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Dissolved Fe (dFe) concentrations were measured in the upper 1300 m of the water column in the vicinity of Kerguelen Island as part of the second Kerguelen Ocean Plateau compared Study (KEOPS2). Concentrations ranged from 0.06 nmol L-1 in offshore, Southern Ocean waters, to 3.82 nmol L-1 within Hillsborough Bay, on the north-eastern coast of Kerguelen Island. Direct island runoff, glacial melting and resuspended sediments were identified as important inputs of dFe that could potentially fertilize the northern part of the plateau. A significant deep dFe enrichment was observed over the plateau with dFe concentrations increasing up to 1.30 nmol L-1 close to the seafloor, probably due to sediment resuspension and pore water release. Biological uptake was identified as a likely explanation for the decrease in dFe concentrations between two visits (28 days apart) at a station above the plateau. Our results allowed studying other processes and sources, such as atmospheric inputs, lateral advection of enriched seawater, remineralization processes and the influence of the Polar Front (PF) as a vector for Fe transport. Overall, heterogeneous sources of Fe over and off the Kerguelen Plateau, in addition to strong variability in Fe supply by vertical or horizontal transport, may explain the high variability in dFe concentrations observed during this study. [ABSTRACT FROM AUTHOR]

Dinitrogen (N2) fixation represents a key source of reactive nitrogen in marine ecosystems. While the process has been rather well-explored in low latitudes of the Atlantic and Pacific Oceans, other higher latitude regions and particularly the Indian Ocean have been chronically overlooked. Here, we characterize N2 fixation and diazotroph community composition across nutrient and trace metals gradients spanning the multifrontal system separating the oligotrophic waters of the Indian Ocean subtropical gyre from the high nutrient low chlorophyll waters of the Southern Ocean. We found a sharp contrasting distribution of diazotroph groups across the frontal system. Notably, cyanobacterial diazotrophs dominated north of fronts, driving high N2 fixation rates (up to 13.96 nmol N l-1 d-1) with notable peaks near the South African coast. South of the fronts non-cyanobacterial diazotrophs prevailed without significant N2 fixation activity being detected. Our results provide new crucial insights into high latitude diazotrophy in the Indian Ocean, which should contribute to improved climate model parameterization and enhanced constraints on global net primary productivity projections., (© The Author(s) 2024. Published by Oxford University Press on behalf of FEMS.)

Hydrothermal vent sites found along mid-ocean ridges are sources of numerous reduced chemical species and trace elements. To establish dissolved iron (II) (dFe(II)) variability along the Mid Atlantic Ridge (between 39.5°N and 26°N), dFe(II) concentrations were measured above six hydrothermal vent sites, as well as at stations with no active hydrothermal activity. The dFe(II) concentrations ranged from 0.00 to 0.12 nmol L -1 (detection limit = 0.02 ± 0.02 nmol L -1 ) in non-hydrothermally affected regions to values as high as 12.8 nmol L -1 within hydrothermal plumes. Iron (II) in seawater is oxidised over a period of minutes to hours, which is on average two times faster than the time required to collect the sample from the deep ocean and its analysis in the onboard laboratory. A multiparametric equation was used to estimate the original dFe(II) concentration in the deep ocean. The in-situ temperature, pH, salinity and delay between sample collection and its analysis were considered. The results showed that dFe(II) plays a more significant role in the iron pool than previously accounted for, constituting a fraction >20 % of the dissolved iron pool, in contrast to <10 % of the iron pool formerly reported. This discrepancy is caused by Fe(II) loss during sampling when between 35 and 90 % of the dFe(II) gets oxidised. In-situ dFe(II) concentrations are therefore significantly higher than values reported in sedimentary and hydrothermal settings where Fe is added to the ocean in its reduced form. Consequently, the high dynamism of dFe(II) in hydrothermal environments masks the magnitude of dFe(II) sourced within the deep ocean., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

Dissolved organic phosphorus (DOP) concentration distributions in the global surface ocean inform our understanding of marine biogeochemical processes such as nitrogen fixation and primary production. The spatial distribution of DOP concentrations in the surface ocean reflect production by primary producers and consumption as an organic nutrient by phytoplankton including diazotrophs and other microbes, as well as other loss processes such as photolysis. Compared to dissolved organic carbon and nitrogen, however, relatively few marine DOP concentration measurements have been made, largely due to the lack of automated analysis techniques. Here we present a database of marine DOP concentration measurements (DOPv2021) that includes new (n = 730) and previously published (n = 3140) observations made over the last ~30 years (1990-2021), including 1751 observations in the upper 50 m. This dataset encompasses observations from all major ocean basins including the poorly represented Indian, South Pacific, and Southern Oceans and provides insight into spatial distributions of DOP in the ocean. It is also valuable for researchers who work on marine primary production and nitrogen fixation., (© 2022. The Author(s).)

Iron (Fe) plays a dual role in atmospheric chemistry: it is involved in chemical and photochemical reactivity and serves as a micronutrient for microorganisms that have recently been shown to produce strong organic ligands. These ligands control the reactivity, mobility, solubility and speciation of Fe, which have a potential impact on Fe bioavailability and cloud water oxidant capacity. In this work, the concentrations of Fe-binding ligands and the conditional stability constants were experimentally measured for the first time by Competitive Ligand Exchange-Adsorptive Cathodic Stripping Voltammetry (CLE-ACSV) technique in cloud water samples collected at puy de Dôme (France). The conditional stability constants, which indicate the strength of the Fe-ligand complexes, are higher than those considered until now in cloud chemistry (mainly Fe-oxalate). To understand the effect of Fe complexation on cloud water reactivity, we used the CLEPS cloud chemistry model. According to the model results, we found that Fe complexation impacts the hydroxyl radical formation rate: contrary to our expectations, Fe complexation by natural organic ligands led to an increase in hydroxyl radical production. These findings have important impacts on cloud chemistry and the global iron cycle., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

Early studies revealed relationships between barium (Ba), particulate organic carbon and silicate, suggesting applications for Ba as a paleoproductivity tracer and as a tracer of modern ocean circulation. But, what controls the distribution of barium (Ba) in the oceans? Here, we investigated the Arctic Ocean Ba cycle through a one-of-a-kind data set containing dissolved (dBa), particulate (pBa), and stable isotope Ba ratio (δ 138 Ba) data from four Arctic GEOTRACES expeditions conducted in 2015. We hypothesized that margins would be a substantial source of Ba to the Arctic Ocean water column. The dBa, pBa, and δ 138 Ba distributions all suggest significant modification of inflowing Pacific seawater over the shelves, and the dBa mass balance implies that ∼50% of the dBa inventory (upper 500 m of the Arctic water column) was supplied by nonconservative inputs. Calculated areal dBa fluxes are up to 10 μmol m -2  day -1 on the margin, which is comparable to fluxes described in other regions. Applying this approach to dBa data from the 1994 Arctic Ocean Survey yields similar results. The Canadian Arctic Archipelago did not appear to have a similar margin source; rather, the dBa distribution in this section is consistent with mixing of Arctic Ocean-derived waters and Baffin Bay-derived waters. Although we lack enough information to identify the specifics of the shelf sediment Ba source, we suspect that a sedimentary remineralization and terrigenous sources (e.g., submarine groundwater discharge or fluvial particles) are contributors., (© 2022 The Authors.)

Variation in the microbial cycling of nutrients and carbon in the ocean is an emergent property of complex planktonic communities. While recent findings have considerably expanded our understanding of the diversity and distribution of nitrogen (N 2 ) fixing marine diazotrophs, knowledge gaps remain regarding ecological interactions between diazotrophs and other community members. Using quantitative 16S and 18S V4 rDNA amplicon sequencing, we surveyed eukaryotic and prokaryotic microbial communities from samples collected in August 2016 and 2017 across the Western North Atlantic. Leveraging and significantly expanding an earlier published 2015 molecular dataset, we examined microbial community structure and ecological co-occurrence relationships associated with intense hotspots of N 2 fixation previously reported at sites off the Southern New England Shelf and Mid-Atlantic Bight. Overall, we observed a negative relationship between eukaryotic diversity and both N 2 fixation and net community production (NCP). Maximum N 2 fixation rates occurred at sites with high abundances of mixotrophic stramenopiles, notably Chrysophyceae. Network analysis revealed such stramenopiles to be keystone taxa alongside the haptophyte diazotroph host Braarudosphaera bigelowii and chlorophytes. Our findings highlight an intriguing relationship between marine stramenopiles and high N 2 fixation coastal sites.

Nitrogen availability limits marine productivity across large ocean regions. Diazotrophs can supply new nitrogen to the marine environment via nitrogen (N 2 ) fixation, relieving nitrogen limitation. The distributions of diazotrophs and N 2 fixation have been hypothesized to be generally controlled by temperature, phosphorus, and iron availability in the global ocean. However, even in the North Atlantic where most research on diazotrophs and N 2 fixation has taken place, environmental controls remain contentious. Here we measure diazotroph composition, abundance, and activity at high resolution using newly developed underway sampling and sensing techniques. We capture a diazotrophic community shift from Trichodesmium to UCYN-A between the oligotrophic, warm (25-29 °C) Sargasso Sea and relatively nutrient-enriched, cold (13-24 °C) subpolar and eastern American coastal waters. Meanwhile, N 2 fixation rates measured in this study are among the highest ever recorded globally and show significant increase with phosphorus availability across the transition from the Gulf Stream into subpolar and coastal waters despite colder temperatures and higher nitrate concentrations. Transcriptional patterns in both Trichodesmium and UCYN-A indicate phosphorus stress in the subtropical gyre. Over this iron-replete transect spanning the western North Atlantic, our results suggest that temperature is the major factor controlling the diazotrophic community structure while phosphorous drives N 2 fixation rates. Overall, the occurrence of record-high UCYN-A abundance and peak N 2 fixation rates in the cold coastal region where nitrate concentrations are highest (~200 nM) challenges current paradigms on what drives the distribution of diazotrophs and N 2 fixation.

Primary production by phytoplankton represents a major pathway whereby atmospheric CO 2 is sequestered in the ocean, but this requires iron, which is in scarce supply. As over 99% of iron is complexed to organic ligands, which increase iron solubility and microbial availability, understanding the processes governing ligand dynamics is of fundamental importance. Ligands within humic-like substances have long been considered important for iron complexation, but their role has never been explained in an oceanographically consistent manner. Here we show iron co-varying with electroactive humic substances at multiple open ocean sites, with the ratio of iron to humics increasing with depth. Our results agree with humic ligands composing a large fraction of the iron-binding ligand pool throughout the water column. We demonstrate how maximum dissolved iron concentrations could be limited by the concentration and binding capacity of humic ligands, and provide a summary of the key processes that could influence these parameters. If this relationship is globally representative, humics could impose a concentration threshold that buffers the deep ocean iron inventory. This study highlights the dearth of humic data, and the immediate need to measure electroactive humics, dissolved iron and iron-binding ligands simultaneously from surface to depth, across different ocean basins.

Heme b is an iron-containing co-factor in hemoproteins. Heme b concentrations are low (<1 pmol L -1 ) in iron limited phytoplankton in cultures and in the field. Here, we determined heme b in marine particulate material (>0.7 μm) from the North Atlantic Ocean (GEOVIDE cruise - GEOTRACES section GA01), which spanned several biogeochemical regimes. We examined the relationship between heme b abundance and the microbial community composition, and its utility for mapping iron limited phytoplankton. Heme b concentrations ranged from 0.16 to 5.1 pmol L -1 (median = 2.0 pmol L -1 , n = 62) in the surface mixed layer (SML) along the cruise track, driven mainly by variability in biomass. However, in the Irminger Basin, the lowest heme b levels (SML: median = 0.53 pmol L -1 , n = 12) were observed, whilst the biomass was highest (particulate organic carbon, median = 14.2 μmol L -1 , n = 25; chlorophyll a : median = 2.0 nmol L -1 , n = 23) pointing to regulatory mechanisms of the heme b pool for growth conservation. Dissolved iron (DFe) was not depleted (SML: median = 0.38 nmol L -1 , n = 11) in the Irminger Basin, but large diatoms ( Rhizosolenia sp.) dominated. Hence, heme b depletion and regulation is likely to occur during bloom progression when phytoplankton class-dependent absolute iron requirements exceed the available ambient concentration of DFe. Furthermore, high heme b concentrations found in the Iceland Basin and Labrador Sea (median = 3.4 pmol L -1 , n = 20), despite having similar DFe concentrations to the Irminger Basin, were attributed to an earlier growth phase of the extant phytoplankton populations. Thus, heme b provides a snapshot of the cellular activity in situ and could both be used as indicator of iron limitation and contribute to understanding phytoplankton adaptation mechanisms to changing iron supplies.

The dinoflagellate Alexandrium minutum produces toxic compounds, including paralytic shellfish toxins, but also some unknown extracellular toxins. Although copper (Cu) is an essential element, it can impair microalgal physiology and increase their toxic potency. This study investigated the effect of different concentrations of dissolved Cu (7 nM, 79 nM and 164 nM) on A. minutum allelochemical potency, here defined as negative effects of a protist on competing protists through the release of chemicals. This was studied in relation to its physiology. The effects of Cu were assessed on A. minutum growth, reactive oxygen species level, photosynthesis proxies, lipid metabolism, exudation of dissolved organic compounds, allelochemical potency and on the associate free bacterial community of A. minutum. Only the highest Cu exposure (164 nM) inhibited and delayed the growth of A. minutum, and only in this treatment did the allelochemical potency significantly increase, when the dissolved Cu concentration was still toxic. Within the first 7 days of the high Cu treatment, the physiology of A. minutum was severely impaired with decreased growth and photosynthesis, and increased stress responses and free bacterial density per algal cell. After 15 days, A. minutum partially recovered from Cu stress as highlighted by the growth rate, reactive oxygen species level and photosystem II yields. This recovery could be attributed to the apparent decrease in background dissolved Cu concentration to a non-toxic level, suggesting that the release of exudates may have partially decreased the bioavailable Cu fraction. Overall, A. minutum appeared quite tolerant to Cu, and this work suggests that the modifications in the physiology and in the exudates help the algae to cope with Cu exposure. Moreover, this study shows the complex interplay between abiotic and biotic factors that can influence the dynamic of A. minutum blooms. Modulation in allelochemical potency of A. minutum by Cu may have ecological implications with an increased competitiveness of this species in environments contaminated with Cu., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Marine N 2 fixation supports a significant portion of oceanic primary production by making N 2 bioavailable to planktonic communities, in the process influencing atmosphere-ocean carbon fluxes and our global climate. However, the geographical distribution and controlling factors of marine N 2 fixation remain elusive largely due to sparse observations. Here we present unprecedented high-resolution underway N 2 fixation estimates across over 6000 kilometers of the western North Atlantic. Unexpectedly, we find increasing N 2 fixation rates from the oligotrophic Sargasso Sea to North America coastal waters, driven primarily by cyanobacterial diazotrophs. N 2 fixation is best correlated to phosphorus availability and chlorophyll-a concentration. Globally, intense N 2 fixation activity in the coastal oceans is validated by a meta-analysis of published observations and we estimate the annual coastal N 2 fixation flux to be 16.7 Tg N. This study broadens the biogeography of N 2 fixation, highlights the interplay of regulating factors, and reveals thriving diazotrophic communities in coastal waters with potential significance to the global nitrogen and carbon cycles.

Certification of trace metals in seawater certified reference materials (CRMs) NASS-7 and CASS-6 is described. At the National Research Council Canada (NRC), column separation was performed to remove the seawater matrix prior to the determination of Cd, Cr, Cu, Fe, Pb, Mn, Mo, Ni, U, V, and Zn, whereas As was directly measured in 10-fold diluted seawater samples, and B was directly measured in 200-fold diluted seawater samples. High-resolution inductively coupled plasma mass spectrometry (HR-ICPMS) was used for elemental analyses, with double isotope dilution for the accurate determination of B, Cd, Cr, Cu, Fe, Pb, Mo, Ni, U, and Zn in seawater NASS-7 and CASS-6, and standard addition calibration for As, Co, Mn, and V. In addition, all analytes were measured using standard addition calibration with triple quadrupole (QQQ)-ICPMS to provide a second set of data at NRC. Expert laboratories worldwide were invited to contribute data to the certification of trace metals in NASS-7 and CASS-6. Various analytical methods were employed by participants including column separation, co-precipitation, and simple dilution coupled to ICPMS detection or flow injection analysis coupled to chemiluminescence detection, with use of double isotope dilution calibration, matrix matching external calibration, and standard addition calibration. Results presented in this study show that majority of laboratories have demonstrated their measurement capabilities for the accurate determination of trace metals in seawater. As a result of this comparison, certified/reference values and associated uncertainties were assigned for 14 elements in seawater CRMs NASS-7 and CASS-6, suitable for the validation of methods used for seawater analysis.

The addition of iron to high-nutrient, low-chlorophyll regions induces phytoplankton blooms that take up carbon. Carbon export from the surface layer and, in particular, the ability of the ocean and sediments to sequester carbon for many years remains, however, poorly quantified. Here we report data from the CROZEX experiment in the Southern Ocean, which was conducted to test the hypothesis that the observed north-south gradient in phytoplankton concentrations in the vicinity of the Crozet Islands is induced by natural iron fertilization that results in enhanced organic carbon flux to the deep ocean. We report annual particulate carbon fluxes out of the surface layer, at three kilometres below the ocean surface and to the ocean floor. We find that carbon fluxes from a highly productive, naturally iron-fertilized region of the sub-Antarctic Southern Ocean are two to three times larger than the carbon fluxes from an adjacent high-nutrient, low-chlorophyll area not fertilized by iron. Our findings support the hypothesis that increased iron supply to the glacial sub-Antarctic may have directly enhanced carbon export to the deep ocean. The CROZEX sequestration efficiency (the amount of carbon sequestered below the depth of winter mixing for a given iron supply) of 8,600 mol mol(-1) was 18 times greater than that of a phytoplankton bloom induced artificially by adding iron, but 77 times smaller than that of another bloom initiated, like CROZEX, by a natural supply of iron. Large losses of purposefully added iron can explain the lower efficiency of the induced bloom(6). The discrepancy between the blooms naturally supplied with iron may result in part from an underestimate of horizontal iron supply.