Behavior of Ions and H2O at NOM, Clay, and Clay-NOM Interfaces with Supercritical Fluids
EMSL Project ID
48812
Abstract
Our research program strives to provide new insight into the fundamental molecular-scale dynamics, energetics, and reactivity of geochemically relevant solid-fluid interfaces through combined spectroscopy and molecular modeling. These data are important to understand nutrient cycling, the global carbon balance, fluid transport in rock nanopores, and inorganic and organic pollutant transport in the lithosphere. This science theme proposal furthers our mission by using the unique capabilities of several EMSL resources to explore the behavior of ions and H2O in natural organic matter (NOM) and hydrated clay minerals with and without NOM coatings in the presence of supercritical CO2 (scCO2) and methane (scCH4). Specific objectives of the proposed research are to characterize the binding sites, dynamic averaging mechanisms, rates of molecular motion on the 10-5 to 10-10 s time scales, and the chemical controls over these processes for alkali and alkaline earth metals in NOM floccs and smectite-NOM composite materials with varying degrees of hydration under in situ scCO2 and scCH4 conditions. We also seek to determine the coordination geometry, dynamic mechanisms, and rates of motion for residual H2O in these systems. The many high-field NMR instruments and the specialized high-pressure NMR rotor system at EMSL are essential to the novel in situ scCO2 and scCH4 experiments and to provide necessary data for comparison with molecular dynamics computer simulations performed by our group off site. Characterizing the spatial arrangement of the clay layers and pore structure of these materials will also be crucial, and can be achieved using SEM/HeIM methods in the EMSL charged beam microscopy facilities and the XRD instruments capable of controlled humidity XRD experiments at EMSL. This work will contribute directly toward several papers combining spectroscopic and computational results over the life of the proposal and serve as the basis for several undergraduate theses and the professional development of at least one post-doc.
Project Details
Project type
Large-Scale EMSL Research
Start Date
2015-10-01
End Date
2017-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Co-Investigator(s)
Team Members
Related Publications
Bowers GM, HT Schaef, JS Loring, DW Hoyt, SD Burton, ED Walter, and RJ Kirkpatrick. 2017. "Role of Cations in CO2 Adsorption, Dynamics, and Hydration in Smectite Clays Under in situ Supercritical CO2 Conditions." Journal of Physical Chemistry C 121(1):577-592. doi:10.1021/acs.jpcc.6b11542
Bowers G.M., J.S. Loring, H.T. Schaef, E.D. Walter, S.D. Burton, D.W. Hoyt, and S.S. Cunniff, et al. 2018. "Interaction of Hydrocarbons with Clays under Reservoir Conditions: In Situ Infrared and Nuclear Magnetic Resonance Spectroscopy and X-ray Diffraction for Expandable Clays with Variably Wet Supercritical Methane." ACS Earth and Space Chemistry 2, no. 7:640-652. PNNL-SA-136218. doi:10.1021/acsearthspacechem.8b00039
Bowers G.M., J.S. Loring, H.T. Schaef, S.S. Cunniff, E.D. Walter, S.D. Burton, and R.K. Larsen, et al. 2019. "Chemical Trapping of CO2 by Clay Minerals at Reservoir Conditions: Two Mechanisms Observed by In Situ High Pressure and Temperature Experiments." ACS Earth and Space Chemistry 3, no. 6:1034-1046. PNNL-SA-140918. doi:10.1021/acsearthspacechem.9b00038
Bowers G.M., S.S. Cunniff, E.S. Ilton, H.T. Schaef, L. Kovarik, S.D. Burton, and Q. Miller, et al. 2018. "Protonation of clay in hydrated supercritical CO2." Chemistry of Materials. PNNL-SA-131616. [Unpublished]
Nanda R., G.M. Bowers, N. Loganathan, S.D. Burton, and R.J. Kirkpatrick. 2019. "Temperature dependent structure and dynamics in smectite interlayers: 23Na MAS NMR spectroscopy of Na-hectorite." Royal Society of Chemistry 9, no. 22:12755-12765. PNNL-SA-145048. doi:10.1039/c9ra01056d
Nanda R., G.M. Bowers, N. Loganathan, S.D. Burton, and R.J. Kirkpatrick. 2019. "Temperature dependent structure and dynamics in smectite interlayers: 23Na MAS NMR spectroscopy of Na-hectorite." Royal Society of Chemistry 9. PNNL-SA-145048.
Schaef HT, N Loganathan, GM Bowers, RJ Kirkpatrick, AO Yazaydin, SD Burton, DW Hoyt, S Thanthiriwatte, DA Dixon, BP McGrail, KM Rosso, ES Ilton, and JS Loring. 2017. "Tipping Point for Expansion of Layered Aluminosilicates in Weakly Polar Solvents: Supercritical CO2." ACS Applied Materials & Interfaces (9):36783?36791. doi:10.1021/acsami.7b10590