The clumped isotopic composition of carbonate‐derived CO2 (denoted Δ47) is a function of carbonate formation temperature and in natural samples can act as a recorder of paleoclimate, burial, or diagenetic conditions. The absolute abundance of heavy isotopes in the universal standards VPDB and VSMOW (defined by four parameters: R13VPDB, R17VSMOW, R18VSMOW, and λ) impact calculated Δ47 values. Here, we investigate whether use of updated and more accurate values for these parameters can remove observed interlaboratory differences in the measured T‐Δ47 relationship. Using the updated parameters, we reprocess 14 published calibration data sets measured in 11 different laboratories, representing many mineralogies, bulk compositions, sample types, reaction temperatures, and sample preparation and analysis methods. Exploiting this large composite data set (n = 1,253 sample replicates), we investigate the possibility for a “universal” clumped isotope calibration. We find that applying updated parameters improves the T‐Δ47 relationship (reduces residuals) within most labs and improves overall agreement but does not eliminate all interlaboratory differences. We reaffirm earlier findings that different mineralogies do not require different calibration equations and that cleaning procedures, method of pressure baseline correction, and mass spectrometer type do not affect interlaboratory agreement. We also present new estimates of the temperature dependence of the acid digestion fractionation for Δ47 (Δ*25‐X), based on combining reprocessed data from four studies, and new theoretical equilibrium values to be used in calculation of the empirical transfer function. Overall, we have ruled out a number of possible causes of interlaboratory disagreement in the T‐Δ47 relationship, but many more remain to be investigated.
The exclusive use of carbonate reference materials is a robust method for the standardization of clumped isotope measurements • Measurements using different acid temperatures, designs of preparation lines, and mass spectrometers are statistically indistinguishable • We propose new consensus values for a set of 7 carbonate reference materials and updated guidelines to report clumped isotope measurements
As the world warms, there is a profound need to improve projections of climate change. Although the latest Earth system models offer an unprecedented number of features, fundamental uncertainties continue to cloud our view of the future. Past climates provide the only opportunity to observe how the Earth system responds to high carbon dioxide, underlining a fundamental role for paleoclimatology in constraining future climate change. Here, we review the relevancy of paleoclimate information for climate prediction and discuss the prospects for emerging methodologies to further insights gained from past climates. Advances in proxy methods and interpretations pave the way for the use of past climates for model evaluation—a practice that we argue should be widely adopted.
The cause of the end-Cretaceous (KPg) mass extinction is still debated due to difficulty separating the influences of two closely timed potential causal events: eruption of the Deccan Traps volcanic province and impact of the Chicxulub meteorite. Here we combine published extinction patterns with a new clumped isotope temperature record from a hiatus-free, expanded KPg boundary section from Seymour Island, Antarctica. We document a 7.8±3.3 °C warming synchronous with the onset of Deccan Traps volcanism and a second, smaller warming at the time of meteorite impact. Local warming may have been amplified due to simultaneous disappearance of continental or sea ice. Intra-shell variability indicates a possible reduction in seasonality after Deccan eruptions began, continuing through the meteorite event. Species extinction at Seymour Island occurred in two pulses that coincide with the two observed warming events, directly linking the end-Cretaceous extinction at this site to both volcanic and meteorite events via climate change.
During the last glacial period, the Laurentide Ice Sheet sporadically discharged huge numbers of icebergs through the Hudson Strait into the North Atlantic Ocean, leaving behind distinct layers of ice-rafted debris in the ocean sediments. Perplexingly, these massive discharge events-Heinrich events-occurred during the cold portion of millennial-scale climate oscillations called Dansgaard-Oeschger cycles. This is in contrast to the expectation that ice sheets expand in colder climates and shrink in warmer climates. Here we use an ice sheet model to show that the magnitude and timing of Heinrich events can be explained by the same processes that drive the retreat of modern marine-terminating glaciers. In our model, subsurface ocean warming associated with variations in the overturning circulation increases underwater melt along the calving face, triggering rapid margin retreat and increased iceberg discharge. On millennial timescales, isostatic adjustment causes the bed to uplift, isolating the terminus from subsurface warming and allowing the ice sheet to advance again until, at its most advanced position, it is poised for another Heinrich event. This mechanism not only explains the timing and magnitude of observed Heinrich events, but also suggests that ice sheets in contact with warming oceans may be vulnerable to catastrophic collapse even with little atmospheric warming.
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