The Role of Interfacial Processes on Mineral Transformations in Wet Supercritical CO2
EMSL Project ID
39937
Abstract
We propose a comprehensive experimental and theoretical investigation of the role of interfacial water and CO2 on the energies, mechanisms, and rates of reactivity of a series of orthosilicate and phyllosilicate minerals in contact with supercritical-CO2 (scCO2) containing variable H2O. The molecular mechanisms for carbonation reactions, as well as the distribution of H2O between scCO2 and mineral surfaces, will be followed using molecular simulations and surface spectroscopy as a function of T, P, mineral composition and structure, and aH2O. The dynamics of water reactivity will be simulated using newly developed molecular dynamics models and reaction barriers will be calculated using density functional and molecular orbital theory electronic structure methods. The theoretical studies will be coupled with high-resolution spectroscopic measurements (e.g., IR/FTIR, NMR) to investigate the formation and structure of water layers at mineral surfaces and in the interlayer region of phyllosilicates, and identify potential interfacial carbonate and silicate species. The macroscopic reactivity of the orthosilicates and the changes in interlayer water structure and reactivity of the phyllosilicates will be determined experimentally using high pressure cells. The proposed research will provide new insights into mineral transformations under extreme conditions and help establish a basis for assessing the effectiveness of CO2 sequestration in geologic disposal sites.
Project Details
Project type
Large-Scale EMSL Research
Start Date
2010-10-01
End Date
2013-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
Arey BW, L Kovarik, O Qafoku, Z Wang, NJ Hess, and AR Felmy. 2013. "Identification of Fragile Microscopic Structures during Mineral Transformations in Wet Supercritical CO2." Microscopy and Microanalysis 19(2):268-275. doi:10.1017/S1431927612014171
Chatman SME, PP Zarzycki, and KM Rosso. 2013. "Surface Potentials of (001), (012), (113) Hematite (?-Fe2O3) Crystal Faces in Aqueous Solution." Physical Chemistry Chemical Physics. PCCP 15(33):13911-139-21. doi:10.1039/c3cp52592a
Chatman SME, PP Zarzycki, T Preocanin, and KM Rosso. 2013. "Effect of Surface Site Interactions on Potentiometric Titration of Hematite (?-Fe2O3) Crystal Faces." Journal of Colloid and Interface Science 391:125-134. doi:10.1016/j.jcis.2012.09.081
Felmy AR, O Qafoku, BW Arey, JZ Hu, MY Hu, HT Schaef, ES Ilton, NJ Hess, CI Pearce, J Feng, and KM Rosso. 2012. "Reaction of Water-Saturated Supercritical CO2 with Forsterite: Evidence for Magnesite Formation at Low Temperatures." Geochimica et Cosmochimica Acta 91:271-282. doi:10.1016/j.gca.2012.05.026
Hoyt DW, RVF Turcu, JA Sears, Jr, KM Rosso, SD Burton, AR Felmy, and JZ Hu. 2011. "High-pressure Magic Angle Spinning Nuclear Magnetic Resonance ." Journal of Magnetic Resonance 212(2):378-385. doi:10.1016/j.jmr.2011.07.019
Ilton ES, HT Schaef, O Qafoku, KM Rosso, and AR Felmy. 2012. "In Situ X-Ray Diffraction Study of Na+ Saturated Montmorillonite Exposed to Variably Wet Super Critical CO2." Environmental Science & Technology 46(7):4241-4248. doi:10.1021/es300234v
Kerisit SN. 2011. "Water Structure at Hematite-Water Interfaces." PNNL-SA-78242, Pacific Northwest National Laboratory, Richland, WA. doi:10.1016/j.gca.2011.01.026
Kerisit SN, JH Weare, and AR Felmy. 2012. "Structure and Dynamics of Forsterite-scCO2/H2O Interfaces as a Function of Water Content." Geochimica et Cosmochimica Acta 84:137-151. doi:10.1016/j.gca.2012.01.038
Kwak JH, JZ Hu, RVF Turcu, KM Rosso, ES Ilton, CM Wang, JA Sears, Jr, MH Engelhard, AR Felmy, and DW Hoyt. 2011. "The Role of H2O in the Carbonation of Forsterite in Supercritical CO2." International Journal of Greenhouse Gas Control 5(4):1081-1092. doi:10.1016/j.ijggc.2011.05.013
Kwak JH, JZ Hu, RVF Turcu, KM Rosso, ES Ilton, CM Wang, JA Sears, Jr, MH Engelhard, AR Felmy, and DW Hoyt. 2011. "The Role of H2O in the Carbonation of Forsterite in Supercritical CO2." International Journal of Greenhouse Gas Control 5(4):1081-1092. doi:10.1016/j.ijggc.2011.05.013
Loring JS, CJ Thompson, Z Wang, AG Joly, DS Sklarew, HT Schaef, ES Ilton, KM Rosso, and AR Felmy. 2011. "In Situ Infrared Spectroscopic Study of Forsterite Carbonation in Wet Supercritical CO2." Environmental Science & Technology 45(14):6204-6210. doi:10.1021/es201284e
Loring JS, HT Schaef, RVF Turcu, CJ Thompson, QRS Miller, PF Martin, JZ Hu, DW Hoyt, O Qafoku, ES Ilton, AR Felmy, and KM Rosso. 2012. "In Situ Molecular Spectroscopic Evidence for CO2 Intercalation into Montmorillonite in Supercritical Carbon Dioxide." Langmuir 28(18):7125-7128. doi:10.1021/la301136w
Qafoku O, L Kovarik, RK Kukkadapu, ES Ilton, BW Arey, J Tucek, and AR Felmy. 2012. "Fayalite Dissolution and Siderite Formation in Water-Saturated Supercritical CO2." Chemical Geology 332-333:124-135. doi:10.1016/j.chemgeo.2012.09.028
Schaef HT, ES Ilton, O Qafoku, PF Martin, AR Felmy, and KM Rosso. 2012. "In situ XRD Study of Ca2+ Saturated Montmorillonite (STX-1) Exposed to Anhydrous and Wet Supercritical Carbon Dioxide." International Journal of Greenhouse Gas Control 6(1):220-229. doi:10.1016/j.ijggc.2011.11.001
Springer RD, Z Wang, A Anderko, P Wang, and AR Felmy. 2012. "A Thermodynamic Model for Predicting Mineral Reactivity in Supercritical Carbon Dioxide: I. Phase Behavior of Carbon Dioxide - Water - Chloride Salt Systems Across the H2O-Rich to the CO2-Rich Regions ." Chemical Geology 322-323:151-171. doi:10.1016/j.chemgeo.2012.07.008
Turcu RVF, DW Hoyt, KM Rosso, JA Sears, Jr, JS Loring, AR Felmy, and JZ Hu. 2013. "Rotor Design for High Pressure Magic Angle Spinning Nuclear Magnetic Resonance." Journal of Magnetic Resonance 226:64-69. doi:10.1016/j.jmr.2012.08.009
Wang Z, AR Felmy, CJ Thompson, JS Loring, AG Joly, KM Rosso, HT Schaef, and DA Dixon. 2013. "Near-Infrared Spectroscopic Investigation of Water in Supercritical CO2 and the Effect of CaCl2." Fluid Phase Equilibria 338:155-163. doi:10.1016/j.fluid.2012.11.012
White MD, BP McGrail, HT Schaef, JZ Hu, DW Hoyt, AR Felmy, KM Rosso, and SK Wurstner. 2011. "Multiphase Sequestration Geochemistry: Model for Mineral Carbonation." Energy Procedia 4:5009-5016. doi:10.1016/j.egypro.2011.02.472