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At least 217 records · Page 12

Nitric oxide, water vapor, and ozone in the atmosphere as measured in SITU from an aircraft

As part of the instrument evaluation plan for the NASA Global Atmospheric Sampling Program, prototype instruments were tested aboard the NASA Convair 990 during four flights in January and February of 1974. All the data were taken in maritime air between Hawaii and San Francisco and between Hawaii and 155 deg W, 35 deg N. A chemiluminescent instrument was used to measure nitric oxide. Water vapor, which was measured by using an aluminum oxide hygrometer, ranged from 5.2 micro g/g to saturation. Ozone was measured by an instrument using the ultraviolet absorption technique and ranged up to 235 ppbv. Typical temporal plots of the concentrations of the three constituents are presented. All the constituents showed considerable spatial and day-to-day variation in concentration at each altitude flown. Measurements of the three constituents were made simultaneously at various altitudes between 7.6 and 12.5 km.

Briehl, D.↗

Temporal and Spatial Dynamics of Nitric Oxide Production at High Latitudes During an ICME-driven Storm on Dec. 14, 2006

During geomagnetic storms driven by interplanetary coronal mass ejections (ICMEs), Earth’s upper atmosphere neutral mass density is directly driven by the geomagnetic storm cycle from intense driving and subsequent recovery. The neutral density heating and cooling times are shorter for stronger storms and longer for weaker storms. The influx of energy (Joule Heating and precipitation) into Earth’s upper atmosphere during the storm main phase allows for the enhanced production of nitric oxide (NO) at high latitudes, which in turn cools the thermosphere by radiating away excess energy. As a result, greater NO production results in quicker thermospheric cooling. Yet while the production of NO on a global scale has been examined in detail, the space and time evolution of NO is not well-known. In this study, we investigate the effects of a particular ICME-driven storm, which occurred on Dec. 14th, 2006, on the production of NO at high latitudes. We compare NO measurements from the Thermosphere, Ionosphere, Mesosphere Dynamics (TIMED) spacecraft to neutral mass density measurements from the Challenging Minisatellite Payload (CHAMP) spacecraft and find that the impact of the shock prior to the storm, not just the onset of the storm itself, is responsible for an increase in NO production. We also observe a dawn-dusk asymmetry in high-latitude NO production and discuss how the geometry of the solar wind driver may play a role in creating this asymmetry. Finally, we discuss how the improved hemispheric and local time coverage provided by the GDC and DYNAMIC missions will enable more robust studies of the spatiotemporal evolution of NO during storms. Since NO is an important factor in regulating the neutral density of the thermosphere, such studies will be relevant for more accurate orbital drag calculations.

Kevin Delano↗

A matrix-isolation-infrared spectroscopic study of the reactions of nitric oxide with oxygen and ozone

An investigation of the oxidation of NO to NO2 by trapping the products of the gas-phase reactions with excess oxygen and ozone identified the transient species by their infrared spectra. The primary products of the NO + NO2 reactions were NO2, N2O3(A), N2O3(B), N2O4, and peroxy nitrate (OONO). The primary products of the NO + O3 reactions were NO2 and peroxy NO3 with the higher nitric oxides in low concentrations compared with the NO + O2 reactions. Isotopic oxygen and ozone were used to identify the infrared absorption frequency of the peroxy nitrate.

Bhatia, S. C.↗

Theoretical nitric oxide production incidental to autoignition and combustion of several fuels homogeneously dispersed in air under some typical hypersonic flight conditions

A reaction package of 100 chemical reactions and attendant reaction rate constants defined for the autoignition and combustion of four carbonaceous fuels, CH4, CH3OH, C2H6, and C2H5OH. Definition of the package was made primarily by means of comparison between trial calculations and experimental data for the autoignition of CH4. Autoignition and combustion of each of these four fuels was calculated under three sets of conditions realistic for hypersonic flight applications, for comparison to hydrogen fuel, particularly with respect to formation of nitric oxide. Results show that, for all of the fuels including hydrogen, if NO production is a significant problem, compromise must be made between approaching equilibrium heat release and approaching equilibrium NO concentration.

Bahn, G. S.↗

Effective photodissociation cross sections for molecular oxygen and nitric oxide in the Schumann-Runge bands

Accurate calculations of the atmospheric opacity and the photodissociation rate of molecular oxygen in the Schumann-Runge bands (175-205) are necessary for modeling chemistry in the terrestrial upper atmosphere. The present investigation is concerned with a single simple parameterization of effective cross sections which can be used to calculate both O2 opacity and dissociation rates. Use is made of a zenith angle dependent factor which accounts for variations shown in detailed calculations. The conducted analysis is based on the results of Frederick and Hudson (1980). Attention is given to molecular oxygen effective cross sections and nitric oxide effective cross sections. It is found that the depth of the atmosphere to which solar radiation in the 175-200 nm spectral region penetrates is a sensitive function of the rotational line widths in the Schumann-Runge bands. The oscillator strength for each band measures the cross section integrated over the band while the line width determine how the absorption is distributed in wavenumber.

Allen, M.↗

Variation of D-region nitric-oxide density with solar activity and season at the dip equator

To study the solar control on electron density (N sub e) in the equatorial D region, a program was initiated with Soviet collaboration in 1979. A total of 31 rockets were launched during the high solar activity period, and 47 rockets during the low solar activity period, from Thumba to measure the N sub e profiles. Analysis of the data shows that the average values of N sub e for the high solar activity period are higher by a factor of about 2 to 3 compared to the low solar activity values. It was found that a single nitric oxide density, (NO), profile cannot reproduce all the observed N sub e profiles. An attempt was made to reproduce theoretically the observed N sub e profiles by introducing variation in (NO) for the different solar activity periods and seasons.

Chakrabarty, D. K.↗

The direct measurement of nitric oxide concentration in the upper atmosphere by a rocket-borne chemiluminescent detector

The paper describes a rocket-borne chemiluminescent NO detector and gives some NO mixing ratios in the altitude range from 42 to 60 km calculated on the basis of data obtained from this instrument. The mixing ratios were calculated from the observed counting rates on the assumption of a standard atmospheric pressure profile and the known vehicle velocity profile. The NO mixing ratio decreased from 4.2 billionths at 42 km to 2.2 billionths at 50 km, and then increased to 5.2 billionths at 60 km. The results are deemed accurate to within 20% and may be viewed as upper bounds on nitric oxide concentration in the absence of any NO loss processes.

Mason, C. J.↗

Effect of water injection on nitric oxide emissions of a gas turbine combustor burning natural gas fuel

The effect of direct water injection on the exhaust gas emissions of a turbojet combustor burning natural gas fuel was investigated. The results are compared with the results from similar tests using ASTM Jet-A fuel. Increasing water injection decreased the emissions of oxides of nitrogen (NOX) and increased the emissions of carbon monoxide and unburned hydrocarbons. The greatest percentage decrease in NOX with increasing water injection was at the lowest inlet-air temperature tested. The effect of increasing inlet-air temperature was to decrease the effect of the water injection. The reduction in NOX due to water injection was almost identical to the results obtained with Jet-A fuel. However, the emission indices of unburned hydrocarbons, carbon monoxide, and percentage nitric oxide in NOX were not.

Marchionna, N. R.↗

Isotopic Fractionation and Kinetic Isotope Effects of a Purified Bacterial Nitric Oxide Reductase (NOR)

Nitrous oxide (N 2 O) is a serious concern due to its role in global warming and ozone destruction. Agricultural practices account for ~80% of all anthropogenic N 2 O produced in the US, due in large part to the stimulation of microbial denitrification. Stable isotopes are uniquely suited to examine both microbial N 2 O sources and the mechanism of N 2 O biosynthesis through the use of 2 Site Preference (δ 15 N SP ; the difference in δ 15 N between the central and outer N atoms in N 2 O) and kinetic isotope effects (KIEs), respectively. Using trace gas isotope ratio mass spectrometry (TG-IRMS), we determined the δ 15 N, δ 15 N α , δ 15 N β , and δ 18 O of N 2 O produced by a purified cytochrome c nitric oxide reductase (cNOR) from Paracoccus denitrificans. We also calculated δ 15 N SP , the KIEs, and associated isotopic enrichment factors (ε) for N bulk , N α , and N β . A normal isotope effect was observed for bulk 15 N, with a KIE value of 1.0086 ± 0.0009 (ε = -8.6 ± 0.9‰). The isotope effects for both 15 N α and 15 N β were also normal, with position-specific KIEs of 1.0072 ± 0.0010 (ε = -7.2 ± 1.0‰) and 1.0100 ± 0.0010 (ε = -9.9 ± 1.0‰), respectively, and δ 15 N SP values ranged from 0.5 to 8.7‰ with no significant trend as the reaction proceeded. Values of δ 18 O increased with N 2 O production (slope of δ 18 O against [-flnf/(1-f)] = -19.9 ± 1.9‰). We present implications for the mechanism of N 2 O production from cNOR based on our data.

Rivett, Elise D. [Michigan State Univ., East Lansi↗

Satellite measurements of the backscattered ultraviolet to determine ozone trends, volcanic SO2, and nitric oxide

Measurements of the atmospheric backscattered UV albedo have been used from satellites for more than 20 years to measure ozone. The longest continuous record has been from the Solar Backscattered Ultraviolet instrument (SBUV) and TOMS on the Nimbus 7 satellite, which have been in operation since November of 1978. Because of degradation in space of the diffuser plate used to measure extraterrestrial solar flux, it has been necessary to develop new techniques to maintain the calibration of these instruments. Calibration is maintained by requiring that ozone measured by different wavelength pairs be consistent, and by requiring that ozone measured at different solar zenith angles be consistent. This technique of using a geophysical quantity, ozone, as a transfer standard for wavelength calibration is very powerful. The recalibrated data have been used to measure total ozone trends to an accuracy of +/- 1.3 percent 2(sigma) error over ten years. No significant trends are found near the equator, but significant trends larger than predicted by homogeneous chemistry are found at middle to high latitudes in both hemispheres. In addition, UV albedo data have been used to measure SO2 using band structure in the 300-310 nm range, and to measure nitric oxide in the upper stratosphere and mesosphere using the (10) and (02) NO gamma band fluorescence features.

Mcpeters, Richard↗

Precision ultranarrow-linewidth resonance excitation (PURE) preparation of a molecular beam of nitric oxide molecules for inelastic scattering with argon

We recently reported a novel technique that utilizes narrow-linewidth lasers to selectively excite molecules into a pure quantum state with a well-resolved, tunable distribution of velocities [O. A. Krohn and D. W. Chandler, J. Phys. Chem. Lett. 15(50), 12455–12463 (2024)]. We refer to the preparation of molecules by this technique as precision ultranarrow-linewidth resonant excitation (PURE) preparation. Here, in this study, we pair this PURE preparation methodology with active frequency stabilization of the quantum cascade laser that drives the excitation. In doing so, highly velocity-resolved packets of molecules are possible, with the limitations of this velocity resolution set by the stability of the laser locking and the spectral linewidth of the transition. We show that side-of-fringe locking to a Doppler-broadened absorption spectrum of our target molecule is sufficiently stable for PURE preparation of molecules for long timescales (several hours) with highly resolved velocity spreads (σ < 3 m/s). To demonstrate the scientific utility of this new capability, we present differential cross sections from scattering between a neat molecular beam of argon and a velocity-selected beam of nitric oxide (NO) in a pure quantum state. We observe well-resolved quantum diffraction oscillations in the forward-scattered collisions as well as general trends consistent with prior characterized collisions of NO + Ar.

Krohn, Olivia A. [Sandia National Laboratories (SN↗

Chemical ionization mass spectrometry utilizing benzene cations for measurements of volatile organic compounds and nitric oxide

We evaluate the capability of chemical ionization mass spectrometry (CIMS) using benzene cations as reagent ions (benzene CIMS) for detecting atmospheric trace gases. We characterize the ionization pathways and product ion distributions for 27 analytes spanning diverse chemical classes. To interpret the complex ion chemistry involving two reagent ions (C 6 H$^{+}_{6}$ and (C 6 H 6 )$^{+}_{2}$) and multiple ionization pathways (charge transfer, proton transfer, adduct formation, and hydride abstraction), we introduce a thermodynamics-based framework that classifies analytes into three categories based on their ionization energy (IE), relative to those of benzene monomer (9.24 eV) and dimer (8.69 eV). Each class exhibits distinct ionization mechanisms and product ions. Analytes with IE smaller than 8.69 eV (low IE) undergo charge transfer with both reagent ions; analytes with IE between 8.69 and 9.24 eV (mid IE) undergo charge transfer with C 6 H$^{+}_{6}$ and potential adduct formation with (C 6 H 6 )$^{+}_{2}$; analytes with IE larger than 9.24 eV (high IE) could undergo adduct formation, proton transfer, or hydride abstraction. Analytes within each class also show similar sensitivity, enabling sensitivity estimation for compounds lacking calibration standards. In addition to volatile organic compounds (VOCs), benzene CIMS detects nitric oxide (NO) with a detection limit of 5 pptv for 1 min integration time, exceeding the performance of most commercial NOx analyzers. Field deployments in Chicago and St. Louis demonstrate good agreement with reference NO measurements. Isoprene measurements show good agreement with a co-located gas chromatography–photoionization detector (GC-PID) in St. Louis, but exhibit substantial positive bias in Chicago, likely due to interferences from anthropogenic VOCs in the polluted urban environment. These results highlight the potential of benzene CIMS for concurrent measurements of NO, VOCs, and their oxidation products using a single instrument, while also underscoring challenges in complex atmospheric conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Active chlorine and nitric oxide formation from chemical rocket plume afterburning

Chlorine and oxides of nitrogen (NO(x)) released into the atmosphere contribute to acid rain (ground level or low-altitude sources) and ozone depletion from the stratosphere (high-altitude sources). Rocket engines have the potential for forming or activating these pollutants in the rocket plume. For instance, H2/O2 rockets can produce thermal NO(x) in their plumes. Emphasis, in the past, has been placed on determining the impact of chlorine release on the stratosphere. To date, very little, if any, information is available to understand what contribution NO(x) emissions from ground-based engine testing and actual rocket launches have on the atmosphere. The goal of this work is to estimate the afterburning emissions from chemical rocket plumes and determine their local stratospheric impact. Our study focuses on the space shuttle rocket motors, which include both the solid rocket boosters (SRB's) and the liquid propellant main engines (SSME's). Rocket plume afterburning is modeled employing a one-dimensional model incorporating two chemical kinetic systems: chemical and thermal equilibria with overlayed nitric oxide chemical kinetics (semi equilibrium) and full finite-rate chemical kinetics. Additionally, the local atmospheric impact immediately following a launch is modeled as the emissions diffuse and chemically react in the stratosphere.

Leone, D. M.↗

Relative rates of nitric oxide and nitrous oxide production by nitrifiers, denitrifiers, and nitrate respirers

An account is given of the atmospheric chemical and photochemical effects of biogenic nitric and nitrous oxide emissions. The magnitude of the biogenic emission of NO is noted to remain uncertain. Possible soil sources of NO and N2O encompass nitrification by autotropic and heterotropic nitrifiers, denitrification by nitrifiers and denitrifiers, nitrate respiration by fermenters, and chemodenitrification. Oxygen availability is the primary determinant of these organisms' relative rates of activity. The characteristics of this major influence are presently investigated in light of the effect of oxygen partial pressure on NO and N2O production by a wide variety of common soil-nitrifying, denitrifying, and nitrate-respiring bacteria under laboratory conditions. The results obtained indicate that aerobic soils are primary sources only when there is sufficient moisture to furnish anaerobic microsites for denitrification.

Anderson, I. C.↗

A Complex Interplay between Nitric Oxide, Quorum Sensing, and the Unique Secondary Metabolite Tundrenone Constitutes the Hypoxia Response in Methylobacter

Methylobacter species, members of the Methylococcales, have recently emerged as some of the globally widespread, cosmopolitan species that play a key role in the environmental consumption of methane across gradients of dioxygen tensions. In this work, we approached the question of howMethylobacter copes with hypoxia, via laboratory manipulation. Through comparative transcriptomics of cultures grown under high dioxygen partial pressure versus cultures exposed to hypoxia, we identified a gene cluster encoding a hybrid cluster protein along with sensing and regulatory functions. Through mutant analysis, we demonstrated that this gene cluster is involved in the hypoxia stress response. Through additional transcriptomic analyses, we uncovered a complex interconnection between the NO-mediated stress response, quorum sensing, the secondary metabolite tundrenone, and methanol dehydrogenase functions. This novel and complex hypoxia stress response system is so far unique to Methylobacter species, and it may play a role in the environmental fitness of these organisms and in their cosmopolitan environmental distribution.Here, we describe a novel and complex hypoxia response system in a methanotrophic bacterium that involves modules of central carbon metabolism, denitrification, quorum sensing, and a secondary metabolite, tundrenone. This intricate stress response system, so far unique to Methylobacter species, may be responsible for the persistence and activity of these species across gradients of dioxygen tensions and for the cosmopolitan distribution of these organisms in freshwater and soil environments in the Northern Hemisphere, including the fast-melting permafrosts.

59 BASIC BIOLOGICAL SCIENCES↗

Arginase reciprocally regulates nitric oxide synthase activity and contributes to endothelial dysfunction in aging blood vessels

BACKGROUND: Although abnormal L-arginine NO signaling contributes to endothelial dysfunction in the aging cardiovascular system, the biochemical mechanisms remain controversial. L-arginine, the NO synthase (NOS) precursor, is also a substrate for arginase. We tested the hypotheses that arginase reciprocally regulates NOS by modulating L-arginine bioavailability and that arginase is upregulated in aging vasculature, contributing to depressed endothelial function. METHODS AND RESULTS: Inhibition of arginase with (S)-(2-boronoethyl)-L-cysteine, HCl (BEC) produced vasodilation in aortic rings from young (Y) adult rats (maximum effect, 46.4+/-9.4% at 10(-5) mol/L, P<0.01). Similar vasorelaxation was elicited with the additional arginase inhibitors N-hydroxy-nor-L-arginine (nor-NOHA) and difluoromethylornithine (DFMO). This effect required intact endothelium and was prevented by 1H-oxadiazole quinoxalin-1-one (P<0.05 and P<0.001, respectively), a soluble guanylyl cyclase inhibitor. DFMO-elicited vasodilation was greater in old (O) compared with Y rat aortic rings (60+/-6% versus 39+/-6%, P<0.05). In addition, BEC restored depressed L-arginine (10(-4) mol/L)-dependent vasorelaxant responses in O rings to those of Y. Arginase activity and expression were increased in O rings, whereas NOS activity and cyclic GMP levels were decreased. BEC and DFMO suppressed arginase activity and restored NOS activity and cyclic GMP levels in O vessels to those of Y. CONCLUSIONS: These findings demonstrate that arginase modulates NOS activity, likely by regulating intracellular L-arginine availability. Arginase upregulation contributes to endothelial dysfunction of aging and may therefore be a therapeutic target.

Non-NASA Center↗

Effects of nitric oxide and nitrogen dioxide on bacterial growth

While it is generally thought that the bactericidal effects of NO and NO2 derive from their reaction with water to form nitrous and nitric acids (Shank et al., 1962), this appears to be true only at high concentrations. The data presented here suggest that at low NO and NO2 concentrations, acids are not present in high enough concentrations to act as toxic agents. Reference is made to a study by Grant et al. (1979), which found that exposing acid forest soil to 1 ppm of NO2 did not cause the soil pH to drop. The results presented here show that at low concentrations of NO and NO2, the NO is bacteriostatic for some organisms and not for others, whereas NO2 may protect some bacteria from the inhibitory effects of NO. Since it has been shown that bacteria can divide while airborne (Dimmick et al., 1979), the present results suggest that NO at the low concentrations found in the atmosphere can select for resistant bacteria in the air and affect the viable airborne bacterial population.

Mancinelli, R. L.↗