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It is known that residential wood combustion (RWC) is an important source of fine particle emissions. The purpose of this work was to characterize the chemical composition of the particulate matter present in the Temuco urban atmosphere during winter, specifically the polycyclic aromatic hydrocarbon (PAH) profile, because PAHs are considered to be among the key compounds in particulate matter toxicity. During the 2008 winter monitoring campaign, samples of particulate matter with aerodynamic diameters of ≤10 (PM10) and ≤2.5 (PM2.5) μm were taken on days with contamination episodes. Sixteen U.S. Environmental Protection Agency (EPA) PAH compounds were extracted with toluene and determined by gas chromatography–mass spectrometry (GC-MS). The results show that phenantrene was the predominant compound associated with particulate matter, at a concentration range between 300 and 600 ng m−3, 18 times higher than the second most abundant PAH compound. High-molecular-mass compounds such as dibenz[a,h]anthracene, benzo[g,h,i]perylene, and indeno[1,2,3,c,d]pyrene were also found, but they were minorities in the set. It was recognized from the PAH concentration ratios of the Temuco atmospheric aerosol that the main contamination source was in fact residential wood combustion; although not all the concentration ratios evaluated match the reported reference values, probably due to the kind of biomass used, the characteristics of Chilean heating appliances and climate.Implications:The study results suggest that if molecular markers (MMs) and concentration ratios (CRs) are dependent on the type of firewood and combustion processes specific to each location, among others factors, then the values of these indicators could be applicable with caution between different areas, although not necessarily they must be totally in accord. Moreover, having representative values of MM and CR of each place, it will achieve a better estimation of the source importance and concentrate the monitoring and the control strategies. Regulatory organizations in each country can have more reliable information and optimize financial and human resources, enabling it to reduce air pollution and improve the health of population.