城市污水处理厂内药品及个人护理品的赋存特征与去除机理
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摘要
近年来,药物及个人护理品(Pharmaceuticals and Personal Care Products, PPCPs)作为一类新兴的环境污染物,在多种环境介质中被频繁检出,以及对人体健康及生态环境具有一定的风险,引起了人们的广泛关注。我国对新兴污染物的研究正在逐渐兴起,现阶段缺乏PPCPs类污染物的排放标准及质量控制标准。污水处理厂是PPCPs类污染物进入环境的主要点源,同时也是去除这类污染物的重要途径。我国现有关于PPCPs类污染物的研究,大多集中在污水处理厂内PPCPs的赋存调研,物质对象上多关注于抗生素类PPCPs,而具体到实验室机理解析甚少。
本研究利用GC/MS和HPLC等高效分析检测手段,以多类别PPCPs为研究对象,揭示了PPCPs在城市污水处理厂中的存在特征与环境风险,并深入探究活性污泥对典型PPCPs的去除规律与机理。
通过为期三年的不间断跟踪监测,摸清了11种目标PPCPs在广东地区三家污水处理厂内的存在特征与环境风险。结果表明：目标PPCPs在城市污水处理厂内的检出率很高,浓度水平低于国外报道的浓度水平,与国内其他报道相近。生活污水是PPCPs的主要污染源。PPCPs的进水浓度主要与PPCPs的人为使用量及旱雨季相关。而其他各工艺段及出水中PPCPs的浓度变化一定程度上受限于进水浓度,而决定因素是各污水处理工艺段的去除效果。目标PPCPs的最大浓度值多出现在1月,最小浓度值多出现在7月。生物处理工艺对目标PPCPs的去除起主要的作用,厌氧池和好氧池是对城市污水处理厂内PPCPs总去除率贡献最大的污水处理单元,缺氧池内目标PPCPs的去除率多出现负值。风险评价表明,城市污水处理厂STP1出水中双氯芬酸对水生生物有高风险,水杨酸和甲芬那酸对水生生物有中等风险；城市污水处理厂STP3出水中氯贝酸和双氯芬酸对水生生物有中等风险；三氯生在三家污水处理厂中的出水浓度均对水生生物有高风险。
在活性污泥去除典型PPCPs的烧杯实验中,活性污泥对罗红霉素有显著的吸附作用,对苯扎贝特及萘普生有较强的生物降解作用。废水中的高浓度药品会对活性污泥系统产生急性毒性,罗红霉素致活性污泥急性毒性浓度值高于布洛芬。活性污泥降解萘普生和苯扎贝特的过程可以用伪一级动力学来进行描述,吸附过程可以用伪二级动力学方程描述。降解及吸附速率常数均与底物初始浓度存在一定的负线性相关性,活性污泥吸附目标污染物是目标物的疏水性及目标物与活性污泥间的静电反应共同起作用的结果,该吸附过程适用于Freundlich吸附等温线。活性污泥中萘普生解吸作用不明显,因此,剩余污泥的处理与处置过程中,萘普生不易造成环境的二次污染。
利用454高通量测序技术,了解了活性污泥系统中微生物群落结构与系统除污(目标PPCPs类污染物萘普生和常规污染物C/N/P)性能的耦合关系,降解萘普生的优势菌群主要集中在变形菌门的p变形菌纲。不同pH进水条件下,驯化后系统中形成的微生物菌落结构存在很大差异。酸性条件下形成的微生物群落能够更好地去除萘普生,但是系统的稳定性差,中性条件下驯化后系统中微生物的多样性程度较高,群落结构复杂,系统的抵抗力、稳定性较强,对于高浓度单一含萘普生的废水呈现较好的去除效果。
In recent years, pharmaceuticals and personal care products (PPCPs) as a kind of emerging environmental pollutants, have attracted widespread concerns due to the frequent detection in various environmental media and the potential risk to human health and ecological environment. The study of emerging contaminants in our country is gradually rise. At this stage, the pollutant emissions standards and quality control standards about this kind of pollutants are absent. Sewage treatment plants identified as the main point source of PPCPs into the environment, is also an important way for removing this type of pollutants. Most studies on the occurrence of PPCPs in our country have been evaluated by investigating the concentration of PPCPs in the sewage treatment plants, and few specific to the laboratory mechanism analysis. The object of these studies is mostly for antibiotic.
In this reseach, using GC/MS and HPLC detection means, we study the occurrence and environmental risks of PPCPs belonging to different therapeutic classes in full-scale sewage treatment plants, and the removal mechanism of to the typical PPCPs by activated sludge in the laboratory.
The concentrations of eleven kinds of target PPCPs in the three sewage treatment plants in Guangdong were monitored over the course of three years, to gain an insight into the occurrence and environmental risks. The results showed that the detection rates of the target PPCPs in the three sewage treatment plants were very high, and the concentration levels were lower than those in the other countries and similar with the other domestic reports. The main source of PPCPs in the water environment was identified as domestic wastewater. The influent concentrations of PPCPs were mainly associated with the human use and the rainy season. The concentrations of PPCPs in sewage treatment units and effluent were restricted to feed concentrations and determined by the removal effects of the sewage treatment units. The maximum concentrations mainly occured in January, while the minimum in July. Biological treatment process played a main role in the total removal efficiencies. Anaerobic tank and aerobic tank were beneficial to remove of PPCPs, and anoxic tank often appeared negative removal rates. Risk assessment showed that diclofenac could pose a high risk to aquatic organisms in the effluent of sewage treatment plant STP1, and salicylic acid and mefenamic acid could pose a medium risk to aquatic organisms. In sewage treatment plant STP3, clofibrate and diclofenac could pose a medium risk to aquatic organisms. Triclosan could pose a high risk to aquatic organisms in the three sewage treatment plants.
This study investigated the degradation characteristics of three acidic pharmaceuticals (naproxen, benzafibrate and ibuprofen) and roxithromycin in the presence of activated sludge under aerobic and anoxic conditions. Experimental results indicated that roxithromycin was significantly adsorbed by activated sludge, and the effective biodegradation of benzafibrate and naproxen was observed both under aerobic and anoxic conditions. The concentration of roxithromycin leading to acute toxicity on activated sludge was higher than that of ibuprofen. The degradation of naproxen and benzafibrate could be described by pseudo first-order kinetic model, while the adsorption data could be well interpreted by pseudo second-order kinetic model. The spiked concentrations of the two-target compounds were negatively correlated with degradation and adsorption rate constant. The adsorption of pharmaceuticals by activated sludge was rapid, and the relative adsorbabilties of the two-target compounds based on their log Kow and pKa values. The adsorption process of naproxen in activated sludge was suitable for the Freundlich adsorption isotherm. Desorption effect of naproxen was not obvious, therefore naproxen was not easy to cause secondary pollution to the environment in the excess sludge treatment and disposal process.
Using454high-throughput sequencing technology, we realized the coupling relationship between the microbial community structure and the capacity of decontamination in activated sludge system. The bacterium group achieved advantage degradation of naproxen were mainly classified as Betaproteobacteria. There are considerable differences of the microbial community structure between different pH conditions in the domestication system. Under the acid condition, the system could better remove naproxen, but poor stability. The high levels of naproxen removal from the high concentration wastewater only containing naproxen was achieved by the domestication system under neutral condition, and the system had complexity and diversity of microbial ecology.
本研究利用GC/MS和HPLC等高效分析检测手段,以多类别PPCPs为研究对象,揭示了PPCPs在城市污水处理厂中的存在特征与环境风险,并深入探究活性污泥对典型PPCPs的去除规律与机理。
通过为期三年的不间断跟踪监测,摸清了11种目标PPCPs在广东地区三家污水处理厂内的存在特征与环境风险。结果表明：目标PPCPs在城市污水处理厂内的检出率很高,浓度水平低于国外报道的浓度水平,与国内其他报道相近。生活污水是PPCPs的主要污染源。PPCPs的进水浓度主要与PPCPs的人为使用量及旱雨季相关。而其他各工艺段及出水中PPCPs的浓度变化一定程度上受限于进水浓度,而决定因素是各污水处理工艺段的去除效果。目标PPCPs的最大浓度值多出现在1月,最小浓度值多出现在7月。生物处理工艺对目标PPCPs的去除起主要的作用,厌氧池和好氧池是对城市污水处理厂内PPCPs总去除率贡献最大的污水处理单元,缺氧池内目标PPCPs的去除率多出现负值。风险评价表明,城市污水处理厂STP1出水中双氯芬酸对水生生物有高风险,水杨酸和甲芬那酸对水生生物有中等风险；城市污水处理厂STP3出水中氯贝酸和双氯芬酸对水生生物有中等风险；三氯生在三家污水处理厂中的出水浓度均对水生生物有高风险。
在活性污泥去除典型PPCPs的烧杯实验中,活性污泥对罗红霉素有显著的吸附作用,对苯扎贝特及萘普生有较强的生物降解作用。废水中的高浓度药品会对活性污泥系统产生急性毒性,罗红霉素致活性污泥急性毒性浓度值高于布洛芬。活性污泥降解萘普生和苯扎贝特的过程可以用伪一级动力学来进行描述,吸附过程可以用伪二级动力学方程描述。降解及吸附速率常数均与底物初始浓度存在一定的负线性相关性,活性污泥吸附目标污染物是目标物的疏水性及目标物与活性污泥间的静电反应共同起作用的结果,该吸附过程适用于Freundlich吸附等温线。活性污泥中萘普生解吸作用不明显,因此,剩余污泥的处理与处置过程中,萘普生不易造成环境的二次污染。
利用454高通量测序技术,了解了活性污泥系统中微生物群落结构与系统除污(目标PPCPs类污染物萘普生和常规污染物C/N/P)性能的耦合关系,降解萘普生的优势菌群主要集中在变形菌门的p变形菌纲。不同pH进水条件下,驯化后系统中形成的微生物菌落结构存在很大差异。酸性条件下形成的微生物群落能够更好地去除萘普生,但是系统的稳定性差,中性条件下驯化后系统中微生物的多样性程度较高,群落结构复杂,系统的抵抗力、稳定性较强,对于高浓度单一含萘普生的废水呈现较好的去除效果。
In recent years, pharmaceuticals and personal care products (PPCPs) as a kind of emerging environmental pollutants, have attracted widespread concerns due to the frequent detection in various environmental media and the potential risk to human health and ecological environment. The study of emerging contaminants in our country is gradually rise. At this stage, the pollutant emissions standards and quality control standards about this kind of pollutants are absent. Sewage treatment plants identified as the main point source of PPCPs into the environment, is also an important way for removing this type of pollutants. Most studies on the occurrence of PPCPs in our country have been evaluated by investigating the concentration of PPCPs in the sewage treatment plants, and few specific to the laboratory mechanism analysis. The object of these studies is mostly for antibiotic.
In this reseach, using GC/MS and HPLC detection means, we study the occurrence and environmental risks of PPCPs belonging to different therapeutic classes in full-scale sewage treatment plants, and the removal mechanism of to the typical PPCPs by activated sludge in the laboratory.
The concentrations of eleven kinds of target PPCPs in the three sewage treatment plants in Guangdong were monitored over the course of three years, to gain an insight into the occurrence and environmental risks. The results showed that the detection rates of the target PPCPs in the three sewage treatment plants were very high, and the concentration levels were lower than those in the other countries and similar with the other domestic reports. The main source of PPCPs in the water environment was identified as domestic wastewater. The influent concentrations of PPCPs were mainly associated with the human use and the rainy season. The concentrations of PPCPs in sewage treatment units and effluent were restricted to feed concentrations and determined by the removal effects of the sewage treatment units. The maximum concentrations mainly occured in January, while the minimum in July. Biological treatment process played a main role in the total removal efficiencies. Anaerobic tank and aerobic tank were beneficial to remove of PPCPs, and anoxic tank often appeared negative removal rates. Risk assessment showed that diclofenac could pose a high risk to aquatic organisms in the effluent of sewage treatment plant STP1, and salicylic acid and mefenamic acid could pose a medium risk to aquatic organisms. In sewage treatment plant STP3, clofibrate and diclofenac could pose a medium risk to aquatic organisms. Triclosan could pose a high risk to aquatic organisms in the three sewage treatment plants.
This study investigated the degradation characteristics of three acidic pharmaceuticals (naproxen, benzafibrate and ibuprofen) and roxithromycin in the presence of activated sludge under aerobic and anoxic conditions. Experimental results indicated that roxithromycin was significantly adsorbed by activated sludge, and the effective biodegradation of benzafibrate and naproxen was observed both under aerobic and anoxic conditions. The concentration of roxithromycin leading to acute toxicity on activated sludge was higher than that of ibuprofen. The degradation of naproxen and benzafibrate could be described by pseudo first-order kinetic model, while the adsorption data could be well interpreted by pseudo second-order kinetic model. The spiked concentrations of the two-target compounds were negatively correlated with degradation and adsorption rate constant. The adsorption of pharmaceuticals by activated sludge was rapid, and the relative adsorbabilties of the two-target compounds based on their log Kow and pKa values. The adsorption process of naproxen in activated sludge was suitable for the Freundlich adsorption isotherm. Desorption effect of naproxen was not obvious, therefore naproxen was not easy to cause secondary pollution to the environment in the excess sludge treatment and disposal process.
Using454high-throughput sequencing technology, we realized the coupling relationship between the microbial community structure and the capacity of decontamination in activated sludge system. The bacterium group achieved advantage degradation of naproxen were mainly classified as Betaproteobacteria. There are considerable differences of the microbial community structure between different pH conditions in the domestication system. Under the acid condition, the system could better remove naproxen, but poor stability. The high levels of naproxen removal from the high concentration wastewater only containing naproxen was achieved by the domestication system under neutral condition, and the system had complexity and diversity of microbial ecology.
引文
[1]Murray K E, Thomas S M, Bodour A A. Prioritizing research for trace pollutants and emerging contaminants in the freshwater environment. Environmental Pollution,2010,158 (12):3462-3471
[2]Kleywegt S, Pileggi V, Yang P, et al. Pharmaceuticals, hormones and bisphenol A in untreated source and finished drinking water in Ontario, Canada-Occurrence and treatment efficiency. Science of The Total Environment,2011, 409 (8):1481-1488
[3]Peng X, Yu Y, Tang C, et al. Occurrence of steroid estrogens, endocrine disrupting phenols, and acid pharmaceutical residues in urban riverine water of the Pearl River Delta, South China. Science of The Total Environment,2008, 397(1-3):158-166
[4]Tauxe Wuersch A, De Alencastro L F, Grandjean D, et al. Occurrence of several acidic drugs in sewage treatment plants in Switzerland and risk assessment. Water Research,2005,39 (9):1761-1772
[5]Richardson S D. Water analysis:emerging contaminants and current issues. Anal Chem,2009 (12):46-55
[6]Daughton C G, Ternes T A. Pharmaceuticals and personal care products in the environment:agents of subtle change? Environmental Health Perspectives,1999 (107):907-938
[7]China IRN (China Industry Research Net).2012-2013 personal care product market development analysis,2012
[8]BosiData (Bosi Data Research Center).2010-2013 personal care product market of China and investment prospect analysis,2011
[9]Kummerer k. (2004)Pharmaceuticals in the environment sources, fate, effect and risks. Berlin, Heidelberg, New York:Springer
[10]Liu J L, Wong M H. Pharmaceuticals and personal care products (PPCPs):A review on environmental contamination in China. Environment International, 2013,59 (0):208-224
[11]Jian Liang Z, Guang Guo Y, Li W, et al. Determination of phenolic endocrine disrupting chemicals and acidic pharmaceuticals in surface water of the Pearl Rivers in South China by gas chromatography negative chemical ionization mass spectrometry. Science of The Total Environment,2009, (407):962-974
[12]Desbrow C, Routledge E J, Brighty J P. Identification of estrogenic chemicals in STW effluent.2.In vivo responses in trout and roach. Environmental Toxicology and Chemistry,1998:1559-1565
[13]Kramer V J, Miles Richardson S, Pierens S L. Reproductive impairment and induction of alkaline labile phosphate, a biomarker of estrogen exposure, in fathead minnows (Pimephales promelas) exposed to waterborne 17β-estradiol. Aquatic Toxicology,1998:335-360
[14]Gimeno S, Komen H, Venderbosch Paul W M. Disruption of sexual differentiation in genetic male common carp (Cyprinous carpio) exposed to an alkylphenol during different life stages. Environmental Science and Technology, 1997,(10):2884-2890
[15]Pomati F, Castiglioni S, Zuccato E, et al. Effects of a Complex Mixture of Therapeutic Drugs at Environmental Levels on Human Embryonic Cells. Environmental Science & Technology,2006,40 (7):2442-2447
[16]Gravel A, Vijayan M M. Salicylate disrupts interrenal steroidogenesis and brain glucocorticoid receptor expression in rainbow trout. Toxicological Sciences, 2006,93 (1):41-49
[17]Oaks J L, Gilbert M, Virani M Z, et al. Diclofenac residues as the cause of vulture population decline in Pakistan. Nature,2004,427 (6975):630-633
[18]Ollaboration Cat N T C. Vascular and upper gastrointestinal effects of non-steroidal anti-inflammatory drugs:meta-analyses of individual participant data from randomised trials. The Lancet,2013
[19]Cleuvers M. Mixture toxicity of the anti-inflammatory drugs diclofenac, ibuprofen, naproxen, and acetylsalicylic acid. Ecotoxicology and Environmental Safety,2004,59(3):309-315
[20]Andreozzi R, Caprio V, Ciniglia C, et al. Antibiotics in the environment: occurrence in Italian STPs, fate, and preliminary assessment on algal toxicity of amoxicillin. Environmental Science and Technology,2004,38 (24):6832-6838
[21]Lin A Y C, Yu T H, Lin C F. Pharmaceutical contamination in residential, industrial, and agricultural waste streams:risk to aqueous environments in Taiwan. Chemosphere,2008,74 (1):131-141
[22]Brillas E, Garcia-Segura S, Skoumal M, et al. Electrochemical incineration of diclofenac in neutral aqueous medium by anodic oxidation using Pt and boron-doped diamond anodes. Chemosphere,2010,79 (6):605-612
[23]何建国,齐红娟,许志强.高度重视药物不良反应.中国医药卫生,2007,8(6)：72-73
[24]Sanderson H, Johnson D J, Wilson C J, et al. Probabilistic hazard assessment of environmentally occurring pharmaceuticals toxicity to fish, daphnids and algae by ECOSAR screening. Toxicology Letters,2003,144 (3):383-395
[25]Ferrari B, Paxeus N, Lo Giudice R, et al. Ecotoxicological impact of pharmaceuticals found in treated wastewaters:study of carbamazepine, clofibric acid, and diclofenac. Ecotox Environ Safe,2003 (55):359-370
[26]Rosal R, Gonzalo MS, Boltes K, et al. Identification of intermediates and assessment of ecotoxicity in the oxidation products generated during the ozonation of clofibric acid. J Hazard Mater,2009 (172):1061-1068
[27]Cleuvers M. Aquatic ecotoxicity of pharmaceuticals including the assessment of combination effects. Toxicol Lett,2003 (142):185-194
[28]Ferrari B, Mons R, Vollat B, et al. Environmental risk assessment of six human pharmaceuticals:are the current environmental risk assessment procedures sufficient for the protection of the aquatic environment? Environ Toxicol Chem, 2004(23):1344-1354
[29]Ra J S, Oh S Y, Lee B C, et al. The effect of suspended particles coated by humic acid on the toxicity of pharmaceuticals, estrogens, and phenolic compounds. Environ Int,2008 (34):184-192
[30]Farre M, Ferrer I, Ginebreda A, et al. Determination of drugs in surface water and wastewater samples by liquid chromatography mass spectrometry:methods and preliminary results including toxicity studies with Vibro fisheri. J Chromatogr A,2001 (938):187-197
[31]Hailing Sorensen B. Algal toxicity of antibacterial agents used in intensive farming. Chemosphere,2000 (40):731-739
[32]Quinn B, Gagne F, Blaise C. An investigation into the acute and chronic toxicity of eleven pharmaceuticals (and their solvents) found in wastewater effluent on the cnidarians, Hydra attenuate. Sci Total Environ,2008 (389):306-314
[33]Boillot C. Evaluation des risques ecotoxicologiques lies aux rejets d'effluents hospitaliers dans les milieux aquatiques. Contribution a l'amelioration de la phase "caraterisation des effets". PhD Thesis. Institut National des Sciences Appliquees de Lyon, France, N°d'ordre 2008 ISAL 0021
[34]Cleuvers M. Mixture toxicity of the anti-inflammatory drugs diclofenac, ibuprofen, naproxen, and acetylsalicylic acid. Ecotox Environ Safe,2004 (5): 309-315
[35]Kim S, Cho J, Kim I, et al. Occurrence and removal of pharmaceuticals and endocrine disruptors in South Korean surface, drinking and wastewaters. Water Res,2007(41):1013-1021
[36]Jones O A H, Voulvoulis N, Lester J N. Aquatic environmental assessment of the top 25 English prescription pharmaceuticals. Water Res,2002 (36): 5013-5022
[37]Jiang M, Wang L, Ji R. Biotic and abiotic degradation of four cephalosporin antibiotics in a lake surface water and sediment. Chemosphere,2010,80 (11): 1399-1405
[38]Zhang S, Zhang Q, Darisaw S, et al. Simultaneous quantification of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and pharmaceuticals and personal care products (PPCPs) in Mississippi river water, in New Orleans, Louisiana, USA. Chemosphere,2007,66 (6):1057-1069
[39]Wang L, Ying G G, Zhao J L, et al. Occurrence and risk assessment of acidic pharmaceuticals in the Yellow River, Hai River and Liao River of north China. Science of The Total Environment,2010,408 (16):3139-3147
[40]Zhao J L, Ying G G, Wang L, et al. Determination of phenolic endocrine disrupting chemicals and acidic pharmaceuticals in surface water of the Pearl Rivers in South China by gas chromatography negative chemical ionization-mass spectrometry. Science of The Total Environment,2009,407 (2): 962-974
[41]胡洪营,王超,郭美婷.药品和个人护理用品PPCPs对环境的污染现状与研究进展.生态环境,2005,14(6)：947-952
[42]Teijon G, Candela L, Tamoh K, et al. Occurrence of emerging contaminants, priority substances (2008/105/CE) and heavy metals in treated wastewater and groundwater at Depurbaix facility (Barcelona, Spain). Science of The Total Environment,2010,408 (17):3584-3595
[43]Yiruhan, Wang Q J, Mo C H, et al. Determination of four fluoroquinolone antibiotics in tap water in Guangzhou and Macao. Environmental Pollution, 2010,158(7):2350-2358
[44]McClellan K, Halden R U. Pharmaceuticals and personal care products in archived U.S. biosolids from the 2001 EPA national sewage sludge survey. Water Research,44 (2):658-668
[45]Chen F, Ying G G, Kong L X, et al. Distribution and accumulation of endocrine-disrupting chemicals and pharmaceuticals in wastewater irrigated soils in Hebei, China. Environmental Pollution,2011,159 (6):1490-1498
[46]Joss A, Keller E, Alder A C, et al. Removal of pharmaceuticals and fragrances in biological wastewater treatment. Water Research,2005,39 (14):3139-3152
[47]Zhang Y, GeiBen S U. In vitro degradation of carbamazepine and diclofenac by crude lignin peroxidase. Journal of Hazardous Materials,2010,176 (1-3): 1089-1092
[48]Volkova N, Ibrahim V, Hatti-Kaul R. Laccase catalysed oxidation of syringic acid:Calorimetric determination of kinetic parameters. Enzyme Microb Tech, 2012,50 (4-5):233-237
[49]Yu Z, Peldszus S, Huck P M. Adsorption characteristics of selected pharmaceuticals and an endocrine disrupting compound—Naproxen, carbamazepine and nonylphenol—on activated carbon. Water Research,2008, 42 (12):2873-2882
[50]Melillo M, Phillips G J, Davies J G, et al. The effect of protein binding on ibuprofen adsorption to activated carbons. Carbon,2004,42 (3):565-571
[51]Hasan Z, Jeon J, Jhung S H. Adsorptive removal of naproxen and clofibric acid from water using metal-organic frameworks. Journal of Hazardous Materials, 2012,209-210(0):151-157
[52]Li W, Lu S, Qiu Z, et al. Clofibric acid degradation in UV254/H2O2 process: Effect of temperature. Journal of Hazardous Materials,2010,176 (1-3): 1051-1057
[53]De Schepper W, Dries J, Geuens L, et al. A kinetic model for multicomponent wastewater substrate removal by partial ozonation and subsequent biodegradation. Water Research,2010,44 (18):5488-5498
[54]Esplugas S, Bila D M, Krause L G T, et al. Ozonation and advanced oxidation technologies to remove endocrine disrupting chemicals (EDCs) and Pharmaceuticals and personal care products (PPCPs) in water effluents. Journal of Hazardous Materials,2007,149 (3):631-642
[55]Kim I, Tanaka H. Photodegradation characteristics of PPCPs in water with UV treatment. Environment International,2009,35 (5):793-802
[56]Kim I, Yamashita N, Tanaka H. Photodegradation of Pharmaceuticals and personal care products during UV and UV/H2O2 treatments. Chemosphere,2009, 77(4):518-525
[57]Alvarez P M, Jaramillo J, Lopez Pinro F, et al. Preparation and characterization of magnetic TiO2 nanoparticles and their utilization for the degradation of emerging pollutants in water. Applied Catalysis B:Environmental,2010,100 (1-2):338-345
[58]Mendez Arriaga F, Torres Palma R A, Pettier C, et al. Ultrasonic treatment of water contaminated with ibuprofen. Water Research,2008,42 (16):4243-4248
[59]Wang Y, Zhang H, Chen L, et al. Ozonation combined with ultrasound for the degradation of tetracycline in a rectangular air-lift reactor. Separation and Purification Technology,2012,84:138-146
[60]Trovo Alam G, Nogueira R F P, Agiiera A, et al. Degradation of sulfamethoxazole in water by solar photo-Fenton. Chemical and toxicological evaluation. Water Research,2009,43 (16):3922-3931
[61]Coelho A D, Sans C, Agiiera A, et al. Effects of ozone pre-treatment on diclofenac:Intermediates, biodegradability and toxicity assessment. Science of The Total Environment,2009,407 (11):3572-3578
[62]Al-Rifai J H, Khabbaz H, Schafer A I. Removal of pharmaceuticals and endocrine disrupting compounds in a water recycling process using reverse osmosis systems. Separation and Purification Technology,77 (1):60-67
[63]Gros M, Petrovic M, Ginebreda A, et al. Removal of pharmaceuticals during wastewater treatment and environmental risk assessment using hazard indexes. Environment International,2010,36 (1):15-26
[64]Lishman L, Smyth S A, Sarafin K, et al. Occurrence and reductions of pharmaceuticals and personal care products and estrogens by municipal wastewater treatment plants in Ontario, Canada. Science of The Total Environment,2006,367 (2-3):544-558
[65]Verlicchi P, Al Aukidy M, Zambello E. Occurrence of pharmaceutical compounds in urban wastewater:Removal, mass load and environmental risk after a secondary treatment—A review. Science of The Total Environment,2012, 429:123-155
[66]Xue W, Wu C, Xiao K, et al. Elimination and fate of selected micro-organic pollutants in a full-scale anaerobic/anoxic/aerobic process combined with membrane bioreactor for municipal wastewater reclamation. Water Research, 2010,44(20):5999-6010
[67]Lin A Y C, Yu T H, Lateef S K. Removal of pharmaceuticals in secondary wastewater treatment processes in Taiwan. Journal of Hazardous Materials, 2009,167(1-3):1163-1169
[68]Leung H W, Minh T B, Murphy M B, et al. Distribution, fate and risk assessment of antibiotics in sewage treatment plants in Hong Kong, South China. Environment International,2012,42 (0):1-9
[69]Gulkowska A, Leung H W, So M K, et al. Removal of antibiotics from wastewater by sewage treatment facilities in Hong Kong and Shenzhen, China. Water Research,2008,42 (1-2):395-403
[70]Xu W H, Zhang G, Zou S C, et al. Determination of selected antibiotics in the Victoria Harbour and the Pearl River, South China using high performance liquid chromatography electrospray ionization tandem mass spectrometry. Environmental Pollution,2007,145 (3):672-679
[71]Jelic A, Gros M, Ginebreda A, et al. Occurrence, partition and removal of pharmaceuticals in sewage water and sludge during wastewater treatment. Water Research,2011,45 (3):1165-1176
[72]Gobel A, McArdell C S, Joss A, et al. Fate of sulfonamides, macrolides, and trimethoprim in different wastewater treatment technologies. Science of The Total Environment,2007,372 (2-3):361-371
[73]Clara M, Strenn B, Gans O, et al. Removal of selected pharmaceuticals, fragrances and endocrine disrupting compounds in a membrane bioreactor and conventional wastewater treatment plants. Water Research,2005,39 (19): 4797-4807
[74]Jia A, Wan Y, Xiao Y, et al. Occurrence and fate of quinolone and fluoroquinolone antibiotics in a municipal sewage treatment plant. Water Research,2012,46 (2):387-394
[75]Bernhard M, Muller J, Knepper T P. Biodegradation of persistent polar pollutants in wastewater:Comparison of an optimised lab-scale membrane bioreactor and activated sludge treatment. Water Research,2006,40 (18): 3419-3428
[76]Joss A, Zabczynski S, Gobel A, et al. Biological degradation of pharmaceuticals in municipal wastewater treatment:Proposing a classification scheme. Water Research,2006,40 (8):1686-1696
[77]Tunkel J, Howard P H, Boethling R S, et al. Predicting ready biodegradability in the Japanese ministry of international trade and industry test. Environ Toxicol Chem,2000,19:2478-2485
[78]Jones O A H, Voulvoulis N, Lester J N. The occurrence and removal of selected pharmaceutical compounds in a sewage treatment works utilising activated sludge treatment. Environmental Pollution,2007,145 (3):738-744
[79]Hai F I, Tessmer K, Nguyen L N, et al. Removal of micropollutants by membrane bioreactor under temperature variation. J Membrane Sci,2011,383 (1-2):144-151
[80]Suarez S, Lema J M, Omil F. Removal of Pharmaceutical and Personal Care Products (PPCPs) under nitrifying and denitrifying conditions. Water Research, 2010,44(10):3214-3224
[81]Carballa M, Omil F, Ternes T, et al. Fate of pharmaceutical and personal care products (PPCPs) during anaerobic digestion of sewage sludge. Water Research, 2007,41 (10):2139-2150
[82]Tadkaew N, Sivakumar M, Khan S J, et al. Effect of mixed liquor pH on the removal of trace organic contaminants in a membrane bioreactor. Bioresource Technology,2010,101 (5):1494-1500
[83]Urase T, Kagawa C, Kikuta T. Factors affecting removal of pharmaceutical substances and estrogens in membrane separation bioreactors. Desalination, 2005,178(1-3):107-113
[84]Clara M, Kreuzinger N, Strenn B, et al. The solids retention time—a suitable design parameter to evaluate the capacity of wastewater treatment plants to remove micropollutants. Water Research,2005,39 (1):97-106
[85]Lesjean B, Gnirss R, Buisson H, et al. Outcomes of a 2-year investigation on enhanced biological nutrients removal and trace organics elimination in membrane bioreactor (MBR). Water Sci Technol,2005,52 (10-11):453-460
[86]Kreuzinger N, Clara M, Strenn B, et al. Relevance of the sludge retention time (SRT) as design criteria for wastewater treatment plants for the removal of endocrine disruptors and pharmaceuticals from wastewater. Water Sci Technol, 2004,50(5):149-156
[87]Koch G, Kuhni M, Siegrist H. Calibration and validation of an ASM3-based steady-state model for activated sludge systems—part I:prediction of nitrogen removal and sludge production. Water Research,2001,35 (9):2235-2245
[88]Majewsky M, Gall T, Yargeau V, et al. Active heterotrophic biomass and sludge retention time (SRT) as determining factors for biodegradation kinetics of pharmaceuticals in activated sludge. Bioresource Technology,2011,102 (16): 7415-7421
[89]Maria Chiara Pietrogrande G B. GC-MS analytical methods for the determination of personal-care products in water matrices. Trends in Analytical Chemistry,2007,26(11):1086-1094
[90]Fang T H, Nan F H, Chin T S, et al. The occurrence and distribution of pharmaceutical compounds in the effluents of a major sewage treatment plant in Northern Taiwan and the receiving coastal waters. Mar Pollut Bull,2012,64 (7): 1435-1444
[91]Sui Q, Huang J, Deng S, et al. Seasonal Variation in the Occurrence and Removal of Pharmaceuticals and Personal Care Products in Different Biological Wastewater Treatment Processes. Environmental Science and Technology,2011, 45 (8):3341-3348
[92]Ort C, Lawrence M G, Rieckermann J, et al. Sampling for Pharmaceuticals and Personal Care Products (PPCPs) and Illicit Drugs in Wastewater Systems:Are Your Conclusions Valid? A Critical Review. Environmental Science and Technology,2010,44 (16):6024-6035
[93]Glelt, A. Estimation for small normal data sets with detection limits. Environ Sci Technol,1985,19:1201-1208
[94]Reemtsma T, Weiss S, Mueller J, et al. Polar pollutants entry into the water cycle by municipal wastewater:A European perspective. Environ Sci Technol, 2006,40,5451-5458
[95]Gabet Giraud V, Miege C, Choubert J M, et al. Occurrence and removal of estrogens and beta blockers by various processes in wastewater treatment plants. Science of The Total Environment,2010,408 (19):4257-4269
[96]Wick A, Fink G, Joss A, et al. Fate of beta blockers and psycho-active drugs in conventional wastewater treatment. Water Research,2009,43 (4):1060-1074
[97]Sui Q, Huang J, Deng S, et al. Occurrence and removal of pharmaceuticals, caffeine and DEET in wastewater treatment plants of Beijing, China. Water Research,2010,44 (2):417-426
[98]Kosma C I, Lambropoulou D A, Albanis T A. Occurrence and removal of PPCPs in municipal and hospital wastewaters in Greece. Journal of Hazardous Materials,2010,179 (1-3):804-817
[99]Brennan P J, Greenberg G, Miall W E, Thompson S G. Seasonal variation in arterial blood pressure. British Medical Journal (Clinical research ed.),1982, 285 (6346):919-923
[100]Ziylan A, Ince N H. The occurrence and fate of anti-inflammatory and analgesic pharmaceuticals in sewage and fresh water:Treatability by conventional and non-conventional processes. Journal of Hazardous Materials,187 (1-3):24-36
[101]Kimura K, Hara H, Watanabe Y. Removal of pharmaceutical compounds by submerged membrane bioreactors (MBRs). Desalination,2005,178:135-140
[102]Zorita S, Martensson L, Mathiasson L. Occurrence and removal of pharmaceuticals in municipal sewage treatment system in the south of Sweden. Sci Total Environ,2009,407:2760-2770
[103]Roberts P H, Thomas K V. The occurrence of selected pharmaceuticals in wastewater effluent and surface waters of the lower Tyne catchment. Sci Total Environ,2006,356:143-153
[104]Joss A, Andersen H, Ternes T, et al. Removal of Estrogens in Municipal Wastewater Treatment under Aerobic and Anaerobic Conditions:Consequences for Plant Optimization. Environmental Science and Technology 38 (11),3047-3055,2004,38 (11): 3047-3055
[105]Radjenovic J, Petrovic M, Barcel D. Advanced mass spectrometric methods applied to the study of fate and removal of pharmaceuticals in wastewater treatment. TrAC Trends in Analytical Chemistry,2007,26 (11):1132-1144
[106]Vieno N, Tuhkanen T, Kronberg L. Elimination of pharmaceuticals in sewage treatment plants in Finland. Water Res,2007,41:1001-1012
[107]Li W, Guang Guo Y, Jian Liang Z, et al. Assessing estrogenic activity in surface water and sediment of the Liao River system in northeast China using combined chemical and biological tools. Environmental Pollution,2011,159:148-156
[108]Wang B, Yu G, Huang J, et al. Tiered aquatic ecological risk assessment of organochlorine pesticides and their mixture in Jiangsu reach of Huaihe River, China. Environ Monit Assess,2009,157:29-42
[109]Backhaus T, Scholze M, Grimme L H. The single substance and mixture toxicity of quinolones to the bioluminescent bacterium Vibrio fischeri. Aquat Toxicol, 2000,49:49-61
[110]Zhao J L, Ying G G, Liu Y S, et al. Occurrence and a screening-level risk assessment of human pharmaceuticals in the Pearl River system, South China. Environmental Toxicology and Chemistry,2010,29 (6):1377-1384
[111]Escher B I, Baumgartner R, Koller M, et al. Environmental toxicology and risk assessment of pharmaceuticals from hospital wastewater. Water Research,2011, 45 (1):75-92
[112]Boyd G R, Palmeri J M, Zhang S, et al. Pharmaceuticals and personal care products (PPCPs) and endocrine disrupting chemicals (EDCs) in stormwater canals and Bayou St. John in New Orleans, Louisiana, USA. Science of The Total Environment,2004,333 (1-3):137-148
[113]Calderon Preciado D, Jimenez Cartagena C, Matamoros V, et al. Screening of 47 organic microcontaminants in agricultural irrigation waters and their soil loading. Water Research,45 (1):221-231
[114]Lissemore L, Hao C, Yang P, et al. An exposure assessment for selected pharmaceuticals within a watershed in Southern Ontario. Chemosphere,2006, 64 (5):717-729
[115]Fent K, Weston A A, Caminada D. Ecotoxicology of human pharmaceuticals. Aquatic Toxicology,2006,76 (2):122-159
[116]Maria H V, Victor M, Javier M V, et al. Assessment of full-scale natural systems for the removal of PPCPs from wastewater in small communities. Water Research,2010,44 (5):1429-1439
[117]APHA-AWWA-WPCF. StandardMethods for the Examination ofWater andWastewater,20th ed. American Public Health Association,Washington DC, USA,2001
[118]Sipma J, Osuna B, Collado N, et al. Comparison of removal of pharmaceuticals in MBR and activated sludge systems. Desalination,2010,250 (2):653-659
[119]Yang S F, Lin C F, Yu C, et al. Sorption and biodegradation of sulfonamide antibiotics by activated sludge:Experimental assessment using batch data obtained under aerobic conditions. Water Research,2011,45 (11):3389-3397
[120]Cheung W H, Szeto Y S, McKay G. Intraparticle diffusion processes during acid dye adsorption onto chitosan. Bioresource Technology,2007,98 (15): 2897-2904
[121]Blanquez P, Casas N, Font X, et al. Mechanism of textile metal dye biotransformation by Trametes versicolor. Water Research,2004,38 (8): 2166-2172
[122]Ni B J, Yu H Q, Sun Y J. Modeling simultaneous autotrophic and heterotrophic growth in aerobic granules. Water Research,2008,42 (6-7):1583-1594
[123]Kraigher B, Kosjek T, Heath E, et al. Influence of pharmaceutical residues on the structure of activated sludge bacterial communities in wastewater treatment bioreactors. Water Research,2008,42 (17):4578-4588
[124]Marco Urrea E, Perez Trujillo M, Blanquez P, et al. Biodegradation of the analgesic naproxen by Trametes versicolor and identification of intermediates using HPLC-DAD-MS and NMR. Bioresource Technology,2010,101 (7): 2159-2166
[125]Parris G E. Covalent binding of aromatic amines to humates.1. Reactions with carbonyls and quinones. Environmental Science and Technology,1980,14 (9): 1099-1106
[126]Weber E J, Spidle D L, Thorn K A. Covalent Binding of Aniline to Humic Substances.1. Kinetic Studies. Environmental Science and Technology,1996, 30 (9):2755-2763
[127]Shen R, Andrews S A. NDMA formation kinetics from three pharmaceuticals in four water matrices. Water Research,2011,45 (17):5687-5694
[128]Caporaso J G, Kuczynski J. et al. QIIME allows analysis of high throughput community sequencing data. Nature Methods,2010,7 (5):335-336
[129]Quast C, Pruesse E, Yilmaz P, et al. The SILVA ribosomal RNA gene database project:improved data processing and web-based tools. Nucl Acids Res,2013, 41 (1):590-596
[130]Tsai Y P, You S J, Pai T Y, et al. Effect of cadmium on composition and diversity of bacterial communities in activated sludges. Int Biodeter Biodegr, 2005,55:285-291
[131]Wong M T, Mino T, Seviour R J, et al. In situ identification and characterization of the microbial community structure of full-scale enhanced biological phosphorous removal plants in Japan. Water Res,2005,39:2901-2914
[132]Wagner M, Loy A. Bacterial community composition and function in sewage treatment systems. Curr Opin Biotech,2002,13:218-227
[133]Lee N, Nielsen P H, Aspegren H, et al. Long-term population dynamics and in situ physiology in activated sludge systems with enhanced biological phosphorus removal operated with and without nitrogen removal. Syst Appl Microbiol,2003,26:211-227
[134]Miller D N, Smith R L. Microbial characterization of nitrification in a shallow, nitrogen-contaminated aquifer, Cape Cod, Massachusetts and detection of a novel cluster associated with nitrifying Betaproteobacteria. J Contam Hydrol, 2009,103:182-193
[135]Schmid M, Thill A, Purkhold U, et al. Characterization of activated sludge flocs byconfocal laser scanning microscopyand image analysis. Water Res,2003,37: 2043-2052
[136]Morgan Sagastume F, Larsen P, Nielsen J L, et al. Characterization of the loosely attached fraction of activated sludge bacteria. Water Res,2008,42: 843-854
[137]Lozada M, Itria R F, Figuerola E L M, et al. Bacterial community shifts in nonylphenol polyethoxylates-enriched activated sludge. Water Res,2004,38: 2077-2086
[138]Kraigher B, Kosjek T, Heath E, et al. Influence of pharmaceutical residues on the structure of activated sludge bacterial communities in wastewater treatment bidreactors. Water Res,42:4578-4588
[139]Riviere D, Desvignes V, Pelletier E, et al. Towards the definition of a core of microorganisms involved in anaerobic digestion of sludge. ISME J,2009,3: 1-15
[2]Kleywegt S, Pileggi V, Yang P, et al. Pharmaceuticals, hormones and bisphenol A in untreated source and finished drinking water in Ontario, Canada-Occurrence and treatment efficiency. Science of The Total Environment,2011, 409 (8):1481-1488
[3]Peng X, Yu Y, Tang C, et al. Occurrence of steroid estrogens, endocrine disrupting phenols, and acid pharmaceutical residues in urban riverine water of the Pearl River Delta, South China. Science of The Total Environment,2008, 397(1-3):158-166
[4]Tauxe Wuersch A, De Alencastro L F, Grandjean D, et al. Occurrence of several acidic drugs in sewage treatment plants in Switzerland and risk assessment. Water Research,2005,39 (9):1761-1772
[5]Richardson S D. Water analysis:emerging contaminants and current issues. Anal Chem,2009 (12):46-55
[6]Daughton C G, Ternes T A. Pharmaceuticals and personal care products in the environment:agents of subtle change? Environmental Health Perspectives,1999 (107):907-938
[7]China IRN (China Industry Research Net).2012-2013 personal care product market development analysis,2012
[8]BosiData (Bosi Data Research Center).2010-2013 personal care product market of China and investment prospect analysis,2011
[9]Kummerer k. (2004)Pharmaceuticals in the environment sources, fate, effect and risks. Berlin, Heidelberg, New York:Springer
[10]Liu J L, Wong M H. Pharmaceuticals and personal care products (PPCPs):A review on environmental contamination in China. Environment International, 2013,59 (0):208-224
[11]Jian Liang Z, Guang Guo Y, Li W, et al. Determination of phenolic endocrine disrupting chemicals and acidic pharmaceuticals in surface water of the Pearl Rivers in South China by gas chromatography negative chemical ionization mass spectrometry. Science of The Total Environment,2009, (407):962-974
[12]Desbrow C, Routledge E J, Brighty J P. Identification of estrogenic chemicals in STW effluent.2.In vivo responses in trout and roach. Environmental Toxicology and Chemistry,1998:1559-1565
[13]Kramer V J, Miles Richardson S, Pierens S L. Reproductive impairment and induction of alkaline labile phosphate, a biomarker of estrogen exposure, in fathead minnows (Pimephales promelas) exposed to waterborne 17β-estradiol. Aquatic Toxicology,1998:335-360
[14]Gimeno S, Komen H, Venderbosch Paul W M. Disruption of sexual differentiation in genetic male common carp (Cyprinous carpio) exposed to an alkylphenol during different life stages. Environmental Science and Technology, 1997,(10):2884-2890
[15]Pomati F, Castiglioni S, Zuccato E, et al. Effects of a Complex Mixture of Therapeutic Drugs at Environmental Levels on Human Embryonic Cells. Environmental Science & Technology,2006,40 (7):2442-2447
[16]Gravel A, Vijayan M M. Salicylate disrupts interrenal steroidogenesis and brain glucocorticoid receptor expression in rainbow trout. Toxicological Sciences, 2006,93 (1):41-49
[17]Oaks J L, Gilbert M, Virani M Z, et al. Diclofenac residues as the cause of vulture population decline in Pakistan. Nature,2004,427 (6975):630-633
[18]Ollaboration Cat N T C. Vascular and upper gastrointestinal effects of non-steroidal anti-inflammatory drugs:meta-analyses of individual participant data from randomised trials. The Lancet,2013
[19]Cleuvers M. Mixture toxicity of the anti-inflammatory drugs diclofenac, ibuprofen, naproxen, and acetylsalicylic acid. Ecotoxicology and Environmental Safety,2004,59(3):309-315
[20]Andreozzi R, Caprio V, Ciniglia C, et al. Antibiotics in the environment: occurrence in Italian STPs, fate, and preliminary assessment on algal toxicity of amoxicillin. Environmental Science and Technology,2004,38 (24):6832-6838
[21]Lin A Y C, Yu T H, Lin C F. Pharmaceutical contamination in residential, industrial, and agricultural waste streams:risk to aqueous environments in Taiwan. Chemosphere,2008,74 (1):131-141
[22]Brillas E, Garcia-Segura S, Skoumal M, et al. Electrochemical incineration of diclofenac in neutral aqueous medium by anodic oxidation using Pt and boron-doped diamond anodes. Chemosphere,2010,79 (6):605-612
[23]何建国,齐红娟,许志强.高度重视药物不良反应.中国医药卫生,2007,8(6)：72-73
[24]Sanderson H, Johnson D J, Wilson C J, et al. Probabilistic hazard assessment of environmentally occurring pharmaceuticals toxicity to fish, daphnids and algae by ECOSAR screening. Toxicology Letters,2003,144 (3):383-395
[25]Ferrari B, Paxeus N, Lo Giudice R, et al. Ecotoxicological impact of pharmaceuticals found in treated wastewaters:study of carbamazepine, clofibric acid, and diclofenac. Ecotox Environ Safe,2003 (55):359-370
[26]Rosal R, Gonzalo MS, Boltes K, et al. Identification of intermediates and assessment of ecotoxicity in the oxidation products generated during the ozonation of clofibric acid. J Hazard Mater,2009 (172):1061-1068
[27]Cleuvers M. Aquatic ecotoxicity of pharmaceuticals including the assessment of combination effects. Toxicol Lett,2003 (142):185-194
[28]Ferrari B, Mons R, Vollat B, et al. Environmental risk assessment of six human pharmaceuticals:are the current environmental risk assessment procedures sufficient for the protection of the aquatic environment? Environ Toxicol Chem, 2004(23):1344-1354
[29]Ra J S, Oh S Y, Lee B C, et al. The effect of suspended particles coated by humic acid on the toxicity of pharmaceuticals, estrogens, and phenolic compounds. Environ Int,2008 (34):184-192
[30]Farre M, Ferrer I, Ginebreda A, et al. Determination of drugs in surface water and wastewater samples by liquid chromatography mass spectrometry:methods and preliminary results including toxicity studies with Vibro fisheri. J Chromatogr A,2001 (938):187-197
[31]Hailing Sorensen B. Algal toxicity of antibacterial agents used in intensive farming. Chemosphere,2000 (40):731-739
[32]Quinn B, Gagne F, Blaise C. An investigation into the acute and chronic toxicity of eleven pharmaceuticals (and their solvents) found in wastewater effluent on the cnidarians, Hydra attenuate. Sci Total Environ,2008 (389):306-314
[33]Boillot C. Evaluation des risques ecotoxicologiques lies aux rejets d'effluents hospitaliers dans les milieux aquatiques. Contribution a l'amelioration de la phase "caraterisation des effets". PhD Thesis. Institut National des Sciences Appliquees de Lyon, France, N°d'ordre 2008 ISAL 0021
[34]Cleuvers M. Mixture toxicity of the anti-inflammatory drugs diclofenac, ibuprofen, naproxen, and acetylsalicylic acid. Ecotox Environ Safe,2004 (5): 309-315
[35]Kim S, Cho J, Kim I, et al. Occurrence and removal of pharmaceuticals and endocrine disruptors in South Korean surface, drinking and wastewaters. Water Res,2007(41):1013-1021
[36]Jones O A H, Voulvoulis N, Lester J N. Aquatic environmental assessment of the top 25 English prescription pharmaceuticals. Water Res,2002 (36): 5013-5022
[37]Jiang M, Wang L, Ji R. Biotic and abiotic degradation of four cephalosporin antibiotics in a lake surface water and sediment. Chemosphere,2010,80 (11): 1399-1405
[38]Zhang S, Zhang Q, Darisaw S, et al. Simultaneous quantification of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and pharmaceuticals and personal care products (PPCPs) in Mississippi river water, in New Orleans, Louisiana, USA. Chemosphere,2007,66 (6):1057-1069
[39]Wang L, Ying G G, Zhao J L, et al. Occurrence and risk assessment of acidic pharmaceuticals in the Yellow River, Hai River and Liao River of north China. Science of The Total Environment,2010,408 (16):3139-3147
[40]Zhao J L, Ying G G, Wang L, et al. Determination of phenolic endocrine disrupting chemicals and acidic pharmaceuticals in surface water of the Pearl Rivers in South China by gas chromatography negative chemical ionization-mass spectrometry. Science of The Total Environment,2009,407 (2): 962-974
[41]胡洪营,王超,郭美婷.药品和个人护理用品PPCPs对环境的污染现状与研究进展.生态环境,2005,14(6)：947-952
[42]Teijon G, Candela L, Tamoh K, et al. Occurrence of emerging contaminants, priority substances (2008/105/CE) and heavy metals in treated wastewater and groundwater at Depurbaix facility (Barcelona, Spain). Science of The Total Environment,2010,408 (17):3584-3595
[43]Yiruhan, Wang Q J, Mo C H, et al. Determination of four fluoroquinolone antibiotics in tap water in Guangzhou and Macao. Environmental Pollution, 2010,158(7):2350-2358
[44]McClellan K, Halden R U. Pharmaceuticals and personal care products in archived U.S. biosolids from the 2001 EPA national sewage sludge survey. Water Research,44 (2):658-668
[45]Chen F, Ying G G, Kong L X, et al. Distribution and accumulation of endocrine-disrupting chemicals and pharmaceuticals in wastewater irrigated soils in Hebei, China. Environmental Pollution,2011,159 (6):1490-1498
[46]Joss A, Keller E, Alder A C, et al. Removal of pharmaceuticals and fragrances in biological wastewater treatment. Water Research,2005,39 (14):3139-3152
[47]Zhang Y, GeiBen S U. In vitro degradation of carbamazepine and diclofenac by crude lignin peroxidase. Journal of Hazardous Materials,2010,176 (1-3): 1089-1092
[48]Volkova N, Ibrahim V, Hatti-Kaul R. Laccase catalysed oxidation of syringic acid:Calorimetric determination of kinetic parameters. Enzyme Microb Tech, 2012,50 (4-5):233-237
[49]Yu Z, Peldszus S, Huck P M. Adsorption characteristics of selected pharmaceuticals and an endocrine disrupting compound—Naproxen, carbamazepine and nonylphenol—on activated carbon. Water Research,2008, 42 (12):2873-2882
[50]Melillo M, Phillips G J, Davies J G, et al. The effect of protein binding on ibuprofen adsorption to activated carbons. Carbon,2004,42 (3):565-571
[51]Hasan Z, Jeon J, Jhung S H. Adsorptive removal of naproxen and clofibric acid from water using metal-organic frameworks. Journal of Hazardous Materials, 2012,209-210(0):151-157
[52]Li W, Lu S, Qiu Z, et al. Clofibric acid degradation in UV254/H2O2 process: Effect of temperature. Journal of Hazardous Materials,2010,176 (1-3): 1051-1057
[53]De Schepper W, Dries J, Geuens L, et al. A kinetic model for multicomponent wastewater substrate removal by partial ozonation and subsequent biodegradation. Water Research,2010,44 (18):5488-5498
[54]Esplugas S, Bila D M, Krause L G T, et al. Ozonation and advanced oxidation technologies to remove endocrine disrupting chemicals (EDCs) and Pharmaceuticals and personal care products (PPCPs) in water effluents. Journal of Hazardous Materials,2007,149 (3):631-642
[55]Kim I, Tanaka H. Photodegradation characteristics of PPCPs in water with UV treatment. Environment International,2009,35 (5):793-802
[56]Kim I, Yamashita N, Tanaka H. Photodegradation of Pharmaceuticals and personal care products during UV and UV/H2O2 treatments. Chemosphere,2009, 77(4):518-525
[57]Alvarez P M, Jaramillo J, Lopez Pinro F, et al. Preparation and characterization of magnetic TiO2 nanoparticles and their utilization for the degradation of emerging pollutants in water. Applied Catalysis B:Environmental,2010,100 (1-2):338-345
[58]Mendez Arriaga F, Torres Palma R A, Pettier C, et al. Ultrasonic treatment of water contaminated with ibuprofen. Water Research,2008,42 (16):4243-4248
[59]Wang Y, Zhang H, Chen L, et al. Ozonation combined with ultrasound for the degradation of tetracycline in a rectangular air-lift reactor. Separation and Purification Technology,2012,84:138-146
[60]Trovo Alam G, Nogueira R F P, Agiiera A, et al. Degradation of sulfamethoxazole in water by solar photo-Fenton. Chemical and toxicological evaluation. Water Research,2009,43 (16):3922-3931
[61]Coelho A D, Sans C, Agiiera A, et al. Effects of ozone pre-treatment on diclofenac:Intermediates, biodegradability and toxicity assessment. Science of The Total Environment,2009,407 (11):3572-3578
[62]Al-Rifai J H, Khabbaz H, Schafer A I. Removal of pharmaceuticals and endocrine disrupting compounds in a water recycling process using reverse osmosis systems. Separation and Purification Technology,77 (1):60-67
[63]Gros M, Petrovic M, Ginebreda A, et al. Removal of pharmaceuticals during wastewater treatment and environmental risk assessment using hazard indexes. Environment International,2010,36 (1):15-26
[64]Lishman L, Smyth S A, Sarafin K, et al. Occurrence and reductions of pharmaceuticals and personal care products and estrogens by municipal wastewater treatment plants in Ontario, Canada. Science of The Total Environment,2006,367 (2-3):544-558
[65]Verlicchi P, Al Aukidy M, Zambello E. Occurrence of pharmaceutical compounds in urban wastewater:Removal, mass load and environmental risk after a secondary treatment—A review. Science of The Total Environment,2012, 429:123-155
[66]Xue W, Wu C, Xiao K, et al. Elimination and fate of selected micro-organic pollutants in a full-scale anaerobic/anoxic/aerobic process combined with membrane bioreactor for municipal wastewater reclamation. Water Research, 2010,44(20):5999-6010
[67]Lin A Y C, Yu T H, Lateef S K. Removal of pharmaceuticals in secondary wastewater treatment processes in Taiwan. Journal of Hazardous Materials, 2009,167(1-3):1163-1169
[68]Leung H W, Minh T B, Murphy M B, et al. Distribution, fate and risk assessment of antibiotics in sewage treatment plants in Hong Kong, South China. Environment International,2012,42 (0):1-9
[69]Gulkowska A, Leung H W, So M K, et al. Removal of antibiotics from wastewater by sewage treatment facilities in Hong Kong and Shenzhen, China. Water Research,2008,42 (1-2):395-403
[70]Xu W H, Zhang G, Zou S C, et al. Determination of selected antibiotics in the Victoria Harbour and the Pearl River, South China using high performance liquid chromatography electrospray ionization tandem mass spectrometry. Environmental Pollution,2007,145 (3):672-679
[71]Jelic A, Gros M, Ginebreda A, et al. Occurrence, partition and removal of pharmaceuticals in sewage water and sludge during wastewater treatment. Water Research,2011,45 (3):1165-1176
[72]Gobel A, McArdell C S, Joss A, et al. Fate of sulfonamides, macrolides, and trimethoprim in different wastewater treatment technologies. Science of The Total Environment,2007,372 (2-3):361-371
[73]Clara M, Strenn B, Gans O, et al. Removal of selected pharmaceuticals, fragrances and endocrine disrupting compounds in a membrane bioreactor and conventional wastewater treatment plants. Water Research,2005,39 (19): 4797-4807
[74]Jia A, Wan Y, Xiao Y, et al. Occurrence and fate of quinolone and fluoroquinolone antibiotics in a municipal sewage treatment plant. Water Research,2012,46 (2):387-394
[75]Bernhard M, Muller J, Knepper T P. Biodegradation of persistent polar pollutants in wastewater:Comparison of an optimised lab-scale membrane bioreactor and activated sludge treatment. Water Research,2006,40 (18): 3419-3428
[76]Joss A, Zabczynski S, Gobel A, et al. Biological degradation of pharmaceuticals in municipal wastewater treatment:Proposing a classification scheme. Water Research,2006,40 (8):1686-1696
[77]Tunkel J, Howard P H, Boethling R S, et al. Predicting ready biodegradability in the Japanese ministry of international trade and industry test. Environ Toxicol Chem,2000,19:2478-2485
[78]Jones O A H, Voulvoulis N, Lester J N. The occurrence and removal of selected pharmaceutical compounds in a sewage treatment works utilising activated sludge treatment. Environmental Pollution,2007,145 (3):738-744
[79]Hai F I, Tessmer K, Nguyen L N, et al. Removal of micropollutants by membrane bioreactor under temperature variation. J Membrane Sci,2011,383 (1-2):144-151
[80]Suarez S, Lema J M, Omil F. Removal of Pharmaceutical and Personal Care Products (PPCPs) under nitrifying and denitrifying conditions. Water Research, 2010,44(10):3214-3224
[81]Carballa M, Omil F, Ternes T, et al. Fate of pharmaceutical and personal care products (PPCPs) during anaerobic digestion of sewage sludge. Water Research, 2007,41 (10):2139-2150
[82]Tadkaew N, Sivakumar M, Khan S J, et al. Effect of mixed liquor pH on the removal of trace organic contaminants in a membrane bioreactor. Bioresource Technology,2010,101 (5):1494-1500
[83]Urase T, Kagawa C, Kikuta T. Factors affecting removal of pharmaceutical substances and estrogens in membrane separation bioreactors. Desalination, 2005,178(1-3):107-113
[84]Clara M, Kreuzinger N, Strenn B, et al. The solids retention time—a suitable design parameter to evaluate the capacity of wastewater treatment plants to remove micropollutants. Water Research,2005,39 (1):97-106
[85]Lesjean B, Gnirss R, Buisson H, et al. Outcomes of a 2-year investigation on enhanced biological nutrients removal and trace organics elimination in membrane bioreactor (MBR). Water Sci Technol,2005,52 (10-11):453-460
[86]Kreuzinger N, Clara M, Strenn B, et al. Relevance of the sludge retention time (SRT) as design criteria for wastewater treatment plants for the removal of endocrine disruptors and pharmaceuticals from wastewater. Water Sci Technol, 2004,50(5):149-156
[87]Koch G, Kuhni M, Siegrist H. Calibration and validation of an ASM3-based steady-state model for activated sludge systems—part I:prediction of nitrogen removal and sludge production. Water Research,2001,35 (9):2235-2245
[88]Majewsky M, Gall T, Yargeau V, et al. Active heterotrophic biomass and sludge retention time (SRT) as determining factors for biodegradation kinetics of pharmaceuticals in activated sludge. Bioresource Technology,2011,102 (16): 7415-7421
[89]Maria Chiara Pietrogrande G B. GC-MS analytical methods for the determination of personal-care products in water matrices. Trends in Analytical Chemistry,2007,26(11):1086-1094
[90]Fang T H, Nan F H, Chin T S, et al. The occurrence and distribution of pharmaceutical compounds in the effluents of a major sewage treatment plant in Northern Taiwan and the receiving coastal waters. Mar Pollut Bull,2012,64 (7): 1435-1444
[91]Sui Q, Huang J, Deng S, et al. Seasonal Variation in the Occurrence and Removal of Pharmaceuticals and Personal Care Products in Different Biological Wastewater Treatment Processes. Environmental Science and Technology,2011, 45 (8):3341-3348
[92]Ort C, Lawrence M G, Rieckermann J, et al. Sampling for Pharmaceuticals and Personal Care Products (PPCPs) and Illicit Drugs in Wastewater Systems:Are Your Conclusions Valid? A Critical Review. Environmental Science and Technology,2010,44 (16):6024-6035
[93]Glelt, A. Estimation for small normal data sets with detection limits. Environ Sci Technol,1985,19:1201-1208
[94]Reemtsma T, Weiss S, Mueller J, et al. Polar pollutants entry into the water cycle by municipal wastewater:A European perspective. Environ Sci Technol, 2006,40,5451-5458
[95]Gabet Giraud V, Miege C, Choubert J M, et al. Occurrence and removal of estrogens and beta blockers by various processes in wastewater treatment plants. Science of The Total Environment,2010,408 (19):4257-4269
[96]Wick A, Fink G, Joss A, et al. Fate of beta blockers and psycho-active drugs in conventional wastewater treatment. Water Research,2009,43 (4):1060-1074
[97]Sui Q, Huang J, Deng S, et al. Occurrence and removal of pharmaceuticals, caffeine and DEET in wastewater treatment plants of Beijing, China. Water Research,2010,44 (2):417-426
[98]Kosma C I, Lambropoulou D A, Albanis T A. Occurrence and removal of PPCPs in municipal and hospital wastewaters in Greece. Journal of Hazardous Materials,2010,179 (1-3):804-817
[99]Brennan P J, Greenberg G, Miall W E, Thompson S G. Seasonal variation in arterial blood pressure. British Medical Journal (Clinical research ed.),1982, 285 (6346):919-923
[100]Ziylan A, Ince N H. The occurrence and fate of anti-inflammatory and analgesic pharmaceuticals in sewage and fresh water:Treatability by conventional and non-conventional processes. Journal of Hazardous Materials,187 (1-3):24-36
[101]Kimura K, Hara H, Watanabe Y. Removal of pharmaceutical compounds by submerged membrane bioreactors (MBRs). Desalination,2005,178:135-140
[102]Zorita S, Martensson L, Mathiasson L. Occurrence and removal of pharmaceuticals in municipal sewage treatment system in the south of Sweden. Sci Total Environ,2009,407:2760-2770
[103]Roberts P H, Thomas K V. The occurrence of selected pharmaceuticals in wastewater effluent and surface waters of the lower Tyne catchment. Sci Total Environ,2006,356:143-153
[104]Joss A, Andersen H, Ternes T, et al. Removal of Estrogens in Municipal Wastewater Treatment under Aerobic and Anaerobic Conditions:Consequences for Plant Optimization. Environmental Science and Technology 38 (11),3047-3055,2004,38 (11): 3047-3055
[105]Radjenovic J, Petrovic M, Barcel D. Advanced mass spectrometric methods applied to the study of fate and removal of pharmaceuticals in wastewater treatment. TrAC Trends in Analytical Chemistry,2007,26 (11):1132-1144
[106]Vieno N, Tuhkanen T, Kronberg L. Elimination of pharmaceuticals in sewage treatment plants in Finland. Water Res,2007,41:1001-1012
[107]Li W, Guang Guo Y, Jian Liang Z, et al. Assessing estrogenic activity in surface water and sediment of the Liao River system in northeast China using combined chemical and biological tools. Environmental Pollution,2011,159:148-156
[108]Wang B, Yu G, Huang J, et al. Tiered aquatic ecological risk assessment of organochlorine pesticides and their mixture in Jiangsu reach of Huaihe River, China. Environ Monit Assess,2009,157:29-42
[109]Backhaus T, Scholze M, Grimme L H. The single substance and mixture toxicity of quinolones to the bioluminescent bacterium Vibrio fischeri. Aquat Toxicol, 2000,49:49-61
[110]Zhao J L, Ying G G, Liu Y S, et al. Occurrence and a screening-level risk assessment of human pharmaceuticals in the Pearl River system, South China. Environmental Toxicology and Chemistry,2010,29 (6):1377-1384
[111]Escher B I, Baumgartner R, Koller M, et al. Environmental toxicology and risk assessment of pharmaceuticals from hospital wastewater. Water Research,2011, 45 (1):75-92
[112]Boyd G R, Palmeri J M, Zhang S, et al. Pharmaceuticals and personal care products (PPCPs) and endocrine disrupting chemicals (EDCs) in stormwater canals and Bayou St. John in New Orleans, Louisiana, USA. Science of The Total Environment,2004,333 (1-3):137-148
[113]Calderon Preciado D, Jimenez Cartagena C, Matamoros V, et al. Screening of 47 organic microcontaminants in agricultural irrigation waters and their soil loading. Water Research,45 (1):221-231
[114]Lissemore L, Hao C, Yang P, et al. An exposure assessment for selected pharmaceuticals within a watershed in Southern Ontario. Chemosphere,2006, 64 (5):717-729
[115]Fent K, Weston A A, Caminada D. Ecotoxicology of human pharmaceuticals. Aquatic Toxicology,2006,76 (2):122-159
[116]Maria H V, Victor M, Javier M V, et al. Assessment of full-scale natural systems for the removal of PPCPs from wastewater in small communities. Water Research,2010,44 (5):1429-1439
[117]APHA-AWWA-WPCF. StandardMethods for the Examination ofWater andWastewater,20th ed. American Public Health Association,Washington DC, USA,2001
[118]Sipma J, Osuna B, Collado N, et al. Comparison of removal of pharmaceuticals in MBR and activated sludge systems. Desalination,2010,250 (2):653-659
[119]Yang S F, Lin C F, Yu C, et al. Sorption and biodegradation of sulfonamide antibiotics by activated sludge:Experimental assessment using batch data obtained under aerobic conditions. Water Research,2011,45 (11):3389-3397
[120]Cheung W H, Szeto Y S, McKay G. Intraparticle diffusion processes during acid dye adsorption onto chitosan. Bioresource Technology,2007,98 (15): 2897-2904
[121]Blanquez P, Casas N, Font X, et al. Mechanism of textile metal dye biotransformation by Trametes versicolor. Water Research,2004,38 (8): 2166-2172
[122]Ni B J, Yu H Q, Sun Y J. Modeling simultaneous autotrophic and heterotrophic growth in aerobic granules. Water Research,2008,42 (6-7):1583-1594
[123]Kraigher B, Kosjek T, Heath E, et al. Influence of pharmaceutical residues on the structure of activated sludge bacterial communities in wastewater treatment bioreactors. Water Research,2008,42 (17):4578-4588
[124]Marco Urrea E, Perez Trujillo M, Blanquez P, et al. Biodegradation of the analgesic naproxen by Trametes versicolor and identification of intermediates using HPLC-DAD-MS and NMR. Bioresource Technology,2010,101 (7): 2159-2166
[125]Parris G E. Covalent binding of aromatic amines to humates.1. Reactions with carbonyls and quinones. Environmental Science and Technology,1980,14 (9): 1099-1106
[126]Weber E J, Spidle D L, Thorn K A. Covalent Binding of Aniline to Humic Substances.1. Kinetic Studies. Environmental Science and Technology,1996, 30 (9):2755-2763
[127]Shen R, Andrews S A. NDMA formation kinetics from three pharmaceuticals in four water matrices. Water Research,2011,45 (17):5687-5694
[128]Caporaso J G, Kuczynski J. et al. QIIME allows analysis of high throughput community sequencing data. Nature Methods,2010,7 (5):335-336
[129]Quast C, Pruesse E, Yilmaz P, et al. The SILVA ribosomal RNA gene database project:improved data processing and web-based tools. Nucl Acids Res,2013, 41 (1):590-596
[130]Tsai Y P, You S J, Pai T Y, et al. Effect of cadmium on composition and diversity of bacterial communities in activated sludges. Int Biodeter Biodegr, 2005,55:285-291
[131]Wong M T, Mino T, Seviour R J, et al. In situ identification and characterization of the microbial community structure of full-scale enhanced biological phosphorous removal plants in Japan. Water Res,2005,39:2901-2914
[132]Wagner M, Loy A. Bacterial community composition and function in sewage treatment systems. Curr Opin Biotech,2002,13:218-227
[133]Lee N, Nielsen P H, Aspegren H, et al. Long-term population dynamics and in situ physiology in activated sludge systems with enhanced biological phosphorus removal operated with and without nitrogen removal. Syst Appl Microbiol,2003,26:211-227
[134]Miller D N, Smith R L. Microbial characterization of nitrification in a shallow, nitrogen-contaminated aquifer, Cape Cod, Massachusetts and detection of a novel cluster associated with nitrifying Betaproteobacteria. J Contam Hydrol, 2009,103:182-193
[135]Schmid M, Thill A, Purkhold U, et al. Characterization of activated sludge flocs byconfocal laser scanning microscopyand image analysis. Water Res,2003,37: 2043-2052
[136]Morgan Sagastume F, Larsen P, Nielsen J L, et al. Characterization of the loosely attached fraction of activated sludge bacteria. Water Res,2008,42: 843-854
[137]Lozada M, Itria R F, Figuerola E L M, et al. Bacterial community shifts in nonylphenol polyethoxylates-enriched activated sludge. Water Res,2004,38: 2077-2086
[138]Kraigher B, Kosjek T, Heath E, et al. Influence of pharmaceutical residues on the structure of activated sludge bacterial communities in wastewater treatment bidreactors. Water Res,42:4578-4588
[139]Riviere D, Desvignes V, Pelletier E, et al. Towards the definition of a core of microorganisms involved in anaerobic digestion of sludge. ISME J,2009,3: 1-15