Organophosphate Flame Retardants in Pregnant Women: Sources, Occurrence, and Potential Risks to Pregnancy Outcomes.

Organophosphate flame retardants (OPFRs) are found in various environmental matrixes and human samples. Exposure to OPFRs during gestation may interfere with pregnancy, for example, inducing maternal oxidative stress and maternal hypertension during pregnancy, interfering maternal and fetal thyroid hormone secretion and fetal neurodevelopment, and causing fetal metabolic abnormalities. However, the consequences of OPFR exposure on pregnant women, impact on mother-to-child transmission of OPFRs, and harmful effects on fetal and pregnancy outcomes have not been evaluated. This review describes the exposure to OPFRs in pregnant women worldwide, based on metabolites of OPFRs (mOPs) in urine for prenatal exposure and OPFRs in breast milk for postnatal exposure. Predictors of maternal exposure to OPFRs and variability of mOPs in urine have been discussed. Mother-to-child transmission pathways of OPFRs have been scrutinized, considering the levels of OPFRs and their metabolites in amniotic fluid, placenta, deciduae, chorionic villi, and cord blood. The results showed that bis(1,3-dichloro-2-propyl) phosphate (BDCIPP) and diphenyl phosphate (DPHP) were the two predominant mOPs in urine, with detection frequencies of >90%. The estimated daily intake (EDIM) indicates low risk when infants are exposed to OPFRs from breast milk. Furthermore, higher exposure levels of OPFRs in pregnant women may increase the risk of adverse pregnancy outcomes and influence the developmental behavior of infants. This review summarizes the knowledge gaps of OPFRs in pregnant women and highlights the crucial steps for assessing health risks in susceptible populations, such as pregnant women and fetuses.

Unexpected Dioxin Formation During Digestion of Soil with Oxidizing Acids.

Dioxins, such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs), are among the most toxic unintentionally produced persistent organic pollutants, and their emission is of great concern. Herein, we discovered abundant dioxin formation in soil and various organic carbon-containing matrices after digestion with aqua regia. Σ17PCDD/Fs concentrations were in the range of 66.6-142,834 pg/g dw (5.6-17,021 pg WHO2005-TEQ/g dw) in 19 soil samples after digestion with aqua regia for 6 h. Σ17PCDD/Fs concentration was significantly and positively correlated with soil organic carbon content (R2 = 0.89; p < 0.01). Compared with cellulose and lignin, humic acid served as an important organic matter component that was converted to PCDD/Fs during soil digestion. Strong oxidation and production of reactive chlorine by aqua regia may be the key factors in the formation of PCDD/Fs. The yearly emission of PCDD/Fs due to digestion with strong acids by the inspection and testing industry was estimated to be 83.8 g TEQ in China in 2021 based on the highest level, which was ∼0.9% of the total dioxin inventory in China. Great attention should be paid to unexpected dioxin formation during digestion processes considering the potential risk of release from laboratories and enterprises.

Effect of Enterohepatic Circulation on the Accumulation of Per- and Polyfluoroalkyl Substances: Evidence from Experimental and Computational Studies.

The pharmacokinetic characteristics of per- and polyfluoroalkyl substances (PFAS) affect their distribution and bioaccumulation in biological systems. The enterohepatic circulation leads to reabsorption of certain chemicals from bile back into blood and the liver and thus influences their elimination, yet its influence on PFAS bioaccumulation remains unclear. We explored the role of enterohepatic circulation in PFAS bioaccumulation by examining tissue distribution of various PFAS in wild fish and a rat model. Computational models were used to determine the reabsorbed fractions of PFAS by calculating binding affinities of PFAS for key transporter proteins of enterohepatic circulation. The results indicated that higher concentrations were observed in blood, the liver, and bile compared to other tissues for some PFAS in fish. Furthermore, exposure to a PFAS mixture on the rat model showed that the reabsorption phenomenon appeared during 8-12 h for most long-chain PFAS. Molecular docking calculations suggest that PFAS can bind to key transporter proteins via electrostatic and hydrophobic interactions. Further regression analysis adds support to the hypothesis that binding affinity of the apical sodium-dependent bile acid transporter is the most important variable to predict the human half-lives of PFAS. This study demonstrated the critical role of enterohepatic circulation in reabsorption, distribution, and accumulation of PFAS.

Quantification of Biodriven Transfer of Per- and Polyfluoroalkyl Substances from the Aquatic to the Terrestrial Environment via Emergent Insects.

Emergent aquatic insects are important food subsidies to riparian food webs but can also transfer waterborne contaminants to the terrestrial environment. This study aimed to quantitatively assess this biodriven transfer for per- and polyfluoroalkyl substances (PFAS). Aquatic insect larvae, emergent aquatic insects, terrestrial consumers, sediment, and water were collected from a contaminated lake and stream and an uncontaminated pond, and analyzed for PFAS and stable isotopes of carbon and nitrogen. Top predators in this study were spiders, which showed the highest average ∑24PFAS concentration of 1400 ± 80 ng g-1 dry weight (dw) at the lake and 630 ng g-1 dw at the stream. The transfer of PFAS from the lake to the riparian zone, via deposition of emergent aquatic insects, was 280 ng ∑24PFAS m-2 d-1 in 2017 and only 23 ng ∑24PFAS m-2 d-1 in 2018. Because of higher production of emergent aquatic insects, the lake had higher PFAS transfer and higher concentrations in terrestrial consumers compared to the stream, despite the stream having higher PFAS concentration in water and aquatic insect larvae. Our results indicate that biodriven transfer of PFAS from the aquatic systems and subsequent uptake in terrestrial food webs depend more on emergence amounts, i.e., aquatic prey availability, rather than on PFAS concentrations in water and aquatic prey.

Characterization of the Chemical Contents of Fluorinated and Fluorine-Free Firefighting Foams Using a Novel Workflow Combining Nontarget Screening and Total Fluorine Analysis.

Aqueous film-forming foams (AFFFs) are widely used to extinguish liquid fires due to their film-forming properties. AFFF formulation historically contains per- and polyfluoroalkyl substances (PFASs) that can be very persistent and pose a health risk to biota and humans. Detailed analysis of the chemical composition of AFFFs can provide a better understanding on the potential environmental impact of the ingredients. In this study, a novel workflow combining target analysis, nontarget screening analysis (NTA), total fluorine (TF) analysis, and inorganic fluoride (IF) analysis was applied to disclose the chemical composition of 24 foams intended for liquid fires. Foams marketed as containing PFASs as well as fluorine-free foams were included. By comparing the sum of targeted PFASs and total organofluorine concentrations, a mass balance of known and unknown organofluorine could be calculated. Known organofluorine accounted for <1% in most fluorine-containing AFFFs, and it was confirmed that the foams marketed as fluorine-free did not contain measurable amounts of organofluorine substances. Five fluorinated substances were tentatively identified, and non-fluorinated zwitterionic betaine compounds, which are considered to be replacement substances for PFASs, were tentatively identified in the organofluorine-free foams.

Per- and Polyfluoroalkyl-Contaminated Freshwater Impacts Adjacent Riparian Food Webs.

The occurrence of per- and polyfluoroalkyl substances (PFASs) in aquatic ecosystems is a global concern because of their persistence, potential bioaccumulation, and toxicity. In this study, we investigated a PFAS-contaminated pond in Sweden to assess the cross-boundary transfer of PFASs from the aquatic environment to the riparian zone via emergent aquatic insects. Aquatic and terrestrial invertebrates, surface water, sediments, soils, and plants were analyzed for 24 PFASs including branched isomers. Stable isotope analysis of carbon and nitrogen was performed to elucidate the importance of diet and trophic position for PFAS uptake. We present the first evidence that PFASs can propagate to the riparian food web via aquatic emergent insects. Elevated Σ24PFAS concentrations were found in aquatic insect larvae, such as dragon- and damselflies, ranging from 1100 to 4600 ng g-1 dry weight (dw), and remained high in emerged adults (120-3500 ng g-1 dw), indicating exposure risks for top predators that prey in riparian zones. In terrestrial invertebrate consumers, PFAS concentrations increased with the degree of aquatic-based diet and at higher trophic levels. Furthermore, stable isotope data together with calculated bioaccumulation factors indicated that bioconcentration of PFASs was the major pathway of exposure in the aquatic food web and bioaccumulation in the riparian food web.

Cooking methods affect the intake of per- and polyfluoroalkyl substances (PFASs) from grass carp.

Consumption of fish is one of the predominant sources of human exposure to per- and polyfluoroalkyl substances (PFASs). In this study, the effect of various cooking methods (boiling, steaming, grilling and frying) on the levels of PFASs in fish muscle and the intake of PFASs was explored by using grass carp collected from Tangxun Lake, Wuhan, China. Perfluorooctane sulfonate (PFOS) was the predominant PFASs in raw fish fillets, with the concentrations ranging from 59.6 to 136 ng/g ww, followed by perfluorobutane sulfonate (PFBS) (7.73-51.9 ng/g ww). The concentrations of long-chain PFASs in fish increased after cooking, while those of short-chain PFASs decreased. The amounts of PFASs in the cooked fish fillets decreased except PFOS. Short-chain PFASs, including PFBS and perfluoroheptanoic acid (PFHpA), were dominant in cooking juice. The highest amounts of PFBS in the juices were observed after boiling and frying, even higher than those in cooked fish fillets, suggesting that the release of short-chain PFASs to the cooking juices could not be neglected. Based on these results, the intake of short-chain PFASs amount through cooked fish fillets slightly decreased, but the intake of PFOS amount increased. However, consumption of cooking juice (fish soup) could increase the exposure risk of PFBS. Comprehensively considering the increase of PFOS and decrease of total PFASs, boiling may be the relatively better method to cook fish. As PFASs are ubiquitous and inevitable in aquatic food, it is thus important to choose appropriate cooking processes and dietary habits for reducing the intake of different PFASs from fish.

Screening of Potential PFOS Alternatives To Decrease Liver Bioaccumulation: Experimental and Computational Approaches.

Perfluorooctanesulfonate (PFOS) is a persistent organic pollutant with significant bioaccumulation potential in liver tissues. Exposure to PFOS could cause increase of liver weight, induce adenomas of the liver, and cause hepatomegaly. Alternatives of PFOS might be designed and synthesized that have significantly lower liver bioaccumulation. In this study, we conducted animal exposure experiments to investigate tissue accumulations of 14 per- and polyfluoroalkyl substances. Correlation analysis demonstrated that accumulation of the compounds in rat liver had strong correlations with their binding affinities of liver fatty acid binding protein (LFABP). Thus, we combined a quantitative structure-activity relationship model with molecular dynamics (MD) simulations to develop computational models to predict the LFABP binding affinities of two newly synthesized alternatives, perfluorodecalin-2-sulfonic acid and N-diperfluorobutanoic acid. The binding characteristics of the PFOS alternatives for LFABP were elaborated to explore how the different structural modifications of molecules influenced the underlying binding mechanisms. Subsequent animal experiments demonstrated that the binding free energy calculations based on the MD simulations provided a good indicator to reflect the relative degree of liver accumulation of the PFOS alternatives in the same exposure doses and durations. Our findings from the combination of experimental exposure and computational model can provide helpful information to design potential alternatives of PFOS with weak LFABP binding capability and low liver accumulation.

Temporal trends of decabromodiphenyl ether and emerging brominated flame retardants in dust, air and window surfaces of newly built low-energy preschools.

The envelope of low-energy buildings is generally constructed with significant amounts of plastics, sealants and insulation materials that are known to contain various chemical additives to improve specific functionalities. A commonly used group of additives are flame retardants to prevent the spread of fire. In this study, decabromodiphenyl ether (BDE-209) and fourteen emerging brominated flame retardants (BFRs) were analyzed in indoor dust, air and on the window surface of newly built low-energy preschools to study their occurrence and distribution. BDE-209 and decabromodiphenyl ethane (DBDPE) were frequently detected in the indoor dust (BDE-209: <4.1-1200 ng/g, DBDPE: <2.2-420 ng/g) and on window surfaces (BDE-209: <1000-20 000 pg/m2 , DBDPE: <34-5900 pg/m2 ) while the other thirteen BFRs were found in low levels (dust: <0.0020-5.2 ng/g, window surface: 0.0078-35 pg/m2 ). In addition, the detection frequencies of BFRs in the indoor air were low in all preschools. Interestingly, the dust levels of BDE-209 and DBDPE were found to be lower in the environmentally certified low-energy preschools, which could be attributed to stricter requirements on the chemical content in building materials and products. However, an increase of some BFR levels in dust was observed which could imply continuous emissions or introduction of new sources.

Distribution, seasonal variation and inhalation risks of polychlorinated dibenzo-p-dioxins and dibenzofurans, polychlorinated biphenyls and polybrominated diphenyl ethers in the atmosphere of Beijing, China.

Spatial distribution, seasonal variation and potential inhalation risks of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were investigated in the atmosphere of Beijing, using passive air samplers equipped with polyurethane foam disks. Concentrations of ΣPCDD/Fs, ΣPCBs and ΣPBDEs ranged from 8.4 to 179 fg WHO2005-TEQ/m3, 38.6-139 and 1.5-176 pg/m3, respectively. PCDFs showed higher air concentrations than those of PCDDs, indicating the influence of industrial activities and other combustion processes. The non-Aroclor congener, PCB-11, was detected in air (12.3-99.4 pg/m3) and dominated the PCB congener profiles (61.7-71.5% to ∑PCBs). The congener patterns of PBDEs showed signatures from both penta-BDE and octa-BDE products. Levels of PCDD/Fs, PCBs and PBDEs at the industrial and residential sites were higher than those at rural site, indicating human activities in urban area as potential sources. Higher air concentrations of PCDD/Fs, PCBs and PBDEs were observed in summer, which could be associated with atmospheric deposition process, re-volatilization from soil surface and volatilization from use of technical products, respectively. Results of inhalation exposure and cancer risk showed that atmospheric PCDD/Fs, dioxin-like PCBs and PBDEs did not cause high risks to the local residents of Beijing. This study provides further aid in evaluating emission sources, influencing factors and potential inhalation risks of the persistent organic pollutants to human health in mega-cities of China.

Geographical Differences in Dietary Exposure to Perfluoroalkyl Acids between Manufacturing and Application Regions in China.

Emissions of perfluoroalkyl acids (PFAAs) have increased in China over the past decade, but human exposure pathways are poorly understood. Here we analyzed 15 PFAAs in commonly consumed food items and calculated body weight normalized dietary intake rates (estimated dietary intake, EDIs) in an area with ongoing PFAA production (Hubei province; n = 121) and an urbanized coastal area (Zhejiang province; n = 106). Geographical differences in concentrations were primarily observed for perfluorooctanesulfonic acid (PFOS) and perfluorohexanesulfonic acid (PFHxS) in animal food items and short-chain PFAAs in vegetable food items. The average EDI of ∑PFAAs for adults in Hubei (998 ng kg-1 day-1) was more than 2 orders of magnitude higher than that in Zhejiang (9.03 ng kg-1 day-1). In Hubei province, the average EDI of PFOS for adults (87 ng kg-1 day-1) was close to or exceeded advisory guidelines used in other countries indicating health risks for the population from long-term exposure. Yet, PFOS could only account for about 10% of the EDI of ∑PFAAs in the Hubei province, which was dominated by short-chain PFAAs through consumption of vegetables. The large contribution of short-chain PFAAs to the total EDIs in manufacturing areas emphasize the need for improved exposure and hazard assessment tools of these substances.

Levels, Isomer Profiles, and Estimated Riverine Mass Discharges of Perfluoroalkyl Acids and Fluorinated Alternatives at the Mouths of Chinese Rivers.

An extensive sampling campaign was undertaken to study the levels, isomer profiles and riverine mass discharges of perfluoroalkyl acids (PFAAs) and fluorinated alternatives in 19 Chinese rivers. The levels and homologue profiles of Σ10PFAAs varied considerably among the 19 rivers (mean 106; median 16.3, range 8.9-1240 ng/L), indicating the influence of specific point sources. Highly branched isomer profiles of perfluorooctanoic acid (18-25% br-PFOA) in rivers with elevated concentrations (96-352 ng/L) indicate that releases during production of PFOA by electrochemical fluorination and/or its use in fluoropolymer manufacture were the dominant sources to these rivers. The fluorinated alternatives 6:2 fluorotelomer sulfonate (detection frequency 21%, < 0.1-3.1 ng/L) and chlorinated polyfluoroalkyl ether sulfonate F-53B (51%, < 0.56-78.5 ng/L) were also found in some rivers. The total Chinese riverine mass discharges of PFOA (mean 80.9; range 16.8-168 t/y) (including monitoring data from this and other studies) were in good agreement with theoretical PFOA emission estimates (17.3-203 t/y) whereas riverine mass discharges of PFOS (mean 3.6; range 1.9-5.6 t/y) could only account for a minor fraction of theoretically estimated PFOS releases (70 t/y). This study provides empirical evidence that emissions from Chinese point sources likely dominate the global emissions of several legacy PFASs (notably PFOA) and fluorinated alternatives (e.g., F-53B).

Identification of Novel Polyfluorinated Ether Sulfonates as PFOS Alternatives in Municipal Sewage Sludge in China.

A 6:2 chlorinated polyfluorinated ether sulfonate (6:2 Cl-PFAES) with the trade name F-53B, is an alternative to perfluorooctanesulfonate (PFOS) in electroplating industry that is uniquely used in China. It was developed as a mist suppressant initially in the 1970s, but the environmental behaviors and potential adverse effects of the 6:2 Cl-PFAES have only recently been investigated. In this work, the occurrence and distribution of perfluoroalkyl sulfonate (PFSA), fluorotelomer sulfonate (FTSA), and PFAES analogues were investigated in municipal sewage sludge samples collected around China. Perfluorobutane, perfluorohexane, perfluorooctane, and perfluorodecanesulfonates, 6:2 and 8:2 FTSAs, and the emerging 6:2 Cl-PFAES were detected. Moreover, 8:2 and 10:2 Cl-PFAESs were identified for the first time as new polyfluorinated contaminants using high resolution mass spectrometry. These fluorinated analytes were further quantified with the aid of commercial and laboratory-purified standards. PFOS was the predominant contaminant with a geometric mean (GM) value of 3.19 ng/g dry weight (d.w.), which was subsequently followed by 6:2 Cl-PFAES and 8:2 Cl-PFAES (GM: 2.15 and 0.50 ng/g d.w., respectively). Both 6:2 and 8:2 Cl-PFAES were positively detected as the major components in the F-53B commercial product, and discrete 6:2 Cl-PFAES/8:2 Cl-PFAES ratios in the product and sludge samples might suggest 8:2 Cl-PFAES had enhanced sorption behavior in the sludge due to the increase in hydrophobicity.

Differential accumulation and elimination behavior of perfluoroalkyl Acid isomers in occupational workers in a manufactory in China.

In this study, serum and urine samples were collected from 36 occupational workers in a fluorochemical manufacturing plant in China from 2008 to 2012 to evaluate the body burden and possible elimination of linear and branched perfluoroalkyl acids (PFAAs). Indoor dust, total suspended particles (TSP), diet, and drinking water samples were also collected to trace the occupational exposure pathway to PFAA isomers. The geometric mean concentrations of perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), and perfluorohexanesulfonate (PFHxS) isomers in the serum were 1386, 371, and 863 ng mL(-1), respectively. The linear isomer of PFOS, PFOA, and PFHxS was the most predominant PFAA in the serum, with mean proportions of 63.3, 91.1, and 92.7% respectively, which were higher than the proportions in urine. The most important exposure routes to PFAA isomers in the occupational workers were considered to be the intake of indoor dust and TSP. A renal clearance estimation indicated that branched PFAA isomers had a higher renal clearance rate than did the corresponding linear isomers. Molecular docking modeling implied that linear PFOS (n-PFOS) had a stronger interaction with human serum albumin (HSA) than branched isomers did, which could decrease the proportion of n-PFOS in the blood of humans via the transport of HSA.

Detection of bioavailable cadmium, lead, and arsenic in polluted soil by tailored multiple Escherichia coli whole-cell sensor set.

Microbial whole-cell sensor has been widely used to assess bioavailability and risk of toxic elements, but their environmental use is still limited due to the presence of other interfering pollutants and the nonspecific binding in cells, which leads to inaccurate results. Here, we proposed a strategy combining Escherichia coli sensor set with binary regression models for the specific detection of bioavailable cadmium (Cd), lead (Pb), and arsenic (As) in a co-polluted environment. Initial tests suggested that the sensor set respectively termed pcadCluc, pzntRluc, and parsRluc could be classified into two groups according to their specific response to Cd, Pb, and As: group 1 (pcadCluc and pzntRluc) induced by a Cd-Pb mix and group 2 (parsRluc) induced by a Cd-As mix. Based on the variance in responses of each sensor to mixtures of target elements, three binary linear equations for two sensor groups were set up to calculate the individual concentrations in the mixture solutions. This method was then used to quantify the bioavailable Cd, Pb, and As in soils from a co-polluted mining region and to compare the results with other methods. Results showed that the conventional single target sensor method overestimated the bioavailability of each element, while sensor set was credible for accurate bioavailable Cd, Pb, and As quantification and comparable with the results from inductively coupled plasma mass spectrometry (ICP-MS) analysis. Our method can potentially be extended to cover the specific detection of other bioavailable toxic elements in different environmental settings.

Highly elevated serum concentrations of perfluoroalkyl substances in fishery employees from Tangxun lake, china.

Increasing production and use of per- and polyfluoroalkyl substances (PFASs) has been reported from China, and a few studies have shown there are subpopulations in China with high and increasing exposure to these chemicals. In this paper, we present a comprehensive exposure assessment of PFASs in fishery employees from Tangxun Lake, China. Exceptionally high serum concentrations of C4 to C12 PFASs were observed in fishery employees (n = 39, median perfluorooctanesulfonic acid (PFOS) 10 400 ng/mL) compared to a reference group from the same city (n = 9, median PFOS 18.7 ng/mL). On the basis of the comparison of different exposure pathways, it was concluded that contaminated fish from Tangxun Lake was the primary source of PFAS exposure to fishery employees, and there was a positive association between serum PFAS concentrations and time of employment in the fishery. PFOS isomer profiles in fishery employees showed a significantly higher proportion of linear PFOS (78.4%) compared to the background-exposed reference group (66.8%), reflecting the highly linear PFOS isomer profile (>90%) of lake fish. Median renal clearance rates (CLrenal) of C4 to C10 perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkanesulfonic acids (PFSAs) ranged from 0.020 to 16.5 mL/day/kg and 0.013 to 9.43 mL/day/kg, respectively. PFCAs with less than eight perfluoroalkyl carbons were primarily eliminated via urine, whereas other routes of excretion may have contributed to the elimination for long-chain PFCAs and PFSAs. Calculated daily PFOS exposures of fishery employees significantly exceeded tolerable daily intake limits, but clinical blood chemistry parameters were mostly within normal reference ranges. However, additional epidemiological studies are needed to address potential associations between PFAS exposure and health effects in the Tangxun Lake area.

Identification and composition of emerging quaternary ammonium compounds in municipal sewage sludge in China.

Quaternary ammonium compounds (QACs) have raised considerable attention due to their wide commercial applications and recent discovery of unknown persistent analogues in aqueous environment. In this work, the occurrence and distribution of alkyltrimethylammonium (ATMAC), benzylakyldimethylethylammonium (BAC) and dialkyldimethylammonium (DADMAC) homologues were investigated in fifty-two municipal sewage sludge samples. ATMAC C10-18, BAC C8-18 and paired DADMAC C8:8-C18:18 as well as emerging homologues such as ATMAC-20, 22 and mixed DADMAC-16:18 and 14:16 were present. Furthermore, paired DADMAC-20:20 and mixed DADMAC-14:18, 18:20 were identified for the first time by nontarget qualitative strategies. A triple quadruple mass spectrometer quantification method was also initially verified with the aid of laboratory synthesized standards for the analysis of the mixed DADMACs with no certificated commercial standards currently available. The total concentrations of ATMACs, BACs and DADMACs were in the range of 0.38-293, 0.09-191 and 0.64-344 µg/g dry weight, respectively, and particularly, mixed DADMACs constituted 39 ± 7% of total DADMAC concentrations. The concentrations and profiles of individual homologues further suggested different QAC applications and fate in China. Significant correlations were also found among the concentrations of various QAC homologues as well as wastewater treatment plant (WWTP) characteristics (total organic carbon contents and daily treatment volumes).

Levels and distributions of hexachlorobutadiene and three chlorobenzenes in biosolids from wastewater treatment plants and in soils within and surrounding a chemical plant in China.

Although hexachlorobutadiene (HCBD) was recently proposed as a candidate persistent organic pollutant (POP) under the Stockholm Convention, information about its environmental levels and distributions is still very limited. In this work, HCBD was determined in the sewage sludge from 37 wastewater treatment plants (WWTPs) in 23 cities and 17 soils near a chemical plant in China. Three chlorobenzenes (CBs) (1,2,4-trichlorobenzene, 1,2,4,5-tetrachlorobenzene, and hexachlorobenzene) were simultaneously studied to help better understand the environmental behavior of HCBD. Concentrations of HCBD in sludge samples ranged from <0.03 to 74.3 ng/g dry weight (dw) with a median value of 0.30 ng/g dw, which was lower than those of the three CBs. Levels of HCBD were not correlated with capacity of the WWTPs and total organic carbon. For soils, high level of HCBD was found in the sample within the plant, with a rapid decreasing concentration trend with the increase of distance from the plant. It was suspected that releasing as a byproduct during manufacturing of chlorinated chemicals was the primary source of HCBD in the studied location. Further risk assessment indicated that the environmental risk of HCBD to soil organisms and the health risk to employees were very low through soil exposure within the plant.

Alterations of endogenous metabolites in urine of rats exposed to decabromodiphenyl ether using metabonomic approaches.

There is large usage of polybrominated diphenyl ethers (PBDEs) especially for decabromodiphenyl ether (BDE-209, Deca-BDE) in controlling the risks of fire. The toxicological effects of PBDEs are worth being concerned about. Female SD rats were daily gavaged with BDE-209 ether at the dose of 100 mg/kg for 20 days. Histological observation was performed for the screening of the target organs for BDE-209 exposure. The distribution and metabolism of PBDEs in the exposed main organs were evidenced by HRGC-HRMS. Alterations of the endogenous metabolite concentrations in urine were investigated using metabonomic approaches based on (1)H NMR spectrum. Histopathological changes including serious edema in kidney, hepatocellular spotty necrosis and perivasculitis in liver indicated that BDE-209 caused potential influences on endogenous metabolism in the exposed liver and the kidney. BDE-209 was found to be highly accumulated in lipid, ovary, kidney and liver after 20 days' exposure. Occurrence of other lower brominated PBDEs in the rats demonstrated that reductive debromination process happened in vivo. Hydroxylated and methoxylated-BDEs, as metabolism products, were also detected in the rat tissues. A total of 12 different endogenous metabolites showed obvious alterations in urine from the exposed rats, indicating the disturbance of the corresponding internal biochemical processes induced by BDE-209 exposure. These findings in vivo suggested the potential health risk might be of concern due to the toxicological effects of BDE-209 as a ubiquitous compound in the environment.

Metabolites of 2,4,4'-tribrominated diphenyl ether (BDE-28) in pumpkin after in vivo and in vitro exposure.

There is currently limited knowledge on PBDE metabolism in plants although they could play an important role in the environmental transformation of these persistent organic pollutants. In this study, pumpkin (Cucurbita maxima × C. moschata) was chosen as the model to understand the fate of BDE-28 in plants. MeO-tri-BDEs, OH-tri-BDEs, and OH-tri-BDEs were found as metabolites in plant samples of both in vivo hydroponic and in vitro tissue culture exposure. Three MeO-tri-BDEs were further identified as para-substituted metabolites. MeO-BDEs and OH-BDEs, respectively, accounted for about 1.6% and 1.5% (recovery corrected) of initial amount of BDE-28 according to the semiquantitative results. Other PBDEs, especially less brominated PBDEs as impurities in the standard of BDE-28, were also detected. The impurities and evaporation of the standard must be considered when trace metabolites are studied in exposure experiments.