Hanford Tank 241-S-112 Residual Waste Composition and Leach Test Data

This report presents the results of laboratory characterization and testing of two samples (designated 20406 and 20407) of residual waste collected from tank S-112 after final waste retrieval. These studies were completed to characterize the residual waste and assess the leachability of contami¬nants from the solids. This is the first report from this PNNL project to describe the composition and leach test data for residual waste from a salt cake tank. All previous PNNL reports (Cantrell et al. 2008; Deutsch et al. 2006, 2007a, 2007b, 2007c) describing contaminant release models, and characterization and testing results for residual waste in single-shell tanks were based on samples from sludge tanks

Rhenium Uptake, as Analogue for Tc-99, by Steel Corrosion Products

Static batch experiments were used to examine the sorption of dissolved perrhenate [Re(VII)], as a surrogate for pertechnetate [Tc(VII)], on corrosion products of A-516 carbon steel coupons contacted with synthetic groundwater or dilute water. After 109 days of contact time, the concentration of dissolved Re(VII) in the synthetic groundwater matrix decreased by approximately 26%; the dilute water matrix experienced a 99% decrease in dissolved Re(VII) over the same time period. Bulk XRD results for the corroded steel coupons showed that the corrosion products consisted primarily of maghemite, lepidocrocite, and goethite. Analyses of the coupons by SEM/EDS indicated that Re was present with the morphologically complex assemblages of Fe oxide/hydroxide corrosion products for samples spiked with the highest dissolved Re(VII) concentration (1.0 mmol/L) used for these experiments. Analyses of corroded steel coupons contacted with solutions containing 1.0 mmol/L Re(VII) by synchrotron-based methods confirmed the presence of Re sorbed with the corrosion product on the steel coupons. Analyses showed that the Re sorbed on these corroded coupons was in the +7 oxidation state, suggesting that the Re(VII) uptake mechanism did not involve reduction of Re to a lower oxidation state, such as +4. The results of our studies using Re(VII) as an analogue for Tc(VII)-99 suggest that Tc(VII)-99 would also be sorbed with steel corrosion products and that the inventory of Tc(VII)-99 released from breached waste packages would be lower than what is now conservatively estimated

A stable nanoporous silicon anode prepared by modified magnesiothermic reactions

Porous silicon prepared by low-cost and scalable magnesiothermic reactions is a promising anode material for Li-ion batteries; yet, retaining good cycling stability for such materials in electrodes of practical loading remains a challenge. Here, we engineered the nanoporous silicon from a modified magnesiothermic reaction by controlled surface oxidization forming a <5 nm oxide layer on the 10–20 nm Si nanocrystallites. High loading electrodes of ~3 mAh/cm² demonstrates stable cycling with ~80% capacity retention over 150 cycles. The specific discharge capacity based on the total electrode weight is ~1000 mAh/g at the lithiation/delithiation current density of 0.5/0.75 mA/cm². This work reveals the importance of the surface treatment on nanostructured Si, which will lead to a well-controlled ratio of silicon and surface oxide layer and provide guidance on further improvement on silicon-based anode materials.This is the publisher’s final pdf. The published article is copyrighted by Elsevier and can be found at: http://www.journals.elsevier.com/nano-energy/Keywords: Silicon anode, Lithium ion batteries, Magnesiothermic reaction, Porous silico

Hanford Tank 241-C-103 Residual Waste Contaminant Release Models and Supporting Data

This report tabulates data generated by laboratory characterization and testing of three samples collected from tank C-103. The data presented here will form the basis for a release model that will be developed for tank C-103. These release models are being developed to support the tank risk assessments performed by CH2M HILL Hanford Group, Inc. for DOE

Hanford Tanks 241-C-202 and 241-C-203 Residual Waste Contaminant Release Models and Supporting Data

As directed by Congress, the U. S. Department of Energy (DOE) established the Office of River Protection in 1998 to manage DOE's largest, most complex environmental cleanup project – retrieval of radioactive waste from Hanford tanks for treatment and eventual disposal. Sixty percent by volume of the nation's high-level radioactive waste is stored at Hanford in aging deteriorating tanks. If not cleaned up, this waste is a threat to the Columbia River and the Pacific Northwest. CH2M Hill Hanford Group, Inc., is the Office of River Protection's prime contractor responsible for the storage, retrieval, and disposal of Hanford's tank waste. As part of this effort, CH2M HILL Hanford Group, Inc. contracted with Pacific Northwest National Laboratory (PNNL) to develop release models for key contaminants that are present in residual sludge remaining after closure of Hanford Tanks 241-C-203 (C-203) and 241-C-204 (C-204). The release models were developed from data generated by laboratory characterization and testing of samples from these two tanks. These release models are being developed to support the tank closure risk assessments performed by CH2M HILL Hanford Group, Inc., for DOE

Uranium Extraction From Laboratory-Synthesized, Uranium-Doped Hydrous Ferric Oxides

The extractability of uranium (U) from synthetic uranium-hydrous ferric oxide (HFO) coprecipitates has been shown to decrease as a function of mineral ripening, consistent with the hypothesis that the ripening process will decrease uranium lability. To evaluate this process, three HFO suspensions were coprecipitated with uranyl (UO22+) and maintained at pH 7.0 ± 0.1. Uranyl was added to the HFO post-precipitation in a fourth suspension. Two suspensions also contained either coprecipitated silicate(Si-U-HFO) or phosphate (P-U-HFO).After precipitation of the HFOs, at time intervals of 1 week, 1 month, 6 months, 1 year, and 2 years, aliquots of each suspension were contacted with five extractant solutions for a range of time. Uranium was preferentially extracted over Fe in varying degrees from all coprecipitates, by all extractants. The preference was dependent on the duration of mineral ripening and adjunct anion. Micro-X-ray diffraction analysis provides evidence for the transformation from amorphous material to phases containing substantial proportions of crystalline goethite and hematite, except the P-U-HFO, which remained primarily amorphous. Analysis of the U-HFO coprecipitate by the Mössbauer technique and scanning electron microscopy provides confirmation of an increase in particle size and evidence of mineral ripening to crystalline phases

Plutonium Mobility Studies: 216-Z-9 Trench Sample Analysis Results

A variety of analyses were conducted on selected sediment samples collected from two wells (299 W15-46 and 299-W15-48) drilled near the 216-Z-9 Trench to elucidate the form and potential for Pu and Am to be mobilized under present conditions and those that could be expected in future remediation scenarios. Analyses included moisture content, determination of the less than sand size fraction (silt plus clay), carbon analysis, SEM/EDS analysis, microwave-assisted acid digestions for total element analysis, and extraction tests using Hanford groundwater as the leachate. Results of the extraction tests were used as input to conduct equilibrium geochemical modeling of the solutions with Geochemist’s Workbench®. Geochemical modeling results for Pu were evaluated in terms of recent conclusions regarding the solubility and redox reactions of Pu by Neck et al. (2007a, 2007b). It was found that the highest concentrations of Pu and Am were associated with sediments of low silt/clay content and occur above silt/clay rich layers within the sediment profile. It was also found that the Pu and Am were relatively enriched in the silt/clay portion of these samples. The fact that the highest concentrations of Pu and Am occurred in sediments with low silt/clay contents suggests that waste solutions had perched on top of the low permeability silt/clay rich layers and interactions with the high silt/clay layers was minimal. SEM/EDS analysis indicated that the Pu and Am in these sediments does not occur as discrete micron size particles, and therefore must occur as mononuclear or polynuclear/ nanoclusters size particles adsorbed throughout the sediment samples. Leaching of these samples with Hanford groundwater indicates that release of Pu and Am from the sediments is correlated most significantly with the acidity of the water and not the initial concentrations of Pu and Am in the sediments. Only extracts that were acidic after contact with the sediments (pH 4.3 to 5.4) contained detectable concentrations of extractable Pu and Am. Water extracts from samples containing high concentrations of TBP suggest that if the TBP degradation products DBP and MBP are available in these sediments, they do not significantly increase the extractability of Pu or Am. Geochemical modeling results suggest that the concentrations of Am in water in contact with these sediments is not controlled by the solubility of Am(OH)3(c), but rather by desorption of Am that has been previously adsorbed to the sediments during the period of active wastewater disposal. Sediment extracts that had measureable concentrations of Am only occurred in samples that were fairly acidic (pH 4.3 to 4.6), indicating that Am will remain effectively sequestered to sediments when pH conditions approach those of normal Hanford groundwater (mildly alkaline, ~ pH 8). The geochemical modeling results indicate that Pu in acidic extracts is significantly undersaturated with respect to PuO2(am). However, recent reviews of Pu solubility and redox reactions suggest that the data used for these calculations is incomplete (Neck et al. 2007a, 2007b). The results of Neck et al. (2007a, 2007b) suggest that Pu concentrations in solutions in contact with the 216-Z-9 Trench sediment samples might be controlled by a mixed valent solid phase [(PuV)2x(PuIV)1-2xO2+x(am)] with various dissolved Pu(V) complexes and Pu(IV)O2(am) colloids or nanoclusters being the dominant species in solution for typical Hanford groundwater conditions. Adsorption is likely to have a major impact on the mobility of these species (Neck et al. 2007a, 2007b; Clark et al. 2006; Kaplan et al. 2006; Powell et al. 2005). Further research is planned to verify these hypotheses

The mineralogic transformation of ferrihydrite induced by heterogeneous reaction with bioreduced anthraquinone disulfonate (AQDS) and the role of phosphate

Bioreduced anthraquinone-2,6-disulfonate (AH2DS; dihydro-anthraquinone) was reacted with a 2-line, Si-substituted ferrihydrite under anoxic conditions at neutral pH in PIPES buffer. Phosphate (P) and bicarbonate (C); common adsorptive oxyanions and media/buffer components known to effect ferrihydrite mineralization; and Fe(II)aq (as a catalytic mineralization agent) were used in comparative experiments. Heterogeneous AH2DS oxidation coupled with Fe(III) reduction occurred within 0.13–1 day, with mineralogic transformation occurring thereafter. The product suite included lepidocrocite, goethite, and/or magnetite, with proportions varing with reductant:oxidant ratio (r:o) and the presence of P or C. Lepidocrocite was the primary product at low r:o in the absence of P or C, with evidence for multiple formation pathways. Phosphate inhibited reductive recrystallization, while C promoted goethite formation. Stoichiometric magnetite was the sole product at higher r:o in the absence and presence of P. Lepidocrocite was the primary mineralization product in the Fe(II)aq system, with magnetite observed at near equal amounts when Fe(II) was high [Fe(II)/Fe(III)] = 0.5 and P was absent. P had a greater effect on reductive mineralization in the Fe(II)aq system, while AQDS was more effective than Fe(II)aq in promoting magnetite formation. The mineral products of the direct AH2DS-driven reductive reaction are different from those observed in AH2DS-ferrihydite systems with metal reducing bacteria, particularly in presence of P