Simultaneous removal of dissolved organic matter and bromide from drinking water source by anion exchange resins for controlling disinfection by-products

Anion exchange resins （AERs） with different properties were evaluated for their ability to remove dissolved organic matter （DOM） and bromide, and to reduce disinfection by-product （DBP） formation potentials of water collected from a eutrophic surface water source in Japan. DOM and bromide were simultaneously removed by all selected AERs in batch adsorption experiments. A polyacrylic magnetic ion exchange resin （MIEX） showed faster dissolved organic carbon （DOC） removal than other AERs because it had the smallest resin bead size. Aromatic DOM fractions with molecular weight larger than 1600 Da and fluorescent organic fractions of fulvic acid- and humic acid-like compounds were efficiently removed by all AERs. Polystyrene AERs were more effective in bromide removal than polyacrylic AERs. This result implied that the properties of AERs, i.e. material and resin size, influenced not only DOM removal but also bromide removal efficiency, MIEX showed significant chlorinated DBP removal because it had the highest DOC removal within 30 rain, whereas polystyrene AERs efficiently removed brominated DBPs, especially brominated trihalomethane species. The results suggested that, depending on source water DOM and bromide concentration, selecting a suitable AER is a key factor in effective control of chlorinated and brominated DBPs in drinking water.     

Formation potentials of typical DBPs and changes of genotoxicity for chlorinated tertiary effluent pretreated by ozone

The effects of ozonation on the formation potential of typical disinfection byproducts (DBPs) and the changes of genotoxicity during post chlorination of tertiary effluent from a sewage treatment plant were investigated. Ozonation enhanced the yields of all detected chlorine DBPs except CHCl3. At a chlorine dose of 5 mg/L, the three brominated THMs and five HAAs increased, while chloroform decreased with the increase of ozone dose from 0 to 10 mg/L (ozone dose in consumption base). At a chlorine dose of 10 mg/L, the two mixed bromochloro species THMs and two dominant HAAs (DCAA and TCAA) firstly increased and then decreased with the increase of ozone dose, with the turning point approximately occurring at an ozone dose of 5 mg/L. The genotoxicity detected using umu test, on the other hand, was removed from 7 μg 4-NQO/L to a negligible level by ozonation under an ozone dose of 5 mg/L. Chlorination could further remove the genotoxicity to some extent. It was found that SUVA (UV absorbance divided by DOC concentration) might be used as an indicative parameter for monitoring the removal of genotoxicity during the oxidation.     

Formation potentials of typical disinfection byproducts and changes of genotoxicity for chlorinated tertiary e uent pretreated by ozone

The effects of ozonation on the formation potential of typical disinfection byproducts (DBPs) and the changes of genotoxicity during post chlorination of tertiary effluent from a sewage treatment plant were investigated. Ozonation enhanced the yields of all detected chlorine DBPs except CHCl3. At a chlorine dose of 5 mg/L, the three brominated THMs and five HAAs increased, while chloroform decreased with the increase of ozone dose from 0 to 10 mg/L (ozone dose in consumption base). At a chlorine dose of 10 mg/L, the two mixed bromochloro species THMs and two dominant HAAs (DCAA and TCAA) firstly increased and then decreased with the increase of ozone dose, with the turning point approximately occurring at an ozone dose of 5 mg/L. The genotoxicity detected using umu test, on the other hand, was removed from 7 μg 4-NQO/L to a negligible level by ozonation under an ozone dose of 5 mg/L. Chlorination could further remove the genotoxicity to some extent. It was found that SUVA (UV absorbance divided by DOC concentration) might be used as an indicative parameter for monitoring the removal of genotoxicity during the oxidation.     

Effects of pre-ozonation on organic matter removal by coagulation with IPF-PACI

Ozone plays an important role as a disinfectant and oxidant in potable water treatment practice and is increasingly being used as a pre-oxidant before coagulation. The purpose of this study is to obtain insight into the mechanisms that are operative in pre-ozonized coagulation. Effects ofpre-ozonation on organic matter removal during coagulation with IPF-PAC1 were investigated by using PDA （photometric disperse analysis）, apparent molecular weight distribution and chemical fractionation. The dynamic formation of flocs during coagulation process was detected. Changes of aquatic organic matter （AOM） structure resulted from the influence of pre-ozonation were evaluated. Results show that dosage of O3 and characteristics of AOM are two of the major factors influencing the performance of O3 on coagulation. No significant coagulation-aid effect of O3 was observed for all experiments using either A1C13 or PAC1. On the contrary, with the application of pre-ozonation, the coagulation efficiency of A1C13 was significantly deteriorated, reflected by the retardation of floc formation, and the removal decreases of turbidity, DOC, and UV254. However, if PACl was used instead of AlCl3, the adverse effects of pre-ozonation were mitigated obviously, particularly when the O3 dosage was less than 0.69 （mg O3/mg TOC）. The difference between removals of UV254, and DOC indicated that pre-ozonation greatly changed the molecular structure of AOM, but its capability of mineralization was not remarkable. Only 5% or so DOC was removed by pre-ozonation at 0.6--0.8 mg/L alone. Fractionation results showed that the organic products of pre-ozonation exhibited lower molecular weight and more hydrophilicity, which impaired the removal of DOC in the following coagulation process.     

UV/H_2O_2氧化处理水中去污剂

表面活性剂是一类特殊的有机污染物,在去污、洗衣、印染等废水中广泛存在.本文以某电厂实用的5种去污剂为研究对象,考察了UV/H2O2对5种去污剂的矿化能力,研究了H2O2和去污剂初始浓度、初始p H值、去污剂种类、辐照时间等因素对氧化效果的影响.结果表明,5种去污剂在254 nm处均无较强吸收,单独UV辐照对其降解效果不明显.当去污剂初始DOC浓度为50 mg·L-1,H2O2最佳投加量为1 m L·L-1,反应时间为90 min时,对5种去污剂的矿化率(即DOC去除率)在53%~87%,矿化率随去污剂种类的不同而不同.对去污剂的矿化率随着UV辐照时间的延长而增大,去除率曲线符合一级反应动力学方程.废水初始p H值对氧化效果的影响不显著,H2O2/DOC比值对氧化效果有显著影响.研究表明,UV/H2O2技术能高效矿化水中的去污剂,H2O2/DOC比值和UV辐照时间是影响氧化效率的关键因素.     

Identification of unknown disinfection byproducts in drinking water produced from Taihu Lake source water

Although disinfection byproducts(DBPs) in drinking water have been suggested as a cancer causing factor, the causative compounds have not yet been clarified. In this study, we used liquid chromatography quadrupole-time-of-flight spectrometry(LC-QTOF MS) to identify the unknown disinfection byproducts(DBPs) in drinking water produced from Taihu Lake source water, which is known as a convergence point for the anthropogenic pollutants discharged from intensive industrial activities in the surroundi...     

Degradation of Reactive Yellow 86 with photo-Fenton process driven by solar light

The decolorization of Reactive Yellow 86(RY 86),one of reactive azo dyes,was investigated in the presence of Fenton reagent under solar light irradiation.The decolorization rate was strongly influenced by pH,initial concentrations of H 2 O 2 and Fe(II),and so on.An initial concentration of 40 mg/L was decolored more than 90% after 20 min under optimum conditions.The activation energy of the solar photo-Fenton reaction was 1.50 kJ/mol for RY 86 in the temperature range of 10-60°C.In the kinetic study,the rate constant of RY 86 with OH· radicals could be estimated to be 1.7 × 10 10 L/(mol·sec).The decolorization efficiency of RY 86 under solar light irradiation was comparable to the artificial light irradiation.The decrease of TOC as a result of mineralization of RY 86 was observed during photo-Fenton process.The rate of RY 86 mineralization was about 83% under UV irradiation after 24 hr.The formation of chloride,sulfate,nitrate and ammonium ions as end-products was observed during the photocatalytic process.The decomposition of RY 86 gave two kinds of intermediate products.The degradation mechanism of RY 86 was proposed on the base of the identified intermediates.     

UV和UV/H2O2工艺对水中二嗪磷的降解

在低压汞灯（LPUV,253.7nm）光照条件下,研究了过氧化氢（H₂O₂）加入量对二嗪磷降解动力学、产物生成和降解途径的影响规律与作用机理.结果表明,二嗪磷水溶液在单独UV和UV/H₂O₂工艺中的降解反应均符合准一级反应动力学,且反应速率常数（k）随H₂O₂加入量的增加而增大,H₂O₂加入量为0,5,10mg/L时的k分别为0.0234,0.0301,0.0341min-1.在UV光照处理条件下,二嗪磷水溶液中的溶解性有机碳（DOC）随H₂O₂加入量的增加而降低,但其矿化度均相对较低（光照120min时的DOC去除率均低于20%）.此外,UV光照处理时,H₂O₂的加入对二嗪磷光氧化降解产物的种类及生成量均存在显著影响.二嗪磷水溶液单独UV光照处理60min时检出了8种中间/降解产物,但经UV/H₂O₂工艺处理60min时仅检出了6种中间/降解产物,且不同H₂O₂加入量时的光氧化降解产物生成量或浓度及随UV光照处理时间的变化幅度与趋势均存在较大程度的差别.基于二嗪磷及其降解产物的定性、（半）定量分析结果,提出了二嗪磷水溶液在单独UV和UV/H₂O₂工艺中的降解途径与机理.     

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.     

以葡萄糖为共基质硝基酚厌氧生物降解性试验研究

在35℃中温厌氧条件下,以葡萄糖为共基质,采用间歇试验法,通过测定甲烷累积产量,研究了2-硝基酚、4-硝基酚、2,4-二硝基酚和2,6-二硝基酚的厌氧生物降解性,利用相对活性值来判断硝基酚对产甲烷菌的抑制程度.研究结果表明:2-硝基酚浓度小于24mg/L时,对产甲烷菌没有产生抑制作用;4-硝基酚浓度小于20mg/L时,对产甲烷菌没有产生抑制作用,浓度为24mg/L时产生轻度抑制;2,6-二硝基酚浓度小于12mg/L时未产生抑制作用,浓度为16mg/L～24mg/L时产生轻度抑制;2,4-二硝基酚浓度小于4mg/L时没有产生抑制作用,浓度为8mg/L～24mg/L时产生中度抑制.4种物质对产甲烷菌活性的抑制由小到大的排列顺序为:2-硝基酚＜4-硝基酚＜2,6-二硝基酚＜2,4-二硝基酚.     

臭氧-紫外预处理对高有机物原水混凝效果的影响

以腐殖酸为模型污染物,分别考察了臭氧氧化、紫外照射及臭氧-紫外联合预处理过程对高有机物原水混凝性能的影响.结果表明,3种预处理方式均对原水中的溶解性腐殖酸具有明显的矿化作用.紫外及臭氧-紫外联合预处理还对后续的混凝过程具有强化作用.随着臭氧投量的增加和紫外照射时间的延长,混凝过滤出水的TOC和浊度呈明显下降趋势.当臭氧浓度(O3/C)达到9.0 mg/mg时,预处理对腐殖酸的去除率可以达到47%,过滤出水TOC含量为3.5 mg/L,浊度为2.6 NTU;紫外光照射3 h可去除原水中52%的溶解性有机物,其出水TOC为2.0 mg/L,浊度低于1.0 NTU.臭氧-紫外联合预处理后的混凝效果要明显优于二者单独作用的系统.在联合预处理系统中,当预臭氧浓度(O3/C)为1.0 mg/mg紫外照射时间为1 h时,过滤出水TOC为2.6 mg/L,且浊度低于1.0 NTU.不同预处理条件下的矿化作用主要是通过.OH实现的,同时.OH还对溶解性腐殖酸的团聚结构产生破坏作用,使其稳定性降低,从而促进了混凝过程对有机物的去除.     

Degradation and detoxification of microcystin-LR in drinking water by sequential use of UV and ozone

Microcystins (MCs) produced by cyanobacteria are strong hepatotoxins and classified as possible carcinogens.MCs pose a considerable threat to human health through tainted drinking and surface waters.Herein filtrated water from a waterworks in Harbin,China,was spiked with microcystin-LR (MC-LR) extracted from a toxic scum of microcystis aeruginosa,and the spiked sample waters were treated using UV irradiation with consequent ozonation process (UV/O3),compared with ozonation at a dose range commonly applied in water treatment plants,UV irradiation at 254 nm and UV irradiation combined with ozonation (UV+O3),respectively.The remaining of toxins were analyzed using high-performance liquid chromatography and also determined using a protein phosphatase type 2A inhibition assay,which was utilized to evaluate the reduction in toxicity.Results indicated that in comparison to other three processes (O3,UV,and UV+O3),UV/O 3 process could effectively decrease both the concentration and toxicity of MC-LR at 100 μg/L level after 5 min UV irradiation with consequent 5 min ozonation at 0.2 mg/L (below 1 μg/L),while 0.5 mg/L ozone dose was required for the level below 0.1 μg/L.The addition of an UV treatment step to the existing treatment train may induce significant transformation of micropollutants and breaks down the natural organic matters into moieties unfavorable for ozone decomposition,stabilizing the ozone residual.These findings suggested that sequential use of UV and ozone may be a suitable method for the removal of these potentially hazardous microcystins from drinking water.     

Characterization of dissolved organic matter in urban sewage using excitation emission matrix fluorescence spectroscopy and parallel factor analysis

Wastewater dissolved organic matter (DOM) from different processing stages of a sewage treatment plant in Xiamen was characterized using fluorescence and absorption spectroscopy. Parallel factor analysis modeling of excitation-emission matrix spectra revealed five fluorescent components occurring in sewage DOM: one protein-like (C1), three humic-like (C2, C4 and C5) and one xenobiotic-like (C3) components. During the aerated grit chamber and primary sedimentation tank stage, there was only a slight decrease in fluorescence intensity and the absorption coefficient at 350 nm (a350). During the second aeration stage, high concentration of protein-like and short-wavelength-excited humic-like components were significantly degraded accompanied by significant loss of DOC (80%) and a350 (30%), indicating that C1 and C2 were the dominant constituents of sewage DOM. As a result, long-wavelengthexcited C4 and C5 became the dominant humic-like components and the DOM molecular size inferred from the variation of spectral slope S (300–650 nm) and specific absorption (a280/DOC) increased. Combination use of Fmax of C1 and the ratio of C1/C5, or a350 may provide a quantitative indication for the relative amount of raw or treated sewage in aquatic environment.     

固定化优势菌种降解2,6-二叔丁基酚

 用海藻酸钙包埋固定优势降解菌(Alcaligenes sp.)降解 2,6-二叔丁基酚(2,6-2DTBP).结果表明,菌株经固定化包埋后,降解底物 2,6-DTBP的能力大大提高,在 100.0mg/L 的初始浓度下其降解率在 12d 可达到 86%.与未固定菌株相比,固定化菌株对 pH 值和温度的适应范围更宽,对底物具有更高的降解能力.对固定化菌株的降解反应过程进行动力学分析,该降解反应符合一级动力学特征,其动力学常数为 0.1519,半衰期为 4.56d.扫描电镜观察到菌种在海藻酸钙包埋载体中能良好地生长和繁殖.     

UV/H2Ｏ2/微曝气联用工艺矿化内分泌干扰物BPA试验研究

采用UV/H₂Ｏ₂/微曝气工艺对水中内分泌干扰物双酚A(BPA)的降解与矿化进行了试验研究.该工艺是在UV/H₂Ｏ₂的基础上发展起来的一种新工艺,微曝气在UV光照射下产生了一定量的O₃,提高了·OH的发生率.本试验研究了UV光强、H₂Ｏ₂投加量以及pH值对BPA矿化速率的影响.结果表明,随着UV光强的增大,BPA的矿化速率呈线性增加;当H₂Ｏ₂投加量由5 mg/L增大到20 mg/L时,BPA矿化速率常数k由0.003 2上升到0.025 0;当pH为6.68时,在相同条件下BPA的矿化效果最好.在同一工况条件下,UV/H₂Ｏ₂/微曝气工艺降解BPA的速率远远大于其矿化速率,分析得出在开始反应阶段BPA首先被降解为小分子有机物,随着反应的进一步进行小分子有机物逐步被矿化为无机物.     

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.     

水质对UV/H_2O_2降解2,4-二氯酚的影响

研究了UV/H2O2工艺对2,4-二氯酚(2,4-DCP)的去除效果和水中阴离子、腐殖酸对该工艺降解2,4-DCP的影响。结果表明:UV/H2O2工艺可以有效的去除水中2,4-DCP,光降解过程符合一级反应动力学模型;在H2O2投加量为8mg/L,1个30W低压汞灯照射下,2,4-DCP在蒸馏水和自来水中光降解速率常数分别为0.0232/min和0.0162/min;NO3-、Cl-、HCO3-对2,4-DCP光降解有抑制作用;当3种离子浓度为0.5mmol/L、10mmol/L、20mmol/L时,对2,4-DCP光降解的抑制程度为HCO3->NO3->Cl-;随着离子浓度增大,抑制作用增强;自来水中的光降解速率常数低于蒸馏水中的光降解速率常数是由于水中多种离子影响的结果;腐殖酸在低浓度时,促进光降解反应的进行,在高浓度时,2,4-DCP的光降解氧化受到抑制。     

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.     

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.     

加氯消毒过程中纯细菌物质生成消毒副产物研究

按照UFC方法对水体中3种常见细菌Acinetobacter junii、Staphylococcussciuri和Escherichia coli进行纯细菌加氯消毒处理,同时考察水中溴离子对纯细菌物质生成DBPs的影响.结果表明,3种细菌均为DBPs前体物,加氯消毒生成的DBPs除水合三氯乙醛(CHD)外,生成的三卤甲烷(THMs)物质主要为氯仿(TCM),卤乙腈(HANs)物质主要为二氯乙腈(DCAN).氯仿的生成量与细菌物质TOC浓度无明显关系,但HANs和CHD生成量均随细菌TOC浓度增大而增加.其中革兰氏阳性细菌Staphylococcus sciuri生成的DCAN和CHD比革兰氏阴性细菌Acinetobacter junii和Escherichia coli生成的要高,说明细胞壁的化学组分可能是DCAN和CHD生成的影响因素之一.Escherichia coli细菌反应液中溴离子(Br-)存在时,除生成CHD、TCM及DCAN外,THMs和HANs中的溴代种类CHBr3随Br-增多而持续增加,相反TCM持续减少.当Br-浓度为4mg.L-1时,TBM浓度增至最高127.9μg.L-1;HANs和CHD生成量随Br-浓度增加先有所增加,随后持续降低至低于检测限;Br离子存在时THMs为主要DBPs种类.