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.
Display omitted
•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.
In this paper we report on the performances of full-scale conventional activated sludge (CAS) treatment and two pilot-scale membrane bioreactors (MBRs) in eliminating various pharmaceutically active ...compounds (PhACs) belonging to different therapeutic groups and with diverse physico-chemical properties. Both aqueous and solid phases were analysed for the presence of 31 pharmaceuticals included in the analytical method. The most ubiquitous contaminants in the sewage water were analgesics and anti-inflammatory drugs ibuprofen (14.6–31.3
μg/L) and acetaminophen (7.1–11.4
μg/L), antibiotic ofloxacin (0.89–31.7
μg/L), lipid regulators gemfibrozil (2.0–5.9
μg/L) and bezafibrate (1.9–29.8
μg/L), β-blocker atenolol (0.84–2.8
μg/L), hypoglycaemic agent glibenclamide (0.12–15.9
μg/L) and a diuretic hydrochlorothiazide (2.3–4.8
μg/L). Also, several pharmaceuticals such as ibuprofen, ketoprofen, diclofenac, ofloxacin and azithromycin were detected in sewage sludge at concentrations up to 741.1, 336.3, 380.7, 454.7 and 299.6
ng/g dry weight. Two pilot-scale MBRs exhibited enhanced elimination of several pharmaceutical residues poorly removed by the CAS treatment (e.g., mefenamic acid, indomethacin, diclofenac, propyphenazone, pravastatin, gemfibrozil), whereas in some cases more stable operation of one of the MBR reactors at prolonged SRT proved to be detrimental for the elimination of some compounds (e.g., β-blockers, ranitidine, famotidine, erythromycin). Moreover, the anti-epileptic drug carbamazepine and diuretic hydrochlorothiazide by-passed all three treatments investigated.
Furthermore, sorption to sewage sludge in the MBRs as well as in the entire treatment line of a full-scale WWTP is discussed for the encountered analytes. Among the pharmaceuticals encountered in sewage sludge, sorption to sludge could be a relevant removal pathway only for several compounds (i.e., mefenamic acid, propranolol, and loratidine). Especially in the case of loratidine the experimentally determined sorption coefficients (
K
ds) were in the range 2214–3321
L/kg (mean). The results obtained for the solid phase indicated that MBR wastewater treatment yielding higher biodegradation rate could reduce the load of pollutants in the sludge. Also, the overall output load in the aqueous and solid phase of the investigated WWTP was calculated, indicating that none of the residual pharmaceuticals initially detected in the sewage sludge were degraded during the anaerobic digestion. Out of the 26 pharmaceutical residues passing through the WWTP, 20 were ultimately detected in the treated sludge that is further applied on farmland.
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.
A wide range of pharmaceuticals and endocrine disrupting compounds enter freshwaters globally. As these contaminants are transported through aquatic food webs, understanding their impacts on both ...aquatic and terrestrial ecosystems remains a major challenge. Here, we provide the first direct evidence of the transfer of pharmaceuticals and endocrine disruptors through the aquatic–terrestrial habitat linkage by emerging aquatic insects. We also show that the type of insect metamorphosis and feeding behavior determine the bioaccumulation patterns of these contaminants. Adult Trichoptera, an important food source for riparian predators, showed an increased body burden of pharmaceuticals and endocrine disruptors. This implies that terrestrial predators, such as spiders, birds, and bats, are exposed to mixtures of pharmaceuticals and endocrine disruptors of aquatic origin, which may impact their physiology and population dynamics. Overall, our study provides valuable insights into the bioaccumulation patterns and trophic cross-ecosystem transfer of these contaminants, from aquatic primary producers to terrestrial predators.
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.
The use of chemicals is continuously growing both in total amount as well as in a number of different substances, among which organic chemicals play a major role. Owing to the growing public ...awareness on the need of protecting both ecosystems and human health from the risks related to chemical pollution, an increasing attention has been drowned to risk assessment and prioritization of organic pollutants. In this context, the aims of this study were (a) to perform an environmental risk assessment for 200 organic micropollutants including both regulated and emerging contaminants (pesticides, alkylphenols, pharmaceuticals, hormones, personal care products, perflourinated compounds and various industrial organic chemicals) monitored in four rivers located in the Mediterranean side of the Iberian Peninsula, namely, the Ebro, Llobregat, Júcar and Guadalquivir rivers; and (b) to prioritize them for each of the four river basins studied, taking into account their observed concentration levels together with their ecotoxicological potential. For this purpose, a prioritization approach has been developed and a resulting ranking index (RI) associated with each compound. Ranking index is based on the measured concentrations of the chemical in each river and its ecotoxicological potential (EC50 values for algae, Daphnia sp. and fish). Ten compounds were identified as most important for the studied rivers: pesticides chlorpyriphos, chlorfenvinphos, diazinon, dichlofenthion, prochloraz, ethion carbofuran and diuron and the industrial organic chemicals nonylphenol and octylphenol that result from the biodegration of polyethoxylated alkyphenol surfactants. Also, further research into chronic toxicity of emerging contaminants is advocated.
•Ranking index has been developed based on toxic units and detection frequency.•Two hundred micropollutants have been prioritized for Iberian rivers.•Pesticides and alkylphenols were identified as priority according to ranking index.•Emerging contaminants do not pose risk of acute effects in studied rivers.•Chronic toxicity research of emerging contaminants is proposed.
The present paper presents the occurrence of 72 pharmaceuticals and 23 transformation products (TPs) in groundwaters (GWs) underlying the city of Barcelona, Spain. Thirty-one samples were collected ...under different districts, and at different depths. Aquifers with different geologic features and source of recharge were included, i.e., natural bank filtration, infiltration from wastewater and water supply pipes, rainfall recharge, etc. Antibiotics were the most frequently found compounds detected at levels reaching 1000 ng L−1. Natural bank filtration from the river that receives large amounts of effluents from waste water treatment plants (WWTPs), turned out being the most influencing source of contamination, thus GW showed high range of compounds and concentrations as high as or even higher than in the river itself. In general, TPs were found at lower concentrations than the corresponding parent compounds, with some exceptions, such as 4OH propranolol and enalaprilat.
► Comprehensive study of 95 pharmaceuticals in Barcelona's groundwater. ► Concentration levels found were higher than expected for groundwater. ► Transformation products significantly contributed to the overall levels.
Ninety-five pharmaceuticals and transformation products are monitored in the groundwater from Barcelona metropolitan area.
Slovenian Štefka Cobelj (1923–1989) saw her work of an art historian and ethnologist as a calling, and dedicated her life entirely to it. She specialized in Baroque and Yugoslavian and international ...contemporary art, but was most passionate about world ethnology. As the director of the Ptuj museum in Slovenia, and later a museum consultant in Mogadishu in Somalia, she was involved in the creation of ethnology collections of national importance. On her numerous travels for both business and pleasure, she compiled a large personal collection of cultural, historical, and ethnological items. This article describes her contribution to the creation of collections in Ptuj and Mogadishu, and her personal heritage, which was bequeathed to the following Slovenian institutions: Celje Regional Museum, Maribor Art Gallery, Maribor Regional Museum, Ivan Potrč Library Ptuj, and Ptuj-Ormož Regional Museum.
The fate and transport of 34 veterinary pharmaceuticals (PhACs) is investigated in swine slurry and dairy cattle manure-amended agricultural soils, from an experimental field site, by using both ...analytical and modelled data. Potential differences on PhACs fate, attributed to the application of distinct swine slurry fractions (total, solid, and liquid), are herein assessed for the first time. Surface and deep soil layers, up to a depth of 120 cm, were analyzed at different periods after an annual fertilization event. Using input data representing typical agricultural soil conditions and the PhACs concentration measured in organic fertilizers the transport of these pollutants was modelled for a period of 10 years, including the monitored annual fertilization event. Fluoroquinolone, tetracycline and pleuromutilin antibiotics, together with anti-helmintics and analgesic and anti-inflammatories, were detected in manure-amended soils, at average concentrations ranging from 0.078 to 150 μg/kg dw in surface layers, with the highest levels found in the fields fertilized with the swine slurry solid fraction. Even though severe disagreements were observed between experimental and simulated PhACs concentrations along the soil column, both approaches pointed out that target compounds strongly adsorb onto surface layers, showing limited mobility along the soil profile. Thus, repeated manure and slurry fertilizations will contribute in building up persistent PhACs residues in the uppermost layers of the soil, while leaching will be a minor process governing their fate towards the subsurface. The ecotoxicological risks posed by the occurrence of PhACs in soils were estimated to be low for terrestrial organisms. Nevertheless the antibiotic enrofloxacin showed some potential to induce negative effects to crops.
Display omitted
•An improved analytical method to determine PhACs in manure and slurry is developed.•PhACs were quantified in these fertilizers at levels up to 20 mg/L and 7500 μg/kg dw.•After repeated manure applications, PhACs mostly accumulate in surface soils.•Modelling results are hampered by a lack of actual sorption parameters for PhACs.•Ecotoxicological effects to terrestrial organisms were estimated to be low.
PDF
