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NASA NTRS2002

Surface Relaxation in Protein Crystals

Surface X-ray diffraction measurements were performed on (111) growth faces of crystals of the Cellular iron-storage protein horse spleen ferritin. Crystal Trunkation Rods (CTR) were measured. A fit of the measured profile of the CTR revealed a surface roughness of 48 +/- 4.5 A and a top layer spacing contraction of 3.9 +/- 1.5%. In addition to the peak from the CTR, the rocking curves of the crystals displayed unexpected extra peaks. Multiple-scattering is demonstrated to account for them. Future applications of the method could allow the exploration of hydration effects on the growth of protein crystals.

Boutet, S.↗

NASA NTRS2003

Magnetic Control of Solutal Buoyancy Driven Convection

Volumetric forces resulting from local density variations and gravitational acceleration cause buoyancy induced convective motion in melts and solutions. Solutal buoyancy is a result of concentration differences in an otherwise isothermal fluid. If the fluid also exhibits variations in magnetic susceptibility with concentration then convection control by external magnetic fields can be hypothesized. Magnetic control of thermal buoyancy induced convection in ferrofluids (dispersions of ferromagnetic particles in a carrier fluid) and paramagnetic fluids have been demonstrated. Here we show the nature of magnetic control of solutal buoyancy driven convection of a paramagnetic fluid, an aqueous solution of Manganese Chloride hydrate. We predict the critical magnetic field required for balancing gravitational solutal buoyancy driven convection and validate it through a simple experiment. We demonstrate that gravity driven flow can be completely reversed by a magnetic field but the exact cancellation of the flow is not possible. This is because the phenomenon is unstable. The technique can be applied to crystal growth processes in order to reduce convection and to heat exchanger devices for enhancing convection. The method can also be applied to impose a desired g-level in reduced gravity applications.

Ramachandran, N.↗

NASA NTRS2003

Mars Exploration Rovers as Virtual Instruments for Determination of Terrain Roughness and Physical Properties

The two 2003 Mars Exploration Rovers (MERs), in combination with the Athena Payload, will be used as virtual instrument systems to infer terrain properties during traverses, in addition to using the rover wheels to excavate trenches, exposing subsurface materials for remote and in-situ observations. The MERs are being modeled using finite element-based rover system transfer functions that utilize the distribution of masses associated with the vehicle, together with suspension and wheel dynamics, to infer surface roughness and mechanical properties from traverse time series data containing vehicle yaw, pitch, roll, encoder counts, and motor currents. These analyses will be supplemented with imaging and other Athena Payload measurements. The approach is being validated using Sojourner data, the FIDO rover, and experiments with MER testbed vehicles. In addition to conducting traverse science and associated analyses, trenches will be excavated by the MERs to depths of approximately 10-20 cm by locking all but one of the front wheels and rotating that wheel backwards so that the excavated material is piled up on the side of the trench away from the vehicle. Soil cohesion and angle of internal friction will be determined from the trench telemetry data. Emission spectroscopy and in-situ observations will be made using the Athena payload before and after imaging. Trenching and observational protocols have been developed using Sojourner results; data from the FIDO rover, including trenches dug into sand, mud cracks, and weakly indurated bedrock; and experiments with MER testbed rovers. Particular attention will be focused on Mini-TES measurements designed to determine the abundance and state of subsurface water (e.g. hydrated, in zeolites, residual pore ice?) predicted to be present from Odyssey GRS/NS/HEND data.

R E Arvidson↗

NASA NTRS2003

Can Hydrous Minerals Account for the Observed Mid-Latitude Water on Mars?

Clays, zeolites, and Mg-sulfates are all phases that could potentially retain H2O in martian regolith. The nature of the hydrogen-containing material observed in the equatorial martian regolith is of particular importance to the question of whether hydrous minerals have formed in the past on Mars. Also, whether these minerals exist in a hydrated (i.e., containing H2O molecules in their structures) or dehydrated state is a crucial question. The purpose of this communication is to estimate the possible magnitude of the H2O reservoir constituted by these H2O-bearing minerals. In other words, can minerals containing H2O and/or OH such clays, zeolites, or Mg-sulfates, reasonably be expected to account for the amounts of near-equatorial H2O-equivalent hydrogen recently documented by Mars Odyssey?

D L Bish↗

NASA NTRS2003

Development and Testing of Laser-induced Breakdown Spectroscopy for the Mars Rover Program: Elemental Analyses at Stand-Off Distances

One of the most fundamental pieces of information about any planetary body is the elemental composition of its surface materials. The Viking Martian landers employed XRF (x-ray fluorescence) and the MER rovers are carrying APXS (alpha-proton x-ray spectrometer) instruments upgraded from that used on the Pathfinder rover to supply elemental composition information for soils and rocks to which direct contact is possible. These in- situ analyses require that the lander or rover be in contact with the sample. In addition to in-situ instrumentation, the present generation of rovers carry instruments that operate at stand-off distances. The Mini-TES is an example of a stand-off instrument on the MER rovers. Other examples for future missions include infrared point spectrometers and microscopic-imagers that can operate at a distance. The main advantage of such types of analyses is obvious: the sensing element does not need to be in contact or even adjacent to the target sample. This opens up new sensing capabilities. For example, targets that cannot be reached by a rover due to impassable terrain or targets positioned on a cliff face can now be accessed using stand-off analysis. In addition, the duty cycle of stand-off analysis can be much greater than that provided by in-situ measurements because the stand-off analysis probe can be aimed rapidly at different features of interest eliminating the need for the rover to actually move to the target. Over the past five years we have been developing a stand-off method of elemental analysis based on atomic emission spectroscopy called laser-induced breakdown spectroscopy (LIBS). A laser-produced spark vaporizes and excites the target material, the elements of which emit at characteristic wavelengths. Using this method, material can be analyzed from within a radius of several tens of meters from the instrument platform. A relatively large area can therefore be sampled from a simple lander without requiring a rover or sampling arms. The placement of such an instrument on a rover would allow the sampling of locations distant from the landing site. Here we give a description of the LIBS method and its advantages. We discuss recent work on determining its characteristics for Mars exploration, including accuracy, detection limits, and suitability for determining the presence of water ice and hydrated minerals. We also give a description of prototype instruments we have tested in field settings.

D A Cremers↗

NASA NTRS2003

Electron Energy-Loss Spectroscopy (EELS) of Fe-bearing Sheet Silicates in CM Chondrites

The primitive character and hydrated mineralogy of the CM chondrites offers insight into some of the earliest reactions between solids and water. Such reactions profoundly affected the matrices and fine-grained rims (FGRs) [1-4], two of the most significant components of these meteorites [5]. We are using EELS combined with a transmission electron microscope (TEM) to investigate the compositions of Fe-bearing minerals, with emphasis on determining oxidation states and quantification of oxidation-state ratios. Iron is among the most abundant elements in the solar system and it can occur naturally in three oxidation states: Fe0, Fe2+, and Fe3+. Determination of oxidation- state ratios is useful because they can be used to infer the redox conditions under which the minerals formed or were last equilibrated [6, 7]. We are particularly interested in understanding how the oxidation state of Fe was affected by the aqueous reactions of the CM chondrites.

Zega, Thomas J.↗

NASA NTRS2003

Mineralogy and Textural Characteristics of Fine-grained Rims in the Yamato 791198 CM2 Carbonaceous Chondrite: Constraints on the Location of Aqueous Alteration

Carbonaceous chondrites provide important clues into the nature of physical and chemical processes in the early solar system. A question of key importance concerns the role of water in solar nebular and asteroidal processes. The effects of water on primary mineral assemblages have been widely recognized in chondritic meteorites, especially the CI and CM carbonaceous chondrites. These meteorites have undergone extensive aqueous alteration that occurred prior to their arrival on Earth. In the case of the CM chondrites, this alteration has resulted in the partial to complete replacement of the primary nebular phases with secondary alteration phases. Considerable controversy exists as to the exact location where the alteration of the CM chondrites occurred. Several textural lines of evidence have been cited in support of aqueous alteration prior to the accretion of the final parent asteroid. An important line of evidence to support this hypothesis is the dis-equilibrium nature of fine-grained rims and matrix materials. [2] also noted the juxtaposition of micron-sized Fe-Ni metal grains and apparently unaltered chondrule glass against hydrated rim silicates. Conversely, there is a large body of evidence in favor of parent body alteration such as the occurrence of undisturbed Fe-rich aureoles and the systematic redistribution of elemental components over millimeters, e.g., Mg(+2) into the matrix and Fe(+2) into chondrules etc.

Chizmadia, Lysa J.↗

NASA NTRS2003

The Tagish Lake Meteorite as a Possible Sample from a T or D Type Asteroid

Since the Tagish Lake meteorite fell in January 2000, the one of the kind meteorite has become the hottest issue among meteoriticists as well as astrobiologists. Meanwhile, concerning the physical origin of the meteorite in our solar system, only Hiroi et al. reported that it likely came from a D asteroid based on comparison of their visible-near-infrared (Vis-NIR) reflectance spectra. However, because asteroid classification is usually performed based on a limited range of wavelength, the asteroid classes and surface compositions may not necessarily have one-to-one correspondence. Also, Hiroi et al. precluded the T-type asteroids simply because their average albedo is much higher than the visible reflectance of Tagish Lake although their spectral matches with Tagish Lake were good, and the 3-mm band spectra compiled in were not enough to compare the degree of hydration or kinds of hydrous minerals between primitive asteroids and Tagish Lake. In this paper, we employ more spectral datasets up to the 3-mm range to address the possible connection between two particular asteroids, 773 Irmintraud and 308 Polyxo, and the Tagish Lake meteorite.

Hiroi, T.↗

NASA NTRS2003

Analysis of Multispectral Galileo SSI Images of the Conamara Chaos Region, Europa

Multispectral imaging of Europa s surface by Galileo s Solid State Imaging (SSI) camera has revealed two major surface color units, which appear as white and red-brown regions in enhanced color images of the surface (see figure). The Galileo Near- Infrared Mapping Spectrometer (NIMS) experiment suggests that the whitish material is icy, almost pure water ice, while the spectral signatures of the reddish regions are dominated by a non-ice material. Two endmember models have been proposed for the composition of the non-ice material: magnesium sulfate hydrates [1] and sulfuric acid and its byproducts [2]. There is also debate concerning whether the origin of this non-ice material is exogenic or endogenic [3].Goals: The key questions this work addresses are: 1) Is the non-ice material exogenic or endogenic in origin? 2) Once emplaced, is this non-ice material primarily modified by exogenic or endogenic processes? 3) Is the non-ice material within ridges, bands, chaos, and lenticulae the same non-ice material across all such geological features? 4) Does the distribution of the non-ice material provide any evidence for or against any of the various models for feature formation? 5) To what extent do the effects of scattered light in SSI images change the spectral signatures of geological features?

Spaun, N. A.↗

NASA NTRS2003

The Origin of Chondrites: Metal-Silicate Separation Experiments Under Microgravity Conditions, Experiment 2

Chondrites are categorized into different groups by several properties, including the metal-to-silicate ratio. Various processes have been suggested to produce distinct metal/silicate ratios, some based on sorting in the early solar nebular and others occurring after accretion on the parent body. Huang et al. suggested that a weak gravitational field accompanied by degassing, could result in metal/silicate separation on parent bodies. We suggest that asteroids were volatile-rich, at least early in their histories. Spectroscopic evidence from asteroid surfaces indicates that one-third of all asteroids maybe rich in clays and hydrated minerals, similar to carbonaceous chondrites. Internal and/or external heating could have caused volatiles to evaporate and pass through a surface dust layer. Spacecraft images of asteroids show they have a thick regoliths. Housen, and Asphaug and Nolan proposed that even a 10 km diameter asteroid could potentially have a significant regolith. Grain size and grain density sorting could occur in the unconsolidated layer by the process known as fluidization. This process occurs when an upward stream of gas is passed through a bed of particles which are lifted against a gravitational force. Fluidization is commonly used commercially to sort particulates. This type of behavior is based upon the bed, as a whole, and differs from aerodynamic sorting. Two sets of reduced gravity experiments were conducted during parabolic flights aboard NASA's KC-135 aircraft. The first experiment employed 310 tubes of 2.5 cm diameter, containing mixtures of sand and metal grains. A gas source was used to fluidize the mixture at reduced gravity conditions and mixtures were analyzed after the flight. However, this experiment did not allow a description of the fluidization as a function of gravity. A second experiment was conducted on the KC-135 aircraft in the summer of 2001, consisting of two Plexiglas cylinders containing a metal/silicate mixture, and video cameras to record the experiment on tape. Here we summarize this experiment and discusses the implications for metalsilicate separation on asteroid bodies.

Moore, S. R.↗

NASA NTRS2003

The I-Xe Age of Orgueil Magnetite: New Results

I-Xe ages of Murchison and Orgueil magnetites were reported to be the oldest [1] and interpreted as the condensation time of the solar nebula. More recent measurements, conducted on a highly magnetic separate from Orgueil (but not pure magnetite), gave much younger I-Xe ages [2]. We have since performed new studies on two pure separates of Orgueil magnetite, confirming the later closing time of the I-Xe system in this mineral phase. In the previous work of Lewis and Anders [1] special attention was paid to the purity of the analyzed material. It was shown, that the trapped Xe resided mostly in hydrated silicates and the radiogenic 129Xe in magnetite [3]. Therefore, Orgueil was finely ground and stirred with a saturated LiCl solution for 8 days at 60 C to remove the silicate-magnetite intergrowth. Although this procedure yields magnetic fractions that are at least 90% pure [1], it could potentially contaminate the magnetite with iodine and produce noncorrelated 128Xe and spurious I-Xe ages. To avoid this possibility, in our first work with Orgueil we deliberately omitted separation in LiCl solution. Instead, the meteorite was ground into a fine powder and the highly magnetic fraction was separated with a hand magnet and was confirmed to be largely magnetite [2]. The new work, reported here, was done in order to confirm our previous results and investigate the effects of the LiCl treatment on the I-Xe system in magnetite.

Pravdivtseva, O. V.↗

NASA NTRS2003

Novel Ordered Crown Ether-Containing Polyimides for Ion Conduction

We report the synthesis and characterization of thermally-stable polyimides for use as battery and fuel cell electrolyte membranes. Dianhydrides used were 1,4,5,8- naphthalenetetracarboxylic dianhydride and/or 4,4'-(hexafluoroisopropylidene)diphthalic anhydride. Diamines used were anti-4,4-diaminodibenzo-l8-crown-6, 4,4'- diaminodibenzo-24-crown-8, 2,2-bis(4-aminophenyl)hexafluoropropane, and/or 2,5- diaminobenzenesulfonic acid. The polymers were characterized using electrochemical impedance spectroscopy (EIS), thermal analysis and X-ray diffraction. Polymers containing the hexafluoroisopropylidene (HFIP) group were soluble in common organic solvents, while polymers without the HFIP group were very poorly soluble. Sulfonation yields polymers that are sparingly soluble in aqueous base and/or methanol. Degree of sulfonation, determined by titration, was between one and three sulfonate groups per repeat unit. Proton conductivity was determined as a function of water content, with a maximum conductivity of l x 10(exp -2) per centimeter when fully hydrated. Crown ether-containing polymers exhibit a high degree of order that may be indicative of crown ether channel formation, which may facilitate Li(+) transport for use in battery membranes.

Irvin, Jennifer A.↗

NASA NTRS2003

Uptake of Small Organic Compounds by Sulfuric Acid Aerosols: Dissolution and Reaction

To assess the role of oxygenated volatile organic compounds in the upper troposphere and lower stratosphere, the interactions of a series of small organic compounds with low-temperature aqueous sulfuric acid will be evaluated. The total amount of organic material which may be taken up from the gas phase by dissolution, surface layer formation, and reaction during the particle lifetime will be quantified. Our current results for acetaldehyde uptake on 40 - 80 wt% sulfuric acid solutions will be compared to those of methanol, formaldehyde, and acetone to investigate the relationships between chemical functionality and heterogeneous activity. Where possible, equilibrium uptake will be ascribed to component pathways (hydration, protonation, etc.) to facilitate evaluation of other species not yet studied in low temperature aqueous sulfuric acid.

Iraci, L. T.↗

NASA NTRS2004

[Calibration, Analysis, and Interpretation of SERTS and EUNIS Observation]

We have made satisfactory and expected progress in the first year of this project. The spectrophotometric data for the S asteroids of interest have been reduced, and lightcurve effects accounted for. We have begun mixing models for spectra of 6 Hebe, and expect to have a publication late in 2004 or early in 2005 on that part of the project. Preliminary models suggest that Hebe requires hydrated minerals to explain its spectrum in the 3-pm region. We will also perform mixing models with additional data which has been recently obtained. We have been able to constrain thermal properties on near-Earth asteroids (NEAs) as a result of thermal modeling done as part of this project. This work provides a means of obtaining albedo data from common visible-near IR data. This portion of the project has been presented at the DPS meeting in Monterey, and is being presented in expanded form at the Yarkovsky workshop at Arecibo Observatory in February. A manuscript is in preparation. In the coming year we expect to finish the thermal corrections for the spectrophotometric data, and complete the mixing models. The results will be prepared for publication, and the data offered to the PDS. It will also be available on the SMASS website (smass.mit.edu), for which the PI is webmaster.

Source record↗

NASA NTRS2003

Efficient Synthesis of 4,8-Ditoluoyl-1,5-Dihydroxynaphthalene

4,8-Ditoluoyl-1,5-dihydroxynaphthalene was synthesized in quantitative yield from the corresponding methylenequinone via base-catalyzed hydration. Alkaline treatment gives the title compound in one step with a 99% yield, an improvement of 80% compared to the acidic, two step literature method for preparing 4,8-dibenzoyl-1,5-dihydroxynaphthalene.

Tyson, Daniel S.↗

NASA NTRS2002

Near-Infrared Spectrophotometry of Phobos and Deimos

We have observed the leading and trailing hemispheres of Phobos from 1.65 to 3.5 microns and Deimos from 1.65 to 3.12 microns near opposition. We find the trailing hemisphere of Phobos to be brighter than its leading hemisphere by 0.24 +/- 0.06 magnitude at 1.65 microns and brighter than Deimos by 0.98 +/- 0.07 magnitude at 1.65 microns. We see no difference larger than observational uncertainties in spectral slope between the leading and trailing hemispheres when the spectra are normalized to 1.65 microns. We find no 3-microns absorption feature due to hydrated minerals on either hemisphere to a level of approx. 5 - 10% on Phobos and approx. 20% on Deimos. When the infrared data are joined to visible and near-IR data obtained by previous workers, our data suggest the leading (Stickney-dominated) side of Phobos is best matched by T-class asteroids. The spectral slope of the trailing side of Phobos and leading side of Deimos are bracketed by the D-class asteroids. The best laboratory spectral matches to these parts of Phobos are mature lunar soils and heated carbonaceous chondrites. The lack of 3-microns absorption features on either side of Phobos argues against the presence of a large interior reservoir of water ice according to current models of Phobos' interior.

Rivkin, A. S.↗

NASA NTRS2004

Hydrocarbon Biomarker Stratigraphy of C-Isotopic Excursions Marking Chemical Changes in the Ocean with Contemporanious Biotic Extinction-Radiation Events

One paper recording progress in this topic has been accepted for publication. We report a method for the rigorous identification of biomarkers (crocetane and PMI) that may be specific for methanotrophic and methanogenic archaea and, perhaps, the process of anaerobic oxidation of methane. If catastrophic methane efflux from sub-sea methane hydrate is responsible for extinction events, as has been hypothesized by many workers, then we might expect to find biomarkers for methane oxidation in sediments marking some extinction boundaries. Unfortunately, identifying crocetane and PMI with certainty is not a trivial exercise and these biomarkers appear to have been mis-identified in a recent publication by workers from Curtin University. Barber et al. (2001) identified crocetane and PMI in sediments deposited in the basal Triassic of the Perth Basin, Australia. However, Barber et al. (2001) also found crocetane and PMI in many other sediments and oils in a way that was inconsistent with our knowledge of these systems.

Summons, Roger E.↗

NASA NTRS2003

Hydrogen Concentrations on C-Class Asteroids Derived from Remote Sensing

We present spectroscopic observations of 16 asteroids from 1.9-3.6 microns collected from the United Kingdom Infrared Telescope (UKIRT) from 1996-2000. Of these 16 asteroids, 11 show some evidence of a 3 microns hydrated mineral absorption feature greater than 2(sigma) at 2.9 microns. Using relations first recognized for carbonaceous chondrite powders by Miyamoto and Zolensky and Sato et al., we have determined the hydrogen to silicon ratio for these asteroids and calculated their equivalent water contents, assuming all the hydrogen was in water. The asteroids split into 2 groups, roughly defined as equivalent water contents approx. greater than 7% (8 asteroids, all with 3 microns band depths approx. greater than 20%) and approx. greater than 3% for the remaining 8 asteroids. This latter group includes some asteroids for which a weak but statistically significant 3 microns band of non-zero depth exists. The G-class asteroids in the survey have higher water contents, consistent with CM chondrites. This strengthens the connection between CM chondrites and G asteroids that was proposed by Burbine. We find that the 0.7 microns and 3 microns band depths are correlated for the population of target objects.

Rivkin, A. S.↗