Formation of Environmentally Persistent Free Radicals during Thermochemical Processes and their Correlations with Unintentional Persistent Organic Pollutants.

Attention is increasingly being paid to environmentally persistent free radicals (EPFRs), which are organic pollutants with the activities of free radicals and stabilities of organic pollutants. EPFRs readily form during thermal processes through the decomposition of organic precursors such as phenols, halogenated phenols, and quinone-type molecules, which are also important precursors of toxic unintentionally produced persistent organic pollutants (UPOPs). We have found that EPFRs are important intermediates for UPOP formation during thermal-related processes. However, interest in EPFRs is currently mostly focused on the toxicities and formation mechanisms of EPFRs themselves. Little information is available on the important roles EPFRs play in toxic UPOP formation during thermal processes. Here, we review the mechanisms involved in EPFR formation and transformation into UPOPs during thermal processes. The review is focused on typical EPFRs, including cyclopentadiene, phenoxy, and semiquinone radicals. The reaction temperature, metal species present, and oxygen concentration strongly affect EPFR and UPOP formation during thermal-related processes. Gaps in current knowledge and future directions for research into EPFR and UPOP formation, transformation, and control are presented. Understanding the relationships between EPFRs and UPOPs will allow synergistic control strategies to be developed for thermal-related industrial sources of EPFRs and UPOPs.