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A B S T R A C TSites contaminated by Dense Non-Aqueous Liquid Phases (DNAPLs) containing chlorinated compounds are a ubiquitous problem caused by spills or the dumping of wastes with no concern for the environment. Their migration by gravity through the subsurface and their accumulation far below ground level make in-situ treatments the most appropriate remediation technologies. In this work, an aqueous solution containing a non-ionic and biodegradable surfactant was injected in the Sardas alluvial layer contaminated at some points with DNAPL (formed by a mixture of more than 28 chlorinated compounds) from lindane production. A volume of 5.28 m 3 of an aqueous surfactant emulsion (13 g L À1 ) was injected at 14.5 m b g.l in the permeable layer (gravel-sand), at a flow rate of 0.6 m 3 h À1 and the groundwater was monitored within a test cell (3.5 m radius) built ad hoc. The flow of the injected fluids in the subsurface was also evaluated using a conservative tracer, bromide (130 mg L À1 ), added to the surfactant solution. Concentration of contaminants, chloride, bromide and surfactant, surface tension and conductivity were measured at the injection point and at three monitoring points over time. High radial dispersion was noticed resulting in high dilution of the injected fluids. The surfactant was not adsorbed in the soil during the injection time, the adsorption of the surfactant took place in the meantime (15 h) between its injection and the groundwater (GW) extraction. The concentration of chlorinated compounds dissolved from the soil in the surfactant aqueous phase when equilibrium was reached (about 850 mg L À1 ) is related to the moderate average contamination of the soil in the test cell (about 1230 mg kg À1 ). In contrast, the extraction of the free DNAPL in the altered marls layer was highly enhanced due to the addition of the surfactant. Finally, it was found that the surfactant and the contamination did not migrate from the capture zone.

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Application of surfactants in the remediation of polluted sites with dense nonaqueous phase liquid (DNAPL) still requires knowledge of partitioning between surfactants and pollutants in the organic and aqueous phases and the time necessary to reach this balance. Two real DNAPLs, generated as wastes in the lindane production and taken from the polluted sites from Sabiñanigo (Spain), were used for investigating the solubilization of 28 chlorinated organic compounds (COCs) applying aqueous surfactant solutions of three nonionic surfactants (E-Mulse® 3 (E3), Tween®80 (T80), and a mixture of Tween®80-Span®80 (TS80)) and an anionic surfactant (sodium dodecyl sulfate (SDS)). The initial concentrations of surfactants were tested within the range of 3–17 g·L−1. The pH was also modified from 7 to >12. The uptake of nonionic surfactants into the organic phase was higher than the anionic surfactants. Solubilization of COCs with the nonionic surfactants showed similar molar solubilization ratios (MSR = 4.33 mmolCOCs·g−1surf), higher than SDS (MSR = 0.70 mmolCOCs·g−1SDS). Furthermore, under strong alkaline conditions, the MSR value of the nonionic surfactants was unchanged, and the MSR of SDS value increased (MSR = 1.32 mmolCOCs·g−1SDS). The nonionic surfactants did not produce preferential solubilization of COCs; meanwhile, SDS preferentially dissolved the more polar compounds in DNAPL. The time required to reach phase equilibrium was between 24 and 48 h, and this contact time should be assured to optimize the effect of the surfactant injected on COC solubilization.