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All sourcesNASA NTRSDOE OSTI
NASA NTRS2013

Timescale of Petrogenetic Processes Recorded in the Mount Perkins Magma System, Northern Colorado River Extension Corridor, Arizona

The Miocene Mt. Perkins Pluton is a small composite intrusive body emplaced in the shallow crust as four separate phases during the earliest stages of crustal extension. Phase 1 (oldest) consists of isotropic hornblende gabbro and a layered cumulate sequence. Phase 2 consists of quartz monzonite to quartz monzodiorite hosting mafic microgranitoid enclaves. Phase 3 is composed of quartz monzonite and is subdivided into mafic enclave-rich zones and enclave-free zones. Phase 4 consists of aphanitic dikes of mafic, intermediate and felsic compositions hosting mafic enclaves. Phases 2-4 enclaves record significant isotopic disequilibrium with surrounding granitoid host rocks, but collectively enclaves and host rocks form a cogenetic suite exhibiting systematic variations in Nd-Sr-Pb isotopes that correlate with major and trace elements. Phases 2-4 record multiple episodes of magma mingling among cogenetic hybrid magmas that formed via magma mixing and fractional crystallization at a deeper crustal. The mafic end-member was alkali basalt similar to nearby 6-4 Ma basalt with enriched OIB-like trace elements and Nd-Sr-Pb isotopes. The felsic end-member was a subalkaline crustal-derived magma. Phase 1 isotropic gabbro exhibits elemental and isotopic compositional variations at relatively constant SiO2, suggesting generation of isotropic gabbro by an open-system process involving two mafic end-members. One end-member is similar in composition to the OIB-like mafic end-member for phases 2-4; the second is similar to nearby 11-8 Ma tholeiite basalt exhibiting low epsilon (sub Nd), and depleted incompatible trace elements. Phase 1 cumulates record in situ fractional crystallization of an OIB-like mafic magma with isotopic evidence of crustal contamination by partial melts generated in adjacent Proterozoic gneiss. The Mt Perkins pluton records a complex history in a lithospheric scale magma system involving two distinct mantle-derived mafic magmas and felsic magma sourced in the crust. Mixing and fractional crystallization of these magmas at various levels in the crust generated a suite of intermediate composition magmas. U-Pb zircon SHRIMP ages of phase 1 (15.7 +/- 0.2 Ma), phase 3 (15.8 +/- 0.2 Ma) and phase 4 (15.4 +/- 0.3 Ma) document a 100-300k year timescale for petrogenetic processes recorded in the Mt Perkins magma system.

Danielson, Lisa R.↗
NASA NTRS2015

Survival of Organic Materials in Ancient Cryovolcanically-Produced Halite Crystals

Spectroscopic evidence supports the presence of Mg-Na-K salts derived from cryovolcanism on the surface of Europa. Halite (NaCl) is effective at very long-term preservation of organic phases and structures. Collection of salt crystals from Europan plumes would provide solid inclusions of organics, potentially also biomaterials, all suitable for analysis. Two thermally-metamorphosed ordinary chondrite regolith breccias (Monahans 1998 (H5) and Zag (H3-6)) contain fluid and solid inclusion-bearing halite crystals, dated to approximately 4.5 billion years, and thus the trapped aqueous fluids and solids are at least as old. Heating/freezing studies of the aqueous fluid inclusions in these halites demonstrated that they were trapped near 25 degrees Centigrade, and their continued presence in the halite grains requires that their incorporation into the H chondrite asteroid occurred after that body's metamorphism ended, since heating would have dessicated the halite. O and H isotopes of the trapped fluids are consistent with mixing of asteroidal and cometary water. Cryovolcanic Origin of the Halite: We hypothesize that these meteoritic halites derive from ancient cryovolcanism based on the following points. (1) Salts crystals are observed as products of current cryovolcanism on Enceladus. (2) In-situ spacecraft analysis of some of the icy grains associated with the Enceladus salt found minor organic or siliceous components, including methane, also found in the Monahans halite. (3) Cryovolcanic fluids are observed to be in chemical disequilibrium, reflecting incomplete reactions between interior volatiles and rocky materials. The coexistence of N2 and HCN in Enceladus' cryovolcanic fluids requires that the plume consists of a mixture of materials whose sources experienced different degrees of aqueous processing, including primordial material trapped in ice that has not been in contact with liquid water. The observed mineral assemblage within the Monahans and Zag halites is also far from equilibrium. Cryovolcanoes on Ceres are a potential source of our halite, however the processes that form halite should also be operating within Europa. Dissolution of Monahans halite grains has revealed a remarkable variety of organics, which dominate the population of solid inclusions. Thermal alteration of this macromolecular carbon (measured by Raman spectroscopy) shows remarkable diversity. We have identified highly-condensed aromatics, diamond, carbonates and chloromethane. Light organic compounds like methane tend to be water soluble and require cold formation temperatures at high hydrogen fugacity - i.e. require water ice. Another indication that these halites have not been heated is that light organics readily volatilize or aromaticize into PAHs. We are currently analyzing the organics by Raman and C-XANES, and measuring the content and exploring the potential chirality of amino acids in the halite. Implications for Europa Plumes: Organic materials and structures erupted by a Europa cryovolcano should be similarly preserved within halite, and other salts, which will be a convenient form for capture and analysis, since halite will serve to encapsulate and protect the organics from spacecraft contamination. Also, being transparent at many wavelengths halite will permit analysis by spacecraft-mounted spectroscopic techniques. In addition, halite is readily dissolved, permitting further analysis of entrained organics.

Zolensky, M.↗
NASA NTRS2015

Characterizing Young Giant Planets with the Gemini Planet Imager: An Iterative Approach to Planet Characterization

After discovery, the first task of exoplanet science is characterization. However experience has shown that the limited spectral range and resolution of most directly imaged exoplanet data requires an iterative approach to spectral modeling. Simple, brown dwarf-like models, must first be tested to ascertain if they are both adequate to reproduce the available data and consistent with additional constraints, including the age of the system and available limits on the planet's mass and luminosity, if any. When agreement is lacking, progressively more complex solutions must be considered, including non-solar composition, partial cloudiness, and disequilibrium chemistry. Such additional complexity must be balanced against an understanding of the limitations of the atmospheric models themselves. For example while great strides have been made in improving the opacities of important molecules, particularly NH3 and CH4, at high temperatures, much more work is needed to understand the opacity of atomic Na and K. The highly pressure broadened fundamental band of Na and K in the optical stretches into the near-infrared, strongly influencing the spectral shape of Y and J spectral bands. Discerning gravity and atmospheric composition is difficult, if not impossible, without both good atomic opacities as well as an excellent understanding of the relevant atmospheric chemistry. I will present examples of the iterative process of directly imaged exoplanet characterization as applied to both known and potentially newly discovered exoplanets with a focus on constraints provided by GPI spectra. If a new GPI planet is lacking, as a case study I will discuss HR 8799 c and d will explain why some solutions, such as spatially inhomogeneous cloudiness, introduce their own additional layers of complexity. If spectra of new planets from GPI are available I will explain the modeling process in the context of understanding these new worlds.

exoplanets↗
NASA NTRS2015

Opportunities for Laboratory Opacity Chemistry Studies to Facilitate Characterization of Young Giant Planets and Brown Dwarfs

The thermal emission spectra of young giant planets is shaped by the opacity of atoms and molecules residing in their atmospheres. While great strides have been made in improving the opacities of important molecules, particularly NH3 and CH4, at high temperatures, much more work is needed to understand the opacity and chemistry of atomic Na and K. The highly pressure broadened fundamental band of Na and K in the optical stretches into the near-infrared, strongly influencing the shape of the Y and K spectral bands. Since young giant planets are bright in these bands it is important to understand the influences on the spectral shape. Discerning gravity and atmospheric composition is difficult, if not impossible, without both good atomic opacities as well as an excellent understanding of the relevant atmospheric chemistry. Since Na and K condense at temperatures near 500 to 600 K, the chemistry of the condensation process must be well understood as well, particularly any disequilibrium chemical pathways. Comparisons of the current generation of sophisticated atmospheric models and available data, however, reveal important shortcomings in the models. We will review the current state of observations and theory of young giant planets and will discuss these and other specific examples where improved laboratory measurements for alkali compounds have the potential of substantially improving our understanding of these atmospheres.

chemistry of the condensation process↗
NASA NTRS2016

Characterizing the Atmosphere of a Young Planet

Since the discovery of the young, directly imaged planet 51 Eri b, its emergent spectrum has proved challenging to interpret. The initial discovery paper (Macintosh et al. 2015) interpreted the spectrum as indicative of a low mass (few Jupiter masses), effective temperature near 700 degrees Kelvin, and partial cloudiness. Subsequent observations in the K band, however, seem to invalidate the early models. In addition, newly improved photochemical data point to the likely presence of exotic haze species in the atmosphere. In my presentation I will explore the photochemistry of the atmosphere and discuss whether disequilibrium chemistry, hazes, clouds, or non-solar abundances of heavy elements may be responsible for the unusual spectrum of this planet. The implications for the interpretation of other young Jupiters in this mass and effective temperature range will also be considered.

51 Eri b↗
NASA NTRS2016

Near-Infrared Spectroscopy of the Y0 WISEP J173835.52+273258.9 and the Y1 WISE J035000.32-565830.2: the Importance of Non-Equilibrium Chemistry

We present new near-infrared spectra, obtained at Gemini Observatory, for two Y dwarfs: WISE J035000.32−565830.2 (W0350) and WISEP J173835.52+273258.9 (W1738). A FLAMINGOS-2 R = 540 spectrum was obtained for W0350, covering 1.0 < λ micrometer < 1.7, and a cross-dispersed GNIRS R = 2800 spectrum was obtained for W1738, covering 0.993 - 1.087 micrometer, 1.191 - 1.305 micrometer, 1.589 - 1.631 micrometer, and 1.985 - 2.175 micrometer, in four orders. We also present revised Y JH photometry for W1738, using new NIRI Y and J imaging, and a re-analysis of the previously published NIRI H band images. We compare these data, together with previously published data for late-T and Y dwarfs, to cloud-free models of solar metallicity, calculated both in chemical equilibrium and with disequilibrium driven by vertical transport. We find that for the Y dwarfs the non-equilibrium models reproduce the near-infrared data better than the equilibrium models. The remaining discrepancies suggest that fine-tuning the CH4/CO and NH3/N2 balance is needed. Improved trigonometric parallaxes would improve the analysis. Despite the uncertainties and discrepancies, the models reproduce the observed near-infrared spectra well. We find that for the Y0, W1738, T(sub eff) = 425 +/- 25K and log g = 4.0 +/- 0.25, and for the Y1, W0350, T(sub eff) = 350 +/- 25K and log g = 4.0 +/- 0.25. W1738 may be metal-rich. Based on evolutionary models, these temperatures and gravities correspond to a mass range for both Y dwarfs of 3 - 9 Jupiter masses, with W0350 being a cooler, slightly older, version of W1738; the age of W0350 is 0.3 - 3 Gyr, and the age of W1738 is 0.15 - 1 Gyr.

two Y dwarfs↗
NASA NTRS2015

Seasonal Variability of Saturn's Tropospheric Temperatures, Winds and Para-H2 from Cassini Far-IR Spectroscopy

Far-IR 16-1000 micrometer spectra of Saturn's hydrogen-helium continuum measured by Cassini's Composite Infrared Spectrometer (CIRS) are inverted to construct a near-continuous record of upper tropospheric (70-700 mbar) temperatures and para-H2 fraction as a function of latitude, pressure and time for a third of a saturnian year (2004-2014, from northern winter to northern spring). The thermal field reveals evidence of reversing summertime asymmetries superimposed onto the belt/zone structure. The temperature structure is almost symmetric about the equator by 2014, with seasonal lag times that increase with depth and are qualitatively consistent with radiative climate models. Localised heating of the tropospheric hazes (100-250 mbar) create a distinct perturbation to the temperature profile that shifts in magnitude and location, declining in the autumn hemisphere and growing in the spring. Changes in the para-H2 (f(sub p)) distribution are subtle, with a 0.02-0.03 rise over the spring hemisphere (200-500 mbar) perturbed by (i) low-f(sub p) air advected by both the springtime storm of 2010 and equatorial upwelling; and (ii) subsidence of high-f(sub p) air at northern high latitudes, responsible for a developing north-south asymmetry in f(sub p). Conversely, the shifting asymmetry in the para-H2 disequilibrium primarily reflects the changing temperature structure (and hence the equilibrium distribution of f(sub p)), rather than actual changes in f(sub p) induced by chemical conversion or transport. CIRS results interpolated to the same point in the seasonal cycle as re-analysed Voyager-1 observations (early northern spring) show qualitative consistency from year to year (i.e., the same tropospheric asymmetries in temperature and f(sub p)), with the exception of the tropical tropopause near the equatorial zones and belts, where downward propagation of a cool temperature anomaly associated with Saturn's stratospheric oscillation could potentially perturb tropopause temperatures, para-H2 and winds. Quantitative differences between the Cassini and Voyager epochs suggest that the oscillation is not in phase with the seasonal cycle at these tropospheric depths (i.e., it should be described as quasi-periodic rather than 'semi annual'). Variability in the zonal wind field derived from latitudinal thermal gradients is small (less than 10 m/s per scale height near the tropopause) and mostly affects the broad retrograde jets, with the notable exception of large variability on the northern flank of the equatorial jet. The meridional potential vorticity (PV) gradient, and hence the 'staircase of PV' associated with spatial variations in the vigour of vertical mixing, has varied over the course of the mission but maintained its overall shape. PV gradients in latitude and altitude are used to estimate the atmospheric refractive index for the propagation of stationary planetary (Rossby) waves, predicting that such wave activity would be confined to regions of real refractivity (tropical regions plus bands at 35-45 in both hemispheres). The penetration depth of these regions into the upper troposphere is temporally variable (potentially associated with stratification changes), whereas the latitudinal structure is largely unchanged over time (associated with the zonal jet system).

Fletcher, Leigh N.↗
NASA NTRS2016

The Effects of Consistent Chemical Kinetics Calculations on the Pressure-Temperature Profiles and Emission Spectra of Hot Jupiters

In this work we investigate the impact of calculating non-equilibrium chemical abundances consistently with the temperature structure for the atmospheres of highly-irradiated, close-in gas giant exoplanets. Chemical kinetics models have been widely used in the literature to investigate the chemical compositions of hot Jupiter atmospheres which are expected to be driven away from chemical equilibrium via processes such as vertical mixing and photochemistry. All of these models have so far used pressure-temperature (P-T) profiles as fixed model input. This results in a decoupling of the chemistry from the radiative and thermal properties of the atmosphere, despite the fact that in nature they are intricately linked. We use a one-dimensional radiative-convective equilibrium model, ATMO, which includes a sophisticated chemistry scheme to calculate P-T profiles which are fully consistent with non-equilibrium chemical abundances, including vertical mixing and photochemistry. Our primary conclusion is that, in cases of strong chemical disequilibrium, consistent calculations can lead to differences in the P-T profile of up to 100 K compared to the P-T profile derived assuming chemical equilibrium. This temperature change can, in turn, have important consequences for the chemical abundances themselves as well as for the simulated emission spectra. In particular, we find that performing the chemical kinetics calculation consistently can reduce the overall impact of non-equilibrium chemistry on the observable emission spectrum of hot Jupiters. Simulated observations derived from non-consistent models could thus yield the wrong interpretation. We show that this behaviour is due to the non-consistent models violating the energy budget balance of the atmosphere.

planets and satellites↗
NASA NTRS2014

Scientific Rationale for Saturn's in Situ Exploration

Remote sensing observations meet some limitations when used to study the bulk atmospheric composition of the giant planets of our solar system. A remarkable example of the superiority of in situ probe measurements is illustrated by the exploration of Jupiter, where key measurements such as the determination of the noble gases׳ abundances and the precise measurement of the helium mixing ratio have only been made available through in situ measurements by the Galileo probe. This paper describes the main scientific goals to be addressed by the future in situ exploration of Saturn placing the Galileo probe exploration of Jupiter in a broader context and before the future probe exploration of the more remote ice giants. In situ exploration of Saturn's atmosphere addresses two broad themes that are discussed throughout this paper: first, the formation history of our solar system and second, the processes at play in planetary atmospheres. In this context, we detail the reasons why measurements of Saturn's bulk elemental and isotopic composition would place important constraints on the volatile reservoirs in the protosolar nebula. We also show that the in situ measurement of CO (or any other disequilibrium species that is depleted by reaction with water) in Saturn's upper troposphere may help constraining its bulk O/H ratio. We compare predictions of Jupiter and Saturn's bulk compositions from different formation scenarios, and highlight the key measurements required to distinguish competing theories to shed light on giant planet formation as a common process in planetary systems with potential applications to most extrasolar systems. In situ measurements of Saturn's stratospheric and tropospheric dynamics, chemistry and cloud-forming processes will provide access to phenomena unreachable to remote sensing studies. Different mission architectures are envisaged, which would benefit from strong international collaborations, all based on an entry probe that would descend through Saturn's stratosphere and troposphere under parachute down to a minimum of 10 bar of atmospheric pressure. We finally discuss the science payload required on a Saturn probe to match the measurement requirements.

Galileo↗
NASA NTRS2018

Exoplanet Biosignatures: A Review of Remotely Detectable Signs of Life

In the coming years and decades, advanced space- and ground-based observatories will allow an unprecedented opportunity to probe the atmospheres and surfaces of potentially habitable exoplanets for signatures of life. Life on Earth, through its gaseous products and reflectance and scattering properties, has left its fingerprint on the spectrum of our planet. Aided by the universality of the laws of physics and chemistry, we turn to Earth's biosphere, both in the present and through geologic time, for analog signatures that will aid in the search for life elsewhere. Considering the insights gained from modern and ancient Earth, and the broader array of hypothetical exoplanet possibilities, we have compiled a comprehensive overview of our current understanding of potential exoplanet biosignatures, including gaseous, surface, and temporal biosignatures. We additionally survey biogenic spectral features that are well known in the specialist literature but have not yet been robustly vetted in the context of exoplanet biosignatures. We briefly review advances in assessing biosignature plausibility, including novel methods for determining chemical disequilibrium from remotely obtainable data and assessment tools for determining the minimum biomass required to maintain short-lived biogenic gases as atmospheric signatures. We focus particularly on advances made since the seminal review by Des Marais et al. The purpose of this work is not to propose new biosignature strategies, a goal left to companion articles in this series, but to review the current literature, draw meaningful connections between seemingly disparate areas, and clear the way for a path forward.

biosignatures↗
NASA NTRS2018

Modeling Clouds in Brown Dwarf and Exoplanet Giant Planet Atmospheres

Clouds and hazes are commonplace in the atmospheres of solar system planets and are likely ubiquitous in the atmospheres of extrasolar planets as well. Clouds affect every aspect of a planetary atmosphere, from the transport of radiation, to atmospheric chemistry, to dynamics and they influence - if not control - aspects such as surface temperature and habitability. In my presentations I aim to provide an introduction to the role and properties of clouds in exoplanetary atmospheres and will discuss the lessons learned from the past two decades of studying clouds in brown dwarf atmospheres. I will consider the role clouds play in influencing the spectra of extrasolar giant planets and will discuss the relative simple approaches that have been taken so far to model exoplanet clouds. I will also review how the scattering and extinction efficiencies of cloud particles may be approximated in certain limiting cases of small and large particles in order to facilitate physical understanding and will discuss the need for optimized cloud models that can be applied to exoplanet transmission spectra. Finally I will discuss the various sources of aerosol opacity, including photochemistry, disequilibrium chemistry, and equilibrium condensation.

Marley, Mark S.↗
NASA NTRS2019

Life's Requirements

Life on Earth is molecular in nature, with its lifelike attributes- e.g., information processing and catalysis- emerging as a result of both the specific properties of those molecules and the interactions among them. If this is a general model for life, then life must require (i) a source of energy, with which to build and sustain molecular complexity and information processing; (ii) elemental raw materials, from which to construct molecules having specific properties and reactivity; (iii)a solvent that supports the synthesis of the full range of molecules required by life and properly mediates the full range of necessary interactions among those molecules; and (iv) physicochemical conditions in which life's molecules can be synthesized, are appropriately stable, and can interact as needed for lifelike function. For life on Earth, these general requirements, respectively, take the specific form: (i) light energy in visible-to-near-infrared wavelengths or chemical energy as provided by oxidation–reduction disequilibrium, (ii) the "biogenic "elements (carbon, hydrogen, oxygen, nitrogen, phosphorus, and sulfur) (iii)liquid water, and (iv) specific ranges in temperature, pH, salinity, pressure, and other environmental factors. Our knowledge of these factors relates to cellula rlife as we observe it now or can infer from the fossil or molecular records. Life's origin may be constrained by a more stringent set of requirements that are, as yet,not fully understood.

Habitability↗
NASA NTRS2014

Methane, Carbon Monoxide, and Ammonia in Brown Dwarfs and Self-Luminous Giant Planets

We address disequilibrum abundances of some simple molecules in the atmospheres of solar composition brown dwarfs and self-luminous extrasolar giant planets using a kinetics-based 1D atmospheric chemistry model. Our approach is to use the full kinetics model to survey the parameter space with effective temperatures between 500 K and 1100 K. In all of these worlds equilibrium chemistry favors CH4 over CO in the parts of the atmosphere that can be seen from Earth, but in most disequilibrium favors CO. The small surface gravity of a planet strongly discriminates against CH4 when compared to an otherwise comparable brown dwarf. If vertical mixing is like Jupiter's, the transition from methane to CO occurs at 500 K in a planet. Sluggish vertical mixing can raise this to 600 K; clouds or more vigorous vertical mixing could lower this to 400 K. The comparable thresholds in brown dwarfs are 1100±100 K. Ammonia is also sensitive to gravity, but unlike CH4/CO, the NH3/N2 ratio is insensitive to mixing, which makes NH3 a potential proxy for gravity. HCN may become interesting in high gravity brown dwarfs with very strong vertical mixing. Detailed analysis of the CO-CH4 reaction network reveals that the bottleneck to CO hydrogenation goes through methanol, in partial agreement with previous work. Simple, easy to use quenching relations are derived by fitting to the complete chemistry of the full ensemble of models. These relations are valid for determining CO, CH4, NH3, HCN, and CO2 abundances in the range of self-luminous worlds we have studied but may not apply if atmospheres are strongly heated at high altitudes by processes not considered here (e.g., wave breaking).

Planets and satellites↗
NASA NTRS2020

Reconstructing Magma Storage Depths for the 2018 Kilauean Eruption from melt inclusion CO2 Contents: The importance of Vapor Bubbles

The 2018 Lower East Rift Zone (LERZ) eruption of Kīlauea Volcano and the accompanying collapse of the summit caldera marked the most destructive phase of activity on Hawai’i in the last 200 years. The integration of petrological data extracted from lava samples collected throughout the eruption with geodetic data examining the caldera collapse event, and estimates of the co-erupted flux of SO2 from the main eruptive fissure (Fissure 8), provides an exceptional opportunity to determine the reservoir geometry and magma transport paths supplying Kīlauea’s LERZ. The forsterite contents of erupted olivines and the degree of disequilibrium with their carrier melts indicate that two distinct olivine populations were erupted from Fissure 8. Melt inclusion entrapment pressures reveal that more evolved olivines (Fo<81.5) crystallized at ~2 km depth within the shallower Halema’uma’u reservoir, while more primitive olivines (Fo>81.5)crystallized within the deeper South Caldera reservoir at ~3–5 km depth. Crucially, primitive olivines experienced extensive post-entrapment crystallization, driving the growth of a vapor bubble. Raman spectroscopy reveals that this bubble contains up to 99% of the total inclusionCO2 budget (median=93%). Measurements of CO2 in only the glass phase would have underestimated entrapment depths by up to 60× (median=11×), and the importance of the SC reservoir as a source of magma to Fissure 8 would have been overlooked. Overall, we demonstrate that Raman measurements of bubbles, along with careful choice of suitably-calibrated H2O-CO2 solubility model, is vital to place accurate constraints on the depths of magma storage regions supplying volcanic eruptions.

SIMS↗
NASA NTRSDate not supplied

Thermodynamic and Diffusion Model Estimates on Metamorphic Temperatures and Timescales for Basaltic Eucrite GRA 98098

Introduction: HED meteorites are thought to rep-resent igneous rocks from Vesta’s basaltic crust and preserve evidence of early crustal metamorphism. Determining the temperatures and timescales of thermal metamorphism is important for reconstructing crustal evolution in the early solar system. Here, we study basaltic eucrite Graves Nunataks (GRA) 98098, which has been identified as a highly metamorphosed eucrite [1]. We present new estimates on metamorphic temperatures determined via thermodynamic modeling as well as the initial results from diffusion models constraining timescales of thermal metamorphism. Sample Description: GRA 98098 is an unbrecciated eucrite with a granoblastic plagioclase and pyroxene mineralogy. Millimeter to cm-long lathes of tridymite cross-cut and poikilitically enclose plagioclase and pyroxene [1,this work]. Pyroxene grains have exsolved into Ca-rich (~Wo38En29Fs33) and Ca-poor (~Wo4.5En36Fs59.5) lamellae. Both unzoned and zoned plagioclase grains are observed. Unzoned plagioclase grains are found solely with tridymite laths. These grains have ~An92 compositions. The cores of the zoned plagioclase grains have the same composition and thin, relatively sodic rims (~An67), (Fig. 1). The bulk sample is unusually enriched in highly in-compatible elements and has one of the most fractionated REE patterns reported [1]. Maximum metamorphic temperatures of 985±78°C have been estimated using two-pyroxene thermometry [2]. Methods: Thermodynamic modeling. Thermodynamic models were constructed using the software Perple_X, which employs a Gibbs free energy minimization in order to determine the most stable phase assemblage for a given bulk rock composition [3]. Bulk composition was calculated using mineral com-positions acquired via EMPA (this study) and the observed abundancies present in the thin section. Two bulk compositions were estimated; 1) includes all phases present in the thin section, (assumes that all phases are present during metamorphism), 2) excludes tridymite from the bulk calculation (assumes that tridymite was not present during metamorphism). In order to determine whether metamorphic equilibria was achieved and estimate temperatures of metamorphism, we compared measured pyroxene compositions with thermodynamically predicted compositions [4, Fig. 2]. Diffusion Modeling. Several time-temperature de-pendent diffusion profiles were calculated in order to determine the best match for XAn chemical profiles observed at the edges of the zoned plagioclase (Fig. 3). We assumed that the start condition was a stepwise gradient at the plagioclase/pyroxene interface. We also assumed an average diffusion coefficient (D) and a constant temperature using the equation in [5]. D was determined for two temperatures (T = 1060ºC; near eucrite solidus [6] and T = 985ºC; metamorphism reported in [4]) and then XAn was calculated as a function of distance from plagioclase core to rim using an error function solution to Fick’s second law. Results: Thermodynamic model results are summarized in Fig. 2. For a bulk composition that includes all phases in the thin section, pyroxene endmember compositions plot in the following temperature ranges: Fs ~660-860ºC, En~1000ºC & 1150ºC, and Wo~760-900ºC (Fig. 2a). For a bulk composition that excludes tridymite from the peak metamorphic assemblage (i.e., the bulk composition minus the contribution from tridymite), a temperature range could not be determined for the Fs component of pyroxene. For Wo, T~760-900ºC and En, T~1000ºC & 1150ºC (Fig. 2b). Fig. 3 summarizes the diffusion model results. For T = 1060°C & 985°C, the most appropriate time interval was estimated based on which diffusion curve most matched (solid lines, Fig. 3) the EMPA data. For T = 1060°C, the best looking match was t = 500 ka. For T = 985°C, the best match was t = 7 Ma. Discussion and future work: Temperature estimates from thermodynamic models are not conclusive because the temperature ranges determined for pyroxene endmember stability do not overlap (colored fields in Fig. 2), thus implying that there is disequilibrium between pyroxene crystals and the bulk composition considered [4]. Thus, additional exploration is needed to define a metamorphically equilibrated do-main that accurately records peak temperature. The utility of defining metamorphically equilibrated do-mains to improve the accuracy and level of detail elucidated regarding the petrogenetic history of metamorphose samples has been demonstrated previously [4,7]. We suggest that in the case of Fig. 2a, the thin section composition is not representative of the length scales over which metamorphic equilibrium was achieve and in the case of Fig. 2b, the assumption that tridymite was not present during metamorphism was incorrect. However, results from thermodynamic models can provide insight into the relative timing of mineral and compositional textures. For example from texture alone, it is unclear whether tridymite was igneous in origin and represents the last bits of melt in a crystallizing magma chamber, or if it formed during (and possibly initiated) open system thermal metamorphism. The latter could be consistent with a partial melt hypothesis [8,9] while the former implies that simple fractional crystallization can yield the textures present in GRA 98098. The lack of coincidence be-tween pyroxene endmember compositions in Fig. 2b suggest that the bulk composition minus tridymite was not the assemblage in equilibrium with the pyroxene, suggesting that tridymite was present during metamorphism and formed during igneous crystallization. We conclude that the development of the Na-rich plagioclase rims likely occurred during or immediately after peak thermal metamorphism, because eucrites of similar metamorphic grade and texture have unzoned plagioclase (~An92) [2,4,8], and Na zoning is only observed in the plagioclase not included in the tridymite. This suggests that the zoning formed after tridymite formation, and therefore after igneous crystallization. Thus, the timescales calculated via diffusion modeling possibly represent the time interval over which thermal metamorphism occurred. Cooling rates approximated for the Vestan crust predict that the crust cooled below 300°C around 35-40 Ma after formation[10]. This is consistent with our modeling results that predict formation of the Na rich plagioclase rims occurring at higher temperatures over a period of 0.5 to 7 Ma years. Future work. Additional thermodynamic modeling work will focus on selecting an equilibrated bulk rock domain in which to elucidate metamorphic conditions. Diffusion models currently provide a minimum time-scale, since diffusion slows down as the system cools. Future work with will focus on integrating cooling into the diffusion models and constraining the depth at which thermal metamorphism occurs because it could be used to determine whether the range of time-scales calculated for thermal metamorphism are consistent with the geologic environment.

J S Gorce↗
NASA NTRSDate not supplied

Assessing Organic Preservation and the Implications for Potential Biosignatures in the Bastide Member of the Séítah Formation, Jezero Crater

Introduction: Olivine has the highest CO2 trapping potential of ultramafic minerals, due to its rapid rate of dissolution and high percentage of divalent cations/unpolymerized silicate tetrahedra [1]. It generates divalent carbonates from CO2 and sequesters CO2 into the mineral matrix of the target lithology. The co-occurrence of olivine and carbonate within abraded targets from the Bastide Member of the Séítah Formation (Fm) of the Jezero crater floor [2] suggests the carbonation of olivine occurred within the mineral matrix hosted in a subsurface system. Hydrothermal origins for the subsurface system are hypothesized from orbital data [3]. This is supported by the detection of hydration features within the rock as well as the carbonate features are solely detected within the abrasion patch but not the rock’s surface. Organic preservation potential of abrasion patches: We incorporated the SHERLOC/WATSON results acquired from the Dourbes, Garde, and Quartier abrasion patches in the Séítah Fm to investigate the organomineral associations, and determine the biosignature preservation potential of these rocks. Dourbes is dominated by olivine and has minor amounts of carbonate, hydrated Ca-sulfate, and amorphous or microcrystalline silicate. Fluorescence features (330-340 nm) are detected in discrete locales and could be consistent with double ring aromatic organic molecules; yet, these features do not appear to be associated with an identified mineral phase. Dark subhedral to euhedral olivine grains within the Garde abrasion patch often co-occur with carbonate-consistent spectral signatures in all analyzed scans. The availability of Fe2+ is a known influence on olivine dissolution rates [1] and SuperCam estimates of the olivine composition (Forsterite-60 average for Sols 202-234) may thereby provide a constraint on the carbonation extent. Carbonated olivine phenocrysts within the matrix may be due to aqueous alteration, as the carbonation of nodules is consistent with observations in other hydrothermal systems and within Martian meteorites (ALH84001) [4]. In comparison, the Quartier abrasion patch represents an extensively altered endmember within the Bastide Member of the Séítah Fm. It contains a fluorescence doublet at 305/325 nm that coexists with multiple species of Na-sulfate and Mg-sulfate, Mg-carbonates, olivine [5]. Aqueous alteration and implications for habitability: The identification of primary and secondary mineral phases observed in the Bastide Member suggests the release of cations from primary ultramafic minerals through aqueous alteration. Within Garde, the carbonate detected appears to be Mg-rich and likely formed from the in situ alteration of Mg-rich olivine within the region as carbonate has only been detected within the rock via in situ analysis. Carbonates derived from abiotic and biotic reactions preserve biosignatures (i.e. indices of habitability) on Earth. The detected carbonate phase found in association with fluorescent features within the rock matrix may also indicate potential organic compounds preserved in a putative hydrothermal system. Fluorescent features (~330 nm) are unique to Garde and Dourbes, though they are co-located to carbonate signatures solely within Garde, and between the light toned minerals. Identification of these fluorescent features may be consistent with 1-2 ring aromatic compounds. The limit of detection for Raman is multiple orders of magnitude greater than the limit of detection required for fluorescence [6]. Implications for provenance: Hydrothermal systems represent disequilibrium chemical conditions that are hypothesized to have supported the emergence of life and also preserve ancient carbon within precipitated carbonates [7]. Hydrothermal system associated carbonates are capable of preserving biosignatures up to an estimated ~3.77 – 4.28 Gya [8]. Thus, carbonated olivine found within the Séítah Fm may represent a high-potential biosignature preserving environment on Mars. The formation of carbonates by an aqueous alteration process, such as carbonation of olivine is also consistent with hypotheses for carbonate within the greater regional-olivine bearing unit [2,3], which contains Garde, Dourbes, and Quartier. Acknowledgments: This work was carried out at the Jet Propulsion Laboratory, The California Institute of Technology under a contract from NASA. References: [1] Wood et al., (2019) ES&T, 6, 10. [2] Stack, K. et al., (2020) Space Sci Rev, 216, 127. [3] Tarnas, J. et al., (2021) JGR: Planets, 126, 11. [4] Steele et al., (2007) Meteorit. Planet. Sci., 42, 9. [5] Murphy, A.E. et al., (2022) LPSC [6] Bhartia et al., (2021) Space Sci Rev, 217, 58. [7] Luther (2021) GRL, 48, e2021GL094869. [8] Dodd et al., (2017) Nature, 543, 60-64

E L Cardarelli↗
NASA NTRS2020

Machiite, Al2Ti3O9, A New Oxide Mineral from the Murchison Carbonaceous Chondrite: A New Ultra-refractory Phase From the Solar Nebula

Machiite (IMA 2016-067), Al2Ti3O9, is a new mineral that occurs as a single euhedral crystal, 4.4 mm in size, in contact with an euhedral corundum grain, 12 mm in size, in a matrix of the Murchison CM2 carbonaceous chondrite. The mean chemical composition of holotype machiite by electron probe microanalysis is (wt%) TiO2 59.75, Al2O3 15.97, Sc2O3 10.29, ZrO2 9.18, Y2O3 2.86, FeO 1.09, CaO 0.44, SiO2 0.20, MgO 0.10, total 99.87, giving rise to an empirical formula (based on 9 oxygen atoms pfu) of (Al1.17Sc0.56Y0.10Ti4+0.08Fe0.06Ca0.03Mg0.01)(Ti4+2.71Zr0.28Si0.01)O9. The general formula is (Al,Sc)2(Ti4+,Zr)3O9. The end-member formula is Al2Ti3O9. Machiite has the C2/c schreyerite-type structure with a = 17.10 Å, b = 5.03 Å, c = 7.06 Å, b = 107°, V = 581 Å3, and Z = 4, as revealed by electron backscatter diffraction. The calculated density using the measured composition is 4.27 g/cm3. The machiite crystal is highly 16O-depleted relative to the coexisting corundum grain (D17O = –0.2 ± 2.4‰ and –24.1 ± 2.6‰, respectively; where D17O = d17O – 0.52 × d18O). Machiite is a new member of the schreyerite (V2Ti3O9) group and a new Sc,Zr-rich ultrarefractory phase formed in the solar nebula, either by gas-solid condensation or as a result of crystallization from a Ca,Al-rich melt having solar-like oxygen isotopic composition (D17O ~ –25‰) under high-temperature (~1400–1500 °C) and low-pressure (~10-4–10-5 bar) conditions in the CAI-forming region near the protosun. The currently observed disequilibrium oxygen isotopic composition between machiite and corundum may indicate that machiite subsequently experienced oxygen isotopic exchange with a planetary-like 16O-poor gaseous reservoir either in the solar nebula or on the CM chondrite parent body. The name machiite is in honor of Chi Ma, mineralogist at California Institute of Technology, for his contributions to meteorite mineralogy and discovery of many new minerals representing extreme conditions of formation.

Alexander N Krot↗
NASA NTRS2020

Machiite, Al2Ti3O9, a New Oxide Mineral from the Murchison Carbonaceous Chondrite: A New Ultra-refractory Phase from the Solar Nebula

Machiite (IMA 2016-067), Al2Ti3O9, is a new mineral that occurs as a single euhedral crystal, 4.4 mm in size, in contact with an euhedral corundum grain, 12 mm in size, in a matrix of the Murchison CM2 carbonaceous chondrite. The mean chemical composition of holotype machiite by electron probe microanalysis is (wt%) TiO2 59.75, Al2O3 15.97, Sc2O3 10.29, ZrO2 9.18, Y2O3 2.86, FeO 1.09, CaO 0.44, SiO2 0.20, MgO 0.10, total 99.87, giving rise to an empirical formula (based on 9 oxygen atoms pfu) of (Al1.17Sc0.56Y0.10Ti4+0.08Fe0.06Ca0.03Mg0.01)(Ti4+2.71Zr0.28Si0.01)O9. The general formula is (Al,Sc)2(Ti4+,Zr)3O9. The end-member formula is Al2Ti3O9. Machiite has the C2/c schreyerite-type structure with a = 17.10 Å, b = 5.03 Å, c = 7.06 Å, b = 107°, V = 581 Å3, and Z = 4, as revealed by electron backscatter diffraction. The calculated density using the measured composition is 4.27 g/cm3. The machiite crystal is highly 16O-depleted relative to the coexisting corundum grain (D17O = –0.2 ±2.4‰ and –24.1 ± 2.6‰, respectively; where D17O = d17O – 0.52 ×d18O). Machiite is a new member of the schreyerite (V2Ti3O9) group and a new Sc,Zr-rich ultrarefractory phase formed in the solar nebula, either by gas-solid condensation or as a result of crystallization from a Ca, Al-rich melt having solar-like oxygen isotopic composition (D17O ~ –25‰) under high-temperature (~1400–1500 °C) and low-pressure (~10-4–10-5 bar) conditions in the CAI-forming region near the protosun. The currently observed disequilibrium oxygen isotopic composition between machiite and corundum may indicate that machiite subsequently experienced oxygen isotopic exchange with a planetary-like 16O-poor gaseous reservoir either in the solar nebula or on the CM chondrite parent body. The name machiite is in honor of Chi Ma, mineralogist at California Institute of Technology, for his contributions to meteorite mineralogy and discovery of many new minerals representing extreme conditions of formation.

Machiite↗