Siderophore-promoted transfer of rare earth elements and iron from volcanic ash into glacial meltwater, river and ocean water

The rare earth elements (REE) are a group of trace elements that have short marine residence times and that in river, lake and marine surface waters are typically associated with organic and inorganic particles. Explosive volcanic eruptions, such as the 2010 eruptions of Eyjafjallajökull volcano in Iceland, produce volcanic ash particles which can be an important source of iron and other nutrients for aquatic organisms. To become bioavailable, however, this iron needs to be solubilized by complexing agents, such as siderophores. A well-studied example of such a chelator is the biogenic siderophore desferrioxamin-B (DFOB). Based on results from incubation experiments with glacial meltwater-rich river waters from southern Iceland, which are rich in suspended volcanic ash and that had been incubated with and without DFOB, respectively, we here show that siderophores not only enhance the release of iron, but also promote the mobilization of REE from these particles. In the presence of DFOB, partial dissolution of volcanic ash (and presumably other lithic particles) produces a flux of dissolved REE into ambient waters, that is characterized by depletion of the light REE over the middle REE and by selective enrichment of cerium, due to the formation of dissolved Ce(IV)-DFOB complexes. In siderophore-rich environments, this siderophore-bound REE flux has the potential to modify the concentrations and distribution of the dissolved REE and of the isotopic composition of dissolved Nd in glacial meltwaters, river waters and seawater and might be a component of the boundary effects between shelf sediments and seawater, which are assumed to account for the “missing Nd flux” to seawater. Thermodynamic data further suggest that siderophore-promoted element mobilization could also be important for other polyvalent (trace) elements, such as Hf.

► Incubation experiments were performed with river waters from Iceland that are rich in suspended volcanic ash. ► Siderophores (DFOB) strongly enhance mobilization of REE and Fe from suspended volcanic ash. ► Siderophores produce a distinctive REE fractionation during incongruent particle dissolution. ► Siderophores promote the oxidative dissolution of Ce, producing positive Ce anomalies in ambient waters. ► REE systematics and Nd isotopic composition in meltwater, river and seawater may be affected by a siderophore-bound REE flux.