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At least 19 records

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.↗

Impact-induced devolatilization of CaSO4 anhydrite and implications for K-T extinctions: Preliminary results

The recent suggestions that the target area for the K-T bolide may have been a sulfate-rich evaporite and that the resulting sulfuric acid-rich aerosol was responsible for the subsequent cooling of the Earth and the resulting biological extinctions has prompted us to experimentally examine the impact-induced devolatization of the sulfate minerals anhydrite (CaSO4) and gypsum (CaSO4(2H2O)). Preliminary results for anhydrite are reported. Up to 42 GPa peak shock pressure, little or no devolatilization occurs, consistent with chemical thermodynamic calculations. Calculation of the influence of the partial pressure of the gas species on impact-induced devolatilization suggests that an even greater amount of sulfur than that proposed by Brett could have been released to the atmosphere by an impact into a sulfate-rich layer. Solid recovery, impact-induced devolatilization experiments were performed on the Caltech 20mm gun using vented, stainless steel sample assemblies.

Tyburczy, James A.↗

Shock-induced devolatilization of calcium sulfate and implications for K-T extinctions

The devolatilization of calcium sulfate, which is present in the target rock of the Chicxulub, Mexico impact structure, and dispersal in the stratosphere of the resultant sulfuric acid aerosol have been suggested as a possible mechanism for the Cretaceous-Tertiary extinctions. We measured the amount of SO2 produced from two shock-induced devolatilization reactions of calcium sulfate up to 42 GPa in the laboratory. We found both to proceed to a much lower extent than calculated by equilibrium thermodynamic calculations. Reaction products are found to be approx. 10(exp -2) times those calculated for equilibrium. Upon modeling the quantity of sulfur oxides degassed into the atmosphere from shock devolatilization of CaSO4 in the Chicxulub lithographic section, the resulting 9 x 10(exp 16) to 6 x 10(exp 17) g (in sulfur mass) is lower by a factor of 10-100 than previous upper limit estimates, the related environmental stress arising from the resultant global cooling and fallout of acid rain is insufficient to explain the widespread K-T extinctions.

Chen, Guangqing↗

Devolatilization of polymer resins

Commercial silicon resin was devolatilized by vacuum distillation, cured at room temperature and tested favorably for outgassing criteria. Applications of the devolatilized resin are potting compounds and conformal coatings.

Seidenberg, B.↗

Shock-induced devolatilization of calcite

Experimental measurements of the release adiabats by Vizgirda (1981) indicate that substantial vaporization takes place upon release from shock pressures of 37 GPa for calcite and 14 GPa for aragonite. The present investigation includes the first controlled partial vaporization experiments on calcite. The experiments were conducted to test the predictions of the release adiabat experiments. The quantities of the gaseous species produced from shocked calcite and their carbon and oxygen isotopic compositions were determined, and the shock-induced effect on the Mn(2+) electron spin resonance spectrum in the shock-recovered calcite was observed. On the basis of the obtained results, it is concluded that shock stresses at the 17-18 GPa level give rise to volatilization of 0.03-0.3 (mole) percent of calcite to CO2 and CO. The devolatilization of calcite occurs at low pressure at significantly lower entropy densities than predicted on the basis of thermodynamic continuum models.

Boslough, M. B.↗

Devolatilized-Allende Partial Melts as an Analog for Primitive Angrite Magmas

We have shown that partial melts of devolatilized Allende chondrite (CV3) have bulk compositions generally similar to those of angrites. Here we show that the recently described D'Orbigny and Sahara 99555 angrites are virtually identical in major-element composition to specific Allende experimental melts from. This observation has petrogenetic significance for the origins of the angrite clan.

Jurewicz, A. J. G.↗

Volatilization-devolatilization reactions

Experiments that explore chemical and physical aspects of volatilization reactions that require the microgravity and low pressure in or near the projected Space Station are proposed.

Gilbert, M. C.↗

Mantle devolatilization and rheology in the framework of planetary evolution

We investigate the thermal history of an Earth-like planet with the help of a parameterized mantle convection model including the volatile exchange between mantle and surface reservoirs. The weakening of mantle silicates by dissolved volatiles is described by a functional relationship between creep rate and water fugacity. We use flow law parameters of diffusion creep in olivine under dry and wet conditions. The mantle degassing rate is considered as directly proportional to the seafloor spreading rate, which is also dependent on the mantle heat flow. To calculate the spreading rate, we assume that the heat flow under the mid-ocean ridges is double the average mantle heat flow. The rate of regassing also depends on the seafloor spreading rate as well as on other factors like the efficiency of volatile recycling through island arc volcanism. Both mechanisms (de- and regassing) are coupled self-consistently with the help of the parameterized convection model under implementation of a temperature and volatile-content-dependent mantle viscosity.

Franck, S.↗

Performance characteristics of a slagging gasifier for MHD combustor systems

The performance of a two stage, coal combustor concept for magnetohydrodynamic (MHD) systems was investigated analytically. The two stage MHD combustor is comprised of an entrained flow, slagging gasifier as the first stage, and a gas phase reactor as the second stage. The first stage was modeled by assuming instantaneous coal devolatilization, and volatiles combustion and char gasification by CO2 and H2O in plug flow. The second stage combustor was modeled assuming adiabatic instantaneous gas phase reactions. Of primary interest was the dependence of char gasification efficiency on first stage particle residence time. The influence of first stage stoichiometry, heat loss, coal moisture, coal size distribution, and degree of coal devolatilization on gasifier performance and second stage exhaust temperature was determined. Performance predictions indicate that particle residence times on the order of 500 msec would be required to achieve gasification efficiencies in the range of 90 to 95 percent. The use of a finer coal size distribution significantly reduces the required gasifier residence time for acceptable levels of fuel use efficiency. Residence time requirements are also decreased by increased levels of coal devolatilization. Combustor design efforts should maximize devolatilization by minimizing mixing times associated with coal injection.

Smith, K. O.↗

Dynamic compression and volatile release of carbonates

Particle velocity profiles upon shock compression and isentropic releases were measured for polycrystalline calcite. The Solenhofen limestone release paths lie, close to the Hugoniot. Calcite 3 to 2 transition, upon release, was observed, but rarefaction shocks were not detected. The equation of state is used to predict the fraction of material devolatilized upon isentropic release as a function of shock pressure. The effect of ambient partial pressure of CO2 on the calculations is demonstrated and considered in models of atmospheric evolution by impact induced mineral devolatilization. The radiative characteristics of shocked calcite indicate that localization of thermal energy occurs under shock compression. Shock entropy calculations result in a minimum estimate of 90% devolatilization upon complete release from 10 GPa. Isentropic release paths from calculated continuum Hugoniot temperatures cross into the CaO (solid) + CO2 (vapor) field at improbably low pressures. It is found that release paths from measured shock temperatures cross into the melt plus vapor field at pressures greater than .5 GPa, which suggests that devolatilization is initiated at the shear banding sites.

Tyburczy, J. A.↗

Shock-induced volatile loss from a carbonaceous chondrite: Implications for planetary accretion

Solid recovery impact-induced volatile loss experiments on the Murchison C2M meteorite indicate that for an impact of a given velocity, H2O and total volatiles are driven from the sample in the same proportion as present initially. The primitive surface volatile budget of a planet growing by accretion would have the same bulk elemental composition as the volatiles in the incident planetesimals. Incipient devolatilization of Murchison occurs at an initial shock pressure of about 11 GPa and complete devolatilization occurs at a pressure of about 30 GPa. For the Earth, incipient and complete devolatilization of accreting planetesimals would occur when the planet reached approximately 12% and 27%, respectively, of its present-day radius. Impact-induced devolatilization would profoundly affect the volatile distribution within the accreting planet. Prior to metallic core formation and internal differentiation the growing planet would have a very small core with the same volatile content as the incident material, a volatile depleted mantle, and an extremely volatile rich surface. In the case of the Earth, 99.4 wt% of the total incident volatile material would end up on or near the planetary surface.

Tyburczy, J. A.↗

Dynamic compression and volatile release of carbonates

Particle velocity profiles upon shock compression and isentropic releases were measured for polycrystalline calcite. The Solenhofen limestone release paths lie close to the Hugoniot. Calcite 3 to 2 transition, upon release was observed, but rarefaction shocks were not detected. The equation of state is used to predict the fraction of material devolatilized upon isentropic release as a function of shock pressure. The effect of ambient partial pressure of CO2 on the calculations is demonstrated and considered in models of atmospheric evolution by impact induced mineral devolatilization. The radiative characteristics of shocked calcite indicate that localization of thermal energy occurs under shock compression. Shock entropy calculations result in a minimum estimate of 90 percent devolatilization upon complete release from 10 GPa. Isentropic release paths from calculated continuum Hugoniot temperatures cross into the CaO (solid) + CO2 (vapor) field at improbably low pressures. It is found that release paths from measured shock temperatures cross into the melt plus vapor field at pressures greater than .5 GPa, which suggests that devolatilization is initiated at the shear banding sites.

Tyburczy, J. A.↗

Shock-induced volatile loss from a carbonaceous chondrite Implications for planetary accretion

Solid recovery impact-induced volatile loss experiments on the Murchison C2M meteorite indicate that for an impact of a given velocity, H2O and total volatiles are driven from the sample in the same proportion as present initially. The primitive surface volatile budget of a planet growing by accretion would have the same bulk elemental composition as the volatiles in the incident planetesimals. Incipient devolatilization of Murchison occurs at an initial shock pressure of about 11 GPa and complete devolatilization occurs at a pressure of about 30 GPa. For the earth, incipient and complete devolatilization of accreting planetesimals would occur when the planet reached approximately 12 percent and 27 percent, respectively, of its present-day radius. Impact-induced devolatilization would profoundly affect the volatile distribution within the accreting planet. Prior to metallic core formation and internal differentiation the growing planet would have a very small core with the same volatile content as the incident material, a volatile depleted mantle, and an extremely volatile rich surface. In the case of the earth, 99.4 wt pct of the total incident volatile material would end up on or near the planetary surface.

Tyburczy, James A.↗

Relative Shock Effects in Mixed Powders of Calcite, Gypsum, and Quartz: A Calibration Scheme from Shock Experiments

The shock behavior of calcite and gypsum is important in understanding the Cretaceous/Tertiary event and other terrestrial impacts that contain evaporite sediments in their targets. Most interest focuses on issues of devolatilization to quantify the production of CO2 or SO2 to better understand their role in generating a temporary atmosphere and its effects on climate and biota [e.g., papers in 1,2,3,4]. Devolatilization of carbonate is also important because the dispersion and fragmentation of ejecta is strongly controlled by the expansion of large volumes of gas during the impact process as well [5,6]. Shock recovery experiments for calcite yield seemingly conflicting results: early experimental devolatilization studies [7,8,9] suggested that calcite was substantially outgassed at 30 GPa (> 50%). However, the recent petrographic work of [10,11,12] presented evidence that essentially intact calcite is recovered from 60 GPa experiments. [13] reported results of shock experiments on anhydrite, gypsum, and mixtures of those phases with silica. Their observations indicate little or no devolatilization of anhydrite shocked to 42 GPa and that the fraction of sulfur, by mass, that degassed is approx.10(exp -2) of theoretical prediction. In another (preliminary) report of shock experiments on calcite, anhydrite, and gypsum, [14] observe calcite recrystallization when shock loaded at 61 GPa, only intensive plastic deformation in anhydrite shock loaded at 63 GPa, and gypsum converted to anhydrite when shock loaded at 56 GPa. [15] shock loaded anhydrite and quartz to a peak pressure of 60 GPa. All of the quartz grains were trans-formed to glass and the platy anhydrite grains were completely pseudomorphed by small crystallized anhydrite grains. However, no evidence of interaction between the two phases could be observed and they suggest that recrystallization of anhydrite grains is the result of a solid state transformation. [16] reanalyzed the calcite and anhydrite shock wave experiments of [17] using improved equations of state of porous materials and vaporized products. They determined the pressures for incipient and complete vaporization to be 32.5 and 122 GPa for anhydrite and 17.8 and 54.1 GPa for calcite, respectively, a factor of 2 to 3 lower than reported earlier by [17].

Bell, Mary S.↗

Modifying a silicone potting compound for space flight applications

RTV-615 has been devolatilized by subjecting the uncatalyzed resin to a temperature of between 125 and 150 C for 24 hours in a vacuum of about 10 to the -6th torr. The resultant resin can be catalyzed and after a room temperature cure the outgassing of the resin is sufficiently low when tested according to ASTM E-595 that it is suitable for space flight use. Tests of physical properties of the cured devolatilized resin were compared with those of the as received silicone. The devolatilized silicones are slightly harder, have a higher tear resistance and higher tensile strengths.

Park, J. J.↗

Mineralogical Studies of Experimentally Shocked Dolomite: Implications for the Outgassing of Carbonates

Common rock-forming rhombohedral carbonates - calcite and dolomite - constitute a considerable fraction of terrestrial sediments that may be shocked during hypervelocity impacts, such as during the Cretaceous-Tertiary (K/T) event or at the Haughton structure. The relatively modest temperatures needed to decompose carbonates and to release their CO2 are easily attained during such impacts. However, detailed and quantitative understanding of the CO2 release of carbonates as a function of shock stress is still the subject of controversy, as are a number of other reactions and phase transitions that were suggested for carbonates. The first devolatilization studies of carbonates in the early 1980s suggested that incipient devolatilization of calcite and/or dolomite commences at modest pressures, in the range < 10-18 GPa (amounting to 0.03-0.3% CO2 loss), with massive decarbonation (30-40% CO2 loss) occurring at shock pressure of 20 GPa and above. However, most later studies revealed that both calcite and dolomite are unexpectedly stable under shock conditions and no significant outgassing has been observed at pressures as high as 40 GPa for calcite and 60 GPa for dolomite. Despite these uncertainties, the calculations of O'Keefe and Ahrens (and others) serve to illustrate that the K/T bolide liberated sufficient CO2 that a substantial temperature increase of the global atmosphere is possible due to CO2-triggered greenhouse effects. The quantitative understanding of the devolatilization of carbonates as a function of shock stress is obviously critical to refine such calculations. Additional information is contained in the original extended abstract.

Skala, R.↗