We compare two methods for estimating the natural source zone depletion (NSZD) rate at fuel release sites that occurs by groundwater flow through the source zone due to dissolution and transport of biodegradation products. Dissolution is addressed identically in both methods. The “mass budget method”, previously proposed and applied by others, estimates the petroleum hydrocarbon biodegradation rate based on dissolved electron acceptor delivery and dissolved biodegradation product removal by groundwater flow. The mass budget method relies on assumed stoichiometry for the degradation reactions and differences in concentrations of dissolved species (oxygen, nitrate, sulfate, reduced iron, reduced manganese, nonvolatile dissolved organic carbon, methane) at monitoring locations upgradient and downgradient of the source zone. We illustrate a refinement to account for degradation reactions associated with loss of reduced iron from solution. The “carbon budget method,” a simplification of approaches applied by others, addresses carbon‐containing species in solution or lost from solution (precipitated) and does not require assumptions about stoichiometry or information about electron acceptors. We apply both methods to a fuel release site with unusually detailed monitoring data and discuss applicability to more typical and less thoroughly monitored sites. The methods, as would typically be applied, yield similar results but have different constraints and uncertainties. Overall, we conclude that the carbon budget method has greater practical utility as it is simpler, requires fewer assumptions, accounts for most iron‐reducing reactions, and does not include CO2 that escapes from the saturated to the unsaturated zone.

Natural source zone depletion (NSZD) refers to processes within chemically impacted vadose and saturated zones that reduce the mass of contaminants remaining in a defined source control volume. Studies of large petroleum hydrocarbon release sites have shown that the depletion rate by vapor phase migration of degradation products from the source control volume through the vadose zone (V‐NSZD) is often considerably higher than the rate of depletion from the source control volume by groundwater flow carrying dissolved petroleum hydrocarbons arising from dissolution, desorption, or back diffusion, and degradation products arising from biodegradation (GW‐NSZD). In this study, we quantified vadose zone and GW‐NSZD at a small unpaved fuel release site in California typical of those in settings with predominantly low permeability media. We estimated vadose zone using a dense network of efflux monitoring locations at four sampling events over 2 years, and GW‐NSZD using groundwater monitoring data downgradient of the source control volume in three depth intervals spanning up to 9 years. On average, vadose zone was 17 times greater than GW‐NSZD during the time interval of comparison, and vadose zone was in the range of rates quantified at other sites with petroleum hydrocarbon releases. Estimating vadose zone and GW‐NSZD rates is challenging but the vadose zone rate is the best indicator of overall source mass depletion, whereas GW‐NSZD rates may be useful as baselines to quantify progress of natural or engineered remediation in portions of the saturated zone in which there are impediments to loss of methane and other gases to the vadose zone.