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At least 1,063 records · Page 59

Columnar Aerosol Single-Scattering Albedo and Phase Function Retrieved from Sky Radiance Over the Ocean: Measurements of African Dust

The single-scattering albedo and phase function of African mineral dust are retrieved from ground-based measurements of sky radiance collected in the Florida Keys. The retrieval algorithm employs the radiative transfer equation to solve by iteration for these two properties which best reproduce the observed sky radiance using an assumed aerosol vertical structure and measured aerosol optical depth. Thus, no assumptions regarding particle size, shape, or composition are required. The single-scattering albedo, presented at fourteen wavelengths between 380 and 870 nm, displays a spectral shape expected of iron-bearing minerals but is much higher than current dust models allow. This indicates the absorption of light by mineral dust is significantly overestimated in climate studies. Uncertainty in the retrieved albedo is less than 0.02 due to the small uncertainty in the solar-reflectance-based calibration (12.2%) method employed. The phase function retrieved at 860 nm is very robust under simulations of expected experimental errors, indicating retrieved phase functions at this wavelength may be confidently used to describe aerosol scattering characteristics. The phase function retrieved at 443 nm is very sensitive to expected experimental errors and should not be used to describe aerosol scattering. Radiative forcing by aerosol is the greatest source of uncertainty in current climate models. These results will help reduce uncertainty in the absorption of light by mineral dust. Assessment of the radiative impact of aerosol species is a key component to NASA's Earth System Enterprise.

Cattrall, Christopher↗

The Shr receptor from Streptococcus pyogenes uses a cap and release mechanism to acquire heme–iron from human hemoglobin

Streptococcus pyogenes (group A Streptococcus ) is a clinically important microbial pathogen that requires iron in order to proliferate. During infections, S. pyogenes uses the surface displayed Shr receptor to capture human hemoglobin (Hb) and acquires its iron-laden heme molecules. Through a poorly understood mechanism, Shr engages Hb via two structurally unique N-terminal Hb-interacting domains (HID1 and HID2) which facilitate heme transfer to proximal NEAr Transporter (NEAT) domains. Based on the results of X-ray crystallography, small angle X-ray scattering, NMR spectroscopy, native mass spectrometry, and heme transfer experiments, we propose that Shr utilizes a “cap and release” mechanism to gather heme from Hb. In the mechanism, Shr uses the HID1 and HID2 modules to preferentially recognize only heme-loaded forms of Hb by contacting the edges of its protoporphyrin rings. Heme transfer is enabled by significant receptor dynamics within the Shr–Hb complex which function to transiently uncap HID1 from the heme bound to Hb’s β subunit, enabling the gated release of its relatively weakly bound heme molecule and subsequent capture by Shr’s NEAT domains. These dynamics may maximize the efficiency of heme scavenging by S. pyogenes , enabling it to preferentially recognize and remove heme from only heme-loaded forms of Hb that contain iron.

59 BASIC BIOLOGICAL SCIENCES↗

Zero-Valent Iron Permeable Reactive Barrier to Remediate Volatile Organic Compounds in Groundwater - 20209

The US DOE-SRS, the US EPA, and the South Carolina Department of Health and Environmental Control determined it was appropriate to perform a non-time critical removal action at the P-Area Groundwater Operable Unit at the SRS to reduce the mass and downgradient transport of trichloroethylene in the P-Area groundwater plume. Contaminated groundwater discharges to a nearby stream, Steel Creek, within the SRS boundaries, resulting in trichloroethylene concentrations above the maximum contaminant level. Impact to surface water is limited in areal extent and supported by recently collected characterization data. The P-Area Groundwater Operable Unit encompasses the groundwater beneath an industrial area within SRS, P Area, where the P-Reactor once operated. The boundaries of the P-Area Groundwater Operable Unit extend northwest to Steel Creek, northeast toward PAR Pond, and southeast to Meyers Branch. Groundwater in the Upper Three Runs Aquifer of the P-Area Groundwater Operable Unit has been impacted by reactor and facility operations between 1954 and 1991, including tritium and volatile organic compounds. The P-Area surface units contributing to groundwater contamination were remediated as part of the P-Area Operable Unit in 2011. The P-Reactor closure is one of the first of its kind in the DOE Complex and is one of only a few full-sized production reactors in the US to undergo completion of final closure activities. The nature and extent of groundwater contamination was determined using a variety of investigative approaches such as groundwater monitoring wells, direct-push technology, and surface water samples. Groundwater contamination associated with trichloroethylene is primarily exhibited in a narrow plume that extends from the source area at P-Reactor and west to Steel Creek. Maximum contaminant level exceedances in groundwater occur over an area of ∼6.9 hectares for trichloroethylene with concentrations as high as 7.7 milligrams per liter. To the west of the P-Area facility area, the trichloroethylene groundwater plume is controlled by a buried geologic feature, assumed to be an old stream bed, that further narrows the groundwater plume in what has been designated as the 'neck area.' This narrowing of the groundwater plume provides an ideal location for a treatment barrier. The non-time critical removal action alternative chosen is to install a zero-valent iron permeable reactive barrier within the neck area of the trichloroethylene groundwater plume, perpendicular to groundwater flow direction. This technology will provide a treatment barrier that will reduce trichloroethylene groundwater concentrations by 90% and has an anticipated useful life of at least 25 years. A pre-design investigation was performed in the neck area to confirm site lithology, hydrogeology, geochemistry, and extent of trichloroethylene contamination prior to a final design. A treatability study, conducted as part of the pre-design investigation, indicated that the subsurface and groundwater in the PArea Groundwater Operable Unit is compatible with the zero-valent iron and will not lead to excessive buildup from mineralization/precipitation or biofouling. Probabilistic modeling was conducted using field and laboratory data to determine the expected performance of the zero-valent iron permeable reactive barrier. The model simulations indicated that a 3.81-centimeter thick barrier would provide greater than 90% reduction of trichloroethylene groundwater concentration. The final design of the zero-valent iron permeable reactive barrier is a barrier that will extend 80.5 linear meters in a 'zigzag' orientation to best transect the trichloroethylene plume and account for varying groundwater flow. The barrier will be installed from 13.7 meters below ground surface to 41.1 meters below ground surface for 65.8 linear meters and from 13.7 meters below ground surface to 36.6 meters below ground surface for 14.6 linear meters, the base of which is 'keyed' into a low permeability zone. The barrier is designed to a thickness of 10.2 centimeters, which was determined to reduce the trichloroethylene groundwater concentrations by greater than 90% with a safety factor of 2.67. A total of approximately 689 metric tons of zero-valent iron will be injected through 22 injection wells spaced 3.66 meters apart, using guar to suspend the zero-valent iron. Zero-valent iron permeable reactive barrier construction will be monitored through 23 installed resistivity receivers offset 7.32 meters from the zerovalent iron permeable reactive barrier. The zero-valent iron will be energized with a low-voltage 100 Hertz signal during injection and will be monitored using the resistivity receivers to ensure complete coalescence of the zero-valent iron permeable reactive barrier. The zero-valent iron was sized to have a hydraulic conductivity greater than the natural subsurface, thus promoting groundwater flow through the barrier. As contaminated groundwater contacts the zero-valent iron, volatile organic compounds, including trichloroethylene, are immediately degraded to harmless compounds such as ethylene. The performance of the zero-valent iron permeable reactive barrier will be monitored using three upgradient monitoring well clusters, six downgradient monitoring well clusters, and four in-wall monitoring wells. The in-wall monitoring wells will indicate immediate reduction of trichloroethylene mass in the groundwater and allow analyses of the zero-valent iron permeable reactive barrier health. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Taxonomic Re-Evaluation and Genomic Comparison of Novel Extracellular Electron Uptake-Capable Rhodovulum visakhapatnamense and Rhodovulum sulfidophilum Isolates

Rhodovulum spp. are anoxygenic phototrophic purple bacteria with versatile metabolisms, including the ability to obtain electrons from minerals in their environment to drive photosynthesis, a relatively novel process called phototrophic extracellular electron uptake (pEEU). A total of 15 strains of Rhodovulum sulfidophilum were isolated from a marine estuary to observe these metabolisms in marine phototrophs. One representative strain, Rhodovulum sulfidophilum strain AB26, can perform phototrophic iron oxidation (photoferrotrophy) and couples carbon dioxide fixation to pEEU. Here, we reclassify two R. sulfidophilum isolates, strainAB26 and strain AB19, as Rhodovulum visakhapatnamense using taxonomic re-evaluation based on 16S and pufM phylogenetic analyses. The strain AB26 genome consists of 4,380,746 base-pairs, including two plasmids, and encodes 4296 predicted protein-coding genes. Strain AB26 contains 22 histidine kinases, 20 response regulators, and dedicates ~16% of its genome to transport. Transcriptomic data under aerobic, photoheterotrophy, photoautotrophy, and pEEU reveals how gene expression varies between metabolisms in a novel R. visakhapatnamense strain. Genome comparison led by transcriptomic data under pEEU reveals potential pEEU-relevant genes both unique to R. visakhapatnamense strains and shared within the R. sulfidophilum genomes. With these data we identify potential pEEU-important transcripts and how speciation may affect molecular mechanisms of pEEU in Rhodovulum species from the same environment.

59 BASIC BIOLOGICAL SCIENCES↗

Refractory spherules in the Murchison meteorite - Are they condrules

The textural and mineralogical features of refractory spherules found in the Murchison meteorite are examined in relation to their probable origin. Based on a study of 12 samples it is found that the refractory spherules, with hibonite-bearing or spinel or spinel-perovskite cores surrounded by an iron-rich silicate layer, have compositions similar to those of coexisting irregular inclusions. The shape and internal textures of the spherules, however, suggest formation from a liquid. It is proposed that the spherules may be melted equivalents of the irregular inclusions, and thus may be properly termed chondrules. It is noted that such melting would have involved very high temperatures.

Macdougall, J. D.↗

Iron rich low cost superalloys

An iron-rich low-cost superalloy was developed. The alloy, when processed by conventional chill casting, has physical and mechanical properties that compare favorably with existing nickel and cobalt based superalloys while containing significantly lower amounts of strategic elements. Studies were also made on the properties of Cr(20)-Mn(10)-C(3.4)-Fe(bal.), a eutectic alloy processed by chill casting and directional solidification which produced an aligned microstructure consisting of M7C3 fibers in a gamma-Fe matrix. Thermal expansion of the M7C3 (M = Fe, Cr, Mn) carbide lattice was measured up to 800 C and found to be highly anisotropic, with the a-axis being the predominant mode of expansion. Repetitive impact sliding wear experiments performed with the Fe rich eutectic alloy showed that the directionally solidified microstructure greatly improved the alloy's wear resistance as compared to the chill cast microstructure and conventional nickel base superalloys. Studies on the molybdenum cementite phase prove that the crystal structure of the xi phase is not orthorhombic. The crystal structure of the xi phase is made up of octahedra building elements consisting of four Mo and two Fe atoms and trigonal prisms consisting of four Fe and two Mo atoms. The voids are occupied by carbon atoms. The previous chemical formula for the molybdenum cementite MoFe2C is now clearly seen to be Mo12Fe22C10.

Wayne, S. F.↗

RSRM-11 (36OW011) ballistics mass properties (STS-35)

The propulsion performance and reconstructed mass properties data from Thiolol's RSRM-11 motors which were assigned to the STS-35 launch are contained. The Thiokol manufacturing designations for the motors were 360W011A/360W011B, which are referred to as RSRM-11A and RSRM-B, respectively. The launch of STS-35 occurred on 2 December 1990 at the Eastern Test Range (ETR). The data contained herein was input to the STS-35 Flight Evaluation Report. The SRM propellant, TP-H1148, is a composite type solid propellants, formulated of polybutediene acrylic acid, acryonitrile terpolymer binder, epoxy curing agent, ammonium perchlorate oxidizer, and aluminum powder fuel. A small amount of burning rate catalyst (iron oxide) was added to achieve the desired propellant burn rate. The propellant evaluation and raw material information for the RSRM-11 are included. The ballistic performance presented was based on the Operational Flight Instrumentation (OFI) 12.5 sample per second pressure data for the steady state and tail off portion of the pressure trace. Recent studies have shown that the transducers are affected by the measuring system at KSC and temperature gradients created by the igniter heaters. Therefore, an adjustment to the data from each transducer is made to make the initial reading match the atmospheric pressure at the time of launch.

Hutchinson, B. J.↗

A model of galactic cosmic rays for use in calculating linear energy transfer spectra

The Galactic Cosmic Rays (GCR) contain fully stripped nuclei, from Hydrogen to beyond the Iron group, accelerated to high energies and are a major component of the background radiation encountered by satellites and interplanetary spacecraft. This paper presents a GCR model which is based upon our current understanding of the astrophysics of GCR transport through interstellar and interplanetary space. The model can be used to predict the energy spectra for all stable and long-lived radioactive species from H to Ni over an energy range from 50 to 50,000 MeV/nucleon as a function of a single parameter, the solar modulation level phi. The details of this model are summarized, phi is derived for the period 1974 to present, and results from this model during the 1990/1991 Combined Release and Radiation Effects Satellite (CRRES) mission are presented.

Chen, J.↗

Robust Exploration and Commercial Missions to the Moon Using LANTR Propulsion and Lunar Liquid Oxygen Derived from FeO-Rich Pyroclastic Deposits

The nuclear thermal rocket (NTR) has frequently been identified as a key space asset required for the human exploration of Mars. This proven technology can also provide the affordable access through cislunar space necessary for commercial development and sustained human presence on the Moon. It is a demonstrated technology capable of generating both high thrust and high specific impulse (Isp approx.900 s) twice that of todays best chemical rockets. Nuclear lunar transfer vehicles consisting of a propulsion stage using three approx.16.5 klbf Small Nuclear Rocket Engines (SNREs), an in-line propellant tank, plus the payload can enable a variety of reusable lunar missions. These include cargo delivery and crewed lunar landing missions. Even weeklong tourism missions carrying passengers into lunar orbit for a day of sightseeing and picture taking are possible. The NTR can play an important role in the next phase of lunar exploration and development by providing a robust in-space lunar transportation system (LTS) that can allow initial outposts to evolve into settlements supported by a variety of commercial activities such as in-situ propellant production used to supply strategically located propellant depots and transportation nodes. The use of lunar liquid oxygen (LLO2) derived from iron oxide (FeO)-rich volcanic glass beads, found in numerous pyroclastic deposits on the Moon, can significantly reduce the launch mass requirements from Earth by enabling reusable, surface-based lunar landing vehicles (LLVs) using liquid oxygen/hydrogen (LO2/H2) chemical rocket engines. Afterwards, a LO2/H2 propellant depot can be established in lunar equatorial orbit to supply the LTS. At this point a modified version of the conventional NTR called the LOX-augmented NTR, or LANTR is introduced into the LTS allowing bipropellant operation and leveraging the mission benefits of refueling with lunar-derived propellants for Earth return. The bipropellant LANTR engine utilizes the large divergent section of its nozzle as an afterburner into which oxygen is injected and supersonically combusted with nuclear preheated hydrogen emerging from the engines choked sonic throat - essentially scramjet propulsion in reverse. By varying the oxygen-to-hydrogen mixture ratio, LANTR engines can operate over a range of thrust and Isp values while the reactor core power level remains relatively constant. A LANTR-based LTS offers unique mission capabilities including short transit time crewed cargo transports. Even a commuter shuttle service may be possible allowing one-way trip times to and from the Moon on the order of 36 hours or less. If only 1 of the extracted LLO2 propellant from identified resource sites were available for use in lunar orbit, such a supply could support daily commuter flights to the Moon for many thousands of years! The proposed paper outlines an evolutionary architecture and examines a variety of mission types and transfer vehicle designs, along with the increasing demands on LLO2 production as mission complexity and (Delta)V requirements increase. A comparison of vehicle features and engine operating characteristics, for both NTR and LANTR engines, is also provided along with a discussion of the propellant production and mining requirements associated with using FeO-rich volcanic glass as source material.

Nuclear rocket engines↗

Robust Exploration and Commercial Missions to the Moon Using Nuclear Thermal Rocket Propulsion and Lunar Liquid Oxygen Derived from FeO-Rich Pyroclasitc Deposits

The nuclear thermal rocket (NTR) has frequently been identified as a key space asset required for the human exploration of Mars. This proven technology can also provide the affordable access through cislunar space necessary for commercial development and sustained human presence on the Moon. It is a demonstrated technology capable of generating both high thrust and high specific impulse (I(sub sp) approx. 900 s) twice that of today's best chemical rockets. Nuclear lunar transfer vehicles-consisting of a propulsion stage using three approx. 16.5-klb(sub f) small nuclear rocket engines (SNREs), an in-line propellant tank, plus the payload-are reusable, enabling a variety of lunar missions. These include cargo delivery and crewed lunar landing missions. Even weeklong ''tourism'' missions carrying passengers into lunar orbit for a day of sightseeing and picture taking are possible. The NTR can play an important role in the next phase of lunar exploration and development by providing a robust in-space lunar transportation system (LTS) that can allow initial outposts to evolve into settlements supported by a variety of commercial activities such as in-situ propellant production used to supply strategically located propellant depots and transportation nodes. The use of lunar liquid oxygen (LLO2) derived from iron oxide (FeO)-rich volcanic glass beads, found in numerous pyroclastic deposits on the Moon, can significantly reduce the launch mass requirements from Earth by enabling reusable, surface-based lunar landing vehicles (LLVs)that use liquid oxygen and hydrogen (LO2/LH2) chemical rocket engines. Afterwards, a LO2/LH2 propellant depot can be established in lunar equatorial orbit to supply the LTS. At this point a modified version of the conventional NTR-called the LO2-augmented NTR, or LANTR-is introduced into the LTS allowing bipropellant operation and leveraging the mission benefits of refueling with lunar-derived propellants for Earth return. The bipropellant LANTR engine utilizes the large divergent section of its nozzle as an ''afterburner'' into which oxygen is injected and supersonically combusted with nuclear preheated hydrogen emerging from the engine's choked sonic throat-essentially ''scramjet propulsion in reverse.'' By varying the oxygen-to-hydrogen mixture ratio, LANTR engines can operate over a range of thrust and I(sub sp) values while the reactor core power level remains relatively constant. A LANTR-based LTS offers unique mission capabilities including short-transit-time crewed cargo transports. Even a ''commuter'' shuttle service may be possible allowing ''one-way'' trip times to and from the Moon on the order of 36 hours or less. If only 1% of the extracted LLO2 propellant from identified resource sites were available for use in lunar orbit, such a supply could support daily commuter flights to the Moon for many thousands of years! This report outlines an evolutionary architecture and examines a variety of mission types and transfer vehicle designs, along with the increasing demands on LLO2 production as mission complexity and velocity change delta V requirements increase. A comparison of vehicle features and engine operating characteristics, for both NTR and LANTR engines, is also provided along with a discussion of the propellant production and mining requirements associated with using FeO-rich volcanic glass as source material.

rocket↗

Dynamic properties of FeCrMnNi, a High Entropy Alloy

The goal of this paper was to assess the dynamic properties of a new class of materials, High entropy alloys (HEAs). Specifically, gas gun experiments coupled with recovery were performed on a specific HEA, FeCrMnNi, to measure its equation of state (EOS) and its spall strength, which is a measure of the stress required to nucleate voids under shock loading conditions. While there has been a plethora of work performed to assess the mechanical properties of these HEAs under uniaxial stress conditions as a function of strain rate, investigation of its properties in dynamic extremes remains rare. The current work fills this gap in knowledge for this novel class of materials. Our results show that the measured EOS for this material at one velocity was in reasonable agreement with an estimated Hugoniot. Furthermore, while the spall strength for this material was found to be ~1.9 GPa, with some variation based on sample location, the main failure mode wasbrittle. This brittle failure leading to formation of cracks in the material is different than the ductile failure observed in pure iron and its alloys. DOE/NV/03624--1298

36 MATERIALS SCIENCE↗

Modulating Iron Crystals with Lattice Chalcophile‐Siderophile Elements for Selective Dechlorinations Over Hydrogen Evolution

Selective dechlorination of organic chlorides over hydrogen evolution reaction (HER) remains a challenge because of their coincidence. Nanoscale zerovalent iron (nFe 0 ) draws a promising picture of in situ groundwater dechlorination, but its indiscriminate reactivity limits the application. Here, nFe 0 crystals are designed with electron shuttles and improved hydrophobic nature based on elemental chalcophile-siderophile characteristics, where chalcophile-siderophile S served as a bridge to allow impregnating nFe 0 crystals with weakly siderophile and strongly chalcophile Cu. Even impregnations of lattice chalcophile-siderophile elements into the nFe 0 crystals are evidenced at both intraparticle and individual-particle levels. The modulated Fe microenvironment and physicochemical properties broke the reactivity-selectivity-longevity-stability trade-off. Compared to nFe 0 , superhydrophobic Cu─S─nFe 0 with lattice expansion promoted dechlorination by 20-fold but inhibited HER by 150-fold, utilizing ≈80–100% electrons from the Fe 0 reservoir. This work demonstrates the concept of engineering nFe 0 lattice with tunable structure-property relationships, mimicking reductive dehalogenases by selectively interacting with halocarbon functional groups for efficient dehalogenation and sustainable groundwater remediation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Techno-Economic Analysis of Recycling Strategies for Catalyst and Acid During Catalytic Graphitization

With the aim of meeting the urgent demand for active anode materials (AAM) in energy storage systems, bio-based graphite (biographite) emerges as an affordable solution to de-risk the turbulent supply chain of critical minerals. Anode grade biographite requires high crystallinity and purity, which can be achieved by catalytic graphitization with iron, followed by acid washing. Therefore, a well-conceived process integration that recycles catalyst can be the starting point to commercialization. This study evaluates closed-loop catalyst recovery, and byproducts valorization scenarios through a technoeconomic framework to help understand the scale-up potential of biographite. For the acid washing, three reactors in series meet the required biographite purity at 99.95%. Iron and acid recovery can reduce material consumption and waste generation by ~95%, albeit at the expense of ~80% increase in capital costs. Recovery scenarios present similar capital and operational expenses, yielding minimum selling prices (MSP) near $6 kg-1 of biographite. Monte Carlo methodology reveals that feedstock price accounts for ~60% of MSP variance, followed by plant capacity ~20%. The likelihood of reaching a competitive profit margin of 30% in the U.S. AAM market sits at 85% average for recovery scenarios, and 103% when iron oxide is sold as byproduct. Additionally, an IRR >= 15% can be achieved for half of Monte Carlo simulations, representing promising early-stage results. Biographite production offers a strategic pathway to stabilize the anode market beyond China by integrating established technologies for a scalable, economically viable, and sustainable process. The role of catalyst recovery and byproducts utilization is critical for advancing the biomaterials industry.

97 MATHEMATICS AND COMPUTING↗

Robust Exploration and Commercial Missions to the Moon Using NTR LANTR Propulsion and Lunar-Derived Propellants

The nuclear thermal rocket (NTR) has frequently been identified as a key space asset required for the human exploration of Mars. This proven technology can also provide the affordable access through cislunar space necessary for commercial development and sustained human presence on the Moon. In his post-Apollo Integrated Space Program Plan (1970-1990), Wernher von Braun, proposed a reusable nuclear thermal propulsion stage (NTPS) to deliver cargo and crew to the Moon to establish a lunar base before undertaking human missions to Mars. The NTR option was selected by von Braun because it was a demonstrated technology capable of generating both high thrust and high specific impulse (Isp 900 s) twice that of todays best chemical rockets. In NASAs Mars Design Reference Architecture (DRA) 5.0 study, the crewed Mars transfer vehicle used three 25 klbf Pewee engines the smallest and highest performing engine tested in the Rover program along with graphite composite fuel. Smaller, lunar transfer vehicles consisting of a NTPS using three approximately 16.5 klbf Small Nuclear Rocket Engines (SNREs), an in-line propellant tank, plus the payload can enable a variety of reusable lunar missions. These include cargo delivery and crewed lunar landing missions. Even weeklong tourism missions carrying passengers into lunar orbit for a day of sightseeing and picture taking are possible. The NTR can play an important role in the next phase of lunar exploration and development by providing an affordable in-space lunar transportation system (LTS) that can allow initial outposts to evolve into settlements supported by a variety of commercial activities such as in-situ propellant production used to supply strategically located propellant depots and transportation nodes. The utilization of iron-rich volcanic glass or lunar polar ice (LPI) deposits (each estimated at billions of metric tons) for propellant production can significantly reduce the launch mass requirements from Earth and can enable reusable, surface-based lunar landing vehicles (LLVs) using liquid oxygen/hydrogen (LOX/LH2) chemical rocket engines. Afterwards, LOX/LH2 propellant depots can be established in lunar equatorial and polar orbits to supply the LTS. At this point a modified version of the conventional NTR called the LOX-augmented NTR, or LANTR would be introduced into the LTS allowing bipropellant operation and leveraging the mission benefits of refueling with lunar-derived propellants for Earth return. The bipropellant LANTR engine utilizes the large divergent section of its nozzle as an afterburner into which oxygen is injected and supersonically combusted with nuclear preheated hydrogen emerging from the engines choked sonic throat essentially scramjet propulsion in reverse. By varying the oxygen-to-hydrogen mixture ratio, LANTR engines can operate over a range of thrust and Isp values while the reactor core power level remains relatively constant. Eventually, a LANTR-based LTS can enable a rapid commuter shuttle with one-way trip times to and from the Moon ranging from 36 to 24 hours. Even if only 1 of the extracted propellant from identified volcanic glass and polar ice deposits were available for use in lunar orbit, such a supply could support daily commuter flights to the Moon for many thousands of years! An evolutionary mission architecture is outlined and a variety of lunar missions and transfer vehicle designs are examined, along with the increasing demands on propellant production as mission complexity increases. A comparison of vehicle features and engine operating characteristics, for both NTR and LANTR engines, is also provided along with a brief discussion on the propellant production issues associated with using volcanic glass and LPI as source material.

Spacecraft design↗

Effect of Anoxic Iron Corrosion on WIPP Brine Geochemistry FY23 Final Report (U)

A 280-day study was completed to evaluate the effect of zero-valent iron (Fe 0 ) on the Waste Isolation Pilot Plant (WIPP) brine geochemistry under anticipated reducing conditions. Hydrogen (H 2 ) gas is expected to be present in the repository after closure due to the anoxic corrosion of a vast quantity of iron contained in the waste forms disposed at WIPP; therefore, a background argon atmosphere containing H 2 was chosen for this study. WIPP groundwater brine pH and E h will impact the mobility and fate of plutonium within the repository. Modeling and laboratory results for Castile WIPP brine indicate that equilibrium fa values relative to the standard hydrogen electrode (SHE) are 40 mV more reducing (i.e., more negative) than those for Salado WIPP brine (-480 mV vs. -440 mV, respectively) because of the higher pH of the Castile brine (pH 9 .3 for Castile vs. pH 8.8 for Salado). The E h and pH data were corrected for the effects of high ionic strength. The experimental results for both brines are consistent with thermodynamic predictions using OLI Systems' Mixed Solvent Electrolyte chemical equilibrium model. The measured and corrected pH and E h data from this study are provided in Table ES-I and Table ES-2, respectively. The experimental study, with four test conditions in triplicate, was performed in a dual glovebox with a nominally 3 vol.% H 2 in argon atmosphere (target H 2 range: 3 ± I vol.%). Simulants containing MgO only ( experimental control) and MgO+Fe 0 (WIPP base case) were prepared for both the Salado and Castile brines. MgO was included in all simulants to account for the use of bulk magnesium oxide in the WIPP repository. Fe 0 was included in some simulants to incorporate the effects of the anoxic corrosion of iron and in-situ hydrogen generation in the study. The brine compositions were developed by Sandia National Laboratory (SNL; Xiong, 2008) and have been used in previous WIPP evaluations. The test method (agitation, etc.) is partially based on ASTM D3987-12. Twelve rounds of periodic measurements of pH and E h were performed over the course of the study. Chemical analysis results for liquids and solids (ICP-MS, ICP-ES, IC Anion, TIC, SEM-EDX) are consistent with the pH, E h , and thermodynamic modeling results. This study included the following conditions that deviate from anticipated post-closure conditions following brine intrusion, but were selected to facilitate bench-scale testing to validate modeling of pH and E h for the post-closure WIP P repository: an anoxic glove box atmosphere containing ≤ 4 vol. % H 2 vs. substantially higher H 2 gas concentrations assumed in the WIPP Performance Assessment (PA); a significantly higher liquid-to-solid test ratio compared to the much lower phase ratio anticipated in the WIP P repository; agitation of the simulant bottles to maximize mass transfer; and finally the use of Fe 0 reagents having a much greater surface area than expected in the WIP P repository. Non-representative conditions were chosen for various reasons such as: to provide bounding conservative results, to provide a margin of safety for testing, or to facilitate simulant sub-sampling and analysis. In a parallel effort, aqueous electrolyte thermodynamic models were developed for the synthetic Salado and Castile brines to inform the experimental design, facilitate laboratory data interpretation, and allow extension of evaluations beyond the parameters tested. Thermodynamic modeling simulations including the MgO and Fe 0 additives that are directly relevant to the experimental measurements (e.g., pH calibration curve, ORP corrections) are included in this report. The measured fa of the simulants was close to the OLI model predictions for both brines and was largely controlled by the background H 2 partial pressure in the vapor phase as well as H 2 generated in situ in the aqueous phase by the Fe 0 corrosion. The H 2 gas-phase concentration tested and thermodynamically evaluated was much lower than is assumed in the WIPP PA; however, H 2 (g) concentrations significantly below this level are still predicted to result in very reducing conditions. In conclusion: • The experimental results are consistent with thermodynamic model predictions for fa, pH, and the effects of high ionic strength. • Evidence to date suggests that the H2 concentration in the glovebox atmosphere ultimately determined the final E h values of the simulants and resulted in highly reducing conditions. As a result, little difference was observed between the control simulants containing only MgO and the WIPP base-case simulants that contained MgO and Fe 0 . • This test methodology is recommended for future studies evaluating WIPP repository conditions. The methodology includes: (1) background H 2 in argon with agitation ( or could alternatively include in-situ-generated H 2 in sealed bottles); (2) carefully measured and corrected ORP data ( with much effort focused on allowing the probes to fully stabilize); and (3) ionic-strength-corrected pH data. Other best practices, such as simulant sparging/handling, ORP probe replacement, etc., should also be considered. • The coupling of experimental studies and thermodynamic modeling is also highly recommended because these methods inform and direct one another leading to greater confidence in and understanding of the results.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Dynamic properties of FeCrMnNi, a high entropy alloy

The goal of this paper was to assess the dynamic properties of a new class of materials, High entropy alloys (HEAs). Specifically, gas gun experiments coupled with recovery were performed on a specific HEA, FeCrMnNi, to measure its equation of state (EOS) and its spall strength, which is a measure of the stress required to nucleate voids under shock loading conditions. While there has been a plethora of work performed to assess the mechanical properties of these HEAs under uniaxial stress conditions as a function of strain rate, investigation of its properties in dynamic extremes remains rare. The current work fills this gap in knowledge for this novel class of materials. Our results show that the measured EOS for this material at one velocity was in reasonable agreement with an estimated Hugoniot. Furthermore, while the spall strength for this material was found to be ~1.9 GPa, with some variation based on sample location, the main failure mode was brittle. This brittle failure leading to formation of cracks in the material is different than the ductile failure observed in pure iron and its alloys.

36 MATERIALS SCIENCE↗

Iraq/Afghanistan war lung injury reflects burn pits exposure

This descriptive case series retrospectively reviewed medical records from thirty-one previously healthy, war-fighting veterans who self-reported exposure to airborne hazards while serving in Iraq and Afghanistan between 2003 and the present. They all noted new-onset dyspnea, which began during deployment or as a military contractor. Twenty-one subjects underwent non-invasive pulmonary diagnostic testing, including maximum expiratory pressure (MEP) and impulse oscillometry (IOS). In addition, five soldiers received a lung biopsy; tissue results were compared to a previously published sample from a soldier in our Iraq Afghanistan War Lung Injury database and others in our database with similar exposures, including burn pits. We also reviewed civilian control samples (5) from the Stony Brook University database. Military personnel were referred to our International Center of Excellence in Deployment Health and Medical Geosciences, Donald and Barbara Zucker School of Medicine at Hofstra/Northwell under the auspices of Northwell IRB: 17-0140-FIMR Feinstein Institution for Medical Research “Clinicopathologic characteristics of Iraq Afghanistan War Lung Injury.” We retrospectively examined medical records, including exposure data, radiologic imaging, and non-invasive pulmonary function testing (MGC Diagnostic Platinum Elite Plethysmograph) using the American Thoracic Society (ATS) standard interpretation based on Morgan et al., and for a limited cohort, biopsy data. Lung tissue, when available, was examined for carbonaceous particles, polycyclic aromatic hydrocarbons (Raman spectroscopy), metals, titanium connected to iron (Brookhaven National Laboratory, National Synchrotron Light Source II, Beamline 5-ID), oxidized metals, combustion temperature, inflammatory cell accumulation and fibrosis, neutrophil extracellular traps, Sirius red, Prussian Blue, as well as polarizable crystals/particulate matter/dust. Among twenty-one previously healthy, deployable soldiers with non-invasive pulmonary diagnostic tests, post-deployment, all had severely decreased MEP values, averaging 42% predicted. These same patients concurrently demonstrated abnormal airways reactance (X5Hz) and peripheral/distal airways resistance (D5–D20%) via IOS, averaging – 1369% and 23% predicted, respectively. These tests support the concept of airways hyperresponsiveness and distal airways narrowing, respectively. Among the five soldiers biopsied, all had constrictive bronchiolitis. We detected the presence of polycyclic aromatic hydrocarbons (PAH)—which are products of incomplete combustion—in the lung tissue of all five warfighters. All also had detectable titanium and iron in the lungs. Metals were all oxidized, supporting the concept of inhaling burned metals. Combustion temperature was consistent with that of burned petrol rather than higher temperatures noted with cigarettes. All were nonsmokers. Neutrophil extracellular traps were reported in two biopsies. Compared to our prior biopsies in our Middle East deployment database, these histopathologic results are similar, since all database biopsies have constrictive bronchiolitis, one has lung fibrosis with titanium bound to iron in fixed mathematical ratios of 1:7 and demonstrated polarizable crystals. These results, particularly constrictive bronchiolitis and polarizable crystals, support the prior data of King et al. (N. Engl. J. Med. 365:222–230, 2011) Soldiers in this cohort deployed to Iraq and Afghanistan since 2003, with exposure to airborne hazards, including sandstorms, burn pits, and improvised explosive devices, are at high risk for developing chronic clinical respiratory problems, including: (1) reduction in respiratory muscle strength; (2) airways hyperresponsiveness; and (3) distal airway narrowing, which may be associated with histopathologic evidence of lung damage, reflecting inhalation of burned particles from burn pits along with particulate matter/dust. Non-invasive pulmonary diagnostic tests are a predictor of burn pit-induced lung injury

36 MATERIALS SCIENCE↗