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.     

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.     

焦化废水尾水O3氧化消除消毒副产物生成潜能的影响分析

焦化废水经生化处理后的尾水中含有多种溶解性有机物(DOM),可能成为消毒副产物的前体物,进而影响受纳水体下游给水厂的水质安全.因此,对焦化废水外排水(尾水)的消毒副产物生成潜能进行了分析,以实际焦化废水厂尾水为基质,采用气相色谱(GC)考察了O3氧化深度处理前后卤乙腈和三卤甲烷的生成潜能,并结合分子质量分布法和三维荧光光谱法分析了O3氧化处理尾水过程中前体物的转化规律.GC结果表明,焦化废水尾水各个分子质量范围的卤乙腈和三卤甲烷生成潜能分别达到1950.5～3965.1μg.L-1和1498.2～2571.2μg.L-1,表明工业废水排放之前需要考虑其对水体消毒副产物生成潜能的贡献.O3氧化作用可以实现尾水中消毒副产物前体物的削减,相同反应时间的条件下O3浓度越高其削减越有效.溶解性有机碳(DOC)及在254nm波长下的吸光度值(UV254)分析结果表明,O3氧化能部分矿化尾水中的有机物,并优先分解不饱和芳香性有机组分.分子质量和荧光光谱分析结果表明,O3氧化优先矿化小分子组分(<1kDa),并将尾水中大分子有机物分解为小分子(<1kDa),对活泼基团进行预氧化,从而实现氯消毒副产物生成潜能的削减.     

Formation of disinfection byproducts in typical Chinese drinking water

Eight typical drinking water supplies in China were selected in this study. Both source and tap water were used to investigate the occurrence of chlorinated disinfection byproducts (DBPs), and seasonal variation in the concentrations of trihalomethanes (THMs) of seven water sources was compared. The results showed that the pollution level for source water in China, as shown by DBP formation potential, was low. The most encountered DBPs were chloroform, dichloroacetic acid, trichloroacetic acid, and chlorodibromoacetic acid. The concentration of every THMs and haloacetic acid (HAA) compound was under the limit of standards for drinking water quality. The highest total THMs concentrations were detected in spring.     

Sequential use of ultraviolet light and chlorine for reclaimed water disinfection

Several disinfection processes of ultraviolet (UV), chlorine or UV followed by chlorine were investigated in municipal wastewater according to the inactivation of Escherichia coli, Shigella dysenteriae and toxicity formation. The UV inactivation of the tested pathogenic bacteria was not affected by the quality of water. It was found that the inactivated bacteria were obviously reactivated after one day in dark. Fluorescent light irradiation increased the bacteria repair. The increase of UV dosage could cause more damage to bacteria to inhibit bacteria self-repair. No photoreactivation was detected when the UV dose was up to 80 mJ/cm² for E. coli DH5αup, and 23 mJ/cm² for S. dysenteriae. Nevertheless, sequential use of 8 mJ/cm² of UV and low concentration of chlorine (1.5 mg/L) could effectively inhibit the photoreactivation and inactivate E. coli below the detection limits within seven days. Compared to chlorination alone, the sequential disinfection decreased the genotoxicity of treated wastewater, especially for the sample with high NH₃-N concentration.     

Effect of ferric and bromide ions on the formation and speciation of disinfection byproducts during chlorination

The e ects of ferric ion, pH, and bromide on the formation and distribution of disinfection byproducts (DBPs) during chlorination were studied. Two raw water samples from Huangpu River and Yangtze River, two typical drinking water sources of Shanghai, were used for the investigation. Compared with the samples from Huangpu River, the raw water samples from Yangtze River had lower content of total organic carbon (TOC) and ferric ions, but higher bromide concentrations. Under controlled chlorination conditions, four trihalomethanes (THMs), nine haloacetic acids (HAAs), total organic halogen (TOX) and its halogen species fractions, including total organic chlorine (TOCl) and total organic bromide (TOBr), were determined. The results showed that co-existent ferric and bromide ions significantly promoted the formation of total THMs and HAAs for both raw water samples. Higher concentration of bromide ions significantly changed the speciation of the formed THMs and HAAs. There was an obvious shift to brominated species, which might result in a more adverse influence on the safety of drinking water. The results also indicated that high levels of bromide ions in raw water samples produced higher percentages of unknown TOBr.     

二氧化氯消毒前后污水毒性的变化及消毒条件的影响

采用发光细菌试验和umu试验,分别考察了二氧化氯投加量和反应时间对污水二氧化氯消毒后急性毒性和遗传毒性变化的影响.结果表明,随着二氧化氯消毒剂投加量的增加,消毒后水样的急性毒性不断增大,但遗传毒性逐渐减小后趋于稳定.随着反应时间的延长,二氧化氯的消耗量不断增大,消毒后水样的急性毒性先增大后减小,遗传毒性逐渐减小后趋于稳定.由于消毒条件对污水急性毒性和遗传毒性有着不同的影响,说明污水中产生急性毒性和产生遗传毒性的物质不同,对于某一种污水,通过控制消毒条件可以使消毒后污水的急性毒性和遗传毒性都较低.     

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.     

城市污水中的生物毒性及其臭氧削减效果研究

分别利用酵母双杂交和umu试验对5个城市9个污水处理厂进出水中生物遗传毒性和视黄酸受体(BAR)结合活性进行了调查.并考察了臭氧氧化对这两种生物效应的去除效果.结果表明,城市污水中存在不同程度的生物遗传毒性和视黄酸受体(RAR)结合活性,通过生物处理可以大幅削减污水中的RAR结合活性和生物遗传毒性,但污水厂出水中仍然普遍具有遗传毒性,部分残留RAR结合活性.5～10mg·L-1的臭氧可以有效削减二级出水中残留的BAR结合活性和遗传毒性,是一种有效的提高水质安全性的污水深度处理技术.     

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.     

New methods for identification of disinfection byproducts of toxicological relevance: Progress and future directions

Disinfection byproducts (DBPs) represent a ubiquitous source of chemical exposure in disinfected water. While over 700 DBPs have been identified, the drivers of toxicity remain poorly understood. Additionally, ever evolving water treatment practices have led to a continually growing list of DBPs. Advancement of analytical technologies have enabled the identification of new classes of DBPs and the quantification of these chemically diverse sets of DBPs. Here we summarize advances in new workflows for DBP analysis, including sample preparation, chromatographic separation with mass spectrometry (MS) detection, and data processing. To aid in the selection of techniques for future studies, we discuss necessary considerations for each step in the strategy. This review focuses on how each step of a workflow can be optimized to capture diverse classes of DBPs within a single method. Additionally, we highlight new MS-based approaches that can be powerful for identifying novel DBPs of toxicological relevance. We discuss current challenges and provide perspectives on future research directions with respect to studying new DBPs of toxicological relevance. As analytical technologies continue to advance, new strategies will be increasingly used to analyze complex DBPs produced in different treatment processes with the aim to identify potential drivers of toxicity.     

Change in genotoxicity of wastewater during chlorine dioxide and chlorine disinfections and the influence of ammonia nitrogen

The effects of chlorine dioxide and chlorine disinfections on the genotoxicity of different biologically treated sewage wastewater samples were studied by umu-test. The experiment results showed that when chlorine dioxide dosage was increased from 0 to 30 mg/L, the genotoxicity of wastewater first decreased rapidly and then tended to be stable, while when the chlorine dosage was increased from 0 to 30 mg/L, the genotoxicity of wastewater changed diversely for different samples. It was then found that ammonia nitrogen did not affect the change of genotoxicity during chlorine dioxide disinfection of wastewater, while it greatly affected the change of genotoxicity during chlorine disinfection of wastewater. When the concentration of ammonia nitrogen was low (< 10–20 mg/L), the genotoxicity of wastewater decreased after chlorine disinfection, and when the concentration of ammonia nitrogen was high (> 10–20 mg/L), the genotoxicity of wastewater increased after chlorine disinfection.     

饮用水含氮与含碳消毒副产物的生成潜能及其毒性

消毒副产物生成潜能测试常用于表征水中消毒副产物的前体物含量.不同于三氯甲烷等含碳消毒副产物,二卤代乙腈(DHANs)与二卤代乙酰胺(DHAcAms)等含氮消毒副产物在氯消毒的余氯存在下易分解,并且在氯胺消毒过程中可由氯胺提供氮源生成,因此常用于含碳消毒副产物的生成潜能测试方法(如Krasner提出的测试法)可能无法有效...     

Formation and speciation of disinfection byproducts during chlor(am)ination of aquarium seawater

The chemistry associated with the disinfection of aquarium seawater is more complicated than that of freshwater, therefore limited information is available on the formation and speciation of disinfection byproducts(DBPs) in marine aquaria. In this study, the effects of organic precursors, bromide(Br-) and pre-ozonation on the formation and speciation of several typical classes of DBPs, including trihalomethanes(THM4), haloacetic acids(HAAs),iodinated trihalomethanes(I-THMs), and haloacetamides(HAc Ams), were investigated during the chlorination/chloramination of aquarium seawater. Results indicate that with an increase in dissolved organic carbon concentration from 4.5 to 9.4 mg/L, the concentrations of THM4 and HAAs increased by 3.2–7.8 times under chlorination and by 1.1–2.3 times under chloramination. An increase in Br-concentration from 3 to 68 mg/L generally enhanced the formation of THM4, I-THMs and HAc Ams and increased the bromine substitution factors of all studied DBPs as well, whereas it impacted insignificantly on the yield of HAAs. Pre-ozonation with 1 mg/L O3 dose substantially reduced the formation of all studied DBPs in the subsequent chlorination and I-THMs in the subsequent chloramination. Because chloramination produces much lower amounts of DBPs than chlorination, it tends to be more suitable for disinfection of aquarium seawater.     

Characterisation of acute toxicity, genotoxicity and oxidative stress posed by textile effluent on zebrafish

Textile industries are important sources of toxic discharges and contribute enormously to water deterioration, while little attention has been paid to the toxicity of textile effluents in discharge regulation. Bioassays with zebrafish were employed to evaluate the toxicity of wastewater samples collected from different stages at a textile factory and sewage treatment plants (STPs). Physico-chemical parameters, acute toxicity, genotoxicity and oxidative stress biomarkers were analyzed. The wastewater samples from bleaching, rinsing and soaping of the textile factory exhibited high acute toxicity and genotoxicity. The coexisting components of dye compounds, as assistants and oxidants, seemed to cause some effect on the toxic response. After treatment employing the anoxic-oxic (A/O) process in STPs, the color and the chemical oxygen demand (COD) were reduced by 40% and 84%, respectively, falling within the criteria of the Chinese Sewage Discharge Standard. In contrast, increases in acute toxicity and genotoxicity were observed in the anaerobic tank, indicating the formation of toxic intermediates. The genotoxicity of the effluent of the STP was not significantly different from that of the influent, suggesting the wastewater treatment processes were not effective in removing the genotoxicity of the dye wastewater. Results indicated that the effluent contains pro-oxidants since the activities of glutathione (GSH), malondialdehyde (MDA), and total anti-oxidation capacity (T-AOC) were all elevated. In addition, decreases in superoxide dismutase (SOD) and glutathione-S transferase (GST) activities observed can be interpreted as a cytotoxicity sign due to an over-production of reactive oxygen species (ROS). The results of the present study suggest that the STPs were not capable of reducing the toxicity of wastewater sufficiently. Further treatment is needed to remove the potential risks posed by textile effluent to ecosystems and human health, and employing a toxicity index is necessary for discharge regulation.     

紫外光-氯联用污水消毒削弱拖尾程度的实验研究

研究了紫外光-氯联用消毒工艺削弱二级出水氯消毒拖尾程度.考察了紫外光-氯使用顺序、pH、氯投量、紫外光剂量等因素对氯消毒大肠杆菌动力学曲线的影响.SS浓度对"拖尾现象"有显著影响,降低SS浓度能够有效提高拖尾区灭活率.紫外光-氯联用消毒能提高一级反应区的灭活速率1.08～1.25倍,并将拖尾区灭活率提高2～2.5个对数级,二者存在明显协同作用.UV/HOCl方式效果优于HOCl/UV方式.降低pH,提高氯投量将加快一级反应区消毒速度而更快进入拖尾区.紫外光剂量变化对拖尾区开始时间没有显著影响.     

臭氧和好氧生物法处理污水处理厂出水的纳米过滤浓缩液

城市污水处理厂出水的纳米过滤浓缩液较难直接生物处理。臭氧氧化该浓缩液降低DOC的速度较慢,但是可以有效地破坏该浓缩液中含苯环和有色基团的大分子有机物,显著增加小分子有机物的相对含量,从而增大其可生化降解性能。研究发现臭氧的投量为52mg/L左右时,臭氧化改善该纳米过滤浓缩液的可生化降解性能的效果最佳。     

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.     

污水中溶解性有机物组分特性及其氯消毒副产物生成潜能

以城市污水厂二级出水为研究对象,采用大孔吸附树脂将污水中溶解性有机物分离成亲水性物质、疏水酸性物质、疏水中性物质和疏水碱性物质4个组分,分析了各组分的有机物特性、三维荧光光谱特征和氯消毒副产物生成潜能.结果表明,亲水性物质和疏水酸性物质分别占水样中溶解性有机碳的33%和30%,其中亲水性物质相对含有较多的生物源腐殖质类物质,疏水酸性物质相对含有更多的芳香族蛋白质和溶解性微生物代谢产物类物质.氯消毒后,亲水性物质的三卤甲烷生成潜能分别为630.4μg.L-1,占污水三卤甲烷生成潜能的73.7%.亲水性物质和疏水酸性物质的卤乙酸生成潜能分别为644.6μg.L-1和123.2μg.L-1,是污水氯消毒副产物的主要前体物.     

UV、O3及UV/O3削减耐药菌和抗性基因性能

从某污水处理厂二级出水分离出粪肠球菌、短芽孢杆菌、假单胞杆菌和大肠杆菌4种耐药菌,通过菌落计数法、qPCR评价UV、O₃及UV/O₃对耐药菌和抗性基因的削减效果.研究表明,3种方式对耐药菌均有较好的削减效果,其中革兰氏阳性菌灭活效果比阴性菌差;对抗性基因的削减受消毒方式和抗性基因的种类影响较大,结果表明短芽孢杆菌在耐药菌和抗性基因削减过程中表现出较强的抗逆性.结合复活实验和扫描电镜发现,UV消毒72h后耐药菌的光复活率为6.93%~11.58%;O₃因破坏了细胞结构未出现光复活现象,这一过程中胞内抗性基因可能释放到环境中;UV/O₃对耐药菌造成的损伤同样具有不可逆性.