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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↗

Volatile Concentrations and H-Isotope Composition of Unequilibrated Eucrites

Eucrites are among the oldest and best studied asteroidal basalts (1). They represent magmatism that occurred on their parent asteroid, likely 4-Vesta, starting at ~ 4563 Ma and continuing for approx. 30 Myr. Two hypotheses are debated for the genesis of eucrites, a magma ocean model (2), and a mantle partial melting model. In general, volatiles (H, C, F, Cl) have been ignored for eucrites and 4-Vesta, but solubility of wt% levels of H2O are possible at Vestan interior PT conditions. Targeted measurements on samples could aid our understanding considerably. Recent studies have found evidence of volatile elements in eucrites, but quantifying the abundance of volatiles remains problematic (6). Volatile elements have a disproportionately large effect on melt properties and phase stability, relative to their low abundance. The source of volatile elements can be elucidated by examining the hydrogen isotope ratio (D/H), as different H reservoirs have drastically different H isotope compositions. Recent studies of apatite in eucrites have shown that the D/H of 4-Vesta matches that of Earth and carbonaceous chondrites, however, the D/H of apatites may not represent the D/H of a primitive 4-Vesta melt due to the possibility of degassing prior to the crystallization of apatite. Therefore, the D/H of early crystallizing phases must be measured to determine if the D/H of 4-Vesta is equal to that of the Earth and carbonaceous chondrites.

Sarafian, Adam R.↗

Overview of Primitive Object Volatile Explorer (PrOVE) CubeSat or Smallsat Concept

Here we describe the Primitive Object Volatile Explorer (PrOVE), a smallsat mission concept to study the surface structure and volatile inventory of comets in their perihelion passage phase when volatile activity is near peak. CubeSat infrastructure imposes limits on propulsion systems, which are compounded by sensitivity to the spacecraft disposal state from the launch platform and potential launch delays. We propose circumventing launch platform complications by using waypoints in space to park a deep space SmallSat or CubeSat while awaiting the opportunity to enter a trajectory to flyby a suitable target. In our Planetary Science Deep Space SmallSat Studies (PSDS3) project, we investigated scientific goals, waypoint options, potential concept of operations (ConOps) for periodic and new comets, spacecraft bus infrastructure requirements, launch platforms, and mission operations and phases. Our payload would include two low-risk instruments: a visible image (VisCAM) for 5-10 m resolution surface maps; and a highly versatile multispectral Comet CAMera (ComCAM) will measure 1) H2O, CO2, CO, and organics non-thermal fluorescence signatures in the 2-5 μm MWIR, and 2) 7-10 and 8-14 μm thermal (LWIR) emission. This payload would return unique data not obtainable from ground-based telescopes and complement data from Earth-orbiting observatories. Thus, the PrOVE mission would (1) acquire visible surface maps, (2) investigate chemical heterogeneity of a comet nucleus by quantifying volatile species abundance and changes with solar insolation, (3) map the spatial distribution of volatiles and determine any variations, and (4) determine the frequency and distribution of outbursts.

Clark, Pamela S.↗

First Results from the Mojave Volatiles Prospector (MVP) Field Campaign, a Lunar Polar Rover Mission Analog

The Mojave Volatiles Prospector (MVP) project is a science-driven field program with the goal to produce critical knowledge for conducting robotic exploration of the Moon. MVP will feed science, payload, and operational lessons learned to the development of a real-time, short-duration lunar polar volatiles prospecting mission. MVP achieves these goals through a simulated lunar rover mission to investigate the composition and distribution of surface and subsurface volatiles in a natural and a priori unknown environment within the Mojave Desert, improving our understanding of how to find, characterize, and access volatiles on the Moon. The MVP field site is the Mojave Desert, selected for its low, naturally occurring water abundance. The Mojave typically has on the order of 2-6% water, making it a suitable lunar analog for this field test. MVP uses the Near Infrared and Visible Spectrometer Subsystem (NIRVSS), Neutron Spectrometer Subsystem (NSS), and a downward facing GroundCam camera on the KREX-2 rover to investigate the relationship between the distribution of volatiles and soil crust variation. Through this investigation, we mature robotic in situ instruments and concepts of instrument operations, improve ground software tools for real time science, and carry out publishable research on the water cycle and its connection to geomorphology and mineralogy in desert environments. A lunar polar rover mission is unlike prior space missions and requires a new concept of operations. The rover must navigate 3-5 km of terrain and examine multiple sites in in just ~6 days. Operational decisions must be made in real time, requiring constant situational awareness, data analysis and rapid turnaround decision support tools. This presentation will focus on the first science results and operational architecture findings from the MVP field deployment relevant to a lunar polar rover mission.

Heldmann, Jennifer L.↗

VIPER – Volatiles Investigating Polar Exploration Rover: Mission Overview

VIPER is a low cost, lunar volatiles detection and measurement mission that will be delivered to the lunar south pole by one of NASA’s Commercial Lunar Payload Services partners and will characterize the nature of the volatiles in the area and extrapolate this data to create global lunar water resource maps. It will be the first mining expedition on another world while simultaneously addressing fundamental planetary science questions. Prospecting for lunar water at the poles is the next step in understanding the resource potential and addressing key theories about water emplacement and retention. It now appears that potentially economically significant amounts of water ice exists at the poles of the Moon, however, the distribution of this water is still not understood at a level sufficient to fully evaluate economic models. The water ice (and other potential volatiles), the “ore body”, needs to be understood at the scales of 10s to 100s of meters to evaluate localization, extraction and processing techniques. To accomplish this, VIPER will survey permanently-shadowed regions, semi-permanent shadowed regions, and even semi and full sunlit areas in order to have a comprehensive survey of polar region volatiles, to best inform future mission architectures. In order to characterize the volatiles, a payload suite consisting of a neutron spectrometer, mass spectrometer, near infrared spectrometer and a 1-meter drill will be hosted on the VIPER mobile lunar rover platform. Since VIPER is a relatively low cost, schedule-constrained, risk-tolerant mission, there are architectural limitations that require unique mission planning constraints to enable exploration of the lunar south pole region. These regions offer unique challenges such as uncertain terrain conditions, rock and crater hazards, lunar dust, multipath communications effects, extreme thermal environments and multiple overlapping planning constraints. Mission design/traverse planning, system design capabilities and mission operations are all highly linked through initial development phases. We will describe the current mission overview and the unique approaches taken by the VIPER project based on our programmatic framework and unique mission environment.

VIPER↗

Lunar Near-Surface Volatile Sample Return

The origin, distribution, depth and volume of lunar volatiles remain open questions. One of the possible sources of Moon's volatiles is their volcanic outgassing during the peak of lunar volcanic activity ~3.5 Ga. This same outgassing would also produce a tenuous transient atmosphere which would promote the delivery of volatiles from the volcanic sources to the polar cold traps. Though such an atmosphere could have played an important role in the evolution of the Moon, little is known about it due to high uncertainty level in the mechanisms involved. The only reliable proxy for the ancient lunar atmosphere are the primordial volatiles deposited by it, which are expected to be preserved in the polar cold traps, and could be studied through sample return. In this white paper we therefore advocate that a volatile sample return from the Moon's polar cold traps should be a fundamental part of the Artemis program.

Instrumentation and Methods for Astrophysics↗

Overview of Primitive Volatile Explorer (PrOVE) Cubesat or Smallsat Concept

Here we describe the Primitive Object Volatile Explorer (PrOVE), a smallsat mission concept to study the surface structure and volatile inventory of comets in their perihelion passage phase when volatile activity is near peak. CubeSat infrastructure imposes limits on propulsion systems, which are compounded by sensitivity to the spacecraft disposal state from the launch platform and potential launch delays. We propose circumventing launch platform complications by using waypoints in space to park a deep space SmallSat or CubeSat while awaiting the opportunity to enter a trajectory to flyby a suitable target. In our Planetary Science Deep Space SmallSat Studies (PSDS3) project, we investigated scientific goals, waypoint options, potential concept of operations (ConOps) for periodic and new comets, spacecraft bus infrastructure requirements, launch platforms, and mission operations and phases. Our payload would include two low-risk instruments: a visible image (VisCAM) for 5-10 m resolution surface maps; and a highly versatile multispectral Comet CAMera (ComCAM) will measure 1) H2O, CO2, CO, and organics non-thermal fluorescence signatures in the 2-5 µm MWIR, and 2) 7-10 and 8-14 µm thermal (LWIR) emission. This payload would return unique data not obtainable from ground-based telescopes and complement data from Earth-orbiting observatories. Thus, the PrOVE mission would (1) acquire visible surface maps, (2) investigate chemical heterogeneity of a comet nucleus by quantifying volatile species abundance and changes with solar insolation, (3) map the spatial distribution of volatiles and determine any variations, and (4) determine the frequency and distribution of outbursts.

Zucherman, Aaron↗

First Comet Observations with NIRSPEC-2 at Keck: Outgassing Sources of Parent Volatiles and Abundances Based on Alternative Taxonomic Compositional Baselines in 46P/Wirtanen

A major upgrade to the NIRSPEC instrument at the Keck II telescope was successfully completed in time for near-infrared spectroscopic observations of comet 46P/Wirtanen during its exceptionally close flyby of Earth in 2018 December. These studies determined the abundances of several volatiles, including C2H2, C2H6, CH3OH, NH3, HCN, H2CO, and H2O. Long-slit spatial distributions of gas rotational temperature and column density are diagnostic for the presence of icy grains in the coma and understanding if different volatiles are associated with common or distinct outgassing sources. These spatial distributions suggest that C2H2, C2H6, and HCN have a common outgassing source, whereas H2O and CH3OH have additional, more extended sources. The synergy of these findings with observations by space missions (Rosetta and EPOXI) motivates continuing studies to address whether or not C2H6, C2H2, and HCN have a common source of release (plausibly associated with CO2) in a larger sample of comets and whether systematic differences exist in the release of these species compared to H2O and CH3OH. Abundances of volatiles are reported relative to H2O, as traditionally done, as well as C2H6. While not unique, the choice of C2H6 demonstrates the value of extending the chemical taxonomy of parent volatiles in comets toward additional compositional "baselines" and, importantly, closer integration between coma abundances and the underlying volatile associations as revealed by spatial distributions. Our findings on composition and sources of outgassing include information relevant to future evaluations of 46P/Wirtanen as a prospective spacecraft target.

Boncho P. Bonev↗

From Source to Surface: An Investigation of Magmatic Lunar Volatiles

Lunar missions led by NASA discovered water ice on the Moon’s surface [1-3], revolutionizing views of the abundance, distribution, and potential sources of H2O and other volatiles. Volatiles play an important role in affecting the rheological properties of minerals and melts and influencing magma eruption processes. In order to determine the indigenous volatile inventory of the Moon, it is vital to identify the magmatic and secondary processes that may have affected the volatile contents in lunar minerals [4]. As part of the Apollo Next Generation Sample Analysis (ANGSA) program we are investigating the petrogenesis of a set of four Apollo lunar basalts collected from the rim of Steno Crater 71035, 71037, 71055, and specially curated sample 71036. Our team is studying the petrology in 2D and 3D (this work), chronology (Pomeroy et al., LPSC 2022), oxidation state of sulfur in apatite (Brounce et al., LPSC 2022), and volatile inventory of the sample set in order to understand the age and genetic relationships among the basalts, their magma ascent conditions and eruptive signatures, and their degassing and surface histories. Here we present the first detailed study of the 2D and 3D mineralogy, textures, 3D vesiculation, and chemistry of these basalts to shed light on their magmatic, volcanic, and post-eruptive histories. Note: Extended abstract on document.

Z. E. Wilbur↗

Constraining the Thermal and Textural Evolution of Evolved Achondrite DOM 10100: Implications for Volatile Loss

Identification of evolved achrondritic clasts suggests that some early planetesimals experienced extensive differentiation and formed chemically evolved crusts. Many of these samples contain volatile-bearing phases (i.e., apatite, merrillite, nominally anhydrous minerals), which can be used to constrain volatile budgets and abundancies via in-situ measurements. These ancient crustal rocks are subject to high heat, moderate pressures, potentially hot mineral-rich fluids, and degassing that has likely modified many of these volatiles, and their abundancies do not represent the composition of the primary magma from which these achondrites formed. In this work we attempt to deconvolve the thermal evolution of these samples to provide petrologic information that can be used for making inferences regarding their volatile history, and ultimately constraining volatile budgets on planetary bodies in the early Solar System. Here, we combine in-situ major element geochemistry, thermodynamic modeling, and detailed textural and microstructural observations to reconstruct the thermal and textural evolution of howardite DOM 10100, which contains a dacite within its matrix. Previous analyses of several sections of DOM 10100 suggest that the dacitic clast is evidence for partial melting of Vesta’s differentiated basaltic crust, making it an ideal candidate for evolved crustal studies. While its igneous petrogenesis has been well constrained, there is still opportunity to better characterize its post-crystallization thermal history, including possible thermal metamorphism and cooling.

J S Gorce↗

Surrogate-assisted optimization under uncertainty for design for remanufacturing considering material price volatility

Remanufacturing is a well-established end-of-life (EOL) strategy that promises significant savings in energy and carbon emissions. However, the current design practices are not remanufacturing-inclusive, i.e., the majority of products are designed for a single life cycle. As a result, potential products that can sustain multiple life cycles are deprived of additional benefits of being designed for remanufacturing, such as reduced material usage, lower cost, and improved environmental impact. Moreover, the uncertainty in design, material selection, and economics are not considered to produce remanufacturable designs. Accordingly, this research proposes a design for remanufacturing (DfRem) framework that accounts for design uncertainty and material price volatility. The framework systematically explores the design space, performs design optimization under uncertainty, followed by topology optimization to provide additional mass savings, and finally, a price volatility analysis for plausible design material choices. The candidate designs are evaluated based on their design mass, material price volatility, failure mode characteristics, carbon footprint, and embodied energy impacts. The proposed framework's utility is demonstrated via the use of an engine cylinder head case study subjected to thermo-mechanical loads along with fatigue and wear failure. Considering grey cast iron and aluminum alloy as the design material choices, it was found that the cast iron design reduced the initial design mass by 6% as opposed to a 5% decrease for aluminum. On the other hand, about 8% area of the cast iron design failed due to fatigue, compared to 3% for aluminum. Here, we further observed that although the aluminum design provided better mechanical performance than the cast iron design, this material was more expensive and volatile in price.

36 MATERIALS SCIENCE↗