ALBERT

Description: It is widely accepted that iron (Fe)-binding organic ligands play a crucial role in Fe distribution in the marine environment and thus in Fe biogeochemistry. Although Competitive Ligand Equilibration – Adsorptive Cathodic Stripping Voltammetry (CLE-AdCSV) is a well-established technique to investigate Fe chemical speciation in marine samples, several impediments still need to be addressed. These include the extrapolation of laboratory measurements to in-situ conditions, the harmonization of the analytical procedures used, and the applicability of the methods over salinity ranges wider than seawater (e.g., sea ice). This work focusses on the calibration of 2-(2-thiazolylazo)-p-cresol (TAC), salicylaldoxime (SA) and 1-nitroso-2-naphthol (NN), along the salinity range 1–90, and titration of natural samples at two different temperatures (4 °C and 20 °C). The artificial ligand concentration was 10 μM for TAC and 5 μM for SA and NN. Calibrations showed that increasing salinity caused a decrease in the conditional stability constants (logK'Fe’AL) for NN and SA (although different behaviours were noted for the two species FeSA and FeSA2). Less accuracy was noted using TAC, which behaved inconsistently outside the 21 〈 S 〈 35 range, and its use is therefore discouraged in fresh and highly saline waters. Titrations of natural samples showed that only SA covered the salinity range selected, up to 78, and its use is therefore recommended in sea-ice studies. The side reaction coefficient (logα'Fe’AL) of each artificial ligand was found to be influenced by temperature differently: logα'Fe’SA was higher at lower temperature (4 °C), whereas logα'Fe’SA2 and logα'Fe’NN3 increased with increasing temperature (to 20 °C). Although titrations performed at 4 °C highlighted that the uncomplexed Fe fraction was 14% lower than at 20 °C, with potential consequences on primary productivity, the percentage of natural Fe complexed was 〉99%. Future investigations should consider the analysis of the samples at a temperature as close as possible to in-situ conditions to reduce the potential temperature effects.

Description: High dissolved iron (dFe) concentrations of the order of 10-100 nmol L-1 are a feature of waters influenced by sedimentary inputs in oxygen minimum zones (OMZ). However, the temporal development of dFe concentrations is poorly defined due to a general reliance on snapshot cross-shelf sections to study marine trace metal dynamics. Multiple cruise campaigns since the 1980s have investigated Fe dynamics over the Peruvian shelf, particularly between 9-17°S where the shelf is broad, extremely productive and known to feature benthic dFe effluxes which are amongst the highest measured globally. This extensive long-term dataset uniquely allows us to study the interannual variability in dFe concentrations and their response to El Niño–Southern Oscillation (ENSO) events. By combining data from 11 cruises during the period 1984-2017 we are able to evaluate dFe dynamics on interannual timescales in a major OMZ. The region where average dFe concentrations are sensitive to variations in ENSO is confined to a subsurface layer at depths between 50-150 m, particularly in the narrow coastal region within 50 km of the coastline. Subsurface dFe concentrations were generally low during El Niño events (0.7-15.4 nmol L-1) and relatively high with a wider range of variability during the cold ENSO phase (1.1-52.1 nmol L-1). Inverse relationships between wind speed and surface/subsurface dFe were evident. In the subsurface layer, this may be attributable to enhanced dFe offshore transport along isopycnals when upwelling-favorable winds relax in accordance with previously outlined theories. Surface layer (〈40 m) dFe variability was likely associated with a dilution and/or oxidation effect depending on the strength of wind driven water column mixing. Upwelling brings macronutrient-rich water into the euphotic zone, but its intensity had a limited impact on upper layer dFe concentrations possibly due to the influence of an onshore geostrophic flow. Interannual variability in surface chlorophyll-a (Chl-a) was found to correlate with dFe concentration in the offshore zone of northern Peru. This is consistent with bioassay experiments and climatological residual nitrate concentrations which both indicate proximal Fe limitation of phytoplankton growth over and beyond the northern Peruvian shelf. Overall, our work highlights the importance of physical factors driving short-term variations in Fe availability in one of the world’s most economically important fishery regions and suggests that, despite pronounced spatial and temporal variability in dFe concentrations, the ENSO phase has an impact on dFe availability.