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Calcite is known to incorporate a range of non-constituent ions during its precipitation from aqueous solutions. Their concentrations (measured as E/Ca ratios, where E denotes the elemental forms of non-constituent ions) in calcite formed in seawater can serve as useful tools for paleoceanographic studies. But this requires concrete understanding of the incorporation patterns and their dependence to environmental factors at the time of mineral precipitation. Here, we present Na/Ca, K/Ca, S/Ca, and B/Ca ratios of inorganic calcite samples generated in laboratory experiments using Mg-free artificial seawater with systematic manipulations of pH, [DIC], and [Ca2+]. The three parameters were varied both individually (the pH, DIC, and Ca experimental series) and in tandem (the pH-Ca and DIC-Ca series) to form calcites under variable versus near-constant precipitation rates (denoted as R). All measured E/Ca ratios showed a robust positive linear dependence to changes in [Ca2+] in the Ca, pH-Ca, and DIC-Ca series, irrespective of changes in R. While K/Ca and S/Ca ratios changed almost exclusively with [Ca2+], Na/Ca and B/Ca ratios showed an additionally strong increase with increasing pH and a more moderate increase with rising [DIC], when R changed accordingly in the pH and DIC series. While R-driven kinetic effects and/or formation of certain cation–anion pairs may be important for the elemental uptake in calcite under some circumstances, these mechanisms or processes cannot fully account for the observed trends in every experimental series for all E/Ca ratios considered here. We propose that the observed E/Ca trends can be comprehensively explained by simultaneously considering the nonequivalent influence of changes in solution [Ca2+] and [CO32−] on step-specific kink formation dynamics and the size difference between the respective non-constituent ions (K+, Na+, SO42−, and B(OH)4− and B(OH)3) relative to Ca2+ and CO32− that constitute the calcite lattice. 

The late Paleocene and early Eocene (LPEE) are characterized by long-term (million years, Myr) global warming and by transient, abrupt (kiloyears, kyr) warming events, termed hyperthermals. Although both have been attributed to greenhouse (CO₂) forcing, the longer-term trend in climate was likely influenced by additional forcing factors (i.e., tectonics) and the extent to which warming was driven by atmospheric CO₂remains unclear. Here, we use a suite of new and existing observations from planktic foraminifera collected at Pacific Ocean Drilling Program Sites 1209 and 1210 and inversion of a multiproxy Bayesian hierarchical model to quantify sea surface temperature (SST) and atmospheric CO₂over a 6-Myr interval. Our reconstructions span the initiation of long-term LPEE warming (~58 Ma), and the two largest Paleogene hyperthermals, the Paleocene–Eocene Thermal Maximum (PETM, ~56 Ma) and Eocene Thermal Maximum 2 (ETM-2, ~54 Ma). Our results show strong coupling between CO₂and temperature over the long- (LPEE) and short-term (PETM and ETM-2) but differing Pacific climate sensitivities over the two timescales. Combined CO₂and carbon isotope trends imply the carbon source driving CO₂increase was likely methanogenic, organic, or mixed for the PETM and organic for ETM-2, whereas a source with higher δ¹³C values (e.g., volcanic degassing) is associated with the long-term LPEE. Reconstructed emissions for the PETM (5,800 Gt C) and ETM-2 (3,800 Gt C) are comparable in mass to future emission scenarios, reinforcing the value of these events as analogs of anthropogenic change. 

The geological record encodes the relationship between climate and atmospheric carbon dioxide (CO₂) over long and short timescales, as well as potential drivers of evolutionary transitions. However, reconstructing CO₂beyond direct measurements requires the use of paleoproxies and herein lies the challenge, as proxies differ in their assumptions, degree of understanding, and even reconstructed values. In this study, we critically evaluated, categorized, and integrated available proxies to create a high-fidelity and transparently constructed atmospheric CO₂record spanning the past 66 million years. This newly constructed record provides clearer evidence for higher Earth system sensitivity in the past and for the role of CO₂thresholds in biological and cryosphere evolution.