Essential trace metals (e.g., Fe, Co, Cu) are vital for phytoplankton metabolism and marine biogeochemical cycles, while toxic metals and emerging contaminants (e.g., Cd, Pb, Hg, Li, microplastics) pose ecological risks. Their bioavailability and transfer through marine food webs depend partly on their chemical form (speciation between dissolved, colloidal, particulate) and biological uptake by plankton. These processes – chemical speciation and trophic transfer - can modify phytoplankton community structure and the entire marine food web with potential consequences for ecosystem functioning.To investigate how metals and contaminants transfer through the water column and plankton, a mesocosm experiment conditions was carried out. Mesocosms with the natural phytoplanktonic assemblage from Villefranche Bay (Mediterranean Sea, France) and copepods collected from the same location were exposed to a gradient of metals, Li and UV-degraded microplastics, ranging from present-day concentration to levels representative of plausible future environmental scenarios.This experiment was conducted in 9 x 300 L with a 1 m high water column allowing the development of export fluxes. Major nutrients were added in all mesocosm to insure the phytoplanktonic development before metals and contaminants additions of treatment. Treatments were as follow : 1 mesocosm control; 3 mesocosms with x1.5, x2 and x5 of natural metals concentrations (Fe, Mn, Zn, Co, Cd, Cu, Ni and Li); 2 mesocosms with addition of different concentrations of UV-degraded polypropylene (10 and 160 µg/L, size distribution centred at ~50 µm); and 3 mesocosms with different concentrations of both metals and microplastics. During the 17-day experiment biological parameters (nutrient concentrations, biovolume, particulate organic carbon and nitrogen, pigment concentration and cell abondance) were monitored throughout the experiment and first results indicate an initial exponential growth phase, followed by nutrient limitation and a transition toward heterotrophic conditions. Metals concentrations will be analysed in colloidal (3kDa – 0.22 µm), dissolved (< 0.22 µm) and particulate (> 0.22µm) fractions. The particulate fraction, included microphytoplankton, was rinsed with EDTA/oxalate to quantify intracellular metals. Zooplankton was sampled at the beginning and the end of the experiment to assess potential bioaccumulation. Exported material was collected daily to quantify and characterize export fluxes. These data will allow determination of partition coefficients and bioaccumulation. Daily photophysiological measurements - including the maximum quantum yield (Fv/Fm), absorption cross-section (SigmaPSII) of photosystem II, photosynthesis–irradiance curves and photoprotection capacity - will enable the detection of any potential adverse effects of the treatment on the physiological status of phytoplankton. This presentation will report on the experiment and present preliminary results on the partition coefficients and bioaccumulation of metals and contaminants, and will explore their potential impact on phytoplankton and zooplankton communities.

The Mediterranean basin faces enhanced wildfire risks associated with human-driven climate and land use changes. Wildfire-generated aerosols can reach the ocean, where they may subsequently impact marine prokaryotic communities, key drivers of global biogeochemical cycles. However, our understanding of the influence of wildfire airborne particles on the abundance and composition of marine microbes remains limited. We conducted experiments in which surface water from the northwestern Mediterranean Sea was incubated in 300 L minicosms amended with varying amounts of wildfire fine ash particles, previously collected during a Mediterranean wildfire. Wet deposition of wildfire fine ash particles had a short-term effect on prokaryotes by increasing their abundance and diversity, likely due to the release of both inorganic and organic substrates, alleviating nutrient limitations. Ash deposition could also indirectly affect prokaryotic communities via changes in the composition of phytoplankton populations. These mechanisms induced changes in prokaryotic community composition, reflecting a succession of taxa likely adapted to different substrate qualities. Ash had a negative effect on Cyanobiaceae but promoted the growth of Flavobacteriaceae, Rhodobacteraceae and SAR11 clade I among other taxa. Our findings demonstrate that wildfire ash can alter Mediterranean prokaryotic communities during oligotrophic periods, further exacerbating the impact of wildfires on marine ecosystems.

The Western Tropical South Pacific has recently been identified as a global hotspot for microbial dinitrogen fixation and shallow hydrothermal activity, yet the dynamics of dissolved organic matter (DOM) in this ecosystem remains understudied. During the TONGA cruise (2019), we investigated the distribution of dissolved organic carbon (DOC), chromophoric DOM (CDOM) and fluorescent DOM (FDOM) from Melanesian waters to the South Pacific Gyre, including the Lau Basin/Tonga-Kermadec Volcanic Arc. DOC concentration, CDOM absorption [aCDOM(254)], the CDOM spectral slope (S275-295) and tyrosine-like fluorescence decreased from surface to deep waters across subregions. In contrast, apparent oxygen utilization (AOU), nutrients, aCDOM(350), specific UV absorbance (SUVA254), humic-like fluorescence, humification (HIX) and combustion (COX) indices increased with depth. These distributions reveal 1) the production of labile, low molecular weight DOM by phytoplankton, and photobleaching in the photic layer, and 2) the production of higher molecular weight, bio-refractory DOM from the remineralization of sinking particulate organic carbon and DOC in deeper waters. Also, the tryptophan-like fluorescence peaks at depth could be associated with the presence of sinking Trichodesmium spp. Regional variations in DOM characteristics were less pronounced than water-mass-related differences but revealed subtle trends along the west-east gradient, with overall higher DOC, CDOM and FDOM levels in the Melanesian and Lau Basin/Arc subregions compared to the South Pacific Gyre. At 200-m depth near the Arc, the release of hydrothermal fluids altered the DOM composition close to the vent, with significant increases in aCDOM(254) and tyrosine-like material, and significant decreases in HIX and COX indices. We further show an indirect, large-scale impact of shallow hydrothermal vents on the DOM stock in the 0–50-m surface layer, driven by the iron fertilization-induced stimulation of planktonic activity in the photic zone. The increased DOM stocks were observed mostly in the Lau Basin/Arc subregion but extending to Melanesian waters and the western edge of South Pacific Gyre. Collectively, these processes shape the optical properties and biogeochemical behavior of DOM, highlighting the importance of hydrothermal systems in the oceanic carbon cycle.

Methylmercury is a bioaccumulative neurotoxin that poses severe risks to marine ecosystems and human health worldwide. Hydrothermal systems and submarine volcanoes are natural sources of mercury, yet the magnitude of emissions, their transport, and their impact on marine ecosystems remain poorly understood. Quantifying natural mercury fluxes is essential to understanding anthropogenic perturbations and guiding effective reduction strategies. We investigate hydrothermal mercury inputs at the Tonga volcanic arc and their impact on the local ecosystem. Our results show that hydrothermal and volcanic activity in the Tonga Arc increases mercury concentrations in seawater. Comprehensive surveys identified mercury-rich plumes (up to 22.7 pmol L-1) associated with high mercury fluxes (4763 pmol m-2 day-1) reaching productive surface waters, resulting in an estimated total flux of 4.23 t y-1 for the entire Tonga Arc. Despite these significant inputs, mercury concentrations in phytoplankton remain unexpectedly low. We demonstrate that phytoplankton blooms, stimulated by natural iron fertilization from hydrothermal sources, dilute mercury at the cellular level, reducing the impact of hydrothermal mercury. Additionally, we provide a revised global estimate of hydrothermal mercury inputs with a maximum of 120 t y-1, which is considerably lower than atmospheric and riverine inputs to the ocean.

Monomethylmercury (MMHg) is a potent neurotoxin causing neurodevelopmental delays and cardiovascular and immunological issues. Human exposure primarily occurs through seafood consumption due to MMHg bioaccumulation and biomagnification from seawater into marine organisms. Determining MMHg in seawater at ultratrace concentrations poses logistical and analytical challenges. Diffusive Gradient in Thin-film (DGT) samplers represent a promising solution, which captures time-averaged concentrations by preconcentrating in situ MMHg over a defined exposure time. DGT manufactured with 3-mercaptopropyl-functionalized silica (3MFS) in agarose and polyacrylamide gels were tested and compared for the determination of MMHg present in open ocean and coastal waters. Different elution methods using acidic thiourea were tested to reach precise, accurate and quantitative elution of MMHg from the binding gel. We found that polyacrylamide-3MFS binding gels display a higher elution efficiency (94 ± 3 %), precision and better handling compared to agarose-3MFS gels (41 ± 6 %). A unique mooring line installed in the South Western Tropical Pacific Ocean, provided monthly DGT-MMHg concentrations over a year showing potential seasonal differences in MMHg concentrations ranging between 18 and 106 fM. DGT were also deployed in shallow Peruvian coastal waters, exhibiting higher MMHg concentrations (170 ± 97, n = 26) with typical benthopelagic gradients. DGT-MMHg concentrations were in good agreement with discrete water samples analyzed by reference methods using isotope dilution. DGTs offer complementary advantages over oceanographic cruises, notably in situ preconcentration, low blanks, minimal logistical requirements and cost-effectiveness. DGTs represent a valuable tool for studying the marine MMHg cycle for evaluating the implementation of the Minamata Convention.

In marine ecosystems, most physiological, ecological, or physical processes are size dependent. These include metabolic rates, the uptake of carbon and other nutrients, swimming and sinking velocities, and trophic interactions, which eventually determine the stocks of commercial species, as well as biogeochemical cycles and carbon sequestration. As such, broad-scale observations of plankton size distribution are important indicators of the general functioning and state of pelagic ecosystems under anthropogenic pressures. Here, we present the first global datasets of the Pelagic Size Structure database (PSSdb), generated from plankton imaging devices. This release includes the bulk particle normalized biovolume size spectrum (NBSS) and the bulk particle size distribution (PSD), along with their related parameters (slope, intercept, and R2) measured within the epipelagic layer (0–200 m) by three imaging sensors: the Imaging FlowCytobot (IFCB), the Underwater Vision Profiler (UVP), and benchtop scanners. Collectively, these instruments effectively image organisms and detrital material in the 7–10 000 µm size range. A total of 92 472 IFCB samples, 3068 UVP profiles, and 2411 scans passed our quality control and were standardized to produce consistent instrument-specific size spectra averaged to 1° × 1° latitude and longitude and by year and month. Our instrument-specific datasets span most major ocean basins, except for the IFCB datasets we have ingested, which were exclusively collected in northern latitudes, and cover decadal time periods (2013–2022 for IFCB, 2008–2021 for UVP, and 1996–2022 for scanners), allowing for a further assessment of the pelagic size spectrum in space and time. The datasets that constitute PSSdb's first release are available at https://doi.org/10.5281/zenodo.11050013 (Dugenne et al., 2024b). In addition, future updates to these data products can be accessed at https://doi.org/10.5281/zenodo.7998799.

During the TONGA cruise (2019), seawater samples were collected to assess the effect of volcanic eruption versus submarine hydrothermal system on the water column. For this purpose, two locations were investigated, the first one located directly under the influence of the New Late’iki island (eruption in October 2019), and the second one showing ongoing submarine hydrothermal activity. At both locations, the total strontium (TSr) and lithium (TLi) concentrations vary between 94.4 and 152.3 µmol/L and 13.2 and 203.5 µmol/L, respectively. When combined, TSr and TLi concentrations of all samples in the water column are higher than those of the oligotrophic water. Both volcanic eruption and submarine hydrothermal activity (e.g. volcanic ashes, particles, gas condensate) can deliver substantial amount of TSr and TLi to the water column. The distribution of TSr versus TLi evidences linear trends either with a negative or positive slope. The negative correlation is observed in the water column at both sites, directly under the influence of the eruption and in the vicinity of the volcano with hydrothermal activity. The positive TSr versus TLi correlation is observed at site under submarine hydrothermal influence and is in line with black smokers related hydrothermal plumes. The 87Sr/86Sr ratios vary between 0.709147 and 0.709210 and δ7Li values vary between +10.1 and +37.6 ‰. While 92% of the measured 87Sr/86Sr ratios are in line with the mean value of oligotrophic waters, once combined with the δ7Li values, only 20% of them remains within this field. The wide range of δ7Li values decreases from sea-surface down to ~140 mbsl, before increasing at greater depth, while defining different linear trend according to the dissolved inorganic carbon concentrations. The variability of δ7Li values reflect hydrothermal contribution, mineral–seawater interaction and potentially biology–environment interaction. In the particular geological setting of the study, where both hydrothermal and volcanic activities were at play, disentangling both contributions on water column implies a combined use of elemental and isotopic signatures of Sr and Li tracers.

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 previously been reported; whether this represents a novel detection of specificities in DOM composition merits further investigation. Competition between Fe and competing metals for ligand binding sites could favor DFe oxidation and precipitation near hydrothermal vents and explain the absence of strong Fe stabilization in the WTSP.

The Western Tropical South Pacific (WTSP) basin has been identified as a hotspot of atmospheric dinitrogen fixation due to the high dissolved iron ([DFe]) concentrations (up to 66 nM) in the photic layer linked with the release of shallow hydrothermal fluids along the Tonga-Kermadec arc. Yet, the effect of such hydrothermal fluids in structuring the plankton community remains poorly studied. During the TONGA cruise (November-December 2019), we collected micro- (20-200 μm) and meso-plankton (>200 μm) samples in the photic layer (0-200 m) along a west to east zonal transect crossing the Tonga volcanic arc, in particular two volcanoes associated with shallow hydrothermal vents (< 500 m) in the Lau Basin, and both sides of the arc represented by Melanesian waters and the South Pacific Gyre. Samples were analyzed by quantitative imaging (FlowCam and ZooScan) and then coupled with acoustic observations, allowing us to study the potential transfer of phytoplankton blooms to higher planktonic trophic levels. We show that micro- and meso-plankton exhibit high abundances and biomasses in the Lau Basin and, to some extent, in Melanesian waters, suggesting that shallow hydrothermal inputs sustain the planktonic food web, creating productive waters in this otherwise oligotrophic region. In terms of planktonic community structure, we identified major changes with high [DFe] inputs, promoting the development of a low diversity planktonic community dominated by diazotrophic cyanobacteria. Furthermore, in order to quantify the effect of the shallow hydrothermal vents on chlorophyll a concentrations, we used Lagrangian dispersal models. We show that chlorophyll a concentrations were significantly higher inside the Lagrangian plume, which came into contact with the two hydrothermal sites, confirming the profound impact of shallow hydrothermal vents on plankton production.

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.

The spatial distribution of marine di-nitrogen (N2) fixation informs our understanding of the sensitivities of this process as well as the potential for this new nitrogen (N) source to drive export production, influencing the global carbon (C) cycle and climate. Using geochemically-derived δ15N budgets, we quantified rates of N2 fixation and its importance for supporting export production at stations sampled near the southwest Pacific Tonga-Kermadec Arc. Recent observations indicate that shallow (<300 m) hydrothermal vents located along the arc provide significant dissolved iron to the euphotic zone, stimulating N2 fixation. Here we compare measurements of water column δ15NNO3+NO2 with sinking particulate δ15N collected by short-term sediment traps deployed at 170 m and 270 m at stations in close proximity to subsurface hydrothermal activity, and the δ15N of N2 fixation. Results from the δ15N budgets yield high geochemically-based N2 fixation rates (282 to 638 µmol N m-2 d-1) at stations impacted by hydrothermal activity, supporting 64 to 92% of export production in late spring. These results are consistent with contemporaneous 15N2 uptake rate estimates and molecular work describing high Trichodesmium spp. and other diazotroph abundances associated with elevated N2 fixation rates. Further, the δ15N of sinking particulate N collected at 1000 m over an annual cycle revealed sinking fluxes peaked in the summer and coincided with the lowest δ15N, while lower winter sinking fluxes had the highest δ15N, indicating isotopically distinct N sources supporting export seasonally, and aligning with observations from most other δ15N budgets in oligotrophic regions. Consequently, the significant regional N2 fixation input to the late spring/summer Western Tropical South Pacific results in the accumulation of low-δ15NNO3+NO2 in the upper thermocline that works to lower the elevated δ15NNO3+NO2 generated in the oxygen deficient zones in the Eastern Tropical South Pacific.

The sea surface microlayer (SSML) is critical to air-sea exchanges of gases and primary aerosols. However, despite the extent of this boundary layer, little is known about its specific bacterial community (bacterioneuston) and how it may affect ocean-atmosphere exchanges. Here, we studied the bacterial community composition in the surface waters of three different basins of the Western Mediterranean Sea and assessed the selective air-sea transfer of marine bacteria through experimental nascent sea spray aerosol production in a 10 L tank with plunging jets. In situ, the bacterioneuston harbored basin-specific enriched taxa and followed a similar spatial pattern as the underlying bacterioplankton community. Aerosolization potential showed that sea spray taxa might be recruited from both the underlying water and the SSML, and that taxa enriched in the bacterioneuston were not always aerosolized. Our results suggest that the Mediterranean nutrient gradient, as well as pulse events such as dust deposition, affect the distribution of the bacterial community at the ocean-atmosphere interface, which may impact biogeochemical processes, climate regulation and bacterial dispersal through aerosolization.

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 (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 nitrogen provided by N2 fixation. These experimental results are in good agreement with in-situ observations, proving the causal link between the supply of hydrothermal fluids emitted at shallow depth into the surface layer and the intense biological productivity largely supported by diazotrophs in the WTSP Ocean. This study highlights the importance of considering shallow hydrothermal systems for a better understanding of the biological carbon pump.