High-density volatiles in the system C-O-H-N for the calibration of a laser Raman microprobe

Three methods have been used to produce high-density volatiles in the system C-O-H-N for the calibration of a laser Raman microprobe (LRM): synthetic fluid-inclusion, sealed fused-quartz-tube, and high-pressure-cell methods. Because quantitative interpretation of a Raman spectrum of mixed-volatile fluid inclusions requires accurate knowledge of pressure- and composition-sensitive Raman scattering efficiencies or quantification factors for each species, calibrations of these parameters for mixtures of volatiles of known composition and pressure are necessary. Two advantages of the synthetic fluid-inclusion method are that the inclusions can be used readily in complementary microthermometry (MT) studies and that they have sizes and optical properties like those in natural samples. Some disadvantages are that producing H2O-free volatile mixtures is difficult, the composition may vary from one inclusion to another, the exact composition and density of the inclusions are difficult to obtain, and the experimental procedures are complicated. The primary advantage of the method using sealed fused-quartz tubes is its simplicity. Some disadvantages are that exact compositions for complex volatile mixtures are difficult to predict, densities can be approximated only, and complementary MT studies on the tubes are difficult to conduct. The advantages of the high-pressure-cell method are that specific, known compositions of volatile mixtures can be produced and that their pressures can be varied easily and are monitored during calibration. Some disadvantages are that complementary MT analysis is impossible, and the setup is bulky. Among the three methods for the calibration of an LRM, the high-pressure-cell method is the most reliable and convenient for control of composition and total pressure. We have used the high-pressure cell to obtain preliminary data on (1) the ratio of the Raman quantification factors for CH4 and N2 in an equimolar CH4N2 mixture and (2) the spectral peak position of ν1 of CH4 in that mixture, as well as in pure CH4, at pressures up to 690 bars. These data were successfully applied to natural inclusions from the Duluth Complex in order to derive their compositions and total pressures.