A correction scheme for calcium carbonate clumped isotope (Δ47) thermometric equation depending on sample preparation technique

Abstract

The CO₂ preparatory methods implemented during carbonate-clumped isotope analysis for the acid digestion of carbonate with the goal of high sample throughput yielded multiple empirical relationships for the thermometry. These methods varied significantly from its original practice of carbonate reaction at 25 °C using sealed vessel method to automated quick performance acid drip or common acid bath method at 70 °C or 90 °C temperatures, respectively; these approaches differed noticeably. Technical development replacing primitive reaction protocols, introduced different reaction conditions, causing significant differences in the chemical reaction procedure and CO₂ trapping, which caused variation in the values of slope and intercept for the linear regression equations governing carbonate-clumped isotope(Δ₄₇) distribution with carbonate growth temperatures. These studies include the Δ₄₇ measurement and analysis of either laboratory-grown or natural carbonates with precise knowledge of their precipitation/depositional temperatures. However, the discrepancies in the existing universal calibration schemes remained poorly understood despite adopting an identical data correction protocol. This is explained here by the reaction kinetics and CO₂ collection methodologies adopted during experimentation. The present study investigated the slope and intercept values of the published carbonate clumped isotope thermometry equations expressed in the accepted Absolute Reference Frame (ARF in CDES) at 25 °C after accounting for the acid correction factor. We observe a systematic shift in the mean slope and intercept values of 0.0154(±0.007) and 0.153(±0.0686) ‰ for 70 °C reaction experiments and offset of 0.0181(±0.008) and 0.197(±0.079) ‰ for the experiments conducted at 90 °C by using the acid drip and/or Common Acid bath method, respectively from the slope and intercept values of the calibration equations proposed using sealed vessel method at 25 °C reaction temperature. The mean values for slope and intercept are compared using ANOVA and paired f-test. These correction factors for slopes and intercepts will allow the transformation of clumped isotope values at different temperatures into ARF scale at 25 °C and enable accurate deduction of temperature for carbonate samples. Correction factors proposed here account for variations in the sample preparation techniques arising due to different reaction temperatures, mechanisms and vapor pressure in the chamber for isotopic exchange reaction to happen for smaller or prolonged time intervals.