Soil plays an important role in the accumulation and transport of potentially toxic elements (PTEs), from surface into aquifer. PTEs can get to the environment naturally, but also from different ...kinds of contamination sources. In this study, a soil profile located in the vicinity of well field Petruševec, one of the most important well fields related to the public water supply of the City of Zagreb, was analyzed. The main aim of this study was to determine soil properties which can influence retention/mobilization of Ni and Cr in alluvial soil, as well as to define their origin in the investigated soil profile. Results suggest that Cr is geogenic, while Ni is probably of dominantly anthropogenic origin. Observed concentrations, enrichment factors and Igeo values showed no enrichment for Cr, while for Ni, they showed minor to very severe enrichment, i.e., that in some soil horizons, moderate to strong pollution exists. Evaluation of wind directions and location of possible contamination sources that prevail in the study area suggest that Ni can come by aerodeposition from different sources. Results showed that mineral composition can have important influence on retention of analyzed PTEs. Soil horizons, which have very high concentrations of Ni, in general have higher proportion of clay minerals, especially chlorites, as well as Fe oxyhydroxides which can act as an adsorption phase for the investigated PTEs. Results suggest that more detailed research about the investigated PTEs presents a necessity if measures for soil and groundwater protection want to be effectively implemented.
Nitrates present one of the main groundwater contaminants in the world and in the Zagreb aquifer. The Zagreb aquifer presents the main source of potable water for the inhabitants of the City of ...Zagreb and it is protected by the Republic of Croatia. The determination of contaminants trends presents one of the main tools in groundwater body status and risk assessment. In this paper, the use of regression analysis on the aggregated data, together with confidence and prediction intervals, at different observation scales has been evaluated. Nitrate concentrations are generally decreasing in almost all areas, observed at different observation scales. It has been shown that linear regression can be efficiently used in the estimation of nitrates trends. Results showed that the calculation of confidence and prediction intervals can provide more useful conclusions than the calculation of the trend’s statistical significance. Also, the results suggest that confidence and prediction intervals can be used in groundwater body chemical status and risk assessment, respectively. Data smoothing and data aggregation are generally desirable, but have certain limitations. If too much data is aggregated, trend estimation by regression analysis can point to false conclusions. Evaluation of trends at different observational scales can provide more realistic trend estimation, as well as more precise identification of areas where groundwater protection measures should be implemented.
This paper presents a conceptual model of the Zagreb aquifer system. The conceptual model can be applied to groundwater status risk assessment and pollution risk assessment at the local scale, thus ...satisfying both environmental and preventative/limitation objectives of the Water Framework Directive (WFD) and Groundwater Directive (GWD). Its main purpose is to apply a risk assessment procedure, according to the WFD requirements, and to serve as a foundation for setting up a numerical model of flow in both the saturated and unsaturated zones in order to identify pressure and impact effects on groundwater quality. The model is divided into two parts, taking into account the WFD requirement to assess a risk for a wide range of source-pathway-receptor relationships. The Global Conceptual Model (GCM) provides insight into the processes and pressures at the level of the groundwater system. It contains the geological and hydrogeological characterization of the Zagreb aquifer system and the description of the most significant point and diffuse sources and pathways of pollution and processes influencing pollutant behaviour in saturated and unsaturated zone of the groundwater system. The main pollutants of the Zagreb aquifer system are potentially toxic metals, nitrates, pesticides, pharmaceuticals and chlorinated aliphatics. A Local Conceptual Model (LCM) supports parameterization of the whole groundwater system through the description of heterogeneities and flow and solute parameters of the system components at two sites representing local conditions in the saturated (Stara Loza) and unsaturated (Kosnica) zones. This concept can be regarded as an effective tool for groundwater management of the groundwater system and its compartments and for communicating the conditions in complex groundwater systems with experts, policy makers and general public in an understandable way.
The main purpose of this study was to understand the interactions between precipitation, surface water, and groundwater in the Zagreb aquifer system using water stable isotopes. The Zagreb aquifer is ...of the unconfined type and strongly hydraulically connected to the Sava River. As the groundwater is the main source of drinking water for one million inhabitants, it is essential to investigate each detail of the recharge processes of the aquifer to ensure adequate protection of the groundwater. Measuring the content of water stable isotopes in surface waters and groundwater enabled the creation of two- and three-component mixing models based on the isotopic mass balance for the purpose of the quantification of each recharge component. The mixing models gave ambiguous results. Observation wells equally distant from the Sava River did not have the same recharge component ratio. This indicated that there were more factors (in addition to the distance from the river) that were affecting groundwater recharge, and the properties of the unsaturated zone and surface cover data were therefore also taken into consideration. The thickness of the unsaturated zone and the characteristics of different soil types were identified as important factors in the recharge of the Zagreb aquifer. The areas with high thickness of the unsaturated zone and well-permeable soil had a very similar recharge component ratio to the areas with small thickness of the unsaturated zone but low-permeable soil.
Groundwater quality is a consequence of cumulative effects of natural and anthropogenic processes occurring in unsaturated and saturated zone, which, in certain conditions, can lead to elevated ...concentrations of chemical substances in groundwater. In this paper, the concept of determining the ambient background value of a chemical substance in groundwater was applied, because the long-term effects of human activity influence the increase in concentrations of substances in the environment. The upper limits of ranges of ambient background values were estimated for targeted chemical substances in four groundwater bodies in the Pannonian region of Croatia, according to the demands of the EU Groundwater Directive. The selected groundwater bodies are typical, according to the aquifer typology, for the Pannonian region of Croatia. Probability plot (PP), the modified Lepeltier method, as well as the simple pre-selection method, were used in this paper, depending on a number of chemical data in analysed data sets and in relation to the proportion of <limit of quantification (LOQ) values in a data set for each groundwater body. Estimates obtained by using PP and the modified Lepeltier method are comparable when data variability is low to moderate, otherwise differences between estimates are notable. These methods should not be used if the proportion of <LOQ values in a data set is higher than 30%; however, the integration of results of both methods can increase the confidence of estimation. If the proportion of <LOQ values is higher than 30%, it is recommended to use the robust pre-selection method with the adequate confidence level. For highly skewed data, the 90th percentile of the pre-selected data set is comparable with other methods and preferable over the 95th percentile. The estimates obtained for inert and mobile substances are comparable on different scales. For highly redox-sensitive substances, estimates may differ by one to two orders of magnitude, in relation to the observed heterogeneity of the aquifer systems. The critical issue in the estimation process is the determination of hydrogeological and geochemical homogeneous units within the heterogeneous aquifer system.
This study demonstrates an approach to estimate the background value of nitrate as a basis for better groundwater management and protection in areas under long-term human impact. The aim was to ...determine the ambient background value (ABV) of nitrate in the catchment area of the Velika Gorica well field, a hydrogeologically homogeneous area within the Zagreb aquifer. ABVs are determined using four well-known model-based objective methods (the iterative 2-σ technique, IT; the calculated distribution function, CDF; the cumulative frequency curve, CFC; and the probability plot, PP), while simultaneously testing the reliability of the results of each method. If the results are not statistically significant, data selection is performed. The results show that using data without selection can lead to statistically non-significant ABVs, but with the additional selection of data, a statistically non-significant result became a statistically significant one. In summary, all final ABVs must be statistically significant and determined using as large a data set as possible. Reducing the size of the data set is acceptable only in the case of a statistically non-significant result.
Nitrates are among the most common groundwater contaminants worldwide, and the same situation is present within the Zagreb aquifer. The Zagreb aquifer presents the only source of potable water for ...inhabitants of the City of Zagreb and part of Zagreb County. Isotopic composition of water (δ2H and δ18O) and nitrates (δ15N and δ18O), groundwater chemistry, and molar ratios, in combination with correlation and multivariate statistical methods, have been used for the estimation of nitrate origin. Nitrate stable isotopes excluded synthetic fertilizer as the main source of nitrate contamination. They showed insignificant influence of denitrification on nitrate concentrations but could not define the main source of nitrate contamination. The usage of molar ratios, especially NO3−/K+, helped to clarify this issue. Waste water has been defined as the main source of nitrate contamination. All results indicate that nitrogen in a large extent enters the aquifer in the form of ammonium ion, which is transformed to nitrates by the process of nitrification.
Nitrates represent one of the main groups of contaminants in the Zagreb aquifer system. Some natural groundwater quality indicators can have a significant influence on their stability and mobility in ...the saturated zone. Correlation and multivariate statistical analyses were used to test the correlation of average values of NO3- with O2, ORP, pH, EC and temperature of groundwater, and to allocate observation wells that belong to the same clusters. ORP values didn't relate to any observed variables, which is probably due to their variability which suggests changes in the oxidation-reduction conditions in the aquifer system. Principal component analysis was used for the determination of variables that are related to the nitrate concentrations and which were then used in cluster analysis. Other variables were excluded from cluster analysis. Three methods were used to perform cluster analysis, where the results calculated with Ward's method were chosen as the most appropriate. In the end, two clusters were identified, one with smaller, and one with higher NO3-, O2 and EC values. Observation wells from cluster 1 are generally located near the Sava River and have similar nitrate concentrations. Lack of other nitrogen species and moderately aerobic conditions suggest very fast nitrification in the shallow Holocene aquifer.
Intensive agricultural practices increase agrochemical pollution, particularly nitrogen (N) based fertilizers, which present an environmental risk. This study aims to evaluate long-term (2009–2020) ...data on soil water regime and nitrate dynamics at an agricultural experimental site on fine-textured soils and to better understand the implications of N management in relation to groundwater pollution. The field site is located in the Biđ field (eastern Croatia), in the proximity of the Sava river. Zero-tension lysimeters were installed at six selected locations. Lysimeters were used to monitor the water regime, i.e., outflows in which nitrate concentration was measured, while additional soil-water samples were collected via 4 and 15-meter-deep monitoring wells. Soil hydraulic parameters were estimated by combining the laboratory measurements, and estimation in RETC software. Water regime and nitrate leaching in lysimeters were simulated using HYDRUS-1D for each year to allow crop rotation and to evaluate their effects individually. The HYDRUS-1D model successfully reproduced lysimeter outflows and nitrate dynamics, which was confirmed with high R2 values (water: 93% above 0.7, and nitrate: 73% above 0.7) indicating the good performance of the model simulating nitrification chain reactions. Principal component analysis (PCA) was performed to identify the relationships among all soil properties and environmental characteristics. The results showed the complex interaction of soil hydraulic properties, precipitation patterns, plant uptake, and N application. All locations have a decreasing trend of nitrate leaching over the investigation period. Most of the lysimeter outflows and elevated nitrate concentrations were connected to the wet period of the year when the soil was saturated, and evapotranspiration was low. The results of this study show that it is important to optimize N fertilizer applications for each particular environmental condition to reduce nitrate loss. The study indicates the importance of long-term field studies, key for agro-hydrological modeling and the improvement of agricultural practices.
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•Interaction of soil hydraulic parameters, rainfall, crops, and nitrogen is presented.•HYDRUS-1D successfully reproduced long-term lysimeter outflows and nitrate dynamics.•Field conditions and evapotranspiration affected outflows and nitrate concentrations.•Long-term field data is key for modeling and improvement of agricultural practices.
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