title: Quantification and modelling of 2,4-dinitrotoluene reduction with high-purity and cast iron.
abstract: Cast iron has been used as a reactive material in permeable reactive barriers (PRBs) for site remediation. While reactions are generally believed to occur on the iron (oxide) surface, a recent study by [Oh, S.Y., Cha, D.K., Chiu, P.C., 2002a. Graphite-mediated reduction of 2,4-dinitrotoluene with elemental iron. Environ. Sci. Technol. 36 (10), 2178-2184] showed that graphite inclusions in cast iron can also serve as reaction sites for 2,4-dinitrotoluene (DNT). These authors also found that graphite-mediated reduction of DNT has a regioselectivity that is different from that for iron surface. In this study, we quantified the observations reported by Oh et al. and examined the role of graphite in cast iron through numerical modelling. Models containing one and two reaction sites were developed to evaluate the mass transfer, sorption and reaction rates for DNT reduction in batch systems containing high-purity and cast iron. Our simulations showed that the regioselectivity, defined as the ratio of the ortho- and para-nitro reduction rate constants, was 0.37+/-0.04 S.E. (S.E.=one estimated standard error) for iron surface and 3.59+/-0.76 S.E. for graphite surface. In the cast iron-water system, we estimated that at least 66+/-2% S.E. of the DNT was reduced on graphite surface, despite the low graphite content and the lower DNT reduction rate with graphite than with iron. Graphite played such an important role because of the rapid adsorption of DNT to graphite. In the batch experiments conducted by Oh et al., external mass transfer was not rate limiting. Surface reaction was the rate-limiting step for DNT reduction on the graphite surface in cast iron, whereas internal mass transfer and/or adsorption and surface reaction were important for high-purity iron.
authors.affiliation: Department of Civil and Environmental Engineering, University of Delaware, Newark, DE 19716, USA.
authors.forename: Behnam
authors.initials: B
authors.lastname: Jafarpour
authors.forename: Benham
authors.initials: B
authors.lastname: Jafarpour
authors.forename: Paul T
authors.initials: PT
authors.lastname: Imhoff
authors.forename: Pei C
authors.initials: PC
authors.lastname: Chiu
mesh_terms: D002273:Carcinogens / Q000737:chemistry*; D004136:Dinitrobenzenes / Q000737:chemistry*; D006108:Graphite / Q000737:chemistry; D007501:Iron / Q000737:chemistry*; D008962:Models, Theoretical; D010084:Oxidation-Reduction; D012989:Soil Pollutants / Q000032:analysis
chemical_list: D002273:Carcinogens; D004136:Dinitrobenzenes; D012989:Soil Pollutants; C016403:2,4-dinitrotoluene; D006108:Graphite; D007501:Iron