56 research outputs found
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O-3, NOY, AND NOX/NOY IN THE UPPER TROPOSPHERE OF THE EQUATORIAL PACIFIC
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MERIDIONAL DISTRIBUTIONS OF NO(X), NO(Y) AND OTHER SPECIES IN THE LOWER STRATOSPHERE AND UPPER TROPOSPHERE DURING AASE-II
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Observations of total RONO2 over the boreal forest: NO x sinks and HNO3 sources
In contrast with the textbook view of remote chemistry where HNO 3 formation is the primary sink of nitrogen oxides, recent theoretical analyses show that formation of RONO2 (Ī£ANs) from isoprene and other terpene precursors is the primary net chemical loss of nitrogen oxides over the remote continents where the concentration of nitrogen oxides is low. This then increases the prominence of questions concerning the chemical lifetime and ultimate fate of Ī£ANs. We present observations of nitrogen oxides and organic molecules collected over the Canadian boreal forest during the summer which show that Ī£ANs account for ā¼20% of total oxidized nitrogen and that their instantaneous production rate is larger than that of HNO3. This confirms the primary role of reactions producing Ī£ANs as a control over the lifetime of NOx (NOx =NO+NO2) in remote, continental environments. However, HNO 3 is generally present in larger concentrations than Ī£ANs indicating that the atmospheric lifetime of Ī£ANs is shorter than the HNO3 lifetime. We in-vestigate a range of proposed loss mechanisms that would explain the inferred lifetime of Ī£ANs finding that in combination with deposition, two processes are consistent with the observations: (1) rapid ozonolysis of isoprene nitrates where at least ā¼40% of the ozonolysis producs t ts release NOx from the carbon backbone and/or (2) hydrolysis of particulate organic nitrates with HNO3 as a product. Implications of these ideas for our understanding of NOx and NOy budget in remote and rural locations are discussed. Ā© Author(s) 2013
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Contribution of particulate nitrate to airborne measurements of total reactive nitrogen
Simultaneous measurements of speciated, total reactive nitrogen (NOy) and particulate NO3 (particle diameter <1.3 Ī¼m) were made on board the NASA P-3B aircraft over the western Pacific in February-April 2001 during the Transport and Chemical Evolution over the Pacific (TRACE-P) experiment. Gas-phase and particulate NOy was measured using a gold tube catalytic converter. For the interpretation of particulate NOy, conversion efficiencies of particulate NH4NO3, KNO3, NaNO3, and Ca(NO3)2 were measured in the laboratory. Only NH4NO3 showed quantitative conversion, and its conversion efficiency was as high as that for HNO3. NOy measured on board the aircraft was found to be systematically higher by 10-30% than the sum of the individual NOy gas components (Ī£(NOy)i) at 0-4 km. Particulate NO3- concentrations measured by a particle-into-liquid sampler (PILS) were nearly equal to NOy - Ī£(NOy)i under low-dust-loading conditions. The PILS data showed that the majority of the particulate NO3- was in the form of NH4NO3 under these conditions, suggesting that NH4NO3 particles were quantitatively converted to detectable NO by the NOy converter, consistent with the laboratory experiments. The contribution of particulate NO3- to NOy was most important at 0-2 km, where NO3- constituted 10-30% of NOy during TRACE-P. On average, the amounts of particulate NO3- and gas-phase HNO3 were comparable in this region. Copyright 2005 by the American Geophysical Union
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Synoptic-scale transport of reactive nitrogen over the western Pacific in spring
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Coupled evolution of BrOx-ClOx-HOx-NOx chemistry during bromine-catalyzed ozone depletion events in the arctic boundary layer
Extensive chemical characterization of ozone (O3) depletion events in the Arctic boundary layer during the TOPSE aircraft mission in March-May 2000 enables analysis of the coupled chemical evolution of bromine (BrOx), chlorine (ClOx), hydrogen oxide (HOx) and nitrogen oxide (NOx) radicals during these events. We project the TOPSE observations onto an O3 chemical coordinate to construct a chronology of radical chemistry during O3 depletion events, and we compare this chronology to results from a photochemical model simulation. Comparison of observed trends in ethyne (oxidized by Br) and ethane (oxidized by Cl) indicates that ClOx chemistry is only active during the early stage Of O3 depletion (O3 > 10 ppbv). We attribute this result to the suppression of BrCl regeneration as O3 decreases. Formaldehyde and peroxy radical concentrations decline by factors of 4 and 2 respectively during O3 depletion and we explain both trends on the basis of the reaction of CH2O with Br. Observed NOx concentrations decline abruptly in the early stages Of O3 depletion and recover as O3 drops below 10 ppbv. We attribute the initial decline to BrNO3 hydrolysis in aerosol, and the subsequent recovery to suppression of BrNO3 formation as O3 drops. Under halogen-free conditions we find that HNO4 heterogeneous chemistry could provide a major NOx sink not included in standard models. Halogen radical chemistry in the model can produce under realistic conditions an oscillatory system with a period of 3 days, which we believe is the fastest oscillation ever reported for a chemical system in the atmosphere
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Ozone depletion events observed in the high latitude surface layer during the TOPSE aircraft program
During the Tropospheric Ozone Production about the Spring Equinox (TOPSE) aircraft program, ozone depletion events (ODEs) in the high latitude surface layer were investigated using lidar and in situ instruments. Flight legs of 100 km or longer distance were flown 32 times at 30 m altitude over a variety of regions north of 58Ā° between early February and late May 2000. ODEs were found on each flight over the Arctic Ocean but their occurrence was rare at more southern latitudes. However, large area events with depletion to over 2 km altitude in one case were found as far south as Baffin Bay and Hudson Bay and as late as 22 May. There is good evidence that these more southern events did not form in situ but were the result of export of ozoneādepleted air from the surface layer of the Arctic Ocean. Surprisingly, relatively intact transport of ODEs occurred over distances of 900ā2000 km and in some cases over rough terrain. Accumulation of constituents in the frozen surface over the dark winter period cannot be a strong prerequisite of ozone depletion since latitudes south of the Arctic Ocean would also experience a long dark period. Some process unique to the Arctic Ocean surface or its coastal regions remains unidentified for the release of ozoneādepleting halogens. There was no correspondence between coarse surface features such as solid ice/snow, open leads, or polynyas with the occurrence of or intensity of ozone depletion over the Arctic or subarctic regions. Depletion events also occurred in the absence of longārange transport of relatively fresh āpollutionā within the high latitude surface layer, at least in spring 2000. Direct measurements of halogen radicals were not made. However, the flights do provide detailed information on the vertical structure of the surface layer and, during the constant 30 m altitude legs, measurements of a variety of constituents including hydroxyl and peroxy radicals. A summary of the behavior of these constituents is made. The measurements were consistent with a source of formaldehyde from the snow/ice surface. Median NOx in the surface layer was 15 pptv or less, suggesting that surface emissions were substantially converted to reservoir constituents by 30 m altitude and that ozone production rates were small (0.15ā1.5 ppbv/d) at this altitude. Peroxyacetylnitrate (PAN) was by far the major constituent of NOy in the surface layer independent of the ozone mixing ratio
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