New methods for identification of disinfection byproducts of toxicological relevance: Progress and future directions

Disinfection byproducts (DBPs) represent a ubiquitous source of chemical exposure in disinfected water. While over 700 DBPs have been identified, the drivers of toxicity remain poorly understood. Additionally, ever evolving water treatment practices have led to a continually growing list of DBPs. Advancement of analytical technologies have enabled the identification of new classes of DBPs and the quantification of these chemically diverse sets of DBPs. Here we summarize advances in new workflows for DBP analysis, including sample preparation, chromatographic separation with mass spectrometry (MS) detection, and data processing. To aid in the selection of techniques for future studies, we discuss necessary considerations for each step in the strategy. This review focuses on how each step of a workflow can be optimized to capture diverse classes of DBPs within a single method. Additionally, we highlight new MS-based approaches that can be powerful for identifying novel DBPs of toxicological relevance. We discuss current challenges and provide perspectives on future research directions with respect to studying new DBPs of toxicological relevance. As analytical technologies continue to advance, new strategies will be increasingly used to analyze complex DBPs produced in different treatment processes with the aim to identify potential drivers of toxicity.     

Volatile organic chloramines formation during ClO2 treatment

Volatile organic chloramines are reported as the disinfection byproducts during chlorination or chloramination.However,ClO_2,as an important alternative disinfectant for chlorine,was not considered to produce halogenated amines.In the present work,volatile organic chloramines including(CH_3)_2 NCl and CH_3 NCl_2 were found to be generated during the reaction of ClO_2 and the dye pollutants.(CH_3)_2 NCl was the dominant volatile DBP to result from ClO_2 treated all four dye pollutants including Methyl Orange,Methyl Red,Methylene Blue and Malachite Green,with molar yields ranging from 2.6% to 38.5% at a ClO_2 to precursor(ClO_2/P) molar ratio of 10.HOCl was identified and proved to be the reactive species for the formation of (CH_3)_2 NCl,which implied(CH_3)_2 NCl was transformed by a combined oxidation of ClO_2 and hypochlorous acid.(CH_3)_2 NCl concentrations in the ppb range were observed when real water samples were treated by ClO_2 in the presence of the dye pollutants.The results suggest that these azo dyes are one of the significant precursors for the formation of HOCl during ClO_2 treatment and that organic chloramines should be considered in ClO_2 disinfection chemistry and water treatment.     

氯、氯胺消毒下钱江源水源水消毒副产物形成特征研究

以钱江源水源水为研究对象,以氯、氯胺为消毒方式,研究了不同消毒条件下,三卤甲烷(THMs)、卤乙腈(HANs)、氯代酮(CKs)、二卤乙酸(DHAAs)、三卤乙酸(THAAs)等消毒副产物(DBPs)的形成情况,以便为水务工作者监测钱江源建库前后水质、DBPs形成的变化提供基础数据.结果显示,氯消毒下DBPs的产量比氯胺消毒高出3~7倍甚至1个数量级,但不管是氯消毒还是氯胺消毒,THMs、HAAs形成量均在我国饮用水标准范围内.氯消毒下,大部分DBPs产量为中、碱性条件酸性条件(除了CKs),氯胺消毒则呈现不同的情况(所有DBPs的产量均为p H=6、p H=7p H=8).消毒剂量对所有DBPs形成具有明显的促进作用;溴离子对THMs、DHANs、DHAAs的形成有明显的促进作用.进一步研究表明,钱江源水源水的水质比钱塘江下游九溪水源水好,DBPs形成也较低,某些指标(如有机碳、有机氮、HANs形成量等)甚至比同省水质较好的金兰水库还要好;而且由于其较高的比紫外吸收值(SUVA),DBPs的溴嵌入能力均比九溪水源水、金兰水库低.此外,就目前的钱江源水源水来说,控制消毒剂量(氯、或氯胺)是控制DBPs形成的有效策略.     

供水管网终端消毒副产物分布特征及预测模型

消毒副产物(disinfection by-products, DBPs)是影响饮用水水质的重要指标.以浙江省H市某区域供水点为调查目标,考察终端龙头水及加热器处理后饮用水中DBPs的含量特征,结合水质理化指标,初步确定管网终端DBPs预测模型,评估经口摄入的健康风险.结果表明,H市某供水点龙头水中共检出THMs、HANs和HAAs这3类共计10种DBPs.龙头水中目标DBPs检出率均为100%,THMs、HANs和HAAs质量浓度分别为10.12～28.39、 0.98～5.19和2.65～7.83μg·L~(-1);热水中TBM、TCAN和DBAN的检出率分别为46.43%、 82.14%和92.86%,BCAN未检出,其它DBPs检出率为100%,THMs、HANs和HAAs质量浓度分别为0.60～12.58、 0.02～0.52和2.42～5.86μg·L~(-1).加热处理后THMs和HANs的含量有所降低,总量分别降低84.22%和91.45%,HAAs变化不明显.水质理化指标pH值和SUVA与DBPs呈正相关关系,余氯和氨氮与DBPs呈负相关关系.根据常规指标与DBPs相关性建立THMs多元线性预测模型,相对误差小于10.00%,准确度较高,可用于管网供水终端THMs的预测.基于美国环保署推荐的健康风险评价模型对经口摄取途径时氯消毒副产物的致癌和非致癌风险进行计算,发现H市龙头水和热水中DBPs通过饮水途径的致癌风险分别为(17.24～84.63)×10~(-6)和(25.49～258.82)×10~(-7);非致癌风险分别为(4.17～50.32)×10~(-2)和(6.52～107.74)×10~(-3).龙头水中BDCM对致癌风险的贡献率最大,而热水系统中TCM贡献率最大;龙头水及热水中非致癌风险主要来自于TCM.热水中THMs的削减量最高达到94.38%,致癌风险降低79.00%.     

A new technique helps to uncover unknown peptides and disinfection by-products in water

正Environmental water samples can be extremely complex,with potentially thousands of molecules that can derive from natural organic matter(NOM)and thousands that derive from anthropogenic contaminants.As complex as these samples are,drinking water can be even more complex.Due to disinfectants that are used to treat drinking water(e.g.,chlorine,chloramines,     

水中微量消毒副产物的光催化降解

采用光催化氧化工艺考察了饮用水部分消毒副产物的光催化降解效果.结果表明,TiO₂薄膜催化剂在低压汞灯照射下能明显提高致癌致突变有机物的光降解速率,其中卤代烷烃的光催化降解较光降解提高了3～7倍,而烯烃和芳香类物质的光催化降解较光降解也提高了2～3倍.总地来说,不同物质的降解规律为苯乙烯的降解速率最大,邻甲酚其次,烯烃较烷烃的光催化降解速率有明显提高,芳香烯烃较脂肪烯烃的降解速率高,而氯代烷烃的光催化降解效果非常接近.     

新冠疫情下武汉典型饮用水水源中DBPs污染特征与风险评估

为了揭示新冠肺炎疫情下武汉典型饮用水水源中消毒副产物（DBPs）的污染特征与风险水平,选取武汉典型饮用水源地26个采样点位,采用N,N-二乙基-1,4-苯二胺分光光度法和气相色谱仪-微池电子捕获检测器（GC-μECD）法分别对水体中残余氯消毒剂和DBPs进行了检测,并开展健康与生态风险评估.结果表明,26个点位中有16个检出了游离氯或总余氯,检出最大浓度为0.04 mg·L^-1,部分点位游离氯超过了国家地表水标准,靠近城市污水厂排水口的点位浓度相对较高.对10个代表性点位进行了34种DBPs的检测,有24种物质被检出,检出率为10.00%～100.00%;ρ（总DBPs）浓度范围为0.11～104.73μg·L^-1,平均值为7.26μg·L^-1.三氯甲烷检出浓度最高,浓度范围为9.98～11.15μg·L^-1,平均值为10.47μg·L^-1;一溴一碘乙酰胺检出浓度最低,浓度范围为ND～0.11μg·L^-1,平均值为0.01μg·L^-1...     

臭氧-混凝交互作用对水体有机物的影响

研究臭氧在纯水和混凝剂[Al_2(SO_4)_3]溶液中残余浓度的变化;采用差异吸收分析(differential absorbance,DA)、三维荧光(three dimensional fluorescence excitation-emission matrix spectroscopy,3D-EEM)和气相色谱(gas chromatograph,GC)、总有机碳分析(total organic carbon analyser,TOC)等研究水体有机物(富里酸)光谱特征、有机物和消毒副产物(DBPs)生成量在预臭氧、预臭氧-混凝(POC)以及臭氧-混凝联用(OC)后的差异;研究臭氧和混凝联合作用对有机物氧化程度及其对DBPs生成的影响.结果表明POC与OC作用存在明显差别,臭氧与混凝剂Al_2(SO_4)_3存在交互作用.交互作用主要体现在:(1)臭氧-混凝联用时臭氧降解速率加快;且臭氧降解中自由基产量相对增加.当臭氧投量2 mg·L~(-1),Al3+含量为1 mg·L~(-1)、3 mg·L~(-1)时,自由基捕获量比单独臭氧分别高15.2%和23.9%.(2)联用和预臭氧-混凝对有机物反应的差异,体现在OC有机物去除率低于POC,二者对有机物的反应途径不同;进而导致有机物与消毒剂反应的差异以及DBPs生成的差异.联用对DOC的去除能力明显强于单独臭氧和单独混凝,但弱于预氧化-混凝.当O3浓度为1 mg·L~(-1)、Al3+1 mg·L~(-1)时POC处理后二氯乙酸生成势(DCAAFP)和三氯乙酸生成势(TCAAFP)分别为47μg·L~(-1)和20.5μg·L~(-1),三氯甲烷生成势(CFFP)为97.8μg·L~(-1),较原水分别降低51%、64.6%和41.5%;而相应臭氧-混凝处理后DCAAFP和TCAAFP分别为48.4μg·L~(-1)和21.4μg·L~(-1),CFFP为117.3μg·L~(-1);较原水分别降低49.6%、63%和29.5%.同等臭氧投量下,增加混凝剂的剂量,POC和OC处理效果的差异进一步扩大.为保证用水安全和处理效率,臭氧和混凝联用时对臭氧的浓度、投加位置、混凝剂的种类等都需要进一步的研究论证,慎重选择.     

饮用水中消毒副产物-卤化酮的生成特性与控制研究进展

卤化酮（haloketones）具有较强的致癌、致畸和致突变性,是饮用水处理领域颇为关注的一类卤代消毒副产物。这类物质可广泛存在于经消毒后的出厂水中,其含量仅次于三卤甲烷、卤乙酸和卤代腈,浓度一般在ng/L与μg/L的水平。鉴于卤化酮具有较强的致癌、致畸和致突变性,是饮用水处理领域颇为关注的一类卤代消毒副产物,本文对其分类特性、检测方法、生成机理、遗传毒性和致癌性、控制方法等进行了综述,这对于国内开展该方向的研究具有参考价值。     

人工回灌过程中胶体对CHCl3形成机制的影响

以揭示回灌过程中CHCl₃耦合胶体效应影响下的二次形成作用为研究目标,通过批实验分析有、无胶体条件下不同水化学条件对CHCl₃生成速率及生成量的影响,并结合切向流超滤技术和原子力电镜扫描（AFM）表征手段分析CHCl₃-SiO₂胶体协同作用模式.结果表明,CHCl₃的生成量随着反应时间的增加而增大,并在特定的反应时间内,高氯/TOC比率、高pH值、低离子强度均会促进CHCl₃的二次形成.SiO₂胶体的存在会影响反应前体物的吸附,使各时刻CHCl₃生成作用均受到抑制,并对水中的CHCl₃有强吸附作用.结果可为人工回灌过程中CHCl₃的二次形成作用提供科学参考.