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As emerging organic contaminants, Polyhalogenated carbazoles (PHCZs) have caused wide concerns due to their wide distribution in the environment and dioxin-like toxicity. Nevertheless, research on the distribution and formation mechanisms of PHCZs in polluted environment of printing and dyeing plants is lacking. Here, 11 PHCZs were detected in samples from the Cao'e River, China, a typical river heavily polluted by printing and dyeing. The PHCZs concentrations in the soil, sediment, and water samples were 8.3-134.5 ng/g (median: 26.3 ng/g), 17.7-348.8 ng/g (median: 64.2 ng/g), and 1.2-41.4 μg/L (median: 4.8 μg/L), respectively. 3,6-dichlorocarbazole was the dominant congener, proved by both analysis results and formation mechanisms. PHCZ migration patterns in water-sediment systems indicated that highly halogenated PHCZs tend to be transferred to sediment. Furthermore, PHCZs are persistent, can undergo long-range transport, and pose high risks to aquatic organisms by models. PHCZs released from dye production into environment can be form through halogenation of carbazole or PHCZs formed during the dye synthesis, heating of halogenated indigo dyes, and photolysis of highly halogenated PHCZs. This is the first comprehensive study to reveal the impact of printing and dyeing plant activities on PHCZs in the environment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Objective: Chlorination is often used to disinfect recreational water in large amusement parks; however, the health hazards of chlorination disinfection by-products (DBPs) to occupational populations are unknown. This study aimed to assess the exposure status of chlorinated DBPs in recreational water and the health risks to employees of large amusement parks., Methods: Exposure parameters of employees of three large amusement parks in Shanghai were investigated using a questionnaire. Seven typical chlorinated DBPs in recreational water and spray samples were quantified by gas chromatography, and the health risks to amusement park employees exposed to chlorinated DBPs were evaluated according to the WHO's risk assessment framework., Results: Trichloroacetic acid, dibromochloromethane, bromodichloromethane, and dichloroacetic acid were detected predominantly in recreational water. The carcinogenic and non-carcinogenic risks of the five DBPs did not exceed the risk thresholds. In addition, the carcinogenic and non-carcinogenic risks of mixed exposure to DBPs were within the acceptable risk limits., Conclusion: Typical DBPs were widely detected in recreational water collected from three large amusement parks in Shanghai; however, the health risks of DBPs and their mixtures were within acceptable limits., (Copyright © 2024 The Editorial Board of Biomedical and Environmental Sciences. Published by China CDC. All rights reserved.)

Dissolved black carbon (DBC), the soluble component of black carbon, which mainly comes from the incomplete combustion of fossil fuels or biomass, is widely spread in source water and significantly contributes to the formation of dissolved organic matter (DOM). However, the origin of DBC in different types of source water in China has not been well studied, as well as its subsequent transformation and toxicity contribution during disinfection of source water DOM by chlor(am)ine. In this study, DBC from 17 different source water in East China at different seasons was collected. The δ 13 C compositions indicated that straw burning was the main origin of DBC in source water. After simulated chlor(am)ination of DBC, 5 categories of aliphatic disinfection byproducts (DBPs) including trihalomethanes, haloacetic acids, haloacetonitriles, haloketones, halonitromethanes and 6 categories of aromatic DBPs including halophenols, halonitrophenols, halohydroxybenzaldehyde, halohydroxybenzoic acid, halobenzoquinones and haloaniline were detected. Compared with chlorination of DBC, higher levels of nitrogenous DBPs and aromatic DBPs were generated during chloramination. Detected DBPs accounted for 42 % of total organic halogen. What's more, Chinese hamster ovary cells cytotoxicity tests showed that the cytotoxicity of DBPs formed by chlor(am)ination of DBC was 4 times higher than that by chlor(am)ination of DOM. Haloacetonitriles contributed to the highest cytotoxicity in the chloramination of DBC, and haloacetic acids contributed to the highest cytotoxicity in chlorination. 67 % of the total cytotoxicity attributed to the undetected DBPs. As a result, DBPs generated from DBC contributed to 11.7 % of the total cytotoxicity in the chlor(am)ination of the source water DOM although DBC only took up 2 % of DOC in the source water. Results obtained from this study systematically revealed the DBPs formation from DBC and their potential cytotoxicity contribution in the chlor(am)ination of source water DOM, which should not be ignored in drinking water treatment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Following the enactment of a generic ban in China in 2021, the synthetic cannabinoid market has been evolving, now encompassing even wider structural diversity. Compounds carrying a brominated core such as ADB-5'Br-BUTINACA (ADMB-B-5Br-INACA) and tail-less analogs, such as ADB-5'Br-INACA (ADMB-5Br-INACA), MDMB-5'Br-INACA, and ADB-INACA (ADMB-INACA), have been detected since late 2021. This study investigated the cannabinoid receptor (CB) activation potential of synthesized (S)-enantiomers of these substances, as well as of two predicted analogs MDMB-5'Br-BUTINACA (MDMB-B-5Br-INACA) and ADB-5'F-BUTINACA (ADMB-B-5F-INACA), using CB 1 and CB 2 β-arrestin 2 recruitment assays and a CB 1 intracellular calcium release assay. Surprisingly, the tail-less (S)-ADB-5'Br-INACA and (S)-MDMB-5'Br-INACA retained CB activity, albeit with a decreased potency compared to their tailed counterparts (S)-ADB-5'Br-BUTINACA and (S)-MDMB-5'Br-BUTINACA, respectively, which were potent and efficacious CB 1 agonists. Also, at CB 2 , tail-less analogs showed a lower potency but increased efficacy. Removing the bromine substitution ((S)-ADB-INACA) resulted in a reduced activity at CB 1 ; however, this effect was less prominent at CB 2 . Looking at tailed analogs, replacing the bromine with a fluorine substitution ((S)-ADB-5'F-BUTINACA) resulted in an increased potency and efficacy at both receptors. Furthermore, as ADB-5'Br-INACA and MDMB-5'Br-INACA have been frequently detected together in Scottish prisons, this study also evaluated the CB 1 receptor activation potential of different mixtures of their respective reference standards, showing no unexpected cannabimimetic effect of combining both substances. Lastly, two powders seized by Belgian Customs and confirmed to contain ADB-5'Br-INACA and MDMB-5'Br-INACA, respectively, were assessed for CB activity. Based on the comparison with their reference standards, varying degrees of purity were suspected., (© 2023 John Wiley & Sons Ltd.)

Studying the geochemical behavior of chlorine is the basis of understanding the chlorine cycle in nature. To explore the spatiotemporal distribution of natural organic chlorine (Cl org ), L layer (litter fall), F-H layer (humification zone), topsoil layer (0-20 cm), and deep soil layer (20-40 cm) samples were collected from 18 sampling sites at different altitudes (851-2918 m) in Shennongjia Forest in May, August, and December. Cl org content was analyzed, and the Cl org stocks were calculated. The major factors affecting the distribution of Cl org were explored. The results revealed that the sum of Cl org content in four layers varied from 7.958 to 184.686 mg/kg, and the highest value was observed in August. Cl org accounted for 46%-77% of total chlorine, with the highest mean ratio in soil layer (0-20 cm). Cl org content exhibited the following trend: F-H layer > L layer > topsoil layer (0-20 cm) > deep soil layer (20-40 cm). The seasonal patterns of Cl org in soil layers were different from that in L and F-H layers, which were mainly controlled by the content and humification degree of organic matter. Cl org storage was much higher in soil layers (61-246 kg/ha) than those in F-H layer (1.1-7.1 kg/ha) and in L layer (0.1-0.8 kg/ha) because of the large thickness of the soil layers. Overall, the Cl org content exhibited an increasing trend with altitude, except at an altitude of approximately 1800 m. Cl org content in L and F-H layers varied more obviously with altitude than that in soil layers. When inorganic chlorine (Cl in ) was not a limiting factor for the chlorination process, Cl org content in L and F-H layers was significantly affected by climate and organic matter controlled by altitude, while Cl org content in soil layers was also mediated by metal ions and pH, and soil particle size. This study could provide a scientific basis for assessing the chlorine cycle in nature., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Some disinfection by-products (DBPs) in drinking water present a potential safety concern. This study focuses on the elements influencing DBPs formation. A total of 120 water samples were collected from 10 different drinking water facilities spanning 5 counties within Huzhou, Zhejiang Province, China. Concentrations of trihalomethanes (THMs) and haloacetic acids (HAAs) were observed to be 14.5 and 27.4 μg/L, respectively, constituting 34 and 64% of the total DBPs. Seasonal fluctuations demonstrated that HAAs, THMs, halonitromethanes (HNMs), and haloacetonitriles (HANs) followed a similar pattern with higher levels in summer or autumn compared to spring. Importantly, the concentrations of HAAs and THMs were markedly higher in Taihu-sourced water compared to other sources. Geographically, Nanxun exhibited the highest levels of total DBPs, HAAs, and THMs, while Deqing and Changxing demonstrated significantly lower levels. Correlation studies between water quality parameters and DBPs revealed that factors such as chloride content, temperature, and residual chlorine positively influenced DBPs formation, whereas turbidity negatively affected it. Principal component analysis suggested similar formation processes for HANs, haloketones (HKs), HNMs, and THMs. Factors such as temperature, chemical oxygen demand (COD), and residual chlorine were identified as significant contributors to the prevalence of HAAs.

Spatial distributions, levels, and comprehensive assessments of post-flood tap water disinfection by-products (DBPs) were first studied in Henan Province after the "7.20" Extreme Rainstorm Event in 2021. DBPs levels and health risks in tap water were higher in areas flooded (waterlogged) by storm or upstream flood discharge (WA) and rainstorm-affected areas (RA) compared with other areas (OA), suggesting that extreme rainstorm and flooding events may somehow exacerbate DBPs contamination of tap water through disinfection. WA sites were characterized as contamination hotspots. The results revealed high haloacetic acids (HAAs) levels in WA (Avg: 57.79 μg·L -1 ) and RA (Avg: 32.63 μg·L -1 ) sites. Compared with normal period, DBPs-caused cancer risk increased by 3 times, exceeding the negligible risk level. Cancer risk came primarily from the ingestion of trihalomethanes (THMs) (>80%), children were the sensitive group. Those between 30 and 69 showed approximately 1.7 times higher disability-adjusted life yearsper person-yearthan other age groups. Apart from regulated DBPs, bromochloracetic acid (BCAA) and dibromoacetonitrile (DBAN) appear to be the main toxicity contributors in these samples. Our results provide a scientific basis for preventing and controlling health risks from tap water DBPs and for assessing the social benefits and burdens of emergency disinfection., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The bioaccumulation and translocation of polyhalogenated compounds (PHCs) in rice planted in the paddy soils of an electronic waste (e-waste) recycling site were investigated, along with the effect of contaminated soils on rice growth. The PHCs included polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), decabromodiphenyl ethane (DBDPE), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), and dechlorane plus (DPs). The morphological development and all measured physiological parameters of rice plants except for peroxidase were significantly inhibited by e-waste contaminated soils. Specifically, soil-root bioaccumulation factors (RCFs) increased with increasing logarithm of octanol–water partition coefficient (log Kow ) for PCBs, but decreased for PBDEs. During translocation from root to stem, translocation factors (TFs) and log Kow were positively correlated. However, the accumulation mechanism in the leaf was concentration-dependent. In the high concentration exposure group, translocation play more important role in determination PHCs burden in leaf than atmospheric uptake, with log TF (from stem to leaf) being positively correlated with log Kow . In contrast, in the low exposure and control groups, log TF (from stem to leaf) was negatively correlated with log Kow . In addition, Syn -DP was selectively accumulated in plant tissues. In conclusion, this study demonstrates that e-waste contaminated soils affect rice growth, revealed the rule of the bioaccumulation and translocation of PHCs in rice plants. [ABSTRACT FROM AUTHOR]

Estimating odor emissions from landfill sites is a complicated task because of the various chemical and biological species that exist in landfill gases. In this study, the relative concentration of ethanol and other odorous compounds emitted from the working surface at a landfill in China was analyzed. Gas sampling was conducted at the landfill on a number of selected days from March 2012 to March 2014, which represented different periods throughout the two years. A total of 41, 59, 66, 54, 63, 54, 41, and 42 species of odorous compounds were identified and quantified in eight sampling activities, respectively; a number of 86 species of odorous compounds were identified and quantified all together in the study. The measured odorous compounds were classified into six different categories (Oxygenated compounds, Halogenated compounds, Terpenes, Sulfur compounds, Aromatics, and Hydrocarbons). The total average concentrations of the oxygenated compounds, sulfur compounds, aromatics, halogenated compounds, hydrocarbons, and terpenes were 2.450 mg/m3, 0.246 mg/m3, 0.203 mg/m3, 0.319 mg/m3, 0.530 mg/m3, and 0.217 mg/m3, respectively. The relative concentrations of 59 odorous compounds with respect to the concentration of ethyl alcohol (1000 ppm) were determined. The dominant contaminants that cause odor pollution around the landfill are ethyl sulfide, methyl mercaptan, acetaldehyde, and hydrogen sulfide; dimethyl disulfide and dimethyl sulfide also contribute to the pollution to a certain degree. [ABSTRACT FROM AUTHOR]

Halogenated flame retardants (HFRs) are a class of ubiquitous pollutants in the environment and attract increasing attention. In the present study, HFR concentrations were measured in indoor and outdoor dust in an important industrial city (Dongguan) in southern China, in which their presence and associated human exposure are unknown. The HFRs were dominated by polybrominated diphenyl ethers (PBDEs) and decabromodiphenyl ethane (DBDPE), with mean concentrations of 2365 and 2441 ng/g in the indoor dust, respectively, which were 2–3 order of magnitude higher the concentrations of other HFRs. However elevated tri- to hepta-BDE concentrations (869 ng/g) were found in Houjie Town, a furniture manufacturing center. The mean indoor/outdoor ( I / O ) ratios of HFR concentrations in the dust were all larger than one (1.55–16.4), suggesting the importance of indoors sources for HFRs in indoor dust in this industrial city. Principal component analysis (PCA) showed that the correlations among the HFRs in the indoor dust probably revealed differences in their commercial applications, while most HFRs in the outdoor dust have similar sources except for phased-out BDE47 and 99. The compositions of lower brominated PBDEs varied among the towns, probably due to their different sources or influence of photo-degradation. Nevertheless, the similar composition of highly brominated congeners indicated little photo-degradation encountered in the ambient environment. The non-cancer risk associated with indoor dust ingestion is low for the general population in Dongguan, but some children in the furniture manufacturing center have significantly high risk of exposure to banned PBDEs. [ABSTRACT FROM AUTHOR]

Highlights: [•] DDTs were the most dominant PHCs in Chinese alligators. [•] Both neonates and eggs had significantly higher ∑PCBs and ∑DDTs than adult muscles. [•] DDTs in Chinese alligator eggs could cause sex reversal. [•] First report on PBDEs in crocodilia and first study on PHCs in Chinese alligators. [Copyright &y& Elsevier]

Disinfection byproducts (DBPs) are initially formed in the process of chlorination in the drinking water treatment plants (DWTPs), then further formed in the distribution system due to the presence of residual chlorine and reactive organic matters. However, in China, DBPs are monitored in the effluent from the DWTPs, but less is known about concentrations of DBPs in tap water since they are usually monitored once per half a year. The smart water service system is establishing real-time monitoring of water indices, although DBPs are an urgent need, they are difficult to monitor in real-time due to their diversity and complicated detection methods. If the correlation between DBP concentration and routinely real-time monitored water quality parameters (e.g., pH value, residual chlorine, ammonia) can be evaluated, the concentration of DBPs can be predicted, which will strengthen the control of tap water safety. This article comprehensively assessed the physicochemical parameters and the occurrence of DBP formation in the tap water with an 18-month investigation in Z city (China). DBP formation in tap water of different seasons and different water sources were compared. Based on the relationship between DBPs and physicochemical parameters, linear prediction and nonlinear prediction models of trihalomethanes (THMs), haloacetonitriles (HANs) and haloacetic acids (HAAs) were established, and the accuracy of these models was verified by measured data. Finally, the toxicity and carcinogenic and non-carcinogenic health risk assessment of DBPs in tap water were analyzed., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Highlights: [•] Eight out of twelve HFRs were detected in the sediment from YRD. [•] TBECH and TBPH were first reported in the Chinese marine environment. [•] PBDEs, DBDPE and TBECH were the three predominant HFRs in the sediment. [•] Spatial patterns may indicate that HFRs originated from the eastern region of China. [Copyright &y& Elsevier]

Abstract: The bacterial growth inhibition test was used to determine toxicity of the halogenated aromatics on the mixed bacteria from the Yangtze River. The concentration values causing 50% reduction of bacteria growth for 24 hr (IC 50) and the maximum tolerance concentration for 7 d (MATC) were gained according to the concentration-response curves. An obvious linear relationship was found between the two toxicity descriptors. The following quantitative structure- activity relationships were developed by using the valence molecular connectivity index method: -lgIC 50 =0.8266 X pc v- 0.2363 X p v +3.811 (R 2 =0.833) and -lgMATC=1.2016 X pc v-0.3783 X p v +4.614 (R 2 =0.900). The two equations were found to fit well. It suggested that the models derived from the molecular connectivity index could be used successfully to predict the toxicity of halogenated aromatic compounds. [Copyright &y& Elsevier]

To evaluate the biomagnification extent of polybrominated diphenyls ethers (PBDEs) and polychlorinated biphenyls (PCBs) in a highly contaminated freshwater food web from South China, trophic magnification factors (TMFs) for 18 PBDE congeners and 53 PCB congeners were calculated. The TMF values ranged 0.26–4.47 for PBDEs and 0.75–5.10 for PCBs. Forty-five of 53 PCBs and BDEs 47, 100 and 154 had TMFs greater than one, suggesting their biomagnification in the present food web. The TMFs for PBDEs were generally smaller than those for PCBs with the same degree of halogenation, indicating a lower biomagnification potential for PBDEs compared to PCBs. For PCBs, it followed a parabolic relationship between TMFs and log K OW (octanol-water partition coefficient). However, this relationship was not significant for PBDEs, possibly due to the more complex behaviors of PBDEs in the food web (e.g., metabolism), compared to that of PCBs. [Copyright &y& Elsevier]

Abstract: The Dongjiang River is the major source of drinking water supply for Hong Kong. The deterioration of the water quality of the Dongjiang River and excessive trihalomethanes (THMs) in the tap water of some districts in Hong Kong have become causes for public concern. The main objective of the present study is to investigate and model THM formation due to the chlorination of the Dongjiang River water under different chlorination conditions. The results showed that the total THM formation ranged between 11.7 and 91.8 mg L−1 and that control of the levels was primarily due to the reaction time and the Br− level in the water. Bromide concentration was a key factor in determining bromine-containing THM formation and consequently the speciation of THMs. Higher concentrations of bromide shifted THM species to more-bromine-containing ones, while the kinetics reflected the competing halogenation reactions. As the two mixed-halogen THMs had high cancer potency, the cancer risk of total THMs appeared to reach a peak at a bromide concentration ranging between 218 and 262 mg L−1 (with a bromide to dissolved organic carbon molar ratio (Br−/DOC) ranging between 15 and 18 mM/mM). [Copyright &y& Elsevier]

The widely used antidiabetic drug metformin has become an emerging contaminant of water systems. In a prior study, we demonstrated the marked mammalian toxicity of the disinfection-derived byproducts (DBPs) Y (yellow, C 4 H 6 ClN 5 ) and C (colorless, C 4 H 6 ClN 3 ), and here assess the distribution, formation, and ecotoxicity of these in Chinese urban water systems. A national tap water assessment showed that metformin and C concentrations were higher in large, dense urban areas and surface water sources than in sparsely populated areas and groundwater sources. Water types' analysis clearly showed that C derived from chlorination of metformin-contaminated water (up to 4308.5 ng/L) circulated from domestic water (0.7-9.7 ng/L) via sewage (2.3 ng/L in effluent) to surface water (0.6-3.5 ng/L). Simulated disinfection and aqueous stability results systematically showed rapid formation and 24 h stability of both byproducts, indicating high exposure odds for water users. Both byproducts showed clear but distinct toxic effects on the growth (72 h IC 50 , 0.6 mg/L for Y and 4.4 mg/L for C) and photosynthesis of the microalgae Pseudokirchneriella subcapitata at milligram levels. Combinedly, our work reveals that metformin byproducts have been disseminated to urban water cycle and contaminated tap water, increasing potential toxic risk for drinking water. Its outcomes provide a preliminary reference for future studies on the environmental fate and ecotoxicological effects of unintended DBPs formed in the chlorination of metformin-contaminated water., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Technical chlorinated paraffins (CPs) are produced via radical chlorination of n-alkane feedstocks with different carbon chain-lengths (∼C 10 -C 30 ). Short-chain CPs (SCCPs, C 10 -C 13 ) are classified as persistent organic pollutants (POPs) under the Stockholm Convention. This regulation has induced a shift to use longer-chain CPs as substitutes. Consequently, medium-chain (MCCPs, C 14 -C 17 ) and long-chain (LCCPs, C > 17 ) CPs have become dominant homologues in recent environmental samples. However, no suitable LCCP-standard materials are available. Herein, we report on the chemical synthesis of single-chain C 18 -CP-materials, starting with a pure n-alkane and sulfuryl chloride (SO 2 Cl 2 ). Fractionation of the crude product by normal-phase liquid-chromatography and pooling of suitable fractions yielded in four C 18 -CP-materials with different chlorination degrees (m Cl,EA  = 39-52%). In addition, polar side-products, tentatively identified as sulfite-, sulfate- and bis-sulfate-diesters, were separated from CPs. The new single-chain materials were characterized by LC-MS, 1 H-NMR and EA. LC-MS provided Relative retention times for different C 18 -CP homologues and side-products. Mathematical deconvolution of full-scan mass spectra revealed the presence of chloroparaffins (57-93%) and chloroolefins (COs, 7-26%) in the four single-chain C 18 -CP-materials. Homologue distributions and chlorination degrees were deduced for CPs and COs. 1 H-NMR revealed chemical shift ranges of mono-chlorinated (δ = 3.2-5.3 ppm) and non-chlorinated (δ = 1.0-3.2 ppm) hydrocarbon moieties. The synthesized C 18 -single-chain standard materials and respective spectroscopic data are useful to identify and quantify LCCPs in various materials and environmental samples. CP- and CO-distributions resemble the ones of existing SCCP and MCCP reference materials and technical mixtures. Furthermore, these materials now allow specific studies on the environmental fate and the transformation of long-chain chloroparaffins and chloroolefins., (Copyright © 2021 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Halobenzoquinones (HBQs) are emerging unregulated drinking water disinfection byproducts (DBPs) that are more toxic than regulated DBPs. This study aimed to determine the distribution and formation of HBQs in drinking water from water treatment plants in China, compare their chronic cytotoxicity and their induction of chromosomal damage in Chinese hamster ovary cells, and analyze the correlation of HBQ toxicity with their physicochemical parameters. Two HBQs, 2,6-dichloro-1,4-benzoquinone (2,6-DCBQ) and 2,6-dibromo-1,4-benzoquinone (2,6-DBBQ), were detected in finished water and tap water in China. The concentrations were in the ranges of <2.6-19.70 ng/L for 2,6-DCBQ and <0.38-1.8 ng/L for 2,6-DBBQ. Chemical oxygen demand and residual chlorine were positively correlated with HBQ formation. The HBQ concentration was lower in a drinking water treatment plant using chlorine dioxide. High Ca 2+ in tap water decreased the HBQ level. The rank order of HBQ by cytotoxicity was 2-chloro-1,4-benzoquinone > 2,3-diiodo-1,4-benzoquinone > 2,6-diiodo-1,4-benzoquinone > 2,6-dibromo-1,4-benzoquinone > 2,5-dibromo-1,4-benzoquinone > 2,5-dichloro-1,4-benzoquinone > 2,6-dichloro-1,4-benzoquinone > tetrachloro-1,4-benzoquinone > 2,3,6-trichloro-1,4-benzoquinone, and for their genotoxicity, 2,5-dichloro-1,4-benzoquinone > 2,6-dichloro-1,4-benzoquinone > 2,3-diiodo-1,4-benzoquinone > 2,6-diiodo-1,4-benzoquinone > tetrachloro-1,4-benzoquinone > 2,5-dibromo-1,4-benzoquinone > 2,6-dibromo-1,4-benzoquinone > 2,3,6-trichloro-1,4-benzoquinone. The cytotoxicity of six dihalo-HBQs was negatively correlated with the octanol-water partition coefficient (r = -0.971, P < 0.05), molar refractivity (r = -0.956, P < 0.05), energy of the highest occupied molecular orbital (E HOMO ) (r = -0.943, P < 0.05), and polar surface area (r = -0.829, P < 0.05). The genotoxicity of these three pairs of dihalo-HBQ isomers followed the same order as their E HOMO values. This study reveals the occurrence and formation of HBQs in drinking water in China and systematically evaluates the chromosomal damage caused by nine HBQs in mammalian cells., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The reuse of the sewage is an effective way to solve the shortage of water resources, but disinfection by-products (DBPs) caused by chlorination may bring potential ecological and health risks to the supplied water. In this study, the occurrence and potential ecological risk of DBPs in SH River in Beijing were evaluated. Four kinds of DBPs were detected in 84 samples by GC-MS, including THM, CH, CTC and TCAN, whose detection rates were 100%, 100%, 100% and 2.38%, respectively. Combining with the relevant standard limitation and corresponding threshold values in China, and the reported concentration in domestic and foreign literatures, the results showed that the number of samples which [THM], [CTC] and [CH] exceeded the threshold values in relevant standard for 23.81%, 100.00% and 89.29%, respectively. CTC showed the highest excess times than the threshold value with [CTC] max was 356.46 μg/L. In addition, the temporal and spatial characteristics of identified DBPs were studied. [THM], [CTC] and [CH] all exhibited the highest concentration in Aug., which was as the same as the variation trend of air and water temperature. With the increase of sampling distance, [THM] and [CTC] fluctuated greatly, and the background values in SH River were higher due to the supplement of the reclaimed water. [CH] and [TCAN] gradually decreased, which may be due to that they were more prone to volatilize in the channel and be degraded by aquatic microorganisms. In addition, the occurrence situation in S2 and S7, were in the order of CTC > CH > THM. Hence, the rank of the occurrence situation of identified DBPs was CTC > CH > THM > TCAN. Multivariate analysis showed that THM was significantly positively correlated with CTC and their sources were similar. Moreover, they were all affected by solution pH and DO. Potential ecological risk assessment indicated that the rank of identified DBPs ecological risk was CTC > THM > CH > TCAN. Among them, the risk level of CTC and THM were high in both daily and extreme situations. Therefore, the potential ecological risk caused by DBPs should be fully considered in the process of reclaimed water supplying landscape water, such as urban river. If a higher level of the ecological risk management is needed, THM, CTC and CH, especially CTC, should be considered firstly., (Copyright © 2021 The Authors. Published by Elsevier Inc. All rights reserved.)

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.

Several in vitro and in vivo studies have demonstrated the toxicity of perfluoroalkyl and polyfluoroalkyl substances (PFASs) alternatives, however, relevant epidemiological findings remain to be performed. In addition, the association between PFASs alternatives and blood pressure has not been explored. To address this gap, we quantified serum levels of alternatives and legacy PFAS in 1273 healthy Chinese, aged 34-94 years, from "isomers of C8 health project". Our results showed that an increase of serum PFASs levels was correlated with elevated blood pressure and higher prevalence of hypertension: per natural log unit (ng/mL) increase of 6:2 chlorinated polyfluorinated ether sulfonic acids (Cl-PFESA) elevated 1.31 (95%CI: 0.13, 2.50) mmHg of diastolic pressure (DBP). Adjusted odds ratios (aORs) for hypertension with per natural log increase of 6:2 and 8:2 Cl-PFESA were 2.57 (95%CI: 1.86, 3.56) and 1.18 (95%CI: 1.06, 1.32), respectively. When stratified by sex, the effects of PFASs alternatives on increased blood pressure and hypertension were stronger in women. Meanwhile, the association between 6:2 Cl-PFESA (aOR = 6.81; 95%CI: 3.54, 13.09) and hypertension was stronger than perfluorooctanoic acid (PFOA) (aOR = 2.32, 95%CI: 1.38, 3.91) in women. In conclusion, our pilot study demonstrates that serum concentrations of PFASs alternatives are positively associated with blood pressure. Moreover, women seem to be more susceptible, and alternatives exhibited stronger effects than legacy PFASs., Competing Interests: Declaration of competing interest All authors declare tey have no actual or potential relationships that could be construed as a conflict of interest., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Chlorinated paraffins (CPs) are highly complex mixtures of polychlorinated n -alkanes with differing chain lengths and chlorination patterns. Knowledge on physicochemical properties of individual congeners is limited but needed to understand their environmental fate and potential risks. This work used a sophisticated but time-demanding quantum chemically based method COSMO-RS and a fast-running fragment contribution approach to enable prediction of partition coefficients for a large number of short-chain chlorinated paraffin (SCCP) congeners. Fragment contribution models (FCMs) were developed using molecular fragments with a length of up to C 4 in CP molecules as explanatory variables and COSMO-RS-calculated partition coefficients as training data. The resulting FCMs could quickly provide COSMO-RS predictions for octanol-water ( K ow ), air-water ( K aw ), and octanol-air ( K oa ) partition coefficients of SCCP congeners with an accuracy of 0.1-0.3 log units root-mean-squared errors. The FCM predictions for K ow agreed with experimental values for individual constitutional isomers within 1 log unit. The distribution of partition coefficients for each SCCP congener group was computed, which successfully reproduced experimental log  K ow ranges of industrial CP mixtures. As an application of the developed FCMs, the predicted K aw and K oa were plotted to evaluate the bioaccumulation potential of each SCCP congener group.

To investigate the status of organophosphate flame retardants (OPFRs) in indoor dust in China, published scientific studies were systematically collected and analyzed. The analysis revealed large variations among microenvironments, including offices (median: 14.59 μg/g) and e-waste workshops (median: 13.36 μg/g), with high levels of OPFRs contamination. Chlorinated organophosphate ester flame retardants (Cl-OPFRs) were the dominant OPFRs (52-75%) in most indoor dust samples; however, in e-waste workshops, aryl- and alkyl-OPFRs were the most abundant. As an alternative flame retardant to polybrominated diphenyl ethers (PBDEs), OPFRs concentrations have increased in recent years in indoor environments in China. Urban sources are of greatest concern: Shanghai (mean: 13.54 μg/g), Guangzhou (mean: 10.76 μg/g), and Beijing (mean: 9.37 μg/g) have high ΣOPFRs contamination levels in indoor dust. Compared to other countries, the OPFRs concentrations in indoor dust in all studied microenvironments from China (median: 8.81 μg/g) were low. The estimated daily intakes of ΣOPFRs by dust ingestion for adults and children were 2.12 and 11.06 ng/kg/body weight/day (average), respectively. Human exposure to OPFRs through the accidental intake of indoor dust does not pose a direct health risk to the Chinese population. However, indoor dust ingestion is an important route for human exposure to OPFRs., Competing Interests: Declaration of competing interest This manuscript is an original work, it has not been previously published, and it is not under consideration for publication elsewhere. All authors have read the manuscript, agree that the work is ready for submission to a journal, and accept responsibility for the manuscript’s contents. All authors have disclosed any competing financial interests in this work, and in fact, there were none., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

In this paper, a comprehensive method for the identification of the unknown halogenated DBPs (X-DBPs, X = Cl, Br, and I) in the tap water of Wuhan, China via liquid chromatography-high resolution mass spectrometry (LC-HRMS) was developed. 123 X-DBPs were identified through the stepwise procedure, 94 of them were newly identified, and 3 of them were confirmed by standards. Most X-DBPs were aliphatic compounds and highly unsaturated and phenolic compounds, some X-DBPs contained multiple halogen atoms and rich in carboxyl groups, such as C 2 H 2 O 2 BrCl, C 2 H 2 O 2 Br 2 , and C 2 H 2 O 2 ClI. It was worth noting that the concentration of some X-DBPs had the same trend with time. Most Cl-DBPs remained stable and I-DBPs were detected occasionally by monitoring the change of concentration of these X-DPBs with the time during three consecutive months. The results demonstrate that the proposed method could provide valuable molecular formula and structure information on unknown multiple halogenated DBPs, or be used for the identification of other multiple halogenated organic compounds in different media., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

In a 3-day duplicate diet study of a nursing mother-infant cohort (n = 20), the levels of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD), and 5 novel brominated flame retardants (BFRs) were measured in 60 24-h duplicate diet samples and 20 breast milk samples provided by the mothers. The dietary BFR intake and related health risks of the mothers and their babies due to food consumption or human milk ingestion were subsequently assessed. At median concentrations of 284, 264 and 177 pg/g wet weight (ww) in the diet, decabrominated diphenyl ethers (BDE-209), decabromodiphenyl ethane (DBDPE) and HBCDD were predominant among the total BFRs. In human milk, HBCDD was the most abundant BFR, followed by BDE-209 and DBDPE, which indicates that BDE-209 and HBCDD have remained ubiquitous in the environment because of their continuous production and use in China. Meanwhile, concentrations of DBDPE were comparative to those of PBDEs and HBCDD in both diet and human milk, and DBDPE also had much higher concentrations than any other NBFRs, which indicates that the BFR consumption pattern in China is shifting from legacy BFRs to NBFRs. The median estimated dietary intakes (EDIs) of BDE-209, HBCDD and DBDPE for the mothers were 6.83, 3.73 and 5.44 ng/kg bw/day, respectively, and EDIs for their nursing babies were 24.7, 41.9 and 7.83 ng/kg bw/day, respectively. The nursing infants showed higher BFR body burden than the mothers. However, the EDIs obtained for both mothers and their babies discloses a low health risk to this mother-infant cohort., Competing Interests: Declaration of Competing interest We have no conflict of interest to declare., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Halogenated aromatic disinfection byproducts (DBPs) are a new group of emerging DBPs identified recently. They have been detected in disinfected drinking water, wastewater effluents, recreational water and oil/gas produced water, at concentrations of ng/L to μg/L in general. Previously studies have demonstrated that most of them can induce developmental toxicity and growth inhibition in aquatic organisms based on in vivo bioassays. In this study, to further understand the adverse effects of aromatic DBPs to human health, the comparative cytotoxicity of 15 halogenated aromatic DBPs belonging to four subgroups (i.e., halophenols, halonitrophenols, halohydroxybenzaldehydes and halohydroxybenzoic acids) was evaluated with mammalian Chinese Hamster Ovary cells. The results indicated that the selected aromatic DBPs exhibited an in vitro toxicity rank order of halonitrophenols > halophenols > halohydroxybenzaldehydes > halohydroxybenzoic acids. The potential toxicity mechanisms involved with the antioxidant system were investigated by using molecular docking analysis between key antioxidant enzymes (i.e., catalase, superoxide dismutase, and glutathione S-transferase) and aromatic DBPs. Based on the observed cytotoxicity data and screening the candidate descriptors (including binding energies between the aromatic DBPs and key antioxidant enzymes as well as physical-chemical/quantum-chemical/topological descriptors), a QSAR model was developed as log (LC 50 ) -1  = - 1.050E CAT  + 0.300E HOMO  - 0.238E LUMO - 0.164, indicating the importance of the interactions of aromatic DBPs towards catalase and the electrophilic/nucleophilic reactivity of aromatic DBPs in the toxicity mechanisms. In addition, the occurrence of the aromatic DBPs in tap water and finished water was studied in a mega city Shenzhen located in South China. Results showed that halogenated aromatic DBPs commonly existed in Shenzhen drinking water at ng/L levels, and three nitrogenous aromatic DBPs were detected in real drinking water for the first time. The major toxicity drivers among the target aromatic DBPs were identified through the integration of the measured concentrations and observed cytotoxicity; notably, DBPs with the highest concentrations may not contribute the highest proportions of overall toxicity., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Disinfection by-products (DBPs) play a significant role in human health. Identification of the precursor of DBPs, which constitutes dissolved organic matter (DOM), can help optimize the processes in a drinking water treatment plant (DWTP). This is very important for obtaining more safe water. In this context, a one-year study was performed in a DWTP. Fluorescence spectra of DOM were quantified for determining DOM composition and properties, and the corresponding DBPs formation was analyzed. Hydrophobic neutral and acidic compounds were found to be the two predominant substances forming DBPs, which also were dominant in the DOM. Coagulation and sedimentation were not effective in DOM elimination. Besides, sand filtration caused organic compounds to increase by 14.8% on average, especially 28.59% for aromatic protein II and 18.7% for soluble microbial product-like compounds, which was due to metabolism by microorganisms present in the filter. Carbonaceous DBPs were elevated from 34.8 μg/L in source water to 42.5 μg/L in effluent, along with organic compounds increasing in filtration, and nitrogenous DBPs were under detection in winter. All DBPs appeared at a high level in summer. Accordingly, enhanced coagulation process and measures that can avoid the release of organic compounds during filtration have been suggested. As the source water was rarely affected by human activities in the study area and owing to the wide use of traditional treatment process, the data of this research can be regarded as environmental background values and the results are considered as a significant reference., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The bromide concentration in water source (WS) of Yancheng City in China increased unexpectedly due to industrial discharge and saltwater intrusion, which leads to the formation of trihalomethane (THMs) in finished water of water treatment plants (WTP), especially brominated THMs. In Yancheng City, drinking water is supplied by WTP1 and WTP2, primarily sourced by WS1 and WS2, respectively. In this paper, the seasonal variations of bromide in WS1 and WS2 and THMs species in WTP1 and WTP2 were analyzed and compared. The effects of bromide in WS on THMs formation in finished water of WTP in terms of bromine substitution factor (BSF) were simulated by statistical linear model. Although the THMs concentrations in WTP1 were approximate to that in WTP2, the brominated THMs concentrations in WTP1 were higher than that in WTP2 due to higher bromide concentration in WS1 than WS2. The cancer risk analysis indicated that THMs' species of DBCM is the dominant THMs for WTP1 as well as WTP2, which can provide more information for WTPs with higher bromide concentration in water source.

The chemical industrial zone located along the Xiaoqing River wetlands adjacent to Bohai Sea is one of the largest production bases for brominated flame retardants in China. Herein, high levels of bisphenol-A, tetrabromobisphenol-A (TBBPA), tribromobisphenol-A, dibromobisphenol-A, and monobromobisphenol-A were detected in sediment, soil, and water samples of this zone in the range of below method detection limit (6  ng/kg dw, 4  ng/kg dw, and 2  ng/L, respectively. They were mainly buried in sediments as their highest levels in sediment samples. The small concentration fluctuation between water samples retrieved in the upstream and downstream zones is likely attributed to seawater backflow. The nearby chemical factories were point pollution sources and the less brominated analogs are largely from debromination of TBBPA. High pollution levels and the ecological risks of these pollutants along the Xiaoqing estuary to Bohai Sea need to be further assessed in future studies., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

This study investigated formation and genotoxicities of disinfection by-products (DBPs) during chlorination of hydrophobic organic compounds (HOCs) extracted from six drinking water reservoirs around the Pearl River Delta region, China. Chemical analyses firstly showed that after chlorination aromatic HOCs (including polycyclic aromatic hydrocarbons, PAHs) decreased but DBPs (including chlorinated PAHs) increased, while genotoxicity assays revealed that the chlorination increased DNA damage in human Caco-2 cells. Although the link between DBPs and the genotoxicity was weak (insignificant correlations, p ≥ 0.05), we observed that chlorination of HOCs from more contaminated reservoirs in general resulted in higher genotoxicity. Secondly, remedial effects of catalase and dietary antioxidants (i.e. vitamin C and epigallocatechin gallate) in protecting cells against DBPs genotoxicity were detected. After 1 h treatment by the antioxidants, the DNA damage in Caco-2 cells (due to previous exposure to DBPs) significantly decreased (p < 0.05) in 7 out of a total of 18 treatments (38.9%). This is the first study demonstrating that catalase, vitamin C and epigallocatechin gallate protected human cells in vitro against DNA damage upon exposure to chlorinated genotoxic DBPs., (Copyright © 2019 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The occurrence, seasonal variation and emission of nine widely used phosphorus flame retardants (PFRs) were investigated in a wastewater treatment plant (WWTP) located in Guangzhou, China, over 1 year. Results showed that PFRs were widely detected in wastewater and sewage sludge. Tris(2-chloroisopropyl) phosphate (TCIPP) was the most dominant PFRs in influent, effluent, and sludge. Significant seasonal variation of total PFRs in the influent was observed (p < 0.05). However, no significant seasonal variation found in chlorinated and alkyl PFRs. The emission of PFRs was comparable with the previously reported values of decabromodiphenyl ether in WWTPs. Risk quotient for PFRs showed low eco-toxicity risk in effluent for aquatic organisms. Since the removal efficiency of total PFRs was less than 30% and the use of PFRs had been increasing, continuous monitoring of the environmental impact on the receiving water is still needed.

Carbamate insecticides, which are common micropollutants in surface waters, were found to generate dichloromethlyamine (DCMA) during chlorination. DCMA formation from other precursors has been reported previously; it is part of the emerging class of nitrogen-based disinfection byproducts (N-DBPs) of health concern in chlorinated water. However, there is a limited understanding about its formation, stability, and toxicity. Four carbamate insecticides (methomyl, carbofuran, carbaryl, and thiodicarb) were examined as DCMA precursors over a range of reaction conditions, based on variables of chlorine/precursor (Cl/P) molar ratio, pH, time, and temperature. DCMA was found to be the dominant volatile DBP to result from chlorination of all four carbamate insecticides, with molar yields ranging from 12% to 150% at a Cl/P molar ratio of 20. Further experiments indicated CH 3 NCl 2 to be relatively stable, with a half-life of up to 35 h in water. The toxicity of CH 3 NCl 2 was investigated using a bacterial bioluminescence inhibition test and survival of human lung tumor cells. The results of these toxicity assays indicated that CH 3 NCl 2 is about 3 orders of magnitude more toxic than CHCl 3 . CH 3 NCl 2 concentrations in the ppb range were observed to result from chlorination of surface water or tap water samples collected from several different locations in China. The results suggest that precursors to CH 3 NCl 2 formation are ubiquitous and that CH 3 NCl 2 poses a hazard to public health and the environment and should be considered in disinfection chemistry and water treatment.

With the phasing out of traditional polybrominated diphenyl ethers (PBDEs), significant volumes of alternative brominated flame retardants (aBFRs) are being used and released into the environment compartment, especially in coastal regions. The levels and distribution of PBDEs, aBFRs, and dechlorane plus (DPs) were investigated in the surface sediments of the Yellow Sea (YS) and East China Sea (ECS) to examine the distribution and sources of these hydrophobic contaminants. The level and distribution of pollutants in the sediments of YS and ECS show obvious regional differences. As a major replacement for decabromodiphenyl ether (BDE 209), decabromodiphenyl ethane (DBDPE) was the dominant compound observed in the surface sediments, with a concentration one order of magnitude higher than that of BDE 209. High concentrations were found in the depositional zones of the YS, indicating that these contaminants may originate from land-based pollution sources (likely from the Laizhou Bay manufacturing base) near the Bohai Sea. The pollutants can be carried by the coastal current together with the sediment from the Yellow River, transported through the Bohai Strait and deposited in the mud zone of Northern and Southern YS. Low levels of halogenated flame retardants (HFRs) were found in the estuary of the Yangtze River and ECS, indicating that Yangtze River contributes less HFRs to the region. Riverine discharge, atmospheric deposition, surface runoff, ocean current system, and mud area deposition effects may be significant factors influencing the distributions of HFRs., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

F-53B (6:2 chlorinated polyfluorinated ether sulfonate) is currently recognized as a safe alternative to long-chain PFASs in China. However, an increasing number of studies have recently authenticated its biotoxicological effects. In this study, for evaluating the gut toxicity of F-53B in mammals, both female and male mice were orally exposed to 0, 1, 3, or 10 μg/L F-53B for 10 weeks. Our results showed that F-53B significantly accumulated in the colon, ileum and serum when exposed to 10 μg/L F-53B for 10 weeks. F-53B exposure not only increased the transcriptional levels of ion transport-related genes but could also interact with the CFTR protein directly. Interestingly, subchronic F-53B exposure also increased the transcription of mucus secretion-related genes, but the protein level of Muc2 decreased after F-53B exposure, indicating that there was a compensatory phenomenon after mucus barrier injury. Furthermore, F-53B exposure also induced colonic inflammation associated with gut microbiota dysbiosis in the colon. Taken together, our results indicated that the potential gut toxicity of F-53B and almost all of the changed parameters were significantly affected in both female and male mice, suggesting that F-53B could disturb the gut barrier without sex dependence in mice., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Natural attenuation of polychlorinated biphenyls (PCBs) by indigenous bacteria is an effective remediation strategy for polluted marine sediments. This study investigated the relationships between PCB concentrations in sediment pore water, humin electron transfer capacity, and potential PCB dechlorinators at eight sediment sampling sites in the southern Yellow Sea, China, with differential PCB contamination. Station A2 showed the highest PCB concentration (453.16 ng L -1 for seven indicator PCBs), especially of less chlorinated PCB congeners (≤5 Cl atoms), humin redox activity, and Dehalococcoides abundance (p < 0.05). Statistical analyses revealed a highly positive correlation between Dehalococcoides abundance and PCB concentration (r = 0.836, p < 0.05) and the electron shuttling ability of humins (r = 0.952, p < 0.01), whereas this was not observed for total bacteria and other potential PCB dechlorinators, e.g., Dehalobacter and Dehalogenimonas. Based on these results, Dehalococcoides might play an important role in the in situ reductive dechlorination of PCBs involving humins in marine sediments, and the natural microbial PCB attenuation capacity at station A2 was high. Chemical characterizations, electrochemical properties, and Fourier transform infrared analysis suggested that humins at station A2 had the highest electron transfer capacity. Furthermore, quinones are likely to be the functional groups that shuttle electrons during PCB dechlorination. Overall, this study provides a useful foundation for evaluating the natural microbial attenuation potential and fates of PCBs in marine sediments and for determining the role of humins as redox mediators in in situ PCB dechlorination by putative indigenous dechlorinators., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Polybrominated diphenyl ethers (PBDEs), decabromodiphenyl ethane (DBDPE), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCDD) and dechlorane plus (DP) were measured in sediments collected from three mangrove wetlands of the Pearl River Estuary (PRE) in South China. This study aims to investigate the distribution of these halogenated flame retardants (HFRs) and the correlations between HFRs and microbial community structure in mangrove sediments. Concentrations of PBDEs, DBDPE, BTBPE, TBBPA, HBCDD and DP in mangrove sediments ranged from 6.97 to 216.1, 3.70-26.0, 0.02-0.73, 0.02-37.5, 0.44-127.5 and 0.07-2.23 ng/g dry weight, respectively. Higher levels of PBDEs, BTBPE, HBCDD and DP were observed in sediments from Futian mangrove wetland of Shenzhen, the only nature reserve located in the downtown of China. The highest concentration of TBBPA found in mangrove sediments from Guangzhou was proximate to a ferry terminal and a dockyard where TBBPA is widely used in the coatings. PBDEs were the predominant HFRs in mangrove sediments, with an average contribution of 63.0%. Mangrove sediments from Guangzhou and Zhuhai showed an enrichment of (-)-α-HBCDD, (-)-β-HBCDD and (-)-γ-HBCDD. Concentrations of HFRs in mangrove sediments from Guangzhou increased significantly from 2012 to 2015, which was probably due to the establishment and rapid development of Nansha Free Trade Zone of Guangzhou. Redundancy analysis showed that HFRs may cause a shift of microbial community structure in mangrove sediments and the variations were significantly correlated with TBBPA, syn-DP and BTBPE., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Effluents containing disinfection byproducts (DBPs) from wastewater treatment plants (WWTPs) may be discharged to the receiving water bodies or reused for irrigation, landscaping, and environmental supplies as well as a source to replenish groundwater. Thus the formation and risk of the DBPs in disinfected wastewater effluents should be concerned. In this study, the occurrence of 44 DBPs including 6 trihalomethanes (THMs), 9 haloaceticacids (HAAs), 2 haloketones (HKs), 9 halonitromethanes (HNMs), 9 haloacetonitriles (HANs) and 9 nitrosamines (NAs) was investigated in 12 chlorinated WWTP effluents from five cities of East China. The contribution of each class of DBPs to the total DBPs concentration and additive toxicity was calculated. The average concentrations of the 6 classes of DBPs were ranked as follows: HAAs (47.0 μg/L) > THMs (28.0 μg/L) > HANs (9.9 μg/L) > HNMs (2.9 μg/L) > HKs (0.79 μg/L) > NAs (0.69 μg/L). The significant positive correlations were observed between the formation of THMs and HAAs, THMs and HANs, as well as HAAs and HANs. The results showed that HAAs and THMs were the dominant DBPs on a mass concentration basis and accounted for 54% and 29%, respectively in the total measured DBPs, but they made a minor contribution to the calculated DBP-associated cytotoxicity. HANs and NAs dominated the DBP-associated cytotoxicity, accounting for 50% and 34% on an additive toxicity basis despite the minor contributions to the mass concentration with 10% and 1%, respectively. The risk quotients for three taxonomic groups (fish, daphnid, and green algae) were calculated to assess the ecological risk of DBPs, and the results demonstrated that both HAAs and HANs had high ecological risk for green algae in chlorinated wastewater effluents., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Trihalomethanes (THMs) and adsorbable organic halides (AOX) were generated in chlorinated water. The purpose of the study was to provide a comprehensive picture of concentration distribution, the seasonal and different water source variability of THMs and AOX. Data for THMs, AOX, and other physico-chemical parameters were from 538 samples of 16 drinking water work through a 3-year sampling program which was conducted in Shandong province with typical temperate and monsoonal climate. Selected samples were considered with the influence of factors such as season, water source, and disinfectant. The THMs and AOX concentration of the samples disinfected with chlorine ranged from 2.1-105 μg/L and 11-238 μg/L, respectively. The THMs and AOX concentration of the samples disinfected chlorine dioxide ranged from N.D.-47.6 μg/L and N.D.-102 μg/L, respectively. The median concentration of THMs and AOX of samples disinfected with chlorine were 35 μg/L and 61 μg/L, much higher than chlorine dioxide, respectively. Ninety-two percent of the samples disinfected with chlorine and all samples disinfected with chlorine dioxide met Chinese drinking water standard for THMs. The ratio of tribromethane (TBM) to THMs of samples disinfected with chlorine was 19%, lower than chlorine dioxide 42%. Bromine substitution factor (BSF) of THMs and initial concentration of bromide showed weak correlation, and the Spearman correlation coefficient was 0.38. THMs and AOX concentrations showed noticeable seasonal variations with the highest median concentrations in spring. The levels of THMs and AOX in drinking water varied with different water sources and followed the order local reservoir > Yellow River reservoir > ground water. The survey results complement the database of THMs and AOX occurrence in drinking water in China, and offer a significant reference data for setting disinfections by-products occurrence in countries or regions with similar climate around the world.

In this study, pine needles were used as biomonitors to investigate the levels, spatial distributions, and possible sources of polybrominated diphenyl ethers (PBDEs) and four emerging halogenated flame retardants (HFRs) in the atmosphere of Shanghai, China. The four emerging HFRs were hexabromocyclododecane (HBCD), decabromodiphenylethane (DBDPE), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), and dechlorane plus (DP), with the first 3 HFRs being non-polybrominated diphenyl ether brominated flame retardants (non-PBDE BFRs). The total concentrations ranged from 3.71 to 4020 ng g -1 dry weight (dw) for 52 PBDE congeners (Σ 52 BDEs), < MDL (method detection limit) to 15.2 ng g -1 dw for three non-PBDE BFRs (Σ 3 non-PBDE BFRs), and 0.815 to 1090 pg g -1 dw for two DP isomers (ΣDP), respectively. High levels of PBDEs, three non-PBDE BFRs, and DP were found in pine needles from suburbs and Pudong, which was a consequence of industrial activities. The fraction of anti-DP isomer (f anti ) in pine needles ranged from 0.515 to 0.939 with a mean value of 0.721, and most of the f anti values were consistent with those of technical DP formulations. Principal component analysis-multiple linear regression (PCA-MLR) model identified four sources of PBDEs in pine needles with the quantified contributions: degradation of technical PBDE formulations (49.5%), technical deca-BDE (6.9%), technical penta-BDE (25.1%), and technical octa-BDE (18.5%). These findings are expected to help understand the pollution level, fate, and possible sources of HFRs in the atmosphere of Shanghai and provide a basis for air pollution control and management in Shanghai.

Municipal wastewater treatment plants (WWTPs) are an important reservoir for heavy metal (e.g., Hg and Ag) resistance genes and antibiotic resistance genes (ARGs). However, current knowledge on Hg/Ag resistance genes and their association with ARGs in WWTPs remains largely unknown. In this study, the fates of five Hg/Ag resistance genes (merB, merD, merR, silE, and silR), five ARGs (sulI, sulII, tetO, tetQ, tetW), and class 1 integrase (intI1) in a WWTP were investigated. Results show that the absolute abundances of all target genes were greatly reduced through the treatment systems. The dynamics of merB, merD and silE were significantly correlated with tetW and sulII. Based on network analysis, Hg/Ag resistance genes might share the same microbial hosts with tetQ and tetW, implying the potential importance of Hg/Ag in ARGs evolution and spread. These findings advanced our understanding of the occurrence of Hg/Ag resistance genes and ARGs in WWTPs., (Copyright © 2018 Elsevier B.V. All rights reserved.)

A comprehensive spatio-vertical survey of short-chain (SCCPs, C 10-13 ) and medium-chain (MCCPs, C 14-17 ) chlorinated paraffins (CPs) was performed in surface and core soils from Chinese nation-wide agricultural lands in 2016, and a total of 48 congener groups were measured. The shorter carbon chain C 10-11 in SCCP and C 14-15 in MCCP homologue groups, and the lower chlorinated congeners (Cl 5-7 ) for both CP groups were predominant. The ∑SCCP and ∑MCCP concentrations in surface soils ranged from 39 to 1609 ng/g and 127-1969 ng/g, dry weight (dw), respectively. The spatial distribution trend showed that SCCP congener groups with relatively low octanol-water partition coefficient (K OW ) and octanol-air partition coefficient (K OA ) are uniformly distributed across surface soils compared to MCCP congener groups. Significant relationships were observed between the spatial variation of SCCP concentrations and the driving factors responsible for dispersion and deposition. The distribution behavior of SCCPs and MCCPs in highland and plain surface soils showed an increasing trend of MCCP concentrations with elevation, indicating the "mountain cold-trapping effect". Vertical distribution profile revealed similar homologue group composition patterns of SCCP and MCCP congener groups as those of surface soils. Furthermore, the penetration potential ratios (r) of chlorine and carbon atoms of CPs demonstrated that the lower chlorinated (Cl 5-7 ) and the shorter carbon chain (C 10-13 ) congener groups are more prone to vertical movement into deeper soil layers compared to the longer carbon chain (C 14-17 ) and highly chlorinated (Cl 8-10 ) congener groups., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Fluoroquinolones (FQs) are very ubiquitous in water environment in China. The commonly application of free available chlorine (FAC) during water treatment stimulated the focus on the transformation of FQs during chlorination. Among these FQs, norfloxacin (NOR) and ofloxacin (OFL) are the representatives of secondary amine FQs and tertiary amine FQs, respectively. To better understand the difference between secondary amine FQs and tertiary amine FQs during chlorination, reaction kinetics, products and mechanisms were determined. The maximum k app of NOR were four orders of magnitude higher than that of OFL. Moreover, eleven products of NOR and twelve products of OFL were obtained by LC-MS/MS analysis. For the two FQs, the common reactive sites were three nitrogen atoms, benzene ring, carboxyl group and double bond by chlorination. For OFL, the ether ring was also active in aqueous system. The formation mechanisms of these products were presented in this study. The main reaction pathways were electrophilic addition to nitrogen, nucleophilic substitution to benzene ring, halodecarboxylation of carboxyl group and hydrolysis of ether ring. Na 2 S 2 O 3 as a reducing agent had large effect on the chlorination of secondary amine FQ, but no effect on tertiary amine FQ. Be different to secondary amine FQ, the opening of quinolone ring happened in tertiary amine FQ after halodecarboxylation of carboxyl group., (Copyright © 2018. Published by Elsevier Ltd.)

Chlorinated paraffins (CPs) are now attracting special concerns worldwide as one type of new persistent toxic substances as classified by the Stockholm Convention. CPs are extensively applied in household goods and indoor decoration materials, but information on their occurrence and exposure risk in such environments is still very scarce. In this study, the current concentrations, particle size distributions, and inhalation exposure characteristics and risk of CPs were investigated in regard to indoor air particulate matter. Both short chain (SCCPs) and medium chain CPs (MCCPs) were determined in all size-fractioned particle samples with a range of 6.20-17.8 and 5.98-40.5 ng m -3 , respectively. MCCPs were more abundant than SCCPs. Size distributions revealed that individual homologs, SCCPs, and MCCPs exhibited a similar unimodal distribution peaking in the fine particles with a diameter of 0.56-1.0 μm. The relative abundance of longer-chain or more heavily chlorinated homologs tend to gradually increase with particle size shift from coarse to fine mode. Vapor pressure may be a critical factor governing the size-dependent distribution of CPs. Deposition of particulate CPs in the human respiratory tract is also size-dependent. The contributions of fine particles to the regional depositions of CPs in the human respiratory tract increase with increasing carbon chain length or chlorine content. Based on the size-dependent distributions of CPs, inhalation exposure assessment from the ICRP model indicated no significant health risk due to CPs in current indoor environments., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Atmospheric particulate matter (PM) can be scavenged by rainfall and contribute dissolved organic matter (DOM) to rainwater. Rainwater may serve as a part or the whole of drinking water sources, leading to the introduction of PM-derived DOM into drinking water. However, little information is available on the role of PM-derived DOM as a remarkable precursor of CX 3 R-type disinfection by-products (DBPs) in rainwater. In this study, samples were collected from ten occurrences of rainfall in Shanghai and batch experiments were executed to explore the contribution of PM-derived DOM to CX 3 R-type DBP formation in rainwater and to further understand some of unknowns regarding its characteristics. Results revealed that a part of PM was scavenged by rainfall and the scavenge performance was better for smaller PM. The formation potentials (FPs) of individual CX 3 R-type DBP were similar among size-isolated PM. TCM was predominant (around 0.5-4.5 μg-C/mg-C) and TCAA was the secondary (around 0.6-3.2 μg-C/mg-C) among all detectable CX 3 R-type DBPs. Based on the PM removal data and DBP FP results, the contribution of PM-derived DOM to CX 3 R-type DBP formation in rainwater was modeled. Furthermore, aromatic proteins and soluble microbial product-like compounds were found to be significant compositions, which were reported to be DBP precursors. And low molecular weight (< 10 kDa) DOM derived from total PM and rainwater exhibited higher CX 3 R-type DBP FPs. DOM fractions with higher SUVA 254 and SUVA 285 values gave relatively higher yields of CX 3 R-type DBPs, indicating that aromatic compounds played an important role in DBP formation., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Microcystis aeruginosa (blue-green alga) commonly blooms in summer and Cyclotella meneghiniana (diatom) outbreaks in fall in the reservoirs that serve as drinking water sources in Southeast China. Herein, an evaluation of disinfection by-product formation potential (DBPFP) from them during chlorination should be conducted. Five DBPs including trichloromethane (TCM), trichloronitromethane (TCNM), dichloroacetonitrile (DCAN), 1,1-dichloropropanone (1,1-DCP) and 1,1,1-trichloropropanone (1,1,1-TCP) were monitored. The formation potential of TCM and TCNM was enhanced with the increase of reaction time and chlorine dosage, whereas that of DCAN, 1,1-DCP and 1,1,1-TCP increased first and then fell with continuing reaction time. M. aeruginosa showed higher DBPFP than C. meneghiniana, the yield of DBPs varied with components of algal cells. The DBPFP order from components of M. aeruginosa was cell suspension (CS) ≈ intracellular organic matter (IOM) > extracellular organic matter (EOM) > cell debris (CD), which indicated that IOM was the main DBP precursors for M. aeruginosa. The yields of DBPs from components of C. meneghiniana were in the order of CS>IOM≈ CD ≈ EOM, suggesting that three components made similar contributions to the total DBP formation. The amount of IOM with higher DBPFP leaked from both algae species increased with the chlorine dosage, indicating that chlorine dosage should be considered carefully in the treatment of eutrophic water for less destroying of the cell integrity. Though fluorescence substances contained in both algae species varied significantly, the soluble microbial products (SMPs) and aromatic protein-like substances were the main cellular components that contributed to DBP formation for both algae., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Identification of novel brominated contaminants in the environment, especially the derivatives and byproducts of brominated flame retardants (BFRs), has become a wide concern because of their adverse effects on human health. Herein, we qualitatively and quantitatively identified three byproducts of tetrabromobisphenol-S bis(2,3-dibromopropyl ether) (TBBPS-BDBPE), including TBBPS mono(allyl ether) (TBBPS-MAE), TBBPS mono(2-bromoallyl ether) (TBBPS-MBAE) and TBBPS mono(2,3-dibromopropyl ether) (TBBPS-MDBPE) as novel brominated contaminants. Meanwhile, the mass spectra and analytical method for determination of TBBPS-BDBPE byproducts were presented for the first time. The detectable concentrations (dry weight) of TBBPS-MAE, TBBPS-MBAE and TBBPS-MDBPE were in the ranges 28-394 μg/g in technical TBBPS-BDBPE and 0.1-4.1 ng/g in mollusks collected from the Chinese Bohai Sea. The detection frequencies in mollusk samples were 5%, 39%, 95% for TBBPS-MAE, TBBPS-MBAE and TBBPS-MDBPE, respectively, indicating their prevailing in the environment. The results showed that they could be co-produced and leaked into the environment with production process, and might be more bioaccumulative and toxic than TBBPS-BDBPE. Therefore, the production and use of TBBPS derivatives lead to unexpected contamination to the surrounding environment. This study also provided an effective approach for identification of novel contaminants in the environment with synthesized standards and Orbitrap high resolution mass spectrometry.

Haloacetamides (HAcAms) are an emerging class of nitrogenous disinfection by-products (N-DBPs) of health concern. However, there are very limited data on the formation and speciation of the nine bromine- and chlorine-containing haloacetamides (HAcAm9). In the study, their formation and speciation during chlor(am)ination were investigated for a group of waters with a range of specific ultraviolet absorbance at 254 nm (SUVA₂₅₄), dissolved organic nitrogen (DON), and bromide levels. The waters that were the least impacted by anthropogenic pollution had the lowest DON levels, the highest ratios of dissolved organic carbon (DOC) to DON, and exhibited the least HAcAm9 formation. DON/DOC may act as an indicator of HAcAm yields during chlorination. HAcAm9 exhibited more formation during chloramination in the low-SUVA waters with no bromide, relative to high-SUVA waters with bromide. The selected waters all formed primarily dihalogenated (di-) HAcAms, followed by trihalogenated (tri-) species and, to a much lesser extent, monohalogenated (mono-) HAcAms. Di-HAcAm formation had similar trends as that of HAcAm9; whereas chloramination formed more mono- and less tri-HAcAms than chlorination. Bromine utilization factors and bromine incorporation factor increased with decreasing and increasing bromide during either chlorination or chloramination, and bromine was easier to incorporate into tri-HAcAms during chloramination than chlorination., (Copyright © 2013 Elsevier B.V. All rights reserved.)

This study was to explore the formation of iodinated disinfection by-products (I-DBPs), including iodoform (CHI3), iodoacetic acid (IAA) and triiodoacetic acid (TIAA), when iodide-containing artificial synthesized waters and raw waters are in contact with chlorine dioxide (ClO2). Among the investigated I-DBPs, CHI3 was the major species during ClO2 oxidation in artificial synthesized waters. Impact factors were evaluated, including the concentrations of ClO2, iodide (I(-)), dissolved organic carbon (DOC) and pH. Formation of CHI3, IAA and TIAA followed an increasing and then decreasing pattern with increased ClO2 or DOC concentration. I-DBPs yield was significantly affected by solution pH. High concentrations of I-DBPs were generated under circumneutral conditions with the maximum formation at pH 8. The increase of I(-) concentration can increase I-DBPs yields, but the increment was suppressed when I(-) concentration was higher than 50 μM. When 100 μg/L I(-)and ClO2 (7.5-44.4 μM) were spiked to the raw water samples from Yangshupu and Minhang drinking water treatment plant, certain amounts of CHI3 and IAA were found under pH 7 and the concentrations were strongly correlated with ClO2 dosage and water qualities, however, no TIAA was detected. Finally, we investigated I-DBPs formation of 18 model compounds, including 4 carboxylic acids, 5 phenols and 8 amino acids, treating with ClO2 when I(-) was present. Results showed that most of these model compounds could form a considerable amount of I-DBPs, especially for propanoic acid, butanoic acid, resorcinol, hydroquinone, alanine, glutamic acid, phenylalanine and serine., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Dissolved natural organic matter (DOM), particularly the low molecular weight DOM, can affect the performance of water treatment processes and serve as a main precursor of disinfection by-products (DBPs) during chlorination. In this study, electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) was used to characterize the low molecular weight DOM along the treatment trait of a conventional drinking water treatment plant. The ESI FT-ICR MS data showed that various C, H, O-only class species were the major components in the source water. According to the van Krevelen diagram analysis, lignin- and tannin-like compounds were the most abundant components. Within an isobaric group, the DOM molecules with a high degree of oxidation (high O/C value) were preferentially removed during coagulation, while those with low degree of oxidation were found to be more reactive toward chlorine. In addition, 357 one-chlorine containing products and 199 two-chlorine containing products formed during chlorination were detected in the chlorination effluent sample at a high confidence level. The chlorinated products can be arranged into series, suggesting that they were originated from C, H, O-only precursor compounds, which were in series related by the replacement of CH(4) against oxygen. For the first time, this study explored the behavior of low molecular weight DOM along a drinking water treatment trait on the molecular level, and revealed the presence of abundant unknown chlorinated products, which are probably rich in carboxylic and phenolic groups, in drinking water., (Copyright © 2012 Elsevier Ltd. All rights reserved.)