In nearly a dozen open‐ocean fertilization experiments conducted by more than 100 researchers from nearly 20 countries, adding iron at the sea surface has led to distinct increases in photosynthesis rates and biomass. These experiments confirmed the hypothesis proposed by the late John Martin [Martin, 1990] that dissolved iron concentration is a key variable that controls phytoplankton processes in ocean surface waters However, the measurement of dissolved iron concentration in seawater remains a difficult task [Bruland and Rue, 2001] with significant interlaboratory differences apparent at times. The availability of a seawater reference solution with well‐known dissolved iron (Fe) concentrations similar to open‐ocean values, which could be used for the calibration of equipment or other tasks, would greatly alleviate these problems [National Research Council (NRC), 2002[.

Siderophores, high‐affinity Fe(III) ligands produced by microorganisms to facilitate iron acquisition, might contribute significantly to dissolved Fe(III) complexation in ocean surface waters. In previous work, we demonstrated the photoreactivity of the ferric ion complexes of several α‐hydroxy carboxylic acid—containing siderophores produced by heterotrophic marine bacteria. Here, we expand on our earlier studies and detail the photoreactivity of additional siderophores produced by both heterotrophic marine bacteria and marine cyanobacteria, making comparisons to synthetic and terrestrial siderophores that lack the α‐hydroxy carboxylate group. Our results suggest that, in addition to secondary photochemical reaction pathways involving reactive oxygen species, direct photolysis of Fe(III)‐siderophore complexes might be a significant source of Fe(II) and reactive Fe(III) in ocean surface waters. Our findings further indicate that the photoreactivity of siderophores is primarily determined by the chemical structure of the Fe(III) binding groups that they possess—hydroxamate, catecholate, or α‐hydroxy carboxylate moieties. Hydroxamate groups are photochemically resistant regardless of Fe(III) complexation. Catecholates, in contrast, are susceptible to photooxidation in the uncomplexed form but stabilized against photooxidation when ferrated. α‐Hydroxy carboxylate groups are stable as the uncomplexed acid, but when coordinated to Fe(III), these moieties undergo light‐induced ligand oxidation and reduction of Fe(III) to Fe(II). These photochemical properties appear to determine the reactivity and fate of Fe(III)‐binding siderophores in ocean surface waters, which in turn might significantly influence the biogeochemical cycling of iron.

Significance: Transport of organic carbon from the sunlit surface ocean to deeper depths drives net oceanic uptake of CO ₂ from the atmosphere. However, mechanisms that control this carbon export remain poorly constrained, limiting our ability to model and predict future changes in this globally important process. We show that the flux of sinking particles (typically considered the dominant form of downward transport of organic carbon) is twice as high at a frontal system, relative to surrounding waters or to nonfrontal conditions. Furthermore, downward transport by subduction leads to additional carbon export at the front that is similar in magnitude to the sinking flux. Such enhanced C export at episodic and mesoscale features needs to be incorporated into biogeochemical forecast models.