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Mercury’s depletion in O and abundance of S substituting in as S2- has fundamental effects on the physicochemical properties of minerals and melts because O2- is the dominant rock-forming anion. These changes exert a first order effect on planetary body evolution, including the initial distribution of elements, crystallization paths, stability of phases, and mineral chemistry. Experimental and empirical data have revealed that most nominally lithophile elements become more chalcophile and/or siderophile at reducing conditions, which can be visualized through a re-interpreted Goldschmidt classification table prepared for McCubbin & Anzures’s Treatises of Geochemistry 3rd edition chapter under review. Additionally, the S bonding environment influences Mercurian phase equilibria by decreasing the stability of forsterite and anorthite while increasing the stability of enstatite, silica, and albite through re-projection of silicate ternaries.

Introduction: Future Artemis missions aim to return the volatile-bearing samples collected near lunar polar craters. We, as advanced curation scientists, are responsible for developing techniques and methodologies for preserving the integrity of returned samples and the science value those samples contain. The extent to which that preservation is possible, and the trade-offs preservation requires (e.g. monetary costs, sample volume limitations) all must be considered. Even less-than pristine volatile-bearing samples will be of tremendous value to the scientific community seeking to unravel the history of lunar surface volatiles and, more broadly, volatiles in the solar system. A sample collected on the lunar surface will experience at least five distinctive periods during which any changes here referred to as “alteration” will certainly occur at some scale: collection on the lunar surface; transportation back to Earth; long-term storage; curatorial processing; and allocation/distribution. The Planetary Exploration and Astromaterials Research Lab (PEARL) seeks to understand temperature and pressure effects on returned volatile samples by working with high-fidelity volatile-containing regolith simulants, setting the foundation for the future of cold curation. This abstract is focused on gas-surface interactions between LCROSS volatiles and readily available lunar regolith simulants. Experiments involved analyzing differences in headspace gas composition for various combinations of volatile and regolith simulants using gas chromatography/mass spectrometry (GC/MS). Experimental Procedure: The volatile simulants were chosen based on the molecules detected during the LCROSS mission.1 Stock solutions of condensed lunar volatile analytes were: methanol, 7 N ammonia in methanol, and 0.4% hydrogen sulfide in water. The regolith simulants used were primarily JSC-1A and NU-LHT-4M. Additional regolith simulant control studies were conducted with <150 μm sieved sand and KBr. A nested vial sample preparation approach separated the liquid stock solutions from the regolith, eliminating potential matrix effects between liquid and solid phases. Fifteen microliter aliquots of liquid volatile simulants were added to a 2 mL liquid GC vial and capped in atmosphere. An 18G needle punctured the 2 mL GC vial immediately before being transferred and sealed in a 20 mL GC vial containing 0-0.3 g of regolith simulant, see Figure 1. Separating the analytes ensures any changes observed in the total headspace gases is a result of gas-surface and/or gas-gas interactions. Equipment and Method: Initial GC/MS method development for the separation and identification of relevant headspace gases can be found in Amick, et al. 2023.2 The only hardware change is a different column: a TG-1701MS 30 m × 0.25 mm × 1.00 μm column. The vials were sampled at 10°C, room temperature (~25°C) and 50°C. Low temperature samples were kept in a chilled autosampler stage for at least 1 hour prior to sampling. High temperature samples were agitated at 50°C for 5 minutes immediately prior to injection onto the column. Headspace chromatograms were collected for each combination of temperature, regolith, and volatile simulant, including controls without one or both types of analytes, in triplicate. The chromatogram elution window for each analyte or significant atmospheric gas was identified using the peak mass spectrum cross-referenced with Figure 1.Picture of the nested vial set-up. a NIST MS library search. Each analyte peak was integrated after filtering the mass spectrum trace for the parent or most unique mass-to-charge ratio. For example, the mass-to-charge ratio used to identify, filter for, and integrate the carbon dioxide peak was centered around 44 m/z. Results: Figure 2 shows the integrated peak area for hydrogen sulfide in all combinations of regolith simulants, temperatures, and the addition of ammonia in methanol solution. Multiple repeat experiments with H2S and regolith simulants have confirmed hydrogen sulfide is removed from the headspace within 1 hour when exposed to JSC-1A, NU-LHT-4M and sand (not pictured). The consumption of H2S by lunar regolith simulants at different temperatures indicates surface chemistry will be an integral component in sample integrity and preservation. It is important to note that while the effect of surface chemistry on gaseous hydrogen sulfide is intriguing, further investigation into more chemically accurate regolith simulants is necessary and ongoing. The sulfur in hydrogen sulfide is in its most reduced state while off-the-shelf, terrestrially sourced JSC-1A and NU-LHT-4M are more oxidized than most lunar materials,3which likely leads to different oxidation-reduction reactions than would be expected in lunar regolith. Figure 3 shows the integrated peak area of carbon dioxide for each sample combination that contained ammonia in methanol solution. The addition of ammonia to the GC vials results in a consistent and reproducible decrease in carbon dioxide gas, even at 50°C. The effect became more pronounced when JSC-1A or NU-LHT-4M were present. This set of experiments demonstrated that the sample composition will affect the chemical and physical state of each component present. Future spectroscopic and microscopy experiments will be geared towards identifying the cause for the CO2(g) concentration decrease and the consumption of hydrogen sulfide. As cold and volatile curation scientists, this information provides necessary insight on how to appropriately handle and analyze volatile bearing returned samples, as well as predict the effect chemical composition has on the various sample phases we will analyze upon return to Earth. Unlike traditional curation of geologic materials, the molecules in a sample cannot be identified or processed using the naked eye or even an optical microscope. Volatile curation will require a combination of analytical techniques, including but not limited to highly sensitive gas and solid/condensed phase spectroscopy. This set of experiments has demonstrated the need for more detailed studies of volatile mixtures with mineralogically and geochemically analogous lunar regolith simulants to prepare for the curation of volatile-rich lunar samples from the south polar region of the Moon. References: [1] Colaprete, A., et al. (2010) Science, 330, (463-468). [2] Amick, C. L., et al.(2023) Houston, Texas, [3] Heiken, G. H., et al.(1991) (778-778)

Recently, continuum Microkinetic Rate Theory (cMRT) has been advanced as a method of studying rates of systems, where deviations between observation and cMRT theory have been found, and it hypothesized that these deviations are linked either to oscillations or fluctuations. Multinomial probability theory (MPT) is used to derive analytical expressions for concentration fluctuations, giving the fluctuations as a function of average concentrations and sample sizes. MPT predictions of fluctuations in kinetically constrained systems are verified against kinetic Monte Carlo, and it analytically shown that MPT predicts canonical and grand canonical ensemble fluctuations. These fluctuation results are discussed in conjunction with cMRT deviations and it argued that fluctuations are not responsible for the deviations., Comment: 9 pages of text, 5 figures

Colossal Ion Conductivity (CIC) is the phenomenon in which large changes in oxygen conductivity are observed when a solid state oxygen electrolyte is placed in a heterolayer super lattice. Several hypotheses have been posed concerning both structural changes of the ion conducting material and of the ion conducting mechanism. The posed structural hypotheses are oxygen sub lattice melting, phase change of the ion conducting material, and that the heterolayer environment does not induce a phase change of the ion conducting material. The posed mechanistic hypotheses are disorder, mechanics, and space charge. Here, first principles molecular dynamics and statics of the ion conducting interface are performed providing evidence that under CIC conditions no sub lattice melting nor phase change has occurred and that the electrolyte remains unchanged. A discussion of the posed mechanistic hypotheses is given and cast as a series of mathematical statements. When these hypotheses are compared with first principles calculations and literature results, they fail to capture CIC; a new alternative dipole hypothesis is offered, which also fails to capture CIC; further analysis of the literature points to CIC being an interface mediated phenomenon, similar to grain boundary diffusion, where the operando mechanism remain unclear., Comment: 9 pages of text, 4 figures, 4 tables, 2 pages of supplementary information, presented at the electrochemical society

Sequential neural networks models are powerful tools in a variety of Natural Language Processing (NLP) tasks. The sequential nature of these models raises the questions: to what extent can these models implicitly learn hierarchical structures typical to human language, and what kind of grammatical phenomena can they acquire? We focus on the task of agreement prediction in Basque, as a case study for a task that requires implicit understanding of sentence structure and the acquisition of a complex but consistent morphological system. Analyzing experimental results from two syntactic prediction tasks -- verb number prediction and suffix recovery -- we find that sequential models perform worse on agreement prediction in Basque than one might expect on the basis of a previous agreement prediction work in English. Tentative findings based on diagnostic classifiers suggest the network makes use of local heuristics as a proxy for the hierarchical structure of the sentence. We propose the Basque agreement prediction task as challenging benchmark for models that attempt to learn regularities in human language., Comment: Accepted to "Analyzing and interpreting neural networks for NLP" workshop at EMNLP 2018

In this paper, the application of hierarchical wireless sensor networks in water quality monitoring is investigated. Adopting a hierarchical structure, the set of sensors is divided into multiple clusters where the value of the sensing parameter is almost constant in each cluster. The members of each cluster transmit their sensing information to the local fusion center (LFC) of their corresponding cluster, where using some fusion rule, the received information is combined, and then possibly sent to a higher-level central fusion center (CFC). A two-phase processing scheme is also envisioned, in which the first phase is dedicated to detection in the LFC, and the second phase is dedicated to estimation in both the LFC and the CFC. The focus of the present paper is on the problem of decision fusion at the LFC: we propose hard- and soft-decision maximum a posteriori (MAP) algorithms, which exhibit flexibility in minimizing the total cost imposed by incorrect detections in the first phase. The proposed algorithms are simulated and compared with conventional fusion techniques. It is shown that the proposed techniques result in lower cost. Furthermore, when the number of sensors or the amount of contamination increases, the performance gap between the proposed algorithms and the existing methods also widens., Comment: 7 pages, 8 figures, ICCE2012