Black Carbon-Mediated Destruction of Nitroglycerin and RDX By Hydrogen Sulfide

The in situ remediation of sediments contaminated with explosives, including nitroglycerin and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), is desirable, particularly at bombing ranges where unexploded ordnance (UXO) renders excavation dangerous. Sulfides generated by biological sulfate reduction in sediments are potent nucleophiles and reductants that may contribute to the destruction of explosives. However, moderately hydrophobic explosives are likely to sorb to black carbons, which can constitute 10−30% of sediment organic carbon. In this study, we evaluated whether the black carbons accelerate these reactions or simply sequester explosives from aqueous phase reactions. Using environmentally-relevant sulfide and black carbon concentrations, our results indicated that black carbons accelerated the destruction of both compounds, yielding relatively harmless products on the time scale of hours. For both compounds, destruction increased with sulfide and graphite concentrations. Using sheet graphite as a model for graphene regions in black carbons, we evaluated whether graphene regions mediated the reduction of explosives by promoting electron transfer from sulfides. Our results demonstrated that the process was more complex. Using an electrochemical cell that enabled electron transfer from sulfides to explosives through graphite, but prevented nucleophilic substitution reactions, we found that nitroglycerin destruction, but not RDX destruction, could be explained by an electron transfer mechanism. Furthermore, surface area-normalized destruction rates for the same explosive varied for different black carbons. While black carbon-mediated destruction of explosives by sulfides is likely to be a significant contributor to their natural attenuation in sediments, a fundamental characterization of the reaction mechanisms is needed to better understand the process.