Validation of a HILIC/ESI-MS/MS method for the wood burning marker levoglucosan and its isomers in airborne...

In the present study, a methodology involving hydrophilic interaction liquid chromatography (HILIC) and electrospray (ESI) tandem mass spectrometry (MS/MS) was developed for measurement of anhydrous monosaccharides as markers for wood burning in atmospheric aerosols, PM₁₀. No extensive sample preparation, other than ultrasound-assisted solvent extraction and evaporation, was applied. A pentahydroxysilica column enabled separation of levoglucosan from mannosan and galactosan within 5 min and the quantitative performance was validated using the standard reference materials (SRM) 1649a and 1649b. The experimentally obtained results for SRMs were in agreement with values previously reported in other studies. Achieved instrumental limits of detection (LODs) were below 10 pg injected on column, corresponding to LODs in air lower than 0.10 ng/m³ for all measured isomers for 2-3 day sampling with 1.0 m^-3 h^-1 sampling rate. The validated method was used for the determination of levoglucosan and its isomers in atmospheric aerosols collected in three different Swedish urban areas during the winter and summer time in 2017. The total measured concentrations for levoglucosan and galactosan + mannosan were determined to be between 78 and 167 ng/m³ in January 2017, which is approximately 10-times higher compared to the levels detected in July, reflecting the higher frequency of wood burning for heating during the cold season. Calculated concentration ratios between levoglucosan and its isomers in the urban area samples indicated mostly mixed softwood/hardwood combustion in winter time; on the other hand, softwood burning was observed as the major emission in summer time.