E. J. Lanzendorf

Observed OH and HO2 in the upper troposphere suggest a major source from convective injection of peroxides

ER-2 aircraft observations of OH and HO_2 concentrations in the upper troposphere during the NASA/STRAT campaign are interpreted using a photochemical model constrained by local observations of O_3, H_2O, NO, CO, hydrocarbons, albedo and overhead ozone column. We find that the reaction Q(^(1)D) + H_2O is minor compared to acetone photolysis as a primary source of HO_x (= OH + peroxy radicals) in the upper troposphere. Calculations using a diel steady state model agree with observed HO_x concentrations in the lower stratosphere and, for some flights, in the upper troposphere. However, for other flights in the upper troposphere, the steady state model underestimates observations by a factor of 2 or more. These model underestimates are found to be related to a recent (< 1 week) convective origin of the air. By conducting time-dependent model calculations along air trajectories determined for the STRAT flights, we show that convective injection of CH_3OOH and H_2O_2 from the boundary layer to the upper troposphere could resolve the discrepancy. These injections of HO_x reservoirs cause large HO_x increases in the tropical upper troposphere for over a week downwind of the convective activity. We propose that this mechanism provides a major source of HO_x in the upper troposphere. Simultaneous measurements of peroxides, formaldehyde and acetone along with OH and HO_2 are needed to test our hypothesis.

Twilight observations suggest unknown sources of HOx

Measurements of the concentrations of OH and HO_(2) (HO_(x)) in the high-latitude lower stratosphere imply the existence of unknown photolytic sources of HO_(x). The strength of the additional HO_(x) source required to match the observations depends only weakly on solar zenith angle (SZA) for 80° < SZA < 93°. The wavelengths responsible for producing this HO_(x) must be longer than 650 nm because the flux at shorter wavelengths is significantly attenuated at high SZA by scattering and absorption. Provided that the sources involve only a single photon, the strength of the bonds being broken must be < 45 kcal mole^(−1). We speculate that peroxynitric acid (HNO_4) dissociates after excitation to an unknown excited state with an integrated band cross section of 2-3 × 10^(−20) cm^(2) molecule^(−1) nm (650 < λ < 1250 nm).

A comparison of observations and model simulations of NOx/NOy in the lower stratosphere

Extensive airborne measurements of the reactive nitrogen reservoir (NO_(y)) and its component nitric oxide (NO) have been made in the lower stratosphere. Box model simulations that are constrained by observations of radical and long-lived species and which include heterogeneous chemistry systematically underpredict the NO_x (= NO + NO_2) to NO_y ratio. The model agreement is substantially improved if newly measured rate coefficients for the OH + NO_2 and OH + HNO_3 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.

Comment on: “The measurement of tropospheric OH radicals by laser‐induced fluorescence spectroscopy during the POPCORN Field Campaign” by Hofzumahaus et al. and “Intercomparison of tropospheric OH radical measurements by multiple folded long‐path laser absorption and laser induced fluorescence” by Brauers et al.

Calibration of laser induced fluorescence (LIF) instruments that measure OH is challenging because it is difficult to reliably introduce a known amount of this reactive radical into a measurement apparatus. In a recent paper, Hofzumahaus et al., [1996] describe a novel and seemingly simple technique to accomplish this goal: they dissociate trace quantities of water vapor in air with a low pressure mercury (Hg) lamp to produce low concentrations (10^5 - 10^9 cm^(-3)) of OH (R1).

Measurements of CO in the upper troposphere and lower stratosphere

In situ measurements of CO were made in the upper troposphere and lower stratosphere (7–21 km altitude) with the Jet Propulsion Laboratory (JPL) Aircraft Laser Infrared Absorption Spectrometer (ALIAS) on 58 flights of the NASA ER-2 aircraft from October 1995 through September 1997, between 90°N and 3°S latitude. Measured upper tropospheric CO was variable and typically ranged between 55 and 115 ppb, except for higher values over Alaska during summer 1997. Tropical stratospheric CO ranged from 58 ± 5 ppb at the tropopause to 12 ± 2 ppb above 20 km, having similar profiles in all seasons of the year. The tropical profile is reproduced by a simple Lagrangian box model of tropical ascent using measured CH4 and OH concentrations, Cl and O(^1D) concentrations from a photochemical model, and diabatic heating rates from a radiative heating model. From measured CO, quasi-horizontal mixing between the tropical and mid-latitude lower stratosphere is inferred to be rapid in the region between 400 K and 450 K potential temperature (altitudes less than 20 km).

Quantitative constraints on the atmospheric chemistry of nitrogen oxides: An analysis along chemical coordinates

In situ observations Of NO_2, NO, NO_y, ClONO_2, OH, O_3, aerosol surface area, spectrally resolved solar radiation, pressure and temperature obtained from the ER-2 aircraft during the Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) experiments are used to examine the factors controlling the fast photochemistry connecting NO and NO_2 and the slower chemistry connecting NO_x and HNO_3. Our analysis uses “chemical coordinates” to examine gradients of the difference between a model and precisely calibrated measurements to provide a quantitative assessment of the accuracy of current photochemical models. The NO/NO_2 analysis suggests that reducing the activation energy for the NO+O_3 reaction by 1.7 kJ/mol will improve model representation of the temperature dependence of the NO/NO_2 ratio in the range 215–235 K. The NO_x/HNO_3 analysis shows that systematic errors in the relative rate coefficients used to describe NO_x loss by the reaction OH + NO_2 → HNO_3 and by the reaction set NO_2 + O_3 → NO_3; NO_2 + NO_3 → N_(2)O_5; N_(2)O_5 + H_(2)O → 2HNO_3 are in error by +8.4% (+30/−45%) (OH+NO_2 too fast) in models using the Jet Propulsion Laboratory 1997 recommendations [DeMore et al., 1997]. Models that use recommendations for OH+NO2 and OH+HNO_3 based on reanalysis of recent and past laboratory measurements are in error by 1.2% (+30/−45%) (OH+NO_2 too slow). The +30%/−45% error limit reflects systematic uncertainties, while the statistical uncertainty is 0.65%. This analysis also shows that the POLARIS observations only modestly constrain the relative rates of the major NO_x production reactions HNO3 + OH → H_(2)O + NO_3 and HNO_3 + hν → OH + NO_2. Even under the assumption that all other aspects of the model are perfect, the POLARIS observations only constrain the rate coefficient for OH+HNO_3 to a range of 65% around the currently recommended value.

Comparing atmospheric [HO2]/[OH] to modeled [HO2]/[OH]: Identifying discrepancies with reaction rates

Reactions that inter-convert OH and HO_2 are directly involved in the catalytic removal of O_3 in the lower stratosphere and in the catalytic production of O_3 in the upper troposphere. The agreement between the measured and modeled [HO_2]/[OH] tests our current understanding of this important chemistry. Recent changes to the recommended rate constants for OH+O_3 and HO_2+O_3 call into question how accurately the chemistry of the stratosphere is understood. [HO_2]/[OH] calculated with the new recommendations is 48% higher than the observations throughout the lower stratosphere, exceeding the uncertainty limits of the observations (20%). The extensive atmospheric data set allows tests of the rates of the individual processes that couple these free radicals. This work shows that the discrepancy is largest when the ratio is controlled by the reactions of OH and HO_2 with ozone.

Ozone destruction and production rates between spring and autumn in the Arctic stratosphere

In situ measurements of radical and long-lived species were made in the lower Arctic stratosphere (18 to 20 km) between spring and early autumn in 1997. The measurements include O_3, ClO, OH, HO_2, NO, NO_2, N_(2)O, CO, and overhead O_3. A photochemical box model constrained by these and other observations is used to compute the diurnally averaged destruction and production rates of O3 in this region. The rates show a strong dependence on solar exposure and ambient O_3. Total destruction rates, which reach 19%/month in summer, reveal the predominant role of NO_x and HO_x catalytic cycles throughout the period. Production of O_3 is significant only in midsummer air parcels. A comparison of observed O_3 changes with destruction rates and transport effects indicates the predominant role of destruction in spring and an increased role of transport by early autumn.

NOy partitioning from measurements of nitrogen and hydrogen radicals in the upper troposphere

Recent studies using NO, NOy, OH and HO2 (HOx) observations have postulated acetone and convection of peroxides as significant sources of HOx in the upper troposphere (UT). This work focuses on the effect these additional HOx sources have on the modeled NOy partitioning and comparisons of the modeled NOx/NOy ratio to observations. The measured NOx/NOy ratio is usually much higher than predicted regardless of the presence of acetone in the model. The exception occurs for air parcels having low NOy and O3 values. For these air parcels the measured NOx/NOy ratio is much lower than the calculated ratio unless acetone is included in the model. In all cases acetone increases the fraction of NOy that is peroxy acetyl nitrate (PAN) from typical values of much less than 0.1 to values as high as 0.35. Including acetone also reduces the scatter in a comparison between modeled and observed NOx/NOy ratios.

Inorganic chlorine partitioning in the summer lower stratosphere : Modeled and measured [ClONO2]/[HCl] during POLARIS

We examine inorganic chlorine (Cl_y,) partitioning in the summer lower stratosphere using in situ ER-2 aircraft observations made during the Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) campaign. New steady state and numerical models estimate [ClONO_2]/[HCl] using currently accepted photochemistry. These models are tightly constrained by observations with OH (parameterized as a function of solar zenith angle) substituting for modeled HO_2 chemistry. We find that inorganic chlorine photochemistry alone overestimates observed [ClONO_2]/[HCl] by approximately 55–60% at mid and high latitudes. On the basis of POLARIS studies of the inorganic chlorine budget, [ClO]/[ClONO_2], and an intercomparison with balloon observations, the most direct explanation for the model-measurement discrepancy in Cl_y, partitioning is an error in the reactions, rate constants, and measured species concentrations linking HCl and ClO (simulated [ClO]/[HCl] too high) in combination with a possible systematic error in the ER-2 ClONO_2 measurement (too low). The high precision of our simulation (±15% 1σ for [ClONO_2]/[HCl], which is compared with observations) increases confidence in the observations, photolysis calculations, and laboratory rate constants. These results, along with other findings, should lead to improvements in both the accuracy and precision of stratospheric photochemical models.