Simplified behaviors from increased heterogeneity: II. 3-D uranium transport at the decimeter scale and intertank comparisons.

Upscaling from bench scale systems to field scale systems incorporates physical and chemical heterogeneities from atomistic up to field scales. Heterogeneities of intermediate scale (~10(-1) m) are impossible to incorporate in a bench scale experiment. To transcend these scale discrepancies, this second in a pair of papers presents results from an intermediate scale, 3-D tank experiment completed using five different particle sizes of uranium contaminated sediment from a former uranium mill field site. The external dimensions of the tank were 2.44 m×0.61 m×0.61 m (L×H×W). The five particle sizes were packed in a heterogeneous manner using roughly 11 cm cubes. Small groundwater wells were installed for spatial characterization of chemical gradients and flow parameters. An approximately six month long bromide tracer test was used for flow field characterization. Within the flow domain, local uranium breakthrough curves exhibited a wide range of behaviors. However, the global effluent breakthrough curve was smooth, and not unlike breakthrough curves observed in column scale experiments. This paper concludes with an inter-tank comparison of all three experimental systems presented in this pair of papers. Although there is a wide range of chemical and physical variability between the three tanks, major chemical constituent behaviors are often quite similar or even identical.

Simplified behaviors from increased heterogeneity: I. 2-D uranium transport experiments at the decimeter scale.

Intermediate scale tank studies were conducted to examine the effects of physical heterogeneity of aquifer material on uranium desorption and subsequent transport in order to bridge the scaling gap between bench and field scale systems. Uranium contaminated sediment from a former uranium mill field site was packed into two 2-D tanks with internal dimensions of 2.44×1.22×0.076 m (tank 1) and 2.44×0.61×0.076 m (tank 2). Tank 1 was packed in a physically homogenous manner, and tank 2 was packed with long lenses of high and low conductivities resulting in different flow fields within the tanks. Chemical gradients within the flow domain were altered by temporal changes in influent water chemistry. The uranium source was desorption from the sediment. Despite the physical differences in the flow fields, there were minimal differences in global uranium leaching behavior between the two tanks. The dominant uranium species in both tanks over time and space was Ca2UO2(CO3)3(0). However, the uranium/alkalinity relationships varied as a function of time in tank 1 and were independent of time in tank 2. After planned stop-flow events, small, short-lived rebounds were observed in tank 1 while no rebound of uranium concentrations was observed in tank 2. Despite appearing to be in local equilibrium with respect to uranium desorption, a previously derived surface complexation model was insufficient to describe uranium partitioning within the flow domain. This is the first in a pair of papers; the companion paper presents an intermediate scale 3-D tank experiment and inter-tank comparisons. For these systems, physical heterogeneity at or above the decimeter scale does not affect global scale uranium desorption and transport. Instead, uranium fluxes are controlled by chemistry dependent desorption patterns induced by changing the influent ionic composition.

Radionuclide interaction with clays in dilute and heavily compacted systems: a critical review.

Given the unique properties of clays (i.e., low permeability and high ion sorption/exchange capacity), clays or clay formations have been proposed either as an engineered material or as a geologic medium for nuclear waste isolation and disposal. A credible evaluation of such disposal systems relies on the ability to predict the behavior of these materials under a wide range of thermal-hydrological-mechanical-chemical (THMc) conditions. Current model couplings between THM and chemical processes are simplistic and limited in scope. This review focuses on the uptake of radionuclides onto clay materials as controlled by mineral composition, structure, and texture (e.g., pore size distribution), and emphasizes the connections between sorption chemistry and mechanical compaction. Variable uptake behavior of an array of elements has been observed on various clays as a function of increasing compaction due to changes in pore size and structure, hydration energy, and overlapping electric double layers. The causes for this variability are divided between "internal" (based on the fundamental structure and composition of the clay minerals) and "external" (caused by a force external to the clay). New techniques need to be developed to exploit known variations in clay mineralogy to separate internal from external effects.

Upscaling sorption/desorption processes in reactive transport models to describe metal/radionuclide transport: a critical review.

Models are a mainstay of the environmental sciences; they allow for both deeper understanding of process knowledge and, to a limited extent, predictive capabilities of current day inputs on the future. Mathematical codes have become increasingly complex with explicit inclusion of many processes that could not be accounted for using simpler solving techniques. And yet, for metal/radionuclide transport in subsurface systems, the inclusion of smaller scale processes in a numerical solver do not always lead to better descriptions of larger scale behavior. The reasons for this are many, but included in this review are the following: unknowable conceptual model errors, discrepancy in the scale of model discretization relative to the scale of the chemical/physical process, and omnipresent chemical and physical heterogeneities. Although it is commonly thought that larger, more complex systems require more complex models to gain insight and predictive capability, there is little to no experimental evidence supporting this thought. Indeed, the evidence points to the fact that larger systems can be well described with simple models. To test this thought and to appreciate the incorporation of scaling behaviors into reactive transport modeling, new experiments are needed that are intermediate in scale between the more traditional bench and field scales.