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SiC and Si3N4 Recession Due to SiO2 Scale Volatility Under Combustor Conditions

SiC and Si3N4 materials were tested under various turbine engine combustion environments, chosen to represent either conventional fuel-lean or fuel-rich mixtures proposed for high speed aircraft. Representative CVD, sintered, and composite materials were evaluated in both furnace and high pressure burner rig exposure. While protective SiO2 scales form in all cases, evidence is presented to support paralinear growth kinetics, i.e. parabolic growth moderated simultaneously by linear volatilization. The volatility rate is dependent on temperature, moisture content, system pressure, and gas velocity. The burner tests were used to map SiO2 volatility (and SiC recession) over a range of temperature, pressure, and velocity. The functional dependency of material recession (volatility) that emerged followed the form: exp(-QIRT) * P(exp x) * v(exp y). These empirical relations were compared to rates predicted from the thermodynamics of volatile SiO and SiO(sub x)H(sub Y) reaction products and a kinetic model of diffusion through a moving, boundary layer. For typical combustion conditions, recession of 0.2 to 2 micron/h is predicted at 1200- 1400C, far in excess of acceptable long term limits.

Smialek, James L.↗

SiC and Si3N4 Recession Due to SiO2 Scale Volatility Under Combustor Conditions

Silicon carbide (SiC) and Si3N4 materials were tested in various turbine engine combustion environments chosen to represent either conventional fuel-lean or fuel-rich mixtures proposed for high-speed aircraft. Representative chemical vapor-deposited (CVD), sintered, and composite materials were evaluated by furnace and high-pressure burner rig exposures. Although protective SiO2 scales formed in all cases, the evidence presented supports a model based on paralinear growth kinetics (i.e., parabolic growth moderated simultaneously by linear volatilization). The volatility rate is dependent on temperature, moisture content, system pressure, and gas velocity. The burner tests were thus used to map SiO2 volatility (and SiC recession) over a range of temperatures, pressures, and velocities. The functional dependency of material recession (volatility) that emerged followed the form A[exp(-Q / RT)](P(sup x)v(sup y). These empirical relations were compared with rates predicted from the thermodynamics of volatile SiO and SiOxHy reaction products and a kinetic model of diffusion through a moving boundary layer. For typical combustion conditions, recession of 0.2 to 2 micrometers/hr is predicted at 1200 to 1400 C, far in excess of acceptable long-term limits.

Smialek, James L.↗

Delivery of Volatiles to Habitable Planets in Extrasolar Planetary Systems

The Earth can support life because: (1) its orbit lies in the Sun's habitable zone', and (2) it contains enough volatile material (e.g. water and organics) for life to flourish. However, it seems likely that the Earth was drier when it formed because it accreted in a part of the Sun's protoplanetary nebula that was too hot for volatiles to condense. If this is correct, water and organics must have been delivered to the habitable zone, after dissipation of the solar nebula, from a 'wet zone' in the asteroid belt or the outer solar system, where the nebula was cool enough for volatiles to condense. Material from the wet zone would have been delivered to the Earth by Jupiter and Saturn. Gravitational perturbations from these giant planets made much of the wet zone unstable, scattering volatile-rich planetesimals and protoplanets across the Solar System. Some of these objects ultimately collided with the inner Planets which themselves lie in a stable part of the Solar System. Giant planets are now being discovered orbiting other sunlike stars. To date, these planets have orbits and masses very different from Jupiter and Saturn, such that few if any of these systems is likely to have terrestrial planets in the star's habitable zone. However, new discoveries are anticipated due to improved detector sensitivity and the increase in the timespan of observations. Here we present numerical experiments examining the range of giant-planet characteristics that: (1) allow stable terrestrial Planets to exist in a star's habitable zone, and (2) make a large part of the star's wet zone weakly unstable, thus delivering volatiles to the terrestrial planets over an extended period of time after the dissipation of the solar nebula.

Chambers, John E.↗

Global Distribution and Sources of Volatile and Nonvolatile Aerosol In the Remote Troposphere

Airborne measurements of aerosol (Condensation Nuclei, CN) and selected trace gases made in the areas of the North Atlantic Ocean during SONEX (October/November 1997), and the south tropical Pacific Ocean during PEM-Tropics A (September/October 1996) and PEM-Tropics B (March/April 1999) have been analyzed. Emphasis is on the interpretations of variations in the number densities of the fine (>17 nm) and ultrafine (>8 nm) CN in the upper troposphere (8-12 km). These data suggest that large number densities of highly volatile CN (10(exp 4)-10(exp 5)/cu cm) are present in the clean upper troposphere with highest values over the tropical1subtropical region. Through marine convection and long-distance horizontal transport, volatile CN originating from the tropical/subtropical regions can frequently impact the abundance of aerosol in the middle and upper troposphere at mid to high latitudes. Nonvolatile aerosol particles behave in a manner similar to tracers of combustion (CO) and photochemical pollution (PAN), implying a source from continental pollution of industrial or biomass burning origin. In the upper troposphere, we find that volatile and nonvolatile partials number densities are inversely correlated. An aerosol microphysical model is used to suggest that coagulation of fine volatile particles with fewer larger nonvolatile particles provides one possible mechanism for this relationship. It appears that nonvolatile particles, of principally anthropogenic origin,provide a highly efficient removal process for the fine volatile aerosol.

Singh, Hanwant B.↗

On the Abundances of Moderately Volatile Elements in Meteorites

The abundances of the moderately volatile elements (those which condense or evaporate in the temperature range 650-1350 K) in chondritic meteorites deviate from solar (or 'cosmic', as defined by CI meteorite composition) in a manner that strongly suggests that they were determined primarily by volatility, independent of chemical affinity. Wasson and collaborators have long argued that the observed correlation of relative abundance with condensation temperature reflects a systematically selective process which favored the accretion of refractory material over volatile material from a nebula cooling from a hot initial state. This view is supported by the detailed examination of chondrules and matrix in carbonaceous meteorites and the contrast between meteorite trace element abundance patterns with those produced in heating experiments. However, the idea that the moderately volatile abundances reflect global condensation has not previously been quantitatively tested or used as a constraint on nebula evolution. We have therefore constructed models of the solar nebula designed specifically for addressing meteoritic data. Calculations so far indicate that the abundance patterns of the moderately volatile elements in chondritic meteorites can be produced naturally in an evolving nebula that cools with the reduction in opacity associated with the accumulation of meteoritic bodies. Additional information is contained in the original extended abstract.

Cassen, Pat↗

Polar Wander on Triton and Pluto Due to Volatile Migration

Polar wander may occur on Triton and Pluto because of volatile migration. Triton, with its low obliquity, can theoretically sublimate volatiles (mostly nitrogen) at the rate of approximately 10(exp 14) kilograms per year from the equatorial regions and deposit them at the poles. Assuming Triton to be rigid on the sublimation timescale, after approximately 10(exp 5) years the polar caps would become large enough to cancel the rotational flattening, with a total mass equivalent to a global layer approximately 120-250 m in depth. At this point the pole wanders about the tidal bulge axis, which is the line joining Triton and Neptune. Rotation about the bulge axis might be expected to disturb the leading side/trailing side cratering statistics. Because no such disturbance is observed, it may be that Triton's mantle viscosity is too high but its surface volatile inventory is too low to permit wander. On the other hand, its mantle viscosity might be low, so that any uncompensated cap load might be expected to wander toward the tidal bulge axis. In this case, the axis of wander passes through the equator from the leading side to the trailing side; rotation about this wander axis would not disturb the cratering statistics. Low-viscosity polar wander may explain the bright southern hemisphere: this is the pole which is wandering toward the equator. In any case the permanent polar caps may be geologically very young. Polar wander may possibly take place on Pluto, due to its obliquity oscillations and perihelion-pole geometry. However, Pluto is probably not experiencing any wander at present. The Sun has been shining strongly on the poles over the last half of the obliquity cycle, so that volatiles should migrate to the equator, stabilizing the planet against wander. Spacecraft missions to Triton and Pluto which measure the dynamical flattening could give information about the accumulation of volatiles at the poles. Such information is best obtained by measuring gravity and topography from orbiters, as was done for Mars with the highly successful Mars Global Surveyor.

Rubincam, David Parry↗

Volatile-rich Crater Interior Deposits in the Polar Regions of Mars: Evidence for Ice Cap Advance and Retreat

Many craters on Mars are partially filled by distinctive material emplaced by post-impact processes. This crater fill material is an interior mound which is generally separated from the walls of the crater by a trough that may be continuous along the crater circumference (i.e. a ring-shaped trough), or which may only partially contact the crater walls (i.e. a crescent-shaped trough). The fill deposit is frequently offset from the crater center and may be asymmetric in plan view. Populations of such craters include those in the circum-south polar cap region, in Arabia Terra, associated with the Medusae Fossae Formation, and in the northern lowlands proximal to the north polar cap. We focus on those craters in circumpolar regions and assess their relationship to polar cap advance and retreat, especially the possibility that fill material represents remnants of a formerly larger contiguous cap. Volatile-rich deposits have the property of being modifiable by the local stability of the solid volatile, which is governed by local energy balance. Here we test the hypothesis that asymmetries in volatile fill shape, profile, and center-location within a crater result from asymmetries in local energy balance within the crater, due mainly to variation of solar insolation and radiative effects of the crater walls over the crater interior. Model profiles of crater fill are compared with MOLA topographic profiles to assess this hypothesis. If asymmetry in morphology and location of crater fill are consistent with radiative-dominated asymmetries in energy budget within the crater, then 1) the volatile-rich composition of the fill is supported (this process should not be effective at shaping volcanic or sedimentary deposits), and 2) the dominant factor determining the observed shape of volatile-rich crater fill is the local radiative energy budget (and erosive processes such as eolian deflation are secondary or unnecessary). We also use a geographic and energy model approach to specifically test the idea that material in partially filled craters around the south pole may once have been contiguous to the cap and may have been sustained and modified by radiative processes specific to the crater environment (as opposed to the surrounding plains) as the cap retreated.

Russell, Patrick S.↗

RESOLVE Projects: Lunar Water Resource Demonstration and Regolith Volatile Characterization

To sustain affordable human and robotic space exploration, the ability to live off the land at the exploration site will be essential. NASA calls this ability in situ resource utilization (ISRU) and is focusing on finding ways to sustain missions first on the Moon and then on Mars. The ISRU project aims to develop capabilities to technology readiness level 6 for the Robotic Lunar Exploration Program and early human missions returning to the Moon. NASA is concentrating on three primary areas of ISRU: (1) excavating, handling, and moving lunar regolith, (2) extracting oxygen from lunar regolith, and (3) finding, characterizing, extracting, separating, and storing volatile lunar resources, especially in the permanently shadowed polar craters. To meet the challenges related to technology development for these three primary focus areas, the Regolith and Environment Science and Oxygen and Lunar Volatile Extraction (RESOLVE) project was initiated in February 2005, through funding by the Exploration Systems Mission Directorate. RESOLVE's objectives are to develop requirements and conceptual designs and to perform breadboard concept verification testing of each experiment module. The final goal is to deliver a flight prototype unit that has been tested in a relevant lunar polar environment. Here we report progress toward the third primary area creating ways to find, characterize, extract, separate, and store volatile lunar resources. The tasks include studying thermal, chemical, and electrical ways to collect such volatile resources as hydrogen, water, nitrogen, methane, and ammonia. We approached this effort through two subtasks: lunar water resource demonstration (LWRD) and regolith volatile characterization (RVC).

Source record↗

Infrared Spectroscopy of Parent Volatiles in Comets: Implications for Astrobiology

Current cometary orbits provide information on their recent dynamical history. However, determining a given comet's formation region from its current dynamical state alone is complicated by radial migration in the proto-planetary disk and by dynamical interactions with the growing giant planets. Because comets reside for long periods of time in the outer Solar System, the ices contained in their nuclei (native ices) retain a relatively well-preserved footprint of when and where they formed, and this in turn can provide clues to conditions in the formation epoch. As a comet approaches the Sun, sublimation of its native ices releases parent volatiles into the coma where they can be measured spectroscopically. The past to - 15 years have seen the advent of infrared spectrometers with high sensitivity between about 2.8 and 5.0 micron, enabling a taxonomy among comets based on abundances of parent volatiles (e.g., H2O, CO, CH4, C2H6, HCN, CH30H, H2CO, NH3). Such molecules are of keen interest to Astrobiology, as they include important pre-biotic species that likely were required for the emergence of life on Earth and perhaps elsewhere. Approximately 20 comets have thus far been characterized, beginning with C/1996 82 (Hyakutake) in 1996. Molecular production rates are established through comparison of observed emission line intensities with those predicted by quantum mechanical fluorescence models. Abundances of parent volatiles (relative to H2O) vary among even the relatively small number of comets sampled, with the most volatile species (CO and CH4) displaying the largest variations. Techniques developed for measuring parent volatile abundances in comets will be discussed, as will possible implications for their formation.

DiSanti, Michael A.↗

Cold and Cryogenic Curation of Lunar Volatile Samples Returned to Earth

The study of volatile compounds and volatile elements, such as H, He, C, N, O, H2O, CH4, SO2, CO, CO2, NH3, HCN, etc., are commonly used for constraining evolutionary processes on planets, satellites, and asteroids, as well as formulating models of solar system formation. For Lunar science, the recent evidence of regolith and rocks containing small amounts of OH- and/or H2O has renewed scientific interest into the study of lunar volatiles [1, 2]. Future lunar sample return missions will include the study of volatiles as a high priority. Comet particles from the Stardust mission, asteroid particles from Hayabusa, meteorites, and subsurface lunar samples all occupied subfreezing environments prior to collection. Valuable geochemical information on volatiles is often lost when these samples are allowed to reach ambient temperatures on Earth. The ability to store, document, subdivide, and transport extraterrestrial geologic samples while maintaining below freezing or cryogenic temperatures is required for the complete scientific study of such samples, as well as future samples from a wide range of solar system bodies.

Calaway, M. J.↗

Volatile Siderophile Elements in Shergottites: Constraints on Core Formation and Magmatic Degassing

Volatile siderophile elements (e.g., As, Sb, Ge, Ga, In, Bi, Zn, Cd, Sn, Cu, Pb) can place constraints both on early differentiation as well as the origin of volatiles. This large group of elements has been used to constrain Earth accretion [1,2], and Earth-Moon geochemistry [3]. Application to Earth has been fostered by new experimental studies of these elements such as Ge, In, and Ga [4,5,6]. Application to Mars has been limited by the lack of data for many of these elements on martian meteorites. Many volatile elements are considered in the pioneering work by [7] but for only the small number of martian samples then available. We have made new measurements on a variety of martian meteorites in order to obtain more substantial datasets for these elements using the analytical approach of [8]. We use the new dataset, together with published data from the literature, to define martian mantle abundances of volatile siderophile elements. Then, we evaluate the possibility that these abundances could have been set by mid-mantle (14 GPa, 2100 C) metal-silicate equilibrium, as suggested by the moderately and slightly siderophile elements [9]. Finally, we examine the possibility that some elements were affected by volatility and magmatic degassing.

Righter, Kevin↗

Volatile Analysis by Pyrolysis of Regolith for Planetary Resource Exploration

The extraction and identification of volatile resources that could be utilized by humans including water, oxygen, noble gases, and hydrocarbons on the Moon, Mars, and small planetary bodies will be critical for future long-term human exploration of these objects. Vacuum pyrolysis at elevated temperatures has been shown to be an efficient way to release volatiles trapped inside solid samples. In order to maximize the extraction of volatiles, including oxygen and noble gases from the breakdown of minerals, a pyrolysis temperature of 1400 C or higher is required, which greatly exceeds the maximum temperatures of current state-of-the-art flight pyrolysis instruments. Here we report on the recent optimization and field testing results of a high temperature pyrolysis oven and sample manipulation system coupled to a mass spectrometer instrument called Volatile Analysis by Pyrolysis of Regolith (VAPoR). VAPoR is capable of heating solid samples under vacuum to temperatures above 1300 C and determining the composition of volatiles released as a function of temperature.

Glavin, Daniel P.↗

Lunar Volatiles: An Earth-Moon Perspective

It has generally been accepted that the Moon is depleted in volatile elements. However, the recent discovery of measurable water in lunar glasses and apatites suggests that volatiles are not as depleted as was once thought. And, in fact, some authors have claimed that water contents of the lunar and terrestrial mantles are similar. Moderately volatile alkali elements may have a bearing on this issue. In general, bulk Moon alkalis are depleted relative to the bulk silicate Earth. Although the bulk lunar chemical composition is difficult to reconstruct, good correlations of alkali elements with refractory lithophile incompatible trace elements make this conclusion robust. These observations have been taken to mean that the Moon overall is depleted in volatiles relative to the Earth. Since water is more volatile than any of the alkali elements, presumably this conclusion is true for water, or even more so.

Jones, John H.↗

Microwave Extraction of Volatiles for Mars Science and ISRU

The greatest advantage of microwave heating for volatiles extraction is that excavation can be greatly reduced. Surface support operations would be simple consisting of rovers with drilling capability for insertion of microwaves down bore holes to heat at desired depths. The rovers would also provide support to scientific instruments for volatiles analysis and for volatiles collection and storage. The process has the potential for a much lower mass and a less complex system than other in-situ processes. Microwave energy penetrates the surface heating within with subsequent sublimation of water or decomposition of volatile containing minerals. On Mars the volatiles should migrate to the surface to be captured with a cold trap. The water extraction and transport process coupled with atmospheric CO2 collection could readily lead to a propellant production process, H2O + CO2 yields CH4 + O2.

Ethridge, Edwin C.↗

Development of Primary Volatile Production in COMET C/20O9 Pl (GARRADD) During its 2011-2O12 Apparition

We quantified primary volatiles in comet C/2009 Pl (Garradd) through pre- and post-perihelion observations acquired during its apparition in 2011-12 [1,2,3]. Detected volatiles include H2O, CO, CH4, C2H2, C2H6, HCN, NH3, H2CO, and CH3OH. We present production rates and chemical abundance ratios (relative to water) for all species, and I-D spatial profiles for multiple primary volatiles. We discuss these findings in the context of an emerging taxonomy based on primary volatiles in comets [4]. We used three spectrometer/telescope combinations. On UT 20ll August 7 (Rh 2.4 AU) and September 17-21 (Rh 2.0 AU), we used CRIRES at ESO's Very Large Telescope (VLT) [1]. On September 8 and 9 (Rh 2.1 AU), we used NIRSPEC at Keck-2 and CSHELL at IRTF [2]. Using NIRSPEC on October 13 and 2012 January 08 (Rh 1.83 and 1.57 AU, respectively), we detected nine primary volatiles pre-perihelion, and six post-perihelion [3]. CO was enriched in Garradd while C2H2 was strongly depleted. C2H6 and CH3OH displayed abundances close to those measured for the majority of Oort cloud comets observed to date. The high fractional abundance of CO identifies comet C12009 P1 as a CO-rich comet. Spatial profiles revealed notable differences among individual primary species. Given the relatively large heliocentric distance of C/2009 Pl, we explored the effect of water not being fully sublimated within our field of view and we identi$, the "missing" water fraction needed to reconcile the retrieved abundance ratios with the mean values found for "organics-normal" comets.

Mumma, M. J.↗

Wells for In Situ Extraction of Volatiles from Regolith (WIEVR)

A document discusses WIEVRs, a means to extract water ice more efficiently than previous approaches. This water may exist in subsurface deposits on the Moon, in many NEOs (Near- Earth Objects), and on Mars. The WIEVR approach utilizes heat from the Sun to vaporize subsurface ice; the water (or other volatile) vapor is transported to a surface collection vessel where it is condensed (and collected). The method does not involve mining and extracting regolith before removing the frozen volatiles, so it uses less energy and is less costly than approaches that require mining of regolith. The only drilling required for establishing the WIEVR collection/recovery system is a well-bore drill hole. In its simplest form, the WIEVRs will function without pumps, compressors, or other gas-moving equipment, relying instead on diffusive transport and thermally induced convection of the vaporized volatiles for transport to the collection location(s). These volatile extraction wells could represent a significant advance in extraction efficiency for recovery of frozen volatiles in subsurface deposits on the Moon, Mars, or other extraterrestrial bodies.

Walton, Otis R.↗

Lunar Flashlight: Mapping Lunar Surface Volatiles Using a Cubesat

Water ice and other volatiles may be located in the Moon's polar regions, with sufficient quantities for in situ extraction and utilization by future human and robotic missions. Evidence from orbiting spacecraft and the LCROSS impactor suggests the presence of surface and/or nearsurface volatiles, including water ice. These deposits are of interest to human exploration to understand their potential for use by astronauts. Understanding the composition, quantity, distribution, and form of water/H species and other volatiles associated with lunar cold traps is identified as a NASA Strategic Knowledge Gap (SKG) for Human Exploration. These polar volatile deposits could also reveal important information about the delivery of water to the Earth- Moon system, so are of scientific interest. The scientific exploration of the lunar polar regions was one of the key recommendations of the Planetary Science Decadal Survey. In order to address NASA's SKGs, the Advanced Exploration Systems (AES) program selected three lowcost 6-U CubeSat missions for launch as secondary payloads on the first test flight (EM1) of the Space Launch System (SLS) scheduled for 2017. The Lunar Flashlight mission was selected as one of these missions, specifically to address the SKG associated with lunar volatiles. Development of the Lunar Flashlight CubeSat concept leverages JPL's Interplanetary Nano- Spacecraft Pathfinder In Relevant Environment (INSPIRE) mission, MSFC's intimate knowledge of the Space Launch System and EM-1 mission, small business development of solar sail and electric propulsion hardware, and JPL experience with specialized miniature sensors. The goal of Lunar Flashlight is to determine the presence or absence of exposed water ice and its physical state, and map its concentration at the kilometer scale within the permanently shadowed regions of the lunar south pole. After being ejected in cislunar space by SLS, Lunar Flashlight deploys its solar panels and solar sail and maneuvers into a low-energy transfer to lunar orbit. The solar sail and attitude control system work to bring the satellite into an elliptical polar orbit spiraling down to a perilune of 30-10 km above the south pole for data collection. Lunar Flashlight uses its solar sail to shine reflected sunlight into permanently shadowed regions, measuring surface albedo with a four-filter point spectrometer at 1.1, 1.5 1.9, and 2.0 microns. Water ice will be distinguished from dry regolith from these measurements in two ways: 1) spatial variations in absolute reflectance (water ice is much brighter in the continuum channels), and 2) reflectance ratios between absorption and continuum channels. Derived reflectance and reflectance ratios will be mapped onto the lunar surface in order to distinguish the composition of the PSRs from that of the sunlit terrain. Lunar Flashlight enables a low-cost path to in-situ resource utilization (ISRU) by identifying operationally useful deposits (if there are any), which is a game-changing capability for expanded human exploration.

Cohen, B. A.↗

The Oxygen and Volatile Extraction Node (OVEN) Subsystem for Resource Prospector

The OVEN (Oxygen and Volatile Extraction Node) Subsystem is part of the RESOLVE (Regolith and Environment Science & Oxygen and Lunar Volatile Extraction) Payload, whose main objective is to verify the presence of water and other volatiles on the lunar surface. The RESOLVE payload is scheduled to fly to the moon as part of the Resource Prospector (RP) in 2019. The OVEN Subsystem accepts regolith (soil) and evolves the volatiles contained in the sample by heating the segment to a temperature of at least 150oC for volatile analysis and as high as 900oC for hydrogen reduction. In general, a regolith segment is deposited into a crucible; the crucible is heated and evolved gases flow to a gas analyzer.

Paz, Aaron↗