A modeling of the structure and favorable H-docking sites and defects for the high-pressure silica polymorph stishovite

Employing first-principles methods, the docking sites for H were determined and H, Al, and vacancy defects were modeled with an infinite periodic array of super unit cells each consisting of 27 contiguous symmetry nonequivalent unit cells of the crystal structure of stishovite. A geometry optimization of the super-cell structure reproduces the observed bulk structure within the experimental error when P1 translational symmetry was assumed and an array of infinite extent was generated. A mapping of the valence electrons for the structure displays mushroom-shaped isosurfaces on the O atom, one on each side of the plane of the OSi₃ triangle in the nonbonded region. An H atom, placed in a cell near the center of the super cell, was found to dock upon geometry optimization at a distance of 1.69 Å from the O atom with the OH vector oriented nearly perpendicular to the plane of the triangle such that the OH vector makes a angle of 91° with respect to [001]. However, an optimization of a super cell with an Al atom replacing Si and an H atom placed nearby in a centrally located cell resulted in an OH distance of 1.02 Å with the OH vector oriented perpendicular to [001] as observed in infrared studies. The geometry-optimized position of the H atom was found to be in close agreement with that (0.44, 0.12, 0.0) determined in an earlier study of the theoretical electron density distribution. The docking of the H atom at this site was found to be 330 kJ mol^–1 more stable than a docking of the atom just off the shared OO edge of the octahedra as determined for rutile. A geometry optimization of a super cell with a missing Si generated a vacant octahedra that is 20% larger than that of the SiO₆ octahedra. The valence electron density distribution displayed by the two-coordinate O atoms that coordinate the vacant octahedral site is very similar to those displayed by the bent SiOSi angles in coesite. The internal distortions induced by the defect were found to diminish rather rapidly with distance, with the structure annealing to that observed in the bulk crystal to within about three coordination spheres.     

Linking gold mineralization to regional-scale drivers of mineral systems using in situ U–Pb geochronology and pyrite LA-ICP-MS element mapping

Proterozoic orogens commonly host a range of hydrothermal ores that form in diverse tectonic settings at different times. However, the link between mineralization and the regional-scale tectonothermal evolution of orogens is usually not well understood, especially in areas subject to multiple hydrothermal events.Regional-scale drivers for mineral systems vary between the different classes of hydrothermal ore, but all involve an energy source and a fluid pathway to focus mineralizing fluids into the upper crust. The Mount Olympus gold deposit in the Proterozoic Capricorn Orogen of Western Australia, was regarded as an orogenic gold deposit that formed at ca. 1738 Ma during the assembly of Proterozoic Australia. However,the trace element chemistry of the pyrite crystals closely resembles those of the Carlin deposits of Nevada,with rims that display solid solution gold accompanied by elevated As, Cu, Sb, Hg, and Tl, surrounding gold-poor cores. New SHRIMP UeP b dating of xenotime intergrown with auriferous pyrite and ore-stage alteration minerals provided a weighted mean~(207) Pb*/~(206) Pb* date of 1769 ± 5 Ma, interpreted as the age of gold mineralization. This was followed by two discrete episodes of hydrothermal alteration at 1727 ± 7 Ma and 1673 ± 8 Ma. The three ages are linked to multiple reactivation of the crustal-scale Nanjilgardy Fault during repeated episodes of intracratonic reworking. The regional-scale drivers for Carlin-like gold mineralization at Mount Olympus are related to a change in tectonic regime during the final stages of the intracratonic 1820 -1770 Ma Capricorn Orogeny. Our results suggest that substantial sized Carlin-like gold deposits can form in an intracratonic setting during regional-scale crustal reworking.     

Quantifying flows along hydrological pathways by applying a new filtering algorithm in conjunction with master recession curve analysis

Quantifying the proportion of the river hydrograph derived from the different hydrological pathways is essential for understanding the behaviour of a catchment. This paper describes a new approach using the output from master recession curve analysis to inform a new algorithm based on the Lyne and Hollick ‘one‐parameter’ signal analysis filtering algorithm. This approach was applied to six catchments (including two subcatchments of these) in Ireland. The conceptual model for each catchment consists of four main flow pathways: overland flow, interflow, shallow groundwater and deep groundwater. The results were compared with those of the master recession curve analysis, a recharge coefficient approach developed in Ireland and the semi‐distributed, lumped and deterministic hydrological model Nedbør‐Afstrømings‐Model. The new algorithm removes the ‘free variable’ aspect that is typically associated with filtering algorithms and provides a means of estimating the contribution of each pathway that is consistent with the results of hydrograph separation in catchments that are dominated by quick response pathways. These types of catchments are underlain by poorly productive aquifers that are not capable of providing large baseflows in the river. Such aquifers underlie over 73% of Ireland, ensuring that this new algorithm is applicable in the majority of catchments in Ireland and potentially in those catchments internationally that are strongly influenced by the quick‐responding hydrological pathways. Copyright © 2013 John Wiley & Sons, Ltd.     

The Moon

Recent geochemical and geophysical data from the Moon enable a revision of earlier interpretations regarding lunar origin, structure and bulk composition. Earth and Moon show many similarities among their isotopic compositions, but they have evolved in totally dissimilar ways, probably related to the deficiency of water and volatile elements in the Moon as well as the vast differences in size and internal pressure. Some global geochemical differences from the Earth such as volatile depletion based on K/U ratios have been established. However, all current lunar samples come from differentiated regions, making the establishment of a bulk composition more reliant on bulk geophysical properties or isotopic similarities; it remains unclear how the latter arose or relate to whole Moon composition. The lack of fractionation effects among the refractory and super-refractory elements indicates that the proto-lunar material seems unlikely to have been vaporized while the presence of volatile elements may place lower limits on proto-lunar temperatures. The apparent lack of geochemical evidence of an impacting body enables other possible impactors, such as comets, to be considered. Although the origin of the Moon remains currently unknown, it is generally believed that the Moon originated as the result of a giant impact on the Earth.