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Relative Bioavailability of Scopolamine Dosage Forms and Interaction with Dextroamphetamine

The NASA Reduced Gravity Office (RGO) uses scopolamine (SCOP) and in combination with dextoamphetamine (DEX) to manage motion sickness symptoms during parabolic flights. The medications are dispensed as custom dosage forms as gelatin capsules. Anecdotal evidence of efficacy suggests that these formulations are unreliable and less efficacious for the treatment of motion sickness. We estimated bioavailability of four different oral formulations used by NASA for the treatment of motion sickness. Twelve healthy, non-smoking subjects between 21and 48 years of age received four treatments on separate days in a randomized fashion; the treatments were 0.8 mg SCOP alone as tablet, 0.8 mg SCOP alone in gel cap, 0.8 mg SCOP and 10 mg DEX as tablets, and 0.8 mg SCOP and 10 mg DEX in gel cap. After each treatment, blood, saliva, and urine samples were collected at scheduled time intervals for 24 h after dosing. Bioavailability and pharmacokinetic parameters were calculated and compared using ANOVA. After administration of SCOP tablets alone, maximum concentration (C(sub max)) and time for maximum concentration (t(sub max)) were 0.26 plus or minus 0.04 ng/mL and 0.71 plus or minus 0.02 h, respectively; volume of distribution, and clearance were 47.6 plus or minus 4.72 L/kg and 23.0 plus or minus 4.58 L/h/kg, respectively. SCOP t(sub max) after administration as gelcaps was significantly longer than that with tablets (1.04 h, p less than 0.05), but no significant differences in other pharmacokinetic parameters of SCOP were observed between the two dosage forms. When coadministered with DEX, the area underneath the concentration versus time curve (AUC) of SCOP was significantly reduced to 0.61 plus or minus 0.09 and 0.64 plus or minus 0.11 ng (raised dot) h/mL after administration as a tablet or gelcap formulation, respectively; SCOP C(sub max) was lower after coadministration with DEX, this difference, however, was not statistically significant. Delayed absorption with gelcaps coupled with reduced bioavailability with DEX coadministration may have resulted in the observed treatment failure with some of these formulations. This could result from failure to reach minimum effective concentrations after treatment with gelcap formulations before parabolic flights. A new nomogram for dosing is proposed for treatment with SCOP gelcaps or SCOP-DEX combination.

Boyd, Jason L.↗

Polar Stratospheric Descent of NO(y) and CO and Arctic Denitrification During Winter 1992-1993

Observations inside the November 1994 Antarctic stratospheric vortex and inside the April 1993 remnant Arctic stratospheric vortex by the Atmospheric Trace Molecule Spectroscopy (ATMOS) Fourier transform spectrometer are reported. In both instances, elevated volume mixing ratios (VMRS) of carbon monoxide (CO) were measured. A peak Antarctic CO VMR of 60 ppbv (where 1 ppbv = 10(exp -9) per unit Volume) was measured at a potential temperature of 710 K (about 27 km), about 1 km below the altitude of a pocket of elevated NO(y) (total reactive nitrogen) at a deep minimum in N2O (<5 ppbv). The Arctic observations also show a region of elevated vortex CO with a peak VMR of 90 ppbv it 630-670 K (-25 km) but no corresponding enhancement in NO(sub y) perhaps because of stronger dynamical activity in the northern hemisphere polar winter and/or interannual variability in the production of mesospheric or lower thermospheric NO. By comparing vortex and extravortex observations of NO(y) obtained at the same N2O VMR, Arctic vortex denitrification of 5 +/- 2 ppbv at 470 K (at approximately 18 km) is inferred. We show that our conclusion of substantial Arctic winter 1992-1993 denitrification is robust by comparing our extravortex observations with previous polar measurements obtained over a wide range of winter conditions. Correlations of NO(y) with N2O measured at the same potential temperature by ATMOS in the Arctic vortex and at midlatitudes on board the ER-2 aircraft several weeks later lie along the same mixing line. The result demonstrates the consistency of the two data sets and confirms that the ER-2 sampled fragments of the denitrified Arctic vortex following its breakup. An analysis of the ATMOS Arctic measurements of total hydrogen shows no evidence for significant dehydration inside the vortex.

Rinsland, C. P.↗

4.32 Billion Year Old Impact Melts at Apollo 14: Dating the Procellarum Basin?

Introduction: Recent work has improved our understanding of lunar crustal structure and basin evolution on the Moon, but its early impact history and implications for solar system dynamics remain poorly established [1,2]. In particular, there is a derth of absolute ages, especially for the period >4.0 Ga, that could be related to basin-forming events. Here we present U-Pb isotopic data for Zr-rich minerals found in impact-melt fragments from Apollo 14 soil sample 14163 that, when combined with previously published data, dates an impact event at 4324±15 Ma. The compositions and ages of these impact-melt fragments provide unique information about the timing of early impact events and the composition of the lunar crust. Results: Fourteen rocklets ranging in size from 1 to 3 mm were extracted from soil 14163. Most are impactmelt rocks with 10-30% clasts of mostly pyroxene and plagioclase (100 to 500 μm) in a crystalline matrix. Textures of the matrix vary from subophitic, formed by intergrowths of 10-20 μm plagioclase and pyroxene crystals, to poikilitic, with plagioclase and pyroxene reaching 20-50 μm size. Some fragments that contain no visible clasts have similar textures are also interpreted as impact-melt rocks. All fragments contain notably large proportions of euhedral to subhedral ilmenite, zircon, apatite/merrillite and less abundant zirconolite and baddeleyite in the melt matrices. These grains often form intricate intergrowths with each other and rock-forming minerals, indicating their crystallization from the melt (Fig. 1). However, some slightly larger (~50 μm) zircon and phosphate grains can be interpreted as relict clasts based on their granular textures and relationships with the surrounding phases (Fig. 1). This implies that zircon and phosphate minerals were present in the target rocks. Some of these grains were profoundly remelted during the impact, which resulted in an oversaturation of the melt in Zr and P and crystallization of new grains of Zrrich minerals and phosphates during melt solidification. The presence of zircon and phosphates indicates that the melts were significantly enriched in KREEP components and ties their provenance to the Procellarum- KREEP Terrane (PKT) [3]. Combined U-Pb zircon data obtained for all fragments form two main clusters on a concordia diagram (Fig. 2), between about 4.3 and 3.9 Ga. Phosphate data mostly concentrate on the younger end of this age range but some analyses are almost as old as the older zircon grains (Fig. 2). Figure 1: Zircon (Zr) and phosphate (Apt; Mer) grains in impact melt fragments from Apollo 14 soil 14161. A-zircon grains crystallized from impact melt; B-phosphate grain inherited from the target; C- granular zircon grains Our interpretation of these data is that all U-rich minerals experienced variable resetting of the U-Pb system, with phosphate, where closure temperature is significantly lower than that in zircon, affected more profoundly by Pb loss than zircon. Our best estimate of the time of formation of zircon and phosphate is based on statistically valid analysis of grains interpreted texturally as grown from the impact melt (Fig. 2). Ten of these analyses define an age of 4324±15 Ma (MSWD=3.0, probability of fit P=0.002). Our best estimate for the time of resetting is obtained by combining data from phosphates that are statistically indistinguishable from 3.9 Ga within the analytical uncertainties. This group is represented by 18 analyses of 15 phosphate grains from different fragments (Fig. 2) and defines an age of 3922±6 Ma (MSWD=1.2, P=0.23). Conversely, a minimum age of the target lithologies, remelted in the impact that produced the rocklets studied here (Fig. 2), can be determined from the five oldest analyses of zircon clasts at 4338±13 Ma (MSWD=1.5, P=0.2), which is indistinguishable from the age of the impact melt within the uncertainties. The obtained ages, combined with textural evidence, imply that the impact melt was formed at 4324±15 Ma, and that it occurred in a zircon-rich target with a minimum age of 4338±13 Ma. Further reworking occurred during a second impact event at 3922±6 Ma. Discussion: The younger age of 3922±6 Ma can be interpreted as the time of the Imbrium impact. The older age of 4324±15 Ma would then be the time of formation of the impact melt, which was then caught in the Imbrium ejecta either at the Apollo 14 landing site or within the target rocks of the Imbrium impact. The presence of abundant accessory phases such as zircons and phosphates is consistent with a substantial KREEP component in the analyzed particles. The current distribution of KREEP on the lunar surface appears to be strongly influenced by Imbrum ejecta [4] so interpretation of the 4.32 Ga age depends in part on assumed structure of the pre-impact crust and distribution of KREEP within the crust. If KREEP was present only in the deep crust at 4.32 Ga, then a basin-scale impact possibly analogous to Imbrium or larger may be necessary to excavate a KREEPy impact melt at this time. However, if KREEPy materials were present closer to the surface perhaps due to redistribution related to Mg-suite magmatism, then smaller impacts might be able to rework KREEPy compositions at shallower depths. The coherence of the data on the particles analysed here suggests a large volume of melt that has been preserved since 4.32 Ga, consistent with a large impact event. Relict zircons and mineral clasts suggests that the igneous crust in the vicinity of this impact was well developed by at least 4.34 Ga, similar to the model age of KREEP and older than the isochron ages of many Mg-suite cumulates [5]. A problem that confronts all lunar sample studies using the current collection is that the pre-Imbrium geology of the PKT (the source of these 4.32 Ga impact melts) is not well constrained. The South Pole-Aitken basin contains regions that are moderately enriched in Th, but its ejecta is Th-poor [6]; therefore these A14 fragments are probably not SPA ejecta. Alternatively, these fragments may represent formation of a hypothesized Procellarum basin [7] although the lack of a clearly defined basin ejecta signature is a potential problem with that interpretation. In any case, they provide a younger limit on the age of lunar differentiation and formation of KREEP within the lunar crust. Figure 2: U-Pb data for zircon and phosphate grains from impact melt fragments. A-all data; B-data used for age calculations. References: [1] Orgel C., Michael G., Fassett C. I., van der Bogert C. H., Riedel C., Kneissl T., and Hiesinger H. (2018) J. Geophys. Res. Planets 123, 748- 762. [2] Evans A. J., Andrews-Hanna J. C., Head J. W., Soderblom J. M., Solomon S. C., and Zuber M. T. (2018) J. Geophys. Planets. 123, 1596-1617. [3] Jolliff, B.L., Gillis, J.J., Haskin, L.A., Korotev, R.L. and Wieczorek, M.A. (2000) J. Geophys. Res: Planets 105, 4197-4216. [4] Haskin L. A. (1998) J. Geophys. Res. Planets 103, 1679-1689. [5] Borg L.E., Gaffney A.M., and Shearer C.K. (2015) MAPS 50, 715-732. [6] Moriarty, D.P., Watkins, R.N., Valencia, S.N., Kendall, J.D., Evans, A.J., Dygert, N. and Petro, N.E. (2021) J. Geophys. Res. Planets 126. [7] Zhu, M.H., Wünnemann, K., Potter, R.W., Kleine, T. and Morbidelli, A. (2019) J. Geophys. Res: Planets 124, 2117-2140

M D Norman↗

Heat Melt Compaction as an Effective Treatment for Eliminating Microorganisms from Solid Waste

One of the technologies being tested at Ames Research Center as part of the logistics and repurposing project is heat melt compaction (HMC) of solid waste to reduce volume, remove water and render a biologically stable and safe product. Studies at Kennedy Space Center have focused on the efficacy of the heat melt compaction process for killing microorganisms in waste and specific compacter operation protocols, i.e., time and temperature required to achieve a sterile, stable product. The work. reported here includes a controlled study to examine the survival and potential re-growth of specific microorganisms over a 6-month period of storage after heating and compaction. Before heating and compaction, ersatz solid wastes were inoculated with Bacillus amyloliquefaciens and Rhodotorula mucilaginosa, previously isolated from recovered space shuttle mission food and packaging waste. Compacted HMC tiles were sampled for microbiological analysis at time points between 0 and 180 days of storage in a controlled environment chamber. In addition, biological indicator strips containing spores of Bacillus atrophaeus and Geobacillus stearothermophilus were imbedded in trash to assess the efficacy of the HMC process to achieve sterilization. Analysis of several tiles compacted at 180deg C for times of 40 minutes to over 2 hours detected organisms in all tile samples with the exception of one exposed to 180deg C for approximately 2 hours. Neither of the inoculated organisms was recovered, and the biological indicator strips were negative for growth in all tiles indicating at least local sterilization of tile areas. The findings suggest that minimum time/temperature combination is required for complete sterilization. Microbial analysis of tiles processed at lower temperatures from 130deg C-150deg C at varying times will be discussed, as well as analysis of the bacteria and fungi present on the compactor hardware as a result of exposure to the waste and the surrounding environment. The two organisms inoculated into the waste were among those isolated and identified from the HMC surfaces indicating the possibility of cross contamination.

Hummerick, Mary P.↗

Heat Melt Compaction as an Effective Treatment for Eliminating Microorganisms from Solid Waste

One of the technologies being tested at Ames Research Center as part of the logistics and repurposing project is heat melt compaction (HMC) of solid waste to reduce volume, remove water and render a biologically stable and safe product. Studies at Kennedy Space Center have focused on the efficacy of the heat melt compaction process for killing microorganisms in waste and specific compacter operation protocols, i.e., time and temperature, required to achieve a sterile, stable product. The work reported here includes a controlled study to examine the survival and potential re-growth of specific microorganisms over a 6-month period of storage after heating and compaction. Before heating and compaction, ersatz solid wastes were inoculated with Bacillus amyloliquefaciens and Rhodotorula mucilaginosa, previously isolated from recovered space shuttle mission food and packaging waste. Compacted HMC tiles were sampled for microbiological analysis at time points between 0 and 180 days of storage in a controlled environment chamber. In addition, biological indicator strips containing spores of Bacillus atrophaeus and Ceo bacillus stearothermophilus were imbedded in trash to assess the efficacy of the HMC process to achieve sterilization. Analysis of several tiles compacted at 180 C for times of 40 minutes to over 2 hours detected organisms in all tile samples with the exception of one exposed to 180 C for approximately 2 hours. Neither of the inoculated organisms was recovered, and the biological indicator strips were negative for growth in all tiles indicating at least local sterilization of tile areas. The findings suggest that minimum time/temperature combination is required for complete sterilization. Microbial analysis of tiles processed at lower temperatures from 130 C-150 C at varying times will be discussed, as well as analysis of the bacteria and fungi present on the compactor hardware as a result of exposure to the waste and the surrounding environment. The two organisms inoculated into the waste were among those isolated and identified from the HMC surfaces indicating the possibility of cross contamination.

Hummerick, Mary P.↗

Hyperspectral Microwave Atmospheric Sounder (HyMAS) Architecture and Design Accommodations

The Hyperspectral Microwave Atmospheric Sounder (HyMAS) is being developed at Lincoln Laboratories and accommodated by the Goddard Space Flight Center for a flight opportunity on a NASA research aircraft. The term "hyperspectral microwave" is used to indicate an all-weather sounding that performs equivalent to hyperspectral infrared sounders in clear air with vertical resolution of approximately 1 km. Deploying the HyMAS equipped scanhead with the existing Conical Scanning Microwave Imaging Radiometer (CoSMIR) shortens the path to a flight demonstration. Hyperspectral microwave is achieved through the use of independent RF antennas that sample the volume of the Earth s atmosphere through various levels of frequencies, thereby producing a set of dense, spaced vertical weighting functions. The simulations proposed for HyMAS 118/183-GHz system should yield surface precipitation rate and water path retrievals for small hail, soft hail, or snow pellets, snow, rainwater, etc. with accuracies comparable to those of the Advanced Technology Microwave Sounder. Further improvements in retrieval methodology (for example, polarization exploitation) are expected. The CoSMIR instrument is a packaging concept re-used on HyMAS to ease the integration features of the scanhead. The HyMAS scanhead will include an ultra-compact Intermediate Frequency Processor (IFP) module that is mounted inside the door to improve thermal management. The IFP is fabricated with materials made of Low-Temperature Co-fired Ceramic (LTCC) technology integrated with detectors, amplifiers, A/D conversion and data aggregation. The IFP will put out 52 channels of 16 bit data comprised of 4-9 channel data streams for temperature profiles and 2-8 channel streams for water vapor. With the limited volume of the existing CoSMIR scanhead and new HyMAS front end components, the HyMAS team at Goddard began preliminary layout work inside the new drum. Importing and re-using models of the shell, the scan head computer, and the slip rings developed for CoSMIR was the starting point. The next step was to modify the antenna faceplate to accommodate the dimensions of the three dual polarization Gaussian Optics Antenna (GOA) assemblies. Two mechanical concepts for the core technology, the hyperspectral IFP, were captured in a design tradeoff. Connector models considered minimum bend radii for the IFP analog connectors. Hyperspectral imaging is accomplished by strategically using a short wavelength intermediate frequency of 18-29 GHz, and thus reducing the size of components in the connection of the front end to the IFP. The SMK (2.92mm) Series connector will lay near the hinge line to minimize its flexing. The digital output of the IFP will use a Serial Peripheral Interface (SPI) that must be accommodated by the scan head computer. To make that computer more reliable, maintainable, and forward compatible with the 52 HyMAS channels, a testbed of the scan head, calibration, and archive computers and the PIC24 microprocessor that resides on the IFP is in development. The computers will be programmed using a new framework application called Interoperable Remote Component (IRC). This software allows flexibility to program computers that communicate with each other and can adapt easily to the emerging HyMAS requirements for data format, algorithms, and graphical user interface (GUI). It is expected that the CoSMIR instrument will cut over to the IRC after it is adapted on an updated CoSMIR testbed.

Hilliard, Lawrence↗

Oxidation of Glycolate in the Defense Waste Processing Facility (DWPF) Recycle Collection Tank - 20305

The Savannah River Site's Defense Waste Processing Facility (DWPF) operations are being upgraded with the introduction of the Nitric-Glycolic Flowsheet. Glycolic acid has been shown superior to formic acid as the reducing acid used during chemical processing. The new flowsheet improves or maintains necessary parameters such as 1) reduction of mercury, 2) adjustment of feed rheology and 3) adjustment of melter oxidation/reduction potential. Further, the potential for catalytic hydrogen generation in DWPF processing is virtually eliminated. DWPF process condensates are collected and returned to the SRS Concentration, Storage and Transfer Facilities (CSTF). The Recycle Collection Tank (RCT) collects off-gas condensate during chemical processing, vitrification, and other unit operations performed in DWPF and is the singular return vessel delivering recycle effluent back to CSTF. Each batch of recycle may contain a small amount of glycolate from chemical processing and melter off-gas condensates. To avoid potential flammability issues due to thermolysis of glycolate in the CSTF, chemical oxidation within the RCT has been investigated as an option for mitigating the transfer of glycolate. Sodium permanganate has been down-selected as the best option for oxidation of glycolate. Testing was performed using both 2-L and 22-L reactors (16,800:1 and 1,530:1 scale by volume) with non-radioactive waste simulants to approximate the expected RCT compositions. RCT simulants were evaluated at various process pH and temperature conditions. Also, RCT operations, namely the sequence of addition of corrosion inhibitors (NaOH and NaNO{sub 2}) versus a permanganate strike, were evaluated. Glycolate was introduced via a sludge simulant to mimic both expected entrainment and abnormal process foam-over conditions - the range being between 68 and 5100 mg/kg glycolate. Glycolate destruction was monitored by ion chromatography (IC). The corresponding manganese behavior was monitored in real-time using in situ ultraviolet-visible (UV-Vis) spectroscopy. RCT glycolate content can be reduced to below the IC detection limit within 90 minutes for all concentrations investigated. Ion Chromatography analysis revealed that under alkaline conditions, glycolate is primarily oxidized to oxalate with no significant formation of CO{sub 2} or carbonate, and nitrite is not oxidized to nitrate. Initially, complete oxidation of organics species and nitrite was assumed. Determination of the mechanistic chemical reaction has allowed the required amount of permanganate to be more accurately predicted and the total addition to be significantly reduced. UV-Vis measurements reveal that permanganate (Mn{sup 7+}) is reduced to manganate (Mn{sup 6+}) in the RCT. The oxidant stoichiometry is defined by using the initial permanganate to glycolate (P/G) molar ratio. At low initial glycolate concentration (68 and 140 mg/kg), the minimum required initial permanganate to glycolate (P/G) molar ratio was found to be 5-6. With high initial glycolate concentrations (5100 mg/kg) a lower (P/G) molar ratio of ∼2.5 was needed. The final portion of this effort supporting the nitric/glycolic flowsheet will be to test actual (fully radioactive) RCT samples as per the above simulant tests. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

End-Use Savings Shapes Measure Documentation: Variable Refrigerant Flow with Heat Recovery and Dedicated Outdoor Air System

Building on the successfully completed effort to calibrate and validate the U.S. Department of Energy's ResStock™ and ComStock™ models over the past 3 years, the objective of this work is to produce national data sets that empower analysts working for federal, state, utility, city, and manufacturer stakeholders to answer a broad range of analysis questions. The goal of this work is to develop energy efficiency, electrification, and demand flexibility end-use load shapes (electricity, gas, propane, or fuel oil) that cover a majority of the high-impact, market-ready (or nearly market-ready) measures. "Measures" refers to energy efficiency variables that can be applied to buildings during modeling. An end-use savings shape is the difference in energy consumption between a baseline building and a building with an energy efficiency, electrification, or demand flexibility measure applied. It results in a time-series profile that is broken down by end use and fuel (electricity or on-site gas, propane, or fuel oil use) at each time step. ComStock is a highly granular, bottom-up model that uses multiple data sources, statistical sampling methods, and advanced building energy simulations to estimate the annual subhourly energy consumption of the commercial building stock across the United States. The baseline model intends to represent the U.S. commercial building stock as it existed in 2018. The methodology and results of the baseline model are discussed in the final technical report of the End-Use Load Profiles project. This documentation focuses on a single heating, ventilation, and air-conditioning (HVAC) end-use savings shape measure - a variable refrigerant flow with heat recovery (VRF HR) heating and cooling system coupled with a dedicated outdoor air system (DOAS) for ventilation. This measure replaces existing multi-zone variable air volume (VAV) systems or single-zone rooftop units (RTU) with a VRF HR system coupled with a DOAS that includes an energy/heat recovery ventilator (E/HRV). The measure covers 53% of exisiting building stock's floor area and is not applicable to HVAC system types using district heating or cooling or buildings/spaces that include high-ventilation spaces such as kitchens where the amount of exhaust air is large. A DOAS with E/HRV is used to provide required outdoor ventilation air to spaces since ventilation air is generally not supplied by a VRF HR system. An exhaust air energy recovery ventilator (ERV ) with sensible and latent heat exchange is added to humid climate zones while a heat recovery ventilator (HRV ) with sensible only exchange is added to drier climate zones. The ERV is modeled as a fixed membrane plate counterflow heat exchanger, while the HRV is modeled as a sensible-only fixed aluminum plate counterflow heat exchanger. Both systems include a bypass (for temperature control and economizer lockout) and minimum exhaust temperature control for frost prevention.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Monitoring of Volcanogenic CO2-Induced Tree Kills with AVIRIS Image Data at Mammoth Mountain, California

Elevated cold CO2 emissions from the flank of Mammoth Mountain volcano on the southwest rim of the Long Valley Caldera, eastern California, have been the cause of over 100 acres of dead trees in that area since 1990. The source of the CO2 gas is thought to be from one or more magmatic intrusion(s) beneath Mammoth Mountain and is probably related to a period of seismic unrest that began in 1989. The gas rises to the surface probably from depths of a few kilometers, along faults and fracture zones. The gas is at ambient temperature and diffuses from the soil rather than discharging from distinct vents. Typically, soil gas concentrations in tree-kill areas range from 10% to over 90% CO2 by volume, as compared to normal background of < 1% in healthy forest. The gas composition is predominantly CO2 mixed with air (sulfur gases are not elevated), and C and He isotopic ratios are consistent with a magmatic origin for the gas. The total CO2 emission has been estimated at 1200 tons/day, comparable to the emissions at Kilauea. Some of the dead trees are as old as 250 years, suggesting that similar anomalous gas discharge has not occurred over the previous few hundred years. The delta C-13/12 ratio in the Mammoth Mountain CO2 emission averages about -4.5 (PDB standard). This is consistent with a mantle source for the carbon. However, the large volume of the emission suggests that not all of the CO2 is necessarily being generated from the 1989 intrusion. The voluminous gas could be leaking from a vapor-rich zone, capped by an impermeable layer, that was supplied CO2 from degassing of many small magma bodies that intruded beneath the mountain over a period of decades or centuries. Earthquakes in 1989 could have fractured the capping layer and provided pathways for the escape Of CO2 to the surface. Alternatively, some of the CO2 could be derived from contact metamorphism of carbonate rocks intruded by magma. Carbonate-bearing Paleozoic roof pendents crop out in close proximity to Mammoth Mountain. It is possible that similar rocks could occur at depth beneath Mammoth Mountain, and could have contributed CO2 from thermal decomposition caused from recent intrusions. We hope to determine the C-13/12 ratio of a suite of samples to demonstrate if the carbonate rocks could be the source of at least part of the 1990-97 CO2 emission. To better understand the behavior of the CO2 gas, we have used hyperspectral imagery data of Mammoth Mountain acquired from the Airborne Visual/Infrared Imaging Spectrometer (AVIRIS) to map out areas of dead trees. The areas of tree kill have increased in size from about 50 acres in 1994 to about 100 acres in 1997. Tree kill is the major surface manifestation of the carbon dioxide flux at Mammoth Mountain, is widely dispersed, and has been cursorily mapped by regular field mapping techniques in the area. Initial investigations using airborne digital imagery from the Thematic Mapper Simulator (NS001) and AVIRIS instruments have shown extremely encouraging results for complete delineation of the vegetation anomalies. The most successful maps (when compared with ground truth) were developed using AVIRIS data with spectral angle mapper and matched filter algorithms with a data set that was reduced to maximum variance via the minimum noise fraction transformation. The result of this work is a series of maps that show the tree kill areas occurring in an halo-pattern surrounding the base of Mammoth Mountain. We are applying these same techniques to earlier AVIRIS images of Mammoth Mountain to examine the progression of the tree kill areas over time. Temporal maps of the tree kill areas may assist in constructing a picture of the structure beneath Mammoth Mountain.

Hausback, Brian P.↗

Intermediate-Term Thermal Aging Effect Evaluation for Grade 92 and 316L at The LWR Relevant Temperature

Life extension of the existing nuclear reactors imposes accumulated damages, such as higher fluences and longer period of corrosion, to structural materials, which would result in significant challenges to the traditional reactor materials such as type 304 and 316 stainless steels. Advanced alloys with superior radiation resistance will increase safety margins, design flexibility, and economics for not only the life extension of the existing fleet but also new builds with advanced reactor designs. The Electric Power Research Institute (EPRI) teamed up with Department of Energy (DOE) on the Advanced Radiation Resistant Materials (ARRM) program, aiming to develop and test degradation resistant alloys from current commercial alloy specifications by 2021 to a new advanced alloy with superior degradation resistance in light water reactor (LWR)-relevant environments by 2024. Based on a comprehensive microstructure and property screening performed in Phase-1 of the ARRM program, a total of five alloys, together with 316L and X-750 as references, were down-selected for Phase-2 neutron irradiation studies. Because thermal aging could exert a synergistic effect on neutron irradiation due to the low neutron damage rate on the order of 10 –7 displacements per atom per second (dpa/s), Grade 92 (one of the five down-selected alloys) and two heats of 316L were selected in this task to study the effect of aging at 350°C for 12.5–12.7 kh on microstructure and mechanical properties. The aging time is approximately corresponding to 5 dpa neutron irradiation, which can be served as a reference for the 5-dpa-irradiated samples of the alloys to help understand the independent neutron damage influence on microstructure and mechanical properties. Optical microscopy and scanning electron microscopy were used for microstructural characterization. Hardness, tensile, Charpy impact toughness, and fracture toughness in the ductile regime of the aged samples were examined. The aging of Grade 92 led to the formation of many Laves phase in sizes of ~100–200 nm and resulted in some reduction in hardness and yield/ultimate tensile strength with some increases in uniform and total plastic elongations, which may have helped the enhancement of Charpy impact toughness, e.g., ~4 J increase in upper-shelf energy and 20.5°C reduction in ductile-brittle transition temperature compared with the unaged condition. The fracture toughness of the aged Grade 92 showed decent toughness of ~303 MPa√m (K Jq ) with ~87 tearing modulus at 22°C, which reduced to ~241 MPa√m (~20% reduction) with ~75 tearing modulus at 300°C. The two heats of 316L are differentiated by their amounts of δ-ferrite, i.e., ~1 vol% in heat T1103 and ~4 vol% in heat N5B8. The two heats of 316L were subjected to 15% cold work (CW) as this condition is often used in nuclear reactors to help trapping radiation-induced defects and thus postpone the steady state swelling stage. The aging did not result in any noticeable microstructure changes, except for possible segregations at grain boundaries that need to be further investigated. The aging resulted in slight reduction in hardness of 316L-T1103 and slight increase in hardness of 316L-N5B8, which is consistent with their tensile testing results. The 15%CW might have introduced some inhomogeneity, resulting in large standard deviations in hardness, which were reduced after the aging. The aged 316L followed the same trend as the unaged condition for the strength and elongation results from the tensile testing. Minimum elongations appeared within ~300–600°C, above which the elongations seem to increase. Unlike the negligible or minor changes in microstructure, hardness and tensile results of the two heats of 316L, their fracture toughness showed noticeable difference. The aged 316L-T1103 showed good toughness of ~350 MPa√m with ~80 tearing modulus at 22°C, which reduced to ~271 MPa√m (~23% reduction) with ~83 tearing modulus at 300°C. In contrast, the aged 316L-N5B8 showed lower toughness of ~244 MPa√m with ~53 tearing modulus at 22°C, which reduced to ~180 MPa√m (~26% reduction) with ~31 tearing modulus at 300°C. The preliminary results indicate that the presence of high volume of δ-ferrite would noticeable impair fracture toughness although it may not influence hardness and tensile properties.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Spectral Induced Polarization-Biogeochemical Relationships for Remediation Amendment Monitoring

Geophysical tools such as electrical resistivity (ER) can indirectly monitor subsurface changes in response to remedial injections. These methods exhibit relatively low spatial resolution compared to sediment core characterization but are advantageous due to the ability to collect measurements non-intrusively over time across large volumes of the subsurface. Moreover, along with confirmatory groundwater or core sampling, geophysical methods can be used during active biogeochemical remedies to monitor short-term contaminant transformations and mobility, as well as part of an overall strategy for long-term monitoring of subsurface contaminated sites. The use of alternating current spectral induced polarization (SIP) provides significantly more information than conventional geophysical methods like direct current ER. SIP allows for monitoring changes in both solution and surface conductivity by separation of real and imaginary conductivity, respectively, as well as surface capacitance. In principle, SIP can measure indicators of remedy progression such as precipitation reactions that sequester contaminants, potentially providing a better indication of amendment delivery and reactivity as compared to conventional ER methods. However, multiple processes and material properties have overlapping (interacting) electrical responses across a range of frequencies. Hence, the purpose of this scoping study was to evaluate if SIP can be used to monitor (a) amendment delivery and (b) precipitation and reactivity of amendments under consideration at Hanford. SIP measurements were collected in fully saturated columns packed with sand and Hanford formation sediments containing (a) amendments that were highly conductive with significant capacitance (zero valent iron – ZVI, sulfur modified iron – SMI) and (b) amendments that exhibited low electrical conductivity with a small capacitance (calcite, apatite, bismuth). The sand was a quartz material with homogenous particle size that exhibited a relatively low surface conductivity. It was used as a control for comparison with the sediments from the Hanford Site, which have a greater surface conductivity because of their complex mineralogy and heterogeneous particle size distribution and may have complex interactions with amendments. The amendment mass fraction was varied to represent the different stages and subsurface locations associated with the delivery of a remedy. The primary objective was to identify the solution and solid surface changes associated with the delivery amendments and their secondary reactions within the subsurface. The figure below summarizes results for the amendments tested through this project. The SIP phase shift or imaginary conductivity change for the high conductivity amendments was more than 10 times that of the low conductivity amendments, highlighting the relative ease of detection of ZVI and SMI independent of the background signal from sand or Hanford sediments. The ZVI phase shift and imaginary conductivity changes occur primarily at high frequency (> 100 Hz) whereas SMI changes were at low frequency (0.01 to 10 Hz). SIP signals of SMI also increased over time and the maximum shifted to lower frequencies. The low conductivity amendments (calcite, abiotic and biotic apatite, bismuth subnitrate) exhibited relatively small phase and imaginary conductivity changes when added to sediments. The changes were above minimum detection limits (0.5 mrad for phase shift, 0.03 µS/cm for imaginary conductivity) for the highest concentration except for the commercial bismuth material. The lowest amendment concentration that can be detected is likely sediment specific, as minerals in sediments (clays, magnetite, Fe-oxides) have some capacitance and, therefore, exhibit a variable phase shift.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Adhesion Capabilities of Permanent Foaming Fixatives

DOE-EM have identified an operational requirement for a fixative that can immobilize and/or encapsulate residual contamination in 3D void volumes (pipes, gloveboxes, waste containers, etc.) during D and D activities. Failure to safely and effectively immobilize residual contamination can: Put workers at risk; Contaminate the public and environment; Drive up costs. Commercial-off-the-shelf (COTS) polyurethane (PU) foams is one possible solution and is currently being investigated by Savannah River National Lab (SRNL). Adhesion testing will dictate how well PU foams will adhere and immobilize residual contamination onto a substrate. Results can provide a performance criteria for Section 5 of ASTM E3191: Standard Specification for Permanent Foaming Fixatives Used to Mitigate Spread of Radioactive Contamination. Initial mechanical testing showed intumescent rigid PU foams were best in class (tensile, compression, TGA/DSC) Application of intumescent rigid PU foam in pipe scenario with 'contamination' showed excellent adhesion capabilities as long as foam had contact with pipe. The foam, however, was not able to penetrate 'contamination' but created pockets where the contamination interacted with the substrate. Pretreatment options of pipe were considered to produce better immobilization capabilities. Pretreatment options included COTS products like baking spray, rubber cement, and soap. Foam was still able to immobilize on a global sense, but not a local sense. Essentially acted as a mechanical plug. A tensile tester (MTS Criterion Series 43) was utilized to evaluate the tensile adhesion strength of 6 COTS PU foams. ASTM D1623: Tensile and Tensile Adhesion Properties of Rigid Cellular Plastics. Procedures: PU foams were cured between two smooth 2'' x 2'' 304 stainless steel coupons with hinges glued on plates for gripping support. Parameters Used: Pull rate of 0.1 in/min. Calculations: Tensile adhesion strength, elongation, and ImageJ analysis of how PU foam is left on substrate. Outcome: The PU foam with the best adhesion capabilities would be downselected for further evaluation to be used as a permanent foaming fixative. The rigid PU foams had the best adhesion capabilities with the R1 foam having a max load of 236 N. One of the I-R2 samples reached almost 450 N and another sample reached 2500 N before slipping. The other intumescent foam, I-F4, had the most coverage on the stainless steel coupon's surface from the ImageJ results (61.43% surface coverage). The intumescent foam, I-R2, will be the foam of choice for future testing due its fire retardant and adhesion capabilities. Future directions: Conduct the following experiment in a pipe scenario with the down-selected PU foam. Procedures: PU foam will be cured between in a 304 stainless steel pipe (ID: 4'', OD: 4.5'', Height: 4''). Parameters Used: Compression testing results will be referenced to determine if foam's adhesion strength would be greater its compression strength as its being compressed. Calculations: Compression strength, shear stress, total time elapsed. Conduct further adhesion testing with the down-selected PU foam (I-R2) to be treated as a permanent foaming fixative (PFF). Determine the minimum contact the PFF should have with the substrate for adequate results. Evaluate if PFF's adhesion capabilities is time dependent (3.1.5 of ASTM E3911). Subject PFF to seismic stressors addressed in Safety Basis of Interim Operation documents (SBIO) to further evaluate adhesion capabilities.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗