An experimental study on the mixing behavior of Ti, Zr, V and Mo in the Elbe, Rhine and Weser estuaries

• Zirconium and titanium showed unexpected increases in their dissolved concentrations at mid-salinities.
• Molybdenum and vanadium showed some deviations from anticipated conservative behavior.
• We assume changes of particle surface properties to be the dominant causes of observed variabilities.

Estuaries are important interfaces between land and ocean, in which the input of trace metals into the ocean via the rivers is often significantly modified along the mixing gradient between freshwater and seawater. In the present study we have carried out mixing experiments using river water from the Rhine, the Elbe and the Weser and seawater from the North Sea with the aim of gaining more insights into the behavior of titanium (Ti), zirconium (Zr), vanadium (V) and molybdenum (Mo) and their distribution between dissolved and particulate forms during mixing in the estuaries. Little is known about the modification of their concentrations in estuaries and these metals increasingly enter the rivers and the ocean due to their application as so-called high-tech metals in industrial activities. Such laboratory experiments at controlled conditions allow the systematic investigation of chemical changes related to the mixing ratios, independent of further influence factors occurring in natural systems. Adsorptive stripping voltammetry was used for the analytical determination of the four metals. Although our data largely confirmed a strong particle-reactive behavior of Ti and Zr and a mostly conservative behavior of Mo, our mixing experiments revealed partial deviation from this behavior. Vanadium mostly does not follow a strict conservative mixing trend but shows both small ad- and desorption effects along the salinity transect. Also Mo shows some deviations from conservative mixing at mid-salinities. The enrichment of dissolved Ti and Zr at about 50:50 river: seawater mixtures agrees with recently published data of similar field studies and appears to be a systematic effect possibly related to charge transitions on particle surfaces or change of the dissolved metal speciation. The observed effects partly differed in experiments with filtered and non-filtered river water samples, especially for Ti and Zr, highlighting the role of riverine particulate matter for the modification of dissolved trace metal fluxes in estuaries.

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