Assesment of disinfection by‐products removal by ozonation coupled with adsorption

This research work was performed to evaluate ozonation and granular activated carbon adsorption processes from the view‐point of controlling the formation of disinfection by products (DBPs). Both the humic acid and raw water were first preozonated and then adsorbed on the activated carbon to assess the potency for removal of total organic carbon (TOC) and DBPs. The disinfection by‐product including THMs and HAAs, in principle, can be successfully removed through a use of the ozonation and granular activated carbon (GAC) adsorption processes. However, in practice dealing with the raw water, it is necessary to introduce the pilot‐plant to obtain the design and operation guidelines for the water treatment plant through the ICA (Instrumentation Control and Automation) program in our future research work.     

Analyses of PAHs (polycyclic aromatic hydrocarbons) and mutagenicity in raw and chlorinated water

Both raw water and chlorinated drinking water samples were collected from and the Liu‐Du water treatment plant in northern Taiwan from October 1990 to April 1992. The polycyclic aromatic hydrocarbons (PAHs) and mutagenicity in these water samples were analyzed by GC/MS and Ames test. The Mutagenicity/DMSO (Dimethyl Sulfoxide) ratio in S. typhimurium TA98 and TA100 with or without S9 mixture increased, even higher than 2, following the sequence of unit process. It was observed that the mutagenicity with TA98 (S9+) was highly related to most of PAHs in the raw water; while the mutagenicity with TA98 (S9+) was only correlated with DbA and BghiPr in the treated water. It could be expected that the mutagenicity level was controlled by other predominant components after the raw water was treated, for example, the chlorination process.     

Characteristics and removal mechanism of the precursors of N-chloro-2,2-dichloroacetamide in a drinking water treatment process at Taihu Lake

• N-Cl-DCAM, an emerging N-DBP in drinking water was investigated. • A new BAC has a better removal efficiency for N-Cl-DCAM precursors than an old BAC. • N-Cl-DCAM precursors are more of low molecular weight and non-polar. • Adsorption of GAC plays a major role in removal of N-Cl-DCAM precursors by an O₃-BAC. N-chloro-2,2-dichloroacetamide (N-Cl-DCAM) is an emerging nitrogenous disinfection by-product (N-DBP) which can occur in drinking water. In this study, an analytical method based on liquid chromatography with tandem mass spectrometry (LC-MS/MS) was developed to validate the concentration of N-Cl-DCAM, which was found to be 1.5 mg/L in the effluent of a waterworks receiving raw water from Taihu Lake, China. The changes of N-Cl-DCAM formation potential (N-Cl-DCAMFP) in the drinking water treatment process and the removal efficiency of its precursors in each unit were evaluated. Non-polar organics accounted for the majority of N-Cl-DCAM precursors, accounting for 70% of the N-Cl-DCAM FP. The effect of conventional water treatment processes on the removal of N-Cl-DCAM precursors was found to be unsatisfactory due to their poor performance in the removal of low molecular weight (MW) or non-polar organics. In the ozonation integrated with biological activated carbon (O₃-BAC) process, the ozonation had little influence on the decrease of N-Cl-DCAM FP. The removal efficiency of precursors by a new BAC filter, in which the granular activated carbon (GAC) had only been used for four months was higher than that achieved by an old BAC filter in which the GAC had been used for two years. The different removal efficiencies of precursors were mainly due to the different adsorption capacities of GAC for individual precursors. Low MW or non-polar organics were predominantly removed by GAC, rather than biodegradation by microorganisms attached to GAC particles.     

Impacts of advanced treatment processes on elimination of antibiotic resistance genes in a municipal wastewater treatment plant

The distributions of ARGs were monitored in a WWTP in Harbin during six months. CASS had the best removal efficacy of ARGs compared to other processes in the WWTP. UV disinfection could effectively control the HGT. AGAC significantly remove ARGs and organics due to its high absorption capacity. Combination of ozone and AGAC significantly improve removal of ARGs and organics. Antibiotic resistance genes (ARGs) pose a serious threat to public health. Wastewater treatment plants (WWTPs) are essential for controlling the release of ARGs into the environment. This study investigated ARG distribution at every step in the treatment process of a municipal WWTP located in Harbin for six consecutive months. Changes in ARG distribution involved in two advanced secondary effluent treatment processes, ozonation and granular activated carbon (GAC) adsorption, were analyzed. Biological treatment resulted in the highest ARG removal (0.76–1.94 log reduction), followed by ultraviolet (UV) disinfection (less than 0.5-log reduction). Primary treatment could not significantly remove ARGs. ARG removal efficiency increased with an increase in the ozone dose below 40 mg/L. However, amorphous GAC (AGAC) adsorption with a hydraulic retention time (HRT) of 1 h showed better removal of ARGs, total organic carbon (TOC), total nitrogen (TN), and total phosphorus (TP) than ozonation at a 60 mg/L dose. UV treatment could efficiently reduce the relative ARG abundance, despite presenting the lowest efficiency for the reduction of absolute ARG abundance compared with GAC and ozone treatments. The combination of ozone and AGAC can significantly improve the removal of ARGs, TOC, TN and TP. These results indicate that a treatment including biological processing, ozonation, and AGAC adsorption is a promising strategy for removing ARGs and refractory organic substances from sewage.     

二氧化氯和液氯消毒饮用水致突变性的比较

本文运用国内外广泛应用的Ａｍｅｓ试验,对二氧化氯与液氯消毒水样进行了致突变性的比较,结果表明,ＣｌＯ２消毒的水样未显示出致突变性,而液氯消毒的水样显示致突变性的研究结果为ＣｌＯ２在饮用水消毒中的应用提供了科学的依据。     

给水深度处理中臭氧副产物的产生及控制

就给水深度处理中臭氧副产物的产生及其化学过程、控制臭氧副产物生成的技术措施等问题进行了探讨。采用臭氧深度处理时,会产生以甲醛为代表的有机副产物,以溴酸根为代表的无机副产物。副产物的形成与溴离子浓度、水中有机物种类和浓度、pH值、臭氧投加量、温度和碱度等因素有关。在应用臭氧进行深度处理时,应根据不同条件,采取适宜的措施,以减少臭氧副产物的生成。     

The occurrence of disinfection by‐products in Taiwan drinking water

In this study, samples were taken from six conventional water treatment plants for disinfection by‐products analysis. Results from the analysis revealed that trihalomethanes (THMs) concentrations in all samples were below regulatory levels (100 μg/L). Although the national standard for haloacetic acids (HAA5) has not yet been promulgated in Taiwan, samples from two water plants contained HAA5 concentrations exceeding the USEPA limit (MCL of HAA5 of Stage 1, 60 μg/L). THMs and HAA5 were found to be the major disinfection by‐products in all water treatment plants. It was noted that the concentration of HAA5 in most samples was higher than that of the trihalomathanes. However, the formation potential of THM (THMFP) was found to be higher than that of HAA (HAAFP). Good correlation also was found between THMFP (or THMFP) and HAA5 (or THMs). In evaluating the performance of the treatment processes, it was found that conventional water treatment processes followed by activated carbon were effective in removing disinfection by‐products (DBPs) from source water with pre‐ozonation. The treatment processes were at their optimum performance in removing contaminants when O₃/TOC₀ was held at 0.75.     

焦化废水处理试验系统出水的生物毒性变化

焦化废水是一种典型的难降解工业废水,组分复杂,生物毒性高,大多采用生物处理联合物化深度处理的工艺,以满足炼焦化学工业的污染排放标准,但其排水安全性仍然令人担忧。为研究工艺排水安全性,选择发光细菌青海弧菌Q67、稀有鮈鲫(Gobiocypris rasus)血红细胞、活性污泥微生物群落为测试生物,研究了焦化废水及各处理阶段出水的急性毒性和遗传毒性变化,进而识别影响生物毒性的水质因子。焦化废水经过序批式生物膜反应器处理后,出水急性毒性比进水下降71%,遗传毒性下降为90%以上的轻度以下损伤,显示生物强化处理对焦化废水生物毒性有良好的去除作用。生物处理出水再经过深度处理后,则表现出不同的毒性变化:活性炭吸附法对生物急性毒性的消除最佳,但遗传毒性较生物处理出水有所升高;臭氧氧化法不仅水质改善效率差,且最终出水的生物急性毒性与遗传毒性均升高;臭氧催化氧化法对水中残留有机物去除效率较高,但也造成出水急性毒性与遗传毒性的升高。各水样对青海弧菌Q67的急性毒性与有机物、氮等水质指标表现出较强相关性,而遗传毒性与水质指标之间的相关性不显著。研究结果可为评价和改进处理工艺、保障水体生态安全提供参考。     

Diazinon leaching through a sandy soil amended with different humic materials

The water leaching of diazinon (O,O‐diethyl‐O‐2‐isopropyl‐6‐methylpyrirnidin‐4‐yl phosphoroth‐ioate) through soil columns, was studied after column amendments with two well characterized humic acids (HA), in both liquid and solid state, and with the original raw organic materials, an oxidized coal and a leonardite, from which the HA were extracted. The percolation curves and the pesticide distribution over the soil columns showed that the addition of the raw organic materials and the solid HAs reduced significantly the mobility of the pesticide along the soil column. The oxidized coal was more effective than the leonardite original material; the different origin of the two carbon‐rich materials had an influence on the diazinon movement along the soil columns and such difference was enhanced with increasing addition rates. Moreover, incubation at field capacity for two months of the soil columns treated with raw oxidized coal and leonardite, largely enhanced the described effects on pesticide behaviour. A complete adsorption of diazinon on columns and a practical absence of leaching was observed when the HA from both materials were added in dissolved form. These results were explained with the swelling of the humic micelles in water and the enhanced availability of inner hydrophobic surfaces for the strong adsorption of diazinon. The water diffusion into the solid humic materials after two months incubation, also explains their high pesticide retention capacity. This work indicates the usefulness of either solid o dissolved humic substances, with the proper hydrophobic character, in preventing the vertical leaching of non‐polar organic pesticides in soils.     

Combined process of biofiltration and ozone oxidation as an advanced treatment process for wastewater reuse

The effluent of a wastewater treatment plant was treated in a pilot plant for reclaimed water production through the denitrification biofilter (DNBF) process, ozonation (O₃), and biologic aerated filtration (BAF). The combined process demonstrated good removal performance of conventional pollutants, including concentrations of chemical oxygen demand (27.8 mg·L⁻¹) and total nitrogen (9.9 mg·L⁻¹) in the final effluent, which met the local discharge standards and water reuse purposes. Micropollutants (e.g., antibiotics and endocrine-disrupting chemicals) were also significantly removed during the proposed process. Ozonation exhibited high antibiotic removal efficiencies, especially for tetracycline (94%). However, micropollutant removal efficiency was negatively affected by the nitrite produced by DNBF. Acute toxicity variations of the combined process were estimated by utilizing luminescent bacteria. Inhibition rate increased from 9% to 15% during ozonation. Carbonyl compound concentrations (e.g., aldehydes and ketones) also increased by 58% as by-products, which consequently increased toxicity. However, toxicity eventually became as low as that of the influent because the by-products were effectively removed by BAF. The combined DNBF/O₃/BAF process is suitable for the advanced treatment of reclaimed water because it can thoroughly remove pollutants and toxicity.     

Catalytic ozonation of organic compounds in water over the catalyst of RuO2/ZrO2-CeO2

This research investigates the performances of RuO₂/ZrO₂-CeO₂ in catalytic ozonation for water treatment. The results show that RuO₂/ZrO₂-CeO₂ was active for the catalytic ozonation of oxalic acid and possessed higher stability than RuO₂/Al₂O₃ and Ru/AC. In the catalytic ozonation of dimethyl phthalate (DMP), RuO₂/ZrO₂-CeO₂ did not enhance the DMP degradation rate but significantly improved the total organic carbon (TOC) removal rate. The TOC removal in catalytic ozonation was 56% more than that in noncatalytic ozonation. However this does not mean the catalyst was very active because the contribution of catalysis to the overall TOC removal was only 30%. The adsorption of the intermediates on RuO₂/ZrO₂-CeO₂ played an important role on the overall TOC removal while the adsorption of DMP on it was negligible. This adsorption difference was due to their different ozonation rates. In the catalytic ozonation of disinfection byproduct precursors with RuO₂/ZrO₂-CeO₂, the reductions of the haloacetic acid and trihalomethane formation potentials (HAAFPs and THMFPs) for the natural water samples were 38%–57% and 50%–64%, respectively. The catalyst significantly promoted the reduction of HAAFPs but insignificantly improved the reduction of THMFPs as ozone reacts fast with the THMs precursors. These results illustrate the good promise of RuO₂/ZrO₂-CeO₂ in catalytic ozonation for water treatment.     

Mechanisms for simultaneous ozonation of sulfamethoxazole and natural organic matters in secondary effluent from sewage treatment plant

• SMX was mainly degraded by hydrolysis, isoxazole oxidation and double-bond addition. • Isoxazole oxidation and bond addition products were formed by direct ozonation. • Hydroxylated products were produced by indirect oxidation. • NOM mainly affected the degradation of SMX by consuming ^•OH rather than O₃. • Inhibitory effect of NOM on SMX removal was related to the components’ aromaticity. Sulfamethoxazole (SMX) is commonly detected in wastewater and cannot be completely decomposed during conventional treatment processes. Ozone (O₃) is often used in water treatment. This study explored the influence of natural organic matters (NOM) in secondary effluent of a sewage treatment plant on the ozonation pathways of SMX. The changes in NOM components during ozonation were also analyzed. SMX was primarily degraded by hydrolysis, isoxazole-ring opening, and double-bond addition, whereas hydroxylation was not the principal route given the low maximum abundances of the hydroxylated products, with m/z of 269 and 287. The hydroxylation process occurred mainly through indirect oxidation because the maximum abundances of the products reduced by about 70% after the radical quencher was added, whereas isoxazole-ring opening and double-bond addition processes mainly depended on direct oxidation, which was unaffected by the quencher. NOM mainly affected the degradation of micropollutants by consuming ^•OH rather than O₃ molecules, resulting in the 63%–85% decrease in indirect oxidation products. The NOM in the effluent were also degraded simultaneously during ozonation, and the components with larger aromaticity were more likely degraded through direct oxidation. The dependences of the three main components of NOM in the effluent on indirect oxidation followed the sequence: humic-like substances>fluvic-like substances>protein-like substances. This study reveals the ozonation mechanism of SMX in secondary effluent and provides a theoretical basis for the control of SMX and its degradation products in actual water treatment.     

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.     

利用微生物检测环境有机化合物的致突变性

运用微生物检测致突变性的方法有很多种，一般都是简便，快速，灵敏，并且样品用量较少，非常适合检测环境有机化合物的致突变性或潜癌性，如果同时用几种方法，则更有说服力，本文介绍了Ａｍｅｓ试验，微量向前突变法和ＳＯＳ显色试验，以及它们的应用实例。     

Occurrence and fate of antibiotics in advanced wastewater treatment facilities and receiving rivers in Beijing,China

The occurrence and removal of 13 antibiotics were investigated in five wastewater treatment plants （WWTPs） with advanced wastewater treatment processes in Beijing, China. Most of the target antibiotics were detected in the secondary and tertiary effluents, with the concentrations of 4.8-1106.0 and 0.3-505.0ng·L^-1. Fluoroquinolone antibiotics showed relatively high concentrations in all samples （782-1814ng·L^-1）. Different tertiary treatment processes showed discrepant antibiotics removal performances. Ozonation process was found more effective in removing target antibiotics compared to the coagulation-flocculation-sedimentation process and sand filtration process. Investigation of the target antibiotics in three typical urban rivers in Beijing was carried out to understand antibiotics occurrence in surface water environment. Eight antibiotics were detected in the studied rivers, with highest concentration of antibiotics in the fiver which was mainly replenished by reclaimed water. This study showed the necessity of employing more effective advanced treatment facilities to further reduce the discharge amount of antibiotics.     

基于umu遗传毒性效应的饮用水致癌风险评价的尝试

化学物质暴露是导致癌症发生的重要诱因,通过饮用水暴露导致的人类致癌风险在饮用水处理技术中日益引起重视.由于水中化学物质种类繁多、组成复杂,准确地检测每个致癌物质的浓度和毒性非常困难.为了控制饮用水的安全,根据DNA损伤诱导SOS反应而表达umuC基因这一基本原理建立的SOS/umu测试法,已经广泛应用于饮用水遗传毒性的检测.论文建立了基于umu遗传毒性效应的饮用水致癌风险评价方法,并对北方某水厂饮用水的遗传毒性进行了umu测试,计算了该地区饮用水的致癌风险,提出了可能的饮用水遗传毒性基准值.结果表明,该水厂常规工艺出水的致癌风险均值为1.55×10-6,存在一定的安全隐患;而深度处理工艺能有效地削减出水致癌风险均值至5.3×10-7,达到目前先进国家水质管理的要求,保障了饮用水的安全.样品中4-硝基喹啉-1-氧化物(4-NQO)的等当量浓度(TEQ4-NQO)0.0948μg·L-1可作为饮用水遗传毒性基准值。     

安全优质饮用水

水中的微量元素是人体微量元素的主要来源，而且饮用水的硬度和总溶解性固体和当地居民心脏病的死亡率有确定的正相关性。ＴＤＳ越高，心脏病发作率越少。健康的水应是去除了有机微污染，三致物质，病原菌，病毒和病原原生动物的，并且含有适量微量元素和矿物质的安全和有益于健康的水。     

高级氧化技术去除水中碘代X射线造影剂研究进展

碘代X射线造影剂在医学上的大量使用导致其在水环境中普遍存在,对生态系统和人体健康构成巨大威胁.传统的污水处理技术对碘代X射线造影剂去除效果不佳,应用高级氧化技术去除水中碘代X射线造影剂成为研究热点.本文系统分析了水环境中碘代X射线造影剂的理化性质、来源、危害及污染现状.综述了声化学氧化、光催化、过硫酸盐活化、芬顿和电化...     

腐植酸臭氧氧化和过氧化氢催化氧化处理特性比较

以TOC和UV254为指标,比较了不同条件下腐植酸的臭氧氧化和过氧化氢催化氧化效果,运用HPLC和热裂解-GC-MS分析考察了氧化前后有机物分子量分布和官能团构造的变化情况．研究结果表明：过氧化氢和臭氧单独作为氧化剂对水中TOC基本上没有去除作用,但均能导致水中UV254浓度的降低;在几种催化剂的作用下,过氧化氢对TOC和UV254的去除效果明显提高,其中以O3作为催化剂的效果最好,Fe^2＋次之,而Mn^2＋和Cu^2＋的催化效果较差;过氧化氢催化氧化和臭氧化均导致有机物分子量分布向小分子的方向转移,氧化后水中以羧酸、醇、胺、酯、醚、烷烃为代表的含氧基团和饱和构造基团明显增多;过氧化氢催化氧化和臭氧氧化均有助于改善混凝处理和活性炭吸附处理的效果．关键词腐植酸,臭氧,过氧化氢,催化氧化．     

Mutagenicity of diesel engine exhaust in the Ames / Salmonella assay using a direct exposure method

The aim of this study was to investigate the potential mutagenic activity of diesel engine exhaust in the Ames/Salmonella assay using a direct aerosol exposure system. So, TA 98 and TA 100 strains, with or without added S9 mix, were exposed to diesel emissions after varying degrees of filtration. Variants of these two strains, deficient in nitroreductase (TA 98NR and TA 100NR) or over-expressing O-Acetyl Transferase (YG 1024 and YG 1029), were also exposed to total (unfiltered) diesel exhaust to highlight the putative mutagenicity of any nitro-PAHs present in these emissions. Mutagenic activity of the diesel exhaust was demonstrated on Salmonella typhimurium, strains TA 100 and variants TA 100 NR and YG1029. The use of a particle filter did not modify the genotoxicity of the diesel emissions, indicating a major contribution of the gas phase to the mutagenicity of these diesel emissions. The prominent role of the particulate-associated nitro-polycyclic aromatic hydrocarbons (nitro-PAHs) claimed by some authors working on diesel exhaust organic extracts was not confirmed by our results with native diesel exhaust exposure. Our results show that the gas phase is potentially more mutagenic than the particles alone.