Polybrominated Diphenyl Ethers In Sediments Research Articles

Determination of polybrominated diphenyl ethers in marine sediments by composite chromatography column purification-gas chromatography-negative chemical ionization-mass spectrometry

Polybrominated diphenyl ethers (PBDEs) are used as additive flame retardants. Because they lack the ability to form chemical bonds, PBDEs can easily enter the sediment environment. The accurate qualitative and quantitative analysis of PBDEs in sediments is of great importance for the accurate assessment of PBDE pollution in this environment. Sediments contain many impurities. Therefore, PBDEs in sediment should be purified before analysis to reduce the matrix effect. A method based on gas chromatography-negative chemical ionization-mass spectrometry (GC-NCI/MS) was developed to determine 13 PBDEs in marine sediment samples using a column packed with deactivated silica gel, acidified silica gel, Florisil, and anhydrous sodium sulfate. Sediment samples were extracted by ultrasonication with a mixed solvent of n-hexane-dichloromethane (3∶1, v/v). After two cycles of ultrasonic extraction, the extract was purified by a composite chromatographic column and eluted with n-hexane-dichloromethane (3∶1, v/v). Thirteen PBDEs were determined by GC-NCI/MS in selected-ion monitoring (SIM) mode. The effects of different fillers, eluents, and elution volumes on the purification of PBDEs in the composite column were compared and analyzed, and the GC-NCI/MS analysis conditions were optimized. Three different packing columns were used to purify the sample extract. The first column was packed with 3 g of deactivated silica, 6 g of acidic silica, 3 g of deactivated silica, 3 g of Florisil, and 6 g of anhydrous sodium sulfate; the second column was packed with 3 g of Florisil, 3 g of deactivated silica, 6 g of acidic silica, 3 g of deactivated silica, and 6 g of anhydrous sodium sulfate; and the third column was packed with 3 g of deactivated silica, 6 g of acidified silica, 3 g of deactivated silica, and 6 g of anhydrous sodium sulfate. Among these columns, that packed with 3 g of deactivated silica, 6 g of acidic silica, 3 g of deactivated silica, 3 g of Florisil, and 6 g of anhydrous sodium sulfate showed the best purification effect. The 13 PBDEs showed good linearity in the mass concentration range of 0.1-20 μg/L with correlation coefficients (r2) greater than 0.995 (decabromodiphenyl oxide (BDE-209), r2>0.99). The limits of quantification (S/N=10) was 0.002-0.126 μg/kg. The average recoveries of the 13 PBDEs at three spiked levels of 0.2, 1.0, and 4.0 μg/kg were 85.3%-101.3%, 84.8%-113.6%, and 86.3%-94.7% with relative standard deviations of 4.4%-14.0%, 0.4%-4.9%, and 1.9%-6.6%, respectively. These findings indicate that the method has high sensitivity and accuracy as well as good precision. Finally, the method was applied to the analysis and detection of PBDEs in actual marine sediment samples. The results revealed that the sediment samples contained different contents of the 13 PBDEs, and high detection rates were obtained for lower-brominated PBDE homologs. The detection rate of bis(4-bromophenyl) ether (BDE-15) was 100%, and the detected content of BDE-209 was as high as 60.49 μg/kg. These results demonstrate that the developed method is suitable for the accurate qualitative and quantitative analysis of PBDEs in marine sediment samples.

Organic matter degradation determines the concentrations of polybrominated diphenyl ethers in sediments. Multivariate learning on environmental and experimental models

Sediment organic matter (SOM) plays an important role in capturing polybrominated diphenyl ethers (PBDEs) due to its affinity to hydrophobic and lipophilic compounds. Previous publications about correlations between PBDE concentrations and SOM content showed discrepancies among the results, reporting either significant positive correlations or no correlations at all. This work aimed to provide a deeper insight into SOM characteristics that might determine the concentrations of PBDEs in sediments. Sediment samples from Mendoza province, Argentina, were analyzed to contrast two models, environmental and experimental, using multivariate learning methods. Mendoza has been going through increasing events of drought and water scarcity, hence the occurrence, transport, and fate of contaminants as PBDEs in aquatic environments is of superlative importance. Principal component analysis (PCA) and partial least squares regression (PLS) were used to evaluate the correlations between physicochemical properties of sediments, semi-quantitative Fourier transform infrared (FTIR) area ratios obtained from SOM spectra, and PBDE concentrations in sediments. Moreover, a linear model was proposed to determine SOM density using FTIR area ratios and it was used as an additional variable in multivariate analyses. The results obtained from PCA and PLS were consistent and revealed that PBDE concentrations in sediments were correlated with a more degraded SOM, characterized by shorter and more branched hydrocarbon chains. PBDE concentrations were also correlated with higher SOM density values, which in turn were correlated with SOM degradation. These findings extend previous understanding and emphasize that not only is the organic matter content a factor in determining PBDE concentrations in sediments, but also and more significantly, its degree of degradation.

Systematic characterization of sediment microbial community structure and function associated with anaerobic microbial degradation of PBDEs in coastal wetland

As the widely used flame retardant, polybrominated diphenyl ethers (PBDEs) have been ubiquitously detected in wetland sediments. Microbial degradation is the importantly natural attenuation process for PBDEs in sediments. In this study, the microbial degradation of PBDEs and inherent alternation of microbial communities were explored in anaerobic sediments from coastal wetland, North China. BDE-47 and BDE-153 could be degraded by the indigenous microbes, with biodegradation following pseudo-first-order kinetic. In sediments, the major genera for BDE-47 and BDE-153 degradation were Paeisporosarcina and Gp7, respectively, in single exposure. However, Marinobacter was dominant genera in the combined exposure to BDE-47 and BDE-153, and competition against Marinobacter existed between BDE-47 and BDE-153 degradation. Analysis of bacterial metabolic function indicated that membrane transport, amino acid and carbohydrate metabolism were included in degradation. This study provides the systematic characterization of the sediment microbial community structure and function associated anaerobic microbial degradation of PBDEs in coastal wetland.

Efficient and Complete Detoxification of Polybrominated Diphenyl Ethers in Sediments Achieved by Bioaugmentation with Dehalococcoides and Microbial Ecological Insights.

Polybrominated diphenyl ethers (PBDEs) are prevalent environmental pollutants, but bioremediation of PBDEs remains to be reported. Here we report accelerated remediation of a penta-BDE mixture in sediments by bioaugmentation with Dehalococcoides mccartyi strains CG1 and TZ50. Bioaugmentation with different amounts of each Dehalococcoides strain enhanced debromination of penta-BDEs compared with the controls. The sediment microcosm spiked with 6.8 × 106 cells/mL strain CG1 showed the highest penta-BDEs removal (89.9 ± 7.3%) to diphenyl ether within 60 days. Interestingly, co-contaminant tetrachloroethene (PCE) improved bioaugmentation performance, resulting in faster and more extensive penta-BDEs debromination using less bioinoculants, which was also completely dechlorinated to ethene by introducing D. mccartyi strain 11a. The better bioaugmentation performance in sediments with PCE could be attributed to the boosted growth of the augmented Dehalococcoides and capability of the PCE-induced reductive dehalogenases to debrominate penta-BDEs. Finally, ecological analyses showed that bioaugmentation resulted in more deterministic microbial communities, where the augmented Dehalococcoides established linkages with indigenous microorganisms but without causing obvious alterations of the overall community diversity and structure. Collectively, this study demonstrates that bioaugmentation with Dehalococcoides is a feasible strategy to completely remove PBDEs in sediments.

Assessment of Polybrominated Diphenyl Ethers (PBDEs) Level and Physico-Chemical Characteristics of Water and Sediment of Gulf of Guinea

The Lagos lagoon is the largest of the four lagoon systems of the Gulf of Guinea coast. This aquatic resource of multiple usages receives diverse organic and inorganic materials from domestic, industrial, emission, and thermal sources. The levels of Polybrominateddiphenyl ethers (PBDEs) were assessed to ascertain the pollution status of surface water and sediment within this lagoon system. Four stations were sampled for PBDEs analysis, and ranged for surface water physicochemical parameters are (27.93 to 28.50 ⁰C), (115.00 to 2152.70 µS/cm), (2.00 to 2.80 mg/L), (6.45 to 7.63), (25.02 to 84.60 NTU), (226.30 to 3999.00 mg/L), for temperature, electrical conductivity, dissolved oxygen, pH, turbidity, and total dissolved solids respectively. While the Total Organic Carbon (TOC) in sampled sediment ranged from 0.5 to 5.71 mg/L., the total concentrations of PBDEs in sediments ranged from 31.6 to 47.5 µg/Kg. Whereas the BDEs concentration in water ranged from 3.7 to 10.5 pg/L, total PBDE concentration of individual congener for water ranged from approximately 0.8 to 12.5 pg/L. The BDE 28 predominates across the locations followed by BDE 99. Impact of PBDEs concentration in the marine environment was evident within the study area.

Sediment Records of Polybrominated Diphenyl Ethers (PBDEs) from the Anhui Province Section of Yangtze River, China.

This study investigated the temporal changes of PBDEs in the sediment cores from the Anhui Province section of Yangtze River (YR), China. The dramatic increase of ∑Br3-Br9-BDEs and BDE-209 concentrations in cores in the period of ca. 1990-2008 was consistent with the booming of regional and national production and consumption of household appliances and electronics. Following declines in BDE-209 and ∑Br3-Br9-BDEs concentrations can be associated with the deceasing use of legacy commercial PBDE mixtures in recent years. Compared with the different regions around the world, sediments in the YR were moderately polluted by PBDEs. The levels and the detection rates of BDE-209 were highest among the detected PBDEs single congener. The composition analysis indicated that Deca-BDE, Octa-BDE, and Penta-BDE were the dominant forms in the YR. The increasing trends of both BDE-209 and ∑Br3-Br9-BDEs in the YR during 1990s and 2000s largely reflected the time periods for transferring PBDE sources from the developed countries to China. TOC and finer particles were strongly correlated with distributions of PBDEs in sediments.

Polybrominated diphenyl ethers (PBDEs) in the Danjiangkou Reservoir, China: identification of priority PBDE congeners.

Although the production of polybrominated diphenyl ethers (PBDEs) has been phased out over the past decade worldwide, they are still potentially hazardous to the environment due to their persistence and toxicity. This study investigated the levels of 55 PBDEs in water and sediments from the Danjiangkou Reservoir, China. The levels of PBDEs were in the range of not detected (ND)-286.67ng/L in water and ND-236.04ng/g in sediments. BDE209 was the predominant PBDE congener and constituted 15-50% and 44-68% of the total PBDEs in water and sediments, respectively. Commercial pentaBDE products (70-5DE, DE-71) were the dominant source of tetraBDE, pentaBDE, and hexaBDE, while commercial octaBDE (79-8DE) and decaBDE (102E and 82-0DE) products were the main sources of nonaBDE and decaBDE in water. PBDEs in sediments mainly stemmed from commercial decaBDE products and combustion sources. BDE-209 posed high ecological risks to aquatic organisms and dominated the total ecological risks of PBDEs. No cancer risks and non-cancer risks were observed for PBDEs. A ranking method based on four criteria, i.e., detection frequency, concentration, ecological risk, and health risks, was proposed, and 17 PBDEs were identified as high priority PBDEs for future monitoring and management in the Danjiangkou Reservoir.

Spatiotemporal Differentiation and Degradation Analysis of Polybrominated Diphenyl Ethers in Sediments of Shanmei Reservoir and Its Inflowing River, Quanzhou, China

To investigate the spatiotemporal differentiation of polybrominated diphenyl ethers (PBDEs) in urban water-source reservoirs and degradation sources of BDE homologues and their contributions, we analyzed the contents, pollution degrees, spatial distributions, hydrological period changes, inventories, profiles, and degradation source contributions of PBDEs in the surface sediments of Shanmei Reservoir and its inflowing river, Quanzhou, China. The results showed that the median ∑PBDEs (1072.1 ng ·g-1) in the inflowing river sediment was 6.7 times than that of the reservoir (160.4 ng ·g-1) and the total amount of ∑PBDEs in sediments per unit area (80.3 kg ·km-2) was 6.3 times than that of Taihu Lake and 188 times than that of the Great Lakes in North America. The pollution degrees of PBDEs in Shanmei Reservoir were more severe than those of most lakes and reservoirs at home and abroad, which was dominated by BDE-209 (84.5%-99.2%). Most of the sampling sites in the reservoir (r 0.564-0.994, P<0.034) and the inflowing river (r 0.953-1.0, P<0.000) had high similarity in the composition of PBDEs. Significantly positive correlations (r 0.779-0.964, P<0.005) were observed between the reservoir entry area and river sampling sites, which were stronger than the other functional areas, indicating that the inflowing river was a major pollution source of PBDEs in the Shanmei Reservoir. The tail region of the reservoir had low correlations with the inflowing river (r 0.454-0.915, P≤0.128), and was relatively much more affected by Jiudu Town. The changes in hydrological period of the ∑PBDEs were relatively consistent at each sampling site (r 0.617-0.714, P≤0.077), but the impact of the changes in the hydrological period on the ∑PBDEs was not statistically significant (P=0.178, Two-Way ANOVA). However, the site changes had a significant influence on the ∑PBDEs (P=0.0001), and significant or nearly differences were observed between the reservoir entry area and other functional areas (P 0.019-0.061), indicating that the spatial distribution variations of the PBDEs in reservoir sediments were greater than the changes in hydrological period. The natural degradation of the PBDEs gradually increased from the river to the reservoir entry area and then to the central reservoir area. The reductive debromination rates varied at different brominated levels, and some BDE homologues accumulated due to their slowly continued degradation velocities. Research on abundance ratios indicated that the lower brominated BDE homologues were mainly derived from the natural degradation of decabromodiphenyl ether by stepwise reductive debromination. Approximately 70% of Nona-BDE produced by Deca-BDE degradation could rapidly be degraded to form Octa-BDE. Approximately 85% of BDE-208 was derived from the degradation of BDE-209. During the degradation process from Octa-BDE to Penta-BDE, some Octa-BDE and Hexa-BDE homologues accumulated due to relatively slower degradation velocities, and the degradation rates of Penta-BDE to Tri-BDE were above 70%.

Concentration profile, spatial distributions and temporal trends of polybrominated diphenyl ethers in sediments across China: Implications for risk assessment

Polybrominated diphenyl ethers (PBDEs) in sediments of China have been extensively investigated; however, most studies conducted to date have focused on specific locations, and the pollution and risk posed by these chemicals in sediments at the national scale remain unknown. Therefore, we analyzed the concentrations and risks of PBDEs in sediments in China and their spatiotemporal variations based on available literature. Overall, the sediments across China contain moderate to high levels of PBDEs, with BDE-209 being the dominant congener, followed by BDE-47 and BDE-99. The sediment concentrations of PBDEs were highest in southern China and lowest in northeastern China. Additionally, based on their PBDE concentrations, 18.4%, 30.0%, and 11.9% of sediment samples from rivers, lakes, and coastal waters, respectively, posed low to moderate eco-toxicological risks, but 6.90% of river sediments posed high risks. Between 2001 and 2017, the concentrations and risks of PBDEs in the sediments from rivers and coastal waters tended to decrease gradually. Additionally, there were low to moderate risks from PBDEs in lake sediments, and the risks in 2012–2017 were 3.30 times higher than those in 2006–2011. However, more studies about the spatial and temporal trends in PBDEs in sediment across China and their impacts on aquatic organisms are needed because there is still a general lack of relevant information.

Field study on bioaccumulation and translocation of polybrominated diphenyl ethers in the sediment-plant system of a national nature reserve, North China

Polybrominated diphenyl ethers (PBDEs) are the ubiquitous contaminants in the coastal wetlands, with high persistence and toxicity. Environmental behaviors of PBDEs in sediment-plant system is a hot research area, where much uncertainties still occurred in field environment. In this study, the sediments and Suaeda heteroptera were synchronously collected to investigate the bioaccumulation and translocation of PBDEs in Liaohe coastal wetland. Mean concentrations of PBDEs in sediments, roots, stems and leaves were 8.37, 6.64, 2.42 and 1.40 ng/g d.w., respectively. Tissue-specific accumulation of PBDEs were detected in Suaeda heteroptera, with predominant accumulation in roots. Congener patterns of PBDEs were similar between sediments and roots, demonstrating root uptake as the key pathway of PBDE bioaccumulation. The proportions of lower brominated congeners increased from roots to leaves, implying the congener-specific translocation. Meanwhile, the lower brominated congeners exhibited higher sediment-tissue bioaccumulation (AFs) and translocation factors (TFs) compared to higher brominated congeners in Suaeda heteroptera, further verifying their preferential translocation. AFs and TFs of PBDEs were both not correlated with their log Kow, which was inconsistent with those of laboratory studies, reflecting the complicated behaviors of PBDEs in field environment. This is the first comprehensive report on bioaccumulation and translocation of PBDEs within Suaeda heteroptera in Liaohe coastal wetland.

Development of a fate and transport model for biodegradation of PBDE congeners in sediments

Polybrominated diphenyl ethers (PBDEs) are a family where each congener possesses different physicochemical properties, persistence and/or toxicity. Biodegradation can selectively change the abundance of congeners. These warrant modeling of individual congeners by considering biodegradation pathways together with fate and transport (F&T) mechanisms. Accordingly, this study aims to develop a F&T model (Fate and Transport model for Hydrophobic Pollutants - FTHP) that integrates congener specific biodegradation of PBDEs in sediments. The model is tested using sediment data from a location representing the Lower South Bay of San Francisco. Results demonstrated settling, resuspension, and biodegradation as important mechanisms. FTHP is then used to predict congener concentrations in a period of 20 years for two cases (constant and time-dependent water column concentrations) and four alternative scenarios: no intervention (i.e., natural attenuation, also serves as the base case), no degradation, dredging and biostimulation. The greatest impact on the reduction of total PBDE concentrations was achieved by a reduction in water column concentrations, i.e. source control, and dredging. On the other hand, biostimulation coupled with source control was the most effective in reducing bioaccumulative PBDE congener concentrations and almost as effective as dredging for the rest of congeners. Proposed FTHP model can distinguish between congeners and help devise informed management plans which focus on decreasing risks associated with persistent and bioaccumulative compounds in contaminated sediments.

Spatial distribution, source analysis, and ecological risk assessment of PBDEs in river sediment around Taihu Lake, China.

The distribution and composition of organic pollutants in sediment are affected by the source and regional environment. To understand the characteristics and risk of polybrominated diphenyl ethers (PBDEs) in the area around Taihu Lake, composite sediment samples (n = 41) were collected in rivers around Taihu Lake to explore the level, spatial distribution, and source of PBDEs. The results showed that the most abundant BDE congener in river sediment was BDE209, followed by BDE99 and BDE47, with median values of 48.7, 2.17, and 1.52ngg-1, respectively. Concentrations of PBDEs in sediments from northern rivers were significantly higher than those from other areas, but the overall risk was at a moderate-lower level compared with research results in other references. Results of principle component analysis (PCA) and source characteristics analysis revealed that most of PBDEs in river sediments around Taihu Lake were mixture of multiple sources, which mainly originated from atmospheric deposition, industrial wastewater, and municipal sewage. TOC showed good correlations with most PBDEs, which implied that PBDE components were influenced by sediment organic matter. Meanwhile, the risk of PBDEs in river sediments in this study area is a moderate-lower level.

Occurrence and Ecological Risk Assessment of Typical Persistent Organic Pollutants in Hengshui Lake

Sediment samples were collected from 11 typical sites in Hengshui Lake separately in August 2018 and March 2019. Characteristics and ecological risk assessment of typical persistent organic pollutants (POPs), including polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs), and polybrominated diphenyl ethers (PBDEs), in these sediments were analyzed. The results showed that the average content of ΣPAHs in sediments of Hengshui Lake was 875.49 ng·g-1 and 1010.17 ng·g-1 in August 2018 and March 2019, respectively. Compared with other regions in China and abroad, ΣPAHs in sediments from Hengshui Lake were at moderate pollution level. Distribution of ΣPAHs varied between different sites, but the values changed within a narrow range in different seasons. Sources of PAHs in sediments from Hengshui Lake were complex, but combustion of wood and coal was the main source, followed by oil pollution. Generally, the ecological risk of PAHs was at a low level. However, fluorene pollution control should be strengthened. For ΣOCPs, the average values in sediments were 35.57 ng·g-1 and 38.39 ng·g-1 in August and March, respectively. Compared with other regions, the pollution of ΣOCPs was at a moderate level. In addition, the distribution of ΣOCPs varied a small amount between different sites. There were significant differences between the two seasons. The contents of DDTs in sediments were mainly related to the residual DDTs after long-term soil weathering and the input of recent DDTs sources. Contents of HCHs in sediments were influenced by the use of HCHs in industrial history and inputs of agricultural lindane. Generally, the ecological risk of OCPs was at a medium level, but the DDTs pollution control should be strengthened. For ΣPBDEs, the average values were 1.77 ng·g-1 and 1.45 ng·g-1 in the sediments in August 2018 and March 2019, respectively. Compared with other regions, they were at a lower pollution level. The distribution of ΣPBDEs showed small differences between different sites, and did not obviously vary between spring and summer. The PBDEs in sediments were mainly low-bromine PBDEs, which might be contaminated with penta-BDEs from textiles and foams. Additionally, PBDEs were also probably input by distant settlement and migration from the atmosphere, and soil flushing into the lake. PBDEs posed no immediate ecological risk.

Uptake and trophic changes in polybrominated diphenyl ethers in the benthic marine food chain in southwestern British Columbia, Canada

We examined the physical and geochemical effects of sediment on the uptake of polybrominated diphenyl ethers (PBDEs) into marine sediment feeders and their transfer to higher trophic fauna. Sediment PBDEs increased with % total organic carbon (%TOC), organic carbon (OC) flux and grain size (%fines). Tissue PBDE variance was best explained ( R2 = 0.70) by sediment acid volatile sulfides (AVS), PBDEs, and organic lability and input, with the highest values near wastewater outfalls. Dry weight tissue/sediment PBDEs declined with increasing sediment PBDEs, resulting in tissue dilution (ratio &lt;1) at &gt;10 000 pg/g in harbours. Ratios also decreased with increasing %fines, resulting in regional differences. These patterns imply that high levels of fines and high sediment concentrations make PBDEs less bioavailable. Dry weight PBDEs increased &gt;100× between background deposit feeders and predators (polychaetes, crabs, bottom fish, seal), but lipid normalized PBDEs barely increased (&lt;1.3%), suggesting remarkably high uptake in low-lipid sediment feeders, and that PBDEs don’t accumulate at higher trophic levels, but lipid content does. Filter feeders had lower lipid-normalized PBDEs than deposit feeders, highlighting the importance of food resources in higher trophic fauna for bioaccumulation. The most profound congener change occurred with sediment uptake, with nona/deca-BDEs declining and tetra-hexa-BDEs increasing. Harbour sediment feeders had more deca-BDEs than other samples, suggesting PBDEs mostly pass unmodifed through them. Deca-BDEs persist patchily in all tissues, reflecting variable dependence on sediment/pelagic food.

In Situ Microbial Degradation of PBDEs in Sediments from an E-Waste Site as Revealed by Positive Matrix Factorization and Compound-Specific Stable Carbon Isotope Analysis.

In the present study, positive matrix factorization (PMF) and compound-specific isotope analysis were used to investigate the in situ biodegradation of polybrominated diphenyl ethers (PBDEs) in sediment cores collected from a pond at an e-waste recycling site in South China. The potential microorganisms relevant to the degradation of PBDEs were also assessed to aid in the understanding of in situ biodegradation. The PMF results suggested that reductive debromination took place in the sediments. The debromination signal (ratio of the concentration of factor 5 (PMF result) to the total PBDE content) was positively correlated with the relative abundance of Dehalococcoidetes at different core depths. The clear 13C enrichment of five PBDE congeners (BDE 28, 47, 49, 99, and 153) with increasing core depth indicated that a measurable change in isotope fractionation might have occurred during PBDE biodegradation. The in situ biodegradation was further validated by the widespread detection of mono-BDE congeners (BDE 2, BDE 3) and diphenyl ether in the sediments. This study provides new evidence to enhance our understanding of the in situ biodegradation of PBDEs and suggests that the extensive removal of bromine from PBDEs was mediated by indigenous microorganisms at the e-waste site.

Reflection of concentrations of polybrominated diphenyl ethers in health risk assessment: A case study in sediments from the metropolitan river, North China

As a developed city in North China, Tsingtao is believed to be suffering from the pollution of polybrominated diphenyl ethers (PBDEs) due to the rapid industrialization and urbanization in recent years. In this work, 8 PBDE congeners were detected in sediments from Moshui River, Tsingtao. BDE-209 and sum of 7 low brominated PBDE congeners (∑7PBDEs, excluding BDE-209) ranged from 10.2 × 10−3 to 237 × 10−3 mg kg−1 and from 1.62 × 10−3 to 23.1 × 10−3 mg kg−1 d.w., respectively. PBDE concentrations decreased in the order of midstream > downstream > upstream, attributing to the discrepancies in anthropogenic activities among these areas. Principal component analysis coupled with multiple linear regression (PCA-MLR) revealed that 24.4% of PBDEs were derived from surface runoff of contaminated soils, 58.2% from direct discharge of local sources and 17.4% from atmospheric deposition. The probabilistic health risk assessment of PBDEs was performed by using Monte Carlo simulation. The carcinogenic and non-carcinogenic risks based on total PBDEs were low for children and teens, whilst severe for adults. However, based on bioaccessible PBDEs (in vitro gastrointestinal model), there was no obvious health risk for the three age groups. To the best of our knowledge, the present study was the first attempt to assess the health risk by using bioaccessible PBDEs in sediments.

Characterization of brominated, chlorinated, and phosphate flame retardants in San Francisco Bay, an urban estuary

Flame retardant chemical additives are incorporated into consumer goods to meet flammability standards, and many have been detected in environmental matrices. A uniquely wide-ranging characterization of flame retardants was conducted, including polybrominated diphenyl ethers (PBDEs) and 52 additional brominated, chlorinated, or phosphate analytes, in water, sediment, bivalves, and harbor seal blubber of San Francisco Bay, a highly urbanized estuary once considered a hot spot for PBDE contamination. Among brominated flame retardants, PBDEs remained the dominant contaminants in all matrices, though declines have been observed over the last decade following their phase-out. Hexabromocyclododecane (HBCD) and other hydrophobic, brominated flame retardants were commonly detected at lower levels than PBDEs in sediment and tissue matrices. Dechlorane Plus (DP) and related chlorinated compounds were also detected at lower levels or not at all across all matrices. In contrast, phosphate flame retardants were widely detected in Bay water samples, with highest median concentrations in the order TCPP > TPhP > TBEP > TDCPP > TCEP. Concentrations in Bay water were often higher than in other estuarine and marine environments. Phosphate flame retardants were also widely detected in sediment, in the order TEHP > TCrP > TPhP > TDCPP > TBEP. Several were present in bivalves, with levels of TDCPP comparable to PBDEs. Only four phosphate flame retardants were detected in harbor seal blubber: TCPP, TDCPP, TCEP, and TPhP. Periodic, multi-matrix screening is recommended to track contaminant trends impacted by changes to flammability standards and manufacturing practices, with a particular focus on contaminants like TDCPP and TPhP that were found at levels comparable to thresholds for aquatic toxicity.

Polybrominated diphenyl ethers (PBDEs) in core sediments from creek ecosystem: occurrence, geochronology, and source contribution.

The levels of 15 polybrominated diphenyl ether (PBDE) congeners in grab sediment and sediment cores from the Thane creek were monitored for their spatial and temporal distribution. Total PBDE (ΣPBDE) concentrations in grab sediments were ranging from 15.98 to 132.72ngg-1 dry weight. BDE-209 was the most abundant congener with percentage contribution in the range of 19-35% to total PBDEs. Total PBDE show multimode concentration with depth in sediment, among which mode at a depth of 10cm is predominant. Results of sediment core also indicates PBDEs were enormously used in last two decades in surrounding area. Sedimentation rate at the creek was also evaluated using Pb210 dating technique. Average percentage contribution of commercial penta-BDE (fP), octa-BDE (fO), and deca-BDE (fD) to the profile found in sediments collected across Thane creek were 24 ± 5, 5 ± 1 and 69 ± 7% (p < 0.001) respectively. Levels of all measured PBDEs in sediment met with guideline values except for the penta-BDE (total, BDE-99 and BDE-100) at few locations.

Distribution and partitioning of polybrominated diphenyl ethers in sediments from the Pearl River Delta and Guiyu, South China.

Polybrominated diphenyl ethers (PBDEs) were investigated by GC-NCI-MS in sediments collected from the Pearl River Delta (PRD) and Guiyu town, South China. The concentrations of ∑39PBDEs and BDE 209 were in the ranges of 0.31-38.9 ng g-1 and 12.2-488 ng g-1 in the PRD, and 2.57-21,207 ng g-1 and 7.02-66,573 ng g-1 in Guiyu, respectively. The levels of PBDEs in Dongjiang River (DJ), Zhujiang River (ZJ), and Beijiang River (BJ), and Guiyu (GY) followed the order: GY > DJ > ZJ > BJ. The very high PBDE concentration (87,779 ng g-1) was detected at G1 sediment in Guiyu compared with those in sediments from other regions around the world. The PBDE mixtures detected were mainly comprised of penta-, octa-, and deca-BDEs, in which deca-BDE was the dominant constituent. The abundant congeners, excluding BDE-209, were BDE-47, BDE-99, and BDE-183, suggesting the diverse use of commercial products containing these congeners in this region. The concentrations of major congeners were significantly correlated with total organic carbon (TOC) contents (p < .01). A good regression between the logarithmic TOC-normalized BDE average concentrations and their log Kow confirmed that the sorption of PBDEs on sediment organic matter governed their spatial distribution, transport, and fate in the sediments. Furthermore, risk quotients (RQs) derived from concentrations of PBDEs in sediments from our study may pose high ecological risks to exposure of benthic organisms.

A 21-year record of methoxylated and hydroxylated polybrominated diphenyl ethers in sediments from the East China Sea

Sediments are major sinks for organic pollutants and therefore can be used as archives of pollutant history. Methoxylated (MeO-) and hydroxylated (OH-) polybrominated diphenyl ethers (PBDE) are of increasing concern because of their potential toxicity and worldwide distribution. However, there is limited information on these compounds in marine environments. Here we determined the contents of nine MeO-PBDE, ten OH-PBDE and total organic carbon in a sediment core collected from the inner shelf of the East China Sea in 2009. The historical trends of 6-MeO-BDE47, 6-OH-BDE47 and total organic carbon were reconstructed. Our results show that 6-MeO-BDE47 concentrations present no significant trend from 1987 to 2005 and then increase from 2005 to 2008. 6-OH-BDE47 concentrations generally increase slightly from 1987 to the end of the 1990s and then decrease. Comparisons between 6-OH-BDE47 and 6-MeO-BDE47 as well as total organic carbon suggest that 6-OH-BDE47 is mainly from terrigenous inputs.