Diffusive isotope fractionation of organic contaminants in aqueous solution is difficult to quantify, and only a few experimental data sets are available for compounds of environmental interest. In this study, we investigate diffusive fractionation of perdeuterated and nondeuterated benzene and toluene. Multitracer experiments were carried out in 1-D gel dissection tubes and in a quasi-2-D flow-through porous medium. The experiments allowed us to simultaneously and directly compare the diffusive and dispersive behavior of benzene and toluene. We observed an unexpected, opposite behavior of the two monoaromatic hydrocarbons. Toluene showed a normal diffusive isotope effect (DC7D8/DC7H8 = 0.96) with enrichment of the nondeuterated isotopologue in the direction of the diffusive and transverse dispersive fluxes. Conversely, the measured trends for benzene indicate inverse diffusive fractionation (DC6D6/DC6H6 = 1.02), with a remarkably faster diffusion rate of the perdeuterated isotopologue that was enriched in the downgradient portion of the diffusion tubes and at the fringes of the contaminant plumes in the flow-through setup. These outcomes can neither be interpreted as mass-dependent fractionation nor be described as purely hydrodynamic (i.e., mass independent) effects. The results of this study are relevant for the use of labeled/nonlabeled mixtures of organic compounds as conservative and (bio)reactive tracers in environmental applications.
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