Si diffusion in zircon

Self-diffusion of Si under anhydrous conditions at 1 atm has been measured in natural zircon. The source of diffusant for experiments was a mixture of ZrO₂ and ³⁰Si-enriched SiO₂ in 1:1 molar proportions; experiments were run in crimped Pt capsules in 1-atm furnaces. ³⁰Si profiles were measured with both Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis with the resonant nuclear reaction ³⁰Si(p,γ)³¹P. For Si diffusion normal to c over the temperature range 1,350–1,550°C, we obtain an Arrhenius relation D = 5.8 exp(−702 ± 54 kJ mol⁻¹/RT) m² s⁻¹ for the NRA measurements, which agrees within uncertainty with an Arrhenius relation determined from the RBS measurements [62 exp(−738 ± 61 kJ mol⁻¹/RT) m² s⁻¹]. Diffusion of Si parallel to c appears slightly faster, but agrees within experimental uncertainty at most temperatures with diffusivities for Si normal to c. Diffusion of Si in zircon is similar to that of Ti, but about an order of magnitude faster than diffusion of Hf and two orders of magnitude faster than diffusion of U and Th. Si diffusion is, however, many orders of magnitude slower than oxygen diffusion under both dry and hydrothermal conditions, with the difference increasing with decreasing temperature because of the larger activation energy for Si diffusion. If we consider Hf as a proxy for Zr, given its similar charge and size, we can rank the diffusivities of the major constituents in zircon as follows: D _Zr < D _Si << D _{O, dry} < D _{O, ‘wet’}.     

Estimation of heterogeneous reaction rates for stratospheric trace gases with particular reference to the diffusional uptake of HCl and ClONO2 by polar stratospheric clouds

The stratosphere holds a variety of particulates like polar stratospheric clouds (PSCs) and sulphate aerosols which catalyse chemical reactions. These reactions cause changes in the composition of the stratosphere, including the redistribution of active chlorine which might lead to ozone destruction. As a result during recent years a lot of effort has been directed towards the quantification of the uptake of trace gases like ClONO₂, HCl, etc. into these particulates. However, it has been observed that many of the two and three dimensional models used in such studies are constrained by the lack of adequate rate constant data. This paper describes a theoretical approach to estimate the reaction rate constants for 23 gases on both types of polar stratospheric clouds (type I and II). It is found that for gases like N₂O₅, ClONO₂ and HCl, diffusional uptake is important and contributes significantly to the heterogeneous reaction rate. A complete Lennard-Jones calculation is used to accurately compute the trace gas diffusion coefficients.     

The SHAND quaternary system for evaluating the supersilicic or subsilicic crystal-chemistry of eclogite minerals, and potential new UHPM pyroxene and garnet end-members

Summary The stoichiometry of pyroxenes {^viiiX^{2+ vi}Y^{2+ iv}Z⁴⁺ ₂ O₆} and garnets {^xiiX²⁺ ₃ ^viY³⁺ ₂ ^ivZ⁴⁺ ₃ O₁₂} is re-evaluated by a theoretical crystal-chemical approach that takes into account natural phenomena that do not fit with conventional anhydrous stoichiometric mineralogy: the existence in eclogites of microinclusions of other minerals that may have been exsolved from previous supersilicic or subsilicic UHPM pyroxene or garnet. Different definitions of supersilicic and subsilicic are discussed and the one based on the ability to exsolve SiO₂ and leave behind a stoichiometric pyroxene or garnet is recommended for general adoption. The SHAND system (S = Si et al.; H = H; A = Al et al.; N = Na et al.; D = divalents) for projecting multivariate chemical space involving 23 cations and 104 selected natural or potential mineral species on to two essential diagrams (SAND and SHND) is described in full for the first time. Numerous possible chemical exchanges are considered and justified with respect to known mineral phenomena such as cation vacancies, octahedral silicon or protonation. Several new potential end-members are presented, in particular “supersilipyx”, “supersiligar” and “subsiligar”. It is suggested that small quantities of these end-members can be incorporated into UHPM solid-solutions and lead to various exsolution phenomena during eclogite exhumation.     

Geiger avalanche photodiodes as tentative light detectors for VHE gamma ray astronomy

Due to its sensitivity and speed, the detector still widely used in Cerenkov astrophysics experiments remains the PhotoMultiplier Tube (PMT). For instance, recent pathbreaking experiments in Very High Energy astrophysics (VHE), such as MAGIC and HESS, have used mainstream PMT technology [Aharonian, F. et al Astron. Astrophys. 492(1):L25–L28 (2008)]. Moreover the Cerenkov Telescope Array (CTA) which is now in its design phase, is also planed to be based on PMT’s. However, there are some disadvantages to the PMT technology: the rather poor quantum efficiency, the use of high voltages, the high cost when used in large number in a matrix arrangement and the large weight. Hence, we have investigated the possibility to design future Cerenkov telescopes based on solid state technology, specifically Geiger avalanche photodiodes. In a preliminary development test, we placed HAMAMATSU avalanche photodiodes at the focal plane of a 60 cm diameter telescope at the Pic du Midi in the French Pyrénées, in order to record incident cosmic rays. In this paper, we describe not only the experimental setup but we also put special emphasis to the reduction of the semi-conductor noise. We also show first data that were recorded during two runs in the fall of 2006, and conclude by the presentation of the design of an “integrated, low-cost solid state photodiode arrangement” which might be an alternative to PMT’s for future VHE telescopes.     

The Ar‐Ar age and petrology of Miller Range 05029: Evidence for a large impact in the very early solar system

Abstract– Miller Range (MIL) 05029 is a slowly cooled melt rock with metal/sulfide depletion and an Ar‐Ar age of 4517 ± 11 Ma. Oxygen isotopes and mineral composition indicate that it is an L chondrite impact melt, and a well‐equilibrated igneous rock texture with a lack of clasts favors a melt pool over a melt dike as its probable depositional setting. A metallographic cooling rate of approximately 14 °C Ma^?1 indicates that the impact occurred at least approximately 20 Ma before the Ar‐Ar closure age of 4517 Ma, possibly even shortly after accretion of its parent body. A metal grain with a Widmanstätten‐like pattern further substantiates slow cooling. The formation age of MIL 05029 is at least as old as the Ar‐Ar age of unshocked L and H chondrites, indicating that endogenous metamorphism on the parent asteroid was still ongoing at the time of impact. Its metallographic cooling rate of approximately 14 °C Ma^?1 is similar to that typical for L6 chondrites, suggesting a collisional event on the L chondrite asteroid that produced impact melt at a minimum depth of 5–12 km. The inferred minimum crater diameter of 25–60 km may have shattered the 100–200 km diameter L chondrite asteroid. Therefore, MIL 05029 could record the timing and petrogenetic setting for the observed lack of correlation of cooling rates with metamorphic grades in many L chondrites.     

Robust adaptive control of underactuated ships on a linear course with comfort

This paper addresses an important problem in ship control application—the robust stabilization of underactuated ships on a linear course with comfort. Specifically, we develop a multivariable controller to stabilize ocean surface ships without a sway actuator on a linear course and to reduce roll and pitch simultaneously. The controller adapts to unknown parameters of the ship and constant environmental disturbances induced by wave, ocean current and wind. It is also robust to time-varying environmental disturbances, time-varying change in ship parameters and other motions of the ship such as surge and heave. The roll and pitch can be made arbitrarily small while the heading angle and sway are kept to be in reasonably small bounds. The controller development is based on Lyapunov’s direct method and backstepping technique. A Lipschitz continuous projection algorithm is used to update the estimate of the unknown parameters to avoid the parameters’ drift due to time-varying environmental disturbances. Simulations on a full-scale catamaran illustrate the effectiveness of our proposed controller.     

The carbon isotopic response of algae, (cyano)bacteria, archaea and higher plants to the late Cenomanian perturbation of the global carbon cycle: Insights from biomarkers in black shales from the Cape Verde Basin (DSDP Site 367)

The stable carbon isotopic compositions of free and sulfur (S)-bound biomarkers derived from algae, (cyano)bacteria, archaea and higher plants and total organic carbon (TOC) during the first phase of the late Cenomanian/Turonian oceanic anoxic event (OAE) were measured in black shales deposited in the southern proto-Atlantic Ocean in the Cape Verde basin (DSDP Site 367) to determine the response of these organisms to this major perturbation of the global carbon cycle resulting from widespread burial of marine organic matter. The average positive isotope excursions of TOC and biomarkers varied from 5.1‰ to 8.3‰. The δ¹³C values were cross correlated to infer potential common sources of biomarkers. This revealed common sources for C₃₁ and C₃₂ hopanes but no 1:1 relationship for pristane and phytane. The correlation of δ¹³C_TOC with the δ¹³C value of sulfur (S)-bound phytane is the strongest. This is because S-bound phytane is derived from phytol that originates from all marine primary producers (algae and cyanobacteria) and thus represents a weighted average of their carbon isotopic compositions. The δ¹³C values of S-bound phytane and C₃₅ hopane were also used to estimate pCO₂ levels. Before the OAE burial event, pCO₂ levels are estimated to be ca. 1300 ppmv using both biomarkers and the independent maximum Rubisco fractionation factors. At times of maximum organic carbon burial rates during the OAE, reconstructed pCO₂ levels are estimated to be ca. 700 ppmv. However, compared to other C/T OAE sections the positive isotope excursion of S-bound phytane is also affected by an increased production during the OAE. When we compensate for this, we arrive at pCO₂ levels around 1000 ppmv, a reduction of ca. 25%. This indicates that burial of organic matter can have a large effect on atmospheric CO₂ levels.