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Materials Data on Ca5(OsN3)2 by Materials Project

Ca5(OsN3)2 crystallizes in the monoclinic C2/c space group. The structure is three-dimensional. there are three inequivalent Ca2+ sites. In the first Ca2+ site, Ca2+ is bonded to six N3- atoms to form distorted CaN6 pentagonal pyramids that share corners with four equivalent CaN6 octahedra, corners with two equivalent CaN5 trigonal bipyramids, edges with four equivalent CaN6 octahedra, and edges with four equivalent CaN5 trigonal bipyramids. The corner-sharing octahedra tilt angles range from 8–29°. There are a spread of Ca–N bond distances ranging from 2.39–2.73 Å. In the second Ca2+ site, Ca2+ is bonded to six N3- atoms to form distorted CaN6 octahedra that share corners with two equivalent CaN6 pentagonal pyramids, corners with six equivalent CaN5 trigonal bipyramids, edges with three equivalent CaN6 octahedra, edges with two equivalent CaN6 pentagonal pyramids, and edges with two equivalent CaN5 trigonal bipyramids. There are a spread of Ca–N bond distances ranging from 2.53–2.84 Å. In the third Ca2+ site, Ca2+ is bonded to five N3- atoms to form distorted CaN5 trigonal bipyramids that share corners with six equivalent CaN6 octahedra, a cornercorner with one CaN6 pentagonal pyramid, corners with two equivalent CaN5 trigonal bipyramids, edges with two equivalent CaN6 octahedra, edges with two equivalent CaN6 pentagonal pyramids, and an edgeedge with one CaN5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 6–79°. There are a spread of Ca–N bond distances ranging from 2.35–2.68 Å. Os4+ is bonded in a distorted trigonal planar geometry to four N3- atoms. There are a spread of Os–N bond distances ranging from 1.87–2.71 Å. There are three inequivalent N3- sites. In the first N3- site, N3- is bonded in a 2-coordinate geometry to four Ca2+ and two equivalent Os4+ atoms. In the second N3- site, N3- is bonded to five Ca2+ and one Os4+ atom to form a mixture of distorted corner, edge, and face-sharing NCa5Os octahedra. The corner-sharing octahedra tilt angles range from 12–73°. In the third N3- site, N3- is bonded to five Ca2+ and one Os4+ atom to form a mixture of distorted corner and edge-sharing NCa5Os octahedra. The corner-sharing octahedra tilt angles range from 12–73°.

36 MATERIALS SCIENCE↗

Materials Data on Li5OsO6 by Materials Project

Li5OsO6 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. there are three inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with six LiO6 octahedra, edges with three equivalent OsO6 octahedra, and edges with nine LiO6 octahedra. The corner-sharing octahedra tilt angles range from 8–12°. There are a spread of Li–O bond distances ranging from 2.08–2.10 Å. In the second Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with two equivalent OsO6 octahedra, corners with four equivalent LiO6 octahedra, edges with two equivalent OsO6 octahedra, and edges with ten LiO6 octahedra. The corner-sharing octahedra tilt angles range from 2–12°. There are a spread of Li–O bond distances ranging from 2.07–2.19 Å. In the third Li1+ site, Li1+ is bonded to six O2- atoms to form LiO6 octahedra that share corners with two equivalent OsO6 octahedra, corners with four equivalent LiO6 octahedra, edges with two equivalent OsO6 octahedra, and edges with ten LiO6 octahedra. The corner-sharing octahedra tilt angles range from 0–8°. There are four shorter (2.07 Å) and two longer (2.24 Å) Li–O bond lengths. Os7+ is bonded to six O2- atoms to form OsO6 octahedra that share corners with six LiO6 octahedra and edges with twelve LiO6 octahedra. The corner-sharing octahedra tilt angles range from 0–2°. There is two shorter (1.89 Å) and four longer (1.93 Å) Os–O bond length. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded to five Li1+ and one Os7+ atom to form a mixture of corner and edge-sharing OLi5Os octahedra. The corner-sharing octahedra tilt angles range from 0–14°. In the second O2- site, O2- is bonded to five Li1+ and one Os7+ atom to form a mixture of corner and edge-sharing OLi5Os octahedra. The corner-sharing octahedra tilt angles range from 0–7°.

36 MATERIALS SCIENCE↗

Online Learning Flight Control for Intelligent Flight Control Systems (IFCS)

The research accomplishments for the cooperative agreement 'Online Learning Flight Control for Intelligent Flight Control Systems (IFCS)' include the following: (1) previous IFC program data collection and analysis; (2) IFC program support site (configured IFC systems support network, configured Tornado/VxWorks OS development system, made Configuration and Documentation Management Systems Internet accessible); (3) Airborne Research Test Systems (ARTS) II Hardware (developed hardware requirements specification, developing environmental testing requirements, hardware design, and hardware design development); (4) ARTS II software development laboratory unit (procurement of lab style hardware, configured lab style hardware, and designed interface module equivalent to ARTS II faceplate); (5) program support documentation (developed software development plan, configuration management plan, and software verification and validation plan); (6) LWR algorithm analysis (performed timing and profiling on algorithm); (7) pre-trained neural network analysis; (8) Dynamic Cell Structures (DCS) Neural Network Analysis (performing timing and profiling on algorithm); and (9) conducted technical interchange and quarterly meetings to define IFC research goals.

Niewoehner, Kevin R.↗

NASA GTE TRACE-P Augmentation

There were three major tasks and objectives that the Tropospheric Trace Gas and Airborne Measurement Group's (TTGAMG) worked on for different aspects of this grant: 1) Migrate the data acquisition system from HP-UX to Linux, thus reducing future costs as the result of software and operating system (OS) upgrades and improving upon usability as membership in the group changes; 2) Rework the Optical Parametric Oscillator (OPO) cavities. These are the OPOs that are integral to the Georgia Institute of Technology Airborne Laser Induced Fluorescent Experiment (GITALIFE) that the TTGAMG flew on TRACE-P. The objective was to improve upon optimizing the pump laser energy and narrowing the linewidth of the UV wavelength generated by the OPOs; 3) Improve and expand the interactive website on http://tmbk2.eas.gatech.edu by adding 3-D graphing, improve the response time for Joe Surfer Dude, improve performance, usability, and expand the database. If I were to assign a letter grade to each of the above tasks, I would give the TTGAMG two Bs and an A to the tasks listed above.

Sandholm, Scott↗

Water in the Oceanic Lithosphere: Salt Lake Crater Xenoliths, Oahu, Hawaii

Water can be present in nominally anhydrous minerals of peridotites in the form of hydrogen bonded to structural oxygen. Such water in the oceanic upper mantle could have a significant effect on its physical and chemical properties. However, the water content of the MORB source has been inferred indirectly from the compositions of basalts. Direct determinations on abyssal peridotites are scarce because they have been heavily hydrothermally altered. Here we present the first water analyses of minerals from spinel peridotite xenoliths of Salt Lake Crater, Oahu, Hawaii, which are exceptionally fresh. These peridotites are thought to represent fragments of the Pacific oceanic lithosphere that was refertilized by alkalic Hawaiian melts. A few have unradiogenic Os and radiogenic Hf isotopes and may be fragments of an ancient (~2 Ga) depleted and recycled lithosphere. Water contents in olivine (Ol), orthopyroxene (Opx), and clinopyroxene (Cpx) were determined by FTIR spectrometry. Preliminary H_{2}O contents show ranges of 8-10 ppm for Ol, 151-277 ppm for Opx, and 337-603 ppm for Cpx. Reconstructed bulk rock H_{2}O contents range from 88-131 ppm overlapping estimates for the MORB source. Water contents between Ol minerals of the same xenolith are heterogeneous and individual OH infrared bands vary within a mineral with lower 3230 cm^{-1} and higher 3650-3400 cm^{-1} band heights from core to edge. This observation suggests disturbance of the hydrogen in Ol likely occurring during xenolith entrainment to the surface. Pyroxene water contents are higher than most water contents in pyroxenes from continental peridotite xenoliths and higher than those of abyssal peridotites. Cpx water contents decrease with increasing degree of depletion (e.g. increasing Fo in Ol and Cr# in spinel) consistent with an incompatible behavior of water. However Cpx water contents also show a positive correlation with LREE/HREE ratios and LREE concentrations consistent with refertilization. Opx water contents increase with increasing degree of depletion and decrease with LREE/HREE ratios which is inconsistent with the incompatible behavior of H. Calculated water contents of melts in equilibrium with Cpx or Opx range from 1.4 to 3.8 wt % which is higher than that of all Hawaiian lavas. Calculated melts in equilibrium with Cpx and Opx have variable but mostly high H_{2}O/Ce ratios (194 to 1146) consistent with those of rejuvenated stage lavas from Niihau and the South Arch volcanic field, but unlike the drier shield building stage tholeiites. Whether the high water contents recorded in Salt Lake Crater xenoliths were acquired before and/or during interaction of the oceanic lithosphere with the Hawaiian plume will be discussed.

Peslier, Anne H.↗

Prophylactic Cranial Irradiation Reduces Brain Metastases and Improves Overall Survival in High-Risk Metastatic Non-Small Cell Lung Cancer Patients: A Randomized phase 2 Study (PRoT-BM trial)

To date, studies regarding the use of prophylactic cranial irradiation (PCI) versus standard of care (SoC) for patients with non-small cell lung cancer (NSCLC) have not shown a significant effect in terms of overall survival (OS). Additionally, the effect of PCI among high-risk patients has been scarcely studied. The objective of this randomized phase 2 study was to evaluate the role of PCI in a population of patients at high risk for development of brain metastases (BM).

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Recommendation on Orbiting Sample Cleanliness

The National Aeronautics and Space Administration-European Space Agency (NASA-ESA) Mars Sample Return (MSR) campaign involves the collection of samples on Mars by the Perseverance (Mars 2020) rover and their return to Earth. To accomplish this, the Orbiting Sample container (OS) will be sent to Mars to accommodate the collected samples then launched from Mars and returned to Earth, where the samples will be removed for examination in the Sample Return Facility (SRF). Crucial to this entire sequence will be establishment of the required level of cleanliness inside the OS. In February 2021, the NASA Headquarters' Mars Sample Return Program and Office of Planetary Protection assembled an MSR OS Tiger Team (OSTT) to discuss the appropriate cleanliness level options of the interior of the OS. The team's remit was primarily focused on evaluating the trade-offs between Planetary Protection cleanliness levels 4a and 4b. These cleanliness levels are determined by the Committee on Space Research (COSPAR) planetary protection regulations, where 4a requires <300 bacterial spores/m^2 and <3 x 10^5 bacterial spores on the spacecraft (in this case, the interior of the OS) and 4b mandates the more stringent requirement of <30 bacterial spores on the spacecraft. This report documents the consensus opinion submitted by the OSTT that recommended the interior of the OS be cleaned to a 4a requirement with any feasible added effort toward 4b. This report provides, as well, the rationale for that decision.

Charles S. Cockell↗

Revisions of ORNL 188 W Process Based on Nonradiological Experiments

Tungsten-188 is in widespread use in the 188 W(t 1/2 = 69 d)/ 188 Re(t 1/2 =16.9 h) biomedical generator. Oak Ridge National Laboratory (ORNL) has been providing this product to the world since 1999. At ORNL, 188 W is produced via irradiation in ORNL’s High Flux Isotope Reactor (HFIR). Enriched 186 W targets in the form of sintered metallic pellets or rings achieve a compact loading in the irradiation vessel, providing a high yield per unit target. The enrichment of the target is >90% 186 W and this isotope undergoes double neutron capture to produce the desired 188W product. While 188 W is produced by neutron bombardment, 191 Os(t 1/2 = 15.4 d) is simultaneously produced as a byproduct requiring separation from 188 W by post irradiation treatment. In the current processing pathway, the irradiated W metal pellets or rings are first converted into an oxide form of WO 3 by heating the irradiated W metal target at 750°C in a quartz reaction vessel inside a vertical furnace under a constant flow of air. During heating, W metal reacts with oxygen in the air to produce WO 3 , which is soluble in 6 M NaOH for later purification process. This oxidation process also converts 188 Os (the decay daughter of 188 W) and 191 Os (the irradiation produced byproduct) into OsO 4 , a highly volatile and toxic gas. The gaseous effluents driven from the quartz reaction vessel are passed through a scrubbing array to remove OsO 4 before the air is discharged from the process. This heterogeneous oxidation method simultaneously achieves two goals: 1). converting metal target to a soluble oxide form and 2). separating volatile OsO 4 away from the solid WO 3 product, although harmful 191 OsO 4 is unfavorable but being taken care of by the down road scrubbing array. In the past twenty years the existing OsO 4 scrubbing array served well in preventing OsO 4 from being released into the environment, until July of 2020 when a minor amount of 191 Os was found to have been released into the environment which resulted in a standby of building 4501 from July 2020 to February 2021.Since October 20 of 2020 a team of researchers from groups of RSTD and NEFD were organized to work for the following tasks: (1) Fully understand the root causes of the July incident of 191 Os release and create a redesigned 191 Os scrubbing array to eliminate the possibility of 191 Os release in future 188 W processes; (2) In Phase-1 tests, select a correct air (O 2 ) flow rate in 188 W process, that provides sufficient oxygen for the oxidation of tungsten metal, while still allowing sufficient resonance time for 191 Os removal by the scrubbers; (3) In Phase-2 tests, confirm the efficiency of the redesigned scrubbing array to absorb excessive amount of non-rad OsO 4 (generated from Os metal powder) at the selected air flow; (4) In Phase-3 tests, simulate the hot cell 188 W process by heating pressed non-rad W-Os pellets in a quartz vessel of new design and the new array under operation parameters selected in Phase-1 and -2; (5) Complete a new operation procedure for 188 W process in hot cell and a TM report as a summary of the Os Mitigation Project. This TM report summarizes the investigation on root causes from technical aspects in July 191 Os release and the correspondent improvement towards the redesigned 191 Os scrubbing system. The report presents the efforts made on selection of optimal operational parameter with the new scrubbing array and the quartz vessel of new design, based on experiment data obtained in Phase-1, -2 and -3 tests. Further renovations for 188 W process and additional improvement of W target treatment will also be discussed.

07 ISOTOPE AND RADIATION SOURCES↗

Materials Data on LaOsN3 by Materials Project

LaOsN3 crystallizes in the monoclinic P2_1/m space group. The structure is one-dimensional and consists of two LaOsN3 ribbons oriented in the (1, 0, 0) direction. La3+ is bonded in a 1-coordinate geometry to one N3- atom. The La–N bond length is 2.47 Å. Os6+ is bonded in a T-shaped geometry to three N3- atoms. There are a spread of Os–N bond distances ranging from 1.91–2.02 Å. There are three inequivalent N3- sites. In the first N3- site, N3- is bonded in a 2-coordinate geometry to one Os6+ and one N3- atom. The N–N bond length is 1.24 Å. In the second N3- site, N3- is bonded in a distorted linear geometry to two equivalent Os6+ atoms. In the third N3- site, N3- is bonded in a 2-coordinate geometry to one La3+ and one N3- atom.

36 MATERIALS SCIENCE↗

Trace element geochemistry and the early lunar differentiation

The results are considered of experiments in which thermal neutron activation analysis was used to measure the halogens, U, Te, Ru, Os, and Hg in lunar samples. A calorimetric method was used for P2O5. Three Apollo 17 basalts, one Apollo 11 basalt, and one Apollo 15 basalt were used for the Ru-Os study. Os and Ru were measured in seven samples of breccia 14305 in a series of experiments to check an apparent anomaly in the isotopic composition of the Hg which it contains. A lunar model for Ru-Os partition is discussed. It is suggested that Ru and Os were partitioned and fractionated in the original differentiation of the lunar surface ocean. Fractionation among near-surface materials was less than a factor of 2 according to the lithic breccia data. Fractionations among basaltic sources were very large, exceeding 100, and primarily due to Ru. A clue to Ru and Os distributions at the depths from which mare basalts were derived may be provided by the relative ages of the basalts. These are interpreted as being related to partial melting in response to temperature increases at depth with time.

Jovanovic, S.↗

Materials Data on KOsN(Cl2O)2 by Materials Project

KOsN(OCl2)2 crystallizes in the orthorhombic Cmc2_1 space group. The structure is three-dimensional. K1+ is bonded in a 7-coordinate geometry to three O2- and four Cl1- atoms. There are a spread of K–O bond distances ranging from 2.75–3.08 Å. There are two shorter (3.39 Å) and two longer (3.67 Å) K–Cl bond lengths. Os2+ is bonded in a distorted octahedral geometry to one N5+, one O2-, and four Cl1- atoms. The Os–N bond length is 1.69 Å. The Os–O bond length is 2.01 Å. There are two shorter (2.31 Å) and two longer (2.39 Å) Os–Cl bond lengths. N5+ is bonded in a single-bond geometry to one Os2+ atom. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a 2-coordinate geometry to one K1+ and one Os2+ atom. In the second O2- site, O2- is bonded in a 4-coordinate geometry to two equivalent K1+ and two equivalent Cl1- atoms. Both O–Cl bond lengths are 2.44 Å. There are two inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a 1-coordinate geometry to one K1+ and one Os2+ atom. In the second Cl1- site, Cl1- is bonded in a 2-coordinate geometry to one K1+, one Os2+, and one O2- atom.

36 MATERIALS SCIENCE↗

Materials Data on H12OsSN4O7 by Materials Project

(OsH12(N2O)2)2(SO4)2O2 crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of four sulfuric acid molecules, four water molecules, and four OsH12(N2O)2 clusters. In two of the OsH12(N2O)2 clusters, Os8+ is bonded in an octahedral geometry to four N1- and two equivalent O2- atoms. All Os–N bond lengths are 2.14 Å. Both Os–O bond lengths are 1.75 Å. There are two inequivalent N1- sites. In the first N1- site, N1- is bonded in a trigonal non-coplanar geometry to one Os8+ and three H1+ atoms. There is one shorter (1.03 Å) and two longer (1.04 Å) N–H bond length. In the second N1- site, N1- is bonded in a trigonal non-coplanar geometry to one Os8+ and three H1+ atoms. There is two shorter (1.03 Å) and one longer (1.04 Å) N–H bond length. There are six inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to one N1- atom. In the second H1+ site, H1+ is bonded in a single-bond geometry to one N1- atom. In the third H1+ site, H1+ is bonded in a single-bond geometry to one N1- atom. In the fourth H1+ site, H1+ is bonded in a single-bond geometry to one N1- atom. In the fifth H1+ site, H1+ is bonded in a single-bond geometry to one N1- atom. In the sixth H1+ site, H1+ is bonded in a single-bond geometry to one N1- atom. O2- is bonded in a single-bond geometry to one Os8+ atom. In two of the OsH12(N2O)2 clusters, Os8+ is bonded in an octahedral geometry to four N1- and two equivalent O2- atoms. All Os–N bond lengths are 2.14 Å. Both Os–O bond lengths are 1.75 Å. There are two inequivalent N1- sites. In the first N1- site, N1- is bonded in a trigonal non-coplanar geometry to one Os8+ and three H1+ atoms. There is two shorter (1.03 Å) and one longer (1.04 Å) N–H bond length. In the second N1- site, N1- is bonded in a trigonal non-coplanar geometry to one Os8+ and three H1+ atoms. There is two shorter (1.03 Å) and one longer (1.04 Å) N–H bond length. There are six inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to one N1- atom. In the second H1+ site, H1+ is bonded in a single-bond geometry to one N1- atom. In the third H1+ site, H1+ is bonded in a single-bond geometry to one N1- atom. In the fourth H1+ site, H1+ is bonded in a single-bond geometry to one N1- atom. In the fifth H1+ site, H1+ is bonded in a single-bond geometry to one N1- atom. In the sixth H1+ site, H1+ is bonded in a single-bond geometry to one N1- atom. O2- is bonded in a single-bond geometry to one Os8+ atom.

36 MATERIALS SCIENCE↗

Surfactant-free syntheses and pair distribution function analysis of osmium nanoparticles

A surfactant-free synthesis of precious metal nanoparticles (NPs) performed in alkaline low-boiling-point solvents has been recently reported. Monoalcohols are here investigated as solvents and reducing agents to obtain colloidal Os nanoparticles by using low-temperature (<100 °C) surfactant-free syntheses. The effect of the precursor (OsCl 3 or H 2 OsCl 6 ), precursor concentration (up to 100 mM), solvent (methanol or ethanol), presence or absence of a base (NaOH), and addition of water (0 to 100 vol %) on the resulting nanomaterials is discussed. It is found that no base is required to obtain Os nanoparticles as opposed to the case of Pt or Ir NPs. The robustness of the synthesis for a precursor concentration up to 100 mM allows for the performance of X-ray total scattering with pair distribution function (PDF) analysis, which shows that 1–2 nm hexagonal close packed (hcp) NPs are formed from chain-like [OsO x Cl y ] complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fleetite, Cu 2 RhIrSb 2 , a New Species of Platinum-Group Mineral from the Miass Placer Zone, Southern Urals, Russia

Fleetite, Cu 2 RhIrSb 2 , a new species of platinum-group mineral (PGM), was discovered intergrown with an Os–Ir–Ru alloy in the Miass Placer Zone (Au–PGE), southern Urals, Russia. A single grain 50 μm across was found. Osmium, ruthenium, and iridium are the main associated minerals; also present are Pt–Fe alloys, laurite, Sb-rich irarsite, Rh-rich tolovkite, kashinite, anduoite, ferronickelplatinum, heazlewoodite, PGE-bearing pentlandite and digenite, as well as micrometric inclusions of forsterite (Fo 93.7 ), chromite–magnesiochromite, and Mg-rich edenite. In reflected light, fleetite is light gray; it is opaque, isotropic, non-pleochroic, and non-bireflectant. We report reflectance values measured in air. A mean of seven point-analyses (wavelength-dispersive spectrometry) gave Cu 13.93, Ni 8.60, Fe 0.10, Ir 28.07, Rh 7.91, Ru 1.96, Sb 39.28, total 99.85 wt.%, corresponding to (Cu 1.41 Ni 0.58 Fe 0.01 ) Σ2.00 (Rh 0.49 Ni 0.36 Ru 0.12 ) Σ0.97 Ir 0.95 Sb 2.08 on the basis of six atoms per formula unit, taking into account the structural results. The calculated density is 10.83 g/cm 3 . Single-crystal X-ray studies show that fleetite is cubic, space group Fdm (#227), a = 11.6682(8) Å, V = 1588.59(19) Å 3 , and Z = 16. A least-squares refinement of X-ray powder-diffraction data gave a = 11.6575(5) Å and V = 1584.22(19) Å 3 . The strongest five reflections in the powder pattern [d in Å(I)(hkl)] are: 6.70(75)(111), 4.13(100)(220), 3.52(30)(311), 2.380(50)(422), 2.064(40)(440). Results of synchrotron micro-Laue diffraction experiments are consistent [a = 11.66(2) Å]. The crystal structure of fleetite was solved and refined to R = 0.0340 based upon 153 reflections with F o > 4σ(F o ). It is isotypic with Pd 11 Bi 2 Se 2 and best described as intermetallic, with all metal atoms in 12-fold coordination. Fleetite and other late exotic phases were formed by reaction of the associated alloy phases with a fluid phase enriched in Sb, As, and S in circulation in the cooling ophiolite source-rock. The mineral is named after Michael E. Fleet (1938–2017) in recognition of his significant contributions to the Earth Sciences.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Transmission Electron Microscopy Study of a Refractory Metal Grain from a Calcium-Aluminum-Rich Inclusion in the Leoville CV3 Chondrite

Introduction: Calcium-aluminum-rich inclusions (CAIs) are an important component of chondritic meteorites. They can contain materials that are thermodynamically predicted and isotopically age dated to be among the first-formed solids in our solar system [1-5]. Observed in some CAIs are micron to sub-micron sized inclusions rich in Fe, Ni, and high-Z elements such as Pt, Os, Ir and W, in the form of refractory metal nuggets (RMNs), fremdlinges, and ‘nugget like objects’ (NLOs) [1,6]. Refractory siderophile elements such as Os, Ir and Ru are thermodynamically predicted to condense at temperatures well in excess of the major CAI phases such as melilite, perovskite, spinel and hibonite [2,7-9]. These refractory metal inclusions in CAIs can therefore serve as probes into the thermodynamic landscape of the early solar protoplanetary disk. Here we report on a refractory grain identified in a CAI of the Leoville CV3 chondrite. This work is part of an ongoing effort to gain insight into the thermochemistry of the early solar system through systematic analyses of the structure and chemistry of various components in CAIs [10-13]. Sample and Analytical Techniques: A fluffy type A CAI (Fig. 1A) was identified in a section of the Leoville, CV3 chondrite (Center for Meteorite Studies, Arizona State University collection, #821_C_3) using a JOEL-JXA 8530F electron microprobe at Arizona State University. Backscattered electron (BSE) imaging and energy-dispersive X-ray spectroscopy (EDS) were used to identify refractory metal grains in the CAI using a Thermo Fisher (formerly FEI) Helios NanoLab 660 G3 focused-ion-beam scanning-electron microscope (FIBSEM) located at the Kuiper Materials Imaging and Characterization Facility (KMICF) at the Lunar and Planetary Laboratory, University of Arizona. The FIB is equipped with an EDAX EDS system. We selected one of the larger (micron-sized) refractory metal grains, designated as ‘Spud’ (Fig. 1B) for further analysis. ‘Spud’ was extracted and thinned to electron transparency (<100 nm) using the FIB-SEM located in KMICF, following methods described by [14- 15]. The FIB section was analyzed using a 200 keV Hitachi HF5000 scanning transmission electron microscope (S/TEM) located at KMICF. The HF5000 is equipped with cold-field emission gun, 3rd-order spherical aberration corrector for STEM imaging, and an Oxford Instruments X-Max N 100 TLE energydispersive spectroscopy (EDS) system with dual 100 mm2 windowless silicon-drift detectors (Ω = 2.0 sr). Selected-area electron-diffraction (SAED) patterns were acquired to aid in determination of crystallinity and phase. Results: The mineralogy, texture, and morphology of the CAI are consistent with that of a fluffy type A (FTA) CAI [16]. BSE imaging at high magnifications revealed grains with high contrast, indicative of compositions rich in elements of higher atomic number relative to surrounding material. These high-Z grains have sizes that range from ∼250 nm to 4 µm. EDS analyses confirm that the bright grains are metal-rich inclusions. A minor fraction of the grains are composed of only Fe and Ni, but the majority (∼60%) of the identified inclusions also contained various refractory siderophiles including Os, Ru, Zr, Ir and Mo. EDS analysis on the FIB-SEM of Spud shows that it contains Fe, Ni, Mo and Ru. High-angle annular dark-field (HAAFD) imaging and EDS mapping in the TEM (Fig. 2) show that Spud occurs in melilite (Ca1.9Al1.99Si1.06O7). Spud contains a subhedral to anhedral morphology and is compositionally heterogenous (polyphasic, Fig. 2). Local spatial correlation occurs among Fe, Ni, and Pt, and also among Os, Ru, and Mo. SAED patterns show that the Fe-Ni-Pt, Fe-Os-Mo-Ru and Fe-Pt regions are crystalline. Discussion: CAIs can contain various types of inclusions rich in Fe, Ni and refractory siderophiles such as Os, Ru, W and Pt [1]. RMNs are micron-sized, single phase alloy grains and can contain Os, Ir, Ru and Rh [1,7,17]. NLOs are also micron-sized inclusions, but contain two phases, a refractory metal, and an oxide [6]. Fremdlinge are the largest of such inclusions (tens of microns in size) and are complex aggregates of Fe-Ni alloy, silicates, oxides, and sulfides [1,17]. While the size of Spud matches previous descriptions of RMNs and NLOs, Spud is neither a single-phase alloy like RMNs, nor does it contain one metal phase and one oxide like NLOs. Spud does not match the above described categories of refractory metal inclusions. The presence of refractory siderophiles such as Mo, Os, Ru, and Pt suggests a high-temperature origin. Thermodynamic modelling by [7] indicates condensation temperatures of 1917 K, 1693 K, 1613 K and 1415 K for Os, Mo, Ru and Pt respectively. These models also show that following the initial condensation of a refractory metal, alloying of solutes such as Fe, Ni and W, occurs in levels proportional to their partial pressures in the surrounding gas. Such alloying occurs at temperatures above the condensation temperatures of common CAI phases such as melilite (1529 K), perovskite (1441 K), spinel (197 K) and forsterite (1354 K) [2]. The polyphasic nature of Spud could be the result of such high-temperature alloying, possibly shortly after the condensation of Mo and Ru at 1693 K and 1613 K respectively. That Spud occurs as an inclusion is consistent with it having formed prior to and at temperature above that of its host melilite in this FTA CAI, which is qualitatively consistent with such prior thermodynamic modeling. Further, the polyphasic nature of Spud is similar to refractory grains from a FTA CAI in the Northwest Africa (NWA) 8323, CV3 chondrite [11-13]. These data suggest that such refractory metal grains could have been widespread in the inner and early solar protoplanetary disk and represent some of the earliest formed solids to have condensed. Acknowledgments: Research and instrumentation supported by NASA grants #NNX12AL47G, #NNX15AJ22G and #80NSSC19K0509, and NSF grants #1531243 and #0619599. Fig 2. STEM data on ‘Spud’. HAADF Image (Top) False-color EDS Maps (Bottom) References: [1] MacPherson G. J. (2014) T. of Geochem. Vol I: Met. And Cosmochem. Processes, 139-179. [2] Lodders K. (2003) ApJ, 591, 1220-1247. [3] Ebel D. S. (2006) Met. & the Early S. Sys. II., 253- 277. [4] Amelin Y. (2002) Science, 297, 1678-1683. [5] Connelly J.N. et.al. (2012) Science, 338, 651-655. [6] Schwander D. et al. (2015) GCA, 18, 70-87. [7] Palme H. and Wlotzka F. (1976) EPSL, 33, 45-60. [8] Berg T. et al. (2009) ApJ, 702, 172-176. [9] Liffman K. et al. (2021) Icarus, 221, 89-105. [10] Zega T.J. et al. (2021) PSJ, 2, 115. [11] Ramprasad T. et al. (2020) LPSC LI, Abstract #2472. [12] Ramprasad T. et al. (2021) Microscopy & Microanalysis, S1, 2792-2794. [13] Ramprasad T. et al. (2021) 84th MetSoc, Abstract #6123. [14] Zega T.J. et al. (2007) MAPS, 42, 1373-1386. [15] Ramprasad T. et al. (2022) MAPS, in revision. [16] Grossman L. (1975), GCA, 39, 433-454. [17] El Goresy A. et al. (1978) LPSC IX, Abstract#1100

T. Ramprasad↗

Ferrotorryweiserite, Rh 5 Fe 10 S 16 , a New Mineral Species from the Sisim Placer Zone, Eastern Sayans, Russia, and the Torryweiserite–Ferrotorryweiserite Series

Ferrotorryweiserite, Rh 5 Fe 10 S 16 , occurs as small grains (≤20 µm) among droplet-like inclusions (up to 50 μm in diameter) of platinum-group minerals (PGM), in association with oberthürite or Rh-bearing pentlandite, laurite, and a Pt-Pd-Fe alloy (likely isoferroplatinum and Fe-Pd-enriched platinum), hosted by placer grains of Os-Ir alloy (≤0.5 mm) in the River Ko deposit. The latter is a part of the Sisim placer zone, which is likely derived from ultramafic units of the Lysanskiy layered complex, southern Krasnoyarskiy kray, Russia. The mineral is opaque, gray to brownish gray in reflected light, very weakly bireflectant, not pleochroic to weakly pleochroic (grayish to light brown tints), and weakly anisotropic. The calculated density is 5.93 g·cm –3 . Mean results (and ranges) of four WDS analyses are: Ir 18.68 (15.55–21.96), Rh 18.34 (16.32–20.32), Pt 0.64 (0.19–1.14), Ru 0.03 (0.00–0.13), Os 0.07 (0.02–0.17), Fe 14.14 (13.63–14.64), Ni 13.63 (12.58–14.66), Cu 4.97 (3.42–6.41), Co 0.09 (0.07–0.11), S 29.06 (28.48–29.44), and total 99.66 wt.%. They correspond to the following formula calculated for a total of 31 atoms per formula unit: (Rh 3.16 Ir 1.72 Pt 0.06 Ru 0.01 Os 0.01 ) Σ 4.95 (Fe 4.48 Ni 4.11 Cu 1.38 Co 0.03 ) Σ10.00 S 16.05 . The results of synchrotron micro-Laue diffraction studies indicate that ferrotorryweiserite is trigonal; its probable space group is $R\bar{3}m$ (#166) based on its Ni-analog, torryweiserite. The unit-cell parameters refined from 177 reflections are a = 7.069 (2) Å, c = 34.286 (11) Å, V = 1484 (1) Å 3 , and Z = 3. The c:a ratio is 4.8502. The strongest eight peaks in the X-ray diffraction pattern derived from results of micro-Laue diffraction study [d in Å(hkil)(I)] are 2.7950 ($20\bar{2}5$) (100); 5.7143 (0006) (60); 1.7671 ($22\bar{4}0$) (44.4); 3.0486 ($20\bar{2}1$) (39.4); 5.7650 ($10\bar{1}2$) (38.6); 2.5956 ($20\bar{2}7$) (37.8); 3.0058 ($11\bar{2}6$) (36.5); and 1.5029 ($4\bar{2}\bar{2}12$) (35.3). Ferrotorryweiserite and the associated PGM crystallized from microvolumes of residual melt at late stages of crystallization of grains of Os- and Ir-dominant alloys occurred in lode zones of chromitites of the Lysanskiy layered complex. In a particular case, the residual melt is disposed peripherally around a core containing a disequilibrium association of magnesian olivine (Fo 72.9–75.6 ) and albite (Ab 81.6–86.4 ), with the development of skeletal crystals of titaniferous augite: Wo 40.8–43.2 En 26.5–29.3 Fs 20.3–22.6 Aeg 6.9–9.5 (2.82–3.12 wt.% TiO 2 ). Ferrotorryweiserite represents the Fe-dominant analog of torryweiserite. We also report occurrences of ferrotorryweiserite in the Marathon deposit, Coldwell Complex, Ontario, Canada, and infer the existence of the torryweiserite–ferrotorryweiserite solid solution in other deposits and complexes.

58 GEOSCIENCES↗

Materials Data on K3NaOs2O9 by Materials Project

K3NaOs2O9 crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. there are two inequivalent K1+ sites. In the first K1+ site, K1+ is bonded to twelve O2- atoms to form distorted KO12 cuboctahedra that share corners with twelve KO12 cuboctahedra, faces with six equivalent KO12 cuboctahedra, faces with two equivalent NaO6 octahedra, and faces with six equivalent OsO6 octahedra. There are six shorter (3.00 Å) and six longer (3.05 Å) K–O bond lengths. In the second K1+ site, K1+ is bonded to twelve O2- atoms to form distorted KO12 cuboctahedra that share corners with nine KO12 cuboctahedra, corners with three equivalent OsO6 octahedra, faces with seven KO12 cuboctahedra, faces with three equivalent NaO6 octahedra, and faces with four equivalent OsO6 octahedra. The corner-sharing octahedral tilt angles are 1°. There are a spread of K–O bond distances ranging from 2.92–3.31 Å. Na1+ is bonded to six equivalent O2- atoms to form NaO6 octahedra that share corners with six equivalent OsO6 octahedra and faces with eight KO12 cuboctahedra. The corner-sharing octahedral tilt angles are 6°. All Na–O bond lengths are 2.32 Å. Os7+ is bonded to six O2- atoms to form distorted OsO6 octahedra that share corners with three equivalent KO12 cuboctahedra, corners with three equivalent NaO6 octahedra, faces with seven KO12 cuboctahedra, and a faceface with one OsO6 octahedra. The corner-sharing octahedral tilt angles are 6°. There is three shorter (1.81 Å) and three longer (2.03 Å) Os–O bond length. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a 2-coordinate geometry to four K1+ and two equivalent Os7+ atoms. In the second O2- site, O2- is bonded in a distorted linear geometry to four K1+, one Na1+, and one Os7+ atom.

36 MATERIALS SCIENCE↗

Materials Data on Sc13Os3Br16 by Materials Project

Sc13Os3Br16 crystallizes in the orthorhombic Pnnm space group. The structure is two-dimensional and consists of two Sc13Os3Br16 sheets oriented in the (0, 0, 1) direction. there are five inequivalent Sc sites. In the first Sc site, Sc is bonded in a 6-coordinate geometry to two Os and four Br atoms. There are one shorter (2.69 Å) and one longer (2.80 Å) Sc–Os bond lengths. There are a spread of Sc–Br bond distances ranging from 2.70–3.31 Å. In the second Sc site, Sc is bonded in a 6-coordinate geometry to two Os and four Br atoms. There are one shorter (2.64 Å) and one longer (2.77 Å) Sc–Os bond lengths. There are a spread of Sc–Br bond distances ranging from 2.80–3.31 Å. In the third Sc site, Sc is bonded to two equivalent Os and four Br atoms to form distorted ScOs2Br4 octahedra that share corners with two equivalent ScBr6 octahedra, an edgeedge with one ScOs2Br4 octahedra, and faces with two equivalent ScOs2Br4 pentagonal pyramids. The corner-sharing octahedral tilt angles are 29°. Both Sc–Os bond lengths are 2.68 Å. There are a spread of Sc–Br bond distances ranging from 2.75–3.02 Å. In the fourth Sc site, Sc is bonded to two equivalent Os and four Br atoms to form a mixture of distorted edge and face-sharing ScOs2Br4 pentagonal pyramids. Both Sc–Os bond lengths are 2.76 Å. There are a spread of Sc–Br bond distances ranging from 2.80–2.84 Å. In the fifth Sc site, Sc is bonded to six Br atoms to form corner-sharing ScBr6 octahedra. The corner-sharing octahedral tilt angles are 29°. There are two shorter (2.69 Å) and four longer (2.73 Å) Sc–Br bond lengths. There are two inequivalent Os sites. In the first Os site, Os is bonded in a 8-coordinate geometry to eight Sc atoms. In the second Os site, Os is bonded in a body-centered cubic geometry to eight Sc atoms. There are six inequivalent Br sites. In the first Br site, Br is bonded in a distorted T-shaped geometry to three Sc atoms. In the second Br site, Br is bonded in a 4-coordinate geometry to four Sc atoms. In the third Br site, Br is bonded in a 3-coordinate geometry to three Sc atoms. In the fourth Br site, Br is bonded in a 4-coordinate geometry to four Sc atoms. In the fifth Br site, Br is bonded in a 2-coordinate geometry to two equivalent Sc atoms. In the sixth Br site, Br is bonded in a 2-coordinate geometry to four Sc atoms.

36 MATERIALS SCIENCE↗