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The Perseverance rover is meant to collect samples of the martian surface for eventual return to Earth. The headspace gas present over the solid samples within the sample tubes will be of significant scientific interest for what it reveals about the interactions of the solid samples with the trapped atmosphere and for what it will reveal about the martian atmosphere itself. However, establishing the composition of the martian atmosphere will require other dedicated samples. The headspace gas as the sole atmospheric sample is problematic for many reasons. The quantity of gas present within the sample tube volume is insufficient for many investigations, and there will be exchange between solid samples, headspace gas, and tube walls. Importantly, the sample tube materials and preparation were not designed for optimal Mars atmospheric gas collection and storage as they were not sent to Mars in a degassed evacuated state and have been exposed to both Earth's and Mars' atmospheres. Additionally, there is a risk of unconstrained seal leakage in transit back to Earth, which would allow fractionation of the sample (leak-out) and contamination (leak-in). The science return can be improved significantly (and, in some cases, dramatically) by adding one or more of several strategies listed here in increasing order of effectiveness and difficulty of implementation: (1) Having Perseverance collect a gas sample in an empty sample tube, (2) Collecting gas in a newly-designed, valved, sample-tube-sized vessel that is flown on either the Sample Fetch Rover (SFR) or the Sample Retrieval Lander (SRL), (3) Adding a larger (50-100 cc) dedicated gas sampling volume to the Orbiting Sample container (OS), (4) Adding a larger (50-100 cc) dedicated gas sampling volume to the OS that can be filled with compressed martian atmosphere. [ABSTRACT FROM AUTHOR]

Samples returned from Mars would be placed under quarantine at a Sample Receiving Facility (SRF) until they are considered safe to release to other laboratories for further study. The process of determining whether samples are safe for release, which may involve detailed analysis and/or sterilization, is expected to take several months. However, the process of breaking the sample tube seal and extracting the headspace gas will perturb local equilibrium conditions between gas and rock and set in motion irreversible processes that proceed as a function of time. Unless these time-sensitive processes are understood, planned for, and/or monitored during the quarantine period, scientific information expected from further analysis may be lost forever. At least four processes underpin the time-sensitivity of Mars returned sample science: (1) degradation of organic material of potential biological origin, (2) modification of sample headspace gas composition, (3) mineral-volatile exchange, and (4) oxidation/reduction of redox-sensitive materials. Available constraints on the timescales associated with these processes supports the conclusion that an SRF must have the capability to characterize attributes such as sample tube headspace gas composition, organic material of potential biological origin, as well as volatiles and their solid-phase hosts. Because most time-sensitive investigations are also sensitive to sterilization, these must be completed inside the SRF and on timescales of several months or less. To that end, we detail recommendations for how sample preparation and analysis could complete these investigations as efficiently as possible within an SRF. Finally, because constraints on characteristic timescales that define time-sensitivity for some processes are uncertain, future work should focus on: (1) quantifying the timescales of volatile exchange for core material physically and mineralogically similar to samples expected to be returned from Mars, and (2) identifying and developing stabilization or temporary storage strategies that mitigate volatile exchange until analysis can be completed. Executive Summary Any samples returned from Mars would be placed under quarantine at a Sample Receiving Facility (SRF) until it can be determined that they are safe to release to other laboratories for further study. The process of determining whether samples are safe for release, which may involve detailed analysis and/or sterilization, is expected to take several months. However, the process of breaking the sample tube seal and extracting the headspace gas would perturb local equilibrium conditions between gas and rock and set in motion irreversible processes that proceed as a function of time. Unless these processes are understood, planned for, and/or monitored during the quarantine period, scientific information expected from further analysis may be lost forever . Specialist members of the Mars Sample Return Planning Group Phase 2 (MSPG-2), referred to here as the Time-Sensitive Focus Group, have identified four processes that underpin the time-sensitivity of Mars returned sample science: (1) degradation of organic material of potential biological origin, (2) modification of sample headspace gas composition, (3) mineral-volatile exchange, and (4) oxidation/reduction of redox-sensitive materials (Figure 2). Consideration of the timescales and the degree to which these processes jeopardize scientific investigations of returned samples supports the conclusion that an SRF must have the capability to characterize: (1) sample tube headspace gas composition, (2) organic material of potential biological origin, (3) volatiles bound to or within minerals, and (4) minerals or other solids that host volatiles (Table 4). Most of the investigations classified as time-sensitive in this report are also sensitive to sterilization by either heat treatment and/or gamma irradiation (Velbel et al., 2022). Therefore, these investigations must be completed inside biocontainment and on timescales that minimize the irrecoverable loss of scientific information (i.e., several months or less; Section 5) . To that end, the Time-Sensitive Focus Group has outlined a number of specific recommendations for sample preparation and instrumentation in order to complete these investigations as efficiently as possible within an SRF (Table 5). Constraints on the characteristic timescales that define time-sensitivity for different processes can range from relatively coarse to uncertain (Section 4). Thus, future work should focus on: (1) quantifying the timescales of volatile exchange for variably lithified core material physically and mineralogically similar to samples expected to be returned from Mars, and (2) identifying and developing stabilization strategies or temporary storage strategies that mitigate volatile exchange until analysis can be completed. List of Findings FINDING T-1: Aqueous phases, and oxidants liberated by exposure of the sample to aqueous phases, mediate and accelerate the degradation of critically important but sensitive organic compounds such as DNA. FINDING T-2: Warming samples increases reaction rates and destroys compounds making biological studies much more time-sensitive. MAJOR FINDING T-3: Given the potential for rapid degradation of biomolecules, (especially in the presence of aqueous phases and/or reactive O-containing compounds) Sample Safety Assessment Protocol (SSAP) and parallel biological analysis are time sensitive and must be carried out as soon as possible. FINDING T-4: If molecules or whole cells from either extant or extinct organisms have persisted under present-day martian conditions in the samples, then it follows that preserving sample aliquots under those same conditions ( i.e., 6 mbar total pressure in a dominantly CO 2 atmosphere and at an average temperature of -80 ° C) in a small isolation chamber is likely to allow for their continued persistence. FINDING T-5: Volatile compounds ( e.g., HCN and formaldehyde) have been lost from Solar System materials stored under standard curation conditions. FINDING T-6: Reactive O-containing species have been identified in situ at the martian surface and so may be present in rock or regolith samples returned from Mars. These species rapidly degrade organic molecules and react more rapidly as temperature and humidity increase. FINDING T-7: Because the sample tubes would not be closed with perfect seals and because, after arrival on Earth, there will be a large pressure gradient across that seal such that the probability of contamination of the tube interiors by terrestrial gases increases with time, the as-received sample tubes are considered a poor choice for long-term gas sample storage. This is an important element of time sensitivity. MAJOR FINDING T-8: To determine how volatiles may have been exchanged with headspace gas during transit to Earth, the composition of martian atmosphere (in a separately sealed reservoir and/or extracted from the witness tubes), sample headspace gas composition, temperature/time history of the samples, and mineral composition (including mineral-bound volatiles) must all be quantified. When the sample tube seal is breached, mineral-bound volatile loss to the curation atmosphere jeopardizes robust determination of volatile exchange history between mineral and headspace. FINDING T-9: Previous experiments with mineral powders show that sulfate minerals are susceptible to H 2 O loss over timescales of hours to days. In addition to volatile loss, these processes are accompanied by mineralogical transformation. Thus, investigations targeting these minerals should be considered time-sensitive. FINDING T-10: Sulfate minerals may be stabilized by storage under fixed relative-humidity conditions, but only if the identity of the sulfate phase(s) is known a priori . In addition, other methods such as freezing may also stabilize these minerals against volatile loss. FINDING T-11: Hydrous perchlorate salts are likely to undergo phase transitions and volatile exchange with ambient surroundings in hours to days under temperature and relative humidity ranges typical of laboratory environments. However, the exact timescale over which these processes occur is likely a function of grain size, lithification, and/or cementation. FINDING T-12: Nanocrystalline or X-ray amorphous materials are typically stabilized by high proportions of surface adsorbed H 2 O. Because this surface adsorbed H 2 O is weakly bound compared to bulk materials, nanocrystalline materials are likely to undergo irreversible ripening reactions in response to volatile loss, which in turn results in decreases in specific surface area and increases in crystallinity. These reactions are expected to occur over the timescale of weeks to months under curation conditions. Therefore, the crystallinity and specific surface area of nanocrystalline materials should be characterized and monitored within a few months of opening the sample tubes. These are considered time-sensitive measurements that must be made as soon as possible. FINDING T-13: Volcanic and impact glasses, as well as opal-CT, are metastable in air and susceptible to alteration and volatile exchange with other solid phases and ambient headspace. However, available constraints indicate that these reactions are expected to proceed slowly under typical laboratory conditions ( i.e., several years) and so analyses targeting these materials are not considered time sensitive. FINDING T-14: Surface adsorbed and interlayer-bound H 2 O in clay minerals is susceptible to exchange with ambient surroundings at timescales of hours to days, although the timescale may be modified depending on the degree of lithification or cementation. Even though structural properties of clay minerals remain unaffected during this process (with the exception of the interlayer spacing), investigations targeting H 2 O or other volatiles bound on or within clay minerals should be considered time sensitive upon opening the sample tube. FINDING T-15: Hydrated Mg-carbonates are susceptible to volatile loss and recrystallization and transformation over timespans of months or longer, though this timescale may be modified by the degree of lithification and cementation. Investigations targeting hydrated carbonate minerals (either the volatiles they host or their bulk mineralogical properties) should be considered time sensitive upon opening the sample tube. MAJOR FINDING T-16: Current understanding of mineral-volatile exchange rates and processes is largely derived from monomineralic experiments and systems with high surface area; lithified sedimentary rocks (accounting for some, but not all, of the samples in the cache) will behave differently in this regard and are likely to be associated with longer time constants controlled in part by grain boundary diffusion. Although insufficient information is available to quantify this at the present time, the timescale of mineral-volatile exchange in lithified samples is likely to overlap with the sample processing and curation workflow ( i.e., 1-10 months; Table 4). This underscores the need to prioritize measurements targeting mineral-hosted volatiles within biocontainment. FINDING T-17: The liberation of reactive O-species through sample treatment or processing involving H 2 O ( e.g., rinsing, solvent extraction, particle size separation in aqueous solution, or other chemical extraction or preparation protocols) is likely to result in oxidation of some component of redox-sensitive materials in a matter of hours. The presence of reactive O-species should be examined before sample processing steps that seek to preserve or target redox-sensitive minerals. Electron paramagnetic resonance spectroscopy (EPR) is one example of an effective analytical method capable of detecting and characterizing the presence of reactive O-species. FINDING T-18: Environments that maintain anoxia under inert gas containing <<1 ppm O 2 are likely to stabilize redox-sensitive minerals over timescales of several years. MAJOR FINDING T-19: MSR investigations targeting organic macromolecular or cellular material, mineral-bound volatile compounds, redox sensitive minerals, and/or hydrous carbonate minerals can become compromised at the timescale of weeks (after opening the sample tube), and scientific information may be completely lost within a time timescale of a few months. Because current considerations indicate that completion of SSAP, sample sterilization, and distribution to investigator laboratories cannot be completed in this time, these investigations must be completed within the Sample Receiving Facility as soon as possible.