Temperature and Salinity Effects on Quantitative Raman Spectroscopic Analysis of Dissolved Volatiles Concentration in Geofluids

The concentration detection of the volatiles such as CH4 and CO2 in the hydrothermal systems and fluid inclusions is critical for understanding the fluxes of volatiles from mantle to crust and atmosphere. In-situ Raman spectroscopy has been developed successfully in laboratory, fluid inclusions and submarine environment because of its non-destructive and non-contact advantages. For improving the ability of detecting different species quantitatively by in-situ Raman spectroscopy in the extreme environment, such as the hydrothermal system and fluid inclusion, we studied the temperature- and salinity-dependence of Raman scattering cross section (RSCS) of the water OH stretching band at temperatures from 20 to 300 oC under 30 MPa. This is important because the water is often used as internal standard in the Raman quantitative application. Based on our previous study of NaCl-H2O system, we made further investigation on the CaCl2-H2O system. Our results revealed that the cation shows negligible effect on the RSCS of water OH stretching band, while the cations seems to have more obvious different effect on the structure of water within high temperatures. Besides the NaCl-CH4-H2O system, we also take the CO2-H2O system into account. Further conclusion can be made that the variation of the Raman quantitative factor (QF) (both PAR/mCH4 and PAR/mCO2) with the temperature and salinity is mainly caused by the temperature- and Cl- concentration-dependence of the relative RSCS of the water OH stretching band. If the Raman quantitative factor at ambient condition still being used, the RSCS of the water OH stretching band would induce about 47%, 34% and 29% error for the determined concentration of dissolved CH4 or CO2 (in mol/kg·H2O) by in-situ Raman spectroscopy for 0 m Cl-, 3 m Cl- and 5 m Cl- aqueous system when the temperature increases from 20 to 300 oC, respectively. Considering the wide range of the temperature and salinity in hydrothermal systems and fluid inclusions, the following equation can be used to calculate the relative QF at different temperatures and salinity referencing to the 0 m Cl- aqueous solution at 20 oC: QF(T, salinity)/QF(20 oC, 0 m Cl-)=k(T-20 oC)+b, where a=-0.0035× mCl-1/2+0.00168, b=-0.03× mCl-+1;