Organoarsenic conversion to As(III) in subcritical hydrothermal reaction of livestock manure

Highlights: • Roxarsone (ROX) is converted to As(III) and As(V) in hydrothermal reaction. • The conversion of ROX is strongly affected by reaction temperature. • Aldehydes and hydrochar as electron donors promotes As(III) formation. • Liquid phase of As-rich livestock manure has high risks in recycling. Liquid phase produced by the subcritical hydrothermal liquefaction (HTL) of livestock manure is extensively used in agronomic and environmental applications, but the potential risks caused by inherent pollutants (e.g., roxarsone, ROX) of the livestock manure have not been considered. This study shows that less toxic ROX is completely converted into highly toxic As(III) and As(V) in the HTL reaction with temperature more than 240 °C. Moreover, more than 81.5% of As is distributed in the liquid phase generated by the livestock manure HTL reaction. Notably, the hydrothermal products of livestock manure facilitate the conversion of As(V) to As(III). The resulting hydrochar and aldehydes act as electron donors for As(V) reduction, thus resulting in the formation of As(III). Furthermore, the dissociated As promotes the depolymerization and deoxygenation of the macromolecular compounds to produce more small oxygen-containing compounds such as aldehydes, further boosting the As(V) reduction to As(III). These results indicate that the liquid phase of the livestock manure has potential risks in applications as a fertilizer. Such findings have substantial implications in biomass utilization and redox reactions of envirotechnical and biogeochemical relevance.