Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) constitute a group of persistent organic pollutants that form almost inexorably in all thermal and combustion operations. This review focuses on mechanisms that govern their formation, chlorination, dechlorination and destruction. As a consequence of their extreme toxicity and propensity to bioaccumulate, PCDD/Fs have been subjected to much scientific research, designed to understand mechanisms and conditions that govern their emission rates and congener distribution (fingerprints). Consensus of opinions in the literature points to heterogeneous pathways contributing Substantially more in the total yield of PCDD/Fs in combustion systems than the gas phase pathway. However, in our view, a great complexity of both homogeneous and heterogeneous routes and uncertainties in many thermochemical and rate parameters enable no conclusive statement about the contribution of each route. Chlorination patterns of precursors appear to play a major role in final congener profiles of PCDD/F emissions. According to the most recent theoretical studies, these congener profiles seem consistent with thermodynamic stabilities of dioxins and furans produced in thermal processes, however, further theoretical investigations at more accurate levels are needed to clarify this matter further. Theoretical studies along with experimental findings reveal that the PCDD/PCDF ratio remains very sensitive to the operating conditions, with pyrolytic conditions favouring the formation of PCDFs. A number of reaction mechanisms has been proposed to answer many of the most intriguing questions about the formation of PCDD/Fs. These mechanisms include models of gaseous and heterogeneous reactions, often inferred from theoretical quantum chemical calculations Studies, which incorporate steps responsible for formation, chlorination, dechlorination and destruction of dioxins and furans. The review identifies gaps in our present understanding of the reaction mechanisms and suggests that further progress in the field needs to be facilitated by development of reliable mechanistic models for (i) catalytic pathways, (ii) chlorination/dechlorination reactions including the Deacon reaction and the direct transfer of chlorine from solid surfaces into the aromatic moieties, and (iii) formation of PCDD/Fs from precursors other than chlorophenols, especially pesticides. (C) 2008 Elsevier Ltd. All rights reserved.