Polybrominated Diphenyl Ethers (Pbdes) and Heavy Metals in Road Dusts from a Plastic Waste

Polybrominated diphenyl ethers (PBDEs) and heavy metals in road dusts from a plastic waste recycling area in north China: implications for human health Zhenwu Tanga,b, Qifei Huangb*, Yufei Yangb, Zhiqiang Nieb, Jiali Chengc*, Jun Yangd, Yuwen Wanga, Miao Chaia aMOE Key Laboratory of Regional Energy and Environmental Systems Optimization, Environmental Research Academy, North China Electric Power University, Beijing 102206, China bState Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China cNational Institute for Nutrition and Health, Chinese Center for Disease Control and Prevention, Beijing 100021, China dCenter for Environmental Remediation, Institute of Geographic Sciences and Natural Resources Research, Chinese Academy of Sciences, Beijing 100101, China

Lists:

S 1 Non-carcinogenic risk assessment S 2 Tables

Table S1 Input parameters and values used to estimate the average daily dose and hazard quotient in the non-cancer risk assessment Table S2 Summary of reference dose (RfD) and dermal absorption factor (ABS) of heavy metals and PBDEs Table S3 Polybrominated diphenyl ether (PBDE) concentrations (ng g-1 dry wt) in dust samples from the plastic waste recycling area and from other areas Table S4 Means and ranges of individual metal concentration (µg g-1 dry wt) in dusts from the waste plastic recycling area and from other areas Table S5 Pearson’s correlations matrix between the contents of heavy metals and total organic carbon (TOC) in dusts S 3 Figures Fig S1. Plot of PC1 versus PC2 from the principal components analyses of dust samples collected from the waste plastic recycling area. Data for the commercial formulations were taken from a report by La Guardia et al. (2006)

1 S 1 Non-carcinogenic risk assessment

Non-carcinogenic risk assessment. According to the Exposure Factors Handbook (USEPA 2001), the average daily doses

-1 -1 (ADDs) (mg kg day ) through ingestion (ADDingest), dermal contact (ADDdermal), and

inhalation (ADDinhale) for both adults and children were estimated using Eqs. as follows:

-6 ADDingest = Csoil × IngR × EF × ED / BW / AT × 10 , ADDdermal = Csoil × CA × AF × ABS × EF ×

-6 ED / BW / AT × 10 , ADDinhale = Csoil × InhR × EF × ED / PEF / BW / AT, where ADDingest,

ADDdermal and ADDinhale are the daily amounts of exposure to metals through soil ingestion,

dermal contact and inhalation absorption, respectively; Csoil is the concentration of metal in soil; IngR and InhR are the ingestion and inhalation rates of soil, respectively; EF is the exposure frequency; ED is the exposure duration; BW is the body weight of the exposed individual; AT is the time period over which the dose is averaged; PEF is the emission factor;

SA is the exposed skin surface area; and AF is the adherence factor. Values for each factor were selected by using reference standards from the USEPA and real data for Chinese locations, given in Table S1. ABS is the dermal absorption factor, given in Table S2.

The human non-cancer risk effects from metals can be assessed using the hazard quotient

(HQ), which is the ratio of the ADD to the reference dose (RfD, mg kg-1 day-1) of a heavy metal for the same exposure pathway. The values of RfD for each metal are given in Table S2.

2 S 2 Tables

Table S1 Input parameters and values used to estimate the average daily dose and hazard quotient in the non-cancer risk assessment Parameter Definition Unit Value Reference Adult Children IngR Soil ingestion rate mg day-1 100 200 USEPA 1989; 2001 EF Exposure frequency day year-1 350 350 days/year USEPA 1989; 2001 ED Exposure duration day 30 6 USEPA 1989; 2001 BW Average body weight kg 60 15 BMBQTS 2009 AT Average time day 365×30 365×6 USEPA 1989 SA Exposed skin surface m2 4350 1600 BMBQTS 2009 area AF Skin adherence factor mg cm-2 day-1 0.2 0.7 USEPA 2001 InhR Inhalation rate m3 day-1 15 5 BMBQTS 2009 PEF Particle emission factor m3 kg-1 1.36×109 1.36×109 USEPA 1989; 2001

3 Table S2 Summary of reference dose (RfD) and dermal absorption factor (ABS) of heavy metals and PBDEs Ingestion RfD Inhalation RfD Dermal RfD ABS (mg kg-1 day-1) (mg kg-1 day-1) (mg kg-1 day-1) (unitless) As 0.0003 a 0.0000086 a 0.000123 a 0.03 b Cd 0.001 a 0.001 a 0.00001 a 0.14 b Cr 0.003 a 0.000029 a 1.50 a 0.04 b Cu 0.04 c 0.042 c 0.012 c 0.1 b Hg 0.00016 a 0.0000857 a 0.000021 a 0.05 b Pb 0.0035 c 0.00352 c 0.000525 c 0.006 b Sb 0.0004 a 0.000014 a 0.000008 a 0.001 a Zn 0.3 c 0.3 c 0.06 c 0.02 b BDE-47 0.0001 d 0.0001 j 0.0001j 1 j BDE-99 0.0001 e 0.0001 j 0.0001 j 1 j BDE-153 0.0002 f 0.0002 j 0.0002 j 1 j BDE-209 0.007 g 0.007 j 0.007 j 1 j Penta-BDE 0.002 h 0.002j 0.002 j 1 j Octa-BDE 0.003 i 0.003 j 0.003 j 1 j a BMBQTS 2009 b Chen et al. 2015 c Wei et al. 2015 d USEPA IRIS 2008a e USEPA IRIS 2008b f USEPA IRIS 2008c g USEPA IRIS 2008d h USEPA IRIS 1990a i USEPA IRIS 1990b j In this study, the inhalation RfD and dermal RfD of BDE-47, 99, 153 and BDE-209, penta-BDE, octa- BDE are assumed to be equal to its corresponding ingestion RfD, respectively; the values of ABS were all assumed to be equal to 1.

4 Table S3 Polybrominated diphenyl ether (PBDE) concentrations (ng g-1 dry wt) in dust samples from the plastic waste recycling area and from other areas Location Sampling times Sampling surroundings BDE 209 ΣPBDEs Reference mean (min-max) mean (min-max) Wen’an, China November 2011 Road dusts from waste plastic recycling area 1430 (2.67–10424) 1541 (3.23–10640) This study Wenling, China October 2013 Outdoor dusts from near workshops in e-waste 4050 (960–10470) 7060 (1980– Xu et al. 2015 recycling region 15000) Wenling, China October 2013 Dusts from main road in e-waste recycling region 103 (82–124) 103 (82–124) Guiyu, China February and September, Dusts from road near intersection in e-waste recycling 271 (101–463) 2265 (2040–2420) Leung et al. 2004 region 2011 Guiyu, China February and September, Dusts from main road in e-waste recycling region 399 (45.6–633) 2190 (1030–3070) 2004 Gurao, China February and September, Road dusts from town 25.3 (10.4–42.1) 328 (182–502) 2004 Shantou, China February and September, Outdoor dusts from Shantou University campus 104 (103–105) 396 (312–473) 2004 Taizhou, China November 2011 Outdoor dusts from e-waste recycling area 23790 (164– 24595 (199– Jiang et al. 240106) 244672) 2014 Qingyuan, October 2006; October, Outdoor dusts from e-waste recycling area 2416 (113–18997) 3312 (212–25881) Wang et al. China 2007 2010 Eastern China July, 2009 Dusts from urban roads in Suzhou, Nantong and 322(4.01–1439) 330 ( 4.21–1471 ) Shi et al. 2014 Wuxi Shanghai, December 2012 Outdoor dusts from a typical industrialized and 51.0 (1.61–294.8) 73.4 (6.71–342.1) Wu et al. 2015 China urbanized area

5 6 Table S4 Means and ranges of individual metal concentration (µg g-1 dry wt) in dusts from the waste plastic recycling area and from other areas Location Sampling Sampling As Cd Cr Cu Hg Pb Sb Zn Reference times surroundings Wen’an, China November Road dusts from 10.1 (5.36– 0.50 (0.15– 112 (68.9– 54.7 (20.7– 0.15 (0.02– 71.8 (18.7– 10.6 (1.19– 186 (58.3– This study 2011 plastic recycling 13.7) 3.04) 160) 554) 0.90) 589) 196) 2025) area Nanjing, China January, Dusts from trunk – – 139 (67– 238 (57– – 113 (43– – 307 (120– Liu et al. 2014 2011 roads 391) 4237) 832) 720) Massachusetts, 2008 Road dusts – – 95 (0–530) 240 (0– – 73 (0–1639) – 240 (35– Apeagyei et al. USA 2130) 1208) 2011 Wenling, October Dusts from main – 0.80 (0.70– 29.7 (26.5– 45.4 (42.2– – 97.2 (91.9– – 89.7 (85.3– Xu et al. 2015 China 2013 road in e-waste 0.90) 32.9) 48.6) 103) 94.1) recycling site Wenling, October Outdoor dust – 4.8 (ND– 69.9 (13.6– 867 (307– – 366–6960 27.1 (ND– 257 (96.6– China 2013 from sites near 10.5) 179) 1790) 112) 523) workshops Guiyu, China December Dusts from e- – 5.00 a 15.0 a 740 a – 1000 a – 580 a Leung et al. 2004 waste recycling 2008 site Xi’an, China October Dusts from 14.5 (6.0– – 160 (88.9– 74.2 (36.2– – 176 (87.5– – 463 (184– Lu et al. 2014 2011 nursery schools 38.3) 751) 162.7) 593) 1838) 39 cities in 1995–2011 Road dusts from 17.8 (3.51– 3.67 (0.08– 153 (52.2– 144 (22.7– 0.66 (0.03– 221 (21.9– – 602 (69.6– Lei et al. 2012 China urban streets 48.8) 15.4) 420) 604) 1.60) 901) 1832) Seven cities in – Dusts from urban – 2.03 (1.17– 109 (51.3– 150 (95.0– – 239 (53.3– – 656 (295– Wei and Wang China roads 3.77) 167) 197) 408) 1450) 2010

7 Kavala, Greece July 2002 Street dusts from 13.7 (ND– 0.20 (ND– 232 (50– 173 (58– 0.20 (ND– 387 (75– – 355 (200– Christoforidis to June Urban area 85) 1.2) 692) 508) 3.3) 2500) 558) and Stamatis 2003 2009 Beijing, China February to Street dusts from – 0.723 84.7 (32.0– 69.9 (5.46– – 105 (16.7– – 222 (57.4– Wei et al. 2015 May 2010 urban areas (0.130–5.01) 227) 623) 2450) 908) a Data derived from graph

8 Table S5 Pearson’s correlations matrix between the contents of heavy metals and total organic carbon (TOC) in dusts As Cd Cr Cu Hg Pb Sb Zn Cd 0.323 1 Cr -0.192 0.384* 1 Cu 0.318 0.821** 0.486** 1 Hg 0.086 0.138 -0.036 0.024 1 Pb 0.144 0.322 0.266 0.354 -0.017 1 Sb 0.337 0.792** 0.435* 0.980** 0.035 0.337 1 Zn 0.307 0.836** 0.476** 0.993** 0.045 0.358* 0.977** 1 TOC -0.304 -0.036 0.140 -0.077 -0.234 -0.082 -0.144 -0.039 * p < 0.05; ** p < 0.01

9 S 3 Figures

W10 W8 W6 W9W7

Fig. S1 Plot of PC1 versus PC2 from the principal components analyses of dust samples collected from the waste plastic recycling area. Data for the commercial formulations were taken from a report by La Guardia et al. (2006)

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