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Mercury Speciation via Direct Mercury Analyzer

Mercury has no known biological role, but is present in every living thing and widespread in the environment. As mercury enters an aqueous system, it is subject to methylation or demethylation. Methylmercury selectively partitions into biota and biomagnifies through the food chain. Nearly all methylmercury exposures in the U.S. occur through eating fish and shellfish that contain higher levels of methylmercury. Methyl mercury and other organomercury compounds are more toxic than inorganic mercury. Thus, monitoring and understanding mercury speciation are key to effective environmental management. It is particularly important to be able to separate and measure bioaccumulative-toxic species of mercury such as methyl mercury. We are developing a protocol for utilizing the Direct Mercury Analyzer (DMA-80) for mercury speciation of water samples and to monitor methylmercury (meHg). Objectives: - Advance the understanding of the performance of the direct mercury analysis (DMA) under a range of DOE relevant water chemistry conditions to quantify total mercury: - Demonstrate the applicability of DMA to analysis of typical DOE high level liquid 'tank' waste samples using nonradioactive simulants; Test innovative sorbents to extend the range of the direct mercury analyzer to environmental concentration levels. - Perform scoping tests to demonstrate proof of principle for the chemical reduction amalgamation modular microcolumns for mercury speciation: Examine various microcolumn configurations and document speciation performance for typical DOE high level liquid 'tank' waste samples using nonradioactive simulants; Perform tests to examine extending the speciation paradigm to environmental concentration levels. General Method: all samples analyzed using a direct mercury analyzer (DMA 80) which automates the following steps: 1) pyrolysis to release the mercury, 2) catalysis to convert all mercury to elemental, 3) amalgamation to trap the mercury, 4) desorption to release the mercury as a pulse and 5) spectroscopy to detect the mercury.. Instrument analyzes all mercury species in solids and liquids. The DMA 'eliminates' sample preparation, reduces labor, decreases waste, and results in more practical and cost effective methods. To test the performance of the DMA for DOE relevant conditions, we analyzed samples representative of at high (mg/L) tank waste concentrations in water and in diluted tank waste simulant and analyzed samples representative of environmental (ng/L levels) in water. High concentration samples were analyzed directly in the instrument. Low concentration samples were analyzed by concentrating the mercury onto sorbents such as silica thiol or a mixture of silica thiol and copper. The concentration was performed using microcolumns and placing the columns into the DMA (see below) or by mixing the sorbent into the bulk sample and then filtering ad analyzing the filter in the DMA. Speciation Methods: The speciation tests were based on the selective reduction of inorganic mercury ions - Hg{sup (+} {sup or} {sup 2+)} - to elemental mercury - Hg(0). The elemental mercury is then trapped by amalgamation into the metal. These reactions do not impact methyl mercury allowing for separation. All reactions were performed using powdered elemental copper. To demonstrate proof-of-principle for the selective collection of inorganic mercury, samples were exposed to different amounts of powdered copper (and a control with no copper). This was done using microcolumns and a vacuum box. The columns were placed directly on the DMA for analysis. All materials and conditions were tested using solutions of both inorganic mercury and methyl mercury and all trials were in triplicate. Results and Observations: Validated DMA for high concentration Hg samples such as DOE tank waste: - Liquid inHg - samples were stable on autosampler carousel and results were accurate; - Liquid meHg - samples required a stabilizer. Si-Thiol (0.02 g) in the sample boat generated reliable meHg results. Stabilizer can be added for routine operations. Successful 'proof of principal' in extending DMA range to near environmental levels - using both microcolumns and filtration; - Filtration - Adding Si-Thiol (0.5 g) to sample extracted both inHg and meHg and preserved sample. Handling filters was labor intensive. - Microcolumns - best performance using a combination of copper and Si-Thiol - columns clogged and flowed slowly in some cases; - Practical limit may be in the range of 1 to 5 ng/L due to blanks; - Path Forward - Test additional packing materials and methods to improve flow and consistency, and approaches to minimize blanks. Successful 'proof of principal' for Hg speciation using chemical reduction and amalgamation; - Copper microcolumns (0.5 g Cu) selectively trapped inHg for high concentration mercury samples; - Copper microcolumns (0.5 g Cu selectively trapped inHg for large volume samples at environmental concentrations; - Some sorption of me Hg so that separations not quantitative; - Path Forward - test additional packing materials and alternate eluents to better trap inHg and minimize meHg retention in column.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molar Absorptivities of U(VI), U(IV), and Pu(III) in Nitric Acid Solutions of Various Concentrations Relevant to Developing Nuclear Fuel Recycling Flowsheets

Testing of a co-decontamination (CoDCon) tributyl phosphate (TBP) based solvent extraction flowsheet is being performed to optimize conditions for achieving a target U/Pu ratio in the Pu-containing product. The flowsheet is designed to directly produce a mixture of U and Pu with a U/Pu mass ratio of 7/3. The system is monitored in real time using optical spectroscopy, which allows for control of the U/Pu ratio in the aqueous U/Pu nitrate product. On-line spectrophotometric monitoring of the aqueous stream at the reductive stripping step involves determination of U(VI), U(IV) and Pu(III) concentrations and relies on molar absorptivities of these species in nitric acid at a number of wavelengths corresponding to their peaks’ maxima. The magnitudes of these molar absorptivities are a sensitive function of nitric acid concentration and have to be determined as precisely as possible using an off-line spectrophotometry under well controlled conditions. This step (called training set acquisition) is typically performed not in a high contamination area of radiological glovebox where flow-through cells and other on-line equipment are installed but in a less aggressive environment of a radiological fume hood with much better control of stock solutions quality, dilution factors, optical absorbance scale calibration, etc. This is followed by the calibration transfer between the off-line instrument and the instrument deployed during extraction and stripping runs. This paper reports values of molar absorptivities of U(VI), U(IV), and Pu(III) in nitric acid solution of 0.5 M to 4 M concentration and compares them with available technical literature data. Results of off-line spectrophotometric analysis of selected aqueous grab samples from one of CoDCon runs show satisfactory agreement with total uranium and plutonium concentrations determined in the same samples by ICP-MS.

Sinkov, Sergey I.↗

Flow Visualization for Plume-Surface Interaction at Martian-Relevant Lander Environments

This paper describes a jet impingement experiment performed in a large-scale vacuum chamber at Martian-relevant ambient pressure conditions, with the motivation of studying plume-surface interaction (PSI) caused by the exhaust plume of a lander interacting with the planetary surface. Flow visualization of an inert supersonic jet was performed using planar laser-induced fluorescence (PLIF), which is a molecular-based, two-dimensional measurement technique. Representative instantaneous and time-averaged visualizations of the impinging jet at two different nozzle flow conditions corresponding to the underexpanded and overexpanded jet regimes are presented for up to six different dimensionless altitudes h/De. The time-averaged measured spatial distribution of impingement pressures at these conditions is also reported. The PLIF visualizations appear to be critical towards explaining unexpected behavior in the impingement pressure, such as a higher impingement pressure for the underexpanded condition at h/De = 10, compared to a lower altitude of h/De = 8. This behavior can be attributed to differences in the stagnation shock structure observed in the PLIF images. The PLIF images also reveal significant flow separation at the nozzle exit for the overexpanded jet conditions. Further analysis of the test data as well as combined flow visualization and surface diagnostics for future ground tests will help inform engineering designs for landings on the Martian surface while mitigating PSI risks.

PLIF↗

Flow Visualization for Plume-Surface Interaction at Martian-Relevant Lander Environments

This paper describes a jet impingement experiment performed in a large-scale vacuum chamber at Martian-relevant ambient pressure conditions, with the motivation of studying plume-surface interaction (PSI) caused by the exhaust plume of a lander interacting with the planetary surface. Flow visualization of an inert supersonic jet was performed using planar laser-induced fluorescence (PLIF), which is a molecular-based, two-dimensional measurement technique. Representative instantaneous and time-averaged visualizations of the impinging jet at two different nozzle flow conditions corresponding to the underexpanded and overexpanded jet regimes are presented for up to six different dimensionless altitudes h/De. The time-averaged measured spatial distribution of impingement pressures at these conditions is also reported. The PLIF visualizations appear to be critical towards explaining unexpected behavior in the impingement pressure, such as a higher impingement pressure for the underexpanded condition at h/De = 10, compared to a lower altitude of h/De = 8. This behavior can be attributed to differences in the stagnation shock structure observed in the PLIF images. The PLIF images also reveal significant flow separation at the nozzle exit for the overexpanded jet conditions. Further analysis of the test data as well as combined flow visualization and surface diagnostics for future ground tests will help inform engineering designs for landings on the Martian surface while mitigating PSI risks.

PLIF↗

The Microbiology of Microgreens Grown in Controlled Environment Chambers under ISS Conditions

Microgreens have been identified as a new type of pick-and-eat salad crop that can be utilized in space crop production systems. The majority of traditionally grown leafy green crops can be grown as microgreens, in addition to crops such as legumes, sunflower, buckwheat, most herbs, and corn, presenting hundreds of microgreen crop options. Notably, microgreens are nutrient dense, high in beneficial compounds like antioxidants, Vitamins C and K, and exhibit a variety of desirable flavors and textures.The short growth cycles (7-14 days), low water requirements and volume optimization potential make them a viable option for sustainable production of nutritious and flavorful crops in space.The crop production team at Kennedy Space Center is investigating the food safety aspects of microgreens grown under spaceflight relevant conditions for crew consumption. Microbiological analysis and screening for potential foodborne pathogens was performed on over 20 varieties of microgreens that have demonstrated positive horticultural attributes.Additionally, a comparison of microgreens grown hydroponically under ISS environmental conditions and similar varieties from local markets was completed to collect baseline data on the microbial load on microgreens. In aneffort to improve microgreen quality, strategies to reduce the microbial load were tested, including bulk seed sanitization, harvest age, exposure to high blue light, and post-harvest chemical disinfection. The efficacy of a citric acid-based produce wash currently used for ISS grown produce and 1% H2O2were investigated at different exposure times for reduction in bacterial and fungal counts on a variety of microgreens. Limited log reduction was achieved depending on exposure time.Our testing also demonstrated that seed sanitization impacted microbial load on microgreens and systems.

Mary E. Hummerick↗

Moisture-Induced Alumina Scale Spallation: The Hydrogen Factor

For some time our community has been concerned with interfacial spallation of protective alumina scales, not just upon immediate cooldown, but as a time-delayed phenomenon. Moisture-induced delayed spallation (MIDS) and desktop spallation (DTS) of TBC's refer to this process. It is most apparent for relatively adherent alumina scales that have survived cool down in a dry environment, built up considerable thickness and strain energy, and have been somewhat damaged, such as by cyclic oxidation cracking. Indeed, a "sweet zone" can be defined that maximizes the observed effect as a function of all the relevant factors. Moisture has been postulated to serve as a source of interfacial hydrogen embrittlement derived from reaction with aluminum in the alloy at an exposed interface. The purpose of this monograph is to trace the close analogy of this phenomenon to other hydrogen effects, such as embrittlement of aluminides and blistering of alloys and anodic alumina films. A formalized, top-down, logic tree structure is presented as a guide to this discussion. A theoretical basis for interfacial weakening by hydrogen is first cited, as are demonstrations of hydrogen as a reaction product or detected interfacial species. Further support is provided by critical experiments that produce the same moisture effect, but by isolating hydrogen from other potential causative factors. These experiments include tests in H2-containing atmospheres or cathodic hydrogen charging.

Smialek, James L.↗

Radiological Recovery Logistics Tool - 20161

Argonne is building and testing a tool, the Radiological Recovery Logistics Tool (RRLT), that can be used during the response and recovery from a radiological or nuclear incident to effectively allocate appropriate commercial and public works equipment to mitigate, remove, and contain radiological contamination. The requirements for this tool - as well as development of the resulting software - is overseen by a steering committee of stakeholders from DHS's National Urban Security Technology Laboratory (NUSTL), the Federal Emergency Management Agency (FEMA), and the Environmental Protection Agency (EPA). One essential requirement is for RRLT to support the efficient and appropriate allocation of resources for a radiological response. Subsequent discussions between ANL and stakeholders have solidified the nature of this support to include identification of the types of resources to be allocated. The study reported in this paper has both factored fundamental concepts and connections out of this identification process and created a Knowledge Base detailing support goals, response scenarios, and efficacy information on dozens of equipment types. In short, RRLT will dynamically apply these findings to situational conditions surrounding contamination incidents. RRLT's Domain, the model of elements, ideas and relationships with which the tool will work, draws concepts from technical reports and stakeholder vocabularies to connect response goals and scenarios to types of equipment that offer utility towards those goals in those scenarios. RRLT's Knowledge Base will contain details on dozens of equipment types and facilitate the operator's discovery and consumption of these details most pertinent to a dynamically selected subset of goals. The core of its Domain Model is based on a report authored by this team. This report [1] contains a comprehensive list of proposed equipment to accomplish various missions or scenarios that might arise after a large-scale radiological contamination incident in an urban environment or critical infrastructure. The report divides potential response and recovery efforts into five support goals: Survey and monitoring of the contaminated area; Mitigation of received dose to first responders: Decontamination (gross and final) of buildings, vehicles, roadways, parks, and other surfaces: Waste management of solid waste generated during recovery operations: and Containment of wastewater and other waste generated during the response and recovery phases. RRLT's development is driven by use cases. A use case is an intention with which a user approaches the software. Use cases are grouped into delivery increments to schedule development, testing, and presentation to stakeholders. This model partitions the system into seven increments: User Arrival and Authentication, Search and Navigation, Equipment Recommendation, Plan Management, Content Management, and Expanded Access. Once a user 15 authenticated, RRLT will present the user with a dashboard that allows them to explore or search RRLT's content. The dashboard will also include a 'Plan' panel for collecting decisions and relevant observations about an incident at hand to facilitate development of an equipment list. RRLT will offer three general modes of access to items in the knowledge base: - Keyword search for direct discovery of items, - Navigation along predetermined paths from recovery goal towards equipment types, and - Interactive guidance towards equipment types by an autonomous software agent: the Equipment Recommendation Wizard. This presentation will detail progress in the development of the RRLT and also discuss opportunities for those interested in providing feedback on its content and functionality. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Measurement of Creep Properties of Ultra-High-Temperature Materials by a Novel Non-Contact Technique

A non-contact technique for measuring the creep properties of materials has been developed and validated as part of a collaboration among the University of Massachusetts, NASA Marshall Space Flight Center Electrostatic Levitation Facility (ESL), and the University of Tennessee. This novel method has several advantages over conventional creep testing. The sample is deformed by the centripetal acceleration from the rapid rotation, and the deformed shapes are analyzed to determine the strain. Since there is no contact with grips, there is no theoretical maximum temperature and no concern about chemical compatibility. Materials may be tested at the service temperature even for extreme environments such as rocket nozzles, or above the service temperature for accelerated testing of materials for applications such as jet engines or turbopumps for liquid-fueled engines. The creep measurements have been demonstrated to 2400 C with niobium, while the test facility, the NASA MSFC ESL, has processed materials up to 3400 C. Furthermore, the ESL creep method employs a distribution of stress to determine the stress exponent from a single test, versus the many tests required by conventional methods. Determination of the stress exponent from the ESL creep tests requires very precise measurement of the surface shape of the deformed sample for comparison to deformations predicted by finite element models for different stress exponents. An error analysis shows that the stress exponent can be determined to about 1% accuracy with the current methods and apparatus. The creep properties of single-crystal niobium at 1985 C showed excellent agreement with conventional tests performed according to ASTM Standard E-139. Tests on other metals, ceramics, and composites relevant to rocket propulsion and turbine engines are underway.

Hyers, Robert W.↗

Evaluation of Neutron Absorbers in the DOE Standardized SNF Canister

The goal of this evaluation was to evaluate different options for a neutron absorber in the U.S. Department of Energy (DOE) Standardized spent nuclear fuel (SNF) Canister. This was accomplished by taking the two most relevant criticality evaluations and replacing the advanced neutron absorber (ANA) basket material with borated stainless steel. This work was initiated, because alternative storage options for DOE SNF has become a priority for DOE. Idaho National Laboratory (INL) is initiating activities to ensure the continued operation of the Advanced Test Reactor (ATR) by providing alternative and redundant storage options for spent ATR fuel. In addition, the DOE Office of Environmental Management (EM) has recently initiated studies to understand and improve the technical basis for long-term dry storage of aluminum clad SNF (e.g., ATR, High Flux Isotope Reactor [HFIR]) (Connolly 2018). While currently in the lab-scale phase, the next step involves validation and verification (V&V) of the lab-scale results. One method to perform V&V is to load aluminum-clad spent fuel in an instrumented DOE Standardized SNF Canister as a demonstration. In order to minimize the need for repackaging before disposal and to provide a representative environment in a demonstration, the fuel is planned to be loaded with an appropriate criticality control mechanism, such as neutron absorbing basket material. While ANA was originally selected as the basket material for ATR fuel in the Yucca Mountain Repository, it has never been produced on a large scale. Therefore, incorporating this material in the DOE Standardized SNF Canister as part of a near-term demonstration could be more challenging than moving forward with a commercially available material, such as borated stainless steel. Past evaluations eliminated borated stainless steel as a long-term neutron absorbing material, because it corroded too quickly and may not always remain in the waste package after degradation. This led to the invention and selection of ANA for use as the basket material in the DOE Standardized SNF Canister. After selecting ANA, new corrosion tests were performed on borated stainless steel using a different method for fabrication. This method of fabrication significantly improved the corrosion resistance properties of borated stainless steel, so much so that it out-performed ANA in corrosion testing. Researchers used the information obtained from these tests to select borated stainless steel as the neutron absorber in the Transportation, Aging, and Disposal Canister (TAD) designed for commercial SNF. This evaluation compares the criticality control of borated stainless steel to ANA. In every case and scenario, the calculated effective neutron multiplication factor (k eff ) using a borated stainless steel basket was lower than that using an ANA basket, though the borated stainless steel must be thicker due to corrosion effects over the regulatory time period. Although the borated stainless steel performed better than the ANA, it still required additional neutron-absorbing material, gadolinium shot, for the calculated k eff to fall below the upper critical limit of 0.93 in a few cases evaluated. More research using thicker baskets or inserts could be performed in an attempt to lower the k eff without the use of gadolinium shot. In addition, a reevaluation of the degraded ATR material used in the previous evaluations may prove that the original assumptions were over-conservative.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Visual Acuity Using Head-fixed Displays During Passive Self and Surround Motion

The ability to read head-fixed displays on various motion platforms requires the suppression of vestibulo-ocular reflexes. This study examined dynamic visual acuity while viewing a head-fixed display during different self and surround rotation conditions. Twelve healthy subjects were asked to report the orientation of Landolt C optotypes presented on a micro-display fixed to a rotating chair at 50 cm distance. Acuity thresholds were determined by the lowest size at which the subjects correctly identified 3 of 5 optotype orientations at peak velocity. Visual acuity was compared across four different conditions, each tested at 0.05 and 0.4 Hz (peak amplitude of 57 deg/s). The four conditions included: subject rotated in semi-darkness (i.e., limited to background illumination of the display), subject stationary while visual scene rotated, subject rotated around a stationary visual background, and both subject and visual scene rotated together. Visual acuity performance was greatest when the subject rotated around a stationary visual background; i.e., when both vestibular and visual inputs provided concordant information about the motion. Visual acuity performance was most reduced when the subject and visual scene rotated together; i.e., when the visual scene provided discordant information about the motion. Ranges of 4-5 logMAR step sizes across the conditions indicated the acuity task was sufficient to discriminate visual performance levels. The background visual scene can influence the ability to read head-fixed displays during passive motion disturbances. Dynamic visual acuity using head-fixed displays can provide an operationally relevant screening tool for visual performance during exposure to novel acceleration environments.

Wood, Scott J.↗

Quantum chemically calculated Abraham parameters for quantifying and predicting polymer hydrophobicity

The leakage and accumulation of plastic in the environment is a significant and growing problem with numerous detrimental impacts and has led to a push toward the design and development of more environmentally benign materials. To this end, we have developed a quantum chemistry-based model for predicting the mobility of polymer materials from molecular structure. Hydrophobicity is used as a surrogate for mobility given that hydrophobic interactions drive much of the partitioning of contaminants in and out of various environmentally relevant compartments. To model polymer hydrophobicity, we adjusted a previously developed Quantum Chemically Calculated Abraham Parameter model to calculate Abraham parameters of small molecules from molecular structure information. The resulting model predicted the octanol-water partition coefficient (K OW ) of polymer repeating units with a root mean square error (RMSE) of 0.48 (log scale). Additionally, the hydrophobicity of high molecular weight polymer materials was captured through solubility parameters and Nile red staining experiments from the literature and predicted with RMSEs of 1.21 (J/cc) 0.5 and 3.42 nm, respectively. Finally, to test the environmental applicability of the model, the relative adsorption capacity of three polymers was predicted and used to unify sorption isotherms across multiple sorbates and polymer sorbents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ch3MS-RF: a random forest model for chemical characterization and improved quantification of unidentified atmospheric organics detected by chromatography–mass spectrometry techniques

Abstract. The chemical composition of ambient organic aerosols plays a critical role in driving their climate and health-relevant properties and holds important clues to the sources and formation mechanisms of secondary aerosol material. In most ambient atmospheric environments, this composition remains incompletely characterized, with the number of identifiable species consistently outnumbered by those that have no mass spectral matches in the literature or the National Institute of Standards and Technology/National Institutes of Health/Environmental Protection Agency (NIST/NIH/EPA) mass spectral databases, making them nearly impossible to definitively identify. This creates significant challenges in utilizing the full analytical capabilities of techniques which separate and generate spectra for complex environmental samples. In this work, we develop the use of machine learning techniques to quantify and characterize novel, or unidentifiable, organic material. This work introduces Ch3MS-RF (Chemical Characterization by Chromatography–Mass Spectrometry Random Forest Modeling), an open-source, R-based software tool, for efficient machine-learning-enabled characterization of compounds separated in chromatography–mass spectrometry applications but not identifiable by comparison to mass spectral databases. A random forest model is trained and tested on a known 130 component representative external standard to predict the response factors of novel environmental organics based on position in volatility–polarity space and mass spectrum, enabling the reproducible, efficient, and optimized quantification of novel environmental species. Quantification accuracy on a reserved 20 % test set randomly split from the external standard compound list indicates that random forest modeling significantly outperforms the commonly used methods in both precision and accuracy, with a median response factor percent error of −2 %, for modeled response factors, compared to > 15 %, for typically used proxy assignment-based methods. Chemical properties modeling, evaluated on the same reserved 20 % test set and an extrapolation set of species identified in ambient organic aerosol samples collected in the Amazon rainforest, also demonstrate robust performance. Extrapolation set property prediction mean absolute errors for carbon number, oxygen to carbon ratio (O : C), average carbon oxidation state (OSc‾), and vapor pressure are 1.8, 0.15, 0.25, and 1.0 (log(atm)), respectively. Extrapolation set out-of-sample R2 for all properties modeled are above 0.75, with the exception of vapor pressure. While predictive performance for vapor pressure is less robust compared to the other chemical properties modeled, random-forest-based modeling was significantly more accurate than other commonly used methods of vapor pressure prediction, decreasing the mean vapor pressure prediction error to 0.24 (log(atm)) from 0.55 (log(atm)) (chromatography-based vapor pressure prediction) and 1.2 (log(atm)) (chemical formula-based vapor pressure prediction). The random forest model significantly advances an untargeted analysis of the full scope of chemical speciation yielded by two-dimensional gas chromatography (GCxGC-MS) techniques and can be applied to gas chromatography coupled with electron ionization mass spectrometry (GC-MS) as well. It enables the accurate estimation of key chemical properties commonly utilized in the atmospheric chemistry community, which may be used to more efficiently identify important tracers for further individual analysis and to characterize compound populations uniquely formed under specific ambient conditions.

54 ENVIRONMENTAL SCIENCES↗

Moisture-Induced Alumina Scale Spallation: The Hydrogen Factor

For some time the oxidation community has been concerned with interfacial spallation of protective alumina scales, not just upon immediate cool down, but as a time-delayed phenomenon. Moisture-induced delayed spallation (MIDS) and desktop spallation (DTS) of thermal barrier coatings (TBCs) refer to this process. It is most apparent for relatively adherent alumina scales that have survived initial cool down in a dry environment, have built up considerable thickness and strain energy, and have been somewhat damaged, such as by cyclic oxidation cracking. Indeed, a "sensitive zone" can be described that maximizes the observed effect as a function of all the relevant factors. Moisture has been postulated to serve as a source of interfacial hydrogen embrittlement. Hydrogen is derived from reaction with aluminum in the alloy at an exposed interface. The purpose of this monograph is to trace the close analogy of this phenomenon to other hydrogen-induced effects, such as embrittlement of aluminides and blistering of alloys and anodic alumina films. A formalized, top-down, logic-tree structure is presented as a guide to this discussion. A theoretical basis for interfacial weakening by hydrogen is first cited, as are demonstrations of hydrogen detection as a reaction product or interfacial species. Further support is provided by critical experiments that recreate the moisture effect, but by isolating hydrogen from other potential causative factors. These experiments include tests in H 2-containing atmospheres or cathodic hydrogen charging. Accordingly, they strongly indicate that interfacial hydrogen, derived from moisture, is the key chemical species accounting for delayed alumina scale spallation.

Smialek, James L.↗

Quantifying radiation quality for space relevant radiation types: Fitting excess risk models to three combined HZE-irradiated mouse datasets

Radiation health risks are predominantly derived from low linear energy transfer (LET) terrestrial exposures; however, space radiation includes exposure to high-LET and high-charge, high-energy (HZE) particles. Accurately quantifying the differences in radiation quality between the space and terrestrial radiation environments is important for assessing and predicting health risks for astronauts. Weil et al. 2009 and 2014 used two different inbred mouse strains to study differences in hepatocellular carcinoma (HCC) tumorigenesis after exposures to low- and high- LET radiation. More recently, Edmundson et al. 2020 provided valuable new tumor data in outbred mice that were exposed to low- and high-LET radiation. The present study aims to rigorously investigate a relative biological effectiveness (RBE) factor by leveraging the HCC tumor data from Weil et al. 2009, Weil et al. 2014, and Edmundson et al. 2020. The three experiments were similarly designed, allowing the raw data to be combined into a pooled dataset to estimate excess relative risk (ERR) and excess absolute risk (EAR) models using Bayesian Poisson regression. These effect estimates from the pooled data provide greater power to calculate a data driven RBE. Extensive sensitivity analyses test the robustness of RBE estimates to various model assumptions. The following questions will be explored through the sensitivity analyses: • Is the shape of the dose response different for low-LET radiation and HZE radiation, indicating that RBE is a function of dose? • Does attained age modify the effect estimates differently for low-LET radiation and HZE radiation, indicating RBE is a function of attained age? • Are the effect estimates and RBE estimates different for inbred mouse strains and outbred mouse strains? • Do assumptions about differences in ERR models and EAR models change the estimated RBE? Additional studies would be needed to validate the findings from these exploratory analyses.

Lori J. Chappell↗

Surface Erosion of Plasma-Facing Materials Using an Electrothermal Plasma Source and Ion Beam Micro-Trenches

Erosion characteristics of tungsten-alternative plasma-facing materials (PFMs) were tested under high heat flux conditions in the electrothermal plasma source facility at Oak Ridge National Laboratory. The PFMs of interest are high-purity β-3C chemical vapor deposition silicon carbide (SiC) and the MAX phases Ti 3 SiC 2 and Ti 2 AlC [MAX = chemical formula M n+1 AX n , where M is an early transition metal (such as Ti or Ta), A is an A-group element (such as Si or Al), and X is carbon or nitrogen]. Additionally, an erosion analysis method was developed using a combination of focused ion beam microscopy and scanning electron microscopy, carving micro-trench geometries into polished sample surfaces. Samples of SiC, Ti 3 SiC 2 , and Ti 2 AlC were exposed to the electrothermal plasma source alongside tungsten and monocrystalline silicon. Samples were exposed to a Lexan polycarbonate (C 16 H 14 O 3 ) electrothermal plasma stream in a He environment, at a specified impact angle, with infrared camera diagnostics. Edge localized mode–relevant heat fluxes of 0.9 to 1 GW/m 2 over 1-ms discharges were generated on the target surfaces. Tungsten samples exhibited pronounced melt-layer formation and deformation, with measured molten pits 2 to 10 μm in diameter and melt-layer depths of up to 7 μm deep. Surface erosion rates for Ti 3 SiC 2 and Ti 2 AlC ranged from 80 to 775 μm/s and 85 to 470 μm/s, respectively. Both MAX phases exhibited extreme surface fracture and material ejection, with damage depths past 4 μm for Ti 2 AlC and 11 μm for Ti 3 SiC 2 . Lastly, SiC displayed the best performance, in one case surviving 15 consecutive electrothermal plasma exposures with an average erosion rate of about 29 μm/s and no surface fracturing. SiC erosion rates ranged from 23 to 128 μm/s.

36 MATERIALS SCIENCE↗

Material Ignition and Suppression Test (MIST) in Space Exploration Atmospheres, Summary of Research

The Material Ignition and Suppression Test (MIST) project has had the objective of evaluating the ease of ignition and the fire suppression of materials used in spacecraft under environmental condition expected in a spacecraft. For this purpose, an experimental and theoretical research program is being conducted on the effect of space exploration atmospheres (SEA) on the piloted ignition of representative combustible materials, and on their fire suppression characteristics. The experimental apparatus and test methodology is derived from the Forced Ignition and Flame Spread Test (FIST), a well-developed bench scale test designed to extract material properties relevant to prediction of material flammability. In the FIST test, materials are exposed to an external radiant flux and the ignition delay and critical mass flux at ignition are determined as a function of the type of material and environmental conditions. In the original MIST design, a small-scale cylindrical flow duct with fuel samples attached to its inside wall was heated by a cylindrical heater located at the central axis of the cylinder. However, as the project evolved it was decided by NASA that it would be better to produce an experimental design that could accommodate other experiments with different experimental concepts. Based on those instructions and input from the requirements of other researchers that may share the hardware in an ISS/CIR experiment, a cylindrical design based on placing the sample at the center of an optically transparent tube with heaters equally spaced along the exterior of the cylinder was developed. Piloted ignition is attained by a hot wire igniter downstream of the fuel sample. Environment variables that can be studied via this experimental apparatus include: external radiant flux, oxidizer oxygen concentration, flow velocity, ambient pressure, and gravity level (if flown in the ISS/CIR). This constitutes the current experimental design, which maintains fairly good consistency with Dr Tien's and Dr Olson's project approaches. A further goal of the project has been to develop a combined solid/gas phase numerical model based on the MIST test methodology to predict the flammability behavior of practical materials in spacecraft.

flammability↗

Pterodactyl: Integrated Control Design for Precision Targeting of Deployable Entry Vehicles

Deployable Entry Vehicles (DEVs) enable in-situ scientific exploration at destinations with atmospheres across the solar system. Because they stow in a compact form and deploy only when ready to enter the atmosphere, DEVs relax the volume constraint imposed by rigid aeroshells. This work seeks to do for a DEV what the Wright Brothers did to propel modern day aviation: develop the guidance and control (G&C) methods that will make maneuvering and precision landing of DEV a reality. The Pterodactyl project objective is to deliver an integrated G&C methodology for a DEV, based on a detailed analysis that utilizes a Multi-disciplinary, Design, Analysis and Optimization (MDAO) framework. The current state-of-the-art for blunt body entry, G&C is rooted in the precision landing of vehicles such as Mars Science Laboratory (MSL) and Apollo, which used a propulsive reaction control system (RCS) to steer. Recent research has taken a particular interest in non-propulsive control for DEVs, including direct force control (angle of attack modulation via control surfaces or mass movement) and drag modulation (discrete change in ballistic coefficient). Using the MDAO framework that includes a guidance and control model to explore multiple control concepts for a DEV will shed light on the best design approach for these vehicles. In Pterodactyl, we will complete this study for a novel DEV concept, and then we will fabricate a functional prototype to help validate the design. The project is expected to down-select to a final control architecture by the end of 2018, and complete fabrication of the prototype by the end of 2019.The DEV chosen for detailed study in this project is the Adaptable Deployable Entry and Placement Technology (ADEPT). ADEPT uses a revolutionary 3D-woven carbon fabric that is foldable, can serve as primary structure, and can survive the extreme heating environment of atmospheric entry. The specific configuration of ADEPT under investigation is called Lifting Nano-ADEPT (LNA). LNA is designed for secondary payloads missions that require precision landing either for scientific objectives at a target destination or for payload recovery at Earth.The MDAO framework being created through this research, called COBRA-Pt (Composite Beam Roll-Up Solar Array-Prototype), will combine three critical elements of the system design: a guidance algorithm with Monte Carlo, a parametric control model, and vehicle geometry details. Novel control models being studied are deployable aerodynamic surfaces as well as shape morphing. These concepts will be compared at the system level with a more traditional propulsive RCS by comparing several key performance parameters. Upon completion of the design study, a functional prototype of LNA will be fabricated that will include the integration of guidance software and relevant control actuators. We expect this study will provide critical data that could feed into the development of an Earth-based flight test of LNA. The COBRA-Pt framework will provide a modular system by which to study any DEV concept in any atmosphere.

Smith, Brandon↗

Ocular Outcomes Comparison Between 14- and 70-day Head-down Tilt Bed Rest

INTRODUCTION: Ophthalmological changes, including optic disc edema with optic nerve sheath distension, posterior globe flattening with hyperopic shift, choroidal folds and cotton wool spots have been detected in some astronauts involved in long-duration spaceflights. (sup 1) It is hypothesized that elevated intracranial pressure resulting from microgravity-induced cephalad fluid shifts may be responsible for most of these findings. Head-down tilt bed rest (HTDBR) is a ground-based microgravity analog which also produces cephalad fluid shifts. It is conceivable that prolonged HDTBR exposure may induce ocular changes similar to those experienced in microgravity. Therefore, the purpose of the present study was to compare structural and functional ocular outcomes between 14- and 70-day HDTBR in healthy human subjects. It is hypothesized that 70-d HDTBR induced ocular changes of greater magnitude as compared to 14-d HDTBR. METHODS: Two HDTBR studies were conducted at the NASA Flight Analogs Research Unit, located at The University of Texas Medical Branch at Galveston, TX. Identical NASA standard screening procedures and BR conditions (e.g., strict sleep-wake cycle, standardized diet, continuous video monitoring) were implemented in both studies. Participants spent 14 and/or 70 consecutive days in a 6deg HDT position and did not engage in exercise. Subjects received weekly ocular examinations before, during, and after HDTBR. Ocular testing included: distance and near best-corrected visual acuity (BCVA), cycloplegic refraction, intraocular pressure (IOP) measurement, color vision, red dot test, modified Amsler grid test, confrontational visual field, color fundus photography and Spectral-domain OCT scans of the macula and the optic disc. Pre/post HDTBR differences between the two studies will be evaluated for BCVA, spherical equivalent, IOP, retinal nerve fiber layer (RNFL) thickness and macular OCT parameters. RESULTS: 16 (12 males and 4 females) and 6 (5 males and 1 female) subjects participated in the 14 and 70-day HDTBR studies, respectively. One subject participated in both studies. The demographic and ophthalmological characteristics of the 14-day HDTBR study have been presented elsewhere.2 In the 70- day study, subjects age averaged 39.5 +/- 7.8 years; pre- and post-HDTBR Goldmann IOP were, on average, 15.4 and 14.6 mmHg in the right eye, and 15.3 and 14.4 mmHg in the left eye, respectively; preand post-HDTBR Spectralis OCT (Heidelberg Engineering, GmbH, Heidelberg, Germany) average RNFL thickness were 103.8 and 106 μm in the right eye, and 103 and 104.3 μm in the left eye, respectively. In both studies, color vision, red dot test, modified Amsler grid test and confrontational visual field were within normal limits at all time points; no changes were detected on stereoscopic color optic disc photography. For the above outcomes, preliminary results of the pre/post HDTBR differences between the two studies will be presented at the 2015 Human Research Program Investigators' Workshop. CONCLUSIONS: Although 14-day HDTBR did not seem to induce clinically relevant ocular changes, (sup 2) a systematic evaluation and comparison with the 70-day HDTBR study results will elucidate whether the magnitude of ocular structural and functional changes is affected by the time spent in the recumbent position. Further research will also address the effects of integrated resistance and aerobic training during HDTBR on the ocular outcomes. REFERENCES: 1. Mader TH et al. Optic disc edema, globe flattening, choroidal folds, and hyperopic shifts observed in astronauts after long-duration space flight. Ophthalmology. 2011;118(10):2058-69. 2. Taibbi G et al. Ocular outcomes evaluation in a 14-day head-down bed rest study. Aviat Space Environ Med. 2014;85(10):983-92.

Cromwell, R.L.↗