Identification of hot spots and co-occurrence patterns of activities on thyroid hormone receptor and transthyretin binding in passive samplers from Czech surface waters.

One of the less studied in vitro biological activities in the aquatic environment are thyroid hormone receptor beta (TRß)-mediated agonistic and antagonistic activities and transthyretin (TTR) binding activity. They were measured mostly using active sampling methods, but rarely found. It is unclear if these activities co-occur, and the drivers of the (anti-)TRß activity are mostly unknown. Therefore, the main aim of the study was to determine (anti-)TRß activities as well as transthyretin (TTR) binding activity in passive samplers from Czech surface waters in combination with the search for the effect drivers based on liquid chromatography-high resolution mass spectrometry (LC-HRMS) analysis by applying suspect screening. Passive samplers (polar organic chemical integrative samplers, POCIS) were deployed at twenty-one sites (all ends of watersheds and other important sites in Elbe River) in the Czech rivers. The (anti-)TRß and TTR binding activity were measured using (anti-)TRß-CALUX and TTR-TRß-CALUX bioassays. Anti-TRß activity was found at eight sites, and TTR binding activity co-occurred there at six of these sites. The co-occurrence of TRß-mediated antagonistic activity and TTR binding indicate that they may have common effect drivers. No sample exhibited TRß agonistic activity. The extract from the site Bílina River, the most burdened with anti-TRß activity, was further successfully fractionated, and this activity was revealed in the fraction, where mid-polar compounds prevailed. However, the suspect LC-HRMS analysis did not reveal the chemical effect drivers. Our results showed that anti-TRß activity can be found in surface waters by employing passive sampling and frequently co-occurs with TTR binding activity. Overall, the fractionation procedure and non-target data acquisition used in this study can serve as a basis for searching the effect drivers in future research.

Current-use pesticide exposure pathways in Czech adults and children from the CELSPAC-SPECIMEn cohort.

INTRODUCTION: In this study, we aimed to characterise exposure to pyrethroids, organophosphates, and tebuconazole through multiple pathways in 110 parent-child pairs participating in the CELSPAC-SPECIMEn study. METHODS: First, we estimated the daily intake (EDI) of pesticides based on measured urinary metabolites. Second, we compared EDI with estimated pesticide intake from food. We used multiple linear regression to identify the main predictors of urinary pesticide concentrations. We also assessed the relationship between urinary pesticide concentrations and organic and non-organic food consumption while controlling for a range of factors. Finally, we employed a model to estimate inhalation and dermal exposure due to spray drift and volatilization after assuming pesticide application in crop fields. RESULTS: EDI was often higher in children in comparison to adults, especially in the winter season. A comparison of food intake estimates and EDI suggested diet as a critical pathway of tebuconazole exposure, less so in the case of organophosphates. Regression models showed that consumption per g of peaches/apricots was associated with an increase of 0.37% CI [0.23% to 0.51%] in urinary tebuconazole metabolite concentrations. Consumption of white bread was associated with an increase of 0.21% CI [0.08% to 0.35%], and consumption of organic strawberries was inversely associated (-61.52% CI [-79.34% to -28.32%]), with urinary pyrethroid metabolite concentrations. Inhalation and dermal exposure seemed to represent a relatively small contribution to pesticide exposure as compared to dietary intake. CONCLUSION: In our study population, findings indicate diet plays a significant role in exposure to the analysed pesticides. We found an influence of potential exposure due to spray drift and volatilization among the subpopulation residing near presumably sprayed crop fields to be minimal in comparison. However, the lack of data indicating actual spraying occurred during the critical 24-hour period prior to urine sample collection could be a significant contributing factor.

Assessment of potential mobility of selected micropollutants in agricultural soils of the Czech Republic using their sorption predicted from soil properties.

The sorption of organic contaminants in soils and sediment is a crucial factor affecting their mobility in the vadose zone environment. The Freundlich sorption isotherms were evaluated for eleven micropollutants and eight soils. The highest Freundlich sorption coefficients, KF, were obtained for triclosan (324 ± 153 cm3/nµg1-1/ng-1) followed by sertraline (120 ± 74), venlafaxine (74.3 ± 41.2), telmisartan (33.3 ± 13.6), atorvastatin (8.66 ± 4.78), bisphenol S (8.03 ± 4.87), lamotrigine (6.92 ± 3.02), 2-phenylbenzimidazole-5-sulfonic acid (3.77 ± 2.25), memantine (3.42 ± 1.64), 1-methyl-1H-benzotriazole (2.05 ± 0.99), and valsartan (0.88 ± 0.89). The KF values for the individual compounds were correlated with soil properties. Multiple linear regressions were used to derive equations for predicting the KF values using the soil properties. The first set of equations contained mainly properties with the strongest correlations with the KF values, e.g., a base cation saturation for positively charged compounds or a hydrolytic acidity for negatively charged compounds. The second set of equations contained properties included in the map of agricultural soils of the Czech Republic. These equations always indicated positive correlations with oxidizable organic carbon and clay content. They also included either a negative or positive correlation with pHKCl. A positive correlation with pHKCl was obtained for venlafaxine, memantine, and sertraline, which were mostly positively charged. A negative correlation with pHKCl was obtained for the remaining compounds. The second set of equations, the soil map, and the database of soil properties were used to predict the KF value distributions within the Czech agricultural soils. It resulted in similar KF distributions' patterns for valsartan, lamotrigine, atorvastatin, and telmisartan (with a positive correlation between KF and hydrolytic acidity), which considerably differed from the KF patterns for the other compounds. These maps were used to delineate areas with a leaching potential of the compounds toward groundwater that will serve as a tool for assessing a potential groundwater vulnerability.

Invertebrates differentially bioaccumulate pharmaceuticals: Implications for routine biomonitoring.

Surface water quality monitoring programs have been developed to examine traditional contaminants, such as persistent organic pollutants (POPs). However, urbanization, which is increasing around the world, is increasing discharge of treated wastewater and raw sewage in many regions. Pharmaceuticals and their metabolites represent typical markers of such trajectories in urbanization. We selected an ongoing monitoring program, which was designed for routine surveillance of nonionizable POPs in different aquatic matrices, to examine the occurrence of 67 pharmaceuticals and their metabolites in water and multiple bioindicator matrices: benthic invertebrates, juvenile fish, and adult fish (plasma and muscle tissue) from ten river systems with varying levels of watershed development. In addition, we placed zebra mussels and passive samplers in situ for a fixed period. A statistically significant relationship between pharmaceutical levels in passive samplers and biota was found for caged zebra mussels and benthic invertebrates, while only a few pharmaceuticals were identified in fish matrices. Invertebrates, which have received relatively limited study for pharmaceutical bioaccumulation, accumulated more pharmaceuticals than fish, up to thirty different substances. The highest concentration was observed for sertraline in zebra mussels and telmisartan in benthic invertebrates (83 and 31 ng/g ww, respectively). Our results across diverse study systems indicate that ongoing surface water quality monitoring programs, which were originally designed for traditional organic pollutants, need to be revised to account for bioaccumulation dynamics of pharmaceuticals and other ionizable contaminants. Aquatic monitoring programs routinely examine accumulation of nonionizable organic pollutants; however, we identified that these efforts need to be revised to account for bioaccumulation of ionizable contaminants, which reached higher levels in invertebrates than in fish.

Bisphenols emerging in Norwegian and Czech aquatic environments show transthyretin binding potency and other less-studied endocrine-disrupting activities.

Bisphenols are increasingly recognized as environmental pollutants with endocrine-disrupting potential. Nonetheless, the study of environmental occurrence and some endocrine-disrupting activities of some bisphenols came widely into focus of research only recently. The aims of the present study were to: 1) determine the predominant bisphenols in Norwegian sewage sludge and sediment and in Czech surface waters, and 2) characterize the binding of bisphenols to a transport protein transthyretin (TTR) and their (anti-)thyroid, (anti-)progestagenic, and (anti-)androgenic activities. High-performance liquid chromatography with atmospheric pressure chemical ionization or photoionization coupled with high resolution mass spectrometry (HPLC-APCI/APPI-HRMS) and Chemically Activated LUciferase gene eXpression (CALUX) in vitro reporter gene bioassays were used to detect the target compounds and to determine endocrine-disrupting activities, respectively. Bisphenol A (BPA), 4,4'-bisphenol F (BPF), bisphenol S (BPS), and bisphenol E (BPE) were the most frequently found compounds in municipal sewage sludge. Furthermore, bisphenol TMC (BPTMC) and bisphenol AF (BPAF) frequently occurred in sediment and surface waters, respectively. BPA was the major contributor to Ʃ of bisphenols in Norwegian sewage sludge with exception of one sample where BPF predominated. We also monitored a few bisphenols in sediment but only BPTMC was found. BPA, BPAF and BPF were the dominant bisphenols in Czech surface waters. Some bisphenols have shown TTR binding potency (BPAF = BPF > BPA = BPE) and some have displayed the following endocrine-disrupting activities: anti-thyroid (BPAF), anti-progestagenic (BPTMC > BPA = BPAF), and anti-androgenic (BPAF > BPE > BPA > BPTMC > BPF > BPS). It is noteworthy that BPAF exhibited stronger or similarly potent endocrine-disrupting activities compared to BPA. Our results provide new insights into these less-studied endocrine-disrupting activities of environmentally relevant bisphenols and may be useful in prioritizing those compounds that deserve further attention in environmental monitoring and eco-toxicological research.

Complex effects of pollution on fish in major rivers in the Czech Republic.

Monitoring the contamination level in aquatic environments and assessing the impact on aquatic life occurs throughout the world. In the present study, an approach based on a combination of biomarkers and the distribution of various industrial and municipal pollutants was used to investigate the effect of aquatic environmental contamination on fish. Monitoring was performed in ten rivers in the Czech Republic (Berounka, Dyje, Elbe, Luznice, Odra, Ohre, Otava, Sázava, Svratka, and Vltava rivers, with one or two locations in each river) at the same sites that were regularly monitored within the Czech National Monitoring Program in 2007-2011. Health status, hepatic ethoxyresorufin-O-deethylase (EROD) activity, total cytochrome P450 content, and the plasma vitellogenin concentration were assessed in wild chub (Squalius cephalus) males caught at the monitored sites. The contamination level was the highest in the Svratka River downstream of Brno. Among all measured persistent organic pollutants (POPs), polychlorinated biphenyls and dichlorodiphenyltrichloroethane and its metabolites were the major contributors of POPs in fish muscle. Elbe, Odra, and Svratka rivers were identified as the most polluted. Fish from these locations showed reduced gonad size, increased vitellogenin concentration in male plasma, EROD, and total cytochrome P450 content. These biomarkers can be used for future environmental monitoring assessments. Overall, this study improves our understanding of the relationship between human activities and pollutant loads and further contributes to the decision to support local watershed managers to protect water quality in this region.

Comparison of passive sampling and biota for monitoring of tonalide in aquatic environment.

Synthetic musk compounds are extensively used in personal care and cosmetic products all over the world. Afterwards, they are discharged into the environment mainly because they are not completely removed in wastewater treatment plants. The aim of this study was to investigate if a passive sampler is applicable for the monitoring of tonalide, a polycyclic musk compound, in the aquatic environment and to compare the levels of tonalide in pesticide-polar organic chemical integrative sampler (POCIS) and biota. For this purpose, four sampling localities on the three biggest rivers in the Czech Republic were selected. Tonalide was determined in POCIS at all sampling sites in the concentration ranging from 9 ng/POCIS (Labe River, Hradec Králové) to 25 ng/POCIS (Morava River, Blatec). The locality with the most frequent occurrence of tonalide in biota samples was the Morava River which well corresponded with the highest tonalide concentration in POCIS among sampling sites. The highest number of positive tonalide detections among all studied biota samples was found in fish plasma. To the best of our knowledge, this is the first evidence that tonalide bioaccumulates in fish blood. Tonalide levels were below the limit of quantification in benthos samples at all sampling sites.

Screening of benzodiazepines in thirty European rivers.

Pharmaceuticals as environmental contaminants have received a lot of interest over the past decade but, for several pharmaceuticals, relatively little is known about their occurrence in European surface waters. Benzodiazepines, a class of pharmaceuticals with anxiolytic properties, have received interest due to their behavioral modifying effect on exposed biota. In this study, our results show the presence of one or more benzodiazepine(s) in 86% of the analyzed surface water samples (n = 138) from 30 rivers, representing seven larger European catchments. Of the 13 benzodiazepines included in the study, we detected 9, which together showed median and mean concentrations (of the results above limit of quantification) of 5.4 and 9.6 ng L-1, respectively. Four benzodiazepines (oxazepam, temazepam, clobazam, and bromazepam) were the most commonly detected. In particular, oxazepam had the highest frequency of detection (85%) and a maximum concentration of 61 ng L-1. Temazepam and clobazam were found in 26% (maximum concentration of 39 ng L-1) and 14% (maximum concentration of 11 ng L-1) of the samples analyzed, respectively. Finally, bromazepam was found only in Germany and in 16 out of total 138 samples (12%), with a maximum concentration of 320 ng L-1. This study clearly shows that benzodiazepines are common micro-contaminants of the largest European river systems at ng L-1 levels. Although these concentrations are more than a magnitude lower than those reported to have effective effects on exposed biota, environmental effects cannot be excluded considering the possibility of additive and sub-lethal effects.

Perfluoroalkyl substances in aquatic environment-comparison of fish and passive sampling approaches.

The concentrations of seven perfluoroalkyl substances (PFASs) were investigated in 36 European chub (Squalius cephalus) individuals from six localities in the Czech Republic. Chub muscle and liver tissue were analysed at all sampling sites. In addition, analyses of 16 target PFASs were performed in Polar Organic Chemical Integrative Samplers (POCISs) deployed in the water at the same sampling sites. We evaluated the possibility of using passive samplers as a standardized method for monitoring PFAS contamination in aquatic environments and the mutual relationships between determined concentrations. Only perfluorooctane sulphonate was above the LOQ in fish muscle samples and 52% of the analysed fish individuals exceeded the Environmental Quality Standard for water biota. Fish muscle concentration is also particularly important for risk assessment of fish consumers. The comparison of fish tissue results with published data showed the similarity of the Czech results with those found in Germany and France. However, fish liver analysis and the passive sampling approach resulted in different fish exposure scenarios. The total concentration of PFASs in fish liver tissue was strongly correlated with POCIS data, but pollutant patterns differed between these two matrices. The differences could be attributed to the metabolic activity of the living organism. In addition to providing a different view regarding the real PFAS cocktail to which the fish are exposed, POCISs fulfil the Three Rs strategy (replacement, reduction, and refinement) in animal testing.

Quantified biotic and abiotic responses to multiple stress in freshwater, marine and ground waters.

We reviewed 219 papers and built an inventory of 532 items of ecological evidence on multiple stressor impacts in rivers, lakes, transitional and coastal waters, as well as groundwaters. Our review revealed that, despite the existence of a huge conceptual knowledge base in aquatic ecology, few studies actually provide quantitative evidence on multi-stress effects. Nutrient stress was involved in 71% to 98% of multi-stress situations in the three types of surface water environments, and in 42% of those in groundwaters. However, their impact manifested differently along the groundwater-river-lake-transitional-coastal continuum, mainly determined by the different hydro-morphological features of these ecosystems. The reviewed papers addressed two-stressor combinations most frequently (42%), corresponding with the actual status-quo of pressures acting on European surface waters as reported by the Member States in the WISE WFD Database (EEA, 2015). Across all biological groups analysed, higher explanatory power of the stress-effect models was discernible for lakes under multi-stressor compared to single stressor conditions, but generally lower for coastal and transitional waters. Across all aquatic environments, the explanatory power of stress-effect models for fish increased when multi-stressor conditions were taken into account in the analysis, qualifying this organism group as a useful indicator of multi-stress effects. In contrast, the explanatory power of models using benthic flora decreased under conditions of multiple stress.

Managing aquatic ecosystems and water resources under multiple stress--an introduction to the MARS project.

Water resources globally are affected by a complex mixture of stressors resulting from a range of drivers, including urban and agricultural land use, hydropower generation and climate change. Understanding how stressors interfere and impact upon ecological status and ecosystem services is essential for developing effective River Basin Management Plans and shaping future environmental policy. This paper details the nature of these problems for Europe's water resources and the need to find solutions at a range of spatial scales. In terms of the latter, we describe the aims and approaches of the EU-funded project MARS (Managing Aquatic ecosystems and water Resources under multiple Stress) and the conceptual and analytical framework that it is adopting to provide this knowledge, understanding and tools needed to address multiple stressors. MARS is operating at three scales: At the water body scale, the mechanistic understanding of stressor interactions and their impact upon water resources, ecological status and ecosystem services will be examined through multi-factorial experiments and the analysis of long time-series. At the river basin scale, modelling and empirical approaches will be adopted to characterise relationships between multiple stressors and ecological responses, functions, services and water resources. The effects of future land use and mitigation scenarios in 16 European river basins will be assessed. At the European scale, large-scale spatial analysis will be carried out to identify the relationships amongst stress intensity, ecological status and service provision, with a special focus on large transboundary rivers, lakes and fish. The project will support managers and policy makers in the practical implementation of the Water Framework Directive (WFD), of related legislation and of the Blueprint to Safeguard Europe's Water Resources by advising the 3rd River Basin Management Planning cycle, the revision of the WFD and by developing new tools for diagnosing and predicting multiple stressors.

Integrated assessment of PAH contamination in the Czech Rivers using a combination of chemical and biological monitoring.

This study investigated polycyclic aromatic hydrocarbons (PAH) pollution of selected rivers in the Czech Republic. Integrated evaluation was carried out using combination of chemical and biological monitoring, in which we measured content of 1-hydroxypyrene (1-OHP) in chub bile and priority PAH in water samples obtained by exposing the semipermeable membrane devices at each location. The concentrations of 1-OHP in bile samples and sum of priority PAH in water sampler ranged from 6.8 ng mg protein(-1) to 106.6 ng mg protein(-1) and from 5.2 ng L(-1) to 173.9 ng L(-1), respectively. The highest levels of biliary metabolite and PAH in water were measured at the Odra River (the Bohumín site), which is located in relatively heavily industrialized and polluted region. Statistically significant positive correlation between biliary 1-OHP and sum of PAH in water was also obtained (P < 0.01, r s = 0.806).

Study of polycyclic aromatic hydrocarbon contamination of major rivers in the Czech Republic using biliary metabolite in chub, Leuciscus cephalus L.

The aim of the present study was to evaluate polycyclic aromatic hydrocarbon (PAH) contamination of the major rivers in the Czech Republic using 1-hydroxypyrene (1-OHP) content in chub bile as a biomarker. The highest concentration of 1-OHP was found in the Otava River at Topelec (80.5 ng mg protein(-1)); the lowest content of 1-OHP was found in the Vltava at Zelcín (9.6 ng mg protein(-1)). At all sites, bottom sediment samples were collected and analyzed for PAH content. The PAH content ranged between 1.2 and 15.2 mg kg dry mass(-1) at all sites. Statistically significant positive correlations (p < 0.05) between biliary 1-OHP and sediment PAH content were found. Correlation coefficients for total and individual priority PAHs ranged from 0.63 to 0.77.

Pesticide adsorption in relation to soil properties and soil type distribution in regional scale.

Study was focused on the evaluation of pesticide adsorption in soils, as one of the parameters, which are necessary to know when assessing possible groundwater contamination caused by pesticides commonly used in agriculture. Batch sorption tests were performed for 11 selected pesticides and 13 representative soils. The Freundlich equations were used to describe adsorption isotherms. Multiple-linear regressions were used to predict the Freundlich adsorption coefficients from measured soil properties. Resulting functions and a soil map of the Czech Republic were used to generate maps of the coefficient distribution. The multiple linear regressions showed that the K(F) coefficient depended on: (a) combination of OM (organic matter content), pH(KCl) and CEC (cation exchange capacity), or OM, SCS (sorption complex saturation) and salinity (terbuthylazine), (b) combination of OM and pH(KCl), or OM, SCS and salinity (prometryne), (c) combination of OM and pH(KCl), or OM and ρ(z) (metribuzin), (d) combination of OM, CEC and clay content, or clay content, CEC and salinity (hexazinone), (e) combination of OM and pH(KCl), or OM and SCS (metolachlor), (f) OM or combination of OM and CaCO(3) (chlorotoluron), (g) OM (azoxystrobin), (h) combination of OM and pH(KCl) (trifluralin), (i) combination of OM and clay content (fipronil), (j) combination of OM and pH(KCl), or OM, pH(KCl) and CaCO(3) (thiacloprid), (k) combination of OM, pH(KCl) and CEC, or sand content, pH(KCl) and salinity (chlormequat chloride).

Passive sampling methods for monitoring endocrine disruptors in the Svratka and Svitava rivers in the Czech Republic.

Endocrine-disrupting chemicals (EDC) are manmade or natural chemicals that have the ability to interfere with the endocrine system of animals. They have not been monitored systematically in the Czech Republic. The goal of the present study was the characterization of aquatic environmental pollution from the Brno (Czech Republic) city agglomeration focusing on EDC. Passive sampling devices, as well as semipermeable membrane devices (SPMD) and polar organic chemical integrative samplers (POCIS), were used for the pilot assessment of EDC. They were deployed for 21- to 28-d periods at nine locations in the Svratka and Svitava Rivers, Brno, Czech Republic, including at the inlet and outlet of Brno's wastewater treatment plant. The SPMDs were used to monitor nonpolar compounds such as polychlorinated biphenyls (PCBs), polynuclear aromatic hydrocarbons (PAHs), and organochlorinated pesticides (OCP). The POCIS were used to monitor polar compounds such as pesticides and their metabolites, perfluoro-organic compounds (PFOC), and pharmaceuticals. The passive samplers allowed very low detection limits for soluble (bioavailable) fractions of pollutants. The contribution of PAH, PCB, and HCB in sewage water to pollution of the Svratka River was low. The Brno wastewater treatment plant was identified as the main source of pharmaceuticals, triclosan, methyl triclosan, and some polar pesticides.