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1 achieved by using specific solvents (or solvent mixtures) for the elution of compounds from 2 chromatographic columns. Schuetzle and co-workers ( 1985) proposed that standard chemical 3 compounds be selected for establishing reference points for the fractionation of diesel POM into 4 nonpolar, moderately polar, and polar fractions by normal-phase HPLC. They proposed that the 5 elution of 1-nitronaphthalene would define the end of the elution of nonpolar compounds and the 6 beginning of the moderately polar fractions. In a similar way, 1,6-pyrene quinone would define 7 the end of elution of moderately polar compounds and the beginning of the polar region. 8 For diesel engine emissions, ::::57% of the extracted organic mass is contained in the 9 nonpolar fraction (Schuetzle, 1983). About 90% of this fraction consists of aliphatic _1 0 hydrocarbons from approximately cl4 to about c40' with a carbon number maximum at c22 to c26 11 (Black and High, 1979; Pierson et al., 1983). Polycyclic aromatic hydrocarbons and alkyl- . 12 substituted P AH account for the remainder of the nonpolar mass. 13 The moderately polar fraction ( ::::9% w/w of extract) consists mainly of oxygenated P AH 14 species and nitrated P AHs. The polar fraction (:::: 32% w/w of extract) is composed mainly of 15 carboxylic and dicarqoxyli-c acids ofPAH, hydroxy-PAH, hydroxynitro-PAH, nitrated 16 N-containing heterocyclic compoimds, etc. (Schuetzle, 1983; Schuetzle et al., 1985). 17 Limited recovery studies have shown that there is little degradation or loss of diesel POM 18 on the HPLC column. More than 90% of the mass and 70% to 100% of the Ames 19 S. typhimurium-active material injected onto the column have been recovered (Schuetzle et al., ·20 1985). 21 22 2.3.2.3.3. Polycyclic aromatic hydrocarbons. Particle-bound P AHs and their derivatives 23 (mainly nitrated PAH) attracted considerable attention relatively early because of their mutagenic 24 and, in some cases, carcinogenic properties (see, for example, National Research Council, 1982). 25 The most widely used methods ofPAH analysis included thin layer chromatography (TLC), 26 capillary gas chromatography (GC), gas chromatography/mass spectrometry (GC/MS), and 27 HPLC with ultraviolet or fluorescence detection (Levsen, 1988). Table 2-8 lists the P AHs and 28 thioarenes identified and quantified by GC/MS in three LDD particulate matter extracts (Tong 29 and Karasek, 1984). Data listed in this table reveal the presence of a large number of alkyl 30 derivatives of P AH, which are sometimes more abundant than the parent P AH. 31 Table 2-9 compares the emission rates of several representative P AHs from HDD, LDD, 32 and gasoline (with and without catalytic converter) engines. 33 34 2.3.2.3.4. Nitrated polycyclic aromatichydrocarbons. Nitro-PAHs (nitroarenes) have been 35 shown to be present in diesel particulate extracts, though in much lower concentration than the 36 . · parent PAHs (Schuetzle et al., 1981, 1982; Paputa-Peck et al., 1983). Because many nitroarenes 211/98 2-19 DRAFT--DO NOT CITE OR QUOTE
Table 2-8. Polycyclic aromatic hydrocarbons identified and quantified in extracts of diesel particles Compound•·b Molecular weight Acenaphthylene 152 Trimethylnaphthalene 170 Fluorene 166 Dimethylbiphenyl 182 C 4-Naphthalene 184 Trimethylbiphenyl 196 Dibenzothiophene 184 Phenanthrene 178 Anthracene . 178 Methyldibenzothiophene 198 Me thy !phenanthrene 192 Methy !anthracene 192 Ethylphenanthrene 206 4 H -Cyclopenta[ dej]phenanthrene 190 Ethyldibenzothiophene 212 2-Pheny !naphthalene 204 Dimethyl(phenanthrene/anthracene) 206 F1uoranthene 202 Benzo[dej]dibenzothiophene 208 Benzacenaphthyle.ne 202 Pyrene 202 Ethylmethyl(phenanthrene/anthracene) 220 Methyl(fluoranthene/pyrene) 216 Berizo[a]fluorene/benzo[b]fluorene 216 Benzo[b]naphtho[2, 1-d]thiophene 234 Cyclopentapyrene 226 Benzo[ghi]fluoranthene 226 Benzonaphthothiophene 234 Benz[ a] anthracene 228 Chrysene or triphenylene 228 1 ,2-Binapthyl 254 Methylbenz[a]anthracene 242 3-Methylchrysene 242 Phenyl(phenanthrene/anthracene.) 254 Benzo[Jlfluoranthene 252 Benzo[b ]fluoranthene 252 Benzo[k]fluoranthene 252 Benzo[e]pyrene 252 Benzo[a]pyrene 252 Berizo[ah]anthracene 278 lndeno[1 ,2,3-[cd]pyrene 276 Benzo[ghtlperylene 276 Dibenzopyrene 302 'Compounds are arraiJ¥ed according to increasing gas chromatography retention times. 'Isomeric alkyl derivanves are not listed separately. 'Concentration range as found in the particulate extracts of three Volkswagen passenger cars. 'Soluble organic fractions accounted for 11.1%, 12.1%, and 14.7% of total particulate matter (w/w) for these three diesel samples. · . Source: Tong and Karasek. 1984. , Concentration (ng/mg extract)c.d 30 140-200 100-168 30-91 285-351 50 129-246 2,186-4,883 155-356 520-772 2,028-2,768 517-1,522 388-464 517-1,033 151-179 650-1,336 1,298-2,354 3,399-7,321 254-333 791-1,643 3,532-8,002 590-717 1,548-2,412 54.1-990 30-53 869-1,671 217-418 30-126 463-1,076 657-1,529 30-50 30-50 50-192 210-559 492-1,367 421-1,090 91-289 487-946 208-558 50-96 30-93 443-1,050 136-254 2/1198 2-20 DRAFT--DO NOT CitE OR QUOTE
Page 1 and 2: DRAFT DO NOT CITE OR QUOTE Health A
Page 4 and 5: CONTENTS (continued) 2.5.1. Volatil
Page 9 and 10: CONTENTS (continued) 11.2.1. H.fl.Z
Page 12: LIST OF TABLES (continued) 2-14. Me
Page 17 and 18: PREFACE This draft health assessmen
Page 20 and 21: AUTHORS, REVIEWERS, AND CONTRIBUTOR
Page 22: l. INTRODUCTION 1 Diesel engines ar
Page 45 and 46: Nitro-PAH• Table 2-10. Concentrat
Page 50: 1 pollutants depends on the amount
Page 56: 1 For the simplest alkoxy radicals,
Page 63 and 64: 1 2 3 4 5 6 7 8 9 10 11 12 13 H ON0
Page 66 and 67: 1 conditions (Pitts et al., 1985c )
Page 69: Table 2-14. Mean particle, gas, and
Page 72 and 73: 1 sample collection. There was no b
Page 75: 1 of downtown Los Angeles (Arey et
Page 81: 1 exposures. This is a complex ques
Page 85: 1 Dunstan, TDJ; Mauldin, RF; Jinxia
Page 88 and 89: 1 Lipkea, WH; DeJoode, AD; Christen
Page 90: 1 Pitts, JN, Jr; Sweetman, JA; Ziel
Page 95:
1 NOTE TO READERS CHAPTER3 2 Becaus
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1 volume basis (Table 4-1 ). This i
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1 Pritchard (1989), utilizing data
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1 4.3.3.3. Potential Mechanisms for
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1 not accurately reflect the actual
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1 Lee, PS; Chan, TL; Hering, WE. (1
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1 one-half units up to 3, strong (O
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Study Ulfvarson et a!. (1987) Batti
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N -,_. -\0 00 VI N ,_. 0 § I I 0 0
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1 control]). Heinrich et al. (1986a
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1 Heinrich et al. ( 1986a; see also
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1 thoracic area at subsequent times
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1 with matched controls for the num
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----- N \0 00 VI I 0'1 N tJ § I I
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1 In related studies, Navarro et al
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1 Mauderly et al. (1987b) evaluated
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1 pattern of adverse effects on res
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1 DPM concentrations) that resulted
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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
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1 Klosterkotter, W; Blinemann, G. (
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1 Misiorowski, RL; Strom, KA; Vosta
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1 Wright, ES. (1986) Effects of sho
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1 Studies showing these effects are
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1 exposure level. In the 0.3 5 mg/m
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1 to derive the RfC. The discussion
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1 The BMC values are the lower 95%
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Table 6-5. Results of benchmark con
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1 U.S. Environmental Protection Age
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1 the latter, 16 were classified as
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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
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1 burdens of the NMRI mice after 12
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1 with four to seven rings), which
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1 five daily doses of2,000 f...lg.
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1 occupations. The observed absence
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1 occupations). Analysis was conduc
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1 the confined space of a truck cab
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1 The corresponding odds ratios for
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1 Approximately 20,000 miners are e
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1 bladder cancer was found in Canad
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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
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1 Kaplan, I. (1959) Relationship of
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9. MUTAGENICITY 1 Since 1978, more
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1 the presence of heritable translo
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1 9.5. REFERENCES 2 3 "Barfknecht,
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1 U.S. Environmental Protection Age
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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
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1 inconsequential in rats relative
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1 response. cell injury, or cell pr
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1 Caution must be exercised in extr
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1 Rister, M: Baehner, RL. ( 1977) E
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1 The potency of the other diesel e
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Table 11-2. Incidence of lung tumor
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Table 11-5. Unit risk estimates per
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1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
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1 to reflect the potency of several
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1 Huisingh. J; Bradow, R; Jungers,
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1 particles are fine and ultrafine
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1 are available. Exposure is most o
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1 · some of which can be informed
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1 For example, in a recent meta-ana
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1 nonthreshold-mutagen driven MOA.
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1 that their developing pulmonary a
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1 impacts. Use of these measures re
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2/1198 Appendix A Experimental Prot
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APPENDIX A. EXPERIMENTAL PROTOCOL A
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Page 511 and 512:
Page 513 and 514:
2/1198 Appendix B Alternative Model
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1 d: Dose of organics, mg/cm 2 of l
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Table B-4. Comparison of observed t
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1 uncertainties below). Based on th
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1 B.lO. RFERENCES 2 3 Bohning D., A
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1 and 2 m.(t) = (y2i - YI/exp[Ap)a/
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1 C.l. INTRODUCTION 2 As discussed
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1 For mouth breathing: 2 (DF)H . =
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TABLE C-1. LUNG MODEL FOR RATS AT T
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TABLE C-3. RATIO OF PULMONARY SURFA
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