Article

Pharmaceuticals in surface waters: Sources, behavior, ecological risk, and possible solutions. Case study of Lake Geneva, Switzerland

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Abstract

Nowadays, pharmaceuticals are present in surface waters as well as in groundwaters of developed countries. In the middle of Lake Geneva, for example, one of the largest European lakes, 14 pharmaceuticals are regularly detected in concentrations up to 0.37 µg/L. This pollution is due to the human consumption of drugs and also veterinary use and industrial releases during production. In the case of Lake Geneva, this latter pollution is significant for some specific compounds. But, as shown in this overview, environmental toxicity data are lacking for most of the pharmaceuticals detected in the aquatic environment. For example, the ecotoxicity of metformin, one of the main compounds detected in Lake Geneva, is mostly unknown for the moment. Furthermore, specific effects like endocrine disruption, genotoxicity, or antibioresistance induction, which may be expected because of the mode of action of some drugs, have not yet been investigated for aquatic species. Ecological risk assessment of pharmaceuticals is therefore tricky and most of the time is not feasible. Owing to this lack of knowledge, also due to high biological potency of the pharmaceuticals, it is critical to reduce the release of these compounds to the aquatic system. This may be achieved by ‘at source’ (e.g., urine collection) methods or ‘end of pipe’ (e.g., wastewater treatment) solutions. WIREs Water 2014, 1:69–86. doi: 10.1002/wat2.1006 Conflict of interest: The authors have declared no conflicts of interest for this article. For further resources related to this article, please visit the WIREs website.

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... For example, the high tonnage of metformin measured in Lake Geneva is explained by its high consumption in the lake catchment, its high elimination rate, and its poor removal in the WWTP. 22 Other substances systematically quantified in the middle of the lake are four radio contrast agents (iohexol, iomeprol, iopromide, iopamidol), three local anesthetics (prilocaine, bupivacaine, mepivacaine), and two antiepileptic drugs (carbamazepine, gabapentin). The load of these compounds in the lake cannot be entirely explained by human consumption and industries located along the River RhôneRhˆRhône are another source of pollution. ...
... The load of these compounds in the lake cannot be entirely explained by human consumption and industries located along the River RhôneRhˆRhône are another source of pollution. 22 In contrary to pesticides that diminish, the concentrations of pharmaceuticals since 2006 do not show a clear tendency and seem rather stable through the different monitoring campaigns ( Figure 6). There are some exceptions like carbamazepine (Figure 6), which has an industrial source. ...
... In the example of Lake Geneva, the reduction of industrial releases should contribute to reduce the risk. 22,87 It is trickier when the risk is due to the sum of the individual risk of several substances co-occurring in the system, substances that do not present a risk individually. Risk reduction measures should therefore focus on global reduction of the release, for example the improvement of the treatment in the WWTP. ...
Article
Aquatic organisms are typically exposed simultaneously to several organic compounds released from human activities like agriculture, industries, or simply from people living in cities. The ecological risk assessment of mixtures of such compounds has therefore to be addressed by scientists. The aims of this paper are (1) to describe the current mixture risk assessment procedures, (2) to apply such approach to a specific case study, Lake Geneva and the River Rhône in Switzerland, and (3) to discuss the outcomes of such an application. Two models, called concentration addition and independent action, are recognized to be robust enough to predict the mixture effect of substances on a given species. They are classically used also to assess the risk of mixtures for the ecosystem, but their use is often limited by the lack of available ecotoxicity data. Adopting a first level assessment, we describe the evolution of the mixture risk for several years of Lake Geneva, and for 2010 for the River Rhône. These first assessments allow identification of the most problematic substances demanding risk reduction measures. Furthermore, again for the two cases studies, we show that the risk levels associated with mixtures of compounds can rapidly exceed critical aquatic thresholds, and therefore, it is the sum of the substances that is problematic, which is more challenging in term of risk management. Further analysis of effects in compound mixtures as well as a better characterization of the overall ecological risk are necessary for the thousands substances co-occuring at very low concentrations. Conflict of interest: The authors have declared no conflicts of interest for this article.
... RODRIGUEZ-MOZAZ et al., 2015;, lakes(CHÈVRE, 2014), oceans(XIE et al., 2012) and even drinking water(QUINLIVAN et al., 2005; JONGH, DE et al., 2012; all over the world. This constitutes a serious environmental and public health problem mainly due to their toxicity and potential hazardous health effects (carcinogenicity, mutagenicity and bactericidality) on living organisms, including human beings(DONNER et al., 2013;YAN et al., 2014).Dyes (YANG, X.; AL-DURI, 2005), chemicals (BOLONG et al., 2009), and pharmaceuticals (SANTOS et al., 2013) are some of the most common recalcitrant organic pollutants.In matter of fact, the activated carbon application for the removal of wastewater is increasing, year by year, as well as the production of these matherials(FREIHARDT et al., 2017). ...
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A discussão da remoção de micropoluentes orgânicos é atualmente necessária, tendo em vista, a problemática causada por estes compostos tanto no meio ambiente ou saúde pública e ambiental. Sua presença ubíqua em várias matrizes ambientais, e suas já estabelecidas metodologias analíticas de quantificações, propiciam aos trabalhos avançar para o próximo passo, estudar processos de remoção em águas e efluentes. Dentre as metodologias de remoção observadas na literatura, destaca-se a adsorção, tendo como prós, a não formação de produtos de degradação e a versatilidade da técnica. Sendo assim, esta tese, objetivou avaliar as características preponderantes a adsorção de micropoluentes orgânicos das classes dos disruptores endócrinos e dos compostos com atividade farmacológica por meio de estudos em adsorventes comercias, e biosorventes sintetizados a partir de cascas de Pinus elliotti spp. Os testes prévios, apontaram uma potencialidade de remoção de 6 hormônios - 17β-estradiol (E2), 17-α-etinilestradiol (EE2), Estrona (E1) e Progesterona (PG), Hidrocortisona (HC) e Dexametasona (DX) - a partir da biosorção em soluções fortificadas, obtendo valores de remoção de 35,67 a 98,89%, sendo que comparativamente com os materiais comercias, foi o material que apresentou a maior eficiência. Sabendo disso, estudou-se quais características foram preponderantes a adsorção de 23 micropoluentes orgânicos de variadas características físicas e químicas em 6 carvões ativados comercias microgranulares, de composição conhecida e variada em matrizes fortificadas e efluentes sanitários tratados. A partir de testes de correlação direta, constatou-se que as matrizes não eram passíveis de extrapolação, e que as características que eram preponderantes à adsorção eram volume de mesoporos (no teste com água fortificada) e quantidade de oxigênio (no teste com águas reais), atingindo correlações médias entre a variável e as remoções de 0,83 e 078 respectivamente. Uma vez identificadas estas características, sintetizou-se biosorventes, a partir de hidrólises ácidas e básicas em cascas de árvore de classificação Pinus eliotti spp. Após, caracterização física e química dos materiais estudou-se se estas características eram capazes de predizer a remoção de produtos com atividade farmacológica a partir da regressão dos quadrados mínimos (PLS-R). Os coeficientes observados para o método variaram de 0,51 a 0,59, dependendo do adsorvente utilizado. O uso da PLS foi extremamente útil para preservar as relações de Pearson entre características físico-químicas e suas remoções. Isso pode facilitar a interpretação dos dados. Por meio dele, pode-se apontar que existem processos de exclusão de moléculas com grande massa molecular em adsorventes com baixo volume de mesoporos, e que superfícies oxigenadas aumentam a eficiência de remoção dos fármacos, especialmente os com carga positiva. Desta forma, com esta potente ferramenta de predição, pode-se aplicar este trabalho para a confecção de novos materiais adsorventes com potencial remoção de micropoluentes orgânicos. Palavras-chave: Micropoluentes Orgânicos; Remoção; PLS-R.
... Residues of pharmaceuticals have been detected in surface waters worldwide, leading scientists as well as non-scientists to wonder about their risks to aquatic systems (Williams, 2005). Aside from veterinary use and industrial releases, the primary source of drugs in water appears to be human consumption (Chèvre, 2014). After pharmaceuticals are absorbed, they are eliminated in intact and/or metabolised forms through human excreta. ...
Article
Although pharmaceutical metabolites are found in the aquatic environment, their toxicity on living organisms is poorly studied in general. Endoxifen and 4-hydroxy-tamoxifen (4OHTam) are two metabolites of the widely used anticancer drug tamoxifen for the prevention and treatment of breast cancers. Both metabolites have a high pharmacological potency in vertebrates, attributing prodrug characteristics to tamoxifen. Tamoxifen and its metabolites are body-excreted by patients, and the parent compound is found in sewage treatment plan effluents and natural waters. The toxicity of these potent metabolites on non-target aquatic species is unknown, which forces environmental risk assessors to predict their toxicity on aquatic species using knowledge on the parent compounds. Therefore, the aim of this study was to assess the sensitivity of two generations of the freshwater microcrustacean Daphnia pulex towards 4OHTam and endoxifen. Two chronic tests of 4OHTam and endoxifen were run in parallel and several endpoints were assessed. The results show that the metabolites 4OHTam and endoxifen induced reproductive and survival effects. For both metabolites, the sensitivity of D. pulex increased in the second generation. The intrinsic rate of natural increase (r) decreased with increasing 4OHTam and endoxifen concentrations. The No-Observed Effect Concentrations (NOECs) calculated for the reproduction of the second generation exposed to 4OHTam and endoxifen were <1.8 and 4.3μg/L, respectively, whereas the NOECs that were calculated for the intrinsic rate of natural increase were <1.8 and 0.4μg/L, respectively. Our study raises questions about prodrug and active metabolites in environmental toxicology assessments of pharmaceuticals. Our findings also emphasize the importance of performing long-term experiments and considering multi-endpoints instead of the standard reproduction outcome. Copyright © 2015 Elsevier B.V. All rights reserved.
... For pharmaceuticals, laboratory studies have confirmed that some antibiotics (e.g., oxytetracycline and tetracycline) and psychiatric drugs (e.g., carbamazepine) have the possibility of bioaccumulation and transfer through aquatic food chains (Boonsaner and Hawker, 2013;Kim et al., 2014;Vernouillet et al., 2010). Therefore, a growing interest has been given to the risk of pharmaceuticals posing for the aquatic trophic chains (Brodin et al., 2014;Chèvre, 2014;Zenker et al., 2014). In a field study investigating the bioaccumulation of various pharmaceuticals in the liver of crucian carp (Carassius auratus) caged in an effluent-receiving river, PRP has showed a higher bioaccumulation factor (BAF) (2782) than the other pharmaceutical substances such as roxithromycin (440), carbamazepine (917) and erythromycin (1482) (Liu et al., 2015a). ...
... Exposure time considered in laboratory nowadays has not been considered realistic also and according to [41], environmental risk assessments based on acute toxicity tests do not adequately reflect the potential for chronic effects following long-term exposure to sub-acute levels. [47] states that although studies addressed to assess the long-term effects of pharmaceuticals in aquatic organisms have been increasing, their number is still very low. Furthermore, there is a need to carry out adequate toxicity tests to evaluate the exposure to metabolites, since pharmaceuticals are only partially excreted in parental form. ...
Article
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It is well known that there is a widespread use of veterinary pharmaceuticals and consequent release into different ecosystems such as freshwater bodies and groundwater systems. Furthermore, the use of organic fertilizers produced from animal waste manure has been also responsible for the occurrence of veterinary pharmaceuticals in agricultural soils. This article is a review of different studies focused on the detection and quantification of such compounds in environmental compartments using different analytical techniques. Furthermore, this paper reports the main challenges regarding veterinary pharmaceuticals in terms of analytical methods, detection/quantification of parent compounds and metabolites and, risks/toxicity to human health and aquatic ecosystems. Based on the existing literature, it is clear that only limited data is available regarding veterinary compounds and there are still considerable gaps to be bridged in order to remediate existing problems and prevent future ones. In terms of analytical methods, there are still considerable challenges to overcome considering the large number of existing compounds and respective metabolites. A number of different studies highlight the lack of attention given to the detection and quantification of transformation products and metabolites. Furthermore more attention needs to be given in relation to the toxic effects and potential risks that veterinary compounds pose to environmental and human health. To conclude, the more research investigations focused on these subjects take place in the near future, more rapidly we will get a better understanding about the behavior of these compounds and the real risks they pose to aquatic and terrestrial environments and how to properly tackle them.
... Pharmaceuticals are among a thousand other xenobiotics that are present in the aquatic environment (for reviews see Kümmerer, 2001;Brausch et al., 2012). Over the last few decades, thousands of tons of drugs have been produced yearly to treat human ailments (Zuccato et al., 2000;Dietrich et al., 2002), and human consumption and subsequent excretion seems to be the primary pathway for pharmaceuticals to reach the aquatic environment (Chèvre, 2014). Once consumed, intact and/or metabolized forms of the drug are excreted via faeces and urine. ...
Article
Tamoxifen and its metabolite 4-hydroxy-tamoxifen (4OHTam) are two potent molecules that have anticancer properties on breast cancers. Their medical use is expected to increase with the increasing global cancer rate. After consumption, patients excrete tamoxifen and the 4OHTam metabolite into wastewaters, and tamoxifen has been already detected in wastewaters and natural waters. The concentrations of 4OHTam in waters have never been reported. A single study reported 4OHTam effects on the microcrustacean Daphnia pulex. The effects of tamoxifen and 4OHTam over more than two generations are unknown in aquatic invertebrates. The main goal of this study was to assess the long-term sensitivity of the microcrustacean D. pulex over four generations, based on size, reproduction, viability and the intrinsic rate of natural increase (r). Additional experiments were carried out to observe whether the effects of tamoxifen and 4OHTam were reversible in the next generation after descendants were withdrawn from chemical stress (i.e., recovery experiment), and whether the lowest test concentration of each chemical induced toxic effects when both concentrations were combined (i.e., mixture experiments). Our results showed that tamoxifen and 4OHTam induced the adverse effects at environmentally relevant concentrations. Tamoxifen and 4OHTam impaired size, viability, reproduction and the r in four generations of treated D. pulex, but these effects were not clearly magnified over generations. Tamoxifen was more potent than 4OHTam on D. pulex. When used in a mixture, the combination of tamoxifen and 4OHTam induced effects in offspring, whereas no effects were observed when these chemicals were tested individually. In the recovery experiment, the reproduction and size were reduced in offspring withdrawn from chemical exposures. Our results suggested that tamoxifen and its metabolite may be a relevant pharmaceutical to consider in risk assessment.
... Among studied anti-inflammatories and anti-blockers, most of them were removed less than 5%, while some antibiotics can be even removed upto 90% by sorption technique onto sludge. 36 Pharmaceutical compounds, particularly tetracyclines, have the propensity to sorb the soil particles or to form complexes with ions, which are present in the terrestrial ecosystem. 37 Numerous pharmaceutical substances might have great impact on their behaviour in spite of being weak acids, weak bases, or zwitterions and site-specific water, soil, or sediment conditions viz. ...
Article
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Pharmaceutical products and their wastes play a major role in the degradation of environment. These drugs have positive as well as negative consequences on different environmental components including biota in different ways. Many types of pharmaceutical substances have been detected with significant concentrations through various advanced instrumental techniques in surface water, subsurface water, ground water, domestic waste water, municipal waste water and industrial effluents. The central as well as state governments in India are providing supports by creating excise duty free zones to promote the pharmaceutical manufacturers for their production. As a result, pharmaceutical companies are producing different types of pharmaceutical products at large scale and also producing complex non-biodegradable toxic wastes byproducts and releasing untreated or partially treated wastes in the environment in absence of strong regulations. These waste pollutants are contaminating all types of drinking water sources. The present paper focuses on water quality pollution by pharmaceutical pollutants, their occurrences, nature, metabolites and their fate in the environment.
... This amount is reached because the individual dosage in imaging treatment is up to 300 g ( Haiß and Kümmerer, 2006). ICM are non-biodegradable and only partially removed in WWTP, so their concentration in surface and drinking water is increasing, with the concentration of Iohexol in Lake Leman, Switzerland being 0.03 mg/L ( Ch evre, 2014), or Iopamidol, which was found in groundwater up to 2.4 mg/L ( Ternes and Hirsch, 2000). Since the proven incapability of the existing WWTPs to handle ICM is established, their discharge to natural water bodies will contain the aforementioned amounts ( Putschew et al., 2000;Ternes and Hirsch, 2000; P erez and Barcel o, 2007). ...
Article
In this work, an Iodinated Contrast Medium (ICM), Iohexol, was subjected to treatment by 3 Advanced Oxidation Processes (AOPs) (UV, UV/H2O2, UV/H2O2/Fe2+). Water, wastewater and urine were spiked with Iohexol, in order to investigate the treatment efficiency of AOPs. A tri-level approach has been deployed to assess the UV-based AOPs efficacy. The treatment was heavily influenced by the UV transmittance and the organics content of the matrix, as dilution and acidification improved the degradation but iron/H2O2 increase only moderately. Furthermore, optimization of the treatment conditions, as well as modeling of the degradation was performed, by step-wise constructed quadratic or product models, and determination of the optimal operational regions was achieved through desirability functions. Finally, global chemical parameters (COD, TOC and UV-Vis absorbance) were followed in parallel with specific analyses to elucidate the degradation process of Iohexol by UV-based AOPs. Through HPLC/MS analysis the degradation pathway and the effects the operational parameters were monitored, thus attributing the pathways the respective modifications. The addition of iron in the UV/H2O2 process inflicted additional pathways beneficial for both Iohexol and organics removal from the matrix.
... Global issues are eutrophication and algal bloom caused by the discharge of nutrient rich water from agricultural activities and domestic sewage (Smith 2003;Palaniappan et al. 2010;Habersack and Samek 2016). The increasing release of personal care and pharmaceuticals products in watercourses is also preoccupying (Chèvre 2014;Aristizabal-Ciro et al. 2017;Ebele et al. 2017). The effects of pollutants on aquatic ecosystems and on the available amount of clean useable water are of particular concern. ...
Article
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Hydro-climatic changes and the increasing release of pollutants into rivers by human activities tend to affect the quality of watercourses, to alter aquatic ecosystems and to reduce the amount of useable water. The ecological and chemical states of rivers and their evolution is thus of growing concern. In Europe and Switzerland, water policies are progressively shifting towards a holistic approach of river systems. The European Commission notably established a framework to highlight rivers’ ecological deficits and to enhance regional or local water management plans. In Switzerland, a similar framework is currently under development. In this paper, both procedures are compared and implemented in a Swiss catchment dominated by agricultural activities. The aim is to define the challenges that still need to be addressed to assess and sustain river health. The hydromorphological, ecological, and ecotoxicological quality of the river was evaluated. Both frameworks highlighted the fact that no section of the river can currently be classified as being in a good environmental state and that the state deteriorates as tributaries and wastewater discharge flow into the main riverbed. Chemical issues and water quality changes due to hydro-climatic variations and management strategies were also pinpointed. Both frameworks are thus useful tools to survey changes in rivers quality in space and over time. However, challenges remain regarding the appropriate strategies to monitor and analyze chemicals, the definition of target values and conditions, the evaluation and integration of human-induced pressures, and the overall evaluation of the state of a river. The development of integrated indicators or of ecosystem services approaches is considered as a potential solution to explore river health and to define efficient restoration measures by water managers.
... igh doses in hospitals. In one standard Swiss university hospital, iohexol consumption reached 725 g/day ( Weissbrodt et al., 2009) and half this was discharged in wastewater. The concentration of iohexol detected in surface water bodies and wastewater effluent is in a range from ng/L to ?g/L, which will pose a high risk to the environmental biota (Ch?vre, 2014). ...
Article
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To improve the degradation ability of anaerobic granular sludge (AGS) toward the iodinated contrast media (ICM) iohexol, biogenic nanoscale palladium (Pd) was formed in AGS via microbial reduction. The Pd hosted in AGS (Pd-AGS) was used for iohexol degradation. The effects of the electron donor, reaction medium, iodide ion fouling, and polymer embedding of the Pd-AGS on the reactivity were investigated. Our results showed the Pd-AGS increased the degradation rate of iohexol, with a conversion rate constant increased by 86.3-fold compared to the AGS control. Various organic compounds were investigated as electron donors to initiate the catalytic activity of Pd-AGS and the promotion achieved with the tested electron donors was in the following order: formate > lactate > ethanol > glucose > acetate. The Pd-AGS had high reactivity in deionized water at mild pH, and almost no reactivity under acidic (pH = 1.2) and alkaline (pH > 11) conditions. The presence of iodide ions in the medium inhibited the catalytic activity of Pd-AGS toward iohexol because of catalyst fouling. Embedding the Pd-AGS in alginate, chitosan, or polyvinyl alcohol (PVA) could prevent Pd loss but it also retarded the iohexol degradation rate. The Pd-AGS, as a combination of Pd catalyst and AGS, provides a novel strategy for iohexol degradation in polluted water and wastewater.
... In our experimental setup, embryos were singly raised under conditions that are arguably close to optimal for their development (e.g., minimizing pathogen growth and mechanical stress). In the wild, embryos are typically exposed to a combination of various types of stressors, such as opportunistic microbes (Wilkins, Rogivue, Schütz, Fumagalli, & Wedekind, 2015) or other micropollutants (Chèvre, 2014;Moschet et al., 2014). If the toxicity of EE2 is amplified by further stress factors (e.g., Segner, Schmitt-Jansen, & Sabater, 2014; ...
Article
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One of the most common and potent pollutants of freshwater habitats is 17‐alpha‐ethynylestradiol (EE2), a synthetic component of oral contraceptives that is not completely eliminated during sewage treatment and that threatens natural populations of fish. Previous studies found additive genetic variance for the tolerance against EE2 in different salmonid fishes and concluded that rapid evolution to this type of pollution seems possible. However, these previous studies were done with fishes that are lake‐dwelling and hence typically less exposed to EE2 than river‐dwelling species. Here, we test whether there is additive genetic variance for the tolerance against EE2 also in river‐dwelling salmonid populations that have been exposed to various concentrations of EE2 over the last decades. We sampled 287 adult brown trout (Salmo trutta) from seven populations that show much genetic diversity within populations, are genetically differentiated, and that vary in their exposure to sewage‐treated effluent. In order to estimate their potential to evolve tolerance to EE2, we collected their gametes to produce 730 experimental families in blockwise full‐factorial in vitro fertilizations. We then raised 7,302 embryos singly in 2‐ml containers each and either exposed them to 1 ng/L EE2 (an ecologically relevant concentration, i.e., 2 pg per embryo added in a single spike to the water) or sham‐treated them. Exposure to EE2 increased embryo mortality, delayed hatching time, and decreased hatchling length. We found no population differences and no additive genetic variance for tolerance to EE2. We conclude that EE2 has detrimental effects that may adversely affect population even at a very low concentration, but that our study populations lack the potential for rapid genetic adaptation to this type of pollution. One possible explanation for the latter is that continuous selection over the last decades has depleted genetic variance for tolerance to this synthetic stressor.
... Advanced oxidation processes (AOPs) are efficient to treat an extensive range of industrial wastewater and an environment-affable green technology (Chèvre 2014). Among all the AOPs, photo-Fenton (PF) and electro-Fenton (EF) have been demonstrated as promising treatment methods for micropollutants along with other pollutants that have received great attention for water remediation because of Editorial responsibility: iskender AKKURT. ...
Article
Heterogeneous photo-electro-Fenton oxidation (hPEF) is known to be a robust technique, which can be employed for promoting organic degradation. This paper describes an environmentally friendly approach with the combination of photocatalysis and electrocatalysis in less acidic pH, aiming to achieve faster mineralization of a pharmaceutical micropollutant without adding any external oxidants. TiO2/GO/loaded Ag non-active electrodes are synthesized for the degradation of bupropion hydrochloride (antidepressant drug). The present work also seeks the parametric modeling and optimization of hPEF process parameters by using R programming. Nonlinear kinetic modeling was performed for the determination of kinetic parameters. The role of selected process parameters on the mineralization of bupropion was also explained in detail. The OH• and O2•− showed their active participation in the degradation process, while Ag and UV-C played an active role in the disinfection of treated wastewater.
... These compounds could be persistent organic pollutants, owing to their resistance to conventional chemical, biological, and photolytic processes (DONNER et al., 2013;EBELE ABDALLAH, HARRAD, 2017;GRANDCLÉMENT et al., 2017). As a result, they have been detected in rivers (BARONTI et al., 2000;RODRIGUEZ-MOZAZ et al., 2015;BERTELKAMP et al., 2016;ARCHER et al., 2017;WEE et al., 2019;LIU et al., 2020), lakes (CHÈVRE, 2014;YAN et al., 2018;GOLOVKO et al., 2020), oceans (XIE et al., 2012;PEREIRA et al., 2016), and even drinking water KNAPPE, 2005;JONGH et al., 2012;KENNEDY et al., 2015) worldwide. ...
Article
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Adsorption is one of the most efficient technologies for the removal of Concerning Emergent Compounds (CECs), also known as Organic Micropollutant (OMP). However, the use of activated carbon in developing countries is still costly. Thus, lignocellulosic residues are used as a base for making new adsorbent materials. This study assessed the relationship between the multicomponent adsorption of CECs in lignin-based adsorbents and the characteristics of the compounds. For this, 27 target compounds were prepared in an aqueous solution and submitted to the adsorption in 3 different materials. All the samples were analyzed in ultra-performance liquid chromatography coupled with mass spectrometry. The results were evaluated with the aid of the multivariate least squares regression (PLS-R) technique. It was observed that the adsorption of pharmaceuticals on activated carbons is a complex process governed by the properties of the adsorbed molecules, and the removal efficiency could be altered by external properties (e.g., adsorbent properties, pH, and organic matter). Even if it was reached an excellent average percentage removal (5.44 – 128.91%), the influence of other organic compounds could not be neglected. Unfortunately, to obtain a good understanding of the interactions between the single chemical molecule and the adsorbents, it would be necessary to study the process for each compound separately from the others and then consider the matrix effect due to the mixing of various pharmaceuticals with very different properties.
... Pesticide use has been identified as a major cause of the pollution of rivers and streams in Europe, China, and the United States (FAO, 2017;Parris, 2011) plus as a likely driver of loss of aquatic biodiversity in addition to nutrient and habitat degradation in streams (Beketov, Kefford, Schäfer, & Liess, 2013;Stehle & Schulz, 2015a). The presence of pesticides in surface water also raises the question of human exposure though drinking water (Chèvre, 2014). Water regulatory jurisdictions worldwide have designed policies to reduce water contamination and have introduced regulatory limits. ...
Article
Awareness of the presence of high concentrations of pesticides in Swiss rivers has increased in the last decade. Since 2017, the Federal Department of the Environment, Transport, Energy and Communications is planning to introduce new regulatory acceptable concentrations for surface water of 38 organic pesticides. Based on pesticide concentration analyses carried out in a small agricultural catchment in the canton of Vaud, over the 2005–2015 period, we review the impacts of this legislative revision on the chemical status of rivers. A first comparison between the historical standard (0.1 μg/L) and revised water quality criteria (WQC) highlights that standards are raised for 12 pesticides and lowered for 25 pesticides, sometimes with very high ratios. Risk coefficients were computed based on the historical standard and revised WQC to determine the chemical status of the river. The worst‐case value was retained to define this status. Individual risk coefficients indicate that more pesticides meet the revised WQC than the historical one, leading to very different chemical status. According to the historical standard, the chemical status of the Boiron River is defined as moderate to poor, and the main problem is the presence of herbicides. According to the revised WQC, the chemical status is good, and periodically moderate or poor. Ninety percent of the pesticides identified had a low to very low ecotoxicological risk coefficient. Other issues related to insecticides were identified. Based on these results, we discuss the importance of the standard chosen when defining regulatory acceptable concentrations. This article is categorized under: Water and Life > Conservation, Management, and Awareness Science of Water > Water Quality Engineering Water > Sustainable Engineering of Water A suggestion for 38 new water quality criteria for pesticides led us to analyze their impacts on the classification of the chemical status of a river in a Swiss canton. We discuss revision of the standards and recommend them as long as ecosystem protection is guaranteed and demonstrated.
... Dünya Sağlık Örgütü'ne (WHO) göre, çevrede bulunan veteriner ilaçlarının su ve toprak matrislerinde dirençli antibiyotiklerin gelişmesinden sorumlu olduğu belirtilmektedir. Son yıllarda ABD ve Avrupa'da veteriner ilaçlarının çevresel risk değerlendirmelerinin oluşturulması ve gereklilikleri ile son gelişmeler giderek hız kazanmaktadır [55]. Farmasötiklerin sucul organizmalardaki uzun vadeli etkilerini değerlendirmek için çok fazla araştırma yapılmasına rağmen, bunların sayısının hala çok düşük olduğunu belirtilmektedir [56]. ...
... Most studies reported in the literature are devoted to the occurrence of PhACs in rivers and lakes (Wilkinson John et al., 2022;Kondor et al., 2020;Fonseca et al., 2020;Guzel et al., 2019;Maasz et al., 2019;Carpenter and Helbling, 2018;Aminot et al., 2016;Golovko et al., 2020;Chèvre, 2014;Giebułtowicz and Nałęcz-Jawecki, 2016;Giebułtowicz and Nałęcz-Jawecki, 2014) as well as coastal waters (Reis-Santos et al., 2018;Borecka et al., 2015;Feo et al., 2020). There are only two reports on the concentration of PhACs in coastal sediments of the Baltic Sea (Siedlewicz et al., 2016;Siedlewicz et al., 2014). ...
Article
The occurrence of 130 pharmaceutically active compounds (PhACs) in sediments collected from 70 sampling sites in the Odra River estuary (SW Baltic Sea) was investigated. The highest concentration levels of the compounds were found in the vicinity of effluent discharge from two main Szczecin wastewater treatment plants: “Pomorzany” and “Zdroje”, and nearby the seaport and shipyard. The highest environmental risks (RQ > 1) were observed for pseudoephedrine (RQ = 14.0), clindamycin (RQ = 7.3), nalidixic acid (RQ = 3.8), carbamazepine (RQ = 1.8), fexofenadine (RQ = 1.4), propranolol (RQ = 1.1), and thiabendazole (RQ = 1.1). RQ for each compound varied depending on the sampling sites. High environmental risk was observed in 30 sampling sites for clindamycin, 22 sampling sites for pseudoephedrine, 19 sampling sites for nalidixic acid, 4 sampling sites for carbamazepine, and 3 sampling sites for fexofenadine. The medium environmental risk (0.1 < RQ < 1) was observed for 16 compounds: amisulpride, amitriptyline, amlodipine, atropine, bisoprolol, chlorpromazine, lincomycin, metoprolol, mirtazapine, moclobemide, ofloxacin, oxazepam, tiapride, tolperisone, verapamil, and xylometazoline. Due to the scarcity of toxicological data related to benthic organisms, only an approximate assessment of the environmental risk of PhACs is possible. Nevertheless, the compounds with medium and high risk should be considered as pollutants of high environmental concern whose occurrence in the environment should remain under close scrutiny.
... Rivers whose catchments include agricultural and urban land receive direct and indirect pesticides influx (Chèvre, 2014;Moschet et al., 2014), and these molecules can threat aquatic organisms even at low concentrations (DeLorenzo et al., 2001;Schulz, 2004). Moschet et al. (2014) developed a broad screening system to detect and quantify pesticides in surface waters and tested it in 5 different catchments of Switzerland. ...
Article
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Pesticides are often toxic to nontarget organisms, especially to those living in rivers that drain agricultural land. The brown trout (Salmo trutta) is a keystone species in many such rivers, and natural populations have hence been chronically exposed to pesticides over multiple generations. The introduction of pesticides decades ago could have induced evolutionary responses within these populations. Such a response would be predicted to reduce the toxicity over time but also deplete any additive genetic variance for the tolerance to the pesticides. If so, populations are now expected to differ in their susceptibility and in the variance for the tolerance depending on the pesticides they have been exposed to. We sampled breeders from seven natural populations that differ in their habitats and that show significant genetic differentiation. We stripped them for their gametes and produced 118 families by in vitro fertilization. We then raised 20 embryos per family singly in experimentally controlled conditions and exposed them to one of two ecologically relevant concentrations of either the herbicide S‐metolachlor or the insecticide diazinon. Both pesticides affected embryo and larval development at all concentrations. We found no statistically significant additive genetic variance for tolerance to these stressors within or between populations. Tolerance to the pesticides could also not be linked to variation in carotenoid content of the eggs. However, pesticide tolerance was linked to egg size, with smaller eggs being more tolerant to the pesticides than larger eggs. We conclude that an evolutionary response to these pesticides is currently unlikely and that (a) continuous selection in the past has either depleted genetic variance in all the populations we studied or (b) that exposure to the pesticides never induced an evolutionary response. The observed toxicity selects against large eggs that are typically spawned by larger and older females.
... Chemical pollution is one of the anthropogenic pressures that can threaten salmonid populations [1][2][3]. Salmonids are particularly exposed to such micropollutants during embryogenesis, because they typically have large eggs and long embryo developmental times, both of which enable greater uptake of ambient micropollutants during this sensitive stage [4,5]. One of the most common pollutant is the synthetic estrogen 17α-ethynylestradiol (EE2) that is an active ingredient of most oral contraceptive pill formulations and has higher stability and estrogenic potency than its natural counterpart 17βestradiol [6,7]. ...
Preprint
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Background: The presence of a novel pollutant can induce rapid evolution if there is additive genetic variance for the tolerance to the stressor. Continuous selection over some generations can then reduce the toxicity of the pollutant but also deplete the additive genetic variance for the tolerance and thereby slow down adaptation. One common pollutant that has been ecologically relevant for some time is 17alpha-ethynylestradiol (EE2), a synthetic compound of oral contraceptives since their market launch in the 1960s. EE2 is typically found in higher concentrations in rivers than in lakes. Recent experimental work revealed significant genetic variance for the tolerance to EE2 in two lake-spawning salmonid species but no such variance in river-spawning brown trout. We used another river-spawning salmonid, the European grayling Thymallus thymallus, to study the toxicity of an ecologically relevant concentration of EE2. We also used a full-factorial in vitro breeding design and singly rearing of 1,555 embryos and larvae of 40 sib groups to test whether there is additive genetic variance for the tolerance to this pollutant. Results: We found that exposure to EE2 reduced larval growth after hatching, but contrary to what has been found in the other salmonids, there were no significant effects of EE2 on embryo growth and survival. We found additive genetic variance for embryo viability, i.e. heritability for fitness. However, there was no significant additive variance for the tolerance to EE2. Conclusions: Our findings support the hypothesis that continuous selection has reduced the toxicity of EE2 and depleted genetic variance for tolerance to this synthetic stressor.
... Dünya Sağlık Örgütü'ne (WHO) göre, çevrede bulunan veteriner ilaçlarının su ve toprak matrislerinde dirençli antibiyotiklerin gelişmesinden sorumlu olduğu belirtilmektedir. Son yıllarda ABD ve Avrupa'da veteriner ilaçlarının çevresel risk değerlendirmelerinin oluşturulması ve gereklilikleri ile son gelişmeler giderek hız kazanmaktadır [55]. Farmasötiklerin sucul organizmalardaki uzun vadeli etkilerini değerlendirmek için çok fazla araştırma yapılmasına rağmen, bunların sayısının hala çok düşük olduğunu belirtilmektedir [56]. ...
Article
Veteriner ilaçları hastalığı tedavi etmek ve hayvan sağılığını korumak için yaygın olarak kullanılmaktadır. Hayvan hastalıklarının tedavisinde ve önlenmesinde kullanılan veteriner ilaçları, yoğun tarımsal ve su ürünleri yetiştiriciliğinden dolayı çevre kirliliğinin önemli bir kaynağını oluşturmaktadır. Hayvancılık ve tavukçuluk üretiminde kullanılan farmasötik maddeler hayvanlar tarafından metabolize edildikten sonra dışkı yoluyla çevresel ortamlara bırakılırlar. Hayvan yemi ve kullanılmayan ilaçların uygunsuz bertarafı sonucunda yüzeysel su kaynaklarına kadar ulaşabilirler. Ayrıca hayvan gübrelerinin tarımsal alanlarda kullanılması veteriner ilaçlarının çevrede bulunmasına neden olmaktadır. Bu derlemede veteriner uygulamalarında yaygın olarak kullanılan ilaçların çevresel ortamlarda bulunuşu, davranışı, dönüşümü ve canlılar üzerindeki toksik etkileri hakkında mevcut bilgiler verilmektedir. Ayrıca düşük konsantrasyondaki ilaçların ve metabolitlerinin uzun vadeli etkileri, ekosistemdeki veteriner ilaçlarının davranışı ve çevresel etkileri araştırılmıştır.
... Chemical pollution is one of the anthropogenic pressures that can threaten salmonid populations [1][2][3]. Salmonids are particularly exposed to such micropollutants during embryogenesis, because they typically have large eggs and long embryo developmental times, both of which enable greater uptake of ambient micropollutants during this sensitive stage [4,5]. One of the most common pollutant is the synthetic estrogen 17α-ethynylestradiol (EE2) that is an active ingredient of most oral contraceptive pill formulations and has higher stability and estrogenic potency than its natural counterpart 17β-estradiol [6,7]. ...
Article
Full-text available
Background: The presence of a novel pollutant can induce rapid evolution if there is additive genetic variance for the tolerance to the stressor. Continuous selection over some generations can then reduce the toxicity of the pollutant but also deplete the additive genetic variance for the tolerance and thereby slow down adaptation. One common pollutant that has been ecologically relevant for some time is 17alpha-ethynylestradiol (EE2), a synthetic compound of oral contraceptives since their market launch in the 1960s. EE2 is typically found in higher concentrations in rivers than in lakes. Recent experimental work revealed significant genetic variance for the tolerance to EE2 in two lake-spawning salmonid species but no such variance in river-spawning brown trout. We used another river-spawning salmonid, the European grayling Thymallus thymallus, to study the toxicity of an ecologically relevant concentration of EE2. We also used a full-factorial in vitro breeding design and singly rearing of 1555 embryos and larvae of 40 sib groups to test whether there is additive genetic variance for the tolerance to this pollutant. Results: We found that exposure to EE2 reduced larval growth after hatching, but contrary to what has been found in the other salmonids, there were no significant effects of EE2 on embryo growth and survival. We found additive genetic variance for embryo viability, i.e. heritability for fitness. However, there was no significant additive variance for the tolerance to EE2. Conclusions: Our findings support the hypothesis that continuous selection has reduced the toxicity of EE2 and depleted genetic variance for tolerance to this synthetic stressor.
Article
In this study, the anti-depressant Venlafaxine, a new emerging contaminant of interest for the Swiss legislation, was subjected to systematic degradation. In order to develop an efficient framework for the treatment of emerging contaminants at industrial scale by AOPs, the photo-Fenton process was employed and the effect of the concentration of the Fenton’s reagents and the implication of the operating pH was assessed. Initially, in order to acquire a simple model that describes the process, a (general) full factorial experimental design was implemented. Generally, Venlafaxine degradation was achieved in minutes range at pH = 3 and increased with higher pH values. However, the changes in pH inflicted considerable modification in the treatment efficiency and imposed the subsequent use of higher order models, obtained by response surface methodology (3 pH-specific central composite designs). The improved, respective second degree models created for the 3 categories of response variables (kinetics, efficiency, Fenton evolution) were used as input for the desirability functions, towards the statistical optimization of the process. The composite desirability values obtained indicated the optimal operating regions (9 mg/L iron and 28 mg/L H2O2), thus contributing to efficient application of the photo-Fenton process. The developed approach can be used as framework when the optimal treatment conditions of new, emerging contaminants are sought at production level, through well-established advanced oxidation processes and effective statistical methods.
A new concern about surface water quality is the occurrence of emerging contaminants that have being recognized as a new class of water contaminants such as antibiotics, hormones, pesticides, personal care products and pharmaceutical products. The occurrence of these contaminants in the aquatic environment and especially in surface water is a serious concern because this is usually the source of water for drinking water treatment plants (DWTP). This review provides a summary of the occurrence and the analytical methodology (extraction process, chromatography analysis, detection systems and ionization source) of emerging contaminant analysis in surface waters including rivers, lakes, creeks and wetlands for their analysis.
Article
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The concept of drug recycle by recovering active pharmaceutical ingredients (APIs) from unused tablets and capsules was demonstrated using acetaminophen, tetracycline HCl, and (R,S)-(±)-ibuprofen as case examples. The recovery process comprised three core unit operations: solid–liquid extraction, filtration, and crystallization. Recovery yields of 58.7 wt %, 73.1 wt %, and 67.6 wt % for acetaminophen, tetracycline HCl, and (R,S)-(±)-ibuprofen were achieved, respectively. More importantly, all of the APIs were of high purity based on high-performance liquid chromatography assay. The crystal forms of the recovered APIs were in conformity with the standards.
Article
This study analyzes the potential of organic substrates to retain both nitrate (NO3-) and the herbicide agent atrazine (ATR) at short hydraulic residence times (HRT). The objective is to implement effective and efficient mitigation zones to improve the quality of tile drain waters. Taking the results of a pre-study at laboratory scale into account, the focus is now on retention of the two contaminants under more realistic conditions. In a one and a half year lasting technical scale experiment the performance of a flow through bioreactor (8.0m long, 2.0m wide, and 0.4m high), filled with straw of common wheat (Triticum aestivum L.) and bark mulch of pine tree (Pinus sp.), was studied at HRT of 0.43 days. The bioreactor was run horizontally and its reaction zone was kept water-saturated throughout most time of the experiment. NO3- (~100mgL-1) and ATR (~30μgL-1) were constantly and continuously dosed into flow. As result NO3- retention varied between 3g-Nm-3d-1 (8%) at 9°C and 30g-Nm-3d-1 (82%) at 21°C. ATR retention was observed in the range of 10mg-ATRm-3d-1 (15%) at 9°C and 22mg-ATRm-3d-1 (48%) at 21°C. ATR- and NO3- retention are positively correlated with temperature. NO3- retention benefits from the labile organic carbon in straw and ATR retention seems to base on high adsorption to bark mulch and formation of bound residues. In conclusion the combined use of straw and bark mulch in mitigation systems has the potential to facilitate effective parallel retention of NO3- and the group of less mobile herbicide agents like ATR, even under the pressure of high flow events as expected in the rainy season.
Article
Pharmaceuticals and personal care products (PPCPs) are receiving global scientific attention due to their occurrence, persistence and risk to aquatic and terrestrial organisms. In this study, we investigated the occurrence of 19 PPCPs in 6 lakes and River Nag in the city of Nagpur, India. Grab samples were collected and screened by LC‐MS/MS. A total of 13 compounds were detected. In the multiple‐site monitoring study, metformin (19‐94 µg/L) and triclosan [upto 74.3 µg/L] were identified as the major PPCPs. In the single‐site study (performed for 2 days at 2 hour interval), a spike was observed in the evening of Day 1, e.g. atenolol (0.39‐35.9 µg/L), metoprolol (ND‐26.4 µg/L), acetaminophen (1.64‐14.2), naproxen (0.5‐15.9 µg/L), etc. The maximum number of compounds was detected in Lake Futala (13), followed by Gandhisagar (7), Khindsi (6), Ambazari (4), Koradi (4) and Gorewada (1). Triclosan and methyl paraben were the major compounds in lake samples.
Article
In recent years, pharmaceutical compounds have emerged as potential contaminants in the aquatic matrices of the environment. High production, consumption, and limited removal through conventional treatment processes/wastewater treatment plants (WWTPs) are the major causes for the occurrence of pharmaceutical compounds in wastewater and aquatic environments worldwide. A number of studies report adverse health effects and risks to aquatic life and the ecosystem because of the presence of pharmaceutical compounds in the aquatic environment. This paper provides a state-of-the-art review of the occurrence of pharmaceutical compounds in treated wastewater from various WWTPs, surface water and groundwater bodies. Additionally, this review provides comprehensive information and pointers for research in wastewater treatment and waterbodies management.
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Among pollutants released into the environment by human activities, residues of pharmaceuticals are an increasing matter of concern because of their potential impact on ecosystems. The aim of this study was to analyse differences of protein expression resulting from acute (2 days) and middle-term (7 days) exposure of aquatic microcrustacean Daphnia pulex to the anticancer drug tamoxifen. Using a liquid chromatography - mass spectrometry shotgun approach, about 4000 proteins could be identified, providing the largest proteomics dataset of D. pulex published up to now. Considering both time points and tested concentrations, 189 proteins showed a significant fold change. The identity of regulated proteins suggested a decrease in translation, an increase in protein degradation and changes in carbohydrate and lipid metabolism as the major effects of the drug. Besides these impacted processes, which reflect a general stress response of the organism, some other regulated proteins play a role in Daphnia reproduction. These latter results are in accordance with our previous observations of the impact of tamoxifen on D. pulex reproduction, and illustrate the potential of ecotoxicoproteomics to unravel links between xenobiotic effects at the biochemical and at the organismal level. Data are available via ProteomeXchange with identifier PXD001257.
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Iohexol can hardly be removed in conventional wastewater treatment processes due to its non-biodegradable and hydrophilic characteristics. In this study, a kinetic model was established to describe iohexol degradation in Fe (II)-activated persulfate system. The developed model can well predict iohexol degradation and evolution of sulfate radical with various initial iohexol and oxidant (ferrous iron and persulfate) concentrations under various water matrix. The rate constant of iohexol reacting with sulfate radical was calculated as (1.83 ± 0.10) × 10 ⁹ M ⁻¹ s ⁻¹ . The effects of the two most common components in natural water bodies, chloride ion and natural organic matter (NOM) on iohexol degradation, were also studied. Both experimental data and model results showed that the low concentration of chloride ion promoted iohexol degradation while high concentration inhibited it, and NOM slightly inhibited iohexol degradation. Besides, radical quenching tests were employed to identify the main radicals formed in the system and further verified the model accuracy. The model is also capable of predicting the atrazine degradation with the correlation coefficients between the experimental data and predicted results above 0.97, suggesting the applicability of the established model for some other recalcitrant contaminant degradation in the Fe ²⁺ /PS system.
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Significant quantities of antibiotics are used in all parts of the globe to treat diseases with bacterial origins. After ingestion, antibiotics are excreted by the patient and transmitted in due course to the aquatic environment. This study examined temporal fluctuations (monthly time scale) in antibiotic sources (ambulatory sales and data from a hospital dispensary) for Lausanne, Switzerland. Source variability (i.e., antibiotic consumption, monthly data for 2006-2010) were examined in detail for nine antibiotics - azithromycin, ciprofloxacin, clarithromycin, clindamycin, metronidazole, norfloxacin, ofloxacin, sulfamethoxazole and trimethoprim, from which two main conclusions were reached. First, some substances - azithromycin, clarithromycin, ciprofloxacin - displayed high seasonality in their consumption, with the winter peak being up to three times higher than the summer minimum. This seasonality in consumption resulted in seasonality in Predicted Environmental Concentrations (PECs). In addition, the seasonality in PECs was also influenced by that in the base wastewater flow. Second, the contribution of hospitals to the total load of antibiotics reaching the Lausanne Wastewater Treatment Plant (WTP) fluctuated markedly on a monthly time scale, but with no seasonal pattern detected. That is, there was no connection between fluctuations in ambulatory and hospital consumption for the substances investigated.
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Ephemeroptera larvae are recognized worldwide for their sensitivity to oxygen depletion in running waters, and are therefore commonly used as bioindicators in many monitoring programmes. Mayflies inhabiting lentic waters, like lakes and ponds, in contrary have been poorly prospected in biomonitoring. For this purpose, a better understanding of their distribution in lentic habitats and of the relations of species presence with environmental conditions are needed. Within this framework, 104 ponds were sampled in Switzerland. The Ephemeroptera are found to be an insect order particularly well represented in the ponds studied here (93% of the lowland ponds). Nevertheless, in terms of diversity, they are relatively poorly represented (mean species number=1.9). Two species dominated: Cloeon dipterum (Baetidae) and Caenis horaria (Caenidae). The investigations contributed to the updating of the geographical distribution of the species in Switzerland, as many of the observations appear to be from new localities. The trophic state of ponds appears here to be important for Ephemeroptera communities. First, there is a negative relationship between total phosphorus (TP) concentrations and species richness. Second, the presence of Caenis horaria or Cloeon dipterum is dependent on the trophic state. Caenis horaria is most closely associated with low levels of TP concentrations, while Cloeon dipterum appears to be less sensitive, and is most frequently found in hypertrophic conditions. A probable consequence of these relations, is that Baetidae are always present when Caenidae are also present. Contrastingly, Baetidae is observed as the only mayflies family present in several ponds.
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Background: Over the past 10–15 years, a substantial amount of work has been done by the scientific, regulatory, and business communities to elucidate the effects and risks of pharmaceuticals and personal care products (PPCPs) in the environment. Objective: This review was undertaken to identify key outstanding issues regarding the effects of PPCPs on human and ecological health in order to ensure that future resources will be focused on the most important areas. Data sources: To better understand and manage the risks of PPCPs in the environment, we used the “key question” approach to identify the principle issues that need to be addressed. Initially, questions were solicited from academic, government, and business communities around the world. A list of 101 questions was then discussed at an international expert workshop, and a top-20 list was developed. Following the workshop, workshop attendees ranked the 20 questions by importance. Data synthesis: The top 20 priority questions fell into seven categories: a) prioritization of substances for assessment, b) pathways of exposure, c) bioavailability and uptake, d) effects characterization, e) risk and relative risk, f ) antibiotic resistance, and g) risk management. Conclusions: A large body of information is now available on PPCPs in the environment. This exercise prioritized the most critical questions to aid in development of future research programs on the topic.
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At present, very little is known about the fate and persistence of multiresistant bacteria (MRB) and their resistance genes in natural aquatic environments. Treated, but partly also untreated sewage of the city of Lausanne, Switzerland is discharged into Vidy Bay (Lake Geneva) resulting in high levels of contamination in this part of the lake. In the present work we have studied the prevalence of MRB and resistance genes in the wastewater stream of Lausanne. Samples from hospital and municipal raw sewage, treated effluent from Lausanne's wastewater treatment plant (WTP) as well as lake water and sediment samples obtained close to the WTP outlet pipe and a remote site close to a drinking water pump were evaluated for the prevalence of MRB. Selected isolates were identified (16S rRNA gene fragment sequencing) and characterized with regards to further resistances, resistance genes, and plasmids. Mostly, studies investigating this issue have relied on cultivation-based approaches. However, the limitations of these tools are well known, in particular for environmental microbial communities, and cultivation-independent molecular tools should be applied in parallel in order to take non-culturable organisms into account. Here we directly quantified the sulfonamide resistance genes sul1 and sul2 from environmental DNA extracts using TaqMan real-time quantitative PCR. Hospital sewage contained the highest load of MRB and antibiotic resistance genes (ARGs). Wastewater treatment reduced the total bacterial load up to 78% but evidence for selection of extremely multiresistant strains and accumulation of resistance genes was observed. Our data clearly indicated pollution of sediments with ARGs in the vicinity of the WTP outlet. The potential of lakes as reservoirs of MRB and potential risks are discussed.
Book
In spite of the growing importance of Species Sensitivity Distribution models (SSDs) in ecological risk assessments, the conceptual basis, strengths, and weaknesses of using them have not been comprehensively reviewed. This book fills that need. Written by a panel of international experts, Species Sensitivity Distributions in Ecotoxicology reviews the current SSD methods from all angles, compiling for the first time the variety of contemporary applications of SSD-based methods. Beginning with an introduction to SSDs, the chapter authors review the issues surrounding SSDs, synthesizing the positions of advocates and critics with their own analysis of each issue. Finally, they discuss the prospects for future development, paving the way for improved future uses. In sum, this book defines the field of SSD modeling and application. It reveals a lively field, with SSD-applications extending beyond legally adopted quality criteria to other applications such as Life-Cycle Analysis. For anyone developing or revising environmental criteria or standards, this book explores the pros and cons of using the SSD approach. For anyone who needs to apply and interpret SSD-based criteria or standards, the book explains the basis for the numbers, thereby making it possible to correctly apply and defend them. For anyone performing ecological risk assessments, the book covers when and how to use SSDs including alternative assumptions, data treatments, computational methods, and available resources. Species Sensitivity Distributions in Ecotoxicology provides you with a clear picture of these standard models for estimating ecological risks from laboratory toxicity data.
Book
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.
Book
When the first green wave appeared in the mid and late 1960s, it was considered a fea­ 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 dis­ 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 purifica­ tion capacity of ecosystems and to set up emission standards, considering the rela­ 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.
Article
The developments made in the field of pharmaceuticals, hormones and fragrances in treated wastewaters, rivers and streams are discussed. Pharmaceuticals and personal care products (PCCP) are present in the water treatment plant effluents, because they are either partially removed or not at all removed. Ozonation is one of the method to eliminate these PCCPs by undertaking a broad upgrading of municipal waters, the risks associated with current effluent quality and then required risk reduction for upgraded works. Ozonation and membrane filtration reduces the emission of pathogens from treatment works into receiving waters. It is possible to define a combination of conventional and advanced treatment technologies to effectively remove PCCPs and microorganisms, that would create a multiple barrier system.
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Plant pathogenic strains of Pseudomonas syringae were isolated from lakes and rivers in the central North Island of New Zealand. These strains were identified by their ability to produce a fluorescent pigment on a modified King's B medium, by their ability to cause a hypersensitive reaction when infiltrated into tobacco plant and by the absence of a cytochrome c oxidase. Different aspects of the protocol used to isolate these strains have been assessed. Some of the strains isolated, and in some cases the majority of them, were resistant to copper and/or streptomycin. Significantly, these plant pathogenic bacteria were isolated from waterways in areas where no agriculture or horticulture is present and waterways used for crop irrigation. These results suggest that natural waterways could be a source of inoculum of plant pathogenic bacteria, and a source of genes that confer streptomycin resistance and/or copper resistance to these bacteria.
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Ecosystems and biocoenoses are exposed to multiple mixtures of environmental pollutants, but the usual risk assessment of chemical toxicities is focussed only on the judgement of single substance toxicity. With the two biometrical models concentration-addition and independent action known from pharmacology and toxicology, a pragmatic way for the analysis of combined effects is possible using the experimental knowledge of single substance toxicity. A short introduction to the models is given and an appropriate experimental design for mixture toxicity analysis is outlined. The principal suitability of the concepts was verifed in two different bioassays (green alga; luminescent bacterium) with the analysis of binary and multiple mixture toxicities of environmental chemicals. In this paper we present the results obtained with the green algae bioassay. Congruent results from the bioluminescence inhibition assay can be found in Grimme (1998). The results obtained indicate that the toxicities of mixtures of chemicals can be studied experimentally, even at low concentrations of the individual components. Mixture toxicities were detected at low, statistically non-significantly acting concentrations of the single compounds. These results force one to take mixture toxicities into account when environmental standards are established.
Article
The direct discharge of effluent wastewater into Vidy Bay (Lake Geneva) results in the formation of an effluent plume with locally high concentrations of wastewater-derived micropollutants. The micropollutant hotspots above the wastewater outfall present a potential ecotoxicological risk, yet the spatial extent of the plume and the associated ecotoxicological risk zone remain unclear. This work combines the two main processes affecting the spreading of the plume, namely dilution of micropollutants due to mixing and degradation by photolysis, into a coupled hydrodynamic-photolysis model, with which we estimated the spatial extent of the risk zone in Vidy Bay. The concentration of micropollutants around the wastewater outfall was simulated for typical wind scenarios and seasons relevant to Vidy Bay, and the resulting ecotoxicological risk was evaluated. Specifically, we determined the direct and indirect photolysis rate constants for 24 wastewater-derived micropollutants and implemented these in a hydrodynamic particle tracking model, which tracked the movement of water parcels from the wastewater outfall. Simulations showed that owing to thermal stratification, the zone of ecotoxicological risk is largest in summer and extends horizontally over 300 m from the outfall. Photolysis processes contribute to reducing the plume extent mainly under unstratified conditions when the plume surfaces. Moreover, it was shown that only a few compounds, mainly antibiotics, dominate the total ecotoxicological risk.
Article
Pharmaceuticals constitute an important environmental issue for receiving waters. A holistic approach, taking into consideration the sources of these compounds (hospitals, domestic use), discharges (wastewater effluent, combined sewer overflows) and related risks to the environment, is therefore needed to develop the best protection strategy. The substance flow analysis (SFA) approach, applied, for example, to the city of Lausanne, Switzerland, is an ideal tool to tackle these issues. Four substances were considered: one antibiotic (ciprofloxacin), an analgesic (diclofenac), and two anti-epileptics (carbamazepine and gabapentin). Consumption data for the main hospital of the city (916 beds) and for the population were available. Micropollutant concentrations were measured at different points of the system: wastewater inlet and outlet (WWTP), combined sewer overflows (CSO) and in the receiving waters (Vidy Bay, Lake Geneva). Measured and predicted concentrations were in agreement, except for diclofenac, for which analytical uncertainties were expected. Seven different scenarios were considered (supplementary treatment at the WWTP, at the hospital or at both places, etc.). Based on the results obtained, the supplementary treatment at the WWTP decreases the load of pharmaceuticals reaching surface water by a factor between 2 and 27, depending on the compound and on the technique. The treatment at the hospitals only influences the amount of ciprofloxacin reaching the environment and decreases the release by one third. The contribution of CSO to surface water pollution is low compared to that of the WWTP for the selected compounds. Regarding the risk for the receiving waters, ciprofloxacin was found to be the most problematic compound, with a risk quotient far above 1. In this particular case, a treatment at the WWTP is not sufficient to reduce the risk, and additional measures at the CSO or at the hospital should be considered. SFA is an ideal tool for developing the best strategy for pharmaceutical elimination, but its application depends on data availability and local conditions.
Article
The presence of potentially persistent and bioactive human metabolites in surface waters gives rise to concern; yet little is known to date about the environmental fate of these compounds. This work investigates the direct photolysis of human metabolites of the antibiotic sulfamethoxazole (SMX). In particular, we determined photolysis kinetics and products, as well as their concentrations in lake water. SMX, sulfamethoxazole β-D-glucuronide, 4-nitroso sulfamethoxazole and 4-nitro sulfamethoxazole were irradiated under various light sources and pH conditions. All investigated metabolites, except SMX-glucuronide were found to be more photostable than SMX under environmentally relevant conditions. Between two and nine confirmed photoproducts were identified for SMX-metabolites through ultra-performance liquid chromatography/high-resolution mass spectrometry. Interestingly, photolytic back-transformation to SMX was observed for 4-nitroso-SMX, indicating that this metabolite may serve as an environmental source of SMX. Moreover, two human metabolites along with SMX were regularly detected in Lake Geneva. The knowledge that some metabolites retain biological activity, combined with their presence in the environment and their potential to retransform to the parent compound, underlines the importance of including human metabolites when assessing the effects of pharmaceuticals in the environment.
Article
Many contaminants are released into aquatic systems intermittently in a series of pulses. Pulse timing and magnitude can vary according to usage, compound-specific physicochemical properties, and use area characteristics. Standard laboratory ecotoxicity tests typically employ continuous exposure concentrations over defined durations and thus may not accurately and realistically reflect the effects of certain compounds on aquatic organisms, resulting in potential over- or underestimation. Consequently, the relative effects of pulsed (2 d and 4 d) and continuous exposures of the duckweed Lemna minor to isoproturon, metsulfuron-methyl, and pentachlorophenol over a period of 42 d were explored in the present study. At the highest test concentrations, exposure of L. minor to pulses of metsulfuron-methyl resulted in effects on growth similar to those of an equivalent continuous exposure. For isoproturon, pulsed exposures had a lower impact than a corresponding continuous exposure, whereas the effect of pentachlorophenol delivered in pulses was greater. These differences may be explained by compound-specific uptake and degradation or dissipation rates in plants and the recovery potential that occurs following pulses for different pesticides. Given these results, use of a simple time-weighted average approach to estimate effects of intermittent exposures from short-term standard toxicity studies may not provide an accurate prediction that reflects realistic exposure scenarios. Development of mechanistic modeling approaches may facilitate better estimates of effects from intermittent exposures. Environ. Toxicol. Chem. © 2012 SETAC.
Article
This study describes an investigation on the occurrence of 27 pharmaceutical compounds, belonging to different classes, in the effluent from two wastewater treatment plants (WWTPs) and their receiving water bodies in the sensitive area of the Po Valley (northern Italy). These canals were monitored upstream and downstream of the effluent discharge points in order to evaluate the effluent impact on the quality of surface waters, commonly used for irrigation. An environmental risk assessment was also conducted by calculating the risk quotient, i.e. the ratio between measured concentration and predicted no effect concentration. Collected data show that, although average values of the selected compounds were in general higher in the effluent than in the surface waters, some compounds not detected in the WWTP effluent were detected in the receiving water (upstream as well as downstream), indicating that sources other than treated effluents are present as contaminations during extraction and analysis have to be excluded. The most critical compounds for the environment were found to be the antibiotics sulfamethoxazole, clarithromycin and azithromycin. The study shows that the potential toxicological effects of persistent micropollutants can be mitigated to some extent by a high dilution capacity, i.e. a high average flow rate in the receiving water body with respect to the effluent.
Article
A study was conducted in an area in north, Italy, on the effluent of two different sized hospitals and the influent and effluent of the receiving municipal treatment plant of one of the examined hospitals. The aim was to investigate 73 selected pharmaceuticals, belonging to twelve different classes, comparing their occurrence in the effluent directly exiting the hospital with that, mixed with the local urban effluent, at the point of its entry and exit from the treatment plant. Consistent differences were found in the concentrations of some antibiotics, analgesics and lipid regulators in the two wastewaters, confirming that hospital effluents should not be considered as possessing the same pollutant nature as urban wastewater. Furthermore, analysis of percentage contributions of the hospital to the treatment plant influent evidences that hospitals represent one of the main sources of pollutants, in particular antibiotics, receptor antagonists and lipid regulators. Hence, an environmental risk assessment, performed on the effluent from the hospital and the influent and effluent from the treatment plant, revealed a high risk for 9 pharmaceuticals in hospital effluent and for 4 of the 9 substances in the treatment plant influent and effluent, with antibiotics being the most critical compounds in terms of contribution and potential environmental risk for the hospital.
Article
There is little quantitative information on the temporal trends of pharmaceuticals and other emerging compounds, including artificial sweeteners, in urban groundwater and their suitability as tracers to inform urban water management. In this study, pharmaceuticals and artificial sweeteners were monitored over 6 years in a shallow urban groundwater body along with a range of conventional sewage tracers in a network of observation wells that were specifically constructed to assess sewer leakage. Out of the 71 substances screened, 24 were detected at above the analytical detection limit. The most frequent compounds were the iodinated X-ray contrast medium amidotrizoic acid (35.3%), the anticonvulsant carbamazepine (33.3%) and the artificial sweetener acesulfame (27.5%), while all other substances occurred in less than 10% of the screened wells. The results from the group of specifically constructed focus wells within 10 m of defective sewers confirmed sewer leaks as being a major entrance pathway into the groundwater. The spatial distribution of pharmaceuticals and artificial sweeteners corresponds well with predictions by pipeline leakage models, which operate on optical sewer condition monitoring data and hydraulic information. Correlations between the concentrations of carbamazepine, iodinated X-ray contrast media and artificial sweeteners were weak to non-existent. Peak concentrations of up to 4130 ng/l of amidotrizoic acid were found in the groundwater downstream of the local hospital. The analysis of 168 samples for amidotrizoic acid, taken at 5 different occasions, did not show significant temporal trends for the years 2002-2008, despite changed recommendations in the medical usage of amidotrizoic acid. The detailed results show that the current mass balance approaches for urban groundwater bodies must be adapted to reflect the spatially distributed leaks and the variable wastewater composition in addition to the lateral and horizontal groundwater fluxes.
Article
This review focuses on 118 pharmaceuticals, belonging to seventeen different therapeutic classes, detected in raw urban wastewater and effluent from an activated sludge system, a usual treatment adopted for urban wastewaters worldwide prior to final discharge into surface water bodies. Data pertaining to 244 conventional activated sludge systems and 20 membrane biological reactors are analysed and the observed ranges of variability of each selected compound in their influent and effluent reported, with particular reference to the substances detected most frequently and in higher concentrations. A snapshot of the ability of these systems to remove such compounds is provided by comparing their global removal efficiencies for each substance. Where possible, the study then evaluates the average daily mass load of the majority of detected pharmaceuticals exiting the secondary treatment step. The final part of the review provides an assessment of the environmental risk posed by their presence in the secondary effluent by means of the risk quotient that is the ratio between the average pharmaceutical concentration measured in the secondary effluent and the predicted no-effect concentration. Finally, mass load rankings of the compounds under review are compared with those based on their risk level. This analysis shows that the highest amounts discharged through secondary effluent pertain to one antihypertensive, and several beta-blockers and analgesics/anti-inflammatories, while the highest risk is posed by antibiotics and several psychiatric drugs and analgesics/anti-inflammatories. These results are reported with a view to aiding scientists and administrators in planning measures aiming to reduce the impact of treated urban wastewater discharge into surface water bodies.
Article
The authors derive predicted-no-effect concentrations (PNECs) for the steroid estrogens (estrone [E1], 17β-estradiol [E2], estriol [E3], and 17α-ethinylestradiol [EE2]) appropriate for use in risk assessment of aquatic organisms. In a previous study, they developed a PNEC of 0.35 ng/L for EE2 from a species sensitivity distribution (SSD) based on all available chronic aquatic toxicity data. The present study updates that PNEC using recently published data to derive a PNEC of 0.1 ng/L for EE2. For E2, fish were the most sensitive taxa, and chronic reproductive effects were the most sensitive endpoint. Using the SSD methodology, we derived a PNEC of 2 ng/L for E2. Insufficient data were available to construct an SSD for E1 or E3. Therefore, the authors used in vivo vitellogenin (VTG) induction studies to determine the relative potency of the steroid estrogens to induce VTG. Based on the relative differences between in vivo VTG induction, they derive PNECs of 6 and 60 ng/L for E1 and E3, respectively. Thus, for long-term exposures to steroid estrogens in surface water (i.e., >60 d), the PNECs are 6, 2, 60, and 0.1 ng/L for E1, E2, E3, and EE2, respectively. Higher PNECs are recommended for short-term (i.e., a few days or weeks) exposures.
Article
Freshwater and marine ecosystems are exposed to various multi-component mixtures of pollutants. Nevertheless, most ecotoxicological research and chemicals regulation focus on hazard and exposure assessment of individual substances only, the problem of chemical mixtures in the environment is ignored to a large extent. In contrast, the assessment of combination effects has a long tradition in pharmacology, where mixtures of chemicals are specifically designed to develop new products, e.g. human and veterinary drugs or agricultural and non-agricultural pesticides. In this area, two concepts are frequently used and are thought to describe fundamental relationships between single substance and mixture effects: Independent Action (Response Addition) and Concentration Addition. The question, to what extent these concepts may also be applied in an ecotoxicological and regulatory context may be considered a research topic of major importance, as the concepts would allow to make use of already existing single substance toxicity data for the predictive assessment of mixture toxicities. Two critical knowledge gaps are identified: (a) There is a lack of environmental realism, as a huge part of our current knowledge about the applicability of the concepts is restricted to artificial situations with respect to mixture composition or biological effect assessment. (b) The knowledge on what exactly is needed for using the concepts as tools for the predictive mixture toxicity assessment is insufficient. Both gaps seriously hamper the necessary, scientifically sound consideration of mixture toxicities in a regulatory context.
Article
This opinion paper assesses for the UK, whether the current use of cytotoxic drugs, one of the most toxic pharmaceuticals in common use, could pose a risk to aquatic organisms and to humans through water recycling. A water quality model was set up for one of these drugs, 5-fluorouracil, in the Aire and Calder catchment in Northern UK. The study predicts 5–50 ng/L concentrations for long stretches of this catchment under low flow conditions. Due to their mode of action, practically all eukaryotic organisms are vulnerable to damage, with teratogenicity being the greatest concern at such levels. However, it is unclear to what extent the predicted low concentrations would affect flora and fauna in receiving waters but there may be an additive effect of a mixture of cytotoxic drugs which should be taken into account. The exposure of the pregnant mother, or more specifically her foetus, to these drugs via drinking water should be minimised. Current drinking water purification technology gives grounds for optimism on removal of these compounds, but no appropriate data exist yet.
Article
Intensive research on pharmaceuticals in the environment started about 15 years ago. Since then a vast amount of literature has been published. The input and presence of active pharmaceutical ingredients (APIs) and their fate in the environment were and is still of high interest. As it has been extensively demonstrated that the active compounds are present in the environment some of the research interest has moved from analysis of the compounds, which is still undertaken, to effect studies in the lab and in field trials. It has been found that environmental concentrations can cause effects in wildlife if proper tools are applied for effect assessment. The question of mixture toxicity has gained more and more attention. It has been learned that classical tests may underestimate effects and risks. Work has been done in the field of risk assessment and risk management. As for risk management strategies to eliminate pharmaceuticals from wastewater or from the effluent of sewage treatment plants have been proposed and investigated. A tremendous amount of literature can now be found describing technical management measures such as oxidative or photolytic effluent treatment, filtering techniques, and application of charcoal. It has been learned however, that each of these approaches has its specific shortcomings. Therefore, additional approaches such as including people handling and using the compounds, and focusing on the properties of the compounds (“green pharmacy”) came into focus. Accordingly, this review gives an overview of the present state of knowledge presenting typical results and lines of discussion. This review makes no claim to give a complete overview including the full detailed body of knowledge of pharmaceuticals in the environment. Rather, it addresses important and typical topics to stimulate discussion.
Article
The behaviour and effects of atorvastatin (ATO), carbamazepine (CBZ), and 17α-ethinylestradiol (EE2) were investigated in spiked lake sediments, at concentrations up to 56.5 mg kg(-1)dry weight (dw), with the benthic invertebrates Chironomus dilutus and Hyalella azteca. Desorption constants were calculated in the presence and absence of animals, using linear isotherms, yielding K(d) values of 28.2, 189.0 and 125.1 L kg(-1) (ATO), 73.7, 201.7 and 263.2 L kg(-1) (CBZ), and 114.9, 114.2 and 519.2 L kg(-1) (EE2) for C. dilutus, H. azteca, and without animals, respectively. For ATO and CBZ, K(d) values were smaller in the presence of C. dilutus, indicating greater desorption to the overlying water from bioturbation, which is consistent with the predominantly benthic occurrence of C. dilutus compared to H. azteca. In contrast, due to its greater hydrophobicity, bioturbation did not significantly affect desorption of EE2. No significant toxicity was observed, indicating decreased bioavailability of the chemicals sorbed to sediments compared with water-only toxicity assays.
Article
This study discusses the occurrence and environmental risk associated with a micropollutant plume originating from the direct discharge of treated wastewater into the Vidy Bay of Lake Geneva, Switzerland. The temporal variations and spatial extent of the plume and its effect on the presence of 39 pharmaceuticals and other micropollutants in the Vidy Bay were assessed over a 10 month period. A pronounced plume was observed from April to October, leading to locally elevated (up to 70-fold) pharmaceutical concentrations compared to the surrounding water column. For three of the measured substances, these plume-associated concentrations were sufficiently high to pose an ecotoxicological risk. The plume depth followed the thermal lake stratification, which moved to lower depths over the course of the warm seasons. Pharmaceutical hotspots associated with the plume were detected as far as 1.5 km downstream of the effluent wastewater outfall, but concentrations typically decreased with increasing distance from the wastewater outfall as a result of dilution and photodegradation. From November to January, when uniform temperature prevailed throughout the water column, no micropollutant plumes were detected. In contrast to pharmaceuticals, most pesticides showed homogeneous concentrations throughout the Vidy Bay during the whole study period, indicating that the effluent wastewater was not their dominant source. A strong linear correlation between electrical conductivity and concentrations of wastewater-derived micropollutants was identified. This relation will allow future estimates of wastewater-derived micropollutant concentrations via simple conductivity measurements.
Article
Wastewater impoundments at concentrated animal feeding operations (CAFOs) represent a potential source of veterinary pharmaceuticals and steroid hormone contamination to shallow groundwater. This study investigates the occurrence of seventeen veterinary pharmaceuticals and thirteen steroid hormones and hormone metabolites in lagoons and adjacent groundwater at operating swine and beef cattle facilities. These sites were chosen because subsurface geology and previous monitoring of nitrate, ammonia and chloride levels in shallow ground water strongly indicated direct infiltration, and as such represent worst cases for ground water contamination by waste water. Pharmaceutical compounds detected in samples obtained from cattle facilities include sulfamerazine; sulfamethazine; erythromycin; monensin; tiamulin; and sulfathiazole. Lincomycin; ractopamine; sulfamethazine; sulfathiazole; erythromycin; tiamulin and sulfadimethoxine were detected in wastewater samples obtained from swine facilities. Steroid hormones were detected less frequently than veterinary pharmaceuticals in this study. Estrone, testosterone, 4-androstenedione, and androsterone were detected in wastewater impoundments at concentrations ranging from 30 to 3600ng/L, while only estrone and testosterone were detected in groundwater samples at concentrations up to 390ng/L. The co-occurrence of veterinary pharmaceutical and steroid hormone contamination in groundwater at these locations and the correlation between pharmaceutical occurrence in lagoon wastewater and hydraulically downgradient groundwater indicates that groundwater underlying some livestock wastewater impoundments is susceptible to contamination by veterinary pharmaceuticals and steroid hormones originating in wastewater lagoons.
Article
There is increasing evidence that the clinical efficacy of tamoxifen, the first and most widely used targeted therapy for estrogen-sensitive breast cancer, depends on the formation of the active metabolites 4-hydroxy-tamoxifen and 4-hydroxy-N-desmethyl-tamoxifen (endoxifen). Large inter-individual variability in endoxifen plasma concentrations has been observed and related both to genetic and environmental (i.e. drug-induced) factors altering CYP450s metabolizing enzymes activity. In this context, we have developed an ultra performance liquid chromatography-tandem mass spectrometry method (UPLC-MS/MS) requiring 100 μL of plasma for the quantification of tamoxifen and three of its major metabolites in breast cancer patients. Plasma is purified by a combination of protein precipitation, evaporation at room temperature under nitrogen, and reconstitution in methanol/20 mM ammonium formate 1:1 (v/v), adjusted to pH 2.9 with formic acid. Reverse-phase chromatographic separation of tamoxifen, N-desmethyl-tamoxifen, 4-hydroxy-tamoxifen and 4-hydroxy-N-desmethyl-tamoxifen is performed within 13 min using elution with a gradient of 10 mM ammonium formate and acetonitrile, both containing 0.1% formic acid. Analytes quantification, using matrix-matched calibration samples spiked with their respective deuterated internal standards, is performed by electrospray ionization-triple quadrupole mass spectrometry using selected reaction monitoring detection in the positive mode. The method was validated according to FDA recommendations, including assessment of relative matrix effects variability, as well as tamoxifen and metabolites short-term stability in plasma and whole blood. The method is precise (inter-day CV%: 2.5-7.8%), accurate (-1.4 to +5.8%) and sensitive (lower limits of quantification comprised between 0.4 and 2.0 ng/mL). Application of this method to patients' samples has made possible the identification of two further metabolites, 4'-hydroxy-tamoxifen and 4'-hydroxy-N-desmethyl-tamoxifen, described for the first time in breast cancer patients. This UPLC-MS/MS assay is currently applied for monitoring plasma levels of tamoxifen and its metabolites in breast cancer patients within the frame of a clinical trial aiming to assess the impact of dose increase on tamoxifen and endoxifen exposure.
Article
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.
Article
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.
Article
A model based on graph theory was developed to efficiently evaluate the impact of the effluent from 742 wastewater treatment plants (WWTPs) on micropollutant loading throughout all river catchments in Switzerland. Model results agree well with measured loads for 12 compounds in river water samples, revealing mean predictive accuracy factors between 0.8 and 3.4. Subsequently, pollutant concentrations were predicted for river sections downstream from 543 WWTPs where hydrological information was available, and compared with recent recommendations for water quality criteria. At base flow conditions, carbamazepine concentrations (parent compound only) are ubiquitously below a water quality criterion of 0.5 mu g L(-1). In contrast, the sum of diclofenac and its metabolites is expected to exceed the corresponding water quality criterion of 0.1 mu g L(-1) in 224 river sections. If diclofenac cannot be eliminated at the source, the model suggests a directed upgrade of 173 WWTPs to meet the condition that concentrations are never to exceed this water quality criterion.
Article
The present study examines the contribution of combined sewer overflows (CSO) to loads and concentrations of trace contaminants in receiving surface water. A simple method to assess the ratio of CSO to wastewater treatment plant (WWTP) effluents was applied to the urban River Spree in Berlin, Germany. The assessment indicated that annual loads are dominated by CSO for substances with removal in WWTP above approximately 95%. Moreover, it showed that substances with high removal in WWTP can lead to concentration peaks in the river during CSO events. The calculated results could be verified based on eight years of monitoring data from the River Spree, collected between 2000 and 2007. Substances that are well removed in WWTP such as NTA (nitrilotriacetic acid) were found to occur in significantly increased concentration during CSO, while the concentration of substances that are poorly removable in WWTP such as EDTA (ethylenediaminetetraacetic acid) decreased in CSO-influenced samples due to dilution effects. The overall results indicate the potential importance of the CSO pathway of well-removable sewage-based trace contaminants to rivers. In particular, high concentrations during CSO events may be relevant for aquatic organisms. Given the results, it is suggested to include well-removable, sewage-based trace contaminants, a substance group often neglected in the past, in future studies on urban rivers in case of combined sewer systems. The presented methodology is suggested for a first assessment, since it is based solely on urban drainage data, which is available in most cities.
Article
The residue of antibiotics is becoming an intractable environmental problem in many organic vegetable bases. However, their residual levels and distribution are still obscure. This work systematically analyzed the occurrence and migration of typical veterinary antibiotics in organic vegetable bases, northern China. The results showed that there was no obvious geographical difference in antibiotic distribution between soil and manure. A simple migration model can be easy and quick to predict the accumulation of antibiotics in soil. Antibiotics were mainly taken up through water transport and passive absorption in vegetables. The distribution of antibiotics in a plant was in the sequence leaf>stem>root, and performed biological accumulation. The residues of antibiotics in all samples in winter were significantly higher than those in summer. Overall, this work can lay the foundation for understanding ecological risk of antibiotics and their potential adverse effects on human health by food chain.
Article
Interest in the public health significance of trace levels of pharmaceuticals in potable water is increasing, particularly with regard to the effects of long-term, low-dose exposures. To assess health risks and establish target concentrations for water treatment, human health risk-based screening levels for 15 pharmaceutically active ingredients and four metabolites were compared to concentrations detected at 19 drinking water treatment plants across the United States. Compounds were selected based on rate of use, likelihood of occurrence, and potential for toxicity. Screening levels were established based on animal toxicity data and adverse effects at therapeutic doses, focusing largely on reproductive and developmental toxicity and carcinogenicity. Calculated drinking water equivalent levels (DWELs) ranged from 0.49 microg/L (risperidone) to 20,000 microg/L (naproxen). None of the 10 detected compounds exceeded their DWEL. Ratios of DWELs to maximum detected concentrations ranged from 110 (phenytoin) to 6,000,000 (sulfamethoxazole). Based on this evaluation, adverse health effects from targeted pharmaceuticals occurring in U.S. drinking water are not expected.
Article
Thèse no 3280 sc. EPF Lausanne. Literaturverz. EPFL, Lausanne
Article
The occurrence of human and veterinary pharmaceuticals in the environment has been a subject of concern for the past decade because many of these emerging contaminants have been shown to persist in soil and water. Although recent studies indicate that pharmaceutical contaminants can pose long-term ecological risks, many of the investigations regarding risk assessment have only considered the ecotoxicity of the parent drug, with very little attention given to the potential contributions that metabolites may have. The scarcity of available environmental data on the human metabolites excreted into the environment or the microbial metabolites formed during environmental biodegradation of pharmaceutical residues can be attributed to the difficulty in analyzing trace amounts of previously unknown compounds in complex sample matrices. However, with the advent of highly sensitive and powerful analytical instrumentations that have become available commercially, it is likely that an increased number of pharmaceutical metabolites will be identified and included in environmental risk assessment. The present study will present a critical review of available literature on pharmaceutical metabolites, primarily focusing on their analysis and toxicological significance. It is also intended to provide an overview on the recent advances in analytical tools and strategies to facilitate metabolite identification in environmental samples. This review aims to provide insight on what future directions might be taken to help scientists in this challenging task of enhancing the available data on the fate, behavior, and ecotoxicity of pharmaceutical metabolites in the environment.
Article
An evaluation of measured and predicted concentrations of 17-ethinylestradiol in surface waters of the United States and Europe was conducted to develop expected long-term exposure concentrations for this compound. Measured environmental concentrations (MECs) in surface waters were identified from the literature. Predicted environmental concentrations (PECs) were generated for European and U.S. watersheds using the GREAT-ER and PhATE models, respectively. The majority of MECs are nondetect and generally consistent with model PECs and conservative mass balance calculations. However, the highest MECs are not consistent with concentrations derived from conservative (worst-case) mass balance estimates or model PECs. A review of analytical methods suggests that tandem or high-resolution mass spectrometry methods with extract cleanup result in lower detection limits and lower reported concentrations consistent with model predictions and bounding estimates. Based on model results using PhATE and GREAT-ER, the 90th-percentile low-flow PECs in surface water are approximately 0.2 and 0.3 ng/L for the United States and Europe, respectively. These levels represent conservative estimates of long-term exposure that can be used for risk assessment purposes. Our analysis also indicates that average concentrations are one to two orders of magnitude lower than these 90th-percentile estimates. Higher reported concentrations (e.g., greater than the 99th-percentile PEC of approximately 1 ng/L) could result from methodological problems or unusual environmental circumstances; however, such concentrations are not representative of levels generally found in the environment, warrant special scrutiny, and are not appropriate for use in risk assessments of long-term exposures.
Article
This research was set up in response to new European legislation to identify cost-effective treatment for removal of steroid estrogens from effluent. This study aimed to compare estrogen removal of two types of granular activated carbon: virgin (F400) and reactivated (C401) carbon. Rapid, small-scale column tests were conducted with a total bed volume of 24.9 cm3 over three columns, and analysis was carried out using high-performance liquid chromatography. Results demonstrated that C401 performed more efficiently with greater than or equal to 81% estrogen removal in wastewater compared to F400 which produced greater than or equal to 65% estrogen removal. Estrogen removal can be affected by competitive adsorption from natural organic matter present in wastewater. In addition, the physical properties of each carbon had the potential to influence adsorption differently, thus resulting in the observed varied adsorption capability of the two carbons.
Article
The effects of embryonic and larval exposure to environmentally relevant (ng/L) concentrations of common antidepressants, fluoxetine, sertraline, venlafaxine, and bupropion (singularly and in mixture) on C-start escape behavior were evaluated in fathead minnows (Pimephales promelas). Embryos (postfertilization until hatching) were exposed for 5 d and, after hatching, were allowed to grow in control well water until 12 d old. Similarly, posthatch fathead minnows were exposed for 12 d to these compounds. High-speed (1,000 frames/s) video recordings of escape behavior were collected and transferred to National Institutes of Health Image for frame-by-frame analysis of latency periods, escape velocities, and total escape response (combination of latency period and escape velocity). When tested 12 d posthatch, fluoxetine and venlafaxine adversely affected C-start performance of larvae exposed as embryos. Conversely, larvae exposed for 12 d posthatch did not exhibit altered escape responses when exposed to fluoxetine but were affected by venlafaxine and bupropion exposure. Mixtures of these four antidepressant pharmaceuticals slowed predator avoidance behaviors in larval fathead minnows regardless of the exposure window. The direct impact of reduced C-start performance on survival and, ultimately, reproductive fitness provides an avenue to assess the ecological relevance of exposure in an assay of relatively short duration.
Article
A method was developed for the simultaneous determination of almost 40 pharmaceuticals; including antidepressants, non-steroidal anti-inflammatories, analgesics, hypolipidemics, alpha- and beta-blockers, an anti cancer drug, anti-fungal agents, an opiate, an antibiotic, an anti-coagulant, a diuretic, an anti-anginal and an anti-diabetic compound. This was used to assess the contribution of pharmaceuticals originating from hospital effluents to one of Oslo city's wastewater treatment works. Some pharmaceuticals were found to contribute to more of the wastewater loading than others. 11% of the propranolol entering the wastewater treatment works stems from hospital effluent, approximately 2% of the atenolol, carbemazepine, metaprolol and atorvastatin, and for several other compounds the contribution is less than 1%. This assessment shows that point sources discharges from hospitals typically make a small contribution to the overall pharmaceutical load when compared to municipal areas, however this varies from substance to substance and is not the case when a drug's use is primarily hospital based.
Article
Pharmaceuticals and personal care products are being increasingly reported in a variety of biological matrices, including fish tissue; however, screening studies have presently not encompassed broad geographical areas. A national pilot study was initiated in the United States to assess the accumulation of pharmaceuticals and personal care products in fish sampled from five effluent-dominated rivers that receive direct discharge from wastewater treatment facilities in Chicago, Illinois; Dallas, Texas; Orlando, Florida; Phoenix, Arizona; and West Chester, Pennsylvania, USA. Fish were also collected from the Gila River, New Mexico, USA, as a reference condition expected to be minimally impacted by anthropogenic influence. High performance liquid chromatography-tandem mass spectrometry analysis of pharmaceuticals revealed the presence of norfluoxetine, sertraline, diphenhydramine, diltiazem, and carbamazepine at nanogram-per-gram concentrations in fillet composites from effluent-dominated sampling locations; the additional presence of fluoxetine and gemfibrozil was confirmed in liver tissue. Sertraline was detected at concentrations as high as 19 and 545 ng/g in fillet and liver tissue, respectively. Gas chromatography-tandem mass spectrometry analysis of personal care products in fillet composites revealed the presence of galaxolide and tonalide at maximum concentrations of 2,100 and 290 ng/g, respectively, and trace levels of triclosan. In general, more pharmaceuticals were detected at higher concentrations and with greater frequency in liver than in fillet tissues. Higher lipid content in liver tissue could not account for this discrepancy as no significant positive correlations were found between accumulated pharmaceutical concentrations and lipid content for either tissue type from any sampling site. In contrast, accumulation of the personal care products galaxolide and tonalide was significantly related to lipid content. Results suggest that the detection of pharmaceuticals and personal care products was dependent on the degree of wastewater treatment employed.
Article
Although antibiotics have been used in large quantities for some decades, until recently the existence of these substances in the environment has received little notice. It is only in recent years that a more complex investigation of antibiotic substances has been undertaken in order to permit an assessment of the environmental risks they may pose. Within the last decade an increasing number of studies covering antibiotic input, occurrence, fate and effects have been published, but there is still a lack of understanding and knowledge about antibiotics in the aquatic environment despite the numerous studies performed. This review addresses the present state of knowledge concerning the input, occurrence, fate and effects of antibiotics in the environment. It brings up important questions that are still open, and addresses some significant issues which must be tackled in the future for a better understanding of the behavior of antibiotics in the environment, as well as the risks associated with their occurrence. Questions related to resistance in the environment that may be caused by antibiotics will be addressed in the second part.
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Although antibiotics have been used in large quantities for some decades, until recently the existence of these substances in the environment has received little notice. It is only in recent years that a more complex investigation of antibiotic substances has been undertaken in order to permit an assessment of the environmental risks they may pose. Within the last decade, an increasing number of studies covering antibiotic input, occurrence, fate and effects have been published. Antibiotics are one of the most important groups of pharmaceuticals. Antibiotic resistance is one of the major challenges for human medicine and veterinary medicine. However, there is still a lack of understanding and knowledge about sources, presence and significance of resistance of bacteria against antibiotics in the aquatic environment despite the numerous studies performed. This review summarizes this topic. It names important open questions and addresses some significant issues which must be tackled in the future for a better understanding of resistance related to antibiotics in the environment.
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We selected eight pharmaceuticals with relatively high potential ecological risk and high consumption-namely, acetaminophen, atenolol, carbamazepine, ibuprofen, ifenprodil, indomethacin, mefenamic acid, and propranolol-and conducted laboratory experiments to examine the persistence and partitioning of these compounds in the aquatic environment. In the results of batch sunlight photolysis experiments, three out of eight pharmaceuticals-propranolol, indomethacin, and ifenprodil-were relatively easily photodegraded (i.e., half-life<24h), whereas the other five pharmaceuticals were relatively stable against sunlight. The results of batch biodegradation experiments using river water suggested relatively slow biodegradation (i.e., half-life>24h) for all eight pharmaceuticals, but the rate constant was dependent on sampling site and time. Batch sorption experiments were also conducted to determine the sorption coefficients to river sediments and a model soil sample. The determined coefficients (K(d) values) were much higher for three amines (atenolol, ifenprodil, and propranolol) than for neutral compounds or carboxylic acids; the K(d) values of the amines were comparable to those of a four-ring polycyclic aromatic hydrocarbon (PAH) pyrene. The coefficients were also higher for sediment/soil with higher organic content, and the organic carbon-based sorption coefficient (logK(oc)) showed a poor linear correlation with the octanol-water distribution coefficient (logD(ow)) at neutral pH. These results suggest other sorption mechanisms-such as electrochemical affinity, in addition to hydrophobic interaction-play an important role in sorption to sediment/soil at neutral pH.
Article
Direct capillary nanofiltration also in combination with an upstream powdered activated carbon treatment was tested for high quality water reuse of tertiary effluent from a municipal wastewater treatment plant. Two endocrine disruptors (BPA and EE2) and two cytostatics (CytR and 5-FU) were spiked in concentrations of 1 to 2 microg/L to evaluate the process performance. In direct NF the real total removal of the micropollutants was between 5 and 40%. Adsorption to the membrane played a major role leading to a seemingly total removal between 35 and 70%. Addition of powdered activated carbon and lignite coke dust largely reduced the influence from adsorption to the membrane and increased the total removal to >95 to 99.9% depending on the PAC type and dose. The cytostatics showed already in direct NF a very high removal due to unspecified losses. Further investigations are ongoing to understand the underlying mechanism. The PAC/NF process provided a consistently high permeate quality with respect to bulk and trace organics.
Article
Medical substances (pharmaceuticals) are a group of substances that until recently have been exposed to the environment with very little attention. The reason why they may be interesting as environmental micropollutants, is that medical substances are developed with the intention of performing a biological effect. Especially antibiotics used as growth promoters, as feed additives in fish farms are anticipated to end up in the environment. Very little is known about the exposure routes of the medical substances to the environment. Only few investigations have reported findings of medical substances in other field samples than sediment or treated waste water samples. Several substances seem to be persistent in the environment. This paper outlines the different anticipated exposure routes to the environment, summarises the legislation on the subject and gives an outline of present knowledge of occurrence, fate and effect on both the aquatic and terrestrial environments of medical substances. Present knowledge does not reveal if regular therapeutic use may be the source of a substance carried by sewage effluent into the aquatic system, even though clofibrate, a lipid lowering agent, has been identified in ground and tap water samples from Berlin. Further research would be necessary to assess the environmental risk involved in exposing medical substances and metabolites to the environment.
Article
Iodinated X-ray contrast media are diagnostic pharmaceuticals that are applied to enhance the contrast between organs or vessels examined and surrounding tissues during radiography. These substances are applied in doses up to ca. 200 g per person (corresponding to approx 100 g iodine) and are rapidly excreted. In the sewage system they contribute to the burden of adsorbable organic halogens (AOX). To assess the potential environmental impact of this release, studies on environmental fate and effects were conducted for a risk assessment of the frequently used X-ray contrast medium iopromide (brand name: Ultravist). A screening test for biological degradation (OECD Screening Test 301 E) led to iopromide being classified as not readily biodegradable. Therefore, the predicted environmental concentration (PEC) in surface water was calculated in a first step. The resulting concentration of 2 microgram/liter was then compared in a second step with the predicted no-effect concentration as derived from a battery of ecotoxicity tests. In short-term toxicity tests with bacteria (Vibrio fisheri, Pseudomonas putida), algae (Scenedesmus subspicatus), crustaceans (Daphnia magna), and fish (Danio rerio, Leuciscus idus) no toxic effects were detected at the highest tested concentration of 10 g/liter. In a chronic toxicity test with D. magna no effect was observed at the highest tested concentration of 1 g/liter. Using an assessment factor of 100 the ratio between the predicted environmental concentration (PEC) and the predicted no-effect concentration (PNEC) was calculated to be </=0.0002. This low value indicates that no environmental risk has to be expected as a result of the release of iopromide into the aquatic environment.