691 research outputs found

    Uranium (VI) Adsorbate Structures on Portlandite [Ca(OH)2] Type Surfaces Determined by Computational Modelling and X-ray Absorption Spectroscopy

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    Portlandite [Ca(OH)2] is a potentially dominant solid phase in the high pH fluids expected within the cementitious engineered barriers of Geological Disposal Facilities (GDF). This study combined X-ray Absorption Spectroscopy with computational modelling in order to provide atomic-scale data which improves our understanding of how a critically important radionuclide (U) will be adsorbed onto this phase under conditions relevant to a GDF environment. Such data are fundamental for predicting radionuclide mass transfer. Surface coordination chemistry and speciation of uranium with portlandite [Ca(OH)2] under alkaline groundwater conditions (ca. pH 12) were determined by both in situ and ex situ grazing incidence extended X-ray absorption fine structure analysis (EXAFS) and by computational modelling at the atomic level. Free energies of sorption of aqueous uranyl hydroxides, [UO2(OH)n]2–n (n = 0–5) with the (001), (100) and (203) or (101) surfaces of portlandite are predicted from the potential of mean force using classical molecular umbrella sampling simulation methods and the structural interactions are further explored using fully periodic density functional theory computations. Although uranyl is predicted to only weakly adsorb to the (001) and (100) clean surfaces, there should be significantly stronger interactions with the (203/101) surface or at hydroxyl vacancies, both prevalent under groundwater conditions. The uranyl surface complex is typically found to include four equatorially coordinated hydroxyl ligands, forming an inner-sphere sorbate by direct interaction of a uranyl oxygen with surface calcium ions in both the (001) and (203/101) cases. In contrast, on the (100) surface, uranyl is sorbed with its axis more parallel to the surface plane. The EXAFS data are largely consistent with a surface structural layer or film similar to calcium uranate, but also show distinct uranyl characteristics, with the uranyl ion exhibiting the classic dioxygenyl oxygens at 1.8 Å and between four and five equatorial oxygen atoms at distances between 2.28 and 2.35 Å from the central U absorber. These experimental data are wholly consistent with the adsorbate configuration predicted by the computational models. These findings suggest that, under the strongly alkaline conditions of a cementitious backfill engineered barrier, there would be significant uptake of uranyl by portlandite to inhibit the mobility of U(VI) from the near field of a geological disposal facility

    Evolutionary games in the multiverse

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    Evolutionary game dynamics of two players with two strategies has been studied in great detail. These games have been used to model many biologically relevant scenarios, ranging from social dilemmas in mammals to microbial diversity. Some of these games may in fact take place between a number of individuals and not just between two. Here, we address one-shot games with multiple players. As long as we have only two strategies, many results from two player games can be generalized to multiple players. For games with multiple players and more than two strategies, we show that statements derived for pairwise interactions do no longer hold. For two player games with any number of strategies there can be at most one isolated internal equilibrium. For any number of players d\boldsymbol{d} with any number of strategies n, there can be at most (d-1)^(n-1) isolated internal equilibria. Multiplayer games show a great dynamical complexity that cannot be captured based on pairwise interactions. Our results hold for any game and can easily be applied for specific cases, e.g. public goods games or multiplayer stag hunts

    In and Out of Equilibrium II: Evolution in Repeated Games with Discounting and Complexity Costs

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    We explore evolutionary dynamics for repeated games with small, but positive complexity costs. To understand the dynamics, we extend a folk theorem result by Cooper (1996) to continuation probabilities, or discount rates, smaller than 1. While this result delineates which payoffs can be supported by neutrally stable strategies, the only strategy that is evolutionarily stable, and has a uniform invasion barrier, is All D. However, with sufficiently small complexity costs, indirect invasions - but now through 'almost neutral' mutants - become an important ingredient of the dynamics. These indirect invasions include stepping stone paths out of full defection

    Mean echogenicity and area of puborectalis muscle in women with stress urinary incontinence during pregnancy and after delivery

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    INTRODUCTION AND HYPOTHESIS: Pregnancy and childbirth are risk factors for the development of stress urinary incontinence (SUI). Urinary continence depends on normal urethral support, which is provided by normal levator ani muscle function. Our objective was to compare mean echogenicity and the area of the puborectalis muscle between women with and those without SUI during and after their first pregnancy. METHODS: We examined 280 nulliparous women at a gestational age of 12 weeks, 36 weeks, and 6 months after delivery. They filled out the validated Urogenital Distress Inventory and underwent perineal ultrasounds. SUI was considered present if the woman answered positively to the question "do you experience urine leakage related to physical activity, coughing, or sneezing?" Mean echogenicity of the puborectalis muscle (MEP) and puborectalis muscle area (PMA) were calculated. The MEP and PMA during pregnancy and after delivery in women with and without SUI were compared using independent Student's t test. RESULTS: After delivery the MEP was higher in women with SUI if the pelvic floor was at rest or in contraction, with effect sizes of 0.30 and 0.31 respectively. No difference was found in the area of the puborectalis muscle between women with and those without SUI. CONCLUSIONS: Women with SUI after delivery had a statistically significant higher mean echogenicity of the puborectalis muscle compared with non-SUI women when the pelvic floor was at rest and in contraction; the effect sizes were small. This higher MEP is indicative of a relatively higher intramuscular extracellular matrix component and could represent diminished contractile function

    In Situ EXAFS Study of Sr Adsorption on TiO2(110) under High Ionic Strength Wastewater Conditions

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    In order to provide important details concerning the adsorption reactions of Sr, batch reactions and a set of both ex situ and in situ Grazing Incidence X-ray Absorption Fine Structure (GIXAFS) adsorption experiments were completed on powdered TiO2 and on rutile(110), both reacted with either SrCl2 or SrCO3 solutions. TiO2 sorption capacity for strontium (Sr) ranges from 550 ppm (SrCl2 solutions, second order kinetics) to 1400 ppm (SrCO3 solutions, first order kinetics), respectively, and is rapid. Sr adsorption decreased as a function of chloride concentration but significantly increased as carbonate concentrations increased. In the presence of carbonate, the ability of TiO2 to remove Sr from the solution increases by a factor of ~4 due to rapid epitaxial surface precipitation of an SrCO3 thin film, which registers itself on the rutile(110) surface as a strontianite-like phase (d-spacing 2.8 Å). Extended X-ray Absorption Fine Structure (EXAFS) results suggest the initial attachment is via tetradental inner-sphere Sr adsorption. Moreover, adsorbates from concentrated SrCl2 solutions contain carbonate and hydroxyl species, which results in both inner- and outer-sphere adsorbates and explains the reduced Sr adsorption in these systems. These results not only provide new insights into Sr kinetics and adsorption on TiO2 but also provide valuable information concerning potential improvements in effluent water treatment models and are pertinent in developing treatment methods for rutile-coated structural materials within nuclear power plants

    Mineral reaction kinetics constrain the length scale of rock matrix diffusion

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    Mass transport by aqueous fluids is a dynamic process in shallow crustal systems, redistributing nutrients as well as contaminants. Rock matrix diffusion into fractures (void space) within crystalline rock has been postulated to play an important role in the transient storage of solutes. The reacted volume of host rock involved, however, will be controlled by fluid-rock reactions. Here we present the results of a study which focusses on defining the length scale over which rock matrix diffusion operates within crystalline rock over timescales that are relevant to safety assessment of radioactive and other long-lived wastes. Through detailed chemical and structural analysis of natural specimens sampled at depth from an active system (Toki Granite, Japan), we show that, contrary to commonly proposed models, the length scale of rock matrix diffusion may be extremely small, on the order of centimetres, even over timescales of millions of years. This implies that in many cases the importance of rock matrix diffusion will be minimal. Additional analyses of a contrasting crystalline rock system (Carnmenellis Granite, UK) corroborate these results
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