Relative stability and significance of dawsonite and aluminum minerals in geologic carbon sequestration

摘要

Computer simulations predict dawsonite, NaAlCO_3(OH)_2, will provide long-term mineral sequestration of anthropogenic CO_2 whereas dawsonite rarely occurs in nature or in laboratory experiments that emulate a carbon repository. Resolving this discrepancy is important to determining the significance of dawsonite mineralization to the long-term security of geologic carbon sequestration. This study is an equilibrium-based experimental and modeling evaluation of underlying causes for inconsistencies between predicted and observed dawsonite stability. Using established hydrothermal methods, 0.05 molal NaHCO_3 aqueous solution and synthetic dawsonite were reacted for 18.7 days (449.2 hours) at 50°C, 20 MPa. Temperature was increased to 75°C and the experiment continued for an additional 12.3 days (295.1 hours). Incongruent dissolution yielded a dawsonite-gibbsite-nordstrandite assemblage. Geochemical simulations using Geochemist's Workbench and the resident database thermo.com.V8.R6+ incorrectly predicted a dawsonite-diaspore assemblage and underestimated dissolved aluminum by roughly 100 times. Higher aqueous aluminum concentrations in the experiment suggest that dawsonite or diaspore is less stable than predicted. Simulations employing an alternate database, thermo.dat, correctly predict dawsonite and dawsonite-gibbsite assemblages at 50 and 75C, respectively, although dissolved aluminum concentrations are still two to three times lower than experimentally measured values. Correctly reproducing dawsonite solubility in standard geochemical simulations requires an as yet undeveloped internally consistent thermodynamic database among dawsonite, gibbsite, boehmite, diaspore, aqueous aluminum complexes and other Al-phases such as albite and kaolinite. These discrepancies question the ability of performance assessment models to correctly predict dawsonite mineralization in a sequestration site.