Manganese oxides occur typically as cryptocrystalline and fine-grained mixtures of different Mn-phases, carbonates, silicates, and Fe oxides/hydroxides; thus their characterization by standard methods, such as X-ray diffraction, is extremely challenging. These materials have been widely used in various applications over the millennia, for example, in art works as pigments for pottery, mural paintings, stained glass, and recently, as nanostructured materials with very attractive physicochemical properties. Furthermore, they are important geomaterials that could play a key role in environmental applications, by controlling the partitioning of arsenic and heavy metals between rocks, soils, and aqueous systems. Raman spectroscopy, which is a punctual and nondestructive technique, has been widely used to characterize these materials. However, literature data are often conflicting and contradictory, usually not allowing a proper identification of the Mn species. In this work, we characterize the most common natural manganese oxides by combining X-ray powder diffraction, Fourier-transform infrared spectroscopy, and Raman spectroscopy. Our data show that some manganese oxides have characteristic Raman spectra and can be easily recognized by using Raman spectroscopy alone, whereas integration of Raman data with other techniques is mandatory to characterize minerals that have almost identical Raman spectra. With this respect, Raman spectroscopy is the only technique allowing an easy discrimination between hollandite [Ba(Mn 4+ 6 ,Mn 3+ 2 )O 16 ] and cryptomelane [K(Mn 4+ 7 ,Mn 3+ )O 16 ]. The final goal of this work is to provide reference Raman spectra, acquired on previously well-characterized Mn samples to facilitate the application of Raman spectroscopy in the study of these geomaterials.

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Manganese oxides are important geomaterials, widespread in terrestrial and Martian environments. Characterisation of the oxidation state of Mn is a central issue in science; this task has been addressed up to the present by X‐ray spectroscopy or diffraction techniques. The former, however, requires access to synchrotron facilities, while the latter does not provide crystal‐chemical information at the local scale. In this work, we compare a large set of Raman data from well‐characterised samples, already published by the same authors of this paper or as found in the literature. We show a clear correlation between the oxidation state of Mn and the wavenumber of peculiar bands; octahedrally co‐ordinated Mn2+ is recognised by a band around 530 cm−1, Mn3+ by a band around 580 cm−1 and Mn4+ by a band around 630 cm−1, while tetrahedrally co‐ordinated Mn2+ is recognisable by a band around 650 cm−1. Strongly distorted Mn3+ octahedra are indicated by the appearance of Jahn–Teller modes. Our method allows a reliable, easily accessible tool to characterise the oxidation states of Mn in oxides, also suitable for microscale mapping. It provides a robust analytical basis for the use of these minerals as redox indicators in geology/geochemistry, in exoplanetary research or for monitoring technological processes.

Opals are naturally occurring hydrous silica materials (SiO2*nH2O), characterized by different degrees of crystallinity and crystal structure. Because of their optical properties, opals have been largely used in jewelry and as decorative elements in artworks. For this reason, a complete characterization and a provenance study of this kind of materials is mandatory in order both to avoid frauds and to reconstruct ancient and modern trade routes of gems. In this work, we present a combined spectroscopic (Raman, FTIR) and X-ray powder diffraction (XRD) investigation of nine opals from the main deposits around the world (Australia, Madagascar, Slovakia, Mexico, Honduras and Ethiopia). Four of these samples are the rare and precious fire opals, characterized by an intense red-orange color. Ethiopia, Honduras and Mexico opals showed spectra and diffraction patterns typical of Opal-CT, generally associated to volcanic genesis, while Australia, Madagascar and Slovakia opals are Opal-A type, associated to sedimentary origin. Unexpectedly the fire opal from Brazil behaves as a CT one. The presence of CO2 was detected only in the latter group, and exceptionally in the Honduras sample; FTIR-FPA imaging showed carbon dioxide to be homogeneously distributed inside the gems. Opals-CT are CO2-free and give much more complex FT-IR spectra in the NIR region where H2O combination modes occur. The obtained results are discussed in terms of relevance of the above experimental techniques for geosourcing opals, and contribute to increase the database of the chemical-physical properties of opals