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GEOS Constituent Data Assimilation Beyond Aura MLS: Assimilating NASA SAGE III/ISS Profiles of Stratospheric Water Vapor

Water vapor in the lower stratosphere is an important trace gas for atmospheric chemistry and radiative budget with direct impact on climate. During the last quarter of the 20th century, the Stratospheric Aerosol and Gas Experiment (SAGE) missions were crucial in monitoring the stratospheric ozone loss and the subsequent recovery as well as trends in water vapor linked to surface temperature trends. The SAGE III instrument aboard the International Space Station (ISS) continues the SAGE mission record, with high vertical resolution profiles of water vapor (and other constituents) since mid-2017. The NASA GEOS Earth system model has the capability to assimilate multi-constituents from ground and space-based instruments using the GEOS Constituent Data Assimilation System (CoDAS). Reanalysis products of stratospheric water vapor without data constraints are historically poor, and two recent reanalyses which assimilated stratospheric constituents observed by the Microwave Limb Sounder (MLS) improve the representation of stratospheric composition, including water vapor, when compared against independent observations. The MLS instrument is on NASA's Aura satellite which is expected to be decommissioned in the coming years. Here we demonstrate that while the number of solar occultation observations a day from SAGE III/ISS is about 1 % of the total number of profiles observed globally by MLS, the chemical timescales of water vapor in the lower stratosphere are long enough that the SAGE III/ISS data can provide a useful constraint on the assimilated product. Analyzed water vapor fields from assimilating only SAGE III/ISS water vapor profiles agree well with independent stratospheric observations, including when compared against the frost-point hygrometers at the three NOAA stations. Over the five-year period from 2017 through 2022, the analyzed water vapor using SAGE III/ISS captures many of the features seen with the assimilation of MLS observations. Note, this ability is reduced over regions where the SAGE III/ISS instrument provides infrequent or no observations (associated with the orbit of the ISS), as highlighted in the case study period following the eruption of the tropical underwater volcano Hunga Tonga in early 2022. Nevertheless, there is a clear benefit to the assimilation of stratospheric water vapor from SAGE III/ISS observations, allowing us to continue to monitor stratospheric composition for climate assessments following the impending loss of Aura.

K. Emma Knowland

GEOS Constituent Data Assimilation Beyond Aura MLS: Assimilating NASA SAGE III/ISS Profiles of Stratospheric Water Vapor

Water vapor in the lower stratosphere is an important trace gas for atmospheric chemistry and radiative budget with direct impact on climate. During the last quarter of the 20th century, the Stratospheric Aerosol and Gas Experiment (SAGE) missions were crucial in monitoring the stratospheric ozone loss and the subsequent recovery as well as trends in water vapor linked to surface temperature trends. The SAGE III instrument aboard the International Space Station (ISS) continues the SAGE mission record, with high vertical resolution profiles of water vapor (and other constituents) since mid-2017. The NASA GEOS Earth system model has the capability to assimilate multi-constituents from ground and space-based instruments using the GEOS Constituent Data Assimilation System (CoDAS). Reanalysis products of stratospheric water vapor without data constraints are historically poor, and two recent reanalyses which assimilated stratospheric constituents observed by the Microwave Limb Sounder (MLS) improve the representation of stratospheric composition, including water vapor, when compared against independent observations. The MLS instrument is on NASA's Aura satellite which is expected to be decommissioned in the coming years. Here we demonstrate that while the number of solar occultation observations a day from SAGE III/ISS is about 1 % of the total number of profiles observed globally by MLS, the chemical timescales of water vapor in the lower stratosphere are long enough that the SAGE III/ISS data can provide a useful constraint on the assimilated product. Analyzed water vapor fields from assimilating only SAGE III/ISS water vapor profiles agree well with independent stratospheric observations, including when compared against the frost-point hygrometers at the three NOAA stations. Over the five-year period from 2017 through 2022, the analyzed water vapor using SAGE III/ISS captures many of the features seen with the assimilation of MLS observations. Note, this ability is reduced over regions where the SAGE III/ISS instrument provides infrequent or no observations (associated with the orbit of the ISS), as highlighted in the case study period following the eruption of the tropical underwater volcano Hunga Tonga in early 2022. Nevertheless, there is a clear benefit to the assimilation of stratospheric water vapor from SAGE III/ISS observations, allowing us to continue to monitor stratospheric composition for climate assessments following the impending loss of Aura.

K. Emma Knowland

Exploring constituent redistribution in irradiated U-19Pu-14Zr fuel via electron probe microanalysis

Here, the phenomena of constituent redistribution, wherein a previously homogeneous metallic fuel forms discrete, radially concentric compositional zones upon irradiation was investigated by examining an irradiated U-19Pu-14Zr fuel (where numbers represent wt. %) with a burnup of 11.5 at.% with electron probe microanalysis (EPMA) and quadruple inductively coupled plasma mass spectroscopy (Q-ICP-MS). EPMA-generated U, Pu, and Zr compositional data obtained from a diameter traverse of the sample was converted to mass and was used to: 1) compare the overall fuel element analysis results between the two methods, 2) determine the number of compositionally distinct zones forming as a result of constituent redistribution; and 3) quantify the post-irradiation loss or gain of U, Pu, and Zr atoms in each distinct compositional zone. Weight percent concentrations of U, Pu, and Zr for the overall cross section compare favorably between the two analytical methods, suggesting that the spatially resolved EPMA analysis complements bulk chemical analysis. Among the four identified compositional zones, post-irradiation quantification of U, Pu, and Zr elemental atom content changes shows that the quantity of U atoms lost from the innermost zone is slightly less than the quantity of U atoms gained by the middle two zones, and the quantity of Zr atoms lost from the high-U third zone is slightly less than is gained by the two innermost zones. Pu is lost from all four zones, although the innermost zone and the high-U third zone lose a significantly higher percentage (> 22 %) of their initial Pu atoms than the other two zones. For all three elements, EPMA cannot distinguish between atoms lost due to transport to a different zone from atoms lost due to nuclear processes; however, the insight gained from using this process can be used to experiment with new modeling techniques to predict constituent redistribution in U-Pu-Zr fuels.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Convective transport of reactive constituents to the tropical and mid-latitude tropopause region: I. Observations

Measurements of ozone, reactive carbon and nitrogen, and other trace constituents from flights of the NASA WB-57F aircraft in the upper troposphere and lower stratosphere reveal that convection in the tropics can present a complex mix of surface-emitted constituents right up to the altitude of the lapse rate tropopause. At higher latitudes over the southern US, the strongest transport signal, in terms of constituent mixing ratios, occurred in the potential temperature range of 340-350K or approximately over the altitude range of 9-11km. Weaker convective signals were also seen up to near the tropopause. There was no evidence of convective transport directly into the lower stratosphere from these flights. $CPY 2003 Elsevier Ltd. All rights reserved.

Transport signals

Examining Constituent Redistribution in U-19Pu-10Zr Fuel as it Evolves with Local Burnup

While constituent redistribution is a known irradiation behavior in U-Pu-Zr fuel, new data have shown it is more complex than our current understanding and predictive capabilities. The size and composition of redistributed rings evolve as a function of pin composition, burnup, geometry, and irradiation temperature. In this work, we extract microstructural information from optical microscopy conducted on U-19Pu-10Zr pins (irradiated between 1.9 at. % and 11.6 at. % peak burnup). Both manual image analysis techniques and machine learning-assisted segmentation are used to quantify the thicknesses of the cladding, fuel-cladding interaction layers, and rings of fuel constituent redistribution in addition to pore distribution. These microstructural features and individual redistributed regions affect local thermomechanical properties, and identifying the relationship between burnup and constituent redistribution will improve accurate prediction of advanced reactor fuel performance.

Constituent Redistribution

Remote sensing of trace constituents from atmospheric infrared emission and absorption spectra

Atmospheric infrared emission and absorption spectra obtained from aircraft and balloon-borne spectrometers are presented. From such spectra, mixing ratio vs altitude profiles are derived for several minor constituents. Recent results for HNO3, CF2Cl2, CFCl3, and HF are presented. In addition, the feasibility of infrared detection of other trace constituents, such as HCl, HF, NH3, NO and SO2, against the rest of the atmospheric background is studied. From this study, made on a line-by-line basis for 'state of the art' airborne spectrometers, potential spectral features for detection of the trace constituents are isolated.

Barker, D. B.

Detection of upper atmospheric constituents using submillimeter wave /SMMW/ heterodyne radiometry

Submillimeter wave heterodyne radiometry has been applied to the detection and sounding of upper atmospheric constituents. The use of room-temperature Schottky-diode mixers for the receivers has yielded measurements of 70,000 K noise temperature. Coupling losses into the diode and matching of the IF output limit are observed to limit noise temperature. The technique is evaluated by calculating spectra with assumed temperature and constituent profiles. Vertical integrations are made with a multilayer atmosphere and the direct summation of absorption coefficients for the individual spectral lines is used. Results are presented for tangent path parameters for a mid-latitude summer model and the fractional parts of upper atmospheric constituents as a function of altitude.

Mcavoy, N.

Trace constituent mixing ratios in the lower stratosphere during the 1977 intertropical convergence zone experiment

Minor constituents in the atmosphere can play an important role as tracers in studies of atmospheric transport and mixing. Simultaneous measurements of the vertical distribution of trace constituents in the troposphere and lower stratosphere were conducted in the region of the Intertropical Convergence Zone (ITCZ). An effort was made to measure the mixing ratios of selected trace constituents. A cryogenic sampling system on board a U-2 aircraft was used to acquire whole-air samples and to cryogenically collect samples at 13.7 to 21.3 km. Simultaneous tropospheric measurements using whole-air sampling canisters on board a Learjet aircraft were also carried out.

Vedder, J. F.

Gaseous constituents in the plume from eruptions of Mount St. Helens

Measurements in the stratosphere of gaseous constituents in the plume of Mount St. Helens were obtained during five flights of the NASA U-2 aircraft between 19 May and 17 June 1980. Mixing ratios from gas chromatographic measurements on samples acquired about 24 hours after the initial eruption show considerable enhancement over nonvolcanic concentrations for sulfur dioxide (more than 1000 times), methyl chloride (about 10 times), and carbon disulfide (more than 3 times). The mixing ratio of carbonyl sulfide was comparable to nonvolcanic mixing ratios although 3 days later it was enhanced two to three times. Ion chromatography measurements on water-soluble constituents are also reported. Very large concentrations of chloride, nitrate, and sulfate ions were measured, implying large mixing ratios for the water-soluble gaseous constituents from which the anions are derived. Measurements of radon-222 present in the plume are also reported.

Inn, E. C. Y.

A ground-based technique for millimeter wave spectroscopic observations of stratospheric trace constituents

Recent concern over possible long term stratospheric changes caused by the introduction of man-made compounds has increased the need for instrumentation that can accurately measure stratospheric minor constituents. The technique of radio spectroscopy at millimeter wavelengths was first used to observe rotational transitions of stratospheric ozone nearly two decades ago, but has not been highly developed until recently. A ground-based observing technique is reported which employs a millimeter-wave superheterodyne receiver and multichannel filter spectrometer for measurements of stratospheric constituents that have peak volume mixing ratios that are less than 10 to the -9th, more than 3 orders of magnitude less than that for ozone. The technique is used for an extensive program of observations of stratospheric chlorine monoxide and also for observations of other stratospheric trace gases such as (O-16)3, vibrationally excited (O-16)3, (O-18)2(O-16), N2O, HO2, and HCN. In the present paper, analysis of the observing technique is given, including the method of calibration and analysis of sources of error. The technique is found to be a reliable means of observing and monitoring important stratospheric trace constituents.

Parrish, A.

Laboratory measurements of microwave and millimeter-wave properties of planetary atmospheric constituents

Accurate data on microwave and millimeter-wave properties of potential planetary atmospheric constituents is critical for the proper interpretation of radio occultation measurements, and of radio astronomical observations of both continuum and spectral line emissions. Such data is also needed to correct for atmospheric effects on radar studies of surface reflectivity. Since the refractive and absorptive properties of atmospheric constituents often vary drastically from theoretically-predicted profiles, especially under the extreme conditions characteristic of the planetary atmosphere, laboratory measurements under simulated planetary conditions are required. This paper reviews the instrumentation and techniques used for laboratory measurement of the refractivity and absorptivity of atmospheric constituents at wavelengths longward of 1 mm, under simulated planetary conditions (temperature, pressure, and broadening gases). Techniques for measuring both gases and condensates are considered. Also reviewed are the relative accuracies of the various techniques. Laboratory measurements are reviewed which have already been made, and additional measurements which are needed for interpretation of data from Venus and the outer planets, are highlighted.

Steffes, Paul G.

Laboratory measurements of microwave and millimeter-wave properties of planetary constituents

Accurate data on microwave and millimeter-wave properties of potential planetary atmospheric constituents is critical for the proper interpretation of radio occultation measurements, and of radio astronomical observations of both continuum and spectral line emissions. Such data is also needed to correct for atmospheric effects on radar studies of surface reflectivity. Since the refractive and absorptive properties of atmospheric constituents often vary drastically from theoretically predicted profiles, especially under the extreme conditions characteristic of the planetary atmosphere, laboratory measurements under simulated planetary conditions are required. The instrumentation and techniques used for laboratory measurement of the refractivity and absorptivity of atmospheric constituents at wavelengths longward of 1 mm, under simulated planetary conditions (temperature, pressure, and broadening gases) are reviewed. Techniques for measuring both gases and condensates are considered. Also reviewed are the relative accuracies of the various techniques. Laboratory measurements are reviewed which have already been made, and additional measurements which are needed for interpretation of data from Venus and the outer planets, are highlighted.

Steffes, Paul G.

Global three-dimensional constituent fields derived from profile data

The success of three-dimensional simulations of stratospheric constituent variability depends critically on the initialization of the constituent fields within the global model. This paper describes a technique for generating global three-dimensional fields from vertical constituent proflies. The technique uses potential vorticity (q) and potential temperature (theta) to map the profiles onto the global domain. The profiles used here are obtained from a two-dimensional model calculation that reproduces the relationship between theta, q, N2O and O3 observed during the Airborne Arctic Stratospheric Expedition. The method is verified by comparison with satellite data, aircraft data, and model simulations.

Douglass, Anne R.

The Origin and Time Dependence of the Amount and Composition of Non-Constituent Gases Present in Crystal Growth Systems

Presence of different, non-constituent gases may be a critical factor in crystal growth systems. In Physical Vapor Transport processes the cras(es) can be used intentionally (to prevent excessively high, unstable growth conditions), or can evolve unintentionally during the course of the process (which may lead to undesired reduction in the -rowth rate). In melt growth, particularly under low gravity conditions (reduced hydrostatic pressure) the gas present in the system may contribute to formation of voids in the growing crystals and even to a separation of the crystal and the liquid phase [1]. On the other hand, some amount of gas may facilitate 'contactless' crystal growth particularly under reduced gravity conditions [2 - 6]. Different non-constituent gases may be present in growth ampoules, and their amount and composition may change during the crystallization process. Some gases can appear even in empty ampoules sealed originally under high vacuum: they may diffuse in from the outside, and/or desorb from the ampoule walls. Residual gases can also be generated by the source materials: even very high purity commercial elements and compounds may contain trace amounts of impurities, particularly oxides. The oxides may have low volatilities themselves but their reaction with other species, particularly carbon and hydrogen, may produce volatile compounds like water or carbon oxides. The non-constituent gases, either added initially to the system or evolved during the material processing, may diffuse out of the ampoule during the course of the experiment. Gases present outside (e.g. as a protective atmosphere or thermal conductor) may diffuse into the ampoule. In either case the growth conditions and the quality of the crystals may be affected. The problem is of a particular importance in sealed systems where the amount of the gases cannot be directly controlled. Therefore a reasonable knowledge and understanding of the origin, composition, magnitude, and change with time of gases present in sealed ampoules may be important for a meaningful control and interpretation of crystal growth processes. This problem is of a particular importance for processing of electronic materials in space because (i) safety considerations require using sealed systems only, and (ii) high cost of crystal growth experiments in microgravity calls for a throughout, accurate description of the processing conditions necessary for a meaningful, efficient, and conclusive interpretation of the space results. In this paper we present the results of our extensive studies on gases in closed crystal growth systems which include: (a) Degassing properties of fused silica; (b) Generation of inert gases by source materials (CdTe, ZnTe, CdZnTe, ZnSe, PbTe, PbSe, PbSeTe); (c) Diffusive cas losses from silica glass ampoules.

Palosz, Witold

Comparison of the Variability of Constituents from a 3D Simulation with Observations in the Tropics

Fields from chemical transport models (CTMs) driven by assimilated winds have been shown to represent many aspects of observations at middle and high latitudes. Comparisons of modeled fields with observations have been much poorer in the tropics. Noise in the tropical winds produces variability in constituents in the tropics that greatly exceeds what is observed, Constituent gradients between the tropics, subtropics and middle latitudes are weaker than observed in the lower stratosphere. Tropical transport is shown to be much more realistic using a CTM driven by winds from the assimilation system that has recently been developed by the Data Assimilation Office at Goddard Space Flight Center. The Finite Volume Community Climate Model (FV-CCM), a general circulation model model that uses the NCAR CCM physics and the Lin and Rood dynamical core, is at the core of the new assimilation system. Realistic transport in the tropics, particularly troposphere to stratosphere exchange, is an obvious requirement for realistic representation of the stratosphere to troposphere transport of ozone and other stratospheric constituents to the middle latitude upper troposphere.

Douglass, A. R.

Global Reference Atmospheric Model and Trace Constituents

Global Reference Atmospheric Model (GRAM-99) is an engineering-level model of the Earth's atmosphere. It provides both mean values and perturbations for density, temperature, pressure, and winds, as well as monthly- and geographically-varying trace constituent concentrations. From 0-27 km, thermodynamics and winds are based on National Oceanic and Atmospheric Administration Global Upper Air Climatic Atlas (GUACA) climatology. Above 120 km, GRAM is based on the NASA Marshall Engineering Thermosphere (MET) model. In the intervening altitude region, GRAM is based on Middle Atmosphere Program (MAP) climatology that also forms the basis of the 1986 COSPAR Intemationa1 Reference Atmosphere (CIRA). MAP data in GRAM are augmented by a specially-derived longitude variation climatology. Atmospheric composition is represented in GRAM by concentrations of both major and minor species. Above 120 km, MET provides concentration values for N2, O2, Ar, O, He, and H. Below 120 km, species represented also include H2O, O3, N2O, CO, CH, and CO2. Water vapor in GRAM is based on a combination of GUACA, Air Force Geophysics Laboratory (AFGL), and NASA Langley Research Center climatologies. Other constituents below 120 km are based on a combination of AFGL and h4AP/CIRA climatologies. This report presents results of comparisons between GRAM Constituent concentrations and those provided by the Naval Research Laboratory (NRL) climatology of Summers (NRL,/MR/7641-93-7416, 1993). GRAM and NRL concentrations were compared for seven species (CH4, CO, CO2, H2O, N2O, O2, and O3) for months January, April, July, and October, over height range 0-115 km, and latitudes -90deg to + 90deg at 10deg increments. Average GRAM-NRL correlations range from 0.878 (for CO) to 0.975 (for O3), with an average over all seven species of 0.936 (standard deviation 0.049).

Justus, C.

Long-term Measurements of Solar Proton Fluxes (1963-present) and the Subsequent Impact on Stratospheric Constituents

The fluxes of solar protons have been measured by satellites for over forty years (1963-present). Eight Interplanetary Monitoring Platform (IMP) satellites measured solar proton fluxes from 1963-1993 and five NOAA Geostationary Operational Environmental Satellites (GOES) were used for the period 1994present. These high energy solar protons precipitate on the Earth's polar atmosphere sporadically, especially during solar proton events (SPEs), which typically last a few days. Solar protons with energies greater than 30 MeV are capable of reaching the stratosphere and causing increases in odd hydrogen (HOx) and odd nitrogen (NOy) constituents at polar latitudes (greater than 60 degrees geomagnetic). The enhanced HOx leads to short-lived ozone depletion (-days) due to the short lifetime of HOx constituents. The enhanced NOy leads to long-lived ozone changes because of the long lifetime of the NOy family in the stratosphere. Several very large SPEs (August 1972, August and October 1989, July and November 2000, September and November 2001, and October 2003) over the 1963-2004 time period were simulated in the GSFC two-dimensional chemistry and transport model and were predicted to cause significant polar upper stratospheric ozone depletion greater than 10%, which lasted for several weeks past the events. Several satellite instruments (BUV, SBUV, SBW/2, SAGE II, HALOE, etc.) have shown constituent changes as a result of SPEs. Long-term (greater than 40 year) model simulations of the influence of the solar protons and satellite measurements during and after some of the very large SPEs will be shown.

Jackman, Charles H.

Statistical Analysis of CMC Constituent and Processing Data

Ceramic Matrix Composites (CMCs) are the next "big thing" in high-temperature structural materials. In the case of jet engines, it is widely believed that the metallic superalloys currently being utilized for hot structures (combustors, shrouds, turbine vanes and blades) are nearing their potential limits of improvement. In order to allow for increased turbine temperatures to increase engine efficiency, material scientists have begun looking toward advanced CMCs and SiC/SiC composites in particular. Ceramic composites provide greater strength-to-weight ratios at higher temperatures than metallic alloys, but at the same time require greater challenges in micro-structural optimization that in turn increases the cost of the material as well as increases the risk of variability in the material s thermo-structural behavior. to model various potential CMC engine materials and examines the current variability in these properties due to variability in component processing conditions and constituent materials; then, to see how processing and constituent variations effect key strength, stiffness, and thermal properties of the finished components. Basically, this means trying to model variations in the component s behavior by knowing what went into creating it. inter-phase and manufactured by chemical vapor infiltration (CVI) and melt infiltration (MI) were considered. Examinations of: (1) the percent constituents by volume, (2) the inter-phase thickness, (3) variations in the total porosity, and (4) variations in the chemical composition of the Sic fiber are carried out and modeled using various codes used here at NASA-Glenn (PCGina, NASALife, CEMCAN, etc...). The effects of these variations and the ranking of their respective influences on the various thermo-mechanical material properties are studied and compared to available test data. The properties of the materials as well as minor changes to geometry are then made to the computer model and the detrimental effects observed using statistical analysis software. The ultimate purpose of this study is to determine what variations in material processing can lead to the most critical changes in the materials property. The work I have taken part in this summer explores, in general, the key properties needed In this study SiC/SiC composites of varying architectures, utilizing a boron-nitride (BN)

Fornuff, Jonathan