Electrical Double-Layer and Ion Bridging Forces between Symmetric and Asymmetric Charged Surfaces in the Presence of Mono- and Divalent Ions.

An atomic force microscope, employing the colloidal probe technique, was used to study the interactions between six different combinations of silane-functionalized silica surfaces in NaCl and CaCl2 solutions. The surfaces consisted of monolayers of the apolar trimethoxy(octyl)silane, the positively charged (3-aminopropyl)trimethoxysilane, and the negatively charged (3-mercaptopropyl)trimethoxysilane. The interactions between the three symmetric systems, as well as between the three asymmetric combinations of surfaces, were measured and compared to calculated electrical double-layer forces. The results demonstrated that the long-range interactions between the surfaces in all cases were dominated by double-layer forces, while short-range interactions, including adhesion, were dominated by ion bridging forces in the cases where both interaction surfaces favored adsorption of calcium ions. The study thus also demonstrates how surface force studies in mono- and divalent salt solutions can be used as an analytical tool for probing specific functional groups on heterogeneous surfaces.

Diffusion measurements in binary liquid mixtures by Raman spectroscopy.

It is shown that Raman spectroscopy allows determination of the molar fractions in mixtures subjected to molecular diffusion. Spectra of three binary systems, benzene/n-hexane, benzene/cyclohexane, and benzene/acetone, were obtained during vertical (exchange) diffusion at several different heights (z) as a function of time. A procedure to determine time-dependent concentration profiles and diffusion coefficients is described in detail for one system, and results are given for the two other cases. For the system benzene/cyclohexane, much lower diffusion coefficients than reported in the literature were found, even in a thermostatically controlled diffusion cell, recording spectra through circulating water. For the system benzene/acetone, the determined diffusion coefficients were in good agreement with the literature data. The limitations of the Raman method are discussed, and it is concluded that many more systems ought to be studied. It is pointed out that diffusion profiles can be obtained in ternary and higher systems, where proper measurements are almost nonexistent.

Composition of in situ burn residue as a function of weathering conditions.

Troll B crude oil was weathered under Arctic conditions with different ice coverage: open water, 50% ice and 90% ice. Samples (100 mL) were taken during the experiment and tested for ignitability in a burning cell. From each burning a residue sample was taken for analysis. The burning process removed the light compounds eluting before C13. No effect from the prior weathering time or the different ice coverage was seen in the burn residue composition. The content of selected Poly Aromatic Hydrocarbons (PAHs) was determined and it was noted that the concentration of PAHs with more than 4 rings were increased. The source origin of the PAHs was investigated by use of relative ratios of PAH isomers and indicated that some formation of PAHs was additionally taking place during burning.

Hydrodynamic impact of particle shape in slurry packed liquid chromatography columns.

We report on a series of flow velocity and efficiency profiles, which were measured across the cross section of preparative chromatographic columns packed with different stationary phase materials using computed tomography. It is shown that this non-invasive technique is very useful for visualization of the inner part of a packed column and measurement of the spatial resolved column packing properties. For evaluation of the influence of the particle shape on the velocity distribution and column performance, irregular and spherical reversed phases were studied in detail. The results showed a decreasing velocity towards the column wall most certainly due to a lower permeability. This effect was much less pronounced in the case of spherical particles, indicating a more homogenous packing structure. The influence of the column packing pressure, as a possible measure for improvement of the packing homogeneity was also studied. It was shown that under the same packing conditions spherical particles always lead to a more homogeneous packing. The overall results of this work contribute to the origin of the fact that spherical material is superior to irregular one from the hydrodynamic point of view.

Compositional evolution of the emplaced fuel source in the vadose zone field experiment at Airbase Verløse, Denmark.

A field experiment was performed in a sandy vadose zone, studying the fate of an emplaced fuel-NAPL source, composed of 13 hydrocarbons and a tracer. The UNIFAC model was used to testthe nonideal behavior of the source, and the numerical model MIN3P was used for assessing the effect of biodegradation on source evolution. The diffusive loss to the surrounding vadose zone and the atmosphere created temporary gradients in mole fractions of the individual compounds within the source NAPL. The evolution of the source composition corresponded in general with expectations based on Raoult's Law, with the exception thatthe mole fractions of aromatic compounds in the source NAPL decreased faster than fractions of aliphatic compounds of similar volatility. Calculation of activity coefficients (y) using the UNIFAC model implied nonideal conditions, with composition-dependent gammas different from 1. Positive deviations were calculated for the aromatic compounds. The effect of biodegradation on source depletion, evaluated by numerical modeling, was greater for the aromatic as compared to the aliphatic compounds. Hence, the faster depletion of the aromatic relative to aliphatic compounds of similar volatility is both a result of the nonideality of the mixture and a result of partitioning and biodegradation in the pore-water. Vapor concentrations of the compounds in the source were in reasonable agreement with predictions based on the modified Raoult's Law with the UNIFAC predicted gammas and the NAPL composition for the most volatile compounds. For the less volatile compounds, the measured vapor concentrations were lower than predicted with the largest deviations for the least volatile compounds. This field experiment illustrated that nonideal behavior and bioenhanced source depletion need to be considered at multicomponent NAPL spill sites.