Controls on potassium incorporation in foraminifera and other marine calcifying organisms

Seawater chemistry exerts an important control on the incorporation of trace elements into the shells of marine calcifying organisms. Variability in the major ion chemistry of seawater is a tracer of past geological processes, and the influence of seawater chemistry on trace element incorporation in calcium carbonate can be harnessed to determine changes in the composition of seawater through time. Here, we investigate whether key oceanographic parameters (temperature, salinity, and the carbonate system) affect the incorporation of potassium (K) into foraminiferal calcite, and explore the utility of K/Ca ratios in foraminifera as an indicator of past variability in the seawater Ca2+ concentration. We analysed both low-Mg and high-Mg modern foraminifera, including planktonic (Globigerinoides ruber) and shallow-dwelling larger benthic (Operculina ammonoides) species, using laser-ablation sector-field inductively-coupled plasma mass spectrometry (LA-SF-ICPMS). Both species show no resolvable influence of temperature, salinity, pH, or [CO32-] on K incorporation across the range that these vary at our samples sites. In order to determine the effect of the seawater Ca concentration ([Ca2+](sw)) on K incorporation, we analysed laboratory-cultured O. ammonoides, the close living relative of the abundant Eocene Nummulites, grown at four different [Ca2+](sw). We find a significant relationship between seawater and shell K/Ca, albeit with a shallower slope compared to most other trace elements which we suggest is driven by a crystal growth rate effect on K incorporation, constrained using culture experiments of O. ammonoides grown at different pH. If the K+ concentration has remained relatively constant throughout the Phanerozoic Eon, our data may pave the way forward for the use of K/Ca as a direct proxy for past [Ca2+](sw) variability. Alternatively, coupling K/Ca with the similar Na/Ca proxy would allow more accurate reconstruction of [Ca2+](sw) or verification of whether [K+](sw) and [Na+](sw) have indeed remained within narrow bounds.

Automated summary

Seawater chemistry plays a crucial role in the incorporation of trace elements into marine calcifying organisms' shells. Variations in seawater's major ion chemistry can be used to trace past geological processes. This study examines the influence of oceanographic parameters on the incorporation of potassium into foraminiferal calcite, and explores the potential of using K/Ca ratios as indicators of past changes in seawater composition. The results show that temperature, salinity, and pH have no significant effect on K incorporation, but seawater's calcium concentration does.