饮用水处理工艺去除两种典型内分泌干扰物的性能

研究了水中两种典型内分泌干扰物———双酚A(BPA)和邻苯二甲酸二甲酯(DMP)在饮用水常规处理、臭氧活性炭和微曝气活性炭深度处理中试工艺中的去除性能。研究发现,饮用水常规处理工艺对BPA和DMP的去除效果有限,进水浓度为200~300μg/L条件下经过混凝、沉淀和砂滤后,BPA和DMP的去除率分别仅为25.38%和13.29%。臭氧活性炭深度处理工艺能有效去除BPA和DMP,但二者在该工艺中的去除特性有所不同:水中BPA经过臭氧氧化后几乎被全部去除,后续的生物活性炭处理单元作用较小;但臭氧氧化仅可部分去除DMP,大部分靠后续生物活性炭柱去除。微曝气活性炭深度处理工艺也能有效去除BPA和DMP,对二者的去除主要靠微曝气活性炭柱的作用,其效果略优于臭氧投加量为0条件下的臭氧活性炭柱,这说明微曝气活性炭柱存在较多的特定降解菌。通过静态吸附试验发现,臭氧活性炭柱和微曝气活性炭柱内活性炭对BPA和DMP的最大吸附容量均远小于新炭,同时臭氧活性炭柱内活性炭吸附容量略高于微曝气活性炭柱。     

万家寨引黄水中内分泌干扰物的去除研究

在引黄原水中存在的环境内分泌干扰物主要为微量但可能超标的邻苯二甲酸二丁酯(DBP)和双酚A(BPA),经太原呼延水厂现行水处理工艺对引黄水进行处理后,仍可能出现超标状况。低浓度DBP和BPA水溶液静态吸附的结果:活性炭对DBP和BPA的吸附平衡时间分别为7h和6h;活性炭对水中DBP和BPA的饱和吸附量分别为35.78mg/g和42.05mg/g;当炭柱内流速为23.28cm/h,DBP和BPA吸附柱穿透吸附量最大分别为32.73mg/g和36.48mg/g。对引黄水中微量但超标准的DBP和BPA进行动态吸附的结果:吸附柱穿透吸附量仅分别为0.048 4mg/g和0.083 8mg/g,表明活性炭对引黄水中微量DBP和BPA的吸附行为与高浓度下取得的研究结果有所不同。采用臭氧进行氧化处理的结果表明,臭氧处理对原水中低浓度的DBP和BPA去除作用有限,处理效果与臭氧加入方式有关。     

GAC对水中内分泌干扰物双酚A的吸附特性及动力学研究

研究了颗粒活性炭(GAC)对水中内分泌干扰物双酚A(BPA)的吸附容量、吸附动力学及其影响因素.结果表明,GAC吸附容量大,吸附等温线符合Langmuir和Freundlich模型;吸附容量受GAC粒径的变化影响较大.Langmuir模型的最大吸附容量qm与粒径dp关系为:ln(qm)=-0.507 5×ln(dp) 14.07;Freundlich模型Kf与dp关系为:ln(kf)=-1.078 ln(dp) 18.307.GAC对BPA为单分子层吸附,400 min基本可达到平衡,且吸附速率变化符合拟二级动力学模型,dp与速率常数k2之间符合ln(k2)=-1.039 ln(dp)-9.014;BPA初始浓度C0与k2关系式为1/k2=529.7 C0-35 979.     

臭氧联合工艺降解典型内分泌干扰物的研究

以两种典型内分泌干扰物(ECDs)——壬基酚(NP)和17α-乙炔基雌二醇(EE2)为目标物,运用GC/MS检测方法,对其在臭氧、臭氧/过氧化氢、臭氧/超声三种工艺中的去除特性进行了研究,并初步研究了臭氧降解的反应动力学。结果表明:联合工艺显著提高了目标物的去除效率,NP和EE2的去除率分别提高9.6%～17.7%和14.6%～23.4%。目标物去除率随臭氧投加量和pH值的增大而增大;随H2O2/O3摩尔比的增加先增大后减小,摩尔比为0.6时,去除率均达到最大;超声强化了臭氧氧化效率,但超声(US)强度(60～240 W)的变化对联合工艺去除目标物效果影响不明显。臭氧氧化两种目标物都遵循假一级反应动力学,碱性条件下的反应速率常数要大于酸性及加入叔丁醇条件下的反应速率常数。     

固相萃取-高效液相色谱检测原水中微量内分泌干扰物

提出了检测饮用水中几种微量存在的内分泌干扰物的仪器分析方法.检测对象包括邻苯二甲酸二甲酯(DMP),邻苯二甲酸二丁酯(DBP),双酚A(BPA),壬基酚(NP),阿特拉津(Atrazine)等,采用固相萃取技术对水样进行预处理,利用高效液相色谱进行分析,DMP,DBP,BPA,NP和Atrazine的超纯水加标回收率、原水加标回收率均可达到70%以上;对上海市饮用水水源黄浦江进行了初步的水质调查,分别检测出较高含量的二丁酯、双酚A、壬基酚和阿特拉津.     

活性炭去除饮用水中溴酸盐的研究进展

臭氧氧化过程中产生的溴酸盐的问题已经成为目前臭氧大规模应用于饮用水中的最大制约因素。活性炭去除法是国内外最常用的去除溴酸盐的方法,且由于活性炭常作为臭氧氧化工艺必备的联用工艺,容易实现生产应用,且不需要增加额外的投资,引起了研究者的极大关注。本文全面阐述了关于活性炭／生物活性炭对溴酸盐的去除效能、去除机理及影响因素的研究进展。针对活性炭去除饮用水中溴酸盐的研究现状,提出了今后研究的主要方向和亟需解决的问题。     

饮用水中致臭微量有机物的强化去除与控制技术述评

系统总结了饮用水中2MIB等致臭微量有机物的去除与控制技术。探讨了活性炭吸附、化学氧化、生物氧化、膜分离等技术去除水中2MIB等致臭微量有机物的作用机制及影响因素;介绍了各技术的应用情况,并对其优缺点进行了评价。通过大量文献结果分析表明:活性炭吸附、化学氧化、生物氧化、膜分离等技术具有良好的强化去除水中致臭微量有机物的效能;不同水质参数及工况条件对各工艺去除2MIB效果有重要影响。生产中应发挥不同单元之间的协同作用、优化工艺参数以实现2MIB等致臭微量有机物去除高效性与经济性的统一。     

饮用水深度净化工艺现场对比试验

考察了实际生产规模的臭氧粒状活性炭工艺以及小型超滤、纳滤、反渗透膜法两种典型饮用水深度净化工艺的处理效果。试验结果发现臭氧活性炭工艺具有优良、稳定的去除有机污染物功能,而孔径较小的活性炭纤维除污染效果并不好,臭氧氧化出水、超滤出水再用压缩活性炭进行吸附处理对有机物的去除效率要比直接处理原水高。超滤膜除有机物效率不高,而反渗透和纳滤膜在较好地去除水中有机物的同时,也去除了水中绝大部分无机物,出水有机物和无机物浓度都比较低。     

臭氧活性炭工艺去除饮用水中COD_(Mn)的应用试验

通过臭氧活性炭工艺去除饮用水中CODMn 的应用试验 ,探讨了工艺参数的选择对CODMn去除效果的影响。在此基础上 ,提出了臭氧活性炭二级串联工艺布置方式 ,试验结果表明能大幅度提高CODMn的去除率。     

饮用水中药品和个人护理用品的研究进展

饮用水中残留药品和个人护理用品(PPCPs)正在成为一种普遍性的污染,已引起人们越来越多地关注。近年来在世界各地的饮用水中不断检出了ng/L水平的PPCPs。常规的混凝、沉淀和过滤等工艺不能有效去除PPCPs;氯和二氧化氯消毒能够部分去除PPCPs;粒状活性炭吸附去除PPCPs的效果优于粉末活性炭吸附;臭氧化等高级氧化工艺能高效去除大多数PPCPs;反渗透和纳滤能高效去除PPCPs,而微滤和超滤效果不佳。目前还缺乏PPCPs在饮用水处理中降解转化中间产物方面的数据。确定饮用水中PPCPs健康效应,建立安全标准,优化现有处理技术,开发新型处理技术和分析中间转化产物等将是行业面临的重要挑战和研究课题。     

Examining the biodegradation of endocrine disrupting bisphenol A and nonylphenol in WWTPs.

The aim of this work was to examine biodegradation of the endocrine disrupting chemicals bisphenol A (BPA) and nonylphenol (NP) in activated sludge. Experiments were performed in a pilot wastewater treatment plant (WWTP) in Copenhagen, Denmark. During standard operation the BPA concentration was halved whereas the NP concentration was unchanged. Step-addition experiments showed that biomass adaptation to increased BPA and NP concentrations took 10 to more than 40 days depending on temperature, hydraulic retention time, and pre-exposure of the biomass. Mass-balance experiments showed that above 99% of the dosed BPA and 90% of the dosed NP is removed by biodegradation at steady-state. Batch experiments showed that BPA biodegradation occur solely under aerobic conditions. The work is believed to add vital knowledge to our understanding of parameters and processes governing biodegradation of EDCs in WWTPs.     

Behaviour of bisphenol A (BPA), 4-nonylphenol (4-NP) and 4-nonylphenol ethoxylates (4-NP1EO, 4-NP2EO) in oxidative water treatment processes.

Endocrine disrupting chemicals (EDCs) such as natural and synthetic hormones or industrial chemicals can adversely affect the endocrine system at very low concentrations. As such substances can be present in raw water used for drinking-water production, they potentially pose a health risk to humans. In this study laboratory tests were performed to determine removal efficiencies of selected oxidative drinking water treatment processes, namely ozonation (1.4 mg/l O3) and chlorination, using sodium hypochlorite (0.5 mg/l NaClO) and chlorine dioxide (0.4-0.6 mg/l ClO2) under conditions applied in technical plants. 500-300,000 ng/l of bisphenol A (BPA), 4-nonylphenol (4-NP) and 4-nonylphenol-n-ethoxylates (NPnEO) were selected for investigations and measured by HPLC/FLD and HPLC/MS. To investigate possible oxidation by-products, adsorbable organic halogens (AOX) were determined and estrogenic activities were assessed with the help of an estrogen receptor binding assay (YES). Ozonation and chlorination with ClO2 removed both 4-NP and BPA below detection limits, corresponding with AOX and estrogenic activity. Concerning NPnEO ozonation removed NP1EO and NP2EO up to 28% and 30%, respectively, whereas ClO2 showed high removal efficiencies, eliminating >94% and 92%, respectively. NaCIO removed 4-NP and BPA below detection limits, but estrogenic activities increased and AOX could be measured. NP1EO and NP2EO were only marginally reduced corresponding to the slight decrease of estrogenic potential.     

臭氧活性炭深度处理工艺除藻效能研究

通过中试除藻试验,研究了臭氧活性炭深度处理工艺的除藻效能。结果表明,经过预臭 氧化和常规工艺处理后,深度处理工艺可再去除67％的含藻量。工艺参数:臭氧投加量2 mg／L,接 触时间15 min,活性炭滤池滤速10 m／h,停留时间12 min。探讨了预臭氧化和深度处理两种组合工 艺的除藻机理和影响因素。     

Removal of endocrine disruptors using homogeneous metal catalyst combined with nanofiltration membrane.

Chemicals that are known or suspected of being endocrine disrupting chemicals (EDCs) have received increased attention over the past decade for their potential presence in drinking water sources. This study focuses on the development of a hybrid system that combines the advantages of nanofiltration (NF) and homogeneous catalytic oxidation, which include compactness, operational facilitation, high treatment efficiency, and selective reaction capability. Iron(lll)-tetrasulfophthalocyanine (Fe-TsPc) was employed as a homogeneous metal catalyst to degrade bisphenol-A (BPA), a representative EDC. The treatment efficiency of BPA as well as operational characteristics of the hybrid system was investigated to examine the applicability of this technique to decrease the concentration of EDCs in drinking water. Fe-TsPc homogeneous catalyst revealed a remarkable activity in degrading BPA under acidic condition. The high rejection of Fe-TsPc catalyst in the feed stream by the membrane for its large molecular weight (976 Da) and functional group (SO3(-) X4) allowed the continuous use of the catalyst for BPA oxidation reaction. The NF with Fe-TsPc/H2O2 hybrid system turned out to have higher BPA treatment efficiency comparing with the NF-only system since the hybrid system reduced BPA concentration in the feed stream by catalytic destruction of BPA as well as it mitigated concentration polarization on the surface of the membrane.     

臭氧-活性炭深度处理滦河水的试验研究

对滦河水进行O3-GAC工艺深度处理中试研究表明O3-GAC能在较长时间内保持对水中有机物的去除,CODMn的平均去除率为60.19%;TOC的平均去除率为64%;UV254的平均去除率为70.41%;NH3-N的平均去除率为53.83%;对水中的浊度和色度都有明显的去除效果,尤其臭氧化对改善难生物降解有机物的可生化性有十分显著的作用;O3-GAC能有效地去除饮用水中的有害、有毒物质,提高饮用水的安全性.     

Removal of bromate and assimilable organic carbon from drinking water using granular activated carbon.

This study investigated the feasibility of using granular activated carbon (GAC) to remove bromate ion (BrO3-) and assimilable organic carbon (AOC) from drinking water through a rapid small-scale column test (RSSCT) method and a pilot-scale study. Results from RSSCT indicated that the GAC capacity for BrO3- removal was dependent on the GAC type, empty bed contact time (EBCT), and source water quality. The GAC with a high number of basic groups and higher pHpzc values showed an increased BrO3- removal capacity. BrO3- removal was improved by increasing EBCT. The high EBCT provides a greater opportunity for BrO3- to be adsorbed and reduced to Br- on the GAC surface. On the other hand, the presence of dissolved organic carbon (DOC) and anions, such as chloride, bromide, and sulfate, resulted in poor BrO3- reduction. In the GAC pilot plant, a GAC column preloaded for 12 months achieved a BrO3- and AOC removal range from 79-96% and 41-75%, respectively. The BrO3- amount removed was found to be proportional to the influent BrO3- concentration. However, the BrO3- removal rate apparently decreased with increasing operation time. In contrast, the AOC apparently increased during the long-term operation period. This may be a result of the contribution due to new GAC being gradually transformed into biological activated carbon (BAC), and the bacterial biomass adsorbed on GAC surface hindering BrO3- reduction by GAC either by blocking pores or adsorbing at the activated sites for BrO3- reduction.     

超声波技术在饮用水中应用的研究进展

就国内外超声波技术在饮用水处理中的研究现状和进展进行了综述.介绍了超声波技术的反应机理、反应条件和主要影响因素.针对水源水中所含有的腐殖质、藻类、内分泌干扰物、细菌以及常规处理后的消毒副产物等物质,通过超声波技术处理以及超声波的协同处理的应用情况进行分析.由于超声波技术具有易与其他水处理技术和设备配套的优势,因此其在饮用水的处理中具有很好的应用前景.     

Efficient taste and odour removal by water treatment plants around the Han River water supply system.

Seven major water treatment plants in Seoul Metropolitan Area, which are under Korea Water Resources Corporation (KOWACO)'s management, take water from the Paldang Reservoir in the Han River System for drinking water supply. There are taste and odour (T&O) problems in the finished water because the conventional treatment processes do not efficiently remove the T&O compounds. This study evaluated T&O removal by ozonation, granular activated carbon (GAC) treatment, powder activated carbon (PAC) and an advanced oxidation process in a pilot-scale treatment plant and bench-scale laboratory experiments. During T&O episodes, PAC alone was not adequate, but as a pretreatment together with GAC it could be a useful option. The optimal range of ozone dose was 1 to 2 mg/L at a contact time of 10 min. However, with ozone alone it was difficult to meet the T&O target of 3 TON and 15 ng/L of MIB or geosmin. The GAC adsorption capacity for DOC in the three GAC systems (F/A, GAC and O3 + GAC) at an EBCT of 14 min is mostly exhausted after 9 months. However, substantial TON removal continued for more than 2 years (>90,000 bed volumes). GAC was found to be effective for T&O control and the main removal mechanisms were adsorption capacity and biodegradation.     

壬基酚聚氧乙烯醚(NPEOs)在净水厂中的监测

低浓度内分泌干扰物长期作用会对人体健康产生不可忽视的负面影响.较详细地研究了北方某给水厂现有净水处理工艺对低浓度NPEOs的控制特性,结果表明,该厂常规工艺单元(无预氯化)对NPEOs(聚合度n＝4～15)基本上没有去除作用,后续活性炭单元对NPEOs的去除作用也不是很明显,有待进一步研究.由于氯的强氧化作用的存在,加氯能明显降低水中的NPEOs浓度.     

Behaviour of endocrine disrupting chemicals during the treatment of municipal sewage sludge.

Agricultural application of municipal sewage sludge has been emotionally discussed in the last decades, because the latter contains endocrine disrupting chemicals (EDCs) and other organic micropollutants with unknown fate and risk potential. Bisphenol A (BPA) was chosen as a model substance to investigate the influence of sludge conditioning on the end-concentration of EDCs in sludge. Adsorption studies with radioactive-labelled BPA showed that more than 75% BPA in anaerobically digested sludge is bound to solids (log Kd = 2.09-2.30; log Koc = 2.72-3.11). Sludge conditioning with polymer or iron (III) chloride alone had no influence on the adsorption of BPA. After conditioning with iron (III) chloride and calcium hydroxide desorption of BPA took place. Apparently, it occurred due to the deprotonation of BPA (pKa= 10.3) as the pH-value reached 12.4 during the process. The same behaviour is expected for other phenolic EDCs with similar pKa (nonylphenol, 17beta-estradiol, estron, estriol, 17alpha-ethinylestradiol). This study shows high affinity of BPA to the anaerobically digested sludge and importance of conditioning in the elimination of EDCs during the sludge treatment. Addition of polymer is favourable in the case of sludge incineration. Conditioning with iron (III) chloride and calcium hydroxide shows advantages for the use of sludge as fertiliser.