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At least 19 records

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NASA NTRS1993

Attenuation of Glass Dissolution in the Presence of Natural Additives

The study described here explored the dissolution kinetics of glasses in aqueous environments in systems which included a variety of natural crystalline solids in addition to the glass itself and the aqueous phase. The results demonstrated the possibility of a dramatic decrease in the rate of dissolution of silicate glass in the presence of certain varieties of olivine-based materials. This decrease in dissolution rate was shown to be due to the fact that these additives consist mostly of Mg-based material but also contain minor amounts of Al and Ca. The combined presence of Mg with these minor species affected the corrosion rate of the glass as a whole, including its most soluble components such as boron. The study has potentially important implications to the durability of glasses exposed to natural environments. The results may be relevant to the use of active backfill materials in burial sites for nuclear waste glasses as well as to better understanding of the environmental degradation of natural and ancient glasses.

Sang, Jing C.↗

NASA NTRS1985

Mathematical Model for Gas Dissolution in Glass

Mathematical model calculates rate of small oxygen-bubble contraction in soda/lime/silicate melts in presence of foreign nondiffusing gas. Process of interest in optical glass fabrication.

Weinberg, M. C.↗

NASA NTRSDate not supplied

Apatite Nanoresponse to Acidic Dissolution

Phosphorus uptake by plants and organisms is one of the most important life-sustaining processes occurring in the critical zone (CZ). Because 95% of Earth’s reserves is relatively immobile in the form of apatite, plants and organisms rely on molecular scale solubilization process to extract available P. As the world experiences a global P shortage, influencing food production, it becomes increasingly important to understand apatite dissolution. The detailed study of chemically weathered apatite surfaces at the μm to nm-scale is key to understanding P solubilization and uptake in the CZ, allowing for better crop management and efficient fertilization. Apatite weathering is generally viewed in terms of a pH-dependent process where protons weaken atomic bonds, this leading to the disintegration of the apatite structure. A general feature of apatite weathering in acid and near neutral pH conditions is an apparent non-stoichiometric dissolution characterized by [Ca/P]aq > 1.66 in both fluorapatites (FAP) and hydroxyapatites (HAP). This process leads to the formation of a surface altered layer (SAL) with a different composition from the bulk, which many have argued is a Ca-depleted “leached layer.” We investigated apatite weathering at the nanoscale using FIB-prepared TEM-foils. Our preliminary results based on laboratory-altered FAP at ambient T and pH 3 show the formation of amorphous SALs with a maximum thickness of ~10 nm. High resolution chemical mapping and profiling using STEM-EELS and STEM-EDXS indicate that the SALs are generally, but not always, depleted in Ca and enriched in P. These results provide an alternate view of the mechanism of apatite dissolution with stoichiometric breakdown of the apatite structure, followed by the reprecipitation of an amorphous surface layer depleted in Ca. This mechanism can be described in terms of coupled interfacial dissolution-reprecipitation (CIDR), which is increasingly viewed as a universal mechanism of silicate mineral and glass dissolution. Our observation that apatite may dissolve similarly to silicates implies not only that apatite weathering may be more complex than originally thought, but also that the CIDR mechanism may extend beyond silicates.

mineralogy↗

NASA NTRS1992

Glass corrosion in natural environments

Experiments carried out during the progress period are summarized. Experiments carried out involving glass samples exposed to solutions of Tris have shown the appearance of 'spikes' upon monitoring glass dissolution as a function of time. The periodic 'spikes' observed in Tris-based media were interpreted in terms of cracking due to excessive stress in the surface region of the glass. Studies of the interactions of silicate glasses with metal ions in buffered media were extended to systems containing Al. Caps buffer was used to establish the pH. The procedures used are described and the results are given. Preliminary studies were initiated as to the feasibility of adding a slowly dissolving solid compound of the additive to the glass-water system to maintain a supply of dissolved additive. It appears that several magnesium compounds have a suitable combination of solubility and affinity towards silicate glass surfaces to have a pronounced retarding effect on the extraction of uranium from the glass. These preliminary findings raise the possibility that introducing a magnesium source into geologic repositories for nuclear waste glass in the form of a sparingly soluble Mg-based backfill material may cause a substantial reduction in the extent of long-term glass corrosion. The studies described also provide mechanistic understanding of the roles of various metal solutes in the leachant. Such understanding forms the basis for developing long-term predictions of nuclear waste glass durability under repository conditions. From what is known about natural highly reduced glasses such as tektites, it is clear that iron is dissolved as ferrous iron with little or no ferric iron. The reducing conditions were high enough to cause metallic iron to exsolve out of the glass in the form of submicroscopic spherules. As the nuclear waste glass is much less reduced, a study was initiated on other natural glasses in addition to the nuclear waste glass. Extensive measurements were carried out on these glasses in order to characterize their magnetic properties. Results of these studies are described.

Thorpe, Arthur N.↗

NASA NTRS2004

Precipitation of Secondary Phases from the Dissolution of Silicate Glasses

Basaltic and anorthositic glasses were subjected to aqueous weathering conditions in the laboratory where the variables were pH, temperature, glass composition, solution composition, and time. Leached layers formed at the surfaces of glasses followed by the precipitation of X-ray amorphous iron and titanium oxides in acidic and neutral solutions at 25 C over time. Glass under oxidative hydrothermal treatments at 150 C yielded a three-layered surface; which included an outer smectite layer, a Fe-Ti oxide layer and an innermost thin leached layer. The introduction of Mg into solutions facilitated the formation of phyllosilicates. Aqueous hydrothermal treatment of anorthositic glasses (high Ca, low Ti) at 200 C readily formed smectite, whereas, the basaltic glasses (high Ti) were more resistant to alteration and smectite was not observed. Alkaline hydrothermal treatment at 2000e produced zeolites and smectites; only smectites formed at 200 C in neutral solutions. These mineralogical changes, although observed under controlled conditions, have direct applications in interpreting planetary (e.g., meteorite parent bodies) and terrestrial aqueous alteration processes.

Ming, Douglas W.↗

NASA NTRS1996

Dissolution kinetics of a lunar glass simulant at 25 degrees C: the effect of pH and organic acids

The dissolution kinetics of a simulated lunar glass were examined at pH 3, 5, and 7. Additionally, the pH 7 experiments were conducted in the presence of citric and oxalic acid at concentrations of 2 and 20 mM. The organic acids were buffered at pH 7 to examine the effect of each molecule in their dissociated form. At pH 3, 5, and 7, the dissolution of the synthetic lunar glass was observed to proceed via a two-stage process. The first stage involved the parabolic release of Ca, Mg, Al, and Fe, and the linear release of Si. Dissolution was incongruent, creating a leached layer rich in Si and Ti which was verified by transmission electron microscopy (TEM). During the second stage the release of Ca, Mg, Al, and Fe was linear. A coupled diffusion/surface dissolution model was proposed for dissolution of the simulated lunar glass at pH 3, 5, and 7. During the first stage the initial release of mobile cations (i.e., Ca, Mg, Al, Fe) was limited by diffusion through the surface leached layer of the glass (parabolic release), while Si release was controlled by the hydrolysis of the Si-O-Al bonds at the glass surface (linear release). As dissolution continued, the mobile cations diffused from greater depths within the glass surface. A steady-state was then reached where the diffusion rate across the increased path lengths equalled the Si release rate from the surface. In the presence of the organic acids, the dissolution of the synthetic lunar glass proceeded by a one stage process. The release of Ca, Mg, Al, and Fe followed a parabolic relationship, while the release of Si was linear. The relative reactivity of the organic acids used in the experiments was citrate > oxalate. A thinner leached layer rich in Si/Ti, as compared to the pH experiments, was observed using TEM. Rate data suggest that the chemisorption of the organic anion to the surface silanol groups was responsible for enhanced dissolution in the presence of the organic acids. It is proposed that the increased rate of Si release is responsible for the one stage parabolic release of mobile cations and the relatively thin leached layer compared to experiments at pH 3 and 5.

NASA Discipline Life Support Systems↗

NASA NTRS1988

Interactions of silicate glasses with aqueous environments under conditions of prolonged contact and flow

This paper discusses mechanisms involving saturation and reactions that lead to the formation of altered phases in silicate glasses considered for use in geologic repositories for nuclear waste. It is shown that the rate of dissolution of silicate glasses exposed to a broad range of contact times, leachant compositions, and surface-to-volume ratios is strongly affected by the presence of reactive species such as Al, Mg, and Fe. The reactive materials may originate in the leachant or, under conditions of high surface-to-volume ratio, in the glass itself. The effects of glass composition on the course of the corrosion process can be viewed in terms of the formation of a surface layer on the leached glass; the type, composition, and structure of this layer control the dissolution behavior of the glass.

Barkatt, Aaron↗

NASA NTRS1996

Experimental Constraints on the Origin of Lunar High-Ti Ultramafic Glasses

Phase equilibria and dissolution rate experiments are used to develop a petrogenetic model for the high-Ti lunar ultramafic glasses. Near-liquidus phase relations of the Apollo 14 black glass, the most Ti-rich lunar ultramafic glass, are determined to 2.2-GPa. The liquidus is saturated with Cr-spinel at 1-atm, olivine between approximately 0.5- and 1.5-GPa, and low-Ca pyroxene + Cr-spinel above 1.5-GPa. Ilmenite does not crystallize near the liquidus and implies that high-Ti ultramafic glasses are not produced by melting of an ilmenite-saturated source. We infer that high-Ti ultramafic magmas are derived from low-Ti ultramafic parent magmas by assimilation of ilmenite +/- clinopyroxene +/- urKREEP +/- pigeonite in the shallow lunar interior. Heat is provided by adiabatic ascent of the low-Ti ultramafic primary magmas from the deeper lunar interior and crystallization of olivine during assimilation. The assimilation reaction is modeled by mass balance and requires that ilmenite and high-Ca pyroxene are assimilated in a approximately 3:1 ratio, a much higher ratio than the proportion in which these minerals are thought to exist in the lunar interior. In an effort to understand the kinetic controls on this reaction, the dissolution of ilmenite is examined experimentally in both low- and high-Ti lunar magmas. We find that ilmenite dissolves incongruently to Cr-spinel and a high-Ti melt. The dissolution reaction proceeds by a diffusion-controlled mechanism. An assimilation model for the origin of high-Ti melts is developed that leaves the magma ocean cumulates in their initial stratigraphic positions and obviates source hybridization models that require lunar overturn.

Wagner, T. P.↗

NASA NTRS1993

Assimilation in lunar basalts and volcanic glasses: Implications for a heterogenous mantle source region

Several scientists have called on assimilation of anorthositic crustal material or KREEP compositions to explain various lunar lithologies. In order to address the practicality of such processes, some techniques for calculating how much assimilation is possible in magma chambers and dikes based on thermal energy balances and simple fluid mechanical constraints are outlined. In a previous effort, it was demonstrated that dissolution of plagioclase in an iron-free basalt was too slow to contaminate magmas, and that the energy cost of melting plagioclase-rich crustal material was prohibitive both in magma chambers and in dike conduits. This analysis was extended to include dissolution rates in an orange glass composition and to quantitatively predict the maximum contamination possible due to assimilation of both lunar crustal material and KREEP.

Finnila, A. B.↗

NASA NTRS1982

Preliminary study of the effects of a reversible chemical reaction on gas bubble dissolution

A preliminary investigation is carried out of the effects of a reversible chemical reaction on the dissolution of an isolated, stationary gas bubble in a glass melt. The exact governing equations for the model system are formulated and analyzed. The approximate quasi-steady-state version of these equations is solved analytically, and a calculation is made of bubble dissolution rates. The results are then compared with numerical solutions obtained from the finite difference form of the exact governing equations. It is pointed out that in the microgravity condition of space, the buoyant rise of a gas bubble in a glass melt will be negligible on the time scale of most experiments. For this reason, a determination of the behavior of a stationary gas bubble in a melt is relevant for an understanding of glass refining in space.

Weinberg, M. C.↗

NASA NTRS2004

Evidence for Differential Comminution/Aeolian Sorting and Chemical Weathering of Martian Soils Preserved in Mars Meteorite EET79001

Impact-melt glasses containing Martian atmospheric gases in Mars meteorite EET79001 are formed from Martian soil fines that had undergone meteoroid-comminution and aeolian sorting accompanied by chemical weathering near Mars surface. Using SiO2 and SO3 as proxy for silicates and salts respectively in Mars soils, we find that SiO2 and SO3 correlate negatively with FeO and MgO and positively with Al2O3 and CaO in these glasses, indicating that the mafic and felsic components are depleted and enriched relative to the bulk host (Lith A/B) respectively as in the case of Moon soils. Though the overall pattern of mineral fractionation is similar between the soil fines on Mars and Moon, the magnitudes of the enrichments/depletions differ between these sample-suites because of pervasive aeolian activity on Mars. In addition to this mechanical processing, the Martian soil fines, prior to impact-melting, have undergone acid-sulfate dissolution under oxidizing/reducing conditions. The S03 content in EET79001,507 (Lith B) glass is approx.18% compared to < 2% in EET79001, 506 (Lith A). SiO2 and SO3 negatively correlate with each other in ,507 glasses similar to Pathfinder soils. The positive correlation found between FeO and SO3 in ,507 glasses as well as Pathfinder rocks and soils is consistent with the deposition of ferric-hydroxysulfate on regolith grains in an oxidizing environment. As in the case of Pathfinder soils, the Al 2O3 vs SiO2 positive correlation and FeO VS S102 negative correlation observed in ,507 glasses indicate that SiO2 from the regolith is mobilized as soluble silicic acid at low pH. The large off-set in the end-member FeO abundance ( SO3=0) between Pathfinder soil-free rock and sulfur-free rock in ,507 glass precursors suggests that the soils comprising the ,507 glasses contain much larger proportion of fine-grained Martian soil fraction that registers strong mafic depletion relative to Lith B. This inference is strongly supported by the Al2O3 - SO3 negative correlation observed in both ,507 glasses and pathfinder soils. Furthermore, the flat MgO-SO3 correlation observed in the case of ,507 glasses shows that the solubilized MgSO4 is mobilized by the aqueous solutions leaving behind the rock-residue with approx.2-3% MgO. This value is similar to the approx.2% MgO found for the soil-free rock at the Pathfinder site. The EET79001 ,506 glasses, in contrast, show that Al2O3 and CaO positively correlate with SO3 indicating that Al is precipitated as amorphous hydroxysulfate at relatively high pH. The FeO - SO3 negative correlation observed in ,506 glasses yields an end-member FeO abundance of approx.21% for the sulfur-free rock, which is consistent with the 22% FeO deduced for the Viking soil-free rock. Further, the FeO and MgO negative correlation with S03 observed in ,506 glasses indicates that the divalent Fe and Mg released from ferromagnesian minerals by acid sulfate dissolution are mobilized away from the reaction sites as soluble sulfates under reducing environment. A similar negative correlation between FeO and SO3 and a positive correlation between Al2O3 and SO3 found in Viking soils suggest that they also had undergone acid-sulfate dissolution under relatively reducing conditions.

Rao, M. N.↗

NASA NTRS2009

Column Experiments to Interpret Weathering in Columbia Hills

Phosphate mobility has been postulated as an indicator of early aqueous activity on Mars. In addition, rock surfaces analyzed by the Mars Exploration Rover Spirit are consistent with the loss of a phosphate- containing mineral To interpret phosphate alteration behavior on Mars, we performed column dissolution experiments leaching the primary phases Durango fluorapatite, San Carlos olivine, and basalt glass (Stapafjell Volcano, courtesy of S. Gislason, University of Iceland) [3,4]) with acidic solutions. These phases were chosen to represent quickly dissolving phases likely present in Columbia Hills. Column dissolution experiments are closer to natural dissolution conditions than batch experiments, although they can be difficult to interpret. Acidic solutions were used because the leached layers on the surfaces of these rocks have been interpreted as resulting from acid solutions [5].

Hausrath, E. M.↗

NASA NTRS1987

Glass properties in the yttria-alumina-silica system

The glass formation region in the yttria-alumina-silica system was investigated. Properties of glasses containing 25 to 55 wt pct yttria were measured and the effect of the composition was determined. The density, refractive index, thermal-expansion coefficient, and microhardness increased with increasing yttria content. The dissolution rate in 1N HCl increased with increasing yttria content and temperature. These glasses were also found to have high electrical resistivity.

Hyatt, M. J.↗

NASA NTRS1984

Zirconium fluoride glass - Surface crystals formed by reaction with water

The hydrated surfaces of a zirconium barium fluoride glass, which has potential for application in optical fibers and other optical elements, were observed by scanning electron microscopy. Crystalline zirconium fluoride was identified by analysis of X-ray diffraction patterns of the surface crystals and found to be the main constituent of the surface material. It was also found that hydrated zirconium fluorides form only in highly acidic fluoride solutions. It is possible that the zirconium fluoride crystals form directly on the glass surface as a result of its depletion of other ions. The solubility of zirconium fluoride is suggested to be probably much lower than that of barium fluoride (0.16 g/100 cu cm at 18 C). Dissolution was determined to be the predominant process in the initial stages of the reaction of the glass with water. Penetration of water into the glass has little effect.

Doremus, R. H.↗

NASA NTRS2011

The Formation of Fe/Mg Smectite Under Mildly Acidic Conditions on Early Mars

The detection of Fe/Mg smectites and carbonate in Noachian and early Hesperian terrain of Mars has been used to suggest that neutral to mildly alkaline conditions prevailed during the early history of Mars. However, if early Mars was neutral to moderately alkaline with a denser CO2 atmosphere than today, then large carbonates deposits should be more widely detected in Noachian terrain. The critical question is: Why have so few carbonate deposits been detected compared to Fe/Mg smectites? We suggest that Fe/Mg smectites on early Mars formed under mildly acidic conditions, which would inhibit the extensive formation of carbonate deposits. The goal of this work is to evaluate the formation of Fe/Mg smectites under mildly acidic conditions. The stability of smectites under mildly acidic conditions is attributed to elevated Fe/Mg activities that inhibit smectite dissolution. Beidelite and saponite have been shown to form from hydrothermal alteration of basaltic glass at pH 3.5-4.0 in seawater solutions. Nontronite is also known to be stable in mildly acidic systems associated with mafic and ultramafic rock. Nontronite was shown to form in acid sulfate soils in the Bangkok Plain, Thailand due to oxidation of Fe-sulfides that transformed saponite to nontronite. Smectite is known to transform to kaolinite in naturally acid soils due to selective leaching of Mg. However, if Mg removal is limited, then based on equilibrium relationships, the dissolution of smectite should be minimized. If Fe and Mg solution activities are sufficiently high, such as might be found in a low water/rock ratio system that is poorly drained, smectite could form and remain stable under mildly acidic conditions on Mars. The sources of mild acidity on early Mars includes elevated atmospheric CO2 levels, Fe-hydrolysis reactions, and the presence of volcanic SO2 aerosols. Equilibrium calculations dictate that water equilibrated with an early Mars CO2 atmosphere at 1 to 4 bar yields a pH of 3.6 to 3.9. Fe hydrolysis reactions on Mars is another source of protons that would have contributed to acidity. The presence of SO2 from volcanic processes could also have contributed to geochemical acidification. These sources of acidity competed with base-forming cations that resulted in mildly acidic solutions that were not favorable for carbonate formation but may have allowed for Fe/Mg smectite formation. Noachian to early Hesperian Mars could have been mildly acidic, allowing Fe/Mg smectite formation but preventing widespread carbonate deposition. This paradigm shift from an early Mars that was neutral-alkaline to mildly acidic may possibly explain why there is a disparity between the occurrence of carbonate and Fe/Mg smectites. Potential microbiological activity would not be eliminated under a mildly acidic Mars; however, there could be tighter constraints as to the type and species of microbiology that could exist.

Sutter, Brad↗

NASA NTRS1986

Physical data measurements and mathematical modelling of simple gas bubble experiments in glass melts

In this work consideration is given to the problem of the extraction of physical data information from gas bubble dissolution and growth measurements. The discussion is limited to the analysis of the simplest experimental systems consisting of a single, one component gas bubble in a glassmelt. It is observed that if the glassmelt is highly under- (super-) saturated, then surface tension effects may be ignored, simplifying the task of extracting gas diffusivity values from the measurements. If, in addition, the bubble rise velocity is very small (or very large) the ease of obtaining physical property data is enhanced. Illustrations are given for typical cases.

Weinberg, Michael C.↗

NASA NTRS2004

Lunar and Planetary Science XXXV: Viewing the Lunar Interior Through Titanium-Colored Glasses

The session"Viewing the Lunar Interior Through Titanium-Colored Glasses" included the following reports:Consequences of High Crystallinity for the Evolution of the Lunar Magma Ocean: Trapped Plagioclase; Low Abundances of Highly Siderophile Elements in the Lunar Mantle: Evidence for Prolonged Late Accretion; Fast Anorthite Dissolution Rates in Lunar Picritic Melts: Petrologic Implications; Searching the Moon for Aluminous Mare Basalts Using Compositional Remote-Sensing Constraints II: Detailed analysis of ROIs; Origin of Lunar High Titanium Ultramafic Glasses: A Hybridized Source?; Ilmenite Solubility in Lunar Basalts as a Function of Temperature and Pressure: Implications for Petrogenesis; Garnet in the Lunar Mantle: Further Evidence from Volcanic Glasses; Preliminary High Pressure Phase Relations of Apollo 15 Green C Glass: Assessment of the Role of Garnet; Oxygen Fugacity of Mare Basalts and the Lunar Mantle. Application of a New Microscale Oxybarometer Based on the Valence State of Vanadium; A Model for the Origin of the Dark Ring at Orientale Basin; Petrology and Geochemistry of LAP 02 205: A New Low-Ti Mare-Basalt Meteorite; Thorium and Samarium in Lunar Pyroclastic Glasses: Insights into the Composition of the Lunar Mantle and Basaltic Magmatism on the Moon; and Eu2+ and REE3+ Diffusion in Enstatite, Diopside, Anorthite, and a Silicate Melt: A Database for Understanding Kinetic Fractionation of REE in the Lunar Mantle and Crust.

Source record↗

NASA NTRS1994

Assimilation by lunar mare basalts: Melting of crustal material and dissolution of anorthite

We discuss techniques for calculating the amount of crustal assimilation possible in lunar magma chambers and dikes based on thermal energy balances, kinetic rates, and simple fluid mechanical constraints. Assuming parent magmas of picritic compositions, we demonstrate the limits on the capacity of such magmas to melt and dissolve wall rock of anorthitic, troctolitic, noritic, and KREEP (quartz monzodiorite) compositions. Significant melting of the plagioclase-rich crustal lithologies requires turbulent convection in the assimilating magma and an efficient method of mixing in the relatively buoyant and viscous new melt. Even when this occurs, the major element chemistry of the picritic magmas will change by less than 1-2 wt %. Diffusion coefficients measured for Al2O3 from an iron-free basalt and an orange glass composition are 10(exp -12) sq m/s at 1340 C and 10(exp -11) sq m/s at 1390 C. These rates are too slow to allow dissolution of plagioclase to significantly affect magma compositions. Picritic magmas can melt significant quantities of KREEP, which suggests that their trace element chemistry may still be affected by assimilation processes; however, mixing viscous melts of KREEP composition with the fluid picritic magmas could be prohibitively difficult. We conclude that only a small part of the total major element chemical variation in the mare basalt and volcanic glass collection is due to assimilation/fractional crystallization processes near the lunar surface. Instead, most of the chemical variation in the lunar basalts and volcanic glasses must result from assimilation at deeper levels or from having distinct source regions in a heterogeneous lunar mantle.

Finnila, A. B.↗