The anion adsorption capability of clays can be improved significantly by modification with certain organic cations. However, surface properties and the microstructure of the clay might change and limit the use of organo-clays in barrier systems. In this study an experimental setup is introduced which allows the rapid determination of effective diffusion coefficients (Deff) for H2O in clay samples. H2O→D2O exchange experiments on hexadecyl-pyridinium (HDPy)-montmorillonite samples were performed in a diffusion cell attached to the ATR unit of a Fourier-transform infrared spectrometer. The mean Deff for H2O in a D2O-saturated original montmorillonite is 2.44 × 10–11 m2/s in the bulk density range of 1.1–1.8 g/cm3. Hydrophobic surfaces increase the diffusivity only at high bulk densities in the saturated state. The mean Deff is lower when HDPy is applied in amounts ⩾80% of the cation exchange capacity in comparison with the original sample. At a saturation degree of the pores of 40%, Deff for all samples is one order of magnitude less than in the saturated state. Results on Deff obtained by ATR-FTIR spectroscopy are in good agreement with through-diffusion studies.

Single crystals of Mg2GeO4 spinel, a stable analogue to mantle ringwoodite at atmospheric pressure up to 800°C, were synthesized from Mg2GeO4 olivine in hydrous conditions at 1.9 GPa and ∼1000°C. Infrared (IR) spectra show OH-stretching peaks at 3531 and 3502 cm–1. Quantification of IR spectra reveals hydrogen in the order of 5 to 10 ppm wt. H2O. A complete hydrogen/deuterium exchange was achieved at 700°C leading to a diffusion coefficient of deuterium of ∼3x10–14 m2/s. This value is of the same order as diffusion coefficients observed in other mantle minerals, such as garnet and diopside.

The O–O distance of ∽ 2.9 Å calculated from the spectra of Mg2GeO4 spinel is consistent with the GeO4 tetrahedra edge length known from crystal-structure data. Whereas the hydration mechanism and the site occupancies involved are still in discussion for mantle spinel, the IR measurements on Mg2GeO4 confirm the idea of protonation at the tetrahedral edges.

A lattice Kinetic Monte Carlo (KMC) approach is considered to study the statistical properties of the diffusion of Pt atom clusters on a Pt(111) surface. The interatomic potential experienced by the diffusing atoms is calculated by the embedded atom method and the hopping barrier for the allowed atomic movements are calculated using the Nudged Elastic Band method. The diffusion coefficient is computed for various cluster sizes and system temperatures. The obtained results are in agreement with the ones obtained in previous experimental and theoretical works. A simple scaling argument is proposed for the size dependence of the diffusion coefficient’s pre-factor. A detailed statistical analysis of the event by event KMC dynamics reveals two important and co-existing mechanisms for the diffusion of the cluster’s center of mass. At low temperatures (below T = 400K) the dominating mechanism responsible for the displacement of the cluster’s center of mass is the periphery (or edge) diffusion of the atoms. At high temperatures (above T = 800K) the dissociation and recombination of the clusters becomes more and more important.

Output least squares stability for the diffusion coefficient in an elliptic equation in dimensiontwo is analyzed. This guarantees Lipschitz stability of the solution of the least squares formulation with respect to perturbations in the data independently of their attainability.The analysis shows the influence of the flow direction on the parameter to be estimated.A scale analysis for multi-scale resolution of the unknown parameter is provided.