• Reliable isomeric assignments for monosaccharide anhydrides using LC-MS/MS. • Robust dual-platform LC-MS/MS and GC–MS analytical workflow. • Column chemistry and isomer-specific MS/MS transitions govern MA identification. • Derivatized and underivatized monosaccharide anhydrides exhibit distinct stability. Monosaccharide anhydrides (MAs), levoglucosan (LVG), mannosan (MAN), and galactosan (GAN) are pyrolysis products of cellulose and hemicellulose during biomass burning (wildfires, crop residu
