To determine the abundance and form of S existing in various states in blast furnace slags, the chem. shifts were used with an ordinary fluorescent x-ray spectrometer.Chem. shifts enabled the oxidation degree of S in slags to be determined from the ratio of S6+/S2-.The degree of S oxidation was determined on the surface and in the volume of bulk specimens.The method is useful also in determining the abundance ratio of S2-, S4+, and S6+.