Ground water chemistry data collected over a six‐year period show that the distribution of contaminants and redox processes in a shallow petroleum hydrocarbon‐contaminated aquifer has changed rapidly over time. Shortly after a gasoline release occurred in 1990, high concentrations of benzene were present near the contaminant source area. In this contaminated zone, dissolved oxygen in ground water was depleted, and by 1994 Fe(lll) reduction and sulfate reduction were the predominant terminal electron accepting processes. Significantly, dissolved methane was below measurable levels in 1994, indicating the absence of significant methanogenesis. By 1996, however, depletion of solid‐phase Fe(lll)‐oxyhydroxides in aquifer sediments and depletion of dissolved sulfate in ground water resulted in the onset of methanogenesis. Between 1996 and 2000, water‐chemistry data indicated that methanogenic metabolism became increasingly prevalent. Molecular analysis of 16S‐rDNA extracted from sediments shows the presence of a more diverse methanogenic community inside as opposed to outside the plume core, and is consistent with water‐chemistry data indicating a shift toward methanogenesis over time. This rapid evolution of redox processes reflects several factors including the large amounts of contaminants, relatively rapid ground water flow (∼0.3 m/day [∼1 foot/day]), and low concentrations of microbially reducible Fe(lll) oxyhydroxides (∼ 1 umol/g) initially present in aquifer sediments. These results illustrate that, under certain hydrologic conditions, redox conditions in petroleum hydrocarbon‐contaminated aquifers can change rapidly in time and space, and that the availability of solid‐phase Fe(lll)‐oxyhydroxides affects this rate of change.