As part of the Experiment for Regional Sources and Sinks of Oxidants (EXPRESSO) conducted over central Africa in November 1996, 24 airborne aerosol samples were obtained and further analyzed for black and organic carbon (BC and OC), water-soluble organic carbon (WSOC), polycyclic aromatic hydrocarbons (PAHs), soluble ions, elemental composition, and morphology. Particles were collected in the different atmospheric layers either above the tropical forest or the savanna of central Africa near the Intertropical Convergence Zone. Particle number concentrations (10–14,000 nm diameter) were found to be high in all atmospheric layers (3100±2060 cm−3, n = 24). Soil-derived particles were less abundant than expected (20±18 μg m−3, n = 21), and their presence was assessed mainly to reentrainment by fires. On the other hand, pyrogenic particles were abundant, and high levels of black carbon (BC) concentrations were found either in the forest boundary layer (3.8±2.3 μg m−3, n = 6), the savanna boundary layer (9.8±3.9 μg m−3, n = 6), or in the Harmattan layer (8.7±1.6 μg m−3, n = 3). Other fire tracers (such as K, oxalate, or PAHs) confirmed the overwhelming impact of savanna fires in the regional troposphere. Another result is the possible occurrence of vertical and horizontal exchanges between the different layers and through the ITCZ. WSOC was measured in our samples representing on average 46±9% (n = 11) of the total particulate organic carbon. High values were found in the Harmattan layer, where on average WSOC accounts for 85±18%, (n = 3) of the total particulate organic carbon, pointing out the potential of biomass burning particles to act as cloud condensation nuclei (CCN). Different chemical indicators were used, which produce convergent information on the aging of biomass burning particles. Among these indicators, the ratio WSOC/OC was found to increase by a factor of 2 to 3 from the ground to the Harmattan layer. A product of this work is also the presence of high concentrations of organic acids (formate, acetate, and also oxalate) in the forest boundary layer suggesting a strong biogenic source for these compounds. Finally, during the EXPRESSO experiment, which took place at the beginning of the dry season, savanna fires were prevailing at a regional scale, whereas dust inputs by Harmattan airflow were still low. Our results suggest that in these conditions nitrate primarily remains in the gaseous phase, and thus the translocation of nitrogen nutrients is confined to the region.