ALBERT

Description: Incorporation of Mg, S, and plant-essential micronutrients into the structure of synthetic hydroxyapatite (HA) may be advantageous for closed-loop systems, such as will be required on Lunar and Martian outposts, because these apatites can be used as slow-release fertilizers. Our objective was to synthesize HA with Ca, P, Mg, S, Fe, Cu, Mn, Zn, Mo, B, and Cl incorporated into the structure, i.e., nutrient-substituted apatites. Hydroxyapatite, carbonate hydroxyapatite (CHA), nutrient-substituted hydroxyapatite (NHA), and nutrient-substituted carbonate hydroxyapatite (NCHA) were synthesized by precipitating from solution. Chemical and mineralogical analysis of precipitated samples indicated a considerable fraction of the added cations were incorporated into HA, without mineral impurities. Particle size of the HA was in the 1 to 40 nm range, and decreased with increased substitution of nutrient elements. The particle shape of HA was elongated in the c-direction in unsubstituted HA and NHA but more spherical in CHA and NCHA. The substitution of cations and anions in the HA structure was confirmed by the decrease of the d[002] spacing of HA with substitution of ions with an ionic radius less than that of Ca or P. The DTPA-extractable Cu ranged from 8 to 8429 mg kg-1, Zn ranged from 57 to 1279 mg kg-1, Fe from 211 to 2573 mg kg-1, and Mn from 190 to 1719 mg kg-1, depending on the substitution level of each element in HA. Nutrient-substituted HA has the potential to be used as a slow-release fertilizer to supply micronutrients, S, and Mg in addition to Ca and P.

Description: The paper characterizes the mineralogy and spectral properties of three slightly palagonitized basaltic tephra samples collected near the summit of Mauna Kea in order to contribute to the basis for inferring mineralogy and processes for Martian surface materials. The mineralogy of size fractions of these samples is examined by diffuse reflectance and FIR spectroscopy, optical microscopy, X-ray diffraction, Moessbauer spectroscopy, magnetic analysis, EMPA, TEM, and SEM. For the 20-1000 micron size fraction, sample HWMK11 (red) is essentially completely oxidized and has a hematite (Ti-hematite) pigment dispersed throughout the silicate matrix. Sample HWMK12 (black) has the lowest proportion of ferric-bearing phases and is thus least weathered. For HWMK11, the amount of hematite is essentially constant, and mica is present only in the coarse clay-sized fraction; smectites are low in structural Fe.

Description: Regenerative life support systems (RLSS) will be required to regenerate air, water, and wastes, and to produce food for human consumption during long-duration stays on the moon. It may be possible to supplement some of the materials needed for RLSS from resources on the moon. Natural materials at the lunar surface may be used for a variety of lunar RLSS needs, including (i) soils or solid-support substrates for plant growth, (ii) sources for extraction of essential, plant-growth nutrients, (iii) substrates for microbial populations in the degradation of wastes, (iv) sources of O2 and H, which may be used to manufacture water, (v) feed stock materials for the synthesis of useful minerals (e.g., molecular sieves), and (vi) shielding materials surrounding the outpost structure to protect humans, plants, and microorganisms from harmful radiation.

Description: Differential Scanning Calorimetry (DSC) combined with evolved gas analysis (EGA) is a well developed technique for the analysis of a wide variety of sample types with broad application in material and soil sciences. However, the use of the technique for samples under conditions of pressure and temperature as found on other planets is one of current development and cutting edge research. The Thermal Evolved Gas Analyzer (TEGA), which was designed, built and tested at the University of Arizona's Lunar and Planetary Lab (LPL), utilizes DSC/EGA. TEGA, which was sent to Mars on the ill-fated Mars Polar Lander, was to be the first application of DSC/EGA on the surface of Mars as well as the first direct measurement of the volatile-bearing mineralogy in martian soil. Additional information is available in the original extended abstract.

Description: Volatile-bearing minerals and phases (e.g., Fe-oxyhydroxides, phyllosilicates, carbonates, sulfates, palagonites, glasses) may be important components of the Martian regolith. However, essentially no information exists on the mineralogical composition of volatile-bearing phases in the regolith. The Thermal Evolved Gas Analyzer (TEGA), which was part of the Mars Polar Lander payload, was to determine the abundances of two of the most important volatile compounds (i.e., water and carbon dioxide) in the martian soil and to identify the minerals or phases that harbor these volatiles. The TEGA instrument was composed of a differential scanning calorimeter (DSC) interfaced with evolved gas analysis (EGA). The EGA consisted of a Herriott cell of a tunable-diode laser (TDL) spectrometer that determines CO2 and H2O abundances. The sample chamber was to operate at about 100 mbar (-76 torr) with a N2 carrier gas flow of 0.4 sccm. Specifications of TEGA are described in detail elsewhere in this volume.

Description: 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.

Description: Hydroponic culture has traditionally been used for controlled environment life support systems (CELSS) because the optimal environment for roots supports high growth rates. Recent developments in zeoponic substrate and microporous tube irrigation (ZPT) also offer high control of the root environment. This study compared the effect of differences in water and nutrient status of ZPT or hydroponic culture on growth and yield of wheat (Triticum aestivum L. cv. USU-Apogee). In a side-by-side test in a controlled environment, wheat was grown in ZPT and recirculating hydroponics to maturity. Water use by plants grown in both culture systems peaked at 15 to 20 L m-2 d-1 up to Day 40, after which it declined more rapidly for plants grown in ZPT culture due to earlier senescence of leaves. No consistent differences in water status were noted between plants grown in the two culture systems. Although yield was similar, harvest index was 28% lower for plants grown in ZPT than in hydroponic culture. Sterile green tillers made up 12 and 0% of the biomass of plants grown in ZPT and hydroponic culture, respectively. Differences in biomass partitioning were attributed primarily to NH4-N nutrition of plants grown in ZPT compared with NO3-N in hydroponic nutrient solution. It is probable that NH4-N-induced Ca deficiency produced excess tillering and lower harvest index for plants grown in ZPT culture. These results suggest that further refinements in zeoponic substrate would make ZPT culture a viable alternative for achieving high productivity in a CELSS.

Description: The Rocknest aeolian deposit is similar to aeolian features analyzed by the Mars Exploration Rovers (MER) Spirit and Opportunity. The fraction of sand 〈150 micron in size contains approx. 55% crystalline material consistent with a basaltic heritage, and approx. 45% X-ray amorphous material. The amorphous component of Rocknest is Fe-rich and Si-poor, and is the host of the volatiles (H2O, O2, SO2, CO2, and Cl) detected by the Surface Analysis at Mars (SAM) instrument and of the fine-grained nanophase oxide (npOx) component first described from basaltic soils analyzed by MER. The similarity between soils and aeolian materials analyzed at Gusev crater, Meridiani Planum and Gale crater implies locally sourced, globally similar basaltic materials, or globally and regionally sourced basaltic components deposited locally at all three locations.

Description: There are several hypotheses regarding the formation of Martian surface fines. These surface fines are thought to be products of weathering processes occurring on Mars. Four major weathering environments of igneous rocks on Mars have been proposed; (1) impact induced hydrothermal alterations; (2) subpermafrost igneous intrusion; (3) solid-gas surface reactions; and (4) subaerial igneous intrusion over permafrost. Although one or more of these processes may be important on the Martian surface, one factor in common for all these processes is the reaction of solid or molten basalt with water (solid, liquid, or gas). These proposed processes, with the exception of solid-gas surface reactions, are transient processes. The most likely product of transient hydrothermal processes are layer silicates, zeolites, hydrous iron oxides and palagonites. The long-term instability of hydrous clay minerals under present Martian conditions has been predicted; however, the persistence of such minerals due to slow kinetics of dehydration, or entrapment in permafrost, where the activity of water is high, can not be excluded. Anhydrous oxides of iron (e.g., hematite and maghemite) are thought to be stable under present Martian surface conditions. Oxidative weathering of sulfide minerals associated with Martian basalts has been proposed. Weathering of sulfide minerals leads to a potentially acidic permafrost and the formation of Fe(3) oxides and sulfates. Weathering of basalts under acidic conditions may lead to the formation of kaolinite through metastable halloysite and metahalloysite. Kaolinite, if present, is thought to be a thermodynamically stable phase at the Martian surface. Fine materials on Mars are important in that they influence the surface spectral properties; these fines are globally distributed on Mars by the dust storms and this fraction will have the highest surface area which should act as a sink for most of the absorbed volatiles near the surface of Mars. Therefore, the objectives of this study were to: (1) examine the fine fraction mineralogy of several palagonitic materials from Hawaii; and (2) compare spectral properties of palagonites and submicron sized synthetic iron oxides with the spectral properties of the Martian surface.

Description: Iron oxide minerals are the prime candidates for Fe(III) signatures in remotely sensed Martian surface spectra. Magnetic, Mossbauer, and reflectance spectroscopy have been carried out in the laboratory in order to understand the mineralogical nature of Martian analog ferric oxide minerals of submicron or nanometer size range. Out of the iron oxide minerals studied, nanometer sized ferric oxides are promising candidates for possible Martian spectral analogs. 'Nanophase ferric oxide (np-Ox)' is a generic term for ferric oxide/oxihydroxide particles having nanoscale (less than 10 nm) particle dimensions. Ferrihydrite, superparamagnetic particles of hematite, maghemite and goethite, and nanometer sized particles of inherently paramagnetic lepidocrocite are all examples of nanophase ferric oxides. np-Ox particles in general do not give X-ray diffraction (XRD) patterns with well defined peaks and would often be classified as X-ray amorphous. Therefore, different np-Oxs preparations should be characterized using a more sensitive technique e.g., high resolution transmission electron microscopy (HRTEM). The purpose of this study is to report the particle size, morphology and crystalline order, of five np-Ox samples by HRTEM imaging and electron diffraction (ED).