John M. Hanchar

Rare earth elements in synthetic zircon: Part 1. Synthesis, and rare earth element and phosphorus doping

Abstract Zircon crystals were grown from a Li-Mo flux (7.5 mol% Li2MoO4; 86.5 mol% MoO3) to which equal molar proportions ZrO2 and Li2SiO3 were added (3 mol% each). The crystals were initially grown undoped, but later Dy was added to the flux without any other charge-compensating species. With Dy and P added, in equal molar proportions, the zircon crystals incorporated 1.37 mol% (6.99 wt%) Dy and 1.36 mol% (1.33 wt%) P, a factor of 5.3 increase in Dy over the crystals grown without P intentionally added to the flux. The other P+REE-doped zircon crystals displayed an approximately 1000-fold increase in REE and P from La through Lu, a result of decreasing ionic radii. The incorporation of P5+ allowed, in a general sense, the xenotime-type coupled substitution of (REE3+, Y3+) + P5+ = Zr4+ + Si4+. From La to Nd, however, P exceeds REE, from Sm to Gd, the REE are generally equal to P, and from Tb to Lu the REE exceed P. The Y- and P-doped zircon behaved more like middle-REE (MREE)-doped zircon than heavy-REE (HREE)-doped zircon crystals in their ability to incorporate Y (and P) and to maintain charge neutrality. To investigate the incorporation of Dy with no P added to the flux, the P to LREE excess, and the HREE to P excess in the doped zircon, secondary ion mass spectrometry (SIMS) analyses were completed on selected crystals. In the Dydoped crystals, the SIMS analyses revealed minor amounts of P, Li, and Mo in the crystals. These elements contributed to charge balance required by the excess Dy. In REE- and P-doped zircon, the SIMS analyses detected Li and Mo, and the Li and Mo may also provide charge balance for excess REE in the HREE+P-doped crystals.

Rare-earth elements in synthetic zircon: Part 2. A single-crystal X-ray study of xenotime substitution

Abstract Zircon crystals synthesized in a Li-Mo oxide melt and doped with trivalent lanthanides and Y (REE), both with and without P, were examined by single-crystal X-ray diffraction (XRD). REE are incorporated into the Zr site in the zircon structure, and some Zr appears to be displaced to the Si site. Crystals doped with middle REE (MREE, Sm to Dy) and Y, plus P follow the xenotime substitution (REE3+ + P5+ = Zr4+ + Si4+) rather closely, whereas crystals doped with heavy REE (HREE, Er to Lu) deviate from the xenotime substitution, having REE:P atomic ratios significantly greater than one. Xenotime substitution requires that P5+ replace Si4+, but this substitution becomes limited by strain at the Si site in HREE-doped crystals. As Si sites become saturated with P5+, additional charge balance in synthetic zircon crystals may be provided by Mo6+ and Li+ from the flux entering interstitial sites, accounting for an additional 0.3 to 0.6 at% HREE beyond that balanced by P5+ ions. Heavy REE are more compatible in the zircon structure than are LREE and MREE, and HREE substitution is ultimately limited by the inability of the zircon structure to further accommodate charge-compensating elements. Thus the limit on REE concentrations in zircon is not a simple function of REE3+ ionic radii but depends in a complex way on structural strain at Zr and Si sites, which act together to limit REE and P incorporation. The mechanisms that limit the coupled xenotime substitution change from LREE to HREE. This change means that REE fractionation in zircon may vary according to the availability of charge-compensating elements. REE partition coefficients between zircon and melt must also depend in part on the availability of charge-compensating elements and their compatibility in the zircon structure.

Gibbsite growth kinetics on gibbsite, kaolinite, and muscovite substrates: atomic force microscopy evidence for epitaxy and an assessment of reactive surface area

Abstract New experimental data for gibbsite growth on powdered kaolinite and single crystal muscovite and published data for gibbsite growth on gibbsite powders at 80°C in pH3 solutions show that all growth rates obey the same linear function of saturation state provided that reactive surface area is evaluated for each mineral substrate. Growth rate (mol m−2 s−1) is expressed by Rateppt = (1.9 ± 0.2) × 10−10|ΔGr|/RT(0.90±0.01), which applies to the range of saturation states from ΔGr = 0 to 8.8 kJ mol−1, where ΔGr = RT[ln(Q/K)] for the reaction Al3+ + 3H2O = Al(OH)3 + 3H+, and equilibrium defined as ΔGr = 0 was previously determined. Identification of the growth phase as gibbsite was confirmed by rotating anode powder x-ray diffraction. Rates on kaolinite were determined using steady-state measured changes between inlet and outlet solutions in single-pass stirred-flow experiments. Rates on muscovite were determined by measuring the volume of precipitated crystals in images obtained by Tapping Mode™ atomic force microscopy (TMAFM). In deriving the single growth rate law, reactive surface area was evaluated for each substrate mineral. Total BET surface area was used for normalizing rates of gibbsite growth onto powdered gibbsite. Eight percent of the BET surface area, representing the approximate amount occupied by the aluminum octahedral sheet exposed at crystal edges, was used for powdered kaolinite. The x - y area of the TMAFM images of the basal surface was used for single crystal muscovite. Linearity of growth rates with saturation state suggests that the dominant nucleation and growth mechanisms are two dimensional. Such mechanisms are supported by observations of the morphologies of gibbsite crystals grown on muscovite at ΔGr = 8.8 kJ mol−1. The morphologies include (1) apparent epitaxial films as determined by hexagonal outlines of edges and thicknesses of 30 to 40 A, (2) elongate crystals 30 to 40 A thick aligned with the structure of the distorted Si-tetrahedral sheet of the 2M1 muscovite, and (3) micrometer-scale three-dimensional clumps of intergrown crystals. Reactive surface area as defined now for heterogeneous crystal growth in reactive-transport models must be modified to include substrates other than that of the growing mineral and to account for the role of structural and chemical controls on epitaxial nucleation and growth.

Quantification of minor phases in growth kinetics experiments with powder X-ray diffraction

Abstract Minor amounts of clay minerals precipitated from aqueous solution can be rapidly identified and quantified in a mineral mixture with powder X-ray diffraction using a rotating-anode source and a position-sensitive detector. For the case of gibbsite precipitated on a kaolinite powder substrate we demonstrate a simple method having a minimum detection limit of 0.1 wt%, using pure gibbsite as the intensity reference in mechanical mixtures of gibbsite and kaolinite. The amount of gibbsite precipitated onto kaolinite at 80 °C, pH 3 is higher when determined from solution chemistry than from the X-ray method, and the difference in amounts increases with increasing Al concentration in solution. This discrepancy can be explained by assuming that a fraction of the precipitated material is effectively invisible to the X-ray diffraction technique, either due to a small diffracting domain size along the gibbsite [001] direction or formation of an Al-phase that is amorphous to X-rays. This method should be generally useful for a range of mineral mixtures where at least one intense reflection for the phase of interest is not obscured. The ability to identify, characterize, and quantify trace phases by X-ray diffraction, especially when combined with surface analysis by electron or atomic force imaging, is an important complement to the conventional approach of monitoring solution composition in growth kinetics experiments.

UO2 CORROSION IN HIGH SURFACE-AREA-TO-VOLUME BATCH EXPERIMENTS

Unsaturated drip tests have been used to investigate the alteration of unirradiated UO{sub 2} and spent UO{sub 2} fuel in an unsaturated environment, such as may be expected in the proposed repository at Yucca Mountain. In these tests, simulated groundwater is periodically injected onto a sample at 90 C in a steel vessel. The solids react with the dripping groundwater and water condensed on surfaces to form a suite of U(VI) alteration phases. Solution chemistry is determined from leachate at the bottom of each vessel after the leachate stops interacting with the solids. A more detailed knowledge of the compositional evolution of the leachate is desirable. By providing just enough water to maintain a thin film of water on a small quantity of fuel in batch experiments, we can more closely monitor the compositional changes to the water as it reacts to form alteration phases.