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A model for studying the composition and chemical effects of stratospheric aerosols

We developed polynomial expressions for the temperature dependence of the mean binary and water activity coefficients for H2SO4 and HNO3 solutions. These activities were used in an equilibrium model to predict the composition of stratospheric aerosols under a wide range of environmental conditions. For typical concentrations of H2O, H2SO4, HNO3, HCl, HBr, HF, and HOCl in the lower stratosphere, the aerosol composition is estimated as a function of the local temperature and the ambient relative humidity. For temperatures below 200 K, our results indicate that (1) HNO3 contributes a significant mass fraction to stratospheric aerosols, and (2) HCl solubility is considerably affected by HNO3 dissolution into sulfate aerosols. We also show that, in volcanically disturbed periods, changes in stratospheric aerosol composition can significantly alter the microphysics that leads to the formation of polar stratospheric clouds. The effects caused by HNO3 dissolution on the physical and chemical properties of stratospheric aerosols are discussed.

Tabazadeh, Azadeh↗

A study of Type I polar stratospheric cloud formation

Mechanisms for the formation of Type I (nitric acid-based) polar stratospheric clouds (PSCs) are discussed. If the pre-existing sulfate aerosols are liquid prior to PSC formation, then nitric acid particles (Type Ib) form by HNO3 dissolution in aqueous H2SO4 solution droplets. This process does not require a nucleation step for the formation of HNO3 aerosols, so most pre-existing aerosols grow to become relatively small HNO3-containing particles. At significantly lower temperatures, the resulting supercooled solutions (Type Ib) may freeze to form HNO3 ice particles (Type Ia). If the pre-existing sulfate aerosols are initially solid before PSC formation, then HNO3 vapor can be deposited directly on the frozen sulfate particles. However, because an energy barrier to the condensation exists a nucleation mechanism is involved. Here, we suggest a unique nucleation mechanism that involves formation of HNO3/H20 solutions on the sulfate ice particles. These nucleation processes may be highly selective, resulting in the formation of relatively small number of large particles.

Tabazadeh, A.↗

Seasonal variation of atmospheric nitric acid over the South Pole in 1992

We conducted year-around measurements of mid infrared atmospheric emission over the South Pole in 1992. We were able to observe a large seasonal change of the total column of nitric acid (HNO3) vapor. During the summer the HNO3 column abundance was about 2 x 10(exp 16) molecules/sq cm. There was a small increase in the fall. A rapid decrease of 50% was observed in late June, soon after the stratospheric temperature reached the threshold for formation of type I polar stratospheric clouds (PSCs). By early July, the stratospheric temperature was cold enough to form type II PSCs, and the HNO3 column decreased to 7 x 10(exp 15) molecules/sq cm. Measured nitric acid values in the spring remained extremely low even after the stratosphere warmed well above PSC temperatures. This may indicate permanent removal of HNO3 by gravitational settling, or long-term sequestering in large particles. Normal summer values were not observed until the vortex dissipated and allowed the lateral transport of HNO3 to the south polar region.

Allen, Renate Van↗

Nitrogen Species in the Post-Pinatubo Stratosphere: Model Analysis Utilizing UARS Measurements

We present an analysis of the impact of heterogeneous chemistry on the partitioning of nitrogen species measured by the Upper Atmosphere Research Satellite (UARS) instruments. The UARS measurements utilized include: N2O, HNO3 and ClONO2 (Cryogen Limb Array Etalon Spectrometer (CLAES), version 7), temperature, methane, ozone, H2O, HCl, NO and NO2 (HALogen Occultation Experiment (HALOE), version 18). The analysis is carried out for the data from January 1992 to September 1994 in the 100-1 mbar (approx.17-47 km) altitude range and over 10 degree latitude bins from 70degS to 70degN. Temporal-spatial evolution of aerosol surface area density (SAD) is adopted according to the Stratospheric Aerosol and Gas Experiment (SAGE) 11 data. A diurnal steady-state photochemical box model, constrained by the temperature, ozone, H2O, CH4, aerosol SAD and columns of O2 and O3 above the point of interest, has been used as the main tool to analyze these data. Total inorganic nitrogen (NO(y)) is obtained by three different methods: (1) as a sum of the UARS measured NO, NO2, HNO3, and ClONO2; (2) from the N2O-NO(y) correlation, and (3) from the CH4-NO(y) correlation. To validate our current understanding of stratospheric heterogeneous chemistry for post-Pinatubo conditions, the model-calculated NO(x)/NO(y) ratios and the NO, NO2, and HNO3 profiles are compared to the UARS-derived data. In general, the UARS-constrained box model captures the main features of nitrogen species partitioning in the post-Pinatubo years. However, the model underestimates the NO2 content, particularly, in the 30-7 mbar (approx. 23-32 km) range. Comparisons of the calculated temporal behavior of the partial columns of NO2 and HNO3 and ground based measurements at 45degS and 45degN are also presented. Our analysis indicates that ground-based and HALOE v. 18 measurements of the NO2 vertical columns are consistent within the range of their uncertainties and are systematically higher (up to 50%) than the model results at mid-latitudes in both hemispheres. Reasonable agreement is obtained for HNO3 columns at 45degS suggesting some problems with nitrogen species partitioning in the model. Outstanding uncertainties are discussed.

Danilin, M. Y.↗

Nitrogen Species in the Post-Pinatubo Stratosphere: Model Analysis Utilizing UARS Measurements

We present an analysis of the impact of heterogeneous chemistry on the partitioning of nitrogen species measured by the Upper Atmosphere Research Satellite (UARS) instruments. The UARS measurements utilized include: N2O, HNO3 and ClONO2 (Cryogen Limb Array Etalon Spectrometer (CLAES), version 7), temperature, methane, ozone, H2O, HCI, NO and NO2 (HALogen Occultation Experiment (HALOE), version 18). The analysis is carried out for the data from January 1992 to September 1994 in the 100-1 mbar (approximately 17-47 km) altitude range and over 10 degree latitude bins from 70 deg S to 70 deg N. Temporal-spatial evolution of aerosol surface area density (SAD) is adopted according to the Stratospheric Aerosol and Gas Experiment (SAGE) II data. A diurnal steady-state photochemical box model, constrained by the temperature, ozone, H2O, CH4, aerosol SAD and columns of O2 and O3 above the point of interest, has been used as the main tool to analyze these data. Total inorganic nitrogen (NOy) is obtained by three different methods: (1) as a sum of the UARS measured NO, NO2, HNO3, and CIONO2; (2) from the N2O-NOy correlation, (3) from the CH4-NOy correlation. To validate our current understanding of stratospheric heterogeneous chemistry for post-Pinatubo conditions, the model-calculated NOx/NOy ratios and the NO, NO2, and HNO3 profiles are compared to the UARS-derived data. In general, the UARS-constrained box model captures the main features of nitrogen species partitioning in the post-Pinatubo years. However, the model underestimates the NO2 content, particularly, in the 30-7 mbar (approximately 23-32 km) range. Comparisons of the calculated temporal behavior of the partial columns of NO2 and HNO3 and ground based measurements at 45 deg S and 45 deg N are also presented. Our analysis indicates that ground-based and HALOE v.18 measurements of the NO2 vertical columns are consistent within the range of their uncertainties and are systematically higher (up to 50%) than the model results at mid-latitudes in both hemispheres. Reasonable agreement is obtained for HNO3 columns at 45 deg S suggesting some problems with nitrogen species partitioning in the model. Outstanding uncertainties are discussed.

Danilin, M. Y.↗

Balloon-Borne Measurements of Total Reactive Nitrogen, Nitric Acid, and Aerosol in the Cold Arctic Stratosphere

Total reactive nitrogen (NO(Y)) between 15 and 29 km was measured for the first time on board a balloon within the Arctic cold vortex. Observations of HNO3, aerosol, and ozone were made by instruments on the same balloon gondola which was launched from Esrange, Sweden (68 deg N, 20 deg E) on January 23, 1989. The NO(y) mixing ratio was observed to increase very rapidly from 6 ppbv at 18 km altitude to a maximum of 21 ppbv at 21 km, forming a sharp layer with a thickness of about 2 km. A minimum in the NO(y) mixing ratio of 5 ppbv was found at 27 km. The measured HNO3 profile shows broad similarities to that of NO(y). This observation, together with the observed very low column amount of NO2, shows that NO(x) had been almost totally converted to HNO3, and that NO(y) was composed mainly of HNO3. The enhanced aerosol concentration between 19 and 22 km suggests that the maximum abundance of HNO3 trapped in the form of nitric acid trihydrate (NAT) was about 6 ppbv at 21 km. The sampled air parcels were highly supersaturated with respect to NAT. Although extensive denitrification throughout the stratosphere did not prevail, an indication of denitrification was found at altitudes of 27 and 22 km, and between 18 and 15 km.

Kondo, Y.↗

Nitrogen Species in the Post-Pinatubo Stratosphere: Model Analysis Utilizing UARS Measurements

We present an analysis of the impact of heterogeneous chemistry on the partitioning of nitrogen species measured by the Upper Atmosphere Research Satellite (UARS) instruments. The UARS measurements utilized include N2O, HNO3, and ClONO2 from the cryogenic limb array etalon spectrometer (CLAES), version 7 (v.7), and temperature, methane, ozone, H2O, HCl, NO and NO2 from the halogen occultation experiment (HALOE), version 18. The analysis is carried out for the UARS data obtained between January 1992 and September 1994 in the 100- to 1-mbar (approx. 17-47 km) altitude range and over 10 deg latitude bins from 70 deg S to 70 deg N. The spatiotemporal evolution of aerosol surface area density (SAD) is adopted from analysis of the Stratospheric Aerosol and Gas Experiment (SAGE) II data. A diurnal steady state photochemical box model, constrained by the temperature, ozone, H2O, CH4, aerosol SAD, and columns of O2 and O3 above the point of interest, has been used as the main tool to analyze these data. Total inorganic nitrogen (NOY) is obtained by three different methods: (1) as a sum of the UARS-measured NO, NO2, HNO3, and ClONO2; (2) from the N2O-NOY correlation; and (3) from the CH4-NOY correlation. To validate our current understanding of stratospheric heterogeneous chemistry for post-Pinatubo conditions, the model-calculated monthly averaged NO(x)/NO(y) ratios and the NO, NO2, and HNO3 profiles are compared with the UARS-derived data. In general, the UARS-constrained box model captures the main features of nitrogen species partitioning in the post-Pinatubo years, such as recovery of NO(x) after the eruption, their seasonal variability and vertical profiles. However, the model underestimates the NO2 content, particularly in the 30- to 7-mbar (approx. 23-32 km) range. Comparisons of the calculated temporal behavior of the partial columns of NO2 and HNO3 and ground-based measurements at 45 deg S and 45 deg N are also presented. Our analysis indicates that ground-based and HALOE v.18 measurements of the NO2 vertical columns are consistent within the range of their uncertainties and are systematically higher (up to 50%) than the model results at midlatitudes in both hemispheres. Reasonable agreement is obtained for HNO3 columns at 45 deg S, suggesting some problems with nitrogen species partitioning in the model. Outstanding uncertainties are discussed.

Danilin, Michael Y.↗

Nitrogen Species in the Post-Pinatubo Stratosphere: Model Analysis Utilizing UARS Measurements

We present an analysis of the impact of heterogeneous chemistry on the partitioning of nitrogen species measured by the Upper Atmosphere Research Satellite (UARS) instruments. The UARS measurements utilized include N2O, HNO3, and ClONO2 from the cryogenic limb array etalon spectrometer (CLAES), version 7 (v.7), and temperature, methane, ozone, H2O, HCl, NO and NO2 from the halogen occultation experiment (HALOE), version 18. The analysis is carried out for the UARS data obtained between January 1992 and September 1994 in the 100-to 1-mbar (approx. 17-47 km) altitude range and over 10 degrees latitude bins from 70 S to 70 N. The spatiotemporal evolution of aerosol surface area density (SAD) is adopted from analysis of the Stratospheric Aerosol and Gas Experiment (SAGE) II data. A diurnal steady state photochemical box model, constrained by the temperature, ozone, H2O, CH4, aerosol SAD, and columns of O2 and O3 above the point of interest, has been used as the main tool to analyze these data. Total inorganic nitrogen (NOy) is obtained by three different methods: (1) as a sum of the UARS-measured NO, NO2, HNO3, and ClONO2; (2) from the N2O-NOy correlation, and (3) from the CH4-NOy correlation. To validate our current understanding of stratospheric heterogeneous chemistry for post-Pinatubo conditions, the model-calculated monthly averaged NOx/NOy ratios and the NO, NO2, and HNO3 profiles are compared with the UARS-derived data. In general, the UARS-constrained box model captures the main features of nitrogen species partitioning in the post-Pinatubo years, such as recovery of NOx after the eruption, their seasonal variability and vertical profiles. However, the model underestimates the NO2 content, particularly in the 30- to 7-mbar (approx.23-32 km) range. Comparisons of the calculated temporal behavior of the partial columns of NO2 and HNO3 and ground-based measurements at 45 S and 45 N are also presented. Our analysis indicates that ground-based and HALOE v.18 measurements of the NO2 vertical columns are consistent within the range of their uncertainties and are systematically higher (up to 50%) than the model results at midlatitudes in both hemispheres. Reasonable agreement is obtained for HNO3 columns at 45 S, suggesting some problems with nitrogen species partitioning in the model. Outstanding uncertainties are discussed.

Danilin, Michael Y.↗

Gas-rich minerals in the Allende meteorite - Attempted chemical characterization

A ten-step etching experiment with HNO3 was performed on a chromite-carbon residue from Allende, in order to characterize the HNO3-soluble minor phase 'Q' that contains most of the primordial Ar, Kr, and Xe. Each etch fraction was analyzed by neutron activation analysis for Cr, Fe, Co, Ir, and Au. The results suggest that Q consists of two minerals, each comprising about 5 per cent of the residue. Phase Q1, of Fe/Cr ratio greater than 20, is soluble in cold dilute HNO3 and seems to contain most of the heavy noble gases. It may be an HCl-insoluble sulfide of nominal composition (Fe84Ni12Cr4)Sx. Phase Q2, of Fe/Cr ratio about 0.5 and somewhat enriched in Co, is slowly soluble in hot concentrated HNO3 and seems to be at least an order of magnitude poorer in heavy noble gases than Q1. It may be daubre-elite or an acid-soluble variety of chromite.

Gros, J.↗

An intercomparison of nitrogen-containing species in Nimbus 7 LIMS and SAMS data

Odd-nitrogen chemistry and transport are analyzed using a two-dimensional model and Nimbus 7 data. The Nimbus 7 data include: measurements of O3, NO2, HNO3, H2O, and temperature by the LIMS instrument; N2O, CH4, and temperature measurements by the SAMS instrument; and O3 data from the SBUV instrument. The characteristics of the two-dimensional model used in the study, a modified Guthrie et al. (1984) model, are described. NO2 and HNO3 are calculated using the two-dimensional model, and the computed data are compared with the LIMS NO2 and HNO3 measurements. The model uncertainties are computed based on the photochemical equilibrium assumption, and the role of stratospheric dynamics in determining NO2 and HNO3 is discussed. It is observed that there is good correlation between the LIMS and model data in the upper stratosphere; however, the data do not correspond in the lower stratosphere. The effect of nitrogen sources, such as lightning, on the stratospheric odd nitrogen distribution is examined.

Jackman, Charles H.↗

Infrared aircraft measurements of stratospheric composition over Antarctica during September 1987

The JPL Mark IV interferometer recorded high resolution, infared solar spectra from the NASA DC-8 aircraft during flights over Antarctica in September 1987. The atmospheric absorption features in these spectra were analyzed to determine the overburdens of O3, NO, NO2, HNO3, ClONO2, HCl, HF, CH4, N2O, CO, H2O and CFC-12. The spectra were obtained at latitudes which ranged between 64 degrees S and 86 degrees S, allowing the composition in the interior of the polar vortex to be compared with that at the edge. The latitude dependence observed for NO, HO2, HNO3, ClONO2, HCl and HF are summerized. The values at 30 deg S were observed on the ferry flight from New Zealand to Hawaii. The dashed lines connecting the two were interpolated across the region for which there are no measurements. The chemically perturbed region is seen to consist of a collar of high HNO3 and ClONO2 surrounding a core in which the overburdens of these and of HCl and NO2 are very low. Clear increases in the overburdens of HF and HNO3 were observed during the course of September in the vortex core. HCl and NO2 exhibited smaller, less significant increases. The overburdens of the tropospheric source gases, N2O, CH4, CF2Cl2, and H2O were observed to much smaller over Antarctica than at mid-latitudes. This, together with the fact that HF over Antarctica was more that double its mid-latitude value, suggests that downwelling has occurred.

Toon, Goeff C.↗

Measurements of stratospheric odd nitrogen at Arrival Heights, Antarctica, in 1991

An FTIR spectrometer was installed at Arrival Heights, Antarctica (78 deg S, 167 deg E) in February 1991 to measure the evolution of stratospheric HNO3 during the year. In particular, it was the intention to make the first observations of HNO3 trends during autumn, concurrently with ongoing measurements of column NO2 made with a grating spectrometer. The time-series of NO2 in the Antarctic shows a rapid decline in the column amount during autumn, and a slow recovery in spring, as the photochemical conditions move the species to and from higher storage reservoirs. The new nitric acid data show for the first time that during autumn the vertical column increases from approximately 1.9 x 10(exp 16) molecule cm(exp -2) at day 30 to approximately 3.1 x 10(exp 16) molecule cm(exp -2) by day 100. When the sun returns in spring, it is found that the column amount has fallen to about half the value at the end of autumn. Spring amounts are variable, but as found in the data from previous years remain low inside the vortex. The autumn increase is attributed to the heterogeneous conversion of N2O5 to gas-phase HNO3 on background aerosols. Low nitric acid column amounts at the start of spring suggest that the HNO3 has moved from the gas to the condensed phase on polar stratospheric clouds with the advent of low temperatures during the polar night.

Keys, J. Gordon↗

Composition and freezing of aqueous H2SO4/HNO3 solutions under polar stratospheric conditions

The results of laboratory investigations of the freezing behavior of aqueous acid solutions indicate that in the stratosphere H2SO/H2O aerosol droplets would not freeze at temperatures above the ice frost point in the absence of HNO3; however, in the presence of typical levels of HNO3 liquid sulfuric acid aerosols take up significant amounts of HNO3 and H2O vapors and freeze much more readily. This is a consequence of the very rapid change in composition of the liquid droplets as the temperature drops to within two to three degrees of the equilibrium temperature at which HNO3 and H2O vapors would co-condense to form a liquid solution. In the high latitude stratosphere this HNO3/H2O 'dew point' is typically around 192-194 K at 100 mbar.

Beyer, K. D.↗

Heterogeneous Reactions of ClONO2, HCl, and HOCl on Liquid Sulfuric Acid Surfaces

The heterogeneous reactions of ClONO2 + H2O yields HNO3 + HOCl (1), ClONO2 + HCl yields C12 + HNO3 (2), and HOCl + HCl yields Cl2 + H2O (3) on liquid sulfuric acid surfaces have been studied using a fast flow reactor coupled to a quadrupole mass spectrometer. The main objectives of the study are to investigate: (a) the temperature dependence of these reactions at a fixed H2O partial pressure typical of the lower stratosphere (that is, by changing temperature at a constant water partial pressure, the H2SO4 content of the surfaces is also changed), (b) the relative importance or competition between reactions 1 and 2, and (c) the effect of HNO3 on the reaction probabilities due to the formation of a H2SO4/HNO3/H2O ternary system. The measurements show that all the reactions depend markedly on temperature at a fixed H2O partial pressure: they proceed efficiently at temperatures near 200 K and much slower at temperatures near 220 K. The reaction probability (gamma(sub 1)) for ClONO2 hydrolysis approaches 0.01 at temperatures below 200 K, whereas the values for gamma(sub 2) and gamma(sub 3) are on the order of a few tenths at 200 K. Although detailed mechanisms for these reactions are still unknown, the present data indicate that the competition between ClONO2 hydrolysis and ClONO2 reaction with HCl may depend on temperature (or H2SO4 Wt %): in the presence of gaseous HCl at stratospheric concentrations, reaction 2 is dominant at lower temperatures (less than 200 K), but reaction 1 becomes important at temperatures above 210 K. Furthermore, reaction probability measurements performed on the H2SO4/HNO3/ H2O ternary solutions do not exhibit noticeable deviation from those performed on the H2SO4/H2O binary system, suggesting little effect of HNO3 in sulfate aerosols on the ClONO2 and HOCl reactions with HCl. The results reveal that significant reductions in the chlorine-containing reservoir species (such as ClONO2 and HCl) can take place on stratospheric sulfate aerosols at high latitudes in winter and early spring, even at temperatures too warm for Polar Stratospheric Clouds (PSCs) to form or in regions where nucleation of PSCs is sparse. This is particularly true under elevated sulfuric acid loading, such as that after the eruption of Mt. Pinatubo. Comparisons between our results and those presently available have also been made.

Zhang, Renyi↗

NO(x) Concentrations in the Upper Troposphere as a Result of Lightning

Upper tropospheric NO(x) controls, in part, the distribution of ozone in this greenhouse-sensitive region of the atmosphere. Many factors control NO(x) in this region. As a result it is difficult to assess uncertainties in anthropogenic perturbations to NO from aircraft, for example, without understanding the role of the other major NO(x) sources in the upper troposphere. These include in situ sources (lightning, aircraft), convection from the surface (biomass burning, fossil fuels, soils), stratospheric intrusions, and photochemical recycling from HNO3. This work examines the separate contribution to upper tropospheric "primary" NO(x) from each source category and uses two different chemical transport models (CTMS) to represent a range of possible atmospheric transport. Because aircraft emissions are tied to particular pressure altitudes, it is important to understand whether those emissions are placed in the model stratosphere or troposphere and to assess whether the models can adequately differentiate stratospheric air from tropospheric air. We examine these issues by defining a point-by-point "tracer tropopause" in order to differentiate stratosphere from troposphere in terms of NO(x) perturbations. Both models predict similar zonal average peak enhancements of primary NO(x) due to aircraft (approx. = 10-20 parts per trillion by volume (pptv) in both January and July); however, the placement of this peak is primarily in a region of large stratospheric influence in one model and centered near the level evaluated as the tracer tropopause in the second. Below the tracer tropopause, both models show negligible NO(x) derived directly from the stratospheric source. Also, they predict a typically low background of 1 - 20 pptv NO(x) when tropospheric HNO3 is constrained to be 100 pptv of HNO3. The two models calculate large differences in the total background NO(x) (defined as the source of NO(x) from lightning + stratosphere + surface + HNO3) when using identical loss frequencies for NO(x). This difference is primarily due to differing treatments of vertical transport. An improved diagnosis of this transport that is relevant to NO(x) requires either measurements of a surface-based tracer with a substantially shorter lifetime than Rn-222 or diagnosis and mapping of tracer correlations with different source signatures. Because of differences in transport by the two models we cannot constrain the source of NO(x) from lightning through comparison of average model concentrations with observations of NO(x).

Penner, Joyce E.↗

A Comparison of Observations and Model Simulations of NO(x)/NO(y) in the Lower Stratosphere

Extensive airborne measurements of the reactive nitrogen reservoir (NOY) and its component nitric oxide (NO) have been made in the lower stratosphere. Box model. simulations that are constrained by observations of radical and longlived species and which include heterogeneous chemistry systematically underpredict the NO(x) (= NO + NO2) to NOY ratio. The model agreement is substantially improved if newly measured rate coefficients for the OH + NO2 and OH + HNO3 reactions are used. When included in 2-D models, the new rate coefficients significantly increase the calculated ozone loss due to NO(x) and modestly change the calculated ozone abundances in the lower stratosphere. Ozone changes associated with the emissions of a fleet of supersonic aircraft are also altered. phase chemistry linking NO(x) and nitric acid (HNO3), which is generally the most abundant NOY species. Because the continuous daylight present at summer high latitudes limits the heterogeneous production of HNO3 by N2O5 hydrolysis, gas-phase reactions primarily control the balance between NO(x) and NO(y). Outside summer polar regions, the N2O5 hydrolysis reaction occurring on stratospheric sulfate aerosols is a more important sink of NO(x), particularly in the lower stratosphere during winter when heterogeneous pathways account for most of the HNO3 production.

Gao, R. S.↗

Chemical Observations of a Polar Vortex Intrusion

An intrusion of vortex edge air in D the interior of the Arctic polar vortex was observed on the January 31,2005 flight of the NASA DC-8 aircraft. This intrusion was identified as anomalously high values of ozone by the AROTAL and DIAL lidars. Our analysis shows that this intrusion formed when a blocking feature near Iceland collapsed, allowing edge air to sweep into the vortex interior. along the DC-8 flight track also shows the intrusion in both ozone and HNO3. Polar Stratospheric Clouds (PSCs) were observed by the DIAL lidar on the DC-8. The spatial variability of the PSCs can be explained using MLS HNO3 and H2O observations and meteorological analysis temperatures. We also estimate vortex denitrification using the relationship between N2O and HNO3. Reverse domain fill back trajectory calculations are used to focus on the features in the MLS data. The trajectory results improve the agreement between lidar measured ozone and MLS ozone and also improve the agreement between the HNO3 measurements PSC locations. The back trajectory calculations allow us to compute the local denitrification rate and reduction of HCl within the filament. We estimate a denitrification rate of about lO%/day after exposure to below PSC formation temperature. Analysis of Aura MLS observations made

Schoeberl, M. R.↗

Space-Based Constraints on the Production of Nitric Oxide by Lightning

.We interpret observations of trace-gases from three satellite platforms to provide top-down constraints on the production of NO by lightning. The space-based observations are tropospheric NO2 columns from SCIAMACHY, tropospheric O3 columns from OMI and MLS, and upper tropospheric HNO3 from ACE-FTS. A global chemical transport model (GEOS-Chem) is used to identify locations and time periods in which lightning would be expected to dominate the trace gas observations. The satellite observations are sampled at those locations and time periods. All three observations exhibit a maximum in the tropical Atlantic region and a minimum in the tropical Pacific. This wave-1 pattern is driven by injection of lightning NO into the upper troposphere over the tropical continents, followed by photochemical production of NO2, HNO3, and O3 during transport. Lightning produces a broad enhancement over the tropical Atlantic and Africa of 2-6 x 10(exp 14) molecules NO2/sq cm, 4 x 10(exp 17) molecules O3/sq cm (15 Dobson Units), and 125 pptv of upper tropospheric HNO3. The lightning background is 25-50% weaker over the tropical Pacific. A global source of 6+/-2 Tg N/yr from lightning in the model best represents the satellite observations of tropospheric NO2, O3, and HNO3.

Martin, Randall V.↗