H.C. Oskierski

Formation of weathering-derived magnesite deposits in the New England Orogen, New South Wales, Australia: Implications from mineralogy, geochemistry and genesis of the Attunga magnesite deposit

Nodular, cryptocrystalline, weathering-derived magnesite deposits in the New England Orogen, Australia, provide a significant source of high-purity magnesite. Common textural features and related isotopic fingerprints indicate a close genetic relationship between weathering-derived magnesite deposits hosted by ultramafic rocks at Attunga and by sediments at Kunwarara while silica-carbonate rock alteration and rare hydrothermal magnesite vein deposits reflect contrasting conditions of formation. Localised weathering of carbonates in a soil environment shifts stable isotopic composition towards low δ13C and high δ18O typical for weathering-derived magnesites while intrusion-related fluids do not significantly change the isotopic composition of affected carbonates. At Attunga, magnesite consists of irregular, nodular veins and masses filling faults and cracks in the weathered serpentinite host rock as well as soft powdery magnesite in pervasive serpentinite alteration zones. The high-grade magnesite at Attunga can be contaminated by amorphous silica and serpentine relicts but does not contain dolomite or ferroan magnesite as observed for its hydrothermal equivalent, the Piedmont magnesite deposit, or other widespread deposits of silica-carbonate rock in the Great Serpentinite Belt. Heavy δ18O values are compatible with a supergene formation from meteoric waters while low δ13C suggests C3-photosynthetic plants as the predominant source of carbon for the Attunga magnesites. We infer that weathering-derived, nodular magnesite deposits hosted in ultramafic rocks like the Attunga magnesite deposit have formed in a two-step process involving the hypogene formation of a pre-cursor magnesite deposit and complete supergene overprinting by meteoric waters that acquired carbon from percolation through soil.

Decomposition of selected chlorinated volatile organic compounds by ceria (CeO2)

Chlorinated volatile organic compounds (CVOCs) are toxic chemical entities emitted invariably from stationary thermal operations when a trace of chlorine is present. Replacing the high-temperature destruction operations of these compounds with catalytic oxidation has led to the formulation of various potent metal oxides catalysts; among them are ceria-based materials. Guided by recent experimental measurements, this study theoretically investigates the initial steps operating in the interactions of ceria surface CeO2(111) with three CVOC model compounds, namely chloroethene (CE), chloroethane (CA) and chlorobenzene (CB). We find that, the CeO2(111) surface mediates fission of the carbon–chlorine bonds in the CE, CA and CB molecules via modest reaction barriers. As a result of localization of excess electrons left behind after creation of oxygen vacancies, analogous fission over an oxygen vacant surface systematically necessitates lower energy barriers. Dehydrochlorination of CE and CA molecules preferentially proceeds via a dissociative addition route; however, subsequent desorption of vinyl and ethyl moieties requires less energy than surface assisted β C–H bond breakage. The profound stability of hydrocarbon species on the surface contributes to the observed deactivation of ceria at temperatures as low as 580 K under pyrolytic conditions. Adsorption of an oxygen molecule at an oxygen vacant site initiates decomposition of the adsorbed phenyl moiety. Likewise, adsorbed surface hydroxyl groups serve as the hydrogen source in the observed conversion of CB into benzene. A plausible mechanism for the formation of 1,4-dichlorobenzene incorporates abstraction of a para hydrogen in the CB molecule by an O− surface anion followed by chlorine transfer from the surface. Plotted conversion–temperature profiles via a simplified kinetic model against corresponding experimental profiles exhibit a reasonable agreement. The results from this study could be useful in the ongoing efforts to improve cerias catalytic capacity for destroying CVOCs.