Dissolved Iron

Journal Pre-proof J o u r n a l P r e -p r o o f 2 ABSTRACT: It is well recognized that the atmospheric deposition of iron (Fe) affects ocean productivity, atmospheric CO 2 uptake, ecosystem diversity, and overall climate. Despite significant advances in measurement techniques and modeling efforts, discrepancies persist between observations and models that hinder accurate predictions of processes and their global effects. Here, we provide an assessment report on where the current state of knowledge is and where future research emphasis would have the highest impact in furthering the field of Fe atmosphere-ocean biogeochemical cycle. These results were determined through consensus reached by diverse researchers from the oceanographic and atmospheric science communities with backgrounds in laboratory and in situ measurements, modeling, and remote sensing. We discuss i) novel measurement methodologies and instrumentation that allow detection and speciation of different forms and oxidation states of Fe in deliquesced mineral aerosol, cloud/rainwater, and seawater; ii) oceanic models that treat Fe cycling with several external sources and sinks, dissolved, colloidal, particulate, inorganic, and organic ligand-complexed forms of Fe, as well as Fe in detritus and phytoplankton; and iii) atmospheric models that consider natural and anthropogenic sources of Fe, mobilization of Fe in mineral aerosols due to the dissolution of Fe-oxides and Fe-substituted aluminosilicates through proton-promoted, organic ligand-promoted, and photo-reductive mechanisms. In addition, the study identifies existing challenges and disconnects (both fundamental and methodological) such as i) inconsistencies in Fe nomenclature and the definition of bioavailable Fe between oceanic and atmospheric disciplines, and ii) the lack of characterization of the processes controlling Fe speciation and residence time at the atmosphere-ocean interface. Such challenges are undoubtedly caused by extremely low concentrations, short lifetime, and the myriad of physical, (photo)chemical, and biological processes affecting global biogeochemical cycling of Fe.

The distribution of dissolved iron (Fe), total organic Fe-binding ligands, and siderophores were measured between the surface and 400 m at Station ALOHA, a long term ecological study site in the North Pacific Subtropical Gyre. Dissolved Fe concentrations were low throughout the water column and strong organic Fe-binding ligands exceeded dissolved Fe at all depths; varying from 0.9 nmol L −1 in the surface to 1.6 nmol L −1 below 150 m. Although Fe does not appear to limit microbial production, we nevertheless found siderophores at nearly all depths, indicating some populations of microbes were responding to Fe stress. Ferrioxamine siderophores were most abundant in the upper water column, with concentrations between 0.1 and 2 pmol L −1 , while a suite of amphibactins were found below 200 m with concentrations between 0.8 and 11 pmol L −1. The distinct vertical distribution of ferrioxamines and amphibactins may indicate disparate strategies for acquiring Fe from dust in the upper water column and recycled organic matter in the lower water column. Amphibactins were found to have conditional stability constants (log K cond FeL 1 ,Fe ′) ranging from 12.0 to 12.5, while ferrioxamines had much stronger conditional stability constants ranging from 14.0 to 14.4, within the range of observed L 1 ligands by voltammetry. We used our data to calculate equilibrium Fe speciation at Station ALOHA to compare the relative concentration of inorganic and siderophore complexed Fe. The results indicate that the concentration of Fe bound to siderophores was up to two orders of magnitude higher than inorganic Fe, suggesting that even if less bioavailable, siderophores were nevertheless a viable pathway for Fe acquisition by microbes at our study site. Finally, we observed rapid production of ferrioxamine E by particle-associated bacteria during incubation of freshly collected sinking organic matter. Fe-limitation may therefore be a factor in regulating carbon metabolism and nutrient regeneration in the mesopelagic.