Metal speciation dynamics in colloidal ligand dispersions. Part 3: Lability features of steady-state systems

A lability criterion is developed for dynamic metal binding by colloidal ligands with convective diffusion as the dominant mode of mass transport. Scanned stripping chronopotentiometric measurements of Pb(II) and Cd(II) binding by carboxylated latex core-shell particles were in good agreement with the predicted values. The dynamic features of metal ion binding by these particles illustrate that the conventional approach of assuming a smeared-out homogeneous ligand distribution overestimates the lability of a colloidal ligand system. Due to the nature of the spatial distribution of the binding sites, the change in lability of a metal species with changing ligand concentration depends on whether the ligand concentration is varied via manipulation of the pH (degree of protonation) or via the particle concentration. In the former case the local ligand density varies, whereas in the latter case it is constant. This feature provides a useful diagnostic tool for the presence of geometrically constrained binding sites.

Metal speciation dynamics in colloidal ligand dispersions. Part 2: electrochemical lability

We investigate the dynamic nature of metal speciation in colloidal dispersions using a recently proposed theory [J.P. Pinheiro, M. Minor, H.P. Van Leeuwen, Langmuir, 21 (2005) 8635] for complexing ligands that are situated on the surface of the particles. The new approach effectively modifies the finite rates of association/dissociation of the colloidal metal complexes, thus invoking consideration of the two basic dynamic criteria: the association/dissociation kinetics of the volume complexation reaction (the ‘‘dynamic’’ criterion), and the interfacial flux of free metal to a macroscopic surface due to dissociation of complex species (the ‘‘lability’’ criterion). We demonstrate that the conventional approach for homogeneous systems that assume a smeared-out ligand distribution, overestimates both the dynamics and the lability of metal complexes when applied to colloidal ligands. It is also shown that the increase of lability with increasing particle radius, as expected for a homogeneous solution, is moderated for spherical microelectrodes and practically eliminated for planar electrodes.

A time frequency approach to blind deconvolution in multipath underwater channels

Blind deconvolution is studied in the underwater acoustic channel context, by time-frequency (TF) processing. The acoustic propagation environment is modelled by ray tracing and mathematically described by a multipath propagation channel. Representation of the received signal by means of a signal-dependent TF distribution (radially Gaussian kernel distribution) allowed to visualize the resolved replicas of the emitted signal, while signi cantly attenuating the inherent interferences of classic quadratic TF distributions. The source signal instantaneous frequency estimation was the starting point for both source and channel estimation. Source signature estimation was performed by either TF inversion, based on the Wigner-Ville distribution of the received signal, or a subspace- -based method. The channel estimate was obtained either via a TF formulation of the conventional matched- lter, or via matched- - ltering with the previously obtained source estimate. A shallow water realistic scenario is considered, comprising a 135-m depth water column and an acoustic source located at 90-m depth and 5.6-km range from the receiver. For the corresponding noiseless simulated data, the quality of the best estimates was 0.856 for the source signal, and 0.9664 and 0.9996 for the amplitudes and time-delays of the impulse response, respectively. Application of the proposed deconvolution method to real data of the INTIMATE '96 sea trial conduced to source and channel estimates with the quality of 0.530 and 0.843, respectively. TF processing has proved to remove the typical ill-conditioning of single sensor deterministic deconvolution techniques.