Using the L* concept to explore controls on the relationship between paired ligand and dissolved iron concentrations in the ocean

Ligand (L) dynamics are inextricably linked to iron biogeochemistry, and their binding characteristics define much of the oceanic distributions of dissolved iron (DFe). Usually, L concentrations [L] are considered to be perennially in excess of [DFe] at any oceanic locale or point in time. Here we use the biogeochemical * concept to investigate whether distinct trends and patterns are evident for L* (the excess of [L] over [DFe]) across the two conventional ligand classes L1 and L2. The largest global datasets are available for L2* and point overwhelmingly to positive L2* values (but clearly establishing whether ligands in published studies are L2 versus L1 can be problematic). This trend is also apparent, for a more limited dataset, for L1*. Negative L2* values are mainly linked to high-iron waters (> 2 nmol L^− 1). Datasets from process studies, such as mesoscale iron-enrichments and shipboard particle remineralisation time-series, provide insights into the main drivers of L* in surface and subsurface waters, respectively. Multiple studies reveal rapid (days) microbial responses to iron-enrichment, with L1* increasing from negative to positive values. Deeper in the water column, particle remineralisation releases L2 concurrently with DFe but at higher concentrations (i.e. + L2*). We propose that + L1* is driven by opportunism within marine bacteria, but the magnitude of L1* is constrained by the energetic demands of producing siderophores, for example in response to episodic iron-enrichment, such that L1 is produced in slight excess only. In contrast, during subsurface particle solubilisation, + L2* values are probably driven by concurrent release of a larger excess of organic compounds (linked to major elements like C, which can act as L2) relative to trace amounts of DFe.