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At least 1,369 records · Page 76

A Simple, Revolutionary Approach to Waste Packaging Utilizing Proven Technology - 20201

Historically, removing hazardous waste from gloveboxes involves the use of bags as the primary containment method. This method can prove tedious, repetitive, and time consuming to ensure the process follows all safeguards required to contain the waste and mitigate any breach of containment. Layers of bags, yards of tape, and multiple filters are added to the waste stream in order to transfer the hazardous waste from the glovebox safely into the drum package. Then, finally, it can be shipped and disposed of. The process to cut, tie, and tape each bag for disposal involves manual effort by multiple operators. Following Administrative Safety Controls, good operators are able to safely perform those tasks; but, since the bag is the only confinement layer, incidents can occur. Operators, in some cases, are also at close proximity to this waste which may increase the risk of radiation exposure. Once the waste is transferred out through these bags, it is nearly impossible to remove packaged waste that may contain higher dosage levels, thus increasing drum disposal costs incurred by the facility. Exceeding the allowable radiation levels, and drums not fully filled, both contribute significantly to excess disposal costs. Central Research Laboratories (CRL), based in Red Wing Minnesota, has developed the Waste Drum Transfer System (WDTS) building upon the proven technology and containment of the Rapid Transfer Port (RTP) as an alternate, more efficient method of waste transfer. This solution consists of an RTP Alpha port mounted inside a glovebox and Beta assembly unit composed of a drum liner fitted inside a standard 55 gallon drum. The use of the Beta drum liner bypasses the typical use of bags, sleeves or tape to provide leak tight containment. The process to connect and disconnect a drum from the glovebox is achieved by the self-docking and rotating system controls of the RTP Alpha, all done with only one operator standing in an upright ergonomic position. This system also allows for greater flexibility in available Beta connection options, expanding the overall functionality of the system. This system can be disconnected and reconnected multiple times to maximize volume containment. This will minimize drum disposal costs and reduce the overall volume of waste output by more efficiently filling the drums. Radiation levels inside each drum can be monitored and adjusted more efficiently by operators utilizing the reconnect option. Minimal As Low As Reasonably Achievable (ALARA) levels are also achievable with this system. This paper will show how highly efficient packaging and disposal of hazardous waste can be accomplished in a cost-effective manner utilizing the proven RTP technology. Maximized operator productivity and safety, as well as minimized radiation dose exposure, are all attainable through the system's engineered controls. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Probing basal planes and edge sites in polygranular nuclear graphite by gas adsorption: Estimation of active surface area

Polygranular nuclear graphite, manufactured at 2800–3000 °C from a carbonized filler and binder mix, has high graphitization degree, crystalline structure close to perfect graphite, and about 20% porosity. The pore surfaces expose large regions of rough, defective prismatic edges of graphite crystallites which are the locus of graphite materials surface sites active for oxidation, chemisorption, and electron transfer. However, we show that high-resolution N 2 and Kr first monolayer adsorption on polygranular graphite (P/P 0 < 0.015) occurs in many ways like adsorption on graphitized carbon blacks. This proves the presence of energetically homogeneous basal planes domains in graphite porosity, which was not fully acknowledged before. Using classical analysis methods (Langmuir, Hill-de Boer, adsorption potential distribution) we quantity the basal plane area (BPA) of several polygranular graphite types and correlate it with their microstructure. Finally, we propose that gas adsorption is uniquely positioned to reliably estimate the active surface area of graphite by subtracting BPA from the BET total surface area. Direct estimation based on adsorption is preferable to indirect calculations based on microstructural information.

36 MATERIALS SCIENCE↗

Searching for correlations between vibrational spectral features and structural parameters of silicate glass network

Infrared (IR) and Raman spectroscopic features of silicate glasses are usually interpreted based on the analogy with those of smaller molecules, molecular clusters, or crystalline counterparts; this study tests the accuracy and validity of these widely cited peak assignment schemes by comparing vibrational spectral features with bond parameters of the glass network created by molecular dynamics (MD) simulations. A series of sodium silicate glasses with compositions of [Na 2 O] x [Al 2 O 3 ] 2 [SiO 2 ] 98- x with x = 7, 12, 17, and 22 were synthesized and analyzed with IR and Raman. A silica glass substrate and a crystalline quartz were also analyzed for comparison. Glass structures with the same compositions were generated with MD simulations using three types of potentials: fixed partial charge pairwise (Teter), partial diffuse charge potential (MGFF), and bond order-based charge transfer potential (ReaxFF). The comparison of simulated and experimental IR spectra showed that, among these three potentials tested, ReaxFF reproduces the concentration dependence of spectral features closest to the experimentally observed trend. Hence, the bond length and angle distributions as well as Si– Q n species and ring size distributions of silica and sodium silicate glasses were obtained from ReaxFF-MD simulations and further compared with the peak assignment or deconvolution schemes—which have been widely used since 1970s and 1980s—(a) correlation between the IR peak position in the Si–O stretch region (1050-1120 cm -1 ) and the Si–O–Si bond angle; (b) deconvolution of the Raman bands in the Si–O stretch region with the Q n speciation; and (c) assignment of the Raman bands in the 420-600 cm -1 region to the bending modes of (SiO) n rings with different sizes (typically, n = 3-6). The comparisons showed that none of these widely used methods is congruent with the bond parameters or structures of silicate glass networks produced via ReaxFF-MD simulations. This result invokes that the adequacy of these spectral interpretation methods must be questioned. Alternative interpretations are proposed, which are to be tested independently in future studies.

36 MATERIALS SCIENCE↗

Reductive chemistry of pyrrolic macrocycles: A PCET dichotomy between metal and ligand

Proton-coupled electron transfer (PCET) is central to the reactivity of porphyrins. The coupling of the electron to the proton is central to a porphyrin’s ability to catalyze energy conversion reactions of which the hydrogen evolution reaction (HER) is exemplary. To understand the mechanistic details of the PCET chemistry of porphyrins and related macrocyclic congeners, we have designed hangman constructs that allow a proton, placed in the secondary coordination sphere (off of the hangman backbone), to be coupled to redox transformations at the macrocycle. For metals whose reduction potentials are positive of the porphyrin macrocycle, such as Co and Fe, HER catalysis is confined to PCET transformations of the metal center where the active catalyst for HER is a reduced metal hydride. Alternatively, the reduction potentials of Ni, Zn, and 2H (freebase) porphyrins allow for redox non-innocence of the macrocycle; here the active “hydridic” catalyst is a phlorin, which gives rise to elaborate HER reaction sequences. Beyond HER catalysis, redox non-innocence of Ni, Zn, and 2H porphyrins and related compounds has been informative for providing detailed mechanistic insight into the multi-site PCET hydrogenation of olefinic bonds of the macrocycle. This mini-review unravels the PCET dichotomy between the metal and macrocycle in promoting HER catalysis and novel chemical transformations that give rise to unusual macrocyclic structures.

Chemistry↗

Interactions of satellite-speed helium atoms with satellite surfaces. 2: Energy distributions of reflected helium atoms

Energy transfer in collisions of satellite-speed (7,000 m/sec) helium atoms with a cleaned 6061-T6 satellite-type aluminum surface was investigated using the molecular-beam technique. The amount of energy transferred was determined from the measured energy of the molecular-beam and the measured spatial and energy distributions of the reflected atoms. Spatial distributions of helium atoms scattered from a 6061-T6 aluminum surface were measured. The scattering pattern exhibits a prominent backscattering, probably due to the gross surface roughness and/or the relative lattice softness of the aluminum surface. Energy distributions of reflected helium atoms from the same surface were measured for six different incidence angles. For each incidence angle, distributions were measured at approximately sixty scattering positions. At a given scattering position, the energy spectra of the reflected helium atoms and the background gas were obtained using the retarding-field energy analyzer.

Liu, S. M.↗

Docking system for spacecraft

A mechanism is disclosed for the docking of a spacecraft to a space station where a connection for transfer of personnel and equipment is desired. The invention comprises an active docking structure on a spacecraft and a passive docking structure on the station. The passive structure includes a docking ring mounted on a tunnel structure fixed to the space station. The active structure includes a docking ring carried by an actuator-attenuator devices, each attached at one end to the ring and at its other end in the spacecraft payload bay. The devices respond to command signals for moving the docking ring between a stowed position in the spacecraft to a deployed position suitable for engagement with the docking ring. The devices comprise means responsive to signals of sensed loadings to absorb impact energy and retraction means for drawing the coupled spacecraft and station into final docked configuration and moving the tunnel structure to a berthed position in the spacecraft. Latches couple the spacecraft and space station upon contact of the docking rings and latches establish a structural tie between the spacecraft when retracted.

Kahn, Jon B.↗

The Application of Remote Sensing Data to GIS Studies of Land Use, Land Cover, and Vegetation Mapping in the State of Hawaii

A land cover-vegetation map with a base classification system for remote sensing use in a tropical island environment was produced of the island of Hawaii for the State of Hawaii to evaluate whether or not useful land cover information can be derived from Landsat TM data. In addition, an island-wide change detection mosaic combining a previously created 1977 MSS land classification with the TM-based classification was produced. In order to reach the goal of transferring remote sensing technology to State of Hawaii personnel, a pilot project was conducted while training State of Hawaii personnel in remote sensing technology and classification systems. Spectral characteristics of young island land cover types were compared to determine if there are differences in vegetation types on lava, vegetation types on soils, and barren lava from soils, and if they can be detected remotely, based on differences in pigments detecting plant physiognomic type, health, stress at senescence, heat, moisture level, and biomass. Geographic information systems (GIS) and global positioning systems (GPS) were used to assist in image rectification and classification. GIS was also used to produce large-format color output maps. An interactive GIS program was written to provide on-line access to scanned photos taken at field sites. The pilot project found Landsat TM to be a credible source of land cover information for geologically young islands, and TM data bands are effective in detecting spectral characteristics of different land cover types through remote sensing. Large agriculture field patterns were resolved and mapped successfully from wildland vegetation, but small agriculture field patterns were not. Additional processing was required to work with the four TM scenes from two separate orbits which span three years, including El Nino and drought dates. Results of the project emphasized the need for further land cover and land use processing and research. Change in vegetation composition was noted in the change detection image.

Hogan, Christine A.↗

Key Issues for Navigation and Time Dissemination in NASA's Space Exploration Program

The renewed emphasis on robotic and human missions within NASA's space exploration program warrants a detailed consideration of how the positions of objects in space will be determined and tracked, whether they be spacecraft, human explorers, robots, surface vehicles, or science instrumentation. The Navigation Team within the NASA Space Communications Architecture Working Group (SCAWG) has addressed several key technical issues in this area and the principle findings are reported here. For navigation in the vicinity of the Moon, a variety of satellite constellations have been investigated that provide global or regional surface position determination and timely services analogous to those offered by GPS at Earth. In the vicinity of Mars, there are options for satellite constellations not available at the Moon due to the gravitational perturbations from Earth, such as two satellites in an aerostationary orbit. Alternate methods of radiometric navigation as considered, including one- and two-way signals, as well as autonomous navigation. The use of a software radio capable of receiving all available signal sources, such as GPS, pseudolites, and communication channels, is discussed. Methods of time transfer and dissemination are also considered in this paper.

Nelson, R. A.↗

Isolation of the Paenibacillus phoenicis, a Spore-Forming Bacterium

A microorganism was isolated from the surfaces of the cleanroom facility in which the Phoenix lander was assembled. The isolated bacterial strain was subjected to a comprehensive polyphasic analysis to characterize its taxonomic position. Both phenotypic and phylogenetic analyses clearly indicate that this isolate belongs to the genus Paenibacillus and represents a novel species. Bacillus spores have been utilized to assess the degree and level of microbiological contamination on spacecraft and their associated spacecraft assembly facilities. Spores of Bacillus species are of particular concern to planetary protection due to the extreme resistance of some members of the genus to space environmental conditions such as UV and gamma radiation, vacuum, oxidation, and temperature fluctuation. These resistive spore phenotypes have enhanced potential for transfer, and subsequent proliferation, of terrestrial microbes on another solar body. Due to decreased nutrient conditions within spacecraft assembly facility clean rooms, the vegetative cells of Bacillus species and other spore-forming Paenibacillus species are induced to sporulate, thereby enhancing their survivability of bioreduction

Benardini, James N.↗

Selective cysteine-to-selenocysteine changes in a [NiFe]-hydrogenase confirm a special position for catalysis and oxygen tolerance

Significance Substitution of cysteine by selenocysteine is held responsible for the increased performance of many enzymes: The higher activity of [NiFeSe]-hydrogenases compared with their [NiFe] counterparts is often attributed to the Sec replacement of one active-site cysteine ligand. Replacing each of the four active-site cysteine residues in an O 2 -tolerant [NiFe]-hydrogenase by selenocysteine shows that this substitution alone does not overcome the inability to evolve H 2 that is a characteristic of the group 1d hydrogenases. A nonbridging cysteine lying on the direct path between the Ni and an adjacent proton-relaying glutamic acid emerges as being very special: Its substitution by selenocysteine confers extreme tolerance to O 2 but disrupts the proton transfer pathway, providing an example of where sulfur is superior to selenium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluation of satellite Leaf Area Index in California vineyards for improving water use estimation

Remote sensing estimation of evapotranspiration (ET) directly quantifies plant water consumption and provides essential information for irrigation scheduling, which is a pressing need for California vineyards as extreme droughts become more frequent. Many ET models take satellite-derived Leaf Area Index (LAI) as a major input, but how uncertainties of LAI estimations propagate to ET and the partitioning between evaporation and transpiration is poorly understood. Here we assessed six satellite-based LAI estimation approaches using Landsat and Sentinel-2 images against ground measurements from four vineyards in California and evaluated ET sensitivity to LAI in the thermal-based two-source energy balance (TSEB) model. We found that radiative transfer modeling-based approaches predicted low to medium LAI well, but they significantly underestimated high LAI in highly clumped vine canopies (RMSE ~ 0.97 to 1.27). Cubist regression models trained with ground LAI measurements from all vineyards achieved high accuracy (RMSE ~ 0.3 to 0.48), but these empirical models did not generalize well between sites. Red edge bands and the related vegetation index (VI) from the Sentinel-2 satellite contain complementary information of LAI to VIs based on near-infrared and red bands. TSEB ET was more sensitive to positive LAI biases than negative ones. Positive LAI errors of 50% resulted in up to 50% changes in ET, while negative biases of 50% in LAI caused less than 10% deviations in ET. However, even when ET changes were minimal, negative LAI errors of 50% led to up to a 40% reduction in modeled transpiration, as soil evaporation and plant transpiration responded to LAI change divergently. These findings call for careful consideration of satellite LAI uncertainties for ET modeling, especially for the partitioning of water loss between vine and soil or cover crop for effective vineyard irrigation management.

54 ENVIRONMENTAL SCIENCES↗

Biocatalytic control of site-selectivity and chain length-selectivity in radical amino acid halogenases

Biocatalytic C–H activation has the potential to merge enzymatic and synthetic strategies for bond formation. Fe II /αKG-dependent halogenases are particularly distinguished for their ability both to control selective C–H activation as well as to direct group transfer of a bound anion along a reaction axis separate from oxygen rebound, enabling the development of new transformations. In this context, we elucidate the basis for the selectivity of enzymes that perform selective halogenation to yield 4-Cl-lysine (BesD), 5-Cl-lysine (HalB), and 4-Cl-ornithine (HalD), allowing us to probe how site-selectivity and chain length selectivity are achieved. We now report the crystal structure of the HalB and HalD, revealing the key role of the substrate-binding lid in positioning the substrate for C 4 vs C 5 chlorination and recognition of lysine vs ornithine. Targeted engineering of the substrate-binding lid further demonstrates that these selectivities can be altered or switched, showcasing the potential to develop halogenases for biocatalytic applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

ASAS J071404+7004.3 – a close, bright nova-like cataclysmic variable with gusty winds

ABSTRACT Despite being bright (V ≃ 11.8) and nearby (d = 212 pc) ASAS J071404+7004.3 has only recently been identified as a nova-like cataclysmic variable. We present time-resolved optical spectroscopy obtained at the Isaac Newton and the Hiltner and McGraw-Hill Telescopes, together with Swift X-ray and ultraviolet observations. We combined these with TESS photometry and find a period of 3.28 h and a mass transfer rate of $4\!-\!9\times 10^{-9}\, {\mathrm{M_{\odot }\, yr}^{-1}}$. Historical photometry shows at least one low state establishing the system as a VY Scl star. Our high-cadence spectroscopy also revealed rapidly changing winds emanating from the accretion disc. We have modelled these using the Monte Carlo python code and shown that all the emission lines could emanate from the wind – which would explain the lack of double-peaked lines in such systems. In passing, we discuss the effect of variability on the position of cataclysmic variables in the Gaia Hertzsprung–Russell diagram.

Inight, K. (ORCID:0000000222002416)↗

Modeled ground magnetic signatures of flux transfer events

The magnetic field on the ground due to a small (not greater than 200 km scale size) localized field-aligned current (FAC) system interacting with the ionosphere is calculated in terms of an integral over the ionospheric distribution of FAC. Two different candidate current systems for flux transfer events (FTEs) are considered: (1) a system which has current flowing down the center of a cylindrical flux tube with a return current uniformly distributed along the outside edge; and (2) a system which has upward current on one half of the perimeter of a cylindrical flux tube with downward current on the opposite half. The peak magnetic field on the ground is found to differ by a factor of 2 between the two systems, and the magnetic perturbations are in different directions depending on the observer's position.

Mchenry, Mark A.↗

Stratospheric feedback from continued increases in tropospheric methane

Tropospheric concentrations of methane have increased steadily over the past ten years at an average rate of 16.5 ppbv per year, to a value in January 1988 of 1.69 ppmv. Measurements of CH sub 4 concentrations in air bubbles trapped in ice cores have shown concentrations of about 0.7 ppmv 200 years ago, with little further change for thousands of years before that. Interpolation earlier into this century suggests a concentration of about 1.1 to 1.2 ppmv in the 1940's. The only important pathway believed to be important for transfer of air from the troposphere to the stratosphere in through the tropical tropopause which is cold enough to reduce the mixing ratio of H sub 2 O in that air to about 3 ppmv. The only other major pathway for the delivery of H to the stratosphere is through the simultaneous injection of gaseous CH sub 4 in the same rising air. The formation of clouds in the stratosphere is dependent upon very low temperatures, and generally upon the amount of water vapor available. The possibility of a positive feedback exists, especially in well-oxidized methane air, that clouds are easier to form than earlier. This could mean enhancement of PSCs in both Antarctic and Arctic locations. Additional H sub 2 O in the stratosphere can also add to some of the greenhouse calculations.

Rowland, F. Sherwood↗

Solar cycle variation in the subauroral electron temperature enhancement - Comparison of AE-C and DE 2 satellite observations

The elevation of the subauroral electron temperature is one of the phenomena showing the energy transfer from the magnetosphere and the response of the ionosphere. This study addresses solar cycle variations in the subauroral Te peak by comparing observations of the subauroral peak by the Atmosphere Explorer C (AE-C) satellite near solar minimum (1974 and 1977) with similar observations by the Dynamics Explorer 2 (DE 2) satellite near solar maximum (1981-1982). Te peaks with magnitudes sufficient to produce observable stable auroral red arc emissions occurred more frequently during solar maximum than in solar minimum, but the variation in the magnitudes and positions of these peaks with magnetic activity did not change significantly with solar cycle. These results are discussed in terms of the solar cycle changes in the ionosphere and the magnetospheric energy source.

Fok, M.-C.↗

Atomic oxygen in the Martian thermosphere

Modern models of thermospheric composition and temperature and of excitation and radiative transfer processes are used to simulate the O I 130-nm emission from Mars measured by the Mariner 9 ultraviolet spectrometer. This paper uses the Mars thermospheric general circulation model calculations (MTGCM) of Bougher et al. (1988) and the Monte Carlo partial frequency redistribution multiple scattering code of Meier and Lee (1982). It is found that the decline in atomic oxygen through the daylight hours predicted by the MTGCM cannot be reconciled with the excess afternoon brightness seen in the data. Oxygen concentrations inferred from the data show a positive gradient through the day, in agreement with the original analysis by Strickland et al. (1973). In addition, the data suggest that the oxygen abundance increases toward high southerly latitudes, in contrast with the MTGCM prediction of high values in the Northern Hemisphere. It appears that solar forcing alone cannot account for the observed characteristics of the Martian thermosphere and that wave and tidal effects may profoundly affect the structure, winds, and composition.

Stewart, A. I. F.↗

Tropical cirrus cloud radiative forcing: Sensitivity studies

We have performed one dimensional radiative transfer calculations to evaluate the impact of cirrus clouds on the tropical radiation budget. We investigate the sensitivity of solar and infrared fluxes to cloud optical depth, particle size distributions, and cloud height. If the observed solar cloud forcing in excess of 100 W/sq m is to be attributed to cirrus anvils alone, then the optical depth of these anvils must be at least 5 (assuming 50% cloud cover and an ice crystal effective radius of 15 microns). The net radiative forcing of cirrus near the tropical tropopause is positive (heating) for cloud optical depths less than about 16 and negative (cooling) for larger optical depths. If cirrus clouds alone are responsible for the equal and opposite shortwave and longwave cloud forcing in excess of 100 W/sq m observed by Earth Radiation Budget Experiment (ERBE), then the cirrus must typically take the form of deep, optically thick clouds with relatively small particles (radii of 10-20 microns) and cloud-tops well below the tropopause. The maintenance of this balance on monthly time scales can be attributed to a variety of correlations: The cloud cover of optically thick cirrus or thin cirrus overlying low-level stratus clouds could vary; or cirrus anvil height cloud increase along with a decrease in the ice crystal effective radius and an increase in optical depth. It would be of great interest to determine observationally which of these correlations is responsible for the observed lack of variation in cloud forcing.

Jensen, E. J.↗