氯对饮用水中可同化有机碳的影响

通过分析太湖水的分子量分布变化以及亲疏组分,考察氯反应生成AOC的效果和机理.结果表明,弱疏组分的AOC生成量最大,其次为强疏,中亲和带负电亲水的生成量最少.氯主要与小分子的疏水性有机物反应,AOC的生成量最多.通过考察深度处理工艺的有机物分子量以及组分的变化,发现疏水性有机物呈逐渐下降而亲水性组分呈上升的趋势,表明氯化产生的AOC呈减少趋势.小分子的疏水性有机物是主要的氯化AOC的前体物.     

京密引水中不同形态天然有机物的卤代活性

用过滤、XAD－8和XAD－4树脂串联吸附等方法将京密引水中的天然有机物定量分离为悬浮固体、憎水有机物、腐殖酸类化合物,XAD－4酸和其它亲水有机物。分别对不同形态有机物进行氯化处理,测定了产物中的挥发性卤代烃。结果表明,京密引水中天然有机物的主要挥发性氯化产物是氯仿,此外还生成一溴、二溴氯甲烷及少量溴仿。溶解态腐殖酸类化合物的悬浮固态和悬浮固态有机物是生成氯仿的最主要母体。亲水有机酸也具有较高的卤代活性,而其它有机成分则表现出相对惰性。     

北京市道路雨水径流溶解性有机物化学组分特性

为探究北京市道路雨水径流溶解性有机物（DOM）的化学特性,采用三维荧光光谱、紫外-可见吸收光谱及红外光谱技术,对北京市不同交通密度道路雨水径流溶解性有机物的化学组分进行分析.结果表明,北京市道路雨水径流DOM以疏水性组分为主,且主要为疏水中性组分.道路雨水径流DOM亲水性组分主要由类芳香蛋白物质组成,疏水性组分除含大量类芳香蛋白物质外,还含有大量类富里酸物质.道路雨水径流DOM疏水性组分的芳香化程度较高、腐殖化程度较低,亲水性组分与之相反.道路雨水径流DOM酸性组分中含异构化的羧基和苯环等官能团,碱性组分和中性组分中多含醚键、酯基、酚类和醇类等官能团.交通密度对道路雨水径流DOM化学组分的物质组成、特性等无明显影响,仅影响各化学组分中的物质含量;交通密度越大,各化学组分中物质的含量越多和芳香化程度越高,腐殖化程度越低.     

长江沿线城市水源氯(胺)化消毒副产物生成潜能研究

以长江上游重庆、中游武汉、下游上海等大城市的长江饮用水源为研究对象,在对溶解性有机物分子量和亲疏水性分离的基础上,分别采用氯和氯胺两种方式消毒,对比分析了相同时期沿江这些城市原水中氯(胺)化常规和新兴含氮消毒副产物生成潜能的分子组成规律.研究表明,重庆、武汉、上海三地的溶解性有机物均以小分子前体物为主,主要分布在<1kDa的区间内,且以强疏水性成分和亲水性成分为主,原水经氯(胺)化可产生三卤甲烷、卤乙酸、卤乙腈、三氯硝基甲烷等类型的消毒副产物;三地的氯(胺)化主要的含碳消毒副产物(C-DBPs)和含氮消毒副产物(N-DBPs)生成潜能均在<1kDa的区间内最大,从上游到下游,在<1kDa的区间内的生成潜能占各自总潜能比例逐渐增加.三地的氯(胺)化的C-DBPs和N-DBPs生成潜能均以强疏水性组分或亲水性组分为主,且氯胺化可导致亲水性组分C-DBPs和N-DBPs生成潜能所占总量比例增加.     

阿哈水库DOM的分离及其对消毒副产物的贡献

为研究高原喀斯特湖库DOM（dissolved organic matter,溶解性有机质）的组成及其化学特征对DBPs（disinfection by-products,消毒副产物）生成路径的影响,以西南喀斯特地区贵阳市阿哈水库的DOM为研究对象,结合XAD大孔树脂分离技术,通过化学表征〔包括UV-Vis（紫外-可见光光谱）、FTIR（红外光谱）和3D-EEM（三维荧光光谱）〕手段来研究各组分对C-DBPs（含碳消毒副产物）和N-DBPs（含氮消毒副产物）的生成贡献.不同组分芳香性的大小依次为HON（憎水中性物）> HIB（亲水碱）> HOA（憎水酸）> HIN（亲水中性物）≈HIA（亲水酸）> HOB（憎水碱）.憎水与亲水DOM的DBPs生成潜能相近.其中,HON最高,其次为HIB和HOA.HIB和HOA的主要卤代反应位分别来源于藻类有机物的蛋白质和富里酸,而HON的DBPs生成潜能的贡献主要为分子中的芳香和共轭不饱和结构.HIA和HIN的构成主要为脂肪烃,贡献较低的DBPs的生成潜能.对于C-DBPs,THMs和HAAs的生成潜能总体相近,不同组分的差异明显.对于N-DBPs,卤乙腈的生成潜能占80%以上,憎水DOM的贡献较高.DBPs的生成路径从UV-Vis、FTIR和3D-EEM的官能团和特征峰解析结果中均得到了较好的响应.      

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.     

水源水中有机物特性及其氯化活性研究

以西南某市一个地表水为水源水的M水厂为研究对象，对其原水中有机物进行富集，有机物按照操作定义分为6个部分，分别为：亲水性有机酸、亲水性有机碱、亲水中性物质、疏水性有机酸、疏水性有机碱和疏水性物质，通过富集、确定了原水中6种有机物的组成分布，研究各种有机物的消毒副产物形成潜力以及替代剂（氯胺、二氧化氯）对卤乙酸形成的影响，提出了控制消毒副产物的主要对策，研究结果表明：1）M水厂水源水属于腐殖质含量的天然水体，受污染较小；2）原水溶解性有机物中疏水性有机酸是卤乙酸的主要前体物；3）用氯胺和二氧化氯代替传统的消毒剂作为替代消毒剂，可大大降低THMs和HAAs的生成量。     

污水中溶解性有机物组分特性及其氯消毒副产物生成潜能

以城市污水厂二级出水为研究对象,采用大孔吸附树脂将污水中溶解性有机物分离成亲水性物质、疏水酸性物质、疏水中性物质和疏水碱性物质4个组分,分析了各组分的有机物特性、三维荧光光谱特征和氯消毒副产物生成潜能.结果表明,亲水性物质和疏水酸性物质分别占水样中溶解性有机碳的33%和30%,其中亲水性物质相对含有较多的生物源腐殖质类物质,疏水酸性物质相对含有更多的芳香族蛋白质和溶解性微生物代谢产物类物质.氯消毒后,亲水性物质的三卤甲烷生成潜能分别为630.4μg.L-1,占污水三卤甲烷生成潜能的73.7%.亲水性物质和疏水酸性物质的卤乙酸生成潜能分别为644.6μg.L-1和123.2μg.L-1,是污水氯消毒副产物的主要前体物.     

Characteristics of molecular weight distribution of dissolved organic matter in bromide-containing water and disinfection by-product formation properties during treatment processes

The characteristics of dissolved organic matter (DOM) and bromide ion concentration have a significant influence on the formation of disinfection by-products (DBPs). In order to identify the main DBP precursors, DOM was divided into five fractions based on molecular weight (MW), trihalomethane formation potential and haloacetic acid formation potential were determined for fractions, and the change in contents of different fractions and total DBPs during treatment processes (pre-chlorination, coagulation, sand filtration, disinfection) were studied. Moreover, the relationship between bromide concentration and DBP generation characteristics in processes was also analyzed. The results showed that the main DBP precursors were the fraction with MW < 1 kDa and fraction with MW 3−10 kDa, and the DBP''s generation ability of lower molecular weight DOM (< 10 kDa) was higher than that of higher molecular weight DOM. During different processes, pre-chlorination and disinfection had limited effect on removing organics but could alter the MW distribution, and coagulation and filtration could effectively remove organics with higher MW. For DBPs, trihalomethanes (THMs) were mainly generated in pre-chlorination and disinfection, while haloacetic acids (HAAs) were mostly generated during pre-chlorination; coagulation and sand filtration had little effect on THMs but resulted in a slight removal of HAAs. In addition, the results of ANOVA tests suggested that molecular sizes and treatment processes have significant influence on DBP formation. With increasing bromide concentration, the brominated DBPs significantly increased, but the bromine incorporation factor in the processes was basically consistent at each concentration.     

Formation and control of disinfection byproducts and toxicity during reclaimed water chlorination: A review

Chlorination is essential to the safety of reclaimed water; however, this process leads to concern regarding the formation of disinfection byproducts (DBPs) and toxicity. This study reviewed the formation and control strategies for DBPs and toxicity in reclaimed water during chlorination. Both regulated and emerging DBPs have been frequently detected in reclaimed water during chlorination at a higher level than those in drinking water, indicating they pose a greater risk to humans. Luminescent bacteria and Daphnia magna acute toxicity, anti-estrogenic activity and cytotoxicity generally increased after chlorination because of the formation of DBPs. Genotoxicity by umu-test and estrogenic activity were decreased after chlorination because of destruction of toxic chemicals. During chlorination, water quality significantly impacted changes in toxicity. Ammonium tended to attenuate toxicity changes by reacting with chlorine to form chloramine, while bromide tended to aggravate toxicity changes by forming hypobromous acid. During pretreatment by ozonation and coagulation, disinfection byproduct formation potential (DBPFP) and toxicity formation potential (TFP) occasionally increase, which is accompanied by DOC removal; thus, the decrease of DOC was limited to indicate the decrease of DBPFP and TFP. It is more important to eliminate the key fraction of precursors such as hydrophobic acid and hydrophilic neutrals. During chlorination, toxicities can increase with the increasing chlorine dose and contact time. To control the excessive toxicity formation, a relatively low chlorine dose and short contact time were required. Quenching chlorine residual with reductive reagents also effectively abated the formation of toxic compounds.     

溶解性有机物在土壤含水层处理系统中的变化

通过实验室模拟土壤含水层处理(SAT)的土壤柱系统研究了二级处理出水中溶解性有机物(DOM)的荧光特性在SAT系统中的变化.利用XAD树脂将二级处理出水中的DOM分为5个部分:疏水性有机酸(HPO-A),疏水性中性有机物(HPO-N),过渡亲水性有机酸(TPI-A),过渡亲水性中性有机物(TPI-N)和亲水性有机物(HPI).结果表明,TPI-N中的类芳香族蛋白质荧光物质在SAT系统中优先去除.经过SAT系统处理后,类芳香族蛋白质荧光物质和类溶解性微生物代谢产物荧光物质在HPO-A,HPO-N,TPI-A和HPI中的相对含量升高.各组分中带有3~5个稠合苯环的荧光物质,以及激发波长/发射波长(λex/λem)=390~410nm/456~476nm的类腐殖酸荧光物质在SAT系统中的去除率低于相应组分中以溶解性有机碳(DOC)表征的整体有机物的去除率.不同组分中的其他荧光物质在SAT系统中去除行为不同.     

The migration and transformation of dissolved organic matter during the freezing processes of water

This study investigated the partitioning behavior of dissolved organic matter(DOM) in liquid and ice phases, as well as the changes in the optical properties and chlorine reactivity of DOM during the freezing processes of water. DOM was rejected from the ice phase and accumulated in the remaining liquid phase during water freezing. Moreover, the decrease in freezing temperature, as well as the increase in dissolved organic carbon(DOC)concentration of feed water, caused an increase in DOM captured in the ice phase. The ultraviolet-absorbing compounds, trihalomethane precursors, as well as fulvic acid- and humic acid-like fluorescent materials, were more liable to be to be rejected from the ice phase and were more easily retained in the unfrozen liquid phase during water freezing, as compared with organics(on average) that comprise DOC. In addition, it was also found a higher accumulation of these organics in the unfrozen liquid phase during water freezing at higher temperature. The freeze/thaw processes altered the quantity, optical properties, and chlorine reactivity of DOM. The decrease in ultraviolet light at 254 nm as well as the production of aromatic protein- and soluble microbial byproduct-like fluorescent materials in DOM due to freeze/thaw were consistently observed. On the other hand, the changes in DOC, trihalomethane formation potential, and fulvic acid- and humic acid-like fluorescence caused by freeze/thaw varied significantly between samples.     

The migration and transformation of dissolved organic matter during the freezing processes of water

This study investigated the partitioning behavior of dissolved organic matter (DOM) in liquid and ice phases, as well as the changes in the optical properties and chlorine reactivity of DOM during the freezing processes of water. DOM was rejected from the ice phase and accumulated in the remaining liquid phase during water freezing. Moreover, the decrease in freezing temperature, as well as the increase in dissolved organic carbon (DOC) concentration of feed water, caused an increase in DOM captured in the ice phase. The ultraviolet-absorbing compounds, trihalomethane precursors, as well as fulvic acid- and humic acid-like fluorescent materials, were more liable to be to be rejected from the ice phase and were more easily retained in the unfrozen liquid phase during water freezing, as compared with organics (on average) that comprise DOC. In addition, it was also found a higher accumulation of these organics in the unfrozen liquid phase during water freezing at higher temperature. The freeze/thaw processes altered the quantity, optical properties, and chlorine reactivity of DOM. The decrease in ultraviolet light at 254 nm as well as the production of aromatic protein- and soluble microbial byproduct-like fluorescent materials in DOM due to freeze/thaw were consistently observed. On the other hand, the changes in DOC, trihalomethane formation potential, and fulvic acid- and humic acid-like fluorescence caused by freeze/thaw varied significantly between samples.     

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.     

强化混凝对二级处理出水中溶解性有机物特性的影响

以沈阳市B污水处理厂二级处理出水为研究对象,采用FeCl3.6H2O作为混凝剂,研究了强化混凝对二级处理出水中溶解性有机物(DOM)的卤代活性和荧光特性的影响.按照DOM在XAD树脂上的吸附特性将其分为5个部分:疏水性有机酸(HPO-A)、疏水性中性有机物(HPO-N)、过渡亲水性有机酸(TPI-A)、过渡亲水性中性有机物(TPI-N)和亲水性有机物(HPI).结果表明,强化混凝(混凝剂投加量为80mg.L-1,pH=5.00)对DOC的去除率为55.3%.强化混凝对HPO-A的去除率最高,而对HPI的去除率最低.强化混凝后,HPO-N的三卤甲烷生成活性(STHMFP)上升,而其他4种DOM组分的STHMFP下降.强化混凝能够有效去除类富里酸荧光物质和具有高环数和高聚合度的稠环类芳香性荧光物质.强化混凝对DOM组分的去除率和DOM组分的荧光强度下降率的相关性不显著.     

水中典型含氮有机物氯化生成消毒副产物的潜能研究

选取了受污染原水中广泛存在的12种含氮有机物（除草剂、杀虫剂、氨基酸、工业品等）,开展了氯化和氯胺化培养生成典型消毒副产物的实验,目的是通过对水中脲类除草剂、嗪类除草剂和其他含氮化合物培养生成不同消毒副产物的生成量,讨论不同种类含氮化合物生成含碳和含氮消毒副产物规律以及考察不同消毒副产物的可能前体物.研究发现,脲类除草...     

水体冻结过程中卤乙酸前体物在水-冰体系中的分配研究

通过室内模拟试验,研究了水体冻结过程中,水体中溶解性有机物(DOM)和卤乙酸前体物在水-冰体系中的分配规律.按照DOM在XAD树脂上的吸附特性将其分为5个部分:疏水性有机酸(HPO-A),疏水性中性有机物(HPO-N),过渡亲水性有机酸(TPI-A),过渡亲水性中性有机物(TPI-N)和亲水性有机物(HPI).结果表明:在水体冻结过程中,5种DOM组分在水相中的DOC浓度均随冷冻时间的增长而增加,呈现冷冻浓缩效应.与溶解性有机碳(DOC)所表征的整体有机物相比,5种DOM组分中的卤乙酸(HAAs)前体物更倾向于停留在水相中浓缩.在5种DOM组分中,HPI是主要的HAAs前体物.5种DOM组分在未冻结水中的UV-254与HAAFP均表现出一定相关性,其中HPO-A, TPI-A和HPI的UV-254与HAAFP达到极显著水平.然而在融冰水中,这5种DOM组分的UV-254与HAAFP的相关性均不显著.     

Characterization of dissolved organic matter fractions from Lake Hongfeng, Southwestern China Plateau

With XAD-series and ion exchange resins, dissolved organic matter (DOM) from Lake Hongfeng in Southwestern China Plateau was isolated into 6 fractions, i.e., humic acid (HA), fulvic acid (FA), hydrophobic neutrals (HON), hydrophilic acids (HIA), hydrophilic bases (HIB) and hydrophilic neutrals (HIN). Those fractions were characterized by high performance size exclusion chromatography, fluorescence spectroscopy and UV absorbance. Among the 6 fractions, FA was predominant and accounted for 51% of the total DOM. The weight-average (M_w) and number-averaged (M_n) molecular weight of these fractions ranged from 1688 to 2355 Da and from 1338 to 1928 Da, respectively. A strong correlation was observed between specific UV absorbance at 280 nm, E₂/E₃ (absorbance at 250 nm to 365 nm), and the molecular weight for DOM fractions. UV-Vis fulvic-like fluorescence peaks were found in all fractions. Protein-like fluorescence peaks existed in HON may indicate that microbial activity was severely in Lake Hongfeng. There was a significant relationship between fluorescence intensities and specific UV absorbance at 254 nm for those DOM fractions, suggesting their similar luminescence characteristics. The values of fluorescence index (f_450/500) indicated that hydrophobic fractions may derive from terrestrial sources, and the hydrophilic fractions from microbial and terrestrial origins. Those results suggest that there were inter-relationships between molecular weight, fluorescence and absorbance characteristics, and also subtle consistencies between the hydrophilic and hydrophobic properties and the sources for these 6 fractions from Lake Hongfeng.     

石化污水厂二级出水溶解性有机物分级解析研究

以某石化污水处理厂二级出水为研究对象,采用大孔吸附树脂将污水中溶解性有机物分离成亲水性物质、疏水酸性物质、疏水中性物质和疏水碱性物质4个组分,分析了各组分的有机物的组成特征、三维荧光光谱特征及红外光谱特征.结果表明,亲水性物质和疏水酸性物质分别占水样中溶解性有机碳的49%和29%,是该石化污水厂二级出水中的主要物质类别.亲水性物质中含有较多的生物源腐殖质类物质,疏水中性物质含有较多的芳香族蛋白质和溶解性微生物代谢产物类物质.4种组分的红外光谱图中600~1200cm-1波数的指纹区波峰数量最多,多为芳香类同分异构体化合物.     

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.