Title: Towards the Calibration of the Globigerinoides ruber (white) paleothermometer
Description: The use of planktonic foraminiferal Mg/Ca ratios to reconstruct past sea surface temperatures (SST) is prevalent in the literature. The perceived simplicity of the underlying chemistry and ease of measurements are alluring. Canonically, temperature is thought to be the primary control on the shell Mg/Ca values. Additionally, an appeal of this proxy is that it can be combined with shell ä18O values to reconstruct changes in the local ä18O of seawater, a proxy for salinity. However, we have identified a salinity effect on the Mg/Ca signal recorded in planktonic foraminifera influencing samples from open ocean locations. This effect causes excess Mg incorporation, higher than predicted by theory, in high salinity regions for the planktonic foraminiferal species, Globigerinoides ruber (white). The shell "excess Mg/Ca" resides within the primary calcite lattice of the shell itself and may be related to the observed cyclic banding of high and low Mg/Ca calcite with the foraminiferal shells. We derive new equations which describe the relationship between shell Mg/Ca, ocean sea surface temperature, salinity, and bottom water ÄCO32-.

We also define new equations for ocean temperature and salinity using shell Mg/Ca, ä18O, and bottom water ÄCO32-, which take advantage of the dual sensitivity of shell Mg/Ca and ä18O to temperature and salinity. We apply these results downcore at several locations to assess the influence on paleo-reconstructions. These results are widely applicable to paleoceanographic studies and should allow more accurate reconstructions of both temperature and salinity. Below are brief outlines of the dissertation chapters: 1) A poor correlation between Mg/Ca derived and observed (WOA05) SST was found for 64 coretops in the (sub)tropical Atlantic. Shell-derived SST values from the subtropical gyres were overestimated and the residual "excess Mg/Ca" was well correlated with surface salinity. In this chapter, new calibration equations are developed for the Atlantic Ocean using paired Mg/Ca and ä18O measurements, along with the bottom water ÄCO32-, to predict temperature and salinity. These equations are validated using published coretop data and yield accurate estimates for SST and salinity. 2) The ITCZ is clearly identified in the oceans as the region where temperatures are the highest and salinities are the lowest.

These oceanographic fingerprints can be used to track ITCZ variability over the ocean through time. Both canonical equations and the new equations from chapter 1 are used here to reconstruct SST and ä18Oseawater/Salinity gradients since the LGM in the equatorial Atlantic. The marine Atlantic ITCZ migrated in excess of 10° latitude away from its modern position, during both the LGM and early Holocene, supporting climate model results as well as coastal and terrestrial paleohydrological records that document the sensitivity of ITCZ position to both high- and low-latitude forcing. 3) The nature of the excess shell Mg/Ca and the mechanism for incorporation is poorly understood. We investigated excess Mg/Ca using SEM, flow through ICP-MS (FT-ICP-MS) and electron microprobe analyses. SEM and FT-ICP-MS results suggest the excess shell Mg resides within the primary structure of the calcite lattice. Electron microprobe maps of shell Mg/Ca confirm that the excess Mg/Ca lies within the shell itself, likely within the high Mg/Ca calcite bands.

These findings suggest the incorporation of shell "excess Mg/Ca" first identified in chapter 1 is not related to post-depositional diagenetic alteration. These results will help elucidate the mechanism responsible for enhanced Mg uptake in high salinity settings. 4) Currently there exist no globally applicable calibration equations relating oceanographic parameters to foraminiferal shell Mg/Ca. In this chapter, we develop new, global calibration equations for G. ruber (white) following the methods of chapter 1. We find that the relationship between shell Mg/Ca and salinity is non-linear, with a threshold value near a salinity of 35, below which there is little influence of salinity on shell Mg/Ca. These equations were validated with published data and appear to be robust. By accounting for the additional influence, alkenone and foraminiferal Mg-Ca derived SST records may be reconciled in for some locations, particularly where there were likely to have been large variations of salinity in the past. These results represent a significant advance for the paleoceanographic community.