Status of hormones and painkillers in wastewater effluents across several European states—considerations for the EU watch list concerning estradiols and diclofenac

Present technologies for wastewater treatment do not sufficiently address the increasing pollution situation of receiving water bodies, especially with the growing use of personal care products and pharmaceuticals (PPCP) in the private household and health sector. The relevance of addressing this problem of organic pollutants was taken into account by the Directive 2013/39/EU that introduced (i) the quality evaluation of aquatic compartments, (ii) the polluter pays principle, (iii) the need for innovative and affordable wastewater treatment technologies, and (iv) the identification of pollution causes including a list of principal compounds to be monitored. In addition, a watch list of 10 other substances was recently defined by Decision 2015/495 on March 20, 2015. This list contains, among several recalcitrant chemicals, the painkiller diclofenac and the hormones 17β-estradiol and 17α-ethinylestradiol. Although some modern approaches for their removal exist, such as advanced oxidation processes (AOPs), retrofitting most wastewater treatment plants with AOPs will not be acceptable as consistent investment at reasonable operational cost. Additionally, by-product and transformation product formation has to be considered. The same is true for membrane-based technologies (nanofiltration, reversed osmosis) despite of the incredible progress that has been made during recent years, because these systems lead to higher operation costs (mainly due to higher energy consumption) so that the majority of communities will not easily accept them. Advanced technologies in wastewater treatment like membrane bioreactors (MBR) that integrate biological degradation of organic matter with membrane filtration have proven a more complete elimination of emerging pollutants in a rather cost- and labor-intensive technology. Still, most of the presently applied methods are incapable of removing critical compounds completely. In this opinion paper, the state of the art of European WWTPs is reflected, and capacities of single methods are described. Furthermore, the need for analytical standards, risk assessment, and economic planning is stressed. The survey results in the conclusion that combinations of different conventional and advanced technologies including biological and plant-based strategies seem to be most promising to solve the burning problem of polluting our environment with hazardous emerging xenobiotics.

[1]  Heinz Singer,et al.  Hospital wastewater treatment by membrane bioreactor: performance and efficiency for organic micropollutant elimination. , 2012, Environmental science & technology.

[2]  L. Schäfer,et al.  Fabrication and application of Diachem® electrodes , 2003 .

[3]  Anne Togola,et al.  Consequences of treated water recycling as regards pharmaceuticals and drugs in surface and ground waters of a medium-sized Mediterranean catchment. , 2006, Environmental science & technology.

[4]  K. Thomas,et al.  Determination of selected human pharmaceutical compounds in effluent and surface water samples by high-performance liquid chromatography-electrospray tandem mass spectrometry. , 2003, Journal of chromatography. A.

[5]  Christopher Bellona,et al.  Factors affecting the rejection of organic solutes during NF/RO treatment--a literature review. , 2004, Water research.

[6]  E. Topuz,et al.  Seasonal variation of diclofenac concentration and its relation with wastewater characteristics at two municipal wastewater treatment plants in Turkey. , 2014, Journal of hazardous materials.

[7]  A. D. Vethaak,et al.  Analysis and occurrence of estrogenic hormones and their glucuronides in surface water and waste water in The Netherlands. , 1999, The Science of the total environment.

[8]  Adriano Joss,et al.  A rapid method to measure the solid-water distribution coefficient (Kd) for pharmaceuticals and musk fragrances in sewage sludge. , 2004, Water research.

[9]  A. Gallipoli,et al.  Exposure of the Main Italian River Basin to Pharmaceuticals , 2011, Journal of toxicology.

[10]  Uta R. Kraus,et al.  Elimination of carbamazepine, diclofenac and naproxen from treated wastewater by nanofiltration. , 2009 .

[11]  M. Ray,et al.  Advanced Oxidation Processes , 2006 .

[12]  Yolanda Picó,et al.  Occurrence of acidic pharmaceuticals and personal care products in Turia River Basin: from waste to drinking water. , 2014, The Science of the total environment.

[13]  Mats Tysklind,et al.  Required ozone doses for removing pharmaceuticals from wastewater effluents. , 2013, The Science of the total environment.

[14]  Tzahi Y Cath,et al.  Removal of natural steroid hormones from wastewater using membrane contactor processes. , 2006, Environmental science & technology.

[15]  J. Comas,et al.  Pharmaceuticals occurrence in a WWTP with significant industrial contribution and its input into the river system. , 2014, Environmental pollution.

[16]  J. Kallas,et al.  Selective photocatalytic oxidation of steroid estrogens in water treatment: urea as co-pollutant. , 2007, Journal of hazardous materials.

[17]  W. Verstraete,et al.  Diclofenac oxidation by biogenic manganese oxides. , 2010, Environmental science & technology.

[18]  M. Carballa,et al.  Influence of nitrifying conditions on the biodegradation and sorption of emerging micropollutants. , 2012, Water research.

[19]  T. Ternes Occurrence of drugs in German sewage treatment plants and rivers 1 Dedicated to Professor Dr. Klaus , 1998 .

[20]  K. Thomasb,et al.  Investigating the environmental transport of human pharmaceuticals to streams in the United Kingdom , 2004 .

[21]  S. Mitra,et al.  Microwave-assisted solvent extraction of solid matrices and subsequent detection of pharmaceuticals and personal care products (PPCPs) using gas chromatography-mass spectrometry. , 2007, Analytica chimica acta.

[22]  M. D. Gurol,et al.  Treatment of persistent organic compounds by integrated advanced oxidation processes and sequential batch reactor. , 2009, Water research.

[23]  Haidong Zhou,et al.  Removal and reduction of selected organic micro-pollutants in effluent sewage by the ozone-based oxidation processes , 2015 .

[24]  Margarita Genius,et al.  Assessing preferences for wastewater treatment in a rural area using choice experiments , 2012 .

[25]  J. Fick,et al.  EU-wide monitoring survey on emerging polar organic contaminants in wastewater treatment plant effluents. , 2013, Water research.

[26]  C. von Sonntag Advanced oxidation processes: mechanistic aspects. , 2008, Water science and technology : a journal of the International Association on Water Pollution Research.

[27]  Martin Krauss,et al.  LC–high resolution MS in environmental analysis: from target screening to the identification of unknowns , 2010, Analytical and bioanalytical chemistry.

[28]  T. Melin,et al.  Efficiency of nanofiltration for the elimination of steroids from water. , 2004, Water science and technology : a journal of the International Association on Water Pollution Research.

[29]  H Kroiss,et al.  Removal of selected pharmaceuticals, fragrances and endocrine disrupting compounds in a membrane bioreactor and conventional wastewater treatment plants. , 2005, Water research.

[30]  Spencer Snowling,et al.  Modeling the Fate of Estrogenic Hormones in Municipal Wastewater Treatment , 2008 .

[31]  Xin Yang,et al.  Occurrence and removal of pharmaceuticals and personal care products (PPCPs) in an advanced wastewater reclamation plant. , 2011, Water research.

[32]  S. Meriç,et al.  Occurrence patterns of pharmaceuticals in water and wastewater environments , 2007, Analytical and bioanalytical chemistry.

[33]  Francisco Omil,et al.  Pre-treatment of hospital wastewater by coagulation-flocculation and flotation. , 2009, Bioresource technology.

[34]  J Gasperi,et al.  Study of a large scale powdered activated carbon pilot: Removals of a wide range of emerging and priority micropollutants from wastewater treatment plant effluents. , 2015, Water research.

[35]  I. Koyuncu,et al.  Removal of hormones and antibiotics by nanofiltration membranes , 2008 .

[36]  Hansruedi Siegrist,et al.  Elimination of micropollutants during post-treatment of hospital wastewater with powdered activated carbon, ozone, and UV. , 2013, Environmental science & technology.

[37]  M. Otero,et al.  Processes for the elimination of estrogenic steroid hormones from water: a review. , 2012, Environmental pollution.

[38]  Martin Kampmann,et al.  Ozonation: a tool for removal of pharmaceuticals, contrast media and musk fragrances from wastewater? , 2003, Water research.

[39]  K. Thomas,et al.  The occurrence of selected pharmaceuticals in wastewater effluent and surface waters of the lower Tyne catchment. , 2006, The Science of the total environment.

[40]  V. Pârvulescu,et al.  Degradation of diclofenac in water using a pulsed corona discharge , 2013 .

[41]  Oliver A.H. Jones,et al.  Pharmaceuticals: a threat to drinking water? , 2005, Trends in biotechnology.

[42]  Isabel Martí,et al.  Occurrence and fate of emerging wastewater contaminants in Western Balkan Region. , 2008, The Science of the total environment.

[43]  Francisco Omil,et al.  Removal of pharmaceutical and personal care products (PPCPs) under nitrifying and denitrifying conditions. , 2010, Water research.

[44]  P. Soudek,et al.  Phytoremediation of Pharmaceuticals—Preliminary Study , 2010, International journal of phytoremediation.

[45]  J. Smits,et al.  Detection and drivers of exposure and effects of pharmaceuticals in higher vertebrates , 2014, Philosophical Transactions of the Royal Society B: Biological Sciences.

[46]  N. Love,et al.  Sorption of 17β-Estradiol and 17α-Ethinylestradiol by Colloidal Organic Carbon Derived from Biological Wastewater Treatment Systems , 2004 .

[47]  Barbora Jarošová,et al.  What level of estrogenic activity determined by in vitro assays in municipal waste waters can be considered as safe? , 2014, Environment international.

[48]  S. Ferro,et al.  Electrochemical oxidation of organic pollutants for the wastewater treatment: direct and indirect processes. , 2006, Chemical Society reviews.

[49]  T. Tuhkanen,et al.  Removal of Pharmaceuticals in Drinking Water Treatment: Effect of Chemical Coagulation , 2006, Environmental technology.

[50]  J. Keller,et al.  Biofiltration of wastewater treatment plant effluent: effective removal of pharmaceuticals and personal care products and reduction of toxicity. , 2011, Water research.

[51]  Andreas N. Angelakis,et al.  Application of Cost Criteria for Selection of Municipal Wastewater Treatment Systems , 2003 .

[52]  Konstantinos P. Tsagarakis,et al.  The social acceptability and valuation of recycled water in Crete: A study of consumers' and farmers' attitudes , 2007 .

[53]  Ime Akanyeti,et al.  Micropollutant sorption to membrane polymers: a review of mechanisms for estrogens. , 2011, Advances in colloid and interface science.

[54]  Athanasios S Stasinakis,et al.  Simultaneous determination of the endocrine disrupting compounds nonylphenol, nonylphenol ethoxylates, triclosan and bisphenol A in wastewater and sewage sludge by gas chromatography-mass spectrometry. , 2007, Journal of chromatography. A.

[55]  H. Hiratsuka,et al.  Treatment of wastewater having estrogen activity by ionizing radiation , 2007 .

[56]  Roberto Andreozzi,et al.  Pharmaceuticals in STP effluents and their solar photodegradation in aquatic environment. , 2003, Chemosphere.

[57]  Rebecca A. Trenholm,et al.  Pilot-scale evaluation of ozone and biological activated carbon for trace organic contaminant mitigation and disinfection. , 2011, Water research.

[58]  Valery Tkachenko,et al.  Identification of “Known Unknowns” Utilizing Accurate Mass Data and ChemSpider , 2011, Journal of The American Society for Mass Spectrometry.

[59]  Emmanuelle Vulliet,et al.  Occurrence of pharmaceuticals and hormones in drinking water treated from surface waters , 2011 .

[60]  Heinz P Singer,et al.  Occurrence and fate of carbamazepine, clofibric acid, diclofenac, ibuprofen, ketoprofen, and naproxen in surface waters. , 2003, Environmental science & technology.

[61]  M. Korkmaz,et al.  The effects of gamma irradiation on diclofenac sodium, liposome and niosome ingredients for rheumatoid arthritis. , 2013, Interventional medicine & applied science.

[62]  John L. Zhou,et al.  Photodegradation of estrone and 17β-estradiol in water , 2007 .

[63]  A. Bignert,et al.  Comments concerning the national Swedish contaminant monitoring programme in marine biota, 2016 , 2004 .

[64]  C. Buisman,et al.  Removal of micropollutants from aerobically treated grey water via ozone and activated carbon. , 2011, Water research.

[65]  Liliana J. G. Silva,et al.  Environmental impact of pharmaceuticals from Portuguese wastewaters: geographical and seasonal occurrence, removal and risk assessment. , 2015, Environmental research.

[66]  Erin M. Snyder,et al.  Identification and quantification of estrogen receptor agonists in wastewater effluents. , 2001, Environmental science & technology.

[67]  C. Pastore,et al.  Identification of low molecular weight organic acids by ion chromatography/hybrid quadrupole time-of-flight mass spectrometry during Uniblu-A ozonation. , 2013, Rapid communications in mass spectrometry : RCM.

[68]  Marta Carballa,et al.  Calculation methods to perform mass balances of micropollutants in sewage treatment plants. application to pharmaceutical and personal care products (PPCPs). , 2007, Environmental science & technology.

[69]  F. Sacher,et al.  Pharmaceutical residues in the river Rhine--results of a one-decade monitoring programme. , 2008, Journal of environmental monitoring : JEM.

[70]  S. Mohan,et al.  Endocrine disruptive synthetic estrogen (17α-ethynylestradiol) removal from aqueous phase through batch and column sorption studies: Mechanistic and kinetic analysis , 2011 .

[71]  Ching-Hua Huang,et al.  Adsorption, desorption, and steady-state removal of 17β-estradiol by nanofiltration membranes , 2008 .

[72]  H D Stensel,et al.  A mechanistic model for fate and removal of estrogens in biological nutrient removal activated sludge systems. , 2012, Water science and technology : a journal of the International Association on Water Pollution Research.

[73]  T. Albanis,et al.  Photocatalytic degradation study of diclofenac over aqueous TiO2 suspensions , 2006 .

[74]  R. Curini,et al.  Determination of Non-Steroidal Anti-Inflammatory Drugs in Surface Water and Wastewater by Liquid Chromatography-Tandem Mass Spectrometry , 2003, Chromatographia.

[75]  A. Kraft,et al.  Anodic oxidation with doped diamond electrodes: a new advanced oxidation process. , 2003, Journal of hazardous materials.

[76]  Yang Feng-lin,et al.  MBR focus: do nonwovens offer a cheaper option? , 2005 .

[77]  M. Sillanpää,et al.  Fate of diclofenac in municipal wastewater treatment plant - a review. , 2014, Environment international.

[78]  Matthew J. Kotchen,et al.  Pharmaceuticals in wastewater: behavior, preferences, and willingness to pay for a disposal program. , 2009, Journal of environmental management.

[79]  J. Rivera-Utrilla,et al.  Pharmaceuticals as emerging contaminants and their removal from water. A review. , 2013, Chemosphere.

[80]  Uta R. Kraus,et al.  Elimination of pharmaceuticals from wastewater by submerged nanofiltration plate modules , 2010 .

[81]  Christopher Bellona,et al.  Comparing nanofiltration and reverse osmosis for drinking water augmentation , 2008 .

[82]  Shane A. Snyder,et al.  Transformation of atrazine, carbamazepine, diclofenac and sulfamethoxazole by low and medium pressure UV and UV/H2O2 treatment , 2012 .

[83]  G. Pojana,et al.  Natural and synthetic endocrine disrupting compounds (EDCs) in water, sediment and biota of a coastal lagoon. , 2007, Environment international.

[84]  M. Murugananthan,et al.  Electrochemical degradation of 17β-estradiol (E2) at boron-doped diamond (Si/BDD) thin film electrode , 2007 .

[85]  A Joss,et al.  Micropollutant removal by attached and suspended growth in a hybrid biofilm-activated sludge process. , 2013, Water research.

[86]  T. Letzel,et al.  Exposure assessment of the pharmaceutical diclofenac based on long-term measurements of the aquatic input. , 2009, Environment international.

[87]  A. Ledin,et al.  Suspended biofilm carrier and activated sludge removal of acidic pharmaceuticals. , 2012, Water research.

[88]  J. Lester,et al.  Binding of Waterborne Steroid Estrogens to Solid Phases in River and Estuarine Systems , 2000 .

[89]  Benedek Gy Plósz,et al.  An activated sludge modeling framework for xenobiotic trace chemicals (ASM‐X): Assessment of diclofenac and carbamazepine , 2012, Biotechnology and bioengineering.

[90]  M. Esperanza,et al.  Reduction of endocrine disruptor emissions in the environment: the benefit of wastewater treatment. , 2009, Water research.

[91]  R. Schwarzenbach,et al.  Environmental Organic Chemistry , 1993 .

[92]  K. Thomas,et al.  Environmental assessment of Norwegian priority pharmaceuticals based on the EMEA guideline. , 2008, Ecotoxicology and environmental safety.

[93]  H. Ngo,et al.  A review on the occurrence of micropollutants in the aquatic environment and their fate and removal during wastewater treatment. , 2014, The Science of the total environment.

[94]  C. Martínez-Huitle,et al.  RECENT ENVIRONMENTAL APPLICATIONS OF DIAMOND ELECTRODE: CRITICAL REVIEW , 2008 .

[95]  Adriano Joss,et al.  Removal of estrogens in municipal wastewater treatment under aerobic and anaerobic conditions: consequences for plant optimization. , 2004, Environmental science & technology.

[96]  N. Thomaidis,et al.  Fate of selected pharmaceuticals and synthetic endocrine disrupting compounds during wastewater treatment and sludge anaerobic digestion. , 2013, Journal of hazardous materials.

[97]  M. Oturan,et al.  Advanced Oxidation Processes in Water/Wastewater Treatment: Principles and Applications. A Review , 2014 .

[98]  Adriano Joss,et al.  Removal of pharmaceuticals and fragrances in biological wastewater treatment. , 2005, Water research.

[99]  J. Marugán,et al.  Emerging micropollutant oxidation during disinfection processes using UV-C, UV-C/H2O2, UV-A/TiO2 and UV-A/TiO2/H2O2. , 2013, Water research.

[100]  Marta Carballa,et al.  How are pharmaceutical and personal care products (PPCPs) removed from urban wastewaters? , 2008 .

[101]  Adriano Joss,et al.  Oxidation of pharmaceuticals during ozonation of municipal wastewater effluents: a pilot study. , 2005, Environmental science & technology.

[102]  Karl G Linden,et al.  Degradation of endocrine disrupting chemicals bisphenol A, ethinyl estradiol, and estradiol during UV photolysis and advanced oxidation processes. , 2004, Environmental science & technology.

[103]  Gang Yu,et al.  Occurrence and removal of pharmaceuticals, caffeine and DEET in wastewater treatment plants of Beijing, China. , 2010, Water research.

[104]  M. Dudziak,et al.  Elimination of steroidal sex hormones by conventional water treatment and membrane processes , 2006 .

[105]  Damià Barceló,et al.  Multi-residue analytical methods using LC-tandem MS for the determination of pharmaceuticals in environmental and wastewater samples: a review , 2006, Analytical and bioanalytical chemistry.

[106]  M. Guida,et al.  Fate of pharmaceuticals in contaminated urban wastewater effluent under ultrasonic irradiation. , 2009, Water research.

[107]  Damià Barceló,et al.  Contribution of hospital effluents to the load of pharmaceuticals in urban wastewaters: identification of ecologically relevant pharmaceuticals. , 2013, The Science of the total environment.

[108]  Adriano Joss,et al.  How to avoid pharmaceuticals in the aquatic environment. , 2004, Journal of biotechnology.

[109]  Giovanni Fraquelli,et al.  Reforming the wastewater treatment sector in Italy: Implications of plant size, structure, and scale economies , 2003 .

[110]  M Molinos-Senante,et al.  Economic feasibility study for intensive and extensive wastewater treatment considering greenhouse gases emissions. , 2013, Journal of environmental management.

[111]  A. Ghauch,et al.  Aqueous removal of diclofenac by plated elemental iron: bimetallic systems. , 2010, Journal of hazardous materials.

[112]  C. Prasse,et al.  Assessing the photochemical transformation pathways of acetaminophen relevant to surface waters: transformation kinetics, intermediates, and modelling. , 2014, Water research.

[113]  P. Verlicchi,et al.  Occurrence of pharmaceutical compounds in urban wastewater: removal, mass load and environmental risk after a secondary treatment--a review. , 2012, The Science of the total environment.

[114]  M. Reis,et al.  Analysis of 65 pharmaceuticals and personal care products in 5 wastewater treatment plants in Portugal using a simplified analytical methodology. , 2010, Water Science and Technology.

[115]  Karl G Linden,et al.  Destruction of estrogenic activity in water using UV advanced oxidation. , 2007, The Science of the total environment.

[116]  D. Barceló,et al.  Tracing pharmaceuticals in a municipal plant for integrated wastewater and organic solid waste treatment. , 2012, The Science of the total environment.

[117]  D. Fatta-Kassinos,et al.  Factors affecting diclofenac decomposition in water by UV-A/TiO2 photocatalysis , 2010 .

[118]  Emilio Benfenati,et al.  Estrogenicity profile and estrogenic compounds determined in river sediments by chemical analysis, ELISA and yeast assays. , 2008, Chemosphere.

[119]  Norman Nowotny,et al.  Quantification and modeling of the elimination behavior of ecologically problematic wastewater micropollutants by adsorption on powdered and granulated activated carbon. , 2007, Environmental science & technology.

[120]  T. Ginn,et al.  Occurrence and fate of pharmaceutically active compounds in the environment, a case study: Höje River in Sweden. , 2005, Journal of hazardous materials.

[121]  John L. Zhou,et al.  Removal of estrone and 17β-estradiol from water by adsorption , 2005 .

[122]  Konstantinos P. Tsagarakis,et al.  Estimation of willingness to pay for wastewater treatment , 2005 .

[123]  F. Rosario‐Ortiz,et al.  Evaluation of enhanced coagulation pretreatment to improve ozone oxidation efficiency in wastewater. , 2011, Water research.

[124]  Christian Stamm,et al.  Micropollutant removal from wastewater: facts and decision-making despite uncertainty. , 2015, Environmental science & technology.

[125]  F. Hai,et al.  Chemical coagulation-based processes for trace organic contaminant removal: current state and future potential. , 2012, Journal of environmental management.

[126]  J. Hartmann,et al.  Degradation of the drug diclofenac in water by sonolysis in presence of catalysts. , 2008, Chemosphere.

[127]  Ulf Jeppsson,et al.  Modelling the occurrence, transport and fate of pharmaceuticals in wastewater systems , 2014, Environ. Model. Softw..

[128]  S. Iwasaki,et al.  Adsorbability of estrone and 17β-estradiol in water onto activated carbon , 2006 .

[129]  Jukka Pellinen,et al.  Critical evaluation of screening techniques for emerging environmental contaminants based on accurate mass measurements with time-of-flight mass spectrometry. , 2012, Journal of mass spectrometry : JMS.

[130]  Oliver A.H. Jones,et al.  Questioning the excessive use of advanced treatment to remove organic micropollutants from wastewater. , 2007, Environmental science & technology.

[131]  M. Poch,et al.  Economic valuation of environmental benefits of removing pharmaceutical and personal care products from WWTP effluents by ozonation. , 2013, The Science of the total environment.

[132]  Thomas Heberer,et al.  Tracking persistent pharmaceutical residues from municipal sewage to drinking water , 2002 .

[133]  Christopher Bellona,et al.  Rejection of wastewater‐derived micropollutants in high‐pressure membrane applications leading to indirect potable reuse , 2005 .

[134]  A Joss,et al.  Are we about to upgrade wastewater treatment for removing organic micropollutants? , 2008, Water science and technology : a journal of the International Association on Water Pollution Research.

[135]  P. Castro,et al.  Enantioselective biodegradation of pharmaceuticals, alprenolol and propranolol, by an activated sludge inoculum. , 2013, Ecotoxicology and environmental safety.

[136]  T Viraraghavan,et al.  Biological treatment processes for fish processing wastewater--a review. , 2010, Bioresource technology.

[137]  Oliver Fiehn,et al.  Advances in structure elucidation of small molecules using mass spectrometry , 2010, Bioanalytical reviews.

[138]  D. Aga,et al.  Micropollutant fate in wastewater treatment: redefining "removal". , 2012, Environmental science & technology.

[139]  D. Barceló,et al.  Determination of 81 pharmaceutical drugs by high performance liquid chromatography coupled to mass spectrometry with hybrid triple quadrupole-linear ion trap in different types of water in Serbia. , 2014, The Science of the total environment.

[140]  Guenter Langergraber,et al.  Using phytoremediation technologies to upgrade waste water treatment in Europe , 2007, Environmental science and pollution research international.

[141]  N. Vieno,et al.  Occurrence of Pharmaceuticals in Finnish Sewage Treatment Plants, Surface Waters, and Their Elimination in Drinking Water Treatment Processes , 2007 .

[142]  Jolanta Dvarionienė,et al.  Presence and Detection of Pharmaceutical Substances (Diclofenac, 17-β-estradiol, 17-α-etilinestradiol) in the Environment. Future Challenges for Lithuania , 2014 .

[143]  R. Cela,et al.  Determination of natural and synthetic estrogens in water by gas chromatography with mass spectrometric detection. , 2004, Journal of chromatography. A.

[144]  Helen Trenerry,et al.  Martindale: The complete drug reference. 37th ed. , 2011 .

[145]  R. Andreozzi,et al.  Advanced oxidation of the pharmaceutical drug diclofenac with UV/H2O2 and ozone. , 2004, Water research.

[146]  E. Brillas,et al.  Remediation of water pollution caused by pharmaceutical residues based on electrochemical separation and degradation technologies: a review. , 2012, Environment international.

[147]  P. Lens,et al.  Removal of estrone, 17α-ethinylestradiol, and 17ß-estradiol in algae and duckweed-based wastewater treatment systems , 2010, Environmental science and pollution research international.

[148]  T. Albanis,et al.  Investigation of PPCPs in wastewater treatment plants in Greece: occurrence, removal and environmental risk assessment. , 2014, The Science of the total environment.

[149]  R. Trueman,et al.  Invasive species may offer advanced phytoremediation of endocrine disrupting chemicals in aquatic ecosystems , 2013 .

[150]  F. Frimmel,et al.  Short-term tests with a pilot sewage plant and biofilm reactors for the biological degradation of the pharmaceutical compounds clofibric acid, ibuprofen, and diclofenac. , 2003, The Science of the total environment.

[151]  U. Gunten Ozonation of drinking water: part I. Oxidation kinetics and product formation. , 2003 .

[152]  C. Volz,et al.  Municipal Wastewater Concentrations of Pharmaceutical and Xeno-Estrogens: Wildlife and Human Health Implications , 2009 .

[153]  R. Goel,et al.  Fate and removal of estrogens in municipal wastewater. , 2010, Journal of environmental monitoring : JEM.

[154]  D. Barceló,et al.  Environmental risk assessment of pharmaceutical residues in wastewater effluents, surface waters and sediments. , 2006, Talanta.

[155]  L. Wojnárovits,et al.  Elimination of diclofenac from water using irradiation technology. , 2011, Chemosphere.

[156]  L. O N,et al.  Pharmaceutical Retention Mechanisms by Nanofiltration Membranes , 2022 .

[157]  Félix Hernández,et al.  Multi-class determination of around 50 pharmaceuticals, including 26 antibiotics, in environmental and wastewater samples by ultra-high performance liquid chromatography-tandem mass spectrometry. , 2011, Journal of chromatography. A.

[158]  Marta Carballa,et al.  Removal of cosmetic ingredients and pharmaceuticals in sewage primary treatment. , 2005, Water research.

[159]  F. Omil,et al.  Mass balance of pharmaceutical and personal care products in a pilot-scale single-sludge system: influence of T, SRT and recirculation ratio. , 2012, Chemosphere.

[160]  Long D Nghiem,et al.  Removal of trace organics by MBR treatment: the role of molecular properties. , 2011, Water research.

[161]  How Yong Ng,et al.  Influence of colloidal fouling on rejection of trace organic contaminants by reverse osmosis , 2004 .

[162]  F. Beltrán,et al.  Diclofenac removal from water by ozone and photolytic TiO2 catalysed processes , 2010 .

[163]  K. Thomas,et al.  The occurrence of selected human pharmaceutical compounds in UK estuaries. , 2004, Marine pollution bulletin.

[164]  Han-Qing Yu,et al.  A new cathodic electrode deposit with palladium nanoparticles for cost-effective hydrogen production , 2011 .

[165]  Yoshimasa Watanabe,et al.  Elimination of selected acidic pharmaceuticals from municipal wastewater by an activated sludge system and membrane bioreactors. , 2007, Environmental science & technology.

[166]  Thomas Ternes,et al.  Pharmaceuticals and Metabolites as Contaminants of the Aquatic Environment , 2001 .

[167]  A. Oikari,et al.  Metabolites of the aquatic pollutant diclofenac in fish bile. , 2010, Environmental science & technology.

[168]  F. Beltrán,et al.  Photocatalytic ozonation to remove the pharmaceutical diclofenac from water: Influence of variables , 2012 .

[169]  P. Grenni,et al.  Simultaneous determination of human pharmaceuticals in water samples by solid phase extraction and HPLC with UV-fluorescence detection , 2013 .

[170]  Martin Schlabach,et al.  Source to sink tracking of selected human pharmaceuticals from two Oslo city hospitals and a wastewater treatment works. , 2007, Journal of environmental monitoring : JEM.

[171]  Sixto Malato,et al.  Advanced oxidation processes for water treatment: advances and trends for R & D , 2008 .

[172]  E. Lai,et al.  Characterization of molecularly imprinted and nonimprinted polymer submicron particles specifically tailored for removal of trace 17β‐estradiol in water treatment , 2009 .

[173]  S. Jobling,et al.  Environmental science: The hidden costs of flexible fertility , 2012, Nature.

[174]  P. Cañizares,et al.  Electrochemical Advanced Oxidation Processes: An Overview of the Current Applications to Actual Industrial Effluents , 2017 .

[175]  D. Barceló,et al.  Determination of pharmaceuticals in sewage sludge by pressurized liquid extraction (PLE) coupled to liquid chromatography-tandem mass spectrometry (LC-MS/MS) , 2009, Analytical and bioanalytical chemistry.

[176]  R. Vahala,et al.  Biodegradation of ibuprofen, diclofenac and carbamazepine in nitrifying activated sludge under 12 °C temperature conditions. , 2014, The Science of the total environment.

[177]  Marta Carballa,et al.  Behavior of pharmaceuticals, cosmetics and hormones in a sewage treatment plant. , 2004, Water research.

[178]  S. Esplugas,et al.  Degradation of 32 emergent contaminants by UV and neutral photo-fenton in domestic wastewater effluent previously treated by activated sludge. , 2012, Water research.

[179]  A. Brenner,et al.  The use of RO to remove emerging micropollutants following CAS/UF or MBR treatment of municipal wastewater , 2011 .

[180]  P. Schröder,et al.  Uptake and metabolism of diclofenac in Typha latifolia--how plants cope with human pharmaceutical pollution. , 2014, Plant science : an international journal of experimental plant biology.

[181]  Mira Petrovic,et al.  Polar pollutants entry into the water cycle by municipal wastewater: a European perspective. , 2006, Environmental science & technology.

[182]  T. Ternes,et al.  Removal of estrogenic activity and formation of oxidation products during ozonation of 17alpha-ethinylestradiol. , 2004, Environmental science & technology.

[183]  N. Thomaidis,et al.  Removal of selected endocrine disrupters in activated sludge systems: effect of sludge retention time on their sorption and biodegradation. , 2010, Bioresource technology.

[184]  N. Ince,et al.  Degradation of diclofenac in water by homogeneous and heterogeneous sonolysis. , 2011, Ultrasonics sonochemistry.

[185]  C. Miège,et al.  Impact of wastewater treatment plants on receiving surface waters and a tentative risk evaluation: the case of estrogens and beta blockers , 2014, Environmental Science and Pollution Research.

[186]  Barbara Kasprzyk-Hordern,et al.  The occurrence of pharmaceuticals, personal care products, endocrine disruptors and illicit drugs in surface water in South Wales, UK. , 2008, Water research.

[187]  J. V. Sancho,et al.  Simultaneous determination of acidic, neutral and basic pharmaceuticals in urban wastewater by ultra high-pressure liquid chromatography-tandem mass spectrometry. , 2010, Journal of chromatography. A.

[188]  P. Schröder,et al.  Metabolism of diclofenac in plants--hydroxylation is followed by glucose conjugation. , 2012, Journal of hazardous materials.

[189]  D. Barceló,et al.  Tracing pharmaceutical residues of different therapeutic classes in environmental waters by using liquid chromatography/quadrupole-linear ion trap mass spectrometry and automated library searching. , 2009, Analytical chemistry.

[190]  N. Getoff Factors influencing the efficiency of radiation-induced degradation of water pollutants , 2002 .

[191]  M. Rodrigo,et al.  Electrochemical advanced oxidation processes: today and tomorrow. A review , 2014, Environmental Science and Pollution Research.

[192]  N. Gondrexon,et al.  Modeling of ultrasonic degradation of non-volatile organic compounds by Langmuir-type kinetics. , 2010, Ultrasonics sonochemistry.

[193]  M. Reinhard,et al.  Impacts of emerging organic contaminants on freshwater resources: review of recent occurrences, sources, fate and effects. , 2010, The Science of the total environment.

[194]  V. Belgiorno,et al.  Ultrasonic degradation, mineralization and detoxification of diclofenac in water: optimization of operating parameters. , 2010, Ultrasonics sonochemistry.

[195]  J. Hollender,et al.  Removal of micropollutants in municipal wastewater treatment plants by powder-activated carbon. , 2012, Water science and technology : a journal of the International Association on Water Pollution Research.

[196]  Adriano Joss,et al.  Scrutinizing pharmaceuticals and personal care products in wastewater treatment. , 2004, Environmental science & technology.

[197]  T. Urase,et al.  The effect of deterioration of nanofiltration membrane on retention of pharmaceuticals , 2007 .

[198]  H R Rogers,et al.  Sources, behaviour and fate of organic contaminants during sewage treatment and in sewage sludges. , 1996, The Science of the total environment.

[199]  Stacy D. Brown,et al.  Identification of “Known Unknowns” Utilizing Accurate Mass Data and Chemical Abstracts Service Databases , 2011, Journal of the American Society for Mass Spectrometry.

[200]  G. Duca,et al.  Pharmaceuticals and Personal Care Products in the Environment , 2009 .

[201]  D. Calamari,et al.  Pharmaceuticals in the Environment in Italy: Causes, Occurrence, Effects and Control , 2006, Environmental science and pollution research international.

[202]  J A Byrne,et al.  Rapid loss of estrogenicity of steroid estrogens by UVA photolysis and photocatalysis over an immobilised titanium dioxide catalyst. , 2004, Water research.

[203]  Roberta Curini,et al.  Monitoring Natural and Synthetic Estrogens at Activated Sludge Sewage Treatment Plants and in a Receiving River Water , 2000 .

[204]  J. Sumpter,et al.  Derivation of an aquatic predicted no-effect concentration for the synthetic hormone, 17 alpha-ethinyl estradiol. , 2008, Environmental science & technology.

[205]  Thomas Letzel,et al.  Serial coupling of RP and zwitterionic hydrophilic interaction LC-MS: suspects screening of diclofenac transformation products by oxidation with a boron-doped diamond electrode. , 2013, Journal of separation science.

[206]  G. Palmisano,et al.  Overview on oxidation mechanisms of organic compounds by TiO2 in heterogeneous photocatalysis , 2012 .

[207]  Christopher Bellona,et al.  Effect of membrane fouling on transport of organic contaminants in NF/RO membrane applications , 2006 .

[208]  K. Fent,et al.  Ecotoxicology of human pharmaceuticals. , 2006, Aquatic toxicology.

[209]  Osamu Nishimura,et al.  Estrogen removal from treated municipal effluent in small-scale constructed wetland with different depth. , 2009, Bioresource technology.

[210]  Yong-Gyun Park,et al.  Adsorption of bisphenol A and 17α-ethinyl estradiol on single walled carbon nanotubes from seawater and brackish water , 2011 .

[211]  A. Ruth Godfrey,et al.  Accurate mass measurements and their appropriate use for reliable analyte identification , 2012, Analytical and Bioanalytical Chemistry.

[212]  A. Ghauch,et al.  Fe0-based trimetallic systems for the removal of aqueous diclofenac: Mechanism and kinetics , 2011 .

[213]  Gun-Young Park,et al.  Oxidation of pharmaceuticals during ozonation and advanced oxidation processes. , 2003, Environmental science & technology.

[214]  C. Prasse,et al.  Is biological treatment a viable alternative for micropollutant removal in drinking water treatment processes? , 2013, Water research.

[215]  I. Oller,et al.  Combination of Advanced Oxidation Processes and biological treatments for wastewater decontamination--a review. , 2011, The Science of the total environment.

[216]  P. Schröder Exploiting Plant Metabolism for the Phytoremediation of Organic Xenobiotics , 2007 .

[217]  John L. Zhou,et al.  Improved removal of estrogenic and pharmaceutical compounds in sewage effluent by full scale granular activated carbon: impact on receiving river water. , 2011, Journal of hazardous materials.

[218]  H. Köhler,et al.  Toxic effects of the non-steroidal anti-inflammatory drug diclofenac. Part II: cytological effects in liver, kidney, gills and intestine of rainbow trout (Oncorhynchus mykiss). , 2004, Aquatic toxicology.

[219]  D. Barceló,et al.  Development of a multi-residue analytical methodology based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) for screening and trace level determination of pharmaceuticals in surface and wastewaters. , 2006, Talanta.

[220]  T. Schmidt,et al.  Oxidation of diclofenac with ozone in aqueous solution. , 2008, Environmental science & technology.

[221]  John P Sumpter,et al.  Predicted‐no‐effect concentrations for the steroid estrogens estrone, 17β‐estradiol, estriol, and 17α‐ethinylestradiol , 2012, Environmental toxicology and chemistry.

[222]  W. Verstraete,et al.  Influence of manganese and ammonium oxidation on the removal of 17 alpha-ethinylestradiol (EE2). , 2009, Water research.

[223]  M. Carballa,et al.  Comparison of predicted and measured concentrations of selected pharmaceuticals, fragrances and hormones in Spanish sewage. , 2008, Chemosphere.

[224]  K. Bobrowski,et al.  Application of ionizing radiation in decomposition of selected organic pollutants in waters , 2012 .

[225]  Thorsten Reemtsma,et al.  Pathways and metabolites of microbial degradation of selected acidic pharmaceutical and their occurrence in municipal wastewater treated by a membrane bioreactor. , 2005, Water research.

[226]  T. Ternes,et al.  Evaluating the efficiency of advanced wastewater treatment: target analysis of organic contaminants and (geno-)toxicity assessment tell a different story. , 2014, Water research.

[227]  E. Somessari,et al.  Radiation processing of sewage and sludge. A review , 1998 .

[228]  D. A. Barry,et al.  Treatment of micropollutants in municipal wastewater: ozone or powdered activated carbon? , 2013, The Science of the total environment.

[229]  É. Caupos,et al.  Photodegradation of estrone enhanced by dissolved organic matter under simulated sunlight. , 2011, Water research.

[230]  C. Martínez-Huitle,et al.  Synthetic diamond films : preparation, electrochemistry, characterization, and applications , 2011 .

[231]  S. Esplugas,et al.  Effects of ozone pre-treatment on diclofenac: intermediates, biodegradability and toxicity assessment. , 2009, The Science of the total environment.

[232]  Reinhard Niessner,et al.  Residue analysis of the pharmaceutical diclofenac in different water types using ELISA and GC-MS. , 2003, Environmental science & technology.

[233]  D. Grandjean,et al.  Degradation of emergent contaminants by UV, UV/H2O2 and neutral photo-Fenton at pilot scale in a domestic wastewater treatment plant. , 2013, Water research.

[234]  Marcel Skoumal,et al.  Electrochemical incineration of diclofenac in neutral aqueous medium by anodic oxidation using Pt and boron-doped diamond anodes. , 2010, Chemosphere.

[235]  Mogens Henze,et al.  Activated sludge models ASM1, ASM2, ASM2d and ASM3 , 2015 .

[236]  Shane A. Snyder,et al.  Removal of endocrine disrupting compounds and pharmaceuticals by nanofiltration and ultrafiltration membranes , 2007 .

[237]  A. K. Pikaev Current status of the application of ionizing radiation to environmental protection: II. Wastewater and other liquid wastes (A review) , 2000 .

[238]  D. Barceló,et al.  Input of pharmaceuticals through coastal surface watercourses into a Mediterranean lagoon (Mar Menor, SE Spain): sources and seasonal variations. , 2014, The Science of the total environment.

[239]  Hung-Suck Park,et al.  Occurrence and removal of antibiotics, hormones and several other pharmaceuticals in wastewater treatment plants of the largest industrial city of Korea. , 2011, The Science of the total environment.

[240]  Capillary electrophoresis characterization of molecularly imprinted polymer particles in fast binding with 17β-estradiol. , 2010, Journal of separation science.

[241]  J. Madden,et al.  Assessing the exposure risk and impacts of pharmaceuticals in the environment on individuals and ecosystems , 2013, Biology Letters.

[242]  Christoph Ort,et al.  Cost-benefit analysis of the Swiss national policy on reducing micropollutants in treated wastewater. , 2014, Environmental science & technology.

[243]  F. Omil,et al.  Influence of the employment of adsorption and coprecipitation agents for the removal of PPCPs in conventional activated sludge (CAS) systems. , 2010, Water science and technology : a journal of the International Association on Water Pollution Research.

[244]  María Molinos-Senante,et al.  Cost modelling for wastewater treatment processes , 2011 .

[245]  F. Beltrán,et al.  Mechanism and kinetic considerations of TOC removal from the powdered activated carbon ozonation of diclofenac aqueous solutions. , 2009, Journal of hazardous materials.

[246]  J. Schwaiger,et al.  Toxic effects of the non-steroidal anti-inflammatory drug diclofenac. Part I: histopathological alterations and bioaccumulation in rainbow trout. , 2004, Aquatic toxicology.

[247]  S. Venkata Mohan,et al.  Removal of natural and synthetic endocrine disrupting estrogens by multi-walled carbon nanotubes (MWCNT) as adsorbent: Kinetic and mechanistic evaluation , 2012 .

[248]  J M Lema,et al.  Removal of persistent pharmaceutical micropollutants from sewage by addition of PAC in a sequential membrane bioreactor. , 2011, Water research.

[249]  V. Matamoros,et al.  Evaluation of a coagulation/flocculation-lamellar clarifier and filtration-UV-chlorination reactor for removing emerging contaminants at full-scale wastewater treatment plants in Spain. , 2013, Journal of environmental management.

[250]  T. Manickum,et al.  Occurrence, fate and environmental risk assessment of endocrine disrupting compounds at the wastewater treatment works in Pietermaritzburg (South Africa). , 2014, The Science of the total environment.

[251]  A. Usobiaga,et al.  Optimisation of microwave-assisted extraction for the determination of nonylphenols and phthalate esters in sediment samples and comparison with pressurised solvent extraction , 2005 .

[252]  Martin Krauss,et al.  Elimination of organic micropollutants in a municipal wastewater treatment plant upgraded with a full-scale post-ozonation followed by sand filtration. , 2009, Environmental science & technology.

[253]  Frederic D L Leusch,et al.  Comparison of five in vitro bioassays to measure estrogenic activity in environmental waters. , 2010, Environmental science & technology.

[254]  Bo Mattiasson,et al.  Selective removal of 17β-estradiol at trace concentration using a molecularly imprinted polymer , 2007 .

[255]  D. Barceló,et al.  Multi-residue analytical method for the determination of endocrine disruptors and related compounds in river and waste water using dual column liquid chromatography switching system coupled to mass spectrometry. , 2013, Journal of chromatography. A.

[256]  Lennart Mathiasson,et al.  Occurrence and removal of pharmaceuticals in a municipal sewage treatment system in the south of Sweden. , 2009, The Science of the total environment.

[257]  S. Esplugas,et al.  Ultrasonic treatment of water contaminated with ibuprofen. , 2008, Water research.

[258]  Adriano Joss,et al.  Biological degradation of pharmaceuticals in municipal wastewater treatment: proposing a classification scheme. , 2006, Water research.

[259]  C. Sonntag,et al.  Advanced oxidation processes: mechanistic aspects. , 2008, Water science and technology : a journal of the International Association on Water Pollution Research.

[260]  T. Reemtsma,et al.  Sensitive determination of acidic drugs and triclosan in surface and wastewater by ion-pair reverse-phase liquid chromatography/tandem mass spectrometry. , 2004, Rapid communications in mass spectrometry : RCM.

[261]  Richard M. Dinsdale,et al.  The removal of pharmaceuticals, personal care products, endocrine disruptors and illicit drugs during wastewater treatment and its impact on the quality of receiving waters. , 2009, Water research.

[262]  M. Dudziak,et al.  Selected factors affecting the elimination of hormones from water using nanofiltration , 2009 .

[263]  D. Barceló,et al.  Fast and comprehensive multi-residue analysis of a broad range of human and veterinary pharmaceuticals and some of their metabolites in surface and treated waters by ultra-high-performance liquid chromatography coupled to quadrupole-linear ion trap tandem mass spectrometry. , 2012, Journal of chromatography. A.

[264]  T. Heberer Occurrence, fate, and removal of pharmaceutical residues in the aquatic environment: a review of recent research data. , 2002, Toxicology letters.

[265]  A Oehmen,et al.  Assessing the removal of pharmaceuticals and personal care products in a full-scale activated sludge plant , 2012, Environmental Science and Pollution Research.

[266]  Shane A. Snyder,et al.  Role of membranes and activated carbon in the removal of endocrine disruptors and pharmaceuticals , 2007 .

[267]  P. Schröder,et al.  Conjugating Enzymes Involved in Xenobiotic Metabolism of Organic Xenobiotics in Plants , 2002 .

[268]  Yong-Jun Zhang,et al.  Selective removal of diclofenac from contaminated water using molecularly imprinted polymer microspheres. , 2011, Environmental pollution.

[269]  Long D. Nghiem,et al.  Combining MBR and NF/RO membrane filtration for the removal of trace organics in indirect potable wa , 2010 .

[270]  M. Servos,et al.  Behavior and occurrence of estrogens in municipal sewage treatment plants--I. Investigations in Germany, Canada and Brazil. , 1999, The Science of the total environment.

[271]  K. Linden,et al.  Comparison of the efficiency of *OH radical formation during ozonation and the advanced oxidation processes O3/H2O2 and UV/H2O2. , 2006, Water research.

[272]  T. T. ter Laak,et al.  Prediction of concentration levels of metformin and other high consumption pharmaceuticals in wastewater and regional surface water based on sales data. , 2013, The Science of the total environment.

[273]  T. Ternes,et al.  Oxidation of pharmaceuticals during water treatment with chlorine dioxide. , 2005, Water research.

[274]  S. Jørgensen,et al.  Occurrence, fate and effects of pharmaceutical substances in the environment--a review. , 1998, Chemosphere.