Abstract-Biochar, a subset of black carbon produced via pyrolysis of biomass, has received much attention in recent years due to its potential to address many important issues, from energy and climate to agriculture and environmental quality. Biochar is known to influence the fate and transport of organic contaminants, although its role has been generally assumed to be as an adsorbent. In this study, the authors investigated the ability of biochar to catalyze the reductive reactions of nitro herbicides and explosives. Two biochars, derived from poultry litter and wastewater biosolids, were found to promote the reductive removal of the dinitro herbicides pendimethalin and trifluralin and the explosives 2,4-dinitrotoluene and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by dithiothreitol. Parallel experiments using another black carbon material, graphite powder or granular activated carbon, in place of a biochar resulted in comparable rate enhancement to show reduction products, such as 2,4-diaminotoluene and formaldehyde. A cyclization product of trifluralin and reduction products of dinitrotoluene and RDX were detected only when biochar and dithiothreitol were both present, supporting the ability of biochar to promote redox reactions. Three possible catalysts, including graphene moieties, surface functional groups, and redox-active metals, in biochar may be responsible for the biochar-mediated reactions. The environmental significance, implications, and applications of this previously unrecognized role of biochar are discussed. Environ. Toxicol. Chem. 2013;32:501-508. # 2012 SETAC