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At least 217 records · Page 12

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.↗

Redistribution of reactive odd nitrogen in the lower arctic stratosphere

In-situ measurements of total reactive odd nitrogen NO(y), were made from the NASA DC-8 aircraft in the lower arctic stratosphere during the 1989 Airborne Arctic Stratospheric Expedition. Throughout January and February, NO(y) mixing ratios were typically between 0.5 and 3 parts per billion by volume (ppbv) at altitudes between 10 and 12.5 km. During several flights late in the mission, events of unusually light NO(y) occurred with mixing ratios up to 12 ppbv at these altitudes. Simultaneous measurements of N2O, O3, and H2O during these events suggest that large changes in NO(y) are not expected. The elevated NO(y) values are interpreted as a vertical redistribution of NO(y) in the lower stratosphere resulting from gravitational sedimentation of aerosol particles containing HNO3. No evidence of the redistribution of H2O is noted, consistent with observations of denitrification without dehydration higher in the stratosphere.

Huebler, G.↗

Simulating the evolution of the chemical composition of the 1988/89 winter vortex

During the 1988/89 Airborne Arctic Stratospheric Expedition (AASE) observations of the chemical composition and aerosol characteristics of the winter vortex were obtained from a NASA ER-2 aircraft. In this paper we present interpretations of observations obtained on three ER-2 flights using a Lagrangian coupled photochemical-microphysical model. It is argued that observations obtained on Jaunary 16 and 19, and February 10, represent different stages of the chemical evolution of the vortex, from the early stages of chlorine release, the onset of denitrification and the intensively processed state.

Jones, R. L.↗

Emission of nitric oxide (NO) from tropical forest soils and exchange of NO between the forest canopy and atmospheric boundary layers

Emissions of NO from soils in the Amazon rain forest were measured at 66 locations using an enclosure technique, and continuous vertical profiles of NO and O3 were measured between the ground and 41-m altitude. Fluxes of NO averaged 8.9 (+ or - 1.5) x 10 to the 9th molecules/sq cm per sec from the dominant (yellow clay) soils of the region, with larger fluxes observed from adjacent white sand soils. Fluxes from clay soils were lower by more than a factor of 5 than fluxes observed during the dry season at a nearby site. Low soil emission rates were reflected in lower concentrations of NO at the top of the forest canopy in the wet season, only 30-50 parts per trillion by volume during the daytime. The measured fluxes are consistent with chemical mass balances for NO within the forest canopy, calculated from the NO and O3 profiles taken at night, and with observations of NO between 150 and 5000 m altitude. Measurements of NO emission rates from soil plots fertilized using NaNO3, NH4Cl, or sucrose indicated that a reductive pathway (denitrification) may have been primarily responsible for production of the NO released by both clay and sand soils.

Bakwin, Peter S.↗

Measurements in polar stratospheric clouds over Antarctica in September 1989

The results of six balloon flights at McMurdo Station, Antarctica, under varying temperature conditions, are used in a study of polar stratospheric clouds during Sept. 1989. A particle counter, with size resolution in the 0.5 micron radius region, indicates that cloud size distributions are always bimodal. Mode radii ranging from 0.05 to 0.10 microns were observed for the small particle mode, representing the sulfate layer or condensational growth enhancements of it. The data are not inconsistent with the expected increase in size with decreasing temperature of the small particle mode in the sulfate layer owing to deliquescence although this phenomenon is often masked by nitric acid trihydrate (NAT) condensation when temperatures are sufficiently low. Mode radii generally ranged from 1.5 to 3.5 micron for the large particle mode at concentrations 3 to 4 orders of magnitude lower than the small particle mode. The large particle mode, which normally comprises most of the mass, is presumably caused by NAT condensation on larger particles of the sulfate layer and indicates HNO3 mixing ratios of 1 to 5 ppbv for most of the cloud layers observed, suggesting substantial denitrification. On several occasions, distributions were observed with mode radii as high as 7 microns, and correspondingly large inferred mass, indicating water ice clouds in the 12 to 15 km region. On other occasions, absence of such clouds at very low temperatures indicated water vapor mixing ratios of less than 3 ppmv suggesting dehydration. Generally, the inferred HNO3 mixing ratios were higher in the lower stratosphere, suggesting redistribution through particle sedimentation.

Deshler, Terry↗

Fourier transform infrared studies of model polar stratospheric cloud surfaces - Growth and evaporation of ice and nitric acid/ice

Fourier-transform infrared surface studies are used to probe the microphysical properties of nitric acid trihydrate (NAT) and ice films representative of type I and II polar stratospheric clouds (PSC). Experiments indicate that, on initial exposure to 1.8 microtorr of HNO3, a layer of ice is quantitatively converted to NAT. However, conversion of ice to NAT does not proceed indefinitely, but rather the system reaches saturation. For longer exposures or higher HNO3 pressures, NAM becomes the dominant nitric acid containing species on the surface. Evaporation studies were performed to test the feasibility of a recent denitrification mechanism. The results indicate that ice coated with 0.20 micron of NAT evaporates at a temperature of about 4 C higher than uncoated ice.

Tolbert, Margaret A.↗

Biospheric-atmospheric coupling on the early Earth

Theoretical calculations performed with a one-dimensional photochemical model have been performed to assess the biospheric-atmospheric transfer of gases. Ozone reached levels to shield the Earth from biologically lethal solar ultraviolet radiation (220-300 nm) when atmospheric oxygen reached about 1/10 of its present atmospheric level. In the present atmosphere, about 90 percent of atmospheric nitrous oxide is destroyed via solar photolysis in the stratosphere with about 10 percent destroyed via reaction with excited oxygen atoms. The reaction between nitrous oxide and excited oxygen atoms leads to the production of nitric oxide in the stratosphere, which is responsible for about 70 percent of the global destruction of oxygen in the stratosphere. In the oxygen/ozone deficient atmosphere, solar photolysis destroyed about 100 percent of the atmospheric nitrous oxide, relegating the production of nitric oxide via reaction with excited oxygen to zero. Our laboratory and field measurements indicate that atmospheric oxygen promotes the biogenic production of N2O and NO via denitrification and the biogenic production of methane by methanogenesis.

Levine, J. S.↗

ATLAS: Airborne Tunable Laser Absorption Spectrometer for stratospheric trace gas measurements

The ATLAS instrument is an advanced technology diode laser based absorption spectrometer designed specifically for stratospheric tracer studies. This technique was used in the acquisition of N2O tracer data sets on the Airborne Antarctic Ozone Experiment and the Airborne Arctic Stratospheric Expedition. These data sets have proved valuable for comparison with atmospheric models, as well as in assisting in the interpretation of the entire ensemble of chemical and meteorological data acquired on these two field studies. The N2O dynamical tracer data set analysis revealed several ramifications concerning the polar atmosphere: the N2O/NO(y) correlation, which is used as a tool to study denitrification in the polar vertex; the N2O Southern Hemisphere morphology, showing subsidence in the winter polar vortex; and the value of the N2O measurements in the interpretation of ClO, O3, and NO(y) measurements and of the derived dynamical tracer, potential vorticity. Field studies also led to improved characterization of the instrument and to improved accuracy.

Loewenstein, Max↗

Particle chemistry impactor experiment

Polar stratospheric cloud (PSC) particles are collected on impactors and studied with regard to physical and chemical properties to help explain the importance of heterogeneous chemical reactions for stratospheric ozone depletion. The nitric, hydrochloric, and sulfuric acid content of stratospheric aerosol particles collected at 18 km altitude was determined. It is suggested that nitric acid is a component of polar stratospheric clouds. This is important for two reasons: (1) it proves that chlorine activation takes place at the surface of PSC particles by converting chemically inert chlorine nitrate to chlorine radicals that can react with ozone; and (2) if the PSC particles are large enough to settle out from the stratosphere, the possibility of nitric acid removal can result in the denitrification of the stratosphere.

Pueschel, R. F.↗

Upper-atmosphere Aerosols: Properties and Natural Cycles

The middle atmosphere is rich in its variety of particulate matter, which ranges from meteorite debris, to sulfate aerosols, to polar stratospheric ice clouds. Volcanic eruptions strongly perturb the stratospheric sulfate (Junge) layer. High-altitude 'noctilucent' ice clouds condense at the summer mesopause. The properties of these particles, including their composition, sizes, and geographical distribution, are discussed, and their global effects, including chemical, radiative, and climatic roles, are reviewed. Polar stratospheric clouds (PSCs) are composed of water and nitric acid in the form of micron-sized ice crystals. These particles catalyze reactions of chlorine compounds that 'activate' otherwise inert chlorine reservoirs, leading to severe ozone depletions in the southern polar stratosphere during austral spring. PSCs also modify the composition of the polar stratosphere through complex physiocochemical processes, including dehydration and denitrification, and the conversion of reactive nitrogen oxides into nitric acid. If water vapor and nitric acid concentrations are enhanced by high-altitude aircraft activity, the frequency, geographical range, and duration of PSCs might increase accordingly, thus enhancing the destruction of the ozone layer (which would be naturally limited in geographical extent by the same factors that confine the ozone hole to high latitudes in winter). The stratospheric sulfate aerosol layer reflects solar radiation and increases the planetary albedo, thereby cooling the surface and possibly altering the climate. Major volcanic eruptions, which increase the sulfate aerosol burden by a factor of 100 or more, may cause significant global climate anomalies. Sulfate aerosols might also be capable of activating stratospheric chlorine reservoirs on a global scale (unlike PCSs, which represent a localized polar winter phenomenon), although existing evidence suggests relatively minor perturbations in chlorine chemistry. Nevertheless, if atmospheric concentrations of chlorine (associated with anthropogenic use of chlorofluorocarbons) continue to increase by a factor of two or more in future decades, aircraft emissions of sulfur dioxide and water vapor may take on greater significance.

Turco, Richard P.↗

Composition measurements of the 1989 Arctic winter stratosphere by airborne infrared solar absorption spectroscopy

The paper reports simultaneous measurements of the stratospheric burdens of H2O, HDO, OCS, CO2, O3, N2O, CO, CH4, CF2Cl2, CFCl3, CHF2Cl, C2H6, HCN, NO, NO2, HNO3, ClNO3, HOCl, HCl, and HF made by the JPL MkIV interferometer on board the NASA DC-8 aircraft during January and early February 1989 as part of the Airborne Arctic Stratosphere Experiment. Data were obtained on 11 flights at altitudes of up to 12 km over a geographic region covering the NE Atlantic Ocean, Iceland, and Greenland. Analyses of the chemically active gases reveal highly perturbed conditions within the vortex. The ClNO3 abundance was chemically enhanced near the edge of the vortex but was then depleted inside. NO2 was severely depleted inside the vortex. In contrast to Antarctica, H2O and HNO3 were both more abundant inside the vortex than outside. It is suggested that although the Arctic vortex did not get cold enough to produce any dehydration, or as vertically extensive denitrification as occurred in Antarctica, nevertheless, enough heterogeneous chemistry occurred to convert over 90 percent of the inorganic chlorine to active forms in the 14- to 27-km altitude range by early February 1989.

Toon, G. C.↗

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.↗

A toy model for estimating N2O emissions from natural soils

A model of N2O emissions from natural soils, whose ultimate objective is to evaluate what contribution natural ecosystems make to the global N2O budget and how the contribution would change with global change, is presented. Topics covered include carbon and nitrogen available in the soil, delivery of nitrifiable N, soil water and oxygen status, soil water budget model, effects of drainage, nitrification and denitrification potentials, soil fertility, N2O production, and a model evaluation. A major implication of the toy model is that the tropics account for more than 80 percent of global emission.

Fung, Inez↗

Evolution of chemically processed air parcels in the lower stratosphere

Aircraft, ground-based, and satellite measurements indicate large concentrations of ClO in the lower stratosphere in and near the polar vortex. The amount of local ozone depletion caused by these large ClO concentrations will depend on the relative rates of ozone loss and ClO recovery. ClO recovery occurs when NO(x), from HNO3 photolysis, reacts with ClO to form ClONO2. We show that air parcels with large amounts of ClO will experience a subsequent ozone depletion that depends on the solar zenith angle. When the solar zenith angle is large in the middle of winter, the recovery of the ClO concentration in the parcel is slow relative to ozone depletion. In the spring, when the solar zenith angle is smaller, the ClO recovery is much faster. After ClO recovery, the chlorine chemistry has not returned to normal. The ClO has been converted to ClONO2. ClO production from further encounters with PSCs will be limited by the heterogeneous reaction of ClONO2 with water. Large ozone depletions, of the type seen in the Antarctic, occur only if there is significant irreversible denitrification in the air parcel.

Stolarski, Richard S.↗

Counting Condensation Nuclei in the Antarctic Ozone Mission

The work done on this grant primarily concerns the measurement of aerosol in the stratosphere from NASA ER-2 aircraft in studies of stratospheric ozone depletion in the northern and southern hemispheres. The ER-2 Condensation Nucleus Counter (CNC) measures the number concentration of particles in the diameter range of approximately 0.01 to 1 micron. The Passive Cavity Aerosol Spectrometer measures size distributions in the 0.17 to 3 micron diameter range. This instrument was upgraded during this grant period to a Focused Cavity Aerosol Spectrometer (FCAS). This upgrade permitted the instrument to measure particles as small as 0.05 micron in diameter. The inlet for the PCAS and FCAS was modified and characterized under this grant so that the modifications to the aerosol due to anisokinetic sampling and heating upon sampling and in transport to the measurement location were accounted for in the data analysis. These measurements permitted observations of particle production in the southern hemisphere winter polar vortex and observation of the impact of denitrification on the number concentration of the aerosol in the denitrified air. In the northern polar vortex, the measurements provided a characterization of the sulfate aerosol. Following the eruption of Mount Pinatubo in 1991, the measurements permitted an accurate characterization of the sulfate aerosol enhancements resulting from the eruption. This led to studies of the impact of heterogeneous chemistry on the partitioning of the partitioning of the reactive nitrogen species and the partitioning of the chlorine reservoir.

Wilson, James Charles↗

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.↗

New observations of the NOy/N2O correlation in the lower stratosphere

During the Airborne Arctic Stratospheric Expedition 2 (AASE 2), September 1991 through March 1992, in situ measurements of reactive nitrogen (NO(y) and N20 were made in the Northern Hemisphere lower stratosphere. We present an analysis of this new data and compare it with results from similar data taken during AASE in the winter of 1989. In the Northern Hemisphere there is consistent linear correlation of N2O and NO(y) which shows no interannual variation. Cases of departure from a linear correlation are examined and classified as being due to denitrification (NO(y) loss) or sampling air from a region where the photochemical lifetime of NO(y) is decreased. The latter case was observed for the first time in the winter of 1992.

Loewenstein, M.↗

Short term responses of nitrogen trace gas emissions to nitrogen fertilization in tropical sugar cane: Variations due to soils and management practices

Nitrogen (N) fertilization of agricultural systems is thought to be a major source of the increase in atmospheric N2O; NO emissions from soils have also been shown to increase due to N fertilization. While N fertilizer use is increasing rapidly in the developing world and in the tropics, nearly all of our information on gas emissions is derived from studies of temperate zone agriculture. Using chambers, we measured fluxes of N2O and NO following urea fertilization in tropical sugar cane systems growing on a variety of soil types in the Hawaiian Islands, USA. On the island of Maui, where urea is applied in irrigation lines and soils are mollisols and inceptisols, N2O fluxes were elevated for a week or less following fertilization; maximum average fluxes were typically less than 30 ng cm(exp -2)/ h. NO fluxes were often an order of magnitude less than N2O. Together, N2O and NO represented from 0.01 - 0.5% of the applied N. In fields on the island of Hawaii, where urea is broadcast on the surface and soils are andisols, N2O fluxes were similar in magnitude to Maui but remained elevated for much longer periods after fertilization. NO emissions were 2-5 times higher than N2O through most of the sampling periods. Together the gases loss represented approximately 1. 1 - 3% of the applied N. Laboratory studies indicate that denitrification is a critical source of N2O in Maui, but that nitrification is more important in Hawaii. Experimental studies suggest that differences in the pattern of N2O/NO and the processes producing them are a result of both carbon availability and placement of fertilizer, and that the more information-intensive fertilizer management practice results in lower emissions.

Matson, P. A.↗