Long‐term evaluation of hydrocarbon degradation rates within the source zone under natural and enhanced attenuation for site closure purposes

Abstract

Despite addressing the cleanup of petroleum hydrocarbon contamination plumes in groundwater, challenges with site closure persist due to the ongoing long‐term contaminant release from source zones. Thus, source zone monitoring even in the presence of residual light nonaqueous‐phase liquid (LNAPL) is mandated by many countries' regulatory agencies before site closure. In this study, four independent controlled‐release sites, each containing a particular fraction of ethanol in gasoline, that is, 10%, 24%, 25%, and 85% (v/v), were subjected to monitored natural attenuation (MNA) alone (E24 and E85), and with nitrate (E25) and sulfate (E10) biostimulation at the vicinity of the source zone. To the best of the authors' knowledge, this is the longest controlled gasohol release monitoring study performed to date at the source zone for site closure (nearly 18 years of monitoring). Both natural source zone depletion and biostimulation were found to reduce benzene concentrations to acceptable remediation target levels according to environmental regulatory councils. Benzene biodegradation rates (λs) were one order of magnitude higher than those reported in the literature for diluted concentrations in groundwater plumes. The decay rate of benzene varied between 0.45 and 1.75/year and was strongly influenced by the mass of ethanol. Compared to biostimulation with nitrate (half‐life of 1.52 years), MNA alone resulted in faster benzene removal rates (half‐life of 0.96 years). Anaerobic biostimulation with sulfate had negligible effects on benzene, toluene, ethylbenzene, and xylene (o‐, m‐, and p‐xylene [BTEX]) biodegradation compared to natural attenuation alone. The highest ethanol concentration (E85) led to faster benzene removal (with a half‐life of 0.40 years), which was even higher than MNA under lower ethanol concentrations (E24). Benzene half‐life was 2.2‐fold slower in the site with the lowest ethanol (E10) compared to E85, indicating that the negative effects of ethanol on BTEX biodegradation appeared to be short‐lived and may need to be re‐evaluated over the long term. Benzene decay rates were approximately six times slower in the source zone than the rates obtained for groundwater plumes, emphasizing the importance of targeting the LNAPL after plume retreat. The study's findings can assist practitioners in better predicting the lines of evidence for BTEX bioremediation and remediation cleanup times at a lower cost in the presence of ethanol, as well as providing guidance for determining whether biostimulation is necessary to expedite source zone remediation for site closure.