An estimation of groundwater type and origin of the complex karst catchment using hydrological and hydrogeochemical parameters: A case study of the Gacka river springs

Karst aquifers are heterogeneous terrains, where it is hard to assess any hydraulic parameter. Therefore, a multidisciplinary approach is necessary for research on karst aquifers. Catchment area of the Gacka river springs is typical Dinaric karst terrain built of karstified carbonates. Groundwater flow is mostly directed by preferential flow paths usually connected with main faults and fracture zones. In the presented case study structural geological and tectonic characteristics were defined. A recession diagram was created, and the water balance was calculated. Tracer-test data were also used for analysis. All these data were compared with the bulk hydrogeochemical and isotopic analyses of spring and surface waters. For this purpose, samples were obtained every month for one hydrological year at 17 sampling locations. Processing of all these data allowed a tenable definition of the Gacka spring catchment area

Definition of the river Gacka springs subcatchment areas on the basis of hydrogeological parameters

The river Gacka springs catchment area is located in the Dinaric karst, which is globally known as the locus typicus, or classical Karst. It is composed of four major and several minor karst springs of different discharge rates. The river Gacka springs are characterised by great discharge and exceptional quality, so the catchment area of the river is indicated in the Water Management Strategy (OFFICIAL GAZETTE NO. 91/08) as an area with strategically important eserves of drinking water for the Republic of Croatia. To determine the hydrogeological characteristics of he subcatchments of this large and complex aquifer system, hydrological and hydrochemical parameters were measured on the main springs. Data collected on the springs were analysed using the recession analysis by the „matching strip“ method, the statistical analysis of a time series of measured data both by autocorrelation (analysis of individual series) and by cross-correlation methods (analysis of interrelationships between time series), multivarilate statistical analysis (Factor Analysis) of hydrochemical parameters using the software package STATISTICA 6.0 (1998), and geochemical modelling of hydrochemical parameters using the NETPATH computer program. Interpretation of lithological, structural and tectonic characteristics of the rocks, together with tracing data and the applied analytical methods, allowed the springs catchment of the river Gacka to be divided into three subcatchments. The results of this study imply the necessity of a multidisciplinary approach to research. </p

Hydrochemical characterization of a Dinaric karst catchment in relation to emerging organic contaminants

The main findings of a hydrochemical investigation conducted within a typical Dinaric karst catchment located in Southern Croatia are outlined. The studied aquifer is drained by the Jadro and Žrnovnica springs, which are important for the regional and local water supplies, respectively. Presumably, there is intercatchment groundwater flow coming from the neighbouring Cetina River catchment. Various factors governing aquifer hydrochemistry and their interplay with emerging organic contaminants (EOCs) that were detected at different water resources in ng/L concentrations was assessed. A total of 26 sampling campaigns (October 2019 – October 2022) were conducted at two springs, in a river and at a deep borehole, all representative of this complex hydrogeological system. Assessment of major ion constituents and saturation indices calculated with PHREEQC revealed the sampled water resources are of a Ca-HCO3 type due to the predominant weathering of the carbonate mineral calcite. Sharp spikes observed in chemographs indicated a highly karstified system with an effective conduit network allowing rapid spring responses to precipitation events. Water resources are of good chemical status, as affirmed by anthropogenic contamination indicators, with nitrates, chlorides and sulphates all below maximum threshold values. Strong positive correlations were found between EOCs concentration, number of detected compounds, and nitrates in the Cetina River, indicating a common origin, most likely wastewater. Identification of persistent EOCs including widely used repellent N,N-diethyl- metatoluamide (DEET) during base flow conditions and its strong positive correlation with the Ca2+ content in both the Cetina and Jadro samples, suggests potential storage in the epikarst and aquifer matrix. This coupling of conventional hydrochemical indicators and novel markers of anthropogenic impacts, including EOCs, in vulnerable karst water resources is a crucial advancement in the assessment and management of emerging environmental and potential human health risks. Such an approach is pivotal for the sustainable protection of hydrogeologically intricate sites

Tracing hydrological processes: insights from hydrochemical and isotopic investigations in the northern part of Croatian Dinaric karst

This study presents the findings derived from a three-year monitoring programme focusing on the hydrochemical composition and stable isotope signatures (δ18O, δ2H) within the vulnerable karst groundwater system in Croatia\u27s northern Dinaric karst region. Covering an area of 1980 km2 across Kapela Mountain and its foothills, this groundwater system falls within the Kupa River basin and encompasses the catchment areas of the main springs across two spring levels of the Dobra, Mrežnica, and Slunjčica Rivers (namely the Vitunj, Zagorska Mrežnica, Dretulja, Veliko Vrelo, Gojak, Tounjčica, Mrežnica, and Slunjčica springs). Given the complex hydrogeological framework, prior studies have not extensively addressed the hydrochemical characteristics of this region, thereby necessitating a comprehensive investigation to elucidate system dynamics. This paper outlines the first investigation employing stable isotopic analyses within the karst groundwater system of Kapela Mt. The main results and conclusions of the research include: (i) the aquifers across Kapela Mt. drain mainly limestones, (ii) water–rock interaction and carbonate weathering are significant contributors to water geochemistry, (iii) there is a slight human impact on the Gojak and Tounjčica spring waters, (iv) the mean residence time of water in the observed aquifer is up to 1.5 years, (v) the new LMWL was calculated for Kapela Mt. based on a three-year dataset (June 2018 – May 2021), (vi) in the north Dinaric karst, the predominant origin of precipitation is from the Mediterranean air mass, (vii) Velebit Mt. has a strong influence on the precipitation isotopic composition of the study area

Characterizing occurrence of emerging organic contaminants in Dinaric karst catchment of Jadro and Žrnovnica springs, Croatia

The occurrence of emerging organic contaminants (EOCs) was investigated in vulnerable Dinaric karst catchment of Jadro and Žrnovnica springs in Croatia, under varying flow conditions and across three different water resource types (groundwater, springs, and surface water). The maximal EOCs concentration in both springs were observed following autumn recharge events, while during peak discharge no detection above the limits of detection (LOD) was recorded due to dilution process. Contrarily to springs, groundwater from deep borehole exhibited highest total EOCs concentration under low flow conditions, underscoring the considerable karst aquifer vulnerability and its oligotrophic nature. The peak EOCs concentration in karstic Cetina River coincided with the river's lowest discharge. The highest mass flux of 1013 g/day was determined for very mobile pharmaceutical metformin detected in Cetina. The presence of potentially persistent to very persistent compounds, like DEET and 1H-benzotriazole, which exhibited highest detection frequencies across all sampling sites, was observed in association with varying hydrological conditions. Hypotheses regarding the occurrence of identified EOCs include surface contamination infiltrating directly through ponors and highly karstified areas, potential persistence in the epikarst and aquifer matrix, and site-specific contamination sources for compounds such as 1H-benzotriazole, gabapentin, and ketoprofen found in groundwater. To evaluate the risk of inadvertent human exposure to EOCs across various age groups, we utilized measured spring concentrations and calculated drinking water equivalent levels (DWEL), which ranged from 1.4 μg/L for cotinine to 503 mg/L for sucralose, both detected in Jadro spring. Although EOCs concentrations in ng/L are unlikely to pose a significant risk to healthy population, long-term exposure to EOCs mixture remains unknown. Given scarcity of research on EOCs in karst environments on both global and national levels, our study enhances comprehension of their occurrence and behaviour across different karst water resources that hold crucial importance for drinking water supply in regions like Dinarides

"Novi onečišćivači" u podzemnim vodama Hrvatske - primjer projekata GeoTwinn i boDEREC-CE

Stanje vodnih resursa i pridruženih ekosustava je pod sve većim pritiskom onečišćenja nastalog kao posljedica neadekvatnih i nereguliranih ljudskih aktivnosti, čiji je utjecaj sve izraženiji gledano s aspekta posljedica promjena klimatskih uvjeta. Tehnološki razvoj analitičkih instrumenata i metoda omogućio je određivanje tzv. novih onečišćivača ( engl. emerging contaminants) odnosno spojeva koji do sada nisu uključeni u redoviti sustav monitoringa, a prepoznat je njihov ekotoksikoloski učinak. U širokom spektru utvrđenih spojeva najčešći su pesticidi, farmaceutici, proizvodi za osobnu njegu, industrijski aditivi i njihovi nusprodukti, dodaci hrani, nusprodukti tretiranja vode, surfaktanti, hormoni i dr. Značajke i uvjeti podzemnog toka i transporta novih onečiščivaća u kompleksnim krškim sredinama uz definiranje učinkovitih mjera (monitoringa, zabrane, prevencije i sl.) koje će ublažiti posljedice spomenutih negativnih utjecaja na stanje podzemnih vodnih resursa istražuju se u sklopu međunarodnih projekata GeoTwinn (Horizon 2020) i boDEREC-CE (Interreg Central Europe). Suradnja s renominiranim stručnjacima obogatit ce dosadašnje spoznaje hrvatskih partnera o ponašanju novih onečiščivaća u ovakvim okolišima te doprinijeti zaštiti i očuvanju podzemnih voda kao neophodnog i strateški važnog resursa pitke vode

Groundwater level and electrical conductivity datasets acquired within pumping tests on Ilovik Island in Croatia

The small karst island of Ilovik is the most southern of inhabited islands in the Croatian part of the Adriatic Sea. During summer tourist season the number of inhabitants increases significantly, and securing the additional freshwater quantities was needed. Given the hydrogeological and geomorphological setting of the island, possibility of brackish groundwater exploitation was considered. Hence, borehole drilling accompanied with pumping tests at three specified locations was carried out. During the pumping tests in two campaigns, groundwater level was measured manually every 2 hours in boreholes, while groundwater electric conductivity and temperature were periodically measured in situ. The sea level was observed at the reference point located near port.Given dataset consists of electrical conductivity, temperature, groundwater and seawater levels. The research article connected with these data (Terzić et al., 2020) provides hydrogeological interpretation of brackish groundwater lens on small karst island