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[en] Reduced sulfur species in ground-granulated blast furnace slag (GGBFS) play an important role in immobilizing radionuclide contaminants in caustic cement-GGBFS mixtures via reductive precipitation reaction. However, sulfur (S) speciation and its stability in GGBFS have not been clearly understood. In this study, S speciation of GGBSF in alkaline radionuclide liquid waste simulant solutions was investigated using S K-edge X-ray absorption near edge structure spectroscopy (XANES) and powder X-ray diffraction (XRD) measurements. Although S mineralogy was not detectable by XRD due to the amorphous nature in GGBFS, XANES analysis revealed that GGBSF contained high concentration of sulfoxide (~ 57%), followed by S(0) (~ 37%), sulfate (~ 3.81%), and sulfonate (~ 2.33%). When GGBFS was reacted with anoxic or oxygenated alkali solutions, it retained most of sulfoxide with some changes in the fraction of elemental S, sulfonate and sulfate, indicating the involvement of reduced S species in the reductive precipitation of radionuclides. This study shows the presence of intermediate S valence species in GGBFS. - Highlights: • Reduced sulfur speciation in blast furnace slag was investigated using S K-edge XANES analysis. • Blast furnace slag contains high concentration of sulfoxide (~ 57%). • The sulfoxide fraction in slag was stable when treated with anoxic or oxygenated alkali solutions.