Scale-dependent desorption of uranium from contaminated subsurface sediments

Column experiments were performed to investigate the scale-dependent desorption of uranyl [U(VI)] from a contaminated sediment collected from the Hanford 300 Area at the U.S. Department of Energy (DOE) Hanford Site, Washington. The sediment was a coarse-textured alluvial flood deposit containing significant mass percentage of river cobble. U(VI) was, however, only associated with its minor fine-grained (\u3c2 mm) mass fraction. U(VI) desorption was investigated both from the field-textured sediment using a large column (80 cm length by 15 cm inner diameter) and from its \u3c2 mm U(VI)- associated mass fraction using a small column (10 cm length by 3.4 cm inner diameter). Dynamic advection conditions with intermittent flow and stop-flow events of variable durations were employed to investigate U(VI) desorption kinetics and its scale dependence. A multicomponent kinetic model that integrated a distributed rate of mass transfer with surface complexation reactions successfully described U(VI) release from the fine-grained U(VI)-associated materials. The field-textured sediment in the large column displayed dual-domain tracer-dependent mass transfer properties that affected the breakthrough curves of bromide, pentafluorobenzoic acid (PFBA), and tritium. The tritium breakthrough curve showed stronger nonequilibrium behavior than did PFBA and bromide and required a larger immobile porosity to describe. The dual-domain mass transfer properties were then used to scale the kinetic model of U(VI) desorption developed for the fine-grained materials to describe U(VI) release and reactive transport in the field-textured sediment. Numerical simulations indicated that the kinetic model that was integrated with the dual-domain properties determined from tracer PFBA and Br best described the experimental results. The kinetic model without consideration of the dual-domain properties overpredicted effluent U(VI) concentrations, while the model based on tritium mass transfer underpredicted the rate of U(VI) release. Overall, our results indicated that the kinetics of U(VI) release from the field-textured sediment were different from that of its fine-grained U(VI)-associated mass fraction. However, the desorption kinetics measured on the U(VI)-containing mass fraction could be scaled to describe U(VI) reactive transport in the contaminated field-textured sediment after proper consideration of the physical transport properties of the sediment. The research also demonstrated a modeling approach to integrate geochemical processes into field-scale reactive transport models

Scale-dependent desorption of uranium from contaminated subsurface sediments

Column experiments were performed to investigate the scale-dependent desorption of uranyl [U(VI)] from a contaminated sediment collected from the Hanford 300 Area at the U.S. Department of Energy (DOE) Hanford Site, Washington. The sediment was a coarse-textured alluvial flood deposit containing significant mass percentage of river cobble. U(VI) was, however, only associated with its minor fine-grained (\u3c2 mm) mass fraction. U(VI) desorption was investigated both from the field-textured sediment using a large column (80 cm length by 15 cm inner diameter) and from its \u3c2 mm U(VI)- associated mass fraction using a small column (10 cm length by 3.4 cm inner diameter). Dynamic advection conditions with intermittent flow and stop-flow events of variable durations were employed to investigate U(VI) desorption kinetics and its scale dependence. A multicomponent kinetic model that integrated a distributed rate of mass transfer with surface complexation reactions successfully described U(VI) release from the fine-grained U(VI)-associated materials. The field-textured sediment in the large column displayed dual-domain tracer-dependent mass transfer properties that affected the breakthrough curves of bromide, pentafluorobenzoic acid (PFBA), and tritium. The tritium breakthrough curve showed stronger nonequilibrium behavior than did PFBA and bromide and required a larger immobile porosity to describe. The dual-domain mass transfer properties were then used to scale the kinetic model of U(VI) desorption developed for the fine-grained materials to describe U(VI) release and reactive transport in the field-textured sediment. Numerical simulations indicated that the kinetic model that was integrated with the dual-domain properties determined from tracer PFBA and Br best described the experimental results. The kinetic model without consideration of the dual-domain properties overpredicted effluent U(VI) concentrations, while the model based on tritium mass transfer underpredicted the rate of U(VI) release. Overall, our results indicated that the kinetics of U(VI) release from the field-textured sediment were different from that of its fine-grained U(VI)-associated mass fraction. However, the desorption kinetics measured on the U(VI)-containing mass fraction could be scaled to describe U(VI) reactive transport in the contaminated field-textured sediment after proper consideration of the physical transport properties of the sediment. The research also demonstrated a modeling approach to integrate geochemical processes into field-scale reactive transport models

Chemical weathering of new pyroclastic deposits from Mt. Merapi (Java), Indonesia.

The Java Island, Indonesia with abundant amount of pyroclastic deposits is located in the very active and dynamic Pacific Ring of Fires. Studying the geochemical weathering indices of these pyroclastic deposits is important to get a clear picture about weathering profiles on deposits resulting from the eruption of Mt. Merapi. Immediately after the first phase of the eruption (March to June 2006), moist and leached pyroclastic deposits were collected. These pyroclastic deposits were found to be composed of volcanic glass, plagioclase feldspar in various proportions, orthopyroxene, clinopyroxene, olivine, amphibole and titanomagnetite. The total elemental composition of the bulk samples (including trace elements and heavy metals) was determined by wet chemical methods and X-ray fluorescence (XRF) analyses. Weathering of the pyroclastic deposits was studied using various weathering indices. The Ruxton ratio, weathering index of Parker, Vought resudual index and chemical index of weathering of moist pyroclastic deposits were lower than those of the leached samples, but the alteration indices (chemical and plagioclase) were slightly higher in the moist compared to the leached pyroclastic deposits

Fluorescence spectroscopy of U(VI)-silicates and U(VI)-contaminated Hanford sediment

Time-resolved U(VI) laser fluorescence spectra (TRLFS) were recorded for a series of natural uranium-silicate minerals including boltwoodite, uranophane, soddyite, kasolite, sklodowskite, cuprosklodowskite, haiweeite, and weeksite, a synthetic boltwoodite, and four U(VI)-contaminated Hanford vadose zone sediments. Lowering the sample temperature from RT to ~5.5 K significantly enhanced the fluorescence intensity and spectral resolution of both the minerals and sediments, offering improved possibilities for identifying uranyl species in environmental samples. At 5.5 K, all of the uranyl silicates showed unique, well-resolved fluorescence spectra. The symmetric O = U = O stretching frequency, as determined from the peak spacing of the vibronic bands in the emission spectra, were between 705 to 823 cm−1 for the uranyl silicates. These were lower than those reported for uranyl phosphate, carbonate, or oxy-hydroxides. The fluorescence emission spectra of all four sediment samples were similar to each other. Their spectra shifted minimally at different time delays or upon contact with basic Na/Ca-carbonate electrolyte solutions that dissolved up to 60% of the precipitated U(VI) pool. The well-resolved vibronic peaks in the fluorescence spectra of the sediments indicated that the major fluorescence species was a crystalline uranyl mineral phase, while the peak spacing of the vibronic bands pointed to the likely presence of uranyl silicate. Although an exact match was not found between the U(VI) fluorescence spectra of the sediments with that of any individual uranyl silicates, the major spectral characteristics indicated that the sediment U(VI) was a uranophane-type solid (uranophane, boltwoodite) or soddyite, as was concluded from microprobe, EXAFS, and solubility analyses

Removal of TcO4- from Representative Nuclear Waste Streams with Layered Potassium Metal Sulfide Materials

Many efforts have focused on the sequestration and immobilization of 99Tc because the radionuclide is highly mobile in oxidizing environments and presents serious health risks due to its radiotoxicity and long half-life (t1/2 = 213 000 a). One of the more common methods for Tc removal from solution and immobilization in solids is based on reducing Tc from highly soluble Tc(VII) to sparingly soluble Tc(IV). Here, we report results obtained with two potassium metal sulfides (KMS-2 and KMS-2-SS) that are capable of reducing Tc(VII) to Tc(IV). Batch sorption experiments were performed in both oxic and anoxic conditions for 15 d in both deionized water (DIW) and a highly caustic (pH ∼ 13.6), high ionic strength (8.0 mol L-1), low-activity waste (LAW) stream simulant solution. Tc removal for both materials in DIW is improved in anoxic conditions compared to oxic conditions as a result of a higher solution pH. In DIW and anoxic conditions, KMS-2 is capable of removing ∼45% of Tc, and KMS-2-SS is capable of removing ∼90% of Tc. Both materials perform even better in the LAW simulant and remove more than 90% of available Tc after 15 d of contact in anoxic conditions. Postreaction solids analyses indicate that Tc(VII) is reduced to Tc(IV) and that Tc(IV) is bonded to S atoms in a Tc2S7 complex. Examination of the materials after Tc removal by X-ray diffraction shows that the initially crystalline KMS-2 materials lose much of their initial long-range order. We suggest a Tc removal mechanism wherein the TcO4- enters the interlayer of the KMS-2 materials where it is reduced by sulfide, which results in a distorted crystalline structure and a solid-state Tc2S7 complex

A coupled microscopy approach to assess the nano-landscape of weathering

Mineral weathering is a balanced interplay among physical, chemical, and biological processes. Fundamental knowledge gaps exist in characterizing the biogeochemical mechanisms that transform microbe-mineral interfaces at submicron scales, particularly in complex field systems. Our objective was to develop methods targeting the nanoscale by using high-resolution microscopy to assess biological and geochemical drivers of weathering in natural settings. Basalt, granite, and quartz (53-250 mu m) were deployed in surface soils (10 cm) of three ecosystems (semiarid, subhumid, humid) for one year. We successfully developed a reference grid method to analyze individual grains using: (1) helium ion microscopy to capture micron to sub-nanometer imagery of mineral-organic interactions; and (2) scanning electron microscopy to quantify elemental distribution on the same surfaces via element mapping and point analyses. We detected locations of biomechanical weathering, secondary mineral precipitation, biofilm formation, and grain coatings across the three contrasting climates. To our knowledge, this is the first time these coupled microscopy techniques were applied in the earth and ecosystem sciences to assess microbe-mineral interfaces and in situ biological contributors to incipient weathering.Oregon State University faculty startup fund; Office of Biological and Environmental Research; NSF [EAR-GEO-1331846, EAR-0724958, IOS-1354219]; [EAR-1023215]Open access journalThis item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at [email protected]