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Despite advancements in high-resolution screening techniques, the identification of novel perfluoroalkyl and polyfluoroalkyl substances (PFAS) remains challenging without prior structural information. In view of this, we proposed and implemented a new data-driven algorithm to calculate spectral similarity among PFAS, facilitating the generation of molecular networks to screen for unknown compounds. Using this approach, 81 PFAS across 12 distinct classes were identified in soil samples collected near an industrial park in Shandong Province, China, including the first reported occurrence of 12 iodine-substituted PFAS. Among them, the standards of four iodine-substituted polyfluorinated ether sulfonates (I-PFESA) were successfully synthesized, enabling structural confirmation and subsequent quantitative analysis. Although the median concentration of ∑I-PFESA (0.74 ng/g dw) in soil samples was lower than that of ∑H-PFESA (hydrogen-substituted, 61.96 ng/g dw) and ∑Cl-PFESA (chlorine-substituted, 2.98 ng/g dw), embryotoxicity assays in zebrafish revealed that 6:2 I-PFESA exhibited greater toxicity compared to 6:2 Cl-PFESA of the same chain length. This highlights the need for a closer examination of the toxic effects of I-PFESA. Notably, the proposed algorithm, based on novel PFAS spectral similarity, provides new perspectives on the environmental behavior and transformation of I-PFESA, although further investigation is required to elucidate the underlying mechanisms of their toxicity.

China aims to actively control the contamination of globally concerning per- and polyfluoroalkyl substances (PFASs). Evaluation of the current situation can provide a critical reference point for tracking the effectiveness of ongoing progress. Herein, we present the first comprehensive assessment of the spatial variations of 20 legacy and 54 novel PFASs in Chinese background soils in 2021. Novel PFASs were extensively detected in 98.4% of the samples, with 21 species being first reported, which greatly facilitated the appointment of diverse emission sources that aligned with local industrial structures. However, legacy PFASs still dominated the ∑ 74 PFAS profile (median 0.51 ng/g, 0.050-8.33 ng/g). The spatial heterogeneity of soil PFASs was positively driven by economic development and atmospheric deposition, enabling the establishment of predictive models to project the national distribution and temporal trends. Elevated PFAS levels were predominantly distributed in the more industrialized eastern and southern regions, as well as other coastal areas with greater precipitation. ∑ 74 PFAS in surface soils was estimated to increase by 12.9 pg/(g year) over 2002-2021, which would continue alongside economic growth, albeit with greater contributions from novel alternatives. Our work provides comprehensive baseline and predictive data to inform policies toward PFAS control in China.

In this study, various crops and farmland soils were collected from the Fen-Wei Plain, China, to investigate the bioavailability of perfluoroalkyl substances (PFAS), their accumulation in edible plant tissues, and the factors impacting their accumulation. PFAS were frequently detected in all of the crops, with total concentrations ranging from 0.61 to 35.8 ng/g. The results of sequential extractions with water, basic methanol, and acidic methanol indicate that water extraction enables to characterize the bioavailability of PFAS in soil to edible plant tissues more accurately, especially for the shorter-chain homologues. The bioavailability of PFAS was remarkably enhanced in the rhizosphere (RS) soil, with the strongest effect observed for leafy vegetables. The water-extracted Σ 16 PFAS in RS soil was strongly correlated with the content of dissolved organic carbon in the soil. Tannins and lignin, identified as the main components of plant root exudates by Fourier transform-ion cyclotron resonance mass spectrometry, were found to enhance the bioavailability of PFAS significantly. Redundancy analysis provided strong evidence that the lipid and protein contents in edible plant tissues play important roles in the accumulation of short- and long-chain PFAS, respectively. Additionally, the high water demand of these tissues during the growth stage greatly facilitated the translocation of PFAS, particularly for the short-chain homologues and perfluorooctanoic acid.

In this study, we measured 15 common organophosphate flame retardants (OPFRs) in six categories of tea samples across China. OPFRs were found in all the tea samples, with the total concentrations of OPFRs (∑OPFRs) at 3.44-432 ng/g [geometric mean (GM): 17.6 ng/g]. Triphenyl phosphate (TPhP) was the dominant OPFR, accounting for 39.0-76.2% of ∑OPFRs across all tea categories. The potential factors influencing the residual OPFRs in tea were thoroughly examined, including the agricultural environment, fermentation, and packaging of teas. Tea packaging materials (TPMs) were then identified as the primary sources of OPFRs in teas. The migration test revealed that OPFRs with lower molecular weights and log K values exhibited a higher propensity for facilitating the migration of OPFRs from TPMs to teas. The estimated daily intakes of OPFRs from teas were relatively higher for the general populations in Mauritania, Gambia, Togo, Morocco, and Senegal (3.18-9.79 ng/kg bw/day) than China (3.12 ng/kg bw/day). The health risks arising from OPFRs in Chinese teas were minor. This study established a baseline concentration and demonstrated the contamination sources of OPFRs in Chinese tea for the first time, with an emphasis on enhancing the hygiene standards for TPMs.ow values exhibited a higher propensity for facilitating the migration of OPFRs from TPMs to teas. The estimated daily intakes of OPFRs from teas were relatively higher for the general populations in Mauritania, Gambia, Togo, Morocco, and Senegal (3.18-9.79 ng/kg bw/day) than China (3.12 ng/kg bw/day). The health risks arising from OPFRs in Chinese teas were minor. This study established a baseline concentration and demonstrated the contamination sources of OPFRs in Chinese tea for the first time, with an emphasis on enhancing the hygiene standards for TPMs.

The contamination status of novel organophosphate esters (NOPEs) and their precursors organophosphite antioxidants (OPAs) and hydroxylated/diester transformation products (OH-OPEs/di-OPEs) in soils across a large-scale area in China were investigated. The total concentrations of the three test NOPEs in soil were 82.4-716 ng g -1 , which were considerably higher than those of traditional OPEs (4.50-430 ng g -1 ), OPAs (n.d.-30.8 ng g -1 ), OH-OPEs (n.d.-0.49 ng g -1 ), and di-OPEs (0.57-21.1 ng g -1 ). One NOPE compound, i.e., tris(2,4-di- tert -butylphenyl) phosphate (AO168 = O) contributed over 65% of the concentrations of the studied OPE-associated contaminants. A 30-day soil incubation experiment was performed to confirm the influence of AO168 = O on soil bacterial communities. Specific genera belonging to Proteobacteria, such as Lysobacter and Ensifer , were enriched in AO168 = O-contaminated soils. Moreover, the ecological function of methylotrophy was observed to be significantly enhanced ( t -test, p < 0.01) in soil treated with AO168 = O, while nitrogen fixation was significantly inhibited ( t -test, p < 0.01). These findings comprehensively revealed the contamination status of OPE-associated contaminants in the soil environment and provided the first evidence of the effects of NOPEs on soil microbial communities.

The investigation of pharmaceuticals as emerging contaminants in marine biota has been insufficient. In this study, we examined the presence of 51 pharmaceuticals in edible oysters along the coasts of the East and South China Seas. Only nine pharmaceuticals were detected. The mean concentrations of all measured pharmaceuticals in oysters per site ranged from 0.804 to 15.1 ng g -1 of dry weight, with antihistamines being the most common. Brompheniramine and promethazine were identified in biota samples for the first time. Although no significant health risks to humans were identified through consumption of oysters, 100-1000 times higher health risks were observed for wildlife like water birds, seasnails, and starfishes. Specifically, sea snails that primarily feed on oysters were found to be at risk of exposure to ciprofloxacin, brompheniramine, and promethazine. These high risks could be attributed to the monotonous diet habits and relatively limited food sources of these organisms. Furthermore, taking chirality into consideration, chlorpheniramine in the oysters was enriched by the S -enantiomer, with a relative potency 1.1-1.3 times higher when chlorpheniramine was considered as a racemate. Overall, this study highlights the prevalence of antihistamines in seafood and underscores the importance of studying enantioselectivities of pharmaceuticals in health risk assessments.

China is one of the major global consumers of veterinary antibiotics. Insufficient recognition of emissions and environmental contamination hamper global efforts to prevent antibiotic resistance development. This pioneering study combined empirical data and modeling approaches to predict total 2010-2020 emissions of 80 veterinary antibiotics ranging from 23,110 to 40,850 tonnes/year, after 36-50% antibiotic removal by manure treatment. Following an initial increase of 10% from 2010 to 2015, emissions declined thereafter by 43%. While 85% of emissions discharged into soils, approximately 56%, 23%, and 18% of environmental residue were ultimately distributed in soils, freshwaters, and seawaters under steady-state conditions. In 2020, 657 (319-1470) tonnes entered the ocean from inland freshwaters. Median ∑antibiotics concentrations were estimated at 4.7 × 10 3 ng/L in freshwaters and 2.9 ng/g in soils, with tetracyclines and sulfonamides as the predominant components. We identified 44 veterinary antibiotics potentially posing high risks of resistance development in freshwaters, with seven exhibiting high risks in >10% of Chinese freshwater areas. Tetracyclines were the category with the most antibiotics exhibiting elevated risks; however, sulfamethylthiazole demonstrated the highest individual compound risk. The Haihe River Basin displayed the highest susceptibility overall. The findings offer valuable support for control of veterinary antibiotic contamination in China.

Vulcanization accelerators (VAs) serve as crucial additives in synthetic rubber on a global scale. Despite their widespread use, the environmental presence, distribution, and associated exposure risks of VAs remain poorly understood. This study compiled a target list and conducted a screening for eight classes encompassing 42 VAs in diverse urban dust samples from South China. A total of 40 of the 42 target VAs were detectable across all four studied regions, among which 30 were identified for the first time in the environment. Among the eight structure-classified VA classes, xanthates exhibited the highest concentrations (median: 3810-81,300 ng/g), followed by thiazoles, guanidines, sulfenamides, dithiocarbamates, thiurams, thioureas, and others. The median total concentrations of all target VAs (∑VAs) were determined to be 5060 ng/g in road dust, 5730 ng/g in parking lot dust, 29,200 ng/g in vehicle repair plant dust, and 84,300 ng/g in household dust, indicating the widespread presence of numerous rubber-derived VAs in various urban environments. This study marked the first systematic effort to identify a wide range of emerging rubber-derived VAs prevalent in urban environments. The findings call for increased attention to these widely utilized but less well-evaluated chemicals in future research and environmental management efforts.

Rapid social-economic development introduces modern lifestyles into rural areas, not only bringing numerous modern products but also new pollutants, such as chlorinated paraffins (CPs). The rural Tibetan Plateau has limited industrial activities and is a unique place to investigate this issue. Herein we collected 90 free-range chicken egg pool samples across the rural Tibetan Plateau to evaluate the pollution status of CPs. Meanwhile, CPs in related soils, free-range chicken eggs from Jiangxi, and farmed eggs from markets were also analyzed. The median concentrations of SCCPs (159 ng g -1 wet weight (ww)) and MCCPs (1390 ng g -1 ww) in Tibetan free-range chicken eggs were comparable to those from Jiangxi (259 and 938 ng g -1 ww) and significantly higher than those in farmed eggs (22.0 and 81.7 ng g -1 ww). In the rural Tibetan Plateau, the median EDI of CPs via egg consumption by adults and children were estimated to be 81.6 and 220.2 ng kg -1 bw day -1 for SCCPs and 483.4 and 1291 ng kg -1 bw day -1 for MCCPs, respectively. MCCPs might pose potential health risks for both adults and children in the worst scenario. Our study demonstrates that new pollutants should not be ignored and need further attention in remote rural areas.

Source characteristics and health risks of indoor organophosphate esters (OPEs) are limited by the lack of knowledge on emission processes. This study attempted to integrate the contents and emissions of OPEs from indoor building materials to assess human health effects. Thirteen OPEs were investigated in 80 pieces of six categories of building materials. OPEs are ubiquitous in the building materials and ∑ 13 OPE contents varied significantly ( p < 0.05) from 72.8 ng/g (seam agent) to 109,900 ng/g (wallpaper). Emission characteristics of OPEs from the building materials were examined based on a microchamber method. Depending on the sample category, the observed initial area-specific emission rates of ∑ 13 OPEs varied from 154 ng/m 2 /h (carpet) to 2760 ng/m 2 /h (wooden floorboard). Moreover, the emission rate model was developed to predict the release levels of individual OPEs, quantify source contributions, and assess associated exposure risks. Source apportionments of indoor OPEs exhibited heterogeneities in multiple environmental media. The joint OPE contribution of wallpaper and wooden floorboard to indoor dust was up to 94.8%, while latex paint and wooden floorboard were the main OPE contributors to indoor air (54.2%) and surface (76.1%), respectively. Risk assessment showed that the carcinogenic risks of tris(2-chloroethyl) phosphate (3.35 × 10 -7 ) were close to the acceptable level (1 × 10 -6 ) and deserved special attention.

There is growing evidence that the transformation products of emerging contaminants in foodstuffs may pose a health risk to humans. However, the exact identities, levels, and estimated dietary intake (EDI) of neonicotinoid transformation products in crops remain poorly understood. We established an extended suspect screening strategy to investigate neonicotinoid insecticides and their transformation products in retail cowpea from 11 cities in Hainan Province, China. Forty-nine transformation products were identified in retail cowpea, of which 22-36 were found in 98.6% of the samples. Notably, 31 new transformation products were derived from new processes or a combination of different transformation processes. The mean concentrations of neonicotinoids and nine of the transformation products (with authentic standards) were in the ranges of 0.0824-5.34 and 0.0636-1.50 ng/g, respectively. The cumulative EDIs of the quantified transformation products were lower than those of parent neonicotinoids with the exception of clothianidin desmethyl, which had a ratio of 1157%. However, the coexistence of the other 40 transformation products (without authentic standards) in cowpea suggested that the exposure risk from all of the transformation products might be higher. This study demonstrated that pesticide transformation products should be considered in food chain risk assessments and included in future regulatory management.

Oil refinery activity can be an emission source of perfluoroalkyl and polyfluoroalkyl substances (PFAS) to the environment, while the contamination profiles in soils remain unknown. This study investigated 44 target PFAS in soil samples collected from an oil refinery in Southeastern China, identified novel PFAS, and characterized their behaviors by assessing their changes before and after employing advanced oxidation using a combination of nontarget analysis and a total oxidizable precursor (TOP) assay. Thirty-four target PFAS were detected in soil samples. Trifluoroacetic acid (TFA) and hexafluoropropylene oxide dimer acid (HFPO-DA) were the dominant PFAS. Twenty-three novel PFAS of 14 classes were identified, including 8 precursors, 11 products, and 4 stable PFAS characterized by the TOP assay. Particularly, three per-/polyfluorinated alcohols were identified for the first time, and hexafluoroisopropanol (HFIP) quantified up to 657 ng/g dw is a novel precursor for TFA. Bistriflimide (NTf2) potentially associated with an oil refinery was also reported for the first time in the soil samples. This study highlighted the advantage of embedding the TOP assay in nontarget analysis to reveal not only the presence of unknown PFAS but also their roles in environmental processes. Overall, this approach provides an efficient way to uncover contamination profiles of PFAS especially in source-impacted areas.

Amphibians are sensitive biomonitors of environmental pollutants but reports regarding per- and polyfluoroalkyl substances (PFAS), a class of synthetic organofluorine substances, are limited. In this study, samples of water and Chinese toads ( Bufo gargarizans ) were collected in Chaohu Lake, China. Tissue-specific bioaccumulation characteristics of 39 PFAS, including 19 perfluoroalkyl acids (PFAAs), 8 emerging PFAS, and 12 PFAA precursors, were investigated, and the levels of some biochemical indicators were determined. The highest PFAS concentrations were found in the liver [215.97 ng/g dry weight (dw)] of Chinese toads, followed by gonads (135.42 ng/g dw) and intestine (114.08 ng/g dw). A similar tissue distribution profile was found between legacy and emerging PFAS in the toads, and the occurrence of two emerging PFAS, 2,3,3,3-tetrafluoro-2-propanoate (HFPO-DA) and 6:2 hydrogen-substituted polyfluorooctane ether sulfonate (6:2 H-PFESA) in the amphibians were for the first time reported. Field-based bioaccumulation factors of HFPO-DA were higher than perfluorooctanoic acid, indicating the higher bioaccumulation potential of this emerging PFAS than the legacy C8 compound. Males had significantly higher gonad PFAS levels than females while estradiol levels in gonads increased with increasing concentrations of certain PFAS (e.g., 6:2 H-PFESA), implying that PFAS may trigger estrogenic effects in the toads, especially for male toads.

Plastic recycling and reprocessing activities may release organophosphate ester (OPE) flame retardants and plasticizers into the surrounding environment. However, the relevant contamination profiles and impacts remain not well studied. This study investigated the occurrence of 28 OPEs and their metabolites (mOPEs) in rainfall runoffs and agricultural soils around one of the largest plastic recycling industrial parks in North China and identified novel organophosphorus compounds (NOPs) using high-resolution mass spectrometry-based nontarget analysis. Twenty and twenty-seven OPEs were detected in runoff water and soil samples, with total concentrations of 86.0-2491 ng/L and 2.53-199 ng/g dw, respectively. Thirteen NOPs were identified, of which eight were reported in the environment for the first time, including a chlorine-containing OPE, an organophosphorus heterocycle, a phosphite, three novel OPE metabolites, and two oligomers. Triphenylphosphine oxide and diphenylphosphinic acid occurred ubiquitously in runoffs and soils, with concentrations up to 390 ng/L and 40.2 ng/g dw, respectively. The downwind areas of the industrial park showed elevated levels of OPEs and NOPs. The contribution of hydroxylated mOPEs was higher in soils than in runoffs. These findings suggest that plastic recycling and reprocessing activities are significant sources of OPEs and NOPs and that biotransformation may further increase the ecological and human exposure risk.

Halogenated flame retardants (HFRs) are a large class of chemical additives intended to meet flammability safety requirements, and at present, they are ubiquitous in the environment. Herein, we conducted the target analysis and suspect screening of legacy and novel HFRs and their metabolites in the blubber of finless porpoises ( Neophocaena phocaenoides ; n = 70) and Indo-Pacific humpback dolphins ( Sousa chinensis ; n = 35) stranded in Hong Kong, a coastal city in the South China Sea, between 2013 and 2020. The average concentrations of total target HFRs (ΣHFRs) were 6.48 × 10 3 ± 1.01 × 10 4 and 1.40 × 10 4 ± 1.51 × 10 4 ng/g lipid weight in porpoises and dolphins, respectively. Significant decreasing temporal trends were observed in the concentrations of tetra-/penta-/ hexa -bromodiphenyl ethers (tetra-/penta-/hexa-BDEs) in adult porpoises stranded from 2013-2015 to 2016-2020 ( p < 0.05), probably because of their phasing out in China. No significant difference was found for the concentrations of decabromodiphenyl ether and hexabromocyclododecane, possibly due to their exemption from the ban in China until 2025 and 2021, respectively. Eight brominated compounds were additionally identified via suspect screening. A positive correlation was found between the concentrations of tetra-BDE and methyl-methoxy-tetra-BDE (Me-MeO-tetra-BDE) ( p < 0.05), indicating that the metabolism of tetra-BDE may be a potential source of Me-MeO-tetra-BDE in marine mammals.

Synthetic phenolic antioxidants (SPAs) are a group of ubiquitous contaminants with multiple toxicities. However, current knowledge on the occurrence of SPAs in baby food and associated infant exposure is lacking. Herein, we analyzed three categories of baby food from China: infant formula, cereal, and puree, for a broad suite of 11 traditional and 19 novel SPAs. In addition to 11 traditional SPAs, up to 13 novel SPAs were detected in the baby food samples. The median concentrations of novel SPAs for infant formula, cereal, and puree were 604, 218, and 24.1 ng/g, respectively, surpassing those of traditional SPAs (53.4, 62.1, and 10.0 ng/g). The prevalent SPAs in the samples were butylated hydroxytoluene, 2,4-di- tert -butylphenol, pentaerythritol tetrakis[3-(3,5-di- tert -butyl-4-hydroxyphenyl)propionate] (AO 1010), and octadecyl 3-(3,5-di- tert -butyl-4-hydroxyphenyl) propionate (AO 1076). Source analysis indicated that the prevalence of these four SPAs in baby food was associated with contamination of packaging materials, mechanical processing, or raw ingredients. Migration experiments demonstrated that contamination of plastic packaging constituted an important source. Exposure assessment suggested that there may be no appreciable health risk posed by the SPAs in baby food. Even so, baby food consumption was still a dominant pathway for infant exposure to SPAs, with a higher contribution than breast milk consumption, dust ingestion, dermal dust absorption, and air inhalation, which requires special attention.

A large-scale survey was conducted by measuring five organophosphite antioxidants (OPAs) and three novel organophosphate esters (NOPEs) in 139 dust samples across China. The median summed concentrations of OPAs and NOPEs in outdoor dust were 33.8 ng/g (range: 0.12-53,400 ng/g) and 7990 ng/g (2390-27,600 ng/g), respectively. The dust concentrations of OPAs associated with the increasing economic development and population density from western to eastern China, whereas the NOPE concentration in Northeast China (median, 11,900 ng/g; range, 4360-16,400 ng/g) was the highest. Geographically, the distribution of NOPEs was significantly associated with annual sunshine duration and precipitation at each sampling site. Results of laboratory experiments further revealed that the simulated sunlight irradiation promoted the heterogeneous phototransformation of OPAs in dust, and this process was accelerated with the existence of reactive oxygen species and enhanced relative humidity. Importantly, during this phototransformation, the hydroxylated, hydrolyzed, dealkylated, and methylated products, e.g., bis(2,4-di- tert -butylphenyl) methyl phosphate, were identified by nontargeted analysis, part of which were estimated to be more toxic than their parent compounds. The heterogeneous phototransformation pathway of OPAs was suggested accordingly. For the first time, the large-scale distribution of OPAs and NOPEs and the phototransformation of these "new chemicals" in dust were revealed.

The accumulation and trophodynamics of organophosphate flame retardants (OPFRs) and their metabolites were investigated in the estuarine food web of the Pearl River, China. The mean ∑OPFR concentration among the investigated species increased in the following order: fish [431 ± 346 ng/g lipid weight (lw)] < snail (1310 ± 621 ng/g lw) < shrimp (1581 ± 1134 ng/g lw) < crab (1744 ± 1397 ng/g lw). The di-alkyl phosphates (DAPs) of di-( n -butyl) phosphate (DNBP), bis(2-butoxyethyl) phosphate (BBOEP), and diphenyl phosphate (DPHP) were the most abundant metabolites, with concentrations same as or even higher than their corresponding parent compounds. The log bioaccumulation factors for most OPFRs were lower than 3.70, and significant biomagnification was only found for trisphenyl phosphate [TPHP, with the trophic magnification factors (TMFs) > 1]. The TMFs of OPFRs, except for TPHP and tributyl phosphate had a positive correlation with lipophilicity (log  K OW , p ≤ 0.05) and a negative correlation with the biotransformation rate (log  K M , p ≤ 0.05). The mean TMF > 1 was observed for all of the OPFR metabolites based on the bootstrap regression method. The "pseudo-biomagnification" of OPFR metabolites might be attributed to the biotransformation of OPFRs in organisms at high trophic levels.

Fluorescent brighteners (FBs) are a group of mass-produced dyestuff chemicals that have been extensively used for decades. However, knowledge of their occurrence in municipal wastewater treatment plants on a large geographical scale remains unknown. Herein, we implemented the first nationwide survey for wastewater-derived FBs in sludge across major cities in China. All 25 target FBs were detected in the nationwide sludge. Ionic FBs exhibited much higher concentrations than nonionic FBs. The total sludge concentrations of 25 FBs (∑ 25 FBs) ranged from 7300 to 1,520,000 ng/g, with a median of 35,300 ng/g. A clear geographical distribution of significantly higher concentrations of FBs was found in East and Central China than in West China ( p < 0.05). The sludge concentrations of ∑ 25 FBs were correlated well with the gross domestic product (GDP) and population size at the provincial level in China ( p < 0.05), demonstrating the significance of anthropogenic impacts on FB levels in urban sludge. The nationwide annual emission of total FBs into sludge in China is estimated to be 835 tons/year, of which 134 tons/year is directly released into sludge-applied soils. Our work highlights another new class of chemicals that significantly contribute to the chemical mixtures in urban sludge and thus require immediate attention.

In this study of extracts of 100 food contact material (FCM) samples collected from South China, we identified 21 organophosphate esters (OPEs) by suspect screening and seven novel OPEs by characteristic fragments-based nontarget screening. Six organophosphite antioxidants (OPAs) were further identified using a suspect list derived from these identified OPEs. Of these compounds, 18 OPEs and 3 OPAs were found for the first time in the extracts of FCMs. (Semi-)quantification revealed that seven of the OPEs [triphenyl phosphate, tris(2,4-di- tert -butylphenyl) phosphate (TDtBPP), bis(2,4-di- tert -butylphenyl) methyl phosphate, (2,4-di- tert -butylphenyl)pentaerythritol phosphate, triethyl phosphate, 2-ethylhexyl-diphenyl phosphate, and trimethyl phosphate] and two of the OPAs [tris(2,4-di- tert -butylphenyl) phosphite (TDtBPPi) and pentabutylated triphenyl phosphite] were present in more than 50 FCM samples and that TDtBPP and TDtBPPi were the dominant OPE and OPA in FCMs, respectively [with median concentrations of 7260 ng/g (range: <8.50-103,879 ng/g) and 31,920 ng/g (range: <9.80-657,399 ng/g), respectively]. A migration test revealed that the migration efficiencies of compounds from a plastic coffee cup to food simulants in the cup increased as the ethanol/water ratio in the food simulants increased. This study significantly enhanced our understanding on the diversity and occurrences of OPEs and OPAs in FCMs used in China and their FCM-to-food migration risk.

Direct emissions from fluorochemical manufactory are an important source of per- and polyfluoroalkyl substances (PFASs) to the environment. In this study, a wide range of PFASs, including 8 legacy PFASs, 8 long-chain perfluoroalkyl carboxylic acids (PFCAs), and 40 emerging PFASs, were investigated through a target screening in multienvironmental matrices from a fluorochemical manufactory in China. Indoor dust was the most polluted matrix, wherein 52 PFASs were detected, and the median concentration of long-chain PFCA was 276 ng/g. A high level of short-chain PFAS in total suspended particles (median concentration = 416 ng/m 3 ) and the effluent in the manufactory (Σ 48 PFAS = 212 μg/L) will undoubtedly increase the burden on the surrounding environment. Twenty-four industrial byproducts were ascertained to be generated during the electrochemical fluorination (ECF) process, and eight fluorinated alternatives were considered to be produced during product development. Twelve PFASs were quantified for the first time in the working environments. Perfluoropropane sulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid (PFEESA), and 2-perfluorohexyl ethanoic acid are abundant fluorinated alternatives, with median levels of 1187-17204 ng/g in the dust. Significant positive correlations between ECF-related PFAS products and byproducts indicate that the detected values are strongly connected with the industrial source. Hierarchical cluster analysis further manifests their affiliation. Our findings raise the need for further investigations of emerging PFAS (including the first report of PFAS, such as PFEESA, in the environment) which may be released during the production process in the fluorochemical manufactories.

Benzotriazole UV stabilizers (BZT-UVs), including 2-(3,5-di- tert -amyl-2-hydroxyphenyl)benzotriazole (UV-328) that is currently under consideration for listing under the Stockholm Convention, are applied in many commodities and industrial products. However, limited information is available on the interannual variation of their environmental occurrence. In this study, an all-in-one strategy combining target, suspect, and nontarget screening analysis was established to comprehensively explore the temporal trends of BZT-UVs in mollusks collected from the Chinese Bohai Sea between 2010 and 2018. Significant residue levels of the target analytes were determined with a maximum total concentration of 6.4 × 10 3 ng/g dry weight. 2-(2-Hydroxy-3- tert -butyl-5-methyl-phenyl)-5-chloro-benzotriazole (UV-326), 5-chloro-2-(3,5-di- tert -butyl-2-hydroxyphenyl)benzotriazole (UV-327), and 2-(2-hydroxy-5-methylphenyl) benzotriazole (UV-P) were the predominant analogues, and UV-328 was the most frequently detected BZT-UV with a detection frequency (DF) of 87%. Whereas five biotransformation products and six impurity-like BZT-UVs were tentatively identified, their low DFs and semi-quantified concentrations suggest that the targeted analytes were the predominant BZT-UVs in the investigated area. A gradual decrease in the total concentrations of BZT-UVs was observed, accompanied by downward trends of the abundant compounds (e.g., UV-326 and UV-P). Consequently, the relative abundance of UV-327 increased because of its consistent environmental presence. These results suggest that continuous monitoring and risk assessment of BZT-UVs other than UV-328 are of importance in China.

Ultraviolet (UV) filters are of great concern due to their wide occurrence, bioaccumulation, and toxicity. Little is known about human exposure to UV filters. A total of 3467 individual human milk samples from 24 Chinese provinces were collected during 2017-2019. The concentrations of 12 UV filters in 100 pooled milk samples were determined. The total UV filter concentration was 78-846 (mean 235 ± 120) ng/g lipid weight. The highest and lowest total mean concentrations were for samples from Qinghai and Sichuan provinces, respectively. A significant positive correlation was found between UV radiation levels and UV concentrations in the samples. The dominant UV filters were 2-(2-hydroxy-5-methylphenyl) benzotriazole (UV-P) and ethylhexyl methoxycinnamate (EHMC), which contributed means of 32 and 22%, respectively, to the total concentrations. Plastic products and sunscreens were probably the sources of UV-P and EHMC in the human milk from China, respectively. The mean 2-(3,5-di- tert -amyl-2-hydroxyphenyl) benzotriazole (UV-328) concentration was 2.6 ± 2.6 ng/g lipid weight. The UV filter profiles were similar to profiles for samples from Japan, the Philippines, and Switzerland but not for samples from Korea and Vietnam. The estimated daily UV filter intake for breastfed infants was below the corresponding reference dose. This was the first large-scale study of UV filters in human milk and will help assess the risks posed.

This study conducted the first extensive and comprehensive investigation of the whole-scale sedimentary antibiotic concentration, possible drivers, environmental fate, and potential ecological risks in the Yangtze River. Totally, 20 antibiotics were detected in the sediments. Results revealed that the order of antibiotic abundance in sediment was fluoroquinolones > tetracyclines > macrolides > sulfonamides > amphenicols. The total antibiotic concentrations were 0.10-134.4 ng/g (mean: 11.88 ng/g). Of these, fluoroquinolones and tetracyclines were the two dominant antibiotic categories. The dominant occurrence of fluoroquinolones and tetracyclines in sediments suggested that the distribution coefficient ( K d ) was one of the important factors to determine their fate. Correlation analysis demonstrated that antibiotic contamination was largely influenced by the local scale of animal husbandry, and the positive correlation between antibiotics and heavy metals was likely driven by their common source of contamination and the complexation. Environmental risk assessment showed that tetracycline and chlortetracycline exhibited potential risks from medium to high in the Yangtze River, although most of the compounds posed minimal and low risks. This work provided a valuable large-scale data set across the whole Yangtze River and revealed the contamination profile of antibiotics. Mitigation and management measures to reduce antibiotic inputs are needed for the Yangtze River basin.

This study reports on the occurrence and distribution of short- and medium-chain chlorinated paraffins (SCCPs and MCCPs, respectively) in edible insects purchased from Asia and Europe. A total of 36 edible insect samples ( n = 24 from Asia, n = 12 from Europe) authorized and prepared for human consumption were purchased and analyzed for SCCPs and MCCPs via gas chromatography and mass spectrometry. SCCPs were detected in 83% of all edible insect samples with an overall median ∑SCCP concentration of 8.7 ng/g dry weight (dw) and a range of <2.0 to 410 ng/g dw, while MCCPs were present in 92% of samples with a median ∑MCCP concentration of 51 ng/g dw and a range of <6.0 to 380 ng/g dw. Median ∑SCCP and ∑MCCP levels in edible insects purchased in Asia were approximately two- and four-times higher, respectively, than those from Europe, while the difference was statistically significant for ∑MCCPs ( p < 0.001). Differences in homologue patterns were also observed between Asian and European samples to suggest diverse sources of CP contamination to insects which may include environmental accumulation, industrial processing equipment and food additives. Estimated daily intake of SCCPs and MCCPs via consumption of edible insects suggested that adverse health outcomes were very unlikely, but that continued monitoring of insect farming and processing practices are warranted.

Following regulations on legacy plasticizers, a large variety of industrial chemicals have been employed as substitutes to manufacture consumer products. However, knowledge remains limited on their environmental distributions, fate, and human exposure risks. In the present work, we screened for a total of 34 emerging plasticizers in house dust from South China and matched hand wipes collected from volunteers ( n = 49 pairs). The results revealed a frequent detection of 27 emerging plasticizers in house dust, with the total concentrations reaching a median level of 106 700 ng/g. Thirteen of them had never been investigated by any environmental studies prior to our work, which included glycerol monooleate (median: 61 600 ng/g), methyl oleate (16 400 ng/g), butyl oleate (411 ng/g), 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (341 ng/g), 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (105 ng/g), isopropyl myristate (154 ng/g), di(2-ethylhexyl) sebacate (69.1 ng/g), triisononyl trimellitate (64.4 ng/g), as well as a few others. Emerging plasticizers were also frequently detected in hand wipes, with a median total level of 4680 ng, indicating potential exposure via hand-to-mouth contact. Several chemicals, including acetyl tributyl citrate, tributyl citrate, di- n -butyl maleate, isopropyl myristate, and isopropyl palmitate, exhibited significant correlations between dust and hand wipe. However, other plasticizers did not follow this pattern, and the chemical compositional profiles differed between dust and hand wipe, suggesting chemical-specific sources and exposure pathways. Although the estimation of daily intake (EDI) indicated no substantial risks through dust ingestion or hand-to-mouth transfer of emerging plasticizers, continuous monitoring is needed to explore whether some of the important plasticizers are safe replacements or regrettable substitutions of the legacy ones.

Pharmaceutical residues in the environment are of great concern as ubiquitous emerging contaminants. This study investigated the presence of 40 pharmaceuticals in water and sediment of the Pearl River Estuary (PRE) in the wet season of 2020. Among psychiatric drugs, only diazepam was found in water samples while six of them were detected in the sediment. The Σantibiotics levels ranged from 6.18 to 35.9 ng/L and 2.63 to 140 ng/g dry weight in water and sediment samples, respectively. Fluoroquinolones and tetracyclines were found well settling in the outlet sediment, while sulfonamides could be released from disturbed sediment under stronger tidal wash-out conditions. After entering the marine waters, pharmaceuticals tended to deposit at the PRE mouth by the influence of the plume bulge and onshore invasion of deep shelf waters. Low ecological risks to the aquatic organisms and of causing antimicrobial resistance were identified. Likewise, hydrological modeling results revealed insignificant risks: erythromycin-H 2 O and sulfamethoxazole discharged through the outlets constituted 30.8% and 6.74% of their environmental capacity, respectively. Source apportionment revealed that pharmaceutical discharges through the Humen and Yamen outlets were predominantly of animal origin. Overall, our findings provide strategic insights on environmental regulations to further minimize the environmental stress of pharmaceuticals in the PRE.

Fluorescent brighteners (FBs) are extensively used as important chemical additives in multiple industrial fields worldwide. The history of the use of global FBs spans over 60 years, but knowledge on their environmental occurrence and risks remains largely unknown. Here, we screened indoor dust and hand wipes from South China for a broad suite of 17 emerging FBs using a new comprehensive analytical method. All 17 FBs were detected in the indoor environment for the first time, most of them having been rarely investigated or never reported in prior environmental studies. Ionic FBs were found to be more abundant than nonionic ones. The median total concentrations of the 17 detectable FBs reached 11,000 ng/g in indoor dust and 2640 ng/m 2 in hand wipes, comparable to or higher than those of well-known indoor pollutants. Human exposure assessment indicated that hand-to-mouth contact is a significant pathway for exposure to FBs, with a comparable contribution to that of dust ingestion. Most of the newly identified FBs are predicted to have persistent, bioaccumulative, or toxic properties. Our work demonstrates that FBs are another class of highly abundant, hazardous, and ubiquitous indoor pollutants that have been overlooked for decades and points to an emerging concern.

Increasing global and domestic food trade and required logistics create uncertainties in food safety inspection due to uncertainties in food origins and extensive trade activities. Modern blockchain techniques have been developed to inform consumers of food origins but do not provide food safety information in many cases. A novel food safety tracking and modeling framework for quantifying toxic chemical levels in the food and the food origins was developed. By integrating chemicals' multimedia environment exchange, food web, and source tracking systems, the framework was implemented to identify short-chain chlorinated paraffin (SCCP) contamination of fresh hairtail fish sold by a Walmart supermarket in Xi'an, northwestern China, and sourced in Eastern China Sea coastal waters. The framework was shown to successfully predict SCCP level with a mean of 17.8 ng g -1 in Walmart-sold hairtails, which was comparable to lab-analyzed 21.9 ng g -1 in Walmart-sold hairtails. The framework provides an alternative and cost-effective approach for safe food inspection compared to traditional food safety inspection techniques. These encouraging results suggest that the approach and rationale reported here could add additional information to the food origin tracking system to enhance transparency and consumers' confidence in the traded food they consumed.

Perfluoroalkyl sulfonates (PFSAs), perfluoroalkyl carboxylates (PFCAs), and emerging alternatives and precursors of these compounds were determined in tissues of finless porpoise ( Neophocaena asiaeorientalis sunameri ) collected from East China Sea in 2009-2010 and 2018-2019. The median hepatic concentrations of emerging poly- and perfluoroalkyl substances (PFASs), including 6:2 chlorinated polyfluorinated ether sulfonate (6:2 Cl-PFESA), 8:2 chlorinated polyfluorinated ether sulfonate (8:2 Cl-PFESA), 2,3,3,3-tetrafluoro-2-propanoate (HFPO-DA), and 4,8-dioxa-3 H -perfluorononanoate (ADONA) were 16.2, 2.16, < LOQ (limit of quantification) and < LOQ ng/g ww (wet weight), respectively. The concentrations of legacy substances, perfluorooctanesulfonate (PFOS), and perfluorooctanoate (PFOA), were 86.9 and 1.95 ng/g ww, respectively. The liver concentrations of 6:2 Cl-PFESA, HFPO-DA, and perfluorohexanesulfonate (PFHxS) increased with time between 2009-2010 and 2018-2019. Further, concentrations of PFOA showed a declining trend in finless porpoise, whereas PFOS and its precursor (i.e., perfluorooctane sulfonamide [FOSA]) showed an increasing trend with time between 2009-2010 and 2018-2019. Analysis of PFASs in nine different tissues/organs of finless porpoise (i.e., liver, heart, intestine, spleen, kidney, stomach, lung, muscle, and skin) revealed a similar distribution pattern between 6:2 Cl-PFESA and PFOS; however, the tissue distribution patterns differed between HFPO-DA and PFOA. The concentrations of PFAS alternatives in kidney were similar or lower than the prototype compounds PFOS and PFOA (i.e., 8:2 Cl-PFESA < 6:2 Cl-PFESA ≈ PFOS; HFPO-DA < PFOA), implying slow renal excretion of PFAS alternatives as that of legacy PFASs. The estimates of body burdens of PFASs in porpoises suggested comparable accumulation of PFAS alternatives and legacy PFSAs and PFCAs. This study provides novel information on temporal trends and tissue distribution of emerging PFASs in marine mammals in China.

Per- and polyfluoroalkyl substances (PFASs) were analyzed in outdoor ( n = 101) and indoor dust ( n = 43, 38 paired with outdoors) samples across mainland China. From 2013 to 2017, the median concentration of ∑PFASs in outdoor dust tripled from 63 to 164 ng/g with an elevated contribution of trifluoroacetic acid and 6:2 fluorotelomer alcohol. In 2017, the indoor dust levels of ∑PFASs were in the range 185-913 ng/g, which were generally higher than the outdoor dust levels (105-321 ng/g). Emerging PFASs were found at high median levels of 5.7-97 ng/g in both indoor and outdoor dust samples. As first revealed by the total oxidized precursors assay, unknown perfluoroalkyl acid (PFAA)-precursors contributed 37-67 mol % to the PFAS profiles in indoor dust samples. A great proportion of C8 PFAA-precursors were precursors for perfluorooctanesulfonic acid, while C6 and C4 PFAA-precursors were mostly fluorotelomer based. Furthermore, daily perfluorooctanoic acid (PFOA) equivalent intakes of PFAAs (C4-C12) mixtures via indoor dust were first estimated at 1.3-1.5 ng/kg b.w./d for toddlers at high scenarios, which exceeds the derived daily threshold of 0.63 ng/kg b.w./d. from the European Food Safety Authority (EFSA). On this basis, an underestimation of 56%-69% likely remains without considering potential risks due to the biotransformation of unknown PFAA-precursors.

As novel alternatives to legacy poly- and perfluoroalkyl substances (PFAS), perfluoroalkyl ether carboxylic acids (PFECAs) have been widely detected in the environment; however, there is limited information and knowledge regarding their bioaccumulation and trophic transfer behavior along the food chain. This research presents the first known published data on the bioaccumulation and trophic transfer characteristics of PFECAs in a source-impacted estuary. Elevated PFECA concentrations were observed in organisms (for instance, conch, with perfluoro-2-methoxyacetic acid (PFMOAA) concentration reaches up to 16 700 ng/g dry weight (dw)), indicating exposure risks to the consumers. Conch can be acted as a potential environmental bioindicator of PFMOAA. PFMOAA, hexafluoropropylene oxide trimer acid (HFPO-TrA) and PFOA were predominant detected in biotas. On the basis of trophic magnification factors (TMFs), PFECAs with ≥6 perfluorinated carbons (HFPO-TrA, hexafluoropropylene oxide tetramer acid (HFPO-TeA) and perfluoro (3, 5, 7, 9, 11-pentaoxadodecanoic) acid (PFO5DoA)) could be biomagnified along the food chain (TMF > 1), while PFMOAA with the least perfluorinated carbons undergone biodilution (TMF < 1). As seafood is an important dietary source of protein to human, there is a potential health risk related to the consuming polluted aquatic products.

Restrictions on legacy per- and polyfluoroalkyl substances (PFASs) have led to the widespread use of emerging PFASs. However, their toxicokinetics have rarely been reported. Here, tissue-specific uptake and depuration kinetics of perfluoroethylcyclohexanesulfonate (PFECHS) and 6:2 and 8:2 chlorinated polyfluoroalkyl ether sulfonates (Cl-PFESAs) were studied in marine medaka ( Oryzias melastigma ). The fish were exposed to these substances for 28 days (0.2 μg/L), followed by a clearance period of 14 days. The depuration constant ( k d (mean ± standard deviation)] was reported for the first time. Among the six studied tissues, the highest concentrations of 6:2 Cl-PFESA, 8:2 Cl-PFESA, and PFECHS were found in the liver [1540, 1230, and 188 ng (g of wet weight) -1 (mean ± standard deviation)] was reported for the first time. Among the six studied tissues, the highest concentrations of 6:2 Cl-PFESA, 8:2 Cl-PFESA, and PFECHS were found in the liver [1540, 1230, and 188 ng (g of wet weight) -1 , respectively] on day 28 while the longest residence times were found in the eyes ( t 1/2 values of 21.7 ± 4.3, 23.9 ± 1.5, and 17.3 ± 0.8 days, respectively). No significant positive correlation was found between the bioconcentration factors of the studied PFASs and the phospholipid or protein contents in different tissues of the studied fish. Potential metabolites of Cl-PFESAs, i.e., their hydrogen-substituted analogues (H-PFESAs), were identified by time-of-flight mass spectrometry. However, the biotransformation rates were low (<0.19%), indicating the poor capacity of marine medaka to metabolize Cl-PFESAs to H-PFESAs.

Triazine UV filters are an important class of UV filters, but knowledge on their environmental occurrence and human exposure remains largely unknown. In this study, we performed a targeted analysis of 17 emerging triazine UV filters in indoor dust and indoor air from South China based on a newly developed LC-MS/MS method. A total of 12 of the 17 emerging triazine UV filters were first positively detected in the dust and air samples. Ethylhexyl triazone (EHT) and bis-ethylhexyloxyphenol methoxyphenyl triazine (BEMT) were identified as the most abundant compounds. The median total concentrations of triazine UV filters reached 3860 ng/g in indoor dust and 1590 pg/m 3 in indoor air. Gas-particle partitioning analysis showed that triazine UV filters were predominant in the particle phase in ambient air. Significant concentration correlations were observed among most triazine UV filters. The estimated daily intake of triazine UV filters through dust ingestion and air inhalation for toddlers under high-end exposure scenarios was up to 839 ng/kg bw/day, but a lack of toxic thresholds hampers accurate risk assessment. Our work highlights another emerging class of UV filters that significantly contribute to indoor chemical mixtures and expresses concerns over their occurrence and human exposure.

The increasing discharge and ubiquitous occurrence of novel brominated flame retardants (NBFRs) in aquatic environments have initiated intense global concerns; however, little information is available regarding their structure-related trophodynamics in marine food webs. In this study, a tropical marine food web including 29 species (18 fish and 11 invertebrate species) was collected from coral reef waters of the Xisha Islands, the South China Sea, for an analysis of 11 representative NBFRs. The mean ∑NBFR concentrations generally increased in the following sequence: sea cucumbers (0.330 ng/g lw) < crabs (0.380 ng/g lw) < shells (2.10 ng/g lw) < herbivorous fishes (2.30 ng/g lw) < carnivorous fishes (4.13 ng/g lw), with decabromodiphenyl ethane (DBDPE) and hexabromobenzene (HBB) as the predominant components. Trophic magnification was observed for all of the investigated NBFRs, with trophic magnification factors (TMFs) ranging from 1.53 (tetrabromobisphenol A bis(dibromopropyl ether)) to 5.32 (HBB). Significant negative correlations were also found between the TMFs and the tested in vitro transformation clearance rates (CL in vitro ) for the target NBFRs except for bis(2-ethylhexyl)-3,4,5,6-tetrabromo-phthalate (TBPH) ( p < 0.05). Multiple linear regression analysis confirmed that the transformation rate is a more powerful predictor for TMFs than the hydrophobicity of NBFRs in this marine food web.

Liquid crystal monomers (LCMs) in liquid crystal displays (LCDs) may be released into the environment, especially in electronic waste (e-waste) recycling industrial parks with a high pollution risk. However, little has been known about the environmental release and human exposure to LCMs until now. Herein, a total of 45 LCMs were detected in LCDs of commonly used smartphones and computers by high-resolution mass spectrometry with suspect screening analysis. Fluorinated biphenyls and their analogs were the dominant LCMs. Based on available standards of the screening results and previous studies, 55 LCMs were quantified in samples from an e-waste recycling industrial park in Central China. The LCMs were frequently detected in outdoor dust ( n = 43), workshop #1 indoor dust ( n = 53), and hand ( n = 43) and forehead wipes ( n = 43), with median concentrations of 6950 ng/g, 67,400 ng/g, 46,100 ng/m 2 , and 62,100 ng/m 2 , respectively. The median estimated daily intake values of the LCMs via dust ingestion and dermal absorption were 48.3 and 16.5 ng/kg body weight/day, respectively, indicating a high occupational exposure risk of these compounds. In addition, 16 LCMs were detected in the serum of eight elderly people (≥60 years old) with over 5 years of experience in e-waste dismantling operations, resulting in a total concentration range of 3.9-26.3 ng/mL.

Dechlorane Plus (DP) has been detected in human serum around the world. Determining how DP binds to human serum albumin (HSA) could improve our understanding of the effects of DP in humans. The results of a fluorescence titration experiment indicated that DP binds to HSA at the interface between domains IIA and IIB, and HSA has more affinity for anti -DP than syn -DP. The DP concentrations in serum from 33 people living in Wuxi City, China, were determined in five consecutive years (2012-2016). The total concentrations of the two DP isomers were 1.73-16.3 ng·g -1 lipid weight (mean 4.7 ng·g -1 lipid weight). No clear increasing or decreasing temporal trend was found in the DP concentrations in serum over the study period. The affinity between DP and HSA will increase as the amount of fatty acids combined with HSA increases. This explained the syn -DP and anti -DP concentrations in serum being higher for overweight people than for normal weight people. Ethanol can occupy the DP binding sites on HSA. This explained the syn -DP and anti -DP concentrations being lower for alcoholic people than for nonalcoholic people.

There is a dearth of information regarding the pollution status of emerging organophosphate esters (OPEs) in wild fish. Here, we optimized and validated a quick, easy, cheap, effective, rugged, and safe (QuEChERS) pretreatment method, which was further applied for target, suspect, and nontarget screening of OPEs in n = 48 samples of wild fishes from Taihu Lake (eastern China). This integrated technique allows us to fully identify 20 OPEs, and 9 out of them are emerging OPEs detected in wild fish for the first time. Importantly, some of the emerging OPEs, i.e., tris(2,4-di- tert -butylphenyl) phosphate (TDtBPP), 4- tert -butylphenyl diphenyl phosphate (BPDP), and 2-isopropylphenyl diphenyl phosphate (IPDP), exhibited greater or at least comparable contamination levels as compared to traditional ones. There were no statistically significant interspecies ( n = 6) differences regarding OPE concentrations. However, we observed significant differences on OPE concentrations among different tissues of silver carp ( Hypophthalmichthys molitrix ), for which the intestine has the highest OPE mean concentration (46.5 ng/g wet weight (ww)), followed by the liver (20.1 ng/g ww) ≈ brain (20.0 ng/g ww) > gill (14.8 ng/g ww) > muscle (11.4 ng/g ww). An interesting exception is IPDP, which presents an unexpectedly high concentration in the brain (0.510 ng/g ww). Collectively, this study expands our understanding of OPE contamination in wild fish and clearly shows that emerging TDtBPP, IPDP, and BPDP could play an equally important role as traditional OPEs in contribution of OPE pollution in wild fish samples.

Novel flame retardants (FRs) are of increasing concern, given growing evidence of health effects and use to replace polybrominated diphenyl ethers (PBDEs). This study modeled combined effects of use policies and decoration on indoor FRs and human exposure for 18 widely used PBDEs, organophosphate esters (OPEs), and novel brominated flame retardants in typical urban indoor environments in China. The current estimated indoor emission rates and average concentrations in air and dust of the 18 FRs were 10 2 -10 3 ng/h, 561 ng/m 3 , and 1.5 × 10 4 ng/g, respectively, with seven OPEs dominant (>69%). Different use patterns exist between China and the US and Europe. Scenarios modeled over 2010-2030 suggested that decoration would affect indoor concentrations of FRs more than use policies, and use policies were mainly responsible for shifts of FR composition. Additional use of hexabromobenzene and 2,3,4,5,6-pentabromotoluene and removal of BDE-209 would make the total human exposure to the modeled FR mixture increase after the restriction of penta- and octa-BDE but decrease after deca-BDE was banned. Better knowledge of the toxicity of substitutes is needed for a complete understanding of the health implications of such changes. Toddlers may be more affected by use changes than adults. Such studies are supportive to the management of FR use.

Surface sediments of polluted urban rivers can be a reservoir of hydrophobic persistent organic pollutants (POPs). In this study, we comprehensively assessed the contamination of two groups of POPs, that is, polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs), in 173 black-odorous urban rivers in China. Spatial distribution of PCBs and PBDEs showed similar patterns but very different contamination levels in surface sediments, that is, average concentrations of 10.73 and 401.16 ng/g dw for the ∑PCBs and ∑PBDEs, respectively. Tetra -/ di -CBs and deca -BDE are major PCBs and PBDEs and accounted for 59.11 and 95.11 wt % of the ∑PCBs and ∑PBDEs, respectively. Compared with the persistence of PBDEs, the EF changes of chiral PCBs together with previous cultivation evidence indicated indigenous bioconversion of PCBs in black-odorous urban rivers, particularly the involvement of uncharacterized Dehalococcoidia in PCB dechlorination. Major PCB sources (and their relative contributions) included pigment/painting (25.36%), e-waste (22.92%), metallurgical industry (13.25%), and e-waste/biological degradation process (10.95%). A risk assessment indicated that exposure of resident organisms in urban river sediments to deca -/ penta -BDEs could pose a high ecological risk. This study provides the first insight into the contamination, conversion and ecological risk of PCBs and PBDEs in nationwide polluted urban rivers in China.

Synthetic antioxidants represent a complex group of additive chemicals broadly used in consumer products. While traditional antioxidants such as 2,6-di- tert -butyl-4-methylphenol (BHT) have been well studied, a variety of "novel" antioxidants have emerged with extensive applications but received much less attention. Our study aimed to explore a suite of 34 emerging antioxidants in house dust from four different regions, including Guangzhou (China), Adelaide (Australia), Carbondale (Illinois), and Hanoi (Vietnam). The results revealed broad occurrence of several rarely investigated chemicals in house dust across regions, including triethylene glycol bis(3- tert -butyl-4-hydroxy-5-methylphenyl)propionate (AO245), 2,6-di- tert -butyl-4-(dimethylamino)methylphenol (AO4703), 2,2'-thiene-2,5-diylbis(5- tert -butyl-1,3-benzoxazole) (BBOT), 1,3-diphenylguanidine (DPG), 2,4-bis(1,1-dimethylethyl)phenol (2,4DtBP), and 2,6-bis(1,1-dimethylethyl)phenol (2,6DtBP). In particular, DPG exhibited a median concentration of 5030-11 400 ng/g in house dust from the studied regions except for Hanoi (305 ng/g), generally 1 order of magnitude greater than that of BHT (890-1060 ng/g) and dominating the compositional profiles of antioxidants. Estimated intake of target antioxidants by toddlers via dust ingestion, even under the high exposure scenario, was determined to be 2-4 orders of magnitude lower than the reference doses of selected antioxidants. However, potential risks from long-term exposure to a cocktail of antioxidants under environmentally relevant concentrations merit further investigations due to insufficient knowledge on the sources, fate, and toxicokinetics of these chemicals to date.

Organophosphite antioxidants (OPAs) are important auxiliary antioxidants used in plastic polymers and can be oxidized to organophosphate esters (OPEs) during production and processing. In this work, the occurrence of OPAs and OPEs in farmlands with or without mulch film applications was investigated. Six OPAs and five OPEs were detected, with the median concentrations of 2.66 ng/g (∑ 6 OPAs) and 100 ng/g (∑ 5 OPEs) in the film-mulching soil and 1.16 ng/g (∑ 6 OPAs) and 47.9 ng/g (∑ 5 OPEs) in the nonfilm-mulching soil, respectively. The oxidative derivative of AO168 (tris (2,4-di- tert -butylphenyl) phosphite), a typical OPA, AO168═O (tris (2,4-di- tert -butylphenyl) phosphate) was frequently detected in farmlands at the concentrations of 0-731 ng/g, which is much higher than that of the commercial OPEs (0-12.1 ng/g). This suggests that the oxidation derivatives of OPAs (OPAs═O) might be important OPE contaminants in soils. Mulch films could be their important source. According to the simulation migration experiment, the emission risk ranges of AO168 and AO168═O from mulch films to soils in China were estimated to be 3.96-87.6 and 10.5-95.3 tons/year, respectively, which were much higher than those of OPEs from sewage sludge applications. Simulation experiments also demonstrated that oxidation was the major pathway for OPAs in soils. OPAs with small substituent groups could be potential sources for organophosphate diesters. For the first time, the serious pollution of OPAs and OPAs═O in soils has been reported, and mulch films have been identified as their potential source.

Organochlorine pesticides (OCPs) have been used worldwide on an enormous scale over the last century but are banned globally due to environmental persistence and ecotoxicity in recent decades. The long-term effects of OCP ban for agricultural use in China since 1983 on the reproductive health of small terrestrial mammals have never been evaluated in the field. We examined the residue dynamics of OCPs and the reproductive performance of Chinese striped hamsters ( Cricetulus barabensis ) in North China Plain during 1983-2010 and concluded that the exposure levels of OCPs in hamsters drastically decreased from 2900 ± 740 to 25.2 ± 6.88 ng/g with an average half-life of 5.08 yrs, coinciding with the observed reproductive recovery of hamsters. The population-based reproductive performance of hamsters was significantly and negatively associated with OCP exposure levels after adjusting the contributions from climate and population density factors, indicating that the ban of OCPs has facilitated the reproductive recovery of hamsters by up to 81% contribution. Our findings suggest that the OCP ban is effective to restore reproduction of small terrestrial mammals. Integration of population biology and environmental science is essential to assess the impacts of persistent organic pollutants on ecological safety and biodiversity loss under accelerated global change.

Despite the popularity of smartphones worldwide, persistent toxic substances (PTSs) in protective cases of mobile phones (PCMPs) and their health risks via direct skin contact have been ignored. This study investigated PTSs in PCMPs made in China with different materials and sales territory and their potential harm to human health. Polybrominated diphenyl ethers (PBDEs, 6.40 ng/g), new brominated flame retardants (NBFRs, 144 ng/g), organophosphate esters (OPEs, 10.1 μg/g), short-chain chlorinated paraffins (SCCPs, 3.58 μg/g), medium-chain chlorinated paraffins (MCCPs, 3.17 μg/g), and heavy metals (HMs, 72.3 μg/g) were detected. It was found that the different concentrations and compositions depend on the material, region, and use. Moreover, the raw materials used to fabricate PCMPs are of variable quality and may include recycled plastic waste. There are no standard quality specifications for PCMPs, and different materials have different properties, including specific surface area and adsorption ability. The risk assessment performed by Monte Carlo simulations indicated that the PTSs evaluated pose no health risks to the general population and may have adverse effects on individual high-exposure populations. According to the results of this work, it is suggested that more stringent global specifications for the selection of raw materials should be established, including the content and structural characteristics of PTSs, limitations on the use of additives in the production process, and the handling after use.

Liquid-crystal monomers (LCMs), especially fluorinated biphenyls and analogues (FBAs), are considered to be a new generation of persistent, bioaccumulative, and toxic organic pollutants, but their emissions from liquid-crystal display (LCD)-associated e-waste dismantling remain unknown. To fill this knowledge gap, a broad range of 46 LCMs, including 39 FBAs and 7 biphenyls/bicyclohexyls and analogues (BAs), were investigated by a dedicated target analysis in e-waste dust samples. Of 39 target FBAs, 34 were detected in LCD dismantling-associated dust. Among these 34 detectable FBAs, 9 were detected in 100% of the samples and 25 were frequently detected in >50% of the samples. The total concentrations of these 34 FBAs (∑ 34 FBAs) detected in LCD e-waste dust were in the range of 225-976,000 (median: 18,500) ng/g, significantly higher than those in non-LCD e-waste dust (range: 292-18,500, median: 2300 ng/g). In addition to FBAs, six of seven BAs were also frequently detected in LCD e-waste dust with total concentrations (∑ 6 BAs) of 29.8-269,000 (median: 3470) ng/g. Very strong and significant correlations ( P < 0.01) were identified in all frequently detected LCMs, indicating their common applications and similar sources. Our findings demonstrate that e-waste dismantling contributes elevated emissions of FBAs and BAs to the ambient environment.

For the most complex artificial chlorinated environmental contaminants, much less is known for medium-chain CPs than short-chain CPs. In this research, the spatial distributions of MCCPs and SCCPs in farmland soil and maize leaves near a CP production facility were found marginally influenced by seasonal winds. The levels of ∑MCCPs and ∑SCCPs were in the ranges of <1.51-188 and 5.41-381 ng/g dw for soils; and 77.6-52930 and 119-61999 ng/g dw for maize leaf, respectively. Bioaccumulation and tissue distributions of the CPs within maize plants were specifically analyzed. Most of the CPs were contained in the tissues directly exposed to airborne CPs. Though the estimated risk of CPs to humans through ingestion of kernels appears to be minimal, the edible safety of MCCPs in maize plants for cattle was nearly in the designated range of adverse effects. To our knowledge, this is the first report on bioaccumulation of CPs in mature maize plants, especially in the parts eaten by humans and domestic animals. It provides a baseline reference to the edible risks of CPs in agricultural food plants and alerts us to the problematic environmental behavior of MCCPs, a probable future replacement for SCCPs commercially.

Upon exposure, most bisphenol analogues (BPs) are rapidly metabolized to BP conjugates in organisms. Monitoring studies on BPs in aquatic organisms have been mainly focused on free-form BPs. However, the relative amount of conjugated BPs in organisms is still not well known, especially in marine organisms. In this study, we collected marine organisms (13 species; n = 74), as well as seawater ( n = 15), from East China Sea, and analyzed them for bisphenol A (BPA) and its eight analogues. In seawater, BPA was the predominant BP (mean ± standard deviation (SD), 18 ± 9.7 ng/L), followed by bisphenol S (BPS; 3.7 ± 2.8 ng/L), bisphenol F (BPF; 0.31 ± 0.17 ng/L), and bisphenol AF (BPAF; 0.24 ± 0.15 ng/L). The whole body of each marine organism was used for BP analysis in this study. BPA (mean 3.8 ng/g, range 1.2-7.7 ng/g) and BPS (1.5 ng/g, 0.19-6.1 ng/g) were still the predominant BPs in marine organisms without hydrolysis. After enzymatic hydrolysis treatment, mean concentrations of BPs increased 1.8 (BPS)-3.7 (BPA) times in marine organisms. Correspondingly, on average, 74, 52, 49, 48, and 45% of BPA, bisphenol Z, BPF, BPS, and BPAF were present in conjugated forms, respectively, in marine organisms. Moreover, bioaccumulation and biomagnification of BPs were evaluated using pooled marine organism samples. We first found that the mean log BAF values of BPs increased 0.091 (BPAF) to 0.31 (BPA) times in marine organisms after hydrolysis. Overall, this study first determines the amount of BPs present in conjugated forms in marine organisms, which are helpful for better understanding the occurrence of BPs in organisms.

Triazole resistance in Aspergillus fumigatus is a growing public health concern. In addition to its emergence in the therapy of invasive aspergillosis by triazole medicines, it has been frequently detected in agricultural fields all over the world. Here, we explore the potential link between residues of azole fungicides with similar chemical structure to triazole medicines in soil and the emergence of resistant A. fumigatus (RAF) through 855 500 km 2 monitoring survey in Eastern China covering 6 provinces. In total, 67.3%, 15.2%, 12.3%, 2.9%, 1.5%, 0.4%, and 0.3% of the soil samples contained these five fungicides (tebuconazole, difenoconazole, propiconazole, hexaconazole, and prochloraz) of 0-100, 100-200, 200-400, 400-600, 600-800, 800-1000, and >1000 ng/g, respectively. The fractions of samples containing RAF isolates were 2.4%, 5.2%, 6.4%, 7.7%, 7.4%, 14.3%, and 20.0% of the samples with total azole fungicide residues of 0-100, 100-200, 200-400, 400-600, 600-800, 800-1000, and >1000 ng/g, respectively. We find that the prevalence of RAFs is positively ( P < 0.0001) correlated with residual levels of azole fungicides in soils. Our results suggest that the use of azole fungicides in agriculture should be minimized and the intervals between treatments expanded to reduce the selective pressure toward the development of resistance in A. fumigatus in agricultural fields.

Several haloalkyl organophosphate triester (OPTE) flame retardants have been restricted in some countries due to their potential health risks, but the usage of alternative haloalkyl OPTEs is of concern. In this study, we comprehensively screened for haloalkyl OPTEs in house dust using high-resolution mass spectrometry. Through halogenation-guided nontarget screening, a rare chloroalkyl OPTE, diethylene glycol bis(bis(2-chloroisopropyl)phosphate) (DEGBBCPP), was unequivocally identified (Level 1) in house dust of Beijing, North China. In addition, by screening a suspect list of 61 haloalkyl OPTEs from the EPA's CompTox Chemicals Dashboard, we tentatively identified diethylene glycol bis(bis(2-chloroethyl)phosphate) (DEGBBCEP) and ethylene bis[bis(2-chloroethyl)phosphate] (EBBCEP) (Level 2). DEGBBCPP was detected in all 45 house dust samples, and the median concentration was 98.4 ng/g (13.6-6217 ng/g), that is, approximately one-half that of tris(1,3-dichloro-2-propyl) phosphate, a traditional high-production chloroalkyl OPTE. The detection frequencies of DEGBBCEP and EBBCEP were 96% and 98%, respectively, but at relatively low median concentrations of 10.6 ng/g (from not detected to 152 ng/g) and 3.79 ng/g (from not detected to 130 ng/g), respectively. In standard house dust SRM2585, DEGBBCEP and EBBCEP were detected at 160 ± 15.7 and 1897 ± 38.8 ng/g, respectively, but DEGBBCPP was not detected. Future studies should evaluate the potential adverse health effects of these emerging flame retardants.

Liquid crystal monomers (LCMs) have been proposed to be persistent, bioaccumulative, and toxic (PBT) substances; however, there is a dearth of information regarding their occurrence in sediment samples. Here, an analytical method was developed for the quantitative determination of LCMs in sediment samples, and n = 76 sediment samples were collected and analyzed to determine accurate concentrations of LCMs. Our results indicated that the developed pretreatment procedure was applicable for the determination of LCM concentrations in sediments. We observed that LCMs were detected in 75 out of the 76 sediment samples, and 23, 18, and 14 out of the 39 target LCMs were quantified in at least one of the analyzed sediments from rivers around LCM or liquid crystal device (LCD) manufacturers, Taihu Lake, and rivers around e-waste recycling sites, respectively. The LCMs in the samples from rivers around LCM/LCD manufacturers exhibited the greatest mean concentrations of 26.1 ng/g dry weight (dw), followed by those from e-waste recycling site areas (1.15 ng/g dw) and Taihu Lake (0.076 ng/g dw). Collectively, this study provided the first analytical method that was able to quantify the concentrations of LCMs in sediment samples and provided the first evidence for the occurrence of LCMs in sediment samples.