Formation of persistent free radicals in sludge biochar by hydrothermal carbonization

The uses of biochar as soil fertilizer can offset global warming and reduce dependence on limited mineral resources in the future circular economy, yet biochar may contain contaminants that can ultimately enter the food chain. In particular, persistent free radicals are emerging contaminants previously detected in biochar but underlying mechanisms of radical formation are not yet established. Here we studied radical generation during hydrothermal carbonization of waste sludge at 160–220 ºC for 0.5–2 h with solid weight ratios of 10%w–40%w using electron paramagnetic resonance and Fourier transform infrared spectrometry. Results reveal that radical concentration increases with temperature, reaction time, and weight ratio in sludge biochars, reaching a content of 47.2 × 10¹⁵ spins/g for 220 ºC, 2 h heating, and 40%w solid ratio. Moreover, low temperature of about 160 ºC favors the production of oxygen-centered radicals, whereas higher temperature of 220 ºC produces carbon-centered radicals. Our findings imply that biochar ecotoxicity should be assessed prior applications to prevent adverse health effects.