•First study evaluating the impact of OSSFs with respect to the discharge of MPs into surface water•High concentrations of MPs were detected at sites exclusively affected by OSSFs•Different ...composition profiles were observed at sites affected by WWTPs and OSSFs•OSSFs were shown to be a heterogeneous emission sources of MPs•Photodegradation reduced the levels of specific MPs
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One of the main risks associated with effluents from both wastewater treatment plants (WWTPs) and on-site sewage treatment facilities (OSSFs) is the release of micropollutants (MPs) in receiving water bodies. However, the impact of MPs present in the effluents of OSSFs in the aquatic environment has not been studied so far. The current study evaluates the impact of the effluents of OSSFs and small-to-large scale WWTPs on natural waters. The discharge of 74 MPs was assessed including pharmaceuticals, personal care products, pesticides, artificial sweeteners and perfluoroalkyl substances (PFASs). The sampling was carried out within a Swedish catchment and included three sites that are exclusively affected by OSSFs and other sites that are mainly affected by WWTPs or a mixture of sources (7 sites, 28 samples). Results show that although OSSFs serve a much smaller total number of people, the MPs emitted from OSSFs reached the aquatic environment in significant quantities (concentrations of >150ngL−1 of ∑MPs). The composition profiles for sites affected by WWTPs were similar and were dominated by sucralose (27% of the ∑MPs), caffeine (27% of the ∑MPs), lamotrigine (10% of the ∑MPs), desvenlafaxine (5% of the ∑MPs), and diclofenac (4% of the ∑MPs). In contrast, the sites affected by OSSFs showed high variability, exhibiting a different profile from those affected by WWTPs and also from each other, demonstrating that OSSFs are not homogeneous sources of MPs. Some specific compounds, such as diethyltoluamide (DEET) and caffeine, were proportionally much more important at sites affected by OSSFs than at sites affected by WWTPs (representing a much higher percentage of the ∑MPs in the OSSFs). In contrast, PFASs did not show high concentration variation among the different sampling sites and the composition profiles were relatively similar, indicating that these substances follow different routes of entry into the aquatic environment.
This study evaluated the occurrence and distribution of 81 pharmaceutically active compounds (PhACs) in the vulnerable area of the Ebro Delta region (Catalonia, Spain), to assess the environmental ...impact of wastewater treatment plants discharge to coastal environments. The occurrence of PhACs was followed along the wastewater-recipient water-sediment chain until they reach estuaries and the Mediterranean Sea. Water and sediment samples were collected in an integrated way at different sampling points covering three different seasons in reaches of the Ebro River located upstream and downstream from wastewater treatment plants (WWTPs), surrounding channels, estuaries, and the associated receiving seawater. 28 out of the 57 compounds detected in effluent wastewater were positively identified in estuary and seawaters, revealing that WWTP discharges are an important source of contamination in coastal environments and that PhACs are suitable markers of urban contamination in these areas. The substances with the highest frequency of detection belonged to the groups of analgesics/anti-inflammatories (acetaminophen, salicylic acid), antihypertensives (valsartan), psychiatric drugs (carbamazepine), and antibiotics (clarithromycin, trimethoprim). In general, a decrease in concentration was observed from inland sampling points towards the Mediterranean Sea, resulting from a dilution in the recipient marine water bodies. A reduced number of PhACs, at concentrations ranging from 0.1 to 12.5 ng g−1 dry weight (d.w.) was detected in sediment samples, indicating that sorption is a minor natural attenuation pathway for these compounds. Finally, a prioritization strategy, based on the compounds concentration and frequency of detection in seawater, removal efficiency in WWTP, bioaccumulation potential, toxicity to marine organisms and persistency, was used to highlight the PhACs of major ecological concern and that could be used as relevant indicators of wastewater contamination in coastal environments.
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•Distribution of PhACs followed along the wastewater-recipient water-sediment chain.•WWTP discharges are an important source of PhACs contamination in the Ebro Delta.•PhACs are subject to dilution once they reached freshwater and marine ecosystems.•Sorption to sediments is a minor natural attenuation pathway.•Ecologically relevant PhACs highlighted as markers of wastewater contamination.
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.
In a long term study, which covered 4 sampling periods over three years, a total number of 84 samples, specifically 28 influent, effluent, from seven WWTP located in the main cities along the Ebro ...river Basin (North East of Spain), as well as receiving river waters, were analyzed to assess the occurrence of 73 pharmaceuticals covering several medicinal classes. Results indicated that pharmaceuticals are widespread pollutants in the aquatic environmental. Linking the calculation of removal rates with half-lives, assuming that compound degradation followed pseudo-first order kinetics, suggested that conventional wastewater treatments applied at the seven WWTP were unable to completely remove most of the pharmaceuticals under study. The evaluation of compound degradability, in terms of half-lives, is an important task to discuss integrated solutions for mitigation of pollutants entry into the water cycle. High half-lives observed for the majority of pharmaceuticals in WWTP suggest that, in order to enhance compound degradation, higher hydraulic retention times should be required.
The wide spectrum of substances detected in receiving river waters indicates that WWTP outlets are major contributors of pharmaceuticals in the aquatic environment. However, municipal wastewater treatment represents an obligatory and final treatment step prior to their release into the aquatic media, since load of pharmaceuticals in outlets were considerably reduced after treatment.
Finally, hazard posed by pharmaceuticals in both surface and effluent wastewaters was assessed toward different aquatic organisms, (algae, daphnids and fish). The overall relative order of susceptibility was estimated to be algae>daphnia>fish. Results indicate that no significant risks could be associated to the presence of pharmaceuticals in those matrices, indicating that reduction of compound concentration after wastewater treatment as well as dilution factor once pharmaceuticals are discharged in receiving river water efficiently mitigate possible environmental hazards.
During 8 sampling campaigns carried out over a period of two years, 72 samples, including influent and effluent wastewater, and sludge samples from three conventional wastewater treatment plants ...(WWTPs), were analyzed to assess the occurrence and fate of 43 pharmaceutical compounds. The selected pharmaceuticals belong to different therapeutic classes, i.e. non-steroidal anti-inflammatory drugs, lipid modifying agents (fibrates and statins), psychiatric drugs (benzodiazepine derivative drugs and antiepileptics), histamine H2-receptor antagonists, antibacterials for systemic use, beta blocking agents, beta-agonists, diuretics, angiotensin converting enzyme (ACE) inhibitors and anti-diabetics. The obtained results showed the presence of 32 target compounds in wastewater influent and 29 in effluent, in concentrations ranging from low ng/L to a few μg/L (e.g. NSAIDs). The analysis of sludge samples showed that 21 pharmaceuticals accumulated in sewage sludge from all three WWTPs in concentrations up to 100 ng/g. This indicates that even good removal rates obtained in aqueous phase (i.e. comparison of influent and effluent wastewater concentrations) do not imply degradation to the same extent. For this reason, the overall removal was estimated as a sum of all the losses of a parent compound produces by different mechanisms of chemical and physical transformation, biodegradation and sorption to solid matter. The target compounds showed very different removal rates and no logical pattern in behaviour even if they belong to the same therapeutic groups. What is clear is that the elimination of most of the substances is incomplete and improvements of the wastewater treatment and subsequent treatments of the produced sludge are required to prevent the introduction of these micro-pollutants in the environment.
► Even though the WWTPs meet the regulatory requirements for wastewater treatment (Directive 91/271/EEC), they are only moderately effective in removing pharmaceutical compounds. ► Out of 43 analyzed pharmaceuticals, 29 were detected in wastewater effluent and 21 in sludge samples. ► Removal rates varied strongly without evident correlation to the compound structure, and were mainly influenced by wastewater characteristics, operational conditions and treatment technology used.
This article describes the development, optimization, and validation of an analytical method for the simultaneous detection and identification of 73 pharmaceutical residues, covering various ...therapeutic groups, in both surface and wastewaters. The method is based on the simultaneous extraction of all target compounds by Solid Phase Extraction (SPE), using a hydrophilic−lipophilic balanced polymer followed by liquid chromatography tandem mass spectrometry, using a hybrid triple quadrupole-linear ion trap mass spectrometer (QqLIT). Quantitative analysis was performed using the 4000 Qtrap tandem mass spectrometer in Selected Reaction Monitoring (SRM) mode, monitoring two SRM transitions to fulfill EC guidelines, as well as to ensure an accurate identification of target compounds in the samples. Quantitation is performed by the internal standard approach, indispensable to correct matrix effects. Moreover, to obtain an extra tool for confirmation and identification of the studied pharmaceuticals, an Information Dependent Acquisition (IDA) experiment was performed, with SRM as the survey scan and an enhanced product ion (EPI) scan, at three different collision energies, as dependent scan. Compound identification was carried out by library search with a developed library, created by the infusion of standards, based on EPI spectra at the three collision energies. The main advantages of the developed method, besides high sensitivity (limits of detection ranging from 0.1−55 ng/L, depending on the matrix), selectivity, and reliability of results, are that all compounds are extracted in a single step, speeding up considerably sample preparation. Recoveries obtained were generally higher than 50% for both surface and wastewaters, with the exception of metronidazole (20−30%), salbutamol (33−43%), atorvastatin (40% in surface water), and nadolol (31% in surface water) that yielded lower but still acceptable recoveries. The overall variability of the method was below 15%, for all compounds and all matrixes tested. Finally, the method developed has been applied to the analysis of various influent and effluent wastewaters as well as river waters from Spain.
The impact of effluent wastewaters from four different hospitals: a university (1456 beds), a general (350 beds), a pediatric (110 beds) and a maternity hospital (96 beds), which are conveyed to the ...same wastewater treatment plant (WWTP), was evaluated in the receiving urban wastewaters. The occurrence of 78 pharmaceuticals belonging to several therapeutic classes was assessed in hospital effluents and WWTP wastewaters (influent and effluent) as well as the contribution of each hospital in WWTP influent in terms of pharmaceutical load. Results indicate that pharmaceuticals are widespread pollutants in both hospital and urban wastewaters. The contribution of hospitals to the input of pharmaceuticals in urban wastewaters widely varies, according to their dimension. The estimated total mass loadings were 306gd−1 for the university hospital, 155gd−1 for the general one, 14gd−1 for the pediatric hospital and 1.5gd−1 for the maternity hospital, showing that the biggest hospitals have a greater contribution to the total mass load of pharmaceuticals. Furthermore, analysis of individual contributions of each therapeutic group showed that NSAIDs, analgesics and antibiotics are among the groups with the highest inputs.
Removal efficiency can go from over 90% for pharmaceuticals like acetaminophen and ibuprofen to not removal for β-blockers and salbutamol. Total mass load of pharmaceuticals into receiving surface waters was estimated between 5 and 14g/d/1000 inhabitants.
Finally, the environmental risk posed by pharmaceuticals detected in hospital and WWTP effluents was assessed by means of hazard quotients toward different trophic levels (algae, daphnids and fish). Several pharmaceuticals present in the different matrices were identified as potentially hazardous to aquatic organisms, showing that especial attention should be paid to antibiotics such as ciprofloxacin, ofloxacin, sulfamethoxazole, azithromycin and clarithromycin, since their hazard quotients in WWTP effluent revealed that they could pose an ecotoxicological risk to algae.
•In-depth monitoring of pharmaceutical presence in hospital effluents of four different types of hospitals•Evaluation of contribution of hospital wastewater into urban wastewater influent in terms of pharmaceutical loads•Environmental Risk Assessment regarding presence of pharmaceuticals in hospital effluents and wastewater effluents•Prioritization of 10 selected pharmaceuticals in hospital and WWTP effluents based on the Environmental Risk Assessment performed
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
This study investigated the potential of biochar filters as a replacement or complement for sand filters for removal of pharmaceutically active compounds (PhACs) from wastewater in onsite sewage ...facilities (OSSF). Specifically, the study investigated the effects of biodegradation, adsorption and a combination of these processes on removal of four model PhACs from wastewater in biochar filters operated under hydraulic loading conditions mimicking those found in onsite infiltration beds. Concentrations and removal of the four PhACs (i.e. carbamazepine, metoprolol, ranitidine and caffeine) were investigated over 22weeks in four treatments: biochar (BC) with active or inactive biofilm (BC-active-biofilm, BC-inactive-biofilm), biochar without biofilm (BC-no-biofilm) and sand with active biofilm (Sand-active-biofilm). The adsorption of carbamazepine was high in BC-no-biofilm (99% removal after 22weeks), while biodegradation was very low in Sand-active-biofilm (7% removal after 22weeks). Removal of carbamazepine in BC-active-biofilm was high and stable over the 22weeks (>98%), showing a significant role of biofilm in filter biogeneration. However, carbamazepine removal declined over time in BC-inactive-biofilm, from 99% in week 13 to 73% in week 22. Metoprolol was poorly degraded in Sand-active-biofilm (37% after 22weeks), while adsorption seemed to be the major pathway for removal of metoprolol in biochar. Ranitidine and caffeine were efficiently removed by either adsorption (97% and 98%, respectively, after 22weeks) or biodegradation (99% and >99%, respectively, after 22weeks). In conclusion, biochar is a promising filter medium for OSSF, especially for persistent PhACs such as carbamazepine and metoprolol.
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•Carbamazepine removal in biochar with no biofilm is high due to adsorption.•Inactivation of biofilm in biochar filters impairs removal of carbamazepine.•Inactivation of biofilm in biochar filters does not affect removal of metoprolol.•Ranitidine and caffeine are efficiently removed by adsorption and biodegradation.•Biochar is a promising medium for pharmaceutical removal in onsite sewage systems.
Even though Ibuprofen is one of the most studied pharmaceutical in the aquatic environment, there is still a lack of information about its fate and the generation of different transformation products ...along wastewater treatment plants (WWTPs). Ibuprofen biotransformation products can be generated by human metabolism or by microorganisms present in WWTPs and in natural waters, soils, and sediments, which increase the probability to find them in environment. In this work, the presence of ibuprofen and its main metabolites: ibuprofen carboxylic acid (CBX IBU), 2-hydroxylated ibuprofen (2-OH IBU) and 1-hydroxylated ibuprofen (1-OH IBU), was monitored quantitatively along the biodegradation processes occurring in different batch activated sludge (BAS) experiments under different working conditions. Total ibuprofen removal, achieved in almost all the experiments, was related in part to the formation of the metabolites mentioned. Another ibuprofen metabolite, 1,2-dihydroxy ibuprofen, was detected in BAS experiments for the first time. The metabolites 2-OH IBU and 1-OH IBU remained in solution at the end of ibuprofen biodegradation experiments whereas CBX IBU disappeared faster than hydroxylated metabolites. In addition, also the biodegradation of 1-OH IBU, 2-OH IBU and CBX IBU was evaluated in batch experiments: CBX IBU removal occurred at the highest rate followed by IBU, 2-OH IBU, and 1-OH IBU, which exhibited the lowest removal rate. Finally, Ibuprofen and ibuprofen metabolites were monitored in sewage and natural water samples, where they were found at higher levels than expected: the maximum concentration in influent wastewater samples were 13.74, 5.8, 38.4, 94.0μg/L for IBU, 1-OH IBU, CBX IBU and 2-OH IBU respectively; whereas maximum levels in effluent wastewater samples were 1.9, 1.4, 10.7, 5.9μg/L for IBU, 1-OH IBU, CBX IBU and 2-OH IBU respectively. High levels of the compounds were also found in river samples, in particular for CBX IBU, which was detected up to 3.9μg/L.
► Fast quantification of ibuprofen and its metabolites in batch studies, real wastewater and river samples ► First detection of 1,2-dihydroxy ibuprofen in activated sludge batch experiments ► First removal study of ibuprofen metabolites in activated sludge batch experiments ► Very high levels of metabolites in comparison to ibuprofen in real influent, effluent and river water
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