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Polybrominated Diphenyl Ethers (PBDEs) In Surface Soils across Five Asian Countries: Levels, Spatial Distribution and Source Contribution Wen-long Li, Wan-Li Ma, Hongliang Jia, Wenjun Hong, Hyo-Bang Moon, Haruhiko Nakata, Nguyen Hung Minh, Ravindra Kumar Sinha, Kai Hsien Chi, Kurunthachalam Kannan, Ed Sverko, and Yi-Fan Li Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.6b04046 • Publication Date (Web): 24 Oct 2016 Downloaded from http://pubs.acs.org on October 27, 2016

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Environmental Science & Technology

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Polybrominated Diphenyl Ethers (PBDEs) In Surface Soils across

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Five Asian Countries: Levels, Spatial Distribution and Source

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Contribution

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Wen-Long Lia, Wan-Li Maa, Hong-Liang Jiab, Wen-Jun Hongb, Hyo-Bang Moonc, Haruhiko Nakatad, Nguyen Hung Minhe, Ravindra Kumar Sinhaf, Kai Hsien Chig, Kurunthachalam Kannanh, Ed Sverkoa, and Yi-Fan Lia,b,i*

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a

International Joint Research Center for Persistent Toxic Substances (IJRC-PTS),

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State Key Laboratory of Urban Water Resource and Environment, School of

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Municipal and Environmental Engineering, Harbin Institute of Technology, Harbin

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150090, China

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b

University, Dalian 116026, China

14 15

c

IJRC-PTS, Department of Marine Sciences and Convergent Technology, Hanyang University, 55 Hanyangdaehak-ro, Sangnok-gu, Ansan city, Gyeonggi-do 426-791,

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Republic of Korea

17 18

d

IJRC-PTS, Graduate School of Science and Technology, Kumamoto University, 2-39-1 Kurokami, Kumamoto 860-8555, Japan

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IJRC-PTS, College of Environmental Science and Engineering, Dalian Maritime

e

Dioxin laboratory, Center for Environmental Monitoring (CEM), Vietnam

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Environmental Administration (VEA), 556 Nguyen Van Cu, Long Bien, Ha Noi,

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Vietnam

23

f

24

g

IJRC-PTS, Department of Zoology, Patna University, Patna 800 005, Bihar, India Institute of Environmental and Occupational Health Sciences, National Yang Ming University, Taipei 112, Taiwan

25 26

h

Wadsworth Center, New York State Department of Health, Department of

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Environmental Health Sciences, School of Public Health, State University of New

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York at Albany, Empire State Plaza, P.O. Box 509, Albany, New York 12201-0509,

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United States

30

i

IJRC-PTS-NA, Toronto, M2N 6X9, Canada

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*Corresponding author: IJRC-PTS, School of Municipal and Environmental

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Engineering, Harbin Institute of Technology, 202 Haihe Road, Nangang District,

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Harbin 150090, Heilongjiang, China.

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ACS Paragon Plus Environment


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Tel. +86-451-8628-9130; Fax: +86-451-8628-9130

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E-mail: [email protected]

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Word count: (Text) 4684+ 2 (Table)*300 + 3 (Figure)*300 = 6184, including text,

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tables and Figures.

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TOC:

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ABSTRACT: A total of 23 PBDE congeners were measured in soil samples collected

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in areas with no known point source (urban/rural/background sites, U/R/B sites) and

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in contaminated areas (brominated flame retardants (BFRs) related industrial and

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e-waste recycling sites) across five Asian countries. The highest PBDE concentrations

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were found in BFRs related industrial and e-waste recycling sites. The concentrations

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of PBDEs in U/R/B sites followed the order of: urban > rural > background sites.

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Total PBDE concentrations were dominated by BDE-209, while BDE-17, -85, -138,

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-191, -204 and -205 were the least abundant compounds. In both urban sites and rural

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sites, the mean concentrations of total PBDEs (∑23BDEs) in soils followed the order

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of: Japan > China > South Korea > India > Vietnam. The concentrations of PBDEs in

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soils were comparable with those reported in other studies. Among the three

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commercial PBDE mixtures, relatively high contribution of commercial penta-BDE

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were observed in Vietnam, whereas deca-BDE was the dominant mixtures

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contributing from 55.8 ± 2.5% to 100.0 ± 1.2% of the total PBDEs in soils collected

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from other four countries. Regression analysis suggested that local population density

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(PD) is a good indicator of PBDEs in soils of each country. Significant and positive

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correlation between soil organic content and PBDE level was observed in Chinese soil

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for most non-deca-BDE homologues with their usage stopped 10 years ago, indicating

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its important role in controlling the re-volatilization of PBDEs from soil and changing

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the spatial trend of PBDE in soil from the primary distribution pattern to the

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secondary distribution pattern, especially when primary emission is ceased.

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KEYWORDS: Polybrominated diphenyl ethers (PBDEs), Surface soil, Spatial

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distribution, Source contributions, Asia

68

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■ INTRODUCTION

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Polybrominated diphenyl ethers (PBDEs) are a group of most widely used brominated

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flame retardants (BFRs) that have been used in electronic equipment, textiles, and

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other materials for over four decades.1-3 The annual global production of PBDEs had

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increased from 1992 (40,000 tones) to 2001 (67,000 tones).4 PBDEs have been

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produced and used in three commercial mixtures: pentabromodiphenyl ether

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(penta-BDE), octabromodiphenyl ether (octa-BDE) and decabromodiphenyl ether

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(deca-BDE). Approximately 46,000, 25,000 and 380,000 tons of commercial

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penta-BDE, octa-BDE and deca-BDE were and will be used in products in the U.S.

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and Canada during 1970 and 2020.5 In Asian countries, the dominated commercial

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product was deca-BDE, with consumption of commercial penta-BDE, octa-BDE, and

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deca-BDE were estimated at 150, 1,500, and 23,000 tons, respectively in 2001.6

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Because of their toxicity, penta- and octa-BDE are now included in the Stockholm

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Convention.7 The deca-BDE mixture has been withdrawn from the U.S. market at the

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end of 2013.8

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PBDEs have been widely detected in the global environments.9-15 In Asia, PBDEs

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were also frequently monitored in South Korea,16-20 Japan,21-23 India,24-27 Vietnam27-29

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and China.30-33 Long-term monitoring of PBDEs in the Great Lakes atmosphere

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suggested that the replacement of the PBDE commercial product by their alternatives

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have not yet become evident.34, 35 After the phase-out of penta-BDE and octa-BDE,

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deca-BDE (BDE-209) has become the dominant contaminant in various environment

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media. For instance, BDE-209 contributed 95.9 ± 7.4% of total PBDE concentrations

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in soils from Northern China.36

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In Asia, the estimated market demand of penta-BDE, octa-BDE and deca-BDE in

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2001 was 2%, 40% and 41% of the world market demand for the three commercial

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products, respectively.6 Several Asian countries are emerging as strong economies

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with the industrial and urban development taking place at an unprecedented rate, with

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increasing production and consumption of PBDEs. Furthermore, these Asian countries

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(China and India, for example) have become a potentially significant new sources of

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PBDEs in the environment due to the import of electronic waste (e-waste) from

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developed countries.37 Approximately 1.5-3.3 million tons of illegal e-waste were

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imported to China annually.38 Another major source of PBDEs was from the

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electronic and chemical manufacturing activities. In Asia, PBDEs were produced

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mainly in the eastern coastal areas of China such as Shandong Province.39-41 No

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management policies or regulations for PBDEs currently exist in China at either

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provincial or central government levels.42 Therefore, monitoring of PBDEs in Asian

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countries is important not only because of their strong economic growth, but also

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because of their potential as a global emission source.

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Asian Soil and Air Monitoring Program (Asia-SAMP)43 is designed to study and

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relate both temporal and spatial trends of POPs and other persistent organic chemicals,

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including PBDEs, in both air and surface soil from five Asian countries (China, India,

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Japan, South Korea, and Vietnam). This study mainly focuses on PBDEs in surface

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soil because (1) soils are still an important reservoir for PBDEs even though

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production of some PBDEs were stopped many years ago; (2) Soils can be secondary

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sources of emissions of PBDEs following regulations on productions and usage of

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these compounds; and (3) Soils can contribute to contamination of air on a local and

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regional scale and therefore monitoring of PBDEs in soil to assess emissions and

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air-soil partitioning is important.

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In this study, we investigated PBDE levels in soils collected from urban, rural and

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background sites (U/R/B sites) across five Asian countries. In addition, soils were

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collected in BFRs related industrial sites (BFR-manufacturing site, F site) and e-waste

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recycling sites (E site) for comparison with the U/R/B sites. A total of 23 PBDE

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congeners (8 homologous from Tri-BDE to Deca-BDE) were measured. Monitoring

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studies of PBDEs in such large areas encompassing several countries is important to

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assess the geographical distribution of these contaminants. Results can be used to

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assess the effectiveness of regulatory measures implemented in Asia. The levels,

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profiles, spatial distributions, source contribution and human health risk of PBDEs

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were investigated in different countries.

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■ MATERIALS AND METHODS

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Sampling. Sampling sites in the 5 Asian countries (Figure S1, Supporting

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Information (SI)) were selected in 82 urban, 80 rural and 10 background locations, as

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well as locations affected by the emissions of industries (10 locations from vicinity of

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a BFR-factory (F) in China) and e-waste recycling activities (10 locations from

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vicinity of two e-waste recycling regions in China, 2 locations near two e-waste

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recycling regions in South Korea, and 1 locations near an e-waste recycling regions in

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Vietnam) (Table S1). Soil samples were collected during the period of September to

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November, 2012. The urban, rural and background area were classified by considering

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the local population density and gross domestic product (GDP). A total of 195

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sampling locations were chosen to collect the soil samples, including 121 from China,

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24 from India, 14 from Japan, 14 from Vietnam and 22 from South Korea.

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Details regarding soil sampling and pretreatment procedures have been reported in

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our previous studies,44, 45 which can also be found in SI. Briefly, each soil sample was

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Soxhlet extracted with acetone and hexane (1:1, v/v) for 24 h. The extracts were

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purified using silica gel column chromatography. Identification and quantification of

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PBDEs was carried out on an Agilent 6890 gas chromatograph/5975 mass 6


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spectrometer in the electron capture negative ionization mode.

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QA/QC and Statistical Analysis. One procedural blank and one native standard

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spiked sample (by using anhydrous sodium sulfate) were simultaneously analyzed

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with each batch of 10 samples. Calibration curves were prepared to calculate the

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concentrations. The levels of PBDEs in the procedural blank were negligible with the

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levels less than 5% of the analyzed concentrations in soil samples. The average

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recoveries of PBDEs in spiked blank samples were in the range of 73 to 95%. The

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average

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13

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respectively. The chromatographic peaks with signal-to-noise (S/N) ratio greater than

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3:1 were integrated. The method detection limits (MDLs) of PBDEs were calculated

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as mean blank values plus 3 times the standard deviation. The MDLs were 0.083 ng/g

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dw for BDE-209 and 0.0010-0.0065 ng/g dw for other PBDEs (Table S2). The values

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below the MDLs were assigned a value half the MDLs for further calculation. The

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concentrations of PBDEs were not corrected for blank concentrations and surrogate

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recoveries. The correlations of PBDE concentrations between two groups were

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considered as statistically significant at p < 0.05. Statistical analyses were performed

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using SPSS V22.0 (IBM SPSS Inc., Chicago, USA) and SigmaPlot V10.0 (Systat

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Software Inc., San Jose, USA).

recoveries

of

13

C12-BDE-209,

13

C10-syn-dechlorane

plus

and

C10-anti-dechlorane plus in soil samples were 81 ± 9%, 83 ± 11% and 85 ± 14%,

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Least Squares Method for PBDE Profile. In order to obtain the percentage

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contribution of the three commercial mixtures to the soil profiles, the observed

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congener profiles were fitted to the profile of the three commercial mixtures by the

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least-squares method,46

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ξ c = ∑ [( f P c i , P + f O c i ,O + f D ci ,d ) − c i ,obs ]2 i

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(1)


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where ci , P , ci ,O and ci , D are the percentage of congener i in the commercial

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penta-BDE, octa-BDE and deca-BDE, respectively (Table S3); ci ,obs is the

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percentage of congener i in the soil samples; f P , fO and f D are the coefficients

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reflect the fraction of commercial penta-BDEs, octa-BDEs and deca-BDEs in the soil

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samples.

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■ RESULTS AND DISCUSSION

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PBDE Concentrations. The summarized statistics for the concentrations of total

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PBDE congeners (∑23BDEs) measured in soil samples from the five Asian countries

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were displayed in Table S4 to Table S9. Generally, PBDE concentrations in soils

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were the highest in e-waste and BFRs related industrial sites (Figure 1). For the five

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countries, total PBDE concentrations was dominated by BDE-209, while BDE-17, -85,

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-138, -191, -204 and -205 were the least abundant congeners with the levels below the

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limit of detection in >50% of the soil samples.

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The descriptive data for PBDE concentrations in Japan (Table S4) showed that

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∑23BDEs is mainly dominated by BDE-209. The concentrations of ∑23BDEs in the

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urban, rural and background sites were 450 ± 370, 160 ± 350 and 22 ± 25 ng/g dw,

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respectively, higher than those found in China, South Korea, Vietnam and India. This

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result may be due to the huge historical consumptions of deca-BDE that ranged from

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3,000 to 10,000 tones/year in Japan during 1986-2001.47

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Table S5 displays descriptive statistics for PBDE concentrations in soils from

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China. Total PBDE concentration is predominated by BDE-209 with the mean

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concentrations of 72 ± 140, 26 ± 54 and 0.66 ± 0.31 ng/g dw, which accounted for

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92.9 ± 5.9%, 90.4 ± 8.9% and 84.9 ± 5.3% of the ∑23BDEs in urban, rural and

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background sites, respectively. The concentration of ∑23BDEs in the urban soils was

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in the range of 0.60 to 800 ng/g dw, with a mean value of 75 ± 140 ng/g dw, which 8


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was lower than that found in Japan, but higher than those found in other three Asian

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countries.

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In South Korea, the concentration of ∑23BDEs in soil samples ranged from 0.95 to

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94 ng/g dw, with the mean value of 16 ± 23 ng/g dw (Table S6). The ∑23BDEs

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concentrations in urban, rural and background sites were 39 ± 36, 10 ± 14 and 1.4 ±

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0.64 ng/g dw, respectively. Among all the PBDE congeners, BDE-209 was the

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dominant congener with the concentrations of 34 ± 35, 8.7 ± 13 and 0.91 ± 0.68 ng/g

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dw in urban, rural and background sites, respectively, followed by BDE-47, -99, -183,

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-206, -207 and -208.

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Table S7 describes the concentrations of PBDEs in soil samples from Vietnam. The

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concentrations of ∑23BDEs in urban, rural and background sites were 1.1 ± 0.96, 0.75

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± 0.51 and 0.23 ng/g dw, respectively, approximately lower by an order of magnitude

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compared with ∑23BDEs concentrations in South Korea. In contrast to the results of

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other countries, BDE-99 was the dominant congener in Vietnam, followed by BDE-47

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and BDE-209.

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As shown in Table S8, the concentrations of BDE-209 in urban and rural sites in

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India were 3.1 ± 4.0 and 0.72 ± 1.1 ng/g dw, respectively, higher than that found in

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Vietnam but lower than those found in other three Asian countries. However, the

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concentrations of ∑22BDEs (excluding 209) in Indian urban sites (0.30 ± 0.25 ng/g dw)

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and rural sites (0.066 ± 0.039 ng/g dw) were lower than those found in all the other 4

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countries.

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Soil samples in the vicinity of BFRs related industrial and e-waste recycling sites in

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China, South Korea and Vietnam were also collected (Table S9). The mean

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concentrations of ∑23BDEs in e-waste recycling sites and BFRs related industrial sites

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(BFR-factory, F) in China were 3,900 ± 5,100 and 6,400 ± 6,700 ng/g dw, respectively,

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significantly higher than those from U/R/B sites (p < 0.001). The proportion of

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BDE-209 to ∑23BDE concentrations in BFRs related industrial and e-waste recycling

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sites in China were very high with the values of 92.8 ± 7.6% and 91.2 ± 5.1%,

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respectively. These results indicate higher pollution levels of BDE-209 in comparison

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to other PBDE congeners, which is in agreement with previous studies48-50 (Table

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S10). In comparison to China, lower levels of PBDEs were detected in e-waste

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recycling sites in South Korea and Vietnam. In Vietnam, the concentrations of PBDEs

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in e-waste recycling sites were much higher than that in urban, rural and background

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sites. For example, the concentrations of BDE-209 in the e-waste recycling site (63

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ng/g dw) was 286 times higher than that found in the urban sites (mean: 0.22 ng/g dw)

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in this country.

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Table S10 summarizes the mean concentrations of BDE-47, -99, -183, -209, total

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PBDEs excluding BDE-209, total PBDEs including BDE-209, and proportion of

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BDE-209 in the surface soils from recent studies around the world. In China, the

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mean concentration of total PBDEs in urban sites (75 ng/g dw) in our study was lower

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than those reported for Northern China (202 ng/g dw),36 but higher than those

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reported from Shanghai (32.5 ng/g dw).51 In the other regional studies on PBDEs in

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China, the mean soil concentrations of BDE-209 were 101 ng/g dw in Kaixian

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County,52 9.48 ng/g dw in Yangtze River Delta,16 62.5 ng/g dw in suburban area of

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Guanzhou,53 and 104 ng/g dw in Yellow River Delta,54 while it was comparable to 28

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ng/g dw in Chinese rural sites obtained from this study. In Vietnam, total PBDE

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concentrations in soils from rice paddies, open burning sites and e-waste recycling

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workshops in Bui Dau were 2.2, 24 and 1,900 ng/g dw, respectively.48 The

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concentrations of total PBDEs in soils collected from urban and agricultural sites

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(0.22 ng/g dw) and e-waste dumping sites (95 ng/g dw) reported earlier24 were

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comparable with those found in our study for the same country (urban: 1.1 ng/g dw;

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e-waste: 68 ng/g dw). In USA, total PBDE concentration ranged from 0.02 to 55.1

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ng/g dw in floodplain soils of the Saginaw River Watershed,55 close to that in Chinese

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rural soil (28 ng/g dw) obtained from this study.

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In agreement with our findings, exceptionally high levels of PBDEs were found in

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BFRs related industrial sites with the mean values of 58,700 ng/g dw from a

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deca-BDE manufacturing factory in China.49 In e-waste recycling areas in China, the

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reported concentrations of total PBDEs were 71.6-5,710 ng/g dw56 and 489-15,400

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ng/g dw in Taizhou,57 168-6,540 ng/g dw in Guiyu,58 13.9-13,300 ng/g dw in

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Qingyuan.50 These PBDE levels were similar to our findings with the total PBDE

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concentrations that ranged from 60 to 14,000 ng/g dw.

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Spatial Distributions. Highest levels of PBDE concentrations were observed in the

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contaminated regions (e-waste recycling and BFRs related industrial sites, Figure 1).

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After years of accumulation, the soils in the BFRs related industrial area and e-waste

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area were highly contaminated by PBDEs, with the concentrations much higher than

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those in urban, rural and background regions. In the U/R/B sites, megacities such as

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Guangzhou and Shanghai in China, and Kyoto in Japan, the soil concentrations of

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BDE-209 exceeded 150 ng/g dw. The overall concentrations of PBDEs in soil

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followed the order of: urban > rural > background sites. This trend can be described as

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urban effect since PBDEs have been used more extensively in urban areas than in

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rural and background areas. This is typical primary distribution pattern,59 “urban

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pulse”60 or urban distribution pattern.61 This kind of distribution pattern was also

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observed for PBDEs in Great Lakes,34, 62 China,63 Kuwait,64 Sweden60 and U.K.65

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In both urban and rural sites, the mean concentrations of ∑23PBDEs in soils

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followed the order of: Japan > China > South Korea > India > Vietnam. This

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distribution of PBDEs may be due to the historical usage of commercial products

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because soils are still an important reservoir for PBDEs even though productions of

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some PBDEs were stopped many years ago. For example, the consumption of

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commercial deca-BDE mixture in Asian countries were 23,000 tons in 2001,6 with

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China (10,000 in 2000)66 South Korea (12,324 in 2002)67 and Japan (2,800 tons in

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2000)47 accounting for the largest proportion of consumption. Based on the soil levels,

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it seems that the consumption of commercial PBDEs in India and Vietnam were low

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in comparison to the other three countries.

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For China, the correlation between the concentrations of PBDE homologues and

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the longitude of sampling location were positive and significant (Table S11),

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especially for the longitude between 84 oE and 125 oE, the correlations were

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significant for all PBDE homologues (r = 0.29 to 0.46, p < 0.01). This longitudinal

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distribution pattern was also reported for PCBs.45 The reason for this distribution

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pattern is that the most developed area in China is along the east coast (such as

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Shanghai City and Tianjin City), resulting in higher consumption and release of

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PBDEs from the consumer products from these source areas. As shown in Figure S2,

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the proportion of BDE-209 decreased with longitude decreased, while the proportion

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of other PBDEs showing a different trend, indicating that BDE-209 was trapped in the

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soil of the source area while other more volatile PBDEs, in comparison to BDE-209,

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can travel longer distance from the source area, which is longitudinal fractionation

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effect, or the typical primary fractionation effect.59

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Co-occurrence among PBDE homologues. Individual PBDE homologues were

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significantly and positively correlated with each other (Figure S3). The correlation

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coefficients ranged from 0.56 to 0.91 (p < 0.001) suggesting their co-occurrence in

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soils and the similar emission pattern among PBDEs. However, their correlation

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coefficients were different among PBDE homologues. The correlation coefficients

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among higher molecular weight homologues (OctaBDE, NonaBDE and DecaBDE)

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were much higher than those between higher molecular weight homologues and lower

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molecular weight homologues, which may be due to the following reasons: (1) the

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ban of penta-BDE, octa-BDE since 2005 while deca-BDE is still used in Asia; (2) the

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diverse composition profiles of the three commercial mixtures;68 (3) their different

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physicochemical property such as logKOA (Table S2), meaning that high molecular

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weight homologues are easier to deposit to soils and lower molecular weight

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homologues tend to re-evaporate into the atmosphere;69,

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microbial degradation of PBDE in soils on the overall congener pattern.71

70

(4) the influence of

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Homologues Profile. The dominant homologue in soil was DecaBDE with higher

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mean and maximum values (Figure 2 and Figure S4). In e-waste recycling and BFRs

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related industrial sites, the homologues in soil decreased from highest brominated

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homologue (DecaBDE) to lowest one (TriBDE). This trend was similar with those in

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the soils collected from an e-waste area50 and a commercial deca-BDE industrial in

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China.72 Interestingly, the levels of DecaBDE in e-waste recycling sites were lower

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than those in BFRs related industrial sites, while lower molecular weight homologues

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showed a different trend (Figure S4(4)), suggesting the greater pollution of

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commercial penta-BDE mixture in e-waste recycling sites, possibly indicating a

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certain portion of those e-wastes treated in the sites was commercial OctaBDE and

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PentaBDE, or/and the production of lower brominated PBDE compounds due to the

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combustion of the e-waste treatment. In U/R/B sites (excluding Vietnam), the

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homologues profiles followed the order of: DecaBDE > NonaBDE > PentaBDE or

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OctaBDE or HeptaBDE > TetraBDE > HexaBDE > TriBDE. These profiles were

317

different from the three commercial penta-BDE, octa-BDE and deca-BDE mixtures.

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318

For example, the predominant homologues in penta-BDE, octa-BDE and deca-BDE

319

were PentaBDE followed by TetraBDE, OctaBDE followed by HeptaBDE, and

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DecaBDE followed by NonaBDE, respectively.68

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Contributions from PBDE commercial mixtures. The PBDE profiles observed in

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present study suggest a combination of the three PBDE commercial mixtures.

323

Modeling results of equation (1) showed significant correlations between the model

324

congener profiles and the measured congener profiles in soils (r = 0.95-0.99, p
0.05).

parameter

influencing

PBDE levels

in

soils.

However,

PBDE

414

The soil organic carbon (SOC) showed no significant influence on the levels of

415

PBDEs for the five Asian countries as a whole (p > 0.05). Interestingly however, the

416

regression coefficients for SOC (d3) for China were significant for most of PBDE

417

homologues with the significant levels at p < 0.05 except for TriBDE (p = 0.10) and

17



418

DecaBDE (p = 0.16) (Tables S12). The non-significant correlation for DecaBDE may

419

be due to the strong primary source of commercial deca-BDE used in China.

420

In summary, currently the most important factor is PD because PBDEs are still

421

being emitted to the environment and there is a net deposition of PBDEs to the soils,

422

thus the spatial trend of PBDE in the 5 countries showed a primary distribution

423

pattern, and the role of SOC or temperature is small at the present stage. However, the

424

greater role of SOC for several PBDE homologues than those for DecaBDE was

425

observed in Chinese soils. The usage of commercial penta-BDE and octa-BDE was

426

stopped in 2006,77 while commercial deca-BDE has still been used at a large amount

427

in China. This trend indicated that SOC is an important factor in controlling the

428

re-volatilization of PBDEs, and changing the spatial trend of PBDE in soil from the

429

primary distribution pattern to the secondary distribution pattern, especially when

430

primary emission is ceased.59

431

■ ASSOCIATED CONTENT

432

Supporting Information

433

Additional tables and additional figures. This material is available free of charge via

434

the Internet at http://pubs.acs.org.

435

■ AUTHOR INFORMATION

436

Corresponding Author

437

*Phone: +86-451-8628-9130. *E-mail: [email protected]

438

Notes

439

The authors declare no competing financial interest.

440

■ ACKNOWLEDGEMENTS

441

This work was supported by the National Natural Science Foundation of China

442

(No. 21277038), the HIT Environment and Ecology Innovation Special Funds (No.

18


Page 18 of 32

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443

EEISF1601) and the Open Project of State Key Laboratory of Urban Water Resource

444

and Environment, Harbin Institute of Technology (No. HCK201533). The authors

445

thank IJRC-PTS colleagues in China, Japan, India, South Korea, and Vietnam for their

446

contributions to this research.

447

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W. W.; Zhang, Z. F.; Li, Y. F., Brominated flame retardants in Chinese air before

711

and after the phase out of polybrominated diphenyl ethers. Atmos. Environ. 2015,

712

117, 156-161 (DOI: 10.1016/j.atmosenv.2015.07.021). 26


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Page 27 of 32


713

(75) Venier, M.; Hites, R. A., Regression Model of Partial Pressures of PCBs, PAHs,

714

and Organochlorine Pesticides in the Great Lakes' Atmosphere. Environ. Sci.

715

Technol. 2010, 44, (2), 618-623.

716 717

(76) Venier, M.; Ma, Y. N.; Hites, R. A., Bromobenzene Flame Retardants in the Great Lakes Atmosphere. Environ. Sci. Technol. 2012, 46, (16), 8653-8660.

718

(77) Zhang, X. L.; Luo, X. J.; Chen, S. J.; Wu, J. P.; Mai, B. X., Spatial distribution

719

and vertical profile of polybrominated diphenyl ethers, tetrabromobisphenol A,

720

and decabromodiphenylethane in river sediment from an industrialized region of

721

South China. Environ. Pollut. 2009, 157, (6), 1917-1923.

722 723

27



Page 28 of 32

724

Table 1. Percentage contributions (%) and significant level of commercial

725

penta-BDEs (fP), octa-BDEs (fO) and deca-BDEs (fD) to the profiles found in soil

726

samples collected across the five countries. Urban sites

Rural sites

Background China

sites

E-waste

sites

Factory sites

fP fO

1.6 ± 1.3 0.0 ± 2.3

NS NS

3.9 ± 1.3 0.0 ± 2.2

** NS

6.9 ± 1.0 3.1 ± 1.7

*** NS

2.0 ± 1.5 0.0 ± 2.6

NS NS

0.6 ± 0.5 3.0 ± 0.9

NS **

fD

98.4 ± 1.0

***

96.1 ± 1.0

***

90.0 ± 0.7

***

98.0 ± 1.1

***

96.5 ± 0.4

***

South Korea fP fO

2.5 ± 1.2 13.3 ± 2.1

NS ***

13.5 ± 1.3 5.2 ± 2.2

*** *

7.8 ± 3.3 36.4 ± 5.6

* ***

0.2 ± 1.3 0.0 ± 2.3

NS NS

fD

84.2 ± 0.9

***

81.3 ± 1.0

***

55.8 ± 2.5

***

99.8 ± 1.0

***

Vietnam fP fO

63.4 ± 5.5 8.4 ± 9.4

*** NS

28.1 ± 4.6 11.3 ± 7.8

*** NS

35.3 ± 5.9 19.5 ± 10.1

*** NS

1.4 ± 0.9 0.0 ± 1.6

NS NS

fD

28.3 ± 4.1

***

60.6 ± 3.5

***

45.2 ± 4.4

***

98.6 ± 0.6

***

Japan fP fO

0.0 ± 1.4 0.0 ± 2.4

NS NS

17.1 ± 2.9 2.1 ± 4.9

*** NS

4.7 ± 1.4 1.3 ± 2.4

** NS

fD

100.0 ± 1.2

***

80.8 ± 2.2

***

94.0 ± 1.1

***

India fP fO

7.9 ± 1.1 4.3 ± 1.9

*** *

12.4 ± 2.5 13.5 ± 4.3

*** **

fD

87.8 ± 0.8

***

74.1 ± 1.9

***

NS: not significant; *: p < 0.05; **: p < 0.01; ***: p < 0.001. 727

28


Page 29 of 32


728

Table 2. Modeling results for slope (a1) and intercept (a0) of the slope and intercept

729

for equation (2). China a1

TriBDE TetraBDE PentaBDE HexaBDE HeptaBDE OctaBDE NonaBDE DecaBDE PBDEs

0.05±0.03 0.15±0.03 0.13±0.03 0.16±0.03 0.18±0.03 0.19±0.03 0.22±0.04 0.25±0.04 0.24±0.04

Japan * *** *** *** *** *** *** *** ***

0.12±0.04 0.26±0.09 0.18±0.08 0.24±0.08 0.25±0.07 0.27±0.08 0.36±0.16 0.46±0.20 0.38±0.16

South Korea * * * ** ** ** * * *

0.05±0.04 0.12±0.06 0.10±0.06 0.21±0.05 0.28±0.05 0.22±0.04 0.27±0.05 0.28±0.07 0.24±0.06

India

Vietnam

NS * * ** *** *** *** ** **

0.11±0.03 0.14±0.03 0.13±0.05 0.20±0.04 0.22±0.05 0.18±0.03 0.15±0.05 0.16±0.08 0.15±0.07

** ** * *** *** *** ** * *

0.13±0.08 0.25±0.08 0.19±0.06 0.08±0.09 0.04±0.06 0.02±0.04 0.04±0.05 0.05±0.06 0.12±0.05

NS ** * NS NS NS NS NS *

*** *** *** *** *** *** *** NS NS

-6.57±0.31 -6.23±0.34 -4.92±0.49 -6.80±0.35 -6.81±0.48 -5.79±0.29 -4.60±0.45 -1.98±0.80 -1.59±0.68

*** *** *** *** *** *** *** * *

-6.69±0.76 -6.38±0.79 -3.85±0.63 -5.25±0.87 -4.70±0.58 -4.28±0.41 -3.48±0.54 -1.77±0.60 -1.59±0.49

*** *** *** *** *** *** *** * **

a0 TriBDE -4.09±0.20 *** -4.44±0.39 *** -5.39±0.32 TetraBDE -4.11±0.27 *** -4.82±0.84 *** -4.18±0.54 PentaBDE -2.61±0.26 *** -2.23±0.77 * -2.48±0.47 HexaBDE -4.40±0.27 *** -5.03±0.74 *** -4.59±0.45 HeptaBDE -4.01±0.26 *** -4.39±0.70 *** -4.53±0.40 OctaBDE -3.68±0.27 *** -4.30±0.80 *** -4.22±0.35 -3.14±0.46 NonaBDE -2.66±0.31 *** -3.24±1.50 * DecaBDE 0.93±0.29 ** -1.04±1.96 NS -0.68±0.63 PBDEs 1.07±0.28 *** 0.03±1.55 NS -0.05±0.49 NS: not significant; *: p < 0.05; **: p < 0.01; ***: p < 0.001.

730

29



731 732

Figure 1. Spatial distributions of BDE-209 and ∑22BDEs (excluding BDE-209) in

733

soil samples across five Asian countries.

734

30


Page 30 of 32

Page 31 of 32


SK(U) VN(U) IN(U) JA(U) CH(U) SK(R) VN(R) IN(R) JA(R) CH(R) SK(B) VN(B) JA(B) CH(B) SK(E) VN(E) CH(E) CH(F) penta octa deca

Proportion

100% 90% 80% 70% 60% 50% 40% 30% 20% 10% 0%

DecaBDE

NonaBDE

OctaBDE

HeptaBDE

HexaBDE

PentaBDE

TetraBDE

TriBDE

735 736

Figure 2. The profiles of PBDE homologues in the urban (U), rural (R), background

737

(B), e-waste (E) and BFRs related industrial sites (BFR-factory, F) regions of South

738

Korea (SK), Vietnam (VN), Japan (JA), China (CH) and India (IN). The profiles of

739

three commercial products (penta, octa and deca-BDE, see reference 68) are also

740

presented for comparison.

741 742 743

31



Page 32 of 32

744

2.5

0.0

-2.5 r = 0.87 p < 0.001

-5.0 -5.0

745

5.0

(a) Samples from China

Modeled ln(C, ng/g dw)

Modeled ln(C, ng/g dw)

5.0

DecaBDE HeptaBDE HexaBDE NonaBDE OctaBDE PentaBDE TetraBDE TriBDE

-2.5 0.0 2.5 Measurement ln(C, ng/g dw)

2.5

0.0

DecaBDE (b) Samples from South Korea HeptaBDE HexaBDE NonaBDE OctaBDE PentaBDE TetraBDE TriBDE

-2.5 r = 0.92 p < 0.001

-5.0

-5.0

5.0

-2.5 0.0 2.5 Measurement ln(C, ng/g dw)

746

Figure 3. Correlations of measured concentrations of PBDE homologues in Chinese

747

soil (a) and in South Korean soil (b) with the modeled values.

748

32


5.0

Polybrominated Diphenyl Ethers (PBDEs) - ACS Publications

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