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Volatile metal deposits on lunar soils - Relation to volcanism

Parallel leaching and volatilization experiments conducted on lunar samples and similar experiments on sphalerite do not supply the information needed to resolve the question of the chemical nature of Pb-204, Zn, Bi, and Tl deposits on lunar soil surfaces. It is proposed that in Apollo 17 mare and terra soils the fractions of Pb-204, Zn, and Tl that are insoluble under mild, hot pH 5 HNO3, leaching conditions and involatile at 600 C were originally surface deposits which became immobilized by migration into the silicate substrate or by chemisorption. Most of the Bi does not seem to be the result of such a deposit. The implication is also that the soils, over their respective times of evolution, were exposed to heavy metal vapors or that an episodic exposure occurred after they had evolved. A sequence of events is proposed to account for orange 74220 and black 74001 glasses by lava fountaining and for soil 74241 as tephra from an explosive volcanic eruption.

Reed, G. W., Jr.

Chemical processing of lunar materials

The paper highlights recent work on the general problem of processing lunar materials. The discussion covers lunar source materials, refined products, motivations for using lunar materials, and general considerations for a lunar or space processing plant. Attention is given to chemical processing through various techniques, including electrolysis of molten silicates, carbothermic/silicothermic reduction, carbo-chlorination process, NaOH basic-leach process, and HF acid-leach process. Several options for chemical processing of lunar materials are well within the state of the art of applied chemistry and chemical engineering to begin development based on the extensive knowledge of lunar materials.

Criswell, D. R.

Silicon oxidation in fluoride solutions

Silicon is produced in a NaF, Na2SiF6, and Na matrix when SiF4 is reduced by metallic sodium. Hydrogen is evolved during acid leaching to separate the silicon from the accompanying reaction products, NaF and Na2SiF6. The hydrogen evolution reaction was studied under conditions simulating leaching conditions by making suspensions of the dry silicon powder in aqueous fluoride solutions. The mechanism for the hydrogen evolution is discussed in terms of spontaneous oxidation of silicon resulting from the cooperative effects of (1) elemental sodium in the silicon that reacts with water to remove a protective silica layer, leaving clean reactive silicon, and (2) fluoride in solution that complexes with the oxidized silicon in solution and retards formation of a protective hydrous oxide gel.

Sancier, K. M.

Extracting Silicon From Sodium-Process Products

New acid leaching process purifies silicon produced in reaction between silicon fluoride and sodium. Concentration of sodium fluoride and other impurities and byproducts remaining in silicon are within acceptable ranges for semi-conductor devices. Leaching process makes sodium reduction process more attractive for making large quantities of silicon for solar cells.

Kapur, V.

Impulsive phase solar flare X-ray polarimetry

The pioneering observational work in solar flare X-ray polarimetry was done in a series of satellite experiments by Tindo and his collaborators in the Soviet Union; initial results showed high levels of polarization in X-ray flares (up to 40%), although of rather low statistical significance, and these were generally interpreted as evidence for strong beaming of suprathermal electrons in the flare energy release process. However, the results of the polarimeter flown by the Columbia Astrophysics Laboratory as part of the STS-3 payload on the Space Shuttle by contrast showed very low levels of polarization. The largest value (observed during the impulsive phase of a single event) was 3.4% + or - 2.2%. At the same time but independent of the observational work, Leach and Petrosian (1983) showed that the high levels of polarization in the Tindo results were difficult to understand theoretically, since the electron beam is isotropized on an energy loss timescale. A subsequent comparison by Leach, Emslie, and Petrosian (1985) of the impulsive phase STS-3 result and the above theoretical treatment shows that the former is consistent with several current models and that a factor of approximately 3 improvement in sensitivity is needed to distinguish properly among the possibilities.

Chanan, Gary

Humidity-induced room-temperature decomposition of Au contacted indium phosphide

It has been found that Au-contacted InP is chemically unstable at room temperature in a humid ambient due to the leaching action of indium nitrate islands that continually remove In from the contact metallization and thus, in effect, from the Inp substrate. While similar appearing islands form on Au-contacted GaAs, that system appears to be stable since leaching of the group III element does not take place.

Fatemi, Navid S.

U-Th-Pb isotopic systematics of lunar norite 78235

A pristine high-Mg noritic cumulate thought to be relict deep-seated lunar crust is studied with an eye to obtaining evidence of initial Pb isotopic composition and U/Pb ratios of early lunar magma sources and possibly of a primary magma ocean. A leaching procedure was conducted on polymineralic separates to assure the removal of secondary Pb components. The Pb from leached separates do not form a linear trend on the Pb-Pb diagram, indicating open-system behavior either from mixtures of Pb or postcrystallization disturbances. Calculated initial Pb compositions and corresponding U-238/Pb-204 (mu) values are presented, with the assumption of reasonably precise radiometric ages from the literature for norite 78236. The results obtained support the contention that high-Mg suite rocks are coeval with the ferroan anorthosites, both being produced during the earliest stages of lunar evolution.

Premo, W. R.

Movement of Trace Elements During Residence in the Antarctic Ice: a Laboratory Simulation

Recent work has determined that differences in the trace element distribution between Antarctic eucrites and non-Antarctic eucrites may be due to weathering during residence in the ice, and samples that demonstrate trace element disturbances do not necessarily correspond to eucrites that appear badly weathered to the naked eye. This study constitutes a preliminary test of the idea that long-term residence in the ice is the cause of the trace element disturbances observed in the eucrites. Samples of a non-Antarctic eucrite were leached in water at room temperature conditions. Liquid samples were analyzed for rare earth element abundances using ion chromatography. The results for the short-term study showed little or no evidence that leaching had occurred. However, there were tantalizing hints that something may be happening. The residual solid samples are currently being analyzed for the unleached trace metals using instrumental neutron activation analysis and should show evidence of disturbance if the chromatography clues were real. In addition, another set of samples continues to be intermittently sampled for later analysis. The results should give us information about the movement of trace elements under our conditions and allow us to make some tentative extrapolations to what we observe in actual Antarctic eucrite samples.

Strait, Melissa M.

Characterization of the Water Soluble Component of Inedible Residue from Candidate CELSS Crops

Recycling of inorganic nutrients required for plant growth will be a necessary component of a fully closed, bioregenerative life support system. This research characterized the recovery of plant nutrients from the inedible fraction of three crop types (wheat, potato, and soybean) by soaking, or leaching, in water. A considerable portion of the dry weight of the inedible biomass was readily soluble (29 percent for soybean, 43 percent for wheat, and 52 percent for potato). Greater weight loss from potato was a result of higher tissue concentrations of potassium, nitrate, and phosphate. Approximately 25 percent of the organic content of the biomass was water soluble, while the majority of most inorganic nutrients, except for calcium and iron, were recovered in the leachate. Direct use of the leachates in hydroponic media could provide between 40-90 percent of plant nutrient demands for wheat, and 20-50 percent of demand for soybean and potato. Further evaluation of leaching as a component of resource recovery scheme in a bioregenerative system requires study of (1) utilization of plant leachates in hydroponic plant culture; and (2) conversion of organic material (both soluble and insoluble) into edible, or other useful, products.

Garland, Jay

The U-Th-Pb, Sm-Nd, and Ar-Ar isotopic systematics of lunar meteorite Yamato-793169

U-Th-Pb, Sm-Nd, and (Ar-40)-(Ar-39) isotopic studies were performed on Yamato (Y)-793169, an unbrecciated diabasic lunar meteorite whose chemical composition is close to low Ti(LT) and very low-Ti (VLT) mare basalts. The isotopic data indicate that the meteorite was formed earlier than 3.9 Ga from a source with low U/Pb and high Sm/Nd and was distributed by a thermal event at 751 Ma. due to the small sample size (104 mg), a plagioclase crystal and glass grains were handpicked for Ar analysis, leaving four fractions for the U-Th-Pb and Sm-Nd studies; a fine-grained fraction (less than 63 microns; Fine) and three medium-grained fractions (63-150 microns). Medium-grained fractions were divided by density; a heavy fraction (rho greater than 3.3) consisting mainly of pyroxene (PX1), a lighter fraction (rho less than 2.8) consisting of plagioclase (PL), and a middle density fraction (predominantly pyroxene; PX2). The fractions were washed with acetone and alcohol, and then leached in 0.01 HBr and 0.1N HBr in order to remove any terrestrial Pb contamination. Analysis of the HBr leaches revealed that this meteorite was heavily contaminated with terrestrial Pb during its residence in Antarctic ice.

Torigoye, Noriko

Amino acids in the Tagish Lake Meteorite

High-performance liquid chromatography (HPLC) based amino acid analysis of a Tagish Lake meteorite sample recovered 3 months after the meteorite fell to Earth have revealed that the amino acid composition of Tagish Lake is strikingly different from that of the CM and CI carbonaceous chondrites. We found that the Tagish Lake meteorite contains only trace levels of amino acids (total abundance = 880 ppb), which is much lower than the total abundance of amino acids in the CI Orgueil (4100 ppb) and the CM Murchison (16 900 ppb). Because most of the same amino acids found in the Tagish Lake meteorite are also present in the Tagish Lake ice melt water, we conclude that the amino acids detected in the meteorite are terrestrial contamination. We found that the exposure of a sample of Murchison to cold water lead to a substantial reduction over a period of several weeks in the amount of amino acids that are not strongly bound to the meteorite matrix. However, strongly bound amino acids that are extracted by direct HCl hydrolysis are not affected by the leaching process. Thus even if there had been leaching of amino acids from our Tagish Lake meteorite sample during its 3 month residence in Tagish Lake ice and melt water, a Murchison type abundance of endogenous amino acids in the meteorite would have still been readily detectable. The low amino acid content of Tagish Lake indicates that this meteorite originated fiom a different type of parent body than the CM and CI chondrites. The parent body was apparently devoid of the reagents such as aldehyldes/ketones, HCN and ammonia needed for the effective abiotic synthesis of amino acids. Based on reflectance spectral measurements, Tagish Lake has been associated with P- or D-type asteroids. If the Tagish Lake meteorite was indeed derived fiom these types of parent bodies, our understanding of these primitive asteroids needs to be reevaluated with respect to their potential inventory of biologically important organic compounds.

Kminek, G.

Recycling crop residues for use in recirculating hydroponic crop production

As part of bioregenerative life support feasibility testing by NASA, crop residues are being used to resupply elemental nutrients to recirculating hydroponic crop production systems. Methods for recovering nutrients from crop residues have evolved from water soaking (leaching) to rapid aerobic bioreactor processing. Leaching residues recovered the majority of elements but it also recovered significant amounts of soluble organics. The high organic content of leachates was detrimental to plant growth. Aerobic bioreactor processing reduced the organic content ten-fold, which reduced or eliminated phytotoxic effects. Wheat and potato production studies were successful using effluents from reactors having with 8- to 1-day retention times. Aerobic bioreactor effluents supplied at least half of the crops elemental mass needs in these studies. Descriptions of leachate and effluent mineral content, biomass productivity, microbial activity, and nutrient budgets for potato and wheat are presented.

NASA Center KSC

Long-term productivity in the cryptoendolithic microbial community of the Ross Desert, Antarctica

Annual gross productivity of the lichen-dominated cryptoendolithic community was calculated from a computer analysis of photosynthetic response based on laboratory measurements of CO2 exchange and three years (1985-1988) of field nanoclimate data. Photosynthetic optimum increased from -3 to 2 degrees C between irradiance levels of 100 and 1500 micromoles photons m-2 s-1, while the upper compensation point rose from 1 to 17 degrees C. The mean yearly total time available for metabolic activity (temperature above -10 degrees C and moisture present) was 771.3 h for horizontal rock, 421.5 h for northeast-oriented sloped rock, and 1042.2 h for a small depression in horizontal rock (the characteristic site of occasional lichen apothecia). The calculated mean gross productivity value for a horizontal rock was 1215 mg C m-2 y-1, and net photosynthetic gain was 606 mg C m-2 y-1. Net ecosystem productivity (annual accretion of cellular biomass) estimated from long-term events amounted to only about 3 mg C m-2 y-1. The difference between these two values may represent the long-term metabolic costs of the frequent dehydration-rehydration and freezing-thawing cycles or of overwintering, and may account for the leaching of organic substances to the rock. The yearly gross productivity of the cryptoendolithic microbial community of the entire Ross Desert area was estimated at approximately 120,000-180,000 kg C. Of this, 600-900 kg C is in microbial biomass, and much of the rest is soluble compounds that leach into the rocks and possibly percolate to the valleys, providing a source of organic matter for lakes, rivers, and soils.

NASA Program Exobiology

Effect of osteoblastic culture conditions on the structure of poly(DL-lactic-co-glycolic acid) foam scaffolds

Poly(DL-lactic-co-glycolic acid) (PLGA) foams are an osteoconductive support that holds promise for the development of bone tissue in vitro and implantation into orthopedic defects. Because it is desirable that foams maintain their shape and size, we examined a variety of foams cultured in vitro with osteoblastic cells. Foams were prepared with different porosities and pore sizes by the method of solvent casting/porogen leaching using 80, 85, and 90 wt% NaCl sieved with particle sizes of 150-300 and 300-500 microm and characterized by mercury intrusion porosimetry. Foams seeded with cells were found to have volumes after 7 days in static culture that decreased with increasing porosity: the least porous exhibited no change in volume while the most porous foams decreased by 39 +/- 10%. In addition, a correlation was observed between decreasing foam volume after 7 days in culture and decreasing internal surface area of the foams prior to seeding. Furthermore, foams prepared with the 300-500 microm porogen had lower porosities, greater mean wall thicknesses between adjacent pores, and larger volumes after 7 days in culture than those prepared with the smaller porogen. Two culture conditions for maintaining cells, static and agitated (in a rotary vessel), were found to have similar influences on foam size, cell density, and osteoblastic function for 7 and 14 days in culture. Finally, we examined unseeded foams in aqueous solutions of pH 3.0, 5.0, and 7.4 and found no significant decrease in foam size with degradation. This study demonstrates that adherent osteoblastic cells may collapse very porous PLGA foams prepared by solvent casting/particulate leaching: a potentially undesirable property for repair of orthopedic defects.

NASA Program Fundamental Space Biology

Laboratory Simulated Acid-Sulfate Weathering of Basaltic Materials: Implications for Formation of Sulfates at Meridiani Planum and Gusev Crater, Mars

Acid-sulfate weathering of basaltic materials is a candidate formation process for the sulfate-rich outcrops and rocks at the MER rover Opportunity and Spirit landing sites. To determine the style of acid-sulfate weathering on Mars, we weathered basaltic materials (olivine-rich glassy basaltic sand and plagioclase feldspar-rich basaltic tephra) in the laboratory under different oxidative, acid-sulfate conditions and characterized the alteration products. We investigated alteration by (1) sulfuric-acid vapor (acid fog), (2) three-step hydrothermal leaching treatment approximating an open system and (3) single-step hydrothermal batch treatment approximating a "closed system." In acid fog experiments, Al, Fe, and Ca sulfates and amorphous silica formed from plagioclase-rich tephra, and Mg and Ca sulfates and amorphous silica formed from the olivine-rich sands. In three-step leaching experiments, only amorphous Si formed from the plagioclase-rich basaltic tephra, and jarosite, Mg and Ca sulfates and amorphous silica formed from olivine-rich basaltic sand. Amorphous silica formed under single-step experiments for both starting materials. Based upon our experiments, jarosite formation in Meridiani outcrop is potential evidence for an open system acid-sulfate weathering regime. Waters rich in sulfuric acid percolated through basaltic sediment, dissolving basaltic phases (e.g., olivine) and forming jarosite, other sulfates, and iron oxides. Aqueous alteration of outcrops and rocks on the West Spur of the Columbia Hills may have occurred when vapors rich in SO2 from volcanic sources reacted with basaltic materials. Soluble ions from the host rock (e.g., olivine) reacted with S to form Ca-, Mg-, and other sulfates along with iron oxides and oxyhydroxides.

Golden, D. C.

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.

Sm-Nd and Rb-Sr Ages for Northwest Africa 2977, A Young Lunar Gabbro from the PKT

Northwest Africa (NWA) 2977 is an olivine gabbro cumulate equivalent to one of the lithologies in lunar mare breccia NWA 773 [1,2,3]. The Ar-39-Ar-40 age is 2.77+/-0.04 Ga based on the last approx.57% of the gas release [4], similar to results for NWA 773 [5]. A Sm-Nd age (T) of 2.865+/-0.031 Ga and Epsilon(sub Nd) = -7.84+/-0.22 for the NWA 773 gabbro reported by [6] has been revised to T = 2.993+/-=0.032 Ga, Epsilon(sub Nd) -4.5+/-0.3 [7]. Sm-147-Nd-143 isochron for NWA 2977: Whole rock, pyroxene, olivine, plagioclase, whole rock leachate (approx.phosphate) and the combined leachates from the mineral separates yield a well defined Sm-Nd isochron for an age T = 3.10+/-0.05 Ga and Epsilon(sub Nd-CHUR) = -3.74+/-0.26 [8], or Epsilon(sub Nd-HEDR) = -4.61+/-0.26 [9]. Rb-87-Sr-87 isochron: NWA 2977 contains only a modest amount of Rb and/or Sr contamination. The Sr-isotopic composition of the contaminant closely resembles that of seawater. The whole rock residue after leaching combined with leach residues for plagioclase and pyroxene define an isochron age of 3.29+/-0.11 Ga for initial Sr-87/Sr-86 = 0.70287+/-18. The olivine residue, with lower Sr abundance of approx 1.5 ppm, is only slightly displaced from the isochron. The relatively small uncertainties of the Rb-Sr isochron parameters and near-concordancy with the Sm-Nd age indicate that both the Rb-Sr and the Sm-Nd ages are reliable.

Nyquist, L. E.

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.