Staňová, Andrea Vojs*
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With increasing demand for aquaculture products, water reuse is likely to increase for aquaculture operations around the world. Herein, wastewater stabilization ponds (WSP) represents low cost and sustainable treatment technologies to reduce nutrients and various contaminants of emerging concern from effluent. In the present study, we examined bioaccumulation of selected pharmaceuticals from several therapeutic classes by two important fish species in aquaculture with different feeding preferences (Cyprinus carpio and Sander lucioperca) and their common prey to test whether species specific accumulation occurs. Forty and nineteen from 66 selected pharmaceuticals and their metabolites were positively found in water and sediment samples, respectively from the representative WSP. After a six-month study, which corresponds to aquaculture operations, fourteen pharmaceuticals and their metabolites were detected (at a frequency of higher than 50% of samples) in at least one fish tissue collected from the WSP. We observed striking differences for species and organ specific BAFs among study compounds. Though muscle tissues consistently accumulated lower levels of the target analytes, several substances were elevated in brain, liver and kidney tissues (e.g., sertraline) of both species. Low residual concentrations of these target analytes in aquaculture products (fish fillets) suggest WSPs are promising to support the water-food nexus in aquaculture.
- MeSH
- bioakumulace MeSH
- chemické látky znečišťující vodu * MeSH
- kapři * MeSH
- léčivé přípravky * MeSH
- odpadní voda MeSH
- rybníky MeSH
- voda MeSH
- vodní hospodářství MeSH
- zvířata MeSH
- Check Tag
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
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.
- MeSH
- chemické látky znečišťující vodu * analýza MeSH
- čištění vody * MeSH
- kvalita vody MeSH
- léčivé přípravky * MeSH
- lidé MeSH
- odpadní voda MeSH
- roční období MeSH
- Check Tag
- lidé MeSH
- Publikační typ
- časopisecké články MeSH
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. Graphical abstract.
- MeSH
- antidepresiva druhé generace analýza MeSH
- chemické látky znečišťující vodu analýza MeSH
- citalopram analýza MeSH
- lasery polovodičové MeSH
- mozek - chemie * MeSH
- Oncorhynchus mykiss * metabolismus MeSH
- potrava z moře (živočišná) analýza MeSH
- selektivní inhibitory zpětného vychytávání serotoninu analýza MeSH
- spektrometrie hmotnostní - ionizace laserem za účasti matrice metody MeSH
- tandemová hmotnostní spektrometrie metody MeSH
- zvířata MeSH
- Check Tag
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
Chemotherapeutics are pharmaceutical compounds the occurrence of which in the environment is of growing concern because of the increase in treatments against cancer diseases. They can reach the aquatic ecosystems after passing through wastewater treatment plants without complete removal. One of the most frequently used chemotherapeutics is 5-fluorouracil which exhibits a strong cytostatic effect. In this paper, an analytical methodology was developed, validated, and applied to determine 5-fluorouracil, its precursor, 5-fluorocytosine, and its major active metabolite, 5-fluorouridine, in hospital wastewater samples. Due to the expected low concentrations after dilution and interferences present in such a complex matrix, a very selective and sensitive detection method is required. Moreover, an extraction method must be implemented prior to the determination in order to purify the sample extract and preconcentrate the target analytes at micrograms per liter concentration levels. Solid-phase extraction followed by liquid chromatography with tandem mass spectrometry was the combination of choice and all included parameters were studied. Under optimized conditions for wastewater samples analysis, recoveries from 63 to 108% were obtained, while intraday and interday relative standard deviations never exceeded 20 and 25%, respectively. Limits of detection between 61 and 620 ng/L were achieved. Finally, the optimized method was applied to samples from hospital wastewater effluents.
- MeSH
- chemické látky znečišťující vodu analýza MeSH
- extrakce na pevné fázi MeSH
- flucytosin analýza MeSH
- fluoruracil analýza MeSH
- molekulární struktura MeSH
- nemocnice * MeSH
- odpadní voda chemie MeSH
- tandemová hmotnostní spektrometrie MeSH
- uridin analogy a deriváty analýza MeSH
- vysokoúčinná kapalinová chromatografie MeSH
- Publikační typ
- časopisecké články MeSH
Capillary isoelectric focusing hyphenated with mass spectrometry detection, following the sequential injection of the carrier ampholytes and the sample zone, is highly efficient for the characterization of proteins. The main advantage of the sequential injection protocol is that ampholytes, with pH ranges, which are not supposed to cover the isoelectric points of the sample components, can be used for separation. The method then allows online mass spectrometry detection of separated analytes either in the absence (substances that have left the pH gradient) or in the presence of low-level ampholytes (substances that are migrating within the pH gradient). The appearance of the substances within, or outside the pH gradient depends on, e.g., the composition of the ampholytes (broad or narrow pH range) or on the composition of electrolyte solutions. The experiments performed in coated capillaries (with polyvinyl alcohol or with polyacrylamide) show that the amount and the injection length of the ampholytes influence the length of the pH gradient formed in the capillary.
Municipal wastewaters can generally provide real-time information on drug consumption, the incidence of specific diseases, or establish exposure to certain agents and determine some lifestyle consequences. From this point of view, wastewater-based epidemiology represents a modern diagnostic tool for describing the health status of a certain part of the population in a specific region. Hospital wastewater is a complex mixture of pharmaceuticals, illegal drugs, and their metabolites as well as different susceptible and antibiotic-resistant microorganisms, including viruses. Many studies pointed out that wastewater from healthcare facilities (including hospital wastewater), significantly contributes to higher loads of micropollutants, including bacteria and viruses, in municipal wastewater. In addition, such a mixture can increase the selective pressure on bacteria, thus contributing to the development and dissemination of antimicrobial resistance. Because many pharmaceuticals, drugs, and microorganisms can pass through wastewater treatment plants without any significant change in their structure and toxicity and enter surface waters, treatment technologies need to be improved. This short review summarizes the recent knowledge from studies on micropollutants, pathogens, antibiotic-resistant bacteria, and viruses (including SARS-CoV-2) in wastewater from healthcare facilities. It also proposes several possibilities for improving the wastewater treatment process in terms of efficiency as well as economy.
- Publikační typ
- časopisecké články MeSH
- přehledy MeSH
Methamphetamine, mainly consumed as an illicit drug, is a potent addictive psychostimulant that has been detected in surface water at concentrations ranging from nanograms to micrograms per litre, especially in Middle and East Europe. The aim of this study was to expose brown trout (Salmo trutta fario) to environmental (1 μg L-1) and higher (50 μg L-1) concentrations of methamphetamine for 35 days with a four-day depuration phase to assess the possible negative effects on fish health. Degenerative liver and heart alterations, similar to those described in mammals, were observed at both concentrations, although at different intensities. Apoptotic changes in hepatocytes, revealed by activated caspase-3, were found in exposed fish. The parent compound and a metabolite (amphetamine) were detected in fish tissues in both concentration groups, in the order of kidney > liver > brain > muscle > plasma. Bioconcentration factors ranged from 0.13 to 80. A therapeutic plasma concentration was reached for both compounds in the high-concentration treatment. This study indicates that chronic environmental concentrations of methamphetamine can lead to health issues in aquatic organisms.
- MeSH
- chemické látky znečišťující vodu toxicita MeSH
- játra metabolismus MeSH
- ledviny patologie MeSH
- methamfetamin toxicita MeSH
- pstruh metabolismus fyziologie MeSH
- zvířata MeSH
- Check Tag
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
- Geografické názvy
- Evropa MeSH
The aim of this study was to analyze 26 various illicit drugs, psychopharmaceuticals and metabolites thereof in sewer from 17 selected wastewater treatment plants (WWTPs) in the Slovak and Czech Republics. Urinary bio-markers used were analyzed using liquid chromatography coupled with the tandem mass spectrometry (LC-MS/MS). We then compared our results with data obtained in other parts of Europe and the world. The present study shows that the Slovak and Czech Republics have one of the highest methamphetamine consumption rates in Europe. Within Slovakia, the highest level of methamphetamine consumption was found in Dunajská Streda with the mean specific load of the drug in sewage being up to 479mg/day/1000 inhabitants; the next highest load was detected in Trnava (354mg/day/1000 inhabitants). The methamphetamine, ecstasy and cannabis consumptions in our study were comparable to those found in other European cities, whereas cocaine consumption was lower. Among all of the studied psychopharmaceuticals, tramadol and venlafaxine were represented in the highest concentrations. The highest mean specific load of tramadol was detected in the spa town of Piešťany (371mg/day/1000 inhabitants) and Košice (372mg/day/1000 inhabitants), while the highest mean loads of venlafaxine were recorded for the towns of Trenčín (230mg/day/1000 inhabitants) and Piešťany (108mg/day/1000 inhabitants).
- MeSH
- chromatografie kapalinová MeSH
- lidé MeSH
- monitorování životního prostředí metody MeSH
- odhalování abúzu drog metody MeSH
- odpadní voda chemie MeSH
- psychotropní léky analýza MeSH
- tandemová hmotnostní spektrometrie MeSH
- tetrahydrokanabinol analogy a deriváty analýza MeSH
- zakázané drogy analýza MeSH
- Check Tag
- lidé MeSH
- Publikační typ
- časopisecké články MeSH
- Geografické názvy
- Slovenská republika MeSH
Unknown compounds with (anti-)androgenic activities enter the aquatic environment via municipal wastewater treatment plants (WWTPs). Progestins are well-known environmental contaminants capable of interfering with androgen receptor (AR) signaling pathway. The aim of the present study was to determine if 15 selected progestins have potential to contribute to (anti-)androgenic activities in municipal wastewaters and the respective recipient surface waters. AR-specific Chemically Activated LUciferase gene eXpression bioassay in agonistic (AR-CALUX) and antagonistic (anti-AR-CALUX) modes and liquid chromatography tandem atmospheric pressure chemical ionization/atmospheric photoionization with hybrid quadrupole/orbital trap mass spectrometry operated in high resolution product scan mode (LC-APCI/APPI-HRPS) methods were used to assess (anti-)androgenic activity and to detect the target compounds, respectively. The contribution of progestins to (anti-)androgenic activities was evaluated by means of a biologically and chemically derived toxicity equivalent approach. Androgenic (0.08-59 ng/L dihydrotestosterone equivalents - DHT EQs) and anti-androgenic (2.4-26 μg/L flutamide equivalents - FLU EQs) activities and progestins (0.19-75 ng/L) were detected in selected aquatic environments. Progestins displayed androgenic potencies (0.01-0.22 fold of dihydrotestosterone) and strong anti-androgenic potencies (9-62 fold of flutamide). Although they accounted to some extent for androgenic (0.3-29%) and anti-androgenic (4.6-27%) activities in influents, the progestins' contribution to (anti-)androgenic activities was negligible (≤2.1%) in effluents and surface waters. We also tested joint effect of equimolar mixtures of target compounds and the results indicate that compounds interact in an additive manner. Even if progestins possess relatively strong (anti-)androgenic activities, when considering their low concentrations (sub-ng/L to ng/L) it seems unlikely that they would be the drivers of (anti-)androgenic effects in Czech aquatic environments.
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.
- MeSH
- bakteriální léková rezistence MeSH
- bor MeSH
- chemické látky znečišťující vodu analýza MeSH
- chromatografie kapalinová MeSH
- diamant MeSH
- elektrody MeSH
- léčivé přípravky analýza MeSH
- nemocnice MeSH
- odpad tekutý - odstraňování přístrojové vybavení metody MeSH
- odpadní voda analýza chemie mikrobiologie MeSH
- oxidace-redukce MeSH
- peroxid vodíku chemie MeSH
- tandemová hmotnostní spektrometrie MeSH
- zakázané drogy analýza MeSH
- zdravotnický odpad MeSH
- železo chemie MeSH
- Publikační typ
- časopisecké články MeSH
- Geografické názvy
- Česká republika MeSH
- Slovenská republika MeSH
