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

Black carbon (BC) is an important class of geosorbents that control the fate and transport of organic pollutants in soil and sediment. We previously demonstrated a new role of BC as an electron transfer mediator in the abiotic reduction of nitroaromatic and nitramine compounds by Oh and Chiu (Environ Sci Technol 43:6983-6988, 2009). We proposed that BC can catalyze the reduction of nitro compounds because it contains microscopic graphitic (graphene) domains, which facilitate both sorption and electron transfer. In this study, we assessed the ability of different types of BC--graphite, activated carbon, and diesel soot--to mediate the reduction of 2,4-dinitrotoluene (DNT) and 2,4-dibromophenol (DBP) by H(2)S. All three types of BC enhanced DNT and DBP reduction. H(2)S supported BC-mediated reduction, as was observed previously with a thiol reductant. The results suggest that BC may influence the fate of organic pollutants in reducing subsurface environments through redox transformation in addition to sorption.

By using various types of black carbon (BC), including chemically converted graphene (CCG), multiwalled carbon nanotubes (MWCNT), and granular activated carbon (GAC), BC-mediated reduction was investigated with 2,4-dinitrotoluene (DNT), a model nitroaromatic compound. We hypothesized that by providing sorption and electron transfer sites, BC can be used as a catalyst to accelerate DNT reduction by dithiothreitol (DTL), a thiol reductant. Results from batch experiments showed that CCG, MWCNT, and GAC could promote reduction of DNT by DTL. The yield ratio of the two aminonitro intermediates was approximately 1:1, which was consistent with that in a graphite system. However, fullerene did not significantly enhance the reduction of DNT, likely due to being a π acceptor. Kinetic data analysis showed that removal of DNT in the presence of BC and DTL was linearly proportional to the electrical conductivity of BC, suggesting that the graphitic structure of BC may be responsible for DNT removal. Our results indicate that the presence of BC materials may affect the fate of nitroaromatic compounds under electron-rich conditions.

No abstract

No abstract