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Vibrational spectroscopies (Fourier Transform Infra Red, FTIR, and Raman) are exceptionally valuable tools for the identification and crystal&ndash, chemical study of fibrous minerals, and asbestos amphiboles in particular. Raman spectroscopy has been widely applied in toxicological studies and thus a large corpus of reference data on regulated species is found in the literature. However, FTIR spectroscopy has been mostly used in crystal&ndash, chemical studies and very few data are found on asbestos amphiboles. This paper is intended to fill this gap. We report new FTIR data collected on a suite of well-characterized samples of the five regulated amphibole species: anthophyllite, amosite, and crocidolite, provided by the Union for International Cancer Control (UICC) Organization, and tremolite and actinolite, from two well-known occurrences. The data from these reference samples have been augmented by results from additional specimens to clarify some aspects of their spectroscopic features. We show that the FTIR spectra in both the OH-stretching region and in the lattice modes region can be effective for rapid identification of the asbestos type.

In this work, we investigate the oxidation behavior of a nearly end-member riebeckite, ideally Na-2(Fe32+Fe23+)Si8O22(OH)(2), by using vibrational FTIR and Raman spectroscopies. Combining these results with previous studies performed on the same sample by single-crystal structure refinement and Mossbauer spectroscopy, we conclude that iron oxidation in riebeckite is a multi-step process. (1) In the similar to 523 K < T < 623 K temperature range, the O-H bond lengthens and both the electrons and the hydrogen cations delocalize. Raman analysis shows that this step is reversible upon cooling to room temperature. (2) In the 623 K < T < 723 K range, the kinetic energy increases so that the electrons can be ejected from the crystal; beyond 723 K an irreversible oxidation of Fe occurs that couples with irreversible changes in the SiO4 double-chains leading to a contraction of the unit-cell volume, i.e., to structural changes detectable at the long-range scale. (3) Beyond 823 K, the irreversible oxidation is completed and H+ ions are forced to leave the crystal bulk. Because of this multi-step process, the onset of the deprotonation process is detected at similar to 700 K by single-crystal XRD analysis of the unit-cell parameters, but starts at 623 K as indicated by Mossbauer spectroscopy on powders (and by changes in the cation distribution observed by structure refinement). Also, Raman scattering shows that the release of H+ from the crystal surface starts similar to 100 K before the complete deprotonation of the crystal bulk is witnessed by FTIR absorption. Hence, the oxidation of Fe starts at the crystal surface and induces electron and H+ migration from the crystal interior to the rim and thus subsequent oxidation through the crystal bulk. No deprotonation is observed by FTIR either in powders embedded in KBr or in crystals heated in N-2 atmosphere, implying that the release of H+ needs surficial (atmospheric) oxygen to form H2O molecules. Fe2+-> Fe3+ oxidation produces a flux of electrons throughout the crystal matrix, which generates electrical conductivity across the amphibole. An important implication of this work, which might have interesting applications in material science, is that iron oxidation in riebeckite (and possibly in other Fe-rich silicates) is reversible in a given range of temperature. Also, this work shows that complex processes cannot be fully understood or even monitored accurately without using a proper combination of independent techniques.

A new approach to extract accurate information on the Fe oxidation state has been tested on three different Fe-rich amphiboles annealed at 194–520 °C. The method is based on the analysis of the pre-edge structure of the X-ray absorption spectra at the Fe-K edge. The pre-edge band is deconvolved into four Gaussian components where the integrated intensities of the pairs of lower- and higher-energy bands are related to the ferrous to ferric ion ratio. These Fe3+/Fetot ratios have been compared with those obtained with independent techniques (X-ray diffraction and Mossbauer spectroscopy) on the same samples. The experimental data allowed establishing a calibration curve that is in good agreement with a recent statistical analysis based on spectroscopic data for the same type of minerals. The method could be extended to the analysis of other complex systems containing both Fe3+ and Fe2+ in octahedral coordination or to study the dynamics of iron under non-ambient conditions.

The crystal structures of six gem-quality pargasites and fluoro-pargasites from Mogok, Myanmar, space group C2/m, Z = 2, have been refined to R1 indices of 2.20–2.90% using MoKα X-radiation. The unit formulae were calculated from the results of electron-microprobe analysis, and were used with the refined site-scattering values and the observed mean bond lengths to assign site populations. TAl occurs at both the T(1) and T(2) sites but is strongly ordered at T(1). [6]Al is partly disordered over the M(2) and M(3) sites but does not occur at the M(1) site. ANa is split between the A(2) and A(m) sites and K occurs at the A(m) site. The infrared spectra in the principal OH-stretching region were measured and the fine structure was fit to component bands. The component bands were assigned to short-range ion arrangements over the configuration symbol M(1)M(1)M(3)–O(3)–A–O(3):T(1)T(1) using the refined site-populations and the expected frequencies from previously assigned spectra in more simple amphibole compositions, and correspond to the local arrangements: (1) MgMgMg–OH–Na–OH:SiAl; (2) MgMgMg–OH–Na–F:SiAl; (3) MgMgAl–OH–Na–OH:SiAl and (4) MgMgAl–OH–Na–F:SiAl.

We investigated the oxidation behaviour of a synthetic potassic-ferro-richterite up to 750 degrees C by using simultaneous X-ray absorption spectroscopy and X-ray diffraction experiments with synchrotron radiation. From the X-ray diffraction results, we observed an abrupt decrease of cell dimensions at approximate to 335 degrees C accompanied by an anomalous increase in the monoclinic cell angle . From the analysis of the XANES spectra at the iron K-edge, we observed that the structural shrinkage is due to the iron oxidation process, coupled to hydrogen loss, occurring at approximate to 315 degrees C, slightly before the cell contraction. Combining these results with previous studies performed on similar samples by single-crystal structure refinement, Mossbauer, high temperature-Fourier transform IR and Raman spectroscopies, we show that the temperature evolution in Fe-amphiboles is a multi-step process. Following the iron oxidation driven by temperature, the structural dynamics in this double-chain silicate is ruled by local strains in the ribbon of iron-filled octahedra, mainly due to the contraction of the M(1) site.

Lutetium beta-tricalcium phosphate Ca9Lu(PO4)(7) was synthesized by solid-state reaction at 1200 degrees C, and investigated by means of a combination of scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), Fourier transform infrared (FTIR) and Raman spectroscopies. SEM morphological analysis reveals the presence of sub spherical and prismatic micro crystalline aggregates, while EDS semi-quantitative analysis confirms the nominal Lu/Ca composition. The unit cell and the space group were determined by X-ray powder diffraction data showing that the compound crystallizes in the rhombohedral R3c whitlockite-type structure, with unit cell constants a = b = 1.04164(1) nm, c = 3.7302(1) nm and cell volume V = 3.5051(1) nm(3). The investigation was completed with the structural refinement by the Rietveld method, and discussion of the distribution of Lu within cationic sites according to the results of the Rietveld refinement. The FTIR and Raman spectra, correlated to isostructural rare earth phosphates from literature, show slight band shifts of the phosphate modes correlated to the evolving size of the rare earth elements. (C) 2018 Chinese Society of Rare Earths. Published by Elsevier B.V. All rights reserved.

Il progetto SMART ENVIRONMENTS, svoltosi negli anni dal 2015 al 2017 presso l’Ateneo Roma Tre, è stato finanziato dalla Regione Lazio con lo scopo di sostenere l’attività di ricerca orientata all’accrescimento della competitività tecnologica del tessuto imprenditoriale della regione e di promuovere il sistema della ricerca e innovazione mediante la valorizzazione delle infrastrutture di ricerca presenti sul territorio. Un indirizzo che aveva, fin da subito, individuato nel trasferimento tecnologico una delle chiavi in grado di sostenere lo sviluppo industriale della Regione Lazio in un periodo difficile dove però la possibile ripresa economica garantiva disponibilità di investimenti. SMART ENVIRONMENTS, con la sua dichiarata progettualità a forte vocazione imprenditoriale, è andato a esplorare, quindi, il nuovo terreno della Terza Missione delle Università, dove il rapporto con il territorio finisce al centro dell’operare accademico non più in una ottica di diffusione del sapere che procede dall’alto verso il basso ma con la pretesa di lavorare insieme al tessuto produttivo

Diamonds from Juina, Brazil, are well-known examples of superdeep diamond crystals formed under sublithospheric conditions and evidence would indicate their origins lie as deep as the Earth’s mantle transition zone and the Lower Mantle. Detailed characterization of these minerals and of inclusions trapped within them may thus provide precious minero-petrogenetic information on their growth history in these inaccessible environments. With the aim of studying non-destructively the structural defects in the entire crystalline volume, two diamond samples from this locality, labelled JUc4 and BZ270, respectively, were studied in transmission mode by means of X-ray Diffraction Topography (XRDT) and micro Fourier Transform InfraRed Spectroscopy (µFTIR). The combined use of these methods shows a good fit between the mapping of spatial distribution of extended defects observed on the topographic images and the µFTIR maps corresponding to the concentration of N and H point defects. The results obtained show that both samples are affected by plastic deformation. In particular, BZ270 shows a lower content of nitrogen and higher deformation, and actually consists of different, slightly misoriented grains that contain sub-grains with a rounded-elongated shape. These features are commonly associated with deformation processes by solid-state diffusion creep under high pressure and high temperature.

Rare earth elements doped (beta-tricalcium phosphates Ca9RE(PO4)(7) (RE = La, Pr, Nd, Eu, Gd, Dy, Tm, Yb) were synthesized by solid-state reaction at T = 1200 degrees C. The obtained RE-doped beta-TCP phases were studied by a combination of Scanning Electron Microscopy (SEM) equipped with energy dispersive X-Ray spectroscopy (EDS), X-ray diffraction (XRD), Fourier Transform Infra Red (FTIR) and Raman spectroscopies. SEM morphological analyses revealed the presence of sub spherical micro crystalline aggregates, while EDS semi quantitative analyses confirmed the nominal RE/Ca composition for all the phases. The unit cell and the space group were determined by X-ray powder diffraction data showing that all phases in the series crystallize in the rhombohedral R3c whitlockite-type structure; the unit cell constants are a linear function of the dimension of the substituting rare-earth element, and range from a = b = 10.4695(3) angstrom, c = 37.500(3) angstrom and V= 3559.7(2) angstrom(3) (La) up to a = b = 10.4073(2) angstrom, c = 37.2725(2) angstrom, V = 3496.2(2) angstrom(3) (Yb). The analysis of each compound was completed with the structure model refinement by the Rietveld method and the distribution of RE within the available structural sites is discussed according to the results of the Rietveld refinement. The FTIR and Raman spectra show slight band shifts of the phosphate modes correlated to the evolving size of the RE element.

New chemical (EMP, SIMS) and structural data are reported for a suite of crystals of oxo-mangani-leakeite and mangano-mangani-ungarettiite from their common type locality, the Hoskins mine (New South Wales, Australia). Notwithstanding the low OH content, FTIR analysis of selected sampleshas provided considerable information on short-range order in these Mn3+-rich amphiboles, and shows that Li is associated with occupied A sites and is linked to the oxo-component at the O(3) site. Comparative analysis of all available data allows us to: (1) further improveour understanding of the crystal-chemistry of these very peculiar compositions of the oxo-amphibole group; and (2) calculate reliable site-populations. The proposed limited compositional variability has been confirmed. The two amphiboles have completely different arrangements of CR3+cations. In oxo-mangani-leakeites, those CR3+ cations related to the oxocomponent occur at the M (1) site, whereas those CR3+ cations related to the leakeite charge-arrangement occur at the M (2) site. In mangano-mangani-ungarettiite,all CR3+ cations order at the M (1) and M (3) sites, and local bond-valence requirements are satisfied by the presence of Mn3+, which assumes a strongly distorted coordination due to its degenerate eg electronic state. Therefore,the inverse patterns observed for both cation-ordering and deformation of the octahedra are incompatible with solid-solution between these two species that coexist at the Hoskins mine.

""We present a study of olivine-hosted glass\\\/melt inclusions (MIs) in the most primitive rocks erupted at Procida Island, within the Phlegraean Volcanic District (PVD), Southern Italy. MIs were analyzed by combined Scanning Electron Microscopy coupled with Energy Dispersive X-ray-detectors, Wavelength Dispersive X-rayequipped Electron Microprobe and Fourier Transform Infrared (FT-IR) Spectroscopy; notably, the novel Focal-Plane-Array mode provided high-resolution FT-IR images evidencing the distribution of the C–H–O species across samples. Olivines range in composition from Fo85 to Fo90, do not show chemical zoning and are totally anhydrous. The majority of the MIs are glassy, while only few are completely crystallized. Some MIs, however, show the occurrence of crystal nuclei, i.e., nano- to micro-sized pyroxenes and oxides, and appear as lowcrystallized MIs. The glass of crystal-free and low-crystallized MIs shows K-affinity and a compositional range along the basalt, trachy-basalt, shoshonite, tephrite basanite and phono-tephrite array. H2O and CO2 contents up to 2.69 wt.% and 2653 ppm, respectively, define a major degassing trend with small isobaric deviations. The collected data allow recalculating entrapment pressures from ~350 MPa to b50 MPa and suggest that the magma ascent was dominated by degassing. Crystallization was aminor process, likely also consequent to local CO2-fluxing. Mingling occurred between variable degassed and crystallized magma portions during decompression. The geochemical and isotopic data of Procida glasses and rocks, and the compositional relationship between our MIs and those from slightly more evolved and radiogenic Phlegraean products, indicate that Procida basalts are an adequate parental end-member for the PVD. Our data suggest that a CO2-rich magma source was stored at depths of at least 13–14 km (i.e., 350 MPa) beneath the PVD. Fast ascent of magma batches directly started from this depth shortly before PVD trachy-basaltic to shoshonitic eruptions. Such results have implication on volcanic hazard assessment in the PVD area.""

The crystal chemistry of wavellite from Zbirov (Czech Republic), ideally Al3(PO4)2(OH,F)3·5H2O, was addressed by means of a multi-methodological approach based on electron microprobe analysis (EMPA) using wave-dispersive spectroscopy, single-crystal X-ray diffraction, powder and singlecrystal infrared spectroscopy and Raman spectroscopy. The EMPA data showed the presence of significant F replacing OH in the sample studied. The structure was solved in thePcmnorthorhombic space group, with the following unit-cell constants:a= 9.6422(7),b= 17.4146(15),c= 7.0094(2) Å,V= 1176.98(10) Å3. Phosphorus atoms display tetrahedral (PO4) coordination, while Al cations display octahedral coordination. The mineral framework can be viewed as the repetition of cationic arrays made up of AlO6polyhedra, bridged by PO4groups and further joined by O–H⋯O hydrogen bonds. The single-crystal unpolarized Fourier transform infrared (FTIR) spectrum shows combination bands indicating the presence of both OH and H2O in the structure. Both FTIR and Raman spectra show a broad absorption extending from 3600 to 2800 cm−1resulting from the overlapping of several components due to the water molecules and the OH group. The frequencies observed are comparable to those expected on the basis of the Libowitzky relationship for the range ofD–H⋯Abond systems in the structure.

Melt inclusions (MIs) are micrometric-sized and variable-shaped impurity parcels of glass vesicles solids present within cavities or fractures of crystals. Because representing melt droplets that were trapped during crystal growth, they are believed to record the variable physico-chemical conditions of the hosting multi-phase system. Therefore, MIs are unique probe of near-liquidus magmatic conditions, otherwise inaccessible to Earth Scientists, and are widely used to integrate and corroborate conventional petrological and volcanological techniques based on mineral phases and whole rocks. Electron microprobe (EMP-WDS) and microscopy (SEM-EDS), and Fourier Transform Infra Red (FT-IR) spectroscopy are well-established analytical techniques, commonly used to determine composition of the magma from which MIs formed. Noteworthy, FT-IR is usually adopted to determine the content of dissolved H2O and CO2, providing i) essential information for entrapment pressures, hence depths of crystal growth, and ii) constraints to the volatile budget of magmas. Assessing such volatile contents has significant implications for the understanding of magma evolution and migration, from the depths of parental magma genesis, through the main depths of crustal storage, up to surface. The MI-based quantification of volatile contents and the recognition of degassing patterns are also vital for deciphering magma rheology, which largely affects eruptive dynamics and style. Limits to melt inclusion studies are i) their typically very small size (< 100 m), ii) the possible late and secondary crystallization, iii) the diffusivity-driven chemical exchange between melt and host crystal, iv) and the alteration phenomena that mask or even delete the original melt composition. Here, we present a study of glass/melt inclusions in phenocrysts from Procida Island (Phlegraean Volcanic District, South Italy), analyzed for combined SEM-EDS electron microscopy, EMP-WDS microchemistry and FT-IR spectroscopy. In particular, we have characterized the distribution of volatile H and C species across both the host crystals and the inclusions, by using a focal-plane-array (FPA) of detectors. The FPA technique allows the acquisition of a large number of IR spectra simultaneously and generate mid-IR images with high resolving power of the target molecules in the H-O-C system. The integration of these analytical techniques is a mandatory step in order to provide definite advances in MI characterization and data interpretation

This chapter is concerned with in situ studies of the structural behavior of amphiboles under non-ambient conditions. Relatively few such studies have been made compared with those on samples studied under ambient conditions (room-P and T), which form the staple of many spectroscopic and diffraction studies of short-range and long-range order.

Extensive spectroscopic, diffraction and theoretical work in the last ten years has shown that short-range order (SRO) of both cations and anions is a common feature of amphiboles (Hawthorne et al. 2005). From an experimental perspective, the problem is that SRO does not obey the translational symmetry of the structure in which it occurs, and hence SRO is diffi cult to detect and decipher directly by standard diffraction methods. There is information on SRO resident in diffuse scattering from a crystal, but this information is quite diffi cult to extract, particularly when the SRO is complicated, and this approach has only been used for simpler materials. SRO can be detected by several spectroscopic techniques [e.g., infrared spectroscopy, magic-angle-spinning nuclear magnetic resonance (MAS NMR) spectroscopy], but the problem is that only part of the local arrangement is derived, and the complete picture of SRO is often not clear. Here, we examine SRO of cations and anions in monoclinic amphiboles, and show that detailed information on SRO can be derived by a combination of infrared spectroscopy and local bond-valence theory, augmented by results from Rietveld and single-crystal diffraction.

In this chapter, we examine the new amphibole compositions which have been found and characterized since 1981, i.e. since the publication of volume 9A of the MSA Reviews in Mineralogy. We divide the chapter in two sections. The fi rst section describes new charge arrangements found in Nature, and the second section describes the extensive studies of synthetic amphiboles of novel composition done to clarify the crystal chemistry of exotic cations which are normally found as minor components. This chapter deals exclusively with monoclinic amphiboles, as the compositional space of orthorhombic amphiboles has not expanded since the former review. Although natural occurrences of protoamphibole (with space group Pnmn) have been described only in the last twenty years (Sueno et al. 1998; Konishi et al. 2003), their composition is within the compositional range previously defi ned for Pnma amphiboles.

A well-characterized suite of vesuvianite samples from the volcanic ejecta (skarn or syenites) from Latium (Italy) was studied by single-crystal, polarized radiation, Fourier-transform infrared (FTIR) spectroscopy and secondary-ion mass-spectrometry (SIMS). OH-stretching FTIR spectra consist of a rather well-defined triplet of broad bands at higher-frequency (3,700-3,300 cm(-1)) and a very broad composite absorption below 3,300 cm(-1). Measurements with E//c or E perpendicular to c show that all bands are strongly polarized with maximum absorption for E//c. They are in agreement with previous band assignments (Groat et al. Can Mineral 33:609, 1995) to the two O(11)-H(1) and O(10)H(2) groups in the structure. Pleochroic measurements with changing direction of the E vector of the incident radiation show that the orientation of the 0(11)-H(l) dipole is OH(boolean AND)c similar to 35 degrees, in excellent agreement with the neutron data of Lager et al. (Can Mineral 37:763, 1999). A SIMS-based calibration curve at similar to 10% rel. accuracy has been worked out and used as reference for the quantitative analysis of H(2)O in vesuvianite by FTIR. Based on previous SIMS results for silicate minerals (Ottolini and Hawthorne in J Anal At Spectrom 16:1266, 2001; Ottolim et al. in Am Mineral 87:1477, 2002) the SiO(2) and FeO content of the matrix were assumed as the major factors to be considered at a first approximation in the selection of the standards for H. The lack of vesuvianite standards for quantitative SIMS analysis of H(2)O has been here overcome by selecting low-silica elbaite crystals (Ottolini et al. in Am Mineral 87:1477, 2002). The resulting integrated molar absorption FTIR coefficient for vesuvianite is epsilon(i) = 100.000 +/- 2.000 l mol(-1) cm(-2). SIMS data for Li, B, F, Sr, Y, Be, Ba REE, U and Th are also provided in the paper.