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Rodriquez, J. M.

Publications and source records attributed to Rodriquez, J. M..

Source Attributions of Pollution to the Western Arctic During the NASA ARCTAS Field Campaign

We use the NASA GEOS-5 transport model with tagged tracers to investigate the contributions of different regional sources of CO and black carbon (BC) to their concentrations in the Western Arctic (i.e., 50-90 deg N and 190- 320 deg E) in spring and summer 2008. The model is evaluated by comparing the results with airborne measurements of CO and BC from the NASA Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) field campaigns to demonstrate the strengths and limitations of our simulations. We also examine the reliability of tagged CO tracers in characterizing air mass origins using the measured fossil fuel tracer of dichloromethane and the biomass burning tracer of acetonitrile. Our tagged CO simulations suggest that most of the enhanced CO concentrations (above background level from CH4 production) observed during April originate from Asian anthropogenic emissions. Boreal biomass burning emissions and Asian anthropogenic emissions are of similar importance in July domain wise, although the biomass burning CO fraction is much larger in the area of the ARCTAS field experiments. The fraction of CO from Asian anthropogenic emissions is larger in spring than in summer. European sources make up no more than 10% of CO levels in the campaign domain during either period. Comparisons of CO concentrations along the flight tracks with regional averages from GEOS-5 show that the alongtrack measurements are representative of the concentrations within the large domain of the Western Arctic in April but not in July.

Black Carbon↗

The Response of Lower Atmospheric Ozone to ENSO in Aura Measurements and a Chemistry-Climate Simulation

The El Nino-Southern Oscillation (ENSO) is the dominant mode of tropical variability on interannual time scales. ENSO appears to extend its influence into the chemical composition of the tropical troposphere. Recent work has revealed an ENSO-induced wave-1 anomaly in observed tropical tropospheric column ozone. This results in a dipole over the western and eastern tropical Pacific, whereby differencing the two regions produces an ozone anomaly with an extremely high correlation to the Nino 3.4 Index. We have successfully reproduced this feature using the Goddard Earth Observing System Version 5 (GEOS-5) general circulation model coupled to a comprehensive stratospheric and tropospheric chemical mechanism forced with observed sea surface temperatures over the past 25 years. An examination of the modeled ozone field reveals the vertical contributions of tropospheric ozone to the column over the western and eastern Pacific region. We will show composition sensitivity in observations from NASA s Aura satellite Microwave Limb Sounder (MLS) and the Tropospheric Emissions Spectrometer (TES) and a simulation to provide insight into the vertical structure of these ENSO-induced ozone changes. The ozone changes due to the Quasi-Biennial Oscillation (QBO) in the extra-polar upper troposphere and lower stratosphere in MLS measurements will also be discussed.

Oman, L. D.↗

Modeling and Observations of the Response of Tropical Tropospheric Ozone to ENSO

The El Nino-Southern Oscillation (ENSO) is the dominant mode of tropical variability on interannual time scales. ENSO appears to extend its influence into the chemical composition of the tropical troposphere, Recent results have revealed an ENSO induced wave-1 anomaly in observed tropical tropospheric column ozone, This results in a dipole over the western and eastern tropical Pacific, whereby differencing the two regions produces an ozone anomaly with an extremely high correlation to the Nino 3.4 Index. We have successfully reproduced this result using the Goddard Earth Observing System Version 5 (GEOS-5) general circulation model coupled to a comprehensive stratospheric and tropospheric chemical mechanism forced with observed sea surface temperatures over the past 25 years, An examination of the modeled ozone field reveals the vertical contributions of tropospheric ozone to the column over the western and eastern Pacific region, We will show targeted comparisons with SHADOZ ozonesondes over these regions to provide insight into the vertical structure. Also, comparisons with NASA's Aura satellite Microwave Limb Sounder (MLS) and Tropospheric Emissions Spectrometer (TES) instruments and other appropriate data sets will be shown. In addition, the water vapor response to ENSO will be compared to help illuminate its role relative to dynamics in impacting ozone concentrations. These results indicate that the tropospheric ozone response to ENSO is potentially a very useful chemistry-climate diagnostic and should be considered in future modeling assessments.

Oman, L. D.↗

Reactive Nitrogen, Ozone and Ozone Production in the Arctic Troposphere and the Impact of Stratosphere-Troposphere Exchange

We analyze the aircraft observations obtained during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellite (ARCTAS) mission together with the GEOS-5 CO simulation to examine O3 and NOy in the Arctic and sub-Arctic region and their source attribution. Using a number of marker tracers and their probability density distributions, we distinguish various air masses from the background troposphere and examine their contribution to NOx, O3, and O3 production in the Arctic troposphere. The background Arctic troposphere has mean O3 of approximately 60 ppbv and NOx of approximately 25 pptv throughout spring and summer with CO decreases from approximately 145 ppbv in spring to approximately 100 ppbv in summer. These observed CO, NOx and O3 mixing ratios are not notably different from the values measured during the 1988 ABLE-3A and the 2002 TOPSE field campaigns despite the significant changes in the past two decades in processes that could have changed the Arctic tropospheric composition. Air masses associated with stratosphere-troposphere exchange are present throughout the mid and upper troposphere during spring and summer. These air masses with mean O3 concentration of 140-160 ppbv are the most important direct sources of O3 in the Arctic troposphere. In addition, air of stratospheric origin is the only notable driver of net O3 formation in the Arctic due to its sustainable high NOx (75 pptv in spring and 110 pptv in summer) and NOy (approximately 800 pptv in spring and approximately 1100 pptv in summer) levels. The ARCTAS measurements present observational evidence suggesting significant conversion of nitrogen from HNO3 to NOx and then to PAN (a net formation of approximately 120 pptv PAN) in summer when air of stratospheric origin is mixed with tropospheric background during stratosphere-to-troposphere transport. These findings imply that an adequate representation of stratospheric O3 and NOy input are essential in accurately simulating O3 and NOx photochemistry as well as the atmospheric budget of PAN in tropospheric chemistry transport models of the Arctic. Anthropogenic and biomass burning pollution plumes observed during ARCTAS show highly elevated hydrocarbons and NOy (mostly in the form of NOx and PAN), but do not contribute significantly to O3 in the Arctic troposphere except in some of the aged biomass burning plumes sampled during spring. Convection and/or lightning influences are negligible sources of O3 in the Arctic troposphere but can have significant impacts in the upper troposphere in the continental sub-Arctic during summer.

Liang, Q.↗

Trend Analysis and Detection of Changes in the Stratospheric Circulation

Increases in the circulation of the stratosphere appear to be a robust result of climate change in chemistry-climate models over decadal time scales. To date observations have yet to show a significant change in this circulation. It is important for the design of future observational missions to identify suitable atmospheric constituents and to determine the accuracy and length of record needed to identify a significant trend that can be attributed to circulation change. First, we determine what atmospheric variables can be used as proxies for stratospheric circulation changes. A few examples are changes in tropical lower stratospheric ozone, phase lag of the water vapor tape recorder, CO2, and SF6. Then, using both the Goddard Earth Observing System Chemistry-Climate Model (GEOS CCM) and observations from satellites and balloon soundings, we calculate the number of years needed to detect a significant trend, taking into account observational uncertainty. Model simulations will be evaluated to see how well they represent observed variability. In addition, the impacts of autocorrelation among the output or data and gaps in the observational record will be discussed.

Oman, Luke↗

Observations and Modeling of Composition of Upper Troposphere/Lower Stratosphere (UTILS): Isentropic Mixing Events and Morphology of HNO3 as Observed by HIRDLS and Comparison with Results from Global Modeling Initiative

isentropic exchange of air masses between the tropical upper troposphere and mid-latitude lowermost stratosphere (the so-called "middle world") is an important pathway for stratospheric-tropospheric exchange. A seasonal, global view of this process has been difficult to obtain, in part due to the lack of the vertical resolution in satellite observations needed to capture the laminar character of these events. Ozone observations at a resolution of about 1 km from the High Resolution Dynamic Limb Sounder (HIRDLS) on NASA's Aura satellite show instances of these intrusions. Such intrusions should also be observable in HN03 observations; however, the abundances of nitric acid could be additionally controlled by chemical processes or incorporation and removal into ice clouds. We present a systematic examination of the HIRDLS data on O3 and HNO3 to determine the seasonal and spatial characteristics of the distribution of isentropic intrusions. At the same time, we compare the observed distributions with those calculated by the Global Modeling Initiative combined tropospheric-stratospheric model, which has a vertical resolution of about I km. This Chemical Transport Model (CTM) is driven by meteorological fields obtained from the GEOS-4 system of NASA/Goddard Global Modeling and Assimilation Office (GMAO), for the Aura time period, at a vertical resolution of about 1 km. Such comparison brings out the successes and limitations of the model in representing isentropic stratospheric-tropospheric exchange, and the different processes controlling HNO3 in the UTAS.

Rodriquez, J. M.↗

Simulations of Tropospheric NO2 by the Global Modeling Initiative (GMI) Model Utilizing Assimilated and Forecast Meteorological Fields: Comparison to Ozone Monitoring Instrument (OMI) Measurements

We present simulations of the tropospheric composition for the years 2004 and 2005, carried out by the GMI Combined Stratosphere-Troposphere (Combo) model, at a resolution of 2degx2.5deg. The model includes a new parameterization of lightning sources of NO(x) which is coupled to the cloud mass fluxes in the adopted meteorological fields. These simulations use two different sets of input meteorological fields: a)late-look assimilated fields from the Global Modeling and Assimilation Office (GMAO), GEOS-4 system and b) 12-hour forecast fields initialized with the assimilated data. Comparison of the forecast to the assimilated fields indicates that the forecast fields exhibit less vigorous convection, and yield tropical precipitation fields in better agreement with observations. Since these simulations include a complete representation of the stratosphere, they provide realistic stratosphere-tropospheric fluxes of O3 and NO(y). Furthermore, the stratospheric contribution to total columns of different troposheric species can be subtracted in a consistent fashion, and the lightning production of NO(y) will depend on the adopted meteorological field. We concentrate here on the simulated tropospheric columns of NO2, and compare them to observations by the OM1 instrument for the years 2004 and 2005. The comparison is used to address these questions: a) is there a significant difference in the agreement/disagreement between simulations for these two different meteorological fields, and if so, what causes these differences?; b) how do the simulations compare to OMI observations, and does this comparison indicate an improvement in simulations with the forecast fields? c) what are the implications of these simulations for our understanding of the NO2 emissions over continental polluted regions?

Rodriquez, J. M.↗

Activities of NASA's Global Modeling Initiative (GMI) in the Assessment of Subsonic Aircraft Impact

The Intergovernmental Panel on Climate Change estimated a peak increase in ozone ranging from 7-12 ppbv (zonal and annual average, and relative to a baseline with no aircraft), due to the subsonic aircraft in the year 2015, corresponding to aircraft emissions of 1.3 TgN/year. This range of values presumably reflects differences in model input (e.g., chemical mechanism, ground emission fluxes, and meteorological fields), and algorithms. The model implemented by the Global Modeling Initiative allows testing the impact of individual model components on the assessment calculations. We present results of the impact of doubling the 1995 aircraft emissions of NOx, corresponding to an extra 0.56 TgN/year, utilizing meteorological data from NASA's Data Assimilation Office (DAO), the Goddard Institute for Space Studies (GISS), and the Middle Atmosphere Community Climate Model, version 3 (MACCM3). Comparison of results to observations can be used to assess the model performance. Peak ozone perturbations ranging from 1.7 to 2.2 ppbv of ozone are calculated using the different fields. These correspond to increases in total tropospheric ozone ranging from 3.3 to 4.1 Tg/Os. These perturbations are consistent with the IPCC results, due to the difference in aircraft emissions. However, the range of values calculated is much smaller than in IPCC.

Rodriquez, J. M.↗

Trajectory Hunting: A Case Study of Rapid Chlorine Activation in December 1992 as Seen by UARS

Trajectory hunting (i.e., a technique to find air parcels sampled at least twice over the course of a few days) is applied to analyze Upper Atmosphere Research Satellite (UARS) measurements in conjunction with the Atmospheric and Environmental Research, Inc. (AER) photochemical box model. As a case study, we investigate rapid chlorine activation in the Arctic lower stratosphere on December 29, 1992 associated with a polar stratospheric cloud (PSC) event. Eleven air parcels that have been sampled several times along 5-day trajectories at the 465 K (approx. 46 hPa), 520 K (approx. 31 hPa), and 585 K (approx. 22 hPa) levels were investigated. For the first time, the latest versions of the Cryogenic Limb Array Etalon Spectrometer (CLAES, version 9) and Microwave Limb Sounder (MLS, version 5) data sets are analyzed, and their consistency is assessed. A detailed sensitivity study with the AER photochemical box model along these trajectories leads to the conclusion that for the December 24-29, 1992 episode (1) the individual CLAES version 9 ClONO2 and MLS version 5 ClO measurements are self-consistent within their uncertainties; and (2) most of the time, UARS measurements of ClO, ClONO2, HNO3, and aerosol extinction at 780 cm (exp -1) agree within the range of their uncertainties with the model calculations. It appears that the HNO3 and aerosol extinction measurements for four parcels at 520 K look more supportive for the nitric acid trihydrate (NAT) scheme. However, the uncertainties in the individual UARS measurements and U.K. Meteorological Office temperature do not allow a definite discrimination between the NAT and supercooled ternary solution (STS) PSC schemes for this chlorine activation episode in December 1992.

Danilin, M. Y.↗

Choosing Meteorological Input for the Global Modeling Initiative Assessment of High Speed Aircraft

The Global Modeling Initiative (GMI) science team is developing a three dimensional chemistry and transport model (CTM) to be used in assessment of the atmospheric effects of aviation. Requirements are that this model be documented be validated against observations, use a realistic atmospheric circulation, and contain numerical transport and photochemical modules representing atmospheric processes. The model must also retain computational efficiency to be tractable to use for multiple scenarios and sensitivity studies. To meet these requirements, a facility model concept was developed in which the different components of the CTM are evaluated separately. The first use of the GMI model will be to evaluate the impact of the exhaust of supersonic aircraft on the stratosphere. The assessment calculations will depend strongly on the wind and temperature fields used by the CTM. Three meteorological data sets for the stratosphere are available to GMI: the National Center for Atmospheric Research Community Climate Model (CCM2), the Goddard Earth Observing System Data Assimilation System (GEOS DAS), and the Goddard Institute for Space Studies general circulation model (GISS). Objective criteria were established by the GMI team to identify the data set which provides the best representation of the stratosphere. Simulations of gases with simple chemical control were chosen to test various aspects of model transport. The three meteorological data sets were evaluated and graded based on their ability to simulate these aspects of stratospheric measurements. This paper describes the criteria used in grading the meteorological fields. The meteorological data set which has the highest score and therefore was selected for GMI is CCM2. This type of objective model evaluation establishes a physical basis for interpretation of differences between models and observations. Further, the method provides a quantitative basis for defining model errors, for discriminating between different models, and for ready re-evaluation of improved models. These in turn will lead to a higher level of confidence in assessment calculations.

Douglass, A. R.↗

Utilization of UARS Data in Validation of Photochemical and Dynamical Mechanisms in Stratospheric Models

The proposed work utilized Upper Atmosphere Research Satellite (UARS) measurements of short-lived and long-lived species, in conjunction with existing photochemical "box" models, trajectory models, and two-dimensional global models, to elucidate outstanding questions in our understanding of photochemical and dynamical mechanisms in the stratosphere. Particular emphasis was given to arriving at the best possible understanding of the chemical and dynamical contributions to the stratospheric ozone budget. Such understanding will increase confidence in the simulations carried out by assessment models.

Ko, M. K. W.↗

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.↗

Trifluoroacetic Acid from Degradation of HCFCs and HFCs: A Three-Dimensional Modeling Study

Trifluoroacetic acid (TFA; CF3COOH) is produced by the degradation of the halocarbon replacements HFC-134a, HCFC-124, and HCFC-123. The formation of TFA occurs by HFC/HCFC reacting with OH to yield CF3COX (X = F or CI), followed by in-cloud hydrolysis of CF3COX to form TFA. The TFA formed in the clouds may be reevaporated but is finally deposited onto the surface by washout or dry deposition. Concern has been expressed about the possible long-term accumulation of TFA in certain aquatic environments, pointing to the need to obtain information on the concentrations of TFA in rainwater over scales ranging from local to continental. Based on projected concentrations for HFC-134a, HCFC-124, and HCFC-123 of 80, 10, and 1 pptv in the year 2010, mass conservation arguments imply an annually averaged global concentration of 0.16 micro g/L if washout were the only removal mechanism for TFA. We present 3-D simulations of the HFC/HCFC precursors of TFA that include the rates of formation and deposition of TFA based on assumed future emissions. An established (GISS/Harvard/ UCI) but coarse-resolution (8 deg latitude by 10 deg longitude) chemical transport model was used. The annually averaged rainwater concentration of 0.12 micro g/L (global) was calculated for the year 2010, when both washout and dry deposition are included as the loss mechanism for TFA from the atmosphere. For some large regions in midnorthern latitudes, values are larger, 0.15-0.20 micro g/L. The highest monthly averaged rainwater concentrations of TFA for northern midlatitudes were calculated for the month of July, corresponding to 0.3-0.45 micro g/L in parts of North America and Europe. Recent laboratory experiments have suggested that a substantial amount of vibrationally excited CF3CHFO is produced in the degradation of HFC-134a, decreasing the yield of TFA from this compound by 60%. This decrease would reduce the calculated amounts of TFA in rainwater in the year 2010 by 26%, for the same projected concentrations of precursors.

Kotamarthi, V. R.↗

Trifluoroacetic Acid from Degradation of HCFCs and HFCs: A Three-Dimensional Modeling Study

Trifluoroacetic acid (TFA; CF3 COOH) is produced by the degradation of the halocarbon replacements HFC-134a, HCFC-124, and HCFC-123. The formation of TFA occurs by HFC/HCFC reacting with OH to yield CF3COX (X = F or CI), followed by in-cloud hydrolysis of CF to form TFA. The TFA formed in the clouds may be reevaporated but is finally deposited onto the surface by washout or dry deposition. Concern has been expressed about the possible long-term accumulation of TFA in certain aquatic environments, pointing to the need to obtain information on the concentrations of TFA in rainwater over scales ranging from local to continental. Based on projected concentrations for HFC-134a, HCFC-124, and HCFC-123 of 80, 10, and 1 pptv in the year 2010, mass conservation arguments imply an annually averaged global concentration of 0.16 micro g/L if washout were the only removal mechanism for TFA. We present 3-D simulations of the HFC/HCFC precursors of TFA that include the rates of formation and deposition of TFA based on assumed future emissions. An established (GISS[Harvard/ UCI) but coarse-resolution (8 deg latitude by 10 deg longitude) chemical transport model was used. The annually averaged rainwater concentration of 0.12 micro g/L (global) was calculated for the year 2010, when both washout and dry deposition are included as the loss mechanism for TFA from the atmosphere. For some large regions in midnorthern latitudes, values are larger. 0.15-0.20 micro g/L. The highest monthly averaged rainwater concentrations of TFA for northern midlatitudes were calculated for the month of July, corresponding to 0.3 - 0.45 micro g/L in parts of North America and Europe. Recent laboratory experiments have suggested that a substantial amount of vibrationally excited CF3CHFO is produced in the degradation of HFC-134a, decreasing the yield of TFA from this compound by 60%. This decrease would reduce the calculated amounts of TFA in rainwater in the year 2010 by 26%, for the same projected concentrations of precursors.

Kotamarthi, V. R.↗

Trajectory Hunting: Analysis of UARS Measurements Showing Rapid Chlorine Activation

Trajectory hunting (i.e., a technique to find air parcels sampled at least twice over the course of a few days) is applied to analyze Upper Atmosphere Research Satellite (UARS) measurements in conjunction with the AER photochemical box model. In this study, we investigate rapid chlorine activation in the Arctic lower stratosphere on 29 Dec. 1992 associated with a polar stratospheric cloud (PSC) event. Six air parcels that have been sampled twice were followed along 5-day trajectories at the 465 K (approx. 46 mb) and 585 K (approxi. 22 mb) levels. A detailed sensitivity study with the AER photochemical box model along these trajectories leads to the following conclusions for the episode considered: 1) model results are in better agreement with UARS measurements at these levels if the U.K. Meteorological Office (UKMO) temperature is decreased by at least 1-2 K; 2) the NAT (nitric acid trihydrate) PSC formation scheme produces results in better agreement with observations than the STS (supercooled ternary solution) scheme; 3) the model can explain the UARS measurements at 585 K, but under-estimates the ClO abundance at 465 K, suggesting some inconsistency between the UARS measurements at this level.

Danilin, M. Y.↗

Choosing Meteorological Input for the Global Modeling Initiative Assessment of High Speed Aircraft

The Global Modeling Initiative (GMI) science team is developing a three dimensional chemistry and transport model (CTM) to be used in assessment of the atmospheric effects of aviation. Requirements are that this model be documented, be validated against observations, use a realistic atmospheric circulation, and contain numerical transport and photochemical modules representing atmospheric processes. The model must also retain computational efficiency to be tractable to use for multiple scenarios and sensitivity studies. To meet these requirements, a facility model concept was developed in which the different components of the CTM are evaluated separately. The first use of the GMI model will be to evaluate the impact of the exhaust of supersonic aircraft on the stratosphere. The assessment calculations will depend strongly on the wind and temperature fields used by the CTM. Three meteorological data sets for the stratosphere are available to GMI: the National Center for Atmospheric Research Community Climate Model (CCM2), the Goddard Earth Observing System Data Assimilation System (GEOS DAS), and the Goddard Institute for Space Studies general circulation model (GISS). Objective criteria were established by the GMI team to identify the data set which provides the best representation of the stratosphere. Simulations of gases with simple chemical control were chosen to test various aspects of model transport. The three meteorological data sets were evaluated and graded based on their ability to simulate these aspects of stratospheric measurements. This paper describes the criteria used in grading the meteorological fields. The meteorological data set which has the highest score and therefore was selected for GMI is CCM2. This type of objective model evaluation establishes a physical basis for interpretation of differences between models and observations. Further, the method provides a quantitative basis for defining model errors, for discriminating between different models, and for ready re-evaluation of improved models. These in turn will lead to a higher level of confidence in assessment calculations.

Douglas, A. R.↗

Trajectory Hunting: Analysis of UARS Measurements showing Rapid Chlorine Activation

Trajectory hunting (i.e., a technique to find air parcels sampled at least twice over the course of a few days) is applied to analyze Upper Atmosphere Research Satellite (UARS) measurements in conjunction with the AER photochemical box model. In this study, we investigate rapid chlorine activation in the Arctic lower stratosphere on 29 Dec 1992 associated with a polar stratospheric cloud (PSC) event. Six air parcels that have been sampled twice were followed along 5-day trajectories at the 465 K (approximately 46 mb) and 585 K (approximately 22 mb) levels. A detailed sensitivity study with the AER. photochemical box model along these trajectories leads to the following conclusions for the episode considered: (1) model results are in better agreement with UARS measurements at these levels if the UKMO temperature is decreased by at least 1-2 K; (2) the NAT (nitric acid trihydrate) PSC formation scheme produces results in better agreement with observations than the STS (supercooled ternary solution) scheme; (3) the model can explain the UARS measurements at 585 K, but under-estimates the ClO abundance at 465 K, suggesting some inconsistency between the UARS measurements at this level.

Danilin, M.Y.↗

Impact of Lightning and Convection on Reactive Nitrogen in the Tropical Free Troposphere

Latitudinal distributions of NO, NO(y), O3, CO, CH3I, and H2O mixing ratios at 8.9-12 km were obtained between 30deg N and 1deg S by DC-8 aircraft measurements made in February 1994 during Pacific Exploratory Mission-West B (PEM-West B). Very low NO(y), mixing ratios with a median value of 51 parts per trillion by volume (pptv) were observed at 9.5-12 km at 1deg N-14deg N during two flights made within 3 days. A very low median O3 mixing ratio of 19 parts per billion by volume (ppbv) and high mixing ratios of H2O and CH3I were simultaneously observed, suggesting that the low NO(y), values were probably due to the convective transport of air from the tropical marine boundary layer to this altitude. The median NO(y)/O3 ratio being a factor of 2 smaller than in the air masses in the tropical marine boundary layer might suggest the possibility that the heterogeneous removal of HNO3 during convective transport further reduced NO(y) levels. In addition to the measurements between 9.5 and 12 km, low values of NO(y) and O3 were observed between 4 and 12 km at 1deg N. Divergent wind fields at 200 and 1000 hPa and infrared (IR) cloud images show that there was large scale convection (greater than 1000 km x 1000 km) in the northeast of New Guinea Island centered around Odeg S and 150deg E as part of systematic convective activity of the Intertropical Convergence Zone (ITCZ) and the South Pacific Convergence Zone (SPCZ). This type of large scale convection could have transported air with low levels of NO(y) and O3 to the middle and upper troposphere over a wide area in the tropics. On the other hand, NO mixing ratios of 50-200 pptv and high NQ,/NOY ratios of 0.4-0.6 were observed at 9.5 km between 4deg S and 10deg S. High H2O Mixing ratios of 600-1200 parts per million by volume (ppmv) and low CO mixing ratios of 65 ppbv observed in the air mass indicated that the high NO values were probably due to NO production by lightning. Satellite observations showed relatively frequent lightning flashes over the New Guinea Island for 3 days prior to the aircraft measurements. These results are considered to be consistent with the idea that, in general, marine convection is not accompanied by lightning activity, whereas convection over land is. Because of the large areal extent of the influences from these processes, the convective transport of low NO(y) air and NO production by lightning should play critical roles in controlling the abundance of reactive nitrogen in the equatorial region.

Kawakami, S.↗