An analytical procedure consisting of ultrasonic extraction with acetonitrile, trimethylsilylation and GC-MS analysis was applied to the determination of levoglucosan (LG) in aerosol collected with three different filter types (teflon, quartz, glass). Methyl-beta-L-arabinopyranoside (MA) and sedoheptulosan (SD, 2,7-anhydro-beta-D-altro-heptulopyranose) were investigated as recovery standards. Mean recovery of MA decreased in the order 82%, 78%, 74% and that of SD from 82% to 76% and 32% from teflon, quartz and glass blank filters, respectively, whereas recovery of LG was little affected (80-86%). The extraction efficiency from glass filters could be increased by using methanol in place of acetonitrile, but recovery of SD remained inadequate. Internal calibration with MA was linear in the 0.035-70 microg mL(-1) LG concentration interval. The method was tested on different air filter materials utilized to sample PM(10) in outdoor air and wood smoke emitted from stove and boiler encompassing LG concentrations from 0.06 to 230 microg m(-3) with RSD in the 2.9-22% range. The application of the method in aerosol sampled in alpine zones of Italy revealed a linear correlation between LG and PM(10) concentrations with a higher proportion of LG in winter and in rural areas where the use of woody biomass for residential heating is widespread.