TY - JOUR A1 - Kaufmann, Felix E.D. A1 - Hoffmann, Marie C. A1 - Bachmann, Kai A1 - Veksler, Ilya V. A1 - Trumbull, Robert B. A1 - Hecht, Lutz T1 - Variations in composition, texture, and platinum group element mineralization in the lower group and middle group chromitites of the Northwestern Bushveld Complex, South Africa N2 - Small-scale variations in mineral chemistry, textures, and platinum group element (PGE) mineralization were investigated in the Lower and Middle Group chromitite layers LG6, LG6a, MG1, MG2, and MG2 II from vertical drill core profiles at the Thaba mine in the northwestern limb of the Bushveld Complex. We present detailed geochemical profiles of chromite composition and chromite crystal size distribution curves to shed light on the processes of chromite accumulation and textural modification as well as mineralization. Multiple samples within each layer were assayed for PGE concentrations, and the respective platinum group mineral association was determined by mineral liberation analysis (MLA). There is strong evidence for postcumulus changes in the chromitites. The crystal size distribution curves suggest that the primary chromite texture was coarsened by a combination of adcumulus growth and textural equilibration, while compaction of the crystal mush played only a minor role. Mineral compositions were also modified by postcumulus processes, but because of the very high modal amount of chromite and its local preservation in orthopyroxene oikocrysts, that phase retained much primary information. Vertical variations of chromite composition within chromitite layers and from one layer to another do not support the idea of chromite accumulation from crystal-rich slurries or crystal settling from a large magma chamber. Instead, we favor a successive buildup of chromitite layers by repeated injections of relatively thin layers of chromite-saturated magmas, with in situ crystallization occurring at the crystal mush-magma interface. The adcumulus growth of chromite grains to form massive chromitite required addition of Cr to the layers, which we attribute to downward percolation from the overlying magma. The PGE concentrations are elevated in all chromitite layers compared to adjacent silicate rocks and show a systematic increase upward from LG6 (avg 807 ppb Ir + Ru + Rh + Pt + Pd + Au) to MG2 II (avg 2,062 ppb). There are also significant internal variations in all layers, with enrichments at hanging and/or footwalls. The enriched nature of chromitites in PGEs compared to host pyroxenites is a General feature, independent of the layer thickness. The MLA results distinguish two principal groups of PGE mineral associations: the LG6, LG6, and MG1 are dominated by the malanite series, laurite, and PGE sulfarsenides, while the MG2 and MG2 II layers are characterized by laurite and PGE sulfides as well as Pt-Fe-Sn and PGE-Sb-Bi-Pb alloys. Differences in the PGE associations are attributed to postcumulus alteration of the MG2 and MG2 II layer, while the chromitites below, particularly LG6 and LG6a, contain a more pristine association. KW - Bushveld Complex KW - Chromitites KW - Platinum PY - 2019 U6 - https://doi.org/10.5382/econgeo.4641 SN - 0361-0128 VL - 114 IS - 3 SP - 569 EP - 590 PB - Society of Economic Geologists AN - OPUS4-48145 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogel, Christian A1 - Hoffmann, Marie A1 - Krüger, O. A1 - Murzin, V. A1 - Caliebe, W. A1 - Adam, Christian T1 - Chromium (VI) in phosphorus fertilizers determined with the diffusive gradients in thin-films (DGT) technique N2 - Phosphorus (P) fertilizers from secondary resources became increasingly important in the last years. However, these novel P-fertilizers can also contain toxic pollutants such as chromium in its hexavalent state (Cr(VI)). This hazardous form of chromium is therefore regulated with low limit values for agricultural products even though the correct determination of Cr(VI) in these fertilizers may be hampered by redox processes, leading to false results. Thus, we applied the novel diffusive gradients in thin-films (DGT) technique for Cr(VI) in fertilizers and compared the results with the standard wet chemical extraction method (German norm DIN EN 15192) and Cr K-edge X-ray Absorption near-edge structure (XANES) spectroscopy. We determined an overall good correlation between the wet chemical extraction and the DGT method. DGT was very sensitive and for most tested materials selective for the analysis of Cr(VI) in P-fertilizers. However, hardly soluble Cr(VI) compounds cannot be detected with the DGT method since only mobile Cr(VI) is analyzed. Furthermore, Cr K-edge XANES spectroscopy showed that the DGT binding layer also adsorbs small amounts of mobile Cr(III) so that Cr(VI) values are overestimated. Since certain types of the P fertilizers contain mobile Cr(III) or partly immobile Cr(VI), it is necessary to optimize the DGT binding layers to avoid aforementioned over- or underestimation. Furthermore, our investigations showed that the Cr K-edge XANES spectroscopy technique is unsuitable to determine small amounts of Cr(VI) in fertilizers (below approx. 1% of Cr(VI) in relation to total Cr). KW - Phosphorus fertilizer KW - Sewage sludge ash KW - Diffusive Gradients in thin films (DGT) KW - Chemical extraction KW - XANES spectroscopy PY - 2020 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-509578 SN - 0944-1344 VL - 27 SP - 24320 EP - 24328 PB - Springer AN - OPUS4-50957 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Vogel, Christian A1 - Hoffmann, Marie A1 - Taube, Mareike A1 - Krüger, O. A1 - Baran, R. A1 - Adam, Christian T1 - Uranium and thorium species in phosphate rock and sewage sludge ash based phosphorus fertilizers N2 - Phosphorus (P) is an essential element for all forms of life and is thus often applied as phosphate rock-based P-fertilizers in agriculture to enable continuous farming. However, these P-fertilizers contain also hazardous uranium (U) and thorium (Th), up to 660 and 220 mg/kg, respectively. On the contrary, novel P-fertilizers made from sewage sludge (ash) contain only low mass fractions of U and Th. In addition to the total amount of U and Th in P-fertilizers, their mobility and bioavailability is important, which depends to a large extent on their chemical state, especially oxidation state and chemical bonding. Thus, we analyzed their chemical state in various P-fertilizers by U and Th L3-edge HERFD-XANES spectroscopy. Phosphate rocks and sewage sludge-based P-fertilizers contain mainly U(IV) compounds which have only a low bioavailability. In contrast, acidic treatment of phosphate rock to produce super phosphates lead to an oxidation to U(VI) compounds (including formation of uranium phosphates) with a strongly increased bioavailability. On the contrary, all analyzed P-fertilizers contain Th in form of strongly insoluble phosphates and oxides with a low bioavailability. Additionally performed water extractions and Diffusive Gradients in Thin-films (DGT) experiments support these findings. KW - Phosphorus fertilizer KW - Sewage sludge KW - X-ray absorption near-edge structure (XANES) spectroscopy KW - Diffusive Gradients in Thin-films (DGT) KW - Extraction PY - 2020 U6 - https://doi.org/10.1016/j.jhazmat.2019.121100 SN - 0304-3894 VL - 382 SP - 121100, 1 EP - 6 AN - OPUS4-48872 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Hoffmann, Marie A1 - Vogel, Christian A1 - Adam, Christian A1 - Stephan-Scherb, Christiane A1 - Hecht, Lutz T1 - Novel approaches to Sc species investigation in bauxite residues by x ray absorption near edge structure spectroscopy N2 - In a rapidly evolving world, the demand on raw materials is increasing steadily and many technologies are dependent on a secure supply of hi-tech metals. Recently, scandium (Sc) has attracted attention since its use in high strength Al-alloys and solid-oxide-fuel-cells strongly improves the performance of those materials. The element Sc is not exceptionally rare but quite resistant to geochemical enrichment processes, it is scarcely found enriched to high concentrations and is recovered as a by-product. Since Sc enrichment in Greek bauxite residues was shown by Ochsenkühn-Petropoulou et. al (1994), intensive research on this material and development of efficient Sc-recovery methods is ongoing. This study investigates Sc-bearing species in bauxite residues from alumina production. It aims to provide direct evidence about the Sc-speciation’s in those secondary resources and tries to find the link to speciation’s in primary resources, e.g. bauxites and laterites. Therefore, Sc K edge XANES (X-ray absorption near edge structure) spectroscopy is performed using synchrotron radiation to determine the presence of certain Sc-components and distinguish between adsorbed and chemically bonded Sc as was shown for lateritic deposits in Australia by Chassé et al. 2016. For comparison, reference standards of Sc-bearing and Sc-adsorbed species are synthesized. Indirect inferences from leaching behavior of bauxites, in cases supported by analyses with LA-ICP-MS, suggest Sc to be associated with either iron- or aluminum phases (Vind et al. 2017); (Suss et al.). It remains unclear how different primary materials influence Sc-speciation in the bauxite residue. Therefore, a comparison between different European bauxite residues is made in this study. The investigations should help to understand Sc chemistry and behavior in different primary and secondary materials and provide fundamentals for metallurgical processing. The research is incorporated in the SCALE project (GA No. 730105) funded by EU Horizon 2020 research and innovation program. T2 - DMG Tagung GeoMünster CY - Westfälische Wilhelms-Universität Münster, Germany DA - 22.09.2019 KW - Scandium KW - Bauxite Residue KW - Red Mud KW - XANES PY - 2019 AN - OPUS4-49389 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Hoffmann, Marie A1 - Adam, Christian T1 - Recovery potential of Scandium and other critical raw materials from European industrial by-products N2 - Technological evolution and modern advances in the field of renewable energies are connected to an increasing demand on critical raw materials and especially technological metals. Recently, interest in the element scandium (Sc) has started to grow due to its positive influence on material properties e.g. in high performance-alloys, solid-oxide-fuel cells and solid-state lasers. Therefore, a rise in value and demand is expected in the near future. This study focuses on the reliable and sufficient methodology of measuring Sc and other critical raw materials in secondary waste products from the Al2O3- and Ti2O producing industry. It also targets the examination of Sc-bearing phases and their potential influence in the recovery of Sc from above mentioned materials. Essentially, chemical and structural analyses and characterization of European red muds and its Sc-bearing mineral phases are carried out. Furthermore, analogue investigations are performed for filter cakes and acid slurries that incur during TiO2 production. Red muds and TiO2 filter cakes from several European countries have been analyzed by X-ray diffraction, X-ray-fluorescence, ICP-MS and -OES. Analytical procedures performed are based on previous studies and different methods are tested and compared to ensure reliable data from ICP-MS and -OES measurements. Red mud samples were found to contain ~60-100 mg/kg Sc. Main mineral phases are Hematite, Gibbsite, Boehmite, Cancrinite, Diaspore, Perovskite, Rutile, Katoite and Quartz in variable amounts. Samples from TiO2-production contain up to 400 mg/kg of Sc and significant amounts of niobium and cerium. The main mineral phases are Rutile, Calcite, Quartz, Graphite and Iron-Oxide-Chloride. Generally, it is assumed that Sc is associated with iron and titanium-bearing phases such as Ilmenite and Rutile as it was found in REE deposits in China. Hence, These phases are studied in more detail with advanced structural analyses such as X-ray Absorption near edge structure (XANES) and point-based mineral chemistry analyses by electron microprobe. The study is incorporated in the SCALE project (GA No. 730105) funded by European Union's Horizon 2020 research and innovation program and aims to secure a European supply chain for Sc from metallurgical by-products. T2 - GeoBremen 2017 CY - Bremen, Germany DA - 24.09.2017 KW - Red mud KW - Critical raw materials KW - Industrial byproducts PY - 2017 AN - OPUS4-43452 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Hoffmann, Marie A1 - Adam, Christian T1 - Scandium and scandium-aluminium alloy production from European metallurgical by-products N2 - The SCALE Project is a Horizon2020 Project (GA°730105) that aims to develope a secure supply chain for Scandium in Europe. To achieve that, the whole value chain is investigated and new methodologies and techniques are being developed. In BAM we are characterizing potential Scandium-bearing industrial by-products. T2 - Poster presentation during Exploration Geology Short Course DMG CY - Freiburg, Germany DA - 19.02.2018 KW - Scandium KW - Red Mud KW - Aluminium KW - SCALE PY - 2018 AN - OPUS4-46539 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Hoffmann, Marie A1 - Adam, Christian T1 - Scandium in industriellen Reststoffen - Die Suche nach der Nadel im Heuhaufen N2 - Im Zusammenhang mit dem Horizon2020 geförderten Projekt SCALE (GA°730105) untersuchen wir an der BAM die Scandium Spezies in industriellen Restsoffen wie zum Beispiel Rotschlamm. Dabei kommen Methoden wie Elektronenmikroskopie, LA-ICP-MS und auch X-ray Adsorption near edge structure an Synchrotron-Lichtquellen zum Einsatz. Das Verständnis der Bindungsformen des Scandiums soll im Weiteren helfen, metallurgische Gewinnungsmethoden zu verbessern und anzupassen. T2 - Posterpräsentation während des Themenfeldtags Umwelt CY - Berlin, Germany DA - 18.10.2018 KW - Scandium KW - Rotschlamm KW - Aluminium KW - SCALE PY - 2018 AN - OPUS4-46540 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -