Anaerobic turnover of organic compounds in oil sands tailings ponds is accomplished by a complex microbial consortium. We examined major electron accepting processes in mature fine tailings (MFT). Beside methanogenesis and sulphate reduction, microbial iron reduction was an important process of anaerobic respiration. Microbial numbers and activity were comparable to those reported for natural lakes. To understand metabolic interactions of indigenous methanogenic and sulphate-reducing communities, we conducted a 6 month microcosm experiment with MFT supplemented with easily available carbon sources and molybdate and/or 2-bromoethane sulphonate (BES) as specific inhibitors for sulphate reduction and methanogenesis. Methanogenesis increased when microcosms were supplemented with extra carbon, but was completely inhibited by the addition of BES. Molybdate not only inhibited sulphate reduction, but also methanogenesis, indicating a positive relation between the two processes. The turnover of extra carbon sources differed between microcosms treated with molybdate and BES. Acetate and propionate were not consumed in microcosms amended with molybdate, indicating that sulphate-reducing bacteria (SRB) were responsible for their metabolisation, and that methane was rather produced by hydrogenotrophic methanogens. In microcosms without molybdate, acetate transiently accumulated, indicating the activity of both incomplete and complete oxidizing SRB. Ethanol and lactate were also consumed in the simultaneous presence of BES and molybdate, demonstrating the occurrence of other anaerobic processes. Biomass increased by the addition of extra carbon, mainly due to a relative increase in the proportion of SRB. The addition of extra carbon lowered the degradation of BTEX compounds.