Article

EU-Wide Survey of Polar Organic Persistent Pollutants in European River Waters

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Abstract

This study provides the first EU-wide reconnaissance of the occurrence of polar organic persistent pollutants in European river waters. More than 100 individual water samples from over 100 European rivers from 27 European Countries were analysed for 35 selected compounds, comprising pharmaceuticals, pesticides, PFOS, PFOA, benzotriazoles, hormones, and endocrine disrupters. Around 40 laboratories participated in this sampling exercise. The most frequently and at the highest concentration levels detected compounds were benzotriazole, caffeine, carbamazepine, tolyltriazole, and nonylphenoxy acetic acid (NPE(1)C). Only about 10% of the river water samples analysed could be classified as "very clean" in terms of chemical pollution. The rivers responsible for the major aqueous emissions of PFOS and PFOA from the European Continent could be identified. For the target compounds chosen, we are proposing "indicative warning levels" in surface waters, which are (for most compounds) close to the 90th percentile of all water samples analysed.

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... The ubiquitous presence of emerging contaminants (ECs) across the environmental matrices requires a multidisciplinary approach for overcoming this both scientific and regulatory conundrum, in order to safeguard water quality, protect aquatic ecosystems, and consequently human health. Owing to significant advances in analytical techniques and instruments, this vast spectrum of natural and synthetic organic compounds (including their metabolites and transformation products) is detected worldwide at ng/L to μg/L levels in both surface water (Loos et al., 2009) and groundwater bodies (Sui et al., 2015). Global and daily use of ECs compounds such as Science of the Total Environment 825 (2022) 153827 pharmaceuticals and personal care products, hormones, lifestyle products, industrial, and agricultural chemicals entails their continual emission into the environment, which is still not adequately monitored nor regulated. ...
... The occurrence of 1H-benzotriazole in water samples at all sites discloses an anthropogenic impact, presumably because of the sewer networks and septic tanks (Seitz and Winzenbacher, 2017). As Loos et al. (2009) report, 1H-benzotriazole is ubiquitously detected even in remote areas, where rivers are characterised as pristine (with ECs detected in low concentrations of <50 ng/L). DEET was the most frequently detected EC (detection frequency of 0.21), with concentrations ranging from 12.7 ng/L to 135 ng/L both measured in Žrnovnica spring (Fig. 2), and average concentration in both surface water and groundwater of around 50 ng/L. ...
... When exhibiting the cumulative RQ site values of all sampling campaigns per site, Cetina River (RQ site of 0.22) comes across as the site with the highest potential environmental risk (Fig. 8). However, this does not imply how the risk is high, as the concentrations of detected ECs are still relatively low compared to other studies (Loos et al., 2009(Loos et al., , 2010. For instance, the Sava River in the alluvial part of Croatia exhibited much greater total risk quotients of up to 20 per sampling site, which are attributed to different pollution sources (Köck-Schulmeyer et al., 2021). ...
Article
Karst aquifers are globally important source of drinking water and harbor specific ecosystems that are vulnerable to anthropogenic contamination. This paper provides insights into the occurrence and ecotoxicological characterization of 21 emerging contaminants (ECs) detected in the karst catchment of Jadro and Žrnovnica springs (Dinarides, Croatia). Karst springs used for water supply, surface water, and groundwater were sampled during seven campaigns. The ECs concentration levels ranged from 0.3 ng/L (tramadol in Jadro spring) to 372 ng/L (1H-benzotriazole in Cetina River). DEET was the most frequently detected ECs with an average concentration of around 50 ng/L in both surface water and groundwater. To prioritise detected ECs, their persistence (P), bioaccumulation (B), mobility (M) and toxicity (T) were assessed based on in silico strategy for PBT assessment and recently developed REACH PMT guidelines. PBT scores ranging below the threshold of 0.5, indicated non-PBT compounds of expected low concern. However, only 4 out of 21 detected ECs were not assessed as PMT/vPvM. Concerningly, 20 ECs were categorised as very mobile. Karst springs exhibited larger proportions of ECs meeting PMT/vPvM criteria than surface water. To characterise the contamination extent and estimate the incidence of adverse effects of detected ECs, a preliminary environmental risk assessment (ERA) was conducted. Most ECs posed no environmental risk with RQ values predominantly below 0.01. The total risk quotient RQsite accentuated Cetina River as having the highest risk compared to other sampling sites. This is the first study on ECs in Croatian karst, contributing to a growing need to understand the impacts of emerging contaminants in karst aquifers, which are still largely unexplored.
... Many studies of EOCs in aquatic environments have been undertaken for wastewater (ww) effluents (Bueno et al., 2012;Petrović et al., 2003) and surface waters (Houtman, 2010;Loos et al., 2009;Matamoros et al., 2012). Fewer studies have been undertaken for groundwater (Bexfield et al., 2019;Lapworth et al., 2012;Loos et al., 2010;Sanchez-Vila et al., 2015;Stuart et al., 2012;Sui et al., 2015). ...
... In Fig. 5 maximum concentrations of EOCs in karst aquifers are compared with values found in a range of aquifers globally and surface waters in Europe (Loos et al., 2009). Maximum concentrations depend upon the presence and nature of contaminant sources within the catchment, which was not assessed in this literature review. ...
... EOCs provide further evidence of There are examples of studies that have demonstrated high vulnerability using EOCs. High vulnerability from fast flow events in a karst aquifer with a leaking sewage pipe was identified using carbamazepine and surface waters (Loos et al., 2009). and caffeine by Dvory et al. (2018a). ...
Article
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A quarter of the world's population uses groundwater from karst aquifers. A range of emerging organic contaminants (EOCs) are considered a potential threat to water resources and dependant ecosystems, and karst aquifers are the most vulnerable groundwater systems to anthropogenic pollution. This paper provides the first global compilation (based on 50 studies) of EOCs in karst aquifers and explores EOC occurrence and the use of EOCs to understand karst systems. Of the 144 compounds detected in the reviewed studies, the vast majority in karst groundwater are pharmaceuticals and pesticides. Maximum concentrations of compounds varied over five orders of magnitude, and nearly half of the detected compounds exceed 100 ng/L. Karst groundwater is shown to have lower frequency of detection and lower concentrations compared to surface waters and local shallow intergranular aquifers, but overall higher concentrations compared to other major aquifer types. A growing number of studies have demonstrated the utility of EOCs and some legacy compounds for groundwater quality assessment and as tracers for characterising karst systems. They can improve understanding of vulnerability, storage, attenuation mechanisms, and in some cases have been used to assist with catchment delineation. This is a growing research area for karst hydrogeology, and more research is needed to understand EOC contamination of karst aquifers, and to develop EOCs as tracers within karst to improve our understanding of this critical water resource.
... Analgesics represent the majority of the highest PPCP concentrations reported in Africa, including 107,000 ng/L of acetaminophen in Ngong River, Kenya (K'oreje et al., 2016); 84,600 ng/L of ibuprofen in Msunduzi River, South Africa (Matongo et al., 2015b); 62,000 ng/L of ibuprofen in Umgeni River, South Africa (Matongo et al., 2015a), and 57,160 ng/L of diclofenac in Ogun State, Nigeria (Olaitan et al., 2014). The concentrations of analgesics detected in North American and European freshwaters are generally lower than those observed in Africa despite having similar median analgesic concentrations in municipal wastewater influent (Table S5) (Loos et al., 2009). Overall, we observed higher concentrations of analgesics in freshwaters of developing countries, regardless of population density (Fig. S3). ...
... The highest concentration of caffeine in freshwater (144,179 ng/L), based on our literature search, was reported in Asia by Tran et al. (2014). Similar caffeine concentrations of 39,813 ng/L, 33,200 ng/L and 32,400 ng/L were reported in a European waterbody (Loos et al., 2009), Msunduzi River (KwaZulu--Natal, South Africa) (Matongo et al., 2015b), and Atibaia River (Brazil), respectively (Sodré et al., 2007). These concentrations, based on the studies we reviewed, represent the highest caffeine concentrations reported in European, African, and South American freshwaters. ...
... Psychoactive drugs are incompletely metabolized in the body (Calisto and Esteves, 2009; Kosjek et al., 2012), and have low removal in WWTPs (Fig. 4d). Based on the studies we reviewed, the highest concentration of carbamazepine, a common psychoactive, observed in freshwater (11,561 ng/L) was reported in a European river by Loos et al. (2009). Relatively high concentrations of antihypertensives have also been reported globally, particularly in freshwaters of developed countries. ...
Article
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Pharmaceuticals and personal care products (PPCPs) are found in wastewater, and thus, the environment. In this study, current knowledge about the occurrence and fate of PPCPs in aquatic systems—including wastewater treatment plants (WWTPs) and natural waters around the world—is critically reviewed to inform the state of the science and highlight existing knowledge gaps. Excretion by humans is the primary route of PPCPs entry into municipal wastewater systems, but significant contributions also occur through emissions from hospitals, PPCPs manufacturers, and agriculture. Abundance of PPCPs in raw wastewater is influenced by several factors, including the population density and demography served by WWTPs, presence of hospitals and drugs manufacturers in the sewershed, disease burden of the population served, local regulations, and climatic conditions. Based on the data obtained from WWTPs, analgesics, antibiotics, and stimulants (e.g., caffeine) are the most abundant PPCPs in raw wastewater. In conventional WWTPs, most removal of PPCPs occurs during secondary treatment, and overall removal exceeds 90% for treatable PPCPs. Regardless, the total PPCP mass discharged with effluent by an average WWTP into receiving waters (7.35 – 20,160 g/day) is still considerable, because potential adverse effects of some PPCPs (such as ibuprofen) on aquatic organisms occur within measured concentrations found in surface waters.
... These compounds were also identified in the USA and Germany, drinking water sources [48]. Other pollutants frequently observed are given in [63], [64], are given in Figure 2.5. Most of the compounds presented in Table 2.1, were also detected in surface and ground waters by Loos et al. [63], [64] (Figure 2.5 (a-b)). ...
... Other pollutants frequently observed are given in [63], [64], are given in Figure 2.5. Most of the compounds presented in Table 2.1, were also detected in surface and ground waters by Loos et al. [63], [64] (Figure 2.5 (a-b)). Pesticides/biocides are artificially synthesised to protect agricultural production against pest infection. ...
... However, alkylphenols are more toxic than their ethoxylates, and therefore, the control measures the release of these compounds via secondary effluents is essential. Figure 2.5 is drawn from the survey of [63], [64], which depict the surface and groundwater contamination. Pie chart presents the relevant information obtained from [63], [64]. ...
Thesis
This thesis aims to develop a robust treatment to achieve pristine water quality. The study amended classical Fenton Oxidation by replacing FeSO4 with iron powder (as Fe (0)). The developed Fe (0)- Fenton oxidation process reciprocates the oxidation and adsorption effects simultaneously. The treatment was optimised to achieve likely maximum dissolved organic carbon (DOC) removal. The pharmaceuticals- Gabapentin and Sulfamethoxazole and, biocide/herbicides- Diuron, Terbutryn and Terbuthylazine were selected from the EU Directives watch list, to develop an effective removal technology. The study used a statistical approach- Taguchi Method, to design laboratory experimentations and accomplished robust process optimisation. Measuring organic carbon provides the quality of the overall process. The innovative elements of the research presented in the thesis are: o The study was able to develop an Iron powder (Fe (0))-modified Fenton Oxidation process, which exerts oxidation and adsorption simultaneously in a single treatment. As a result, non-toxic effluent and high DOC removal (~70%) was achieved. o The thesis provides evidence for adsorption effect from sludge in classical Fenton Oxidation Process. o Fe (0) itself as a solo demonstrated an effective adsorbent which removed almost 90% gabapentin when 100% gabapentin was degraded if used as Fenton reagent. Fe (0) effectiveness in removing organic contaminants from water is demonstrated. o The rate kinetics of the organic micropollutants mineralisation was estimated. Among several kinetic models developed, BMG kinetic model best suited and showed maximum linearity to the Fe (0)-Fenton Oxidation process. The BMG Kinetic model was used to estimate the theoretical oxidation capacities of organic micropollutants in the treatment. o The Fe (0) in the treatment used as a catalyst, was reused up to three times in consecutive treatments without compromising the oxidation efficiency and micropollutants degradation. o The treatment effluents did not inhibit bacterial growth when analysed using Microtox protocol and thus, was interpreted as non-toxic. o The study identified the oxidation by-products and suggested their structural configuration. The possible degradation pathway/s during a Fe (0)-modified Fenton Oxidation process was predicted. o The study also assessed the feasible operating conditions/ sustainability of the developed water treatment method and discussed its limitations. Finally, the thesis proposed future work in the research areas that include the extent of reactions’ mechanisms governed by Fe (0) and hydroxyl radical solution interface; confirmation of the fate of micropollutants towards oxidation; more researches on the role of iron powder as an adsorbent; the necessary of running pilot- and full-scale trials to test the sustainability and cost-effectiveness of the technology.
... Among these substances, various medicines, cosmetics, disinfectants and even their metabolites are included. These compounds have been found in different water environments, such as wastewater, surface water, groundwater and tap water [5][6][7][8]. Their presence in the environment mostly results from excretion of compounds by organisms and the passing of these compounds into wastewater. ...
... Therefore, slowly degradable contaminants enter the natural environment and migrate to water bodies, including those which serve as drinking water supplies. In this regard, PPCPs may pose a threat to aquatic organisms and may be ingested by humans in tap water [7,19]. ...
Article
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The issue of pharmaceuticals and personal care products (PPCPs) in the water environment has gained increasing interest worldwide. To determine the nature and extent of this problem for Poland, this paper presents a review of research on the presence of PPCPs in Poland, looking at results for different water samples, including wastewater (before and after treatment), landfill leachate, surface water (standing water bodies and rivers), seawater, groundwater and drinking water. The review is based on over 50 scientific articles and dissertations referring to studies of PPCPs. It also briefly outlines possible sources and the fate of PPCPs in the aquatic environment. The review of Polish research has revealed that studies have previously covered at least 39 PPCP groups (270 compounds in total). These studies focused mainly on wastewater and rivers, and only a few concerned landfill leachate and seawater. They most often reported on nonsteroidal anti-inflammatory drugs and antibiotics. The highest concentrations of the analysed PPCPs were found mainly in raw wastewater (e.g., naproxen, up to 551,960 ng/L), but they were also occasionally found in surface water (e.g., azithromycin, erythromycin, irbesartan and metoprolol) and in groundwater (e.g., N,N-diethyl-meta-toluamide, known as DEET, up to 17,280 ng/L). Extremely high concentrations of bisphenol A (up to 2,202,000 ng/L) and diclofenac (up to 108,340 ng/L) were found in landfill leachate. Although numerous substances have been detected, PPCPs are still not monitored regularly, which makes it difficult to obtain a clear understanding of their incidence in the water environment.
... The sampling point 2 was immediately downstream from a Sewage Treatment Plant (processing 180,000-200,000 m 3 sewage per day). The sampling procedures adopted for this study were those applied in several works on European rivers [60,61]. The samplings were performed in April 2017, November 2017 and October 2018. ...
... In this work, SMX and CIP were found as the most abundant contaminants at all the points investigated. The amounts of these antibiotics were lower (SMX up to 30.93 ng/L, CIP up to 16.31 ng/L), than those found in a smaller river, such as the Tiber [4,60], presum-Water 2021, 13, 3402 9 of 13 ably because of the "dilution effect". The river Danube is in fact longer and wider than the Tiber. ...
Article
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River contamination is due to a chemical mixture of point and diffuse pollution, which can compromise water quality. Polycyclic Aromatic Hydrocarbons (PAHs) and emerging compounds such as pharmaceuticals and antibiotics are frequently found in rivers flowing through big cities. This work evaluated the presence of fifteen priority PAHs, eight pharmaceuticals including the antibiotics ciprofloxacin (CIP) and sulfamethoxazole (SMX), together with their main antibiotic resistant genes (ARGs) and the structure of the natural bacterioplankton community, in an urbanized stretch of the river Danube. SMX and diclofenac were the most abundant chemicals found (up to 20 ng/L). ARGs were also found to be detected as ubiquitous contaminants. A principal component analysis of the overall microbiological and chemical data revealed which contaminants were correlated with the presence of certain bacterial groups. The highest concentrations of naphthalene were associated with Deltaproteobacteria and intI1 gene. Overall, the most contaminated site was inside the city and located immediately downstream of a wastewater treatment plant. However, both the sampling points before the river reached the city and in its southern suburban area were still affected by emerging and legacy contamination. The diffuse presence of antibiotics and ARGs causes particular concern because the river water is used for drinking purposes.
... These xenobiotics are not only detectable in industrially and agriculturally developed areas but in distant locations as well [6,7]. Many of them can disperse and circulate afterwards, infiltrating environmental compartments and persist for several years (or maybe decades) due to their physical-chemical properties and resistance to degradation processes [8]. ...
... Many studies have focused on the influence of pesticides on the surface-, subsurface-, and groundwater systems surrounding agricultural catchment areas in EUwide surveys, and according to the results, the number of detected pesticide residues and their concentrations have increased over the years [8][9][10][11][12][13][14][15][16]. In most cases, these residues were found in surface waters at relatively high concentrations, which were three orders of magnitude higher than the maximum values for individual pesticides (0.1 µg/L) and total pesticides (0.5 µg/L) established by the Drinking Water European Directive 98/83/EC [10,16,17]. ...
Article
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Background The present study aimed to gain a comprehensive knowledge of the presence and environmental risks of pesticide and repellent residues in Lake Balaton and its sub-catchment area (Hungary). A unique analysis of 439 active substances and 17 metabolites was carried out on surface waters and one effluent wastewater as the only direct discharge into Lake Balaton from June 2017 until August 2020. Altogether 203 water- and 85 sediment samples were collected and analysed during the 3-year monitoring period. To determine the environmental risks of the detected pesticides to aquatic ecosystems, environmental risk assessment (ERA) was carried out using two approaches (worst- and general-case scenarios). Results Fifty-two pesticides and one insect repellent were detected, of which 26 belonged to herbicides (24 active substances and two metabolites), 15 to fungicides (15 active substances), and 11 to insecticides (eight active substances and three metabolites), of which only nine of the total analysed compounds are listed to be monitored in surface waters with threshold limit values (TLVs). The most frequently detected compounds were terbuthylazine, diethyltoluamide (DEET), desethyl-atrazine, and metolachlor. Glyphosate, aminomethylphosphonic acid (AMPA), and DEET were found with the highest concentrations of 3.0, 2.0, and 1.57 µg/L, respectively. The pesticide exposures were higher during the summer periods indicating a stable seasonal pattern. According to the performed ERA, the calculated Risk Quotients (RQs) indicated 18 compounds with a high level of risk including nine that had been banned for at least a decade. Discussion This study expands knowledge on the spatiotemporal occurrence of pesticides in inland surface waters and highlights the need to consider widening the number of analysed pesticides beyond the European Water Framework Directive (EWFD). According to our results, additional authority and legislation procedures should come into force for pesticides not indexed in the priority European Union Watch List.
... In 2015, 89% and 100% of the rivers in Germany did not meet the requirements of the WFD for an ecological good status and chemical good status (BMUB and UBA, 2016) and the presence of OMPs in surface waters is one reason for this poor result. OMPs have already been detected in every EU country (Loos et al., 2009). As they have been identified as pollutants of significant concern for surface water and drinking water quality, actions regarding measures to reduce OMP pollution are highly recommended by researchers (Hofman-Caris et al., 2019;Sousa et al., 2019). ...
... The variety and the concentrations of OMPs found in surface waters in Europe (Loos et al., 2009) and in the Swist ; Chapter 3), together with the European and German legislations, exemplify the need for the reduction of OMPs in rivers towards an enhanced water quality. ...
... The information gathered is of value in determining whether a particular substance is of pan-European relevance or if it is a local issue. In addition, technical guidance and best practice for analysing priority substances has arisen from the work to support implementation of the WFD (Lepom et al., 2009;Loos et al., 2009). ...
... Frequency of detection for selected substances (% of samples) in rivers and groundwaterSource:Loos et al., 2009;Loos et al., 2010. ...
Technical Report
An overview of hazardous substances, including emerging contaminants, in both fresh and marine waters. The report addresses, sources, risk to aquatic life and human health, policy and legislation and mitigation
... In recent decades, there has been a significant increase in the pollution of freshwater systems. An ever-increasing number of contaminants such as carbamazepine, bisphenol-A and caffeine could be detected worldwide [1][2][3][4]. The effects of the increased occurrence of these contaminants can hardly be estimated today. ...
... In the case of the rhodamine-B removal, the pseudo first-order kinetic model using the first-order rate equation (Equation (2)) was applied to derive the rate constant. Ct = C0 · exp(−k/t) (2) herein, k represents the first-order reaction rate, t can be ascribed as the degradation time, C0 is the initial and Ct the time-dependent rhodamine-B concentration. These results suggest that the mesoframes are a reliable candidate for the oxidative degradation of rhodamine-B. ...
Article
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The tetramethylammonium hydroxide (TMAH)-controlled alkaline etching of nickel hexacyanoferrate (NiHCF) mesocrystals is explored. The alkaline etching enables the formation of hollow framework structures with an increased surface area, the exposure of active Ni and Fe sites and the retention of morphology. The ambient reaction conditions enable the establishment of a sustainable production. Our work reveals novel perspectives on the eco-friendly synthesis of hollow and colloidal superstructures for the efficient degradation of the organic contaminants rhodamine-B and bisphenol-A. In the case of peroxomonosulfate (PMS)-mediated bisphenol-A degradation, the rate constant of the etched mesoframes was 10,000 times higher indicating their significant catalytic activity.
... Scientific evidence on environmental exposures to multiple hazardous chemicals is increasing [44]. Data from monitoring studies of European surface waters demonstrate the co-occurrence of multiple chemicals in time and space [11,45]. Substance concentrations in European surface waters may exceed regulatory thresholds for single substances and potential risks have been shown to increase with the number of chemicals found [12,46]. ...
Article
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It is acknowledged that a variety of chemicals enter the environment and may cause joint effects. Chemicals regulated under the European Chemicals Regulation REACH are often part of formulated mixtures and during their processing and use in various products they can be jointly released via sewage treatment plants or diffuse sources, and may combine in the environment. One can differentiate between intentional mixtures, and unintentional mixtures. In contrast to other substance-oriented legislations, REACH contains no explicit requirements for an assessment of combined effects, exposures and risks of several components. Still, it requires ensuring the safe use of substances on their own, in mixtures, and in articles. The available options to address intentional as well as unintentional mixtures are presented and discussed with respect to their feasibility under REACH, considering the responsibilities, communication tasks and information availability of the different actors (registrants, downstream-user and authorities). Specific mixture assessments via component-based approaches require a comprehensive knowledge on substances properties, uses, fate and behaviour, and the composition of the mixture under consideration. This information is often not available to the responsible actor. In principle, intentional mixtures of known composition can be assessed by the downstream-user. But approaches have to be improved to ensure a transparent communication and sound mixture assessment. In contrast, unintentional mixtures appear to be better addressable via generic approaches such as a mixture allocation factor during the chemical safety assessment, although questions on the magnitude, implementation and legal mandates remain. Authorities can conduct specific mixture risk assessments in well-defined and prioritized cases, followed by subsequent regulatory measures. In order to address intentional and unintentional mixtures within the current REACH framework, legal mandates together with guidance for the different actors are needed. Furthermore, further data on mixture compositions, uses and co-exposures need to be made accessible via shared databases.
... Among chemical contaminants, the model herbicide diuron is a water framework directive (WFD) priority substance (2000/06/EC) broadly detected in European aquatic systems (Loos et al. 2009) and that has been widely used as a model photosynthesis inhibitor in ecotoxicology. Indeed, as an inhibitor of photosystem II (i.e., blocker of the electron transfer through interaction with the plastoquinone binding site), diuron has been shown to strongly reduce photosynthetic activity in both microalgae and freshwater biofilms (Moisset et al. 2015;Tlili et al. 2008). ...
Article
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Freshwater biofilms have been increasingly used during the last decade in ecotoxicology due to their ecological relevance to assess the effect(s) of environmental stress at the community level. Despite growing knowledge about the effect of various stressors on the structure and the function of these microbial communities, a strong research effort is still required to better understand their response to chemical stress and the influence of environmental stressors in this response. To tackle this challenge, untargeted metabolomics is an approach of choice because of its capacity to give an integrative picture of the exposure to multiple stress and associated effect as well as identifying the molecular pathways involved in these responses. In this context, the present study aimed to explore the use of an untargeted metabolomics approach to unravel at the molecular/biochemical level the response of the whole biofilm to chemical stress and the influence of various environmental factors in this response. To this end, archived high-resolution mass spectrometry data from previous experiments at our laboratory on the effect of the model photosynthesis inhibitor diuron on freshwater biofilm were investigated by using innovative solutions for OMICs data (e.g., DRomics) and more usual chemometric approaches (multivariate and univariate statistical analyses). The results showed a faster (1 min) and more sensitive response of the metabolome to diuron than usual functional descriptors, including photosynthesis. Also, the metabolomics response to diuron resulted from metabolites following various trends (increasing, decreasing, U/bell shape) along increasing concentration and time. This metabolomics response was influenced by the temperature, photoperiod, and flow. A focus on a plant-specific omega-3 (eicosapentaenoic acid) playing a key role in the trophic chain highlighted the potential relevance of metabolomics approach to establish the link between molecular alteration and ecosystem structure/functioning impairment but also how complex is the response and the influence of all the tested factors on this response at the metabolomics level. Altogether, our results underline that more fundamental researches are needed to decipher the metabolomics response of freshwater biofilm to chemical stress and its link with physiological, structural, and functional responses toward the unraveling of adverse outcome pathways (AOP) for key ecosystem functions (e.g., primary production).
... Most surface water forms display many anthropogenically generated compounds; moreover, 10% of European lakes are only labeled 'very clean' based on their chemical grade [21]. Besides, the United Nations resolution in 2010 stated water as the 'new gold of 21st century. ...
Article
Pharmaceuticals, steroids, personal care products, and disruptive endocrine substances are increasingly being used for healthcare objectives and to improve living conditions, resulting in the widespread presence of micropollutants in various water sources. Traditional water/ sewage and wastewater treatment plants are limited in their ability to cope with faced with these pollutants, making it challenging to supply safe and clean water for drinking and other domestic purposes. In this review, carbon nanotubes (CNTs) and CNTs related composites/ membranes have been considered suitable for settling this emerging issue. The existence of emerging micropollutants and their deleterious effects on human and animal health are discussed in this review. The efficient removal of micropollutants from different water sources using different types of CNTs (pristine/ functionalized) and CNTs-based composites/ membranes have been reviewed and evaluated. Moreover, fabrication approaches CNTs- based composites/membranes are also presented with their merits and demerits. Lastly, the current barriers and future perspectives are discussed in detail. The present review provides an in-depth understanding of the removal of micropollutants from CNTs and CNTs related composites/ membrane and allows future researchers to resolve the barriers related to their applications at an industrial scale.
... The highest levels of glyphosate and its metabolites were identified regularly. Existence of several pesticides in the surface water, river and lakes throughout Europe were revealed which may cause probable risk for the aquatic organisms (Loos et al., 2009;Brown and Beinum, 2009;Proia et al., 2013;Silva et al., 2019). ...
Article
Celastrus paniculatus is a traditional herb belonging to the family Celastraceae and is widely used for a number of medicinal activities in the Indian Unani and Ayurvedic systems. In this study, the extensive literature search was carried out on phytochemistry, ethnobotanical uses and pharmacological activities of C. paniculatus (Willd.) in various scientific databases as well as patents. Research on phytochemical investigation has shown the presence of monoterpenes (linalool, α‐terpinyl acetate, nerol acetate), sesqueterpene esters (such as malkanguniol, malkangunin, valerenal, globulol, viridiflorol, cubenol and agarofuran derivatives), diterpenoids (such as phytone, isophytol), triterpenoids (such as lupeol, pristimerin, paniculatadiol, zeylasteral, zeylasterone, β‐amyrin, squalene), alkaloids (celapanin, celapanigin, celapagin, paniculatine, celastrine, maymyrsine), fatty acids, steroids (β‐sitosterol, carpesterol benzoate), flavonoids (paniculatin), benzoic acid, and vitamin C in this plant. All the reported pharmacological activities of this plant could be due to the presence of these phytochemicals. This plant possesses strong antioxidant activity which includes total flavonoid content, total phenolic content, nitric oxide scavenging activity and free radical scavenging activity. This plant possesses multiple pharmacological activities including cognition‐enhancing, neuroprotective, antipsychotic, anti‐depressant, antibacterial, anti‐arthritic, anti‐malarial, analgesic, anti‐inflammatory, anti‐fertility, cardiovascular, locomotor, anxiolytic, wound healing activity, anti‐spasmodic, hypolipidemic, anti‐cancerous and iron‐chelating activity with different extracts of this plant as well as various phytoconstituents present in this plant. The objective of this review article is to discuss in detail the reported ethnopharmacological uses, phytochemistry and various pharmacological activities of C. paniculatus.
... Additionally, it is important to notify that MET belongs to carbamate class, which are high potential to persist, bio-accumulate and transfer to living organisms in intensified toxic forms. It is well known that MET exhibits toxicity to organisms such as bluegill sunfish [10]. It can also contaminate soil (bioaccumulation in plants) and groundwater (persistent substance) [11]. ...
Article
Gamma irradiation degradation of the extensively used muscle relaxant in the world methocarbamol (MET) was studied. MET aqueous solutions were irradiated by gamma rays emitted by a Cobalt 60 source at doses of 1-4 kGy.Our findings demonstrated that gamma irradiation degraded more than 98.5% of MET. Absorption spectra analysis revealed that when increased irradiation dose the absorption bands declined with complete disappearance at 4 kGy dose. Additionally, the most radiolytic degradation rate was recorded at neutral pH, marked by Total Organic Carbon (TOC) removal rate of 98% reflecting the total mineralization of MET at 4 kGy. In-depth spectrophotometric analyses advocated a pseudo-first-order type of MET degradation kinetics. The obtained apparent rate constant value was kapp, MET = (0.02167 ± 0.0006) min-1. Gas chromatography-mass spectrometry (GC-MS) allowed the detection of 3-(o-Methoxyphenoxy)-1,2 propanediol,2-Methoxyphenol, 1,2,3 propanetriol, 1,2-dihydroxybenzene and 1,2,4 benzentriol identified as by-products generated during radiolytic degradation. Finally, an outline of the degradation mechanism was suggested according to the obtained by-products.
... The Rhine is used in many ways: as a source for leisure and recreation, as a waterway, for the discharge of wastewater, and as a source of drinking water. It comes as no surprise that the surface water of the Rhine, has a strong influence on the quality of drinking water (Loos et al., 2009) if not treated adequately. ...
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Surface water of rivers like the Rhine is a highly relevant environmental and an important source of the Dutch drinking water. To improve protection of the environment and drinking water supply, it is important to have a continuous overview of the chemical composition of the river. Such an overview may be obtained with contemporary, untargeted analytical platforms like gas chromatography-mass spectrometry. Interpretation of such untargeted data is however challenged by the presence of many chemicals of natural origin. We developed a novel approach to screen for anthropogenic chemicals using nonparametric tests on the time trends of yet unidentified chemicals. The approach uses PARAFAC2 to extract unknown components present in GC–MS data and provides an assessment of whether such components may be anthropogenic. This significantly reduces screening efforts required by human laboratory staff. In total, out of twelve suspect unknown components, eleven were classified as anthropogenic, providing compelling evidence that studying unknown components can be highly valuable for regulatory bodies. This approach filters out many naturally occurring compounds, leaving more resources available for wet-lab identification of suspected anthropogenic chemicals.
... It is roughly estimated that a person consumes 300 mg of caffeine per day, while only 16 mg of caffeine ends up in the sewer system because of transformations in the human body [5]. Loose et al. [6] detected amounts of caffeine in 95% of the river and stream water samples tested across Europe. The concentration of caffeine found in surface water varies between 10 ng/L to 194 ng/L, and in groundwater, it is about 9.8 µg/L [7]. ...
Article
Activated carbon from Acacia mangium wood was prepared by chemical activation using H3PO4 under optimum conditions (OAMW-AC). In this study, a rotatable central composite design of response surface methodology was used to optimize the adsorption capacity of OAMW-AC against caffeine molecules. The maximum removal capacity of the OAMW-AC was found to be 29.2 mg/g under optimized conditions. The experimental results established optimized conditions for maximum caffeine removal were; 61 min of contact time, 3.0 g/L of adsorbent dosage, 100 mg/L of initial caffeine concentration, and 7.60 solution pH. The surface morphology, surface elemental composition, and surface functional group changes on the OAMW-AC were monitored by field emission scanning electron microscopy images, energy dispersive x-ray spectroscopy, and Fourier transform infrared spectroscopy, respectively. The characterization data showed OAMW-AC had a Brunauer-Emmet-Teller (BET) surface area of 1767 m²/g with dominated mesopore area (94.8%). The pH at the point of zero charges (pHzpc) was 2.25, and the negative value of proton binding capacity (Q = - 0.23 mmol/g) showing proton dissociation from the carbon surface at pH above pHzpc. A desorption study of the caffeine through 95% ethanol solution was also carried out. It was observed that 37.2 % of the adsorbed caffeine could be reclaimed from activated carbon.
... While environmental monitoring has long been focused on nonpolar persistent organic pollutants, the last two decades of research have seen increasing attention paid to the large number of polar organic pollutants. A specific focus was given to pharmaceuticals and personal care products that were considered particularly relevant (Daughton and Ternes, 1999;Ternes, 1998) and European surveys were launched to screen for polar compounds, typically addressing 30-50 targets including synthetic chelating agents, surfactants, dispersants, biocides and corrosion inhibitors, personal care products, pharmaceuticals and pesticides (Loos et al., 2009;Reemtsma et al., 2006). Since then, the number of detected chemicals in the water cycle continuously increased, with 125 chemicals out of 156 polar organic contaminants detected in wastewater treatment plant effluents (WWTP) in 2013 (Loos et al., 2013). ...
Article
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In this study, 56 effluent samples from 52 European wastewater treatment plants (WWTPs) were investigated for the occurrence of 499 emerging chemicals (ECs) and their associated potential risks to the environment. The two main objectives were (i) to extend our knowledge on chemicals occurring in treated wastewater, and (ii) to identify and prioritise compounds of concern based on three different risk assessment approaches for the identification of consensus mixture risk drivers of concern. Approaches include (i) PNEC and EQS-based regulatory risk quotients (RQs), (ii) species sensitivity distribution (SSD)-based hazard units (HUs) and (iii) toxic units (TUs) for three biological quality elements (BQEs) algae, crustacean, and fish. For this purpose, solid-phase extracts were analysed with wide-scope chemical target screening via liquid chromatography high-resolution mass spectrometry (LC-HRMS), resulting in 366 detected compounds, with concentrations ranging from <1 ng/L to >100 µg/L. The detected chemicals were categorized with respect to critical information relevant for risk assessment and management prioritization including: (1) frequency of occurrence, (2) measured concentrations, (3) use groups, (4) persistence & bioaccumulation, and (5) modes of action. A comprehensive assessment using RQ, HU and TU indicated exceedance of risk thresholds for the majority of effluents with RQ being the most sensitive metric. In total, 293 out of the 366 compounds were identified as mixture risk contributors in one of the approaches, while 32 chemicals were established as consensus mixture risk contributors of high concern, including a high percentage (66%) of pesticides and biocides. For samples which have passed an advanced treatment using ozonation or activated carbon (AC), consistently much lower risks were estimated.
... Monitoring studies have measured pesticides and TPs in concentrations in the order of μg L −1 in surface water and groundwater (e.g. Amalric et al., 2013;Loos et al., 2009;Moschet et al., 2014). Pesticides and TP concentrations as low as 10 or 2 μg L −1 , respectively, have been shown to impact groundwater microbial communities (Mauffret et al., 2017) and reduce denitrification (Michel et al., 2021). ...
Article
Hyporheic sediments are influenced by physical, biological, and chemical processes due to the interactions with river water and has been shown to play an important role in the environmental fate of pesticides. Therefore, this study evaluated the bacterial degradation potential of MCPA, metolachlor and propiconazole in hyporheic sediments sampled along a 20 km long stretch of an agriculturally impacted river dominated primarily by water losing conditions. Water physicochemical parameters in the river and nearby groundwater wells were assessed along with pesticide sorption to sediments and bacterial community composition. Degradation and mineralisation batch experiments were set up from six locations (five water losing, one water gaining) using environmentally relevant concentrations of pesticides (10 μg kg⁻¹). Highly variable DT50 values from 11 to 44 days for MCPA, 11–27 days for metolachlor (MTC) and 60–147 days for propiconazole were calculated based on ~140 day studies. Degradation of MTC led to accumulation of the transformation products MOA and MESA in batch experiments. Noteworthy, MESA was detected in the groundwater wells adjacent to the part of the river impacted by losing conditions suggesting that degradation processes in hyporheic sediments may lead to the formation of transformation products (TP) leaching towards groundwater. Further, from propiconazole was identified a persistent transformation product being different from 1,2,4-triazole. Specific calculated DT50 values could not the linked to bacterial diversity. However, generally all sediment samples were characterised by high bacterial diversity, where approximately 80% of the relative sequence abundances were < 1%, which may increase the likelihood of finding contaminant-degrading genes, thereby explaining the general high contaminant-degrading activity. The studied sediments revealed a high potential to degrade pesticides despite only being exposed to low diffuse pollutant concentrations that is similar to calculated DT50 values in agricultural soils.
... These include pharmaceuticals and hormones, pesticides, illicit drugs, artificial sweeteners, personal care products, disinfection byproducts, perfluorinated compounds, and UV filters, as well as other industrial chemicals that have been found in the ng/L-g/L range [7]. Emerging contaminants (ECs) have been found in wastewater, groundwater, and surface waters, including pharmaceuticals, X-ray contrast media, cosmetics, and personal care products [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25]. After invading the environment via leaky sewage pipes and septic systems, these chemicals penetrate groundwater, travel through wastewater treatment facilities, and finally discharge into receiving rivers. ...
Article
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Emerging contaminants (ECs) are synthetic or naturally occurring chemicals or any microorganisms that are not commonly monitored in the environment but have the potential to enter the environment and cause known or suspected adverse ecological or human health effects. The issue of ECs persistent in the environment and can disrupt the physiology of target receptors, they are recognized as Contaminants of emerging environmental concerns. The prominent classes of ECs include pharmaceuticals and personal care products (PPCPs), plasticizers, surfactants, fire retardants, nanomaterials, and pesticides. Several ECs have been recognized as endocrine disruptive compounds (EDCs) due to their deleterious effects on endocrine systems (EDCs). The contaminants present in the aquatic environment resources are a major cause of concern for human health and the environment and safety concern. These contaminations have risen into a major threat to the water distribution system. The impact of emerging contaminants (ECs) such as medicines, x-ray media, endocrine disruptors, insecticides, and personal care items has been reported in surface water, wastewater, and groundwater sources worldwide in recent years. Various techniques have been explored for ECs degradation and removal to mitigate their harmful effect. Numerous prior or continuing investigations have focused on the degradation and removal of contaminants using a variety of treatment techniques, including (1) physical, (2) chemical, and (3) biological. However, experimental data is insufficient to provide precise predictions regarding the mechanistic degradation and removal fate of ECs across various in-practice systems. The membrane technology can remove particles as fine as 10 μm and colloidal particles, It can be effectively eliminated by up to 99% through the use of MBR and treatment technologies such as reverse osmosis, ultrafiltration, or nanofiltration at concentrations up to 5 g/liter. In this paper, the emerging contaminants overview, their sources, and their removal by application of various treatments based on recent studies have been presented.
... These include pharmaceuticals and hormones, pesticides, illicit drugs, artificial sweeteners, personal care products, disinfection byproducts, perfluorinated compounds, and UV filters, as well as other industrial chemicals that have been found in the ng/L-g/L range [7]. Emerging contaminants (ECs) have been found in wastewater, groundwater, and surface waters, including pharmaceuticals, X-ray contrast media, cosmetics, and personal care products [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25]. After invading the environment via leaky sewage pipes and septic systems, these chemicals penetrate groundwater, travel through wastewater treatment facilities, and finally discharge into receiving rivers. ...
Article
Full-text available
Emerging contaminants (ECs) are synthetic or naturally occurring chemicals or any microorganisms that are not commonly monitored in the environment but have the potential to enter the environment and cause known or suspected adverse ecological or human health effects. The issue of ECs persistent in the environment and can disrupt the physiology of target receptors, they are recognized as Contaminants of emerging environmental concerns. The prominent classes of ECs include pharmaceuticals and personal care products (PPCPs), plasticizers, surfactants, fire retardants, nanomaterials, and pesticides. Several ECs have been recognized as endocrine disruptive compounds (EDCs) due to their deleterious effects on endocrine systems (EDCs). The contaminants present in the aquatic environment resources are a major cause of concern for human health and the environment and safety concern. These contaminations have risen into a major threat to the water distribution system. The impact of emerging contaminants (ECs) such as medicines, x-ray media, endocrine disruptors, insecticides, and personal care items has been reported in surface water, wastewater, and groundwater sources worldwide in recent years. Various techniques have been explored for ECs degradation and removal to mitigate their harmful effect. Numerous prior or continuing investigations have focused on the degradation and removal of contaminants using a variety of treatment techniques, including (1) physical, (2) chemical, and (3) biological. However, experimental data is insufficient to provide precise predictions regarding the mechanistic degradation and removal fate of ECs across various in-practice systems. The membrane technology can remove particles as fine as 10 μm and colloidal particles, It can be effectively eliminated by up to 99% through the use of MBR and treatment technologies such as reverse osmosis, ultrafiltration, or nanofiltration at concentrations up to 5 g/liter. In this paper, the emerging contaminants overview, their sources, and their removal by application of various treatments based on recent studies have been presented.
... To explore the effects of CBZ and MPs on shell formation and exclude the potential influence of the solvent used, the following five experimental groups were conducted in this study: a control group without CBZ or MPs, a solvent control group with 0.00033 % DMSO (v:v), a CBZ exposure group with 10 μg/L (nominal) CBZ, an MP exposure group with 0.26 mg/L (nominal) MPs, and a CBZ-MP coexposure group with both MPs and CBZ at the abovementioned concentrations. Since comparable concentrations of MPs and CBZ have been detected in natural environments, i.e., approximately 0.25 mg/L of MPs has been detected in the survey carried out in North Pacific Subtropical Gyre, Alaska, the California Current, and the Eastern Tropical Pacific; and CBZ ranged from 0.03 to 11.6 μg/L was found in various aqueous environments such as surface water (Loos et al., 2009;Lechner et al., 2014;Goldstein et al., 2012;Oliveira et al., 2017;Sousa et al., 2018), following those reported previously (Laura et al., 2009;Aguirre-Martínez et al., 2016;Franzellitti et al., 2017Franzellitti et al., , 2019, 0.26 mg/L and 10 μg/L were chosen as the exposure concentrations of MPs and CBZ in this study to mimic environmentally realistic pollution conditions of these two pollutants. The exposure lasted for 4 weeks (a duration accounts for approximately 5.6 %8 ...
Article
Forming calcareous exoskeletons is crucial for the health and survival of calcifiers such as bivalves. However, the impacts of waterborne emergent pollutants on this important process remain largely unknown. In this study, the effects of two types of emergent pollutants, microplastics (MPs) and carbamazepine (CBZ), which are ubiquitously present in ocean environments, on shell formation were assessed in the thick-shell mussel (Mytilus coruscus) with a shell regeneration experiment. In addition, their impacts on the in vivo contents of ATP, Ca²⁺, carbonic anhydrase (CA), and bone morphogenetic protein receptor type-2 (BMPR2), the activity of phosphofructokinase (PFK) and Ca²⁺-ATPase, and the expression of shell-formation related genes were analyzed. The data collected demonstrated that shell regeneration after mechanical injury was significantly arrested by CBZ and/or MPs. Besides, all the physiological and molecular parameters investigated were markedly suppressed by these two pollutants. Furthermore, synergistic impacts on most of the parameters examined were observed between CBZ and MPs. Our results indicate that these two pollutants may disrupt shell formation by constraining the availability of raw materials and energy, inhibiting the formation of the organic shell matrix, and interfering with the regulation of crystallization, which may have far-reaching impacts on the health of marine calcifiers.
... Bacteriological contamination of the river should be detected in order to know about the possibility of water and find out an effective method of treatment (Storck et al., 2015). Organic micro-pollutants are presented in most river water, and the capacity of RBF for the expulsion of common micro-pollutants is ideal (Glorian et al., 2018;Loos et al., 2009;Maeng et al., 2008;Sprenger et al., 2014). Kim and Zoh (2016) claimed that micro-pollutants may not be completely removed through drinking water treatment in typical technique, such as flocculation, aeration, filtration, and carbon filtration. ...
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The point of the study is to discover the significance of Sirwan riverbank filtration in water treatment, and to compare the quality of Sirwan riverbank filtration water to other two sources, such as Sirwan River and the lake adjacent to Sirwan River, which is semi-riverbank filtration. Water samples have been taken month to month for three months from three sources of water in Kalar City, Iraq, which are Sirwan River, lake and riverbank. In arranging to evaluate the quality of each source of water some physical, chemical and bacteriological parameters were surveyed, such as turbidity, total dissolved solid, calcium, magnesium, sodium, potassium, nitrate, sulfate, pH, coliform, Escherichia coli, and natural organic materials. Turbidities of Sirwan River and lake are typically high which are 13.47 and 6.9 NTU, respectively, however, turbidity is in excellent range in Sirwan riverbank filtration which is 0.3 NTU. Total dissolved solid level of Sirwan riverbank filtration is a bit critical, but it is still in safe range, which is 284 (mg/l). Coliform and Escherichia coli counts are greater than 100 (count/100 ml) in Sirwan River, and lower than 50 (count/100 ml) in lake water, while they are not recorded in Sirwan riverbank filtration. The study concluded that the quality of Sirwan riverbank filtration is best compared to other two sources, since it is ideal in expelling bacteria, organic materials and turbidity. Water treatment plant and profound well that utilized as the sources of potable water in Kalar City can be supplanted with Sirwan riverbank filtration.
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Perfluorooctanoic acid (PFOA), a hazardous environmental pollutant, has been found to enhance hepatic synthesis of fibroblast growth factor 21 (FGF21). FGF21 can enter the brain and increase the expression of corticotropin-releasing factor (CRF) in the paraventricular nucleus (PVN). In this study, adult male mice were orally administered PFOA to evaluate how it regulates emotion. Exposure of mice to PFOA (1 mg kg-1 bw) for 10 consecutive days (PFOA-mice) caused anxiety-like behaviors and a peroxisome proliferator-activated receptor α (PPARα)-dependent increase in hepatic FGF21 synthesis. The levels of CRF expression in not only PVN but also basolateral amygdala complex (BLA) neurons of PFOA-mice were increased via FGF receptor 1 (FGF-R1) activation. However, the microinjection of FGF-R1 or CRF 1 receptor (CRF-R1) antagonist in the BLA rather than the PVN of PFOA-mice could relieve their anxiety-like behaviors. In addition, external capsule-BLA synaptic transmission in PFOA-mice was enhanced by increasing CRF-R1-mediated presynaptic glutamate release, which was corrected by the blockade of PPARα, FGF-R1 and CRF-R1 or the inhibition of PKA. Furthermore, the threshold of frequency-dependent long-term potentiation (LTP) induction was decreased in the BLA of PFOA-mice, which depended on the activation of PPARα, FGF-R1, CRF-R1, PKA and NMDA receptor (NMDAR), whereas long-term depression (LTD) induction was unchanged. Thus, the results indicate that the exposure of male mice to PFOA (1 mg kg-1 bw) enhances CRF expression in BLA neurons by increasing hepatic FGF21 synthesis, which then enhances CRF-R1-mediated presynaptic glutamate release to facilitate NMDAR-dependent BLA-LTP induction, leading to the production of anxiety-like behaviors.
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Benzotriazole and its derivatives (BTRs), classified as high-volume production chemicals, have been widely detected in various environmental media, including the atmosphere, water, soil and dust, as well as organisms. However, studies on the pollution characteristics and health impact of PM2.5 related BTRs are so far limited. This study is the first to demonstrate the regional scale distribution of PM2.5-bound BTRs and their potential cardiotoxicities. Optimized methods of extraction, purification and GC-EI-MS/MS were applied to characterize and analyze PM2.5-bound BTRs from three cities in China during the winter of 2018. The concentration of ∑BTRs in Taiyuan (6.28 ng·m-3) was more than three times that in Shanghai (1.53 ng·m-3) and Guangzhou (1.99 ng·m-3). Benzotriazole (BTR) and 5-methyl-1H-benzotriazole (5TTR) contributed more than 80% of ∑BTRs concentration as the major pollutants among three cities. The correlation analysis indicated that there was a positive correlation between temperature and concentration of BTR and a negative correlation between temperature and concentration of 5TTR. In addition, the risk of BTRs exposure to toddlers should be paid more attention in Taiyuan by the human exposure assessment. Furthermore, toxicity screening by experimental methods indicated that 4-methyl-1H-benzotriazole (4TTR) was the most harmful to cardiomyocytes. The western blot assay showed a ROS-mediated mitochondrial apoptosis signaling pathway was activated after exposure to 4TTR in neonatal rat cardiomyocytes (NRCMs). On the other hand, metabolomics revealed that exposure of 4TTR to NRCMs disturbed mitochondrial energy metabolism by disturbing pantothenate and coenzyme A synthesis pathway. Our study not only clarifies the contamination profiles of PM2.5-bound BTRs in typical Chinese cities but also reveals their cardiotoxicities associated with mitochondrial dysfunction.
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Organic contaminants can be removed from water/wastewater by oxidative degradation, using oxidants such as manganese oxides and/or aqueous manganese ions. The Mn species show a wide range of activity, which is related to the oxidation state of Mn. Here, we use ab initio molecular dynamics simulations to address Mn oxidation states in these systems. We first develop a correlation between Mn partial atomic charge and the oxidation state, based on results of 31 simulations on known Mn aqueous complexes. The results collapse to a master curve; the dependence of partial atomic charge on oxidation state weakens with increasing oxidation state, which concurs with a previously proposed feedback effect. This correlation is then used to address oxidation states in Mn systems used as oxidants. Simulations of MnO2 polymorphs immersed in water give average oxidation states (AOS) in excellent agreement with experimental results, in that β-MnO2 has the highest AOS, α-MnO2 has an intermediate AOS, and δ-MnO2 has the lowest AOS. Furthermore, the oxidation state varies substantially with the atom's environment, and these structures include Mn(III) and Mn(V) species that are expected to be active. In regard to the MnO4⁻/HSO3⁻/O2 system that has been shown to be a highly effective oxidant, we propose a novel Mn complex that could give rise to the oxidative activity, where Mn(III) is stabilized by sulfite and dissolved O2 ligands. Our simulations also show that the O2 would be activated to O2²⁻ in this complex under acidic conditions, and could lead to the formation of OH radicals that serve as oxidants.
Thesis
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Déterminer et quantifier le rôle de la phase particulaire dans les grands cycles géochimiques et le transport des contaminants, est devenu indispensable pour établir des bilans de masse précis et discuter de l’incidence du facteur de forçage d’origine anthropique sur les écosystèmes. Durant ces travaux, le transport particulaire a été étudié à l’échelle du bassin versant périurbain de l’Egoutier selon une démarche sources-puits. Affluent de la Loire situé à l’est de la métropole d’Orléans, l’hydrosystème est défini par un gradient d’anthropisation amont/aval et des rejets anthropiques ponctuels. L’étude a pour objectif (1) de comprendre la dynamique hydrosédimentaire des cours d’eau en contexte peu morphogène et périurbain, (2) d’identifier des traceurs spécifiques des sources de matériel soumis à l’érosion mécanique dans le bassin versant, et (3) de discuter du rôle de la dynamique hydrosédimentaire et de l’occupation du sol dans le cycle géochimique des éléments et des contaminants. Les différents traceurs ont été explorés par géochimie multi-élémentaire et par quantification des ETM et des PPs, afin de discriminer la signature géochimique des sources et les chemins de transfert de la matière particulaire. Le comportement hydro-sédimentaire de l’Egoutier est également suivi en temps réel en trois endroits clés. Des modes d’érosion et une dynamique sédimentaire différente ont été mis en évidence entre la partie amont du bassin versant sous couvert forestier, et la partie aval en contexte périurbain. Dans cette dernière, l’imperméabilisation des surfaces entraîne des évènements de crues plus rapides et intenses, favorisant le transport sédimentaire et limitant l’accumulation des particules. En plus de modifier la géomorphologie et la dynamique sédimentaire des cours d’eau, l’urbanisation croissante modifie les cycles biogéochimiques des éléments et entraîne une propagation des contaminants sur des distances plus importantes.
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The article deals with the still not much described issue of the process safety of municipal wastewater treatment plants. An author's database describing 232 accidents was created. These accidents were firstly classified into categories. Basic statistics, including an analysis of the number of accidents, were subsequently implemented for these categories. The potential consequences of accidents on human lives, the environment, and property have been referred to. An important part of the article is a description of the causes of accidents, which also points out the possibilities of how to prevent the respective accidents. Special attention is paid to the storage and handling of hazardous chemicals. The analysis of the information contained in the database shows that the environment is most often damaged in the event of an accident at WWTP; this occurs in 58% of cases, the most common cause being device or structural failure. It also transpires that a significant number of accidents at WWTPs are caused by extreme weather conditions, such as torrential rains, floods, etc., totalling 13% of all accidents. It can be estimated that, due to the higher frequency of extreme weather conditions, the number of such accidents will increase. WWTP operators should be prepared for this.
Thesis
Contaminants of emerging concern (CECs) show great environmental concern due to their potential toxic effect and persistence. More and more detected every year; they became ubiquitous as anthropogenic activities increase and their harmful effects were shown on aquatic organisms and human health. Conventional wastewater treatment plans do not fully remove CECs, as they were not designed to remove these pollutants. Developing and understanding novel water treatment approaches is essential to improve water quality and protect the environment. Processes based on light irradiation are very promising in this way. It is of high interest to evaluate the formation of potential photoproducts and their related toxicity; it also aims at understanding sunlight-induced transformation mechanisms of contaminants in the environment.The aim of this project was to apply different approaches to study the photodegradation of contaminants. Firstly, a laboratory modeling approach was applied to five contaminants: benzisothiazolinone, naproxen, perfluorooctanoic acid, maprotiline, and enrofloxacin. Direct photolysis and advanced oxidation processes, such as peroxide/UV, photocatalysis, photosensitizers, and Fenton reactions, were employed. They were either carried out under laboratory conditions in ultrapure water or on a pilot plant scale in secondary treated wastewater to model realistic conditions and study the matrix effect. The photodegradation efficiencies were studied using LC-MS analysis and UV-Vis spectroscopy. As mineralization is rarely achieved, LC-MS measurements were performed for the untargeted detection of photoproducts on an ultra-high-resolution FT-ICR mass spectrometer. This made the accurate identification of molecular formulas possible; structural elucidation of numerous photoproducts was achieved owing to MS2 experiments. Based on these structures, in silico toxicity calculations were performed to obtain information on their potential toxic effects. In parallel, in vitro bioassays were used to study the mixture's toxicity at each step of the photodegradation reaction. Through this approach, the scientific achievements include assessing the fate of contaminants, proposing and optimizing viable photodegradation processes, and elucidating photochemical reaction pathways.In parallel with the modeling approach, a non-targeted analytical approach was used to study complex mixtures. Direct infusion mass spectrometry was used to detect thousands of molecular ions and assess their formulas accurately. To better process these datafiles, the SPIX software was developed. One of its features is to find all the ions that undergo changes between two conditions. The other feature includes comparing a series of conditions, proposing kinetic models for each of them individually. The exportation of statistically relevant changes and further data processing was carried out. The software's application and mathematical background are presented through the analysis of contaminants in complex matrices, such as secondary treated wastewater and natural organic matter. The extension of the software to process 3D LC-MS datasets represents the latest developments. This software helped with rapid data processing and is innovative and unique in studying molecules' kinetics in complex samples. The holistic approach provided by SPIX constitutes a complementary tool to modeling approaches; it allows to detect and monitor relevant reactions in very complex media and contributes to reducing operator subjectivity during results interpretation.
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Surface water of rivers like the Rhine is a highly relevant environmental and an important source of the Dutch drinking water. To improve protection of the environment and drinking water supply, it is important to have a continuous overview of the chemical composition of the river. Such an overview may be obtained with contemporary, untargeted analytical platforms like gas chromatography-mass spectrometry. Interpretation of such untargeted data is however challenged by the presence of many chemicals of natural origin. We developed a novel approach to screen for anthropogenic chemicals using non-parametric tests on the time trends of yet unidentified chemicals. The approach uses PARAFAC2 to extract unknown components present in GC–MS data and provides an assessment of whether such components may be anthropogenic. This significantly reduces screening efforts required by human laboratory staff. In total, out of twelve suspect unknown components, eleven were classified as anthropogenic, providing compelling evidence that studying unknown components can be highly valuable for regulatory bodies. This approach filters out many naturally occurring compounds, leaving more resources available for wet-lab identification of suspected anthropogenic chemicals.
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Pesticides used in agriculture can end up in nearby streams and can have a negative impact on nontarget organisms such as aquatic invertebrates. During registration, bioaccumulation potential is often investigated using laboratory tests only. Recent studies showed that the magnitude of bioaccumulation in the field substantially differs from laboratory conditions. To investigate this discrepancy, we conducted a field bioaccumulation study in a stream known to receive pollutant loadings from agriculture. Our work incorporates measurements of stream pesticide concentrations at high temporal resolution (every 20 min), as well as sediment, leaves, and caged gammarid analyses (every 2–24 h) over several weeks. Of 49 investigated pesticides, 14 were detected in gammarids with highly variable concentrations of up to 140 ± 28 ng/gww. Toxicokinetic modeling using laboratory-derived uptake and depuration rate constants for azoxystrobin, cyprodinil, and fluopyram showed that despite the highly resolved water concentrations measured, the pesticide burden on gammarids remains underestimated by a factor of 1.9 ± 0.1 to 31 ± 3.0, with the highest underestimations occurring after rain events. Including dietary uptake from polluted detritus leaves and sediment in the model explained this underestimation only to a minor proportion. However, suspended solids analyzed during rain events had high pesticide concentrations, and uptake from them could partially explain the underestimation after rain events. Additional comparison between the measured and modeled data showed that the pesticide depuration in gammarids is slower in the field. This observation suggests that several unknown mechanisms may play a role, including lowered enzyme expression and mixture effects. Thus, it is important to conduct such retrospective risk assessments based on field investigations and adapt the registration accordingly.
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Human-sourced organic compounds like pesticides, pharmaceuticals, surfactants, personal care products, food, and industrial additives are used daily, across multiple sectors, globally. These compounds when found in the environment in undesirable or detrimental concentrations, are grouped and termed as emerging organic contaminants (EOCs). Groundwater are typically major sources of the community drinking water plants. EOCs can get introduced in the community drinking water sources via numerous point and non-point sources such as agricultural runoff, artificial recharge, or effluents from wastewater treatment plants (WWTPs). Several EOCs have been recently reported from community drinking water sources across the world. EOCs like carbamazepine, atrazine, caffeine, and metolachlor are frequently detected contaminants in drinking water sources. These EOCs are known to pose a severe risk to human health to these contaminated water ingesting communities. Conventional drinking water treatment plants fail to remove EOCs from the sources. These EOCs, along with other organics, lead to the formation of carcinogenic disinfection byproducts (DBPs) in community drinking water treatment plants. Researchers have explored various remedial measures ranging from in-situ treatments to ex-situ treatments. Researchers are presently exploring various emerging remedial measures like membrane separation or nanotechnology. All the treatment measures have their specific advantages and disadvantages. However, most of the remedial measures are investigated on a lab-scale. This fact highlights the need for proper field-scale experiments before being successfully used in community treatment plants to provide clean water to the masses to achieve sustainable development goal (SDG) 6.
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A field survey was conducted on five fish farms to trace glyphosate and malathion pollution with some physicochemical parameters. A precise half-life time, LC 50-96h, of these agrochemicals on Oreochromis niloticus, as well as chronic exposure with organic selenium (OS) supplementation, were experimentally investigated. Oreochromis niloticus was subjected to the following: (negative control); (2 mg L −1 glyphosate); (0.5 mg L −1 malathion); (glyphosate 1.6 mg L −1 and 0.3 mg L −1 malathion); (glyphosate 2 mg L −1 and OS 0.8 g kg −1 diet); (malathion 0.5 mg L −1 and OS 0.8 g kg −1 diet) and (glyphosate 1.6 mg L −1 ; malathion 0.3 mg L −1 and OS 0.8 g kg −1 diet). Furthermore, data from the analyzed pond revealed a medium risk quotient (RQ) for both agrochemicals. The detected agrochemicals were related to their application, and vegetation type surrounding the farms, also their biodegradation was correlated to water pH, temperature, and salinity. Glyphosate and malathion had half-lives of 2.8 and 2.3 days and LC 50-96h of 2.331 and 0.738 mg L −1 , respectively. The severest nervous symptoms; increased oxidative stress markers, as well as high bacterial count in the livers and kidneys of fish challenged with Aeromonas hydrophila, were observed in the combined exposure, followed by a single exposure to malathion and then glyphosate. Organic selenium mitigated these impacts.
Article
Worldwide, the anticonvulsant drug carbamazepine (CBZ) is the most frequently identified pharmaceutical residue detected in rivers. Reported chronic effects of CBZ in non-target freshwater organisms, particularly fish, include oxidative stress and damage to liver tissues. Studies on CBZ effects in fish are mostly limited to zebrafish and rainbow trout studies. Furthermore, there are only a few chronic CBZ studies using near environmental concentrations. In this study, we provide data on subacute effects of CBZ exposure (28 days) to common carp (Cyprinus carpio), employing a set of biochemical markers of damage and exposure. CBZ was found to induce a significant change in the hepatic antioxidant status of fish subjected to 5 µg/L. Moreover, with increasing concentrations, enzymatic and non-enzymatic biomarkers of oxidative defence (catalase (CAT), superoxide dismutase (SOD), glutathione reductase (GR), DNA strand breaks)), toxicant biotransformation (ethoxyresorufin-o-demethylase (EROD), glutathione-S-transferase (GST)), and organ and tissue damage (lactate dehydrogenase (LDH), cetylcholinesterase (AChE)) were altered. The AChE, LDH, and lipid peroxidation (LPO) results indicate the occurrence of apoptotic process activation and tissue damage after 28 days of exposure to CBZ. These findings suggest significant adverse effects of CBZ exposure to common carp at concentrations often found in surface waters.
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In this chapter, we report on the state of PFAS in a major South Indian River Periyar, for the first time. These substances are classified as a pollutant in many countries. Ingestion of these substances is known to cause adverse effects on the humans. Periyar is the largest west-flowing river in southern India (5398 km2 area covering 300 km in length). River water samples were collected from 16 stations (including the source, mouth, estuaries and main tributaries) in May 2013. HPLC MS/MS was used to measure the concentration of PFAS. The recovery of 13C labeled standards ranged between 60 and 100%. Perfluorobutanoic acid (PFBA), perfluorooctanoic acid (PFOA) and perfluorononanoic acid (PFNA) were found in all the 16 sampling stations. The PFBA concentration varied between 58 and 2174 ng/L. PFOA concentration varied between 22 and 1503 ng/L, and PFNA varied between 20 and 705 ng/L. Out of the six major PFAS analyzed, three perfluorosulfonates (PFSA) and three perfluoroalkyl carboxylic acids (PFCA) were detected. The highest concentration of PFAS was found near the Periyar estuary (12,958 ng/L).
Article
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The objective of this study was to critically review studies published up to November 2021 that investigated the presence of pesticides in surface freshwater to answer three questions: (1) in which countries were the studies conducted? (2) which pesticides are most evaluated and detected? and (3) which pesticides have the highest concentrations? Using the Prisma protocol, 146 articles published from 1976 to November 2021 were included in this analysis: 127 studies used grab sampling, 10 used passive sampling, and 9 used both sampling techniques. In the 45-year historical series, the USA, China, and Spain were the countries that conducted the highest number of studies. Atrazine was the most evaluated pesticide (56% of the studies), detected in 43% of the studies using grab sampling, and the most detected in passive sampling studies (68%). The compounds with the highest maximum and mean concentrations in the grab sampling were molinate (211.38 µg/L) and bentazone (53 µg/L), respectively, and in passive sampling, they were oxyfluorfen (16.8 µg/L) and atrazine (4.8 μg/L), respectively. The levels found for atrazine, p,p′-DDD, and heptachlor in Brazil were higher than the regulatory levels for superficial water in the country. The concentrations exceeded the toxicological endpoint for at least 11 pesticides, including atrazine (Daphnia LC50 and fish NOAEC), cypermethrin (algae EC50, Daphnia and fish LC50; fish NOAEC), and chlorpyrifos (Daphnia and fish LC50; fish NOAEC). These results can be used for planning pesticide monitoring programs in surface freshwater, at regional and global levels, and for establishing or updating water quality regulations.
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Emerging organic contaminants (EOCs) are widely detected in the environment including aquatic systems where they pose potential ecological and human health risks. Bio- and chemical surfactants are an emerging technology for the remediation of EOCs in aqueous environments. In this chapter, we present an overview of the various surfactants, and discuss how surfactant-based remediation techniques can be used to reduce environmental pollution from various groups of EOCs. Evidence of the capacity to remove various EOCs in aqueous systems is presented. The efficiency of surfactant-assisted remediation techniques is predicated on manipulating the solubility of target pollutants matrix. The procedures and mechanisms involved in the employment of surfactant-assisted technologies are summarized.
Article
The study addressed the mechanisms of toxicity induced to cyanobacteria Synechococcus sp by its exposure to sulfamethoxazole (SMX). Here, transcriptomics analysis was used to investigate variations in the molecular level of Synechococcus sp under SMX stress at concentrations of 0.5 and 10 μg L⁻¹. There were insignificant differences in algal density between 0.5 μg L⁻¹ and the control group, whereas a conspicuous reduction of 56% in the 10 μg L⁻¹ group was discovered. Additionally, 12 and 133 differentially expressed genes (DEGs) were found in the different treatment groups. Experimental results show that SMX at the environmentally realistic concentration may not disrupt the algal physiological status. Cyanobacteria are similar to bacterial in structure, and SMX has been recognized antibacterial effect of inhibiting folate synthesis. However, DEGs were dominantly enriched in the porphyrin and chlorophyll metabolism, photosynthesis, selenocompound metabolism, and tocopherol biosynthesis rather than folate biosynthesis pathway, indicating SMX has different mode of action between Synechococcus sp and bacteria. briefly, the Synechococcus sp was used as model organisms to reveal the mechanism of SMX.
Article
Nowadays, steroid hormonal analysis becomes important in maintaining reproduction, metabolism, growth, endocrine function and environmental applications, as they are concerned with immunological effects, developmental and cancer-causing substances. The review provides a brief description on steroids with particular emphasis on sexual steroid hormones (gonads) and their importance for determination. The review also describes different recognition elements such as antibodies, aptamers, molecularly imprinted polymers (MIPs) and enzymatic pathways in the determination of steroid hormones. In addition, this manuscript describes on different biosensing technologies used for monitoring steroid hormones and the progress achieved with the emerging carbonaceous nanomaterials for sensitivity, selectivity, excellent stability, reproducibility enhancement in detection methods due to the large surface area and excellent optical and electric conductivity. Finally, the latest trend on steroid hormones and their methods of detecting trace levels in complex environments was examined, along with existing challenges and future prospects in their analysis.
Article
Nitrophenolic compounds are hazardous substances, listed as priority pollutants by World Health Organization, due to their toxicity on both the environment and human health. They are used in agriculture as insecticides and fungicides substances, and they can contaminate water reserves by filtering through the soil into groundwater. Therefore, these substances must be removed from agricultural wastewater before being discharged. In this work, several Deep Eutectic Solvents, based on menthol, thymol and organic acid, are used as separation agents in liquid-liquid extraction to remove 2-nitrophenol and 4-nitrophenol from water. The optimal extraction conditions were studied and the better extraction yields were obtained using: (1:1) VDES:VW ratio and 30 min of stirring time. All extraction experiments were carried out at 298.15 K and 30 min of centrifugation time at 6000 rpm. As the results show, these deep eutectic solvents based on menthol can be used to extract both nitrophenolic compounds, while those based on thymol can only be applied for the removal of 4-nitrophenol. All studied solvents present high extraction efficiencies, over to 90%, assuring their capability as extraction agents in aqueous systems.
Chapter
The wastewater treatment plants performance is a function of various factors including wastewater quality, management conditions of the treatment plant, and environmental issues. Disposal of wastewater with acceptable quality characteristics to a variety of receiving sources is one of the environmental problems that today's societies face. In addition to transmitting microbial and chemical pathogens to humans, wastewater release destroys many aquatic species in rivers, lakes, and oceans. Due to its inherent and nonlinear characteristics, modeling a municipal sewage refinery is complex and difficult. Due to the increasing concerns about the environmental effects of refineries due to poor operation, fluctuations of process variables, and problems of online analyzers, artificial process control algorithms such as artificial neural networks have attracted a lot of attention due to increasing intelligence. An artificial intelligence network is a set of neurons that are located in different layers, forming a special architecture based on the connection between neurons. So that, the neuron is a nonlinear mathematical unit, and as a result, a neural network will be a complex and nonlinear system. This chapter discusses the literature to conduct a large-scale bibliometric analysis of traits inside the application of artificial intelligence generation to wastewater treatment. In addition, the use of marine sensors for simultaneous collection of relevant environmental data in parallel with the acquisition of visual data in error detection and detection, online estimation, and analysis of multivariate models will be investigated.
Article
The presence and distribution of ketoprofen, fenoprofen, diclofenac ibuprofen, naproxen, gemfibrozil, clofibric acid, estrone, 17β-estradiol, 17α-ethinylestradiol, and carbamazepine were investigated in water and surface sediment of the Golden Horn Estuary (Sea of Marmara, Turkey). Water samples were collected seasonally from different depths in nine sampling stations. Surface sediment samples were taken at four stations once a year. Liquid-liquid and solid-phase extraction (SPE) methods were performed on water samples. Sediment samples were extracted by ultrasonic extraction and then SPE method was applied for clean-up. Subsequently, all samples were analyzed by High-Performance Liquid Chromatography (HPLC). The most dominant compounds were found as gemfibrozil (<0.054-3.18 μg L⁻¹), fenoprofen (<0.017-1.28 μg L⁻¹), ibuprofen (<0.015-2.46 μg L⁻¹) and 17α-ethinylestradiol (<0.010-1.49 μg L⁻¹) in water samples. Only five of these eleven studied pharmaceuticals in surface sediments of the Golden Horn Estuary were able to identify. 17α-ethinylestradiol (319 ng g⁻¹), fenoprofen (242 ng g⁻¹), ibuprofen (215 ng g⁻¹), gemfibrozil (124 ng g⁻¹), carbamazepine (118 ng g⁻¹) were detected in the surface sediments. Diclofenac, ketoprofen, naproxen, clofibric acid, estrone and 17β-estradiol were found below the method detection limits in surface sediments. Generally, the environmental concentrations of pharmaceuticals in water and surface sediment were much higher than those reported worldwide.
Article
Contaminants of emerging concern (CECs) are a concern in aquatic environments due to possible adverse effects on the environment and humans. This study assessed the occurrence and mass flows of CECs in Sweden's three largest lakes and 24 associated rivers. The occurrence and distribution of 105 CECs was investigated, comprising 71 pharmaceuticals, 13 perfluoroalkyl substances (PFASs), eight industrial chemicals, four personal care products (PCPs), three parabens, two pesticides, and four other CECs (mostly anthropogenic markers). This is the first systematic study of CECs in Sweden's main lakes and one of the first to report environmental concentrations of the industrial chemicals tributyl citrate acetate and 2,2′-dimorpholinyldiethyl-ether. The ∑CEC concentration was generally higher in river water (31–5200 ng/L; median 440 ng/L) than in lake water (36–900 ng/L; median 190 ng/L). At urban lake sites, seasonal variations were observed for PCPs and parabens, and also for antihistamines, antidiabetics, antineoplastic agents, antibiotics, and fungicides. The median mass CEC load in river water was 180 g/day (range 4.0–4300 g/day), with a total mass load of 5000 g/day to Lake Vänern, 510 g/day to Lake Vättern, and 5600 g/day to Lake Mälaren. All three lakes are used as drinking water reservoirs, so further investigations of the impact of CECs on the ecosystem and human health are needed.
Article
The research focused on a very dangerous and commonly used compound which has carcinogenic and mutagenic impact on living organisms. 1H-benzotriazole (1H-BTR) is used as a corrosion inhibitor for installations in industrial plants, in the production of biocides, detergents, drugs, tires, rubber, in refrigeration systems and de-icing substances, while its derivates are UV stabilizers in plastics, paints, films and sunscreens. It is also an additive in petroleum products (lubricants, hydraulic fluids). The paper presents quantitative changes of 1H-BTR after sequencing batch reactor (SBR) process. The studies have been carried out for 411 cycles of SBR during which concentration of 1H-BTR was changed in the range of 50–1000 μg L⁻¹. SBR operating cycle consisted of 6 phases: filling (dilution-40 min.), mixing I (dephospatation-20 min.), aeration with stirring (nitrification and oxidation of organic compounds-300 min.), mixing II (denitrification-30 or 60 min.), settling and decantation (separation-40 min.), downtime (90 or 60 min.). The technological parameters of the activated sludge (sludge volume index, solids and hydraulic retention time) were as similar as possible to those maintained in the real wastewater treatment plant (WWTP). Mixed liquor suspended solids concentration was 3.50 kg m⁻³. Conducted studies showed that industrial wastewater containing 1H-BTR can be effectively treated in SBR. The conducted studies showed that removal of 1H-BTR with more than 80% efficiency is possible at effluent concentrations not exceeding 200 μg L⁻¹. Higher concentrations of 1H-BTR in wastewater lead to a sharp decrease in removal efficiency. The lowest removal efficiency (56.6%) was recorded at the initial 1H-BTR concentration of 100 μg L⁻¹. On the other hand, the highest efficiency (88.2%) at the initial concentration of 1000 μg L⁻¹. The concentration of 1H-BTR in treated wastewater was 1.1 μg L⁻¹ in the control reactor and from 7.2 to 434.0 μg L⁻¹ for an initial concentration from 50 to 1000 μg L⁻¹, respectively. The aeration phase was superior in terms of 1H-BTR removal, regardless of the benzotriazole doze in the raw wastewater. In the anaerobic mixing phases I and II in the SBR, the decomposition of the 1H-BTR was 5.3 and 4.9 times slower, respectively, compared to aerobic conditions.
Article
Long-term and excessive herbicide use has led to some environmental concerns and especially, herbicide resistance evolution in weeds. Here, we confirmed acetolactate synthase (ALS) inhibiting herbicide penoxsulam resistance and cross resistance to acetyl-coenzyme carboxylase (ACCase) inhibiting herbicides (cyhalofop-butyl and metamifop) in a global weed Echinochloa crus-galli population resistant to these herbicides (R). Penoxsulam metabolism study indicated that degradation rate was significantly higher in R than susceptible E. crus-galli population (S). RNA-sequencing revealed that a cytochrome P450 (P450) gene, CYP81A68, expressed higher in R versus S. Rice seedlings overexpressing this CYP81A68 gene are resistant to penoxsulam, cyhalofop-butyl and metamifop, and penoxsulam resistance is due to enhanced metabolism via O-demethylation. Deletion analysis of the CYP81A68 gene promoter identified an efficient region, in which differential methylation of CpG islands occurred between R and S. Collectively, these results demonstrate that upregulation of E. crus-galli CYP81A68 gene endows generalist metabolic resistance to commonly used ALS- and ACCase-inhibiting herbicides in rice fields and epigenetic regulation may play a role in the resistance evolution. This research could contribute to strategies reducing herbicide environmental impacts by judicious selection of alternative herbicide and non-chemical control tactics.
Article
1,2,3-benzotriazole (BT) is used in large amounts around the world and is one of the substances derived from household chemicals that are of concern for risk when discharged to aquatic environments. Therefore, several studies have been conducted on the aquatic toxicity effects of BT, but the chronic impact assessment studies to evaluate the developmental effects on the early-life stage of fish are insufficient. In this study, the acute toxicity test and subchronic toxicity test (fish, early-life stage toxicity test, ELS test) using embryos of Japanese medaka (Oryzias latipes) were performed to evaluate the acute toxicity, developmental toxicity, growth (indicated by total length and weight at the end of the test), and histopathological effect of BT. In the short-term toxicity test on embryo and sac-fry stage, toxicity value was calculated to be 41 mg/L (NOEC). Based on this value, the exposure concentration of the ELS test was determined as 0.04, 0.4, 4 and 40 mg/L, and total exposure duration was 42 days. At the highest concentration group (40 mg/L), failure of swim bladder inflation and decrease of survival and size (total length and weight) were observed. Moreover, in the histopathological analysis, abnormal findings were detected in swim bladders from the 40 mg/L group such as inflammation and tumor changes. On the other hands, condition index (weight-length relationships, CI) was statistically significantly lower in all exposed groups compared to the control group. NOEC for the survival of BT was calculated to be 4 mg/L. LOEC for CI was 0.04 mg/L, which means BT inhibited weight gain relative to its length on larvae of medaka.
Article
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Pharmaceuticals are an important class of micropollutants within the freshwater environment. There is sufficient evidence of their impacts on exposed biota to warrant further research to better assess their risk. We reviewed ecotoxicological freshwater studies conducted from 2010-2020 on carbamazepine, diclofenac, and ibuprofen, three high-use pharmaceuticals frequently detected globally in surface waters. One hundred and thirteen studies encompassing short-term (mean exposure duration 6.4 days) and long-term exposures (mean 37.8 days) were reviewed. Study designs were examined and critiqued using a qualitative analysis, and a quantitative analysis compared toxicities (lowest observed effect concentration, LOEC) between the three pharmaceuticals in both short- and long-term tests. Short-term tests were predominant (60% of studies), as reported in past related reviews. Examination of experimental designs highlighted important limitations. Most studies had low replication (n=3 per treatment) and provided no effect sizes for their findings, and 55% of studies did not supply measurements of actual exposure concentrations. Thirty-five percent of studies detected clear effects (mostly negative) at environmentally relevant concentrations. In short-term studies, biomarkers were the most sensitive endpoints; the same applied to community-level endpoints in long-term studies. The LOECs of all three pharmaceuticals (0.05-10 μg L⁻¹) were similar in both short- and long-term studies. Future research should prioritise long-term, environmentally relevant exposures, using a combination of biomarker and community-level endpoints. Due to the acute toxicity of pharmaceuticals, future studies should investigate how these contaminants may modify communities and ecosystems, rather than single-species approaches. Finally, a comprehensive meta-analysis would be pertinent when enough long-term, environmentally relevant studies with rigorous designs and effect size information have accumulated.
Article
The industrial intervention had a profound impact on our environment and the amount of damage it has bestowed is in the form of polluted water and solid waste accumulation. With upgradation of technologies in the industrial upfront there is also an increase in the robust nature of industrial waste. Keeping in view of the various environmental aspects, advanced techniques were developed by the inculcation of nanotechnology. Among the diverse technologies that have gained prominence is the use of nanoparticles as a medium to monitor and treatment process. One of them is the use of organic techniques, i.e., the use of nano-chitosan. The review article focuses on the new data pertaining to the study and improvement of various nano-scale treatment technologies implemented for wastewater treatment with an environment friendly biodegradation. The eradication of harmful toxicants is an exhaustive process, but this is required to invigorate the sustainable development. Various strategies were promulgated but the inculcation of nanomaterial provided a low-cost, efficient and simple method for removal of contaminants by adsorption. These nanomaterials provide the best adsorbent due to its simple structural properties that provide a better surface area with high absorption capacity. This comprehensive review gives a glimpse of the various green and other nanotechnologies used for wastewater and contaminated soil treatments.
Article
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In support of the implementation of the European Union (EU) Water Framework Directive (WFD), the European Commission (EC) Joint Research Centre (JRC) organized a laboratory and sampling intercomparison study for the chemical monitoring of polyaromatic hydrocarbons (PAHs), polybrominated diphenyl ethers (PBDEs), and nonylphenol and octylphenol (NP/OP), priority substances of the WFD, in river water. EU Member State laboratories were invited to analyze a standard solution with unknown concentration levels and a river-water extract, as well as a real water sample from the River Po (Italy). For the standard solution and the river-water extract, good agreement was achieved for five laboratories. Triple-quadrupole liquid chromatography with tandem mass spectrometry (LC-MS2) and gas chromatography with MS (GC-MS) with or without derivatization proved to be comparable methods for the analysis of NP and OP. Fluorescence detection can also be used to analyze NP and OP, but it is less specific. The results of the River Po water sample showed that some laboratories have problems in analyzing NP at concentration levels below 100 ng/L due to contamination of laboratory blanks. Plastics materials should not be used during extraction and sample preparation.
Article
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Pharmaceutical residues are environmental contaminants of recent concern and the requirements for analytical methods are mainly dictated by low concentrations found in aqueous and solid environmental samples. In the current article, a review of the liquid chromatography-tandem mass spectrometry (LC-MS/MS) based methods published so far for the determination of pharmaceuticals in the environment is presented. Pharmaceuticals included in this review are antibiotics, non-steroidal anti-inflammatory drugs, beta-blockers, lipid regulating agents and psychiatric drugs. Advanced aspects of current LC-MS/MS methodology, including sample preparation and matrix effects, are discussed.
Article
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The increasing worldwide contamination of freshwater systems with thousands of industrial and natural chemical compounds is one of the key environmental problems facing humanity. Although most of these compounds are present at low concentrations, many of them raise considerable toxicological concerns, particularly when present as components of complex mixtures. Here we review three scientific challenges in addressing water-quality problems caused by such micropollutants. First, tools to assess the impact of these pollutants on aquatic life and human health must be further developed and refined. Second, cost-effective and appropriate remediation and water-treatment technologies must be explored and implemented. Third, usage and disposal strategies, coupled with the search for environmentally more benign products and processes, should aim to minimize introduction of critical pollutants into the aquatic environment.
Article
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A survey of contamination of surface and drinking waters around Lake Maggiore in Northern Italy with polar anthropogenic environmental pollutants has been conducted. The target analytes were polar herbicides, pharmaceuticals (including antibiotics), steroid estrogens, perfluorooctanesulfonate (PFOS), perfluoroalkyl carboxylates (including perfluorooctanoate PFOA), nonylphenol and its carboxylates and ethoxylates (NPEO surfactants), and triclosan, a bactericide used in personal-care products. Analysis of water samples was performed by solid-phase extraction (SPE) then liquid chromatography–triple-quadrupole (tandem) mass spectrometry (LC–MS–MS). By extraction of 1-L water samples and concentration of the extract to 100 μL, method detection limits (MDLs) as low as 0.05–0.1 ng L−1 were achieved for most compounds. Lake-water samples from seven different locations in the Southern part of Lake Maggiore and eleven samples from different tributary rivers and creeks were investigated. Rain water was also analyzed to investigate atmospheric input of the contaminants. Compounds regularly detected at very low concentrations in the lake water included: caffeine (max. concentration 124 ng L−1), the herbicides terbutylazine (7 ng L−1), atrazine (5 ng L−1), simazine (16 ng L−1), diuron (11 ng L−1), and atrazine-desethyl (11 ng L−1), the pharmaceuticals carbamazepine (9 ng L−1), sulfamethoxazole (10 ng L−1), gemfibrozil (1.7 ng L−1), and benzafibrate (1.2 ng L−1), the surfactant metabolite nonylphenol (15 ng L−1), its carboxylates (NPE1C 120 ng L−1, NPE2C 7 ng L−1, NPE3C 15 ng L−1) and ethoxylates (NPEn Os, n = 3-17; 300 ng L−1), perfluorinated surfactants (PFOS 9 ng L−1, PFOA 3 ng L−1), and estrone (0.4 ng L−1). Levels of these compounds in drinking water produced from Lake Maggiore were almost identical with those found in the lake itself, revealing the poor performance of sand filtration and chlorination applied by the local waterworks.
Article
A survey was done in the river Po (Italy) to check for therapeutic drugs in the environment. A number of pharmaceuticals were selected for analysis on the basis of high consumption and excretion as parent compound in humans. Eight sampling stations along the rivers Po and Lambro made it possible to plot the patterns of contamination in a highly populated region with a large number of animal farms. Atenolol, lincomycin, erythromycin, clarithromycin, bezafibrate, and furosemide were present at all the sampling sites, and other drugs were found only in some. Concentrations ranged from 0.1 to 250 ng/L, and several drugs exceeded the trigger value (10 ng/L) suggested by recent documents from the European Agency for the Evaluation of Medicinal Products (EMEA), assessing environmental risks for these chemicals. The patterns of contamination showed differences among sub-basins which correlated with the presence of large human settlements and/or animal farms. The ratio of measured to predicted concentrations (MEC/PEC) allowed a gross division of the drugs into two groups. The first consisted of pharmaceuticals with a MEC/PEC in the range 0.01−0.3, where the ratio is probably determined by the environmental behavior and the extent of degradation of the molecule. The other group consisted of pharmaceuticals found at concentrations higher than those predicted (MEC/PEC > 1). In this group, which consists of drugs sold without prescription or for veterinary use, market justifications (sales load uncertainty) have more role than chemical properties and environmental fate in explaining the differences between measured and predicted environmental concentrations.
Article
13 pages, 5 tables, 6 figures. This paper describes development, optimization and validation of a method for the simultaneous determination of 29 multi-class pharmaceuticals using off line solid phase extraction (SPE) followed by liquid chromatography–triple quadrupole mass spectrometry (LC–MS–MS). Target compounds include analgesics and non-steroidal anti-inflammatories (NSAIDs), lipid regulators, psychiatric drugs, anti-histaminics, anti-ulcer agent, antibiotics and β-blockers. Recoveries obtained were generally higher than 60% for both surface and wastewaters, with exception of several compounds that yielded lower, but still acceptable recoveries: ranitidine (50%), sotalol (50%), famotidine (50%) and mevastatin (34%). The overall variability of the method was below 15%, for all compounds and all tested matrices. Method detection limits (MDL) varied between 1 and 30 ng/L and from 3 to 160 ng/L for surface and wastewaters, respectively. The precision of the method, calculated as relative standard deviation (R.S.D.), ranged from 0.2 to 6% and from 1 to 11% for inter and intra-day analysis, respectively. A detailed study of matrix effects was performed in order to evaluate the suitability of different calibration approaches (matrix-matched external calibration, internal calibration, extract dilution) to reduce analyte suppression or enhancement during instrumental analysis. The main advantages and drawbacks of each approach are demonstrated, justifying the selection of internal standard calibration as the most suitable approach for our study. The developed analytical method was successfully applied to the analysis of pharmaceutical residues in WWTP influents and effluents, as well as in river water. For both, river and wastewaters, the most ubiquitous compounds belonged to the group of anti-inflammatories and analgesics, antibiotics, the lipid regulators being acetaminophen, trimethoprim, ibuprofen, ketoprofen, atenolol, propranolol, mevastatin, carbamazepine and ranitidine the most frequently detected compounds. This work was financially supported by the European Union EMCO project (INCO-CT-2004-509188) and by the Spanish Ministerio de Ciencia y Tecnología (EVITA project – CTM2004-06265-C03-01).Waters Corporation (USA) and 1ST (UK) are gratefully acknowledged for providing the SPE cartridges. Merck (Germany) is acknowledged for providing the SPE cartridges and HPLC columns. R. Chaler and D. Fanjul are also acknowledged for their excellent assistance in LC–MS troubleshooting. Peer reviewed
Article
This biennial review covers developments in water analysis for emerging environmental contaminants over the period of October 2013-October 2015. Analytical Chemistry's policy is to limit reviews to a maximum of 250 significant references and to mainly focus on new trends. Therefore, only a small fraction of the quality research publications are discussed. The previous Water Analysis review (with Thomas Ternes) was published in 2014. This year, Susana Y. Kimura joined me to cover the section on Pharmaceuticals and Hormones. We welcome any comments you have on this Review (richardson.susan@sc.edu). Numerous abstracts were consulted before choosing the best representative ones to present here. Abstract searches were carried out using Web of Science, and in many cases, full articles were obtained. A table of acronyms is provided (Table 1) as a quick reference to the acronyms of analytical techniques and other terms discussed in this Review. Table 2 provides some useful websites.
Article
A new method, developed in an EC project (SMT4-CT96-2142) for the determination of 22 pesticides in drinking and related waters, has been used to analyze source and drinking water samples in the area of Barcelona (NE Spain). The procedure includes solid-phase extraction of water and subsequent analysis by GC-MS using few selected ions (SIR) in order to increase their sensitivity. The method was subjected to intra and interlaboratory tests and met the requirements of the EC Directive in terms of accuracy, precision and detection limit (0.025 microg/l range in water samples). A detailed analysis of the uncertainty sources of this method is included, which allows to estimate expanded uncertainties in the 10-20% range. The dominant sources of uncertainty are the solid-phase extraction procedure and the chromatographic quantification. Two triazine compounds, simazine and atrazine, are the main pesticides detected in wells of the Llobregat river and in water of the Ter river, respectively.
Article
To provide the first nationwide reconnaissance of the occurrence of pharmaceuticals, hormones, and other organic wastewater contaminants (OWCs) in water resources, the U.S. Geological Survey used five newly developed analytical methods to measure concentrations of 95 OWCs in water samples from a network of 139 streams across 30 states during 1999 and 2000. The selection of sampling sites was biased toward streams susceptible to contamination (i.e. downstream of intense urbanization and livestock production). OWCs were prevalent during this study, being found in 80% of the streams sampled. The compounds detected represent a wide range of residential, industrial, and agricultural origins and uses with 82 of the 95 OWCs being found during this study. The most frequently detected compounds were coprostanol (fecal steroid), cholesterol (plant and animal steroid), N,N-diethyltoluamide (insect repellant), caffeine (stimulant), triclosan (antimicrobial disinfectant), tri(2-chloroethyl)phosphate (fire retardant), and 4-nonylphenol (nonionic detergent metabolite). Measured concentrations for this study were generally low and rarely exceeded drinking-water guidelines, drinking-water health advisories, or aquatic-life criteria. Many compounds, however, do not have such guidelines established. The detection of multiple OWCs was common for this study, with a median of seven and as many as 38 OWCs being found in a given water sample. Little is known about the potential interactive effects (such as synergistic or antagonistic toxicity) that may occur from complex mixtures of OWCs in the environment. In addition, results of this study demonstrate the importance of obtaining data on metabolites to fully understand not only the fate and transport of OWCs in the hydrologic system but also their ultimate overall effect on human health and the environment.
Article
Although various single-concentration measurements of pharmaceuticals are available in the literature, detailed information on the variation over time of the concentration and the load in wastewater effluents and rivers and on the fate of these compounds in the aquatic environment are lacking. We measured the concentrations of six pharmaceuticals, carbamazepine, clofibric acid, diclofenac, ibuprofen, ketoprofen, and naproxen, in the effluents of three wastewater treatment plants (WWTPs), in two rivers and in the water column of Lake Greifensee (Switzerland) over a time period of three months. In WWTP effluents, the concentrations reached 0.95 microg/L for carbamazepine, 0.06 microg/L for clofibric acid, 0.99 microg/L for diclofenac, 1.3 microg/L for ibuprofen, 0.18 microg/L for ketoprofen, and 2.6 microg/L for naproxen. The relative importance in terms of loads was carbamazepine, followed by diclofenac, naproxen, ibuprofen, clofibric acid, and ketoprofen. An overall removal rate of all these pharmaceuticals was estimated in surface waters, under real-world conditions (in a lake), using field measurements and modeling. Carbamazepine and clofibric acid were fairly persistent. Phototransformation was identified as the main elimination process of diclofenac in the lake water during the study period. With a relatively high sorption coefficient to particles, ibuprofen might be eliminated by sedimentation. For ketoprofen and naproxen, biodegradation and phototransformation might be elimination processes. For the first time, quantitative data regarding removal rates were determined in surface waters under real-world conditions. All these findings are important data for a risk assessment of these compounds in surface waters.
Article
4-Alkylphenols, 4-alkylphenol ethoxylates, 4-alkylphenoxy carboxylates, bisphenol A, bisphenol F, 4-hydroxyacetophenon, 4-hydroxybenzoic acid and steroid hormones were analyzed in water samples of the River Elbe and its tributaries Schwarze Elster, Mulde, Saale, Havel and Schwinge. Additionally, freshly deposited sediments (FDS, composite samples) of the River Elbe and its tributaries were analyzed. The concentrations in water samples ranged from (in ng/l): bisphenol A 4 to 92, branched nonylphenol 13 to 87, branched nonylphenol ethoxylates <0.5 to 120, 4-tert. nonylphenoxy carboxylates <10 to 940 and 4-hydroxybenzoic acid 4 to 12. Steroid hormones were only detected in the Czech tributaries Jizera and Vltava in concentrations near the limit of quantification. In FDS samples the concentrations amounted to (in g/kg d.w.): bisphenol A 10-380, branched nonylphenol 27-430, branched nonylphenol ethoxylates 24-3700, nonylphenoxy carboxylates <50 and 4-hydroxybenzoic acid 23-4400. Increased bisphenol A concentrations were found in water and FDS samples taken from the Czech-German border at Schmilka and the mouth of the Schwinge (only water sample). According to studies conducted in the Elbe Estuary and the German Bight, the River Elbe must be considered as a major source of pollution for the North Sea in respect of the compounds analyzed. A comparison of bisphenol A concentrations, 4-alkylphenols and the corresponding ethoxylates analyzed in the River Elbe and its tributaries with those found in other German surface waters indicated a low level of contamination. The evaluation of the data based on LOEC-values indicated that the concentrations were well below the effectivity threshold for some 4-alkylphenols. According to recent ecotoxicological investigations, for example, with prosobranch snails, bisphenol A concentrations found in water samples of the River Elbe and its tributaries may well be detrimental to aquatic organisms. On the basis of the monitoring data and its implications for estrogenic potency the inclusion of bisphenol A in the list of priority substances (European Union Directive 2000/60/EC, Annex X) should be considered.
Article
Medicinal drugs were found to be ubiquitous in the river Elbe, its tributary the river Saale and in other tributaries at their points of entry into the Elbe. The distribution of concentration peaks along the investigated river stretches provides an indication that they are mainly due to the emission of treated waste water from municipal sewage treatment works. This leads to the conclusion that medicinal substances can be regarded as faecal indicators for water pollution caused by human activity. The main substances found in the Elbe in 1998 were diclofenac, ibuprofen and carbamazepine as well as various antibiotics and lipid regulators in the concentration range of <20-140 ng/l. The more thorough investigations carried out in 1999 and 2000 show that in addition to the drugs (phenazone, isopropyl-phenazone and paracetamol) metabolite concentrations contributed significantly to the total concentration of pharmaceuticals in the Elbe. The metamizole metabolites N-acetyl-4-aminoantipyrine (AAA) and N-formyl-4-aminoantipyrine (FAA) were found in concentrations from <20 to 939 ng/l. A multivariate statistical analysis revealed a high correlation in respect of the distribution of persistent substances. The metoprolol distribution throughout the Saale demonstrated that the tributaries cause either an increase (Weisse Elster, Unstrut, Ilm) or a reduction (Wipper, Bode) in the concentration, depending on the respective load of waste water. Wide scale sampling in Saxony during 2002 showed the ubiquitous occurrence of carbamazepine in surface waters. The ecotoxicological effects of this contamination cannot be assessed at present. This is due to the fact that no legal framework in respect of these medicinal drugs for human consumption has been established and therefore little research and no risk assessment has been carried out. Therefore it is urgently necessary to include at least the quantitatively most significant substances in the new assessment concept of the EC White Paper.
Article
Widespread use of perfluorooctane surfactants has led to ubiquitous presence of these chemicals in biological tissues. While perfluorooctane surfactants have been measured in blood and liver tissue samples of fish, birds, and mammals in the Great Lakes region, data for the aqueous concentrations of these compounds in the Great Lakes or other ambient waters is lacking. Sixteen Great Lakes water samples were analyzed for eight perfluorooctane surfactants. The monitored perfluorooctane surfactants were quantitatively determined using single quadrupole HPLC/MS and qualitatively confirmed using ion trap MS/MS. Additionally, PFOS was quantitatively confirmed using triple quadrupole LC/MS/MS. Concentrations of PFOS and PFOA in the two lakes ranged from 21-70 and 27-50 ng/L, respectively. Analysis also showed the presence of PFOS precursors, N-EtFOSAA (range of 4.2-11 ng/L) and FOSA (range of 0.6-1.3 ng/L), in all samples above the LOQ. PFOSulfinate, another precursor, was identified at six of eight locations with a concentration range, when present, of <2.2-17 ng/L. Other PFOS precursors, N-EtFOSE, PFOSAA, and N-EtFOSA were not observed at any of the sampling locations. These are the first reported concentrations of perfluorooctane surfactants in Great Lakes water and the first report of PFOS precursors in any water body.
Article
Perfluorinated acids (PFAs) and their salts have emerged as an important class of global environmental contaminants. Determination of sub-parts-per-trillion or parts-per-quadrillion concentrations of perfluorinated acids in aqueous media has been impeded by relatively high background levels arising from procedural or instrumental blanks. To understand the role of the oceans in the transport and fate of perfluorinated acids, methods to determine ultratrace levels of these compounds in seawater are needed. In this study, sources of procedural and instrumental blank contamination by perfluorinated acids have been identified and eliminated, to reduce background levels in blanks and thereby improve limits of quantitation. The method developed in this study is capable of detecting perfluorooctanesulfonate (PFOS), perfluorohexanesulfonate (PFHS), perfluorobutanesulfonate (PFBS), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), and perfluorooctanesulfonamide (PFOSA) at low pg/L levels in oceanic waters. PFOA is the major perfluorinated compound detected in oceanic waters, followed by PFOS. Further studies are being conducted to elucidate the distribution and fate of perfluorinated acids in oceans.
Article
An extensive study was carried out in the Netherlands on the occurrence of a number of estrogenic compounds in surface water, sediment, biota, wastewater, rainwater and on the associated effects in fish. Compounds investigated included natural and synthetic hormones, phthalates, alkylphenol(ethoxylate)s and bisphenol-A. The results showed that almost all selected (xeno-)estrogens were present at low concentrations in the aquatic environment. Locally, they were found at higher levels. Hormones and nonylphenol(ethoxylate)s were present in concentrations that are reportedly high enough to cause estrogenic effects in fish. Field surveys did not disclose significant estrogenic effects in male flounder (Platichthys flesus) in the open sea and in Dutch estuaries. Minor to moderate estrogenic effects were observed in bream (Abramis brama) in major inland surface waters such as lowland rivers and a harbor area. The prevalence of feminizing effects in male fish is largest in small regional surface waters that are strongly influenced by sources of potential hormone-disrupting compounds. High concentrations of plasma vitellogenin and an increased prevalence of ovotestes occurred in wild male bream in a small river receiving a considerable load of effluent from a large sewage treatment plant. After employing in vitro and in vivo bioassays, both in situ and in the laboratory, we conclude that in this case hormones (especially 17 alpha-ethynylestradiol) and possibly also nonylphenol(ethoxylate)s are primarily responsible for these effects.
Article
This paper presents the results of a survey of the wastewater effluent and surface waters of the lower river Tyne, UK. Samples were analysed by reversed-phase high-performance liquid chromatography-electrospray tandem mass spectrometry following solid phase extraction, for the presence of 13 pharmaceuticals selected from the priority lists of the UK Environment Agency and the Oslo and Paris Commission (OSPAR). The pharmaceutical compounds measured were acetyl-sulfamethoxazole, clofibric acid, clotrimazole, dextropropoxyphene, diclofenac, erythromycin, ibuprofen, mefenamic acid, paracetamol, propranolol, sulfamethoxazole, tamoxifen and trimethoprim. Of the wastewater treatment works (WTW) samples (n=9) analysed, all compounds except sulfamethoxazole and acetyl-sulfamethoxazole were detected at concentrations ranging from 11 to 69,570 ng l(-1) (in raw effluent). In the surface water samples (n=18), clotrimazole, dextropropoxyphene, erythromycin, ibuprofen, propranolol, tamoxifen and trimethoprim were detected at concentrations ranging from 4 to 2370 ng l(-1). Results of this study show that various pharmaceutical compounds are effectively reduced during their passage through a tertiary wastewater treatment works, whilst others are sufficiently persistent to occur in estuarine systems.
Article
This review evaluates and summarizes the results of long-term research projects, monitoring programs and published papers concerning the pollution of surface waters (rivers and lakes) of Greece by pesticides. Pesticide classes mostly detected involve herbicides used extensively in corn, cotton and rice production, organophosphorus insecticides as well as the banned organochlorines insecticides due to their persistence in the aquatic environment. The compounds most frequently detected were atrazine, simazine, alachlor, metolachlor and trifluralin of the herbicides, diazinon, parathion methyl of the insecticides and lindane, endosulfan and aldrin of the organochlorine pesticides. Rivers were found to be more polluted than lakes. The detected concentrations of most pesticides follow a seasonal variation, with maximum values occurring during the late spring and summer period followed by a decrease during winter. Nationwide, in many cases the reported concentrations ranged in low ppb levels. However, elevated concentrations were recorded in areas of high pesticide use and intense agricultural practices. Generally, similar trends and levels of pesticides were found in Greek rivers compared to pesticide contamination in other European rivers. Monitoring of the Greek water resources for pesticide residues must continue, especially in agricultural regions, because the nationwide patterns of pesticide use are constantly changing. Moreover, emphasis should be placed on degradation products not sufficiently studied so far.
Article
The occurrence of pharmaceutical and personal care products (PPCPs) was investigated in the Somes River. The aim of this study was to obtain a first overview about the contamination of Somes River (Transylvania) with PPCPs. The samples were preconcentrated by Solid Phase Extraction (SPE) procedures and analysed by GC/MS. A number of 15 compounds including pharmaceutics, metabolites, intermediates and musk fragrances were detected in concentration ranging from 30 ng/l to 10 microg/l. The detected pharmaceuticals are included in following therapeutic groups: analgesics, antiepileptics, psychiatric, stimulants, anticoagulants, antineoplastic and disinfectants.
Article
This work studies the presence of a total number of 44 substances found in waters of the Ebro river basin (Spain), all included in the Pesticides Control Network, whose purpose is to monitor diffuse pollution of surface waters caused by pesticides contained in some of the dangerous substances lists established in existing legislation and their high degree of use in the basin. Most of the pesticide sampling points are located in the sections of river that receive run-off waters from various agricultural areas shortly before opening out onto the main river (the Ebro), in areas of special agricultural importance. Water samples are subjected to a solid-liquid extraction as a previous step to their analysis by GC/MS (gas chromatography/mass spectrometry). Pesticides most frequently found and in greater concentrations in the waters of the Ebro river basin are 3,4-dichloroaniline, molinate, desethylatrazine, dimetoate, simazine, atrazine, metolachlor and chlorpyrifos. There are certain compounds that are not detected or their concentrations are below the quantification limit, such as 4-isopropylaniline, ametryn, beta-HCH, delta-HCH, aldrin, isodrin, dieldrin, heptachlor epoxide, endosulfan and endosulfan-sulfate. Diuron appears at specific points in some of the stations.
Article
This study presents a quantitative estimation of the analysis and fate of several emerging pollutants, some of them endocrine-disrupting compounds, in surface water samples collected at several locations along the Ter River and two of its tributaries. Influent and effluent waters and particulate matter from five sewage treatment plants (STP) that discharge into these rivers were also studied. The target compounds analyzed were: nonylphenol ethoxylates (NPEO), nonylphenol (NP), octylphenol (OP), bisphenol A (BPA), phthalates, alcohol ethoxylates (AEO) and benzothiazoles. Chemical analysis by liquid chromatography-mass spectrometry using an electrospray interface (LC-ESI-MS) revealed the presence of low amounts (between 0.06 and 17.5 microg L(-1)) of the target compounds NPE(1+2)O and NP, which were detected in 100% and 84% of the samples respectively. Maximum concentrations occurred in the STPs associated with the municipalities of Vic and Girona. From the fate and behavior data obtained for the various compounds analyzed in the STP influent and effluent, we can conclude that the STPs are effective at removing large amounts (more than 70%) of the compounds studied from the water.
Article
A method based on isotope dilution gas chromatography/mass spectrometry (GC/MS) with automated solid-phase extraction (SPE) is described for the analysis of 32 pesticides and metabolites in surface waters. This approach consist in the use of nine isotopically labelled representative pesticides as internal standards, which allows high accuracy (trueness and precision) and sensitivity for most analysed compounds, as it is required for isotope dilution-based methods. Uncertainties associated with pesticide determination in real samples were estimated using quality assurance/quality control (QA/QC) data. For most pesticides expanded uncertainty was below 40%, according to the commonly established requirements for analytical results. Ninety three Spanish surface waters collected in June-July and September-November 2004 were analysed. Concentration and occurrence of pesticides were evaluated. These parameters were higher in the summer than in the autumn period. In summer four pesticides were found in more than 50% of the analysed samples and four compounds were detected above the concentration level of 1 microg/l (atrazine, terbutylazine, 3,4-dichloroaniline and fenitrothion), while in autumn percentage of detection was below 50% for all pesticides and only one compound (terbutylazine) exceeded 1 microg/l.
Article
The effluents of eight municipal wastewater treatment plants (WWTP) in Western Europe were analyzed by liquid-chromatography-mass spectrometry for the occurrence of 36 polar pollutants, comprising household and industrial chemicals, pharmaceuticals, and personal care products. In a long-term study of the effluents of three WWTP over 10 months, sulfophenyl carboxylates and ethylene diamino tetraacetate (EDTA) were detected above 10 microg/L on average, while benzotriazoles, benzothiazole-2-sulfonate, diclofenac, and carbamazepine showed mean concentrations of 1-10 microg/L, followed by some flame retardants, naphthalene disulfonates, and personal care products in the range of 0.1-1 microg/L. Half of the determined compounds were not significantly removed in tertiary wastewater treatment. By dividing the effluent concentration of a compound by its relative removal in WWTP a water cycle spreading index (WCSI) was calculated for each compound. We propose that this index provides a measure for the potential of a polar compound to spread along a partially closed water cycle after discharge with municipal wastewater and to occur in raw waters used for drinking water production. Polar pollutants in surface water samples of different catchments showed increasing concentration for compounds with increasing WCSI.
Article
Barbiturates have been widely used as sedative hypnotics in the mid-1960s and since then mainly as veterinary drugs. To monitor their presence and fate in the aquatic environment, a method based on gas chromatography-mass spectrometry (GC-MS) has been developed to quantify butalbital, secobarbital, hexobarbital, aprobarbital, phenobarbital, and pentobarbital, all with a limit of detection (LOD) down to 1 ng/L. From the various investigated waste and surface water samples, barbiturates were only, but regularly detected in the Mulde, a tributary of the river Elbe in Germany at relevant concentrations up to several microg/L. Investigations of groundwater being affected with wastewater infiltration several decades ago also revealed a barbiturate pattern, indicating a strong recalcitrance of these drugs. To confirm this hypothesis, studies were carried out on biotic and abiotic degradation. Both, the biodegradability under aerobic conditions and hydrolysis did not show any degradation, implementing, that the investigated barbiturates, once released into the aquatic environment, show high stability over a long period of time.
Article
A set of three benzotriazole corrosion inhibitors was analyzed by liquid chromatography-mass spectrometry in wastewaters and in a partially closed water cycle in the Berlin region. Benzotriazole (BTri) and two isomers of tolyltriazole (TTri) were determined in untreated municipal wastewater with mean dissolved concentrations of 12 microg/L (BTri), 2.1 microg/L (4-TTri), and 1.3 microg/L (5-TTri). Removal in conventional activated sludge (CAS) municipal wastewater treatment ranged from 37% for BTri to insignificant removal for 4-TTri. In laboratory batch tests 5-TTri was mineralized completely and 4-TTri was mineralized to only 25%. This different behavior of the three benzotriazoles was confirmed by following the triazoles through a partially closed water cycle, into bank filtrate used for drinking water production, where BTri (0.1 microg/L) and 4-TTri (0.03 microg/ L) but no 5-TTri were detected after a travel time of several months. The environmental half-life appears to increase from 5-TTri over BTri to 4-TTri. Treatment of municipal wastewater by a lab-scale membrane bioreactor (MBR) instead of CAS improved the removal of BTri and 5-TTri but could not avoid their discharge. Almost complete removal was achieved by ozonation of the treatment plant effluent with 1 mg O3/mg DOC.
Article
A new method is presented for the quantitative determination of ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) from aqueous samples without an enrichment step. It consist of the formation of the Fe(III) complexes of EDTA and DTPA, liquid-chromatography with a volatile ion-pairing agent and determination by electrospray ionization-tandem mass spectrometry (ESI-MS/MS). Limits of quantification (LOQ) of 1.0 and 0.6 microgL(-1) for EDTA and DTPA were obtained, allowing the direct injection of most aqueous environmental samples without any preceding enrichment. With a more recent mass spectrometer, the LOQ could be further decreased by almost one order of magnitude. Parallel analysis of real samples by a standardized method employing enrichment, derivatization and GC-MS analysis yielded comparable results. The method was applied to the determination of both complexing agents in several wastewater, surface water and drinking water samples, showing that EDTA is an omnipresent contaminant in partially closed water cycles.
Article
Perfluorinated acids (PFAs) such as perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) are global environmental contaminants. The physicochemical properties of PFAs are unique in that they have high water solubilities despite the low reactivity of carbon-fluorine bond, which also imparts high stability in the environment. Because of the high water solubilities, the open-ocean water column is suggested to be the final sink for PFOS and PFOA. However, little is known on the distribution of PFAs in the oceans around the world. Here we describe the horizontal (spatial) and vertical distribution of PFAs in ocean waters worldwide. PFOS and PFOA concentrations in the North Atlantic Ocean ranged from 8.6 to 36pg l(-1) and from 52 to 338pg l(-1), respectively, whereas the corresponding concentrations in the Mid Atlantic Ocean were 13-73pg l(-1) and 67-439pg l(-1). These were completely different from the surface waters of the South Pacific Ocean and the Indian Ocean (overall range of <5-11pg l(-1) for PFOS and PFOA). Vertical profiles of PFAs in the marine water column were associated with the global ocean circulation theory. Vertical profiles of PFAs in water columns from the Labrador Sea reflected the influx of the North Atlantic Current in surface waters, the Labrador Current in subsurface waters, and the Denmark Strait Overflow Water in deep layers below 2000m. Striking differences in the vertical and spatial distribution of PFAs, depending on the oceans, suggest that these persistent acids can serve as useful chemical tracers to allow us to study oceanic transportation by major water currents. The results provide evidence that PFA concentrations and profiles in the oceans adhere to a pattern consistent with the global "Broecker's Conveyor Belt" theory of open ocean water circulation.
Article
C7-C11 perfluorinated carboxylates (PFACs) and perfluorooctansulfonate (PFOS) were analysed in selected stretches of the River Po and its major tributaries. Analyses were performed by solid-phase extraction (SPE) with Oasis HLB cartridges and methanol elution followed by LC-MS-MS detection using 13C-labelled internal standards. High concentration levels ( approximately 1.3 microg l(-1)) of perfluorooctanoate (PFOA) were detected in the Tánaro River close to the city Alessandria. After this tributary, levels between 60 and 337 ng l(-1) were measured in the Po River on several occasions. The PFOA concentration close to the river mouth in Ferrara was between 60 and 174 ng l(-1). Using the river discharge flow data in m3 s(-1) at this point (average approximately 920 m3 s(-1) for the year 2006), a mass load of approximately 0.3 kg PFOA per hour or approximately 2.6 tons per year discharged in the Adriatic Sea has been calculated. PFOS concentration levels in the Po River at Ferrara were approximately 10 ng l(-1).
Article
The discharge of C6-C9 perfluorinated carboxylates (PFCAs) from major European rivers was studied and employed to assess European emissions of these compounds. Water samples were collected close to the mouths of 14 major rivers including the Rhine, Danube, Elbe, Oder, Seine, Loire, and Po. PFCA concentrations were determined using LC-MS/MS and used together with the mean annual water flow to estimate the riverine discharge of the PFCAs. The highest concentration measured was 200 ng/L for perfluorooctanoate (PFOA) in the Po River. The Po accounted for two-thirds of the total PFOA discharge of all the rivers studied, suggesting a major industrial source of PFOA in the Po watershed. All other nonremote rivers showed PFOA concentrations in the lower ng/L range, which indicates that widely distributed sources are also significant contributors to PFOA emissions in Europe. The total discharge of PFOA from the European rivers was estimated to be 14 tonnes/year, which is in reasonable agreement with reported emissions estimates. However, the total riverine discharge of perfluorohexanoate (PFHxA) of 2.8 tonnes/year estimated in this study was three times greater than the reported global emissions estimate, suggesting that there are significant, as yet unidentified sources of this compound.
Article
Occurrence and fate of 17 antibiotics were investigated in the aqueous phase of river water under different hydrological conditions at 5 sampling locations in the Seine River inner estuary. The target analytes belonged to 4 groups: quinolones, sulfonamides, nitro-imidazoles and diaminopyrimidines. This six-month survey (from January to June 2006) showed that different compounds were occurring at individual concentrations reaching 544 ng L(-)(1) (sulfamethoxazole). All 17 compounds were detected at least once in the survey. Sulfamethoxazole was detected in every sample, and showed the highest concentrations. Norfloxacin and flumequine were found to be the most ubiquitous quinolones, with detection frequencies of 33 and 75% respectively at the most contaminated site (Poses). Investigations concerning the origins of this contamination were made by means of a longitudinal profile along the Seine River between Paris and Poses. It showed large inputs of norfloxacin, ofloxacin, trimethoprim and sulfamethoxazole from wastewater treatment plants, with an increase in norfloxacin and sulfamethoxazole concentrations of 84% and 70% respectively, both reaching 155 ng L(-)(1) in the river, downstream from a wastewater outlet. The detected compounds showed different dissipation patterns and behaviours under different hydrological conditions. Higher inputs of norfloxacin were found in low flow conditions, which were rapidly attenuated along the stream. In contrast, sulfamethoxazole inputs were increasing in high flow conditions, and dissipation of this compound was found to be slow. Similar behaviour was observed for the synergist trimethoprim. Flumequine was also frequently detected and its input increased during flood events.