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At least 469 records · Page 26

Probing the Radial Chemistry of Getter Components in Light Water Reactors via Controlled Electrochemical Dissolution

Getters are among the key functional components in the Tritium Producing Burnable Absorber Rods (TPBARs) of Light Water Reactors, and are used to capture the released tritium gas. They are cylindrical tubes comprised of the alloy zircaloy-4 which is coated with nickel plating both internally and externally. Their exposure to tritium as well as the irradiation environments in the light water reactors changes their structure, chemical composition and chemistry. Understanding the radial tritium distribution is key to gaining insight into the evolution of new chemistry upon irradiation in order to predict getter performance. Consequently, efforts are underway to devise a method that can allow selective probing into the getter core radially to probe the chemistry akin to carefully and selectively peeling of the layers of an onion. We have recently devised an electrochemical dissolution technique for controlled radial dissolution of zirconium based liners; this work describes the first proof-of-concept demonstration of the applicability of this technique on the controlled radial dissolution of nickel plated getters. The technique is complemented with periodic analysis of the electrolyte solution to measure the rates of release of the various elemental components and therefore glean information on their radial distribution across the getter; further complementary microscopy on the exposed surfaces allows us insight into the chemistry at the getter core.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Characterizing Cold Giant Planets in Reflected Light: Lessons from 50 Years of Outer Solar System Exploration and Observation

A space based coronagraph, whether as part of the WFIRST/AFTA mission or on a dedicated space telescope such as Exo-C or -S, will be able to obtain photometry and spectra of multiple gas giant planets around nearby stars, including many known from radial velocity detections. Such observations will constrain the masses, atmospheric compositions, clouds, and photochemistry of these worlds. Giant planet albedo models, such as those of Cahoy et al. (2010) and Lewis et al. (this meeting), will be crucial for mission planning and interpreting the data. However it is equally important that insights gleaned from decades of solar system imaging and spectroscopy of giant planets be leveraged to optimize both instrument design and data interpretation. To illustrate these points we will draw on examples from solar system observations, by both HST and ground based telescopes, as well as by Voyager, Galileo, and Cassini, to demonstrate the importance clouds, photochemical hazes, and various molecular absorbers play in sculpting the light scattered by solar system giant planets. We will demonstrate how measurements of the relative depths of multiple methane absorption bands of varying strengths have been key to disentangling the competing effects of gas column abundances, variations in cloud height and opacity, and scattering by high altitude photochemical hazes. We will highlight both the successes, such as the accurate remote determination of the atmospheric methane abundance of Jupiter, and a few failures from these types of observations. These lessons provide insights into technical issues facing spacecraft designers, from the selection of the most valuable camera filters to carry to the required capabilities of the flight spectrometer, as well as mission design questions such as choosing the most favorable phase angles for atmospheric characterization.

atmospheric methane abundance↗

The Composite Spectrum of QSO Absorption Line Systems in DESI DR2

We present details regarding the construction of a composite spectrum of quasar (QSO) absorption line systems. In this composite spectrum we identify more than 70 absorption lines, and observe oxygen and hydrogen emission features at a higher signal-to-noise ratio than in any previous study. As the light from a distant quasar travels towards an observer, it may interact with the circumgalactic medium environment of an intervening galaxy, forming absorption lines. In order to maximize the signal of these absorption lines, we have selected a sample of 238,838 quasar spectra from the second data release of the Dark Energy Spectroscopic Instrument (DESI), each identified to have absorption lines resulting from such an interaction. By stacking these spectra in the restframe of the absorption, and calculating a median composite spectrum, we are able to isolate and enhance these absorption lines. We provide a full atlas of all detected absorption and emission lines as well as their fit centroids and equivalent width values. This atlas should aid in future studies investigating the compositions and physical conditions of these absorbers.

Napolitano, Lucas [Wyoming U.] (ORCID:000000025166↗

Microscale spatiotemporal patterns of water, soil organic carbon, and enzymes in plant litter detritusphere

Understanding biophysical and biochemical processes in detritusphere is critical to quantifying and modeling plant residue decomposition dynamics and subsequent soil organic carbon (C) accrual. The objectives of the study were to explore (i) micro-environmental conditions within the detritusphere formed around decomposing corn and soybean leaves, and (ii) the relationships between moisture distribution, enzyme activity, and C dynamics during decomposition. We assessed spatial and temporal dynamics of moisture distribution using X-ray and neutron computed tomography, and activities of β-glucosidase and chitinase, two enzymes involved in soil C and N processing, using zymography. We used 13 C labeled residue to track residue contribution to atmospheric CO 2 and soil organic C. Moisture redistribution pattern varied depending on the residue type. While the water was immediately absorbed by the corn leaves and maintained afterward, switchgrass leaves absorbed water more slowly and created water-deficient zones within ~1mm from the residue. This initial moisture depletion led to lower chitinase activity and residue-derived CO 2 emissions in switchgrass. In contrast to chitinase, β-glucosidase activity was influenced by a combination of vegetation history and residue type, and it was higher when the origin of the residue matched the vegetation history of the soil. Pore size had an opposite impact on the studied enzymes, supporting the notion that contrasting soil pore architecture can stimulate activities of different enzymes through a selection of dominant enzyme producers. We concluded that the decomposition dynamics of plant residues is not only a simple function of residue chemistry, but rather a combined effect of the vegetation history, in part through its effect on microbial community composition, the plant residue chemical and likely physical characteristics, and the soil pore structure in the detritusphere. Together, they create temporally dynamic micro-environmental conditions influencing decomposition. Specifically, our study demonstrated that the initial micro-environment formulated in detritusphere can play an important role in enzyme activities and consequent C dynamics.

59 BASIC BIOLOGICAL SCIENCES↗

Short-wavelength-sensitive 2 (Sws2) visual photopigment models combined with atomistic molecular simulations to predict spectral peaks of absorbance

For many species, vision is one of the most important sensory modalities for mediating essential tasks that include navigation, predation and foraging, predator avoidance, and numerous social behaviors. The vertebrate visual process begins when photons of the light interact with rod and cone photoreceptors that are present in the neural retina. Vertebrate visual photopigments are housed within these photoreceptor cells and are sensitive to a wide range of wavelengths that peak within the light spectrum, the latter of which is a function of the type of chromophore used and how it interacts with specific amino acid residues found within the opsin protein sequence. Minor differences in the amino acid sequences of the opsins are known to lead to large differences in the spectral peak of absorbance (i.e. the λ max value). In our prior studies, we developed a new approach that combined homology modeling and molecular dynamics simulations to gather structural information associated with chromophore conformation, then used it to generate statistical models for the accurate prediction of λ max values for photopigments derived from Rh1 and Rh2 amino acid sequences. In the present study, we test our novel approach to predict the λ max of phylogenetically distant Sws2 cone opsins. To build a model that can predict the λ max using our approach presented in our prior studies, we selected a spectrally-diverse set of 11 teleost Sws2 photopigments for which both amino acid sequence information and experimentally measured λ max values are known. The final first-order regression model, consisting of three terms associated with chromophore conformation, was sufficient to predict the λ max of Sws2 photopigments with high accuracy. This study further highlights the breadth of our approach in reliably predicting λ max values of Sws2 cone photopigments, evolutionary-more distant from template bovine RH1, and provided mechanistic insights into the role of known spectral tuning sites.

59 BASIC BIOLOGICAL SCIENCES↗

Elevated Temperature Ballistic Impact Testing of PBO and Kevlar Fabrics for Application in Supersonic Jet Engine Fan Containment Systems

Ballistic impact tests were conducted on fabric made from both Poly(phenylene benzobizoxazole) (PBO) and Kevlar 29 which were selected to be similar in weave pattern, areal density, and fiber denier. The projectiles were 2.54-cm- (1-in.-) long aluminum cylinders with a diameter of 1.27 cm (0.5 in.). The fabric specimens were clamped on four sides in a 30.5-cm- (12-in.-) square frame. Tests on PBO were conducted at room temperature and at 260 C (500 F). A number of PBO specimens were aged in air at 204 and 260 C (400 and 500 F) before impact testing. Kevlar specimens were tested only at room temperature and with no aging. The PBO absorbed significantly more energy than the Kevlar at both room and elevated temperatures. However, after aging at temperatures of 204 C (400 F) and above, the PBO fabric lost almost all of its energy absorbing ability. It was concluded that PBO fabric is not a feasible candidate for fan containment system applications in supersonic jet engines where operating temperatures exceed this level.

Pereira, J. Michael↗

Artificial Photosynthesis with Next Generation Molecular Catalysts

The objective of this project was to develop a new class of molecular photocatalysts for CO 2 reduction that will enable breakthrough advances in artificial photosynthesis. A major limitation of existing photocatalytic assemblies is that only a small fraction of absorbed photons are converted into fuel due to inefficiencies in electron transport between the different system components. In the case of molecular catalysts for reduction of CO 2 , highly reducing electron equivalents are required for catalysis. As a result, the electron flux between the photosensitizer and CO 2 reduction catalyst is heavily biased towards the photosensitizer. One method to direct the electron flux towards productive photocatalysis is to design molecular catalysts for CO 2 reduction that operate at more favorable potentials than existing catalysts. The conventional approach is to tune the potential of the catalyst through selection of the supporting ligands, however, this only leads to incremental improvements due to the existence of an unfavorable scaling relationship between the rate and potential of catalysis. Our hypothesis is that the catalytic rate and potential can be simultaneously enhanced using bimetallic catalysts in which one metal improves the potential of catalysis and the second metal increases the rate of catalysis. During the course of this project, a few studies reported some success in improving photocatalytic CO 2 reduction with heterobimetallic complexes, demonstrating the potential of this approach to catalyst design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Contamination effects from materials selected for spacecraft instruments

Measurements of the Total Mass Loss (TML) and the Collected Volatile Condensable Materials (CVCM) are used as a guide for selecting those materials being low in outgassing. A contamination modelling method utilizing the data and also the rate at which a material outgasses in a system with a known conductance has been developed and has been applied to the problem encountered with the Very High Resolution Radiometer (VHRR). Recently, the contamination model has been applied to the problem with the 5th band of the Multi-Spectral Scanner on the Landsat-C satellite. In the MSS design, the volumes involved and their respective conductance in a molecular flow field demonstrated that the water vapor adsorbed and absorbed by an epoxy paint was being pumped off and re-ad(b)sorbed, with a resultant very slow loss of water during each degassing temperature cycle of the instrument's cooler. Recommendations for designing improved coolers are presented.

Heslin, T. M.↗

Shear sensitive monomer-polymer laminate structure and method of using same

Monomer cholesteric liquid crystals have helical structures which result in a phenomenon known as selective reflection, wherein incident white light is reflected in such a way that its wavelength is governed by the instantaneous pitch of the helix structure. The pitch is dependent on temperature and external stress fields. It is possible to use such monomers in flow visualization and temperature measurement. However, the required thin layers of these monomers are quickly washed away by a flow, making their application time dependent for a given flow rate. The laminate structure according to the present invention comprises a liquid crystal polymer substrate attached to a test surface of an article. A light absorbing coating is applied to the substrate and is thin enough to permit bonding steric interaction between the liquid crystal polymer substrate and an overlying liquid crystal monomer thin film. Light is directed through and reflected by the liquid crystal monomer thin film and unreflected light is absorbed by the underlying coating. The wavelength of the reflected light is indicative of the shear stress experienced by the test surface. Novel aspects of the invention include its firm bonding of a liquid crystal monomer to a model and its use of a coating to reduce interference from light unreflected by the monomer helical structure.

Singh, Jag J.↗

Shadowing the soft x-ray background by infrared cirrus: A study of selected regions

Using the ROSAT and IRAS data achieves, we studied shadows in the diffuse 0.25 keV background toward infrared cirrus clouds to infer the distribution of the hot interstellar medium (ISM). Surprisingly, we found that anticorrelation between infrared emission from cirrus clouds and background x-ray intensity was present in all five galactic latitude (b approx. greater than 25 deg) fields that we selected. In two fieds, the anticorrelation is more than 30% deep, and shows particularly convincing evidence that they are due to x-ray absorption by the clouds. Assuming an average density for the local x-ray-emitting gas (T approximately 10(exp 6) K), we estimated the minimum distances to the clouds based on our best-fit x-ray intensities originating in front of the clouds. These distances are in the range of 60 to 160 pc. Therefore, we conclude that there are a considerable number of degree-size, x-ray-absorbing gas clouds at approximately 10(exp 2) pc and that large amounts of x-ray-emitting gas exist in regions beyonds these clouds.

Wang, Q. Daniel↗

Acoustical properties of highly porous fibrous materials

Highly porous, fibrous bulk sound absorbing materials are studied with a view toward understanding their acoustical properties and performance in a wide variety of applications including liners of flow ducts. The basis and criteria for decoupling of acoustic waves in the pores of the frame and compressional waves in the frame structure are established. The equations of motion are recast in a form that elucidates the coupling mechanisms. The normal incidence surface impedance and absorption coefficient of two types of Kevlar 29 and an open celled foam material are studied. Experimental values and theoretical results are brought into agreement when the structure factor is selected to provide a fit to the experimental data. A parametric procedure for achieving that fit is established. Both a bulk material quality factor and a high frequency impedance level are required to characterize the real and imaginary part of the surface impedance and absorption coefficient. A derivation of the concepts of equivalent density and dynamic resistance is presented.

Lambert, R. F.↗

Electronic Absorption Spectroscopy and Photochemistry of Criegee Intermediates

Interest in Criegee intermediates (CIs), often termed carbonyl oxides, and their role in tropospheric chemistry has grown massively since the demonstration of laboratory-based routes to their formation and characterization in the gas phase. This article reviews current knowledge regarding the electronic spectroscopy of atmospherically relevant CIs like CH 2 OO, CH 3 CHOO, (CH 3 ) 2 COO and larger CIs like methyl vinyl ketone oxide and methacrolein oxide that are formed in the ozonolysis of isoprene, and of selected conjugated carbene-derived CIs of interest in the synthetic chemistry community. Of the aforementioned atmospherically relevant CIs, all except CH 2 OO and (CH 3 ) 2 COO exist in different conformers which, under tropospheric conditions, can display strikingly different thermal loss rates via unimolecular and bimolecular processes. Calculated photolysis rates based on their absorption properties suggest that solar photolysis will rarely be a significant contributor to the total loss rate for any CI under tropospheric conditions. Nonetheless, there is ever-growing interest in the absorption cross sections and primary photochemistry of CIs following excitation to the strongly absorbing 1 ππ* state, and how this varies with CI, with conformer and with excitation wavelength. Furthermore, the later part of this review surveys the photochemical data reported to date, including a range of studies that demonstrate prompt photo-induced fission of the terminal O–O bond, and speculates about possible alternate decay processes that could occur following non-adiabatic coupling to, and dissociation from, highly internally excited levels of the electronic ground state of a CI.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Information extraction techniques for multi-spectral scanner data

Multispectral data recognition and information extraction problems considered are: (1) signature extension for improved recognition processing over large areas; (2) choice of density functions for recognition decision rules; (3) channel selection for cost reduction; and (4) radiation balance mapping for interpretation of wide spectrum scanner data. The formulation of a simulation model and reprocessing of both aircraft and space data reduces scan angle variations and extends signatures from one altitude to another. Comparison of the usefulness of empirical density functions and that of Gaussian density functions for recognition processing establishes the advantages of normal assumption for individual fields in processing of multispectral scanner data. Also reported is a procedure for producing radiation balance maps from wide spectra by analyzing energy budgets of vegetation and other surface materials through partitioning net absorbed radiant energy and estimating incoming power density at both short and long wavelengths.

Malila, W. A.↗

SUMS experiment flight results on STS-35

Calibrated pressure measurements for species with mass to charge ratios up to 50 amu/e(-) were obtained from the Shuttle Upper Atmosphere Mass Spectrometer (SUMS) experiment during reentry on the STS-35 mission. Data were collected from 180 km, when the signal rose above the background, to about 87 km, when the SUMS system automatically closed the gas inlet value. However, data above 115 km was contaminated from a source of gas emanating from pressure transducers connected in parallel to the mass spectrometer. At lower altitudes, the pressure transducer data is compared with the mass spectrometer total pressure with excellent agreement. The free-stream density in the rarefied flow flight regime is calculated using an orifice pressure coefficient model based upon direct simulation Monte Carlo results. This density, when compared with the 1976 U.S. standard atmosphere model, exhibits the wave-like nature seen on previous flights using accelerometry. In addition, selected spectra are presented at higher altitudes (320 km) showing the effects of the ingestion of gases from a forward fuselage fuel dump. An analysis of the spectra data from this event is presented to show that no significant permanent changes occurred which affected the data interpretation at lower altitudes. Further, the localized chemistry from the individual species during the onset of aerodynamic heating is examined to the extent possible for a closed source system, such as SUMS. Near the orifice entrance, a significant amount of CO2 was generated from chemical reactions with the carbon panels of the Orbiter and absorbed oxygen on the system tubing.

Blanchard, Robert C.↗

Biosentinel: Improving Desiccation Tolerance of Yeast Biosensors for Deep-Space Missions

BioSentinel is one of 13 secondary payloads to be deployed on Exploration Mission 1 (EM-1) in 2019. We will use the budding yeast Saccharomyces cerevisiae as a biosensor to determine how deep-space radiation affects living organisms and to potentially quantify radiation levels through radiation damage analysis. Radiation can damage DNA through double strand breaks (DSBs), which can normally be repaired by homologous recombination. Two yeast strains will be air-dried and stored in microfluidic cards within the payload: a wild-type control strain and a radiation sensitive rad51 mutant that is deficient in DSB repairs. Throughout the mission, the microfluidic cards will be rehydrated with growth medium and an indicator dye. Growth rates of each strain will be measured through LED detection of the reduction of the indicator dye, which correlates with DNA repair and the amount of radiation damage accumulated. Results from BioSentinel will be compared to analog experiments on the ISS and on Earth. It is well known that desiccation can damage yeast cells and decrease viability over time. We performed a screen for desiccation-tolerant rad51 strains. We selected 20 re-isolates of rad51 and ran a weekly screen for desiccation-tolerant mutants for five weeks. Our data shows that viability decreases over time, confirming previous research findings. Isolates L2, L5 and L14 indicate desiccation tolerance and are candidates for whole-genome sequencing. More time is needed to determine whether a specific strain is truly desiccation tolerant. Furthermore, we conducted an intracellular trehalose assay to test how intracellular trehalose concentrations affect or protect the mutant strains against desiccation stress. S. cerevisiae cell and reagent concentrations from a previously established intracellular trehalose protocol did not yield significant absorbance measurements, so we tested varying cell and reagent concentrations and determined proper concentrations for successful protocol use.

BioSentinel↗

Biosentinel: Improving Desiccation Tolerance of Yeast Biosensors for Deep-Space Missions

BioSentinel is one of 13 secondary payloads to be deployed on Exploration Mission 1 (EM-1) in 2019. We will use the budding yeast Saccharomyces cerevisiae as a biosensor to determine how deep-space radiation affects living organisms and to potentially quantify radiation levels through radiation damage analysis. Radiation can damage DNA through double strand breaks (DSBs), which can normally be repaired by homologous recombination. Two yeast strains will be air-dried and stored in microfluidic cards within the payload: a wild-type control strain and a radiation sensitive rad51 mutant that is deficient in DSB repairs. Throughout the mission, the microfluidic cards will be rehydrated with growth medium and an indicator dye. Growth rates of each strain will be measured through LED detection of the reduction of the indicator dye, which correlates with DNA repair and the amount of radiation damage accumulated. Results from BioSentinel will be compared to analog experiments on the ISS and on Earth. It is well known that desiccation can damage yeast cells and decrease viability over time. We performed a screen for desiccation-tolerant rad51 strains. We selected 20 re-isolates of rad51 and ran a weekly screen for desiccation-tolerant mutants for five weeks. Our data shows that viability decreases over time, confirming previous research findings. Isolates L2, L5 and L14 indicate desiccation tolerance and are candidates for whole-genome sequencing. More time is needed to determine whether a specific strain is truly desiccation tolerant. Furthermore, we conducted an intracellular trehalose assay to test how intracellular trehalose concentrations affect or protect the mutant strains against desiccation stress. S. cerevisiae cell and reagent concentrations from a previously established intracellular trehalose protocol did not yield significant absorbance measurements, so we tested varying cell and reagent concentrations and determined proper concentrations for successful protocol use.

BioSentinel↗

Microkinetic simulation and fitting of the temperature programmed reaction of methanol on CeO 2 (111): H 2 and H 2 O + V production

The kinetics and mechanism for temperature programmed reaction following adsorption of an adsorbate can be better understood by simulation and fitting with comparison to experiment. A case study is presented here for the chemistry of adsorption of methanol on a CeO 2 (111) surface followed by heating. The gas products observed are CH 3 OH, CH 2 O, H 2 , H 2 O, CO, CO 2 . At low temperatures (< 500 K), there is formation of H 2 and H 2 O, where the H 2 O formation is accompanied by lattice oxygen vacancy (V) formation and is thus important in determining the selectivity towards different products. Microkinetic modeling was performed using a recently published method for fitting to gain mechanistic knowledge of the H 2 and H 2 O + V formation at < 500 K. In the kinetic models used here, most of the H 2 and H 2 O + V V formation can be explained by a mechanism in which a metastable state of hydrogen on the surface (H*) acts as an intermediate. Two possibilities were investigated for the source of the metastable H* intermediate: H* from CH bond breaking of methoxies, or promotion of H+ to H* via electron transfer from ionic methoxies absorbed in oxygen vacancies (CH 3 O - /V). From this study, we consider the latter to be more likely at < 500 K. For the H 2 O formation, it was found to be critical that H 2 O cannot dissociate directly on oxygen vacancies. Finally, catalytic chemistry was observed in simulations, including catalytic formation of oxygen vacancies. Various features of the experimental results were reproduced, including methoxies being the major carbon containing species on the surface at < 500 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interface Finite Elements for the Analysis of Fracture Initiation and Progression

Progressive failure analyses (PFA) are important for the prediction of residual strength and damage tolerance of vehicle structures, and to predict the energy absorbing capability of vehicle structures under crash-type loads. Typically continuum damage mechanics (CDM) and fracture mechanics (FM) are the methods used for PFA. The method of interfacial damage mechanics (IDM) is used for PFA in this research. IDM has capabilities intermediate between CDM and FM, and is used to numerically model the initiation, growth, and arrest of cracks. IDM smooths the stress singularity at the crack tip, and is easily adaptable with other nonlinearties such as plasticity and material damage. IDM is implemented by user-defined interface elements in the ABAQUS/ Standard structural analysis software package. The structural components selected to demonstrate the effectiveness PFA using interface elements are, for the most part, those with published test data. These structural components were subjected to quasi-static loading in the tests. Thus, the ABAQUS analyses are used to predict geometrically and materially nonlinear equilibrium states. Impact loading, dynamic fracture, reflected stress waves, inertia, and time dependent material behavior are not considered.

Ambur, Damodar R.↗