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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
NASA NTRS1989

Infrared aircraft measurements of stratospheric composition over Antarctica during September 1987

The Jet Propulsion Laboratory Mark IV interferometer recorded high-resolution, infrared solar spectra from the NASA DC-8 aircraft during flights over Antarctica in September 1987. The atmospheric absorption features in these spectra have been analyzed to determine the burdens of O3, NO, NO2, HNO3, ClNO3, HCl, HF, CO2, CH4, N2O, HCN, CO, H2O, CFCl3, and CF2Cl2. The results show a 'collar' of high HNO3 and ClNO3 surrounding a 'core' in which the burdens of these and of HCl and NO2 are very low. Clear increases in the burdens of HF and HNO3 were observed during the course of September in the vortex core. HCl and NO2 exhibited smaller, less significant increases. The burdens of the tropospheric source gases, N2O, CH4, HCN, CFCl3, CF2Cl2, CO, and H2O, were observed to be much smaller over Antarctica than at midlatitudes. This, together with the fact that HF over Antarctica was more than double its midlatidue value, suggests that downwelling had occurred.

Toon, G. C.↗
NASA NTRS1990

The vapor pressures of supercooled NHO3/H2O solutions

A procedure utilizing the Gibbs-Duhem relation is used to extrapolate vapor pressures of supercooled HNO3 mixtures to 190 K. Values of A and B from the equation logP = A - B/T are presented for solutions between 0.20 and 0.25 mole fraction HNO3. In the stratosphere, if sufficient HNO3 vapor is present because it has not come into equilibrium with the nitric acid trihydrate, supercooled nitric acid solutions could condense at temperatures up to 1.5 + or - 0.8 K above the ice point.

Hanson, David R.↗
NASA NTRS1990

Effects of atmospheric transport on column abundances of nitrogen and chlorine compounds in the arctic stratosphere

In the absence of heterogeneous processes, distributions of NO(y), HNO3, Cl(x) and HCl in the polar winter stratosphere should be determined by transport. A model simulating distributions of these species in the arctic for January and February 1989 is developed using observed fields of potential vorticity and potential temperature. Comparison of model results with column measurements from the DC-8 indicates conversion of NO(x) to HNO3, condensation of HNO3, conversion of HCl to CINO3, and conversion of HCl plus CINO3 to an unmeasured species. Heterogeneous processes strongly affect abundances of NO(y) and Cl(x) species in the winter arctic stratosphere.

Yatteau, John H.↗
NASA NTRS1990

A tunable diode laser system for aircraft measurements of trace gases

The advantages of tunable-diode-laser absorption spectrometry (TDLAS) for measuring trace atmospheric gases are universality, positive identification, good sensitivity, and rapid response time. A TDLAS system is described which is capable of making measurements aboard an aircraft. The instrument was employed during the Chemical Instrumentation Test and Evaluation (CITE) 2 program to measure NO2 on 11 flights and HNO3 on five flights. Detection limits were determined to be 25 parts per trillion by volume (pptv) for NO2 and 75 pptv for HNO3 with response times of 3 min. This was sufficient to permit measurements of NO2 in the free troposphere and HNO3 in the continental boundary layer a significant fraction of the time.

Schiff, H. I.↗
NASA NTRS1991

Annular denuders for use in global climate and stratospheric measurements of acidic gases and particles

Measurements of acidic and basic gases that coexist with fine particle (less than 2.5 micron) may be useful for determining the impact of these species on global climate changes and determining species that influence stratospheric ozone levels. Annular denuders are well suited for this purpose. A new concentric annular denuder system, consisting of a three channel denuder, a Teflon coated cyclone preseparator, and a multistage filter pack was developed, evaluated, and shown to provide reliable atmospheric measurements of SO2, HNO2, HNO3, NH3, SO4(=), NH4(+), NO3(-), and H(+). For example, the precision of the annular denuder for the ambient measurements of HNO3 and nitrates at concentrations between 0.1 to 3 microgram/cu m was + or - 12 and 16 pct., respectively. The 120 x 25 mm three channel denuder is encased in a stainless steel sheath and has annular spaces that are 1 mm wide. This design was shown to have nearly identical capacity for removal of SO2 as conventional 210 x 25 mm single channel denuder configurations. The cyclone preseparator was designed and tested to have a D sub 50 cutoff diameter of 2.5 micron and minimal retention of HNO3.

Stevens, Robert K.↗
NASA NTRS1991

Annular denuder systems: Precision and applicability to stratospheric sampling

Annular denuder systems (ADS) are designed to sample both gases and particles from ambient air without cross interference. The ADS's were used to detect chemical gradients over rural forest canopies. Accurate and precise methods for the sampling and analysis of low concentrations of gaseous and particulate species over short sampling periods were developed. Typical analytical precision data for nitrate and sulfate are shown. Both sampling and analytical precision data for a 2 hour test using four collocated ADS's are presented. On this particular day, the overall precision for HNO3 was unusually poor. The overall precision for the major constituents of interest is generally about 3 to 5 percent for typical ambient concentrations. The ADS's could potentially be used to determine the concentrations of HNO3 and fine-particle nitrate in the stratosphere, and to simultaneously characterize the chemical composition of stratospheric aerosols. Assuming 50 mb pressure, a 2 hour sampling time, a 50 Lpm sampling rate, and a low blank value, an overal precision of about 15 percent should be possible for 1 ppbv of HNO3 or nitrate, which would include nitric-acid trihydrate (NAT); and pump-driven systems could accommodate more complex systems involving denuders and filter packs in sequence. Alternate coatings could possibly be developed to selectively sample species such as Cl2 and ClNO3. The ADS's might also be useful in laboratory studies of heterogeneous chemical reactions involving NAT aerosols.

Randtke, Stephen J.↗
NASA NTRS1990

Wintertime nitric acid chemistry - Implications from three-dimensional model calculations

A three-dimensional simulation of the evolution of HNO3 has been run for the winter of 1979. Winds and temperatures are taken from a stratospheric data assimilation analysis, and the chemistry is based on Limb Infrared Monitor of the Stratosphere (LIMS) observations. The model is compared to LIMS observations to investigate the problem of 'missing' nitric acid chemistry in the winter hemisphere. Both the model and observations support the contention that a nitric acid source is needed outside of the polar vortex and north of the subtropics. Observations suggest that HNO3 is not dynamically controlled in middle latitudes. The model shows that given the time scales of conventional chemistry, dynamical control is expected. Therefore, an error exists in the conventional chemistry or additional processes are needed to bring the model and data into agreement. Since the polar vortex is dynamically isolated from the middle latitudes, and since the highest HNO3 values are observed in October and November, a source associated solely with polar stratospheric clouds cannot explain the deficiencies in the chemistry. The role of heterogeneous processes on background aerosols is reviewed in light of these results.

Rood, Richard B.↗
NASA NTRS1992

Reactive nitrogen, ozone, and nitrate aerosols observed in the Arctic stratosphere in January 1990

Ozone mixing ratios in the vicinity of the 525-K potential temperature surface in January and early February of 1990 were observed to decrease sharply across the edge of the vortex boundary, where the vortex position was estimated from Ertel's potential vorticity. The changes in NO(y) mixing ratio with respect to altitude measured on January 18 and 31 were quite well correlated with those of ozone between 15 and 24 km, indicating that NO(y) also had a large gradient across the edge of the vortex. This is interpreted as being mainly due to the significant denitrification that occurred inside the vortex. The total amount of gas and particulate phase HNO3 was close to the NO(y) amount at the altitude of the 22- to 23-km region, suggesting that the conversion of non-HNO3 reactive nitrogen to HNO3 had occurred with a PSC.

Kondo, Y.↗
NASA NTRS1992

Formation of model polar stratospheric cloud films

Fourier transform infrared spectroscopy was used to examine the competitive growth of films representative of polar stratospheric clouds. These experiments show that either crystalline nitric acid trihydrate (beta-NAT) or amorphous films with H2O:HNO3 ratios close to 3:1 formed at temperatures 3-7 K warmer than the ice frost point under stratospheric pressure conditions. In addition, with higher HNO3 pressure, we observed nitric acid dihydrate (NAD) formation at temperatures warmer than ice formation. However, our experiments also show that NAD surfaces converted to beta-NAT upon exposure to stratospheric water pressures. Finally, we determined that the net uptake coefficient for HNO3 on beta-NAT is close to unity, whereas the net uptake coefficient for H2O is much less.

Middlebrook, Ann M.↗
NASA NTRS1991

Determination of the altitude of the nitric acid layer from very high resolution ground-based IR solar spectra

A ground-based solar spectrum at a spectral resolution of about 0.002/cm is used to determine the altitude of the HNO3 layer. The 870/cm spectral region, which is essentially free from absorptions from other species, is employed. The data were obtained with the University of Denver 2.5-m maximum path difference Fourier Transform interferometer spectrometer system. A set of 13 HNO3 vertical profiles were used in the analysis. The best fit obtained for the 'starting' profile (which is centered at 24 km), and the best fit for the profile centered at 26 km are shown. For displacements of greater than 2 km, the discrepancy between the synthetic and observed spectra becomes readily discernible by inspection of the spectra. It is shown that the 'best fit' rms residuals are quite sensitive to the assumed altitude of the HNO3 layer.

Blatherwick, R. D.↗
NASA NTRS1993

Physical chemistry of the H2SO4/HNO3/H2O system - Implications for polar stratospheric clouds

Polar stratospheric clouds (PSCs) play a key role in stratospheric ozone depletion. Surface-catalyzed reactions on PSC particles generate chlorine compounds that photolyze readily to yield chlorine radicals, which in turn destroy ozone very efficiently. The most prevalent PSCs form at temperatures several degrees above the ice frost point and are believed to consist of HNO3 hydrates; however, their formation mechanism is unclear. Results of laboratory experiments are presented which indicate that the background stratospheric H2SO4/H2O aerosols provide an essential link in this mechanism: These liquid aerosols absorb significant amounts of HNO3 vapor, leading most likely to the crystallization of nitric acid trihydrate (NAT). The frozen particles then grow to form PSCs by condensation of additional amounts of HNO3 and H2O vapor. Furthermore, reaction probability measurements reveal that the chlorine radical precursors are formed readily at polar stratospheric temperatures not just on NAT and ice crystals, but also on liquid H2SO4 solutions and on solid H2SO4 hydrates. These results imply that the chlorine activation efficiency of the aerosol particles increases rapidly as the temperature approaches the ice frost point regardless of the phase or composition of the particles.

Molina, M. J.↗
NASA NTRS1994

Laboratory measurements of heterogeneous reactions on sulfuric acid surfaces

Increasing evidence from field, modeling, and laboratory studies suggests that heterogeneous reactions on stratospheric sulfate aerosol particles may contribute to global ozone depletion. Using a Knudsen cell reactor technique, the authors have studied the uptake, reactivity, and solubility of several trace atmospheric species on cold sulfuric acid surfaces representative of stratospheric aerosol particles. The results suggest that the heterogeneous conversion of N2O5 to HNO3 is fast enough to significantly affect the partitioning of nitrogen species in the global stratosphere and thus contribute to global ozone depletion. The hydrolysis of ClONO2 is slower and unlikely to be important under normal conditions at midlatitudes. The solubilities of HCl and HNO3 in sulfuric acid down to 200 K were found to be quite low. For HCl, this means that little HCl is available for reaction on the surfaces of stratospheric sulfate aerosol particles. The low solubility of HNO3 means that this product of heterogeneous reactions will enter the gas phase, and the denitrification observed in polar regions is unlikely to occur in the global stratosphere.

Williams, Leah R.↗
NASA NTRS1994

Energetic particle-induced enhancements of stratospheric nitric acid

Inclusion of complete ion chemistry in the calculation of minor species production during energetic particle deposition events leads to significant enhancement in the calculated nitric acid concentration during precipitation. An ionization rate of 1.2 x 10(exp 3)/cu cm/s imposed for 1 day increases HNO3 from 3 x 10(exp 5) to 6 x 10(exp 7)/cu cm at 50 km. With an ionization rate of 600 cu cm/s, the maximum HNO3 is 3 x 10(exp 7)/cu cm. Calculations which neglect negative ions predict the nitric acid will fall during precipitation events. The decay time for converting HNO3 into odd nitrogen and hydrogen is more than 1 day for equinoctial periods at 70 deg latitude. Examination of nitric acid data should yield important information on the magnitude and frequency of charged particle events.

Aikin, Arthur C.↗
NASA NTRS1993

Observations of the loss of stratospheric NO2 following volcanic eruptions

Observations of stratospheric column amounts of nitrogen dioxide (NO2), nitric oxide (NO) and nitric acid (HNO3) have been made following major eruptions of the El Chichon and Mt. Pintatubo volcanoes. Midlatitude abundances of NO2 and NO were reduced by as much as 70% in the months following the appearance of the volcanic aerosols as compared to volcanically quite periods. There are heterogeneous reactions which could occur on the volcanic aerosols to convert NO2 into HNO3 but no commensurate increase in HNO3 column amounts was observed at the times of NO2 decrease.

Coffey, M. T.↗
NASA NTRS1994

Anomalous HNO3/NO(x) ratio of remote tropospheric air: Conversion of nitric acid to formic acid and NO(x)?

The N oxidation ratio, (HNO3)/(NO(x)), in the free troposphere is measured at approx. 1 to 9 (averaging approx. 5), consistently lower than the values of 15-100 which known theory suggests to be reached rapidly. This discrepancy casts doubt on current models' abilities to predict effects of NO sources on remote (NO), and so also (O3) and (OH). HNO3-to-NO(x) recycling processes involving HCHO in solution are appealing explanations for the ratio. Known chemical theory are illustrated using a Lagrangian box model of the mid-troposphere which simulates characteristic episodes form NO(x) input to HNO3 washout. Ratio and budget constraint equations for No(y) can usefully restrict conceivable explanations of missing chemistry of fast nitrogen cycling; most explanations could be called 'fast-cycles' or 're-NO(x)-ification.' These equations also show how current global models may suggest spuriously good N oxidation ratios and errors in OH. Aerosol or cloud droplets reactions with HCHO may produce (a) formic acid (which needs an appropriate source) and NO(x), or alternatively, (b) hydroxymethyl nitrate (or methyl dinitrate), which might supply a large, variable amount of 'missing NO(y) not currently measurable except by NO(y) instruments.

Chatfield, Robert B.↗
NASA NTRS1997

The Kinetic Nonequilibrium Processes in the Internal Flow and in the Plume of Subsonic and Supersonic Aircrafts

(1) Our results show that under combustion of thermal destruction products of n-C8H18, and other hydrocarbon fuels with air at the equivalent ratio -0.5 and less the chemical equilibrium is not realized at the exit plane of combustion chamber and in the gas turbine and nozzle for most of small components such as NO2, NO3, HNO, HNO2, HNO3, N(x)H(y), HO2, OH. The chemical equilibrium is not realized in the internal flow of ramjet hydrogen combustion engine too. So at the nozzle exit plane both of gas-turbine hydrocarbon combustion engine and of ramjet hydrogen combustion engine the relatively large values of concentration of such small components as NO3, HNO2, N2O, HNO3, HNO, NH, N2H, HO2, H2O2 may be realized. The exact definition of these component concentration as well as concentration of NO(x), OH, SO2, O, H, H2, H2O at the nozzle exit plane is very important for plume chemistry. (2) The results which were obtained for subsonic and hypersonic aircrafts indicate on the considerable change of the composition of the gas mixture along the plume. This change can be caused not only by the mixture of combustion products with the atmosphere air but by proceeding of whole complex of nonequilibrium photochemical reactions. The photodissociation processes begin to influence on the formation of the free atoms and radicals at flight altitude H greater than or equal to 18 km. Neglect of these processes can result in essential (up to 10(exp 4) times) mistakes of values gamma(sub OH), gamma(sub O), gamma(sub H), gamma(sub HSO3) and some products of CFC's disintegration. It was found that penetration of Cl-containing species from the atmosphere into the exhaust flow and its interaction with nitrogen oxides leads to essential increasing of the concentration of Cl, Cl2, ClO2, ClNO3, CH3Cl and sometimes HCl and the decreasing of ClO concentration by comparison with background values. The results of our analysis show that the plume aircraft with both hydrocarbon and hydrogen combustion engine may be source of various pollutant components such as HNO, HNO4,ClO2, CH3NO2, CH3NO3, CH2O, Cl, H2O2, but not only NO, NO2, HNO2, HNO3, N2O5, SO2, SO3, H2SO4 as it was supposed before.

Starik, Alexander M.↗
NASA NTRS1997

Large-Scale Distributions of Tropospheric Nitric, Formic, and Acetic acids Over the Westerm Pacific Basin During Wintertime

We report here measurements of the acidic gases nitric (HNO3), formic (HCOOH), and acetic (CH3COOH) over the western Pacific basin during the February-March 1994 Pacific Exploratory Mission-West (PEM-West B). These data were obtained aboard the NASA DC-8 research aircraft as it flew missions in the altitude range of 0.3 - 12.5 km over equatorial regions near Guam and then further westward encompassing the entire Pacific Rim arc. Aged marine air over the equatorial Pacific generally exhibited mixing ratios of acidic gases less than 100 parts per trillion by volume (pptv). Near the Asian continent, discrete plumes encountered below 6 km altitude contained up to 8 parts per billion by volume (ppbv) HNO3 and 10 ppbv HCOOH and CH3COOH. Overall there was a general correlation between mixing ratios of acidic gases with those of CO, C2H2, and C2Cl4, indicative of emissions from combustion and industrial sources. The latitudinal distributions of HNO3 and CO showed that the largest mixing ratios were centered around 15 deg N, while HCOOH, CH3COOH, and C2Cl4 peaked at 25 deg N. The mixing ratios of HCOOH and CH3COOH were highly correlated (r(sup 2) = 0.87) below 6 km altitude, with a slope (0.89) characteristic of the nongrowing season at midlatitudes in the northern hemisphere. Above 6 km altitude, HCOOH and CH3COOH were marginally correlated (r(sup 2) = 0.50), and plumes well defined by CO, C2H2, and C2Cl4 were depleted in acidic gases, most likely due to scavenging during vertical transport of air masses through convective cloud systems over the Asian continent. In stratospheric air masses, HNO, mixing ratios were several parts per billion by volume (ppbv), yielding relationships with 03 and N2O consistent with those previously reported for NO(y).

Talbot, R. W.↗
NASA NTRS1999

Measurements of Nitric Acid and Aerosol Species Aboard the NASA DC-8 Aircraft During the SASS Ozone and Nitrogen Oxide Experiment (SONEX)

The SASS Ozone and Nitrogen Oxides Experiment (SONEX) over the North Atlantic during October/November 1997 offered an excellent opportunity to examine the budget of total reactive nitrogen (NO(sub y)) in the upper troposphere (8 - 12 km altitude). The median measured NO(sub y) mixing ratio was 425 parts per trillion by volume (pptv). Two different methods were used to measure HNO3: (1) the mist chamber technique and, (2) chemical ionization mass spectrometry. Two merged data sets using these HNO3 measurements were used to calculate NO(sub y) by summing the reactive nitrogen species (a combination of measured plus modeled results) and comparing the resultant values to measured NO(sub y) (gold catalytic reduction method). Both comparisons showed good agreement in the two quantities (slope > 0.9 and r(exp 2) > 0.9). Thus, the total reactive nitrogen budget in the upper troposphere over the North Atlantic can be explained in a general manner as a simple mixture of NO(sub x). (NO + NO2), HNO3, and PAN. Median values of NO(sub x)/NO(sub y) were approximately equal to 0.25, HNO3/NO(sub y) were approximately equal to 0.35 and Peroxyacetyl Nitrate (PAN)/NO(sub y) were approximately equal to 0. 17. Particulate NO3 and alkyl nitrates together composed <10 % of NO(sub y), while model estimated HNO4 averaged 12%.

Talbot, Robert W.↗