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Isotopic constraints on the origin of meteoritic organic matter

Salient features of the isotopic distribution of H, C and N in the organic material found in carbonaceous meteorites are noted. Most organic fractions are strongly enriched in D with respect to the D/H ratio characteristic of H2 in the protosolar system; substantial variations in C-13/C-12 ratio are found among different molecular species, with oxidised species tending to be C-13 enriched relative to reduced species; some homologous series reveal systematic decrease in C-13/C-12 with increasing C number; considerable variation in N-15/N-14 ratio is observed within organic matter, though no systematic pattern to its distribution has yet emerged; no interelement correlations have been observed between isotope enrichments for the different biogenic elements. The isotopic complexity echoes the molecular diversity observed in meteoritic organic matter and suggests that the organic matter was formed by multiple processes and/or from multiple sources. However, existence of a few systematic patterns points towards survival of isotopic signatures characteristic of one or more specific processes. The widespread D enrichment implies either survival of many species of interstellar molecule or synthesis from a reservoir containing a significant interstellar component. Several of the questions raised above can be addressed by more detailed determination of the distribution of the H, C and N isotopes among different well-characterized molecular fractions. Thus, the present study is aimed at discovering whether the different amino acids have comparable D enrichments, which would imply local synthesis from a D-enriched reservoir, or very viable D enrichments, which would imply survival of some interstellar amino acids. The same approach is also being applied to polycyclic aromatic hydrocarbons. Because the analytical technique employed (secondary ion mass spectrometry) can acquire data for all three isotopic systems from each molecular fraction, any presently obscured interelement isotopic correlation should also be revealed, which will aid in identifying pertinent synthetic processes.

Kerridge, J. F.↗

SNC Meteorites, Organic Matter and a New Look at Viking

Recently, evidence has begun to grow supporting the possibility that the Viking GC-MS would not have detected certain carboxylate salts that could have been present as metastable oxidation products of high molecular weight organic species. Additionally, despite the instrument's high sensitivity, the possibility had remained that very low levels of organic matter, below the instrument's detection limit, could have been present. In fact, a recent study indicates that the degradation products of several million microorganisms per gram of soil on Mars would not have been detected by the Viking GC-MS. Since the strength of the GC-MS findings was considered enough to dismiss the biology packet, particularly the LR results, any subsequent evidence suggesting that organic molecules may in fact be present on the Martian surface necessitates a re-evaluation of the Viking LR data. In addition to an advanced mass spectrometer to look for isotopic signatures of biogenic processes, future lander missions will include the ability to detect methane produced by methanogenic bacteria, as well as techniques based on biotechnology. Meanwhile, the identification of Mars samples already present on Earth in the form of the SNC meteorites has provided us with the ability to study samples of the Martian upper crust a decade or more in advance of any planned sample return missions. While contamination issues are of serious concern, the presence of indigenous organic matter in the form of polycyclic aromatic hydrocarbons has been detected in the Martian meteorites ALH84001 and Nakhla, while there is circumstantial evidence for carbonaceous material in Chassigny. The radiochronological ages of these meteorites are 4.5 Ga, 1.3 Ga, and 165 Ma respectively representing a span of time in Earth history from the earliest single-celled organisms to the present day. Given this perspective on organic material, a biological interpretation to the Viking LR results can no longer be ruled out. In the LR experiment, a solution containing C-14 labeled organic compounds was injected into soil samples. The detection of radioactivity in the overhead space would indicate that one or more of the substrates had been chemically converted into a carbon-containing gas. To serve as a control, some samples were heated enough to destroy most known terrestrial microbes so that an indication for life would be a positive response from unheated samples and a negative response from heated samples. On Mars, the LR results had met minimum criteria for a biological interpretation but due to the GC-MS results, the LR responses were later attributed to putative soil inorganic oxidants. Since the time of Viking, studies have been carried out with the objective of determining an oxidant or combination of oxidants that might exist on Mars and have produced the observed kinetics of the LR response. To date, no such agent has been found that produces all aspects of the LR results on Mars. While the above considerations in no way imply the existence of life forms at the two Viking landing sites, inorganic and biological explanations for the Viking LR data should now be considered equally plausible until more complete studies of the Martian surface are carried out. Therefore, in light of the SNC meteorites data and their implications for the possibility of organic matter near or on the Martian surface the Viking biology experiments should thus be seen, not as failures for their inability to provide unambiguous evidence for or against Martian life, but as a foundation for the development of future life-detection instruments. Additional information is contained in the original extended abstract.

Warmflash, David M.↗

In-Situ XRD/XRF to Support Life Detection on Mars

X-ray diffraction / X-ray fluorescence (XRD/XRF) analysis provides the most comprehensive mineralogical / compositional characterization of rocks and soils of any flight-capable technique. XRD data provide quantitative mineralogy (including abundance of X-ray amorphous materials) and crystal chemistry (structure, elemental composition and valence state), and XRF data provide complimentary major, minor, and some trace element abundances. Both types of data are important in evaluating habitability (environment of formation) and biosignature preservation/degradation (post-depositional diagenetic change). Whether or not a relict biosignature is detected, the mineral assemblage and its geochemistry can be used to determine the habitability of an ancient environment (e.g., salinity, pH, temperature), and to identify potential sources of energy for life (e.g., elements in different redox states). In this respect, a null result (a habitable environment lacking evidence of life) can play an important role in constraining the parameters of the search. Conversely, diagenetic alteration (taphonomic change) resulting from post-depositional variations in temperature, pressure or fluid chemistry can preserve evidence of biogenicity, erase such evidence completely or indeed can provide for post-depositional habitable conditions in the subsurface. XRD / XRF data are critical to these determinations. The CheMin instrument on the Mars Science Laboratory (MSL) Curiosity rover is the first XRD instrument flown in space. CheMin operates in transmission geometry with a Co X-ray source to minimize fluorescence from iron. Diffracted photons are collected with an energy-sensitive charge-coupled device (CCD). The position of the diffracted photons provides structural information for minerals, whereas the energy of sample-generated X-ray fluorescence photons provides elemental information, though these XRF data are qualitative. Mineralogical data from the CheMin XRD identified the three circumstances above: habitable depositional environments (e.g., Yellowknife Bay), habitable subsurface/diagenetic environments (e.g., throughout the Murray formation), and diagenetic conditions that may destroy evidence of habitability (e.g., oxidative and acidic environments at Vera Rubin ridge). Technological advances in X-ray technology and lessons learned from the operation of CheMin on Mars have resulted in a next-generation XRD/XRF, called CheMinX. Replacement of CheMin’s CCD with an array of hybrid pixel detectors and improvements in focusing optics dramatically decrease analysis time (15 minutes vs. 22 hours for MSL-CheMin) and result in a better angular resolution (0.18 vs. 0.30 °2θ for MSL-CheMin). This increased resolution improves mineral detection, including discrimination between types of pyroxenes, which is not possible with MSL-CheMin data. The hybrid pixel detectors do not require cooling like the MSL-CheMin CCD, therefore reducing the power needed to operate CheMinX. CheMinX has a silicon-drift detector (SDD) to measure fluoresced photons, enabling the quantification of major, minor, and some trace elements via XRF. XRD/XRF data are collected simultaneously in CheMinX, obviating the need for multiple compositional instruments. The CheMinX design also improves upon MSL-CheMin’s sample handling. Instead of sample cells on wheel, which are often not reusable and add complexity in commanding the instrument, CheMinX has single-use cells in a cartridge/dispenser configuration. Because of these improvements, CheMinX is an ideal instrument for Discovery-class life-detection missions, including Mars Life Explorer that was recommended for development in the Planetary Science and Astrobiology Decadal Survey 2023-2032.

E B Rampe↗

Mineralogical and Geochemical Analyses of Antarctic Lake Sediments: A Reflectance and Moessbauer Spectroscopy Study with Applications for Remote Sensing on Mars

Lakebottom sediments from the Dry Valleys region of Antarctica have been analyzed here in order to study the influence of water chemistry on the mineralogy and geochemistry of these sediments, as well as to evaluate techniques for remote spectral identification of potential biomarker minerals on Mars. Lakes from the Dry Valleys region of Antarctica have been investigated as possible analogs for extinct lake environments on early Mars. Sediment cores were collected in the present study from perennially ice-covered Lake Hoare in the Taylor Valley. These sediments were taken from a core in an oxic region of the lake and another core in an anoxic zone. Differences between the two cores were observed in the sediment color, Fe(II)/Fe(III) ratio, the presence of pyrite, the abundance of Fe, S and some trace elements, and the C, N and S isotope fractionation patterns. The results of visible-infrared reflectance spectroscopy (0.3-25 microns) Mossbauer spectroscopy (77 and 4 K) and X-ray diffraction are combined to determine the mineralogy and composition of these samples. The sediments are dominated by plagioclase, K-feldspar, quartz and pyroxene. Algal mats grow on the bottom of the lake and organic material has been found throughout the cores. Calcite is abundant in some layers of the aerobic core (shallow region) and pyrite is abundant in some layers of the anaerobic core (deep region). Analysis of the spectroscopic features due to organics and carbonates with respect to the abundance of organic C and carbonate contents was performed in order to select optimal spectral bands for remote identification of these components in planetary regoliths. Carbonate bands near 4 and 6.8 microns (approx.2500 and 1500/cm) were detected for carbonate abundances as low as 0.1 wt.% CO2. Organic features at 3.38, 3.42 and 3.51 microns (2960, 2925 and 2850/cm) were detected for organic C abundances as low as 0.06 wt.% C. The d13C trends show a more complex organic history for the anaerobic sediments than for the aerobic sediments. The biogenic pyrite found in the anaerobic core is associated with lighter d34S values and high organic C levels and could be used as a biomarker mineral for paleolakes on Mars.

Froeschl, Heinz↗

LDEF post-retrieval evaluation of exobiology interests

Cursory examination of the Long Duration Exposure Facility (LDEF) shows the existence of thousands of impact craters of which less than 1/3 exceed 0.3 mm in diameter; the largest crater is 5.5 mm. Few craters show oblique impact morphology and, surprisingly, only a low number of craters have recognizable impact debris. Study of this debris could be of interest to exobiology in terms of C content and carbonaceous materials. All craters greater that 0.3 mm have been imaged and recorded into a data base by the preliminary examination team. Various portions of the LDEF surfaces are contaminated by outgassed materials from experimenters trays, in addition to the LDEF autocontamination and impact with orbital debris not of extraterrestrial origin. Because interplanetary dust particles (IDP's) nominally impacted the LDEF at velocities greater than 3 km/s, the potential for intact survival of carbonaceous compounds is mostly unknown for hypervelocity impacts. Calculations show that for solid phthalic acid (a test impactor), molecular dissociation would not necessarily occur below 3 km/s, if all of the impact energy was directed at breaking molecular bonds, which is not the case. Hypervelocity impact experiments (LDEF analogs) were performed using the Ames Vertical Gun Facility. Grains of phthalic acid and the Murchison meteorite (grain diameter = 0.2 for both) were fired into an Al plate at 2.1 and 4.1 km/s respectively. The results of the study are presented, and it is concluded that meaningful biogenic elemental and compound information can be obtained from IDP impacts on the LDEF.

Bunch, T. E.↗

Beagle 2: The Next Exobiology Mission to Mars

Beagle 2 is a 60 kg probe (with a 30 kg lander) developed in the United Kingdom for inclusion on the European Space Agency's 2003 Mars Express. Beagle 2 will deliver to the Martian surface a payload which consists of a high percentage of science instruments to landed spacecraft mass. Beagle 2 will be launched in June, 2003 with Mars Express on a Soyuz-Fregat rocket from the Baikonur Cosmodrome in Kazakhstan. Beagle 2 will land on Mars on December 26, 2003 in the Isidis Planitia basin (approximately 10 degrees N and 275 degrees W), a large sedimentary basin that overlies the boundary between ancient highlands and northern plains. Isidis Planitia, the third largest basin on Mars, which is possibly filled with sediment deposited at the bottom of long-standing lakes or seas, offers an ideal environment for preserving traces of life. Beagle 2 was developed to search for organic material and other volatiles on and below the surface of Mars in addition to the study of the inorganic chemistry and mineralogy. Beagle 2 will utilize a mechanical mole and grinder to obtain samples from below the surface, under rocks and inside rocks. A pair of stereo cameras will image the landing site along with a microscope for examination of surface and rock samples. Analyses will include both rock and soil samples at various wavelengths, X-ray spectrometer and Mossbauer spectrometer as well as a search for organics and other light element species (e.g. carbonates and water) and measurement of their isotopic compositions. Beagle 2 has as its focus the goal of establishing whether evidence for life existed in the past on Mars at the Isidis Planitia site or at least establishing if the conditions were ever suitable. Carbonates and organic components were first recognized as existing on Mars when they were found in the Martian meteorite Nakhla. Romanek et al showed the carbonates in ALH84001 were formed at low temperatures. McKay et al noted possible evidence of early life on Mars within the ALH84001 meteorite. Thomas-Keprta et al showed the magnetite biomarkers in ALH84001's carbonates are indistinguishable from those formed by magnetotactic bacteria found on Earth. Gibson et al showed there was significant evidence for liquid water and biogenic products present on Mars across a 3.9 billion year period. A mechanical arm (PAW) operates from the lander and is used for science operations along with sample acquisition. Instruments attached to the PAW include: stereo cameras, Mossbauer instrument, X-ray fluorescence instrument, microscope, environmental sensors, rock corer/grinder, a spoon, mirror, brushes, a mole attachment for acquisition of subsurface to depths of 1 to 2 meters and an illumination device. Each camera has 14 filters which have been optimized for mineralogy composition, dust and water vapor detection. The microscope's camera is designed for viewing the size and shape of dust particles, rock surfaces, microfossils, and characteristics of the samples prior to introduction into the gas analysis package (GAP). The camera has a resolution of 4 microns/pixel, features four color capability (red, green, blue and UV (ultraviolet) fluoresence), a depth of focus of 40 micrometers and translation stage of +3 millimeters. The heart of the Beagle 2's life detection package is the gas analysis package (GAP), which consists of a mass spectrometer with collectors at fixed masses for precise isotopic ratio measurements and voltage scanning for spectral analysis. Primary aim of the GAP is to search for the presence of bulk constituents, individual species, and isotopic fractionations for both extinct and extent life along with studying the low-temperature geochemistry of the hydrogen, carbon, nitrogen and oxygen components on Mars from both the surface and atmosphere. GAP is a magnetic sector mass spectrometer with the range of 1 to 140 amu which can be operated in both the static and dynamic modes. A triple Faraday collector array will be used for C, N and O ratios along with a double Faraday array for H/D. Pulse counting electron multiplier will be utilized for noble gases and selected organics. Anticipated detection limits are at the picomole level for operation in the static mode of operation and high precision isotopic measurements will be made in the dynamic mode. Sample processing and preparation system consists of reaction vessels along with references. Sample ovens capable of being heated are attached to the manifold for sample combustion. Surface, subsurface materials and interior rock specimens will be combusted in pure oxygen gas at various temperature intervals to release organic matter and volatiles. Combustion process will permit detection of all forms and all atoms of carbon present in the samples. A chemical processing system is capable of a variety of conversion reactions. Gases are manipulated either by cryogenic or chemical reactions and passed through the gas handling portion of the vacuum system. There are two modes of operation: quantitative analysis and precise isotopic measurements. Additional information is contained in the original extended abstract.

Gibson, Everett K., Jr.↗

Highly Sensitive Tunable Diode Laser Spectrometers for In Situ Planetary Exploration

This paper describes highly sensitive tunable diode laser spectrometers suitable for in situ planetary exploration. The technology developed at JPL is based on wavelength modulated cavity enhanced absorption spectroscopy. It is capable of sensitively detecting chemical signatures of life through the abundance of biogenic molecules and their isotopic composition, and chemicals such as water necessary for habitats of life. The technology would be suitable for searching for biomarkers, extinct life, potential habitats of extant life, and signatures of ancient climates on Mars; and for detecting biomarkers, prebiotic chemicals and habitats of life in the outer Solar System. It would be useful for prospecting for water on the Moon and asteroids, and characterizing its isotopic composition. Deployment on the Moon could provide ground truth to the recent remote measurements and help to uncover precious records of the early bombardment history of the inner Solar System buried at the shadowed poles, and elucidate the mechanism for the generation of near-surface water in the illuminated regions. The technology would also be useful for detecting other volatile molecules in planetary atmospheres and subsurface reservoirs, isotopic characterization of planetary materials, and searching for signatures of extinct life preserved in solid matrices.

Vasudev, Ram↗

Spectroscopic and Geochemical Analyses of Ferrihydrite from Hydrothermal Springs in Iceland and Applications to Mars

Ferrihydrite samples were collected from a thermal spring and a cold stream in the Landmannalaugar region of Iceland. Chemical and spectroscopic analyses have been performed on the air-dried and fine-grained fractions of these samples. The ferrihydrite from the cold stream is a pure sample, containing small amounts of Ca, P and Si, which do not form minerals detectable with X-ray diffraction (XRD) or reflectance and transmittance spectroscopy. The ferrihydrite from the thermal pool is a less pure sample, containing larger amounts of amorphous Si and P. The XRD and spectral features for this sample are also consistent with a less crystalline structure. Some of the Si is incorporated in the structure of the ferrihydrite. The Ca, P and possibly some of the Si may be biogenic. The spectral character of these Icelandic ferrihydrites is compared with those of synthetic ferrihydrites and other iron oxide/oxyhydroxide minerals. Ferrihydrite is characterized by a broad Fe3+ excitation band near 0.92 microns (approx. 10900/cm) and a strong Fe-O absorption feature near 475/cm (approx. 21 microns) in transmittance spectra. Multiple bands due to H2O and OH are also present for ferrihydrite. Natural ferrihydrites frequently exhibit a band near 950-1050/cm (approx. 10 microns) that is typically not observed for synthetic ferrihydrites and may be due to some Si in the structure. An additional pair of spectral bands near 1400 and 1500/cm (approx. 7 microns) are characteristic of pure ferrihydrites from natural and synthetic sources. Hydrothermal springs may have been present at one time on Mars in association with volcanic activity. Ferrihydrite formation in such an environment may have contributed to the ferric oxide-rich surface material on Mars.

Bishop, Janice↗

Comet coma sample return instrument

The sample collection technology and instrument concept for the Sample of Comet Coma Earth Return Mission (SOCCER) are described. The scientific goals of this Flyby Sample Return are to return to coma dust and volatile samples from a known comet source, which will permit accurate elemental and isotopic measurements for thousands of individual solid particles and volatiles, detailed analysis of the dust structure, morphology, and mineralogy of the intact samples, and identification of the biogenic elements or compounds in the solid and volatile samples. Having these intact samples, morphologic, petrographic, and phase structural features can be determined. Information on dust particle size, shape, and density can be ascertained by analyzing penetration holes and tracks in the capture medium. Time and spatial data of dust capture will provide understanding of the flux dynamics of the coma and the jets. Additional information will include the identification of cosmic ray tracks in the cometary grains, which can provide a particle's process history and perhaps even the age of the comet. The measurements will be made with the same equipment used for studying micrometeorites for decades past; hence, the results can be directly compared without extrapolation or modification. The data will provide a powerful and direct technique for comparing the cometary samples with all known types of meteorites and interplanetary dust. This sample collection system will provide the first sample return from a specifically identified primitive body and will allow, for the first time, a direct method of matching meteoritic materials captured on Earth with known parent bodies.

Albee, A. L.↗

Biological potential of extraterrestrial materials. 2. Microbial and plant responses to nutrients in the Murchison carbonaceous meteorite

Meteoritic materials are investigated as potential early planetary nutrients. Aqueous extracts of the Murchison C2 carbonaceous meteorite are utilized as a sole carbon source by microorganisms, as demonstrated by the genetically modified Pseudomonas fluorescence equipped with the lux gene. Nutrient effects are observed also with the soil microorganisms Nocardia asteroides and Arthrobacter pascens that reach populations up to 5 x 10(7) CFU/ml in meteorite extracts, similar to populations in terrestrial soil extracts. Plant tissue cultures of Asparagus officinalis and Solanum tuberosum (potato) exhibit enhanced pigmentation and some enhanced growth when meteorite extracts are added to partial nutrient media, but inhibited growth when added to full nutrient solution. The meteorite extracts lead to large increases in S, Ca, Mg, and Fe plant tissue contents as shown by X-ray fluorescence, while P, K, and Cl contents show mixed effects. In both microbiological and plant tissue experiments, the nutrient and inhibitory effects appear to be best balanced for growth at about 1:20 (extracted solid : H2O) ratios. The results suggest that solutions in cavities in meteorites can provide efficient concentrated biogenic and early nutrient environments, including high phosphate levels, which may be the limiting nutrient. The results also suggest that carbonaceous asteroid resources can sustain soil microbial activity and provide essential macronutrients for future space-based ecosystems.

Non-NASA Center↗

Laboratory and observational study of the interrelation of the carbonaceous component of interstellar dust and solar system materials

By studying the chemical and isotopic composition of interstellar ice and dust, one gains insight into the composition and chemical evolution of the solid bodies in the solar nebula and the nature of the material subsequently brought into the inner part of the solar system by comets and meteorites. It is now possible to spectroscopically probe the composition of interstellar ice and dust in the mid-infrared, the spectral range which is most diagnostic of fundamental molecular vibrations. We can compare these spectra of various astronomical objects (including the diffuse and dense interstellar medium, comets, and the icy outer planets and their satellites) with the spectra of analogs we produce in the laboratory under conditions which mimic those in these different objects. In this way one can determine the composition and abundances of the major constituents of the various ices and place general constraints on the types of organics coating the grains in the diffuse interstellar medium. In particular we have shown the ices in the dense clouds contain H2O, CH3OH, CO, perhaps some NH3 and H2CO, we well as nitriles and ketones or esters. Furthermore, by studying the photochemistry of these ice analogs in the laboratory, one gains insight into the chemistry which takes place in interstellar/precometary ices. Chemical and spectroscopic studies of photolyzed analogs (including deuterated species) are now underway. The results of some of these studies will be presented and implications for the evolution of the biogenic elements in interstellar dust and comets will be discussed.

Allamandola, L. J.↗

Coordinated Analyses of Antarctic Sediments as Mars Analog Materials Using Reflectance Spectroscopy and Current Flight-Like Instruments for CheMin, SAM and MOMA

Coordinated analyses of mineralogy and chemistry of sediments from the Antarctic Dry Valleys illustrate how data obtained using flight-ready technology of current NASA and ESA missions can be combined for greater understanding of the samples. Mineralogy was measured by X-ray diffraction (XRD) and visible/ near-infrared (VNIR) reflectance spectroscopy. Chemical analyses utilized a quadrupole mass spectrometer (QMS) to perform pyrolysis-evolved gas analysis (EGA) and gas chromatography-mass spectrometry (GC/MS) both with and without derivatization, as well as laser desorption-mass spectrometry (LD/MS) techniques. These analyses are designed to demonstrate some of the capabilities of near-term landed Mars missions, to provide ground truthing of VNIR reflectance data acquired from orbit by the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) on MRO and to provide detection limits for surface- operated instruments: the Chemistry and Mineralogy (CheMin) and Sample Analysis at Mars (SAM) instrument suites onboard Mars Science Laboratory (MSL) and the Mars Organic Molecule Analyzer (MOMA) onboard ExoMars-2018. The new data from this study are compared with previous analyses of the sediments performed with other techniques. Tremolite was found in the oxic region samples for the first time using the CheMin-like XRD instrument. The NIR spectral features of tremolite are consistent with those observed in these samples. Although the tremolite bands are weak in spectra of these samples, spectral features near 2.32 and 2.39 micrometers could be detected by CRISM if tremolite is present on the martian surface. Allophane was found to be a good match to weak NIR features at 1.37-1.41, 1.92, and 2.19 micrometers in spectra of the oxic region sediments and is a common component of immature volcanic soils. Biogenic methane was found to be associated with calcite in the oxic region samples by the SAM/EGA instrument and a phosphoric acid derivative was found in the anoxic region sample using the SAM/MTBSTFA technique.

Mars↗

Overview of Micrometeoroid and Orbital Debris Analysis Process for Mars Sample Return Earth Entry System

Introduction: Micrometeoroid and orbital debris (MMOD) risk analyses for the Mars Sample Return (MSR) Earth Entry System (EES) have been significantly more rigorous than previously flown missions because of its categorization as a Class V restricted return mission. This means the returned samples present significant concern for biogenic contamination. These analyses seek to determine if a micrometeoroid or orbital debris strike would result in loss of containment assurance and are summarized in the flowchart in Fig. 1. Methodology: The mission is considered in two MMOD phases: a pre-release phase where the EES is protected by a Micrometeoroid Protection System (MMPS) and a post-release phase called “free-flight” where the EES is exposed directly to the MMOD environment. These phases correspond to interplanetary cruise and imminent re-entry, respectively. To inform the MMPS design, a 30-shot high velocity impact testing (HVIT) series on candidate configurations at NASA White Sands Test Facility was completed in the summer of 2022. Sample post-shot images are shown in Fig 2 [1]. These data are used to baseline the MMPS design and to tune the hydrocode simulations. ALE3D, CTH, and SPHC are the hydrocodes that simulate physics of high-speed impacts [2]. Results generated with these populate a penetration depth versus energy space beyond the testable velocity regime of HVIT (~7 km/s). The penetration depth versus energy space data are used to define a critical projectile diameter function called a Ballistic Limit Equation (BLE), where the projectile “criticality” is determined by zone dependent failure criteria defined a-priori [3]. For example, the nose of the heatshield has a failure criterion of 50% TPS penetration, assigned because the landing loads are concentrated on that region and no substructure damage is permitted. The BLEs for each vehicle material zone are input into the BUMPER 3 code, along with the vehicle surface mesh and the corresponding space environment model, to calculate a probability of penetration or number of penetrations. The environment models, MEM3 for MM and ORDEM 3.2 for OD, simulate the meteoroid environment from 0.2 to 2 au based on the Grün flux equation, and the debris environment up to 40,000 km altitude from Earth surface, respectively [4,5]. Presentation Focus: The presentation or poster will present the results to-date focusing on the full risk analysis process flow seen in Fig. 1. Details on the derivation of the failure criteria will be discussed, along with HVIT results and how these influenced the MMPS configuration baseline decision. Further, results of hydrocode simulations will be presented and the tuning to HVIT outputs will be described. Finally, the strategies that direct the BLE formulation will be reviewed, specifically, for the EES elements that are most exposed to the MMOD environment.

mmod↗

Visualization of Microbial Biomarkers by Scanning Electron Microscopy

We are developing tools to link the biochemical structure of selected biomarkers with putative biogenic structures observed in mineralized samples. The detection of evidence of life on Mars and other planets will rely on methods that can discriminate compounds formed exclusively by living organisms. While biogenic compounds, such as amino acids and nucleotides have been discovered in extraterrestrial sources, such as meteorites and comets, their formation can be explained by abiotic means. The formation of cellular structures, or more elaborate organic molecules, such as complex lipids, proteins or nucleic acids, however, is strongly correlated to the presence of even the most primitive life processes. Recent evidence lends support to the hypothesis that life may have once existed on Mars. Carbonate globules and ppm concentrations of polycyclic aromatic hydrocarbons (PAHs) have been described in ALH84001, a meteorite originating from Mars ejecta captured by Earth over 13,000 years ago. The localized high concentration of PAHs that follow an increasing gradient from the intact fusion crust towards the interior corresponds to microgram quantities of hydrocarbon. Even though ALH84001 and other similar meteorites have withstood the forces capable of ejecting rock through Mars' escape velocity, upon entering Earth's atmosphere, their core temperatures are likely not to have been raised significantly, as evidenced by the survival of remanent magnetic signatures. Ideal biomarkers of ancient or modern biological life would include molecules that are (or were) pervasive and highly resistant to degradation. Also, requisite methods of detection should be simple, extremely sensitive and broadly inclusive (NASA SP-530). Lipopolysaccharide (LPS), peptidoglycan or pseudopeptidoglycan and beta-glucan are microbial cell wall components which together cover the entire microbial spectrum of eubacteria, archea and fungi. They are all remarkably resistant to thermal degradation. Fortunately, many antimicrobial defense systems of higher organisms require sensitive detection to combat microbial pathogens. We employ here the primitive immune system of the evolutionarily ancient horseshoe crab, Limulus polyphemus. This species relies on multi-enzyme signal amplification detection of cell wall molecules and they can be applied to the development of useful detectors of life. An extension of this work includes the visualization of microbial signatures by labeling LAL components with chromogenic or electron dense markers. The protein Limulus Anti-LPS Factor (LALF) has an extremely high affinity for LPS. By coupling LALF binding with colloidal gold labels we demonstrate a correlation of the structures visible by electron microscopy with biochemical evidence of microbial cell wall materials. Pure silica particles were mixed with cultures of E. coli (10(exp 6) cfu/mL). Samples were washed sequentially with buffered saline, LALF, antibody to LALF and finally colloidal gold-labeled Protein A. Negative controls were not exposed to E. coli but received identical treatment otherwise. Samples were coated with carbon and imaged on a JEOL JSM-840 scanning electron microscope with LaB6 source in the back scatter mode with the JEOL annular back scatter detector. 20 nm-scale black spots in this contrast-reversed image originate from electrons back-scattered by gold atoms. Negative controls did not give any signal. Future work will expand application of this technique to soil simulants and mineralized rock samples.

Wainwright, Norman R.↗

Xenon Fractionation, Hydrogen Escape, and the Oxidation of the Earth

Xenon in Earth's atmosphere is severely mass fractionated and depleted compared to any plausible solar system source material, yet Kr is unfractionated. These observations seem to imply that Xe has escaped from Earth. But to date no process has been identified that can cause Xe, which is heavier than Kr, to escape while Kr does not. Vigorous hydrodynamic hydrogen escape can produce mass fractionation in heavy gases. The required hydrogen flux is very high but within the possible range permitted by solar Extreme Ultraviolet radiation (EUV, which here means radiation at wavelengths short enough to be absorbed efficiently by hydrogen) heating when Earth was on the order of 100 Myrs old or younger. However this model cannot explain why Xe escapes but Kr does not. Recently, what appears to be ancient atmospheric xenon has been recovered from several very ancient (3-3.5 Ga) terrestrial hydrothermal barites and cherts. What is eye-catching about this ancient Xe is that it is less fractionated that Xe in modern air. In other words, it appears that a process was active on Earth some 3 to 3.5 billion years ago that caused xenon to fractionate. By this time the Sun was no longer the EUV source that it used to. If xenon was being fractionated by escape — currently the only viable hypothesis — it had to be in the less unfamiliar context of Earth’s Archean atmosphere and under rather modest levels of EUV forcing. This requires a new model. Here we address the circumstances in which Xe, but not Kr, could escape from Earth as an ion. In a hydrodynamically escaping hydrogen wind the hydrogen is partially photo-ionized. The key concepts are that ions are much more strongly coupled to the escaping flow than are neutrals (so that a relatively modest flow of H and H+ to space could carry Xe+ along with it), and that xenon alone among the noble gases is more easily ionized than hydrogen. This sort of escape is possible if not prevented by a planetary magnetic field. The best prospects for Earth are therefore escape along the polar field lines, although a very weak or absent magnetic field would likely work as well. As applied to the Archean Earth the discussion will be constrained by diffusion-limited hydrogen escape. The extended history of hydrogen escape implicit in Xe escape in the Archean is consistent with suggestions that hydrogen escape from the anoxic Archean atmosphere was considerable, because biogenic methane is expected to have been rather abundant. Hydrogen escape plausibly played the key role in creating oxidizing condition at the surface of the Earth and setting the stage for the creation of an O2 atmosphere.

photo-ionized gases↗