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In this work, we address the kinetics of dehydrogenation occurring at high temperatures (HT) in riebeckite, a sodic amphibole with the ideal composition Na 2 Fe 2 3 + Fe 3 2 + Si 8 O 22 (OH) 2. ${\rm{N}}{{\rm{a}}_2}{\rm{Fe}}_2^{3 + }{\rm{Fe}}_3^{2 + }{\rm{S}}{{\rm{i}}_8}{{\rm{O}}_{22}}{({\rm{OH}})_2}.$ We performed isothermal experiments on both powders and single-crystals up to 560 °C and monitored the O-H stretching signal by Fourier transform infrared (FTIR) spectroscopy. Single-crystals show an initial increase in IR absorption intensity due to increasing vibrational amplitudes of the O-H bond stretching, not observed for powders. The OH-intensities vs. time were fitted using the formalism for first-order reactions. The calculated activation energies for H+ diffusion in riebeckite are 159 ± 15 kJ/mol for powders and 216 ± 20 kJ/mol for single crystals, respectively. The exponential factor m in the Avrami-Erofeev equation obtained for crystals ranges between 1.02 and 1.31, suggesting that, unlike powders, the dehydration process in crystals is not a purely first-order reaction. This implies that a second energy barrier must be considered, i.e., diffusion of H+ through the crystal. FTIR imaging showed that H+ diffusion occurs mainly perpendicular to the silicate double-chain. Our results confirm that the release of H+ from riebeckite occurs after the irreversible Fe2+-to-Fe3+ exchange, thus at temperatures >550 °C. To be effective, the process needs the presence of external oxygen that, by interacting with H+ at the crystal surface, triggers the release of H2O molecules. This implies that oxidizing conditions are required for the amphibole to be an efficient water source at depth. [ABSTRACT FROM AUTHOR]

Six sub-alkaline glasses with compositions progressively shifting from the tholeiitic basalt (B 100) end-member to the rhyolite (R 100) end-member were investigated and analysed in the same frequency domain by both Raman and FTIR. This approach highlights spectroscopic similarities and differences such as positions, widths and intensities of Raman and FTIR bands, which may also exhibit significant overlapping. Both the Raman and FTIR spectra show several peaks grouped in three main vibrational windows: 200–650 (low frequency region, named F-I in this study), 650–850 (intermediate region, F-II) and 850–1250 cm−1 (high-frequency region, F-III). In line with previous investigations, the F-I interval can be ascribed to vibrational modes involving rings of tetrahedrally coordinated cations linked by bridging oxygens. It can be fitted with three components, whereas F-II involves the motion of Si atoms within its oxygen cage and is adequately represented by two components. Finally, F-III contains different T-O (T = tetrahedrally coordinated network-forming cation) stretching bands that can be tied to the overall degree of polymerization of the glass and are fitted with four components. In some glasses, the three and the two components within F-I and F-II are identifiable in both Raman and FTIR spectra; in cases of strong peak overlap, these peaks can be complementary to one another towards our interpretation of the molecular arrangement(s) in these glasses. Indeed, the positions of the four components in F-III are first constrained in the Raman spectra, which are more identifiable, then further refined using available Raman spectra for corresponding chemically simple silicate systems. The nine fitted components can reproduce the Raman and FTIR spectra extremely well. As a function of the amount of SiO 2 , the positions and intensities of the three low frequency components progressively shift in both Raman and FTIR. Similarly, the two bands in the F-II intermediate region exhibit a monotonic shifting of their positions. Indeed, the components at high frequency display less significant shifting of their positions as a function of SiO 2 , while their intensities change more markedly in the Raman spectrum compared to those for FTIR. The vibrational components measured in this study provide a referenced dataset of assignations of the most abundant natural volcanic glasses. Therefore, it provides a diagnostic tool based on the cross-validation of Raman and FTIR spectra to quickly identify the glass chemistry, offering the possibility to expand the applicability of remote investigations. [ABSTRACT FROM AUTHOR]

Crystal-chemical variations of pyroxene (px) and plagioclase (plg) have been analysed by X-ray electron-microprobe (EPMA) mapping to quantify their actual chemical dispersions. These phases were experimentally crystallised from a basaltic liquid (B 100 , MORB from Iceland) at cooling rates of 1, 7, 60 and 180 °C/h from 1300 °C down to 800 °C. Experiments were run at ambient conditions applying defined temperature paths mirroring characteristic cooling rates from innermost to outermost portions of metre- to centimetre-thick lavas, dikes and bombs emplaced under submarine to subaerial conditions. As the cooling rate increases from 1 to 180 °C/h, the run-products become progressively enriched in pyroxene and depleted in plagioclase, while spinel is invariably low (few area%) and glass is significant only at 180 °C/h. An increase of cooling rate generally leads to enrichment of Al 2 O 3 and depletion of MgO in px, while the opposite behaviour is observed for plg; these trends are mirrored by calculated cations (apfu: atom per formula unit) and components. Average variations as a function of cooling rate are similar to those already observed through classical analysis performed by single point EPMA. However, the actual chemical distributions of CaO versus MgO, Al 2 O 3 and FeOtot oxides unveil the presence of a wider range in pyroxene chemistry. In particular, one px (px-1, CaO-rich, diopsidic type) is present at all the applied cooling rates; a very low CaO-px (px-2, pigeonite or orthopyroxene type) is detected at 1 °C/h; and, finally, once more population of px (px-3, CaO-poor diopsidic type) appears at 60 and 180 °C/h. By contrast, plg analyses yield invariably identical compositions. Textural variations as a function of cooling rate and geothermometric estimations indicate that px-1 crystallised at high- T (or low Δ T), while plg mainly grew in the residual melt produced by the saturation of px. If only textures were evaluated, this order of segregation would like remain unrecognised since px at low cooling rates is smaller than plg. The abundance of phases, their crystal-chemical features, and their order of segregation can be regarded through a theoretical framework of a time-temperature-transformation (TTT) diagram. The most significant chemical variations are displayed by MgO and Al 2 O 3 for both px and plg, which faithfully capture the evolution of cooling conditions. The chemical compositions of px-1 is close to the thermodynamic equilibrium only at 1 °C/h. As the cooling rates increase, the px chemistry indicates disequilibrium conditions. Finally, this study shows that as Δ T /Δ t increases, the most abundant px (px-1) and plg are forced towards compositions that become progressively closer to those of the parental liquid. [ABSTRACT FROM AUTHOR]

Exposure to styrene is a major safety concern in the fibreglass processing industry. This compound is classified by the International Agency for Research on Cancer as a possible human carcinogen. Several types of analytical equipment exist for detecting volatile organic compounds (VOCs) in the atmosphere; however, most of them operate ex-situ or do not provide easy discrimination between different molecules. This work introduces an improved and portable method based on FTIR spectroscopy to analyse toxic gaseous substances in working sites down to a concentration of less than 4 ppm. Styrene and a combination of VOCs typically associated with it in industrial processes, such as acetone, ethanol, xylene and isopropanol, have been used to calibrate and test the methodology. The results demonstrate that the technique offers the possibility to discriminate between different gaseous compounds in the atmosphere with a high degree of confidence and obtain very accurate quantitative information on their concentration, down to the ppm level, even when different VOCs are present in a mixture. [Display omitted] • Exposure to VOCs is a serious safety issue for industrial processing. • An FTIR-based sensing method allows for a fast and reliable VOCs' detection down to ppm. • The method easily discriminates acetone, styrene, xylene, isopropanol, and acetone vapors. • Precise calibration to determine styrene concentration in the atmosphere is achieved. [ABSTRACT FROM AUTHOR]

Microporous organic-inorganic hybrid silica films have been designed as active platforms to realise a styrene gas sensor. The microporous film has been synthesized by using tetraethylorthosilicate and phenyltriethoxysilane as precursors and a triblock copolymer (Pluronic F127) as a template for the pores. Multilayer films have been employed to increase the performance of the sensor and infrared spectroscopy has been used to probe the absorbed styrene molecules. The sensing response has been investigated by repeated exposures to different concentrations of styrene gas from 10 to 100 ppm. The microporous film has shown a better response compared to dense layers because of the increased surface area and the presence of the phenyl groups that enable a selective adsorption-desorption of the styrene. The diffusion coefficient of the microporous hybrid films has been calculated using a monodimensional plane-sheet diffusion model. This study shows that the microporous hybrid films have great potential to be used as simple and effective sensing materials for styrene and other Volatile Organic Compounds. Image 1 • Phenyl-based mesoporous films enable adsorption of styrene molecules. • FTIR spectroscopy allows selective sensing of adsorbed styrene. • Multilayer mesoporous films improve the sensing performances. • Diffusion coefficient in mesoporous films follows a monodimensional plane-sheet model. [ABSTRACT FROM AUTHOR]

In this work we address the stability of riebeckite at high temperatures and compare the different behaviors observed under various oxidation conditions. For this purpose, we annealed powders of a sample from Mt. Malosa (Malawi), which is compositionally close to the end-member; the run products obtained after annealing in air vs. in vacuum were studied by Mossbauer spectroscopy and powder X-ray diffraction. The results show that riebeckite follows two distinct paths depending on the external environment. Under oxidizing conditions, it is stable in the hydrous form up to relatively low temperatures (400-450 °C), then it undergoes a rapid (within ~50 °C) dehydrogenation, forming oxo-riebeckite, which is stable up to ~900 °C. The final breakdown products of the oxo-amphibole include aegirine + cristobalite + hematite. Based on the relative intensity of the (310) Bragg reflection, the activation energy (Ea) for the riebeckite to oxo-riebeckite transition is 166 ± 6 kJ/mol. Under vacuum conditions, no Fe oxidation is observed, and riebeckite is stable up to much higher temperatures (750-800 °C); however, in the 550 < T < 700 °C range, it undergoes a significant rearrangement of the C cations (those hosted in the strip of octahedra). Indeed, the amphibole stable in the 700-800 °C range has the same chemical formula as riebeckite but has a disordered and nonstandard cation distribution at the octahedra, i.e., ^(1)(Fe3+Fe2+)M(2)(Fe3+Fe2+)M(3)Fe2+; we call this phase "CR3+ disordered riebeckite". For T > 800 °C, it decomposes to aegirine + fayalite + cristobalite + H2O. External oxygen is required for the release of water into the surrounding system, being a prerequisite for the Fe-amphiboles to be a carrier of H2O in the lower crust and upper mantle. One important implication of our results is that characterization of the overall oxidation state of iron does not necessarily provide the redox conditions of the environment of formation because a crystal-chemical re-arrangement under reducing conditions allows riebeckite to maintain its Fe3+/Fe2+ composition up to higher temperatures. [ABSTRACT FROM AUTHOR]

Human exposure to Volatile Organic Compounds (VOCs) and their presence in indoor and working environments is recognized as a serious health risk, causing impairments of varying severities. Different detecting systems able to monitor VOCs are available in the market; however, they have significant limitations for both sensitivity and chemical discrimination capability. During the last years we studied systematically the use of Fourier Transform Infrared (FTIR) spectroscopy as an alternative, powerful tool for quantifying VOCs in air. We calibrated the method for a set of compounds (styrene, acetone, ethanol and isopropanol) by using both laboratory and portable infrared spectrometers. The aim was to develop a new, and highly sensitive sensor system for VOCs monitoring. In this paper, we improved the setup performance, testing the feasibility of using a multipass cell with the aim of extending the sensitivity of our system down to the part per million (ppm) level. Considering that multipass cells are now also available for portable instruments, this study opens the road for the design of new high-resolution devices for environmental monitoring. [ABSTRACT FROM AUTHOR]

The new mineral species braccoite, ideally NaMn2+5 [Si5AsO17(OH)](OH), has been discovered in the Valletta mine dumps, in Maira Valley, Cuneo province, Piedmont, Italy. Its origin is probably related to the reaction between ore minerals and hydrothermal fluids. It occurs as subhedral crystals in brown-red coloured thin masses, with a pale-yellow streak and vitreous to resinous lustre. Braccoite is associated with tiragalloite, for which new data are provided, as well as gamagarite, hematite, manganberzeliite, palenzonaite, quartz, saneroite, tokyoite, unidentified Mn oxides, organic compounds, and Mn arsenates and silicates under study. Braccoite is biaxial positive with refractive indices α = 1.749(1), β = 1.750(1), γ = 1.760(1). It is triclinic, space group P1̄ , with a = 9.7354(4), b = 9.9572(3), c = 9.0657(3) Å, α = 92̄691(2), β = 117.057(4), γ = 105.323(3)°, V = 740.37(4) Å3 and Z = 2. Its calculated density is 3.56 g/cm3. The ten strongest diffraction lines of the observed powder X-ray diffraction (XRD) pattern are [d in Å, (I), (hkl)]: 3.055 (69)(22̄1), 3.042 (43)(102), 3.012 (65)(32̄1̄ ), 2.985 (55)(23̄1̄ ), 2.825 (100)(213̄), 2.708 (92)(220), 2.627 (43)(23̄2̄), 2.381 (58)(41̄1̄ ), 2.226 (25)(214̄) and 1.680 (433̄)(36). Chemical analyses by wavelength-dispersive spectroscopy electron microprobe gave (wt.%): Na2O 4.06, CaO 0.05, MnO 41.76, MgO 0.96, Al2O3 0.04, CuO 0.02, SiO2 39.73, As2O5 6.87, V2O5 1.43, SO3 0.01 and F 0.04. H2O 2.20 was calculated on the basis of 2OH groups p.f.u. Raman spectroscopy confirmed the presence of (SiO4)4-, (AsO4)3- and OH groups. The empirical formula, calculated on the basis of Σ cations-(Na,K) = 11 p.f.u., in agreement with the results of the crystal structure, is Na1.06(Mn2+4.46Mn3+0.32Mg0.19V3+0.01Al0.01Ca0.01)[Si5(As0.48Si0.37V5+0.15)O17(OH)](OH0.98F0.02); the simplified formula is Na(Mn,Mg,Al,Ca)5[Si5(As,V,Si)O17(OH)](OH,F). Single-crystal XRD allowed the structure to be solved by direct methods and revealed that braccoite is the As-dominant analogue of saneroite. The structure model was refined on the basis of 4389 observed reflections to R1 = 3.47%. Braccoite is named in honour of Dr Roberto Bracco (b. 1959), a systematic minerals collector with a special interest in manganese minerals. The new mineral was approved by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (IMA 2013-093). [ABSTRACT FROM AUTHOR]

The thermal behavior of melanterite from the Fornovolasco mine (Tuscany, Italy) has been investigated via differential thermal analysis (DTA), thermogravimetry (TG), in situ high-temperature X-ray powder diffraction (XRPD) and Fourier-transform infrared spectroscopy (FTIR). The DTA curve showed endothermic peaks at 70, 100, 260, 500–560 and 660 °C whereas the TG curve evidenced a total mass decrease of ~68%, in keeping with the loss of all H2O and SO4 groups. Rietveld refinements were performed for all the collected patterns in the 25–775 °C range and converged at 1.57 ≤ R (%) ≤ 2.75 and 1.98 ≤ Rwp (%) ≤ 3.74. The decomposition steps FeSO4·7H2O → FeSO4·4H2O (25 ≤ T ≤ 50 °C) → FeSO4·H2O (50 < T ≤ 100 °C) → FeOHSO4 (75 < T ≤ 200 °C) → Fe2(SO4)3 (400 < T ≤ 500 °C) → Fe2O3 (500 < T ≤ 775 °C) were obtained. The high-temperature infrared analysis confirmed that melanterite undergoes a three-step dehydration in the 25–300 °C temperature range. The FeOHSO4 phase is stable over a wide range of temperature and transforms partially to Fe2(SO4)3 without the formation of Fe2O(SO4)2. The findings highlight a different behavior of the studied sample with respect to the synthetic salt. [ABSTRACT FROM AUTHOR]

Muong Nong-type (MN) tektites are a layered type of tektite associated to the Australasian strewn field, the youngest (790 kyr) and largest on Earth. In some MN tektites, coesite is observed in association with relict quartz and silica glass within inclusions surrounded by a froth layer. The formation of coesite-bearing frothy inclusions is here investigated through a 3D textural multiscale analysis of the vesicles contained in a MN tektite sample, combined with compositional and spectroscopic data. The vesicle size distribution testifies to a post-shock decompression that induced melting and extensive vesiculation in the tektite melt. Compared to free vesicles, nucleated homogeneously in the tektite melt, froth vesicles nucleated heterogeneously on relict quartz surfaces at the margins of coesite-bearing inclusions. The rapid detachment of the froth vesicles and prompt reactivation of the nucleation site favoured the packing of vesicles and the formation of the froth structure. Vesicle relaxation time scales suggest that the vesiculation process lasted few seconds. The formation of the froth layer was instrumental for the preservation of coesite, promoting quenching of the inclusion core through the subtraction of heat during froth expansion, thereby physically insulating the inclusion until the final quench of the tektite melt. [ABSTRACT FROM AUTHOR]