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Niklas J Lehto

Publications and source records attributed to Niklas J Lehto.

2 recordsLinked to original sources

An evaluation of DGT performance using a dynamic numerical model.

A numerical model of the transport and dynamics of metal complexes in the resin and gel layers of a DGT (diffusive gradients in thin films) device was developed and used to investigate how the chelating resin and metal-ligand complexes in solution affect metal uptake. Decreasing the stability constant or concentration of the binding resin increases the competition for free metal ions by ligands in solution, lowering the rate of mass uptake. Such effects would be rarely observed for moderately or strongly binding resins (K> 10(12)), including Chelex, which out-compete labile ligands in solution. With weakly binding resins, strongly bound solution complexes can diffuse into the resin layer before a measurable amount of dissociation occurs, such that concentrations of bound metal at the rear and front surfaces of the resin layer are equal. With more strongly binding resins, metal mainly binds to the front surface of the resin. Only complexes with the largest binding constants penetrate the gel layer containing Chelex, buttheir lack of lability means thatthe DGT sensitivity to the complex is, in any case, very low. The slow diffusion of complexes, such as those of fulvic acids, which increases the time required to establish steady state, compromises the use of the simple DGT equation. Errors are negligible for 24 h deployments, when diffusive layer thicknesses are less than 1 mm, but 3 day deployments are required to ensure accuracy with 2.4 mm thick layers. The extent to which the commonly used equation, that accounts for the concentration and diffusion of metal-complex species, overestimates DGT uptake if the rate of dissociation is slow, was estimated.

Diffusion↗

Dynamic aspects of DGT as demonstrated by experiments with lanthanide complexes of a multidentate ligand.

Sampling of metals with the technique of diffusive gradients in thin-films (DGT) depends on the rates of diffusion and on the kinetics of interconversion of the species present. In this study the discrimination between metal complexes with different dissociation kinetics is investigated. Samplers with differentthicknesses of diffusive and resin gels were deployed in solutions containing 10 microg/L of each metal in the lanthanide (Ln) series (except Pm) and 2.0 x 10(-6) M of the ligand quin2 at an ionic strength of 0.1 M (KNO3) and pH 7.0. Diffusion coefficients of Ln3+ ions and Ln-quin2 complexes were determined in a diffusion cell experiment. The equilibrium speciation of the metals was calculated from available stability constants. The sampling rate (mass/time) was highly dependent on the dissociation-rate constant of the complexes. For complexes with dissociation kinetics that appreciably limited the uptake, the sampling rate decreased significantly with increasing deployment times (12, 24, and 76 h) and was virtually independent of the thickness of the diffusive gel. Placing a layer of diffusive gel behind the resin did not influence the accumulation of Lns in the resin gel, but doubling the thickness of the layer containing resin increased the uptake, and more so for the Lns forming less labile complexes. The Lns forming more labile complexes were enriched in the outer layer of the resin, and there was a trend toward even distribution between the outer and deeper parts of the resin layer for the Lns forming less labile complexes. The measured DGT sampling rates (mass/ time) were reasonably well predicted by a dynamic model that used independently determined kinetic constants. This new knowledge of how metal complexes behave in the sampling process paves the way for using DGT to obtain in situ kinetic information in natural waters.

Biophysics↗