Sulfur isotopes in ancient sediments provide a record of past environmental conditions. The long-time-scale variability and apparent asymmetry in the magnitude of minor sulfur isotope fractionation in Archean sediments remain unexplained. Using an integrated biogeochemical model of the Archean sulfur cycle, we find that the preservation of mass-independent sulfur is influenced by a variety of extra-atmospheric mechanisms, including biological activity and continental crust formation. Preservation of atmospherically produced mass-independent sulfur implies limited metabolic sulfur cycling before similar to 2500 million years ago; the asymmetry in the record indicates that bacterial sulfate reduction was geochemically unimportant at this time. Our results suggest that the large-scale structure of the record reflects variability in the oxidation state of volcanic sulfur volatiles.