Enthalpies of formation of lanthanide oxyapatite phases

A family of lanthanide silicates adopts an oxyapatite-like structure with structural formula Ln9.33∎0.67(SiO4)6O2 (Ln 4 La, Sm, Nd, Gd, ∎ = vacancy). The enthalpies of solution, DHS, for these materials and their corresponding binary oxides were determined by high-temperature oxide melt solution calorimetry using molten 2PbO·B2O3 at 1078 K. These data were used to complete thermodynamic cycles to calculate enthalpies of formation from the oxides, ΔHs f-oxides (kJ/mol): La9.33∎0.67(SiO4)6O2 = −776.3 ± 17.9, Nd9.33∎0.67(SiO4)6O2 = −760.4 ± 31.9, Sm9.33∎0.67(SiO4)6O2 = −590.3 ± 18.6, and Gd9.33∎0.67(SiO4)6O2 = −446.9 ± 21.9. Reference data were used to calculate the standard enthalpies of formation from the elements, ΔH0 f (kJ/mol): La9.33∎0.67(SiO4)6O2 = −14611.0 ± 19.4, Nd9.33∎0.67(SiO4)6O2 = −14661.5 ± 32.2, Sm9.33∎0.67(SiO4)6O2 = −14561.7 ± 20.8, and Gd9.33∎0.67(SiO4)6O2 = −14402.7 ± 28.2. The formation enthalpies become more endothermic as the ionic radius of the lanthanide ion decreases

Nuclear Waste Package Mockups: A Study of In-Situ Redox State

The proposed Yucca Mountain Repository (YMR), located in southern Nevada, is to be the first facility in the US for the permanent disposal of high-level radioactive waste and spent nuclear fuels. Performance assessments have indicated that among the major radionuclides contributing to dose to a Reasonably Maximally Exposed Individual are Np, Tc, and I. These three radionuclides are mobile in most geochemical settings, and therefore sequestering them within the repository horizon would provide an effective limit to their migration. Corroding steel may offset radionuclide transport processes within the proposed waste packages at YMR by retaining radionuclides, creating locally reducing conditions, and reducing porosity. Ferrous iron containing materials such as magnetite have been shown to reduce UO{sub 2}{sup 2+} to UO{sub 2(s)}, and some ferrous iron-bearing ion-exchange materials have been shown to adsorb radionuclides and heavy metals (e.g. green rust). Locally reducing conditions may lead to the reduction and subsequent immobilization of problematic dissolved species such as TcO{sub 4}{sup -}, NpO{sub 2}{sup +}, and UO{sub 2}{sup 2+} and can also inhibit corrosion of spent nuclear fuel. Water occluded during corrosion produces bulky corrosion products, and consequently less porosity is available for water and radionuclide transport. The focus of this study is on the nature of Yucca Mountain waste package corrosion products and their effects on local redox conditions, radionuclide transport, and porosity. In order to measure in-situ redox, six small-scale (1:40) waste package mockups were constructed using A516 and 316 stainless steel, the same materials as the proposed Yucca Mountain waste packages. The mockups are periodically injected with a simulated groundwater and the accumulated effluent and corrosion products are evaluated for their Fe(II)/Fe(III) content and mineralogy. Oxygen fugacities are then calculated and, thus, in-situ redox conditions are determined. Early results indicate that corrosion products are amorphous Fe-oxyhydroxides, and nanocrystalline goethite and magnetite. That information together with the measured Fe(II)/Fe(III) ratios in the mockup effluent constrain the oxygen fugacity to a minimum of 10{sup -38} atm, many orders of magnitude below ambient. These results and their impact on radionuclide migration from YMR is discussed

Perrhenate and Pertechnetate Behavior on Iron and Sulfur-Bearing Compounds.

Investigations on the behavior of the radioactive element technetium frequently use a stable isotope of rhenium as an analogue. This is justified by citing the elements similar radii and major oxidation states of +7 and +4. However, at least one study [1] has shown this analogy to be imperfect. Therefore, one goal of our study is to compare the adsorption behavior of perrhenate and pertechnetate (the major forms of Re and Tc in natural waters) on a number of different mineral surfaces. Quantum mechanical calculations were performed on the adsorption of these two anions on a series of iron oxides and sulfides. With these calculations, we gain insight into any differences between the anions adsorption behavior, including geometry, adsorption energies, and electronic structure such as density of states and orbital shapes and energies at the adsorption site. Differences between interactions on terraces and step edges, the effects of co-adsorbates such as Na{sup +} or H{sup +}, and possible reduction mechanisms are also explored. The influence of water was calculated using homogeneous dielectric fluids and explicit water molecules. As a complement to the calculations, batch sorption tests are in progress involving ReO{sub 4}{sup -}/TcO{sub 4}{sup -} solution in contact with Fe metal, 10% Fe-doped hydroxyapatite, goethite, hematite, magnetite, pyrite, galena, and sphalerite

Waste Package Corrosion Studies Using Small Mockup Experiments

The corrosion of spent nuclear fuel and subsequent mobilization of radionuclides is of great concern in a geologic repository, particularly if conditions are oxidizing. Corroding A516 steel may offset these transport processes within the proposed waste packages at the Yucca Mountain Repository (YMR) by retaining radionuclides, creating locally reducing conditions, and reducing porosity. Ferrous iron, Fe{sup 2+}, has been shown to reduce UO{sub 2}{sup 2+} to UO{sub 2(s)} [1], and some ferrous iron-bearing ion-exchange materials adsorb radionuclides and heavy metals [2]. Of particular interest is magnetite, a potential corrosion product that has been shown to remove TcO{sub 4}{sup -} from solution [3]. Furthermore, if Fe{sup 2+} minerals, rather than fully oxidized minerals such as goethite, are produced during corrosion, then locally reducing conditions may be present. High electron availability leads to the reduction and subsequent immobilization of problematic dissolved species such as TcO{sub 4}{sup -}, NpO{sub 2}{sup +}, and UO{sub 2}{sup 2+} and can also inhibit corrosion of spent nuclear fuel. Finally, because the molar volume of iron material increases during corrosion due to oxygen and water incorporation, pore space may be significantly reduced over long time periods. The more water is occluded, the bulkier the corrosion products, and the less porosity is available for water and radionuclide transport. The focus of this paper is on the nature of Yucca Mountain waste package steel corrosion products and their effects on local redox state, radionuclide transport, and porosity

Sequestration of Radionuclides and Heavy Metal by Hydroxyapatite Doped with Fe, Cu and Sn

Apatite, Ca{sub 5}(PO{sub 4}){sub 3}(F,OH,Cl) (P6{sub 3}/m, Z=2), is the most abundant phosphate mineral on Earth. The end-member hydroxyapatite, Ca{sub 5}(PO{sub 4}){sub 3}OH (P2{sub 1}/b), is the primary mineral component in bones and teeth and tends to scavenge and sequester heavy metals in the human body. Hydroxyapatite has also been shown to be effective at sequestering radionuclides and heavy metals in certain natural systems (Dybowska et al., 2004). Hydroxyapatite has been the focus of many laboratory studies and is utilized for environmental remediation of contaminated sites (Moore et al., 2002). The crystal structure of apatite tolerates a great deal of distortion caused by extensive chemical substitutions. Metal cations (e.g. REE, actinides, K, Na, Mn, Ni, Cu, Co, Zn, Sr, Ba, Pb, Cd, Fe) substitute for Ca, and oxyanions (e.g. AsO{sub 4}{sup 3-}, SO{sub 4}{sup 2-}, CO{sub 3}{sup 2-}, SiO{sub 4}{sup 4-}, CrO{sub 4}{sup 2-}) replace PO{sub 4}{sup 3-} through a series of coupled substitutions that preserve electroneutrality. Owing to the ability of apatite to incorporate ''impurities'' (including actinides) gives rise to its proposed use as a waste form for radionuclides. Recent work at Sandia National Laboratory demonstrated that hydroxyapatite has a strong affinity for U, Pu, Np, Sr and Tc reduced from pertechnetate (TcO{sub 4}{sup -}) by SnCl{sub 2} (Moore et al., 2002). Based on these earlier promising results, an investigation was initiated into the use of apatite-type materials doped with aliovalent cations including Fe, Cu and Sn as Tc-scavengers. Synthetic Fe and Cu-doped hydroxyapatite samples were prepared by precipitation of Ca, from Ca-acetate, and P, from ammonium phosphate. The Fe and Cu were introduced as chlorides into the Ca-acetate solution. Stannous chloride was used as a reducing agent and was apparently incorporated into the crystal structures of the hydroxyapatite samples in small, as yet undetermined quantities

A HOST PHASE FOR THE DISPOSAL OF WEAPONS PLUTONIUM

Research was conducted into the possible use of zircon (ZrSiO{sub 4}) as a host phase for storage or disposal of excess weapons plutonium. Zircon is one of the most chemically durable minerals. Its structure can accommodate a variety of elements, including plutonium and uranium. Natural zircon contains uranium and thorium together in different quantities, usually in the range of less than one weight percent up to several weight percent. Zircon occurs in nature as a crystalline or a partially to fully metamict mineral, depending on age and actinide element concentration, i.e., on radiation damage. These zircon samples have been studied extensively and the results are documented in the literature in terms of radiation damage to the crystal structure and related property changes, e.g., density, hardness, loss of uranium and lead, etc. Thus, a unique suite of natural analogues are available to describe the effect of decay of {sup 239}Pu on zircon's structure and how zircon's physical and chemical properties will be affected over very long periods of time. Actually, the oldest zircon samples known are over 3 billion years old. This period covers the time for decay of {sup 239}Pu (half-life 24,300 yr.) and most of its daughter {sup 235}U (half-life 700 million yr.). Because of its chemical durability, even under extreme geological conditions, zircon is the most widely used mineral for geochronological dating (7,000 publications). It is the oldest dated mineral on earth and in the universe. Zircon has already been doped with about 10 weight percent of plutonium. Pure PuSiO{sub 4} has also been synthesized and has the same crystal structure as zircon. However, use of zircon as a storage medium or waste form for plutonium requires further materials characterization. Experiments can either be conducted in laboratories where plutonium can be handled or plutonium can be simulated by other elements, and experiments can be done under less restricted conditions. The authors conducted work with zircon doped with thorium, uranium and cerium, respectively. They synthesized various zircon compositions and studied the solid solution properties of mixed (Zr,X)SiO{sub 4} [X represents Th, U, Ce, respectively]. They measured the dissolution rate of pure crystalline zircon at elevated temperatures and of an amorphous hydrated zircon. This final report together with two previous annual reports summarize the accomplishments made in two areas: (1) synthesis of zircon solid solutions with Th, U, and Ce; and (2) measurement of the chemical durability of zircon. The focus of the final report is on the measurement of zircon's dissolution rate in water and on the determination of volubility limits of Th, U, and Ce in zircon

Enthalpies of Formation of Cerium Zirconate: (Ce,Zr)O2 Fluorite and Ce2Zr2O7 Pyrochlore

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/87715/2/286_1.pd