Search for: All records

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. 

Rock metamorphism releases substantial CO2 over geologic timescales (>1 My), potentially driving long-term planetary climate trends. The nature of carbonate sediments and crustal thermal regimes exert a strong control on the efficiency of metamorphic CO2 release; thus, it is likely that metamorphic CO2 degassing has not been constant throughout time. The Proterozoic Earth was characterized by a high proportion of dolomite-bearing mixed carbonate-silicate rocks and hotter crustal regimes, both of which would be expected to enhance metamorphic decarbonation. Thermodynamic phase equilibria modeling predicts that the metamorphic carbon flux was likely ~1.7 times greater in the Mesoproterozoic Era compared to the modern Earth. Analytical and numerical approaches (the carbon cycle model PreCOSCIOUS) are used to estimate the impact this would have on Proterozoic carbon cycling and global atmospheric compositions. This enhanced metamorphic CO2 release alone could increase pCO2 by a factor of four or more when compared to modern degassing rates, contributing to a stronger greenhouse effect and warmer global temperatures during the expansion of life on the early Earth. 

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. 

Multiple abrupt warming events (“hyperthermals”) punctuated the Early Eocene and were associated with deep-sea temperature increases of 2 to 4 °C, seafloor carbonate dissolution, and negative carbon isotope (δ¹³C) excursions. Whether hyperthermals were associated with changes in the global ocean overturning circulation is important for understanding their driving mechanisms and feedbacks and for gaining insight into the circulation’s sensitivity to climatic warming. Here, we present high-resolution benthic foraminiferal stable isotope records (δ¹³C and δ¹⁸O) throughout the Early Eocene Climate Optimum (~53.26 to 49.14 Ma) from the deep equatorial and North Atlantic. Combined with existing records from the South Atlantic and Pacific, these indicate consistently amplified δ¹³C excursion sizes during hyperthermals in the deep equatorial Atlantic. We compare these observations with results from an intermediate complexity Earth system model to demonstrate that this spatial pattern of δ¹³C excursion size is a predictable consequence of global warming-induced changes in ocean overturning circulation. In our model, transient warming drives the weakening of Southern Ocean-sourced overturning circulation, strengthens Atlantic meridional water mass aging gradients, and amplifies the magnitude of negative δ¹³C excursions in the equatorial to North Atlantic. Based on model-data consistency, we conclude that Eocene hyperthermals coincided with repeated weakening of the global overturning circulation. Not accounting for ocean circulation impacts on δ¹³C excursions will lead to incorrect estimates of the magnitude of carbon release driving hyperthermals. Our finding of weakening overturning in response to past transient climatic warming is consistent with predictions of declining Atlantic Ocean overturning strength in our warm future. 

Abstract Earth's hydrological cycle was profoundly perturbed by massive carbon emissions during an ancient (56 Ma) global warming event referred to as the Paleocene‐Eocene thermal maximum (PETM). One approach to gaining valuable insight into the response of the hydrological cycle is to construct sea‐surface salinity (SSS) records that can be used to gauge changes in the rates of evaporation and precipitation during the PETM in such climatically sensitive areas as the circum‐Antarctic region. Here, we pair oxygen isotope (δ¹⁸O) and magnesium‐calcium (Mg/Ca) measurements to reconstruct PETM sea‐surface temperatures (SSTs) and δ¹⁸O composition of seawater (δ¹⁸O_sw) at austral Site 690 (Weddell Sea). Several discrepancies emerge between the δ¹⁸O‐ and Mg/Ca‐based SST records, with the latter indicating that the earliest PETM was punctuated by a short‐lived ~4°C increase in local SSTs. Conversion of the δ¹⁸O_swvalues to SSS reveals a ~4 ppt decrease ~50 ka after peak PETM warming at Site 690. This negative SSS (δ¹⁸O_sw) anomaly coincides with a prominent minimum in the planktic foraminifer δ¹⁸O record published for the Site 690 PETM section. Thus, our revised interpretation posits that this δ¹⁸O minimum signals a decrease in surface‐ocean δ¹⁸O_swfostered by a transient increase in mean annual precipitation in the Weddell Sea region. The results of this study corroborate the view that the poleward flux of atmospheric moisture temporarily increased during a distinctive stage of the PETM.