Distal transport of dissolved hydrothermal iron in the deep South Pacific 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 [superscript 3]He and dissolved Mn (dFe:[superscript 3]He of 0.9–2.7 × 10[superscript 6]). 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).National Science Foundation (U.S.). Graduate Research Fellowship (Award 0645960)Center for Microbial Oceanography: Research and Education (NSF-OIA Award EF-0424599)Gordon and Betty Moore Foundatio

SpoT Induces Intracellular Salmonella Virulence Programs in the Phagosome.

Guanosine tetraphosphate (ppGpp) and guanosine pentaphosphate (pppGpp), together named (p)ppGpp, regulate diverse aspects of Salmonella pathogenesis, including synthesis of nutrients, resistance to inflammatory mediators, and expression of secretion systems. In Salmonella, these nucleotide alarmones are generated by the synthetase activities of RelA and SpoT proteins. In addition, the (p)ppGpp hydrolase activity of the bifunctional SpoT protein is essential to preserve cell viability. The contribution of SpoT to physiology and pathogenesis has proven elusive in organisms such as Salmonella, because the hydrolytic activity of this RelA and SpoT homologue (RSH) is vital to prevent inhibitory effects of (p)ppGpp produced by a functional RelA. Here, we describe the biochemical and functional characterization of a spoT-Δctd mutant Salmonella strain encoding a SpoT protein that lacks the C-terminal regulatory elements collectively referred to as "ctd." Salmonella expressing the spoT-Δctd variant hydrolyzes (p)ppGpp with similar kinetics to those of wild-type bacteria, but it is defective at synthesizing (p)ppGpp in response to acidic pH. Salmonella spoT-Δctd mutants have virtually normal adaptations to nutritional, nitrosative, and oxidative stresses, but poorly induce metal cation uptake systems and Salmonella pathogenicity island 2 (SPI-2) genes in response to the acidic pH of the phagosome. Importantly, spoT-Δctd mutant Salmonella replicates poorly intracellularly and is attenuated in a murine model of acute salmonellosis. Collectively, these investigations indicate that (p)ppGpp synthesized by SpoT serves a unique function in the adaptation of Salmonella to the intracellular environment of host phagocytes that cannot be compensated by the presence of a functional RelA.IMPORTANCE Pathogenic bacteria experience nutritional challenges during colonization and infection of mammalian hosts. Binding of the alarmone nucleotide guanosine tetraphosphate (ppGpp) to RNA polymerase coordinates metabolic adaptations and virulence gene transcription, increasing the fitness of diverse Gram-positive and Gram-negative bacteria as well as that of actinomycetes. Gammaproteobacteria such as Salmonella synthesize ppGpp by the combined activities of the closely related RelA and SpoT synthetases. Due to its profound inhibitory effects on growth, ppGpp must be removed; in Salmonella, this process is catalyzed by the vital hydrolytic activity of the bifunctional SpoT protein. Because SpoT hydrolase activity is essential in cells expressing a functional RelA, we have a very limited understanding of unique roles these two synthetases may assume during interactions of bacterial pathogens with their hosts. We describe here a SpoT truncation mutant that lacks ppGpp synthetase activity and all C-terminal regulatory domains but retains excellent hydrolase activity. Our studies of this mutant reveal that SpoT uniquely senses the acidification of phagosomes, inducing virulence programs that increase Salmonella fitness in an acute model of infection. Our investigations indicate that the coexistence of RelA/SpoT homologues in a bacterial cell is driven by the need to mount a stringent response to a myriad of physiological and host-specific signatures

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

Dissolved Al in the zonal N Atlantic section of the US GEOTRACES 2010/2011 cruises and the importance of hydrothermal inputs

Author Posting. © The Author(s), 2014. This is the author's version of the work. It is posted here by permission of Elsevier for personal use, not for redistribution. The definitive version was published in Deep Sea Research Part II: Topical Studies in Oceanography 116 (2015): 176-186, doi:10.1016/j.dsr2.2014.07.006.The distribution of dissolved aluminium determined during GA03, the US GEOTRACES North Atlantic Transects (US GT NAZT) shows large inputs to the basin from three main sources, atmospheric deposition, outflow from the Mediterranean, and inputs from hydrothermal sources along the Mid Atlantic Ridge (MAR). The partial dissolution of atmospheric aerosols emanating from the Sahara yield high concentrations of dissolved Al in the surface waters of the basin and are used to estimate the geographical pattern of dust deposition. The Mediterranean outflow delivers a large source of dissolved Al to the intermediate waters of the eastern basin and its subsequent distribution within the basin can be explained by simple isopycnal mixing with surrounding water masses. Hydrothermal venting at the Trans-Atlantic Geotraverse (TAG) hydrothermal field in the MAR produces a neutrally buoyant plume that introduces copious quantities of dissolved Al (with concentrations of up to 40nM) to the deeper waters of the North Atlantic that can be seen advecting to the west of the MAR. The concentration of dissolved Al in the deep waters of the eastern basin of the Atlantic can be accounted for by admixing the MAR Al enriched plume water and Antarctic Bottom Water (AABW) as they pass through the Vema Fracture Zone. The data sets show no evidence for biological remineralisation of dissolved Al from Si carrier phases in deep waters.This work was supported by NSF OCE-0928741 and OCE-1137812 to CIM

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

Author Posting. © The Author(s), 2015. This is the author's version of the work. It is posted here by permission of Elsevier for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 169 (2015): 1-16, doi:10.1016/j.gca.2015.07.019.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 (232 Th and 230 Th) 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.We acknowledge funding from the W.O. Crosby Postdoctoral Fellowship to CTH and the National Science Foundation through C-MORE, NSF-OIA EF-0424599 to EAB, and NSF-DMR Author Posting

The composition of dissolved iron in the dusty surface ocean : an exploration using size-fractionated iron-binding ligands

Author Posting. © The Author(s), 2014. This is the author's version of the work. It is posted here by permission of Elsevier for personal use, not for redistribution. The definitive version was published in Marine Chemistry 173 (2015): 125-135, doi:10.1016/j.marchem.2014.09.002.The size partitioning of dissolved iron and organic iron-binding ligands into soluble and colloidal phases was investigated in the upper 150 m of two stations along the GA03 U.S. GEOTRACES North Atlantic transect. The size fractionation was completed using cross-flow filtration methods, followed by analysis by isotope dilution inductively-coupled plasma mass spectrometry (ID-ICP-MS) for iron and competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV) for iron-binding ligands. On average, 80% of the 0.1-0.65 nM dissolved iron (<0.2 μm) was partitioned into the colloidal iron (cFe) size fraction (10 kDa < cFe < 0.2 μm), as expected for areas of the ocean underlying a dust plume. The 1.3-2.0 nM strong organic iron-binding ligands, however, overwhelmingly (75-77%) fell into the soluble size fraction (<10 kDa). As a result, modeling the dissolved iron size fractionation at equilibrium using the observed ligand partitioning did not accurately predict the iron partitioning into colloidal and soluble pools. This suggests that either a portion of colloidal ligands are missed by current electrochemical methods because they react with iron more slowly than the equilibration time of our CLE-ACSV method, or part of the observed colloidal iron is actually inorganic in composition and thus cannot be predicted by our model of unbound iron-binding ligands. This potentially contradicts the prevailing view that greater than 99% of dissolved iron in the ocean is organically complexed. Untangling the chemical form of iron in the upper ocean has important implications for surface ocean biogeochemistry and may affect iron uptake by phytoplankton.J.N. Fitzsimmons was funded by a National Science Foundation Graduate Research Fellowship (NSF Award #0645960). Research funding was provided by the National Science Foundation (OCE #0926204 and OCE #0926197) and the Center for Microbial Oceanography: Research and Education (NSF-OIA Award #EF-0424599) to E.A. Boyle. R.M. Bundy was partially funded by NSF OCE-0550302 and NSF OCE-1233733 to K.A. Barbeau and an NSF-GK12 graduate fellowship

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

Near-field iron and carbon chemistry of non-buoyant hydrothermal plume particles, Southern East Pacific Rise 15°S

Author Posting. © The Author(s), 2018. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Marine Chemistry 201 (2018): 183-197, doi:10.1016/j.marchem.2018.01.011.Iron (Fe)-poor surface waters limit phytoplankton growth and their ability to remove carbon (C) from the atmosphere and surface ocean. Over the past few decades, research has focused on constraining the global Fe cycle and its impacts on the global C cycle. Hydrothermal vents have become a highly debated potential source of Fe to the surface ocean. Two main mechanisms for transport of Fe over long distances have been proposed: Fe-bearing nanoparticles and organic C complexation with Fe in the dissolved (dFe) and particulate (pFe) pools. However, the ubiquity and importance of these processes is unknown at present, and very few vents have been investigated for Fe-Corg interactions or the transport of such materials away from the vent. Here we describe the near-field contributions (first ~100 km from ridge) of pFe and Corg to the Southern East Pacific Rise (SEPR) plume, one of the largest known hydrothermal plume features in the global ocean. Plume particles (> 0.2 μm) were collected as part of the U.S. GEOTRACES Eastern Pacific Zonal Transect cruise (GP16) by in-situ filtration. Sediment cores were also collected to investigate the properties of settling particles. In this study, X-ray absorption near edge structure (XANES) spectroscopy was used in two complementary X-ray synchrotron approaches, scanning transmission X-ray microscopy (STXM) and X-ray microprobe, to investigate the Fe and C speciation of particles within the near-field non-buoyant SEPR plume. When used in concert, STXM and X-ray microprobe provide fine-scale and representative information on particle morphology, elemental co-location, and chemical speciation. Bulk chemistry depth profiles for particulate Corg (POC), particulate manganese (pMn), and pFe indicated that the source of these materials to the non-buoyant plume is hydrothermal in origin. The plume particles at stations within the first ~100 km down-stream of the ridge were composites of mineral (oxidized Fe) and biological materials (organic C, Corg). Iron chemistry in the plume and in the core-top suspended sediment fluff layer were both dominated by Fe(III) phases, such as Fe(III) oxyhydroxides and Fe(III) phyllosilicates. Particulate sulfur (pS) was a rare component of our plume and sediment samples. When pS was detected, it was in the form of an Fe sulfide mineral phase, composing ≤ 0.4% of the Fe on a per atom basis. The resuspended sediment fluff layer contained a mixture of inorganic (coccolith fragments) and Corg bearing (lipid-rich biofilm-like) materials. The particle morphology and co-location of C and Fe in the sediment was different from that in plume particles. This indicates that if the Fe-Corg composite particles settle rapidly to the sediments, then they experience strong alteration during settling and/or within the sediments. Overall, our observations indicate that the particles within the first ~ 100 km of the laterally advected plume are S-depleted, Fe(III)-Corg composites indicative of a chemically oxidizing plume with strong biological modification. These findings confirm that the Fe-Corg relationships observed for non-buoyant plume particles within ~ 100 m of the vent site are representative of particles within this region of the non-buoyant plume (~100 km). These findings also point to dynamic alteration of Fe-Corg bearing particles during transport and settling. The specific biogeochemical processes at play, and the implications for nutrient cycling in the ocean are currently unknown and represent an area of future investigation