Forest, savannah, and agricultural fires in the tropics and subtropics are sources for widespread pollution and release many organic substances into the air and soil, including persistent organic pollutants, i.e., polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs). The significance of this source for the exposure of humans and the environment in Africa toward phenanthrene, fluoranthene, pyrene, benzo(a)pyrene, 2,3,7,8-tetrachlorodibenzo-p-dioxin, 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin, and octachlorodibenzo-p-dioxin is studied using daily global emissions from vegetation fires observed by satellite and a global multicompartment chemistry-transport model. Near-ground atmospheric concentrations of model-predicted vegetation fire related concentrations of PAHs and PCDDs were in the 10-1000 and 10(-5)-10(-3) pg m(-3) ranges, respectively. Vegetation fires in Africa are found to emit 180 ± 25 kg yr(-1) of PCDD/Fs. By comparison with observations, it is found that fires explain 1-10% of the PCDD (5% of 2,3,7,8- tetrachlorodibenzo-p-dioxin) concentrations in the rural and background atmosphere of sub-Saharan Africa. The contribution of vegetation fires to exposure to PAH is probably >10%, but cannot be quantified due to lack of knowledge with regard to both emission factors and photochemistry. A sensitivity analysis suggests that the heterogeneous reaction of PAHs with ozone is effectively limiting atmospheric lifetime and long-range transport.