模拟泳池水中氯化消毒副产物的生成规律

以模拟泳池水为研究对象,研究不同的氯化时间、氯投加量、pH值、反应温度条件对泳池水在氯化消毒过程中生成消毒副产物（DBPs）的影响.研究结果表明：延长氯化反应时间,二氯乙酸（DCAA）、三氯乙酸（TCAA）和三氯甲烷（TCM）的浓度不断升高,二氯乙腈（DCAN）、三氯硝基甲烷（TCNM）和1,1,1-三氯丙酮（1,1,1-TCP）的浓度则先升高再降低.DBPs浓度在氯化反应的前24h增幅较大,48h后趋于平缓;随着氯投加量的增加,DCAA、TCAA、TCM、TCNM和1,1,1-TCP浓度一直呈上升趋势,而DCAN浓度则先升高再降低.在氯投加量为2mg/L时,DBPs的浓度较低;在pH值从6升高到8的过程中,DCAA、TCAA、DCAN和1,1,1-TCP浓度先升高再降低,TCM和TCNM浓度则一直升高.pH值在6~7范围内可有效控制DBPs的形成;随着反应温度的升高,DCAA、TCAA、TCM和TCNM浓度持续升高,DCAN和1,1,1-TCP则逐渐降低.综上所述,应合理调节泳池水的氯化消毒条件,在保证舒适度的同时有效控制DBPs的生成.     

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.      

高锰酸钾预氧化对剑水蚤DBPsFP的去除特征研究

以剑水蚤为试验对象,研究在不同条件下,高锰酸钾预氧化对剑水蚤代谢产物在氯化消毒过程中消毒副产物前体物的去除特征.研究表明:随高锰酸钾投加量的增加,水合氯醛(CH)、1,1,1-三氯丙酮(1,1,1-TCP)、三氯甲烷(TCM)总体呈上升趋势,二氯乙酸(DCAA)逐渐减少,而三氯硝基甲(TCNM)、1,1-二氯丙酮(1,1-DCP)、二氯乙腈(DCAN)和三氯乙酸(TCAA)先上升后下降,在本试验高锰酸钾投量范围内,高锰酸钾浓度为5mg/L时 CH、TCNM、DCAN、TCAN、DCAA、TCAA和1,1-DCP的去除效果最佳,去除率最高可达72.2%;延长预氧化时间,DCAN、DCAA、TCAA浓度逐渐降低,TCM、CH浓度逐渐升高,TCNM、TCAN、1,1,1-TCP浓度先升高后降低,而1,1-DCP浓度先迅速下降后逐渐升高,预氧化时间宜控制在20min;pH<7可有效抑制TCM的生成.pH=7时TCAA达到最小值,而1,1-DCP含量最高,pH>7有助于1,1-DCP的减少,CH、DCAA、DCAN、TCAN、TCNM和1,1,1-TCP随pH的增加而减少.在pH=9时生成量均最小, 最高去除率为80%;最佳温度为30℃,随着温度的升高,DCAA、TCAA和TCM浓度有所增加,1,1-DCP、DCAN和1,1,1-TCP生成量减少,在20℃时,CH的浓度最小,而TCAN的浓度最大.     

高锰酸盐复合药剂预氧化对摇蚊幼虫DBPsFP的去除控制研究

以花翅摇蚊幼虫为试验对象,研究高锰酸盐复合药剂预氧化对摇蚊幼虫代谢产物在氯化消毒过程中消毒副产物前体物的去除控制.研究表明:在p H由5升高到9时,三氯乙酸(TCAA)与二氯乙酸(DCAA)的浓度呈逐渐减少趋势;p H由5升高到7时,三氯甲烷(TCM)和三氯乙腈(TCAN)的浓度减幅最大,1,1-二氯丙酮(1,1-DCP)和1,1,1-三氯丙酮(1,1,1-TCP)则在p H为8时浓度达到最低值;随着药剂投加量的增加,TCM呈现出持续稳定增长趋势,DCAA呈总体下降趋势,而TCAN、1,1-DCP、1,1,1-TCP和TCAA则先增加后减少,高锰酸盐的投加量为3mg·L-1时,消毒副产物去除效果显著;延长预反应时间,TCM呈总体上升趋势,1,1-DCP、DCAA、TCAA呈下降趋势,TCAN、1,1,1-TCP呈先增加后减少的趋势,综合考虑最佳预氧化时间为30 min;投加混凝剂能够有效控制消毒副产物前体物的生成,随着混凝剂的不断增加,TCM、1,1,1-TCP呈先增加后减少的趋势,TCAN、1,1-DCP、DCAA、TCAA浓度则逐渐降低,在投量为40 mg·L-1时,达到最低值.     

饮用水中典型微生物消毒过程中消毒副产物的生成规律

以饮用水中典型微生物--大肠杆菌（Escherichia coli）为试验对象,研究pH值、氯化时间、氯投量及细菌浓度对大肠杆菌在氯化消毒过程中生成消毒副产物（DBPs）的影响,并分析何种氯化条件下,DBPs控制效果最佳.研究表明：随氯投量增加,二氯乙腈（DCAN）呈先上升后下降趋势;随氯化时间延长,三氯丙酮（1,1,1-TCP）和DCAN先增加后减少;在pH值从5升高到9时,1,1,1-DCP、三氯硝基甲烷（TCNM）、二氯乙酸（DCAA）和三氯乙酸（TCAA）持续降低;细菌污染水源事件在近年常有报道,当水源水中细菌浓度增加时,饮用水中三氯甲烷（TCM）、TCNM、DCAA和TCAA浓度增加,但DCAN、三氯乙腈（TCAN）、二氯丙酮（1,1-DCP）和1,1,1-TCP不一定增加.为了达到低毒性的目的,氯投量浓度不宜太高,同时控制氯化时间为6h和pH>8.     

铜均相和非均相催化氯化消毒反应研究

在不同的入水pH值条件下,考察了铜离子存在时的均相情况和铜氧化物存在时的非均相情况下,水中余氯的分解和消毒副产物的生成规律.结果表明,与不含铜的情况相比,铜的存在,无论是均相还是非均相,对余氯的分解均有促进作用.不同的pH值条件下,铜均相和非均相对挥发性氯化消毒副产物三卤甲烷(THMs)的生成和非挥发性氯化消毒副产物二氯乙酸(DCAA)和三氯乙酸(TCAA)生成的影响不同,这主要是由于pH值影响了水中可溶性铜离子的浓度造成的.随着pH值的升高,在铜均相和非均相催化下,水中可溶性铜离子的浓度均降低.可溶性铜离子的浓度会影响水中消毒副产物的生成.对于挥发性氯化消毒副产物THMs来说,当铜离子浓度小于2.5 mg·L-1时,随着铜离子浓度增加,对THMs生成的促进作用加强;当铜离子浓度大于2.5 mg·L-1后,对THMs生成的促进作用减弱;对于非挥发性氯化消毒副产物DCAA和TCAA,随着铜离子浓度增加,DCAA的生成量逐渐增加,TCAA的生成量逐渐减少.     

我国地表水新烟碱类杀虫剂对水生生物安全的威胁

针对我国新烟碱类杀虫剂（NNIs）使用量大且地表水中浓度逐渐上升的现状,基于物种敏感度分布法,利用危害商法和概率风险评价法评估了我国地表水中NNIs对淡水水生生物的单一和复合生态风险,并对我国地表水质监管NNIs提出了目标建议值.结果表明：（1）单一化合物,吡虫啉的急性危害最大,吡虫啉和啶虫脒的慢性危害较大,最敏感生物均为昆虫;（2）海南省是地表水NNIs浓度最高的地区,急慢性危害最大;（3）联合毒性的概率曲线表明,5种NNIs对5%淡水水生生物产生慢性联合毒性的概率高达92.12%,严重威胁我国水生生物的安全;（4）基于物种敏感度分布曲线得到毒性参考值,结合危害商和概率风险评价的结果,建议我国保护水生生物安全的地表水质监管目标值分别为吡虫啉0.01μg·L^-1、噻虫啉0.03μg·L^-1、啶虫脒0.04μg·L^-1、噻虫胺0.22μg·L^-1和噻虫嗪0.24μg·L^-1.总之,我国地表水中NNIs浓度已经威胁到水生生物的安全,必须加强监管.     

扑草净水环境质量基准及风险评估

选择田间使用量大的扑草净为研究对象,分析了扑草净在南四湖流域地表水中的空间分布,推导了扑草净的水质基准,通过定性与定量风险评估方法评估了扑草净的生态风险.结果表明,南四湖流域28个地表水采样点中扑草净浓度为0~667.7ng/L,平均值为69.2ng/L.搜集筛选了15种水生生物慢性毒性数据,利用物种敏感度分布法,推导出扑草净的水质基准为82.4ng/L.使用商值法评估南四湖流域生态风险,结果表明,扑草净生态风险最高区域位于NS09,主要来源是地表径流与雨水冲刷.采用联合概率曲线法进一步分析生态风险,发现南四湖水体中扑草净对1%~5%的水生生物产生危害的概率为11.2%~6.4%.总体来看,南四湖流域扑草净的生态环境风险处于较低水平.     

全国自来水厂卤乙酸浓度调查、风险评估与标准建议

采用高特异性和高灵敏度的UPLC-MS/MS方法对中国34个城市的117个自来水厂出水中9种卤乙酸进行检测,其中二氯乙酸和三氯乙酸的检出率和检出浓度最高,检出率分别为78.6%和81.2%,平均浓度分别为3.47μg/L和3.31μg/L.风险评价结果表明,二氯乙酸导致我国饮用水致癌风险的期望值为5.72′10-6,处于较低风险水平;全国只有1.7%水厂出水TCAA浓度超过20μg/L的健康指导值.在风险评价的基础上结合我国水厂的卤乙酸浓度数据,建议我国饮用水的二氯乙酸和三氯乙酸标准分别修改为16μg/L和20μg/L.     

含氯消毒副产物的种类、危害与地表水污染现状

新型冠状病毒肺炎（COVID-19,简称“新冠肺炎”）疫情期间,含氯消毒剂被大量使用,含氯消毒剂会与水中本底存在的有机物反应生成含氯消毒副产物（CDBPs）,CDBPs包括卤甲烷、卤乙酸、无机卤氧酸盐、卤代乙腈、卤化氰、卤化硝基甲烷、卤代乙醛和其他CDBPs.梳理了各类CDBPs的危害,结果表明:大部分CDBPs具有致癌、致畸和致突变的“三致”毒性,在自然水体中威胁水生生物安全和人群健康;虽然现阶段大量研究集中于饮用水中的消毒副产物,但也有少量研究证实地表水中已有消毒副产物的检出.新冠肺炎疫情期间含氯消毒剂使用量较大,建议对余氯呈阳性的地表水继续开展主要CDBPs的筛查,有针对性地开展监测,推动含氯消毒剂的合理使用;同时,应加强监管,在地表水质量标准修订时完善消毒副产物指标,在相关行业废水控制标准中增加消毒副产物指标,避免对地表水生态系统造成次生环境影响.      

Influencing factors of disinfection byproducts formation during chloramination of Cyclops metabolite solutions

Effects of reaction time, chlorine dosage, pH and temperature on the formation of disinfection byproducts(DBPs), were investigated during the chloramination of Cyclops metabolite solutions. The results showed that some species of DBPs like trichloromethane(TCM), dichloroacetic acid(DCAA) and trichloroacetic acid(TCAA) could accumulate to their respective stable values with a progressive elevation in reaction time and monochloramine concentration. And 1,1,1-2-trichloropropanone(1,1,1-TCP) content decreased correspondingly with a continuous increase of reaction time. The amounts of chloral hydrate(CH), chloropicrin(TCNM), 1,1,1-TCP and DCAA firstly increased and then decreased with increasing monochloramine doses. Higher temperature resulted in a decrease of CH, dichloroacetonitrile(DCAN), 1,1-dichloropropanone(1,1-DCP), 1,1,1-TCP, DCAA and TCAA concentration. pH affected the formation of the different DBPs distinctly. TCM accumulateded with the increase of pH under 9, and DCAA, TCAA, CH and 1,1-DCP decreased continuously with increasing pH from 5 to 10, and other DBPs had the maximum concentrations at pH 6–7.     

膜生物反应器处理城市污水的后续次氯酸钠消毒研究

针对膜生物反应器（membrane bioreactor,MBR）处理城市污水的后续次氯酸钠消毒,分别开展了不同氯的投加剂量对指示微生物（总大肠菌群和粪大肠菌群）的灭活效果、消毒副产物（disinfection by-products,DBPs）生成量以及消毒后出水发光菌急性毒性研究.结果表明,在工程应用中MBR处理工...     

饮用水处理中活性炭吸附卤乙酸的特性

采用静态和动态试验研究了活性炭对卤乙酸的物理吸附特性。静态试验表明：在单吸附质条件下,二氯乙酸和三氯乙酸的吸附等温线在低浓度区（Ｃｅ〈５０μｇ／Ｌ）表现为单层吸附,在高浓度区表现为多层吸附。活性炭对三氯乙酸的吸附能力高于二氯乙酸。在饮用水处理常见的浓度范围内,活性炭对三氯乙酸的吸附容量约为二氯乙酸的２倍。在多吸附质条件下,对三氯乙酸的吸附容量只略的降低,对二氯乙酸的吸附容量则显著下降,这与有机物的     

Formation potentials of typical DBPs 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 mg/L, the two mixed bromochloro species THMs and two dominant HAAs (DCAA and TCAA) firstly increased and then decreased with the increase of ozone dose, with the turning point approximately occurring at an ozone dose of 5 mg/L. The genotoxicity detected using umu test, on the other hand, was removed from 7 μg 4-NQO/L to a negligible level by ozonation under an ozone dose of 5 mg/L. Chlorination could further remove the genotoxicity to some extent. It was found that SUVA (UV absorbance divided by DOC concentration) might be used as an indicative parameter for monitoring the removal of genotoxicity during the oxidation.     

Formation potentials of typical disinfection byproducts and changes of genotoxicity for chlorinated tertiary e uent 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 mg/L, the two mixed bromochloro species THMs and two dominant HAAs (DCAA and TCAA) firstly increased and then decreased with the increase of ozone dose, with the turning point approximately occurring at an ozone dose of 5 mg/L. The genotoxicity detected using umu test, on the other hand, was removed from 7 μg 4-NQO/L to a negligible level by ozonation under an ozone dose of 5 mg/L. Chlorination could further remove the genotoxicity to some extent. It was found that SUVA (UV absorbance divided by DOC concentration) might be used as an indicative parameter for monitoring the removal of genotoxicity during the oxidation.     

Fatty acids and algal lipids as precursors of chlorination by-products

Six common algal fatty acids (FAs) with different numbers of double bonds, lipophilic fractions and proteins extracted from the diatom Navicula pelliculosa and algal cells were chlorinated to evaluate their potential in generating disinfection by-products (DBPs). The result showed that the more double bonds in the FAs, the higher the amounts of chloroform and dichloroacetic acid (DCAA) produced, but such a pattern was not observed for trichloroacetic acid (TCAA). Based on the previously reported composition of fatty acids in algal lipids, the DBP generation potentials of algal lipids were calculated. These predicted values were much lower than those measured in the chlorinated algal lipophilic fraction, suggesting unknown lipophilic fraction(s) served as potent DBPs precursors. Another calculation attempted to predict DBP production in algal cells based on algal lipid and protein composition, given quantified measured DBP production per unit algal lipid and proteins. The analysis showed that the observed DBP production was similar to that predicted (< 35% difference), suggesting that algal biochemical compositions may serve as a bioindicator for preliminary estimation of chloroform, DCAA and TCAA formation upon chlorinating algae.     

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.