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On the origin of resistive switching volatility in Ni/TiO{sub 2}/Ni stacks

Resistive switching and resistive random access memories have attracted huge interest for next generation nonvolatile memory applications, also thought to be able to overcome flash memories limitations when arranged in crossbar arrays. A cornerstone of their potential success is that the toggling between two distinct resistance states, usually a High Resistive State (HRS) and a Low Resistive State (LRS), is an intrinsic non-volatile phenomenon with the two states being thermodynamically stable. TiO{sub 2} is one of the most common materials known to support non-volatile RS. In this paper, we report a volatile resistive switching in a titanium dioxide thin film sandwiched by two nickel electrodes. The aim of this work is to understand the underlying physical mechanism that triggers the volatile effect, which is ascribed to the presence of a NiO layer at the bottom interface. The NiO layer alters the equilibrium between electric field driven filament formation and thermal enhanced ion diffusion, resulting in the volatile behaviour. Although the volatility is not ideal for non-volatile memory applications, it shows merit for access devices in crossbar arrays due to its high LRS/HRS ratio, which are also briefly discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Biochemical basis for the formation of organ-specific volatile blends in mint

Above-ground material of members of the mint family is commercially distilled to extract essential oils, which are then formulated into a myriad of consumer products. Most of the research aimed at characterizing the processes involved in the formation of terpenoid oil constituents has focused on leaves. We now demonstrate, by investigating three mint species, peppermint ( Mentha ˣ piperita L.), spearmint ( Mentha spicata L.) and horsemint ( Mentha longifolia (L.) Huds.; accessions CMEN 585 and CMEN 584), that other organs – namely stems, rhizomes and roots – also emit volatiles and that the terpenoid volatile composition of these organs can vary substantially from that of leaves, supporting the notion that substantial, currently underappreciated, chemical diversity exists. Differences in volatile quantities released by plants whose roots had been dipped in a Verticillium dahliae -spore suspension (experimental) or dipped in water (controls) were evident: increases of some volatiles in the root headspace of mint species that are susceptible to Verticillium wilt disease (peppermint and M. longifolia CMEN 584) were detected, while the quantities of certain volatiles decreased in rhizomes of species that show resistance to the disease (spearmint and M. longifolia CMEN 585). To address the genetic and biochemical basis underlying chemical diversity, we took advantage of the newly sequenced M. longifolia CMEN 585 genome to identify candidate genes putatively coding for monoterpene synthases (MTSs), the enzymes that catalyze the first committed step in the biosynthesis of monoterpenoid volatiles. The functions of these genes were established by heterologous expression in Escherichia coli , purification of the corresponding recombinant proteins, and enzyme assays, thereby establishing the existence of MTSs with activities to convert a common substrate, geranyl diphosphate, to (+)-α-terpineol, 1,8-cineole, γ-terpinene, and (–)-bornyl diphosphate, but were not active with other potential substrates. In conjunction with previously described MTSs that catalyze the formation of (–)-β-pinene and (–)-limonene, the product profiles of the MTSs identified here can explain the generation of all major monoterpene skeletons represented in the volatiles released by different mint organs.

59 BASIC BIOLOGICAL SCIENCES↗

Real-Time Science Operations to Support a Lunar Polar Volatiles Rover Mission

Future human exploration of the Moon will likely rely on in situ resource utilization (ISRU) to enable long duration lunar missions. Prior to utilizing ISRU on the Moon, the natural resources (in this case lunar volatiles) must be identified and characterized, and ISRU demonstrated on the lunar surface. To enable future uses of ISRU, NASA and the CSA are developing a lunar rover payload that can (1) locate near subsurface volatiles, (2) excavate and analyze samples of the volatile-bearing regolith, and (3) demonstrate the form, extractability and usefulness of the materials. Such investigations are important both for ISRU purposes and for understanding the scientific nature of these intriguing lunar volatile deposits. Temperature models and orbital data suggest near surface volatile concentrations may exist at briefly lit lunar polar locations outside persistently shadowed regions. A lunar rover could be remotely operated at some of these locations for the approx. 2-14 days of expected sunlight at relatively low cost. Due to the limited operational time available, both science and rover operations decisions must be made in real time, requiring immediate situational awareness, data analysis, and decision support tools. Given these constraints, such a mission requires a new concept of operations. In this paper we outline the results and lessons learned from an analog field campaign in July 2012 which tested operations for a lunar polar rover concept. A rover was operated in the analog environment of Hawaii by an off-site Flight Control Center, a rover navigation center in Canada, a Science Backroom at NASA Ames Research Center in California, and support teams at NASA Johnson Space Center in Texas and NASA Kennedy Space Center in Florida. We find that this type of mission requires highly efficient, real time, remotely operated rover operations to enable low cost, scientifically relevant exploration of the distribution and nature of lunar polar volatiles. The field demonstration illustrated the need for science operations personnel in constant communications with the flight mission operators and the Science Backroom to provide immediate and continual science support and validation throughout the mission. Specific data analysis tools are also required to enable immediate data monitoring, visualization, and decision making. The field campaign demonstrated that this novel methodology of real-time science operations is possible and applicable to providing important new insights regarding lunar polar volatiles for both science and exploration.

Moon; Volatiles; Rover; Missions↗

Volatile Abundance of Paired Lunar Troctolites and the Early Lunar Crust

Nominally anhydrous minerals (NAMs) such as plagioclase, pyroxene, and olivine can contain small amounts of water and other volatile elements, typically within crystal lattice defects. Given the volumetric abundance of NAMs, these minerals can contain a significant volatile reservoir despite their low abundances. At least one NAM is present in nearly all lunar rocks, unlike the more commonly studied volatile-bearing mineral apatite, making NAM-based hygrometry more widely applicable. NAMs are also not subject to enrichment in H due to self-fractionation of F, as is the case for apatite. Recent developments in secondary ion mass spectrometry (SIMS) techniques (e.g., the reduction of analytical background) have allowed the evaluation of volatiles in samples that were previously too low in abundance to measure. The ability to make volatile measurements in the sub-10 ppm range opens up a suite of samples where volatile-bearing phases, such as melt inclusions and apatite, are rare or entirely absent. In this study we measure the abundances of H, C, F, P, S, and Cl in plagioclase from two paired lunar troctolites to better understand the volatile inventory of the early lunar crust and its implications for the bulk Moon.

volatiles↗

The Effect of Glass Chemistry on Caesium Volatility in Iron Phosphate Glass Systems - 19344

The UK currently has a stockpile of 99,000 m{sup 3} of intermediate level waste (ILW), with this figure expected to rise to 191,000 m{sup 3} by 2125. Current immobilisation options include cementation and thermal treatment, with cementation being the preferred candidate due to the simplicity of processing. However, thermal processing such as vitrification could offer significant volume reductions, up to 75 % for some waste-streams. In comparison, cementation is generally associated with a volume increase, with a typical waste package seeing a volume increase of 200 - 400 %. For vitrification to be accepted as the preferred treatment option of ILW in the UK, the issue of volatility during the vitrification process must be addressed. Volatile components of ILW such as Cs-137 and Sr-90 account for almost 50 % of the current total radioactivity produced by the UK's ILW stockpile. Therefore, the efficient retention of these elements into the glass immobilisation medium must be considered. Various approaches can be employed when trying to increase volatile retention, however this project has focussed on the influence of glass chemistry on volatility. A series of iron phosphate glasses containing 5 mol % of B{sub 2}O{sub 3}, MnO and ZnO have been produced, where additives have been substituted in place of Fe{sub 2}O{sub 3} in a standard 40Fe{sub 2}O{sub 3}-60P{sub 2}O{sub 5} system. All glass samples were characterised using Raman spectroscopy, SEM-EDX, thermal analysis, XRD and XRF. The glasses were then doped with caesium carbonate and re-melted in the system described below. A simple off-gas system has been developed and commissioned to capture and characterise volatiles released from the glass during melting. The off-gas system has been refined several times, with the most recent design comprising of a sealed stainless steel system, connected to two gas washing bottles containing 150 ml of 50 % nitric acid. Nitrogen gas is passed through the system for the duration of the experiment at a flow rate of ∼ 0.9 L/min to ensure efficient carryover of the volatiles released from the glass melt into the solutions in the gas washing bottles. The total retention of the volatiles can be measuring by analysing the contents of the gas washing bottles using ICP-MS and XRF of the final glass product. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Volatility characterization of nanoparticles from single and dual-fuel low temperature combustion in compression ignition engines

Our work explores the volatility of particles produced from two diesel low temperature combustion (LTC) modes proposed for high-efficiency compression ignition engines. It also explores mechanisms of particulate formation and growth upon dilution in the near-tailpipe environment. Moreover, the number distribution of exhaust particles from low- and mid-load dual-fuel reactivity controlled compression ignition (RCCI) and single-fuel premixed charge compression ignition (PPCI) modes were experimentally studied over a gradient of dilution temperature. Particle volatility of select particle diameters was investigated using volatility tandem differential mobility analysis (V-TDMA). Evaporation rates for exhaust particles were compared with V-TDMA results for candidate pure n-alkanes to identify species with similar volatility characteristics. The results show that LTC particles are mostly comprised of material with volatility similar to engine oil alkanes. V-TDMA results were used as inputs to an aerosol condensation and evaporation model to support the finding that smaller particles in the distribution are comprised of lower volatility material than large particles under primary dilution conditions. Although the results show that saturation levels are high enough to drive condensation of alkanes onto existing particles under the dilution conditions investigated, they are not high We conclude that observed particles from LTC operation must grow from low concentrations of highly non-volatile compounds present in the exhaust.

33 ADVANCED PROPULSION SYSTEMS↗

Bacterial volatile organic compound specialists in the phycosphere

Abstract Labile dissolved organic carbon in the surface oceans accounts for about one-fourth of carbon produced through photosynthesis and turns over on average every 3 days, fueling one of the largest engines of microbial heterotrophic production on the planet. Volatile organic compounds are poorly constrained components of dissolved organic carbon. Here, we detected 72 m/z signals, corresponding to unique volatile organic compounds, including petroleum hydrocarbons, totaling ~18.5 nM in the culture medium of a model diatom. In five cocultures with bacteria adapted to grow with this diatom, 1–59 m/z signals were depleted. Two of the most active volatile organic compound consumers, Marinobacter and Roseibium, contained more genes encoding volatile organic compound oxidation proteins, and attached to the diatom, suggesting volatile organic compound specialism. With nanoscale secondary ion mass spectrometry and stable isotope labeling, we confirmed that Marinobacter incorporated carbon from benzene, one of the depleted m/z signals detected in the co-culture. Diatom gross carbon production increased by up to 29% in the presence of volatile organic compound consumers, indicating that volatile organic compound consumption by heterotrophic bacteria in the phycosphere—a region of rapid organic carbon oxidation that surrounds phytoplankton cells—could impact global rates of gross primary production.

Environmental Sciences & Ecology↗

Space exploration and the history of solar-system volatiles

The thermochemical history of volatile substances in all solar-system planets, satellites, and planetoids is discussed extensively. The volatiles are viewed as an interface between the abiotic and biotic worlds and as a key to the history of bodies of the solar system. A flowsheet of processes and states is exhibited. Differences in bulk volatiles distribution between the planetary bodies and between the interior, surface, and atmosphere of each body are considered, as well as sinks for volatiles in degassing. The volatiles-rich Jovian and Saturnian satellites, the effect of large-planet magnetosphere sweeps on nearby satellites, volatiles of asteroids and comets, and the crucial importance of seismic, gravity, and libration data are treated. A research program encompassing analysis of the elemental and isotopic composition of rare gas in atmospheres, assay of volatiles-containing phases in regoliths, and examination of present or past atmospheric escape/accretion processes is recommended.

Fanale, F. P.↗

Martian impact crater ejecta morphologies and their potential as indicators of subsurface volatile distribution

Many martian impact craters ejecta morphologies suggestive of fluidization during ejecta emplacement. Impact into subsurface volatile reserviors (i.e., water, ice, CO2, etc.) is the mechanism favored by many scientists, although acceptance of this mechanism is not unanimous. In recent years, a number of studies were undertaken to better understand possible relationships between ejecta morphology and latitude, longitude, crater diameter, and terrain. These results suggest that subsurface volatiles do influence the formation of specific ejecta morphologies and may provide clues to the vertical and horizontal distribution of volatiles in more localized regions of Mars. The location of these volatile reservoirs will be important to humans exploring and settling Mars in the future. Qualitative descriptions of ejecta morphology and quantitative analyses of ejecta sinuosity and ejecta lobe areal extent from the basis of the studies. Ejecta morphology studies indicate that morphology is correlated with crater diameter and latitude, and, using depth-diameter relationships, these correlations strongly suggest that changes in morphology are related to transition among subsurface layers with varying amounts of volatiles. Ejecta sinuosity studies reveal correlations between degree of sinuosity (lobateness) and crater morphology, diameter, latitude, and terrain. Lobateness, together with variations in areal extent of the lobate ejecta blanket with morphology and latitude, probably depends most directly on the ejecta emplacement process. The physical parameters measured here can be compared with those predicted by existing ejecta emplacement models. Some of these parameters are best reproduced by models requiring incorporation of volatiles within the ejecta. However, inconsistencies between other parameters and the models indicate that more detailed modeling is necessary before the location of volatile reservoirs can be confidently predicted based on ejecta morphology studies alone.

Barlow, Nadine G.↗

Feasibility and Definition of a Lunar Polar Volatiles Prospecting Mission

The recent Lunar Crater Observing and Sensing Satellite (LCROSS) mission has provided evidence for significant amounts of cold trapped volatiles in Cabeus crater near the Moon's south pole. Moreover, LRO/Diviner measurements of extremely cold lunar polar surface temperatures imply that volatiles can be stable outside or areas of strict permanent shadows. These discoveries suggest that orbital neutron spectrometer data point to extensive deposits at both lunar poles. The physical state, composition and distribution of these volatiles are key scientific issues that relate to source and emplacement mechanisms. These issues are also important for enabling lunar in situ resource utilization (ISRU). An assessment of the feasibility of cold-trapped volatile ISRU requires a priori information regarding the location, form, quantity, and potential for extraction of available resources. A robotic mission to a mostly shadowed but briefly .unlit location with suitable environmental conditions (e.g. short periods of oblique sunlight and subsurface cryogenic temperatures which permit volatile trapping) can help answer these scientific and exploration questions. Key parameters must be defined in order to identify suitable landing sites, plan surface operations, and achieve mission success. To address this need, we have conducted an initial study for a lunar polar volatile prospecting mission, assuming the use of a solar-powered robotic lander and rover. Here we present the mission concept, goals and objectives, and landing site selection analysis for a short-duration, landed, solar-powered mission to a potential hydrogen volatile-rich site.

Heldmann, Jennifer↗

Regolith Volatile Characterization (RVC) in RESOLVE

Resource investigation in the lunar poles is of importance to the potential impact of in-situ resource utilization (ISRU). The RESOLVE project developed a payload to investigate the permanently shadowed areas of the lunar poles and demonstrate ISRU technology. As a part of the RESOLVE project, the regolith volatile characterization (RVC) subsystem was designed to examine the release of volatiles from sample cores. The test sample was heated in the reactor to release the volatiles where they were analyzed with gas chromatography. Subsequently, the volatile sample was introduced into the lunar water resource demonstration (LWRD) subsystem where the released hydrogen and water were selectively captured. The objective of the Regolith Volatile Characterization (RVC) subsystem was to heat the crushed core sample and determine the desorption of volatile species of interest. The RVC subsystem encompasses the reactor and the system for volatile analysis. The system was designed to analyze H2, He, CO, CO2, N2, 02, CH4, H2S and H2O. The GC chosen for this work is a Siemens MicroSAM process GC with 3 columns and 8 TCD detectors. Neon was chosen as the carrier gas to enhance the analysis of hydrogen and helium.The limit of detection for the gases is approx.1000ppm for H2, CO. CO2 , N2, O2 and H2 S. The limit of detection for CH4 is approx.4000ppm and the water limit of detection is -10000 ppm with a sample analysis time of 2-3 minutes. These values (with the exception of water and H2S) were determined by dilution of a six gas mixture from Scott Gas (5% CO2, CO, O2, N2, 4% CH4 and H2) using mass flow controllers (MFC5). Water was calibrated at low levels using an in house relative humidity (RH) generator. H 2S and high concentrations of H2 were calibrated by diluting a pure stream of gas with MFCs. Higher concentrations of N2 and 02 were calibrated using Air again diluting with MFCs. There were three modification goals for the GC in EBU2 that would allow this process GC to be used in the field demo for RESOLVE. The first modification was to decrease the weight associated with the GC, this included eliminating the explosion proof case (Figure 1) and replacing it with a lightweight case as well as using an on board COPV tank for the neon carrier gas. The next goal was to add a second oven for the molecular sieve column to allow for dual temperature control during GC operation; the separation of hydrogen and helium is optimum at lower temperatures while the water analysis required higher temperatures creating a competing design requirement. The second oven also allows a lower limit of detection for water quantification and avoids the possibility of water condensing in the GC which could ruin the column characteristics. The final goal was to modify the column arrangement to optimize the system for our specific application. Figure 2 shows the internal details of the module optimized optimized for our field application. The modifications and performance of the gas analysis system will be discussed in detail.

Captain, Janine↗

An Overview of the Volatiles Investigating Polar Exploration Rover (VIPER) Mission

A critical goal to both science and exploration is to understand the form and location of lunar polar volatiles. The lateral and vertical distributions of these volatiles inform us of the processes that control the emplacement and retention of these volatiles, as well as helping to formulate in-situ resource utilization (ISRU) architectures. While significant progress has been made from orbital observations, measurements at a range of scales from centimeters to kilometers across the lunar surface are needed to generate adequate "volatile mineral models" for use in evaluating the resource potential of volatiles at the Moon. VIPER is a solar and battery powered rover mission designed to operate over multiple lunar days, traversing several kilometers as it continuously monitors for subsurface hydrogen and other surface volatiles. In specific thermal terrain types, including permanently shadowed terrain and locales that permit near-surface ice stability, subsurface samples will be examined for volatile content using a one-meter drill. This talk will provide an overview of the VIPER mission which is scheduled for flight to the Lunar South Pole in December 2022.

Colaprete, Anthony↗

Comparing the Volatile Contents of Basaltic Rocks Through the Inner Solar System

Volatiles in planetary interiors play important roles in magma genesis, crust formation, eruption style, and even habitability of planetary surfaces. Allan Treiman’s career has touched on volatiles in the Moon, Mars, HED-parent body, the Earth, Venus, and other planetary bodies through studies of igneous rocks, volatile-bearing igneous minerals within these rocks, and the secondary alteration products produced from these rocks and minerals. His seminal work in many of these fields has inspired our careers and many others in our field. Here, we will build on and summarize what we know of the volatile content of basaltic rocks in the inner solar system. Specifically, this talk will focus on using volatile-bearing minerals (amphibole and apatite) along with bulk compositions to constrain the pre-eruptive, and potentially predegassed, volatile content of the magma and their source regions. We will then use these estimates to compare the volatile content of the Earth, Moon, Mars, Venus, and Mercury and what open questions there are for each planetary body.

Justin Filiberto↗

Volatile species of technetium and rhenium during waste vitrification

Volatile loss of technetium (Tc) during vitrification of low-activity wastes is a technical challenge for treating and immobilizing the large volumes of radioactive and hazardous wastes stored at the U.S. Department of Energy's Hanford Site. There are various research efforts being pursued to develop technologies that can be implemented for cost effective management of Tc, including studies to understand the behavior of Tc during vitrification, with the goal of eventually increasing Tc retention in glass. Furthermore, one of these studies has focused on identifying the form or species of Tc and Re (surrogate for Tc) that evolve during the waste-to-glass conversion process. This information is important for understanding the mechanism of Tc volatilization. In this paper, available information collected from the literature is critically evaluated to clarify the volatile species of Tc and Re and, more specifically, whether they volatilize as alkali pertechnetate and perrhenate or as technetium and rhenium oxides after decomposition of alkali pertechnetate and perrhenate. The evaluated data ranged from mass spectrometric identification of species volatilized from pure and binary alkali pertechnetate and perrhenate salts to structural and chemical analyses of volatilized materials during crucible melting and scaled melter processing of simulated wastes.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Estimation of stochastic volatility with long memory for index prices of FTSE Bursa Malaysia KLCI

In recent years, modeling in long memory properties or fractionally integrated processes in stochastic volatility has been applied in the financial time series. A time series with structural breaks can generate a strong persistence in the autocorrelation function, which is an observed behaviour of a long memory process. This paper considers the structural break of data in order to determine true long memory time series data. Unlike usual short memory models for log volatility, the fractional Ornstein-Uhlenbeck process is neither a Markovian process nor can it be easily transformed into a Markovian process. This makes the likelihood evaluation and parameter estimation for the long memory stochastic volatility (LMSV) model challenging tasks. The drift and volatility parameters of the fractional Ornstein-Unlenbeck model are estimated separately using the least square estimator (lse) and quadratic generalized variations (qgv) method respectively. Finally, the empirical distribution of unobserved volatility is estimated using the particle filtering with sequential important sampling-resampling (SIR) method. The mean square error (MSE) between the estimated and empirical volatility indicates that the performance of the model towards the index prices of FTSE Bursa Malaysia KLCI is fairly well.

97 MATHEMATICS AND COMPUTING↗

Electrically-driven IMT and volatile memristor behavior in NdNiO 3 films

Abstract Transition metal oxides with insulator-metal transitions (IMTs) are uniquely suited for volatile memristor devices that mimic the spiking of biological neurons. Unlike most non-volatile memristors, which often operate via ion migration into filaments, volatile devices utilize a reversible phase change that returns to a ground state in the absence of applied stimulus. In these devices, Joule heating triggers the IMT and changes the bulk resistivity rather than influencing conduction through defects, as in previous studies. This volatile resistive switching behavior has previous been leveraged in niobium and vanadium oxides, but not in rare-earth nickelates, despite their tunable transition temperatures. This study demonstrates an electrically driven IMT in the prototypical rare-earth nickelate, NdNiO 3 , in large area devices. While previous work examining the electrically-driven IMT in NdNiO 3 suggests defect-dominated conduction, this study shows clear s-type negative differential resistance (NDR) consistent with temperature-dependent resistivity measurements. The NDR peak-to-valley voltage scales linearly with temperature as expected for conductivity pathways dominated by bulk IMT behavior. Unlike other transition metal oxides, which are modeled using the insulator-metal phase fraction as the internal state variable, a thermoelectric model with temperature as the internal state variable is found to more accurately describe the current–voltage characteristic of NdNiO 3 volatile memristors. Overall, we report the synthesis, fabrication, and characterization of NdNiO 3 volatile memristors with resistivity dominated by bulk-like IMT behavior which is scalable and not dependent upon oxygen vacancy migration or defect mediated conduction pathways.

36 MATERIALS SCIENCE↗

A robust statistical analysis of the role of hydropower on the system electricity price and price volatility

Abstract Hydroelectric power (hydropower) is unique in that it can function as both a conventional source of electricity and as backup storage (pumped hydroelectric storage and large reservoir storage) for providing energy in times of high demand on the grid (S. Rehman, L M Al-Hadhrami, and M M Alam), (2015 Renewable and Sustainable Energy Reviews , 44 , 586–98). This study examines the impact of hydropower on system electricity price and price volatility in the region served by the New England Independent System Operator (ISONE) from 2014-2020 (ISONE, ISO New England Web Services API v1.1 .” https://webservices.iso-ne.com/docs/v1.1/ , 2021. Accessed: 2021-01-10). We perform a robust holistic analysis of the mean and quantile effects, as well as the marginal contributing effects of hydropower in the presence of solar and wind resources. First, the price data is adjusted for deterministic temporal trends, correcting for seasonal, weekend, and diurnal effects that may obscure actual representative trends in the data. Using multiple linear regression and quantile regression, we observe that hydropower contributes to a reduction in the system electricity price and price volatility. While hydropower has a weak impact on decreasing price and volatility at the mean, it has greater impact at extreme quantiles (>70th percentile). At these higher percentiles, we find that hydropower provides a stabilizing effect on price volatility in the presence of volatile resources such as wind. We conclude with a discussion of the observed relationship between hydropower and system electricity price and volatility.

13 HYDRO ENERGY↗

Impact of Storage Time on the Needed Capture Efficiency for Volatile Radionuclides - 13369

During the processing of used nuclear fuel (UNF), volatile radionuclides will be discharged from the facility stack if no recovery processes are in place to limit their release. The volatile radionuclides of concern are {sup 3}H, {sup 14}C, {sup 85}Kr, and {sup 129}I. There are three key regulations that address the release of these radionuclides to the environment- 40 CFR 61, 40 CFR 190, and 10 CFR 20. These regulations apply to the total radionuclide release and establish dose limits for the maximum exposed individual (MEI) in the public both in terms of whole body dose and dose to specific organs such as the thyroid. Each radionuclide released to the environment contributes to the total dose to some degree. In this paper we attempt to evaluate the efficiency requirements for the capture processes to limit the doses to the MEI to regulatory levels. Since the total amount of each volatile radionuclide present in the UNF changes with the age of the fuel, the respective capture requirements also change with time. Specifically, we are interested in the impact of the decreasing contribution of {sup 3}H and {sup 85}Kr, which have relatively short half-lives, 12.32 y and 10.76 y, respectively, with the increasing age of the fuel (i.e., time between when the UNF is removed from the reactor and the time it is processed) on the capture requirements. In this paper we examine the capture requirements for these four radionuclides for three fuel types (pressurized water reactor [PWR] with uranium oxide fuel [UOX], PWR with mixed oxide fuel [MOX], and an advanced high temperature gas-cooled reactor [AHTGR]), several burnup values, and time out of reactor extending to 200 y. We calculate doses to the MEI with the EPA code CAP-88 and look at two dose contribution cases. In the first case, we assume that the total allowable dose is attributed to only the four volatile radionuclides. This establishes the lowest capture efficiency value possible. Since this is unrealistic, because it assumes zero dose contribution from all other radionuclides, we also examine a second case, where only 10% of the allowable dose is assigned to the four volatile radionuclides. We calculate the required decontamination factors (DFs) for both of these cases for the three fuel types, multiple fuel burnups, and fuel ages and determine whether or not the dose to the whole body or to the thyroid that drives the capture requirements would require additional effluent controls for the shorter half-life volatile radionuclides based on dose considerations. This analysis indicates that the principal isotopes of concern are generally {sup 3}H and {sup 129}I, the latter requiring the highest DFs. The maximum DF value for {sup 129}I is 8000 for the evaluated cases and assumptions used. ∼60 for fresh fuels. The DF for {sup 14}C could be as high as 30 for certain fuels. These values are based on just meeting the regulatory limits, and additional engineering margins (perhaps 3x to 10x or higher) should be applied to provide a safety factor for compliance. However, by assuming less conservative dose allocations, taller stacks, different radionuclide speciation, fuel aging, and other reprocessing facility design and location parameters, the DF requirements could be significantly reduced. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗