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NASA NTRS1999

Seasonal Distributions of Global Ocean Chlorophyll and Nutrients: Analysis with a Coupled Ocean General Circulation Biogeochemical, and Radiative Model

A coupled general ocean circulation, biogeochemical, and radiative model was constructed to evaluate and understand the nature of seasonal variability of chlorophyll and nutrients in the global oceans. The model is driven by climatological meteorological conditions, cloud cover, and sea surface temperature. Biogeochemical processes in the model are determined from the influences of circulation and turbulence dynamics, irradiance availability, and the interactions among three functional phytoplankton groups (diatoms, chorophytes, and picoplankton) and three nutrient groups (nitrate, ammonium, and silicate). Phytoplankton groups are initialized as homogeneous fields horizontally and vertically, and allowed to distribute themselves according to the prevailing conditions. Basin-scale model chlorophyll results are in very good agreement with CZCS pigments in virtually every global region. Seasonal variability observed in the CZCS is also well represented in the model. Synoptic scale (100-1000 km) comparisons of imagery are also in good conformance, although occasional departures are apparent. Agreement of nitrate distributions with in situ data is even better, including seasonal dynamics, except for the equatorial Atlantic. The good agreement of the model with satellite and in situ data sources indicates that the model dynamics realistically simulate phytoplankton and nutrient dynamics on synoptic scales. This is especially true given that initial conditions are homogenous chlorophyll fields. The success of the model in producing a reasonable representation of chlorophyll and nutrient distributions and seasonal variability in the global oceans is attributed to the application of a generalized, processes-driven approach as opposed to regional parameterization, and the existence of multiple phytoplankton groups with different physiological and physical properties. These factors enable the model to simultaneously represent the great diversity of physical, biological, chemical, and radiative environments encountered in the global oceans.

Gregg, Watson W.↗

NASA NTRS1998

Location of Bromide Ions in Tetragonal Lysozyme Crystals

Anions have been shown to play a dominant role in the crystallization of chicken egg white lysozyme from salt solutions. Previous studies employing X-ray crystallography had found one chloride ion binding site in the tetragonal crystal form of the protein and four nitrate ion binding sites in the monoclinic form. In this study the anion positions in the tetragonal form were determined from the difference Fourier map obtained from lysozyme crystal grown in bromide and chloride solutions. Five possible anion binding sites were found in this manner. Some of these sites were in pockets containing basic residues while others were near neutral, but polar, residues. The sole chloride ion binding site found in previous studies was confirmed, while four of these sites corresponded to four binding sites found for nitrate ions in monoclinic crystals. The study suggests that most of the anion binding sites in lysozyme remain unchanged, even when different anions and different crystal forms of lysozyme are employed.

Lim, Kap↗

NASA NTRS1995

A Coupled-Cluster Study of the Molecular Structure, Vibrational Spectrum, and Heats of Formation of XONO2 (X=H, F, Cl)

The equilibrium structures, harmonic vibrational frequencies, dipole moments, and IR intensities of nitric acid, fluorine nitrate, and chlorine nitrate have been investigated by using the singles and doubles coupled cluster method that also includes a perturbational estimate of the effects of connected triple excitations, CCSD(T). A standard triple-zeta double-polarized basis set was utilized. The equilibrium geometries and vibrational spectra of HONO2 and ClONO2 are shown to be in excellent agreement with the available experimental data. The ab initio vibrational spectrum of FONO2 is also shown to be in excellent agreement with experiment. Unlike the FOOF and FON molecules, but similar to the cis- and trans-FONO molecules, FONO2 is shown to possess normal bond distances. The bonding in FONO2 is shown to be more similar to that in ClONO2 than that in HONO2, although there are still significant differences, especially in the partial atomic charges as deduced from Mulliken populations. This causes FONO2 to possess almost no dipole moment, which is very different to both HONO2 and ClONO2. By using large atomic natural orbital basis sets, CCSD(T) energies are computed for four isodesmic reactions in order to determine an accurate heat of formation for FONO2. Our best estimate for DELTA H(raised circle) (sub f,298) is 3.1 plus or minus 2.0 kcal/mol, indicating that the F-ONO2 bond energy is 31.3 kcal/mol.

Lee, Timothy J.↗

NASA NTRS2000

Role of Vibration-Induced Streaming in Float-Zone Crystal Growth

This presentation will examine in detail the role of vibration-induced streaming flow in the context of float-zone crystal growth. It is very well known that during float-zone materials processing, the naturally occurring temperature gradients along the zone surface impose a thermocapillary flow in the zone. Under certain processing conditions, the thermocapillary flow can also become nonsteady (oscillatory). The presence of thermocapillary flow is detrimental to crystal quality, for it can promote non-uniform dopant distribution and crystal striations. To null this effect we have imposed a counter streaming flow in the zone, via end-wall vibration. This technique has been adapted to float-zone processing of Sodium Nitrate-Barium Nitrate eutectic alloys, under both steady and nonsteady thermocapillary flow conditions. The beneficial effects of counter streaming flow have been clearly brought out through the before and after comparisons of the crystal microstructure. In addition, we are also examining the theoretical underpinnings of the balancing of thermocapillary flows with vibration-driven counter flows in float-zones.

Anilkumar, A. V.↗

NASA NTRS2000

A Coupled Ocean General Circulation, Biogeochemical, and Radiative Model of the Global Oceans: Seasonal Distributions of Ocean Chlorophyll and Nutrients

A coupled ocean general circulation, biogeochemical, and radiative model was constructed to evaluate and understand the nature of seasonal variability of chlorophyll and nutrients in the global oceans. Biogeochemical processes in the model are determined from the influences of circulation and turbulence dynamics, irradiance availability. and the interactions among three functional phytoplankton groups (diatoms. chlorophytes, and picoplankton) and three nutrients (nitrate, ammonium, and silicate). Basin scale (greater than 1000 km) model chlorophyll results are in overall agreement with CZCS pigments in many global regions. Seasonal variability observed in the CZCS is also represented in the model. Synoptic scale (100-1000 km) comparisons of imagery are generally in conformance although occasional departures are apparent. Model nitrate distributions agree with in situ data, including seasonal dynamics, except for the equatorial Atlantic. The overall agreement of the model with satellite and in situ data sources indicates that the model dynamics offer a reasonably realistic simulation of phytoplankton and nutrient dynamics on synoptic scales. This is especially true given that initial conditions are homogenous chlorophyll fields. The success of the model in producing a reasonable representation of chlorophyll and nutrient distributions and seasonal variability in the global oceans is attributed to the application of a generalized, processes-driven approach as opposed to regional parameterization and the existence of multiple phytoplankton groups with different physiological and physical properties. These factors enable the model to simultaneously represent many aspects of the great diversity of physical, biological, chemical, and radiative environments encountered in the global oceans.

Gregg, Watson W.↗

NASA NTRS2000

Significant Findings: Seasonal Distributions of Global Ocean Chlorophyll and Nutrients With a Coupled Ocean General Circulation, Biogeochemical, and Radiative Model: Comparisons With Satellite and In Situ Data - 2

A coupled ocean general circulation, biogeochemical, and radiative model was constructed to evaluate and understand the nature of seasonal variability of chlorophyll and nutrients in the global oceans. Biogeochemical processes in the model were determined from the influences of circulation and turbulence dynamics, irradiance availability, and the interactions among three functional phytoplankton groups (diatoms, chlorophytes, and picoplankton) and three nutrients (nitrate, ammonium, and silicate). Basin scale (>1000 km) model chlorophyll seasonal distributions were statistically positively correlated with CZCS chlorophyll in 10 of 12 major oceanographic regions, and with SeaWiFS in all 12. Notable disparities in magnitudes occurred, however, in the tropical Pacific, the spring/summer bloom in the Antarctic, autumn in the northern high latitudes, and during the southwest monsoon in the North Indian Ocean. Synoptic scale (100-1000 km) comparisons of satellite and in situ data exhibited broad agreement, although occasional departures were apparent. Model nitrate distributions agreed with in situ data, including seasonal dynamics, except for the equatorial Atlantic. The overall agreement of the model with satellite and in situ data sources indicated that the model dynamics offer a reasonably realistic simulation of phytoplankton and nutrient dynamics on basin and synoptic scales.

Gregg, Watson W.↗

NASA NTRS2001

Role of Vibration-Induced Streaming in Float-Zone Crystal Growth

Anikumar, A. V.↗

NASA NTRS2001

Comustion of HAN-Based Monopropellant Droplets in Reduced Gravity

Hydroxylammonium nitrate (HAN) is a major constituent in a class of liquid monopropellants that have many attractive characteristics and which display phenomena that differ significantly from other liquid monopropellants. They are composed primarily of HAN, H2O and a fuel species, often triethanolammonium nitrate (TEAN). HAN-based propellants have attracted attention as liquid gun propellants, and are attractive for NASA spacecraft propulsion applications. A representative propellant is XM46. This mixture is 60.8% HAN, 19.2% TEAN and 20% H2O by weight. Other HAN-based propellant mixtures are also of interest. For example, methanol and glycine have been investigated as potential fuel species for HAN-based monopropellants for thruster applications. In the present research, experimental and theoretical studies are performed on combustion of HAN-based monopropellant droplets. The fuel species considered are TEAN, methanol and glycine. Droplets initially in the mm size range are studied at pressures up to 30 atm. These pressures are applicable to spacecraft thruster applications. The droplets are placed in environments with various amounts of Ar, N2, O2, NO2 and N2O. Reduced gravity is employed to enable observations of burning rates and flame structures to be made without the complicating effects of buoyant and forced convection. Normal gravity experiments are also performed in this research program. The experiment goals are to provide accurate fundamental data on deflagration rates, gasphase temperature profiles, transient gas-phase flame behaviors, the onset of bubbling in droplets at lower pressures, and the low-pressure deflagration limit. Theoretical studies are performed to provide rational models of deflagration mechanisms of HAN-based liquid propellants. Besides advancing fundamental knowledge, this research should aid in applications (e.g., spacecraft thrusters and liquid propellant guns) of this unique class of monopropellants.

Shaw, B. D.↗

NASA NTRS2000

Controlling Microbial Byproducts using Model-Based Substrate Monitoring and Control Strategies

We have developed a computer-controlled bioreactor system to study various aspects of microbially-mediated nitrogen cycling. The system has been used to investigate methods for controlling microbial denitrification (the dissimilatory reduction of nitrate to N2O and N2) in hydroponic plant growth chambers. Such chambers are key elements of advanced life support systems being designed for use on long duration space missions, but nitrogen use efficiency in them is reduced by denitrification. Control software architecture was designed which permits the heterogeneous control of system hardware using traditional feedback control, and quantitative and qualitative models of various system features. Model-based feed forward control entails prediction of future systems in states and automated regulation of system parameters to achieve desired and avoid undesirable system states. A bacterial growth rate model based on the classic Monod model of saturation kinetics was used to evaluate the response of several individual denitrifying species to varying environmental conditions. The system and models are now being applied to mixed microbial communities harvested from the root zone of a hydroponic growth chamber. The use of a modified Monod organism interaction model was evaluated as a means of achieving more accurate description of the dynamic behavior of the communities. A minimum variance parameter estimation routine was also' used to calibrate the constant parameters in the model by iterative evaluation of substrate (nitrate) uptake and growth kinetics. This representation of processes and interactions aids in the formulation of control laws. The feed forward control strategy being developed will increase system autonomy, reduce crew intervention and limit the accumulation of undesirable waste products (NOx).

Smernoff, David T.↗

NASA NTRS1999

Mesoscale Variations of Biogeochemical Properties in the Sargasso Sea

A mesoscale resolution biogeochemical survey was carried out in the vicinity of the US Joint Global Ocean Flux Study Bermuda Atlantic Time-Series Study (BATS) site during the summer of 1996. Real-time nowcasting and forecasting of the flow field facilitated adaptive sampling of several eddy features in the area. Variations in upper ocean nutrient and pigment distributions were largely controlled by vertical isopycnal displacements associated with the mesoscale field. Shoaling density surfaces tended to introduce cold, nutrient-rich water into the euphotic zone, while deepening isopycnals displaced nutrient-depleted water downward. Chlorophyll concentration was generally enhanced in the former case and reduced in the latter. Eddy-induced upwelling at the base of the euphotic zone was affected by features of two different types captured in this survey: (1) a typical mid-ocean cyclone in which doming of the main thermocline raised the near-surface stratification upward; and (2) a mode water eddy composed of a thick lens of 18 C water, which pushed up the seasonal thermocline and depressed the main thermocline. Model hindcasts using all available data provide a four-dimensional context in which to interpret temporal trends at the BATS site and two other locations during the two weeks subsequent to the survey. Observed changes in near-surface structure at the BATS site included shoaling iscpycnals, increased nutrient availability at the base of the euphotic zone, and enhanced chlorophyll concentration within the euphotic zone. These trends are explicable in terms of a newly formed cyclone that impinged upon the site during this time period. These observations reveal that eddy upwelling has a demonstrable impact on the way in which the nitrate-density relationship changes with depth from the aphotic zone into the euphotic zone. A similar transition is present in the BATS record, suggesting that eddy-driven upwelling events are present in the time series of upper ocean biogeochemical properties. The variability in main thermocline temperature and nitrate in this synoptic spatial survey spans the range observed in these quantities in the 10-year time series available at BATS to date (1988-1998).

McGillicuddy Dennis J., Jr.↗

NASA NTRS1999

Mesoscale Variations of Biogeochemical Properties in the Sargasso Sea

A mesoscale resolution biogeochemical survey was carried out in the vicinity of the U.S. Joint Global Ocean Flux Study Bermuda Atlantic Time-series Study (BATS) site during the summer of 1996. Real-time nowcasting and forecasting of the flow field facilitated adaptive sampling of several eddy features in the area. Variations in upper ocean nutrient and pigment distributions were largely controlled by vertical isopycnal displacements associated with the mesoscale field. Shoaling density surfaces tended to introduce cold, nutrient-rich water into the euphotic zone, while deepening isopycnals displaced nutrient-depleted water downward. Chlorophyll concentration was generally enhanced in the former case and reduced in the latter. Eddy-induced upwelling at the base of the euphotic zone was affected by features of two different types captured in this survey-, (1) a typical mid-ocean cyclone in which doming of the main thermocline raised the near-surface stratification upward and (2) a mode water eddy composed of a thick lens of 18C water, which pushed up the seasonal thermocline and depressed the main thermocline. Model hindcasts using all available data provide a four-dimensional context in which to interpret temporal trends at the BATS site and two other locations during the 2 weeks subsequent to the survey. Observed changes in near-surface structure at the BATS site included shoaling isopycnals, increased nutrient availability at the base of the euphotic zone, and enhanced chlorophyll concentration within the cuphotic zone. These trends are explicable in terms of a newly formed cyclone that impinged upon the site during this time period. These observations reveal that eddy upwelling has a demonstrable impact on the way in which the nitrate-density relationship changes with depth from the aphotic zone into the euphotic zone. A similar transition is present in the BATS record, suggesting that eddy-driven upwelling events are present in the time series of upper ocean biogeochemical properties. The variability in main thermocline temperature and nitrate in this synoptic spatial survey spans the range observed in these quantities in the 10-year time series available at BATS to date (1988-1998).

McGillicuddy, D. J.↗

NASA NTRS2003

Solar Energetic Particle Variations

In the largest solar energetic-particle (SEP) events, acceleration occurs at shock waves driven out from the Sun by coronal mass ejections (CMEs). In fact, the highest proton intensities directly measured near Earth at energies up to approximately 1 GeV occur at the time of passage of shocks, which arrive about a day after the CMEs leave the Sun. CME-driven shocks expanding across magnetic fields can fill over half of the heliosphere with SEPs. Proton-generated Alfven waves trap particles near the shock for efficient acceleration but also throttle the intensities at Earth to the streaming limit early in the events. At high energies, particles begin to leak from the shock and the spectrum rolls downward to form an energy-spectral 'knee' that can vary in energy from approximately 1 MeV to approximately 1 GeV in different events. All of these factors affect the radiation dose as a function of depth and latitude in the Earth's atmosphere and the risk to astronauts and equipment in space. SEP ionization of the polar atmosphere produces nitrates that precipitate to become trapped in the polar ice. Observations of nitrate deposits in ice cores reveal individual large SEP events and extend back approximately 400 years. Unlike sunspots, SEP events follow the approximately 80-100-year Gleissberg cycle rather faithfully and are now at a minimum in that cycle. The largest SEP event in the last 400 years appears to be related to the flare observed by Carrington in 1859, but the probability of SEP events with such large fluences falls off sharply because of the streaming limit.

Reames, D. V.↗

NASA NTRS2003

Experiments on Suppression of Thermocapillary Oscillations in Float-Zones by High-Frequency End-Wall Vibrations

Experiments to suppress thermocapillary oscillations using high-frequency vibrations were performed on float-zones. Such a float-zone is formed by melting one end of a vertically held sodium nitrate-barium nitrate crystal rod in contact with a hot surface at the top. In the experiments, when thermocapillary oscillation occurred, the bottom end of the rod was vibrated at a high frequency to generate fine ripples on the melt surface, driving a streaming flow in the opposite direction to that of the thermocapillary convection. It was observed that by generating a sufficiently strong streaming flow the thermocapillary flow can be offset enough such that the associated thermocapillarity oscillations can be quenched.

Anilkumar, A. V.↗

NASA NTRS2004

Analysis of North Atlantic Aircraft Data on Oxygenated Intermediate Species Using an Adapted Regional Chemistry-Transport Model

Our study is on the interaction of nitrogen oxides with organics as they are exported from their complex sources in Eastern North America. Both urban and specific industrial emissions contribute the nitrogen of the C-H-O-N compounds that affect the global atmosphere, helping determine both ozone and the self-cleaning radical chemistry of the troposphere mediated by the OH radical. Different industrial sources, urban, and natural emissions contribute the organic C. Peroxyacetyl nitrate, CH3C(double bonds O)OONO2 is the most interesting compound for which we can measure the outflow to the full depth of the Atlantic troposphere. As we adapt the 3-d chemical model to describe outflow for specific periods with sufficient accuracy, we are analyzing some valuable information in the NARE-97 complete airborne dataset. (NARE: North Atlantic Regional Experiment). Ames researchers find that there are substantial puzzles in the ratios of PAN/NO2. Peroxy acetyl nitrate provides one of the major long-distance export pathways for active nitrogen from Eastern North America. It should be closely linked with NO, (defined as the sum NO + NO2) by simple thermal association and decomposition reactions, at least when the ambient temperature is substantially above 5 C.

Chatfield, Robert↗

NASA NTRS1988

Characteristics of injury and recovery of net NO3- transport of barley seedlings from treatments of NaCl

The nature of the injury and recovery of nitrate uptake (net uptake) from NaCl stress in young barley (Hordeum vulgare L, var CM 72) seedlings was investigated. Nitrate uptake was inhibited rapidly by NaCl, within 1 minute after exposure to 200 millimolar NaCl. The duration of exposure to saline conditions determined the time of recovery of NO3- uptake from NaCl stress. Recovery was dependent on the presence of NO3- and was inhibited by cycloheximide, 6-methylpurine, and cerulenin, respective inhibitors of protein, RNA, and sterol/fatty acid synthesis. These inhibitors also prevented the induction of the NO3- uptake system in uninduced seedlings. Uninduced seedlings exhibited endogenous NO3- transport activity that appeared to be constitutive. This constitutive activity was also inhibited by NaCl. Recovery of constitutive NO3- uptake did not require the presence of NO3-.

Non-NASA Center↗

NASA NTRS1985

Cryptococcus socialis sp. nov. and Cryptococcus consortionis sp. nov., Antarctic basidioblastomycetes

New yeasts from the Ross Desert (dry valley area) of Antarctica include Cryptococcus socialis sp. nov. and Cryptococcus consortionis sp. nov. Cryptococcus socialis MYSW A801-3aY1 (= ATCC 56685) requires no vitamins, assimilates L-arabinose, cellobiose, D-glucuronate, maltose, melezitose, raffinose, soluble starch, sucrose, and trehalose, and may be distinguished from all other basidioblastomycetes by the combination of amylose production, cellobiose assimilation, and failure to utilize nitrate, D-galactose, myo-inositol, and mannitol. Its guanine-plus-cytosine content is 56 mol%. Cryptococcus consortionis MYSW A801-3aY92 (= ATCC 56686) requires thiamine, assimilates L-arabinose, D-glucuronate, 2-ketogluconate, salicin, succinate, sucrose, trehalose, and D-xylose, and may be distinguished from all other basidioblastomycetes by the combination of amylose production and failure to utilize nitrate, cellobiose, D-galactose, myo-inositol, and mannitol. Its guanine-plus-cytosine content is 56 mol%.

Nitrates/metabolism↗

NASA NTRS1987

Magnetic particles

Metal oxide containing polymers and particularly styrene, acrylic or protein polymers containing fine, magnetic iron oxide particles are formed by combining a NO.sub.2 -substituted polymer with an acid such as hydrochloric acid in the presence of metal, particularly iron particles. The iron is oxidized to fine, black Fe.sub.3 O.sub.4 particles which deposit selectively on the polymer particles. Nitrated polymers are formed by reacting functionally substituted, nitrated organic compounds such as trinitrobenzene sulfonate or dinitrofluoro benzene with a functionally coreactive polymer such as an amine modified acrylic polymer or a protein. Other transition metals such as cobalt can also be incorporated into polymers using this method.

Chang, Manchium↗

NASA NTRS2007

Reactive Nitrogen Distribution and Partitioning in the North American Troposphere and Lowermost Stratosphere

A comprehensive group of reactive nitrogen species (NO, NO2, HNO3, HO2NO2, PANs, alkyl nitrates, and aerosol-NO3) were measured in the troposphere and lowermost stratosphere over North America and the Atlantic during July/August 2004 (INTEX-A) from the NASA DC-8 platform (0.1-12 km). Less reactive nitrogen species (HCN and CH3CN), that are also unique tracers of biomass combustion, were also measured along with a host of other gaseous (CO, VOC, OVOC, halocarbon) and aerosol tracers. Clean background air as well as air with influences from biogenic emissions, anthropogenic pollution, biomass combustion, and stratosphere was sampled both over continental U. S., Atlantic and Pacific. The North American upper troposphere was found to be greatly influenced by both lightning NO(x) and surface pollution lofted via convection and contained elevated concentrations of PAN, ozone, hydrocarbons, and NO(x). Under polluted conditions PAN was a dominant carrier of reactive nitrogen in the upper troposphere while nitric acid dominated in the lower troposphere. Peroxynitric acid (HO2NO2) was present in sizable concentrations always peaking at around 8 km. Aerosol nitrate appeared to be mostly contained in large soil based particles in the lower troposphere. Plumes from Alaskan fires contained large amounts of PAN and very little enhancement in ozone. Observational data suggest that lightning was a far greater contributor to NO(x) in the upper troposphere than previously believed. NO(x) and NO(y) reservoir appeared to be in steady state only in the middle troposphere where NO(x)/NO(y) was independent of air mass age. A first comparison of observed data with simulations from four 3-D models shows significant differences between observations and models as well as among models. These uncertainties likely propagate themselves in satellites derived NOx data. Observed data are interpreted to suggest that soil sinks of HCN/CH3CN are at best very small. We investigate the partitioning and interplay of the reactive nitrogen species within characteristic air masses and further examine their role in ozone formation.

Singh, H. B.↗