The chlorination transformation characteristics of benzophenone-4 in the presence of iodide ions

Benzophenone-type UV filters are a group of compounds widely used to protect human skin from damage of UV irradiation. Benzophenone-4 (BP-4) was targeted to explore its transformation behaviors during chlorination disinfection treatment in the presence of iodide ions. With the help of ultra performance liquid phase chromatograph and high-resolution quadrupole time-of-flight mass spectrometer, totally fifteen halogenated products were identified, and five out of them were iodinated products. The transformation mechanisms of BP-4 involved electrophilic substitution generating mono- or di-halogenated products, which would be oxidized into esters and further hydrolyzed into phenolic derivatives. The desulfonation and decarboxylation were observed in chlorination system either. Obeying the transformation pathways, five iodinated products formed. The pH conditions of chlorination system determined the reaction types of transformation and corresponding species of products. The more important was that, the acute toxicity had significant increase after chlorination treatment on BP-4, especially in the presence of iodide ions. When the chlorination treatment was performed on ambient water spiked with BP-4 and iodide ions, iodinated by-products could be detected.     

Effect of ferric and bromide ions on the formation and speciation of disinfection byproducts during chlorination

The e ects of ferric ion, pH, and bromide on the formation and distribution of disinfection byproducts (DBPs) during chlorination were studied. Two raw water samples from Huangpu River and Yangtze River, two typical drinking water sources of Shanghai, were used for the investigation. Compared with the samples from Huangpu River, the raw water samples from Yangtze River had lower content of total organic carbon (TOC) and ferric ions, but higher bromide concentrations. Under controlled chlorination conditions, four trihalomethanes (THMs), nine haloacetic acids (HAAs), total organic halogen (TOX) and its halogen species fractions, including total organic chlorine (TOCl) and total organic bromide (TOBr), were determined. The results showed that co-existent ferric and bromide ions significantly promoted the formation of total THMs and HAAs for both raw water samples. Higher concentration of bromide ions significantly changed the speciation of the formed THMs and HAAs. There was an obvious shift to brominated species, which might result in a more adverse influence on the safety of drinking water. The results also indicated that high levels of bromide ions in raw water samples produced higher percentages of unknown TOBr.     

Interactions of fluoroquinolone antibiotics with sodium hypochlorite in bromide-containing synthetic water: Reaction kinetics and transformation pathways

Seven popular fluoroquinolone antibiotics (FQs) in synthetic marine aquaculture water were subject to sodium hypochlorite (NaClO) disinfection scenario to investigate their reaction kinetics and transformation during chlorination. Reactivity of each FQ to NaClO was following the order of ofloxacin (OFL) > enrofloxacin (ENR) > lomefloxacin (LOM) > ciprofloxacin (CIP) ~ norfloxacin (NOR) >> pipemedic acid (PIP), while flumequine did not exhibit reactivity. The coexisting chlorine ions and sulfate ions in the water slightly facilitated the oxidation of FQs by NaClO, while humic acid was inhibitable to their degradation. The bromide ions promoted degradation of CIP and LOM, but restrained oxidation of OFL and ENR. By analysis of liquid chromatography with tandem mass spectrometry (LC-MS/MS), eight kinds of emerging brominated disinfection byproducts (Br-DBPs) caused by FQ_S were primarily identified in the chlorinated synthetic marine culture water. Through density functional theory calculation, the highest-occupied molecular orbital (HOMO) and the lowest-unoccupied molecular orbital (LUMO) characteristic as well as the charge distribution of the FQs were obtained to clarify transformation mechanisms. Their formation involved decarboxylation, ring-opening/closure, dealkylation and halogenation. Chlorine substitution occurred on the ortho-position of FQs's N4 and bromine substitution occurred on C8 position. The piperazine ring containing tertiary amine was comparatively stable, while this moiety with a secondary amine structure would break down during chlorination. Additionally, logK_ow and logBAF of transformation products were calculated by EPI-Suite^TM to analyze their bioaccumulation. The values indicated that Br-DBPs are easier to accumulate in the aquatic organism relative to their chloro-analogues and parent compounds.     

加氯消毒过程中纯细菌物质生成消毒副产物研究

按照UFC方法对水体中3种常见细菌Acinetobacter junii、Staphylococcussciuri和Escherichia coli进行纯细菌加氯消毒处理,同时考察水中溴离子对纯细菌物质生成DBPs的影响.结果表明,3种细菌均为DBPs前体物,加氯消毒生成的DBPs除水合三氯乙醛(CHD)外,生成的三卤甲烷(THMs)物质主要为氯仿(TCM),卤乙腈(HANs)物质主要为二氯乙腈(DCAN).氯仿的生成量与细菌物质TOC浓度无明显关系,但HANs和CHD生成量均随细菌TOC浓度增大而增加.其中革兰氏阳性细菌Staphylococcus sciuri生成的DCAN和CHD比革兰氏阴性细菌Acinetobacter junii和Escherichia coli生成的要高,说明细胞壁的化学组分可能是DCAN和CHD生成的影响因素之一.Escherichia coli细菌反应液中溴离子(Br-)存在时,除生成CHD、TCM及DCAN外,THMs和HANs中的溴代种类CHBr3随Br-增多而持续增加,相反TCM持续减少.当Br-浓度为4mg.L-1时,TBM浓度增至最高127.9μg.L-1;HANs和CHD生成量随Br-浓度增加先有所增加,随后持续降低至低于检测限;Br离子存在时THMs为主要DBPs种类.     

南水北调丹江口水库水氯(胺)化消毒副产物产生特性与消毒工艺对比

系统研究了南水北调中线工程水源——丹江口水库水在氯(胺)化消毒条件下,常规消毒副产物的产生特性,考察了消毒方式、消毒剂投加量、接触时间、p H和溴离子浓度等因素的影响,并对消毒工艺参数进行了优化.结果发现,丹江口水库水经氯化消毒可产生三氯甲烷、二氯一溴甲烷等常规含碳和较低浓度二氯乙腈、三氯硝基甲烷等含氮消毒副产物,而氯胺化消毒仅产生三氯甲烷和三氯硝基甲烷等消毒副产物(disinfection by-products,DBPs).自由氯消毒过程产生的各类型DBPs浓度约为氯胺消毒的7.5倍,短时自由氯转氯胺方式DBPs产生量介于两者之间;随着自由氯投加量增加,各类型消毒副产物均呈现增加趋势,投加量大于2 mg·L-1后DBPs增加量较少.随氯胺投加量增加,三氯甲烷生成量变化不大,投加量大于2mg·L-1后可产生三氯硝基甲烷等副产物.随反应时间延长,自由氯的衰减速率明显大于氯胺,同时消毒副产物增长量明显快于氯胺消毒.随着p H升高,自由氯消毒后三卤甲烷含量呈现增加趋势,而氯胺消毒后变化不明显.随溴离子浓度的增加,自由氯和氯胺消毒后副产物类型均向溴代DBPs转变,同时总生成量明显增加,自由氯消毒DBPs增长量明显大于氯胺消毒过程.丹江口水库水采用氯胺化消毒可以降低消毒副产物的生成风险,如采用自由氯消毒方式,水厂需根据实际常规处理工艺重点控制自由氯的投加量等参数.     

含溴黄浦江水消毒过程中溴代三卤甲烷和卤乙酸的生成特性

通过水厂出水DBPs调查和氯化培养实验探讨了黄浦江水中溴离子（Br-）在消毒过程中的迁移及对含溴副产物（溴代三卤甲烷和卤乙酸）生成的影响.结果表明,采用氯胺消毒的水厂出水中约10%的Br-迁移至Br-THMs和Br-HAAs.氯化培养时,在余氯充足的前提下增加Br-浓度,总有机溴（TOBr）和含溴副产物均增加.延长氯化...     

新型溴代苯酚类消毒副产物的氯化降解机制

最近,13种新型极性卤代苯酚类消毒副产物在氯化消毒后的饮用水中被发现,它们按结构被分成4组,分别是二卤-4-羟基苯甲醛、二卤-4-羟基苯甲酸、二卤水杨酸和三卤苯酚.为研究它们在氯化消毒过程中的降解机制,选取了其中的4种全溴代种类,即3,5-二溴-4-羟基苯甲醛、3,5-二溴-4-羟基苯甲酸、3,5-二溴水杨酸以及2,4,6-三溴苯酚,利用UPLC/ESI-tq MS中的前体离子扫描,多反应监测和子离子扫描,鉴定了这几种消毒副产物在氯化消毒过程中的中间产物以及终产物,并根据这些中间产物和终产物与消毒时间的关系推测了其降解路径.结果表明,除了3,5-二溴水杨酸相对较稳定外,其余3种消毒副产物在氯化消毒过程中不稳定,通过取代、水解以及氧化等过程最终降解为卤乙酸等脂肪族小分子消毒副产物.在降解过程中有许多中间产物被检测并鉴定出来,其中包含一组具有五元环结构的新型消毒副产物(三卤代-羟基环戊烯二酮).     

Characterization of disinfection byproduct formation potential in 13 source waters in China

The formation potential of four trihalomethanes (THMFP) and seven haloacetic acids (HAA7FP) in 13 source waters taken from four major water basin areas in China was evaluated using the simulated distribution system (SDS) chlorination method. The specific ultraviolet absorbance (SUVA254: the ratio of UV254 to dissolved organic carbon (DOC)), which ranged between 0.9 and 5.0 L/(mg m), showed that the organic compounds in di erent source waters exhibited di erent reactivities with chlorine. The HAA7FP of source waters ranged from 20 to 448 g/L and the THMFP ranged from 29 to 259 g/L. The HAA7FP concentrations were higher than the THMFP concentrations in all but one of the samples. Therefore, the risks of haloacetic acids (HAAs) should be of concern in some source waters. TCM (chloroform) and BDCM (bromodichloromethane) were the major THM constituents, while TCAA (trichloroacetic acid) and DCAA (dichloroacetic acid) were the major HAA species. Br-THM (brominated THM species) were much higher than Br- HAA (brominated HAA species), and the formation of Br-DBP (Br-THM and Br-HAA) should be of concern when the bromide concentration is over 100 g/L.     

Disinfection byproduct regulatory compliance surrogates and bromide-associated risk

Natural and anthropogenic factors can alter bromide concentrations in drinking water sources. Increasing source water bromide concentrations increases the formation and alters the speciation of disinfection byproducts (DBPs) formed during drinking water treatment. Brominated DBPs are more toxic than their chlorinated analogs, and thus have a greater impact on human health. However, DBPs are regulated based on the mass sum of DBPs within a given class (e.g., trihalomethanes and haloacetic acids), not based on species-specific risk or extent of bromine incorporation. The regulated surrogate measures are intended to protect against not only the species they directly represent, but also against unregulated DBPs that are not routinely measured. Surrogates that do not incorporate effects of increasing bromide may not adequately capture human health risk associated with drinking water when source water bromide is elevated. The present study analyzes trihalomethanes (THMs), measured as TTHM, with varying source water bromide concentrations, and assesses its correlation with brominated THM, TTHM risk and species-specific THM concentrations and associated risk. Alternative potential surrogates are evaluated to assess their ability to capture THM risk under different source water bromide concentration conditions. The results of the present study indicate that TTHM does not adequately capture risk of the regulated species when source water bromide concentrations are elevated, and thus would also likely be an inadequate surrogate for many unregulated brominated species. Alternative surrogate measures, including THM3 and the bromodichloromethane concentration, are more robust surrogates for species-specific THM risk at varying source water bromide concentrations.     

水加氯处理时NHCl2与溴化物的反应特性研究

含氨水进行氯化处理时会产生ＮＨ２Ｃｌ和ＮＨＣｌ２,当水中含有溴化物时,氯胺类会与会中的Ｂｒ＾－反应,ＮＨ２Ｃｌ与Ｂｒ＾－的反应速度随ｐＨ增加和Ｂｒ＾－浓度降低而减慢;ＮＨＣｌ２与溴化物的反应比较复杂,２者的反应存在着一个诱导期,诱导期的长短与Ｂｒ＾－浓度对数成反比,ＮＨＣｌ２与Ｂｒ＾－的反应速度对ＮＨＣｌ２为一级反应;用紫外光谱,气相色谱和疏水微孔渗透法研究了该反应产物,确认反应产物为Ｂｒ＾－的反     

Formation of regulated and unregulated disinfection byproducts during chlorination and chloramination: Roles of dissolved organic matter type, bromide, and iodide

Algal blooms and wastewater effluents can introduce algal organic matter (AOM) and effluent organic matter (EfOM) into surface waters, respectively. In this study, the impact of bromide and iodide on the formation of halogenated disinfection byproducts (DBPs) during chlorination and chloramination from various types of dissolved organic matter (DOM, e.g., natural organic matter (NOM), AOM, and EfOM) were investigated based on the data collected from literature. In general, higher formation of trihalomethanes (THMs) and haloacetic acids (HAAs) was observed in NOM than AOM and EfOM, indicating high reactivities of phenolic moieties with both chlorine and monochloramine. The formation of haloacetaldehydes (HALs), haloacetonitriles (HANs) and haloacetamides (HAMs) was much lower than THMs and HAAs. Increasing initial bromide concentrations increased the formation of THMs, HAAs, HANs, and HAMs, but not HALs. Bromine substitution factor (BSF) values of DBPs formed in chlorination decreased as specific ultraviolet absorbance (SUVA) increased. AOM favored the formation of iodinated THMs (I-THMs) during chloramination using preformed chloramines and chlorination-chloramination processes. Increasing prechlorination time can reduce the I-THM concentrations because of the conversion of iodide to iodate, but this increased the formation of chlorinated and brominated DBPs. In an analogous way, iodine substitution factor (ISF) values of I-THMs formed in chloramination decreased as SUVA values of DOM increased. Compared to chlorination, the formation of noniodinated DBPs is low in chloramination.     

Fe3+和Br-对饮用水氯消毒过程中挥发性卤代烃生成的影响

以腐殖酸模拟天然水体中的活性消毒副产物的前体物,研究了含腐殖酸水样中溴离子和三价铁离子对氯消毒反应过程中挥发性卤代烃三卤甲烷(THMs)的生成量和相对分布的影响.结果表明,水样中的溴离子浓度增加将增加溴代三卤甲烷和总三卤甲烷的生成量, 在Br^-离子浓度1.0 mg/L时,THMs的总量为不含Br^-时的2.7倍;当水样中含有溴离子时,在偏酸性条件下三价铁对三卤甲烷的生成有一定的抑制作用,在偏碱性条件下三价铁离子提高了溴离子与腐殖酸的反应活性,从而提高了三卤甲烷的生成总量.Fe³⁺浓度为5 mg/L时,三溴甲烷的生成量与无Fe³⁺存在时相比,由51.7 μg/L增加到79.4 μg/L, 增加幅度达54%,THMs的总量从113.49 μg/L增加到162.09 μg/L.溴离子对饮用水的安全性具有较大的负面影响,溴离子和三价铁离子共存于偏碱性环境中时对加氯消毒后饮用水的致癌风险的影响显著增大,当Br^-含量为0.2 mg/L、Fe³⁺含量为5 mg/L时,在pH为6和8的条件下,致癌风险比饮用水中不含Br^-和Fe³⁺时分别增加2.5和5.1倍.     

氯消毒中有机防晒剂BP9的去除转化与风险评价

对典型有机防晒剂二苯甲酮-9（BP9）在氯消毒过程中的氧化反应进行研究,考察BP9初始浓度、余氯初始浓度、溶液pH值和氨氮浓度对反应的影响,探究BP9氯氧化降解机理,评估其生态风险.结果表明,在BP9初始浓度5mg/L、余氯初始浓度5mg/L的条件下,90s内BP9去除率达到91.3%,符合准一级反应动力学.降解速率常数随着BP9初始浓度及氨氮浓度增加而减小,随余氯初始浓度增大而增大,中性条件下有利于BP9氯氧化反应.基于HPLC-MS/MS和GC-MS解析出7种中间产物,提出可能降解路径.发光细菌毒性分析和ECOSAR预测均表明,BP9氯氧化反应生成了比母物质毒性更高的中间产物,对饮用水水质安全造成潜在风险.     

溴代阻燃剂对氧化亚铁硫杆菌浸提废旧电脑主板覆层铜的影响

以破碎至10~20目(0.84~2.00 mm)的废旧电脑主板颗粒为试验材料,分为未处理(未去除溴代阻燃剂的主板颗粒)、处理(去除30%溴代阻燃剂的主板颗粒)、加萃取物(处理主板颗粒和萃取物)、对照4组. 以CCl₄作为萃取剂,采用固液萃取技术,分析了在微生物作用下不同处理组中ρ(Cu2+)、ρ(Fe3+)、E_h(氧化还原电位)和pH的变化,以考察溴代阻燃剂对氧化亚铁硫杆菌(Thiobacillus ferrooxidans)浸Cu率的影响. 结果表明:随着浸提时间的增加,氧化亚铁硫杆菌对未处理、处理和加萃取物3组的浸Cu率不同,其中处理组最好,加萃取物组最差. 浸提过程中,ρ(Fe3+)、E_h和pH与微生物活性、浸Cu率显著相关,表现为微生物活性越好,ρ(Cu2+)和pH越大,ρ(Fe3+)和E_h越小. 浸提24和168 h,处理组的浸Cu率比未处理组分别提高了14.11%和17.37%; 而加萃取物组的浸Cu率比未处理组分别降低了27.69%和21.67%. 表明废旧电脑主板中的溴代阻燃剂是影响微生物浸Cu率的重要因素之一. 为进一步提高浸Cu率,必须考虑溴代阻燃剂对微生物生长的影响.      

水中利谷隆氯化降解动力学和消毒副产物生成特性

采用常用消毒剂次氯酸钠对含氮除草剂利谷隆开展了氯化降解实验研究,系统考察了加氯量、p H值、加Br-量以及温度对降解效果的影响,分析了氯化反应过程中消毒副产物生成特性.结果表明,次氯酸钠对利谷隆的氧化降解过程符合二级反应动力学;p H值对该降解反应影响较大,当p H值为7时反应速率最快,其中HOCl、OCl-与利谷隆的基元反应速率常数分别为4.84×102L·(mol·h)-1和3.80×102L·(mol·h)-1.在添加溴离子时,反应速率随着溴离子的加入逐渐减小.改变温度时,反应速率随着温度的增加而逐渐增大.利谷隆在氯化降解过程中可产生三氯甲烷、二氯乙腈、三氯硝基甲烷、卤代丙酮等多类型消毒副产物.在不同p H值和添加溴离子条件下,消毒副产物种类与浓度会出现显著差异.     

Formation potentials of typical disinfection byproducts and changes of genotoxicity for chlorinated tertiary effluent pretreated by ozone

The effects of ozonation on the formation potential of typical disinfection byproducts (DBPs) and the changes of genotoxicity during post chlorination of tertiary effluent from a sewage treatment plant were investigated. Ozonation enhanced the yields of all detected chlorine DBPs except CHCl3. At a chlorine dose of 5 mg/L, the three brominated THMs and five HAAs increased, while chloroform decreased with the increase of ozone dose from 0 to 10 mg/L (ozone dose in consumption base). At a chlorine dose of 10 ...     

Simultaneous removal of dissolved organic matter and bromide from drinking water source by anion exchange resins for controlling disinfection by-products

Anion exchange resins （AERs） with different properties were evaluated for their ability to remove dissolved organic matter （DOM） and bromide, and to reduce disinfection by-product （DBP） formation potentials of water collected from a eutrophic surface water source in Japan. DOM and bromide were simultaneously removed by all selected AERs in batch adsorption experiments. A polyacrylic magnetic ion exchange resin （MIEX） showed faster dissolved organic carbon （DOC） removal than other AERs because it had the smallest resin bead size. Aromatic DOM fractions with molecular weight larger than 1600 Da and fluorescent organic fractions of fulvic acid- and humic acid-like compounds were efficiently removed by all AERs. Polystyrene AERs were more effective in bromide removal than polyacrylic AERs. This result implied that the properties of AERs, i.e. material and resin size, influenced not only DOM removal but also bromide removal efficiency, MIEX showed significant chlorinated DBP removal because it had the highest DOC removal within 30 rain, whereas polystyrene AERs efficiently removed brominated DBPs, especially brominated trihalomethane species. The results suggested that, depending on source water DOM and bromide concentration, selecting a suitable AER is a key factor in effective control of chlorinated and brominated DBPs in drinking water.     

Formation of iodo-trihalomethanes, iodo-haloacetic acids, and haloacetaldehydes during chlorination and chloramination of iodine containing waters in laboratory controlled reactions

Iodine containing disinfection by-products (I-DBPs) and haloacetaldehydes (HALs) are emerging disinfection by-product (DBP) classes of concern. The former due to its increased potential toxicity and the latter because it was found to be the third most relevant DBP class in mass in a U.S. nationwide drinking water study. These DBP classes have been scarcely investigated, and this work was performed to further explore their formation in drinking water under chlorination and chloramination scenarios. In order to do this, iodo-trihalomethanes (I-THMs), iodo-haloacetic acids (I-HAAs) and selected HALs (mono-HALs and di-HALs species, including iodoacetaldehyde) were investigated in DBP mixtures generated after chlorination and chloramination of different water matrices containing different levels of bromide and iodide in laboratory controlled reactions. Results confirmed the enhancement of I-DBP formation in the presence of monochloramine. While I-THMs and I-HAAs contributed almost equally to total I-DBP concentrations in chlorinated water, I-THMs contributed the most to total I-DBP levels in the case of chloraminated water. The most abundant and common I-THM species generated were bromochloroiodomethane, dichloroiodomethane, and chlorodiiodomethane. Iodoacetic acid and chloroiodoacetic acid contributed the most to the total I-HAA concentrations measured in the investigated disinfected water. As for the studied HALs, dihalogenated species were the compounds that predominantly formed under both investigated treatments.     

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.     

太湖、钱塘江取水口底泥及周边土壤有机物形成消毒副产物的特征研究

底泥、土壤均是水体有机物的重要来源,但目前相关消毒副产物(DBPs)形成方面的研究偏少.本研究以长三角重要水源地太湖、钱塘江取水口的底泥和周边土壤的浸出液为研究对象,探索氯、臭氧+氯、氯胺、臭氧+氯胺4种消毒方式下,三卤甲烷(THMs)、卤代酮(HKs)、卤乙腈(HANs)、卤代硝基甲烷(HNMs)的形成情况.结果表明,太湖、钱塘江取水口的底泥、周边土壤有机物的芳香度均很低(SUVA254(即比紫外吸光值)2),与腐殖质(Sigma)相比,底泥、土壤有机物不是氯消毒中THMs的重要前驱物,但却是HANs特别是HNMs的重要前驱物.相比氯消毒,氯胺消毒能大幅降低土壤、底泥有机物THMs、HKs、HANs、HNMs的生成量,而且也可抑制含溴DBPs的形成.臭氧预处理大幅提高了氯、氯胺消毒中HKs、HNMs的产量,但对THMs、HANs则不一定.太湖、钱塘江的土壤、底泥存在一定的溴污染,但不管是哪种消毒方式,均是HNMs的溴嵌入因子最大.