Sorption kinetics of strontium in porous hydrous ferric oxide aggregates I. The Donnan diffusion model

Sorption of ions by hydrous ferric oxide (HFO) often shows a fast initial sorption reaction followed by a much slower sorption process. The second step is diffusion-controlled and can continue for days or months before equilibrium is reached. In this paper, we demonstrate that the diffusion rate may be explained by electrostatic interactions. The internal and external surfaces of HFO are generally positively charged and therefore repel cations. This can result in extremely low cation concentrations in pores, and therefore a significant reduction in pore diffusion rate. The theory is demonstrated here for sorption of Sr(2+) in HFO aggregates. The ion concentrations in the pore space are calculated using a Donnan model and diffusion is calculated from the Donnan concentration and potential gradients. This diffusion model is compared with nonelectrostatic pore diffusion, which does not take electrostatic interactions into account. The Donnan model predicts very low concentrations of Sr(2+) in the pores and diffusion rates that are up to 8000 times lower than predicted with a nonelectrostatic model.     

Small-scale forward smouldering experiments for remediation of coal tar in inert media

This paper presents a series of experiments conducted to assess the potential of smouldering combustion as a novel technology for remediation of contaminated land by water-immiscible organic compounds. The results from a detailed study of the conditions under which a smouldering reaction propagates in sand embedded with coal tar are presented. The objective of the study is to provide further understanding of the governing mechanisms of smouldering combustion of liquids in porous media. A small-scale apparatus consisting of a 100-mm in diameter quartz cylinder arranged in an upward configuration was used for the experiments. Thermocouple measurements and visible digital imaging served to track and characterize the ignition and propagation of the smouldering reaction. These two diagnostics are combined here to provide valuable information on the development of the reaction front. Post-treatment analyses of the sand were used to assess the amount of coal tar remaining in the soil. Experiments explored a range of inlet airflows and fuel concentrations. The smouldering ignition of coal tar was achieved for all the conditions presented here and self-sustained propagation was established after the igniter was turned off. It was found that the combustion is oxygen limited and peak temperatures in the range 800–1080 °C were observed. The peak temperature increased with the airflow at the lower range of flows but decreased with airflow at the higher range of flows. Higher airflows were found to produce faster propagation. Higher fuel concentrations were found to produce higher peak temperatures and slower propagation. The measured mass removal of coal tar was above 99% for sand obtained from the core and 98% for sand in the periphery of the apparatus.     

Bödeker’s effective theory: From Langevin dynamics to Dyson–Schwinger equations

The dynamics of weakly coupled, non-abelian gauge fields at high temperature is non-perturbative if the characteristic momentum scale is of order |k|g²T. Such a situation is typical for the processes of electroweak baryon number violation in the early Universe. Bödeker has derived an effective theory that describes the dynamics of the soft field modes by means of a Langevin equation. This effective theory has been used for lattice calculations so far [G.D. Moore, Nucl. Phys. B568 (2000) 367. Available from: <hep-ph/9810313>; G.D. Moore, Phys. Rev. D62 (2000) 085011. Available from: <hep-ph/0001216>]. In this work we provide a complementary, more analytic approach based on Dyson–Schwinger equations. Using methods known from stochastic quantitation, we recast Bödeker’s Langevin equation in the form of a field theoretic path integral. We introduce gauge ghosts in order to help control possible gauge artefacts that might appear after truncation, and which leads to a BRST symmetric formulation and to corresponding Ward identities. A second set of Ward identities, reflecting the origin of the theory in a stochastic differential equation, is also obtained. Finally, Dyson–Schwinger equations are derived.     

“Click-switch” – one-step conversion of organic azides into photochromic diarylethenes for the generation of light-controlled systems

Diarylethenes (DAEs) are an established class of photochromic molecules, but their effective incorporation into pre-existing targets is synthetically difficult. Here we describe a new class of DAEs in which one of the aryl rings is a 1,2,3-triazole that is formed by “click” chemistry between an azide on the target and a matching alkyne–cyclopentene–thiophene component. This late-stage zero-length linking allows for tight integration of the DAE with the target, thereby increasing the chances for photomodulation of target functions. Nineteen different DAEs were synthesized and their properties investigated. All showed photochromism. Electron-withdrawing groups, and in particular −M-substituents at the triazole and/or thiophene moiety resulted in DAEs with high photo- and thermostability. Further, the chemical nature of the cyclopentene bridge had a strong influence on the behaviour upon UV light irradiation. Incorporation of perfluorinated cyclopentene led to compounds with high photo- and thermostability, but the reversible photochromic reaction was restricted to halogenated solvents. Compounds containing the perhydrogenated cyclopentene bridge, on the other hand, allowed the reversible photochromic reaction in a wide range of solvents, but had on average lower photo- and thermostabilities. The combination of the perhydrocyclopentene bridge and electron-withdrawing groups resulted in a DAE with improved photostability and no solvent restriction. Quantum chemical calculations helped to identify the photoproducts formed in halogenated as well as non-halogenated solvents. For two optimized DAE photoswitches, photostationary state composition and reaction quantum yields were determined. These data revealed efficient photochemical ring closure and opening. We envision applications of these new photochromic diarylethenes in photonics, nanotechnology, photobiology, photopharmacology and materials science.

New photochromic diarylethenes are reported in which one aryl ring is a 1,2,3-triazole that is formed by “click” chemistry between an azide on the target and a matching alkyne–cyclopentene–thiophene component.     

The Footprint of the CO<Subscript>2</Subscript> Plume during Carbon Dioxide Storage in Saline Aquifers: Storage Efficiency for Capillary Trapping at the Basin Scale

We study a sharp-interface mathematical model of CO₂ migration in deep saline aquifers, which accounts for gravity override, capillary trapping, natural groundwater flow, and the shape of the plume during the injection period. The model leads to a nonlinear advection–diffusion equation, where the diffusive term is due to buoyancy forces, not physical diffusion. For the case of interest in geological CO₂ storage, in which the mobility ratio is very unfavorable, the mathematical model can be simplified to a hyperbolic equation. We present a complete analytical solution to the hyperbolic model. The main outcome is a closed-form expression that predicts the ultimate footprint on the CO₂ plume, and the time scale required for complete trapping. The capillary trapping coefficient and the mobility ratio between CO₂ and brine emerge as the key parameters in the assessment of CO₂ storage in saline aquifers. Despite the many approximations, the model captures the essence of the flow dynamics and therefore reflects proper dependencies on the mobility ratio and the capillary trapping coefficient, which are basin-specific. The expressions derived here have applicability to capacity estimates by capillary trapping at the basin scale.     

Calabi–Yau Black Holes and (0,4) Sigma Models

When an M-theory fivebrane wraps a holomorphic surface › in a Calabi-Yau 3-fold X the low energy dynamics is that of a black string in 5 dimensional — =1 supergravity. The infrared dynamics on the string worldsheet is an — = (0,4) 2D conformal field theory. Assuming the 2D CFT can be described as a nonlinear sigma model, we describe the target space geometry of this model in terms of the data of X and ›. Variations of weight two Hodge structures enter the construction of the model in an interesting way.     

Fermi surface in the new organic quasi-two-dimensional metal α-(BETS)2TlHg(SeCN)4

Quantum oscillations of de Haas-van Alphen and Shubnikov-de Haas and semiclassical angular oscillations of the magnetoresistance have been observed in the quasi-two-dimensional organic metal α-(BETS)₂TlHg(SeCN)₄. The quantum oscillations are connected with the cylindrical part of the Fermi surface. The angular oscillations are associated with the carrier motion on both the cylindrical part and quasi-planar sheets of the Fermi surface. The values of the Dingle temperature, T _D ≈ 2–3 K, and the effective mass, m* ≈ 1.03m ₀, have been defined. The possibility of the weakening of multibody interactions has been shown in this compound.