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Title: Termination and hydration of forsteritic olivine (010) surface

Abstract

Termination and hydration of the forsteritic (Fo90Fa10) olivine (010) surface have been investigated with high-resolution specular X-ray reflectivity and Atomic Force Microscopy. The surface was prepared by polishing a naturally grown {010} face, from which we found the polished surface in acidic (pH 3.5) alumina suspension exhibits regular steps while the basic (pH 9.5) silica polished surface is irregularly roughened, indicating there are two distinguishable mechanochemical processes for the surface dissolution. The quantitative interpretation of the regular steps from the alumina polished surface suggests that the observed step heights correspond to multiples of crystallographic unit cell. The terrace surface is investigated with the high-resolution specular X-ray reflectivity to determine the crystallographic termination and hydration. The alumina polished olivine (010) surface in equilibrium with water is terminated at a plane including half-occupied metal ion sites (M1), an oxygen vacancy site, and a silicate tetrahedral unit with one of its apices pointing outward with respect to the surface. An ideal termination with the oxygen vacancy would fulfill the stoichiometry of the formula unit; however, in the observation, the vacancy site is filled by an adsorbed water species and about a quarter of the remaining metal ions are further depleted. The terminating planemore » generates two distinct atomic layers in the laterally averaged electron density profile, on which two highly ordered adsorbed water layers are formed. The first layer formation is likely through interaction with the M1 plane and the second layer is due to the hydrogen bonding interaction with the oxygen apex of the surface silicate tetrahedron. With this multilayered adsorbed water structure, the surface metal ion is partially hydrated by the vacancy-filling and the adsorbed water molecules. The bulk water links to these distinct adsorbed water layers, with weak density 2 oscillations that almost completely damp out after the first bulk water layer. The total thickness of the layered water structure including the two distinct adsorbed layers and the first layer of bulk water is slightly less than 1 nm, which corresponds to roughly three molecular layers of water. These results describe the steric constraints of the surface metal ion hydration and the iron redox environment during water-olivine interactions in this particular crystallographic orientation.« less

Authors:
; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science - Office of Basic Energy Sciences - Materials Sciences and Engineering Division
OSTI Identifier:
1356618
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Geochimica et Cosmochimica Acta
Additional Journal Information:
Journal Volume: 145; Journal ID: ISSN 0016-7037
Publisher:
The Geochemical Society; The Meteoritical Society
Country of Publication:
United States
Language:
English

Citation Formats

Yan, Hongping, Park, Changyong, Ahn, Gun, Hong, Seungbum, Keane, Denis T., Kenney-Benson, Curtis, Chow, Paul, Xiao, Yuming, and Shen, Guoyin. Termination and hydration of forsteritic olivine (010) surface. United States: N. p., 2014. Web. doi:10.1016/j.gca.2014.09.005.
Yan, Hongping, Park, Changyong, Ahn, Gun, Hong, Seungbum, Keane, Denis T., Kenney-Benson, Curtis, Chow, Paul, Xiao, Yuming, & Shen, Guoyin. Termination and hydration of forsteritic olivine (010) surface. United States. doi:10.1016/j.gca.2014.09.005.
Yan, Hongping, Park, Changyong, Ahn, Gun, Hong, Seungbum, Keane, Denis T., Kenney-Benson, Curtis, Chow, Paul, Xiao, Yuming, and Shen, Guoyin. Sat . "Termination and hydration of forsteritic olivine (010) surface". United States. doi:10.1016/j.gca.2014.09.005.
@article{osti_1356618,
title = {Termination and hydration of forsteritic olivine (010) surface},
author = {Yan, Hongping and Park, Changyong and Ahn, Gun and Hong, Seungbum and Keane, Denis T. and Kenney-Benson, Curtis and Chow, Paul and Xiao, Yuming and Shen, Guoyin},
abstractNote = {Termination and hydration of the forsteritic (Fo90Fa10) olivine (010) surface have been investigated with high-resolution specular X-ray reflectivity and Atomic Force Microscopy. The surface was prepared by polishing a naturally grown {010} face, from which we found the polished surface in acidic (pH 3.5) alumina suspension exhibits regular steps while the basic (pH 9.5) silica polished surface is irregularly roughened, indicating there are two distinguishable mechanochemical processes for the surface dissolution. The quantitative interpretation of the regular steps from the alumina polished surface suggests that the observed step heights correspond to multiples of crystallographic unit cell. The terrace surface is investigated with the high-resolution specular X-ray reflectivity to determine the crystallographic termination and hydration. The alumina polished olivine (010) surface in equilibrium with water is terminated at a plane including half-occupied metal ion sites (M1), an oxygen vacancy site, and a silicate tetrahedral unit with one of its apices pointing outward with respect to the surface. An ideal termination with the oxygen vacancy would fulfill the stoichiometry of the formula unit; however, in the observation, the vacancy site is filled by an adsorbed water species and about a quarter of the remaining metal ions are further depleted. The terminating plane generates two distinct atomic layers in the laterally averaged electron density profile, on which two highly ordered adsorbed water layers are formed. The first layer formation is likely through interaction with the M1 plane and the second layer is due to the hydrogen bonding interaction with the oxygen apex of the surface silicate tetrahedron. With this multilayered adsorbed water structure, the surface metal ion is partially hydrated by the vacancy-filling and the adsorbed water molecules. The bulk water links to these distinct adsorbed water layers, with weak density 2 oscillations that almost completely damp out after the first bulk water layer. The total thickness of the layered water structure including the two distinct adsorbed layers and the first layer of bulk water is slightly less than 1 nm, which corresponds to roughly three molecular layers of water. These results describe the steric constraints of the surface metal ion hydration and the iron redox environment during water-olivine interactions in this particular crystallographic orientation.},
doi = {10.1016/j.gca.2014.09.005},
journal = {Geochimica et Cosmochimica Acta},
issn = {0016-7037},
number = ,
volume = 145,
place = {United States},
year = {2014},
month = {11}
}