Abstract. A large number of oxygenated organic chemicals (peroxyacyl nitrates, alkyl nitrates, acetone, formaldehyde, methanol, methylhydroperoxide, acetic acid and formic acid) were measured during the 1997 Subsonic Assessment (SASS) Ozone and Nitrogen Oxide Experiment (SONEX) airborne field campaign over the Atlantic. In this paper, we present a first picture of the distribution of these oxygenated organic chemicals (Ox-organic) in the troposphere and the lower stratosphere, and assess their source and sink relationships. In both the troposphere and the lower stratosphere, the total atmospheric abundance of these oxygenated species (ZOx-organic) nearly equals that of total nonmethane hydrocarbons (ZNMHC), which have been traditionally measured.

The photochemistry of the troposphere over the South Atlantic basin is examined by modeling of aircraft observations up to 12‐km altitude taken during the TRACE A expedition in September–October 1992. A close balance is found in the 0 to 12‐km column between photochemical production and loss of O3, with net production at high altitudes compensating for weak net loss at low altitudes. This balance implies that O3 concentrations in the 0–12 km column can be explained solely by in situ photochemistry; influx from the stratosphere is negligible. Simulation of H2O2, CH3OOH, and CH2O concentrations measured aboard the aircraft lends confidence in the computations of O3 production and loss rates, although there appears to be a major gap in current understanding of CH2O chemistry in the marine boundary layer. The primary sources of NOx over the South Atlantic Basin appear to be continental (biomass burning, lightning, soils). There is evidence that NOx throughout the 0 to 12‐km column is recycled from its oxidation products rather than directly transported from its primary sources. There is also evidence for rapid conversion of HNO3 to NOx in the upper troposphere by a mechanism not included in current models. A general representation of the O3 budget in the tropical troposphere is proposed that couples the large‐scale Walker circulation and in situ photochemistry. Deep convection in the rising branches of the Walker circulation injects NOx from combustion, soils, and lightning to the upper troposphere, leading to O3 production; eventually, the air subsides and net O3 loss takes place in the lower troposphere, closing the O3 cycle. This scheme implies a great sensitivity of the oxidizing power of the atmosphere to NOx emissions in the tropics.

Biomass‐burning plumes and haze layers were observed during the ABLE 2A flights in July/August 1985 over the central Amazon Basin. The haze layers occurred at altitudes between 1000 and 4000 m and were usually only some 100 to 300‐m thick but extended horizontally over several 100 km. They could be traced by satellite imaging and trajectory studies to biomass burning at the southern perimeter of the Amazon Basin, with transport times estimated to be 1–2 days. These layers strongly influenced the chemical and optical characteristics of the atmosphere over the eastern Amazon Basin. The concentrations of CO, CO2, O3, and NO were significantly elevated in the plumes and haze layers relative to the regional background. The NO/CO ratio in fresh plumes was much higher than in the aged haze layers, suggesting that more than 80% of the NOx in the haze layers had been converted to nitrate and organic nitrogen species subsequent to emission. The haze aerosol was composed predominantly of organic material, NH4+, K+, NO3−, SO4=, and anionic organic species (formate, acetate, and oxalate). While the concentrations of most aerosol ions were substantially higher in the haze layers than in the regional background aerosol, the ratios between the aerosol ions in the haze layer aerosols were very similar to those in the boundary layer aerosol over the central Amazon region. Simultaneous measurements of trace gas and aerosol species in the haze layers made it possible to derive emission ratios for CO, NOx, NH3, sulfur oxides, and aerosol constituents relative to CO2. Regional and global emission estimates based on these ratios indicate that biomass burning is an important contributor in the global and regional cycles of carbon, sulfur, and nitrogen species. Similar considerations suggest that photochemical ozone production in the biomass‐burning plumes contributes significantly to the regional ozone budget.

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A series of large mesoscale convective systems that occurred during the Brazilian phase of GTE/TRACE A (Transport and Atmospheric Chemistry near the Equator‐Atlantic) provided an opportunity to observe deep convective transport of trace gases from biomass burning. This paper reports a detailed analysis of flight 6, on September 27, 1992, which sampled cloud‐ and biomass‐burning‐perturbed regions north of Brasilia. High‐frequency sampling of cloud outflow at 9–12 km from the NASA DC‐8 showed enhancement of CO mixing ratios typically a factor of 3 above background (200–300 parts per billion by volume (ppbv) versus 90 ppbv) and significant increases in NOx and hydrocarbons. Clear signals of lightning‐generated NO were detected; we estimate that at least 40% of NOx at the 9.5‐km level and 32% at 11.3 km originated from lightning. Four types of model studies have been performed to analyze the dynamical and photochemical characteristics of the series of convective events. (1) Regional simulations for the period have been performed with the NCAR/Penn State mesoscale model (MM5), including tracer transport of carbon monoxide, initialized with observations. Middle‐upper tropospheric enhancements of a factor of 3 above background are reproduced. (2) A cloud‐resolving model (the Goddard cumulus ensemble (GCE) model) has been run for one representative convective cell during the September 26–27 episode. (3) Photochemical calculations (the Goddard tropospheric chemical model), initialized with trace gas observations (e.g., CO, NOx, hydrocarbons, O3) observed in cloud outflow, show appreciable O3 formation postconvection, initially up to 7–8 ppbv O3/d. (4) Forward trajectories from cloud outflow levels (postconvective conditions) put the ozone‐producing air masses in eastern Brazil and the tropical Atlantic within 2–4 days and over the Atlantic, Africa, and the Indian Ocean in 6–8 days. Indeed, 3–4 days after the convective episode (September 30, 1992), upper tropospheric levels in the Natal ozone sounding show an average increase of ∼30 ppbv (3 Dobson units (DU) integrated) compared to the September 28 sounding. Our simulated net O3 production rates in cloud outflow are a factor of 3 or more greater than those in air undisturbed by the storms. Integrated over the 8‐ to 16‐km cloud outflow layer, the postconvection net O3 production (∼5–6 DU over 8 days) accounts for ∼25% of the excess O3 (15–25 DU) over the South Atlantic. Comparison of TRACE A Brazilian ozonesondes and the frequency of deep convection with climatology [Kirchhoff et al., this issue] suggests that the late September 1992 conditions represented an unusually active period for both convection and upper tropospheric ozone formation.