Abstract. Organic ligands are a key factor determining the availability of dissolved iron (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 the surface water on the shelf are associated with ice-algal exudates, possibly combined with melting of sea ice. Organic ligands in the deeper shelf water are supplied via the 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 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 concentrations (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 (αFe'L; the product of [L′] and conditional binding strength of ligands, KFe'Lcond). 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.
Light and iron availability are intertwined in controlling Southern Ocean primary production because several photosynthetic proteins require iron. Changes in light and iron availability can also affect phytoplankton species composition, which impacts nutrient cycling, carbon drawdown, and food web structure. To investigate the interactive effects of light and iron on phytoplankton growth, photosynthesis, photoacclimation strategy, micronutrient stressinduced protein expression, and species composition, we conducted five bioassay experiments during spring in waters along the western Antarctic Peninsula with four treatments: low light (LL) or high light (HL) combined with or without iron addition. This region has rarely been studied in spring. We found that light limits growth while iron does not, despite overall low iron concentrations. Our results demonstrate that phytoplankton were LL acclimated in situ but photosynthetically optimized for higher light than they were experiencing, likely due to a highly dynamic light regime. Expression patterns of micronutrient stress-induced proteins were consistent with iron stress in off-shelf regions, but remarkably this iron stress did not result in lower carbon fixation and growth rates. Notably, manganese drawdown was highest under elevated light, suggesting a possible role in managing HL, although high flavodoxin expression indicated that Phaeocystis antarctica may not have been manganese-limited. Although light and iron treatments did not impact species composition, high methionine synthase indicated that diatoms could have experienced stress induced by low vitamin B 12 , potentially contributing to P. antarctica's general dominance throughout the experiments. Our results indicate that P. antarctica may be better adapted to spring conditions than diatoms.
Abstract. Organic ligands are a key factor determining the availability of dissolved iron (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 (αFe'L; the product of [L'] and conditional binding strength of ligands, KFe'Lcond). 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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