我国淡水环境中卤乙酸类消毒副产物的预测无效应浓度研究

新型冠状病毒肺炎（COVID-19,简称“新冠肺炎”）疫情期间,消毒剂超量使用,导致大量DBPs（disinfection by-products,消毒副产物）进入自然水体,可能对水生态环境产生不良影响.以5种HAAs（卤乙酸类）消毒副产物（一氯乙酸、二氯乙酸、三氯乙酸、一溴乙酸和二溴乙酸）为研究目标,基于筛选的本土水生生物的毒性数据,采用欧盟《风险评价技术指导文件》中的评估系数法和平衡分配法分别推导了5种HAAs在水体和沉积物两种介质中的PNEC（预测无效应浓度）值.结果表明:5种HAAs对水生生物的急、慢性毒性大小顺序均为一溴乙酸>一氯乙酸>二氯乙酸>三氯乙酸>二溴乙酸;5种HAAs（一氯乙酸、二氯乙酸、三氯乙酸、一溴乙酸和二溴乙酸）的PNEC_w（水体的预测无效应浓度）分别为0.025、0.030、0.060、0.016和1.956 mg/L,PNEC_s（沉积物的预测无效应浓度）分别为0.021、0.026、0.057、0.013和1.679 mg/kg（以湿质量计）.研究显示,污水处理厂出水中排放的DBPs对水生态环境可能造成潜在的风险和危害,应加强对污水处理厂出水中5种HAAs的监测和去除,从而减少排入到自然水体中的HAAs含量.      

对二甲苯及其代谢物对HepG2的细胞毒性效应研究

对二甲苯作为一种重要的苯系物化工原料,生产使用量非常大.进入人体的对二甲苯主要在肝脏中代谢,生成对甲基苄醇和对甲基苯甲酸.目前,关于对二甲苯及其代谢物的肝脏毒性数据仍不够充分.本研究以人肝癌细胞(HepG2)作为实验模型,在细胞层面评价了对二甲苯及其代谢产物(对甲基苄醇和对甲基苯甲酸)的毒性效应,着重探讨了化合物对细胞活力、细胞膜完整性、细胞凋亡的影响.研究结果显示,对二甲苯及其代谢产物对HepG2细胞的急性毒性大小顺序为:对甲基苄醇对甲基苯甲酸对二甲苯.显然,对二甲苯在机体内发生代谢转化后具有毒性增加的趋势.另外,对二甲苯及其代谢产物暴露能够引起细胞膜破损,导致细胞坏死,并诱导一定程度的细胞凋亡现象.该研究发现为对二甲苯作为常见溶剂的生产使用提供了安全性评价的重要科学数据.     

HepG2细胞对垃圾渗滤液经SND/UF/RO处理前后的毒性评估

垃圾渗滤液含有高浓度难降解毒性污染物及致癌、致诱变和致畸物质,其较为成熟的处理工艺主要有硝化反硝化（SND）、超滤（UF）和反渗透（RO）等.目前,关于SND/UF/RO技术对渗滤液处理前后的毒性降低情况尤其与细胞凋亡相关的研究较缺乏,故本文选用HepG2细胞为评价对象,研究经SND/UF/RO处理前后垃圾渗滤液的细胞毒性、遗传毒性.细胞毒性结果表明,经SND/UF/RO处理后,暴露在浓度为30%渗滤液中HepG2细胞活力从38.3%上升至88.4%;同时,凋亡试验和细胞周期分析表明,经SND/UF/RO处理后的出水清液无法诱导细胞发生凋亡,但可将细胞阻滞在G2期诱导细胞内染色体畸变.这是由于出水清液对HepG2细胞有明显的氧化损伤,但渗滤液原液可诱导细胞凋亡且阻滞细胞停留在S期而影响其增殖.微核试验数据显示,出水清液的遗传毒性是阴性对照组的2倍,彗星实验佐证了出水清液对细胞内DNA有微弱损伤.实验表明,SND/UF/RO工艺可将垃圾渗滤液原液的毒性减少约95%,出水清液仍具有微弱的细胞毒性和遗传毒性.因此,需对经SND/UF/RO处理后的排放液毒性高度重视.     

五氯苯酚与邻氯苯酚和2,4-二氯苯酚对斑马鱼的联合毒性

在五氯苯酚(PCP)与邻氯苯酚(2-CP)和2,4-二氯苯酚(2,4-DCP)3种物质单一毒性试验结果的基础上,按照等毒性单位设计,采用相加指数法,对五氯苯酚(PCP)与邻氯苯酚(2-CP)或2,4-二氯苯酚(2,4-DCP)以及这3种物质共存对斑马鱼(Brachydanio rerio)的联合毒性进行了试验研究.结果表明,邻氯苯酚(2-CP)和2,4-二氯苯酚(2,4-DCP)与五氯苯酚的联合毒性效应均表现为协同作用,使五氯苯酚的毒性剧增.由于邻氯苯酚或2,4-二氯苯酚的存在以及3种物质共存,使五氯苯酚对斑马鱼的48 h LC50由原来的0.102 mg/L,分别下降到0.031,0.029及0.022 mg/L.因此可见,水体污染评价目前只考虑单一毒物的影响还远远不够,由此制定的控制标准对水体的保护不利,必须从联合毒性的角度对水质污染进行综合评价.      

紫外/亚硫酸钠还原降解三氯乙酰胺的效能

卤乙酰胺(HAc Ams)是一类具有高细胞毒性和高遗传毒性的饮用水含氮消毒副产物(N-DBPs),并在饮用水中被广泛检出,其中三氯乙酰胺(TCAc Am)的毒性显著高于传统DBPs.本实验以配置的TCAc Am溶液作为目标污染物,采用紫外(UV)活化亚硫酸钠(Na_2SO_3)体系降解水中的TCAc Am,并探究在该体系下光强、还原剂投加剂量(Na_2SO_3)和p H对还原降解TCAc Am效果的影响.结果表明,采用UV/Na_2SO_3体系可快速降解TCAc Am,其降解效果与光强、Na_2SO_3投加剂量和p H均呈正相关,且p H值对反应速率与降解率有显著影响,当p H值从6提高至9,TCAc Am的降解率在反应120 min时从12. 8%提高至99. 6%.在光强为450μW·cm~(-2),p H为9,Na_2SO_3投加剂量为1. 00 mmol·L~(-1),连续30 min光照条件下,TCAc Am降解率达到99. 4%.实验证明UV/Na_2SO_3体系是一种有效消减TCAc Am的高级还原技术,并且具备还原降解其他卤代DBPs的潜力,可用于饮用水中卤代DBPs的降解.     

取代苯对人体细胞的定量结构—遗传毒性研究

通过微核实验,测定了 36 种取代苯类化合物对人体外周血淋巴细胞的遗传毒性;并构建了遗传毒性与分子结构参数之间的 QSAR 模型.结果表明,有 34 种化合物显著地导致了微核的产生,具有明显的遗传毒性;遗传毒性的大小与分子结构描述符辛醇-水分配系数(MlogP)、x 轴主惯性矩(Principalx)、γ 极化率[Polar(γ)]等存在良好的结构-活性相关关系,所建模型的相关系数 R² =0.718,具有较高的预测能力,可用来预测取代苯类化合物的遗传毒性.     

重金属和氯酚对霍甫水丝蚓的急性毒性及水环境安全评价

研究了Hg2+、Cr6+和Pb2+等重金属及2,4-二氯酚、2,4,6-三氯酚和五氯酚等氯酚类物质对霍甫水丝蚓(Limnodrilus hoffmeisteri)的急性毒性效应.结果表明, Hg2+、Cr6+和Pb2+对霍甫水丝蚓的96h-LC50分别为0.16,4.25,76.24mg/L;2,4-二氯酚、2,4,6-三氯酚和五氯酚对霍甫水丝蚓的96h-LC50分别为20.73,7.86,2.42mg/L. 根据6种污染物对霍甫水丝蚓的毒性实验结果,预测水体中Hg2+、Cr6+和Pb2+对霍甫水丝蚓的安全浓度SC分别为16,425,7624μg/L,最大允许浓度分别为1.6,42.5,762.4μg/L;2,4-二氯酚、2,4,6-三氯酚和五氯酚对霍甫水丝蚓的安全浓度SC分别为2073,786,242μg/L,最大允许浓度MPC分别为207.3,78.6,24.2μg/L.6种污染物的毒性评估结果显示,Hg2+对霍甫水丝蚓表现为极高毒性,Cr6+、2,4,6-三氯酚和五氯酚对其表现为高等毒性,Pb2+和2,4-二氯酚表现为中等毒性.3种重金属对其毒性顺序为:Hg2+ > Cr6+ > Pb2+;3种氯酚类物质对其毒性大小依次为:五氯酚 > 2,4,6-三氯酚 > 2,4-二氯酚.     

煮沸对氯、氯胺模拟消毒饮用水中六大类DBPs的去除规律研究

以陆生来源有机物为原料制备了模拟氯、氯胺消毒饮用水,系统研究了煮沸对六大类46种消毒副产物（disinfection by-products, DBPs）的去除规律.结果显示,相比氯消毒,氯胺消毒可有效减少三卤甲烷（THMs）、卤乙酸（HAAs）、卤乙醛（HALs）、卤代硝基甲烷（HNMs）、卤乙腈（HANs）等DBPs的生成,但会提高碘代DBPs (I-DBPs)、卤乙酰胺（HAcAms）的生成.煮沸对于绝大多数DBPs （除了二卤乙酸）有良好的去除效果,并发现如下规律：(1)就单种DBP而言,消毒方式对煮沸去除DBPs并无显著影响;(2)在同类型的DBPs中,取代程度高的DBPs普遍比取代程度低的DBPs容易去除;(3)取代程度相同的同类型DBPs,煮沸后DBPs去除率大部分遵循I-DBPs> Br-DBPs> Cl-DBPs的规律;(4)少部分DBPs （如Cl/Br-THMs、二卤乙腈）,煮沸去除率表现出沸点或亨利常数依赖性.总体来看,DBPs去除率排序为THMs≈HANs≈HALs≈HNMs> HAcAms>>HAAs.此外,煮沸后各类DBPs的...     

利用斑马鱼胚胎研究污水处理工艺中DOM与DBPs的关系

以模式生物斑马鱼胚胎为试验材料,通过暴露试验研究了污水处理工艺不同阶段出水中溶解性有机物(DOM)与消毒副产物(DBPs)毒性效应关系,揭示污水处理工艺中DBPs前体物DOM的生成变化规律以及对再生水生态安全性的影响。结果表明,污水处理各阶段DOM和DBPs水样对斑马鱼胚胎均有不同程度的致死效应,改良A2/O工艺段水样暴露的斑马鱼胚胎死亡率较大,DOM暴露的斑马鱼胚胎致死毒性效应低于DBPs,且DBPs对斑马鱼胚胎的半致死毒性效应较大;污水处理过程中增加的腐殖酸类物质主要来自于好氧过程微生物的生化合成;污水处理各阶段水样中腐殖酸类物质含量水平与斑马鱼胚胎的致死毒性效应存在正相关关系,因此污水生物处理会增大水中消毒前体物(DOM)特别是腐殖酸类物质的含量,从而增加了DBPs的产生量和再生水的生物毒性及环境风险。     

蛋白核小球藻(Chlorella pyrenoidosa)微板毒性分析方法优化

以蛋白核小球藻(Chlorella pyrenoidosa,CP)为指示生物,96孔微板为暴露载体,污染物对藻的72 h生长抑制率为毒性指标,通过系统地检测蛋白核小球藻的生长曲线和吸收光谱,确定藻细胞密度和683 nm波长处光密度(D₆₈₃)之间的线性关系,考察不同初始藻密度、照度、暴露时间和暴露体积对藻生长的影响,建立了蛋白核小球藻微板毒性分析方法(CP-MTA法).将CP-MTA法应用于重金属盐、除草剂、杀虫剂以及离子液体等8种化学品对蛋白核小球藻的生长抑制毒性测试,以pEC₅₀为毒性指标,毒性大小顺序为敌草快>CuSO₄·5H₂O≈CdCl₂·2.5H₂O>氯化1-甲基-3-辛基咪唑(［Omim］Cl)>草甘膦>氯化1-甲基-3-丁基咪唑(［Bmim］Cl)>敌敌畏>乐果,与文献结果一致.CP-MTA法由于以微板为反应载体,所需样品少,便于多次平行,数据重复性好.      

Evaluation of drinking water treatment combined filter backwash water recycling technology based on comet and micronucleus assay

Based on the fact that recycling of combined filter backwash water（CFBW）directly to drinking water treatment plants（WTP）is considered to be a feasible method to enhance pollutant removal efficiency,we were motivated to evaluate the genotoxicity of water samples from two pilot-scale drinking water treatment systems,one with recycling of combined backwash water,the other one with a conventional process.An integrated approach of the comet and micronucleus（MN）assays was used with zebrafish（Danio rerio）to investigate the water genotoxicity in this study.The total organic carbon（TOC）,dissolved organic carbon（DOC）,and trihalomethane formation potential（THMFP）,of the recycling process were lower than that of the conventional process.All the results showed that there was no statistically significant difference（P>0.05）between the conventional and recycling processes,and indicated that the genotoxicity of water samples from the recycling process did not accumulate in 15 day continuous recycling trial.It was worth noting that there was correlation between the concentrations of TOC,DOC,UV₂₅₄,and THMFPs in water and the DNA damage score,with corresponding R² values of 0.68,0.63,0.28,and 0.64.Nevertheless,both DNA strand breaks and MN frequency of all water samples after disinfection were higher than that of water samples from the two treatment units,which meant that the disinfection by-products（DBPs）formed by disinfection could increase the DNA damage.Both the comet and MN tests suggest that the recycling process did not increase the genotoxicity risk,compared to the traditional process.     

CHO cell cytotoxicity and genotoxicity analyses of disinfection by-products: An updated review

The disinfection of drinking water is an important public health service that generates high quality, safe and palatable tap water. The disinfection of drinking water to reduce waterborne disease was an outstanding public health achievement of the 20th century. An unintended consequence is the reaction of disinfectants with natural organic matter, anthropogenic contaminants and bromide/iodide to form disinfection by-products (DBPs). A large number of DBPs are cytotoxic, neurotoxic, mutagenic, genotoxic, carcinogenic and teratogenic. Epidemiological studies demonstrated low but significant associations between disinfected drinking water and adverse health effects. The distribution of DBPs in disinfected waters has been well defined by advances in high precision analytical chemistry. Progress in the analytical biology and toxicology of DBPs has been forthcoming. The objective of this review was to provide a detailed presentation of the methodology for the quantitative, comparative analyses on the induction of cytotoxicity and genotoxicity of 103 DBPs using an identical analytical biological platform and endpoints. A single Chinese hamster ovary cell line was employed in the assays. The data presented are derived from papers published in the literature as well as additional new data and represent the largest direct quantitative comparison on the toxic potency of both regulated and emerging DBPs. These data may form the foundation of novel research to define the major forcing agents of DBP-mediated toxicity in disinfected water and may play an important role in achieving the goal of making safe drinking water better.     

Formation and cytotoxicity of a new disinfection by-product (DBP) phenazine by chloramination of water containing diphenylamine

Disinfection by-products (DBPs) in drinking water have caused worldwide concern due to their potential carcinogenic effects. The formation of phenazine from diphenylamine (DPhA) chloramination was studied and its cytotoxicities for two human cancer cells were also investigated. Phenazine was detected synchronously with the consumption of DPhA by chloramination, which further confirmed that the new DBP phenazine can be produced along with N-nitrosodiphenylamine (NDPhA) from DPhA chloramination. The formation of phenazine had a maximum molar yield with solution pH increasing from 5.0 to 9.0, with phenazine as the main product for DPhA chloramination at lower pH, but higher pH favored the formation of NDPhA. Thus, solution pH is the key factor in controlling the formation of phenazine and NDPhA. Both the initial DPhA and chloramine concentrations did not show a significant effect on the molar yields of phenazine, although increasing the chloramine concentration could speed up the reaction rate of DPhA with chloramines. The cytotoxicity assays showed that phenazine had significant cell-specific toxicity towards T24 (bladder cancer cell lines) and HepG2 (hepatic tumor cell lines) cells with IC50 values of 0.50 and 2.04 mmol/L, respectively, and T24 cells being more sensitive to phenazine than HepG2 cells. The IC50 values of phenazine, DPhA, and NDPhA for T24 cells were of the same order of magnitude and the cytotoxicity of phenazine for T24 cells was slightly lower than that of NDPhA (IC50, 0.16 mmol/L), suggesting that phenazine in drinking water may have an adverse effect on human health.     

Genotoxicity evaluation of drinking water sources in human peripheral blood lymphocytes using the comet assay

The potential harm of organic pollutants in drinking water to human health is widely focused on in the wodd; more and more pollutants with genotoxic substances are released into the aquatic environment. Water source samples were collected from 7 different localities of Nanjing City. The potential genotoxicity of organic extracts from drinking water sources were investigated by means of the comet assay in human peripheral lymphocytes. The results showed that all the organic extracts from all the water source samples could induce DNA damages of human peripheral blood lymphocytes at different levels. A significant difference （P 〈 0.01） was observed when compared with the solvent control, The DNA damage increased with the increase of the dosage of the original water source. Significant differences of DNA damage were observed in different drinking water sources, as shown by the multiple comparisons analysis at the dosage of 100x; the degree of DNA damage treated by Hushu waterworks （at town level） was the most serious, the arbitrary units （AU） was 141.62±6.96, however, that of Shangyuanmen waterworks （at city level） was only 109.64±2.97. The analysis also revealed that the genotoxicity of town＇s water sources was higher than that of the city. The results demonstrated that the comet assay can be successfully applied to the genotoxicity monitoring programs of drinking water sources.     

Identification of unknown disinfection byproducts in drinking water produced from Taihu Lake source water

Although disinfection byproducts(DBPs) in drinking water have been suggested as a cancer causing factor, the causative compounds have not yet been clarified. In this study, we used liquid chromatography quadrupole-time-of-flight spectrometry(LC-QTOF MS) to identify the unknown disinfection byproducts(DBPs) in drinking water produced from Taihu Lake source water, which is known as a convergence point for the anthropogenic pollutants discharged from intensive industrial activities in the surroundi...     

Disinfection by-product (DBP) research in China: Are we on the track?

Disinfection by-products (DBPs) formed during water disinfection has drawn significant public concern due to its toxicity. Since the first discovery of the trihalomethanes in 1974, continued effort has been devoted on DBPs worldwide to investigate the formation mechanism, levels, toxicity and control measures in drinking water. This review summarizes the main achievements on DBP research in China, which included: (1) the investigation of known DBP occurrence in drinking water of China; (2) the enhanced removal of DBP precursor by water treatment process; (3) the disinfection optimization to minimize DBP formation; and (4) the identification of unknown DBPs in drinking water. Although the research of DBPs in China cover the whole formation process of DBPs, there is still a challenge in effectively controlling the drinking water quality risk induced by DBPs, an integrated research framework including chemistry, toxicology, engineering, and epidemiology is especially crucial.     

蓝藻AOM特征与DBPs生成关系的研究进展

蓝藻水华期间,藻细胞因自然生长或受水处理工艺影响(如预氧化和混凝),会向水中释放大量藻源有机物(AOM),能够与氯消毒剂反应生成大量消毒副产物(DBPs),增加了饮用水安全风险.了解AOM的特征及其对DBPs生成的影响对于AOM的控制和饮用水安全保障至关重要.本文综述了蓝藻AOM的主要理化特征(溶解性有机碳、溶解性有机氮、亲疏水性、光学特性、分子量、化学结构)及其对饮用水处理过程中AOM的削减转化规律和DBPs生成的影响,并讨论了AOM前体表征技术在蓝藻水处理过程中追踪AOM变化和预测DBPs的应用前景,最后展望了未来的研究方向.     

饮用水消毒技术发展趋势的文献计量学分析

消毒过程是饮用水安全保障研究的热点,本文采用文献计量学的方法对2000—2012年间的学术论文和发明专利进行了分析,明确了全球在饮用水消毒领域的研究动态和趋势以及我国存在的主要差距.结果表明全球对该领域研究的关注度持续增加,其研究热点主要集中在消毒技术工艺和消毒副产物两方面,其中氯化、臭氧氧化、氯化消毒副产物是近十余年的关注焦点.美国和瑞士作为本领域研究的主要领先国家分别在文章产出量和研究水平上位列第一,值得注意的是瑞士在本领域的研究偏重于高级氧化技术和新型消毒副产物.我国的发文量仅次于美国而专利申请量仅次于日本,但研究水平远落后于世界领先国家.我国的研究工作主要集中在氯氧化消毒工艺和常规消毒副产物生成与控制,原创性研究有待加强.本研究对明确我国饮用水消毒技术的发展趋势和研究人员选题具有重要意义.     

饮用水中的消毒副产物及其控制策略

消毒副产物（disinfection by-products,DBPs）是在饮用水消毒时由消毒剂与有机或无机前体物反应生成的一类次生污染物,其由于具有致癌、致畸和致突变的三致特性在全球范围内广受关注.聚焦于饮用水中的DBPs,介绍了DBPs的主要分类和研究历程,汇总了多地饮用水中常见DBPs的浓度水平以及全球饮用水水质标准对DBP指标的管控要求.随后系统介绍了饮用水中DBPs的控制策略,包括源头控制、过程控制、末端控制以及协同控制这4大类,并对各类控制方法的优缺点进行了分析.评述了中国的DBPs研究的现有水平和未来趋势,并展望了未来有关DBPs控制方法的研究方向.一方面,在评价某种工艺或技术对DBPs的控制效果时需要考虑DBPs浓度和水质综合毒性的变化,另一方面,建议关注耦合源头、过程和末端控制技术的协同控制方法,兼顾从源头到龙头每个节点,实现对饮用水中各类DBPs的高效控制.     

全球饮用水标准中消毒副产物管控指标对比与启示

饮用水水质安全是关乎千家万户的重大民生问题,其中消毒工艺是保障饮用水微生物安全不可或缺的重要措施,然而由消毒剂与前体物反应生成的DBPs（消毒副产物）被发现具有潜在的健康风险,如致癌及引起发育副作用等.随着对饮用水中DBPs的重视程度不断提高,世界上多个国家、地区或组织将DBPs指标纳入标准.为对我国饮用水水质标准中DBPs指标的制定和修订提出可参考的建议,比较了国内外饮用水和再生水饮用回用水质标准中的DBPs指标,包括DBPs种类、对应的浓度限值和监测要求等.结果表明:①我国饮用水水质标准中涵盖的DBPs种类较多,其中地方标准相较于国标而言对DBPs指标的要求更为严格,但较少考虑综合性指标（如总有机卤素）和高毒性含氮DBPs（如卤乙腈）;②国外多部饮用水水质标准或准则中包含一些无浓度限值规定但已知具有较高健康风险的DBPs,此举可指导有关部门进一步开展浓度调研和毒性试验,为未来水质标准的制定提供参考依据.研究显示,我国饮用水标准中DBPs指标需要考虑综合性指标的选取与管控以及高风险指标的甄别和筛查,另外还需因地制宜加强地方性标准的建设工作.