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Investigation and modeling of the degradation of Zr-based fuel claddings during corrosion in steam and air-steam mixtures at high temperatures - 6.3 STP-2016-0033

This paper presents the main results of a study conducted to quantify and to model the degradation state of Zr-based fuel claddings submitted to severe accident conditions in a nuclear reactor core: high temperatures and either pure steam or air-steam mixture. Due to the progressive thickening of a dense and protective ZrO{sub 2} layer, the oxidation kinetics of Zr-based claddings in steam at high temperatures typical of nuclear severe accidents, is generally cubic or parabolic. However, for some temperature domains, this oxide layer may crack, becoming porous and non-protective anymore. In these 'breakaway' conditions, the oxidation kinetics change from (sub-)parabolic to linear or even accelerated. Additionally, the temperature increase can lead core materials to melt and to relocate down to the vessel lower head, threatening its integrity. If it fails, and for specific conditions, air ingress may take place into the reactor. Hence, oxygen and nitrogen both react with Zr-based claddings, successively through oxidation of Zr (forming ZrO{sub 2} layer), nitriding of Zr (forming ZrN particles) and oxidation of ZrN (forming ZrO{sub 2} and releasing nitrogen). These self-sustained chemical reactions enhance the deterioration of Zr-based claddings and of their ZrO{sub 2} layers, inducing a rise of their open porosity. To quantify this porosity, a series of two-step experiments was conducted. First, Zirlo{sup TM} cladding samples were isothermally oxidized in various conditions: in pure steam or in 50- 50 mol% air-steam mix, at several temperatures, and for different durations. The main thermal effects on reaction kinetics and the high impact of air on the cladding degradation are all confirmed by experimental results. Second, pioneering porosimetry measurements by Hg intrusion were realized for the first time on such corroded cladding samples. In both atmospheres, it is pointed out that 1200 and 1250 K lead to particularly porous oxide layers, especially due to strong 'breakaway' effects. Moreover, it is confirmed that the presence of air strongly enhances the oxide cracking: cladding samples are more porous when oxidized in the air-steam mixture than under pure steam. Finally, it is observed that in all conditions, the open porous volume fraction of Zirlo{sup TM} claddings continuously rises during their corrosion process. Hence, for each experimental condition, porosity correlations are determined through linear regressions, and porosity increase rates are deduced by derivation versus time and validated against porosimetry results of cladding samples corroded in transient (nonisothermal) conditions. (authors)

36 MATERIALS SCIENCE↗

Microbiological sampling of the spacecraft atmosphere during a simulated Skylab mission

A Skylab Air Sampler (SAS) has been developed for use during Skylab missions. The SAS was used in the Skylab Medical Experiments Altitude Test (SMEAT) to gather baseline data which could be directly compared to data obtained during actual Skylab missions. The results obtained in the SMEAT gave no evidence of consistent change in either concentration or types of microorganisms in the SMEAT atmosphere over the 56-d test. Microorganisms found included some potential pathogens but were largely normal human microflora. Few typical soil microorganisms were found. These findings are related to commonly anticipated effects of long-term spaceflights on environmental microflora and to other closed environment studies.

Brockett, R. M.↗

Examination of long-stored uranium metal

A small quantity of unirradiated uranium from Magnox fuel elements is currently held in archive storage. Some of these samples date back to the late fifties. This material has been stored, untreated, in unsealed containers in air at ambient temperature, humidity and pressure conditions. Such conditions are relevant to those that may exist in a passive storage facility. A sample of this material has been subject to optical, electron-optical and Raman spectroscopic examination to determine the extent of corrosion and the composition of corrosion product arising from long-term, low-temperature oxidation of uranium metal in air. The examinations have established that, even after a period in excess of 40 years, there was no observable spalling of uranium oxide from the sample during storage. The extent of oxidation of the metal, derived by SEM analysis, was slight and insignificant in relation to overall structural stability of the material. Raman spectroscopy data showed that the bulk of the oxide layer was comprised of hyper-stoichiometric UO{sub 2}, with U{sub 4}O{sub 9} being the dominant component. The oxygen/uranium ratio was observed to be decreased at the metal/oxide interface, with a very thin layer that consisted of mainly UO{sub 2} at the metal surface. At the oxide/air interface, a very thin U{sub 3}O{sub 8} layer was detected. U{sub 4}O{sub 9} is relatively mechanically stable, due to a significantly higher density than UO{sub 2} and U{sub 3}O{sub 8}. It is likely that the lower internal stresses in the thick U{sub 4}O{sub 9} layer have resulted in less oxide film cracking than would be expected from UO{sub 2} or U{sub 3}O{sub 8} and hence the low oxidation rate observed. These results suggest that storage of uranium metal in air over decades is a safe and credible option. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Molecular Characterization of S- and N-containing Organic Constituents in Ambient Aerosols by negative ion mode High-Resolution Nanospray Desorption Electrospray Ionization Mass Spectrometry: CalNex 2010 field study

Samples of ambient aerosols from the 2010 California Research at the Nexus of Air Quality and Climate Change (CalNex) field study were analyzed using Nanospray Desorption Electrospray Ionization High Resolution Mass Spectrometry (nano-DESI/MS). Four samples per day were collected in Bakersfield, CA on June 20-24 with a collection time of 6 hours per sample. Four characteristic groups of organic constituents were identified in the samples: compounds containing carbon, hydrogen, and oxygen only (CHO), sulfur- (CHOS), nitrogen-(CHON), and both nitrogen- and sulfur-containing organics (CHONS). Within the groups, organonitrates, organosulfates, and nitroxy organosulfates were assigned based on accurate mass measurements and elemental ratio comparisons. Changes in the chemical composition of the aerosol samples were observed throughout the day. The number of observed CHO compounds increased in the afternoon samples, suggesting regional photochemical processing as a source. The average number of CHOS compounds had the smallest changes throughout the day, consistent with a more broadly distributed source. Both of the nitrogen-containing groups (CHON and CHONS) had greater numbers of compounds in the night and morning samples, indicating that nitrate radical chemistry was likely a source for those compounds. Most of the compounds were found in submicron particles. The size distribution of CHON compounds was bimodal. We conclude that the majority of the compounds observed were secondary in nature with both biogenic and anthropogenic sources.

Environmental Molecular Sciences Laboratory↗

Absorbance and fluorometric sensing with capillary wells microplates

Detection and readout from small volume assays in microplates are a challenge. The capillary wells microplate approach [Ng et al., Appl. Phys. Lett. 93, 174105 (2008)] offers strong advantages in small liquid volume management. An adapted design is described and shown here to be able to detect, in a nonimaging manner, fluorescence and absorbance assays minus the error often associated with meniscus forming at the air-liquid interface. The presence of bubbles in liquid samples residing in microplate wells can cause inaccuracies. Pipetting errors, if not adequately managed, can result in misleading data and wrong interpretations of assay results; particularly in the context of high throughput screening. We show that the adapted design is also able to detect for bubbles and pipetting errors during actual assay runs to ensure accuracy in screening.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Airborne measurements of air pollution chemistry and transport. 1: Initial survey of major air basins in California

An instrumented aircraft has been used to study photochemical air pollution in the State of California. Simultaneous measurements of the most important chemical constituents (ozone, total oxidant, hydrocarbons, and nitrogen oxides, as well as several meteorological variables) were made. State-of-the-art measurement techniques and sampling procedures are discussed. Data from flights over the South Coast Air Basin, the San Francisco Bay Area, the San Joaquin Valley, the Santa Clara and Salinas Valleys, and the Pacific Ocean within 200 miles of the California coast are presented. Pollutants were found to be concentrated in distant layers up to at least 18,000 feet. In many of these layers, the pollutant concentrations were much higher than at ground level. These findings bring into serious question the validity of the present practice of depending solely on data from ground-based monitoring stations for predictive models.

Gloria, H. R.↗

The use of aluminum nitride to improve Aluminum-26 Accelerator Mass Spectrometry measurements and production of Radioactive Ion Beams

We present results and discuss the use of aluminum nitride as a promising source material for Accelerator Mass Spectrometry (AMS) and Radioactive Ion Beams (RIBs) science applications of 26 Al isotopes. The measurement of 26 Al in geological samples by AMS is typically conducted on Al 2 O 3 targets. However, Al 2 O 3 is not an ideal source material because it does not form a prolific beam of Al- required for measuring low-levels of 26 Al. Multiple samples of aluminum oxide (Al 2 O 3 ), aluminum nitride (AlN), mixed Al 2 O 3 –AlN as well as aluminum fluoride (AlF 3 ) were tested and compared using the ion source test facility and the stable ion beam (SIB) injector platform at the 25-MV tandem electrostatic accelerator at Oak Ridge National Laboratory. Negative ion currents of atomic and molecular aluminum were examined for each source material. It was found that pure AlN targets produced substantially higher beam currents than the other materials and that there was some dependence on the exposure of AlN to air. The applicability of using AlN as a source material for geological samples was explored by preparing quartz samples as Al 2 O 3 and converting them to AlN using a carbothermal reduction technique, which involved reducing the Al 2 O 3 with graphite powder at 1600 °C within a nitrogen atmosphere. The quartz material was successfully converted to AlN. Thus far, AlN proves to be a promising source material and could lead towards increasing the sensitivity of low-level 26 Al AMS measurements. The potential of using AlN as a source material for nuclear physics is also very promising by placing 26 AlN directly into a source to produce more intense radioactive beams of 26 Al.

Janzen, Meghan S.↗

Micro arc oxidation of aluminum for nuclear applications

Dry cask storage and transport of used (spent) nuclear fuel rely upon the basket and shell of the cask to transfer the decay heat from the fuel assemblies. Cask licensees have considered the use of light metal (aluminum) oxidation to enhance the emissivity of aluminum alloy or aluminum based Metal Matrix Composites (MMC) used in the cask basket. However, traditional anodization techniques suffer from issues that make fabrication and regulatory acceptance problematic. The Micro Arc Oxidation (MAO) technology overcomes the problems associated with traditional anodization in the production of consistent, uniform and reliable high emissivity coatings of aluminum alloys. Samples of AA 2219 and an aluminum-based MMC were treated using a proprietary MAO process and subjected to a number of tests to confirm suitability of the coated material. The treated material was inspected using macro photography and Scanning Electron Microscopy (SEM). A consistent, uniform black, porous surface with a typical surface roughness of Ra = 7-8 μm was observed. Emissivity of treated surfaces with thicknesses ranging from 24 microns to 40 microns was measured using an integrating sphere. In all cases, the emissivity coefficient at room temperature in the ranges of 400 to 700 nanometers and 1000 to 1650 nanometers was above 0.8, reaching 0.94 depending on the thickness. The MAO process yield was tested by coating 400 spent fuel basket components to ensure a minimum specified thickness. 97% of the tested points met or exceeded the minimum thickness required. The defect density was very low and 100% of the components met the quality assurance criteria. In-service surface performance was tested by exposing the treated surface to a number of high temperature environments (air, vacuum, nitrogen) and thermal cycling in air. In all cases, the surface remained unchanged. Test samples were exposed to 90 Celsius degrees borated and demineralized water for 48 hours with no change to the sample treated surface. Finally, tests sample were exposed to 60 C. degrees borated water for 168 hours with no change to the sample treated surface. MAO technology appears to be a viable method to provide consistent, durable, and high emissivity coatings, that can be used in the fabrication and licensing of dry storage/transportation casks.

36 MATERIALS SCIENCE↗

Handling and Properties of Methanol as a Marine Fuel

Given the increasing concern around greenhouse gas emissions and the decline in the availability of fossil fuels, there is increasing global demand to develop alternate fuels for maritime transportation that are sustainable and which have lower greenhouse gas emissions. Methanol is one such alternative fuel that has garnered considerable attention given its potential to be produced by more sustainable processes and its more favorable greenhouse gas emission profile in comparison with current fossil fuels. Understanding the physical and chemical properties of methanol under a range of conditions is essential for its development as a marine fuel. In this study, we seek to define physical and chemical properties of different methanol samples to simulate real-world storage conditions as these data are lacking in the literature. Several methanol samples were evaluated: nearly pure methanol; International Organization for Standardization (ISO) marine methanol (MM) grades A, B, and C; and methanol plus higher alcohols. We first evaluated all methanol samples for impurities, acetic acid content, density, and distillation range. We then characterized the effects of water absorption and found that methanol can easily absorb unacceptable water content from humid air within hours, necessitating storage conditions that prevent this process. In eight-week aging experiments at 20 °C and 40 °C in ambient air, we did not observe significant oxidation for any of the methanol samples; however, we did observe increases in acid number. We assessed the impact of contamination of methanol with water, marine gas oil (MGO), and an MGO–biodiesel mixture on density, viscosity, distillation range, and lubricity. Finally, we show that MGO contamination of methanol results in a slight increase in sooting tendency. In aggregate, our results provide an in-depth analysis of physical and chemical properties of methanol as well as the impacts of storage conditions and impurities on the properties of fuel methanol.

09 BIOMASS FUELS↗

Phase state of ambient aerosol linked with water uptake and chemical aging in the southeastern US

During the summer 2013 Southern Aerosol and Oxidant Study (SOAS) field campaign in a rural site in the southeastern United States, the effect of hygroscopicity and composition on the phase state of atmospheric aerosol particles dominated by the organic fraction was studied. The analysis is based on hygroscopicity measurements by a Hygroscopic Tandem Differential Mobility Analyzer (HTDMA), physical phase state investigations by an Aerosol Bounce Instrument (ABI) and composition measurements using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). To study the effect of atmospheric aging on these properties, an OH-radical oxidation flow reactor (OFR) was used to simulate longer atmospheric aging times of up to 3 weeks. Hygroscopicity and bounce behavior of the particles had a clear relationship showing higher bounce at elevated relative humidity (RH) values for less hygroscopic particles, which agrees well with earlier laboratory studies. Additional OH oxidation of the aerosol particles in the OFR increased the O:C and the hygroscopicity resulting in liquefying of the particles at lower RH values. At the highest OH exposures, the inorganic fraction starts to dominate the bounce process due to production of inorganics and concurrent loss of organics in the OFR. Our results indicate that at typical ambient RH and temperature, organic-dominated particles stay mostly liquid in the atmospheric conditions in the southeastern US, but they often turn semisolid when dried below ~50 % RH in the sampling inlets. Furthermore, while the liquid phase state suggests solution behavior and equilibrium partitioning for the SOA particles in ambient air, the possible phase change in the drying process highlights the importance of thoroughly considered sampling techniques of SOA particles.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Evaluation of three portable samplers for monitoring airborne fungi

Airborne fungi were monitored at five sample sites with the Burkard portable, the RCS Plus, and the SAS Super 90 air samplers; the Andersen 2-stage impactor was used for comparison. All samplers were calibrated before being used simultaneously to collect 100-liter samples at each site. The Andersen and Burkard samplers retrieved equivalent volumes of airborne fungi; the SAS Super 90 and RCS Plus measurements did not differ from each other but were significantly lower than those obtained with the Andersen or Burkard samplers. Total fungal counts correlated linearly with Cladosporium and Penicillium counts. Alternaria species, although present at all sites, did not correlate with total count or with amounts of any other fungal genera. Sampler and location significantly influenced fungal counts, but no interactions between samplers and locations were found.

NASA Center JSC↗

Monitoring Trace Contaminants in Air Via Ion Trap Mass Spectrometry

Recent passage of the Clean Air Act with its stricter regulation of toxic gas emissions, and the ever-growing number of applications which require faster turnaround times between sampling and analysis are two major factors which are helping to drive the development of new instrument technologies for in-situ, on-line, real-time monitoring. The ion trap, with its small size, excellent sensitivity, and tandem mass spectrometry capability is a rapidly evolving technology which is well-suited for these applications. In this paper, we describe the use of a commercial ion trap instrument for monitoring trace levels of chlorofluorocarbons (CFCs) and volatile organic compounds (VOCs) in air. A number of sample introduction devices including a direct transfer line interface, short column GC, and a cryotrapping interface are employed to achieve increasing levels of sensitivity. MS, MS/MS, and MS/MS/MS methods are compared to illustrate trade-offs between sensitivity and selectivity. Filtered Noise Field (FNF) technology is found to be an excellent means for achieving lower detection limits through selective storage of the ion(s) of interest during ionization. Figures of merit including typical sample sizes, detection limits, and response times are provided. The results indicate the potential of these techniques for atmospheric assessments, the High Speed Research Program, and advanced life support monitoring applications for NASA.

Palmer, Peter T.↗

In Situ Observations and Sampling of Volcanic Emissions with Unmanned Aircraft: A NASA/UCR Case Study at Turrialba Volcano, Costa Rica

Burgeoning new technology in the design and development of robotic aircraft-unmanned aerial vehicles (UAVs)-presents unprecedented opportunities for the volcanology community to observe, measure, and sample eruption plumes and drifting volcanic clouds in situ. While manned aircraft can sample dilute parts of such emissions, demonstrated hazards to air breathing, and most particularly turbine, engines preclude penetration of the zones of highest ash concentrations. Such areas within plumes are often of highest interest with respect to boundary conditions of applicable mass-loading retrieval models, as well as Lagrangian, Eulerian, and hybrid transport models used by hazard responders to predict plume trajectories, particularly in the context of airborne hazards. Before the 2010 Ejyafyallajokull eruption in Iceland, ICAO zero-ash-tolerance rules were typically followed, particularly for relatively uncrowded Pacific Rim airspace, and over North and South America, where often diversion of aircraft around ash plumes and clouds was practical. The 2010 eruption in Iceland radically changed the paradigm, in that critical airspace over continental Europe and the United Kingdom were summarily shut by local civil aviation authorities and EURO CONTROL. A strong desire emerged for better real-time knowledge of ash cloud characteristics, particularly ash concentrations, and especially for validation of orbital multispectral imaging. UAV platforms appear to provide a viable adjunct, if not a primary source, of such in situ data for volcanic plumes and drifting volcanic clouds from explosive eruptions, with prompt and comprehensive application to aviation safety and to the basic science of volcanology. Current work is underway in Costa Rica at Turrialba volcano by the authors, with the goal of developing and testing new small, economical UAV platforms, with miniaturized instrument payloads, within a volcanic plume. We are underway with bi-monthly deployments of tethered SO2-sondes and are in the planning stages for the deployment of the SIERRA UAV to our site in March 2013. We will be conducting in situ observations simultaneously with ASTER orbital multispectral TIR data acquisitions, in order to compare in situ measurements with estimates of SO2 mass loading and dispersion derived from ASTER data. Though small UAVs are now being considered for use in active volcanic areas for in situ sampling of emissions (e.g., efforts by our group, and by our colleagues at the INGV in Italy and the Applied Science University in Dusseldorf, Germany, and others in the United Kingdom and Iceland), and also for remote sensing, much more needs to be done in the way of instrument development, and in developing small UAVs for both low altitude (tropospheric) and high altitude (stratospheric) applications. In particular, the development of all weather and day/night operational flight capabilities in close proximity to hazardous topography is crucial to a truly responsive volcano in situ measurement system. Finally, it is imperative that national civil aviation authorities recognize the unique benefits of such platforms. It is important that authorities understand that severely restricting or not deploying such tools in airspace over restless volcanoes or within eruption plumes, ostensibly because of the perceived (small) risk that such unmanned aircraft pose to manned air operations, itself poses a bigger transcendental risk to proximal populations and particularly to the aviation community, itself.

Volcanic Ash Advisory Centers (VAACs)↗

Investigating Commercial Off-The-Shelf (COTS) Glovebox and Support Components Compared to Custom Curatorial Laboratories

There is a need envisioned to investigate the application of commercial off-the-shelf (COTS) systems as tools that could be used within commercial preliminary curation as the expected space economy is supported and begins to take flight. NASA is involved with supporting and developing the space economy [1] and therefore it’s feasible that at some point, a commercial space company would bring back materials and either store initially, or permanently, within COTS equipment as a stand-in for custom curation laboratories. While utilizing opportunities to explore this capability at NASA-Johnson Space Center (JSC) during the establishment of other laboratories [2] it was realized that cleanliness and/or other properties could be evaluated for these COTS systems during their installation in advanced research facilities that are not ISO-class rated clean rooms. Several aspects of a COTS-Curation system were explored including various gloves for curation manipulation within a negative pressure glovebox (Fig.1), Balazs organic and inorganic contaminant levels testing prior to glovebox ever being used, mode swapping comparison of recirculation vs. single pass, constant monitoring of oxygen (O2) and moisture (H2O) levels in various conditions, etc. To acquire inorganic and organic compound loads inside the glovebox, Balazs wafer testing and gas sampling were implemented. These are standardized analytical tests provided by Balazs™ NanoAnalysis, a division of Air Liquide USA. Deployment of 8-inch silicon wafer witness plates for 24-hours in an undisturbed environment capture the organic compound load and inorganic trace metal contents which can be obtained by Vapor Phase Decomposition Inductively Coupled Plasma Mass Spectrometry (VPD ICP-MS). Balazs gas sample analysis was also performed for better measurements of volatile organic compounds (VOC) in glovebox air analyzed by Thermal Desorption Gas Chromatography Mass Spectrometry (TD GC-MS). These analytical testings were carried out in a controlled ultra high pure (UHP) gaseous nitrogen (N2)-purged environment where oxygen and moisture contents were continuously monitored at certain temperature and pressure. The preliminary outcomes of these testings are promising. The COTS systems appear to maintain the steady-state controlled environment for days, if not weeks, with uninterrupted gaseous N2-supply which was operated from a standard medium pressure LN2 250L 230L dewar, exchanged as needed. The outgassing load can be maintained by selecting the glove materials that have the least outgassing and particle shedding performances. Further experiments will be considered to validate the preliminary findings. While this project is exploratory, it is not intended as an endorsement by NASA Curation for approved materials or usage for advanced curatorial activities. NASA does not endorse nor promote any one particular product or company. References: [1] McCubbin F. M. et al. (2019) Space Science Reviews 215:A48. [2] Lewis, E.K. et. al (2024) LPSC LV, Abstract #2457.

Curation↗

Federal Radiological Monitoring and Assessment Center Monitoring Manual Volume 1, Operations

The Monitoring division is primarily responsible for the coordination and direction of: Aerial measurements to delineate the footprint of radioactive contaminants that have been released into the environment. Monitoring of radiation levels in the environment; Sampling to determine the extent of contaminant deposition in soil, water, air and on vegetation; Preliminary field analyses to quantify soil concentrations or depositions; and Environmental and personal dosimetry for FRMAC field personnel, during a Consequence Management Response Team (CMRT) and Federal Radiological Monitoring and Assessment Center (FRMAC) response. Monitoring and sampling techniques used during CM/FRMAC operations are specifically selected for use during radiological emergencies where large numbers of measurements and samples must be acquired, analyzed, and interpreted in the shortest amount of time possible. In addition, techniques and procedures are flexible so that they can be used during a variety of different scenarios; e.g., accidents involving releases from nuclear reactors, contamination by nuclear waste, nuclear weapon accidents, space vehicle reentries, or contamination from a radiological dispersal device. The Monitoring division also provides technicians to support specific Health and Safety Division activities including: The operation of the Hotline; FRMAC facility surveys; Assistance with Health and Safety at Check Points; and Assistance at population assembly areas which require support from the FRMAC. This volume covers deployment activities, initial FRMAC activities, development and implementation of the monitoring and assessment plan, the briefing of field teams, and the transfer of FRMAC to the EPA.

61 RADIATION PROTECTION AND DOSIMETRY↗

Implementation of a DOD ELAP Conforming Quality System at a FUSRAP Site Field Temporary Radiological Screening Laboratory - 13500

A case study is presented on specific program elements that supported the transition of a temporary field radiological screening lab to an accredited operation capable of meeting client quality objectives for definitive results data. The temporary field lab is located at the Formerly Utilized Sites Remedial Action Program Linde Site in Tonawanda, NY. The site is undergoing remediation under the direction of the United States Army Corps of Engineers - Buffalo District, with Cabrera Services Inc. as the remediation contractor and operator of the on-site lab. Analysis methods employed in the on-site lab include gross counting of alpha and beta particle activity on swipes and air filters and gamma spectroscopy of soils and other solid samples. A discussion of key program elements and lessons learned may help other organizations considering pursuit of accreditation for on-site screening laboratories. (authors)

54 ENVIRONMENTAL SCIENCES↗