chemical industry. Illustrative materials will be provided, and a hands-on demonstra tion of olfactory threshold testing will be available. American Academy of Occupational Medicine American Academy of Industrial Hygiene Joint Conference on Occupational Health Orlando, Florida, October 21-25, 19B5 2 DO A 039746 OONFTDFNT TAl Key References (review articles)i Fundamentals of Odor Science: Odor theory and odor classification. J. E* Amoore. In "Fragrance Chemistry." 1982, 27-76. E. T. Theimer, Editor. Academic Press, New York. Olfactory Threshold Testing: The pyridine scale for clinical measurement of olfactory threshold: a quantitative reevaluation. A. H. Sherman, J. E. Amoore and V. Weigel. Otolaryngology and Head and Neck Surgery, `1979, 82* 717-733* Odor as an Aid to Chemical Safety: Odor as an aid to chemical safety: odor thresholds compared with threshold limit values and volatilities for 214 industrial chemicals in air and water dilution. J. E. Amoore and E. Hautala. Journal of Applied Toxicology, 1983* 1* 272-290. Effects of Chemical Exposure on the Sense of Smell: Effects of chemical exposure on olfaction in humans. J. E. Amoore. In "Toxicology of the NaBal Passages," 1985* 155-190*- C. S. Barrow, Editor. Hemisphere Publishing Corp., New York. ((.n* TV-tJsJ O0O7A7 3 00 0 OFNTT^ C.ONF I Useful Formulae! At 25 C* ppm x mol. vt. - mg/ra^ (European practice). 24.4 Air/water partition coefficient at 25 (v/v) vapor press, (mm Hg) eoly. (g/l) x mol. vt. x 538 x: 10r5 To prepare water or air dilutions from the pure odorant (solid or liquid)* 1 ppm (v/v) - 1 mg (or l/D jil) per liter of water M.V, M.V. 1 ppm (v/v) ---------- mg. (or ------------- pi) per cubic meter of air 24.4 24.4 x D Avogadro's Number* Mol. wt. in gm of a pure compound contains* OX 6,02 1 10 ; molecules Effect of pH on ionization of weak acids and bases: acid: concn. of acid ----------------------- - antilogy (pK& - pH) concn. of anion base: concn. of base ------------------- ------ - concn. of cation - antilogy (pH - pl^) where Kfi and are the acid and basic dissociation constants, respectively. Quantity of odorant adsorbed mass of adsorbant x k x concn, of odorant'* where k is a constant, and exponent b is less than unity. 0 4 cv Formulae (continued)! Stevens' (i960) Power Law for odor intensity! intensity - k x concn. of odorant where k is a constant, and exponent n is in the vicinity of 0.6 on log intensity n x log concn. 4 log k Hence, perceived intensity of odor increases about 1.5 times for each doubling of the odorant concentration. Conversions in the binary step (log2) concentration scale for odorants: concentration ratio antilogy (binary steps x O.JOl) log^Q concn. ratio binary steps ----- ^----------------------0.301 actual concn. of odorant Odor Units (U) - ------------------------ ------------ TM"" threshold concn, of odorant Cuadagni'B (1966) Rule of Additivity; Odor Units of a mixture is the sum of the odor units of all its components; U U 4 U_ 4 U. 4 . m12 3 _ ^^7 AQ 5 Odorant TnmethyUmine Pyridine Isobutyl isobutyrate /Cars one Phenyl ether i-Chloroacetophenone i^Pentadecalactone Musk ketone Volatilities of Odorous Compounds ai 23 C Vapor pressure (mmHg) Molecular weight Concentration in atr (g Inert (mg m'l (ppm. v \ ) 1700 20 42 0 i: 0 022 0.0075 . 0 00045 0 0000021 59 54 * I0r 5 4 a 10* 2,200.000 79 8 5 a 10 * 8 5 a 10* 26.000 144 33 * 10'* 3.3 a 10* 5500 150 97 * 10 * 9.7 a 10* 160 170 20 * io-4 20 a 10* 29 155 0.3 * 10'f 63 a I01 99 240 5.8 a 10'* 5.8 a J0 0 59 294 3 3 a 10 * 3.3 a 10- * 0 0028 Calculated air/water partition coefficients of normal 5<arboo compounds at 25*. Compound Vapor pressure (mm H|) Solubility m water t*/l) Molecular weight (|) Partition cocfridcnt (calculated) Pentane Propyl ethylene Propyl acetylene Pawyl chloride Pentyl mercaptan Methyl butyl ether Methyl butyrate Nitto pentane Pcnryl aldehyde Bury) cyanide Methyl propyl ketone Pentyl amine Pentyl alcohol Peatanoic add 520 640 440 33 15 170* 32 1.7 16* 7.6 2186 2.5 0.29 0.038 0.11 1.0 0.20 0.16 1.9 15 1.3 12 13fc 34 9 23 30 72.1 70.1 68 I 106.6 104.2 18.1 102.1 117.1 6.1 3.1 6.1 r.2 8.1 102 1 52 22 1.6 0.93 0.55 0.091 0.011 0.0085 0.0063 0.0026 0.0013 0:0013' 0.00052 0.000031 A 03^7^0 6 00 fOF^Tl OONF Odor Deterrtoo Thrr-sholdi of Selected Compound! Odor threshold eoncn in air Compound (mg m*) (ppm. v v) Ethane Methanol y Chloroform Benzene Camphor t Furfural lsoamyl acetate r Jj-Androst-l6-en-3-one 2-Meihox>-3-isobut>lp> razine IS X 10' 6.6 X 10* 3.2 X I03 1.7 X 10' l.l X I06 2 3 X 10'' 3 8 X I0'3 2.1 X 10'* 36 X I0-* r" rtr ^rz 120.000 500 65 5.2 0.17 0 059 0 0071 000019 0.00000054 ju*^~ Bulonol ppm, by volume The butanol reference scale for odor intensity. plotted in log log coordinates (Re printed from Moskowiu rt ai. 1974. o397BA 00 A Number of thresholds Concentration in air (ppm) Serial dilutions in water (binary steps) Normal distribution of olfactory threshold sensitivities in the human population. Bimodal distribution of olfactory thresholds to isobutyraldehyde. Car'**-. e A 03975? oonftdfnttai NUMBER OF SUBJECTS Thresholds of a panel of epecific anosmics (stippled) compared with a panel of normal observers (outlined). hQu. U o u ton z < NUMBER OF CARBON ATOMS Mapping the range of the specific anosmia to aliphatic aldehydes. / DO A 039753 C.ONFTDFNTTAL > CM, s \ OH c ACID CM,--------CM, || CM, .CM 1-PYRROLINE r .H /\ CM, CM, TRIMETHYL AMINE ^CH-CM CM, ISOBUTYRALDEHYDE -CH Iv t I CH ^CHV|'i jtN / ., VCH ^CHi I|I K S** CM]i CM] H 5a*ANDR0ST -16-EN-3-ONE CH, CM, .CM,--CH, Vs`CHj '"CM,-CM, Wi C-0 'cm,--CM, ^CM, ^CH,--O 'CM, 'CM, f-PENTADECALACTONE ^CM-- CM,-- C / CM, /CARVONE 1,8-CINEOLE Structural formulas of eight of the primary odorants. Olfaetometric properties of eight of the primary odorants. Primary odorant Primary Odor Norma] threshold In air In water (ppm, v/v) <ppm.w/v) Anosmics* occurrence (*/.) lsov,ter>c Kid Sweaty l-Pyrrolme Spermous Tnmethylamtne Fiahy Isobutyraldehyde Malty 3a*Androst-16-en-3-one Urinous w-Pentadecalactone Musky ACarvone Minty ] ,8-Cineole Camphor 0.0010 0.0018 0.0010 0.0050 0.00019 0.018 0.0056 0.011 012 ' 0.020 000047 0.0018 0.00018 0.0018 0.041 0.020 3 16 6 36 47 12 t 33 Anosmics' defect (factor) 42 39 130 340 770 13 13 56 J* &to jj DO 0 ,07 6A 03' df^ er* SEREIAl IDOI CLASSIFICATIONS SttCtriC ANOSMIA ANALYSES UK M 1 t minimi lamit MM mi Mttni tutut ttutut mm > on i (TOl 4 * M i Ml 4IBVATK A vmm 7 n * mi to Bn 11 BIND 13 tmm 13 IUMI 14 mu limn fiitmr 13 UT 1* TNLU ir imu ii \9 * lull MUT eiihiul 30 31 * im FIUT ftUlittllt 33 Hiihii 33 (Mir 34 WIIUC 33 * CIMIIC Utttit 34 cm mat 37 MlCITlt uriitnE 31 Hint 3t * UBIttB MtSftll 30 FU1L 31 33 33 34 33 34 mum Mil i timu nci raaitt fllfCIf him miiMt fiil CtKItl 4 MMntM M1 MUM MU Miim t tutut ttvtiut CIlFHI IMF iiiiim ruin iisir HIM timm mm Hi turn N44 1 tuuts (Tlltfli Mil 4 mm Mill nu M44 M4I 1 CUUtl 44 (UlUl MCb> UMMt MM1WII MMTIt IMIITK 4IIIRI4 lllllllll* nidii mint Bin ititin rntn 7 unco own lltllll Kiun Mom KTILIISI _tniaT_ UKFMI TlliUi MMiTIC VKI Mill rvumi Suet Bin Ultitll Tticnaii Katiini mini t.fcwim iirttitiiii I IlCILIII Minn ncuiL mm iiciiit cum tiiitu umui iimtn prim IPMI ____!*!____ IHiABUH 1ICMBU MUMIt (Tin u aim Ulnaii (41IIII LUM1X 1MMI uum wan ITlIflll tlBil CttIMI IliiniL immi MMM CMPM r* Hitt riinm 4U1III mtu rutmi ftit ntiiMi mu IfltT VlllLLA If111 Wtl Ulttc iislvii HIM Nil Fiiscin taunt T*U 111 Kl m unman t1CL|T(l[ min 4UUTI MUMI AttlCttUC T|| ISIS HI mi in IIIULIIE w-aaTMici UMBt AUH (II man iti Titictmn TnicuaiTf lUtCJ* J MIMIU iFcaic ice* IlfLMdl IBM Tin a( Ftflu ntBauMC TIlPITlU MlB( Mtirin w tm* mu inicnvi mu CilHLIt tWCiTT raw Mfn tCMtl BMt UK iLTBlTK FKITUCITtCi 1C9S 11} ( tnm U1MIS 111 iHttmm tMiriK ITIBS 111 MtMl tltCllMt ItltiLtllC Mil 4MI0ST 11 tl I4M tauti PNHl Kill IILFNHI itinilS annual FIUL, illfll Kiimi Fiiai Mill ttlFMHI Kit Mt BUT mm men Hum nuuc rumcui i-PTWim ituiu Mill i-pTtanvt mmi hbml ItlCilUlt liunu 111 tttVlFlII milt 4C icitk icn TMiraiat mm SMI ML auam acini 1 HU! thu IBM 37 Mill J MUT ! itMtain 141 BUfU ii mum 3* 4HIT 40 emu VlllTillE M timbal 41 mi irfiltti iumii 43 Mil Bimit 41MITM CtBBTTl at acam ULT 43 mim aniKu S*U 44 45 46 47 ' oo * 4| 11 CONP t 4V SO mi iincim * -- i ft j IHICEIT , T|l((PilAl | | J ylilti fBMiLltatlt PYRIDINE DILUTION SERIES DILUENT Binary step .fewt-0 1 2 3 4 5 6 7 B 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 26 29 WATER MINERAL OIL AIR CLINICAL SIGNIFICANCE Concentration Concentration Concentration (percent) (percent) (ppm, v/v) OF THRESHOLD 100 50 25 12 6 3 1.5 0.8 0.4 0.2 100 27,000 Henry s Law not obeyed in this concentration range 3 1.5 0.8 0.4 2,700 1,400 700 340 Complete anosmia. (no I, V, IX or X nerve function) Hvposmia type I. (no 1st nerv function but Vth nerve is functional) 0.1 0.05 0.025 0.012 0.2 0.1 0.05 0.025 170 80 40 20 Hvposmia type II. (abnormally weak let nerve function) 0.006 0.003 0.0015 0.0008 0.0004 0.0002 0.0001 0.00005 0.012 0.006 0.003 0.0015 0.0008 0.0004 0,0002 0.0001 10 5 2.6 1.3 0.66 0.33 0.16 0.08 Normal ranee. (Average = 16.0 st p S.D. 2.0) 0.000025 0.000012 0.000006 0.000003 0.0000015 0.0000008 0.0000004 0.0000002 0.00005 0.000025 0.000012 0.000006 0.000003 0.0000015 0.0000008 0.0000004 0.04 0.02 0.01 0.005 0.0025 0.0012 0.0006 0.0003 Hvoerosmla. (abnormally sensitive 1st nerve function) 12 00 A 039756 CONFIDENTIAL TEST PROCEDURE Select the pair of bottles for step #14. Flip open the spouts, and Bwlrl the contents to hasten equilibration. Instruct the patient to direct the spout closely towards the nostril, then to aqueez the bottle while inhaling through the nose. Ash the patient to pick out the odorous, or most odorous, bottle. Extra sniffs are permitted, before making the choice. Detection only is required, not recognition of the odor. Raise bottle above eye level to see the label on bottom of bottle. If the patient's choice Is correct (PIR-14) enter "C" in 1st. test column for step #14. Swirl the bottles again, and randomize their positions until neither the tester nor the patient remeab rs which is the odorous bottle. Ask the patient to repeat the test a 2nd. and a 3rd. time at step #14. A wrong selection (BIA-14) is indicated by "x" in the appropriate column. In order for the patient to pass a given sensitivity step, the correct selection must be made all three times. Flip the air-spouts closed, and replace the bottles in the carton. Proceed to the next higher, or lower, sensitivity step, as requir d to establish the patient's threshold olfactory sensitivity to pyridine on this occasion. At least two consecutive concentration steps should be passed, in order to establish a valid threshold, which is defined as the highest sensitivity step yielding all-correct responses. DO A 039757 CONFTDFNTTAl 15 SCORE-SHEET OLFACTORY SENSITIVITY TEST (PYRIDINE SCALE) Questionnaire Patient's name:_________________________________________ Referring M.D.: Date: m order to avoid permanently contaminating the bottles with foreign odorB, and to obtain a reliable test result, It Is essential that:- Patlent has not emoted In last 15 min.? No food, beverage or candy In last 15 min.?_____ No perfume or hand lotion used today? Not Buffering from a cold or influenza?_______ Not experiencing a nasal allergy (hay fever)? At least one nostril 1b clear right now? Precautions Th* bottles are on*-quarter filled vlth ninsral oil, and aunt not be knocked over, ehaken or inverted, because oil nay enter the air epout. Zf this accidentally occur*, the dlapenser cap ehould be uncraved, any oil lnalde the cap and air delivery tub* reaoved vlth tvlete of clean tissue, and the cap tightly replaoed. Xach test odor bottle should always be ooapared vlth Its ovn aatehed blank bottle. PyTldlne In th* strongest concentrations (step 06 contains 3% In th* oil) nay be oaustlo or Irritating. Xach successive higher sensitivity step contains pyridine at one-half the concentration of the preceding step. This ollnleal olfactory test kit aust be used only by trained personnel, and kept out of the reach of children. Clinical background Olfactory evaluation Pyridln threshold Is Step #_ T st d by: oo A 039?5ft rONFlDF/VT TA( 14 SENSIf1T TIAVP 1Yf1ll V1 STEP 29 28 27 26 25 24 23 22 21 20 19 18 17 16 15 14 13 12 11 10 9 6 7 6 TESTS i 1st 2nd 3rd t _____!____ . i NUMBERS OF PATIEN TS CLINICAL OLFACTORY THRESHOLDS Hyposmla 20 Normal 15 subjects 10 Normal Hyperosmla -------------- T" Pltuitary tumor ----------------r Rhinltls n in m. rB r.n-fl Post head trauma CLrr r~i.. n T Salim ami's H. syndrome __cBn l 10 I IS _r- 20 T 25 PYRIDINE SENSITIVITY STEP 30 15 DO A 039759 OONFTDFNTIAl CLINICAL INDICATIONS Hvposmla type I (pyridine sensitivity step #9 or lower) Mechanlcel blockage of airway by intranasal polyps, ethmoid Blnusitls, allergic rhinitis, or carcinoma of paranasal sinuses or nasopharynx. Damage to olfactory epithelium by acute or chronic Infection, atrophic rhinitis, or certain Industrial fumes and vapors. Damage to olfactory nerves or bulbs by head trauma causing fracture, shearing, hemorrhage or concussion. Abnormalities In the region of the floor of the anterior f ssa, Including meningioma, frontal lobe tumor, meningitis at base of frontal lobe, abscess of frontal or ethmoid bone, vascular tumor, or arteriosclerosis of the anterior cerebral artery. Congenital defects such as deviated Beptum, absence of olfactory bulbs, familial dysautonomia, or hypogonadotrophic hypogonadism. Miscellaneous problems, Including nasal medication, surgical Interference, radiation therapy to the head, Idiopathic hypoguesia with hyposmla; also hysteria and malingering. H.vposmla type II (pyridine threshold steps #10 through #13) Milder Incidence of the above conditions. Upper turbinate congestion due to allergy or head cold. Acute viral hepatitis, poliomyelitis, advanced syphilis, diphtheria, leprosy. Heavy smoking, chronic alcoholism, sniffing cocaine. Diabetes mellitus, hypothyroidism, some forms of hypopituitarism, hyperactive adrenal cortex. Some systemic medications and antibiotics. Miscellaneous conditions, including vitamin A deficiency, pernicious anemia, uremia, tine deficiency. Hvoerosmla (pyridine sensitivity step #22 or higher) Glucocortlcosterold insufficiency (Addison's disease). Some drugs, such as caffeine and strychnine. Some cases of pituitary tumor. Epilepsy, schizophrenia, specific allergy. DO a 03^760 CONFTnFNTTAl 16 Literature odor threaholds for n-butyl alcohol* Water-dilution threshold Air-dilution threshold Original data SI" 0.005% (v/v) 1 mg!1 1.00 ppm (w/vl 2.5 ppm (v/v) 0.50 ppm (v/v) 4.03X10" 1.00X10" 1,00X10" 2.01 X10" 4.02 X10" 2.0 mg/kg 3.6X10" M/i 2.77 ppm (vv/v) 2.00X10" 2.67 X10" 2.77X10" 6,6 X 10'1 9/1 6.50X10" Original data 1 mb/i 0.565 X10" mol 1" 0.000223 mg/I Act,, * 6X10" Act,,-: 7.0X10" 15 ppm (v/v) Act,, = 6X10" 33 mg/m1 1.10 X10'* mol/ce 1.2 mg/m' 0.013 mg/I -)og,t M/I = 7.81 0 JO ppm IvM 3.16 ppm (v/v) 62 ppm (v/v) 0.0231 mmHg 0.390 ppm (v/v) 2.8 X10'' ppm (v/v) 3.5 ppm (v/v) tog, ppb = 10 42 Bl" 1.00X10" 4.18X10" 2.23X10" 1.61 X10" 4.09X10" 1.45X10" 4.66X10" 3.60X10" 3.60X10" 7.24X10" 1.40X10" 3.30X10" 1.45X10" 04X10" 1.20X10" 1.30X10" 9.12X10" 9.11 X10" 9.60X10" 1.88x10" 7.20X10" 9.61 X10" 9.97X10" 9.23X10" 1.18X10" 8.50X10" 2.34X10" 1.06x10" 4.15X10" First reference Patsy, 1892 Beckman. 1917 Jung, 1936 Gevauden, 1948 Mullins. 1955 Moncrieff, 1957 ScherPerger, 1958 Nazarenko, 1962 Rosen, 1962 Baker. 1963 Gevauden, 1966 May, 1966 Flath. 1967 Dravnieks, 1968 Khachaturyan, 1969 Corbitt. 1971 Leffort, 1973 Heilman, 1974 Motkowitz, 1974 Moikowitz, 1974 de Grunt, 1975 Hertz, 1975 Lilterd, 1975 Pipgott, 1975 Dravnieks, 1976 Williams. 1977 Amoore, 1978 Leing. 1978 Punter, 1980 Geometric mean, air-dilution threshold = 2.54 X10" 9 1" <N = 29I * 2.54 mg m" -- * 0.B35 ppm tv/vj Stenderd devietion = Mh 7.14, Standard error = */- 1.44 * MW -- 74.1 B; D,, 0.806 9 ml"; VP,, = 6 99 mmHj, S,, = 73.0 9 1"; ti'-vvater partition coefficient et 26eC = 3.6 x 10'* leapt.). 3.61 X10" (eelc.l. K5 'jab*- ^v*^* / t44)44^ft*v*. IiAJL, /&*K&&**~* >7lt4Wi-A4i. 1^0 A 039761 0ONFTDFNTIAI 17 Explanation of column headings in Tables 2(a) and 2(b) Column 1. TLV's listed by ACGIH, 1982. 2. Volatility * vapor presB. (mm Hg at 25c) x 1,316 3. Air odor thresholdis geometric mean of all literature data (including converted water threshold data). 4. Standard error of mean odor threshold value. 5. Safe dilution factor (for saturated vapor) - volatility divided by TLV, 6. Odor safety factor TLV divided by odor threshold, 7. Odor safety class: see Table on page 28 for interpretation. 8. Water TLV equivalent: the aqueous odorant concn. that is in equilibrium with air TLV concn. 9. Solubility - literature soly. (g/l) x 1,000 10, Water odor threshold: the aqueous odorant concn. that is in equilibrium with the air threshold concn. 11 & 12. Molecular weight and density are needed when measuring out odorants to prepare water or air dilutions (see Useful Formulae). 13. Water-air distribution ratio reciprocal of the air-water partition coefficient (both concentrations in g/l). 14* The number(s) of literature reference values that were averaged to obtain the mean odor threshold in column 3. 18 DO A 039767 CONFTDFNTTAl WORK PAGE DO A 030783 CONFTDFNTTAl 19 J.l. AMyUKL ANlJL HAL 1 ALA Tbl* 2(a) Air-dilution odor threshold data on 214 industrlil chemicals. The numerics! dita are mostly rounded off to two significant figures. Note that ppm on this half f Table 2 are in */v units (jd l'1) for the gaseous chemical to air dilution. See Methods for further explanation of each column. TLVs are reproduced from Ref. 1 (1982) with permission from ACGIH Substance Acetaldehyde Acetic acid Acetic anhydride Acetone Acetonitrile Acetylene Acrolein Acrylic acid Acrylonitrile Ally! alcohol Ally! chloride Ammonia /Amyl acetate aec-Amyl acetate Aniline Artine Benzene Benzyl chloride Biphenyl Bromine Bromcrform 1,3-Butadiene Butane 2'Butoxyethanol /-Butyl acetate /Butyl acrylate /-Butyl alcohol arc-Butyl alcohol Mrr-Butyi alcohol /-Butylamme z-Butyl lactate /butyl mercaptan p-rerr-Butyltoiuane Camphor Carbon dioxide Carbon diaultide Carbon monoxide Carbon tetrachloride Chlorine Chlorine dioxide a-Chloroaceiophenone Chlorobenzene Chlorobromomethane Chloroform Chloropicrin 8-ChtorOprene o-Ch lorotoluene m-Cresol t/anr-Crotonaldehyde Cumene 1 Threshold limit value (ppm; v/v) 100 10 B 760 40 140 0001 0.1 10 2 2 1 25 100 125 2 0.05 10 1 0.2 0.1 0.5 1000 BOO 25 150 10 50 100 100 5 5 0.5 10 2 5000 10 50 5 1 0.1 0.05 75 200 . 10 0.1 10 50 5 2 SO 2 Volatility at 25'C (ppm; v/v) S 20 000 6700 290 000 120 000 0 360 000 5800 140 000 33 000 480 000 s 5200 9200 630 s 120 000 1600 11 270 000 8000 S B 1300 16 000 7100 9200 23 000 55 000 93 000 690 -49 000 850 450 B 470 000 B 140 000 B B 8.9 15000 190 000 250 000 34 000 290 000 4700 180 -41 000 6900 3 Air odor threshold (ppm; v/v) 4 Standard error U/-> 0.050 0.48 0.13 13 170 1.7 1.5 1.1 1.6 2.8 620 0.16 0.094 17 1.1 2.8 1.5 -- 2.4 1.3 1.2 5.2 0.054 0.0020 1.1 2.5 2.0 2.1 - 1.6 0.50 12 0.044 0.00083 0.051 _ 1.6 1.1 -- 2.2 1.3 1j6 2700 0.10 0.39 2.3 2.5 1.4 -- 2.5 0.035 0 83 2.6 47 1.B 5:3 14 2.0 2.6 2.5 7.0 0.00097 5.0 0.27 74 000 __ 1.4 -- 1.B 1.5 0.11 100 000 R 96 0.31 9.4 1.9 10 1.8 1.8 1.6 0.035 0.6B 400 85 0.78 1.1 1.6 -. 1.7 1.4 15 0.32 0.00028 0.12 0.0B8 7.9 1.6 2.4 1.1 2.9 5 Safe dilution factor 10 000 2000 1300 390 3000 7 3600 000 580 72 000 16 000 480000 40 000 52 74 310 20 000 000 12000 1600 56 2 700 000 16 000 1000 1300 52 110 720 180 230 650 19 000 120 97 000 85 230 200 47 000 20 000 29 000 1 000 000 10000 000 200 200 940 26 000 340 000 29 000 94 36 ' 20 000 120 274 JOURNAL OF APPLIED TOXICOLOGY. VOL. 3. NO. 6,1983 2Q #. y~< /#/< , 1% we = /e> X nJ- *** 6 Odor safety factor 7 Odor safety dess 2000 21 39 57 0.23 A C 8 6 D 230 0.61 110 0.12 1.8 8 0 6 E C 0.84 4.8 1800 61 000 1.9 0 c A A C 0.10 0.85 23 240 2.0 E D C B C 0.39 640 0.29 250 390 D A 0 8 B 290 60 38 2.1 27 B B B C c 0.71 510 2.0 7.3 0.067 D 6 C c E 92 0.00050 0.052 3.2 0.011 B 1 E C E 1.4 110 0.50 0.12 0.13 C B 0 E e 0.68 150 17000 17 570 D 8 A C A ff-- f.ONFTOFNT ODOR AS AN AID TO CHEMICAL SAFETY Table 2(b) Water-dilution odor threshold data n the amt 214 chemicals. Note that ppm on this half of Table 2 are In wft units (mg l*1);f r the chemical in aqueous solution. The numerical values in Table 2 are almost invariably compiled, averaged , re-caJculaied or extrapolated from the literature, and are nor new experimental determinations Substance e Water TLV equivalent (ppm. w/v) B 10 Solubility at 25 *C (ppm; w/v) Water odor threshold (ppm. w/v) 11 Molecular fveiQht 8> 12 Density at 20-25* C (g ml*') 13 Water-air distribution ratio (w/v) 14 Number pi thresholds performed ir wittr Acetaldehyde Acetic acid (A/4 7) Acetic anhydride Acetone Acetonitrile Acetylene Acrolein Acrylic acid (A/4.3) Acrylonitrile Ally! alcohol Ally I chloride Ammonia (B'9.2) n-Amyl acetate rec-Amyl acetate Aniline (B/4.6) Art me Benzene Benzyl chloride Biphenyl Bromine 67 2000 d 1100 70 - d ** (150) 0.066 1.1 26 1000 200 00C - 73 000 - (0 0075) 71 68 110 120 T600,,> 280 000 1800,o 1700 37 000 10.000035) (0 15) 0.28 0.12 0.012 670 1800 460,o 6.7 33 000 0 034 97 d 20 300 44 60 102 68 41 (0.67) 0.11 9.1 14 26 66 72 53 68 (0.00B9) 1.5 0.037 00017 65 (000035) (0.171 0.012 0.00050 0 0063 76 17 130 130 93 78 78 127 164 160 0 79,. 1.05 1.08 0.79 0.78 B 0.84 1.05 0 80 0.85 -0.94 B 0.88 0.B7 1.02 S 0 88 1.10 1 3 12 370 82 000 d 620 1000 1.0 2B0 240 6600 24 400 130 160 16 000 0.22 4.6 65 95 19 63 14 4 2- 20 8 3-- 2-- 71 122 4 2-- 11 2 54 -i 9i 1 m19 4 2-1 4-- Bromotorm 1,3-Butadiene Butane 2-Buioxyethenoi n-Butyl acetate 020 <0.881 <0.051) 65 3100 850 61 6800 0.51 (0 0014) (0.171 0.17 253 64 58 118 116 2.89 B B 0.90 0 88 38 0 40 0.027 91 41 641- 93 n-Butyi acrylate n-Butyl alcohol aec-Butyi alcohol rerr-Butyi alcohol n-Butylemme (B/1061 n-Butyl lactate n-Butyl mercaptan (A/10 8) p-rerr-Butyitoluene Camphor Carbon dioxide (A/6.4) Carbon disulfide Carbon monoxide Carbon tetrachloride Chlorine Chlorine dioxide (A) o-Chloroacetophe none Chlorobenzene Chlorobromomethane Chlorolorm ChlorppiCrin 22 420 730 620 17 1600,o 73 000 200 000 - - 370 10 00611 (0.064) 7.5 (7.5) 42 000 600,o - 5.5 1700,, 1400 (0 0361 (0.0013) <0 0271 (0.0065) 0 0071 1700 26 770 6300 87 000,, dd 5 5 1100 17 -16 000 (0.28) 7100 (0.0048) 1600 0 0078 7.1 19 290 6.2 128 74 74 74 73 520 (0 000012) (0 032) 1.0 (110) 146 90 148 152 44 (0.00039) (2.7) (0.52) 10.0020) 0.67 76 28 164 71 67 d 0.050 34 (2.4) 10.037) 155 113 129 119 164 0.90 o.ei 08 k 0 78 0.73 0.98 0.84 086 1 8 1.26 9 1.59 B 9 1.10 193 148 1.65 43 2800 2400 2000 1100 21 20 9 51 41 32 12000 3.3 1.1 600 0.83 1_ 6193 2- 1.2 6 _ 0.023 2- 0.85 10 1 2.2 7 - 26 1 1 d 16 16 6.7 7.1 2 62 114 1 11 P-Chloroprene o-Chiorotoluene m-Cretoi I A/10.1) rranr-Crotonaidehyde Cumene (0.016) (11) 640 7.2 (0 451 480,o 100W 23 000 150 000,o 63 (0.024) (0.0069) 0.037 0 42 10.00080) 88 127 108 70 120 0.96 1.08 1.03 0 85 0.86 0.45 41 29 000 1200 1.8 21 11 33 11 61 21 DO A 039765 CONFIDENT! Al Table -Continued Subelance Cycldhexene Cydohtxenol Cydohe xenone Cydohexene Cydbhexylamine Cydbpentediene Detaborene Diacetone alcohol Diborane o*Dichlorobenzene p-Diehlorobenzene tram 1,2-Dich loroeth y It ne ,S'-Dichioroethyl ether Dicyclopentediene Diethanolamine Difthylamine Oiethylaminoethanol Diethyl ketone Dntobotyl ketone Dnaopropylemme /V-Dimethyiaeet amide Dimethylamine /V-Dimethylanihne A/-Dimethylformamide 1,1 -Dimethy Ihydtazine 1,4-DiOxane Epichlorhydnn Ethane Ethanoiamine 2-Ethoxyethanoi 2-Ethoxyethyl acetate Ethyl acetate Ethyl ac'ylate Ethyl alcohol Ethylamine Ethyl n-amyl ketone Ethyl benzene Ethyl bromide Ethyl chloride Ethylene Ethylenediemine Ethylene bichloride Ethylene oxide Ethylenimine Ethyl ether Ethyl formate Ethylidene norbornene Ethyl mercaptan flf-Ethylmorphoiine Ethyl ulicate Fluorine Formaldehyde Fornuc acid Furfural Furfuryl alcohol 1 Threeho Id limit value (ppm; v/v) 2 Volatility ei25*C (ppm; v/v) 300 130 000 GO 2000 2G eooo 300 99 000 10 15 000 75 0.05 50 0.1 50 -560 000 -110 1600 e 1800 75 1200 200 420 000 5 1500 5 3600 3 78 10 10 200 25 5 310 000 2900 22 000 3300 110000 10 10 5 10 0.5 2600 9 1000 3100 210 000 25 2 140 000' 3 5" 52 000 21 000 9 780 7100 5" 400 5 1000 10 25 100 200 1000 140 000 10 10 r 0.5 400 100 5 0.5 5 10 1 r 5 2 10 2700 120 000 50 000 75 000 9 3600 13 000 610 000 9 9 16 000 110 000 9 260 000 700 000 320 000 710 000 11 000 3000 9 9 57 000 2100 810 3 Air odor thrtthold (ppm; v/v) 4 Standard error U/+I 25 0.15 0.88 0.1B 2.6 ia 0.060 0.28 2.5 0.30 2.8 2.1 2.2 -- 4.2 0.18 17 0.049 0.0057 0.27 4.1 16 1.9 -- 0.13 0.011 2.0 0.11 1.B 2.9 - 2.1 ' T 39 47 0.34 0.013 2.2 1.7 - 3.1 3.8 46 5.5 24 0.93 120 000 2.6 2.7 2.4 12 5.9 - 9.0 0.056 3.9 0.0012 84 0.95 -- 1.8 4.1 1.8 2.6 6.0 2.3 3.1 4.2 290 _ 2.7 2.6 1.0 88 430 1.5 8.9 -- 2.1 1.6 1.3 3.3 31 0,014 1.6 1.4 0.00076 2.0 1.4 18 17 4.9 0,14 0.83 49 0.078 8.0 23 1.9 1.7 - 6 Safe dilution feclbr 430 39 240 330 1500 7500 2300 33 10 000 000 37 17 2100 290 720 26 31 000 290 110 130 21 000 260 100 000 200 310 410 000 1000 11 000 7 260 1400 530 300 10 000 75 too 000 140 130 3100 1000 7 1600 11 000 1 000 000 520 000 1800 3200 1 400 000 2100 300 1000 000 1 000 000 11 000 1000 81 6 Odor eefety (actor 7 Odor efety date 12 340 28 1600 3.8 40 0.83 180 0.040 160 420 12 100 870 11 C 8 B A C 8 D 8 E B 8 C 6 A C 77 910 97 230 2.7 8 A 8 B C 0.21 29 400 4.6 0.30 D B 8 C D 1.1 C 2.1 C 1,2 C 1.2 c 1.8 c 89 100 4000 12 11 4,2 44 64 240 490 B e A c c c B 8 B B 10 0.11 0.0023 0.32 45 C E E D B 3.3 350 650 3.5 0.57 C B A C D 7.3 1.2 0.10 25 1.2 C c E C c 22 DO A 03976ft CONFTDFNTTAL Tab)* 2(b)--Contmutd 9 Subttance Warn TIV aquivaient (ppm;w/v) Solubility at 25 *C (ppm; wM Cyclohexane Cyeiohexanol Cyclohexanone Cve'ohextne Cyeiohexylamme (B/10.61 (013) 940 240 (0.65) 04 65 36 000 -54 000 210 t Cyeiopentadiene Deceborane Diacetone aicoboi Diborane dDiChlorObenzene (0.24) d 3.9 - 1800 m d 140 p*DiehtOrpbem*n* rra/M-1,2-Diehtoroethylene JJ'-Diehtoronhyl ether ^pieyctopentadiene " Diethanolamine (8/8.9) 4.7 13.0) 36 240 000 Diethytamine (8 T 1.0) Dtethylaminoethanol (B/8.BI Diethyl keiooe DusObutyl ketone Dusopropylamme (8/11.0) 36 450 3.3 3.5 79 6300 11 000 - * * 48 000 430 A'-Dimethylacetam ide Dimethylamme (8/10.7) /V-Dimethytamlm* (B'5 2l N-DimethyMormamKje 1,1-Dimethylhydrazine (B7.2) 8.6 9.9 1,4-Dioiene Epiehlorhydrin Ethane Ethanolamme (B/9,5) 2*Ethoxyeth*rvol 240 64 (B8i 23 000 *550 000 2000 - m ~ 65 000 60 - m 2'Ethonyethyi acetate Ethyl acetate Ethyl acrylate Ethyl alcohol Ethylamme (B '10 7) 450 270 1.5 8000 45 200 000,,, 73 000 15000 * It Ethyl n-amyl ketone Ethyl benzene Ethyl bromide Ethyl chloride Ethylene 10 (1.3) 12 9) (4.71 (19) -1500 160 9000 4700 130 Ethylenadiamine (B'10.01 Ethylene dichloride Ethylene oxide Ethylemmine IB/B 0) Ethyl ethe' 080 0.33 d 34 8600 270 000 d 56 000 Ethyl formate Ethylidene norbornene Ethyl mercaptan (A/10 51 M-Ethylmorphpline (B/ ) Ethyl silicate 35 100 000 (0.0049) 7000 m dd Fluorine Formaldehyde Formic acid (A/3 71 Furfural Furfuryl alcohol d 0.73 170 89 d d 650 000 - 86 000 --d 10 11 Mater odor threshold (ppm. *v/v) Molecular weight (9) (0011) 28 8.3 (0 00039) 25 84 100 98 82 99 10.0060) 64 d 0.024 66 122 116 28 147 0.011 10.26) 0.36 22 000 147 97 143 132 105 0.47 4.7 0.014 13 0.29 0.025 50 73 117 86 142 101 87 45 121 73 60 230 30 (7.5) 20 000 190 88 92 30 61 90 5.0 2.6 000038 760 4.3 132 88 100 46 45 2.5 (0.029) (0.046) (0.019) (0.039) 128 106 109 64 28 16 000 7.0 140 170d 0 75 60 99 44 43 74 11 74 120 10.0000075) 62 115 d 208 d 0.60 1700 3.5 d 38 30 46 96 98 12 Daniity at 2025*C (a mf'l 13 Wat*rair distribution ratio (w/v) 14 Number of thrtthohfc performed -----------------air water 0.78 095 095 0 81 0.87 0 12 4600 2400 0.64 2300 632 82 1 -1 080 . 0.94 g 1.30 1-2 d 13 1- 112 1 32 t 1.26 1,21 1.10 10 3.8 1200 19 000000 23 2 -1 2- 1 0.71 0.88 0.81 081 0.72 1200 640 23 -170 61 1 31 21 0 94 0 0.96 0.94 0.79 1 460 6 2 400 3 21 2 1.03 1.18 0 1.02 0.93 0.97 0.90 0.92 0.79 0.69,, 0.83 0.87 1.43 0 0 0.90 1.26 0 0.83 0.71 2700 840 0.051 3 100 000 16 000 180 74 4800 2400 80 2.9 3.3 1.8 0.12 20 180 d 28 71 2 2- 1 21 1 84 21 13 5 33 1 23 1 1 41 11 82 2 21 7 0.92 0.83 0.90 0.93 9 0 1.22 1 16 1.13 120 3.9 d d 590 18 00C 11 000 d 1 2 12 2 2 1 94 45 23 1 23 DO A 039767 OONFTOFNT JA! Table 2(a) --Continued Substance Haiothane Heptane Hexaehloroeyclopentadiene Hexaehioroethane Hexane Hexylene 9'yeol Hydrazine Hydrogen bromide Hydrogen chloride Hydrogen cyanide Hydrogen fluoride Hydrogen telenide Hydrogen sulfide Indene Iodoform Itoemyi acetate lioamyl alcohol Isobutyl acetate Isobutyl alcohol leophorone leopropyl acetate Isopropyl alcohol lOpropy famine Isopropyl ether Maloc anhydride Mesityl Oxide 2-Methoxyeihanol Methyl acetate Methyl acrylate Methyl acrylonitrile Methyl alcohol Methyiamine Methyl n-amyl ketone W-Methylaniline Methyl n-butyl ketone Methyl chloroform Methyl 2-cyanoacrylate Methylcyclohexane p/s-3-Methylcyclohexanol Methylene chloride Methyl ethyl ketone Methyl formate Methyl hydrazine Methyl rsoamyl ketone Methyl iiobutyl eartsino! Methyl mbutyl ketone Methyl isocyanate Methyl isopropyl ketone Methyl mercaptan Methyl methacrylate Methyl n-propyl ketone o-Methyl styrene Morpholine Naphthalene Nickel carbonyl 1 Threshold limit value (ppm; y/v) 2 Volatility at 25 *C (ppm; v/vl so" 400 0.01 10 so 390 000 60 000 78 770 200 000 25 0.1 3 5 10 100 18000 9 9 970 000 3 0.05 10 10 0.6 9 9 9 2200 '49 100 7100 too 4300 150 26 000 SO 16 000 s 450 250 400 s 250 0.25 79 000 67 000 740 000 210000 '170 15 5" 200 10 1 13000 16000 270 000 110000 88 000 200 10 so 0.5 5 160 000 9 2000 640 5000 350 160 000 2 -530 400 61 000 SO 710 100 SSOOOO 200 100 0.2 SO 25 130 000 760 000 65 000 4800 7800 so 0.02 200 0.5 100 6500 630 000 39 000 9 62 000 200 SO 20 10 0.05 21 000 3800 13000 120 620 000 3 Air Pdor threshold (ppm. v/v) 33 ISO 0.030 0.15 130 SO 3.7 2.0 0.77 0.58 4 Standard trrpr lx/') -- 1.7 6.1 2.0 1.1 2.2 1.9 0.042 0.30 0.0081 0.015 0.0050 1.2 1.5 3.9 1.8 0.025 0.042 0.64 1.6 0.20 1JB 1.3 1.8 2.0 -- 2.7 22 1,2 0.017 0.32 2.9 1.8 2.8 - -- 0.45 2.3 4.6 0.004$ 7.0 26 26 3.5 ' -- 100 3.2 0.35 1.7 0.076 2.0 4.6 2.1 - -- 120 2.2 630 500 250 6.4 600 1.7 0.012 0.070 2.8 1.2 ia 2.9 -- 0.68 21 IS 0.0016 0.083 2.3 23 2.0 1.9 11 0.29 0.01 0.084 0.30 2.2 4.0 - 1.9 3.3 24 6 Safa dikit ion factor 6 Odor aafaty factor 7 Odor tafety class 7900 150 7800 77 4000 1.5 2.7 0.34 64 0.37 C c D B D 4.0 180 000 330 000 200 000 97 000 0.50 0.027 1.5 6.5 17 D E C c c 330 000 20 000 000 100 000 220 81 71 0.17 1200 690 120 6 E A A 6 71 3900 A 43 2300 A 170 230 8 330 30 B 89 25 C 320 140 150 000 850 670 93 18 4.1 15000 0.77 8 C c A D 850 3200 1400 11 000 88 000 33 2.1 44 2100 0.14 6 C 8 A E 800 100 000 40 1300 1000 2.0 3.1 140 0.29 66 C c 8 0 8 470 260 150 14 5500 2.8 0.91 0.63 0.10 0.40 C 0 D E D 660 7600 330 000 96 310 37 0.17 0.12 4200 360 8 E E A 8 190 32 000 000 200 2000 000 620 73 0.0094 IOC 300 1200 6 E 6 8 A 110 76 670 12 10 000 000 18 170 2000 120 0.17 C 8 A 8 E DO A 039768 CONFTDFNTTAl T*>le 2(bl-Contmu*0 8 Subttance Water TLV equivalent (ppm, m/v) Solubility t 25`C Ippm. yy/v) Haiothene Heptane Hexachioroeyeiopentadiene Hexaehloroeihane Hemint (0.441 10.020) 0.0026 (0.661 (0.0024) 3400 2.9 20 50 9.5 Hexylene glycol Hydrazine IB/8.5) Hydrogen bromide (A) Hydrogen chloride (A) Hydrogen cytmde (A/9.2) d d 3.0 1 200 000 00 000 m Hydrogen fluoride (A/3.21 Hydrogen eelenide (A/3.9) 'Hydrogen tuftide (A/7.01 Indent Iodoform d m 19 (000036) 6800 (0.036) 3500 (0.18) '40 1.3 110 Itoemyl acetate Itoamyl alcohol Itobutyl acetate Itobutyi alcohol <topt>orone 66 630 34 310 140 1400 26 000 5900 89 000 12 000 Itopropyl acetate Itopropyl alcohol Uopropyl*rrune (B/10,5) laopropylether Maleic anhydride 97 3000 20 12 d 30 000 * 10 000 d Metityl oxide 2-Methoxyethano! Methyl acetate Methyl acrylate Methyl aerylonittile Methyl flcohol Methylemihe (B/106) Methyl n-amyl ketone A/-Methylenilme IB < 8) Methyl n-butyl ketone 36 130 45 0.29 1500 7.4 40 53 17 29 000 220 000 49 000 25 000 550 000 4300 6700 16 000 Methyl eftfotaform Methyl 2<yanoecrylaie Methylcyclohexane Ci*-3-Methylcyctohexanol Methylene chtoride (2.BI <0.0921 660 3.6 1300 14 9300 19 000 Methyl ethyl ketone Methyl formate Methyl hydrazine (B/7.9) Methyl iioamyl ketone Methyl itobutyl carteinol 310 210000 25 170 000 66 400 3 15000 Methyl itobutyl ketone Methyl itocyanate Methyl itopropyl ketone Methyl mercaptan (A/10.7) Methyl methacrylate 94 18000 dd 320 60 000 (0.0075) '14000 30 15000 Methyl n-propyl ketone a-Methyl ttyrene Morpholine IB/8.7) Naphthalene Nickel carbonyl 270 7.4 4 000 60 25 (0000012) 30 130 10 11 Water odor threthoid (ppm, w/v) (0.79) (0.0073) O.OC77 (0.010) (0.0064) Molecular yveight <9' 197 100 273 237 86 ' 160 d d 0.17 118 32 81 36 27 d 20 (0.0021) 81 (0.000029) 34 10.00026) 116 0.011 394 0.017 0.27 0.16 10 5,4 130 88 116 74 138 io 160 4.9 0.00080 d 102 60 9 102 98 1.0 3.0 0.0021 2.1 98 76 74 86 7 740 2.4 0.28 18 0.25 32 31 114 107 100 (0.97) 10.15) 6600 9.1 133 111 98 114 86 84 ISO 0.013 0.V6 72 60 46 114 102 1.3 100 d 67 3.1 96 - (0.000024) 48 0.025 100 15 0.043 0.021 (0.000072) 86 118 87 128 171 25 12 Dantity at 20-25*0 (g ml"1) 13 Watfr-air dittributiOn ratio (w/y) 14 Number of thrathoidt performed T 1.87 0.68 1.70 % 066 0.97 1.01 B 9 0.70 1.1 0.012 23 6,7 0.014 d d 270 1- 4-- 11 2 121 1 6 23 0.96 9 9 1.01 ft d 21 2.6 3.7 130 21" 26 1 11 3 0.87 0.80 0.87 0.80 0.92 0.87 0.78 0.69 0.73 120 1700 48 2100 4800 92 3000 '1700 11 d 83 $3 31 7 1 412 4 21 1" 1 085 0.97 0.93 0.95 0 80 079 t 0.81 0.99 0.81 570 210 130 110 600 80 170 2400 BOO 22 & 1" 1 13 4 23 22 1 1 1.34 1.11 077 0.91 1.34 1.4 0.057 2800 10 31 1 1 41 0 80 0.97 087 0.81 091 0.80 096 0.80 0 0.94 0.B1 0.91 1.00 I 192 530 100 240 10 460 d 460 7.6 73 380 31 47 0.035 81 3" 1" 1 51 11 62 41 2i 31 1 64 3-- D0 A 03^76^ CONFTDFNTIAl Table 11)-Ct>niinud ` Subttance 1 ThreahoW limit value (ppm; v/v) 2 Volatility t 25 *C (ppm, vM Nitrobeniene Nitroethane Nitrogen dioxide Nitromethane 1-Nitropropane 1 360 100 27 000 3B 100 47 000 25 13000 2-Nitropropane m-Nitrotoluene Nonane Octane Oirmum tetroxide 10" 2 200 300 0.0002 22 000 " 280 6000 18000 12000 Oxygen difludride Ozone Penteborene w- Pentane Perchioroethylene 0.05 0.1 0.005 600 50 g B 270 000 670000 25 000 Phenol Phenyl ether Phenyl mercaptan Photgene Photphine 5 460 1 29 0.5 2000 0.1 B 0.3 B Phthahe anhydride Propane Propionic acid />-Propyl acetate n-Propyl alcohol 1 140 000' 10 200 200 0.67 B 5400 43 000 26 000 Propylene Propylene dichloride Propylene glycol 1-methyl ether Propylene Oxide n-Propyi nitrate 140 000' 75 100 20 25 S 69 000 16 000 700 000 30 000 Pyridine Quinone Styrene Sollur dioxide 1.1,2,2 Teuechloroethene 5 01 50 2 5 27 000 130 9600 B 8400 Trtrahydrofuran Toluene Toluene-2,4-dinocyanate o-Toluidme 1,2,4-Triehiorobeniene 200 100 0.005" 2 5 230 000 37 000 *21 330 570 Trichloroethylene Triehtorotiuoromeihane 1.1,2Trichlorol,2,2- triliuoroethane Tnethylanmne Ttimethyiamine 50 1000 1000 to" 10" 99 000 B 430 000 93 000 B 1,3,5-T rimethylbeneene Trimethyl phoiphite n-Valeraldehyde Vinyl acetate Vinyl chloride 25 3600 2 34 000 50 21 000 10 140 000 5B Vihylidene chloride Vinyl toluene m-Xylene 2,4-Xylidi ne 5" 50 100 2 790 000 2400 11 000 190 3 Air odor threthold (ppm, vM 4 Standard error U/+) 0.01 B 2.1 0.39 3.5 11 1.7 - 2.6 - 4.2 70 0.045 47 48 0.0019 2.2 4.1 3.2 - 0.10 0.045 0.96 400 27 _ 1.9 - 1.9 1.8 0.040 0.0012 0.00094 0.90 0.51 1.5 3.7 4.4 1.7 2.5 0.053 16 000 0,16 0.67 2.6 _ 1.3 1.8 4.1 1.7 76 0.25 10 44 50 3.0 - - 4.5 - 0.17 0.084 032 1.1 1.5 1.4 3.0 2.0 1.3 21 2.0 2.9 0.17 0.25 14 5.4 1.6 2.9 4.1 2.1 28 5.0 45 1.7 ~ 0.48 2.1 0.00044 1.4 0.65 0.00010 0.028 0,50 3000 1J9 2.5 16 3.7 190 10 1.1 0.056 3.7 - 2.1 - 5 Sale dilution factor 360 270 330 000 470 620 2200 140 30 61 61 000 000 20 000 000 10000 000 64 000 000 1100 490 92 29 4100 10 000 000 3 300 000 0,7 7 540 220 130 7 920 160 35 000 1200 5300 1300 190 500 000 1700 1100 370 4200 170 110 2000 1000 430 9300 100 000 ISO 17000 420 14000 200 000 160 000 48 110 97 6 Odor aalety factor 7 Odor efeiy Clan 56 46 7.8 29 2.3 B B C 8 C 0 14 45 4.3 6.3 0.10 E 6 C C E 0.50 2.2 0.0052 1.5 1.8 O c E C c 130 <00 530 on 0.58 B A B E D 19 8.8 61 300 78 C C 6 8 8 1800 300 10 0 45 0.50 A 6 C D D 30 1.2 160 1.7 34 B C B C C 99 34 0.030 8.0 3.6 1.8 200 22 21 23 000 B B E C c c B c c A 45 20 000 1800 20 0.0017 B A A C E 0.027 50 82 36 E C 6 B 26 DO A 039770 C0NFTDFNTTA1 , Table 1\b)-Continued Subttanee Water TLV equivalent (ppm. v*/vl 9 10 Solubility t 25*C (ppm; im/v) Water odor threshold (ppm, Wi/v) 11 Molecular yveight <g> 12 Dantity *t 20-25 *C (g ml"') 13 Watar-eir distribution ret io (w/vl 14 Number el thretho'di parlor med ir wre Nitrobenzene N'troethane (A/8 4) Nitrogen dioxide (A) Nitromethane (A/10.2) 1-Nitropropane (A/' 8) 2-Nitropropene (A/7.7) m*Niirotoluene Nonane Octane Otmum tetroxide (A/12.0) 60 100 d 260 29 2100 27 000 d 110 000 15 000 0.11 2.2 d 9.1 12 7.6 3.6 (0.00561 (0.011) 0.0012 16000 500.. -0.17 0.66 69 000 53 O.OBO (0.00131 (0.0017) 0.012 123 75 46 61 89 89 137 128 114 254 1.20 1.05 g ,1.13 1.00 0.98 1.16 0.72 0.70 ft 1200 330 d 1000 310 13 6 -- 2 210 320 0.0054 0.0077 680 1 1 2 2 1 2 1 1 1 1 -- Oxygen dilluoride Oione Pentaborane -^Pentane Parchloroethylene Phenol (A/10.0) Phenyl ether Phenyl mertftptin (A/6.51 Phoigene Photphine Phthelic anhydride Propane Propionic acid (A/4.9) n-Propyi acetate n-Propyl alcohol (0.0000054id 100.,,d (0.00001 lid 54 (0.00064) 6100 (0.00028) 48 d dd 63 (0.033) 38 (0.022) 72 (0.311 150 (0.17) 166 1000 160 0.15 d (0.000111 85 000 4300 610 d 370,, 7,9 94 0.18 170 0.00028 110 d 9 (0.00020) 34 d (9 01 1700 92 1800 d 62 * 19 000 m d (1.01 28 0.31 23 148 44 74 102 60 g g 0.63 0.62 1.61 ft 107 1.08 g e ft 9 1.00 0.89 0.80 0.049d 1 - 3.2 6 -- d 1 0.019 3 - 0.90 31 62 000 21 000 66 d 0.27 16 6 23 22 6 6 d 1- 0.036 2- 56 000 11 2 110 4 - 3600 12 5 Propylene Propylene dichloride Propylene glycol 1-methyl iether Propylene oxide n-Propyl nitrate (50) 13.01 14 7.4 350 2800 370 000 8800.,, (0.028) (0.010) 31 15 42 113 90 58 105 9 1.16 0.92 0.83 1.05 0.21 8.8 300 69 31 11-- 2-- 1 Pyridine (B/5.21 Qu inone Styrene SuHur dtOxtdt (A'V9> 1,1,2,2-Tetrachtoroethane 28 11 (1.7) 0 19 1.7 m 14 000 320 8 000 2900 0.95 93 10.011) 0.11 0.50 79 108 104 64 168 0.98 ft 0.90 9^ 1.60 1700 25 000 7.8 37 50 15 10 21 10 3 13 3 Tetrahydro/uran Toluene Toioene-24-di itocyanate o-Toluidine (B/4.4) 1,2,4 Triehlorobenzene (1.4) d 91 10.23) 540 d 15 000 -26 10.042) d 11 (0.064) 72 92 174 107 1B1 0.89 0.86 1.22 1.00 1.45 3.8 d 10000 6.1 318 2 431 11 Trichloroethylene Trichlorolluoro methane l,1.2-Triehloro-1,2,2- tnlluoroethane Triethylamme (B/10 9) Trimathylamme (B/9.7) (055) 1100 88 71 000 4.5 410 000,. (0.31) 0.42 0.00020 131 137 187 101 59 1.46 1.49 1 56 0.73 9 2.1 210 190 71 1-- 1- 41 31 1,3.5-Trimethy Ibenzene Trimethyl phoephite n-Valeraldehyde Vinyl acetate Vinyl chloride (0.67) 97 dd 29 12 000 1.8 25 000,,, (0.0057) 1100 (0.015) d 0.017 0.088 (3 4) 120 124 86 86 62 0.86 1.05 0.81 0.93 9 6.4 d 170 60 0.44 63 1-- 13 41 3 Vinylidenc chloride Vinyl toluene rrt-Xylene 2,4 Xylidme IB/4.9) (0.041) (2 1) (1.6) 66 6400 -100 170 6400 (1.5) (0.421 (0.017) 1.8 97 118 106 121 1.22 0.90 0.86 0.97 2.0 8.7 3.7 6600 21" 82 1-- 27 DO CONF Binary step* (iog2) -4-3 0 3 4 6 6 10 13 Odor sofety factor (multiple of threshold) A practical guide to the quantitative interpretation of odor safety factors. The coordinates are log/probit, so care is required in interpolating between marked intervals. The sloping lines indicate the percentages of the population expected to respond to various fractions or multiples of the mean detection threshold concentration (1.0 on the x axis). The detection line represents the performance of fully attentive persons under good laboratory con ditions. The warning line shows what may be expected for distracted persons under factory or field conditions. The warning line is based on the results of Whisman er at.19 for the gas odorants ethyl mercaptan and thiophane. * ft /Sp>n.t tr* m ****** J fc Odor mfety cludficatioa Odor tafrty Ciwt factor Interpretation A >550 B 26-580C 1-26 D 0 16-1 E <0.16 More than 90V of directed parioni perceive warning of TLV eonoantration in tha air 80-40% of dittractad paraom parcaiva warning Of TLV Lett than 50V of detracted ptrtont perceive warning of TLV 10-50% of attentive pereoni can detect TLV concentration in the air Lett than 10% of attentive pereont can detect tha TLV DO A 03977? rONFTDFNTTAl I ~f" \ lrritsnt threshold concentrations of ten industrial chemicals. 1 Substance Acetaldehyde Acetic acid Acrolein Allyl alcohol Benzyl chloride o-Chloroacetophenone rranj-Crotonaldehyde Formic acid Propionic acid Pyridine Odor threshold (ppm; v/v) 0 066 0 16 18 1.4 0.040 0.040 0.11 130 0 24 0.71 * Detection threshold lot a ueneral anotmic 23 Irritation thresholds Nose (ppm; v/v) Eye (ppm, v/v) 2200 160* 11 30 35 0.034 14 1100* 370* 700* 11000 12 89 8.0 0.022 19 4 Ratio ol irritation and odor thresholds 33000 1000 61 21 200 0.55 130 8.5 1500 990 5 Irritation hazard (actor 22 16 110 15 8.0 0.44 7.0 220 37 140 DO A 397?3 29 CON/F r^DNrrAi Odorlzatlon of Industrial Cases Gas Natural (methane) Bottled (propane) Inert (argon) Oxidant (oxygen) Danger level in air * Typical odorization practice Odorant Threshold Concentration ppn ppm Safety factor 5 t-Butyl mercaptan 0.00025 2 Ethyl mercaptan 0.00076 7 Ethyl mercaptan* 0.00076 2* Dimethyl sulfide 0.0067 3 15 6* 6 600 400 550* 18 * Proposed b In addition to the normal 21< oxygen in airt i. e. a total level of ~~ Properties of Fuel'-Gas Odorants Odorant Threshold* ppm Hydrogen sulfide Methyl mercaptan Ethyl mercaptan n-Propyl mercaptan iv-Butyl mercaptan t-Butyl mercaptan Dimethyl sulfide Thiophene Dimethyl disulfide 0.0081 (26) 0.0016 (10) 0.00076 (1J) 0.0017 (5) 0.00097 (6) 0.00025 (3) 0.0067 (10) 0.00076 (9) 0.041 (7) ^ Pregzesc Molecular* Relative TLV f weight reactivity* ppm -62 -85 6 -121 36 -148 68 -115 97 -116 64 1 38 -98 121 -97 110 -85 34 5,000* 10 48 1,800 0.5 62 250 0.5 76 98 - 90 91 0.5 90 1 - 62 20s ee - 94 - * In parentheses is the number of literature references that were averaged. b Helps to predict volatility and co-distillation. c To be considered for liquid or regenerated cryogenic gases. * Ftr comparing vapor concentrations * Relative to tert-butyl mercaptan, arbitrarily aet at 1. Threshold Limit Value, to avoid adverse health effects (U.S. standards) * USSR standard) none quoted in U.S. 30 oo Co/s/F J 397?4 rDfrNTTAl Proposed rating and assessment of individual olfactory threshold sensitivities, using the pyridine scale for illustrative purposes* Pyridine scale step Sensitivity rating 23 A above 22 21 20 19 18 17 16 15 14 15 12 11 10 9 A below ;o ^5 4 *5 +2 41 A -1 -2 -3 -4 -5 -6 -7 -6 < -9 4 -16 Sensitivity assessment Hyperosmia High normal Above average Average Belov average Low normal Hyposmia Anosmia Complete anosmia Approximate frequency )a 2 14 66 14 2 0.2 0.02 * Calculated for a normal distribution, assuming SB - 2 binary steps. 51 DO A 039775 OONFTDENTTAt Factors affecting the normal smell sensitivities of healthy people. Thresholds are for pyridine in water Class of persons* Average 40 yr. man Average woman 18 yr. person 62 yr. person Moderate smoker Smoking during test Chewing during test Head cold Nasal allergy Un-trained Un-directed test Mis-directed test Odor recognition threshold Factor 1 1 0.5 2 1 4 4 4 4 1.4 4 26 3 Threshold (ppm) 4.0 4.0 2.0 8.0 4.0 16 16 16 16 5.6 16 100 12 * Understood to be average 40 yr. persons, unless indicated. A O3977. cn^rnFNTT^ 52 A classification of chemically induced hyposmias, according to the extent of the exposure and the duration of the resulting hypoamia. Exposure Hyposmia Duration Examples ACUTE (sec/min/hr) A Temporary J Reeuperable 1 Permanent CHRONIC (mo/yr) C Recuperable 1 Permanent minutes weeks years weeks years HgS HCN H2Se ZnS04 POClj so2 Acetone 2nCrO4 Cl2- -J 039777 00 A 0pMTT Al conf t 33 Subatencet Reported to Cauti Acuta Olfactory Injury in Man, Ratulting in Temporary, Racuparable, or Permanent Hypowniat. The table conclude* with one cate of chronic, but recuperable, hypotmia. Substance Expotun Cone. Time tetidwm of hypotmia Olfatfometric Frequency method (percant) Aatwtmerit A. Acuta axpoaura. tamporary hypotmia Formaldahyda Hydrogen cyanide Hydrogen aelenide Hydrogen tulfida OJJ ppm 100 ppm mm ut min IK B. Acuta axpoaura, racuparabla hypotmia Hydrogen aelenide /V-Methylformimino-methylettar Sulfuric acid Zinc tutfate get t*t. Vp. 6%toln.* 1% toin.t 2tee 2 tec 2 tec tec C. Acute exposure, permanent hypcnmva Cesspool Decomp. cadavar Pepper 1 Cratol j Phg^phorui oxychloride Sulfur dioxide h h powder 270 ppmt 2 tec tec 2 tec 0. Chronic expoture, racuparabla hypotmia Acetone Tatrahydrofuran l Cyclohexanone -) 3 mo symptom symptom symptom symptom symptom symptom symptom symptom symptom symptom symptom symptom symptom recognition 1 eeae 1 uu 1 cate 25 1 cote 1 cate 1 cate 1 case t cate 1 ewe hypotmia ftoimif hypotmia onosmi* onosmi* anosmia* onotmi* notmii notmie onotmis oootmis anosmis ( hypotmia r phantoamia I! Patient fall into t ditinfectent bath, the anosmia mav have been an indirKt consequence of tha reaultent chronic rhinitil. t Natal tpray intended at a prophylactic egaintt poliomyelitis. ^Concentration taamt underestimated. Thit toot the head apace of a 6 percent aolution of Mrljyroui acid, which it nearly latur* atad with ojlfur dioxide. 11 Two-mc exposure" indicates a tingle miff or inhalation. ^Confirmed in teru with mica 15). After OJSaoc axpoaura to tha aaturatad vapor, en anotmia of --30 binary ttapt aevarity raaulted, which paaiatad for 3 week*. *Tarma for olfactory perceptual abnormality OOI. cacoamia, obnoxious tmall tanaation cauatd by normally plaatant or nautral odoranu; phantoamia, partiitant odor aantation, even whan no odorant it inhaled. 00 oosip rn?397^ Tofnt JAI 34 Metallurgical Processes Considered Responsible, on Chronic Exposure, for Permanent Hyposmia In Man Incidence of hyposmie Substance Exposure Offectometric time (years) method Frequency (per cant) Rating (steps) Aasmsment Chromium Chromium plating Lead Lead (severe into*.) Lead (severe into*,) Magnet production* Mercury (chronic into*.) Nickel plating Nickel refining (electrolytic) Silver plating Steel production Zinc production 18 4 8 10 99 4 >6 6 4 >5 Elsberg recognition Elsberg Elsberg Elsberg recognition Elsberg recognition recognition recognition Elsberg Elsberg 17 cohort 33 cohort Cohort 10 cases 85 cohort 33 cohort 6 3 *lron, Aluminum, nickel, cobelt, end chromium powderi. tjust one worker wet effected, end he had e unilateral hyposmia. (-0.7) (-08)1 -1.2 -13 -38 - <-33 <-27 below average low normal below average below smrege below average hyposmie low normal low normal anosmia below average low normal low normal ' Metallic Compounds Considered Responsible, on Chronic Exposure, for Permanent Hyposmia in Man Eapoura Incidence of Hyposmu Subttanc* Cone Tune Olfectometric Frequency (mg/rn1) (years) method (per cant) Rating (steps) cf i Cedmiti'f compounds Cadmium compounds* Cadmium oxide Cadmium oxide 7 Nickel hydroxide 5 Cadmium oxide 1 Nickel hydroxide j Chromate setts Zinc chromate 13 9t 80 0.5t 031 10 7 3 20 15 18 10 Elsberg Elsberg recognition symptom Proett TliT Rosvburg 13 66 1 case 44 27 27 30 <-7 <-18 * -7 anosmia hypesmis 5 anosmia anosmia hyposmi anosmia hyposmie* *Oxide, sulfate, carbonate, nitrate, sulfide, aetemde, stearate, tBefore dust control. tAfter installation of industrial hygiene equipment. (The hyposmie was ameliorated by giving caffeine. Ia follow-up study on 11 of the seme workers 4 years later (after reducing the chrome-dust expoeure in the factory) showed no recovery of olfactory performance (99). 35 00 A 039779 OONFTDFNTTAI Duiti Considered Responsible, on Chronic Exposure, (or Permanent Hypotmia in Man Incidence of Hypoemie Substance Expoeure Olfactomatric time (yean) mat hod Frequency (par com) Rating (state) AaiWSHwnt Cement Chemicals Hardwoods Hardwoods Lime Printing Silicosis (first stage)* Pioett 2 hypotmia 6 Proett 8 <-M hypotmia symptom 6 ioosmi* symptom nosmi* Proeu 6 hyposmiat Naut 24 -2.0 low normal Eltberg cohort -1.2 below average First*, second*, end thirdetage silicosis cohorts ell showed about the same olfactory deficit. tDemegs to the olfectory epithelium, sensory ceils, end bulber fibers wet Observed in rets exposed 2 months in the dustiest locations in the fectory 164). Nonmetallic Inorganic Compounds Considered Responsible, on Chronic Exposure, for Permanent Hypotmia in Man Exposure Incidence of Hypoemia Substance Cone. Time Oifsctometric Frequency (mgteM (yean) method (percant) Rating letspi) Aaassment Carbon disulfide Carbon disulfide (average intox.l Carbon dituifida (intox.) Carbon monoxide Carbon monoxide (intox.)* Chlorine Hydrazine Nitrogen dioxide (NOx) "l Ammonia } Nitrogen dioxide (NOx) X Sulfur dioxide (SOa) , Sulfur dioxide Sulfur dioxide Sulfur dioxide 7 Ammomat j Sulfur dioxide (SO,,l ") Nitrogen dioxide (NOx) | Fluorides (HF7) 62t > 100 3 30 90 155 SO 15 Eltberg Eltberg 20 Eltberg! 13 recognition Eltberg 3 Proett Eltberg 5 Eltberg 8 Proeu 4 symptom 20 Eltberg >32 TST >5 Eltberg 22 cohort 14 1 case 8 70 cohort cohort 60 14 cohort cohort cohort -3.4 <-66 -08. tow normal low normal hypotmia aftotmi* nosmi* hypoemie below aversge -0.7 <-66 -3.4 ' below average hyposmie hypoemie low normal -4.4 hyposmie -12 below average `Includes both acute and chronie intoxications. tworkers exposed to ammonia alone showed no significant ollectory deficit, t Information given by 2enk (11). I The hyposmie could be partially or completely reversed, for 1 or 2 h, by injections of caffeine or tterine. n0 c^ro^r 56 Organic Compounds Considered Responsible, on Chronic Exposurefor Permanent Hyposmia in Man Capo*ura Incident* af hypotmit Subetance Actions Acetophenone Beniene Bensme Bennne *7 Ethyl acetaie > Butyl acetate Chloromethanes * Menthol Menthol PtnUchlorophenol Trichloroethylene Trichloroethylene (intermittent abuse) Cone. (ppm) Time (yaers) Otfectometric Frequency JMating method (percent) [Utepei Assessment 8 rtcogniuon 1 ease hyposmia 6 Elsberg 12 K-28) low normal 10 Elsberg Cohort --0.8 below average 400 8 Pioeti 37 -6 hyposmia 60 8 Elsberg 30 <-3.1 low normal 380 Ut. MP. 45 10 B Elsberg recognition tymptom symptom Neus symptom 44 cohort 1 cate 1 cate . cohort 1 case -2.7 low normal O hyposmia hyposmia ahosmiat -3.lt low normal complete anosmia ch, a. cH,ct,. chci, . ca4. tTested at beginning of ihift. ij., a permanent hyposmia. Whan tested at the end of the ihilt. an additional --2.1 steps o< temporary hyposmia wet demonstrated. (May have been due to upper respiratory tract infection, not occupational exposure. Manufacturing Processes Considered Responsible, on Chronic Exposure, for Permanent Hyposmia in Man Incidence of Hypotmia Subetance Exposure Otfectometric time lyaars) method Frequency (percent) Rating ' fstaga) Aesaasirwnt Acids (organic and inorganic) Asphalt (oxidised) Cutting oils (machining) Fragrances Faint (lead) Papnkf 'Tawnol" (sewing)* Spices Tobacco Varnishes Varnishes Waste-water (refineryl 7 Proets 5 <-58 hyposmia 6 Elsberg IB <-28 low normal Elsberg cohort -08 below average 4 recognition 50 below average Neus 56 -28 low normal 14 Elsberg 4 hypotmia Elsberg- 55 < --28 low normal 11 Nous Cohort -1J>t below average 12 Elsberg 1 hyposmia 10 recognition 7B low normal 5 Elsberg 1 hyposmia 7 Elsberg 18 <-28 low normal *A synthetic leather. The material contains a slightly volatile plasticiser, dibutyl phthalate, which may be rsaponsitee for the hyposmic effect. tTested et the beginning of the shift. ia..a permanent hyposmia. When tested at thaand of thathift.an additional -- 18 steps of temporery hyposmia was demonstrated. 37 00 ^ 39781 r.ONr TDFNTTAt ' Incidental Report* of Induttrial Subftancei Suipeeied of an Aiiociation with Hypoamia in Man, but with Inwfficiant Detail* Subtleno* Typa of hypoamia Metallurgical proeeitet Aluminum fumvt Artenic Chromium fumet Copper fume* Menpneie fumet Tin fumet Vanadium fumet Zinc fumet Metallic compoundt Alum Artenic compound! Bit-(diethyldithiocarbamato)admium Chlorovmylariine chloride* Chromic acid Copper artenite D>chromatet Ive Otmium tetroxide Potaitium tuifide Silver nitrate Strontium tuifide Duttt Cotton Cyanidet Flax flour Potath Nonmetatlie inorganic compound! Ammonia Bromine Flue pi ICO/SO, 7) Hydrazine Hydrogen chloride Hydrogen fluoride Nitric acid Nitrogen dioxide (N0,,! Photgene Selenium dioxide Sewer get <Ht5?) Sulfuric acid Chronic Chronic Chronic Chronic Chronic Chronic Chronic Chronic Acuta, recuperabia Chronic Acute, permanent Chronic, permanent Chronic, permanent Chronic Chronic Chronic, permanent Acute, recupereble Chronic Chronic, permanent Chronic Chronic Chronic Chronic, permanent Acuta, temporary Chronic, permanent Chronic, permanent Chronic, permanent Chronic, permanent Chronic, permanent Chronic, permanent Acute, temporary Chronic Chronic, permanent Chronic, permanent Organic compoondi Acetaldehyde Acetic acid Acetonitrile Acid Chloridet __BennJdehyde Butylene glycol Carbon tetrachloride Chloroform Dimethyl tulfate Ethyl ether Fluorine compoundi Formaldehyde Furfural Halogen compound! Iodoform Itocyanetet (TDI.etc.) Nitro compound! Phenylene diamine Selenium compound! tolatile) Sulfur compound! Tetrechloroethane Trichloroethane War getei (WW 1) m-Xylene Menufacturing proeeuei Bleating powder Coal ter fumea Perfume! Iconcantratad) Rubber wrlcaniiation Tanning Chronic, permanent Chronic, permanent Acute, temporary Chronic, permanent Acute, permanent*1 Chronic, permanent Acuta, permanent Acute, temporary Chronic, permanent Chronic, permanent Chronic Chronic Chronic Chronic Chrome Acute, temporary Chronic Chronic Chronic Acuta, permanent Chronic, permanent Chronic, permanent Chronic, permanent Chronic, permanent Chronic, permanent Dn A 039783 OONFIOFNITAI 3B Industrial chemicals reported to reduce the sensitivity of the trigeminal nerve to irritants. Substance Exposure Neuropathy Reference Carbon monoxide Chioromethanes* Dichloroethylene Smoke and soot*1 Trichloroethylene Trichloroethylene g Trichloroethylene Trichioroethylened 15 hr 6 wk 9 yx 2 mo > 1 yr > 1 yr Herberhold (1975) Fokina (1967) Koelseh (1959) Schwab (1965) Feldman (1970) Mitchell (1969) James (1963} Barret (1962)* a CHjCl, CH2C12, CHCIj, CC14 ^ Locomotive drivers. c Intermittent abuse. Also caused anosmia. d Of 168 chronically exposed degreasers, 17^ suffered neuropathy. * Includes literature review. +~jp r>o A COt\lfr 59 0FNTT^i Average chronic exposure coneentrailone associated with hyposmia, compared with threshold limit values (TLV, 8 hr 1VA) recommended by ACGIH (1984). Substance Table no* Units Concentration Exposure TLV Ratio Exposur /TLV ft Ammonia 7 Benzine 6 Cadmium compounds 5 Cadmium oxide Cadmium oxide 5 Carbon disulfide 7 Carbon monoxide 7 Nitrogen dioxide 7 (NO,) Sulfur dioxide 7 Sulfur dioxide 7 Sulfur dioxide 7 Trichloroethylene 8 Zinc chromate 5 ppm ppm mg/m^ mg/m^ mg/m ^ ppm ppm ppm 30 400 1.3 9 0.5 62 > 100 3 ppm ppm ppm ppm X mg/mr 90 155 80 580 10 25 300b 0.05 0.05 0.05 10 50 3 2 22 50 0.05 1.2 1.3 26 180 10 6 >2 1 45 77 40 7 200 & Not proven to cause hyposmia at this concentration. See footnote^ of Tabl TLV for gasoline. c Suspected carcinogenic potential for man. DO A 397ft CONF 4 rDr^TTO( 40 Odor pollution and odor aimoyanoe noar industrial plants in tha Ruhr* Estimated data^intsrpolatsd fros figures 5, 1 and 2 of Vinneke and Kastka (1977)* Source Dietanoe fros plant (netere) Pollution Odor units* 50?6 99* Odor-JLnduoed disturbances Headache (*) Nausea (*) Insulati <m plant (phenolice) 100 400 1600 13 110 5 16 -- 92 5 26 70 45 4 Tar-oil plant (hydrocarbons & sulfur opde.) 10 400 1400 15 110 40 450 20 100 65 74 70 44 64 56 Degrees of annoyance by odors Sensory Social Sosatic 5.2 4.0 3.5 3.4 2.0 1.1 0.0 0.8 0.0 4.2 2.8 1.8 4.5 2.6 2.4 3.9 2.8 1.9 a Odor concentrations that were not exceeded 50^ or 99* of the time, respectively - *7 /--2^4* j f^ ^ c~~c. [JO A 0 3 9 7 8 5 conftofntjal Predicted effects of ambient h)drogen sulfide level on frequency of odor detection, intensity of odor sensation, and incidence of annoyance by odor. Hydrogen sulfide (ppb) Persons able to detect odor4 <*) Perceived odor intensity*1 (ratio) Odor unitsc 5096 Persons annoyed by odor4 <*) 200 100 SO 40 35 30 25 20 15 10 e 6 4 2 1 05 99e 96* 91 86 87 83 80 74 69 56 50 42 30 14 6 2 2.31 25 1.93 12 1.61 6.2 1 52 5.0 1.47 4.4 1.41 3.7 1.34 3.1 1.27 2.5 1.18 1.9 1.06 1.2 1.00 1.00 0.93 0.75 0.83 0.50 0.70 0.25 058 0.12 049 0.06 88 75 56 50 47 40 37 31 22 17 11 6 5 2 1 a Based on adopted mean detection threshold of 8.0 ppb and S.D. * 2.0 binary steps. b For those vho can detect die odor. Based on LindvaJTs (1974) value for the intensity exponent, p0.26. c Hydrogen sulfide level divided by mean detection threshold (8.0 ppb). 4 Based on assumption that mean annoyance threshold is 5 x mean detection threshold, and S.D. *2.0 binary steps. e Theoretical for a normal distribution. These percentages may be reduced by the occurrence of selective smell-blindness. 43 ^ A/! T.C-, DOW CHEMICAL U.S.A. /=/ S/B LATEX TECHNOLOGY CENTER August 21, 1984 -MICHIGAN DIVISION MIDLAND.' MICHIGAN *8610 H. Ahlich .. H. Barenburg L. Battisti J. Bornenann R. Brown ... J. Cortinas. M. Dahley .. C. Davis ... .... Freeport Rh e irsme ns ter ........... Livorno San Lorenzo ...... Sarnia ........... Bilbao Midland (743) ............. Altona cc: C. Royalty . Midland (2040) C. Baldwin Midland (1803) C. Fioranti .....................Guaru j a J. Geaaan................................... Dalton J. Martin............. Pittsburg T. Mathewson .... Allyn's Point M. Piche Varennes C. Salway ..................... King's Lynn G. Tegg..................... Norrkoping N. Tilwans ............... Terneuzen Reference: ODOR AS AN AID TO CHEMICAL SAFETY I recently came across an article in the Journal of Applied Toxicology which I have attached in full. Additionally I have extracted the major raw materials that we handle in our S/B Latex Plants; note the impact of the probable change in the butadiene TLV. ?he concept of an Odor Safety Class is, 1 felt, an excellent one as it highlights those chemicals which - "YOU CANNOT SMELL BEFORE YOU ARE IN TROUBLE". These chemicals are the ones which we need to put at the top of our industrial hygiene monitoring program. We need to pay special atten tion to abnormal jobs (i.e., line breaking) and put extra effort into plant design to minimize all exposures. I intend to incorporate this idea into an update of our Industrial Hygiene Manual and future Plant Audit Books. If you have any data on raw materials that are not covered, please send it to me and we will distribute. Dave Waite, Technical Manager S/B Latex Technology Center 433 Building - Midland, Michigan Enc. (20 pages) 039786 DO 8 gonft PjFNTI A' dgr cUtlVED * AN OFERATINO UNIT Of THE DOW CHEMICAL COMPANY S/B LATEX RAW MATERIALS ODOR SAFETY CLASSIFICATIONS, RAW MATERIAL Threshold Limit Value (ppm; v/v) Air Odor Threshold (ppm; v/v) Odor Safety Classification Acrylic Acid---------------- -------- 10.0 ------------------- -- 0.094 ---------------------- B Acrylonitrile ------------- ----- 2.0 --- ----------- 17.000 -------------------------E Ammonia --- ------------------------------ 25.0 -------------------- 5.200 -------------------------C Bromoform ----------------------------- 0.5 ~-- -----------------Butadiene (Current) ----------- 50.0 Butadiene (Proposed) ---------- 10.0 n-Butyl Acrylate------------------- 10.0 1.300 --- ---------------- D 1.600 B 1.600 C 0.035 B Carbon Tetrachloride ----------- 5.0 -------------------- 96.000 --------------- -------- E Formaldehyde------------------------------ 1.0 0.830 C Styrene------------------------------------- 50.0------------ ;------------ 0.320 -------------------------B Vinylidene Chloride ---------------- 5.0 190.000 E ODOR SAFETY CLASSIFICATIONS Class Odor Safety Factor _________________Interpretation A More than 550 ---------- More than 90% of distracted persons perceive warning of TLV concentration in air. g --------- 26 to 550 --------------- 50 to 90% of distracted persons perceive warning of TLV. C----------- 1 to 26 --------------------- Less than 50% of distracted persons perceive warning of TLV. D----------- 0.18 to 1.00-----------10 to 50% of attentive persons can detect TLV concentration in the air. E Lass than 0.18------Less than 10% of attentive persons can detect the TLV. D. Waite 08-2 1-84 dgr on ? 039787 C-Onf TDF/mA( Odor as an Aid to Chemical Safety: Odor Thresholds Compared with Threshold Limit Values and Volatilities for 214 Industrial Chemicals in Air and Water Dilution * John E. Amooret OlTsclo-Labi, fO Box 7J7, El Cerrito, California 94JJ0, USA Earl Ibulala Weitttn Rteionsl Research Center, US Department oT Apiculture, Agricultural Research Servlet, Berkeley, California 9*110, USA Key words: odor threshold; threshold limit value; volatility, solubility; distribution ratio; chemical safety. The body of infoimnlort in this paper b directed to specialist) in industrial health and safely, and air and wsrer pollution, who need quantitative data on the odor thresholds of potentially hazardous chemical eipors and jues. The literature, largely unorganized, has been reviewed for 2J4 compounds and condensed Into tables based on consistent unit). Data on the volatility, solubility, ionization and wator-air distribution ratio at *5*C are included. From the currently recommended threshold limit value (TLV), a safe dilution factor and an odor safety factor are calculated for tarh compound. The equivalent diti are presented for both air and water dilutions of the chemicals. Available data are summarized on the variability of odor sensitivities in the population, and the increased odor concentrations that ire required to elicit responses from persons whose attention is distracted, or who are sleeping. This Information is reduced to calibration charts that may be used to estimate the relative detectability, warning potential and rousing capacity of the odorous vapors. Each compound has been issigned a letter classification, (tom A to E, to indicate the mtigin of safety, if any, that may be aflotded by the odor of the compound as warning (hit Its threshold limit value is being exceeded. INTRODUCTION The human sense of smell, although not as acute as that of some other mammals and certain insects, can be a valuable source of information about chemicals in (he environment. The nose is exceedingly sensitive to certain repulsive smelling compounds, produced In trace amounts by patho genic or putrifying bacteria and molds, such as methyl metcaptan, Itimethylamine, l-pytroline and isovaletic acid. Although these chemicals themselves ate generally harmless to man in the concentrations occurring naturally in air, waiti or food, heightened odor sensitivities to them may have developed from the protection offered against dangerous or fatal infection ot food poisoning. With the ad'ent of the industrial revolution, persons have been exposed to diverse chemicals, many of which are commonly found in workplace settings at concentrations much higher than occur naturally. Some of these pose an inherent risk to health at certain concentrations. In tecognition of this potential haiatd, the Amctican Con ference of Governmental Industrial Hygienists (ACCIII) publishes an annual listing of Threshold Limit Values {TLV).1 {TLNf i$ a registered ttadcmaik of ACCIH, whom we thank fot permission to use the TLV designation in this paper.) The TLV used in this papet is the time-weighted average value. Based on the best available inJusttial health data, it is defined as the lime-weighted average concentra tion for a normal S-h work-day and a 40-h work-week, to t Ault.or to *bem correspondence should be addressed. which neatly all workets may be repeatedly exposed, day after day, without adverse effect. The actual concentrations of specific chemicals in the working environment can^ be sampled and analyzed by various chemical and instrumental means, to determine whether the TLV is being exceeded. The necessary equip ment, however, is often expensive, cumbersome and slow, and tequires professional skills to operate and interpret. Nevertheless, there is a littleconsideted alternative, the human nose, that could serve as a first-line warning system fot hazatdous concentrations of many chemical vapors The nose Is peiftctly placed to sample iht inspired ait, monitors rapidly and continuously, and may tvtn exceed the sensi tivity of the best instruments. It is, however, at best only seml-quantitative, and it tequires calibration to detetmr.e its sensitivity to those chemicals that ate of Importance in industrial practice. In this trgard, it is necessary to evaluate the Increased concentration of a compound that may be required to alert the acetate person to the presence or an odor, while engaged in another activity which tequites attention. The typical variability of the population for odrr sensitivity and responsiveness should also be taken into consideration. METHODS Literature search for basic data A starch was conducted lor the olfactory and physiocherucal characteristics of all volatile Compounds and gases listed ccc-o:6o-4j7\/sj'Oooj-o:7;scs.so 272 JOURNAL OF APPLIED TOXICOLOGY, VOL. 3.NO. S. 1983 ...................... .. JM) A 0397R8 9 0 N F TDFNTTAL ODOR AS \M AID TOCHt.'IICAL SAI CTY in the JlircihoU Limit IViirj' Tot 1982. The fiul objective wit to find lileraluie yglues for the odni-dctecliun thresholds, measured by dilution In either air or water. Dilulion of odotanit in air can be achieved either dynami cally. by adding a calibrated flow of odorant vapor to an ai(itieani, or statically. by dispersing a known amount of odorant In a vessel or chamber. In the water-dilution procedure, the odorant is prepared as a series of aqueous dilutions in dosed, partially filled vessels from which the head space vapors can be sniffed. Previous reviews Include those of LalTor!,1 Patte tt at.,1 van Geinert and Nettenbteijer.4 van Center!,1 Fanalarl* and the ACGIH Documen tation of ThrtihoU Limit I'ahtcs.1 In practically every case, we consulted the original articles, so as to minimize errors of transcription, calcula tion or duplication. Nearly all of the odor thresholds and references are available in the recent comprehensive com pilations by van Centert.4'1 If an author gave only a recognition threshold, this was accepted, because recognition oF an odor requires on average only about three times the detection thteshold concentration.* If, for any compound, an odor threshold could be located, then a further scatch was conduct'ed for relevant physical data. The molecular weights, liquid densities and Ionization constants (of acids and bates) for theie common compounds can be found In laboratory handbooks. The vapor pressures at 25 *C were usually interpolated by linear regression computations from the tables of Stull.* Solu bilities In water at 25 *C wet* often Interpolated graphically front data collected by Seidell and co-wotkers.*1 n More current Information Is given in Verschueten's handbook.11 Certain missing data on vapor pressures, solubilities, ioniza tion constants, and also occasionally data on the air-water partition coefficient, were found In Bcilatein's Handbuch'1 and Us four supplements. A few solubilities were estimated by extrapolation of homologous series or by comparison with isomers. The air-water partition coefficient describes the relative distribution of a chemical In this two-phase system. Quanti tatively, it Is the ratio oT the concentrations of the chemical in air and water (both expressed as g I*1) at equilibrium. For compounds of finite water solubility, the coefficient Table l. Literature odor thresholds for n-butyl alcohol* Wntr^ilutlon thruhold Alr-dUvtlon threshold Origin*! data gi" Original data 1*' First nlsrieet O.OOS\ N/v) 1 mjr! 1,00 pom lr/v) 2,5 pom lv/v) 0 50 pom (v/v) 4.03 X 10" 1.00X10" 1.00X10" 3.01 XI0" 4.03 X 10" 2,0 mg/Vg 3.6 x 10" M/I 2.7 7 ppm (vy/vI 2.00X10" 2.67X10" 2.77X10" 6.S x 1Q'1 g/l 6.50X 10" 1 vg/i 0.565X 10" mol 1" 0.000323 mg/1 Act,, >9Z 10" Aei,, - 7.0 X 10" 1 5 ppm (v/v) Act,, * 5X 10" 33 mg/m* 1.10X10" mol/ee 1.2 mq/m1 0.013 mg/1 -tog,, m/I = 7.91 0 JO ppm (v/v) 3.16 POm (v/v) 62 ppm (v/v) 0.0231 mmHg 0.390 ppm |v/v) 2.8 X 10" ppm (v/vl 3.S ppm (v/v) log, ppb - 10.42 1.00X10" 4.18X10" 2.23X10" 1.61 X10" 4.09X10" 1.45X10" 4.56 X 10" 3.60X10" 360X10" 7.34x10" 1.40X10" 3JO x10" 1.45X10" 1.34X10" 1.30X10" 1JOX10" 9.12X10" 9.11 X10" 9.60X10" 1.88X10" 7.20X10" 9.61 X 10" 9.97X10" 9.33 x 10" 1.18X10" 6.50X10" 2.34X10" 1.06x10" 4.15X10" Fairy, 1892 Baekman, 1917 Jung. 1936 Gavaudan, 1948 MuHint, 1955 Moneriefl, 1957 Schrprg*r. 1958 Nttinnks, 1962 Roicn, 1962 laker, 1963 G***udan( 1966 May. 1966 Flaih, 1967 O'avnieks, 1968 Khaehatury an. 1969 Corbitt. 1971 Laltort, 1973 Hallman, 1974 Moikowitz, 1974 Motkowiii. 1974 da Grunt. 1975 Hani, 1975 l/Hard. 1975 Piggoit. 1975 DtavnliVj, 1976 Williams, 1977 Amoo't, 1978 Lain*. 1978 Punt*r# i960 Gtomttric mun( tir-dilutlon threshold * 2.54 X 10" g 1" (A/ - 291 w 2.54 mg m" * 0.835 opm (v/v) Standard deviation - a/* 7,14; Standard trrof ** j/+ 1.44 * MW a 74, t g; 0 ,,0 606 g ml"; VP , * 6,99 mmHg; S-i^TOOgr*; sr-vitr pa^itton cotlliciant at 25 `C - 3.6 X 10' * (evpt.l. 3.61 X 10' lea'e.l. JOURNAL OF APPLIED TOXICOLOGY, VQL. 3.N0, 6. 15*3 27 I. E. AMOOHC AND L. HAUTALA Table 2(a) Air-dilution odor threshold dal* on 214 Industrial chemicals. The numerical data tre mostly rounded off to to significant figures. Not* that ppm on this half of Table 2 art In / units (*rl I"1) for the gaseous chemical in air dilution. Sec Methods for further explanation of each column. TLVt are reproduced from Ref. I (1982) with permission from ACGIH Substance Acmidfhyd* Acme atiO ActtC inhydrid* Acetone -t... Aettpnitril* Acetylene Actolcin Acrylic tcid Acrylonitrjlt Ally( tlcsSol AHyl cMoride Ammonti n-A^yi ftcttji* Jec-Amyl ecetsit Antlin* Af lint Benrtne Cmiyl cMoridi Biphenyl 6f"imtn B'Onto^crm 1f3-Buldient Buttnt 7 Eutc*y*thnc! n-Bgtyl Ktittt /i-6uryi acylitr /`Butyl |CDhl jT'8u(yi titohoi rtrf-Butyl ilcohol n-Butylirnm* n-Suiyf t*ette p-ttrT-Butyltoibtnc Camphor Carbon dec*id* Cartoon diiulftdc Carbon monov*dC Carbon tttracMorJd* Chlonnt Ch<orm dioxide 2o 7 i^ 1O CO sO \/ o 0'loroceioD*s*nont Chlorobenitnt Chip' obfotnp^-te^htri* Chlorofofrm 0> lo f 00 krm d.D'torcprtna O-OiiOfCtoluf"* fn-Onoi v/ni'Ooioni~t iyd Cdmffle 1 Thrffhotd limit vlut (ppm; y/v) 2 Volatility at 35 *C (ppm; y/v) 100 ID s 750 40 140 ooo1 0.1 10 2 2 20 OOO 6700 290 000 130 000 9 360 000 5800 140 000 33 000 1 35 TOO 135 3 480 000 8 5200 9200 630 0.05 10 1 0.3 0.1 8 130 000 1600 11 270 000 0.5 1000 Ijo) 800 25 150 8000 8 8 1300 16 000 10 50 100 100 5 7100 9200 23 000 55 000 93 000 5 0.5 10 3 5000 90 -*9 000 850 450 8 10 so 5 1 0.1 470 000 8 140 000 8 0.05 75 200 10 0.1 96 15 000 190 000 250 000 34 000 10 290 000 so 4700 5 180 3 -41 000 SO 5900 3 Air odor threshold (ppm: vM 4 Standard rror la/e) 0.050 0.48 0.13 13 170 1.7 1.5 1.1 1.6 3.8 620 0.16 0.094 17 1.1 2.8 1.5 2.4 lj 1.2 5.2 0.054 0.0020 1.1 3.5 2.0 2.1 16 0.50 _ 12 1.6 0.044 1.1 0.00083 - 0.051 2.2 IJ 1.6 2700 0.10 0.39 2.3 2,5 1.4 - 2.5 0.035 0.83 2.6 47 1.8 5.3 1.4 2.0 3.6 2.5 7.0 0.00097 5.0 027 74 000 _ 1.4 - 1.9 1.5 0.11 100 000 96 0.31 9.4 16 10 1.8 IB 1.6 0 035 0.68 400 85 0 78 1.1 16 1.7 1.4 15 023 0 00028 0.13 0 088 76 1.5 2.4 1.1 26 27 journal of appi tFn Tnxi'.nt nr.Y vm i tin i i9Bi S Sat* dilution factor 10 000 2000 1300 390 3000 7 3 600 000 580 72 000 16 000 480 000 40 OOO 52 74 310 20 000 000 12 000 1600 56 2 700 000 16 000 1000 1300 2 no 720 180 230 550 19 000 120 97 000 85 230 200 47 000 20 000 29 000 1 OOOOOO 10 000 000 200 200 940 25 000 3*0 000 29 000 94 36 20 000 120 6 Odor saterv factor 7 Odo' utery elan 2000 21 39 87 0.23 A c 8 8 0 230 0.61 110 0.12 1.8 8 0 8 E C 0.B4 4.8 1800 61 000 .; 16 0.10 0.8$ 23 240 2.0 0.39 640 0.29 250 390 0 c A A C E 0 c 8 C D A (O D B 8 290 60 38 2.1 Z7 8 8 B C c 0.71 510 2.0 76 0.067 D B C c E 92 0.00050 0.057 3.2 0.011 B E f 4" c^ E 1.4 110 0.50 0.12 0.13 C 8 0 E C 0 68 150 17 000 17 570 0 8 A c A OUOH AS \N AIU tnriir.'JItALSAI I.IY Table 2(b) Water-dilution odor tlirethold dill on ihe him 214 chemical*. Nnlt llul ppm on Ihiihilf of Table J ate in w/v unid (rn| I*1) (or the chemical In tqucoui lotulion, The numerical value* In Table 2 are almoit invariably com piled, averaged, re calculated or extrapolated from the literature, and arc nor new experimental dercrminaiion* Sutit *nc# > Weter TLV equivalent (ppm; w/-v| 9 10 Solubility (ppm; wM Water odor thretnoid (ppm; yv/vl 11 Molecule' (fl> 12 Denuty ar 20-25 'C <9 ml'M 13 ftittr-iir d UtibutiOn ratio lM 14 Nymbif of thretfcold! performed 4ctlAldhyd Acetic *c>d IA/4.7) Aeenc anhydride Action* Acetonitrile 67 2000 d 1100 70 - d * M 0 034 97 d 20 300 44 80 102 58 41 0.79.. 1.05 1.08 0.79 0.78 370 83 000 d 820 1000 3 14 4 330 3-- Acetylene Acrclem Acrylic Kid (A/4 3) Afy tomtrile Ally 1 alcohol 1150) 0.068 1.1 26 1000 200 00C 73 000 * (0.671 0.11 9.1 14 26 56 72 53 58 9 0 84 1.05 0 30 0.85 1.0 290 240 5600 371 1-- 22 4-- Allyl c^lOrtde Ammenn (B/9,2) n-Amyl acetate jrc-Amyl acetate Amlin# (B/4 5) I0 007S) 7.1 68 110 120 3600 ,, 280 000 18001, 1700 37 000 10.0083) 1.5 0.037 0.0017 65 76 17 130 130 93 0 94 0 88 0.87 1.02 2.4 400 130 160 16 000 311 2 54 -i 9i .Arym# Bfn*en Benryl chloride 8p h t n y l Bromin# (0.0000351 10,15) 0.28 0.12 0.012 670 1800 460,. 6.7 33 000 10.00035) 10.17) 0.012 0.00050 0.0063 78 78 127 154 160 9 0.83 1.10 s 3.12 0.22 46 55 95 19 1-- 19 4 2-i 4-- 8romofOrm 1,3BuTadre Butane 2'8utyeth"ol o-Eutyl acetate 0.20 10.88) (0.051) 65 3100 850 61 6800 0.51 (0 0014) (0.171 0.17 253 54 58 118 116 2.89 9 9 0.90 0.88 38 0 40 0027 91 4i 64i- 93 n-Bwtyl acrylate ff-Buryl afcorol ttc Butyl alcohol ferr Butyl aicohol /'Buryiamtne (B/10.6) 2.2 *20 730 620 17 1600,, 73 0C0 200 000 * 0.0073 7.1 19 290 8.2 128 74 74 74 73 0 90 0 81 0.81 0.78 0.73 43 2800 2400 2000 1100 21 20 9 51 41 32 "Butyl lactate n-Sutyl mercaptan (A/10,S 1 p-'frf-Butyltolucne Camphor Girbon diot*de (A/6.4) Carton dtrjlfidt C#fbon moroi'd# Carbon tetrachloride Chlorine Chlorme dioindt (A) o-'CHloroftcetophenpnc Chlorcoen/ene Chlorobromome thane Chloroform Chloroptcrm 370 I0OC6D (0 06a) 7.S (7.5) 42 000 600., -5 5 1700,. 1400 (0.036) 10.0013) (0.027) (0.0C65) 0.0071 1700 26 770 6300 87 000,, dd 5.5 1100 17 -16 000 10.281 7100 (0.00481 1600 520 (0 00C012) (0.032) 1.0 (110) 146 90 148 152 44 10,00039) 12.7) 10.52) (0 0020) 0.67 76 28 154 71 67 d 0.050 34 (2.4) 10.037) 155 113 129 119 164 0 98 0.84 0.86 1 9 . 7 -26 9 1.59 1 9 1.10 1.93 1.43 1.65 12 000 3.3 1.1 600 0.83 1-2 0 023 0.85 2.2 26 d 16 16 5.7 7.1 1_ 6 193 2 8_ 2 w10 1 711 3_ 62 1 14 1 t1 0*Chloroprne 0-ChiQfoto`uc ne m-Creiol (A/10 1) fr*nj-Crotonaid*nyde Cwmen# 10.016) 11.11 640 7.2 10 45) 00 A 039?9i cnatd fnttai 480., 100,, 23 OCO 150 000 ,, 53 10 024) 10 0069) 0.037 0.42 I0 0008CI 88 127 ioa 70 130 0.96 1.08 1.03 0 85 0 86 0.45 4.1 29 000 1200 1.8 21 11 33 V1 61 JOURNAL of applie 0 TOXICOLOGY VOL. 1. NO. 6.1583 Taba rial -- fonrmvftf Subtiti-iet CrCloM*at Cye)ohanot CydOMOnont Cycloht p# Cyc!h4*Yl*rnif\* Cydo&f ntic3i*n# Dtcaborani OUctiOA* alcohol O'bor#nt e*OicMof bbtrwant pDicMorobtntf nf f/#Ai-l,2'D`Chlroethyl*nt fi.f -Okhlofcxthyl *\h*r 3icydco*ntidirvt Oijih>Aolfrr>in* D! f t * v 19 m i n ^lHhyiamihcathanol Diaihyl VttOn* Ciilbbulyl kttona D>'cfCpy limin# N D1 m et h y Uc t *m *d D'mrthyUrTMAf A/-D^fthyltm|inl //Oirntthy l*ormvr%tdi l.l'D^flhylhydrUiA* 1,4-Die * Eo-chlorhydrin Ethtnt E th* ncl* th At 2-ElhOytth*nol J Eihoiyeihy) vcttait ihyl acttait Iihyl aerylait Ethyl alcohol Elhylmtra Ethyl A myJ fcatonv E thyl ba A2t a* Ethyl bromtda Ethyl ch>ordf Elhyltn* Ethyltnvdiamint Ethylena d<Chlcrd Ethyttnf oiidt Fthylenimin* Ethyl\h*f Ethyl lotmait lhyfdtn* nort>orn*nc Ethyl mtfcaotan ^/EthylmOrpholiA* Ethyl tipcat* FK>oma F u-.'nf'df hyd* Fo*me c*d Fyi-funl FwHury 1 alcohol 1 Thff fhold limit vttwt Ippm; v/v) 300 SO 35 300 10 75 0.05 SO 0.1 50 75 300 S 5 3 10 10 300 35 5 10 10 s 10 0.5 35 3 140 COO1 3 5" 5" 400 5 1000 10 35 100 300 1000 140 ooo1 10 10 r o.s 400 100 5 0.5 5 10 1 r 5 3 10 3 Volatility 1 35 *C (ppm; vM 130 OOO 3000 6000 99 000 15 000 560 000 - no 1600 i 1800 1300 430 OOO 1500 3600 78 310 000 3900 33 000 3300 110 000 3600 1000 3100 210 000 53 000 31 000 g 780 7100 2700 120 000 60 000 75 000 1 3600 13 OOO 610 000 9 16 000 110 OOO * 260 000 700 000 330 OOO 310 000 11 000 3000 9 S3 000 3100 10 :76 JOURNAL OF APPLIED TOXICOLOGY o n -J O > i Air odor thitihold Ippm; v/vl 4 Standard rror UA) 35 0 15 0.88 0.18 3.6 38 21 3.3 - " 13 o.oso 0.38 3.5 `0.30 _ * - 4.2 0.18 4.1 17 18 0,049 -- 0.0057 13 0.37 - - 0.13 0.011 2.0 0.11 1.8 2.9 3,1 33 47 0.34 o.ota 32 1.7 3.1 3.8 46 5.5 34 033 120 000 26 2.7 3.4 13 5.9 -- 9.0 0.056 3.9 0.0012 84 0.95 6.0 2.3 3.1 4.2 390 1.8 4.1 1.8 3.6 --. 3.7 _ 3.6 1.0 88 430 1.5 8.9 _, 7.1 13 13 3.3 31 13 0 014 1:4 0.00076 2 0 1.4 18 17 43 0.14 0.83 *9 0 078 80 2.3 1.9 1.7 - 6. 1953 5 Sa'a dilution (actor , Odor llUty * (actor 7 Odor ta'aty data 430 13 C 39 30 a 340 38 9 330 1600 A 1500 3J c 7500 2300 33 10 ooo ooo 37 *0 0.83 180 0.0*0 160 8 0 * 1 8 17 3100 390 730 36 31 000 390 110 130 21 000 260 100 000 200 310 *10 000 430 13 100 70 11 77 910 97 330 a.r o.:i 39 *00 4.6 0J0 8 C 8 A c 8 A 8 C o 8 8 C 0 1000 11 000 7 760 1*00 1.1 c 3.1 c 1.2 c 1.3 c 1.8 c 530 - 300 10 000 75 100 000 89 5 100 8 4000 A 13 c 11 c 140 130 3100 1000 7 4.2 44 64 3*0 490 c 8 B 8 8 1600 11 OOO 1 000 000 530 000 1800 10 0 11 0.0023 0.33 45 C E t 0 3300 1 *00 000 2100 300 3J 350 650 3.5 0.57 c A c 0 1 OOO ooo 1 OOO ooo 11 ooo 1000 1 7.3 1.3 0.10 75 12 DO A 03979? CONFTDFNTT At, c c t c c  SutMUnc* Cyc'oH^i^n* CfdoKe*oi Cyc'o^fno* Cve'ohfit n* CvdoMiy tamm* (BH0 6) W(*f TLV fqgivelcM (ppm; I 10 01 940 J40 10 SSI 94 CyclO0ntdi*n* Otciboran* D>actont alcohol Oibonne 0'0ichtorOb*oj|n (0.241 d 3.9 P'OicMorobtnirn* ,2.0'ehloroethyltn* 0JT-Oichlorothyl ether ClcyclOpent*dito Olfthanolamm* 18/8.91 4.7 (3.01 36 240 000 Oltlhylamlnt IB/1 1.01 Oiethylamlnoelhinol (0/0.8) 0>ethyl ketone DHiObutyl ketone O'itoprppy famine (8/11.0) 36 4SO 3.3 3.5 A/.Dimethy lac* timid# 0*rn*thyl*min# (0/10,7) W-OimtthyWniUni (8/5 2) N-0)m f l hy 1 f 0 rm a m Id * l.l-Oimnhylhydralln# (0/7.2) 86 9.9 9 Sohjfttivy 25*C (ppm: wM ss 36 000 -54 000 310 - leoo 4d 140 79 6300 11 000 - 48 000 430 to 550 coo 2000 * 10 11 Water odor ihrcihold (ppm: vt/vl Molaculac Vdpf^ht If) 1001 11 28 3 (0.000391 35 64 100 98 82 99 10.00601 64 d 0.034 66 137 lie 38 147 0.011 (0.26) 0.36 32 000 147 97 143 133 105 0.47 4.7 0.014 1.3 0.29 0.025 SO 73 117 86 142 101 87 45 121 73 60 12 Otoi'iy M 20 2S*C If ml"') (1 Watif.air dtiribwtio* , rafip f**M 14 Numb" ol ttmiKgift performed )e wwt tt 0 78 0 95 0.95 081 0 87 0.13 4600 3400 0 64 3300 633 2 1_1 0.80 0.94 1J0 t 136 131 1 1.10 1.3 d 13 10 38 1200 19 000 000 1 1 13 t32 13 3 *1 2 1 071 0 88 081 081 0.73 0.94 0.96 0.94 0.79 1300 640 23 -170 1 1 3 1 31 .1 460 400 1 83 3 31 2- 1,4-Oioxmc EpiChlorhydrin Ethane Elhanoiimint 10/3,5) 2EIhOiythnol 340 8.4 (6 8) 23 000 to 65 000 60 4 330 3.0 17.5) 20 000 190 88 1.03 3700 71 92 1.18 840 2 30 f 0.051 3- 61 1.02 3 100 000 1 90 0.92 31 2'Ethoiytihy! acetate Ethyl acetate Ethyl acrylate Ethyl alcohol Ethylamn# (0/)O.7) Cthyf mamyl keton# Ethylbenztnc Ethyl bromide Ethyl chloride Ethylene Ethylenediemin# (B/10.0) Ethylene dichlor;d* Ethylene Olid* Ethy'tmmin* 18/9 0) Ethylether 450 270 l.S 9000 45 10 (1.3) (2 9) (4.7) 119) 0.80 0.33 d 34 200 0C0., 73 000 15 000 - -1. -- 1500 160 9000 4700 130 to 8600 270 000,, -d 56 OOO 50 3.6 0.00038 760 4.3 3.5 (00291 10 0461 (0.019) 10.039) 16 000 7.0 140 170d 0.75 132 88 100 46 45 128 106 109 64 38 60 99 44 43 74 0.97 090 0 92 0.79 0.69., 0.83 087 1.43 f 0.90 136 < 0 83 0.71 16 OOO 180 74 4800 3*00 SO 2.9 3.3 1.8 0.13 30 180 d 38 1 84 31 13 5 33 1 23 11 41 11 83 2 31 7 Ethyl format* Ethylidfne norbornen# Ethyl mrreiot** (A/1Q 5) /V-EthylmorDholm* (0/ ) Ethyl illicit* 35 100 000 10,00491 7000 dd 11 74 120 (0.0000075) 62 115 d 208 0.92 0 33 0 90 0.93 120 3.9 d 11 2 13 1 3 2 Fluorine Formaldehyde Formic led (A/3.7) Furfu r! Fgrfuryl icohol d 0.73 170 89 d d 550 000 to 86 000 -d DO A 039793 OONFTDFNTTAl d 38 f 0 60 30 f 1700 46 133 3.5 96 1.16 d 98 1.13 d 590 18000 11 COO d 1 a4 4s 23 1 JOURNAL OF APPLIED TOXtCOLOGf. VOL. 3. NO. 5,1983 277 7ll--Conyad Sublltnci 1 ThrtlKold limit vp!u lppm; Wvl 3 Volatility *< 25*C (ocfn;Nl 3 Air odor thrfthold tppm; M 4 Sltndl'd rrof UA> 9 ( dilution Ucier OOor fKlor 7 Odor M>*tV clou Hfptan* H*#chkKOCyCle>p*ntdif n* Wf i chlorot7hjr>f so" *00 0 01 10 so 390 000 60 000 78 770 200 000 33 ISO 0.030 0 IS 130 1.7 8.1 _ 2.0 7900 ISO 7800 77 4000 1.8 C 2.7 c- 0.34 D 64 8 / 0.37 0 Htiytfnt flycol Hyd'llln* Hydte^cn bromld# Mvd'o?*" eM>id Hyd'o^tn cyantd* 3S 0.1 3 S 10 100 18 000 970 000 SO 3.7 2.0 0.77 0.58 1.1 7.2 1.9 4.0 180 000 330 000 200 000 97 000 O.SO 0.017 1.9 6.5 17 0 C c c/ c HydtPQt* lluor<d HytfTOgtn feint'd* Hydrogen fulftda Ind* n* Iodoform 3 O.OS 10 10 0,6 9 1 2200 -*9 0.0*2 0.30 0.0081 0.015 0.0050 17 - 1.S 3.9 1.8 330 000 30 000 000 100 000 220 81 71 0.17 1200 690 120 a E A A B lica^yl acttlti Uoimyl ilcohp! hebUTyl aetiatt liothityl ilcohol hophoron* 100 7100 100 *300 ISO 26 OOO so 16 000 5 *50 0.025 0.0*2 0.6* 1.6 0.20 1.6 IJ 1.8 3.0 - 71 3900 A *3 2300 A 170 230 8 330 30 8 89 2S C tlQOrppyt Kftatt IlCpropyt !cohl IlCP'OPYlaTiint Isopropyl ther tnbydiidt 250 *00 s 250 0.25 79 000 57 000 7*0 000 210 000 -170 2.7 22 1.2 0.017 0J2 3.9 1.8 2.8 -- -- 320 1*0 ISO 000 BSO 670 93 18 4.1 1S 000 0.77 a c c A 0 Mityl Paid* J.Mt fhpty* thirtol Mtthyl actuate Mfthyl tcrylan Mfthyl aery lonitrilf 15 5" 200 10 1 13 000 16 000 270 000 110 000 88 000 0.*5 2.3 4.6 0.0048 7.0 26 26 3.5 -- - 8SO 3200 1*00 11 000 88 000 33 2.1 44 2100 0.1* a c a A E Mfthyl alcohol M*ihyl*mint Mfthyl /i^myt kftona A/-Mf thy lnltn* * Mfthyl ft-butyl kftom TOO 10 SO 0.5 5 160 000 9 2000 6*0 5000 100 3.2 0.35 1.7 0.076 2.0 4.6 2.1 -- - 800 100 000 *0 1300 1000 2.0 3.1 1*0 0.29 86 c c a D a Mfthyl chlorplprm Methyl 2<y-'cacryln* Mtthylt yCloht i)nf cji-3-Mt thylcyeioheianol Mfthylfn# chlorld* Mfthyl ftlhyt kfion* Mfthyl fprmttf Mtthyl hydrailn* Mfthyl feoamyl krtpna Mfthyl itebutyl Catbinol Mfthyl iiobviyl kiton* Mfthyl rsocvnatf Mfthyl iteotcpyl kttonf Mfihyl mtrcipian Mfthyl mtthacryltf Mfthyl A<CfCvt Vtio'n* Mfihyl it y ft MO'phol'ftf N*phf* Af N<W*t carbonyl 350 2 *00 50 100 200 100 OJ 50 25 50 0.02 200 0.5 100 200 50 20 10 0.05 160 000 -530 61 000 710 550 000 130 000 760 000 65 000 *800 7800 9500 630 000 39 OOO 9 52 000 21 000 3800 13 OOO 170 520 000 120 2J 630 600 250 2.B -- -- _ !J 5.4 13 30 2S 1.7 - 0 .012 ' 0.070 -- 0.68 2.1 1.9 0 0016 0.0B3 2 J3 - 3J 3.0 1J9 11 0 29 0 Ot 0 OB* 0.30 2.2 4.0 -- 1.9 3.3 278 JOURNAL OF APPLIED 7OXICOLOCY, VOL. 3. NO. 6. 1987 470 260 150 14 5500 660 7600 330 000 96 310 190 32 000 000 200 2 000 000 520 110 76 6>0 12 10 000 000 3.8 ' 0.91 063 0.10 0.*0 c o 0 E 0 37 0.17 0.13 4200 360 73 0.0094 100 300 1200 is 170 7000 170 0.17 C a A a a * i 00 A 039794 CONFIDENTIAL .U l* *'* .* i ** ' 1 \ i -U '9 6 -4 3 1 *1 ij iis * C.4 ., r'. 'f` \ . >; .V -``Jr . g -. 1; 7<> " ,a .-. : i 1 Tab'* 2lbl-Cenhnt/*d Subtlmct 1 W.I.r TUV Ouivateni (pom; *M 9 10 Solubility tt 25`C (pom; y*Av| W*lr sdO' threshold (ppm; w/v) 11 Moltoi'ir vghi i*i 12 *. 0*"(ty t 20-2S*C 13 14 Wliu-lir distribution nil* (wM three*** Hr hw Helothana Henaehioroeyetapent adienf Mtiachloroe thane Hcian Htiylln# glycol Hydratme (S/3 31 Hydrogen bromide (A) Hydrogen chloride (A) Hydrogen cyanide (A/9.2) Hydrogen fluoride IA/3.2) Hydrogen itlenidi IA/3.9) Hydrogen Jyllid* tA/7.0) Indtne lodO^Orm 1044) 10 020) 0 002S I0 6SI 10.0024) 3400 2.9 20 50 9.3 -- d d 3.0 1 200 000 500 000 " d (0,00035) (0036) (0.1 B) 1J 6800 3500 -40 no 10 29) (0 0073) 0 OC77 10 0101 <0.00641 197 100 273 237 16 160 d d 0.17 118 32 1 36 27 d 20 (0.0021) 81 (0 000029) 34 (0.0007$) 116 0.011 394 1.87 0 68 1.70 1 0.66 097 1.01 f 0.70 0.96 t * 1.01 1 1.1 1 0.013 4- 33 i * 8.7 - 0.014 2- d d 270 1 2I 1 821 d 2.1 28 3.7 130 2125 1 11 3- lioamyl acetate IfOamyt alcohol liobutyi acetate Itobuiyl alcohol Uophoronf laopropyl acetate llOprOpyl alcohol liopropyiamne (6/10.5) liopropyl ather Maleic anhydride 66 630 34 310 140 97 3000 20 12 d 1400 26 000 5900 89 000 12 000 30 000 - 10 000 d 0.017 0.27 0.15 10 5.4 130 88 116 74 138 1 JO 160 4.9 0.00080 d 102 60 59 102 93 0.87 0 80 0 87 0.80 0.92 0.87 0.73 0 69 0.73 130 1700 48 2100 4800 92 3000 -1700 11 d 8S S3 31 75 1 412 4 31 1 1 Mesityl o>ide J.Metho ay ethanol Methyl acetate Methyl aery late Methyl acrylonitrile 35 130 45 0.29 29 000 - 220 000 49 000 25 000 1.0 30 0,0021 2.1 98 76 74 86 67 0.85 0.97 0 93 0 9$ 0.80 570 210 130 110 2351 1 Methyl a'cohol Methylamlna (9/10 5) Vethyln-amyl Itetcne N.Mtthytin.llnt (S/4 81 Methyl n buryt Vttcne 1500 74 40 5.3 17 * 550 000 4300 6700,, 16 000 740 2.4 0.23 18 0.25 32 31 114 107 100 0.79 9 0.81 0.99 0.81 5600 580 170 2400 800 13 4 33 33 11- Methyl ch'hmjforiri Methyl 2<yjnoacrylate Methylcy cfohf a *n Cr#*3*Methy!cy clohea ar.ol MaihyJent cMoridt 12.8) (0.0921 660 3.6 1300 14 9300 19 000 (0.97) (0.151 6600 9.1 133 111 98 114 85 1.34 1.11 0.77 091 1.34 1.4 0.057 2800 10 311141 Methyl ethyl ketona Methyl formate Wnflyl hydruin. (8/7.91 Methyl ifoamyl ketone Methyl iioburyl carbinol Methyl ifobuty! ketona Methyl isocyanate Methyl isopropyl keton* Methyl mercaptan (A/10,7) Mth/| mathacrylata 310 25 56 53 210 000 170 000 - 5400 16 000 94 18 000 dd 320 60 000 (0 00751 -14 000 30 15 000 8.4 ISO 0.013 0.15 72 60 46 114 102 1J d 100 57 3.1 10.0000241 86 48 0.025 100 0.80 097 0.87 081 0.81 0.80 0.96 0.60 0.94 530 10O 240 510 460 d 460 76 73 81 j111- 5- 111 83 41 Methyl n "propyl ketona 'M^hy! styrene Mof^hoiln. IB/8.7) Naohthaiene Hicktl carbonyl 270 7.4 54 000 560 - 2.5 (0.000012) 30 130 15 0.043 0 021 10.0000 721 86 118 7 128 171 081 091 1.00 % 1.32 380 31 47 0.035 31 31 t84 J- C,0^1D *, JOURNAL Of APPLIED TOXICOLOGY. VOL. 3.N0. 8.H13 279 Tfbi ?ll-Ce*/nv*d 5ubtt*nc Thttthold limit valuv (ppm; v/y| 2 Volatility t 25*C Ipp'n; *M 3 Air odor Ihrtjhold (ppm; vM 4 Standard rror U/t| Niuobf r>;en# Nlwotthtnt NHtoyin d<o*id* Ninomt thin# 1NitrODrct>an t 100 3 100 25 350 27 000 *7 000 13 000 o.on 2.1 0.39 3.5 11 1.7 - 2.6 - 4.2 2-M;tfop'opii># /n-NifrotOluvni Non*nt Odin* Oimiwm tctrex'fdt 10" 2 200 300 0.0003 22 000 -280 6000 18 000 12000 70 0.0*5 47 *8 0.0019 2.2 -- 4.1 3.2 - Oftyfftn diMuorldt Oien* Ftm*borna Ftnt*** Fifcbloronhyl^n# 0.05 0.1 0.005 too 50 270 000 670 000 25 000 0.10 0.0*5 0.96 400 27 15 - IJ 1.8 Fhnol Fhtnylt^her Fh*nyf mercaptan Fborgan* Phoipt'-m 5 *50 1 29 0.5 3000 0.1 t OJ 0.0*0 0.0012 0 00094 0.90 0.51 1.5 3.7 4.4 1.7 2.5 Fhthjlic anhydrid* Fropant Fropionic atid n-Propyl Kttlt* ft-F rOpy 1 aicohoi 1 1*0 ooo1 10 200 200 Fropyl*nt FtopvItnf dic^'oftd* rFropykne glycol 1 ^methyl th*r Frppylfnt Oxidf ft-Fropyl nitrile 1*0 ooo' 75 100 20 25 0.67 9 5400 *3 000 26 000 8 69 000 16 000 700 000 30 000 0.053 16 000 0.16 0.67 2.6 _ lj 1.8 4.1 1.7 76 0 25 10 14 50 3.0 _ -- 4.5 - Fy rrdiot Quiftona Slyrtn* Sulfur ti.oxide 1.1.?.2'T>traehloro thane 5 0.1 50 2 6 27 000 130 9600 8 B*00 0.17 0.084 0.32 1.1 ________ 1-5 1.4 3.0 2.0 1.3 2.1 Teirahydrofuran Tduf n# Totuin*-7,4^i ii&cy*nata o-Toluidina 1^.4.T rich loro btnitna 200 100 0.005" 2 5 230 000 37 000 -21 330 570 2.0 2.9 0.17 0.25 1.4 5.4 1.6 IS 4.1 2.1 Trichloroethylene T rlchioofluoromth*r>f 1,1.7-Tilchlorot,2.2. trlfhioroathent Tricthylamlnf Trlmtthy Itmint 50 1000 1000 10" 10" 99 000 9 430 000 93 000 9 28 5.0 4`5 1.7 -- _ 0*8 2.1 0.000** 1.4 1.0.S^T rimtthyfbt ftitna Trimethyl pnotphiie ft?V*lera1dehyda Vinyl acttiti Vinyl chloride Vifiyltdfnf chlpiide Vinyl toki*n4 m-XyWn# 2,4-Xyl<d*n* 25 2 50 10 5 5" 50 100 2 3600 3* OOO 21 000 140 000 9 790 000 2*00 11 000 190 0.55 0.00010 - 0 028 2.5 0.50 1 3000 3.7 190 10 1.1 0.056 3.7 - 2.1 " 9 UU dilution lacior 360 270 330 000 470 520 2200 140 30 61 61 000 000 20 000 000 10 000 000 54 000 000 1100 490 92 29 4100 10 000 000 3 300 000 0.7 7 540 220 130 7 920 160 35 000 1200 5300 1300 190 500 000 1700 1100 370 4200 170 no 2000 1000 430 9300 100 000 ISO 17 000 420 14 000 200 000 160 OOO 48 110 97 6 Odor , t*litv (actor 7 Odo* (1*11* elm 56 46 7.8 29 2.3 0.14 45 4.1 63 0.10 B C > c E C c c 0.50 2.2 0.0052 1.5 1.8 D c E C c 130 BOO 530 0.11 0.58 19 8.1 61 300 78 A 8 f/ 0 c c 8 8 1800 300 10 0.45 0.50 A 8/ C 0 D 30 1.2 160 1.7 34 8 C B c c/ 99 34 0.030 8.0 3-6 8 8 E C C 1.8 200 22 c 8 c 21 23 000 c A 45 20 000 1800 20 0.0017 A A C E 0 077 5.0 2 36 E C 280 JOURNAL OF APPLIED TOXICOLOGY.VOL. l.NO. 6. 1383 * Table 2lbUC0n(f^v*(/ .i 4 $ubiian(f , NitfObtO/*n# M.trofth^ff (A/8.4* i Nitroijyn diand* (Al # 4 Nilromtihtnt (A/10 31 'i "" 4 l-NilrOpropan IA/-8) Wlttr TLV Owivalrnl Ippm; *>/vl 0 100 d 360 39 10 Solubility 1 35*C Ippfn: #/vl 3100 37 000 d 110 000 1SOOO Water odor thr tfhokJ (ppm; n/v| 0.11 3.3 d 9.1 13 II MaUcul*' ll 13 '* 0*niny tt 30-25'C If ml-'l 13 14 NyrtitFf of Wat'*it dltU'buIppn * ftliO tn/vl thrtiholdt pftfoimad ilr watar 133 75 46 1 *9 1 30 1.06 1.13 1.00 1300 330 d 1000 310 13 3 -1 - 1 31 \i 2Nitroproein IA/7.71 m-Nit/ptoluf r 7.6 16 000 53 19 0.98 3.6 500 ,, 0.080 137 1.16 FiOnant 10 0056) -0.17 (0.00131 138 0.72 Octmt 10.011) 0.66 (0.0017) 114 0.70 i Oirr>kjm ttro*ida (A/12.0) 0.0013 69 OOO 0.013 354 210 t1 330 1 0.0054 2 0.0077 3 - >80 1 * - Sc >* * * Ovygtn diMuorida Otonc Fimebor*n* Ptmana Farchloroethylena Phtnol (A/10.0) PTltnyl f thi'r Fhnyl marcjDlm (A/6 5) Phoigtn* .hpiphine (0.0000054)d 100,,d (0.000011 Id 54 (0.00064) 6100 10.000381 48 d dd 63 (0 0331 38 10 0331 73 (0.31) 150 10.17) 166 1000 150 0.15 d (0.00011) 85 000 4300 610 d 370,, 7.9 94 0.18 0.00028 170 110 d (0.00020) 99 34 1 063 0 62 1.61 1.07 1.08 1 0.049d 1 3.2 6 d1 0.019 3 0.90 31 53 000 31 000 66 d 0.37 16 33 33 6 6 Fhthflie anhydridt d d d_ 146 I d 1 tr FfOpant 19 0) 63 11.01 44 8 0.036 3 Fropionie acid (A/4 9) 1700 38 74 1.00 6 000 11 3 A-Propyl acatiia 93 19 000,. 0.31 102 0 89 110 4* /i*Ffopy| alcohol 1800 - 33 60 0.80 3600 13 8 ** Fropyla ^a (501 350 (0 0281 42 * ` Ffopylana dichlo/ld* (3.01 3800 (0.010) 113 1.16 `> Frppylene glycol 1-maihyl tther 90 092 i Ffopylan* oxida -4*\ n-Fropyl nitrate 14 7.4 370 000 8800.. 31 15 58 105 0 83 1.05 0.21 8.8 300 69 31 1 1 3 1 " ^yridlot (8/5 11 38 - 0 95 79 098 1700 15 10 Oulnon# 1 1 14 000 9J 10B f 25 OOO 31 Styrtra (1.7) 320 (0.0111 104 0.90 7.8 10 3 SuHur d.o.de (A/1.91 0.19 88 000 0.11 64 9 *? 141,2,2-TttracHlorcfthjna 1.7 3900 0.50 168 1.60 37 13 50 3 1 Tvwahydrofuran * 72 0.89 3- Tofuena (1.4) 540 (0.043) 92 0.66 3.8 18 3 Tolu* ne*2.4-^ii toe y *nite d dd 174 1.22 d 4 0*Toluidin# (8/4.4) 91 15 000 11 107 1.00 10 000 31 - 1,2.4-T ricMorebeni tn 10.331 -36 10.064) 181 1.45 6.1 11 Trichloroethylene -t T/khloroHuOrOrrethinf ; l,1.2.Tnchloro-1,2.3- trifluorocthi"* - Tfifthytamin* (8/10 91 Trimethyfaminf (8/9.7) (0 55) 1100 >8 4.5 71 000 410 000,, (0.31) 0.43 - 0.00020 131 137 187 101 59 1.46 1.49. 1.56 0.73 f 3.1 310 190 71 1- 1 41 31 t,3,5*Trimethyltf hren* (0.67) 97 (0.0151 130 086 5.4 6 3 Tfimtthyl phptphit* d dd 134 1 05 d 1 r aldehyde 39 13 000 0017 86 031 170 1 3 Vinyl icrilt* 1 B 35 000., 0.088 86 0.93 50 4 1 Vinyl chloride V (0.0057) 1100 (3.4) 63 9 0.44 3 Vinylid'na c^OMd* Vinyl toluenf m. Xy lent 3,4.Xylidin# IB/4 91 4 10 041) (3 1) 11 6) 66 6400 ~ 100 170 6400 (1.51 10.42) 10.017) 1.8 97 118 106 131 1.22 0.90 0.36 0 97 7.0 87 3.7 6600 3 1 3 1 < i DO A 039797 OONFTDFNTT Al JOURNAL OF APPLIED TOXICOLOGY, VOL. 3.N0. 6, 1981 281 at 25 *C can be calculated'* (turn the vapor pressure attJ the solubility at 25 *C. The coefficients for some of the com pounds that ate Infinitely soluble In water at 25 *C were calculated ftom tabulated activity data" or measured experimentally,'* The results for n-butyl alcohol, width has provided the most plentiful odor-thiesliold data, are |iven In Tabic I as a demonstration of data reduction. The original threshold data. In a variety of concentration units, were converted5 Into common units of f l"'. Any water dilution thresholds were further converted to the equivalent air dilution threshold, ihroufh multiplication by the air'water partition coefficient.1* The relationship between odor-intensity sensation and odorant concentration is exponential.** Therefore, in order to preserve the normal distributions of olfactory-threshold measurements, aU chemical concen trations of odorants were calculated on a logarithmic scale. Hence the geometric mean of all 29 odor thresholds, expressed in air dilution, was computed (by converting to the logarithms, finding their arithmetic mean, and talcing its antilogaritlim).1 The mean air dilution threshold, In g l*1, was finally converted to mg m'1, and to ppm by volume. Explanation of Table 2 (odor thresholds) Column l. Threshold limit values (TLV) adopted by ACCIH. 1982.1 The superscript n indicates that the TLV used ii the value proposed in the 1982 Notice of Intended Changes. The superscript l indicates an Inert gas (simple asphyxiant) for which no TLV Is assigned by ACCIH, merely a requirement that the oxygen content of the air not be reduced below 18ft. This would be expected to occur If the asphyxiant reaches 14%, or 140000 ppm, which is in effect the TLV Tot inert gases. Column 2. The volatility in ppm (v/v) is given by the literature vapor pressure (in rnmHg at 25 *C) multiplied by 1316 (1 000 000 ppm per 760 rnmHg), -- indicates approxi mate value obtained by extrapolating the lineat regression ftom vapor pressures recorded at substantially higher temperatures, g, gaseous at 25*C. Column 3. Air-dilution odor thresholds are geometric averages of all available literature data, omitting extreme points and duplicate quotations. Odor thresholds originally measured in water dilution were converted to the equivalent aJr dilution, as Illustrated in Table 1 for n-butyl alcohol. Column 4. .When two or mote acceptable literature thresholds were located, the standard error of their mean was calculated. The standard error Is the standard deviation divided by the square tool of the number of literature thresholds. This factor is applicable to the data in columns 3,6 and 10. The imaller the standard error, the greater the confidence that may be placed in the accuracy of the mean threshold value. (It should be borne in mind, however, that a small standard error, based on only two thresholds, could itself be the result of a fairly probable coincidence.) Column 5. Safe dilution Taclor. for the saturated vapor at 25 *C. Is the volatility divided by the threshold limit value (column 2 divided by column t). For substances thar are less than infinitely soluble In water. the same safe dilution factor applies to the saturated solution at 25 *C (column 9). Column 4. Odor safety factot Is the threshold limit value divided by the odor threshold (column I divided by column 3). This factor may be Interpreted quantitatively by reference to Fig. 2, In terms of what percentage of attentive persons can detect the TLV concentration, and what percentage of distracted persons will perceive a warning of the TLV concentration. Column 7. The scale of odor safety classes is explained in Table 3. Gass A substances provide the strongest odorous warning of their presence at threshold limit value concen trations, whereas class E substances are practically odorless at the TLV concentration. Table 3. Odor safety classification Odor safety Dm factor Interpretation A >550 1 26-550 C 1-2S D 0.18-1 E <0.18 ' More than 90% ot distracted persons parcel** warning of TLV concentration In the air 50-90% of distracted persona pttcaiva warning of TLV Lets than 50% Of diftraciad panont parettw warning of TLV 10-50% of ausntiv* parsons can datact TLV concentration in tha air Lais than 10% ot ttuMrn parsons can datact tha TLV Column 8. Water TLV equivalent is the concentration of the substance in water, which will generate the air TLV concentration in the headspace of a stoppered flask or other closed system. It is calculated from column I by multiplying by the distribution ratio in column 13, then dividing by 24 400 (volume in ml of one gram molecule of vapor at 25 *C) and multiplying by the molecular weight. Solutions with values in parentheses lack enough per sistence for reference purposes, due to an unfavorably low water-air distribution ratio (<10) in column 13; d, decom poses In water. Column 9. Solubility in ppm (w/v) h the literature solubility (expressed as gl'1 of saturated solution it 25*C) multiplied by 1000. ~ indicates uncertain or extrapolated values. Temperatures other than 25 *C ate indicated by subscripts. Columns 10. Water-dilution odor threshold js the concen tration of the substance in water which will generate the ait odor threshold concentration in the headspace of a stoppered flask. It is calculated from column 3 by multi plying by the distribution ratio in column 13, then dividing by 24 400 and multiplying by the molecular weight. VaUrts In parentheses have tire same meaning as in column 8. Column II. The molecular weight (MW, sounded off to the nearest whole number expressed in grams) can be used to convert the air concentrations in ppm (v/v) (columns t, 2 and 3) Into mg m*\ Multiply by MW and divide by 24.4 (volume In liteis of one gram molecule f vapor at 25 *C). 282 JOURNAL OF APPLIED TOXICOLOGY, VOL. 3, NO. 6, 1983 WWw*s mj n .itw iw w r - i/ Column II. Tito density ID. at 20-25 "C) i* needed when measuring out liquid odorants by volume to prepare water or ait dilutions: 1 ppm (w/v) I mg [or (IID) pi) per liter of water MW / MW \ I ppm (v/v) -2--4--.4- ni*t \[or-2--4-.-4---*---0--ul Irpoerfcliufbic meter plottlng the data on probability graph paper. The result In probit approximates a Straight line if the distribution c sensitivities In the population Is in fact normal. Llteratur data on the percentages of persons responding to odotatu when they wete attentive, distracted,1* oi asleep1* wet teplotted as probits In Figs 1,2 and 3. -a p. jaseous at 20 *C; i, solid at 20*C. ;- Column 13. The water-air distribution ratio Is the reciprocal of the air-water partition coelTiclent. Where experimental values are unavailable in the literature, which Is usually the case, the ratio has been calculated from data in columns 9, 2 and II, or from other approaches mentioned earlier. An estimate of the water-air distribution ratio is given by dividing the solubility (column 9) by the volatility (column 2), then multiplying by 24 400 and dividing by the v* molecular weight (column 11). M Column 14. The numbers indicate how many original literature odor thresholds were included in calculating the average threshold in column 3 and the standard error in column 4. On the left is the number of air-dilution thresholds, and on the tight the number measured in water dilution. lonizable odorants (weak acids and bases) are indicated in Table 2(b) by appending to the compound name the symbol A for acid and B for base, followed by the acid dissociation constant p/T,. Data given for such compounds in columns 8. 9. 10 and 13 are accurate only for solutions In which the odorant Is practically un-ionized and hence CM* O.*?. 23 0 40 l0 $40 2*tO QdO'QM Conc<Atf4>i* (pftfcl potentially volatile. That is, the pH of the solution should FifU't 1, Tilts of rtloOAiivtncit Ot perio*! to fual 9*1 OdOrar *< be less than two pH units lower than the pAT, for an acid, Tht data were taken from tha report by Whitman #r Fiji and 13. >nd Tabfa 23. then repotted on log/probit coordinates, or should be more than two pH units higher than the pJCj the misdirected tests, the mention of th subjects was dvfibe'tr for a base. The odorant volatilities at pH values outside of Channeled to other matters. Note that tha concentration unity these limits can be estimated by calculating the concen ,, this Ftfure are peb t*M. tration of the un ionized species using the Henderson- Hasselbalch equation.11 For demonstration purposes, it will suffice to make solutions of the acids in 0.01 H HjSO* and the bases In 0.01 N NaOH. The data in Table 2 are incomplete for some physical properties of 25 compounds, because no literature values could be located, and no justifiable estimates could be made. The missing data ate mostly water solubilities or water-air distribution ratios, which In turn preclude estimates of TLV equivalents In water and water-dilution odor thresholds. If the leader is aware of valuei for the missing data, or knows of more accurate measurements or estimates of the recorded data, the authors would be grate Some chemicals, but not all, besides having a true od` also cause immediate irritation in the nose, eyes tx thio The sensation of stinging, prickling or burning, conveyed the trigeminal or 5th cranial nerve, is quite distinct frt the smell sensation carried by the olfactory or 1st eran nerve.'1 Irritation usually tequires a higher them! concentration than odor, and trained normal subjects c readily report the distinct Irritation threshold." Anotf approach is to use subjects who have suffered a chro> loss of their olfactory nerve function, but still set: an active trigeminal nerve sensitivity.13 ful for the information. Odor threshold data on TLV-liited compounds not included in Table 2 would also be welcome. Explanation of Table 4 (irritant thresholds) Variance of human responsiveness to odors When the individual olfactory detection thresholds for a given compound are determined on a sample of the human population, the data typically generate a (log)normal or Caussian distribution.1' For this result, it is necessary to use a logarithmic scale for the odorant concentration, such is a binary or decadic dilution series. The quantitative interpretation of a Caussian curve is facilitated by te- Column 1. In this Table, each odor threshold was deri> from the same source which reported the Ittitat threshold; hence the odor threshold In Table 4 may dil from that given for the same compound in Table 2t column 3, which may be an average of several literal values. Columns 2 and 3. Irritation thresholds ate the lowest c centrations that cause immediate stinging oi burn sensations In the nose, or stinging oi Uctimation of the e A 039799 conftofnttai JOURNAL OF APPLIED TOXICOLOGY, VOL. 3, NO. 6.1183 : ** . < .1 e l*Mf facts' Figura 2. A practical guld* to \ht pun(it*Uva Imtrpfttatlpn of odor uft faetDfl, Th# coordinates r log/prObit. to car* l| repaired in inierpoutlnQ between marked tntervati. The sloping lines Indicate the percentage! of the population impacted to respond to vtnoui fraction! or multiples of the mean detection threshold concentration n.O on the x axis). Tha detection fine represents the performance of fully attentive persons under good laboratory con* ditionv Tha warning line ibowi what may be expected for distracted persons under factory or field conditions. Tha warning tine is based on th* result! f Whisman *r #/.M for the gai odorants ethyl mercaptan and thiophana. In Tour compounds, designated by superscript *, they arc the lowest concentrations that could bt distinguished from pure ait by a general anosmie, i.e. by a person w|io has no olfactory nerve sensation, bur whose trigeminal nerve sensitivity is intact. Column 4, The lowet of the nose and eye thresholds (if both are available) was used for calculating this ratio of Irritation and odor thresholds. Column J. The Irritation hazard factor is obtained by dividing the nose or eye irritation threshold (wluchever is lower, columns 2 or 3) by the threshold limit value Horn Ode' Ie!!j leeio' (nwlilpta at irvis*e>4l Figure 3. An Illustration of the tlficacy of terrain vtpon in wakenlng.tlteolng pi'tont. The Cm were teVen from the neri at Fiildner ft f/.,n Tahiti 8. S3 end Id, than plotted on k>g/probit eoordinttti. The trmanti were allyl alcohol on the Ith. end crenoneldehvdt on the right. The odorants were ethyl mutimm (!. phenyl ether (*1 end lioamyl acetate 1*1. The concentrations in this Figure ere iteted et mulilplei o> the odor thrtiholdi reported by Fteidner et *t. ** Table 2(a), column 1. This datum Indicates by what multiple the TLV is exceeded, if eye or nose irritation can be detected. Column 6. References In italics indicate that thresholds were obtained using water dilutions. RESULTS AND DISCUSSION Literature search for odor jhrcsholds The ACGIH compilation includes approximately 350 appreciably volatile compounds for which time-weighted average threshold limit values have been adopted or pro- TabU4. Irritant threshold concentrations of len Industrial chemicals. See Methods for funher explanation of each column Subttanct t Odor IhrtiKold Ippm; v/v) 23 Irritation ihrtiholdi Non tppm;v/w| Cya -ppm;vM 4 Ratio ef Irritation and odor thrtiholdi 8 (filiation hail'd laetor ActixkJthyda Aciiie ckf Acfoltrn Ally! >>co^ol Caniyl chlordt O-ChlC<0*C* iDphf nQftv (r*l'C/otonldehydt Formic eeid FrOpionie acid Pft kfina 0 066 0.16 1.8 1.4 0.040 0 040 0.11 130 0 34 0.71 3300 160* 11 30 35 0.034 14 1100* 370* 700* 11000 13 59 SO 0.033 19 33 000 1000 6.1 21 3D0 0.55 130 8.5 1500 990 22 16 110 IS 80 0.44 7,0 230 37 140 DelfCIton thteihotd tor a flenttel anoirn.c ------------------------------------------------________ _________________________ 00 A 039800 . CONFTDFNTTAt 264 JOURNAL OF AFPltEQ TOXICOLOGY, VOL. 3, NO. 6, 1983 8 Rtliranct 22 33 22 23 33 23 33 33 33 37 4 t/1/WH ,\iu IU 'tf 11 posed.' Among these, there are 2N compound} Tui illicit Safe dilution factors for saturated vapors wt were able to locate at least one literature value far the olfactory detection or recognition llircsliold, inejtntcd In The procedure of expressing threshold limit vjfccs. air or water dilution. The data are widely scattered In (lie volatilities and odor thresholds all in the tame units (ppm; literatute, and there It tittle conformity in the choice of v/v) brings to light certain relationships that ate not units for expressing the result). For example, the 29 apparent when miscellaneous units are used. Nearly aR of reported thresholds for rt-hutyl alcohol (Table I) were the compounds in Table 2(a) have volatilities it 25*C gathered from the works of 26 principal authors, who which exceed, sometimes by an enormous factor, their used IS different systems of concentration units In publish threshold limit values. Accordingly, a sniff, from the head ing their data. In 24 journals. Furthermore, no two of these space of a bottle or drum, or from a confined space con 29 thresholds were measured by precisely the tame experi taining a spill, of almost any of these substances, inevitably mental method. exceeds the TLV. The safe dilution factor in column 5 4 The lack of standardization, taken In conjunction with Indicates the minimum number of volumes of uncon- the inconsistent potity of the chemical samples and the tamlnated air that would be required to dilute, to the nfe variability of human sensitivity, Is responsible for the rather level, one volume of air that has been saturated by exposure wide range of threshold concentrations usually found in the to the named compound (assuming perfect mixing). Vbnt literature for a given compound. As indicated it the foot of Table I, the mean threshold for n-butyl alcohol Is location, layout, ventilation, chjmneys and emergency procedures should be designed with the realization of the 4 0.835 ppm. (In this compilation, the data were collected and calculated to three significant figures, then rounded off safe dilution factor in mind, at least for compounds for which dilution ventilation is an allowable method of *3 to two significant figures for the Tables.) The threshold control. Any Increase in temperature of the chemical above '( concentrations having been calculated as logarithms, 25*C increases the required safe dilution factor, in pro statistical deviations and errors from the geometric mean portion to the vapor pressure. should be stated In the form of factors (rather than the A majority of these compounds are not completely differences used with ordinary arithmetic means). The miscible with water. Nevertheless, a saturated solution of standard deviation of the logarithms of the observed any volatile compound is theoretically capable of saturating thresholds was 10.854 logunits, for which the antilog the headspace to the same concentration as the pure com yields a factor of x/f7.14. Taking into account all 29 pound could achieve. Whether or not it will do so In a finite '1 literature values (l.e. dividing by v29), this reduces to a time depends upon the water-air distribution ratio, the standard error of 0.159 logt0 units, corresponding to a relative volumes of air and water, and the decree of factor of This Indicates that there is approxi agitation. To err on the safe side. It would be prudent to mately a 68% probability ( lo or SD) that the true Use the same safe dilution factor in calculating the number threshold for n-butyl alcohol lies between (0.835/1.44) = of volumes oT clean water which would be needed to dilute 0.58 ppm and (0.835 x 1.44) = 1.20 ppm. There is a 96% one volume oT a saturated aqueous solution of the probability (t lo) that It lies between (0.58/1.44) = 0.40 compound before discharge to a sewer, lagoon or river, ppm and (1.30 x 1.44) = 1.73 ppm. Olfactory thresholds where (his Is permitted. could, if necessary, be obtained with greater consistency and smaller standard errors, by determining conversion factors between different experimental methods.13,M or Odor safety factors as chemical safeguards by redetermining the thresholds by using a standardized 4 procedure with careful minimization of known sources of erjor. When the threshold limit value is substantially higher than the odor threshold, the Intrinsic odor of the compound In the literature, we found for these 214 compounds a usually, but not Invariably, provides an indication of its total of 1054 acceptable thresholds. Some thresholds had presence, at a concentration level low enough that no harm to be rejected on the grounds that they had been measured is likely to the human observer. Conversely. If the odor without consideration of substantial ionization, unfavorable threshold is much higher than the TLV, then anybody partition coefficients, likely impurities or the inapplic detecting the odor of the compound lias a warning that a ability of Raoult's law. A few remaining extreme points safe vapor concentration has already been exceeded. The were discarded because they diverged more than 100-fold exposed worker would be well advised to request a pro from the nearest of two or more other thresholds for the fessional evaluation and perhaps instrumental assessment same compound.1* For 152 of the compounds, we found of the situation. It should be determined whether the two or more acceptable thresholds. We calculated the applicable TLV criterion (time-weighted average, short mean threshold and Its standard deviation for each com term exposure limit or ceiling value)' Is likely lo be pound. The average of the individual standard deviations exceeded in the particular working regime, and if so. what for all these 152 multiple threshold compounds was a the health significance may be. factor of'x/-^ 7,0. The remaining 62 compounds each The potential warning power of a given chemical Is yielded only one usable threshold, so no standard error conveniently expressed by the odor safety factor (column could be calculated, which accounts for the dashes In 6 of Table 2(al), which is simply the TLV divided by the column 4 of Table 2(a). The uncertainty in a given odor threshold. Any chemical with an odor safety factor olfactory threshold measurement should be independent less than 1.0 carries the risk that hazardous conceMtations of wheiher the compound has been reported several limes will not be detected by odor. Conversely, an odm safety in the literature, or only once. As a tough guide, we may factor greater than 1.0 bears the promise that a hazardous assume the same average standard error factor of x/* 7,0 concentration could be perceived by smell. Nevertheless, for these single threshold compounds. the question of whether or not a hazardous concentra- DO A 039801 orJOURNAL APPLIED TOXICOLOGY. VQL. 3. NO. S. 13 28S OONFTDFNTTAl s i.t *v tnk<t lion will actually bf imclt. ii quite complex, and depend! upon a variety or dn.uimtani.ci. (A very few people, roughly I In JDO. have no true sente ol *mell at all;1* the existence of anosmie persons. while of some practical Importance, is omitted ftorn our discussion.) The average odor threshold has not been sufficiently rigorously evaluated for all these compounds, many of which possets measured or Implied standard errors as large as seven fold. This Is not. In prlnciple.au insurmountable problem, because 63 compounds In Tabic '(a), column 4, already have thresholds evaluated with standard etrots less than two-fold. Equal, or belter, accuracy could readily be attained by new experimental measurements on the deficient compounds. The ability of members of the population to detect a given odot is strongly Influenced by the innate variability if different persons' olfactory powers, their prior experience with that odor, and by the degjee of attention they accord to the matter. The thresholds listed In column 3 of Table 2fa) .represent the most favorable conditions for testing. The subjects were well aware that these were tests of their sense of smell, they were attentive and they were trying their best to detect the presence of the odor. Even so, the odor-detecting ability of different people varies over quite a wide range. The compilation of individual sensitivities to a given compound typically yields a Gaussian or bell-shaped curve,1' ptovlded that a logarith mic concentration scale is employed. For this normal distribution, the standard deviation Is a measute of the spread of odor sensitivity In the population. We have evaluated this standard deviation with seven odorants: bobutyl Isobutyrate, isovaleric acid, 1-pyrroline, trimethylamine, Isobutyraldehyde, androst-l6-en-3-one and pemadecalactone, each tested with 18-443 normal observers. The avetage standard deviation was 11,97 binary steps, which may be rounded off at two binary steps.'* The standard deviation indicates that 68% of people tested, on the average, will have a personal threshold that lies within the ranee from one-fourth of the mean, to four times the mtan, threshold of the population. The effect oT distracted attention In connection with testing the efficacy of certain odorants is warning agents for Tuel gas, Whisman et el.1* conducted a thorough study of the Influence of various degrees of distraction on the responsiveness of people to these wellknown warning odors. Their 'directed' lest corresponds with usual laboratory conditions. In which the mention of the subject is purposely focused on the sole objective of detecting an odor. In the `semi-directed' test, the subjects were asked to report Qn visual, tactile, aural and nasal stimuli in tire test room. In the 'undirected' test, the subjects were given no indication of the object of the exercise. In the 'misdirected' test, the attention of the participants was deliberately distracted by asking each to try to read some prim in a dim light and to judge the temperature of the loom. All except the directed tests were performed with Inexperienced subjects recruited by a mobile laboratory arriving unannounced at shopping centers, and each volunteer was used for one test only at one odorant concentration. Whitman tt el. found that the responsiveness of the subjects to a given concentration of odorant w-it tub- stantially decreased In the semldirected. undirected and misdirected tests, compared with their performance In the directed test mode. The misdirected test was probably the most difficult set of conditions Imposed upon the subjects. In our opinion, the misdirected test Is the most appropriate of the, available models for evaluating the effects of con ditions encountered In Industrial practice. A factory worker would not be familiar with odor-threshold testing tech niques. but would hopefully be aware that chemical vapors may b< hazardous, and might know that a distinct smell indicates the presence of appreciable vapor In the air. On the other hand, the worker is likely lobe concentrating on following Instructions, reading charts, controlling equip ment and generally trying to get the work done. Such a degree of mental distraction, as Whitman et eL showed. Is ample to divert attention away from any but the most obvious of odors. In Fig. 1. the results of Whisman et el'* for their directed and misdirected test modes are presented in log*/ probit coordinates, which have the advantage of exhibiting an approximately linear relationship between olfactory stimulus and response. Each data point in the directed tests was obtained from 22 subjects, and in the misdirected tests from over 100 subjects. The data points were fitted by a logarithmic transformation linear regression, from which the slope and 50% response intercept were obtained. The directed test threshold for ethyl mercaptan, at which 50`S of the subjects would respond, was found by extrapolation to be 0.17 ppb- In the misdirected test situation, however, the 50% response threshold was tt 4.8 ppb, or 28 times higher. Furthermore, the slope of the regtession line is shallower, so that disproportionately higher concentrations are required to elicit a response from 90% of the partici pants. The results for thiophane ftetrahydrothiophen) are virtually super Impotable upon those fot ethyl mercaptan, except that about double the concentration of odorant is needed to achieve a given level of tesponse. That is. 035 ppb for detection tlueshold and 8.7 ppb fot mis directed threshold, or 24 times higher. The good agreement between the results for ethyl mercaptan and for thiophane encourages us to generalize the data, so as to provide a practical guide Tor interpreting threshold ratios and odot safety factors (Fig. 2). This graph Is set In log/probit coordinates. Since neither the logarith mic nor the probit scales go to zero, the origin of the graph Is considered to be the Intersection of threshold multiple 1.0 on the x axis, with 50% persons lesponding on the y axis. This, by definition. Is the average detection threshold, measured under laboratory conditions, l.e. a directed test. The logarithmic binary step concentration scale and the standard deviation intervals are also entered In Fig. 2. It was previously demonstrated11 that the sensitivities of people to various odorants exhibit standard deviations close to 2.0 binary steps. Hence, the detection line in Fig. 2 b based on tltis generalization, and constructed by drawing a line with a slope of 2.0 binary steps per standard deviation unit, through the origin of the graph. The detec tion line is shown as a broken line above 95% response, because there are some indications that a small percentage of the population has specific anosmias to one or more of the sulfurous odorants.*' Such persons, while they may perceive most other odors normally, are found to have an innate lowet sensitivity or 'odor blindness' to the typical gat odorants. IBG JOURNAL OF AFPLIEO TOXICOLOGY,VOL. 3.N0.S. 1983 CONFJOFNTTai UIXJK A* A.V AIM lUS.III.*". .a *' I < 1 The warning line In Fig. 2 Is bawd on (lie average of the misdirected data for botli ethyl mercaptan and thinphane. It wai committed as follows. The reiulti for ethyl mer captan and for thlophane (Fig. I) showed that the ratios litre si sold. Al the other extreme, class C compounds at their TLV concentration can be detected by less than 10% of attentive persons. In this category, the odor safety factor Is below 0.13. The quantitative ranges for tl.e intermediate of lire 50%~deiectiun thresholds In the misdirected and directed test protocols were 23..' and 24.5, respectively. 0. C and D classifications are as Indicated in Table 3. The zones of odor safely factor fur the five classes are also Ar, Their geometric mean Is 26.3, which was rounded off to 26 for the threshold multiple. In Fig. 2, the warning line is labeled on Fig. 2. The odor safety class of each of the 214 compounds, for wlucli adequate data are available, are drawn to intersect the 50% response level at the threshold entered In column 7 of Table 2(a). Gass A compounds multiple value of 26-fold. The slope of the warning tine was provide the strongest odorous warning of their presence likewise determined by averaging tlte slopes of the at the TLV level, whereas class E compounds are practically * regression lines for tlte misdirected tests In Fig. I. The undetectable by odor at their TLV concentration. averaged warning tine has a slope of 3.5 binjry steps per standard deviation unit. Therefore, in order to be perceived by 50% or distracted The effect of sleeping 4 subjects, the concentration of gas odorant had to be raised to 26 times the concentration that could be detected by Although It Is not considered relevant to most workplace 50% of attentive subjects in laboratory test conditions. This situations, the power of an odorant to waken a sleeping illustration lends emphasis to the compelling conclusion of person Is significant where industrial products can escape .. Whisman tt al. '* that there is a substantial difference Into a residential area. This is an obvious risk with house *> between the level of odorant that can be detected, and the hold gas, and Ihe question was Included In a study by level that will be detected, In a given jet of circumstances. Fleldner er al.v Their data for several odorants are The available data do not permit extrapolation of the displayed In log10/probit coordinates In Fig. 3. They tested warning line In Fig. 2 below die 50% response level. three compounds (ethyl mercaptan, phenyl ether and Odor safety classification of chemicals boamyl acetate) which can be regarded as more or less purely olfactory stimulants, l.e. they have little or no irritating power for the trigeminal nerve. Each data point Figure 2 represents a provisional synthesis of the best available data. The slope of the detection line appears quite soundly established, and to be applicable to many chemicals. For those uncommon chemicals that exhibit a pronounced and frequently occurring specific anosmia among members of the population/* the curve is expected to flatten at higher response percentages. The slope and intercept of the warning line, however, are based on only two. quite closely related, fuel gas odorants. Intuitively, we feel that the results for ethyl metcaptan and thiophane represent a relatively favorable case, because, thanks to the public awareness developed by the suppliers of household anj bottled gas, it Is a widely known fact that the 'smell of gas' is an indication of danger. In other words, gas odotanls may have a belter chance of penetrating the consciousness of a distracted person than many other odors that ate not mentally associated with harmful consequences. Until more data become available, we propose that the relationships In Fig, 2 can be used to set up a provisional classification of the 214 chemicals, according to the level of fifety indicated by their odors. For tliis purpose, we are adopting the 10%, 50%> and 90% response levels as practical guides. According to Fig. 2, the obvious benchmarks are the detection threshold at which 50% of people can perceive in Fig. 3 was calculated from the ttsults of tests with three to eight sleepers. The points were then fitted by linear regression. The performances of these three odorants seem fairly concordant, and Imply that an odorant concentration about 20000 times the normal detection threshold Is required to awaken 50% of soundly sleeping persons. That Is more than 700 times stronger a stimulus than suffices to serve as a warning for wakeful, but misdirected, observers (Fig. 2). If this result were applicable to ail odorants, It would mean that virtually none of the 214 compounds examined in Table 2(a) would awaken the average person, without exceeding the TLV. Thete is. however, a complicating factor. Some odorants, besides stimulating the olfactory nerve, also irritate the trigeminal nerve. Two examples ate Included on the left side of Fig. 3. These substances were far more effective In waking the sleepers. A 50% response was obtained al 27 times the odor threshold of ctotonaldehyde, and at only three times the odor threshold of allyl alcohol. From the comments of those that woke up, it is obvious that the irritation was the determining factor, it la an interesting observation that the ttigeminai nerve has some sort of a 'hot line' directly into the subconscious, that Is denied to the olfactory nerve. the odor, and the higher warning threshold at which 50% of people will notice the odor even when they are dis tracted. Secondary criteria are provided by the concentta- Some data on irritant thresholds tions at which 10% of attentive people can detect the odor, and the other extreme where 90% of distracted people get a warning of the odor. These four borderlines are indicated by vertical lines in Fig. 2. Our tentative odor safety classification Is presented in Table 3. At their threshold limit value concentration, class A compounds will be perceived by 90% of distracted persons. To achieve this rating, the odor safety factor must be at least 550; l.e. the threshold limit value for the compound is more than 550 times higher than its odor Trained normal observers can report distinct concentration levels at which a vapor produces nasal or eye Irritation, quite apart from its odor. Katz and Talbert" tabulated considerable data, front which we have selected those compounds that are on the ACCIIi list (Table 4). We have also added a few compounds from our own work. In which nasal irritation thtesholds were obtainrd from an anosmic person lacking the ability to perceive true odors as opposed to irritants. The ratio of the Irritation and odor 00 A 039803 , OONFTDfFNTTAl JOURNAL OF APPLIED TOXICOLOGY, VOL. 3.NO/S. 1333 287 1 J. L. AMOURI AND t',, II.VUTALA I * thresholds for these compound! tanges from 33 000 fot those solutions lack enough pttsistenet to serve as ttliablt acetaldehyde, to loss than unity for o-cliioroacetophenone. standards In setting up ivatei dilution snlff-tcsrs for tiaining Where this ratio It relatively tmall. It seems very likely tliat Irritation would become an important factor In determining or testing petsonncl. the intercept and tiope of the warning lint In Fig. 2. If irritation of tire trigeminal nerve can wake a sleeping person so effectively. It teems very likely also to be able to preempt the attention of a distracted person. No quanti CONCLUSION tative t'catment of this factor Is possible at piesent, because Irritant thresholds are available for so few of the compounds on the TLV list, and no tests have been reported on perception of Irritants by distracted persons. It may. however, be worth noting the Irritation hazard factor In column 5 or Table 4. These figures Indicate the degree to which the TLV Is bting exceeded, If there is appreciable eye or nose Irritation for an attentive subject. The Interpretation of these data In any particular safety or pollution problem wjU depend markedly on the Individual circumstances. Tire threshold data In the Tables and Figures are based on averages for samples of the population, pre sumably In good health. Individuals can differ quite markedly from the population iveragt In their smell sensi tivity. due to any of a variety or innate, chronic or acute physiological conditions."-Likewise, the time- weighted average threshold limit values are for workers, Threshold In water dilution who by the mete fact or being able to work evidently represent a generally healthy segment of the population. Many of the odor thresholds found In out literature survey had been measured by sniff-tests ftom the head-space Continuing exposutt to an odor usually results In a gradual diminution or even disappearance of the smell above aqueous dilutions. Theoretically, the air-dilution sensation. This phenomenon Is known as olfactory adapta threshold and the water-dilution threshold ate simply tion or smell fatigue.10 If the adaptation has not been too related by the air-water partition coefficient of the severe or too prolonged, sensitivity can often be restored odoiant, provided the concentrations are measured in by stepping aside for a few moments to an unconlaminated equivalent weight per volume units. This expectation has atmosphere, If available. Unfortunately, workers chronically been borne out In comparisons made for n-butyl alcohol, pyridine and isovaleric acid,14 and has been farther supported by the data for many compounds listed in Table 2(b). For example, the data for n-butyl alcohol in Table 1 exhibit, for the reported olfactory thresholds, mote than a 1000-fold tange, yet the gtoup means of the 20 air thresholds and the nine water thresholds differ by a factor of only about three-fold, and this is not considered signifi cant (/*>0,1). Odor thresholds measured in air and water dilutions art generally concordant, unless the water-air distribution ratio Is lesi than approximately ten. In that case, the ttpotted water-dilution threshold concentration is liable to be too high, due to substantial evaporative loss of odoiant from the solution during the coutse of conducting the odor threshold tests. The air-dilution thresholds in column 3 of Table 2(a) are based on a pool of all available data from both ait- and water-dilution measurement!, omitting water thresholds for compounds with unfavorable water-air distribution tatios. The water dilution thresholds in column 10 of Table 2(b) wtit generally calculated ftom the data in column 3 of Table 2(a), by applying the water-air distribution ratio. In this way, we have been able to calculate wattt-dilution ihtesholds fot many compounds for which only air-dilution threshold data were previously available. By applying the same distribution ratio, the water equivalent concentrations were also calculated for the TLV, and are listed in column 8 of Table 2(b). With odorants that ate lonlzable (acids and bases), these calculations art strictly valid only within specified pH limits, as explained in the Methods section. We felt that It would be Informative to provide the theoretital water threshold and TLV data,'even for com pounds with distribution ratios of less than ten. The equi librium air concentration can develop and persist in conditions of high liquid-vapor volume ratio and low vapor loss, such as a dosed vessel pr a sewer. TLV and threshold data for odorants with distribution ratios less than ten art In parentheses in Table 2(b). This Is to Indicate that exposed to a Strong odor can develop a desensitization which persists up to two weeks or more after their de parture from Lite contaminated atmosphere. In such cases, it should be the responsibility of supervisor and inspectors to note the odot and take appropriate action. Hydrogen sulfide and pethaps other dangerous gases can very quickly lose their characteristic odor at high concentrations. At levels of H;S above 100 ppm (over 10 000 times the average detection threshold), the sense of smell is rapidly abolished, so that potentially lethal concen trations may not be detected by odot at aU.11 Certain commercial diffusible odor masking or suppressing agents may reduce the perceptibility of odots, without removing (lie chemical source. The use of such agents might interfere with the capability of the nose to provide a warning at the expected concentration level. There are many potential applications of these data in chemical safety and in air- and water-pollution control, some or which have been mentioned pieviously. In addition, we believe that the data might find some less - apparent uses: Table 2 is also a guide to what data are in the literature on odor thresholds, on TLV-listed substances, it unavailable, unconfirmed or erratic. Readily ptepared water dilutions could be used to test the individual smell thresholds of workers to the chemicals they handle. A water TLV dilution of an odorant could be prepared to demonstrate quickly to workers the practical experience of its TLV concentration. The general experimental pro cedures for preparing and testing aqueous solutions of odorants have been described." These concepts could Impiove the reliability of odor breakthough as an indication of when to change the organic vapor cartridge in a respirator. The feasibility might be considered of using class A or B compounds as warning odorants to be added to class D or E substances, or to pesticides. The water-sir distribution tatios could also be a guide to iht possible Success of water-scrubbing aa a means of removing vapors from effluent gases. 2B8 JOUTNAL OF APPLIED TOXICOLOGY,VOL. J.N0.6. 19B3 00 A 039804 CO NFTDFNTIAi UlAJK AS AN Ain IO LMI.MH.AL >AI I.IT The TLVj used hi Table 2 and discussed In (hit paper are last warning. During chemical operations, when an odor llioie moininended by the ACGIII in its 1982 lining.' la detected, the source should be located and the concen The values are ic published annually, and are subject to tration determine-!. Then effective steps can be taken to revision, usually with two yean notice of Intended changes. prevent the escape of vapor, and restore a neutral and The US Government Occupational Safety and Health healthful odor background. Even In the unnatural environ Administration (01I5A) and many State Administrations ment of the Industrial workplace, our sense of smell has have established their own lists of permitted exposures. much to offer as a natural safety warning system. Mule the values adopted ate often based on the ACGIII i recommendations, they may not coincide with current ACGIII TLVs, and quite different standards may be set for Acknowledgements ctrtain compounds. Some foreign governments issue guide We art very grateful to Dr R. G. Buttery far measuring the air-water lines with Independently derived limits. If the applicable partition coefficients of some Infinitely soluble compounds by gas exposure limit for a particular compound Is different from chromatography, and ro Mr C I. Thompson for an advance copy of ^I the TLV cited In Table 2. column I, It will be necessary to his manuscript with Whitman er et. on the ittponiWencss of people to gas odosants,'* We thank Ms W. D. Kelly, Executive Secretary of adjust the values In columns 5, 6 and 8 by the appropriate the American Conference of Governmental InduiUlal Hygienists. fat ratio, and perhaps reassign the odor safety class (column 7). Inc., for peimiislon la use the TLV data from Ref 1 In Tabic 2(a). Values In Table 4, column 5 may also have to be altered. The preparation cf this paper was supported in part wish funding Every chemical that can be detected by smell exhibits provided under Service Order No. 34 016, from the Hazard Evalua tion System and Information Service, Department of Health il a properly that can be turned to advantage as an aid in Setvlces-Department of Industrial Relations, State or Catilomia. maintaining safe operating conditions. It mutt be This repott has been teviewed by the staff of the Hazard Evalua recognized that background odors, odor fatigue, preocupa- tion System and Information Service Section. Department of Health tlon and individual Insensitivity may combine to reduce the margin, if any, between odor detection and safe operating conditions. No odor safety factor is large enough to justify Servicer-Department of Industrial Relations, State of California, and approved for publication. Approval does not signify that the Contents necessarily reflect the views and policies of the Hazard Evaluation System and Information Service Section, nor does condoning the presence of a fleeting odor, let alone a per mention of Dade names or commercial products constitute endorse sistent stench, unless professional assurance has been ment or recoinmend.-tion far use. ,, K obtained that the working conditions arc safe. Reference to a company and/or product In this publication b only for purpose* of biformation and does not imply approval or The first detectable odor should be a sure signal that recommendation for the product by the US Department of Agri something abnormal has happened somewhere. It may be the culture to the exclusion of others which may also be suitable. * 1 REFERENCES Thrttbold Limit Valuer for Chemical Substance! tnd Physical Agents in me Workroom Environment, American Conference of Governmental Induiirial Hygienists. Cincinnati 11932). P. Latfort. Esiii de standardisation des sculls ollactifs humaint Pour 192 corps puts. PrcS, Set. Physiol. 17.75-10$ (1SS31. 2. F. Petti. M. Etcfeto end P. Lilfort. Selected and standardised valuer of tuorainreihokj odor Inteniities (or 110 substances. Chem. Sant Plt.cr 1. 333-305 11975). L. J. van Gemfit and A. H. Netttnbreijer. Compilation of Odour Threshold Values In Air end Water, Ctntttt Institute for Nutrition and Food Research. Ztist 11977). 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An instigation of stanches and Odors (or industrial purposes, ind, Eng. Chem. 11, 336-338 (1919) 25. P. M. Patterson and 9 A. Lauder, The incidence and probab'e Inheritance ol smelt blindness. / Heredity 39, 295-297 (1948). 26. J. E. Amoore. Specific anosmia and Ihe concept ol primary odors. Chem. Sent Flevgr 2, 267-381 (1977). JOURNAL OF APPLIE Q TOXICOLOGY. VOL. 3. NO. 6, 1983 289 J. I,. AUUUKI \.NL> I., II At' I ALA 27. A. H J, E. Amnorfl *nd V, Weigel, The pvndlna teslt for Clm<Ct measurement Of OlfC!Ory threshold 1 Quantitative rrtvilumon, Oioltiyngol. Htsd Ntck Surg. 17, 717-733 (1979). 28. A, A, Schneider, The sens# of jm!| in man -- its physiologic tut>i N*w ngtt J. Mtd. 277, 299-303 (1967). 29. R, L. Doty, A ftvurv of Olfactory dysfunctions in man. Am, J, Otoltryngof, 11 57-79 (1979). 30 G. T. Pryor, G. $innmti r\d H. Stone, Changes In absolute detection threshold and in subjective intensity of supra- threshold Stimuli during olfactory adaptation end recovery Pirttpt, Ptychontoft 8,331-335(1970). 31. Occup*tton/ *po\ufi to Hydro*)** Suit'd*- C/rferre tot # A*comm*nd*d Ztrui*rd, National Institute for Occupational Safety and Health. Washington DC (19771 32, J, E. Amoorf, Directioni for preparing aqueous solutions 0* primary odorants to diegnost fight types Of specific anosmia, Chtm, Sens. Fistor 4, 153-161 (1979). Received 17 August 1982, accepted (revised) 15 February 1983 ^on imieiiM nc * obi ten THYirm AflV Vfll 3 NO 6 1983 00 A 039806 C0NFT0FNT JAl DOW INDUSTRIAL HYGIENE GUIDES (IBGs) COMPLETE CURRENT LISTING** M. G. Swank October, 1986 I. CHEMICAL AGENTS Material___________________________ ______IHG________________ Date Acfc'.e cya'o-yer.r, 1 ppm Ceiling-Sr * 1 SEC Ace^-.e^e lefab'omiCe see 1,1,2.2-tefat'omcethane N-Acety -p-am nopbeno! 10 mg 1975 Ac'yiam.de 0 03 mg-Skin 1 98a Ac*yiic a: c 2 ppm-Skin i960 Ac-y xn.tvie 1 ppm-Skin; 10 ppm Excursion 1 96 - -**-AVa ce'vcse 2 mg. as NaOH 1975 A-^apasr Ye'isw-lndandone 0 05 mg 1975 A--,as as* Ye' da PFL .0.05 mg 1975 A~ -oe,ky ema^c'arn.re 2 mg-Sk:n se: A~ *.rc e Am-p-. j- b'P--i'ce C 1 mg 10 mg 1976 i SEC A -- :* pe-s^ate 5 mg 1975 A": > \ z ' 2 mg 1960 A-p: . - 2 mg i se2 Aspr.n 10 mg 1976 At-azme 3 mg 1977 Benzene 10 ppm Ceiling 1977 B!PPE (B pbe-yiy: phenyl e1ber) 10 mg 1575 3 3-5,s.'b,omcme*.,~y')oxe!a',.e 1 mg 1 9" E s lz~ c'se^y. .etr.e- C.5 ppm 1577 E z-z spc'esy'jetr.e- use WEE L E Er~e*: A 5 mg 1976 E' -e 10 mg 1975 15 ppm. 1 975 B-z-zz-zi 10 mg ` 576 * ,2-5_:ac e'e 50 ppm. 2C0 pp~ Excj'sor 953 A-te"-6-tx .ce:ecboi 5 ppm-Skin I960 E-yie^e cx ce AC ppm. 100 pp- Exc-'s or '.950 **''*E^:y',sccyane!e 0.02 ppm-Skm 1565 1er'-B^:y: pe'be-zoate 0 1 ppm 1 975 p-ten-Buty Ip7.er.pl 2 mg 1575 BuTy. stearate 150 ppm I960 p-'ert-Butylstyrene 10 ppm 1978 Cab-O-S: 1 mg respirable NOTES Units given as "mg" = mg/nr . Indicates changes or new additions since last list. Glossary of terms is on last page of this list. 1976 DO A 039807 OONFTDFNTTAl -2- Cs c w>m b'pm.oe Material Ca z jm chior.ce (32% trine; Cac.u'r steafate Ca zo ai ;anne cyan.ne Caro Chinclme Yelcw ZSD Ca<co Rec (4775) -i-Ca!co Rec ZiR (5020) Catechp; **Cbiorarnphenicel (and esters) Chicrcacetyl chloride i-t3-Cr, icrcaiiyij-S.S^.-triaza-i- arcn 6acamanto,'e cnionde Cno'cmethy. mery etKe' p-Ch'o'c-c-cresO' o-C-iS'dphenoi p-C"iOropheno! Chlpropnenylphenoi 1 -Chioro-2-propanol 2-Chloroproplomc ac>d "Ch.orcsu'lpnic acid Chr-p-.e-./amme ma eate C.:*: arc C;oa * c* cnce Cy*co,` p'oTiide Cya'J'iC CK>C'>C6 Do D-" Dea'PC"" 922 in-,:ptC' DecaC'o'nociphery etr.eDiP'CTcaceton:!' ;e * .2-D brorno-3-ch,orop'opane Dib'pmorr,ethane Dib'omoneopenty! g'yccl Dibrornonitriiopropionamide Dichiomacet.c acid 1,1 - dic.hlcro-2,2-d/fljoroefhylene 10 mg IHG 10 mg 10 mg 0.05 mg 0 05 mg 0 05 mg 0 05 mg 5 mg-Skm use WEEL 10 ppb-Skin, 50 ppp E*Cj'Sion 1 mg 0.1 ppm 1 ppm 0.2 ppm 1 ppm see DOWICIDE* 32 see Propylene chlorohydnn 1 ppm use WEEL . 0 1 mg 10 mg 0.1 mg as Cc 0.3 ppm Ceiling, S*t;n 0 C3 mg see Dowpon 1 mg use WEEL 0,1 ppm Ceii.ng, S,:n 0.1 ppm-Skm see Methylene bromide 7 mg 2 mg Ceiling' 400 ppb-Skin see Freon 1112-A Date 1 960 1975 iS^S 1975 1975 1975 1 975 1975 196- 1 977 *976 * QT 1 9"5 1975 is:: * 96* * S* *975 1 9f4 1976 * 9~5 *964 *s:e 1 9~E 1579 1977 *Trademark of The Dow Chemical Company Do A 039808 CONFTDFNTJAi 2 <-Dichiorophenol Material 5.5-DicMcKop.co'inic aod 2 3-Dichloropropene 2,2-Dichloropropi0nic add, sodium sal: D:electnc Fluid C4 2-(Dielhylamino)ethano! Diethylbenzene. mixed isomers Diethyl disulfide DiethylenB glycol butyl ether Diethylene giyco' ethyl ether D ethylene g'yco methy' ether D ethyl phosphorochlo'idoth'cate (DEPOT) 1 .f -e Vucroethai-e * 2-C'f;uorctefachio'oe'mane D"sopropybehzehe neta, para isomers Dim,ethyl disulfide "Dimethyl ether Dimethyl phosphorochlondothioate (DMPCT) Dimethyl sulfide Dmitro-o-sec-butylphene! D'Octy adipate VS 2.6-D-te,t-buiy'-p-C''e6Cl 2 4-Q ;cet-b,,ty ,p`'e"'p 2,^-D,;ter`-bj,yi;phehol 2 6 - D1; t e': b u t y1p h e n c i 2 ^-Dilte't-b-ty'ipnehc;. soc.um sa" D o~e"y su" ce Distea-y' th,oo p'op'cmate DOWANOL* DB DOWANOL DE DOWANOL DM DOWANOL EE DOWANOL EM DOWANOL EPh DOWCO* 290 1 ppm IHG 10 mg i ppm-Skm see Dowpon 10 mg 10 ppm 10 ppm 1 ppm 35 ppm 30 ppm 30 ppm 0.1 ppm-Skm see Freon 152-4 see Freon V2-A 10 ppm 3 ppm use WEEL 0.1 ppm-Skin 10 ppm 0.3 mg-Skm see V9 DOA see lono' 5 mg 5 mg 5 mg 5 mg 1 ppm 10 mg see Diethyien.e 5 .:o b-'y ether see DiBthyiene g. :o et~v ether see Diethylene g yoo metnyi ether see Ethylene g'yco monoethyi ether see Ethylene giyco moncmethyl ether see Ethylene g'yco pneny' ethe' see 3.6-Dichio'oo :o n.o acid Trademark of The Dow Chemical Company Date 1S75 197S tse: i o~ 1975 i s~r i 975 : 952 952 1982 157* 1977 1979 1977 : 975 195; 1 1975 19-5 'S~5 1c~~ 1975 -4- DOWCO* 356 Material Pc* Com.ng Fluid 550 DOWFAX* 2Al surfactant Dowfiake calcium chionde [11%, solid) DOWlCIDE* 1 DOWlCIDE A ^.DOWICIDE 32 DOWICIL* 75. 100 ano 200 DOWPOIM* DCWTHERM* G DOV/THERM J DOW7HERM SR-1 " E r y f r, r c m y c' n ethdcei* Emop'opncs Ev~y! chio'cacefafe Etrylere dbrormde Ethylene glycol monoetny1 ether Ethylene g'ycol monomethy1 etner Etnyiene g'yco pnenyi ether 2-Etfy hexy' aery,ate 2-Etny -E-cxazcl ne Et"y';c'jene ;m,e:a pa-a isome'S' FREE' FRt 135 F-e = n -12-A Freon 12-A Freon 1112-A F-eon E-6 5 Fjma'ic acic GARLON* Gasolme Glyoxa! "Haicxytop ethoxyethyi "Haicxyfop methyl 1 ppm IHG Date 1979 10 mg 1976 5 mg, as achve mg-ed ent 1976 10 mg see o-phe"y pheno 1975 5 mg 1 ppm 1975 1976 see Chlora'iy!l',&2aa2on,aadamantone chloride 3 mg 1976 use TLV 1o' phe"y ether see Diefy oe'rene use TLV fc efylere g'ycol use V.'EEL 10 mg 0.01 ppm S x1 n 100 ppb-S* r 0,5 pprrvSx.n 5 ppm-Skin. 10 ppm Excursion 3 ppm-Skm 6 ppm. Excursion 1975 1978 1977 1980 1981 1981 25 ppm-Sxi' 25 ppm 3 ppm 10 ppm 1 98* 1976 1976 1977 see pentacomochrcrocycichexane see <j,bre'-cnecse*:y oyoC 50 ppm 500 ppm i 9"5 * q"*5 50 ppm 1975 1000 ppm 1 975 10 mg 1976 see Trichloro-2-pynoyicxyacetic acid use TLV 2 ppm 0 05 mg-Sxin 1975 i see 0 05 rng-Skm 1986 Trademark of The Dow Chemical Company Of, A OR9R10 CONFIDENT! Al -5- __________________ Mater ial__________________________________ IHG_______________ Date Hansa Yellow 4R (421) 0.05 mg 1975 Hexachlorpbenzene 150 ppb in the blood (Biological Limit Guide) 1978 Hexadene use WEEL Hydrogen iodide 3 ppm 1976 p-Hydroxybenzaide^yde 10 mg 1975 2-Hydrpxyethy. acrylate 1 ppm-Skin 1976 ^Hydrcxyethy1 ce'ijicse 10 mg 1975 Hydroxyethyl methyl cellulose 10 mg 1975 Hydroxypropyl celljlcse 10 mg 1975 Hyd'Oxyp'Opy! methyl ce^j'ose Ipnpl Irgancx 101C Fganox iC~6 1 0 mg 1C mg 10 mg 1C mg 1975 1975 1975 1980 lfcn 10 mg 1975 Iscbj'.ane 600 ppm 1978 Isobutylene see Methylpr&pe-e 2`lsocyanatoe`hyl metnacylate 25 ppb Ceil.ng-S*.- 1978 Isomazid 1 mg 1980 2-lsopropenyl.2-oxazolir.e 0.1 ppm-Skin 1979 Isop'opy' chioroiprmaie Ke'osene LONTREl* 0 1 ppm-Skin 10 mg see 3.6-Dich;prop co'.me aoc 1978 1 97S Magees _*- "yc'c* oe 10 mg 1975 MethacyOc ac c 20 ppm-Skin 1976 METHDCEl* 10 mg 1575 Methcxy'.ura-e 1C ppm 1 975 Me^y1 b:p-e-. Methyl chio'ice Methyl chlo-oace'ate 0.2 ppm 25 ppm, 75 ppm Excursion. 100 ppb-Skm 1980 196* 1 977 2-Metnyl-<-chiO'cphenoxy acetic 5 mg 1976 Methyl chlorpynfos see RELDAN* Methylene bisacrylarmde 3 mg 1976 Methylene bromice 15 ppm 1980 2-Melhylprppene 1000 ppm 1975 Metoclop-amide 0.3 mg 198C Trademark of The Dow Chemical Company DO A 039811 CONFIDENT TAI -6- ___________________ Material________ V:'c:,vo'ca:e,x aoc M:-.oet`.y' picsp'-.oroc.thioridolhioate (MEPCT) Nop-'.-.s p-N t'cbe'tza ce-tyde c-N tropheno p-N tropbeny' serme 'acetic methyl ester threo i-N'trcsO'A-methyl p,perazine Ncpcowax 22-DS Ncpcowax DS-'Ci N;.05FE'EO 6X G- 2 "r'e~\a2'C~zz-,D'oz; z o* stare Pera:- s'cse-re'e c'pp>r 3 re Fe*rc a'j'Pne-ate br^e Phenylephrine hydroch'or.de o-Pne-yiphe-ro, p-Phe^y pfce''C o*P-.e,"y<pKe'ic sod j" sa1' P'6"> p'ooano a~ re rycccrorise Fne-y sa o. a'e Pv-a p:yar' re B _e '*'3 p-'-s y s_'E'e*~,arc e "a o^a-Proo ,-e pc a~ ce Pp vC'vCD S Pc ystyene latex. Dry 9<S F 0 y"y alcoo; Potass jm bfcmaie Potassum bfo"".ioe Potassum carbonate Potassium chlpMde Potass:jt, lodate Potass j-n ioc.ce use WEEL 0 1 ppm-Skin IHG__________ 350 mg-Vapor, 1C mg-Ae'OSOl 3 mg 1 mg 10 mg 2 pp" 10 mg 10 mg 3 mg 1C mg 3 mg 0 i ppm 7 mg 5 mg 5 ppm 0.5 mg 5 mg 5 mg see DOWtCIDE A 1 mfi 10 mg 0 05 mg 10 mg use WEtL 10 mg use WEEL 10 mg 10 mg use WEEL 10 mg 10 mg 10 mg 5 mg 5 mg Date 1677 1979 1981 1977 1981 1978 1975 1975 1980 1975 1986 1976 1977 1975 1975 1981 1977 1977 1981 1975 1975 i960 1 67 1975 1979 i960 1975 1975 1975 1975 D0 A 039813 CONFTDFNTT Al -7- __________________ Material Potassium pe-su'fate Potassium sulfate Probucol Propachlor Prop.onalcehyde d-Propoxyphene hydrochloride ^"Propylene chlo'ohydr.n "Propylene g!ycol Propylene oxide RELDAN (Metny! eh'o'pyn'es R 'arnpxin R/a^ycn SV Saccnann, see j~ sa t Se'icya'ce^yce Sa cy:,c aoc Sa'oi Santonox Sodum acetate Sodom bicarbonate Sodom bO'onyo'`Ce Sod -m pro-ate Sodom b'c^'ce Sec _rr, catenate Sodom encode Sodom ch o' te Sod um hexametaonespnate ScP.m hyc'cs-1'ce Sccom, monochic'oacetate Sodom persj'fate Sooum phenate Sooiurn polyacrylate Sodium sulfate Sodium thiosulfate Sodium frichlorcacetate Stearic ana IHG________________ Date 5 mg 19?6 10 mg 1975 10 mg 1979 0,5 mg 1980 5 ppm 1978 1 mg 1978 3 ppm Ceiling-S^. 1976 useWEEl 20 ppm; 100 ppm Excu'Sion 1980 0 1 mg-Skm 1976 2 mg 1977 5 mg 1977 10 mg IBS' 5 mg 1575 2 mg 1975 see phenyl salicylate 10 mg 1975 10 mg 10 mg 1975 1975 2 mg 1978 5 mg 1987 10 mg i960 10 mg 1978 10 mg 0 5 mg 1975 1975 iC mg se: 3 mg ' 975 1 mg 1977 5 mg 1576 5 ppm 1975 3 mg 1976 10 mg 1975 10 mg 1976 1 mg-Skin 1976 10 mg 1975 OfiV A 03- oo 1 AV C.ONF 8- __________________ Material______________ Streptomycin Styrene dime's and tnme's Sultadimethoxine Sulfolane Terfenadme Tetrabromobisphenol A **l,l ,2,2-Tetrabromoethane 2,3,7,8-Tetrachlorodiben.2o-p-dioxin 1.2.3.4- Tetrachlorober.zene 1.2.4.5- Tetrachlorobenzere l,l,2.2-Tetrachloree`hane 3.<.5.G-Tetrachicropicc!inic acid 2 3.S,6-Te*,racMioropyric;ne T efacyc.me Thicphosphoryi chlorice T nipjrea Tnjvm P Titanium tetraiodide Toluene disocyanate Topano' CA Trip'CT'.cneopenty' aicohc T fich.opyr 2 4.5-Tr,cnicros,",soie 2.4.5- Triphlo'ophenoi 2 ^.6-Tricn:0'opheno', sod.jm sal; 3.5 6-Thchioro-2-phr:d:nc' **T ricMorcp'opane 1,2.3-T ricbioropropene 315.6- Tricl'.loro-2-pyndinoi, sodum sa't 3.5.6- Trichloro*2-pyridyl dimethyl phosphate 3.5.6- T nchloro-2-pyndyioxyacetic acid 3.5 6-Tnchloro-2-pyndyloxyacetic acid, DOWANOL EB 3.5.6- TricMoro-2-pyndyloxyacetic acid, methyl ester 3.5 6-Trichloro*2-pyridylcxyacetic acid, tr.ethylamme T richlorphon tHG________ 1 mg 100 ppm 2 mg 4 ppm 1 mg 5 mg 0.1 ppm 0.01 ug 0.4 ppm 0 4 ppm 0 1 ppm-S*:" 2 mg-S*,n 2 mg 1 mg O.i ppm. 0.1 mg-Skin 10 mg 0.1 ppm, as lod ne 0 02 ppm. Ce.I.ng 10 mg 5 mg see Trich:aro-p, * ccxyacet: ac'= 10 mg 1 ppm 5 mg 7 mg 1 ppm-Skm 1 ppm-Skm 7 mg 1 mg-Skin 10 mg 10 mg. as acid ec.. valent 10 mg, as acid ecu vaient 10 mg. as acc ec^ va!e~: 10 mg Date 16r 7 1975 1 SBC 1561 1 4 *.976 1976 1975 1977 *5" *^ . 1675 : C"? 15"c 1 976 * sec 1975 1975 1964 1575 1976 i C' 1976 * C~ . 5E 1976 1977 *577 * 96" 1981 1981 1961 1976 oo C-ONF 0,"-?1< 9814 TOfrNTTAl -9- _Mater Tnsodum phosphate Uii'ama'ine Blue (5045) V9/DOA (D'CTy! adiphate V9) Viny1 benzyl chlonde V.tamin C VORANOL* CP700 ~"Z-6 2-11 methyl ester Z-200 Z^C brom.se Z 'K sul'ide d "jse' 2693 lajIHGDate use WEE L 10 mg 500 ppm 0.5 ppm Ceiling. S'mn 10 mg 10 mg 1 mg 1 ppm 0.5 ppm 5 mg 10 mg 1975 1975 198A 1976 1975 1977 1977 1977 1 SBC 1975 II. PHYSICAL AGENTS Noise Bearing conservation (8-hr day): 85 dBA with 5 d exchange rate. Engineering controls (8-hr day): 90 dBA with 5 dB exchange rat . Trademark of The Dov Chemical Company DO A qDDBI-F dfnttai CONFT GLCSSiPV Ceiling - This concentration should ret be exceeded, even for brief periods. Excursion - Excursion guides, as opposed to ceilings, are not intended as absolute limits in either concentration or time. They indicate that sustained exposures at or above the guide number are not appropriate. Excursion exposures should last minutes, not hours, but do not need to be arbitrarily limited to any specific time period. Likewise, the concentration at ary given time might exceed the guideline by a moderate amount, but should average out to the excursion guice level over the period of the excursion. The longer the excursion, the more important it is for,the average level during the excursion to be at or below the guideline. Excursions should not follow quickly one after another and the shift-length time-weighted average (TWA) should not be exceed. This definition does not preclude decisions to arbitrarily set definite time limits or more conservative concentration limits in particular plant situations. IhG - The Industrial Hygiene Guide (IHG' is the internal Dow guideline for 8-hcun TWA exposures to airborne concentrations of materials. These guidelines were prepared by industrial hygienists in cooperation with toxicology, medical, production and product department representatives and were approved by the Dow Industrial Health Board. Skin - This material may be absorbed through the skin in amounts sufficient to cause toxic effects. Although the IHG is for inhalation exposures, skin contact with this material can contribute to the overall exposure and invalidate the "WA exposure evaluations. It is reoorimendec that skir contact be avoidec. TLVs 3rd WE EL Guides - The exposure guidelines established by the ACGIH (TLVs) or the AI HA (WE EL s) are usee by Dow unless a lower Dow IHG already exists or a new, highe- IHG is adopted. Therefore, some IHGs have been replaced by TLVs or WEELs. Those IHGs which will no longer be used are indicated in this list and will be dropped fror future lists. M. G. Swank, IHG Coordinator Health & Environmental Sciences Information Center 1803 Building (S17) 636-3976 MS/maf 00 A 039816 CONF TDFNTTAI, IWORKPLACE American INDUSTRIAL HYGIENE ASSOCIATIC AIHA WEEL GUIDES 1986 t-Hr TWA Short*T*f?n TWA B*ni*jC*nyO* 2 ppm B'-(2<?Moroiopropyi 3 ppm 4 ppm. 15 min -- Cr.OrVr.snniCO' 0. mg. mJ -p Cr.'crosuifonic e:C 0.3 ppm - O.*ii0rotnfluoro#:*iy:e'i# 5 ppm - C*c*e'omoO.E*i*ny! 5 mg^ mJ -- CAiOi pi!r.yi*r># gtyepi 50 ppm. total 10 mgjmJ *'0*01 only O''oeuryitn* 600 ppm -- thar 50C ppm -- C>m#:nyi ;*r*pn;ri*,at* 10 mgfli1, totAJ $ mg/m\ rvapiraoi* Erytriromyein 3 mg/mJ -- HkCi*`1# 100 ppm -- H**nCioi Ciac-yitit 1 mg/mJ - utnium hyCrOnfl* - 1 mg/mJ. } mm L.tf'iurr, Okie* -- 1 mg/m3, 1 min 3-M*tfic*yprepyi*mi'i* 10 ppm 20 ppm 15 mtn Monotliorotcatic c:C 0.3 ppm,, Sum ,\ pom, ''S mtn i-Gctanoi 3ert**'yrnnt0' tnic^v-iie SC ppm 1 mg-itt -- P.coim*a 2 ppm Skm 5 POm Ppii-iOi'i# 1 ppm -- cS'ytnvi*n* giyCOU 10 mg, mr -- sO'yprOPyie^* g'yCOi* i0 mg. rrr - ps:i*.ufr. p'omt* 0 1 mg. m' -- P'Ppyi*-.* gi.co. Cu^Ount 5C pom. ioi*i 10 mg. nr a'0*oi only 0 i ppm. tun r*!'**myi''egiycoi ei*crv*te 1 mg.mJ -- p-TOiu*ie lullony! enionoe -- 5 nia/lti' i min -nt!hyi*r,*gtycoi oi*c*yi*te . nm*tnyi*min# 1 mg/mr i ppm -- -- T nm*t*iyiOiO'ODne tn*cryit# 1 mg, mJ -- nm*inyioiproc*n* mo/ m' -- tnme:nvi*c-yi*te 'ftooiwm pnoscnait - wfei ^Q mg, m' S mgmJ, 15 min R*vi*#a S-66 NOTE- For convenience, may oe cut to tit insic* a pocket manual. Workplace Environmental Exposure Level Guides (WEE^j are developed by the AIHA WEEL Committee for age"which have no current exposure guidelines establish by other organizations. They represent the workpia: exposure levels to which, it is believed, nearly all empic^ ees could be repeatedly exposed without adverse effect All WEEL's are expressed as time-weighted average cor centrations; however, different time periods are specifie depending on the properties of the agent. An 8-hr TWA indicates a time-weighted average eoncc tration for a normal B-hr workday ano 40-nr worxwee When it is believed that excursion levels shouic be me limited, a one to 30 minute TWA may oe recommences either in conjunction with, or in place of. an 8-nr TW value. The time specified is relevant to exposure. r.; necessarily to sampling. The word "Skin" indicates that the material may ; absorbed through the skin. Therefore. Skin contact cz contribute to the overall exposure and invalidate :r TWA exposure evaluations. DO A OOAfllJ COMF1 DFNT1A1