Trace element incorporation in modern speleothem calcite and implications for paleoclimate reconstruction

Trace element compositions, expressed as ratios relative to Ca (Mg/Ca, Sr/Ca and Ba/Ca), in drip water and modern speleothem calcite were measured at multiple sites within a single cave system (Natural Bridge Caverns) in central Texas. These measurements are used to investigate how water and calcite compositions respond to changes in climate. Drip water trace element ratios respond to changes in climate and in soil, vadose zone and/or in-cave processes, which are in turn influenced by climate. It is commonly assumed that speleothem calcite directly reflects these changes in the drip water composition. To test this assumption, this study quantifies the partitioning of trace elements into speleothem calcite in a natural cave setting. To determine the controls on calcite trace element ratios, empirical partition coefficients (K [subscript D]) for Mg, Sr, and Ba are measured using a unique time series of water and modern calcite geochemistry at two drip sites. One drip site, dominantly supplied by conduit flow, has relatively invariant calcite trace element compositions that reflect correspondingly small variations in drip water chemistry. A second drip site, supplied by a combination of conduit and diffuse flow, exhibits a seasonal change in drip water composition due to changes in cave-air CO₂ concentrations. The drip water seasonality at this site is recorded in the calcite trace element compositions; however the partitioning of Mg/Ca from drip water to calcite is not controlled by the same mechanism(s) that control Sr/Ca and Ba/Ca partitioning. Results of this study indicate that the partitioning of Mg changes with drip water Mg concentration, temperature and location of the calcite relative to the point of drip impact. Calcite Sr/Ca and Ba/Ca ratios are more strongly influenced by changes in cave-air CO₂ that cause changes in CO₂ degassing, affecting calcite precipitation. This element specific partitioning complicates the interpretation of speleothem trace element records, since calcite Mg/Ca and Sr/Ca may not always covary even at drip sites that experience PCP. Although there is a strong correlation between Mg/Ca and Sr/Ca ratios in the drip water at these sites, there is considerable scatter between these two values in calcite. Average K [subscript D] values at both sites fall within the range of previous theoretical and empirical studies and are 0.025, 0.12 and 0.15 for Mg, Sr and Ba respectively. It is important to note that not all trace element partitioning is controlled by the same mechanism, since this has implications for interpretations of hydrologic processes from speleothems.