The influence of the presence of humic acids of different origin on the catalytic transformation of pentachlorophenol (PCP) by two metal oxides, ferrihydrite and birnessite, using mechanochemical contact was studied. The mechanochemical dry contact with light grinding of PCP and birnessite was more effective than that observed in the presence of ferrihydrite (approximately 70 and 40% of PCP removal after 20 days, respectively). The removal of PCP by birnessite and ferrihydrite was significantly enhanced in the presence of humic acid (HA). The different origin of humic acids (agricultural, forest and commercial) showed a slight influence on the overall reaction. The commercial HA, when mixed with birnessite, was more effective in reducing PCP concentration compared to the others two HAs investigated. The transformation process in the presence of birnessite with and without HA was accompanied by the release of four chlorides per molecule of PCP transformed. (C) 2004 Kluwer Academic Publishers.