Evaluating the e ects of granular and membrane filtrations on chlorine demand in drinking water

In this study, chlorine decay experiments were conducted for the raw water from Nakdong River that is treated by Chilseo Water Treatment Plant (CWTP) situated in Haman, Korea as well as the e uents from sand and granular activated carbon (GAC) filters of CWTP and fitted using a chlorine decay model. The model estimated the fast and slow reacting nitrogenous as well as organic/inorganic compounds that were present in the water. It was found that the chlorine demand due to fast and slow reacting (FRA and SRA) organic/inorganic substances was not reduced significantly by sand as well as GAC filters. However, the treated e uents from those filters contained FRA and SRA that are less reactive and had small reaction rate constants. For the e uents from microfiltration, ultrafiltration, and nanofiltration the chlorine demand because FRA and SRA were further reduced but the reaction rate constants were larger compared to those of sand and GAC filter e uents. This has implications in the formation of disinfection by products (DBPs). If DBPs are assumed to form due to the interactions between chlorine and SRA, then it is possible that the DBP formation potential in the e uents from membrane filtrations could be higher than that in the e uents from granular media filters.     

Particle properties in granular activated carbon filter during drinking water treatment

The elemental composition and bacteria attached in particles were investigated during granular activated carbon (GAC) filtration.The experimental results showed that trapped influent particles could form new,larger particles on GAC surface.The sloughing of individuals off GAC surface caused an increase in effluent particles in the size range from 5 to 25 μm.The selectivity for element removal in GAC filters caused an increasing proportion of metallic elements in the effluent particles.The distribution of molar ratio indicated a complicated composition for large particles,involving organic and inorganic substances.The organic proportion accounted for 40% of total carbon attached to the particles.Compared with dissolved carbon,there was potential for the formation of trihalomethanes by organic carbon attached to particles,especially for those with size larger than 10 μm.The pure carbon energy spectrum was found only in the GAC effluent and the size distribution of carbon fines was mainly above 10 μm.The larger carbon fines provided more space for bacterial colonization and stronger protection for attached bacteria against disinfection.The residual attached bacteria after chorine disinfection was increased to 10 2-10 3 CFU/mL within 24 hours at 25°C.     

GAC-石英砂滤池处理高氨氮原水的生产研究

以广州市珠江流溪河下游为水源,采用GAC-石英砂滤池处理沉淀池出水,研究了该工艺对枯水期高氨氮原水的去除规律及其影响因素。结果表明:GAC-石英砂滤池滤与普通砂滤池相比氨氮的去除显著提高,滤后水氨氮平均值为2.08mg/L,去除量约为1.0mg/L,去除率为33.8%。研究显示氨氮处理效果受余氯的灭菌作用、溶解氧不足、原水水质下降、pH值不足、活性炭滤料吸附性能下降、空床接触时间短、反冲洗周期与强度的影响。建议降低前投氯而加强后投氯量,同时使用无氯水进行反冲洗;保持滤后水溶解氧在2～4mg/L且pH值7.5;延长反冲洗周期至36h;适当降低运行负荷可提高GAC-石英砂滤池对氨氮的去除效果。     

Chloramine demand estimation using surrogate chemical and microbiological parameters

A model is developed to enable estimation of chloramine demand in full scale drinking water supplies based on chemical and microbiological factors that affect chloramine decay rate via nonlinear regression analysis method. The model is based on organic character (specific ultraviolet absorbance (SUVA)) of the water samples and a laboratory measure of the microbiological (F m ) decay of chloramine. The applicability of the model for estimation of chloramine residual (and hence chloramine demand) was tested on several waters from different water treatment plants in Australia through statistical test analysis between the experimental and predicted data. Results showed that the model was able to simulate and estimate chloramine demand at various times in real drinking water systems. To elucidate the loss of chloramine over the wide variation of water quality used in this study, the model incorporates both the fast and slow chloramine decay pathways. The significance of estimated fast and slow decay rate constants as the kinetic parameters of the model for three water sources in Australia was discussed. It was found that with the same water source, the kinetic parameters remain the same. This modelling approach has the potential to be used by water treatment operators as a decision support tool in order to manage chloramine disinfection.     

Chloramination of wastewater effluent: Toxicity and formation of disinfection byproducts

The reclamation and disinfection of waters impacted by human activities (e.g., wastewater effluent discharges) are of growing interest for various applications but has been associated with the formation of toxic nitrogenous disinfection byproducts (N-DBPs). Monochloramine used as an alternative disinfectant to chlorine can be an additional source of nitrogen in the formation of N-DBPs. Individual toxicity assays have been performed on many DBPs, but few studies have been conducted with complex mixtures such as wastewater effluents. In this work, we compared the cytotoxicity and genotoxicity of wastewater effluent organic matter (EfOM) before and after chloramination. The toxicity of chloraminated EfOM was significantly higher than the toxicity of raw EfOM, and the more hydrophobic fraction (HPO) isolated on XAD-8 resin was more toxic than the fraction isolated on XAD-4 resin. More DBPs were also isolated on the XAD-8 resin. N-DBPs (i.e., haloacetonitriles or haloacetamides) were responsible for the majority of the cytotoxicity estimated from DBP concentrations measured in the XAD-8 and XAD-4 fractions (99.4% and 78.5%, respectively). Measured DBPs accounted for minor proportions of total brominated and chlorinated products, which means that many unknown halogenated compounds were formed and can be responsible for a significant part of the toxicity. Other non-halogenated byproducts (e.g., nitrosamines) may contribute to the toxicity of chloraminated effluents as well.     

活性炭深度处理工艺用于地下回灌的水质研究

以北京高碑店污水处理厂二级生化出水为对象,研究了用于地下回灌的活性炭三级处理工艺.活性炭可有效降低DOC,UV-254和COD,部分去除可吸附有机卤化物(AOX).再经过土壤含水层处理,约90%的可吸附有机溴化物(AOBr)可被去除.Ames试验结果显示活性炭工艺可有效降低二级生化出水中的致突物.GC/MS分析表明,活性炭吸附可降低有机物含量,再经土壤含水层处理,大部分有机物及优先控制的污染物可被去除.      

不同深度处理工艺再生水中余氯衰减规律及溶解性有机物变化特性比较

考察了余氯在不同深度处理工艺再生水中的衰减规律,并利用紫外-可见吸收差光谱和三维荧光光谱对余氯衰减过程的有机物变化进行了初步解析.结果表明,再生水中的余氯衰减迅速,加氯前0.5 h内的氯消耗占8 h内氯消耗的50%以上.混凝出水水样的余氯衰减速率大于超滤出水和臭氧出水.加氯后,混凝出水和超滤出水的紫外-可见吸收差光谱在230 nm和280 nm附近出现特征峰,表明余氯衰减过程中,水中具有不饱和键和生色团的物质被破坏.臭氧出水在波长230 nm附近出现特征峰.加氯使再生水的荧光强度减弱,混凝出水中腐殖质类物质荧光强度的降低程度大于超滤出水和臭氧出水,表明该类物质可能是影响余氯衰减速率的主要物质.     

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.     

The role of metal oxides on oxidant decay and disinfection byproduct formation in drinking waters: Relevance to distribution systems

Maintaining a residual disinfectant/oxidant (e.g., chlorine and chlorine dioxide), is a generally used strategy to control microbial contaminants and bacterial regrowth in distribution systems. Secondarily oxidant, such as hypobromous acid (HOBr), can be formed during chlorination of bromide-containing waters. The decay of oxidants and formation of disinfection byproducts (DBPs) due to the interaction between oxidants and selected metal oxides were studied. Selected metal oxides generally enhanced the decay of these halogen-containing oxidants via three pathways: (1) catalytic disproportionation to yield an oxidized form of halogen (i.e., halate) and reduced form (halide for chlorine and bromine or chlorite for chlorine dioxide), (2) oxygen formation, and (3) oxidation of a metal in a reduced form (e.g., cuprous oxide) to a higher oxidation state. Cupric oxide (CuO) and nickel oxide (NiO) showed significantly strong abilities for the first pathway, and oxygen formation was a side reaction. Cuprous oxide can react with oxidants via the third pathway, while goethite was not involved in these reactions. The ability of CuO on catalytic disproportionation of HOBr remained stable up to four cycles. In chlorination process, bromate formation tends to be important (exceeding 10 µg/L) when initial bromide concentration is above 400 µg/L in the presence of dissolved organic matter. Increasing initial bromide concentrations increased the formation of DBPs and calculated cytotoxicity, and the maximum was observed at pH 8.6 during chlorination process. Therefore, the possible disinfectant loss and DBP formation should be carefully considered in drinking water distribution systems.     

Evaluate HAA removal in biologically active carbon filters using the ICR database

The effects of biologically active carbon (BAC) filtration on haloacetic acid (HAA) levels in plant effluents and distribution systems were investigated using the United States Environmental Protection Agency’s Information Collection Rule (ICR) database. The results showed that average HAA5 concentrations in all locations were 20.4 μg·L⁻¹ and 29.6 μg·L⁻¹ in ICR plants with granular activated carbon (GAC) and ICR plants without GAC process, respectively. For plants without GAC, the highest HAA levels were observed in the quarters of April to June and July to September. However, for plants with GAC, the highest HAA levels were observed in the quarters of April to June and January to March. This HAA level profile inversely correlated well with water temperature, or biologic activity. For GAC plants, simulated distribution samples matched well with distribution system equivalent samples for Cl₃AA and THMs. For plants with and without GAC, simulated distribution samples overestimated readily biodegradable HAAs in distribution systems. The study indicated that through HAA biodegradation, GAC process plays an important role in lowering HAA levels in finished drinking water.     

Zebrafish embryo toxicity of 15 chlorinated, brominated, and iodinated disinfection by-products

Disinfection to protect human health occurs at drinking water and wastewater facilities through application of non-selective oxidants including chlorine. Oxidants also transform organic material and form disinfection by-products (DBPs), many of which are halogenated and cyto- and genotoxic. Only a handful of assays have been used to compare DBP toxicity, and researchers are unsure which DBP(s) drive the increased cancer risk associated with drinking chlorinated water. The most extensive data set employs an in vitro model cell, Chinese hamster ovary cells. Traditionally, most DBP research focuses on the threat to human health, but the effects on aquatic species exposed to DBPs in wastewater effluents remain ill defined. We present the developmental toxicity for 15 DBPs and a chlorinated wastewater to a model aquatic vertebrate, zebrafish. Mono-halogenated DBPs followed the in vivo toxicity rank order: acetamides > acetic acids > acetonitriles ~ nitrosamines, which agrees well with previously published mammalian in vitro data. Di- and tri-halogenated acetonitriles were more toxic than their mono-halogenated analogues, and bromine- and iodine-substituted DBPs tended to be more toxic than chlorinated analogues. No zebrafish development effects were observed after exposure to undiluted or non-concentrated, chlorinated wastewater. We find zebrafish development to be a viable in vivo alternative or confirmatory assay to mammalian in vitro cell assays.     

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.     

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.     

A balancing act: Optimizing free chlorine contact time to minimize iodo-DBPs, NDMA, and regulated DBPs in chloraminated drinking water

Many drinking water treatment plants in the U.S. have switched from chlorination to chloramination to lower levels of regulated trihalomethane (THM) and haloacetic acid (HAA) disinfection byproducts (DBPs) in drinking water and meet the current regulations. However, chloramination can also produce other highly toxic/carcinogenic, unregulated DBPs: iodo-acids, iodo-THMs, and N-nitrosodimethylamine (NDMA). In practice, chloramines are generated by the addition of chlorine with ammonia, and plants use varying amounts of free chlorine contact time prior to ammonia addition to effectively kill pathogens and meet DBP regulations. However, iodo-DBPs and nitrosamines are generally not considered in this balancing of free chlorine contact time. The goal of our work was to determine whether an optimal free chlorine contact time could be established in which iodo-DBPs and NDMA could be minimized, while keeping regulated THMs and HAAs below their regulatory limits. The effect of free chlorine contact time was evaluated for the formation of six iodo-trihalomethanes (iodo-THMs), six iodo-acids, and NDMA during the chloramination of drinking water. Ten different free chlorine contact times were examined for two source waters with different dissolved organic carbon (DOC) and bromide/iodide. For the low DOC water at pH 7 and 8, an optimized free chlorine contact time of up to 1 h could control regulated THMs and HAAs, as well as iodo-DBPs and NDMA. For the high DOC water, a free chlorine contact time of 5 min could control iodo-DBPs and NDMA at both pHs, but the regulated DBPs could exceed the regulations at pH 7.     

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.     

城市污水深度处理中有机物的去除

以城市污水地下水回灌为回用目的 ,研究不同的污水深度处理工艺及对二级生物处理出水中有机物的去除 .研究结果表明 ,原水若未经深度处理 ,直接由土壤含水层处理的出水不能满足推荐的回灌水水质要求 .对原水分别采用混凝沉淀、过滤、臭氧氧化、粉末活性炭和粒状活性炭吸附等处理单元及组合工艺进行深度处理效果的对比 ,最终选用由混凝沉淀 ,砂滤 ,粒状活性炭过滤与土壤含水层处理相结合的工艺流程 .城市污水处理厂的二级出水经该工艺处理后 ,出水中的 DOC可降至 3mg/L以下 ,且活性炭柱的产水床体积可达 350 0 BV.     

南水北调丹江口水库水氯(胺)化消毒副产物产生特性与消毒工艺对比

系统研究了南水北调中线工程水源——丹江口水库水在氯(胺)化消毒条件下,常规消毒副产物的产生特性,考察了消毒方式、消毒剂投加量、接触时间、p H和溴离子浓度等因素的影响,并对消毒工艺参数进行了优化.结果发现,丹江口水库水经氯化消毒可产生三氯甲烷、二氯一溴甲烷等常规含碳和较低浓度二氯乙腈、三氯硝基甲烷等含氮消毒副产物,而氯胺化消毒仅产生三氯甲烷和三氯硝基甲烷等消毒副产物(disinfection by-products,DBPs).自由氯消毒过程产生的各类型DBPs浓度约为氯胺消毒的7.5倍,短时自由氯转氯胺方式DBPs产生量介于两者之间;随着自由氯投加量增加,各类型消毒副产物均呈现增加趋势,投加量大于2 mg·L-1后DBPs增加量较少.随氯胺投加量增加,三氯甲烷生成量变化不大,投加量大于2mg·L-1后可产生三氯硝基甲烷等副产物.随反应时间延长,自由氯的衰减速率明显大于氯胺,同时消毒副产物增长量明显快于氯胺消毒.随着p H升高,自由氯消毒后三卤甲烷含量呈现增加趋势,而氯胺消毒后变化不明显.随溴离子浓度的增加,自由氯和氯胺消毒后副产物类型均向溴代DBPs转变,同时总生成量明显增加,自由氯消毒DBPs增长量明显大于氯胺消毒过程.丹江口水库水采用氯胺化消毒可以降低消毒副产物的生成风险,如采用自由氯消毒方式,水厂需根据实际常规处理工艺重点控制自由氯的投加量等参数.     

Electrochemical in situ regeneration of granular activated carbon using a three-dimensional reactor

Electrochemical in situ regeneration of granular activated carbon (GAC) saturated with phenol was experimentally investigated using a three-dimensional electrode reactor with titanium filter electrode arrays. The feasibility of the electrochemical regeneration has been assessed by monitoring the regeneration efficiency and chemical oxygen demand (COD). The influence of the applied current, the effluent flow rate, and the effluent path of the electrochemical cell have been systematically studied. Under the optimum conditions, the regeneration efficiency of GAC could reach 94% in 2 hr, and no significant declination was observed after five-time continuous adsorption-regeneration cycles. The adsorption of organic pollutants was almost completely mineralized due to electrochemical oxidation, indicating that this regeneration process is much more potentially cost-effective for application.     

Electrochemical in situ regeneration of granular activated carbon using a three-dimensional reactor

Electrochemical in situ regeneration of granular activated carbon (GAC) saturated with phenol was experimentally investigated using a three-dimensional electrode reactor with titanium filter electrode arrays. The feasibility of the electrochemical regeneration has been assessed by monitoring the regeneration efficiency and chemical oxygen demand (COD). The influence of the applied current, the effluent flow rate, and the effluent path of the electrochemical cell have been systematically studied. Under the optimum conditions, the regeneration efficiency of GAC could reach 94% in 2 hr, and no significant declination was observed after five-time continuous adsorption-regeneration cycles. The adsorption of organic pollutants was almost completely mineralized due to electrochemical oxidation, indicating that this regeneration process is much more potentially cost-effective for application.     

Degradation of H-acid in aqueous solution by microwave assisted wet air oxidation using Ni-loaded GAC as catalyst

A novel process, microwave assisted catalytic wet air oxidation( MW-CWO), was applied for the degradation of H-acid( l-amino8-naphthol-3, 6-disulfonic acid) in aqueous solution, Ni-loaded granular activated carbon (GAC), prepared by immersion-calcination method, was used as catalyst. The results showed that the MW-CWO process was very effective for the degradation of H-acid in aqueous solution under atmospheric pressure with 87.4% TOC (total organic carbon) reduction in 20 min. Ni on GAC existed in the form of NiO as specified by XRD. Loss of Ni was significant in the initial stage, and then remained almost constant after 20 min reaction. BET surface area results showed that the surface property of GAC after MW-CWO process was superior to that of blank GAC.