A critical review of environmentally persistent free radical (EPFR) solvent extraction methodology and retrieval...

Long-lived environmentally persistent free radical (EPFR) exposures have been shown in toxicology studies to lead to respiratory and cardiovascular effects, which were thought to be due to the persistence of EPFR and their ability to produce reactive oxygen species. To characterize EPFR exposure and resulting health impacts, it is necessary to identify and systematize analysis protocols. Both direct measurement and solvent extraction methods have been applied to analyze environmental samples containing EPFR. The use of different protocols and solvents in EPFR analyses makes it difficult to compare results among studies. In this work, we reviewed EPFR studies that involved solvent extraction and carefully reported the details of the extraction methodology and retrieval recovery. EPFR recovery depends on the structure of the radical species and the solvent. For the limited number of studies available for review, the polar solvents had superior recovery in more studies. Radicals appeared to be more oxygen-centered following extraction for fly ash and particulate matter (PM) samples. Different solvent extraction methods to retrieve EPFR may produce molecular products during the extraction, thus potentially changing the sample toxicity. The number of studies reporting detailed methodologies is limited, and data in these studies were not consistently reported. Thus, inference about the solvent and protocol that leads to the highest EPFR extraction efficiency for certain types of radicals is not currently possible. Based on our review, we proposed reporting criteria to be included for future EPFR studies.