水环境中内分泌干扰物的检测评估及风险控制

针对水环境中日益严重的内分泌干扰物(EDCs)污染风险,从EDCs的来源分类、检测评估、控制去除、迁移归趋等方面对近年来EDCs的研究进展进行评述。仪器分析法和生物分析法的联用为EDCs识别检测的优选技术方法,而风险评估、环境行为、迁移归趋等方面的研究成果为水环境中EDCs控制消除提供了重要依据。     

我国饮用水中内分泌干扰物的去除研究进展

对我国水源水中内分泌干扰物（EDCs）的存在现状以及采用常规饮用水处理工艺、深度处理工艺和高级氧化技术去除EDCs的研究现状和进展进行了综述。我国水源水已受到EDCs的严重污染，其中主要包括农药类、壬基酚、双酚A、邻苯二甲酸酯类以及多氯联苯类等；常规饮用水处理工艺对EDCs的去除非常有限；饮用水深度处理工艺可降解一定的EDCs；生物处理技术具有成本低、可去除多种EDCs的特点，具有很好的应用前景。     

典型内分泌干扰物在城市污水处理过程中的去除研究进展

内分泌干扰物(EDCs)作为一类新型污染物,在环境水体中ng/L浓度水平即可对受纳水生生物及人体健康产生不利影响,因此引起了全社会的广泛关注.污水处理厂是天然水体中EDCs的重要来源渠道,以2类主要内分泌干扰物(类固醇雌激素和酚类内分泌干扰物)为研究对象,综述了它们的物理化学性质及其在传统污水处理厂中的归趋、浓度水平以及相应的去除效率,并探讨了它们的深度处理技术及其在再生水厂中的去除情况,并展望了该领域未来研究发展方向.     

多级AO+潜流湿地对生活污水中的EDCs及常规污染物的去除试验研究

针对生活污水中内分泌干扰物(EDCs)可能引起的生物生态危害问题,以类固醇类内分泌干扰物为处理对象,应用生物生态耦合技术,进行多级AO+潜流式人工湿地处理试验,考察了水力停留时间(HRT)对COD_(Cr)、氨氮(NH_4~+-N)、总磷(TP)、总氮(TN)等污染物去除影响,同时,采用固相萃取法和GC-MS检测各反应器进、出水中雌酮(E1)、17β-雌二醇(E2)、雌三醇(E3)、17α-乙炔基雌二醇(EE2)4种内分泌干扰物浓度变化。结果表明,当多级AO与湿地的HRT分别为9.5h、10.3d时,多级AO+潜流式人工湿地对COD_(Cr)、NH_4~+-N、TP、TN等污染物去除率可分别达78.64%、97.16%、91.84%、90.55%,出水浓度均低于《太湖地区城镇污水处理厂及重点工业行业主要水污染物排放限值》(DB 32/1072—2017)排放浓度限值。多级AO+人工湿地对内分泌干扰物E1、E2、E3和EE2的总去除率可分别达96.04%、92.45%、85.09%、88.38%;其中,多级AO系统对E1、E2、E3和EE2的去除率分别达到75.50%、72.00%、65.08%和63.35%,且一级好氧池对4种EDCs的去除贡献最大,均为27%以上;湿地系统对前3种EDCs的去除率约为20%、EE2为25%。Alpha多样性指数分析表明,好氧池物种数量和多样性多于未加EDCs前,门分类、属分类的微生物群落物种及其丰度分析表明,群落门水平、属水平相对丰度均发生变化,其中,增加的优势菌种可能对系统中EDCs的去除起到了促进作用。     

南宁某污水厂各处理单元中典型EDCs的分布

采用固相萃取前处理技术和高效液相色谱分析方法,研究了典型内分泌干扰物(EDCs)在南宁某城市污水处理厂各处理单元中的分布状况,并对各单元的处理情况进行了分析.结果表明:进水中双酚A(BPA)、雌酮(E1)、雌二醇(E2)和雌三醇(E3)的平均浓度分别为2.86、10.32、4.62和1.78 μg/L,出水平均浓度分别为0.87、2.65、2.45和0.53 μg/L,进、出水浓度均偏高,具有一定的环境风险.E1和BPA主要在氧化沟工艺中被去除,E2主要在沉淀池中被去除,而E3主要在沉砂池和氧化沟中被去除.     

超高流速金属膜过滤性能及其微粒子去除特性

一些病原性微生物,如隐孢子虫(Cryptosporidium)等不能被传统净水处理工艺有效去除,对人类身体健康带来了隐患.以完全去除类似隐孢子虫等微粒子为目标,选用与隐孢子虫外观尺寸相似的Crypto-tracer-1号示踪微粒子,对金属膜过滤系统在饮用水中的处理性能进行评价.选用了三种金属膜--金属薄片筛网膜过滤器(Fuji FP-0.3)、金属非织网式膜过滤器(Fuji FA-3)、金属粉末烧结膜过滤器(SIKA-R0.5AS),对金属膜处理工艺中的水质参数和膜间压力进行测试分析.结果表明,在大规模给水处理厂中,采用金属膜过滤系统可以在高滤速下完全将类似于隐孢子虫的微粒子去除.     

城镇排水内分泌干扰物综合毒性效应的CALUX检测方法

针对当前城镇水环境中日益严重的内分泌干扰物(EDCs)污染,参照已取得ISO17025认证、美国环保局(EPA)批准的荧光素酶表达基因法(CALUX),研究建立了污水和污泥中二口恶英、雌激素、雄激素、肾上腺皮质激素等四类主要EDCs的综合毒性效应检测方法,并通过重复试验对方法的精密度进行了验证。结果表明,CALUX方法作为一种EDCs综合毒性效应的快速生物检测方法,具有较好的灵敏度、重现性、可靠性,可作为仪器分析的有效补充方法。     

膜过滤对饮用水中药品和个人护理品去除研究进展

饮用水中药品和个人护理品(PPCPs)等痕量有机物污染物正在引起越来越多的关注,但传统工艺很难去除此类污染物。过去十年内,膜工艺去除PPCPs的研究逐渐增多。文章综述了超滤、纳滤、反渗透和正渗透四种典型膜工艺对PPCPs的去除效果。重点分析了不同膜工艺对PPCPs的去除棚理,总结了影响PPCPs去除效率的主要因素。提出了膜及其组合工艺在去除PPCPs方面的应用形式及发展方向。     

饮用水消毒过程中典型内分泌干扰物的迁移转化

总结了壬基酚、双酚A、阿特拉津、多氯联苯和雌激素等典型内分泌干扰物（EDCs）在饮用水消毒过程中的去除效果以及副产物的生成情况，分析了由此引起的内分泌干扰作用及其毒性变化。典型EDCs母体在消毒过程中均有一定程度的降解，并以多种途径生成了不同的消毒副产物，依母体结构和消毒方式的不同，最后表现的毒性会有不同程度的改变，其中双酚A消毒后的产物毒性将大大增加。因此研究饮用水中EDCs在消毒工艺中的降解特性和物质迁移变化，对指导饮用水消毒的运行和管理具有重要意义。     

北京市饮用水内分泌干扰物及其前体物的研究

内分泌干扰物(EDCs)是指干扰生物体内维持自稳及调节发育过程中激素的产生、释放、代谢、结合、排泄、交互作用的外源性物质.内分泌干扰物问题引起了公众的广泛关注.为了掌握北京市水源水和自来水中内分泌干扰物质的状况,对北京市主要供水水源的内分泌干扰物进行了调查,研究了水处理工艺对于内分泌干扰物的去除特点,指出壬基酚(NP)及其前体物(NPEOs)是北京地区饮用水中内分泌干扰物,地表水厂常规工艺(混凝-沉淀-过滤)对聚合度n为4～15的低浓度NPEOs(＜1μg/L)基本上没有去除作用,后续活性炭工艺及加氯能降低NPEOs.对于NP(浓度＞10μg/L)常规工艺与深度处理(活性炭或臭氧-活性炭工艺)相结合即可将NP浓度降低到环境推荐安全值(1μg/L)以下.     

北京污水厂进、出水中内分泌干扰物的分布

以三种酚类化合物(4-OP、4-n-NP、BPA)、五种雌激素(E1、E2、E3、17α-E2、EE2)为目标物,对其在北京市三个污水处理厂进、出水中的浓度及工艺流程中的分布、迁移进行了研究.结果表明,污水处理厂出水中浓度最高的物质是BPA、EE2,分别为(56～140)、(78～115)ng/L.BPA和天然雌激素(17α-E2除外)主要被生物降解去除,而对EE2的去除主要发生在初级处理过程,去除率约为63%.两种烷基酚在污水处理厂并不能被有效去除.与欧美国家、日本等相比,北京市污水处理厂进、出水中的内分泌干扰物浓度偏高,尤其是出水中的雌激素浓度较高,具有一定的环境风险.     

Pre-treatment and bioconversion of wastewater sludge to value-added products—Fate of endocrine disrupting compounds

Development of processes for the production of value added products (VAPs), such as biopesticides, microbial inoculants or industrial enzymes through biotransformation of raw or pre-treated wastewater sludge (WWS) has undergone a substantial progress over the last decade. WWS based VAPs are low cost biological alternatives that can compete with chemicals or other cost intensive biological products in the current markets. However, when WWS is used as a raw material for VAPs production, questions still remains on the persistence of organic pollutants within the biotransformed WWS, especially, endocrine disrupting compounds (EDCs) and the production of their toxic intermediates. WWS pre-treatment prior to biotransformation as well as the microbial strains used for biotransformation can possibly remove these organic pollutants. The literature findings concerning the impact of WWS pre-treatment and value added products on EDCs removal are reviewed in this paper. The microbial potential to degrade or detoxify EDCs and toxic intermediates concomitant with value-addition is also discussed. The concept of obtaining EDCs free-WWS based VAPs and simultaneously achieving the objective of pollution control is presented.     

Removal mechanisms for endocrine disrupting compounds (EDCs) in wastewater treatment - physical means, biodegradation, and chemical advanced oxidation: a review

Endocrine disrupting compounds (EDCs) are pollutants with estrogenic or androgenic activity at very low concentrations and are emerging as a major concern for water quality. Within the past few decades, more and more target chemicals were monitored as the source of estrogenic or androgenic activity in wastewater, and great endeavors have been done on the removal of EDCs in wastewater. This article reviewed removal of EDCs from three aspects, that is, physical means, biodegradation, and chemical advanced oxidation (CAO).     

PAEs and BPA removal in landfill leachate with Fenton process and its relationship with leachate DOM composition

An increasing attention has been paid to the trace endocrine disrupting compounds (EDCs) in landfill leachate. In this paper, the removal of EDCs including phthalic acid esters (PAEs) and bisphenol A (BPA) from the fresh and mature landfill leachate by Fenton treatment was studied. More than 40% of PAEs and about 62% of BPA were removed from the raw mature leachate while only 20% of PAEs and 37% of BPA in the raw fresh leachate were reduced, respectively. After the fresh and mature leachates were spiked with PAEs to 1.5 mg L^− 1 and BPA to 0.08 mg L^− 1, the removal efficiencies of BPA and PAEs increased to more than 88%. The results indicated that the removing efficiencies of the EDCs in the leachate had a relationship with their concentrations, and that the trace levels of EDCs in leachate challenged the treatment capacity of the Fenton process. Most of the EDCs in the enriched leachate were removed by oxidation, which had no clear correlation with the hydrophobicity of the EDCs. The flocculation played an important role in the removal of di-(2-ethylhexyl) phthalate that could not be completely oxidized in the Fenton process, in that the EDCs with high n-octanol/water partition coefficient inclined to precipitate after the Fenton process. The dissolved organic matter (DOM) in the fresh leachate inhibited the EDCs removal more than the DOM in the mature leachate did. Both the composition of the leachate DOM and the characteristics of the EDCs determined the removing efficiencies of the EDCs in the Fenton process.     

Hybrid flotation--membrane filtration process for the removal of heavy metal ions from wastewater

A promising process for the removal of heavy metal ions from aqueous solutions involves bonding the metals firstly to a special bonding agent and then separating the loaded bonding agents from the wastewater stream by separation processes. For the separation stage, a new hybrid process of flotation and membrane separation has been developed in this work by integrating specially designed submerged microfiltration modules directly into a flotation reactor. This made it possible to combine the advantages of both flotation and membrane separation while overcoming the limitations. The feasibility of this hybrid process was proven using powdered synthetic zeolites as bonding agents. Stable fluxes of up to 80l m(-2)h(-1) were achieved with the ceramic flat-sheet multi-channel membranes applied at low transmembrane pressure (<100 mbar). The process was applied in lab-scale to treat wastewater from the electronics industry. All toxic metals in question, namely copper, nickel and zinc, were reduced from initial concentrations of 474, 3.3 and 167mg x l(-1), respectively, to below 0.05 mg x l(-1), consistently meeting the discharge limits.     

Fate of steroid hormones and endocrine activities in swine manure disposal and treatment facilities

Manure may contain high concern endocrine-disrupting compounds (EDCs) such as steroid hormones, naturally produced by pigs, which are present at μg L⁻¹ levels. Manure may also contain other EDCs such as nonylphenols (NP), polycyclic aromatic hydrocarbons (PAHs) and dioxins. Thus, once manure is applied to the land as soil fertilizer these compounds may reach aquifers and consequently living organisms, inducing abnormal endocrine responses. In France, manure is generally stored in anaerobic tanks prior spreading on land; when nitrogen removal is requested, manure is treated by aerobic processes before spreading. However, little is known about the fate of hormones and multiple endocrine-disrupting activities in such manure disposal and treatment systems. Here, we determined the fate of hormones and diverse endocrine activities during manure storage and treatment by combining chemical analysis and in vitro quantification of estrogen (ER), aryl hydrocarbon (AhR), androgen (AR), pregnane-X (PXR) and peroxysome proliferator-activated γ (PPARγ) receptor-mediated activities. Our results show that manure contains large quantities of hormones and activates ER and AhR, two of the nuclear receptors studied. Most of these endocrine activities were found in the solid fraction of manure and appeared to be induced mainly by hormones and other unidentified pollutants. Hormones, ER and AhR activities found in manure were poorly removed during manure storage but were efficiently removed by aerobic treatment of manure.     

Hybrid photocatalysis/membrane treatment for surface waters containing low concentrations of natural organic matters

Since the mid-1990s, numerous studies on the treatment of drinking water by photocatalysis have been reported. Once optimised, the photocatalytic process can completely degrade numerous natural and artificial organic compounds. In this study, a hybrid photocatalysis/membrane process was used as a polishing treatment of surface water containing a small concentration of natural organic matters (i.e. total organic carbon (TOC) concentration of around 3mg/L) which may be difficult to remove using conventional filtration or coagulation. An optimum pH of 4.5 and a TiO(2) concentration of 0.1g/L were found to lead to the highest removal efficiencies. The relative effect of the individual processes featuring in the hybrid system (UV radiation, TiO(2) adsorption and membrane filtration) was also assessed for different pH values. The membrane separation process was accounted to remove around 18% of the initial TOC concentration, while TiO(2) adsorption alone was generally responsible for less than 5% of TOC removal during the 120 min of the experiments. However, when the natural water was only radiated by UV light, up to 70% of TOC was removed. A synergetic effect was observed when the three processes (TiO(2), UV and membrane) were used together. Comparison of removal efficiencies obtained during real and model (International Humic Substance Society) waters treatment by photocatalysis is also presented, revealing the importance of the nature of the feed in this type of treatment.     

Bacteriophage MS-2 removal by submerged membrane bioreactor

A membrane bioreactor (MBR) may serve as a pre-disinfection or disinfection unit, in addition to its solid/liquid separation and biological conversion functions, to produce sewage effluent of high quality. This bench-scale pilot study focuses on investigating the performance of a submerged MBR in pathogen removal and the factors affecting the removal, using a 0.4-microm hollow-fiber membrane module submerged in an aeration tank and bacteriophage MS-2 as the indicator organism. Removal of the MS-2 phage was found to be contributed by physical filtration by the membrane itself, biomass activity in the aeration tank and bio-filtration achieved by the biofilm developed on the membrane surface. The membrane alone gave poor virus removal (0.4+/-0.1 log) but the overall removal increased substantially with the presence of biomass and the membrane-surface-attached biofilm. The contributions of the suspended biomass and attached biofilm to the phage removal are dependent on the inter-related parameters including the concentration of mixed liquor suspended solids (MLSS), the sludge retention time (SRT) and the food to mass (F/M) ratio. The correlations between effluent flux/trans-membrane pressure and virus removal give evidence that phage removal in the MBR is most likely susceptible to both biological and physical factors including the quantity and property of the biomass and the biofilm and the membrane pore size reduction.     

预处理对东江原水超滤过程中膜污染的控制作用

以珠江流域东江水作为原水,研究不同预处理(混凝、吸附、氧化)及其组合对水体中有机污染物的去除效果及对超滤膜污染的控制作用。试验结果表明,针对东江原水中天然有机物的去除,聚合氯化铝(PACl)、粉末活性炭(PAC)和高锰酸钾(KMnO4)的最佳投加量分别为20、30、0. 1 mg/L;三种单一预处理方法能够在一定程度上缓解膜通量衰减,而两两组合预处理则能够进一步提高膜运行通量;对于聚偏氟乙烯膜,PACl+PAC组合预处理对膜污染的控制作用最好。对于UV254和蛋白质,PACl和KMn O4对其去除效果优于PAC;对于多糖,三种预处理方法对其去除效果均不佳(<40%),其中PAC略好于PACl和KMn O4。此外,三种单一预处理方法对腐殖酸类荧光物质的去除效果高于蛋白质类荧光物质,而组合预处理能够更加显著地降低这两类荧光物质的响应强度,其中PACl+PAC组合预处理对有机物各荧光组分的去除效果最佳。通过对膜污染物成分的识别分析可知,东江原水中造成超滤膜污染的物质有腐殖酸类、多糖类和蛋白质类物质,而化学不可逆污染物主要为多糖类物质及少量的腐殖酸类物质,化学可逆污染物主要为蛋白质类物质及部分腐殖酸类物质。