Title: The Influence of Paleo-Seawater Chemistry on Foraminifera Trace Element Proxies and their Application to Deep-Time Paleo-Reconstructions
Description: The fossilized remains of the calcite shells of foraminifera comprise one of the most continuous and reliable records of the geologic evolution of climate and ocean chemistry. The trace elemental composition of foraminiferal shells has been shown to systematically respond to seawater properties, providing a way to reconstruct oceanic conditions throughout the last 170 million years. In particular, the boron/calcium ratio of foraminiferal calcite (B/Ca) is an emerging proxy for the seawater carbonate system, which plays a major role in regulating atmospheric CO2 and thus Earth’s climate. In planktic foraminifera, previous culture studies have shown that shell B/Ca increases with seawater pH, which is hypothesized to result from increased incorporation of borate ion (B(OH)4 -) at high pH; increasing pH increases the [B(OH)4 -] of seawater. However, further experiments showed that B/Ca responds to both pH and seawater dissolved inorganic carbon concentration (DIC), leading to the hypothesis that B/Ca is driven by the [B(OH)4 -/DIC] ratio of seawater.

Because pH (and thus B(OH)4 -) can be determined via the δ11B composition of foraminiferal calcite, B/Ca therefore may provide an opportunity to determine seawater DIC in the geologic past. The magnesium/calcium ratio (Mg/Ca) of foraminifer shells is a well-established proxy for seawater temperatures, where foraminiferal Mg/Ca increases at greater temperatures. However, foraminifera shell chemistry such as B/Ca and Mg/Ca ratios also depend on the major ion chemistry of seawater. For example, the seawater Mg/Ca ratio (Mg/Casw), which has increased significantly over the last 60 million years, is known to affect the sensitivity of the Mg/Ca proxy to temperature. In addition, the seawater boron concentration ([B]sw) has also increased across the Cenozoic. The dependence of B/Ca proxy relationships on Mg/Casw and [B]sw composition remains unknown. During the Paleogene era (65-34 Ma), Earth’s climate was characterized by a number of rapid warming events termed ”hyperthermals”. Evidence from the sedimentary record suggests that hyperthermals were catalyzed by rapid carbon release and caused widespread ocean acidification and deep-sea deoxygenation.

These hyperthermal events present the best geologic analog conditions to anthropogenic climate change, and their study can therefore help to illuminate how the Earth system responds to rapid carbon release and warming. Planktic foraminiferal B/Ca records from the largest hyperthermal event, the Paleocene-Eocene Thermal Maximum (PETM), show a large decrease, which agrees with the theory that ocean acidification should cause B/Ca to decline. However, the decrease is larger than can be reconciled from existing proxy calibrations conducted in modern seawater, begging the question of whether the low Mg/Casw of the Paleogene Ocean affected the sensitivity of B/Ca to the seawater carbonate system. Because there are also a number of outstanding uncertainties regarding the controls on B/Ca- including seawater [Ca] and shell growth rate, light intensity, and phosphate concentration- it is also possible that these factors contributed to the PETM B/Ca excursion. The influence of these additional parameters on B/Ca, as well as the influence of Mg/Casw, needs to be tested in controlled culture experiments.

To address these outstanding questions in proxy development, I conducted a series of culture experiments in three living planktic foraminifer species- Orbulina universa, Trilobatus sacculifer, and Globigerinoides ruber (pink). In order to refine our understanding of proxy controls on foraminiferal B/Ca, I investigated how foraminiferal B/Ca is affected by variable light intensity, growth rate (indirectly via seawater [Ca] manipulation), and seawater [B]. Subsequently I tested the influence of low seawater Mg/Ca, analogous to that of the Paleocene ocean, on B/Ca-carbonate chemistry relationships. In Chapters 2 and 3, I detail how my results support the notion that planktic foraminiferal B/Ca in these three symbiont-bearing species is driven by the B(OH)4 -/DIC ratio of seawater and is not compromised by growth rate effects. Furthermore, the sensitivity of B/Ca to B(OH)4 -/DIC is increased under low Mg/Casw in both O. universa and T. sacculifer. In Chapters 2 and 3, I hypothesize that this increased sensitivity is due to decreased cellular pH regulation under low Mg/Casw, leading to a greater sensitivity of the foraminiferal microenvironment’s carbon system to external forcing.

I define new culture calibrations that can be applied to records from Paleocene seawater in Chapter 3, and use these calibrations to reconstruct surface ocean DIC and the overall size of the carbon system perturbation across the PETM in Chapter 4. Finally, in Chapter 5, I show how foraminiferal Mg/Ca responds to seawater Mg/Ca and the carbon system from these same experiments, with implications for accounting for carbon system influences on Mg/Ca from early Cenozoic proxy records.