The molecular mechanism of Mo isotope fractionation during adsorption to birnessite

Fractionation of Mo isotopes during adsorption to manganese oxides is a primary control on the global ocean Mo isotope budget. Previous attempts to explain what drives the surprisingly large isotope effect δ^97/95Mo_dissolved-δ^97/95Mo_adsorbed=1.8‰ have not successfully resolved the fractionation mechanism. New evidence from extended X-ray absorption fine structure analysis and density functional theory suggests that Mo forms a polymolybdate complex on the surfaces of experimental and natural samples. Mo in this polynuclear structure is in distorted octahedral coordination, while Mo remaining in solution is predominantly in tetrahedral coordination as . Our results indicate that the difference in coordination environment between dissolved Mo and adsorbed Mo is the cause of isotope fractionation. The molecular mechanism of metal isotope fractionation in this system should enable us to explain and possibly predict metal isotope effects in other systems where transition metals adsorb to mineral surfaces.     

Diagenesis of diatomite from the Kolubara Coal Basin,Baroševac,Serbia

Diatomite associated with the Kolubara Coal Basin was studied to better understand early stage silica diagenesis of shallow water deposits. The Kolubara Basin consists of Neogene siliciclastic rocks, diatomite, marlstone and rare carbonates. Palaeozoic metamorphic and Mesozoic sedimentary and igneous basement rocks are transgressively overlain by Upper Miocene sandstone, siltstone, shale and mudstone. This Upper Miocene section is transgressively overlain by the Pontian section, which contains diatomite and coal beds. White and grey diatomite forms beds 0.7-2.2 m thick that are continuous over an area of about 2 km². Siliceous rocks vary in composition from diatomite (81-89 per cent SiO₂) to diatom-bearing shale (58-60 per cent SiO₂). Siliceous deposits are laminated in places, with the laminae defined by variations in clay minerals, organic matter and diatoms. Diatomite shows only incipient diagenesis characterized by the fragmentation of diatom frustules, the minor to moderate corrosion of frustules and the formation of minor amounts of opal-A' (X-ray amorphous inorganic opal) cement. The low degree of diagenesis results from the young age of the deposits, low burial temperatures and possibly also from the presence of abundant organic matter and the dissolution of kaolinite. The presence of only weak diagenesis is also reflected by the characteristically poor consolidation of the rocks and low rank of the associated coal.