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So far, studies on the conversion of stereochemistry under photo-Fenton conditions and their atmospheric implication are still rare. Here, we found that the biomass burning marker, the chiral compound levoglucosan (L), undergoes oxidative degradation under photo-Fenton conditions and can be isomerized into mannosan (M) and galactosan (G) simultaneously. Among the formic acid, acetic acid, and oxalic acid in the degradation products of levoglucosan, it was found that the yield of formation of formic acid in the photo-Fenton pathway can be as high as 86%. It