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NASA NTRS1988

Emissions of N2O from tropical forest soils - Response to fertilization with NH4(+), NO3(-), and PO4(3-)

Undisturbed oxisols in a central Amazon tropical forest were fertilized with ammonium, nitrate, or phosphate. Enhanced emissions of N2O were observed for all treatments within one day of fertilization, with the response NO3(-) much greater than NH4(+) much greater than PO4(3-). Approximately, 0.5 percent of applied NO3(-) was converted to N2O within two weeks after application, with less than 0.1 percent of the NH4(+) converted to N2O. These experiments reveal a potentially large source of N2O from microbial reduction of NO3(-) in the clay soils of Amazonia.

Keller, M.↗

NASA NTRS1988

Interactions between HCl, NO(x), and H2O ice in the Antarctic stratosphere - Implications for ozone

The role of PSC particles in determining the distributions of HCl and chlorine radicals is studied. The thermodynamics of HCl in ice is discussed, showing that significant quantities of HCl may be dissolved in ice when PSCs form. It is argued that HCl and HNO3 will be removed from the gas phase early in the condensation process, when only small quantities of H2O have been condensed, reflecting the thermodynamic properties of the solid phases of HCl, HNO3, and H2O. Rapid heterogeneous chemical reactions then volatilize reactive chlorine gases and convert NO(x) to solid-phase nitrates, which can be removed by gravitational settling. Analysis of the suite of heterogeneous chemical processes in the polar stratosphere implies a threshold for HCl concentrations, above which chemical loss rates for ozone increase dramatically.

Wofsy, S. C.↗

NASA NTRS1988

Influence of polar stratospheric clouds on the depletion of Antarctic ozone

Precipitation of nitrate in polar stratospheric clouds (PSCs) can provide a significant sink for Antarctic stratospheric odd nitrogen. It is argued that the depth of the Ozone Hole is sensitive to the occurrence of temperatures below about 196 K. An increase in the prevalence of temperatures below 196 K would enhance ozone loss by increasing the spatial extent and persistence of PSCs, and by decreasing the level of HNO3 that remains following PSC evaporation. Concentrations of halogen gases in the 1960s and earlier were insufficient to support major ozone loss, even if thermal conditions were favorable.

Salawitch, Ross J.↗

NASA NTRS1989

Making MgO/SiO2 Glasses By The Sol-Gel Process

Silicon dioxide glasses containing 15 mole percent magnesium oxide prepared by sol-gel process. Not made by conventional melting because ingredients immiscible liquids. Synthesis of MgO/SiO2 glass starts with mixing of magnesium nitrate hexahydrate with silicon tetraethoxide, both in alcohol. Water added, and transparent gel forms. Subsequent processing converts gel into glass. Besides producing glasses of new composition at lower processing temperatures, sol-gel method leads to improved homogeneity and higher purity.

Bansal, Narottam P.↗

NASA NTRS1988

Phase transformations in xerogels of mullite composition

Monophasic and diphasic xerogels have been prepared as precursors for mullite (3Al2O3-2SiO2). Monophasic xerogel was synthesized from tetraethyl orthosilicate and aluminum nitrate nanohydrate and the diphasic xerogel from colloidal suspension of silica and boehmite. The chemical and structural evolutions, as a function of thermal treatment, in these two types of sol-gel derived mullite precursor powders have been characterized by DTA, TGA, X-ray diffraction, SEM and infrared spectroscopy. Monophasic xerogel transforms to an Al-Si spinel from an amorphous structure at approximately 980 C. The spinel then changes into mullite on further heating. Diphasic xerogel forms mullite at approximately 1360 C. The components of the diphasic powder react independently up to the point of mullite formation. The transformation in the monophasic powder occurs rapidly and yields strongly crystalline mullite with no other phases present. The diphasic powder, however, transforms rather slowly and contains remnants of the starting materials (alpha-Al2O3, cristobalite) even after heating at high temperatures for long times (1600 C, 6 hr). The diphasic powder could be sintered to high density but not the monophasic powder in spite of its molecular level homogeneity.

Hyatt, Mark J.↗

NASA NTRS1988

Chemical interactions between the present-day Martian atmosphere and surface minerals: Implications for sample return

Thermochemical and photochemical reactions between surface minerals and present-day atmospheric constituents are predicted to produce microscopic effects on the surface of mineral grains. Relevant reactions hypothesized in the literature include conversions of silicates and volcanic glasses to clay minerals, conversion of ferrous to ferric compounds, and formation of carbonates, nitrates, and sulfates. These types of surface-atmosphere weathering of minerals, biological potential of the surface environment, and atmospheric stability in both present and past Martian epochs. It is emphasized that the product of these reactions will be observable and interpretable on the microscopic surface layers of Martian surface rocks using modern techniques with obvious implications for sample return from Mars. Macroscopic products of chemical weathering reactions in past Martian epochs are also expected in Martian surface materials. These products are expected not only as a result of reactions similar to those proceeding today but also due to aqueous reactions in past epochs in which liquid water was putatively present. It may prove very difficult or impossible, however, to determine definitively from the relic macroscopic product alone either the exact weathering process which led to its formation of the identity of its weathering parent mineral. The enormous advantages of studying the Martian chemical weathering by investigating the microscopic products of present-day chemical reactions on sample surfaces are very apparent.

Prinn, Ronald↗

NASA NTRS1988

Nitrogen geochemistry of a Cretaceous-Tertiary boundary site in New Zealand

Nitrogen in the basal layer of the K-T boundary clay at Woodside Creek, New Zealand, has an abundance of 1100 ppm, a 20-fold enrichment over Cretaceous and Tertiary values. The enrichment parallels that for Ir and elemental carbon (soot); all decrease over the next 6 mm of the boundary clay. The C/N ratio, assuming the nitrogen to be associated with organic rather than elemental carbon, is approximately 5 for the basal layer compared to 20 to 30 for the remainder of the boundary clay. The correlation between N and Ir abundances appears to persist above the boundary, implying that the N is intimately associated with the primary fallout and remained with it during the secondary redeposition processes that kept the Ir abundance relatively high into the lowermost Tertiary. Apparently the basal layer of the boundary clay represents the accumulation of a substantial quantity of N with an isotopic composition approximately 10 percent heavier than background delta value of N-15 values. If the boundary clay represents an altered impact glass from a meteorite impact than it probably denotes a time period of less than 1 year. Therefore, the changes in nitrogen geochemistry apparently occurred over a very short period of time. The high abundance of N and the correspondingly low C/N ratio may reflect enhanced preservation of organic material as a result of the rapid sweepout and burial of plankton by impact ejecta, with little or no bacterial degradation. It is conceivable that the shift in delta value of N-15 may represent an influx of nitrogen from a different source deposited contemporaneously with the impact ejecta. An interesting possibility is that it may be derived from nitrate, produced from the combustion of atmospheric nitrogen.

Gilmour, Iain↗

NASA NTRS1988

Influence of several metal ions on the gelation activation energy of silicon tetraethoxide

The effects of nine metal cations (Li(+), Na(+), Mg(2+), Ca(2+), Sr(2+), Cu(2+), Al(3+), La(3+), and Y(3+) on silica gel formation has been investigated by studying the hydrolysis and polycondensation of silicon tetraethoxide (TEOS) in the presence of metal nitrates. The influence of water: TEOS mole ratio, metal ion concentration, and the reaction temperature has been investigated. The overall activation energy for gel formation has been determined from the temperature dependence of the time of gelation for each system. The activation energy for -Si-O-Si- network formation is found to be 54.5 kJ/mol. The gel formation time as well as the activation energy sharply increase in the presence of Cu(2+), Al(3+), La(3+) and Y(3+). In contrast, the presence of Li(+), Na(+), Mg(2+), Ca(2+), or, Sr(2+) lowers the gelation time, but has no appreciable effect on the activation energy. This difference may be attributed to the participation or nonparticipation of the metal ions in the formation of the three-dimensional polymeric network during the polycondensation step. The concentration of metal ion (Mg(2+), Ca(2+), Y(3+) or the water: TEOS mole ratio had no appreciable effect on the gelation activation energy. A simple test has been proposed to determine whether a metal ion would act as a network intermediate or modifier in silica and other glassy networks.

Bansal, Narottam P.↗

NASA NTRS1988

Characterization of Spirulina biomass for CELSS diet potential

Spirulina sp. as a bioregenerative photosynthetic and an edible alga for space craft crew in a CELSS, was characterized for growth rate and biomass yield in batch cultures, under various environmental conditions. The cell characteristics were identified for two strains of Spirulina: S. maxima and S. plantensis. Fast growth rate and high yield of both strains were obtained under the following conditions: temperature (30 to 35 C), light irradiance (60 to 100 uE/m/s), nitrate (30 mM), phosphate (2 mM), aeration (300 ml/min), and ph (9 to 10). The partitioning of the assimalatory products (proteins, carbohydrates, lipids) were manipulated by varying the environmental growth conditions. The experiments with Spirulina demonstrated that under stress conditions (high light 120 uE/m/s, temperature 38 C, nitrogen or phosphate limitation; 0.1 M sodium chloride) carbohydrate increased at the expense of protein. In other experiments, where the growth media were sufficient in nutrients and incubated under optimum growth conditions, the total proteins were increased up to almost 70 percent of the organic weight. Conclusion: The nutritional quality of the alga could be manipulated by growth conditions, and therefore usful as a subsystem in CELSS.

Tadros, Mahasin G.↗

NASA NTRS1989

Viking and Mars Rover exobiology

Other than Earth, Mars is the planet generating the greatest interest among those researching and contemplating the origin and distribution of life throughout the universe. The similarity of the early environments of Earth and Mars, and the biological evolution on early Earth provides the motivation to seriously consider the possibility of a primordial Martian biosphere. In 1975 the Viking project launched two unmanned spacecraft to Mars with the intent of finding evidence of the existence of present or past life on this planet. Three Viking Biology experiments were employed: the Labeled Release experiment, the Gas Exchange Experiment, and the Pyrolytic Release experiment. Each of these three experiments tested for microbial existence and utilization of a substrate by examining the gases evolved from specific chemical reactions. Although the results of these experiments were inconclusive, they inferred that there are no traces of extant life on Mars. However, the experiments did not specifically look for indication of extinct life. Therefore, most of the exobiologic strategies and experiments suggested for the Mars Rover Sample Return Mission involve searching for signature of extinct life. The most significant biological signatures and chemical traces to detect include: isotopic and chemical signatures of metabolic activity, anomalous concentrations of certain metals, trace and microfossils, organically preserved materials, carbonates, nitrates, and evaporites.

Schwartz, D. E.↗

NASA NTRS1988

The effects of fire on biogenic soil emissions of nitric oxide and nitrous oxide

Measurements of biogenic soil emissions of nitric oxide (NO) and nitrous oxide (N2O) before and after a controlled burn conducted in a chaparral ecosystem on June 22, 1987, showed significantly enhanced emissions of both gases after the burn. Mean NO emissions from heavily burned and wetted (to simulate rainfall) sites exceeded 40 ng N/sq m s, and increase of 2 to 3 compared to preburn wetted site measurements. N2O emissions from burned and wetted sites ranged from 9 to 22 ng N/sq m s. Preburn N2O emissions from these wetted sites were all below the detection level of the instrumentation, indicating a flux below 2 ng N/sq m s. The flux of NO exceeded the N2O flux from burned wetted sites by factors ranging from 2.7 to 3.4. These measurements, coupled with preburn and postburn measurements of ammonium and nitrate in the soil of this chaparral ecosystem and measurements of NO and N2O emissions obtained under controlled laboratory conditions, suggest that the postfire enhancement of NO and N2O emissions is due to production of these gases by nitrifying bacteria.

Levine, Joel S.↗

NASA NTRS1989

Filter measurement results from the Airborne Antarctic Ozone Experiment

Filter samples obtained as part of the AAOE to determine the total nitrate, sulfate, acidic chloride, and acidic fluoride content along the flight path of the NASA ER-2 are studied. These compounds were obtained in the aerosol and vapor phase. The ratio of particulate sulfate observed outside the chemically perturbed region (CPR) of the vortex to that inside the CPR was 2.6. The ratio of total acidic chloride to total acidic flouride within the CPR is near 1, indicating the removal of chloride from the air mass or the partitioning of chloride into an unmeasured species.

Gandrud, B. W.↗

NASA NTRS1989

The 1-((diorganooxyphosphonyl)-methyl)-2,4- and -2,6-diamido benzenes

1-((Diorgano oxyphosphonyl) methyl)-2,4- and -2,6-dinitro and diamino benzenes are prepared by nitrating an (organophosphonyl) methyl benzene to produce the dinitro compounds which are then reduced to the diamino compounds. The organo grounds (alkyl, haloalkyl, aryl) on the phosphorus may be removed to give the free acids (HO)2P(double bond O)single bond. The diamino compounds may be polymerized with dianhydrides or diacyl halides to produce fire and flame resistant polymers which are useful in the manufacture of aircraft structures.

Mikroyannidis, John A.↗

NASA NTRS1989

Some 1-(diorganooxyphosphonyl)methyl-2,4- and -2,6-dinitro-benzenes

1-(Diorgano oxyphosphonyl) methyl) 2,4- and 2,6-dinitro- and diamino benzenes are prepared by nitrating an (organophosphonyl)methly benzene to produce the dinitro compounds which are then reduced to the diamino compounds. The organo group (alkyl, haloalkyl, aryl) on the phosphorus may be removed to give the free acids, (HO)2P(double bond O) single bond. The diamino compounds may be polymerized with dianhydrides or diacyl halides to produce fire and flame resistant polymers which are useful in the manufacture of aircraft structures.

Mikroyannidis, John A.↗

NASA NTRS1989

Ignitability test method

To overcome serious weaknesses in determining the performance of initiating devices, a novel 'ignitability test method', representing actual design interfaces and ignition materials, has been developed. Ignition device output consists of heat, light, gas an burning particles. Past research methods have evaluated these parameters individually. This paper describes the development and demonstration of an ignitability test method combining all these parameters, and the quantitative assessment of the ignition performance of two widely used percussion primers, the M42C1-PA101 and the M42C2-793. The ignition materials used for this evaluation were several powder, granule and pellet sizes of black powder and boron-potassium nitrate. This test method should be useful for performance evaluation of all initiator types, quality assurance, evaluation of ignition interfaces, and service life studies of initiators and ignition materials.

Bement, Laurence J.↗

NASA NTRS1989

Laboratory chemistry and stratospheric clouds

Results are presented from laboratory experiments on the chemistry of ice particles to study the role of HCl and ClONO2 from CFCs in stratospheric ozone depletion over Antarctica. It is found that gaseous HCl is scavenged with high efficiency by the ice and the gas phase chlorine nitrate may react with the HCL-containing ice to produce Cl2. Also, consideration is given ot the behavior of solid nitric acid trihydrate and sulfuric acid aerosols.

Molina, Mario J.↗

NASA NTRS1989

Electrophoresis and isoelectric focusing of whole cell and membrane proteins from the extremely halophilic archaebacteria

The subunits from two purified halobacterial membrane enzymes (ATPase and nitrate reductase) behaved differently with respect to isoelectric focusing, silver staining and interaction with ampholytes. Differential behavior was also observed in whole cell proteins from Halobacterium saccharovorum regarding resolution in two-dimensional gels and silver staining. It is proposed that these differences reflect the existence of two classes of halobacterial proteins.

Stan-Lotter, Helga↗

NASA NTRS1990

The effects of fire on biogenic emissions of methane and nitric oxide from wetlands

Enhanced emissions of methane (CH4) and nitric oxide (NO) were measured following three controlled burns in a Florida wetlands in 1987 and 1988. Wetlands are the major global source of methane resulting from metabolic activity of methanogenic bacteria. Methanogens require carbon dioxide, acetate, or formate for their growth and the metabolic production of methane. All three water-soluble compounds are produced in large concentrations during biomass burning. Postfire methane emissions exceeded 0.15 g CH 4/sq m per day. Preburn and postburn measurements of soil nutrients indicate significant postburn increases in soil ammonium, from 8.35 to 13.49 parts per million (ppm) in the upper 5 cm of the Juncus marsh and from 8.83 to 23.75 ppm in the upper 5 cm of the Spartina marsh. Soil nitrate concentrations were found to decrease in both marshes after the fire. These measurements indicate that the combustion products of biomass burning exert an important 'fertilizing' effect on the biosphere and on the biogenic production of environmentally significant atmospheric gases.

Levine, Joel S.↗