title: Calibration of carbonate composition using micro-Raman analysis: application to planetary surface exploration.
abstract: Stromatolite structures in Early Archean carbonate deposits form an important clue for the existence of life in the earliest part of Earth's history. Since Mars is thought to have had similar environmental conditions early in its history, the question arises as to whether such stromatolite structures also evolved there. Here, we explore the capability of Raman spectroscopy to make semiquantitative estimates of solid solutions in the Ca-Mg-Fe(+Mn) carbonate system, and we assess its use as a rover-based technique for stromatolite characterization during future Mars missions. Raman microspectroscopy analysis was performed on a set of carbonate standards (calcite, ankerite, dolomite, siderite, and magnesite) of known composition. We show that Raman band shifts of siderite-magnesite and ankerite-dolomite solid solutions display a well-defined positive correlation (r(2) > 0.9) with the Mg# = 100 x Mg/(Mg + Fe + Mn + Ca) of the carbonate analyzed. Raman shifts calibrated as a function of Mg# were used in turn to evaluate the chemical composition of carbonates. Raman analysis of a suite of carbonates (siderite, sidero-magnesite, ankerite, and dolomite) of hydrothermal and sedimentary origin from the ca. 3.2 Ga old Barite Syncline, Barberton greenstone belt, South Africa, and from the ca. 3.5 Ga old Dresser Formation, Pilbara Craton, Western Australia, show good compositional agreement with electron microprobe analyses. These results indicate that Raman spectroscopy can provide direct information on the composition and structure of carbonates on planetary surfaces.
authors.affiliation: Géobiosphère Actuelle et Primitive, Institut de Physique du Globe de Paris, IMPMC, Université Paris Diderot, CNRS UMR7154, 4 place Jussieu, 75005 Paris, France. rividi@ipgp.jussieu.fr
authors.forename: Nicolas
authors.initials: N
authors.lastname: Rividi
authors.forename: Mark
authors.initials: M
authors.lastname: van Zuilen
authors.forename: Pascal
authors.initials: P
authors.lastname: Philippot
authors.forename: Bénédicte
authors.initials: B
authors.lastname: Ménez
authors.forename: Gaston
authors.initials: G
authors.lastname: Godard
authors.forename: Emmanuel
authors.initials: E
authors.lastname: Poidatz
mesh_terms: D001105:Archaea; D002138:Calibration; D002254:Carbonates / Q000737:chemistry*; D005118:Extraterrestrial Environment; D016083:Planets; D012015:Reference Standards; D013026:Space Flight; D013059:Spectrum Analysis, Raman; D013499:Surface Properties
chemical_list: D002254:Carbonates