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Polybrominated diphenyl ethers (PBDEs) were measured in 182 sediments from the Huron–Erie Corridor, North America. The median (5–95 percentile) Corridor ∑PBDE concentration was 1.03 ng/g dry wt (0.25–13.48 ng/g dry wt). Dry weight ∑PBDEs were elevated in U.S. waters of the Detroit River (US DR) and lowest in Canadian waters of Lake St. Clair (CA LSC). Sediment total organic carbon (TOC) explained some of the variation in ∑PBDEs, particularly in upstream waterbodies except for the Detroit River where local sources were apparent in the US DR and TOC-dilution occurred in CA DR. Canadian Federal Sediment Quality guidelines were exceeded at 19 stations, 14 occurring in the US DR. ∑Hazard Quotients (∑HQ) had a median (5–95 percentile) Corridor value of 0.46 (ND to 2.27). By strata, 43.2% of US DR stations had ∑HQ's greater than 1 while 21.3% of US SCR stations exceeded a value of 1. [ABSTRACT FROM AUTHOR]

Background Polybrominated diphenyl ethers (PBDEs), a widely utilized class of flame retardants in various commercial products, represent a prominent source of environmental contaminants. PBDEs tend to accumulate in adipose tissue, potentially altering the function of this endocrine organ and increasing risk of insulin resistance. The aim of this study was to compare levels of PBDEs in adipose tissues from two metabolically distinct obese groups; the insulin sensitive (IS) and the insulin resistant (IR). Methods Levels of 28 PBDE congeners were assessed in subcutaneous and omental adipose tissues from 34 obese Qatari individuals (11 IS and 23 IR) using gas chromatography (Trace GC Ultra) coupled to a TSQ Quantum triple Quadrupole mass spectrometer. Correlations of identified PBDEs and mediators of metabolic disease were established and effects of PBDEs treatment on insulin signaling in primary omental preadipocytes were determined. Results Out of 22 detectable PBDEs in subcutaneous and omental adipose tissues, PBDEs 28, 47, 99 and 153 were predominant in omental adipose tissues from obese Qatari subjects. PBDEs 99, 28, and 47 were significantly higher in IR individuals compared to their IS counterparts. Significant positive correlations were identified between PBDEs 28 and 99 in the omental tissues and with fasting insulin levels. When considering PBDEs congeners, penta congeners were also higher in IR compared to IS individuals, while no significant differences were detected in mono, tri, tertra, hexa, hepta and octa congeners between the two studied groups. Treatment of human omental preadipocytes from insulin sensitive individuals with PBDE28 caused inhibition of phosphorylation of GSK3 α/β (Ser 21 /Ser 9 ), mTOR (Ser 2448 ), p70 S6 kinase (Thr 389 ) and S6 ribosomal protein (Ser 235 /Ser 236 ) and activation of PTEN (Ser 380 ) phosphorylation, suggesting inhibition of insulin signaling. Conclusion This pilot data suggests that accumulation of specific PBDEs in human adipose tissues is associated with insulin resistance in obese individuals. Further investigation of the functional role of PBDEs in the pathology of insulin resistance should help developing therapeutic strategies targeting obese individuals at higher risk. [ABSTRACT FROM AUTHOR]

Two prominent polybrominated diphenyl ether (PBDE) congeners have been included in the persistent organic pollutant list, 2,2′,4,4′,5-tetrabromodiphenyl ether (BDE-99) and 2,2,4,4′-tetrabromodiphenyl ether (BDE-47), which have been detected in treated municipal wastewater, river water, and sediments in China. A lab-scale column experiment was established to investigate the effects of the competitive sorption of BDE-47 on BDE-99 biodegradation and migration in two types of river-based aquifer soils during groundwater recharge with reclaimed water. Two types of recharge columns were used, filled with either silty clay (SC) or black carbon-amended silty clay (BCA). The decay rate constants of BDE-99 in the BCA and SC systems were 0.186 and 0.13 m−1 in the single-solute system and 0.128 and 0.071 m−1 in the binary-solute system, respectively, showing that the decay of BDE-99 was inhibited by the coexistence of BDE-47. This was particularly evident in the SC system because the higher hydrophobicity of BDE-99 determined the higher affinity and competition for sorption sites onto black carbon. The biodegradation of BDE-99 was suppressed by the coexistence of BDE-47, especially in the SC system. Lesser-brominated congeners (BDE-47 and BDE-28) and higher-brominated congeners (BDE-100, BDE-153, BDE-154, and BDE-183) were generated in the four recharge systems, albeit at different ratios. Bacterial biodiversity was influenced by the presence of BDE-47 in the SC system, while it had no significant effect on the BCA system, because the high sorption capacity of black carbon on the hydrophobic PBDEs effectively reduced their toxicity. The ranking order of the most abundant classes changed markedly due to the coexistence of BDE-47 in both the SC and BCA systems. The ranking order of the most abundant genera changed from Azospira, Methylotenera, Desulfovibrio, Methylibium, and Bradyrhizobium to Halomonas, Hyphomicrobium, Pseudomonas, Methylophaga, and Shewanella, which could be involved in PBDE degradation. [ABSTRACT FROM AUTHOR]

Indigenous microorganisms in sediments could degrade polybrominated diphenyl ethers (PBDEs), but how the microbial communities respond to PBDEs was seldom reported. The effect of BDE-153, a common congener in aquatic environments, on the microbial communities in four types of aquatic sediments was evaluated during the 150 days' incubation under an anaerobic condition. The intrinsic potential to remove BDE-153 varied significantly among four sediment types, and the removal rates of mangrove, mudflat, marine and freshwater sediments were 0.013, 0.013, 0.011, and 0.009 day − 1 , respectively. The observed microbial species, Simpson, Shannon, and Chao1 indices in all sediments were rather stable and were not changed significantly by BDE-153 amendment. However, BDE-153 amendment altered the microbial community compositions in three saline sediments at the end of the incubation period. Distance-based multivariate multiple regression analysis revealed that salinity, total organic carbon (TOC) and BDE-52, the major debromination product of BDE-153, were the three main factors explaining the variations in microbial community compositions in BDE-treated sediments; whereas salinity, TOC and pH were the main contributing factors in control sediments without BDE-153. The daughter congeners generated during anaerobic debromination process need more attention, especially their effect on the microbial communities in aquatic sediments. [ABSTRACT FROM AUTHOR]

A three-year monitoring campaign (Jan 2011–2014) of polychlorinated biphenyl (PCBs) and polybrominated diphenyl ethers (PBDEs) was conducted using a high-volume air sampler at the Chinese Great Wall Station in King George Island, West Antarctica. The results showed that the Σ 20 PCB and Σ 27 PBDE concentrations (gas + particle) were 5.87–72.7 pg m −3 and 0.60–16.1 pg m −3 , respectively. The lighter congeners especially PCB-11 (a non-Aroclor congener) dominated Σ 20 PCBs, while BDE-209 made a significant contribution to Σ 27 PBDEs apart from the lighter congeners (e.g., BDE-28 and -17). The chiral signature indicated nonracemic residues of chiral PCBs in the samples, suggesting potential influence of the secondary source, i.e. air-seawater exchange, on the atropisomer composition of chiral PCBs in air. Lighter PCBs (excluding PCB-11) showed significant temperature dependence in 2011 and 2012, reflecting the influence of revolatilization emission from the local surface. However, the shallow slopes of the regression lines for gaseous concentrations of POPs against reciprocal temperature (1/ T ) suggested long-range atmospheric transport (LRAT) as an important pathway for both PCBs and PBDEs into the Antarctic environment. Furthermore, correlations and ratios between different signature congeners deriving from the technical formulations indicated a local source of Deca-BDE and photodegradation of higher brominated BDEs. The gas/particle partitioning of POPs was also evaluated and the newly developed steady-state-based model generally showed a better performance than the equilibrium-state-based model. However, the former still underestimated the partitioning of most PCBs (log K OA <11) in particle phase, implying that further optimization is necessary when using it for those compounds with lower log K OA . [ABSTRACT FROM AUTHOR]

Polybrominated diphenyl ethers (PBDEs) are used as flame retardants in many applications; however, certain PBDE congeners are persistent, bioaccumulative, and toxic to both humans and the environment. PBDEs have been found in human specimens, and a variety of analytical techniques have been used for their determination in biological matrixes. Nevertheless, obtaining a relatively clean analytical blank sample during PBDE analysis is a big challenge because of the ubiquitous nature of these compounds. Thus, the present study was conducted to compare the PBDE background levels associated with the three most commonly used extraction techniques: liquid-liquid extraction (LLE), SPE, and accelerated solvent extraction (ASE). Conventionally used blank matrixes (HPLC grade water, Milli-Q water, and air) were spiked with internal standards and extracted using LLE, SPE, or ASE. The extracts were analyzed by GC/electron ionization-tandem MS. The ASE method achieved the lowest background levels for nearly all the PBDE congeners analyzed, which may be attributed to the stainless steel and closed-vessel nature of the ASE cells. [ABSTRACT FROM AUTHOR]

An analytical method has been developed for the pressurized liquid extraction (PLE) of a wide range of semi-volatile organic compounds (SVOCs) from atmospheric particulate matter. Approximately 130 SVOCs from eight compound classes were selected as molecular markers of (1) agricultural activity (30 current and historic-use pesticides), (2) industrial activity (18 PCBs), (3) consumer products and building materials (16 PBDEs, 11 OPEs), and (4) motor vehicle exhaust (22 PAHs, 16 alkanes, 9 hopanes, 8 steranes). Currently, there is no analytical method validated for the extraction of all eight compound classes in a single automated technique. The extraction efficiencies of varying solvents and solvent combinations at high temperatures and pressures were examined. Extracts were concentrated and analyzed by gas chromatography coupled with mass spectrometry. The optimized PLE method utilized methylene chloride:acetone (2:1 v/v) at 100 °C with three (5 min) static cycles, flush volume of 80%, and a 100 s N 2 purge. Spike and recovery experiments ( n = 7) provided average percent recoveries for pesticides, PCBs, PBDEs, OPEs, PAHs, alkanes, hopanes, and steranes of 88.8 ± 4.0%, 86.9 ± 2.6%, 83.8 ± 2.9%, 101 ± 6%, 90.3 ± 6.1%, 74.4 ± 8.8%, 104 ± 8%, and 86.5 ± 8.6%, respectively. The developed method was applied to atmospheric particulate matter samples collected in the greater Houston, TX metropolitan area. Ambient concentrations of eight classes of compounds (92 SVOCs) were reported in pg m −3 . [ABSTRACT FROM AUTHOR]

The Water Framework Directive (WFD) includes some polybrominated diphenyl ethers (PBDEs) in the list of priority substances that must be measured in surface waters at very low concentrations. The typical approaches applied to the determination of PBDEs in environmental samples might not meet the demanding requirements of the WFD. In this work, the instrumental capabilities of the mass-spectrometry (MS) techniques most frequently used in the determination of PBDEs, namely gas chromatography-negative-chemical-ionisation MS (GC-NCI MS) and GC-electrospray-ionisation tandem MS (EI MS-MS), are evaluated in comparison with highly sensitive GC-inductively-coupled-plasma MS (ICP-MS) for the reliable determination of PBDEs according to the WFD. Three analytical methods based on the liquid-liquid extraction of water samples and measurement of the extracts by GC-NCI MS, GC-EI MS-MS, or GC-ICP-MS are described. The priority PBDEs were quantified in different types of water sample by means of isotope-dilution mass spectrometry (IDMS) using Br-labelled or C-labelled PBDEs spikes, depending on the selected ionisation source. The three proposed methods met the requirements of the European legislation in terms of LOQs and expanded uncertainties. The determination method using Br-labelled PBDEs and GC-ICP-MS had the highest sensitivity and the lowest instrumental limits of detection and expanded uncertainties. [ABSTRACT FROM AUTHOR]

This study investigated the material/substance flow of polybrominated diphenyl ethers listed in the Stockholm Convention (SC) as persistent organic pollutant (POP-PBDEs) in the most relevant plastic fractions in Nigeria. Considering the prohibition of production and the use of POP-PBDEs and knowing that these pollutants are still contained in electrical and electronic equipment (EEE) and associated wastes (WEEE), it is necessary to determine their flows, especially in developing countries with limited end-of-life management. Following the inventory approach of the SC Guidance and utilizing the existing national e-waste inventory together with monitoring data, a material/substance flow analysis was conducted using the STAN tool. Within the period of 2000 to 2010, the total import for EEE/WEEE in Category 3 and 4 was approximately 8 million tonnes (Mt) containing approximately 2.4 Mt of polymers. For the inventory year 2010, it was estimated that from these polymers, about 0.8 Mt was still in stock and 1.6 Mt has reached the end-of-life. It was also estimated that approximately 1.1 Mt has ended in dumpsites, 0.3 Mt was burned in the open, and 0.2 Mt was recycled. In the plastic fractions, 1,270 t of POP-PBDEs was contained with about 370 t still in use/stock and approximately 900 t has entered the end-of-life phase. All three major end-of-life treatments result in environmental pollution with associated exposure risk. The implementation of the Stockholm Convention represents an important opportunity to improve this management situation in Nigeria and other developing countries. [ABSTRACT FROM AUTHOR]

Indoor environment is an important source of human exposure to several toxicants, such as brominated flame retardants. Indoor dust samples were collected in winter season in 2010, which covered 23 provinces across China, for the analysis of polybrominated diphenyl ethers (PBDEs). Concentrations of PBDEs ( Σ 14 PBDEs) ranged from 8.92 to 37 500 ng/g, with the mean of 3520 ng/g. BDE-209 was the most dominate congener, followed by BDE-183, BDE-47 and BDE-99. PBDE concentrations and the longitude were significantly correlated ( p <0.05), which was consistent with the status of social-economic development and human activities. The results of exposure to PBDEs through dust ingestion and dermal absorption indicated that the toddlers had the highest exposure dose, with the median value of 6.0 ng/kg-bw/day. According to the hazard quotients, health risk of PBDEs via dust ingestion in China is currently acceptable. Monte Carlo simulation was implemented to quantify the uncertainty and sensitivity of exposure models for determining the most influential variables. The results suggested that more specific and accurate parameters should be used for dust ingestion and dermal absorption exposure models in future. [ABSTRACT FROM AUTHOR]

This study investigates the distribution of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD) and a group of novel flame retardants (NFRs) on atmospheric aerosols. Two high volume cascade impactors were used to collect particulate fractions of ambient air over a one year period at urban and rural sites. The majority of FRs were found on the finest aerosols (<0.95 μm). Concentrations of HBCD were higher than those of ΣPBDEs. Moreover, we noted seasonality and spatial differences in particle size distributions, yet a large portion of the observed differences were due to differences in particulate matter (PM) itself. When normalized by PM, the size distributions of the FRs exhibited much greater heterogeneity. Differences existed between the FR distributions by molecular weight, with the higher molecular weight FRs (e.g., BDE-209, Dechlorane Plus) distributed more uniformly across all particulate size fractions. The seasonal, spatial, and compound-specific differences are of crucial importance when estimating dry and wet deposition of FRs as smaller aerosols have longer atmospheric residence times. Estimated wet and dry deposition of four representative FRs (BDE-47, BDE-209, HBCD, and Dechlorane Plus) using size-segregated aerosol data resulted in lower deposition estimates than when bulk aerosol data were used. This has implications for estimates of long-range atmospheric transport and atmospheric residence times, as it suggests that without size-specific distributions, these parameters could be underestimated for FRs. [ABSTRACT FROM AUTHOR]

Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD) are bioaccumulative flame retardants. PBDEs increased in many ecosystems during the late 20th century, but recently have declined in some environments. To examine trends in the northern Pacific, we analysed PBDEs, HBCDD and carbon and nitrogen stable isotopes (δ 13 C and δ 15 N) to account for dietary effects in archived eggs of three seabird species from British Columbia, Canada, 1990–2011 (rhinoceros auklets, Cerorhinca monocerata ; Leach's storm-petrels, Oceanodroma leucorhoa ; ancient murrelets, Synthliboramphus antiquus , 2009 only). PBDEs increased until approximately 2000 and then decreased, while HBCDD increased exponentially throughout the examined period. No significant changes in dietary tracers were observed. HBCDD and ΣPBDE levels varied among species; ΣPBDE also varied among sites. Temporal changes in contaminant concentrations are unlikely to have been caused by dietary changes, and likely reflect the build-up followed by decreases associated with voluntary phase-outs and regulations implemented in North America to control PBDEs. [ABSTRACT FROM AUTHOR]

This study assessed the level of 24 polybrominated diphenyl ethers (PBDEs) in Korean foods following a Progressive Total Diet Study (TDS). The experiments comprised 96 types of dietetically representative foods, all were either cooked or edible raw. PBDEs were widely encountered in foodstuffs with the highest concentration in plant oils, fishes and shellfishes. Of all congeners tested for, BDE-47 was the most predominant and encountered in almost all food items except meats. The presence of nona-BDEs at significant levels indicated that Korean environments are still contaminated by deca-BDE. The daily dietary intake of PBDEs was estimated to be 63 ng d-1. The highest PBDEs intake was observed in the 19–39 year old group and gradually decreased as age increased. Our study suggests that the TDS approach using foods in the table-ready form should be used for a better estimation of dietary exposure to PBDEs. [ABSTRACT FROM AUTHOR]

As part of a broader study of budgets, transport, and bioaccumulation of persistent organic contaminants in the Strait of Georgia, Canada, matching samples of sediment and bulk benthos were collected near two marine sewage outfalls, two large urban harbours, and background areas. Samples were analyzed for polychlorinated biphenyl (PCB) and polybrominated diphenyl ether (PBDE) congeners. We present data for those congeners that fell within the top six rankings by concentration (23 PCBs and 10 PBDEs) within at least one of the environmental media measured in other studies (air, water, sediments, benthos, pelagic biota). Multifactor regression analyses incorporating sediment characteristics (total organic carbon, fines) predicted uptake ( r = 0.74 to 0.98, p < 0.04) over the range of congeners and habitats examined. PBDEs were taken up by biota more readily than PCBs, suggesting a large, potentially available biological reservoir of PBDEs in sediments. Dominant congeners in benthos comprised PBDEs 47, 99, 209, and 100 and PCBs 138/163, 153, 101, 118, and 110. PBDE uptake was anomalously high near one wastewater outfall, likely due to selective feeding on PBDE-enriched particulates from that source. Conversely, outfalls supply food and sediments with PCB concentrations similar to ambient sediments. However, organic enrichment of sediments near outfalls clearly enhanced PCB uptake by benthos, probably due to greatly increased biomass turnover near these sources. Data suggest there to be an initial reservoir of PCBs in newly settled juvenile benthos, which is much less evident for PBDEs. This is likely a consequence of the ecosystem-wide distribution of legacy PCBs but not the more current-use PBDEs. Congener-uptake patterns were dependent on source and input dynamics, feeding methods, and contaminant metabolism or debromination, particularly of deca-BDE. [ABSTRACT FROM AUTHOR]

Atmospheric polybrominated diphenyl ethers (PBDEs) were monitored monthly from 2010 to 2013 at rural and urban sites near a large shallow Chinese lake (Lake Chaohu). The urban areas had higher air PBDEs than the rural areas because of endogenic pollution. The highest and lowest concentrations of Σ13BDEs were observed in the winter and in the summer, respectively. A weak temperature dependence and significant positive correlations between certain PBDE congeners and the PM10 (p < 0.01) suggest transport with particulate matter. Using air-mass back-trajectories, we determined that the main sources of the PBDEs were the areas to the north, such as Shandong Province, and to the east, such as Zhejiang Province. PBDEs did not pose an appreciable risk to human health based on the inhalation exposure assessment. The residents in urban areas were exposed to higher levels of PBDEs, and wintertime exposures posed the greatest human health risk. [ABSTRACT FROM AUTHOR]

The vertical distribution of polybrominated diphenyl ethers (PBDEs) in soil at four sites within an e-waste recycling region of South China was investigated. PBDE concentrations in soil ranged from 1.38 to 765 ng/g. There was a trend of decreasing PBDE concentration with soil depth, especially in the paddy field. However, high concentrations of BDE-209 were found in deeper soils indicating a highly preferential migration. There was a stronger correlation between PBDEs and total organic carbon (TOC), compared to dissolved organic carbon (DOC), which suggests that the association between non-dissolved organic carbon (NDOC) and PBDEs is stronger than for DOC. Different land use types, in particular differences in farming activities, significantly influenced the vertical distribution of PBDEs in soils. PBDEs displayed a higher leaching tendency in moist paddy soil than in drier soils. The frequent flooding condition in paddy field may facilitate the vertical transfer of PBDEs to the deeper soils. [Copyright &y& Elsevier]

Tri-decabrominated diphenyl ethers and 21 other flame retardants were determined in matched serum samples from 24 Swedish mothers (Uppsala county) and their toddlers (11-15 months of age). The median concentrations of individual polybrominated diphenyl ethers (PBDEs) ranged from 0.036 to 0.95 ng/g lipid in mothers and from 0.057 to 1.5 ng/g lipid in toddlers. BDE-209 was detected in all but one sample. BDE-153 was the predominant congener in the mothers while in toddlers, BDE-209 was found in the highest concentrations. The levels of BDE-47, -100, -207, -208, and -209 in toddlers were significantly higher (p < 0.05) than those in their mothers. Dechlorane Plus (anti- and syn-) and α- and β-tetrabromoethylcyclohexane were detected in a few (2-4) serum samples from both mothers and toddlers. This study also reports concentrations of α-HBCD and eight emerging brominated flame retardants (EBFRs) in the standard reference material serum (SRM 1958, NIST). Lack of correlations between the matched serum samples indicate different exposure routes for octa-decaBDEs in mothers versus toddlers. Congener-to-congener correlations within the mother or toddler cohorts suggest diet as an important exposure pathway for tetra-nonaBDEs for mothers, breastfeeding as a predominant exposure pathway for tetra-hexaBDEs, and dust for octa-decaBDEs for toddlers. [ABSTRACT FROM AUTHOR]

Air pollutants are transported by dry deposition, wet deposition, and gas exchange accumulated in soil. Therefore, soil is an important environmental medium reflecting the level and the spatial distribution of air pollutants such as polybrominated diphenyl ethers (PBDEs) and heavy metals. Soil concentrations of seven PBDE congeners and 21 trace elements were determined in a heavily industrialized region (Dilovasi) in Kocaeli, Turkey. At all sites, ΣPBDE concentrations ranged from 0.70 to 203 with a mean value of 26.3 μg kg (dry weight). The congener profiles and mass inventories of PBDEs and their interactions with soil organic matter (SOM) were also investigated. BDE-209 was the dominant congener at all sites, followed by BDE-99 and/or -47. The estimated inventory of PBDEs for the Dilovasi district was 310 kg. However, there are several additional industrial regions in Kocaeli city. Considering the total land area, the potential inventory would be much larger for this city. The relationship between the PBDE concentrations in soil and SOM content indicated that factors other than soil properties have a greater influence on soil concentrations. Crustal enrichment factors (EFs) were determined; correlation analysis and factor analysis (FA) were also applied to generated data set to identify and apportion the sources polluting the soil. Sn, Mn, Ca, As, Zn, Pb, and Cd had significantly high average EF values, indicating that their soil concentrations were mainly influenced by anthropogenic activities. In FA, six factors were extracted with a cumulative variance of 84.4 % and industrial activities and traffic were found to be the main factors affecting the soil profile. [ABSTRACT FROM AUTHOR]

Polybrominated diphenyl ethers (PBDEs), a group of flame retardants, and perfluoroalkyl substances (PFASs) were analysed in serum samples of pregnant women from Denmark to provide information about their exposure and to study indications of common exposure pathways. The main BDE congener was the fully brominated BDE-209 with a median value of 7.5 ng/g lipid (46 pg/mL; 9.8 pmol/g lipid). Other BDE congeners decreased in the order BDE-47 > BDE-99 > BDE-153. The summed concentration of tri- to hepta-BDEs was 7.7 ng/g lipid, i.e. in the higher end of previously reported concentrations from Europe, including plasma samples of pregnant Danish women. Total lipid contents were relatively low, on average 5.9 g/L (9.0 mmol/L). The main PFAS compound was perfluorooctane sulfonate with a median concentration of 8.4 ng/mL. Other PFASs decreased in the order perfluorooctanoic acid > perfluorononanoic acid > perfluorodecanoic acid > perfluorohexane sulfonate and resulted in a ΣPFAS of 12 ng/mL. Within each group, compounds were highly intercorrelated with the exception of BDE-209, which was not correlated with any of the other compounds. No correlations were found either between PFASs and PBDEs suggesting different sources of exposure and/or pharmacokinetic and metabolisation processes. PBDE and PFAS concentrations were in the range associated with adverse effects in some epidemiological studies. [ABSTRACT FROM AUTHOR]

The authors summarize the scientific literature on toxic organic microcontaminants in vegetables published during the last 15 years. A wide range of persistent, bioaccumulative, and toxic organic pollutants have been studied, namely polycyclic aromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), phthalic acid esters (PAEs), and perfluorinated substances. The available literature data covers the occurrence of organic contaminants in vegetables and the subsequent human exposure, through ingestion. Benzo[a]pyrene equivalents (BaPeq) were calculated following the concentrations of individual PAH in the literature and then compared. This review also summarizes Toxic Equivalent Concentrations (TEQ) and daily intake of PCDD/Fs, PCBs, and PBDEs through vegetable consumption. Temporal and spatial variations in contaminants concentrations are discussed. The existing scientific literature is critically evaluated regarding gaps, implications, and needs for future research. [ABSTRACT FROM PUBLISHER]

In order to characterize polybrominated diphenyl ethers (PBDEs), and hydroxylated and methoxylated PBDEs (OH-PBDEs and MeO-PBDEs) in the soil–plant system, soil and plant samples were collected from an e-waste recycling area in China. Forty one PBDEs, twelve OH-PBDEs and MeO-PBDEs were detected in the soil and plant samples. Concentrations of PBDEs in roots were significantly correlated to their concentrations in the soils, but the percentages of lower brominated congeners in the plants were higher than those in the soils. Significant positive linear relationships exist between concentrations of ∑OH-PBDEs and ∑MeO-PBDEs with higher levels of ∑MeO-PBDEs than those of ∑OH-PBDEs in the soils, plant roots and leaves. A majority of the OH-/MeO-PBDEs had the hydroxyl or methoxy group at the ortho-positions to the biphenyl bond for most of the plant species. However the occurrence of meta- and para- substituted OH-/MeO-PBDEs in soils and plants were also confirmed. [Copyright &y& Elsevier]

Abstract: Polybrominated diphenylethers (PBDEs), one of the most common brominated flame retardants, are toxic and persistent, generally detected by the chromatographic method. In this work, qualitative and quantitative detection of PBDEs were explored based on surface-enhanced Raman spectroscopy (SERS) technique using a portable Raman spectrometer. Alkanethiol modified silver nanoparticle aggregates were used as the substrate and PBDEs could be pre-concentrated close to the substrate surface through their hydrophobic interactions with alkanethiol. The effect of alkanethiols with different chain length on the SERS detection of PBDEs was evaluated. It was shown that 1-hexanethiol (HT) modified substrate has higher sensitivity, good stability and reusability. Qualitative and quantitative SERS detection of PBDEs in real sea water was accomplished, with the measured detection limits at 1.2×102 μgL−1. These results illustrate SERS could be used as an effective method for the detection of PBDEs. [Copyright &y& Elsevier]

Two fish species (mud carp and northern snakehead) forming a predator/prey relationship and sediment samples were collected from a pond contaminated by e-waste. The concentrations and stable carbon isotope ratios (δ13C) of individual polychlorinated biphenyl (PCB) and polybrominated diphenyl ether (PBDE) congeners were measured to determine if compound-specific carbon isotope analysis (CSIA) could be used to provide insight into the metabolism and trophic dynamics of PCBs and PBDEs. Significant correlations were found in die isotopic data of PCB congeners between the sediment and the fish species and between the two fish indicating identical origin of PCBs in sediment and fish. Most PCB congeners in the fish species were enriched in 13C compared with die PCB congeners in the sediments as a result of isotopic fractionation during the metabolism of PCBs in fish. The isotopic data of several PCB congeners showing isotopic agreement or isotopic depletion could be used for source apportionment or to trace the reductive dechlorination process of PCBs in the environment. The PCB isotopic data covaried more in the northern snakehead than in the mud carp when compared to the sediment, implying that a similar isotopic fractionation occurs from the prey to the predator fish for a PCB congener possibly due to similar metabolic pathways. The PBDE congener patterns differed in the three sample types with a high abundance of BDE209, 183, 99, and 47 in the sediment, BDE47, 153, and 49 in the mud carp and BDE47, 100, and 154 in the northern snakehead. The isotopic change of BDE congeners, such as BDE47 and BDE49, in two fish species, provides evidence for biotransformation of PBDEs in biota. The results of this study suggest that CSIA is a promising tool for deciphering the fate of PCBs and PBDEs in the environment [ABSTRACT FROM AUTHOR]

Polybrominated diphenyl ethers (PBDEs) along with hydroxylated polybrominated diphenyl ethers (OH-PBDEs) and methoxylated polybrominated diphenyl ethers (MeO-PBDEs) were found in plant and soil samples collected surrounding a seafood processing factory and a seafood market in China. The profiles of MeO-PBDE congeners were different between seafood processing factory and seafood market. The detection frequency and concentration of 6-OH-BDE-47 were lower than that of MeO-PBDEs. Near seafood processing factory, a decreasing trend of analyte concentrations in plants was found downstream the river where factory wastewater was discharged. Concentrations of ΣMeO-PBDEs in plant and soil samples showed difference as root > soil > leaf. However, at seafood market, the concentrations of ΣMeO-PBDEs were much higher in leaves than those in soil. The concentration of ΣMeO-PBDEs in leaves showed a remarkable difference between Calystegia soldanella (Linn.) R. Br. and Setaira viridis (L.) Beauv. [Copyright &y& Elsevier]

Residue levels and patterns of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), their hydroxylated metabolites (OH-PCBs, OH-PBDEs), and methoxylated PBDEs (MeO-PBDEs) in the blood of various terrestrial mammals in Japan, including cats, raccoon dogs, dogs, masked palm civets, foxes, raccoons, badgers, and mongooses were determined. Tri- through penta-chlorinated OH-PCBs were predominant in cat blood, whereas hexa- through octa-chlorinated OH-PCBs were found in other species. High proportion of BDE209 was found in all species, suggesting exposure to municipal waste and soil containing higher levels of deca-BDE products. 6OH-/MeO-BDE47 and 2′OH-/MeO-BDE68 were dominant in all terrestrial mammals. This is first report on the detection of OH-/MeO-PBDEs in the blood of terrestrial mammals. High concentrations of OH-/MeO-PBDEs were found in cats, suggesting the intake of these compounds from seafood. Cats exhibited higher accumulation and specific patterns of OH-PCBs, OH-PBDEs, and MeO-PBDEs, they may be at a high risk from these metabolites. [Copyright &y& Elsevier]

Abstract: A multi-class, multi-residue method for the analysis of 13 novel flame retardants, 18 representative pesticides, 14 polychlorinated biphenyl (PCB) congeners, 16 polycyclic aromatic hydrocarbons (PAHs), and 7 polybrominated diphenyl ether (PBDE) congeners in catfish muscle was developed and evaluated using fast low pressure gas chromatography triple quadrupole tandem mass spectrometry (LP-GC/MS–MS). The method was based on a QuEChERS (quick, easy, cheap, effective, rugged, safe) extraction with acetonitrile and dispersive solid-phase extraction (d-SPE) clean-up with zirconium-based sorbent prior to LP-GC/MS–MS analysis. The developed method was evaluated at 4 spiking levels and further validated by analysis of NIST Standard Reference Materials (SRMs) 1974B and 1947. Sample preparation for a batch of 10 homogenized samples took about 1h/analyst, and LP-GC/MS–MS analysis provided fast separation of multiple analytes within 9min achieving high throughput. With the use of isotopically labeled internal standards, recoveries of all but one analyte were between 70 and 120% with relative standard deviations less than 20% (n =5). The measured values for both SRMs agreed with certified/reference values (72–119% accuracy) for the majority of analytes. The detection limits were 0.1–0.5ngg−1 for PCBs, 0.5–10ngg−1 for PBDEs, 0.5–5ngg−1 for select pesticides and PAHs and 1–10ngg−1 for flame retardants. The developed method was successfully applied for analysis of catfish samples from the market. [Copyright &y& Elsevier]

A field investigation was carried out to determine PBDE concentrations over a one-year period in agricultural soils onto which 80 tonnes biosolids/hectare had been applied. The PBDE concentrations increased from 80 to 300 pg/g dry weight basis to 300 × 103–600 × 103 pg/g dw due to biosolids application, and PBDEs migrated downwards to depths of at least 0.85 m. Concentrations decreased non-uniformly with depth. PBDE levels decreased exponentially in the topmost biosolids-amended soils layer, while increasing in the next underlying soil layer over the one-year period. The rate of decrease of total PBDE mass in the top 0.00–0.05 m layer was almost two orders of magnitude greater than the rates of increase in total PBDE mass in the lower layers, indicating that effects such as photodegradation and/or volatilization likely were to have been significant in the surface layer. [Copyright &y& Elsevier]

High levels of polybrominated diphenyl ethers (PBDEs) have been extensively reported in urban areas and at e-waste recycling sites in coastal China. However, data are scarce in northern China and are not available in rural areas at all. In addition, it is often believed that air concentrations in rural areas are lower than those in urban areas without distinguishing rural residential areas and open fields. In this study, air samples were collected at 17 sites covering urban and rural (residential and open field) areas in northern China using active samplers. With BDE-209 dominated in all congeners, the average concentrations of BDE-209 (41 ± 72 pg/m3) and other 13 PBDEs (16 ± 12 pg/m3) were significantly lower than those found in south China, such as in Guangzhou or Hong Kong. On average, the total PBDE concentrations at the urban sites were 2.2 and 2.9 times of those at the rural residential and field sites, respectively. [Copyright &y& Elsevier]

Air samples were collected at different sites in and around two wastewater treatment plants (WWTPs) located in central Italy to determine the concentrations, compositional profiles and contribution to ambient levels of eight polybrominated diphenyl ethers (PBDEs). The investigated WWTPs were selected as they treat industrial wastewater produced by local textile industries along with municipal wastewater. PBDE concentrations within the WWTPs were higher than those measured at reference sites located 4 and 5km away with BDE-209 dominating the BDE congener composition in all air samples in 2008. Ambient PBDE concentrations measured in and around the WWTPs and estimates of emissions from aeration tanks suggest that WWTPs are sources of PBDEs to ambient air. Principal component analysis and Pearson correlations confirmed this result. The effect of distance from the plant and wind direction on atmospheric concentrations was also investigated. Although the primary fate of PBDEs in WWTPs will be partitioning to sewage sludge, this study suggests that plants can provide a measurable source of these compounds to local ambient air. [Copyright &y& Elsevier]

Polybromodiphenyl ethers (PBDEs) in superficial sediments from the Gulf of Lion were studied. They were largely predominated by BDE 209 (98.7% of all PBDEs) indicating that the main source of these pollutants was the commercial mixture deca-BDE. This compound and the less brominated BDE exhibited a southwestward decreasing concentration gradient following the dominant marine currents and bottom relief, e.g. the Mud Belt, the submarine canyons and the Open Continental Slope. All PBDEs exhibited statistically significant correlations confirming the common origin. However, a progressive transformation of the dumped BDE 209 was identified showing a depletion paralleled by increases of the less brominated BDEs (from 8.6% to 22%). These less brominated compounds were accumulated at about 100–140km away from the Rhone prodelta, e.g. at the end of the submarine canyons, evidencing that these transformation compounds can be accumulated at long distances from the dumping sites in the marine system. [Copyright &y& Elsevier]

To compare legacy and emerging flame retardant (FR) contamination in Canadian marine and freshwater ecosystems, eggs of four gull species (Laridae) were collected from 26 colonies spanning Pacific to Atlantic Canada, including in the Great Lakes basin. Fourteen polybrominated diphenyl ether (PBDE) congeners and 20 non-PBDE FRs were analyzed, but BDE-47, -99, -100, -153, -154 and -209, hexabromocyclododecane (HBCD) and Dechlorane Plus (DP) syn- and anti-isomers were common, and where concentrations of ∑PBDEs (37–610 ng/g wet weight, ww) ≫ HBCD (0.5–12 ng/g ww) > ∑DP (not quantifiable-5.5 ng/g ww). All other FRs were generally not detectable. Stable nitrogen and carbon isotopes used as dietary tracers provided insights into the diet choice influences on the exposure sources and contamination patterns (e.g., PBDE congener compositions) for individual gulls from the same colony. Eggs from gulls breeding near metropolitan regions of higher human densities showed greater PBDE burdens than from other ecosystems. [Copyright &y& Elsevier]

Abstract: Polybrominated diphenyl ethers (PBDEs), extensively used as flame retardants, are ubiquitous environmental contaminants that are found in both abiotic and biotic environmental samples. Sufficient evidence shows that PBDEs have been rapidly accumulating in the environment of China, especially in the Southeast regions. This paper summarizes and critically reviews the published scientific data on PBDEs in China, including the levels of PBDEs in the air, soil, water, sediment, the terrestrial and marine organisms, and human samples in China. The data preliminarily reveal the state of PBDEs in China. [Copyright &y& Elsevier]

The latitudinal distribution of persistent organic pollutants (POPs: legacy organochlorines [OCs], polybrominated diphenyl ethers [PBDEs,] and hexabromocyclododecane [HBCD]) was examined in livers of two species of marine fish, the pelagic saithe (Pollachius virens,n = 40) and the demersal cod (Gadus morhua,n = 40), along a south-north gradient (59°-70°N) on the Norwegian Coast. Cod had in general two to three times higher concentrations of POPs than saithe, probably because of higher exposure in the benthic food chain. The concentrations of heavy halogenated compounds were higher in the southernmost region than further north. Moreover, the POP pattern showed a gradual shift in the compositions from south to north, especially for OCs in cod: i.e. the relative importance of low-chlorinated polychlorinated biphenyl (PCB) congeners and some OC-pesticides (e.g., hexachlorobenzen [HCB]) in the contaminant burdens increased with latitude. The latitudinal fractionation signal was weaker in saithe, possibly due to its pelagic and nomadic behavior. Hence, this study shows not only a strong latitudinal fractionation in the compositional patterns of POPs in marine fish but also the effects of habitat use and fish behavior. [ABSTRACT FROM AUTHOR]

Modified polymer-coated glass samplers (POGs), termed EVA samplers, consist of micrometer-thin layers of ethylene vinyl acetate (EVA) coated onto a glass fiber filter or aluminum foil substrate. These samplers were designed to equilibrate rapidly with priority pollutants in air, making them ideal for short-term spatial studies in ambient or indoor air. The EVA sampler was calibrated by measuring the uptake of polychlorinated biphenyls (PCBs) over 8 weeks in an indoor environment, and four different film thicknesses were monitored that ranged from 0.1 to 30 μm. The results were used to calculate the average mass transfer coefficient (50.5 m/day) and generate contour maps that provide guidance in choosing an appropriate EVA sampler for a particular study based on film thickness, deployment time, and the log KOA of the anlayte. A range of air pollutant classes was also added to the EVA sampler prior to deployment to assess depuration rates. These included polychlorinated biphenyls (PCBs), current-use pesticides (CUPs), perfluorinated compounds (PFCs), and polybrominated diphenyl ethers (PBDEs). On the basis of the depuration profiles, the EVA sampler was a suitable equilibrium sampler for several CUPs and PCBs; however, for the high molecular weight PCBs and PBDEs, the EVA sampler operates as a linear uptake sampler. Samplers were also evaluated for their use as a rapid screening tool for assessing concentrations of siloxanes in indoor air. The EVA sampler was used to estimate air concentrations for D4 and D5 in laboratory air to be 118 and 89 ng/m³, respectively. Analyses were performed directly using thermal desorption gas chromatography/mass spectrometry (TDS-GC-MS). EVA samplers show promise due to their relatively low cost and ease of deployment and applicability to a wide range of priority chemicals. The ability to alter the film thickness, and hence the sorption capacity and performance of the EVA sampler, allows for a versatile sampler that can be used under varying sampling conditions and deployment times. [ABSTRACT FROM AUTHOR]

High levels of polybrominated dibenzo-p-dioxins (PBDDs) have been found in Baltic Sea biota, where the toxic load owing to, for example, polychlorinated dibenzo-p-dioxins and other organic pollutants is already high. The levels and geographic pattern of PBDDs suggest biogenic rather than anthropogenic origin, and both biotic and abiotic formation pathways have been proposed. Photochemical formation from hydroxylated polybrominated diphenyl ethers (OH-PBDE) is a proposed pathway for PBDDs in marine environments. Ultraviolet radiation-initiated transformations of OH-BDEs 47, 68, 85, 90, 99, and 123, which all are abundant in the environment, were investigated. It was shown that the most abundant PBDDs in the environment (1,3,7-triBDD and 1,3,8-triBDD) can be formed from the most abundant OH-BDEs (OH-BDE 47 and OH-BDE 68) at high rates and with percentage yields. In fact, most of the PBDDs that have been identified in the Baltic Sea environment were formed with high yield from the six studied OH-PBDE, through initial cyclization and subsequent debromination reactions. The high formation yields point to this route as an important source of PBDDs in biota. However, congeners showing relatively high retention in fish, specifically 1,3,6,8- and 1,3,7,9-tetraBDD, were not formed. These are likely formed by enzymatic coupling of brominated phenols. [ABSTRACT FROM AUTHOR]

We report a multi-residue pretreatment technique, termed temperature-assisted ionic liquid dispersive liquid-liquid microextraction, and demonstrate its application to simultaneous extraction of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). An ionic liquid was used as the extraction solvent and dispersed into the liquid sample (water, urine) with the help of methanol and at elevated temperature. Parameters such as extraction solvent and its volume, disperser solvent and its volume, extraction time, centrifugation time, salt addition, extraction temperature and sample pH were optimized. Under the optimized conditions, an up to 278-fold enrichment factor and an >83.4% extraction recovery were obtained. A linear relationship is obtained in the range of 0.5-500 ng mL. The limits of detection (at S/N = 3) and relative standard deviations (for n = 5) range from 0.1 to 0.4 ng mL and from 1.0% to 5.6%, respectively. The recoveries for water and urine samples additionally spiked with PCBs and PBDEs are between 81.0 and 127.1% and 84.0 and 110.3%, respectively. The method was successfully applied to the determination of PCBs and PBDEs in real river water and in human urine samples. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Due to migration of harbour porpoises towards more polluted areas like the North Sea and their sensitivity towards pollution, there is a need for proper conservation measures for this species. As a consequence, knowledge about the pollutant’s kinetics is required. The present study is the first to investigate the kinetics of PBDEs in marine mammals using PBPK modeling as a non-destructive tool for describing the chemical’s kinetics in a protected animal species. The models were developed and parameterized using data from the literature and Black Sea harbour porpoises through computer optimization. The predictability of these models in time was assessed by reverse dosimetry modeling using data from North Sea porpoises (1990–2008). From these predictions, PBDE 99 levels were found to decrease the fastest, followed by PBDE 153, 47 and 100. Results show that the PBPK models can be applied for harbour porpoises from different regions and also simulate time trends. [Copyright &y& Elsevier]