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.