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At least 19 records

Oxygen and hydrogen isotope geochemistry of zeolites

Oxygen and hydrogen isotope ratios for natural samples of the zeolites analcime, chabazite, clinoptilolite, laumontite, mordenite, and natrolite have been obtained. The zeolite samples were classified into sedimentary, hydrothermal, and igneous groups. The ratios for each species of zeolite are reported. The results are used to discuss the origin of channel water, the role of zeolites in water-rock interaction, and the possibility that a calibrated zeolite could be used as a low-temperature geothermometer.

Karlsson, Haraldur R.

Impact-induced devolatilization and hydrogen isotopic fractionation of serpentine: Implications for planetary accretion

Impact-induced devolatilization of porous serpentine was investigated using two independent experimental methods, the gas recovery and the solid recovery method, each yielding nearly identical results. For shock pressures near incipient devolatilization, the hydrogen isotopic composition of the evolved H2O is very close to that of the starting material. For shock pressures at which up to 12 percent impact-induced devolatilization occurs, the bulk evolved gas is significantly lower in deuterium than the starting material. There is also significant reduction of H2O to H2 in gases recovered at these higher shock pressures, probably caused by reaction of evolved H2O with the metal gas recovery fixture. Gaseous H2O-H2 isotopic fractionation suggests high temperature isotopic equilibrium between the gaseous species, indicating initiation of devolatilization at sites of greater than average energy deposition. Bulk gas-residual solid isotopic fractionations indicate nonequilibrium, kinetic control of gas-solid isotopic ratios. Impact-induced hydrogen isotopic fractionation of hydrous silicates during accretion can strongly affect the long-term planetary isotopic ratios of planetary bodies, leaving the interiors enriched in deuterium. Depending on the model used for extrapolation of the isotopic fractionation to devolatilization fractions greater than those investigated experimentally can result from this process.

Tyburczy, James A.

Hydrogen-isotope evidence for extrusion mechanisms of the Mount St Helens lava dome

Hydrogen isotope analyses were used to determine water content and deuterium content for 18 samples of the Mount St Helens dome dacite in an attempt to identify the triggering mechanisms for periodic dome-building eruptions of lava. These isotope data, the first ever collected from an active lava dome, suggest a steady-state process of magma evolution combining crystallization-induced volatile production in the chamber with three different degassing mechanisms: closed-system volatile loss in the magma chamber, open-system volatile release during ascent, and kinetically controlled degassing upon eruption at the surface. The data suggest the future dome-building eruptions may require a new influx of volatile-rich magma into the chamber.

Anderson, Steven W.

SAMPEX observations of energetic hydrogen isotopes in the inner zone

We report observations of geomagnetically-trapped hydrogen isotopes at low altitudes, near the feet of field lines in the inner zone, made with the PET instrument aboard the SAMPEX satellite. We have mapped protons from 19 to 500 MeV, and have discovered a collocated belt of deuterons, which we have mapped from 18 to 58 MeV/nucleon. We found deuterium at about 1% of the level of the proton flux at the same energy per nucleon, and no tritium at energies of tens of MeV/nucleon with an upper limit of about 0.1% of the proton flux. Protons and deuterons showed similar time dependence, with fluxes approximately tripling from July 1992 to March 1996, and similar pitch-angle dependence. The high-L limits of the proton and deuteron belts as functions of energy were organized by rigidity, as was to be expected if these limits were set for both species by inability of particles to sustain adiabatic motion and stable trapping.

SAMPEX Project

On-line technique for measuring stable oxygen and hydrogen isotopes from microliter quantities of water

Detailed here is a method for extracting and analyzing oxygen and hydrogen isotopes from 10 microL-sized water samples. Based on the traditional CO2-H2O equilibration technique, the oxygen isotope exchange reaction is done exclusively in sealed 6-mm (o.d.) Pyrex tubes at 25 degrees C, with full isotope exchange completed in at least 28 h. Using the same water sample employed in the 18O equilibration, D/H extractions are done in separate sealed 6-mm (o.d.) Pyrex tubes by reaction with Zn at 450 degrees C to form H2(g). Provided that a correction factor is applied to 18O analyses, accuracy and precision for both 18O and D/H are comparable to standard techniques using much larger samples.

NASA Center JSC

Ultrafiltration by a compacted clay membrane. I - Oxygen and hydrogen isotopic fractionation. II - Sodium ion exclusion at various ionic strengths.

Laboratory experiments were carried out to determine the magnitude of the isotopic fractionation of distilled water and of 0.01N NaCl forced to flow at ambient temperature under a hydraulic pressure drop of 100 bars across a montmorillonite disk compacted to a porosity of 35% by a pressure of 330 bars. The ultrafiltrates in both experiments were depleted in D by 2.5% and in O-18 by 0.8% relative to the residual solution. No additional isotopic fractionation due to a salt-filtering mechanism was observed at NaCl concentrations up to 0.01N. Adsorption is most likely the principal mechanism which produces isotopic fractionation, but molecular diffusion may play a minor role. The results suggest that oxygen and hydrogen isotopic fractionation of ground water during passage through compacted clayey sediments should be a common occurrence, in accord with published interpretations of isotopic data from the Illinois and Alberta basins. It is shown how it is possible to proceed from the ion exchange capacity of clay minerals and, by means of the Donnan membrane equilibrium concept and the Teorell-Meyer-Siever theory, develop a theory to explain why and to what extent ultrafiltration occurs when solutions of known concentration are forced to flow through a clay membrane.

Coplen, T. B.

Collision integrals for isotopic hydrogen molecules.

The study was undertaken to determine the effects of reduced mass and differences in asymmetry on the collision integrals and thermal diffusion factors of isotopic hydrogen systems. Each system selected for study consisted of two diatoms, one in the j = 0 rotation state and the other in the j = 1 state. The molecules interacted with a Lennard-Jones type potential modified to include angular terms. A set of cross sections and collision integrals were obtained for each system.

Brown, N. J.

Carbon and hydrogen isotopic characterization of methane from wetlands and lakes of the Yukon-Kuskokwim Delta, Western Alaska

The results are reported of a study of the carbon and hydrogen isotopic composition of methane from tundra environments of the Yukon-Kuskokwin Delta of western Alaska. The delta C-13 value of diffusive methane emissions from wet meadow tundra of the Delta is -65.82 +/- 2.21 per mil (n=18). Detritus-rich sediments of tundra lakes are loaded with methane-rich gas bubbles during the warm season. Spatial trend is the major gas concentration and isotopic values of methane in these gas bubbles appear to reflect processes associated with production rate and mechanisms; high methane concentrations, lightest delta C-13 values, the heaviest delta D value occur in detritus-rich sediments isolated from emergent vegetation. Heavier delta C-13 and lighter delta D values in methane from heavily vegetated lake margins suggest a shift toward a larger role for acetate fermentation in association with aquatic plants and plant detritus. Bubble ebullition is estimated to account for up to 17 percent of total Delta methane emissions.

Martens, Christopher S.

Sulfur and Hydrogen Isotope Anomalies in Meteorite Sulfonic Acids

Intramolecular carbon, hydrogen, and sulfur isotope ratios were measured on a homologous series of organic sulfonic acids discovered in the Murchison meteorite. Mass-independent sulfur isotope fractionations were observed along with high deuterium/hydrogen ratios. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low-temperature environment that is consistent with that of interstellar clouds. Sulfur-33 enrichments observed in methanesulfonic acid could have resulted from gas-phase ultraviolet irradiation of a precursor, carbon disulfide. The source of the sulfonic acid precursors may have been the reactive interstellar molecule carbon monosulfide.

Cooper, George W.

Sulfur and Hydrogen Isotope Anomalies in Organic Compounds from the Murchison Meteorite

Isotopic measurements have been made on organic sulfur and phosphorus compounds recently discovered in the Murchison meteorite. Carbon, hydrogen and sulfur measurements were performed on individual members of the organic sulfur compounds, alkyl sulfonates; and carbon and hydrogen measurements were made on bulk alkyl phosphonates. Cooper and Chang reported the first carbon isotopic measurements of Murchison organic sulfonates, providing insight into the potential synthetic mechanisms of these and, possibly, other organic species. Hydrogen isotopic measurements of the sulforiates now reveal deuterium excesses ranging from +660 to +2730 %. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low temperature astrophysical environment consistent with that of dense molecular clouds. Measurements of the sulfur isotopes provide further constraints on the origin and mechanism of formation of these organic molecules. Recently, there has been growing documentation of sulfur isotopic anomalies in meteoritic material. Thiemens and Jackson have shown that some bulk ureilites possess excess S-33 and Thiemens et al. have reported excess S-33 in an oldhamite separate from the Norton County meteorite. Rees and Thode reported a large S-33 excess in an Allende acid residue, however, attempts to verify this measurements have been unsuccessful, possibly due to the heterogeneous nature of the carrier phase. With the recognition that sulfur isotopes may reflect chemistry in the protosolar nebula or the precursor molecular cloud, identification of potential carriers is of considerable interest. In the present study, the stable isotopes of sulfur were measured in methane sulfonic acid extracted from the Murchison meteorite. The isotopic composition was found to be: (delta)S-33 = 2.48 %, (delta)S-34 = 2.49 % and (delta)S-36 = 6.76 %. Based upon analysis of more than 60 meteoritic and numerous terrestrial samples, the mass fractionation lines are defined by Delta-33 = (delta)S-33 -0.50(delta)S-34 and Delta-36 = (delta)s-36 - 1.97 (delta)S-34. From these relationships Delta-33 = 1.24 % and Delta-36 = 0.89 % are observed. These anomalies, particularly the Delta-33, lie well outside the range of analytical uncertainty. They are the largest observed in any meteoritic component and the first found in an organosulfur compound. As discussed by Thiemens and Jackson, due to it's position on the periodic chart, sulfur undergoes chemically induced mass independent isotopic fractionations as does oxygen. Experiments by Mauersberger et. al. show that in such processes, the magnitude of fractionation for the different isotopically substituted species varies with mass and angular momentum; thus, anomalies are expected for both S-33 and S-36, but not necessarily of the same magnitude. Laboratory experiments have also confirmed that chemically produced, mass independent fractionations are mediated by molecular symmetry factors. A chemical source of fractionation requires that the sulfur isotopic anomaly was established in the gas phase, probably in reactions involving symmetric CS2. The discovery of an anomalous sulfur isotopic composition in a specific molecule containing excess deuterium is an important advance in the understanding of the cosmochemistry of sulfur. This evidence suggests that methanesulfonic acid was synthesized by interstellar processes. Further measurements and details of possible synthesis and fractionation mechanisms will be presented.

Cooper, G. W.

A hydrogen isotope study of CO3 type carbonaceous chondrites; comparison with type 3 ordinary chondrites

Meteorites of the Ornans type 3 carbonaceous chondrites exhibit a range in degree of equilibration, attributed to differing amounts of thermal metamorphism. These differences have been used to split the CO3 chondrites into petrologic sub-types from 3.0, least equilibrated, to 3.7, being most equilibrated. This is similar to the system of assigning the type 3 ordinary chondrites into petrologic sub-types 3.0 to 3.9 based upon thermoluminescence (TL) and other properties; however, the actual range of thermal metamorphism experienced by CO3 chondrites is much less than that of the type 3 ordinary chondrites. The least equilibrated ordinary chondrites show evidence of aqueous alteration and have high D/H ratios possibly due to a deuterium-rich organic carrier. The aim of this study was to determine whether the CO3 chondrites, which have experienced similar secondary conditions to the type 3 ordinary chondrites, also contain a similar deuterium-rich carrier. To date a total of 5 CO3 meteorites, out of a set of 11 for which carbon and nitrogen isotopic data are available, have been analyzed. Ornans has not been analyzed yet, because it does not appear to fit in with the metamorphic sequence exhibited by the other CO3 chondrites; it also has an extremely high delta-D value of +2150 percent, unusual for such a comparatively equilibrated meteorite (type 3.4). Initial results indicate that the more equilibrated CO3's tend to have lower delta-D values, analogous to the higher petrologic type ordinary chondrites. However this is complicated by the effects of terrestrial weathering and the small data-set.

Morse, A. D.

Isotopic composition of hydrogen in insoluble organic matter from cherts

Robert (1989) reported the presence of unusually enriched hydrogen in the insoluble HF-HCl residue extracted from two chert samples of Eocene and Pliocene ages. Since the presence of heavy hydrogen might be due to the incorporation of extraterrestrial materials, we desired to reexamine the same samples to isolate the D-rich components. Our experiments did not reveal any D-rich components, but the hydrogen isotope composition of the insoluble residue of the two chert samples was well within the range expected for terrestrial organic matter. We also describe a protocol that needs to be followed in the hydrogen isotope analysis of any insoluble organic matter.

Non-NASA Center