UV/氯联合处理含溴溶液中溴酸根的生成

研究了UV和氯联合作用下溴酸根离子(BrO^-₃)在低浓度含溴溶液中的生成,旨在探讨pH、次氯酸钠(NaOCl)浓度、溶解氧(DO)、光强和温度等因素对其生成的影响.研究表明,暗反应条件下H₂O-NaOCl-Br^-体系较稳定,而UV照射可使游离氯浓度持续降低,同时伴有部分Br^-（6 .6%～32%）被氧化成BrO^-₃离子;pH、温度和光强恒定时余氯的分解可用拟一级反应速率方程拟合;实验条件下（I为610～1 896 μW/cm²,T为12 .2～36 .1℃）,拟一级反应速率常数分别与体系温度和光强值有线性关系;BrO^-₃的生成大致可以分为快速、慢速和平缓3个阶段;在慢速生成阶段,BrO^-₃的生成量与余氯的分解量有良好的线性关系（绝大部分相关系数在0 .96以上）;实验范围内（pH为4 .41～11 .07,DO为1 .5～9 　mg/L,Cl₂为1 .23～4 .50 　mg/L）,低pH、低DO和高初始NaOCl（以氯计）浓度有利于溴酸根的生成,提高温度与光强均不同程度提高溴酸根生成速度,但同时因加速余氯的分解而减少了溴酸根的总生成时间.     

长江原水臭氧化生成溴酸根的影响因素

同济大学污染控制与资源化研究国家重点实验室,上海200092     

再生水紫外线-氯联合消毒工艺特性研究

以二级出水作为消毒对象,比较了紫外线-氯联合消毒与单一紫外线消毒对水中肠道指示菌的灭活效果,考察了联合消毒工艺副产物(三卤甲烷)生成情况.结果表明,单一紫外线消毒对肠道指示菌的灭活曲线在剂量大于10mJ/cm2时存在拖尾现象,剂量为80mJ/cm2时对总大肠菌群最高对数灭活率约为2.5;而在紫外线剂量20mJ/cm2、氯投加量8mg/L(接触时间30min)条件下,紫外线-氯联合消毒对总大肠菌群的对数灭活率达到7.0.20mJ/cm2紫外线与8mg/L氯消毒组合及80mJ/cm2紫外线与3mg/L氯消毒组合均可有效灭活总大肠菌群浓度至3CFU/L以下.经紫外线照射后再氯消毒,二级出水中三卤甲烷生成量仅为10~55mg/L.80mJ/cm2紫外线照射再氯消毒后三卤甲烷生成量略高于20mJ/cm2紫外线照射再氯消毒的情形.紫外线消毒后投加氯消毒,可有效提高再生水消毒效果,控制消毒副产物生成量.     

不同预氧化剂对长江原水氯(胺)化DBPs生成潜能的影响

以取自上海市杨树浦水厂的长江原水为研究对象,对比分析了3种常见预氧化剂二氧化氯(ClO2)、高锰酸钾(KMnO4)及氯(Cl2)预氧化对削减氯化和氯胺化消毒副产物(DBPs)生成潜能的效果情况.氯化培养实验结果表明,3种预氧化剂的处理对DBPs总量的去除效果均不显著,经ClO2、Cl2及KMnO4作用后可分别削减8.4%、5.7%及3.9%,效果为ClO2>Cl2>KMnO4.对于长江原水使用氯化消毒时,采用ClO2作为预氧化剂可取得对消毒副产物较好的去除效果.氯胺化培养实验结果表明,3种预氧化剂处理对长江原水氯胺化DBPs的生成潜能影响有较大差异,经ClO2和KMnO4作用后可分别削减18.1%及4.1%,而预氯化后则增高12.3%,对于长江原水使用氯胺化消毒时,采用ClO2作为预氧化剂可取得对消毒副产物较为明显的去除效果.同时,应尽量避免使用预氯化后加氯胺化的组合,以防止在水处理过程中生成更多的DBPs而影响出水水质.     

几种模型物质在氯化中形成THMs、HAAs的特性研究

以胃蛋白酶(蛋白质)、谷胱甘肽(氨基酸多肽)、葡萄糖(糖类)作为模型物质代表藻来源有机物,并以Fluka腐殖酸为对照,研究其耗氯量、三卤甲烷(主要是氯仿)、卤乙酸(主要是二氯乙酸(DCAA)、三氯乙酸(TCAA))的形成情况.结果显示4种模型物质在氯化后,其余氯在前2 h迅速降低,6 h后则下降速度渐缓;其中耗氯量最大的是谷胱甘肽(96 h:7.1 mg·mg^-1(以每毫克碳计,下同)),其次是胃蛋白酶(96 h:4.2 mg·mg^-1)、腐殖酸(96 h:3.0 mg·mg^-1),而葡萄糖最小(96 h:0.7 mg·mg^-1).4种模型物质氯仿、DCAA、TCAA的生成速度也是在起初的2 h较快,随后渐缓;但从单位碳的产量来看,腐殖酸和胃蛋白酶形成氯仿(96h: 15.1~55.2 μg·mg^-1(以每毫克碳计,下同))、DCAA(96 h: 15.1~55.2 μg·mg^-1)、TCAA(96h: 15.1~55.2 μg·mg^-1)均较多,而谷胱甘肽、葡萄糖则相对较少(氯仿-96 h:2.5~5.1 μg·mg^-1;DCAA-96 h:0.6~8.0 μg·mg^-1;TCAA-96 h:0.12~3.8 μg·mg^-1);而从前驱物特性来说,氯仿、TCAA的前驱物具有较高的芳香度(即高的SUV₂₅₄值),而DCAA前驱物的SUV₂₅₄相对较低.对于富含蛋白质、多肽、糖类等的富营养化饮用水源,则要格外注意饮用水中DCAA所带来的健康风险.     

长三角部分水源水氯化消毒后卤乙酸形成的多元回归模型研究

以长三角比较有代表性的3处水源(太湖、钱塘江、金兰水库)为实验对象,研究不同消毒条件下9种卤乙酸(haloacetic acids,HAAs)的形成及其影响因素,并通过建立多元回归模型来评估水源水氯化后HAAs的形成.结果表明:HAAs的形成水平依次为太湖钱塘江金兰水库,且均以二卤乙酸(dihaloacetic acid,DHAA)、三卤乙酸(trihaloacetic acid,THAA)为主.二氯乙酸(dichloroacetic acid,DCAA)、总二卤乙酸(ΣDHAA)、HAA5(USEPA规定的5种HAAs)、HAA9(9种HAA的简称)的回归模型具有良好的预测潜力,准确率达83.3%~94.4%,而三氯乙酸(trichloroacetic acid,TCAA)、一溴二氯乙酸(bromodichloroacetic acid,BDCAA)、ΣTHAA(总三卤乙酸)模型的预测准确率较低,只有47.2%~61.1%.根据偏相关系数分析,影响DCAA、ΣDHAA、HAA5的关键的因子是溶解性有机碳;影响TCAA、ΣTHAA、HAA9的关键的因子是投氯量;影响BDCAA形成的最关键因子是溴离子.     

Fe-Al/Al2O3催化臭氧化去除水中有机污染物2,4-D过程中溴酸盐的生成控制研究

采用浸渍、强化水解和后续水浴加热的方法制得催化剂Fe-Al/Al2O3,并通过XRD和XPS等表征手段对其结构性能进行了研究.结果表明,催化剂中铁是以二价和三价存在,且以三价铁为主;铝则以Al2O3和AlOOH形态存在.与单独臭氧化相比,Fe-Al/Al2 O3既能高效矿化水中的难降解有机物2,4-二氯苯氧乙酸(2,4-D),又能明显抑制溴酸盐的生成,体现出很好的循环使用稳定性.进一步探讨了臭氧投加量和溴离子初始浓度对催化臭氧化效率和溴酸盐生成的影响.研究表明,在Fe-Al/Al2O3催化臭氧化过程中,水中溴酸盐浓度受臭氧投加量和溴离子初始浓度的影响较小,均可明显抑制溴酸盐的生成,且有机物的矿化效率随着臭氧投加量的增加而显著提高.     

MIEX预处理技术对长江原水中有机物的去除效能

利用烧杯试验研究了磁性离子交换树脂（magnetic ion exchange resin,MIEX）预处理对长江原水中有机物的去除效能,以总溶解有机碳(DOC)、254 nm紫外吸收值(UV254)、有机物相对分子质量分布、有机物分级、紫外扫描以及消毒副产物生成量等指标进行表征.结果表明,长江水源水中的有机物主要为小分子亲水性有机物,其含量占有机物总量的50%以上;MIEX预处理可以有效降低水中有机物的含量,投加量为10 mL/L、接触时间为15 min时,DOC的去除率超过35%,相对分子质量和分级的测定结果表明,小分子亲水性部分有机物的去除导致了DOC去除效果的改善;从紫外扫描结果可看出,MIEX预处理对在190～250 nm波长时有强吸收的有机物去除效果非常明显,但对在高于250 nm波长处有吸收的有机物去除效果与混凝阶段的效果相近.     

Determination of haloacetic acids in hospital effuent after chlorination by ion chromatography

The ion chromatography combined solid phase extraction (SPE) method was developed for the analysis of low concentration haloacetic acids (HAAs), a class of disinfection by-products formed from chlorination of hospital wastewater. The monitored HAAs included monochloroacetic acid, monobromoacetic acid, dichloroacetic acid, dibromoacetic acid and trichloroacetic acid. The method employed a sodium hydroxide eluent at a flow rate of 0.8 mlmin, electrolytically generated gradients, and suppressed conductivity detection. To analyze the HAAs in real hospital wastewater samples, C18 pretreatment cartridge was utilized to reduce samples' turbidity. Preconcentration with SPE and matrix elimination with treatment cartridges were investigated and found to be able to obtain acceptable detection limits. Linearity, repeatability and detection limits of the above method were evaluated. The detection limits of monobromoacetic acid and dibromoacetic acid were 2.61 μgL and 1.30 μgL, respectively, and the other three acids are ranging from 0.48 to 0.82 μgL under 25-fold preconcentration. When the above optimization procedure was applied to three hospital wastewater samples with different treatment processes in Tianjin, it was found that the dichloroacetic acid was the major compound, and the growth ratios of the HAAs after disinfection by sodium hypochlorite were 91.28%, 63.61% and 79.50%, respectively.     

Determination of haloacetic acids in hospital e uent after chlorination by ion chromatography

The ion chromatography combined solid phase extraction （SPE） method was developed for the analysis of low concentration haloacetic acids （HAAs）, a class of disinfection by-products formed from chlorination of hospital wastewater. The monitored HAAs included monochloroacetic acid, monobromoacetic acid, dichloroacetic acid, dibromoacetic acid and trichloroacetic acid. The method employed a sodium hydroxide eluent at a flow rate of 0.8 ml/min, electrolytically generated gradients, and suppressed conductivity detection. To analyze the HAAs in real hospital wastewater samples, C18 pretreatment cartridge was utilized to reduce samples＇ turbidity. Preconcentration with SPE and matrix elimination with treatment cartridges were investigated and found to be able to obtain acceptable detection limits. Linearity, repeatability and detection limits of the above method were evaluated. The detection limits of monobromoacetic acid and dibromoacetic acid were 2.61 μg/L and 1.30 μg/L, respectively, and the other three acids are ranging from 0.48 to 0.82μg/L under 25-fold preconcentration. When the above optimization procedure was applied to three hospital wastewater samples with different treatment processes in Tianjin, it was found that the dichloroacetic acid was the major compound, and the growth ratios of the HAAs after disinfection by sodium hypochlorite were 91.28%, 63.61% and 79.50%, respectively.     

Seasonal variation effects on the formation of trihalomethane during chlorination of water from Yangtze River and associated cancer risk assessment

For the system of water samples collected from Yangtze River,the effects of seasonal variation and Fe(III) concentrations on the formation and distribution of trihalomethanes (THMs) during chlorination have been investigated.The corresponding lifetime cancer risk of the formed THMs to human beings was estimated using the parameters and procedure issued by the US EPA.The results indicated that the average concentration of THMs (100.81 μg/L) in spring was significantly higher than that in other seasons,which ...     

Enhanced cyanogen chloride formation after UV/PS and UV/H2O2 pre-oxidation and chlorination in natural river water

Ultraviolet/persulfate (UV/PS) and Ultraviolet/hydrogen peroxide (UV/H₂O₂) have attracted much attention in recent years as advanced oxidation processes for water treatment. However, it is not all clear how these two methods affect the formation of cyanogen chloride (CNCl) in the subsequent water chlorination process. In this study, it was found that both UV/H₂O₂ and UV/PS pre-oxidation promoted the formation of CNCl in six actual water samples collected from urban rivers. Glycine, uric acid, arginine and histidine were investigated as the model compounds to explore the effects of different methods on the production of CNCl. The results showed that compared with chlorination alone, pre-oxidation by UV/H₂O₂ and UV/PS can reduce the production of CNCl for glycine and uric acid by up to 95% during post-chlorination process. However, they can greatly promote the formation of CNCl for arginine and histidine by up to 120-fold. In a more detailed investigation, pre-oxidation of histidine formed highly reactive intermediates to chlorine, leading to increased CNCl formation and chlorine consumption. The results showed that the precursors of CNCl was altered after pre-oxidation, and need to be re-evaluated.     

O3/UV降解水中的乙酸和硝基苯

利用O3 /UV和O3/H2O2降解了水中的乙酸,结果表明,在相同条件下处理60min后,O3/UV对乙酸的去除率仅比单独臭氧化处理提高了3%,而O3/H2O2在此条件下完全降解乙酸.O3/UV在处理硝基苯过程中却显示较好的氧化降解能力,通过分析表明,硝基苯降解过程中所产生的副产物H2O2对有机物的去除具有很重要的作用.因此,O3/UV氧化降解能力的提高可能有2方面的原因,紫外光对有机物的活化作用;中间产物H2O2催化臭氧分解产生了高活性的羟基自由基. 单独紫外光催化臭氧分解产生羟基自由基的效率极低.     

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.     

长江中下游浅水湖泊紫外辐射的衰减

基于对长江中下游22个浅水湖泊有色可溶性有机物吸收的测量,运用经验模式估算了紫外辐射(UV-B、UV-A)在长江中下游湖泊的衰减及对应的穿透深度,并利用在武汉东湖实测的紫外辐射衰减进行了检验.结果表明,UV-B波段的320nm和UV-A波段的380nm衰减系数变化范围分别为2.05～21.00m^-1,1.07～12.85m^-1,对应的1%穿透深度分别为0.22～2.25m,0.36～4.29m.估算得到的紫外辐射衰减系数与DOC浓度均存在显著性正相关,但UV-B波段要高于UV-A波段.武汉东湖实测的紫外辐射衰减检验发现,基于CDOM吸收系数估算UV-B辐射衰减较为精确,而由于浮游植物吸收和悬浮物散射等影响对UV-A波段估算精度则明显下降.     

长江、黄河、松花江60-80年代水质变化趋势与社会经济发展的关系

对我国“水年鉴”上所载长江、黄河和松花江自５０年代末至８０年代中期所有站点的水化学监测数据进行统计分析，发现，在此时段内，就天然水主要离子成分而言，长河、黄河和松花江表现出各自独特的水质变化趋势。对其成因和机理进行了探讨，认为长江中上游水质的酸化趋势起因于该地区不断增长的燃煤硫排放所引起的严重酸沉降过程和不断增加的农田流失氮肥的氧化成酸过程。松花江水质的碱化趋势主要与黑龙江省造纸废水排放所引起的     

黄河原水中消毒副产物前体物的组成特征及其化学预氧化处理效果对比

以取自河南省郑州市石佛原水厂的黄河原水为研究对象,系统研究了原水中消毒副产物(DBPs)前体物的组成规律,对比分析了3种预氧化剂(高锰酸钾、自由氯和二氧化氯)对原水中DBPs生成潜能的消减规律.试验结果表明:原水中DBPs的前体物均以小分子有机物和疏水性组分(52.51%)为主;分子量小于1 k Da有机物组分是生成含氮消毒副产物(N-DBPs)和三卤甲烷(THMs)的主要前体物;疏水性有机物是生成THMs的主要前体物,亲水性有机物是生成N-DBPs的主要前体物.经Cl2预氧化后,直接生成的DBPs随着自由氯投加量的增加而增加,Cl O2和KMn O4预氧化直接增加DBPs产生量.经3种预氧化剂氧化后,原水中三卤甲烷生成潜能(THMFP)均呈现一定的下降,其降低量依次为Cl O2Cl2KMn O4;然而3种预氧化剂都不能有效的减少含氮消毒副产物生成潜能(N-DBPFP),Cl O2预氧化和Cl2预氧化可增加N-DBPs生成潜能,尤其在较高投加量下,Cl2预氧化将大大增加N-DBPs生成潜能.为有效消减总DBPs生成潜能,水厂可优先采用KMn O4或Cl O2作为预氧化剂处理引黄水库或沉砂池水.     

长江流域典型城市河段黑臭水体生态整治案例分析

童套河、西沙河是长江流域有代表性的河网型河道水体,也是扬州市中心城区典型的黑臭水体。分析并阐述了童套河、西沙河主要水环境问题、治理措施、典型治理技术以及治理成效。治理前河道水体存在两岸污水收集能力不足、生活垃圾任意堆放,河道内水体流动性差、底泥淤积严重、水生态系统退化等问题,水质表现为黑臭,扬州市采取了控源截污、内源清理,水动力复氧、生态修复、活水换水、长效管理的治理思路,主要实施包括管网雨污分流改造,河道清淤疏浚,增设水循环造流增氧设备,构建生态河床、生态岸坡,活水换水等技术措施,取得了良好的环境效益、经济效益和社会效益。     

Occurrence and formation potential of nitrosamines in river water and ground water along the Songhua River, China

The presence of mutagenic and carcinogenic nitrosamines in water is of great concern. In this study, seven nitrosamines including N-nitrosodimethylamine (NDMA), N-nitrosodiethylamine (NDEA), N-nitrosomethylethylamine (NMEA), N-nitrosopyrrolidine (NPyr), N-nitrosopiperidine (NPip), N-nitrosodi-n-propylamine (NDPA), and N-nitrosodi-n-butyl-amine (NDBA) were investigated in river water and ground water samples collected from 5 representative cities (Jilin, Songyuan, Harbin, Jiamusi and Tongjiang) along the Songhua River. The total concentrations of nitrosamines in ground water were n.d. (not detected) to 60.8 ng/L, NDMA was the most frequently detected nitrosamines in ground water, followed by NDEA and NPip. Relatively high detected frequency and concentrations of NDMA were also observed in river water samples, and the total nitrosamines'' concentration at midstream is always higher than that at upstream and downstream. After 24 hr chlorination, concentration of NDMA, NDBA was obviously increased but NDEA was reduced. Furthermore, UV₂₅₄ showed a better relationship with NDMA-FP rather than dissolved organic carbon (DOC), NH₄-N, and TDN.     

北京晴天紫外辐射的传输、损失及其长期变化

基于北京1990年晴天太阳辐射和气象观测资料的分析,考虑了影响紫外辐射(UV)的主要因子——臭氧、光化学、散射等对UV能量的吸收、利用和散射作用,发展了晴天UV的经验模式.研究表明,1990和1991年UV计算值与UV测量值吻合较好,二者相对偏差的平均值分别为3.68％、3.83％.利用此经验模式计算了大气上界的UV,计算结果较为合理.采用经验模式及考虑太阳活动、轨道参数、大气成分等因素的订正,计算了北京1979-1998年晴天的UV,其表现为下降趋势,年均下降率为0.20％.1979-1998年晴天,受臭氧、光化学和散射等因子影响,损失于大气中的各个UV能量都表现出增长趋势,年增长率分别为6.93％、7.56％、7.13％;损失于大气的UV能量以吸收和利用作用为主,并表现为冬季最大的特征.