Stepwise heating of lunar anorthosites 60025, 60215, 65315 possibly reveals an indigenous noble gas component on the Moon

Despite extensive effort during the last four decades, no clear signature of a lunar indigenous noble gas component has been found. In order to further investigate the possible occurrence of indigenous volatiles in the Moon, we have re-analyzed the noble gas and nitrogen isotopic compositions in three anorthosite samples. Lunar anorthosites 60025, 60215 and 65315 have the lowest exposure duration (∼2 Ma) among Apollo samples and consequently contain only limited cosmogenic (e.g. ^(124,126)Xe) and solar wind (SW) noble gases. Furthermore, anorthosites have negligible contributions of fissiogenic Xe isotopes because of their very low Pu and U contents. As observed in previous studies (Lightner and Marti, 1974; Leich and Niemeyer, 1975), lunar anorthosite Xe presents an isotopic composition very close to that of terrestrial atmospheric Xe, previously attributed to “anomalous adsorption” of terrestrial Xe after sample return. The presumed atmospheric Xe contamination can only be removed by heating the samples at medium to high temperatures under vacuum, and is therefore different from common adsorption. To test this hypothesis, we monitored the adsorption of Xe onto lunar anorthositic powder using infrared reflectance spectroscopy. A clear shift in the anorthosite IR absorbance peaks is detected when comparing the IR absorbance spectra of the lunar anorthositic powder before and after exposure to a neutral Xe-rich atmosphere. This observation accounts for the chemical bonding (chemisorption) of Xe onto anorthosite, which is stronger than the common physical bonding (physisorption) and could account for the anomalous adsorption of Xe onto lunar samples. Our high precision Xe isotope analyses show slight mass fractionation patterns across ^(128–136)Xe isotopes with systematic deficits in the heavy Xe isotopes (mostly ^(136)Xe and marginally ^(134)Xe) that have not previously been observed. This composition could be the result of mixing between an irreversibly adsorbed terrestrial contaminant that is mostly released at high temperature and an additional signature. Solar Wind (SW) Xe contents, estimated from SW-Ne and SW-Ar concentrations and SW-Ne/Ar/Xe elemental ratios, do not support SW as the additional contribution. Using a χ^2 test, the latter is best accounted for by cometary Xe as measured in the coma of Comet 67P/Churyumov-Gerasimenko (Marty et al., 2017) or by the primordial U-Xe composition inferred to be the precursor of atmospheric Xe (Pepin, 1994; Avice et al., 2017). It could have been contributed to the lunar budget by volatile-rich bodies that participated to the building of the terrestrial atmosphere inventory (Marty et al., 2017)

The Holy Grail: A road map for unlocking the climate record stored within Mars' polar layered deposits

In its polar layered deposits (PLD), Mars possesses a record of its recent climate, analogous to terrestrial ice sheets containing climate records on Earth. Each PLD is greater than 2 ​km thick and contains thousands of layers, each containing information on the climatic and atmospheric state during its deposition, creating a climate archive. With detailed measurements of layer composition, it may be possible to extract age, accumulation rates, atmospheric conditions, and surface activity at the time of deposition, among other important parameters; gaining the information would allow us to “read” the climate record. Because Mars has fewer complicating factors than Earth (e.g. oceans, biology, and human-modified climate), the planet offers a unique opportunity to study the history of a terrestrial planet’s climate, which in turn can teach us about our own planet and the thousands of terrestrial exoplanets waiting to be discovered. During a two-part workshop, the Keck Institute for Space Studies (KISS) hosted 38 Mars scientists and engineers who focused on determining the measurements needed to extract the climate record contained in the PLD. The group converged on four fundamental questions that must be answered with the goal of interpreting the climate record and finding its history based on the climate drivers. The group then proposed numerous measurements in order to answer these questions and detailed a sequence of missions and architecture to complete the measurements. In all, several missions are required, including an orbiter that can characterize the present climate and volatile reservoirs; a static reconnaissance lander capable of characterizing near surface atmospheric processes, annual accumulation, surface properties, and layer formation mechanism in the upper 50 ​cm of the PLD; a network of SmallSat landers focused on meteorology for ground truth of the low-altitude orbiter data; and finally, a second landed platform to access ~500 ​m of layers to measure layer variability through time. This mission architecture, with two landers, would meet the science goals and is designed to save costs compared to a single very capable landed mission. The rationale for this plan is presented below. In this paper we discuss numerous aspects, including our motivation, background of polar science, the climate science that drives polar layer formation, modeling of the atmosphere and climate to create hypotheses for what the layers mean, and terrestrial analogs to climatological studies. Finally, we present a list of measurements and missions required to answer the four major questions and read the climate record. 1. What are present and past fluxes of volatiles, dust, and other materials into and out of the polar regions? 2. How do orbital forcing and exchange with other reservoirs affect those fluxes? 3. What chemical and physical processes form and modify layers? 4. What is the timespan, completeness, and temporal resolution of the climate history recorded in the PLD

Photophysical pore control in an azobenzene- containing metal-organic framework †

The synthesis and structure of an azobenzene functionalized isoreticular metal-organic framework (azo-IRMOF-74-III) [Mg 2 (C 26 H 16 O 6 N 2 )] are described and the ability to controllably release a guest from its pores in response to an external stimulus has been demonstrated. Azo-IRMOF-74-III is an isoreticular expansion of MOF-74 with an etb topology and a 1-D hexagonal pore structure. The structure of azo-IRMOF-74-III is analogous to that of MOF-74, as demonstrated by powder X-ray diffraction, with a surface area of 2410 m 2 g À1 BET. Each organic unit within azo-IRMOF-74-III is decorated with a photoswitchable azobenzene unit, which can be toggled between its cis and trans conformation by excitation at 408 nm. When propidium iodide dye was loaded into the MOF, spectroscopic studies showed that no release of the luminescent dye was observed under ambient conditions. Upon irradiation of the MOF at 408 nm, however, the rapid wagging motion inherent to the repetitive isomerization of the azobenzene functionality triggered the release of the dye from the pores. This light-induced release of cargo can be modulated between an on and an off state by controlling the conformation of the azobenzene with the appropriate wavelength of light. This report highlights the ability to capture and release small molecules and demonstrates the utility of self-contained photoactive switches located inside highly porous MOFs

The Need for Laboratory Measurements and Ab Initio Studies to Aid Understanding of Exoplanetary Atmospheres

We are now on a clear trajectory for improvements in exoplanet observations that will revolutionize our ability to characterize their atmospheric structure, composition, and circulation, from gas giants to rocky planets. However, exoplanet atmospheric models capable of interpreting the upcoming observations are often limited by insufficiencies in the laboratory and theoretical data that serve as critical inputs to atmospheric physical and chemical tools. Here we provide an up-to-date and condensed description of areas where laboratory and/or ab initio investigations could fill critical gaps in our ability to model exoplanet atmospheric opacities, clouds, and chemistry, building off a larger 2016 white paper, and endorsed by the NAS Exoplanet Science Strategy report. Now is the ideal time for progress in these areas, but this progress requires better access to, understanding of, and training in the production of spectroscopic data as well as a better insight into chemical reaction kinetics both thermal and radiation-induced at a broad range of temperatures. Given that most published efforts have emphasized relatively Earth-like conditions, we can expect significant and enlightening discoveries as emphasis moves to the exotic atmospheres of exoplanets.Comment: Submitted as an Astro2020 Science White Pape

The Holy Grail: A road map for unlocking the climate record stored within Mars' polar layered deposits

In its polar layered deposits (PLD), Mars possesses a record of its recent climate, analogous to terrestrial ice sheets containing climate records on Earth. Each PLD is greater than 2 ​km thick and contains thousands of layers, each containing information on the climatic and atmospheric state during its deposition, creating a climate archive. With detailed measurements of layer composition, it may be possible to extract age, accumulation rates, atmospheric conditions, and surface activity at the time of deposition, among other important parameters; gaining the information would allow us to “read” the climate record. Because Mars has fewer complicating factors than Earth (e.g. oceans, biology, and human-modified climate), the planet offers a unique opportunity to study the history of a terrestrial planet’s climate, which in turn can teach us about our own planet and the thousands of terrestrial exoplanets waiting to be discovered. During a two-part workshop, the Keck Institute for Space Studies (KISS) hosted 38 Mars scientists and engineers who focused on determining the measurements needed to extract the climate record contained in the PLD. The group converged on four fundamental questions that must be answered with the goal of interpreting the climate record and finding its history based on the climate drivers. The group then proposed numerous measurements in order to answer these questions and detailed a sequence of missions and architecture to complete the measurements. In all, several missions are required, including an orbiter that can characterize the present climate and volatile reservoirs; a static reconnaissance lander capable of characterizing near surface atmospheric processes, annual accumulation, surface properties, and layer formation mechanism in the upper 50 ​cm of the PLD; a network of SmallSat landers focused on meteorology for ground truth of the low-altitude orbiter data; and finally, a second landed platform to access ~500 ​m of layers to measure layer variability through time. This mission architecture, with two landers, would meet the science goals and is designed to save costs compared to a single very capable landed mission. The rationale for this plan is presented below. In this paper we discuss numerous aspects, including our motivation, background of polar science, the climate science that drives polar layer formation, modeling of the atmosphere and climate to create hypotheses for what the layers mean, and terrestrial analogs to climatological studies. Finally, we present a list of measurements and missions required to answer the four major questions and read the climate record. 1. What are present and past fluxes of volatiles, dust, and other materials into and out of the polar regions? 2. How do orbital forcing and exchange with other reservoirs affect those fluxes? 3. What chemical and physical processes form and modify layers? 4. What is the timespan, completeness, and temporal resolution of the climate history recorded in the PLD

Unlocking the Climate Record Stored within Mars’ Polar Layered Deposits

In the icy beds of its polar layered deposits (PLD), Mars likely possesses a record of its recent climate history, analogous to terrestrial ice sheets that contain records of Earth's past climate. Both northern and southern PLDs store information on the climatic and atmospheric state during the deposition of each layer (WPs: Becerra et al.; Smith et al). Reading the climate record stored in these layers requires detailed measurements of layer composition, thickness, isotope variability, and near-surface atmospheric measurements. We identify four fundamental questions that must be answered in order to interpret this climate record and decipher the recent climatic history of Mars: 1. Fluxes: What are the present and past fluxes of volatiles, dust, and other materials into and out of the polar regions? 2. Forcings: How do orbital/axial forcing and exchange with other reservoirs affect those fluxes? 3. Layer Processes: What chemical and physical processes form and modify layers? 4. Record: What is the timespan, completeness, and temporal resolution of the climate history recorded in the PLD? In a peer reviewed report (1), we detailed a sequence of missions, instruments, and architecture needed to answer these questions. Here, we present the science drivers and a mission concept for a polar lander that would enable a future reading of the past few million years of the Martian climate record. The mission addresses as-yet-unachieved science goals of the current Decadal Survey and of MEPAG for obtaining a record of Mars climate and has parallel goals to the NEXSAG and ICE-SAG reports

High-fidelity Reaction Kinetic Modeling of Hot-Jupiter Atmospheres Incorporating Thermal and UV Photochemistry Enhanced by Metastable CO(a3Π)

A detailed modeling of simultaneous UV-photochemical and thermochemical processes in exoplanet atmosphere-like conditions is essential for the analysis and interpretation of a vast amount of current and future spectral data from exoplanets. However, a detailed reaction kinetic model that incorporates both UV photochemistry and thermal chemistry is challenging due to the massive size of the chemical system as well as the lack of understanding of photochemistry compared to thermal-only chemistry. Here, we utilize an automatic chemical reaction mechanism generator to build a high-fidelity thermochemical reaction kinetic model later then incorporated with UV photochemistry enhanced by metastable triplet-state carbon monoxide (a ^3 Π). Our model results show that two different photochemical reactions driven by Ly α photons (i.e., H _2 + CO(a ^3 Π) → H + HCO and CO(X ^1 Σ ^+ ) + CO(a ^3 Π) → C( ^3 P) + CO _2 ) can enhance thermal chemistry resulting in significant increases in the formation of CH _4 , H _2 O, and CO _2 in H _2 -dominated systems with trace amounts of CO, which qualitatively matches the observations from previous experimental studies. Our model also suggests that at temperatures above 2000 K, thermal chemistry becomes the dominant process. Finally, the chemistry simulated up to 2500 K does not produce any larger species such as C _3 species, benzene, or larger (i.e., PAHs). This might indicate that the photochemistry of C _2 species such as C _2 H _2 might play a key role in the formation of organic aerosols observed in a previous experimental study

Comparison of Titan’s atmospheric and surface organic aerosols in the infrared spectral regions

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