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Iron (Fe) is an essential micronutrient for phytoplankton growth, but its scarcity in seawater limits primary productivity across much of the ocean. Most dissolved Fe (DFe) in seawater is complexed with Fe-binding organic ligands, a poorly constrained fraction of dissolved organic matter (DOM), which increase Fe residence time and impact Fe bioavailability. Here, we present the conditional concentration (LFe) and binding-strength (log KFe'Lcond) of Fe-binding ligands in the Western Tropical South Pacific (WTSP) Ocean during the GEOTRACES TONGA cruise (GPpr14). The transect crossed the Lau basin, a region subject to shallow hydrothermal Fe inputs that fuel intense diazotrophic activity, the oligotrophic South Pacific gyre, and the Melanesian basin. Organic speciation was analyzed by competitive ligand exchange adsorptive cathodic stripping voltammetry (CLE-AdCSV) using salicylaldoxime at 25 µM. We found a high mean LFe of 5.2 ± 1.2 nMeqFe (n = 103) across the entire transect, predominantly consisting of intermediate strength L2 ligands (84%; mean log KFe'Lcond of 11.6 ± 0.4), consistent with humic-like substances. DFe correlated with the humic-like component of the fluorescent DOM (HS-like FDOM), yet the electroactive Fe-binding humic-like substances (LFeHS) accounted for only 20 ± 13% of LFe in the mixed layer and 8 ± 6% in deep waters. Ligands were in large excess compared to DFe (mean excess ligand eLFe = 4.6 ± 1.1 nMeqFe), suggesting poor stabilization of DFe inputs. High LFe (up to 9 nMeqFe) in samples close to hydrothermal sites could be due to detoxification strategies from plankton communities toward hydrothermally-fueled toxic trace metals other than Fe, with an apparent dilution of the DOM from the Lau basin into neighboring regions. We also observed a different peak potential of the Fe salicylaldoxime complex detected by CLE-AdCSV between the Lau and Melanesian basins, and between surface and deep waters. To our knowledge, this change in potential has not

Iron (Fe) is an essential micronutrient for phytoplankton, particularly diazotrophs, which are abundant in the Western Tropical South Pacific Ocean (WTSP). Their success depends on the numerous trace metals, particularly iron, released from shallow hydrothermal vents along the Tonga Arc. This study aimed to explore the impact of hydrothermal fluids on particulate trace metal concentrations and biological activity. To identify the composition of sinking particles across a wide area of the WTSP, we deployed sediment traps at various depths, both close and further west of the Tonga Arc. Seafloor sediments were cored at these deployment sites, including at a remote location in the South Pacific Gyre. The sinking particles were composed of a large amount of biological material, indicative of the high productivity of the Lau Basin. A significant portion of this material was lithogenic of hydrothermal origin, as revealed through Al-Fe-Mn tracing. The sinking material showed similar patterns between lithogenic and biogenic fractions, indicating that hydrothermal input within the photic layer triggered surface production. A hydrothermal fingerprint was suggested in the sediments due to the high sedimentation rates and the presence of large, heterogeneous, trace metal-rich particles. The presence of nearby active deep hydrothermal sources was suspected near the Lau Ridge due to the large particle size and the significant enrichment of Fe and Mn. Overall, this study revealed that deep and shallow hydrothermal sources along with submarine volcanism have a significant influence on the biogeochemical signature of particles in the Lau Basin at large spatial and temporal scales.

In the Western Tropical South Pacific (WTSP) Ocean, a hotspot of dinitrogen fixation has been identified. The survival of diazotrophs depends, among others, on the availability of dissolved iron (DFe) largely originating, as recently revealed, from shallow hydrothermal sources located along the Tonga-Kermadec arc that fertilize the Lau Basin with this element. On the opposite, these fluids, released directly close to the photic layer, can introduce numerous trace metals at concentrations that can be toxic to surface communities. Here, we performed an innovative 9-day experiment in 300 L reactors onboard the TONGA expedition, to examine the effects of hydrothermal fluids on natural plankton communities in the WTSP Ocean. Different volumes of fluids were mixed with non-hydrothermally influenced surface waters (mixing ratio from 0 to 14.5%) and the response of the communities was studied by monitoring numerous stocks and fluxes (phytoplankton biomass, community composition, net community production, N2 fixation, thiol production, organic carbon and metal concentrations in exported material). Despite an initial toxic effect of hydrothermal fluids on phytoplankton communities, these inputs led to higher net community production and N2 fixation rates, as well as elevated export of organic matter relative to control. This fertilizing effect was achieved through detoxification of the environment, rich in potentially toxic elements (e.g., Cu, Cd, Hg), likely by resistant Synechococcus ecotypes able to produce strong binding ligands, especially thiols (thioacetamide-like and glutathione-like compounds). The striking increase of thiols quickly after fluid addition likely detoxified the environment, rendering it more favorable for phytoplankton growth. Indeed, phytoplankton groups stressed by the addition of fluids were then able to recover important growth rates, probably favored by the supply of numerous fertilizing trace metals (notably Fe) from hydrothermal fluids and new n

The high N2 fixation rate observed in the Lau Basin of the western tropical South Pacific Ocean (WTSP) is fueled by iron (Fe) released from shallow hydrothermal systems. Understanding Fe bioavailability is crucial but the controls on the stability and bioavailability of hydrothermal Fe inputs are still poorly understood. Here, we provide new data on the spatial and vertical distribution of the soluble ubiquitous humic-like ligands (LFeHS) and their associated dissolved Fe (DFe) in the WTSP, including in samples near hydrothermal vents. Our data show that LFeHS are heterogenous ligands with binding sites of both strong and intermediate strengths. These ligands are primarily produced in surface waters and partially mineralized in mesopelagic waters. A substantial fraction of DFe was complexed by LFeHS (mean ~30%). The DFe complexed by LFeHS is likely bioavailable to phytoplankton and LFeHS stabilized Fe released by the mineralization of sinking biomass. However, unsaturation of LFeHS by Fe suggest that part of DFe is not available for complexation with LFeHS. Possible reasons are competition between DFe and other metals, such as dissolved copper, or the inability of LFeHS to access colloidal DFe. The study of two volcanic sites indicates that LFeHS were not produced in these hydrothermal systems. At the active site (DFe ~50 nmol L-1), LFeHS can only partially solubilize the hydrothermal DFe released in this area (1~5.5% of the total DFe). We performed controlled laboratory experiments which show that the observed low solubilization yield result from the inability of LFeHS to solubilize aged Fe oxyhydroxides (FeOx - a kinetically mediated process) and to form stable complexes with Fe(II) species. Our study provides new understanding of the role of LFeHS on the bioavailability and stabilization of hydrothermal DFe.

Iron is an essential nutrient that regulates productivity in ~30% of the ocean. Compared with deep (>2000 meter) hydrothermal activity at mid-ocean ridges that provide iron to the ocean’s interior, shallow (<500 meter) hydrothermal fluids are likely to influence the surface’s ecosystem. However, their effect is unknown. In this work, we show that fluids emitted along the Tonga volcanic arc (South Pacific) have a substantial impact on iron concentrations in the photic layer through vertical diffusion. This enrichment stimulates biological activity, resulting in an extensive patch of chlorophyll (360,000 square kilometers). Diazotroph activity is two to eight times higher and carbon export fluxes are two to three times higher in iron-enriched waters than in adjacent unfertilized waters. Such findings reveal a previously undescribed mechanism of natural iron fertilization in the ocean that fuels regional hotspot sinks for atmospheric CO2.

In the Western Tropical South Pacific, a hotspot of N2-fixing organisms has recently been identified. The survival of these species depends on the availability of dissolved iron (dFe). dFe was measured along a transect from 175 °E to 166 °W near 19-21 °S. The distribution of dFe showed high spatial variability: low concentrations (~0.2 nmol kg-1) in the South Pacific gyre and high concentrations (up to 50 nmol kg-1) west of the Tonga arc, indicating that this arc is a clear boundary between iron-poor and iron-rich waters. An optimal multiparameter analysis was used to distinguish the relative importance of physical transport relative to non-conservative processes on the observed dFe distribution. This analysis demonstrated that distant sources of iron play a minor role in its distribution along the transect. The high concentrations observed were therefore attributed to shallow hydrothermal sources massively present along the Tonga-Kermadec arc. Nevertheless, in contrast to what has been observed for deep hydrothermal plumes, our results highlighted the rapid decrease in dFe concentrations near shallow hydrothermal sources. This is likely due to a shorter residence time of surface water masses combined with several biogeochemical processes at play (e.g., precipitation, photoreduction, scavenging, biological uptake). This study clearly highlights the role of shallow hydrothermal sources on the dFe cycle within the Tonga-Kermadec arc where a strong link to biological activity in surface waters can be assessed. It also emphasizes the need to consider the impact of these shallow hydrothermal sources for a better understanding of the global iron cycle.

The unicellular diazotrophic cyanobacterium Crocosphaera contributes significantly to fixed nitrogen inputs in the oligotrophic ocean. In the western tropical South Pacific Ocean (WTSP), these diazotrophs abound thanks to the phosphorus-rich waters provided by the South Equatorial Current, and iron provided aeolian and subsurface volcanic activity. East of the WTSP, the South Pacific Gyre (SPG) harbors the most oligotrophic and transparent waters of the world's oceans, where only heterotrophic diazotrophs have been reported before. Here, in the SPG, we detected unexpected accumulation of Crocosphaera at 50 m with peak abundances of 5.26 × 105 nifH gene copies l–1. The abundance of Crocosphaera at 50 m was in the same order of magnitude as those detected westwards in the WTSP and represented 100% of volumetric N2 fixation rates. This accumulation at 50 m was likely due to a deeper penetration of UV light in the clear waters of the SPG being detrimental for Crocosphaera growth and N2 fixation activity. Nutrient and trace metal addition experiments did not induce any significant changes in N2 fixation or Crocosphaera abundance, indicating that this population was not limited by the resources tested and could develop in high numbers despite the oligotrophic conditions. Our findings indicate that the distribution of Crocosphaera can extend into subtropical gyres and further understanding of their controlling factors is needed.

his study reports the only recent characterisation of two contrasted wet deposition events collected during the PEACETIME cruise in the Mediterranean open seawater, and their impact on trace metals (TMS) marine stocks. Rain samples were analysed for Al, 12 trace metals (TMs hereafter, including Co, Cd, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Ti, V and Zn) and nutrients (N, P, DOC) concentrations. The first rain sample collected in the Ionian Sea (rain ION) was a wet typical regional background deposition event whereas the second rain collected in the Algerian Basin (rain FAST) was a Saharan dust wet deposition. The concentrations of TMs in the two rain samples were significantly lower compared to concentrations in rains collected at coastal sites reported in the literature, suggesting either less anthropogenic influence in the remote Mediterranean environment, or decreased emissions during the last decades in the Mediterranean Sea. The TMs inventories in the surface microlayer and mixed layer (0–20 m) at ION and FAST stations before and after the events, compared to atmospheric fluxes, showed that the atmospheric inputs were a significant source of particulate TMs for both layers. At the scale of the western and central Mediterranean, the atmospheric inputs were of the same order of magnitude as marine stocks within the ML for dissolved Fe, Co and Zn, underlining the role of the atmosphere in their biogeochemical cycle in the stratified Mediterranean Sea. In case of intense wet dust deposition event, the contribution of atmospheric inputs could be critical for dissolved stocks of the majority of TMs.

In the oligotrophic waters of the Mediterranean Sea, during the stratification period, the microbial loop relies on pulsed inputs of nutrients through atmospheric deposition of aerosols from both natural (Saharan dust) and anthropogenic origins. While the influence of dust deposition on microbial processes and community composition is still not fully constrained, the extent to which future environmental conditions will affect dust inputs and the microbial response is not known. The impact of atmospheric wet dust deposition was studied both under present and future (warming and acidification) environmental conditions through experiments in 300 L climate reactors. Three dust addition experiments were performed with surface seawater collected from the Tyrrhenian Sea, Ionian Sea and Algerian basin in the Western Mediterranean Sea during the PEACETIME cruise in May–June 2017. Top-down controls on bacteria, viral processes and community, as well as microbial community structure (16S and 18S rDNA amplicon sequencing) were followed over the 3–4 days experiments. Different microbial and viral responses to dust were observed rapidly after addition and were most of the time higher when combined to future environmental conditions. The input of nutrients and trace metals changed the microbial ecosystem from bottom-up limited to a top-down controlled bacterial community, likely from grazing and induced lysogeny. The composition of mixotrophic microeukaryotes and phototrophic prokaryotes was also altered. Overall, these results suggest that the effect of dust deposition on the microbial loop is dependent on the initial microbial assemblage and metabolic state of the tested water, and that predicted warming, and acidification will intensify these responses, affecting food web processes and biogeochemical cycles.

This study reports the only recent characterization of two contrasted wet deposition events collected during the PEACETIME (ProcEss studies at the Air–sEa Interface after dust deposition in the MEditerranean Sea) cruise in the open Mediterranean Sea (Med Sea) and their impact on trace metal (TM) marine stocks. Rain samples were analysed for Al, 12 TMs (Co, Cd, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Ti, V and Zn) and nutrient (N, P, dissolved organic carbon) concentrations. The first rain sample collected in the Ionian Sea (Rain ION) was a typical regional background wet deposition event, whereas the second rain sample collected in the Algerian Basin (Rain FAST) was a Saharan dust wet deposition event. Even in the remote Med Sea, all background TM inputs presented an anthropogenic signature, except for Fe, Mn and Ti. The concentrations of TMs in the two rain samples were significantly lower compared to concentrations in rains collected at coastal sites reported in the literature, due to the decrease in anthropogenic emissions during the preceding decades. The atmospheric TM inputs were mainly dissolved forms, even in dusty Rain FAST. The TM stocks in the mixed layer (ML, 0–20 m) at the FAST station before and after the event showed that the atmospheric inputs were a significant supply of particulate TMs and dissolved Fe and Co for surface seawater. Even if the wet deposition delivers TMs mainly in soluble form, the post-deposition aerosol dissolution could to be a key additional pathway in the supply of dissolved TMs. At the scale of the western and central Mediterranean, the atmospheric inputs were of the same order of magnitude as ML stocks for dissolved Fe, Co and Zn, highlighting the role of the atmosphere in their biogeochemical cycles in the stratified Med Sea. In case of intense dust-rich wet deposition events, the role of atmospheric inputs as an external source was extended to dissolved Co, Fe, Mn, Pb and Zn. Our results suggest that the wet deposition constitutes only

N2 fixation rates were measured in the 0-1000ĝ€¯m layer at 13 stations located in the open western and central Mediterranean Sea (MS) during the PEACETIME cruise (late spring 2017). While the spatial variability in N2 fixation was not related to Fe, P nor N stocks, the surface composition of the diazotrophic community indicated a strong longitudinal gradient increasing eastward for the relative abundance of non-cyanobacterial diazotrophs (NCDs) (mainly 3-Proteobacteria) and conversely decreasing eastward for photo-heterotrophic group A (UCYN-A) (mainly UCYN-A1 and UCYN-A3), as did N2 fixation rates. UCYN-A4 and UCYN-A3 were identified for the first time in the MS. The westernmost station influenced by Atlantic waters and characterized by highest stocks of N and P displayed a patchy distribution of diazotrophic activity with an exceptionally high rate in the euphotic layer of 72.1ĝ€¯nmolNL-1d-1, which could support up to 19ĝ€¯% of primary production. At this station at 1ĝ€¯%PAR (photosynthetically available radiation) depth, UCYN-A4 represented up to 94ĝ€¯% of the diazotrophic community. These in situ observations of greater relative abundance of UCYN-A at stations with higher nutrient concentrations and dominance of NCDs at more oligotrophic stations suggest that nutrient conditions-even in the nanomolar range-may determine the composition of diazotrophic communities and in turn N2 fixation rates. The impact of Saharan dust deposition on N2 fixation and diazotrophic communities was also investigated, under present and future projected conditions of temperature and pH during short-Term (3-4ĝ€¯d) experiments at three stations. New nutrients from simulated dust deposition triggered a significant stimulation of N2 fixation (from 41ĝ€¯% to 565ĝ€¯%). The strongest increase in N2 fixation was observed at the stations dominated by NCDs and did not lead on this short timescale to changes in the diazotrophic community composition. Under projected future conditions, N2 fixatio