Biochar-Derived Persistent Free Radicals: A Plethora of Environmental Applications in a Light and Shadows Scenario

Biochar (BC) is a carbonaceous material obtained by pyrolysis at 200-1000 °C in the limited presence of O₂ from different vegetable and animal biomass feedstocks. BC has demonstrated great potential, mainly in environmental applications, due to its high sorption ability and persistent free radicals (PFRs) content. These characteristics enable BC to carry out the direct and PFRs-mediated removal/degradation of environmental organic and inorganic contaminants. The types of PFRs that are possibly present in BC depend mainly on the pyrolysis temperature and the kind of pristine biomass. Since they can also cause ecological and human damage, a systematic evaluation of the environmental behavior, risks, or management techniques of BC-derived PFRs is urgent. PFRs generally consist of a mixture of carbon- and oxygen-centered radicals and of oxygenated carbon-centered radicals, depending on the pyrolytic conditions. Here, to promote the more productive and beneficial use of BC and the related PFRs and to stimulate further studies to make them environmentally safer and less hazardous to humans, we have first reviewed the most common methods used to produce BC, its main environmental applications, and the primary mechanisms by which BC remove xenobiotics, as well as the reported mechanisms for PFR formation in BC. Secondly, we have discussed the environmental migration and transformation of PFRs; we have reported the main PFR-mediated application of BC to degrade inorganic and organic pollutants, the potential correlated environmental risks, and the possible strategies to limit them.