In situ carbon and oxygen isotopes measurements in carbonates by fiber coupled laser diode-induced calcination: A step towards field isotopic characterization

Natural stable isotopes ratios (δ13Ccarb and δ18Ocarb) of carbonates archived in the geological record are routinely used to reconstruct local and global paleo temperatures and the secular evolution of the biogeochemical carbon cycle. The state-of-the-art technique, employed since the mid 20th century, to measure these isotopic ratios starts with field sampling followed by several steps of physical and chemical laboratory preparation including: (i) microdrilling and/or sawing and crushing, (ii) CO2 release by wet acid digestion, (iii) gas equilibration, purification and transfer, before (iv) gas phase IRMS measurements. While these steps are time and resource consuming, they provide accurate measurements of δ13Ccarb, δ18Ocarb and carbonate contents. This study presents a new protocol involving a compact and modernized laser calcination system that decreases drastically the analyses time by reducing the number of preparations steps together with offering the possibility of performing spatially resolved analysis at the mm scale. This new method is based on the use of a fiber coupled laser diode device emitting 30 W in the near infrared at 880 nm. The energy provided by the laser source induces the decomposition of calcium carbonate into lime and carbon dioxide. In this work, the CO2 was collected in sample tubes under a controlled atmosphere for offline analysis, however additional developments should permit online analysis in the near future. We analyzed 9 different types of carbonate minerals encompassing a range of isotopic compositions VPDB between +3.3 and − 18.2‰ and between −1.7 and − 14.6‰ for δ13Ccarb and δ18Ocarb, respectively. A comparison of isotopic results was performed for carbonate zones analyzed both by classic methods (micro-drilling followed by acid digestion) and laser calcination. This isotopic cross-calibration exercise shows a direct positive co-variation between both methods with a correlation coefficient of 0.99 and a regression slope of 1 within uncertainties for the δ13Ccarb values. The δ18Ocarb values also compared well with a correlation coefficient of 0.96, suggesting a constant gas-solid phase isotopic equilibrium between carbon dioxide and lime. The reproducibility of our laser calcination method performed on replicate analyses of dolomite, siderite and malachite shows a 1σ standard deviation of 0.31 and 0.77 for δ13Ccarb and δ18Ocarb, respectively. These reproducibilities are within the observed isotopic natural inhomogeneity of samples (up to 1.3 and 0.57‰ for the δ13Ccarb and δ18Ocarb, respectively) as assessed by microdrilling and acid digestion. Based on the suit of samples analyzed in this study, we demonstrate that (i) fiber coupled laser diode calcination enables accurate and reproducible C and O isotopic characterization of natural carbonates, (ii) physical effects during calcination do not introduce any isotopic fractionation for C and is accompanied by a constant isotopic offset for O over a range of isotopic compositions and mineral matrices. These findings pave the way for a new range of possibilities for carbonate δ13C and δ18O measurements directly in the field using rapid, portable, and easy to manipulate laser preparation devices paired with CRDS/IRIS optical-mass spectrometers