First Report on the Trophic Transfer and Priority List of Liquid Crystal Monomers in the Pearl River Estuary.

Liquid crystal monomers (LCMs) are emerging organic pollutants due to their potential persistence, toxicity, and bioaccumulation. This study first characterized the levels and compositions of 19 LCMs in organisms in the Pearl River Estuary (PRE), estimated their bioaccumulation and trophic transfer potential, and identified priority contaminants. LCMs were generally accumulated in organisms from sediment, and the LCM concentrations in all organisms ranged from 32.35 to 1367 ng/g lipid weight. The main LCMs in organisms were biphenyls and analogues (BAs) (76.6%), followed by cyanobiphenyls and analogues (CBAs) (15.1%), and the least were fluorinated biphenyls and analogues (FBAs) (11.2%). The most abundant LCM monomers of BAs, FBAs, and CBAs in LCMs in organisms were 1-(4-propylcyclohexyl)-4-vinylcyclohexane (15.1%), 1-ethoxy-2,3-difluoro-4-(4-(4-propylcyclohexyl) cyclohexyl) benzene (EDPBB, 10.1%), and 4'-propoxy-4-biphenylcarbonitrile (5.1%), respectively. The niche studies indicated that the PRE food web was composed of terrestrial-based diet and marine food chains. Most LCMs exhibited biodilution in the terrestrial-based diet and marine food chains, except for EDPBB and 4,4'-bis(4-propylcyclohexyl) biphenyl (BPCHB). The hydrophobicity, position of fluorine substitution of LCMs, and biological habits may be important factors affecting the bioaccumulation and trophic transfer of LCMs. BPCHB, 1-(prop-1-enyl)-4-(4-propylcyclohexyl) cyclohexane, and EDPBB were characterized as priority contaminants. This study first reports the trophic transfer processes and mechanisms of LCMs and the biomonitoring in PRE.

First Insight into Fetal Exposure to Legacy and Emerging Plasticizers Revealed by Infant Hair and Meconium: Occurrence, Biotransformation, and Accumulation.

Epidemiological studies have demonstrated the embryonic and developmental toxicity of plasticizers. Thus, understanding the in utero biotransformation and accumulation of plasticizers is essential to assessing their fate and potential toxicity in early life. In the present study, 311 infant hair samples and 271 paired meconium samples were collected at birth in Guangzhou, China, to characterize fetal exposure to legacy and emerging plasticizers and their metabolites. Results showed that most of the target plasticizers were detected in infant hair, with medians of 9.30, 27.6, and 0.145 ng/g for phthalate esters (PAEs), organic phosphate ester (OPEs), and alternative plasticizers (APs), and 1.44, 0.313, and 0.066 ng/g for the metabolites of PAEs, OPEs, and APs, respectively. Positive correlations between plasticizers and their corresponding primary metabolites, as well as correlations among the oxidative metabolites of bis(2-ethylhexyl) phthalate (DEHP) and 1,2-cyclohexane dicarboxylic acid diisononyl ester (DINCH), were observed, indicating that infant hair retained the major phase-I metabolism of the target plasticizers. While no positive correlations were found in parent compounds or their primary metabolites between paired infant hair and meconium, significant positive correlations were observed among secondary oxidative metabolites of DEHP and DINCH in hair and meconium, suggesting that the primary metabolites in meconium come from hydrolysis of plasticizers in the fetus but most of the oxidative metabolites come from maternal-fetal transmission. The parent compound/metabolite ratios in infant hair showed a decreasing trend across pregnancy, suggesting in utero accumulation and deposition of plasticizers. To the best of our knowledge, this study is the first to report in utero exposure to both parent compounds and metabolites of plasticizers by using paired infant hair and meconium as noninvasive biomonitoring matrices and provides novel insights into the fetal biotransformation and accumulation of plasticizers across pregnancy.

Tetrabromobisphenol-A/S and their derivatives in surface particulates from workshop floors of three representative e-waste recycling sites in China.

Surface particulates collected from the workshop floors of three major e-waste recycling sites (Taizhou, Qingyuan, and Guiyu) in China were analyzed for tetrabromobisphenol A/S (TBBPA/S) and their derivatives to investigate the environmental pollution caused by e-waste recycling activities. Mean concentrations of total TBBPA/S analogs in surface particulates were 31,471-116,059 ng/g dry weight (dw). TBBPA, TBBPA-BGE, and TBBPA-BDBPE were the most frequently detected in particulates with average concentration ranges of 17,929-78,406, 5601-15,842, and 5929-21,383 ng/g dw, respectively. Meanwhile, TBBPA, TBBPA-BGE, and TBBPA-BDBPE were the most abundant TBBPA/S analogs, accounting for around 96% of the total. The composition profiles of TBBPA/S analogs differed significantly among three e-waste sites. Similarly, principal component analysis uncovered different pollution patterns among different sites. The discrepancy in the profiles of TBBPA/S analogs largely relied on the e-waste types recycled in different areas. E-waste recycling led to the release of TBBPA/S analogs, and TBBPA/S analogs produced differentiation during migration from source (surface particulates) to nearby soil. More researches are necessary to find a definite relationship between pollution status and e-waste types and study differentiation behavior of TBBPA/S analogs in migration and diffusion from source to environmental medium.

Species-specific metabolism of triphenyl phosphate and its mono-hydroxylated product by human and rat CYP2E1 and the carp ortholog.

Organophosphorus flame retardants (PFRs) are a class of flame retardants and environmental pollutants with various biological effects. Recentstudies have evidenced activation of some PFRs by human CYP enzymes (including CYP2E1) for genotoxic effects. However, the activity of CYPs in fish species toward PFR metabolism remains unclear. This study was aimed on comparing the metabolism of triphenyl phosphate (TPHP) and 4-OH-TPHP in human, rat, and common carp, and the involvement of human CYP2E1 and its orthologs in the metabolism, by using fomepizole (4-MP, CYP2E1 inhibitor) as a modulator, in silico molecular docking and dynamics analyses. The rate of TPHP metabolism was apparently faster with human and rat, microsomes than with fish microsomes, the major metabolites were phosphodiester and hydroxylated phosphate, with 30-80 % of TPHP forming unidentified metabolites in the system of each species. 4-OH-TPHP was readily metabolized by both human and rat microsomes, whereas it was hardly metabolized in carp assays. Meanwhile, with 4-MP the transformation of TPHP to 4-OH-TPHP was enhanced in the human/rat systems while suppressed in the carp system. Moreover, the formation of unidentified metabolites in human and rat systems was mostly inhibited by 4-MP. Through molecular dynamics analysis TPHP and its primary metabolites showed high affinity for human and rat CYP2E1, as well as the carp ortholog (CYP2G1-like enzyme), however, the 4-OH-TPHP bond to the latter was too far from the heme to permit a biochemical reaction. This study suggests that the metabolism/activation of TPHP might be favored in mammals rather than carp, a fish species.

Nontarget and Comprehensive Analyses of Halogenated Organic Additives in Electrical Product Plastics by GC-NCI-Q-Orbitrap-HRMS and Cl/Br-Screening Algorithms.

Halogenated organic additives (HOAs) are used in plastic components of various electrical products, potentially causing detrimental effects on the eco-environment and humans. Besides reported HOAs, many unknown HOAs may be present in electrical product plastics and urgently require identification and characterization. This study performed nontarget analysis and comprehensive characterization of HOAs in three typical electrical product plastics by nontarget analysis using gas chromatography-negative chemical ionization-high-resolution mass spectrometry in association with in-house-developed chlorine/bromine-specific data-processing algorithms. A total of 674 formulas of HOAs were identified in the plastics dismantled from three electrical products, among which 166, 362, and 146 were organochlorines, organobromines, and mix-chlorinated/brominated organic compounds, respectively. The identified HOAs were semiquantified, and the total concentrations of HOAs in individual plastics were 445-1549 ng/g. Organobromines showed the most species and the highest abundances in all of the plastics, of which the abundances accounted for 86.6-98.0% of the total HOAs. Partial HOAs (209 formulas) were tentatively structurally elucidated, which were classified into 13 groups, i.e., halogenated alkyl phenoxyethyls (H-alkyl phenoxyethyls), H-alkylbenzenes, H-benzenes, H-bisphenol A (H-BPAs), H-dioxins, H-diphenyl ethers, H-biphenyls/terphenyls, H-polycyclic aromatic hydrocarbons, H-phenols, H-phenyl esters, H-phenyl-aldehydes/ketones, H-quinones, and an undefined group containing the HOAs such as dechlorane plus and chlordane. H-BPAs were the predominant HOAs in the plastics, showing relatively high concentrations (13-281 ng/g), and tetrabromobisphenol A was the most abundant H-BPA, with the concentrations of 9-196 ng/g. The comprehensive characterization results represent a holistic picture on the species features and abundance distributions of HOAs in electrical product plastics and provide an inventory of crucial HOAs worthy of concern. HOAs may migrate from plastics and release into the environment and are possibly an important source of halogenated organic pollutants in the environment, thus calling for further investigation and proper regulation.

Sex-Specific Bioaccumulation, Maternal Transfer, and Tissue Distribution of Legacy and Emerging Per- and Polyfluoroalkyl Substances in Snakes (Enhydris chinensis) and the Impact of Pregnancy.

The effects of sex and pregnancy on the bioaccumulation and tissue distribution of legacy and emerging per- and polyfluoroalkyl substances (PFASs) in Chinese water snakes were investigated. The bioaccumulation factor of PFASs showed a positive correlation with their protein-water partition coefficients (log KPW), and steric hindrance effects were observed when the molecular volume was > 357 Å3. PFAS levels in females were significantly lower than those in males. The chemical composition of pregnant females was significantly different from that of non-pregnant females and males. The maternal transfer efficiencies of perfluorooctane sulfonic acid were higher than those of other PFASs, and a positive correlation between the maternal transfer potential and log KPW was observed for other PFASs. Tissues with high phospholipid content exhibited higher concentrations of ∑PFASs. Numerous physiological changes occurred in maternal organ systems during pregnancy, leading to the re-distribution of chemicals among different tissues. The change in tissue distribution of PFASs that are easily and not-so-easily maternally transferred was in the opposite direction. The extent of compound transfer from the liver to the egg determined tissue re-distribution during pregnancy.

Trophic Transfer of Halogenated Organic Pollutants in a Wetland Food Web: Insights from Compound-Specific Nitrogen Isotope of Amino Acids and Food Source Analysis.

A trophic position (TP) model (TPmix model) that simultaneously considered trophic discrimination factor and ßGlu/Phe variations was developed in this study and was first applied to investigate the trophic transfer of halogenated organic pollutants (HOPs) in wetland food webs. The TPmix model characterized the structure of the wetland food web more accurately and significantly improved the reliability of TMF compared to the TPbulk, TPAAs, and TPsimmr models, which were calculated based on the methods of stable nitrogen isotope analysis of bulk, traditional AAs-N-CSIA, and weighted ßGlu/Phe, respectively. Food source analysis revealed three interlocking food webs (kingfisher, crab, and frogs) in this wetland. The highest HOP biomagnification capacities (TMFmix) were found in the kingfisher food web (0.24-82.0), followed by the frog (0.08-34.0) and crab (0.56-11.7) food webs. The parabolic trends of TMFmix across combinations of log KOW in the frog food web were distinct from those of aquatic food webs (kingfisher and crab), which may be related to differences in food web composition and HOP bioaccumulation behaviors between aquatic and terrestrial organisms. This study provides a new tool to accurately study the trophic transfer of contaminants in wetlands and terrestrial food webs with diverse species and complex feeding relationships.

Nontarget Analysis and Comprehensive Characterization of Iodinated Polyfluoroalkyl Acids in Wastewater and River Water by LC-HRMS with Cascade Precursor-Ion Exclusions and Algorithmic Approach.

Poly- and perfluoroalkyl acids (PFAAs) are a large family of widespread contaminants of worldwide concern and well-known as "forever chemicals". Direct emission of PFAAs from the fluorochemical industry is a crucial source of PFAA pollutants in the environment. This study implemented nontarget analysis and comprehensive characterization for a category of new PFAA contaminants, i.e., iodinated PFAAs (IPFAAs), in fluorochemical industry wastewater and relevant contaminated river water by liquid chromatography-high-resolution mass spectrometry with a cascade precursor ion exclusion (PIE) strategy and in-house developed data extraction and processing algorithms. A total of 26 IPFAAs (including 2 isomers of an IPFAA) were found and identified with tentative molecular structures. Semiquantification of the IPFAAs was implemented, and the total concentrations of IPFAAs were 0.16-285.52 and 0.15-0.17 µg/L in wastewater and river water, respectively. The high concentrations in association with the predicted ecotoxicities and environmental behaviors demonstrate that these IPFAAs are worthy of more concern and further in-depth research. The cascade PIE strategy along with the data extraction and processing algorithms can be extended to nontarget analysis for other pollutants beyond IPFAAs. The nontarget identification and characterization outcomes provide new understanding on the environmental occurrence and pollution status of IPFAAs from a comprehensive perspective.

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

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

Covalent immobilization of tyrosinase on magnetic multi-walled carbon nanotubes for inhibitor screening.

The inhibition of tyrosinase is considered to be a common therapeutic strategy for some hyperpigmentation disorders. Screening of tyrosinase inhibitors is of great significance to the treatment of pigmentation diseases. In this study, tyrosinase was covalently immobilized on magnetic multi-walled carbon nanotubes for the first time, and the immobilized tyrosinase was applied for ligand fishing of tyrosinase inhibitors from complex medicinal plants. The immobilized tyrosinase was characterized by transmission electron microscopy, atomic force microscopy, Fourier-transform infrared spectroscopy, vibrating sample magnetometry, and thermo-gravimetric analyzer, which indicated that tyrosinase was immobilized onto magnetic multi-walled carbon nanotubes. The immobilized tyrosinase showed better thermal stability and reusability than the free one. The ligand was fished out from Radix Paeoniae Alba and identified as 1,2,3,4,6-pentagalloylglucose by ultra-performance liquid chromatography-quadrupole time-of-flight high-resolution mass spectrometry. 1,2,3,4,6-pentagalloylglucose was found to be a tyrosinase inhibitor with similar half maximal inhibitory concentration values of 57.13 ± 0.91 µM compared to kojic acid (41.96 ± 0.78 µM). This work not only established a new method for screening tyrosinase inhibitors but also holds considerable potential for exploring the new medicinal value of medicinal plants.

Biomagnification of Persistent Organic Pollutants from Terrestrial and Aquatic Invertebrates to Songbirds: Associations with Physiochemical and Ecological Indicators.

Biomagnification of persistent organic pollutants (POPs) is affected by physiochemical properties of POPs and ecological factors of wildlife. In this study, influences on species-specific biomagnification of POPs from aquatic and terrestrial invertebrates to eight songbird species were investigated. The median concentrations of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in birds were 175 to 13 200 ng/g lipid weight (lw) and 62.7 to 3710 ng/g lw, respectively. Diet compositions of different invertebrate taxa for songbird species were quantified by quantitative fatty acid signature analysis. Aquatic insects had more contributions of more hydrophobic POPs, while terrestrial invertebrates had more contributions of less hydrophobic PCBs in songbirds. Biomagnification factors (BMFs) and trophic magnification factors had parabolic relationships with log KOW and log KOA. The partition ratios of POPs between bird muscle and air were significantly and positively correlated with log KOA of POPs, indicating respiratory elimination as an important determinant in biomagnification of POPs in songbirds. In this study, the species-specific biomagnification of POPs in songbird species cannot be explained by stable isotopes of carbon and nitrogen and body parameters of bird species. BMFs of most studied POPs were significantly correlated with proportions of polyunsaturated fatty acids in different species of songbirds.

Investigating the spatial distribution of polychlorinated biphenyls in sediment in the Pearl River Delta, South China.

One hundred forty-three surface sediment (0-5 cm depth) samples were collected from locations representing industrialized areas, less-industrialized areas, and e-waste recycling areas in the Pearl River Delta (PRD). The spatial distribution of polychlorinated biphenyls (PCBs) and their potential adverse effects on aquatic organisms were investigated. The average PCB concentration in the less-industrialized areas (background) in the PRD was approximately 10 ng/g dry weight (dw), which was generally half that found in the industrialized areas (approximately 22 ng/g dw). Severe PCB contamination, with concentrations ranging from 1000 to 26500 ng/g dw, was found in pond sediments collected from e-waste recycling areas. It is very likely that such contamination would have had adverse effects on the aquatic biota there. PCBs in the e-waste recycling areas were dominated by penta- and hex-PCB congeners, which made them significantly different from those found in other regions, where tri- and tetra-PCB congeners were predominant. Higher abundances of less chlorinated congeners were seen in the less-industrialized areas compared to the industrialized areas. Differences in the transport abilities of different congeners, together with dechlorination of higher chlorinated congeners, is the most likely reasons for this.

Sex-Specific Bioamplification of Halogenated Organic Pollutants during Silkworm (Bombyx mori) Metamorphosis and Their Adverse Effects on Silkworm Development.

A partial life cycle test was performed with silkworms (Bombyx mori) exposed to different levels of halogenated organic pollutants (HOPs). The aims were to investigate the fate of HOPs during metamorphosis and the adverse effects of HOP exposures on silkworm development. Contaminant exposures resulted in decreased body weights, increased development times, and reductions of fecundity in silkworms. Assimilation efficiencies of HOPs decreased with an increasing octanol-water partition coefficient (log KOW). From the larvae to the pupae stage, bioamplification factors (BAmFs) exhibited concentration-dependent results, in which there was a positive correlation with the log KOW at the high concentrations but no correlation at the low concentrations. From the pupae to the moth stage, BAmFs were linearly negatively correlated with the log KOW for males, but a parabolic correlation with the log KOW was more suitable for females. Regarding reproductive activities, female moths selectively transferred low log KOW HOPs to eggs by the oviposition except for highly halogenated lipophilic pollutants. However, BAmFs of male moths during mating showed no correlation with the log KOW, although highly halogenated lipophilic pollutants had the highest BAmF values. The sex-specific bioamplification processes and special behaviors of highly halogenated lipophilic pollutants deserve further research.

Contaminant-related oxidative distress in common kingfisher (Alcedo atthis) breeding at an e-waste site in South China.

The crude electronic waste (e-waste) recycling has caused severe contamination of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in the local environment, begging the question of whether wildlife like birds living at e-waste sites are suffering from adverse effects. We examined several oxidative status markers and their relationships with hepatic concentrations of PCBs and PBDEs in common kingfisher (Alcedo atthis) that inhabit an e-waste site in South China. The results showed that the mean concentrations of ∑PCBs (19100 ng/g) and ∑PBDEs (507 ng/g) in kingfishers from e-waste site were several orders of magnitude higher than those in the species from a reference site. Correspondingly, hepatic concentrations of malondialdehyde (MDA) and reactive oxygen species (ROS) in kingfishers from the e-waste site were significantly higher than those detected in the reference population, suggesting oxidative distress in the birds breeding at the e-waste site. The activities of superoxide dismutase (SOD) and catalase (CAT) in the liver from the exposed group were significantly lower compared with the reference group, while the opposite trend was observed for glutathione peroxidase (GPx). Significantly positive correlations were observed between PCB or PBDE concentrations and the levels of MDA and ROS; while negative correlations were found for enzymatic activities of SOD and CAT. Overall, our results may suggest a potential linkage between exposure to e-waste-derived pollutants and elevated oxidative stress, thereby indicating a potential oxidative stress-related health effects in common kingfisher breeding at the e-waste site.

Simultaneous determination of legacy and emerging organophosphorus flame retardants and plasticizers in indoor dust using liquid and gas chromatography-tandem mass spectrometry: method development, validation, and application.

In the present study, an analytical method has been developed and validated for the simultaneous detection and quantification of 19 PFRs (14 legacy organophosphorus flame retardants (PFRs) and 5 emerging PFRs (ePFRs)) and 20 plasticizers (7 legacy plasticizers (LPs) and 13 alternative plasticizers (APs)). Sample preparation was based on the combination of previously validated analytical protocols including ultrasonic extraction and Florisil fractionation/cleanup. The analysis was performed by using liquid chromatography-tandem mass spectrometry (LC-MS/MS) for all targeted compounds, except for bis (2-ethylhexyl) phthalate (DEHP) and bis (2-ethylhexyl) terephthalate (DEHT), for which the separation of the isomers resulted in more favorable gas chromatography-electron ionization-mass spectrometry (GC-EI-MS). The new method was in-house validated by applying two levels of fortification in dust. The achieved linearity (R2) ranged between 0.993 and 0.999. Limits of detection and quantification (LODs and LOQs) ranged between 1 and 265 ng/g and between 1 and 870 ng/g for all analytes, respectively, except for DEHP and DEHT, for which relatively higher LODs (665 and 1100 ng/g, respectively) and LOQs (2100 and 3500 ng/g, respectively) were observed. Accuracy ranged between 75 and 125% for most of the targeted analytes, and repeatability was good with relative standard deviation (RSD) < 15% for most compounds. Finally, the method was applied for the determination and quantification of the targeted chemicals in house dust samples (n = 10) from the megacity of Guangzhou (China). Median values ranged from 3 to 210 ng/g for PFRs, from 4 to 165 ng/g for ePFRs, from 30 to 100,000 ng/g for LPs, and from 6 to 34,000 ng/g for APs. Main contributors to the total contamination were LPs 63% and APs 37% in total plasticizers, whereas PFRs and ePFRs contributed 90% and 10% in total flame retardants. Graphical abstract.

Bioaccumulation of Persistent Halogenated Organic Pollutants in Insects: Common Alterations to the Pollutant Pattern for Different Insects during Metamorphosis.

Few studies have examined the accumulation and fate of persistent halogenated organic pollutants (HOPs) in insects. We measured HOPs, including dichlorodiphenyltrichloroethanes (DDTs), polychlorinated biphenyls, and halogenated flame retardants, in insects from four taxonomic groups collected from an e-waste site. Dragonfly larvae collected from a pond contained the highest concentrations of all chemicals except DDTs, while the litchi stinkbugs contained the lowest. Different insect taxa exhibited different contaminant patterns which could be attributed to their habitats and feeding strategies. Bioaccumulation factors for dragonfly larvae and biomagnification factors for moth and grasshopper larvae were significantly positively correlated with the octanol-water partition coefficient of the chemicals (log KOW < 8). Common nonlinear correlations between the ratio of larval to adult concentrations and log KOW were observed for all taxa studied. The ratio of concentrations decreased with increasing values of log KOW (log KOW < 6-6.5), then increased (6 < log KOW < 8) and decreased again (log KOW > 8). This result implies that the mechanism that regulates organic pollutants in insects during metamorphosis is common to all the taxa studied.

Characterizing the Influence of Metabolism on the Halogenated Organic Contaminant Biomagnification in Two Artificial Food Chains Using Compound- and Enantiomer-Specific Stable Carbon Isotope Analysis.

Two artificial food chains, food tiger barb-oscar fish and food tiger barb-redtail catfish, were established in the laboratory. The species-specific biotransformation of ortho, para'-dichlorodiphenyltrichloroethane, 12 polychlorinated biphenyl, and five polybrominated diphenyl ether congeners were characterized by measuring the compound- and enantiomer-specific stable carbon isotope composition (δ13C), enantiomeric fraction of the chiral chemicals, and metabolites in the fish. Compound- and enantiomer-specific biotransformations were revealed by the alteration of δ13C and EF in both predator fish species. Significant correlations between the carbon stable isotope signatures and the depuration rates and biomagnification factors (BMF) were observed. Chemicals that exhibited changes in δ13C during the experiment have higher kd and lower BMF values than those with unchanged δ13C. Specifically, the difference between the predicted BMF based on the log Kow and the measured BMF, ΔBMF, was significantly positively and linearly correlated to the change in the δ13C (expressed by Δδ13C/δ13Cinitial, the percentage of Δδ13C: δ13Cending-δ13Cinitial to the initial δ13Cinitial) in both food chains. These results indicated that the impact of metabolism on the bioaccumulation potential of organic contaminants can be predicted by the stable carbon isotope fractionation of chemicals in the fish.

Organophosphorus esters (OPEs) in PM2.5 in urban and e-waste recycling regions in southern China: concentrations, sources, and emissions.

Organophosphate esters (OPEs) are novel ubiquitous contaminants that are attracting growing concern, but their emissions into the environment are still poorly understood. In this study, 12 OPEs were measured in fine particulate matter (PM2.5) at 20 industrial sites in an urban region and four e-waste recycling facilities in a rural region in southern China. There was no significant difference in the concentrations of ∑OPEs between the urban region (519-62,747 pg/m3, median = 2854 pg/m3) and the rural e-waste region (775-13,823 pg/m3, 3321 pg/m3). High OPE concentrations in urban PM2.5 were generally associated with the electrical, electronic, plastic, and chemical industries. There were no significant correlations between most OPEs in these two regions, suggesting different emission mechanisms. The average emissions of ∑OPEs estimated using a simplified dispersion model were 73.0 kg/yr from the urban industrial point sources and 33.2 kg/yr from the e-waste recycling facilities. The estimated emission inventory from industrial activities in the whole city (3228-4452 kg/yr) was approximately 30-fold higher than that from the e-waste recycling (133 kg/yr) facilities because urban region has a much larger industrial scale. To the best of our knowledge, this is the first effort to model the emissions of OPEs from industrial and e-waste recycling activities to the atmosphere.

Tracing the Biotransformation of PCBs and PBDEs in Common Carp (Cyprinus carpio) Using Compound-Specific and Enantiomer-Specific Stable Carbon Isotope Analysis.

Compound-specific and enantiomer-specific carbon isotope composition was investigated in terms of biotransformation of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) as well as atropisomers of chiral PCB congeners in fish by exposing common carp (Cyprinus carpio) to certain PCB and PBDE congeners. The calculated carbon isotope enrichment factors (εC) for PCB 8, 18, and 45 were -1.99, -1.84, and -1.70‰, respectively, providing evidence of the metabolism of these congeners in fish. The stable carbon isotopic compositions of PBDE congeners clearly reflect the debromination of PBDEs in carp. Significant isotopic fractionation was also observed during the debromination process of BDE 153 (εC = -0.86‰). Stereoselective elimination of chiral PCB congeners 45, 91, and 95 was observed, indicating a stereoselective biotransformation process. The similar εC values for E1-PCB 45 (-1.63‰) and E2-PCB 45 (-1.74‰) indicated that both atropisomers were metabolized by the same reaction mechanisms and stereoselection did not occur at carbon bond cleavage. However, the εC values of (+)-PCB 91 (-1.5‰) and (-)-PCB 95 (-0.77‰) were significantly different from those of (-)-PCB 91 and (+)-PCB 95, respectively. In the latter, no significant isotopic fractionations were observed, indicating that the stereoselective elimination of PCB 91 and 95 could be caused by a different reaction mechanism in the two atropisomers.

Polychlorinated Biphenyls (PCBs) in Human Hair and Serum from E-Waste Recycling Workers in Southern China: Concentrations, Chiral Signatures, Correlations, and Source Identification.

Hair is increasingly used as a biomarker for human exposure to persistent organic pollutants (POPs). However, the internal and external sources of hair POPs remain a controversial issue. This study analyzed polychlorinated biphenyls (PCBs) in human hair and serum from electronic waste recycling workers. The median concentrations were 894 ng/g and 2868 ng/g lipid in hair and serum, respectively. The PCB concentrations in male and female serum were similar, while concentrations in male hair were significantly lower than in female hair. Significant correlations between the hair and serum PCB levels and congener profiles suggest that air is the predominant PCB source in hair and that hair and blood PCB levels are largely dependent on recent accumulation. The PCB95, 132, and 183 chiral signatures in serum were significantly nonracemic, with mean enantiomer fractions (EFs) of 0.440-0.693. Nevertheless, the hair EFs were essentially racemic (mean EFs = 0.495-0.503). Source apportionment using the Chemical Mass Balance model also indicated primary external PCB sources in human hair from the study area. Air, blood, and indoor dust are responsible for, on average, 64.2%, 27.2%, and 8.79% of the hair PCBs, respectively. This study evidenced that hair is a reliable matrix for monitoring human POP exposure.