Multispecies transport of metal–EDTA complexes and chromate through undisturbed columns of weathered fractured saprolite

Laboratory-scale tracer experiments were conducted to investigate the geochemical and hydrological processes that govern the fate and transport of organically chelated radionuclides and toxic metals in undisturbed saturated columns of weathered, fractured shale saprolite. Three long-term, reactive contaminant injections were pulsed onto three separate soil columns, with the following influent mixtures: (1) ¹⁰⁹CdEDTA²⁻, (2) ¹⁰⁹CdEDTA²⁻ and ^57,58Co(II)EDTA²⁻, and (3) ¹⁰⁹CdEDTA²⁻, ⁵⁷Co(III)EDTA⁻, and H⁵¹CrO₄⁻. Both single and multiple species experiments were conducted to determine the importance of interaction between the contaminants and competition for surface sites. Flow interruption was used to identify physical and chemical non-equilibrium (PNE and CNE) which were caused by multiple pore-region flow and rate-limited chemical reactions, respectively. Reactive contaminant transport through the fractured, weathered shale was affected by sorption, redox, and dissociation reactions, which were mediated by soil organic matter and surficial oxides of Fe, Mn, and Al. The transport of CdEDTA²⁻ was significantly influenced by ligand-promoted dissolution of subsurface Fe and Al sources, resulting in the liberation of Cd²⁺, Al(III)EDTA⁻ and Fe(III)EDTA⁻. Flow interruption confirmed that the surface-mediated dissociation reaction was time-dependent, with the stability of the CdEDTA²⁻ complex dependent on its residence time within the soil. The migration of Co(II)EDTA²⁻ was dominated by oxidization to the highly stable Co(III)EDTA⁻ species, and elevated effluent Mn²⁺ suggested that surficial Mn(IV) oxides likely catalyzed the redox reaction, though Fe-oxides may have also contributed to the reaction. Dissociation (12%) of the Co(II)EDTA²⁻ complex was first observed during flow interruption, indicating that rate-limited dissociation of the complex by Fe-oxides may be significant under equilibrium conditions. The transport of HCrO₄⁻ was significantly altered by the reduction of mobile Cr(VI) to irreversibly bound Cr(III). The reduction reaction was catalyzed by surface-bound natural organic matter and flow interruption confirmed that the reaction was time-dependent. There was little evidence of competitive effects between the various contaminants in the multispecies experiments, since each was influenced by a different geochemical process during transport through the soil. The results of this study further support research findings that suggest anionic toxic metals and radionuclide–organic complexes can be significantly influenced by soil geochemical processes that can both enhance and impede the subsurface migration of these contaminants.