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J. D. Pasteris

Publications and source records attributed to J. D. Pasteris.

4 recordsLinked to original sources

Fluid-deposited graphitic inclusions in quartz: Comparison between KTB (German Continental Deep-Drilling) core samples and artificially reequilibrated natural inclusions

We used Raman microsampling spectroscopy (RMS) to determine the degree of crystallinity of minute (2–15 μm) graphite inclusions in quartz in two sets of samples: experimentally reequilibrated fluid inclusions in a natural quartz grain and biotite-bearing paragneisses from the KTB deep drillhole in SE Germany. Our sequential reequilibration experiments at 725°C on initially pure CO 2 inclusions in a quartz wafer and the J. Krautheim 1993 experiments at 900–1100°C on organic compounds heated in gold or platinum capsules suggest that, at a given temperature, (1) fluid-deposited graphite will have a lower crystallinity than metamorphosed organic matter and (2) that the crystallinity of fluid-deposited graphite is affected by the composition of the fluid from which it was deposited. We determined that the precipitation of more-crystalline graphite is favored by lower f H 2 (higher f O 2 ), and that the crystallinity of graphite is established by the conditions (including gas fugacities) that pertain as the fluid first reaches graphite saturation. Graphite inclusions within quartz grains in the KTB rocks show a wide range in crystallinity index, reflecting three episodes of carbon entrapment under different metamorphic conditions. Isolated graphite inclusions have the spectral properties of totally ordered, completely crystalline graphite. Such crystallinity suggests that the graphite was incorporated from the surrounding metasedimentary rocks, which underwent metamorphism at upper amphibolite-facies conditions. Much of the fluid-deposited graphite in fluid inclusions, however, shows some spectral disorder. The properties of that graphite resemble those of experimental precipitates at temperatures in excess of 700°C and at elevated pressures, suggesting that the inclusions represent precipitates from C-O-H fluids trapped under conditions near those of peak metamorphism at the KTB site. In contrast, graphite that is intimately associated with chlorite and other (presumably low-temperature) silicates in inclusions is highly disordered and spectrally resembles kerogens. This graphite probably was deposited during later greenschist-facies retrograde metamorphism at about 400–500°C. The degree of crystallinity of fluid-deposited graphite is shown to be a much more complex function of temperature than is the crystallinity of metamorphic graphite. To some extent, experiments can provide temperature-calibration of the crystallinity index. However, the difference in time scales between experimental runs and geologic processes makes it difficult to infer specific temperatures for naturally precipitated graphite.

Bohemian Massif

Extremely acid Permian lakes and ground waters in North America

Evaporites hosted by red beds (red shales and sandstones), some 275-265 million years old, extend over a large area of the North American mid- continent. They were deposited in non-marine saline lakes, pans and mud- flats, settings that are typically assumed to have been alkaline. Here we use laser Raman microprobe analyses of fluid inclusions trapped in halites from these Permian deposits to argue for the existence of highly acidic (pH < 1) lakes and ground waters. These extremely acidic systems may have extended over an area of 200,000 km2. Modern analogues of such systems may be natural acid lake and groundwater systems (pH ~2-4) in southern Australia. Both the ancient and modern acid systems are characterized by closed drainage, arid climate, low acid-neutralizing capacity, and the oxidation of minerals such as pyrite to generate acidity. The discovery of widespread ancient acid lake and groundwater systems demands a re-evaluation of reconstructions of surface conditions of the past, and further investigations of the geochemistry and ecology of acid systems in general.

Nature

Raman spectroscopic characterization of gas mixtures. II. Quantitative composition and pressure determination of the CO2-CH4 system

Raman spectral parameters were determined for the v 1 band of CH4 and the v 1 and 2 v 2 bands (Fermi diad) of CO 2 in pure CO 2 and CO 2 -CH 4 mixtures at pressures up to 700 bars and room temperature. Peak position, area, height, and width were investigated as functions of pressure and composition. The peak positions of the CH 4 and CO 2 bands shift to lower relative wavenumbers as fluid pressure is increased. The peak position of the lower-wavenumber member of the Fermi diad for CO 2 is sensitive to fluid composition, whereas the peak positions of the CH 4 band and the upper Fermi diad member for CO 2 are relatively insensitive in the CO 2 -CH 4 system. The magnitude of the shifts in each of the three peak positions (as a function of pressure) is sufficient to be useful as a monitor of fluid pressure. The relative molar proportions in a CO 2 -CH 4 mixture may be determined from the peak areas: the ratio of the peak areas of the CH 4 band and the CO 2 upper Fermi diad member is very sensitive to composition, whereas above about 100 bars, it is insensitive to pressure. Likewise, the peak height ratio is very sensitive to composition but also to fluid pressure. The individual peak widths of CO 2 and CH 4 , as well as the ratios of the widths of the CH 4 peak to the CO 2 peaks are a sensitive function of pressure and, to a lesser extent, composition. Thus, upon determination of fluid composition, the peak width ratios may be used as a monitor of fluid pressure. The application of these spectral parameters to a suite of natural CO 2 -CH 4 inclusions has yielded internally-consistent, quantitative determinations of the fluid composition and density.

American Journal of Science

Speciation in experimental C-O-H fluids produced by the thermal dissociation of oxalic acid dihydrate

Fluid speciations and their related reaction pathways were studied in C-O-H-system fluids produced by the thermal dissociation of oxalic acid dihydrate (OAD: H 2 C 2 O 4 · 2H 2 O) sealed in silica glass capsules. Experiments were conducted in the temperature range 230–750°C, with bulk fluid densities in the range 0.01–0.53 g/cm 3 . Pressure was controlled by temperature and density in the isochoric systems. The quenched products of dissociation experiments were an aqueous liquid and one (supercritical fluid) or, rarely, two (vapor plus liquid) carbonic phase (s). In-situ Raman microanalyses were performed on the quenched carbonic phases at room temperature, at which fluid pressures ranged from about 50 to 340 bars. Bulk fluid speciations were reconstructed from the Raman analyses via mass balance constraints, and appear to monitor the true fluid speciations at run conditions. In experiments from the lowtemperature range (230–350°C), fluid speciations record the dissociation of OAD according to the reaction OAD = CO 2 + CO + 3 H 2 O . A process of the form CO + H 2 O = CO 2 + H 2 is driven to the right with increasing temperature. The hydrogen gas produced tends to escape from the sample systems via diffusion into/through the silica glass capsules, shifting bulk compositions toward equimolar binary H 2 O-CO 2 mixtures. The speciations of fluids in experiments with minimal hydrogen loss show poor agreement with speciations calculated for equilibrium fluids by the corresponding-states model of Saxena and Fei (1988). Such disagreement suggests that the formations of CH 4 and graphite are metastably inhibited in the current experiments, which correlates with their absence or trivial abundances in experimental products. Moreover, calculations in which the stabilities of methane and graphite are suppressed suggest that such metastable equilibrium is approached only in experiments at temperatures greater than about 600–650°C. These results have applications to fluid processes in geological environments, in addition to considerations of using oxalate compounds as volatile sources in experimental studies. It is possible that disequilibrium or metastable fluids may be entrapped as inclusions; re-speciation (toward metastable or stable equilibrium) during P-T evolution of a given terrain would place the fluid inclusion on a new isochore that would not project through the original conditions of entrapment. Moreover, the disequilibrium to metastable nature of dissociation reactions, coupled with the diffusional mobility of hydrogen gas observed in the current experiments, suggests that the predominance of binary H 2 O-CO 2 fluid mixtures in natural inclusions from medium- to high-grade metamorphic terrains may be more than a coincidence of similar initial bulk compositions.

Geochimica et Cosmochimica Acta