Impact of biochar, fertilizers and cultivation type on environmentally persistent free radicals in agricultural soil.

Environmentally persistent free radicals (EPFRs) have been considered as emerging contaminants due to their detrimental effects on human health. The adverse health impacts are attributed to oxidative stress induced by EPFRs through the formation of reactive oxygen species (ROS). In soils, it may also increase the degradation process of polymeric organic matter and/or undesired organic pollutants through hydroxyl radical activity. The biochar pyrolysis process entails the thermal decomposition of organic compounds in the biomass, with the carbonization conditions and feedstock type facilitating the formation of EPFRs. When biochar is used to amend soil, these radicals may promote the formation of ROS, and thus influence the transformation of organic and inorganic contaminants in soil and impact the rhizosphere. Agricultural soils are being amended with biochar to mainly increase carbon content and facilitate the plant growing conditions. Therefore, agricultural soils may become a source of EPFRs. However, the fate and transformations of EPFRs in soils after biochar amendment are not well understood or studied. This paper presents the first (to our knowledge) studies of EPFRs behaviour in agricultural soil with different input of biochar, cultivation types and residence time period. Different cultivation types, addition of fertilisers and variation in biochar input, on the one hand, and presence of metals in soil, biochar and fertilizers, on the other hand, provide different conditions for EPFRs formation, accumulation and fate in agricultural soils. Two significant factors have been found to determine the fate of EPFRs in soil: transition metal content (particularly those in reaction available form) and cultivation level of soil. Cultivation significantly decreased presence of EPFRs, both carbon-centered and oxygen-centered, in relatively short periods of time, while metal presence (and particularly through fertilizer supplementation) increases the half-life of radicals and transforms organic matter to more oxygen-centered EPFRs. The amount of biochar addition plays a secondary role as the EPFRs content in the soils is in a longer term primarily controlled by the other two factors.