Soil contamination by brominated flame retardants in open waste dumping sitesin Asian developing countries Akifimi Eguchia, Tomohiko Isobea,b, Karri Ramua, Nguyen Minh Tuea, Agus Sudaryant
Trang 1Soil contamination by brominated flame retardants in open waste dumping sites
in Asian developing countries
Akifimi Eguchia, Tomohiko Isobea,b, Karri Ramua, Nguyen Minh Tuea, Agus Sudaryantoa,c,
Annamalai Subramaniana, Shinsuke Tanabea,⇑
a
Center for Marine Environmental Studies (CMES), Ehime University, Bunkyo-cho 2-5, Matsuyama 790-8577, Japan
b
Senior Research Fellow Center, Ehime University, Bunkyo-cho 2-5, Matsuyama 790-8577, Japan
c
Technology Center for Marine Survey, Agency for the Assessment and Application of Technology (BPPT), Jl M.H Thamrin 8, Jakarta, Indonesia
d
Centre for Environmental Technology and Sustainable Development, Hanoi University of Science, 334 Nguyen Trai, Hanoi, Viet Nam
e Economic, Social and Cultural Observation Unit, Office of the Council of Minister, Sahapoan Russi Blvd., Phnom Penh, Cambodia
h i g h l i g h t s
"PBDE levels in municipal dumping sites were higher than those in reference sites
"HBCD levels in municipal dumping sites and reference sites were comparable
"BDE-209 was the dominant PBDE congener, whilec-HBCD was the dominant isomer
"Waste burning may be causing the elevated ratios of octa- and nona-BDEs, anda-HBCD
"PBDE level and the TOC content of soils at dumping sites were not correlated
a r t i c l e i n f o
Article history:
Received 12 January 2012
Received in revised form 29 September 2012
Accepted 17 October 2012
Available online 11 November 2012
Keywords:
Polybrominated diphenyl ethers (PBDEs)
Hexabromocyclododecanes (HBCDs)
Municipal waste dumping sites
Soil
Asian developing countries
a b s t r a c t
In Asian developing countries, large amounts of municipal wastes are dumped into open dumping sites each day without adequate management This practice may cause several adverse environmental conse-quences and increase health risks to local communities These dumping sites are contaminated with many chemicals including brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs)
BFRs may be released into the environment through production processes and through the disposal of plastics and electronic wastes that contain them
The purpose of this study was to elucidate the status of BFR pollution in municipal waste dumping sites
in Asian developing countries Soil samples were collected from six open waste dumping sites and five reference sites in Cambodia, India, Indonesia, Malaysia, and Vietnam from 1999 to 2007 The results sug-gest that PBDEs are the dominant contaminants in the dumping sites in Asian developing countries, whereas HBCD contamination remains low Concentrations of PBDEs and HBCDs ranged from ND to
180lg/kg dry wt and ND to 1.4lg/kg dry wt, respectively, in the reference sites and from 0.20 to
430lg/kg dry wt and ND to 2.5lg/kg dry wt, respectively, in the dumping sites Contamination levels
of PBDEs in Asian municipal dumping sites were comparable with those reported from electronic waste dismantling areas in Pearl River delta, China
Ó 2012 Elsevier Ltd All rights reserved
1 Introduction
Environmental contamination by brominated flame retardants
(BFRs), such as polybrominated diethyl ethers (PBDEs) and
hexab-romocyclododecanes (HBCDs), has received increasing public
attention because of the persistence, bioaccumulation potential, and possible adverse effects of these chemicals on humans and wildlife (Hites, 2004; Covaci et al., 2006)
PBDEs can have adverse in vitro and in vivo physiological effects, including endocrine disruption and interference with neurobehav-ioral development (Darnerud, 2003; Birnbaum and Staskal, 2004; Herbstman et al., 2010) Several studies have shown that effects
of PBDEs are similar to those of organohalogen compounds, such 0045-6535/$ - see front matter Ó 2012 Elsevier Ltd All rights reserved.
⇑ Corresponding author.
E-mail address: shinsuke@agr.ehime-u.ac.jp (S Tanabe).
Contents lists available atSciVerse ScienceDirect
Chemosphere
j o u r n a l h o m e p a g e : w w w e l s e v i e r c o m / l o c a t e / c h e m o s p h e r e
Trang 2as reduction in serum thyroid hormone levels (Hallgren et al.,
2001) Reported toxicities of HBCDs include developmental
neuro-toxic effects such as aberrations in spontaneous behavior, learning,
and memory functions (Eriksson et al., 2002, 2004) HBCDs also
al-ter the normal transport of neurotransmital-ters in rat brain (
Marius-sen and Fonnum, 2003; Ibhazehiebo et al., 2011)
PBDEs and HBCDs are used as flame-retardant additives in a wide
variety of commercial and household products such as plastics,
tex-tiles, and electronic appliances including computers and televisions
(Kemmlein et al., 2009) In 2001, global consumption of the
techni-cal PBDE mixtures penta-, octa-, and deca-BDE and HBCDs was
7500, 3800, 56 000, and 15 900 tons, respectively In Asia, the total
consumption volumes of penta-, octa-, deca-BDEs and HBCDs were
150, 2000, 23 000, and 3900 tons, respectively, during 2001 (BSEF,
2003; Watanabe and Sakai, 2003) This widespread usage and
bioac-cumulation potential of BFRs resulted in both classes of these
chem-icals being present in air, water, fish, birds, marine mammals, and
humans throughout the world (Law et al., 2008)
In Asian developing countries, the majority of the municipal
so-lid waste, which consists of a wide variety of materials such as food
waste, paper, plastics, building material, metal wastes, and ash
(Gullett et al., 2010; Fiedler and Solorzano Ochoa, 2010), were
dis-posed directly into open waste dumping sites without appropriate
processes (Minh et al., 2003) Apart from the enormous amounts of
waste dumped in such areas, not much information on their
qual-ity and quantqual-ity is available from Asian developing countries As a
result, these open dumping sites could be a major source of
con-taminant emission on the environment and human exposure route
This practice has led to public concerns over potential impacts on
the environment and local communities These concerns were
jus-tified by more recent intensive studies that demonstrated an
in-creased human health risk caused by exposure to toxic chemicals
such as persistent organic pollutants (POPs) from dumping sites
(Minh et al., 2006) However, previous studies on BFRs in soil
sam-ples from Asian developing countries were confined to Chinese
e-waste recycling sites and Indonesian municipal waste dumping
sites (Leung et al., 2007; Zou et al., 2007; Ilyas et al., 2011) A
com-prehensive survey monitoring BFRs in background soils in Asian
developing countries has not yet been conducted Thus, the present
study investigated BFR contamination of soils from municipal
waste dumping sites and background areas in five Asian
develop-ing countries to elucidate the role of municipal waste dumpdevelop-ing
sites as potential sources of BFR pollution in these countries
2 Materials and methods
2.1 Sample collection
Soil samples were collected from municipal waste dumping
sites and reference sites in India, Vietnam, Malaysia, Indonesia,
and Cambodia between 1999 and 2007 (Fig S1) and stocked in
the es-Bank of Ehime University (Tanabe, 2006), Japan were used
for the present study Sampling was made in the municipal
dump-ing sites and uncontaminated sites in many Asian developdump-ing
countries under our various research programs for about a decade
starting from the late 1990s At each location, samples were
col-lected at depths of 0–10 cm at five points within an area of
approx-imately 25 m2 and then combined together and treated as a
representative sample for the respective location The frozen
sam-ples were transported to the Environmental Specimen Bank for
Global Monitoring (es-BANK) (Tanabe, 2006) at Ehime University
with permission from the Ministry of Agriculture, Forestry and
Fisheries, Japan Samples were sieved through a 2-mm sieve, air
dried, packed in polyethylene bags, and stored at 25 °C until
chemical analysis
2.2 Chemical analysis PBDEs were analyzed according to a previously published
meth-od (Eguchi et al., 2011) with slight modification In brief, 5 g of each air-dried soil sample was extracted using a mixture of hexane and acetone (50:50, v:v, 50 mL), initially with an electric shaker for
15 min, (SR-2W model, TAITEC, Japan) and then twice using an ultrasonic bath (AU-80C model, EYELA, Japan) for 15 min each time
An aliquot of the combined extract was spiked with13C12-labeled BDE-3, -15, -28, -47, -99, -153, -154, -183, -197, -207, and -209 (5 ng each) and 13C12-labeled a-, b-, and c-HBCD (10 ng each) before being passed through a multilayer silica gel column The extract was treated with sulfuric acid and loaded onto a gel perme-ation chromatography column (GPC) The GPC fraction containing the target compounds was concentrated and purified by passage though a column containing 4 g of activated silica gel (Wakogel
DX, Wako Pure Chemical Industries Ltd., Japan) The first fraction, eluted with 5% dichloromethane in hexane (v/v), contained PBDEs, whereas the second fraction, eluted with 25% dichloromethane in hexane, contained HBCDs The PBDE fraction was treated with acti-vated copper to remove any sulfur and it was spiked with13C12 -BDE-139 to be used as an internal standard Fourteen major PBDE congeners (BDE-3, -15, -28, -47, -99, -100, -153, -154, -183, -196, -197, -206, -207, and -209) were quantified using a gas chromatog-raphy (GC) system (Agilent 7890A) equipped with a mass spec-trometer (MS, Agilent 5975C) using electron ionization with selective ion monitoring mode The GC columns used for quantifica-tion were DB-1MS fused silica capillaries (J&W Scientific Inc.) mea-suring 30 m length 0.25 mm i.d with 0.25lm film thickness for di- to hepta-BDEs, and 15 m 0.25 mm with 0.1lm film thickness for octa- to deca-BDEs All the congeners were quantified using the isotope dilution method for the corresponding labeled congeners Recovery of labeled BDEs ranged between 60% and 120% The HBCD fraction of silica gel column was evaporated and redissolved in a solution of labeled HBCD (a-, b-, and c-HBCD-d18) before liquid chromatography–tandem mass spectrometry (LC–MS/MS) analysis The diastereomeric analysis of HBCDs was performed by LC–MS/
MS, according to a previously published method (Isobe et al.,
2007) Samples were analyzed using ACQUITY UPLC (Waters, Tokyo, Japan) equipped with a Quattro Micro API triple quadrupole mass spectrometer (Waters/Micromass, Tokyo, Japan) HBCD isomers (a-, b-, and c-) were separated using an Extend-C18 column (2.1 mm i.d., 100 mm, 1.8lm particle size, Agilent, Tokyo, Japan) The mobile phase comprised water/acetonitrile/methanol (20:20:60) at 0.2 mL/min initially for 5 min, before ramping up methanol for 2 min, and then water/acetonitrile/methanol (20:20:60) for 3 min The MS/MS analysis was operated in negative electrospray ionization mode and was performed in multiple reac-tion monitoring mode (MRM) Quantificareac-tion of native HBCDs was based on the mean value of the response of two MRM transitions (i.e., m/z 640 > 81, m/z 642 > 81), which was corrected with the MRM transition response for 13C12-HBCDs (i.e., m/z 652 > 81) Recovery of13C12-HBCDs spiked in the sample extracts was always
in the range of 50%–120% Concentrations of BFRs were calculated
by isotope dilution procedure For total organic carbon (TOC) anal-ysis, approximately 2 g of dried and homogenized soil sample was treated with 6 M HCl to remove inorganic carbon, washed with Milli-Q water five times, and dried overnight at 40 °C TOC was then determined using a Yanaco CHN corder MT-5 Acetanilide, antipy-rine, and 4-nitroaniline were used as external standards
2.3 Quality control and assurance
A certified sediment sample (NIES CRM Air Dried Sediment#1) that was prepared for a previous interlaboratory calibration exer-cise (Takahashi et al., 2004) was analyzed to determine specific
Trang 3PBDEs and HBCDs The data produced by our laboratory were in
good agreement with the certified concentrations (relative
stan-dard deviation < 10%) The limit of detection (LOD) for the target
compounds was based on a signal-to-noise ratio (S/N) of >3 for
the chromatogram of the actual sample, while the limit of
quanti-fication (LOQ) was defined as the amount of target compounds
with a S/N of 10 The LODs were 0.003, 0.005, and 0.005lg/kg
dry wt for mono- to hepta-BDEs, octa- to deca-BDEs, and HBCDs,
respectively A procedural blank sample was analyzed with every
batch of seven samples No peaks were detected in the
chromato-grams of the blank samples
2.4 Statistical analysis
Statistical analyses were performed with the R program, Ver
2.12.0 The Wilcoxon rank-sum test was used to determine any
dif-ferences in the concentrations of PBDEs and HBCDs between the
municipal waste dumping sites and the reference sites Spearman’s
rank correlation test was used to test the significance of correlation
between the concentration of BFR and organic carbon Principal
component analysis (PCA) was employed to categorize PBDE
cong-eners according to variations in the patterns of their proportions in
the total PBDEs This analysis included only the congeners that
were detected in at least 75% of the samples A p value of <0.05
was considered to be statistically significant Results below LOQ
were given a value of 0.5 LOQ
3 Results and discussion
3.1 Contamination levels
3.1.1 BFR contamination in reference sites
BFR soil levels in Asian developing countries have only been
re-ported by a limited number of studies from contamination
hot-spots, such as e-waste recycling sites in China (Leung et al.,
2007; Zou et al., 2007) and municipal waste dumping sites in
Indo-nesia (Ilyas et al., 2011) In this study, 27 soil samples from urban
and agricultural sites in India, Vietnam, Malaysia, Indonesia, and
Cambodia were analyzed as reference sites PBDEs were detected
in 25 samples and HBCDs were detected in 21 samples The PBDE
and HBCD concentrations were significantly higher (p < 0.05) in
Cambodian reference sites than in soil samples from other
refer-ence sites (Table 1) As shown inTable 2, the PBDE levels in soils
from other Asian developing countries were comparable to the
background levels in Japan and Pearl River delta, China, whereas
the levels in Cambodian soils were 2–10 times higher (Hayakawa
et al., 2004; Sellstrom et al., 2005; Leung et al., 2007; Zou et al.,
2007) The higher levels observed in Cambodia may be related to
the proximity of some collection points to roads The levels of total
HBCDs from most reference sites were comparable to those
re-ported in urban areas in Guangzhou, China (Yu et al., 2008) and
background areas in Surabaya, Indonesia (Ilyas et al., 2011) This
indicates that significant and ubiquitous BFR pollution sources
are present in Asian developing countries
3.1.2 BFR contamination in municipal waste dumping sites
Since, contamination levels of PBDEs and HBCDs in Indonesian
waste dumping sites were not significantly different between
2002–2003 and 2007, these samples were merged Recent studies
have demonstrated that open waste dumping sites found in Asian
developing countries may be hotspots for toxic chemicals, such as
PCBs and dioxin-like compounds, and exposure to these
contami-nants may have adverse effects on the health of people living in
affected areas (Minh et al., 2003, 2006) However, only one
previ-ous study has reported the BFR contamination level of soil from a
dumping site which was in Surabaya, Indonesia (Ilyas et al.,
2011) The current study detected PBDEs in all dumping site soils
at significantly higher levels than that in their respective reference sites (Table 1, p < 0.05), suggesting that municipal waste dumping sites are a potential source of PBDEs in Asian developing countries The levels were highest in Vietnam (mean: 95lg/kg dry wt, range: 1.2–430lg/kg dry wt), followed by Indonesia, Cambodia, India, and Malaysia (mean: 6.2–32lg/kg dry wt, range: 0.12–260lg/kg dry wt) (Table 1) However, these levels were one to two orders
of magnitude lower than that found in soils from contamination hotspots in other countries such as sludge application areas in Sweden, (mean: 350lg/kg dry wt) (Sellstrom et al., 2005) and e-waste recycling sites in China (2719–4250lg/kg dry wt) (Leung
et al., 2007)
HBCDs were detected in 30/45 samples and the HBCD levels were not significantly different between municipal waste dumping sites and reference sites in all countries (Table 1), indicating that municipal waste dumping sites may not be a major source of HBCDs
in Asian developing countries The HBCD levels in soil samples from municipal waste dumping sites (mean: 0.29lg/kg dry wt, range:
<0.05–2.4lg/kg dry wt) were two to six orders of magnitude lower than the levels reported for near point sources in Sweden (mean:
810lg/kg dry wt) (Remberger et al., 2004) and other European countries (mean: 4300lg/kg dry wt) (Malte et al., 2004) (Table
2) Moreover, the HBCD concentrations were one to two orders of magnitude lower than those of PBDEs at all locations These results suggest that HBCDs have not been used extensively in Asian devel-oping countries Indeed, statistical data on BFR consumption indi-cates a lower usage of HBCDs in Asia, when compared with PBDEs (Watanabe and Sakai, 2003) The low levels of HBCDs could also
be due to the high levels of transformation processes for these com-pounds, via biotic and/or abiotic mechanisms in the soil medium For example, significant decomposition of HBCDs in aerobic (75%
in 119 d) and anaerobic (92% in 21 d) soils was reported in a micro-cosm study (Davis et al., 2005) However, there are currently no reg-ulations on the production and usage of HBCDs, so it is anticipated that the environmental levels may rise in the near future Thus, fur-ther monitoring of the HBCD levels and alternative compounds that were introduced after restrictions on PBDE mixtures are needed in order to determine their contamination status and provide future risk assessments
3.2 Congener and isomer profiles Principal component analysis (PCA) was employed to categorize PBDE congeners according to the variation in the patterns of their relative proportions (%) in total PBDEs Based on the results, soil samples were divided into three categories as lower brominated BDEs (3–6Br), 7–9Br BDEs, and BDE-209 (Fig 1) Deca-BDE was aligned with the first principal component (PC1, accounting for 39.2% of total variance) 7–9Br-congeners, and lower brominated PBDEs contributed to both PCs, but in an opposite manner in PC2 (23.5% of variance) Most soil samples aligned with BDE-209, reflecting its high abundance (48–93% of total PBDEs) in those par-ticular samples This predominance was consistent with the high volume of consumption of deca-BDE technical mixtures (Watanabe and Sakai, 2003) in Asia and the strong binding affinity of BDE-209 with soil particles Some samples from municipal waste dumping sites aligned with 7–9Br-BDEs, especially in Vietnam and Indonesia, indicating the higher abundance of these congeners compared with samples from the reference sites (Table 1) Lower brominated BDEs were aligned with samples from the reference sites and the Cambodian municipal waste dumping site The proportion of octa- and nona-BDE congeners in samples from dumping sites (7.8–30%) was higher than that in deca-BDE technical mixtures (2.4–9.3%) (La Guardia et al., 2006), possibly due to a higher degree
Trang 4Table 1
Concentrations (lg/kg, dry weight) of PBDEs and HBCDs in soils from Asian developing countries.
Cambodia, mean (min–max) India, mean (min–max) Indonesia, mean (min–max) Malaysia, mean (min–max) Vietnam, mean (min–max)
Reference site Dumping site Reference site Dumping site Reference site
2002–2003
Dumping site 2002–
2003
Dumping site 2007 Reference site Dumping site Reference site Dumping site TOC (%) 1.1 (0.0–2.7) 7.7 (0.44–24) 0.80 (0.34–1.1) 4.9 (0.98–10) 8.4 (0.92–15) 11 (1.1–27) 7.9 (0.97–27) 1.9 (0.36–3.4) 4.5 (3.3–5.7) 6.7 (0.28–24) 8.7 (1.4–15)
PBDEs
BDE3 <0.003 <0.003 <0.003 <0.003 <0.003 <0.003 <0.003 <0.003 <0.003 <0.003 <0.003
BDE15 <0.003 0.13 (<0.003–0.71) <0.003 0.01 (<0.003–0.05) 0.004 (<0.003–0.01) 0.02 (<0.003–0.06) <0.003 0.003 (<0.003–0.006) 0.12 (0.007–0.24) <0.003 0.03 (<0.003–0.05) BDE28 0.01 (<0.003–0.02) 0.98 (0.009–5.6) <0.003 0.01 (<0.003–0.05) 0.002 (<0.003–0.01) 0.06 (<0.003–0.29) 0.01 (<0.003–0.05) <0.003 0.32 (0.02–0.62) <0.003 0.07 (<0.003–0.30) BDE47 0.34 (<0.003–1.2) 3.5 (0.08–18) 0.01 (<0.003–0.02) 0.19 (0.05–0.50) 0.18 (0.05–0.71) 0.79 (<0.003–10) 0.28 (0.10–0.77) 0.02 (0.02) 0.41 (0.29–0.54) 0.01 (<0.003–0.05) 0.14 (<0.003–0.34) BDE99 0.48 (<0.003–1.5) 1.8 (0.11–7.5) 0.01 (<0.003–0.05) 0.33 (0.10–0.86) 0.14 (<0.003–0.33) 0.99 (<0.003–14) 0.36 (<0.003–0.94) 0.01 (0.01–0.02) 0.36 (0.25–0.48) 0.01 (<0.003–0.08) 0.66 (<0.003–2.4) BDE100 0.04 (<0.003–0.18) 0.20 (<0.003–0.65) <0.003 0.05 (<0.003–0.24) 0.01 (<0.003–0.05) 0.08 (<0.003–0.46) 0.05 (<0.003–0.23) 0.008 (0.007–0.01) 0.03 (<0.003–0.05) 0.02 (<0.003–0.14) 0.10 (<0.003–0.50) BDE153 0.07 (<0.003–0.2) 0.48 (0.02–1.5) <0.003 0.05 (<0.003–0.23) 0.02 (<0.003–0.11) 0.37 (<0.003–4.3) 0.10 (<0.003–0.40) 0.005 (<0.003–0.01) 0.02 (<0.003–0.05) <0.003 1.6 (<0.003–6.1)
BDE154 0.03 (<0.003–0.09) 0.17 (0.01–0.54) <0.003 0.01 (<0.003–0.05) 0.01 (<0.003–0.03) 0.24 (<0.003–2.7) 0.05 (<0.003–0.17) 0.01 (0.008–0.02) 0.44 (0.02–0.85) <0.003 0.97 (<0.003–4.9) BDE183 0.10 (<0.003–0.33) 1.1 (0.03–5.5) <0.003 0.15 (<0.003–0.29) 0.20 (0.04–0.44) 0.63 (<0.003–4.1) 0.23 (<0.003–1.1) 0.02 (0.02–0.03) 0.53 (0.09–0.97) 0.01 (<0.003–0.02) 7.3 (<0.003–28)
BDE196 0.30 (<0.003–1.08) 0.20 (0.01–0.81) <0.003 0.07 (0.02–0.20) 0.15 (0.02–0.45) 1.1 (0.005–8.7) 0.25 (<0.003–1.0) 0.01 (0.006–0.02) 0.18 (0.04–0.32) 0.01 (<0.003–0.03) 4.1 (0.02–16)
BDE197 0.05 (<0.003–0.17) 0.28 (0.01–1.3) <0.003 0.04 (<0.003–0.18) 0.12 (0.008–0.26) 0.91 (0.01–7.3) 0.26 (<0.003–1.0) 0.02 (0.01–0.03) 0.33 (0.01–0.65) 0.01 (<0.003–0.05) 5.6 (0.02–25)
BDE206 0.63 (<0.003–2.9) 1.1 (0.02–4.9) <0.003 0.41 (0.02–1.9) 0.60 (0.08–2.5) 2.1 (<0.003–13) 0.44 (<0.003–1.7) 0.07 (0.05–0.09) 0.21 (0.14–0.28) <0.003 5.1 (0.06–24)
BDE207 0.40 (<0.003–1.8) 0.80 (0.02–3.6) <0.003 0.63 (0.04–2.7) 0.52 (0.08–1.7) 2.8 (0.009–27) 0.57 (0.12–1.9) 0.08 (0.05–0.1) 0.29 (0.14–0.43) 0.01 (<0.003–0.04) 14 (0.05–64)
BDE209 35 (<0.003–170) 21 (0.16–71) 0.05 (<0.003–0.18) 5.4 (0.48–16) 8.3 (0.48–38) 31 (0.07–250) 9.9 (1.0–49) 2.1 (1.1–3.0) 3.0 (2.4–3.5) 0.14 (<0.003–0.27) 56 (1.0–260)
P
9 PBDEs a 1.1 (<0.003–5.2) 8.3 (0.31–35) 0.02 (<0.003–0.06) 0.81 (0.18–1.7) 0.57 (0.15–1.3) 3.2 (<0.003–35) 1.1 (0.10–3.7) 0.09 (0.07–0.11) 2.2 (0.78–3.7) 0.05 (<0.003–0.28) 11 (<0.003–43)
P
PBDEs b 38 (<0.003–180) 32 (0.54–91) 0.07 (<0.003–0.18) 7.3 (0.82–19) 10 (0.99–44) 41 (0.12–260) 13 (2.4–58) 2.4 (1.3–3.4) 6.2 (4.6–7.8) 0.22 (0.02–0.42) 95 (1.2–430)
HBCDs
a-HBCD 0.03 (<0.005–0.15) 0.12 (<0.005–0.41) 0.01 (<0.005–0.06) 0.37 (<0.005–0.94) 0.09 (0.04–0.19) 0.07 (<0.005–0.38) 0.02 (<0.005–0.21) 0.007 (<0.005–0.01) 0.06 (<0.005–0.12) 0.03 (<0.005–0.22) 0.03 (<0.005–0.05) b-HBCD 0.03 (<0.005–0.08) 0.02 (<0.005–0.06) 0.01 (<0.005–0.04) 0.14 (<0.005–0.35) 0.008 (<0.005–0.02) 0.02 (<0.005–0.09) 0.004 (<0.005–0.04) <0.005 0.009 (<0.005–0.02) 0.02 (<0.005–0.13) 0.02 (<0.005–0.04)
c-HBCD 0.49 (<0.005–1.2) 0.05 (<0.005–0.16) 0.06 (<0.005–0.30) 0.56 (<0.005–1.3) 0.01 (<0.005–0.02) 0.11 (<0.005–0.51) 0.02 (<0.005–0.07) 0.04 (<0.005–0.08) 0.03 (<0.005–0.06) 0.18 (<0.005–0.95) 0.09 (<0.005–0.2)
PHBCDsc 0.54 (<0.005–1.4) 0.20 (<0.005–0.40) 0.09 (<0.005–0.40) 1.1 (<0.005–2.4) 0.11 (0.06–0.21) 0.23 (<0.005–0.83) 0.04 (<0.005–0.31) 0.05 (<0.005–0.10) 0.10 (<0.005–0.20) 0.23 (<0.005–1.3) 0.14 (<0.005–0.3) a
Sum of mono- to hepta-BDE congeners (BDE3, 15, 28, 47, 99, 100, 153, 154 and 183).
b
Sum of mono- to deca-BDE congeners (BDE3, 15, 28, 47, 99, 100, 153, 154, 183, 196, 197, 206, 207 and 209).
c
Sum ofa-, b- andc-HBCDs.
Trang 5Concentrations (lg/kg, dry weight) of PBDEs and HBCDs in soils from Asian developing countries in the present study and those from other countries reported.
Reference site Dumping site Background Surface Point-source Background Near acid bath Background Sludge application soil Background Near HBCD processing plant PBDEs
P
9 PBDEs a
P
PBDEs b
HBCDs
P
HBCDs c
a Sum of mono- to hepta-BDE congeners (BDE3, 15, 28, 47, 99, 100, 153, 154 and 183).
b Sum of mono- to deca-BDE congeners (BDE3, 15, 28, 47, 99, 100, 153, 154, 183, 196, 197, 206, 207 and 209).
c
Sum ofa-, b- andc-HBCDs.
Trang 6waste materials containing PBDEs HBCD concentrations had no
significant relationship with the TOC contents in reference or
dumping sites, possibly due to low contamination levels and the
different chemical properties of HBCDs compared with PCBs and
PBDEs
4 Conclusions
This study demonstrated ubiquitous BFR contaminations in
Asian developing countries, especially in municipal waste dumping
sites PBDE levels in municipal waste dumping sites were higher
than those in reference sites, indicating the presence of prominent
sources of PBDE contaminations in municipal waste dumping sites
Recycling and disposing of PBDE-containing materials in Asian
developing countries may lead to serious environmental
contami-nations at those sites HBCD levels at all locations were relatively
low indicating the minimum pollution No significant difference
in the HBCD levels were found between municipal waste dumping
sites and reference sites, possibly due to HBCD usage remains
low-er than that of PBDEs BDE-209 was the dominant PBDE congenlow-er,
whilec-HBCD was the dominant isomer in soils from Asian
devel-oping countries However, waste burning may be responsible for
the elevated proportions of octa- and nona-BDEs, anda-HBCD in
dumping sites Unlike the reference site soils, the lack of
correla-tion between the PBDE levels and the TOC contents of soils at
dumping sites indicated that the contamination was affected by the proximity of waste materials rather than atmospheric transport
Acknowledgments This study was supported by ‘‘Global COE Program’’, Grants-in-Aid for Scientific Research (S) (No 20221003) from the Ministry
of Education, Culture, Sports, Science and Technology, Japan (MEXT) and Japan Society for the Promotion of Science (JSPS) and the Waste Management Research Grant (K2062, K2129, K2121) from the Ministry of Environment, Japan We also acknowledge the JSPS Research Fellowships for Young Scientists (DC1) in Japan provided to Mr A Eguchi (226331)
Appendix A Supplementary material Supplementary data associated with this article can be found, in the online version, athttp://dx.doi.org/10.1016/j.chemosphere.2012 10.027
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