Overview of Natural Source Zone Depletion: Processes, Controlling Factors, and Composition Change

Natural source zone depletion (NSZD) has emerged as a practical alternative for restoration of light non-aqueous phase liquid (LNAPL) sites that are in the later stages of their remediation lifecycle. Due to significant research, the NSZD conceptual model has evolved dramatically in recent years, and methanogenesis is now accepted as a dominant attenuation process (e.g., Lundegard and Johnson ; Ng et al. ). Most of the methane is generated within the pore space adjacent to LNAPL (Ng et al. ) from where it migrates through the unsaturated zone (e.g., Amos and Mayer ), where it is oxidized. While great progress has been made, there are still some important gaps in our understanding of NSZD. NSZD measurements provide little insight on which constituents are actually degrading; it is unclear which rate-limiting factors that can be manipulated to increase NSZD rates; and how longevity of the bulk LNAPL and its key constituents can be predicted. Various threads of literature were pursued to shed light on some of the questions listed above. Several processes that may influence NSZD or its measurement were identified: temperature, inhibition from acetate buildup, protozoa predation, presence of electron acceptors, inhibition from volatile hydrocarbons, alkalinity/pH, and the availability of nutrients can all affect methanogenesis rates, while factors such as moisture content and soil type can influence its measurement. The methanogenic process appears to have a sequenced utilization of the constituents or chemical classes present in the LNAPL due to varying thermodynamic feasibility, biodegradability, and effects of inhibition, but the bulk NSZD rate appears to remain quasi-zero order. A simplified version of the reactive transport model presented by Ng et al. has the potential to be a useful tool for predicting the longevity of key LNAPL constituents or chemical fractions, and of bulk LNAPL, but more work is needed to obtain key input parameters such as chemical classes and their biodegradation rates and any potential inhibitions.