Thomas Kerestedjian

Oxygen-bearing platinum group minerals (O-bearing PGMs) are intergrown with base metal sulfides (BMS, e.g., pentlandite–[NiFe]₉S₈) within fractures in chromite grains from chromitite bodies on Ouen Island, New Caledonia. These PGMs are hosted in chlorite and serpentine, which formed during serpentinization of olivine and pyroxene. The O-bearing PGM grains are polygonal, show microfracturing (indicating volume loss), and contain Pt-Pd-rich sulfide remnants, suggesting pseudomorphic replacement of primary (magmatic) sulfides. They display chemical zonation, with Pt(-Pd-Ni-Fe) relict sulfide cores replaced by Pt-Fe-Ni oxidized alloy mantles and Pt-Cu-Fe(-Pd) alloy rims (tulameenite), indicating desulfurization. The core and mantle show a nanoporous structure, interpreted as the result of coupled dissolution–reprecipitation reactions between magmatic sulfides and low fO₂–fS₂ serpentinite-related fluids, probably formed during olivine transformation to serpentine + magnetite (early stages of serpentinization). This fluid infiltrated magmatic sulfides (PGE-rich and BMS), degrading them to secondary products and releasing S and metals that were accommodated in the mantle and rim of O-bearing PGMs. Upon olivine exhaustion, an increase in fO₂ might have stabilized Pt-Fe-O compounds (likely Pt⁰/Pt-Fe + Fe oxyhydroxides) alongside Ni-Fe alloys. Our results show that post-magmatic desulfurization of primary sulfides produces complex nano-scale intergrowths, mainly driven by changes in the fluid’s physicochemical properties during serpentinization.

The raw materials obtained from the Earth’s crust (Geomaterials) are of fundamental importance for a wide range of industries

The Rietveld method using X-ray powder diffraction data was applied to selected skarn samples for quantitative determination of the present minerals. The specimens include garnet, clinopyroxene–garnet, plagioclase–clinopyroxene–wollastonite–garnet, plagioclase–clinopyroxene–wollastonite, plagioclase–clinopyroxene–wollastonite–epidote, and plagioclase–clinopyroxene skarns. The rocks are coarse- to fine-grained and characterized by an uneven distribution of the constituent minerals. The traditional methods for quantitative analysis (point-counting and norm calculations) are not applicable for such inhomogeneous samples containing minerals with highly variable chemical compositions. Up to eight individual mineral phases have been measured in each sample. To obtain the mineral quantities in the skarn rocks preliminary optical microscopy and chemical investigation by electron probe microanalysis (EPMA) were performed for the identification of some starting components for the Rietveld analysis and to make comparison with the Rietveld X-ray powder diffraction results. All of the refinements are acceptable, as can be judged by the standard indices of agreement and by the visual fits of the observed and calculated diffraction profiles. A good correlation between the refined mineral compositions and the data of the EPMA measurements was achieved.

The present study demonstrates the capabilities of the Rietveld procedure to track the structural transformations and framework flexibility on the example of the natural water-containing zirconosilicate elpidite, subjected (in bulk) to thermal treatment from room temperature to 300 °C. The methodological approach to the performed refinements and the obtained results are in accordance with the previously reported data from in situ single crystal X-ray diffraction studies on heated samples of the same mineral. More light has been drawn on the temperature interval in which the non-reconstructive topotactic phase transition occurs upon partial dehydration. The framework flexibility observed as a response to the water loss and subsequent thermal expansion was evaluated in terms of intentionally introduced set of geometric parameters characterizing the spatial orientation of symmetrically related zirconium octahedra in the structure, the coordination polyhedra volumes, their distortion indices, and bond angle variances.

Chiprovtsi silver-lead and Martinovo iron mines represent the biggest mining area in Northwestern Bulgaria, which was operated till 1999. Their long-lived operation leads to proved pollution of the environment in the vicinity of the mines, especially water and soil. Seasonal monitoring of heavy metal (Cu, Zn, Cd and Pb) and metalloid (As and Sb) concentrations in mine, surface (river) and drinking waters was carried out during May and August 2006 to determine the level of contamination of the Chiprovska Ogosta river basin resulting from the long-lived mining activity and whether these abandoned mines continue to be potential source for water pollution. This study proves significant As concentrations in mine (up to 170 μg/l) and surface waters (between 50 and 621 μg/l). The presence of other heavy metals, such as Cu, Cd, Zn and Pb, and metalloid — Sb is also recorded. Among them, Pb was found in considerable concentrations - up to 1456 pg/l during May 2006 sampling exhibiting great concentration variability between dry and wet sampling seasons. Sb is also determined in mine waters (up to 25 pg/l), but not exists in surface and drinking waters. Drinking waters are proved to be free of heavy metals and metalloids.