High-precision analysis of carbon isotopic composition for individual CO₂ inclusions via Raman spectroscopy to reveal the multiple-stages evolution of CO₂- bearing fluids and melts

The carbon isotopic composition of CO₂ inclusions trapped in minerals reflects the origin and evolution of CO₂-bearing fluids and melts, and records the multiple-stages carbon geodynamic cycle, as CO₂ took part in various geological processes widely. However, the practical method for determination isotope composition of individual CO₂ inclusion is still lacking. Developing a microanalytical technique with spatial resolution in micrometers to precisely determinate the δ¹³C value of individual CO₂ inclusion, will make it possible to analyze a tiny portion of a zoning mineral crystal, distinguish the differences in micro-scale, and possible to find many useful information that could not be obtained with the bulk extraction and analysis techniques. In this study, we systematically collected Raman spectra of CO₂ standards with different δ¹³C values (−34.9 ‰ to 3.58 ‰) at 32.0 °C and from ~7.0 MPa to 120.0 MPa, and developed a new procedure to precisely determinate the δ¹³C value of individual CO₂ inclusion. We investigated the relationship among the Raman peak intensity ratio, δ¹³C value, and CO₂ density, and established a calibration model with high accuracy (0.5 ‰−1.5 ‰), sufficient for geological application to distinguish different source of CO₂ with varying δ¹³CO₂. As a demonstration, we measured the δ¹³C values and the density of CO₂ inclusions in the growth zones of alkali basalt-hosted corundum megacrysts from Changle, Shandong Province. We found the significant differences of density and δ¹³C between the CO₂ inclusions in the core of corundum and those inclusions in the outer growth zones, the δ¹³C value decreases from core to rim with decreasing density: δ¹³C values are from −7.5 ‰ to −9.2 ‰ for the inclusions in the core, indicating the corundum core was crystallized from mantle-derived magmas; from −13.5 ‰ to −18.5 ‰ for CO₂ inclusions in zone 1 and from −16.5 ‰ to -22.0 ‰ for inclusions in zone 2, indicating the outer zones of corundum grew in a low δ¹³C value environment, resulted from an infilling of low δ¹³C value fluid and/or degassing of the ascending basaltic magma.