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Harvey, Ralph P.

Publications and source records attributed to Harvey, Ralph P..

Chemical and Microstructural Changes in Metallic and Ceramic Materials Exposed to Venusian Surface Conditions

The chemical and microstructural behavior of steels (304, 310, 316, and 1018), nickel-based alloys (beta-NiAl, G30, and 625), gold, coatings (4YSZ, SilcoNert(TradeMark) 1040 (SilcoTek Co.), Dursan(TradeMark) (SilcoTek Co.), and porcelain), and bulk ceramics (alpha-Al2O3, fused quartz, beta-SiC, and alpha-Si3N4) were probed after exposure to supercritical fluid with temperature, pressure, and composition mimicking the Venus lower atmosphere. Exposures were carried out in the Glenn Extreme Environments Rig (GEER) chamber with the Venusian gas mixture (96.5% CO2, 3.5% N2, 30 ppm H2O, 150 ppm SO2, 28 ppm CO, 15 ppm OCS, 3 ppm H2S, 0.5 ppm HCl, and 5 ppb HF) at 92 bar (1330 psi) and 467 C (873 F) for durations of 10 and 42 days. An additional 21-day exposure was done to stainless steel uncoated and coated with SilcoNert(TradeMark) and Dursan(TradeMark). Samples were characterized before and after the experiment by gravimetric analysis, X-ray diffraction, X-ray photoelectron and Auger electron spectroscopies, and cross section electron microscopy analysis. All steels exposed for 10 and 42 days formed double-layered scales consisting mainly of metal (Cr, Fe, Ni) oxides and sulfides showing different chemistry, microstructure, and crystalline phases. The alloys G30 and 625 formed double-layered scales consisting mainly of nickel sulfides. After 10 days, the beta-NiAl exhibited no detectable scale, suggesting only a very thin film was formed. The 304 and 316 stainless steels coated with 4YSZ that were exposed for 10 and 42 days exhibited no significant oxidation. Steel 1018 coated with 4YSZ exhibited a corrosion scale of iron and/or chromium oxide formed at the base of the alloy. The 304 steel coated with porcelain did not exhibit corrosion, although the coating exhibited recession. SilcoNert(TradeMark) exposed for 10 and 42 days exhibited recession, although no oxidation was found to occur at the base of the alloy. Stainless steel 316 coated with Dursan(TradeMark)  exhibited corrosion at the base of the alloy. All ceramics tested showed no clear evidence of reaction. The weight-gain-per-area performance of the materials exposed in the GEER for 10 and 42 days are reported from the lowest to the highest weight gain per area as follows: gold did not exhibit any weight change; nickel-based alloys: beta- NiAl < G30 < 625; steels: 304 < 310 < 316 < 1018; ceramics: considering the experimental uncertainties, no weight change was observed for all ceramics of this work (alpha-Al2O3, Si3N4, SiC, and amorphous SiO2).

Costa, Gustavo C. C.↗

Sources of Sulfate Found in Mounds and Lakes at the Lewis Cliffs Ice Tongue, Transantarctic

Massive but highly localized Na-sulfate mounds (mirabilite, Na2SO4.10H2O) have been found at the terminal moraine of the Lewis Cliffs Ice Tongue (LCIT), Antarctica. (Sigma)34S and (Sigma)18O values of LCIT mirabilite range from +48.8 to +49.3% (CDT), and -16.6 to -17.1% (V-SMOW), respectively, while (Delta)17O average -0.37% (V-SMOW). LCIT mirabilite mounds are isotopically different from other mirabilite mounds found in coastal regions of Antarctica, which have isotope values close to seawater compositions. (Sigma)18O and (Delta)17O values suggest the incorporation of isotopically light glacial water. Data point to initial sulfate formation in an anoxic water body, either as a stratified anoxic deep lake on the surface, a sub-glacial water reservoir, or a sub-glacial lake. Several surface lakes of varying size are also present within this region of the LCIT, and in some cases are adjacent to the mirabilite mounds. O and D isotope compositions of surface lakes confirm they are derived from a mixture of glacial ice and snow that underwent moderate evaporation. (Sigma)18O and (Sigma)D (V-SMOW) values of snow, ice, and lake water range from -64.2 to -29.7%, and -456.0 to -231.7%, respectively. However, the isotope chemistry of these surface lakes is extremely different from the mounds. Dissolved SO4-2 (Sigma)34S and (Sigma)18O values range from +12.0 to +20.0% and -12.8 to -22.2% (the most negative (Sigma)18O of terrestrial sulfate ever reported), respectively, with sulfate (Delta)17O ranging from +0.93 to 2.24%. Ion chromatography data show that lake water is fresh to brackish in origin, with TDS less than 1500 ppm, and sulfate concentration less than 431 ppm. Isotope and chemical data suggest that these lakes are unlikely the source of the mirabilite mounds. We suggest that lake water sulfate is potentially composed of a mixture of atmospheric sulfate and minor components of sulfate of weathering origin, much like the sulfate in the polar plateau soils of the McMurdo Dry Valleys. A simple model explains mirabilite mound formation at the LCIT. Sulfur redox processes could occur sub-glacially as a result of liquid-water-based glacial conditions (Alpine style glacier), most likely formed by pressure melting of overlying ice (Aharon, GCA, 52, 2321-2331). We suggest that the aqueous base of the LCIT contains dissolved SO42- and is anoxic where sulfate reduction to H2S, HS-, or native sulfur takes place. Sulfide is removed by either precipitation as sulfide minerals or by escape of H2S (neither of which have been observed). Mirabilite precipitation is likely the result of evaporation or freezing of sulfate-rich brines as they reach the surface where they manifest themselves as mounds. Pressure from the overlying ice contributing to a pressure-melting scenario that creates the sub-glacial aqueous environment also contributes to the mechanism of upward transport of the sulfate-rich fluids. Further evidence to support this upward transport model comes from the nature of ice motion at the LCIT. Cassidy et al (Meteoritics, 27, 490-525, 1992) pointed out that it is the vertical ice motion in this area that creates the meteorite-stranding surface that could also account for upward transport of sulfate-rich fluids. Alternatively, mirabilite was deposited in a similar condition as present-day coastal Antarctica when the LCIT was wetter and warmer

Socki, Richard↗

Antarctic Mirabilite Mounds as Mars Analogs: The Lewis Cliffs Ice Tongue Revisited

It has been proposed, based on geomorphic and geochemical arguments, that subsurface water has played an important role in the history of water on the planet Mars [1]. Subsurface water, if present, could provide a protected and long lived environment for potential life. Discovery of gullies [2] and recurring slopes [3] on Mars suggest the potential for subsurface liquid water or brines. Recent attention has also focused on small (< approx. 1km dia.) mound-like geomorphic features discovered within the mid to high latitudes on the surface of Mars which may be caused by eruptions of subsurface fluids [4, 5]. We have identified massive but highly localized Na-sulfate deposits (mirabilite mounds, Na2SO4 .10H2O) that may be derived from subsurface fluids and may provide insight into the processes associated with subsurface fluids on Mars. The mounds are found on the end moraine of the Lewis Cliffs Ice Tongue (LCIT) [6] in the Transantarctic Mountains, Antarctica, and are potential terrestrial analogs for mounds observed on the martian surface. The following characteristics distinguish LCIT evaporite mounds from other evaporite mounds found in Antarctic coastal environments and/or the McMurdo Dry Valleys: (1) much greater distance from the open ocean (approx.500 km); (2) higher elevation (approx.2200 meters); and (3) colder average annual temperature (average annual temperature = -30 C for LCIT [7] vs. 20 C at sea level in the McMurdo region [8]. Furthermore, the recent detection of subsurface water ice (inferred as debris-covered glacial ice) by the Mars Reconnaissance Orbiter [9] supports the use of an Antarctic glacial environment, particularly with respect to the mirabilite deposits described in this work, as an ideal terrestrial analog for understanding the geochemistry associated with near-surface martian processes. S and O isotopic compositions.

Socki, Richard A.↗

A Search for Impact Debris in the Pliocene Age Sirius Group, Transantarctic Mountains

The Sirius Group is a mixed sequence of interbedded diamictite and mudstone of Pliocene age found at scattered locations along the length of the Transantarctic Mountains. Sirius Group rocks are usually considered tillites, but contain some very "un-tillite" elements. Within section and from site to site, Sirius Group rocks vary considerably in terms of texture and relative abundance of clast lithologies, recording a history that includes shifting influences of glacial, lacustrine, fluvial and wetland processes. The colorful heritage of the Sirius Group has generated a lot of interest due to its potential as a record of changes in the behavior of the East Antarctic icesheet during a climatologically interesting period.

Harvey, Ralph P.↗

Oxygen Isotopic Constraints on the Genesis of Carbonates from Martian Meteorite ALH84001

Ion microprobe oxygen isotopic measurements of a chemically diverse suite of carbonates from Martian meteorite ALH84001 are reported. The delta(sup 18)O values are highly variable, ranging from +5.4 to + 25.3%, and are correlated with major element compositions of the carbonate. The earliest forming (Ca-rich) carbonates have the lowest delta(sup 18)O values and the late-forming (Mg-rich) carbonates have the highest delta(sup 18)O values. Two models are presented which can explain the isotopic variations. The carbonates could have formed in a water rich environment at relatively low, but highly variable temperatures. In this open-system case the lower limit to the temperature variation is approx. 125 C, with fluctuations of over 250 C possible within the constraints of the model. Alternatively, the data can be explained by a closed-system model in which the carbonates precipitated from a limited amount of CO2-rich fluid. This scenario can reproduce the isotopic variations observed at a range of temperatures, including relatively high temperatures (less than 500 C). Thus the oxygen isotopic compositions do not provide unequivocal evidence for formation of the carbonates at low temperature. Although more information is needed in order to distinguish between the models, neither of the implied environments is consistent with biological activity. Thus, we suggest that features associated with the carbonates which have been interpreted to be the result of biological activity were most probably formed by inorganic processes.

Leshin, Laurie A.↗

Studies of Magmatic Inclusions in the Basaltic Martian Meteorites Shergotty, Zagami, EETA 79001 and QUE 94201

Currently there are 12 meteorites thought by planetary scientists to be martian samples, delivered to the Earth after violent impacts on that planet's surface. Of these 12 specimens, 4 are basaltic: Shergotty, Zagami, EETA 79001 and QUE 94201. Basalts are particularly important rocks to planetary geologists- they are the most common rocks found on the surfaces of the terrestrial planets, representing volcanic activity of their parent worlds. In addition, because they are generated by partial melting of the mantle and/or lower crust, they can serve as guide posts to the composition and internal processes of a planet. Consequently these four meteorites can serve as 'ground-truth' representatives of the predominant volcanic surface rocks of Mars, and offer researchers a glimpse of the magmatic history of that planet. Unfortunately, unraveling the parentage of a basaltic rock is not always straightforward. While many basalts are simple, unaltered partial melts of the mantle, others have undergone secondary processes which change the original parental chemistry, such as assimilation of other crustal rocks, mixing with other magmas, accumulation, re-equilibration between mineral species after crystallization, loss of late-stage magmatic fluids and alteration by metamorphic or metasomatic processes. Fortunately, magmatic inclusions can trap the evolving magmatic liquid, isolating it from many of these secondary processes and offering a direct look at the magma during different stages of development. These inclusions form when major or minor phases grow skeletally, surrounding small amounts of the parental magma within pockets in the growing crystal. The inclusion as a whole (usually consisting of glass with enclosed crystals) continues to represent the composition of the parental magma at the time the melt pocket closed, even when the rock as a whole evolves under changing conditions. The four basaltic martian meteorites contain several distinct generations of melt inclusions; those found within early-forming pigeonite, intermediate and late-forming Ti, Fe-oxides and sulfides, and intermediate to late-forming phosphates. In this summer' s study we have made a detailed study of all of the various forms of inclusions found within the 4 basaltic martian meteorites listed above. Glasses and minerals within the inclusions were analyzed using the Camera SX-100 Electron Microprobe in Building 31. The mineralogy and textural context of the inclusions will then be used to explore the crystallization history of these specimens, and to investigate any differences in crystallization history or parental magma compositions between these rocks. In this manner, the magmatic inclusions provide a road map backwards toward the 'parental' compositions for the basaltic martian meteorites and provide significant insight into the igneous processes found within the crust of Mars.

Harvey, Ralph P.↗

Outgassed water on Mars - Constraints from melt inclusions in SNC meteorites

The SNC (shergottite-nakhlite-chassignite) meteorites, thought to be igneous rocks from Mars, contain melt inclusions trapped at depth in early-formed crystals. Determination of the pre-eruptive water contents of SNC parental magmas from calculations of the solidification histories of these amphibole-bearing inclusions indicates that Martian magmas commonly contained 1.4 percent water by weight. When combined with an estimate of the volume of igneous materials on Mars, this information suggests that the total amount of water outgassed since 3.9 billion years ago corresponds to global depths on the order of 200 meters. This value is significantly higher than previous geochemical estimates but lower than estimates based on erosion by floods. These results imply a wetter Mars interior than has been previously thought and support suggestions of significant outgassing before formation of a stable crust or heterogeneous accretion of a veneer of cometary matter.

Mcsween, Harry Y., Jr.↗

The parent magma of the nakhlite meteorites - Clues from melt inclusions

Several forms of trapped liquid found within nakhlite meteorites have been examined, including interstitial melt and magmatic inclusions within the cores of large olivine grains. Differences in the mineralogy and texture between two types of trapped melt inclusions, and between these inclusions and the mesostasis, indicate that vitrophyric inclusions are most appropriate for estimating the composition of a nakhlite parental magma in equilibrium with early-forming olivine and augite. Parent liquids were calculated from the mineralogy of large inclusions in Nakhla and Governador Valadares, using a system of mass-balance equations solved by linear regression methods. The chosen parental liquids were cosaturated in olivine and augite and had Mg/Fe values consistent with measured augite/liquid Kds. These parental magma compositions are similar to other published compositions for Nakhla, Chassigny, and Shergotty parental melts, and may correspond to a significant magma type on Mars.

Harvey, Ralph P.↗

Petrogenesis of the nakhlite meteorites - Evidence from cumulate mineral zoning

Attention is given to a simple igneous petrogenesis for the meteorite Nakhla, which was previously called into question because Mg/Fe ratios in olivine indicate substantial disequilibrium between the predominant cumulus minerals (olivine and augite). Comparative analyses of simulated diffusive zoning and the observed cumulus mineral zoning for all three nakhlites (Nakhla, Governador Valadares, and Lafayette) show that their current compositions do not necessarily reflect parental magma compositions. Diffusion has altered primary cumulus compositions to varying degrees, Nakhla being the least affected, and Lafayette being almost completely reequilibrated. Since mineral zoning in each meteorite is strongly concentric around mesostasis areas, it is inferred that reaction with intercumulus liquid has controlled the observed zoning. It is argued that the nakhlites appear to be a series of relatively simple cumulate rocks which have undergone various amounts of late-magmatic and subsolidus diffusion, possibly reflecting their relative positions in a cooling cumulate pile.

Harvey, Ralph P.↗