不同种类氨基酸在氯化后形成三卤甲烷和卤乙酸潜能特性

水体中的氨基酸作为饮用水消毒副产物(DBPs)的重要前驱体之一,已成为环境毒理学研究的焦点问题.本文对典型的20种氨基酸进行模拟氯化消毒实验,确定其耗氯量,以甲基叔丁基醚(MTBE)萃取消毒副产物三卤甲烷(THMs)、卤乙酸(HAAs)和三氯硝基甲烷(TCNM),并用气相色谱仪测试分析THMs、HAAs和TCNM的生成势,同时通过数理统计方法分析不同氨基酸的化学结构与生成消毒副产物浓度的关系.结果表明:(1)各氨基酸的耗氯能力与其结构密切相关,侧链上具有芳香性环状结构的氨基酸的耗氯量较大,其中芳香环上有羟基和氮取代基的酪氨酸和色氨酸分别表现出较高的耗氯量(13.58、14.10 mg·mg~(-1)),而没有官能团的苯丙氨酸耗氯量低(4.24 mg·mg~(-1)).(2)20种氨基酸氯化过程中DBPs生成能力的差异与氨基酸侧链官能团的结构与性质有一定关系,其中侧链上具有芳香性环状结构、羟基、氨基和硫自由基等官能团结构的氨基酸可形成较高浓度DBPs;氯化色氨酸生成THMs能力最强,其生成三卤甲烷量达338.5μg·L~(-1).天冬氨酸生成HAAs(390.61μg·L~(-1))能力最强,酪氨酸生成TCNM(56.38μg·L~(-1))能力最强.(3)通过回归分析得出20种氨基酸在氯化消毒过程中HAAs生成能力大小与耗氯量大小具有较明显的相关性,耗氯量较大的氨基酸生成的HAAs也较高.     

饮用水中消毒副产物的消减措施

为了去除水中的病毒和细菌等有毒物质,在饮用水中添加氯是最常用的一种消毒方法.但是由于加入的氯会与水中的天然有机物(NOM)反应,产生包括三卤甲烷(THMs)和卤乙酸(HAAs)在内的各种氯化消毒副产物.这些消毒副产物的去除对饮用水的安全是一个值得关注的问题.     

超高效液相色谱/质谱联用仪分析消毒副产物——卤乙酸

目前,大多数自来水的消毒主要是采用氯消毒法,该法便捷、经济,目的是控制水中致病菌,使其满足人类的健康要求,然而,氯消毒会产生副产物,如三卤甲烷(THMs)、卤乙酸(HAAs)等.这使得饮用水的致癌风险明显增加,研究表明:饮用氯消毒水使患膀胱癌、直肠癌和结肠癌的危险增加,早期消毒副产物的毒理学研究偏重于三卤甲烷类,最近对卤乙酸的致癌性研究逐渐增加,目前,消毒副产物问题是国际给水界的热点问题之一.     

高锰酸盐复合剂对三卤甲烷生成形态的影响

研究了高锰酸盐复合剂(PPC)对腐殖酸氯化过程中三卤甲烷生成量及生成形态的影响.结果表明,高锰酸盐复合剂氧化增加了腐殖酸氯化过程中三卤甲烷生成量和水样的卤代活性,增加了腐殖酸氯化的反应速度,在PPC投加量为0.75mg·l~(-1)时,卤代活性由原来的18.1μg·mg~(-1)升至26.6μg·mg~(-1).Br~-的浓度对三卤甲烷生成量及生成形态影响较大,随着Br~-离子浓度增加,三卤甲烷生成量及溴代甲烷的相对含量升高.高锰酸盐复合剂氧化改变了水样加氯消毒时三卤甲烷的形态分布,降低了溴代甲烷在三卤甲烷中的含量.高锰酸盐复合剂与混凝工艺相结合时,可显著降低三卤甲烷的生成量,如高锰酸盐复合剂投量为1mg·l~(-1)时,可使THMs降低到26.3μg·l~(-1).     

高锰酸盐复合药剂强化预氯化控制THMs生成量

通过小试和中试实验研究了高锰酸盐复合药剂(PPC)与氯联合预氧化工艺对三卤甲烷(THMs)的控制效果.小试的研究结果表明,适当投加PPC(1.0 mg·l-1)可使预氯化的THMs生成量降低14.1%,预加氯量是联合预氧化工艺THMs生成量的决定因素,pH值降低,THMs生成量减少,并且在pH6.0的条件下,PPC显著降低了预氯化工艺的THMs生成量;中试的研究结果表明,与单独预氯化(3.0mg·l-1)相比,联合预氧化工艺(PPC 1.0 mg·l-1 Cl22.0 mg·l-1)过滤后水中的THMs减少了47.9%;模拟管网系统试验的研究结果表明,联合预氧化工艺的THMs生成量与单独预氯化相比降低了17.2%.因此,PPC和氯联合预氧化工艺可降低饮用水的THMs生成量,提高饮用水的化学物安全性.     

卤代醛/酮消毒副产物的生成潜能及其前驱物的结构特征

卤代醛和卤代酮类消毒副产物因具有"致畸、致癌、致突变"作用而倍受关注.对卤代醛/酮类消毒副产物控制及其前体物识别对饮用水安全保障具有重要意义.以大分子酸、疏水性酸、芳香族类亲水酸、亲水酸、糖类和氨基酸6类共14种常见有机物为对象,研究了不同有机物在氯化消毒过程中的卤代醛/酮生成潜力.结果表明,富里酸、柠檬酸、苹果酸、L-苏氨酸和L-天冬酰胺具有较高的卤代醛/酮生成势.有机物生成卤代醛/酮的过程包括2个阶段:前体物首先经氧化、脱羧等过程生成乙醛和丙酮,乙醛和丙酮被逐步氯代而生成氯代醛和氯代酮.实际水体的消毒实验表明,卤代醛/酮的生成势与水样中有机物的浓度无必然联系,但与水样中醇羟基及羰基官能团的含量呈正相关(R~2=0.69—0.98).     

饮用水消毒副产物:化学特征与毒性

饮用水消毒过程中消毒剂与天然有机物(NOMs)反应生成消毒副产物(DBPs).本文针对氯、氯胺、二氧化氯、臭氧4种主要消毒方式产生的消毒副产物,综述了10类DBPs的化学特性、毒性和分析方法.具体包括:三卤甲烷(THMs)、卤乙酸(HAAs)、溴酸盐(BrO3-)、亚氯酸盐(CIO2-)、卤乙腈(HANs)、致诱变化合...     

离子色谱-质谱联用技术在饮用水分析中的应用(续)

3　IC MS测定饮用水中卤代乙酸卤代乙酸 (haloaceticacids,HAAs)是饮用水加氯消毒的副产物 ,共有 9种HAAs,一氯乙酸(MCAA)、二氯乙酸 (DCAA)、三氯乙酸 (TCAA)、一溴乙酸 (MBAA)、二溴乙酸 (DBAA)、三溴乙酸(TBAA)、氯溴乙酸 (BCAA)、一氯二溴乙酸 (DCBAA)、二氯一溴乙酸 (DBCA     

UV/H_2O_2技术对上海青草沙水源水砂滤后溴酸根和三卤甲烷的生成控制

针对含溴离子(Br-)的上海某水厂滤后水的高级氧化处理,考察了紫外/过氧化氢(UV/H_2O_2)技术对UV254和总有机碳(TOC)的削减效率、控制消毒副产物溴酸根(Br O-3)和三卤甲烷(THMs)的生成情况,同时研究了水中溴离子(Br-)浓度的改变对UV/H_2O_2处理效果的影响.结果表明,UV/H_2O_2处理工艺不产生Br O-3;500 m J·cm-2的UV剂量和5 mg·L-1H_2O_2投加量下,出水UV254和TOC分别降低了35%和21%;后续氯消毒过程中的THMs生成势随H_2O_2投加量的增加显著降低,500 m J·cm-2的UV剂量下,H_2O_2投加量为5 mg·L-1和10 mg·L-1时,THMs生成势的削减率分别为49.4%和79.9%;水中Br-浓度的改变不影响UV/H_2O_2工艺的运行效果;相比UV,UV/H_2O_2还可使9种农药的降解率提高50%—85%.因此,UV/H_2O_2在含Br-水源水深度处理方面有着较好的应用前景.     

膜-紫外/氯组合工艺中微量有机污染物的去除及卤代消毒副产物的生成

本研究探究了膜-UV/氯组合工艺对污水二级出水中23种微量有机污染物(TrOCs)的降解动力学和降解机制,并考察了该组合工艺中卤代消毒副产物(X-DBPs)的生成及其生成潜能(X-DBPsFP),同时对处理后水样的细胞毒性和基因毒性进行了评估.结果 表明,膜预处理能有效促进UV/氯体系中TrOCs的降解,且纳滤(NF)比超滤(UF)的促进效果更明显.相比于UF,NF截留更多的溶解性有机质(DOM)从而更大程度地减弱了光屏蔽效应、对氯的消耗及对自由基的猝灭.研究发现TrOCs的降解机制可归为以下四类:HO·主导、活性卤素物种(RHS)主导、氯和RHS共同主导及氯主导.膜预处理能很好地削减X-DBPs的生成,其中UF和NF分别对卤代乙酰胺(HAMs)和三卤甲烷(THMs)的生成削减最明显,而NF对X-DBPs和X-DBPsFP的削减以及对水样毒性的削弱作用都远强于UF.此外,NF-UV/氯能显著去除X-DBPs的前驱体,从而有效控制后氯化过程水样细胞毒性和基因毒性的增强.研究结果推动了污水深度处理技术的发展并为相关研究提供了理论指导.     

Formation of disinfection by-products during sodium hypochlorite cleaning of fouled membranes from membrane bioreactors

•HAAs was dominant among the DBPs of interest. •Rising time, dose, temperature and pH raised TCM and HAAs but reduced HANs and HKs. •Low time, dose and temperature and non-neutrality pH reduced toxic risks of DBPs. •The presence of EPS decelerated the production of DBPs. •EPS, particularly polysaccharides were highly resistant to chlorine. Periodic chemical cleaning with sodium hypochlorite (NaClO) is essential to restore the membrane permeability in a membrane bioreactor (MBR). However, the chlorination of membrane foulants results in the formation of disinfection by-products (DBPs), which will cause the deterioration of the MBR effluent and increase the antibiotic resistance in bacteria in the MBR tank. In this study, the formation of 14 DBPs during chemical cleaning of fouled MBR membrane modules was investigated. Together with the effects of biofilm extracellular polymeric substances (EPS), influences of reaction time, NaClO dosage, initial pH, and cleaning temperature on the DBP formation were investigated. Haloacetic acids (HAAs) and trichloromethane (TCM), composed over 90% of the DBPs, were increasingly accumulated as the NaClO cleaning time extended. By increasing the chlorine dosage, temperature, and pH, the yield of TCM and dichloroacetic acid (DCAA) was increased by up to a factor of 1‒14, whereas the yields of haloacetonitriles (HANs) and haloketones (HKs) were decreased. Either decreasing in the chlorine dosage and cleaning temperature or adjusting the pH of cleaning reagents toward acidic or alkaline could effectively reduce the toxic risks caused by DBPs. After the EPS extraction pretreatment, the formation of DBPs was accelerated in the first 12 h due to the damage of biofilm structure. Confocal laser scanning microscopy (CLSM) images showed that EPS, particularly polysaccharides, were highly resistant to chlorine and might be able to protect the cells exposed to chlorination.     

Assesment of disinfection by‐products removal by ozonation coupled with adsorption

This research work was performed to evaluate ozonation and granular activated carbon adsorption processes from the view‐point of controlling the formation of disinfection by products (DBPs). Both the humic acid and raw water were first preozonated and then adsorbed on the activated carbon to assess the potency for removal of total organic carbon (TOC) and DBPs. The disinfection by‐product including THMs and HAAs, in principle, can be successfully removed through a use of the ozonation and granular activated carbon (GAC) adsorption processes. However, in practice dealing with the raw water, it is necessary to introduce the pilot‐plant to obtain the design and operation guidelines for the water treatment plant through the ICA (Instrumentation Control and Automation) program in our future research work.     

Removal of organic matter and disinfection by-products precursors in a hybrid process combining ozonation with ceramic membrane ultrafiltration

The performance of an integrated process including coagulation, ozonation, ceramic ultrafiltration (UF) and biologic activated carbon (BAC) filtration was investigated for the removal of organic matter and disinfection by-products (DBPs) precursors from micro-polluted surface water. A pilot scale plant with the capacity of 120 m³ per day was set up and operated for the treatment of drinking water. Ceramic membranes were used with the filtration area of 50 m² and a pore size of 60 nm. Dissolved organic matter was divided into five fractions including hydrophobic acid (HoA), base (HoB) and neutral (HoN), weakly hydrophobic acid (WHoA) and hydrophilic matter (HiM) by DAX-8 and XAD-4 resins. The experiment results showed that the removal of organic matter was significantly improved with ozonation in advance. In sum, the integrated process removed 73% of dissolved organic carbon (DOC), 87% of UV₂₅₄, 77% of trihalomethane (THMs) precursors, 76% of haloacetic acid (HAAs) precursors, 83%of trichloracetic aldehyde (CH) precursor, 77% of dichloroacetonitrile (DCAN) precursor, 51% of trichloroacetonitrile (TCAN) precursor, 96% of 1,1,1-trichloroacetone (TCP) precursor and 63% of trichloronitromethane (TCNM) precursor. Hydrophobic organic matter was converted into hydrophilic organic matter during ozonation/UF, while the organic matter with molecular weight of 1000–3000 Da was remarkably decreased and converted into lower molecular weight organic matter ranged from 200–500 Da. DOC had a close linear relationship with the formation potential of DBPs.     

广州市饮用水中挥发性有机物的研究

饮用水中的挥发性有机化合物（VOCs）来源于水源水受到的环境污染或是在净化消毒工艺处理工程中反应产生的副产物,可对人体健康造成极大的危害。改革开放以来,广州人口和经济得到突飞猛进的发展,也带来了包括饮用水安全在内的诸多严重的社会和环境问题。虽然饮用水中VOCs的研究已经得到越来越多的重视,但是目前对广州市饮用水中挥发性有机物的研究还鲜有报道。本文在广州市中心城区选取15个不同位置的采样点进行了自来水水样采集,并利用吹扫-捕集-气相色谱-质谱（GC-MS）联用系统分析技术测定水中 VOCs 的种类和三卤甲烷的质量浓度。结果表明,广州市中心城区的自来水中VOCs有20种,以三卤甲烷（THMs）和芳香烃类为主,占了所检出的物质总量的78%以上。THMs中四种化合物（氯仿、一溴二氯甲烷、二溴一氯甲烷、溴仿）的检出率达100%,总三卤甲烷的平均质量浓度为46.46μg· L-1,最大值为53.31μg· L-1,最小值39.91μg· L-1。根据2006版国家饮用水标准,四种三卤甲烷质量浓度均低于标准限值,符合标准要求。对市面上一般的瓶装水的研究发现,瓶装水中三卤甲烷的质量浓度非常低,总三卤甲烷平均质量浓度仅为1.47μg·L-1,约是自来水中质量浓度的1/30。为了解温度及煮沸对自来水中 THMs 质量浓度的影响,本研究设计了实验进行探究。结果发现加热至沸腾过程中,THMs质量浓度随温度升高而升高,而沸腾后THMs骤降,煮沸5 min可降低水中约95%的THMs,接近瓶装水中THMs质量浓度。     

Identification of important precursors and theoretical toxicity evaluation of byproducts driving cytotoxicity and genotoxicity in chlorination

• NOM formed more C-DBPs while amino acids formed more N-DBPs during chlorination • Aspartic acid and asparagine showed the highest toxicity index during chlorination • Dichloroacetonitrile might be a driving DBP for cytotoxicity and genotoxicity • Dichloroacetonitrile dominated the toxicity under different chlorination conditions Chlorination, the most widely used disinfection process for water treatment, is unfortunately always accompanied with the formation of hazardous disinfection byproducts (DBPs). Various organic matter species, like natural organic matter (NOM) and amino acids, can serve as precursors of DBPs during chlorination but it is not clear what types of organic matter have higher potential risks. Although regulation of DBPs such as trihalomethanes has received much attention, further investigation of the DBPs driving toxicity is required. This study aimed to identify the important precursors of chlorination by measuring DBP formation from NOM and amino acids, and to determine the main DBPs driving toxicity using a theoretical toxicity evaluation of contributions to the cytotoxicity index (CTI) and genotoxicity index (GTI). The results showed that NOM mainly formed carbonaceous DBPs (C-DBPs), such as trichloromethane, while amino acids mainly formed nitrogenous DBPs (N-DBPs), such as dichloroacetonitrile (DCAN). Among the DBPs, DCAN had the largest contribution to the toxicity index and might be the main driver of toxicity. Among the precursors, aspartic acid and asparagine gave the highest DCAN concentration (200 g/L) and the highest CTI and GTI. Therefore, aspartic acid and asparagine are important precursors for toxicity and their concentrations should be reduced as much as possible before chlorination to minimize the formation of DBPs. During chlorination of NOM, tryptophan, and asparagine solutions with different chlorine doses and reaction times, changes in the CTI and GTI were consistent with changes in the DCAN concentration.     

Concentration levels of disinfection by-products in 14 swimming pools of China

Swimming has become a popular exercising and recreational activity in China but little is known about the disinfection by-products (DBPs) concentration levels in the pools. This study was conducted as a survey of the DBPs in China swimming pools, and to establish the correlations between the DBP concentrations and the pool water quality parameters. A total of 14 public indoor and outdoor pools in Beijing were included in the survey. Results showed that the median concentrations for total trihalomethanes (TTHM), nine haloacetic acids (HAA9), chloral hydrate (CH), four haloacetonitriles (HAN4), 1,1-dichloropropanone, 1,1,1-trichloropropanone and trichloronitromethane were 33.8, 109.1, 30.1, 3.2, 0.3, 0.6 µg∙L⁻¹ and below detection limit, respectively. The TTHM and HAA9 levels were in the same magnitude of that in many regions of the world. The levels of CH and nitrogenous DBPs were greatly higher than and were comparable to that in typical drinking water, respectively. Disinfection by chlorine dioxide or trichloroisocyanuric acid could substantially lower the DBP levels. The outdoor pools had higher TTHM and HAA9 levels, but lower trihaloacetic acids (THAA) levels than the indoor pools. The TTHM and HAA9 concentrations could be moderately correlated with the free chlorine and total chlorine residuals but not with the total organic carbon (TOC) contents. When the DBP concentration levels from other survey studies were also included for statistical analysis, a good correlation could be established between the TTHM levels and the TOC concentration. The influence of chlorine residual on DBP levels could also be significant.     

Haloacetic acids in swimming pool and spa water in the United States and China

The objective of this study is to investigate the occurrence of haloacetic acids （HAAs）, a group of disinfection byproducts, in swimming pool and spa water. The samples were collected from six indoor pools, six outdoor pools and three spas in Pennsylvania, the United States, and from five outdoor pools and nine indoor pools in Beijing, China. Five HAAs （HAA5）, including monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monobromoacetic acid, and dibromoacetic acid were analyzed. Total chlorine, pH and total organic carbon concentration were analyzed as well. Results indicated that the levels of HAA5 in swimming pools and spas in the United States ranged from 70 to 3980μg·L^-1, with an arithmetic average at 1440μg·L^-1 and a median level at 1150μg·L^-1. These levels are much higher than the levels reported in chlorinated drinking water and are likely due to organic matters released from swimmers＇ bodies. The levels of HAA5 in swimming pools in China ranged from 13 to 332μg·L^-1, with an arithmetic average at 117μg·L^-1 and a median level at 114μg·L^-1. The lower HAA levels in swimming pools in China were due to the lower chlorine residuals. Results from this study can help water professionals to better understand the formation and stability of HAAs in chlorinated water and assess risks associated with exposures to HAAs in swimming pools and spas.     

二氧化氯对水中病毒、藻类和浮游动物的失活效果

本文研究了二氧化氯对水中一些主要病毒、藻类和浮游动物的失活效果,以及在不同消毒剂投量、接触时间和pH值等条件下,二氧化氯(ClO_2)对水体中一些微生物的杀灭和失活效果.与液氯对比的结果表明:ClO_2对藻类失活效果优于或相当于液氯;ClO_2对病毒和浮游动物的失活效果显著优于液氯;ClO_2可在一广泛的pH值范围内杀灭微生物.此外,还从理论上初步探讨了ClO_2对病毒的失活机理.研究结果表明,ClO_2是一种优良的液氯替代消毒剂,这对开展ClO_2的研究及其应用有重要意义.     

Whole pictures of halogenated disinfection byproducts in tap water from China’s cities

When bromide/iodide is present in source water, hypobromous acid/hypoiodous acid will be formed with addition of chlorine, chloramine, or other disinfectants. Hypobromous acid/hypoiodous acid undergoes reactions with natural organic matter in source water to form numerous brominated/iodinated disinfection byproducts (DBPs). In this study, tap water samples were collected from eight cities in China. With the aid of electrospray ionization-triple quadrupole mass spectrometry by setting precursor ion scans of m/z 35, m/z 81, and m/z 126.9, whole pictures of polar chlorinated, brominated, and iodinated DBPs in the tap water samples were revealed for the first time. Numerous polar halogenated DBPs were detected, including haloacetic acids, newly identified halogenated phenols, and many new/unknown halogenated compounds. Total organic chlorine, total organic bromine, and total organic iodine were also measured to indicate the total levels of all chlorinated, brominated, and iodinated DBPs in the tap water samples. The total organic chlorine concentrations ranged from 26.8 to 194.0 μg·L^–1 as Cl, with an average of 109.2 μg·L^–1 as Cl; the total organic bromine concentrations ranged from below detection limit to 113.3 μg·L^–1 as Br, with an average of 34.7 μg·L^–1 as Br; the total organic iodine concentrations ranged from below detection limit to 16.4 μg·L^–1 as I, with an average of 9.1 μg·L^–1 as I; the total organic halogen concentrations ranged from 31.3 to 220.4 μg·L^–1 as Cl, with an average of 127.2 μg·L^–1 as Cl.