Natural Source Zone Depletion of Crude Oil in the Subsurface: Processes Controlling Mass Losses of Individual Compounds

Abstract At many petroleum hydrocarbon spill sites, residual spilled product forms a long‐term source of groundwater contamination. The phrase source zone natural depletion is used to refer to the mass loss rates. Overall mass lost under environmental conditions was analyzed using conservative biomarker concentrations for a 1979 oil spill in northern Minnesota, USA. After 40–41 years, an average of 50% of the mass was lost with values ranging from 22% to 57% depending on location. It is also important to understand the composition changes in the source. To understand controls on the losses of individual compounds, concentrations of volatile hydrocarbons in oil samples were compared with aqueous solubilities, and pore‐space oil saturations. The results of the comparison show that losses of the oil compounds were controlled by pore‐space oil saturations, solubility, and susceptibility to degradation under methanogenic conditions. Compounds that degrade under methanogenic conditions, including toluene, o ‐xylene, and n ‐alkanes are more depleted compared to benzene, ethylbenzene, and m ‐ and p ‐xylene for which losses are dominated by dissolution. These rates and compound‐specific behaviors form a foundation for improved modeling approaches and risk analyses.