Polychlorinated dibenzo-p-dioxins (PCDDs), a group of recalcitrant toxic compounds, are ubiquitous in nature. Amongst them, octachlorodibenzo-p-dioxin (OCDD) is not only prevalent in soil and sediment due to its high lipophilicity and hydrophobicity, but also detected in ground water and surface water. The present study examined the degradation of OCDD in aqueous solutions using four different zero-valent metal nanoparticles; zero-valent aluminum (nZVAL), zero-valent zinc (nZVZ), zero-valent iron (nZVI) and zero-valent nickel (nZVN). Only nZVZ was found to efficiently degrade OCDD into lower chlorinated congeners [OCDD -> 1,2,3,4,6,7,9-HxCDD (63%) -> 1,2,3,6,8,9-HpCDD (21%) -> 1,2,4,7,8-PeCDD (46%) -> 1,2,4,7-TeCDD (19%)] under ambient conditions. Simulations were also performed to predict the OCDD dechlorination pathway using a linear free energy relationship (LFER) model. Additionally, toxic equivalent quantity (TEQ) and homologue patterns were calculated by LFER modeling. The experimentally observed congener profiles were in excellent agreement with the model-predicted results, especially considering the complexity of the OCDD dechlorination pathway (256 theoretically possible reactions). This study proposes nZVZ as a suitable candidate for OCDD dechlorination and constitutes the first report on OCDD degradation using zero-valent metal nanoparticles under ambient conditions. (C) 2013 Elsevier B.V. All rights reserved.