The geochemical and isotopic composition of surface waters and groundwater in the Velenje Basin, Slovenia, was investigated seasonally to determine the relationship between major aquifers and surface waters, water–rock reactions, relative ages of groundwater, and biogeochemical processes. Groundwater in the Triassic aquifer is dominated by HCO₃–, Ca²⁺, Mg²⁺and δ¹³CDICindicating degradation of soil organic matter and dissolution of carbonate minerals, similar to surface waters. In addition, groundwater in the Triassic aquifer has δ¹⁸O and δD values that plot near surface waters on the local and global meteoric water lines, and detectable tritium, likely reflecting recent (<50 years) recharge. In contrast, groundwater in the Pliocene aquifers is enriched in Mg²⁺, Na⁺, Ca²⁺, K⁺, and Si, and has high alkalinity and δ¹³CDICvalues, with low SO₄²–and NO₃–concentrations. These waters have likely been influenced by sulfate reduction and microbial methanogenesis associated with coal seams and dissolution of feldspars and Mg-rich clay minerals. Pliocene aquifer waters are also depleted in¹⁸O and²H, and have³H concentrations near the detection limit, suggesting these waters are older, had a different recharge source, and have not mixed extensively with groundwater in the Triassic aquifer.

Research into the unsaturated zone and groundwater recharge can greatly improve understanding of hydrological processes and assist in sustainable groundwater management. Groundwater recharge of the Ljubljana Field aquifer, a coarse-gravel porous aquifer in Slovenia, was estimated with reference to soil characteristics, outflow data from a weighing lysimeter, and water-table fluctuation. The specific yield of the upper unsaturated zone determined from soil characteristics was 0.141 for the top soil layer (0–0.35 m), between 0.042 and 0.066 for the layer below the top soil (0.35–1.3 m), and between 0.239 and 0.219 for the underlying upper coarse layer. During long dry periods, especially in combination with times of high plant-water requirements, only substantial precipitation events directly contribute to considerable groundwater recharge, as ‘substantial precipitation’ is defined as those rainfall events that fill storage and exceed retention capacity of the upper soil layer. Lysimeter measurements show that 50% of the precipitation is lost by evapotranspiration and the other 50% contributes to groundwater recharge. Most infiltrated water was stored for a short time in the unsaturated zone and did not result in a significant discharge from the lysimeter. Average specific yield, calculated using the water-table fluctuation method, was 0.144. The nature of the gravely unsaturated zone is that once the retention buffer of the soil is exceeded, the water front travels through relatively quickly, which can be seen as an advantage for recharge or a disadvantage for prevention of groundwater pollution.