STOTEN-17363; No of Pages Science of the Total Environment xxx (2015) xxx–xxx Contents lists available at ScienceDirect Science of the Total Environment journal homepage: www.elsevier.com/locate/scitotenv Flame retardant emission from e-waste recycling operation in northern Vietnam: Environmental occurrence of emerging organophosphorus esters used as alternatives for PBDEs Hidenori Matsukami a,b,⁎, Nguyen Minh Tue c,d, Go Suzuki a, Masayuki Someya e, Le Huu Tuyen d, Pham Hung Viet d, Shin Takahashi c,f, Shinsuke Tanabe c, Hidetaka Takigami a,b a Center for Material Cycles and Waste Management Research, National Institute for Environmental Studies (NIES), 16-2 Onogawa, Tsukuba 305-8506, Japan Graduate School of Frontier Sciences, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa 277-8563, Japan Center for Marine Environmental Studies (CMES), Ehime University, 2-5 Bunkyo-cho, Matsuyama 790-8577, Japan d Centre for Environmental Technology and Sustainable Development (CETASD), Hanoi University of Science, 334 Nguyen Trai, Hanoi, Viet Nam e Tokyo Metropolitan Research Institute for Environmental Protection, 1-7-5 Shinsuna Koto, Tokyo 136-0075, Japan f Center of Advanced Technology for the Environment, Faculty of Agriculture, Ehime University, 3-5-7 Tarumi, Matsuyama 790-8566, Japan b c H I G H L I G H T S G R A P H I C A L A B S T R A C T • Open storage and burning of e-waste contributed to emission of FRs • Types of FRs currently in emission are shifting in response to regulations of PBDEs • Emerging PFRs were detected in soils and sediments around e-waste recycling area • Presence of alternatives for PBDEs should be regarded as a risk factor a r t i c l e i n f o Article history: Received 17 December 2014 Received in revised form February 2015 Accepted February 2015 Available online xxxx Editor: Adrian Covaci Keywords: Organophosphorus flame retardants Tetrabromobisphenol A Polybrominated diphenyl ethers E-waste recycling Open storage Open burning a b s t r a c t Three oligomeric organophosphorus flame retardants (o-PFRs), eight monomeric PFRs (m-PFRs), tetrabromobisphenol A (TBBPA), and polybrominated diphenyl ethers (PBDEs) were identified and quantified in surface soils and river sediments around the e-waste recycling area in Bui Dau, northern Vietnam Around the e-waste recycling workshops, 1,3-phenylene bis(diphenyl phosphate) (PBDPP), bisphenol A bis(diphenyl phosphate) (BPA-BDPP), triphenyl phosphate (TPHP), TBBPA, and PBDEs were dominant among the investigated flame retardants (FRs) The respective concentrations of PBDPP, BPA-BDPP, TPHP, TBBPA and the total PBDEs were 6.6–14000 ng/g-dry, b2–1500 ng/g-dry, 11–3300 ng/g-dry, b 5–2900 ng/g-dry, and 67–9200 ng/g-dry in surface soils, and 4.4–78 ng/g-dry, b 2–20 ng/g-dry, 7.3–38 ng/g-dry, 6.0–44 ng/g-dry and 100–350 ng/g-dry in river sediments Near the open burning site of e-waste, tris(methylphenyl) phosphate (TMPP), (2ethylhexyl)diphenyl phosphate (EHDPP), TPHP, and the total PBDEs were abundantly with respective concentrations of b 2–190 ng/g-dry, b 2–69 ng/g-dry, b3–51 ng/g-dry and 1.7–67 ng/g-dry in surface soils Open storage and burning of e-waste have been determined to be important factors contributing to the emissions of FRs The environmental occurrence of emerging FRs, especially o-PFRs, indicates that the alternation of FRs addition ⁎ Corresponding author at: Center for Material Cycles and Waste Management Research, National Institute for Environmental Studies (NIES), 16-2 Onogawa, Tsukuba 305-8506, Japan E-mail address: matsukami.hidenori@nies.go.jp (H Matsukami) http://dx.doi.org/10.1016/j.scitotenv.2015.02.008 0048-9697/© 2015 Elsevier B.V All rights reserved Please cite this article as: Matsukami, H., et al., Flame retardant emission from e-waste recycling operation in northern Vietnam: Environmental occurrence of emerging organophosphorus esters used as alterna , Sci Total Environ (2015), http://dx.doi.org/10.1016/j.scitotenv.2015.02.008 H Matsukami et al / Science of the Total Environment xxx (2015) xxx–xxx in electronic products is shifting in response to domestic and international regulations of PBDEs The emissions of alternatives from open storage and burning of e-waste might become greater than those of PBDEs in the following years The presence and environmental effects of alternatives should be regarded as a risk factor along with ewaste recycling © 2015 Elsevier B.V All rights reserved Introduction Electronic waste, commonly known as e-waste, constitutes the most rapidly growing waste problem worldwide E-waste amounts have been increasing because of the increased ownership and shortened lifespan of electronic products E-waste is generated globally at a rate of approximately 40 million tons per year (Huisman et al., 2008) E-waste originates from electronic products containing valuable and reusable materials such as noble metals and plastics Recycling of e-waste has been recognized as the most appropriate strategy for e-waste disposal (Scharnhorst et al., 2005; Rousis et al., 2008) E-waste is generated in economically developed regions and is exported to economically developing regions as secondhand products (Widmer et al., 2005; Terazono and Yoshida, 2008; Shinkuma and Nguyen, 2009) The hazard of e-waste lies in the high content of toxic substances including heavy metals and flame retardants (FRs) that pose both environmental and human health risks (Robinson, 2009) Nevertheless, they are then processed in uncontrolled and primitive recycling operations that might include toner-sweeping, cracking and dumping of cathode ray tubes, open burning of insulated copper wires, and acidstripping of circuit boards to extract gold (The Basel Action Network and Silicon Valley Toxics Coalition, 2002) Recycling of ewaste in economically developing regions has caused severe environmental contamination by FRs, such as polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) (Wong et al., 2007; Leung et al., 2007; Bi et al., 2007; Luo et al., 2007, 2009; Tue et al., 2010, 2013; Labunska et al., 2013, 2014, 2015) Appropriate strategies and policies for e-waste recycling in economically developing countries or regions need to be improved to reduce and control the risk of FRs contamination to local environment and public health The information of FRs emission caused by improper recycling operation in developing countries and regions remains limited This information is rather crucial for assessing the contamination status of local ecosystem and for the green development of e-waste recycling area in the future Therefore, we undertook environmental investigations of FRs around the e-waste recycling area in Bui Dau, Hung Yen province, northern Vietnam Due to the contamination of the indoor environment in ewaste recycling workshops, dust ingestion has been estimated to be an important exposure pathway of PBDEs (Tue et al., 2013) The levels of PBDEs in human tissues from e-waste recycling residents in Bui Dau have been found to be among the highest ever reported (Tue et al., 2010) However, the current status of environmental emissions of FRs from e-waste recycling operations has not been elucidated Environmental occurrence of FRs was regarded as indicators of contaminations derived from e-waste recycling because FRs are incorporated into polymeric materials for electronic products to meet fire safety standard requirements by passing standardized fire tests (European Flame Retardants Association, 2008) The various types of FRs have been used depending on the application and fire safety requirements Among polymeric materials, brominated flame retardants (BFRs) and organophosphorus flame retardants (PFRs) are present in great abundance According to The Chemical Daily of Japan (2005), the total consumption of FRs in 2004 in Japan was approximately 190,000 tons, of which BFRs accounted for 39%, whereas PFRs accounted for 15% (The Chemical Daily of Japan, 2005) In Europe, the total consumption of FRs in 2006 was approximately 465,000 tons, of which BFRs accounted for 10%, whereas PFRs accounted for 20% (Van der Veen and de Boer, 2012) PBDEs were extremely common FR mixtures before 2004 Each commercial formulation of PBDE technical mixtures, Penta- BDE, Octa-BDE, and Deca-BDE was incorporated into different polymeric materials such as high-impact polystyrene (HIPS), acrylonitrile–butadiene–styrene (ABS), wire and cable insulation, and electrical and electronic connectors (WHO, 1994) In the last decade, Penta-BDE and Octa-BDE have been gradually banned world widely (UNEP, 2009) and Deca-BDE has been gradually phased out in many countries (Dodson, et al., 2012), because of their persistence, bioaccumulation, and potentially toxic effects (Eriksson et al., 2002; Darnerud, 2003; Branchi et al., 2003; Viberg et al., 2004) Tetrabromobisphenol A (TBBPA) is a current-use high production volume BFR, with similar applications to PBDEs which is not regulated It is mainly used in printed circuit boards as a reactive agent and in ABS as an additive (WHO, 1995; de Wit et al., 2010) PFRs are chemical additives that have been used in widely diverse combustible products Halogen-free PFRs such as triphenyl phosphate (TPHP), (methylphenyl)diphenyl phosphate (MPDPP), (2-ethylhexyl)diphenyl phosphate (EHDPP), tris(methylphenyl) phosphate (TMPP), and tris(dimethylphenyl) phosphate (TDMPP) are also used as lubricants and plasticizers Chlorinated PFRs such as tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP) and tris(1,3dichloroisopropyl) phosphate (TDCIPP) are used as FRs in polyurethane form Restrictions and bans on the production and new usage of PBDEs have engendered an increase of those monomeric PFR (m-PFR) applications (Pakalin et al., 2007; Van der Veen and de Boer, 2012) Because of the semi-volatility of m-PFRs, emerging oligomeric PFRs (o-PFRs) such as 1,3-phenylene bis(diphenyl phosphate) (PBDPP), bisphenol A bis(diphenyl phosphate) (BPA-BDPP), and 1,3-phenylene bis[di(2,6dimethylphenyl) phosphate)] (PBDMPP) are widely used today in plastics of poly(phenylene oxide)/HIPS and polycarbonate/ABS blends (Syracuse Research Corporation, 2006; Pakalin et al., 2007; Rossi and Heine, 2007) Higher thermal stability and lower volatility of those oPFRs compared to m-PFRs make the former ideal for use in applications that demand high processing temperatures (Pawlowski and Schartel, 2007) Particularly in electronic housings, PBDPP, BPA-BDPP, and PBDMPP are used as alternatives to Deca-BDE Although several studies have elucidated the emissions of FRs to the outdoor environment in the e-waste recycling area in China (Wong et al., 2007; Leung et al., 2007; Luo et al., 2007, 2009), the current status of the emissions of FRs, especially o-PFRs, via e-waste recycling operations has not been considered The present study investigated the emissions of three o-PFRs (PBDPP, BPA-BDPP, and PBDMPP), eight m-PFRs (TPHP, MPDPP, EHDPP, TMPP, TDMPP, TCEP, TCIPP, and TDCIPP), TBBPA, and PBDEs to surface soils and river sediments around e-waste recycling area in Vietnam The current status of their emissions around the e-waste recycling workshops and the sites for open burning of insulated copper wires was elucidated Materials and methods 2.1 Sample collection The study area was an informal e-waste recycling area in Bui Dau, Hung Yen province, northern Vietnam This area had small rural communes with 283 households and approximately 1000 people as of January 2012 (Suzuki et al., 2013) Recycling operations were family based and took place on a small scale in the backyards of homes, often within 20 m distance from living area The main recycling process included recovery of metals and plastics not only by collection, storage, and manual dismantling in workshops as well as shredding electronic housings into chips from e-waste such as disposed computers, TVs, video players, phones, and printers, but also from open burning to Please cite this article as: Matsukami, H., et al., Flame retardant emission from e-waste recycling operation in northern Vietnam: Environmental occurrence of emerging organophosphorus esters used as alterna , Sci Total Environ (2015), http://dx.doi.org/10.1016/j.scitotenv.2015.02.008 H Matsukami et al / Science of the Total Environment xxx (2015) xxx–xxx recover copper wires at footpaths in rice paddies as well as washing wire residues along the river since the early 2000s Other details related to the area have been presented elsewhere (Tue et al., 2010, 2013; Suzuki et al., 2013) A map of Bui Dau and sampling sites of surface soils and river sediments are shown in Fig In January 2012, surface soil samples (0–5 cm) were collected from the footpaths around the rice fields (n = 19, SS-1 to SS-19), the open burning sites (n = 3, SS-20 to SS-22), and the workshops (n = 10, SS-23 to SS-32) River sediment samples were collected from the upstream area (RS-1), the e-waste recycling area (n = 3, RS-2 to RS-4), and the downstream area (n = 4, RS-5 to RS-8) Each sample comprised five subsamples and was collected with a stainless-steel shovel into a zip-locked polyethylene bag from an area of approximately 10 m2 All samples were air-dried and manually homogenized with a wooden hammer after removal of pebbles, weeds, and twigs Air-dried samples were transferred to a stainless-steel sieve (b2.0 mm) covered with a steel lid and were shaken manually Sieved samples were collected and stored in amber glass bottles at −20 °C until chemical analysis 2.2 Materials Native TPHP, MPDPP, and TCEP were purchased from Tokyo Chemical Industry Co., Ltd (Tokyo, Japan) Native EHDPP was purchased from Fluka Chemie AG (Buchs, Switzerland) Native TMPP, TCIPP, and TDCIPP were purchased from Wako Pure Chemical Industries Ltd (Osaka, Japan) Deuterium-labeled TPHP (TPHP-d15) was purchased from Cambridge Isotope Laboratories Inc (Tewksbury, MA, USA) Native TDMPP, deuterium-labeled TMPP, TDMPP, and TCEP (TMPP-d21, TDMPP-d9, and TCEP-d12) were purchased from Hayashi Pure Chemical Ind., Ltd (Osaka, Japan) Technical mixtures of PBDPP (product name of CR733S), BPA-BDPP (product name of CR-741), and PBDMPP (product name of PX-200) were used for quantification in the present study Fourteen native PBDE congeners (BDE-3, 15, 28, 47, 99, 100, 153, 154, 183, 196, 197, 206, 207, and 209) and eleven 13C-labeled PBDE congeners (13C12-BDE-3, 15, 28, 47, 99, 153, 154, 183, 197, 207, and 209) were obtained from Wellington Laboratories Inc (Guelph, Canada) 2.3 Chemical analysis Approximately 15 g of each sample was extracted firstly using a rapid solvent extractor (SE-100; Mitsubishi Chemical Analytech Co., Ltd.) at 35 °C for 40 with acetone:n-hexane (1:1, v/v) mixture at flow rate of mL/min, and secondary at 80 °C for 40 with toluene at flow rate of mL/min The combined extract was evaporated to 10 mL and then stored as a crude extract at °C until cleanup For the analysis of 11 PFRs and TBBPA, a portion of crude extract (equal to 1.0 g of sample) was spiked with four deuterium-labeled m-PFRs, was evaporated and passed through two cleanup columns composed of g of florisil (Kanto Chemical Co Inc., Tokyo, Japan) and 0.1 g of monomeric octadecyl, end-capped silica gel (DSC-18Lt; Sigma-Aldrich Corp., St Louis, MO, USA) and then eluted with mL of Acetonitrile Measurements of PFRs and TBBPA were done using an ultra high performance liquid chromatograph (1290 Infinity; Agilent Technologies Inc., Santa Clara, CA, USA) equipped with a tandem mass spectrometer (Quattro Ultima; Waters Corp., Milford, MA, USA) with a column (ZORBAX Eclipse Plus C18 RRHD, 100 mm × 2.1 mm i.d., 1.8 μm; Agilent Technologies Inc., Santa Clara, CA, USA) Nitrogen was used as desolvation and nebulizer gas and argon as collision gas The LC injection volume was μL The flow rate of the mobile phase was set at 0.3 mL/min A water solution containing 10 mM ammonium acetate was used as eluent A and 100% methanol containing 10 mM ammonium acetate was used as eluent B The following gradient was used: (60% B), 15 (99% B), 20 (99% B), and 20.1 (60% B) The tandem mass spectrometer was run in the electron spray ionization interface using the positive mode for PFRs and the negative mode for TBBPA The capillary voltage was set to 3000 V, with source temperature of 120 °C, and desolvation temperature of 400 °C The desolvation gas flow was 700 L/h, cone gas flow 50 L/h, with collision gas pressure 3.0 × 10−3 mbar Transitions measured using multiple-reactionmonitoring for quantification are given in Table S1 of Supplementary data The analytical procedure used for PBDEs is given elsewhere (Tue et al., 2010, 2013), but a brief summary follows A portion of crude extract (equal to 2.0 g of sample) was spiked with the 13C-labeled PBDE congeners, treated with sulfuric acid (Wako Pure Chemical Industries SS-22 Bui Dau Map Bui Dau SS-6 SS-9 SS-5 SS-10 SS-7 SS-19 Vietnam SS-4 SS-8 SS-3 SS-21 SS-29 RS-1 SS-18 SS-27 SS-26 SS-32 SS-17 SS-20 SS-30 SS-28 SS-11 SS-31 SS-25 SS-24 SS-23 RS-2 RS-3 SS-2 RS-4 SS-1 SS-12 SS-16 SS-15 Surface soil E-waste recycling workshop Open burning site Rice paddy RS-5 SS-13 RS-6 River sediment RS-7 SS-14 200 m RS-8 Upstream area E-waste recycling area Downstream area Fig Map of the surface soil and river sediment sampling sites in Bui Dau, northern Vietnam SS-1 to SS-32: surface soil samples RS-1 to RS-8: river sediment samples Please cite this article as: Matsukami, H., et al., Flame retardant emission from e-waste recycling operation in northern Vietnam: Environmental occurrence of emerging organophosphorus esters used as alterna , Sci Total Environ (2015), http://dx.doi.org/10.1016/j.scitotenv.2015.02.008 H Matsukami et al / Science of the Total Environment xxx (2015) xxx–xxx Ltd., Osaka, Japan), and passed through a multilayer silica gel column (Wako Pure Chemical Industries Ltd., Osaka, Japan) Measurements of mono-PBDE to hepta-PBDE congeners were conducted on a gas chromatograph (GC) (7890 series; Agilent Technologies Inc., Santa Clara, CA, USA) equipped with a mass spectrometer (MS) (5975C MSD; Agilent Technologies Inc., Santa Clara, CA, USA) using a DB-1 capillary column (30 m × 0.25 mm i.d., 0.25 μm film thickness; Agilent Technologies Inc., Santa Clara, CA, USA) Measurement of Octa-BDE to Deca-BDE congeners was performed on another GC– MS system of the same models with a DB-1 capillary column (15 m × 0.25 mm i.d., 0.1 μm film thickness; Agilent Technologies Inc., Santa Clara, CA, USA) Results and discussion 3.1 FR concentrations in surface soils and river sediments Three o-PFRs and eight m-PFRs, TBBPA, and PBDE congeners were identified and quantified in surface soils and river sediments around the e-waste recycling area in Bui Dau This is the first reported occurrence of o-PFRs in the outdoor environment, although o-PFRs have been identified and quantified in air and dust from indoor environment (Matsukami et al., 2010; Brandsma et al., 2013) The concentrations of FRs in surface soil samples from the footpaths around the rice paddies, the open burning sites, and the workshops are shown in Fig Detailed concentration data in surface soil samples are shown in Table The concentrations of FRs in river sediment samples are given in Table The detected concentrations of FRs were highest in surface soils around the workshop (Table 1), where PBDPP, BPA-BDPP, TPHP, the total PBDEs, and TBBPA were detected in concentrations up to micrograms per gram The respective concentrations of PBDPP, BPA-BDPP, TPHP, TBBPA and the total PBDEs in surface soils were 6.6–14,000 ng/ g-dry, b 2–1500 ng/g-dry, 11–3300 ng/g-dry, b5–2900 ng/g-dry, and 67–9200 ng/g-dry The concentrations of FRs in soils from the sampling sites SS-26 and SS-29 were higher than in those from other workshop sites PBDPP was the most abundant FR at SS-26, whereas the total PBDEs were the most abundant at SS-29 In contrast, the concentrations of FRs at SS-27 and SS-31 were lower than those from other workshop sites In soils around the open burning sites, TMPP, EHDPP, TPHP, and PBDEs were dominant among the investigated FRs The respective concentrations of TMPP, EHDPP, TPHP, and the total PBDEs in surface soils were b 2–190 ng/g-dry, b 2–69 ng/g-dry, b 3–51 ng/g-dry and 1.7–67 ng/g-dry In soils from the footpaths around rice paddies, all FRs were detected with concentrations of up to 10 ng/g-dry 2.4 QA/QC Samples were analyzed using established laboratory QA/QC procedures All analytical processes were conducted under UV-cutoff conditions by taking the degradation of PBDEs and TBBPA into consideration Results of triplicate spike experiments to verify the recovery of PFRs in surface soil and river sediment samples are available in Supplementary data: Table S2 The average recoveries of PFRs were 56–104% from spiked surface soil samples and 59–103% from spiked river sediment samples For TPHP-d15, TMPP-d21, TDMPP-d9, and TCEP-d12, the average recoveries for all samples were 64–74% For 13C-labeled PBDE congeners, the average recoveries for all samples were 65–130% The limit of quantification (LOQ) values of PFRs, TBBPA, and PBDEs were calculated using the signal-to-noise ratio and shown in Tables and Procedural blanks were analyzed simultaneously with samples to check for interferences and contamination The concentrations of all the target compounds in procedural blanks were below the LOQ values Table Concentrations (ng/g-dry) of flame retardants in surface soil samples in the present study.a Compound Rice paddy (n = 19) Mean BDE-3 BDE-15 BDE-28 BDE-47 BDE-99 BDE-100 BDE-153 BDE-154 BDE-183 BDE-196 BDE-197 BDE-206 BDE-207 BDE-209 Total PBDEs TBBPA TPHP MPDPP EHDPP TMPP TDMPP TCEP TCIPP TDCIPP PBDPP BPA-BDPP PBDMPP 0.046 0.026 0.23 0.38 0.61 0.10 0.21 0.13 0.68 0.088 0.10 0.13 0.16 1.4 2.2 10 2.3 7.3 6.3 2.4 Median 0.046 0.026 0.24 0.038 0.45 0.10 0.19 0.13 0.31 0.066 0.12 0.059 0.073 0.46 0.50 10 2.3 7.3 6.3 2.4 Open burning site (n = 3) Range % detection Mean Median bLOQ–0.046 bLOQ–0.052 bLOQ–0.41 bLOQ–2.2 bLOQ–1.5 bLOQ–0.11 bLOQ–0.39 bLOQ–0.16 bLOQ–2.0 bLOQ–0.20 bLOQ–0.23 bLOQ–0.32 bLOQ–0.50 bLOQ–7.1 bLOQ–8.2 bLOQ bLOQ–10 bLOQ bLOQ bLOQ–2.3 bLOQ bLOQ bLOQ bLOQ 7.3 6.3 2.4 32 16 53 21 11 16 11 21 21 26 47 42 95 95 0 0 0 5 0.074 0.18 0.77 1.7 2.4 0.41 0.73 0.71 2.4 1.6 1.2 1.9 3.1 9.8 24 0.074 0.18 0.77 1.5 2.4 0.41 0.73 0.71 2.4 1.6 0.38 0.31 0.57 2.0 7.7 51 9.4 69 97 51 9.4 69 97 2.1 2.1 2.5 1.1 2.5 1.1 E-waste recycling workshop (n = 10) LOQ Range % detection Mean Median Range % detection bLOQ–0.074 bLOQ–0.27 bLOQ–1.1 0.049–3.7 bLOQ–3.9 bLOQ–0.69 bLOQ–1.2 bLOQ–1.2 bLOQ–4.2 bLOQ–2.9 0.023–3.3 0.076–5.4 0.060–8.8 1.4–26 1.6–63 bLOQ bLOQ–51 bLOQ–9.4 bLOQ–69 bLOQ–190 bLOQ bLOQ–2.1 bLOQ bLOQ–2.5 bLOQ–1.1 bLOQ bLOQ 33 67 67 100 67 67 67 67 67 67 100 100 100 100 100 33 33 33 67 33 33 33 0 0.034 0.38 3.3 20 21 1.6 9.7 2.5 46 10 14 68 38 1700 1900 1200 620 44 24 25 12 4.0 19 21 2000 350 79 0.035 0.16 1.1 7.3 8.5 0.66 2.9 0.72 7.2 3.7 3.3 35 21 1100 1200 1100 110 26 18 19 6.4 4.3 19 23 350 38 15 bLOQ–0.048 0.017–2.2 0.066–21 0.47–120 0.33–130 bLOQ–8.4 0.13–40 bLOQ–9.0 0.46–230 0.19–65 0.28–82 2.1–350 1.3–180 62–8200 68–9200 bLOQ–2900 11–3300 bLOQ–140 bLOQ–67 bLOQ–67 bLOQ–34 bLOQ–5.2 bLOQ–36 bLOQ–40 6.6–14000 bLOQ–1500 bLOQ–320 50 100 100 100 100 90 100 70 100 100 100 100 100 100 100 60 100 80 70 70 40 40 70 50 100 90 80 0.01 0.01 0.02 0.02 0.04 0.04 0.04 0.04 0.1 0.02 0.02 0.02 0.02 0.09 0.09 2 2 0.7 0.7 BDE — brominated diphenyl ether; TBBPA — tetrabromobisphenol A; TPHP — triphenyl phosphate; MPDPP — methylphenyl diphenyl phosphate; EHDPP — 2-ethylhexyl diphenyl phosphate; TMPP — tris(methylphenyl) phosphate; TDMPP — tris(dimethylphenyl) phosphate; TCEP — tris(2-chloroethyl) phosphate; TCIPP — tris(2-chloroisopropyl) phosphate; TDCIPP — tris(1,3-dichloroisopropyl) phosphate; PBDPP — 1,3-phenylene bis(diphenyl phosphate); BPA-BDPP — bisphenol A bis(diphenyl phosphate); PBDMPP — 1,3-phenylene bis[di(2,6dimethylphenyl) phosphate] a Sampling points for surface soil samples are shown in Fig Please cite this article as: Matsukami, H., et al., Flame retardant emission from e-waste recycling operation in northern Vietnam: Environmental occurrence of emerging organophosphorus esters used as alterna , Sci Total Environ (2015), http://dx.doi.org/10.1016/j.scitotenv.2015.02.008 H Matsukami et al / Science of the Total Environment xxx (2015) xxx–xxx Table Concentrations (ng/g-dry) of flame retardants in river sediment samples in the present study.a Compound BDE-3 BDE-15 BDE-28 BDE-47 BDE-99 BDE-100 BDE-153 BDE-154 BDE-183 BDE-196 BDE-197 BDE-206 BDE-207 BDE-209 Total PBDEs TBBPA TPHP MPDPP EHDPP TMPP TDMPP TCEP TCIPP TDCIPP PBDPP BPA-BDPP PBDMPP Upstream area E-waste recycling area RS-1 RS-2 RS-3 RS-4 RS-5 Downstream area RS-6 RS-7 RS-8 LOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ 0.023 0.028 0.10 0.080 2.6 2.8 bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ 0.027 0.044 0.26 2.0 1.6 0.14 1.0 0.27 5.8 1.6 2.5 11 7.6 320 350 36 38 2.7 bLOQ 2.9 bLOQ bLOQ bLOQ 2.5 78 20 1.1 bLOQ 0.033 0.18 1.1 0.83 0.052 0.29 0.062 1.1 0.35 0.51 3.4 2.2 90 100 6.0 7.3 bLOQ bLOQ bLOQ bLOQ bLOQ 4.5 bLOQ 4.6 bLOQ 0.012 0.017 0.083 0.60 0.47 bLOQ 0.56 0.078 3.7 0.85 1.6 6.8 5.9 260 280 44 4.3 bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ 1.7 bLOQ bLOQ bLOQ bLOQ bLOQ 0.039 0.040 bLOQ 0.091 bLOQ 0.75 0.23 0.34 2.1 1.2 56 61 11 4.1 bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ 4.4 3.5 bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ 0.062 bLOQ 0.86 0.14 0.41 0.36 0.53 12 14 bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ 1.9 bLOQ bLOQ bLOQ 0.010 0.023 0.16 0.13 bLOQ 0.078 bLOQ 0.25 0.083 0.14 0.33 0.31 9.7 11 bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ 0.43 0.43 bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ bLOQ 0.01 0.01 0.02 0.02 0.04 0.04 0.04 0.04 0.1 0.02 0.02 0.02 0.02 0.09 0.09 2 2 0.7 0.7 BDE — brominated diphenyl ether; TBBPA — tetrabromobisphenol A; TPHP — triphenyl phosphate; MPDPP — methylphenyl diphenyl phosphate; EHDPP — 2-ethylhexyl diphenyl phosphate; TMPP — tris(methylphenyl) phosphate; TDMPP — tris(dimethylphenyl) phosphate; TCEP — tris(2-chloroethyl) phosphate; TCIPP — tris(2-chloroisopropyl) phosphate; TDCIPP — tris(1,3-dichloroisopropyl) phosphate; PBDPP — 1,3-phenylene bis(diphenyl phosphate); BPA-BDPP — bisphenol A bis(diphenyl phosphate); PBDMPP — 1,3-phenylene bis[di(2,6dimethylphenyl) phosphate] a Sampling points for surface soil samples are shown in Fig It is readily apparent that the concentrations of FRs in river sediments were highest in the e-waste recycling area (Table 2), 1–2 orders of magnitude higher than those from the upstream area PBDPP, BPA-BDPP, TPHP, TBBPA and the total PBDEs were abundant FRs at sampling site RS-2 in the e-waste recycling area The respective concentrations of PBDPP, BPA-BDPP, TPHP, TBBPA and the total PBDEs in river sediments were 4.4–78 ng/g-dry, b 2–20 ng/g-dry, 7.3–38 ng/g-dry, 6.0–44 ng/g-dry and 100–350 ng/g-dry The concentrations of FRs in sediments from downstream areas decreased in the flow direction At sampling site RS-8, approximately km downstream of the e-waste recycling area, the concentrations of FRs were within the same order of magnitude of those from the upstream area Results show that BDE-209 was the most abundant PBDE congener in each type of sample The proportions of BDE-209 in surface soils around the rice paddies, the open-burning sites, and the workshops were 27–100%, 26–87%, and 69–95% of the total PBDEs, respectively, whereas those in river sediments were 84–93% of the total PBDEs In soil around the open-burning sites, the proportions of BDE-47 were 3.0–20% of the total PBDEs, which were higher than those in soils around the workshops, which were 0.038–5.5% of the total PBDEs 3.2 Comparison of FR concentrations in surface Soil and river sediments The respective concentrations of the total PBDEs and TBBPA detected in soils were 1.7–9200 ng/g-dry and 19–2900 ng/g-dry In previous studies, those concentrations in soils from e-waste recycling areas in China were 2.9–9156 ng/g-dry for total PBDEs and 26–104 ng/g-dry for TBBPA (Leung et al., 2007; Luo et al., 2009; Xu et al., 2012) Those concentrations in sediments from Bui Dau were 0.43–350 ng/g-dry for the total PBDEs and 1.2–44 ng/g-dry for TBBPA In comparison, those concentrations in the bottom sediments from China were 52–445 ng/g-dry for the total PBDEs and 0.2–22 ng/g-dry for TBBPA (Luo et al., 2007; Xu et al., 2012) Comparisons of the concentrations of the total PBDEs and TBBPA detected in soils and sediments from the present and previous studies indicate that the concentrations of the total PBDEs in soils and sediments collected from Bui Dau were within the same order of magnitude of those reported from e-waste recycling areas in China Data related to the concentrations of PBDEs, TBBPA, TPHP, TCEP, TCIPP, and TDCIPP in European rural and urban soils have been reported (Hassanin et al., 2004; Harrad and Hunter, 2006; Sánchez-Brunete et al., 2009; Mihajlovic et al., 2011) Previous studies found that the concentrations of the total PBDEs and TBBPA in soils from UK, Norway, and Spain were, respectively, 0.015–5.6 ng/g-dry and 0.34–32.2 ng/g-dry (Hassanin et al., 2004; Harrad and Hunter, 2006; Sánchez-Brunete et al., 2009) The average concentrations of TPHP, TCEP, and TCIPP in urban soil samples collected from a university campus in Germany were 1.23–4.96 ng/g-dry TDCIPP could not be detected (Mihajlovic et al., 2011) Comparisons of the concentrations of FRs detected in soils indicate that the concentrations of FRs in soils around the workshops and the open burning sites in Bui Dau were 1–3 orders of magnitude higher than those in soils from general rural and urban areas in Europe However, the concentrations of flame retardants in soils from footpaths around the rice paddies in Bui Dau were within the same order of magnitude of those from general rural and urban areas in Europe Numerous comparable data related to the concentrations of PBDEs and TBBPA in sediments from urban areas around the world are available from earlier studies (Watanabe et al., 1983; Sellström et al., 1998; Allchin and de Boer, 2001; de Wit, 2002; de Boer et al., 2003; Quade et al., 2003; Eljarrat et al., 2004; Morris et al., 2004; Mai et al., 2005; Zhang et al., 2009; Guerra et al., 2010) For example, PBDEs and TBBPA in the sediments from urban areas in Europe, USA, China, and Japan have been detected with respective concentrations of 0.5–59 ng/g-dry, 0.6–11600 ng/g-dry, and 0.6–9750 Please cite this article as: Matsukami, H., et al., Flame retardant emission from e-waste recycling operation in northern Vietnam: Environmental occurrence of emerging organophosphorus esters used as alterna , Sci Total Environ (2015), http://dx.doi.org/10.1016/j.scitotenv.2015.02.008 H Matsukami et al / Science of the Total Environment xxx (2015) xxx–xxx Open burning site 500 20000 400 300 200 Rice paddy 100 15000 o-PFRs 10000 m-PFRs TBBPA PBDEs 5000 SS-1 SS-2 SS-3 SS-4 SS-5 SS-6 SS-7 SS-8 SS-9 SS-10 SS-11 SS-12 SS-13 SS-14 SS-15 SS-16 SS-17 SS-18 SS-19 SS-20 SS-21 SS-22 SS-23 SS-24 SS-25 SS-26 SS-27 SS-28 SS-29 SS-30 SS-31 SS-32 Concentration (ng/g dry weight) E-waste recycling workshop Concentration (ng/g dry weight) Fig Concentrations (ng/g-dry) of flame retardants in surface soil samples around e-waste recycling areas in Bui Dau PBDEs – polybrominated diphenyl ethers; TBBPA – tetrabromobisphenol A; o-PFRs – oligomeric organophosphorus flame retardants; m-PFRs – monomeric organophosphorus flame retardants Sampling sites are displayed in Fig ng/g-dry Comparable data related to the concentrations of PFRs are few The concentrations of TPHP, TMPP, TCEP, TCIPP, and TDCIPP in sediments have been reported from Austria and The Netherlands (Martínez-Carballo et al., 2007; Brandsma et al., 2015) Comparisons of FR concentrations detected in sediments examined in present and previous studies indicate that the concentrations of FRs in sediments from e-waste recycling area in Bui Dau were within the same orders of magnitude of those from the contaminated sites in urban areas in Europe, USA, China, and Japan The concentrations of FRs in sediments from downstream area in Bui Dau were found to reduce along the steam, while the FR contaminations were rarely detected in the soil outside e-waste area and burning site These results suggest that e-waste recycle operation might only contaminate the environment within the range of a few hundred meters Additional studies must be conducted to clarify details of spatial diffusions of FRs around the workshops and the open burning sites 3.3 Current status of FR emissions from e-waste recycling operations As described above, the occurrence of FRs was confirmed around the workshops and open burning sites in Bui Dau The concentrations of FRs in soils collected at the sampling sites of SS-26 and SS-29 were higher than those at other sites The respective concentrations of PBDPP and the total PBDEs were 14,000 ng/g-dry and 680 ng/g-dry at SS-26, and 2600 ng/g-dry and 9200 ng/g-dry at SS-29 Those sites at which higher concentrations of FRs detected were found exhibited open storage of large amounts of e-waste such as cathode ray tubes, electronic housings, and printed circuit boards around the roadside (Fig S1) In contrast, the concentrations of FRs in soils at sampling sites of SS-27 and SS-31 were lower than those at other sites The respective concentrations of PBDPP and the total PBDEs were in the range of 6.6–29 ng/g-dry and 68–110 ng/g-dry Those sites with lower detected concentrations of FRs were not found to have open storage of e-waste (Fig S1) Thus, it could be assumed that open storage of e-waste is an important source of environmental contamination by FRs The presence of FRs in soils and sediments apparently reflects their use in the electronic products being recycled BDE-209 is the major component of technical Deca-BDE The presence of BDE-209 as the major PBDE congener in soils around the workshops and open burning sites indicates that e-waste originating from flame-retarded products containing technical Deca-BDE have been processed within Bui Dau The presence of PFRs and TBBPA in soils and sediments, which are increasingly used as alternatives for PBDEs, indicates that the types of FRs incorporated into flame-retarded plastics for electronic products are shifting in response to domestic and international regulations of PBDEs In fact, a survey of FRs in TVs and laptop computers on the Japanese market in 2008 revealed the predominant use of m-PFRs and TBBPA other than PBDEs in electronic housings and printed circuit boards (Kajiwara et al., 2011) TPHP itself was used as a FR and plasticizer, while it is also a probable impurity of PBDPP and BPA-BDPP commercial products (Syracuse Research Corporation, 2006; Rossi and Heine, 2007; Pawlowski and Schartel, 2007) TPHP impurity in those commercial products might contribute to TPHP contamination in e-waste area The volume of e-waste containing PFRs and TBBPA is estimated to have increased gradually worldwide The emissions of PFRs and TBBPA from open storage of e-waste might become greater than those of PBDEs in the future For TBBPA, the apparent half-life under anaerobic conditions was b1 d; more than two orders of magnitude shorter than the persistence criteria of six months for PBTs for soil and sediment of the Stockholm Convention on Persistent Organic Pollutants (Gerecke et al., 2006) Recent studies of the respective patterns of biodegradation of TPHP, PBDPP, and BPA-BDPP in activated sludge showed complete degradation of TPHP and PBDPP within a few days, but high persistence of the structurally similar BPA-BDPP within 56 d for mineralization tests (Jurgens et al., 2014) Based on results obtained from these previous studies, TBBPA, TPHP, and PBDPP released from e-waste recycling operations might decompose eventually, but BPA-BDPP might persist together with PBDEs around e-waste recycling area For residents around e-waste recycling area, high concentrations of FRs in surface soils and river sediments are expected to be associated with exposure concerns during their daily life They could expose to contaminants via laundry or swimming in the river or unconscious intake of soil Such contamination could also enter the domestic food chain Diet has been highlighted as an important pathway of human exposure to PBDEs released from e-waste recycling areas Consumption of locally produced foods such as chicken meat, chicken eggs, fish, and pork has been recognized as an important pathway to human exposure to PBDEs around e-waste recycling areas in China (Zhao et al., 2009; Ni et al., 2012; Chan et al., 2013; Su et al., 2012; Yu et al., 2011; Labunska et al., 2013, 2014, 2015) However, information related to human exposure to PFRs and TBBPA is not obtained from e-waste recycling area The behavior of PFRs and TBBPA should be regarded as a risk factor along with e-waste recycling operations Additional studies must be conducted to clarify details of contaminations of PFRs and TBBPA in foods that locally produced around e-waste recycling area Please cite this article as: Matsukami, H., et al., Flame retardant emission from e-waste recycling operation in northern Vietnam: Environmental occurrence of emerging organophosphorus esters used as alterna , Sci Total Environ (2015), http://dx.doi.org/10.1016/j.scitotenv.2015.02.008 H Matsukami et al / Science of the Total Environment xxx (2015) xxx–xxx Conclusions Results of the present study provided information related to the environmental emissions of FRs by uncontrolled and primitive recycling operations Open storage of e-waste and open burning of insulated copper wires have been determined to be important factors contributing to the emissions of FRs to the surrounding environment Serious contaminations by FRs could be observed in surface soils and river sediments near the e-waste recycling workshops or open burning sites, but low concentrations of FRs were found in the soils from footpaths around rice paddies and the contaminations by FRs reduced along with the stream in the downstream sediments For the actual operations, restrictions of open storage and burning of e-waste might mitigate the environmental and human health risks of FRs posed by e-waste recycling operations This information obtained from the present study will be useful for planning outdoor exposure avoidance and appropriate measures for emission control of FRs The environmental occurrence of emerging PFRs used increasingly as alternatives for PBDEs indicates that the types of flame retardants incorporated into flame-retarded plastics are shifting in response to domestic and international regulations of PBDEs Considering the increasing consumption of 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organophosphorus esters used as alterna , Sci Total Environ (2015), http://dx.doi.org/10.1016/j.scitotenv.2015.02.008 ... appropriate measures for emission control of FRs The environmental occurrence of emerging PFRs used increasingly as alternatives for PBDEs indicates that the types of flame retardants incorporated into... emissions of FRs from e-waste recycling operations has not been elucidated Environmental occurrence of FRs was regarded as indicators of contaminations derived from e-waste recycling because FRs are incorporated... Please cite this article as: Matsukami, H., et al., Flame retardant emission from e-waste recycling operation in northern Vietnam: Environmental occurrence of emerging organophosphorus esters used