Tissue-Specific Distribution and Maternal Transfer of Persistent Organic Halogenated Pollutants in Frogs.

Persistent organic pollutants pose a great threat to amphibian populations, but information on the bioaccumulation of contaminants in amphibians remains scarce. To examine the tissue distribution and maternal transfer of organic halogenated pollutants (OHPs) in frogs, seven types of tissues from black-spotted frog (muscle, liver, kidney, stomach, intestine, heart, and egg) were collected from an e-waste-polluted area in South China. Among the seven frog tissues, median total OHP concentrations of 2.3 to 9.7 µg/g lipid weight were found (in 31 polychlorinated biphenyl [PCB] individuals and 15 polybrominated diphenyl ether [PBDE], dechlorane plus [syn-DP and anti-DP], bexabromobenzene [HBB], polybrominated biphenyl] PBB153 and -209], and decabromodiphenyl ethane [DBDPE] individuals). Sex-specific differences in contaminant concentration and compound compositions were observed among the frog tissues, and eggs had a significantly higher contaminant burden on the whole body of female frogs. In addition, a significant sex difference in the concentration ratios of other tissues to the liver was observed in most tissues except for muscle. These results suggest that egg production may involve the mobilization of other maternal tissues besides muscle, which resulted in the sex-specific distribution. Different parental tissues had similar maternal transfer mechanisms; factors other than lipophilicity (e.g., molecular size and proteinophilic characteristics) could influence the maternal transfer of OHPs in frogs. Environ Toxicol Chem 2024;00:1-12. © 2024 SETAC.

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, 5,601-15,842, and 5,929-21,383 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.

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.

Comprehensive characterization and prioritization of halogenated organic compounds in fish and their implications for exposure.

Fish are an important pollution indicator for biomonitoring of halogenated organic compounds (HOCs) in aquatic environments, and HOCs in fish may pose health threats to consumers. This study performed nontarget and comprehensive analyses of HOCs in fish from an e-waste recycling zone by gas chromatography-high-resolution mass spectrometry, and further prioritized their human exposure risks. A total of 1652 formulas of HOCs were found in the fish, of which 1222, 117, and 313 were organochlorines, organobromines, and organochlorine-bromines, respectively. The total concentrations of HOCs were 15.4-18.7 µg/g (wet weight), and organobromines were the predominant (14.1-16.8 µg/g). Of the HOCs, 41 % were elucidated with tentative structures and divided into 13 groups. The estimated total daily exposures of HOCs via dietary consumption of the fish for local adult residents were 3082-3744 ng/kg bw/day. The total exposures were dominated by several groups of HOCs with the following contribution order: polyhalogenated biphenyls and their derivatives > polyhalogenated diphenyl ethers > halo- (H-)alkanes/olefines > H-benzenes > H-dioxins > H-polycyclic aromatic hydrocarbons > H-phenols. The comprehensive characterization and prioritization results provide an overview of the species and distributions of HOCs in edible fish, and propose an inventory of crucial HOCs associated with high exposure risks.

ThermomiR-377-3p-induced suppression of Cirbp expression is required for effective elimination of cancer cells and cancer stem-like cells by hyperthermia.

BACKGROUND: In recent years, the development of adjunctive therapeutic hyperthermia for cancer therapy has received considerable attention. However, the mechanisms underlying hyperthermia resistance are still poorly understood. In this study, we investigated the roles of cold­inducible RNA binding protein (Cirbp) in regulating hyperthermia resistance and underlying mechanisms in nasopharyngeal carcinoma (NPC). METHODS: CCK-8 assay, colony formation assay, tumor sphere formation assay, qRT-PCR, Western blot were employed to examine the effects of hyperthermia (HT), HT + oridonin(Ori) or HT + radiotherapy (RT) on the proliferation and stemness of NPC cells. RNA sequencing was applied to gain differentially expressed genes upon hyperthermia. Gain-of-function and loss-of-function experiments were used to evaluate the effects of RNAi-mediated Cirbp silencing or Cirbp overexpression on the sensitivity or resistance of NPC cells and cancer stem-like cells to hyperthermia by CCK-8 assay, colony formation assay, tumorsphere formation assay and apoptosis assay, and in subcutaneous xenograft animal model. miRNA transient transfection and luciferase reporter assay were used to demonstrate that Cirbp is a direct target of miR-377-3p. The phosphorylation levels of key members in ATM-Chk2 and ATR-Chk1 pathways were detected by Western blot. RESULTS: Our results firstly revealed that hyperthermia significantly attenuated the stemness of NPC cells, while combination treatment of hyperthermia and oridonin dramatically increased the killing effect on NPC cells and cancer stem cell (CSC)­like population. Moreover, hyperthermia substantially improved the sensitivity of radiation­resistant NPC cells and CSC­like cells to radiotherapy. Hyperthermia noticeably suppressed Cirbp expression in NPC cells and xenograft tumor tissues. Furthermore, Cirbp inhibition remarkably boosted anti­tumor­killing activity of hyperthermia against NPC cells and CSC­like cells, whereas ectopic expression of Cirbp compromised tumor­killing effect of hyperthermia on these cells, indicating that Cirbp overexpression induces hyperthermia resistance. ThermomiR-377-3p improved the sensitivity of NPC cells and CSC­like cells to hyperthermia in vitro by directly suppressing Cirbp expression. More importantly, our results displayed the significantly boosted sensitization of tumor xenografts to hyperthermia by Cirbp silencing in vivo, but ectopic expression of Cirbp almost completely counteracted hyperthermia-mediated tumor cell-killing effect against tumor xenografts in vivo. Mechanistically, Cirbp silencing-induced inhibition of DNA damage repair by inactivating ATM-Chk2 and ATR-Chk1 pathways, decrease in stemness and increase in cell death contributed to hyperthermic sensitization; conversely, Cirbp overexpression-induced promotion of DNA damage repair, increase in stemness and decrease in cell apoptosis contributed to hyperthermia resistance. CONCLUSION: Taken together, these findings reveal a previously unrecognized role for Cirbp in positively regulating hyperthermia resistance and suggest that thermomiR-377-3p and its target gene Cirbp represent promising targets for therapeutic hyperthermia.

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

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

A comprehensive assessment of external exposure to persistent halogenated organic pollutants for residents in an e-waste recycling site, South China.

Human skin wipes from 30 participants, air, dust, and food items were collected from a former electronic waste site in South China to provide a comprehensive understanding of residents' exposure to halogenated flame retardants (HFRs) and polychlorinated biphenyls (PCBs). The total concentration of halogenated organic pollutants (HOPs) in the dust, air, food and skin wipes ranged 240-25000 ng/g, 130-2500 pg/m3, 0.08-590 ng/g wet weight, and 69-28000 ng/m2, respectively. Wild fish, vegetables, and air were dominated by PCBs, whereas dust, livestock, and poultry were dominated by HFRs. The HOP concentrations were several orders of magnitude higher in local foodstuffs than in market foodstuffs. The chemical composition on the forehead was remarkably different from that on the hand. The importance of different exposure routes depends on the residents' food choices, except decabromodiphenyl ethane (DBDPE). For residents who consumed a 100-foot diet (mainly egg) and local wild fish, diet ingestion overwhelmed other exposure routes, and PCBs were mainly contributed by fish and HFRs by egg. For residents who consumed market food, the dermal absorption of most PCB congeners and dust ingestion of highly brominated flame retardants were relatively prominent. Inhalation was found to be a crucial route for pentabromoethylbenzene (PBEB).

Multi-pathway exposure assessment of organophosphate flame retardants in a southern Chinese population: Main route identification with compound-specificity.

In this study, we conducted comprehensive organophosphorus flame retardant (PFR) exposure assessments of both dietary and non-dietary pathways in a rural population in southern China. Skin wipes were collected from 30 volunteers. Indoor and outdoor air (gas and particles), dust in the houses of these volunteers, and foodstuffs consumed by these volunteers were simultaneously collected. The total PFR concentrations in dust, gas, and PM2.5 varied from 53.8 to 5.14 × 105 ng/g, 0.528 to 4.27 ng/m3, and 0.390 to 16.5 ng/m3, respectively. The forehead (median of 1.36 × 103 ng/m2) and hand (median of 920 ng/m2) exhibited relatively high PFR concentrations, followed by the forearm (median of 440 ng/m2) and upper arm (median of 230 ng/m2). The PFR concentrations in the food samples varied from 0.0700 to 10.9 ng/g wet weight in the order of egg > roast duck/goose and vegetable > pork > chicken > fish. Tris(1-chloro-isopropyl) phosphate (TCPP) was the main PFR in the non-diet samples, whereas the profiles of PFR individuals varied by food type. Among the multiple pathways investigated (inhalation, dermal exposure, dust ingestion, and food ingestion), dermal absorption and dust ingestion were the predominant pathways for tris(2-chloroethyl) phosphate (TCEP) and bisphenol A-bis(diphenyl phosphate) (BDP), respectively, whereas dietary exposure was the most important route for other chemicals.

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.

Bioaccumulation, tissue distributions, and maternal transfer of perfluoroalkyl carboxylates (PFCAs) in laying hens.

Laying hens were exposed to feeds spiked with a series of perfluoroalkyl carboxylates (PFCAs) ranging from perfluorobutanoic acid (C4) to perfluorooctadecanoic acid (C18) to investigate their bioaccumulation, tissue distribution, and maternal transfer. We found that PFCAs with longer carbon chains (>8) were more efficiently absorbed in the gastrointestinal tract than those with shorter chains (≤8), and that the rate of depuration varied inversely with the carbon chain length in a U-shaped pattern. Moreover, bioaccumulation potential increased with increasing carbon-chain length, except for C4. Distinct affinities were observed for specific carbon-chain PFCAs across various tissues, evident from their differential accumulation during both uptake and depuration phases. Specifically, C9 showed a higher affinity for serum and liver, C12 was more prevalent in yolk, C14 was notably abundant in the brain, and C18 was predominant in other tissues. Furthermore, the egg-maternal ratio (EMR) increased with increasing carbon-chain length from C7 to C11 and reached a plateau phase for C12 to C18. Our study also confirmed the key role of phospholipids in the tissue distribution and maternal transfer of long-chain PFCAs. This study sheds light on the interaction between PFCAs and biological tissues and reveals the toxicokinetic factors that influence the bioaccumulation of PFCAs. Further research is needed to identify the specific proteins or components that mediate the tissue-specific affinity for different carbon-chain lengths of PFCAs.

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

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

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.

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.

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.

A new insight into the emission source of DDT in indoor environment from rural area of South China and comprehensive human health exposure assessment.

Human exposure to dichlorodiphenyltrichloroethanes (DDTs) and the subsequent risk to human health remain an important concern due to the "new" input of DDTs in the environment, especially since exposure to DDTs in indoor microenvironments is often ignored. In this study, we identified a new source of DDT emission in indoor environments and evaluated the health risk from the exposure to DDTs by investigating DDTs in indoor and outdoor dust, air, and coatings of household items in rural areas of Qingyuan, South China. The concentrations of DDTs in house dust and air were < MQL (method quantification limit)-3450 ng/g (median 42.4 ng/g) and 22.7-965 pg/m3 (median 49.5 pg/m3), respectively, which were significantly higher than the outdoor DDT values. Dichlorodiphenyldichloroethylene (DDE) was the main isomer in air samples, while DDT was the dominant isomer in indoor dust. Significant correlations between different DDT isomers were observed in indoor samples but not in outdoor samples. Furniture coating was identified as a source of DDTs in the indoor dust. The total daily exposure dose of DDTs (1.75 × 10-2 ng/kg bw/day for adults and 1.28 × 10-1 ng/kg bw/day for toddlers) through inhalation, dust ingestion, and dermal contact was found unlikely to pose a health risk. Our findings provide new insights into the emission sources and health risks caused by DDT indoors, highlighting the need to further investigate the toxicity mechanisms of parent DDT compound.

Fetal exposure to organic contaminants revealed by infant hair: A preliminary study in south China.

Fetal exposure to multiple organic contaminants (OCs) is a public concern because of the adverse effects of OCs on early life development. Infant hair has the potential to be used as an alternative matrix to identify susceptible fetuses, owing to its reliability, sensitivity, and advantages associated with sampling, handling, and ethics. However, the applicability of infant hair for assessing in utero exposure to OCs is still limited. In this study, 57 infant hair samples were collected in Guangzhou, South China, to evaluate the levels and compositions of typical OCs in the fetus. Most of the target OCs were detected in infant hair, with medians of 144 µg/g, 17.7 µg/g, 192 ng/g, 46.9 ng/g, and 1.36 ng/g for phthalate esters (PAEs), alternative plasticizers (APs), organophosphorus flame retardants (OPFRs), polybrominated diphenyl ethers (PBDEs), and organochlorine pesticides (OCPs), respectively. Meanwhile, paired maternal hair (0-9 cm from the scalp) was collected to examine the associations between maternal and infant hair for individual compounds. Low-brominated PBDEs tended to deposit in infant hair, with median concentrations approximately two times higher than those in maternal samples. Levels of PBDEs and 4,4'-dichlorodiphenyldichloroethylene (p,p'-DDE) in paired maternal and infant hair showed strong positive correlations (p < 0.05), while most plasticizers (PAEs and APs) were poorly correlated between paired hair samples. Exposure sources were responsible for the variation in correlation between OC levels in the paired infant and maternal samples. Crude relationships between fetal exposure to OCs and birth size were examined using the Bayesian kernel machine regression (BKMR) model. BDE-28 was found to be adversely associated with the birth size. This study provides referential information for evaluating in utero exposure to OCs and their health risks based on infant hair.

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.

Occurrence, spatial distribution, and risk assessment of short- and medium-chain chlorinated paraffins in sediment from black-odorous rivers across China.

Chlorinated paraffins (CPs) were massively produced for varied industrial purposes, of which improper handling and consequent environmental release resulted in worldwide contamination. The present study investigated the occurrence and spatial distribution of short- and medium-chain chlorinated paraffins (SCCP/MCCPs) in 171 sediment samples from black-odorous urban rivers across China. Total SCCP and MCCP concentrations ranged from 8.3 to 9.4 × 104 (median: 1.1 × 103) ng/g dw, and from not-detected-value to 1.0 × 106 (median: 1.3 × 104) ng/g dw, respectively. No clear spatial distribution of SCCPs and MCCPs was observed since black-odorous urban rivers were polluted by point-sources of the SCCP/MCCPs. Significant positive correlations were identified between SCCP/MCCPs and total organic carbon, and between SCCP/MCCPs and other persistent organic matter, including polybrominated diethyl ethers, polychlorinated biphenyls, antibiotics, and plasticizers. The average ratios of MCCPs to SCCPs in most samples were divided into 11 and 16, implying the manufacturing and use of at least two types of CP technical mixtures in China. The composition of SCCP/MCCPs were similar to that in their commercial products. Ecological risk assessments by two approaches, including the Federal Environmental Quality Guidelines and Risk Quotient, both revealed that SCCP/MCCP in surface sediments confer an ecological risk. ENVIRONMENTAL IMPLICATION: SCCPs and MCCPs can be considered "hazardous materials" because of their massive production and their potential persistence, long-distance transfer, bioaccumulation potential, and toxicity. This research conducted a comprehensive study on SCCP/MCCP in black-odorous urban river sediments across China and revealed their environmental risk, which may improve understanding of SCCP/MCCP contamination characteristics.

Comparative in vitro metabolism of short chain chlorinated paraffins (SCCPs) by human and chicken liver microsomes: First insight into heptachlorodecanes.

Short chain chlorinated paraffins (SCCPs) are emerging persistent organic pollutants of great concern due to their ubiquitous distribution in the environment. However, little information is available on the biotransformation of SCCPs in organisms. In this study, a chlorinated decane: 1, 2, 5, 5, 6, 9, 10-heptachlorodecanes (HeptaCDs) was subjected to in vitro metabolism by human and chicken liver microsomes at environmentally relevant concentration. Using ultra-performance liquid chromatography-Q-Exactive Orbitrap mass spectrometry, two metabolites: monohydroxylated hexachlorodecane (HO-HexCD) and monohydroxy heptachlorodecane (HO-HeptaCD) were detected in human liver microsomal assays, while only one metabolite (HO-HexCD) was identified in chicken liver microsomal assays. The formation of HO-HexCD was fitted to a Michaelis-Menten model for chicken liver microsomes with a Vmax (maximum metabolic rate) value of 4.52 pmol/mg/min. Metabolic kinetic parameters could not be obtained for human liver microsomes as steady state conditions were not reached under our experimental conditions. Notwithstanding this, the observed average biotransformation rate of HeptaCDs was much faster for human liver microsomes than for chicken liver microsomes. Due to the lack of authentic standards for the identified metabolites, the detailed structure of each metabolite could not be confirmed due to the possibility of conformational isomers. This study provides first insights into the biotransformation of SCCPs, providing potential biomarkers and enhancing understanding of bioaccumulation studies.