In-line quantitative estimation of ammonium polyphosphate flame retardant in polyolefins via industrial hyperspectral imaging system and machine learning.

Due to developments in European legislation, several halogenated flame retardants are banned due to their toxicity, and the use of phosphor-based flame retardants in plastics is increasing. A revision of ammonium polyphosphate (APP) flame retardant revealed that it is an eye irritant and toxic, thus posing a health issue. Hence APP identification is needed for enabling safe recycling of plastic waste streams. Herein an industrial in-line method for quantitative estimation of APP in low density polyethylene (LDPE) and polypropylene (PP) is demonstrated, by using an industrial hyperspectral imaging system (955 to 1700 nm) and principal component analysis (PCA). Spectra of plastic samples with varying concentrations of APP were applied to build and calibrate a quantitative determination method. PCA and band area ratios (of selected bands) were made and fitted with continuous functions for concentration determination. The plastic samples were characterised by elemental analysis, attenuated total reflection, differential scanning calorimetry, and thermogravimetric analysis. The PCA model outperforms the band area ratio model and predicts APP concentrations between 24.3 and 1.5 wt% in LDPE (R2 = 0.98) and 20.0 and 1.7 wt% in PP (R2 = 0.97). Unknown samples with APP ranging from 23.7 to 2.7 wt% in LDPE and from 18.6 to 2.3 wt% in PP were predicted and correlated to the actual concentrations. The proposed approach is valuable for the plastic recyclers and waste management industries where inline concentration determination of flame retardants is key.

Biotransformation of Dec-604 and potential effect on thyroid deiodinase activity in highly flame retardant-exposed gulls.

Several halogenated flame retardants (HFRs) have been identified as thyroid disruptors in birds including the polybrominated diphenyl ether (PBDE) mixtures, which have been replaced with other HFRs such as Dechlorane-604 (Dec-604). Dec-604 Component B (Dec-604 CB), a putative debrominated product of Dec-604, has been frequently reported in urban-adapted ring-billed gulls (Larus delawarensis) breeding in the Montreal area (QC, Canada). The metabolic pathways of Dec-604 are yet to be characterized, although the occurrence of Dec-604 CB in gulls may suggest that enzyme-mediated dehalogenation may occur, potentially involving the thyroid deiodinases. The objective of this study was to investigate the effect of Dec-604 on type 1 deiodinase (DIO1) in the presence of thyroxine (T4) in an in vitro DIO1 assay using liver microsomes of ring-billed gulls that are highly exposed to HFRs in the Montreal area, and to determine whether DIO1 is involved in the in vitro debromination of Dec-604. We tested the in vitro activity of DIO1 in gull liver microsomes in the presence of five concentrations of Dec-604 ranging from 0.86 to 86.21 nM. HFR concentrations (Σ40HFR) were also determined in liver samples of gulls. Results showed that total DIO1 activity in gull liver microsomes was increased by three of the five concentrations of Dec-604. No relationship between liver Σ40HFR concentrations and DIO1 activity was observed, except for T2 formation rates that significantly decreased with increasing liver HFR concentrations. Moreover, greater Dec-604 CB to Dec-604 concentration ratios in activated gull microsomes (with the DIO1 cofactor dithiothreitol) were found at the intermediate Dec-604 concentration compared to controls. These results suggested that liver microsome DIO1 activity may be perturbed in ring-billed gulls exposed to Dec-604, and be involved at least in part, in the debromination of Dec-604 leading to the formation of Dec-604 CB.

Determination of low-density polyethylene-water partition coefficients for novel halogenated flame retardants with the large volume model and co-solvent model.

The partition coefficient (Kpew) of an analyte between low-density polyethylene (LDPE) film and water is a critical parameter for measuring freely dissolved concentrations of the analyte with PE passive sampling devices. Measuring log Kpew for super hydrophobic organic chemicals (HOCs) have been proven extremely difficult. The present study developed a large volume model for measuring log Kpew of super HOCs, i.e., novel halogenated flame retardants (NHFRs). Results showed that the measured log Kpew values of selected PAHs and PCBs obtained by the large volume model were in line with those from the co-solvent model and the literature data within less 0.3 log units of difference, while those of NHFRs (6.27-7.34) except for hexachlorocyclopentadienyldibromocyclooctane (HCDBCO) and Decabromodiphenyl ethane (DBDPE) were significantly lower than those (6.51-8.89) from the co-solvent model. A curvilinear relationship was observed between log Kpew and log Kow of all target compounds, with the turning point at log Kow = âˆ¼8.0 in the large volume model, but that was not found for the co-solvent model. These can be attributed to the large molecular volumes (> 450 Å3) for NHFRs, which require high Gibbs free energy to penetrate into the inside structures of LDPE in the large volume model. However, the solvent swelling effects in the co-solvent model needs to be investigated. Therefore, the large volume model is robust to determine the Kpew values of super HOCs for facilitating the application of aquatic passive sampling techniques.

Metabolomic profiles of the endangered St. Lawrence Estuary beluga population and associations with organohalogen contaminants.

The endangered beluga (Delphinapterus leucas) population residing in the St. Lawrence Estuary (SLE; Eastern Canada) is declining. The elevated tissue concentrations of a wide range of organohalogen contaminants might play a role in the non-recovery of this whale population. Organohalogens have been reported to impair the regulation of several metabolic products from cellular reactions in mammals such as amino acids and fatty acids. The objective of this study was to investigate a suite of organohalogens including polychlorinated biphenyls, organochlorine pesticides, short-chain chlorinated paraffins (SCCPs), polybrominated diphenyl ethers, and selected emerging flame retardants in blubber (biopsy) collected from 40 SLE male belugas, and their relationships to skin concentrations of targeted metabolites (i.e., 21 amino acids, 22 biogenic amines, 18 fatty acids, and 17 energy metabolites). A cluster analysis based on metabolomic profiles distinguished two main subgroups of belugas in the upper and lower sector of their summer habitat in the SLE. These results indicate that ecological factors such as local prey availability and diet composition played a role in shaping the metabolite profiles of belugas. Moreover, SCCP concentrations in SLE male belugas correlated negatively with those of four unsaturated fatty acids (C16:1ω7, C22:5ω3c1, C22:5ω3c2, and C22:6ω3), and positively with those of acetylornithine (biogenic amine). These findings suggest that biological functions such as lipid metabolism represent potential targets for organohalogens in this population, and further our understanding on potential health risks associated with elevated organohalogen exposure in cetaceans. Our results also underscore the necessity of considering ecological factors (e.g., diet and habitat use) in metabolomic studies.

Landfills represent significant atmospheric sources of exposure to halogenated flame retardants for urban-adapted gulls.

Halogenated flame retardants (HFRs) are contaminants that are abundantly emitted from waste management facilities (WMFs) and that became ubiquitous in air of urbanized regions. Urban birds including gulls have adapted to exploiting human food resources (refuse) in WMFs, and have thus experienced population explosions worldwide. However, foraging in WMFs for birds may result in exposure to HFRs that have been shown to be toxic for animals. The objective of this study was to determine the influence of foraging near or in various WMFs on the atmospheric exposure of birds to HFRs, and to localize other sources of HFRs at the regional scale in a highly urbanized environment. We measured the atmospheric exposure to HFRs in one of the most abundant gull species in North America, the ring-billed gull (Larus delawarensis), breeding in the densely-populated Montreal area (Canada) using a novel approach combining bird-borne GPS dataloggers and miniature passive air samplers (PASs). We determined concentrations of 11 polybrominated diphenyl ethers (PBDEs) and three emerging HFRs of high environmental concern in PASs carried by gulls. We show that the daily sampling rates (pg/day) of PBDEs in PASs were highest in gulls foraging in or around landfills, but were not influenced by meteorological variables. In contrast, the daily sampling rates of emerging HFRs were lower compared to PBDEs and were not influenced by the presence of gulls in or near WMFs. This study demonstrates that atmospheric exposure to HFRs and perhaps other semi-volatile contaminants is underestimated, yet important for birds foraging in landfills.

Polybrominated diphenyl ethers and alternative halogenated flame retardants in mollusks from the Chinese Bohai Sea: Levels and interspecific differences.

Polybrominated diphenyl ethers (PBDEs) and alternative halogenated flame retardants (AHFRs) were measured in eleven mollusk species collected from the Chinese Bohai Sea. PBDEs and AHFRs were detected in all species, and their average total concentrations were in the range of 22.5-355 and 10.0-84.3 ng/g lipid weight, respectively. Decabromodiphenyl ether (BDE-209) and decabromodiphenylethane (DBDPE) were the dominant halogenated flame retardants (HFRs), contributing 22.5% to 73.6% and 3.1% to 38.3% of the total HFRs, respectively. The levels of PBDEs and AHFRs were moderate to high from a global perspective. Interspecific differences in the accumulation of PBDEs and AHFRs were characterized by heat map and cluster analysis. Composition profile differences were also observed, with higher proportions of AHFRs in gastropods than in bivalves. These species-specific differences in concentrations and profiles in mollusks were attributed to different species traits, including feeding habit, trophic level, and metabolic potential.

Vertical profile of soil/sediment pollution and microbial community change by e-waste recycling operation.

The present study aims to assess the effect of electronic waste (e-waste) recycling on microbial community and the underlying modulation mechanism. Core soil/sediment samples were collected from an abandoned e-waste burning site and neighboring farmland/stream sites in Guiyu, China. High concentrations and health risks of toxic heavy metals, particularly, Sb and Sn, and halogenated flame retardants (HFRs), including decabromodiphenyl ether (BDE 209) and decabromodiphenyl ethane (DBDPE) were mostly retained at the top surface layers of soils/sediments (0-30cm) after more than one year of natural vertical diffusion and microbe-facilitated biodegradation. Heavy metals, such as Ag, Cd, Cu, Pb, Sb, and Sn, played a critical role for the reduction of microbial diversity. This is the first study reporting the open burning of e-waste caused an obvious heat effect and enriched thermophilic/mesophilic microbes in local area. The acid washing during e-waste recycling process may result in the enrichment of acidophilic microbes. This investigation showed that e-waste processing operation resulted in not only severe pollution of the soils/sediments by various pollutants, but also reduction of microbial diversity that was difficult to self-store by the local ecosystem.

Trace metals in e-waste lead to serious health risk through consumption of rice growing near an abandoned e-waste recycling site: Comparisons with PBDEs and AHFRs.

Despite the endeavour to eradicate informal e-waste recycling, remediation of polluted sites is not mandatory in many developing countries and thus the hazard of pollutants remaining in soil is often overlooked. It is noteworthy that a majority of previous studies only analysed a few pollutants in e-waste to reflect the impact of informal e-waste recycling. However, the actual impact may have been largely underestimated since e-waste contains various groups of pollutants and the effect of some emerging pollutants in e-waste remains unexplored. Thus, this study examined the contamination of metals, PBDEs and AHFRs in the vicinity of an abandoned e-waste recycling site. The accumulation and translocation of these pollutants in rice plants cultivated at the nearby paddy field were measured to estimate the health risk through rice consumption. We revealed that the former e-waste burning site was still seriously contaminated with some metals (e.g. Sn, Sb and Ag, Igeo > 5), PBDEs (Igeo > 3) and AHFRs (Igeo > 3), which can disperse to the nearby paddy field and stream. The rice plants can effectively absorb some metals (e.g. Mo, Cr and Mn, BCF > 1), but not PBDEs and AHFRs (BCF < 0.15), from soil and translocate them to the leaves. Alarmingly, the health risk through rice consumption was high primarily due to Sb and Sn (HQ > 20), whereas PBDEs and AHFRs had limited contribution (HQ < 0.08). Our results imply that abandoned e-waste recycling sites still act as the pollution source, jeopardising the surrounding environment and human health. Since some trace metals (e.g. Sb and Sn) are seldom monitored, the impact of informal e-waste recycling would be more notorious than previously thought. Remediation work should be conducted promptly in abandoned e-waste recycling sites to protect the environment and human health.

Is the urban-adapted ring-billed gull a biovector for flame retardants?

Birds may act as biovectors of nutrients and contaminants at the regional scale and potentially increase the exposure to such substances in ecosystems frequented by these birds. However, no study has estimated biotransport of contaminants by individual birds through their feces (guano). Elevated concentrations of halogenated flame retardants (HFRs) have been reported in ring-billed gulls (Larus delawarensis) breeding near Montreal (QC, Canada)- a known hotspot for HFRs. The objective of the present study was to investigate the concentrations of polybrominated diphenyl ethers (PBDEs) and selected emerging HFRs (e.g., Dechlorane-related compounds) in guano of individual ring-billed gulls, and to assess the relative accumulation of these HFRs by comparing concentrations in plasma (absorbed) versus guano (excreted). A second objective was to determine the importance of one of the largest ring-billed gull colony (Deslauriers Island) in North America located near Montreal as a vector of HFR biotransport at the regional scale. Elevated concentrations of PBDEs and Dechlorane plus were determined in guano and plasma of ring-billed gulls, although in general no difference was found between males and females. However, plasma to guano concentration ratios were significantly greater in females for the highly hydrophobic BDE-209 and Dechlorane plus compared to males. Overall, for both sexes combined, the total amount of HFRs (sum of the 16 major PBDEs and five emerging HFRs) deposited by this entire colony (64,980 gulls) in the Montreal area through guano during the 28-days incubation period was estimated to 1 g. This study showed that urban-adapted ring-billed gulls from this large colony represent an underestimated biovector of HFRs, which may contribute to augment exposure to these toxic compounds in nearby ecosystems.

Screening of organic flame retardants in Swedish river water.

Alternative flame retardants (FRs) have now replaced legacy FRs (such as polybrominated diphenyl ethers, PBDEs), but little is known about their fate in the aquatic environment. In this study, a range of legacy FRs (n=10) and alternative FRs, including halogenated FRs (HFRs, n=32) and organophosphorus FRs (OPFRs, n=19), were screened in water samples collected from 23 rivers covering the whole latitudinal range of Sweden. Of the 61 targeted FRs, 26 were detected in at least one of the river samples, with ΣFR concentrations ranging up to 170ngL-1 (mean 31±45ngL-1). In general, higher concentrations and a larger variety of FRs were detected in southern Sweden (ΣFR=60±56ngL-1) compared with the north (ΣFR=9.0±16ngL-1). In the south, HFRs were dominant, constituting on average 59% of ∑FRs, whereas in the north, OPFRs were dominant, constituting on average 82% of ∑FRs. This difference was best explained by higher population density in the south. The total daily flux of FRs into the Baltic Sea was estimated to be ~31kg and comprised mainly tetrabromobisphenol-A (TBBPA), 3,4,5,6-tetrabromophthalic anhydride (TEBP-Anh), and 2,4,6-tribromophenol (TBP). To the best of our knowledge, this is the first report of environmental occurrence of TEBP-Anh, which was detected in two rivers and is suggested to originate from airports located near the sampling sites.

Unusually high Deca-BDE concentrations and new flame retardants in a Canadian Arctic top predator, the glaucous gull.

Despite a sustained effort in surveying flame retardants (FRs) in wildlife from industrialized regions, their occurrence in birds or any other wildlife species spanning the Arctic regions, particularly in North America, has received limited attention. This study investigated in the top predator glaucous gull (Larus hyperboreus) breeding in the Eastern Canadian Arctic (Cape Dorset, Nunavut) a comprehensive suite of FRs including unstudied halogenated and non-halogenated FRs of potential health concern, along with legacy organochlorines and mercury. The influence of diet acquired locally and in wintering areas on the tissue contaminant profiles was also investigated using δ15N and δ13C signatures in liver and feathers. The principal constituent in the Deca-brominated diphenyl ether (BDE) mixture, BDE-209, was remarkably the most concentrated PBDE congener determined in liver samples of Eastern Canadian Arctic glaucous gulls. This suggests dietary exposure from the local marine food web and perhaps also from nearby community landfills. Moreover, this study revealed for the first time the presence of 16 emerging halogenated and non-halogenated FRs in glaucous gulls from this Arctic region including HBB, DDC-CO (anti and syn isomers), PBEB, EHTBB, BEHTBP as well as a series of organophosphate esters (OPEs) (TCEP, TCIPP, TPP, TDCIPP, TDBPP, TBNP, TBOEP, TBEP, TCrP, EHDPP, and TEHP). With the exception of BDE-209, concentrations of other halogenated FRs and organochlorines were found to be in the lower range in liver of Eastern Canadian Arctic glaucous gulls compared to individuals from other circumpolar populations (Svalbard and Greenland). Mercury and methylmercury concentrations, however, were greater than reported elsewhere for glaucous gull populations.

Environmental exposure to a major urban wastewater effluent: Effects on the energy metabolism of northern pike.

Municipal wastewater effluents (MWWEs) consist of dynamic and complex mixtures of chemical and biological compounds that can alter the health of exposed aquatic organisms. Disturbance of energy metabolism has been reported in fish exposed to MWWEs. However, there is a scarcity of knowledge on the physiological events leading to perturbation of energy balance and thyroid regulation, and associated lipid metabolism. The objective of the present study was to use a set of biomarkers, from gene transcription to body condition, to investigate the effects of a chronic environmental exposure to a major primary MWWE on fatty acid metabolism and thyroid hormone levels in northern pike (Esox lucius) collected from the St. Lawrence River near Montreal (QC, Canada). The exposure of pike to MWWE was examined through determination of a suite of persistent and bioaccumulative halogenated flame retardants in liver as this effluent is a known regional source for these chemicals. Greater hepatic concentrations of polybrominated diphenyl ethers (PBDEs, range: 29.6-465ng/g w.w. and 88.8-823ng/g w.w. in females and males, respectively) and other halogenated flame retardants (e.g., dechlorane-related compounds) were determined in fish collected downstream of the MWWE's point of discharge relative to the upstream site. This exposure in male pike was associated with decreased acyl-coA oxidase (acox1) and fatty acid synthase (fasn) mRNA levels as well as a decreased acyl-coA oxidase (ACOX) activity in liver. In female pike, MWWE exposure was associated with lower circulating free and total triiodothyronine (T3) levels and a tendency for greater total lipid percentages in liver. Present findings provide evidence that chronic exposure of a top predator fish to MWWE can be related to gender-specific effects on fatty acid metabolism and thyroid hormone homeostasis, and highlight the need for further investigation.

Historical trends and ecological risks of polybrominated diphenyl ethers (PBDEs) and alternative halogenated flame retardants (AHFRs) in a mangrove in South China.

While the production of polybrominated diphenyl ethers (PBDEs) was gradually phased out in the last decade, they may still pose hidden danger to the environment due to their toxicity and persistence. On the other hand, alternative halogenated flame retardants (AHFRs) have been increasingly used as substitutes for PBDEs and may further worsen environmental health. To determine the environmental impact of PBDEs and AHFRs, we examined the historical trends and ecological risks of PBDEs and AHFRs in a typical industrialized city in South China by measuring their concentrations in mangrove sediment. Results showed that the concentrations of PBDEs increased abruptly from 1997 to 2009 due to the use of commercial deca-BDE mixture, but were stabilized in recent years. The concentrations of AHFRs, mainly contributed by decabromodiphenyl ethane (DBDPE), kept increasing from 1997 onwards. Based on the temporal trends, DBDPE is predicted to be predominant over BDE 209 in future. Despite the observed similar concentration between BDE 209 and DBDPE, the former posed a high ecological risk, while the ecological risk of the latter was negligible. Therefore, more attention is required to manage the contamination of BDE 209 in the environment.

A miniature bird-borne passive air sampler for monitoring halogenated flame retardants.

Birds have been used intensively as biomonitors of halogenated flame retardants (HFRs), and several studies have reported elevated tissue concentrations and inter-individual variability for these contaminants. While diet is known to be an important exposure pathway for HFRs in birds, it has been suggested that exposure through air may represent an underestimated source of HFRs for certain species. However, a method was not available for measuring the atmospheric exposure of individual birds to HFRs or other semi-volatile contaminants. The goal of this study was to develop a bird-borne passive air sampler (PAS) enabling the determination of individual atmospheric exposure to gas- and particle-phase HFRs using the ring-billed gull (Larus delawarensis) nesting in the Montreal area (QC, Canada). The new miniaturized elliptical-shaped PAS (mean weight: 2.72g) was tested using two sorbent types during three exposure periods (one, two and three weeks). Results showed that PAS using polyurethane foam (PUF) combined with a glass fiber filter collected all major polybrominated diphenyl ethers (PBDEs) and exhibited better performance for collecting highly hydrophobic DecaBDE mixture congeners compared to the PAS using polydimethylsiloxane (PDMS). Emerging HFRs including hexabromobenzene, Dechlorane 604 Component B, and Dechlorane plus (DP) isomers also were sampled by the PUF-based PAS. Sampling rates for most HFRs were comparable between the three exposure periods. This novel bird-borne PAS provides valuable information on the non-dietary exposure of free-ranging birds to HFRs.

Temporal trends of PBDEs and emerging flame retardants in belugas from the St. Lawrence Estuary (Canada) and comparisons with minke whales and Canadian Arctic belugas.

An exponential level increase of the ubiquitous halogenated flame retardant (HFR) class polybrominated diphenyl ether (PBDE) has been documented during the 1990s in endangered belugas (Delphinapterus leucas) from the St. Lawrence Estuary (SLE), Eastern Canada. The recent worldwide bans and regulations of PBDE mixtures led to their replacement by alternative HFRs (so-called emerging HFRs) that are increasingly being reported in various environmental compartments. There are, however, limited knowledge on the spatial and temporal trends of PBDEs and emerging HFRs in cetaceans, especially after restrictions on PBDE usage. The first objective of this study was to investigate the occurrence of HFRs (35 PBDE congeners and 13 emerging compounds) in the blubber of belugas and minke whales (Balænoptera acutorostrata) found dead in the Estuary or Gulf of St. Lawrence as well as belugas from Nunavik (Canadian Arctic) collected as part of the Inuit subsistence hunt. A second objective was to investigate the trends of HFR concentrations in SLE beluga males between 1997 and 2013. PBDEs were the most abundant HFRs in all three whale populations, while hexabromobenzene (HBB), Chlordene Plus (CPlus), Dechlorane Plus (DP), and Dechlorane 604 Component B (Dec-604 CB) were quantified in the majority of blubber samples. Overall, concentrations of emerging HFRs were notably greater in SLE belugas compared to the two other whale populations, with the exception of DP and Dec-604 CB that were found in greater concentrations in Canadian Arctic belugas. No significant trend in blubber PBDE concentrations was found in SLE belugas during this 17-year period. This suggests that global PBDE regulations are too recent to observe changes in PBDE concentrations in belugas from this highly HFR-exposed environment. In contrast, concentrations of HBB and CPlus in SLE belugas decreased slightly from 1997 to 2013, while DP increased up until 2000 and decreased slightly thereafter. The occurrence and temporal variations of PBDEs and their replacement products in these cetaceans warrant continuous monitoring.

Screening for halogenated flame retardants in European consumer products, building materials and wastes.

To fulfill national and international fire safety standards, flame retardants (FRs) are being added to a wide range of consumer products and building materials consisting of flammable materials like plastic, wood and textiles. While the FR composition of some products and materials has been identified in recent years, the limited global coverage of the data and the large diversity in consumer products necessitates more information for an overall picture of the FR composition in common products/materials. To address this issue, 137 individual samples of various consumer products, building materials and wastes were collected. To identify and characterize potential sources of FRs in indoor environment, all samples were analyzed for content of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDDs) and novel flame retardants (NFRs). The most frequently detected were HBCDDs (85%), with the highest median concentration of Σ4HBCDDs of 300 mg kg-1 in polystyrenes. The highest median concentration of Σ10PBDEs was found in recycled plastic materials, reaching 4 mg kg-1. The lowest concentrations were observed for NFRs, where the median of Σ12NFRs reached 0.4 mg kg-1 in the group of electrical & electronic equipment wastes. This suggests that for consumer products and building materials that are currently in-use, legacy compounds still contribute to the overall burden of FRs. Additionally, contrasting patterns of FR composition in recycled and virgin plastics, revealed using principle component analysis (PCA), suggest that legacy flame retardants are reentering the market through recycled products, perpetuating the potential for emissions to indoor environments and thus for human exposure.

[Bioaccumulation of Halogenated Flame Retardants in Fish of Dongjiang River].

Bioaccumulation factor (BAF) plays a key role in identification of bioaccumulative substance and in assessment of chemical risks.In order to reveal the bioaccumulation behavior of fish in Dongjiang River,sediment,water and fish samples were collected from Dongjiang River and PBDEs,DBDPE,DP,TBBPA and HBCDs were measured.The ranges of lgBAF were 5.0-7.4,6.1-7.1,4.6-7.9,2.6-4.6 and 4.8-7.7,respectively.In the present study,most HFRs had a lgBAF of higher than 3.7,which suggested that they might be bioaccumulative.The BAF values of HFRs increased with increasing lgKow,when lgKow>7,the bioaccumulation extent decreased with the increase of lgKow.Biotransformation of γ-HBCD toward α-HBCD and the metabolism of BDE66 and BDE99 of these isomers might attribute to the deviation from the general trend predicted by Kow.More attention should be paid to DBDPE,since its BAF value was higher than that of BDE209.The BSAF values of most PBDEs,DBDPE,DP,TBBPA and HBCDs congeners in three fish species were less than 1,indicating that these compounds were unlikely to become a source of pollution to the aquatic organisms due to the poor bioavailability.

Characterization of anthropogenic impacts in a large urban center by examining the spatial distribution of halogenated flame retardants.

Anthropogenic impacts have continuously intensified in mega urban centers with increasing urbanization and growing population. The spatial distribution pattern of such impacts can be assessed with soil halogenated flame retardants (HFRs) as HFRs are mostly derived from the production and use of various consumer products. In the present study, soil samples were collected from the Pearl River Delta (PRD), a large urbanized region in southern China, and its surrounding areas and analyzed for a group of HFRs, i.e., polybrominated diphenyl ethers (PBDEs), decabromodiphenyl ethane, bis(hexachlorocyclopentadieno)cyclooctane (DP) and hexabromobenzene. The sum concentrations of HFRs and PBDEs were in the ranges of 0.66-6500 and 0.37-5700 (mean: 290 and 250) ng g(-1) dry weight, respectively, around the middle level of the global range. BDE-209 was the predominant compound likely due to the huge amounts of usage and its persistence. The concentrations of HFRs were greater in the land-use types of residency, industry and landfill than in agriculture, forestry and drinking water source, and were also greater in the central PRD than in its surrounding areas. The concentrations of HFRs were moderately significantly (r(2) = 0.32-0.57; p < 0.05) correlated with urbanization levels, population densities and gross domestic productions in fifteen administrative districts. The spatial distribution of DP isomers appeared to be stereoselective as indicated by the similarity in the spatial patterns for the ratio of anti-DP versus the sum of DP isomers (fanti-DP) and DP concentrations. Finally, the concentrations of HFRs sharply decreased with increasing distance from an e-waste recycling site, indicating that e-waste derived HFRs largely remained in local soil.

Contamination and distribution of heavy metals, polybrominated diphenyl ethers and alternative halogenated flame retardants in a pristine mangrove.

Owing to the expanding metal and electronics industries, pollution in the Pearl River Estuary needs special concern. Given the hydrodynamic effect, the pristine mangrove in Qi'ao Island would be contaminated by tidal flushing. Thus, we examined (1) the contamination of pollutants in this mangrove, including heavy metals, polybrominated diphenyl ethers (PBDEs) and alternative halogenated flame retardants (AHFRs), and (2) how habitat characteristics and sediment properties affect their distribution. Results showed that the sediment in Qi'ao mangrove had higher concentrations of heavy metals, PBDEs and AHFRs than that in other pristine mangroves, and similar concentrations to those mangroves impacted by point sources. Heavy metal concentrations were lower in the vegetated areas than mudflat, while the opposite was found for PBDEs and AHFRs. The findings imply that tidal flushing was an important pollution source, while mangrove plants have the capacity to minimize the impact of heavy metals, but not PBDEs and AHFRs.

[Concentrations and Partitioning of Halogenated Flame Retardants in Industrial Water of Dongjiang River].

The concentrations and partitioning of Halogented Flame Retardants (HFRs) were measured in industrial water of Dongjiang River. Polybrominated biphenyl ether (PBDEs) was the predominant pollutant accounting for 41.0% of the HFRs, dominated by BDE209 in the particulate phase, with the concentration ranging from 1102.3-3666.9 pg·L-1. The concentrations of Tetrabromobisphenol A (TBBPA) ranged from 1120.9-2856.5 pg·L-1, accounting for 32.4% of total halogenated flame retardants. The concentrations of other flame retardants, such as Decabromodiphenyl ethane(DBDPE), dechlorane plus (DP) and Hexabromocyclododecanes (HBCDs), accounting for 16.3%, 7.3% and 3.0%, were in the ranges of 397.7-1736.8, 235.7-778.1 and 9.5-266.8 pg·L-1, respectively. PBDEs, DBDPE, DP and HBCDs mainly existed in the particle phase, while TBBPA mainly existed in the dissolved phase due to its higher water solubility. Significant correlation between lgKoc and lgKow of HFRs was observed in the partitioning between the particulate phase and dissolved phase, but the observed organic carbon partition coefficients (lgKoc) were different from the predicted organic carbon partition coefficient (lgKoc), which may be controlled by the suspended particulate matter (SPM) content and dissolved organic carbon (DOC). In addition, whether the equilibrium was attained between dissolved phase and particle phase is another influencing factor for the observation.