Investigation of the Characteristics and the Sources of Polycyclic Aromatic Hydrocarbons in the Atmosphere
Department of Environmental Engineering and Management, Chaoyang University of Technology Thesis for the Degree of Master Investigation of the Characteristics and the Sources of Polycyclic Aromatic Hydrocarbons in the Atmosphere (Hsi-Hsien Yang) (Chia-Mei Chen) 17, July 2003
(Polyclic Aromatic Hydrocarons, PAHs) PS-1 PAHs 21 PAHs (GC/MS) 20 PAHs (ISCST3) (Cluster analysis) (Chi-square test) (CMB) CMB (1) PAHs (2) ISCST3 PAHs PAHs PAHs (3) PAHs PAHs PAHs (4) CMB PAHs (5) CMB 8.0 20 PAHs 36.5% 4.03% 47.9% 8.33% 3.21% (6) CMB 8.0 CMB PAHs CMB PAHs -I-
Abstract The characteristics and the sources of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere were investigated. Particulate and PAHs samples were collected by high volume samplers, micro-orifice uniform deposit impactor (MOUDI), dry deposition sampling devices and wet deposition sampling devices. Twenty-one PAHs were analyzed by a gas chromatography/mass spectrometer (GC/MS). ISCST3 model, cluster analysis, chi-square test and chemical mass balance (CMB) receptor model were used to identify and quantify the PAHs emission sources. The results of CMB modeling were validated by emission inventories and ground-based trajectories.the results of this study are as follows: (1) The concentration, dry deposition, wet deposition and the particle size distributions of the particulate matter and PAHs in the atmosphere of the central Taiwan were characterized in this study. (2) The results of ISCST3 model analysis showed that the contribution of PAHs from the municipal solid waste incinerator (MSWI) was insignificant for the seven sampling sites. However, the results of cluster analysis and chi-square test indicated the atmospheric PAHs profiles at these sampling sites were correlated to that of MSWI. (3) Seven low reactive PAHs did not provide good estimation for CMB model analysis. The reason could be that less species were chosen. (4) The validation of CMB model analysis for particulate phase PAHs was not well examined by ground-based trajectories. The results showed that total (gas + particulate) phase PAHs should be considered for CMB analysis. (5) CMB receptor model for PAHs showed that the apportionment of the sources are: mobile source 36.5%, heavy oil combustion 4.03%, natural gas combustion 47.9%, coal combustion 8.33% and diesel combustion 3.21% (6) The validation of CMB model analysis with emission inventories and ground-based trajectories showed that CMB could be used to apportion source emission of PAHs. -II-
-III-
...I... II... III...IV...IX... XII... 1 1-1... 1 1-2... 2... 3 2-1 PAHs... 3 2-1-1 PAHs... 3 2-1-2 PAHs... 3 2-1-3 PAHs... 8 2-1-4 PAHs... 13 2-1-5 PAHs... 17 2-1-6 PAHs... 19 2-1-7 PAHs... 23 2-1-8 PAHs... 24 -IV-
2-2... 26 2-2-1... 26 2-2-2... 27 2-2-3... 28 2-2-4... 31 2-3... 33 2-3-1... 34 2-3-2 PAHs... 36 2-3-3 PAHs... 39 2-4... 41 2-4-1... 41 2-4-2... 42 2-4-3... 43 2-5 ISC... 46 2-5-1 ISC... 48 2-5-2... 49 2-6... 51 2-6-1... 51 2-6-2... 53 2-6-3 CMB... 56 2-6-3-1 VOCs... 56 2-6-3-2 PAHs... 58 2-6-4 CMB... 63... 65 3-1... 65 -V-
3-1-1... 65 3-1-2... 66 3-2... 67 3-2-1... 67 3-2-1-1 PS-1... 67 3-2-1-2... 73 3-2-2... 77 3-2-3... 80 3-2-4... 81 3-3 PAHs... 84 PAHs... 88 4-1... 88 4-1-1... 88 4-1-2... 88 4-1-3... 88 4-1-4... 89 4-2... 89 4-2-1... 89 4-2-2... 89 4-3... 92 4-4... 94 4-4-1... 94 4-4-2... 94 4-5... 95 -VI-
4-6 PAHs...105 4-7... 111... 112 5-1... 112 5-1-1... 112 5-1-2 PAHs... 114 5-1-2-1 PAHs... 114 5-1-2-2 PAHs... 116 5-1-2-3 PAHs...120 5-2...122 5-2-1...122 5-2-2 PAHs...126 5-3...127 5-4...130 5-4-1...130 5-4-2 PAHs...131 5-4-3 PAHs...134 5-5 PAHs...140 5-5-1 ISCST3...140 5-5-1-1 ISCST...140 5-5-1-2 ISCST...144 5-5-2 PAHs...147 5-5-2-1 PAHs...147 5-5-2-2 PAHs...148 -VII-
5-5-2-3...152 5-5-2-4...153 5-5-3...155 5-5-3-1...155 5-5-3-2...163 5-5-3-3 PAHs...167 5-5-3-4 PAHs...173 5-5-4...174 5-5-4-1 CMB 8.0...174 5-5-4-2 PAHs...177 5-5-5 CMB...189...197 6-1...197 6-2...199...200...224 -VIII-
-IX- 2-1-1 21 PAHs... 5 2-1-2 PAHs 25 C (Eπ)... 7 2-1-3 21 PAHs... 12 2-1-4 PAHs... 13 2-6-1 PAHs... 62 3-1-1... 66 3-2-1 MOUDI... 74 4-2-1 PAHs... 91 4-3-1 GC/MS... 93 4-4-1 PAHs (Chem Service)...102 4-4-2 PAHs (Gravimetric Certificate)...102 4-4-3 PAHs 10 µg ml -1 GC/MS..103 4-4-4 PAHs 10 µg ml -1 GC/MS...104 4-5-1...106 4-5-2 PAHs...107 4-6-1 21 PAHs GC/MS...108 4-6-2 21 PAHs GC/MS...109 4-6-3 21 PAHs... 110 5-1-1... 112 5-1-2 PAHs... 115 5-1-3 PAHs... 116
5-1-4 PAHs... 118 5-2-1...124 5-2-2...125 5-3-1 21 PAHs...128 5-3-2 PAHs...129 5-4-1 PAHs MMD o g, o...138 5-4-2 PAHs MMD g...139 5-5-1...143 5-5-2...143 5-5-3 ISCST3 PAHs...145 5-5-4 PAHs...149 5-5-5 PAHs...150 5-5-6...154 5-5-7...158 5-5-8...161 5-5-9...162 5-5-10...162 5-5-11...162 5-5-12 PAHs...168 5-5-13 PAHs...168 5-5-14...168 5-5-15...169 5-5-16...170 5-5-17 PAHs...171 5-5-18 PAHs...172 -X-
5-5-19 PAHs (%)...172 5-5-20 PAHs (%)...176 5-5-21 CMB 8.0 20 PAHs...178 5-5-22 CMB 8.0 8 PAHs...181 5-5-23 CMB 8.0 20 PAHs...184 5-5-24 CMB 8.0 8 PAHs...185 5-5-25 CMB 8.0 20 PAHs -...188 -XI-
2-1-1 Bap DNA... 11 2-4-1... 42 3-1-1... 65 3-2-1 PS-1... 68 3-2-2... 70 3-2-3 PS-1... 72 3-2-4 PS-1... 72 3-2-5 MOUDI... 74 3-2-6 MOUDI... 76 3-2-7... 78 3-2-8... 79 4-2-1... 90 4-4-1 Nap, AcPy, Acp Flu... 96 4-4-2 PA, Ant, FL Pyr... 97 4-4-3 CYC, BaA, CHR BbF... 98 4-4-4 BkF, BeP, BaP PER... 99 4-4-5 IND, DBA, BbC BghiP...100 4-4-6 COR...101 5-1-1... 113 5-1-2 PAHs...121 5-2-1 (a) (b)...123 5-2-2 PAHs...126 5-3-1 PAHs PAHs...129 -XII-
5-4-1...132 5-4-2 PAHs...133 5-5-1...141 5-5-2 ISC...142 5-5-3 PAHs...151 5-5-4...153 5-5-5 PAHs...165 5-5-6 PAHs...166 5-5-7 PAHs PAHs...173 5-5-8 20 PAHs...179 5-5-9 8 PAHs...182 5-5-10 20 PAHs ( MSWI)...189 5-5-11...193 5-5-12...194 5-5-13 CMB 20 PAHs...195 5-5-14 CMB 8 PAHs...196 -XIII-
1-1 (Polycyclic Aromatic Hydrocarbons, PAHs) 30 PAHs PAHs PAHs PAHs PAHs PAHs PAHs PAHs PAHs PAHs PAHs PAHs PAHs (Receptor model) (CMB) PAHs CMB 21 PAHs PAHs 20 PAHs (ISCST3) (Cluster analysis) -1-
(Chi-square test) (CMB) CMB 1-2 PS-1 PAHs 1. PAHs PAHs PAHs 2. PAHs 3. 21 PAHs PAHs PAHs PAHs 4. PAHs PAHs (MMD) ( g ) 5. ISCST3 6. 20 PAHs (CMB) CMB -2-
2-1 PAHs 2-1-1 PAHs 1775 Pott Pott, 1775 (Polycyclic Aromatic Hydro-carbons PAHs) PAHs 1930 PAH Dibenz(a,h)anthracene (DBA) 1933 Benzo(a)pyrene (BaP) Cook, 1933 1976 30 PAHs PAHs Dipple, 1976 PAHs PAHs (Soot) BaP PAHs PAHs 82 Clean Air Act, Title 30 (Polycyclic Aromatic Hydrocarbons, PAHs) / 2-1-2 PAHs PAHs 21 PAHs 2-1-1 21 PAHs PAHs -3-
2-1-1 16 PAHs Benzo(a)anthracene Benzo(a)pyrene Chrysene Benzo(b)fluoranthene Benzo(k)fluoranthene Indeno(1,2,3,c-d)pyrene Dibenzo(a,h)anthracene Bezno(g,h,i)perylene 8 PAHs Menzie et al, 1992 PAHs PAHs PAHs 82 PAHs 333 PAHs 1896 Karcher, 1983; Zandere, 1985; USEPA, 1987 PAHs (gas phase vapor phase) (particle phase) 2-1-2 21 PAHs ( 25 ) (Electrophilic reaction, Eπ) PAHs 10-2 ~ 10-11 atm (Semi-Volatile Organic Compounds, SVOCs) 10-8 atm 230 PAHs SVOCs PAHs 2000 PAHs PAHs PAHs Eπ PAHs PAHs Bjørseth and Ramahl, 1985; Dias, 1987; Ebert, 1988; Li and Kamens, 1993-4-
2-1-1 21 PAHs ( o C) ( o C) Naphthalene Nap 128 81 218 Acenaphthylene AcPy 152 93 270 Acenaphthene Acp 154 96 279 Fluorene Flu 165 117 294 Phenanthrene PA 178 101 340 Anthracene Ant 178 216 340 Fluoranthene FL 202 111 383 Pyrene Pyr 202 156 404 Cyclopenta[c,d]pyrene CYC 228 N.A. N.A. Benz[a]anthracene BaA 228 162 400 Chrysene CHR 228 256 448 Benzo[b]fluoranthene BbF 252 168 481 Benzo[k]fluoranthene BkF 252 217 481-5-
2-1-1 21 PAHs ( ) ( o C) ( o C) Benz[e]pyrene BeP 252 179 493 Benzo[a]pyrene BaP 252 177 496 Perylene PER 252 278 NR Indeno[1,2,3-cd]pyrene IND 276 N.A. 534 Dibenz[a,h]anthracene DBA 278 270 535 Benzo[b]chrycene BbC 278 294 N.A. Benzo[ghi]perylene BghiP 276 278 542 Coronene COR 300 439 525 N.A. -6-
2-1-2 PAHs 25 C (Eπ) PAHs (mmhg) (µg L -1 ) Nap 7.8 10-2 31700 13.68 AcPy 6.7 10-3 N.A. N.A. Acp 2.15 10-3 3930 N.A. Flu 6.0 10-4 1980 N.A. PA 1.2 10-4 1290 19.45 Ant 6.0 10-6 73 19.31 FL 9.2 10-6 260 N.A. Pyr 4.5 10-6 135 22.51 CYC N.A. N.A. N.A. BaA 2.1 10-7 N.A. 25.10 CHR 6.4 10-9 2.0 25.19 BbF N.A. 2.0 N.A. BkF N.A. N.A. N.A. BeP 5.6 10-9 3.8 28.34 BaP N.A. 0.05 (20 C) 28.22 PER N.A. 0.4 28.25 IND N.A. N.A. N.A. DBA N.A. N.A. 30.88 BbC N.A. N.A. 30.84 BghiP N.A. 0.3 31.43 COR N.A. 0.1 34.57 N.A. Eπ -7-
PAHs PAHs 10-6 mmhg PAHs PAHs (Condensation) (Adsorption) Brostroem and Loevblad, 1991 PAHs ( ) 10-6 mmhg 10 µm 2000 PAHs PAHs PAHs PAHs 25 Nap 31.7 mg L -1 CHR 0.002 mg L -1 Babara and Kames, 1986 PAHs 2000 2-1-3 PAHs PAHs PAHs (Causative agent) (Automobile Exhaust Condensate, AEC) Katz (1980) 5 µm 70~90% Grimmer (1983) 4~7 PAHs PAHs PAHs (C + ) DNA (Complementary base pair) T-A G-C (Cross-linking) -8-
DNA Josephson, 1984 (Ames) (Salmonella/Microsome reversion assay) Hecht, 1988 PAHs PAHs BaA CHR BbF BkF Bep BaP IND DBA Bghip BaP 2-1-1 P-450 BaP BaP-7,8-Arene Oxide epoxide hydrolase BaP-7,8-Dihydrodiol P-450 BaP-7,8-Dihydrodiol 9,10-Epoxide DNA BaP-7,8-Dihydrodiol 9,10-Epoxide I-Deoxyguanosine adduct Rathore, 1991 BaP PAHs Promutagens PAHs (Direct acting mutagens) Perera and Ahmed (1979) 1 ng BaP 5% Levin et al. (1985) PAHs BaP Laskin (1970) SO 2 BaP SO 2 2-1-3 (International Agency for Research on Cancer, IARC) (USEPA) (National Academy of Sciences, NAS) PAHs NAS, 1983; IARC, 1987; -9-
USEPA, 1991 IARC PAHs 2 A B 3 2 B2 PAHs D (Not classifiable) 2-3 S (Sufficient evidence) L (Limited evidence) I (Inadequate evidence) No Bjørseth and Becher, 1986 PAHs PAHs Tuominen (1988) 2~3 PAHs (Nitro-PAHs) (Screening test) PAHs ( PMS) PAHs ( Nitro-PAHs Choloric-PAHs ) (Activation) 2-1-4 Longwell, 1982 CYC epoxide PAHs Davis et al., 1987-10-
2-1-1 Bap DNA -11-
2-1-3 21 PAHs PAHs IARC USEPA NAS Nap 0 AcPy 0 Acp Flu 3 D I PA 3 D 0 I Ant 3 D 0 L FL 3 D + No Pyr 3 D 0 No CYC + L BaA 2A B2 + S CHR 3 B2 0/+ L BbF 2B B2 S BkF 2B B2 S BeP 0/+ I BaP 2A B2 ++ S PER 3 0 I IND DBA 2A B2 S BbC BghiP D + I COR 3 0/+ I 1. IARC 2A 2B 3 2. B2 PAHs D 3. S L I No S -12-
2-1-4 PAHs (µg ml -1 ) PMS PMS PMS PMS Bap 1 20 0.25 20 PA 53 53 9 9 FL 1 10 0.4 10 CYC 1.4 9 1.6 20 CYC epoxde 1.5 0.17 4.8 0.097 Longewll (1982). 2-1-4 PAHs PAHs (Pyro1ysis) PAHs PAHs PAHs PAHs 2000 ( ) PAHs PAHs Tuominen, 1988 Wybranies and Jong (1996) Cracow, Poland PAHs Harrison Sisovic (Birmingham) Zagreb PAHs 88% BaP BaP PAHs Harrison -13-
et al., 1996; Sisovic and Fugas, 1997 Mi (1996) ( 40 km hr -1 80 km hr -1 110 km hr -1 ) ( ) PAHs PAHs (5210 µg L -1 ) PAHs (3720 µg L -1 ) (1997) PAHs PAHs (49200 µg L -1 ) PAHs (1810 µg L -1 ) (1999) PAHs 27.2 mg min -1 18.3 mg min -1 14.6 mg min -1 7.31 mg min -1 2.41 mg min -1 1.89 mg min -1 (1995) PAHs 31 µg km -1 PAHs 19.6 µg km -1 (1994) PAHs 10 Sheu et a1. (1996) 1.0 2.5 10 µm PAHs 50.9 74.2 90.8% (1998) PAHs 87.8% PAHs PAHs 91.8% Barfknecht (1983) PAHs 10 PAHs Maschet et al. (1986) PAHs FL Pyr COR ( ) PAHs PAHs -14-
(Smoky coal) Mumford et al., 1987 PAHs PAHs 3,000 µg m -3 PAHs BaP 60 µg m -3 Ramdahl et al., 1982 Greenberg (New Jersey) PAHs 98% BaP Greenberg et al., 1985; Harkov and Greenberg, 1985 Michael et al. (1998) 70% 20~30% Teschke et al. (1989) Berg et al., 1988; Lofroth et al., 1991 (1994) ( ) PAHs PAHs PAHs Bjørseth Bjørseth and Ramahl, 1983 PAHs 19 µg kg -1 10 µg kg -1-15-
1 µg kg -1 (1999) PAHs 4350 µg kg -1 6050 µg L -1 2670 µg Kw -1 h -1 (1998) PAHs (3.10 mg L -1 ) (27.0 mg L -1 ( ) PAHs PAHs Akio and Youki (1987) PAHs 1,700~3,000 Wey and Shi (1997) PAHs Bjørseth and Ramahl (1983) PAHs 17 mg kg -1 240 mg kg -1 Li et al. (1994) PAHs PAHs 1782 µg Nm -3 PAHs 6 µg g -1 PAHs 92% (1640 µg m -3 ) Li et al. (1995) PE PAHs PAHs PAHs PAHs ( ) PAHs (Coke) PAHs PAHs Trenholm and Beck, 1978 15 g ton -1 (Sintering) PAHs PAHs Bjorseth and Ramahl, 1983 (1999) PAHs 2140 µg -16-
Nm -3 2 Nap (86.5%) 7 COR (0.013%) (1998) PAHs PAHs 77.0~3970 µg kg -1 BaP 1.87~15.5 µg kg -1 ( ) PAHs PAHs PAHs Hoffman et al., 1984; Hoffman et al., 1985 2-1-5 PAHs PAHs PAHs (Pyrolysis) (Carbonization) Edwards, 1977 1. PAHs Badger PAHs Badger and Spotswood (1960) BaP BaP PAHs -17-
Frenklach (1985) PAHs A i + H A i +H 2 A i + C 2 H 2 A i C 2 H 2 A i C 2 H 2 +C 2 H 2 A i+1 +H A i i (I = 0~ ) Crittendern and Long (1976) (Styrene) PAHs PAHs PAHs PAHs PAHs Bjørseth and Ramahl, 1983 PAHs (Dehydrogenation) (Polymerization) 2000 2. (Carbonization process) PAHs (200 ) PAHs -18-
2000 Chen et al. (1997) PAHs 69.1% PAHs 1 µm 2.5 µm PAHs 73.9% PAHs ( 93%) 10 µm 2-1-6 PAHs PAHs (Sub-micron-sized soot particle) Baek et al., 1991 PAHs ( ) 10-6 mmhg 10 µm PAHs Langmuir Langmuir PAHs Yamasaki et al., 1982 Langmuir : log K y =log C g / (C p / TSP) =-a (1/ T+b) (2-1) K y = - C g / (C p / TSP) = C g = PAHs C p = PAHs TSP= T= A,B= C g -19-
PAHs 10-6 mmhg PAHs PAHs PAHs PAHs Beck et al., 1991; Brostroem and Loevblad, 1991; Rudolph and Neue, 1991 1. 2. 3. 4. PAHs (Primary pollutants) (NO 2 -AR/PAH) PAHs 290~400 nm PAHs PAHs 2000 Mcdow (1994) PAHs (Methoxyphenols) (Hexadecare) PAHs BaA BaP Jang Mcdow (1997) BaA 9, 10-anthraquinone 9-xanthone vaillin BaA benzo[a]anthracene-7 12-dione phthalic acid phthalic anhydride 1, 2-benzenedicar-boxaldehyde Sanders (1993) 11 PAHs Anthracene Benzo(a)pyrene Fluoranthene -20-
PAHs PAHs PAHs PAHs / (Blow-off) PAHs PAHs PAHs Bidleman et al., 1986 PAHs / Vaeck et al., 1984 1. PAHs 2. PAHs 3. PAHs 4. PAHs ; PAHs PAHs (Aging prosecc) PAHs Vaeck et al., 1984 Thrane Mikalsen (1981) CHR 1% 25% PAHs Coutant (1988) PAHs PA Ant 30~90% 5 PAHs PAHs Coleinar (1997) 1991~1995 PAHs -21-
PAHs 20~150 ng m -3 PAHs Sheu et al. (1996) PAHs PAHs 0.32 cm s -1 0.23 cm s -1 PAHs 0.22 0.188 cm s -1 Aceves Grimalt (1993) PAHs PAHs Lee et al. (1995) PAHs 46.1% 18.7% 20.6% PAHs ( ) 5.3 8.3 PAHs (1995) PAHs 19870 2187 798 775 ng m -3 PAHs 54% 31% 10% 8.0% (Respirable particulate) PAHs PAHs (Cascade impactor) Vaeck (1979) Sierra Anderson PAHs PAHs 2.5 µm 20% PAHs Aceves Grimalt (1993) PAHs 1.5 µm PAHs Venkatarainan Fried1ander (1994) mode mode I -22-
mode II PAHs PAHs 85% PAHs 0.12 µm PAHs 0.05~0.12 µm (mode I) 0.5~1.0 µm (mode II) Allen (1997) Oxygenated PAH (OPAH) OPAH PAHs OPAH 168~208 OPAH ( 2 µm) ( 2 µm) 248 OPAH 2-1-7 PAHs PAHs PAHs Davies et al., 1976; Eiceman et al., 1981; Colmsjo et al., 1986 PAHs PAHs PAHs PAHs PAHs Hangebrauck (1967) PAHs 95% 87% Davies (1976) PAHs FL Pyr BaA + CHR BeP + BaP IND COR 58 49 171 147 < 10 < 20 µg kg -1 PAHs 0.62 0.54 0.64 0.14 < 0.01 < 0.01 µg kg -1 Huynh -23-
(1984) 70% PAHs 25% Morselli (1989) PAHs AcPy Flu CHR BkF BaP 223 636 108 135 5490 µg kg -1 (1997) PAHs 0.03% ~ 8.96% 2.28% PAHs Rantanen (1993) ( 50 ppm 20% 49) 56% 74% Westerholm (1986) 70% PAHs 30% PAHs PAHs 2-1-8 PAHs PAHs PAHs PAHs PAHs -24-
1999 PAHs 1999 1. PAHs 2. PAHs PAHs ( ) PAHs 1999 1. (Dry Deposition) ( ) PAHs PAHs 2. (Wet Deposition) : (1) (rainout) (interception) (impaction) 1 µm (2) (washout) -25-
1 µm 2-2 (Nonprecipitation) Wu et al., 1992 (Eddy diffusion) Noll et al., 1988 2-2-1 (Aerodynamic transport) (Viscous sublayer) (Boundary layer transport) (Bounce-off) (Resuspension) 1/Vd = Ra + Rb + Rc (2-2) Ra = (Aerodynamic resistance) Rb = (Boundary layer resistance) Rc = (Surface resistance) -26-
1995 2-2-2 Hicks (1986) (Suface analysis) (Atmospheric Flux) (Surrogate suface) (Through-Fall) (Foliar Extraction) (Vertical gradient method) (Eddy correlation method) (Variance method) Davison (1985), 1995-27-
Holsen et al. (1992) Lin et al. (1993) 2-2-3 Sehmel (1980) 1. 0.1 µm (Brownian diffusion) (Eddy diffusion) 0.1 µm (Diffusion) -28-
2. 3. 24 Wu (1992) 4 8 12 17 Vandberg Knoerr (1985) ( ) Davidson (1985) Noll (1988) 65% 2.8-29-
(1994) Wu (1992) Holsen Noll (1992) Mylar 8 mg (Apiezon L Grease) 8 µm (1995) 20 mg (silicon grease) (1994) Ibrahim (1983) 7.5 µm 0.7 µm 15 Milford Dacidson (1987) (Mass Median Diameter, MMD) Nicholson (1988) Coe and Lindberg, 1987; Noll et al., 1988, 1990 Sehmel (1980) Davies Nicholson (1982) Sehmel Hodgson -30-
(1987) Gould Dacidson (1992) Wesely (1977) Ibrahim (1983) 40% Sehmel Hodgson (1987) Hillamo (1993) 0% 99% 8.5 2-2-4 Z : Vd = F C ( z) (2-3) Vd F C (z) Z (Downward flux) (Resistance) -31-
Ra Rb Rc Vd = 1 Ra + Rb + Rc (2-4) Ra Rb Rc (mg m -2 day -1 ) (µg m -3 ) 1~15 10~15 cm/s 0.001~180 Sehmel, 1980 1~20 µm 20 µm Sehmel (1980) 0.1 µm 0.1~1 µm 1 µm Noll et al., 1990; Holsen et al., 1992; Ottley et al., 1993 Mcveety Hites (1998) PAHs 0.5 0.13 cm s -1 PAHs 0.13~1.1 cm s -1 PAHs ( 2.5µm ) ( 0.1 µm 2.5 µm ) ( 0.1 µm) -32-
Holsen and Noll, 1992 Ligocki et al. (1985) PAHs (Washout) PAHs Mcveety Hites (1988) PAHs Siskiwit PAHs 9 Sheu et al. (1996) PAHs PAHs 0.31~3.2 µm PAHs (1998) PAHs 1.88% PAHs Nap AcPy 27.0% 36.5% PAHs 3.05% 95% 2-3 Lee et a1., 1993 ( ) -33-
1999 2-3-1 Van Noort (1985) (In-cloud) (Below-cloud) (Diffusion) (Interception) (Impaction) ( ) Franz, 1998 Lee et al. (1993) Slinn et al., 1978 1992-34-
1999 0.1 µm 1992 (1) (2) (3) -35-
1992 1999 Lovett and Kinsman, 1990 ( ) Horstmann and Mclachlan, 1998 1999 2-3-2 PAHs PAHs (Henry s low constant) Slinn et a1., 1978; Eisenreich et al., 1981 Butler (1981) PAHs -36-
PAHs PAHs Paul et al., 1985 PAHs PAHs PAHs Van Noort, 1985; Bidleman, 1988 - (Air-water coefficient) PAHs 2~4 PAHs Franz, 1998 (1998) PAHs PAHs PAHs 73% PAHs 27% Khemani (1985) Koelmans (1997) (Hydrophobic organic compounds) -37-
(Partition coefficient) PAHs ( ) 1996 PAHs PCBs 0.5 µm 0.5 µm 1999 Slinn (1978) ( ) / H(T) (atm m -3 mol) C v,atm (ng m -3 ) : C v,atm = 10 3 Cr H(T) / R T (2-5) (Washout) (2-6) (2-7) Slinn et al., 1978; Dickhut and Gustafson, 1995 W g = C d,rain / C v,atm (2-6) -38-
W p = C p,rain / C p,atm (2-7) C d,rain = (ng L -1 ) C p,rain = (ng L -1 ) W p = [(ng L -1 ) precipitation / (ng L -1 )air] Poster (1996) PAHs PAHs (< 0.05 µm) 0.05~1 µm S1inn et al., 1978; Wang, 1998 0.1~10 µm 0.5 µm (WD, F) [C p,r > 0.5 µm] / [ C p,air > 0.5 µm] (WD, nf) [C p,air < 0.5 µm] / [ C p,air < 0.5 µm] C p,air < 0.5 µm S1inn et al., 1978; 1999 2-3-3 PAHs 1992 - MaCkay and Paterson, 1998-39-
PAHs PAHs (Soot carbon) PAHs PAHs 1996 (1) (2) (3) PAHs Readman, 1984; Boulzubassi, 1991; Brornan, 1991 ( PAHs) Poster and Baker (1996) (W g ) [C d ] / [C g ] [C d ] [C g W p [C p ] / [C p, air ] [C p ] [C p, air ] [C p, air ] / [C g + C p, air ] W p 2000 106 Bidleman, 1988 W g 900 31000 Ligocki et al., 1985-40-
2-4 2-4-1 PAHs (Nucleation) (Coagulation) (Adsorption) (1) (2) (3) (4) (5) (1) (2) (3) (4) Perera, 1980 2000 : (1) 0.1 µm (2) 0.1~2 µm 1 (3) 2 µm 2-4-1 Frederica, 1980-41-
µ 2-4-1 Frederica, 1980 2-4-2 2000-42-
5 µm 5 µm 2 µm 2000 2-4-3 (TSP) ( PM 10 ) (Respirable suspended particulate PM 2.5 ) 2.5 µm 2.5 µm Watson et al., 1998a (Coarse mode) (Accumulation mode) (Nucleation mode) Watson et al., 1998a; Lundgren and Burton, 1995 0.08 µm 0.08 µm ~ 2 µm 2 ~ 3 µm -43-
Lundgren and Burton, 1995 PM 10 PM 2.5 1993 8 ~ 1994 3 5 2 Hi-vol PM 10 Dichotomous PM 10 PM 2.5 50.5% ~ 60.6% PM 10 PM 2.5 1994 3.2 ~ 5.6 µm 0.56 ~ 1.0 µm 1999 ( ) SO 2-4 NO - 3 NH + 4 1999 Li and Okada (1999) 100 km (0.2 ~ 4 µm) Pierce Katz (1975) Toronto PAHs -44-
5 µm 85~90% 70~85% Vaeck (1979) 85~90% 90~95% PAHs Aceves (1993) 0.5 µm PAHs 1.5 PAHs (MW 202) Venkataraman Friedlander (1994) PAHs PAHs 85% PAHs 0.12 µm 0.5~1.0 µm PAHs 0.05~4.0 µm 0.05~0.12 µm (model I) 0.5~1.0 µm (model ) Model I model Accumulative mode (1995) PAHs 1.0 µm 1.0 µm (1996) PAHs PAHs 5.6~10 µm 0.31~0.52 µm 0.31~3.2 µm 0.52~1.0 µm (Cumulative distribution) MMD (Mass median of diameter) g -45-
(Geometric standard deviation) 2.5 µm ( 2.5 µm) ( 2.5 µm) (Mass median diamneter, MMD) 50% Pierce Katz (1975) CHR BaA BaP BkF PER BghiP Ant COR PAHs MMD 2.0~2.8 µm 1.2~1.6 µm PAHs Katz Chen (1980) Hamilton PAHs BghiP BaP BeP BkF MMD 1.79 2.21 1.42 1.35 µm (1995) PAHs MMD 0.48 1.61 1.19 µm (1996) PAHs MMD 1.61 1.28 0.84 1.67 µm PAHs MMED (Mass mean equivalent diameter) TSP PAHs (Aging process) Vaeck et al., 1979; Vaeck, 1985 2-5 ISC (Industrial source complex, ISC) U.S. EPA 1970 (Steady-state) ( ) ISC ISCST3 (Industrial source complex -46-
short-term) (U.S. EPA, 1995) ISC ( ) ( ) ISCST3 ISCST3 1. (Control pathway) ( ) ( ) 2. (Source pathway) UTM (m) (g s -1 ) (m) (K) (m s -1 ) 3. (Receptor pathway) UTM (m) 4. (Meteorology pathway) -47-
5. (Output pathway) (1) (2) Overall (3) 2-5-1 ISC ISCST3 (Downwash) x y x z x y -48-
C ( x, y) = QKVD 2πu σ σ s y z y exp 0.5 σ y 2 (2-8) : C (x, y) (x (m), y (m)) Q ( / ) K ( Q g s -1 µg m -3 ) V ( ) D σ y σ z (m) u s (m s -1 ) (2-8) ( 0.1 µm) 2-5-2 ISC (1992) ISC -49-
(1994) ISC SO 2 Pasquill ISC (1999) 1997 ISC3 MESOPUFFII SO 2 (1999) ISC PM 10 PM 10 PM 10 (2000) ISC CMB (2000) PM 10 ISC PM 10 (2000) ISC (2000) ISC Hao et al. (2000) ISCST3-50-
Lorber et al. (2000) ISCST3 10 Basham and Whitwell (2000) ISCST3 Honaganahalli and Seiber (2000) Salinas Valley ISCST3 CAMET ISCST3 0.7 CALPUFF 0.55 0.82 Ma et al. (2002) ISCST3 8 km 8 km 2-6 2-6-1 (Source model) (Receptor model) (Dispersion model) (Emission strength) -51-
(Finger print) 2000 1970 1973 Friedlander (1973) Hopke, 1991 U.S. EPA, 1984; U.S. EPA, 1990 Eulerian Langrangian 1998-52-
(Tracer) 1998 20~30% (Chemical mass balance, CMB) Belsley et al., 1980 (Multivariate receptor model) (Principal component analysis) (Factor (Multiple linear regression) 2-6-2 CMB CMB 1972 Miller Friedlander Hidy (Chemical element balance CEB) Hopke, 1985 1996 1980 Cooper Waston (CMB) -53-
Cheng, 2001 C i = p j= 1 α F ij ij S j (2-9) C i i α ij i F ij j i S j j i j α 1 (2-9) C i (2-10) S j C i = p j= 1 F ij S j (2-10) CMB C = F S (2-11) C = n 1 n F = n p p S = p 1 p -54-
(Tracer property solution) (Linear least-square fitting) Watson, 1984 Waston Watson, 1984 1. (Composition) 2. 3. 4. 5. 6. CMB Glover (1991) CMB (Granite City) PM 10 CMB (Source profile) Sharma Patial (1994) Chow (1992) (San Joaquin Valley) PM 10 Bakerfield (54%) -55-
(15%) (10%) (8%) 4% Waston (1994) Chow (1995) (San Joaquin) PM 10 45% 15~20% 5% Vega (1997) CMB PM 2.5 PM 2.5 50% 38% Chen (1997) ( 2.5 µm) ( 2.5 µm ) 2-6-3 CMB 2-6-3-1 VOCs (Volatial organic compounds, VOCs) VOCs Carter, 1994 1971 VOCs Seinfeld (1991) VOCs ( ) VOCs 2~4-56-
VOCs VOCs NMHC 33% 31% 15% 1% 8% 1998 VOCs CMB CMB 8.0 Watson, 1998b Fujita, 1998 Fujita et al. (1997) CMB VOCs CMB 6.6~10 Fujita et al. (1998) CMB VOCs VOCs 60~70% 10~13.5 % 2~19% 3~10% 1% VOCs VOCs 3.9~7.9 2~4 Conner et al. (1995) Lin and Milford (1994) Lewis et al. (1998) 1990 Canister VOCs CMB ( ) Lin and Milford (1994) 2 61~65 % 4~8.2% Conner Lewis VOCs Conner 20~30% Conner CMB ( -57-
MOBILE ) NMOC 10% 30% NMOC 10% 20% CMB (1993) VOCs VOCs 54~72% 30~35% 7~10% (1999) TO-14 4 56 VOCs CMB CMB 8.0 VOCs ( ) 47~68% 8~22% 6~20% 0.1~3% 6~21% VOCs 2-6-3-2 PAHs 20 CMB 1972 1-2 µg m -3 Friedlander, 1973 1982 180 ng m -3 Dzubay et al., 1989 1990 Gordon, 1988; Daisey et al., 1986 30-100 -58-
PAHs Gordon and Bryan, 1973; Daisey et al., 1979; Daisey and Lioy, 1981 PAHs Daisey et al., 1979; Miguel and Pereria, 1989; Pistikopoulos et al., 1990; Li and Kamens, 1993 PAHs CMB Miguel and Pereria, 1989; Pistikopoulos et al., 1990; Li and Kamens, 1993 Daisey (1979) PAHs PAHs Gordon and Bryan, 1973 PAHs Rogge et al., 1991 Peters (1981) PAHs PAHs PAHs PAHs PAHs PAHs CMB PAHs Mastclet et al., 1986 Pitts et al. (1978) PAHs CMB CMB CMB PAHs -59-
Kamens et al., 1985, 1988 PAHs PAHs (Depletion) Masclet et al., 1986 1. (Gaseous oxidizing agents ) (Luminosity) 2. 3. PAHs 4. PAHs PAHs 5. PAHs 6. Nikolaou et al., 1984 PAHs Pistikopoulos (1990) PAHs (Relative decay index, RDI) Fluoranthene ( ) PAHs Fluoranthene (Decay factor) CMB PAHs ( ) PAHs PAHs Cheng Richard (1993) (Smog chamber) PAHs CMB PAHs -60-
CMB 66~85% 32~58% 22~69% PAHs PAHs CMB PAHs PAHs PAHs Masclet (1986) RDI RDI R PAH R Fla R Fla R Fla 1 RDI RDI ( 21~32 ) BaP DiBah Ant BghiPe InP COR BaA Ant BkF CHR BeP Pyr Fla RDI Bap Ant DiBahAnt BaA BeP Pyr BkF BbF Katz et al., 1979 Bap BghiPe BaA Pyr BeP CHR Fla COR Butler and Crossley, 1981 Venkatarman Friedlander (1994) CMB PAHs CMB PAHs PAHs BkF BkF BkF CMB PAHs PAHs PAHs PAHs BaA BaP BghiP DBA BbF CHR Pyr Flu InP BkF RDI COR PAHs PAH 2-6-1 PAHs (FL Pyr BaA CHR BbF BkF BeP COR) -61-
PAHs D 1 b 2-6-1 PAHs RDI a RDI f RDF e Masclet et al. (1986) D 2 c Pico Rivera Pistikopouls et al. (1990) Upland D 3 d Venkataraman et al. (1994) Winter Summer NaP - - - - - - - AcPy - - - - - - - AcP - - - - - - - Flu - - 0.93 0.90 - - - Phen - - - - - - - Ant 1,5 1,7 - - 3,0 - - FL 1 1 - - 1 - - Pyr 1,5 1,7 0.93 0.90 1,7 - - CYC - - - - - - - BaA 2,5 3 0.60 0.50 3 - - CHR 0,9 1,3 0.93 0.90 3,0 - - BbF 1,2 1,7 0.87 0.81 3,0 1 1 BkF 1 1 1 1 BeP 1,3 1,3 - - 2,7 - - BaP 3 3,5 0.73 0.72 7 2.22 1.89 PER - - - - - - - IND 1,4 1,7 0.94 0.92 3,0 1 1.33 DBA - - 0.80 0.72 - - - BbC - - - - - - - Bghip 1,8 1,7 0.80 0.72 4,3 1 1.33 COR 3 3 - - 3 1.62 1.1 a: RDI= Relative Decay RDI=R PAH /R Fla (Fla FL) R=C M /C m (C M C m ) b: 1 ~ 5 c: 8 ~ 11 d: 21 ~ 32 e: RDF=Relative decay factors = i / BkF = i=(1+k i ) -1 f: RDI=Relative decay index -62-
PAHs CMB ( ) PAHs 2-6-4 CMB CMB Winchester and Nifong (1971) Hidy and Friedlander (1972) Kneip et al. (1973) Friedlander (1973) CMB CMB (Oregon Graduate Center) FORTRAN IV PRIME 300 CMB Watson, 1979 PRIME 300 3 MB 64 KB CMB 1 6 CMB 7 C FORTRAN 10 MB 640 KB CMB 8.0 CMB 7 DOS MS Windows US EPA, 2001 CMB 8.0 PAHs PAHs CMB C = F S C F S ng/g -63-
C (ng m -3 ) = F (ng g -1 ) S (g m -3 ) CMB 1 7 CMB 8.0 VOCs VOCs CMB 8.0 CMB 8.0 VOCs (2002) CMB VOCs CMB 8.0 VOCs VOCs PAHs PAHs PAH PAH (%) F ij = [PAH i ] / [[PAH total ] Miguel et al., 1989; Pistikopouls et al., 1990; Cheng and Richard, 1993 Li and Kamens, 1993 CMB 8.0 j PAHs ( BkF) F ij = [PAH i ] / [BkF] PAHs Venkataraman and Friedlander, 1994-64-
Super highway 3-1 3-1-1 2001 7 ~2002 5 (A~G) PAHs A B D C E F G 900 tons 800 120 m de-nox 0.5 km (site B) ~8 km (site F) 3-1-1 (6~9 m) N B MSW A incinerator E C G F 0 1 2 3 4 Km 3-1-1-65-
3-1-2 PAHs 3-1-1 48 30 PAHs 2001 7 3 3 3-1-1 PAHs 2001/7/9~7/10 A C D E F G 7/2~7/4 A B C D G 7/3~7/4 E F 7/2~8/1 A B C D ( ) 8/2~9/3 E F G 7/9~7/11 D 7/3 PAHs 10/11~10/12 C E G 10/3~10/5 A B C D E F G ( ) 9/3~10/2 A B C D 10/2~11/2 E F G PAHs 12/24~12/25 E F G 12/10~12/12 A B C D E F G ( ) 12/10~1/21 A B C D E F G 12/24~12/25 D G PAHs 2002/3/11~3/12 A B C D 3/12~3/14 A B C D E F G ( ) 3/4~4/2 A B C D E F G -66-
3-2 PS-1 (High volume air sampler) (Mirco-orifice uniform deposit impactor, MOUDI) PS-1 PAHs PAHs MOUDI PAHs PAHs 3-2-1 PS-1 MOUDI PS-1 PAHs PAHs PAHs PAHs 3-2-1-1 PS-1 1. General Metal Work Co. GPS1 PUF Sampler 3-2 -1 PAHs PAHs ( ) XAD-16 PAHs (1) (Dual chamber sampling module) (2) (Flow venturi) (3) (Magnehelic gage) -67-
(4) (Voltage variator) (5) (Elapsed time indicator) (6) (Blower motor) (7) (Timer) (8) (Exhaust hose) (9) (Aluminum shelter) 3-2-1 PS-1-68-
2. Whatman International Ltd. 10.2 cm 0.8 µm PAHs 450 C PAHs 8 3. PAHs 20 mm 30 mm XAD-16 50 mm ( 3-2-2 ) PAHs XAD-16 XAD-16 (Soxhlet extractor) 1000 ml 4. PAHs PS-1 PAHs PAHs -69-
3-2-2 5. GMW High Volume Air Samplers (GMW Inc. ) GPS1 General Metal Works Inc. GMW-25 (GMW-25 calibration kit) (1) GPS1 (2) GMW-25 (3) (4) (5) 5 10 15 20 25 30 35 40 45 50-70-
(6) 5 5 50 5 (7) 5 6 ( 3-2-3) 3-2-2 General Metal Works Inc. ( 3-2-4) GPS1-71-
3-2-3 PS-1 3-2-4 PS-1-72-
3-2-1-2 1. MSP MOUDI Model No. 100 MOUDI 3-2-5 (Cascade impactor) (Rotator) 9 (Stages) (Cutsize) 3-2-1 9 ( 300 ) MOUDI 30 L min -1 (Impaction) MOUDI -73-
3-2-5 MOUDI 3-2-1 MOUDI (µm) ( ) Stage 1 18 ~ 10 Stage 2 10 ~ 5.6 Stage 3 5.6 ~ 3.2 Stage 4 3.2 ~ 1.8 Stage 5 1.8 ~ 1.0 Stage 6 1.0 ~ 0.556 Stage 7 0.556 ~ 0.33 Stage 8 0.33 ~ 0.167 Stage 9 0.167~0.1-74-
2. MOUDI MSP (Aluminum foil 37 mm) Gelman Sciences Zefluor ( 37 mm 2 µm) (Afterfilter) 1 1 24 40% 24 60 C 90 24 8 3. MOUDI SHINAGAWA SEIKI Model DC-5A (Dry gas meter) 10 L MOUDI 30 L/min 20 (1) MOUDI (2) (3) 1 2 3-75-
4 5 6 7 8 9 10 (4) 3 ( 3-2-6) 20 30 L min -1 30 25 (sec) 20 15 10 y = 1.95x + 10.43 R 2 = 0.9978 5 0 0 1 2 3 4 5 6 7 8 9 ( ) 3-2-6 MOUDI -76-
3-2-2 1. (PVC) 21.6 cm 8.0 cm 0.8 cm ( 10 ) 10 cm 8 3-2-7 150 cm 50 cm 8.0 5.5 cm ( 3-2-8) 2. 1 1 24 40% 24 60 C 90 0.03 cm 8 3. PAHs PAHs PAHs V d,tm = K (F t,tm ) / (C tsp ) (3-1) -77-
V d,tm = PAHs (cm s -1 ) K = F t,tm = PAHs (mg m -2 day -1 ) C tsp = PAHs (µg m -3 ) 50 cm 150 cm 3-2-7-78-
8 cm 0.65 cm 5.5 cm 10 cm 8.0 cm 3-2-8-79-
3-2-3 1. 30 cm 30 cm 2 8 cm 3 cm 3 cm PAHs 2. PAHs (MFS A045F047A 0.45 µm 47 mm) PAHs 1 1 24 40% 24 ( Sartorius BP 211D 0.01 mg) (25 ) 24-80-
3. 30 3-2-4 1. Graseby Anderson Auto5 TM (Auto5 TM Automatic Stack Sampler) Universal Analyzers Inc. (Sample cooler Model 1090) Auto5 TM PAHs Auto5 TM Universal Analyzers Inc. 4 C PAHs (Probe) PAHs (1) (Coaxial dust collection tube) 4 mm ~ 14 mm (Nozzle) T (Thermocouple) (Compensation wire) 1300 mm (2) (Model-1090, Universal Analyzers Inc.) (Stainless steel heat exchanger drainer) -81-
4~5 C PAHs (3) PAHs PAHs (Cartridge) 20 mm 30 mm XAD-16 50 mm PAHs (Breakthrough test) PAHs (4) (Total pressure) (Static pressure) (Main body) (Z80-CPU) (Coefficient of pilot tube) 30 L min -1-82-
(5) 0.6 (Teflon) 35 2. (1) (a) PAHs 20 mm 30 mm XAD-16 50 mm PAHs 8 ( XAD-16) Anderson 0.025 g cm -3 XAD-16 AMBERLITE 800 m 2 g -1 62~70% XAD-16 (Soxhlet extractor) 1000 ml (b) PAHs 50% -83-
(2) PAHs PAHs PAHs ( PUF XAD-16 ) PAHs (3) ( 1 1) PAHs QA/AC / ( 6 4) PAHs PAHs 2 ml 3-3 PAHs PAHs PAHs 1. PAHs ( 16 cm 4 cm) 300 ml 250 ml ( 1 1) 24 4-84-
PAHs PAHs ( ) ( 20 cm 7 cm) 800 ml ( 1 1) 24 4 ( 1 1) PAHs QA/AC / ( 6 4) PAHs PAHs 2 ml 0.5 1 150 ml l ( 1 1) 100 m 5 10 cm 20 30 ml 2. 1.5 ml 3. -85-
(Silica gel) 17 g 1 g 105 C 8 15 g 3% 400 C 24 2 ml 25 ml PAHs 10 ml 200 ml 4. 0.5 ml GC/MS PAHs 5. PAHs Agilent 6890/5973N (Gas Chromatograph / Mass Spectrometer, GC/MS) Agilent 7683 1 µl Agilent Ultra 2 0.32 mm 0.17 µm 50 m 3 4 50 C 20 C min -1-86-
100 C 3 C min -1 290 C 40 GC/MS 310 C (Ion source) 310 C -87-
PAHs 4-1 4-1-1 (Reagent Blank) 250 ml 0.5 ml GC/MS 21 PAHs (IDL) 4-1-2 (Field Blank) 4-1-3 (Trip Blank) -88-
4-1-4 ( ) 4-2 4-2-1 (1998) PAHs 25.3% PAHs 6% PAHs 4.5% 4-2-2 PAHs PAHs 3 cm XAD-16 PAHs (Breakthrough test) XAD-16 ( 4-2-1 ) XAD-16 PAHs 4-2-1-89-
6.3 cm PUF XAD-16 resin PUF XAD-16 resin PUF 3 cm 2 cm 1 cm 2 cm 2 cm 4-2-1-90-
PAHs 4-2-1 PAHs XAD-16 PAHs (ng Nm -3 (%) ) N.D. XAD-16 PAHs (ng Nm -3 (%) ) Nap 175 99.2 1.47 0.832 AcPy 28.3 99.9 0.0241 0.085 Acp 2.95 93.2 0.2162 6.82 Flu 4.37 98.9 0.0477 1.08 PA 9.77 99.3 0.0677 0.688 Ant 0.798 98.0 0.0161 1.98 FL 1.99 99.5 0.0096 0.481 Pyr 2.71 98.5 0.0410 1.49 CYC 0.084 99.8 0.0001 0.155 BaA 0.231 97.2 0.0066 2.76 CHR 0.309 98.8 0.0037 1.19 BbF 0.0649 99.0 0.0007 1.00 BkF 0.0336 99.1 0.0003 0.940 BeP 0.120 99.2 0.0010 0.794 BaP 0.124 99.5 0.0007 0.522 PER 0.235 99.5 0.0012 0.493 IND 0.0196 100 N.D. 0.00 DBA 0.0063 100 N.D. 0.00 BbC 0.180 99.6 0.0008 0.433 BghiP 0.152 99.9 0.0002 0.141 COR 0.936 99.7 0.0028 0.300 230 99.8 0.479 0.208-91-
(2 cm ) XAD-16 PAHs 99.8% XAD-16 PAHs 0.208% 3 cm XAD-16 PAHs 99.8% 4-3 (Method Detection Limit, MDL) 99% (Confidence) MDL MDL MDL PAHs PAHs MDL Long Winefordner Long and Winefordner, 1983 MDL = 3 (S b 2 + S i 2 +(i/m) 2 S m 2 ) 1/2 /m (4-1) S b S i S m i m PAHs GC/MS 4-3-1 MDL 0.024 ~ 0.740 ng GC/MS Nap BaA 0.042 ~ 1.28 ng m -3-92-
PAHs 4-3-1 GC/MS MDL (ng) Nap 0.740 1.28 AcPy 0.406 0.705 Acp 0.319 0.553 Flu 0.115 0.200 PA 0.061 0.107 Ant 0.097 0.168 FL 0.197 0.341 Pyr 0.575 0.998 CYC 0.045 0.079 BaA 0.024 0.042 CHR 0.097 0.168 BbF 0.143 0.249 BkF 0.040 0.070 BeP 0.041 0.072 BaP 0.027 0.047 PER 0.027 0.047 IND 0.073 0.126 DBA 0.153 0.266 BbC 0.172 0.299 BghiP 0.062 0.109 COR 0.110 0.191 (ng m -3 ) -93-
4-4 (Calibration curve) 4-4-1 1999 1. 2. ( ) 3. 4. 5. (Least square srror equation) r 6. r 0.995 4-4-2 1. 12 2. ± 20% 3. -94-
4. 21 PAHs GC/MS 4-4-1 ~ 4-4-6 ( 4-4-1 4-4-2) 10 µg ml -1 GC/MS 4-4-3 (RSD) 4-4-4 4-5 (Accuracy) (Precision) PAHs GC/MS GC/MS PAHs (X) X n= X + X +... X n 1 2 n (4-2) Χn Χ(%) = 100% (4-3) C X i n Xn C (RSD) n S 2 = [ ( X i Xn ) ] n 1 i= 1 S RSD(%) = X 100 n 1 2 (4-4) (4-5) -95-
2.5e+7 2.5e+7 Integrated Area 2.0e+7 1.5e+7 1.0e+7 5.0e+6 Nap R 2 =0.9974 2.0e+7 1.5e+7 1.0e+7 5.0e+6 AcPy R 2 =0.9917 0.0 0 2 4 6 8 10 12 0.0 0 2 4 6 8 10 12 The Mass Injected to the GC/MS(ng) 2.5e+7 3.0e+7 Integrated Area 2.0e+7 1.5e+7 1.0e+7 Acp R 2 =0.9940 2.5e+7 2.0e+7 1.5e+7 1.0e+7 Flu R 2 =0.9946 5.0e+6 5.0e+6 0.0 0 2 4 6 8 10 12 0.0 0 2 4 6 8 10 12 The Mass Injected to the GC/MS(ng) 4-4-1 Nap, AcPy, Acp Flu -96-
2.5e+7 2.5e+7 Integrated Area 2.0e+7 1.5e+7 1.0e+7 5.0e+6 PA R 2 =0.9943 2.0e+7 1.5e+7 1.0e+7 5.0e+6 Ant R 2 =0.9911 0.0 0 2 4 6 8 10 12 0.0 0 2 4 6 8 10 12 The Mass Injected to the GC/MS(ng) Integrated Area 2.5e+7 2.0e+7 1.5e+7 1.0e+7 5.0e+6 FL R 2 =0.9935 2.5e+7 2.0e+7 1.5e+7 1.0e+7 5.0e+6 Pyr R 2 =0.9930 0.0 0 2 4 6 8 10 12 0.0 0 2 4 6 8 10 12 The Mass Injected to the GC/MS(ng) 4-4-2 PA, Ant, FL Pyr -97-
Integrated Area 3.5e+6 3.0e+6 2.5e+6 2.0e+6 1.5e+6 1.0e+6 CYC R 2 =0.9974 2.5e+7 2.0e+7 1.5e+7 1.0e+7 BaA R 2 =0.9949 5.0e+5 5.0e+6 0.0 0 2 4 6 8 10 12 0.0 0 2 4 6 8 10 12 The Mass Injected to the GC/MS(ng) Integrated Area 2.5e+7 2.0e+7 1.5e+7 1.0e+7 5.0e+6 CHR R 2 =0.9901 2.5e+7 2.0e+7 1.5e+7 1.0e+7 5.0e+6 BbF R 2 =0.9924 0.0 0 2 4 6 8 10 12 0.0 0 2 4 6 8 10 12 The Mass Injected to the GC/MS(ng) 4-4-3 CYC, BaA, CHR BbF -98-
Integrated Area 3.0e+7 2.5e+7 2.0e+7 1.5e+7 1.0e+7 5.0e+6 BkF R 2 =0.9960 7.0e+6 6.0e+6 5.0e+6 4.0e+6 3.0e+6 2.0e+6 1.0e+6 BeF R 2 =0.9940 0.0 0 2 4 6 8 10 12 0.0 0 2 4 6 8 10 12 The Mass Injected to the GC/MS(ng) Integrated Area 2.5e+7 2.0e+7 1.5e+7 1.0e+7 5.0e+6 BaP R 2 =0.9931 7.0e+6 6.0e+6 5.0e+6 4.0e+6 3.0e+6 2.0e+6 1.0e+6 PER R 2 =0.9975 0.0 0 2 4 6 8 10 12 0.0 0 2 4 6 8 10 12 The Mass Injected to the GC/MS(ng) 4-4-4 BkF, BeP, BaP PER -99-
Integrated Area 2.0e+7 1.5e+7 1.0e+7 5.0e+6 IND R 2 =0.9918 6.0e+6 5.0e+6 4.0e+6 3.0e+6 2.0e+6 1.0e+6 DBA R 2 =0.9925 0.0 0 2 4 6 8 10 12 0.0 0 2 4 6 8 10 12 The Mass Injected to the GC/MS(ng) Integrated Area 1.6e+6 1.2e+6 8.0e+5 4.0e+5 BbC R 2 =0.9956 1.2e+7 8.0e+6 4.0e+6 BghiP R 2 =0.9988 0.0 0 2 4 6 8 10 12 0.0 0 2 4 6 8 10 12 The Mass Injected to the GC/MS(ng) 4-4-5 IND, DBA, BbC BghiP -100-
Integrated Area 6.0e+6 4.0e+6 2.0e+6 COR R 2 =0.9975 0.0 0 2 4 6 8 10 12 The Mass Injected to the GC/MS(ng) 4-4-6 COR -101-
4-4-1 PAHs (Chem Service) (µg ml -1 ) Acenaphthene Acp 2000 Fluoranthene FL 2000 Naphthalene Nap 2000 Benzo(a)anthracene BaA 2000 Benzo(a)pyrene BaP 2000 Benzo(b)fluoranthene BbF 2000 Benzo(k)fluoranthene BkF 2000 Chrysene (93%) CHR 2000 Acenaphthylene AcPy 2000 Anthracene Ant 2000 Benzo(ghi)perylene BghiP 2000 Fluorene Flu 2000 Phenanthrene PA 2000 Dibenzo(a,h)anthracene DBA 2000 Indeno(1,2,3-cd)pyrene IND 2000 Pyrene Pyr 2000 Perylene PER 100 Benzo(e)pyrene BeP 100 Coronene COR 100 4-4-2 PAHs (Gravimetric Certificate) (µg ml -1 ) Cyclopenta(c,d)pyrene CYC 10 Benzo(b)chrysene BbC 10-102-
PAHs 4-4-3 PAHs 10 µg ml -1 GC/MS Nap 18386324 17324411 17411858 16959302 16287576 15682434 15126506 AcPy 20377751 18320317 18861545 18237402 17408673 16756412 16148896 Acp 16950666 16602297 16938048 16575749 16048539 15445615 15012759 Flu 20114710 19086051 19201097 18810565 18034989 17341091 16852433 PA 18130142 17039812 17048679 16708082 15981088 15417212 14994321 Ant 17853358 16486131 16513454 16243653 15448988 14908622 14585342 FL 20420316 19382871 19297872 18971453 18031267 17418177 16993745 Pyr 20868638 19997547 19881512 19581730 18631665 18017158 17600534 CYC 846978 834158 818791 837683 848297 873831 903310 BaA 21339633 19971626 19998877 19656355 18762090 18074756 17698033 CHR 21172338 20454982 20417610 20035601 19093554 18446752 18077771 BbF 22806226 21541670 21556561 21208667 20238903 19509865 19122962 BkF 22694250 21816538 21810492 21458550 20520984 19799161 19377545 BeP 11517138 11529144 11700795 11680595 11859987 11990791 12064911 BaP 19575625 19059258 19306806 18611539 17782341 17156128 16910517 PER 11152850 10898262 10934499 11064445 11040010 11034780 11150820 IND 12611018 13532784 13214504 14183246 12021315 11971000 13214504 DBA 5232587 5035330 4987038 4924663 4701842 4539849 4510762 BbC 9516365 9511651 9611287 10238526 9902796 9789216 10282280 BghiP 6914884 7435952 8805780 8277586 8828118 8828118 8042579 COR 1520966 1347854 1403521 1391368 1317888 1332246 1312320-103-
4-4-4 PAHs 10 µg ml -1 GC/MS PAHs (%) Nap 16739773 1116386 6.67 AcPy 18015857 1406883 7.81 Acp 16224810 753714.6 4.65 Flu 18491562 1141053 6.17 PA 16474191 1079908 6.56 Ant 16005650 1117290 6.98 FL 18645100 1213632 6.51 Pyr 19225541 1176609 6.12 CYC 851864 28208.34 3.31 BaA 19357339 1262303 6.52 CHR 19671230 1149609 5.84 BbF 20854979 1296469 6.22 BkF 21068217 1202472 5.71 BeP 11763337 215345.3 1.83 BaP 18343173 1065241 5.81 PER 11039381 97346.84 0.88 IND 12964053 809823.1 6.25 DBA 4847439 270263.7 5.58 BbC 9836017 322931.4 3.28 BghiP 8161860 754093.8 9.24 COR 1375166 73192.23 5.32-104-
S X i Xn n 4-5-1 71.54 ± 4.55% ~ 97.64 ± 3.93% 0.27% ~ 9.15% ( 4-5-2) 4-6 PAHs 3 3 (SD) ± 3 SD GC/MS SCAN mode (Primary ion number) (Secondary ion number) SIM mode (Selectivity ion monitoring mode) 21 PAHs GC/MS 72 24 3 24 2 24 2 7 (SD) 3 SD 21 PAHs GC/MS 4-6-1 4-6-2 GC/MS SIM mode SIM mode (Primary ion) (Secondary ion) 4-6-3-105-
PAHs 4-5-1 (%) (%) (%) Nap 73.15 83.74 70.67 AcPy 70.46 74.16 70.01 Acp 95.60 90.45 87.02 Flu 94.74 85.29 80.21 PA 96.47 93.93 90.16 Ant 97.76 99.83 92.69 FL 94.87 94.22 88.94 Pyr 86.49 92.19 84.25 CYC 83.91 93.54 90.00 BaA 93.36 91.09 88.19 CHR 80.92 86.68 94.08 BbF 81.22 87.78 94.98 BkF 90.45 87.40 86.12 BeP 95.52 96.32 97.50 BaP 87.64 88.33 87.06 PER 84.16 94.90 86.50 IND 85.28 90.60 95.41 DBA 97.58 99.63 95.70 BbC 87.98 95.77 99.37 BghiP 96.94 96.43 96.81 COR 96.87 97.71 96.20-106-
4-5-2 PAHs PAHs (%) (%) (%) (%) Nap 75.9 6.94 9.15 75.9 ± 13.9 AcPy 71.5 2.27 3.18 71.5 ± 4.55 Acp 91.0 4.32 4.74 91.0 ± 8.63 Flu 86.7 7.37 8.50 86.7 ± 14.7 PA 93.5 3.18 3.40 93.5 ± 6.35 Ant 96.8 3.67 3.80 96.8 ± 7.35 FL 92.7 3.25 3.51 92.7 ± 6.50 Pyr 87.6 4.10 4.67 87.6 ± 8.19 CYC 89.2 4.87 5.46 89.2 ± 9.74 BaA 90.9 2.59 2.85 90.9 ± 5.18 CHR 87.3 6.60 7.57 87.3 ± 13.2 BbF 88.0 6.88 7.82 88.0 ± 13.8 BkF 88.0 2.22 2.53 88.0 ± 4.45 BeP 96.5 1.00 1.03 96.5 ± 1.99 BaP 87.7 0.63 0.72 87.7 ± 1.27 PER 88.5 5.65 6.38 88.5 ± 11.3 IND 90.4 5.06 5.60 90.4 ± 10.1 DBA 97.6 1.96 2.01 97.6 ± 3.93 BbC 94.4 5.82 6.17 94.4 ± 11.6 BghiP 96.7 0.27 0.27 96.7 ± 0.53 COR 96.9 0.75 0.78 96.9 ± 1.51-107-
4-6-1 21 PAHs GC/MS (min) PAHs Nap 10.812 10.850 10.860 10.826 10.850 10.821 10.850 AcPy 17.982 18.049 18.064 18.006 18.049 18.001 18.054 Acp 19.049 19.112 19.126 19.069 19.117 19.069 19.112 Flu 22.012 22.084 22.098 22.036 22.084 22.036 22.084 PA 27.845 27.927 27.946 27.874 27.927 27.874 27.927 Ant 28.133 28.023 28.258 28.172 28.234 28.167 28.234 FL 35.539 35.621 35.645 35.568 35.626 35.568 35.626 Pyr 36.866 36.963 36.991 36.905 36.962 36.900 36.963 CYC 44.671 44.662 44.667 44.667 44.676 44.667 44.662 BaA 44.926 45.018 45.051 44.960 45.017 44.955 45.022 CHR 45.186 45.306 45.359 45.239 45.306 45.215 45.311 BbF 51.596 51.702 51.745 51.639 51.707 51.630 51.702 BkF 51.774 51.914 51.976 51.832 51.913 51.812 51.918 BeP 52.981 52.981 52.986 52.991 53.053 52.967 53.005 BaP 53.318 53.348 53.491 53.371 53.447 53.361 53.443 PER 53.717 53.712 53.702 53.707 53.722 53.779 53.727 IND 59.146 59.286 59.262 59.024 59.281 59.199 59.261 DBA 59.415 59.555 59.622 59.478 59.564 59.444 59.550 BbC 59.762 59.762 59.742 59.742 59.762 59.762 59.742 BghiP 60.392 60.584 60.541 60.473 60.584 60.411 60.589 COR 70.034 70.043 70.048 70.077 70.250 70.370 70.096-108-
4-6-2 21 PAHs GC/MS PAHs 3SD (min) (SD) (min) Nap 10.838 0.018 10.838 0.054 AcPy 18.029 0.032 18.029 0.096 Acp 19.093 0.030 19.093 0.090 Flu 22.062 0.033 22.062 0.099 PA 27.903 0.038 27.903 0.114 Ant 28.174 0.080 28.174 0. 240 FL 35.599 0.040 35.599 0.120 Pyr 36.936 0.045 36.936 0.135 CYC 44.667 0.005 44.667 0.015 BaA 44.993 0.046 44.993 0.138 CHR 45.275 0.062 45.275 0.186 BbF 51.674 0.053 51.674 0.159 BkF 51.877 0.072 51.877 0.216 BeP 52.995 0.028 52.995 0.084 BaP 53.410 0.061 53.410 0.183 PER 53.724 0.026 53.724 0.078 IND 59.208 0.096 59.208 0.288 DBA 59.518 0.074 59.518 0.222 BbC 59.753 0.011 59.753 0.033 BghiP 60.511 0.085 60.511 0.255 COR 70.131 0.129 70.131 0.387-109-
4-6-3 21 PAHs (Primary ion) (Secondary ion) PAHs Primary ion Secondary ion Nap 128 127.10 AcPy 152 151.10 Acp 153.10 154.10 Flu 166.10 165.10 PA 178.10 176 Ant 178.10 176 FL 202.10 200.00 Pyr 202.10 200.00 CYC 226.10 224.00 BaA 228.10 226.10 CHR 228.10 226.10 BbF 252.10 250.10 BkF 252.10 250.10 BeP 252.10 250.00 BaP 252.10 250.10 PER 252.10 250.00 IND 276.10 277.10 DBA 278.10 279.10 BbC 278.10 276.10 BghiP 276.10 277.10 COR 300.00 150.00-110-
4-7 (1 2 3 6 ) -111-
5-1 90 7 9~10 ( ) 10 11~12 ( ) 12 24~25 ( ) 91 3 11~12 ( ) PAHs A C D E F G C E G E F G A B C D 5-1-1 5-1-1 (µg m -3 ) A B C D E F G 142 112 141 129 38.6 37.2 21.1 39.3 48.4 45.7 94.3 87.4 90.5 191 120 84.7 90.2 112 90.9 75.0 106 84.3 73.7 5-1-1 A 38.6~142 µg m -3 90.2 µg m -3 B 112 µg m -3 C 37.2~141 µg m -3 90.9 µg m -3 D 21.1~129 µg m -3 75.0 µg m -3 E 39.3~191 µg m -3 106 µg m -3 F 48.4~120 µg m -3 84.3 µg m -3 G 45.7~90.5 µg m -3 73.7 µg m -3 24 (250 µg m -3 ) (1994) (112, 122 µg m -3 ) (2000) -112-
(148, 237, 322 412 µg m -3 ) Concentration (µg m -3 ) 250 200 150 100 Spring Summer Fall Winter 50 0 A B C D E F G Sampling sites 5-1-1 5-1-1 131 38.4 91.7 132 µg m -3-113-
(Mixing height) (Boundary layer) 2000 (1992) 5-1-2 PAHs 5-1-2-1 PAHs 5-1-2 2001 7 ~2002 5 PAHs ( + ) F (666 ng m -3 ) D (235 ng m -3 ) 5-1-3 21 PAHs (1993) 1794 ng m -3 (1998) 1496 ng m -3 (1995) 1324 ng m -3 (1998) (1508 402 ng m -3 ) (1996) (468 231 ng m -3 ) (1998) (198 298 ng m -3 ) PAHs PAHs -114-
-115-5-1-2 PAHs (ng m -3 ) PAHs Site A (n=2) Site B (n=1) Site C (n=3) Site D (n=2) Site E (n=3) Site F (n=2) Site G (n=3) Nap 332 (223~441) 372 412 (70~680) 203 (24~382) 456 (15~836) 618 (49~1187) 398 (15~756) AcPy 4.03 (3.30~4.75) 1.77 2.45 (1.46~3.19) 1.52 (0.60~2.43) 4.51 (0.12~12.7) 6.32 (1.79~10.8) 3.78 (0.10~10.0) Acp 5.3 (5.25~5.34) 3.46 9.42 (8.23~10.1) 2.37 (0.72~4.0) 3.23 (0.29~6.57) 3.21 (0.10~6.31) 2.38 (0.28~4.83) Flu 10 (9.53~10.5) 7.67 12.9 (12.2~13.8) 5.68 (3.18~8.17) 8.33 (0.96~17.1) 4.71 (3.32~6.09) 6.86 (0.48~14.7) PA 23 (20.7~25.2) 15.6 27.3 (22.5~31.0) 10.9 (5.05~16.6) 15.8 (2.86~30.9) 16.8 (11.3~22.3) 14.6 (4.72~28.3) Ant 1.89 (1.07~2.71) 0.7 1.91 (1.52~2.29) 0.89 (0.73~1.05) 0.41 (0.29~0.61) 0.72 (0.26~1.17) 0.58 (0.29~0.70) FL 6.08 (5.61~6.53) 4.46 6.9 (5.51~8.33) 2.87 (1.31~4.43) 3.09 (0.55~5.21) 4.82 (0.92~8.72) 3.14 (0.69~6.25) Pyr 3.21 (0.73~5.68) 3.84 5.23 (3.86~6.10) 2.06 (0.40~3.70) 2.97 (0.44~5.64) 5.71 (5.44~5.97) 2.98 (0.50~6.34) CYC 0.1 (0.16~0.02) 0.02 0.09 (0.006~0.22) 0.09 (0.16~0.20) 0.15 (0.03~0.28) 0.04 (0.02~0.06) 0.37 (0.19~0.56) BaA 0.25 (0.11~0.39) 0.03 0.17 (0.05~0.35) 0.13 (0.059~0.20) 0.07 (0.003~0.10) 0.03 (0.01~0.05) 0.69 (0.08~1.05) CHR 0.73 (0.17~1.29) 1.36 0.71 (0.33~1.26) 0.98 (0.28~1.676) 0.63 (0.003~0.99) 0.36 (0.003~0.72) 1.39 (0.30~2.91) BbF 0.1 (0.04~0.14) 0.08 0.13 (0.02~0.29) 0.2 (0.09~0.29) 0.59 (0.46~0.74) 0.24 (0.07~0.41) 1.51 (1.05~2.05) BkF 0.16 (0.14~0.16) 0.18 0.28 (0.21~0.41) 0.23 (0.18~0.27) 0.68 (0.13~1.08) 0.44 (0.06~0.81) 1.63 (1.22~2.37) BeP 0.24 (0.16~0.31) 0.700 0.41 (0.16~0.83) 0.88 (0.66~1.10) 1 (0.56~1.42) 0.63 (0.16~1.09) 1.56 (0.61~2.21) BaP 0.12 (0.06~0.18) 0.06 0.19 (0.091~0.31) 0.08 (0.026~0.14) 0.5 (0.19~0.77) 0.78 (0.017~1.54) 0.85 (0.22~1.62) PER 0.13 (0.073~0.19) 0.52 0.26 (0.13~0.42) 0.8 (0.67~0.92) 0.49 (0.09~1.12) 0.35 (0.016~0.69) 0.33 (0.04~0.53) IND 0.2 (0.053~0.35) 0.06 0.09 (0.04~0.17) 0.44 (0.06~0.82) 0.79 (0.70~0.86) 0.33 (0.30~0.34) 1.35 (1.05~1.83) DBA 0.02 (0.008~0.03) 0.09 0.25 (0.07~0.52) 0.15 (0.12~0.16) 0.3 (0.04~0.58) 0.3 (0.04~0.54) 0.34 (0.08~0.55) BbC 0.2 (0.13~0.27) 0.12 0.18 (0.06~0.29) 0.17 (0.15~0.19) 0.41 (0.08~0.89) 0.88 (0.02~1.74) 0.21 (0.15~0.25) BghiP 0.08 (0.005~0.15) 0.01 0.18 (0.006~0.48) 0.38 (0.20~0.55) 0.52 (0.17~0.91) 0.08 (0.004~0.15) 1.29 (0.30~2.22) COR 0.78 (0.45~1.10) 0.23 0.62 (0.36~1.04) 0.77 (0.50~1.04) 1.13 (0.64~1.40) 0.98 (0.05~1.90) 1.74 (1.39~1.92) Total 389 413 481 235 502 666 446
5-1-3 PAHs (ng m -3 ) PAHs + 1 N.A. N.A. 508 (1998) 2 N.A. N.A. 442 (1998) 1650 144 1794 (1993) 1 418 50 468 (1996) 2 214 17 231 (1996) 1274 222 1496 (1998) 810 163 973 (1994) 1120 151 1271 (1994) N.A. N.A. 198 (1998) N.A. N.A. 298 (1998) 1 352 150 502 (1995) 2 1030 294 1324 (1995) N.A. 5-1-2-2 PAHs PAHs PAHs PAHs PAHs PAHs 5-1-4 PAHs A~G ( / + ) 1.76% 2.15% 1.77% 3.97% 2.84% 1.09% 4.14% 1993 1994 1994 1996 1998 PAHs (7.35~16.7%) PAHs PAHs PAHs -116-
(Blow-off) PAHs PAHs PAHs Bidleman, 1986 (1998) PAHs 1274 ng m -3 PAHs 222 ng m -3 PAHs 85% PAHs 15% 5-1-4 PAHs PAHs (Nap AcPy Acp Flu PA) (1998) PAHs 4 (MW 252) PAHs Grojean, 1983 PAHs PAHs PAHs ; PAHs Vaeck et al., 1984-117-
PAHs 5-1-4 (Cp) (Cg) PAHs A (n=2) B (n=1) C (n=3) D (n=2) Cg Cp Cp / Cg Cp Cp / Cg Cp Cp / Cg Cp (ng m -3 ) (ng m -3 ) PAHs (%) (ng m -3 ) (ng m -3 ) PAHs (%) (ng m -3 ) (ng m -3 ) PAHs (%) (ng m -3 ) (ng m -3 ) Cp / PAHs (%) Nap 329 2.85 0.857 368 4.12 1.11 407 4.63 1.13 200 2.82 1.39 AcPy 3.98 0.051 1.27 1.72 0.057 3.19 2.41 0.033 1.34 1.45 0.069 4.57 Acp 5.24 0.058 1.1 3.42 0.036 1.05 9.37 0.046 0.49 2.28 0.082 3.48 Flu 9.81 0.221 2.2 7.49 0.177 2.3 12.6 0.213 1.66 5.41 0.273 4.8 PA 22.1 0.854 3.72 14.8 0.802 5.14 26.5 0.778 2.85 9.73 1.126 10.4 Ant 1.85 0.039 2.08 0.698 0 0 1.88 0.037 1.94.831 0.06 6.77 FL 5.67 0.407 6.69 3.84 0.624 14 6.71 0.186 2.69 2.17 0.701 24.4 Pyr 2.74 0.468 14.6 3.11 0.737 19.2 4.93 0.3 5.73 1.44 0.619 30.1 CYC 0.029 0.067 69.6 0.009 0.013 57.9 0.009 0.082 90.5 0.012 0.078 86.4 BaA 0.229 0.024 9.49 0.004 0.024 86.3 0.144 0.026 15.2 0.081 0.051 39 CHR 0.649 0.086 11.7 0.893 0.463 34.1 0.627 0.086 12 0.408 0.574 58.5 BbF 0.009 0.088 90.9 0.015 0.068 81.7 0.012 0.121 91.3 0.056 0.141 71.6 BkF 0.047 0.109 69.7 0.046 0.132 74.2 0.061 0.221 78.5 0.046 0.186 80.1 BeP 0.002 0.234 99.1 0.016 0.684 97.7 0.023 0.386 94.4 0.117 0.764 86.7 BaP 0.057 0.065 53 0.057 0 0 0.036 0.152 81 0.013 0.071 84.2 PER 0.008 0.124 93.7 0.009 0.507 98.3 0.081 0.175 68.3 0.273 0.524 65.7 IND 0.058 0.144 71.3 0.001 0.057 98.9 0.49 0.041 45.8 0.276 0.168 37.7 DBA 0.004 0.016 81.1 0.003 0.084 96.9 0.019 0.226 92.3 0.054 0.092 62.8 BbC 0.017 0.186 91.7 0.006 0.119 95.3 0.29 0.151 84 0.051 0.124 71 BghiP 0.002 0.078 97.2 0 0.005 98.7 0.001 0.181 99.3 0.007 0.373 98.1 COR 0.105 0.671 86.4 0.071 0.163 69.7 0.171 0.448 72.3 0.360 0.412 53.4 Total 382 6.84 1.76 404 8.88 2.15 473 8.52 1.77 226 9.31 3.97-118-
PAHs 5-1-4 (Cp) (Cg) PAHs ( ) E (n=3) F (n=2) G (n=3) Cg Cp Cp / Cg Cp Cp / Cg Cp (ng m -3 ) (ng m -3 ) PAHs (%) (ng m -3 ) (ng m -3 ) PAHs (%) (ng m -3 ) (ng m -3 ) Cp / PAHs (%) Nap 451 5.57 1.22 617 1.02 0.16 394 3.79 0.953 AcPy 4.45 0.057 1.26 6.29 0.039 0.61 3.74 0.044 1.16 Acp 3.16 0.067 2.08 3.14 0.066 2.05 2.32 0.061 2.55 Flu 8.09 0.237 2.84 4.44 0.264 5.61 6.62 0.231 3.37 PA 14.7 1.061 6.71 15.4 1.411 8.37 13.4 1.21 8.32 Ant 0.360 0.052 12.6 0.664 0.056 7.84 0.520 0.060 10.3 FL 2.56 0.535 17.3 4.16 0.665 13.8 2.63 0.510 16.2 Pyr 2.32 0.647 21.8 4.76 0.948 16.6 2.18 0.799 26.8 CYC 0.021 0.126 85.9 0.024 0.017 41.9 0.032 0.334 91.3 BaA 0 0.068 99.4 0.001 0.032 95.8 0.004 0.684 99.4 CHR 0.033 0.595 94.7 0.317 0.045 12.4 0.072 1.32 94.8 BbF 0.065 0.522 88.9 0.081 0.163 66.9 0.391 1.12 74.0 BkF 0.042 0.639 93.8 0.099 0.340 77.5 0.352 1.28 78.3 BeP 0.105 0.897 89.5 0.208 0.422 66.9 0.016 1.55 98.9 BaP 0.083 0.415 83.3 0.366 0.416 53.3 0.009 0.844 98.9 PER 0.317 0.178 35.9 0.193 0.162 45.6 0.011 0.317 96.7 IND 0.031 0.754 96.1 0.157 0.170 51.9 0.189 1.16 86.0 DBA 0.016 0.285 94.8 0.040 0.256 86.4 0.016 0.328 95.4 BbC 0.128 0.283 68.9 0.328 0.553 62.8 0.014 0.194 93.1 BghiP 0.015 0.509 97.2 0.017 0.061 78.8 0.001 1.29 99.9 COR 0.359 0.769 68.2 0.811 0.165 16.9 0.417 1.33 76.0 Total 488 14.2 2.84 658 7.27 1.09 427 18.5 4.14-119-
5-1-2-3 PAHs 5-1-2 PAHs 21 PAHs Nap 2 3 PAHs Acpy Acp Flu PA Ant 4 PAHs FL Pyr BaA CHR 5 PAHs CYC BbF BkF BeP BaP PER DBA BbC 6 PAHs IND Bghip 7 PAHs COR 5-1-2 PAHs ( Nap) 3 PAHs C (75.7 ng m -3 ) A (75.6 ng m -3 ) ( 687 ng m -3 ) ( 115 ng m -3 ) PAHs (Aceves, 1993 2001) Müller (1998) PAHs 3~6 PAHs Dörr (1996) PAHs 1.9~14 Müller (1998) Dörr (1996) 5-1-2 PAHs ( Nap) 3 PAHs 79% 4 PAHs 5~7 PAHs 1992 2001-120-
80 60 40 3-rings A B C D E F G 20 15 10 4-rings A B C D E F G 20 5 PAHs concentration (ng m -3 ) 0 0 spring summer fall winter A 10 5-rings 6-rings 8 6 4 2 0 spring summer fall winter spring summer fall winter B C D E F G 5 4 3 2 1 0 spring summer fall winter A B C D E F G 3.0 2.5 2.0 1.5 7-rings A A B B C C D D E E F F G G 1000 800 600 Total PAHs A B C D E F G 1.0 400 0.5 200 0.0 spring summer fall winter 0 spring summer fall winter Season Season 5-1-2 PAHs -121-
5-2 5-2-1 5-2-1 A 119~215 mg m -2 day -1 207 mg m -2 day -1 B 148~205 mg m -2 day -1 167 mg m -2 day -1 C 91~183 mg m -2 day -1 123 mg m -2 day -1 D 121~209 mg m -2 day -1 173 mg m -2 day -1 E 102~207 mg m -2 day -1 159 mg m -2 day -1 F 70~181 mg m -2 day -1 118 mg m -2 day -1 G 69~259 mg m -2 day -1 127 mg m -2 day -1 5-2-2 Holsen et al., 1991; Lee, 1991; Fang, 1992; Lin et al., 1993 1996 (2000) -122-
(a) Dry depostion flux (mg m -2 day -1 ) 400 300 200 100 Spring Summer Fall Winter 0 A B C D E F G Sites (b) Dry depostion velocity (cm s -1 ) 12 10 8 6 4 2 Spring Summer Fall Winter 0 A B C D E F G Sites 5-2-1 (a) (b) -123-
5-2-1 (mg m -2 day -1 ) 142~209 175 Noll et al., 1990 94.2~299 172 Lee, 1991 111~258 193 Holsen and Noll, 1992 90~267 163 Lin et al., 1993 210~433 328 121~144 132 129~182 147 240~355 279 532~709 607 328~1009 698 573~832 761 94.1~215 155 69.8~208 135 85.0~206 137 133~259 189 1996 2000 V d,tm =K (F T,TM ) (C TSP ) (5-1) V d,tm = (cm s -1 ) K = F T,TM = (mg m -2 day -1 ) C TSP = (µg m -3 ) -124-
5-2-1 (b) A 1.68~6.44 cm s -1 4.06 cm s -1 B 1.53 cm s -1 C 1.50~2.91 cm s -1 1.98 cm s -1 D 1.87~9.81 cm s -1 5.84 cm s -1 E 0.61~6.10 cm s -1 3.10 cm s -1 F 0.81~3.33 cm s -1 2.07 cm s -1 G 0.89~2.38 cm s -1 1.49 cm s -1 5-2-3 1996 2000 Fang (1996) 5-2-2 (cm s -1 ) Tunghai University 6.93 Jongieng Elementary School 9.21 Fang, 1996 Shingang Elementary School 15.6 2.08 0.96 1.19 2.21 2.99 2.69 2.04 1.65 5.17 1.67 0.88 1996 2000-125-
5-2-2 PAHs PAHs PAHs PAHs PAHs 1996 5-2-2 PAHs A PAHs 88.0~190 µg m -2 day -1 136 µg m -2 day -1 B 108~202 µg m -2 day -1 143 µg m -2 day -1 C 63.4~260 µg m -2 day -1 133 µg m -2 day -1 D 94.9~181 µg m -2 day -1 140 µg m -2 day -1 E 99.7~419 µg m -2 day -1 230 µg m -2 day -1 F 88.0~355 µg m -2 day -1 220 µg m -2 day -1 G 83.7~210 µg m -2 day -1 147 µg m -2 day -1 (1996) PAHs (131~194 µg m -2 day -1 ) 400 Dry deposition flux (µg m -2 day -1 ) 300 200 100 0 A B C D E F G Sampling sites 5-2-2 PAHs -126-