Kinetic studies of Ni organic complexes using diffusive gradients in thin films (DGT) with double binding layers and a dynamic numerical model.

In situ deployments of diffusive gradients in thin films (DGT) can provide direct information on complex dissociation rates in natural waters. Recent advances in understanding the dynamics of the interactions of metal complexes within DGT devices have highlighted the characteristics of the binding layer, but there are few data to complement these theoretical developments. In this work the penetration into the Chelex binding layer of complexes of Ni with nitrilotriacetic (NTA) and Suwannee River fulvic and humic acids (FA and HA) in solution at pH 7 was investigated by deployment of DGT devices with two sequential binding layers, a "front" and a "back" layer. In Ni-NTA experiments, the masses of Ni bound by the front and back binding layers were similar, as predicted for slowly dissociating complexes. For Ni-FA/HA solutions, a higher mass of Ni was taken up by the front binding layer, consistent with fast dissociation from a high proportion of the binding sites. The ratio of Ni in the front to back binding layers was significantly lower (p < 0.05) for solutions of Ni-HA compared to those of Ni-FA, indicating that Ni-HA complexes are less labile than Ni-FA complexes in similar solutions (FA = 10 mg L(-1) and HA = 8 mg L(-1)). A dynamic numerical model of the complexes in a DGT system was used to estimate the dissociation rate constants that provided the best agreement with the experimental data. Values obtained of 2 ± 0.5 × 10(-4) s(-1) for Ni-NTA and 2.5 × 10(-3) s(-1) for Ni-FA when FA = 20 mg L(-1) and 3.42 × 10(-4) s(-1) for Ni-HA when HA = 8 mg L(-1), could be rationalized with current knowledge of the dynamics of these systems. This approach can improve kinetic information obtainable using DGT and widen the range of considered complex labilities.

Estimation of diffusive boundary layer thickness in studies involving diffusive gradients in thin films (DGT).

Recent laboratory experiments and field investigations involving diffusive gradients in thin films (DGT) have shown that the thickness (delta) of the diffusive boundary layer (DBL), which can affect the accuracy of the technique, is generally not negligible. Accordingly, the determination of delta has become a matter of considerable practical importance. Though the problem has been addressed in the recent literature, there is room for some improvement. An expression for estimation of delta is presented here, and a practical procedure for determining delta and the concentration of DGT-labile species from sparse experimental data is proposed and illustrated by analyzing data from four experiments with DGT samplers of different diffusive gel thicknesses.

Antioxidative stress proteins and their gene expression in brown trout (Salmo trutta) from three rivers with different heavy metal levels.

Three populations of brown trout (Salmo trutta) exposed to different metal levels in their natural environments, were studied with respect to antioxidants metallothionein (MT), superoxide dismutase (SOD) and catalase (CAT) as well as for corresponding mRNA levels. In addition, mRNA levels were studied for glutathione peroxidase (GPx) and glutathione reductase (GR). The Cd/Zn-exposed trout (Naustebekken River) had higher accumulated levels of Cd, Cu and Zn in gills, and higher levels of MT (both protein and mRNA) in liver and kidney as well as in gills compared to the Cu-exposed trout (Rugla River) and trout from an uncontaminated reference river (Stribekken River). Less MT found in the Cu-exposed trout may increase susceptibility to oxidative stress, but no higher levels of antioxidant mRNAs were found in gills of these trouts. The data indicated that chronic exposures of brown trout to Cd, Zn and/or Cu did not involve maintenance of high activities of SOD and CAT enzymes in gills, although SOD mRNA levels were higher in the Cd/Zn-exposed trout. In livers, mRNA levels of SOD, CAT and GPx were higher in the metal-exposed trout, but in the case of GR this was only seen in kidneys of Cd/Zn-exposed trout. However, both metal-exposed groups had higher activities of SOD enzyme in liver compared to the unexposed reference trout, and CAT activity was found to be higher in kidneys of Cu-exposed trout. The Cu-exposed trout did not seem to rely on MT production to avoid Cu toxicity in gills, but rather by keeping the Cu uptake at a low level. A coordinated expression of different stress genes may also be important in chronic metal exposure. It may be concluded that the observed metal effects relies on acclimation rather than on genetic adaptation in the metal exposed populations.