Raman quantification factor calibration for CO-CO2 gas mixture in synthetic fluid inclusions: Application to oxygen fugacity calculation in magmatic systems

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JUN 30
With a combined approach using Solid-State C-13-MAS NMR and Laser Raman Microspectroscopy, we investigated the CO2-CO gas composition (X(CO2)) in fluid inclusions synthesized under high pressure (200-300 MPa), high temperature (1225-1250 degrees C) and reducing conditions (17 <P(H-2) <62 bars). Fluid inclusions are entrapped in a volatile-bearing basaltic glass which was characterized by FTIR for determining the water solubility (H2Om). C-13-MAS NMR is used as a standard analysis for determining the X(CO2). The Raman quantification factors between (CO2)-C-13 and 13 CO are determined from peak area (F-factor), peak height (G-factor) and according to the Placzek's polarizability theory. The calibration is derived for both CO2 Fermi diad resonances: 2 nu(2) and nu(t). We obtain similar values for the main CO2 resonance (2 nu(2)) with 1.956 and 1.809 for F and G respectively. Results are consistent with the fact that peak height and area will measure the same quantity. For nu(1), multiple calibration trends are observed. The different trends are explained by the different C-13/C-12 ratio observed in between the samples. However, we suggest that such resonance is not suitable for determining the fluid inclusion compositions. We extended the C-13 results for calibrating the F- and G-factors for (CO2)-C-12-(CO)-C-12 gas mixture in the fluid inclusions and for the main CO2 resonance, For (CO2)-C-12-(CO)-C-12 mixture, F and G values are 1.856 and 1.756 which is in the same order as the derived values for C-13 species. Thus, we propose that no significant C-13/C-12 fractionation occurs in the fluid phase and both isotopes will behave in a similar way. Using the derived calibration for C-12 and C-13 species, the X(CO2) in the fluid phase was recalculated. Results are similar for both isotopes witnessing the similar behaviour of C-12 and C-13 fluid species during the experiments. The log f(O-2) experienced by each sample has been calculated through a thermodynamic approach using 2 independent methods. The log f(O-2) calculated from the H2Om in the glass and the X(CO2) in the fluid phase are in good agreement. Large discrepancy is observed for low H2Om content which gives lower log f(O-2) value than expected from experimental conditions. Large uncertainties on the H2Om measurements will induce a very approximate value for the 10002). This method may not be accurate enough at low H2Om and using the WOO in the fluid phase would therefore provide a better estimate of the log f(O-2). (c) 2009 Elsevier B.V. All rights reserved.