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This dataset includes the concentrations of dissolved inorganic macronutrients (phosphate, nitrate plus nitrite (N+N), silicic acid, and nitrite), chlorophyll a and phaeophytin, dissolved trace metals (iron, manganese, nickel, zinc, copper), and labile dissolved nickel, as well as pH and total alkalinity measurements, from discrete depth profile samples collected on the FeOA cruise SKQ202209S on R/V Sikuliaq in the Northeast Pacific from June to July 2022. This project investigates the effects of ocean acidification on the associations between iron and organic ligands in seawater and on iron bioavailability to marine phytoplankton communities. The project used a combination of shipboard incubation experiments and depth profiles to characterize iron speciation and cycling across coastal upwelling, oligotrophic open ocean, and iron-limited subarctic oceanographic regimes in the NE Pacific. Surface seawater was incubated at pH of 8.1, 7.6, and 7.1 with natural iron and with dissolved iron amendments in order to investigate interactions between pH and iron bioavailability across the different regimes. Understanding how pH influences iron and its relationship with ligands provides important information for assessing the impacts of ocean acidification on primary production and biogeochemical processes.more » « less
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This dataset includes trace metal (iron, manganese, cobalt, nickel, copper, zinc, cadmium, lead) and macronutrient (nitrate&nitrite, nitrite, phosphate, silicic acid) concentration data from incubation experiments conducted on board the RRS Discovery during the EXPORTS North Atlantic campaign at the Porcupine Abyssal Plain-Sustained Observatory (PAP-SO) site (DY131). In these experiments, additions of macronutrients (N, P, Si) and Fe were used to assess the level of Si, N, and Fe stress being experienced by the phytoplankton and to contextualize taxa-specific metatranscriptome responses for resolving gene expression profiles in the in-situ communities. This research project focuses on the vertical export of the carbon associated with a major group of phytoplankton, the diatoms in the North Atlantic near the Porcupine Abyssal Plain. The major objective is to understand how diatom community composition and the prevailing nutrient conditions create taxonomic differences in metabolic state that combine to direct diatom taxa to different carbon export pathways. The focus is on diatoms, given their large contribution to global marine primary productivity and carbon export which translates into a significant contribution to the biogeochemical cycling of carbon (C), nitrogen (N), phosphorus (P), iron (Fe) and silicon (Si). It is hypothesized that the type and degree of diatom physiological stress are vital aspects of ecosystem state that drive export. To test this hypothesis, combined investigator expertise in phytoplankton physiology, genomics, and trace element chemistry is used to assess the rates of nutrient use and the genetic composition and response of diatom communities, with measurements of silicon and iron stress to evaluate stress as a predictor of the path of diatom carbon export. The EXPORTS field campaign in the North Atlantic sampled a retentive eddy over nearly a month in May 2021, which coincided with the decline of the North Atlantic Spring Bloom.more » « less
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The method of competitive ligand exchange followed by adsorptive cathodic stripping voltammetry (CLEAdCSV) allows for the determination of dissolved iron (DFe) organic speciation parameters, i.e., ligand concentration (LFe) and conditional stability constant (log Kcond Fe′L ). Investigation of DFe organic speciation by CLEAdCSV has been conducted in a wide range of marine systems, but aspects of its application pose challenges that have yet to be explicitly addressed. Here, we present a set of observations and recommendations to work toward establishing best practice for DFe organic speciation measurements using the added ligand salicylaldoxime (SA). We detail conditioning procedures to ensure a stable AdCSV signal and discuss the processes at play during conditioning. We also present step-by-step guidelines to simplify CLE-AdCSV data treatment and interpretation using the softwares ECDSoft and ProMCC and a custom spreadsheet. We validate our application and interpretation methodology with the model siderophore deferoxamine B (DFO-B) in a natural seawater sample. The reproducibility of our application and interpretation methodology was evaluated by running duplicate titrations on 19 samples, many of which had been refrozen prior to the duplicate analysis. Nevertheless, 50% of the duplicate analyses agreed within 10% of their relative standard deviation (RSD), and up to 80% within 25% RSD, for both LFe and log Kcond Fe′L . Finally, we compared the sequential addition and equilibration of DFe and SA with overnight equilibration after simultaneous addition of DFe and SA on 24 samples. We found a rather good agreement between both procedures, with 60% of samples within 25% RSD for LFe (and 43% of samples for log KcondFe′L ), and it was not possible to predict differences in LFe or log KcondFe′L based on the method applied, suggesting specific association/dissociation kinetics for different ligand assemblages. Further investigation of the equilibration kinetics against SA may be helpful as a potential way to distinguish natural ligand assemblages.more » « less
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This dataset includes the total dissolved, dissolved labile, and soluble nickel concentration results determined in water column samples collected using a trace-metal clean CTD rosette, or an inflatable dinghy, during four cruises in the Bermuda Atlantic Time-series Study (BATS) region in March, May, August, and November 2019. The samples and associated data were collected for the Bermuda Atlantic Iron Time-series (BAIT) project (GEOTRACES Process Study GApr13). Post-cruise sample analyses were performed at the University of South Florida (labile dissolved nickel) and Old Dominion University (dissolved nickel, soluble nickel).more » « less
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This dataset includes the concentrations of dissolved inorganic macronutrients (phosphate, nitrate plus nitrite (N+N), silicic acid, and nitrite), chlorophyll a and phaeophytin, and particulate organic nitrogen and carbon measured shipboard in samples collected from phytoplankton shipboard incubation experiments conducted on the FeOA cruise SKQ202209S on R/V Sikuliaq in the Northeast Pacific from June to July 2022. This project investigates the effects of ocean acidification on the associations between iron and organic ligands in seawater and on iron bioavailability to marine phytoplankton communities. The project used a combination of shipboard incubation experiments and depth profiles to characterize iron speciation and cycling across coastal upwelling, oligotrophic open ocean, and iron-limited subarctic oceanographic regimes in the NE Pacific. Surface seawater was incubated at pH of 8.1, 7.6, and 7.1 with natural iron and with dissolved iron amendments in order to investigate interactions between pH and iron bioavailability across the different regimes. Understanding how pH influences iron and its relationship with ligands provides important information for assessing the impacts of ocean acidification on primary production and biogeochemical processes.more » « less
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Concentrations of inorganic dissolved macronutrients, including phosphate, nitrate plus nitrite (N+N), silicic acid, and nitrite, from phytoplankton shipboard incubation experiments and depth profiles collected on STING I cruise AE2305 on R/V Atlantic Explorer in the Gulf of Mexico from February to March 2023. This project investigates how groundwater discharge delivers important nutrients to the coastal ecosystems of the West Florida Shelf. Preliminary studies indicate that groundwater may supply both dissolved organic nitrogen (DON) and iron in this region. In coastal ecosystems like the West Florida Shelf that have very low nitrate and ammonium concentrations, DON is the main form of nitrogen available to organisms. Nitrogen cycling is strongly affected by iron availability because iron is essential for both photosynthesis and for nitrogen fixation. This study will investigate the sources and composition of DON and iron, and their influence on the coastal ecosystem. The team will sample offshore groundwater wells, river and estuarine waters, and conduct two expeditions across the West Florida Shelf in winter and summer.more » « less
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Abstract Particulate phases transport trace metals (TM) and thereby exert a major control on TM distribution in the ocean. Particulate TMs can be classified by their origin as lithogenic (crustal material), biogenic (cellular), or authigenic (formed in situ), but distinguishing these fractions analytically in field samples is a challenge often addressed using operational definitions and assumptions. These different phases require accurate characterization because they have distinct roles in the biogeochemical iron cycle. Particles collected from the upper 2,000 m of the northwest subtropical Atlantic Ocean over four seasonal cruises throughout 2019 were digested with a chemical leach to operationally distinguish labile particulate material from refractory lithogenics. Direct measurements of cellular iron (Fe) were used to calculate the biogenic contribution to the labile Fe fraction, and any remaining labile material was defined as authigenic. Total particulate Fe (PFe) inventories varied <15% between seasons despite strong seasonality in dust inputs. Across seasons, the total PFe inventory (±1SD) was composed of 73 ± 13% lithogenic, 18 ± 7% authigenic, and 10 ± 8% biogenic Fe above the deep chlorophyll maximum (DCM), and 69 ± 8% lithogenic, 30 ± 8% authigenic, and 1.1 ± 0.5% biogenic Fe below the DCM. Data from three other ocean regions further reveal the importance of the authigenic fraction across broad productivity and Fe gradients, comprising ca. 20%–27% of total PFe.more » « less
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The cyanobacterium Trichodesmium plays an essential role supporting ocean productivity by relieving nitrogen limitation via dinitrogen (N 2 ) fixation. The two common Trichodesmium clades, T. erythraeum and T. thiebautii , are both observed in waters along the West Florida Shelf (WFS). We hypothesized that these taxa occupy distinct realized niches, where T. thiebautii is the more oceanic clade. Samples for DNA and water chemistry analyses were collected on three separate WFS expeditions (2015, 2018, and 2019) spanning multiple seasons; abundances of the single copy housekeeping gene rnpB from both clades were enumerated via quantitative PCR. We conducted a suite of statistical analyses to assess Trichodesmium clade abundances in the context of the physicochemical data. We observed a consistent coastal vs. open ocean separation of the two clades: T. erythraeum was found in shallow waters where the concentrations of dissolved iron (dFe) and the groundwater tracer Ba were significantly higher, while T. thiebautii abundance was positively correlated with water column depth. The Loop Current intrusion in 2015 with entrained Missisippi River water brought higher dFe and elevated abundance of both clades offshore of the 50 m isobath, suggesting that both clades are subject to Fe limitation on the outer shelf. Whereas, previous work has observed that T. thiebautii is more abundant than T. erythraeum in open ocean surface waters, this is the first study to examine Trichodesmium niche differentiation in a coastal environment. Understanding the environmental niches of these two key taxa bears important implications for their contributions to global nitrogen and carbon cycling and their response to global climate change.more » « less
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