The marine biogeochemistry of dissolved and colloidal iron

Thesis (Ph. D.)--Joint Program in Chemical Oceanography (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2013.Cataloged from PDF version of thesis.Includes bibliographical references.Iron is a redox active trace metal micronutrient essential for primary production and nitrogen acquisition in the open ocean. Dissolved iron (dFe) has extremely low concentrations in marine waters that can drive phytoplankton to Fe limitation, effectively linking the Fe and carbon cycles. Understanding the marine biogeochemical cycling and composition of dFe was the focus of this thesis, with an emphasis on the role of the size partitioning of dFe (I nmol/kg) concentrations coincident with the oxygen minimum zone were determined to be caused by remineralization of a high Fe:C organic material (vertical flux), instead of a laterally advected low oxygen-high dFe plume from the African margin. In the South Pacific Ocean, dFe maxima near 2000m were determined by comparison with dissolved manganese and 3He to be caused by hydrothermal venting. The location of these stations hundreds to thousands of kilometers from the nearest vents confirms the "leaky vent" hypothesis that enough dFe escapes precipitation at the vent site to contribute significantly to abyssal dFe inventories. The size partitioning of dFe was also investigated in order to trace the role of dFe composition on its cycling. First, the two most commonly utilized methods of sFe filtration were compared: cross flow filtration (CFF) and Anopore filtration. Both were found to be robust sFe collection methods, and sFe filtrate through CFF (10 kDa) was found to be only 74±21% of the sFe through Anopore (0.02pjm) filters at 28 locations, a function of both pore size differences and the natural variability in distribution of 1 OkDa- 0.02 [m colloids. In the North Atlantic, a colloidal-dominated partitioning was observed in the surface ocean underlying the North African dust plume, in and downstream of the TAG hydrothermal system, and along the western Atlantic margin. However, cFe was depleted or absent at the deep chlorophyll maximum. A summary model of dFe size partitioning in the North Atlantic open ocean is presented in conclusion, hypothesizing that a constant dFe exchange between soluble and colloidal pools modulates the constant partitioning of nearly 50% dFe into the colloidal phase throughout the subsurface North Atlantic Ocean, while sFe and cFe cycle independently in the upper ocean.by Jessica Nicole Fitzsimmons.Ph.D

The GEOTRACES Intermediate Data Product 2014

The GEOTRACES Intermediate Data Product 2014 (IDP2014) is the first publicly available data product of the international GEOTRACES programme, and contains data measured and quality controlled before the end of 2013. It consists of two parts: (1) a compilation of digital data for more than 200 trace elements and isotopes (TEIs) as well as classical hydrographic parameters, and (2) the eGEOTRACES Electronic Atlas providing a strongly inter-linked on-line atlas including more than 300 section plots and 90 animated 3D scenes. The IDP2014 covers the Atlantic, Arctic, and Indian oceans, exhibiting highest data density in the Atlantic. The TEI data in the IDP2014 are quality controlled by careful assessment of intercalibration results and multi-laboratory data comparisons at cross-over stations. The digital data are provided in several formats, including ASCII spreadsheet, Excel spreadsheet, netCDF, and Ocean Data View collection. In addition to the actual data values the IDP2014 also contains data quality flags and 1-σ data error values where available. Quality flags and error values are useful for data filtering. Metadata about data originators, analytical methods and original publications related to the data are linked to the data in an easily accessible way. The eGEOTRACES Electronic Atlas is the visual representation of the IDP2014 data providing section plots and a new kind of animated 3D scenes. The basin-wide 3D scenes allow for viewing of data from many cruises at the same time, thereby providing quick overviews of large-scale tracer distributions. In addition, the 3D scenes provide geographical and bathymetric context that is crucial for the interpretation and assessment of observed tracer plumes, as well as for making inferences about controlling processes.National Science Foundation (U.S.) (OCE-0608600)National Science Foundation (U.S.) (OCE-0938349)National Science Foundation (U.S.) (OCE-1243377

Analysis of trace metals (Cu, Cd, Pb, and Fe) in seawater using single batch nitrilotriacetate resin extraction and isotope dilution inductively coupled plasma mass spectrometry

A simple and accurate low-blank method has been developed for the analysis of total dissolved copper, cadmium, lead, and iron in a small volume (1.3–1.5 mL per element) of seawater. Pre-concentration and salt-separation of a stable isotope spiked sample are achieved by single batch extraction onto nitrilotriacetate (NTA)-type Superflow® chelating resin beads (100–2400 beads depending on the element). Metals are released into 0.1–0.5 M HNO[subscript 3], and trace metal isotope ratios are determined by ICPMS. The benefit of this method compared to our previous Mg(OH)2 coprecipitation method is that the final matrix is very dilute so cone-clogging and matrix sensitivity suppression are minimal, while still retaining the high accuracy of the isotope dilution technique. Recovery efficiencies are sensitive to sample pH, number of resin beads added, and the length of time allowed for sample–resin binding and elution; these factors are optimized for each element to yield the highest recovery. The method has a low procedural blank and high sensitivity sufficient for the analysis of pM–nM open-ocean trace metal concentrations. Application of this method to samples from the Bermuda Atlantic Time-Series Study station provides oceanographically consistent Cu, Cd, Pb, and Fe profiles that are in good agreement with other reliable data for this site. In addition, the method can potentially be modified for the simultaneous analysis of multiple elements, which will be beneficial for the analysis of large number of samples.National Science Foundation (U.S.) (NSF frant OCE-0751409)Kuwait Foundation for the Advancement of SciencesNational Science Foundation (U.S.) (NSF award OCE-0751409)National Science Foundation (U.S.) (NSF award OCE-0926197

Thorium isotopes tracing the iron cycle at the Hawaii Ocean Time-series Station ALOHA

The role of iron as a limiting micronutrient motivates an effort to understand the supply and removal of lithogenic trace metals in the ocean. The long-lived thorium isotopes (²³²Th and ²³⁰Th) in seawater can be used to quantify the input of lithogenic metals attributable to the partial dissolution of aerosol dust. Thus, Th can help in disentangling the Fe cycle by providing an estimate of its ultimate supply and turnover rate. Here we present time-series (1994–2014) data on thorium isotopes and iron concentrations in seawater from the Hawaii Ocean Time-series Station ALOHA. By comparing Th-based dissolved Fe fluxes with measured dissolved Fe inventories, we derive Fe residence times of 6–12 months for the surface ocean. Therefore, Fe inventories in the surface ocean are sensitive to seasonal changes in dust input. Ultrafiltration results further reveal that Th has a much lower colloidal content than Fe does, despite a common source. On this basis, we suggest Fe colloids may be predominantly organic in composition, at least at Station ALOHA. In the deep ocean (>2 km), Fe approaches a solubility limit while Th, surprisingly, is continually leached from lithogenic particles. This distinction has implications for the relevance of Fe ligand availability in the deep ocean, but also suggests Th is not a good tracer for Fe in deep waters. While uncovering divergent behavior of these elements in the water column, this study finds that dissolved Th flux is a suitable proxy for the supply of Fe from dust in the remote surface ocean.National Science Foundation (U.S.) (Grant NS-OIA E-0424599

Testing the Canyon Hypothesis: Evaluating light and nutrient controls of phytoplankton growth in penguin foraging hotspots along the West Antarctic Peninsula

Biological hotspots along the West Antarctic Peninsula (WAP) are characterized by high phytoplankton productivity and biomass as well as spatially focused penguin foraging activity. While unique physical concentrating processes were identified in one of these hotspots, understanding the mechanisms driving the blooms at these locations is of high importance. Factors posited to explain the blooms include the upwelling of macronutrient‐ and micronutrient‐enriched modified Upper Circumpolar Deep Water (mUCDW) and the depth of the mixed layer influencing overall light availability for phytoplankton. Using shipboard trace‐metal clean incubation experiments in three different coastal biological hotspots spanning a north‐south gradient along the WAP, we tested the Canyon Hypothesis (upwelling) for enhanced phytoplankton growth. Diatoms dominated the Southern region, while the Northern region was characterized by a combination of diatoms and cryptophytes. There was ample concentration of macronutrients at the surface and no phytoplankton growth response was detected with the addition of nutrient‐enriched mUCDW water or iron solution to surface waters. For all treatments, addition of mUCDW showed no enhancement in phytoplankton growth, suggesting that local upwelling of nutrient‐enriched deep water in these hotspots was not the main driver of high phytoplankton biomass. Furthermore, the dynamics in the photoprotective pigments were consistent with the light levels used during these incubations showing that phytoplankton are able to photoacclimate rapidly to higher irradiances and that in situ cells are low light adapted. Light availability appears to be the critical variable for the development of hotspot phytoplankton blooms, which in turn supports the highly productive regional food web

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

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.National Science Foundation (U.S.) (OCE-1356747)National Science Foundation (U.S.) (OCE-1233261)National Science Foundation (U.S.) (OCE-1237034)National Science Foundation (U.S.) (DBI-0424599)Gordon and Betty Moore Foundation (Grant GBMF3298)Gordon and Betty Moore Foundation (Grant GBMF3934)Simons Foundation (329108

WTO must ban harmful fisheries subsidies

Sustainably managed wild fisheries support food and nutritional security, livelihoods, and cultures (1). Harmful fisheries subsidies—government payments that incentivize overcapacity and lead to overfishing—undermine these benefits yet are increasing globally (2). World Trade Organization (WTO) members have a unique opportunity at their ministerial meeting in November to reach an agreement that eliminates harmful subsidies (3). We—a group of scientists spanning 46 countries and 6 continents—urge the WTO to make this commitment..