Surface structural controls on compositional zoning of SO 2- 4 and SeO 2- 4 in synthetic calcite single crystals

Details Surface structural controls on compositional zoning of SO 2- 4 and SeO 2- 4 in synthetic calcite single crystals Surface structural controls on compositional zoning of SO 2- 4 and SeO 2- 4 in synthetic calcite single crystals

May 1994

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=1994gecoa..58.2087s&link_type=abstract

Geochimica et Cosmochimica Acta, vol. 58, Issue 9, pp.2087-2098

Physics

10

Scientific paper

Coprecipitation experiments show that structural characteristics of growth surfaces on synthetic calcite single crystals are a primary control on SO 2- 4 and SeO 2- 4 incorporation. Electron probe microanalyses of sections through sectorally zoned crystals show that SO 2- 4 concentrations in 1014 sectors are 50% higher than in 0112 sectors. Electron probe and synchrotron X-ray fluorescence microanalyses within 1014 sectors document a twofold to threefold difference in SO 2- 4 and SeO 2- 4 contents between subsectors associated with nonequivalent vicinal faces of growth hillocks. This differential incorporation of SO 2- 4 and SeO 2- 4 documents path-dependent, nonequilibrium partitioning behavior. Models of nearest-neighbor and second-nearest-neighbor coordination environments of nonequivalent kink sites reveal differences in site sizes and geometries. Vicinal faces that consist of steps with larger and geometrically less constrained kink sites have greater SO 2- 4 and SeO 2- 4 incorporation, whereas vicinal faces with smaller, more constrained kink sites always have less SO 2- 4 and SeO 2- 4 incorporation. This correlation requires surface-structural, i.e., crystallographic, controls on SO 2- 4 and SeO 2- 4 incorporation and, therefore, is consistent with SO 2- 4 and SeO 2- 4 substitution for CO 2- 3 . Our results clearly show that consideration of surface structural controls on trace ion partitioning is essential for a better understanding of trace ion studies in carbonate geochemistry and of crystal surface processes.

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