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At least 19 records

Radioactive nuclear waste stabilization - Aspects of solid-state molecular engineering and applied geochemistry

Stabilization techniques for the storage of radioactive wastes are surveyed, with emphasis on immobilization in a primary barrier of synthetic rock. The composition, half-life, and thermal-emission characteristics of the wastes are shown to require thermally stable immobilization enduring at least 100,000 years. Glass materials are determined to be incapable of withstanding the expected conditions, average temperatures of 100-500 C for the first 100 years. The geological-time stability of crystalline materials, ceramics or synthetic rocks, is examined in detail by comparing their components with similar naturally occurring minerals, especially those containing the same radioactive elements. The high-temperature environment over the first 100 years is seen as stabilizing, since it can recrystallize radiation-induced metamicts. The synthetic-rock stabilization technique is found to be essentially feasible, and improvements are suggested, including the substitution of nepheline with freudenbergite and priderite for alkaline-waste stabilization, the maintenance of low oxygen fugacity, and the dilution of the synthetic-rock pellets into an inert medium.

Haggerty, S. E.↗

Sintering and hot pressing of Fra Mauro composition glass and the lithification of lunar breccias.

It is proposed that Apollo 14 type breccias lithify by sintering of particles of matrix glass under stress-free conditions. Meteorite impacts generate the heat necessary for sintering. Compacted angular particles of glass with the composition of an Apollo 14 rock were sintered experimentally. Loose clods of sub 37 micron grains form in several days at 700 C. Synthetic rocks, which texturally resemble the breccias, were produced at 795 C and above in 7.5 hours. Glass devitrified with increasing temperature. At 850 C, devitrification prevents much further densification of the synthetic breccias after 2 hours. Experiments compressing glass at 500 bars at 600 C produced dense vitreous masses which did not resemble lunar breccias. Confining pressure does not play a major role in lithifying the breccias. It is concluded that Apollo 14 type lunar breccias form at shallow depths at 800 C+ in a period of minutes to days.

Simonds, C. H.↗

Elastic velocity and Q factor measurements on Apollo 12, 14, and 15 rocks.

The Rayleigh wave velocities (vR) in one Apollo 12, one Apollo 15, and two Apollo 14 rocks were measured by the impulse technique. For 14310 vR = 1.20 km/sec; for 14321 vR = 0.9 km/sec; for 12063, on which the orientation dependence was studied, vR = 1.16-1.59 km/sec; for 15555 vR = 0.32 km/sec; and for synthetic rock 10017 analogue vR = 2.26 km/sec. This represents a larger spread by a factor of 3 than previously reported on lunar igneous rock. Absolute Q factor measurements were performed on one Apollo 14 rock by the vibrating bar technique. Under exposure to high vacuum and low temperatures, the Q factor is shown to increase towards values approaching the low end of the range of estimates from seismic data.

Tittmann, B. R.↗

Cerium Stable Isotope Analysis of Synthetic and Terrestrial Rock Reference Materials by MC-ICPMS

Cerium is the most abundant rare earth element (REE) in the solar photosphere, CI chondrites, and the Earth. It has four main stable isotopes (masses: 136,138,140, and 142), with 138Ce being the most studied species, used in geochronology and petrogenesis. In addition, more abundant 140Ce and 142Ce are suggested to be potentially applicable in geochemical investigations. In this work, we developed a modified four-step ion chromatography procedure for Ce chemical separation. Using a MC-ICPMS, we designed a cup configuration to measure 142Ce/140Ce ratio of the samples with an optimized Nd correction equation. A 0.03‰ (2SD) reproducibility was obtained for Ce Ames metal standard. We analyzed ten different igneous and one sedimentary geochemical reference materials. Mean δ142Ce range from −0.07 to 0.32‰. Most of the samples show a heavier Ce isotopic composition than the Ce Ames standard. The majority of rocks have a homogenous δ142Ce. The δ142Ce does not show any correlation with rock chemical composition including their Ce content or rock types. A carbonatite (SARM 40) has a mean δ142Ce of −0.07 ± 0.13‰ (2SD), lower than the other rocks, suggesting the possibility of a pronounced isotopic fractionation. Our work demonstrates the applicability of the developed methodology and the potential of Ce stable isotopes for future geochemical studies. Production of a larger database of δ142Ce values is required to obtain a clearer view on the similarities and differences between different geological material and explaining Ce stable isotope dynamics.

Cerium↗

Development of New Lunar Highland Regolith Simulant, NUW-LHT-5M

Introduction: NASA has a need for large quantities of lunar simulants that closely match future manned lunar missions at landing sites near the Lunar South Pole. The current simulant was designed to approximate NU-LHT-2M, and -4M, except using natural minerals and a fully synthetic, non-basaltic, high calcium glass. Washington Mills in Niagara Falls, NY was contracted to produce this new simulant due to their electric arc furnace (EAF) fusion technology and capabilities for crushing and sizing ceramics. The primary objectives of this work were: (1) to create a commercially produced simulant that contains a high fidelity, high calcium (An90+), low Mg/Fe glass without basaltic constituents; (2) to create a simulant that uses existing, terrestrially mined, and readily available minerals blended with a synthetic glass, and (3) accomplish objectives (1) and (2) using conventional processing methods capable of production levels that can meet substantial current and future demands of NASA projects. Another consideration was that highland simulants closest to meeting these requirements, NU-LHT-2M and -4M types, are out of production and largely out of stock. Design: The design chosen for development and production for this work is NU-LHT-2M, de-signed by Doug Stoeser and Douglas Rickman, which uses Stillwater anorthosite and norite rocks and synthetic glass. The composition targeted the average composition, glass content and particle size distribution of Apollo 16 samples [1]. The design utilizes two Stillwater minerals, anorthosite (37.7 wt.%), norite (17.6 wt.%), a commercially sourced olivine (4.7 wt.%), and a synthetic glass (40 wt.%). Processing: Stillwater rocks were hand collected and initially crushed by the USGS. Further crushing and milling was performed at Washing-ton Mills. For the glass, oxides were blended in the ap-propriate ratios, blended in a v-blender, and placed in a graphite lined, water cooled pot. The mixture was fused in Washington Mills’ pilot scale, 500 kW EAF. The molten glass was then poured into water and quenched to inhibit crystallization. Several pour/quench cycles were required to produce the total quantity of glass needed. Anorthosite, norite and olivine were milled together to the target particle size in a ball mill. The glass was ball milled separately. The complete simulant was produced by blending the milled materials. Particle size distribution, phase and chemical analyses of the materials was were per-formed at Washington Mills. Results: The glass composition was found to match the Apollo 16 oxide content average [1] quite well, with the exception of SiO2 and Fe2O3. The deviation of SiO2 and Fe2O3 from batched content was believed to be due to limitations inherent in the use of the arc furnace technique for these types of materials. A particle size distribution of the full simulant formulation closely matching the average for the Apollo 16 samples was also achieved. Fig. 1 shows the morphology of the final simulant particles. The size distribution is compared to the target in Fig. 2. Conclusions: A new lunar highlands type simulant containing a high-quality synthetic glass, closely matching an average composition of the Apollo 16 regolith was produced. Processing utilized easily scalable mineral and glass making methods.

simulant↗

Partition coefficients of Hf, Zr, and REE between phenocrysts and groundmasses

Partition coefficients of Hf, Zr, and REE between olivine, orthopyroxene, clinopyroxene, plagioclase, garnet, amphibole, ilmenite, phlogopite, and liquid are presented. Samples consist of megacrysts in kimberlite, phenocrysts in alkaline basalts, tholeiitic basalts and andesitic to dacitic rocks, and synthetic garnet and clinopyroxene in Hawaiian tholeiites. The Hf-Lu and Zr-Lu elemental fractionations are as large as the Lu-Sm or Lu-Nd fractionation. The Hf and Zr partition coefficients between mafic phenocrysts and liquids are smaller than the Lu partition coefficients, but are similar to the Nd or Sm partition coefficients. The Hf and Zr partition coefficients between ilmenite, phlogopite, and liquid are larger than the Lu partition coefficients for these minerals and their corresponding liquids. The Hf-Zr elemental fractionation does not occur except for extreme fractionation involving Zr-minerals and extremely low fO2. These data have an important bearing on chronological and petrogenetic tracer studies involving the Lu-Hf isotopic system.

Fujimaki, H.↗

The kinetics of ulvoespinel reduction - Synthetic study and applications to lunar rocks.

The kinetics of Fe2TiO4 reduction to FeTiO3 + Fe were studied using CO-CO2 gas mixtures with fO2 measured by a solid ceramic (calcia-zirconia) oxygen electrolyte cell. Isothermal rate studies at 900 C suggest that the mechanism of Fe2TiO4 reduction is one of nucleation and growth, where the growth stage may be controlled by the diffusion of the reactant through the product layer or volume diffusion. The activation energy for the growth stage of the process was determined to be 46 plus or minus 4 kcal/mole.

Mccallister, R. H.↗

Iron-titanium-chromite, a possible new carrier of remanent magnetization in lunar rocks.

Magnetic measurements of synthetic titanchromites reveal a characteristic transition at low temperature, making it possible to identify the presence of titanchromites in lunar rocks 12063, 14321 (dark clasts), and 14310. It is shown that titanchromites with a high chromium content could be the carriers of intermediate stability natural remanent magnetization observed in lunar rocks. Such natural remanent magnetization is acquired by transition thermoremanent magnetization at low temperature and cannot be duplicated by laboratory thermoremanent magnetization imparted above room temperature. The latter process will not yield the correct lunar paleointensity.

Banerjee, S. K.↗

Rayleigh wave studies in lunar rocks.

An ultrasonic surface wave technique described by the author (1971) is used to verify a hypothesis that links the seismic wave propagation velocities in lunar crust, much too low as compared to those on earth, to the extensive fracturing of lunar rock in the absence of liquids and gases which changed drastically the elastic and inelastic properties of lunar rock. Measurements on lunar rock samples and synthetic analogs suggest that the presence of microfractures have influence on both the wave velocity and Q factor in lunar rocks.

Tittmann, B. R.↗

Rheology of Diabase: Implications for Tectonics on Venus and Mars

Two important goals of our experimental investigation of the rheological behavior of diabase rocks were: (1) to determine flow laws describing their creep behavior over wide ranges of temperature, stress and strain rate and (2) to develop an understanding of the physical mechanisms by which these rocks flow under laboratory conditions. With this basis, a primary objective then was to construct constitutive equations that can be used to extrapolate from laboratory to planetary conditions. We specifically studied the rheological properties of both natural rock samples and synthetic aggregates. The former provided constraints for geologic systems, while the latter defined the relative contributions of the constituent mineral phases and avoided the influence of glass/melt found in natural samples. In addition, partially molten samples of crustal rock composition were deformed in shear to large strains (greater than 200%) important in crustal environments. The results of this research yielded essential rheological properties essential for models of crustal deformation on terrestrial planets, specifically Venus and Mars, as well as on the geodynamical evolution of these planets. Over the past three years, we also completed our investigation of the creep behavior of water ice with applications to the glaciers, ice sheets and icy satellites. Constitutive equations were determined that describe flow over a wide ranged of stress, strain rate, grain size and temperature. In the case of ice, three creep regimes were delineate. Extrapolation demonstrates that dislocation glide and grain boundary sliding processes dominate flow in ice I under planetary conditions and that diffusion creep is not an important deformation mechanism either in the laboratory or on icy satellites. These results have already been incorporated by other investigators into models describing, for example, the thickness and stability of the ice shell on Europa and to unravel long-standing discrepancies between field observations on glaciers and laboratory results.

Kohlstedt, David L.↗

C-O-H ratios of silicate melt inclusions in basalts from the Galapagos Spreading Center near 95 degrees W: a laser decrepitation mass spectrometry study

Volatile ratios (primarily of H2O and CO2) in individual silicate melt (glass) inclusions in minerals have been analyzed using laser volatilization and mass spectrometry. A Nd-glass laser was used to produce 50-micrometer diameter pits in silicate melt inclusions. Released volatiles were analyzed directly with a computer-controlled quadrupole mass spectrometer. The detection limits for CO2 and H2O were on the order of 3 x 10(-14) and 3 x 10(-13) moles, respectively. The reproducibility for CO2/H2O was better than +/- 9%. The total range of volatile ratios from vitreous silicate glass inclusions contained in a suite of Galapagos lavas were: 0.018 to 1.193 for CO2/H2O; 0.002 to 0.758 for CO/H2O; 0 to 0.454 for CH4/H2O; and 0 to 0.432 for Ar/H2O. The mean CO2/H2O from the propagating rift (0.245 +/- 0.068) silicate glass inclusions is significantly lower than that of the actively failing rift (0.641 +/- 0.241); this difference probably reflects different degrees of degassing during magmatic histories for the two regions. Relatively undifferentiated failing rift magmas must have relatively short crustal residence times prior to eruption and, therefore, have not undergone significant degassing of CO2, as would appear to be the case for the more highly fractionated propagating rift magmas. The laser-mass spectrometric system described herein has the ability to act as a point-source probing device that can differentiate between the various volatile sites in minerals and rocks (as well as synthetic materials) on a micrometer scale.

NASA Discipline Exobiology↗

Ferromagnetic phases of lunar fines and breccias - Electron magnetic resonance spectra of Apollo 16 samples

Electron magnetic resonance measurements have been made at 9 GHz and at temperatures from 1.2 to 400 K and 35 GHz (300 K) on samples of fines and breccias from Apollo 11-16. Unsorted Apollo 16 fines (less than 1 mm) have Delta H (average) = 580 G and specific intensities that have the same range as fines from the other Apollo collections. The magnetic properties of the 'characteristic' resonance are not in accord with those of iron particles. On the bases of the properties of the 'characteristic' resonance as a function of temperature and Apollo site, laboratory heat treatments on synthetic materials and lunar crystalline rocks and a comparison with the 'characteristic' resonance of the resonance spectra of breccia specimens for which iron particle sizes have been determined from other measurements, it is suggested that some fraction (about 20%) of the 'characteristic' resonance is due to sub-micron particles of ferric oxide phases.

Weeks, R. A.↗

Lunar resources: Oxygen from rocks and soil

The first set of hydrogen reduction experiments to use actual lunar material was recently completed. The sample, 70035, is a coarse-grained vesicular basalt containing 18.46 wt. percent FeO and 12.97 wt. percent TiO2. The mineralogy includes pyroxene, ilmenite, plagioclase, and minor olivine. The sample was crushed to a grain size of less than 500 microns. The crushed basalt was reduced with hydrogen in seven tests at temperatures of 900-1050 C and pressures of 1-10 atm for 30-60 minutes. A capacitance probe, measuring the dew point of the gas stream, was used to follow reaction progress. Experiments were also conducted using a terrestrial basalt similar to some lunar mare samples. Minnesota Lunar Simulant (MLS-1) contains 13.29 wt. percent FeO, 2.96 wt. percent Fe2O3, and 6.56 wt. percent TiO2. The major minerals include plagioclase, pyroxene, olivine, ilmenite, and magnetite. The rock was ground and seived, and experiments were run on the less than 74- and 500-1168-micron fractions. Experiments were also conducted on less than 74-micron powders of olivine, pyroxene, synthetic ilmenite, and TiO2. The terrestrial rock and mineral samples were reduced with flowing hydrogen at 1100 C in a microbalance furnace, with reaction progress monitored by weight loss. Experiments were run at atmospheric pressure for durations of 3-4 hr. Solid samples from both sets of experiments were analyzed by Mossbauer spectroscopy, petrographic microscopy, scanning electron microscopy, tunneling electron microscopy, and x-ray diffraction. Apollo 17 soil 78221 was examined for evidence of natural reduction in the lunar environment. This sample was chosen based on its high maturity level (I sub s/FeO = 93.0). The FeO content is 11.68 wt. percent and the TiO2 content is 3.84 wt. percent. A polished thin section of the 90-150 micron size fraction was analyzed by petrographic microscopy and scanning electron microscopy.

Allen, C. C.↗

Beta-FeOOH, akaganeite, in lunar rocks

Experiments were conducted to determine the nature of the alteration process in lunar rocks. Mixtures of 10 wt.% Fe + 10 wt.% FeCl2 + 80 wt.% basalt (terrestrial) were pelletized and allowed to set for 48 hrs at 25 C, at 40% and at 100% relative humidity. The end products were examined by reflected-light microscopy and by X-ray diffraction. The degree of reaction appears to depend upon the amount of FeCl2, the availability of water and the Ni content of the metallic Fe. The experiments showed the extremely rapid rate at which the oxyhydration can occur in air and that the product is beta-FeOOH. The data from the FeOOH mineral in rock 66095 were compared with those obtained from synthetic beta-FeOOH and found to be identical. The 'rust' in the Apollo 16 rocks could result from oxyhydration of the samples, caused by water vapor contamination, all or part of which occurred in the Apollo spacecraft and/or upon return to earth. The akageneite (beta-FeOOH) in lunar rocks could be entirely of terrestrial origin as originally suggested by Taylor et al. (1973).

Taylor, L. A.↗

Subcritical crack growth and other time- and environment-dependent behavior in crustal rocks

Stable crack growth strongly influences both the fracture strength of brittle rocks and some of the phenomena precursory to catastrophic failure. Quantification of the time and environment dependence of fracture propagation is attempted with the use of a fracture mechanics technique. Some of the difficulties encountered when applying techniques originally developed for simple synthetic materials to complex materials like rocks are examined. A picture of subcritical fracture propagation is developed that embraces the essential ingredients of the microstructure, a microcrack process zone, and the different roles that the environment plays. To do this, the results of (1) fracture mechanics experiments on five rock types, (2) optical and scanning electron microscopy, (3) studies of microstructural aspects of fracture in ceramics, and (4) exploratory tests examining the time-dependent response of rock to the application of water are examined.

Swanson, P. L.↗

In-Situ and Experimental Evidence for Acidic Weathering of Rocks and Soils on Mars

Experimental data for alteration of synthetic Martian basalts at pH=0-1 indicate that chemical fractionations at low pH are vastly different from those observed during terrestrial weathering. Rock analyses from Gusev crater are well described by the relationships apparent from low pH experimental alteration data. A model for rock surface alteration is developed which indicates that a leached alteration zone is present on rock surfaces at Gusev. This zone is not chemically fractionated to a large degree from the underlying rock interior, indicating that the rock surface alteration process has occurred at low fluid-to-rock ratio. The geochemistry of natural rock surfaces analyzed by APXS is consistent with a mixture between adhering soil/dust and the leached alteration zone. The chemistry of rock surfaces analyzed after brushing with the RAT is largely representative of the leached alteration zone. The chemistry of rock surfaces analyzed after grinding with the RAT is largely representative of the interior of the rock, relatively unaffected by the alteration process occurring at the rock surface. Elemental measurements from the Spirit, Opportunity, Pathfinder and Viking 1 landing sites indicate that soil chemistry from widely separated locations is consistent with the low-pH, low fluid to rock ratio alteration relationships developed for Gusev rocks. Soils are affected principally by mobility of FeO and MgO, consistent with alteration of olivine-bearing basalt and subsequent precipitation of FeO and MgO bearing secondary minerals as the primary control on soil geochemistry.

Hurowitz, J. A.↗