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PubMed1989

Interplanetary dust particles collected in the stratosphere: observations of atmospheric heating and constraints on their interrelationships and sources.

The majority of the interplanetary dust particles (IDPs) collected in the stratosphere belong to one of three major classes, the first two dominated by the anhydrous minerals olivine and pyroxene, and the third by hydrous layer-lattice silicates. Infrared spectroscopy and transmission electron microscopy studies show that the different IDP classes represent different types of dust that exist as individual particles in interplanetary space. The majority of the collected IDPs smaller than 30 micrometers in diameter in the layer-lattice silicate and pyroxene classes appear not to have been heated to temperatures above 600 degrees C during atmospheric entry. The relatively low maximum temperatures experienced by these IDPs during atmospheric entry imply that they arrive at the top of the atmosphere with low geocentric encounter velocities. This limits the possible encounter trajectories for these particles to relatively circular, prograde orbits. As a result, it is unlikely that these IDPs are from Earth-crossing comets or asteroids. Asteroids, and comets having low inclinations and perihelia outside 1.2 AU, appear to be the best candidates for the parent bodies of the pyroxene and layer-lattice silicate particles. Chemical and mineralogical information suggests that the pyroxene-rich IDPs are from comets and the layer-lattice silicate-rich IDPs are from asteroids. The collected IDPs dominated by olivine appear to include a larger fraction of particles heating above 600 degrees C, suggesting that these particles were captured from more eccentric orbits. This, and the observation of the infrared spectral features of olivine in several comets suggest these particles have a cometary origin. Since much of the collected dust has apparently been captured from nearly circular, prograde orbits and since there are no appropriate parent bodies presently in such orbits, these results provide an experimental confirmation that the Poynting-Robertson effect exists as a nongravitational force important in the orbital evolution of dust in the Solar System.

Atmosphere↗
PubMed1991

Are some chondrule rims formed by impact processes? Observations and experiments.

Observations and experimental evidence are presented to support the hypothesis that high-speed impact into a parent body regolith can best explain certain textures and compositions observed for rims on some chondrules. A study of 19 interclastic rimmed chondrules in the Weston (H 3/4) ordinary chondrite shows that two main rim types are present on porphyritic olivine-pyroxene (POP) and porphyritic pyroxene (PP) chondrules: granular and opaque rims. Granular rims are composed of welded, fine-grained host chondrule fragments. Bulk compositions of granular rims vary among chondrules, but each rim is compositionally dependent on that of the host chondrule. Opaque rims contain mineral and glass compositions distinctly different from those of the host, partially reacted chondrule mantle components, and some matrix grains. Opaque rims are greatly enriched in FeO (up to 63 wt%). The original chondrule pyroxene compositional zonation patterns and euhedral grain outlines are discontinuous at the chondrule/rim interface. Opaque rims are dominated by fayalitic olivine (Fa92-56), with high Al2O3 content (0.78-3.15%), which makes them distinctly different from primary olivine, but similar to Fe-olivine in chondrule rims of other meteorites. Thin zones of chondrule minerals adjacent to the present rims are intermediate in FeO content between the Mg-rich interior and the Fe-rich rim, which indicates a reaction relationship. Regardless of conclusions drawn regarding other types of rims, granular and opaque rim characteristics appear to be inconsistent with nebular condensation, in that host and matrix fragments are included within the rim. We have initiated a series of experiments, using the Ames two-stage light gas gun, to investigate the hypothesis that the Weston chondrule rims are the result of thermal and mechanical alteration upon impact into a low-density medium. Clusters of approximately 200-micron-sized silicate particles were fired into aerogel (density = 0.1 g cm-3) at velocities of 5.6, 4.7, and 2.2 km sec-1. Recovered grains show characteristics that range from fragmented projectile grains mixed with melted aerogel that nearly rim the grains to grains that have melted aerogel clumps mixed with partially melted projectile. These experimental results demonstrate that rim-like thermal and mechanical alteration of projectiles can result from a high-velocity encounter with a low-density target. Therefore, experiments using appropriately chosen projectile and target materials can provide a test of the hypothesis that chondrule rims common to Weston and possibly other ordinary chondrites were formed by such a process.

Astronomical Phenomena↗
PubMed2005

The use of a high-FeO olivine rock as a redox buffer in a nuclear waste repository.

Due to the higher stability of the spent nuclear fuel (mainly composed of UO2) under reducing conditions, and in order to enhance the retention/retardation of some key radionuclides, the olivine rock from the Lovasjärvi intrusion has been proposed as a potential redox-active backfill-additive in deep high-level nuclear waste (HLNW) repositories. In this work, two different approaches have been undertaken in order to establish the redox buffer capacity of olivine rock: (1) The capacity of the rock to respond to changes in pH or pe has been demonstrated and the final (pH, pe) coordinates agree with the control exerted by the system Fe(II)/Fe(III). (2) The rate of consumption of oxygen has been determined at different pH values. These rates are higher than the ones reported in the literature for other solids, what would point to the possibility of using this rock as an additive to the backfill material in a HLNW.

Buffers↗
PubMed2006

FTIR features of lithium-iron phosphates as electrode materials for rechargeable lithium batteries.

The essential structural features of lithium-metal phosphates (LMP) have been studied using FTIR spectroscopy which is a sensitive tool to probe the local environment in the solid materials. Various LMP materials where M is iron have been investigated including phospho-olivine LiFePO(4), diphosphate LiFeP(2)O(7), Nasicon-type phosphate Li(3)Fe(2)(PO(4))(3) and dihydrate FePO(4).2H(2)O. Vitreous and amorphous materials are also considered. Analysis of internal and external modes of vibration allows to distinguish between the different phases and the type of cationic environment in the framework. Results corroborate the contribution of the main factors which are responsible for the complexity of the spectra, i.e. departure from ideal symmetry, interactions between polyhedra, bridging atoms and lattice distortion.

Diphosphates↗
PubMed2007

Uptake of Cd, Zn and Mn by willow increases during terrestrialisation of initially ponded polluted sediments.

Metal concentration of plants growing on contaminated soils among other factors may depend on changes in the hydrological regime of the soil. Foliar and stem metal concentrations in Salix cinerea (grey sallow) were measured in 2 consecutive growing seasons on a submerged sediment-derived soil that underwent gradual terrestrialisation. Foliar and stem cutting concentrations for Cd, Zn and Mn increased on plots that were submerged during the first year, but emerged in the second year of monitoring. The litter layer was sampled under the shrubs of a plot with a recent abrupt change in hydrological regime and on the reference plot. It was separated in three size fractions through sieving. Analysis of the litter fractions suggested that Cd and Zn concentrations remained constant during fragmentation. However, Cr, Cu, Ni and Pb concentrations increased, which was attributed to adhesion of mineral soil particles on the fine fraction. After correction for the metal content in the mineral fraction, an increase in Cd, Mn and Cu concentration during fragmentation of the organic part of the litter layer was observed for the polluted plot. Net litter layer decomposition rate was low, which may indicate low colonisation by the decomposing community. Terrestrialisation resulted in higher Cd, Mn and Zn uptake by willows. The deviant litter layer metal concentrations for Cd, Zn and Mn and low decomposition rate must be further monitored. Feasibility of measures aiming at re-establishing wetland conditions for the dredged sediment landfill must be considered.

Belgium↗
PubMed1997

Origin of magnetite in oxidized CV chondrites: in situ measurement of oxygen isotope compositions of Allende magnetite and olivine.

Magnetite in the oxidized CV chondrite Allende mainly occurs as spherical nodules in porphyritic-olivine (PO) chondrules, where it is associated with Ni-rich metal and/or sulfides. To help constrain the origin of the magnetite, we measured oxygen isotopic compositions of magnetite and coexisting olivine grains in PO chondrules of Allende by an in situ ion microprobe technique. Five magnetite nodules form a relatively tight cluster in oxygen isotopic composition with delta 18O values from -4.8 to -7.1% and delta 17O values from -2.9 to -6.3%. Seven coexisting olivine grains have oxygen isotopic compositions from -0.9 to -6.3% in delta 18O and from -4.6 to -7.9% in delta 17O. The delta 17O values of the magnetite and coexisting olivine do not overlap; they range from -0.4 to -2.6%, and from -4.0 to -5.7%, respectively. Thus, the magnetite is not in isotopic equilibrium with the olivine in PO chondrules, implying that it formed after the chondrule formation. The delta 17O of the magnetite is somewhat more negative than estimates for the ambient solar nebula gas. We infer that the magnetite formed on the parent asteroid by oxidation of metal by H2O which had previously experienced minor O isotope exchange with fine-grained silicates.

Ferrosoferric Oxide↗
PubMed1997

The primitive matrix components of the unique carbonaceous chondrite Acfer 094: a TEM study.

The mineralogical and chemical characteristics of the fine-grained matrix (< or = 3 micrometers) of the unique primitive carbonaceous chondrite Acfer 094 have been investigated in detail by scanning electron microscopy (SEM) and analytical transmission electron microscopy (ATEM). Generally, the fine-grained matrix represents a highly unequilibrated assemblage of an amorphous material, small forsteritic olivines (200-300 nm), low Ca-pyroxenes (300-400 nm), and Fe,Ni-sulfides (100-300 nm). The matrix is basically unaffected by secondary processes. Only minor amounts of serpentine and ferrihydrite, as products of hydrous alteration, are present. Texturally, the amorphous material acts as a groundmass to olivines, pyroxenes, and sulfides, mostly exhibiting rounded or elongated morphologies. Only very few clastic mineral grains have been found. The texture and chemical composition of the amorphous material are consistent with an origin by disequilibrium condensation in either the cooling solar nebula or a circumstellar environment. As such, the amorphous material may be considered as a possible precursor of matrix materials in other types of chondrites. The non-clastic matrix olivines (Fo98-99) and pyroxenes (En97-100) are suggested to have formed either by condensation in the solar nebula under highly oxidizing conditions or by recrystallization from the amorphous material. The formation of these grains by fragmentation of chondrule components is unlikely due to chemical and microstructural reasons. Rapid cooling caused the observed intergrowths of clino/orthoenstatite in the Mg-rich matrix pyroxenes. Although some similarities exist comparing the fine-grained matrix of Acfer 094 with the matrices of the unequilibrated CO3 chondrite ALHA77307 and the unique type 3 chondrite Kakangari, Acfer 094 remains unique. Since it contains the highest measured concentrations of circumstellar SiC and the second highest of diamond (highest is Orgueil), it seems reasonable to suggested that at least parts of the amorphous material in the fine-grained matrix may be of circumstellar origin.

Carbon↗
PubMed1984

Gas chromatographic analysis of volatiles in fluid and gas inclusions.

Most geological samples and some synthetic materials contain fluid inclusions. These inclusions preserve for us tiny samples of the liquid and/or the gas phase that was present during formation, although in some cases they may have undergone significant changes from the original material. Studies of the current composition of the inclusions provide data on both the original composition and the change since trapping. These conclusions are seldom larger than 1 millimeter in diameter. The composition varies from a single major compound (e.g., water) in a single phase to a very complex mixture in one or more phases. The concentration of some of the compounds present may be at trace levels. We present here some analyses of inclusion on a variety of geological samples, including diamonds. We used a sample crusher and a gas chromatography-mass spectrometry (GC-MS) system to analyze for organic and inorganic volatiles present as major to trace constituents in inclusions. The crusher is a hardened stainless-steel piston cylinder apparatus with tungsten carbide crushing surfaces, and is operated in a pure helium atmosphere at a controlled temperature. Samples ranging from 1 mg to 1 g were crushed and the released volatiles were analyzed using multi-chromatographic columns and detectors, including the sensitive helium ionization detector. Identification of the GC peaks was carried out by GC-MS. This combination of procedures has been shown to provide geochemically useful information on the processes involved in the history of the samples analyzed.

Aluminum Oxide↗
PubMed1987

Extracorporeal shock wave lithotripsy: the use of chemical treatments for improved stone comminution.

Extracorporeal shock wave lithotripsy (ESWL) can require more than two thousand acoustic shocks to achieve an adequate degree of renal calculus comminution. A decrease in the number of shocks necessary for effective treatment offers both technical and clinical benefits. The results presented here demonstrate that it is possible in particular cases to increase substantially the degree of comminution produced using a fixed number of acoustic impulses by exposing the stones to solutions of controlled pH and chemical composition during acoustic shock treatment. The largest increase in comminution was observed for magnesium ammonium phosphate hexahydrate/apatite stones exposed to citrate solutions. The smaller particle sizes are shown to result not only from stone dissolution but also from an increase in the ease of stone fracture during acoustic shocking. The degree of comminution of the largest fragment sizes was also found to be slightly increased for calcium oxalate stones by exposure to synthetic urine of elevated pH. These chemical methods of increased stone comminution appear to be directly applicable to particular cases and may have general clinical utility if suitable conditions affecting all stones can be found.

Calcium Oxalate↗
PubMed2003

A new method for preparing powders for transmission electron microscopy examination.

In this paper we describe a novel method to prepare powder specimens for transmission electron microscopy examination. The powder samples are embedded in a metallic matrix by a route based on the plastic flow of a soft metal, using a small laboratory type hand driven hydraulic press. The resulting composites are processed with the conventional procedure based on grinding polishing and ion beam milling. The resulting TEM specimens have a self-supporting structure, good thermal and electrical conductivity while showing a well-polished surface resulting from the ion milling process. The method can be applied to a large variety of samples with sufficiently strong mechanical properties; a few examples are reported. The limits, mainly due to the mechanical toughness of the powder, are discussed.

Copper↗
PubMed1999

Study of fossil tracks due to 50 < or = Z < or = 92 galactic cosmic ray nuclei in meteoritic crystals: results and perspectives.

A new approach to the problem of investigation of charge and energy spectra of ultra heavy Galactic cosmic ray nuclei, based on fossil track study of extraterrestrial olivine crystals has been developed. The results of an investigation of ultra heavy Galactic cosmic ray nuclei (Z=50-92) in meteoritic olivine crystals are presented. The technique was based on calibration of olivine crystals with accelerated Xe, Au, Pb and U ions and well-controlled partial annealing of "fresh" and "fossil" tracks. It allows us to determine the charge spectra and abundances of cosmic ray nuclei based on fossil track length study in meteoritic and Moon crystals. The comparative studies of the spectra of "fossil' tracks and tracks due to 208Pb and 238U nuclei have shown that the group of 210 micrometers "fossil" tracks, first observed in 1980 at JINR is due to Th-U nuclei-products of recent r-process nucleosynthesis in our Galaxy. The method in principle allows one to resolve Pt-Pb peaks in fossil tracks, to establish the upper limit of the abundance of Z>110 nuclei in the Galactic cosmic rays at the level < or = 10(-3) to the abundance of actinide nuclei and to get information on the history of Z>50 cosmic ray nuclei in time interval up to 220 M.Y.

Calibration↗
PubMed2006

Carbon sequestration via aqueous olivine mineral carbonation: role of passivating layer formation.

CO2 sequestration via carbonation of widely available low-cost minerals, such as olivine, can permanently dispose of CO2 in an environmentally benign and a geologically stable form. We report the results of studies of the mechanisms that limit aqueous olivine carbonation reactivity under the optimum sequestration reaction conditions observed to date: 1 M NaCl + 0.64 M NaHCO3 at Te 185 degrees C and P(CO2) approximately equal to 135 bar. A reaction limiting silica-rich passivating layer (PL) forms on the feedstock grains, slowing carbonate formation and raising process cost. The morphology and composition of the passivating layers are investigated using scanning and transmission electron microscopy and atomic level modeling. Postreaction analysis of feedstock particles, recovered from stirred autoclave experiments at 1500 rpm, provides unequivocal evidence of local mechanical removal (chipping) of PL material, suggesting particle abrasion. This is corroborated by our observation that carbonation increases dramatically with solid particle concentration in stirred experiments. Multiphase hydrodynamic calculations are combined with experimentto better understand the associated slurry-flow effects. Large-scale atomic-level simulations of the reaction zone suggest that the PL possesses a "glassy" but highly defective SiO2 structure that can permit diffusion of key reactants. Mitigating passivating layer effectiveness is critical to enhancing carbonation and lowering sequestration process cost.

Carbon↗
PubMed2004

Use of a byproduct of magnesium oxide production to precipitate phosphorus and nitrogen as struvite from wastewater treatment liquors.

This paper describes a series of experiments designed to recover phosphorus and nitrogen from sewage in the form of struvite (MgNH(4)PO(4).6H(2)O), a potential fertilizer. Nitrogen and phosphate were recovered from a filtrate of digested sludge dewatered at the Arroyo del Soto Waste Water Treatment Plant (WWTP) (Madrid, Spain). A byproduct of the Spanish magnesite mining and MgO production industry was used as the magnesium source. The precipitating performance of this byproduct was compared to that of conventional chemical reagents such as pure MgO. The precipitates obtained were subjected to chemical, light microscopy, and X-ray diffraction analysis. The findings indicate the precipitate recovered using this byproduct contains several minerals with a predominance of struvite. Optimal purity ( approximately 80% struvite) was achieved using the sieved <0.04 mm grain size fraction of the byproduct at doses corresponding to a molar Mg:P ratio of 1.6.

Chemical Precipitation↗
PubMed1998

Petrologic evidence for low-temperature, possibly flood evaporitic origin of carbonates in the ALH84001 meteorite.

High-temperature models for origin of the carbonates in Martian meteorite ALH84001 are implausible. The impact metasomatism model, invoking reaction between CO2 rich fluid and the host orthopyroxenite, requires conversion of olivine into orthopyroxene, yet olivine in ALH84001 shows no depletion in carbonate-rich areas; or else conversion of orthopyroxene into silica, which should have yielded a higher silica/carbonate ratio. The impact melt model implies that the fracture-linked carbonates, as products of melt injection, should appear as continuous planar veins, but in many areas they do not. Both vapor deposition and impact melting seem inconsistent with the zoned poikilotopic texture of many large carbonates. The popular hydrothermal model is inconsistent with the virtual absence of secondary hydrated silicates in ALH84001. Prior brecciation should have facilitated alteration. Hydrothermal fluids would be warm, and rate of hydration of mafic silicates obeys an Arrhenius law, at least up to approximately 100 degrees C. Most important, hydrothermal episodes tend to last for many years. Many areas of the ancient Martian crust show evidence for massive flooding. I propose that the carbonates formed as evaporite deposits from floodwaters that percolated through the fractures of ALH84001, but only briefly, as evaporation and groundwater flow caused the water table to quickly recede beneath the level of this rock during the later stages of the flood episode. The setting might have been a layer of megaregolith beneath a surface catchment of pooled floodwater, analogous to a playa lake. Carbonate precipitation would occur in response to evaporative concentration of the water. To explain the scarcity of sulfates in ALH84001, the water table must be assumed to recede quickly relative to the rate of evaporation. During the period when ALH84001 was above the water table, evaporation would have slowed, as the evaporation front passed beneath the surface of the debris layer, and possibly earlier, if the shrinking pool of surface water developed a porous sulfate crust. Alternatively, ALH84001 may have developed as a Martian form of calcrete, i.e., the evaporating flood(s) may have been entirely below ground as it (they) passed slowly through ALH84001. The greatest advantage of the flood evaporite model is that it exposes ALH84001 to carbonate precipitation without prolonged exposure to aqueous alteration. The model also seems consistent with the heavy and extremely heterogeneous oxygen isotopic compositions of the carbonates. However, this hypothesis seems no more than marginally consistent with the suggestion of McKay et al. [1996] that the carbonates are biogenic.

Carbon Dioxide↗
PubMed2001

Loss of superconductivity with the addition of Al to MgB2 and a structural transition in Mg1-x AlxB2.

The basic magnetic and electronic properties of most binary compounds have been well known for decades. The recent discovery of superconductivity at 39 K in the simple binary ceramic compound magnesium diboride, MgB2, was therefore surprising. Indeed, this material has been known and structurally characterized since the mid 1950s (ref. 2), and is readily available from chemical suppliers (it is commonly used as a starting material for chemical metathesis reactions). Here we show that the addition of electrons to MgB2, through partial substitution of Al for Mg, results in the loss of superconductivity. Associated with the Al substitution is a subtle but distinct structural transition, reflected in the partial collapse of the spacing between boron layers near an Al content of 10 per cent. This indicates that superconducting MgB2 is poised very near a structural instability at slightly higher electron concentrations.

Journal Article↗
PubMed2003

Carbon solubility in olivine and the mode of carbon storage in the Earth's mantle.

The total amount of carbon in the atmosphere, oceans and other near-surface reservoirs is thought to be negligible compared to that stored in the Earth's mantle. Although the mode of carbon storage in the mantle is largely unknown, observations of microbubbles on dislocations in minerals from mantle xenoliths has led to the suggestion that carbon may be soluble in silicates at high pressure. Here we report measurements of carbon solubility in olivine, the major constituent of the upper mantle, at pressures up to 3.5 GPa. We have found that, contrary to previous expectations, carbon solubility in olivine is exceedingly low--of the order of 0.1 to 1 parts per million by weight. Together with similar data for pyroxenes, garnet and spinel, we interpret this to imply that most carbon must be present as a separate phase in the deeper parts of the upper mantle, probably as a carbonate phase. Large-scale volcanic eruptions tapping such a carbonate-bearing mantle reservoir might therefore rapidly transfer large amounts of carbon dioxide into the atmosphere, consistent with models that link global mass extinctions to flood basalt eruptions via a sudden increase in atmospheric carbon dioxide levels.

Atmosphere↗
PubMed2005

An integrated view of the chemistry and mineralogy of martian soils.

The mineralogical and elemental compositions of the martian soil are indicators of chemical and physical weathering processes. Using data from the Mars Exploration Rovers, we show that bright dust deposits on opposite sides of the planet are part of a global unit and not dominated by the composition of local rocks. Dark soil deposits at both sites have similar basaltic mineralogies, and could reflect either a global component or the general similarity in the compositions of the rocks from which they were derived. Increased levels of bromine are consistent with mobilization of soluble salts by thin films of liquid water, but the presence of olivine in analysed soil samples indicates that the extent of aqueous alteration of soils has been limited. Nickel abundances are enhanced at the immediate surface and indicate that the upper few millimetres of soil could contain up to one per cent meteoritic material.

Bromine↗