Compositional evolution of the emplaced fuel source in the vadose zone field experiment at airbase Vaerlose, Denmark

A field experiment was performed in a sandy vadose zone, studying the fate of an emplaced fuel-NAPL source, composed of 13 hydrocarbons and a tracer. The UNIFAC model was used to test the nonideal behavior of the source, and the numerical model MIN3P was used for assessing the effect of biodegradation on source evolution.

The diffusive loss to the surrounding vadose zone and the atmosphere created temporary gradients in mole fractions of the individual compounds within the source NAPL. The evolution of the source composition corresponded in general with expectations based on Raoult's Law, with the exception that the mole fractions of aromatic compounds in the source NAPL decreased faster than fractions of aliphatic compounds of similar volatility.

Calculation of activity coefficients (gamma) using the UNIFAC model implied nonideal conditions, with composition-dependent gamma's different from 1. Positive deviations were calculated for the aromatic compounds. The effect of biodegradation on source depletion, evaluated by numerical modeling, was greater for the aromatic as compared to the aliphatic compounds.

Hence, the faster depletion of the aromatic relative to aliphatic compounds of similar volatility is both a result of the nonideality of the mixture and a result of partitioning and biodegradation in the pore-water. Vapor concentrations of the compounds in the source were in reasonable agreement with predictions based on the modified Raoult's Law with the UNIFAC predicted gamma's and the NAPL composition for the most volatile compounds.

For the less volatile compounds, the measured vapor concentrations were lower than predicted with the largest deviations for the least volatile compounds. This field experiment illustrated that nonideal behavior and bioenhanced source depletion need to be considered at multicomponent NAPL spill sites.