In summer 2010, twenty eight (14 PM2.5 samples plus 14 samples PM2.5–10) smoke samples were collected during wildfires that occurred in central Portugal. A portable high-volume sampler was used to perform the sampling, on quartz fibre filters of coarse (PM2.5–10) and fine (PM2.5) smoke samples. The carbonaceous content (elemental and organic carbon) of particulate matter was analysed by a thermal–optical technique. Subsequently, the particulate samples were solvent extracted and fractionated by vacuum flash chromatography into three different classes of organic compounds (aliphatics, polycyclic aromatic hydrocarbons (PAHs) and carbonyl compounds). The organic speciation was performed by gas chromatography–mass spectrometry (GC–MS). Emissions were dominated by the fine particles, which represented around 92% of the PM10. A clear predominance of carbonaceous constituents was observed, with organic to elemental carbon (OC/EC) ratios ranging between 1.69 and 245 in both size fractions. The isoprenoid ketone 6,10,14-trimethyl-2-pentadecanone, a tracer for secondary organic aerosol formation, was one of the dominant constituents in both fine and coarse particles. Retene was the most abundant compound in all samples. Good correlations were obtained between OC and both aliphatic and PAH compounds. Pyrogenic processes, thermal release of biogenic compounds and secondary processing accounted for 97% of the apportioned PM2.5 levels.
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