Organic contaminants in groundwater are among the most challenging chemical compound contaminants today, particularly when it comes to understanding their occurrence, origin, and relations in groundwater, as well as the transport processes, fate, and environmental impacts involved. This paper presents the use of active carbon fibre (AFC) passive sampling and multivariate statistical processing of the results to predict the possible occurrence of organic compounds (OCs) in groundwater and to determine the origin of various anthropogenic activity. This study aims to deepen our knowledge on the control of OCs in groundwater by introducing a multi-analytical and multi-elemental holistic approach, using the Dravsko polje aquifer, the largest intergranular aquifer in Slovenia, as an example. The occurrence of OCs in groundwater was determined by means of ACFs and compared against the characteristics of the recharge area and the type of compounds detected. We combined hierarchical cluster analysis (HCA) and principal component analysis (PCA) to identify the relationship between different OCs in groundwater. The relationships between their occurrence, environmental setting and type of compound were determined using multiple linear regression (MLR). From the total of 343 organic compounds detected using passive sampling, 47 were included in further statistical analysis. MLR shows that the environmental setting is one of the most important factors affecting the different types of pollutants in groundwater. MLR models were calculated for different sources of pollution (agricultural, urban, and industrial) based on the environmental setting, land use, agglomeration, infrastructure networks, and hydrogeological characteristics of the aquifer. By means of HCA and PCA, we identified the relationships between different OCs in groundwater. As expected, the strongest correlations were found between primary compounds and their degradation products (e.g. atrazine and desethylatrazine) and compounds of similar use (e.g. atrazine and propazine, also desethylatrazine and propazine, atrazine and simazine). Some of them were also found to have a similar molecular structure (e.g. palmitic and stearic acid, 5-methoxygramine and 5-methoxytryptamine). The use of the same substances in different environments (agricultural/urban) makes them markers of both (different) origins. Therefore, it is particularly important to determine the combination of markers of different origin using multivariate statistical methods, especially in the case of mixed land use. This study identifies the main factors influencing the distribution of groundwater OCs and thus contributes to a more comprehensive understanding of the vulnerability of shallow groundwater to surface-derived contamination in similar environments.

With increasing exploitation of groundwater resources and implementation of various activities in their recharge areas, it is vital to conduct a comprehensive assessment of aquifers to ensure their conservation and sustainable management. In the present study, we used a comprehensive approach to conceptualise and identify the functioning of two connected aquifer systems in north-eastern Slovenia: the Quaternary porous aquifers Dravsko polje and Ptujsko polje. The study presents the conceptual models of both aquifers and their interconnectedness using separate mathematical-numerical models with the aim of ensuring an integrated management of these alluvial aquifer systems. It also highlights the importance of understanding connections between such systems for simulating groundwater flow and transport of different contaminants. To describe the entire aquifer system, the study defines its three essential elements: the geometry of the aquifers, their recharge by precipitation, and other boundary conditions. The geometry of the Quaternary aquifers was defined using Sequential Indicator Simulation (SIS) with the ESRI’s ArcMap software. Next, LIDAR was used for determining their surface geometry. The hydrogeologic model was designed using the Groundwater Modelling System (GMS) developed by AQUAVEO. We used the MODFLOW 2000 calculation method based on the finite difference method (FDM). The model was calibrated with the PEST module, which was used to calibrate hydraulic conductivity and hydraulic heads between the measured and modelled data. Finally, the model was validated using the Nash–Sutcliffe (NSE) efficiency coefficient. In addition, the model results estimated using the PEST tool were validated with the hydraulic conductivities determined at the pumping sites (pumping tests), each belonging to water protection zones that define the maximum travel time of the particles. This was performed using the MODPATH method. The paper also presents the possibility of modelling heterogeneous but interdependent aquifers in a groundwater body. Modelling the connection between the two aquifers, which are the most important ones in the region, is essential for a comprehensive management of the entire system of water resources. The models allow for a better understanding of groundwater flow in both aquifers. Moreover, their interconnectedness will be used for further studies in this field, as well as for integrated water management.

Legislation addressing the quality of groundwater and increasing concerns over public health calls for the development of analytical methods that can produce accurate and precise results at the ppt level. Passive sampling has been recognised as a helpful tool in identifying various organic pollutants in groundwater, even when their presence had not yet been identified through conventional groundwater quality monitoring. The article presents an analytical method involving a simple and cost-effective passive sampling device using Zorflex^® activated carbon fibres (ACFs) for the qualitative monitoring of a broad range of organic pollutants in water in a single run. The applicability of the method developed was tested in three hydrogeological studies. In the first case, we present a non-targeted qualitative screening and a list of 892 different contaminants detected in the groundwater in Slovenia. In the second case, we discuss the presence and origin of organic compounds in the groundwater from a pilot area of the urban aquifer, Ljubljansko polje. The third case presents a comparison of results between passive and grab sampling. Passive sampling with ACFs confirmed the presence of a pollutant, even when it had not been previously detected through a quantitative method.

Determining the transport characteristics of pollutants in a gravel unsaturated zone is particularly difficult, owing to the heterogeneity of the geological media. Understanding the mechanisms and rates of movement of pollutants in the unsaturated zone is an important issue in the process of groundwater protection. One of the most valuable ways of investigating the characteristics, groundwater flow and solute transport in the unsaturated zone is by conducting experimental research, namely tracer experiments. Flow and transport parameters of propyphenazone, caffeine and carbamazepine have been studied with tracer experiments using a lysimeter facility in the Selniška Dobrava (NE Slovenia). The lysimeter site is designed as a field laboratory. The dimensions are 2x2 m, 5 m deep, with 0.2 m thick walls. There are 10 sampling and measuring points at different depths (from JV-1 to JV-10) with approximately equal distances in depth. For the purpose of sampling groundwater in the unsaturated zone, drainage samplers were installed and connected to a water sampling system. The tracer experiment lasted over a time period of approximately two years. The organic pollutants selected to determine the processes of migration and degradation through the aquifer were carbamazepine, propyphenazone and caffeine. Compounds differ in their physical and chemical properties, which results in different transport paths and velocities of individual pollutants through the aquifer. Due to its conservative behaviour, deuterated water was used as the conservative tracer. For the evaluation of flow and transport parameters the HYDRUS 1-D software was used. In the conference contribution, modelling and estimation of hydraulic properties of the soil and selected pharmaceuticals within a coarse gravel unsaturated zone will be presented.