XAFS study of the coordination and local relaxation around Co (super 2+) , Zn (super 2+) , Pb (super 2+) , and Ba (super 2+) trace elements in calcite
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Analysis of divalent Co, Zn, Pb, and Ba XAFS spectra of synthetic and natural calcite samples containing trace concentrations of these heavy metals confirms their substitution in the unique Ca site in octahedral coordination with varying degrees of local distortion. The existence of each trace metal at the single site in the bulk crystal is significant in view of previous studies showing that these trace elements are incorporated differentially at multiple, structurally distinct surface sites occurring in nonequivalent growth steps on calcite surfaces. The octahedral coordination for Ba is particularly noteworthy because of its large size (35% larger than host Ca) and the fact that it rarely exists as a major constituent with such a low coordination number. Analysis of the local distortion and relaxation around the impurities shows a nearly complete contraction of the structure around Co 2+ and Zn 2+ . The Co-O and Zn-O first-shell distances are only slightly longer than in CoCO 3 and ZnCO 3 , with a site compliance of ~80-90%. Displacements of higher shells relative to those in calcite decrease rapidly, but irregularly, over a short distance, and the relaxation may be largely confined within 6-7 Å of the impurity. The dilation around the large Pb 2+ and Ba 2+ ions in calcite also shows a high degree of site compliance (85-90%). Relaxation around Pb and Ba also appears to be restricted, but extending further for Ba than for Pb. The limited observations suggest that compliance of the octahedral site in calcite is larger than for the cation site in the rocksalt structure. The high compliance for the metal site in calcite may reflect the corner-sharing topology of the structure and is also probably the reason that calcite shows such a wide range of isovalent substitutions in nature. The findings also provide a direct indication of the local strain associated with a dilute substitutional solid solution.
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Reeder et al. (1999) observed that the radial strain decreases rapidly as a function of distance from the central impurity and approaches zero over the distance to neighboring octahedra.
“Reeder et al. (1999) observed that the radial strain (R–R0 , where R0 is the distance in ideal calcite) decreases rapidly as a function of distance from the central impurity and approaches zero over the distance to neighboring octahedra.”
From Structural relaxation in the MnCO 3 -CaCO 3 solid solution: a Mn K -edge EXAFS study (2002) · cites this paper as Reeder et al. 1999
The Higher shells section says that R−R₀ generally tends toward zero as distance from the impurity increases. But Ba remains well above zero at the nearest neighboring octahedra (about 4 Å), and the authors estimate that most relaxation occurs within 6–7 Å. The claim overstates how quickly and uniformly the strain approaches zero. (LLM, conf=0.88)
Experimental — accuracy not yet measuredThe Zn-O distance in dilute Zn-containing calcite is 2.14-2.15 Å, relative to 2.11 Å in pure ZnCO3.
“the Zn–O distance is 2.14–2.15 Å (relative to 2.11 Å in pure ZnCO3) (Reeder et al. 1999).”
From Structural relaxation in the MnCO 3 -CaCO 3 solid solution: a Mn K -edge EXAFS study (2002) · cites this paper as Reeder et al. 1999
Strain occurs through bond bending, which is facilitated by the exclusively corner-sharing topology of calcite.
“Strain occurs through bond bending, which is facilitated by the exclusively corner-sharing topology of calcite.”
From Structural relaxation in the MnCO 3 -CaCO 3 solid solution: a Mn K -edge EXAFS study (2002) · cites this paper as Reeder et al. 1999
The calcite structure exhibits a high degree of compliance, which was explained by the exclusively corner-sharing linkage of the polyhedra.
“Hence, the calcite structure exhibits a high degree of compliance, which was explained by the exclusively corner-sharing linkage of the polyhedra (Reeder et al. 1999).”
From Structural relaxation in the MnCO 3 -CaCO 3 solid solution: a Mn K -edge EXAFS study (2002) · cites this paper as Reeder et al. 1999
The slight increase in the Mn-O distance observed for the dilute limit samples is similar to the behavior for Co(II) and Zn(II) impurities in calcite.
“The slight increase in the Mn–O distance observed for the dilute limit samples is similar to the behavior for Co(II) and Zn(II) impurities in calcite (Reeder et al. 1999).”
From Structural relaxation in the MnCO 3 -CaCO 3 solid solution: a Mn K -edge EXAFS study (2002) · cites this paper as Reeder et al. 1999
The Co-O distance in dilute Co-containing calcite is 2.14-2.16 Å, relative to 2.11 Å in pure CoCO3.
“For example, the Co–O distance in di-”
From Structural relaxation in the MnCO 3 -CaCO 3 solid solution: a Mn K -edge EXAFS study (2002) · cites this paper as Reeder et al. 1999
Previous studies of dilute, divalent metal substitution in calcite have shown that the strain is highly localized around the substituent.
“Previous studies of dilute, divalent metal substitution in calcite have shown that the strain is highly localized around the substituent.”
From Structural relaxation in the MnCO 3 -CaCO 3 solid solution: a Mn K -edge EXAFS study (2002) · cites this paper as Reeder et al. 1999
This compares well with the 80-90% compliance found for divalent Co, Zn, Pb, and Ba substitution in calcite.
“This compares well with the 80–90% compliance found for divalent Co, Zn, Pb, and Ba substitution in calcite (Reeder et al. 1999).”
From Structural relaxation in the MnCO 3 -CaCO 3 solid solution: a Mn K -edge EXAFS study (2002) · cites this paper as Reeder et al. 1999
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Structural relaxation in the MnCO 3 -CaCO 3 solid solution: a Mn K -edge EXAFS study
Lee, Y. J., Reeder, R. J., Wenskus, R. W., & Elzinga, E. J. (2002) · Physics and Chemistry of Minerals · doi:10.1007/s00269-002-0274-2 · Cited by 32 · see citing works
Self-citation
- Authors
- Reeder, R. J., Lamble, G. M., & Northrup, P. A.
- Affiliations
- Stony Brook University (US)
- Lawrence Berkeley National Laboratory (US)
- Brookhaven National Laboratory (US)
- Corresponding author
- Reeder, Richard J.
- ORCID
- Northrup, Paul A.
- Venue
- American Mineralogist
- Publisher
- Mineralogical Society of America
- Published
- 1999-08-01
- Volume
- 84
- Issue
- 7-8
- Pages
- 1049-1060
- ISSN
- 0003-004X (ISSN-L)
- OpenAlex
- W1827306820
- Cited by
- 185
- References
- 0
- Citations by year
- 2026: 12 · 2025: 10 · 2024: 10 · 2023: 11 · 2022: 8 · 2021: 12 · 2020: 10 · 2019: 13 · 2018: 5 · 2017: 6 · 2016: 3 · 2015: 2 · 2014: 4 · 2013: 7 · 2012: 7
- FWCI
- 5.65
- Type
- journal article
- Language
- en
- Open access
- bronze
- doi.org
- Locations
- American Mineralogist (publishedVersion)
- Funders
- National Science Foundation (9706012)
- Smithsonian Institution
- National Museum of Natural History
- Topics
- Physical Sciences › Physics and Astronomy › Radiation › X-ray Spectroscopy and Fluorescence Analysis
- Physical Sciences › Earth and Planetary Sciences › Geochemistry and Petrology › Mineralogy and Gemology Studies
- Physical Sciences › Earth and Planetary Sciences › Geochemistry and Petrology › Geochemistry and Elemental Analysis
- Keywords
- calcite, trace element substitution, divalent cations, cobalt, zinc, lead, barium, octahedral coordination, local structural distortion, substitutional solid solutions, local strain, cation binding sites, isovalent substitution, calcite surface
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