The occurrence, environmental risks and contribution of organic UV filters to detected (anti-)progestogenic activities were examined in samples of wastewater treatment plant influents and effluents, various surface waters and fish from the Czech Republic. Of the 20 targeted UV filters, 15 were detected in the WWTP influent samples, 11 in the effluents, and 13 in the surface water samples. Benzophenone-3, benzophenone-4, and phenyl benzimidazole sulfonic acid (PBSA) were found in all water samples. Octocrylene, UV-327 and 4-methylbenzylidene camphor exceeded the risk quotient of 1 at some sites. In the anti-progestogenic CALUX assay, 10 out of the 20 targeted UV filters were active. Anti-progestogenic activities reaching up to 7.7 ng/L, 3.8 ng/L, and 4.5 ng/L mifepristone equivalents were detected in influents, effluents, and surface waters, respectively. UV filters were responsible for up to 37 % of anti-progestogenic activities in influents. Anti-progestogenic activities were also measured in fish tissues from the control pond and Podroužek (pond with the highest number of detected UV filters) and ranged from 2.2 to 9.5 and 1.9 to 8.6 ng/g dw mifepristone equivalents, respectively. However, only benzophenone was found in fish, but it does not display anti-progestogenic activity and thus could not explain the observed activities.
- MeSH
- chemické látky znečišťující vodu * analýza toxicita MeSH
- hodnocení rizik MeSH
- monitorování životního prostředí MeSH
- odpadní voda MeSH
- přípravky chránící proti slunci * analýza toxicita MeSH
- progestiny analýza MeSH
- ryby * metabolismus MeSH
- ultrafialové záření MeSH
- zvířata MeSH
- Check Tag
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Geografické názvy
- Česká republika MeSH
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.
Despite their low concentrations in many aquatic environments, evidence exists to suggest that herbicides do affect non-target organisms. Given that burrowing is a primary life-history trait in crayfish, herbicides could potentially have serious negative effects on these ecologically important freshwater macroinvertebrates. In this study, we exposed the red swamp crayfish Procambarus clarkii to terbuthylazine (a triazine) and metazachlor (a chloroacetanilide) at an environmental concentration of 2.0 μg/L for 28 days, and then observed their burrowing behaviour for two days. The metazachlor-exposed males excavated a greater number of burrows than the other tested groups, with comparable depths and volumes relative to individual specimen weight. The relative depth and volume of female burrows were identical in all groups. The natural habit of female crayfish of constructing deeper burrows than males was marginally significant in the control and META groups but was not significant for relative volume. The hypothesized adverse effects of chronic exposure to real environmental concentrations of herbicides were not documented in terms of either relative depth or volume. However, the increased number of burrows in metazachlor-exposed animals may mean that this invasive species will cause greater damage to embankments and river banks. The mechanisms behind these effects require closer study.
- MeSH
- acetamidy MeSH
- herbicidy * toxicita MeSH
- severní raci * MeSH
- triaziny toxicita MeSH
- zvířata MeSH
- Check Tag
- mužské pohlaví MeSH
- ženské pohlaví MeSH
- 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
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.
- MeSH
- chemické látky znečišťující vodu * analýza toxicita MeSH
- krevní plazma chemie MeSH
- léčivé přípravky * MeSH
- lidé MeSH
- monitorování životního prostředí MeSH
- zvířata MeSH
- Check Tag
- lidé MeSH
- zvířata MeSH
- Publikační typ
- časopisecké články MeSH
- práce podpořená grantem MeSH
- Geografické názvy
- Česká republika MeSH
- Německo MeSH
Gene-directed enzyme/prodrug therapy represents one of the experimental treatment approaches. The system based on conversion of nontoxic prodrug 5-fluorocytosine to chemotherapeutic 5-fluorouracil by cytosine deaminase or fusion cytosine deaminase::uracil phosphoribosyl transferase belongs to the most frequently used. The detailed analysis of 5-fluorocytosine, 5-fluorouracil and its metabolites enables to understand various responses of tumour cells to treatment as well as mechanisms of resistance. A fast, sensitive and accurate methods based on liquid chromatography with high-resolution mass spectrometry (LC-HRMS) for the identification and quantification of 5-fluorocytosine, 5-fluorouracil and its major metabolites were developed. Two different hybrid high-resolution mass spectrometers sufficient for study of metabolic pathways were used. The LC-ESI IT-TOF MS method was successfully used for identification of 5-fluorocytosine, 5-fluorouracil and its metabolites in complex biological matrices (mesenchymal stromal cells and tumour cells media) and for confirmation of the metabolic conversion of 5-fluorocytosine even in chemoresistant tumour cells media samples. For quantification, the LC-HESI QExactive MS method was developed and validated. The developed method demonstrated a very good linear range for 5-fluorocytosine from 1 ng/mL to 1000 ng/mL and for its major metabolites from 5 ng/mL to 1000 ng/mL. The limits of detection and limits of quantification ranged from 1.1 to 26 ng/mL and from 3.6 to 87 ng/mL, respectively. Both developed methods confirmed the ability of gene-directed enzyme prodrug therapy to metabolically convert 5-fluorocytosine to 5-fluorouracil and its major metabolites in real samples of tumour cell media and mesenchymal stromal cells.
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
Sorption of pharmaceuticals, which can occur in soils, may differ when present in a soil solution as a single compound or in a solution with other pharmaceuticals. Therefore, the sorption isotherms described by the Freundlich equations were evaluated for 6 compounds, which were applied in solutions of a single pharmaceutical, two pharmaceuticals or all pharmaceuticals to seven soils. Study mainly focused on a behavior of fexofenadine and irbesartan that occurred in soils in 3 forms (cationic, zwitter-ionic or neutral, anionic). Sorption of both compounds slightly increased (in some soils) when applied together, largely increased when applied with carbamazepine (neutral), and extremely increased when applied in solutions with citalopram (strongly sorbed cation), which could be explained by a cooperative multilayer sorption on soil constituents. On the other hand, sorption of both compounds moderately decreased when applied with clindamycin (cation and neutral) or sulfamethoxazole (neutral or anion). The magnitude of an increase or decrease in the Freundlich sorption coefficient (KF) for a particular compound depended on soil conditions, a form of compound's molecule and its interaction with molecules of other compounds. Despite sorption being influenced by other compound(s) in solution, the KF coefficients evaluated for a particular compound under the different conditions were mostly correlated with the same soil properties: KF,CAR with an organic carbon content, KF,CIT and KF,CLI with a base cation saturation, KF,SUL with hydrolytic acidity, and KF,FEX and KF,IRB with sorption complex saturation.
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
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
