Abiotic reduction of aquifer materials by dithionite: A promising in-situ remediation technology

Laboratory batch and column experiments were conducted with Hanford sediments to develop the capability to predict (1) the longevity of dithionite in these systems, (2) its efficiency as a reductant of structural iron, and (3) the longevity and reactivity of the reduced iron with soluble inorganic and organic species. After an initial induction period, the loss of dithionite by disproportionation and oxidation could be described by pseudo-first-order (PFO) kinetics. Other than the initial reaction with ferric iron, the primary factor promoting loss of dithionite in this system was disproportion nation via heterogeneous catalysis at mineral surfaces. The efficiency of the reduction of structural iron was nearly 100% for the first fourth of the ferric iron, but declined exponentially with higher degrees of reduction so that 75% of the ferric iron could be reduced. This decrease in reduction efficiency probably was related to differences in the accessibility of ferric iron in the mineral particles, with iron in clay-sized particles being the most accessible and that in silt- and sand-sized particles less accessible. Flow-through column studies showed that a reduced-sediment barrier created in this manner could maintain a reducing environment

Egg rejection in blackbirds Turdus merula: a by-product of conspecific parasitism or successful resistance against interspecific brood parasites?

Traditional theory assumes that egg recognition and rejection abilities arise as a response against interspecific brood parasitism (IBP). However, rejection also appears in some species that are currently not exploited by interspecific parasites, such as Turdus thrushes. Recent evidences suggest that rejection abilities evolved in these species as a response to conspecific brood parasitism (CBP). To test these two alternative hypotheses, we performed an experimental study by parasitizing nests of the common blackbird (Turdus merula) with conspecifics or heterospecific eggs under different risk of parasitism (presence of interspecific or conspecific parasites near the nest). Common blackbird is a potential host of the common cuckoo (Cuculus canorus) but suffers low levels of CBP too. Results: We found that blackbirds were able to recognize and eject heterospecific eggs at high rates whereas most of conspecifics eggs were not recognized and, therefore, accepted. Ejection rates of conspecific eggs did not exceed 13 %, even in situations of high risk of CBP (blackbird female placed near the nest), which contradict the main prediction derived from the CBP hypothesis. Conversely, ejection rates of experimental eggs simulating IBP were much higher (80–100 %). Furthermore, female blackbirds were more aggressive towards cuckoos than towards blackbird dummies. Conclusions: Our results considered together support the IBP hypothesis, indicating that recognition and rejection of parasitic eggs in blackbirds have probably evolved due to previous cuckoo parasitism. The current absence of IBP in blackbirds may be due to the highly efficient rejection abilities in this species. Thus, these abilities have been retained in absence of brood parasitism as a consequence of the low costs involved for blackbirds, resulting in a successful resistance against interspecific brood parasitism.Financial support has been provided by the Consejería Economía, Innovación, Ciencia y Empleo. Junta de Andalucia (research project CVI-6653)

Evaluation of the Long-Term Performance of Titanate Ceramics for Immobilization of Excess Weapons Plutonium: Results from Pressurized Unsaturated Flow and Single Pass Flow-Through Testing

This report summarizes our findings from pressurized unsaturated flow (PUF) and single-pass flow-through (SPFT) experiments to date. Results from the PUF test of a Pu-bearing ceramic with enclosing surrogate high-level waste glass show that the glass reacts rapidly to alteration products. Glass reaction causes variations in the solution pH in contact with the ceramic materials. We also document variable concentrations of Pu in solution, primarily in colloidal form, which appear to be related to secular variations in solution composition. The apparent dissolution rate of the ceramic waste form, based on Ba concentrations in the effluent, is estimated at {le} 10{sup {minus}5} g/(m{sup 2} {center_dot} d). Pu-bearing colloids were recovered in the size range of 0.2 to 2 {micro}m, but it is not clear that such entities would be transported in a system that is not advective-flow dominated. Results from SPFT experiments give information on the corrosion resistance of two surrogate Pu-ceramics (Ce-pyrochlore and Ce-zirconolite) at 90 C over a pH range of 2 to 12. The two ceramics were doped with minor quantities ({approximately}0.1 mass%) of MoO{sub 3}, so that concentrations of Mo in the effluent solution could be used to monitor the reaction behavior of the materials. The data obtained thus far from experiments with durations up to 150 d do not conclusively prove that the solid-aqueous solution systems have reached steady-state conditions. Therefore, the dissolution mechanism cannot be determined. Apparent dissolution rates of the two ceramic materials based on Ce, Gd, and Mo concentrations in the effluent solutions from the SPFT are nearly identical and vary between 1.1 to 8.5 x 10{sup {minus}4} g/(m{sup 2} {center_dot} d). In addition, the data reveal a slightly amphoteric dissolution behavior, with a minimum apparent rate at pH = 7 to 8, over the pH range examined. Results from two related ceramic samples suggest that radiation damage can have a measurable effect on the dissolution of titanium-based ceramics. The rare earth pyrochlores, Gd{sub 2}Ti{sub 2}O{sub 7} and Lu{sub 2}Ti{sub 2}O{sub 7}, are being studied as part of the DOE Environmental Management Science Program, and the results are germane to this study. The corrosion resistances of both heavy-ion bombarded and pristine (non-bombarded) specimens are being examined with the SPFT test. Initial data indicate that the dissolution rate may increase by a factor of 3 times or more when these materials become amorphous from radiation damage

Characterization of Vadose Zone Sediment: Uncontaminated RCRA Borehole Core Samples and Composite Samples

The overall goal of the of the Tank Farm Vadose Zone Project, led by CH2M HILL Hanford Group, Inc., is to define risks from past and future single-shell tank farm activities. To meet this goal, CH2M HILL Hanford Group, Inc. asked scientists from Pacific Northwest National Laboratory to perform detailed analyses on vadose zone sediment from within the S-SX Waste Management Area. This report is one in a series of four reports to present the results of these analyses. Specifically, this report contains all the geologic, geochemical, and selected physical characterization data collected on vadose zone sediment recovered from Resource Conservation and Recovery Act (RCRA) borehole bore samples and composite samples. Intact cores from two “clean” RCRA boreholes (299-W22-48 and 299-W22-50) near the SX Tank Farm and four, large-quantity grab samples from outcrop sediment on the Hanford Site were sampled to better understand the fate of contaminants in the vadose zone beneath underground storage tanks at the Hanford Site. Borehole and outcrop samples analyzed for this report are located outside the tank farms, and therefore may be considered standard or background samples from which to compare contaminated sediments within the tank farms themselves. This report presents our interpretation of the physical, chemical, and mineralogical properties of the uncontaminated vadose zone sediments, and variations in the vertical distribution of these properties. The information presented in this report is intended to support preparation of the S-SX field investigation report(a) prepared by CH2M HILL Hanford Group, Inc. as well as future remediation actions at the S-SX Tank Farm. The geology under the SX Tank Farm forms the framework through which the contaminants move, and provides the basis with which to interpret and extrapolate the physical and geochemical properties that control the migration and distribution of contaminants. Of particular interest are the interrelationships between the coarser- and finer-grained facies, and the degree of contrast in their physical and geochemical properties. For the two boreholes, lithologic sections were constructed using detailed geologic descriptions and geophysical logs. In some cases the results of laboratory analyses (e.g., particle-size distribution, moisture, calcium carbonate content) helped to refine the resulting stratigraphic and lithologic interpretations

In Situ Study of CO 2 and H 2 O Partitioning between Na–Montmorillonite and Variably Wet Supercritical Carbon Dioxide

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