| Summary: | Organic ligands are a key factor determining availability of dissolved-Fe (DFe) in the high nutrient low chlorophyll (HNLC) areas of the Southern Ocean. In this study, organic speciation of Fe is investigated along a natural gradient of the western Antarctic Peninsula, from an ice covered shelf to the open ocean. An electrochemical approach, competitive ligand exchange - adsorptive cathodic stripping voltammetry (CLE-AdCSV) was applied. Our results indicated that organic ligands in surface water on the shelf are associated with ice-algal exudates, possibly combined with melting of sea-ice. Organic ligands in deeper shelf water are supplied via resuspension of slope or shelf sediments. Further offshore, organic ligands are most likely related to the development of phytoplankton blooms in open ocean waters. On the shelf, total ligand concentrations ([Lt]) were between 1.2 nM eq. Fe and 6.4 nM eq. Fe. The organic ligands offshore ranged between 1.0 and 3.0 nM eq. Fe. The southern boundary of the Antarctic Circumpolar Current (SB ACC) separated the organic ligands on the shelf from bloom-associated ligands offshore. Overall, organic ligand concentrations always exceeded DFe concentration (excess ligand concentration, [L??] = 0.8 - 5.0 nM eq. Fe). The [L??] made up to 80% of [Lt], suggesting that any additional Fe input can be stabilized in the dissolved form via organic complexation. The denser modified Circumpolar Deep Water (mCDW) on the shelf showed the highest complexation capacity of Fe (??Fe??L the product of [L??] and binding strength of ligands, K??Fe??L). Since Fe is also supplied by shelf sediments and glacial discharge, the high complexation capacity over the shelf can keep Fe dissolved and available for local primary productivity later in the season upon sea ice melting.
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