Grain boundary diffusion in enstatite

We have investigated grain boundary diffusion rates in enstatite by heating single crystals of quartz packed in powdered San Carlos olivine (Mg_0.90Fe_0.10)₂SiO₄ at controlled oxygen fugacities in the range 10^?5.7 to 10^?8.7?atm and temperatures from 1350° to 1450?°C for times from 5 to 100?h at 1?atm total pressure. Following the experiments, the thickness of the coherent polycrystalline reaction rim of pyroxene that had formed between the quartz and olivine was measured using backscatter scanning imaging in the electron microprobe. Quantitative microprobe analysis indicated that the composition of this reaction phase is (Mg_0.92Fe_0.08)₂Si₂O₆. The rate of growth of the pyroxene increases with increasing temperature, is independent of the oxygen fugacity, and is consistent with a parabolic rate law, indicating that the growth rate is controlled by ionic diffusion through the pyroxene rim. Microstructural observations and platinum marker experiments suggest that the reaction phase is formed at the olivine-pyroxene interface, and is therefore controlled by the diffusion of silicon and oxygen. The parabolic rate constants determined from the experiments were analyzed in terms of the oxide activity gradient across the rim to yield mean effective diffusivities for the rate-limiting ionic species, assuming bulk transport through the pyroxene layer. These effective diffusivities are faster than the lattice diffusivities for the slowest species (silicon) calculated from creep experiments, but slower than measured lattice diffusivities for oxygen in enstatite. Thus, silicon grain boundary diffusion is most likely to be the rate-limiting process in the growth of the pyroxene rims. Also, as oxygen transport through the pyroxene rims must be faster than silicon transport, diffusion of oxygen along the grain boundaries must be faster than through the lattice. The grain boundary diffusivity for silicon in orthopyroxenite is then given by D¯gbSiδ=(3.3±3.0)×10^?9f0.0O₂e^?400±65/RT?m³s^?1, where the activation energy for diffusion is in kJ/mol, and δ is the grain boundary width in m. Calculated growth rates for enstatite under these conditions are significantly slower than predicted by an extrapolation from similar experiments performed at 1000?°C under high pressure (hydrous) conditions by Yund and Tullis (1992), perhaps due to water-enhancement of diffusion in their experiments.     

A techno-economic comparison of power systems for autonomousunderwater vehicles

This paper compares lead-acid batteries, sodium-sulfur batteries, solid polymer fuel cells and closed-cycle diesel engines for autonomous underwater vehicle (AUV) applications. The service is described in terms of a parametric mission and life cycle. A generic AUV is used as a basis for comparison. Power systems are evaluated by two criteria: (1) submerged endurance capability and (2) life cycle cost. This study determines categories of service for which each power system is preferred. The solid polymer fuel cell can provide greater submerged endurance than other power systems examined. For extremely long duration AUV missions, the fuel cell is the required system, indicating a possible market niche for today's fuel cell technology. Considering cost projections for each power system, the results also show that the SPFC can become cost-competitive with conventional technologies, particularly for services characterized by high levels of utilization     

Metamorphic evolution of exhumed middle to lower crustal rocks in the Mojave Extensional Belt, southern California, USA

The Waterman Metamorphic Complex of the central Mojave Desert was exposed as a consequence of early Miocene detachment-dominated extension. However, it has evidence consistent with a more extensive geological history that involves collision of a crustal fragment(s), tectonic thickening by overthrusting and two periods of extension. The metamorphic complex contains granitoid intrusives and felsic mylonitic gneisses as well as polymetamorphic rocks that include marble, calc-silicate, quartzite. mafic granulite, pyribolite, amphibolite, migmatite and biotite schist. The latter group of rocks was affected by an initial series of high-grade metamorphic events (M1 and M2) and a localized lower grade overprint (M3). The initial metamorphism (M1) can be separated into two stages along its high-grade P–T path: M1a, a granulite facies metamorphism at 800–850° C and 7.5–9 kbar and Mlb, an upper amphibolite facies overprint at 750–800° C and 10–12 kbar. M1a developed mineral assemblages and textures consistent with granulite facies conditions at a reduced activity of H₂O and is associated with intense ductile deformation (D1) and minor local partial melting. M1b overprinted the granulite assemblages with a series of hydrous phases under conditions of increasing pressure and H₂O activity and is accompanied by little or no deformation. M2 developed at lower pressures and temperatures (650–750° C, 4.5–5.5 kbar) and is distinguished by a second local overprint of hydrous phases that reflects an input of aqueous fluids probably associated with the intrusion of a series of granitic dykes and veins. Effects of M3 are confined to the Mitchel detachment zone, an anastomosing early Miocene detachment fault, and are characterized by local ductile/brittle deformation (D2) of the pre-existing high-grade rocks and granitoid intrusives and by the production of mylonites and mylonitic gneisses under greenschist facies conditions (300–350° C, 3–5 kbar). The initial overprint (M1a) represents metamorphism, devolatilization and minor partial melting of supracrustal rocks under granulite facies conditions as a consequence of tectonic and, possibly, magmatic thickening. The increasing pressure transition of M1a to M1b reflects a period of continued compressional tectonism, thrusting and influx of H₂O, in part, locally related to crystallization of partial melts. The near isothermal decompression between M1b and M2 probably represents a pre-112-Ma extensional episode that may have been the result of a decompressional readjustment of a thickened crust. Following the initial extensional event, the metamorphic complex remained at depths of 10–17 km for at least 90 Ma until it was uplifted following Miocene extension. M3 develops locally in response to this second extensional period resulting from the early Miocene detachment faulting.     

Recurrent Red-tides in the Southampton Water Estuary Caused by the Phototrophic CiliateMesodinium rubrum

In the Southampton Water estuary (southern England, U.K.), red-tides caused by the planktonic, phototrophic ciliateMesodinium rubrum(=Myrionecta rubra) occur during most summers and sometimes in autumn. These events were investigated in detail between 1985 and 1987 and were characterized by levels of chlorophylla(chl a) of over 100 μg l⁻¹, cell numbers ofM. rubrumof over 1×10³ ml⁻¹, oxygen saturations of around 150%, and depleted numbers of macrozooplankton. Initiation of red-water did not appear to be triggered by irradiance or nutrients, but coincided with an increase in temperature and water column stability. This enhanced stability was promoted by increased surface to bottom gradients of both temperature and salinity, and by reduced mixing during neap tides. Development of red-water was accompanied by removal of most of the dissolved NH⁺₄from the water column, whereas some NO⁻₃persisted, presumably maintained by freshwater input. NO⁻₃and NH⁺₄gradually returned to pre-bloom concentrations as the red-water declined in late summer. Maximal biomass ofM. rubrumappeared to be limited by irradiance, and self-shading probably imposed an upper limit of around 300 mg chl a m⁻²within the water column. At the observed levels of chl a, irradiance values within the population maximum between 1 and 3 m depth were only just of the order (≈15 μmol photons m⁻² s⁻¹) required to balance estimated respiratory demands. Oxygen concentration became undersaturated during the late bloom phase, with minimal values of 20–30% saturation recorded in deeper waters; however, despite this and reduced numbers of macrozooplankton, direct deleterious effects on other organisms were not observed.     

Trace-element contents and cathodoluminescence of “trapiche” rubies from Mong Hsu, Myanmar (Burma): geological significance

Summary ?Mong Hsu rubies of the “trapiche” type are sporadically seen in the gem market. However, they have never been described in the field. The study of the nature of solid inclusions, the variation of trace-element contents, as well as the cathodoluminescence behaviour of six “trapiche” rubies permit the conclusion that these rubies crystallised in the same geological environment (marble-type deposit) as the normal rubies from Mong Hsu: (1) Cr and V are the main chromophorous elements in both ruby types; they act, together with Ti, as activators or quenchers for cathodoluminescence; (2) calcite, dolomite, rutile, mica, diaspore, apatite, chlorite, and feldspar are solid inclusions found in both ruby types; (3) the presence of bastn?site in trapiche ruby and fluorite in non-trapiche ruby indicates the circulation of F-bearing fluids during ruby deposition; (4) the distribution of trace-element contents in the crystal is similar for both ruby types. In the Cr₂O₃ vs. Fe₂O₃ and Cr₂O₃ vs. Fe₂O₃/TiO₂ diagrams, the population fields of Mong Hsu “trapiche” and non-“trapiche” rubies overlap. They are distinct from those of rubies and sapphires hosted in basalts from South-east Asia. Received October 30, 2001; revised version accepted March 25, 2002     

A 2000-YEAR CONTEXT FOR MODERN CLIMATE CHANGE

ABSTRACT. Although considerable attention has been paid to the record of temperature change over the last few centuries, the range and rate of change of atmospheric circulation and hydrology remain elusive. Here, eight latitudinally well-distributed (pole-equator-pole), highly resolved (annual to decadal) climate proxy records are presented that demonstrate major changes in these variables over the last 2000 years. A comparison between atmospheric ¹⁴C and these changes in climate demonstrates a first-order relationship between a variable Sun and climate. The relationship is seen on a global scale.     

Coulometric TCO2 analyses for marine studies; an introduction

Progress in the introduction of coulometry for the analysis of total carbon dioxide (TCO₂) in marine waters is described. An extractor—stripper removes CO₂ that is measured coulometrically by the quantity of electricity (coulombs) used to electrogenerate OH^? ions for the titration of the acid formed by the reaction of CO₂ and ethanolamine. The equivalence point is detected photometrically with thymolphthalein as the indicator, and Faraday's Law relates coulombs to equivalents of titrant generated and CO₂ determined so that there are no standard curves needed or titrants to standardize or store. Accuracy was determined by adding gelatin capsules containing 100–1500 μg C of pure CaCO₃ into the stripper, and accuracies of better than ± 1 μg C were achieved. The best precision for natural seawater (± 1 standard error) of ± 0.5 μmol l^?1 was found for 17 samples of Bermuda coastal waters having a mean TCO₂ of 2007.2 μmol l^?1 (0.05% CV). Sources of error and precautions are discussed. This method, which has been used successfully at sea, can be used to study a variety of marine phenomena involving TCO₂.