High‐pressure phase transitions of α‐quartz under nonhydrostatic dynamic conditions: A reconnaissance study at PETRA III

Hypervelocity collisions of solid bodies occur frequently in the solar system and affect rocks by shock waves and dynamic loading. A range of shock metamorphic effects and high‐pressure polymorphs in rock‐forming minerals are known from meteorites and terrestrial impact craters. Here, we investigate the formation of high‐pressure polymorphs of α‐quartz under dynamic and nonhydrostatic conditions and compare these disequilibrium states with those predicted by phase diagrams derived from static experiments under equilibrium conditions. We create highly dynamic conditions utilizing a mDAC and study the phase transformations in α‐quartz in situ by synchrotron powder X‐ray diffraction. Phase transitions of α‐quartz are studied at pressures up to 66.1 and different loading rates. At compression rates between 0.14 and 1.96 GPa s^?1, experiments reveal that α‐quartz is amorphized and partially converted to stishovite between 20.7 GPa and 28.0 GPa. Therefore, coesite is not formed as would be expected from equilibrium conditions. With the increasing compression rate, a slight increase in the transition pressure occurs. The experiments show that dynamic compression causes an instantaneous formation of structures consisting only of SiO₆ octahedra rather than the rearrangement of the SiO₄ tetrahedra to form a coesite. Although shock compression rates are orders of magnitude faster, a similar mechanism could operate in impact events.     

Convective energy transport in stellar atmospheres

The motion of convective cells in an environment which changes rapidly with depth is examined. In such an environment a cell may move through regions with different levels of ionization and with associated differences in heat capacity. The energy equation is cast in a manner which is independent of the history of these cells. The convective flux at a given level of the atmosphere is written as an average over an ensemble of cells originating at a range of other levels. A procedure for correcting the temperature gradient for these non-local effects is described and results for a model solar atmosphere are given. The principal results are: (1) The rms velocity varies smoothly and is non-zero well into the photosphere (e.g.,v _rsm=1.4 km/sec at =0.2); (2) Convective overshoot reduces the radiative flux to 60% and 90% of the total at =2.5 and 0.2 respectively; and (3) The interior adiabat of the convective envelope is less sensitive to the assumed value of the average cell size than in the usual treatment of convection.Supported in part by the National Science Foundation [GP-9433, GP-9114], the Office of Naval Research [Nonr-220(47)], and Air Force Grant AG-AFOSR-171-67.     

The Messinian Sicilian stratigraphy revisited: new insights for the Messinian salinity crisis

Controversies around the Messinian salinity crisis (MSC) are because of the difficulties in establishing genetic and stratigraphic relationships between its deep and shallow‐water record. Actually, the Sicilian foreland basin shows both shallow and deep‐water Messinian records, thus offering the chance to reconstruct comprehensive MSC scenarios. The Lower Gypsum of Sicily comprises primary and resedimented evaporites separated in space and time by the intra‐Messinian unconformity. A composite unit including halite, resedimented gypsum and Calcare di Base accumulated between 5.6 and 5.55 Ma in the main depocentres; it records the acme of the Messinian Salinity Crisis during a tectonic phase coupled with sea‐level falls at glacials TG14‐TG12. These deposits fully post‐date primary gypsum, which precipitated in shallow‐water wedge‐top and foreland ramp basins between 5.96 and 5.6 Ma. This new stratigraphic framework results in a three‐stage MSC scenario characterized by different primary evaporite associations: selenite in the first and third stages, carbonate, halite and potash salt in the second one associated with hybrid resedimented evaporites.     

Transfer and early diagenesis of biogenic silica oxygen isotope signals during settling and sedimentation of diatoms in a temperate freshwater lake (Lake Holzmaar, Germany)

We have investigated the transfer of oxygen isotope signals of diatomaceous silica (δ¹⁸O_diatom) from the epilimnion (0-7 m) through the hypolimnion to the lake bottom (∼20 m) in freshwater Lake Holzmaar, Germany. Sediment-traps were deployed in 2001 at depths of 7 and 16 m to harvest fresh diatoms every 28 days. The 7 m trap collected diatoms from the epilimnion being the main zone of primary production, while the 16 m trap collected material already settled through the hypolimnion. Also a bottom sediment sample was taken containing diatom frustules from approximately the last 25 years. The δ¹⁸O_diatom values of the 7 m trap varied from 29.4‰ in spring/autumn to 26.2‰ in summer according to the temperature dependence of oxygen isotope fractionation and represent the initial isotope signal in this study. Remarkably, despite the short settling distance δ¹⁸O_diatom values of the 7 and the 16 m trap were identical only during spring and autumn seasons while from April to September δ¹⁸O_diatom values of the 16 m trap were roughly ∼1.5‰ enriched in ¹⁸O compared to those of the 7 m trap. Isotopic exchange with the isotopically lighter water of the hypolimnion would shift the δ¹⁸O_diatom value to lower values during settling from 7 to 16 m excluding this process as a cause for the deviation. Dissolution of opal during settling with intact organic coatings of the diatom cells and near neutral pH of the water should only cause a minor enrichment of the 16 m values. Nevertheless, opal from the bottom sediment was found to be 2.5‰ enriched in ¹⁸O compared to the weighted average of the opal from the 7 m trap. Thus, resuspension of bottom material must have contributed to the intermediate δ¹⁸O_diatom signal of the 16 m trap during summer. Dissolution experiments allowed further investigation of the cause for the remarkably enriched δ¹⁸O_diatom value of the bottom sediment. Experiments with different fresh diatomaceous materials show an increase of opaline ¹⁸O at high pH values which is remarkably reduced when organic coatings of the cells still exist or at near neutral pH. In contrast, high pH conditions do not affect the δ¹⁸O_diatom values of sub-fossil and even fossil opal. IR analyses show that the ¹⁸O enrichment of the sedimentary silica is associated with a decrease in Si-OH groups and the formation of Si-O-Si linkages. This indicates a silica dehydroxylation process as cause for the isotopic enrichment of the bottom sediment. Silica dissolution and dehydroxylation clearly induce a maturation process of the diatom oxygen isotope signal presumably following an exponential behaviour with a rapid initial phase of signal alteration. The dynamics of this process is of particular importance for the quantitative interpretation of sedimentary δ¹⁸O_diatom values in terms of palaeothermometry.     

Fluid inclusion study of the Wunugetu Cu–Mo deposit,Inner Mongolia,China

Hydrothermal alteration and mineralization at the Wunugetu porphyry Cu–Mo deposit, China, include four stages, i.e., the early stage characterized by quartz, K-feldspar and minor mineralization, followed by a molybdenum mineralization stage associated with potassic alteration, copper mineralization associated with sericitization, and the last Pb–Zn mineralization stage associated with carbonation. Hydrothermal quartz contains three types of fluid inclusions, namely aqueous (W-type), daughter mineral-bearing (S-type) and CO₂-rich (C-type) inclusion, with the latter two types absent in the late stage. Fluid inclusions in the early stage display homogenization temperatures above 510°C, with salinities up to 75.8 wt.% NaCl equivalent. The presence of S-type inclusions containing anhydrite and hematite daughter minerals and C-type inclusions indicates an oxidizing, CO₂-bearing environment. Fluid inclusions in the Mo- and Cu-mineralization stages yield homogenization temperatures of 342–508°C and 241–336°C, and salinities of 8.6–49.4 and 6.3–35.7 wt.% NaCl equivalent, respectively. The presence of chalcopyrite instead of hematite and anhydrite daughter minerals in S-type inclusions indicates a decreasing of oxygen fugacity. In the late stage, fluid inclusions yield homogenization temperatures of 115–234°C and salinities lower than 12.4 wt.% NaCl equivalent. It is concluded that the early stage fluids were CO₂ bearing, magmatic in origin, and characterized by high temperature, high salinity, and high oxygen fugacity. Phase separation occurred during the Mo- and Cu-mineralization stages, resulting in CO₂ release, oxygen fugacity decrease and rapid precipitation of sulfides. The late-stage fluids were meteoric in origin and characterized by low temperature, low salinity, and CO₂ poor.     

Coesite in suevite from the Ries impact structure (Germany): From formation to postshock evolution

Coesite is one of the most common and abundant high‐pressure phases occurring in impactites. The mechanism of formation of coesite and its postshock evolution is revisited in this paper based on Raman microspectroscopy, and scanning and transmission electron microscopy of a coesite‐bearing suevite from the Ries impact structure. Our data indicate that coesite forms through a single process, i.e., by crystallization from high‐pressure silica melt, and that its formation is related to fluid inclusions in precursor quartz. During the postshock phase, coesite aggregates are partially modified by annealing and interactions with fluids. In an early stage of the postshock evolution, coesite is back‐transformed to quartz and the surrounding diaplectic glass devitrifies into β‐cristobalite, which transforms into α‐cristobalite and then into microcrystalline quartz during subsequent stages of the postshock evolution. Altogether these postshock modifications result in a significant volume loss and extensional fracturing. During a late postshock stage, the fractures are filled with clay minerals due to circulation of hydrothermal fluids.     

Noble gases in mineral separates from three shergottites: Shergotty,Zagami, and EETA79001

Abstract— This study provides a complete data set of all five noble gases for bulk samples and mineral separates from three Martian shergottites: Shergotty (bulk, pyroxene, maskelynite), Zagami (bulk, pyroxene, maskelynite), and Elephant Moraine (EET) A79001, lithology A (bulk, pyroxene). We also give a compilation of all noble gas and nitrogen studies performed on these meteorites. Our mean values for cosmic‐ray exposure ages from ³He, ²¹Ne, and ³⁸Ar are 2.48 Myr for Shergotty, 2.73 Myr for Zagami, and 0.65 Myr for EETA79001 lith. A. Serious loss of radiogenic ⁴He due to shock is observed. Cosmogenic neon results for bulk samples from 13 Martian meteorites (new data and literature data) are used in addition to the mineral separates of this study in a new approach to explore evidence of solar cosmic‐ray effects. While a contribution of this low‐energy irradiation is strongly indicated for all of the shergottites, spallation Ne in Chassigny, Allan Hills (ALH) 84001, and the nakhlites is fully explained by galactic cosmic‐ray spallation. Implanted Martian atmospheric gases are present in all mineral separates and the thermal release indicates a near‐surface siting. We derive an estimate for the ⁴⁰Ar/³⁶Ar ratio of the Martian interior component by subtracting from measured Ar in the (K‐poor) pyroxenes the (small) radiogenic component as well as the implanted atmospheric component as indicated from ¹²⁹Xe, * excesses. Unless compromised by the presence of additional components, a high ratio of ～2000 is indicated for Martian interior argon, similar to that in the Martian atmosphere. Since much lower ratios have been inferred for Chassigny and ALH 84001, the result may indicate spatial and/or temporal variations of ⁴⁰Ar/³⁶Ar in the Martian mantle.