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At least 37 records · Page 2

Chemical Constraints Governing the Origin of Metabolism: The Thermodynamic Landscape of Carbon Group Transformations

The thermodynamics of organic chemistry under mild aqueous conditions was examined in order to begin to understand its influence on the structure and operation of metabolism and its antecedents. Free energies were estimated for four types reactions of biochemical importance carbon-carbon bond cleavage and synthesis, hydrogen transfer between carbon groups, dehydration of alcohol groups, and aldo-keto isomerization. The energies were calculated for mainly aliphatic groups composed of carbon, hydrogen, and oxygen. The energy values showed that (1) when carbon-carbon bond cleavage involves two different types of functional groups, transfer of the shared electron-pair to the more reduced carbon group is energetically favored over transfer to the more oxidized carbon group, and (2) the energy of carbon-carbon bond transformation is strongly dependent on the type of functional group that donates the shared electron-pair during cleavage, and the group that accepts the shared electron-pair during synthesis, and (3) the energetics of C-C bond transformation is determined primarily by the half-reaction energies of the couples: carbonyl/carboxylic acid, carboxylic acid/carbon dioxide, alcohol/carbonyl, and hydrocarbon/alcohol. The energy of hydrogen-transfer between carbon groups was found to depend on the functional group class of both the hydrogen-donor and hydrogen-acceptor. From these and other observations we concluded that the chemistry of the origin of metabolism (and to a lesser degree modem metabolism) is strongly constrained by the (1) limited disproportionation energy of organic substrates that can be dissipated in a few irreversible reactions, (2) the energy-dominance of few half-reaction couples in carbon-carbon bond transformation that establishes whether a chemical reaction is energetically irreversible, reversible or unfeasible, and (3) the dependence of the transformation-energy on the oxidation state of carbon groups (functional group type) which is contingent on prior reactions in the synthetic pathway.

Weber, Arthur L.↗

The Impacts of Fossil Fuel Emission Uncertainties and Accounting for 3-D Chemical CO2 Production on Inverse Natural Carbon Flux Estimates from Satellite and In Situ Data

Atmospheric carbon dioxide (CO2) inversions for estimating natural carbon fluxes typically do not allow for adjustment of fossil fuel CO2 emissions, despite significant uncertainties in emission inventories and inadequacies in the specification of international bunker emissions in inversions. Also, most inversions place CO2 release from fossil fuel combustion and biospheric sources entirely at the surface. However, a non-negligible portion of the emissions actually occurs in the form of reduced carbon species, which are eventually oxidized to CO2 downwind. Omission of this ‘chemical pump’ can result in a significant redistribution of the inferred total carbon fluxes among regions. We assess the impacts of different prescriptions of fossil fuel emissions and accounting for the chemical pump on flux estimation, with a novel aspect of conducting both satellite CO2 observation-based and surface in situ-based inversions. We apply 3-D carbon monoxide (CO) loss rates archived from a state-of-the-art GEOS chemistry and climate model simulation in a forward transport model run to simulate the distribution of CO2 originating from oxidation of carbon species. We also subtract amounts from the prior surface CO2 fluxes that are actually emitted in the form of fossil and biospheric CO, methane, and nonmethane volatile organic compounds (VOCs). We find that the posterior large-scale fluxes are generally insensitive to the finer-scale spatial differences between the ODIAC and CDIAC fossil fuel CO2 gridded datasets and assumptions about international bunker emissions. However, accounting for 3-D chemical CO2 production and the surface correction shifts the global carbon sink, e.g., from land to ocean and from the tropics to the north, with a magnitude and even direction that depend on assumptions about the surface correction. A GOSAT satellite-based inversion is more sensitive to the chemical pump than one using in situ observations, exhibiting substantial flux impacts of 0.28, 0.53, and -0.47 Pg C yr(exp -1) over tropical land, global land, and oceans, due to differences in the horizontal and vertical sampling of the wo observation types. Overall, the biases from neglecting the chemical pump appear to be minor relative to the flux estimate uncertainties and the differences between the in situ and GOSAT inversions, but their relative importance will grow in the future as observational coverage further increases and satellite retrieval biases decrease.

James S Wang↗

Electrolytic pretreatment of urine

Electrolysis has been under evaluation for several years as a process to pretreat urine for ultimate recovery of potable water in manned spacecraft applications. The conclusions that were drawn from this investigation are the following: (1) A platinum alloy containing 10 percent rhodium has been shown to be an effective, corrosion-resistant anode material for the electrolytic pretreatment of urine. Black platinum has been found to be suitable as a cathode material. (2) The mechanism of the reactions occurring during the electrolysis of urine is two-stage: (a) a total Kjeldahl nitrogen and total organic carbon (TOC) removal in the first stage is the result of electrochemical oxidation of urea to CO2, H2O, and ammonia followed by chloride interaction to produce N2 from ammonia, (b) after the urea has been essentially removed and the chloride ions have no more ammonia to interact with, the chloride ions start to oxidize to higher valence states, thus producing perchlorates. (3) Formation of perchlorates can be suppressed by high/low current operation, elevated temperature, and pH adjustment. (4) UV-radiation showed promise in assisting electrolytic TOC removal in beaker tests, but was not substantiated in limited single cell testing. This may have been due to non-optimum configurations of the single cell test rig and the light source.

Source record↗

Remote sensing of soils in the eastern Palouse region with Landsat Thematic Mapper

Soils of the Palouse region of eastern Washington State were investigated using Landsat Thematic Mapper (TM) band ratios to discriminate areas where erosion has caused paleosols to be exposed. Ratioed data were clustered and plotted to show soil lines which could be subdivided into various levels of organic matter and iron oxides. Successfully classified scenes of a summer fallow (bare soil) field were obtained with band ratios 1/4, 3/4, and 5/4 to map organic carbon and 3/4, 5/4, and 5/3 for the iron/carbon ratio indicator of erosion. Regression models were made with 5/4 data and organic carbon and 5/3 data and the iron/carbon ratio. Based on this analysis, 21 percent of the test field soils are exposed or nearly exposed paleosols.

Frazier, B. E.↗

Significant Tropospheric O3 Production from Extratropical Forest Fires:When? When Not?

There is significant controversy on whether extratropical fires contribute importantly to widespread ozone productionabsent the addition of urban pollutant nitrogen oxides (Jaffe and Widger, 2012, Singh et al., 2012,2013). Wereport a significant range of O3 production early in the fire plume history and report controls on which notable O3production occurs. The current data set is the airborne observations made on board NASAs highly instrumentedDC-8 aircraft during the ARCTAS (2008) and SEAC4RS (2013) campaigns within the Western United States. Aclear analysis of fire emissions was aided considerably by MERET (a Mixed Effects Regressions Emissions Technique).This technique allows consistent emission factors and enhancement ratios for O3 for individual aircraftsamples largely free from uncertainties resulting from mixing and entrainment which plague many published estimates.(Yokelson et al, 2013, Chatfield and Andreae, 2016). We find support for the reasonable idea that the ratioof nitrogen oxides (NOx) to volatile organic carbon (VOC) emissions controls new O3 production. The evidence isfor significant O3 production from high-fuel-nitrogen fuels (as evidenced by acetonitrile) and extremely hot largefires (like the Yosemite Rim Fire of 2013 which we analyze), while others do not. VOC emissions factors varysignificantly from fire to fire (and from different samples in the Rim Fire). Relative CO production (aka modifiedcombustion efficiency) is only one factor describing VOC emissions factors.

Chatfield, R.↗

Total Observed Organic Carbon (TOOC): A Synthesis of North American Observations

Measurements of organic carbon compounds in both the gas and particle phases made upwind, over and downwind of North America are synthesized to examine the total observed organic carbon (TOOC) in the atmosphere over this region. These include measurements made aboard the NOAA WP-3 and BAe-146 aircraft, the NOAA research vessel Ronald H. Brown, and at the Thompson Farm and Chebogue Point surface sites during the summer 2004 ICARTT campaign. Both winter and summer 2002 measurements during the Pittsburgh Air Quality Study are also included. Lastly, the spring 2002 observations at Trinidad Head, CA, surface measurements made in March 2006 in Mexico City and coincidentally aboard the C-130 aircraft during the MILAGRO campaign and later during the IMPEX campaign off the northwestern United States are incorporated. Concentrations of TOOC in these datasets span more than two orders of magnitude. The daytime mean TOOC ranges from 4.0 to 456 microg C/cubic m from the cleanest site (Trinidad Head) to the most polluted (Mexico City). Organic aerosol makes up 3-17% of this mean TOOC, with highest fractions reported over the northeastern United States, where organic aerosol can comprise up to 50% of TOOC. Carbon monoxide concentrations explain 46 to 86% of the variability in TOOC, with highest TOOC/CO slopes in regions with fresh anthropogenic influence, where we also expect the highest degree of mass closure for TOOC. Correlation with isoprene, formaldehyde, methyl vinyl ketone and methacrolein also indicates that biogenic activity contributes substantially to the variability of TOOC, yet these tracers of biogenic oxidation sources do not explain the variability in organic aerosol observed over North America. We highlight the critical need to develop measurement techniques to routinely detect total gas phase VOCs, and to deploy comprehensive suites of TOOC instruments in diverse environments to quantify the ambient evolution of organic carbon from source to sink.

Heald, C. L.↗

Diploptene: an indicator of terrigenous organic carbon in Washington coastal sediments

The pentacyclic triterpene 17 beta(H),21 beta(H)-hop-22(29)-ene (diploptene) occurs in sediments throughout the Columbia River drainage basin and off the southern coast of Washington state in concentrations comparable to long-chain plantwax n-alkanes. The same relationship is evident for diploptene and long-chain n-alkanes in soils from the Willamette Valley. Microorganisms indigenous to soils and soil erosion are indicated as the biological source and physical process, respectively, for diploptene in coastal sediments. Similarity between the stable carbon isotopic composition (delta 13CPDB) of diploptene isolated from soil in the Willamette Valley (-31.2 +/- 0.3%) and from sediments deposited throughout the Washington coastal environment (-31.2 +/- 0.5%) supports this argument. Values of delta for diploptene in river sediments are variable and 8-17% lighter, indicating that an additional biological source such as methane-oxidizing bacteria makes a significant contribution to the diploptene record in river sediments. Selective biodegradation resulting from a difference in the physicochemical association within eroded particles can explain the absence of the more-13C-depleted form of diploptene in Washington coastal sediments, but this mechanism remains unproven.

Non-NASA Center↗

Analysis of minerals containing dissolved traces of the fluid phase components water and carbon dioxide

Substantial progress has been made towards a better understanding of the dissolution of common gas/fluid phase components, notably H2O and CO2, in minerals. It has been shown that the dissolution mechanisms are significantly more complex than currently believed. By judiciously combining various solid state analytical techniques, convincing evidence was obtained that traces of dissolved gas/fluid phase components undergo, at least in part, a redox conversion by which they split into reduced H2 and and reduced C on one hand and oxidized oxygen, O(-), on the other. Analysis for 2 and C as well as for any organic molecules which may form during the process of co-segregation are still impeded by the omnipresent danger of extraneous contamination. However, the presence of O(-), an unusual oxidized form of oxygen, has been proven beyond a reasonable doubt. The presence of O(-) testifies to the fact that a redox reaction must have taken place in the solid state involving the dissolved traces of gas/fluid phase components. Detailed information on the techniques used and the results obtained are given.

Freund, Friedemann↗

The oxidation of isoprene in the troposphere - Mechanism and model calculations

Calculations have been performed for 15 deg N and 45 deg N latitude continental conditions using a one-dimensional, steady state photochemical model that incorporates a chemical mechanism describing the oxidation of isoprene by OH and O3 in the troposphere. At the higher latitude, anthropogenic hydrocarbon emission effects on NO(x) vertical profiles, as well as those of HNO3, overshadow isoprene emissions effects; at the lower latitude, reduced anthropogenic emissions and increased isoprene emissions respectively yield 26 and 4 percent increases in NO(x) and HNO3 column contents. It is suggested that a significant quantity of isoprene goes to the formation of longer carbon chain oxygenated organic species.

Brewer, D. A.↗

Biogeochemical cycles of carbon, sulfur, and free oxygen in a microbial mat

Complete budgets for carbon and oxygen have been constructed for cyanobacterial mats dominated by Microcoleus chthonoplastes from the evaporating ponds of a salt works. We infer from the data the various sinks for O2 as well as the sources of carbon for primary production. Although seasonal variability exists, a major percentage of the O2 produced during the day did not diffuse out of the mat but was used within the mat to oxidize both organic carbon and the sulfide produced by sulfate reduction. At night, most of the O2 that diffused into the mat was used to oxidize sulfide, with O2 respiration of minor importance. During the day, the internal mat processes of sulfate reduction and O2 respiration generated as much or more inorganic carbon (DIC) for primary production as diffusion into the mat. Oxygenic photosynthesis was the most important process of carbon fixation. At night, the DIC lost from the mat was mostly from sulfate reduction. Elemental fluxes across the mat/brine interface indicated that carbon with an oxidation state of greater than zero was taken up by the mat during the day and liberated from the mat at night. Overall, carbon with an average oxidation state of near zero accumulated in the mat. Both carbon fixation and carbon oxidation rates varied with temperature by a similar amount.

Canfield, Donald E.↗

Study of Stable Cathodes and Electrolytes for High Specific Density Lithium-Air Battery

Future NASA missions require high specific energy battery technologies, greater than 400 Wh/kg. Current NASA missions are using "state-of-the-art" (SOA) Li-ion batteries (LIB), which consist of a metal oxide cathode, a graphite anode and an organic electrolyte. NASA Glenn Research Center is currently studying the physical and electrochemical properties of the anode-electrolyte interface for ionic liquid based Li-air batteries. The voltage-time profiles for Pyr13FSI and Pyr14TFSI ionic liquids electrolytes studies on symmetric cells show low over-potentials and no dendritic lithium morphology. Cyclic voltammetry measurements indicate that these ionic liquids have a wide electrochemical window. As a continuation of this work, sp2 carbon cathode and these low flammability electrolytes were paired and the physical and electrochemical properties were studied in a Li-air battery system under an oxygen environment.

cathodes↗

Comet Shoemaker-Levy 9, Jupiter, and Impact Shock Chemistry

Four years ago this month, a hitherto unknown comet in loose orbit around Jupiter passed so near the giant planet that it was torn apart into 20 fragments by tides. One orbit later, two years ago this month, the fragments of doomed comet P/Shoemaker Levy (SL9) fell into Jupiter. The enormous energies of these impacts (the largest fragments were nearly 1 km across and, hitting at 60 km/s, released some 2-4 x 10(exp 27) ergs) produced enormous explosions. Several of the ejecta plumes were imaged towering 3000 km above Jupiter's limb. The heat released when the plumes fell was considerable and easily observed on Earth. The impacts produced strong shocks, both promptly at the impact site and again, later, and over thousands of kilometers, when the ejecta plume reentered the atmosphere. The focus of this talk will be to discuss what the SL9 impacts taught us about impact shock chemistry - the processes, the ingredients, the results - and what inferences we may draw for impacts on early Earth. Shock chemistry generates a suite of molecules not usually seen on Jupiter. The most surprising report was of a huge amount of diatomic sulfur S2 at the site of the G impact. Other unusual products include CS, CS2, OCS, H2S, SO2, HCN, CO, and H2O; although H2S and H2O are doubtless abundant below the visible clouds. Hot or enhanced CH4 and NH3 were also detected. A general rule of shock chemistry is that CO forms until either C or O is exhausted. If O greater than C, the other products are oxidized, and excess O goes to H2O. If C greater than O, the other products are reduced, and excess C goes to HCN, C2H2, and a wide variety of more complicated organics. Ultimately, given time, the carbon would react all the way to graphite, but in practice the reactions are incomplete. The dark ejecta debris were probably composed in part of carbonaceous particles generated by the shocks. In a sense, the SL9 impacts performed the famous Miller-Urey experiment on a grand scale, with one result being the production of a lot of complex brown organic solids (called "tholins"). We use, a straightforward chemical kinetics model for the H, N, C, O, S system to follow the nonequilibrium chemistry behind the shocks. The model traces the evolving chemical composition of a parcel of gas by directly integrating the web of chemical reactions. Pressure and temperature histories of the parcels are patterned after those calculated by numerical hydrodynamic simulations of the ejecta plume. A given plume parcel is generally shocked twice; t.e a parcel shocked near the impact site is ejected at high velocity and is shocked again when it reenters the atmosphere. The final state of the gas depends mostly on the second shock, provided that the latter is hot enough. The chemical evidence is ambiguous, but most indications are that C greater than O in the shocked, reacting gas. Telltale signatures of abundant oxygen - SO2, SO, CO2, O2 - were not seen, while signatures of abundant carbon - CS, CS2, and HCN - were. On the other hand, abundant H2O would appear to require O greater than C, and two other observed sulfur species, S2 and OCS, appear to form more easily in a somewhat oxidized gas, presumable vaporized from the comet itself. Since on general principles one expects the -comet to have had a more-or-less cosmic composition, i.e. O greater than C, the production of CS, CS2, and HCN probably requires C greater than O in the shocked jovian air. This in turn implies that even the largest fragments released the bulk of their energy above the jovian water table, in all likelihood above 5 bars . There is no evidence in favor of the proposition that a significant amount of wet jovian air was shocked strongly enough to coax water to react; i.e. wet jovian air saw only temperatures significantly below 2000 K.

Zahnle, Kevin↗

Energy Efficient Microlith-Based Catalytic Reactor and Recuperator for Air Quality Control Applications

Precision Combustion, Inc. (PCI) and NASA’s Marshall Space Flight Center (MSFC) have been developing, characterizing, and optimizing high temperature catalytic oxidizers (HTCO) based on PCI’s patented Microlith technology to meet the requirements of future extended human spaceflight explorations. Previous efforts focused on integrating PCI’s HTCO unit with a compact, simple recuperative heat exchanger to reduce the overall system size and weight. Significant improvement was demonstrated over traditional approaches of integrating the HTCO with an external recuperative heat exchanger. While the critical target performance metrics were achieved, the thermal effectiveness of PCI’s recuperator remained a potential area of improvement to further reduce the energy requirements of the integrated system. Using the same material combinations and an improved recuperator design, the redesigned prototype has experimentally demonstrated 20 – 30% reduction (flow dependent) in steady state power consumption compared to the earlier prototype without compromising the destruction efficiency of methane and volatile organic compounds (VOCs). Moreover, design modifications and improvements allow our redesigned prototype to be more easily manufactured compared to traditional brazed plate-fin recuperator designs. The redesigned prototype was delivered to MSFC for validation testing. Here, we report and discuss the performance of the improved prototype HTCO unit with a high efficiency recuperative heat exchanger based on testing at PCI and MSFC. The device is expected to provide a reliable and robust means of disposing of trace levels of methane and VOCs by oxidizing them into carbon dioxide and water in order to maintain clean air in enclosed spaces, such as crewed spacecraft cabins.

Vilekar, Saurabh A.↗

Observations on gas exchange and element recycle within a gas-closed algal-mouse system

Life support systems based on bioregeneration rely on the control and manipulation of organisms. Algae are potentially useful for a variety of Closed Ecological Life Support System (CELSS) functions including the revitalization of atmospheres, production of food and for nitrogen fixation. The results of experiments conducted with a gas-closed algal-mouse system designed to investigate gas exchange phenomena under varying algal environmental conditions, and the ability of algae to utilize oxidized mouse solid waste are reported. Inherent instabilities exist between the uptake and release of carbon dioxide (CO2) and oxygen (O2) by the mouse and algae in a gas-closed system. Variations in light intensity and cell density alter the photosynthetic rate of the algae and enable short-term steady-state concentrations of atmospheric CO2 and O2. Different nitrogen sources (urea and nitrate) result in different algal assimilatory quotients (AQ). Combinations of photosynthetic rate and AQ ratio manipulations were examined for their potential in stabilizing atmospheric gas concentrations in the gas-closed algal-mouse system.

Smernoff, D. T.↗

Diamondites: Evidence for a Distinct Tectono-Thermal Diamond-Forming Event Beneath the Kaapvaal Craton

The petrogenesis and relationship of diamondite to well-studied monocrystalline and fibrous diamonds are poorly understood yet would potentially reveal new aspects of how diamond-forming fluids are transported through the lithosphere and equilibrate with surrounding silicates. Of twenty-two silicate- and oxide-bearing diamondites investigated, most yielded garnet intergrowths (n = 15) with major element geochemistry (i.e. Ca-Cr) classifying these samples as low-Ca websteritic or eclogitic. The garnet REE patterns fit an equilibrium model suggesting the diamond-forming fluid shares an affinity with high-density fluids (HDF) observed in fibrous diamonds, specifically on the join between the saline–carbonate end- members. The δ13C values for the diamonds range from -5.27 to -22.48 ‰ (V-PDB) with δ18O values for websteritic garnets ranging from +7.6 to +5.9 ‰ (V-SMOW). The combined C-O stable isotope data support a model for a hydrothermally altered and organic carbon-bearing subducted crustal source(s) for the diamond- and garnet-forming media. The nitrogen aggregation states of the diamonds require that diamondite-formation event(s) pre-dates fibrous diamond-formation and post-dates most of the gem monocrystalline diamond-formation events at Orapa. The modelled fluid compositions responsible for the precipitation of diamondites match the fluid-poor and fluid-rich (fibrous) monocrystalline diamonds, where all grow from HDFs within the saline-silicic-carbonatitic ternary system. However, while the nature of the parental fluid(s) share a common lithophile element geochemical affinity, the origin(s) of the saline, silicic, and/or carbonatitic components of these HDFs do not always share a common origin. Therefore, it is wholly conceivable that the diamondites are evidence of a distinct and temporally unconstrained tectono-thermal diamond-forming event beneath the Kaapvaal craton.

S Mikhail↗

Electrochemical incineration of wastes

The disposal of domestic organic waste in its raw state is a matter of increasing public concern. Earlier, it was regarded as permissible to reject wastes into the apparently infinite sink of the sea but, during the last 20 years, it has become clear that this is environmentally unacceptable. On the other hand, sewage farms and drainage systems for cities and for new housing developments are cumbersome and expensive to build and operate. New technology whereby waste is converted to acceptable chemicals and pollution-free gases at site is desirable. The problems posed by wastes are particularly demanding in space vehicles where it is desirable to utilize treatments that will convert wastes into chemicals that can be recycled. In this situation, the combustion of waste is undesirable due to the inevitable presence of oxides of nitrogen and carbon monoxide in the effluent gases. Here, in particular, electrochemical techniques offer several advantages including the low temperatures which may be used and the absence of any NO and CO in the evolved gases. Work done in this area was restricted to technological papers, and the present report is an attempt to give a more fundamental basis to the early stages of a potentially valuable technology.

Kaba, L.↗

In-situ Raman Instrumentation and Measurements in Supercritical Water Oxidation Systems

Due to the advent of recent advances in reactor designs and operational procedures, renewed attention has been given to a host of supercritical water oxidation (SCWO) technology applications. This includes resource recovery, water reclamation, and solid waste destruction. SCWO is often recognized as a “green technology” because of its ability to extract useful energy while producing benign products from environmentally challenging waste streams (e.g., wet organic wastes, pharmaceutical wastes, military wastes). The present work was motivated by NASA’s interests in solid waste management and water recovery for long-duration space missions. To that end, the main focus of this paper is to present work on characterizing the behavior of supercritical water oxidation systems utilizing state of the art laser Raman spectroscopy. The main benefit of Raman diagnostics is its ability to identify chemical composition and to measure concentrations of the compounds involved in the reaction. Two separate Raman systems for SCWO measurements that have been developed for this study will be described. The first system is a 2-D traversing system useful for making in-situ measurements in conditions where spatial gradients of species and temperature are important and has been successfully utilized in making species (ethanol, oxygen, water, nitrogen and carbon dioxide) concentrations and temperature measurements in ethanol hydrothermal jet flames. The second system is a packaged modular Raman probe unit for portable deployment to different reactors and is more suitable for relatively homogeneous systems such as a batch reactor. The design, development, and examples of obtained results from both systems will be presented for various reactant streams. Reaction rate and fuel conversion estimates from chemistry models will also be presented.

supercritical water oxidation↗

The Athena Mars Rover Science Payload

The Mars Surveyor missions that will be launched in April of 2001 will include a highly capable rover that is a successor to the Mars Pathfinder mission's Sojourner rover. The design goals for this rover are a total traverse distance of at least 10 km and a total lifetime of at least one Earth year. The rover's job will be to explore a site in Mars' ancient terrain, searching for materials likely to preserve a record of ancient martian water, climate, and possibly biology. The rover will collect rock and soil samples, and will store them for return to Earth by a subsequent Mars Surveyor mission in 2005. The Athena Mars rover science payload is the suite of scientific instruments and sample collection tools that will be used to perform this job. The specific science objectives that NASA has identified for the '01 rover payload are to: (1) Provide color stereo imaging of martian surface environments, and remotely-sensed point discrimination of mineralogical composition. (2) Determine the elemental and mineralogical composition of martian surface materials. (3) Determine the fine-scale textural properties of these materials. (4) Collect and store samples. The Athena payload has been designed to meet these objectives. The focus of the design is on field operations: making sure the rover can locate, characterize, and collect scientifically important samples in a dusty, dirty, real-world environment. The topography, morphology, and mineralogy of the scene around the rover will be revealed by Pancam/Mini-TES, an integrated imager and IR spectrometer. Pancam views the surface around the rover in stereo and color. It uses two high-resolution cameras that are identical in most respects to the rover's navigation cameras. The detectors are low-power, low-mass active pixel sensors with on-chip 12-bit analog-to-digital conversion. Filters provide 8-12 color spectral bandpasses over the spectral region from 0.4 to 1.1 micron Narrow-angle optics provide an angular resolution of 0.28 mrad/pixel, nearly a factor of four higher than that of the Mars Pathfinder and Mars Surveyor '98 cameras. Image compression will be performed using a wavelet compression algorithm. The Mini-Thermal Emission Spectrometer (Mini-TES) is a point spectrometer operating in -the thermal IR. It produces high spectral resolution (5 /cm) image cubes with a wavelength range of 5-40 gm, a nominal signal/noise ratio of 500:1, and a maximum angular resolution of 7 mrad (7 cm at a distance of 10 in). The wavelength region over which it operates samples the diagnostic fundamental absorption features of rockforming minerals, and also provides some capability to see through dust coatings that could tend to obscure spectral features. The mineralogical information that Mini-TES provides will be used to select from a distance the rocks and soils that will be investigated in more detail and ultimately sampled. Mini-TES is derived from the MO/MGS TES instrument, but is significantly smaller and simpler. The instrument uses an 8-cm Cassegrain telescope, a Michelson interferometer, and uncooled pyroelectric detectors. Along with its mineralogical capabilities, Mini-TES can provide information on the thermophysical properties of rocks and soils. Viewing upward, it can also provide temperature profiles through the martian atmospheric boundary layer. Elemental and Mineralogical Composition: Once promising samples have been identified from a distance using Pancam/Mini-TES, they will be studied in detail using up to three compositional sensors that can be placed directly against them by an Instrument Arm. The two compositional sensors, presently on the payload are an Alpha-Proton-X-Ray Spectrometer (APXS), and a Mossbauer Spectrometer. The APXS is derived closely from the instrument that flew on Mars Pathfinder. Radioactive alpha sources and three detection modes (alpha, proton, and x-ray) provide elemental abundances of rocks and soils to complement and constrain mineralogical data. The Athena APXS will have a revised mechanical design that will cut down significantly on backscattering of alpha particles from martian atmospheric carbon. It will also include a target of known elemental composition that will be used for calibration purposes. The Athena Mossbauer Spectrometer is a diagnostic instrument for the mineralogy and oxidation state of Fe-bearing phases, which are particularly important on Mars. The instrument measures the resonant absorption of gamma rays produced by a Co-57 source to determine splitting of nuclear energy levels in Fe atoms that is related to the electronic environment surrounding them. It has been under development for space flight for many years at the Technical University of Darmstadt. The Mossbauer Spectrometer (and the other arm instruments) will be able to view a small permanent magnet array that will attract magnetic particles in the martian soil. The payload may also include a Raman Spectrometer. If included, the Raman Spectrometer will provide precise identification of major and minor mineral phases. It requires no sample preparation, and is also sensitive to organics. Fine-Scale Texture: The Instrument Arm a also carries a Microscopic Imager that will obtain high-resolution monochromatic images of the same materials for which compositional data will be obtained. Its spatial resolution is 20 micron/pixel over a 1 cm depth of field, and 40 micron/pixel over a 1-cm depth of field. Like Pancam, it uses the same active pixel sensor detectors and electronics as the rover's navigation cameras. The Instrument Arm is a three degree-of-freedom arm that uses designs and components from the Mars Pathfinder and Mars Surveyor '98 projects. Its primary function is instrument positioning. Along with the instruments noted above, it also carries a brush that can be used to remove dust and other loose coatings from rocks. Sample Collection and Storage: Martian rock and soil samples will be collected using a low-power rotary coring drill called the Mini-Corer. An important characteristic of this device is that it can obtain intact samples of rock from up to 5 cm within strong boulders and bedrock, Nominal core dimensions are 8xl7 mm. The Mini-Corer drills a core to the commanded depth in a rock, shears it off, retains it, and extracts it. It can also acquire samples of loose soil, using soil sample cups that are pressed downward into loose material. The Mini-Corer can drill at angles from vertical to 45' off vertical. It has six interchangeable bits for long life. Mechanical damage to the sample during drilling is minimal, and heating is negligible. After acquisition, the sample may be viewed by the arm instruments, and/or placed in one of 104 compartments in the Sample Container. A subset of the acquired samples may be replaced with other samples obtained later if desired. The Sample Container has no moving parts, and is mounted external to the rover for easy removal by the Mars Surveyor 2005 flight system. Operation of the rover will make extensive use of automated onboard navigation and hazard avoidance capabilities. Otherwise, use of onboard autonomy is minimal. Data downlink capability is about 40 Mbit/sol, and the use of the Mars Surveyor '01 orbiter for data relay imposes a limit of at most two command cycles per sol. Because of the significant amount of time available between command cycles, all payload elements will be operated sequentially, rather than in parallel.; this approach also significantly simplifies operations and minimizes peak power usage. The landing site for the '01 rover has not been selected yet. Site selection will make as full use as possible of Mars Global Surveyor data, and will involve substantial input from the broad Mars science community. Summary: The following table describes the mass, power, providers, and key scientific objectives of all the major elements of the Athena payload. Additional Athena payload information may be found at: http://astrosun.tn.cornell.edu/athena/index.html. Additional information contained in the original.

Squyes, S. W.↗