Biomass burning is an important source of smoke aerosol particles, which contain water-soluble inorganic and organic species, and thus have a great potential of affecting cloud formation, precipitation, and climate on global and regional scales. In this study, we have developed a new chromatographic method for the determination of levoglucosan (a specific tracer for biomass burning particles), related polyhydroxy compounds, and 2-methylerythritol (recently identified as isoprene oxidation product in fine aerosols in the Amazon) in smoke and in rainwater samples. The new method is based on water extraction and utilizes ion-exclusion high-performance liquid chromatography (IEC-HPLC) separation and spectroscopic detection at 194 nm. The new method allows the analysis of wet samples, such as rainwater samples. In addition, aliquots of the same extracts can be used for further analyses, such as ion chromatography. The overall method uncertainty for sample analysis is 15%. The method was applied to the analysis of high-volume and size-segregated smoke samples and to rainwater samples, all collected during and following the deforestation fires season in Rondonia, Brazil. From the analysis of size-segregated samples, it is evident that levoglucosan is a primary vegetation combustion product, emitted mostly in the 0.175-1 microm size bins. Levoglucosan concentrations decrease below the detection limit atthe end of the deforestation fires period, implying that it is not present in significant amounts in background Amazon forest aerosols. The ratio of daytime levoglucosan concentration to particulate matter (PM) concentration was about half the nighttime ratio. This observation is rationalized by the prevalence of flaming combustion during day as opposed to smoldering combustion during night. This work broadens the speciation possibilities