Seasonal trends of atmospheric PAHs in five Asian megacities and source detection using suitable biomarkers

1 2 3 Supporting information: Seasonal trends of atmospheric PAHs in five Asian megacities and source detection using suitable biomarkers 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Mahua Saha 1, Dusmant Maharana 1, Rina Kurumisawa 2, Hideshige Takada 2, Geok Bee Yeo 2, Andrea C. Rodrigues 1, BadalBhattacharya 3, Hidetoshi Kumata 4, Tomoaki Okuda 5, Kebin He 6, Yongliang Ma 6,Fumiyuki Nakajima 7, Mohamad Pauzi Zakaria 8, Duong Hoang Giang 9, Pham Hung Viet 9 1 Chemical Oceanography Division, CSIR-National Institute of Oceanography, Dona Paula, Goa 403 004, India 2 Laboratory of Organic Geochemistry, Tokyo University of Agriculture and Technology, Fuchu, Tokyo 183 8509, Japan 3 Institute of Ecotoxicology and Environmental Sciences, Salt Lake, Kolkata 700097, West Bengal, India 4 Tokyo University of Pharmacy and Life Sciences, 1432-1 Horinouchi, Hachioji, Tokyo 192-0392, Japan 5 Department of Applied Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan 6 School of Environment, Tsinghua University, Beijing 100084, China 7 The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan 8 Department of Environmental Sciences, Faculty of Environmental Studies, Universiti Putra Malaysia, 43400 UPM, Serdang, Selangor Darul Ehsan, Malaysia. 9 Research Center for Environmental Technology and Sustainable Development, Hanoi University of Science, Hanoi, Vietnam 1

Table S1 Sampling Information on Air samples on preliminary survey in Asia City (district) Sampe code Sampling date Air Temperature TSP* Location type (ºC) (µg/m 3 ) Cordinate Japan Fuchu Tokyo (summer) Jul. 31, 2001 29.4 19 University Campus N 35.684818 E 139.484156 Japan Fuchu Tokyo (winter) Nov. 20, 2001 9.5 77 University Campus N 35.684818 E 139.484156 India Kolkata Circular Road Dec.9th, 2004 20.8 162 Roadside N 22.528139 E 88.359233 India Kolkata Park circus Dec.11th, 2004 20.4 183 Roadside N 22.538147 E 88.365944 Malaysia Klang Klang Jul. 20, 2004 ~30 45 Roadside N 3.036167 E 101.433333 Malaysia Kuala Lumpur KL-center Jul. 21, 2004 ~30 80 Roadside N 3.151583 E 101.694555 Vitenam Ho Chi Minh City HCMC-1 May 17, 2004 ~30 207 Roadside not available not available Vitenam Ho Chi Minh City HCMC-2 May 18, 2004 ~30 156 Roadside N 10.790611 E 106.697472 Cambodia Kratie Kratie Sep. 9, 2004 ~30 64 Remote site N 12.486666 E 106.016166 Cambodia Phnom Penh Phnom Penh Sep.11, 2004 ~30 87 Roadside N 11.544666 E 104.928138 *Total suspended particles

Table S2. Distribution of PAHs in series of PUFs and Particles in air sample collected by High-volume air sampler* Concentration of PAH (ng/m 3 ) Series of PUF Gas** Particulates*** Total**** 1st 2nd 3rd 4th Phe 31.23 9.58 0.91 0.055 41.77 0.16 41.93 Anth 1.72 0.47 0.05 0.012 2.26 0.03 2.29 3-MP 1.87 0.08 0.00 0.003 1.96 0.02 1.97 2-MP 2.61 0.09 0.00 0.005 2.71 0.03 2.74 9-MP 1.22 0.04 0.00 0.003 1.26 0.01 1.28 1-MP 1.36 0.03 0.00 0.003 1.39 0.02 1.41 Fluo 6.57 0.00 0.00 0.002 6.57 0.30 6.87 Pyr 3.42 0.00 0.00 0.002 3.42 0.22 3.64 BaA n.d. n.d. n.d. n.d. n.d. 0.15 0.15 Chry 0.34 n.d. n.d. n.d. 0.34 0.33 0.67 BbF n.d. n.d. n.d. n.d. n.d. 0.41 0.41 BF n.d. n.d. n.d. n.d. n.d. 0.44 0.44 BeP n.d. n.d. n.d. n.d. n.d. 0.41 0.41 BaP n.d. n.d. n.d. n.d. n.d. 0.33 0.33 Pery n.d. n.d. n.d. n.d. n.d. 0.07 0.07 IndPy n.d. n.d. n.d. n.d. n.d. 0.42 0.42 BghiP n.d. n.d. n.d. n.d. n.d. 0.47 0.47 Cor n.d. n.d. n.d. n.d. n.d. 0.17 0.17 % PAH in individual PUFs 1st 2nd 3rd 4th Phe 74.8 22.9 2.2 0.1 Anth 76.1 21.0 2.4 0.5 3-MP 95.5 4.1 0.2 0.2 2-MP 96.3 3.4 0.1 0.2 9-MP 96.8 2.8 0.1 0.3 1-MP 97.8 1.9 0.1 0.2 Fluo 99.9 0.0 0.0 0.0 Pyr 99.9 0.1 0.0 0.0 BaA n.d. n.d. n.d. n.d. Chry 100 n.d. n.d. n.d. BbF n.d. n.d. n.d. n.d. BF n.d. n.d. n.d. n.d. BeP n.d. n.d. n.d. n.d. BaP n.d. n.d. n.d. n.d. Pery n.d. n.d. n.d. n.d. IndPy n.d. n.d. n.d. n.d. BghiP n.d. n.d. n.d. n.d. Cor n.d. n.d. n.d. n.d. *Air sample was collected at FS Tama of TUAT, Tokyo, Japan on Aug.4th - 5th (20 hours), 1999; AverageAir temperature : 27 o C **Sum of concentrations of PAHs in 1st to 4th PUF ***PAHs in particles collected on quartz filter (Pallflex membrane filter 2500QAT-UP) ****sum of concentrations of PAHs in gas and particulate phases

Table S3. PAH concentrations (ng/m 3 ) in particulate and gas phases in air samples collecte from Asian countries Japan Tokyo (summer) Tokyo (winter) Gas Particulate Total %Particulate Gas Particulate Total %Particulate Phe 2.641 0.199 2.84 7% 2.297 0.402 2.70 15% Anth 0.039 0.024 0.06 39% 0.227 0.000 0.23 0% 3-MP 0.437 0.009 0.45 2% 0.241 0.060 0.30 20% 2-MP 0.608 0.013 0.62 2% 0.273 0.086 0.36 24% 9-MP 0.314 0.010 0.32 3% 0.198 0.058 0.26 23% 1-MP 0.344 0.009 0.35 3% 0.153 0.054 0.21 26% Fluo 2.060 0.110 2.17 5% 0.387 0.742 1.13 66% Pyr 0.955 0.087 1.04 8% 0.324 0.759 1.08 70% BaA 0.017 0.036 0.05 68% 0.017 0.883 0.90 98% Chry 0.091 0.088 0.18 49% 0.022 1.458 1.48 99% BbF 0.005 0.062 0.07 93% 0.001 1.396 1.40 100% BF 0.007 0.150 0.16 95% 0.001 1.152 1.15 100% BeP 0.005 0.090 0.10 95% 0.001 1.028 1.03 100% BaP 0.002 0.056 0.06 97% 0.001 1.310 1.31 100% Pery 0.002 0.006 0.01 77% 0.000 0.210 0.21 100% IndPy 0.003 0.101 0.10 97% 0.001 1.246 1.25 100% BghiP 0.003 0.127 0.13 97% 0.001 1.735 1.74 100% Cor 0.002 0.099 0.10 98% 0.001 1.333 1.33 100% T-PAH 7.5 1.3 8.8 14% 4.1 13.9 18.1 77% 12 PAHs 5.8 1.1 7.0 16% 3.3 12.1 15.4 79% HMW-PAHs 0.03 0.69 0.71 96% 0.01 9.20 9.21 100% India Circular Road Park circus Gas Particulate Total %Particulate Gas Particulate Total %Particulate Phe 202.1 9.8 211.9 5% 374.5 14.3 388.8 4% Anth 21.7 1.4 23.1 6% 44.8 2.6 47.4 6% 3-MP 39.9 3.7 43.6 8% 48.9 2.8 51.6 5% 2-MP 46.1 4.8 51.0 9% 56.4 3.6 60.0 6% 9-MP 34.3 3.7 38.0 10% 42.3 2.9 45.3 6% 1-MP 26.4 2.9 29.4 10% 33.4 2.4 35.8 7% Fluo 39.9 17.1 57.1 30% 85.4 24.6 110.0 22% Pyr 44.6 24.3 68.9 35% 79.9 28.9 108.8 27% BaA 1.6 6.2 7.8 79% 1.5 14.2 15.7 90% Chry 1.6 10.6 12.3 87% 4.9 19.9 24.8 80% BbF 0.2 8.1 8.3 98% 0.9 18.4 19.4 95% BF 0.1 6.3 6.4 98% 1.1 13.5 14.6 92% BeP 0.2 7.4 7.5 98% 1.1 16.8 17.9 94% BaP 0.1 7.0 7.2 98% 0.8 16.8 17.6 96% Pery 0.0 1.3 1.3 100% 0.2 2.6 2.8 93% IndPy 0.1 6.3 6.4 99% 0.6 13.0 13.6 96% BghiP 0.2 9.9 10.1 98% 1.0 19.3 20.3 95% Cor 0.1 6.8 6.9 99% 0.4 11.5 11.8 97% T-PAH 459 138 597 23% 778 228 1006 23% 12 PAHs 312 114 427 27% 596 202 799 25% HMW-PAHs 1.01 51.8 52.8 98% 5.89 109 115 95%

Table S3 (cont.) Malaysia Klang KL center Gas Particulate Total %Particulate Gas Particulate Total %Particulate Phe 49.51 0.94 50.45 2% 127.8 1.6 129.4 1% Anth 13.46 0.27 13.72 2% 38.7 0.4 39.1 1% 3-MP 17.86 0.28 18.14 2% 39.8 0.7 40.5 2% 2-MP 19.29 0.40 19.70 2% 42.8 0.9 43.7 2% 9-MP 16.17 0.25 16.41 2% 36.3 0.6 37.0 2% 1-MP 9.61 0.19 9.80 2% 21.9 0.5 22.4 2% Fluo 15.41 0.94 16.35 6% 27.2 2.4 29.5 8% Pyr 19.26 1.24 20.50 6% 34.9 4.0 38.9 10% BaA 0.86 1.04 1.90 55% 1.3 2.6 3.9 66% Chry 1.22 1.20 2.42 50% 1.6 2.9 4.5 64% BbF 0.07 1.11 1.18 94% 0.1 2.3 2.3 97% BF 0.06 0.82 0.88 93% 0.1 1.5 1.6 96% BeP 0.05 1.17 1.22 96% 0.1 2.5 2.6 97% BaP 0.02 0.97 1.00 98% 0.05 2.3 2.4 98% Pery 0.00 0.15 0.15 98% 0.0 0.4 0.4 97% IndPy 0.02 0.98 0.99 98% 0.0 1.9 2.0 98% BghiP 0.04 2.24 2.28 98% 0.1 5.2 5.2 99% Cor 0.03 1.35 1.37 98% 0.1 3.6 3.7 99% T-PAH 162.9 15.5 178 9% 372.8 36.2 408.9 9% 12 PAHs 100.0 12.9 113 11% 231.9 29.4 261.3 11% HMW-PAHs 0.29 8.64 8.92 97% 0.43 19.3 19.75 98% Vietnam HCMC center 1 HCMC center 2 Gas Particulate Total %Particulate Gas Particulate Total %Particulate Phe 165.7 1.7 167.4 1% 82.3 0.4 82.7 1% Anth 36.6 0.5 37.1 1% 18.0 0.1 18.1 1% 3-MP 41.1 0.5 41.6 1% 15.2 0.1 15.3 1% 2-MP 47.7 0.6 48.3 1% 17.5 0.1 17.7 1% 9-MP 48.9 0.6 49.5 1% 17.0 0.1 17.1 1% 1-MP 29.1 0.4 29.5 1% 10.5 0.1 10.5 1% Fluo 125.5 4.6 130.1 4% 34.4 1.3 35.7 4% Pyr 185.3 8.8 194.1 5% 47.5 2.4 49.9 5% BaA 4.2 2.1 6.3 33% 1.9 0.9 2.8 32% Chry 5.4 2.4 7.9 31% 2.9 1.1 4.0 29% BbF 0.2 3.7 3.9 94% 0.3 1.9 2.1 87% BF 0.2 3.2 3.4 94% 0.30 1.5 1.82 83% BeP 0.2 4.9 5.0 97% 0.30 2.0 2.3 87% BaP 0.1 5.0 5.1 98% 0.3 1.1 1.4 81% Pery 0.0 0.8 0.8 99% 0.0 0.2 0.2 81% IndPy 0.1 5.6 5.8 98% 0.2 2.3 2.5 92% BghiP 0.2 16.2 16.5 99% 0.6 5.9 6.6 90% Cor 0.2 13.4 13.6 99% 0.6 5.1 5.7 90% T-PAH 690.8 75.1 766 10% 250 26.8 277 10% 12 PAHs 523.8 58.8 583 10% 189 21.0 210 10% HMW-PAHs 1.20 52.1 53.30 98% 2.52 19.9 22.4 89%

Table S3 (cont.) Cmbodia Kratie Phnom Penh Gas Particulate Total %Particulate Gas Particulate Total %Particulate Phe 12.17 0.15 12.32 1% 63.0 0.8 63.8 1% Anth 2.38 0.02 2.40 1% 11.6 0.2 11.8 1% 3-MP 3.39 0.04 3.42 1% 17.1 0.1 17.2 1% 2-MP 4.23 0.05 4.28 1% 20.9 0.2 21.1 1% 9-MP 4.03 0.05 4.08 1% 22.2 0.2 22.4 1% 1-MP 2.70 0.03 2.73 1% 14.3 0.1 14.5 1% Fluo 7.18 0.21 7.39 3% 42.0 1.5 43.6 4% Pyr 7.64 0.27 7.91 3% 44.7 1.9 46.6 4% BaA 0.88 0.18 1.06 17% 3.9 1.4 5.3 27% Chry 1.22 0.24 1.47 17% 6.3 2.1 8.4 25% BbF 0.15 0.45 0.60 74% 0.5 3.8 4.3 89% BF 0.19 0.29 0.48 60% 0.7 3.4 4.1 83% BeP 0.09 0.35 0.44 79% 0.4 3.4 3.8 91% BaP 0.04 0.25 0.28 87% 0.3 2.4 2.7 91% Pery 0.00 0.03 0.04 89% 0.0 0.4 0.5 89% IndPy 0.02 0.43 0.45 95% 0.2 4.2 4.5 95% BghiP 0.04 0.61 0.65 94% 0.3 6.5 6.9 95% Cor 0.02 0.40 0.42 95% 0.2 4.3 4.5 95% T-PAH 46.4 4.0 50.4 8% 249 37.1 286 13% 12 PAHs 32.0 3.4 35.4 10% 174 31.7 206 15% HMW-PAHs 0.56 2.77 3.32 83% 2.60 28.1 30.7 92%

26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 Figure SI 1. Seasonal variation of % particulate of several PAH species (bottom) with air temperature (top). Air samples (gas and particulate phases) were collected in Fuchu campus of Tokyo University of Agriculture and Technology (TUAT) from June to November 2001. 2

48 49 50 51 52 Figure SI 2. PAHs profile of the five Asian metropolitan cities: (a) Tokyo, (b) Beijing, (c) Kolkata, (d) Hanoi, (e) Kuala Lumpur 53 54 55 56 57 58 59 60 3

61 62 63 64 65 66 Figure SI 3. Seasonal changes in hopane profile of aerosols from five mega cities, a) Tokyo, b) Beijing, c) Kolkata, d) Hanoi, e) Kuala Lumpur, and comparison with that in different source materials f) wood soot, g) coal soot and h) Automobile soot 4

67 68 69 70 71 Figure SI 4. Seasonal variation of C30 17α/C30 17β ratios in (a) Tokyo, (b) Beijing, (c) Kolkata, (d) Hanoi, (e) Kuala Lumpur 72 73 74 75 76 77 78 5