Publication
Names
  • Shu-hei Urashima
  • Tomoya Nishioka
  • Hiroharu Yui
Title
Micro-Raman spectroscopic analysis on natural carbonates: linear relations found via biaxial plotting of peak frequencies for cation substituted species
Abstract
Carbonates are ubiquitous minerals carrying important information on aqueous environments where they precipitated on the Earth and space. While their ideal chemical formulae are denoted as simple as $MCO_3$ or $M_1M_2(CO_3)_2$ (M: metal cations), natural carbonates generally form solid-solution series and their compositions deviate from the ideal formulae. Since their cation composition due to the substitution provides a sensitive indicator for chemical and thermodynamic environments of aqueous solutions where they precipitated, their composition analysis has been widely carried out from the environmental/geochemical/astrochemical aspects. However, in widely used back-scattered electron and energy dispersion X-Ray analyses, samples should be generally sliced and/or their surface be polished prior to the measurements. For analyzing rare samples with small sizes, such as ones sampled from deep-sea and/or meteorites and asteroids, a non-destructive method without any pretreatments has been strongly desired. Here, a novel analytical method for discriminating various carbonates with Raman micro-spectroscopy is demonstrated, showing that the biaxial plot of the peak frequencies of their lattice modes linearly moves upon partial substitution of the cations. The cation substitution leads to linear movement in the biaxial map, and the slopes of the movement were different for $Mg^{2+}-Fe^{2+}$ and $Mn^{2+}-Fe^{2+}$ substitutions. This finding suggests that the micro-Raman analysis would be a non-destructive analytical method for evaluating the relative amount of $Mg^{2+}$, $Fe^{2+}$, and $Mn^{2+}$ in dolomite-ankerite-kutnohorite solid-solution series, as well as $Mg^{2+}/Fe^{2+}$ ratio for magnesite-breunnerite-siderite. It would be helpful for analyzing the present and past terrestrial and cosmochemical environments.
Keywords
Raman spectroscopy, Raman spectra, data analysis, band position, sample composition, mineral, carbonate, calcite, ankerite, dolomite, siderite, magnesite, rhodochrosite, breunnerite, kutnohorite, Ca, Mg, Fe, Mn
Content
spectral data, band list data, experimental physics
Year
2022
Journal
Analytical Sciences
Volume
38
Pages
921 - 929
Pages number
9
Document type
article
Publication state
published