The isotope composition of precipitation has been monitored in monthly precipitation at Zagreb, Croatia, since 1976. Here, we present a statistical analysis of available long-term isotope data (³H activity concentration, δ²H, δ¹⁸O, and deuterium excess) and compare them to basic meteorological data. The aim was to see whether isotope composition reflected observed climate changes in Zagreb: a significant increase in the annual air temperature and larger variations in the precipitation amount. Annual mean δ¹⁸O and δ²H values showed an increase of 0.017‰ and 0.14‰ per year, respectively, with larger differences in monthly mean values in the first half of the year than in the second half. Mean annual d-excess remained constant over the whole long-term period, with a tendency for monthly mean d-excess values to decrease in the first half of the year and increase in the second half due to the influence of air masses originating from the eastern Mediterranean. Changes in the stable isotope composition of precipitation thus resembled changes in the temperature, the circulation pattern of air masses, and the precipitation regime. A local meteoric water line was obtained using different regression methods, which did not result in significant differences between nonweighted and precipitation-weighted slope and intercept values. Deviations from the Global Meteoric Water Line GMWL (lower slopes and intercepts) were observed in two recent periods and could be explained by changes in climate parameters. The temperature gradient of δ¹⁸O was 0.33‰/°C. The tritium activity concentrations in precipitation showed slight decreases during the last two decades, and the mean A in the most recent period, 2012–2018, was 7.6 ± 0.8 Tritium Units (TU).

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.

The availability and quality of freshwater currently represent one of the great issues for mankind

The application of tritium, ²H, and ¹⁸O in the characterization of the precipitation, groundwater, and surface and lake water of the Plitvice Lakes (PL), Croatia, over the 1979–2019 period is presented. An increase in the mean annual air temperature of 0.06 °C/year and in the annual precipitation amount of 10 mm/year is observed. The good correlation of the tritium activity concentration in the PL and Zagreb precipitation implies that the tritium data for Zagreb are applicable for the study of the PL area. The best local meteoric water line at PL was obtained by the reduced major axis regression (RMA) and precipitation-weighted ordinary least squares regression (PWLSR) approaches: δ²H_PWLSR = (7.97 ± 0.12) δ¹⁸O + (13.8 ± 1.3). The higher deuterium excess at PL (14.0 ± 2.2 ‰) than that at Zagreb reflects the higher altitude and influence of the Mediterranean precipitation. The δ²H in precipitation ranges from −132.4‰ to −22.3‰ and δ¹⁸O from −18.3 ‰ to −4.1‰. The much narrower ranges in the groundwater (<1‰ in δ¹⁸O, <10‰ in δ²H) indicate the good mixing of waters in aquifers and short mean residence times. The higher average δ²H in all three karst springs observed after 2003 can be attributed to the increase in the mean air temperature. The mean δ²H and δ¹⁸O values in the surface and lake water increase downstream due to the evaporation of surface waters. There is no significant difference between the surface water line and the lake water line (2011–2014). The stable isotope composition of the surface and lake waters reacts to extreme hydrological conditions.

Tufa is a fresh-water surface calcium carbonate deposit precipitated at or near ambient temperature, and commonly contains the remains of macro- and microphytes. Many Holocene tufas are found along the Zrmanja River, Dalmatian karst, Croatia. In this work we present radiocarbon dating results of older tufa that was found for the first time at the Zrmanja River near the Village of Sanaderi. Tufa outcrops were observed at different levels, between the river bed and up to 26 m above its present level. Radiocarbon dating of the carbonate fraction revealed ages from modern, at the river bed, up to 40 kBP ~20 m above its present level. These ages fit well with the hypothesis that the Zrmanja River had a previous surface connection with the Krka River, and changed its flow direction toward the Novigrad Sea approximately 40 kBP (Marine Isotope Stage 3). Radiocarbon AMS dating of tufa organic residue yielded a maximum conventional age of 17 kBP for the highest outcrop position indicating probable penetration of younger organic material to hollow tufa structures, as confirmed by radiocarbon analyses of humin extracted from the samples. Stable carbon isotope composition (δ¹³C) of the carbonate fraction of (−10.4 ± 0.6)‰ and (−9.7 ± 0.8)‰ for the Holocene and the older samples, respectively, indicate the autochthonous origin of the carbonate. The δ¹³C values of (−30.5 ± 0.3)‰ and (−29.6 ± 0.6)‰ for organic residue, having ages 5000 BP, respectively, suggest a unique carbon source for photosynthesis, mainly atmospheric CO₂, with an indication of the Suess effect in δ¹³C during last centuries. The oxygen isotopic composition (δ¹⁸O) agrees well with deposition of tufa samples in two stages, the Holocene (−8.02 ± 0.72‰) and “old” (mainly MIS 3 and the beginning of MIS 2) (−6.89 ± 0.34‰), suggesting a ~4 °C lower temperature in MIS 3 compared to the current one.

Isotope studies, using ¹⁴C dating, δ¹³C and δ¹⁸O measurements, were performed at eight speleothems taken from three submerged caves situated along the eastern Adriatic coast, Croatia. The speleothems were taken from 17 m to 38.5 m depth below mean sea level. The samples consist of four stalagmites and four stalactites in position of growth, covered with marine biogenic overgrowth, and the length of speleothems ranges from ~80 mm to ~190 mm. The youngest (surface) and the oldest (base) layers of speleothems were radiocarbon dated and the ¹⁴C ages range from 21,600 cal B.P. to 37,000 yr B.P. During that period the global sea level was more than 40 m below the recent one, so presently submerged objects were under the subaerial conditions necessary for speleothem deposition. ¹⁴C ages of the youngest layer range from 21,600 to 32,200 cal B.P. for different submerged speleothems. This indicates the time when the speleothem growth ceased, most probably due to flooding of the cave with either fresh or brackish water. Speleothem growth during the Last Glacial Maximum (30–19 kyr ago) and different time of growth cessation for the different speleothem samples suggest that climate change was not the reason for cessation of deposition. Samples for δ¹³C and δ¹⁸O measurements were taken from six submerged speleothems with sampling distances of ca. 5–10 mm from the surface to the base of speleothems. Most of the δ¹³C values are in the range from −10.5‰ to −8.5‰, with few exceptions to −6‰. These values are typical for Dinaric karst, and very different values for marine biogenic overgrowth indicate that no isotopic exchange took place during the submerged period. δ¹⁸O values range from −6.7‰ to −4.1‰. A weak correlation between δ¹³C and δ¹⁸O values indicates possible kinetic isotope fractionation during the calcite precipitation. If the δ¹⁸O record is interpreted as climatic signal, it suggests similar climatic conditions for the late Pleistocene and the Holocene, especially no significant differences in temperature and/or moisture transport.