Environmentally Persistent Free Radicals in Biochar: Environmental Context and Future Research Needs

Environmentally persistent free radicals (EPFRs) are produced during biochar pyrolysis and, depending on biochar application, can be either detrimental or beneficial. High levels of EPFRs may interfere with cellular metabolism and be toxic, because EPFR-generated reactive oxygen species (e.g., hydroxyl radicals (•OH)) attack organic molecules. However, •OH can be useful in remediating recalcitrant organic contaminants in soils. Understanding the (system-specific) safe range of EPFRs produced by biochars requires knowing both the context of their use and their overall significance in the existing suite of environmental radicals, which has rarely been addressed. Here we place EPFRs in a broader environmental context, showing that biochar can have EPFR concentrations from 10⁸-fold lower to 10⁹-fold higher than EPFRs from other environmental sources, depending on feedstock, production conditions, and degree of environmental aging. We also demonstrate that •OH radical concentrations from biochar EPFRs can be from 10⁴-fold lower to 10¹⁷-fold higher than other environmental sources, depending on EPFR type and concentration, reaction time, oxidant concentration, and extent of environmental EPFR persistence. For both EPFR and •OH concentrations, major uncertainties derive from the range of biochar properties and the range of data reporting practices. Controlling feedstock lignin content and pyrolysis conditions are the most immediate options for managing EPFRs. Co-application of compost to provide organics may serve as a postpyrolysis method to quench and reduce biochar EPFRs.