New analytical method for the evaluation of heterogeneity in cation compositions of dolomites by micro-XRF and Raman spectroscopies

Dolomite (CaMg(CO 3 ) 2 ) is an abundant carbonate mineral contained in sedimentary rocks and plays significant roles in water and carbon cycle in geo/cosmochemical environments. Since the cation compositions of carbonates are sensitive to the aqueous environment where they were precipitated and persisted, quantitative analysis of their cation compositions provides valuable information on the aqueous environments and their changes. The difficulty for the analysis of natural dolomite is that Mg 2+ is continuously substituted by Fe 2+ or Mn 2+ , and hence they sometimes possess micrometer-scale heterogeneity. Such heterogeneity carries quite important information on the gradual changes in aqueous environments due to changes in thermodynamic conditions and/or aqueous chemical compositions. In the present study, we explored a new quantitative scale to assess such heterogeneity of cation composition in natural dolomite and ferroan dolomite by combining X-ray fluorescence (XRF) and Raman spectroscopy. While the Fe + Mn content differed spot-by-spot, it was found that the Raman wavenumber and Fe + Mn content linearly correlated with each other. Since the spatial resolution of micro-Raman spectroscopy is as high as 1 μm, it does not require vacuum conditions, and is free from so-called matrix effect faced in other methods utilizing X-Rays and electron beams, the proposed qualitative analytical scale can provide a useful tool to assess the cation compositions in dolomites found in nature. Graphical abstract