Abstract

The analytical technique DGT (Diffusive Gradients in Thin-films) is able to gain access to a wealth of information by carefully interpreting accumulation data from passive samplers with different configurations (i.e. different thicknesses of its constituent layers). A set of DGT devices were simultaneously deployed in solutions of Ni and nitrilotriacetic acid (NTA) of different concentrations to measure the availability of Ni in these solutions. Accumulations indicate that the availability of Ni depends on both the thickness of the resin and the thickness of the diffusive gel. In both cases, the lability degree increases as the thickness increases. As the formation of successive complexes (such as Ni(NTA)2) proceeds, the availability of the metal decreases, which is quantitatively explained by reducing the formulation to a case with only one complex, but with an effective dissociation rate constant that decreases as the concentration of NTA increases. Simple analytical expressions are reported to quantify the lability degree in the different DGT configurations. These results indicate that a set of different DGT devices can characterize the availability of a cation in a natural sample with uptake processes at different spatial or time scales. Alternatively, and from a more fundamental point of view, information on speciation, mobilities and labilities of the species present in natural samples can be obtained with a set of DGT configurations.

Highlights

  • Despite many efforts, the measurement of trace metal speciation in freshwaters is still challenging

  • A set of DGT devices were simultaneously deployed in solutions of Ni and nitrilotriacetic acid (NTA) of different concentrations to measure the availability of Ni in these solutions

  • Simple analytical expressions are reported to quantify the lability degree in the different DGT configurations. These results indicate that a set of different DGT devices can characterize the availability of a cation in a natural sample with uptake processes at different spatial or time scales

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Summary

Introduction

The measurement of trace metal speciation in freshwaters is still challenging. The dependence of the lability on the thickness of the diffusive and resin gels in DGT opens the way to obtain complementary information on the availability of a metal cation in a natural sample which can be summarized in a kinetic signature, i.e., a set of availabilities at different spatial and time scales covered by the set of sensors (Levy et al, 2012a; van Leeuwen et al, 2005) This information can be used to assess which are the complexes that contribute to the metal availability and, eventually, to determine the speciation, dissociation rate constants or diffusion coefficients of the species present in a natural sample (Warnken et al, 2008) which is an important task to understand the functioning of natural systems. The use of ξM h=L1 measured in single ligand systems provides reasonably approximate values when predicting metal accumulation in mixtures

Experimental set-up for DGT measurements
Experimental set-up for measurements with diffusion cell
Determination of diffusion coefficients
Determination of kinetic constants
Numerical simulation of concentration profiles and accumulations
Characterization of the solutions described in Table 1
Dependence of the lability degree on the NTA concentration
Conclusions
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