城市污水再生氯消毒过程中HAAs生成及迁移转化

针对城市污水再生处理工艺中卤乙酸类(HAAs)消毒副产物和卤乙酸生成潜能(HAAFP),结合三维荧光光谱,分析HAAs及其前体物的变化规律。结果表明,二级出水经2次加氯过程后,再生出水中的总卤乙酸浓度增加了90%,其中溴代乙酸的增幅最大,占增加量的82%。卤乙酸生成潜能较大的为氯代乙酸类物质,说明水中存在大量的氯代乙酸前体物。从工艺过程来看,总卤乙酸生成潜能与总有机物荧光强度分别下降了32%和28%,表明该再生处理工艺对HAAs前体物有一定的去除作用。     

管网末梢水中DOM分布特征及影响因素

为探明长期运行的供水管网末梢出水的溶解性有机物(DOM)分布特征及影响因素,采用三维荧光技术结合平行因子分析法(PARAFAC)对西北某高校管网水质进行了研究,并利用荧光区域积分(FRI)法得到各类DOM占比,通过实验揭示了加氯与DOM的相互关系。结果表明:该区域管网水中DOM主要为溶解性微生物副产物(SMP)、富里酸类(fulvic acid-like)和腐殖酸类(humic acid-like)有机物;DOM平均相对浓度约为2.0×106AU·nm2,其中类蛋白有机物较少,SMP占30%~34%、富里酸类占23%~25%、腐殖酸类占25%~28%;铸铁管出水中SMP总量(80 643 AU·nm2)和占比(34%)比不锈钢管出水中的SMP总量(72 420 AU·nm2)和占比(30%)有所升高;加氯对腐殖质类有机物具有一定的去除效果,且在前10 min内去除率最高。研究结果可为供水管网水质维护和加氯机制提供理论依据。     

臭氧对饮用水管网中溶解性有机物的影响

利用生物膜环状反应器模拟配水管网系统,将水厂砂滤池出水经过臭氧氧化后投加氯然后进入该模拟管网,另外把水厂砂滤池出水加氯后通入另一模拟管网作为对照实验。通过对两管网出水余氯、总铁、浊度、溶解性有机物(DOC)、以及消毒副产物三卤甲烷(THMs)、卤乙酸(HAAs)生成情况的测定,研究了饮用水臭氧处理对管网出水水质的影响。单因素方差分析结果表明,两管网出水的余氯、总铁、浊度以及THMs、HAAs含量相差不大,但DOC在臭氧氯管网中消耗较多。同时通过高效凝胶色谱(HPSEC),红外光谱(FTIR)和三维荧光光谱(EEM)表征了不同管网进出水DOC变化,结果表明,臭氧氧化后的管网出水中溶解性有机物荧光光谱中三区富里酸和五区腐植酸荧光峰值(ФⅢ+Ⅴ,n)减小较多,管网出水消毒副产物稍有增加。     

改良型AO法组合工艺中有机物的三维荧光分析

采用三维荧光(EEM)光谱技术,对上海竹园第二污水处理厂改良型AO法组合工艺运行过程中的各种溶解性有机物(DOM)进行分析,并对比研究传统好氧活性污泥法曝气池出水和A/O脱氮工艺硝化池出水DOM的EEM光谱的迁移变化特性.结果表明,各种DOM中主要的荧光物质有类蛋白质(荧光峰A和B)及类腐殖质(荧光峰C),经改良型AO法组合工艺处理后,荧光峰的强度降低了14％～60％,同时类蛋白质和腐殖质的结构也发生了变化;腐殖酸溯源表明DOM中的腐殖酸以微生物代谢产生的带有荧光基团的腐殖酸类为主.     

Al_2(SO_4)_3和FeCl_3混凝对红枫湖溶解性有机质的去除及卤代烃控制的影响

以三价阳离子(Al_2(SO_4)_3和FeCl_3)为混凝剂,在不同的投加量和水力条件下对贵阳市红枫湖取水口处溶解性有机质(DOM)的去除和卤代烃(THMs)生成势控制变化趋势进行研究。实验结果表明,在不同的混凝条件下,对DOM的去除率在60%左右,随着快速搅拌速率的增加,去除率略有提高;UV_(254)的去除率为85%左右,不同的混凝剂投加量和水力条件对其影响不大。混凝前后DOM的THM生成势降低约60%,二氯一溴甲烷(CHCl_2Br)和一氯二溴甲烷(CHClBr_2)占THMs的80%以上;对于不同的混凝剂类型,投加量和水力条件均对THMs生成势变化没有明显差异。三维荧光光谱(3DEEM)结果表明,DOM中腐殖酸部分在混凝过程中有较大去除,红外光谱(FTIR)验证了混凝去除的基团主要为羰基(C=O)的类共轭结构。而在强化混凝过程中没有得到较大去除的内源有机质(藻源有机物)可能是混凝后THMs的主要前体物质。因此,传统的混凝工艺主要去除DOM的腐殖酸部分,还需要结合其他的预处理方法对DOM中的其他组分进行有效去除,以控制THMs的生成势,提高饮用水的安全性。     

污水处理对黑水/灰水中溶解性有机物紫外光谱及荧光光谱特性的影响

为了考察黑水/灰水中溶解性有机物(DOM)光谱特征在污水处理过程中的变化规律以及生物处理前后黑水/灰水中DOM特性上的异同,对污水处理过程中黑水/灰水DOM的紫外光谱及荧光光谱特征进行了测定分析。结果表明,黑水原水中DOM的含量远高于灰水,且含有较多难降解有机物。生物处理可实现对黑水与灰水中易降解DOM的有效去除,MBR系统中的膜分离过程也可以起到截留溶解性有机物的作用。经MBR处理后,同黑水出水相比,灰水出水中的DOM含量更低,且主要为饱和有机物,苯环C骨架的聚合程度较高,THMs生成活性更低。生物处理过程可有效去除黑水/灰水中蛋白质类物质与易降解腐殖质类物质。生物处理后,黑水与灰水的蛋白峰均消失,黑水出水类腐殖酸峰F荧光强度高于灰水出水。与黑水出水相比,灰水出水更适用作再生水加以回收利用。     

SBR-混凝处理渗滤液过程中有机物的变化特征

考察了SBR-混凝组合工艺对垃圾渗滤液中溶解性有机物(DOM)不同分子量区间物质及组分腐殖酸(HA)、富里酸(FA)和亲水性有机物(Hy I)的去除效果,同时利用傅里叶红外光谱及三维荧光光谱对处理过程中DOM各组分变化特性进行了分析。结果表明,组合工艺对表观分子量为2 000~4 000及2 000的DOM去除率分别为89.3%和72.1%;对渗滤液DOM组分HA、FA和Hy I的去除率分别为-52.0%、73.1%和77.1%。红外光谱显示,DOM各组分都含有醇、羧酸、脂等多种有机物,SBR对糖、醇、羧酸等去除效果较好,而混凝对脂肪族及芳香族化合物去除效果较好;三维荧光光谱分析表明,经组合工艺处理,DOM各组分荧光峰强度及复杂化程度明显降低,且SBR工艺对色氨酸等类蛋白物质去除效果较好,混凝工艺对类腐殖酸、类富里酸等大分子物质的去除效果较好。     

臭氧氧化对二级出水有机物(EfOM)特性机制的影响

开展了臭氧氧化对二级出水有机物(effluent organic matter,Ef OM)的去除效能研究,并进一步采用超滤分离、三维荧光光谱等方法,系统研究了不同臭氧投加量下,Ef OM的分子量分布、亲疏水特性以及荧光特性的变化规律。结果表明,臭氧化去除Ef OM的效果有限,但能够有效分解二级出水中具有强烈紫外吸收的有机物。此外,臭氧能优先氧化分解二级出水中大分子有机物,有效提高二级出水的可生化性。臭氧氧化过程中,分子质量(molecular weight,MW)100 k Da的有机物组分被完全氧化分解,10 k DaMW100 k Da和1 k DaMW10 k D的有机物组分含量总体呈下降趋势,而MW1k Da的有机物组分随臭氧投加时间的延长含量不断上升。臭氧化后,Ef OM中疏水组分减少,亲水组分升高;酸性组分减少。随着臭氧投量的增加,蛋白质与腐殖酸类物质的荧光吸收强度迅速下降。     

三维荧光光谱技术对污水处理中溶解性有机物转化过程的分析

采用三维荧光光谱技术研究合肥市某污水处理厂污水处理过程中溶解性有机物(DOM)变化过程及荧光强度与COD浓度的关系。三维荧光光谱结果显示,原水中DOM主要由低激发波长色氨酸、高激发波长色氨酸和可见光区类腐殖酸组成;经过厌氧处理后,高激发波长色氨酸、低激发波长色氨酸荧光强度明显降低,分别从759.5、849.3降到388.6、387.4,同时在厌氧处理阶段有可见光区类富里酸生成,荧光强度为459.8。后续缺氧—好氧—沉淀—过滤—消毒处理中,低激发波长色氨酸、高激发波长色氨酸荧光强度基本都呈现降低趋势,最终出水的荧光强度分别为201.9、164.3。低激发波长色氨酸荧光强度、高激发波长色氨酸荧光强度、色氨酸荧光强度之和与COD浓度的相关系数(R2)分别为0.973 2、0.938 4、0.957 6。研究表明,利用三维荧光光谱技术可以阐明污水处理过程中DOM的变化过程及快速准确测量COD浓度。     

饮用水中三卤甲烷的生成机理与影响因素研究进展

在饮用水消毒过程中,氯会与天然有机物(NOM)等反应生成消毒副产物(DBPs),三卤甲烷(THMs)是一种主要的DBPs,长期低浓度的THMs暴露对人体有一定的健康风险。THMs和其前驱物种类繁多、生成机理复杂且影响因素诸多,如何抑制消毒过程中THMs的形成是饮用水安全领域的研究热点。通过查阅大量文献,从THMs形成机理及影响因素等方面归纳了目前THMs研究现状,总结了甲基酮、腐殖酸、氨基酸、β-二酮等重要前驱物生成THMs的反应途径,探讨了操作条件以及离子对THMs生成的影响,对该领域未来研究方向进行了展望。     

The organic precursors affecting the formation of disinfection by-products with chlorine dioxide

The object of this research was to study the formation of disinfection by-products by using chlorine dioxide (ClO2) as a disinfectant reacting with different properties of organic substance in natural aquatic environment. The adsorbent resin (XAD-4, XAD-7) was used to divide the organic matters in raw water into three groups. The influence of the function groups on structure, reaction tendency, and formation of disinfection by-products generated by the reaction of these organic substances with chlorine dioxide was explored. The experimental results show that the three different organic groups formed using adsorbent resin were hydrophobic substance, hydrophilic acid, and non-acid hydrophilics in proportions of 43%, 41%, and 16%, respectively. Within the raw water in our study, the hydrophilic substance had a higher distribution proportion than that described in general articles and journals, which indicates that this water was contaminated with pollution from human beings. The exploration of the reactivity of the three different organic substances with chlorine dioxide shows that the unit consumption of disinfection agent per unit organic matters (represented by ClO2/DOC) is in the following sequence hydrophobic substance > hydrophilic substance > non-acid hydrophilics. It indicated that larger molecular organic precursors had larger consumption of disinfectant. We also discovered that after the reaction of the three different organic substances with chlorine dioxide, the largest amount of disinfection by-products were generated by the non-acid hydrophilics.     

Transformation of effluent organic matter during subsurface wetland treatment in the Sonoran Desert

The fate of dissolved organic matter (DOM) during subsurface wetland treatment of wastewater effluent in a hot, semi-arid environment was examined. The study objectives were to (1) discern changes in the character of dissolved organics as consequence of wetland treatment (2) establish the nature of wetland-derived organic matter, and (3) investigate the impact of wetland treatment on the formation potential of trihalomethanes (THMs). Subsurface wetland treatment produced little change in DOM polarity (hydrophobic-hydrophilic) distribution. Biodegradation of labile effluent organic matter (EfOM) and internal loading of wetland-derived natural organic matter (NOM) together produced only minor changes in the distribution of carbon moieties in hydrophobic acid (HPO-A) and transphilic acid (TPI-A) isolates of wetland effluent. Aliphatic carbon decreased as a percentage of total carbon during wetland treatment. The ratio of atomic C:N in wetland-derived NOM suggests that its character is determined by microbial activity. Formation of THMs upon chlorination of HPO-A and TPI-A isolates increased as a consequence of wetland treatment. Wetland-derived NOM was more reactive in forming THMs and less biodegradable than EfOM. For both HPO-A and TPI-A fractions, relationships between biodegradability and THM formation potential were similar among EfOM and NOM isolates; the less biodegradable isolates exhibited greater THM formation potential.     

Microbial transformation of dissolved organic matter from different sources and its influence on disinfection byproduct formation potentials

Biodegradation-induced changes in the characteristics of dissolved organic matter (DOM) and the subsequent effects on disinfection byproduct formation potentials (DBPFPs) were investigated using six different sources of DOM (algae, leaf litter, reed, compost, paddy water, and treated municipal sewage effluent). Microbial incubation of the DOM samples increased the specific ultraviolet absorbance and humic-like fluorescence but decreased the protein/tannin-like fluorescence and relative distribution of smaller-sized DOM components. Comparison of the original versus biodegraded DOM samples using resin fractionation and pyrolysis–gas chromatography/mass spectrometry revealed that the biodegradation-induced changes were highly dependent on DOM sources and exhibited no consistent trends among the different sources. Changes in DBPFPs also differed with DOM source. Vascular plant-derived DOM (leaf litter and reed) demonstrated an enhancement in specific DBPFP after biodegradation, whereas little change or even a slight decrease was observed for the other DOM sources. Correlations that were significant between specific DBPFPs and the aromatic content or humic-like fluorescence for the original DOM samples were no longer significant after microbial degradation. The relative abundance of hydrophobic to hydrophilic structures in DOM is suggested to be a general indicator for the formation potential of trihalomethanes irrespective of DOM source and the state of biodegradation.     

Modeling and optimization of trihalomethanes formation potential of surface water (a drinking water source) using Box–Behnken design

Purpose  

The present research aims to investigate the individual and interactive effects of chlorine dose/dissolved organic carbon ratio, pH, temperature, bromide concentration, and reaction time on trihalomethanes (THMs) formation in surface water (a drinking water source) during disinfection by chlorination in a prototype laboratory-scale simulation and to develop a model for the prediction and optimization of THMs levels in chlorinated water for their effective control.     

回用生活污水的电化学消毒试验研究

对北京某中水站回用于杂用水的生活污水进行电化学消毒试验。试验结果表明 ,生活污水经生物接触氧化、活性炭吸附后 ,流经电化学消毒器停留 2 0s、耗电 0 .30kWh/m3 、消毒器出水放置 1h后 ,总大肠菌群数 <3个 /L ,满足生活杂用水的卫生学指标。当余氯浓度及接触时间相等的条件下 ,电化学消毒法的杀菌效果好于加氯消毒。E .coli细胞经电化学消毒和加氯消毒处理后 ,扫描电镜观察的结果表明 :2种方法作用后的细胞在形态上的变化是不相同的 ,说明电化学消毒的消毒机制不仅仅取决于电解产氯的作用 ,还有其他的杀菌作用     

The formation and control of disinfection by-products using chlorine dioxide

In this study, chlorine dioxide (ClO2) was used as an alternative disinfectant with vanillic acid, p-hydroxybenzoic acid, and humic acid as the organic precursors in a natural aquatic environment. The primary disinfection by-products (DBPs) formed were trihalomethanes (THMs) and haloacetic acids (HAAs). Under neutral conditions (pH = 7) for vanillic acid, more total haloacetic acids (THAAs) than total trihalomethanes (TTHMs) were found, with a substantial increase during the later stages of the reaction. In the case of p-hydroxybenzoic acid, the amount of THAAs produced was minimal. Raising the concentration of ClO2 was not favorable for the control of THAAs in low concentrations of vanillic acid. ClO2 could reduce the total amount of TTHMs and THAAs for higher concentration of vanillic acid. It was found that the humic acid treatment dosage was not significant. Under alkaline conditions (pH = 9), the control of TTHMs and THAAs for the treatment of vanillic acid was better and more economical, however, an appreciable amount of inorganic by-products were observed. Under the same alkaline condition, the control of THAA for the treatment of p-hydroxybenzoic acid was not beneficial and for the treatment of humic acid was not significant.     

Effects of thiocyanate on the formation of free cyanide during chlorination and ultraviolet disinfection of publicly owned treatment works secondary effluent.

Cyanide has been detected in effluent of some publicly owned treatment works (POTWs) at levels exceeding influent concentration. Thiocyanate (SCN-) is a cyanide-related compound encountered in most POTW influents and may be decomposed to free cyanide (CN-) under some circumstances. Effects of SCN- on the formation of cyanide during chlorination and UV disinfection were studied through a laboratory study with synthetic solutions and POTW secondary effluent. Results indicated that CN- was detected in SCN- solutions after chlorination in which the chlorine dose or reaction time was not sufficient to destroy SCN-completely, thus ensuring no residual chlorine to destroy any CN-produced. It was also found that SCN can be broken down to yield cyanide by UV irradiation. In addition, SCN- was observed to cause significant positive error in the conventional total cyanide analysis technique involving acidic distillation and colorimetric measurement when nitrate was present in the sample.     

紫外线杀菌效能的研究

自来水的消毒目前普遍采用氯及含氯化合物药剂，消毒过程中产生三卤甲烷等致癌或致突变物质，从而造成水体的二次污染，许多国家已经禁止在消毒中使用含氯药剂。因此，具有安全可靠高效杀菌作用的紫外线消毒技术逐渐发展起来，并越来越受到人们的关注。但是紫外线的使用也有一定的限制，通过紫外线照射时间及进水浊度的变化，研究了具有一定照射强度的紫外灯的杀菌效能变化，并得出了紫外线具有最佳杀菌效果的进水极限浊度和照射时间。同时还研究了紫外线对具有不同抗性的细菌的系灭效率，为饮用水和污水的消毒处理提供了实验基础。     

Monitoring of effluent DOM biodegradation using fluorescence, UV and DOC measurements

The potential of effluent DOM to undergo microbial degradation was assessed in batch experiments. Effluent samples from Haifa wastewater treatment plant and Qishon reservoir (Greater Haifa wastewater reclamation complex, Israel) were incubated either with effluent or soil microorganisms for a period of 2-4 months and were characterized by dissolved organic carbon contents (DOC), UV(254) absorbance and by fluorescence excitation-emission matrices. Three main fluorescence peaks were identified that can be attributed to humic/fulvic components and "protein-like" structures. During biodegradation, specific fluorescences (F/DOC) of the three peaks were increased at various extents, suggesting selective degradation of non-fluorescing constituents. In some cases increase in the effluent fluorescence (F) was observed thus proposing (i) the formation of new fluorescing material associated with DOM biodegradation and/or (ii) degradation of certain organic components capable of quenching DOM fluorescence. Based on the ratio between fluorescence intensity and UV(254), different biodegradation dynamics for fluorescent DOM constituents as compared with other UV-absorbing molecules was delineated. Overall, about 50% of the total DOM was found to be readily degradable such that residual resistant DOC levels were between 8 and 10 mg l(-1). Enhanced levels of residual DOM in effluent-irrigated soils may contribute to the DOM pool capable of carrying pollutants to groundwater.     

Minimization of the formation of disinfection by-products

The drinking water industry is required to minimize DBPs levels while ensuring adequate disinfection. In this study, efficient and appropriate treatment scheme for the reduction of disinfection by-product (DBPs) formation in drinking water containing natural organic matter has been established. This was carried out by the investigation of different treatment schemes consisting of enhanced coagulation, sedimentation, disinfection by using chlorine dioxide/ozone, filtration by sand filter, or granular activated carbon (GAC). Bench scale treatment schemes were applied on actual samples from different selected sites to identify the best conditions for the treatment of water. Samples were collected from effluent of each step in the treatment train in order to analyze pH, UV absorbance at 254 nm (UVA₂₅₄), specific UV absorbance at 254 nm (SUVA₂₅₄), dissolved organic carbon (DOC), haloacetic acids (HAAs) and trihalomethanes (THMs). The obtained results indicated that using pre-ozonation/enhanced coagulation/activated carbon filtration treatment train appears to be the most effective method for reducing DBPs precursors in drinking water treatment.