AbstractMany chlorinated aromatic and aliphatic hydrocarbons dissolved in water can be rapidly and selectively hydrodechlorinated by means of Pd catalysts. However, if they appear in a complex water matrix, as is common for wastewater treatment or after soil extraction, the protection of the Pd sites against catalyst poisons may become the key step for applicability of this reaction. In the present study, Pd/Al2O3 was tested as hydrodechlorination (HDC) catalyst in various soil-washing effluents. As probe compounds 3-chlorobiphenyl (3-CBP), monochlorobenzene (MCB) and trichloroethene (TCE) were chosen. Specific catalyst activities up to APd = 200 L g−1 min−1 were measured in clean water. The influence of surfactants and co-solvents was studied. In addition, soil slurry supernatant was employed as reaction medium to appraise the influence of soil co-extractants (dissolved organic matter, DOM) on the dechlorination reaction. Results show that commercially available surfactants such as Tween 80, Triton X-100, SDBS, and CTMAOH as well as methanol as co-solvent with concentrations up to 20 vol% did not strongly affect the catalyst activity. However, the catalyst performance was heavily decreased in the presence of a soil slurry supernatant (40 mg L−1 DOM). Hydrophobic coating of the catalyst by silicone polymers was successful in protecting the Pd sites against ionic catalyst poisons such as DOM and bisulphite for at least 24 h.