High concentrations of aliphatic organic acids (∼1 mM acetate) in groundwater from a petroleum hydrocarbon‐contaminated aquifer are associated with elevated concentrations (∼30 μg/L) of lead. This pattern suggests that toxic effects of lead have contributed to the observed accumulation of organic acids. This hypothesis was tested by examining the effects of lead on carbon mineralization and organic acid accumulation in petroleum‐contaminated aquifer material incubated under different terminal electron‐accepting conditions. Lead was found to inhibit fermentation (organic acid accumulation) as well as microbial carbon mineralization (CO2or CH4production) under aerobic, nitrate‐reducing, sulfate‐reducing, and methanogenic conditions. Thus Pb does not appear to be the primary cause of organic acid accumulation at the field site. Rather, substantial accumulation of aliphatic organic acids occurred only in methanogenic microcosms, and only trace amounts of acetic acid were detected in sulfate‐reducing microcosms. This pattern parallels field observations in which high organic acid concentrations were detected in methanogenic zones, but only low concentrations of acetic acid were detected in sulfate‐reducing zones.