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Geochronology, or determination of absolute ages for geologic events, underpins many inquiries into the formation and evolution of planets and our Solar System. Absolute ages of ancient and recent magmatic products provide strong constraints on the dynamics of magma oceans and crustal formation, as well as the longevity and evolution of interior heat engines and distinct mantle/crustal source regions. Absolute dating also relates habitability markers to the timescale of evolution of life on Earth. However, the number of geochronologically-significant terrains across the inner Solar System far exceeds our ability to conduct sample return from all of them. In preparation for the upcoming Decadal Survey, our team formulated a set of medium-class (New Frontiers) mission concepts to three different locations (the Moon, Mars, and Vesta) where sites that record Solar System bombardment, magmatism, and/or habitability are uniquely preserved and accessible. We developed a notional payload to directly date planetary surfaces, consisting of two instruments capable of measuring radiometric ages in situ, an imaging spectrometer, optical cameras to provide site geologic context and sample characterization, a trace element analyzer to augment sample contextualization, and a sample acquisition and handling system. Landers carrying this payload to the Moon, Mars, and Vesta would likely fit into the New Frontiers cost cap in our study (~$1B). A mission of this type would provide crucial constraints on planetary history while also enabling a broad suite of investigations such as basic geologic characterization, geomorphologic analysis, ground truth for remote sensing analyses, analyses of major, minor, trace, and volatile elements, atmospheric and other long-lived monitoring, organic molecule analyses, and soil and geotechnical properties., Comment: Submitted to the Planetary Science Journal, October 2020

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.

Currently, the absolute chronology of Martian rocks, deposits and events is based mainly on crater counting and remains highly imprecise with epoch boundary uncertainties in excess of 2 billion years. Answers to key questions concerning the comparative origin and evolution of Mars and Earth will not be forthcoming without a rigid Martian chronology, enabling the construction of a time scale comparable to Earth's. Priorities for exploration include calibration of the cratering rate, dating major volcanic and fluvial events and establishing chronology of the polar layered deposits. If extinct andor extant life is discovered, the chronology of the biosphere will be of paramount importance. Many radiometric and cosmogenic techniques applicable on Earth and the Moon will apply to Mars after certain baselines (e.g. composition of the atmosphere, trace species, chemical and physical characteristics of Martian dust) are established. The high radiation regime may pose a problem for dosimetry-based techniques (e.g. luminescence). The unique isotopic composition of nitrogen in the Martian atmosphere may permit a Mars-specific chronometer for tracing the time-evolution of the atmosphere and of lithic phases with trapped atmospheric gases. Other Mars-specific chronometers include measurement of gas fluxes and accumulation of platinum group elements (PGE) in the regolith. Putting collected samples into geologic context is deemed essential, as is using multiple techniques on multiple samples. If in situ measurements are restricted to a single technique it must be shown to give consistent results on multiple samples, but in all cases, using two or more techniques (e.g. on the same lander) will reduce error. While there is no question that returned samples will yield the best ages, in situ techniques have the potential to be flown on multiple missions providing a larger data set and broader context in which to place the more accurate dates.

Precise measurements of the chemical, elemental, and isotopic composition of planetary surface material and gases, and observed variations in these compositions, can contribute significantly to our knowledge of the source(s), ages, and evolution of solar system materials. The analyses discussed in this paper are mostly made by mass spectrometers or some other type of mass analyzer, and address three broad areas of interest: (1) atmospheric composition - isotopic, elemental, and molecular, (2) gases evolved from solids, and (3) solids. Current isotopic data on nine elements, mostly from in situ analysis, but also from meteorites and telescopic observations are summarized. Potential instruments for isotopic analysis of lunar, Martian, Venusian, Mercury, and Pluto surfaces, along with asteroid, cometary and icy satellites, surfaces are discussed.

Considerable evidence points to a martian origin of the shergottite-nakhlite-chassignite (SNC) meteorites. Noble gas isotopic compositions have been measured in most SNC meteorites. The Xe-129/Xe-132 vs. Kr-84/Xe-132 ratios in Chassigny, most shergottites, and lithology C of EETA 79001 define a linear array. This array is thought to be a mixing line between martian mantle and martian atmosphere. One of the SNC meteorites, Nakhla, contains a leachable component that has an elevated Xe-129/Xe-132 ratio relative to its Kr-84/Xe-132 ratio when compared to this approximately linear array. The leachable component probably consists in part of iddingsite, an alteration product produced by interaction of olivine with aqueous fluid at temperatures lower than 150 C. The elevated Xe isotopic ratio may represent a distinct reservoir in the martian crust or mantle. More plausibly, it is elementally fractionated martian atmosphere. Formation of sediments fractionates the noble gases in the correct direction. The range of sediment/atmosphere fractionation factors is consistent with the elevated Xe-129/Xe-132 component in Nakhla being contained in iddingsite, a low temperature weathering product. The crystallization age of Nakhla is 1.3 Ga. Its low-shock state suggests that it was ejected from near the surface of Mars. As liquid water is required for the formation of iddingsite, these observations provide further evidence for the near surface existence of aqueous fluids on Mars more recently than 1.3 Ga.

Analytical and numerical results presented here suggest that acceleration of photoions by the solar wind motional field is a significant loss process for Xe on asteroids about 200 km in radius or larger, if the Xe is thermalized by its interactions with the surface. For Ar, photoion acceleration can only become important for asteroids nearly 500 km in radius. Thus photoion acceleration, previously invoked for lunar samples, could be responsible for excess fission-produced Xe found associated with solar wind Xe in howarditic meteorites. The lack of such Xe in other types of meteorites may reflect either smaller parent bodies or later times of regolith exposure. Similarly, the failure to observe solar-wind-associated radiogenic Ar-40 in meteorites is consistent with the much smaller likelihood that Ar will be photoionized.

Volatiles implanted into the lunar regolith by the solar wind are potentially important lunar resources. Wittenberg et al. (1986) have proposed that lunar He-3 could be used as a fuel for terrestrial nuclear fusion reactors. They argue that a fusion scheme involving D and He-3 would be cleaner and more efficient than currently-proposed schemes involving D and T. However, since the terrestrial inventory of He-3 is so small, they suggest that the lunar regolith, with concentrations of the order of parts per billion (by mass) would be an economical source of He-3. Solar-wind implantation is also the primary source of H, C, and N in lunar soil. These elements could also be important, particularly for life support and for propellant production. In a SERC study of the feasibility of obtaining the necessary amount of He-3, Swindle et al. (1990) concluded that the available amount is sufficient for early reactors, at least, but that the mining problems, while not necessarily insurmountable, are prodigious. The volatiles H, C, and N, on the other hand, come in parts per million level abundances. The differences in abundances mean that (1) a comparable amount of H, C, and/or N could be extracted with orders of magnitude smaller operations than required for He-3, and (2) if He-3 extraction ever becomes important, huge quantities of H, C, and N will be produced as by-products.

Argon and Xe in the Martian atmosphere are radiogenic relative to the Martian mantle if the SNC meteorites are from Mars. Decay of the short lived isotope I-129 to Xe-129 (t sub 1/2 = 16 m.y.) is the most plausible source of the radiogenic Xe. This short half life constrains any process responsible for the elevated Xe-129/Xe-132 ratio of the Martian atmosphere to occur very early in solar system history. Musselwhite et al. proposed that the differential solubility of I and Xe in liquid water played a key role in producing the radiogenic signature in the Martian atmosphere. Here we explore an alternative hypothesis involving purely igneous processes, and motivated in part by new experimental results on the partitioning of I and Xe between minerals and melt.

The Martian atmosphere has a high X-129/Xe-132 ratio compared to the Martian mantle. As Xe-129 is the daughter product of the extinct nuclide I-129, a means of fractionating iodine from xenon early in Martian history appears necessary to account for the X-129/Xe-132 ratios of its known reservoirs. A model is presented here to account for the Marian xenon data which relies on the very different solubilities of xenon and iodine in water to fractionate them after outgassing. Atmospheric xenon is lost by impact erosion during heavy bombardment, followed by release of Xe-129 produced from I-129 decay in the crust.

The trapped noble gases in meteorites come in two main varieties, usually referred to as solar and planetary. The solar noble gases are implanted solar-wind or solar-flare materials, and thus their relative elemental abundances provide a good estimate of those of the sun. The planetary noble gases have relative elemental abundances similar to those in the terrestrial atmosphere, but there are also important distinctions. At least one other elemental pattern (subsolar) and several isotopic patterns have also been identified.