Quantitative localized proton-promoted dissolution kinetics of calcite using scanning electrochemical microscopy (SECM)

Scanning electrochemical microscopy (SECM) has been used to determine quantitatively the kinetics of proton-promoted dissolution of the calcite (101̅4) cleavage surface (from natural “Iceland Spar”) at the microscopic scale. By working under conditions where the probe size is much less than the characteristic dislocation spacing (as revealed from etching), it has been possible to measure kinetics mainly in regions of the surface which are free from dislocations, for the first time. To clearly reveal the locations of measurements, studies focused on cleaved “mirror” surfaces, where one of the two faces produced by cleavage was etched freely to reveal defects intersecting the surface, while the other (mirror) face was etched locally (and quantitatively) using SECM to generate high proton fluxes with a 25 μm diameter Pt disk ultramicroelectrode (UME) positioned at a defined (known) distance from a crystal surface. The etch pits formed at various etch times were measured using white light interferometry to ascertain pit dimensions. To determine quantitative dissolution kinetics, a moving boundary finite element model was formulated in which experimental time-dependent pit expansion data formed the input for simulations, from which solution and interfacial concentrations of key chemical species, and interfacial fluxes, could then be determined and visualized. This novel analysis allowed the rate constant for proton attack on calcite, and the order of the reaction with respect to the interfacial proton concentration, to be determined unambiguously. The process was found to be first order in terms of interfacial proton concentration with a rate constant k = 6.3 (± 1.3) × 10–4 m s–1. Significantly, this value is similar to previous macroscopic rate measurements of calcite dissolution which averaged over large areas and many dislocation sites, and where such sites provided a continuous source of steps for dissolution. Since the local measurements reported herein are mainly made in regions without dislocations, this study demonstrates that dislocations and steps that arise from such sites are not needed for fast proton-promoted calcite dissolution. Other sites, such as point defects, which are naturally abundant in calcite, are likely to be key reaction sites

Literacy practices of primary education children in Andalusia (Spain): a family-based perspective

Primary school children develop literacy practices in various domains and situations in everyday life. This study focused on the analysis of literacy practices of children aged 8–12 years from the perspec- tive of their families. 1,843 families participated in the non-experimental explanatory study. The children in these families speak Spanish as a first language and are schooled in this language. The instrument used was a self-report questionnaire about children’s home-literacy practices. The data obtained were analysed using categorical principal components analysis (CATPCA) and analysis of variance (ANOVA). The results show the complex relationship between literacy practices developed by children in the domains of home and school and the limited development of a literacy-promoting ‘third space’. In conclusion, the families in our study had limited awareness of their role as literacy- promoting agents and thought of literacy learning as restricted to formal or academic spaces

Characterizing the Hofstadter butterfly's outline with Chern numbers

In this work, we report original properties inherent to independent particles subjected to a magnetic field by emphasizing the existence of regular structures in the energy spectrum's outline. We show that this fractal curve, the well-known Hofstadter butterfly's outline, is associated to a specific sequence of Chern numbers that correspond to the quantized transverse conductivity. Indeed the topological invariant that characterizes the fundamental energy band depicts successive stairways as the magnetic flux varies. Moreover each stairway is shown to be labeled by another Chern number which measures the charge transported under displacement of the periodic potential. We put forward the universal character of these properties by comparing the results obtained for the square and the honeycomb geometries.Comment: Accepted for publication in J. Phys. B (Jan 2009

Phase-Control of Photoabsorption in Optically Dense Media

We present a self-consistent theory, as well as an illustrative application to a realistic system, of phase control of photoabsorption in an optically dense medium. We demonstrate that, when propagation effects are taken into consideration, the impact on phase control is significant. Independently of the value of the initial phase difference between the two fields, over a short scaled distance of propagation, the medium tends to settle the relative phase so that it cancels the atomic excitation. In addition, we find some rather unusual behavior for an optically thin layer.Comment: 5 pages, 3 figures, submitted to PR

The Implications of the Microwave Background Anisotropies for Laser-Interferometer-Tested Gravitational Waves

The observed microwave background anisotropies in combination with the theory of quantum mechanically generated cosmological perturbations predict a well measurable amount of relic gravitational waves in the frequency intervals tested by LISA and ground-based laser interferometers.Comment: revised, corrected, and slightly expanded version to be published in Classical and Quantum Gravity; 22 pages, 1 Postscript figure, Latex; Based on a talk presented at the First Internationsl LISA Symposium, 9 - 12 July 1996, RAL, U

Group cognitive analytic music therapy: a quasi-experimental feasibility study conducted in a high secure hospital

This study conducted a feasibility patient preference quasi-experimental study of group cognitive analytic music therapy (G-CAMT) for mentally disordered offenders. Participants either chose or were randomised to 16 sessions of manualised G-CAMT (N = 10) plus treatment as usual (TAU) or TAU alone (N = 10). Self-rated and staff-rated outcomes were assessed at baseline, post-intervention and 8-weeks post-intervention. Residency was assessed at 2-year follow-up. Results indicate that G-CAMT was easily implemented; 9/10 participants completed G-CAMT and attendees had high satisfaction with the approach. Session attendance was high; 4/10 participants attended all sessions. At the 8-week follow-up, 3/9 G-CAMT participants had reliable reductions (i.e. statistically reliable pre to 8-week follow-up change results) in intrusive/possessive behaviours and fear of separation/abandonment. On the staff-rated outcome measure G-CAMT participants as a group were statistically significantly friendlier compared to TAU at 8-week follow-up (U = 0.50, p = 0.009, d = 1.92, CI 0.44 to 3.11). There were no differences between the arms in terms of residency outcomes at 2-year follow-up. The study is discussed in terms of G-CAMT’s theoretical grounding and high acceptability. The study is limited by its small sample size, but indicates the possibility of progressing onto a full trial

On Second-Order Monadic Monoidal and Groupoidal Quantifiers

We study logics defined in terms of second-order monadic monoidal and groupoidal quantifiers. These are generalized quantifiers defined by monoid and groupoid word-problems, equivalently, by regular and context-free languages. We give a computational classification of the expressive power of these logics over strings with varying built-in predicates. In particular, we show that ATIME(n) can be logically characterized in terms of second-order monadic monoidal quantifiers

Negative ion formation in potassium–nitromethane collisions

Ion-pair formation in gaseous nitromethane (CH3NO2) induced by electron transfer has been studied by investigating the products of collisions between fast potassium atoms and nitromethane molecules using a crossed molecular-beam technique. The negative ions formed in such collisions were analysed using time-of-flight mass spectroscopy. The six most dominant product anions are NO2?, O?, CH3NO2?, OH?, CH2NO2? and CNO?. By using nitromethane-d3 (CD3NO2), we found that previous mass 17 amu assignment to O? delayed fragment, is in the present experiment may be unambiguously assigned to OH?. The formation of CH2NO2? may be explained in terms of dissociative electron attachment to highly vibrationally excited molecules

Logics of Finite Hankel Rank

We discuss the Feferman-Vaught Theorem in the setting of abstract model theory for finite structures. We look at sum-like and product-like binary operations on finite structures and their Hankel matrices. We show the connection between Hankel matrices and the Feferman-Vaught Theorem. The largest logic known to satisfy a Feferman-Vaught Theorem for product-like operations is CFOL, first order logic with modular counting quantifiers. For sum-like operations it is CMSOL, the corresponding monadic second order logic. We discuss whether there are maximal logics satisfying Feferman-Vaught Theorems for finite structures.Comment: Appeared in YuriFest 2015, held in honor of Yuri Gurevich's 75th birthday. The final publication is available at Springer via http://dx.doi.org/10.1007/978-3-319-23534-9_1