Z-contrast imaging and ab initio study on "d" superstructure in sedimentary dolomite

TL;DR

This study combines Z-contrast imaging and ab initio calculations to characterize a nanoscale d superstructure in sedimentary dolomite, revealing its atomic arrangement and chemical composition.

Contribution

It introduces a novel approach integrating Z-contrast imaging with ab initio calculations to analyze nanoscale superstructures in sedimentary rocks.

Findings

Confirmed d reflections correspond to nanoscale precipitates aligned with (001)

Determined the cation ordering sequence Ca-Ca-Mg-Ca-Ca-Mg in the superstructure

Calculated the crystal structure with DFT, revealing parameters between dolomite and calcite

Abstract

Nano-precipitates with tripled periodicity along the c-axis are observed in a Ca-rich dolomite sample from Proterozoic carbonate rocks with "molar tooth" structure. This observation is consistent with previous description of d reflections. High-angle annular dark-field STEM imaging (or Z-contrast imaging) that avoids dynamic diffraction as seen in electron diffraction and high-resolution TEM imaging modes, confirms that d reflections correspond to nanoscale precipitates aligned parallel to (001) of the host dolomite. The lamellae precipitates have a cation ordering sequence of Ca-Ca-Mg-Ca-Ca- Mg along the c direction resulting in a chemical composition of Ca0.67Mg0.33CO3. This superstructure is attributed to the extra or d reflections, thus is referred to as the d superstructure in this study. The structure can be simply described as interstratified calcite/dolomite. The crystal structure of the d superstructure calculated from density functional theory (DFT) has a space group of P31c and has a and c unit-cell parameters of 4.879 and 16.260 {\AA}, respectively, values between those of dolomite and calcite. The detailed structural characteristics and parameters obtained from ab initio calculations are also reported in this paper. The method of combining Z-contrast imaging and ab initio calculations can be used for solving structures of other nano-precipitates and nano-phases.