Natural nanomaterials : reappraising the elusive structure of the nano-sized mineral ferrihydrite through X-Ray absorption spectroscopy at the iron K-edge

Ferrihydrite is natural ferric oxyhydroxide occurring exclusively nanocrystalline. With ideal formula 5 Fe2 O3 . 9 H2 O, ferrihydrite is quite abundant in sediments, weathering crusts and mine wastes, being characteristic of red pre-soils formed by loose weathered rock plus mineral debris (regoliths) and commonly designated as “2-line” or “6-line” on the basis of the broadened maxima observed in the X-ray diffraction pattern. Synthetic nanocrystalline “6-line” ferrihydrite was recently studied through methods based on atomic-pair distribution functions disclosing the possible occurrence of icosahedral clusters formed by twelve octahedra centred by an inner tetrahedron, all filled by Fe 3+ ions. However, Mössbauer studies were inconclusive about the existence of 4-coordinated iron, thus suggesting that the tetrahedral cation may well be Si4+. In view of such structural uncertainty, a XANES study at the Fe K-edge was undertaken on ferrihydrite from a regolith to ascertain the occurrence of tetrahedral iron. Comparison with data collected from well crystallized iron oxide and hydroxide minerals where Fe 3+/2+ ions occur in octahedral and tetrahedral coordination is described and the results so far obtained are discussed, showing that supplementary study is needed on the elusive structure of ferrihydrite

Cultural Heritage analysis using Synchrotron Radiaon: case studies in Ceramics, Glasses, and Lithologic Materials

ABSTRACT: Synchrotron radiaton is a powerful tool for non‐destructve analysis of materials in cultural heritage research. It has revolutonized our ability to understand the compositon, structure, and history of cultural heritage objects, leading to significant advances in fields such as archaeology, art conservation, and materials science. Dedicated beamlines for cultural heritage research are available at synchrotron facilites around the world, such as the European Synchrotron Radiation Facility (ESRF), SOLEIL synchrotron, and ALBA synchrotron, providing specialized support and instrumentation for high‐resolution analysis of cultural heritage objects using various techniques, such as X‐ray absorption spectroscopy, X‐ray fluorescence, X‐ray diffraction, and X‐ray imaging.N/

Molybdenite as a rhenium carrier : first results of a spectroscopic approach using synchrotron radiation

The chemical and physical properties of rhenium render it a highly demanded metal for advanced applications in important industrial fields. This very scarce element occurs mainly in ores of porphyry copper-molybdenum deposits associated with the mineral molybdenite, MoS2, but it has also been found in granite pegmatites and quartz veins as well as in volcanic gases. Molybdenite is a typical polytype mineral which crystal structure is based on the stacking of [S-Mo-S] with molybdenum in prismatic coordination by sulphide anions; however, it is not yet clearly established if rhenium ions replace Mo4+ cations in a disordered way or else, if such replacement gives rise to dispersed nanodomains of a rhenium-rich phase. As a contribution to clarify this question, an X-ray absorption spectroscopy (XANES) study using synchrotron radiation was performed at the Re L3-edge of rhenium-containing molybdenite samples. Obtained results are described and discussed supporting the generally accepted structural perspective that rhenium is mainly carried by molybdenite through the isomorphous replacement of Mo, rather than by the formation of dispersed Re-specific nanophase(s)

Development of a Simple Method for Labeling and Identification of Protein Binders in Art

Easel paintings are assets with an important historic and cultural value. They usually possess a multi-tiered structure, composed of di erent layers some of which may present protein binders, making it important to identify these materials for restoration and conservation purposes. We propose the identification of di erent protein binders by a new fluorescent labeling method employing a coumarin based chromophore, C392STP (sodium(E/Z)-4-(4-(2-(6,7-dimethoxycoumarin-3-yl)vinyl)benzoyl)-2,3,5,6-tetrafluorobenzenesulfo-nate). The method was optimized using commercial proteins and was further tested on proteins extracted from hen’s egg yolk, white bovine milk, and rabbit skin glue. To model more realistic conditions, paint models of easel paintings were prepared. The paint models were made with hen’s egg yolk, white bovine milk, and rabbit skin glue, mixed with di erent pigments and submitted to artificial aging. Then the extracted proteins from the paint models were labeled with C392 which allowed a sensitive and selective identification by polyacrylamide gel electrophoresis (PAGE) of the di erent protein binders used. As a final test, three 19th century easel paintings, from the Italian painter Giorgio Marini, were analyzed. The results show the potential of the proposed method for the identification of protein binders present in easel paintings

Selenium speciation in waste materials from an exhausted Iberian Pyrite Belt mine

Selenium is an essential nutrient for humans, animals and microorganisms, but it becomes toxic at concentrations slightly above the nutritional levels. This naturally occurring trace element can be released to the environment from various anthropogenic sources such as mining, agricultural, petrochemical and industrial processes and its toxicity is developed along a complex cycle involving adsorption by soil components and subsequent accumulation by plants. In the environment, selenium can occur in several oxidation states ranging from selenide (Se=) to elemental selenium (Se0), selenite (Se4+) and selenate (Se6+). Selenium contents above 900 ppm were recently assigned in mine wastes from the sulphur factory at the São Domingos exhausted pyrite mine exploited in the Iberian Pyrite Belt (south Portugal) since Roman times until 1966. Aiming at a sustainable remediation of this mining site, an X-ray absorption spectroscopy study using synchrotron radiation, combined with X-ray diffraction, was undertaken to clarify the speciation state of selenium and the nature of Se-carrier phase(s). The results show that selenium does not significantly replace sulphur under the form of selenate in the dominant sulphate phases and occasionally remains as a substituting selenide anion in debris of the original sulphides present in the mine waste materials