The first samples collected by the Mars 2020 mission represent units exposed on the Jezero Crater floor, from the potentially oldest Séítah formation outcrops to the potentially youngest rocks of the heavily cratered Máaz formation. Surface investigations reveal landscape‐to‐microscopic textural, mineralogical, and geochemical evidence for igneous lithologies, some possibly emplaced as lava flows. The samples contain major rock‐forming minerals such as pyroxene, olivine, and feldspar, accessory minerals including oxides and phosphates, and evidence for various degrees of aqueous activity in the form of water‐soluble salt, carbonate, sulfate, iron oxide, and iron silicate minerals. Following sample return, the compositions and ages of these variably altered igneous rocks are expected to reveal the geophysical and geochemical nature of the planet's interior at the time of emplacement, characterize martian magmatism, and place timing constraints on geologic processes, both in Jezero Crater and more widely on Mars. Petrographic observations and geochemical analyses, coupled with geochronology of secondary minerals, can also reveal the timing of aqueous activity as well as constrain the chemical and physical conditions of the environments in which these minerals precipitated, and the nature and composition of organic compounds preserved in association with these phases. Returned samples from these units will help constrain the crater chronology of Mars and the global evolution of the planet's interior, for understanding the processes that formed Jezero Crater floor units, and for constraining the style and duration of aqueous activity in Jezero Crater, past habitability, and cycling of organic elements in Jezero Crater.
Introduction: Amino acids (AAs) are the building blocks of proteins and are essential for life on Earth. Sources of AAs on early Earth range from exogenous sources such as delivery from extraterrestrial materials (i.e., meteorites, interplanetary dust particles, comets, etc.) to endogenous sources including chemical reactions in hydrothermal vents or atmospheric mixtures [1]. Analyses of AAs of extraterrestrial origin from meteorites and laboratory studies of simulated prebiotic environments revealed that a diverse set of abiotically produced AAs may have been present on early Earth. However only a fraction of these AAs is found within the proteins of living organisms. Of the 22 genetically encoded (proteinogenic) AAs, 20 occur in the standard genetic code (SGC) and are used by nearly all living organisms to build proteins. The universality of this AA alphabet suggests the presence and incorporation of these specific AAs occurred early in the evolution of life. Combined observational and experimental data on AA abundances in meteorites and laboratory studies suggest that only a subset of modern proteinogenic AAs are synthesized in measurable quantities by theorized prebiotic pathways [2]. Based on these results, many researchers have postulated that protein synthesis occurred in two phases. During the first phase, protein synthesis occurred with a limited AA alphabet, consisting of those AAs that are easily synthesized by prebiotic reactions or those that are abundant in meteorites. During the second phase, new AA biosynthetic pathways evolved thus expanding the AA alphabet to its modern form [3,4]. Statistical studies of AA frequency in a variety of diverse taxa bolster this claim. Several authors have found that “early” AAs decrease in frequency while “late” AAs increase, indicating that late proteinogenic AAs may not have been present in prebiotic environments during early protein synthesis [5-7]. While the chronological order of AA appearance can vary slightly based on the criteria used (i.e., thermodynamic properties versus trends in the genetic code), all methods predict the late arrival of aromatic AAs (Figure 1, Table 1). Examples of abiotic syntheses of phenylalanine, tyrosine, and tryptophan are rare in modern terrestrial environments and have not been easily recreated in laboratory settings [8,9]. Furthermore, aromatic AAs in meteorites have rarely been reported and, where reported, their abundances are significantly lower than abundances of ‘early’ proteinogenic AAs, such as glycine or alanine [10]. If prebiotic chemical reactions cannot produce aromatic AAs in meaningful quantities, an alternate explanation for their incorporation into the SCG is that they are biotic inventions.
Laboratory simulations have demonstrated that hydrothermal systems have the potential to produce a range of organic compounds through Fischer-Tropsch type (FTT) chemistry. The distribution of products depends on several factors, including the abundance and composition of feed-stock molecules, reaction temperature, and the physical and chemical characteristics of catalytic materials included in the reactions. The majority of studies per-formed to date have focused solely on inclusion of CO2 or CO and H2 as the carbon, oxygen and hydrogen sources, which limits the possible products to hydro-carbons, alcohols and carboxylic acids. A few studies have included nitrogen in the form of ammonia, which led to the production of amino acids and nitrogenous bases; and a separate suite of studies included sulfur as sulfide minerals or H2S, which yielded products such as thiols and amino acids. Although these demonstrations provide compelling evidence that FTT reactions can produce compounds of interest for the origins of life, such reactions have been conducted under a very limited range of conditions and the synthetic reaction mechanisms have generally not been well-characterized. As a consequence, it is difficult to extrapolate these results to geologic systems or to evaluate how variations in reactant compositions would affect the distribution of products over time. We have begun a series of laboratory experiments that will incorporate a range of precursor molecules in varying compositions to determine how these variables affect the relative amounts and speciation of life-essential elements in organic molecules produced under FTT conditions. In the present work, we focus on systems containing C, H, O and N.
Introduction: Carbonate minerals of martian origin are present in several martian meteorites in trace concentrations (< 1%) and possess unique isotopic signatures that suggest that the martian environment and/or isotopic reservoirs are very different from the Earth’s [1–3]. Carbonates are most common in the older martian meteorites (Allan Hills 84001 and the nakhlites), however, there have been reports of carbonate in the younger shergottites including Elephant Moraine A79001 [1,4]. Acidification studies of Zagami and Shergotty have shown that CO2 is released suggesting that carbonate phases are present in these meteorites [4], but the origin of these phases is controversial. The young ages of the shergottites [5] makes them important samples for understanding the modern martian environment. The carbonates in EETA 79001 are the best-characterized secondary minerals in a shergottite, but their origin remains controversial. Gooding et al. [1] argued that two types of carbonate occur within the glassy parts of the meteorite. One type, nearly pure CaCO3 associated with Ca-sulfate shows textural evidence for being present in the rock prior to it being shocked, suggesting formation on Mars. The second was more abundant and consists of Ca-rich carbonate, possibly with finely intergrown Mg-phosphate, but does not possess any textural relationships indicative of a martian origin. Carbon and oxygen isotopic studies of this carbonate yielded oxygen isotopes that potentially suggest a martian origin as well [6, 7] (Fig 1). Are Elephant Moraine A79001 Carbonates Terrestrial? Many of the ordinary chondrites collected in Antarctica exhibit some form of weathering, and studies have shown that carbonates are a typical weathering product [8, 9]. Velbel et al. [9] suggest that at least 5% ordinary chondrites collected in Antarctica show visible white crusts, while spectroscopic measurements suggest that this weathering may be ubiquitous [10]. The most well studied example of Antarctic carbonate formation would be LEW 85320 which has been shown to contain hydrated Mg-carbonate with an isotopic composition consistent with formation from terrestrial reservoirs [11]. In addition, the C signature of this carbonate weathering product suggests formation in the past 40 years [11]. Indigenous carbonate is rare in ordinary chondrites of higher petrologic type (types 4-6) which therefore can serve as reliable witness plates for Antarctic weathering processes. A few studies have analyzed the isotopic composition of carbonates in Antarctic ordinary chondrites [12, 13]. The carbonate analyses have focused primarily on meteorites recovered from the Allan Hills region with a few exceptions. When compared with data from the martian meteorites (Fig. 1) a number of interesting observations can be made raising some unanswered questions.
Amino acids, the building blocks of proteins, have been found to be indigenous in the eight carbonaceous chondrite groups. The abundances, structural, enantiomeric and isotopic compositions of amino acids differ significantly among meteorites of different groups and petrologic types. These results suggest parent-body conditions (thermal or aqueous alteration), mineralogy, and the preservation of amino acids are linked. Previously, elucidating specific relationships between amino acids and mineralogy was not possible because the samples analyzed for amino acids were much larger than the scale at which petrologic heterogeneity is observed (sub mm-scale differences corresponding to sub-mg samples); for example, Pizzarello and coworkers measured amino acid abundances and performed X-ray diffraction (XRD) on several samples of the Murchison meteorite, but these analyses were performed on bulk samples that were 500 mg or larger. Advances in the sensitivity of amino acid measurements by liquid chromatography with fluorescence detection/time-of-flight mass spectrometry (LC-FD/TOF-MS), and application of techniques such as high resolution X-ray diffraction (HR-XRD) and scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS) for mineralogical characterizations have now enabled coordinated analyses on the scale at which mineral heterogeneity is observed. In this work, we have analyzed samples of the Lonewolf Nunataks (LON) 94101 CM2 carbonaceous chondrite. We are investigating the link(s) between parent body processes, mineralogical context, and amino acid compositions in meteorites on bulk samples (approx. 20mg) and mineral separates (< or = 3mg) from several of spatial locations within our allocated samples. Preliminary results of these analyses are presented here.
Eucrites are a class of basaltic meteorites that, along with the howardites and diogenites, likely derive from the asteroid 4-Vesta. This asteroid is depleted in moderately volatile elements relative to the Earth and carbonaceous chondrites. Extrapolation of this depletion trend predicts that bulk silicate 4-Vesta (BSV) contains at most 250-1000 μg/g H2O, which is approximately a factor of two lower than the H2O content of Earth. To obtain more accurate H2O and F estimates for BSV, we examined four unequilibrated antarctic meteorites, Yamato(Y)-793548, Y-82210, Y-75011, and Y-74450, by EPMA and SIMS. Pyroxenes contain MgO-rich cores and FeO-rich rims, consistent with primary magmatic zoning. Volatile concentrations generally follow patterns expected for growth zoning with lower values in the cores and higher in the rims. These features indicate that thermal metamorphism and other post-crystallization processes did not significantly perturb the volatile contents of these unequilibrated eucrite pyroxenes. We used these data to derive best estimates for the BSV H2O and F content based on experimentally determined pyroxene-melt partition coefficients and models for magma generation on Vesta. In addition, we measured D/H in the early crystallizing pyroxenes and late crystallzing apatites. We find that the D/H of pyroxene and apatite are within error of one another as well as previous measurements of apatite in equilibrated eucrites. These results imply that degassing was minimal or did not fractionate D/H. Degassing may have been limited if eucrites were shallowly emplaced sills or dykes, or the total H2O content of the magmas was too low for vapor saturation. An alternative mechanism for limited D/H fractionation is that degassing did occur, but the H2/H2O of the exsolved vapor was approximately 15:85, as predicted from experiments.
Sulfide assemblages are commonly found in chondritic meteorites as small inclusions in the matrix or in association with chondrules. These assemblages are widely hypothesized to form through pre-accretionary corrosion of metal by H2S gas or through parent body processes. We report here on two unequilibrated R chondrite samples that contain large, chondrule-sized sulfide nodules in the matrix. Both samples are from Mount Prestrud (PRE) 95404. Chemical maps and spot and broad-beam electron microprobe analyses (EMPA) were used to assess the distribution, stoichiometry, and bulk composition of sulfide nodules and silicate chondrules in the clasts. Oxygen isotope data were collected via secondary ion mass spectrometry (SIMS) to assess the relationship of chondrules to other chondrite groups. Scanning electron microscopy (SEM), focused ion beam (FIB), and transmission electron microscopy (TEM) analyses were used to assess fine-scale features and identify crystal structures in sulfide assemblages. Thermodynamic models were used to assess the temperature, sulfur fugacity (fS(2)), total pressure, dust-to-gas ratio, and oxygen fugacity (fO(2)) conditions during sulfide nodule and chondrule formation.The unequilibrated clasts include a mixture of type I and type II chondrules, as well as non-porphyritic chondrules. Chondrule oxygen isotopes overlap with ordinary-chondrite chondrules. Sulfide nodules average 200 mm in diameter, have rounded shapes, and are primarily composed of pyrrhotite, pentlandite, and magnetite. Some are deformed around chondrules in a petrologic relationship similar in appearance to compound chondrules. Both nodules and sulfides in chondrules include phosphate inclusions and Cu-rich lamellae, which suggests a genetic relationship between sulfides in chondrules and in the matrix. Ni/Co ratios for matrix and chondrule sulfides are solar, while Fe and Ni are non-solar and inversely related.We hypothesize that sulfide nodules formed via pre-accretionary melt processes. During chondrule formation, precursors composed of a mixture of silicate and sulfide material were heated to form immiscible melt droplets, which separated and cooled to form Si-rich chondrules and S-rich nodules. Sulfide melt was stabilized by a high total pressure (similar to 1 atm) in a dust-or ice-enriched environment. Heating of this material contributed to a high fS(2) (2 x 10(-3) atm at 1138 degrees C), and high fO(2) (IW -1 to IW -4), in an environment with peak temperatures between 1539 degrees C and 1750 degrees C. Oxygen isotopic compositions in this region were similar to those recorded by the LL-chondrite chondrules. (C) 2017 Elsevier Ltd. All rights reserved.
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.
Pasamonte is a clast-rich polymict basaltic breccia with O- and Cr-isotopic compositions that are resolved from those of most eucrites. It is dominated by two mafic clast types: (i) very-fine- to fine-grained, variolitic, subophitic and ophitic basalts, usually containing zoned pyroxenes; and (ii) fine- to medium grained hypidiomorphic-granular and allotriomorphic-granular microgabbros containing pyroxenes composed of augite lamellae in homogeneous pigeonite hosts. Minor clast types are fine-grained impact-melt, mafic-breccia and mafic-granular clasts; coarse matrix mineral fragments include pyroxene, plagioclase, silica, ferroan olivine and ilmenite. Our petrologic studies include determination of plagioclase compositions for the two major clast types and matrix grains, which we report here.
Primitive carbonaceous chondrites contain a wide variety of organic material, ranging from soluble discrete molecules to insoluble nanoglobules of macro-molecular carbon. The relationship between the soluble organic molecules, macromolecular organic material, and host minerals are poorly understood. Large H, C and N isotopic anomalies suggest some organic components formed in low-T interstellar or outer Solar System environments. The highest isotope anomalies occur in m-scale inclusions in the most primitive materials, such as cometary dust and the least altered carbonaceous chondrites. Often, the hosts of these isotopically anomalous 'hotspots' are discrete organic nanoglobules that probably formed in the outermost reaches of the protosolar disk or cold molecular cloud. Molecular and isotopic studies of meteoritic organic matter are aimed at identifying the chemical properties and formation processes of interstellar organic materials and the subsequent chemical evolutionary pathways in various Solar System environments. The combination of soluble and insoluble analyses with in situ and bulk studies provides powerful constraints on the origin and evolution of organic matter in the Solar System. Using macroscale extraction and analysis techniques as well as microscale in situ observations we have been studying both insoluble and soluble organic material in primitive astromaterial samples. Here, we present results of bulk C and N isotopic measurements and coordinated in situ C and N isotopic imaging and mineralogical and textural studies of carbonaceous materials in a Cr2 carbonaceous chondrite. In accompanying abstracts we discuss the morphology and distribution of carbonaceous components and soluble organic species of this meteorite.
Equilibrated Rumuruti (R) chondrites record an oxygen fugacity between 0 and 3.5 log units below the fayalite-magnetite-quartz buffer, and a sulfur fugacity (fS2) 2 log units above the iron-troilite buffer. They are more than an order of magnitude more oxidized than the ordinary chondrites [1], and orders of magnitude more sulfidized than solar values. Although the R chondrites have the highest (delta)O-17 value of any meteorites, analyses of unequilibrated R chondrites indicate chondrule formation in an oxygen isotope reservoir similar to that of the ordinary chondrite chondrules. We present the relationship of the R chondrite parent body to pre-accretionary volatiles O and S based on our analyses of unequilibrated R chondrite material in two thin sections from the meteorite Mount Prestrud (PRE) 95404.
Space weathering processes - driven primarily by solar wind ion and micrometeorite bombardment, are constantly changing the surface regoliths of airless bodies, such as the Moon. It is essential to study lunar soils in order to fully under-stand the processes of space weathering, and how they alter the optical reflectance spectral properties of the lunar surface relative to bedrock. Lunar agglutinates are aggregates of regolith grains fused together in a glassy matrix of shock melt produced during micrometeorite impacts into the lunar regolith. The formation of the shock melt component in agglutinates involves reduction of Fe in the target material to generate nm-scale spherules of metallic Fe (nanophase Fe0 or npFe0). The ratio of elemental Fe, in the form of npFe0, to FeO in a given bulk soil indicates its maturity, which increases with length of surface exposure as well as being typically higher in the finer-size fraction of soils. The melting and mixing process in agglutinate formation remain poorly understood. This includes incomplete knowledge regarding how the homogeneity and overall compositional trends of the agglutinate glass portions (agglutinitic glass) evolve with maturity. The aim of this study is to use sub-micrometer scale X-ray compositional mapping and image analysis to quantify the chemical homogeneity of agglutinitic glass, correlate its homogeneity to its parent soil maturity, and identify the principal chemical components contributing to the shock melt composition variations. An additional focus is to see if agglutinitic glass contains anomalously high Fe sub-micron scale compositional domains similar to those recently reported in glassy patina coatings on lunar rocks.
Primitive carbonaceous chondrites contain a wide variety of organic material, ranging from soluble discrete molecules to insoluble, unstructured kerogen-like components, as well as structured nano-globules of macromolecular carbon. The relationship between the soluble organic molecules, macromolecular organic material, and host minerals are poorly understood. Due to the differences in extractability of soluble and insoluble organic materials, the analysis methods for each differ and are often performed independently. The combination of soluble and insoluble analyses, when performed concurrently, can provide a wider understanding of spatial distribution, and elemental, structural and isotopic composition of organic material in primitive meteorites. Using macroscale extraction and analysis techniques in combination with in situ microscale observation, we have been studying both insoluble and soluble organic material in the primitive CR2 chondrite Miller Range (MIL) 090657. In accompanying abstracts (Cao et al. and Messenger et al.) we discuss insoluble organic material in the samples. By performing the consortium studies, we aim to improve our understanding of the relationship between the meteorite minerals and the soluble and insoluble organic phases and to delineate which species formed within the meteorite and those that formed in nebular or presolar environments. In this abstract, we present the results of amino acid analyses of MIL 090657 by ultra performance liquid chromatography with fluorescence detection and quadrupole-time of flight mass spectrometry. Amino acids are of interest because they are essential to life on Earth, and because they are present in sufficient structural, enantiomeric and isotopic diversity to allow insights into early solar system chemical processes. Furthermore, these are among the most isotopically anomalous species, yet at least some fraction are thought to have formed by aqueously-mediated processes during parent body alteration.
Olivine is a major constituent of chondritic bodies and its response to space weathering processes likely dominates the optical properties of asteroid regoliths (e.g. S- and many C-type asteroids). Analyses of olivine in returned samples and laboratory experiments provide details and insights regarding the mechanisms and rates of space weathering. Analyses of olivine grains from lunar soils and asteroid Itokawa reveal that they display solar wind damaged rims that are typically not amorphized despite long surface exposure ages, which are inferred from solar flare track densities (up to 10 (sup 7 y)). The olivine damaged rim width rapidly approaches approximately 120 nm in approximately 10 (sup 6 y) and then reaches steady-state with longer exposure times. The damaged rims are nanocrystalline with high dislocation densities, but crystalline order exists up to the outermost exposed surface. Sparse nanophase Fe metal inclusions occur in the damaged rims and are believed to be produced during irradiation through preferential sputtering of oxygen from the rims. The observed space weathering effects in lunar and Itokawa olivine grains are difficult to reconcile with laboratory irradiation studies and our numerical models that indicate that olivine surfaces should readily blister and amorphize on relatively short time scales (less than 10 (sup 3 y)). These results suggest that it is not just the ion fluence alone, but other variable, the ion flux that controls the type and extent of irradiation damage that develops in olivine. This flux dependence argues for caution in extrapolating between high flux laboratory experiments and the natural case. Additional measurements, experiments, and modeling are required to resolve the discrepancies among the observations and calculations involving solar wind processing of olivine.
Three masses of the Chelyabinsk meteorite have been studied with a wide range of analytical techniques to understand the mineralogical variation and thermal history of the Chelyabinsk parent body. The samples exhibit little to no postentry oxidation via Mössbauer and Raman spectroscopy indicating their fresh character, but despite the rapid collection and care of handling some low levels of terrestrial contamination did nonetheless result. Detailed studies show three distinct lithologies, indicative of a genomict breccia. A light‐colored lithology is LL 5 material that has experienced thermal metamorphism and subsequent shock at levels near S4. The second lithology is a shock‐darkened LL 5 material in which the darkening is caused by melt and metal‐troilite veins along grain boundaries. The third lithology is an impact melt breccia that formed at high temperatures (~1600 °C), and it experienced rapid cooling and degassing of S 2 gas. Portions of light and dark lithologies from Chel‐101, and the impact melt breccias (Chel‐102 and Chel‐103) were prepared and analyzed for Rb‐Sr, Sm‐Nd, and Ar‐Ar dating. When combined with results from other studies and chronometers, at least eight impact events (e.g., ~4.53 Ga, ~4.45 Ga, ~3.73 Ga, ~2.81 Ga, ~1.46 Ga, ~852 Ma, ~312 Ma, and ~27 Ma) are clearly identified for Chelyabinsk, indicating a complex history of impacts and heating events. Finally, noble gases yield young cosmic ray exposure ages, near 1 Ma. These young ages, together with the absence of measurable cosmogenic derived Sm and Cr, indicate that Chelyabinsk may have been derived from a recent breakup event on an NEO of LL chondrite composition.
Mineral grains in lunar and asteroidal regolith samples provide a unique record of their interaction with the space environment. Space weathering effects result from multiple processes including: exposure to the solar wind, which results in ion damage and implantation effects that are preserved in the rims of grains (typically the outermost 100 nm); cosmic ray and solar flare activity, which result in track formation; and impact processes that result in the accumulation of vapor-deposited elements, impact melts and adhering grains on particle surfaces. Determining the rate at which these effects accumulate in the grains during their space exposure is critical to studies of the surface evolution of airless bodies. Solar flare energetic particles (mainly Fe-group nuclei) have a penetration depth of a few millimeters and leave a trail of ionization damage in insulating materials that is readily observable by transmission electron microscope (TEM) imaging. The density of solar flare particle tracks is used to infer the length of time an object was at or near the regolith surface (i.e., its exposure age). Track measurements by TEM methods are routine, yet track production rate calibrations have only been determined using chemical etching techniques [e.g., 1, and references therein]. We used focused ion beam-scanning electron microscope (FIB-SEM) sample preparation techniques combined with TEM imaging to determine the track density/exposure age relations for lunar rock 64455. The 64455 sample was used earlier by [2] to determine a track production rate by chemical etching of tracks in anorthite. Here, we show that combined FIB/TEM techniques provide a more accurate determination of a track production rate and also allow us to extend the calibration to solar flare tracks in olivine.