The potential of LNAPL delineation by 222 Rn soil-gas monitoring in a chemically heterogeneous vadose zone was investigated in this study based on laboratory (batch and columns) experiments and numerical modeling. An enhanced version of the MIN3P reactive transport code was used to simulate Rn transport in both uncontaminated and NAPL-contaminated vadose zones and results were validated against analytical solutions and laboratory experiments. Results show that 222 Rn activity profiles are mainly controlled by porous media 222 Rn production, vadose zone fluid saturations and especially the type and distribution of NAPL in contaminated areas. The results also show that decreases in 222 Rn activity and variations in activity gradients provide evidence for the presence and saturation of NAPL. This study demonstrates that LNAPL delineation via 222 Rn gas surveys at contaminated sites works best, if gas measurements extend as deep as possible and include regions where 222 Rn activity decreases due to elevated NAPL. In addition, collection and analysis of depth-discrete gas samples allows the characterization of vertical NAPL distribution based on the 222 Rn activity gradient. The determination of 222 Rn production in the unsaturated zone, as well as water capillary pressure curves are of key importance in enabling the discrimination of an uncontaminated from a NAPL-contaminated area.

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