Yuliya Vystavna

Pharmaceuticals in Rivers of Two Regions with Contrasted Socio-Economic Conditions: Occurrence, Accumulation, and Comparison for Ukraine and France

The goal of our study was to identify pharmaceuticals, their potential sources and consumption level in two different socioeconomic and geographical regions—Bordeaux, France and Kharkiv, Ukraine. These substances were monitored in rivers water during contrasted seasonal conditions with application of passive samplers. The 21 pharmaceuticals (psychiatric drugs: alprazolam, amitriptyline, diazepam, fluoxetine, nordiazepam, carbamazepine, bromazepam; analgesics: aspirin, paracetamol; broncholidator: clenbuterol, salbutamol, terbutaline; non-steroidal anti-inflammatory drug: diclofenac, ibuprofen, ketoprofen, naproxen; lipid regulator: gemfibrozil; stimulants: caffeine, theophylline) were identified in sites upstream and downstream of urban areas and discharge of wastewaters. Caffeine, carbamazepine, and diclofenac were relatively abundant into the surface water and could be considered as potential anthropogenic markers of wastewater discharges into rivers. A mass balance modeling has been applied to calculate approximate consumption rates for carbamazepine, diclofenac, and caffeine in both regions to assess socio-economic factors linked with pharmaceuticals behavior.

Monitoring of trace metals and pharmaceuticals as anthropogenic and socio-economic indicators of urban and industrial impact on surface waters.

The research focuses on the monitoring of trace metals and pharmaceuticals as potential anthropogenic indicators of industrial and urban influences on surface water. This study includes analysis of tracers use for the indication of water pollution events and discussion of the detection method of these chemicals. The following criteria were proposed for the evaluation of indicators: specificity (physical chemical properties), variability (spatial and temporal), and practicality (capacity of the sampling and analytical techniques). The combination of grab and passive water sampling (i.e., diffusive gradient in the thin film and polar organic chemical integrated samplers) procedure was applied for the determination of dissolved and labile trace metals (Ag, Cd, Cr, Cu, Ni, Pb, and Zn) and pharmaceuticals (carbamazepine, diazepam, paracetamol, caffeine, diclofenac, and ketoprofen). Samples were analyzed using inductively coupled plasma mass spectrometry (MS; trace metals) and liquid chromatography–tandem MS electrospray ionization+/− (pharmaceuticals). Our results demonstrate the distinctive spatial and temporal patterns of trace elements distribution along an urban watercourse. Accordingly, two general groups of trace metals have been discriminated: “stable” (Cd and Cr) and “time varying” (Cu, Zn, Ni, and Pb). The relationship Cd ≫ Cu > Ag > Cr ≥ Zn was proposed as an anthropogenic signature of the industrial and urban activities pressuring the environment from point sources (municipal wastewaters) and the group Pb–Ni was discussed as a relevant fingerprint of the economic activity (industry and transport) mainly from non-point sources (runoff, atmospheric depositions, etc.). Pharmaceuticals with contrasting hydro-chemical properties of molecules (water solubility, bioaccumulation, persistence during wastewater treatment processes) were discriminated on conservative, labile, and with combined properties in order to provide information on wastewater treatment plant efficiency, punctual events (e.g., accidents on sewage works, runoff), and uncontrolled discharges. Applying mass balance modeling, medicaments were described as relevant socio-economic indicators, which can give a picture of main social aspects of the region.

Trace metals in wine and vineyard environment in southern Ukraine

The study was focused on measuring the concentration levels of trace metals in the environment, vines and wine within the wine-growing region of Ukraine and comparing the findings to the data from well known wine-growing areas. Analysis was carried out of Cr, Cu, Ni, Pb and Zn in irrigation water, grape juice and wine, Cu, Pb and Zn in soil (pseudo-total and acid-soluble fractions) and Vitis vinifera L. in leaves and grapes. The accumulation levels of Cu and Zn from soil to leaves were significantly higher than from soil to grapes. Pb had lower potential to accumulate in aerial parts than Cu and Zn. Higher contents of Cu and Zn were observed in Muscat white grape juice compared to Chardonnay. The concentration levels of Zn and Cu were higher in wine than in juice. Trace metals were regulated by the soil composition and biological specificity of cultivars. The data obtained from the study area did not exceed the international limits.

Monitoring and flux determination of trace metals in rivers of the Seversky Donets basin (Ukraine) using DGT passive samplers

This paper reports the results of the in situ application of diffusive gradients in thin-films (DGT) passive samplers for trace metals (Cd, Co, Cr, Cu, Ni, Pb and Zn) monitoring in transboundary Udy and Lopan rivers of the Seversky Donets watershed in the Kharkiv region (Ukraine), which has a long history of industrial development. The research discusses potential sources of DGT-measured labile metals in water and seasonal variations. Our results demonstrate the application of DGT for identifying and measuring labile metal concentrations in contrasted climate conditions (cold snowy winter and hot summer) and appropriateness of such a tool for continuous water monitoring with the presence of an ice cover. Results show that DGT-measured concentrations of most of trace metals were much higher downstream of the wastewater treatment plants discharges than upstream; thus wastewater treatment plants seemed not able to reduce or to remove trace metals’ contaminations and become major sources of pollutants in the studied rivers. The calculation of the average metal fluxes based on the DGT-measured concentrations confirmed that the urban wastewater discharges significantly contribute to the metal fluxes into the Udy and the Lopan rivers during both low-flow and high-flow periods. Compared to the wastewaters inputs to the rivers, the transboundary effect is limited, but should be taken into account as the origin of some metals is from sources located on the adjacent Russian territory.

Nitrate contamination in a shallow urban aquifer in East Ukraine: evidence from hydrochemical, stable isotopes of nitrate and land use analysis

Abstract A combined hydrochemical and stable isotope approach was used to investigate the origin of nitrate in the shallow unconfined groundwater of Kharkiv city, Eastern Ukraine. The contamination was investigated in the context of land use within the catchment area. The observed enrichment of sulfate, chloride and nitrate suggests significant groundwater contamination in the shallow urban aquifer, which is widely used as drinking water source for the urban population. Characteristic nitrate/chloride ratios as well as stable isotope ratios (N and O) of nitrate in the most contaminated springs confirmed that septic waste from leaky sewer systems was the main source of nitrate contamination in the groundwater. Nitrate contamination is linked to the type of land use and sewage treatment regime in the catchment area. It is also modulated by the regional hydrogeology, which determines the susceptibility of a given aquifer toward groundwater pollution. A more quantitative assessment of nitrate sources based on the nitrate isotope analysis alone is rather difficult. However, our study confirms that the combination of hydrochemical tracers, robust land-use analysis and nitrate stable isotope measurements represents a valuable approach to identify the origin of the nitrate contamination.

Trace metals transfer during vine cultivation and winemaking processes: Trace metals transfer during vine cultivation and winemaking

BACKGROUND The study was focused on Zn, Cu and Pb transfer in the system of soil-grape-must-juice-wine in a Chardonnay grape variety from Ukrainian vine growing regions. The analyses of soil, grape, must, pomace, juice and wine were done at the study plot in the south-west of Crimea. RESULTS Commercial white wines of Chardonnay from different vine growing regions in Ukraine were analysed for trace metals content. Results revealed that trace elements transfer was related to diverse Zn, Cu and Pb sources, trace metals bioavailability, their speciation and complexes during the wine making processes. The analysed commercial wines had lower Cu, Zn and Pb concentrations than wine from the Inkerman study plot. CONCLUSION Trace metals concentrations were comparable to those in European wines and lower than limits recommended by International Organization of Vine and Wine. The tentative relationship between wine and soil was found for Zn at the study plot. The method can be used to describe the relationship between the soil and wine in other study areas.

Water laws of Georgia, Moldova and Ukraine: current problems and integration with EU legislation

ABSTRACT The water laws of Georgia, Moldova and Ukraine are reviewed and compared with the Water Framework Directive of the European Union with a focus on water quality, water pollution and water management. Theoretical aspects and the implementation of the laws are discussed in terms of integration with European water legislation. Discrepancies are identified that should be addressed in future national legislation.

Priority substances and emerging pollutants in urban rivers in Ukraine: Occurrence, fluxes and loading to transboundary European Union watersheds

The occurrence and fluxes of 18 priority substances and emerging pollutants listed in the European Union Water Framework Directive and a Watch List (trace metals (Cd, Pb and Ni), nonylphenols, octylphenols, 8 polyaromatic hydrocarbons, 4 dioxin-like polychlorinated biphenyls and diclofenac) were investigated in a Ukrainian city and the mass discharge loads of these compounds into EU-transboundary watersheds were estimated. Fluxes of chemicals were calculated per capita and per area of the Ukrainian urban territory and used to estimate mass loading of priority and emerging concern compounds from Lviv, Uzhorod and Chernivtsi (West Ukraine) to neighbouring EU-transboundary rivers. The highest loading was found for trace metals (1.15 t a-1), diclofenac (0.7 t a-1) and nonylphenols (0.4 t a-1). Transboundary water contamination must be considered in order to successfully manage water resources in a manner that fulfils the requirements of EU environmental quality standards.

Defining a stable water isotope framework for isotope hydrology application in a large trans-boundary watershed (Russian Federation/Ukraine)

ABSTRACT Stable isotopes of hydrogen (2H) and oxygen (18O) of the water molecule were used to assess the relationship between precipitation, surface water and groundwater in a large Russia/Ukraine trans-boundary river basin. Precipitation was sampled from November 2013 to February 2015, and surface water and groundwater were sampled during high and low flow in 2014. A local meteoric water line was defined for the Ukrainian part of the basin. The isotopic seasonality in precipitation was evident with depletion in heavy isotopes in November–March and an enrichment in April–October, indicating continental and temperature effects. Surface water was enriched in stable water isotopes from upstream to downstream sites due to progressive evaporation. Stable water isotopes in groundwater indicated that recharge occurs mainly during winter and spring. A one-year data set is probably not sufficient to report the seasonality of groundwater recharge, but this survey can be used to identify the stable water isotopes framework in a weakly gauged basin for further hydrological and geochemical studies.

Long-term trends of phosphorus concentrations in an artificial lake: Socio-economic and climate drivers

European freshwater ecosystems have undergone significant human-induced and environmentally-driven variations in nutrient export from catchments throughout the past five decades, mainly in connection with changes in land-use, agricultural practice, waste water production and treatment, and climatic conditions. We analysed the relations among concentration of total phosphorus (TP) in the Slapy Reservoir (a middle reservoir of the Vltava River Cascade, Czechia), and socio-economic and climatic factors from 1963 to 2015. The study was based on a time series analysis, using conventional statistical tools, and the identification of breaking points, using a segmented regression. Results indicated clear long-term trends and seasonal patterns of TP, with annual average TP increasing up until 1991 and decreasing from 1992 to 2015. Trends in annual, winter and spring average TP concentrations reflected a shift in development of sewerage and sanitary infrastructure, agricultural application of fertilizers, and livestock production in the early 1990s that was associated with changes from the planned to the market economy. No trends were observed for average TP in autumn. The summer average TP has fluctuated with increased amplitude since 1991 in connection with recent climate warming, changes in thermal stratification stability, increased water flow irregularities, and short-circuiting of TP-rich inflow during high flow events. The climate-change-induced processes confound the generally declining trend in lake-water TP concentration and can result in eutrophication despite decreased phosphorus loads from the catchment. Our findings indicate the need of further reduction of phosphorus sources to meet ecological quality standards of the EU Water Framework Directive because the climate change may lead to a greater susceptibility of the aquatic ecosystem to the supply of nutrients.