TY - JOUR

T1 - CO2 solubility in dacitic melts equilibrated with H2O-CO2 fluids

T2 - Implications for modeling the solubility of CO2 in silicic melts

AU - Behrens, Harald

AU - Ohlhorst, Susanne

AU - Holtz, Francois

AU - Champenois, Michel

N1 - Funding Information: This study was supported by the Deutsche Forschungsgemeinschaft (DFG grant Ho 1337/3+7). Fruitful comments of Hans Keppler, Yang Liu and two anonymous reviewers helped to improve the manuscript. Copyright: Copyright 2011 Elsevier B.V., All rights reserved.

PY - 2004/11/15

Y1 - 2004/11/15

N2 - The solubility of CO2 in dacitic melts equilibrated with H2O-CO2 fluids was experimentally investigated at 1250°C and 100 to 500 MPa. CO2 is dissolved in dacitic glasses as molecular CO2 and carbonate. The quantification of total CO2 in the glasses by mid-infrared (MIR) spectroscopy is difficult because the weak carbonate bands at 1430 and 1530 cm-1 can not be reliably separated from background features in the spectra. Furthermore, the ratio of CO2,mol/carbonate in the quenched glasses strongly decreases with increasing water content. Due to the difficulties in quantifying CO2 species concentrations from the MIR spectra we have measured total CO2 contents of dacitic glasses by secondary ion mass spectrometry (SIMS). At all pressures, the dependence of CO2 solubility in dacitic melts on xfluidCO2,total shows a strong positive deviation from linearity with almost constant CO2 solubility at xCO2fluid > 0.8 (maximum CO2 solubility of 795 ± 41, 1376 ± 73 and 2949 ± 166 ppm at 100, 200 and 500 MPa, respectively), indicating that dissolved water strongly enhances the solubility of CO2. A similar nonlinear variation of CO2 solubility with XCO2fluid has been observed for rhyolitic melts in which carbon dioxide is incorporated exclusively as molecular CO2 (Tamic et al., 2001 ). We infer that water species in the melt do not only stabilize carbonate groups as has been suggested earlier but also CO2 molecules. A thermodynamic model describing the dependen ce of the CO2 solubility in hydrous rhyolitic and dacitic melts on T, P, fCO2 and the mol fraction of water in the melt (xwater) has been developed. An exponential variation of the equilibrium constant K1 with xwater is proposed to account for the nonlinear dependence of xCO2,totalmelt on xCO2fluid. The model reproduces the CO2 solubility data for dacitic melts within ±14% relative and the data for rhyolitic melts within 10% relative in the pressure range 100-500 MPa (except for six outliers at low xCO2fluid). Data obtained for rhyolitic melts at 75 MPa and 850°C show a stronger deviation from the model, suggesting a change in the solubility behavior of CO2 at low pressures (a Henrian behavior of the CO2 solubility is observed at low pressure and low H2O concentrations in the melt). We recommend to use our model only in the pressure range 100-500 MPa and in the xCO2fluid range 0.1-0.95. The thermodynamic modeling indicates that the partial molar volume of total CO2 is much lower in rhyolitic melts (31.7 cm3/mol) than in dacitic melts (46.6 cm3/mol). The dissolution enthalpy for CO2 in hydrous rhyolitic melts was found to be negligible. This result suggests that temperature is of minor importance for CO2 solubility in silicic melts.

AB - The solubility of CO2 in dacitic melts equilibrated with H2O-CO2 fluids was experimentally investigated at 1250°C and 100 to 500 MPa. CO2 is dissolved in dacitic glasses as molecular CO2 and carbonate. The quantification of total CO2 in the glasses by mid-infrared (MIR) spectroscopy is difficult because the weak carbonate bands at 1430 and 1530 cm-1 can not be reliably separated from background features in the spectra. Furthermore, the ratio of CO2,mol/carbonate in the quenched glasses strongly decreases with increasing water content. Due to the difficulties in quantifying CO2 species concentrations from the MIR spectra we have measured total CO2 contents of dacitic glasses by secondary ion mass spectrometry (SIMS). At all pressures, the dependence of CO2 solubility in dacitic melts on xfluidCO2,total shows a strong positive deviation from linearity with almost constant CO2 solubility at xCO2fluid > 0.8 (maximum CO2 solubility of 795 ± 41, 1376 ± 73 and 2949 ± 166 ppm at 100, 200 and 500 MPa, respectively), indicating that dissolved water strongly enhances the solubility of CO2. A similar nonlinear variation of CO2 solubility with XCO2fluid has been observed for rhyolitic melts in which carbon dioxide is incorporated exclusively as molecular CO2 (Tamic et al., 2001 ). We infer that water species in the melt do not only stabilize carbonate groups as has been suggested earlier but also CO2 molecules. A thermodynamic model describing the dependen ce of the CO2 solubility in hydrous rhyolitic and dacitic melts on T, P, fCO2 and the mol fraction of water in the melt (xwater) has been developed. An exponential variation of the equilibrium constant K1 with xwater is proposed to account for the nonlinear dependence of xCO2,totalmelt on xCO2fluid. The model reproduces the CO2 solubility data for dacitic melts within ±14% relative and the data for rhyolitic melts within 10% relative in the pressure range 100-500 MPa (except for six outliers at low xCO2fluid). Data obtained for rhyolitic melts at 75 MPa and 850°C show a stronger deviation from the model, suggesting a change in the solubility behavior of CO2 at low pressures (a Henrian behavior of the CO2 solubility is observed at low pressure and low H2O concentrations in the melt). We recommend to use our model only in the pressure range 100-500 MPa and in the xCO2fluid range 0.1-0.95. The thermodynamic modeling indicates that the partial molar volume of total CO2 is much lower in rhyolitic melts (31.7 cm3/mol) than in dacitic melts (46.6 cm3/mol). The dissolution enthalpy for CO2 in hydrous rhyolitic melts was found to be negligible. This result suggests that temperature is of minor importance for CO2 solubility in silicic melts.

UR - http://www.scopus.com/inward/record.url?scp=7744224739&partnerID=8YFLogxK

U2 - 10.1016/j.gca.2004.04.019

DO - 10.1016/j.gca.2004.04.019

M3 - Article

AN - SCOPUS:7744224739

VL - 68

SP - 4687

EP - 4703

JO - Geochimica et Cosmochimica Acta

JF - Geochimica et Cosmochimica Acta

SN - 0016-7037

IS - 22

ER -