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1 Ann. Rep. Tokyo Metr. Inst. Pub. Health, 63, 247-253, 2012 a 169-0073 3-24-1 b 169-0073 3-24-1 DNPH /HPLC a a a b DNPH /HPLC 1 DNPH1 DNPH 1 mL mL 65 C 15 HPLC DNPH CNET DNPH CNET DNPH CNET

2 2,4- DNPH HPLC 1,2) 3,4) 100% 30 20% 120 10% 4) 1 DNPH1 1 2 DNPH 2 3 5,6) DNPH 7-10) DNPH 11-14) o- 4- -2- CNET 82 91 10) CNET DNPH DNPH 1.

3 10 mg/mL AccuStandard / DNPH Mix 15 Supelco CNET HPLC 85% HPLC HPLC 2. DNPH A ORBO-DNPH tubes Supelco 120 Ann. Rep. Tokyo Metr. Inst. Pub. Health, 63, 2012 248 mg B XPoSure Aldehyde Sampler Wa t e r s 350 mg CNET CNET-A 3. HPLC LC-10AT DGU-14A CTO-10AC SPD-10AV SPD-M10 AVP DNPH Table 1 CNET Table 2 4. -DNPH L 5 A 4 C 0 1 2 3 7 2 mL HPLC 5. A B L 4 6.

4 L 5 A 0 1 2 3 7 CNET 7. NFAD-50-EX 309 cc B 30 L 0 1 3 5 L HPLC 3 1. 0 7 HPLC Fig. 1 AC1 AC2 AC3 UV Fig. 2 AC1 373 nm AC2 356 nm AC3 354 nm AC1 AC2 AC3 UV Schulte-Ladbeck 5) AC1 1 DNPH1 AC2 1 DNPH2 AC3 2 DNPH3 Fig. 3 AC1 0 1 0 7 0 1/10 AC2 0 1 7 AC3 0 1 7 ColumnZORBAX Bonus RP 25cm, 5 m Column CEluent AAcetonitrile/Water/THF 50/50 BAcetonitrile/Water/THF 80/20 % 025142517100261002725 Flow mL/minInjection LWave Length360 nmTHF TetrahydrofuranTable 1.

5 HPLC Conditions for Acrolein-DNPHC olumnZORBAX Bonus RP 25cm, 5 m Column CEluent AAcetonitrile/Water/THF 50/50 BAcetonitrile/Water/THF 80/20 % 025102511100201002125 Flow mL/minInjection LWave Length240 nmTHF TetrahydrofuranTable 2. HPLC Conditions for Acrolein-CNET 63, 2012 249 2. AC2 AC3 AC1 - Fig. 3 1) A 4 1 mL 0 14 32 mL 25 C 60 C 6 25 C 60 C AC1 Fig. 4 60 C 2) A 4 1 mL mL 60 C 6 15 24 AC1 6 60% 15 85% 24 86% 15 24 AC1 15 AC1AC2AC30day1day2day3day7dayFig.

6 1. HPLC Chromatograms of Acrolein-DNPH (AC1)and its reaction p roducts (AC2 and AC3)AbundanceAbundanceAbundanceAbundance AbundanceAfter keep ing samp lers at 4 C from 0 day to 7 day s,t he acrolein-DNPH were analy z ed in each day 2. UV Sp ectra of AC1, AC2 and AC3AC1AC2AC3 NHNNNOOCOOHCHC H2AC3 Fig. 3. Presumed Structures of AC1, AC2 and AC3 5)Arrows indicat e t he exp ect ed at t ack p oint s by acid t reat ment .AC2AC1 NHNNNOCCH2CH2 NCH2CH2 CNOOOHHNHNNOOOONHNNOOOONHNNCCH2CH2 NHNOOOOHNHNNOOOO-204060800 1020 304050 Concentration of Phosp horic Acid(%)AC1 (%)25 C60 CFig. 4. Effect of Concentration of Phosp horicAcid Solution and Temp erature on Prop ortionChange of AC1T he p ercent ages of AC1 were calculat ed fromthe p eak height of AC1 and the sum of thoseof AC1, AC2 and Rep. Tokyo Metr. Inst. Pub. Health, 63, 2012 250 3) A B 4 1 mL mL A 40 C 70 C B 55 C 65 C 15 A 60 C B 65 C AC1 Fig.

7 5 1 mL mL 65 C 15 3. 0 7 HPLC 1 7 Fig. 6 Fig. 7 AC1 AC2 AC3 Fig. 6 7 0 1/10 0 7 5,630 6,100 g/m3 3% 7 Fig. 7 CNET 5,500 g/m3 020406080100304050607080T emp erat ure ( C)AC1 (%)Samp ler ASamp ler BFig. 5. Effect of T emp erat ure onProp ortion Change of AC1T he p ercent ages of AC1 were calculat ed fromthe p eak height of AC1 and the sum of thoseof AC1, AC2 and (A)7day s (A)AC1AC2 Fig. 6. Changes of HPLC Chromatograms before (B) andafter (A) Acid Treatment of ExtractsAC31day (B)7day s (B)AC3 AbundanceAbundanceAbundanceAbundanceExtr acts were obtained from samp ler A p reserved from1 day or 7 day s in cool after adsorp tion of acrolein ,0004,0006,0008,000A_0d A_1d A_2d A_3d A_7d C_0dConcentration of Acrolein g/m3 BeforeAfterFig.

8 7. Estimated Acrolein Concentration before and afterT reat ing Ext ract s wit h AcidA_0d-7d : The extract obtained from DNPH derivativesamp ler (samp ler A) which adsorbed acrolein gas andp reserved 0 - 7 day s in : The extract obtained from CNET derivativesamp ler which adsorbed acrolein gas on the 0 daywit hout acid t reat ment .AC1AC2F ig. 8 . C h an ges o f H P LC C h r o mat o gr ams b ef o r e an dafter Acid Treatment of Extracts obtained from SamplerB which Adsorbed Diesel Exhaust 1 BeforeAfterAbundanceAbundance 63, 2012 251 4. HPLC Fig. 8 Table 3 AC1 AC2 15) 16) 5% 24% 215 g/m3 12 36% 24 48% 5) 4)

9 DNPH CNET 23 2011 12 1) 27 23 4 1 2012 9 20 URL 2) 0207002 2002 3) IPCS: Acrolein, CICAD, 2002. 4) 14 118-119, 2002. 5) Schulte-Ladbeck, R., Lindahl, R., Levin, , et al.,: J. Environ.

10 Monit., 3, 306-310, 2001. 6) 20 234-235, 2008. 7) Knighton, , Herndon, S. C., Shorter, , et al.,: J. Air & Waste manage. Assoc., 57, 1370-1378, 2007. 8) Ho, and Yu, ,: J. Environ. Monit., 4, 728-733, 2002. 9) 15 616-617, 2006. 10) 18(1), 73-80, 2008. 11) 18 124-125, 2009. 12) Liu, , Dills, , Paulsen, M., et al.,: Environ. Sci. Te c h n o l. 35, 2301-2308, 2001. 13) , 59(3), 251-256, 2010. 2 Exhaust 3 Table 3. Concentration of Carbonyl Compounds in Diesel Exhaust before and after Acid Treatment of DNPHE xhaust 1 Derivatives g/m3 Ann. Rep. Tokyo Metr. Inst. Pub. Health, 63, 2012 252 14) Uchiyama, S., Inaba, Y., Kunugita, N.,: J. Chromatogr. A, 1217, 4383-4388, 2010. 15) 101015002 2010 16) PRTR 22 9.