Bisulfite anions and sulfinic acids are shown by ESR spectroscopy to undergo reduction with radiolytically produced free electrons and oxidation by hole centers (Cl-2(.-)) in a low-temperature aqueous LiCl glass. Electron; reduced intermediates display g anisotropy within the 2.010-2.002 range and are considered as neutral or singly deprotonated forms of sulfuranyl radicals (HO)(3)S-., (RO)(2)SOH., and RS(OH)(2)(.). The oxidized species produced by hole trapping are sulfite (SO3.-) and sulfonyl (RSO(2)(.)) radicals. Dialkyl sulfites scavenge free electrons only and are not oxidized by Cl-2(.-). Both oxidized and reduced intermediates add oxygen on annealing forming peroxyl radicals which are identified by their characteristic oxygen-17 hyperfine couplings. A large 100 G oxygen-17 coupling with the terminal oxygen atom found for oxidized sulfite-oxygen adduct (O3SOO.)-O-- is in accord with its known high reactivity. Sulfuranyl peroxyls formed by the reductive pathway show lower O-17 couplings (e.g., 90 G with terminal oxygens) and are expected to be far less reactive than alkyl peroxyls. Ab initio MO calculations predict stable structures for these sulfuranyl peroxyls, suggesting a trigonal-bipyramid coordination of the central sulfur atom. However, the sulfuranyl intermediates formed through one-electron reduction of dimethyl and methylphenyl sulfoxides are found to be unstable even in low-temperature glass, fragmenting into a methyl radical and sulfenic acid or into a hydroxyl anion and sulfide radical cation, respectively.