Article

Occurrence and fate of micropollutants in the Vidy Bay of Lake Geneva, Switzerland. Part II: Micropollutant removal between wastewater and raw drinking water

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Abstract

The occurrence and removal of 58 pharmaceuticals, endocrine disruptors, corrosion inhibitors, biocides, and pesticides, were assessed in the wastewater treatment plant (WWTP) of the city of Lausanne, Switzerland, as well as in the effluent-receiving water body, the Vidy Bay of Lake Geneva. An analytical screening method to simultaneously measure all of the 58 micropollutants was developed based on ultra performance liquid chromatography coupled to a tandem mass spectrometer (UPLC-MS/MS). The selection of pharmaceuticals was primarily based on a prioritization study, which designated them as environmentally relevant for the Lake Geneva region. Except for the endocrine disruptor 17alpha-ethinylestradiol, all substances were detected in 24-h composite samples of wastewater entering the WWTP or in the treated effluent. Of these compounds, 40% were also detected in raw drinking water, pumped from the lake 3 km downstream of the WWTP. The contributions of dilution and degradation to micropollutant elimination between the WWTP outlet and the raw drinking water intake were established in different model scenarios using hypothetical residence times of the wastewater in Vidy Bay of 1, 4, or 90 d. Concentration decrease due to processes other than dilution was observed for diclofenac, beta-blockers, several antibiotics, corrosion inhibitors, and pesticides. Measured environmental concentrations (MECs) of pharmaceuticals were compared to the predicted environmental concentrations (PECs) determined in the prioritization study and agreed within one order of magnitude, but MECs were typically greater than the corresponding PECs. Predicted no-effect concentrations of the analgesic paracetamol, and the two antibiotics ciprofloxacin and sulfamethoxazole, were exceeded in raw drinking water samples and therefore present a potential risk to the ecosystem.

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... Most sulphonamides are polar compounds and water-soluble, thus, they have been detected in many environmental matrices such as water, soil, and sediment [54,55]. In particular, sulfamethoxazole is detected in wastewater, surface water, and drinking water at concentrations of 100-2500, 60-150 and 12 ng/L, respectively [56][57][58]. Due to the inefficiency of conventional wastewater treatments in removing low concentrations of antibiotics, many authors have tested photo-Fenton as an alternative for the removal of sulfamethoxazole [16,28,30,56]. For example, Nawaz et al. [30] evaluated their degradation with a MWCNTs-NiFe 2 O 4 composite prepared by a one-step hydrothermal treatment. ...
... In particular, sulfamethoxazole is detected in wastewater, surface water, and drinking water at concentrations of 100-2500, 60-150 and 12 ng/L, respectively [56][57][58]. Due to the inefficiency of conventional wastewater treatments in removing low concentrations of antibiotics, many authors have tested photo-Fenton as an alternative for the removal of sulfamethoxazole [16,28,30,56]. For example, Nawaz et al. [30] evaluated their degradation with a MWCNTs-NiFe 2 O 4 composite prepared by a one-step hydrothermal treatment. ...
Article
Contaminants of emerging concern including pharmaceuticals and personal care products are increasingly detected at low concentrations in surface waters. Given the associated toxicity of these compounds, there is the potential for significant impacts on aquatic life and the food chain. Since most pharmaceuticals are not biodegradable, they cannot be removed by secondary treatment processes in conventional wastewater treatment plants. Therefore, the development of alternative treatment methods plays a critical role in the removal of pharmaceuticals. Energy consumption is a key factor in technology selection, and the use of solar energy may help minimise operating costs. Thus, this work provides a comprehensive review of relevant research published between 2016 and 2021 targeting the removal of active pharmaceutical ingredients using ultraviolet processes, including photo-Fenton, photocatalysis and photoelectrocatalysis. While the focus remains on the development of novel catalysts and some efforts have been made to demonstrate the reuse of these materials for multiple cycles, there is little work aimed at scaling up the systems or investigating their efficacy in real water matrices to test the potential beyond the laboratory setting. The review concludes with some recommendations for future studies, highlighting the importance of comparing technologies in terms of life cycle assessment, energy use, and financial considerations to provide a holistic understanding of the role that these technologies can play in removing trace pharmaceutical compounds from wastewater.
... The EDCs have been detected in different environmental media including wastewaters (Rowsell et al. 2009, Musolff et al. 2010, surface water and groundwaters (Latorre et al. 2003, Cailleaud et al. 2007, sediments (Fu et al. 2007), aquatic organisms (Belfroid et al. 2002, Pojana et al. 2007) and drinking waters (Maeng et al. 2010, Schriks et al. 2010, Morasch et al. 2010. Some studies aiming at assessing whether different groups of organisms show similar or dissimilar responses to selected EDCs have also been reported (Sumpter and Johnson, 2005). ...
... Some studies aiming at assessing whether different groups of organisms show similar or dissimilar responses to selected EDCs have also been reported (Sumpter and Johnson, 2005). Besides, health impairment has been demonstrated in aquatic species exposed to EDCs in urbanized and industrialized areas (Couillard et al. 2008, Harris et al. 2011 (Morasch et al. 2010, Musolff et al. 2010, Rowsell et al. 2009). recycling of sludge to agriculture land is in most cases the least expensive option for disposal, and also results in a degree of recycling of carbon, nitrogen, phosphorus and other minerals. ...
... Samples were diluted 1:1 with acidified Evian water (pH 2.5) and deuterated CBZ compounds were spiked to every sample as internal standards. The analytical method was adapted from previous work (Margot, 2015;Morasch et al., 2010), and details are given in the SI. UV 254 in SWG samples was measured using a 10 cm quartz cuvette. ...
... UV 254 was determined in a 10 cm cuvette. CBZ abatement was quantified using solid phase extraction, followed by UPLC-MS as described elsewhere (Morasch et al., 2010). For MS2 enumeration, the samples were concentrated 50-fold using a 100 kD Amicon filter (Millipore). ...
Article
Ozone treatment is an effective barrier against viral pathogens, wherefore it is an integral part of many water and wastewater treatment trains. However, the efficacy of ozone treatment remains difficult to monitor, due to the lack of methods to track virus inactivation in real-time. The goal of this work was to identify easy-to-measure proxies to monitor virus inactivation during water and wastewater treatment by ozone. Proxies considered were the abatement in UV absorbance at 254 nm (UV254) and carbamazepine (CBZ), a ubiquitous organic micropollutant with a similar abatement rate constant as human viruses. The proxies, as well as the inactivation of two viruses (MS2 coliphage and coxsackievirus B5) were measured in surface water and in a secondary wastewater effluent as a function of the specific ozone dose (mgO3/mg dissolved organic carbon). Virus inactivation was rapid in both matrices, but was more efficient in surface water. This trend was also evident when inactivation was assessed as a function of the ozone exposure to account for the different ozone demand of the two water types. Both proxies, as well as the specific ozone dose, were correlated with virus inactivation. The correlations depended only weakly on the virus species, but - with the exception of CBZ abatement - differed between the two water types. Finally, predictive relationships were established using Bayesian power models, to estimate virus inactivation based on the measurement of a proxy. The models were then applied to estimate the MS2 inactivation in a pilot-scale ozone reactor that treats surface water of Lake Zurich. All proxies yielded good estimates of the actual MS2 inactivation in the pilot plant, indicating that the proxy-inactivation relationships established in the laboratory can also be applied to flow-through reactors. This study confirms that ozone is a highly effective disinfectant for viruses in both surface water and wastewater, and that the abatement of UV254 and CBZ can be used to track virus inactivation during water and wastewater treatment.
... Cytotoxicity assessment on A549 cancer cells demonstrated that all photoproducts formed at pH 7 were less toxic than the parent compound.3.1.2. IntroductionPharmaceuticals and their degradation products are detected in surface waters, wastewater and groundwater at a range of ng/L to mg/L (aus derBeek et al. 2016;Morasch et al. 2010) and even in drinking waters(Benotti et al. 2009;. Because more than 2,000 active ingredients are approved in Europe,Perazzolo et al. (2010) proposed a priority list of 57 compounds for pharmaceuticals risks assessment. ...
Thesis
Les composés pharmaceutiques sont fréquemment détectés dans les eaux naturelles en raison de leur élimination partielle par les stations d’épuration. Ils peuvent avoir un impact sur les organismes aquatiques comme sur la santé humaine, en particulier les plus persistants dont des traces peuvent se retrouver dans l'eau potable. De plus, leurs produits de transformation (TPs) ne sont pas souvent identifiés, et leurs impacts rarement évalués.Un levier prometteur est l'écoconception, prenant en compte le devenir et l'impact environnemental dès le développement des molécules pharmaceutiques. Une molécule éco-conçue serait alors une molécule qui se dégrade facilement et qui produirait des TPs inoffensifs une fois excrétés dans l'environnement.Cette approche innovante a été évaluée en utilisant l’anticancéreux méthotrexate (MTX) comme modèle, en raison de son action cytotoxique, de sa présence dans les eaux usées et de l’apparition d’un métabolite nocif et persistant (le 7-hydroxy-methotrexate), par rapport à un analogue (OMTX) synthétisé selon l'hypothèse qu'il sera moins persistant et produira des composés moins toxiques. Cette hypothèse a été testée via l’étude i) de la photodégradation avec la mise en évidence de 11 TPs du MTX et de 12 du OMTX, révélant des voies de dégradation similaires mais une dégradation plus rapide à 254 nm pour OMTX; ii) de la biodégradation par une boue activée et l’impact en retour sur les communautés microbiennes ne montrant pas d’effet écotoxicologique majeur. 8 TPs additionnels ont été mis en évidence pour le MTX, le 7-OH-MTX est apparu mineur et transitoire, et 4 TPs pour l'OMTX, biodégradé plus rapidement ; iii) de la cytotoxicité au cours de la photo et de la biodégradation montrant une perte de l'action pharmaceutique d'origine et enfin iv) l'évaluation de l’écotoxicité aiguë sur des organismes aquatiques en faveur de l'OMTX.
... Furthermore, the presence of plants played an important role in the removal of MPs, as a higher removal efficiency was found compared to batches with the absence of plants, except for IBT, CAF, and SMZ where similar removals were found (Table 1). Especially, the value of plant presence was most pronounced for CBZ, MCPP, and DFC, which are often poorly removed by WWTPs as reported by e.g., Morasch et al. (2010) and Luo et al. (2014). ...
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Article
Micropollutants (MPs) include organic chemicals, for example, pharmaceuticals and personal care products. MPs have been detected in the aquatic environment at low concentrations (ng/L-µg/L), which may lead to negative impacts on the ecosystem and humans. Phytoremediation is a green clean-up technology, which utilizes plants and their associated rhizosphere microorganisms to remove pollutants. The selection of plant species is important for the effectiveness of the phytoremediation of MPs. The plant species Phragmites australis, Typha angustifolia, and Juncus effuses are often used for MP removal. In this study, batch experiments were conducted to select plant species with an optimal ability to remove MPs, study the effect of temperature on MP removal in plants and the phytotoxicity of MPs. This study also explored the degradation of a persistent MP propranolol in plants in more detail. Data show that all three investigated plant species removed most MPs efficiently (close to 100 %) at both 10 and 21.5 °C. The tested plant species showed a different ability to translocate and accumulate propranolol in plant tissues. Typha angustifolia and Juncus effuses had a higher tolerance to the tested MPs than Phragmites australis. Typha angustifolia and Juncus effuses are recommended to be applied for phytoremediation of MPs.Novelty statement The novelty of this study is the selection of Typha angustifolia and Juncus effuses as proper plant species for phytoremediation of micropollutants (MPs). These two plant species were selected due to their good ability to remove MPs, tolerate low temperature, and resist the toxicity of MPs. The outcomes from this study can also be applied for constructed wetlands in removing MPs from wastewater. This study demonstrates the uptake and degradation processes of persistent MP propranolol in plants in more detail. Understanding the degradation mechanisms of a MP in plants is significant not only for the application of phytoremediation on MP removal but also for the development of constructed wetland studies.
... Quinolone antibiotic average concentrations in influents (a) and effluents (b) of global sewage treatment plants (ng·L -1 ). Data sources:(Ghosh et al., 2009;Morasch et al., 2010;Prieto et al., 2011;Sim et al., 2011;Gao et al., 2012Gao et al., , 2016Gros et al., 2012;Gan et al., 2014;Zhang et al., 2016Zhang et al., , 2017K'Oreje et al., 2016;Mohapatra et al., 2016;Papageorgiou et al., 2016;Tran et al., 2016;Aydin et al., 2019;Faleye et al., 2019; Castrignanò et al., 2020;Ajibola et al., 2021). ...
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Article
According to the existing research results, this paper reviews the influent and effluent concentrations, migration and transformation, and influencing factors of quinolone antibiotics in sewage treatment plants (STPs) with activated sludge treatment processes. Animal breeding and slaughtering wastewater, pharmaceutical wastewater and medical and domestic sewage may be the main sources of quinolone antibiotics. The compounds and concentrations of quinolone antibiotics in influents and effluents around the world are quite different, which is generally due to the difference in social and environmental factors in different regions, and the different treatment processes and operating parameters adopted. The migration and transformation of quinolone antibiotics is usually the result of the synergistic effect of sludge adsorption, biodegradation and photolysis. Sludge adsorption based on electrostatic interaction, hydrophobic forces and other mechanisms is the dominant route to remove quinolone antibiotics, but it does not reduce the total amount of the target antibiotics. An appropriate selection of conditions and control of process variables are beneficial to improve the removal of quinolone antibiotics by biodegradation with co-metabolism. Sources control, treatment processes improvement, fate understanding and prediction, monitoring strategies and risks assessment are potential options for improving the elimination and controlling the pollution of quinolone antibiotics in the future.
... During the last decade a wide range of pharmaceuticals have been identified and quantified in the aquatic environment across several countries and their impacts on exposed environmental species [1][2][3][4] and humans [5] have been reported. However, currently it is not feasible to monitor all the pharmaceuticals released into the aquatic environment due to analytical feasibility and monetary limitations [6]. Recently, several procedures have been established to predict the total amount of pharmaceuticals emitted to the environment for risk assessment of pharmaceuticals in water by public authorities in both Europe [7,8] and the United States [9]. ...
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Article
Background The objective of this work to calculate prescribed quantity of an active pharmaceutical ingredient (API) in prescription medications for human use, to facilitate research on the prediction of amount of API released to the environment and create an open-data tool to facilitate spatiotemporal and long-term prescription trends for wider usage. Design We have developed an R package, PrAna to calculate the prescribed quantity (in kg) of an APIs by postcode using England’s national level prescription data provided by National Health Service, for the years 2015–2018. Datasets generated using PrAna can be visualized in a real-time interactive web-based tool, PrAnaViz to explore spatiotemporal and long-term trends. The visualisations can be customised by selecting month, year, API, and region. Results PrAnaViz’s targeted API approach is demonstrated with the visualisation of prescribed quantities of 14 APIs in the Bath and North East Somerset (BANES) region during 2018. Once the APIs list is loaded, the back end retrieves relevant data and populates the graphs based on user-defined data features in real-time. These plots include the prescribed quantity of APIs over a year, by month, and individual API by month, general practice, postcode, and medicinal form. The non-targeted API approach is demonstrated with the visualisation of clarithromycin prescribed quantities at different postcodes in the BANES region. Conclusion PrAna and PrAnaViz enables the analysis of spatio-temporal and long-term trends with prescribed quantities of different APIs by postcode. This can be used as a support tool for policymakers, academics and researchers in public healthcare, and environmental scientist to monitor different group of pharmaceuticals emitted to the environment and for prospective risk assessment of pharmaceuticals in the environment.
... 68,69 For a better exposure assessment, an advisable strategy is to combine those two complementary approaches together (i.e., prediction and measurement for occurrence levels lower and higher than LOQ, respectively), which has been adopted in some risk assessment studies. 70,71 Moreover, the fluctuation of the chemical concentrations over time in a pollution hotspot is also of concern. On the one hand, analytical measurement usually only presents a snapshot rather than a continuous picture of the pollution. ...
... Taux d'abattement moyens en STEU Seine centre (n=6). Les barres d'erreur représentent les valeurs minimales et maximales mesurées.Dans la littérature, les valeurs des taux d'abattement des biocides étudiés ici sont variables mais sont généralement inférieures à 50 %(Margot et al., 2013;Köck-Schulmeyer et al., 2013;Chen et al., 2012;Singer et al., 2010;Wick et al., 2010;Guillossou et al., 2019;Clara et al., 2012;Morasch et al., 2010). Concernant la STEU Seine centre,Guillossou et al. (2019) reportent aussi un taux d'abattement négatif pour le diuron (-19 %) l'année précédant la période de prélèvement de notre étude, avec une variabilité très importante (500 %). ...
Thesis
Ce travail de thèse s’est intéressé aux biocides utilisés dans les matériaux de construction extérieurs, à leur transfert vers les rejets urbains de temps de pluie (RUTP) et in fine vers le milieu récepteur. Les objectifs de ce travail étaient (i) d’identifier les familles de biocides utilisés dans les matériaux de construction, (ii) d’étudier la dynamique de ces biocides dans les eaux de l’agglomération parisienne et (iii) de prioriser leurs sources d’émission vers le milieu récepteur.Dans un premier temps, une méthodologie de priorisation, basée sur les émissions de biocides, l’exposition des populations aquatiques, l’écotoxicité des composés et la faisabilité technique de leur suivi simultané a été développée et a permis de sélectionner 18 biocides : diuron, isoproturon, méthylisothiazolinone (MIT), chlorométhylisothiazolinone (CMIT), benzisothiazolinone (BIT), octylisothiazolinone (OIT), dichloro-octylisothiazolinone (DCOIT), chlorure de diméthyldidécyl ammonium, chlorures de benzalkonium (C12-C16), terbutryne, cybutryne, terbuthylazine, carbendazime, butylcarbamate d’iodopropynyle (IPBC), thiabendazole, tébuconazole et mécoprop. Une méthode d’analyse par chromatographie liquide couplée à la spectrométrie de masse en tandem a ensuite été mise en place pour analyser ces biocides dans les fractions dissoute et particulaire des échantillons. Ils ont été suivis en entrée et en sortie de station de traitement des eaux usées (STEU), dans des RUTP et dans des eaux de rivière en amont et en aval de l’agglomération parisienne, constituant une base de données unique en France pour certaines des molécules considérées. Les résultats ont montré que les biocides suivis étaient ubiquistes dans l’ensemble de ces eaux, en particulier les benzalkoniums mesurés aux plus fortes concentrations (de l’ordre du µg/L dans les RUTP et en STEU et supérieures à 100 ng/L dans les eaux de surface pour le C12). Dans les eaux usées (EU), la MIT et la BIT ont aussi été retrouvées à des concentrations significativement supérieures à 100 ng/L. Dans les RUTP, le diuron, la MIT, la carbendazime et le mécoprop ont été quantifiés à 100 ng/L environ. Les résultats en Seine ont été comparées aux concentrations prédites sans effet et ont mis en avant le risque potentiellement élevé pour les populations aquatiques, notamment dû au diuron, à la carbendazime, à la DCOIT et aux benzalkoniums.Les origines des biocides dans les rejets de déversoirs d’orage (DO) de Clichy ont été étudiées. Elles sont mixtes pour la plupart des biocides qui sont donc apportés aussi bien par les EU que les eaux pluviales (EP). La MIT, la BIT et l’IPBC, très utilisés dans les produits cosmétiques et ménagers, sont principalement apportés par les EU. Au contraire, le diuron, l’isoproturon, la terbutryne, la carbendazime, le tébuconazole et le mécoprop sont majoritairement apportés par les EP en raison de leur utilisation dans les matériaux de construction et du phénomène de lixiviation par temps de pluie. La CMIT, l’OIT, la DCOIT, les benzalkoniums, la cybutryne, la terbuthylazine et le thiabendazole sont apportés de manière équivalente par les EU et les EP dans les DO en raison de leur utilisations dans les produits quotidiens (ménagers, cosmétiques, alimentaires, pharmaceutiques, etc.) et dans les matériaux de construction.Enfin, à partir des concentrations mesurées, les flux rejetés de manière continue par la STEU Seine centre par temps sec et de manière ponctuelle par le DO de Clichy ont été estimés et comparés aux flux transitant en Seine en amont des déversements. Les résultats ont souligné un impact ponctuel des DO sur la contamination de la Seine plus important que les rejets continus de la STEU Seine centre. Toutefois, les flux annuels rejetés par temps sec et temps de pluie estimés à l’échelle de l’agglomération parisienne ont montré que les STEU étaient la principale voie d’introduction des biocides dans le milieu récepteur
... Pharmaceuticals and their degradation products are detected in surface waters, wastewater, and groundwater at a range of ng/ L to mg/L (aus der Beek et al. 2016;Morasch et al. 2010) and even in drinking waters (Benotti et al. 2009;Mompelat et al. 2011). Because more than 2000 active ingredients are approved in Europe, Perazzolo et al. (2010) proposed a priority list of 57 compounds for pharmaceutical risk assessment. ...
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Article
Methotrexate is an antineoplastic folate analog of high environmental concern, due to its low biodegradability and toxicological properties. This study focused on its photodegradation under two irradiation conditions, aiming to be representative of environment (300–450 nm) and drinking water treatment (254 nm). The photodegradation experiments were conducted at two pH, to vary the methotrexate ionization state and to produce a large variety of transformation products (TPs). The degradation kinetics determined through LC-UV monitoring were contrasted according to pH and irradiation wavelength. However, the quantum yields were independent of ionization state at 254 nm and the changes in kinetics at higher wavelengths were attributed to a change in the degradation mechanism. The TPs formed during the reactions were identified by UHPLC-MS/MS, using both the positive and negative modes. Among the eleven proposed structures, five were described as methotrexate TPs for the first time. The TPs result from N-demethylation, glutamic acid oxidation, and C–N cleavage, all of them leading to further degraded photoproducts presenting modified or lost glutamic acid part. This was made possible thanks to the negative mode, which allowed the exploration of the glutamic acid moiety modifications. Cytotoxicity assessment on A549 cancer cells demonstrated that all photoproducts formed at pH 7 were less toxic than the parent compound.
... The increasing presence of harmful contaminants of emerging concern (CECs) in water resources (Carrera et al. 2019;Liang et al. 2013;Matamoros et al. 2012;Morasch et al. 2010;Snyder et al. 2005) and the limitations of conventional urban wastewater (UWW) treatment plants in removing them (Moreira et al. 2016;Sirtori et al. 2011;Szymański et al. 2018) have become an environmental global concern. ...
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Article
This work aims to integrate several hydrogen peroxide (H2O2) activation mechanisms, photolysis (UVC irradiation), chemical electron transfer (TiO2-P25 photocatalysis), and reaction with TiO2-P25 in dark conditions, for reactive oxygen species (ROS) generation towards the removal of contaminants of emerging concern (CECs), in a single unit operated in continuous-flow mode. An H2O2 stock solution is fed by the lumen side of a tubular ceramic membrane, delivering the oxidant to the (i) catalyst immobilized in the membrane shell-side and (ii) annular reaction zone (ARZ, space between membrane shell-side and outer quartz tube) where CECs contaminated water flows with a helix trajectory, being activated by UV light provided by four lamps placed symmetrically around the reactor. First, the effect of several parameters in the removal of a CEC target molecule, amoxicillin (AMX), was evaluated using a synthetic solution ([AMX]inlet = 2.0 mg L⁻¹): (i) light source (UVA or UVC radiation), (ii) H2O2 dose, (iii) H2O2 injection method (radial permeation vs. upstream injection), and (iv) number of TiO2-P25 layers deposited on the membrane. The UVC/H2O2/TiO2 system with radial addition of H2O2 (20 mg L⁻¹) and 9-TiO2-P25 layers provided the highest AMX removal efficiency (72.2 ± 0.5%) with a UV fluence of 45 mJ cm⁻² (residence time of 4.6 s), due to the synergic effect of four mechanisms: (i) AMX photolysis, (ii) H2O2 photocleavage, (iii) TiO2-P25 photoactivation, and (iv) chemical reactions between H2O2 and TiO2-P25. The urban wastewater matrix showed a negative effect on AMX removal (~44%) due to the presence of ROS scavengers and light-filtering species. Graphical abstract
... Hence, there is interest to provide efficient techniques for its qualitative and quantitative determination, either to test the accuracy of the amounts present in pharmaceuticals or to monitor its presence in human fluid samples and in the environment. Among analgesic pharmaceuticals, paracetamol (acetaminophen, APAP, figure 2) is the most frequent one, as environment pollutant and a potential risk to the ecosystem [15][16][17][18][19]. These studies bring out the question of monitoring of pharmaceutical compounds in ecosystem. ...
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Article
Electrochemical methods used for analysis and detection of chemical compounds have significant advantages, such as simplicity and speed of work and low limits of detection. Methods of choice include cyclic, adsorptive stripping, differential pulse and square wave voltammetry. From the point of view of health sciences, environmental sciences and pharmaceutical industry, it is important to develop reliable techniques of pharmaceutical compounds determination. Paracetamol, as one of the most frequently prescribed analgesic medications, is widely present in households and environment. Therefore, it is of scientific and practical interest to test possible ways of its determination in order to find the most suitable ones. In order to provide economic means of detection, numerous authors tested pencil graphite electrodes, as widely available and low cost material suitable for surface modifications, and proved that they can be efficiently used to detect very low concentrations, around 10⁻⁹ M, of paracetamol.
... Because poor removal at conventional wastewater treatment plants and little decomposition in sewers, the SMX largely enters the aquatic environment. At a typical occurrence level of 0.01-2.5 μg/L in surface water and wastewater effluent (Al Aukidy et al., 2012;Kolpin et al., 2002;Morasch et al., 2010;Padhye et al., 2014;Ratola et al., 2012), SMX exhibits a high resistance against biodegradation and photo hydrolysis (Osorio et al., 2016;Shimabuku et al., 2016;Yin et al., 2019). Its long-term and subtle chronic effects on human beings is also a concern owing to the proliferation of antibacterial resistant genes (Kummerer, 2009a(Kummerer, , 2009bRizzo et al., 2013). ...
Article
Perovskites with flexible texture structures and excellent catalytic properties have attracted considerable attention in peroxymonosulfate (PMS) activation for addressing organic contaminants in water. In this study, the role of copper to promote PMS activation performance of LaMnO3 was investigated. 100% sulfamethoxazole (SMX) degradation and 34% mineralization were achieved over copper doped LaMnO3 while only 60% SMX was removed without TOC removal by LaMnO3. Especially, compared with LaMnO3, the pseudo-first-order reaction rate constants was increased by 8.30 times when the atomic ratio of Cu/Mn was 1:3. It proved that only ¹O2 was generated in LaMnO3 while ¹O2, especially •OH and SO4•⁻ were all detected in Cu-LaMnO3/PMS system. The characterization results showed that Cu induced the formation of LaMnO3 and La2CuO4 heterostructure with enhanced content of relatively low-valence Mn and Cu and abundant oxygen vacancies (OVs). Hence, the efficient PMS activation by Cu-LaMnO3 was due to regulating the produced reactive oxygen species (ROS). A radical dominant instead of ¹O2 involved PMS activation mechanism over LaMnO3-La2CuO4 was proposed for efficient degradation of SMX. Finally, the possible degradation pathways of SMX were discussed based on HPLC-MS analysis. This study provided a new insight of improving the catalytic activity of perovskites in PMS activation in water treatment.
... Pesticides like atrazine, parathion, lindane, endosulfan, dichlorodiphenylaceticacid, endrin and oxychlordane are used in agricultural fields and domestic places (Devi and Raha 2013). The recalcitrant nature of the contaminants headed to development of various advanced efficient techniques based on engineered nanomaterials that are cheap, accessable and can able to complete removal or degradation of pesticides (Morasch et al. 2010;Ormad et al. 2011;Pitarch et al. 2010). Engineered nanomaterials are promoted to industrial scale due to their enhanced characteristic, wide band gap and improved output of applications. ...
Book
This book reviews advanced techniques for the determination of pesticide residues, with focus on extraction, detectors and cleaning protocols. Chapters also discuss pesticide occurrence, toxicity and remediation.
... Many of these micropollutants, especially pharmaceuticals, reach surface water via wastewater effluents (Schwarzenbach et al., 2006). Two pharmaceuticals frequently found in wastewater and surface water are metoprolol (METO) and diclofenac (DCF) (aus der Beek et al., 2016;Chávez et al., 2019;Fernández et al., 2010;Hughes et al., 2013;Morasch et al., 2010;Verlicchi et al., 2012;Zhang et al., 2008). Isoproturon (ISO) is an example of a herbicide still found in surface water (Cui et al., 2020) and secondary wastewater effluents (Chávez et al., 2019), despite the fact that is was banned in the European Union in 2016 (The European Comission, 2016). ...
Article
Micropollutants reach the aquatic environment through wastewater treatment plant effluents. Ozonation, applied in wastewater treatment for micropollutants abatement, can yield transformation products (TP), which might be of ecotoxicological concern. Previous studies on TP formation were mostly performed in ultrapure water. However, the water matrix can have a substantial influence and lead to unpredictable yields of TPs with toxicological potential. In this study the acute toxicity (immobilization) of the parent substances (isoproturon and metoprolol) and also of available TPs of isoproturon, metoprolol and diclofenac towards Daphnia magna (D. magna) were investigated. Further, the acute toxicity of TP mixtures, formed during ozonation of isoproturon, metoprolol and diclofenac was evaluated in the following systems: in the presence of radical scavengers (tert-butanol and dimethyl sulfoxide) and in the presence of hypobromous acid (HOBr), a secondary oxidant in ozonation. For all tested substances and TP standards, except 2,6-dichloroaniline (EC50 1.02 mg/L (48 h)), no immobilization of D. magna was detected. Ozonated pure water and wastewater did not show an immobilization effect either. After ozonation of diclofenac in the presence of dimethyl sulfoxide 95% (48 h) of the daphnids were immobile. Ozonation of parent substances, after the reaction with HOBr, showed no effect for isoproturon but a high effect on D. magna for diclofenac (95% immobilization (48 h)) and an even higher effect for metoprolol (100% immobilization (48 h)). These results emphasize that complex water matrices can influence the toxicity of TPs as shown in this study for D. magna.
... In the literature, biocide removals vary from one study to another but are usually lower than 50 % (Margot et al., 2013;Singer et al., 2010;Wick et al., 2010;Guillossou et al., 2019;Chen et al., 2012;Juksu et al., 2019;Köck-Schulmeyer et al., 2013;Clara et al., 2012;Morasch et al., 2010;Liu et al., 2017). Similar to this study, a good removal of DCOIT (75 %), OIT (80 %) and BIT (> 80 %) was observed by Chen et al. (2012), Liu et al. (2017) and Juksu et al. (2019), respectively. ...
Article
Eighteen biocides used in building materials and domestic products were monitored in wastewater treatment plants (WWTPs) during dry weather and in combined sewer overflows (CSOs) during wet weather in the Paris conurbation. The aims of this study were to (i) acquire data on biocides in urban waters, which are very scarce up to now, (ii) identify their origins in CSOs with the perspective of reducing these contaminants at source, and (iii) compare and rank biocide pathways to the river (dry vs. wet weather) at the annual and conurbation scales. The results showed the ubiquity of the 18-targeted biocides in WWTP waters and CSOs. High concentrations of methylisothiazolinone, benzisothiazolinone (0.2-0.9 µg/L) and benzalkonium C12 (0.5-6 µg/L) were measured in wastewater. Poor WWTP removals (< 50%) were observed for most of the biocides. Both wastewater (mainly domestic uses) and stormwater (leaching from building materials) contributed to the CSO contamination. However, benzisothiazolinone mainly came from wastewater whereas diuron, isoproturon, terbutryn, carbendazim, tebuconazole, and mecoprop mainly came from stormwater. Annual mass loads discharged by WWTPs and CSOs into the Seine River were estimated using a stochastic approach (Monte Carlo simulations) at the conurbation scale and showed that WWTP discharges are the major entry pathway.
... Samples were diluted 1:1 with acidified Evian water (pH ~2.5, HCl 25%) and a deuterated analogue of each target TrOC was spiked into every sample as an internal standard. The analytical method was adapted from previous work ( Bonvin, 2013 ;Margot, 2015 ;Morasch et al., 2010 ) and details can be found in the supplementary information. TrOC concentrations were calculated based on calibration curves using all 8 calibration points for high concentrations and only the 5 lowest standards for low concentrations. ...
Article
Powdered activated carbon (PAC) is increasingly used as tertiary treatment for the removal of trace organic contaminants (TrOCs) from wastewater (WW). To enhance the sorption kinetics and capacity, the PAC particles can be milled down to super fine powdered activated carbon (SPAC). However, the small-grained SPAC particles are prone to aggregation, which may impact their treatment performance. In this study we examined the effect of SPAC dispersion and aggregation on TrOCs removal kinetics and sorption capacity. Specifically, we assessed how two interventions that modulate the apparent size of SPAC - ultrasonication and coagulation - affect the uptake of TrOCs in secondary WW effluent. We quantified the removal of fourteen TrOCs, of which twelve are indicator substances for micropollutant removal in WWTPs as designated by the Swiss Water Protection Ordinance. We determined that at high SPAC doses (> 1.6 mgSPAC/mg Dissolved Organic Carbon [DOC]), the TrOC removal kinetics were fast even for aggregated SPAC, such that SPAC dispersal by ultrasonication yielded no benefit. At low SPAC doses (< 1.6 mgSPAC/mgDOC) and contact times (< 2 minutes) ultrasonication was beneficial, in particular if the SPAC particles reached complete dispersion prior to exposure to TrOCs. However, the energy consumption of such an ultrasonication step should be carefully weighed against the additional energy requirement associated with using a higher SPAC dose. Finally, a coagulant to mitigate membrane fouling can be added simultaneously with the SPAC without compromising the TrOC removal efficiency. We conclude that under realistic SPAC application scenarios in WWTPs, interventions that disperse SPAC during TrOC sorption are not necessary, and processes that aggregate SPAC are acceptable.
... A WWTP in Lausanne, Switzerland that uses chemical precipitation techniques, followed by either activated sludge or sedimentation, showed a good removal rate of various pesticides including chloridazon, tebufenozide, and irgarol. However, other pesticides were removed to a lesser extends, while atrazine, mecoprop, and propiconazole were not removed at all (Morasch et al., 2010). Moreover, Samir et al. (2015) have studied the possibility of biodegradation of 2,4-D (up to 700 mg/L) using two microbial consortia containing bacteria and protozoa. ...
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The levels of pesticides in water have increased due to their excessive use in the modern agricultural domain. Choosing a suitable water treatment method for pesticide removal depends on the type of pesticide and the efficacy of the treatment process. This review critically discusses and provides a detailed description of a variety of chemical, physical, and biological approaches for pesticide removal from water, such as advanced oxidation processes, adsorption, activated sludge, membrane bioreactors, and membrane technologies. Both single-treatment and hybrid methods are thoroughly described and critically discussed. The use of hybrid removal techniques offers potential opportunities to develop innovative pesticide removal techniques. A thorough analysis of influent composition and recognition of the best removal technique is very important to design a water treatment plant that targets the maximum possible removal rate for different types of pesticides. Furthermore, the decentralization of water treatment was also discussed in which it is an important approach that would lead to better effluent water quality for lower prices. Many affordable techniques such as activated sludge and adsorption by agricultural adsorbents showed high efficacy in treating high levels of different pesticides.
... The fate of antibiotics and pharmaceuticals in the pilot-scale water treatment process of present water plants showed that most drugs could be fully eliminated through the ozonation and two-step granular activated carbon filtration. However, the high-use fluoroquinolone antibiotic ciprofloxacin (CIP) was found to directly pass through the whole treatment process with extremely low adsorption (Vieno et al., 2007;Morasch et al., 2010). It is imperative to explore an efficient absorbent for the removal of CIP fluoroquinolone antibiotic from drinking water and wastewater. ...
Article
Extensively used antibiotic ciprofloxacin increases in water environment, which is not efficiently removed by means of conventional adsorbents. MCM-41 has great potential for ciprofloxacin removal. There has been little research on ciprofloxacin removal by MCM-41 and their corresponding adsorption/desorption behaviors. In this study, amorphous SiO2, MCM-41 and diamine-functionalized MCM-41 were used as adsorbents to remove ciprofloxacin. In the adsorption process, their adsorption capacity followed the order of SiO2≪MCM-41< diamine-functionalized MCM-41. Ciprofloxacin adsorption behaviors were revealed through the analysis of adsorption isotherms and kinetics model: i. Adsorption process for MCM-41/diamine-functionalized MCM-41 mainly included three steps; and ii. Diamine-functionalized MCM-41 had higher adsorption capacity because of its more and stronger chemical-monolayer adsorption. In the desorption process, strong acid facilitated desorption by inhibiting the interaction between ciprofloxacin and diamine-functionalized MCM-41, and the mechanism was proposed and then supported by salt elution experiment. Last, the breakthrough bed volume and capacity of these absorbents were tested in column operation. Diamine-functionalized MCM-41 had better performance with 550 bed volume and 18.3 mg/g adsorption capacity in the treatment of 5.0 mg/L ciprofloxacin. Both batch and column results demonstrated that diamine-functionalized MCM-41 was highly efficient for ciprofloxacin removal. This study indicates great application prospect of mesoporous silica materials for ciprofloxacin removal and reveals their adsorption/desorption behaviors, which could provide guidance on adsorbent modification/regeneration for antibiotics removal.
... Researchers have therefore employed certain criteria related to PEC/MEC to evaluate the prediction results. For example, Morasch et al. and Tauxe-Wuersch et al. adopted the following criteria to classify PEC: 0.1 < PEC/MEC < 10, acceptable (Morasch et al., 2010;Tauxe-Wuersch et al., 2005); PEC/MEC < 0.1, unacceptably low; PEC/MEC > 10, unacceptably high. Stricter criteria were proposed by Ort et al.: 0.5 < PEC/MEC < 2, acceptable, PEC/MEC < 0.5, unacceptably low; and PEC/MEC > 2, unacceptably high (Ort et al., 2009). ...
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Information on sales and emission of selected pharmaceuticals were used to predict their concentrations in Japanese wastewater influent through a >300 of pharmaceuticals data sink. A combined wastewater-based epidemiology and environmental risk analysis follow was established. By comparing predicted environmental concentrations (PECs) of pharmaceuticals in wastewater influent against measured environmental concentrations (MECs) reported in previous studies, it was found that the model gave accurate results for 17 pharmaceuticals (0.5
... The sheer amount of different OMPs, their multi-facetted behaviors and complex correlations of environmental factors underline the challenge to depict fate and transport of OMP's in surface water. The impact of OMPs on drinking water source areas have been reported for Switzerland (Bonvin et al., 2011;Hoerger et al., 2014;Morasch et al., 2010), Germany (Schimmelpfennig et al., 2016) and China (Hu et al., 2017;Ma et al., 2016). Extensive studies about the occurrence of OMPs in Scandinavia are, however, scarce. ...
Article
The main objective of this study was to comprehensively investigate the occurrence of organic micropollutants (OMPs) in the surface water in Lake Mälaren over a period of one year and assess the spatial (horizontal and vertical) distribution and seasonal trends of OMPs. The applied multi-residue method comprised 111 OMPs covering compounds with wide range of physicalal-chemical properties. In total, 46 OMPs were detected at least once above limit of quantification (LOQ). DEET (diethyltoluamide), lamotrigine, bicalutamide, tolyltriazole, caffeine, carbamazepine, metoprolol, oxazepam, cetirizine, fexofenadine, lidocaine and tramadol were detected in more than 75% of the sampling points. The highest detected concentration was found for lamotrigine with 140 ng/L. The locations Ekoln and Västeråsfjärden were identified to be most affected by OMPs pollution. In the surface water (0.5 m depth) most highest concentrations of OMPs were observed in spring and lower concentrations in summer. Antihistamine demonstrated a seasonal trend that can be related to seasonal consumption patterns. The investigation of the vertical distribution of OMPs demonstrated that thermal lake stratification can lead to different concentrations within the water column. For instance, in February the highest concentration for most OMPs was observed in the deepest sampled water depth (30 m). Two industrial chemicals, tolyltriazole and tris(2-butoxylethyl)phosphate were detected frequently and it is recommended to incorporate these compounds more regularly in future analysis. To the best of our knowledge, this study is the first one to report the occurrence and distribution of OMPs representing such wide physico-chemical properties, including industrial chemicals, in a Swedish lake.
... A few studies reported a decreasing trend of biocide concentrations from 1 year to the next because of bans on some (Öllers et al. 2001;Kupper et al. 2006;Burkhardt et al. 2007;Gómez et al. 2007;Kahle et al. 2008;Bartelt-Hunt et al. 2009;Benvenuto et al. 2010;Morasch et al. 2010;Singer et al. 2010;Stamatis et al. 2010;Wick et al. 2010;Chen et al. 2012;Clara et al. 2012;Gros et al. 2012;Barco-Bonilla et al. 2013;Campo et al. 2013;Margot et al. 2013;Masiá et al. 2013;Luft et al. 2014;Bollmann et al. 2014a;Mailler et al. 2015;Launay et al. 2016;Peris-Vicente et al. 2016;Wluka et al. 2016). I influents and E effluents. ...
... The lakes Patancheru, Kazipeli, Ambazari, Futala, Nandi Hills, Biwa, Yen So, al-Asfar, and al-Hubail were reported to have very high pharmaceutical concentrations in Asia, which were associated with insufficiently treated municipal, industrial and agricultural wastewaters, pharmaceutical industries, and intentional wastewater disposal into lakes (Fick et al., 2009;Mutiyar and Mittal, 2014;Archana et al., 2017;Gopal et al., 2020;Chen et al., 2017;Tran et al., 2019;Picó et al., 2020). The lakes Buyukcekmece, Pamvotis, Polifitos, Tegel, Paijanne, Geneva, and Mjosa exhibited the highest pharmaceutical concentrations in Europe, which were originated from controlled or uncontrolled municipal and hospital wastewater discharges (Aydin and Talinli, 2013;Nannou et al., 2015;Kosma et al., 2014;Schimmelpfennig et al., 2012;Lindholm-Lehto, et al., 2015;Morasch et al., 2010;Balmer et al., 2004;Singer et al., 2002;Borga et al., 2012;Borga et al., 2013). The lakes Michigan, Erie, Ontario, Table S4. ...
Article
This study presents an estimation of the urine volume in the wastewater from a real, private clinic in Crete, Greece, during a seven-month period (01/06/2018 to 31/12/2018). Separate estimates were obtained for the volume of urine belonging to patients receiving antibiotics. It was found that the clinic disposed into the local municipal sewage network on the average 3,263 L/month of urine, from which 1,331 L/month (40.8%) belonged to patients receiving antibiotics. According to the pharmacy department of the private clinic, during the period of the study, the most frequently administered groups of antibiotics were on the average 779 g/month cephalosporins (68.1%), 108 g/month fluoroquinolones (9.5%) and others (11.2%), with various active substances including cefuroxime, ciprofloxacin, metronidazole and doxycycline. These active substances act like pollutants when disposed via the municipal sewer network into the environment.
... A few studies reported a decreasing trend of biocide concentrations from 1 year to the next because of bans on some (Öllers et al. 2001;Kupper et al. 2006;Burkhardt et al. 2007;Gómez et al. 2007;Kahle et al. 2008;Bartelt-Hunt et al. 2009;Benvenuto et al. 2010;Morasch et al. 2010;Singer et al. 2010;Stamatis et al. 2010;Wick et al. 2010;Chen et al. 2012;Clara et al. 2012;Gros et al. 2012;Barco-Bonilla et al. 2013;Campo et al. 2013;Margot et al. 2013;Masiá et al. 2013;Luft et al. 2014;Bollmann et al. 2014a;Mailler et al. 2015;Launay et al. 2016;Peris-Vicente et al. 2016;Wluka et al. 2016). I influents and E effluents. ...
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Biocides are added to or applied on building materials to prevent microorganisms from growing on their surface or to treat them. They are leached into building runoff and contribute to diffuse contamination of receiving waters. This review aimed at summarizing the current state of knowledge concerning the impact of biocides from buildings on the aquatic environment. The objectives were (i) to assess the key parameters influencing the leaching of biocides and to quantify their emission from buildings, (ii) to determine the different pathways from urban sources into receiving waters and (iii) to assess the associated environmental risk. Based on consumption data and leaching studies, a list of substances to monitor in receiving water was established. Literature review of their concentrations in the urban water cycle showed evidences of contamination and risk for aquatic life, which should put them into consideration for inclusion to European or international monitoring programs. However, some biocide concentration data in urban and receiving waters is still missing to fully assess their environmental risk, especially for isothiazolinones, iodopropynyl carbamate, zinc pyrithione and quaternary ammonium compounds, and little is known about their transformation products. Although some models supported by actual data were developed to extrapolate emissions on larger scales (watershed or city scales), they are not sufficient to prioritize the pathways of biocides from urban sources into receiving waters during both dry and wet weathers. Our review highlights the need to reduce emissions and limit their transfer into rivers and reports several solutions to address these issues.
... These micropollutants have based on the anthropogenic effects, such as pharmaceuticals, pesticides, personal care products and industrial chemicals (Luo et al., 2014). It is known that all these micropollutants have toxic effects on aquatic species (Morasch et al., 2010;Pochodylo & Helbling, 2015;Minguez et al., 2016). Aquatic communities can be dramatically affected by the cocktail of low concentrations of micropollutants (Morash et al., 2010). ...
Article
Stagnant freshwaters can be affected by anthropogenic pollution and eutrophication that leads to massive growth of cyanobacteria and microalgae forming complex water blooms. These can produce various types of bioactive compounds, some of which may cause embryotoxicity, teratogenicity, endocrine disruption and impair animal or human health. This study focused on potential co-occurrence of estrogenic and retinoid-like activities in diverse stagnant freshwaters affected by phytoplankton blooms with varying taxonomic composition. Samples of phytoplankton bloom biomass and its surrounding water were collected from 17 independent stagnant water bodies in the Czech Republic and Hungary. Total estrogenic equivalents (EEQ) of the most potent samples reached up to 4.9 ng·g⁻¹ dry mass (dm) of biomass extract and 2.99 ng·L⁻¹ in surrounding water. Retinoic acid equivalent (REQ) measured by in vitro assay reached up to 3043 ng·g⁻¹ dm in phytoplankton biomass and 1202 ng·L⁻¹in surrounding water. Retinoid-like and estrogenic activities at some sites exceeded their PNEC and effect-based trigger values, respectively. The observed effects were not associated with any particular species of cyanobacteria or algae dominating the water blooms nor related to phytoplankton density. We found that taxonomically diverse phytoplankton communities can produce and release retinoid-like compounds to surrounding water, while estrogenic potency is likely related to estrogens of anthropogenic origin adsorbed to phytoplankton biomass. Retinoids occurring in water blooms are ubiquitous signalling molecules, which can affect development and neurogenesis. Selected water bloom samples (both water and biomass extracts) with retinoid-like activity caused effects on neurodifferentiation in vitro corresponding to those of equivalent all-trans-retinoic acid concentrations. Co-occurrence of estrogenic and retinoid-like activities in stagnant water bodies as well as the potential of compounds produced by water blooms to interfere with neural differentiation should be considered in the assessment of risks associated with water blooms, which can comprise complex mixtures of natural and anthropogenic bioactive compounds.
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Biodegradable plant-based plastics are made and used as a substitute for plastics made from petrochemicals. However, the negative impacts of plant-based plastics are not well studied. This study addressed the question as to whether or not corn-based microplastic beads affect the lifehistory traits of the harlequin fly Chironomus riparius, a species of non-biting midge. The effects of microplastic beads made from corn (polylactic acid: PLA) on the life history traits of chironomid larvae were compared against the effects of microplastic beads made from petrochemical (polystyrene: PS) and a control (without microplastic beads), by exposing them to artificial sediment spiked with PLA and PS for 10 days and 28 days exposures. The endpoints used in this research to determine performances of chironomid larvae were survival and development time. Results showed that there were no differences in survival between treatments after 10 days of exposure. However after 28 days of exposure chironomid larvae exposed to PS and PLA showed a trend for a significantly lower survival compared to the control without microplastics(P = 0.059). Development time of Day 28 exposure did not differ between any of the treatments: PS, PLA and control. Female chironomid larvae did however show a significantly longer development time but this was not affected by treatment. In summary, there were no differences between polylactic acid (PLA) and polystyrene (PS) based microplastics in terms of survival and development time.
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The high use of antibiotics worldwide has poses a serious threat to both human and environmental health. Lakes are served as reservoirs for antibiotics, however, there is a lack of information available on antibiotics emissions and the subsequent pollution. Here, the emission and fate of 34 frequently detected antibiotics were studied in 226 Chinese lakes, via the built emission estimation method and a temperature-dependent multimedia lake model. It has been estimated that totally 5711 tons antibiotic were discharged into the lakes of China in 2019. Antibiotics emissions are due to human activities, with 3800-fold higher emissions in the Eastern China than that in Western China. The antibiotic fate in lakes has been successfully modelled by simulating the lake stratification, freeze-melt cycles and the stable condition throughout the year. Both stratification and freeze-melt cycles can lead to increased antibiotic concentrations in lake water. Deep-water lakes were shown to serve as a highly effective natural storage medium for antibiotics. The reliability of the model was confirmed by published measured concentrations and Monte Carlo method. This is the first study to comprehensively investigate the antibiotic fate in lakes of China, providing valuable guidance for the remediation of contaminated lakes.
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Rapid development of pharmaceuticals outpaces the efforts to regulate and monitor their trace concentrations in the environment. This emerging issue can only be solved through field studies, solid fate and transport models, and adequate risk assessment of the concerned contaminants. This approach requires the availability of toxicological information about the contaminants along with an understanding of their full potential in different media of the environment. This review paper focuses on commonly used seven pharmaceutical families across the globe: antacids, antibiotics, antidepressants, antiepileptics, beta blockers, lipid lowering drugs, and nonsteroidal anti-inflammatory drugs. Within each family, pharmaceuticals which are widely prescribed, studied, and frequently detected in environment were selected. The concentration levels in the environment, updated physicochemical properties, main natural removal mechanism, and ecological risk assessment towards the receptors of those pharmaceuticals in aquatic and terrestrial systems were analyzed. The following results were observed in the literature: 1) removal of the pharmaceuticals from wastewater treatment plants is reduced when the dissolved organic matter present; 2) many studies have cited older physicochemical properties of the concerned pharmaceuticals assuming relative conditions in their studies which can affect the accuracy of a model; 3) the number of studies are very limited for fate and transport in the soil; and 4) there is lack of cumulative risk assessment of mixed pharmaceutical substances. Therefore, this review will provide modeler with updated physiochemical properties; it will guide researchers to focus on removal of those contaminants at different lifecycle stages; and it will provide guidance to policy makers to develop effective policies and regulations.
Chapter
Micropollutants being an integral part of human lifestyle starting for, food material to cosmetics and pharmaceuticals are difficult to control. But these things causes serious hazard to both human and environment. The aquatic ecosystem is highly affected by these contaminants and this further biomagnifies. Hence the work focuses on occurrence of emerging contaminants in surface and ground water and their fate in waste water treatment plants with special reference to Indian scenario. Data deficiency in impacts, fate and concentration levels of emerging contaminants creates difficult for the government to create concrete plan to control their utilization and management in the environment. So concrete research, legal amendments and upgradation of existing technologies must be done to curb this hazard.
Article
Pharmaceuticals pollutions causes inevitable threat for both water environment and human health. However, both the selective and efficient accumulation together with degradation in real wastewater is still one of the major challenges which need further exploration. Here, we designed and synthesized MIL-100 based mesoporous carries supported surface molecularly imprinted polymers. The functional monomer was successfully grafted on the metal organic frameworks (MOFs) carries with magnetic core (Fe3O4). The simultaneous hydrolysis of functional precursor and condensation of the hydrolyzed precursors form a three–dimensional polymer network. Thanks to the high surface area and abundant mesoporous channels formed by the fast microwave irradiation method, it can facilitate mass transfer process and achieve high uptake capacity. This MIL-100 based imprinted polymer showed both ultrahigh selectivity (α(QMIP/QNIP) = 3.54) and highest uptake capacity calculated by the Langmuir equation (273.65 mg/g) for Ciprofloxacin so far. In order to prove the role of MIL-100 insides, pore size distribution, surface area, high angle annular dark field-scanning transmission electron microscopy (HAADF–STEM) images were studied detailly. Adsorption mechanism have been proposed based on X-ray Photoelectron Spectroscopy (XPS) and Infrared Spectroscopy (IR) spectra before and after the treatment. Importantly, the influence of environmental competitors including the inorganic ions and natural organic matters have been evaluated separately. Furthermore, the material can effectively remove targeted compound which was spiked in real secondary effluents from Beijing, substantiating that this novel MOFs–based material is among the rank of excellent CIP adsorbent. Furthermore, the iron-based active sites can be accessible for CIP, resulting the completely degradation under visible−light irradiation with small amount of hydrogen peroxide added. Our study presents a facile approach by introducing MILs to improve the performance of imprinted polymers.
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This review presents a compilation of pharmaceuticals and personal care products (PPCPs) that have been detected in waters, sediments and biota of lakes throughout the world by various researchers, over a 26-year time period (1996–2021). Numerous studies published in the literature reported that 286 pharmaceuticals and 70 personal care products (PCPs) were present in waters, 101 pharmaceuticals and 50 PCPs were present in sediments, and 63 pharmaceuticals and 19 PCPs were present in biota of lakes throughout the world. Among the pharmaceuticals present in lake waters, 194 had concentrations of over 5 ng/L, 173 were present in only one continent, whereas several (e.g. caffeine, carbamazepine and sulfamethoxazole) were detected in lake waters of almost every continent (6/7). Among the PCPs present in lake waters, 56 had concentrations of over 5 ng/L, whereas 41 were present in only one continent. PPCPs were found in 260 lakes, located within 44 countries, the majority of them present in Asian, European and North American lakes. Lakes with high pharmaceutical concentrations were affected by either controlled or uncontrolled wastewater originated from various types of sources. Based on this study, of high concern is the Asian continent, where PPCP pollution should be strictly controlled in order to prevent possible serious health threats to humans and living organisms.
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Lake sediments are natural receptors for a wide range of anthropogenic contaminants including organic matter and toxicants such as trace metals, polycyclic aromatic hydrocarbons, polychlorinated biphenyls that accumulate over time. This contamination can impact benthic communities, including microorganisms which play a crucial role in biogeochemical cycling and food-webs. The present survey aimed at exploring whether anthropogenic contamination, at a large lake scale, can influence the diversity, structure and functions of microbial communities associated to surface sediment, as well as their genetic potential for resistance to metals and antibiotics. Changes in the characteristics of these communities were assessed in surface sediments collected in Lake Geneva from eight sampling sites in October 2017 and May 2018. These sampling sites were characterized by a large concentration range of metal and organic compound contamination. Variation between the two sampling periods were very limited for all sampling sites and measured microbial parameters. In contrast, spatial variations were observed, with two sites being distinct from each other, and from the other six sites. Benthic communities from the most contaminated sampling site (Vidy Bay, near the city of Lausanne) were characterized by the lowest bacterial and archaeal diversity, a distinct community composition, the highest abundance of antibiotic resistance genes and functional (respiration, denitrification, methanogenesis, phosphatase, and beta-glucosidase) activity levels. The second sampling site which is highly influenced by inputs from the Rhône River, exhibited low levels of diversity, a distinct community composition, high abundance of antibiotic resistance genes and the highest bacterial abundance. Overall, our results suggest that local anthropogenic contamination, including organic matter and toxicants, is a major driver of the diversity and functioning of sediment-microbial communities in Lake Geneva. This highlights the need to consider benthic microbial communities and a suite of complementary ecotoxicological endpoints for more effective environmental risk assessments of contaminants in lake sediments.
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The consumption of pharmaceuticals and personal care products (PPCPs) has been widely increasing, yet up to 90–95% of PPCPs consumed by human are excreted unmetabolized. Moreover, the most of PPCPs cannot be fully removed by wastewater treatment plants (WWTPs), which release PPCPs to natural water bodies, affecting aquatic ecosystems and potentially humans. This study sought to review the occurrence of PPCPs in natural water bodies globally, and assess the effects of important factors on the fluxes of pollutants into receiving waterways. The highest ibuprofen concentration (3738 ng/L) in tap water was reported in Nigeria, and the highest naproxen concentration (37,700 ng/L) was reported in groundwater wells in Penn State, USA. Moreover, the PPCPs have affected aquatic organisms such as fish. For instance, up to 24.4 × 10 3 ng/g of atenolol was detected in P. lineatus. Amongst different technologies to eliminate PPCPs, algae-based systems are environmentally friendly and effective because of the photosynthetic ability of algae to absorb CO 2 and their flexibility to grow in different wastewater. Up to 99% of triclosan and less than 10% of trimethoprim were removed by Nannochloris sp., green algae. Moreover, variable concentrations of PPCPs might adversely affect the growth and production of algae. The exposure of algae to high concentrations of PPCPs can reduce the content of chlorophyll and protein due to producing reactive oxygen species (ROS), and affecting expression of some genes in chlorophyll ( rbcL, psbA, psaB and psbc ).
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In recent years, Non-Steroidal Anti-Inflammatory Drugs (NSAIDs) have surfaced as a novel class of pollutants due to their incomplete degradation in wastewater treatment plants and their inherent ability to promote physiological predicaments in humans even at low doses. The occurrence of the most common NSAIDs (diclofenac, ibuprofen, naproxen, and ketoprofen) in river water, groundwater, finished water samples, WWTPs, and hospital wastewater effluents along with their toxicity effects were reviewed. The typical concentrations of NSAIDs in natural waters were mostly below 1 μg/L, the rivers receiving untreated wastewater discharge have often showed higher concentrations, highlighting the importance of effective wastewater treatment. The critical analysis of potential, pathways and mechanisms of microbial degradation of NSAIDs were also done. Although studies on algal and fungal strains were limited, several bacterial strains were known to degrade NSAIDs. This microbial ability is attributed to hydroxylation by cytochrome P450 because of the decrease in drug concentrations in fungal cultures of Phanerochaete sordida YK-624 on incubation with 1-aminobenzotriazole. Moreover, processes like decarboxylation, dehydrogenation, dechlorination, subsequent oxidation, demethylation, etc. also constitute the degradation pathways. A wide array of enzymes like dehydrogenase, oxidoreductase, dioxygenase, monooxygenase, decarboxylase, and many more are upregulated during the degradation process, which indicates the possibility of their involvement in microbial degradation. Specific hindrances in upscaling the process along with analytical research needs were also identified, and novel investigative approaches for future monitoring studies are proposed.
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Background The objective of this work to calculate prescribed quantity of an active pharmaceutical ingredient (API) in prescription medications for human use, to facilitate research on the prediction of amount of API released to the environment and create an open-data tool to facilitate spatiotemporal and long-term prescription trends for wider usage. Design We have developed an R package, PrAna to calculate the prescribed quantity (in kg) of an APIs by postcode using England’s national level prescription data provided by National Health Service, for the years 2015–2018. Datasets generated using Prana can be visualized in a real-time interactive web-based tool, PrAnaViz to explore spatiotemporal and long-term trends. The visualisations can be customised by selecting month, year, API, and region. Results PrAnaViz’s targeted API approach is demonstrated with the visualisation of prescribed quantities of 14 APIs in the Bath and North East Somerset (BANES) region during 2018. Once the APIs list is loaded, the back end retrieves relevant data and populates the graphs based on user-defined data features in real-time. These plots include the prescribed quantity of APIs over a year, by month, and individual API by month, general practice, postcode, and medicinal form. The non-targeted API approach is demonstrated with the visualisation of clarithromycin prescribed quantities at different postcodes in the BANES region. Conclusion PrAna and PrAnaViz enables the analysis of spatio-temporal and long-term trends with prescribed quantities of different APIs by postcode. This can be used as a support tool for policymakers, academics and researchers in public healthcare, and environmental scientist to monitor different group of pharmaceuticals emitted to the environment and for prospective risk assessment of pharmaceuticals in the environment.
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Active pharmaceutical ingredients (APIs) are increasingly being identified as contaminants of emerging concern (CECs). They have potentially detrimental ecological human health impacts but are not currently subject to environmental regulation....
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The extensively used pesticides have severely impacted on environment in view of their toxicity and persistence. Among them, organochlorines are highly toxic with half-lives of many years followed by organophosphates. Being banned in many countries, most of pesticides are still persisting into the environment. Traditional methods are not enough for removal of those structurally stable and naturally persistent toxicants. Sustainable technologies based on engineered nanomaterials have better treatment efficiency credited to enhanced multidimensional properties including surface functionalization and porosity, specific targeting capabilities, increased surface-area, and catalysis. Further, improvisation in engineered nanomaterials for potential adsorption of pollutants could be achieved by application of organic ligands, enzyme immobilization, inorganic moieties and surface polymerization.
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Currently, the global production and usage of plastics have increased rapidly with the expansion of synthetic polymers. Since plastics' degradation processes are prolonged and thus microplastics (MPs) potentially persist for very long periods in the environment. To date, there is a need for knowledge on the relevance of different potential entry pathways and the number of MPs entering the environment via different routes. Despite the vast quantity of studies that have been undertaken, many unanswered issues remain about the environmental impacts of MPs. The real impacts on a population subjected to many MPs of different structure, dimensions, and shapes over a lifetime are still hard to elucidate. Significantly, MPs can accumulate toxic substances, such as persistent organic pollutants, on their material surface. Hence, it represents a potential concentrated source of environmental pollution or acts as a vector of toxic pollutants in the food chain's interconnection with some severe health implications. Herein, we mainly discussed the global challenges in MPs, including the current production and use status of plastics and their impact on the environment. Additionally, finding the degradation of tiny fragment plastics (MPs level) is essential to remove plastics altogether. Some of the approaches to methods, including biodegradation, physical degradation, physicochemical degradation, have been successfully reviewed. More importantly, the sustainable concepts of using microorganisms and photocatalysis for MPs' degradation have been successfully proposed and demonstrated.
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Current demographic trends, the rise of chronic diseases, the accessibility of inexpensive generic treatments, and the emergence of “lifestyle” drugs have been the key to increased pharmaceutical medicine use throughout the world. These pharmaceuticals are now the group of emerging contaminants with rising concern in the scientific world due to their presence in surface water, such as lake and river, groundwater, soil, and even drinking water and their associated impact on invertebrates, vertebrates, and ecosystem structure and function. The two main routes of such contaminations are (1) when such drugs taken are excreted in faces and urine and (2) when unused drugs are thrown down. Research undertaken has found that 60–80% of these pharmaceutical medicines are flushed down the toilet or dumped as regular household waste that ends up in sewage treatment plants, which are generally not designed to remove such pollutants from wastewater. Bioremediation is a process where degradation of contamination is done with the help of different microorganisms, which is one of the cost-effective methods that has been used until now. Though there are some interesting reports on the bioremediation of pharmaceuticals from water, further research is crucial for the systematic development of novel technologies to deal with such emerging contaminants. This chapter, therefore, is focused on summarizing and consolidating findings from the current state of the art in the area of pharmaceutical bioremediation.
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The ever-increasing production of plastics and concomitant poor plastic waste disposal systems explain the recent rising concerns over the occurrence of microplastics in freshwater resources. Microplastics are presently recognized as emerging contaminants owing to the increasing reports on their occurrence in the environment and the associated toxicological effects. This chapter discusses the recent trends in the monitoring of microplastics in freshwater resources, the toxicological effects of microplastics, and the sampling and analysis techniques available for detection and quantification. The challenges in analysis and comparison of various studies and future prospects have also been highlighted.
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In modern developing world, micropollutants of concern have emerged as a result of increased use of pharmaceuticals, hormones and personal care products. These pollutants have negative impacts on aquatic life due to their properties of persistence and bioaccumulation. Many of the micropollutants are resistant to biological treatments and therefore can not be completely removed from wastewater treatment plants. These contaminants can end up in to the receiving environment like surface water, ground water and even drinking water through different channels. In recent years, it has been determined that these emerging contaminants can be treated by different innovative advance treatment methods (adsorption, nanofiltration, reverse osmosis membranes and advanced oxidation processes etc.). Studies conducted on advanced oxidation processes have reported reliable removal efficiencies for micropollutants in literature. This review examines the source of micropollutants, their occurrence (aquatic environment, wastewater, surface water, groundwater, drinking water, sediments) and their removal with the help of advanced oxidation processes.
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In this study, magnetically recyclable spinel nickel ferrite (NiFe2O4) and multi-walled carbon nanotubes (MWCNTs) incorporated NiFe2O4 (NiFe-CNT) composite with different CNT contents were successfully synthesized by one-step hydrothermal treatment. The photo-Fenton efficiency of the synthesized materials was assessed by the degradation of recalcitrant sulfamethoxazole (SMX) under ultraviolet (UV)-A and visible light. The efficiency of poorly active NiFe2O4 was significantly enhanced by the incorporation of 25 wt% CNT, and complete degradation of SMX (5 mg/L) was achieved within 2 h using NiFe-CNT composite (0.025 g/L) in the presence of H2O2 under UV-A light. Higher mineralization (total organic carbon (TOC) removal = 68%) was obtained in case of NiFe-CNT composite than bare NiFe2O4 (TOC removal = 39%). The effects of catalyst dosage, SMX concentration, H2O2 concentration, and pH on the degradation of SMX were investigated in order to identify the optimized reaction conditions. No leaching or degradation of MWCNTs was observed in the reaction solution and iron leaching from the composite was also under permissible limits. Photocurrent and Electrochemical Impedance Spectroscopy studies were performed to check the effective charge separation. The improved photocatalytic activity of the NiFe-CNT composite reflects (1) the synergy effect between NiFe2O4 and MWCNTs, (2) effective charge separation that retards the recombination of photogenerated charges, and (3) the generation of more reactive oxidation species (especially OH radicals). Moreover, ease of separation due to the significant magnetic properties of the NiFe-CNT composite provides an efficient method to treat recalcitrant organic pollutant.
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In this article, the utilization of fungi for the degradation of xenobiotic organic compounds (XOCs) from different wastewater and aqueous solutions has been reviewed. The myco-remediation (myco-enzymes, myco-degradation, and myco-sorption) process is widely used to remove XOCs, which are not easily biodegradable. The removal of XOCs from textile wastewaters through chemical and physical processes has been addressed by many researchers. Currently, the application of oxidative enzymes [manganese peroxidase (MnP), lignin peroxidase (LiP), and laccase] and myco-adsorption is becoming more common for the removal of XOCs from wastewater. Although the advanced oxidation process (AOPs) is a preferred technology for removing XOCs, its use is restricted due to its relatively high cost, which led to research studies on non-traditional and low-cost technology. The current review aimed to organize the scattered available information on the potential of myco-remediation for XOC removal. Moreover, the utilization of agricultural wastes as a production substrate for oxidative enzymes has been reported by many authors. Agricultural waste materials are highly inducible for oxidative enzyme production by fungi and are cost-effective in comparison to commercial substances. It is evident from the literature survey of 80 recently published papers that myco-enzymes have demonstrated outstanding XOC removal capabilities. Graphical Abstract Fungal laccase enzyme is the first step to degrade the lignin and then to get the carbon source form the cellulose by cellulose enzyme. Open image in new window
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This paper describes analytical modeling of degradation of water treatment plants (WTP) during their extended operation; it also describes the algorithms for configuring such models on the basis of current WTP status readings so as to predict when the WTP deteriorates to the point it is no longer usable (time to failure). Model selection is based on analyzing and generalizing a bulk of experimental data on various WTPs. Configuration algorithms are model-agnostic, which means the proposed approach can be used universally to improve water treatment quality while also cutting its costs.
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For over 70 years, scientists have reported that certain synthetic and natural compounds could mimic nat-ural hormones in the endocrine systems of animals. These substances are now collectively known as en-docrine-disrupting compounds (EDCs), and have been linked to a variety of adverse effects in both humans and wildlife. More recently, pharmaceuticals and personal care products (PPCPs) have been discovered in various surface and ground waters, some of which have been linked to ecological impacts at trace con-centrations. The majority of EDCs and PPCPs are more polar than traditional contaminants and several have acidic or basic functional groups. These properties, coupled with occurrence at trace levels (i.e., ,1 mg/L), create unique challenges for both removal processes and analytical detection. Reports of EDCs and PPCPs in water have raised substantial concern among the public and regulatory agencies; however, very little is known about the fate of these compounds during drinking and wastewater treatment. Numerous studies have shown that conventional drinking and wastewater treatment plants can not completely remove many EDCs and PPCPs. Oxidation with chlorine and ozone can result in transformation of some com-pounds with reactive functional groups under the conditions employed in water and wastewater treatment plants. Advanced treatment technologies, such as activated carbon and reverse osmosis, appear viable for the removal of many trace contaminants including EDCs and PPCPs. Future research needs include more detailed fate and transport data, standardized analytical methodology, predictive models, removal kinetics, and determination of the toxicological relevance of trace levels of EDCs and PPCPs in water.
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Pharmaceutically active compounds (PhACs) in the environment lately have been acknowledged to constitute a health risk for humans and terrestrial and aquatic ecosystems. Human and veterinary applications are the main sources of PhACs in the environment and the major pathways are excretion and discharge to the environment through sewage treatment plants (STPs). In this study, the occurrence and fate of selected human PhACs belonging to different therapeutic classes (non-steroidal anti-inflammatory drugs, lipid regulators, anti-epileptics, antibiotics and beta-blockers) were investigated in a small river in the very south of Sweden. The objectives of the study were to evaluate the impact of a high and rather constant load in sewage influent on downstream concentrations and whether substances that are metabolized to a high degree in humans also show a low persistency in a natural aquatic environment. Water samples were collected from the influent and effluent of the STP, in a series of dammed reservoirs leading to discharge into the Höje River in Sweden, and at several locations in the river downstream of the outfall. After enrichment by solid-phase extraction, the compounds were analyzed using GC-MS (methylated derivatives) or LC-MS/MS. In addition to the targeted pharmaceuticals, GC-MS analysis of the samples revealed the presence of other sewage-related pollutants (triclosan, caffeine, flame-retardants, antioxidants) and these results where included for comparison. Removal efficiencies were calculated in the STP and found to display a wide range with numerous species surviving treatment at greater than half their influent concentrations, including diclofenac, the anti-epileptic carbamazepine, a beta-blocker (propanolol), and antibiotics trimetoprim and sulfamethoxazole. Low removals were also observed for Tris(2-chloroisopropyl)phosphate (flame retardant), BHT-aldehyde (oxidation product of BHT) and synthetic musk (HHCB). The concentrations of chloride (Cl(-)) and boron (B) were used as natural inert tracers to estimate the relative extent of dilution of PhACs measured in the effluent of the STP on concentrations measured further downstream. Based on spatial trends of concentrations (recalculated to reflect a hypothetical scenario with no dilution), ibuprofen, ketoprofen, naproxen and dicofenac were shown to be subject to significant abiotic or biotic transformations or physical sequestration in the river. The beta-blockers atenolol, metoprolol and propanolol, the antibiotics trimetoprim and sulfametoxazole, and carbamazepine demonstrated a high degree of persistence. Fluctuations in the concentration of carbamazepine and gemfibrozil were observed along the series of reservoirs and within the river and are hypothesized to be due to release of parent compound from glucuronides. Several of the investigated substances (metaprolol, propanolol and carbamazepin) that exhibit low excretion rates as parent compounds demonstrate a surprising persistence in the aquatic environment. It is concluded that pharmaceutical substances with a high metabolic rate in humans (low excretion rate) do not necessarily induce a short lifetime in aquatic environments. Results from this study emphasize the need for a broader view on the concept of persistence that accounts for loading rates, in addition to removal mechanisms (e.g., transformation, volatility and physical sequestration by solids), under a variety of spatial and temporal scales.
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A survey of contamination of surface and drinking waters around Lake Maggiore in Northern Italy with polar anthropogenic environmental pollutants has been conducted. The target analytes were polar herbicides, pharmaceuticals (including antibiotics), steroid estrogens, perfluorooctanesulfonate (PFOS), perfluoroalkyl carboxylates (including perfluorooctanoate PFOA), nonylphenol and its carboxylates and ethoxylates (NPEO surfactants), and triclosan, a bactericide used in personal-care products. Analysis of water samples was performed by solid-phase extraction (SPE) then liquid chromatography–triple-quadrupole (tandem) mass spectrometry (LC–MS–MS). By extraction of 1-L water samples and concentration of the extract to 100 μL, method detection limits (MDLs) as low as 0.05–0.1 ng L−1 were achieved for most compounds. Lake-water samples from seven different locations in the Southern part of Lake Maggiore and eleven samples from different tributary rivers and creeks were investigated. Rain water was also analyzed to investigate atmospheric input of the contaminants. Compounds regularly detected at very low concentrations in the lake water included: caffeine (max. concentration 124 ng L−1), the herbicides terbutylazine (7 ng L−1), atrazine (5 ng L−1), simazine (16 ng L−1), diuron (11 ng L−1), and atrazine-desethyl (11 ng L−1), the pharmaceuticals carbamazepine (9 ng L−1), sulfamethoxazole (10 ng L−1), gemfibrozil (1.7 ng L−1), and benzafibrate (1.2 ng L−1), the surfactant metabolite nonylphenol (15 ng L−1), its carboxylates (NPE1C 120 ng L−1, NPE2C 7 ng L−1, NPE3C 15 ng L−1) and ethoxylates (NPEn Os, n = 3-17; 300 ng L−1), perfluorinated surfactants (PFOS 9 ng L−1, PFOA 3 ng L−1), and estrone (0.4 ng L−1). Levels of these compounds in drinking water produced from Lake Maggiore were almost identical with those found in the lake itself, revealing the poor performance of sand filtration and chlorination applied by the local waterworks.
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There is increasing concern about diffuse pollution of aquatic systems by biocides used in urban areas. We investigated sources and pathways of biocides significant for the pollution of storm water runoff. Main sources seem to be building envelopes, i.e. facades (paints, plasters) and roof sealing membranes. First results from a defined urban catchment drained by a separated sewer system without any agricultural activities reveal a substantial occurrence. Even after the first flush, concentrations of terbutryn, carbendazim, mecoprop as well as Irgarol 1051 and its metabolite exceeded the Swiss water quality standard of 0.1 microg/L. In laboratory experiments, leaching of mecoprop used as a root protection agent in bitumen sheets for roof waterproofing was determined. The concentrations differed in 16 different sheets two orders of magnitude, depending on the product composition. Using optimized products, it is expected to be the most efficient and sustainable way to reduce the environmental impact. To understand transport dynamics and environmental risk, further storm water events will be analyzed. Based on the ongoing project URBIC, first measures will be proposed to limit the release to surface and ground water.
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The origin and distribution of microbial contamination in Lake Geneva's most polluted bay were assessed using faecal indicator bacteria (FIB). The lake is used as drinking water, for recreation and fishing. During 1 year, water samples were taken at 23 points in the bay and three contamination sources: a wastewater treatment plant (WWTP), a river and a storm water outlet. Analyses included Escherichia coli, enterococci (ENT), total coliforms (TC), and heterotrophic plate counts (HPC). E. coli input flux rates from the WWTP can reach 2.5 x 10(10) CFU/s; those from the river are one to three orders of magnitude lower. Different pathogenic Salmonella serotypes were identified in water from these sources. FIB levels in the bay are highly variable. Results demonstrate that (1) the WWTP outlet at 30 m depth impacts near-surface water quality during holomixis in winter; (2) when the lake is stratified, the effluent water is generally trapped below the thermocline; (3) during major floods, upwelling across the thermocline may occur; (4) the river permanently contributes to contamination, mainly near the river mouth and during floods, when the storm water outlet contributes additionally; (5) the lowest FIB levels in the near-surface water occur during low-flow periods in the bathing season.
Article
Human pharmaceuticals are widely used and can reach surface waters, where they have the potential to exert biological effects on aquatic non-target organisms. Due to the high number of pharmaceutical drugs used in human medicine throughout the world, it is necessary to select the pharmaceuticals to search for, prior to implementing any environmental measurements and any extensive environmental risk assessment (ERA). This paper describes a methodology developed in order to define this selection. The prioritization scheme consists of two main tiers. First, a preliminary classification based on the assessment of exposure is implemented. The exposure assessment is determined by calculating predicted environmental concentrations (PECs) for each pharmaceutical, according to the EMEA's environmental risk assessment guidelines (European Medicine Evaluation Agency, 2006). In the second step, the preliminary classification is reviewed on a case-by-case hypothesis basis using all the biological data available: ecotoxicological, pharmacological (mechanism of action, enzyme modulation, adverse effects) and physicochemical data (log Kow). We applied this methodology to the French situation and prioritized 120 parent molecules and 30 metabolites. The final prioritization list gathers 40 parent compounds and 13 metabolites. Among the 40 parent molecules, 21 have already been found in the aquatic environment, indicating a good agreement between the theoretical approach and the environmental measurements. Parameters used to construct the effect criteria are discussed for their relevance.
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When the first green wave appeared in the mid and late 1960s, it was considered a f- sible task to solve pollution problems. The visible problems were mostly limited to point sources, and a comprehensive “end of the pipe technology” (= environmental technology) was available. It was even seriously discussed in the US that what was called “zero d- charge” could be attained by 1985. It became clear in the early 1970s that zero discharge would be too expensive, and that we should also rely on the self purification ability of ecosystems. That called for the development of environmental and ecological models to assess the self purifi- tion capacity of ecosystems and to set up emission standards, considering the re- tionship between impacts and effects in the ecosystems. This idea is illustrated in Fig. 0.1. A model is used to relate an emission to its effect on the ecosystem and its components. The relationship is applied to select a good solution to environmental problems by application of environmental technology.
Chapter
In the 1970s, for the first time, pharmaceuticals in the environment (namely hormones) were the subject of scientific interest and public awareness (Tabak and Brunch 1970; Norpoth et al. 1973). The conclusion most often reached was that the hormones are not easily biodegraded. During the 1980s, there has been only little interest in this topic. Other substances of environmental relevance such as heavy metals, polycyclic aromatic hydrocarbons, or chlorinated dioxins and furans as well as pesticides or detergents have been investigated very extensively during this period. Since the middle of the 1990s, awareness of pharmaceuticals in the environment has been growing. Parallel to this, the discussion of endocrine disrupting (sometimes called endocrine modulating) substances (EDS) and non-hormone pharmaceuticals, like lipid lowering agents and others, came into focus (Stan and Linkerhägner 1992). Since then, quite a lot of activities have been initiated relating to EDS, beginning in the USA, and for other pharmaceuticals mainly in Europe. Substances have been detected in sewage, the effluents of sewage treatment plants, surface water, manure and soil since the 1980s (Table 1.1). Most of those investigated so far were not easily biodegradable in test systems (see Chap. 4, 6, 7 and 8) and are only slowly eliminated in the environment — if at all.
Article
The suitability of caffeine as a chemical marker for surface water pollution by domestic wastewaters was assessed in this study. Caffeine concentrations in influents and effluents of Swiss wastewater treatment plants (WWTP's, 7-73 and 0.03-9.5 mug/L, respectively) indicated an efficient elimination of 81-99.9%. Corresponding loads in untreated wastewater showed small variations when normalized for the population discharging to the WWTPs (15.8 +/- 3.8 mg person(-1) d(-1)), reflecting a rather constant consumption. WWTP effluent loads were considerably lower (0.06 +/- 0.03 mg person(-1) d(-1)), apart from installations with low sludge age (less than or equal to5 d, loads up to 4.4 mg person(-1) d(-1)). Despite the efficient removal in most WWTPs, caffeine was ubiquitously found in Swiss lakes and rivers(6-250 ng/L, except for remote mountain lakes (<2 ng/L; analytical procedure for wastewater and natural waters: SPE, GCMS-SIM or GC-MS-MS-MRM, internal standard C-13(3)-labeled caffeine). Caffeine concentrations in lakes correlated with the anthropogenic burden by domestic wastewaters, demonstrating the suitability of caffeine as a marker. A mass balance for Greifensee revealed that;: approximate to1-4% of the wastewaters had been discharged without treatment, presumably on rainy days when the capacity of WWTPs had been exceeded. For Zurichsee, it could be shown that the monthly inputs of caffeine correlated with precipitation data. The depth- and seasonal-dependent concentrations in this lake were adequately rationalized by a numerical model considering flushing, biodegradation, and indirect photodegradation via HO. radicals as elimination processes and caffeine inputs as fitting variables.
Article
Pharmaceutical residues are found as contaminants in sewage, surface, ground and drinking water. Drug residues originating from therapeutical use in human medical care are discharged into the aquatic system from municipal sewage treatment plants which act as point sources for surface water contaminations. Wherever contaminated surface water is used for groundwater recharge in drinking water production, the drug contaminants can also cause problems to drinking water supplies. Until now, the environmental assessment for this new class of contaminants is not clear or even regulated.
Article
The occurrence of iodinated X-ray contrast media derived from radiological examinations was investigated in German municipal sewage, sewage treatment plant (STP) effluents, rivers, and groundwater using LC-electrospray tandem MS detection. The four X-ray contrast media, diatrizoate, iopamidol, iopromide, and iomeprol are ubiquitously distributed in the sewage and in the aquatic environment. The X-ray contrast media were not significantly eliminated during the sewage treatment processes close to Frankfurt/Main. On weekdays the loading of the X-ray contrast media was significantly increased, because X-ray examinations are performed in hospitals and radiological practices predominately from Monday to Friday. The maximum concentration measured in STP effluents was 15 μg/L for iopamidol. Due to the high contamination of STP effluents with X-ray contrast media, the respective receiving waters (rivers and creeks) were also highly polluted. Median values up to 0.49 μg/L for iopamidol and 0.23 μg/L for diatrizoate were determined. In groundwater these polar compounds were present up to concentrations as high as 2.4 μg/L for iopamidol. Since X-ray contrast media are predominantly applied in human medicine, the polluted municipal STP effluents are presumably the sole sources for the contamination of the aquatic environment.
Article
Pharmaceuticals are chemicals that are used because of their biological activity. They are often excreted unchanged and can reach the environment. Throughout developed countries, the pharmaceutical concentrations in the aquatic environment are in the same range (μg L and below); however, it is not clear whether this holds for less-developed countries too. The health risks of active pharmaceutical ingredients (APIs) remain poorly understood. Although there are no known short-term effects on humans, long-term effects cannot be ruled out until there is more research. The significance of metabolites and transformation products resulting from the parent APIs is not yet known. Awareness of the presence of pharmaceuticals in the environment, coupled with some evidence of effects, suggests that precautionary management action to reduce the release of pharmaceuticals to the environment should be considered. As for effluent treatment, no technology works well for all compounds. Advanced effluent treatment is not sustainable because of energy consumption, efficiency, and efficacy. Therefore, its appropriateness must be assessed on a case-by-case basis. Increased handling and use measures at the source and better biodegradable pharmaceuticals are necessary in the long run for the new paradigm called “sustainable pharmacy.”
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Human activity results in the production of a wide range of pollutants that can enter the water cycle through stormwater or wastewater. Among others, heavy metals are still detected in high concentrations around urban areas and their impact on aquatic organisms is of major concern. In this study, we propose to use a substance flow analysis as a tool for heavy metals management in urban areas. We illustrate the approach with the case of copper in Lausanne, Switzerland. The results show that around 1,500 kg of copper enter the aquatic compartment yearly. This amount contributes to sediment enrichment, which may pose a long-term risk for benthic organisms. The major sources of copper in receiving surface water are roofs and catenaries of trolleybuses. They represent 75% of the total input of copper into the urban water system. Actions to reduce copper pollution should therefore focus on these sources. Substance flow analysis also highlights that copper enters surface water mainly during rain events, i.e., without passing through any treatment procedure. A reduction in pollution could also be achieved by improving stormwater management. In conclusion, the study showed that substance flow analysis is a very effective tool for sustainable urban water management.
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Pharmaceuticals are substances designed to have a biological effect in humans. Their presence in the environment, especially in surface waters, is of increasing concern because of their potential risk to non-target species. A large number of pharmaceuticals are on the market; for example, approximately 2,000 active ingredients are approved in Europe, and many of them have already been detected in surface water. It is therefore crucial to select the substances that may do the most harm to the environment prior to performing measurements and extensive risk assessment. In the present study, a method to determine a list of pharmaceuticals to survey in surface water is proposed. Inclusion of substances on the list was based on a screening procedure, the analytical feasibility, and previous knowledge of pharmaceuticals detected in water. The screening procedure proposed here is an improvement on the standard procedure of the European Medicine Evaluation Agency (EMEA). It is designed to decrease the number of pharmaceuticals to be evaluated in a stepwise manner, thus decreasing the number of data necessary for the evaluation. We applied our approach to determine a list of 37 pharmaceuticals and four hormones to survey in a specific region of Switzerland, the Lake Geneva area, and discussed the advantages and weak points of the method.
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The removal efficiency for 220 micropollutants was studied at the scale of a municipal wastewater treatment plant (WWTP) upgraded with post-ozonation followed by sand filtration. During post-ozonation, compounds with activated aromatic moieties, amine functions, or double bonds such as sulfamethoxazole, diclofenac, or carbamazepine with second-order rate constants for the reaction with ozone >10(4) M(-1) s(-1) at pH 7 (fast-reacting) were eliminated to concentrations below the detection limit for an ozone dose of 0.47 g O3 g(-1) dissolved organic carbon (DOC). Compounds more resistant to oxidation by ozone such as atenolol and benzotriazole were increasingly eliminated with increasing ozone doses, resulting in >85% removal for a medium ozone dose (approximately 0.6 g O3 g(-1) DOC). Only a few micropollutants such as some X-ray contrast media and triazine herbicides with second-order rate constants <10(2) M(-1) s(-1) (slowly reacting) persisted to a large extent. With a medium ozone dose, only 11 micropollutants of 55 detected in the secondary effluent were found at >100 ng L(-1). The combination of reaction kinetics and reactor hydraulics, based on laboratory-and full-scale data, enabled a quantification of the results by model calculations. This conceptual approach allows a direct upscaling from laboratory- to full-scale systems and can be applied to other similar systems. The carcinogenic by-products N-nitrosodimethylamine (NDMA) (< or =14 ng L(-1)) and bromate (<10 microg L(-1)) were produced during ozonation, however their concentrations were below or in the range of the drinking water standards. Furthermore, it could be demonstrated that biological sand filtration is an efficient additional barrier for the elimination of biodegradable compounds formed during ozonation such as NDMA. The energy requirement for the additional post-ozonation step is about 0.035 kWh m(-3), which corresponds to 12% of a typical medium-sized nutrient removal plant (5 g DOC m(-3)).
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The occurrence of pharmaceuticals in different water bodies and the findings of effects on aquatic organisms in ecotoxicity tests have raised concerns about environmental risks of pharmaceuticals in receiving waters. Due to the fact that the amount of ecotoxicological studies has increased significantly during the last decade, probabilistic approaches for risk characterization of these compounds may be feasible. This approach was evaluated by applying it to 22 human-used pharmaceuticals covering both pharmaceuticals with a high volume and high ecotoxicity, using ecotoxicological effect data from laboratory studies and comparing these to monitoring data on the effluents from sewage treatment plants in Europe and pharmaceutical sales quantities. We found that for 19 of the 22 selected pharmaceuticals the existing data were sufficient for probabilistic risk characterizations. The subsequently modeled ratios between monitored concentrations and low-effect concentrations were mostly above a factor of 100. Compared to the current paradigm for EU environmental risk assessment where a safety factor of 10 or 100 might have been used it seems that for the modeled compounds there's a low environmental risk. However, similarly calculated ratios for five pharmaceuticals (propranolol, ibuprofen, furosemide, ofloxacin, and ciprofloxacin) were below 100, while ibuprofen and ciprofloxacin are considered to be of high concern due to lack of ecotoxicity studies. This paper shows that by applying probabilistic approaches, existing data can be used to execute a comprehensive study on probability of impacts, thereby contributing to a more comprehensive environmental risk assessment of pharmaceuticals.