The primary structures of four major sialylated saccharide alditols derived from mucus glycoproteins of human seminal plasma were established by fast-atom-bombardment mass spectrometry and methylation analysis. Anomeric configurations of the glycosidic bonds were determined by exoglycosidase digestion and C r 0 3 oxidation.GalN Ac-01 Based on quantitative data from high-pressure liquid chromatography and on structural information, the biosynthetic pathways for neutral and sialylated saccharides related to the Lewis system were proposed. Expression of saccharides A 6, A 7 and A 8 and their asialo counterparts, which are characterized by antigenic determinants H, Le" and Ley, respectively, is qualitatively and quantitatively dependent on the Lewis blood type of the respective donor and correlates with Ca 19-9 activity of its seminal plasma.