Simulation of immiscible multiphase flow in porous media: A focus on the capillary fringe of oil-contaminated aquifers

This paper deals with the analysis of some aspects of the vertical and lateral migration of oil spills in the unsaturated and the capillary zone of a phreatic aquifer. Our motivation stems from the fact that such contamination represents a severe danger for ground-water resources all over the world and from the present acute problem of jet-fuel contamination in some location of Israel. In the present study, we shall focus our efforts on the analysis of the upper layers of the aquifer which are often subjected to the most significant oil contamination. Neglecting coupled processes effects such as dilution, adsorption and volatilization, also adopting Richard's assumption, a three-phase flow model is introduced with capillary heads of the water and the oil as variables. The resulting model which is coupled and strongly non-linear is solved using a vertical two-dimensional Finite-Element procedure together with a quasi-Newton optimization algorithm. Applying that scheme, various scenarios of oil migration in the unsaturated and the capillary zone were simulated. Some migration characteristics prediced by the numerical simulations are discussed. In particular, the dynamics of the water and oil phases during the migration process is discussed.     

The influence of free convection on soil salinization in arid regions

Evaporation of groundwater in a region with a shallow water table and small natural replenishment causes accumulation of salts near the ground surface. Water in the upper soil layer becomes denser than in the depth. This is a potentially unstable situation which may result in convective currents. When free convection takes place, estimates of the salinity profile, salt precipitation rate, etc., obtained within the framework of a 1-D (vertical) model fail.Very simplified model of the process is proposed, in which the unsaturated zone is represented by a horizontal soil layer at a constant water saturation, and temperature changes are neglected. The purpose of the model is to obtain a rough estimate of the role of natural convection in the salinization process.A linear stability analysis of a uniform vertical flow is given, and the stability limit is determined numerically as a function of evaporation rate, salt concentration in groundwater, and porous medium dispersivity. The loss of stability corresponds to quite realistic Rayleigh numbers. The stability limit depends in nonmonotonic way on the evaporation rate.The developed convective regime was simulated numerically for a 2-D vertical domain, using finite volume element discretization and FAS multigrid solver. The dependence of the average salt concentration in the upper layer on the Rayleigh number was obtained.List of Main Symbols horizontal wavenumber - _L , _T dispersivities (longitudinal and transversal) - D ^* diffusion coefficient (in a porous medium) - g acceleration of gravity - H thickness of the vadoze zone - k permeability - p pressure - Pe Péclet number - q mass flux - Ra Rayleigh number Greek _L , _T dimensionless dispersivities - coefficient of concentration expansion - coefficient of viscosity variation - volumetric fraction of the liquid phase - viscosity - density - stream function - mass fraction of salt in water Vectors and tensors D dispersion coefficient - e unit vector - I unit tensor - J nonadvective salt flux - V liquid phase velocity - x radius-vector     

Desch‐Schappacher perturbation of one‐parameter semigroups on locally convex spaces

We prove a Desch‐Schappacher type perturbation theorem for strongly continuous and locally equicontinuous one‐parameter semigroups which are defined on a sequentially complete locally convex space.     

Functionalization of Quinazolin‐4‐ones Part 1: Synthesis of Novel 7‐Substituted‐2‐thioxo Quinazolin‐4‐ones from 4‐Substituted‐2‐Aminobenzoic Acids and PPh3(SCN)2

4‐(Nitro, amino, acetylamino)‐2‐aminobenzoic acid were allowed to react with PPh₃(SCN)₂ and gave the crossholding 7‐nitro, 7‐acetylamino‐ and 7‐amino‐2‐thioxo quinazolin‐4‐ones respectively. The nature of the substituent at position 4 of the 2‐aminobenzoic acids has significant influence on the outcome of the cyclisation reaction with PPh₃(SCN)₂. Similarly, the nature of the substituent at position 7 of the 2‐substituted quinazolin‐4‐ones significantly affected the ease with which alkylation reactions could be performed. The alkylation selectivity of the 7‐ substiuted‐2‐thioxo quinazolin‐4‐ones was found to depend on the nature of the alkyl halide and the nature of the substituent at position 2.     

The Number of Accumulated Photons and the Quality of Stimulated Emission Depletion Lifetime Images

Time binning is used to increase the number of photon counts in the peak channel of stimulated emission depletion fluorescence lifetime decay curves to determine how it affects the resulting lifetime image. The fluorescence lifetime of the fluorophore, Alexa Fluor 594 phalloidin, bound to F‐actin is probed in cultured S2 cells at a spatial resolution of ~40 nm. This corresponds to a 10‐fold smaller probe volume compared to confocal imaging, and a reduced number of photons contributing to the signal. Pixel‐by‐pixel fluorescence lifetime measurements and error analysis show that an average of 40 ± 30 photon counts in the peak channel with a signal‐to‐noise ratio of 20 is enough to calculate a reliable fluorescence lifetime from a single exponential fluorescence decay. No heterogeneity in the actin cytoskeleton in different regions of the cultured cells was measured in the 40–400 nm spatial regime.     

Computational protocols for prediction of solute NMR relative chemical shifts. a case study of L-tryptophan in aqueous solution

In this study, we have applied two different spanning protocols for obtaining the molecular conformations of L-tryptophan in aqueous solution, namely a molecular dynamics simulation and a molecular mechanics conformational search with subsequent geometry re-optimization of the stable conformers using a quantum mechanically based method. These spanning protocols represent standard ways of obtaining a set of conformations on which NMR calculations may be performed. The results stemming from the solute-solvent configurations extracted from the MD simulation at 300 K are found to be inferior to the results stemming from the conformations extracted from the MM conformational search in terms of replicating an experimental reference as well as in achieving the correct sequence of the NMR relative chemical shifts of L-tryptophan in aqueous solution. We find this to be due to missing conformations visited during the molecular dynamics run as well as inaccuracies in geometrical parameters generated from the classical molecular dynamics simulations.     

Spontaneous waveguide Raman spectroscopy of self-assembled monolayers in silica micropores

Advances in nanoscience are critically dependent on the ability to control and probe chemical and physical phenomena in confined geometries. A key challenge is to identify confinement structures with high surface area to volume ratios and controlled surface boundaries that can be probed quantitatively at the molecular level. Herein we report an approach for probing molecular structures within nano- to microscale pores by the application of spontaneous Raman spectroscopy. We demonstrate the method by characterization of the structural features of picomole quantities of well-organized octadecyltrichlorosilane (OTS) monolayers self-assembled on the interior pore surfaces of high aspect ratio (1 μm diameter × 1-10 cm length), near-atomically smooth silica microstructured optical fibers (MOFs). The simple Raman backscattering collection geometry employed is well suited for a wide variety of diagnostic applications as demonstrated by tracking the combustion of the hydrocarbon chains of the OTS self-assembled monolayer (SAM) and spectral confirmation of the formation of an adsorbed monolayer of human serum albumin (HSA) protein. Using this MOF Raman approach, molecular processes in precisely defined, highly confined geometries can be probed at high pressures and temperatures, with a wide range of excitation wavelengths from the visible to the near-IR, and under other external perturbations such as electric and magnetic fields.     

Temperature- and pH-responsive self-assembly of poly(propylene oxide)-b-poly(lysine) block copolymers in aqueous solution

A series of poly(propylene oxide)-b-poly(L-lysine) (PPO-PK) block copolymers were synthesized using Huisgen's 1,3-dipolar cycloaddition, and the solution self-assembly was studied using transmission electron microscopy, circular dichroism spectroscopy, and dynamic and static light scattering techniques. In contrast to previous studies of poly(lysine)-based block copolymers, PPO-PK exhibits a significant shift in the pH associated with the helix-coil transition of the poly(lysine) block, potentially a result of decreased hydrophobicity in the core PPO block. Given the proximity of the lower critical solution temperature of the PPO block, these materials exhibit both pH and temperature-responsive (i.e., "schizophrenic") self-assembly, the latter of which was interpreted in terms of changes in the second osmotic virial coefficient. Finally, the vesicle morphology obtained from these polymers was studied for the propensity in drug encapsulation and passive release.