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NASA NTRS1991

Purification and properties of a dissimilatory nitrate reductase from Haloferax denitrificans

A membrane-bound nitrate reductase (nitrite:(acceptor) oxidoreductase, EC 1.7.99.4) from the extremely halophilic bacterium Haloferax denitrificans was solubilized by incubating membranes in buffer lacking NaCl and purified by DEAE, hydroxylapatite, and Sepharose 6B gel filtration chromatography. The purified nitrate reductase reduced chlorate and was inhibited by azide and cyanide. Preincubating the enzyme with cyanide increased the extent of inhibition which in turn was intensified when dithionite was present. Although cyanide was a noncompetitive inhibitor with respect to nitrate, nitrate protected against inhibition. The enzyme, as isolated, was composed of two subunits (Mr 116,000 and 60,000) and behaved as a dimer during gel filtration (Mr 380,000). Unlike other halobacterial enzymes, this nitrate reductase was most active, as well as stable, in the absence of salt.

Halobacteriaceae/enzymology↗

NASA NTRS1979

Sulfate and nitrate mixing ratios in the vicinity of the tropopause

Measurements of sulfate and nitrate in filter samples made during the Global Atmospheric Sampling Program (GASP) from aircraft flying near the tropopause over a period of 28 months beginning in early 1976 are presented. Sulfate and nitrate mixing ratios show a peak near or just above the tropopause during the winter-spring seasons. No peak is evident for sulfate during the summer-fall seasons. The sulfate mixing ratios show a constant average level in 1977-78 of 0.12 + or 0.04 ppbm above the tropopause and 0.05 + or - 0.04 ppbm below the tropopause with higher levels in the spring. Nitrate levels are similar but exhibit greater variability. Correlations between sulfate and nitrate (r = 0.78) and between sulfate and nitrate, on ozone (r = 0.80, 0.78) suggest a predominately stratospheric source for these species.

Lezberg, E. A.↗

NASA NTRS1985

Tentative identification of the 780/cm nu-4 band Q branch of chlorine nitrate in high-resolution solar absorption spectra of the stratosphere

According to models of the photochemistry of the stratosphere, chlorine nitrate (ClONO2) is an important temporary reservoir of stratospheric chlorine. At night, ClO is believed to combine in a three-body reaction with NO2 to form chlorine nitrate. During daylight, chlorine nitrate is destroyed by photolysis to form free chlorine and NO3. Infrared spectroscopy has the potential to provide a technique for conducting important quantitative measurements of stratospheric chlorine nitrate. The present paper reports a detailed study of spectra in the 780/cm region. This study has led to the tentative identification of the nu-4 band Q branch of ClONO2 as a significant contributor to the observed stratospheric absorption near 780.21 per cm.

Rinsland, C. P.↗

NASA NTRS1991

Saturation point model for the formation of metal nitrate in nitrogen tetroxide oxidizer

A model was developed for the formation of metal nitrate in nitrogen tetroxide (N2O4). The basis of this model is the saturation point of metal nitrate in N2O4. This basis is chosen mainly because of the White Sands Test Facility's metal nitrate in N2O4 experience. Means of reaching the saturation point are examined, and a relationship is made for the reaction/formation rate and diffusion rate of metal nitrate in N2O4.

Torrance, Paul R.↗

NASA NTRS1992

Proton affinity of methyl nitrate - Less than proton affinity of nitric acid

Several state-of-the-art ab initio quantum mechanical methods were used to investigate the equilibrium structure, dipole moments, harmonic vibrational frequencies, and IR intensities of methyl nitrate, methanol, and several structures of protonated methyl nitrate, using the same theoretical methods as in an earlier study (Lee and Rice, 1992) of nitric acid. The ab initio results for methyl nitrate and methanol were found to be in good agreement with available experimental data. The proton affinity (PA) of methyl nitrate was calculated to be 176.9 +/-5 kcal/mol, in excellent agreement with the experimental value 176 kcal/mol obtained by Attina et al. (1987) and less than the PA value of nitric acid. An explanation of the discrepancy of the present results with those of an earlier study on protonated nitric acid is proposed.

Lee, Timothy J.↗

NASA NTRS1994

Ab Initio Calculations of Singlet and Triplet Excited States of Chlorine Nitrate and Nitric Acid

Ab initio calculations of vertical excitations to singlet and triplet excited states of chlorine nitrate and nitric acid are reported. The nature of the electronic transitions are examined by decomposing the difference density into the sum of detachment and attachment densities. Counterparts for the three lowest singlet excited states of nitric acid survive relatively unperturbed in chlorine nitrate, while other low-lying singlet states of chlorine nitrate appear to be directly dissociative in the ClO chromophore. These results suggest an assignment of the two main peaks in the experimental chlorine nitrate absorption spectrum. In addition, triplet vertical excitations and the lowest optimized triplet geometries of both molecules are studied.

Grana, Ana M.↗

NASA NTRS2014

Detection of Nitric Oxide by the Sample Analysis at Mars (SAM) Instrument Implications for the Presence of Nitrates

One of the main goals of the Mars Science Laboratory is to determine whether the planet ever had environmental conditions able to support microbial life. Nitrogen is a fundamental element for life, and is present in structural (e.g., proteins), catalytic (e.g., enzymes and ribozymes), energy transfer (e.g., ATP) and information storage (RNA and DNA) biomolecules. Planetary models suggest that molecular nitrogen was abundant in the early Martian atmosphere, but was rapidly lost to space by photochemistry, sputtering impact erosion, and oxidized and deposited to the surface as nitrate. Nitrates are a fundamental source for nitrogen to terrestrial microorganisms. Therefore, the detection of nitrates in soils and rocks is important to assess the habitability of a Martian environment. SAM is capable of detecting nitrates by their thermal decomposition into nitric oxide, NO. Here we analyze the release of NO from soils and rocks examined by the SAM instrument at Gale crater, and discuss its origin.

Navarro-Gonzalez, R.↗

NASA NTRS1990

Comparative effects of selenite and selenate on nitrate assimilation in barley seedlings

The effect of SeO3= and SeO4= on NO3- assimilation in 8-d-old barley (Hordeum vulgare L.) seedlings was studied over a 24-h period. Selenite at 0.1 mol m-3 in the uptake solutions severely inhibited the induction of NO3- uptake and active nitrate reductases. Selenate, at 1.0 mol m-3 in the nutrient solution, had little effect on induction of activities of these systems until after 12 h; however, when the seedlings were pretreated with 1.0 mol m-3 SeO4= for 24 h, subsequent NO3- uptake from SeO4(=) -free solutions was inhibited about 60%. Sulphate partially alleviated the inhibitory effect of SeO3= when supplied together in the ambient solutions, but had no effect in seedlings pretreated with SeO3=. By contrast, SO4= partially alleviated the inhibitory effect of SeO4= even in seedlings pretreated with SeO4=. Since uptake of NO3- by intact seedlings was also inhibited by SO3=, the percentage of the absorbed NO3- that was reduced was not affected. By contrast, SeO4=, which affected NO3- uptake much less, inhibited the percentage reduced of that absorbed. However, when supplied to detached leaves, both SeO3= and SeO4= inhibited the in vivo reduction of NO3- as well as induction of nitrate reductase and nitrite reductase activities. Selenite was more inhibitory than SeO4= ; approximately a five to 10 times higher concentration of SeO4= than SeO3= was required to achieve similar inhibition. In detached leaves, the inhibitory effect of both SeO3= and SeO4= on in vivo NO3- reduction as well as on the induction of nitrate reductase activity was partially alleviated by SO4=. The inhibitory effects of Se salts on the induction of the nitrite reductase were, however, completely alleviated by SO4=. The results show that in barley seedlings SeO3= is more toxic than SeO4=. The reduction of SeO4= to SeO3= may be a rate limiting step in causing Se toxicity.

NASA Discipline Life Support Systems↗

NASA NTRS2014

Investigating the Sensitivity of Surface-Level Nitrate Seasonality in Antarctica to Primary Sources Using a Global Model

Determining the sources of total nitrate (TNIT NO-3 + HNO3) reaching Antarctica is a long-standing challenge. Here we analyze the monthly sensitivity of surface-level TNIT in Antarctica to primary sources using a global 3-D chemical transport model, GEOS-Chem, and its adjoint. Modeled seasonal variation of TNIT concentrations shows good agreement with several measurement studies, given that the lack of post-depositional processing in the model leads to an expected underestimate of maximum values in November through January. Remote NOx sources have the greatest impact May-July, during when the model background concentrations are sensitive to NOx emissions from fossil fuel combustion, soil, and lightning originating from 25S to 65S. In this season, NOx is transported to Antarctica as TNIT, which is formed above continental source regions at an altitude of 5-11 km. In other seasons, more NOx is transported as a reservoir species (e.g., peroxyacetyl nitrate, PAN) through the free troposphere, transforming into TNIT within a cone of influence that extends to 35S and above 4 km altitude. Photolysis of PAN over Antarctica is the main driver of modeled NOx seasonality. Stratospheric production and loss of tracers are relatively unimportant in monthly sensitivities in GEOS-Chem, driving only a few percent of surface level variability of TNIT. A small peak concentration in August is captured by the model, although some measured values in August fall outside the range of simulated concentrations. Modifications to the model to represent sedimentation of polar stratospheric clouds (PSCs) lead to increased surface level August TNIT concentrations. However, this simple representation does not explicitly account for PSC particle deposition or disappearance of the tropopause in the middle of winter, and thus the influence of stratospheric nitrate sources estimated in this study is likely a lower bound.

stratosphere↗

NASA NTRS1984

Nitrate in the Greenland ice sheet in the years following the 1908 Tunguska event

The Tunguska event on June 30, 1908 has been subjected to much speculation within different fields of research. Publication of the results of the 1961 expedition to the Tunguska area (Florensky, 1963) supports the view that a cometary impact caused the event. Based on this interpretation, calculations of the impactor energy release and explosion height have been reported by Ben-Menahem (1975), and velocity, mass, and density of the impactor by Petrov and Stulov (1975). Park (1978) and Turco et al. (1981, 1982) used these numbers to calculate a production of ca. 30,000,000 tons of NO during atmospheric transit. This paper presents a high-resolution study of nitrate concentration in the Greenland ice sheet in ca. 10 years covering the Tunguska event. No signs of excess nitrate are found in three ice cores from two different sites in Greenland in the years following the Tunguska event. By comparing these results with results for other aerosols generally found in the ice, the lack of excess NO3(-) following the Tunguska event can be interpreted as indicating that the impactor nitrate production calculated by Park (1978) and Turco et al. (1981, 1982) are 1-2 orders of magnitude too high. To explain this, it is suggested, from other lines of reasoning, that the impactor density determined by Petrov and Stulov (1975) probably is too low.

Rasmussen, K. L.↗

NASA NTRS1985

Effects of tyrosine-26 and tyrosine-64 nitration on the photoreactions of bacteriorhodopsin

The photoreactions of nitrated bacteriorhodopsin (bR) are examined. Flash-induced difference spectra of bR, bR with aminotyrosine in position 26 (bR-N26R) and bR with aminotyrosine in position 64 are analyzed. It is observed that changes in the actinic wavelength (from 520 to 500 or 580 nm) have no affect on the shape of the spectra and the formation and decay kinetics of the O and M intermediates. Nitration of tyrosine-64 decreases the chromophore absorbance, shifts the absorption maximum to 535 nm, and affects photocycle kinetics independent of the pK of its phenolic group. Light-dark adaptation spectra for bR are studied. The kinetics of the M and O intermediates in bR with nitrotyrosine in position 64 (bR-N64) and bR with aminotyrosine in position 64 and bR with nitrotyrosine in position 26 and bR-N26R are described and compared to bR; the pH dependence and M and O decay rates are considered. The deprotonation of bR-N64 during the photoreaction cycle and the effects of nitration on the activity of proton pumping are investigated.

Scherrer, P.↗

NASA NTRS1989

Nitrate in the atmospheric boundary layer of the tropical South Pacific - Implications regarding sources and transport

Weekly bulk aerosol samples collected at three sites in the tropical South Pacific from 1983 to 1987 are analyzed. The mean nitrate concentrations obtained for the sites range from 0.107 to 0.117 microg/cu m. The results suggest that the region is minimally affected by the transport of soil material and pollutants from the continents. Measurements from sites in the tropical North Pacific show mean nitrate concentrations that are about three times higher than those in the South Pacific, showing that the North Pacific is significantly impacted by the transport of material from Asia and North America. The relationships between the nitrate concentrations to other constituents at American Samoa are discussed, including nonseasalt sulfate, Pb-210, and Be-7.

Savoie, Dennis L.↗

NASA NTRS1992

Efflux Of Nitrate From Hydroponically Grown Wheat

Report describes experiments to measure influx, and efflux of nitrate from hydroponically grown wheat seedlings. Ratio between efflux and influx greater in darkness than in light; increased with concentration of nitrate in nutrient solution. On basis of experiments, authors suggest nutrient solution optimized at lowest possible concentration of nitrate.

Huffaker, R. C.↗

NASA NTRS1996

Electrolytic Removal of Nitrate From CELSS Crop Residues

The controlled ecological life support system (CELSS) resource recovery system is a waste processing system using aerobic and anaerobic bioreactors to recover plant nutrients and secondary foods from inedible biomass. Crop residues contain significant amounts of nitrate which presents two problems: (1) both CELSS biomass production and resource recovery consume large quantities of nitric acid, (2) nitrate causes a variety of problems in both aerobic and anaerobic bioreactors. A technique was proposed to remove the nitrate from potato inedible biomass leachate and to satisfy the nitric acid demand using a four compartment electrolytic cell.

Colon, Guillermo↗

NASA NTRS2000

Cylodextrin Polymer Nitrate

The development of the use of cyclodextrin nitrates as possible components of insensitive, high-energy energetics is outlined over a time period of 12 years. Four different types of cyclodextrin polymers were synthesized, nitrated, and evaluated regarding their potential use for the military and aerospace community. The synthesis of these novel cyclodextrin polymers and different nitration techniques are shown and the potential of these new materials is discussed.

Kosowski, Bernard↗

NASA NTRS1994

Long Term Dynamic Stream Nitrate and Phosphate Changes Following Watershed Wildfires

During and following the 1988 Yellowstone National Park wildfires, airborne remotely sensed data were collected in order to characterize various vegetative components, fire front movements and bum intensities. ER-2 derived Thematic Mapper Simulator (TMS) data were used in conjunction with water sampling and chemistry analysis to determine fire intensities in various watersheds and aquatic system condition changes. The airborne Daedalus multispectral TMS data allowed the characterization of various bum intensities in watersheds. Stream sampling was then conducted in those various burned watersheds to determine nitrate and phosphate concentration changes. Six stream watersheds were monitored for five years (1989-1993) during non-snow periods (May/June through September): Cache Creek (intensely burned), Blacktail Deer Creek (intensely burned), Snake River (moderately burned), Lamar River (mixed burning), Soda Butte Creek (lightly burned), and Amphitheatre Creek (unburned). One litre samples were collected from those streams with ISCO water samplers every 12 hours. The samples were removed every 14 days .(28 Samples), and water chemistry analysis was performed. Chemistry analysis indicated that nitrate and phosphate concentrations were elevated in moderately burned watersheds and significantly elevated in severely burned watersheds. The results during the five year study indicate that bum intensities regulate stream water nitrate and phosphate concentrations, and that remotely sensed data can be used effectively to predict watershed chemical changes which will affect aquatic conditions.

Ambrosia, Vincent G.↗

NASA NTRS1989

Latent nitrate reductase activity is associated with the plasma membrane of corn roots

Latent nitrate reductase activity (NRA) was detected in corn (Zea mays L., Golden Jubilee) root microsome fractions. Microsome-associated NRA was stimulated up to 20-fold by Triton X-100 (octylphenoxy polyethoxyethanol) whereas soluble NRA was only increased up to 1.2-fold. Microsome-associated NRA represented up to 19% of the total root NRA. Analysis of microsomal fractions by aqueous two-phase partitioning showed that the membrane-associated NRA was localized in the second upper phase (U2). Analysis with marker enzymes indicated that the U2 fraction was plasma membrane (PM). The PM-associated NRA was not removed by washing vesicles with up to 1.0 M NACl but was solubilized from the PM with 0.05% Triton X-100. In contrast, vanadate-sensitive ATPase activity was not solubilized from the PM by treatment with 0.1% Triton X-100. The results show that a protein capable of reducing nitrate is embedded in the hydrophobic region of the PM of corn roots.

NASA Discipline Number 61-10↗

NASA NTRS1994

Characterization of the association of nitrate reductase with barley (Hordeum vulgare L.) root membranes

The nature of the association between nitrate reductase (NR) and membranes was examined. Nitrate reductase activity (NRA) associated with the microsomal fraction of barley (Hordeum vulgare L.) roots amounted to 0.6 to 0.8% of soluble NRA following sonication in the presence of 250 mM KI and repeated osmotic shock. This treatment removed all contaminating soluble NRA from microsomes of uninduced barley roots that had been homogenized in a soluble extract from roots of NO3(-)-induced plants. On continuous sucrose gradients, NRA co-migrated specifically with VO4(-)-sensitive ATPase activity, a plasma membrane (PM) marker; activity of glucose-6-phosphate dehydrogenase, assayed as cytosolic marker, co-migrated with NRA. Microsomal NRA was absent in barley deficient in soluble NR. Perturbation and trypsinolysis experiments with PM vesicles isolated by aqueous two-phase partitioning indicated that NR is associated with the periphery of the cytoplasmic face of the bilayer. These results demonstrate that PM and soluble NRs are essentially the same protein but that the membrane-associated form is tightly bound. Although it is possible that PM-associated NR exists in vivo, unequivocal evidence for this has yet to be shown. However, PM NR is definitely present in vitro.

Non-NASA Center↗