Jessica N. Fitzsimmons

Distal transport of dissolved hydrothermal iron in the deep South Pacific Ocean

Significance Low concentrations of the micronutrient iron in seawater are known to limit primary production and nitrogen fixation in large regions of the global ocean. Thus, it is important to constrain the sources and sinks controlling the marine dissolved iron distribution and consequent micronutrient supply to surface plankton. Although the major dissolved iron sources have been historically thought to be atmospheric dust inputs and fluxes from the continental margin, we show here the first data to our knowledge demonstrating that dissolved iron from hydrothermal vents can be transported thousands of kilometers from the venting site, which to date has only been suggested and modeled. Thus, hydrothermal vents must be considered when determining the marine dissolved iron inventory, especially in the abyssal ocean. Until recently, hydrothermal vents were not considered to be an important source to the marine dissolved Fe (dFe) inventory because hydrothermal Fe was believed to precipitate quantitatively near the vent site. Based on recent abyssal dFe enrichments near hydrothermal vents, however, the leaky vent hypothesis [Toner BM, et al. (2012) Oceanography 25(1):209–212] argues that some hydrothermal Fe persists in the dissolved phase and contributes a significant flux of dFe to the global ocean. We show here the first, to our knowledge, dFe (<0.4 µm) measurements from the abyssal southeast and southwest Pacific Ocean, where dFe of 1.0–1.5 nmol/kg near 2,000 m depth (0.4–0.9 nmol/kg above typical deep-sea dFe concentrations) was determined to be hydrothermally derived based on its correlation with primordial 3He and dissolved Mn (dFe:3He of 0.9–2.7 × 106). Given the known sites of hydrothermal venting in these regions, this dFe must have been transported thousands of kilometers away from its vent site to reach our sampling stations. Additionally, changes in the size partitioning of the hydrothermal dFe between soluble (<0.02 µm) and colloidal (0.02–0.4 µm) phases with increasing distance from the vents indicate that dFe transformations continue to occur far from the vent source. This study confirms that although the southern East Pacific Rise only leaks 0.02–1% of total Fe vented into the abyssal Pacific, this dFe persists thousands of kilometers away from the vent source with sufficient magnitude that hydrothermal vents can have far-field effects on global dFe distributions and inventories (≥3% of global aerosol dFe input).

Detection of iron ligands in seawater and marine cyanobacteria cultures by high-performance liquid chromatography-inductively coupled plasma-mass spectrometry.

Organic ligands dominate the speciation of iron in the ocean. Little is known, however, about the chemical composition and distribution of these compounds. Here, we describe a method to detect low concentrations of organic Fe ligands using reverse-phase high-performance liquid chromatography (HPLC) tandem multicollector inductively coupled plasma mass spectrometry. This technique can be used to screen seawater and marine cultures for target compounds that can be isolated and structurally characterized. Sensitive detection (<1 picomole Fe) is achieved using an iron-free HPLC system to reduce background Fe levels, minimizing (40)Ar(16)O(+) interferences on (56)Fe with a hexapole collision cell, and introducing oxygen into the sample carrier gas to prevent the formation of reduced carbon deposits that decrease sensitivity. This method was tested with a chromatographic separation of five trace metal complexes that represent the polarity range likely found in seawater. Good separation was achieved with a 20 min water/methanol gradient, although sensitivity decreased by a factor of 2 at high organic solvent concentrations. Finally, Fe ligand complexes were detected from the organic extract of surface South Pacific seawater and from culture media of the siderophore producing cyanobacteria Synechococcus sp. PCC 7002.

Siderophore-based microbial adaptations to iron scarcity across the eastern Pacific Ocean

Significance Iron limits marine production across one third of the surface ocean. The chemical form of iron in these regions is unknown, but it is well established that molecular speciation affects microbial competition for iron uptake. Here we show that the abundance and identity of siderophores, strong iron-binding compounds secreted by microbes to enhance iron uptake, changes across iron-replete and iron-deficient regions of the South Pacific Ocean. In low-iron regions, amphiphilic siderophores are particularly abundant, suggesting a microbial strategy designed to minimize diffusive loss of metabolically expensive compounds while facilitating iron acquisition. Phylogenetic analysis further suggests that the ability to produce amphiphilic siderophores has been transferred across multiple bacterial lineages, suggesting a possible mechanism of adaptation. Nearly all iron dissolved in the ocean is complexed by strong organic ligands of unknown composition. The effect of ligand composition on microbial iron acquisition is poorly understood, but amendment experiments using model ligands show they can facilitate or impede iron uptake depending on their identity. Here we show that siderophores, organic compounds synthesized by microbes to facilitate iron uptake, are a dynamic component of the marine ligand pool in the eastern tropical Pacific Ocean. Siderophore concentrations in iron-deficient waters averaged 9 pM, up to fivefold higher than in iron-rich coastal and nutrient-depleted oligotrophic waters, and were dominated by amphibactins, amphiphilic siderophores with cell membrane affinity. Phylogenetic analysis of amphibactin biosynthetic genes suggests that the ability to produce amphibactins has transferred horizontally across multiple Gammaproteobacteria, potentially driven by pressures to compete for iron. In coastal and oligotrophic regions of the eastern Pacific Ocean, amphibactins were replaced with lower concentrations (1–2 pM) of hydrophilic ferrioxamine siderophores. Our results suggest that organic ligand composition changes across the surface ocean in response to environmental pressures. Hydrophilic siderophores are predominantly found across regions of the ocean where iron is not expected to be the limiting nutrient for the microbial community at large. However, in regions with intense competition for iron, some microbes optimize iron acquisition by producing siderophores that minimize diffusive losses to the environment. These siderophores affect iron bioavailability and thus may be an important component of the marine iron cycle.

Coordinated regulation of growth, activity and transcription in natural populations of the unicellular nitrogen-fixing cyanobacterium Crocosphaera

The temporal dynamics of phytoplankton growth and activity have large impacts on fluxes of matter and energy, yet obtaining in situ metabolic measurements of sufficient resolution for even dominant microorganisms remains a considerable challenge. We performed Lagrangian diel sampling with synoptic measurements of population abundances, dinitrogen (N2) fixation, mortality, productivity, export and transcription in a bloom of Crocosphaera over eight days in the North Pacific Subtropical Gyre (NPSG). Quantitative transcriptomic analyses revealed clear diel oscillations in transcript abundances for 34% of Crocosphaera genes identified, reflecting a systematic progression of gene expression in diverse metabolic pathways. Significant time-lagged correspondence was evident between nifH transcript abundance and maximal N2 fixation, as well as sepF transcript abundance and cell division, demonstrating the utility of transcriptomics to predict the occurrence and timing of physiological and biogeochemical processes in natural populations. Indirect estimates of carbon fixation by Crocosphaera were equivalent to 11% of net community production, suggesting that under bloom conditions this diazotroph has a considerable impact on the wider carbon cycle. Our cross-scale synthesis of molecular, population and community-wide data underscores the tightly coordinated in situ metabolism of the keystone N2-fixing cyanobacterium Crocosphaera, as well as the broader ecosystem-wide implications of its activities.

Dissolved iron and iron isotopes in the southeastern Pacific Ocean

The Southeast Pacific Ocean is a severely understudied yet dynamic region for trace metals such as iron, since it experiences steep redox and productivity gradients in upper waters and strong hydrothermal iron inputs to deep waters. In this study, we report the dissolved iron (dFe) distribution from seven stations and Fe isotope ratios (δ56Fe) from three of these stations across a near-zonal transect from 20 to 27°S. We found elevated dFe concentrations associated with the oxygen-deficient zone (ODZ), with light δ56Fe implicating porewater fluxes of reduced Fe. However, temporal dFe variability and rapid δ56Fe shifts with depth suggest gradients in ODZ Fe source and/or redox processes vary over short-depth/spatial scales. The dFe concentrations decreased rapidly offshore, and in the upper ocean dFe was controlled by biological processes, resulting in an Fe:C ratio of 4.2 µmol/mol. Calculated vertical diffusive Fe fluxes were greater than published dust inputs to surface waters, but both were orders of magnitude lower than horizontal diffusive fluxes, which dominate dFe delivery to the gyre. The δ56Fe data in the deep sea showed evidence for a −0.2‰ Antarctic Intermediate Water end-member and a heavy δ56Fe of +0.55‰ for distally transported hydrothermal dissolved Fe from the East Pacific Rise. These heavy δ56Fe values were contrasted with the near-crustal δ56Fe recorded in the hydrothermal plume reaching Station ALOHA in the North Pacific. The heavy hydrothermal δ56Fe precludes a nanopyrite composition of hydrothermal dFe and instead suggests the presence of oxides or, more likely, binding of hydrothermal dFe by organic ligands in the distal plume.

Short-term variability in euphotic zone biogeochemistry and primary productivity at Station ALOHA: A case study of summer 2012

Time-series observations are critical to understand the structure, function, and dynamics of marine ecosystems. The Hawaii Ocean Time-series program has maintained near-monthly sampling at Station ...

A ‘shallow bathtub ring’ of local sedimentary iron input maintains the Palmer Deep biological hotspot on the West Antarctic Peninsula shelf

Palmer Deep (PD) is one of several regional hotspots of biological productivity along the inner shelf of the West Antarctic Peninsula. The proximity of hotspots to shelf-crossing deep troughs has led to the ‘canyon hypothesis’, which proposes that circumpolar deep water flowing shoreward along the canyons is upwelled on the inner shelf, carrying nutrients including iron (Fe) to surface waters, maintaining phytoplankton blooms. We present here full-depth profiles of dissolved and particulate Fe and manganese (Mn) from eight stations around PD, sampled in January and early February of 2015 and 2016, allowing the first detailed evaluation of Fe sources to the areas euphotic zone. We show that upwelling of deep water does not control Fe flux to the surface; instead, shallow sediment-sourced Fe inputs are transported horizontally from surrounding coastlines, creating strong vertical gradients of dissolved Fe within the upper 100 m that supply this limiting nutrient to the local ecosystem. The supply of bioavailable Fe is, therefore, not significantly related to the canyon transport of deep water. Near shore time-series samples reveal that local glacial meltwater appears to be an important Mn source but, surprisingly, is not a large direct Fe input to this biological hotspot. This article is part of the theme issue ‘The marine system of the West Antarctic Peninsula: status and strategy for progress in a region of rapid change’.

Arctic deep-water ferromanganese-oxide deposits reflect the unique characteristics of the Arctic Ocean

Little is known about marine mineral deposits in the Arctic Ocean, an ocean dominated by continental shelf and basins semi-closed to deep-water circulation. Here, we present data for ferromanganese crusts and nodules collected from the Amerasia Arctic Ocean in 2008, 2009, and 2012 (HLY0805, HLY0905, HLY1202). We determined mineral and chemical compositions of the crusts and nodules and the onset of their formation. Water column samples from the GEOTRACES program were analyzed for dissolved and particulate scandium concentrations, an element uniquely enriched in these deposits. The Arctic crusts and nodules are characterized by unique mineral and chemical compositions with atypically high growth rates, detrital contents, Fe/Mn ratios, and low Si/Al ratios, compared to deposits found elsewhere. High detritus reflects erosion of submarine outcrops and North America and Siberia cratons, transport by rivers and glaciers to the sea, and distribution by sea ice, brines, and currents. Uniquely high Fe/Mn ratios are attributed to expansive continental shelves, where diagenetic cycling releases Fe to bottom waters, and density flows transport shelf bottom water to the open Arctic Ocean. Low Mn contents reflect the lack of a mid-water oxygen minimum zone that would act as a reservoir for dissolved Mn. The potential host phases and sources for elements with uniquely high contents are discussed with an emphasis on scandium. Scandium sorption onto Fe oxyhydroxides and Sc-rich detritus account for atypically high scandium contents. The opening of Fram Strait in the Miocene and ventilation of the deep basins initiated Fe-Mn crust growth ∼15 Myr ago.