Odor Thresholds and Irritation Levels of Several Chemical
Transcription
Odor Thresholds and Irritation Levels of Several Chemical
Odor Thresholds and Irritation Levels of Several Chemical Substances: A Review JON H. RUTH Wausau Insurance Companies, 550 California Street, San Francisco, CA 94120. A collation of odor threshold data ,for approximately 450 chemical substances is presented. The range of odor thresholds reported in the literature is showlf along with any reported threshold of irritation to humans. Th~se data can assist the industrial hygienist in determining . when an "odor"may be in excess of the Threshold Limit Value®, when an organic vapor respirator is not acceptable due to the lack of an odor warning at the end of a cartridge life, and where odors may not indicate a hazard due to extremely low odor thresholds which may be well below the respective TLVs. Introduction Although the sense of smell cannot be relied upon to evalu ate the hazards of chemicals used in the workplace, the ind ustrial hygienist can use the odor threshold of a chemical in the recognition phase as a rough estimation of airborne concentration. The purpose of this effort is to gather together, in one listing, the odor threshold and irritation level data published in several less accessible formats. The range from the lowest reported odor threshold to the highest reported odor threshold is reported. A brief review of the information available on our sense of smell and odors is presented along with a short review of several methods of defining a threshold of odor. Through an understanding of how the odor data have been developed ,and knowing the range of odor thresholds, the industrial hygienist can use these odor thresholds intelligently as a tool in the recogni tion of potential hazards. Methodology The odor thresholds and irritation levels.of several hundred chemicals were taken from the industrial hygiene literature(l-lO) and other compilations of odor threshold data.(1l-24) The odor thresholds were recorded as a range from the lowest to the highest concentration reported. Whenever information was discovered with a reported odor threshold lower or higher than the current data base range, the appropriate value was changed. The concentration level where irritation begins was recorded where available. Subjective descriptions of the odors were also included where they have been determined. Finally, the American Conference of Governmental Indust,/~ial Hygienists - Threshold Limit Value(25) was added to th~' comput¢r data base where a TLV has been assigned; These data w,kreentered into a personal computer database program (Apple II+ using DB Master software) for manipulation (conversion of ppm data into mg/ m3 ), alphabetization and custom report generation (e.g., potential for separation ~f chemicals into groiJps with odors below the TLV vs. those with odors above the TLV)., In Table I, the data are presented in alphabetical order with both the lowest and highest thresholds given in mg/ m3 • The range of odor thresholds reported for a given chemical should allow the industrial hygienist to interpret the odor with a proper sense of caution. A description of the odor and the threshold of irritation are also presented. The TLVs, available in the computer data base, have not been included in Table I since they are not directly used in this format for the data. History In early times, Plato categorized odors as either pleasant or unpleasant. Several centuries later, Linnaeus, a Swedish scientist, proposed seven odoriferous qualities: I) aromatic, , 2) fragrant, 3) musky, 4) garlicky, 5) goaty, 6) repulsive, and 7) nauseous. A 20th Century Dutch physiologist added ethe real (fruity) and empyreumatic (b1.!rnt organic matter) plus several subdivisions to the previous classifications.(26) In " those early times, the research consisted of categorizing various chemicals based on the description of their odor quality. More recent research has concentrated on determin ation of the odor threshold, or the quantitative amount of chemical in air which can be detected by the human sense of smell. Physiology of Smell For a person to smell something, air containing odoriferous molecules must reach a tiny cluster of specialized nerve cells well inside the nasal cavity. These nerve cells, the olfactory neurons, are at the top of the nose, just above the bridge, and are positioned out of the major airstream. Each nasal cavity has about five million ofthese receptors which are the only nerve cells in the body which have the ability to regen erate. Inhaled air first passes across a series of small bones, the turbinates, which create turbulence and cause a sm.all amount of air to reach the odor receptors. Sniffing creates strong eddy currents that force more air into the upper portion of the nose and greatly increases the sense of smell.(17,26) Together with the actual flow rate of the air in the nose, it has been shown that air temperature and relative humidity also affect the perception of odors.(21) ;-<,~ Copyright 1986, American Industrial Hygiene Association A-142 Am, Ind, Hyg, Assoc, J. (47) March, 1986 Am, :;i The ten million olfactory neurons can perceive some 4000 ifdifferent odors.(17) A Yale University study has shown that 4the average person can correctly name only a handful of ~~'common odors. This limitation, however, seems to be a ~result of an inability to think of the name of the substance .\1~ rather than a failure t~~ detect the differences between the 10dors.(26) Although women are not better able to detect ~i odors than men, they are more a ware of the odor environ illlent and can identify more odors than men.(26) Constant . ;;f ~xposure to odors can ind uce non-perception as the olfac tory neurons become fatigued. People tend to become accus ,;' tomed to odors, even those which they initially find unpleas ant. Two different odors presented simultaneously can be distinguished from one another if their characteristic odors are sufficiently different from each other. Chemicals used to mask odors can eventually be detected separately from the odor these chemicals were supposed to be masking. '1 f c' i' t' f €~ Determination of Threshold The method of defining and determining the threshold of odor varies widely, giving rise to a significant range from low to high in the odor thresholds reported. A wide variation in threshold definition, sample presentation, panel selection, purity of chemicals used and data interpretation have resulted in data that seem to lack consistency. (21) A classical definition of odor threshold is the minimum concentration of an odorant which produces a noticeable change in the odor of the system.(21) The threshold is often designated as the lowest concentration perceived after no anomalies OCCUr.(27) Common anomalies are the perception of an odor when a blank or zero concentration sample is presented and not perceiving an odor at a concentration higher than that at which an odor was previously noticed. Another definition sometimes used is the recognition odor threshold: the minimum concentration at which the odor quality (description of smell) of the compound can be de scribed. Minor differences in concentration are beyond olfac tory discrimination. It takes approximately a 30% to 60% increase in the concentration to allow the subject panel to consistently identify the higher concentration as higher.(17,21) Samples may be presented in several fashions. Most simply, the odor concentrations may be presented in simple order of increasing concentration from zero to the concen tration level first perceived. Another protocol randomly mixes blanks, or zero concentration samples, in with the odor samples which are presented otherwise in simple order of increasing concentration. These presentations in order of increasing concentration are called serial tests.(28) Finally, the odor concentrations may be presented in a random fashion to minimize any sample order bias. Where odor recognition is the definition of the threshold, a triangle test is used most often, in which two odors are presented and compared.(2o.28) Panel selection ranges from trained "sniffers" to the general population. A quick sniff of the sample yields a better perception of the odor than a slow, even inhalation. Trained "sniffers" would understand how to sniff for the odor and be more experienced in describing the quality of the odor. Acenaphthene Acetaldehyd.e Acetic acid Acetic anhydride Acetone Acetonitrile Acetophenone Acetyl acetone Acetylene Acrolein Acrylic acid Acrylonitrile Aldrin Allyl alcohol Allyl Alcohol (N-) Allyl amine Allyl chloride Allyl disulfide Allyl glycidyl ether Allyl isocyanide Allyl isothiocyanate Allyl mercaptan Allyl sulfide Ammonia Am. Ind. Hyg. Assoc. I (47) March, 1986 Odor.Low mg/m" 0.5048 0.0002 2.5000 0.5600 47.4666 70.0000 0.8347 0.0409 657.2000 0.0525 0.2820 8.1000 0.2536 1.9500 150.0000 14.5080 1.4100 0.0005 44.0000 0.0610 0.0325 0.0002 0.0007 0.0266 1: OJ .~ 0 o U 'uj ::> >. .c "0 2 2 iC,,) e 0 ,,2 >. Cll E "0 C Cll ~ Cll 0 "E ;S Cll >. .c Q) c 'u '6 Q) :2 15 ~ Cll .c :.::i 'iii c o 16 z 'Q) Data may be interpreted in several different ways. The odor threshold may be set at the lowest concentration per ceived by a single subject (absolute threshold), which, of course, would yield the lowest concentration of an odor threshold. Other researchers determine the threshold as that concentration where 50% of the test subjects notice the odor TABLE I Odor Thresholds and Irritation Concentrations of Chemicals Chemical Compound ~ Odor High Description mg/m" of Odor 0.5048 4.1400 250.0000 1.4400 1613.8600 70.0000 2.9460 0.0409 657.2000 37.5000 3.1200 78.7500 0.4027 5.0000 150.0000 14.5080 75.0000 0.0005 44.0000 5.4240 1.7052 0.0515 0.0007 39.6000 Green, sweet, fruity Sour, vinegar-like Sharp odor, sour acid Minty chemical, sweet Ether-like Sweet, almond Burnt, sweet Rancid, sweet Onion-Garlic pungency Pungent, mustard Green, garlic, oniony Sweet Sweet, repulsive Mustard oil Garlic-like Pungent, irritating Irritating Cone. mg/m" 90.00 25.00 20.00 474.67 875.00 1.25 12.50 187.20 75.00 38.06 1144.00 17.02 17.05 454.50 6500.64 72.00 A-143 , :E 15 c o 13 ~ "8 Q) :E ODOR THRESHOLDS AND IRRITATION LEVELS: A REVIEW TABLE I Odor Thresholds and Irritation Concentrations of Chemicals Odor Low Chemical Compound -I ::r CD 3 III CD ~ 0 =' 50. iii' "0 III to CD ::E III IJl 8, "2. , ~ _I a 3 50 CD () Q. CD () "=''" 0 - 0 50 CD z ~ =' Q!. 0 r 5' iii -<0 s: CD - 0.. 5: =' CD cr '< III 50 a "0 III ;:+ '< III =' 0.. 3 III '< cr CD "0 a CD CD 0.. () cr '< c 0 0 0 "0 '< ~. mg/m 3 Carbon tetrachloride 300.0000 from CH, Caryophyllene 0.5350 Cellosolve 2.0350 Cellosolve 'acetate 0.3024 Cellosolve solvent 1.1040 Chloral 0.2825 Chlordane 0.0084 Chlorinated Camphene 23689 Toxaphene Chlorine 0.0300 Chlorine Dioxide 0.3000 Ch loroacetaldehyde 3.0000 Chloroacetophe none (alpha-) 0.1020 Chlorobenzene 0.9800 Chlorobenzylidene malonitrile (ortho-) Chlorobromomethane 2100.0000 Chloroform 250.0000 Chlorophenol 0.0189 Chloropicrin 5.4600 Chlorotoluene 0.2350 Citral 0.3738 Coumarin 0.0020 0.0012 Cresol 0.1050 Crotonaldehyde Cumene 0.0392 500.0000 Cyanogen 2.0000 Cyanogen chloride Cyclobutylamine 97.1750 309.2600 Cycloheptylamine Cyclohexane 1.4350 Cyclohexanol 400.0000 Cyclohexanone 0.4800 106.0000 Cyclohexylamine 5.0667 Cyclopentadiene 0.1031 Cyclopentyl acetate 676.4000 Cyclopentylamine 153.5170 Cyclopropylamine 5.0725 OOT 0.3600 Decaborane 565.0000 Decalin 11.9510 Decanoic acid 0.0006 Decanol 1.3440 Diacetone alcohol 0.0035 Diacetyl 0.0005 Diallyl sulphide 0.7752 Dibenzofuran Diborane 2.0000 Dibromo-3-chloropropane (1,2-) 0.0965 Dibutylamine 0.4224 0.4232 Dibutylamine (N-) 1.2144 Dichloroacetic acid Dichloroanisole (2,6-) 0.0003 Dichlorobenzene (ortho-) 12.0000 Dichlorobenzene (para-) 90.0000 Dichloroethane 445.5000 Dichloroethyl ether 90.0000 Dichloroethylene (1,2-) 0.3358 Dichlorophenol (2,4-) 1.4007 Dicyclo pentadiene 0.0297 Diethyl disulfide 0.0195 Diethyl ethanolamine 0.0536 3.1725 Diethyl ketone Diethyl pyrazine (2,5-) 0.0336 Diethyl selenide 0.0617 Odor High Description mg/m" of Odor Irritating Cone. mg/m 3 1500.0000 Sweet, pungent 0.5350 185.0000 270.0000 Sweet, musty 2.0240 0.2825 Sweet 0.0419 2.3689 15.0000 0.3000 3.0000 0.1500 280.0000 Bleachy, pungent Sharp, pungent Sharp, irritating Sharp, irritating Sweet, almond-like Peppery 2100.0000 Sweet 1000.0000 6.5224 Medicinal, empyrumatic 7.7000 Sharp, penetrating 0.2350 Pungent, irritating 0.3738 0.0120 Pleasant, vanilla 22.0000 Sweet, creosote, tar 3.0000 Pungent, suffocating 6.3700 Sharp, aromatic 500.0000 Pungent 2.0000 340.8600 573.4000 1.4350 Sweet, aromatic 400.0000 Camphor-like 400.0000 Sweet, pepperminty 448.0000 5.0667 0.1031 2278.4000 153.5170 5.0725 0.3600 565.0000 112.4800 43.2820 480.0000 Sweet 0.0880 0.1491 Garlicky 1.6150 4.0000 Repulsively sweet 0.2895 1.4256 2.5392 Fishy, amine 1.2144 0.0003 300.0000 180.0000 Mothballs 810.0000 Chloroform-like 2160.0000 1975.0000 Acrid, eth.ereal 1.4007 0.0540 Sharp. sweet 0.0195 0.1948 Amine 49.3500 0.1120 0.0617 Putrid 9.00 15.00 3.00 0.05 933.33 1.52 20480.00 6801.18 2.10 23.01 32.00 1050.00 200.00 100.00 565.00 240.00 1.93 150.00 240.00 . 600.00 2.70 ;:r iii ::E Am. Ind. Hyg. Assoc. 1. (47) TABLE I (cont.) Chemical Compound Amyl acetate (N-) Amyl acetate (sec-) Amyl alcohol (iso-) Amyl alcohol (N-) Amyl alcohol (tert-) Amyl amine (N-) Amyl mercaptan Amyl mercaptan Oso-) Aniline Anisole Apiole Arsine Azelidine Azine Azole Benzaldehyde Benzene Benzene hexachloride Benzenethiol Benzothiazole Benzyl chloride Benzyl mercaptan Benzyl sulfide Biphenyl Boron trifluoride Bromine Bromoacetophenone Bromochloromethane Bromoform Butadiene (1,3-) Butadiene dioxide Butane Butenethiol (2-) Butyl acetate (iso-) Butyl acetate (N-) Butyl acrylate Oso-) Butyl alcohol (iso-) Butyl alcohol (N-) Butyl alcohol (secondary-) Butyl alcohol (tertiary-) Butyl amine (N-) Butyl celloso/ve Butyl cellosolve acetate Butyl chloride (N-) Butyl ether (N-) Butyl formate Butyl furan (2-) Butyl lactate (N-) Butyl mercaptan Butyl sulfide Butyl toluene (P-, tertiary-) Butylamine Butylene Butylene oxide Butylthiazole (2, iso-) Butyraldehyde Butyric acid Butyric acid Oso-) Camphor (synthetic) Caprolactam Capryl alcohol Carbitol Carbitol acetate Carbon disulfide Carbon tetrachloride from CS 2 -l = (1) 3t\) 'iii' ~ 0 ::l g. a "'0 t\) ~ t\) ::l a. 3 t\) '< 0- ct> "'0 a m: n, 'iii' 0., rr '< C en • I O. 0 "'0 ~ cO' ;r . Hyg Assoc. J (47) March, 1986 Odor Low mg/m" Odor High Description mg/m" of Odor 00265 0.0107 25.2000 04332 0.8303 566G40 0.0001 0.0018 0.0002 0.2210 0.0570 0.8400 51.9200 31.6480 134.2600 0.0008 4.5000 0.0015 0.0012 04424 0.2350 0.0132 0.0184 0.0062 4.5000 0.3290 0.1221 16800000 5300.0000 0.3520 176000 2.8500 0.0001 0.0090 33.1333 0.0110 0.3600 0.3600 131.1500 219.0000 0.2400 0.4800 0.7194 3.3352 0.3731 70.8900 50.8000 35.0000 0.0016 0.0897 300000 3.0000 54.9600 0.2058 0.0202 0.0136 0.0010 29.1600 7.8000 28.0000 371000 00107 25.2000 72.2000 0.8303 132.0760 0.0018 0.0018 350.000d 0.2210 0.0570 2.0000 169.9200 66.2400 295.9200 0.1823 270.0000 142.8000 279.0000 2.2120 1.5500 0.2028 0.0184 0.3000 4.5000 24.5000 1.3838 1680.0000 5300.0000 2.8600 17.6000 14.6300 0.0001 90.0000 94.6666 0.0660 225.0000 150.0000 131.1500 219.0000 6.0000 288.0000 1.3080 6.3293 2.5051 834000 50.8000 35.0000 00033 0.0897 30.0000 378.0000 54.9600 2.0874 0.0202 26.5500 9.0000 29.1600 1200.0000 28.0000 1.1508 0.1872 0.0243 60.0000 6.0280 1.8936 23.1000 128.4000 '~ Fruity, banana, pear Irritating Cone. mg/m.l 530.00 Sweet Pungent, amine-like Garlic-like Pleasant, bitter Sweet, solventy Solventy Unpleasant Sulfidy 20.01 9000.00 41.00 22.81 750 Pungent, irritating Bleachy, penetrating Unpleasant 2.10 0.33 Similar to chloroform 35.20 Pleasant, fruity Fruity Sweet, musty Mild, non-residual Sweet Strong, pleasant Camphor-like Ammonical Sweet, ester Sweet, ester Pungent Fruity, sweet 1350.00 473.33 300.00 75.00 30.00 Stinks! Gasoline-like Ammonia, fishy Gassy Sweet, alcohol 48.00 30.00 Sweet, rancid Sour, perspi ration 10.62 Sweet, pungent Sweet, musty Sweet Disagreeable, sweet Sweet, pungent A-145 ODOR THRESHOLDS AND IRRITATION LEVELS: A REVIEW TABLE I (cont.) Chemical Compound -t ::T CD 3Q) ~ ![ 0 ::J 5' 00' "0 Q) co CD ::E Q) en ("): 0, "0 CD' Co =r i 0 3 5' CD (") Q. CD (") g ::J 0 5 ' CD z Q) = 0 ::J Q!. r cr ill ~ 0 ~ CD Co n' S' CD cr '< Q) 5' a "0 Q) Q Q) ::J Co 3Q) '< cr CD "0 <3 CD (") CD Co cr '< c 0 0 0 "0 ~ ciS' ~ Q) ::;: Diethyl sulphide Diethyltrisulfide Diethylamine Diglycidyl ether Diisobutyl carbinol Diisobutyl ketone Diisopropyl amine Dimethoxy dimethyl pyrazine Dimethyl acetamide Dimethyl amine Dimethyl disulfide Dimethyl ethanolamine Dimethyl formamide (N,N-) Dimethyl napthalene Dimethyl sulfide Di methyl trisulfide Dimethyltrithiocarbonate Dimethylacetamide (N,N-) Dimethylamine Dimethylformamide (N,N-) Dimethylhydrazine (1,1-) Dioxane (1,4-) Dioxane (para-) Dioxolane (1,3-) Dipentene Diphenyl ether (perfume) Diphenyl sulfide Dipropylamine Dipropylamine (N-) Dipropylene glycol methyl ether Dodecanol (1-) Dodecyl Mercaptan (N-) Dowtherm A Endrin Epichlorohydrin Ethane Ethanolamine Ethoxy 3,4 dihydro 1,2 pyran (2-) Ethoxy 3,4-dihyro 1,2 pyran Ethyl acetate Ethyl acrylate Ethyl alcohol (synthetic) Ethyl amine Ethyl amyl ketone Ethyl benzene Ethyl benzoate Ethyl bromide Ethyl butanol (2-) Ethyl ether Ethyl formate Ethyl hexanol (2-) Ethyl hexyl acetate Ethyl hexyl acrylate (2-) Ethyl isothiocyanate Ethyl lactate Ethyl mercaptan Ethyl methyl disulfide Ethyl methylamine Ethyl morpholine (N-) Ethyl phenylacetate Ethyl propyl amine Ethyl selenide Ethyl selenomercaptan Ethyl silicate Ethyl su Ifide Odor Low mg/m' Odor High Description of Odor mg/m" 0.0177 0.0044 0.0600 25.0000 0.1885 0.6600 0.5200 1.2366 161.0000 0.0846 0.0001 0.0546 300.0000 0.0428 0.0025 0.0062 0.0331 163.8000 0.0378 300.0000 12.0000 0.0108 20.1600 44.5400 0.0117 0.0044 114.0000 25.0000 0.9424 1.8600 3.4000 1.2366 163.8000 0.0846 0.3465 0.1638 300.0000 0.0428 0.0508 0.0062 0.0331 163.8000 55.8000 300.0000 20.0000 612.0000 972.0000 335.3600 0.6950 0.0026 0.0826 0.4140 210.0000 0.0152 4222.8000 0.7000 0.2808 50.0000 184.5000 5.3333 3.1440 0.1048 0.0196 0.0008 0.3420 0.4860 31.2000 8.7000 3.8068 890.0000 0.2919 0.9900 0.6950 0.0358 227.1500 0.8280 6000.0000 0.0533 4222.8000 7.0000 6.3963 80.0000 1105.7700 10.6666 3.1440 3.1440 665.0000 32.0000 9690.000 396.0000 31.2000 870.0000 3.8068 890.0000 3.2109 3.0000 0.3990 0.5132 0.5497 6.0520 67.6200 3.2 x 10-5 0.0487 21.6900 0.3680 4.3615 60.5200 0.0003 8.0 x 10- 6 722.5000 0.0009 0.7342 1.4763 1.3554 6.0520 67.6200 0.0920 0.0487 79.5300 1.1500 4.3615 181.5600 0.003 0.0054 722.5000 0.0103 Irritating Cone. mg/m" Foul, garlickly Fishy, ammonical 150.00 50.00 Sweet, alcohol Sweet, ester Fishy, amine 150.00 100.00 174.60 Amine Decayed cabbage Amine, burnt, oily Fishy, ammonical Fishy, pungent Ammonical, amine-like Ether-like Sweet, musty Lemon-like Pleasant, geraniums Burnt, rubbery Ammonical, amine Ammonical, amine Ether-like 450.00 Aromatic, disagreeable Chloroform-like Ammonia Sweet, fruity Sweet, fru ity Fruity, pleasant Earthy, acrid, plastic Sweet, alcoholic Sharp, ammonical Mild, fruity Aromatic Ether-like Musty, sweet Sweet, ether-like Fruity Musty Sweet Sharp, musty Mustard, unpleasant 792.00 720.00 21.00 325.00 13.33 350.00 16.00 9500.00 180.00 260.00 870.00 28925.00 300.00 990.00 65.15 Garlic Ammonia Foul Alcohol-like, sharp 184.00 5950.00 Am. 1M Hyg. Assoc. J (47) TABLE I (cont.) Odor Low Chemical Compound 9' a -c Q) ;::\. '< Q) ::J c.. 3 Q) '< g, -c a CD ~ c.. 0" '< c 0 0 0 -c ~ cO' Ethyl valerate Ethyl vinyl ketone Ethylene Ethylene diamine Ethylene dibromide Ethylene dichloride Ethylene glycol Ethylene glycol dinitrate Ethylene oxide Ethylenediamine Ethyleneimine Ethylidene norborene Fluorine Formaldehyde Formamide Formic acid Furfural Furfuryl alcohol Glycol diacetate Heptachlor Heptanal Heptane Heptyl alcohol (N-) Heptyl isobutyrate Heptyl propionate Hexachlorobutadiene Hexachlorocyclopentadiene Hexadiene Hexane (N-) Hexanol (1-) Hexyl acetate (secondary-) Hexyl isobutyrate Hexyl propionate Hexylene glycol Hydrazine Hydrochloric acid Hydrofluoric acid Hydrogen bromide Hydrogen cyanide Hydrogen peroxide Hydrogen selenide Hydrogen sulfide Iodine Iodoform Ion one Isoamyl alcohol Isobutyl2-methoxypyrazine Isobutyl 3-methoxypyrazine Isobutyl 3-methyl pyrazine Isobutyl butyrate Isobutyl mercaptan Isobutyl pyrazine (2-) Isodecanol Isopentanoic acid Isophorone Isopropyl acetate Isopropyl alcohol Isopropyl amine Isopropyl ether Isopropyl glycidylether Kerosene Ketene Lauraldehyde Linalyl acetate Malathion Maleic anhydride mg/m 3 Odor High Description mg/m 3 of Odor 0.0266 0.0004 299.0000 2.5000 76.8000 24.0000 62.5000 0.0266 0.0069 4600.0000 28.0000 76.8000 440.0000 62.5000 520.0000 25.0000 4.0000 0.0700 6.0000 1.4700 150.0000 0.0450 0.0240 32.0000 0.5552 0.3060 0.0140 200.0000 98.3250 0.0989 0.0281 12.0000 1.5000 1.6750 1400.0000 28.0000 4.0000 0.3650 6.0000 73.5000 150.0000 37.8000 20.0000 32.0000 1.8626 0.3060 0.0932 1280.0000 98.3250 0.0989 0.0281 12.0000 3.3000 127.3000 0.0417 0.0120 0.0422 0.0514 250.0000 3.0000 7.0000 0.0333 6.6667 0.9000 21.6840 600.0000 0.0422 0.0514 250.0000 4.0000 49.0000 0.1333 6.6667 5.0000 Olefinic Ammonical, musty Mild, sweet Sweet Sweet Irritating Cone. mg/m 3 250.00 0.18 Sweet, olefinic Musty, ammonical Ammonical Sweet, ~romatic Pungent, hay Pungent, penetrating Almonds 500.00 200.00 30.00 50.00 1.50 27.00 48.00 Fruity, acid Gasoline-like 1800.00 0.0016 0.0007 9.0000 0.0062 4.63 x 10- 7 36.0000 13.5800 1.3 x 10-5 0.2146 12.3690 0.0020 2.2080 0.1292 0.0209 1.0000 0.1900 7.8400 0.5040 0.0714 1440.0000 0.5517 0.0151 50.5260 13.5000 1.8400 Sweet, alcohol Unpleasant 250.00 Ammonical, fishy Irritating, pungent Strong, irritating Sharp, irritating Bitter almond Slightly sharp 12.0000 Decayed horseradish 0.0140 Rotten eggs 9.0000 0.0833 573.0500 126.0000 13.5800 0.2146 17.6700 0.0020 2.2080 0.2713 0.1084 50.0000 1520,0000 490.0000 480.0000 1260.0000 1440.0000 0.5517 600.00 Musty, alc()hol Goaty Sharp, objectionable Fruity Pleasant Pungent, ammonia Sweet, sharp, ether 49.00 4.17 10.00 150.00 6.00 14.00 2.00 360.00 50.00 380.00 490.00 24.00 1260.00 Sharp 122.60 41.40 0.0151 50.5260 13.5000 1.9600 Acrid 5.48 ~ March. 1986 A-147 , il'!I1I i ODOR THRESHOLDS AND IRRITATION LEVELS: A REVIEW TABLE I (cont.) Chemical Compound II Mercaptobenzothiazole Mercaptoethanol Mesityl Oxide Methyl 2, cyanoacrylate Methyl acetate Methyl acetylene-propadiene MAPP gas Methyl acrylate Methyl acrylonitrile (alpha-) Methyl alcohol Methyl amine Methyl amyl acetate Methyl amyl alcohol Methyl anthranilate Methyl benzyl alcohol Methyl bromide Methyl butanol (2-) Methyl butenoic acid (2-) Methyl butyl acetate Methyl cellosolve Methyl cellosolve acetate Methyl chloride Methyl chloroform Methyl cyclohexane Methyl cyclohexanol Methyl disulfide Methyl ethanolamine Methyl ethyl ketone Methyl ethyl pyridine Methyl formate Methyl furan (2-) Methyl glycol Methyl heptanoate Methyl hexyl ketone Methyl hydrazine Methyl iodide Methyl isoamyl alcohol Methyl isoamyl ketone . Methyl isobutyl'carbinol Methyl isobutyl ketone Methyl isocyanate Methyl isopropenyl ketone Methyl mercaptan Methyl methacrylate Methyl n-amyl carbinol Methyl n-amyl ketone Methyl n-propyl ketone Methyl naphthalene (2-) Methyl paratRion Methyl pentaldehyde (2-) Methyl pentane (2-) Methyl propanol (2-) Methyl propene (2-) Methyl pyrazine (2-) Methyl salicylate Methyl styrene (alpha-) Methyl thiocyanate Methyl vinyl ketone Methylamine Methylene chloride Methylene chlorobromide Methylene glycol Mineral spirits Monochlorobenzene Morpholine I" -l =r CD 3 * :::!. ~ 0 ::> 9' 00' "0 til to CD ::;;; til en, n' 0, ~" 0 ~ 0 3 9" CD n Q. CD g 0 ::> 0--., 9' CD Z !a 0' ::> ~ r 6' 03 -<0 --., :5::: CD 0- 5: ::> CD cr '< til 9' ~ "0 til ~ til ::> 0- 3 til '< cr CD "0 a CD n CD 0- cr '< c 0 () 0 "0 '< Odor Low mg/m 3 12.0208 0.3828 0.0680 4.0000 610.0000 180.0000 70.0000 6.0000 13.1150 0.0252 0.4123 1.3761 0.0581 7235.5000 80.0000 0.0450 0.0528 0.0266 0.2880 1.6320 21.0000 542.8570 2000.0000 2350.0000 0.0012 3.0700 0.7375 0.0297 500.0000 90.4500 186.6000 0.0236 1299.5200 1.7500 Irritating Cone. mg/m 3 Odor High Description mg/m 3 of Odor 12.0208 2.0416 100.0000 Sweet 12.0000 915.0000 Fragrant, fruity 180.0000 Foul, objectionable 70.0000 42.0000 26840.0000 12.0000 2.3560 2.1684 0.0581 5235.5000 4000.0000 0.8280 0.0528 0.0266 288.0000 240.0000 21.0000 3800.0000 2000.0000 2350.0000 0.0039 10.4380 147.5000 94.0500 6875.0000 90.4500 279.9000 0.0236 1299.5200 5.2500 100.00 12.00 30496.90 Sharp, sweet, fruity 262.50 6.00 22875.00 24.00 Sweet Sweet, ester Sweet, alcohol Sweetish Sour, sharp Body odor Mild, non-residual Sweet, ester Sweet, ethereal Chloroform-like Faint, benzene-like Weak, coconut oil 368.00 1050.00 5428.57 2350.00 Musty, ammonical Sweet, acetone-like Sour, pungent Pleasant 590.00 8750.00 21500.00 0.2919 0.0576 2.0800 0.4100 1.0222 4.0 x 10'5 0.2050 0.0989 0.0940 28.0000 0.0581 0.1328 0.3681 0.2886 0.0027 45.8000 231.0000 0.6220 0.2496 0.7475 0.5720 0.0252 540.0000 2120.0000 76.2000 157.5000 0.9800 0.0350 0.8340 Pungent 0.3360 200.0000 Sweat, mild odor 192.7000 Sweet, sharp 1.0222 0.0820 1.3940 0.3378 0.0940 45.5000 0.2905 0.1328 0.5562 0.2886 0.1303 45.8000 231.0000 0.8708 960.0000 0.7475 0.5720 12.0000 2160.0000 2120.0000 76.2000 787.5000 0.9800 0.4900 100.00 410.00 5.00 Sulfidy Arid, fruity, sulfidy Sweet, alcohol 697.00 Sweet, rancid Gassy 960.00 480.19 Sweet, aromatic Sweet, unpleasant 30.00 8280.00 Fishy, pungent Sweet Chlorinated, mothball Fishy, amine :::!. to ;or A-148 Am. Ind. Hyg. Assoc. J. (47) 3i ~ TABLE I (cont.) .E C) .~ Chemical Compound Musk oil Mustard gas Myrcene Naphthalene Nickel carbonyl Nitric acid Nitric oxide Nitrobenzene Nitroethane Nitrogen dioxide Nitromethane Nitropropane (1-) Nitropropane (2-) Nonane Nonanol (2-) Octadiene (1,3-) Octane Octyl alcohol Oxygen difluoride Ozone Parathion Pentaborane Pentachlorophenol Pentane Pentanedione (2,4-) Pentanol (n-) Perchloroethylene Perchloromethyl mercaptan Perchloryl fluoride Phenol Phenyl ether Phenyl ethyl alcohol (beta-) Phenyl sulfide Phenylacetaldehyde Phosgene Phosphine Phthalic Anhydride Picoline (2-) Picric aciel Propane Propionaldehyde Propionic acid Propyl acetate (n-) Propyl alcohol Propyl alcohol (n-) Propyl mercaptan Propyl nitrate (n-) Propyl sulfide Propylene Propylene diamine Propylene dichloride Propylene glycol dinitrate Propylene glycol isobutyl ether Propylene glycol methylether Propylene oxide Pyridine Pyrrolidine Quinone Rotenone Safrole Silicon tetrafluoride Skatole Stoddard solvent Styrene (inhibited) Styrene (uninhibited) Styrene oxide . Ind. Hyg. Assoc. I (47) March, 1986 Odor Low mg/m 3 Odor High Description mg/m'J of Odor 3.8 x 10'6 0.0150 0.0723 1.5000 0.2100 0.7500 0.3600 0.0235 620.0000 2.0000 250.0000 ro80.0000 17.5000 3412.5000 0.0005 54.0000 725.0000 0.6916 0.2000 0.0010 0.4760 2.5000 0.0487 0.0150 0.0723 125.0000 21.0000 2.5000 1.2000 9.5000 620.0000 10.0000 250.0000 1080.0000 1029.0000 3412.5000 20.6150 90.0000 1208.3300 0.6916 1.0000 1.0200 0.4760 2.5000 6.6000 0.0409 0.7560 31.3560 0.0075 46.6666 0.1786 0.0070 35.0000 0.0026 0.0010 2.0000 0.0280 0.0532 0.0005 1800.0000 0.0225 0.0840 0.2100 75.0000 0.0750 0.0002 210.0000 0.0531 39.5600 0.0424 1.1667 1.2000 60.5000 360.0000 24.7500 0.0090 58.0000 0.4000 5.7960 1.4586 4.2500 4.0 x 10'7 5.2500 0.4300 0.2021 0.3093 3000.0000 0.0982 1.1160 469.0000 0.0075 46.6666 22.4200 0.7000 35.0000 0.0358 0.0196 4.0000 3.6000 0.1748 0.0005 36000.0000 0.4029 60.0000 105.0000 500.0000 150.0000 0.0746 210.0000 0.0531 116.2720 0.2030 606.6660 1.5600 60.5000 360.0000 500.0000 15.0000 187.3400 0.4000 5.7960 1.4586 4.2500 0.2680 157.5000 860.0000 860.0000 1.9640 c.. Irritating Cone. mg/m 3 0 () u:i :::> >. .0 "t:l Mothball, tar-like Musty 75.00 • ~ Q) ....... ,e ]~ 155:00 c.. Q) .0 Shoe polish, pungent Mild, fruity Sweetish, acrid Mild, fruity Mild, fruity >. 230.00 310.00 20.00 500.00 360.00 co E c "t:l co >. t co c.. "E ;S co >. Gasoline-like .0 1450.00 Q) c '0 Foul Pleasant, clover-like Garlic-like Strong, pungent Pungent when hot Gasoline-like Sour, rancid Sweet, alcohol Chlorinated solvent '5 Q) - ::2: 2.00 0 i::" ~ 10.90 .0 :.:J ro c 0 10 z 1340.00 - Q) :E Sweet Medicinal, sweet Disag reeable 0 c 182.40 21.00 0 1:5 ~ (5 u Q) :E Musty hay, green corn Oniony, mustard, fish 8.00 10.67 30.00 E 0 .t:: "t:l Q) '0 Sweet 0 t.'l Ul 1Il 3: Ql c 1Il c Sweet, ester Sour Sweet, ester u: ;5 13750.00 c Sweet, alcohol c Ether-like Ii: .;:: a: it E a: 2801.40 Aromatic Sharp, amine Sweet Sweet, alcoholic Burnt, sickening Acrid .J: I 121.00 3600.00 1125.00 90.00 2.00 42.50 Perfume Kerosene-like Solventy, rubbery Solventy, rubbery Sweet 2100.00 4300.00 430.00 A-149 ODOR THRESHOLDS AND IRRITATION LEVELS: A REJIIEW 3 .!!1 ..... .c TABLE I (cont.) Chemical Compound Sulfur dichloride Sulfur dioxide Sulfur monochloride Sulfuric acid Tetrachloroethane (1,1,2,2-) Tetrachloroe.thyelene TetraethylorthoSilicate Tetrahydrofuran Tetra/in Tetramethylenediamine Thiophene Thiophenol mercaptan Toluene petroleum Toluene from coke Toluene 2,4 diisocyanate TO! Toxaphene Trichloro fluoromethane Freon 11 Trichloro trifluoroethane Freon 113 Trichlorobenzene (1,2,4-) Trichloroethylene TCE Trichloropropane (1,2,3-) Tricycloketone Triethyl amine Trimethyl amine Trimethyl phosphite Trimethylenediamine Trinitro tert-butylxylene musk oil Turpentine Valerie acid Vanillin Vinyl acetate Vinyl amyl ketone Vinyl butyl ketone Vinyl propyl ketone Vinyl pyridine Vinyl toluene Vinylidene chloride VM&P naphtha Xylene Xylidene Odor low mg/m 3 0.0042 1.1750 Odor High Description mg/m 3 of Odor 1.0000 21.0000 31.3560 30.6360 7.3750 97.2000 79.2000 0.0026 0.0012 8.0250 0.0042 Sulfidy 12.5000 Yech! Nauseating 1.0000 35.0000 Sickly sweet 469.0000 Chlorinated solvent 61.2720 Sweet, alcohol 177.0000 Ether-like 97.2000 79.2000 0.0026 Aromatic 382.5000 150.0000 Rubbery, mothballs 17.5500 262.5000 Floral, pungent od e> by- .~ 0 ca 0 () Sl u:j pr ::> >. ml .0 'C tw 2 () th 2 er e 0 Ql res' .0 th >. ('(J E su 'C Irritating Conc. mg/m~ 5.00 12.00 1.10 1302.00 710.20 c:: co ~ co 750.00 0 'E 750.00 ;5 4.00 .0 Ql co 3.2000 17.1200 Sweet, fruity, acrid >. c:: '(3 2.3660 28.0000 2.3660 1170.4000 Sweet '6 342.0000 1026.0000 Sweet '0 i::' Ql ~ ~ 24.0000 1.1340 24.0000 2160.0000 Solventy .0 40.00 864.00 :.:J m c:: o Strong, acrid 1.8660 0.3600 0.0008 0.0005 3757.2000 3.8 x 10'6 15 300.00 870.8000 1.1200 Fishy, amine 0.0008 Fishy, pungent 0.0005 Pyridine-like 11968.5000 0.0487 '1.2 Re~ 200.00 c:: o 2. 560.0000 0.0026 2.0 x 10'7 0.3600 0.5150 0.0321 0.0201 1.1670 240.0000 2000.0000 3.8700 0.3480 0.0240 1120.0000 0.0026 1.6500 0.5150 0.0321 0.0201 1.9450 240.0000 4000.0000 3.8700 174.0000 0.0240 Perfume Sour, sharp 3. The influence of chemical contaminants may explain some of the variation in thresholds observed.(21) Note the differences in odor thresholds in Table I o(toluene manufac tured from two different ra w materials, or carbon tetrachlo ride from different sources, or inhibited vs. uninhibited sty rene. There has been a tendency for lower thresholds to be identified in the more recent research, which has been attrib A·150 Ql .g 'C Ql '0 Nauseating Disagreeable Sweet, chloroformish 4. : 8 .' Ul .co .:;: 5. ! Ql C 240.00 ~ 435.00 ;S 6.. § Ul ro ~ 71 or recognize an9 describe the odor. Finally, some researchers look for a 100% panel resportse. This latter method would generate higher concentration levels as the defined thresh old. One stutlY, which reported both the absolute thresh old and the 100% recognition threshold, showed the 100% recognitionthresho~d to be approximately two to ten times higher than the absolute threshold.(24) ~ "8 £ E 560.00 Sweet Weak, amine-like :5 1. 15 uted to greater purity of samples and better techniques sample presentation, 0 \ I 8. Discussion It must be remembered that the data listed in Table I an~' essentially for the single chemical constituent with no othe~ chemicals present in the air. Mixtures of different chemical~' have received very little study.(28) The question is whetheQ two chemicals at concentrations below their odor thresholds (RA and R B ) can add up to constitute one combined "odor" (RAB) which is perceived, or whether the olfactory receptor~ react very specifically to each chemical so that no odor i{ perceived(17) (Figure I - Independence). There have been several studies where two mixed chemicals, each at 50% of its Am. Ind. Hyg Assoc. J. (47)' ~ <.U .c 9. 10. Am. odor threshold, have produced an odor which was perceived 'by test subjects(17) (Figure I - Addition). While mixed chemi cals may betotally independent of one another or produce simple additive effects, it is also possible that the mixture produces an enhanced or a suppressed reaction from what might be predicted. An enhanced reaction would result from two mixed chemicals, each at less than 50% of its odor threshold, which produce a perceived odor (Figure I - Syn ergism). A suppressed reaction, or counteraction, would result when two mixed chemicals, each at 100% of its odor threshold, fail to produce a perceptible oeor among test subjects (Figure I - Counteraction). Hygiene and Toxicology, Vol. IIC - Toxicology, 3rd rev. ed. New York: John Wiley & Sons, 1982. 11. Hille, V.E.: Bestehen BeZiehungen Zwishen den Geruchs schwellenwerten undden Immissionsgrenzwerten Chemis cherSubstanzen? Staub Reinhalt. Luft 37(5):199-201. (1977). 12. Braker, W., A.L. Mossman and D. Siegel: Effects of Expo sure to Toxic Gases.- First Aid and Medical Treatment, 2nd ed. Lyndhurst, N.J.: Matheson, 1977. pp. 7-151. 13. Manufacturing Chemists Association: Chemiclli Safety Data Sheets. Washington" DC. 14. Summer, W.: Odour Pollution of Air - Causes and Control. London: Leonard Hill, 1971. pp. 22-24, 28, 43, 159. 15. National Research Council, Committee on Odors from Sta tionary and Mobile Sources: Odors from Stationary and Independence, Mobile Sources. Washington, D.C.: National Academy of RAB = RA or RB Sciences, 1979. pp. 24-27, .182-183. Addition 16. American Society for Testing and Materials, Committee RAE = RA + RB E-18 on Sensory Evaluation of Materials and Products: Compilation of Odor and Taste Threshold Values Data. Synergism Edited by FA Fazzalari. Philadelphia: ASTM. RAB >RA + RB 17. May, J.: Odor Thresholds of Solvents for Assessment of Counteraction SOlvent Odors in the Air (UDC 614.718:66.062-911. RAE < RA or RB 3:613.155.3:612.867). Staub Reinhalt. Luft 26(9):34-38 (1966). 18. Cheremisinoff, P.N. and R.A. Young, eds.: Industrial Odor where RAB = odor threshold of mixture of chemical A and Technology Assessment. Table 8-11. Ann Arbor, Mich.: chemical B, Ann Arbor Science Publishers, 1975. RA = odor threshold of pure chemical A, and 19. Katz, S.H. and E.J. Talbert: Intensities of Odors and Irritat RB = odor threshold of pure chemical B. ing Effects of Warning Agents for Inflammable and Poison Figure 1 - Mixed Chemicals Odor RelationshipsYSJ ous Gases. Bureau of Mines Technical Paper 480. Washington, D.C.: U.S. Government Printing Office, 1930. References 20. Matsushitia, H., J. Arito, Y. Suzuki and R. Sod~: Determina 1. American Conference of Governmental Industrial Hygien tion of Threshold Values for Olfactory Percep'~ion of Prim ists,Committee on Industrial Hygiene: Industrial Ventila ary Odour Substances. Ind. Health 5:221-237 (1967). tion - A Manual of Recommended Practice, 17th ed. Lans (National Institute of Industrial Health, Kawasaki, Japan). ing, Mich.: ACGIH, 1982. pp. 13-20. 21. Arthur D. Little, Inc.: Research on Chemical Odors, Part I 2. Billings, C.E. and L.C. Jonas: Odor Thresholds in Air as Odor Thresholds for 53 Commercial Chemicals. Washing Compared to Threshold Limit Values. Am. Ind. Hyg. Assoc. ton, D.C.: Manufacturing Chemists Association, 1965. pp. E J. 42:479-480 (1981). 1-26. .g 3. American Industrial Hygiene Association: Hygienic Guide 22. Trayer, D.M.: Odor Thresholds for Air Contaminants. Safety ',r~ Series, Vol. I. Akron, Ohio: AIHA. "0. Newsletter - Public Utilities Section June 1976. Chicago, 8 III.: National Safety Council, 1976. p.2. 4. American Industrial Hygiene Association: Hygienic Guide Series, Vol. II. Akron, Ohio: AIHA. 23. Occupational Health Resource Center, Oregon Lung Asso Q) 5. National Institute for Occupational Safety and Health: ciation: Warning Properties of Industrial Chemicals. c ro Portland, Oreg. NIOSH/OSHA Occupational Health Guidelines for Chemi a cal Hazards (DHHS/NIO$H Pub, No. 81-123). Washington, rn 24. Hellman, T.M. and F.H. Small: Characterization of the Odor £ D.C.: Government Printing Office, 1981. Properties of 101 Petrochemicals Using Sensory Methods. c: o 6. Alliance of American Insurers: Technical Guide No.6 J. Air Poll. Control Assoc. 24:979-982 (1974). ro Handbook of Organic Industrial Solvents, 5th ed. Chicago, .;:: 25. American Conference of Governmental Industrial Hygie III.: AAI, 1980. pp. 55-107. nists: Threshold Limit Values® for Chemical Substances E and Physical Agents in the Work Environment with Intended 7. Alliance of American Insurers: Technical Guide No. 7 G.l Changes for 1984-85. Cincinnati, Ohio: ACGIH. 19'84. pp. .c: Handbook of Hazardous Materials, 2nd ed. Schaumburg, r 9-33. III.: AAI, 1983. pp. 70-210. 8. Clayton, G.D. and F.E. Clayton, eds.: Patty's Industrial 26. Brody, J.E.: What the Nose Knows. This World July 24, 1983. pp. 13-14. Hygiene and Toxicology•. Vo. IIA - Toxicology, 3rd rev. ed. New York: John Wiley and Sons, 1981. 27. Wilby, F.V.: Variation in Recognition Odor Threshold of a Panel. J. Air Poll. Control Assoc. 19:96-100 (1969). 9. Clayton, G.D. and F.E. Clayton, eds.: Patty's Industrial Hygiene and Toxicology, Vol. liB - Toxicology. 3rd rev. ed. 28. Rosen, A.A., J.B. Peter and F.M. Middleton: Odor Thre New York: John Wiley & Sons, 1981. sholds of Mixed Organic Chemicals. Journal WPCF. 34(1 ):7-14 (1962). 10. Clayton, G.D. and F.E. Clayton, eds.: Patty's Industrial ~ * Am. Ind. Hyg Assoc. J. (47) March, 1986 A·l5l
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