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In Situ Identification of Reaction Intermediates and Mechanistic Understandings of Methane Oxidation over Hematite: A Combined Experimental and Theoretical Study

Effective methane utilization for either clean power generation or value-added chemical production has been a subject of growing attention worldwide for decades, yet challenges persist mostly in relation to methane activation under mild conditions. Here, we report hematite, an earth-abundant material, to be highly effective and thermally stable to catalyze methane combustion at low temperatures (<500 °C) with a low light-off temperature of 230 °C and 100% selectivity to CO 2 . The reported performance is impressive and comparable to those of precious-metal-based catalysts, with a low apparent activation energy of 17.60 kcal·mol –1 . Our theoretical analysis shows that the excellent performance stems from a tetra-iron center with an antiferromagnetically coupled iron dimer on the hematite (110) surface, analogous to that of the methanotroph enzyme methane monooxygenase that activates methane at ambient conditions in nature. Isotopic oxygen tracer experiments support a Mars van Krevelen redox mechanism where CH 4 is activated by reaction with a hematite surface oxygen first, followed by a catalytic cycle through a molecular-dioxygen-assisted pathway. Surface studies with in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT) calculations reveal the evolution of reaction intermediates from a methoxy CH 3 –O–Fe, to a bridging bidentate formate b-HCOO–Fe, to a monodentate formate m-HCOO–Fe, before CO 2 is eventually formed via a combination of thermal hydrogen-atom transfer (HAT) and proton-coupled electron transfer (PCET) processes. Finally, the elucidation of the reaction mechanism and the intermediate evolutionary profile may allow future development of catalytic syntheses of oxygenated products from CH 4 in gas-phase heterogeneous catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The s process in massive stars, a benchmark for neutron capture reaction rates

A clear definition of the contribution from the slow neutron-capture process (s process) to the solar abundances between Fe and the Sr-Zr region is a crucial challenge for nuclear astrophysics. Robust s-process predictions are necessary to disentangle the contribution from other stellar processes producing elements in the same mass region. Nuclear uncertainties are affecting s-process calculations, but most of the needed nuclear input are accessible to present nuclear experiments or they will be in the near future. Neutron-capture rates have a great impact on the s process in massive stars, which is a fundamental source for the solar abundances of the lighter s-process elements heavier than Fe (weak s-process component). In this work we present a new nuclear sensitivity study to explore the impact on the s process in massive stars of 86 neutron-capture rates, including all the reactions between C and Si and between Fe and Zr. We derive the impact of the rates at the end of the He-burning core and at the end of the C-burning shell, where the 22 Ne(α,n) 25 Mg reaction is is the main neutron source. We confirm the relevance of the light isotopes capturing neutrons in competition with the Fe seeds as a crucial feature of the s process in massive stars. For heavy isotopes we study the propagation of the neutron-capture uncertainties, finding a clear difference of the impact of Fe and Co isotope rates with respect to the rates of heavier stable isotopes. The local uncertainty propagation due to the neutron-capture rates at the s-process branching points is also considered, discussing the example of 85 Kr. The complete results of our study for all the 86 neutron-capture rates are available online. Finally, we present the impact on the weak s process of the neutron-capture rates included in the new ASTRAL library (v0.2).

79 ASTRONOMY AND ASTROPHYSICS↗

Sorption of noble gases by solids, with reference to meteorites. II - Chromite and carbon. III - Sulfides, spinels, and other substances; on the origin of planetary gases

The trapping of noble gases by chromite and carbon, two putative carriers of primordial noble gases in meteorites, was studied by synthesizing 19 samples in a Ne-Ar-Kr-Xe atmosphere at 440-720 K. Noble gas contents are found to approximately obey Henry's Law, but only slight correlations are found with composition, surface area, or adsorption temperature. Geometric mean distribution coefficients for bulk samples and HCl residues in 10 cu cm STP/g atm are: Xe 100, Kr 15, Ar 3.5, and Ne 0.62. Elemental fractionation data support the suggestion of Lewis et al. (1977) that chromite and carbon in C2 and C3 chondrites were formed by the reaction: Fe, Cr + 4CO yields (Fe, Cr)3O4 + 4C + carbides. In contrast to meteoritic minerals, the synthetic specimens show no isotopic fractionation of noble gases. In a subsequent study, attention is given to the cases of sulfides and spinels, on the way to consideration of the origin of planetary gases. Sulfides showed three distinctive trends relative to chromite or magnetite. The elemental fractionation pattern of Ar, Kr and Xe in meteorites, terrestrial rocks and planets resembles the adsorption patterns on the carbons, spinels, sulfides, and other solids studied. The high release temperature of meteoritic noble gases may be explained by transformation of the physisorbed or chemisorbed gas. The ready loss of meteoritic heavy gases on surficial oxidation is consistent with adsorption, as is the high abundance.

Yang, J.↗

Sm-Nd Age and Nd- and Sr- Isotopic Evidence for the Petrogenesis of Dhofar 378

Dhofar 378 (hereafter Dho 378) is one of the most ferroan lithologies among martian meteorites, resembling the Los Angeles basaltic shergottite in lithology and mineral chemistry, although it is more highly shocked than Los Angeles. All plagioclase (Pl) grains in the original lithology were melted by an intense shock in the range 55-75 GPa. Clinopyroxenes (Cpx) sometimes show mosaic extinction under a microscope showing that they, too, experienced intense shock. Nevertheless, they zone from magnesian cores to ferroan rims, reflecting the original lithology. Cpx grains also often contain exsolution lamellae, showing that the original lithology cooled slowly enough for the lamellae to form. Because all plagioclase grains were melted by the intense shock and subsequently quenched, the main plagioclase component is glass (Pl-glass) rather than maskelynite. Like Los Angeles, but unlike most basaltic shergottites, Dho 378 contains approximately equal modal abundances of Cpx and Pl-glass. The grain sizes of the original minerals were comparatively large (approximately 1 mm). The original plagioclase zoning has been severely modified. Following shock melting, the plagioclase melts crystallized from the outside inward, first forming outer rims of Cpx-Pl intergrowths (approximately 10 micrometers) followed by inner rims (10's to 100 micrometers) of An(sub 40-50) feldspar, and finally Pl-gl cores of compositions An(sub 33-50) with orthoclase compositions up to Or(sub 12).

Nyquist, L. E.↗

Generative models for simulation of KamLAND-Zen

Abstract The next generation of searches for neutrinoless double beta decay ($$0 \nu \beta \beta $$ 0 ν β β ) are poised to answer deep questions on the nature of neutrinos and the source of the Universe’s matter–antimatter asymmetry. They will be looking for event rates of less than one event per ton of instrumented isotope per year. To claim discovery, accurate and efficient simulations of detector events that mimic$$0 \nu \beta \beta $$ 0 ν β β is critical. Traditional Monte Carlo (MC) simulations can be supplemented by machine-learning-based generative models. This work describes the performance of generative models that we designed for monolithic liquid scintillator detectors like KamLAND to produce accurate simulation data without a predefined physics model. We present their current ability to recover low-level features and perform interpolation. In the future, the results of these generative models can be used to improve event classification and background rejection by providing high-quality abundant generated data.

Physics↗

Abundances and Transients from Neutron Star–White Dwarf Mergers

Abstract We systematically investigate the mergers of neutron star–white dwarf binaries from beginning to end, with a focus on the properties of the inflows and outflows in accretion disks and their electromagnetic emissions. Using population synthesis models, we determine a subset of these binaries in which the white dwarf companion undergoes unstable mass transfer and complete tidal disruption, forming a large accretion disk around the neutron star. The material evolves according to a one-dimensional advection-dominated accretion-disk model with nuclear burning, neutrino emissions, and disk-surface wind ejection. The extreme dynamics of the entire process have proven difficult to analyze, and thus currently, the properties are poorly understood. The outflows from the mergers are iron- and nickel-rich, giving rise to optical and infrared emissions powered by the decay of the radioactive iron-type isotopes, calculated via the SuperNu light-curve code. We find these systems capable of powering bright, yet short-lived, optical transients with the potential to power gamma-ray bursts.

79 ASTRONOMY AND ASTROPHYSICS↗

Lunar and Planetary Science XXXVI, Part 19

The topics include: 1) The abundances of Iron-60 in Pyroxene Chondrules from Unequilibrated Ordinary Chondrites; 2) LL-Ordinary Chondrite Impact on the Moon: Results from the 3.9 Ga Impact Melt at the Landing Site of Appolo 17; 3) Evaluation of Chemical Methods for Projectile Identification in Terrestrial and Lunar Impactites; 4) Impact Cratering Experiments in Microgravity Environment; 5) New Achondrites with High-Calcium Pyroxene and Its implication for Igneous Differentiation of Asteroids; 6) Climate History of the Polar Regions of Mars Deduced form Geologic Mapping Results; 7) The crater Production Function for Mars: A-2 Cumulative Power-Law Slope for Pristine Craters Greater than 5 km in Diameter Based on Crater Distribution for Northern Plains Materials; 8) High Resolution Al-26 Chronology: Resolved Time Interval Between Rim and Interior of a Highly Fractionated Compact Type a CAI from Efremovka; 9) Assessing Aqueous Alteration on Mars Using Global Distributions of K and Th; 10) FeNi Metal Grains in LaPaz Mare Basalt Meteorites and Appolo 12 Basalts; 11) Unique Properties of Lunar Soil for In Situ Resource Utilization on the Moon; 12) U-Pb Systematics of Phosphates in Nakhlites; 13) Measurements of Sound Speed in Granular Materials Simulated Regolith; 14) The Effects of Oxygen, Sulphur and Silicon on the Dihedral Angles Between Fe-rich Liquid Metal and Olivine, Ringwoodite and Silicate Perovskite: Implications for Planetary Core Formation; 15) Seismic Shaking Removal of Craters 0.2-0.5 km in Diameter on Asteroid 433 Eros; 16) Focused Ion Beam Microscoopy of ALH84001 Carbonate Disks; 17) Simulating Micro-Gravity in the Laboratory; 18) Mars Atmospheric Sample Return Instrument Development; 19) Combined Remote LIBS and Raman Spectroscopy Measurements; 20) Unusual Radar Backscatter Properties Along the Northern Rim of Imbrium Basin; 21) The Mars Express/NASAS Project at JPL; 22) The Geology of the Viking 2 Lander Site Revisited; 23) An Impact Genesis for Loki Patera? 24) Mars Polar Cap Edges Tracked over 3 Full Mars Years; 25) Elemental Abundance in Presolar SiC: Comparing Grains Separated by Acid Residue and Gently Separation Procedures; 26) First Results from the Descent Imager/Spectral Radiometer (DISR) Experiment on the Huygens Entry Probe of Titan; 27) Minor Element Behavior of Pallasite Olivine: Understanding Pallasite Thermal History and Chronology; 28) Canonical Anorthite in a Grosnaja Forsterite-bearing CAI; 29) Experimental Evidence for Condensation of 'Astrophysical' Carbonate; 30) Distribution and Classification of Multiple Coronae on Venus; 31) Recognition of Rayed Craters on Mars in THEMIS Thermal Infrared Imagery: Implications for Martian Meteorite Source Regions; 32) Geochemical Modeling of Evaporites on Mars: Insight from Meridiani Planum; 33) Hadean Crustal Processes Revealed from Oxygen Isotopes and U-Th-Pb Depth Profiling of Pre-4.0 Ga Detrital Zircons from Western Australia; 34) On Modeling the Seepage of Water into the Martian Subsurface; 35) Martial Gullies and Groundwater: A Series of Unfortunate Exceptions; 36) Olivine and Carbonate Globules in ALH84001: A Terrestrial Analog, and Implications for Water on Mars; 37) A Reevaluation of Mass Movements Within the Valles Marineris Region of Mars Using MOLA and MOC Data; 38) Evidence of Hydrated 109P/Swift-Tuttle Meteoroids from Meteor Spectroscopy; 39) Cr-54 Anomalies in the Solar System: Their Extent and Origin; 40) Reevaluation of the Mn-53-Cr-53 Systematic in the Basaltic Achondrites; 41) Effective Liquid Metal-Silicate Mixing Upon Shock by Power-Law Droplet Size Scaling in Richtmyer-Meshkov Like Perturbations; 42) Post-Impact Deformation of Impact Craters: Towards a Better Understanding Through the Study of Mjolnir Crater; 43) Cutting Silica Aerogel for Particle Extraction; 44) Liquid Hydrocarbons on Titan's Surface? How Cassini ISS Observations Fit into the Story (So Far); and 45) Mesoscale Simulations of Polar Circulations: Late Spring to Late Summe

Source record↗

The isotopic composition of hydrogen and helium in low energy cosmic rays

The Caltech Electron/Isotope Spectrometer on IMP-7 has been used to identify the isotopes H-2 and He-3 in low energy cosmic rays during solar quiet periods from October 1972 to October 1974. These observations cover the energy intervals 5 to 29 MeV/nuc for H-2 and 7 to 50 MeV/nuc for He-3. The energy spectra of H-1, H-2, and He-3 all fall rapidly with decreasing energy, giving H-2/H-1 and He-3/H-1 ratios essentially independent of energy as expected from adiabatic acceleration. The measured He-4 spectrum, however, was essentially flat over this energy interval, and therefore the H-2/He-4 ratio observed at 1 AU is not simply related to the interstellar abundances of these nuclei. However, comparisons of the H-2/H-1 and He-3/H-1 ratios with calculated spectra are possible.

Mewaldt, R. A.↗

Elemental GCR Observations during the 2009-2010 Solar Minimum Period

Using observations from the Cosmic Ray Isotope Spectrometer (CRIS) onboard the Advanced Composition Explorer (ACE), we present new measurements of the galactic cosmic ray (GCR) elemental composition and energy spectra for the species B through Ni in the energy range approx. 50-550 MeV/nucleon during the record setting 2009-2010 solar minimum period. These data are compared with our observations from the 1997-1998 solar minimum period, when solar modulation in the heliosphere was somewhat higher. For these species, we find that the intensities during the 2009-2010 solar minimum were approx. 20% higher than those in the previous solar minimum, and in fact were the highest GCR intensities recorded during the space age. Relative abundances for these species during the two solar minimum periods differed by small but statistically significant amounts, which are attributed to the combination of spectral shape differences between primary and secondary GCRs in the interstellar medium and differences between the levels of solar modulation in the two solar minima. We also present the secondary-to-primary ratios B/C and (Sc+Ti+V)/Fe for both solar minimum periods, and demonstrate that these ratios are reasonably well fit by a simple "leaky-box" galactic transport model that is combined with a spherically symmetric solar modulation model.

Solar Modulation↗

Assessing Ceres’ Past and Current Habitability

Dwarf planet Ceres is a compelling target as an evolved ocean world with, at least, regional brine reservoirs and potentially ongoing geological activity. Situated in the Main Belt of asteroids, Ceres is the most water-rich body in the inner solar system (in relative abundance) and is accessible enough for a sample return with the resources of a typical medium-class (New Frontiers) NASA mission. NASA’s Dawn mission at Ceres revealed the presence of liquid, brine-driven activity, organic matter, and a rich salt chemistry. With this evidence, the overarching goals of the mission concept presented herein are to quantify Ceres’ current habitability potential and origin. A sample return from young evaporite deposits in Occator crater offers greater science return than an in situ exploration mission by enabling high-resolution analysis of (1) organic matter expected from terrestrial and chondritic analogs that are trapped in salt minerals and (2) isotopes of refractory elements for a similar cost and less science risk. The sample return concept would be executed with a single flight system due to Ceres’ relative proximity to Earth and low gravity. Solar electric propulsion was identified as the most cost-effective approach for getting to Ceres and back. De-orbiting, landing, and takeoff are performed with a throttleable monopropellant hydrazine system. The solar arrays are stowed prior to landing and takeoff. Sample acquisition builds on the pneumatic system designed by Honeybee Robotics. The sample return mission concept relies on the availability of key technologies: an enhanced landing vision system leveraging investments from Mars 2020; retractable/redeployable solar arrays, which have been demonstrated on the International Space Station but not at Ceres’ gravity; and an emerging design from upcoming missions for sample transfer from the pneumatic sampling system to the sample return capsule. Return of a sample of mass ~100 g from Ceres, maintained at ≤ -20°C, is without precedent for any currently advocated Ocean World mission, enabling a vast range of experimental techniques back on Earth with sensitivities and accuracies far beyond those feasible with in situ instruments. A sample of this size also enables analyses to benefit from techniques that will become available in the future.

Casillas, Raul Polit↗

He, Xe and Ne isotopes in a steady-state mass transport model and implications about terrestrial volatiles

We present a model of the steady-state transport assuming three reservoirs: a lower mantle (P) with a relatively undepleted inventory of U, Th, Pu, I, He, Ne, Xe, Ar; an upper mantle that has been extensively outgassed (D); and the atmosphere. There is mass transport at a rate M(sub PD) by plumes from the lower mantle, a fraction of which is outgassed directly into the atmosphere, while the remainder feeds matter and associated nuclei into D. D is well outgassed at spreading centers and has material containing atmospheric gases added to it by subduction. In the case of He, there is no subduction component. The approach follows the treatment of Kellogg and Wasserburg. A summary of the pertinent equations and constraints was reported earlier. The U, Th and Pu in P are estimated for Earth models from refractory element abundances in meteorites. In this model the inventory of rare gases in D is governed by the simple mixing of components from P (both radiogenic and original) with distinctive atmospheric components. In addition, alpha decay and spontaneous fission of U, and (alpha, n) reaction on oxygen from energetic alpha particles produce radiogenic/nuclear daughter products in D. These include (4)He, (136)Xe and (21)Ne. (40)K in D generates excess radiogenic (40)Ar.

Wasserburg, G. J.↗

Calibration of the Quadrupole Mass Spectrometer of the Sample Analysis at Mars Instrument Suite

The SAM suite of instruments on the "Curiosity" Rover of the Mars Science Laboratory (MSL) is designed to provide chemical and isotopic analysis of organic and inorganic volatiles for both atmospheric and solid samples. The mission of the MSL investigations is to advance beyond the successful search for aqueous transformation in surface environments at Mars toward a quantitative assessment of habitability and preservation through a series of chemical and geological measurements. The SAM suite was delivered in December 2010 (Figure 1) to the Jet Propulsion Laboratory for integration into the Curiosity Rover. We previously outlined the range of SAM solid and gas calibrations implemented or planned and here we discuss a specific set of calibration experiments to establish the response of the SAM Quadrupole Mass Spectrometer (QMS) to the four most abundant gases in the Martian atmosphere CO2, N2, Ar, and O2, A full SAM instrument description and calibration report is presently in preparation.

Mahaffy, P. R.↗

SULI Intern Final Report: Computationally Investigating Hydrogen Thermo-Diffusion in Yttrium Hydride Using Multiscale Methods

The renaissance of nuclear energy has arrived, heralding an age of abundant inexpensive clean energy, and renewed space exploration. In nuclear-powered spacecraft and microreactors, safety and size are of utmost importance. Yttrium Hydride (YHx) is being researched for its utility as a neutron moderator in nuclear reactors; the hydrogen in YHx slows down neutrons, enabling a continuous nuclear reaction in the reactor. This has the benefit of allowing reactors to be more safe, compact, and efficient. The goal of this effort is to computationally predict the coefficient of temperature-dependent hydrogen diffusion within YHx, the Soret coefficient. This parameter is essential for determining the safe operating modes of YHx moderators. Zirconium Hydride (ZrHx) is used in the Training, Research, Isotopes, General Atomics (TRIGA) reactor, is the reference material for these calculations. In this work, nanoscale atomic modeling in the Vienna Ab initio Simulation Package (VASP) is combined with the mesoscale finite element phase-field module in the Multiphysics Object-Oriented Simulation Environment (MOOSE); this culminates in a new multiscale computational method to simulate Soret diffusion of hydrogen in YHx. This data is useful for predicting experimental outcomes. This workflow involves convergence testing followed by static, Nudged Elastic Band (NEB), Quasi-Harmonic Approximation (QHA), and Molecular Dynamics (MD) calculations - linked with phase field simulation. NEB simulates hydrogen migration, while QHA and MD predict temperature-dependent properties. The static calculations align with literature, and preliminary NEB and QHA calculations yield accurate results. Once the atomic calculations are complete, we will incorporate Electron Backscatter Diffraction (EBSD) images and VASP-generated parameters into the phase field module to simulate intra- and intergranular transport of hydrogen in ZrHx and YHx. Future research will extend our approach to fuel-moderator materials systems such as Uranium-Yttrium Hydride (U-YHx). This work contributes to the development of advanced nuclear energy solutions for space travel.

36 - MATERIALS SCIENCE↗

Petrography and Origin of the Unique Achondrite GRA 06128 and 06129: Preliminary Results

GRA 06128 & 06129 are paired achondrites [1], with unique mineral proportions (75% oligoclase), mineral compositions, and oxygen isotope ratios. They appear to represent alkalic igneous rock from a hitherto unsampled differentiated parent body, modified significantly by thermal and shock metamorphism. Samples and Methods: Bulk samples were examined at JSC during splitting for consortium analyses. Microscope and BSE images here are on thick section GRA06128,40. Chemical analyses of minerals were acquired at Johnson Space Center with the Cameca SX100, operated at 15 kV. Feldspar was analyzed with a defocused 5 micron beam @ 5 nA; other minerals were analyzed with a focused beam @ 20 nA. Moessbauer spectra were obtained at ARES, JSC [2]. Intrinsic radioactivity was measured in the low-level counting facility at ARES JSC [3]. An estimated abundance of Al-26 of approx. 70 dpm/kg is within the range determined for eucrites.

Treiman, A. H.↗

Early Archean spherule beds of possible impact origin from Barberton, South Africa: A detailed mineralogical and geochemical study

The Barberton Greenstone belt is a 3.5- to 3.2-Ga-old formation situated in the Swaziland Supergroup near Barberton, northeast Transvaal, South Africa. The belt includes a lower, predominantly volcanic sequence, and an upper sedimentary sequence (e.g., the Fig Tree Group). Within this upper sedimentary sequence, Lowe and Byerly identified a series of different beds of spherules with diameters of around 0.5-2 mm. Lowe and Byerly and Lowe et al. have interpreted these spherules to be condensates of rock vapor produced by large meteorite impacts in the early Archean. We have collected a series of samples from drill cores from the Mt. Morgan and Princeton sections near Barberton, as well as samples taken from underground exposures in the Sheba and Agnes mines. These samples seem much better preserved than the surface samples described by Lowe and Byerly and Lowe et al. Over a scale of just under 30 cm, several well-defined spherule beds are visible, interspaced with shales and/or layers of banded iron formation. Some spherules have clearly been deposited on top of a sedimentary unit because the shale layer shows indentions from the overlying spherules. Although fresher than the surface samples (e.g., spherule bed S-2), there is abundant evidence for extensive alteration, presumably by hydrothermal processes. In some sections of the cores sulfide mineralization is common. For our mineralogical and petrographical studies we have prepared detailed thin sections of all core and underground samples (as well as some surface samples from the S-2 layer for comparison). For geochemical work, layers with thicknesses in the order of 1-5 mm were separated from selected core and underground samples. The chemical analyses are being performed using neutron activation analysis in order to obtain data for about 35 trace elements in each sample. Major elements are being determined by XRF and plasma spectrometry. To clarify the history of the sulfide mineralization, sulfur isotopic compositions are being determined.

Koeberl, Christian↗

The Th and U abundances in chondritic meteorites

We present new analyses of Th-232/U-238 in CI and CM meteorites. The relative abundance of these nuclides is important in estimates of the age of r-process elements. The cosmochronology based upon the Th-232/U-238 ratio (kappa) depends on the precise determinations of these two different elements in meteorites and on the production ratios. Both parameters are subject to substantial errors. Recent recalculations of this chronology have used selected values from compilations but do not adequately address the errors in terms of a reliable data base. Morgan and Lovering provided extensive neutron activation analyses for ordinary chondrites which yield an average kappa of 3.6 +/- 0.4. Their work on carbonaceous chondrites showed a wide range in kappa from 2 to 6. More recent investigations by isotopic dilution have established the following: (1) highly variable kappa from 2.7 to 11 in Allende Ca-Al-rich inclusions and a value of 3.6 in the Orgueil CI1 chondrite; (2) a range from 2.71 to 6.63 for 7 L-type chondrites and a range from 2.7 to 4.4 for 6 L, H, and LL chondrites. A further investigation of this subject matter is presented.

Chen, J. H.↗

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↗

Exhaustive Product Analysis of Three Benzene Discharges by Microwave Spectroscopy

Using chirped and cavity microwave spectroscopies, automated double resonance, new high-speed fitting and deep learning algorithms, and large databases of computed structures, the discharge products of benzene alone, or in combination with molecular oxygen or nitrogen, have been exhaustively characterized between 6.5 and 26 GHz. In total, more than 3300 spectral features were observed; 89% of these, accounting for 97% of the total intensity, have now been assigned to 152 distinct chemical species and 60 of their variants (i.e., isotopic species and vibrationally excited states). Roughly 50 of the products are entirely new or poorly characterized at high resolution, including many heavier by mass than the precursor benzene. These findings provide direct evidence for a rich architecture of two- and three-dimensional carbon and indicate that benzene growth, particularly the formation of ring–chain molecules, occurs facilely under our experimental conditions. The present analysis also illustrates the utility of microwave spectroscopy as a precision tool for complex mixture analysis, irrespective of whether the rotational spectrum of a product species is known a priori or not. From this large quantity of data, for example, it is possible to determine with confidence the relative abundances of different product masses, but more importantly the relative abundances of different isomers with the same mass. We review the complementary nature of this type of analysis to traditional mass spectrometry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗