南京市雪水中有机磷阻燃剂的污染特征及健康风险评价

采用超高效液相色谱-串联质谱仪（HPLC-MS/MS）分析了南京雪水中的13种有机磷酸酯阻燃剂（Organophosphate esters,OPEs）,研究了其浓度水平及污染特征,利用主成分分析阐述了OPEs可能的来源,并评估了其健康风险.结果表明,雪水中共检出11种OPEs,11种检出OPEs总浓度水平范围为229.1~1175.0ng/L,平均浓度为746.0ng/L,其中∑₁₁OPEs的最大值区域为商业区和住宅区密集的马群,最小值区域为城郊的化工园区.磷酸三（1,3-二氯-2-丙基）酯（Tris（1,3-dichloropropyl）phosphate,TDCPP）和磷酸三（2-丁氧基乙基）酯（Tris（2-butoxyethyl）phosphate,TBEP）是雪水中主要的OPEs污染单体,两者的贡献率分别为26.6%、20.4%.主成分分析表明雪水中TBEP与磷酸三（2-氯异丙基）酯（Tris（1-chloro-2-propyl）phosphate,TCPP）、磷酸三甲酯（TriMethyl Phosphate,TMP）与磷酸三乙酯（Triethyl phosphate,TEP）两两之间可能存在共同的来源,大气的远距离迁移和干湿沉降可能是雪水中附着OPEs的重要原因.不同人群通过饮水摄入11种OPEs的日均暴露量范围为26.6~39.0ng/（kg·d）,通过饮水摄入的OPEs的非致癌风险和致癌风险均低于理论风险值,研究区内雪水中OPEs所致人体健康风险处于较低水平.     

长江南京段水源水中有机磷酸酯的污染特征与风险评估

为探究长江南京段水源水中有机磷酸酯(organophosphate esters,OPEs)的污染特征、时空分布、生态风险和健康风险,利用固相萃取-高效液相色谱-串联质谱法测定了13种OPEs.结果表明,除磷酸三(2,3-二溴丙基)酯外,其余12种OPEs均有不同程度的检出,总浓度范围为85. 21～1 557. 96 ng·L^-1,氯代烷基磷酸酯是主要化合物,其中检出浓度最高的是磷酸三(2-氯乙基)酯[tri(2-chloroethyl) phosphate,TCEP],高达447. 08 ng·L^-1.长江南京段水源水中OPEs呈现明显的季节变化特征,夏季总检出浓度为220～1557. 96 ng·L^-1,平均浓度是493. 78 ng·L^-1,是春秋季的1. 7～2. 6倍.生态风险评估显示磷酸三甲苯酯和2-乙基己基二苯基磷酸酯对有机体(藻类,甲壳类动物和鱼类)具有中或高等风险.高暴露浓度下,OPEs的总非致癌风险为4. 41×10^-3～2. 91×10^-2     

污泥中有机磷酸酯检测的预处理优化

基于“富集（加速溶剂萃取）+净化+检测”的步骤，进行污泥取样量、萃取条件、净化柱类型、淋洗液极性和洗脱液极性的优化.确定了0.2g污泥取样量、130℃萃取温度、1：1（V/V）的丙酮/二氯甲烷混合溶液为萃取剂、氨基柱净化、2：5（V/V）的二氯甲烷/正己烷混合溶液为淋洗液、二氯甲烷为洗脱液，最后用超高效液相色谱-串联质谱对有机磷酸酯进行定性定量检测.结果表明，各物质的基质加标回收率均在60%~120%之间，基质效应也基本控制在±15%.净化方法同样适用于污水样品，用此方法成功测定了北京市某污水处理厂各工艺单元的水相及固相样品，显示出良好的适用性.     

Comparison of two methods for detection of fecal indicator bacteria used in water quality monitoring of the Three Gorges Reservoir

Scientifically sound methods to rapidly measure fecal indicator bacteria are important to ensure safe water for drinking and recreational purposes.A total of 200 water samples obtained from the Three Gorges Reservoir during three successive one-year study periods(October 2009 to September 2012) were analyzed using multiple-tube fermentation(MTF)and most probable numbers combined with polymerase chain reaction(MPN–PCR).The MPN–PCR method was found to be significantly more sensitive than the MTF method for detecting Escherichia coli and Enterococcus spp.,and of equal sensitivity for detecting total coliforms when all surface water samples were grouped together.The two analytical methods had a strong,significant relationship,but MPN–PCR took only 12–18 hr,compared with the 3–8 days needed using the MTF method.Bacterial concentrations varied per sampling site but were significantly lower in the mainstream of the Yangtze River than those in the backwater areas of tributaries.The water quality of 85.8% of water samples from the mainstream was suitable for use as a centralized potable water source,while the water quality of 52.5% of water samples from the backwater areas was unsuitable for recreational activities.Relationships between fecal indicator bacteria showed significant correlation(r = 0.636–0.909,p 0.01,n = 200),while a weak but significant correlation was found between fecal indicators and water turbidity,water temperature,daily inflow,and total dissolved solids(r = 0.237–0.532,p 0.05,n = 200).The study indicated that MPN–PCR is a rapid and easily performed deoxyribonucleic acid(DNA)-based method for quantitative detection of viable total coliforms,E.coli,and Enterococcus spp.in surface water.     

A case study of aggregation behaviors of titanium dioxide nanoparticles in the presence of dodecylbenzene sulfonate in natural water

The present work aims to ascertain the mechanisms of surfactant (dodecylbenzene sulfonate; DBS) effects on the aggregation behaviors of TiO₂ nanoparticles (TiO₂-NPs) in natural water samples. Aggregation experiments were conducted at a TiO₂-NPs concentration of 10 mg/L in deionized water and in natural water samples via dynamic light scattering and Zeta potential determination. Average attachment efficiency was calculated to compare the aggregation behaviors of nanoparticles in the two aqueous media. Results showed that the effects of DBS on aggregation could be interpreted by both Derjaguin–Landau–Verwey–Overbeek (DLVO) and non-DLVO mechanisms. In natural water samples, aggregation did not occur rapidly and was able to develop slowly under all conditions, and the roles of DBS were obvious at high DBS concentration owing to the impacts of inherent components of natural water samples, such as colloids and natural organic compounds. Future aggregation studies should concentrate on multi-factor, multi-colloidal and dynamic aspects under similar environmental conditions.     

钦州湾海水养殖区水体有机磷酸酯的污染特征及生态风险

本文对广西钦州湾养殖区水体中11种常见的有机磷酸酯（OPEs）阻燃剂和增塑剂采用固相萃取和气质联用的分析方法进行了研究,结果表明11种OPEs的总浓度范围为32.9～227 ng/L,平均126 ng/L,处于国际上类似区域的较低水平。钦州湾养殖塘不同OPEs单体的含量水平主要受其自身的水溶性和辛醇-水分配系数（K_OW）影响。OPEs的生产与消费量也在一定程度上影响其含量水平。因此,TCEP、TCPP和TBEP是钦州湾养殖区水体中浓度最高的三种OPEs。总体上,OPEs在养殖塘水体中的浓度高于附近开放的河口与近岸海水,这可能是人为排放的OPEs通过养殖水源（河流与近岸海水）进入养殖塘并得以蓄积的结果。氯代OPEs在养殖塘表现出比非氯代OPEs更高的蓄积能力或持久性。目前,研究区域OPEs浓度水平对周围环境无显著生态影响,但由于其可能会富集在海产品中并通过食物暴露给人体,其健康风险不容忽视。     

北京清河水体中有机磷酸酯的污染特征与生态风险评估

为了探究城市地表水中有机磷酸酯(OPEs)污染水平和生态风险,采用超高效液相色谱-质谱联用仪(UPLC-MS/MS)分析测定了北京清河地表水中10种OPEs的浓度水平和成分组成,使用相关性分析和主成分分析对地表水中OPEs进行源解析,并评估生态风险.结果表明：北京清河地表水中∑₁₀OPEs浓度范围为439.61～1 053.06 ng/L,浓度中位值为768.85 ng/L,平均值为761.77 ng/L,其中磷酸三(1-氯-2-丙基)酯(TCIPP)以及磷酸三(1-氯-2-丙基)酯(TCEP)是主要污染物.∑₁₀OPEs浓度沿河流方向呈先稳定后降低再缓慢升高的特征.源解析结果表明,污水处理厂、道路交通、建筑装饰材料及汽车维修可能是北京清河地表水中OPEs的主要来源.风险熵评估结果表明,水体中TCEP等10种OPEs的生态风险相对较低,但其引起的联合效应值得进一步关注.研究显示,北京清河地表水中OPEs污染水平相对较高,受人为活动影响较大,造成的生态风险可以忽略.     

Preparation and characterization of PVDF-glass fiber composite membrane reinforced by interfacial UV-grafting copolymerization

A novel inorganic–organic composite membrane,namely poly(vinylidene fluoride) PVDF-glass fiber(PGF) composite membrane,was prepared and reinforced by interfacial ultraviolet(UV)-grafting copolymerization to improve the interfacial bonding strength between the membrane layer and the glass fiber.The interfacial polymerization between inorganic–organic interfaces is a chemical cross-linking reaction that depends on the functionalized glass fiber with silane coupling(KH570) as the initiator and the polymer solution with acrylamide monomer(AM) as the grafting block.The Fourier transform infrared spectrometer-attenuated total reflectance(FTIR-ATR) spectra and the energy dispersive X-ray(EDX) pictures of the interface between the glass fiber and polymer matrix confirmed that the AM was grafted to the surface of the glass fiber fabric and that the grafting polymer was successfully embedded in the membrane matrix.The formation mechanisms,permeation,and anti-fouling performance of the PGF composite membrane were measured with different amounts of AM in the doping solutions.The results showed that the grafting composite membrane improved the interfacial bonding strength and permeability,and the peeling strength was improved by 32.6% for PGF composite membranes with an AM concentration at 2 wt.%.     

室内环境中的有机磷酸酯及环境毒理研究

随着全球对溴代阻燃剂的禁用,有机磷酸酯类化合物(OPEs)已成为溴代阻燃剂的主要替代品,其产量与用量逐年升高,并且OPEs极易释放到环境中,因此,近年来OPEs逐渐引起了人们的广泛关注.本文重点查阅了不同国家建筑物室内的灰尘(粉尘)和部分电子产品和家用装饰材料中的OPEs残留浓度等资料,对其毒理学研究进展进行了综述,并介绍了OPEs的风险评价方法和模式,展望了其未来的研究方向和研究重点.     

辽河干流河岸带土壤有机磷酸酯污染特征研究

本研究分析了辽河干流河岸带土壤中有机磷酸酯（OPEs）的含量水平,阐明了其空间分布特征,探讨了OPEs含量与土壤总有机碳（TOC）的关系,评估了OPEs造成的潜在生态风险.结果表明,13种OPEs在辽河干流河岸带土壤中的总浓度范围为19.6~89.4ng/g,平均浓度为44.2ng/g,处于国内外研究的较低水平;河岸带土壤中OPEs的含量总体上表现为上游较低、中下游较高,辽河上游主要由烷基OPEs和TPPO（Triphenylphosphine oxide）组成,辽河中下游主要是烷基OPEs;辽河干流河岸带土壤中OPEs的含量与土壤TOC含量没有相关性,这与OPEs的疏水特性有关;各OPEs单体的危害熵以及12种OPEs的总危害熵均低于1,表明辽河干流河岸带土壤中OPEs造成的生态风险较小.     

Recent advances in thin film composites membranes for brackish groundwater treatment with critical focus on Saskatchewan water sources

Drinking water scarcity is an ever-increasing global concern. This issue appears as a greater threat to the countries with no access to sea water resources or rivers, since their potential water resources are only limited to ground waters only. There are serious concerns with the treatment of ground water resources, including landfill leachates, agricultural contaminations (pesticides, herbicides, and fertilizers), and rural contaminations. Membrane separation has been proved to be the governing technology in water and wastewater treatment plants, as these methods are responsible for more than half of the market share of the world's desalination capacity. This study intends to offer a holistic view of the groundwater contamination with specific focus on Saskatchewan province in Canada, and the recent efforts in the groundwater treatment using thin film composite membrane technology. This study begins with an introduction of the general aspects of ground water and membrane separation, polluting agents, and their sources. It is followed by a discussion of Saskatchewan's groundwater status and various issues. Furthermore, the recent research that became available since 2010 is reviewed in details and the results are summarized with respect to purification efficiency. Different affecting parameters in a groundwater-thin film composite system are synthesized and an in-depth overview is presented.     

基于PCR-DGGE和拟杆菌(Bacteroides)16S rRNA的岩溶地下水粪便污染来源示踪研究:以重庆南山老龙洞地下河系统为例

岩溶地下水的微生物污染日益严重,其来源的研究得到国际学术界的广泛关注.本研究以重庆南山老龙洞岩溶地下河系统为对象,采用滤膜法监测地下水中的总细菌、大肠杆菌、粪大肠菌及粪链球菌等微生物指标,以拟杆菌(Bacteriodes)为指示细菌,采用PCR-DGGE示踪地下水中大肠杆菌/粪大肠杆菌的来源.结果表明,老龙洞地下河流域各类细菌含量严重超标,总细菌数为10~2.9×10~7CFU·m L~(-1),大肠菌群总数达4.3~4.0×10~5CFU·m L~(-1),其中粪大肠菌群(FC)和粪链球菌(FS)分别最高达到1.1×10~6CFU·(100 m L)~(-1)、1.1×10~5CFU·(100 m L)~(-1);FC/FS多数为2以上,暗示流域地下水受人类粪便影响为主.地下水样和粪便样品的拟杆菌群落的PCR-DGGE比对分析表明地下水与人粪之间相似性为7.1%~69.1%,其中地下河出口处达到69.1%.地下水与猪粪之间相似性为1.1%~53.4%,地下河出口处仅为1.5%.因此,人类粪便为地下河污染的主要来源,猪粪污染为动物粪便污染的一部分,还存在其他动物粪便污染来源.此外,PCR-DGGE产物切胶测序发现大部分Bacteroides为人类肠道或粪便来源的细菌.     

Detection Method for Avian Influenza Viruses in Water

Recent events have shown that humans may become infected with some pathogenic avian influenza A viruses (AIV). Since soil and water, including lakes, rivers, and seashores, may be contaminated by AIV excreted by birds, effective methods are needed for monitoring water for emerging viruses. Combining water filtration with molecular methods such as PCR is a fast and effective way for detecting viruses. The objective of this study was to apply a convenient method for the detection of AIV in natural water samples. Distilled water and lake, river, and seawater were artificially contaminated with AIV (H5N3) and passed through a filter system. AIV was detected from filter membrane by real-time RT-PCR. The performance of Zetapor, SMWP, and Sartobind D5F membranes in recovering influenza viruses was first evaluated using contaminated distilled water. SWMP, which gave the highest virus recoveries, was then compared with a pre-filter combined GF/F filter membrane in a trial using natural water samples. In this study, the cellulose membrane SMWP was found to be practical for recovery of AIVs in water. Viral yields varied between 62.1 and 65.9% in distilled water and between 1 and 16.7% in natural water samples. The borosilicate glass membrane GF/F combined with pre-filter was also feasible in filtering natural water samples with viral yields from 1.98 to 7.33%. The methods described can be used for monitoring fresh and seawater samples for the presence of AIV and to determine the source of AIV transmission in an outbreak situation.     

2019—2020年天津市津南区多环芳烃和有机磷阻燃剂气固分配特征及健康风险评价

多环芳烃(PAHs)及有机磷阻燃剂(OPEs)种类繁多且具有易挥发性,通过气固分配行为完成气态和颗粒态的转化. 为准确评估天津市津南区PAHs、OPEs和各组分气固分配行为及风险评价,选择16种PAHs及7种OPEs作为研究对象,利用色谱质谱联用技术测定2019—2020年天津市津南区大气环境中的PAHs和OPEs浓度水平,利用气固分配实测及预测模型研究PAHs及OPEs分配行为,并通过健康风险评价模型对其健康风险进行评估. 结果表明:①天津市津南区2019—2020年∑G-PAHs (气态PAHs总和)年均浓度为36.7 ng/m3,PM_2.5中∑P-PAHs (颗粒态PAHs总和)年均浓度为7.3 ng/m3;∑G-OPEs (气态OPEs总和)年均浓度为5 142.0 pg/m3,PM_2.5中∑P-OPEs (颗粒态OPEs总和)年均浓度为2 752.0 pg/m3. ②研究期间,PAHs气固分配机制受吸收和吸附机制共同影响,低分子量、高分子量PAHs分别受吸附机制、吸收机制影响,而OPEs则主要受有机物吸收机制影响. ③颗粒态的2~3环PAHs、4环PAHs和5~6环PAHs的非致癌风险值占比分别为0.01%~8%、1%~31%和62%~98%,颗粒态的2~3环PAHs、4环PAHs和5~6环PAHs的致癌风险值占比分别为0.2%~1.5%、3%~71%和70%~99%,颗粒态的TNBP (磷酸三丁酯)、TCEP〔三-(β-氯乙基)磷酸酯〕、TCPP〔三(异氯丙基)磷酸盐〕、TPHP (磷酸三苯酯)和TDCPP〔三(1,3 -二氯异丙基)磷酸盐〕的非致癌风险值占比分别为36% (范围为10%~58%)、40% (范围为11%~72%)、45% (范围为13%~67%)、51% (范围为38%~75%)和49% (范围为37%~60%). 研究显示,OPEs的健康风险远低于PAHs,气态OPEs和颗粒态PAHs对人体健康的影响较显著.      

Seasonal Occurrence of Human Enteric Viruses in River Water Samples Collected from Rural Areas of South-East Poland

The study was carried out in 2007, and its main aim was 1 year monitoring of surface water of the River Wieprz in Poland for the presence of human adenoviruses group F and noroviruses (NoVs). In total, 60 water samples were collected from four sampling sites situated along the river. The viruses were concentrated from water samples using glass wool, followed by elution with a glycine buffer containing skimmed milk powder. Subsequently, the viral nucleic acids were extracted and purified from water concentrates using a NucliSENS^® kit and a QIAamp Viral RNA Mini Kit^®. The presence of viral nucleic acids was confirmed by applying traditional PCR-based methods with incorporated internal amplification controls. Human pathogenic viruses were detected in 35% of analysed water samples. Adenoviruses were detected in 28.3% of analysed samples, and were present at all seasons of the year. 11.6% of the samples were positive for NoVs; they were present only during summer, in contrast to conventional findings. Molecular identification of norovirus strains revealed that they belong to genogroup I and II.     

湖泊水体悬浮物中痕量砷的测定方法

重金属在悬浮物和水相中的分配是水体重金属形态研究的重要组成部分,对于追踪水体中重金属元素的来源、迁移转化规律以及重金属生态与健康效应具有重要意义.水中砷元素以其极强的毒性严重危害人类的健康,已越来越引起政府和社会的广泛关注.然而,目前关于痕量悬浮物中砷测定的前处理过程及室内分析的方法与质量控制的叙述不够详尽,有必要对此做深入的研究.本文针对悬浮物较少的水域,选用7个滇池水样,采用不同滤膜、不同预处理方法、不同消解用酸及消解时间,测定并比较砷空白值,试图通过改变实验条件降低空白值,探索前处理的最佳条件及步骤.结果表明,对于悬浮物较少的湖泊水域,采用预称重的醋酸纤维膜过滤水样、载有颗粒物的滤膜冷冻干燥、HNO3-HCl O4加热共消解36 h,消解上清液用氢化物发生原子荧光光度计测定砷空白值低于悬浮物一个数量级以上,膜空白砷相对标准偏差为2.80%~11.38%,膜空白加标回收率为83%~103%;与滇池5个实际样品验证误差范围0.27%~6.92%.此方法可以可靠地获得悬浮物中的砷含量,在砷含量较低的水体悬浮物测定方面具有优势.     

Evaluation of Bacterial Contamination as an Indicator of Viral Contamination in a Sedimentary Aquifer in Uruguay

In Uruguay, groundwater is frequently used for agricultural activities, as well as for human consumption in urban and rural areas. As in many countries worldwide, drinking water microbiological quality is evaluated only according to bacteriological standards and virological analyses are not mentioned in the legislation. In this work, the incidence of human viral (Rotavirus A, Norovirus GII, and human Adenovirus) and bacterial (total and thermotolerant coliform and Pseudomonas aeruginosa) contamination in groundwater in the Salto district, Uruguay, as well as the possible correlation between these groups of microorganisms, was studied. From a total of 134 groundwater samples, 42 (32.1%) were positive for Rotavirus, only 1 (0.7%) for both Rotavirus and Adenovirus, and 96 (72.6%) samples were positive for bacterial indicators. Results also show that Rotavirus presence was not associated with changes in chemical composition of the aquifer water. Bacteriological indicators were not adequate to predict the presence of viruses in individual groundwater samples (well scale), but a deeper spatial–temporal analysis showed that they are promising candidates to assess the viral contamination degree at aquifer scale, since from the number of wells with bacterial contamination the number of wells with viral contamination could be estimated.     

水环境中有机磷酸酯的污染现状及其生物毒性

为有效评估有机磷酸酯（OPEs）潜在的生态健康风险,综述了OPEs在全球水和沉积物中的污染现状,并重点关注OPEs对水生生物的毒性效应,根据浮游生物、游泳生物和底栖生物等不同生物类群的特点分析其潜在的毒性作用机制,进而展望本领域未来的研究方向和科学问题,以期有效评估OPEs的生态效应和健康风险,推动我国OPEs食品安全监控和生态毒理学研究,为规范其绿色应用提供参考.     

浅层地下水氯代烃污染的天然生物降解

对我国北方某城市的浅层地下水进行了有机污染调查,局部地区发现了严重的氯代烃污染.PCE和TCE对地下水的污染程度远远大于CF和CT,是主要污染物,最高浓度分别为487.55μg/L和63.74μg/L.本文根据所掌握的资料,结合氯代烃天然条件下生物降解判定方法,对研究区地下水氯代烃生物降解衰减可能性进行研究.结果表明,该市地下水氯代烃污染区浅层地下水环境、Eh、pH值、生物降解的间接标志NO₃^-浓度变化,以及PCE和TCE生物降解中间产物等均有助于证实氯代烃生物降解转化的存在.多数点为Eh小于100mV的还原环境,将综合污染评价分级中1、2级,3、4级和5级所对应的NO₃^-/Cl^-值求平均分别为0.804,0.754和0.596,在所有检出DCE的点中,cis-1,2-DCE的百分比均超过了DCE总量的80%.室内模拟实验进一步说明,氯代烃污染区地下水环境中,氯代烃完全可能产生共代谢生物降解转化,因此,确认PCE存在向TCE的生物降解转化,能够更加合理地解释这一地区TCE和PCE的污染现状.     

Nutrient variability and its influence on nitrogen processes in a highly turbid tropical estuary (Bangpakong, Gulf of Thailand)

Estuarine ecosystems in SE Asia have been poorly studied when compared to other tropical environments. Important gaps exist particularly in the understanding of their biogeochemical function and contribution to global change. In this work we looked into N-turnover in the water column and sediments of the Bangpakong estuary(13°N). A seasonal sampling program was performed along the salinity gradient covering different stretches of the estuary(68 km).Key physical and chemical characteristics were also monitored in order to unravel possible environmental controls. Results showed the occurrence of active denitrification in sediments(5.7–50.9 nmol N-N2/(cm3·hr)), and water column(3.5–1044 pmol N-N2/(cm3·hr)). No seasonal or spatial variability was detected for denitrification potential in sediment samples. However, in the water column, the denitrification activity peaked during the transition season in the downstream sites coinciding with high turbidity levels. Therefore, in that period of the year, the water column compartment may be an important contributor to nitrate reduction within the estuary. The rather low nitrification rates detected were not always measurable, probably due to the reduced oxygen content and high siltation. This study is one of the few dealing simultaneously with sediments and water column processes in a highly turbid tropical estuary.Therefore, it emerges as a valuable contribution for the understanding of the dynamics of the nitrogen cycle in tropical environments by exploring the role of estuarine N microbial activity in reducing the effects of increased nitrogen loads.