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At least 127 records · Page 7

Optical Studies of Nitrogen Oxides in the Stratosphere

Several observational approaches were used to study the oxides of nitrogen in the stratosphere. Two species are accessible in the visible range: NO2 (400 to 450 nm) and NO3 (620 to 670 nm). In the infrared NO, NO2 and HNO3 can be studied easily only if measurements are made from above the tropopause where the water density becomes low. Measurements were carried out both by ground-based techniques as well as aircraft and balloons.

Noxon, J. F.↗

MAP/GLOBUS campaign 1983

The major scientific objectives of the campaign are the accurate measurement of ozone and its short-term variability together with the determination of members of the NO sub x family as NO, NO2, NO3, N2O5, and HNO3. Related important solar fluxes (including scattered fluxes) shall be measured as much as possible. Other important trace species (as H2O) shall be determined simultaneously. The detailed scientific objectives for the ozone and NO sub x measurements are given. A further scientific objective is the study of atmospheric dynamics, especially of the meteorological background. Therefore special analysis will be performed of the data of respective network stations and satellites. Local wind and turbulence measurements will also be performed.

Offerman, D.↗

Role of chemotaxis in the ecology of denitrifiers

It has been recognized that the process of denitrification represents a major sequence in the nitrogen cycle. It involves the anaerobic reduction of nitrate or nitrite to nitrous oxide or elemental nitrogen. This process is responsible for significant losses of nitrogen from agricultural soils. Up to now, little attention has been paid to the ecology of the organisms responsible for denitrification. It is pointed out that chemotaxis would probably offer a strong competitive mechanism for denitrifiers, since chemotaxis would allow denitrifiers to actively reach nitrate by directed motility, rather than by random movement or diffusion of nitrate. The present investigation was initiated to examine the chemotactic responses of several denitrifiers to nitrate and nitrite. Attention is given to bacterial strains, culture media and cell preparation, chemotaxis assays, and competition experiments. It was found that several denitrifiers, including P. aeruginosa, P. fluorescens, and P. Stutzeri, were strongly attracted to NO3(-) and NO2(-).

Kennedy, M. J.↗

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.↗

Production rates of neon xenon isotopes by energetic neutrons

As a first step in an experimental program to study the behavior of noble gases produced in situ in minerals, a suite of minerals and pure chemicals were irradiated with 14.5 MeV neutrons at LLNL's Rotating Target Neutron Source (RTNS-II) and production rates for noble gases were determined. While neutron effects in meteorites and lunar samples are dominated by low-energy neutron capture, more energetic cosmic-ray secondary neutrons can provide significant depth-dependent contributions to production of cosmogenic nuclides through endothermic reactions such as (n,2n), (n,np), (n,d) and (n,alpha). Production rates for nuclides produced by cosmic-ray secondary neutrons are therefore useful in interpreting shielding histories from the relative abundances of cosmogenic nuclides. Absolute production cross sections were calculated from isotope dilution analyses of NaCl, Mg, CsCl, and Ba(NO3)2 samples, assuming purity, stoichiometry, and quantitative noble gas retention and extraction. Relative production cross sections determined from neon isotopic ratios in the mineral samples were also considered in evaluating the neon production cross sections. Results are presented.

Leich, D. A.↗

Evaluation of a catalytic reduction technique for the measurement of total reactive odd-nitrogen NOy in the atmosphere

The suitability of a technique for the measurement of total reactive odd-nitrogen NOy-containing species in the atmosphere has been examined. In the technique, an NOy component species, which may include NO, NO2, NO3, HNO3, peroxyacetyl nitrate, and particulate nitrate, are catalytically reduced by CO to form NO molecules on the surface of a metal converter tube, and the NO product is detected by chemiluminescence produced in reaction with O3. Among the catalysts tested in the temperature range of 25-500 C, Au was the preferred catalyst. The results of laboratory tests investigating the effects of pressure, O3, and H2O on NOy conversion, and the possible sources of interference, have shown that the technique is suitable for atmospheric analyses. The results of a test in ambient air at a remote ground-based field site are included.

Fahey, D. W.↗

Photochemistry of biogenic emissions over the Amazon forest

The boundary layer chemistry over the Amazon forest during the dry season is simulated with a photochemical model. Results are in good agreement with measurements of isoprene, NO, ozone, and organic acids. Photochemical reactions of biogenic isoprene and NOx can supply most of the ozone observed in the boundary layer. Production of ozone is very sensitive to the availability of NOx, but is insensitive to the isoprene source strength. High concentrations of total odd nitrogen (NOy) are predicted for the planetary boundary layer, about 1 ppb in the mixed layer and 0.75 ppb in the convective cloud layer. Most of the odd nitrogen is present as PAN-type species, which are removed by dry deposition to the forest. The observed daytime variations of isoprene are explained by a strong dependence of the isoprene emission flux on sun angle. Nighttime losses of isoprene exceed rates of reaction with NO3 and O3 and appear to reflect dry-deposition processes. The 24-hour averaged isoprene emission flux is calculated to be 38 mg/sq m per day. Photooxidation of isoprene could account for a large fraction of the CO enrichment observed in the boundary layer under unpolluted conditions and could constitute an important atmospheric source of formic acid, methacrylic acid, and pyruvic acid.

Jacob, Daniel J.↗

Biomass-burning emissions and associated haze layers over Amazonia

The characteristics of haze layers, which were visually observed over the central Amazon Basin during many of the Amazon Boundary Layer Experiment 2A flights in July/August 1985, were investigated by remote and in situ measurements, using the broad range of instrumentation and sampling equipment on board the Electra aircraft. It was found that these layers strongly influenced the chemical and optical characteristics of the atmosphere over the eastern Amazon Basin. Relative to the regional background, the concentrations of CO, CO2, O3, and NO were significantly elevated in the plumes and haze layers, with the NO/CO ratio in fresh plumes much higher than in the aged haze layers. The haze aerosol was composed predominantly of organic material, NH4, K(+), NO3(-), SO4(2-), and organic anions (formate, acetate, and oxalate).

Andreae, M. O.↗

Particulate emissions from a mid-latitude prescribed chaparral fire

Particulate emission from a 400-acre prescribed chaparral fire in the San Dimas Experimental Forest was investigated by collecting smoke aerosol on Teflon and glass-fiber filters from a helicopter, and using SEM and EDAX to study the features of the particles. Aerosol particles ranged in size from about 0.1 to 100 microns, with carbon, oxygen, magnesium, aluminum, silicon, calcium, and iron as the primary elements. The results of ion chromatographic analysis of aerosol-particle extracts (in water-methanol) revealed the presence of significant levels of NO2(-), NO3(-), SO4(2-), Cl(-), PO4(3-), C2O4(2-), Na(+), NH4(+), and K(+). The soluble ionic portion of the aerosol was estimated to be about 2 percent by weight.

Cofer, Wesley R., III↗

Antarctic polar stratospheric aerosols: The roles of nitrates, chlorides and sulfates

Nitric and hydrochloric acids have been postulated to condense in the winter polar stratosphere to become an important component of polar stratospheric clouds. One implication is that the removal of NO(y) from the gas phase by this mechanism allows high Cl(x) concentrations to react with O3, because the formation of ClNO3 is inhibited. Contributions of NO3 and Cl to the stratospheric aerosol were determined during the 1987 Airborne Antarctic Ozone Experiment by testing for the presence of nitrates and chlorides in the condensed phase. Aerosol particles were collected on four 500 micron diameter gold wires, each pretreated differently to give results that were specific to certain physical and chemical aerosol properties. One wire was carbon-coated for concentration and size analyses by scanning electron microscopy; X-ray energy dispersive analyses permitted the detection of S and Cl in individual particles. Three more wires were coated with Nitron, barium chloride and silver nitrate, respectively, to detect nitrate, sulfate and chloride in aerosol particles. All three ions, viz., sulfates, nitrates and chlorides were detected in the Antarctic stratospheric aerosol. In terms of number concentrations, the aerosol was dominated by sulfates, followed by chlorides and nitrates. An inverse linear regression can be established between nitrate concentrations and ozone mixing ratio, and between temperature and nitrates.

Pueschel, R. F.↗

Measurements of NO and total reactive odd-nitrogen, NOy, in the Antarctic stratosphere

Measurements of NO and total reactive N, NOy, were made as part of the Airborne Antarctic Ozone Experiment conducted in Punta Arenas, Chile during Aug. and Sept. 1987. The total reactive N reservoir includes the species NO, NO2, NO3, N2 O5, HNO3, and ClONO2. The instrument was located on board the NASA ER2 aircraft which conducted 12 flights over the Antarctic continent reaching altitudes of 18 km at 72 deg S latitude. The NOy technique utilized the conversion of component NOy species to NO on a gold catalyst and the subsequent detection of NO by the chemiluminescence reaction of NO with ozone. Since the inlet sample line is heated and the catalyst operates at 300 C, NOy incorporated in aerosols evaporates and is converted to NO. NO was measured on two separate flights by removing the catalyst from the sample inlet line.

Fahey, D. W.↗

The evolution of nitrogen cycling

The energetics of nitrogen transformation reactions and the evolution of nitrogen cycling are examined. It is suggested that meteor impact-produced fixed nitrogen could have caused the entire reservoir of the earth's N2 to convert into fixed nitrogen at the end of accretion. The abiotic fixation rate on the early earth by lightning is estimated at about 1-3 X 10 to the 16th molecules of NO/J. It is found that biological nitrogen fixation may have evolved after the development of an aerobic atmosphere. It is shown that HNO could eventually become NO2(-) and NO3(-) after reaching the earth's surface. It is concluded that the evolutionary sequence for the biological transformation of nitrogen compounds is ammonification - denitrification - nitrification - nitrogen fixation.

Mancinelli, Rocco L.↗

Bio-markers and the search for extinct life on Mars

In order to predict what biomarkers could be used on Mars, several biomarkers, or key signatures, of extinct life on earth are identified. Some of these biomarkers which may be applicable to Mars include reduced carbon and nitrogen compounds, CO3(2-), SO4(2-), NO3(-), Mg, Mn, Fe, and the isotopic ratios of C, N, and S. It is suggested that a fully equipped Mars rover might be able to perform analyses to measure most of these biomarkers while on the Martian surface.

Schwartz, D. E.↗

Condensed nitrate, sulfate, and chloride in Antarctic stratospheric aerosols

The 1987 Airborne Antarctic Ozone Experiment, in which the NO3, Cl, and SO4 contents of stratospheric aerosols were estimated, is discussed. The aerosol size and chemical composition measurements were carried out on samples collected during August 17 to September 4, 1987. The data indicate that condensed nitrate is found below a threshold temperature of 193.6 + or - 3.0 K, which is generally found at latitudes exceeding 64 deg S. A negative correlation exists between condensed nitrate and ozone correlation.

Pueschel, R. F.↗

Measurements of nitric oxide and total reactive nitrogen in the Antarctic stratosphere - Observations and chemical implications

Results are presented on measurements of NO and the sum of reactive nitrogen species, NO(y), which include NO, NO2, NO3, N2O5, HNO3, and ClONO2 (in addition to ClO, O3, H2O, and N2O measurements), obtained aboard the NASA ER-2 aircraft flying over the Antarctica between the latitudes of 53 and 72 deg S during the Airborne Antarctic Ozone Experiment. The boundary of the chemically perturbed region (CPR), as indicated by a sharp increase in the level of ClO, occurred near 66 deg S; outside or equatorward of the CPR, the NO(y) mixing ratios ranged between 6 and 12 ppbv, with values decreasing poleward and reaching total NO(y) levels of 4 ppbv or less within 5-deg poleward of the boundary. Data presented in this paper clearly associate the Antarctic ozone decrease with perturbed conditions of ClO, NO(y), and H2O, which are in turn associated with processes defined as nonstandard heterogeneous chemistry, denitrification, and dehydration, respectively.

Fahey, D. W.↗

Measuring tropospheric HNO3 - Problems and prospects for Nylon filter and mist chamber techniques

A series of laboratory and field measurements was performed to evaluate the mist chamber technique for determining tropospheric HNO3 concentrations. Both the mist chamber and standard Nylon filter techniques exhibit high collection efficiency and excellent agreement measuring HNO3 vapors from a permeation source. When simultaneously sampling ambient air in eastern Virginia, the Nylon filter measured an average of 70 percent higher HNO3 concentration than the mist chamber technique. The results indicate that O3 causes a low-level positive artifact interference in HNO3 measurements performed with the filter technique. This O3-induced error is small, however, compared to the large difference between atmospheric HNO3 concentrations determined with the two techniques. It is hypothesized that unidentified (organic?) nitrogen species in the atmosphere react for form NO3(-) on the filter and this phenomenon may interfere with Nylon filter measurements of HNO3 vapor. These potential interferences did not appear to affect measurements of HNO3 with the mist chamber method.

Talbot, R. W.↗

New insights in the photochemistry of grain mantles: The identification of the 4.62 and 6.87 micron bands

The mid-IR spectral region of molecular clouds is known to show the fingerprints of molecules frozen in the icy mantles of the interstellar grains. To study the complex chemical and physical interactions on the ice mantles accreted on grains in molecular clouds numerous UV irradiation and diffusion experiments were performed. The irradiation of binary ices was studied. Using isotopic labelling on NH3/CO and NH3/O2 ices numerous compounds were identified, of which OCN(-), NO2(-), NO3(-), and NH4(+) ions reveal a new type of chemical reactions. It appeared that these compounds were formed by proton transfer reactions induced by the interaction between an acid (HNCO, HNO2, HNO3) and a base (NH3) through a hydrogen bond. This mechanism was confirmed by a study of photolyzed diluted argon mixtures. The main astrophysically relevant data from the overall study are presented. The 4.62 micron band in W33A can be reproduced with NH3/CO containing irradiated ices and was identified with OCN(-). The 6.87 micron band in W33A and other photostellar objects is reproduced with NH3/O2 containing ices and is identified with NH4(+).

Grim, Ruud↗

Dynamics of vegetation and soils of oak/saw palmetto scrub after fire: Observations from permanent transects

Ten permanent 15 m transects previously established in two oak/saw palmetto scrub stands burned in December 1986, while two transects remained unburned. Vegetation in the greater than 0.5 m and the less than 0.5 m layers on these transects was sampled at 6, 12, 18, 24, and 36 months postburn and determined structural features of the vegetation (height, percent bare ground, total cover). The vegetation data were analyzed from each sampling by height layer using detrended correspondence analysis ordination. Vegetation data for the greater than 0.5 m layer for the entire time sequence were combined and analyzed using detrended correspondence analysis ordination. Soils were sampled at 6, 12, 18, and 24 months postburn and analyzed for pH, conductivity, organic matter, exchangeable cations (Ca, Mg, K, Na), NO3-N, NH4-N, Al, available metals (Cu, Fe, Mn, Zn), and PO4-P. Shrub species recovered at different rates postfire with saw palmetto reestablishing cover greater than 0.5 m within one year, but the scrub oaks had not returned to preburn cover greater than 0.5 m in 3 years after the fire. These differences in growth rates resulted in dominance shifts after the fire with saw palmetto increasing relative to the scrub oaks. Overall changes in species richness were minor, although changes occurred in species richness by height layers due to different growth rates. Soils of well drained and poorly drained sites differed markedly. Soil responses to the fire appeared minor. Soil pH increased at 6 and 12 months postfire; calcium increased at 6 months postburn. Nitrate-nitrogen increased at 12 months postburn. Low values of conductivity, PO4-P, Mg, K, Na, and Fe at 12 months postburn may be related to heavy rainfall the preceding month. Seasonal variability in some soil parameters appeared to occur.

Schmalzer, Paul A.↗