Carbonate clumped isotope evidence for latitudinal seawater temperature gradients and the oxygen isotope composition of Early Cretaceous seas

In this study, we investigated Early Cretaceous (Valanginian, ca. 135 million years ago) climate from subtropical to boreal palaeolatitudes. Combined carbonate clumped isotope and oxygen isotope data derived from subarctic, boreal, and sub-tropical fossil belemnite rostra (Mollusca: Cephalopoda) provide new palaeotemperature estimates as well as a constraint on the oxygen isotope composition of seawater. Our belemnite data reveal balmy high-latitude marine temperatures (ca. 22 degrees C) and warm sub-tropical temperatures (ca. 31 degrees C). Supplementing our clumped isotope-based temperature estimates with published TEX 86 data results in a conservative reconstruction of a latitudinal temperature gradient that is reduced compared to modern conditions. We find that modelling efforts are close to reproducing tropical temperatures when high pCO(2) levels are considered. Warm polar temperatures imply, however, that data-model discrepancies remain. Early Cretaceous seawater oxygen isotope values show a modern profile and are much more positive (up to 1.5 parts per thousand SMOW) than typically assumed. Based on our findings, if the positive Cretaceous seawater delta O-18 values are not considered, carbonate delta O-1(8) thermometry would underestimate temperatures, most acute at middle and tropical latitudes

Assessing kinetic fractionation in brachiopod calcite usingclumped isotopes

Brachiopod shells are the most widely used geological archive for the reconstruction of the temperature and the oxygen isotope composition of Phanerozoic seawater. However, it is not conclusive whether brachiopods precipitate their shells in thermodynamic equilibrium. In this study, we investigated the potential impact of kinetic controls on the isotope composition of modern brachiopods by measuring the oxygen and clumped isotope compositions of their shells. Our results show that clumped and oxygen isotope compositions depart from thermodynamic equilibrium due to growth rate-induced kinetic effects. These departures are in line with incomplete hydration and hydroxylation of dissolved CO2. These findings imply that the determination of taxon-specific growth rates alongside clumped and bulk oxygen isotope analyses is essential to ensure accurate estimates of past ocean temperatures and seawater oxygen isotope compositions from brachiopods

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

InterCarb: a community effort to improve interlaboratory standardization of the carbonate clumped isotope thermometer using carbonate standards

Increased use and improved methodology of carbonate clumped isotope thermometry has greatly enhanced our ability to interrogate a suite of Earth-system processes. However, interlaboratory discrepancies in quantifying carbonate clumped isotope (Δ47) measurements persist, and their specific sources remain unclear. To address interlaboratory differences, we first provide consensus values from the clumped isotope community for four carbonate standards relative to heated and equilibrated gases with 1,819 individual analyses from 10 laboratories. Then we analyzed the four carbonate standards along with three additional standards, spanning a broad range of δ47 and Δ47 values, for a total of 5,329 analyses on 25 individual mass spectrometers from 22 different laboratories. Treating three of the materials as known standards and the other four as unknowns, we find that the use of carbonate reference materials is a robust method for standardization that yields interlaboratory discrepancies entirely consistent with intralaboratory analytical uncertainties. Carbonate reference materials, along with measurement and data processing practices described herein, provide the carbonate clumped isotope community with a robust approach to achieve interlaboratory agreement as we continue to use and improve this powerful geochemical tool. We propose that carbonate clumped isotope data normalized to the carbonate reference materials described in this publication should be reported as Δ47 (I-CDES) values for Intercarb-Carbon Dioxide Equilibrium Scale

A high-resolution belemnite geochemical analysis of Early Cretaceous (Valanginian-Hauterivian) environmental and climatic perturbations

International audienceThe Early Cretaceous Weissert event, characterized by a positive carbon isotope excursion and coincident with the Paraná-Etendeka volcanism, saw a biogeochemical chain of events that ultimately led to an increase in carbon burial. A conclusive link between the Paraná-Etendeka volcanism and its impact upon the environment remains, however, elusive. Here we reconstruct temperature through the Weissert event from Mg/Ca ratios of belemnites from the Vocontian Trough (France) and SE Spain and use carbon isotopes to link our temperature reconstruction to marine records of carbon cycling. We provide evidence that the Paraná-Etendeka volcanism, unlike some large igneous provinces, did not cause a climate warming. The case can be made for cooling in the last stages of the Weissert event, which possibly reflects substantial CO 2 drawdown. In the absence of warming and consequent accelerated hydrological cycling and the relatively long duration of the eruptive phase of the Paraná-Etendeka, an alternate trigger for increased fertilization of the oceans is implicated