Insight into biomass feedstock on formation of biochar-bound environmentally persistent free radicals under different pyrolysis temperatures.

Environmentally persistent free radicals (EPFRs) in biochars have the ability of catalytic formation of reactive oxygen species, which may pose potential oxidative stresses to eco-environment and human health. Therefore, comprehending the formation and characteristics of EPFRs in biochars is important for their further applications. In this study, the woody lignocellulosic biomass (wood chips, pine needle and barks), non-woody lignocellulosic biomass (rice husk, corn stover, and duckweed), and non-lignocellulosic biomass (anaerobically digested sludge) were selected as biomass feedstock to prepare biochars under different pyrolysis temperatures (200-700 °C). The impact of biomass feedstock on formation of biochar-bound EPFRs was systematically compared. Elemental compositions and atomic ratios of H/C and O/C varied greatly among different biomass feedstocks and the subsequently resulting biochars. EPFRs in biochars derived from the studied lignocellulosic biomass have similar levels of spin concentrations (10-10 spins per g) except for lower EPFRs in biochars under 200 and 700 °C; however, sludge-based biochars, a typical non-lignocellulosic-biomass-based biochar, have much lower EPFRs (10 spins per g) than lignocellulosic-biomass-based biochars under all the studied pyrolysis temperatures. Values of factors ranged from 2.0025 to 2.0042 and line width was in the range of 2.15-11.3 for EPFRs in the resulting biochars. Spin concentrations of biochar-bound EPFRs increased with the increasing pyrolysis temperatures from 200 to 500 °C, and then decreased rapidly from 500 to 700 °C and oxygen-centered radicals shifted to carbon-centered radicals with the increasing pyrolysis temperatures from 200 to 700 °C for all the studied biomass feedstock. 300-500 °C was the appropriate pyrolysis temperature range for higher levels of spin concentrations of biochar-bound EPFRs. Moreover, EPFRs' concentrations had significantly positive correlation with C contents and weak or none correlation with contents of transition metals. Overall, different types of biomass feedstock have significant impact on the formation of EPFRs in the resulting biochars.