Measurements of HNO(sub 4): implications for HO(sub x)
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photochemistry of middle atmosphere↗
Engineering topics
Wennberg, P. O.
Publications and source records attributed to Wennberg, P. O..
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.↗
Measurements of CO in the Upper Troposphere and Lower Stratosphere
In situ measurements of CO were made in the upper troposphere and lower stratosphere (7 to 22 km altitude) with the JPL Aircraft Laser Infrared Absorption Spectrometer (ALIAS) on 58 flights of the NASA ER-2 aircraft from October 1995 through September 1997, between 90 degrees North and 3 degrees South latitude.
Caborn Monoxide ALIAS ER-2↗
Hydrogen Radicals, Nitrogen Radicals, and the Production of O3 in the Upper Troposphere
The concentrations of the hydrogen radicals OH and HO2 in the middle and upper troposphere were measured simultaneously with those of NO, O3, CO, H2O, CH4, non-methane hydrocarbons, and with the ultraviolet and visible radiation field. The data allow a direct examination of the processes that produce O3 in this region of the atmosphere. Comparison of the measured concentrations of OH and HO2 with calculations based on their production from water vapor, ozone, and methane demonstrate that these sources are insufficient to explain the observed radical concentrations in the upper troposphere. The photolysis of carbonyl and peroxide compounds transported to this region from the lower troposphere may provide the source of HO, required to sustain the measured abundances of these radical species. The mechanism by which NO affects the production Of O3 is also illustrated by the measurements. In the upper tropospheric air masses sampled, the production rate for ozone (determined from the measured concentrations of HO2 and NO) is calculated to be about I part per billion by volume each day. This production rate is faster than previously thought and implies that anthropogenic activities that add NO to the upper troposphere, such as biomass burning and aviation, will lead to production of more 03 than expected.
Wennberg, P. O.↗
Hydrogen Radicals, Nitrogen Radicals, and the Production of O3 in the Upper Troposphere
The concentrations of the hydrogen radicals OH and HO2 in the middle and upper troposphere were measured simultaneously with those of NO, O3, CO, H2O, CH4, non-methane hydrocarbons, and with the ultraviolet and visible radiation field. The data allow a direct examination of the processes that produce O3 in this region of the atmosphere. Comparison of the measured concentrations of OH and HO2 with calculations based on their production from water vapor, ozone, and methane demonstrate that these sources are insufficient to explain the observed radical concentrations in the upper troposphere. The photolysis of carbonyl and peroxide compounds transported to this region from the lower troposphere may provide the source of HO(sub x) required to sustain the measured abundances of these radical species. The mechanism by which NO affects the production of O3 is also illustrated by the measurements. In the upper tropospheric air masses sampled, the production rate for ozone (determined from the measured concentrations of HO2 and NO) is calculated to be about 1 part per billion by volume each day. This production rate is faster than previously thought and implies that anthropogenic activities that add NO to the upper troposphere, such as biomass burning and aviation, will lead to production of more O3 than expected.
Wennberg, P. O.↗
Hydrogen Radicals, Nitrogen Radicals, and the Production of O3 in the Upper Troposphere
The concentrations of the hydrogen radicals OH and HO2 in the middle and upper troposphere were measured simultaneously with those of NO, O3, CO, H2O, CH4, non-methane hydrocarbons, and with the ultraviolet and visible radiation field. The data allow a direct examination of the processes that produce O3, in this region of the atmosphere. Comparison of the measured concentrations of OH and HO2 with calculations based on their production from water vapor, ozone, and methane demonstrate that these sources are insufficient to explain the observed radical concentrations in the upper troposphere. The photolysis of carbonyl and peroxide compounds transported to this region from the lower troposphere may provide the source of HO(x) required to sustain the measured abundances of these radical species. The mechanism by which NO affects the production of 03 is also illustrated by the measurements. In the upper tropospheric air masses sampled, the production rate for ozone (determined from the measured concentrations of HO2 and NO) is calculated to be about 1 part per billion by volume each day.This production rate is faster than previously thought and implies that anthropogenic activities that add NO to the upper troposphere, such as biomass burning and aviation, will lead to production of more 03 than expected.
Wennberg, P. O.↗
Measurements and Model Calculations of HNO4: Implications for HO(x)
Establishing a quantitative understanding of the abundance of peroxynitric acid (HNO4) is of interest because the reaction of OH with HNO4 is believed to be a significant sink for HO(x) in the lower stratosphere and upper troposphere. We present concentration profiles of KNO4 obtained by the MkIV Fourier transform infrared spectrometer using the solar occultation technique during two flights, one at 35 N on 25 September 1993 (930925) and the other near 66 N on 7 May 1997 (970507). The observations of HN04 present an apparent dilemma: the calculated profile for HNO4 found using standard kinetics is in relatively good agreement with the mid-latitude observations, but the calculated profile for HNO4 found using the same kinetics overestimates the high-latitude summer observations by nearly a factor of two. Resolution of this dilemma is the focus of our investigation. We show that introduction into our photochemical model of a speculative long-wave (lambda greater than 650 nm) photolytic pathway for HNO4 leads to good agreement between theory and observation of HN04 for both the mid-latitude and high-latitude regions. Implications for the budget of HO(x) are also discussed.
Osterman, G. B.↗
The Role of HOx in Super-and Subsonic Aircraft Exhaust Plumes
The generation of sulfuric acid aerosols in aircraft exhaust has emerged as a critical issue in determining the impact of supersonic aircraft on stratospheric ozone. It has long been held that the first step in the mechanism of aerosol formation is the oxidation of SO2 emitted from the engine by OH in the exhaust plume. We report in situ measurements of OH and HO2 in the exhaust plumes of a supersonic (Air France Concorde) and a subsonic (NASA ER-2) aircraft in the lower stratosphere. These measurements imply that reactions with OH are responsible for oxidizing only a small fraction of SO2 (2%), and thus cannot explain the large number of particles observed in the exhaust wake of the Concorde.
Hanisco, T. F.↗
The Role of HO(x) in Super- and Subsonic Aircraft Exhaust Plumes
The generation of sulfuric acid aerosols in aircraft exhaust has emerged as a critical issue in determining the impact of supersonic aircraft on stratospheric ozone. It has long been held that the first step in the mechanism of aerosol formation is the oxidation of SO2, emitted from the engine by OH in the exhaust plume. We report in situ measurements of OH and HO, in the exhaust plumes of a supersonic (Air France Concorde) and a subsonic (NASA ER-2) aircraft in the lower stratosphere. These measurements imply that reactions with OH are responsible for oxidizing only a small fraction of SO2 (2%), and thus cannot explain the large number of particles observed in the exhaust wake of the Concorde.
Hanisco, T. F.↗
The Role of HO(x) in Super- and Subsonic Aircraft Exhaust Plumes
The generation of sulfuric acid aerosols in aircraft exhaust has emerged as a critical issue in determining the impact of supersonic aircraft on stratospheric ozone. It has long been held that the first step in the mechanism of aerosol formation is the oxidation of SO2 emitted from the engine by OH in the exhaust plume. We report in situ measurements of OH and HO2 in the exhaust plumes of a supersonic (Air France Concorde) and a subsonic (NASA ER-2) aircraft in the lower stratosphere. These measurements imply that reactions with OH are responsible for oxidizing only a small fraction of SO2 (2%), and thus cannot explain the large number of particles observed in the exhaust wake of the Concorde.
Hanisco, T. F.↗
Are models of catalytic removal of O3 by HO(x) accurate? Constraints from in situ measurements of the OH to HO2 ratio
Measurements of the ratio OH/HO2, NO, O3, ClO, and BrO were obtained at altitudes from 15-20 km and latitudes from 15-60 deg N. A method is presented for interpreting the rates of chemical transformations that (1) are responsible for over half the ozone removal rate in the lower stratosphere via reactions of HO2; and (2) control the abundance of HO2 through coupling to nitrogen and halogen radicals. The results show our understanding of the chemical reactions controlling the partitioning of OH and HO2 is complete and accurate and that the potential effects of 'missing chemistry' are strickly constrained in the region of the atmosphere encompassed by the observations. The analysis demonstrates that the sensitivity of the ratio OH/HO2 to changes in NO is described to within 12% by current models. This reduces by more than a factor of 2 the effect of uncertainty in the coupling of hydrogen and nitrogen radicals on the analysis of the potential effects of perturbations to odd notrogen in the lower statosphere.
Cohen, R. C.↗
The response of C1O radical concentrations to variations in NO2 radical concentrations in the lower stratosphere
The respose of ClO concentrations to changes in NO2 concentrations has been inferred from simultaneous observations of (ClO), (NO), (NO2) and (O3) in the midlatitude lower stratosphere. This analysis demonstrates that (ClO) is inversely correlated with (NO2), consistent with formation and photolysis of (ClONO2). A factor of ten range in the concentration if NO2 was sampled (0.1 to 1 x 10(exp 9) mol/cu cm), with a comparable range in the ratio of (ClO) to total available inorganic chlorine (1% less than or equal to (ClO)/(Cl(sub y)) less than or equal to 5%. This analysis leads to an estimate of (ClONO2)/(Cl(sub y)) = 0.12 (x/2), in the mid-latitude, lower-stratospheric air masses sampled.
Stimfle, R. M.↗
The diurnal variation of hydrogen, nitrogen, and chlorine radicals: Implications for the heterogeneous production of HNO2
In situ measurements of hydrogen, nitrogen, and chlorine radicals obtained through sunrise and sunset in the lower statosphere during SPADE are compared to results from a photochemical model constrained by observed concentrations of radical precursors and environmental conditions. Models allowing for heteogeneous hydrolysis of N2O5 on sulfate aerosols agree with measured concentrations of NO, NO2, and ClO throughout the day, but fail to account for high concentrations of OH and HO2 observed near sunrise and sunset. The morning burst of (OH) and (HO2) coincides with the rise of (NO) from photolysis of NO2, suggesting a new source of HO(x) that photolyzes in the near UV (350 to 400 nm) spectral region. A model that allow for the heterogeneous production of HNO2 results in an excellent simulation of the diurnal variations of (OH) and (HO2).
Salawitch, R. J.↗
The Diurnal Variation of Hydrogen, Nitrogen, and Chlorine Radicals: Implications for the Heterogeneous Production of HNO2
In situ measurements of hydrogen, nitrogen, and chlorine radicals obtained through sunrise and sunset in the lower stratosphere during SPADE are compared to results from a photochemical model constrained by observed concentrations of radical precursors and environmental conditions. Models allowing for heterogeneous hydrolysis of N205 on sulfate aerosols agree with measured concentrations of NO, NO2, and ClO throughout the day, but fail to account for high concentrations of OH and H02 observed near sunrise and sunset. The morning burst of [OH] and [HO2] coincides with the rise of [NO] from photolysis of N02, suggesting a new source of HO, that photolyzes in the near UV (350 to 400 nm) spectral region. A model that allows for the heterogeneous production of HN02 results in an excellent simulation of the diurnal variations of [OH] and [HO2].
Salawitch, R. J.↗
The Distribution of Hydrogen, Nitrogen, and Chlorine Radicals in the Lower Stratosphere: Implications for Changes in O3 due to Emission of NO(y) from Supersonic Aircraft
In situ measurements of hydrogen, nitrogen, and chlorine radicals obtained in the lower stratosphere during the Stratospheric Photochemistry, Aerosols and Dynamics Expedition (SPADE) are compared to results from a photochemical model that assimilates measurements of radical precursors and environmental conditions. Models allowing for heterogeneous hydrolysis of N2O5 agree well with measured concentrations of NO and ClO, but concentrations of HO2 and OH are underestimated by 10 to 25%, concentrations of NO2 are overestimated by 10 to 30%, and concentrations of HCl are overestimated by a factor of 2. Discrepancies for [OH] and [HO2] are reduced if we allow for higher yields of O(sup 1)D) from 03 photolysis and for heterogeneous production of HNO2. The data suggest more efficient catalytic removal of O3 by hydrogen and halogen radicals relative to nitrogen oxide radicals than predicted by models using recommended rates and cross sections. Increases in [O3] in the lower stratosphere may be larger in response to inputs of NO(sub y) from supersonic aircraft than estimated by current assessment models.
Salawitch, R. J.↗
The Response of ClO Radical Concentrations to Variations in NO2 Radical Concentrations in the Lower Stratosphere
The response of ClO concentrations to changes in NO2 concentrations has been inferred from simultaneous observations of [ClO], [NO], [NO2] and [O3] in the mid-latitude lower stratosphere. This analysis demonstrates that [ClO] is inversely correlated with [NO2], consistent with formation and photolysis of [ClONO2]. A factor of ten range in the concentration of NO2 was sampled (0.1 to 1 x 10(exp 9) mol/cc), with a comparable range in the ratio of [ClO] to total available inorganic chlorine (1% <= [ClO]/[Cl(sub y)] <= 5%). This analysis leads to an estimate of [ClONO2]/[Cl(sub y)] = 0.12 (x/divided by 2), in the mid-latitude, lower-stratospheric air masses sampled.
Stimpfle, R. M.↗
Aircraft-borne, laser-induced fluorescence instrument for the in situ detection of hydroxyl and hydroperoxyl radicals
The odd-hydrogen radicals OH and HO2 are central to most of the gas-phase chemical transformations that occur in the atmosphere. Of particular interest is the role that these species play in controlling the concentration of stratospheric ozone. This paper describes an instrument that measures both of these species at volume mixing ratios below one part in 10(exp 14) in the upper troposphere and lower stratosphere. The hydroxyl radical (OH) is measured by laser induced fluorescence at 309 nm. Tunable UV light is used to pump OH to the first electric state near 282 nm. the laser light is produced by a high-repetition rate pulsed dye-laser powered with all solid-state pump lasers. HO2 is measured as OH after gas-phase titration with nitric oxide. Measurements aboard a NASA ER-2 aircraft demonstrate the capability of this instrument to perform reliably with very high signal-to-noise ratios (greater than 30) achieved in short integration times (less than 20 sec).
Wennberg, P. O.↗
Simultaneous, in situ measurements of OH and HO2 in the stratosphere
Stratospheric OH and HO2 radical densities have been measured between 36 and 23 km using a balloon-borne, in situ instrument launched from Palestine, Texas on August 25, 1989. OH is detected using the laser-induced fluorescence technique (LIF) employing a Cu-vapor-laser pumped dye laser coupled with an enclosed-flow detection chamber. HO2 is detected nearly simultaneously by adding NO to the sample flow to convert ambient HO2 to OH. Observed OH and HO2 densities ranged from 8.0 + or - 2.8 x 10 to the 6th and 1.4 + or - 0.5 x 10 to the 7th molec/cu cm, respectively, at 36 km, to 1.4 + or - 0.5 x 10 to the 6th and 3.0 + or - 1.0 x 10 to the 6th at 23 km, where the uncertainty is + or - sigma. The HO2 density exhibits a maximum in the 34-30 km region of 1.7 + or - 0.6 x 10 to the 7th. The data were obtained over a solar zenith angle variation of 51 deg at 36 km to 61 deg at 23 km. O3 and H2O densitites also were measured simultaneously with separate instruments.
Stimpfle, R. M.↗