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.

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. Sigma 17PCDD/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. Sigma 17PCDD/Fs concentration was significantly and positively correlated with soil organic carbon content (R-2 = 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 similar to 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.

Omics-based technologies have enabled comprehensive characterization of our exposure to environmental chemicals (chemical exposome) as well as assessment of the corresponding biological responses at the molecular level (eg, metabolome, lipidome, proteome, and genome). By systematically measuring personal exposures and linking these stimuli to biological perturbations, researchers can determine specific chemical exposures of concern, identify mechanisms and biomarkers of toxicity, and design interventions to reduce exposures. However, further advancement of metabolomics and exposomics approaches is limited by a lack of standardization and approaches for assigning confidence to chemical annotations. While a wealth of chemical data is generated by gas chromatography high-resolution mass spectrometry (GC-HRMS), incorporating GC-HRMS data into an annotation framework and communicating confidence in these assignments is challenging. It is essential to be able to compare chemical data for exposomics studies across platforms to build upon prior knowledge and advance the technology. Here, we discuss the major pieces of evidence provided by common GC-HRMS workflows, including retention time and retention index, electron ionization, positive chemical ionization, electron capture negative ionization, and atmospheric pressure chemical ionization spectral matching, molecular ion, accurate mass, isotopic patterns, database occurrence, and occurrence in blanks. We then provide a qualitative framework for incorporating these various lines of evidence for communicating confidence in GC-HRMS data by adapting the Schymanski scoring schema developed for reporting confidence levels by liquid chromatography HRMS (LC-HRMS). Validation of our framework is presented using standards spiked in plasma, and confident annotations in outdoor and indoor air samples, showing a false-positive rate of 12% for suspect screening for chemical identifications assigned as Level 2 (when structurally similar isomers are not considered false positives). This framework is easily adaptable to various workflows and provides a concise means to communicate confidence in annotations. Further validation, refinements, and adoption of this framework will ideally lead to harmonization across the field, helping to improve the quality and interpretability of compound annotations obtained in GC-HRMS.

Monitoring the vast number of micropollutants in the environment by using comprehensive chemical screening is a major analytical challenge. The aim of this study was to evaluate a comprehensive analysis method for screening purposes of fish muscle samples by comparing sample preparation methods for a broad range of mid-to non-polar contaminants. Five extraction and three clean-up methods were evaluated for the analysis of 60 compounds with a log Kow range between 0.8 and 8.3 in fish. Both fresh and freeze-dried muscle tissue and extraction sodium sulphate blanks were included to assess recoveries and matrix effects. The performance of the different methods was evaluated using both comprehensive target and nontarget analysis using high resolution mass spectrometry (HRMS). The results showed that open-column and ultrasonication extractions (recoveries mostly between 20 and 160 %) resulted in higher recoveries than accelerated solvent extraction (ASE) (recoveries mostly between 20 and 80 %) and bead mixer homogenization extractions (recoveries between 0 and 50 % for the whole Kow range). Multilayer silica was the clean-up method resulting in the lowest matrix effects and highest recoveries, however some compounds (mostly pesticides) were denatured under the acidic conditions used. The convenient and time efficient ultrasonication extraction followed by deactivated silica clean-up proved to be promising for both target and nontarget approaches. The large difference in recoveries and number of detected peaks using target and nontarget approaches between fresh and freeze-dried fish seen for all methods calls for careful consideration, and further studies are needed to improve performance for screening of mid-to non-polar compounds in freeze-dried fish.

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.

With the recent improvements in high-resolution mass spectrometry (HRMS), retrospective chemical analysis has been increasingly used in environmental sciences. This enables new insights into the chemical content of previously analysed samples with new data analysis methods or new information about emerging contaminants. This study aimed to conduct an in-depth investigation into the chemical content of various indoor dust samples using retrospective analysis. The samples were previously extracted using liquid-solid extraction without clean-up to increase the chemical coverage and thereafter analysed both using liquid chromatography (positive and negative ionisations) and gas chromatography coupled with high-resolution mass spectrometry. A retrospective data processing workflow was conducted in this new study by using both suspect screening analysis and non-target analysis. Among 30 dust samples from four different indoor settings, 298 compounds were tentatively identified with an identification confidence level of ≥ 3. The discussion was conducted on both individual compounds as well as their chemical compound groups and functional uses. Main detected chemical groups were plant natural products (n = 57), personal care products (n = 44), pharmaceuticals (n = 44), food additives (n = 43), plasticisers (n = 43), flame retardants (n = 43), colourants (n = 42) and pesticides (n = 31). Although some detected compounds were already reported for the same samples in our previous study, this retrospective analysis enabled the tentative identification of compounds such as polyethylene glycols, per- and polyfluoroalkyl substances, pesticides, benzotriazoles, benzothiazoles, fragrances, colourants and UV stabilizers. This study showed the usefulness of retrospective analysis on indoor dust samples to further characterise the chemical content, which can help to better estimate the exposure risks of organic contaminants to humans in the indoor environment.

Polycyclic aromatic compounds (PACs) are organic compounds commonly found in contaminated soil. Previous studies have shown the removal of polycyclic aromatic hydrocarbons (PAHs) in creosote-contaminated soils during steam enhanced extraction (SEE). However, less is known about the removal of alkyl-PAHs and heterocyclic compounds, such as azaarenes, and oxygen- and sulfur-heterocyclic PACs (OPACs and PASHs, respectively). Further, the impact of SEE on the freely dissolved concentration of PACs in soil as well as the soil bioactivity pre- and post-SEE have yet to be addressed. To fulfil these research gaps, chemical and bioanalytical analysis of a creosote-contaminated soil, collected from a U.S. Superfund site, pre- and post-SEE were performed. The decrease of 64 PACs (5-100%) and increase in the concentrations of nine oxygenated-PAHs (OPAHs) (150%) during SEE, some of which are known to be toxic and can potentially contaminate ground water, were observed. The freely dissolved concentrations of PACs in soil were assed using polyoxymethylene (POM) strips and the concentrations of 66 PACs decreased post-SEE (1-100%). Three in vitro reporter gene bioassays (DR-CALUX®, ERα-CALUX® and anti-AR CALUX®) were used to measure soil bioactivities pre- and post-SEE and all reporter gene bioassays measured soil bioactivity decreases post-SEE. Mass defect suspect screening tentatively identified 27 unique isomers of azaarenes and OPAC in the soil. As a remediation technique, SEE was found to remove alkyl-PAHs and heterocyclic PACs, reduce the concentrations of freely dissolved PACs, and decrease soil bioactivities.

The vast number of per- and polyfluoroalkyl substances (PFASs) that are in global commerce (n > 4700) pose immense challenges for environmental monitoring. The large discrepancy between this large number and the few PFASs usually monitored suggest that environmental exposure might be substantially underestimated. This study applied a workflow, which included analysis of total fluorine (TF), extractable organofluorine (EOF), 24 target PFASs and suspect screening. The workflow aimed to close the organofluorine mass balance and to tentatively identify overlooked PFASs in various matrices from an aqueous film forming foam (AFFF) contaminated pond and its adjacent riparian zone. PFAS target analysis revealed that water, aquatic invertebrates as well as emergent aquatic insects had high concentrations with up to 2870 ng L-1, 9230 ng g-1 dry weight (dw) and 1470 ng g-1 dw ∑24PFASs, respectively. The EOF mass balance could be explained by target PFAS analysis for most biota samples such as aquatic invertebrates, emergent aquatic insects and terrestrial spiders and earthworms (i.e. EOF ≈ ∑24PFASs). In the pond surface water, 42-58% of the EOF was not explained by target PFASs. However most new tentatively identified PFASs (n = 25) were detected in water, which could contribute to the unknown EOF. Nine suspects could be further identified, which where perfluoroalkyl sulfonamide-based compounds and derivatives that all have been found in historical AFFFs produced by electrochemical fluorination. One suspect, F5S-PFOS, was also detected for the first time in aquatic and terrestrial invertebrates. 

Since humans spend more than 90% of their time in indoor environments, indoor exposure can be an important non-dietary pathway to hazardous organic contaminants. It is thus important to characterize the chemical composition of indoor dust to assess the total contaminant exposure and estimate human health risks. The aim of this investigation was to perform a comprehensive chemical characterization of indoor dust. First, the robustness of an adopted extraction method using ultrasonication was evaluated for 85 target compounds. Thereafter, a workflow combining target analysis, suspect screening analysis (SSA) and nontarget analysis (NTA) was applied to dust samples from different indoor environments. Chemical analysis was performed using both gas chromatography and liquid chromatography coupled with high resolution mass spectrometry. Although suppressing matrix effects were prominent, target analysis enabled the quantification of organophosphate/brominated flame retardants (OPFRs/BFRs), liquid crystal monomers (LCMs), toluene diisocyanate, bisphenols, pesticides and tributyl citrate. The SSA confirmed the presence of OPFRs but also enabled the detection of polyethylene glycols (PEGs) and phthalates/parabens. The combination of hierarchical cluster analysis and scaled mass defect plots in the NTA workflow confirmed the presence of the above mentioned compounds, as well as detect other contaminants such as tetrabromobisphenol A, triclocarban, diclofenac and 3,5,6-trichloro-2-pyridinol, which were further confirmed using pure standards.

Recent publications have highlighted the ubiquitous presence of unidentified organofluorine compounds, whose environmental occurrence is poorly understood. In this study, wastewater treatment plant (WWTP) effluent and sludge samples from seven countries were analyzed for extractable organofluorine (EOF) and target PFAS, to evaluate which compounds are released back into the environment. Fluorine mass balance analysis of effluent samples (n = 14) revealed that on average 90% of the EOF could not be explained by the 73 PFAS monitored in this investigation. The levels of EOF in effluent (324–1460 ng of F/L) and sludge (39–210 ng of F/g of dry weight) indicate that a substantial amount of organofluorine compounds is released back into nature. A commonly overlooked PFAS class, ultra-short-chain PFCAs, accounted for 4% of EOF on average, while the remaining 71 compounds explained only a further 6% of EOF on average. The highest number of PFAS was detected in the effluent dissolved phase (37), compared to 29 and 23 PFAS in sludge and effluent particulate phase, respectively. The increased concentrations of EOF in both WWTP effluent and sludge are of concern, as the chemical species contained therein remain largely unknown, and thus, their potential health and environmental risks cannot be assessed.

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. 

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.

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.

During a fire event, potentially hazardous chemicals are formed from the combustion of burning materials and are released to the surrounding environment, both via gas and soot particles. The aim of this investigation was to study if firefighting techniques influence the emission of chemicals in gas phase and soot particles. Five full-scale fire tests were extinguished using four different firefighting techniques. A nontarget chemical analysis approach showed that important contaminants in gas and soot separating the different tests were brominated flame retardants (BFRs), organophosphate flame retardants (OPFR), polycyclic aromatic hydrocarbons (PAHs) and linear hydrocarbons. Reproducibility was evaluated by a field replicate test and it was determined that the temperature curve during the event had a bigger impact on the released chemicals than the firefighting technique used. However, despite fire intensity being a confounding factor, multivariate statistics concluded that water mist with additive resulted in less BFR emissions compared to foam extinguishing. The analysis also showed that the conventional spray nozzle method released more PAHs compared with the water mist method. The comprehensive chemical analysis of gas and soot released during fire events was able to show that different firefighting techniques influenced the release of chemicals. 

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.

Perfluorooctansulfonate (PFOS) is a persistent organic pollutant that has attracted a great deal of attention due to toxic effects such as its lipid metabolism-disrupting potential. Exposure to PFOS can cause hepatomegaly and lipoatrophy in mice, but the underlying mechanisms are still unknown. Considering that glyceroneogenesis is the essential pathway for balancing the triglyceride (TG) cycle between liver and white adipose tissue (WAT), we speculate that PFOS acts via glyceroneogenesis inhibition to alter TG metabolism in the two tissues. Combining gene expression, protein expression, an enzyme activity assay, and molecular docking analysis, we report here that PFOS can interact with cytosolic phosphoenolpyruvate carboxykinase (PEPCK), the rate-limiting enzyme of glyceroneogenesis. Specifically, by repression of PEPCK, PFOS can inhibit the glyceroneogenesis process and thus decrease the glyceroneogenesis-derived glycerol level, leading to a reduced re-esterified TG level and causing atrophy in WAT. Moreover, in PFOS-exposed liver tissue, despite the fact that free glycerol and fatty acids released from WAT were being used for TG synthesis, the export of TG slowed. This eventually resulted in the continuous lipolysis of WAT and accumulation of lipid in the liver. PEPCK can be used as a key biomarker to assess the lipid metabolism disorders induced by other conventional and emerging per- and polyfluoroalkyl substances.

This review summarizes and discusses eight analytical methods for organofluorine (OF) analysis, which offer detection limits suitable for consumer products and environmental samples. Direct sample analysis of OF only applies to some techniques on consumer products, whereas others require sample pretreatment or concentration before measurements. Comparison between methods for OF analysis were found to be difficult because of different selectivity (between OF and fluoride), sensitivity and type of samples (bulk, extract, surface) analysed. Neither inter-laboratory comparison on OF analysis nor suitable certified reference materials have been used for method validation, which makes data comparability between studies challenging. A top down approach for the comprehensive assessment of OF is proposed, where OF/extractable OF is first measured, followed by target analysis to obtain unquantifiable OF concentrations using the mass balance approach. For further identification of unquantifiable OF, approaches such as total oxidizable precursor assay, suspect and non-target screening are briefly discussed.

Annual air samples were collected at various sites in the Fildes Peninsula, West Antarctica from December 2010 to January 2018 using XAD-2 resin passive air samplers to investigate concentrations, temporal trends and potential sources of persistent organic pollutants (POPs) in Antarctic air. Relatively low concentrations of polychlorinated biphenyls (PCBs) (Σ₁₉PCBs: 1.5-29.7 pg/m³), polybrominated diphenyl ethers (PBDEs) (Σ₁₂PBDEs: 0.2-2.9 pg/m³) and organochlorine pesticides (OCPs) (Σ₁₃OCPs: 101-278 pg/m³) were found in the atmosphere of West Antarctica. PCB-11, BDE-47 and hexachlorobenzene (HCB) were the predominant compounds in the atmosphere. The concentrations of PCBs, HCHs, DDTs and endosulfans were found to show decreasing temporal trends, whereas uniform temporal trends were observed for HCB. The atmospheric half-life values for PCBs, HCHs, DDTs and endosulfans in Antarctic air were estimated for the first time, using regressions of the natural logarithm of the concentrations versus the number of years, obtaining the values of 2.0, 2.0, 2.4 and 1.2 year, respectively. An increasing ratio of α-HCH/γ-HCH indicated long residence time for α-HCH and possible transformation of γ-HCH to α-HCH in the atmosphere. The ratios of p,p'-DDT/p,p'-DDE were mostly lower than unity in this study, which could be attributed to aged sources. It was found that long-range atmospheric transport was still considered to be the main contributing factor to the atmospheric levels of the POPs in West Antarctica whereas the contribution of human activities at the Chinese Great Wall Station was minor. The results of this study give a view on the most recent temporal trends and provide new insights regarding the occurrence of various POPs in the Antarctic atmosphere.

The use of an airtight frame in low-energy buildings could increase the risk of health-related problems, such as allergies and sick building syndromes (SBS), associated with chemical emissions from building materials, especially if the ventilation system is not functioning properly. In this study, the indoor air quality (IAQ) was investigated in newly built low-energy and conventional preschools by monitoring the indoor air temperature, relative humidity, particle-size distribution and levels of carbon dioxide (CO2), nitrogen dioxide (NO2), formaldehyde and total volatile organic compounds (TVOC). The thermal comfort was satisfactory in all preschools, with average indoor air temperature and a relative humidity at 21.4C and 36%, respectively. The highest levels of TVOC (range: 130–1650 mg/m3 toluene equivalents) and formaldehyde (range: 1.9–28.8 mg/m3) occurred during the first sampling period associated with strong emissions from building materials. However, those preschools constructed with environmental friendly building materials (such as Swan Eco-label) had lower initial TVOC levels compared to those preschools constructed with conventional building materials. The IAQ and indoor chemical emissions were also strongly dependent on the functioning of the ventilation system. Preliminary risk assessment indicated that exposure to acrolein and crotonaldehyde might lead to respiratory-tract irritation among occupants.

This report describes a screening study of in all ninety-nine conventional and emerging per- and polyfluoroalkyl substances (PFASs) in the Nordic environment. In addition, extractable organic fluorine (EOF) was analysed. The latter can provide the amount, but not identity, of organofluorine in the samples, which in turn can be used to assess the mass balance between known and unknown PFASs. The study was initiated by the Nordic Screening Group and funded by these and the Nordic Council of Ministers through the Chemicals Group. A total of 102 samples were analyzed in this study, including bird eggs, fish, marine mammals, terrestrial mammals, surface water, WWTP effluents and sludge, and air. Samples were collected by institutes from the participating countries and self-governing areas; Denmark, Faroe Islands, Finland, Greenland, Iceland, Norway, and Sweden.

Major point sources of per- and polyfluoroalkyl substances (PFASs) cause ubiquitous spread of PFASs in the environment. In this study, surface water and aquatic invertebrates at three Swedish sites impacted by PFAS point sources were characterized, using homologue, isomer and extractable organofluorine (EOF) profiling as well as estimation of bioaccumulation factors (BAFs) and mass discharge. Two sites were impacted by fire training (sites A and R) and the third by industrial runoff (site K). Mean Σ25PFASs concentration in water was 1920 ng L-1 at site R (n = 3), which was more than 20- and 10-fold higher than those from sites A and K, respectively. PFOS was the most predominant PFAS in all waters samples, constituting 29-79% of Σ25PFAS concentrations. Several branched isomers were detected and they substantially contributed to concentrations in surface water (e.g. 49-78% of ΣPFOS) and aquatic invertebrates (e.g. 15-28% of ΣPFOS). BAFs in the aquatic invertebrates indicated higher bioaccumulation for long chain PFASs and lower bioaccumulation for branched PFOS isomers compared to linear PFOS. EOF mass balance showed that Σ25target PFASs in water could explain up to 55% of EOF at site R. However, larger proportions of EOF (>92%) remained unknown in water from sites A and K. Mass discharges were for the first time estimated for EOF and revealed that high amounts of EOF (e.g. 8.2 g F day-1 at site A) could be transported by water to recipient water bodies relative to Σ25PFASs (e.g. 0.15 g day-1 at site A). Overall, we showed that composition profiling, BAFs and EOF mass balance can improve the characterization of PFASs around point sources.

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.

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.

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/m(3), 38.6-139 and 1.5-176 pg/m(3), 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/m(3)) 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.

The construction of extremely airtight and energy efficient low-energy buildings is achieved by using functional building materials, such as age-resistant plastics, insulation, adhesives, and sealants. Additives such as organophosphate flame retardants (OPFRs) can be added to some of these building materials as flame retardants and plasticizers. Some OPFRs are considered persistent, bioaccumulative and toxic. Therefore, in this pilot study, the occurrence and distribution of nine OPFRs were determined for dust, air, and window wipe samples collected in newly built low-energy preschools with and without environmental certifications. Tris(1,3-dichloroisopropyl) phosphate (TDCIPP) and triphenyl phosphate (TPHP) were detected in all indoor dust samples at concentrations ranging from 0.014 to 10 μg/g and 0.0069 to 79 μg/g, respectively. Only six OPFRs (predominantly chlorinated OPFRs) were detected in the indoor air. All nine OPFRs were found on the window surfaces and the highest concentrations, which occurred in the reference preschool, were measured for 2-ethylhexyl diphenyl phosphate (EHDPP) (maximum concentration: 1500 ng/m²). Interestingly, the OPFR levels in the environmental certified low-energy preschools were lower than those in the reference preschool and the non-certified low-energy preschool, probably attributed to the usage of environmental friendly and low-emitting building materials, interior decorations, and consumer products.

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 Sigma 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 Sigma 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.

A method using a novel atmospheric pressure chemical ionization source for coupling gas chromatography (GC/APCI) to triple quadrupole mass spectrometry (MS/MS) for the determination of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) regulated by the Stockholm Convention is presented. One microliter injection of a six-point calibration curve of native PCBs and OCPs, ranging from 0.04 to 300 pg/μL, was performed. The relative standard deviation (RSD) of the relative response factors (RRFs) was less than 15% with a coefficient of determination (r2) &gt;0.995. Meanwhile, two calibration solutions (CS), CS 2 (0.4 pg/μL) and CS 3 (4 pg/μL) were analyzed to study the repeatability calculated for both area and RRFs. The RSD for RRF ranged from 3.1 to 16% and 3.6 to 5.5% for CS 2 and CS 3, respectively. The limits of detection (LOD) determined by peak-to-peak signal-to-noise ratio (S/N) of 3 were compared between the GC/APCI/MS/MS and a GC coupled to high resolution mass spectrometry (GC/HRMS) system. GC/APCI/MS/MS resulted in lower LOD for most of the compounds, except for PCB#74, cis-chlordane and trans-chlordane. GC/APCI/MS/MS and GC/HRMS were also compared by performing analysis on 75 human serum samples together with eight QA/QC serum samples. The comparison between GC/APCI/MS/MS system and GC/HRMS system for 16 of the targeted compounds was carried out. No statistically significant difference was discovered. Due to increased sensitivity and user friendly operation under atmospheric pressure, GC/APCI/MS/MS is a powerful alternative technique that can easily meet the specification of GC/HRMS.

The distribution and fate of polybrominated diphenyl ethers (PBDEs) in a riparian ecosystem nearby a wastewater treatment plant effluent were investigated. Different aqueous and terrestrial samples such as soil, sediment, plants, and invertebrates were collected and analyzed for tri- to heptabrominated PBDEs. Furthermore, the food web structure was elucidated using stable carbon and nitrogen isotopes. The highest PBDE levels were found for sediment- and soil-dwelling invertebrates, such as earthworms (Σ13 PBDEs 144 ng/g lipid weight), Tubifex tubifex (77 ng/g lw), and scarab larvae (49 ng/g lw). Differences in congener composition profiles among the different matrices show that the environmental distribution and fate of PBDEs in ecosystems can be very complex. Among the analyzed PBDEs in this ecosystem, the tetra-brominated BDE-47 was the dominant PBDE congener and followed by the penta-brominated BDE-99. A potential trend of increasing BDE-47/99 ratio with the increase of δ(15)N was observed for species with similar energy sources (δ(13)C), indicating a higher bioaccumulation potential for BDE-47 in this ecosystem. A significant correlation was also found between PBDEs and polychlorinated biphenyls (PCBs), indicating similar sources and fate between the two compound groups in this area. The biota-soil or biota-sediment accumulation factors (BSAFs) were somewhat different among the PBDE congeners and species, but were generally highest for those with log Kow values around 6.5-7.

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).

Although Dechlorane Plus (DP) has been used as a polychlorinated flame retardant for almost half a century, its detection in the environment was not reported until 2006. The subsequent intensive research has confirmed its global ubiquity. A few reviews have presented the properties, analytical methods and environmental occurrence of DP and related compounds in the past several years. The present review emphasizes on the environmental behavior of DP isomers which is assessed by the variation of the isomer ratio of DP in various matrices. Other aspects including the analytical methods, emission sources, general environmental occurrence and bioaccumulation of DP are also summarized.

In this review, three typical emission sources in the environment are categorized after introducing the measurement method of DP. The temporal-spatial distribution is then evaluated at the global scale, which provides an integrated representation of the environmental occurrence of DP and potential impact on the human health and ecosystems. The variations of DP isomer ratio in various matrices reinforce its source related distribution and their stereoselective bioaccumulation. Thereafter, DP related compounds and dechlorinated analogs are briefly summarized in regards to their occurrence in various matrices, suggesting their ubiquity in the environment and bioavailability. Further studies are required to better assess the exposures and toxicological effects of DP and its analogs. A special concern is the serious contamination in e-waste recycling areas in developing countries, where long-term monitoring data on the association of DP exposure and adverse effects to human health and ecosystems is urgently needed.

It is hard to quantify the trace pollutants in the environment without the corresponding reference standards. Structure identifications of unknown organic pollutants are thus of great importance in environmental analysis. As for polybrominated diphenyl ethers (PBDE) with one substituent of methoxyl group, there are 837 congeners, but only 32 standards are commercially available. In this work, an effective method based on gas chromatography coupled with mass spectrometry (GC-MS) was proposed to predict the potential structures of methoxylated polybrominated diphenyl ethers (MeO-PBDEs). The mass fragmentation pattern using SIM mode not only provided the useful information on the substitution position of methoxyl group, the number of Br atoms, but also guaranteed the high sensitivity for trace analysis. Br distribution patterns of the unknown MeO-PBDEs were revealed by a linear regression model with dummy variables which described the retention time relationship between MeO-PBDEs and the corresponding PBDEs on different types of GC columns. This method was successfully used to identify three new MeO-PBDEs metabolites of BDE-28 as 4-MeO-BDE-22, 4'-MeO-BDE-25 and 4-MeO-BDE-31 in the pumpkins. Therefore, the newly developed structure prediction model based on GC-MS behavior is helpful in the evaluation of unknown PBDE metabolites in the environment.

The aim of this study was to measure perfluoroalkyl substances in a selection of imported consumer products (n = 45) and estimate population normalized emission rates during the use phase. 6:2 and 8:2 fluorotelomer alcohol (FTOH) were found in the highest concentrations ranging from <MDL to 374 and 163 mu g m(-2) respectively. Concentrations of FTOHs were approximately 2-3 orders of magnitude higher than those of perfluoroalkyl carboxylic acids (PFCAs). Although perfluorooctane sulfonate (PFOS) was detected in one carpet sample at 1.7 mu g m(-2), the majority of samples complied with regulatory limits for PFOS in the EU. Population normalized emission rates of perfluorooctanoic acid, 6:2 FTOH and 8:2 FTOH from imported consumer products were estimated to be 6.6, 2130 and 197 mu g year(-1) capita(-1) respectively for the "intermediate" emistion scenario. The results from this study suggest that emissions from imported products would have a small impact on the environmental concentrations of perfluoroalkyl acids on a regional scale.

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.

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.

The exposure pathways of perfluoroalkyl acids (PFAAs) to humans are still not clear because of the complex living environment, and few studies have simultaneously investigated the bioaccumulative behaviour of different PFAAs in humans. In this study, serum, dust, duplicate diet, and other matrices were collected around a manufacturing plant in China, and homologous series of PFAAs were analysed. PFAA levels in dust and serum of local residents in this area were considerably higher than those in non-polluted area. Although dietary intake was the major exposure pathway in the present study, dust ingestion played an important role in this case. Serum PFAAs in local residents was significantly correlated with dust PFAAs levels in their living or working microenvironment. Serum PFAAs and dust PFAAs were significantly higher in family members of occupational workers (FM) than in ordinary residents (OR) (p<0.01). After a careful analysis of the PFAAs exposure pathway, a potential pathway in addition to direct dust ingestion was suggested: PFAAs might transferred from occupational worker's clothes to dinners via cooking processes. The bioaccumulative potential of PFHxS and PFOS were higher than other PFAAs, which suggested a substantial difference between the bioaccumulative ability of perfluorinated sulfonic acids and perfluorinated carboxylic acids.

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.

Short chain chlorinated paraffins (SCCPs) have been of considerable concern in recent years due to their high production volumes, environmental persistency and potential for long range atmospheric transport. Vegetation can take up considerable amounts of semivolatile organic compounds from the atmosphere and can act as indicators of local contamination. Paired pine needles and bark were sampled around Beijing during winter and summertime to investigate the distribution of SCCPs in urban areas. Levels in bark samples ranged 5.79-37.5 mu g/g on a lipid normalized basis (lw) with a geometric mean (GM) of 16.9 mu g/g lw whereas levels were 3.03-40.8 (GM 11.8) mu g/g lw for needles. Average congener group abundance profiles showed equal contribution of all four carbon groups (C10-13) in wintertime whereas higher abundances of C-10 and C-11 groups were found during summer. Uptake of SCCPs occurred mainly via kinetically limited gaseous deposition and particle bound deposition in the investigated area.

This study investigated a wide range of semi-volatile organic compounds (SVOCs), including 28 persistent organochlorine pesticides (OCPs), 18 polychlorinated biphenyls (PCBs), 13 polybrominated diphenyl ethers (PBDEs), and 3 hexabromocyclododecane (HBCD) congeners in lichen, moss and soil collected from the southeastern Tibetan Plateau, China. This allows research provides insight into elevation gradient distributions and possible cold trapping effects of SVOCs in this high mountain area, and compares lichens and mosses as air passive samplers for indicating SVOC occurrences. DDTs, endosulfans, HCHs and hexachlorobenzene predominated in all of the samples. Source analysis indicted that there were fresh inputs of DDTs and HCHs in the sampling region. Lichens and mosses shared commonalities in revealing the profiles and levels of SVOCs based on their lipid-content-normalized concentrations. The concentrations of 12 OCPs and 14 PCBs in lichens were significantly linearly correlated with altitudes, whereas the correlations for mosses and soil with altitudes were insignificant. Both a frequency distribution diagram and the Mountain Contamination Potential Model indicated that SVOCs with specific values of log K-OA (8-11) and log K-WA (2-4) had relative high mountain contamination potential on the Tibetan Plateau.

A total of 155 rice plants were collected from ten mining areas in three provinces of China (Hunan, Guizhou and Guangdong), where most of mercury (Hg) mining takes place in China. During the harvest season, whole rice plants were sampled and divided into root, stalk & leaf, husk and seed (brown rice), together with soil from root zone. Although the degree of Hg contamination varied significantly among different mining areas, rice seed showed the highest ability for methylmercury (MeHg) accumulation. Both concentrations of total mercury (THg) and MeHg in rice plants were significantly correlated with Hg levels in soil, indicating soil is still an important source for both inorganic mercury (IHg) and MeHg in rice plants. The obvious discrepancy between the distribution patterns of THg and MeHg reflected different pathways of IHg and MeHg accumulation. Water soluble Hg may play more important role in MeHg accumulation in rice plants.

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.

A method using automated on-line solid phase extraction coupled with a high-performance liquid chromatography-tandem mass spectrometry system was developed for the determination of emerging benzotriazole UV stabilizers (BZTs) in different environmental water matrices including river water, sewage influent and effluent. Water sample was injected directly and the analytes were preconcentrated on a Polar Advantage II on-line SPE cartridge. After cleanup step the target BZTs were eluted in back flush mode and then separated on a liquid chromatography column. Experimental parameters such as sample loading flow rate, SPE cartridge, pH value and methanol ratio in the sample were optimized in detail. The method detection limits ranged from 0.21 to 2.17 ng/L. Recoveries of the target BZTs at 50 ng/L spiking level ranged from 76% to 114% and the inter-day RSDs ranged from 1% to 15%. The optimized method was successfully applied to analyze twelve water samples collected from different wastewater treatment plants and rivers, and five BZTs (UV-P, UV-329, UV-350, UV-234 and UV-328) were detected with concentrations up to 37.1 ng/L. The proposed method is simple, sensitive and suitable for simultaneous analysis and monitoring of BZTs in water samples.

Pristine mountains are ideal settings to study transport and behavior of persistent organic pollutants (POPs) along gradients of climate and land cover. The present work investigated the concentrations and patterns of 28 organochlorine pesticides (OCPs), 25 polychlorinated biphenyl (PCBs), 13 polybrominated diphenyl ethers (PBDEs), and 3 hexabromocyclododecane (HBCDs) isomers in the air of the Shergyla Mountain, southeastern Tibetan Plateau. Endosulfan І, hexachlorobenzene, pentachlorobenzene, hexachlorocyclohexanes and dichlorodibenzotrichloroethane and its degradation products (DDTs) were the predominant compounds while PBDEs and HBCDs showed the lowest background concentrations. Most of the target POPs had significantly higher concentrations in summer than those in winter. Increasing trends of the concentrations of DDTs and endosulfan were found with increasing altitude on the western slope in the Shergyla Mountain. Potential forest filter effect was observed based on the lower air concentrations of the target POPs in the forest than the ones out of the forest.

Graphenized pencil lead fiber was facilely prepared by in situ chemical exfoliation of graphite in pencil lead fiber to few-layered graphene sheets via a one-pot, one-step pressurized oxidation reaction for the first time. This new fiber was characterized and demonstrated to be a highly efficient but low-cost solid-phase microextraction (SPME) fiber. The extraction performance of the fiber was evaluated with four bisphenol analogs [bisphenol A (BPA), bisphenol S (BPS), bisphenol AF (BPAF), and tetrabromobisphenol A (TBBPA)] as model analytes in direct SPME mode. Unlike commercially available fibers, the graphenized pencil lead fiber showed an excellent chemical stability in highly saline, acidic, alkaline and organic conditions due to its coating-free configuration. The fiber also showed a very long lifespan. Furthermore, high extraction efficiency and good selectivity for the analytes with a wide polarity range could be obtained due to the exceptional properties of graphene. The detection limits (LODs) for the analytes were in the range of 1.1-25ng/L. The fiber was successfully applied in the analysis of tap water and effluent samples from a waste water treatment plant with spike recoveries ranging from 68.5 to 105.1%. Therefore, the graphenized pencil lead fiber provides a high performance, cheap, robust, and reliable tool for SPME.

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.

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).

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.

Extensive use of bisphenol A and its analogues has caused increasing concern over the potential adverse health impacts of these chemicals. In this study, the presence and profiles of 13 bisphenols (BPs) were investigated in 52 municipal sewage sludge samples collected from 30 cities in China. Tetrabromobisphenol A was the most frequently observed analogue (geometric mean: 20.5 ng/g dw). Bisphenol A (4.69 ng/g dw), bisphenol S (3.02 ng/g dw), and bisphenol F (3.84 ng/g dw) were found with similar frequency. Other BP analogues such as tetrachlorobisphenol A, bisphenol AF, bisphenol E, and dihydroxybiphenyl were identified for the first time in sewage sludge in China. Significant correlations were found among BP concentrations, but no relationships were found with wastewater treatment plant characteristics. Profiles of the relative estradiol equivalents suggested that the estrogenic potential of BP mixtures may be associated with the occurrence and contributions of specific analogues.

Benzotriazole ultraviolet stabilizers (BZT-UVs) have previously been found in sludge from wastewater treatment plants (WWTPs), which might be potential sources of BZT-UVs to the surrounding environment. In this work, the occurrence and fate of seven emerging 2-hydroxyphenyl substituted BZT-UVs were investigated in a Chinese WWTP. This group of hydrophobic BZT-UVs possess log K_ow values ranging from 4.31 to 7.67 which could be associated with their fate in WWTPs. Field samples including 24 h flow composites of influent, effluent and grab sludge samples from different treatment processes were collected and analyzed. Concentrations of BZT-UVs dissolved in aqueous-phases were in the range of 4.88±1.35 (UV-234) to 34.5±12.4 ng L^-1 (UV-P) in the primary influent, while only UV-P and UV-328 were detected in the final effluent at concentrations of 10.5±6.59 and 2.74±1.73 ng L^-1, respectively. Considering the amount of target BZT-UVs adsorbed to total suspended solids (TSS), the daily mass flux in the primary influent of the WWTP ranged from 22.3 g day(-1) (UV-P, 7.99%) to 74.0 g day^-1 (UV-234, 26.5%). Total removal efficiency of the integrated treatment process ranged from 89.7% for UV-P to 99.7% for UV-234 suggesting nearly complete removal. Organic solid sedimentation in primary and secondary clarifiers was the dominant elimination route for BZT-UV analogues, which constituted 96.3% of the total removal efficiency. Advanced treatment (using ultraviolet disinfection) in this plant might further contribute to the high removal efficiencies (ranging from 19.6% to 77.3%).

Polychlorinated naphthalenes (PCNs) were nominated as persistent organic pollutants candidate in the Stockholm Convention in 2011. In this study, the profiles, concentrations and spatial distributions of PCNs were analyzed in 30 sewage sludge samples from wastewater treatment plants (WWTPs) in China. Concentrations of Σ75PCNs in sludge samples were in the range of 1.05-10.9 ng/g dry weight (dw) with a mean value of 3.98 ng/g dw. The predominant homologues in the sludge were mono- to tetra-CNs, accounting for approximately 85% of total PCNs. The total toxic equivalent quantities (TEQs) of dioxin-like PCN congeners ranged from 0.04 to 2.28 pg/g dw with a mean value of 0.36 pg/g dw, which were lower than the maximum permissible TEQ concentrations in sludge for land application in China. Levels of PCNs and TEQs in sludge were relatively higher in samples from highly industrialized and developed cities in eastern China, implying a possible link between PCN contamination and the local economic development, but more studies are warranted to corroborate this. Industrial sources might be important contributors of PCNs to sewage sludge in China.