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Title: Manganese-calcium intermixing facilitates heteroepitaxial growth at the (1014) calcite-water interface

For this research, in situ atomic force microscopy (AFM) measurements were performed to probe surface precipitates that formed on the (10$$\bar{1}$$4) surface of calcite (CaCO 3) single crystals following reaction with Mn2 +-bearing aqueous solutions. Three-dimensional epitaxial islands were observed to precipitate and grow on the surfaces. In situ time-sequenced measurements demonstrated that the growth rates were commensurate with those obtained for epitaxial islands formed on calcite crystals reacted with Cd2 +-bearing aqueous solutions of the same range in supersaturation with respect to the pure metal carbonate phase. This finding was unexpected as rhodochrosite (MnCO 3) and calcite display a 10% lattice mismatch, based on the area of their (10$$\bar{1}$$4) surface unit cells, whereas the lattice mismatch is only 4% for otavite (CdCO 3) and calcite. Coatings of varying thicknesses were therefore synthesized by reacting calcite single crystals in calcite-equilibrated aqueous solutions with up to 250 μM MnCl 2. Ex situ X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), X-ray reflectivity (XRR), and AFM measurements of the reacted crystals demonstrated the formation of an epitaxial (Mn,Ca)CO 3 solid solution. The epitaxial solid solution had a spatially complex composition, whereby the first few nanometers were rich in Ca and the Mn content increased with distance from the original calcite surface, culminating in a topmost region of almost pure MnCO 3 for the thickest coatings. The effective lattice mismatch was therefore much smaller than the nominal mismatch thus explaining the measured growth rates. Lastly, these findings highlight the strong influence played by the substrate on the composition of surface precipitates in aqueous conditions.
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  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical and Computational Sciences Directorate, Physical Sciences Division
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Earth and Biological Sciences Directorate, Environmental Molecular Sciences Division
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Energy and Environment Directorate, Nuclear Sciences Division
Publication Date:
Report Number(s):
Journal ID: ISSN 0009-2541; PII: S0009254117304904
Grant/Contract Number:
Accepted Manuscript
Journal Name:
Chemical Geology
Additional Journal Information:
Journal Volume: 470; Journal ID: ISSN 0009-2541
Research Org:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
Country of Publication:
United States
36 MATERIALS SCIENCE; 58 GEOSCIENCES; Metal carbonates; Epitaxy; Mineral growth; Lattice mismatch; Mineral coatings
OSTI Identifier: