Monitoring of various naturally present substances or physical properties of the water, commonly called environmental tracers, can provide valuable insight in characteristics of groundwater flow systems and intrinsic processes. Analysis of individual tracer data most often gives an ambiguous interpretation, but employment of multiple diverse tracers can greatly increase interpretation reliability. We monitored multiple natural tracers including spring water electrical conductivity, temperature, loads of major anions and cations, stable isotopes of water, and total organic carbon together with discharge dynamics on Krbavica springs located in the Croatian part of Dinaric Karst region. We also monitored dissolved oxygen concentration as an indicator of “excess air” dynamics in the spring water, which is a very rarely recognized and not properly understood phenomenon in the karst groundwater studies. Analysis of the monitoring data revealed main characteristics of the karst system, among which following can be emphasized: (1) oxygen concentration together with conductivity and temperature (parameters monitored with high temporal resolution) were strongly related to discharge dynamics, while seasonal patterns were absent; (2) supersaturation with oxygen confirmed presence of “excess air”, most pronounced in high water conditions following the hydrograph peaks, indicating prevalence of closed flow conditions within the system; (3) electrical conductivity showed “anomalous” gradual decrease during the hydrograph recessions, attributed both to CO₂ dynamics and mobilization of water from tiny fissures during high recharge conditions; and (4) stable isotope measurements confirmed good mixing of water within the system with mean residence time of a few years. Simultaneous monitoring of diverse tracer dynamics enabled detailed characterization of the karst system without excessive ambiguity.

Crystalline rocks are generally characterized by negligible porosity and permeability in terms of groundwater exploitability. However, alteration processes can greatly increase their fracture permeability and induce formation of modest, but locally important aquifers. Therefore, subsurface characteristics of alteration zones are of major importance for hydrogeological evaluation of crystalline terrains. Alteration processes greatly affect rock total porosity and water content, causing contrasting electrical resistivity of rocks affected by varying degrees of weathering. This makes electrical resistivity tomography (ERT) a preferable geophysical method for the exploration of alteration zones in crystalline rocks. In our research, we used an integrated approach, combining the ERT method with monitoring of spring discharge and hydrochemistry to characterize metamorphic aquifers on slopes of the Medvednica Mountain (Croatia). Significant fracture flow aquifers are found to be formed in intensely fractured but not highly weathered rock masses (medium to high resistivity values), while highly weathered masses (low resistivity values) form local barriers for fracture flows. Subsurface structure of the alteration zone proved to be highly irregular, with sharp contacts between more and less weathered rocks. Decrease of permeability below the alteration zone keeps the water level near the surface and enables spring occurrence on the mountain slopes. Studied aquifers have relatively limited extent, resulting in typical capacity of major springs of a few l/s. More frequent but less productive springs are attributed to the draining of the shallow part of the alteration zone (mostly saprolite). Combination of the ERT method with spring monitoring proved to be very effective as a first and relatively inexpensive methodology for hydrogeological characterization of crystalline terrains, both in local and catchment scales.

Hydrodynamic characteristics of Mt. Biokovo foothill springs in Croatia

Emerging organic contaminants (EOCs) have become of increasing interest due to concerns about their impact on humans and the wider environment. Karst aquifers are globally widespread, providing critical water supplies and sustaining rivers and ecosystems, and are particularly susceptible to pollution. However, EOC distributions in karst remain quite poorly understood. This study looks at the occurrence of EOCs in the Croatian karst, which is an example of the "classical" karst, a highly developed type of karst that occurs throughout the Dinaric region of Europe. Samples were collected from 17 karst springs and one karst lake used for water supply in Croatia during two sampling campaigns. From a screen of 740 compounds, a total of 65 compounds were detected. EOC compounds from the pharmaceutical (n = 26) and agrochemical groups (n = 26) were the most frequently detected, while industrials and artificial sweeteners had the highest concentrations (range 8-440 ng/L). The number of detected compounds and the frequency of detection demonstrate the vulnerability of karst to EOC pollution. Concentrations of 5 compounds (acesulfame, sucralose, perfluorobutane sulfonate, emamectin B1b, and triphenyl phosphate) exceeded EU standards and occurred at concentrations that are likely to be harmful to ecosystems. Overall, most detections were at low concentrations (50 % <1 ng/L). This may be due to high dilution within the exceptionally large springs of the Classical karst, or due to relatively few pollution sources within the catchments. Nevertheless, EOC fluxes are considerable (10 to 10⁶ ng/s) due to the high discharge of the springs. Temporal differences were observed, but without a clear pattern, reflecting the highly variable nature of karst springs that occurs over both seasonal and short-term timescales. This research is one of a handful of regional EOC investigations in karst groundwater, and the first regional study in the Dinaric karst. It demonstrates the need for more frequent and extensive sampling of EOCs in karst to protect human health and the environment.