Hydrochemical and isotopic effects associated with petroleum fuel biodegradation pathways in a chalk aquifer

Hydrochemical data, compound specific carbon isotope analysis and isotopic enrichment trends in dissolved hydrocarbons and residual electron acceptors have been used to deduce BTEX and MTBE degradation pathways in a fractured chalk aquifer. BTEX compounds are mineralised sequentially within specific redox environments, with changes in electron acceptor utilisation being defined by the exhaustion of specific BTEX components. A zone of oxygen and nitrate exhaustion extends approximately 100 m downstream from the plume source, with residual sulphate, toluene, ethylbenzene and xylene. Within this zone complete removal of the TEX components occurs by bacterial sulphate reduction, with sulphur and oxygen isotopic enrichment of residual sulphate (epsilon(s) =- 14.4 parts per thousand to - 16.0 parts per thousand). Towards the plume margins and at greater distance along the plume flow path nitrate concentrations increase with delta N-15 values of up to +40 parts per thousand indicating extensive denitrification. Benzene and MTBE persist into the denitrification zone, with carbon isotope enrichment of benzene indicating biodegradation along the flow path. A Rayleigh kinetic isotope enrichment model for C-13-enrichment of residual benzene gives an apparent epsilon value of -0.66 parts per thousand. MTBE shows no significant isotopic enrichment (delta C-13 = -29.3 parts per thousand to -30.7 parts per thousand) and is isotopically similar to a refinery sample (delta C-13 = -30.1 parts per thousand). No significant isotopic variation in dissolved MTBE implies that either the magnitude of any biodegradation-induced isotopic fractionation is small, or that relatively little degradation has taken place in the presence of BTEX hydrocarbons. It is possible, however, that MTBE degradation occurs under aerobic conditions in the absence of BTEX since no groundwater samples were taken with co-existing MTBE and oxygen. Low benzene delta C-13 values are correlated with high sulphate delta S-34, indicating that little benzene degradation has occurred in the sulphate reduction zone. Benzene degradation may be associated with denitrification since increased benzene delta C-13 is associated with increased delta N-15 in residual nitrate. Re-supply of electron acceptors by diffusion from the matrix into fractures and dispersive mixing is an important constraint on degradation rates and natural attenuation capacity in this dual-porosity aquifer. (c) 2005 Published by Elsevier B.V.