The disposal of toxic metals [e.g., Cr(VI)] generated by the Department of Energy during the cold war era has historically involved shallow land burial in unconfined pits and trenches. The objectives of this study were to investigate the impact of coupled hydrologic and geochemical processes on the fate and transport of Cr(VI) in undisturbed soil cores obtained from a fractured, acidic inceptisol that are commonly used in the disposal of waste at the Oak Ridge National Laboratory. The mobility of Cr(VI) was significantly retarded relative to a nonreactive Br- tracer, and the mobility decreased with increased loading of the solid phase with natural organic matter (NOM). A significant portion of added Cr(VI) did not elute from the columns, and X-ray absorption near-edge structure (XANES) revealed that both Cr(VI) and Cr(III) resided on the soil mineral surfaces. The reduction of Cr(VI) to Cr(III) was dramatically more significant on soils with higher levels of surface-bound NOM. This indicated that NOM was serving as a suitable reductant during Cr(VI) transport even in the presence of potentially competing geochemical oxidation reactions involving Cr. The redox reaction was catalyzed by the presence of soil mineral surfaces, and the reduced product Cr(III) was immobilized as a tightly bound moiety. The effectiveness of surface-bound NOM to reduce toxic Cr(VI) to Cr(III) under acidic conditions has important implications regarding the design and implementation of in situ remedial strategies.
A significant limitation in defining remediation needs at contaminated sites often results from an insufficient understanding of the transport processes that control contaminant migration. The objectives of this research were to help resolve this dilemma by providing an improved understanding of contaminant transport processes in highly structured, heterogeneous subsurface environments that are complicated by fracture flow and matrix diffusion. Our approach involved a unique long‐term, steady state natural gradient injection of multiple tracers with different diffusion coefficients (Br, He, Ne) into a fracture zone of a contaminated shale bedrock. The spatial and temporal distribution of the tracers was monitored for 550 days using an array of groundwater sampling wells instrumented within a fast flowing fracture regime and a slow flowing matrix regime. The tracers were transported preferentially along strike‐parallel fractures, with a significant portion of the tracer plumes migrating slowly into the bedrock matrix. Movement into the matrix was controlled by concentration gradients established between preferential flow paths and the adjacent rock matrix. Observed differences in tracer mobility into the matrix were found to be a function of their free‐water molecular diffusion coefficients. The multiple tracer technique confirmed that matrix diffusion was a significant process that contributed to the overall physical nonequilibrium that controlled contaminant transport in the shale bedrock. The experimental observations were consistent with numerical simulations of the multitracer breakthrough curves using a simple fracture flow model. The simulated results also demonstrated the significance of contaminant diffusion into the bedrock matrix. The multiple tracer technique and ability to monitor the fracture and matrix regimes provided the necessary experimental constraints for the accurate numerical quantification of the diffusive mass transfer process. The experimental and numerical results of the tracer study were also consistent with indigenous contaminant discharge concentrations within the fracture and matrix regimes of the field site. These findings suggest that the secondary source contribution of the bedrock matrix to the total off‐site transport of contaminants is relatively large and potentially long‐lived.
The possibility of relatively fast neutron oscillations into a mirror neutron state is not excluded experimentally when a mirror magnetic field is considered. Direct searches for the disappearance of neutrons into mirror neutrons in a controlled magnetic field have previously been performed using ultracold neutrons, with some anomalous results reported. We describe a technique using cold neutrons to perform a disappearance and regeneration search, which would allow us to unambiguously identify a possible oscillation signal. An experiment using the existing General Purpose-Small Angle Neutron Scattering instrument at the High Flux Isotope Reactor at Oak Ridge National Laboratory will have the sensitivity to fully explore the parameter space of prior ultracold neutron searches and confirm or refute previous claims of observation. This instrument can also conclusively test the validity of recently suggested oscillation-based explanations for the neutron lifetime anomaly.
Chromium has served as an exceptional and necessary elemental component of many industrial processes and consumer products. Its prevalence in the global environment as both a dissolved and wind‐borne constituent has prompted concern during the last several decades due to the large migration potential and biological toxicity of various Cr chemical species. The objective of this study was to develop an improved understanding and predictive capability of the rates and mechanisms of competing geochemical redox and sorption reactions that govern the fate and transport of Cr(III) and C(VI) in heterogeneous subsurface environments. Batch and miscible displacement experiments, coupled with solid‐phase spectroscopy methods, were utilized to quantify the interaction of Cr with subsurface materials acquired from three geographically distinct locations within the continental United States that represented soils from different Department of Energy facilities known to have issues regarding Cr contamination. Soil chemical and mineralogical properties were found to be important factors controlling the mechanisms of Cr–solid phase interactions, with many of the reactive processes being time dependent. Both sorption and redox reactions impacted Cr(III)– and Cr(VI)–solid phase interactions and were modeled as nonlinear, nonequilibrium or equilibrium, reversible or nonreversible reactive processes. The research investigations within this study highlight the environmental significance of Cr speciation and solid‐phase reactivity in heterogeneous subsurface soil systems with contrasting geochemical and mineralogical properties.
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