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In Situ Nuclear Magnetic Resonance Investigations of Trapping Mechanisms in CO2 Storage

EMSL Project ID


Global increases in carbon emissions and the rapid decrease in energy securities have resulted in an increased global commitment to develop technology for stabilizing CO2 released into the environment. One proposed method for reducing this greenhouse gas in the atmosphere is to store the CO2 underground. Natural reservoirs of the gas exist, suggesting that geologic carbon sequestration is feasible. However, little is known about the molecular based mechanisms that govern the storage of CO2. This requires an understanding of the geochemical processes associated with CO2 sequestration in complex and heterogeneous subsurface mineral assemblages comprising porous rock formations, and in the equally complex fluids that may reside in and flow through those formations.

We propose to develop unique in situ NMR capabilities, including the application of the existing advanced NMR techniques available in EMSL, to advance the understanding of geochemical processes associated with the precipitation and dissolution of CO2 at molecular level. In particular, we will study the interfacial structure, kinetics and mechanisms of common primary and secondary mineral phase dissolution in CO2/water mixtures and carbonate nucleation and mineralization reactions as a function of composition, temperature, and pressure. We will study the detailed molecular interaction between the CO2 molecules and the surface moieties/functional groups of selected geological media, including mineral interfacial reactions with CO2, or mixed solvent CO2-water solutions in porous media, and the interaction of CO2 with H2O molecules at the relevant geological temperature (from -20 to 80°C) and pressure (from less than 1.0 to 80 atmospheres).

This project is the first year of a three year LDRD and the NMR scope will be limited to probing surface chemistry and molecular dynamics using low pressure in situ MAS NMR. Both the sealed MAS rotor approach and the atmospheric pressure Large-Sample-Volume-Constant-Flow-MAS capability will be utilized. The systems to be investigated include MgO, CaO, Mg2SiO4, hydroxides Mg(OH)2 and Ca(OH)2 as a function of CO2 and H2O concentrations.

Summary of Expected Outcomes (over 3 years)

From our studies, our hope to provide new insights into the physical/chemical phenomena that underlie the carbon sequestration at the subsurface, in particular the molecular mechanisms of mineral interfacial reactions with CO2, the effects of a varied amounts of water on this reaction, the effects of structural and chemical heterogeneity at the interfaces on the reaction kinetics, and the macroscopic dynamics of CO2 and water at relevant geological temperature and pressure. At the end of the work, EMSLs competitive capabilities and distinctive signature, i.e., the unique in situ NMR capabilities will be established, which will better position PNNL to support DOEs missions in carbon sequestration.

Project Details

Start Date
End Date


Principal Investigator

David Hoyt
Environmental Molecular Sciences Laboratory

Team Members

Jason Skouson
Pacific Northwest National Laboratory

Ja Hun Kwak
Ulsan National Institute of Science and Technology

Jesse Sears
Environmental Molecular Sciences Laboratory

Jian-zhi Hu
Pacific Northwest National Laboratory

Related Publications

Hu JZ, JA Sears, Jr, HS Mehta, JJ Ford, JH Kwak, K Zhu, Y Wang, J Liu, DW Hoyt, and CHF Peden. 2012. "A Large Sample Volume Magic Angle Spinning Nuclear Magnetic Resonance Probe for In-Situ Investigations with Constant Flow of Reactants." Physical Chemistry Chemical Physics. PCCP 14(7):2137-2143. doi:10.1039/c1cp22692d
Metal Carbonation of Forsterite in Supercritical CO2 and H2O Using Solid State 29Si, 13C NMR Spectroscopy Ja Hun Kwak, Jian Zhi Hu, David W. Hoyt, Jesse A. Sears, Chongming Wang, Kevin M. Rosso, and Andrew R. Felmy J. Phys. Chem. C 2010, 114, 4126–4134 10.1021/jp1001308 2010 American Chemical Society Published on Web 02/17/2010
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