Iron organic speciation determination in rainwater using cathodic stripping voltammetry

A sensitive method using Competitive Ligand Exchange-Adsorptive Cathodic Stripping Voltammetry (CLE-ACSV) has been developed to determine for the first time iron (Fe) organic speciation in rainwater over the typical natural range of pH. We have adapted techniques previously developed in other natural waters to rainwater samples, using the competing ligand 1-nitroso-2-naphthol (NN). The blank was equal to 0.17 ± 0.05 nM (n = 14) and the detection limit (DL) for labile Fe was 0.15 nM which is 10–70 times lower than that of previously published methods. The conditional stability constant for NN under rainwater conditions was calibrated over the pH range 5.52–6.20 through competition with ethylenediaminetetraacetic acid (EDTA). The calculated value of the logarithm of β′Fe3+3(NN)β′Fe3+(NN)3 increased linearly with increasing pH according to log β′Fe3+3(NN)=2.4±0.6×pH+11.9±3.5log β′Fe3+(NN)3=2.4±0.6×pH+11.9±3.5 (salinity = 2.9, T = 20 °C). The validation of the method was carried out using desferrioxamine mesylate B (DFOB) as a natural model ligand for Fe. Adequate detection windows were defined to detect this class of ligands in rainwater with 40 μM of NN from pH 5.52 to 6.20. The concentration of Fe-complexing natural ligands was determined for the first time in three unfiltered and one filtered rainwater samples. Organic Fe-complexing ligand concentrations varied from 104.2 ± 4.1 nM equivalent of Fe(III) to 336.2 ± 19.0 nM equivalent of Fe(III) and the logarithm of the conditional stability constants, with respect to Fe3+, varied from 21.1 ± 0.2 to 22.8 ± 0.3. This method will provide important data for improving our understanding of the role of wet deposition in the biogeochemical cycling of iron.

Natural iron fertilization of the Atlantic sector of the Southern Ocean by continental shelf sources of the Antarctic Peninsula

In large parts of the Southern Ocean, primary production is limited due to shortage of iron (Fe). We measured vertical Fe profiles in the western Weddell Sea, Weddell-Scotia Confluence, and Antarctic Circumpolar Current (ACC), showing that Fe is derived from benthic Fe diffusion and sediment resuspension in areas characterized by high turbulence due to rugged bottom topography. Our data together with literature data reveal an exponential decrease of dissolved Fe (DFe) concentrations with increasing distance from the continental shelves of the Antarctic Peninsula and the western Weddell Sea. This decrease can be observed 3500 km eastward of the Antarctic Peninsula area, downstream the ACC. We estimated DFe summer fluxes into the upper mixed layer of the Atlantic sector of the Southern Ocean and found that horizontal advection dominates DFe supply, representing 54 ± 15% of the total flux, with significant vertical advection second most important at 29 ± 13%. Horizontal and vertical diffusion are weak with 1 ± 2% and 1 ± 1%, respectively. The atmospheric contribution is insignificant close to the Antarctic continent but increases to 15 ± 10% in the remotest waters (>1500 km offshore) of the ACC. Translating Southern Ocean carbon fixation by primary producers into biogenic Fe fixation shows a twofold excess of new DFe input close to the Antarctic continent and a one-third shortage in the open ocean. Fe recycling, with an estimated “fe” ratio of 0.59, is the likely pathway to balance new DFe supply and Fe fixation.

Estimation of atmospheric nutrient inputs to the Atlantic Ocean from 50°N to 50°S based on large-scale field sampling: Iron and other dust-associated elements

Atmospheric inputs of mineral dust supply iron and other trace metals to the remote ocean and can influence the marine carbon cycle due to iron's role as a potentially limiting micronutrient. Dust generation, transport, and deposition are highly heterogeneous, and there are very few remote marine locations where dust concentrations and chemistry (e.g., iron solubility) are routinely monitored. Here we use aerosol and rainwater samples collected during 10 large-scale research cruises to estimate the atmospheric input of iron, aluminum, and manganese to four broad regions of the Atlantic Ocean over two 3 month periods for the years 2001–2005. We estimate total inputs of these metals to our study regions to be 4.2, 17, and 0.27 Gmol in April–June and 4.9, 14, and 0.19 Gmol in September–November, respectively. Inputs were highest in regions of high rainfall (the intertropical convergence zone and South Atlantic storm track), and rainfall contributed higher proportions of total input to wetter regions. By combining input estimates for total and soluble metals for these time periods, we calculated overall percentage solubilities for each metal that account for the contributions from both wet and dry depositions and the relative contributions from different aerosol types. Calculated solubilities were in the range 2.4%–9.1% for iron, 6.1%–15% for aluminum, and 54%–73% for manganese. We discuss sources of uncertainty in our estimates and compare our results to some recent estimates of atmospheric iron input to the Atlantic.

The biogeochemical structuring role of horizontal stirring: Lagrangian perspectives on iron delivery downstream of the Kerguelen Plateau

Field campaigns are instrumental in providing ground truth for understanding and modeling global ocean biogeochemical budgets. A survey however can only inspect a fraction of the global oceans, typically a region hundreds of kilometers wide for a temporal window of the order of (at most) several weeks. This spatiotemporal domain is also the one in which the mesoscale activity induces through horizontal stirring a strong variability in the biogeochemical tracers, with ephemeral, local contrasts which can easily mask the regional and seasonal gradients. Therefore, whenever local in situ measures are used to infer larger-scale budgets, one faces the challenge of identifying the mesoscale structuring effect, if not simply to filter it out. In the case of the KEOPS2 investigation of biogeochemical responses to natural iron fertilization, this problem was tackled by designing an adaptive sampling strategy based on regionally optimized multisatellite products analyzed in real time by specifically designed Lagrangian diagnostics. This strategy identified the different mesoscale and stirring structures present in the region and tracked the dynamical frontiers among them. It also enabled back trajectories for the ship-sampled stations to be estimated, providing important insights into the timing and pathways of iron supply, which were explored further using a model based on first-order iron removal. This context was essential for the interpretation of the field results. The mesoscale circulation-based strategy was also validated post-cruise by comparing the Lagrangian maps derived from satellites with the patterns of more than one hundred drifters, including some adaptively released during KEOPS2 and a subsequent research voyage. The KEOPS2 strategy was adapted to the specific biogeochemical characteristics of the region, but its principles are general and will be useful for future in situ biogeochemical surveys.