Forest soils that have accumulated anthropogenic sulfur (S) as a result of historical air pollution may gradually or suddenly release inorganic sulfate either by desorption of inorganic sulfate or by mineralization of organic S, even after mitigation of previous air pollution. The release of inorganic sulfate from soil to surface water leads directly to watershed acidification. Thus, whether the organic S compounds that have accumulated in soils are resistant to microbial activity, due to formation of organo-mineral complexes, is essential information for management of forest soil ecosystem services. A nationwide air pollution monitoring survey by the Japanese Ministry of the Environment identified acidification of both surface water and soil in the Lake Ijira watershed of central Japan, presumably sourced from the Chukyo Industrial Area which lies upwind of the watershed. We compared the amount of S accumulated in the Ijira soils (Dystrudepts) with that in comparable soils in other watersheds in central Japan that were less affected by industrial air pollution. To determine how much mineral-associated organic S had accumulated in the Ijira soils, we measured pyrophosphate- extractable S. We used high-resolution x-ray fluorescence (HRXRF) spectroscopy with a double-crystal type high energy resolution spectrometer to estimate the oxidation states of both mineral-associated and free organic S. We also measured isotope compositions to explore S dynamics in the soils. We found that more S had accumulated in the Ijira soils than in the comparable soils from other watersheds in central Japan. Concentrations of total S in the Ijira soils varied among soil horizons, reaching more than 1000 mg S kg(-1) in some horizons. Mineral-associated organic accounted for more than half of the total accumulated S. High-resolution x-ray fluorescence spectrum analyses showed that mineral-associated organic S was retained at both high and low oxidation states. The delta S-34 values of total S in the deeper horizons tended to be higher than those of the uppermost horizons of the Ijira soils and correlated positively with concentrations of extractable Al and Fe oxides (which characterize pedogenic minerals). Our results suggest that about half of total accumulated S in Ijira soils is stabilized in pedogenic minerals and the remainder comprises free organic S and adsorbed inorganic sulfates. There might have been repetitive mobilization and immobilization of S and the degraded organic S might have greater affinity with pedogenic minerals. Further, the ratio of total C to mineral-associated organic S correlated negatively with concentrations of extractable Al and Fe oxides, suggesting that organic S is more resistant to mineralization than organic C because is preferentially associated with the pedogenic minerals. Monitoring of the chemical states of S compounds in soils historically exposed to air pollution is recommended to assist in prediction of the fate of the S compounds that have accumulated in them.