Аннотация:Abstract Soil‐gas monitoring is a widely used tool to observe the migration of volatile organic compounds (VOCs) at contaminated sites. By combining this technique with natural gradient tracer methods, diffusive contaminant fluxes can be measured in situ, and non–aqueous phase liquid (NAPL) can be detected and roughly quantified. This work describes the new approach and its application at a field site in Denmark with an emplaced NAPL contamination. Soil‐gas probes with a low dead volume were installed at 1‐m depths in the sandy vadose zone, and a small volume of gas containing conservative and partitioning tracers was injected. Soil‐gas samples were withdrawn subsequently during 1 to 4 h and analyzed simultaneously for VOCs and tracers. Tracers detected the NAPL reliably, and the combined data allowed for a close delineation of the source zone. The calculated NAPL saturation deviated by up to a factor of 3 from the analyses of soil cores. Better agreement was found by taking the NAPL composition into consideration, which is, however, generally unknown at the actual field sites. In addition, the tracers were also used to estimate effective diffusion coefficients in situ, which varied by a factor of 2 between various locations. From these data, diffusive contaminant vapor fluxes were quantified without additional laboratory experiments or the use of empirical relationships. The new approach yields a better site investigation with a few additional measurements.
