Yucca Mountain, Nevada is the proposed site of a geologic repository for the disposal of spent nuclear fuel and high-level radioactive waste in the United States. In the event repository engineered barriers fail, the saturated alluvium located south of Yucca Mountain is expected to serve as a natural barrier to the migration of radionuclides to the accessible environment. The purpose of this study is to improve the characterization of uranium retardation in the saturated zone at Yucca Mountain to support refinement of an assessment model. The distribution of uranium desorption rates from alluvium obtained from Nye County bore holes EWDP-19IM1, EWDP-10SA, EWDP-22SA were studied to address inconsistencies between results from batch sorption and column transport experiments. The alluvium and groundwater were characterized to better understand the underlying mechanisms of the observed behavior. Desorption rate constants were obtained using an activity based mass balance equation and column desorption experiments were analyzed using a mathematical model utilizing multiple sorption sites with different first-order forward and reverse reaction rates. The uranium desorption rate constants decreased over time, suggesting that the alluvium has multiple types of active sorption sites with different affinities for uranium. While a significant fraction of the initially sorbed uranium desorbed …

Atmospheric iron (Fe) is thought to play an important role in cloudwater chemistry (e.g., S(IV) oxidation, oxidant production, etc.), and is also an important source of Fe to certain regions of the worlds oceans where Fe is believed to be a rate-limiting nutrient for primary productivity. This thesis focuses on understanding the chemistry, speciation and abundance of Fe in cloudwater and aerosol in the troposphere, through observations of Fe speciation in the cloudwater and aerosol samples collected over the continental United States and the Arabian Sea. Different chemical species of atmospheric Fe were measured in aerosol and cloudwater samples to help assess the role of Fe in cloudwater chemistry.

This study was undertaken to determine if strontium chloride could be used to create a trans-generational otolith mark in steelhead (Oncorhynchus mykiss). I completed two strontium injection trials and a survey of juvenile steelhead from various steelhead hatcheries. The two trials measured Sr:Ca ratios in otoliths in response to injections and the survey measured the natural variation in Sr:Ca ratios in otoliths of juvenile hatchery steelhead in response to the natural variation. In 2003, adult female Wallowa River, Oregon O. mykiss, were captured at the hatchery and evenly divided between a control group and two treatment groups. These females received an intraperitoneal injection of 1cc/500 g of body weight of a physiologically isotonic solution (0.9% saline) containing concentrations of 0 (control), 1000, or 5000 parts per million (ppm) of strontium chloride hexahydrate (SrCl{sub 2}* 6H{sub 2}O). Females were housed in a single outdoor tank until spawned artificially, and a distinct external tag identified each female within each treatment group. In 2004, female steelhead were captured throughout the duration of the adult returns to the Umatilla River basin and injected with 0, 1000, 5000, or 20,000-ppm strontium. In both trials, progeny of fish treated with strontium had significantly higher Sr:Ca ratios …

Mortandad Canyon is a discharge site for treated industrial effluents containing radionuclides and other chemicals at Los Alamos National Laboratory, New Mexico. This study was conducted to develop an understanding of the unsaturated hydrologic behavior below the canyon floor. The main goal of this study was to evaluate the hypothetical performance of the vadose zone above the water table. Numerical simulations of unsaturated groundwater flow at the site were conducted using the Finite Element Heat and Mass Transfer (FEHM) code. A two-dimensional cross-section along the canyon's axis was used to model flow between an alluvial groundwater system and the regional aquifer approximately 300 m below. Using recharge estimated from a water budget developed in 1967, the simulations showed waters from the perched water table reaching the regional aquifer in 13.8 years, much faster than previously thought. Additionally, simulations indicate that saturation is occurring in the Guaje pumice bed an d that the Tshirege Unit 1B is near saturation. Lithologic boundaries between the eight materials play an important role in flow and solute transport within the system. Horizontal flow is shown to occur in three thin zones above capillary barriers; however, vertical flow dominates the system. Other simulations were conducted to …

The ammonia synthesis reaction has been studied using single crystal model catalysis combined with sum frequency generation (SFG) vibrational spectroscopy. The adsorption of gases N{sub 2}, H{sub 2}, O{sub 2} and NH{sub 3} that play a role in ammonia synthesis have been studied on the Fe(111) crystal surface by sum frequency generation vibrational spectroscopy using an integrated Ultra-High Vacuum (UHV)/high-pressure system. SFG spectra are presented for the dissociation intermediates, NH{sub 2} ({approx}3325 cm{sup -1}) and NH ({approx}3235 cm{sup -1}) under high pressure of ammonia or equilibrium concentrations of reactants and products on Fe(111) surfaces. Special attention was paid to understand how potassium promotion of the iron catalyst affects the intermediates of ammonia synthesis. An Fe(111) surface promoted with 0.2 monolayers of potassium red shifts the vibrational frequencies of the reactive surface intermediates, NH and NH{sub 2}, providing evidence for weakened the nitrogen-hydrogen bonds relative to clean Fe(111). Spectral features of these surface intermediates persisted to higher temperatures for promoted iron surfaces than for clean Fe(111) surfaces implying that nitrogen-iron bonds are stronger for the promoted surface. The ratio of the NH to NH{sub 2} signal changed for promoted surfaces in the presence of equilibrium concentrations of reactants and products. The …

The absolute branching fractions for the decays D{sub s}{sup -} {yields} {ell}{sup -}{bar {nu}}{sub {ell}} ({ell} = e, {mu}, or {tau}) are measured using a data sample corresponding to an integrated luminosity of 521 fb{sup -1} collected at center of mass energies near 10.58 GeV with the BABAR detector at the PEPII e{sup +}e{sup -} collider at SLAC. The number of D{sub s}{sup -} mesons is determined by reconstructing the recoiling system DKX{gamma} in events of the type e{sup +}e{sup -} {yields} DKXD*{sub s}{sup -}, where D*{sub s}{sup -} {yields} D{sub s}{sup -} {gamma} and X represents additional pions from fragmentation. The D{sub s}{sup -} {yields} {ell}{sup -}{nu}{sub {ell}} events are detected by full or partial reconstruction of the recoiling system DKX{gamma}{ell}. The following results are obtained: {Beta}(D{sub s}{sup -} {yields} {mu}{sup -}{nu}) = (6.02 {+-} 0.38 {+-} 0.34) x 10{sup -3}, {Beta}(D{sub s}{sup -} {yields} {tau}{sup -}{nu}) = (5.00 {+-} 0.35 {+-} 0.49) x 10{sup -2}, and B(D{sub s}{sup -} {yields} e{sup -}{nu}) < 2.8 x 10{sup -4} at 90% C.L., where the first uncertainty is statistical and the second is systematic. The branching fraction measurements are combined to determine the D{sub s}{sup -} decay constant f{sub D{sub s}} …