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Occurrence, Profiles, and Toxic Equivalents of Chlorinated and Brominated Polycyclic Aromatic Hydrocarbons in E-waste Open Burning Soils Chiya Nishimura1, Yuichi Horii2, Shuhei Tanaka1,3, Kwadwo Ansong Asante4, Florencio Ballesteros Jr.5, Pham Hung Viet 6, Takaaki Itai7, Hidetaka Takigami8, Shinsuke Tanabe7, Takashi Fujimori1,9* 1. Department of Environmental Engineering, Graduate School of Engineering, Kyoto University, 6158540, Kyoto, Japan 2. Center for Environmental Science in Saitama, 347-0115, Saitama, Japan 3. Department of Technology and Ecology, Graduate School of Global Environmental Studies, Kyoto University, 606-8501, Kyoto, Japan 4. CSIR Water Research Institute, P.O. Box AH 38, Achimota, Accra, Ghana 5. College of Engineering, University of the Philippines Diliman, Quezon City 1101, Metro Manila, the Philippines 6. Center for Environmental Technology and Sustainable Development, Hanoi University of Science, 334 Nguyen Trai, Hanoi, Vietnam

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7. Center for Marine Environmental studies, Ehime University, 790-8577, Matsuyama, Japan 8. Center for Material Cycles and Waste Management Research, National Institute for Environmental Studies, 305-8506, Tsukuba, Japan 9. Department of Global Ecology, Graduate School of Global Environmental Studies, Kyoto University, 615-8540, Kyoto, Japan *To whom correspondence should be addressed. E-mail: [email protected] Contents: 10 Pages, 5 Tables, 2 Figures.

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Table S1 Concentrations (ng/g) of PAHs in soil samples. Abbrev number iation of rings Nap 2 Ace 3 Fle 3 Phe 3 Ant 3 Flu 4 Pyr 4 BaA 4 Chr 4 BbF 5 BkF 5 BaP 5 DA 5 IP 6 BP 6

Naphthalene Acenaphthene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Benz[a]anthracene Chrysene Benzo[b]fluoranthene Benzo[k]fluoranthene Benzo[a]pyrene Dibenz[a,h]anthracene Indeno[1,2,3-cd]pyrene Benzo[g,h,i]perylene ∑15 PAHs (ng/g) LMW PAHs HMW PAHs LMW/HMW Phe/Ant ratio Flu/Pyr ratio Σ 2-ring PAHs Σ 3-ring PAHs Σ 4-ring PAHs Σ 5-ring PAHs Σ 6-ring PAHs Σ10 New Dutch List PAHs (ng/g)

Control

GH-1

GH-2

PHI-1

PHI-2

VN-1

VN-2

LOD

2.0 ND. ND. 8.9 ND. ND. 1.7 1.0 ND. 14 0.63 1.8 ND. 0.13 0.079 30 11 19 0.57 NC. 0 2.0 8.9 2.7 16 0.21 15

84 ND. 8.6 150 ND. ND. 120 15 11 4.2 ND. ND. ND. ND. ND. 390 240 150 1.6 NC. 0 84 160 140 4.2 ND. 260

51 ND. 11 180 30 69 160 31 32 37 25 43 2.3 5.2 30 710 270 430 0.63 6.1 0.43 51 220 290 110 35 500

920 110 360 510 ND. 470 80 190 100 44 15 23 20 14 1.9 2900 1900 960 2.0 NC. 5.9 920 980 840 100 16 2200

1100 83 410 1100 ND. 190 290 310 230 120 0.10 35 ND. 22 84 4000 2700 1300 2.1 4300 0.66 1100 1600 1000 150 110 3100

570 6.0 390 3800 110 ND. 700 270 390 840 6.2 51 11 5.9 ND. 7200 4900 2300 2.2 36 0 570 4300 1400 910 5.9 5200

420 8.7 250 1800 87 ND. 690 630 920 1400 34 110 57 66 73 6500 2600 3900 0.65 21 0 420 2200 2200 1600 140 4100

0.36 0.05 0.15 0.24 0.03 0.56 0.10 0.04 0.08 0.05 0.05 0.02 0.03 0.03 0.39

※LOD: limit of detection. ND.: not detected. NC.: not calculated. ※LMWPAHs：Low Molecular Weight PAHs including 2-3 ring PAHs. HMW PAHs：High Molecular Weight PAHs including 4-6 ring PAHs. ※10 PAHs New Dutch List: Naphtalene, Acenaphthene, Phenanthrene, Fluoranthene, Benzo[a]anthracene, Chrysene, Benzo[a]pyrene, Benzo[g,h,i]perylene, Benzo[b+k]fluoranthene, Indeno[1,2,3-cd]pyrene.

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Table S2 Concentrations (ng/g) of Cl-PAHs in soil samples. N.D., not detected. 9-ClFle 9-ClPhe 2-ClAnt 9-ClAnt 3,9-Cl2Phe 1,9-Cl2Phe 9,10-Cl2Ant 9,10-Cl2Phe 3-ClFlu 8-ClFlu 1-ClPyr 3,9,10-Cl3Phe 1,5,9-Cl3Ant 5,7-Cl2Flu 3,8-Cl2Flu 3,4-Cl2Flu Cl2Pyr-1 Cl2Pyr-2 6-ClChr 7-ClBaA 1,5,9,10-Cl4Ant Cl3-Pyr 6,12-Cl2Chr 7,12-Cl2BaA Cl4Pyr 6-ClBaP Σ26 Cl-PAHs (ng/g)

Control N.D. 0.022 0.049 N.D. N.D. N.D. N.D. N.D. 0.008 N.D. 0.017 N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. 0.096

GH-1 0.27 6.8 1.1 2.8 1.9 0.16 1.4 1.4 1.6 0.61 4.2 0.28 N.D. N.D. 0.26 N.D. 0.40 0.52 0.44 1.8 0.035 0.42 0.15 0.078 0.36 1.9 29

GH-2 0.31 7.4 1.3 0.48 1.6 0.21 0.12 1.4 2.2 0.86 2.3 0.27 N.D. N.D. 0.24 N.D. 0.12 0.11 0.25 0.68 0.020 0.14 0.043 0.023 0.25 0.61 21

PHI-1 1.6 34 4.5 1.9 28 N.D. N.D. 21 2.4 1.3 4.5 0.20 N.D. N.D. 0.33 N.D. 0.44 0.58 1.0 3.1 0.83 0.65 0.071 0.046 0.31 0.89 110

PHI-2 1.7 27 7.1 35 6.4 0.80 31 3.5 6.8 3.1 47 0.42 N.D. N.D. 0.90 N.D. 7.0 9.6 3.2 34 0.069 4.7 0.72 1.0 1.6 22 250

VN-1 4.1 300 24 320 150 N.D. 580 96 45 17 350 3.5 N.D. N.D. 5.1 N.D. 70 92 52 410 2.5 58 11 20 17 170 2,800

VN-2 4.4 200 18 230 62 7.3 310 42 40 14 280 5.1 N.D. N.D. 5.7 N.D. 51 64 32 240 1.8 39 7.7 11 16 97 1,800

limit of detection 0.011 0.008 0.009 0.006 0.009 0.009 0.011 0.008 0.007 0.004 0.007 0.009 0.011 0.009 0.009 0.013 0.019 0.009 0.010 0.015 0.010 0.012 0.011 0.011 0.021 0.027

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Table S3 Concentrations (ng/g) of Br-PAHs in soil samples. N.D., not detected. 9-BrPhe 1-BrAnt 2-BrAnt 9-BrAnt 1,5-Br2Ant 9,10-Br2Ant 2,6-Br2Ant 1-BrPyr 7-BrBaA 7,11-Br2BaA 7,12-Br2BaA 5,7-Br2BaA 4,7-Br2BaA 6-BrBaP Σ14 Br-PAHs (ng/g)

Control N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. ND.

GH-1 2.1 1.9 0.043 0.10 3.7 3.0 0.38 0.47 0.072 N.D. N.D. N.D. N.D. 0.17 12

GH-2 1.3 1.0 0.052 0.035 1.7 1.4 0.13 0.17 0.013 N.D. N.D. N.D. N.D. 0.012 5.8

PHI-1 10 10 0.14 0.058 19 17 2.4 0.61 0.062 N.D. 0.11 N.D. N.D. 0.014 60

PHI-2 3.9 3.4 0.14 0.33 10 9.5 1.5 1.8 0.37 N.D. 0.091 N.D. N.D. 0.18 32

VN-1 91 89 1.1 6.2 140 130 25 22 6.3 N.D. 0.77 0.10 0.38 6.3 520

VN-2 15 11 0.29 3.7 16 16 3.0 12 3.7 N.D. 0.12 N.D. N.D. 2.0 84

limit of detection 0.006 0.012 0.014 0.004 0.014 0.006 0.006 0.010 0.006 0.011 0.014 0.014 0.016 0.018

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Table S4 Relative potencies to 2,3,7,8-tetrachloro-p-dibenzodioxin (REPTCDD) of individual PAH and Cl-/Br-PAH congeners (Villeneuve et al., 2002; Horii et al., 2009), and toxic equivalencies (pg-TEQ/g) calculated using the REPTCDD in soil samples. REPTCDD Naphthalene NA Acenaphthene NA Fluorene NA Phenanthrene NA Anthracene NA Fluoranthene NA Pyrene NA Benzo[a]anthracene 1.4E-06 Chrysene 1.6E-06 Benzo[b]fluoranthene 4.0E-06 Benzo[k]flooranthene 1.1E-04 Benzo[a]pyrene 1.3E-06 Dibenz[a,h]anthracene 4.0E-06 Indeno[1,2,3-cd]pyrene 1.3E-05 Benzo[g,h,i]perylene NA TEQ ∑7PAHs-TCDD(pg TEQ/g) 9-ClFle NA 9-ClPhe NA 2-ClAnt NA 9-ClAnt NA 3,9-Cl2Phe NA 1,9-Cl2Phe NA 9,10-Cl2Ant NA 9,10-Cl2Phe NA 3-ClFlu NA 8-ClFlu NA 1-ClPyr NA 3,9,10-Cl3Phe NA 1,5,9-Cl3Ant 5,7-Cl2Flu 3,8-Cl2Flu 3,4-Cl2Flu Cl2Pyr-1 Cl2Pyr-2 6-ClChr 0.000026 7-ClBaA 0.0000063 1,5,9,10-Cl4Ant Cl3-Pyr 6,12-Cl2Chr NA 7,12-Cl2BaA NA Cl4Pyr 6-ClBaP NA TEQ Σ2 Cl-PAHs (pg TEQ/g) 9-BrPhe NA 1-BrAnt 2-BrAnt 9-BrAnt NA 1,5-Br2Ant 9,10-Br2Ant NA 2,6-Br2Ant 1-BrPyr NA 7-BrBaA 0.000021 7,11-Br2BaA NA 7,12-Br2BaA NA 5,7-Br2BaA NA 4,7-Br2BaA 0.000023 6-BrBaP NA TEQ Σ2 Br-PAHs (pg TEQ/g)

Control

GH-1

GH-2

PHI-1

PHI-2

VN-1

VN-2

0.0014 NC 0.055 0.070 0.0024 NC 0.0016

0.020 0.018 0.017 NC NC NC NC

0.044 0.051 0.15 2.7 0.056 0.0092 0.068

0.27 0.16 0.18 1.6 0.030 0.081 0.18

0.44 0.36 0.48 0.011 0.045 NC 0.29

0.38 0.62 3.4 0.68 0.067 0.043 0.077

0.88 1.5 5.4 3.8 0.15 0.23 0.86

0.13

0.055

3.1

2.5

1.6

5.2

13

NC NC

0.012 0.012

0.0065 0.0043

0.026 0.020

0.082 0.21

1.4 2.6

0.84 1.5

NC

0.023

0.011

0.046

0.30

3.9

2.4

NC

0.0015

0.00028

0.0013

0.0078

0.13

0.078

NC 0

NC 0.0015

NC 0.00028

NC 0.0013

NC 0.0078

0.0088 0.14

NC 0.078

※NA: not able to calculate REP; dose-response relationship insufficient for estimate. ※NC: not able to calculate TEQ; the compound was not be detected. ※ - : Aryl hydrocarbon receptor activity bioassay was not conducted.

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Table S5 Relative potencies to benzo[a]pyrene (REPBaP) of individual PAH and Cl-/Br-PAH congeners (Ohura et al., 2007, 2009) and toxic equivalencies (pg TEQ/g) calculated using the REPBaP in soil samples. REPBaP Naphthalene Acenaphthene Fluorene Phenanthrene 0.004 Anthracene 0.01 Fluoranthene 0.01 Pyrene 0.05 Benzo[a]anthracene 1.4 Chrysene 2.5 Benzo[b]fluoranthene Benzo[k]flooranthene Benzo[a]pyrene 1 Dibenz[a,h]anthracene Indeno[1,2,3-cd]pyrene Benzo[g,h,i]perylene TEQ∑7PAHs-BaP (pg TEQ/g) 9-ClFle 9-ClPhe 0.03 2-ClAnt 0.10 9-ClAnt 0.03 3,9-Cl2Phe 0.32 1,9-Cl2Phe 0.12 9,10-Cl2Ant 0.20 9,10-Cl2Phe 0.16 3-ClFlu 0.17 8-ClFlu 0.18 1-ClPyr 0.10 3,9,10-Cl3Phe 0.77 1,5,9-Cl3Ant 5,7-Cl2Flu 3,8-Cl2Flu 5.70 3,4-Cl2Flu Cl2Pyr-1 Cl2Pyr-2 6-ClChr 2.10 7-ClBaA 0.83 1,5,9,10-Cl4Ant Cl3-Pyr 6,12-Cl2Chr 0.03 7,12-Cl2BaA 0.10 Cl4Pyr 6-ClBaP 0.09 TEQ Σ17 Cl-PAHs (pg TEQ/g) 9-BrPhe 0.02 1-BrAnt 0.01 2-BrAnt NA 9-BrAnt 0.01 1,5-Br2Ant 9,10-Br2Ant NA 2,6-Br2Ant 1-BrPyr 0.04 7-BrBaA 0.84 7,11-Br2BaA 0.06 7,12-Br2BaA 0.09 5,7-Br2BaA 0.02 4,7-Br2BaA 0.77 6-BrBaP 0.002 TEQ Σ9 Br-PAHs (pg TEQ/g)

Control

GH-1

GH-2

PHI-1

PHI-2

VN-1

VN-2

0.59 NC NC 1.4 24 NC

10 NC NC 97 340 480

12 5.0 11 130 730 1,300

34 NC 78 67 4,500 4,200

72 0.042 32 250 7,300 9,500

250 18 NC 580 6,300 16,000

120 15 NC 580 15,000 38,000

31

NC

720

390

580

860

1,900

56

930

2,900

9,200

18,000

24,000

55,507

0.011 0.082 NC NC NC NC NC 0.022 NC 0.028 NC

3.4 1.8 1.4 10 0.31 4.7 3.8 4.4 1.8 7.0 3.5

3.7 2.2 0.24 8.7 0.42 0.41 3.6 6.1 2.6 3.9 3.5

17 7.6 1.0 150 NC NC 55 6.8 3.9 7.5 2.6

13 12 18 34 1.6 100 9.2 19 9.3 79 5.4

150 41 160 820 NC 1900 260 127 51 590 45

98 30 120 330 15 1000 110 110 42 470 65

NC

25

23

31

86

480

540

NC NC

16 25

8.8 9.5

35 43

111 472

1800 5600

1100 3300

NC NC

0.074 0.13

0.022 0.038

0.036 0.076

0.36 1.6

5.3 33

3.9 19

NC 0.14 NC NC

2.9 110 0.68 0.32

0.91 78 0.42 0.17

1.3 360 3.4 1.7

32 1,000 1.3 0.56

260 12,000 30 15

150 7,600 5.1 1.9

NC

0.017

0.0058

0.010

0.054

1.0

0.62

NC NC NC NC NC NC NC NC

0.31 1.0 NC NC NC NC 0.0058 2.3

0.12 0.19 NC NC NC NC 0.0004 0.90

0.40 0.87 NC 0.16 NC NC 0.0005 6.6

1.2 5.2 NC 0.14 NC NC 0.0061 8.5

14 89 NC 1.1 0.032 4.9 0.21 160

8.1 52 NC 0.18 NC NC 0.067 68

※NA: not able to calculate REP; dose-response relationship insufficient for estimate. ※NC: not able to calculate TEQ; the compound was not be detected. ※ - : Aryl hydrocarbon receptor activity bioassay was not conducted.

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Figure S1 Photographs of sampling locations in this study: (a) Duong Quang, Vietnam, (b)Accra, Ghana (c), Caloocan, Philippines, and (d) Bui Dau, Vietnam.

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2 2

1 8

8

1

1

9

7

2

8

3 7

2

6

3

7

4 6

3

5

6

4

10

5

12

1

9

4

4 5

5

6

6

4

4

10 5

11

2

10

3

9 4

8 7

6

5

benzo[a]pryrene (BaP)

13

14

9

5 6 7

7

6

9

Dibenz[a,h]anthracene (DA)

11 10 7

12

8

2

3

10 9 8

4 5

9

Benzo[b]fluoranthene 1 BbF

10

11

2 3

8

12

12

5

10

1

4

6

11

12

11

3

Benzo[k]fluoranthene (BkF)

1

4

6

2 3

12 4 5

8

3

1

11

7

Fluoranthene (Flu)

10

6

7

4 5

8

2

12

11

4

10

10

Anthracene (Ant) 1

Benz[a]anthracene (BaA)

1

5

3

2

12

3

2

8

Chrysene (Chr)

2 9

6

3

4

5

1

9

7

Phenanthrene (Phe)

9

6

7

Pyrene (Pyr)

2

1

3

8

1

7

2

10

3 9

8

Fluorene (Fle)

8

8

1

11

2

7

5

Acenaphthene (Ace)

Naphthene (Nap)

3

1

10

9

6

7

Indeno[1,2,3-cd]pyrene (IP)

4

9 8 7

5 6

Benzo[g,h,i]perylene (BP)

Figure S2 Structures, substitution positions, and abbreviations of 15 polycyclic aromatic hydrocarbons (PAHs), including 7 parent PAHs, measured in this study.

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Reference Ohura, T., Morita, M., Makino, M., Amagai, T., Shimoi, K., 2007. Aryl hydrocarbon receptor-mediated effects of chlorinated polycyclic aromatic hydrocarbons. Chem. Res. Toxicol. 20, 1237-1241. Ohura, T., Sawada, K., Amagai, T., Shinomiya, M., 2009. Discovery of novel halogenated polycyclic aromatic hydrocarbons in urban particulate matters: occurrence, photostability, and AhR activity. Environ. Sci. Technol. 43, 2269-2275. Horii, Y., Khim, J.S., Higley, E.B., Giesy, J.P., Ohura, T., Kannan, K., 2009. Relative potencies of individual chlorinated and brominated polycyclic aromatic hydrocarbons for induction of aryl hydrocarbon receptor-mediated responses. Environ. Sci. Technol. 43, 2159-2165.

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