城市污水石灰法深度处理工艺中有毒物质的变化规律

分别采用7-乙氧基异酚恶唑酮．脱乙基酶（EROD）活性测定法，重组人激素受体基因的酵母测试和Q67发光菌试验方法，对北京市某生活污水处理厂的进水、二沉出水以及经过石灰法深度处理后的出水中的类二恶英物质、类雌激素物质和急性毒性物质进行了分析。进水中的三类生物毒性效应物质中的急性毒性物质，可通过活性污泥法基本去除，而对类雌激素物质和类二恶英物质的去除率分别为76％和52％。经过石灰沉淀法的深度处理后，可使上述两类物质的总去除率达到95％和68％。出水中的雌激素当量水平与欧洲国家污水处理厂出水水平相当，而类二恶英物质的总浓度低于美国EPA饮用水中二恶英的最大允许浓度。展示了生物毒性测试方法在排水生态风险和工艺评价方面的应用潜力。     

生活污水的臭氧深度处理及其急性毒性

以生活污水处理厂二级生物处理出水为研究对象,利用固相萃取、吸附树脂层析等手段,研究了臭氧氧化过程中进出水及不同分级组分的发光细菌急性毒性的变化,揭示了无机离子浓度对臭氧氧化出水急性毒性的影响,并采用三维荧光光谱对急性毒性相关的物质组分进行了解析。结果表明,在反应时间为15 min,臭氧投加速率为2.1 mg·(L·min)-1,臭氧氧化出水的急性毒性明显下降,出水的急性毒性仅为进水的24.7%。水样不同分级组分的生物毒性测试结果显示,生物处理出水中的亲水性物质和疏水中性物质分别贡献了44.6%和27.8%的毒性当量。当生物处理出水的氯离子含量为75~400 mg·L~(-1)时,经臭氧氧化后,出水的急性生物毒性与氯离子浓度成正相关关系,当生物处理出水的硫酸根离子和硝酸根离子含量分别在150~300 mg·L~(-1)和20~110 mg·L~(-1)变化时,经臭氧氧化后,出水的急性生物毒性变化不大,结合三维荧光光谱的分析结果,臭氧氧化出水中急性毒性物质可能主要存在于芳香族蛋白质类似物(Ⅱ区)和类腐殖酸类物质(Ⅴ区)中。     

改良型Carrousel氧化沟工艺生物脱氮除磷效果研究

为了提高改良型Carrousel氧化沟工艺污水处理厂的脱氮除磷效果,结合某污水处理厂3年的运行实践,讨论了该工艺的处理效果,生物脱氮除磷原理及影响出水效果的因素.分析表明将DO控制在0.3～0.7 mg/L范围内,能够使出水中的TN浓度低于20 mg/L;在氧化沟中发生的同步硝化反硝化反应(SND)对总氮的去除的贡献占总系统脱氮的66%;该系统剩余污泥的含磷率为3.0%,生物细胞中平均含磷量可达细胞干重的4.2%;总磷去除率与污泥龄具有很好的线性关系,加大污泥排放量可以提高除磷效果.     

生物生态耦合系统对分散式农村生活污水的深度净化

针对分散式农村生活污水排放标准的提升,通过集约式立体生物生态耦合系统对农村生活污水二级处理出水进行深度净化,采用国家标准方法对系统进出水中的COD、氨氮、TN和TP进行了测定,评价了系统对各污染物质的去除效果。结果表明:在实验进水COD,氨氮,TN和TP均属于《城镇污水处理厂污染物排放标准》(GB 18918-2002)一级B标准时,系统稳定后实验出水的COD,氨氮,TN和TP的浓度分别可降至9～35、1～7、8.0～14.9、0.20～0.47 mg·L~(-1),均满足一级A标准。随着流水分区不同,COD,氨氮,TN和TP的浓度逐渐降低。采用集约式立体生物生态耦合系统可使农村生活污水二级处理出水水质达到一级A排放标准,实现深度净化的需求。     

采用水解酸化-复合好氧处理制药工业废水的工艺评价

以制药工业综合废水处理为例对其采用的两级水解酸化复合好氧工艺的处理效果进行评估。按常规指标进行评估,该工艺对于制药综合废水的处理效果达到了设计目的,COD去除率可达到78.2%以上,NH+4-N的去除率达到99.3%,出水质量基本满足"污水综合排放标准(GB8978-1996)"二级标准和"辽宁省污水综合排放标准(DB21.1627-2008)";急性毒性的检测表明,经过该工艺处理后出水为低毒性;三维荧光谱分析(EEM)表明,制药综合废水经生物处理后的可溶性有机物中仍然存在难降解物质,建议增加物化处理以提高处理效果;并且制药废水经处理后的出水中的盐度对排入的生态系统存在风险,建议纳入排放标准以加强管理。     

高效液相色谱-二极管紫外阵列/荧光串联测定雌激素的方法及污水处理厂对雌激素的去除特性

建立了高效液相色谱-二极管紫外阵列(PDA)/荧光(FLD)串联法测定雌酮(E1)、雌二醇(E2)、乙炔雌二醇(EE2)、雌三醇(E3)和双酚A(BPA)5种典型雌激素的方法,并利用该方法测定了某城市污水处理厂5种雌激素的分布情况及去除特性。研究结果表明,二极管紫外阵列/荧光检测器对5种雌激素的检出限在4.30~9.54μg·L~(-1)之间,定量限在12.90~28.62μg·L~(-1)之间。5种雌激素日内精密度的相对标准偏差小于6.86%,日间精密度相对标准偏差小于9.47%;对100、500和1 000 ng·L~(-1)3个浓度的5种雌激素经富集浓缩后测定的加标回收率在62.8%~96.0%之间,方法符合痕量分析要求。利用该方法对城市某污水处理厂雌激素的含量进行测定,结果表明污水处理厂进水中5种雌激素的总浓度为3 073.1 ng·L~(-1),其中雌三醇(E3)的浓度最大,占5种雌激素总量的40.1%。出水中5种雌激素的总浓度为124.7 ng·L~(-1),5种雌激素的总去除率为95.9%。不同处理单元对雌激素的去除效率存在明显差异,生物处理单元对5种雌激素的去除效果最好,5种雌激素的去除率在73.6%~96.6%之间;一级处理工艺和消毒工艺对雌激素的去除效果较差。     

木屑-硫磺填充床反硝化生物滤池强化硝酸盐去除

针对污水处理厂二级出水深度脱氮的需求,设计了以木屑与硫磺颗粒为填料(质量比1:1)的反硝化生物滤池,对碳氮比失衡的污水处理厂二级出水进行深度脱氮处理。结果表明,木屑释放碳源速率在10 d之后趋于稳定,COD中(40.6±10.0)%是反硝化菌可直接利用的VFA。反硝化生物滤池运行的最佳HRT为10 h,在此条件下,进水硝酸盐(以N计)浓度为30 mg·L~(-1)时,出水硝酸盐浓度最低为11.5 mg·L~(-1),亚硝酸盐(以N计)浓度最低为1.4 mg·L~(-1),反硝化生物滤池内未发生硝酸盐异化还原(DNRA)作用,出水无氨氮积累。出水SO42-浓度最高为73.8 mg·L~(-1)。反硝化生物滤池运行稳定后,出水中COD未超过30 mg·L~(-1),木屑释放的碳源与异养反硝化过程消耗的碳源持平,经反硝化生物滤池深度处理的出水中无过量残留有机物。出水pH稳定在6.9～7.4范围内,反硝化生物滤池无需外加碱类物质。     

生物活性炭法深度处理印染废水及其生物毒性的表征

采用负载经驯化后微生物的活性炭深度处理实际印染废水,研究生物活性炭系统中存在的生物相及其降解有机污染物的作用,并表征了处理后印染废水的生物毒性.结果表明,生物相中含有草履虫、轮虫及钟虫等原生动物.随着运行次数的增加,活性炭反应器在运行5次后出水的COD、NH3-N及色度去除率骤降,但是生物活性炭处理后出水的COD、NH3-N及色度去除率缓慢下降.生物活性炭能很好地降解印染废水中的苯酚类和稠环芳烃污染物.本研究中生物活性炭反应器对氨氮和COD的去除符合一级动力学方程,去除动力学常数分别为1.02和0.96.经过生物活性炭的处理可以将印染废水的生物毒性降到适于小球藻生长的水平.     

高原城市污水处理厂中5种典型有机紫外防晒剂含量及其去除

有机紫外防晒剂具有内分泌干扰效应、遗传毒性和生殖毒性等多种负面生物效应,其进入环境中的一个主要途径为工业废水排放及污水处理厂出水的排放。昆明地处高原,紫外线较强,有机紫外防晒剂的使用量逐年增多,因此选择了5种典型有机紫外防晒剂:胡莫柳酯(HMS)、甲氧基肉桂酸乙基已酯(EHMC)、二苯酮-3(BP-3)、4-甲基苄亚基樟脑(4-MBC)和奥克立林(OC)作为目标物质,利用气相色谱-质谱联用技术,检测了昆明市5座城市污水处理厂进水、二级生化处理及深度处理进出水中有机紫外防晒剂的含量,分析了不同二级生化处理及深度处理工艺对目标物质去除效率的影响。结果表明,目标物质的去除主要依靠二级生化处理工艺,3种工艺都有比较好的去除效果,其中缺氧-厌氧-缺氧膜生物反应器工艺相对来说更好。此外,深度处理也能有效去除目标物质,紫外消毒去除效果更好。5种目标物质的总去除率达58.76%~94.0%,可见还有一部分的有机紫外防晒剂迁移到了环境中,具有一定的环境与健康风险。     

高膜通量厌氧微网生物反应器处理生活污水的研究

将动态膜技术与厌氧膜生物反应器相结合,形成一体式厌氧微网生物反应器(AnFBR),用于城市生活污水的处理,研究了在高膜通量条件下,AnFBR的运行情况和对生活污水的处理效果。结果表明,AnFBR在膜通量为72 L/(m2.h)条件下可连续稳定运行40 d;系统对COD平均去除率为58.4%,对TN和NH3-N有一定的去除效果;出水SS最高为15.0 mg/L,出水中污染物粒径在10μm以下;微网动态膜对小分子物质的截留量不高,但对分子量大于1 000 kU的物质有明显的截留效果,进水中的大部分大分子物质被转化为小分子物质;AnFBR在保留了泥水分离特点的情况下还具有结构简单、膜通量高、微网过滤周期长等优点。     

Performance evaluation and application of surface-molecular-imprinted polymer-modified TiO2 nanotubes for the removal of estrogenic chemicals from secondary effluents

The removal of estrogenic chemicals during wastewater reclamation has been a great concern. Current advanced treatment processes are inefficient for the removal of estrogenic chemicals from secondary effluents of municipal wastewater treatment plants (WWTPs) due to the coexistence of other pollutants with less environmental significance which are also removed simultaneously. The search for highly selective and low-cost removal methods is warranted. Therefore, surface-molecular-imprinted polymer-modified TiO₂ nanotube (S-MIP-TiO₂ NT) photocatalysts were fabricated, characterized, and tested for the removal of estrogenic pollutants from wastewater in this study for the first time. Scanning electron microscopy and Fourier-transform infrared spectroscopy studies showed that the TiO₂ NTs (with an average diameter of 60 nm) were successfully imprinted with functional groups (i.e., carboxyl). The adsorption selectivity and photocatalytic activity of the S-MIP-TiO₂ NTs towards template compound (17β-estradiol, E2) were improved, compared with neat TiO₂ NTs. Interestingly, S-MIP-TiO₂ NTs exhibited higher adsorption intensity and photocatalytic selectivity at low concentrations (from 10 ng/L to 100 μg/L, as normal estrogenic chemical concentrations in secondary effluents) of E2 than that at high concentrations (from 10 to 1,000 mg/L). It was also found that some representative estrogenic chemicals and estrogenic activity could be selectively and rapidly removed from secondary effluents of municipal wastewater treatment plants using S-MIP-TiO₂ NTs as photocatalysts. In addition, S-MIP-TiO₂ NT photocatalysts exhibited excellent regeneration characteristics. Photocatalytic treatment using S-MIP-TiO₂ NTs could be a promising approach for the effective removal of estrogenic chemicals from secondary effluents of municipal WWTPs.     

Estrogenic and dioxin-like potency in each step of a controlled landfill leachate treatment plant in Japan

The estrogenic activity (by E-screen bioassay), the concentrations of PCBs, PCDDs/PCDFs (and their resulting toxicity equivalents, TEQ) and several endocrine disrupting chemicals (EDCs: e.g., bisphenol A, nonylphenol, Butyl benzylpthalate (BBP), di-n-butylphthalate (DBP), 17alpha-ethynyl-estradiol or 4-octylphenol) have been analyzed from leachates of each step (before treatment, after biodegradation/sedimentation and after charcoal treatment) of a controlled landfill leachate treatment plant. The comparison of the effluent of the examined landfill leachate treatment plant with water from a nearby river in this study indicated no additional dioxin-like (e.g., TEQ: 0.027 compared to 1.01 pg TEQ/l; PCBs: 1.2 compared to 3.9 ng/l) or estrogenic impact (2.8 compared to 3.5 ng estradiol equivalents EE/l; analyzed by E-screen bioassay) from the leachate treatment plant into the surrounding water environment. The impact of dioxin-like compounds from uncleaned leachates into the final cleaned effluents could be sufficiently reduced by the leachate treatment plant for PCDDs (75%), PCDFs (62%), dioxin-like PCBs (97%), and the sum of TEQ (78%). The leachate treatment plant also achieved a reduction of the estrogenic activity as determined by E-screen (from 4.8 to 2.8 ng EE/l = 42%), by GC/MS for bisphenol A (>96% and nonylphenol (>98%) or by ELISA for estradiol (>80%). Additionally, for the validation of the E-screen, five known endocrine disrupting chemicals (EDCs: bisphenol A, BBP, DBP, 17 alpha-ethynyl-estradiol, 4-octylphenol) were analyzed. The EC50 values and estradiol equivalents factors (EEFs) for the five EDCs determined in this study were comparable to previously published data. The combined biological and chemical trace analysis data have provided valuable information on the relative contribution of natural, synthetic, and non-steroidal anthropogenic chemicals to the estrogenic and dioxin-like activity in leachates from a wastewater treatment plant, and water from a nearby river.     

An assessment of endocrine disrupting activity changes during wastewater treatment through the use of bioassays and chemical measurements.

The objective of this study was to assess the removal efficiencies of secondary wastewater treatment processes for compounds causing endocrine disrupting activity. The study used bioassays and chemical measurements, such as gas chromatography with mass spectrometry and enzyme immunosorbent assays. A total of seven full-scale water reclamation facilities using different unit operations and two pilot-scale membrane bioreactors were examined. Findings of this study imply that estrogenic disrupting activity in primary effluent is mainly caused by two steroidal hormones (17beta-estradiol and estriol) and, to a lesser extent, by synthetic chemicals, such as bisphenol A, 4-nonylphenol, and 4-tert-octylphenol. During secondary treatment, steroidal hormones were removed to a higher degree than nonylphenol and bisphenol A. The total estrogenic activity was removed by an average of 96%. The remaining concentrations of targeted steroids in secondary effluents, except for estriol, still had the potential to elicit a positive response in the human breast cell cancer assay. For the majority of facilities, the remaining activity was likely attributed to residual concentrations of two steroidal hormones (17beta-estradiol and estriol).     

Determination of estrogenic compounds in wastewater using liquid chromatography-tandem mass spectrometry with electrospray and atmospheric pressure photoionization following desalting extraction

Two complementary LC-MS ionization methods, electrospray (ESI) and atmospheric pressure photoionization (APPI), have been optimized to determine three natural estrogenic compounds (estrone, 17beta-estradiol and estriol) and two synthetic estrogenic compounds (17alpha-ethynylestradiol and diethylstilbestrol) in the influent and effluent of wastewater treatment plants (WWTPs). The wastewater samples were first subjected to solid-phase extraction coupled with desalting extraction to remove matrix interference. The analytes were then detected using liquid chromatography-tandem mass spectrometry (LC-MS-MS) with ESI and dopant-assisted (DA) APPI to evaluate the ion suppression effect and to complement the detection and quantification of estrogenic compounds in complex wastewater samples. The average ion suppression factors for the extracts of the WWTP influent analyzed using ESI and APPI were 52+/-5% and 27+/-7%, respectively. The sensitivity and ionization efficiency of the LC-ESI-MS-MS system decreased dramatically when a complex matrix was present in the WWTP influent sample. Estrogenic compounds could be detected in the WWTP influent and effluent samples at concentrations below the parts-per-billion level. The lower detection limits obtained when using ESI and the higher matrix tolerance of the APPI method allowed the complete quantification of estrogenic compounds in very complex samples in a complementary manner.     

Input/output balance of estrogenic active compounds in a major municipal sewage plant in Germany

24 h samples of untreated and treated wastewater were taken in parallel from a modern municipal sewage plant in southern Germany in March and June 1998. After solid phase extraction, total estrogenic activity was quantitatively measured with a miniaturized E-screen assay and the levels of nine estrogenic phenolic chemicals analyzed by HRGC/LRMS. 17Beta-estradiol equivalent concentrations (EEQ) were 58 and 70 ng/l in the influent and 6 ng/l in the effluent, indicating that the load of estrogenic activity of the wastewater was reduced by about 90% in the sewage plant. Less than 3% of the estrogenic activity was found in the sludge. 4-t-octylphenol, 4-nonylphenol, bisphenol A, 2-hydroxybiphenyl, and 4-chloro-3-methylphenol were detected in the untreated wastewater at levels from 0.13 to 3.6 microg/l. 4-t-octylphenol, 4-nonylphenol, and bisphenol A were present in the effluent at concentrations from 0.16 to 0.36 microg/l, 2-hydroxybiphenyl and 4-chloro-3-methylphenol were not detectable. The contribution of the quantified levels of phenolic xenoestrogens to total estrogenic activity in the sewage was 0.7-4.3%.     

Occurrence of estrogenic effects in sewage and industrial wastewaters in Beijing, China

Estrogenic potencies of the effluents or water samples from wastewater treatment plants (WWTPs), industries and hospitals and some receiving rivers in Beijing city were estimated by using a human estrogen receptor recombinant yeast assay. Estrogenic activity of industrial wastewaters was found to range from 0.1 to 13.3 ng EEQ/L and decreased to the range of 0.03-1.6 ng EEQ/L after treatment. Estrogenic activity in WWTP influent ranged from 0.3 to 1.7 ng EEQ/L and decreased to the range of 0.05-0.5 ng EEQ/L after treatment. In the receiving river waters, the estrogenic effect range was 0.1-4.7 ng EEQ/L. These data suggest that treated industrial effluents and WWTP effluents of concern are not the only source of estrogenic pollution in surface waters in Beijing city. EEQ levels in Beijing river water are likely attributable to untreated municipal and industrial wastewaters discharged directly into the river.     

Comparison of the removal efficiency of endocrine disrupting compounds in pilot scale sewage treatment processes

The removal efficiency of endocrine disrupting compounds from effluents using pilot scale sewage treatment processes, including various treatment technologies, such as membrane bioreactors (MBR), nanofiltration (NF) and reverse osmosis (RO) for the purpose of water reuse, were estimated and compared. The calculated estrogenic activity, expressed in ng-EEQ/l, based on the concentration detected by GC/MS, and relative potencies for each target compound were compared to those measured using the E-screen assay. The removal efficiencies for nonylphenol, was within the range of 55-83% in effluents. High removal efficiencies of approximately >70% based on the detection limits were obtained for bisphenol A, E1, EE2 and genistein with each treatment processes, with the exception of E1 ( approximately 64%) using the MBR process. The measured EEQ values for the effluents from the MBR, NF and RO processes also indicated low estrogenic activities of 0.65, 0.23 and 0.05 ng-EEQ/l, respectively. These were markedly reduced values compared with the value of 1.2 ng-EEQ/l in influent. Consequently, the removals of EDCs in terms of the EEQ value from the biological and chemical determinations were sufficiently achieved by the treatment process applied in this study, especially in the cases of the NF and RO treatments.     

组合人工湿地处理工业园区污水厂尾水的中试研究

在巢湖流域水环境治理中,依托工业园区污水厂,进行了组合人工湿地处理工业园区污水厂尾水的中试研究。介绍了工艺流程和设计参数,运行结果表明,整个处理系统运行稳定,对COD、NH4+-N和TP的平均去除率分别为65.5%、75.5%和49.2%,其中一级潜流湿地对各污染物的去除贡献率最高。系统出水COD、氨氮、总磷基本达到了《地表水环境质量标准》(GB3838-2002)中的Ⅴ类水标准。此外还利用GC/MS初步对系统进出水进行了有机物组分分析,结果表明尾水中含有除草剂及农药中间体等难降解有机物,组合人工湿地对这些物质有一定去除效果。     

Physico-chemical treatments for the complete removal of non-ionic surfactants from effluents

Adsorption isotherms for a selection of non-ionic surfactants on activated carbons indicated the effectiveness of the latter in the removal of these pollutants from secondary effluents. The removal efficiencies were found to be improved when the secondary effluent was first flocculated with ferric chloride. This effectively removed some 80% of the non-ionic surfactant in the effluent. Batch adsorption experiments with powdered activated carbon removed 97% of the surfactant at low carbon dosage. A granular carbon with the best adsorption capacity was selected for continuous-flow operation in which non-ionic surfactants, COD and anionic surfactant alkyl benzene sulphonate were monitored. The breakthrough capacity for the non-ionic surfactants was in excess of 6000 bed volumes throughput of flocculated, sand-filtered effluent in a laboratory scale carbon column. Such a procedure is suggested for the complete removal of such pollutants from effluents.     

序批式反应器用于牛场污水的处理

对序批式反应器 (SBR)用于牛场污水的处理进行了试验研究 ,主要研究了三个水力停留时间 (HRT)和有机负荷率对污染物去除率、出水水质和污泥特性的影响。试验结果表明 ,对 10 0 0 0mg/LCOD牛场污水 ,使用 1dHRT ,相应有机负荷率为 10gCOD/L·d时 ,混合出水COD、TS、VS、TKN和TN的去除率分别为 45 %、2 1.4%、34 .2 %、5 3.2 %和 2 2 .2 % ,上清液出水的分别为 80 .2 %、6 3.4%、6 6 .2 %、75 %和 38.3% ;两种出水的SCOD和NH3 N去除率相同 ,分别为 5 0 .0 %和 76 .5 %。经SBR处理后 ,污泥的沉降浓缩性能也有了比较明显的改善。