Applications of speleothem calcite geochemistry in climate change studies require the evaluation of the accuracy and sensitivity of speleothem proxies to correctly infer paleoclimatic information. The present study of Harrison's Cave, Barbados, uses the analysis of the modern climatology and groundwater system to evaluate controls on the C and O isotopic composition of modern speleothems. This new approach directly compares the δ18O and δ13C values of modern speleothems with the values for their corresponding drip waters in order to assess the degree to which isotopic equilibrium is achieved during calcite precipitation. If modern speleothems can be demonstrated to precipitate in isotopic equilibrium, then ancient speleothems, suitable for paleoclimatic studies, from the same cave environment may also have been precipitated in isotopic equilibrium. If modern speleothems are precipitated out of isotopic equilibrium, then the magnitude and direction of the C and O isotopic offsets may allow specific kinetic and/or equilibrium isotopic fractionation mechanisms to be identified. Carbon isotope values for the majority of modern speleothem samples from Harrison's Cave fall within the range of equilibrium values predicted from the combined use of (1) calcite-water fractionation factors from the literature, (2) measured temperatures, and (3) measured δ13C values of the dissolved inorganic carbon of drip waters. Calcite samples range from ∼0.8‰ higher to ∼1.1‰ lower than predicted values. The 13C depletions are likely caused by kinetically driven departures in the fractionation between HCO3- (aq) and CaCO3 from equilibrium conditions, caused by rapid calcite growth. 13C enrichments can be accounted for by Rayleigh distillation of the HCO3- (aq) reservoir during degassing of 13C-depleted CO2. Modern speleothems from Harrison's Cave are not in O isotopic equilibrium with their corresponding drip waters and are 0.2‰ to 2.3‰ enriched in 18O relative to equilibrium values. δ18O variations in modern calcite are likely controlled by kinetically driven changes in the fractionation between HCO3- (aq) and CaCO3 from equilibrium conditions to nonequilibrium conditions, consistent with rapid calcite growth. In contrast to δ13C, δ18O values of modern calcite may not be affected by Rayleigh distillation during degassing because CO2 hydration and hydroxylation reactions will buffer the O isotopic composition of the HCO3 - (aq) reservoir. If the effects of Rayleigh distillation manifest themselves in the O isotopic system, they will result in 18O enrichment in the HCO3- (aq) reservoir and ultimately in the precipitated CaCO3.
Bibliographical noteFunding Information:
This work was supported by grants from the Geology Foundation of the University of Texas at Austin, the US Department of Energy (DE-FG03-97ER14812), the National Science Foundation (EAR95-26714 and EAR02-14041), and the Geological Society of America (7220-02). We would like to thank the following contributing GNIP laboratories; International Atomic Energy Agency, Vienna, Austria, the Faculty of Physics and Nuclear Techniques, University of Mining and Metallurgy, Krakow, Poland and the University of Copenhagen, Copenhagen, Denmark. We appreciate the assistance provided by the management of Harrison’s Cave, the Barbados National Trust, and Bwalya Mwansa of the Barbados Water Authority, Tony Mason and Larry Mack. We would also like to thank Dr. Robert Criss and two anonymous reviewers for useful comments during preparation of this manuscript.