An alkaline brine containing uranyl (UO 2 2+ ) leaked to the thick unsaturated zone at the Hanford Site. We examined samples from this zone at microscopic scale to determine the mode of uranium occurrence-microprecipitates of uranyl (UO 2 2+ ) silicate within lithic-clast microfractures-and constructed a conceptual model for its emplacement, which we tested using a model of reactive diffusion at that scale. The study was driven by the need to understand the heterogeneous distribution of uranium and the chemical processes that controlled it. X-ray and electron microprobe imaging showed that the uranium was associated with a minority of clasts, specifically granitic clasts occupying less than four percent of the sediment volume. XANES analysis at micron resolution showed the uranium to be hexavalent. The uranium was precipitated in microfractures as radiating clusters of uranyl silicates, and sorbed uranium was not observed on other surfaces. Compositional determinations of the 1-3 lm precipitates were difficult, but indicated a uranyl silicate. These observations suggested that uranyl was removed from pore waters by diffusion and precipitation in microfractures, where dissolved silica within the granite-equilibrated solution would cause supersaturation with respect to sodium boltwoodite. This hypothesis was tested using a reactive diffusion model operating at microscale. Conditions favoring precipitation were simulated to be transient, and driven by the compositional contrast between pore and fracture space. Pore-space conditions, including alkaline pH, were eventually imposed on the microfracture environment. However, conditions favoring precipitation were prolonged within the microfracture by reaction at the silicate mineral surface to buffer pH in a solubility limiting acidic state, and to replenish dissolved silica. During this time, uranyl was additionally removed to the fracture space by diffusion from pore space. Uranyl is effectively immobilized within the microfracture environment within the presently unsaturated Vadose Zone.
A focused ion beam (FIB) instrument has been used to mill surfaces in singlecrystal Si and single-crystal Cu for subsequent electron backscattering diffraction (EBSD) analysis. The FIB cuts were performed using a 30 keV and a 5 keV Ga ϩ ion beam at a stage tilt of 20°to provide a readily obtainable 70°surface for direct EBSD investigation in a scanning electron microscope (SEM). The quality of the patterns is related to the amount of FIB damage induced in the Cu and Si. These or similar methods should be directly transferable to a FIB/SEM dual beam instrument equipped with an EBSD detector.
Articles you may be interested inMilling of submicron channels on gold layer using double charged arsenic ion beam The use of focused ion beam ͑FIB͒ instruments for device modification and specimen preparation has become a mainstay in the microelectronics industry and in thin film characterization. The role of the FIB as a tool to rapidly prepare high quality transmission electron microscopy specimens is particularly significant. Special attention has been given to FIB milling of Cu and Si in the microelectronics arena. Although FIB applications involving Si have been extremely successful, it has been noted that Cu tends to present significant challenges to FIB milling because of effects such as the development of milling induced topographical features. We show evidence that links the occurrence of milling induced topography to the severity of redeposition. Specifically, Cu, which sputters ϳ2.5 times faster than Si, exhibits an increased susceptibility to redeposition related artifacts. In addition, the effects and the mechanism of Ga ϩ channeling in Cu is used to illustrate that Ga ϩ channeling reduces the sputtering yield, improves the quality of FIB mill cuts, and improves the surface characteristics of FIB milled Cu. Finally, a technique for improving FIB milling across grain boundaries or interfaces using ion channeling contrast is suggested.
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