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.
Understanding the response of the El Niño-Southern Oscillation (ENSO) to global warming requires quantitative data on ENSO under different climate regimes. Here, we present a reconstruction of ENSO in the eastern tropical Pacific spanning the past 10,000 years derived from oxygen isotopes in fossil mollusk shells from Peru. We found that ENSO variance was close to the modern level in the early Holocene and severely damped ~4000 to 5000 years ago. In addition, ENSO variability was skewed toward cold events along coastal Peru 6700 to 7500 years ago owing to a shift of warm anomalies toward the Central Pacific. The modern ENSO regime was established ~3000 to 4500 years ago. We conclude that ENSO was sensitive to changes in climate boundary conditions during the Holocene, including but not limited to insolation.
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