Σ 40. Levels Distribution and Possible Sources of Polybrominated Diphenyl Ethers in River Sediments from an Electronic Waste Recycling Area

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1 ENVIRONMENTAL SCIENCE Vol 32 No 4 Apr GC-NCI-MS 41 PBDEs Σ 40 PBDEs BDE ~ 161 ng g ng g -1 BDE ~ 958 ng g ng g -1 BDE % ~ 96 0% 74 4% PBDEs PBDEs 3 3% ~ 25 8% 0 01% ~ 14 1% PBDEs PBDEs deca-bde deca-bde octa-bde PBDEs X131 A Levels Distribution and Possible Sources of Polybrominated Diphenyl Ethers in River Sediments from an Electronic Waste Recycling Area WANG Xue-tong 1 WANG Fei 1 JIA Jin-pan 1 LI Yuan-cheng 1 SUN Yang-zhao 2 WU Ming-hong 1 SHENG Guo-ying 1 3 FU Jia-mo Institute of Environmental Pollution and Health School of Environmental and Chemical Engineering Shanghai University Shanghai China 2 Ministry of Environmental Protection of the People s Republic of China Beijing China 3 State Key Laboratory of Organic Geochemistry Guangzhou Institute of Geochemistry Chinese Academy of Sciences Guangzhou China Abstract The concentrations of 41 polybrominated diphenyl ethers PBDEs in the river sediments from Luqiao were analyzed by GC-NCI-MS The objectives of this study were to understand the contents spatial distribution and sources The Σ PBDEs 40 excluding BDE209 concentrations in sediments sampled were in the range of to 161 ng g -1 with a mean of 22 5 ng g -1 and the concentrations of BDE209 were from 0 36 to 958 ng g -1 with a mean of 148 ng g -1 Deca-BDE was the most predominant in 9 PBDE homologues in most of samples accounting for 38 4% -96 0% with an average of 74 4% followed by nona-bdes and hepta-bdes accounting for 3 3% -25 8% and 0 01% -14 1% respectively Significant correlations were observed among all of PBDEs congeners which suggested these PBDEs might have the similar sources The homologue composition of PBDEs and hierarchical cluster analysis HCA showed that most of sampling sites were mainly polluted by deca-bde formulation and others polluted by deca-bde and octa-bde formulations Compared to other studies from different countries and regions the PBDEs concentrations in the present study were at a medium-to-low level But it should be concerned that a few of sampling sites were highly contaminated by point sources Key words electronic waste sediment polybrominated diphenyl ethers PBDEs distribution hierarchical cluster analysis HCA source polybrominated diphenyl ethers PBDEs PBDEs deca-bde octa-bde penta-bde t 83 3% 11 1% BAC32B BAA24B04 S ~ wangxt0323@ yahoo com cn

2 % ~ ~ h PBDEs 44 g /100 g 6% 2 PBDEs 24 h R-215 BUCHI Milli-Q Millipore PBDEs 41 PBDE PBDEs PBDEs PBDEs BDE PBDEs BDE PBDEs PBDEs BDE PBDEs 3 PBDEs BDE PBDEs BDE PBDEs BDE PBDEs BDE203 PBDEs BDE ~ 9 PBDE BDE209 Accustandard BDE50 13 C 12 -BDE209 CIL PCB209 Accustandard PBDEs g 10 g mL 39 0 ~ 10 cm 50 ml / ml GC-MS Fig 1 1 Schematic graph of sampling sites of sediment in Luqiao 150 ml h / 1 4 Agilent 6890N Agilent ml min -1 PBDEs ~ PBDEs DB-5MS 30 m 0 25 mm 0 25 μm J&W Scientific min 20 min min 2 min min 5 min min 20 min min PBDEs ~ BDE209 DB-5MS m 0 25 mm 0 25 μm J &W Scientific 90 1 min 10 min min 20

3 min min Σ PBDEs > 500 ng g NCI 22 Σ PBDEs ng g SIM PBDEs ~ PBDEs m / z BDE209 m / z C 12 -BDE209 m / z PCB209 m / z TOC ng g -1 10% HCl TOC Σ PBDEs ng g -1 BDE50 13 C 12 -BDE209 PCB % ~ 105 7% n = ng g -1 < Σ PBDEs < < 15% 3 ng g -1 LODs PBDEs ~ PBDEs PBDEs ~ 0 05 ng g -1 BDE ng g PBDEs BDE50 PBDEs 13 PBDEs C 12 -BDE209 80% PBDEs 1 6 PBDEs 10 SPSS18 0 PBDEs LOD 1 /2 LOD 2 BDE % ~ 96 0% PBDEs 74 4% 16 BDE209 PBDEs 80% 6 90% 94 5% 25 6% ~ 100% 61 9% 41 BDE47 BDE49 BDE99 BDE153 BDE183 BDE203 BDE206 BDE207 BDE208 BDE209 > 90% BDE203 BDE206 BDE207 BDE208 BDE % BDE7 BDE8 BDE10 BDE11 BDE12 BDE13 BDE30 BDE32 BDE33 BDE126 BDE155 < 50% PBDEs Σ PBDEs 40 BDE209 BDE PBDEs ~ 161 ng g ng g -1 BDE ~ 958 ng g -1 PBDEs 0 01% ~ 148 ng g PBDEs 41 PBDEs Σ PBDEs 41 < 10 PBDEs 9 PBDEs 2 2 PBDEs BDE209 50% BDE209 50% 49 9% 43 4% PBDEs 3 3% ~ 25 8% 14 0% Saytex 102E PBDEs 2 49% PBDEs ~ PBDEs 14 1% 2 2% 3 PBDEs

4 Fig 2 2 PBDEs Relative compositions of PBDEs homologues in river sediments PBDEs 39 3 PBDEs 13 hierarchical cluster analysis HCA deca-bde 2 15 octa-bde 3 penta-bde PBDEs 1 24 PBDEs deca-bde 24 deca-bde 2 15 deca-bde octa-bde penta-bde 2 3 PBDEs TOC PBDEs TOC PBDEs α = 0 05 p < 0 03 PBDEs BDE7 BDE138 BDE190 BDE207 TOC α = 0 05 p < 0 05 PBDEs TOC α = 0 05 p > PBDEs 14 Scheldt 15 Vero PBDEs Clyde Fig 3 PBDEs Tree diagram for river sediment samples and PBDEs technical formulations

5 Tokyo Great Lake 23 ~ Busan 22 PBDEs 1 PBDEs / ng g - 1 Table 1 Concentrations of PBDEs in sediments all over the world dw / ng g - 1 Σ PBDEs 1 BDE209 Clyde 16 1 ~ ~ Scheldt ~ ~ Vero ~ ~ Tokyo ~ ~ Busan ~ Great Lake ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ nd 2 ~ ~ ~ ~ Σ PBDEs BDE209 2 nd 3 1 PBDEs Σ 40 PBDEs BDE ~ 161 ng g ng g -1 BDE ~ 958 ng g ng g -1 2 PBDEs PBDEs BDE % ~ 96 0% 74 4% 94 5% BDE209 50% PBDEs PBDEs 3 3% ~ 25 8% 0 01% ~ 14 1% 3 deca-bde deca-bde octa-bde PBDEs PBDEs 4 PBDEs 1 Law R J Allchin C R de Boer J et al Levels and trends of brominated flame retardants in the European environment J Chemosphere J Wang Z Ma X D Lin Z S et al Congener specific distributions of polybrominated diphenyl ethers PBDEs in sediment and mussel Mytilus edulis of the Bo Sea China J Chemosphere J Zhao G F Wang Z J Dong M H et al PBBs PBDEs and PCBs levels in hair of residents around e-waste disassembly sites in Zhejiang Province China and their potential sources J Science of the Total Environment Luo Y Luo X J Lin Z et al Polybrominated diphenyl ethers in road and farmland soils from an e-waste recycling region in Southern China Concentrations source profiles and potential dispersion and deposition J Science of the Total Environment Wen S Yang F Li J G et al Polychlorinated dibenzo-p-dioxin and dibenzofurans PCDD / Fs polybrominated diphenyl ethers PBDEs and polychlorinated biphenyls PCBs monitored by tree bark in an e-waste recycling area J Chemosphere Zhao G F Zhou H D Wang D H et al PBBs PBDEs and PCBs in foods collected from e-waste disassembly sites and daily intake by local residents J Science of the Total Environment J

6 J J Gerecke A C Hartmann P C Heeb N V et al Anaerobic degradation of decabromodiphenyl ether J Environmental Science and Technology Nose K Hashimoto S Takahashi S et al Degradation pathways of decabromodiphenyl ether during hydrothermal treatment J Chemosphere Guardia M J Hale R C Harvey E et al Detailed polybrominated diphenyl ether PBDE congener composition of the widely used penta- octa- and deca-pbde technical flameretardant mixtures J Environmental Science and Technology Vane C H Ma Y J Chen S J et al Increasing polybrominated diphenyl ether PBDE contamination in sediment cores from the inner Clyde Estuary UK J Environmental Geochemistry and Health Verslycke T A Vethaak A D Arijs K et al Flame retardants surfactants and organotins in sediment and mysid shrimp of the Scheldt estuary The Netherlands J Environmental Pollution Eljarrat E Labandeira A Marsh G et al Decabrominated diphenyl ether in river fish and sediment samples collected downstream an industrial park J Chemosphere Xiang C H Luo X J Chen S J et al Polybrominated diphenyl ethers in biota and sediments of the Pearl River Estuary South China J Environmental Toxicology and Chemistry Minh N H Isobe T Ueno D et al Spatial distribution and vertical profile of polybrominated diphenyl ethers and hexabromocyclododecanes in sediment core from Tokyo Bay Japan J Environmental Pollution Li Q Z Yan C Z Luo Z X et al Occurrence and levels of polybrominated diphenyl ethers PBDEs in recent sediments and marine organisms from Xiamen offshore areas China J Marine Pollution Bulletin Chen S J Gao X J Mai B X et al Polybrominated diphenyl ethers in surface sediments of the Yangtze River Delta Levels distribution and potential hydrodynamic influence J Environmental Pollution Moon H B Kannan K Choi M et al Polybrominated diphenyl ethers PBDEs in marine sediments from industrialized bays of Korea J Marine Pollution Bulletin Song W Ford J C Li A et al Polybrominated diphenyl ethers in the sediments of the Great Lakes 1 Lake Superior J Environmental Science and Technology Song W Li A Ford J C Sturchio N C et al Polybrominated diphenyl ethers in the sediments of the Great Lakes 2 Lakes Michigan and Huron J Environmental Science and Technology Song W Ford J C Li A et al Polybrominated diphenyl ethers in the sediments of the Great Lakes 3 Lakes Ontario and Erie J Environmental Science and Technology

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