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Mid-infrared transmission spectra of crystalline and nanophase iron oxides/oxyhydroxides and implications for remote sensing of Mars

Ferric-iron-bearing materials play an important role in the interpretation of visible to near-IR Mars spectra, and they may play a similarly important role in the analysis of new mid-IR spacecraft spectral observations to be obtained over the next decade. We review exisiting data on mid-IR transmission spectra of ferric oxides/oxyhydroxides and present new transmission spectra for ferric-bearing materials spanning a wide range of mineralogy and crystallinity. These materials include 11 samples of well-crystallized ferric oxides (hematite, maghemite, and magnetite) and ferric oxyhydroxides (goethite, lepidocrocite). We also report the first transmission spectra for purely nanophase ferric oxide samples that have been shown to exhibit spectral similarities to Mars in the visible to near-IR and we compare these data to previous and new transmission spectra of terrestial palagonites. Most of these samples show numerous, diagnostic absorption features in the mid-IR due to Fe(3+) - 0(2-) vibrational transitions, structural and/or bound OH, and/or silicates. These data indicate that high spatial resolution, moderate spectral resolution mid-IR ground-based and spacecraft observations of Mars may be able to detect and uniquely discriminate among different ferric-iron-bearing phases on the Martian surface or in the airborne dust.

Bell, James F., III↗

Mid-infrared transmission spectra of crystalline and nanophase iron oxides/oxyhydroxides and implications for remote sensing of Mars

Ferric-iron-bearing materials play an important role in the interpretation of visible to near-IR Mars spectra, and they may play a similarly important role in the analysis of new mid-IR spacecraft spectral observations to be obtained over the next decade. We review existing data on mid-IR transmission spectra of ferric oxides/oxyhydroxides and present new transmission spectra for ferric-bearing materials spanning a wide range of mineralogy and crystallinity. These materials include 11 samples of well-crystallized ferric oxides (hematite, maghemite, and magnetite) and ferric oxyhydroxides (goethite, lepidocrocite). We also report the first transmission spectra for purely nanophase ferric oxide samples that have been shown to exhibit spectral similarities to Mars in the visible to near-IR and we compare these data to previous and new transmission spectra of terrestrial palagonites. Most of these samples show numerous, diagnostic absorption features in the mid-IR due to Fe(3+)-O(2-) vibrational transitions, structural and/or bound OH, and/or silicates. These data indicate that high spatial resolution, moderate spectral resolution mid-IR ground-based and spacecraft observations of Mars may be able to detect and uniquely discriminate among different ferric-iron-bearing phases on the Martian surface or in the airborne dust.

Bell, James F., III↗

NASA's Atmospheric Effects of Aviation Project: Results of the August 1999 Aerosol Measurement Intercomparison Workshop, Laboratory Phase

During August 1-14, 1999, NASA's Atmospheric Effects of Aviation Project (AEAP) convened a workshop at the NASA Langley Research Center to try to determine why such a wide variation in aerosol emissions indices and chemical and physical properties have been reported by various independent AEAP-supported research teams trying to characterize the exhaust emissions of subsonic commercial aircraft. This workshop was divided into two phases, a laboratory phase and a field phase. The laboratory phase consisted of supplying known particle number densities (concentrations) and particle size distributions to a common manifold for the participating research teams to sample and analyze. The field phase was conducted on an aircraft run-up pad. Participating teams actually sampled aircraft exhaust generated by a Langley T-38 Talon aircraft at 1 and 9 m behind the engine at engine powers ranging from 48 to 100 percent. Results from the laboratory phase of this intercomparison workshop are reported in this paper.

Cofer, W. Randy, III↗

NASA's Atmospheric Effects of Aviation Project

During August 1-14, 1999, NASA's Atmospheric Effects of Aviation Project (AEAP) convened a workshop at the NASA Langley Research Center to try to determine why such a wide variation in aerosol emissions indices and chemical and physical properties has been reported by various independent AEAP-supported research teams trying to characterize the exhaust emissions of subsonic commercial aircraft. This workshop was divided into two phases, a laboratory phase and a field phase. The laboratory phase consisted of supplying known particle number densities (concentrations) and particle size distributions to a common manifold for the participating research teams to sample and analyze. The field phase was conducted on an aircraft run-up pad. Participating teams actually sampled aircraft exhaust generated by a Langley T-38 Talon aircraft at 1 and 9 m behind the engine at engine powers ranging from 48 to 100 percent. Results from the laboratory phase of this intercomparison workshop are reported in this paper.

Cofer, W. Randy, III↗

Subsurface Uranium Fate and Transport: Integrated Experiments and Modeling of Coupled Biogeochemical Mechanisms of Nanocrystalline Uraninite Oxidation by Fe(III)-(hydr)oxides - Project Final Report

Subsurface bacteria including sulfate reducing bacteria (SRB) reduce soluble U(VI) to insoluble U(IV) with subsequent precipitation of UO 2 . We have shown that SRB reduce U(VI) to nanometer-sized UO 2 particles (1-5 nm) which are both intra- and extracellular, with UO 2 inside the cell likely physically shielded from subsequent oxidation processes. We evaluated the UO 2 nanoparticles produced by Desulfovibrio desulfuricans G20 under growth and non-growth conditions in the presence of lactate or pyruvate and sulfate, thiosulfate, or fumarate, using ultrafiltration and HR-TEM. Results showed that a significant mass fraction of bioreduced U (35-60%) existed as a mobile phase when the initial concentration of U(VI) was 160 µM. Further experiments with different initial U(VI) concentrations (25 - 900 M) in MTM with PIPES or bicarbonate buffers indicated that aggregation of uraninite depended on the initial concentrations of U(VI) and type of buffer. It is known that under some conditions SRB-mediated UO 2 nanocrystals can be reoxidized (and thus remobilized) by Fe(III)-(hydr)oxides, common constituents of soils and sediments. To elucidate the mechanism of UO 2 reoxidation by Fe(III) (hydr)oxides, we studied the impact of Fe and U chelating compounds (citrate, NTA, and EDTA) on reoxidation rates. Experiments were conducted in anaerobic batch systems in PIPES buffer. Results showed EDTA significantly accelerated UO 2 reoxidation with an initial rate of 9.5 M day-1 for ferrihydrite. In all cases, bicarbonate increased the rate and extent of UO 2 reoxidation with ferrihydrite. The highest rate of UO 2 reoxidation occurred when the chelator promoted UO 2 and Fe(III) (hydr)oxide dissolution as demonstrated with EDTA. When UO 2 dissolution did not occur, UO 2 reoxidation likely proceeded through an aqueous Fe(III) intermediate as observed for both NTA and citrate. To complement to these laboratory studies, we collected U-bearing samples from a surface seep at the Rifle field site and have measured elevated U concentrations in oxic iron-rich sediments. To translate experimental results into numerical analysis of U fate and transport, a reaction network was developed based on Sani et al. (2004) to simulate U(VI) bioreduction with concomitant UO 2 reoxidation in the presence of hematite or ferrihydrite. The reduction phase considers SRB reduction (using lactate) with the reductive dissolution of Fe(III) solids, which is set to be microbially mediated as well as abiotically driven by sulfide. Model results show the oxidation of HS– by Fe(III) directly competes with UO 2 reoxidation as Fe(III) oxidizes HS– preferentially over UO 2 . The majority of Fe reduction is predicted to be abiotic, with ferrihydrite becoming fully consumed by reaction with sulfide. Predicted total dissolved carbonate concentrations from the degradation of lactate are elevated (log(pCO 2 ) ~ –1) and, in the hematite system, yield close to two orders-of-magnitude higher U(VI) concentrations than under initial carbonate concentrations of 3 mM. Modeling of U(VI) bioreduction with concomitant reoxidation of UO 2 in the presence of ferrihydrite was also extended to a two-dimensional field-scale groundwater flow and biogeochemically reactive transport model for the South Oyster site in eastern Virginia. This model was developed to simulate the field-scale immobilization and subsequent reoxidation of U by a biologically mediated reaction network.

54 ENVIRONMENTAL SCIENCES↗

Chromium basalts - Experimental determination of redox states and partitioning among synthetic silicate phases

Experiments were performed on silicate compositions in the forsterite-anorthite-silica and forsterite-anorthite-diopside systems to determine the relative amounts of Cr(II), Cr(III), and Cr(VI) over a wide range of oxygen partial pressures from 10 to the -10th to 1 atm at 1500 and 1550 C. Redox states were measured by visible absorption spectroscopy and electron paramagnetic resonance spectroscopy and titration. It was found that Cr is present almost exclusively as Cr(III) in terrestrial basaltic liquids and as a mixture of Cr(III) and Cr(II) in lunar basaltic liquids.

Schreiber, H. D.↗

Studies of Brazilian meteorites. III - Origin and history of the Angra dos Reis achondrite

The mineral composition of the Angra dos Reis meteorite, which fell in 1869, is described. This achondrite contains phases reported in a meteorite for the first time. Petrofabric analysis shows that fassaite has a preferred orientation and lineation, which is interpreted as being due to cumulus processes, possibly the effect of post-depositional magmatic current flow or laminar flow of a crystalline mush. The mineral chemistry indicates crystallization from a highly silica-undersaturated melt at low pressure. Several aspects of the mineral composition are discussed with reference to the implications of crystallization conditions.

Prinz, M.↗

Single- and dual-variant atomic ordering in GaAsP compositionally graded buffers on GaP and Si substrates

Here, we investigate the material properties of GaAsP graded buffers on both GaP and Si substrates in order to determine limitations to dislocation glide in GaAsP. Phase separation is not observed in these GaAsP buffers, but CuPt B atomic ordering is present, and has an impact on the Burgers vector distribution of gliding dislocations. Tellurium surfactant eliminates ordering in GaAsP, allowing control over the glide plane distribution while highlighting the importance of the growth surface and choice of dopant. The impact of single-variant CuPtB ordering of GaAsP buffers grown on GaP substrates is investigated by monitoring the threading dislocation density throughout the buffer in sequential steps. The dislocation density rises steadily throughout the graded buffer, implying that factors other than ordering-induced glide plane switches play a dominant role in the final dislocation density. We observe an increase in surface roughness throughout the buffer and speculate that a dislocation nucleation source on the surface has a low activation energy and may lead to increased threading dislocation density. On Si substrates, the GaAsP buffer displays dual-variant CuPt B ordering rather than single-variant ordering due to the surface step geometry. We discuss how dual-variant ordering leads to a variable glide force, and thus has a different impact on dislocation dynamics than single-variant ordering. Because the III-V on Si nucleation procedure determines the step geometry, it also influences the dislocation dynamics.

36 MATERIALS SCIENCE↗

Ultraviolet observations of the gas phase abundances in the diffuse clouds toward Zeta Ophiuchi at 3.5 kilometers per second resolution

Goddard High Resolution Spectrograph echelle mode measurements at 3.5 km/s resolution are presented for interstellar absorption produced by C II, O I, Mg I, Mg II, Al III, P II, Cr II, Mn II, Fe II, Ni II, Cu II, Zn II, Ga II, Ge II, and Kr I. The absorption line measurements are converted into representations of apparent column density per unit velocity in order to study the multicomponent nature of the absorption. The high spectral resolution of the measurements allows a comparative study of gas phase abundances for many species in the absorbing clouds near -27 and -15 km/s with a typical precision of about 0.05 dex. The matter absorbing near -27 km/s is situated in the local interstellar medium and has log N(H I) of about 19.74. This absorption provides information about the modest 'base' depletion associated with the lower density interstellar medium. The depletion results suggest that accretion processes are operating interstellar clouds that exhibit similar depletion efficiencies for some elements but much higher depletion efficiencies for others.

Savage, Blair D.↗

Insights into the Oxidant/Polymer Interfacial Growth of Vapor Phase Polymerized PEDOT Thin Films

Abstract The vapor phase polymerization (VPP) technique is used to produce thin films of poly(3,4‐ethylenedioxythiopene) (PEDOT) in which the Fe(III)Tosylate oxidant is altered. The oxidant is changed with the addition of an amphiphilic co‐polymer having different molecular weights, namely 2800 Da. and 5800 Da. Resulting PEDOT films produce conductivities of ≈1500 and ≈3000 S cm −1 respectively. Small angle X‐ray diffraction (SA‐XRD) indicates that the oxidant incorporating the larger molecular weight co‐polymer possesses ordered structure and that this in turn helps “template” the PEDOT during film formation. The structure and composition of the bottom (i.e. initial film formation) and top (i.e. final film formation) PEDOT surfaces are studied using surface sensitive analytical techniques; small angle X‐ray diffraction (SA‐XRD), ultraviolet photoelectron spectroscopy (UPS), 2D grazing incidence X‐ray diffraction (2D‐GIXD), metastable induced electron spectroscopy (MIES) and neutral impact collision ion scattering spectroscopy (NICISS). The results indicate that the increase in conductivity using the larger molecular weight co‐polymer additive is due to the film having larger lamella‐ and π‐stacking regions in addition to doping levels which remain unchanged throughout film formation. These conclusions are further supported by results obtained on a model PEDOT:Tosylate system using density functional theory (DFT) calculations.

Sharma, Anirudh↗

PandaX-III: Searching for neutrinoless double beta decay with high pressure 136 Xe gas time projection chambers

Searching for the neutrinoless double beta decay (NLDBD) is now regarded as the topmost promising technique to explore the nature of neutrinos after the discovery of neutrino masses in oscillation experiments. PandaX-III (particle and astrophysical xenon experiment III) will search for the NLDBD of 136 Xe at the China Jin Ping Underground Laboratory (CJPL). In the first phase of the experiment, a high pressure gas Time Projection Chamber (TPC) will contain 200 kg, 90% 136 Xe enriched gas operated at 10 bar. Fine pitch micro-pattern gas detector (Microbulk Micromegas) will be used at both ends of the TPC for the charge readout with a cathode in the middle. Charge signals can be used to reconstruct the electron tracks of the NLDBD events and provide good energy and spatial resolution. The detector will be immersed in a large water tank to ensure ∼5 m of water shielding in all directions. Furthermore, the second phase, a ton-scale experiment, will consist of five TPCs in the same water tank, with improved energy resolution and better control over backgrounds.

TPC↗

ELECTRON AND PROTON ACCELERATION DURING THE FIRST GROUND LEVEL ENHANCEMENT EVENT OF SOLAR CYCLE 24

High-energy particles were recorded by near-Earth spacecraft and ground-based neutron monitors (NMs) on 2012 May 17. This event was the first ground level enhancement (GLE) of solar cycle 24. In this study, we try to identify the acceleration source(s) of solar energetic particles by combining in situ particle measurements from the WIND/3DP, GOES 13, and solar cosmic rays registered by several NMs, as well as remote-sensing solar observations from SDO/AIA, SOHO/LASCO, and RHESSI. We derive the interplanetary magnetic field (IMF) path length (1.25 {+-} 0.05 AU) and solar particle release time (01:29 {+-} 00:01 UT) of the first arriving electrons by using their velocity dispersion and taking into account contamination effects. We found that the electron impulsive injection phase, indicated by the dramatic change in the spectral index, is consistent with flare non-thermal emission and type III radio bursts. Based on the potential field source surface concept, modeling of the open-field lines rooted in the active region has been performed to provide escape channels for flare-accelerated electrons. Meanwhile, relativistic protons are found to be released {approx}10 minutes later than the electrons, assuming their scatter-free travel along the same IMF path length. Combining multi-wavelength imaging data of the prominence eruption and coronal mass ejection (CME), we obtain evidence that GLE protons, with an estimated kinetic energy of {approx}1.12 GeV, are probably accelerated by the CME-driven shock when it travels to {approx}3.07 solar radii. The time-of-maximum spectrum of protons is typical for shock wave acceleration.

79 ASTRONOMY AND ASTROPHYSICS↗

Background Information on the Protection Requirements in IEEE Std 1547-2018

As the DER penetration level has risen significantly in recent times, parameter settings and configuration of installed DERs are having direct impact on local electric distribution utilities as well as bulk power systems during normal and abnormal grid conditions. On the other hand, all grid-connected DERs in the United States of America must conform to the interconnection requirements prescribed in the IEEE Std 1547-2018. Because of these reasons, it is crucial to understand the expected DER performance during abnormal grid conditions considering the requirements of the IEEE Std 1547-2018. The aim of this document is twofold: (1) to summarize requirements in IEEE Std 1547-2018 having direct implications in distribution network protection, and (2) to provide the reader with knowledge and information that will be required for users to apply the requirements specified. Since the focus of this document is on distribution network protection in the presence of DERs, it is assumed that the readers have basic understanding of distribution network protection as well as working principles of DERs. This document starts with a brief introduction on protection systems for distribution network followed by a discussion on the impact of DER on the protection systems. Current practices to provide network protection in the presence of DER is briefly discussed. The document then explores the DER performance requirements in IEEE Std. 1547-2018; especially on those related to distribution network protection. Section 6.1 in IEEE Std. 1547-2018 provides an overview of capabilities and control requirements for DER under abnormal operating conditions. This section also introduces abnormal operating performance categories I, II, III. The DER response to various types of faults and grid conditions such as short-circuit faults and open phase conditions are discussed in section 6.2 in the standard while requirements for coordination with the Area EPS reclosing scheme are provided in section 6.3. Section 6.4 in the IEEE Std 1547-2018 specifies requirements for mandatory voltage tripping and ride-through requirements during low and high voltage disturbances and section 6.5 specifies similar requirements for low and high frequency disturbances. IEEE Std. 1547 requires that the conformance of the DERs to IEEE Std 1547-2018 requirements should be verified in accordance with IEEE Std. 1547. 1. There are several parameters and settings of DERs that need to be properly selected for reliable operation during abnormal grid condition while applying the requirements of IEEE Std 1547-2018. Key decisions for proper selections of parameter and settings are: 1. Determination of required DER abnormal operating performance category, 2. Determination of DER response (shall trip) to abnormal voltages and 3. Determination of DER response (shall trip) to abnormal frequency.

24 POWER TRANSMISSION AND DISTRIBUTION↗

A Perspective Around Cephalopods and Their Parasites, and Suggestions on How to Increase Knowledge in the Field

Although interest in several areas of cephalopod research has emerged over the last decades (e.g., neurobiology, aquaculture, genetics, and welfare), especially following their 2010 inclusion in the EU Directive on the use of animals for experimental purposes, knowledge regarding the parasites of cephalopods is lacking. Cephalopods can be intermediate, paratenic, or definitive hosts to a range of parasites with a wide variety of life cycle strategies. Here, we briefly review the current knowledge in cephalopod parasitological research, summarizing the main parasite groups that affect these animals. We also emphasize some topics that, in our view, should be addressed in future research, including: (i) better understanding of life cycles and transmission pathways of common cephalopod parasites; (ii) improve knowledge of all phases of the life cycle (i.e., paralarvae, juveniles, adults and senescent animals) and on species from polar deep sea regions; (iii) exploration of the potential of using cephalopod-parasite specificity to assess population boundaries of both, hosts and parasites; (iv) risk evaluation of the potential of standard aquacultural practices to result in parasite outbreaks; (v) evaluation and description of the physiological and behavioral effects of parasites on their cephalopod hosts; (vi) standardization of the methods for accurate parasite sampling and identification; (vii) implementation of the latest molecular methods to facilitate and enable research in above mentioned areas; (viii) sharing of information and samples among researchers and aquaculturists. In our view, addressing these topics would allow us to better understand complex host-parasite interactions, yield insights into cephalopod life history, and help improve the rearing and welfare of these animals in captivity.

59 BASIC BIOLOGICAL SCIENCES↗

Phase lock acquisition for sampled data PLLs using the sweep technique

Simulation results of the swept-acquisition performance of residual carrier phase-locked loops (PLLs) are reported. The loops investigated are sampled data counterparts of the continuous time type II and III loops currently in use in Deep Space Network receivers. It was found that sweep rates of 0.2 B(sub L)(2) to 0.4 B(sub L)(2) Hz/s can be used, depending on the loop parameters and loop signal-to-noise ratio (SNR), where B(sub L) is the one-sided loop noise bandwidth. Type III loops are shown to be not as reliable as type II loops for acquisition using this technique, especially at low SNRs.

Aguirre, S.↗

H II regions and the abundance properties of spiral galaxies

We investigate the relationships between the characteristic oxygen abundance, the radial abundance gradient, and the macroscopic properties of spiral galaxies by examining the properties of individual H II regions within those galaxies. Our observations of the line flux ratio (O II) lambda lambda 3726, 3729 + (O III) lambda lambda 4959, 5007)/H beta for 159 H II regions in 14 spiral galaxies are combined with published data to provide a sample of 39 disk galaxies for which (O II) + (O III)/H beta has been measured for at least five H II regions. We find that the characteristic gas-phase abundances and luminosities of spiral galaxies are strongly correlated. This relationship maps almost directly onto the luminosity-metallicity relationship of irregular galaxies and is also quite similar to that found for elliptical and dwarf spheroidal galaxies. Within our sample of spirals, a strong correlation between characteristic abundance and Hubble type also exists. The correlation between luminosity and Hubble type complicates the issue, but we discuss several interpretations of the correlations. The relationship between circular velocity and characteristic abundance is also discussed. We find that the slopes of the radial abundance gradients, when expressed in units of dex/isophotal radius, do not significantly correlate with either luminosity or Hubble type. However, the hypothesis that both early and very late type spirals have shallower gradients than intermediate spirals is consistent with the data. We find suggestive evidence that the presence of a bar induces a flatter gradient and also briefly discuss whether abundance gradients are exponential, as is usually assumed. We investigate the properties of individual H II regions in a subset of 42 regions for which we have spectra that cover almost the entire spectral range from 3500 to 9800 A. We use those data to estimate the densitites and ionizing spectra within the H II regions. We confirm that the ionizing spectrum hardens with increasing radius and decreasing abundance. We find no correlation between the ionization parameter and either radius or abundance, but this may be due to significant scatter introduced by the simple conversion of line ratios to ionization parameter.

Zaritsky, Dennis↗

Thermodynamic constraints on the textural evolution of eucrite, EET 90020

Basaltic eucrites, which are possibly parts of the Vestan crust, formed as either lava flows or intrusions, and can offer insights into early crust formation. However most eucrites have experienced thermal metamorphism, which exacerbates the challenges of understanding these samples. A variety of petrogenetic models such as, partial melting of a primitive source, fractional crystallization of magmas emplaced in a primitive crust, and/or partial melting of a eucritic source coupled with melt mixing and assimilation have been proposed in order to explain observed petrologic and chemical characteristics of eucrites. EET 90020 is an unbrecciated eucrite that has experienced significant thermal metamorphism, with temperatures of metamorphic equilibration calculated to be ~840-1040°C. Its petrologic history remains contentious, in part due to differences in trace element analyses [10,17, this work], which has led to multiple metamorphic interpretations [8,10-11]. Here, we combined petrologic observations, chemical analyses, and thermodynamic modeling, to interpret micro-domain textures identified in EET 90020 and better constrain its petrologic history. Ultimately, the development of such textures is a direct result of the geologic processes operating on a young Vesta or similar asteroid. Sample description: We identified three textural domains in EET 90020 (Figure 1); (I) A coarse grain domain with granoblastic plagioclase and pyroxene, (II) a medium grain domain with curved grain boundaries between plagioclase and pyroxene, and (III) a fine grain domain dominated by tridymite that fills in interstitial space between spherical plagioclase. Major element chemistry in phases is consistent across domains. Pyroxene have distinctive high Ca lamellae (Wo40.92En28.1Fs31.0) forming from the low-Ca pigeonite host (Wo3.5En33.7Fs62.8). There are small amounts of fayalitic olivine along pyroxene/oxide grain boundaries, where pyroxenes have reacted with ilmenite/chromite clasts. Plagioclase is anorthitic (Avg ~An88), with little variation (An86-92.5). Trace element bulk rock analyses were collected via ICP-MS and individual mineral analyses with LA-ICP-MS (Figure 2). The bulk sample has an observable enrichment in light rare earth elements, with a notable depletion in Eu. Plagioclase is enriched in LREEs, depleted in HREEs, and has a positive Eu anomaly while pyroxene is enriched in HREEs with a negative Eu anomaly. Variations in trace element analyses is likely influenced by the presence of phosphates because are highly enriched in REEs and have a dramatic effect on the bulk domain compositions. Thermodynamic modeling: The software package, Perple_X, was used to calculate mineral phase equilibria over a range of conditions using a Gibbs free energy minimization approach [12]. Models used all major/minor elements except P2O5. Thermodynamic properties from [13] were used to constrain endmember phase stabilities. Activity models were used to describe mixing in phases with solid solution. Isochemical P-T phase diagrams were constructed for the bulk thin section, and the coarse, medium and fine grain domain compositions. Domain compositions were determined using microprobe analyses of phases identified in each domain and observed modal mineral abundancies. Thermodynamically stable pyroxene compositions were extracted from model results and compared to pyroxene compositions collected via EMPA, allowing us to calculate temperatures for metamorphic equilibrium. Results: Results that use the coarse domain composition (Fig. 3a) demonstrate overlap at T ~ 1020°C indicating high T equilibration. There was no overlap for the medium and fine grain domains, or the bulk composition (e.g., Fig. 3b) indicating that these are not equilibrium assemblages. These results were replicated using data from [8,20]. Discussion: The disequilibrium results from the bulk rock, fine grain and medium grain models imply that EET 90020 was modified during and/or after peak metamorphism (open system behavior). However, this is in contrast to the coarse domain where it appears as if equilibrium was maintained. We suggest that this conflict is explained by highly localized equilibrium occurring at millimeter length-scales, which has been observed in terrestrial metamorphism where aqueous fluid infiltrate [14] or melt loss occurs [15]. It is unlikely that aqueous alteration was significant in modifying the bulk composition of EET 90020, because it lacks hydrated minerals. However, the presence of melt is supported by the presence of an abundance of curved grain boundaries and spherical grains in the medium and fine grain domains This contrasts the coarse domain, where grain boundaries are angular. Given the evidence for disequilibrium in the medium and fine grain domains, it would be inappropriate to draw additional conclusions about textural evolution using thermodynamic models of those domains. However, modeling results of the coarse grain domain, where equilibrium was maintained, can provide useful insights into the geologic evolution of EET 90020. We approximate maximum metamorphic temperatures, using the Ca component in pyroxene, at ~1020°C (Fig. 4), which is consistent with previous two-pyroxene thermometry [11]. At this temperature, up to 10 vol % melt can be produced in the coarse grain domain, which is at the boundary of minimum melt needed in order to segregate and form a melt network [16]. Tridymite and plagioclase would be the first minerals to melt out during heating starting ~990°C. This is consistent with the observed melt textures formed by tridymite and plagioclase in the fine grain domain. We suggest that a partial melting model best explains the textural development of EET 90020. Upon heating, melt generated was either trapped, resulting in no net change in the localized rock composition, or migrated, resulting in disequilibrium between pyroxene and the surrounding matrix. A positive Eu anomaly in plagioclase indicates that all of the plagioclase was melted previously. This is consistent with previous studies that have suggested that EET 90020 represents a residual eucrite that experienced partial melting and subsequent melt loss [8]. We speculate that partial melting could have occurred when EET 90020 was heated in the asteroid’s lower crust or adjacent to an intrusion [7]. Future work will study other, texturally heterogeneous samples to see if EET 90020 presents a unique circumstance or whether crustal partial melting was ubiquitous on the eucrite asteroid.

Eucrites↗

DFT-based investigation of solvation of Nd(III)/Yb(III) cations in room-temperature ionic-liquid

We report a DFT study on the solvation of bare rare-earth (RE) cations [Nd(III) and Yb(III)] in the room-temperature ionic-liquid (RTIL) based on 1,3-dimethyl-imidazolium + , PF 6 - , [MMI][PF 6 ]. In the present article, we aim to investigate whether the chosen RTIL can preferentially solvate any of the RE cations under study. First, the RTIL binding to the RE cation is studied in the gas phase, and then explored with continuum solvation model employing RTIL parameters. First, we considered the formation of the first solvation shell, where the PF 6 - anions directly bond with the Ln(III) cation. We then further surrounded the first solvation shell with [MMI]+ cations to form the second solvation shell. The stability of PF 6 - coordinated complexes is studied by calculating the binding energy values. The number of PF 6 - anions for both Ln(III) cations starts with three ligands and goes until the maximum binding energy in the RTIL medium is reached. The coordination number and binding modes of PF 6 - depend on the size of the RE cation. Comparing the binding energy values between the RE cations for the first solvation shell complexes, it is noticed that Yb-complexes have relatively greater binding energy than Nd-complexes. We have further performed a Boltzmann population analysis to find out the most dominant conformer among each category of PF 6 - coordinated complexes. A study using Natural Population Analysis shows that after complexation with PF 6 - the charge on the Yb-centers lower to a greater extent than Nd-centers, implying stronger bonding between Yb and PF 6 - , which is in harmony with the binding energy analysis. Overall, the computational investigation provides an in-depth understanding of the complexation phenomena of RE cations in RTIL, which can be useful for the practical separation of RE cations using RTIL.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗