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At least 19 records

Interdisciplinary study of atmospheric processes and constituents of the mid-Atlantic coastal region. Attachment 4: Data set for background investigation of atmospheric constituents for Nansemond River site

Background data was provided for the assessment of the environmental impact of a proposed oil refinery location. Climatic background, particulate data, digitized portrayal of site molecular and meteorological data, graphical portrayal of molecular data, hourly meteorological data, and streamflow charts and radiosonde data are given

Kindle, E. C.↗

Interdisciplinary study of atmospheric processes and constituents of the mid-Atlantic coastal region. Attachment 5: Data set for background investigation of atmospheric constituents for Richmond, Virginia area

Background data is provided for the photochemical oxident problem in the Richmond area. Particulate data, digitized portrayal of site molecular and meteorological data, and graphical portrayal of molecular data, hourly meteorological data, and streamflow charts and radiosonde data are also given.

Kindle, E. C.↗

Quantitative Representativeness and Constituency of the Long-Term Agroecosystem Research Network and Analysis of Complementarity with Existing Ecological Networks

Abstract Studies conducted at sites across ecological research networks usually strive to scale their results to larger areas, trying to reach conclusions that are valid throughout larger enclosing regions. Network representativeness and constituency can show how well conditions at sampling locations represent conditions also found elsewhere and can be used to help scale-up results over larger regions. Multivariate statistical methods have been used to design networks and select sites that optimize regional representation, thereby maximizing the value of datasets and research. However, in networks created from already established sites, an immediate challenge is to understand how well existing sites represent the range of environments in the whole area of interest. We performed an analysis to show how well sites in the USDA Long-Term Agroecosystem Research (LTAR) Network represent all agricultural working lands within the conterminous United States (CONUS). Our analysis of 18 LTAR sites, based on 15 climatic and edaphic characteristics, produced maps of representativeness and constituency. Representativeness of the LTAR sites was quantified through an exhaustive pairwise Euclidean distance calculation in multivariate space, between the locations of experiments within each LTAR site and every 1 km cell across the CONUS. Network representativeness is from the perspective of all CONUS locations, but we also considered the perspective from each LTAR site. For every LTAR site, we identified the region that is best represented by that particular site—its constituency—as the set of 1 km grid locations best represented by the environmental drivers at that particular LTAR site. Representativeness shows how well the combination of characteristics at each CONUS location was represented by the LTAR sites’ environments, while constituency shows which LTAR site was the closest match for each location. LTAR representativeness was good across most of the CONUS. Representativeness for croplands was higher than for grazinglands, probably because croplands have more specific environmental criteria. Constituencies resemble ecoregions but have their environmental conditions “centered” on those at particular existing LTAR sites. Constituency of LTAR sites can be used to prioritize the locations of experimental research at or even within particular sites, or to identify the extents that can likely be included when generalizing knowledge across larger regions of the CONUS. Sites with a large constituency have generalist environments, while those with smaller constituency areas have more specialized environmental combinations. These “specialist” sites are the best representatives for smaller, more unusual areas. The potential of sharing complementary sites from the Long-Term Ecological Research (LTER) Network and the National Ecological Observatory Network (NEON) to boost representativeness was also explored. LTAR network representativeness would benefit from borrowing several NEON sites and the Sevilleta LTER site. Later network additions must include such specialist sites that are targeted to represent unique missing environments. While this analysis exhaustively considered principal environmental characteristics related to production on working lands, we did not consider the focal agronomic systems under study, or their socio-economic context.

54 ENVIRONMENTAL SCIENCES↗

Parametric Study of Used Nuclear Oxide Fuel Constituent Dissolution in Molten LiCl-KCl-UCl 3

Prior work identified dissolution of used nuclear oxide fuel constituents from a uranium oxide matrix into molten LiCl-KCl-UCl 3 at 500°C, prompting a subsequent series of three progressive studies (including an initial scoping study, an electrolytic dissolution study, and a chemical-seeded dissolution study) to further investigate associated parameters and mechanisms. Thermodynamic calculations were performed to identify possible reaction mechanisms and their propensities in used oxide fuel constituent dissolution. Used nuclear oxide fuels with varying preconditions from fast and thermal test reactors were separately immersed in the subject salt system to assess fuel constituent migration from the bulk fuel matrix to the salt phase in an initial scoping study. Dissolution of expected fuel constituents, including alkali, alkaline earth, lanthanide, and transuranium oxides, into the chloride salt phase varied widely, ranging from 12% to 99% in the initial study. Uranium isotope blending between the salt phase and bulk fuel matrix was also observed, which was attributed to reducing conditions in the fuel matrix. Electrolytic and chemical-seeded dissolution studies were subsequently performed to effect reducing conditions in the fuel. Other parameters, including temperature (at 500°C, 650°C, 725°C, and 800°C) and uranium trichloride concentrations (at 6, 9, and 19 wt% uranium), were investigated in the latter two studies, resulting in fuel constituent dissolution above 90%. Extents of dissolution were based on initial and final fuel constituent concentrations in the oxide fuels following operations in the salt and subsequent removal of the salt via distillation. Finally, in this series of progressive studies, oxide fuel preconditioning and in situ reducing conditions, along with elevated temperature and uranium trichloride concentrations, were the primary parameters promoting used nuclear oxide fuel constituent dissolution in accordance with identified reaction mechanisms.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Earth GRAM-99 and Trace Constituents

Global Reference Atmospheric Model (GRAM-99) is an engineering-level model of 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, GRAM 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 International Reference Atmosphere (CIRA). 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, CH4, and CO2. At COSPAR 2002 a comparison was made between GRAM constituents below 120 km and those provided by Naval Research Laboratory (NRL) climatology. No current need to update GRAM constituent climatology in that height range was identified. This report examines GRAM (MET) constituents between 100 and 1000 km altitudes. Discrepancies are noted between GRAM (MET) constituent number densities and mass density or molecular weight. Near 110 km altitude, there is up to about 25% discrepancy between MET number density and mass density (with mass density being valid and number densities requiring adjustment). Near 700 km altitude there is also up to about 25% discrepancy between MET number density and mean molecular weight (with molecular weight requiring adjustment). In neither case are MET mass density estimates invalidated. These discrepancies have been traced to MET subroutines SLV (which affects 90-170 km height range) and SLVH (which affects helium above 440 km altitude). With these discrepancies corrected, results are presented to illustrate GRAM (MET) constituent mole fractions in terms of height-latitude cross sections from 100 to 1000 km altitude, and latitude-longitude 'maps' at 450 km (approximate height of International Space Station). Plans are discussed for an update of MET (and GRAM) to correct these constituent inconsistencies and to incorporate several new thermospheric model features.

Justus, C. G.↗

Constituent-Based Life Models Being Developed for SiC/SiC Composites

For the successful utilization of ceramic matrix composites (CMC) as hot-section components in advanced aeropropulsion engines, the CMC constituents will need to be tailored and optimized to meet all the critical property demands of each component. Under the High-Speed Research (HSR) and Advanced High-Temperature Engine Materials Technology (HITEMP) Programs, the NASA Glenn Research Center at Lewis Field initiated research to develop mechanistic models for key CMC thermostructural properties. These models would describe the effects of different constituent factors (composition, geometry, and volume fraction) and of potential application conditions (stress, time, temperature, and environment) on these properties. Particular focus was placed on both analytical and numerical modeling of state-of-the-art SiC/SiC composites where the primary load-bearing constituents are stoichiometric SiC fibers in a complex multiphase SiC matrix produced by chemical vapor infiltration and melt infiltration. Recent studies have resulted in computer-based numerical models for the elastic modulus, thermal expansion, and thermal conductivity properties of the SiC/SiC system. Additional studies have generated analytical and empirical models for the time dependence of composite rupture strength at temperatures above 2200 F (1200 C), where CMC's have an important thermostructural advantage over current nickel-based superalloys. These life models utilize thermal activation theory and fiber stress-rupture results measured at Glenn to generate Larson-Miller (L M) plots of fiber rupture strength versus q, a single time- and temperature-dependent parameter. Assuming a worse case in which the SiC matrix is cracked, rupture is then controlled by the time-dependent fracture characteristics of the fiber bundles bridging the matrix cracks. With this as the controlling mechanism, one can then use simple composite theory and the fiber L M plots to predict CMC rupture strength versus the q parameter. The dashed line shows the predicted rupture strength of a SiC/SiC composite that is reinforced by a state-of-the-art stoichiometric SiC fiber. For the q parameter, time is in hours and temperature in degrees kelvin. To generate these predictions, a two-dimensional 0 /90 composite with approximately 16 percent fiber in the applied stress direction and an air test environment were assumed. As such, it is possible to compare the model predictions against limited stress-rupture data for this CMC as shown by the data points. The good agreement confirms the rupture model at least for the selected CMC and test conditions. Thus for this particular SiC/SiC composite, one can estimate a 1000-hr rupture strength of approximately 12 ksi at 2400 F (T = 1588 K and q = 39 700 K). At lower CMC application stresses, the SiC matrix is typically uncracked, so both the fiber and matrix constituents share the composite load. In this case, CMC rupture is controlled by the constituent with the longest rupture time based on the creep rate of the composite. Measured Monkman-Grant plots of rupture time versus creep rate for the two SiC constituents have been used to develop CMC life models for this important application condition. NASA and DOD are currently using this information to establish application and material goals for more advanced CMC's that can be used at even higher temperatures.

DiCarlo, James A.↗

Investigation of constituent redistribution in U-Pu-Zr fuels and its dependence on varying Zr content

This contribution investigates fuel constituent segregation and fuel-cladding chemical interactions (FCCI) in three U-Pu-Zr fuel pins irradiated to ~11% burnup in Experimental Breeder Reactor-II as part of the X441 DP-1 experiment. In examined pins, Zr content ranged from 6 to 10 and 14 wt.%, while Pu concentration was constant at 19 wt.% Pu. The primary goal of the investigation was to determine the role Zr content plays in fuel performance and this manuscript provides assessment of both constituent redistribution and FCCI as a function of axial position. FCCI was observed in all pins, though no cladding failure was noted. Optical and scanning electron microscopy (SEM) results show that variation in Zr content alters the number and relative size of constituent redistribution zones in the fuel. For example, larger Zr-rich central regions and smaller U-rich intermediate regions were observed in 14 wt.% Zr fuels. More importantly, all examined fuels have four or more discrete constituent redistribution regions, where each region has dissimilar morphological features. The existence of four to six distinctive regions deviates from traditionally accepted three region redistribution model, highlights complexity of constituent redistribution in this metal fuel, and identifies the need to conduct additional studies using state-of-the-art instrumentation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Impact of carbonation on leaching of constituents from a cementitious waste form for treatment of low activity waste at the DOE Hanford site

Carbonation can be a major aging process during disposal of alkaline cementitious waste forms and can impact constituent leaching by changes in material alkalinity, pore structure, and controlling mineral phases. The effect of carbonation on the leaching of major and trace constituents from Cast Stone, a cementitious waste form developed to treat high salt content low activity waste, was studied through a combination of leaching experiments and reactive transport simulations. Diffusive transport of constituents in the waste form was evaluated using reactive transport modeling of diffusion-controlled leaching test results and a geochemical speciation model derived from pH-dependent leaching. Comparisons between Cast Stone materials aged under nitrogen, air, and 2% carbon dioxide in nitrogen showed that carbonation impacts solubility, physical retention and observed diffusivity of major and trace constituents. Carbonation under 2% CO 2 decreased the diffusion-controlled leaching of chromium by two orders of magnitude. Finally, modeling results suggest that carbonation may also decrease solubility of technetium while changes to microstructure by carbonation increases effective diffusivity of constituents in Cast Stone.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Relation of ultrasonic energy loss factors and constituent properties in unidirectional composites

A model is developed relating composite constituents properties with ultrasonic energy loss factors for longitudinal waves propagating in the principal directions of a unidirectional graphite/epoxy fiber composite. All the constituents are assumed to behave as linear viscoelastic materials with energy dissipation properties defined by loss factors. It is found that by introducing a new constituent called the interface material, the composite and constituent properties can be brought into consistency with simple series and parallel models. An expression relating the composite loss factors to the loss factors of the constituents is derived and its coefficients are evaluated.

Williams, J. H., Jr.↗

Ultrasonic wave propagation loss factor in composite in terms of constituent properties

A model is developed to relate the energy loss factors of ultrasonic longitudinal waves propagating in the principal directions of a unidirectional graphite fiber composite to the composite constituent properties. All the constituents are assumed to behave as linear viscoelastic materials with energy dissipation properties defined by loss factors. It is found that by introducing a new constituent called the interface material, the composite and constituent properties can be brought into consistency with simple series and parallel models. An expression relating the composite loss factors to the loss factors of the constituents is derived and its coefficients are evaluated.

Williams, J. H., Jr.↗

The Effect of Solar Proton Events on Ozone and Other Constituents

Solar proton events (SPEs) can cause changes in constituents in the Earth's middle atmosphere. The highly energetic protons cause ionizations, excitations, dissociations, and dissociative ionizations of the background constituents. Complicated ion chemistry leads to HO(x) production and dissociation of N2 leads to NO(y) production. Both the HO(x) and NO(y) increases can result in changes to ozone in the stratosphere and mesosphere. The HO(x) increases lead to short-lived ozone decreases in the mesosphere and upper stratosphere due to the short lifetimes of the HO(x) constituents. The NO(y) increases lead to long-lived stratospheric ozone changes because of the long lifetime of NO(y) constituents in this region. The NO(y) induced ozone changes are generally decreases, however, the NO(y) constituents can interfere with chlorine and bromine radicals in the lowest part of the stratosphere and cause ozone increases. Temperature changes have been predicted to occur as a result of the larger SPEs. Eleven SPEs have caused measurable atmospheric variations since 1969. Neutral wind variations were measured shortly after the July 1982 and April 1984 SPEs. The recent July 2000 SPE caused NO(x) increases that lasted for two months past the event. The two periods of largest SPEs (August 1972 and October 1989) caused ozone decreases that lasted for several weeks past the events.

Jackman, Charles H.↗

Modeling of Alkane Oxidation Using Constituents and Species

It is currently not possible to perform simulations of turbulent reactive flows due in particular to complex chemistry, which may contain thousands of reactions and hundreds of species. This complex chemistry results in additional differential equations, making the numerical solution of the equation set computationally prohibitive. Reducing the chemical kinetics mathematical description is one of several important goals in turbulent reactive flow modeling. A chemical kinetics reduction model is proposed for alkane oxidation in air that is based on a parallel methodology to that used in turbulence modeling in the context of the Large Eddy Simulation. The objective of kinetic modeling is to predict the heat release and temperature evolution. This kinetic mechanism is valid over a pressure range from atmospheric to 60 bar, temperatures from 600 K to 2,500 K, and equivalence ratios from 0.125 to 8. This range encompasses diesel, HCCI, and gas-turbine engines, including cold ignition. A computationally efficient kinetic reduction has been proposed for alkanes that has been illustrated for n-heptane using the LLNL heptane mechanism. This model is consistent with turbulence modeling in that scales were first categorized into either those modeled or those computed as progress variables. Species were identified as being either light or heavy. The heavy species were decomposed into defined 13 constituents, and their total molar density was shown to evolve in a quasi-steady manner. The light species behave either in a quasi-steady or unsteady manner. The modeled scales are the total constituent molar density, Nc, and the molar density of the quasi-steady light species. The progress variables are the total constituent molar density rate evolution and the molar densities of the unsteady light species. The unsteady equations for the light species contain contributions of the type gain/loss rates from the heavy species that are modeled consistent with the developed mathematical forms for the total constituent molar density rate evolution; indeed, examination of these gain/loss rates shows that they also have a good quasi-steady behavior with a functional form resembling that of the constituent rate. This finding highlights the fact that the fitting technique provides a methodology that can be repeatedly used to obtain an accurate representation of full or skeletal kinetic models. Assuming success with the modified reduced model, the advantage of the modeling approach is clear. Because this model is based on the Nc rate rather than on that of individual heavy species, even if the number of species increases with increased carbon number in the alkane group, providing that the quasi-steady rate aspect persists, then extension of this model to higher alkanes should be conceptually straightforward, although it remains to be seen if the functional fits would remain valid or would require reconstruction.

Bellan, Jasette↗

The effect of finite-amplitude baroclinic waves on passive, low-level, atmospheric constituents, with applications to comma cloud evolution

The redistribution of a low-level, passive constituent of the atmosphere under the influence of a growing baroclinic wave is examined by a series of analytical calculations based on a two-level, highly truncated model. It is shown that a constituent confined to the lower half of the atmosphere, and initially homogeneous in the horizontal, will tend to achieve maximum concentration in the low pressure/warm sector portion of the wave and minimum concentration in the high pressure/cold outbreak region with sharpest gradient between the maxima and minima roughly coinciding with the cold front. This distribution is further accentuated if an initial meridional gradient of the constituent exists. Assuming as a rough first approximation, that water vapor can be considered to be such a passive constituent, it is shown that the implied relative humidity field and cloud distribution will tend to evolve into the comma-type form commonly observed on satellite images of mid-latitude cyclone waves. Moreover, the solution is shown to replicate the complex flow regime associated with the comma formation, elucidating the dynamical roles of vertical motion and advection in the cloud evolution.

Saltzman, B.↗

Infrared measurements of atmospheric constituents

The objective of this program is to obtain data concerning the concentration versus altitude of various constituents of interest in the photochemistry of the stratospheric ozone layer. Data pertinent to this objective are obtained using balloon-borne instruments to measure the atmospheric transmission and emission in the mid infrared. In addition to obtaining constituent profile information, the spectral data obtained are also used to identify absorption or emission features which may interfere with the retrieval of constituent data from satellite instruments using lower spectral resolution. The spectral resolution obtained with the solar spectral system is 0.0025 cm(exp -1) and represents about a factor of 5 greater resolution than any solar spectra previously obtained in this spectral region. As a result of the increase in spectral resolution, a large number of features are observed in these spectra which were not observed in previous studies. Identification and analysis of these features is in progress. The results of this analysis to date shows a number of HNO3 features which have not been observed before, and these occur where they will interfere with the retrieval of other constituents. An example of the interference is the occurrence of features in the 780.2 cm(exp -1) region which overlap the ClONO2 feature which will be used for retrieval of ClONO2 by the CLAES instrument on UARS. A number of features due to COF2 were also identified in the 1250 cm(exp -1) region which may interfere with retrieval of N2O5.

Murcray, David G.↗

Analysis of stratospheric ozone, temperature, and minor constituent data

The objective of this research is to use available satellite measurements of temperature and constituent concentrations to test the conceptual picture of stratospheric chemistry and transport. This was originally broken down into two sub-goals: first, to use the constituent data to search for critical tests of our understanding of stratospheric chemistry and second, to examine constituent transport processes emphasizing interactions with chemistry on various time scales. A third important goal which has evolved is to use the available solar backscattered ultraviolet (SBUV) and Total Ozone Mapping Spectrometer (TOMS) data from Nimbus 7 to describe the morphology of recent changes in Antarctic and global ozone with emphasis on searching for constraints to theories. The major effort now being pursued relative to the two original goals is our effort as a theoretical team for the Arctic Airborne Stratospheric Expedition (AASE). Our effort for the AASE is based on the 3D transport and chemistry model at Goddard. Our goal is to use this model to place the results from the mission data in a regional and global context. Specifically, we set out to make model runs starting in late December and running through March of 1989, both with and without heterogeneous chemistry. The transport is to be carried out using dynamical fields from a 4D data assimilation model being developed under separate funding from this task. We have successfully carried out a series of single constituent transport experiments. One of the things demonstrated by these runs was the difficulty in obtaining observed low N2O abundances in the vortex without simultaneously obtaining very high ozone values. Because the runs start in late December, this difficulty arises in the attempt to define consistent initial conditions for the 3D model. To accomplish a consistent set of initial conditions, we are using the 2D photochemistry-transport model of Jackman and Douglass and mapping in potential temperature, potential vorticity space as developed by Schoeberl and coworkers.

Stolarski, Richard S.↗

Three Dimensional Model Simulation of Constituent Transport in the Lowermost Stratosphere

The composition, transport and photochemistry of the lowermost stratosphere, i.e., that part of the atmosphere which is above the tropopause, poleward of the tropics, and at potential temperature lower than the potential temperature of the tropical tropopause (about 380K) are of practical interest for understanding global ozone behavior. Because this region is a transition between transport regimes characterized by different scales of dynamics, it is especially difficult to model realistically. Through comparisons of observations of ozone, carbon dioxide and water vapor with results from a chemistry and transport model using winds from a global meteorological assimilation system, we have established that the model provides a good representation of several important aspects of constituent behavior. These include the constituent gradients near the tropopause as well as the annual cycle of constituents and the altitude dependence of the annual cycle from the tropopause into the middle stratosphere. This talk draws together these results to form a unified picture of transport into the lowermost extratropical stratosphere. In particular, the importance of convective transport to the distribution of both short-lived, and long-lived constituents in the lowermost stratosphere will be evaluated.

Douglass, Anne R.↗

The Effect of Solar Proton Events on Ozone and Other Constituents in the Middle Atmosphere

Solar proton events (SPEs) can result in increases in both HO(x) (H, OH, HO2) and NO(x) (N, NO, NO2) constituents in the middle atmosphere polar region (>60 degrees geomagnetic). FlO(x) constituents produced by SPEs caused decreases in mesospheric and upper stratospheric ozone observed during several events. Recent SPEs in July and November of 2000 caused ozone decreases of over 30 percent during the event as measured by UARS HALOE and NOAA 14 SBUV/2. These HO(x)-driven ozone depletions last only during the SPEs (several hours to a few days) because of the short lifetimes of HO(x) constituents in the atmosphere. The NO(x) species feed into the entire odd nitrogen family NO(y) (N, NO, NO2, NO3, N2O5, HNO,14NO4, CIONO2, BrONO2) over a period of hours to weeks. The NO(y) family lasts several months or more in the stratosphere with low sun conditions. The two largest SPEs in the past 30 years, October 1989 and August 1972, caused polar stratospheric ozone depletions >10 percent for weeks past the events. The SPE in July 2000, third largest in 30 years, was measured by NOAA 14 SBUV/2 to decrease ozone by several percent for days past the event. Enhancements in mesospheric NO(x) of over 50 ppbv were also measured by UARS HALOE during this event. A review of the influence of SPEs on ozone and other constituents in the middle atmosphere will be given in this talk.

Jackman, Charles H.↗