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Abstract Observations of dissolved iron (dFe) in the subtropical North Atlantic revealed remarkable features: While the near‐surface dFe concentration is low despite receiving high dust deposition, the subsurface dFe concentration is high. We test several hypotheses that might explain this feature in an ocean biogeochemistry model with a refined Fe cycling scheme. These hypotheses invoke a stronger lithogenic scavenging rate, rapid biological uptake, and a weaker binding between Fe and a ubiquitous, refractory ligand. While the standard model overestimates the surface dFe concentration, a 10‐time stronger biological uptake run causes a slight reduction in the model surface dFe. A tenfold decrease in the binding strength of the refractory ligand, suggested by recent observations, starts reproducing the observed dFe pattern, with a potential impact for the global nutrient distribution. An extreme value for the lithogenic scavenging rate can also match the model dFe with observations, but this process is still poorly constrained.
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Recommendations for best practice for iron speciation by competitive ligand exchange adsorptive cathodic stripping voltammetry with salicylaldoxime
The method of competitive ligand exchange followed by adsorptive cathodic stripping voltammetry (CLEAdCSV) allows for the determination of dissolved iron (DFe) organic speciation parameters, i.e., ligand concentration (LFe) and conditional stability constant (log Kcond Fe′L ). Investigation of DFe organic speciation by CLEAdCSV has been conducted in a wide range of marine systems, but aspects of its application pose challenges that have yet to be explicitly addressed. Here, we present a set of observations and recommendations to work toward establishing best practice for DFe organic speciation measurements using the added ligand salicylaldoxime (SA). We detail conditioning procedures to ensure a stable AdCSV signal and discuss the processes at play during conditioning. We also present step-by-step guidelines to simplify CLE-AdCSV data treatment and interpretation using the softwares ECDSoft and ProMCC and a custom spreadsheet. We validate our application and interpretation methodology with the model siderophore deferoxamine B (DFO-B) in a natural seawater sample. The reproducibility of our application and interpretation methodology was evaluated by running duplicate titrations on 19 samples, many of which had been refrozen prior to the duplicate analysis. Nevertheless, 50% of the duplicate analyses agreed within 10% of their relative standard deviation (RSD), and up to 80% within 25% RSD, for both LFe and log Kcond Fe′L . Finally, we compared the sequential addition and equilibration of DFe and SA with overnight equilibration after simultaneous addition of DFe and SA on 24 samples. We found a rather good agreement between both procedures, with 60% of samples within 25% RSD for LFe (and 43% of samples for log KcondFe′L ), and it was not possible to predict differences in LFe or log KcondFe′L based on the method applied, suggesting specific association/dissociation kinetics for different ligand assemblages. Further investigation of the equilibration kinetics against SA may be helpful as a potential way to distinguish natural ligand assemblages.
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- PAR ID:
- 10514131
- Publisher / Repository:
- Elsevier
- Date Published:
- Journal Name:
- Marine Chemistry
- Volume:
- 259
- Issue:
- C
- ISSN:
- 0304-4203
- Page Range / eLocation ID:
- 104348
- Subject(s) / Keyword(s):
- iron ligands competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-AdCSV) Salicylaldoxime (SA) Conditioning Interpretation Comparison
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1016/j.marchem.2023.104348
