Body fluid analog chlorination: Application to the determination of disinfection byproduct formation kinetics in swimming pool water

Disinfection by-products(DBPs) are formed in swimming pools by the reactions of bather inputs with the disinfectant.Although a wide range of molecules has been identified within DBPs,only few kinetic rates have been reported.This study investigates the kinetics of chlorine consumption,chloroform formation and dichloroacetonitrile formation caused by human releases.Since the flux and main components of human inputs have been determined and formalized through Body Fluid Analogs(BFAs),it is possible to model the DBPs formation kinetics by studying a limited number of precursor molecules.For each parameter the individual contributions of BFA components have been quantified and kinetic rates have been determined,based on reaction mechanisms proposed in the literature.With a molar consumption of 4 mol Cl_2/mol,urea is confirmed as the major chlorine consumer in the BFA because of its high concentration in human releases.The higher reactivity of ammonia is however highlighted.Citric acid is responsible for most of the chloroform produced during BFA chlorination.Chloroform formation is relatively slow with a limiting rate constant determined at 5.50 × 10~(-3) L/mol/sec.L-histidine is the only precursor for dichloroacetonitrile in the BFA.This DBP is rapidly formed and its degradation by hydrolysis and by reaction with hypochlorite shortens its lifetime in the basin.Reaction rates of dichloroacetonitrile formation by L-histidine chlorination have been established based on the latest chlorination mechanisms proposed.Moreover,this study shows that the reactivity toward chlorine differs whether L-histidine is isolated or mixed with BFA components.     

利用制糖副产物土壤化赤泥的效果

赤泥因具有碱性高、孔隙率低、团聚性差和养分缺乏等问题,同时因其生产性状差,堆场植被复垦难以实现;而且在堆存过程中,重金属元素具有潜在的长期浸出性,存在污染环境的风险。利用富含多种有机成分且蓬松度好的制糖副产物酒精废醪液、蔗渣对赤泥进行改性,可实现土壤化及植被复垦。结果表明,添加制糖副产物对赤泥理化性质及所含重金属迁移性具有显著影响,蔗渣能使孔隙度得到改善,酒精废醪液与赤泥比值（mL:g）＞3时,赤泥的pH可降至8以下,配合添加酒精废醪液和蔗渣可使赤泥的有机质含量从（19.8±1.2）g·kg-1增加到200 g·kg-1左右,经土柱模拟实验发现添加剂可使赤泥所含重金属的生物有效性增强。     

太阳光/NH2Cl体系降解微污染物的效能及动力学

利用太阳光和一氯胺(太阳光/NH₂Cl)体系降解阿司匹林((aspirin, ASA)、氟尼辛葡甲胺(flunixin meglumine, FMME)、苯甲酸(benzoic acid, BA)以及硝基苯(nitrobenzene, NB)4种代表性微污染物,探究该体系对于微污染物的降解效能以及动力学特征。结果表明,单独太阳光以及单独NH₂Cl体系对污染物几乎均无降解效果(降解率<5%),而太阳光/NH₂Cl体系中污染物的降解效能显著提升,pH的改变对4种污染物降解效能的影响各不相同。在实验pH条件下,以活性氮自由基和活性氯自由基为主的其他活性组分和NH₂Cl对FMME的降解起主要作用(贡献率为79.27%~89.39%),而羟基自由基(HO·)始终是ASA的降解中贡献最大的活性组分(贡献率为44.9%~76.8%)。在酸性环境中,太阳光/NH₂Cl体系产生的消毒副产物质量浓度及毒性方面均大于单独NH₂Cl体系,而在碱性条件下其产生的消毒副产物质量浓度则明显降低,实际中应用本体系进行消毒时应考虑将pH调至碱性。     

Ru/AC催化臭氧氧化难生物降解有机物

研究了臭氧单独氧化和Ru/AC催化臭氧氧化DMP、酚类物质和消毒副产物前体物.结果表明,Ru/AC能显著提高臭氧氧化中有机物的矿化效果.在DMP降解中,反应100 min后TOC的去除率由单独臭氧氧化的28.84%提高到66.13%.在23种酚类物质降解中,反应60min后TOC的去除率由单独臭氧的9.57%~56.08%提高到41.81%~82.32%.相对于单独臭氧,Ru/AC催化臭氧氧化更能有效地降低水源水中消毒副产物的生成势,以卤乙酸生成势的降低最为明显,100 min后卤乙酸生成势由144.02μg/L降到58.50μg/L,低于美国环保局规定的限制浓度60μg/L.而使用单独臭氧处理并不能使卤乙酸生成势降到符合美国EPA的规定.比较了BAC、O3+BAC、O3/AC+BAC以及Ru/AC+O3+BAC工艺处理水源水的效果,TOC平均去除率分别为3.80%、20.14%、27.45%和48.30%;COD平均去除率分别为4.37%、27.22%、39.91%和50.00%;UV254去除率分别为8.16%、62.24%、67.03%和84.95%.Ru/AC+O3+BAC工艺相比其他工艺,更能有效地...     

umu试验研究饮用水氯和氯胺消毒过程中遗传毒性的变化以及消毒条件的影响

采用umu遗传毒性测试方法考察了消毒剂投加量、反应时间和消毒剂氯氮比对某饮用水厂臭氧-生物活性炭出水加氯或氯胺消毒前后遗传毒性的影响.结果表明,炭后水具有一定的遗传毒性(20～70 ng/L),加氯或氯胺消毒后遗传毒性增加.反应时间为24 h,在相同投加量下氯消毒遗传毒性(40～95 ng/L)高于氯胺消毒遗传毒性(20～40 ng/L);当氯初始投加量从0 mg/L增加到10 mg/L时,炭后水的遗传毒性先迅速增加,在0.5～1 mg左右达到极大值,然后再降低,在3～5 mg左右达到极小值后缓慢上升,但是氯胺消毒后水样遗传毒性变化规律不如氯消毒的明显.当投加量为3 mg/L时,随着反应时间从0 h延长至72 h,无论是氯消毒还是氯胺消毒,炭后水遗传毒性均是先迅速增加,在2 h时达到极大值后再下降,在18 h左右达到极小值然后缓慢上升,而且任意反应时间内,氯胺消毒的遗传毒性(20～62 ng/L)均小于氯消毒(83～120 ng/L).本试验还研究了消毒剂氯氮比对炭后水氯消毒后遗传毒性的影响.在本试验条件下,从遗传毒性的角度看,对于饮用水消毒氯胺比氯更安全,而且2种消毒方式的遗传毒性的变化规律均不同于总HAAs的变化规律.     

溶解性有机氮乙酰胺氯化生成饮用水THMs的影响因素研究

氯化消毒可以有效杀灭细菌,但同时会产生危害人体健康的消毒副产物(DBPs).溶解性有机氮(DON)是DBPs的重要前体物,为考察DON对THMs的影响,首次选取乙酰胺(AcAm)作为前体物DON的代表物质,采用Plackett-Burman和Box-Behnken方法设计试验,考察了AcAm初始浓度、加氯量、pH、温度、溴离子浓度和反应时间等因素对三卤甲烷(THMs)生成的影响.结果表明,在AcAm生成THMs的过程中,AcAm初始浓度、pH和反应温度3个因素的影响程度较小,溴离子、有效氯和反应时间3因素的影响较大,其中溴离子的影响最为显著.溴离子浓度一定时,改变有效氯的含量,生成的THMs总量变化不大,溴离子对THMs的生成有一定的催化作用,控制溴离子的浓度是减少AcAm生成THMs的有效措施.在有效氯为8.77 mg/Ｌ、溴离子为0.77 mg/Ｌ及接触时间为6.20 h的条件下,THMs存在最大生成量为45.82 μg/L.随着反应时间的推移,溴分配系数n呈上升趋势,控制消毒反应时间,是减少THMs致癌风险的有效方法.同时探讨了AcAm生成THMs的反应路径,表述了溴离子的催化作用机制.     

Effect of NOM characteristics on brominated organics formation by ozonation

In this study, organic fractions, namely, humic acid, fulvic acid, hydrophobic base and neutral, and hydrophilic acid, base, and -neutral, were extracted from source water. First, the characteristics of the organic fractions, such as carboxylic acidity, phenolic acidity, ultraviolet absorbance, and aromatic content, were analyzed. Further, a systematic study was carried out to the by-products obtained when organic fractions, to which various amounts of bromide had been added, were oxidized with ozone. Samples after ozonation were analyzed for several brominated organics. The results indicate that the characteristics of the aquatic organic matter, including carboxylic/phenolic acidity, aromatic/aliphatic content, and ultraviolet absorbance, appear to affect the formation of halogenated organics. In general, hydrophobic organics having higher phenolic acidity, aromatic content, and ultraviolet absorbance have higher ozone consumption and produce higher concentrations of brominated organics than hydrophilic organics. It was also found that humic acid demonstrated the highest bromoform (CHBr(3)), dibromoacetic acid (DBAA), and 2,4-dibromophenol (2,4-DBP) formation, whereas hydrophilic neutral produced less CHBr(3) and 2,4-DBP than the rest of the organic fractions but produced the highest amount of dibromoacetone (DBAC) and dibromoacetonitrile (DBAN).     

微生物对饮用水典型消毒副产物前体物的降解效能及其群落特征

相对于CF（氯仿）等C-DBPs（含碳消毒副产物）,DCAN（二氯乙腈）等N-DBPs（含氮消毒副产物）具有更高的毒性.控制DBPs（消毒副产物）的前体物是抑制DBPs产生的最有效方法之一.为考察微生物降解DBPs前体物对生成DBPs的影响,分别选取C-DBPs和N-DBPs的典型代表物CF和DCAN及其相应的典型前体物Tyr（酪氨酸）和Asp（天冬氨酸）为研究对象,采用微生物培养前体物的方式,探究微生物对典型前体物Tyr和Asp的降解效果及其对生成CF和DCAN的控制效果.结果表明:①Tyr和Asp两种前体物经微生物降解后,DOC（溶解性有机碳）的去除率分别为94.0%和85.6%,DON（溶解性有机氮）的去除率分别为69.0%和81.0%.②在前体物经微生物降解后的水样中,氯化或氯胺化消毒后生成CF和DCAN的量较降解前均大大减少.以Tyr为前体物,水样经微生物降解、氯化消毒后生成CF和DCAN的量分别降低了56.1%和89.5%,氯胺化消毒后生成CF的量降低了68.5%;以Asp为前体物,水样经微生物降解、氯化消毒后生成DCAN的量最高可降低99.9%,经微生物降解、氯胺化消毒后生成的CF可降低50.7%.③对水样中微生物菌群分析发现,在门水平上的菌群主要有变形菌门（Proteobacteria）、放线菌门（Actinobacteria）和拟杆菌门（Bacteroidetes）,在属水平上的菌属主要有伯克氏菌属（Burkholderia-paraburkholderia）、半角藻属（Haliangium）、分枝杆菌属（Mycobacterium）、沉积小杆菌属（Sediminibacterium）、norank_f_Chitinophagaceae和动胶菌属（Zoogloea）.研究显示,微生物降解对DBPs典型前体物Tyr和Asp的去除,以及对生成CF和DCAN的控制具有较大的潜力,变形菌和放线菌在降解DBPs前体物中起到了重要作用.      

The fate of prazosin and levonorgestrel after electrochemical degradation process: Monitoring by-products using LC-TOF/MS

Prazosin (PRZ) and levonorgestrel (LNG) are widely used as an anti-disease drugs due to their biological activity in the human body. The frequent detection of these compounds in water samples requires alternative technologies for the removal of both compounds. After electrochemical degradation of PRZ and LNG, the parent compounds could be completely removed after treatment, but the identification and characterization of by-products are necessary as well. In this study, the effects of NaCl concentration and applied voltage were investigated during the electrochemical degradation process. The results revealed that the increase of NaCl concentration and applied voltage could promote the generation of hypochlorite OCl? and then enhance the degradation of PRZ and LNG. After initial study, 6 V and 0.2 g NaCl were selected for further experiments (96% and 99% removal of PRZ and LNG after 40 min, respectively). Energy consumption was also evaluated and calculated for PRZ and LNG at 3, 6 and 8 V. Solid phase extraction (SPE) method plays an important role in enhancing the detection limit of by-products. Furthermore, characterization and identification of chlorinated and non-chlorinated by-products were conducted using an accurate liquid chromatography-time of flight/mass spectrometry LC-TOF/MS instrument. The monitoring of products during the electrochemical degradation process was performed at 6 V and 0.2 g NaCl in a 50 mL solution. The results indicated that two chlorinated products were formed during the electrochemical process. The toxicity of by-products toward E. coli bacteria was investigated at 37°C and 20 hr incubation time.     

过滤式碳纤维电极消毒效果比较与机理研究

过滤式电极消毒作为一种安全、高效的新型消毒技术备受关注,然而目前使用的电极材料比较单一,且稳定性和高效性难以兼备,制约了该技术的设备化发展.本文采用过滤式消毒方式,考察了几种高孔隙率的导电碳纤维毡的消毒效果.结果表明,碳纤维毡电极具有优异的消毒能力,活性碳纤维电极可在几伏的电压下使细菌死亡,与传统电化学消毒相比,电压降低了1~2个数量级.其中A-PCF(聚丙烯腈基活性碳纤维)电极在外接电压2 V,水力停留时间2 s时即可对大肠杆菌菌液实现6.5log的去除.当外接电压≤2 V时,流出物中未检测到氯,pH保持不变,排除了电化学产物的影响.A-PCF可作为过滤式电极消毒的优选电极材料.