Evaluation of VOC fluxes at the soil-air interface using different flux chambers and a quasi-analytical approach

Dense nonaqueous-phase liquids (DNAPLs) spilled on the soil migrate vertically depending upon gravity and capillary forces through the unsaturated zone of the porous aquifer, forming a vapour plume. These volatile organic compounds (VOCs) can be transferred by advection-diffusion to the groundwater or to the atmosphere. Evaluating DNAPL vapour fluxes at the soil-air interface is one of the key challenges in the remediation of contaminated sites. This work discusses the results of a large-scale vapour plume experiment with a well-defined trichloroethylene (TCE) spill, including a sequential raising and lowering of the water table, where the TCE vapour fluxes at the soil surface were experimentally quantified in two ways: (i) directly, with measurements at the soil-air interface using different flux chambers at various operational modes under both transient and steady-state conditions of the vapour plume, and (ii) indirectly, using a quasi-analytical approach based on soil gas measurements. It was shown that upward displacement of the water-air front during the controlled raising of the water table (approximately 10 cm h⁻¹) increased the TCE vapour flux measured at the soil surface by factors of 4 to 10. Under steady-state transport conditions, TCE vapour fluxes measured using five types of flux chambers and three operational modes were similar. The effects of the flux chamber geometry, the accumulation of TCE vapours in the chamber headspace or the air recirculation at a low flow rate on the measured TCE vapour fluxes were low. At steady-state transport conditions, TCE vapour fluxes measured with the flux chambers and estimated using the quasi-analytical approach were of the same order of magnitude. However, under transient conditions of the vapour plume, the TCE vapour flux predicted by the quasi-analytical approach greatly underestimated or overestimated the real TCE vapour flux at the soil-air interface.