75As Nuclear Magnetic Resonance Spectroscopic Investigation of the Thioarsenate Speciation in Strongly Alkaline Sulfidic Leaching Solutions.

Copper ores and concentrates thereof feature an increasingly notable content of impurities such as arsenic and other hazardous elements. As an alternative to the state-of-the-art partial roasting process, arsenic could be removed by the alkaline sulfide leaching of the copper concentrates. In order to optimize and understand the processes, knowledge of the speciation and oxidation states is essential. In addition to methods such as UV/Vis spectroscopy, chromatography and ICP/MS methods, 75As NMR spectroscopy may be useful for the differentiation and quantification of the various species. Although arsenate(V) has been characterized by 75As NMR some time ago, to our knowledge, there are no data on tetrathioarsenate(V) AsS43- and the mixed oxygen/sulfur substituted mono-, di- and trithioarsenates(V) AsOxS4-x3-, x = 3, 2, 1, respectively. Therefore, we investigated several model solutions and samples from Cu-As leaching with 75As NMR. The strongly alkaline conditions of the leaching solution proved to be very advantageous for that purpose. Both the tetrathioarsenate(V) and the mixed species AsOxS4-x3- (x = 1-3) could be characterized and provide valuable data for the quantification of the material flows in the leaching process.

Creation of a 3D Goethite-Spongin Composite Using an Extreme Biomimetics Approach.

The structural biopolymer spongin in the form of a 3D scaffold resembles in shape and size numerous species of industrially useful marine keratosan demosponges. Due to the large-scale aquaculture of these sponges worldwide, it represents a unique renewable source of biological material, which has already been successfully applied in biomedicine and bioinspired materials science. In the present study, spongin from the demosponge Hippospongia communis was used as a microporous template for the development of a new 3D composite containing goethite [α-FeO(OH)]. For this purpose, an extreme biomimetic technique using iron powder, crystalline iodine, and fibrous spongin was applied under laboratory conditions for the first time. The product was characterized using SEM and digital light microscopy, infrared and Raman spectroscopy, XRD, thermogravimetry (TG/DTG), and confocal micro X-ray fluorescence spectroscopy (CMXRF). A potential application of the obtained goethite-spongin composite in the electrochemical sensing of dopamine (DA) in human urine samples was investigated, with satisfactory recoveries (96% to 116%) being obtained.

Spongin as a Unique 3D Template for the Development of Functional Iron-Based Composites Using Biomimetic Approach In Vitro.

Marine sponges of the subclass Keratosa originated on our planet about 900 million years ago and represent evolutionarily ancient and hierarchically structured biological materials. One of them, proteinaceous spongin, is responsible for the formation of 3D structured fibrous skeletons and remains enigmatic with complex chemistry. The objective of this study was to investigate the interaction of spongin with iron ions in a marine environment due to biocorrosion, leading to the occurrence of lepidocrocite. For this purpose, a biomimetic approach for the development of a new lepidocrocite-containing 3D spongin scaffold under laboratory conditions at 24 °C using artificial seawater and iron is described for the first time. This method helps to obtain a new composite as "Iron-Spongin", which was characterized by infrared spectroscopy and thermogravimetry. Furthermore, sophisticated techniques such as X-ray fluorescence, microscope technique, and X-Ray diffraction were used to determine the structure. This research proposed a corresponding mechanism of lepidocrocite formation, which may be connected with the spongin amino acids functional groups. Moreover, the potential application of the biocomposite as an electrochemical dopamine sensor is proposed. The conducted research not only shows the mechanism or sensor properties of "Iron-spongin" but also opens the door to other applications of these multifunctional materials.

Refining of Precious Metal Bearing Materials from Secondary Sources-Methanesulfonic Acid Leaching of Raw Silver Granules as a Promising Approach towards a Green Way of Silver Refining.

The state-of-the-art technology of raw silver refining in a silver nitrate-based electrorefining process (Moebius-electrolysis) is accompanied by several disadvantages, both from a technological and from an ecological point of view. In addition, increasing concentrations of critical impurities from secondary sources, like palladium, in raw silver are a further challenge for the future of silver refining. Thus, there is strong motivation for the development of an adequate, alternative process of raw silver refining to substitute the existing Moebius-electrolysis. Due to its less environmentally toxic character and the high aqueous solubility of its silver salt, methanesulfonic acid (MSA) is a possible base chemical for the design of an efficient refining method based on leaching of raw silver followed by electrowinning, with less ecological and technological complications. In this paper the results of some fundamental investigations on the leaching of raw silver granules, containing approx. 94% silver, with methanesulfonic acid and hydrogen peroxide as an oxidation agent are presented. Agitation leaching experiments were conducted on a laboratory scale and the effects of the solid concentration, the hydrogen peroxide dosage and the temperature as leaching parameters were studied. The obtained results indicate that silver leaching yields of more than 90% are achievable with leaching at elevated temperatures of 65 °C or 80 °C, solid concentrations of 500 g/L and at a stoichiometric H2O2:Ag-ratio of 3:1. Increased solid concentrations greater than 500 g/L and elevated temperatures of 65 °C or 80 °C additionally improved the selectivity of the process regarding the leaching of Pd.

Aluminum Melt Filtration with Carbon Bonded Alumina Filters.

The wetting behavior was measured for Al2O3-C in contact with AlSi7Mg with a conventional sessile drop test (vacuum, 950 °C and 180 min) and a sessile drop test with a capillary purification unit (vacuum, 730 °C and 30 min). The conventional test yielded contact angles of around 92°, whereas the sessile drop measurement with capillary purification showed a strongly non-wetting behavior with a determined apparent contact angle of the rolling drop of 157°. Filtration tests, which were repeated twice, showed that the Al2O3-C filter possessed a better filtration behavior than the Al2O3 reference filter. For both filtration trials, the PoDFA (porous disc filtration analysis) index of the Al2O3-C filter sample was equal to half of the PoDFA index of the Al2O3 reference filter sample, indicating a significantly improved filtration performance when using Al2O3-C filter. Notable is the observation of a newly formed layer between the aluminum and the Al2O3-C coating. The layer possessed a thickness between 10 µm up to 50 µm and consisted of Al, C, and O, however, with different ratios than the original Al2O3-C coating. Thermodynamic calculations based on parameters of the wetting and filtration trials underline the possible formation of an Al4O4C-layer.