Thermodynamics of Element Volatility and its Application to Planetary Processes

Despite its importance in geological sciences, our understanding of interactions between gas and condensed phases (comprising solids and liquids) remains clouded by the fact that, often, only indirect evidence remains for their occurrence. This arises from the tendency for the vapour phase to escape from the condensed phase with which it interacts, owing to its much lower density and thus greater volume. For a gas that is sufficiently tenuous that interactions do not occur between its constituent molecules, this relationship is quantified in the ideal gas law (Clapeyron 1834): $PV=nRT$ (1) where $P$ is the total pressure exerted by the gas, $V$ its volume, $n$ is the number of moles, $R$ the gas constant 8.3145 $Jmol^{-1}K^{-1}$, Horstmann, 1873) and $T$ the absolute temperature. One mole of an ideal gas at 273.15 $K$ and $10^5$ $Pa$ (standard temperature and pressure for gases) has a molar volume of 22,711 $cm^3/mol$, $10^3$ x greater than typical silicate liquids or minerals. As a result, vaporisation processes in nature are often informed by chemical and textural evidence remaining in the condensed phase.Comment: 95 pages 19 figures 5 table

Retention of water in terrestrial magma oceans and carbon-rich early atmospheres

Massive steam and CO$_2$ atmospheres have been proposed for magma ocean outgassing of Earth and terrestrial planets. Yet formation of such atmospheres depends on volatile exchange with the molten interior, governed by volatile solubilities and redox reactions. We determine the evolution of magma ocean--atmosphere systems for a range of oxygen fugacities, C/H ratios and hydrogen budgets that include redox reactions for hydrogen (H$_2$--H$_2$O), carbon (CO--CO$_2$), methane (CH$_4$), and solubility laws for H$_2$O and CO$_2$. We find that small initial budgets of hydrogen, high C/H ratios, and oxidizing conditions, suppress outgassing of hydrogen until the late stage of magma ocean crystallization. Hence early atmospheres in equilibrium with magma oceans are dominantly carbon-rich, and specifically CO-rich except at the most oxidizing conditions. The high solubility of H$_2$O limits its outgassing to melt fractions below $\sim$30\%, the fraction at which the mantle transitions from vigorous to sluggish convection with melt percolation. Sluggish melt percolation could enable a surface lid to form, trapping water in the interior and thereby maintaining a carbon-rich atmosphere (equilibrium crystallization). Alternatively, efficient crystal settling could maintain a molten surface, promoting a transition to a water-rich atmosphere (fractional crystallization). However, additional processes, including melt trapping and H dissolution in crystallizing minerals, further conspire to limit the extent of H outgassing, even for fractional crystallization. Hence, much of the water delivered to planets during their accretion can be safely harbored in their interiors during the magma ocean stage, particularly at oxidizing conditions.Comment: 35 pages, 16 figures, accepted version in The Planetary Science Journa

VapoRock: Thermodynamics of vaporized silicate melts for modeling volcanic outgassing and magma ocean atmospheres

Silicate vapors play a key role in planetary evolution, especially dominating early stages of rocky planet formation through outgassed magma ocean atmospheres. Our open-source thermodynamic modeling software "VapoRock" combines the MELTS liquid model (Ghiorso et al., 1995) with gas-species properties from multiple thermochemistry tables (e.g., Chase et al., 1998). VapoRock calculates the partial pressures of 34 gaseous species in equilibrium with magmatic liquid in the system Si-Mg-Fe-Al-Ca-Na-K-Ti-Cr-O at desired temperatures and oxygen fugacities (fO2, or partial pressure of O2). Comparison with experiments shows that pressures and melt-oxide activities (which vary over many orders of magnitude) are reproduced to within a factor of ~3, consistent with measurement uncertainties. We also benchmark the model against a wide selection of igneous rock compositions including bulk silicate Earth, predicting elemental vapor abundances that are comparable (Na, Ca, & Al) or more realistic (K, Si, Mg, Fe, & Ti) than those of the closed-source MAGMA code (with maximum deviations by factors of 10-300 for K & Si). Vapor abundances depend critically on the activities of liquid components. The MELTS model underpinning VapoRock was calibrated and extensively tested on natural igneous liquids. In contrast, MAGMA's liquid model assumes ideal mixtures of a limited set of chemically simplified pseudo-species, which only roughly approximates the non-ideal compositional interactions typical of many-component natural silicate melts. Finally, we explore how relative abundances of SiO and SiO2 provide a spectroscopically measurable proxy for oxygen fugacity in devolatilized exoplanetary atmospheres, potentially constraining fO2 in outgassed exoplanetary mantles

Study of a convergent subsetized list-mode EM reconstruction algorithm

Abstract-We have implemented a convergent subsetized (CS) list-mode reconstruction algorithm, based on previous work [1]- [3] on complete-data OS-EM reconstruction. The first step of the convergent algorithm is exactly equivalent (unlike the histogrammode case) to the regular subsetized list-mode EM algorithm, while the second and final step takes the form of additive updates in image space. A hybrid algorithm based on the ordinary and the convergent algorithms is also proposed, and is shown to combine the advantages of the two algorithms: it is able to reach a higher image quality in fewer iterations while maintaining the convergent behavior, making the hybrid approach a good alternative to the ordinary subsetized list-mode EM algorithm. Reconstructions using various LOR-driven projection techniques (Siddon method, trilinear and bilinear interpolation) were considered and it was demonstrated that in terms of FWHM, the Siddon technique is inferior to the other two algorithms, with the bilinear interpolation technique performing nearly similarly as the trilinear while being considerably faster

Measuring dopaminergic function in the 6-OHDA-lesioned rat: a comparison of PET and microdialysis

BACKGROUND: [(18) F]fluorodopa (FDOPA) positron emission tomography (PET) allows assessment of levodopa (LDOPA) metabolism and is widely used to study Parkinson's disease. We examined how [(18) F]FDOPA PET-derived kinetic parameters relate the dopamine (DA) and DA metabolite content of extracellular fluid measured by microdialysis to aid in the interpretation of data from both techniques. METHODS: [(18) F]FDOPA PET imaging and microdialysis measurements were performed in unilaterally 6-hydroxydopamine-lesioned rats (n = 8) and normal control rats (n = 3). Microdialysis testing included baseline measurements and measurements following acute administration of LDOPA. PET imaging was also performed using [(11)C]dihydrotetrabenazine (DTBZ), which is a ligand for the vesicular monoamine transporter marker and allowed assessment of denervation severity. RESULTS: The different methods provided highly correlated data. Lesioned rats had reduced DA metabolite concentrations ipsilateral to the lesion (p < 0.05 compared to controls), with the concentration being correlated with FDOPA's effective distribution volume ratio (EDVR; r = 0.86, p < 0.01) and DTBZ's binding potential (BP(ND); r = 0.89, p < 0.01). The DA metabolite concentration in the contralateral striatum of severely (>80%) lesioned rats was lower (p < 0.05) than that of less severely lesioned rats (<80%) and was correlated with the ipsilateral PET measures (r = 0.89, p < 0.01 for BP(ND)) but not with the contralateral PET measures. EDVR and BP(ND) in the contralateral striatum were not different from controls and were not correlated with the denervation severity. CONCLUSIONS: The demonstrated strong correlations between the PET and microdialysis measures can aid in the interpretation of [(18) F]FDOPA-derived kinetic parameters and help compare results from different studies. The contralateral striatum was affected by the lesioning and so cannot always serve as an unaffected control

Standardized approach to extract candidate outcomes from literature for a standard outcome set:a case- and simulation study

Aims: Standard outcome sets enable the value-based evaluation of health care delivery. Whereas the attainment of expert opinion has been structured using methods such as the modified-Delphi process, standardized guidelines for extraction of candidate outcomes from literature are lacking. As such, we aimed to describe an approach to obtain a comprehensive list of candidate outcomes for potential inclusion in standard outcome sets. Methods: This study describes an iterative saturation approach, using randomly selected batches from a systematic literature search to develop a long list of candidate outcomes to evaluate healthcare. This approach can be preceded with an optional benchmark review of relevant registries and Clinical Practice Guidelines and data visualization techniques (e.g. as a WordCloud) to potentially decrease the number of iterations. The development of the International Consortium of Health Outcome Measures Heart valve disease set is used to illustrate the approach. Batch cutoff choices of the iterative saturation approach were validated using data of 1000 simulated cases. Results: Simulation showed that on average 98% (range 92–100%) saturation is reached using a 100-article batch initially, with 25 articles in the subsequent batches. On average 4.7 repeating rounds (range 1–9) of 25 new articles were necessary to achieve saturation if no outcomes are first identified from a benchmark review or a data visualization. Conclusion: In this paper a standardized approach is proposed to identify relevant candidate outcomes for a standard outcome set. This approach creates a balance between comprehensiveness and feasibility in conducting literature reviews for the identification of candidate outcomes.</p

Liquid Xenon Detectors for Positron Emission Tomography

PET is a functional imaging technique based on detection of annihilation photons following beta decay producing positrons. In this paper, we present the concept of a new PET system for preclinical applications consisting of a ring of twelve time projection chambers filled with liquid xenon viewed by avalanche photodiodes. Simultaneous measurement of ionization charge and scintillation light leads to a significant improvement to spatial resolution, image quality, and sensitivity. Simulated performance shows that an energy resolution of <10% (FWHM) and a sensitivity of 15% are achievable. First tests with a prototype TPC indicate position resolution <1 mm (FWHM).Comment: Paper presented at the International Nuclear Physics Conference, Vancouver, Canada, 201

Atomic structure and physical properties of peridotite glasses at 1 bar

Earth’s mantle, whose bulk composition is broadly peridotitic, likely experienced periods of extensive melting in its early history that formed magma oceans and led to its differentiation and formation of an atmosphere. However, the physical behaviour of magma oceans is poorly understood, as the high liquidus temperatures and rapid quench rates required to preserve peridotite liquids as glasses have so far limited their investigation. In order to better characterize the atomic structure and estimate the physical properties of such glasses, we examined the Raman spectra of quenched peridotite melts, equilibrated at 1900 °C ± 50 °C at ambient pressure under different oxygen fugacities (fO2), from 1.9 log units below to 6.0 log units above the Iron-Wüstite buffer. Fitting the spectra with Gaussian components assigned to different molecular entities (Q-species) permits extraction of the mean state of polymerisation of the glass. We find that the proportions of Q1 (0.36–0.32), Q2 (0.50–0.43), and Q3 (0.16–0.23) vary with Fe3+/FeTOT (FeTOT = Fe2+ + Fe3+), where increasing Fe3+/FeTOT produces an increase in Q3 at the expense of Q2 at near-constant Q1. To account for the offset between Raman-derived NBO/T (2.06–2.27) with those determined by assuming Fe2+ exists entirely as a network modifier and Fe3+ a network former (2.10–2.44), ∼2/3 of the ferric iron and ∼90% of the ferrous iron in peridotite glasses must behave as network modifiers. We employ a deep neural network model, trained to predict alkali and alkaline-earth aluminosilicate melts properties, to observe how small variations in the atomic structure of peridotite-like melts affect their viscosity. For Fe-free peridotite-like melts, the model yields a viscosity of ∼ −1.75 log Pa s at 2000 °C, similar to experimental determinations for iron-bearing peridotite melts. The model predicts that changes in the peridotite melt atomic structure with Fe3+/FeTOT yield variations in melt viscosity lower than 0.1 log Pa s, barely affecting the Rayleigh number. Therefore, at the high temperatures typical of magma oceans, at least at 1 bar, small changes in melt structure from variations in oxidation state are unlikely to affect magma ocean fluid dynamics

Modeling of [F-18]FEOBV Pharmacokinetics in Rat Brain

Purpose: [18F]Fluoroethoxybenzovesamicol ([18F]FEOBV) is a radioligand for the vesicular acetylcholine transporter (VAChT), a marker of the cholinergic system. We evaluated the quantification of [18F]FEOBV in rats in control conditions and after partial saturation of VAChT using plasma and reference tissue input models and test-retest reliability. Procedure: Ninety-minute dynamic [18F]FEOBV PET scans with arterial blood sampling were performed in control rats and rats pretreated with 10 μg/kg FEOBV. Kinetic analyses were performed using one- (1TCM) and two-tissue compartmental models (2TCM), Logan and Patlak graphical analyses with metabolite-corrected plasma input, reference tissue Patlak with cerebellum as reference tissue, standard uptake value (SUV) and SUV ratio (SUVR) using 60- or 90-min acquisition. To assess test-retest reliability, two dynamic [18F]FEOBV scans were performed 1 week apart. Results: The 1TCM did not fit the data. Time-activity curves were more reliably estimated by the irreversible than the reversible 2TCM for 60 and 90 min as the influx rate Ki showed a lower coefficient of variation (COV, 14–24 %) than the volume of distribution VT (16–108 %). Patlak graphical analysis showed a good fit to the data for both acquisition times with a COV (12–27 %) comparable to the irreversible 2TCM. For 60 min, Logan analysis performed comparably to both irreversible models (COV 14–32 %) but showed lower sensitivity to VAChT saturation. Partial saturation of VAChT did not affect model selection when using plasma input. However, poor correlations were found between irreversible 2TCM and SUV and SUVR in partially saturated VAChT states. Test-retest reliability and intraclass correlation for SUV were good. Conclusion: [18F]FEOBV is best modeled using the irreversible 2TCM or Patlak graphical analysis. SUV should only be used if blood sampling is not possible