Correlated Structure and Dynamics of Ions and Water at Mineralogical Solid-Water Interfaces
EMSL Project ID
44600
Abstract
The objective of this work is to gain new insight into fundamental processes that occur at solid-fluid interfaces by performing a detailed, molecular-scale study of cation and H2O behavior at surfaces in clay-water and carbonate-water systems. Solid-fluid interfacial behavior has direct and important implications on reactive transport and transport modeling of metal contaminants, surface chemistry and biochemistry, biomineralization, heterogeneous catalysis, and long-term sequestration of nuclear waste. In this science-theme proposal, we will complete ongoing studies of the alkali metal and alkaline earth metal binding structures and dynamics at the interlayer and external surfaces of smectites (swelling clays) and will explore the structure and dynamics of hydrous amorphous calcium carbonates (ACCs) as a function of water content and temperature. Dynamics on the 10-5 to 10-10 s time scales of both cations (39K, 23Na, 133Cs, 43Ca, 25Mg, 87Sr) and H2O (2H) will be investigated using variable temperature NMR and relaxation measurements. The high-field NMR instrumentation at EMSL is essential to overcome sensitivity limitations associated with the low-gamma quadrupolar nuclei in these studies (39K, 43Ca, 25Mg, 87Sr), and our proposed VT/relaxation studies will be the first of their kind for many of these species. Characterizing the spatial arrangement of the clay layers and pore structure of these materials will also be crucial, and can be achieved without destructive heating/dehydration using recently developed cryogenic SEM/TEM methods and the EMSL electron microscopy facilities. This work will contribute directly toward several papers combining experimental data and in-house molecular dynamics computations over the life of the proposal.
Project Details
Project type
Large-Scale EMSL Research
Start Date
2011-10-01
End Date
2014-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
Bowers GM, DW Hoyt, SD Burton, BO Ferguson, T Varga, and RJ Kirkpatrick. 2014. "In Situ 13C and 23Na MAS NMR Investigation of Supercritical CO2 Incorporation in Smectite-Natural Organic Matter Composites ." Journal of Physical Chemistry C. doi:10.1021/jp410535d
Bowers GM, JW Singer, DL Bish, and RJ Kirkpatrick. 2014. "Structural and Dynamical Relationships of Ca2+ and H2O in Smectite/2H2O Systems." American Mineralogist 99(2-3):318-331. doi:10.2138/am.2014.4499
Kirkpatrick R J,Kalinichev A G,Bowers G M,Yazaydin A O,Krishnan M ,Saharay M ,Morrow C P 2015. "NMR and Computational Molecular Modeling Studies of Mineral Surfaces and Interlayer Galleries: A Review" The American Mineralogist 100(7):1341-1354. 10.2138/am-2015-5141