Experimental Study of Basalt Carbonatization

Abstract : The increasing levels of CO2 in the atmosphere and the potential dangers this pose to the Earth through climate change, ocean acidification and sea-level rise has lead to a substantial number of projects attempting to find a safe and benign way to capture and store CO2 in geological formations, also referred to as the CCS (Carbon Capture Storage) technology. One of these CCS attempts is currently taking place in Iceland at the geothermal power plant Hellisheiði, located close to the capital Reykjavik (the CarbFix project). CO2 and other gasses (H2S, N2, H2, CH4) are waste products of the geothermal energy exploitation and the aim is with time to store all of this anthropogenic-made CO2 in the basaltic formations underlying Hellisheiði. The CO2 is dissolved in groundwater as it is pumped down to 350 meters depth and then injected into mixed horizons of basaltic glass and crystalline basalt. The basaltic rocks are characterized by high contents of divalent cations like Mg2+, Fe2+ and Ca2+ and relatively fast dissolution rates. The acidic CO2-loaded water will dissolve the basalt thereby releasing cations, which can react with the aqueous carbonate ions to form carbonate minerals (magnesite, siderite, calcite, ankerite and Ca-Mg-Fe solid solutions). The rate-limiting step of this carbon sequestration process is thought to be the dissolution of basaltic rocks, thus any effect that could potentially limit basalt dissolution would be detrimental to the overall CO2 sequestration process. My part of the CarbFix project has been to look at the effects the formation of calcium carbonate coatings would have on the dissolution of the primary phase, in this case basaltic glass and the clinopyroxene diopside, so there would be a glass phase to compare with the results of a mineral phase. Furthermore, a series of experiments were conducted where we tested the primary mineral structure's affect on calcite nucleation. This was done in order to test if different silicate structures would lead to different extent of calcite nucleation and growth. Finally, extensive series were conducted on the dissolution of basaltic glass in the presence of dead and live heterotrophic bacteria, Pseudomonas reactans in order to determine the potential effect of bacteria on the carbon storage effort at the Hellisheiði site. The basaltic glass and diopside dissolution experiments were run at 25 and 70 ºC and pH 7-8 in mixed-flow reactors connected to solutions containing CaCl2±NaHCO3 with ionic strengths > 0.03 mol/kg. Two sets of experimental series were run simultaneously, one series called the "precipitation" experiments in which the solution inside the reactor was supersaturated with respect to calcite, and the other series called the "control" experiments, where PHREEQC modeling foretold no major secondary mineral formation. By this, it was possible to compare dissolution rates of basaltic glass and diopside at 25 ºC with and without calcium carbonate and other secondary mineral formation in order to deduce the effect on their dissolution rates. Scanning electron microscope images showed substantial amounts of calcium carbonate had precipitated in the "precipitation" experiments, but in the case of basaltic glass the primary growth appeared as big, discrete cluster of calcite and aragonite with no growth on the glass itself. Opposed to this, several of the diopside crystals were extensively overgrown by calcite coatings and no aragonite was found. In neither cases did the presence of calcite/aragonite have an effect on the dissolution rates of basaltic glass and diopside when compared to the "control' dissolution rates. It appears the discontinuous cover of the carbonate allows the ions of the primary phases to continue to diffuse through the secondary layer unhindered. To further assess the effect of silicate surface on the nucleation of calcite, the dissolution rates of six selected silicate minerals and rocks were measured in mixed-flow reactors in solutions supersaturated with respect to calcite at 25 ºC and pH ~9.1. The silicate phases were: Mg-rich olivine, enstatite, augite, labradorite, basaltic glass and peridotite. The results show different onset time of calcite nucleation and thus different extent of carbonate coverage with elapsed time depending on silicate phase. Within the same timeframe olivine, enstatite and peridotite (mainly composed of Mg-rich olivine) were the most covered by calcite precipitations, followed by augite, labradorite and finally basaltic glass. All calcite growth took place on the silicate surface including on the basaltic glass. Kinetics favor calcite nucleation growth on the orthorhombic minerals (enstatite and olivine) over the monoclinic and triclinic minerals. Least calcite was found on the glass, which has no ordered silicate structure. Heterotrophic bacteria, Pseudomonas reactans was extracted from one of the monitoring wells at Hellisheiði, and then separated, purified and cultured in the laboratory. Its optimal growth conditions were found to be 5-37 ºC and pH 7.0-8.2 on Brain Heart Broth nutrient. Being a common water- and soil bacteria it offered a good candidacy to test what could be expected of heterotrophic bacteria in general when storing CO2 in a natural aquifers like the one at the Hellisheiði site, in Iceland. Basaltic glass dissolution rates were measured at 25 ºC in newly developed Bacterial Mixed-Flow reactors (BMFR) in buffer solutions carrying 0.1-0.4 g/L of dead bacteria and 0.9-19 g/L of live bacteria at 4 ≤ pH ≤10. The results show that the presence had either no or a slightly rate-limiting effect. The overall conclusion is that neither the carbonate coatings nor the bacteria had major impact on the measured dissolution rates of the primary silicate phases, thus their effect are expected to be negligible on the CO2 sequestration process in basalt. Crystalline basalt might be faster covered by calcium carbonate, but also basaltic glass can act as a nucleation platform for calcite nucleation.
Document type :
Theses
Geochemistry. Université Paul Sabatier - Toulouse III, 2012. English


https://tel.archives-ouvertes.fr/tel-00712597
Contributor : Williams Exbrayat <>
Submitted on : Wednesday, June 27, 2012 - 2:03:14 PM
Last modification on : Thursday, March 12, 2015 - 12:03:03 PM

Identifiers

  • HAL Id : tel-00712597, version 1

Collections

Citation

Gabrielle J. Stockmann. Experimental Study of Basalt Carbonatization. Geochemistry. Université Paul Sabatier - Toulouse III, 2012. English. <tel-00712597>

Export

Share

Metrics

Consultation de
la notice

524

Téléchargement du document

201