ABSTRACT
The climate and environmental significance of the Deccan Traps large igneous province of west-central India has been the subject of debate in paleontological communities. Nearly one million years of semi-continuous Deccan eruptive activity spanned the Cretaceous-Paleogene boundary, which is renowned for the extinction of most dinosaur groups. Whereas the Chicxulub impactor is acknowledged as the principal cause of these extinctions, the Deccan Traps eruptions are believed to have contributed to extinction patterns and/or enhanced ecological pressures on biota during this interval of geologic time. We present the first coupled records of biogenic carbonate clumped isotope paleothermometry and mercury concentrations as measured from a broad geographic distribution of marine mollusk fossils. These fossils preserve evidence of simultaneous increases in coastal marine temperatures and mercury concentrations at a global scale, which appear attributable to volcanic CO2 and mercury emissions. These early findings warrant further investigation with additional records of combined Late Cretaceous temperatures and mercury concentrations of biogenic carbonate.
ABSTRACT
RATIONALE: The clumped isotope paleothermometer, a new proxy widely applicable in studies of paleoclimate, tectonics, and paleontology, relates the abundance of doubly substituted isotopologues of carbonate-derived CO2 to the temperature of formation of the carbonate phase. As this technique becomes more widely used, more is discovered about the effects of everyday laboratory procedures on the clumped isotopic composition of CO2 gas. METHODS: Preparation of CO2 for clumped isotope analysis requires the removal of isobaric contaminants prior to measurement, achieved dynamically by passing the CO2 through a gas chromatography column using a helium carrier gas or cryogenically pumping CO2 through a static trap filled with Porapak™ Q (PPQ) material. The stable and clumped isotopic compositions of carbonate standards prepared at PPQ trap temperatures between -40°C and -10°C were measured by isotope ratio mass spectrometry to evaluate potential artifacts introduced by the static PPQ trap method. RESULTS: The stable isotopic composition of carbonates run at temperatures below -20°C was fractionated, despite achieving >99% retrieval of gas at temperatures as cold as -30°C. The δ(13)C and δ(18)O values decreased by ~0.01 and ~0.03 /(°C below -20°C). The raw Δ47 values decreased by 0.003-0.005 /(°C below -20°C), but the final reference-frame-corrected values (Δ47-RFAC ) were unaffected as long as the carbonate samples and standard gases were prepared identically. CONCLUSIONS: Preparing carbonate samples for clumped isotope analysis using a PPQ trap that is too cold can result in erroneous stable isotopic compositions. New and existing labs using the static PPQ trap cleaning procedure should determine the ideal PPQ trap temperature for their particular system through monitoring not only yield through the PPQ trap, but also stable isotopic composition at various PPQ trap temperatures.
