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At least 181 records · Page 10

DCP-collected absolute target reflectance signatures assist accurate interpretation of ERTS-1 imagery

Data collection platforms (DCP's) are being used at a Black Hills, South Dakota, test site (MMC 226A) to record radiometric measurements needed to determine solar and atmospheric parameters that affect ERTS-1 multispectral scanner radiance measurements. A total of 72 channels of analog data transmitted from an unattended ground truth site via three DCP's at least six times a day. The system has operated with only minor problems since September, sending forth daily measurements of biophysical responses and atmospheric conditions. Comparisons of scene radiance data calculated from ERTS images with that measured on the ground show the image-measured values to be 35 percent higher for the green channel and 20 percent higher for the red channel for the same scene targets. Radiance values for channels 6 and 7 are nearly the same from the ground data and from the imagery.

Weber, F. P.↗

NASA/ESMD Analogue Mission Plans

A viewgraph presentation exploring Earth and its analogues is shown. The topics include: 1) ESMD Goals for the Use of Earth Analogues; 2) Stakeholders Summary; 3) Issues with Current Analogue Situation; 4) Current state of Analogues; 5) External Implementation Plan (Second Step); 6) Recent Progress in Utilizing Analogues; 7) Website Layout Example-Home Page; 8) Website Layout Example-Analogue Site; 9) Website Layout Example-Analogue Mission; 10) Objectives of ARDIG Analog Initiatives; 11) Future Plans; 12) Example: Cold-Trap Sample Return; 13) Example: Site Characterization Matrix; 14) Integrated Analogue Studies-Prerequisites for Human Exploration; and 15) Rating Scale Definitions.

Hoffman, Stephen J.↗

Mars Pathfinder Landing Site Workshop 2: Characteristics of the Ares Vallis Region and Field Trips in the Channeled Scabland, Washington

Mars Pathfinder will place a single lander on the surface of Mars on July 4, 1997, following a December 1996 launch. As a result of the very successful first Mars Pathfinder Landing Site Workshop, the project has selected the Ares Vallis outflow channel in Chryse Planitia as the landing site. This location is where a large catastrophic outflow channel debouches into the northern lowlands. A second workshop and series of field trips, entitled Mars Pathfinder Landing Site Workshop 2: Characteristics of the Ares Vallis Region and Field Trips in the Channeled Scabland, Washington, were held in Spokane and Moses Lake, Washington. The purpose of the workshop was to provide a focus for learning as much as possible about the Ares Vallis region on Mars before landing there. The rationale is that the more that can be learned about the general area prior to landing, the better scientists will be able interpret the observations made by the lander and rover and place them in the proper geologic context. The field trip included overflights and surface investigations of the Channeled Scabland (an Earth analog for the martian catastrophic outflow channels), focusing on areas particularly analogous to Ares Vallis and the landing site. The overflights were essential for placing the enormous erosional and depositional features of the Channeled Scabland into proper three-dimensional context. The field trips were a joint educational outreach activity involving K-12 science educators, Mars Pathfinder scientists and engineers, and interested scientists from the Mars scientific community. Part 1 of the technical report on this workshop includes a description of the Mars Pathfinder mission, abstracts accepted for presentation at the workshop, an introduction to the Channeled Scabland, and field trip guides for the overflight and two field trips. This part, Part 2, includes the program for the workshop, summaries of the workshop technical sessions, a summary of the field trips and ensuing discussions, late abstracts of workshop presentations, reports on the education and public outreach activities carried out by the educators, and a list of the workshop and field trip participants.

Golombek, M. P.↗

Planar Defect Layers Template a High-Pressure InBi Polymorph

The short- and long-range order of III–V materials under high pressure has long been the subject of debate, with advancements in structural characterization leading to significant revisions to the accepted structural models. Despite these revisions, previous high-pressure structural assignments in the In–Bi system include the site-disordered β-Sn structure type, a structure type demonstrated to be nonexistent in analogous III–V systems. While X-ray diffraction is consistent with site disordering in InBi at high pressure, cluster expansion calculations indicate that disordering requires temperatures above 3000 K. Here, we propose InBi as a model material for studying unique high-pressure planar defects due to its highly anisotropic stress-dependent properties and structure. Specifically, we identify two sets of planar defects that mimic the diffraction pattern of a site disordered β-Sn structure type and are compatible with the calculated disorder barrier. We derive these defects by symmetry relations over crystallographic transitions. Density functional theory calculations of the proposed defects suggest that these defects are stabilized by diminishing interlayer separations with pressure. Further, we find that one of the proposed defects closely resembles a bulk high-pressure phase of InBi, InBi-ϵ, and we assert that the proposed defects order upon heating, acting as a template for InBi-ϵ growth. The proposed defects and their electronic structure provide a basis for the trend of superconducting critical temperature with increasing pressure. These methods for identifying defects are generalizable to other materials with reports of site disorder at high pressure, prompting a broader search for related high-pressure defects.

36 MATERIALS SCIENCE↗

Emplacement of Fahrenheit crater ejecta at the Luna-24 site

The likelihood that the gabbroic and monomineralic fragments in the Luna-24 soils were excavated during the Fahrenheit cratering event can be assessed by considering the quantity, characteristics, and mode of deposition of Fahrenheit ejecta in the vicinity of the Luna-24 site. The original morphology of Fahrenheit's ejecta deposits is inferred by examining a fresh crater, Lichtenberg B, of a comparable site that formed in a similar type of target material. On the basis of this analogy, a probability of over 80% was calculated that the Luna-24 site was morphologically disturbed by the deposition of Fahrenheit ejecta. The relative abundance, gabbroic composition, and unshocked character of the holocrystalline fragments discovered in the Luna-24 core sample are consistent with the widespread occurrence of Fahrenheit deposits and the characteristics of Fahrenheit ejecta anticipated at the Luna-24 range.

Settle, M.↗

Lunar and Planetary Science XXXV: Mars: Radar, Gamma Ray Spectrometer, and Cratering Mineralogy

The session "Mars: Radar, Gamma Ray Spectrometer, and Cratering Mineralogy" contained the following reports:The Dielectric Properties of Martian Soil Simulant JSC Mars-1 in the Range from 20Hz to 10kHz; Eastern Sahara Geology from Orbital Radar: Potential Analog to Mars On the Dielectric Properties of the Martian-like Surface Sediments; Radar Observations of Recent Mars Landing Sites; Sounding of Subsurface Water Through Conductive Media in Mars Analog Environments Using Transient Electromagnetics and Low Frequency Ground-penetrating Radar; Burial Depth of the Reservoirs of Hydrogen at the Equatorial Latitudes on Mars; Elemental Composition Variations for Large Dusty and Rocky Regions on Mars Using Gamma-Ray Data from the Mars Odyssey Gamma-Ray Spectrometer; The Distribution of Non-Volatile Elements on Mars: Mars Odyssey GRS Results; Using Mars Odyssey GRS Data to Assess Models for the Bulk Composition of Mars; Mars: The Terra Arabia Low Epithermal Neutron Flux Anomaly; The Isidis Basin of Mars: New Results from MOLA, MOC, and THEMIS; Remote Sensing of the Haughton Impact Structure (HIS): A Terrestrial Proof of Concept for Using the Remote Sensing of Martian Craters as a Probe of Subsurface Composition;and Thermal Emission Spectra of Impact Glass and Shocked Deccan Basalt from Lonar Crater, India and Implications for Remote Sensing of Mars.

Source record↗

Human cytochrome P450 17A1 structures with metabolites of prostate cancer drug abiraterone reveal substrate-binding plasticity and a second binding site

Abiraterone acetate is a first-line therapy for castration-resistant prostate cancer. This prodrug is deacetylated in vivo to abiraterone, which is a potent and specific inhibitor of cytochrome P450 17A1 (CYP17A1). CYP17A1 performs two sequential steps that are required for the biosynthesis of androgens that drive prostate cancer proliferation, analogous to estrogens in breast cancer. Abiraterone can be further metabolized in vivo on the steroid A ring to multiple metabolites that also inhibit CYP17A1. Despite its design as an active-site-directed substrate analog, abiraterone and its metabolites demonstrate mixed competitive/noncompetitive inhibition. To understand their binding, we solved the X-ray structures of CYP17A1 with three primary abiraterone metabolites. Despite different conformations of the steroid A ring and substituents, all three bound in the CYP17A1 active site with the steroid core packed against the I helix and the A ring C3 keto or hydroxyl oxygen forming a hydrogen bond with N202 similar to abiraterone itself. The structure of CYP17A1 with 3-keto, 5α-abiraterone was solved to 2.0 Å, the highest resolution to date for a CYP17A1 complex. This structure had additional electron density near the F/G loop, which is likely a second molecule of the inhibitor and which may explain the noncompetitive inhibition. Mutation of the adjacent Asn52 to Tyr positions its side chain in this space, maintains enzyme activity, and prevents binding of the peripheral ligand. Collectively, our findings provide further insight into abiraterone metabolite binding and CYP17A1 function.

59 BASIC BIOLOGICAL SCIENCES↗

The 2.4 Å structure of Zymomonas mobilis pyruvate kinase: Implications for stability and regulation

Human liver pyruvate kinase (hlPYK) catalyzes the final step in glycolysis, the formation of pyruvate (PYR) and ATP from phosphoenolpyruvate (PEP) and ADP. Fructose 1,6-bisphosphate (FBP), a pathway intermediate of glycolysis, serves as an allosteric activator of hlPYK. Zymomonas mobilis pyruvate kinase (ZmPYK) performs the final step of the Entner-Doudoroff pathway, which is similar to glycolysis in that energy is harvested from glucose and pyruvate is generated. The Entner-Doudoroff pathway does not have FBP as a pathway intermediate, and ZmPYK is not allosterically activated. In this work, we solved the 2.4 Å X-ray crystallographic structure of ZmPYK. The protein is dimeric in solution as determined by gel filtration chromatography, but crystallizes as a tetramer. The buried surface area of the ZmPYK tetramerization interface is significantly smaller than that of hlPYK, and yet tetramerization using the standard interfaces from higher organisms provides an accessible low energy crystallization pathway. Interestingly, the ZmPYK structure showed a phosphate ion in the analogous location to the 6-phosphate binding site of FBP in hlPYK. Circular Dichroism (CD) was used to measure melting temperatures of hlPYK and ZmPYK in the absence and presence of substrates and effectors. The only significant difference was an additional phase of small amplitude for the ZmPYK melting curves. We conclude that the phosphate ion plays neither a structural or allosteric role in ZmPYK under the conditions tested. In conclusion, we hypothesize that ZmPYK does not have sufficient protein stability for activity to be tuned by allosteric effectors as described for rheostat positions in the allosteric homologues.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metallic particles in the Apollo 14 lunar soil.

The metallographic structures, silicate associations and bulk compositions (Ni, Co, P, S, and Si) were determined by microprobe analysis for 205 metal particles selected by magnetic separation from the less than 1 mm, greater than 125 micron fraction of soil samples 14003,18 and 14163,165. A small number of exotic particles were encountered but almost all the metal could be accommodated within one of four subpopulations, the characteristics and genetic significance of which may be stated as follows: (1) the major proportion has Ni and Co contents corresponding to the range of meteoritic metal; (2) small proportion (about 5%) that not only has meteoritic contents of Ni and Co but also shows still distinguishable indications of meteoritic microstructure; (3) another small population (about 10%) consists of metal excavated from lunar mare basalts by cratering events, and thrown onto the Apollo 14 site; and (4) metallic spheroids (about 5%), analogous to those encountered in the vicinity of the Barringer Meteorite Crater, Arizona.

Goldstein, J. I.↗

Groundwater sapping valleys: Experimental studies, geological controls and implications to the interpretation of valley networks on Mars

An integrated approach using experimental laboratory models, field studies of terrestrial analogs, and remote studies of terrestrial field sites were applied to the goals of understanding the nature and morphology of valley networks formed by groundwater sapping. In spite of problems with scaling, the experimental studies provide valuable insights into concepts relating to the initiation, development, and evolution of valleys by groundwater sapping. These investigations are also aimed at developing geomorphic criteria for distinguishing valleys formed by surface runoff from those formed by groundwater sapping processes. Channels that were field classified as sapping vs. runoff were successfully distinguished using statistical analysis of their respective morphologies; therefore, it may be possible to use similar techniques to interpret channel genesis on Mars. The terrestrial and flume studies provide the ground truth dataset which can be used (and will be during the present year) to help interpret the genesis of valley networks on Mars.

Kochel, R. Craig↗

Mars Redox Chemistry: Atacama Desert Soils as a Terrestrial Analog

The motivation for this work is to perform quantitative site characterizations of soil chemical processes to allow further development and field validation of the Mars Oxidant Instrument (MOI). The MOI is an in situ survey instrument designed to establish the presence of reactive chemical species in the martian soil, dust, or atmosphere, and to provide detailed reaction model system measurements to enable comprehensive Earthbased study. Functioning as a survey instrument, MOI tests the broad range of hypotheses explaining the reactivity of the martian surface material that have been put forth since the Viking experiments. This work is currently being carried out under the NASA ASTEP funded AstroBioLab (Jeffery Bada, PI). A second objective is to use Atacama field and Viking data to perform comparative studies, with the goal of furthering the understanding of the formation mechanisms and properties of martian oxidants.

Quinn, R. C.↗

Sulfur cycling at natural hydrocarbon and sulfur seeps in Santa Paula Creek, CA

Biogeochemical cycling of sulfur is relatively understudied in terrestrial environments compared to marine environments. However, the comparative ease of access, observation, and sampling of terrestrial settings can expand our understanding of organisms and processes important in the modern sulfur cycle. Furthermore, these sites may allow for the discovery of useful process analogs for ancient sulfur-metabolizing microbial communities at times in Earth's past when atmospheric O 2 concentrations were lower and sulfide was more prevalent in Earth surface environments. Here, we identified a new site at Santa Paula Creek (SPC) in Ventura County, CA—a remarkable freshwater, gravel-bedded mountain stream charged with a range of oxidized and reduced sulfur species and heavy hydrocarbons from the emergence of subsurface fluids within the underlying sulfur- and organic-rich Miocene-age Monterey Formation. SPC hosts a suite of morphologically distinct microbial biofacies that form in association with the naturally occurring hydrocarbon seeps and sulfur springs. We characterized the geology, stream geochemistry, and microbial facies and diversity of the Santa Paula Creek ecosystem. Using geochemical analyses and 16S rRNA gene sequencing, we found that SPC supports a dynamic sulfur cycle that is largely driven by sulfide-oxidizing microbial taxa, with contributions from smaller populations of sulfate-reducing and sulfur-disproportionating taxa. This preliminary characterization of SPC revealed an intriguing site in which to study geological and geochemical controls on microbial community composition and to expand our understanding of sulfur cycling in terrestrial environments.

58 GEOSCIENCES↗

Number of surface sites and turnover frequencies for oxide catalysts

Unlike for metal catalysts where selective chemisorption probes (H 2 , O 2 , CO and N 2 O) have been successfully applied to count the number of active surface sites and allow determination of TOF values, the analogous situation for oxide catalysts has developed very slowly. The reason for the sluggish development of selective chemisorption probes for oxides is that the same chemisorption probes that work well with metals aren’t compatible with oxides since these chemical probes weakly adsorb on oxides. Methanol, however, is a very reactive molecule that has been found to readily chemisorb on oxides and allows for quantitative determination of the number of active surface sites (Ns). Here, in this mini-review, the determination of the number of active sites by methanol chemisorption is reviewed with examples for pure oxides (one-component oxides), supported oxides (submonolayer, monolayer and above monolayer) and bulk mixed oxides (surface enriched oxide present in submonolayer, monolayer and in excess of monolayer coverages).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mars: Periglacial Morphology and Implications for Future Landing Sites

At the Mars Phoenix landing site and in much of the Martian northern plains, there is ice-cemented ground beneath a layer of dry permafrost. Unlike most permafrost on Earth, though, this ice is not liquid at any time of year. However, in past epochs at higher obliquity the surface conditions during summer may have resulted in warmer conditions and possible melting. This situation indicates that the ice-cemented ground in the north polar plains is likely to be a candidate for the most recently habitable place on Mars as near-surface ice likely provided adequate water activity approximately 5 Myr ago. The high elevation Dry Valleys of Antarctica provide the best analog on Earth of Martian ground ice. These locations are the only places on Earth where ice-cemented ground is found beneath dry permafrost. The Dry Valleys are a hyper-arid polar desert environment and in locations above 1500 m elevation, such as University Valley, air temperatures do not exceed 0 C. Thus, similarly to Mars, liquid water is largely absent here and instead the hydrologic cycle is dominated by frozen ice and vapor phase processes such as sublimation. These conditions make the high elevation Dry Valleys a key Mars analog location where periglacial processes and geomorphic features can be studied in situ. This talk will focus on studies of University Valley as a Mars analog for periglacial morphology and ice stability. We will review a landing site selection study encompassing this information gleaned from the Antarctic terrestrial analog studies plus Mars spacecraft data analysis to identify candidate landing sites for a future mission to search for life on Mars.

Martian ground ice↗

Mechanistic insights into carbon–carbon coupling on NiAu and PdAu single-atom alloys

Carbon–carbon coupling is an important step in many catalytic reactions, and performing sp 3 –sp 3 carbon–carbon coupling heterogeneously is particularly challenging. It has been reported that PdAu single-atom alloy (SAA) model catalytic surfaces are able to selectively couple methyl groups, producing ethane from methyl iodide. In this work, we extend this study to NiAu SAAs and find that Ni atoms in Au are active for C–I cleavage and selective sp 3 –sp 3 carbon–carbon coupling to produce ethane. Furthermore, we perform ab initio kinetic Monte Carlo simulations that include the effect of the iodine atom, which was previously considered a bystander species. We find that model NiAu surfaces exhibit a similar chemistry to PdAu, but the reason for the similarity is due to the role the iodine atoms play in terms of blocking the Ni atom active sites. Specifically, on NiAu SAAs, the iodine atoms outcompete the methyl groups for occupancy of the Ni sites leaving the Me groups on Au, while on PdAu SAAs, the binding strengths of methyl groups and iodine atoms at the Pd atom active site are more similar. These simulations shed light on the mechanism of this important sp 3 –sp 3 carbon–carbon coupling chemistry on SAAs. Furthermore, we discuss the effect of the iodine atoms on the reaction energetics and make an analogy between the effect of iodine as an active site blocker on this model heterogeneous catalyst and homogeneous catalysts in which ligands must detach in order for the active site to be accessed by the reactants.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Decoupling of catalysis and transition state analog binding from mutations throughout a phosphatase revealed by high-throughput enzymology

Using high-throughput microfluidic enzyme kinetics (HT-MEK), we measured over 9,000 inhibition curves detailing impacts of 1,004 single-site mutations throughout the alkaline phosphatase PafA on binding affinity for two transition state analogs (TSAs), vanadate and tungstate. As predicted by catalytic models invoking transition state complementary, mutations to active site and active-site-contacting residues had highly similar impacts on catalysis and TSA binding. Unexpectedly, most mutations to more distal residues that reduced catalysis had little or no impact on TSA binding and many even increased tungstate affinity. These disparate effects can be accounted for by a model in which distal mutations alter the enzyme’s conformational landscape, increasing the occupancy of microstates that are catalytically less effective but better able to accommodate larger transition state analogs. In support of this ensemble model, glycine substitutions (rather than valine) were more likely to increase tungstate affinity (but not more likely to impact catalysis), presumably due to increased conformational flexibility that allows previously disfavored microstates to increase in occupancy. These results indicate that residues throughout an enzyme provide specificity for the transition state and discriminate against analogs that are larger only by tenths of an Ångström. Thus, engineering enzymes that rival the most powerful natural enzymes will likely require consideration of distal residues that shape the enzyme’s conformational landscape and fine-tune active-site residues. Biologically, the evolution of extensive communication between the active site and remote residues to aid catalysis may have provided the foundation for allostery to make it a highly evolvable trait.

59 BASIC BIOLOGICAL SCIENCES↗

Mud Volcanoes - A New Class of Sites for Geological and Astrobiological Exploration of Mars

Mud volcanoes provide a unique low-temperature window into the Earth s subsurface - including the deep biosphere - and may prove to be significant sources of atmospheric methane. The identification of analogous features on Mars would provide an important new class of sites for geological and astrobiological exploration. We report new work suggesting that features in Acidalia Planitia are most consistent with their being mud volcanoes.

Allen, C.C.↗

Final report: Insights from ARM observations into aerosol processing and transport by extratropical cyclones and aerosol effects on cyclone clouds

This project advanced understanding of aerosol–cloud interactions in extratropical cyclones using observations from the Atmospheric Radiation Measurement (ARM) Eastern North Atlantic (ENA) observatory and ACE-ENA field campaigns, along with satellite datasets and numerical modeling. We have quantified the susceptibility of frontal clouds to aerosols, showing that this susceptibility is similar to that in non-frontal clouds despite substantial (factor 2) differences in droplet concentrations between these cloud types, and also significant differences in cloud albedo. A key finding was that Aitken-mode (here, 60-100nm diameter) aerosols play a disproportionately important role in droplet activation in frontal clouds, and concentrations of these particles are frequently strongly biased in climate models. Activation of aerosols depends strongly on updraft speeds, and via collaboration with Argonne National Laboratory we contributed to quantifying these better with the ARM radar wind profiler at the ENA site. Our studies in the North Atlantic have analogs in the Southern Ocean, and to draw these out we examined data from the MARCUS and SOCRATES field campaigns. We identified new particle formation within extratropical cyclones as a potentially important source of cloud condensation nuclei in these pristine marine environments. By combining ARM observations with perturbed parameter ensemble simulations, we demonstrated that surface observations can effectively constrain aerosol–cloud adjustments and reduce uncertainty in simulated cloud liquid water path responses by approximately 15%, yielding stronger constraints on historical aerosol cooling effects. The work further established precipitation processes as a dominant control on aerosol–cloud interactions and Earth system predictability.

Gordon, Hamish [Department of Chemical Engineering↗