The use of chemical substances has brought great benefits to human well-being; however, the dark side of the coin is that they may pose risks to human health and the environment [...]

Effluent discharged from urban wastewater treatment plants (WWTPs) is a major source of emerging contaminants (ECs) requiring effective regulation. To this end, we collected discharge datasets of pharmaceuticals (PHACs) and endocrine-disrupting chemicals (EDCs), representing two primary categories of ECs, from Chinese WWTP effluent from 2012 to 2022 to establish an exposure database. Moreover, high-risk ECs’ long-term water quality criteria (LWQC) were derived using the species sensitivity distribution (SSD) method. A total of 140 ECs (124 PHACs and 16 EDCs) were identified, with concentrations ranging from N.D. (not detected) to 706 μg/L. Most data were concentrated in coastal regions and Gansu, with high ecological risk observed in Gansu, Hebei, Shandong, Guangdong, and Hong Kong. Using the assessment factor (AF) method, 18 high-risk ECs requiring regulation were identified. However, only three of them, namely carbamazepine, ibuprofen, and bisphenol-A, met the derivation requirements of the SSD method. The LWQC for these three ECs were determined as 96.4, 1010, and 288 ng/L, respectively. Exposure data for carbamazepine and bisphenol-A surpassed their derived LWQC, indicating a need for heightened attention to these contaminants. This study elucidates the occurrence and risks of ECs in Chinese WWTPs and provides theoretical and data foundations for EC management in urban sewage facilities.

As a replacement for polybrominated diphenyl ethers (PBDEs), organophosphorus flame retardants (OPFRs) have been widely used and detected in different indoor environments all over the world. This paper comprehensively describes the concentration levels and distribution information of 11 kinds of OPFRs from 33 indoor dust and 10 air environments, from which TBOEP, TCIPP, and TDCIPP were observed to have higher concentrations in indoor environments. The ΣOPFRs displayed higher concentrations in indoor dust than in indoor air due to the higher molecular weight and vapor pressure of ΣOPFRs in building decoration materials, specifically for TCIPP and TDCIPP compounds. Considering that it is inevitable that people will be exposed to these chemicals in the indoor environments in which they work and live, we estimated their potential health risks through three human exposure pathways and found that the ingestion exposure to TBOEP for toddlers in Japan may reach up to 1270.80 ng/kg/day, which comprises a significant pathway compared to dermal contact and indoor air inhalation. Specifically, the combined total exposure to OPFRs by air inhalation, dust ingestion, and dermal contact was generally below the RfD values for both adults and toddlers, with a few notable higher exposures of some typical OPFRs.

Halogenated methanesulfonic acids (HMSAs) are an important new class of organic compounds as they were universal in the water cycle and drinking water sources. However, no study has investigated the presence of HMSAs in surface water and sediment from China. The present study reports the occurrence and spatiotemporal distribution of seven HMSAs in water and sediment samples from Hangzhou Bay, China. Tri-fluoromethanesulfonic acid (TFMSA) was the main contributor to the concentrations of HMSAs in water and sediment samples from spring, summer, autumn and winter which were 30.8-541 ng/L, n. d.-86.6 ng/L, 4.22-70.9 ng/L and 8.86-192 ng/L, separately, while in sediment samples were n. d.-11.1 ng/g, n. d.-12.9 ng/g, n. d.-22.5 ng/g, n. d.-4.60 ng/g, respectively. The levels of HMSAs in water from winter and spring were higher than those in summer and autumn, and the concentrations of the target HMSAs in water presents a seasonal pattern affected by the temperature, the precipitation and river flow variations. Nevertheless, the levels of HMSAs in sediment were highest in the area near the industrial area and the confluences of rivers. Correlation analysis revealed that the concentrations of TFMSA were significantly positively correlated with total organic carbon (TOC) in water samples. Although TFMSA is regarded as low toxic based on the EC50 value of acute toxicity, the potential risks to aquatic ecology should be paid more attention due to its high concentrations in the aquatic system and the environmental persistency.

采集长江下游典型城市江段干流、河汊以及入江涵闸口、支流汇入口共8个点位水样,基于高通量非靶向筛查技术,结合多元统计分析方法,分析目标江段水中有机氮磷污染物种类、来源和传输路径,结果表明:目标江段共识别出60种有机污染物,其中有机氮包括氨基甲磺酸、尿素、苯甲腈等11种,有机磷包括4-羟基苯基膦酸和硫代磷酸三甲酯2种,主要涉及医药、农药原辅料、个人护理品和材料制造原辅料.目标江段有机氮磷污染物存在3条传输路径:路径I为有机氮叠加有机磷传输;路径Ⅱ以无机磷传输为主,也存在一定的有机氮传输;路径Ⅲ以有机氮传输为主,也存在一定的有机磷传输.目标江段有机氮磷污染物传输,主要受水文要素控制,与水流向基本一致.此外还存在上游来水汇入和区域内自身产生两个途径.

Organophosphate flame retardants (OPFRs) and organophosphate pesticides (OPPs), pertaining to organophosphate esters, are ubiquitous in environment and have been verified to pose noticeable risks to human health. To evaluate human exposures to OPFRs and OPPs, a fast and sensitive approach based on a solid phase extraction (SPE) followed by the ultra-high-performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS/MS) detection has been developed for the simultaneous analysis of multiple organophosphorus metabolites in urine. The method allows the identification and quantification of ten metabolites of the most common OPFRs and all six dialkylphosphates (DAPs) of OPPs concerning the population exposure characteristics. The method provided good linearities (R2 = 0.998-0.999), satisfactory method detection limits (MDLs) (0.030-1.129 ng/mL) and only needed a small volume (200 μL) of urine. Recovery rates ranged 73.4-127.1% at three spiking levels (2, 10 and 25 ng/mL urine), with both intra- and inter-day precision less than 14%. The good correlations for DAPs in a cross-validation test with a previous gas chromatography-mass spectrometry (GC-MS) method and a good inter-laboratory agreement for several OPFR metabolites in a standard reference material (SRM 3673) re-enforced the precision and validity of our method. Finally, the established method was successfully applied to analyze 16 organophosphorus metabolites in 35 Chinese children's urine samples. Overall, by validating the method's sensitivity, accuracy, precision, reproducibility, etc., data reliability and robustness were ensured; and the satisfactory pilot application on real urine samples demonstrated feasibility and acceptability of this method for being implemented in large population-based studies.

In this study, we investigated the emission and fate of 9 organophosphate esters (OPEs) from a natural environment chamber, in which three environment matrices (i.e., air, dust, and window film samples) as well as three decoration materials (i.e., laminate flooring, latex paint, and nonwoven paper) were collected within gradient variation of room temperature and relative humidity. ΣAlkyl-OPEs and ΣCl-OPEs were the predominant classes in the three environment matrices, accounting - on average - for 98.7%, 99.8% and 99.3% of ΣOPEs in indoor dust, air and window film, respectively. TBOEP was the most abundant OPE in air, dust, and laminate flooring, respectively, while tris (2-chloro-isopropyl) phosphate (TCIPP) and tris (1,3-dichloro-2-propyl) phosphate (TDCIPP) in nonwoven paper and latex paint, respectively. The results showed that higher room temperature expedited the emission of OPEs to indoor air. However, the room temperature and relative humidity had no effect on the levels of OPEs in dust. The OPEs equilibrium time in indoor environment may be dependent on room temperature and relative humidity. The area specific emission rates (SERs) of the three materials were calculated, and an optimal expression based on the concept of mass balance model was constructed, preliminarily revealing a general relationship between OPEs source and sink effects in indoor environment.

长江水环境污染物识别和溯源分析是保护长江水生态环境的前提.于2021年11月26-27日对长江南京段有机磷进行溯源调查,采用有机物指纹图谱识别技术对9个干流监测点位和7个临近入河排口监测点位之间以有机磷为代表的有机污染物的耦合关联性进行研究,筛查重点潜在污染水域及可能来源.研究结果表明,应用指纹图谱技术共识别出25类有机污染物,其中干流XC-02点位有机磷等有机污染物输入明显,主要受临近陆域污水处理厂、制药企业、石化企业及表面加工企业等的工业废水排放影响;干流XC-07点位有机磷离子峰强度升高,受上游传输与陆域入河排口 XA-07点位共同影响.研究为河流有机污染物溯源提出了指纹图谱解析方法思路并得以应用,为水环境有机污染物管控提供技术支撑和决策依据.

The production and emission of short-chain perfluoroalkyl acids (PFAAs) has increased over the years to replace long-chain PFAAs, leading to frequent detection in the environment and raising global concerns about the potential impacts on human health. In this study, the specific urine levels of 10 PFAAs were obtained from 189 children (age 8–12 years) from two primary schools located in urban and suburban areas of Shanghai in 2019, and the contributions of dietary factors were investigated. Perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), and perfluorobutane sulfonate (PFBS) were detected in 100%, 99.5%, and 87.3% of the samples, with median concentrations of 20.20 ng/L, 46.50 ng/L, and 20.95 ng/L, respectively. The most abundant PFAA was perfluorooctanoic acid (PFOA), with a median concentration of 78.90 ng/L. The concentration of ∑PFAAs ranged from 61.10 to 4108.93 ng/L, with a median concentration of 253.12 ng/L. Children aged 8–9 years had higher median levels of PFBS, perfluorohexane sulfonate (PFHxS), and perfluorooctane sulfonate (PFOS) than children aged 10–12 years. Obese/overweight children had lower levels of PFHpA, PFBS, and PFOS. The intake of red meats, tubers, sugared beverages, fish and seafood, and eggs contributed to higher concentrations of PFAAs, while frequent intake of poultry and soy milk was associated with lower PFAA concentrations.

In the last decades, there has been an increasing concern about the human exposure to indoor dust. Therefore, it is imperative to assess the toxicity of indoor dust and associated dust extracts. In this study, the acute toxicity assessment of indoor dust was performed using a bioluminescence test, with Photobacterium phosphoreum T3 (PPT3) chosen as the test bacterium. The different indoor dust samples were collected from residences, offices, dormitories and laboratories in Shanghai, China. Our data reveal that PPT3 is more active to water-soluble ions and organic contaminants at low concentrations, while extract solutions elicit increased bacterial toxicity at high concentrations. The results of a bioluminescence assay by PPT3 indicated that the dust organic extracts exhibited increased toxicity compared with the water exacts. Dust extracts from the laboratory exhibited the greatest bacterial toxicity when compared with office, dormitory and residence samples. Moreover, office dust exhibited higher bacterial toxicity than residence dust. Furthermore, the comprehensive toxicity of dust on PPT3 was assessed by extracts toxicity -addition (i.e. IRaddition). The calculated values were close to the corresponding experimental data. The bioluminescence test showed the indoor dust samples are weakly toxic to PPT3, which are equivalent to 0.046-0.123 mg Hg center dot L-1. Different dust extracts among the different sampling sites showed varying toxicity to PPT3. This study provides some important information to understand the potential health risk from different indoor environment using a rapid bioluminescence assay.

Oxidation is an attractive treatment method to effectively remove organic contaminants in water. In this study, degradation of 30 organic compounds in different oxidation systems was evaluated, including oxygen (O-2), hydrogen peroxide (H2O2), ozone (O-3) and hydroxyl radical (HO center dot). First, a quantitative structure-activity relationship (QSAR) model for oxidation-reduction potentials (ORPs) of organics was developed and exhibited a good performance to predict ORP values of organics with evaluation indices of squared correlation coefficient (R-2) = 0.866, internal validation (q(2)) = 0.811 and external validation (Q(ext)(2)) = 0.669. Four quantum parameters, including f(+)(n), f(-)(n), E-HOMO and E-B3LYP dominate the ORP values. Subsequently, a relationship between reaction rates (k) and the difference of ORP for oxidants and organics (Delta Eoxi-org) was established, however, which was limited (R-2 = 0.697). Therefore, two new predictors (slopes and intercepts) are proposed based on the linear relationships between k values and ORPs of oxidants. These new predictors can be applied to estimate the reaction rates and minimum oxidation potential for organic compounds. Afterwards, to express the two predictors, QSAR models were established. The two optimal QSAR models fitted very well with experimental values and were demonstrated to be stable and accurate based on R-2 (0.982 and 0.965), q(2) (0.950 and 0.950) and Q(ext)(2) (0.985 and 0.989). BOx, q(H)(+) and q(C)(x) were main factors influencing the slopes and intercepts. This study developed methods to predict ORPs of organics and established two new predictors to estimate the reaction rates undergoing different oxidation processes, offering new insights into the oxidant selection. (C) 2019 Published by Elsevier Ltd.

有机磷阻燃剂(OPFRs)是目前室内环境中普遍关注的一类新兴污染物,低浓度长期暴露会对人体健康造成不良影响,因此研究其在室内装修材料中的污染释放规律尤为重要.本文以3种典型室内装修材料为研究对象,通过在标准环境舱中连续测试20 d及GC-MS定量分析污染源中9种有机磷阻燃剂的含量水平变化,得到OPFRs在无纺布墙纸、乳胶漆和强化木地板等3种污染源中的平均浓度分别为3874.18、19225.33、4137.30 ng·g-1,其中磷酸三(丁氧基乙基)酯(TBEP)为最主要的污染物;计算得到3种典型材料中OPFRs的挥发强度系数,按大小排序为:强化木地板＞乳胶漆＞无纺布墙纸,为后续模型建立奠定基础;计算得到无纺布墙纸、乳胶漆和强化木地板释放OPFRs的平衡半衰期分别为6.53、5.98、9.43 d,衰减半衰期分别为30.01、17.15、116.55 d.环境舱实验获得的挥发强度系数及两类半衰期对于揭示室内典型污染源挥发释放OPFRs的规律和特征具有重要意义,同时也为真实室内环境中OPFRs污染源解析奠定了基础.

Organophosphate flame retardants (OPFRs) have been increasingly utilized as flame retardants in various fields due to the phasing out of polybrominated diphenyl ethers. To achieve a better understanding of the degradation of OPFRs undergoing supercritical water oxidation (SCWO) process, two-dimensional and three-dimensional quantitative structure-activity relationship (2D-QSAR and 3D-QSAR) models were established to investigate the factors influencing the total carbon degradation rates (kTOC). Results of the QSAR models demonstrated reliable results to estimate the kTOC values, but varied in the influencing factors. Two distinct degradation mechanisms were subsequently proposed based on the distribution of LUMO in molecules for the 2D-QSAR model. CoMFA and CoMSIA methods were applied to develop the 3D-QSAR models. Steric fields were observed to influence kTOC values more than electrostatic fields in the CoMFA model with the contribution rates of 87.2% and 12.8%, respectively. In the CoMSIA model, influence on kTOC values varies between different types of fields with the hydrophobic field being the most influential at 62.1%, followed by the steric field at 25.7% and then the electrostatic field at 10.8%. Results from this study generated critical knowledge of influencing factors on OPFRs degradation and yielded theoretical basis for estimating removal behaviors of OPFRs undergoing SCWO process.

为构建海水中邻苯二甲酸二乙酯(DEP)快速检测方法,采用胶体金酶联免疫层析技术,利用抗DEP单克隆抗体杂交瘤细胞株进行腹水制备.以邻苯二甲酸单乙酯(MEP)-OVA为包被抗原,羊抗鼠IgG为二抗,优化抗原抗体配对组合和胶体金-抗体标记条件,最后组装获得快速检测DEP胶体金免疫层析试纸条.利用包括DEP在内的12种邻苯二甲酸酯类化合物标准溶液检测试纸条的灵敏度和特异性,并利用人造海水作为稀释溶剂检测试纸条的海水环境适应性.结果显示∶纯化后抗体效价最高可以达到1∶30 000以上,胶体金溶液与抗体最佳标记条件为pH=7.2,抗体最佳标记量为6μL· mL-1;所制备胶体金酶联免疫层析(GICA)试纸条对DEP的检测特异性较高,在人造海水条件下试纸条对DEP的检测限可达20 μg·L-1,适用于海水中DEP的快速检测.

A hybrid electrode material is constructed based on self-assembly of reduced graphene oxide-cellulose nanocrystals (rGO-CNC) as the matrix and then decorating with manganese dioxide (α-MnO2). Cellulose nanocrystals (CNCs) were introduced between graphene sheets as a spacer and MnO2 nanoparticles were deposited as an electrochemically active component on the surface of rGO-CNC via an in-situ hydrothermal method. The resultant composite exhibited an excellent specific capacitance of 397.7 ​F ​g−1 at the current density of 0.2 ​A ​g−1, a negligible capacitance retention over 2000 cycles, and a good energy-power profile of 23.52 ​Wh kg−1 and 1.51 ​kW ​kg−1. The proposed simple assembly strategy is useful for the design of high performance multi-component hybrid electrodes for supercapacitors.

Per- and polyfluoroalkyl Substances (PFAS) are ubiquitous in the environmental matrix, and their eco-toxicity on wide life and health risks on humans arising concerns. Due to the information gap, current risk assessments of PFAS ignore the indoor exposure pathway such as indoor dust and the different sources of drinking water. We collected and analyzed 168 indoor dust and 27 drinking water samples (including tap water, filtered water and bottled water). The mean concentrations of six typical PFAS measured in indoor dust and drinking water are in the range of 15.13-491.07 ng g(-1) and 0.31 4.14 ng L-1, respectively. For drinking water, PFOA and PFOS were the dominant compounds, while PFHxS was the most abundant in indoor dust. Short-chain PFAS concentrations were higher than long chain PFAS in both drinking water and indoor dust. Higher concentration of PFAS was observed in tap water and filtered water than bottled water. The total daily intake (TDI) of six PFAS are 20.67 52.97 ng kg(-1) d(-1) for infants, children, teenagers, and adults. As to children, teenagers, and adults, perfluorooctanoate (PFOA) is the major compound, accounting for 72.9-74.7% of the total daily intake. And PFOA (38.7%) and perfluorooctane sulfonate (PFOS, 42.2%) are the dominant PFAS for infants. The quantitative proportions of exposure sources are firstly revealed in this study, which in the order of foodstuff > indoor dust > drinking water > indoor air. Although the contribution to the PFAS intake of drinking water and indoor dust was not predominant (<9%), the health risks caused by long-term exposure need our attention. The hazard quotient (HQ) values of total PFAS were in the range of 0.154-0.498, which suggesting the relatively lower exposure risk in Chinese population. This study provides important reference to understand PFAS exposure status other than foodstuff. (C) 2019 Elsevier Ltd. All rights reserved.

为构建针对水环境中邻苯二甲酸二乙酯(Diethyl phthalate,DEP)等邻苯二甲酸酯类(Phthalates,PAEs)化合物的免疫学快速检测方法,需获得高效稳定的分泌抗DEP单克隆抗体的杂交瘤细胞株.以邻苯二甲酸单乙酯(Monoethylphthalate,MEP)-BSA为免疫抗原免疫BALb/c小鼠,间接竞争ELISA测定小鼠血清效价,用细胞融合筛选技术筛选抗DEP单克隆抗体杂交瘤细胞株.结果显示,实验小鼠免疫血清效价最高能达到1∶5 000,经过HAT筛选、复检和亚克隆后得到9个能分泌抗DEP单克隆抗体的细胞株,细胞株上清液效价最高能达到1∶10 000,对DEP的抑制率最高能达到86.5％,且其对11种结构类似物的交叉反应率均低于0.1％,特异性较好.本研究成功构建的杂交瘤细胞株能稳定高效分泌抗DEP单克隆抗体,可为DEP的ELISA检测方法建立及胶体金免疫层析(Colloidal gold immunochromatography assay,GICA)试纸条的研制提供稳定高效的单克隆抗体源.

A high-efficiency electro-thermal heater requires simultaneously high electrical and thermal conductivities to generate and dissipate Joule heat efficiently. A low input voltage is essential to ensure the heater’s safe applications. However, the low voltage generally leads to low saturated temperature and heating rate and hence a low thermal efficiency. How to reduce the input voltage while maintaining a high electro-thermal efficiency is still a challenge. Herein, a highly electrical and thermal conductive film was constructed using a graphene-based composite which has an internal three-dimensional (3D) conductive network. In the 3D framework, cellulose nanocrystalline (CNC) phase with chiral liquid crystal manner presents in the form of aligned helix between the graphene oxide (GO) layers. Carbon nanodots (CDs) are assembled inside the composite as conductive nanofillers. Subsequent annealing and compression results in the formation of the assembled GO-CNC-CDs film. The carbonized CNC nanorods (CNR) with the helical alignment act as in-plane and through-plane connections of neighboring reduced GO (rGO) nanosheets, forming a conductive network in the composite film. The CDs with ultrafast electrons transfer rates provide additional electrons and phonons transport paths for the composite. As a result, the obtained graphene-based composite film (rGO-CNR-CDs) exhibited a high thermal conductivity of 1,978.6 W·m−1·K−1 and electrical conductivity of 2,053.4 S·cm−1, respectively. The composite film showed an outstanding electro-thermal heating efficiency with the saturated temperature of 315 °C and maximum heating rate of 44.9 °C·s−1 at a very low input voltage of 10 V. The freestanding graphene composite film with the delicate nanostructure design has a great potential to be integrated into electro-thermal devices.

In this study, we found a novel and efficient way of recycling graphene oxide (GO) by adding ZnO colloid into the GO solution. GO flocculates immediately when mixed with ZnO colloids. Interestingly, the flocculation would disappear and disperse homogeneously in solution if a certain amount of HCl is added. The study offers a solution to recover and reuse GO throughout its production procedures. More importantly, in the obtained reduced GO/ZnO (rGO/ZnO) flocculant, ZnO nanorods are observed self-assembled into an ordered structure in between the rGO sheets. This prevents the rGO sheets from re-stacking and facilitates the movement of the electrolyte into ZnO if the prepared rGO/ZnO is used as an electrode for supercapacitor. Electrochemical measurements have proved that the rGO/ZnO composite with a weight ratio of 1: 1 exhibits a gravimetric specific capacitance of 175 F g(-1) and the rGO/ZnO electrode maintains 89.6% of the initial capacitance after 5000 cycles of uses.