Comprehensive exploration of the anaerobic biotransformation of polychlorinated biphenyls in Dehalococcoides mccartyi CG1: Kinetics, enantioselectivity, and isotope fractionation.

Anaerobic microbial transformation is a key pathway in the natural attenuation of polychlorinated biphenyls (PCBs). Much less is known about the transformation behaviors induced by pure organohalide-respiring bacteria, especially kinetic isotope effects. Therefore, the kinetics, pathways, enantioselectivity, and carbon and chlorine isotope fractionation of PCBs transformation by Dehalococcoides mccartyi CG1 were comprehensively explored. The results indicated that the PCBs were mainly dechlorinated via removing their double-flanked meta-chlorine, with their first-order kinetic constants following the order of PCB132 > PCB174 > PCB85 > PCB183 > PCB138. However, PCBs occurred great loss of stoichiometric mass balance during microbial transformation, suggesting the generation of other non-dehalogenation products and/or stable intermediates. The preferential transformation of (-)-atropisomers and generation of (+)-atropisomers were observed during PCB132 and PCB174 biotransformation with the enantiomeric enrichment factors of -0.8609 ± 0.1077 and -0.4503 ± 0.1334 (first half incubation times)/-0.1888 ± 0.1354 (second half incubation times), respectively, whereas no enantioselectivity occurred during PCB183 biotransformation. More importantly, although there was no carbon and chlorine isotope fractionation occurring for studied substrates, the δ13C values of dechlorination products, including PCB47 (-28.15 ± 0.35‰ âˆ¼ -27.77 ± 0.20‰), PCB91 (-36.36 ± 0.09‰ âˆ¼ -34.71 ± 0.49‰), and PCB149 (-28.08 ± 0.26‰ âˆ¼ -26.83 ± 0.10‰), were all significantly different from those of their corresponding substrates (PCB85: -30.81 ± 0.02‰ âˆ¼ -30.22 ± 0.21‰, PCB132: -33.57 ± 0.15‰ âˆ¼ -33.13 ± 0.14‰, and PCB174: -26.30 ± 0.09‰ âˆ¼ -26.01 ± 0.07‰), which further supported the generation of other non-dehalogenation products and/or stable intermediates with enrichment or depletion of 13C. These findings provide deeper insights into the anaerobic microbial transformation behaviors of PCBs.

Occurrence, composition, and spatial distribution of dechlorane plus in surface sediments of black-odorous urban rivers across China.

China, one of the two dechlorane plus (DP) producers, might have become a major area of DP pollution. The environmental contamination status of DP in sediments across the whole of China has not yet been studied. In the current study, the pollution levels, spatial distribution, and compositions of DP were investigated comprehensively in surface sediments from 173 black-odorous urban rivers across China for the first time. Total DP concentrations varied from not-detected to 39.71 ng/g dw, with an average concentration of 3.20 ± 4.74 ng/g dw, which was polluted by local emission sources and presented significant differences among different sampling cities. Among the seven administrative regions of China, DP concentrations were the highest in South China and showed a decreasing trend from southeastern coastal areas to northwest inland regions. Spearman's correlation analysis suggested that the gross industrial output, gross domestic product, and daily wastewater treatment capacity were not the principal factors controlling the spatial distribution of DP. The fanti values (the concentration ratios of anti-DP to the sum of anti-DP and syn-DP) varied from 0.19 to 0.88, with those in most sediments falling in the range of DP technical product (0.60 ~ 0.80), suggesting no apparent stereoselective enrichment occurred. Moreover, the anti-Cl11-DP was detected in sediments (n.d. ~ 0.40 ng/g dw), which showed significantly and insignificantly positive correlation with the anti-DP levels and fanti, respectively, implying it might mainly originate from the byproduct of DP technical product rather than the dechlorination of anti-DP.

Insights into the occurrence, spatial distribution, and ecological implications of organophosphate triesters in surface sediments from polluted urban rivers across China.

Organophosphate triesters (tri-OPEs) are a kind of widespread contaminants in the world, particularly in China, which is a major producer and user of tri-OPEs. However, tri-OPE pollution in urban river sediments in China remains unclear. In current work, we carried out the first nationwide investigation to comprehensively monitor 10 conventional and five emerging tri-OPEs in sediments of 173 black-odorous urban rivers throughout China. Concentrations of 10 conventional and five emerging tri-OPEs were 3.8-1240 ng/g dw (mean: 253 ng/g dw) and 0.21-1107 ng/g dw (68 ng/g dw), respectively, and significantly differed among the cities sampled but generally decreased from Northeast and East China to Central and West China. These spatial patterns suggest that tri-OPE pollution was mainly from local sources and was controlled by the industrial and economic development levels in these four areas, as indicated by the significant correlations between tri-OPE concentrations and gross domestic production, gross industrial output, and daily wastewater treatment capacity. Although the tri-OPE composition varied spatially at different sites, which indicated different tri-OPE input patterns, it was commonly dominated by tris(2-chloroethyl) phosphate, tris(2-ethylhexyl) phosphate, and tris(1-chloro-2-propyl) phosphate (conventional tri-OPEs) and bisphenol A-bis(diphenyl phosphate) and isodecyl diphenyl phosphate (emerging tri-OPEs). A risk assessment indicated that tri-OPEs in most sampling sediments had a low to moderate risk to aquatic organisms.

Historical Occurrence and Composition of Novel Brominated Flame Retardants and Dechlorane Plus in Sediments from an Electronic Waste Recycling Site in South China.

Novel brominated flame retardants (NBFRs) and dechlorane plus (DP) have been widely used as alternatives to traditional BFRs. However, little is known about the temporal trends of NBFR and DP pollution in e-waste recycling sites. In the current study, three composite sediment cores were collected from an e-waste-polluted pond located in a typical e-waste recycling site in South China to investigate the historical occurrence and composition of NBFRs and DP. The NBFRs and DP were detected in all layers of the sediment cores with concentration ranges of 5.71~180,895 and 4.95~109,847 ng/g dw, respectively. Except for 2,3,5,6-tetrabromo-p-xylene (pTBX) and 2,3,4,5,6-pentabromoethylbenzene (PBEB), all the NBFR compounds and DP showed a clear increasing trend from the bottom to top layers. These results implied the long-term and severe contamination of NBFRs and DP. Decabromodiphenyl ethane (DBDPE) was the most abundant NBFR with the contribution proportions of 58 ± 15%, 73 ± 15%, and 71 ± 18% in three sediment cores, followed by 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE) and pentabromobenzene (HBB). The ratios of BTBPE/Octa-BDEs and DBDPE/Deca-BDEs varied from 0.12 to 60 and from 0.03 to 0.49, respectively, which had no clear increase trends with a decrease in sediment depth. As for DP, the fanti values (the concentration ratios of anti-DP to the sum of anti-DP and syn-DP) in sediment cores ranged from 0.41 to 0.83, almost falling in the range of those in DP technical products, suggesting that DP degradation did not occur in sediment cores. The environmental burdens of DBDPE, BTBPE, HBB, PBT, PBEB, pTBX, and DP were estimated to be 34.0, 5.67, 10.1, 0.02, 0.02, 0.01, and 34.8 kg, respectively. This work provides the first insight into the historical contamination status of NBFRs and DP in the sediments of an e-waste recycling site.

Spatial distribution, conversion, and ecological risk assessment of hexabromocyclododecanes in the sediments of black-odorous urban rivers nationwide in China.

Hexabromocyclododecanes (HBCDs) have become a global pollution problem, particularly in China-a major producer and user of HBCDs. However, little is known about the HBCD pollution status in urban rivers nationwide in China. In this study, we comprehensively investigated the pollution characteristics of HBCDs in 173 sediment samples from black-odorous urban rivers across China. Total HBCD concentrations ranged from not-detected to 848 ng/g dw, showing significant differences among the various sampling cities, but generally increasing from west to east China. This distribution pattern of HBCDs was strongly associated with the local industrial output, gross domestic product, and daily wastewater treatment capacity. α-HBCD was the predominant diastereoisomer in most sediments, with an average proportion of 63.8 ± 18.8 %, followed by γ-HBCD (23.8 ± 19.5 %) and ß-HBCD (12.4 ± 6.49 %), showing a significant increase of the α-HBCD proportions relative to those in HBCD commercial mixtures and an opposite trend for that of γ-HBCD. These results suggested that HBCDs might undergo isomerization from γ- to α-HBCD and biotic/abiotic degradation with preference for γ-HBCD. Of these conversions, the microbial degradation of HBCDs was further verified by the preferential transformation of (-)-α-, (+)-ß-, and (-)-γ-HBCDs and the detection of HBCD-degrading bacteria, including Dehalococcoides, Bacillus, Sphingobium, and Pseudomonas. A risk assessment indicated that HBCDs pose low to moderate risks to aquatic organisms in most black-odorous urban river sediments.

Organophosphate diesters (DAPs) and hydroxylated organophosphate flame retardants (HO-OPFRs) as biomarkers of OPFR contamination in a typical freshwater food chain.

Organophosphate flame retardants (OPFRs) can rapidly biotransform into two types of metabolites in biota: (1) organophosphate diesters (DAPs) and (2) hydroxylated OPFRs (HO-OPFRs). Therefore, the levels of parent OPFRs alone are not sufficient to indicate OPFR pollution in biological organisms. This study analyzed 12 OPFR metabolites, including 6 DAPs and 6 HO-OPFRs, in a typical freshwater food chain consisted of crucian carp, catfish, mud carp, snakehead, and oriental river prawn. The total concentrations of OPFR metabolites were comparable to those of parent OPFRs, and ranged from 0.65 to 17 ng/g ww. Bis(2-butoxyethyl) 3'-hydroxy-2-butoxyethyl phosphate (14%-77%), di-n-butyl phosphate (DNBP) (6.7%-24%), bis(1-chloro-2-propyl) phosphate (BCIPP) (0.7%-35%), and 1-hydroxy-2-propyl bis(1-chloro-2-propyl) phosphate (BCIPHIPP) (6.0%-24%) were the major OPFR metabolites. Various aquatic species exhibited significant differences in their OPFR metabolite/parent ratios (MPR) (p < 0.05), indicating varying biotransformation potentials of different organisms for various OPFRs. The growth-independent accumulation of tri-n-butyl phosphate (TNBP), tris(chloro-2-propyl) phosphate (TCIPP), triphenyl phosphate, and 2-ethylhexyl diphenyl phosphate in mud carps could be explained by their biotransformation potential. A significant negative correlation was found between the concentration of bis(2-butoxyethyl) phosphate and δ15N values (p < 0.05), with a calculated trophic magnification factor (TMF) of 0.66. Significant positive correlations were observed between BCIPP and TCIPP (R2 = 0.25, p < 0.05), as well as between DNBP and TNBP (R2 = 0.30, p < 0.01), implying that these two DAPs could be used as biomarkers to quantitatively assess TCIPP and TNBP contamination in wild aquatic organisms.

Anaerobic biotransformation of two novel brominated flame retardants: Kinetics, isotope fractionation and reaction mechanisms.

1,2,5,6-tetrabromocyclooctane (TBCO) and 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), as safer alternatives to traditional brominated flame retardants, have been extensively detected in various environmental media and pose emerging risks. However, much less is known about their fate in the environment. Anaerobic microbial transformation is a key pathway for the natural attenuation of contaminants. This study investigated, for the first time, the microbial transformation behaviors of ß-TBCO and DPTE by Dehalococcoides mccartyi strain CG1. The results indicated that both ß-TBCO and DPTE could be easily transformed by D. mccartyi CG1 with kobs values of 0.0218 ± 0.0015 h-1 and 0.0089 ± 0.0003 h-1, respectively. In particular, ß-TBCO seemed to undergo dibromo-elimination and then epoxidation to form 4,5-dibromo-9-oxabicyclo[6.1.0]nonane, while DPTE experienced debromination at the benzene ring (ortho-bromine being removed prior to para-bromine) rather than at the carbon chain. Additionally, pronounced carbon and bromine isotope fractionations were observed during biotransformation of ß-TBCO and DPTE, suggesting that C-Br bond breaking is the rate-limiting step of their biotransformation. Finally, coupled with identified products and isotope fractionation patterns, ß-elimination (E2) and Sn2-nucleophilic substitution were considered the most likely microbial transformation mechanisms for ß-TBCO and DPTE, respectively. This work provides important information for assessing the potential of natural attenuation and environmental risks of ß-TBCO and DPTE.

Presence of novel and legacy flame retardants and other pollutants in an e-waste site in China and associated risks.

Electrical and Electronic Equipment (EEE) residues and their management have been widely identified as potential sources of plasticizers and flame retardants to the environment, especially in non-formal e-waste facilities. This study evaluates the distribution, partitioning and environmental and human impact of organophosphate esters (OPEs), legacy polychlorinated biphenyls (PCBs), polybromodiphenyl ethers (PBDEs) and organochlorine pesticides (OCPs) in the e-waste recycling area of Baihe Tang village, in the Qingyuan county, Guangdong province, China. A plastic debris lump accumulated in a small pond during years was identified as the main source of pollution with ∑pollutants of 8400 µg/g dw, being OPEs the main contaminants detected, followed by PBDEs. This lump produced the contamination of water, sediments, soils and hen eggs in the surrounding area at high concentrations. Plastic-water and water-sediment partitioning coefficients explained the migration of OPEs to the water body and accumulation in sediments, with a strong dependence according to the KOW. Triphenyl phosphate (TPhP), tricresyl phosphate (TCPs) and high chlorination degree PCBs produced a risk in soils and sediments, considering the lowest predicted no effect concentration, while the presence of PCBs and PBDEs in free range hen eggs exceeded the acceptable daily intake. OCPs were detected at low concentrations in all samples. The presence of organic contaminants in e-waste facilities worldwide is discussed to highlight the need for a strict control of EEE management to minimize environmental and human risks.

Legacy and alternative plasticizers in surface sediment of black-odorous urban rivers across China: Occurrence, spatial distribution, and ecological risk assessment.

In this study, surface sediment samples from 173 black-odorous urban rivers in 74 cities of China were investigated regarding the occurrence, spatial distribution, and ecological risk of legacy phthalates (LPs) and alternative plasticizers (APs). The total concentrations of Σ7LPs and Σ6APs ranged from 0.0035 to 522 µg/g dw (median: 33 µg/g dw; mean: 60 µg/g dw) and from 0.0015 to 16 µg/g dw (median: 16 µg/g dw; mean: 2.2 µg/g dw), respectively. Di(2-ethylhexyl) phthalate (DEHP), di-n-butyl phthalate (DnBP), and di-iso-butyl phthalate (DiBP) were the dominant LPs, and di-iso-decyl phthalate and di-iso-nonylcyclohexane-1,2-dicarboxylate were the dominant APs. The concentrations and compositions of the LPs and APs varied among different sites and regions, implying location-specific use or production of LPs and APs. The pollutant concentrations in southern and central China were higher than those in northern China. Among the seven regions, Northwest China had the lowest concentrations of LPs and APs. This could be related to industry development level, municipal facilities, and population density. Total organic carbon (TOC) was significantly and positively correlated with the pollutant concentrations, implying that TOC could be an important influencing factor for the distribution of LPs and APs in sediments. The risk quotients of DiBP and DnBP in almost all sediment samples were above 1, indicating the high ecological risks to aquatic organisms. Nevertheless, DEHP, di-methyl phthalate, di-ethyl phthalate, and di-n-octyl phthalate showed low or moderate ecological risks for most sampling sites.

Tissue-Specific Distribution of Legacy and Emerging Organophosphorus Flame Retardants and Plasticizers in Frogs.

Five types of tissues, including the liver, kidney, intestine, lung, and heart, were collected from black-spotted frogs and bullfrogs to study the tissue-specific accumulation of organophosphorus flame retardants (PFRs) and plasticizers. Thirteen PFRs and nine plasticizers were detected, with average total concentrations of 1.4-13 ng/g ww and 858-5503 ng/g ww in black-spotted frogs, 3.6-46 ng/g ww and 355-3504 ng/g ww in bullfrogs. Significant differences in pollutant concentrations among different tissues in the two frog species were found, indicating the specific selectivity distribution of PFRs and plasticizers. Overall, liver tissues exhibited significantly higher pollutant concentrations. The pollutant concentration ratios of other tissue to the sum of liver tissue and other tissues (OLR, Cother/(Cother + Cliver)) corresponding to male frogs were significantly greater than those of females, suggesting that male frogs could have higher metabolic potentials for PFRs and plasticizers. No obvious correlations between OLR and log KOW were found, indicating that the other factors (e.g., bioaccumulation pathway and metabolism) besides lipophicity could influence the deposition of PFRs and plasticizers in frog livers. Different parental transfer patterns for PFRs and plasticizers were observed in frogs when using different tissues as parental tissues. Moreover, the liver tissues had similar parental transfer mechanism with muscle tissues.

Mechanistic Aspects Regarding the Ultraviolet Degradation of Polychlorinated Biphenyls in Different Media: Insights from Carbon and Chlorine Isotope Fractionation.

In this study, the carbon and chlorine isotope fractionation during ultraviolet-photolysis of polychlorinated biphenyls (PCBs, including PCB18, PCB77, PCB110, and PCB138) in n-hexane (Hex), methanol/water (MeOH/H2O), and silica gel was first investigated to explore their mechanistic processes. We observed a significant variation in ΛCl-C (εCl/εC) for the same PCBs in different photochemical systems, implying that PCB degradation processes in various photoreaction systems could differ. Although all substrates showed normal apparent carbon/chlorine kinetic isotope effects (C-/Cl-AKIE >1), the putative inverse C-AKIE of nondechlorinated pathways was suggested by 13C depletion of the average carbon isotope composition of PCB138 and corresponding dechlorinated products in MeOH/H2O, which might originate from the magnetic isotope effect. Significant negative correlations were found between C-AKIE and relative disappearance quantum yields ("Φ") of ortho-dechlorinated substrates (PCB18, PCB110, and PCB138) in Hex and MeOH/H2O. However, the C-AKIE and "Φ" of PCB77 (meta/para-dechlorinated congener) obviously deviated from the above correlations. Furthermore, significantly different product-related carbon isotope enrichment factors of PCB77 in Hex were found. These results demonstrated the existence of dechlorination position-specific and masking effects in carbon isotope fractionations.

Bioaccumulation of legacy and emerging organophosphorus flame retardants and plasticizers in insects during metamorphosis.

Seven insect taxa belonging to five different orders were collected from a former Chinese e-waste dumping site to investigate the occurrences of organophosphorus flame retardants (PFRs) and plasticizers. The total PFR and plasticizer concentrations were in the ranges of 2.3-91 ng/g ww (median: 20 ng/g ww) and 420-15600 ng/g ww (4040 ng/g ww), respectively. The contaminant patterns varied greatly among different insect taxa owing to their specific habitats and feeding habits. The larvae of litchi stinkbugs and grasshoppers exhibited significantly higher PFR concentrations than their adult counterparts. In contrast, the adults of butterflies, moths, and dragonflies exhibited significantly higher PFR concentrations than their larvae. Additionally, negative linear correlations were frequently observed between the ratios of PFR and plasticizer concentrations in adult to larva (A/L) and log KOW in the four studied insect taxa, which were different from those corresponding to persistent organic pollutants. Notably, the contaminant concentrations of dragonfly ecdysis were significantly higher than those of dragonfly larvae, indicating that ecdysis is an important pathway by which dragonflies remove PFRs and plasticizers.

Legacy and emerging organophosphorus flame retardants and plasticizers in frogs: Sex difference and parental transfer.

Black-spotted frogs and bullfrogs from an e-waste polluted area were collected and examined for legacy and emerging organophosphorus flame retardants (PFRs) and plasticizers. Total concentrations of PFRs and plasticizers were 0.62-15 ng/g wet weight (ww) and 316-4904 ng/g ww in muscles, 2.2-59 ng/g ww and 127-5757 ng/g ww in eggs and gonads, and 1.2-15 ng/g ww and 51-1510 ng/g ww in oviducts, respectively. For muscle tissues, concentrations of ∑PFRs, triethyl phosphate, tris-(2-chloroethyl) phosphate, and tris-(chloro-2-propyl) phosphate were significantly higher in the males than females (p < 0.05). However, for reproductive tissues, eggs exhibited higher levels of those contaminants than gonads (p < 0.05). No significant sex difference in levels of plasticizers was observed in muscles. In contrast, levels for (2-ethylhexyl) phthalate, di-n-butyl phthalate, and di-iso-butyl phthalate in gonads were significantly higher than those in eggs (p < 0.05). Significantly negative linear correlations between maternal transfer ratios and log KOW were found in female frogs. Paternal transfer potentials were first significantly and positively correlated to log KOW (<6) and then decreased afterward in the males. These results indicated that parental transfer was answer for the sex-specific accumulation of PFRs and plasticizers in frogs.

Legacy and emerging organophosphorus flame retardants and plasticizers in indoor microenvironments from Guangzhou, South China.

Indoor dust has been extensively used for assessment of indoor contamination, especially for semi-volatile organic compounds (SVOCs). In the present study, the occurrence of four groups of SVOCs, i.e. organophosphorus flame retardants (PFRs), emerging PFRs (ePFRs), legacy phthalates (LPs), and alternative plasticizers (APs), was investigated in the indoor dust and air collected from floors, table surfaces, windows, and air conditioner (A/C) filters in bedrooms and offices in Guangzhou, South China. In bedrooms, A/C filter dust showed the highest median concentrations of PFRs (4670 ng/g) and ePFRs (586 ng/g), whilst the highest median concentrations of LPs and APs were found in floor (240,880 ng/g) and window dust (157,160 ng/g), respectively. In offices, A/C filter dust showed the highest median concentrations for PFRs (6750 ng/g) and APs (504,520 ng/g), while the highest ePFR median level was found in PC table dust (5810 ng/g) and LPs in floor dust (296,270 ng/g). Median air concentrations of PFRs, ePFRs, LPs, and APs were measured at 4.6, 0.12, 399, and 25 ng/m3 in bedrooms, and at 8.0, 0.05, 332, and 43 ng/m3 in offices, respectively. Tris(1-chloro-iso-propyl) phosphate (TCIPP) was the predominant PFRs/ePFRs in both dust and air. Di(2-ethylhexyl) phthalate (DEHP), di-iso-decyl phthalate (DIDP) and di-iso-nonyl phthalate (DINP) were the main LP/AP compounds in dust, whilst di-iso-butyl phthalate (DIBP) and di-n-butyl phthalate (DNBP) were the most abundant LPs/APs in air. A significant correlation (p < 0.05) was found between dust and air levels for chemicals with log Koa < 14, indicating that equilibrium was achieved for these chemicals but not for those with log Koa > 14. Among the investigated human exposure pathways (i.e. dust ingestion, dermal absorption, and air inhalation), dust ingestion was the predominant one for all chemicals. Human exposures of this magnitude to these chemicals through the investigated pathways was unlikely to present a health risk in the present study.

Occurrence, biomagnification and maternal transfer of legacy and emerging organophosphorus flame retardants and plasticizers in water snake from an e-waste site.

Water snake and small common carp samples collected from a Chinese pond polluted with electronic waste (e-waste) were analyzed for organophosphorus flame retardants (PFRs), PFR metabolites, and plasticizers to investigate their occurrence, biomagnification, and maternal transfer in ovoviviparous species. Mean concentrations of total PFRs, PFR metabolites, and plasticizers were 2.2-16, 1.3-2.8 and 151-1320 ng/g wet weight (ww), respectively in analyzed organisms. Metabolites of PFRs were found in the same order of magnitude as or even higher than their parent compounds, indicating the importance of monitoring metabolites to evaluate the internal exposure of PFRs in organisms. Biomagnification factors (BMFs) were below 1 for all targeted chemicals and negatively correlated with metabolite/parent ratios (MPRs), suggesting a biodilution driven by metabolism. The lipid normalized concentrations were lower in eggs than in muscle for most of targeted chemicals. The maternal transfer potential was significantly and positively correlated with log KOW (p < 0.05) when log KOW was below 6.

Organophosphorus flame retardants in a typical freshwater food web: Bioaccumulation factors, tissue distribution, and trophic transfer.

Water, sediment, and wild aquatic species were collected from an electronic waste (e-waste) polluted pond in South China. This study aimed to investigate the bioaccumulation, tissue distribution, and trophic transfer of organophosphorus flame retardants (PFRs) in these aquatic organisms. The concentrations of PFRs detected in the analyzed organisms were between 1.7 and 47 ng/g wet weight (ww). Oriental river prawn and snakehead exhibited the highest and lowest levels, respectively. Tri-n-butyl phosphate (TnBP), tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCPP) and triphenyl phosphate (TPhP) were dominant contaminants, accounting for approximately 86% of the total sum. The mean values of bioaccumulation factors (BCFs) and logarithmic biota-sediment accumulation factors (log BSAFs) for individual PFRs varied from 6.6 to 1109 and from -2.0 to 0.41, respectively. Both log BCFs and log BSAFs of PFRs were significantly and positively correlated with their octanol-water partitioning coefficient (log KOW). The concentrations of PFRs in tissues of large mud carp and snakehead were significantly and positively correlated with the lipid content (each p < 0.05) and the liver, kidney, and gill exhibited high PFR levels. When the concentration was expressed on a lipid basis, liver exhibited the lowest level, indicating the probable effects of metabolism. Significantly positive correlation was also found between lipid content and total PFR concentration in muscle of all aquatic organisms, given the strong correlation between lipid content and the concentration of TnBP. Trophic magnification factors (TMF) of TnBP and TPhP were lower than 1 (0.57 and 0.62), indicating that these PFRs undergo trophic dilution in this aquatic food web.

Organophosphorus flame retardants in fish from Rivers in the Pearl River Delta, South China.

Twelve organophosphorus flame retardants (PFRs) were detected in the muscle of 3 species of fish, mud carp (Cirrhinus molitorella), tilapia (Tilapia nilotica), and plecostomus (Hypostomus plecostomus), from rivers in the Pearl River Delta (PRD) region. The total concentrations of PFRs in the mud carp, tilapia, and plecostomus ranged from 2.3 to 16, 3.4 to 16, and 3.5 to 30 ng/g wet weight (ww), respectively. Generally, tris(2-ethylhexyl) phosphate (TEHP), tris (2-chloro-isopropyl) phosphate (TCPP), tris (2-chloroethyl) phosphate (TCEP), and tri-n-butyl phosphate (TnBP) were the dominant compounds of the PFRs, collectively accounting for up to 90% of the total PFR levels. Concentrations of PFRs were significantly higher in the plecostomus than in the mud carp and tilapia (p < 0.05), which could be explained by differences in habitat and feeding habits of the fish species. High concentrations of PFRs were found mainly in the Guangzhou section of the Pearl River (site P1, P2, and P3) and site B3, which was similar to our previous study of PFRs in sediment from the Pearl River Delta, indicating a relatively high level of PFRs pollution in these regions. The estimated daily intake (EDI) of total PFRs from consumption of fish was 17 ng/kg bw/day to 98 ng/kg bw/day for adults and children, which was three to four orders of magnitude lower than reference dose values.

Level changes and human dietary exposure assessment of halogenated flame retardant levels in free-range chicken eggs: A case study of a former e-waste recycling site, South China.

To assess the impacts of e-waste regulations on environmental pollution, we built on a previous study from 2010 to investigate the levels and human dietary exposure of halogenated flame retardants (HFRs) in free-range chicken eggs from Baihe village in 2013 and 2016. The concentrations of PBDEs, PBBs, HBCDs, and DBDPE showed a significant decrease (p<0.05) from 2010 to 2013/2016, suggesting the efficacy of regulatory policies. The relative contribution of BDE209 were higher in 2013 and 2016 than in 2010, accounting for 67.8%, 61.4%, and 27.7%, respectively. The concentration ratios of PBB209:PBB153 were much lower in 2013 (1.51) and 2016 (1.32) than in 2010 (29.5). These observed different profiles likely due to the different environmental behaviors of HFRs (e.g. the different atmospheric migration abilities of PBDE congeners and degradation of PBB209). Our exposure estimates suggested high dietary intake of HFRs via home-produced eggs. As for PBDEs, considering the worst situation (highly polluted eggs were consumed), the margin of exposure (MOE) of BDE99 for both adults and children were 1.5 and 0.3 in 2013, and 1.1 and 0.2 in 2016, respectively, which were below 2.5. According to the CONTAM panel, an MOE larger than 2.5 indicates no health concern. Therefore, these MOE values represent a significant potential health concern due to the adverse impacts of PBDEs on human neurodevelopment and fertility.

Determination of organophosphorus flame retardants in fish by freezing-lipid precipitation, solid-phase extraction and gas chromatography-mass spectrometry.

An analytical method has been developed for measuring 12 organophosphorus flame retardants (PFRs) in fish tissue samples. After the Soxhlet extraction of PFRs with dichloromethane. The experimental parameters of the clean-up were systematically optimized. Methanol was found to be a more effective solvent than acetonitrile used in freezing-lipid precipitation. Methanol (5%) in ultrapure water, was finally selected to perform solid-phase extraction (SPE, Oasis HLB cartridge), with mean lipid removal efficiency of 94% after freezing-lipid precipitation. Further purification followed by 200mg of Z-Sep and C18 dispersant to eliminate the remaining interferences. Quantification was performed using gas chromatography-mass spectrometry in selective ion monitoring mode. The recovery, precision, and the method detection limits (MDLs) were verified by spiking experiments. All chemicals except triethyl phosphate (TEP) showed satisfactory recoveries in the range of 73-107% and 56-108% in the spiked blanks samples and spiked fish tissue samples, respectively. MDLs for PFRs in the biological samples ranged from 0.004 to 0.059ng/g. The proposed method successfully applied to the determination of PFRs in real fish samples with recoveries of four internal standards varying from 75 to 97%. The results demonstrated that the proposed method is highly effective for analyzing PFRs in fish samples.