► Simultaneous determination of 81 pharmaceuticals and some metabolites. ► Speed-up of sample preparation is achieved. ► High sample throughput and high sensitivity are achieved. ► IDA and library ...searching is a powerful tool for the confirmation of positive findings. ► Levels for carbamazepine metabolites are more prominent than the parent compound.
The present work describes the development of an analytical method, based on automated off-line solid phase extraction (SPE) followed by ultra-high-performance liquid chromatography coupled to quadrupole linear ion trap tandem mass spectrometry (UPLC-QqLIT) for the determination of 81 pharmaceutical residues, covering various therapeutic groups, and some of their main metabolites, in surface and treated waters (influent and effluent wastewaters, river, reservoir, sea and drinking water). For unequivocal identification and confirmation, two selected reaction monitoring (SRM) transitions per compound are monitored. Quantification is performed by the internal standard approach, indispensable to correct matrix effects. Moreover, to obtain an extra tool for confirmation of positive findings, an information dependent acquisition (IDA) experiment was performed, with SRM as survey scan and an enhanced product ion (EPI) scan as dependent scan. Compound identification was carried out by library search, matching the EPI spectra achieved at one fixed collision energy with those present in a library. The main advantages of the method are automation and speed-up of sample preparation by the reduction of extraction volumes for some matrices, the fast separation of a big number of pharmaceuticals, its high sensitivity (limits of detection in the low ng/L range), selectivity, due to the use of tandem mass spectrometry, reliability since a significant number of isotopically labeled compounds are used as internal standards for quantification and finally, the analysis of tap, reservoir and sea waters, since information about occurrence of pharmaceuticals in these matrices is still sparse. As part of the validation procedure, the method developed was applied to the analysis of pharmaceutical residues in waste and surface waters from different sites in Catalonia (North East of Spain).
► Simultaneous determination of 53 antibiotics and some metabolites. ► High sample throughput (fast sample preparation and chromatographic separation). ► High sensitivity by using advanced mass ...spectrometry. ► Good analytical performances for β-lactam antibiotics. ► Analysis of antibiotics in hospital wastewaters.
The present work describes the development of a fast and robust analytical method for the determination of 53 antibiotic residues, covering various chemical groups and some of their metabolites, in environmental matrices that are considered important sources of antibiotic pollution, namely hospital and urban wastewaters, as well as in river waters. The method is based on automated off-line solid phase extraction (SPE) followed by ultra-high-performance liquid chromatography coupled to quadrupole linear ion trap tandem mass spectrometry (UHPLC–QqLIT). For unequivocal identification and confirmation, and in order to fulfill EU guidelines, two selected reaction monitoring (SRM) transitions per compound are monitored (the most intense one is used for quantification and the second one for confirmation). Quantification of target antibiotics is performed by the internal standard approach, using one isotopically labeled compound for each chemical group, in order to correct matrix effects. The main advantages of the method are automation and speed-up of sample preparation, by the reduction of extraction volumes for all matrices, the fast separation of a wide spectrum of antibiotics by using ultra-high-performance liquid chromatography, its sensitivity (limits of detection in the low ng/L range) and selectivity (due to the use of tandem mass spectrometry) The inclusion of β-lactam antibiotics (penicillins and cephalosporins), which are compounds difficult to analyze in multi-residue methods due to their instability in water matrices, and some antibiotics metabolites are other important benefits of the method developed. As part of the validation procedure, the method developed was applied to the analysis of antibiotics residues in hospital, urban influent and effluent wastewaters as well as in river water samples.
The occurrence and removal of 49 antibiotics and 11 selected antibiotic resistance genes (ARGs) were investigated in 2 vertical subsurface flow (VF) constructed wetlands (1.5 m2 each): an unsaturated ...(UVF) unit and a partially saturated (SVF) unit (0.35 m saturated out of 0.8 m) operating in parallel and treating urban wastewater. Thirteen antibiotics were detected in influent wastewater, 6 of which were present in all samples. The SVF showed statistical significance on the removal of 4 compounds (namely ciprofloxacin, ofloxacin, pipemidic acid and azithromycin), suggesting that the wider range of pH and/or redox conditions of this configuration might promote the microbial degradation of some antibiotics. In contrast, the concentration of the latter (except pipemidic acid) and also clindamycin was higher in the effluent than in the influent of the UVF. Five ARGs were detected in influent wastewater, sul1 and sul2, blaTEM, ermB and qnrS. All of them were detected also in the biofilm of both wetlands, except qnrS. Average removal rates of ARGs showed no statistical differences between both wetland units, and ranged between 46 and 97% for sul1, 33 and 97% for sul2, 9 and 99% for ermB, 18 and 97% for qnrS and 11 and 98% for blaTEM.
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•The fate of antibiotics and ARGs in vertical flow constructed wetlands was studied.•Saturated and partially saturated conditions were compared.•Removal efficiency was generally low and variable for ARGs.•Average removals of ARGs showed no statistical differences between both wetlands.•The partially saturated wetland yielded significantly lower abundances of ARGs.
A multitude of pharmaceuticals enter surface waters via discharges of wastewater treatment plants (WWTPs), and many raise environmental and health concerns. Chemical fate models predict their ...concentrations using estimates of mass loading, dilution and in-stream attenuation. However, current comprehension of the attenuation rates remains a limiting factor for predictive models. We assessed in-stream attenuation of 75 pharmaceuticals in 4 river segments, aiming to characterize in-stream attenuation variability among different pharmaceutical compounds, as well as among river segments differing in environmental conditions. Our study revealed that in-stream attenuation was highly variable among pharmaceuticals and river segments and that none of the considered pharmaceutical physicochemical and molecular properties proved to be relevant in determining the mean attenuation rates. Instead, the octanol–water partition coefficient (Kow) influenced the variability of rates among river segments, likely due to its effect on sorption to sediments and suspended particles, and therefore influencing the balance between the different attenuation mechanisms (biotransformation, photolysis, sorption, and volatilization). The magnitude of the measured attenuation rates urges scientists to consider them as important as dilution when aiming to predict concentrations in freshwater ecosystems.
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•In-stream attenuation was highly variable among pharmaceuticals and river segments.•Kow influenced attenuation through effect on sorption to sediments.•Likely coupling between pharmaceuticals and phosphorus attenuation.•In-stream attenuation as important as dilution to explain concentrations.
Recent technological developments have increased the number of variables being monitored in lakes and reservoirs using automatic high frequency monitoring (AHFM). However, design of AHFM systems and ...posterior data handling and interpretation are currently being developed on a site-by-site and issue-by-issue basis with minimal standardization of protocols or knowledge sharing. As a result, many deployments become short-lived or underutilized, and many new scientific developments that are potentially useful for water management and environmental legislation remain underexplored. This Critical Review bridges scientific uses of AHFM with their applications by providing an overview of the current AHFM capabilities, together with examples of successful applications. We review the use of AHFM for maximizing the provision of ecosystem services supplied by lakes and reservoirs (consumptive and non consumptive uses, food production, and recreation), and for reporting lake status in the EU Water Framework Directive. We also highlight critical issues to enhance the application of AHFM, and suggest the establishment of appropriate networks to facilitate knowledge sharing and technological transfer between potential users. Finally, we give advice on how modern sensor technology can successfully be applied on a larger scale to the management of lakes and reservoirs and maximize the ecosystem services they provide.
Antibiotic resistance represents a growing global health concern due to the overuse and misuse of antibiotics. There is, however, little information about how the selective pressure of clinical ...antibiotic usage can affect environmental communities in aquatic ecosystems and which bacterial groups might be responsible for dissemination of antibiotic resistance genes (ARGs) into the environment. In this study, chemical and biological characterization of water and sediments from three water supply reservoirs subjected to a wide pollution gradient allowed to draw an accurate picture of the concentration of antibiotics and prevalence of ARGs, in order to evaluate the potential role of ARGs in shaping bacterial communities, and to identify the bacterial groups most probably carrying and disseminating ARGs. Results showed significant correlation between the presence of ARG conferring resistance to macrolides and the composition of bacterial communities, suggesting that antibiotic pollution and the spreading of ARG might play a role in the conformation of bacterial communities in reservoirs. Results also pointed out the bacterial groups Actinobacteria and Firmicutes as the ones probably carrying and disseminating ARGs. The potential effect of antibiotic pollution and the presence of ARGs on the composition of bacterial communities in lacustrine ecosystems prompt the fundamental question about potential effects on bacterial-related ecosystem services supplied by lakes and reservoirs.
•Antibiotics and prevalence of antibiotic resistance genes in reservoirs•No clear associations between antibiotic occurrence and resistance genes•Composition of microbial communities explained by the presence of resistance genes•Actinobacteria and Firmicutes associated to the presence of resistance genes
In this study, a 1200L outdoor pilot scale microalgal photobioreactor (PBR) was used for toilet wastewater (WW) treatment and evaluate its ability to remove pharmaceutically active compounds (PhACs). ...The PBR was operated at two different hydraulic retention times (HRTs), which were 8 and 12days, during Period I (September–October) and Period II (October–December), respectively. Algal biomass concentrations varied by operating period because of seasonal changes. Nutrients (ammonia, nitrogen and total phosphorous) and chemical oxygen demand (COD) were monitored and efficiently removed in both periods (>80%), attaining the legislation limits. At the theoretical hydraulic steady state in both periods, pharmaceutical removal reached high levels (>48%). Two harvesting techniques were applied to the PBR microalgae effluent. Gravity sedimentation was efficient for biomass removal (>99% in 7min) in Period I when large particles, flocs and aggregates were present. In contrast, a longer sedimentation time was required when biomass was mainly composed of single cells (88% clarification in a 24h in Period II). The second harvesting technique investigated was the co-pelletization of algal biomass with the ligninolytic fungus Trametes versicolor, attaining >98% clarification for Period II biomass once pellets were formed. The novel technology of co-pelletization enabled the complete harvesting of single algae cells from the liquid medium in a sustainable way, which benefits the subsequent use of both biomass and the clarified effluent.
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•A pilot microalgal photobioreactor was successfully operated for wastewater treatment.•The microalgal system was able to operate under various regimes and seasonal periods.•The microalgal system could remove 30–80% of pharmaceutically active compounds.•Fungal co-pelletization was an efficient harvesting technique in effluent clarification.
Wastewater-based epidemiology (WBE) can be a useful complementary approach to assess human exposure to potentially harmful chemicals, including those from personal care and household products. In ...this work, a fully automated multiresidue method, based on on-line solid-phase extraction liquid chromatography – tandem mass spectrometry, was developed for the determination of 27 biomarkers of human exposure to selected chemicals from personal care and household products, including parabens, UV filters, phthalates and alternative plasticizers, phosphorous flame retardants/plasticizers (PFRs), and bisphenols. These biomarkers include both the parent compounds and their human metabolites. In addition, two oxidative stress biomarkers, 8-epi-prostaglandin F2α and 4-hydroxy nonenal mercapturic acid, were also considered in the study. The method was carefully optimized to tackle the challenges of analyzing compounds with different physico-chemical properties in a highly complex raw wastewater matrix, while model experiments were performed to investigate filtration losses and analyte stability. The applicability of the developed method was tested by analyzing raw wastewater from four European cities: Antwerp, Brussels (Belgium), Girona (Spain), and Zagreb (Croatia). Twenty-one biomarkers (10 parent compounds and 11 metabolites) were detected in all analyzed wastewater samples. The parent compounds with the highest mass loads were PFRs, parabens, and bisphenol S, while phthalate monoesters were the most prominent metabolites. The mass loads of most compounds were quite similar across cities, but geographic differences were observed for some biomarkers, such as metabolites of phthalates and alternative plasticizers. Exposure was then assessed for seven substances for which quantitative urinary excretion data are known. Our results indicate that safe reference values were exceeded for several contaminants, including butylated phthalates, bisphenol A, and tris(2-butoxyethyl) phosphate, particularly for toddlers. With this relatively simple method, which requires less sample manipulation, it is possible to promptly identify and monitor exposure to harmful chemicals at the population level using the WBE approach.
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•Biomarkers of human exposure to personal care and household products were studied.•A fully automated method for their determination in wastewater was developed.•More than 20 biomarkers were detected in the wastewater of 4 European cities.•Exposure to selected chemicals was assessed by wastewater-based epidemiology.•Safe reference values were exceeded for several substances.
This study was aimed to determine the abundance of four antibiotic resistance genes (blaTEM, ermB, qnrS and sulI), as well as bacterial community composition associated with the intestinal mucus of ...wild freshwater fish species collected from the Foix and La Llosa del Cavall reservoirs, which represent ecosystems with high and low anthropogenic disturbance, respectively. Water and sediments from these reservoirs were also collected and analyzed to determine the pollution level by antibiotics. The blaTEM gene was only detected in brown trout and Ebro barbel, which were collected from La Llosa del Cavall reservoir. In contrast, the sulI and qnrS genes were only detected in common carp, which were collected from the Foix reservoir. Although the ermB gene was also detected in common carp, the values were below the limit of quantification. Likewise, water and sediment samples from the Foix reservoir had higher concentrations and more classes of antibiotics than those from La Llosa del Cavall. Pyrosequencing analysis of 16S rRNA genes revealed significant differences in bacterial communities associated with the intestinal mucus of fish species. Therefore, these findings suggest that anthropogenic activities are not only increasing the pollution of aquatic environments, but also contributing to the emergence and spread of antibiotic resistance in organisms that inhabit such environments.
•Antibiotic pollution in two reservoirs was investigated.•Antibiotic resistance in fish species from these reservoirs was analyzed.•The sul I and qnrS genes were detected in fish from the reservoir with higher pollution load.•Significant differences were observed in bacterial community composition between fish species.
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