LAUSR

Abstract Here we present novel cave-analogue experiments directly investigating stable carbon and oxygen isotope fractionation between the major involved species of the carbonate system (HCO3−, CO2, CaCO3 and H2O). In these experiments, which were performed under controlled conditions inside a climate box, a thin film of solution flew down an inclined marble or glass plate. After different distances of flow and, thus, residence times on the plate, pH, electrical conductivity, supersaturation with respect to calcite, precipitation rate as well as the δ18O and δ13C values of the dissolved inorganic carbon (DIC) and the precipitated CaCO3 were obtained. Progressive precipitation of CaCO3 along the plate is accompanied by degassing of CO2 and stable isotope fractionation, and the system is driven out of isotope equilibrium. We observe a strong enrichment of the δ13C values with increasing residence time and a smaller enrichment in δ18O. The temporal evolution of the δ18O and δ13C values of both the DIC and the precipitated CaCO3 can be explained by a Rayleigh fractionation model, but the observed enrichment in δ13C values is much larger than expected based on isotope equilibrium fractionation factors. Our setup enables to determine the fractionation between CaCO3 and HCO3−, i.e., eCaCO3/HCO3−. Carbon isotope fractionation, 13eCaCO3/HCO3−, is strongly negative for all experiments and much lower than equilibrium isotope fractionation (0–1‰). In addition, 13eCaCO3/HCO3− decreases with increasing residence time on the plate, and thus decreasing supersaturation with respect to calcite. Thus, isotope fractionation depends on precipitation rate and consequently occurs under kinetic conditions. This is in contrast to previous studies, which found no rate-dependence and no or even a positive carbon isotope fractionation between CaCO3 and HCO3−. Oxygen isotope fractionation, 18eCaCO3/HCO3−, is also negative and dependent on precipitation rate. Since no literature values for 18eCaCO3/HCO3− are available, we calculated 18eCaCO3/HCO3− using equilibrium oxygen isotope fractionation factors between water and calcite and water and HCO3−, respectively. At the beginning of the plate, the fractionation is in agreement with the fractionation calculated using fractionation factors determined in cave systems. The observed fractionation between CaCO3 and water, 1000ln18α, is also in good agreement with the values determined in cave systems and shows a very similar temperature dependence 1000 ln 18 α = 16.516 ± 1.267 ∗ 10 3 T − 26.141 ± 4.356 . However, with progressive precipitation of CaCO3 along the plate, the system is forced out of isotope equilibrium with the water, and 1000ln18α increases. The large, negative, rate-dependent isotope fractionations observed in this study suggest that precipitation of speleothem calcite is strongly kinetically controlled and may, thus, have a large effect on speleothem δ18O and δ13C values. Since these values may erroneously be interpreted as reflecting changes in past temperature, precipitation and/or vegetation density, these results have important implications for paleoclimate reconstructions from speleothems.