Framework of the Integrated Approach to Formation Mechanisms of Typical Combustion Byproducts─Polyhalogenated Dibenzo-p-dioxins/Dibenzofurans (PXDD/Fs)

Understanding the mechanisms through which persistent organic pollutants (POPs) form during combustion processes is critical for controlling emissions of POPs, but the mechanisms through which most POPs form are poorly understood. Polyhalogenated dibenzo-p-dioxins and dibenzofurans (PXDD/Fs) are typical toxic POPs, and the formation mechanisms of PXDD/Fs are better understood than the mechanisms through which other POPs form. In this study, a framework for identifying detailed PXDD/Fs formation mechanisms was developed and reviewed. The latest laboratory studies in which organic free radical intermediates of PXDD/Fs have been detected in situ and isotope labeling methods have been used to trace transformation pathways were reviewed. These studies provided direct evidence for PXDD/Fs formation pathways. Quantum chemical calculations were performed to determine the rationality of proposed PXDD/Fs formation pathways involving different elementary reactions. Many field studies have been performed, and the PXDD/Fs congener patterns found were compared with PXDD/Fs congener patterns obtained in laboratory simulation studies and theoretical studies to mutually verify the dominant PXDD/Fs formation mechanisms. The integrated method involving laboratory simulation studies, theoretical calculations, and field studies described and reviewed here can be used to clarify the mechanisms involved in PXDD/Fs formation. This review brings together information about PXDD/Fs formation mechanisms and provides a methodological framework for investigating PXDD/Fs and other POPs formation mechanisms during combustion processes, which will help in the development of strategies for controlling POPs emissions.