Iceberg-hosted nanoparticulate Fe in the Southern Ocean: Mineralogy, origin, dissolution kinetics and source of bioavailable Fe

Sediments from icebergs and glaciers contain nanopartculate Fe(III) oxyhydroxides (including ferrihydrite) which form in aqueous, oxic (micro)environments where Fe(II)-bearing rock minerals oxidise and high degrees of supersaturation are promoted by freezing and thawing. An ascorbic acid extraction dissolves only labile Fe present in fresh (loosely aggregated) ferrihydrite that is directly or indirectly bioavailable. Glacial and iceberg sediments contain ferrihydrite aggregates that provide 0.04 to 0.17% Fe soluble in ascorbic acid, rather larger than the concentrations in a limited suite of atmospheric dusts. The dissolution behaviour of labile Fe from glacial and iceberg sediments by ascorbic acid is controlled by the access of reactant, or removal of solute, through micropores to or from active sites in the interior of ferrihydrite aggregates. A first-order kinetic model is presented to examine the rates at which bioavailable Fe can be supplied by melting icebergs in the Weddell Sea. The model utilizes rate constants from the literature for the processes which solubilise Fe from nanoparticulate ferrihydrite (dissolution, photochemical reduction and grazing) and the processes that remove Fe nanoparticulates (sinking, scavenging and incorporation in faecal material), and render them less reactive (transformation, aging). Model results demonstrate that icebergs can supply bioavailable Fe to the Weddell Sea by the dissolution of nanoparticulate ferrihydrite (despite loss/removal of nanoparticles by sinking, aging, transformation, scavenging and incorporation into faecal pellets) at rates that are comparable to atmospheric dust. Dissolution enhanced by photochemical reduction and grazing provides the most rapid rates of bioavailable Fe production.