STRUCTURE AND BONDING ENVIRONMENTS AT THE CALCITE SURFACE AS OBSERVED WITH X-RAY PHOTOELECTRON-SPECTROSCOPY (XPS) AND LOW-ENERGY ELECTRON-DIFFRACTION (LEED)

被引:486
作者
STIPP, SL
HOCHELLA, MF
机构
[1] STANFORD UNIV,DEPT CIVIL ENGN,WATER QUAL GRP,STANFORD,CA 94305
[2] STANFORD UNIV,DEPT GEOL,STANFORD,CA 94305
关键词
D O I
10.1016/0016-7037(91)90142-R
中图分类号
P3 [地球物理学]; P59 [地球化学];
学科分类号
0708 ; 070902 ;
摘要
The pure calcite surface was examined using techniques sensitive to the near-surface (XPS and LEED) immediately after fracture in ultra-high vacuum (10(-10) mbar) and then following exposure to various atmospheres and aqueous solutions that were free of trace metals. These spectroscopic techniques allow molecular-level observations that offer the possibility of gaining more insight into geochemical processes elucidated from macroscopic solution studies. Several absolute electron binding energies for the atoms in calcite were redetermined with XPS using the gold dot method. The results are 290.1 +/- 0.1 eV for C1s, 347.7 and 351.2 +/- 0.15 eV for Ca2p3/2 and Ca2p1/2, respectively, and 531.9 +/- 0.15 eV for O1s. Photoelectron energy shifts from main peak positions suggest that immediately after fracture in ultra-high vacuum, bond reconfiguration leads to the formation of carbide-like bonds between Ca and C at the surface. Calcite that has been exposed to water, even as vapour from the atmosphere, shows binding energy shifts that indicate the presence of S . CO3H and S . CaOH where S . represents the calcite surface. Surface hydration is also supported, independently, by the XPS peak intensity ratios and is consistent with adsorption theory derived from macroscopic solution studies. The modified oxygen Auger parameter, alpha', (using O1s and O(KVV)), was found to be 1043.9 eV for all samples of calcite tested, whether powder or cleaved from Iceland Spar, clean or contaminated by adventitious carbon, freshly fractured, or exposed briefly to water, or in the process of dissolution or precipitation. LEED patterns of the {101} cleavage surface of samples that were freshly fractured in air and that were exposed to dissolving or precipitating solutions showed that the top few atomic layers exhibit long range order. Lattice spacings at the surface are statistically identical to those of bulk calcite, though some surface CO3 groups may be rotated relative to the bulk structure. This work provides direct, molecular-level evidence for the processes of reconfiguration and hydration at the calcite surface. These results provide a basis for future spectroscopic studies of trace metal adsorption on calcite and subsequent solid-solution formation.
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页码:1723 / 1736
页数:14
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