Dual clumped isotope thermometry resolves kinetic biases in carbonate formation temperatures

© The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Bajnai, D., Guo, W., Spötl, C., Coplen, T. B., Methner, K., Löffler, N., Krsnik, E., Gischler, E., Hansen, M., Henkel, D., Price, G. D., Raddatz, J., Scholz, D., & Fiebig, J. Dual clumped isotope thermometry resolves kinetic biases in carbonate formation temperatures. Nature Communications, 11(1), (2020): 4005, doi:10.1038/s41467-020-17501-0.Surface temperature is a fundamental parameter of Earth’s climate. Its evolution through time is commonly reconstructed using the oxygen isotope and the clumped isotope compositions of carbonate archives. However, reaction kinetics involved in the precipitation of carbonates can introduce inaccuracies in the derived temperatures. Here, we show that dual clumped isotope analyses, i.e., simultaneous ∆47 and ∆48 measurements on the single carbonate phase, can identify the origin and quantify the extent of these kinetic biases. Our results verify theoretical predictions and evidence that the isotopic disequilibrium commonly observed in speleothems and scleractinian coral skeletons is inherited from the dissolved inorganic carbon pool of their parent solutions. Further, we show that dual clumped isotope thermometry can achieve reliable palaeotemperature reconstructions, devoid of kinetic bias. Analysis of a belemnite rostrum implies that it precipitated near isotopic equilibrium and confirms the warmer-than-present temperatures during the Early Cretaceous at southern high latitudes.This work became possible through DFG grant “INST 161/871-1” and the Investment in Science Fund at Woods Hole Oceanographic Institution. The authors would like to thank Sven Hofmann and Manuel Schumann for their assistance in the joint Goethe University – Senckenberg BiK-F Stable Isotope Facility at the Institute of Geosciences, Goethe University Frankfurt. K.M. acknowledges funding through “DFG ME 4955/1-1”, E.K. through “DFG MU 2845/6-1”, D.S. through “DFG SCHO 1274/8-1” and “DFG SCHO 1274/11-1”, and M.H. through “DFG HA 8694/1-1”. C.S. acknowledges funding from the University of Innsbruck. A review of the manuscript by David Evans on behalf of the USGS is acknowledged

Effects of elevated seawater pCO2 on gene expression patterns in the gills of the green crab, Carcinus maenas

Background: The green crab Carcinus maenas is known for its high acclimation potential to varying environmental abiotic conditions. A high ability for ion and acid-base regulation is mainly based on an efficient regulation apparatus located in gill epithelia. However, at present it is neither known which ion transport proteins play a key role in the acid-base compensation response nor how gill epithelia respond to elevated seawater pCO2 as predicted for the future. In order to promote our understanding of the responses of green crab acid-base regulatory epithelia to high pCO2, Baltic Sea green crabs were exposed to a pCO2 of 400 Pa. Gills were screened for differentially expressed gene transcripts using a 4,462-feature microarray and quantitative real-time PCR. Results: Crabs responded mainly through fine scale adjustment of gene expression to elevated pCO2. However, 2% of all investigated transcripts were significantly regulated 1.3 to 2.2-fold upon one-week exposure to CO2 stress. Most of the genes known to code for proteins involved in osmo- and acid-base regulation, as well as cellular stress response, were were not impacted by elevated pCO2. However, after one week of exposure, significant changes were detected in a calcium-activated chloride channel, a hyperpolarization activated nucleotide-gated potassium channel, a tetraspanin, and an integrin. Furthermore, a putative syntaxin-binding protein, a protein of the transmembrane 9 superfamily, and a Cl-/HCO3 - exchanger of the SLC 4 family were differentially regulated. These genes were also affected in a previously published hypoosmotic acclimation response study. Conclusions: The moderate, but specific response of C. maenas gill gene expression indicates that (1) seawater acidification does not act as a strong stressor on the cellular level in gill epithelia; (2) the response to hypercapnia is to some degree comparable to a hypoosmotic acclimation response; (3) the specialization of each of the posterior gill arches might go beyond what has been demonstrated up to date; and (4) a re-configuration of gill epithelia might occur in response to hypercapnia

Patterns and mechanisms of early Pliocene warmth

About five to four million years ago, in the early Pliocene epoch, Earth had a warm, temperate climate. The gradual cooling that followed led to the establishment of modern temperature patterns, possibly in response to a decrease in atmospheric CO2 concentration, of the order of 100 parts per million, towards preindustrial values. Here we synthesize the available geochemical proxy records of sea surface temperature and show that, compared with that of today, the early Pliocene climate had substantially lower meridional and zonal temperature gradients but similar maximum ocean temperatures. Using an Earth system model, we show that none of the mechanisms currently proposed to explain Pliocene warmth can simultaneously reproduce all three crucial features. We suggest that a combination of several dynamical feedbacks underestimated in the models at present, such as those related to ocean mixing and cloud albedo, may have been responsible for these climate conditions

Proxy evidence for state-dependence of climate sensitivity in the Eocene greenhouse

Despite recent advances, the link between the evolution of atmospheric CO2 and climate during the Eocene greenhouse remains uncertain. In particular, modelling studies suggest that in order to achieve the global warmth that characterised the early Eocene, warmer climates must be more sensitive to CO2 forcing than colder climates. Here, we test this assertion in the geological record by combining a new high-resolution boron isotope-based CO2 record with novel estimates of Global Mean Temperature. We find that Equilibrium Climate Sensitivity (ECS) was indeed higher during the warmest intervals of the Eocene, agreeing well with recent model simulations, and declined through the Eocene as global climate cooled. These observations indicate that the canonical IPCC range of ECS (1.5 to 4.5 °C per doubling) is unlikely to be appropriate for high-CO2 warm climates of the past, and the state dependency of ECS may play an increasingly important role in determining the state of future climate as the Earth continues to warm

Theoretical constraints on the effects of pH, salinity, and temperature on clumped isotope signatures of dissolved inorganic carbon species and precipitating carbonate minerals

The use of carbonate 'clumped isotope' thermometry as a geochemical technique to determine temperature of formation of a carbonate mineral is predicated on the assumption that the mineral has attained an internal thermodynamic equilibrium. If true, then the clumped isotope signature is dependent solely upon the temperature of formation of the mineral without the need to know the isotopic or elemental composition of coeval fluids. However, anomalous signatures can arise under disequilibrium conditions that can make the estimation of temperatures uncertain by several degrees Celsius. Here we use ab initio calculations to examine the potential disequilibrium mineral signatures that may arise from the incorporation of dissolved inorganic carbon (DIC) species (predominantly aqueous carbonate and bicarbonate ions) into growing crystals without full equilibration with the crystal lattice.We explore theoretically the nature of clumping in the individual DIC species and the composite DIC pool under varying pH, salinity, temperature, and isotopic composition, and speculate about their effects upon the resultant disequilibrium clumping of the precipitates. We also calculate equilibrium clumped signatures for the carbonate minerals calcite, aragonite, and witherite. Our models indicate that each DIC species has a distinct equilibrium clumped isotope signature such that, δ47(H2CO3)>δ47HCO3->δ47(equilibrium calcite)>δ47CO32-, and predict a difference between δ47HCO3-andδ47CO32->0.033‰ at 25°C, and that δ47 (aragonite)>δ47 (calcite)>δ47 (witherite). We define the calcite clumped crossover pH as the pH at which the composite δ47 (DIC pool)=δ47 (equilibrium calcite). If disequilibrium δ47 (calcite) is misinterpreted as equilibrium δ47 (calcite), it is possible to overestimate or underestimate the growth temperature by small but significant amounts. Increases in salinity lower the clumped crossover pH and may cause larger effects. Extreme effects of pH, salinity, and temperature, such as between cold freshwater lakes at high latitudes to hot hypersaline environments, are predicted to have sizeable effects on the clumped isotope composition of aqueous DIC pools.In order to determine the most reliable and efficient modeling methods to represent aqueous dissolved inorganic carbon (DIC) species and carbonate minerals, we performed convergence and sensitivity testing on several different levels of theory. We used 4 different techniques for modeling the hydration of DIC: gas phase, implicit solvation (PCM and SMD), explicit solvation (ion with 3 water molecules) and supermolecular clusters (ion plus 21 to 32 water molecules with geometries generated by molecular dynamics). For each solvation technique, we performed sensitivity testing by combining different levels of theory (up to 8 ab initio/hybrid methods, each with up to 5 different sizes of basis sets) to understand the limits of each technique. We looked at the degree of convergence with the most complex (and accurate) models in order to select the most reliable and efficient modeling methods. The B3LYP method combined with the 6-311++G(2d,2p) basis set with supermolecular clusters worked well. © 2013 Elsevier Ltd