A 20 million year record of planktic foraminiferal B/Ca ratios: Systematics and uncertainties in pCO 2 reconstructions

Abstract

We use new and published data representing a 20 million long record to discuss the systematics of interpreting planktic foraminiferal B/Ca ratios. B/Ca-based reconstructions of seawater carbonate chemistry and atmospheric pCO 2 assume that the incorporation of boron into foraminiferal tests can be empirically described by an apparent partition coefficient, K D = B / Ca CaCO 3 B OH 4 - / HCO 3 - seawater ( Hemming and Hanson, 1992). It has also been proposed that there is a species-specific relationship between K D and temperature ( Yu et al., 2007). As we discuss, although these relationships may be robust, there remain significant uncertainties over the controls on boron incorporation into foraminifera. It is difficult to be certain that the empirically defined correlation between temperature and K D is not simply a result of covariance of temperature and other hydrographic variables in the ocean, including carbonate system parameters. There is also some evidence that K D may be affected by solution [ HCO 3 - ] / [ CO 3 2 - ] ratios (i.e., pH), or by [ CO 3 2 - ] . In addition, the theoretical basis for the definition of K D and for a temperature control on K D is of debate. We also discuss the sensitivity of pCO 2 reconstructions to different K D –temperature calibrations and seawater B/Ca. If a K D –temperature calibration is estimated using ice core pCO 2 values between 0 and 200 ka, B/Ca ratios can be used to reasonably approximate atmospheric pCO 2 between 200 and 800 ka; however, the absolute values of pCO 2 calculated are sensitive to the choice of K D –temperature relationship. For older time periods, the absolute values of pCO 2 are also dependent on the evolution of seawater B concentrations. However, we find that over the last 20 Ma, reconstructed changes in declining pCO 2 across the Mid-Pleistocene Transition, Pliocene glacial intensification, and the Middle Miocene Climate Transition are supported by the B/Ca record even if a constant coretop K D is used, or different K D –temperature calibrations and models of seawater B evolution are applied to the data. The inferred influence of temperature on K D from coretop data therefore cannot itself explain the structure of a published pCO 2 reconstruction ( Tripati et al., 2009). We conclude the raw B/Ca data supports a coupling between pCO 2 and climate over the past 20 Ma. Finally, we explore possible implications of B/Ca-based pCO 2 estimates for the interpretation of other marine pCO 2 proxies.