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The accumulation of six pharmaceuticals of different therapeutic uses has been thoroughly investigated and compared between onion, spinach, and radish plants grown in six soil types. While neutral molecules (e.g., carbamazepine (CAR) and some of its metabolites) were efficiently accumulated and easily translocated to the plant leaves (onion > radish > spinach), the same for ionic (both anionic and cationic) molecules seems to be minor to moderate. The maximum accumulation of CAR crosses 38,000 (onion), 42,000 (radish), and 7000 (spinach) ng g−1 (dry weight) respectively, in which the most majority of them happened within the plant leaves. Among the metabolites, the accumulation of carbamazepine 10,11-epoxide (EPC — a primary CAR metabolite) was approximately 19,000 (onion), 7000 (radish), and 6000 (spinach) ng g−1 (dry weight) respectively. This trend was considerably similar even when all these pharmaceuticals applied together. The accumulation of most other molecules (e.g., citalopram, clindamycin, clindamycin sulfoxide, fexofenadine, irbesartan, and sulfamethoxazole) was restricted to plant roots, except for certain cases (e.g., clindamycin and clindamycin sulfoxide in onion leaves). Our results clearly demonstrated the potential role of this accumulation process on the entrance of pharmaceuticals/metabolites into the food chain, which eventually becomes a threat to associated living biota.

A conventional evaluation methodology for drinking water pollution focuses on analysing hundreds of compounds, usually by liquid chromatography–tandem mass spectrometry. High-resolution mass spectrometry allows comprehensive evaluation of all detected signals (compounds) based on their elemental composition, intensity, and numbers. We combined target analysis of 192 emerging micropollutants with nontarget (NT) full-scan/MS/MS methods to describe the impact of treatment steps in detail and assess drinking water treatment efficiency without compound identification. The removal efficiency based on target analytes ranged from − 143 to 97%, depending on the treatment section, technologies, and season. The same effect calculated for all signals detected in raw water by the NT method ranged between 19 and 65%. Ozonation increased the removal of micropollutants from the raw water but simultaneously caused the formation of new compounds. Moreover, ozonation byproducts showed higher persistence than products formed during other types of treatment. We evaluated chlorinated and brominated organics detected by specific isotopic patterns within the developed workflow. These compounds indicated anthropogenic raw water pollution but also potential treatment byproducts. We could match some of these compounds with libraries available in the software. We can conclude that passive sampling combined with nontargeted analysis shows to be a promising approach for water treatment control, especially for long-term monitoring of changes in technology lines because passive sampling dramatically reduces the number of samples and provides time-weighted average information for 2 to 4 weeks.

An upscaled passive sampler variant (diffusive hydrogel-based passive sampler; HPS) based on diffusive gradients in thin films for polar organic compounds (o-DGT) with seven times higher surface area (22.7 cm2) than a typical o-DGT sampler (3.14 cm2) was tested in several field studies. HPS performance was tested in situ within a calibration study in the treated effluent of a municipal wastewater treatment plant and in a verification study in the raw municipal wastewater influent. HPS sampled integratively for up to 14 days in the effluent, and 8 days in the influent. Sampling rates (Rs) were derived for 44 pharmaceuticals and personal care products, 3 perfluoroalkyl substances, 2 anticorro-sives, and 21 pesticides and metabolites, ranging from 6 to 132 mL d-1. Robustness and repeatability of HPS deterio-rated after exposures longer than 14 days due to microbial and physical damage of the diffusive agarose layer. In situ Rs values for the HPS can be applied to estimate the aqueous concentration of the calibrated polar organic compounds in wastewater within an uncertainty factor of four. When accepting this level of accuracy, the HPS can be applied for monitoring trends of organic micropollutants in wastewater.

The sorption of organic contaminants in soils and sediment is a crucial factor affecting their mobility in the vadose zone environment. The Freundlich sorption isotherms were evaluated for eleven micropollutants and eight soils. The highest Freundlich sorption coefficients, K

Determining pharmaceutical levels in fish plasma represents an increasingly valuable approach for environmental assessments of pharmaceuticals. These fish plasma observations are compared to human therapeutic plasma doses because of the high evolutionary conservation of many drug targets among vertebrates. In the present study, we initially identified highly variable information regarding plasma sampling practices in the literature and then tested the hypothesis that fish plasma levels of selected pharmaceuticals and per- and polyfluoroalkyl substances (PFASs) would not change with time to process samples from the field. After common carp were placed in a wastewater-fed pond for one month, we immediately sampled fish plasma nonlethally in the field or after transferring fish to clean water and held them under these conditions for either 3 or 20 h. We then quantitated pharmaceuticals in water, and pharmaceuticals and PFASs in plasma by LC-MSMS. Whereas plasma levels of most pharmaceuticals decreased even after 3 h that fish spent in clean water, plasma concentrations of the PFASs examined here remained stable over 20 h. Collectively, our examination of these time-dependent sampling approaches and associated findings highlight the importance of appropriate and consistent sampling for bioaccumulation studies, biomonitoring activities, and aquaculture product safety evaluations.

Various micropollutants (including pharmaceuticals, UV filters, cosmetics, cleansers, etc.), are increasingly being detected in the environment because of their partial or incomplete removal from wastewater in wastewater treatment plants (WWTPs). These compounds can be taken up by plants if treated wastewater is used for irrigation or if biosolids are used for soil amendment. Previous studies focused on this subject were usually performed under greenhouse conditions. Therefore, the aim of this study was to evaluate a behavior of studied compounds under natural climatic conditions. Experiment was carried out directly in the wastewater treatment plant, where nine raised beds were installed, which contained soils taken from topsoil of two soil types Arenosol (two beds) and Cambisol (seven beds). Either maize or a mixture of different vegetables (lettuce, carrot and onion) was grown in these beds. Of the seven beds with the Cambisol, one of the beds containing either maize or vegetables was irrigated with tap water and other pair of beds (maize or vegetables) was irrigated with treated wastewater (i.e., WWTP effluent). In another pair of beds (maize or vegetables), composted sludge from WWTP Three beds containing both types of biosolids were irrigated with tap water. Only vegetables were grown in the beds with the Arenosol, which were irrigated with either tap water or treated wastewater. Climatic data, irrigation doses, drainage water volumes, soil water contents and plant growth were monitored during the experiment. Selected compounds concentrations were measured in WWTP effluent, both biosolids, drainage water, soils, and plant tissues. Fifty five of 77 analyzed compounds were quantified in WWTP effluent. Main compounds were pharmaceuticals (e.g., telmisartan, gabapentin, diclofenac, carbamazepine, and its metabolites), UV filters (e.g., phenylbenzimidazole sulfonic acid) and compounds used in anticorrosive paints (e.g., 1H-benzotriazole). In the case of both biosolids, the dominant compounds were telmisartan, sertraline, trazodone, citalopram, diclofenac (i.e., pharmaceuticals) and 1H-benzotriazole. Uptake of different compounds by plants depended on a plant and properties of organic molecules, which affected their sorption in soils and mainly their ability to be taken up and translocated in plants. For instance, pharmaceuticals carbamazepine, gabapentin tramadol and venlafaxine were mainly found in lettuce leaves. Acknowledgement: Study was supported by the Ministry of Agriculture of the Czech Republic, project "The fate of selected micropollutants, which occur in treated water and sludge from wastewater treatment plants, in soil" (No. QK21020080) and partly also by the European Structural and Investment Funds, projects NutRisk (No. CZ.02.1.01/0.0/0.0/16_019/0000845).

Treated water from wastewater treatment plants that is increasingly used for irrigation may contain pharmaceuticals and, thus, contaminate soils. Therefore, this study focused on the impact of soil conditions on the root uptake of selected pharmaceuticals and their transformation in a chosen soil–plant system. Green pea plants were planted in 3 soils. Plants were initially irrigated with tap water. Next, they were irrigated for 20 days with a solution of either atenolol (ATE), sulfamethoxazole (SUL), carbamazepine (CAR), or all of these three compounds. The concentrations of pharmaceuticals and their metabolites [atenolol acid (AAC), N1-acetyl sulfamethoxazole (N1AS), N4-acetyl sulfamethoxazole (N4AS), carbamazepine 10,11-epoxide (EPC), 10,11-dihydrocarbamazepine (DHC), trans-10,11-dihydro-10,11-dihydroxy carbamazepine (RTC), and oxcarbazepine (OXC)] in soils and plant tissues were evaluated after harvest. The study confirmed high (CAR), moderate (ATE, AAC, SUL), and minor (N4AC) root uptake of the studied compounds by the green pea plants, nonrestricted transfer of the CAR species into the different plant tissues, and a very high efficiency in metabolizing CAR in the stems and leaves. The results showed neither a synergic nor competitive influence of the application of all compounds in the solution on their uptake by plants. The statistical analysis proved the negative relationships between the CAR sorption coefficients and the concentrations of CAR, EPC, and OXC in the roots (R = –0.916, –0.932, and –0.925, respectively) and stems (R = –0.837, –0.844, and –0.847, respectively).

Within this study, we were interested in the effects of wastewater on the development of antimicrobial resistance. Microorganisms can relatively promptly adapt to evolutionary pressures of the environment, including antibiotics. Therefore, we tested how the adaptability of the model microorganism Salmonella enterica is affected by wastewater full of pharmaceuticals, illicit drugs, and other micropollutants. Wastewater samples had been taken from effluent of hospitals and from wastewater treatment plant (WWTP) Petržalka influent and effluent. In these samples, presence of 38 substances was monitored. The highest concentration was observed in case of tramadol, citalopram, venlafaxine, cotinine, atenolol, valsartan, carbamazepine, azithromycin, and ciprofloxacin. According to this data, we focused also on individual pharmaceutical compounds presented in wastewater samples in elevated concentrations. Effect on resistance development of two pain relief medications (carbamazepine, tramadol), hypotensive medications (atenolol, valsartan), and the nicotine metabolite (cotinine) was also investigated. For this study, we employed concentrations presented in wastewater as well as in urine of patients and/or users. To determine the frequency of mutations leading to ciprofloxacin resistance, we applied the modified Ames test employing the strain Salmonella Typhimurium. Resistance index increased in the case of all wastewater samples from conventional hospitals where we observed a 1.22-1.69-fold increase of mutations leading to ciprofloxacin resistance. Tested compounds caused rise of resistance index in lower concentrations found in wastewater. The most significant increase of resistance index was detected after carbamazepine treatment.

Surface water quality monitoring programs have been developed to examine traditional contaminants, such as persistent organic pollutants (POPs). However, urbanization, which is increasing around the world, is increasing discharge of treated wastewater and raw sewage in many regions. Pharmaceuticals and their metabolites represent typical markers of such trajectories in urbanization. We selected an ongoing monitoring program, which was designed for routine surveillance of nonionizable POPs in different aquatic matrices, to examine the occurrence of 67 pharmaceuticals and their metabolites in water and multiple bioindicator matrices: benthic invertebrates, juvenile fish, and adult fish (plasma and muscle tissue) from ten river systems with varying levels of watershed development. In addition, we placed zebra mussels and passive samplers in situ for a fixed period. A statistically significant relationship between pharmaceutical levels in passive samplers and biota was found for caged zebra mussels and benthic invertebrates, while only a few pharmaceuticals were identified in fish matrices. Invertebrates, which have received relatively limited study for pharmaceutical bioaccumulation, accumulated more pharmaceuticals than fish, up to thirty different substances. The highest concentration was observed for sertraline in zebra mussels and telmisartan in benthic invertebrates (83 and 31 ng/g ww, respectively). Our results across diverse study systems indicate that ongoing surface water quality monitoring programs, which were originally designed for traditional organic pollutants, need to be revised to account for bioaccumulation dynamics of pharmaceuticals and other ionizable contaminants. Aquatic monitoring programs routinely examine accumulation of nonionizable organic pollutants; however, we identified that these efforts need to be revised to account for bioaccumulation of ionizable contaminants, which reached higher levels in invertebrates than in fish.

Non-target analysis (NTA) employing high-resolution mass spectrometry is a commonly applied approach for the detection of novel chemicals of emerging concern in complex environmental samples. NTA typically results in large and information-rich datasets that require computer aided (ideally automated) strategies for their processing and interpretation. Such strategies do however raise the challenge of reproducibility between and within different processing workflows. An effective strategy to mitigate such problems is the implementation of inter-laboratory studies (ILS) with the aim to evaluate different workflows and agree on harmonized/standardized quality control procedures. Here we present the data generated during such an ILS. This study was organized through the Norman Network and included 21 participants from 11 countries. A set of samples based on the passive sampling of drinking water pre and post treatment was shipped to all the participating laboratories for analysis, using one pre-defined method and one locally (i.e. in-house) developed method. The data generated represents a valuable resource (i.e. benchmark) for future developments of algorithms and workflows for NTA experiments., Measurement(s)chemical • drinking waterTechnology Type(s)high resolution mass spectrometry • non-target analysis • InterlaboratoryFactor Type(s)methodSample Characteristic - Environmentlaboratory environment Machine-accessible metadata file describing the reported data: 10.6084/m9.figshare.15028665

Traces of psychoactive substances have been found in freshwaters globally. Fish are chronically exposed to pollution at low concentrations. The changes of aggressive behaviour of chub (Squalius cephalus) were determined under the exposure to four psychoactive compounds (sertraline, citalopram, tramadol, methamphetamine) at environmentally relevant concentrations of 1 μg/L for 42 days. We tested whether (A) the behavioural effect of compounds varies within a single species; (B) there is a correlation between the individual brain concentration of the tested pollutants and fish aggression using the novel analysis of pollutants in brain; and (C) there is detectable threshold to effective pollutant concentration in brain. Behaviour and pollutant concentrations in brain were determined repeatedly (1st, 7th, 21st, 42nd and 56th days), including a two-week-long depuration period. The effect of particular compounds varied. Citalopram and methamphetamine generally increased the fish aggression, while no such effect was found after exposure to tramadol or sertraline. The longitudinal analysis showed an aggression increase after depuration, indicating the presence of withdrawal effects in methamphetamine- and tramadol-exposed fish. The analysis of pollutant concentration in brain revealed a positive linear relationship of citalopram concentration and aggression, while no such effect was detected for other compounds and/or their metabolites. Structural break analyses detected concentration thresholds of citalopram (1 and 3 ng/g) and sertraline (1000 ng/g) in brain tissue, from which a significant effect on behaviour was manifested. While the effect of sertraline was not detected using traditional approaches, there was a reduction in aggression after considering its threshold concentration in the brain. Our results suggest that pursuing the concentration threshold of psychoactive compounds can help to reduce false negative results and provide more realistic predictions on behavioural outcomes in freshwater environments, especially in the case of compounds with bioaccumulation potential such as sertraline.

Streptomyces sp. TR1341 was isolated from the sputum of a man with a history of lung and kidney tuberculosis, recurrent respiratory infections, and COPD. It produces secondary metabolites associated with cytotoxicity and immune response modulation. In this study, we complement our previous results by identifying the genetic features associated with the production of these secondary metabolites and other characteristics that could benefit the strain during its colonization of human tissues (virulence factors, modification of the host immune response, or the production of siderophores). We performed a comparative phylogenetic analysis to identify the genetic features that are shared by environmental isolates and human respiratory pathogens. The results showed a high genomic similarity of Streptomyces sp. TR1341 to the plant-associated Streptomyces sp. endophyte_N2, inferring a soil origin of the strain. Putative virulence genes, such as mammalian cell entry (mce) genes were not detected in the TR1341’s genome. The presence of a type VII secretion system, distinct from the ones found in Mycobacterium species, suggests a different colonization strategy than the one used by other actinomycete lung pathogens. We identified a higher diversity of genes related to iron acquisition and demonstrated that the strain produces ferrioxamine B in vitro. These results indicate that TR1341 may have an advantage in colonizing environments that are low in iron, such as human tissue.

Wastewater-based epidemiology is an additional indicator of drug use that is gaining reliability to complement the current established panel of indicators. The aims of this study were to: (i) assess spatial and temporal trends of population-normalized mass loads of benzoylecgonine, amphetamine, methamphetamine and 3,4-methylenedioxymethamphetamine (MDMA) in raw wastewater over 7 years (2011-17); (ii) address overall drug use by estimating the average number of combined doses consumed per day in each city; and (iii) compare these with existing prevalence and seizure data.Analysis of daily raw wastewater composite samples collected over 1 week per year from 2011 to 2017.Catchment areas of 143 wastewater treatment plants in 120 cities in 37 countries.Parent substances (amphetamine, methamphetamine and MDMA) and the metabolites of cocaine (benzoylecgonine) and of ΔBenzoylecgonine was the stimulant metabolite detected at higher loads in southern and western Europe, and amphetamine, MDMA and methamphetamine in East and North-Central Europe. In other continents, methamphetamine showed the highest levels in the United States and Australia and benzoylecgonine in South America. During the reporting period, benzoylecgonine loads increased in general across Europe, amphetamine and methamphetamine levels fluctuated and MDMA underwent an intermittent upsurge.The analysis of wastewater to quantify drug loads provides near real-time drug use estimates that globally correspond to prevalence and seizure data.

Antibiotic resistance is an emerging global health crisis, driven largely by overuse and misuse of antibiotics. However, there are examples in which the production of these antimicrobial agents has polluted the environment with active antibiotic residues, selecting for antibiotic resistant bacteria and the genes they carry. In this work, we have used shotgun metagenomics to investigate the taxonomic structure and resistance gene composition of sludge communities in a treatment plant in Croatia receiving wastewater from production of the macrolide antibiotic azithromycin. We found that the total abundance of antibiotic resistance genes was three times higher in sludge from the treatment plant receiving wastewater from pharmaceutical production than in municipal sludge from a sewage treatment plant in Zagreb. Surprisingly, macrolide resistance genes did not have higher abundances in the industrial sludge, but genes associated with mobile genetic elements such as integrons had. We conclude that at high concentrations of antibiotics, selection may favor taxonomic shifts towards intrinsically resistant species or strains harboring chromosomal resistance mutations rather than acquisition of mobile resistance determinants. Our results underscore the need for regulatory action also within Europe to avoid release of antibiotics into the environment.

Various types of micropollutants, e.g., pharmaceuticals and their metabolites and resistant strains of pathogenic microorganisms, are usually found in hospital wastewaters. The aim of this paper was to study the presence of 74 frequently used pharmaceuticals, legal and illegal drugs, and antibiotic-resistant bacteria in 5 hospital wastewaters in Slovakia and Czechia and to compare the efficiency of several advanced oxidations processes (AOPs) for sanitation and treatment of such highly polluted wastewaters. The occurrence of micropollutants and antibiotic-resistant bacteria was investigated by in-line SPE-LC-MS/MS technique and cultivation on antibiotic and antibiotic-free selective diagnostic media, respectively. The highest maximum concentrations were found for cotinine (6700 ng/L), bisoprolol (5200 ng/L), metoprolol (2600 ng/L), tramadol (2400 ng/L), sulfamethoxazole (1500 ng/L), and ranitidine (1400 ng/L). In the second part of the study, different advanced oxidation processes, modified Fenton reaction, ferrate(VI), and oxidation by boron-doped diamond electrode were tested in order to eliminate the abovementioned pollutants. Obtained results indicate that the modified Fenton reaction and application of boron-doped diamond electrode were able to eliminate almost the whole spectrum of selected micropollutants with efficiency higher than 90%. All studied methods achieved complete removal of the antibiotic-resistant bacteria present in hospital wastewaters.

Drug consumption in individual cities, regions, and at various music events and festivals across the EU has generally been monitored via questionnaires, patients' medical data, and police reports. However, an overview of drug consumption obtained from these methods can be negatively affected by various subjective factors. We aimed to investigate an association between levels of target drugs in wastewater, music genres, and festival courses. The occurrence of illicit drugs, their metabolites, and psychoactive compounds was investigated in the influent of six wastewater treatment plants in the Czech and Slovak Republic during seven large-scale music festivals from different music genres: metal, rock, pop, country and folk, ethnic, multi-genre, dance, and trance. The total number of participants included >130,000 active festival attendees. The association between music genre and illicit drug and/or psychoactive pharmaceutical consumptions is discussed on the basis of the results obtained through wastewater analyses. The observed trend was similar to worldwide published data with a specific local phenomenon of methamphetamine prevalence that did not significantly change between music events. Increased specific loads of cocaine (measured as its metabolite benzoylecgonine) and Ecstasy, along with some cannabis, were mainly observed during pop/rock and dance music festivals. However, there was no significant increase observed in the specific loads of all monitored psychoactive pharmaceuticals. This study demonstrates that the abuse of some illicit drugs is closely associated with specific music preferences.

Soils can be contaminated by pharmaceuticals. The aim of this study was to evaluate the impact of soil conditions (influencing sorption and persistence of pharmaceuticals in soils) and plant type on the root uptake of selected pharmaceuticals and their transformation in plant-soil systems. Four plants (lamb's lettuce, spinach, arugula, radish) planted in 3 soils were irrigated for 20 days (26) with water contaminated by one of 3 pharmaceuticals (carbamazepine, atenolol, sulfamethoxazole) or their mixture. The concentrations of pharmaceuticals and their metabolites in soils and plant tissues were evaluated after the harvest. Sulfamethoxazole and atenolol dissipated rapidly from soils. The larger concentrations of both compounds and an atenolol metabolite were found in roots than in leaves. Sulfamethoxazole metabolites were below the limits of quantifications. Carbamazepine was stable in soils, easily uptaken, accumulated, and metabolized in plant leaves. The efficiency of radish and arugula (both family Brassicaceae) in metabolizing was very low contrary to the high and moderate efficiencies of lamb's lettuce and spinach, respectively. Compounds' transformations mostly masked the soil impact on their accumulation in plant tissues. The negative relationships were found between the carbamazepine sorption coefficients and its concentrations in roots of radish, lamb's lettuce, and spinach.

Pharmaceutical and illicit drug residues in sewage sludge may present important risks following direct application to agricultural soils, potentially resulting in uptake by plants. Leaching/desorption tests were performed on different types of stabilized sewage sludge originating from multiple treatment technologies in the Slovak Republic. Acid rain and base-rich condition of soil with different pH conditions were simulated to model the effect of widely varying pH (pH 2, 4, 7, 9, and 12) on the leaching/desorption of pharmaceuticals and illicit drugs. Twenty-nine of 93 target analytes were found above the limit of quantification in sludge or associated leachates. Total desorbed amounts of pharmaceuticals and illicit drugs ranged from 810 to 4000 µg/kg, and 110 to 3600 µg/kg of the dry mass of anaerobic and aerobic sludge, respectively. Desorbed fractions were calculated as these values are normalized to initial sludge concentration and, therefore, were more suitable for qualitative description of the behavior of individual compounds. Using principal component analysis, qualitative analysis of the desorbed fraction confirmed the differences among sludge types, pharmaceuticals, and desorption pH. Desorbed fractions could not be related to the octanol/water distribution coefficient. Desorbed fractions also did not reflect the expected ionization of studied molecules unless converted into their relative values. Generally, the lowest mobility was observed within the environmentally relevant pH range of 4-9, and high pH generally resulted in high desorption, especially in anaerobically stabilized sludges.

Treated wastewater ponds (TWPs) serve as recipients and passive tertiary treatment mediators for recycled water. These nutrient-rich habitats are increasingly utilised in aquaculture, nevertheless multiple loads of various contaminants with adverse effects on aquatic fauna, including fish, have been recorded. In the present study, we investigated the effects of fish transfer in response to altered levels of pollution on liver metabolic profiles and tissue-specific oxidative stress biomarkers during short- and long-term exposure. In a field experiment, common carp (Cyprinus carpio) originating in severely polluted TWP were restocked after one year to a reference pond with a background pollutant concentration typical of the regional river. In contrast, fish that originated in the reference pond were restocked to TWP. Fish were sampled 0, 7, 14, 60, and 180 days after restocking and fish liver, kidney, intestine, and gill tissues were subjected to biomarker analysis. Pharmaceutically active compounds (PhACs) and metabolic profiles were determined in fish liver using liquid chromatography high-resolution mass spectrometry (LC-HRMS). Fish transferred from reference to polluted pond increased the antioxidant response and absorbed PhACs into metabolism within seven days. Fish liver metabolic profiles were shifted rapidly, but after 180 days to a lesser extent than profiles in fish already adapted in polluted water. Restocked fish from polluted to reference pond eliminated PhACs during the short phase within 14 days, and the highest antioxidant response accompanied the depuration process. Numerous elevated metabolic compounds persisted in such exposed fish for at least 60 days. The period of two weeks was suggested as sufficient for PhACs depuration, but more than two months after restocking is needed for fish to stabilise their metabolism. This study contributed to determining the safe handling with marketed fish commonly restocked to wastewaters and clarified that water pollution irreversibly altered fish metabolic profile.

Zayandeh Rood river is the most important river in central Iran supplying water for a variety of uses including drinking water for approximately three million inhabitants. The study aimed to investigate the quality of water concerning the presence of pharmaceutical active compounds (PhACs) and hormonelike compounds, which have been only poorly studied in this region. Sampling was performed at seven sites along the river (from headwater sites to downstream drinking water source, corresponding drinking water, and treated wastewater) affected by wastewater effluents, specific drought conditions, and high river-water demand. The targeted and nontargeted chemical analyses and in vitro bioassays were used to evaluate the presence of PhACs and hormonelike compounds in river water. In the samples, 57 PhACs and estrogens were detected with LC-MS/MS with the most common and abundant compounds valsartan, carbamazepine, and caffeine present in the highest concentrations in the treated wastewater in the concentrations of 8.4, 19, and 140 μg/L, respectively. A battery of in vitro bioassays detected high estrogenicity, androgenicity, and AhR-mediated activity (viz., in treated wastewater) in the concentrations 24.2 ng/L, 62.2 ng/L, and 0.98 ng/L of 17β-estradiol, dihydrotestosterone and 2,3,7,8-TCDD equivalents, respectively. In surface water samples, estrogenicity was detected in the range of

Tramadol is a widely used analgesic with additional antidepressant and anxiolytic effects. This compound has been reported in continental waters reaching concentrations of µg/L as a consequence of its inefficient removal in sewage treatment plants and increasing use over time. In this study, European chubs (Squalius cephalus) were exposed to 1 µg/L of tramadol in water for 42 days with a subsequent 14 days of depuration. Our results revealed that chubs exposed to this analgesic underwent changes in their behaviour as compared to the control group. The behavioural outcome was also influenced by the individual concentration of tramadol in brain tissue. In particular, experimental fish presented anxiolytic-like effects, characterized by less bold and less social individuals. Exposed animals were less frequently out of the shelter and moved a shorter distance, indicating that they explored the new environment less during the boldness test. In the novel object recognition experiment, although they distinguished the new item, they examined it less and displayed a reduced activity. Shoal cohesion was disrupted as observed in an increased distance between individuals. After the depuration phase, this alteration remained whereas the boldness effect disappeared. Moreover, the degree of behavioural changes was correlated with the concentration of the substance in brain. According to our findings, chronic presence of tramadol in the environment can impact the fitness of exposed aquatic fauna by altering evolutionary crucial behaviours.

Food contamination is a major worldwide risk for human health. Dynamic plant uptake of pollutants from contaminated environments is the preferred pathway into the human and animal food chain. Mechanistic models represent a fundamental tool for risk assessment and the development of mitigation strategies. However, difficulty in obtaining comprehensive observations in the soil-plant continuum hinders their calibration, undermining their generalizability and raising doubts about their widespread applicability. To address these issues, a Bayesian probabilistic framework is used, for the first time, to calibrate and assess the predictive uncertainty of a mechanistic soil-plant model against comprehensive observations from an experiment on the translocation of carbamazepine in green pea plants. Results demonstrate that the model can reproduce the dynamics of water flow and solute reactive transport in the soil-plant domain accurately and with limited uncertainty. The role of different physicochemical processes in bioaccumulation of carbamazepine in fruits is investigated through Global Sensitivity Analysis, which shows how soil hydraulic properties and soil solute sorption regulate transpiration streams and bioavailability of carbamazepine. Overall, the analysis demonstrates the usefulness of mechanistic models and proposes a comprehensive numerical framework for their assessment and use.

To gain a better understanding of which pharmaceuticals could pose a risk to fish, 94 pharmaceuticals representing 23 classes were analyzed in blood plasma from wild bream, chub, and roach captured at 18 sites in Germany, the Czech Republic and the UK, respectively. Based on read across from humans, we evaluated the risks of pharmacological effects occurring in the fish for each measured pharmaceutical. Twenty-three compounds were found in fish plasma, with the highest levels measured in chub from the Czech Republic. None of the German bream had detectable levels of pharmaceuticals, whereas roach from the Thames had mostly low concentrations. For two pharmaceuticals, four individual Czech fish had plasma concentrations higher than the concentrations reached in the blood of human patients taking the corresponding medication. For nine additional compounds, determined concentrations exceeded 10% of the corresponding human therapeutic plasma concentration in 12 fish. The majority of the pharmaceuticals where a clear risk for pharmacological effects was identified targets the central nervous system. These include e.g. flupentixol, haloperidol, and risperidone, all of which have the potential to affect fish behavior. In addition to identifying pharmaceuticals of environmental concern, the results emphasize the value of environmental monitoring of internal drug levels in aquatic wildlife, as well as the need for more research to establish concentration-response relationships.

Illicit drug abuse presents pervasive adverse consequences for human societies around the world. Illicit drug consumption also plays an unexpected role in contamination of aquatic ecosystems that receive wastewater discharges. Here, we show that methamphetamine, considered as one of the most important global health threats, causes addiction and behavior alteration of brown trout Salmo trutta at environmentally relevant concentrations (1 µg l−1). Altered movement behavior and preference for methamphetamine during withdrawal were linked to drug residues in fish brain tissues and accompanied by brain metabolome changes. Our results suggest that emission of illicit drugs into freshwater ecosystems causes addiction in fish and modifies habitat preferences with unexpected adverse consequences of relevance at the individual and population levels. As such, our study identifies transmission of human societal problems to aquatic ecosystems.

With increasing population growth and climate change, de facto reuse practices are predicted to increase globally. We investigated a longitudinal gradient within the Uhlava River, a representative watershed, where de facto reuse is actively occurring, during Fall and Spring seasons when instream flows vary. We observed human pharmaceutical levels in the river to continuously increase from the mountainous areas upstream to downstream locations and a potable intake location, with the highest concentrations found in small tributaries. Significant relationship was identified between mass flow of pharmaceuticals and the size of human populations contributing to wastewater treatment plant discharges. Advanced ozonation and granular activated carbon filtration effectively removed pharmaceuticals from potable source waters. We observed a higher probability of encountering a number of targeted pharmaceuticals during colder Spring months when stream flows were elevated compared to warmer conditions with lower flows in the Fall despite a dilution paradigm routinely applied for surface water quality assessment and management efforts. Such observations translated to greater water quality hazards during these higher Spring flows. Future water monitoring efforts should account for periods when higher chemical uses occur, particularly in the face of climate change for regions experiencing population growth and de facto reuse.

POCIS is the most widely applied passive sampler of polar organic substances, because it was one of the first commercially available samplers for that purpose on the market, but also for its applicability for a wide range of substances and conditions. Its main weakness is the variability of sampling performance with exposure conditions. In our study we took a pragmatic approach and performed in situ calibration for a set of 76 pharmaceuticals and their metabolites in five sampling campaigns in surface water, covering various temperature and flow conditions. In individual campaigns, RS were calculated for up to 47 compounds ranging from 0.01 to 0.63 L d−1, with the overall median value of 0.10 L d−1. No clear changes of RS with water temperature or discharge could be found for any of the investigated substances. The absence of correlation of experimental RS with physical-chemical properties in combination with the lack of mechanistic understanding of compound uptake to POCIS implies that practical estimation of aqueous concentrations from uptake in POCIS depends on compound-specific experimental calibration data. Performance of POCIS was compared with grab sampling of water in seven field campaigns comprising multiple sampling sites, where sampling by both methods was done in parallel. The comparison showed that for 25 of 36 tested compounds more than 50% of POCIS-derived aqueous concentrations did not differ from median of grab sampling values more than by a factor of 2. Further, for 30 of 36 compounds, more than 80% of POCIS data did not differ from grab sampling data more than by a factor of 5. When accepting this level of accuracy, in situ derived sampling rates are sufficiently robust for application of POCIS for identification of spatial and temporal contamination trends in surface waters.

Recent state-of-the-art methods developed for the analysis of polar xenobiotics from different types of biological matrices usually employ liquid chromatography with mass spectrometry. However, there are limitations when a small amount of sample mass is available. For example, individual benthic invertebrates or fish tissue samples often weigh less than 100 mg (e.g., brain, liver) but are necessary to understand environmental fate and bioaccumulation dynamics. We developed ultra-fast methods based on a direct sample introduction technique. This included coupling laser diode thermal desorption with atmospheric pressure chemical ionization mass spectrometry (LDTD-APCI-MS). We then quantitated a common selective serotonin reuptake inhibitor (citalopram) in brain tissues of individual juvenile fish after in vivo exposure to environmentally relevant concentration. Two mass spectrometric methods based on low (LDTD-APCI-triple quadrupole (QqQ)-MS/MS) and high (LDTD-APCI-high-resolution product scan (HRPS)) resolutions were developed and evaluated. Individual instrument conditions were optimized to achieve an accurate and robust analytical method with minimum sample preparation requirements. We achieved very good recovery (97–108%) across the range of 1–100 ng g−1 for LDTD-APCI-HRPS. LDTD-APCI-QqQ-MS/MS showed poorer performance due to interferences from the matrix at the lowest concentration level. LDTD-APCI ionization was successfully validated for analysis of non-filtered sample extracts. Evaluation of final methods was performed for a set of real fish brain samples, including comparison of LDTD-APCI-HRPS with a previously validated LC-heated electrospray ionization-HRPS method. This new LDTD-APCI-HRPS method avoids the chromatographic step and provides important benefits such as analysis of limited sample masses, lower total sample volume (typically μL), and reduction in analysis time per sample run to a few seconds.