Diffusion of14C in dense saturated bentonite under steady-state conditions

Diffusion coefficients are critical parameters for predicting migration rates and fluxes of contaminants through clay-based barrier materials used in many waste containment strategies. Cabon-14 is present in high-level nuclear fuel waste and also in many low-level wastes such as those generated from some medical research activities. Diffusion coefficients were measured for¹⁴C (in the form of carbonate) in bentonite compacted to a series of dry bulk densities, _b, ranging from about 0.9 to 1.6 Mg/m³. The clay was saturated with a Na-Ca-Cl-dominated groundwater solution typical of those found deep in plutonic rock on the Canadian Shield. Both effective,D _e, and apparent,D _a, diffusion coefficients were determined.D _e is defined asD _{0 a} n _e, where D₀ is the diffusion coefficient in pure bulk water, _a the apparent tortuosity factor, andn _e the effective porosity available for diffusion; andD _a is defined asD _{0 a} n _e/(n _e + _b K _d ), where K_d is the solid/liquid distribution coefficient. BothD _e andD _a decrease with increasing _b:D _e values range from about 10×10^–12 m²/s at _b0.9 Mg/m³ to 0.6×10^–12 m²/s at 1.6 Mg/m³, andD _a values vary from approximately 40×10^–12 to 4×10^–12 m²/s over the same density range. The decrease inD _e andD _a is attributed to a decrease in both _a andn _e as _b increases. The data indicate thatn _e is <10% of the total solution-filled porosity of the clay at all densities.K _d values for¹⁴C with the clay range from about 0.3 to <0.1 m³/Mg; this indicates there is a small amount of¹⁴C sorbed on the clay and/or some¹⁴C is isotopically exchanged with¹²C in carbonate phases present in the clay. Finally, theD _e values for¹⁴C are lower than those of other diffusants — I^–, Cl^–, TcO₄ ^–, and Cs⁺ — that have been measured in this clay and pore-water solution. This is attributed to lower values for bothn _e andD ₀ for¹⁴C species relative to those of the other diffusants.     

Trapped-ion state detection through coherent motion

We demonstrate a general method for state detection of trapped ions that can be applied to a large class of atomic and molecular species. We couple a spectroscopy ion (27Al+) to a control ion (25Mg+) in the same trap and perform state detection through off-resonant laser excitation of the spectroscopy ion that induces coherent motion. The motional amplitude, dependent on the spectroscopy ion state, is measured either by time-resolved photon counting or by resolved sideband excitations on the control ion. The first method provides a simplified way to distinguish clock states in 27Al+, which avoids ground-state cooling and sideband transitions. The second method reduces spontaneous emission and optical pumping on the spectroscopy ion, which we demonstrate by nondestructively distinguishing Zeeman sublevels in the (1)S0 ground state of 27Al+.     

Rhodium-catalyzed selective olefination of arene esters via C-H bond activation

A new catalytic procedure of ortho-olefination of benzoates and benzaldehydes has been developed. Ester and carboxaldehyde units were revealed to be effective chelating groups in focusing the activation of aryl C-H bonds ortho to the directing moieties under the Rh-catalyzed oxidative conditions. The reaction is highly regioselective with a range of benzoates and benzaldehydes enabling the efficient olefination with acrylates, acrylic acid, and styrenes.     

Analysis of coefficient identification problems associated to the inverse Euler-Bernoulli beam theory

A rigorous investigation of the identification of a heterogeneousflexural rigidity coefficient in the Euler-Bernoulli steady-statebeam theory in the presence of a prescribed load is presented.Mathematically, this study is an extension to higher-order differentialequations of the coefficient identification problem analysedby Marcellini (1982) for the one-dimensional Poisson equation.In addition, various types of boundary conditions are discussed.Conditions for the well-posedness of these inverse problemsare established and, furthermore, numerical results obtainedusing a regularization algorithm are presented.     

A critical investigation of the effects of the radio frequency potential on the trapping of externally injected ions in ion trap mass spectrometry

The sensitivity of all ion trap mass spectrometry (ITMS) methods is dependent on the trapping efficiency of the instrument. For ITMS instruments utilizing external ion sources, such as laser desorption, trapping efficiency is known to depend on the phase and amplitude of the radio frequency (RF) potential applied to the ring electrode at the time of ion introduction. It is remarkable that, in a considerable body of literature, no consensus exists regarding the effects of these parameters on the efficacy of trapping externally generated ions. In this paper, a summary of the literature is presented in order to highlight significant discrepancies. New laser desorption ion trap mass spectrometry (LD-ITMS) data are also presented, from which conclusions are drawn in our effort to clarify some of the confusion. Copyright 1999 John Wiley & Sons, Ltd.     

Value for Money and Prison Perimeters—Goal-programming for Gaols

A computer model has been developed to address the problem of attaining the most cost-effective balance when providing perimeter security at any given prison. The generalized analysis of security of perimeters (GASP) model evaluates the cost and performance of different prison perimeters in terms of several measures. The modelling process takes account not only of the site-specific problems such as perimeter shape, but also of the policy input of trade-offs between the various output measures of cost and effectiveness. Goal-programming and multi-criteria decision-making techniques have been used.     

Carbon dioxide versus xenon as a mobile phase for flow cell packed column SFC/FT-IR

Xenon is compared to carbon dioxide as a mobile phase for super critical fluid chromatography/Fourier transform infrared spectrometry. The study showed xenon to be comparable to carbon dioxide in terms of resulting chromatography for non-polar analytes. Xenon was confirmed to be a very poor mobile phase, however, for polar analytes. It was determined that small wavenumber shifts in the infrared spectra of probe analytes occurred as either the density or temperature of the mobile phase was increased. The degree of these shifts was often similar for xenon and carbon dioxide. Analyte spectra for five different compounds were produced in both super critical xenon and carbon dioxide and compared to condensed phase and vapor phase library spectra. In all cases, carbon dioxide spectra were readily matched to their corresponding vapor phase spectra, despite having blanked portions of the spectrum due to carbon dioxide infrared absorption. Xenon produced technically superior spectra without such blanked regions, but at a much higher economical cost than carbon dioxide and with no real improvement in terms of library matching.     

Direct determination of bismuth and antimony in sea water by anodic stripping voltammetry

A method based on anodic stripping voltammetry at the mercury-coated graphite electrode has been developed for the direct determination of bismuth and antimony at their natural levels in sea water. Bismuth plated at -0.4 V from sea water made 1 M in hydrochloric acid gives a stripping peak proportional to concentration at -0.2 V without interference from antimony or other metals normally present. Antimony may be plated from sea water made 4 M in hydrochloric acid and gives a stripping peak at -0.2 V proportional to the sum of bismuth and antimony. By use of the standard addition technique, satisfactory results were obtained for sea water samples with concentration ranges of 0.02–0.09 μg kg^?1 for bismuth and 0.2–0.5 μg kg^?1 for antimony.