Investigation of the stable isotope fractionation in speleothems with laboratory experiments

Many speleothems show evidence for calcite precipitation under disequilibrium conditions. To improve the understanding of these kinetic processes, several laboratory experiments were performed to study the fractionation of stable oxygen and carbon isotopes during the precipitation of calcite. Carbonate was precipitated under controlled conditions from both a body of standing water (beaker experiments) and a solution flowing along a channel (channel experiments) at a relative humidity of 100%. Slow degassing of CO2, simulated by the beaker experiments, results in δ18O values in equilibrium with the solution. In contrast, the δ13C values show a significant enrichment, inversely proportional to the height of the solution in the beakers. Fast degassing of CO2, simulated by the channel experiments, showed an enrichment of both δ13C and δ18O and a slope of Δδ13C/Δδ18O of 1.4±0.6. These results represent experimental evidence for the Hendy effect, which is manifested in (i) a progressive increase in δ18O and δ13C away from the growth axis and (ii) a positive correlation between δ18O and δ13C along a single growth layer of a stalagmite.