Quantifying kinetic fractionation in Bunker Cave speleothems using Δ47

Isotopic signals in speleothems are used for investigating paleoclimate variability on land and are useful to constrain the dating of prominent climate events. A quantitative use, however, is limited by an incomplete understanding of parameters contributing to the carbon and oxygen isotope signals. These include external and environmental parameters such as delta O-18 of cave drip waters as well as internal parameters associated with speleothem formation, such as the presence of non-equilibrium effects and especially the magnitude of their isotopic shifts. We explore the use of clumped isotopes as a new tool for investigating the kinetic isotope effect in speleothems. Holocene and modern speleothems from Bunker Cave (Germany) as well as modern material from the adjacent Dechen Cave are all offset from the equilibrium relationship due to kinetic fractionation. This kinetic offset in clumped isotopes is observed in a stalagmite despite mostly negative Hendy tests, providing a sensitive indicator for kinetic fractionation in cave carbonates. The temperature dependence of the clumped isotope values (0.005 parts per thousand, per degrees C) is low compared to the observed magnitude of kinetic offsets (between -0.021 and -0.075 parts per thousand), so that the mean offsets in apparent temperatures due to kinetic isotope effects are on the order of 10 degrees C. As a result clumped isotopes are useful in identifying temporal variations in the kinetic fractionation in a stalagmite, when the temperatures during the speleothem growth period are either relatively constant (variations <2 degrees C) or can be independently constrained. The variations in the kinetic isotope fractionation in Bunker Cave are associated with changing drip water super saturation with periods of stronger prior calcite precipitation associated with lower kinetic offsets in the speleothem calcite. In contrast, stalagmite growth rates show no direct correlation with the degree of kinetic fractionation in the investigated range (13-1500 mu m/a). (C) 2012 Elsevier Ltd. All rights reserved.