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We report in this paper a new crystal-chemical study of synthetic basic ferric sulfate FeOHSO4. The structure solution performed by the Endeavour program, from new X-ray powder diffraction (XRPD) data, indicated that the correct space group of the monoclinic polytype of FeOHSO4 is C2/c. Selected Area Electron Diffraction (SAED) patterns are also consistent with this structure solution. The arrangement of Fe and S atoms, based on linear chains of Fe3+ octahedra cross-linked by SO4 tetrahedra, corresponds to that of the order/disorder (OD) family. The positions of the hydrogen atoms were located based on DFT calculations. IR and Raman spectra are presented and discussed according to this new structure model. The decomposition of FeOHSO4 during heating was further investigated by means of variable temperature XRPD, thermogravimetry, and differential thermal analysis as well as IR and Raman spectroscopies.

A multi-methodical characterization of a sauconite (Zn-bearing trioctahedral smectite) specimen from the Skorpion ore deposit (Namibia) was performed by combining X‑ray powder diffraction (XRPD), cation exchange capacity (CEC) analysis, differential thermal analysis (DTA), thermo‑ gravimetry (TG), Fourier transform infrared spectroscopy (FTIR), and transmission electron microscopy (TEM‑HRTEM‑AEM). The X‑ray diffraction pattern exhibits the typical features of turbostratic stacking disorder with symmetrical basal 00l reflections and long‑tailed hk bands, as confirmed by TEM observations. Besides sauconite, the sample contains minor amounts of kaolinite, dioctahedral smectite, and quartz. CEC analysis provides a total of Ca (~69%), Mg (~26%), Na (~4%), and K (0.7%) exchangeable cations. Therefore, Zn is located exclusively within the octahedral site of sauconite. TG analysis of the sample yields a total mass loss of about 17%. Three endothermic peaks can be observed in the DTA curve, associated with dehydration and dehydroxylation of the material. An exothermic peak at 820 °C is also present as a consequence of decomposition and recrystallization. The infrared spectrum shows the typical ZnOH stretching signature at 3648 cm, whereas, in the OH/HO stretching region two bands at 3585 and 3440 cm can be attributed to stretching vibrations of the inner hydration sphere of the interlayer cations and to absorbed HO stretching vibration, respectively. Diagnostic bands of kaolinite impurity at ~3698 and 3620 cm are also found, whereas 2:1 dioctahedral layer silicates may contribute to the 3585 and 3620 cm bands. Finally, using the one-layer supercell approach implemented in the BGMN software, a satisfactory XRPD profile fitting model for the Skorpion sauconite was obtained. These findings have implications not only for economic geology/recovery of critical metals but also, more generally, in the field of environmental sciences., The XRPD laboratory at the Dipartimento di Scienze della Terra and Geoambientali, University of Bari “Aldo Moro”, was funded by Potenziamento Strutturale PONa3_00369 “Laboratorio per lo Sviluppo Integrato delle Scienze e delle TEcnologie dei Materiali Avanzati e per dispositivi innovativi (SISTEMA)”. The XRPD facility at the DiSTAR, University “Federico II” Napoli, is acknowledged. The authors acknowledge Annett Steudel and Katja Emmerich for CEC measurement at the Competence Center for Material Moisture, University of Karlshrue, Germany. GB and NM thank Maria Boni, invaluable scientific guide who promoted the study of the economic geology of worldwide nonsulfide ore deposits, and G. Arfè who firstly characterized the Skorpion samples and for continuous help and fruitful discussions. This work was partly supported by DiSTAR fund 2017 (University of Naples Federico II, Italy) granted to G. Balassone, as well as by the research projects PGC2018-094573-B-100 from the Spanish Government and the Research Group RNM-179 of the Junta de Andalucía granted to F. Nieto. Two anonymous referees are thanked for insightful comments that helped to improve the quality of the manuscript.

The garnierite ore at Campello Monti occurs as dark green colloform concretions covering surfaces, fractures, and filling veins in harzburgite rocks. The representative composition (Ni2.45Mg0.14Cu0.12Co0.05)Σ2.76Si2.10O5(OH)4 is consistent with a 7 Å phase, namely pecoraite or népouite. Relevant chemical features are an exceptionally high Ni/Mg ratio, a significant level of Cu substituting for Ni, and a low content of S, possibly in tetrahedral sites. Olivine and orthopyroxene in the harzburgite host rock are only partially serpentinized, do not contain detectable Ni, and are almost iron free. The green coating probably originated from groundwater solutions that leached nearby weathered peridotites and sulfide ores, and deposited less-mobile elements along fractures and voids of the host peridotite, just outside their provenance area. Bulk techniques such as X-ray powder diffraction and infrared spectroscopy do not confidently distinguish between népouite and pecoraite, although the comparison with synthetic, implicitly pure polymorphs indicates népouite as the best matching phase. On the other hand, HRTEM clearly shows that garnierite is mostly constituted by plumose aggregates made of curved crystals with frayed tips, a few nanometers thick along the stacks and a few tens of nanometers long (nanoflakes). All known lizardite stacking sequences, namely 1T, 2H1, and 2H2, have been locally observed, even though most crystals show stacking disorder. The recorded nanostructure suggests possible explanations for the recurrent anomalies (low oxide totals, high IVT/VIM cation ratios, etc.) found in EMP analyses of garnierites. The small grain size, the high density of defects, and the structural arrangement actually intermediate between lizardite and chrysotile probably explain the ambiguities that occurred during the characterization with bulk techniques. The results obtained in this study may have important implications for ore processing methods

Magnetite nanoparticles (NPs) were synthetized by partial oxidation of hot Fe(II) sulfate aqueous solutions upon addition of variable amounts of alkali/nitrate ions in a N2 atmosphere. The resulting NPs were extensively characterized by Scanning Electron Microscopy (SEM), X-Ray Powder Diffraction (XRPD), Dynamic Light Scattering (DLS) and Brunauer-Emmett-Teller (BET) analysis. Depending on the final pH after synthesis, partially oxidized magnetite NPs were obtained with average crystallite size ranging from 29 to 116 nm. The potential of NPs as arsenic adsorbents was investigated through batch adsorption experiments. The analysis of the adsorption isotherms performed on the basis of both Freundlich and Langmuir models, revealed that arsenic adsorption capacity was more efficient for magnetite NPs synthetized at final pH ≤ 6.56, characterized by polydisperse submicrometric aggregates with coarse macro- and mesopore distributions.

The crystal structure of calcium tartrate esahydrate, CaC4H4O6·6H2O, has been solved by the charge-flipping method from single-crystal X-ray diffraction data and refined toR= 0.021, based on 1700 unique observed diffractions. Salient crystallographic data are:a= 7.7390 (1),b= 12.8030 (2),c= 5.8290 (1) Å,Z= 2, and space groupP21212. During the refinement step it was possible to locate all H atoms by difference Fourier synthesis. The tartrate molecule has a (−)-gaucheconformation and is coordinated to two calcium ions to form infinite chains along theaaxis which alternate Ca polyhedra with tartrate molecules. The chains are interlinked by a three-dimensional network of hydrogen bonds from four water molecules surrounding the Ca ion, reinforced by hydrogen bonds from one interstitial water molecule. Micro-Raman and FT–IR spectroscopic data are provided.

The thermal dehydration process of fibroferrite, FeOH(SO4)·5H2O, a secondary iron-bearing hydrous sulfate, was investigated by in situ high-temperature synchrotron X-ray powder diffraction (HT-XRPD), in situ high-temperature Fourier transform infrared spectroscopy (HT-FTIR) and thermal analysis (TGA-DTA) combined with evolved gas mass spectrometry. The data analysis allowed the determination of the stability fields and the reaction paths for this mineral as well as characterization of its high-temperature products. Five main endothermic peaks are observed in the DTA curve collected from room T up to 800 °C. Mass spectrometry of gases evolved during thermogravimetric analysis confirms that the first four mass loss steps are due to water emission, while the fifth is due to a dehydroxylation process; the final step is due to the decomposition of the remaining sulfate ion. The temperature behavior of the different phases occurring during the heating process was analyzed, and the induced structural changes are discussed. In particular, the crystal structure of a new phase, FeOH(SO4)·4H2O, appearing at about 80 °C due to release of one interstitial H2O molecule, was solved by ab initio real-space and reciprocal-space methods. This study contributes to further understanding of the dehydration mechanism and thermal stability of secondary sulfate minerals.

Trioctahedral mica samples, collected at Cava St. Antonio (Mt. Vulture, Italy) were studied by combining electron-microprobe and C-H-N elemental analyses, single-crystal X-ray diffraction refinement, Mossbauer and Fourier transform infrared spectroscopies. Electron-microprobe analyses show the crystals to be quite homogeneous with TiO2 similar to 3 wt % and F ranging from 0.42 to 0.59 wt% Quantitative analyses of H combined with ferric/ferrous ratios from Mossbauer data allowed reliable crystal-chemical formulae to be derived. The results suggest that the entry of both Ti4+ and Fe3+ in the structure occurs through R-oxy substitution mechanisms involving deprotonation at O(4). This inference is supported by X-ray structure-refinement results (notably the c cell-parameter. the off-centering of the M2 cation towards O(4), the bond-length distortions of the cis-M2 octahedron) obtained using anisotropic thermal parameters in space group C2/m. The amount of oxy-substitutions from both electron-microprobe and X-ray data is in agreement with carbon-hydrogen-nitrogen analyses which give an average anion composition (OH1.25O0.65F0.10). Polarized-light infrared spectroscopy shows a complex OH-stretching spectrum which is composed of several overlapping (at least five) components. These can be assigned to the main octahedral local configurations that are compatible with the chemical composition. Pleochroic Fourier transform infrared spectroscopy measurements done along the principal optical directions show that the O-H bond axis is tilted from [001] and provide the average orientation of the O-H dipole in the structure: O-H (boolean AND) alpha similar to 23 degrees and O-H (boolean AND) gamma similar to 56 degrees.

The crystal structure of cyanotrichite, having general formula Cu4Al2(SO4)(OH)12·2H2O, from the Dachang deposit (China) was studied by means of conventional transmission electron microscopy, automated electron diffraction tomography (ADT) and synchrotron X-ray powder diffraction (XRPD). ADT revealed the presence of two different cyanotrichite-like phases. The same phases were also recognized in the XRPD pattern, allowing the perfect indexing of all peaks leading, after refinement to the following cell parameters: (1) a = 12.417(2) Å, b = 2.907(1) Å, c = 10.157(1) Å and β = 98.12(1); (2) a = 12.660(2) Å, b = 2.897(1) Å, c = 10.162(1) Å and β = 92.42(1)°. Only for the former phase, labeled cyanotrichite-98, a partial structure, corresponding to the [Cu4Al2(OH)12 2+] cluster, was obtained ab initio by direct methods in space group C2/m on the basis of electron diffraction data. Geometric and charge-balance considerations allowed to reach the whole structure model for the cyanotrichite-98 phase. The sulfate group and water molecule result to be statistically disordered over two possible positions, but keeping the average structure consistent with the C-centering symmetry, in agreement with ADT results.

This paper relates an infrared (IR) (6000–2500; 1400–400 cm–1) spectroscopic study of sideronatrite, Na2Fe3+(SO4)2(OH)·3H2O. Spectra in the 600–1250 cm–1 range are dominated by fundamental S–O absorption bands. Factor-group analysis based on the space group P212121(D42) is in accordance with the observed band multiplicity. A broad and convolute absorption centred around 3400 cm–1 and a sharp band at 3605 cm–1 are observed in the 2900–3900 cm–1 frequency region. The resolution of the broad band is significantly improved at liquid nitrogen temperature; seven components can be fitted to the pattern and these can be assigned to H2O/OH molecules in the structure. All components in the broad band and the sharp absorption at 3605 cm–1 are strongly polarized for E//a, in accordance with the structure analysis results. Infrared transmission spectroscopy is a useful tool to identify these sulfate minerals occurring in specific geological environments.

"The thermal stability of sideronatrite, ideally Na2Fe3+(SO4)(2)(OH)center dot 3(H2O), and its decomposition products were investigated by combining thermogravimetric and differential thermal analysis, in situ high-temperature X-ray powder diffraction (HT-XRPD) and Fourier transform infrared spectroscopy (HT-FTIR). The data show that for increasing temperature there are four main dehydration\/transformation steps in sideronatrite: (a) between 30 and 40 A degrees C sideronatrite transforms into metasideronatrite after the loss of two water molecules; both XRD and FTIR suggest that this transformation occurs via minor adjustments in the building block. (b) between 120 and 300 A degrees C metasideronatrite transforms into metasideronatrite II, a still poorly characterized phase with possible orthorhombic symmetry, consequently to the loss of an additional water molecule; X-ray diffraction data suggest that metasideronatrite disappears from the assemblage above 175 A degrees C. (c) between 315 and 415 A degrees C metasideronatrite II transforms into the anhydrous Na3Fe(SO4)(3) compound. This step occurs via the loss of hydroxyl groups that involves the breakdown of the [Fe3+(SO4)(2)(OH)] (a) (2-) chains and the formation of an intermediate transient amorphous phase precursor of Na3Fe(SO4)(3). (d) for T > 500 A degrees C, the Na3Fe(SO4)(3) compound is replaced by the Na-sulfate thenardite, Na2SO4, plus Fe-oxides, according to the Na3Fe3+(SO4)(3) -> 3\/2 Na-2(SO4) + 1\/2 Fe2O3 + SOx reaction products. The Na-Fe sulfate disappears around 540 A degrees C. For higher temperatures, the Na-sulfates decomposes and only hematite survives in the final product. The understanding of the thermal behavior of minerals such as sideronatrite and related sulfates is important both from an environmental point of view, due to the presence of these phases in evaporitic deposits, soils and sediments including extraterrestrial occurrences, and from the technological point of view, due to the use of these materials in many industrial applications"