α, β and γ-hexachlorocyclohexane (HCH) are persistent and bioaccumulative pollutants and they were included in the Stockholm Convention on Persistent Organic Pollutants (POPs). Old lindane factories generated high amounts of wastes with HCH and other Chlorinated Organic Compounds (COCS). These were often dumped in the surroundings of the production sites, polluting soil and groundwaters with the associated risk of surface pollution. This is the case of the Sardas and Bailin landfills, located in Sabiñánigo (Huesca, Spain). Among the waste from lindane production, a liquid residue was detected in the landfill subsurfaces, forming a dense non-aqueous phase liquid (DNAPL) composed of HCH isomers, benzene and chlorobenzenes, with a high impact on groundwater pollution. In this study, six DNAPL samples obtained from the Bailin and Sardas landfills were analyzed by GC/MSD and GC/FID/ECD. Compounds were identified using mass spectra and the retention index from pure standards and literature information. Pure positional isomers of dichlorobenzene (DCB), trichlorobenzene (TCB), tetrachlorobenzene (TetraCB), HCH and pentachlorocyclohexene (PentaCX) were distinguished and quantified. In addition, heptachlorocyclohexane (HeptaCH) isomers, precursors of hexacholorocylohexene (HexaCX), were also identified and quantified in the DNAPL samples, although the corresponding isomers could not be discriminated. Information about PentaCX, HexaCx and HeptaCH identification is very limited in the literature. HCH contents in the DNAPL ranged from 22% to 30% in weight, the major isomers being lindane and δ-HCH, followed by α-HCH. The β isomer was the least abundant. HeptaCH contents were present in the same order of magnitude as HCHs in the DNAPL. PentaCXs and HexaCXs could have appeared as dehydrochlorination derivatives of HCHs and HeptaCHs, respectively. Two of the DNAPLs analyzed showed a higher content of TCBs and TetraCBs, associated with lower HCH and HeptaCH contents. Variations of these compounds in the DNAPL could be related to an alkaline dehydrochlorination in the landfill conditions.

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.

Sardas Landfill at Sabiñánigo Huesca is polluted with Dense Non-Aqueous Liquid Phases (DNAPLs) composed of a complex mixture of chlorinated organic compounds (COCs). This DNAPL was produced as liquid waste from lindane production being dumped decades ago in the unlined landfills close to the lindane factory. This DNAPL migrated by gravity through the subsurface and accumulated in the contact between the alluvial and marls layers (about 15 m b.g.l.). Seven injections of an aqueous emulsion of a biodegradable non-ionic surfactant (E-Mulse 3 ®) were carried out at the most polluted areas of the Sardas alluvial. Injections were carried out between April and November 2021 using different surfactant concentrations (6.7, 20, 25 and 50 g/L), injection volumes (0.2 to 7 m3) and injection flow rates (0.08–0.85 m3/h). Injected fluids were extracted in the same well or surrounding wells, and the time elapsed between surfactant injection and extraction varied between 24 and 72 h. A total of 22 m3 were injected into the alluvial, and more than double this injected volume was extracted. Injection and extraction points were in the contact between the marls and the alluvial layer. Extracted fluid accumulated in tanks, and phases separated. DNAPL recovered here was mobilized rather than solubilized and managed as toxic waste. The aqueous supernatant was treated in a wastewater treatment plant with physicochemical treatment (including adsorption in activated carbon) before being discharged into the environment. The transport of the injected fluids was monitored by conductivity profiles using bromide (260–538 mg·L−1) as a conservative tracer. High radial dispersion of the injected fluid was found. Surfactant losses by adsorption in the alluvial and absorption in DNAPL were noticed, and both surfactant and contamination did not escape from the capture zone. Monitoring since 2018 of the COCS in groundwater and the DNAPL presence in the contact between alluvial and marls layers showed a significant reduction of COCs in the treated zone with the surfactant injections.

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