AbstractQuantitative methods of monitoring natural source zone depletion (NSZD) via biodegradation of petroleum hydrocarbons (PHC) are required to investigate source zone longevity and guide long‐term management of PHC impacted sites. Vadose zone NSZD processes can be monitored using analysis of surficial CO2 effluxes, soil‐gas gradients, and thermal gradients. This study describes an applied research and development program conducted at a former refinery site over a 4‐year period (2015 to 2019) on quantitative technologies for evaluation of NSZD of PHC light nonaqueous phase liquid (LNAPL) present within a shallow soil zone. A multiyear study using discrete CO2 efflux measurements from dynamic closed chambers was compared with estimates obtained using static traps and continuous monitoring using forced diffusion (FD) technology. Thermistor strings along a transect were used to monitor hourly thermal gradients and assess NSZD rates using the temperature gradient method. Discrete soil‐gas data were used to quantify the vertical oxygen gradient to estimate NSZD rates using the concentration gradient method (CGM). Results of discrete and continuous monitoring methods provide estimates of monthly NSZD rates that range seasonally from 80 to 1300 US gal/acre/year using radiocarbon corrected CO2 efflux method for decane (C10H22) equivalent, 120 to 1600 US gal/acre/year using CGM (for wet to dry conditions) and 400 to 2000 US gal/acre/year using the temperature gradient method. Both seasonal temperature and precipitation fluctuations contribute to variability in rates. Continuous methods are shown to provide for improved resolution of temporal variability and seasonal estimates, although discrete methods provide for improved spatial quantification.
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