Batch experiments, combined with in situ spectroscopic methods, are used to examine the coprecipitation of Cr(VI) with calcite, including partitioning behavior, site-specific distribution of Cr on the surface of calcite single crystals, and local coordination of Cr(VI) in the calcite structure. It is found that the concentration of Cr incorporated in calcite increases with increasing Cr concentration in solution. The calculated apparent partition coefficient, Kd*, is highest at low Cr solution concentration, and decreases to a constant value with increasing Cr solution concentration. DIC images of the (1 0 over(1, ̄) 4) surface of calcite single crystals grown in the presence of CrO42 - exhibit well-defined growth hillocks composed of two pairs of symmetrically nonequivalent vicinal faces, denoted as + and -, which reflect the orientation of structurally nonequivalent growth steps. Micro-XRF mapping of the Cr distribution over a growth hillock shows preferential incorporation of Cr into the-steps, which is considered to result from differences in surface structure geometry. XANES spectra confirm that incorporated Cr is hexavalent, and no reduction of Cr(VI) in the X-ray beam was observed up to 2 days at room temperature. EXAFS fit results show the incorporated Cr(VI) has the expected first shell of 4 O at ∼1.64 ± 0.01 Å, consistent with CrO42 -. Best fit results show that the second shell is split with ∼2.5 Ca at ∼3.33 ± 0.05 and ∼2.2 Ca at ∼3.55 ± 0.05 Å, which confirms the incorporation of chromate into calcite. Consideration of possible local coordination indicates that significant distortion or disruption is required to accommodate CrO42 - in the calcite structure.
Bibliographical noteFunding Information:
This work was supported by the Center for Environmental Molecular Science through NSF Grant CHE-0221924. We thank A. Lanzirotti (X26A, NSLS), K. Pandya (X11A, B, NSLS), N. Leyarovska (BESSRC, APS), and M. Balasurbramanian (PNC-CAT, APS) for assistance with data collection. Comments from the associate editor Dr. Roy Wogelius and two anonymous reviewers greatly improved the manuscript.
ASJC Scopus subject areas
- Geochemistry and Petrology