<div><p>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)],</p><p>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 3 properties and biogeochemical behavior of DOM, highlighting the importance of hydrothermal systems in the oceanic carbon cycle.</p></div>

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.

Abstract. Particles of marine origin may act as ice nuclei when clouds form and therefore influence cloud properties and lifetime. Here we investigate the abundance of Ice Nuclei Particles in bulk seawater (INPSW) collected in natural seawater of the Western Tropical South Pacific and in sea spray aerosol (INPSSA) artificially generated from the surface seawater. The study area was separated into two oligotrophic zones (the Melanesian Basin and the Western South Pacific Gyre), and a mesotrophic one (the Lau basin), characterized by high plankton biomass due iron fertilization by underwater hydrothermal activity of the Tonga volcanic arc. Our results show that INPSW were on average 80 % heat labile, strongly suggesting a biological origin. INPSW concentrations were two-fold higher in the Lau basin as compared to both oligotrophic areas at all freezing temperatures. This trend is consistent with a higher abundance of planktonic microorganisms, pigments and particulate organic carbon (POC) concentrations in the Lau basin. Over the whole cruise transect, medium to strong correlations were found between INPSW concentrations and pigments (notably with bacteriochlorophyll-a and carotene), bacterial abundance and POC. The heat stable fraction of INPSW exhibited correlations with Dissolved Organic Carbon (DOC) concentrations and were not as variable as the heat labile INPSW. In the nascent sea spray, INPSSA were also mostly heat labile in coherence with the INPSW. INPSSA were predominantly (60 %), submicron in size (presumed originating from film drops), but the supermicron INPSSA constituted 40 % of the INPSSA and were all heat labile (presumably originating from jet drops). Supermicron INPSSA were between 60 to 80 % heat stable with a high variability between samples, indicating different nature of the two fractions of INPs. Supermicron INPSSA were generally more abundant in the Lau basin, while submicron INPSSA did not exhibit any significant difference between the three regions. We report a transfer function of seawater INPs to SSA INPs of 1.70 m-2.LSW and 3.3 m-2.LSW for heat stable INPs, hinting that heat stable INPs were more efficiently transferred to the SSA. Our results suggest that hydrothermal activity indirectly enhances the INP concentration of surface waters, through boosting the biological activity, which results in increases of the ice forming ability of supermicron sea spray particle. Given the extent of hydrothermal activity throughout the global Ocean, its impact on cloud properties should be considered in future ocean-atmosphere interaction studies.

Methylmercury is a bioaccumulative neurotoxin that poses severe risks to marine ecosystems 31 and human health worldwide. Hydrothermal systems and submarine volcanoes are natural 32 sources of mercury, yet the magnitude of emissions, their transport, and their impact on marine 33 ecosystems remain poorly understood. Quantifying natural mercury fluxes is essential to 34 understanding anthropogenic perturbations and guiding effective reduction strategies. We 35 investigate hydrothermal mercury inputs at the Tonga volcanic arc and their impact on the 36 local ecosystem. Our results show that hydrothermal and volcanic activity in the Tonga Arc 37 increases mercury concentrations in seawater. Comprehensive surveys identified mercury-38 rich plumes (up to 22.7 pmol l -1 ) associated with high mercury fluxes (4,763 pmol m -2 day -1 ) 39 reaching productive surface waters, resulting in an estimated total flux of 4.23 t y -1 for the 40 entire Tonga Arc. Despite these significant inputs, mercury concentrations in phytoplankton 41 remain unexpectedly low. We demonstrate that phytoplankton blooms, stimulated by natural 42 iron fertilization from hydrothermal sources, dilute mercury at the cellular level, reducing the 43 impact of hydrothermal mercury. Additionally, we provide a revised global estimate of 44 hydrothermal mercury inputs with a maximum of 120 t y -1 , which is considerably lower than 45 atmospheric and riverine inputs to the ocean.

Le long de l'arc volcanique des Tonga, au large de la Nouvelle-Calédonie, une zone très productive et importante pour la pêche a été identifiée dans le vaste désert océanique du Pacifique tropical. Un mystère éclairci grâce à une campagne océanographique.

Along Tonga's volcanic arc, off the coast of New Caledonia, a highly productive major fishing zone has been identified in the vast ocean 'desert' of the tropical Pacific. A mysterious phenomenon brought to light by oceanographic research.

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 (L Fe ) and binding-strength (log K F e ' L c o n d ) 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 L Fe of 5.2 ± 1.2 nMeqFe (n = 103) across the entire transect, predominantly consisting of intermediate strength L2 ligands (84%; mean log K F e ' L c o n d 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 (L FeHS ) accounted for only 20 ± 13% of L Fe in the mixed layer and 8 ± 6% in deep waters. Ligands were in large excess compared to DFe (mean excess ligand eL Fe = 4.6 ± 1.1 nMeqFe), suggesting poor stabilization of DFe inputs. High L Fe (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.

Abstract. 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 87 Sr/ 86 Sr ratios vary between 0.709147 and 0.709210 and d 7 Li values vary between +10.1 and +37.6 ‰. While 92% of the measured 87 Sr/ 86 Sr ratios are in line with the mean value of oligotrophic waters, once combined with the d 7 Li values, only 20% of them remains within this field. The wide range of d 7 Li 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 d 7 Li 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.

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 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.

The high N 2 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 (L FeHS) and their associated dissolved Fe (DFe) in the WTSP, including in samples near hydrothermal vents. Our data show that L FeHS 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 L FeHS (mean ~30%). The DFe complexed by L FeHS is likely bioavailable to phytoplankton and L FeHS stabilized Fe released by the mineralization of sinking biomass. However, unsaturation of L FeHS by Fe suggest that part of DFe is not available for complexation with L FeHS. Possible reasons are competition between DFe and other metals, such as dissolved copper, or the inability of L FeHS to access colloidal DFe. The study of two volcanic sites indicates that L FeHS were not produced in these hydrothermal systems. At the active site (DFe ~50 nmol L-1), L FeHS 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 L FeHS 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 L FeHS on the bioavailability and stabilization of hydrothermal DFe.

Abstract Iron (Fe) is an essential micronutrient for diazotrophs, which are abundant in the Western Tropical South Pacific Ocean (WTSP). Their success depends on the numerous trace metals, particularly Fe, released from shallow hydrothermal vents along the Tonga Arc. This study aimed to explore the spatio‐temporal 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 (up to 88 mg d −1 ), indicative of the high productivity of the region. A significant portion of this material (∼21 ± 12 wt.%) 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 (>47 cm kyr −1 ) and the presence of large, heterogeneous, metal‐rich particles. The presence of nearby active deep hydrothermal sources was suspected near the Lau Ridge due to the large particle size (1–976 μm) and the significant excess of Fe and Mn (2–20 wt.%). Overall, this study revealed that hydrothermal sources have a significant influence on the biogeochemical signature of particles in the region.

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 CO 2 .

The spatial distribution of marine di-nitrogen (N 2 ) 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 δ 15 N budgets, we quantified rates of N 2 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 N 2 fixation. Here we compare measurements of water column δ 15 N NO3+NO2 with sinking particulate δ 15 N collected by short-term sediment traps deployed at 170 m and 270 m at stations in close proximity to subsurface hydrothermal activity, and the δ 15 N of N 2 fixation. Results from the δ 15 N budgets yield high geochemically-based N 2 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 15 N 2 uptake rate estimates and molecular work describing high Trichodesmium spp. and other diazotroph abundances associated with elevated N 2 fixation rates. Further, the δ 15 N of sinking particulate N collected at 1000 m over an annual cycle revealed sinking fluxes peaked in the summer and coincided with the lowest δ 15 N, while lower winter sinking fluxes had the highest δ 15 N, indicating isotopically distinct N sources supporting export seasonally, and aligning with observations from most other δ 15 N budgets in oligotrophic regions. Consequently, the significant regional N 2 fixation input to the late spring/summer Western Tropical South Pacific results in the accumulation of low-δ 15 N NO3+NO2 in the upper thermocline that works to lower the elevated δ 15 N NO3+NO2 generated in the oxygen deficient zones in the Eastern Tropical South Pacific.

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.

The objective of the TONGA oceanographic expedition was to study the control of productivity and carbon sequestration by micronutrients of shallow hydrothermal origin in the Western Tropical South Pacific (WTSP) Ocean. The 37-day oceanographic survey took place on board the R/V L’Atalante in 2019 between Oct. 31 to Dec. 6 (Nouméa-Nouméa). Over a large area of the WTSP the team acquired numerous results on both the entire water column (up to the sediment) and the atmosphere. Specific task are represented on figure 1: (task 1) to characterize chemically and optically shallow hydrothermal fluids and to compare the source from below (shallow hydrothermal fluids) with the source from above (atmospheric deposition); (task 2) to quantify the dynamical dispersion of the fluids at small and regional scale; (task 3) to investigate the impact of the shallow hydrothermal sources on the biological activity and diversity, and the feedback to the atmosphere via the oceanic emissions of primary and secondary aerosols. (Task 4) to communicate about the campaign (see for example our Tweeter account (https://twitter.com/tongaproject) and the movie (26’) both in French (https://www.youtube.com/watch?v=e5kAd0i6Dck) and English (https://www.youtube.com/watch?v=UeABf-cVR-k). A long west to east (up to the blue waters of the gyre) transect allowed to characterize the different biogeochemical provinces crossed and a focus in the region of the Lau Basin allowed to investigate the impact of shallow hydrothermal sources. A series of short and long stations allowed to fully characterize the stocks and the fluxes in the different provinces. Short-term (up to 10 days) processes studies have been conducted (drifting moorings and minicosms experiments). Part of these results will feed into important modeling work. A fixed mooring line launched at the end of the campaign and recovered in Nov. 2020 as well as the 7 ARGO floats and 20 drifting buoys that were dropped during the campaign provide a broader temporal context of the acquisitions done during the campaign. An important focus of the campaign was the trace metal characterization of the entire water column. For this, TONGA has been labeled by the international program GEOTRACES (https://www.geotraces.org/). The impact on biological communities of fluids is supported by the international IMBER program (https://imber.info/). The TONGA project is also part of the LEFE program (funding by LEFE-CYBER and LEFE-GMMC), the ANR (Appel à projets génériques) and the Fondation A-MIDeX of the Aix-Marseille Université.

N2 fixation rates were measured in the 0–1000 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 of N2 fixation was not related to Fe, P nor N stocks, the surface composition of the diazotrophic community indicated a strong eastward increasing longitudinal gradient for the relative abundance of non-cyanobacterial diazotrophs (NCD) (mainly γ-Proteobacteria) and conversely eastward decreasing for UCYN-A (mainly -A1 and -A3) as did N2 fixation rates. UCYN-A4 and 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 72.1 nmol N L−1 d−1, which could support up to 19 % of primary production. At this station at 1 %PAR depth, UCYN-A4 represented up to 94 % of the diazotrophic community. These in situ observations of higher UCYN-A relative abundance in nutrient rich stations while NCD increased in the more oligotrophic stations, suggest that the nutrient conditions could determine the composition of the diazotrophic communities and in turn the 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 (3–4 days) experiments at three stations. New nutrients from simulated dust deposition triggered a significant stimulation of N2 fixation (from 41 % to 565 %). The strongest increase in N2 fixation was observed at the stations dominated by NCD and did not lead on this short time scale to change in the diazotrophic community composition. Under projected future conditions, N2 fixation was either exacerbated or unchanged, in that later case this was probably due to a too low nutrient bioavailability or an increased grazing pressure. The future warming and acidification likely benefited NCD (Pseudomonas) and UCYN-A2 while disadvantaged UCYN-A3 without knowing which effect (alone or in combination) is the driver, especially since we do not know the temperature optima of these species not yet cultivated as well as the effect of acidification.

In the oligotrophic waters of the Mediterranean Sea, during the stratification period, the microbial loop relies on pulsed inputs of nutrients through the atmospheric deposition of aerosols from both natural (e.g., Saharan dust), anthropogenic, or mixed 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 environmental conditions (+3 <SUP>∘</SUP>C warming and acidification of −0.3 pH units), through experiments in 300 L climate reactors. In total, three Saharan 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 (ProcEss studies at the Air-sEa Interface after dust deposition in the MEditerranean sea) 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 d experiments. Different microbial and viral responses to dust were observed rapidly after addition and were, most of the time, more pronounced when combined with future environmental conditions. The dust input of nutrients and trace metals changed the microbial ecosystem from a bottom-up limited to a top-down controlled bacterial community, likely from grazing and induced lysogeny. The relative abundance of mixotrophic microeukaryotes and phototrophic prokaryotes also increased. 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 chapter presents the current knowledge on the impact of atmospheric deposition from natural sources, such as Saharan dust, and from anthropogenic activities, on marine chemistry and biogeochemistry of the open Mediterranean Sea. Results from process studies and observations at sea that have been conducted over the past decade are summarized along with recent findings from a numerical biogeochemical model of the ocean that accounts for atmospheric deposition.

A key Earth system science question is the role of atmospheric deposition in supplying vital nutrients to the phytoplankton that form the base of marine food webs. Industrial and vehicular pollution, wildfires, volcanoes, biogenic debris, and desert dust all carry nutrients within their plumes throughout the globe. In remote ocean ecosystems, aerosol deposition represents an essential new source of nutrients for primary production. The large spatiotemporal variability in aerosols from myriad sources combined with the differential responses of marine biota to changing fluxes makes it crucially important to understand where, when, and how much nutrients from the atmosphere enter marine ecosystems. This review brings together existing literature, experimental evidence of impacts, and new atmospheric nutrient observations that can be compared with atmospheric and ocean biogeochemistry modeling. We evaluate the contribution and spatiotemporal variability of nutrient-bearing aerosols from desert dust, wildfire, volcanic, and anthropogenic sources, including the organic component, deposition fluxes, and oceanic impacts. Expected final online publication date for the Annual Review of Marine Science, Volume 14 is January 2022. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.

In the Western Tropical South Pacific, a hotspot of dinitrogen-fixing organisms has been identified. The survival of these species depends on the availability of dissolved iron (DFe); however, the source of this DFe is still unclear. 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) in the 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 distribution. This analysis demonstrated that the shallow hydrothermal sources present along the Tonga-Kermadec arc are responsible for the high concentrations observed in the photic layer. 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 (precipitation, scavenging, biological uptake, and photoreduction). 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, despite the small but significant fraction of DFe ultimately stabilized. It also emphasizes the need to consider the impact of these sources for a better understanding of the global iron cycle.

Mediterranean atmospheric pollution sources, processes, and impacts are summarized in this chapter. The companion Volume 1 describes the context and the distribution of gaseous and particulate pollutants. The present volume is composed of six sections that make the synthesis of our knowledge on air pollutant sources (Part V), atmospheric chemical processes (VI), aerosol properties (VII), atmospheric deposition fluxes (VIII), and the impacts of air pollution on the chemical composition of precipitation and climate (IX) and on human health and ecosystems (X). The conclusions presented in this volume demonstrate large variety of impacts of air pollution on the environment in the Mediterranean, including the impacts on human health, ecosystems, and climate. Accurate emission evaluation of gaseous and particulate pollutants and understanding of their chemical transformation are critical for representation and prediction of atmospheric pollution and climate change in this region. Long-term observations of physical and chemical parameters describing atmospheric composition together with climate variables are essential to constrain models and to better quantify interactions between climate change and air quality. Addressing the impacts of pollution and supporting mitigation measures require holistic and integrated approach to the related studies, putting together scientific communities working on atmosphere, on health, as well as on both terrestrial and marine ecosystems.

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.

In the vast low-nutrient—low-chlorophyll (LNLC) ocean, the vertical nutrient supply from the subsurface to the sunlit surface waters is low, and atmospheric contribution of nutrients may be 1 order of magnitude greater over short timescales. Recently, significant experimental, field and modeling work allowed us to better link atmospheric deposition with nutrient availability, ocean productivity, carbon cycling and marine emissions. By improving our understanding on how atmospheric inputs are impacting biological activity and the carbon balance in oligotrophic environments, their representation in biogeochemical models at different timescales and space scales will be better assessed. In particular, processes may be affected by ongoing environmental changes in the ocean such as a decrease in pH and an increase in temperature.\n\nThis special issue aims at gathering contributions from both experimental and modeling approaches showing how natural or anthropogenic inputs from the atmosphere can impact biogeochemical and ecological processes in the present and future oligotrophic ocean. It will present the results obtained during the PEACETIME (ProcEss studies at the Air-sEa Interface after dust deposition in the MEditerranean sea) cruise conducted in 2017 in the Mediterranean Sea, but the special issue is open to any submissions provided that the subject is consistent with the objectives defined above.

Abstract. N2 fixation rates were measured in the 0–1000 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 γ-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 72.1 nmolNL-1d-1, which could support up to 19 % of primary production. At this station at 1 % PAR (photosynthetically available radiation) depth, UCYN-A4 represented up to 94 % 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 (3–4 d) experiments at three stations. New nutrients from simulated dust deposition triggered a significant stimulation of N2 fixation (from 41 % to 565 %). 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 fixation was either increased or unchanged; in that later case this was probably due to a too-low nutrient bioavailability or an increased grazing pressure. The future warming and acidification likely benefited NCDs (Pseudomonas) and UCYN-A2, while disadvantaged UCYN-A3 without knowing which effect (alone or in combination) is the driver, especially since we do not know the temperature optima of these species not yet cultivated as well as the effect of acidification.

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 Published by Copernicus Publications on behalf of the European Geosciences Union. 2310 K. Desboeufs et al.: Wet deposition in the remote western and central Mediterranean 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 a source of some of dissolved TMs for Med Sea surface waters. The contribution of dry deposition to the atmospheric TM inputs needs to be investigated.

Diazotrophs are often limited by iron (Fe) availability in the oligotrophic ocean. The Western Tropical South Pacific (WTSP) ocean has been suggested as an intense N 2 fixation area due to Fe fertilizations through shallow hydrothermal activity. Yet, the Fe demand of diazotrophs in their natural habitat, where they cohabit with other microbial organisms also requiring Fe, remains unknown. Here we develop and apply a method consisting of coupling 55 Fe uptake experiments with cell-sorting by flow cytometry, and provide group-specific rates of in situ Fe uptake by the microbial community in the WTSP, in addition to bulk and size fractionation rates. We reveal that the diazotrophs Crocosphaera watsonii and Trichodesmium contribute substantially to the bulk in situ Fe uptake (~33% on average over the studied area), despite being numerically less abundant compared to the rest of the planktonic community. Trichodesmium had the highest cell-specific Fe uptake rates, followed by C. watsonii, picoeukaryotes, Prochlorococcus, Synechococcus and finally heterotrophic bacteria. Calculated Fe:C quotas were higher (by 2 to 52-fold) for both studied diazotrophs compared to those of the non-diazotrophic plankton, reflecting their high intrinsic Fe demand. This translates into a diazotroph biogeographical distribution that appears to be influenced by ambient dissolved Fe concentrations in the WTSP. Despite having low cell-specific uptake rates, Prochlorococcus and heterotrophic bacteria were largely the main contributors to the bulk Fe uptake (~23% and ~12%, respectively). Overall, this group-specific approach increases our ability to examine the ecophysiological role of functional groups, including those of less abundant and/or less active microbes.

Abstract. The study of phosphorus cycling in phosphate-depleted oceanic regions, such as the Mediterranean Sea, has long suffered from methodological limitations, leading to a simplistic view of a homogeneous surface phosphate pool with concentrations below the detection limit of measurement above the phosphacline. During the PEACETIME (Process studies at the air-sea interface after dust deposition in the Mediterranean Sea) cruise, carried out from 10 May to 11 June 2017, we conducted co-located measurements of phosphate pools at the nanomolar level, alkaline phosphatase activities and atmospheric deposition of phosphorus, across a longitudinal gradient from the west to the central Mediterranean Sea. In the phosphate-depleted layer (PDL), between the surface and the phosphacline, nanomolar phosphate was low and showed little variability across the transect spanning from 6 ± 1 nmol L−1 in the Ionian basin to 15 ± 4 nmol L−1 in the westernmost station. The low variability in phosphate concentration contrasted with that of alkaline phosphatase activity, which varied over 1 order of magnitude across the transect. Nanomolar phosphate data revealed gradients of phosphate concentration over density inside the PDL ranging between 10.6 ± 2.2 µmol kg−1 in the westernmost station to values close to zero towards the east. Using the density gradients, we estimated diapycnal fluxes of phosphate to the PDL and compared them to atmospheric deposition, another external source of phosphate to the PDL. Phosphate supply to the PDL from dry deposition and diapycnal fluxes was comparable in the western part of the transect. This result contrasts with the longtime idea that, under stratification conditions, the upper waters of the Mediterranean Sea receive new P almost exclusively from the atmosphere. The contribution of atmospheric deposition to external P supply increased under the occurrence of rain and Saharan dust. Although this finding must be taken cautiously given the uncertainties in the estimation of diapycnal fluxes, it opens exciting questions on the biogeochemical response of the Mediterranean Sea, and more generally of marine oligotrophic regions, to expected changes in atmospheric inputs and stratification regimes. Taken together, external sources of phosphate to the PDL contributed little to total phosphate requirements which were mainly sustained by in situ hydrolysis of dissolved organic phosphorus. The results obtained in this study show a highly dynamic phosphorus pool in the upper layer of the euphotic zone, above the phosphacline, and highlight the convenience of combining highly sensitive measurements and high-resolution sampling to precisely depict the shape of phosphate profiles in the euphotic zone with still unexplored consequences on P fluxes supplying this crucial layer for biogeochemical cycles.

The surface mixed layer (ML) in the Mediterranean Sea is a well-stratified domain characterized by low macronutrients and low chlorophyll content for almost 6 months of the year. In this study we characterize the biogeochemical cycling of nitrogen (N) in the ML by analyzing simultaneous in situ measurements of atmospheric deposition, nutrients in seawater, hydrological conditions, primary production, heterotrophic prokaryotic production, N2 fixation and leucine aminopeptidase activity. Dry deposition was continuously measured across the central and western open Mediterranean Sea, and two wet deposition events were sampled, one in the Ionian Sea and one in the Algerian Basin. Along the transect, N budgets were computed to compare the sources and sinks of N in the mixed layer. In situ leucine aminopeptidase activity made up 14 % to 66 % of the heterotrophic prokaryotic N demand, and the N2 fixation rate represented 1 % to 4.5 % of the phytoplankton N demand. Dry atmospheric deposition of inorganic nitrogen, estimated from dry deposition of nitrate and ammonium in aerosols, was higher than the N2 fixation rates in the ML (on average 4.8-fold). The dry atmospheric input of inorganic N represented a highly variable proportion of biological N demand in the ML among the stations, 10 %–82 % for heterotrophic prokaryotes and 1 %–30 % for phytoplankton. As some sites were visited on several days, the evolution of biogeochemical properties in the ML and within the nutrient-depleted layers could be followed. At the Algerian Basin site, the biogeochemical consequences of a wet dust deposition event were monitored through high-frequency sampling. Notably, just after the rain, nitrate was higher in the ML than in the nutrient-depleted layer below. Estimates of nutrient transfer from the ML into the nutrient-depleted layer could explain up to a third of the nitrate loss from the ML. Phytoplankton did not benefit directly from the atmospheric inputs into the ML, probably due to high competition with heterotrophic prokaryotes, also limited by N and phosphorus (P) availability at the time of this study. Primary producers decreased their production after the rain but recovered their initial state of activity after a 2 d lag in the vicinity of the deep chlorophyll maximum layer.

Anthropogenic emissions to the atmosphere have increased the flux of nutrients, especially nitrogen, to the ocean, but they have also altered the acidity of aerosol, cloud water, and precipitation over much of the marine atmosphere. For nitrogen, acidity-driven changes in chemical speciation result in altered partitioning between the gas and particulate phases that subsequently affect long-range transport. Other important nutrients, notably iron and phosphorus, are affected, because their soluble fractions increase upon exposure to acidic environments during atmospheric transport. These changes affect the magnitude, distribution, and deposition mode of individual nutrients supplied to the ocean, the extent to which nutrient deposition interacts with the sea surface microlayer during its passage into bulk seawater, and the relative abundances of soluble nutrients in atmospheric deposition. Atmospheric acidity change therefore affects ecosystem composition, in addition to overall marine productivity, and these effects will continue to evolve with changing anthropogenic emissions in the future.

Lithogenic elements such as aluminum (Al), iron (Fe), rare earth elements (REEs), thorium (232Th and 230Th, given as Th) and protactinium (Pa) are often assumed to be insoluble. In this study, their dissolution from Saharan dust reaching Mediterranean seawater was studied through tank experiments over 3 to 4 d under controlled conditions including controls without dust addition as well as dust seeding under present and future climate conditions (+3 °C and −0.3 pH). Unfiltered surface seawater from three oligotrophic regions (Tyrrhenian Sea, Ionian Sea and Algerian Basin) were used. The maximum dissolution was low for all seeding experiments: less than 0.3 % for Fe, 1 % for 232Th and Al, about 2 %–5 % for REEs and less than 6 % for Pa. Different behaviors were observed: dissolved Al increased until the end of the experiments, Fe did not dissolve significantly, and Th and light REEs were scavenged back on particles after a fast initial release. The constant 230Th/232Th ratio during the scavenging phase suggests that there is little or no further dissolution after the initial Th release. Quite unexpectedly, comparison of present and future conditions indicates that changes in temperature and/or pH influence the release of Th and REEs in seawater, leading to lower Th release and a higher light REE release under increased greenhouse conditions.

Abstract. Although atmospheric dust fluxes from arid as well as human-impacted areas represent a significant source of nutrients to surface waters of the Mediterranean Sea, studies focusing on the evolution of the metabolic balance of the plankton community following a dust deposition event are scarce, and none were conducted in the context of projected future levels of temperature and pH. Moreover, most of the experiments took place in coastal areas. In the framework of the PEACETIME project, three dust-addition perturbation experiments were conducted in 300 L tanks filled with surface seawater collected in the Tyrrhenian Sea (TYR), Ionian Sea (ION) and Algerian basin (FAST) on board the R/V Pourquoi Pas? in late spring 2017. For each experiment, six tanks were used to follow the evolution of chemical and biological stocks, biological activity and particle export. The impacts of a dust deposition event simulated at their surface were followed under present environmental conditions and under a realistic climate change scenario for 2100 (ca. +3 ∘C and −0.3 pH units). The tested waters were all typical of stratified oligotrophic conditions encountered in the open Mediterranean Sea at this period of the year, with low rates of primary production and a metabolic balance towards net heterotrophy. The release of nutrients after dust seeding had very contrasting impacts on the metabolism of the communities, depending on the station investigated. At TYR, the release of new nutrients was followed by a negative impact on both particulate and dissolved 14C-based production rates, while heterotrophic bacterial production strongly increased, driving the community to an even more heterotrophic state. At ION and FAST, the efficiency of organic matter export due to mineral/organic aggregation processes was lower than at TYR and likely related to a lower quantity/age of dissolved organic matter present at the time of the seeding and a smaller production of DOM following dust addition. This was also reflected by lower initial concentrations in transparent exopolymer particles (TEPs) and a lower increase in TEP concentrations following the dust addition, as compared to TYR. At ION and FAST, both the autotrophic and heterotrophic community benefited from dust addition, with a stronger relative increase in autotrophic processes observed at FAST. Our study showed that the potential positive impact of dust deposition on primary production depends on the initial composition and metabolic state of the investigated community. This impact is constrained by the quantity of nutrients added in order to sustain both the fast response of heterotrophic prokaryotes and the delayed one of primary producers. Finally, under future environmental conditions, heterotrophic metabolism was overall more impacted than primary production, with the consequence that all integrated net community production rates decreased with no detectable impact on carbon export, therefore reducing the capacity of surface waters to sequester anthropogenic CO2.

In low-nutrient low-chlorophyll areas, such as the Mediterranean Sea, atmospheric fluxes represent a considerable external source of nutrients likely supporting primary production, especially during periods of stratification. These areas are expected to expand in the future due to lower nutrient supply from sub-surface waters caused by climate-driven enhanced stratification, likely further increasing the role of atmospheric deposition as a source of new nutrients to surface waters. Whether plankton communities will react differently to dust deposition in a warmer and acidified environment remains; however, an open question. The potential impact of dust deposition both in present and future climate conditions was investigated in three perturbation experiments in the open Mediterranean Sea. Climate reactors (300 L) were filled with surface water collected in the Tyrrhenian Sea, Ionian Sea and in the Algerian basin during a cruise conducted in the frame of the PEACETIME project in May–June 2017. The experiments comprised two unmodified control tanks, two tanks enriched with a Saharan dust analogue and two tanks enriched with the dust analogue and maintained under warmer (+3 ∘C) and acidified (−0.3 pH unit) conditions. Samples for the analysis of an extensive number of biogeochemical parameters and processes were taken over the duration (3–4 d) of the experiments. Dust addition led to a rapid release of nitrate and phosphate, however, nitrate inputs were much higher than phosphate. Our results showed that the impacts of Saharan dust deposition in three different basins of the open northwestern Mediterranean Sea are at least as strong as those observed previously, all performed in coastal waters. The effects of dust deposition on biological stocks were different for the three investigated stations and could not be attributed to differences in their degree of oligotrophy but rather to the initial metabolic state of the community. Ocean acidification and warming did not drastically modify the composition of the autotrophic assemblage, with all groups positively impacted by warming and acidification. Although autotrophic biomass was more positively impacted than heterotrophic biomass under future environmental conditions, a stronger impact of warming and acidification on mineralization processes suggests a decreased capacity of Mediterranean surface plankton communities to sequester atmospheric CO2 following the deposition of atmospheric particles.

Abstract. Ice-nucleating particles (INPs) have a large impact on the climate-relevant properties of clouds over the oceans. Studies have shown that sea spray aerosols (SSAs), produced upon bursting of bubbles at the ocean surface, can be an important source of marine INPs, particularly during periods of enhanced biological productivity. Recent mesocosm experiments using natural seawater spiked with nutrients have revealed that marine INPs are derived from two separate classes of organic matter in SSAs. Despite this finding, existing parameterizations for marine INP abundance are based solely on single variables such as SSA organic carbon (OC) or SSA surface area, which may mask specific trends in the separate classes of INP. The goal of this paper is to improve the understanding of the connection between ocean biology and marine INP abundance by reporting results from a field study and proposing a new parameterization of marine INPs that accounts for the two associated classes of organic matter. The PEACETIME cruise took place from 10 May to 10 June 2017 in the Mediterranean Sea. Throughout the cruise, INP concentrations in the surface microlayer (INPSML) and in SSAs (INPSSA) produced using a plunging aquarium apparatus were continuously monitored while surface seawater (SSW) and SML biological properties were measured in parallel. The organic content of artificially generated SSAs was also evaluated. INPSML concentrations were found to be lower than those reported in the literature, presumably due to the oligotrophic nature of the Mediterranean Sea. A dust wet deposition event that occurred during the cruise increased the INP concentrations measured in the SML by an order of magnitude, in line with increases in iron in the SML and bacterial abundances. Increases in INPSSA were not observed until after a delay of 3 days compared to increases in the SML and are likely a result of a strong influence of bulk SSW INPs for the temperatures investigated (T=-18 ∘C for SSAs, T=-15 ∘C for SSW). Results confirmed that INPSSA are divided into two classes depending on their associated organic matter. Here we find that warm (T≥-22 ∘C) INPSSA concentrations are correlated with water-soluble organic matter (WSOC) in the SSAs, but also with SSW parameters (particulate organic carbon, POCSSW and INPSSW,-16C) while cold INPSSA (T<-22 ∘C) are correlated with SSA water-insoluble organic carbon (WIOC) and SML dissolved organic carbon (DOC) concentrations. A relationship was also found between cold INPSSA and SSW nano- and microphytoplankton cell abundances, indicating that these species might be a source of water-insoluble organic matter with surfactant properties and specific IN activities. Guided by these results, we formulated and tested multiple parameterizations for the abundance of INPs in marine SSAs, including a single-component model based on POCSSW and a two-component model based on SSA WIOC and OC. We also altered a previous model based on OCSSA content to account for oligotrophy of the Mediterranean Sea. We then compared this formulation with the previous models. This new parameterization should improve attempts to incorporate marine INP emissions into numerical models.

Mineral dust deposition is an important supply mechanism for trace elements in the low-latitude ocean. Our understanding of the controls of such inputs has been mostly built onto laboratory and surface ocean studies. The lack of direct observations and the tendency to focus on near surface waters prevent a comprehensive evaluation of the role of dust in oceanic biogeochemical cycles. In the frame of the PEACETIME project (ProcEss studies at the Air-sEa Interface after dust deposition in the MEditerranean sea), the responses of the aluminium (Al) and iron (Fe) cycles to two dust wet deposition events over the central and western Mediterranean Sea were investigated at a timescale of hours to days using a comprehensive dataset gathering dissolved and suspended particulate concentrations, along with sinking fluxes.Dissolved Al (dAl) removal was dominant over dAl released from dust. Fe / Al ratio of suspended and sinking particles revealed that biogenic particles, and in particular diatoms, were key in accumulating and exporting Al relative to Fe. By combining these observations with published Al / Si ratios of diatoms, we show that adsorption onto biogenic particles, rather than active uptake, represents the main sink for dAl in Mediterranean waters. In contrast, systematic dissolved Fe (dFe) accumulation occurred in subsurface waters (~100–1000 m), while dFe input from dust was only transient in the surface mixed-layer. The rapid transfer of dust to depth (up to ~180 m d⁻¹), the Fe-binding ligand pool in excess to dFe in subsurface (while nearly-saturated in surface), and low scavenging rates in this particle-poor depth horizon are all important drivers of this subsurface dFe enrichment.At the annual scale, this previously overlooked mechanism may represent an additional pathway of dFe supply for the surface ocean through diapycnal diffusion and vertical mixing. However, low subsurface dFe concentrations observed at the basin scale (< 0.5 nmol kg⁻¹) questions the residence time for this dust-derived subsurface reservoir, and hence its role as a supply mechanism for the surface ocean, stressing the need for further studies. Finally, these contrasting responses indicate that dAl is a poor tracer of dFe input in the Mediterranean Sea.

Abstract. Mineral dust deposition is an important supply mechanism for trace elements in the low-latitude ocean. Our understanding of the controls of such inputs has been mostly built on laboratory and surface ocean studies. The lack of direct observations and the tendency to focus on near-surface waters prevent a comprehensive evaluation of the role of dust in oceanic biogeochemical cycles. In the frame of the PEACETIME project (ProcEss studies at the Air-sEa Interface after dust deposition in the MEditerranean sea), the responses of the aluminum (Al) and iron (Fe) cycles to two dust wet deposition events over the central and western Mediterranean Sea were investigated at a timescale of hours to days using a comprehensive dataset gathering dissolved and suspended particulate concentrations, along with sinking fluxes. Dissolved Al (dAl) removal was dominant over dAl released from dust. The Fe/Al ratio of suspended and sinking particles revealed that biogenic particles, and in particular diatoms, were key in accumulating and exporting Al relative to Fe. By combining these observations with published Al/Si ratios of diatoms, we show that adsorption onto biogenic particles, rather than active uptake, represents the main sink for dAl in Mediterranean waters. In contrast, systematic dissolved Fe (dFe) accumulation occurred in subsurface waters (∼ 100–1000 m), while dFe input from dust was only transient in the surface mixed layer. The rapid transfer of dust to depth, the Fe-binding ligand pool in excess to dFe in subsurface (while nearly saturated in surface), and low scavenging rates in this particle-poor depth horizon are all important drivers of this subsurface dFe enrichment. At the annual scale, this previously overlooked mechanism may represent an additional pathway of dFe supply for the surface ocean through diapycnal diffusion and vertical mixing. However, low subsurface dFe concentrations observed at the basin scale (< 0.5 nmol kg−1) cause us to question the residence time for this dust-derived subsurface reservoir and hence its role as a supply mechanism for the surface ocean, stressing the need for further studies. Finally, these contrasting responses indicate that dAl is a poor tracer of dFe input in the Mediterranean Sea.

One pathway by which the oceans influence climate is via the emission of sea spray that may subsequently influence cloud properties. Sea spray emissions are known to be dependent on atmospheric and oceanic physicochemical parameters, but the potential role of ocean biology on sea spray fluxes remains poorly characterized. Here we show a consistent significant relationship between seawater nanophytoplankton cell abundances and sea-spray derived Cloud Condensation Nuclei (CCN) number fluxes, generated using water from three different oceanic regions. This sensitivity of CCN number fluxes to ocean biology is currently unaccounted for in climate models yet our measurements indicate that it influences fluxes by more than one order of magnitude over the range of phytoplankton investigated.

Abstract. The organic mass fraction from sea spray aerosol (SSA) is currently a subject of intense research. The majority of this research is dedicated to measurements in ambient air. However a number of studies have recently started to focus on nascent sea spray aerosol. This work presents measurements collected during a 5-week cruise in May and June 2017 in the central and western Mediterranean Sea, an oligotrophic marine region with low phytoplankton biomass. Surface seawater was continuously pumped into a bubble-bursting apparatus to generate nascent sea spray aerosol. Size distributions were measured with a differential mobility particle sizer (DMPS). Chemical characterization of the submicron aerosol was performed with a time-of- flight aerosol chemical speciation monitor (ToF-ACSM) operating with 10 min time resolution and with filter-based chemical analysis on a daily basis. Using positive matrix factorization analysis, the ToF-ACSM non-refractory organic matter (OMNR) was separated into four different organic aerosol types, identified as primary OA (POANR), oxidized OA (OOANR), methanesulfonic acid type OA (MSA-OANR), and mixed OA (MOANR). In parallel, surface seawater biogeochemical properties were monitored providing information on phytoplankton cell abundance and seawater particulate organic carbon (1 h time resolution) and seawater surface microlayer (SML) dissolved organic carbon (DOC) (on a daily basis). Statistically robust correlations (for n > 500) were found between MOANR and nanophytoplankton cell abundance, as well as between POANR, OOANR, and particulate organic carbon (POC). Parameterizations of the contributions of different types of organics to the submicron nascent sea spray aerosol are proposed as a function of the seawater biogeochemical properties for use in models.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

The Sea Surface Microlayer (SML) is known to be enriched by trace metals relative to the underlying water and harbor diverse microbial communities (i.e., neuston). However, the processes linking metals and biota in the SML are not yet fully understood. The metal (Cd, Co, Cu, Fe, Ni, Mo, V, Zn and Pb) concentrations in aerosol samples in the SML (dissolved and total fractions) and in subsurface waters (SSWs; dissolved fraction at ∼ 1 m depth) from the western Mediterranean Sea were analyzed in this study during a cruise in May-June 2017. The composition and abundance of the bacterial community in the SML and SSW, the primary production, and Chl a in the SSW were measured simultaneously at all stations during the cruise. Residence times in the SML of metals derived from aerosol depositions were highly variable and ranged from minutes for Fe (3.6 ± 6.0 min) to a few hours for Cu (5.8 ± 6.2 h). Concentrations of most of the dissolved metals in both the SML and SSW were positively correlated with the salinity gradient and showed the characteristic eastward increase in the surface waters of the Mediterranean Sea (MS). In contrast, the total fraction of some reactive metals in the SML (i.e., Cu, Fe, Pb and Zn) showed a negative correlation with salinity and a positive correlation with microbial abundance, which might be associated with microbial uptake. Our results show a strong negative correlation between the dissolved and total Ni concentration and heterotrophic bacterial abundance in the SML and SSW, but we cannot ascertain whether this correlation reflects a toxicity effect or is the result of some other process .

Iron is a key micronutrient in seawater, but concentrations would be negligible without the presence of organic ligands. The processes influencing the ligand pool composition are poorly constrained, limiting our understanding of the controls on dissolved iron distributions. To address this, the release of iron and iron-binding ligands during the microbial remineralization of sinking particles was investigated by deploying in situ particle interceptor/incubator devices at subsurface sites in the Mediterranean Sea and Subantarctic. Analyses revealed that the pool of released ligands was largely dominated by electroactive humic substances (74 ± 28%). The release of ligands during remineralization ensured that concurrently released iron remained in solution, which is crucial for iron regeneration. This study presents compelling evidence of the key role of humic ligands in the subsurface replenishment of dissolved iron and thus on the wider oceanic dissolved iron inventory, which ultimately controls the magnitude of iron resupplied to the euphotic zone.

The dissolved iron supply controls half of the oceans’ primary productivity. Resupply by the remineralization of sinking particles, and subsequent vertical mixing, largely sustains this productivity. However, our understanding of the drivers of dissolved iron resupply, and their influence on its vertical distribution across the oceans, is still limited due to sparse observations. There is a lack of empirical evidence as to what controls the subsurface iron remineralization due to difficulties in studying mesopelagic biogeochemistry. Here we present estimates of particulate transformations to dissolved iron, concurrent oxygen consumption and iron-binding ligand replenishment based on in situ mesopelagic experiments. Dissolved iron regeneration efficiencies (that is, replenishment over oxygen consumption) were 10- to 100-fold higher in low-dust subantarctic waters relative to higher-dust Mediterranean sites. Regeneration efficiencies are heavily influenced by particle composition. Their make-up dictates ligand release, controls scavenging, modulates ballasting and may lead to the differential remineralization of biogenic versus lithogenic iron. At high-dust sites, these processes together increase the iron remineralization length scale. Modelling reveals that in oceanic regions near deserts, enhanced lithogenic fluxes deepen the ferricline, which alter the vertical patterns of dissolved iron replenishment, and set its redistribution at the global scale. Such wide-ranging regeneration efficiencies drive different vertical patterns in dissolved iron replenishment across oceanic provinces.

1. Atmospheric iron deposition is essential to sustain the high levels of productivity during the summer monsoon 2. Nitrogen fixation remains low despite large iron deposition 3. Atmospheric deposition of nitrogen and phosphorus also play a negligible role

Atmospheric deposition is a source of potentially bioavailable iron (Fe) and thus can partially control biological productivity in large parts of the ocean. However, the explanation of observed high aerosol Fe solubility compared to that in soil particles is still controversial, as several hypotheses have been proposed to explain this observation. Here, a statistical analysis of aerosol Fe solubility estimated from four models and observations compiled from multiple field campaigns suggests that pyrogenic aerosols are the main sources of aerosols with high Fe solubility at low concentration. Additionally, we find that field data over the Southern Ocean display a much wider range in aerosol Fe solubility compared to the models, which indicate an underestimation of labile Fe concentrations by a factor of 15. These findings suggest that pyrogenic Fe-containing aerosols are important sources of atmospheric bioavailable Fe to the open ocean and crucial for predicting anthropogenic perturbations to marine productivity.

Atmospheric deposition represents a significant source of nutrients at the Mediterranean basin scale. We apply aerosol deposition fields simulated from atmospheric models into the high resolution oceanic biogeochemical model NEMOMED12/PISCES with nutrient ratios used for plankton growth set to Redfield ratio. We perform 3 simulations to determine the impact of nutrients on productivity over the period 1997–2012: (i) without atmospheric deposition, (ii) with nitrogen deposition from anthropogenic and natural sources, and (iii) with deposition of both nitrogen (from anthropogenic and natural sources) and phosphate from desert dust. Time series of modeled deposition fluxes are compared to available measurements. This comparison with measurements shows that both variability and intensity ranges are realistic enough for our main purpose of estimating the atmospheric deposition impact on Mediterranean biogeochemical tracers such as surface nutrient concentrations, chlorophyll a and plankton concentrations. Our results show that atmospheric deposition is one of the major sources of nitrogen and phosphorus for some regions of the oligotrophic Mediterranean Sea. More than 18 · 10⁹gN month⁻¹ are deposited to the whole Mediterranean Sea. This deposition is responsible for an average increase of 30–50% in primary production over vast regions. Natural dust-derived deposition of phosphorus is sparser in space and time (0.5 · 10⁹ g month⁻¹ on average over the entire basin). However, dust deposition events can significantly affect biological production. We calculate fertilizing effects of phosphate from dust to be low on average (6–10%) but up to 30% increase in primary productivity can be observed during the months when surface water stratification occurs. Finally, these fertilizing effects are shown to be transmitted along the biological chain (primary production, Chl a, phytoplankton, zooplankton, grazing). We also perform a preliminary study on the maximal biological response of the Mediterranean by simulating extreme deposition events throughout the basin over a full year period. We show that nitrogen deposition effects observed in our long-term simulations (1997–2012) are close to maximal effects (i.e. those produced by high intensity deposition events) whereas dust-derived phosphate effects are substantially weaker than the effect on productivity reached when an extreme deposition event occurs.

N 2 fixation by the genus Trichodesmium is predicted to support a large proportion of the primary productivity across the oligotrophic oceans, regions that are considered among the largest biomes on Earth. Many of these environments remain poorly sampled, limiting our understanding of Trichodesmium physiological ecology in these critical oligotrophic regions. Trichodesmium colonies, communities that consist of the Trichodesmium host and their associated microbiome, were collected across the oligotrophic western tropical South Pacific (WTSP). These samples were used to assess host clade distribution, host and microbiome metabolic potential, and functional gene expression, with a focus on identifying Trichodesmium physiological ecology in this region. Genes sets related to phosphorus, iron, and phosphorus-iron co-limitation were dynamically expressed across the WTSP transect, suggestive of the importance of these resources in driving Trichodesmium physiological ecology in this region. A gene cassette for phosphonate biosynthesis was detected in Trichodesmium, the expression of which co-varied with the abundance of Trichodesmium Clade III, which was unusually abundant relative to Clade I in this environment. Coincident with the expression of the gene cassette, phosphate reduction to phosphite and low-molecular-weight phosphonate compounds was measured in Trichodesmium colonies. The expression of genes that enable use of such reduced-phosphorus compounds were also measured in both Trichodesmium and the microbiome. Overall , these results highlight physiological strategies employed by consortia in an undersampled region of the oligotrophic WTSP and reveal the molecular mechanisms underlying previously observed high rates of phosphorus reduction in Tri-chodesmium colonies.

We performed nitrogen (N) budgets in the photic layer of three contrasting stations representing different trophic conditions in the western tropical South Pacific (WTSP) Ocean during austral summer conditions (FebruaryMarch 2015). Using a Lagrangian strategy, we sampled the same water mass for the entire duration of each long-duration (5 days) station, allowing us to consider only vertical exchanges for the budgets. We quantified all major vertical N fluxes both entering (N-2 fixation, nitrate turbulent diffusion, atmospheric deposition) and leaving the photic layer (particulate N export). The three stations were characterized by a strong nitracline and contrasted deep chlorophyll maximum depths, which were lower in the oligotrophic Melanesian archipelago (MA, stations LD A and LD B) than in the ultra-oligotrophic waters of the South Pacific Gyre (SPG, station LD C). N-2 fixation rates were extremely high at both LD A (593 +/- 51 mu mol N m(-2) d(-1)) and LD B (706 +/- 302 mu mol N m(-2)d(-1)), and the diazotroph community was dominated by Trichodesmium. N-2 fixation rates were lower (59 +/- 16 mu mol N m(-2) d(-1)) at LD C, and the diazotroph community was dominated by unicellular N-2-fixing cyanobacteria (UCYN). At all stations, N-2 fixation was the major source of new N (> 90 %) before atmospheric deposition and upward nitrate fluxes induced by turbulence. N-2 fixation contributed circa 1318 % of primary production in the MA region and 3 in the SPG water and sustained nearly all new primary production at all stations. The e ratio (e ratio articulate carbon export / primary production) was maximum at LD A (9.7 ) and was higher than the e ratio in most studied oligotrophic regions (< 5), indicating a high efficiency of the WTSP to export carbon relative to primary production. The direct export of diazotrophs assessed by qPCR of the nifH gene in sediment traps represented up to 30.6 of the PC export at LD A, while their contribution was 5 and < 0.1 % at LD B and LD C, respectively. At the three studied stations, the sum of all N input to the photic layer exceeded the N output through organic matter export. This disequilibrium leading to N accumulation in the upper layer appears as a characteristic of the WTSP during the summer season.

Here we report N 2 fixation rates from a ∼ 4000 km transect in the western and central tropical South Pacific , a particularly undersampled region in the world ocean. Water samples were collected in the euphotic layer along a west to east transect from 160 • E to 160 • W that covered contrasting trophic regimes, from oligotro-phy in the Melanesian archipelago (MA) waters to ultra-oligotrophy in the South Pacific Gyre (GY) waters. N 2 fixation was detected at all 17 sampled stations with an average depth-integrated rate of 631 ± 286 µmol N m −2 d −1 (range 196-1153 µmol N m −2 d −1) in MA waters and of 85 ± 79 µmol N m −2 d −1 (range 18-172 µmol N m −2 d −1) in GY waters. Two cyanobacteria, the larger colonial filamen-tous Trichodesmium and the smaller UCYN-B, dominated the enumerated diazotroph community (> 80 %) and gene expression of the nifH gene (cDNA > 10 5 nifH copies L −1) in MA waters. Single-cell isotopic analyses performed by nanoscale secondary ion mass spectrometry (nanoSIMS) at selected stations revealed that Trichodesmium was always the major contributor to N 2 fixation in MA waters, accounting for 47.1-83.8 % of bulk N 2 fixation. The most plausible environmental factors explaining such exceptionally high rates of N 2 fixation in MA waters are discussed in detail, emphasizing the role of macro-and micro-nutrient (e.g., iron) availability , seawater temperature and currents.

In the Western Tropical South Pacific, patches of high chlorophyll concentrations linked to the occurrence of N₂-fixing organisms are found in the vicinity of volcanic islands. The survival of these organisms relies on a high bioavailable iron supply whose origin and fluxes remain unknown. Here, we measured high dissolved iron (DFe) concentrations (up to 66 nM) in the euphotic layer, extending zonally over 10 degrees longitude (174 E−175 W) at ∼20°S latitude. DFe atmospheric fluxes were at the lower end of reported values of the remote ocean and could not explain the high DFe concentrations measured in the water column in the vicinity of Tonga. We argue that the high DFe concentrations may be sustained by a submarine source, also characterized by freshwater input and recorded as salinity anomalies by Argo float in situ measurements and atlas data. The observed negative salinity anomalies are reproduced by simulations from a general ocean circulation model. Submarine iron sources reaching the euphotic layer may impact nitrogen fixation across the whole region.

Regionalisation aims at delimiting provinces within which physical conditions, chemical properties, and biological communities are reasonably homogeneous. This article proposes a synthesis of the many recent regionalisations of the open-sea regions of the Mediterranean Sea. The nine studies considered here defined regions based on different, and sometimes complementary, criteria: dynamics of surface chlorophyll concentration, ocean currents, three-dimensional hydrological and biogeochemical properties, or the distribution of organisms. Although they identified different numbers and patterns of homogeneous regions, their compilation in the epipelagic zone identifies nine consensus frontiers, eleven consensus regions with relatively homogeneous conditions, and four heterogeneous regions with highly dynamical conditions. The consensus frontiers and regions are in agreement with well-known hydrodynamical features of the Mediterranean Sea, which constrain the distribution of hydrological and ecological variables. The heterogeneous regions are rather defined by intense mesoscale activity. The synthesis proposed here could constitute a reference step for management actions and spatial planning, such as the application of the European Marine Strategy Framework Directive, and for future biogeochemical and ecological studies in the Mediterranean Sea.

Modifications in the strength of the biological pump as a consequence of ocean acidification, whether positive or negative, have the potential to impact atmospheric CO2 and therefore climate. So far, most plankton community perturbation studies have been performed in nutrient-rich areas although there are some indications that CO2-dependent growth could differ in nutrient-replete vs. -limited regions and with different community compositions. Two in situ mesocosm experiments were performed in the NW Mediterranean Sea during two seasons with contrasted environmental conditions: summer oligotrophic stratified waters in the Bay of Calvi vs. winter mesotrophic well-mixed waters in the Bay of Villefranche. Nine mesocosms were deployed for 20 and 12 d, respectively, and subjected to seven CO2 levels (3 controls, 6 elevated levels). Both phytoplankton assemblages were dominated by pico- and nano-phytoplankton cells. Although haptophyceae and dinoflagellates benefited from short-term CO2 enrichment in summer, their response remained small with no consequences on organic matter export due to strong environmental constraints (nutrient availability). In winter, most of the plankton growth and associated nutrient consumption occurred during the 4-day acidification period (before the experimental phase). During the remaining experimental period, characterized by low nutrient availability, plankton growth was minimal and no clear CO2-dependency was found for any of the tested parameters. While there is a strong confidence on the absence of significant effect of short-term CO2 addition under oligotrophic conditions, more investigations are needed to assess the response of plankton communities in winter when vertical mixing and weather conditions are major factors controlling plankton dynamics.

When dividing the ocean, the aim is generally to summarise a complex system into a representative number of units, each representing a specific environment, a biological community or a socio-economical specificity. Recently, several geographical partitions of the global ocean have been proposed using statistical approaches applied to remote sensing or observations gathered during oceanographic cruises. Such geographical frameworks defined at a macroscale appear hardly applicable to characterise the biogeochemical features of semi-enclosed seas that are driven by smaller-scale chemical and physical processes. Following the Longhurst’s biogeochemical partitioning of the pelagic realm, this study investigates the environmental divisions of the Mediterranean Sea using a large set of environmental parameters. These parameters were informed in the horizontal and the vertical dimensions to provide a 3D spatial framework for environmental management (12 regions found for the epipelagic, 12 for the mesopelagic, 13 for the bathypelagic and 26 for the seafloor). We show that: (1) the contribution of the longitudinal environmental gradient to the biogeochemical partitions decreases with depth; (2) the partition of the surface layer cannot be extrapolated to other vertical layers as the partition is driven by a different set of environmental variables. This new partitioning of the Mediterranean Sea has strong implications for conservation as it highlights that management must account for the differences in zoning with depth at a regional scale.

Oligotrophic areas account for about 30% of oceanic primary production and are projected to expand in a warm, high-CO2 world. Changes in primary production in these areas could have important impacts on future global carbon cycling. To assess the response of primary production and respiration of plankton communities to increasing partial pressure of CO2 (pCO2) levels in Low Nutrient Low Chorophyll areas, two mesocosm experiments were conducted in the Bay of Calvi (Corsica, France) and in the Bay of Villefranche (France) in June–July 2012 and February–March 2013 under different trophic state, temperature and irradiance conditions. Nine mesocosms of 50 m3 were deployed for 20 and 12 days, respectively, and were subjected to seven pCO2 levels (3 control and 6 elevated levels). The metabolism of the community was studied using several methods based on in situ incubations (oxygen light–dark, 18O and 14C uptake). Increasing pCO2 had no significant effect on gross primary production, net community production, particulate and dissolved carbon production, as well as on community respiration. These two mesocosm experiments, the first performed under maintained low nutrient and low chlorophyll, suggest that in large areas of the ocean, increasing pCO2 levels may not lead to a significant change in plankton metabolic rates and sea surface biological carbon fixation.

Two pelagic mesocosm experiments were conducted to study the impact of ocean acidification on Mediterranean plankton communities. A first experiment took place in summer 2012 in the Bay of Calvi (France) followed by an experiment in winter 2013 in the Bay of Villefranche (France) under pre-bloom conditions. Nine mesocosms were deployed: three served as controls and six were acidified in a targeted partial pressure of CO2 (pCO2) gradient from 450 to 1250 μatm. The evolution of dissolved organic and inorganic nutrient concentrations was observed using nanomolar techniques. The experiments were characterized by a large contribution of organic nutrients to nutrient pools and contrasting in situ conditions with an inorganic N/P ratio of 1.7 in summer and of 117 in winter. In the Bay of Calvi, initial conditions were representative of the summer oligotrophic Mediterranean Sea. While inorganic phosphate concentrations were depleted during both experiments, in situ inorganic nitrogen concentrations were higher in winter. However, nitrate was rapidly consumed in winter in all mesocosms during the acidification phase, leading to a decrease in N/P ratio to 13. During these first mesocosm experiments conducted in a low nutrient low chlorophyll area, nutrient dynamics were insensitive to CO2 enrichment, indicating that nutrient speciation and related biological processes were likely not impacted. During both experiments, nitrate and phosphate dynamics were controlled by the activity of small species that are favored in low nutrient conditions. In contrast to the theoretical knowledge, no increase in iron solubility at high pCO2 was observed.

The evolution of organic carbon export to the deep ocean, under anthropogenic forcing such as ocean warming and acidification, needs to be investigated in order to evaluate potential positive or negative feedbacks on atmospheric CO 2 concentrations, and therefore on climate. As such, modifications of aggregation processes driven by transparent exopolymer particles (TEP) formation have the potential to affect carbon export. The objectives of this study were to experimentally assess the dynamics of organic matter, after the simulation of a Saharan dust deposition event, through the measurement over one week of TEP abundance and size, and to evaluate the effects of ocean acidification on TEP formation and carbon export following a dust deposition event. Three experiments were performed in the laboratory using 300 L tanks filled with filtered seawater collected in the Mediterranean Sea, during two 'no bloom' periods (spring at the start of the stratification period and autumn at the end of this stratification period) and during the winter bloom period. For each experiment, one of the two tanks was acidified to reach pH conditions slightly below values projected for 2100 (~ 7.6–7.8). In both tanks, a dust deposition event of 10 g m-2 was simulated at the surface. Our results suggest that Saharan dust deposition triggered the abiotic formation of TEP, leading to the formation of organic-mineral aggregates. The amount of particulate organic carbon (POC) exported was proportional to the flux of lithogenic particles to the sediment traps. Depending on the season, the POC flux following artificial dust deposition ranged between 38 and 90 mg m-2 over six experimental days. Such variability is likely linked to the seasonal differences in the quality and quantity of TEP-precursors initially present in seawater. Finally, these export fluxes were not significantly different at the completion of the three experiments between the two pH conditions.

There is a growing international interest in studying the effects of ocean acidification on plankton communities that play a major role in the global carbon cycle and in the consumption of atmospheric CO2 via the so-called biological pump. Recently, several mesocosm experiments reported on the effect of ocean acidification on marine plankton communities, although the majority were performed in eutrophic conditions or following nutrient addition. The objective of the present study was to perform two mesocosm experiments in the oligo-to meso-trophic Northwestern Mediterranean Sea during two seasons with contrasting environmental conditions: in summer 2012 in the Bay of Calvi (Corsica, France) and in winter 2013 in the Bay of Villefranche (France). This paper describes the objectives of these experiments, the study sites, the experimental set-up and the environmental and experimental conditions during the two experiments. The 20-day experiment in the Bay of Calvi was undoubtedly representative of summer conditions in the Northwestern Mediterranean Sea with low nutrient and chlorophyll a concentrations, warm waters and high surface solar irradiance. In contrast, the winter experiment, which was reduced to 12 days because of bad weather conditions, failed to reproduce the mesotrophic conditions typical of the wintertime in this area. Indeed, a rapid increase in phytoplankton biomass during the acidification phase led to a strong decrease in nitrate concentrations and an unrealistic N and P co-limitation at this period of the year. An overview of the 11 papers related to this study and published in this special issue is provided.

Planet Earth has entered a new geological era, the Anthropocene, in which geologically significant conditions and processes are profoundly altered by human activities (Waters et al., 2016). Among many impacts, human activities have released excessive amounts of carbon dioxide (CO2) in the atmosphere leading to warming and ocean acidification: a decrease in pH and CO32- concentration and an increase in CO2 and HCO3- concentrations (Gattuso and Hansson, 2011). On average, at the global scale, surface ocean pH has decreased by 0.1 units since the beginning of the industrial era, equivalent to an increased acidity of 26% (Ciais et al., 2013). An additional decrease of pH is expected by 2100, ranging from 0.07 to 0.33, depending on the CO2 emission scenario considered (Gattuso et al., 2015).

The dynamics of dissolved inorganic nitrogen and phosphorus in seawater after a dust event were followed to better understand the impact of dust deposition in low nutrient waters of the Mediterranean Sea. Three independent abiotic experiments were performed over three seasons (winter, spring, end of summer) characterized by contrasted biogeochemical conditions. Experiments consisted of seeding evapocondensed Saharan dust at the surface of a polyethylene tank filled with filtered surface seawater. Phosphate (PO43-), nitrate (NO3-), size and number of particles and transparent exopolymeric particles production (TEP) were measured over the course of 1 week following seeding. Dust deposition was followed by a transient increase in [PO43-] during the first 3 h with a maximum input of 33, 9, and 39 nM, respectively in May, October and February. The removal of almost all the PO43- initially released suggests a scavenging process of PO43- back onto ferric oxide-rich particles leading to concentrations at the end of the experiment close to the initial values (7 nM in May and October, and 6 nM in February). NO3- released from dust was high especially in May and October (maximum input of 23 and 11 mu M, respectively) and was attributed to nitrogen dissolution from the large amount of small particles (<1 mu m) rich in nitrogen in the evapocondensed dust. [NO3-] remained high until the end of the experiment (16 mu M in May and 11 mu M in October), indicating that NO3- from dust is likely to be bioavailable for a longer period compared to PO43- from dust. The release of PO43- and NO3- was intrinsically linked to particle dynamics, governed by the quality/quantity of dissolved organic matter.

PERSEUS project aims to identify the most relevant pressures exerted on the ecosystems of the Southern European Seas (SES), highlighting knowledge and data gaps that endanger the achievement of SES Good Environmental Status (GES) as mandated by the Marine Strategy Framework Directive (MSFD). A complementary approach has been adopted, by a meta-analysis of existing literature on pressure/impact/knowledge gaps summarized in tables related to the MSFD descriptors, discriminating open waters from coastal areas. A comparative assessment of the Initial Assessments (IAs) for five SES countries has been also independently performed. The comparison between meta-analysis results and IAs shows similarities for coastal areas only. Major knowledge gaps have been detected for the biodiversity, marine food web, marine litter and underwater noise descriptors. The meta-analysis also allowed the identification of additional research themes targeting research topics that are requested to the achievement of GES.

The effect of ocean acidification and changing water conditions on primary (and secondary) marine aerosol emissions is not well understood on a regional or a global scale. To investigate this effect as well as the indirect effect on aerosol that changing biogeochemical parameters can have, ~ 52 m3 pelagic mesocosms were deployed for several weeks in the Mediterranean Sea during both winter pre-bloom and summer oligotrophic conditions and were subjected to various levels of CO2 to simulate the conditions foreseen in this region for the coming decades. After seawater sampling, primary bubble-bursting aerosol experiments were performed using a plunging water jet system to test both chemical and physical aerosol parameters (10–400 nm). Comparing results obtained during pre-bloom and oligotrophic conditions, we find the same four log-normal modal diameters (18.5 ± 0.6, 37.5 ± 1.4, 91.5 ± 2.0, 260 ± 3.2 nm) describing the aerosol size distribution during both campaigns, yet pre-bloom conditions significantly increased the number fraction of the second (Aitken) mode, with an amplitude correlated to virus-like particles, heterotrophic prokaryotes, TEPs (transparent exopolymeric particles), chlorophyll a and other pigments. Organic fractions determined from kappa closure calculations for the diameter, Dp ~ 50 nm, were much larger during the pre-bloom period (64 %) than during the oligotrophic period (38 %), and the organic fraction decreased as the particle size increased. Combining data from both campaigns together, strong positive correlations were found between the organic fraction of the aerosol and chlorophyll a concentrations, heterotrophic and autotrophic bacteria abundance, and dissolved organic carbon (DOC) concentrations. As a consequence of the changes in the organic fraction and the size distributions between pre-bloom and oligotrophic periods, we find that the ratio of cloud condensation nuclei (CCN) to condensation nuclei (CN) slightly decreased during the pre-bloom period. The enrichment of the seawater samples with microlayer samples did not have any effect on the size distribution, organic content or the CCN activity of the generated primary aerosol. Partial pressure of CO2, pCO2, perturbations had little effect on the physical or chemical parameters of the aerosol emissions, with larger effects observed due to the differences between a pre-bloom and oligotrophic environment.

In the vast Low Nutrient Low-Chlorophyll (LNLC) Ocean, the vertical nutrient supply from the sub-surface to the sunlit surface waters is low, and atmospheric contribution of nutrients may be one order of magnitude greater over short timescales. The short turnover time of atmospheric Fe and N supply (<1 month for nitrate) further supports deposition being an important source of nutrients in LNLC regions. Yet, the extent to which atmospheric inputs are impacting biological activity and modifying the carbon balance in oligotrophic environments has not been constrained. Here, we quantify and compare the biogeochemical impacts of atmospheric deposition in LNLC regions using both a compilation of experimental data and model outputs. A metadata-analysis of recently conducted field and laboratory bioassay experiments reveals complex responses, and the overall impact is not a simple "fertilization effect of increasing phytoplankton biomass" as observed in HNLC regions. Although phytoplankton growth may be enhanced, increases in bacterial activity and respiration result in weakening of biological carbon sequestration. The application of models using cli-matological or time-averaged non-synoptic deposition rates produced responses that were generally much lower than observed in the bioassay experiments. We demonstrate that experimental data and model outputs show better agreement on short timescale (days to weeks) when strong synoptic pulse of aerosols deposition, similar in magnitude to those observed in the field and introduced in bioassay experiments, is superimposed over the mean atmospheric deposition fields. These results suggest that atmospheric impacts in LNLC regions have been underestimated by models, at least at daily to weekly timescales, as they typically overlook large synoptic variations in atmospheric deposition and associated nutrient and particle inputs. Inclusion of the large synoptic variability of atmospheric input, and improved representation and parameterization of key processes that respond to atmospheric deposition, is required to better constrain impacts in ocean biogeochemical models. This is critical for understanding and prediction of current and future functioning of LNLC regions and their contribution to the global carbon cycle.

We report here the elemental composition of sinking particles in sediment traps and in the water column following four artificial dust seeding experiments (each representing a flux of 10 g m−2). Dry or wet dust deposition were simulated during two large mesocosms field campaigns that took place in the coastal water of Corsica (NW Mediterranean Sea) representative of oligotrophic conditions. The dust additions were carried out with fresh or artificially aged dust (i.e., enriched in nitrate and sulfate by mimicking cloud processing) for various biogeochemical conditions, enabling us to test the effect of these parameters on the chemical composition and settling of dust after deposition. The rates and mechanisms of total mass, particulate organic carbon (POC) and chemical elements (Al, Ba, Ca, Co, Cu, Fe, K, Li, Mg, Mn, Mo, N, Nd, P, S, Sr and Ti) transfer from the mesocosm surface to the sediment traps installed at the base of the mesocosms after dust deposition show that (1) 15% of the initial dust mass was dissolved in the water column in the first 24 h after seeding. Except for Ca, S and N, the elemental composition of dust particles was constant during their settling, showing the relevance of using interelemental ratios, such as Ti/Al as proxy of lithogenic fluxes. (2) Whatever the type of seeding (using fresh dust to simulate dry deposition or artificially aged dust to simulate wet deposition), the particulate phase both in the water column and in the sediment traps was dominated by dust particles. (3) Due to the high Ba content in dust, Ba/Al cannot be used as productivity proxy in the case of high dust input in the sediment traps. Instead, our data suggests that the ratio Co/Al could be a good productivity proxy in this case. (4) After 7 days, between 30 and 68% of added dust was still in suspension in the mesocosms. This difference in the dust settling was directly associated with a difference in POC export, since POC fluxes were highly correlated to dust lithogenic fluxes signifying a ballast effect of dust. The highest fraction of remaining dust in suspension in the mesocosm at the end of the experiment was found inversely correlated to Chl a increase. This suggests that the fertilizing effect of dust on autotrophs organisms, the ballast effect, and POC fluxes are strongly correlated. (5) Our data emphasize a typical mass ratio Lithogenic/POC fluxes around 30 which could be used as reference to estimate the POC export triggered by wet dust deposition event.

Results from the DUNE experiments reported in this issue have shown that nutrient input from dust deposition in large mesocosms deployed in the western Mediterranean induced a response of the microbial food web, with an increase of primary production rates (PP), bacterial respiration rates (BR), as well as autotrophic and heterotrophic biomasses. Additionally, it was found that nutrient inputs strengthened the net heterotrophy of the system, with NPP : BR ratios < 1. In this study we used a simple microbial food web model, inspired from previous modelling studies, to explore how C, N and P stoichiometric mismatch between producers and consumers along the food chain can influence the dynamics and the trophic status of the ecosystem. Attention was paid to the mechanisms involved in the balance between net autotrophy vs. net heterotrophy. Although the model was kept simple, predicted changes in biomass and PP were qualitatively consistent with observations from DUNE experiments. Additionally, the model shed light on how ecological stoichiometric mismatch between producers and consumers can control food web dynamics and drive the system toward net heterotrophy. In the model, net heterotrophy was notably driven by the parameterisation of the production and excretion of extra DOC from phytoplankton under nutrient-limited conditions. This mechanism yielded to high C : P and C : N ratios of the DOM pool, and subsequent postabsorptive respiration of C by bacteria. The model also predicted that nutrient inputs from dust strengthened the net heterotrophy of the system; a pattern also observed during two of the three DUNE experiments (P and Q). However, the model was not able to account for the low NPP : BR ratios (down to 0.1) recorded during the DUNE experiments. Possible mechanisms involved in this discrepancy were discussed.

In the paper "Microbial food web dynamics in response to a Saharan dust event: results from a mesocosm study in the oligotrophic Mediterranean Sea" by E. Pulido-Villena et al. (2014), the following error occurred: Figs. 7 and 8 were incorrectly switched; that is, Fig. 8 appears with the Fig. 7 caption and vice versa. The figures with the correct captions are presented on the next page.

By bringing new nutrients and particles to the surface ocean, atmospheric deposition impacts biogeochemical cycles. The extent to which those changes are modifying the carbon balance in oligotrophic environments such as the Mediterranean Sea that receives important Saharan dust fluxes is unknown. DUNE project provides the first attempt to evaluate the changes induced in the carbon budget of an oligotrophic system after simulated Saharan dust wet and dry deposition events. Here we report the results for the 3 distinct artificial dust seeding experiments in large mesocosms that were conducted in the oligotrophic waters of the Mediterranean Sea in summer 2008 and 2010. Simultaneous measurements of the metabolic rates (C fixation, C respiration) in the water column have shown that the dust deposition did not change drastically the metabolic balance as the tested waters remained net heterotroph (i.e. net primary production to bacteria respiration ratio < 1) and in some cases the net heterotrophy was even enhanced by the dust deposition. Considering the different terms of the carbon budget, we estimate that it was balanced with a dissolved organic carbon (DOC) consumption of at least 10% of the initial stock. This corresponds to a fraction of the DOC stock of the surface mixed layer that consequently will not be exported during the winter mixing. Although heterotrophic bacteria were found to be the key players in the response to dust deposition, net primary production increased about twice in case of simulated wet deposition (that includes anthropogenic nitrogen) and a small fraction of particulate organic carbon was still exported. Our estimated carbon budgets are an important step forward in the way we understand dust deposition and associated impacts on the oceanic cycles. They are providing knowledge about the key processes (i.e. bacteria respiration, aggregation) that need to be considered for an integration of atmospheric deposition in marine biogeochemical modeling.

By bringing new nutrients and particles to the surface ocean, atmospheric deposition impacts biogeochemical cycles. The extent to which those changes are modifying the carbon balance in oligotrophic environments such as the Mediterranean Sea that receives important Saharan dust fluxes is unknown. The DUNE (DUst experiment in a low Nutrient, low chlorophyll Ecosystem) project provides the first attempt to evaluate the changes induced in the carbon budget of a large body of oligotrophic waters after simulated Saharan dust wet or dry deposition events, allowing us to measure (1) the metabolic fluxes while the particles are sinking and (2) the particulate organic carbon export. Here we report the results for the three distinct artificial dust seeding experiments simulating wet or dry atmospheric deposition onto large mesocosms (52 m³) that were conducted in the oligotrophic waters of the Mediterranean Sea in the summers of 2008 and 2010. Although heterotrophic bacteria were found to be the key players in the response to dust deposition, net primary production increased about twice in case of simulated wet deposition (that includes anthropogenic nitrogen). The dust deposition did not produce a shift in the metabolic balance as the tested waters remained net heterotrophic (i.e., net primary production to bacteria respiration ratio <1) and in some cases the net heterotrophy was even enhanced by the dust deposition. The change induced by the dust addition on the total organic carbon pool inside the mesocosm over the 7 days of the experiments, was a carbon loss dominated by bacteria respiration that was at least 5–10 times higher than any other term involved in the budget. This loss of organic carbon from the system in all the experiments was particularly marked after the simulation of wet deposition. Changes in biomass were mostly due to an increase in phytoplankton biomass but when considering the whole particulate organic carbon pool it was dominated by the organic carbon aggregated to the lithogenic particles still in suspension in the mesocosm at the end of the experiment. Assuming that the budget is balanced, the dissolved organic carbon (DOC) pool was estimated by the difference between the total organic carbon and the particulate organic carbon (POC) pool. The partitioning between dissolved and particulate organic carbon was dominated by the dissolved pool with a DOC consumption over 7 days of ∼1 μmol C L^-1 d^-1 (dry deposition) to ∼2–5 μmol C L^-1 d^-1 (wet deposition). This consumption in the absence of any allochthonous inputs in the closed mesocosms meant a small <10% decrease of the initial DOC stock after a dry deposition but a ∼30–40% decrease of the initial DOC stock after wet deposition. After wet deposition, the tested waters, although dominated by heterotrophy, were still maintaining a net export (corrected from controls) of particulate organic carbon (0.5 g in 7 days) even in the absence of allochthonous carbon inputs. This tentative assessment of the changes in carbon budget induced by a strong dust deposition indicates that wet deposition by bringing new nutrients has higher impact than dry deposition in oligotrophic environments. In the western Mediterranean Sea, the mineral dust deposition is dominated by wet deposition and one perspective of this work is to extrapolate our numbers to time series of deposition during similar oligotrophic conditions to evaluate the overall impact on the carbon budget at the event and seasonal scale in the surface waters of the northwestern Mediterranean Sea. These estimated carbon budgets are also highlighting the key processes (i.e., bacterial respiration) that need to be considered for an integration of atmospheric deposition in marine biogeochemical modeling.

Lithogenic particles, such as desert dust, have been postulated to influence particulate organic carbon (POC) export to the deep ocean by acting as mineral ballasts. However, an accurate understanding and quantification of the POC-dust association that occurs within the upper ocean is required in order to affine the "ballast hypothesis". In the framework of the DUNE project, two artificial seedings were performed seven days apart within large mesocosms. A suite of optical and biogeochemical measurements were used to quantify surface POC export following simulated dust events within a low-nutrient low-chlorophyll ecosystem. The two successive seedings led to a 2.3-6.7 fold higher POC flux as compared to the POC flux observed in controlled mesocosms. A simple linear regression analysis revealed that the lithogenic fluxes explained more than 85% of the variance in POC fluxes. At the scale of a dust deposition event, we estimated that 42-50% of POC fluxes were strictly associated with lithogenic particles through an aggregation process. Lithogenic ballasting also likely impacted the remaining POC fraction which resulted from the fertilization effect. The observations support the "ballast hypothesis" and provide a quantitative estimation of the surface POC export abiotically triggered by dust deposition. In this work, we demonstrate that the strength of such a "lithogenic carbon pump" depends on the biogeochemical conditions of the water column at the time of deposition. Based on these observations, we suggest that this "lithogenic carbon pump" could represent a major component of the biological pump in oceanic areas subjected to intense atmospheric forcing.

The response of the phytoplanktonic community (primary production and algal biomass) to contrasted Saharan dust events (wet and dry deposition) was studied in the framework of the DUNE "a DUst experiment in a low-Nutrient, low-chlorophyll Ecosystem" project. We simulated realistic dust deposition events (10 g m^-2) into large mesocosms (52 m³). Three distinct experimental dust additions were conducted in June 2008 (DUNE-1-P: simulation of a wet deposition, DUNE-1-Q: simulation of a dry deposition) and 2010 (DUNE-2-R1, -R2: simulation of 2 successive wet depositions) in the northwestern oligotrophic Mediterranean Sea. No changes in primary production (PP) and chlorophyll a concentration (Chl a) were observed after a dry deposition event while a wet deposition event resulted in a rapid (24 h after dust additions), strong (up 2.4 fold) and long (at least a week duration) increase in PP and Chl a. We show that in addition to being a source of dissolved inorganic phosphorus (DIP), simulated wet deposition events were also a significant source of NO₃^- (net increases up to +9.8 μM NO₃^- at 0.1 m depth) to the nutrient depleted surface waters due to cloud processes and mixing with anthropogenic species such as HNO₃. The dry deposition event was shown to be a negligible source of NO₃^-. By transiently increasing DIP and NO₃^- concentrations in P-N starved surface waters, wet deposition of Saharan dust was able to relieve the potential N or NP co-limitation of the phytoplanktonic activity. Due to the higher input of NO₃^- relative to DIP, a wet deposition event resulted in a strong increase in the NO₃^-/DIP ratio from initially < 6 to over 150 at the end of the DUNE-2-R1 experiment suggesting a switch from an initial N or NP co-limitation towards a severe P limitation. We also show that the contribution of new production to PP increased after wet dust deposition events from initially 15% to 60-70% 24 h after seeding, indicating a switch from a regenerated-production based system to a new-production based system. DUNE experiments show that wet and dry dust deposition events induce contrasted responses of the phytoplanktonic community due to differences in the atmospheric supply of bioavailable new nutrients. Our results from original mesocosm experiments demonstrate that atmospheric dust wet deposition greatly influences primary productivity and algal biomass in LNLC environments, changes nutrient stocks and alters the NO₃^-/DIP ratio leading to a switch in the nutrient limitation of the phytoplanktonic activity.

The response of the phytoplanktonic community (primary production and algal biomass) to contrasted Sa-haran dust events (wet and dry deposition) was studied in the framework of the DUNE ("a DUst experiment in a low-Nutrient, low-chlorophyll Ecosystem") project. We simu-lated realistic dust deposition events (10 g m −2) into large mesocosms (52 m 3). Three distinct dust addition experiments were conducted in June 2008 (DUNE-1-P: simulation of a wet deposition; DUNE-1-Q: simulation of a dry deposition) and 2010 (DUNE-2-R1 and DUNE-2-R2: simulation of two successive wet depositions) in the northwestern oligotrophic Mediterranean Sea. No changes in primary production (PP) and chlorophyll a concentrations (Chl a) were observed after a dry deposition event, while a wet deposition event resulted in a rapid (24 h after dust addition), strong (up to 2.4-fold) and long (at least a week in duration) increase in PP and Chl a. We show that, in addition to being a source of dis-solved inorganic phosphorus (DIP), simulated wet deposition events were also a significant source of nitrate (NO − 3) (net in-creases up to +9.8 µM NO − 3 at 0.1 m in depth) to the nutrient-depleted surface waters, due to cloud processes and mixing with anthropogenic species such as HNO 3 . The dry deposi-tion event was shown to be a negligible source of NO − 3 . By transiently increasing DIP and NO − 3 concentrations in N–P starved surface waters, wet deposition of Saharan dust was able to relieve the potential N or NP co-limitation of the phy-toplanktonic activity. Due to the higher input of NO − 3 relative to DIP, and taking into account the stimulation of the bio-logical activity, a wet deposition event resulted in a strong increase in the NO − 3 /DIP ratio, from initially less than 6, to over 150 at the end of the DUNE-2-R1 experiment, suggest-ing a switch from an initial N or NP co-limitation towards a severe P limitation. We also show that the contribution of new production to PP strongly increased after wet dust de-position events, from initially 15 % to 60–70 % 24 h after seeding, indicating a switch from a regenerated-production based system to a new-production based system. DUNE ex-periments show that wet and dry dust deposition events in-duce contrasting responses of the phytoplanktonic commu-nity due to differences in the atmospheric supply of bioavail-able new nutrients. Our results from original mesocosm ex-periments demonstrate that atmospheric dust wet deposition Published by Copernicus Publications on behalf of the European Geosciences Union. 4784 C. Ridame et al.: Phytoplanktonic response to Saharan dust events greatly influences primary productivity and algal biomass in LNLC environments through changes in the nutrient stocks, and alters the NO − 3 /DIP ratio, leading to a switch in the nu-trient limitation of the phytoplanktonic activity.

By bringing new nutrients and particles to the surface ocean, atmospheric deposition impacts biogeochemical cycles. The extent to which those changes are modifying the carbon balance in oligotrophic environments such as the Mediterranean Sea that receives important Saharan dust fluxes is unknown. DUNE project provides the first attempt to evaluate the changes induced in the carbon budget of an oligotrophic system after simulated Saharan dust wet and dry deposition events. Here we report the results for the 3 distinct artificial dust seeding experiments in large mesocosms that were conducted in the oligotrophic waters of the Mediterranean Sea in summer 2008 and 2010. Simultaneous measurements of the metabolic rates (C fixation, C respiration) in the water column have shown that the dust deposition did not change drastically the metabolic balance as the tested waters remained net heterotroph (i.e. net primary production to bacteria respiration ratio < 1) and in some cases the net heterotrophy was even enhanced by the dust deposition. Considering the different terms of the carbon budget, we estimate that it was balanced with a dissolved organic carbon (DOC) consumption of at least 10% of the initial stock. This corresponds to a fraction of the DOC stock of the surface mixed layer that consequently will not be exported during the winter mixing. Although heterotrophic bacteria were found to be the key players in the response to dust deposition, net primary production increased about twice in case of simulated wet deposition (that includes anthropogenic nitrogen) and a small fraction of particulate organic carbon was still exported. Our estimated carbon budgets are an important step forward in the way we understand dust deposition and associated impacts on the oceanic cycles. They are providing knowledge about the key processes (i.e. bacteria respiration, aggregation) that need to be considered for an integration of atmospheric deposition in marine biogeochemical modeling.

This chapter provides an overview of the current knowledge on aerosols in the marine atmosphere and the effects of aerosols on climate and on processes in the oceanic surface layer. Aerosol particles in the marine atmosphere originate predominantly from direct production at the sea surface due to the interaction between wind and waves (sea spray aerosol, or SSA) and indirect production by gas to particle conversion. These aerosols are supplemented by aerosols produced over the continents, as well as aerosols emitted by volcanoes and ship traffic, a large part of it being deposited to the ocean surface by dry and wet deposition. The SSA sources, chemical composition and ensuing physical and optical effects, are discussed. An overview is presented of continental sources and their ageing and mixing processes during transport. The current status of our knowledge on effects of marine aerosols on the Earth radiative balance, both direct by their interaction with solar radiation and indirect through their effects on cloud properties, is discussed. The deposition on the ocean surface of some key species, such as nutrients, their bioavailability and how they impact biogeochemical cycles are shown and discussed through different time and space scales approaches.

The main goal of project DUNE was to estimate the impact of atmospheric deposition on an oligotrophic ecosystem based on mesocosm experiments simulating strong atmospheric inputs of eolian mineral dust. Our mesocosm experiments aimed at being representative of real atmospheric deposition events onto the surface of oligotrophic marine waters and were an original attempt to consider the vertical dimension after atmospheric deposition at the sea surface. This introductory paper describes the objectives of DUNE and the implementation plan of a series of mesocosm experiments conducted in the Mediterranean Sea in 2008 and 2010 during which either wet or dry and a succession of two wet deposition fluxes of 10 g m^-2 of Saharan dust have been simulated based on the production of dust analogs from erodible soils of a source region. After the presentation of the main biogeochemical initial conditions of the site at the time of each experiment, a general overview of the papers published in this special issue is presented. From laboratory results on the solubility of trace elements in dust to biogeochemical results from the mesocosm experiments and associated modeling, these papers describe how the strong simulated dust deposition events impacted the marine biogeochemistry. Those multidisciplinary results are bringing new insights into the role of atmospheric deposition on oligotrophic ecosystems and its impact on the carbon budget. The dissolved trace metals with crustal origin - Mn, Al and Fe - showed different behaviors as a function of time after the seeding. The increase in dissolved Mn and Al concentrations was attributed to dissolution processes. The observed decrease in dissolved Fe was due to scavenging on sinking dust particles and aggregates. When a second dust seeding followed, a dissolution of Fe from the dust particles was then observed due to the excess Fe binding ligand concentrations present at that time. Calcium nitrate and sulfate were formed in the dust analog for wet deposition following evapocondensation with acids for simulating cloud processing by polluted air masses under anthropogenic influence. Using a number of particulate tracers that were followed in the water column and in the sediment traps, it was shown that the dust composition evolves after seeding by total dissolution of these salts. This provided a large source of new dissolved inorganic nitrogen (DIN) in the surface waters. In spite of this dissolution, the typical inter-elemental ratios in the particulate matter, such as Ti / Al or Ba / Al, are not affected during the dust settling, confirming their values as proxies of lithogenic fluxes or of productivity in sediment traps. DUNE experiments have clearly shown the potential for Saharan wet deposition to modify the in situ concentrations of dissolved elements of biogeochemical interest such as Fe and also P and N. Indeed, wet deposition yielded a transient increase in dissolved inorganic phosphorus (DIP) followed by a very rapid return to initial conditions or no return to initial conditions when a second dust seeding followed. By transiently increasing DIP and DIN concentrations in P- and N-starved surface waters of the Mediterranean Sea, wet deposition of Saharan dust can likely relieve the potential P and/or N limitation of biological activity; this has been directly quantified in terms of biological response. Wet deposition of dust strongly stimulated primary production and phytoplanktonic biomass during several days. Small phytoplankton (< 3 μm) was more stimulated after the first dust addition, whereas the larger size class (> 3 μm) significantly increased after the second one, indicating that larger-sized cells need further nutrient supply in order to be able to adjust their physiology and compete for resource acquisition and biomass increase. Among the microorganisms responding to the atmospheric inputs, diazotrophs were stimulated by both wet and dry atmospheric deposition, although N₂ fixation was shown to be only responsible for a few percent of the induced new production. Dust deposition modified the bacterial community structure by selectively stimulating and inhibiting certain members of the bacterial community. The microbial food web dynamics were strongly impacted by dust deposition. The carbon budget indicates that the net heterotrophic character (i.e., ratio of net primary production to bacteria respiration < 1) of the tested waters remained (or was even increased) after simulated wet or dry deposition despite the significant stimulation of autotrophs after wet events. This indicates that the oligotrophic tested waters submitted to dust deposition are a net CO₂ source. Nonetheless, the system was able to export organic material, half of it being associated with lithogenic particles through aggregation processes between lithogenic particles and organic matter. These observations support the "ballast" hypothesis and suggest that this "lithogenic carbon pump" could represent a major contribution of the global carbon export to deep waters in areas receiving high rates of atmospheric deposition. Furthermore, a theoretical microbial food web model showed that, all other things being equal, carbon, nitrogen and phosphorus stoichiometric mismatch along the food chain can have a substantial impact on the ecosystem response to nutrient inputs from dusts, with changes in the biomass of all biological compartments by a factor of ~ 2-4, and shifts from net autotrophy to net heterotrophy. Although the model was kept simple, it highlights the importance of stoichiometric constrains on the dynamics of microbial food webs.

The significant impact of dust deposition on het-erotrophic bacterial dynamics in the surface oligotrophic ocean has recently been evidenced. Considering the central role of bacteria in the microbial loop, it is likely that dust deposition also affects the structure and the functioning of the whole microbial food web. In the frame of the DUNE project, aiming to estimate the impact of dust deposition on the oligotrophic Mediterranean Sea through mesocosm ex-periments, the main goal of the present paper was to as-sess how two successive dust deposition events affect the dynamics of the microbial food web. The first dust seeding delivered new P and N to the amended mesocosms and re-sulted in a pronounced stimulation of bacterial respiration. It also induced pronounced, but transient, changes in the bac-terial community composition. No significant effects were observed on the abundances of viruses and heterotrophic nanoflagellates. The second dust seeding also delivered new P and N to the amended mesocosms, but the effect on the microbial food web was very different. Bacterial respira-tion remained constant and bacterial abundance decreased. Compositional changes following the second seeding were minor compared to the first one. The decrease in bacterial abundance coincided with an increase in virus abundance, resulting in higher virus : bacteria ratios throughout the sec-ond seeding period. Our study shows that dust deposition to the surface oligotrophic ocean may involve important mod-ifications of the trophic links among the components of the microbial food web with presumed consequences on C and nutrient cycling.

Abiotic iron removal processes such as scavenging can significantly and rapidly modify iron distribution in the dissolved-colloidal-particulate continuum. Therefore, these processes could be considered, in addition to ligand complexation, as a major control on atmospheric iron dissolution in seawater. In this work, we investigated the seasonal abiotic processes occurring once dust deposited on surface seawater using a series of artificial seeding experiments (allowing us to take into consideration the settling of particles on a 1m depth layer). Here, we demonstrate that atmospheric dissolved iron concentration ([DFe]) is driven by the processes governed by the dissolved organic matter (DOM) pool. Following artificial dust seeding, an order magnitude range increase in the [DFe] (12 - 181nmolL(-1)) was observed depending on the season. Under high and fresh DOM conditions (spring and summer), the rapid formation of aggregates induced a negative feedback on the [DFe] through scavenging, while a fraction of the DFe was likely organically complexed. In contrast, in low-DOM surface waters (winter), aggregation was not observed, allowing a very large transient increase in [DFe] (181nmolL(-1)) before being removed by adsorption onto settling particles. A key result of the findings is that depending on the age and quantity of DOM, the lithogenic carbon pump is likely a major pathway for organic carbon export. Modeling studies should therefore relate both atmospheric iron dissolution in seawater and the intensity of the subsequent biological response, to the age and quantity of DOM.

In this study, we investigate the response of the phytoplankton community, with emphasis on ecophysiology and succession, after two experimental additions of Saharan dust in the surface water layer of a low-nutrient low-chlorophyll ecosystem in the Mediterranean Sea. Three mesocosms were amended with evapocondensed dust to simulate realistic Saharan dust events, while three additional mesocosms were kept unamended and served as controls. The experiment consisted in two consecutive dust additions and samples were daily collected at different depths (-0.1, -5 and -10 m) during one week, starting before each addition occurred. Data concerning HPLC pigment analysis on two size classes (< 3 and > 3 μm), electron transport rate (ETR) vs. irradiance curves, non-photochemical fluorescence quenching (NPQ) and phytoplankton cell abundance (measured by flow cytometry), are presented and discussed in this paper. Results show that picophytoplankton mainly respond to the first dust addition, while the second addition leads to an increase of both pico- and nano-/microphytoplankton. Ecophysiological changes in the phytoplankton community occur, with NPQ and pigment concentration per cell increasing after dust additions. While biomass increases after pulses of new nutrients, ETR does not greatly vary between dust-amended and control conditions, in relation with ecophysiological changes within the phytoplankton community, such as the increase in NPQ and pigment cellular concentration. A quantitative assessment and parameterisation of the onset of a phytoplankton bloom in a nutrient-limited ecosystem is attempted on the basis of the increase in phytoplankton biomass observed during the experiment. The results of this study are discussed focusing on the adaptation of picophytoplankton to nutrient limitation in the surface water layer, as well as on size-dependent competition ability in phytoplankton.

The deposition of atmospheric dust is the primary process supplying trace elements abundant in crustal rocks (e.g. Al, Mn and Fe) to the surface ocean. Upon deposition, the residence time in surface waters for each of these elements differs according to their chemical speciation and biological utilization. Presently, however, the chemical and physical processes occurring after atmospheric deposition are poorly constrained, principally because of the difficulty in following natural dust events in situ. In the present work we examined the temporal changes in the biogeochemistry of crustal metals (in particular Al, Mn and Fe) after an artificial dust deposition event. The experiment was contained inside trace metal clean mesocosms (0–12.5 m depths) deployed in the surface waters of the northwestern Mediterranean, close to the coast of Corsica within the frame of the DUNE project (a DUst experiment in a low Nutrient, low chlorophyll Ecosystem). Two consecutive artificial dust deposition events, each mimicking a wet deposition of 10 g m−2 of dust, were performed during the course of this DUNE-2 experiment. The changes in dissolved manganese (Mn), iron (Fe) and aluminum (Al) concentrations were followed immediately after the seeding with dust and over the following week. The Mn, Fe and Al inventories and loss or dissolution rates were determined. The evolution of the inventories after the two consecutive additions of dust showed distinct behaviors for dissolved Mn, Al and Fe. Even though the mixing conditions differed from one seeding to the other, Mn and Al showed clear increases directly after both seedings due to dissolution processes. Three days after the dust additions, Al concentrations decreased as a consequence of scavenging on sinking particles. Al appeared to be highly affected by the concentrations of biogenic particles, with an order of magnitude difference in its loss rates related to the increase of biomass after the addition of dust. In the case of dissolved Fe, it appears that the first dust addition resulted in a decrease as it was scavenged by sinking dust particles, whereas the second seeding induced dissolution of Fe from the dust particles due to the excess Fe binding ligand concentrations present at that time. This difference, which might be related to a change in Fe binding ligand concentration in the mesocosms, highlights the complex processes that control the solubility of Fe. Based on the inventories at the mesocosm scale, the estimations of the fractional solubility of metals from dust particles in seawater were 1.44 ± 0.19% and 0.91 ± 0.83% for Al and 41 ± 9% and 27 ± 19% for Mn for the first and the second dust addition. These values are in good agreement with laboratory-based estimates. For Fe no fractional solubility was obtained after the first seeding, but 0.12 ± 0.03% was estimated after the second seeding. Overall, the trace metal dataset presented here makes a significant contribution to enhancing our knowledge on the processes influencing trace metal release from Saharan dust and the subsequent processes of bio-uptake and scavenging in a low nutrient, low chlorophyll area.

This review focuses on critical issues in ocean-atmosphere exchange that will be addressed by new research strategies developed by the international Surface Ocean-Lower Atmosphere Study (SOLAS) research community. Eastern boundary upwelling systems are important sites for CO2 and trace gas emission to the atmosphere, and the proposed research will examine how heterotrophic processes in the underlying oxygen-deficient waters interact with the climate system. The second regional research focus will examine the role of sea-ice biogeochemistry and its interaction with atmospheric chemistry. Marine aerosols are the focus of a research theme directed at understanding the processes that determine their abundance, chemistry and radiative properties. A further area of aerosol-related research examines atmospheric nutrient deposition in the surface ocean, and how differences in origin, atmospheric processing and composition influence surface ocean biogeochemistry. Ship emissions are an increasing source of aerosols, nutrients and toxins to the atmosphere and ocean surface, and an emerging area of research will examine their effect on ocean biogeochemistry and atmospheric chemistry. The primary role of SOLAS is to coordinate coupled multi-disciplinary research within research strategies that address these issues, to achieve robust representation of critical ocean-atmosphere exchange processes in Earth System models.

The response of N₂ (dinitrogen) fixation to contrasted (wet and dry) Saharan dust deposition was studied in the framework of the DUNE project (a DUst experiment in a low-Nutrient, low-chlorophyll Ecosystem) during which realistic simulations of dust deposition (10 g m^-2) into large mesocosms (52 m³) were performed. Three distinct experimental dust additions were conducted in June 2008 (DUNE-1-P: simulation of a wet deposition, DUNE-1-Q: simulation of a dry deposition) and 2010 (DUNE-2-R: simulation of 2 successive wet depositions) in the northwestern oligotrophic Mediterranean Sea. Here we show that wet and dry dust deposition induced a rapid (24 h or 48 h after dust additions), strong (from 2- to 5.3-fold) and long (at least 4-6 days duration) increase in N₂ fixation, indicating that both wet and dry Saharan dust deposition was able to relieve efficiently the nutrient limitation(s) of N₂ fixation. This means in particular that N₂ fixation activity was not inhibited by the significant input of nitrate associated with the simulated wet deposition (~ 9 mmol NO₃^- m^-2). The input of new nitrogen associated with N₂ fixation was negligible relative to the atmospheric NO₃^- input associated with the dust. The contribution of N₂ fixation to primary production was negligible (≤ 1%) before and after dust addition in all experiments, indicating that N₂ fixation was a poor contributor to the nitrogen demand for primary production. Despite the stimulation of N₂ fixation by dust addition, the rates remained low, and did not significantly change the contribution of N₂ fixation to new production since only a maximum contribution of 10% was observed. The response of N₂ fixation by diazotrophs and CO₂ fixation by the whole phytoplankton community suggests that these metabolic processes were limited or co-limited by different nutrients. With this novel approach, which allows us to study processes as a function of time while atmospheric particles are sinking, we show that new atmospheric nutrients associated with Saharan dust pulses do significantly stimulate N₂ fixation in the Mediterranean Sea and that N₂ fixation is not a key process in the carbon cycle in such oligotrophic environments.

It has recently been postulated that lithogenic particles such as Saharan dust strongly influence particulate organic carbon export to the deep ocean by acting as mineral ballast. However, our understanding of the processes involved remains scant. In the present study, optical measurements were performed to monitor variations in the concentration, composition and size distribution of particles in suspension within the water column after simulating a Saharan dust event in very clear Mediterranean waters off Corsica in June 2010. A new methodology set up in large mesocosms proved very successful in this regard. Values obtained simultaneously from three instruments (WetLabs ECO-BB3, WetLabs ac-9, Sequoia Scientific LISST-100) provided evidence that (1) part of the Saharan dust pool has a rapid settling velocity (similar to 24-86 m day(-1)), (2) particulate export following a dust event is a nonlinear multi-step process and (3) export is controlled in part by the formation of organic-mineral aggregates. This experimental study provides the first insight of the complex export processes occurring after a dust event involving both physical and biogeochemical forcings in clear oligotrophic waters.

Aerosol particle samples representative of polluted air, dust‐laden air, and clean marine air were collected in marine regions and used in a series of dissolution studies. These samples were exposed to seawater for varying lengths of time and to deionized (Milli‐Q®) water at various values of p H. The percentage of aerosol Mn dissolved in Milli‐Q® water increased from 55 to 80% between p H 8 and p H 2 for pollution aerosols. Less dissolution occurred with the mineral aerosol particles, for which the dissolved Mn increased from 25 to 50% between p H 8 and p H 2. As similar behavior is found for particles collected in clean marine air, we conclude that the dissolution process for aerosol particles from a remote marine area, where crustal Mn dominates pollution Mn, is controlled by the background mineral content. The kinetics of Mn dissolution in seawater are rapid for all the samples: a concentration plateau is reached after 10 min or less of exposure. Release of dissolved Mn from polluted aerosols in seawater was approximately twice the value obtained with mineral particles (55 and 30%, respectively). Apparently, no additional Mn dissolution beyond that which has clearly taken place in rain occurs when rainwater enters the ocean. A positive relationship evidently exists between the total Mn concentration of the aerosol and the dissolved concentration after exposure in seawater. Extrapolating the relationship from the available data suggests that the dissolved saturation value is approximately 60 nmol L −1 . Considering the different behavior found for the different types of particles, at least two cases must be considered when assessing mass balances or calculating atmospheric fluxes of Mn to the ocean. Based on the results of our dissolution studies, the resulting dissolved fluxes of Mn of atmospheric origin during a pulse of Saharan dust range from 0.16 to 0.33 μmol m −2 d −1 over the duration of the pulse. The total dissolved Mn flux from anthropogenic sources in western North Europe is estimated to be 0.3 μmol m −2 d −1 . Fluxes of dissolved Mn of mineral and anthropogenic origin resulting from this calculation in the two examples selected are of the same order of magnitude. The spatial and temporal patterns of these different sources and the dynamics of the upper water column have to be taken into account to estimate quantitatively the impact of atmospheric input on Mn concentrations in the water column.

An exceptional flood event, accompanying a marine storm, was investigated simultaneously at the entrance and the exit of the Gulf of Lion's hydrosystem (NW Mediterranean) in December 2003. Cs, Cr, Co, Ni, Cu, Zn, Cd and Pb signatures of both riverine and shelf-exported particles indicate that continental inputs and resuspended prodeltaic sediments were intensively mixed with resuspended sediments from middle/outer shelf areas during advective transport. As a result, particles leaving the Gulf of Lion inherited the mean signature of shelf bottom sediments, exporting anthropogenic Pb and Zn out into the open sea. When assessing the particulate metal budget in relation with the event, it appears that the output fluxes accounted for between 15% and 60% of the input fluxes, depending on the element and the period of reference. This trend is also observed for annual budgets, which were drawn up by compiling the data from this study and the literature. Results evidenced that, except some element fluxes during extreme output scenario, outputs never counter-balance the inputs. In its current functioning, the Gulf of Lion's shelf seems to act as a retention/sink zone for particulate metals. Regarding anthropogenic fluxes, the contribution of the oceanic flood of December 2003 to the mean annual scenario is considerable. Environmental impacts onto coastal and deep-sea ecosystems should therefore tightly depend on both the intensity and the frequency of event-dominated sediment transport.

The French community working in marine biogeochemistry and biological ecosystems is currently structured to initiate the MERMeX project (Marine Ecosystems Response in the Mediterranean Experiment; http://MERMeX.com.univ-mrs.fr/). This project is part of the large program MISTRALS devoted to the understanding of the Mediterranean environment. MISTRALS is led by the “Institut National des Sciences de l‘Univers” (CNRS-INSU), and it includes several projects, such as HYMeX, related to the study of the hydrological cycle, and CHARMeX, related to the study of the atmospheric chemistry in the Mediterranean basin. MERMeX aims at deepening the current understanding of the Mediterranean marine ecosystems to better anticipate their upcoming evolution in the context of global and anthropogenic changes. It focuses on the response of ecosystems to modifications of physico-chemical forcing at various scales, both in time and space, linked to changing environmental conditions and increasing human pressure. Here, we present general features of the Mediterranean Sea ecosystem functioning as well as the key questions that need to be addressed concerning the Mediterranean Sea to predict the response of the Ecosystem to global change in the twenty-first century as well as ideas for implementation. Most of the information given here will be extended and fully described in the review paper published by the MERMeX group (2011).

A better understanding of the factors controlling N₂ fixation is a pre-requisite for improving our knowledge on the contribution of N₂ fixation process in the nitrogen cycling. Trace-metal clean nutrient/dust addition bioassays (+P, +PFe, +dust) were performed at three stations located in the western, central and eastern Mediterranean Sea, in summer 2008 as part of the BOUM cruise. The main goals were (1) to investigate the nutrient factor(s) limiting N₂ fixation (uptake of ¹⁵N₂) and (2) to evaluate the potential impact of a Saharan dust event on this biological process during the stratification period. Initially, surface waters at the three stations were DIP-depleted (<10 nM) while the DFe concentrations were relatively high (from 1.2 to 2.3 nM) most likely due to atmospheric iron accumulation in the surface mixed layer. At all stations, Saharan dust input relieved the ambient nutrient limitation of the diazotrophic activity as demonstrated by the strong stimulation of N₂ fixation (from 130 % to 430 %). The highest dust stimulation of N₂ fixation was recorded at the station located in the eastern basin. The response of diazotrophic activity to nutrient additions was variable between the sampled stations suggesting a spatial variability of the factor controlling N₂ fixation over the whole basin. At all stations, N₂ fixation was not limited by Fe nor co-limited by P and Fe. At the western station, N₂ fixation was DIP limited while at the eastern one, N₂ fixation was first DIP limited, then was limited by one or several chemical element(s) released by dust. Our results demonstrated that a Saharan dust input was able to relieve these successive on going limitations. Very interestingly, at the station located in the central basin, N₂ fixation was not limited by the availability of P yet it was strongly stimulated by dust addition (x3.1). A chemical element or a combination of several, released by the added dust may have been responsible for the observed stimulations of N₂ fixation. These results indicated that Saharan dust pulses to the surface Mediterranean waters, in addition to P and Fe, could be a source of chemical(s) element(s) that are necessary for metabolic processes and therefore influence rates of N₂ fixation.

The semi-enclosed nature of the Mediterranean Sea, together with its smaller inertia due to the relative short residence time of its water masses, make it highly reactive to external forcings, in particular variations of water, energy and matter fluxes at the interfaces. This region, which has been identified as a “hotspot” for climate change, is therefore expected to experience environmental impacts that are considerably greater than those in many other places around the world. These natural pressures interact with the increasing demographic and economic developments occurring heterogeneously in the coastal zone, making the Mediterranean even more sensitive. This review paper aims to provide a review of the state of current functioning and responses of Mediterranean marine biogeochemical cycles and ecosystems with respect to key natural and anthropogenic drivers and to consider the ecosystems’ responses to likely changes in physical, chemical and socio-economical forcings induced by global change and by growing anthropogenic pressure at the regional scale. The current knowledge on and expected changes due to single forcing (hydrodynamics, solar radiation, temperature and acidification, chemical contaminants) and combined forcing (nutrient sources and stoichiometry, extreme events) affecting the biogeochemical fluxes and ecosystem functioning are explored. Expected changes in biodiversity resulting from the combined action of the different forcings are proposed. Finally, modeling capabilities and necessity for modeling are presented. A synthesis of our current knowledge of expected changes is proposed, highlighting relevant questions for the future of the Mediterranean ecosystems that are current research priorities for the scientific community. Finally, we discuss how these priorities can be approached by national and international multi-disciplinary research, which should be implemented on several levels, including observational studies and modeling at different temporal and spatial scales.

The Mediterranean Sea is a semi-enclosed basin characterized by a strong thermal stratification during summer during which the atmosphere is the main source of new nutrients to the nutrient-depleted surface layer. From aerosol sampling and microcosm experiments performed during the TransMed BOUM cruise (June-July 2008) we showed that: (i) the Mediterranean atmosphere composition (Al, Fe, P) was homogeneous over ~28° of longitude and was a mixture with a constant proportion of anthropogenic contribution and a variable but modest contribution of crustal aerosols. This quite stable composition over a one month period and a long transect (~2500 km) allowed to define the Mediterranean atmospheric "background" that characterizes the summer season in the absence of major Saharan event and forest fires, (ii) primary production significantly increased at all tested stations after aerosols addition collected on-board and after Saharan dust analog addition, indicating that both additions relieved on-going (co)-limitations. Although both additions significantly increased the N₂ fixation rates at the western station, diazotrophic activity remained very low (~0.2 nmol N L−1 d−1), (iii) due to the presence of anthropogenic particles, the probable higher solubility of nutrients associated with mixed aerosols (crustal + anthropogenic contribution), conferred a higher fertilizing potential to on-board collected aerosol as compared to Saharan dust analog. Finally, those experiments showed that atmospheric inputs from a mixed atmospheric event ("summer rain" type) or from a high-intensity Saharan event would induce comparable response by the biota in the stratified Mediterranean SML, during summer.

A significant decrease of dissolved iron (DFe) concentration has been observed after dust addition into mesocosms during the DUst experiment in a low Nutrient low chlorophyll Ecosystem (DUNE), carried out in the summer of 2008. Due to low biological productivity at the experiment site, biological consumption of iron can not explain the magnitude of DFe decrease. To understand processes regulating the observed DFe variation, we simulated the experiment using a one-dimensional model of the Fe biogeochemi-cal cycle, coupled with a simple ecosystem model. Different size classes of particles and particle aggregation are taken into account to describe the particle dynamics. DFe concentration is regulated in the model by dissolution from dust particles and adsorption onto particle surfaces, biological uptake , and photochemical mobilisation of particulate iron. The model reproduces the observed DFe decrease after dust addition well. This is essentially explained by particle adsorption and particle aggregation that produces a high export within the first 24 h. The estimated particle adsorption rates range between the measured adsorption rates of soluble iron and those of colloidal iron, indicating both processes controlling the DFe removal during the experiment. A dissolution timescale of 3 days is used in the model, instead of an instantaneous dissolution, underlining the importance of dissolution kinetics on the short-term impact of dust deposition on seawater DFe. Sensitivity studies reveal that initial DFe concentration before dust addition was crucial for the net impact of dust addition on DFe during the DUNE experiment. Based on the balance between abiotic sinks and sources of DFe, a critical DFe concentration has been defined, above which dust depo-Correspondence to: Y. Ye () sition acts as a net sink of DFe, rather than a source. Taking into account the role of excess iron binding ligands and biotic processes, the critical DFe concentration might be applied to explain the short-term variability of DFe after natural dust deposition in various different ocean regions.

The response of the microbial community to Saharan dust deposition was investigated in 6 large mesocosms (52 m(3)) deployed at an oligotrophic coastal site in the NW Mediterranean Sea in June 2008 (DUNE project). The mesocosms represented well the environmental conditions observed at the study site during the 8 d experimental period, and the triplicate mesocosms exhibited high reproducibility for each treatment. Dust deposition resulted in an increase in chlorophyll a concentration (0.22 +/- 0.03 mu g l(-1)), as compared to that in the control treatments (0.12 +/- 0.01 mu g l(-1)), but no treatment effect was observed for bacterial heterotrophic abundance at 5 m depth. Results from the fingerprinting technique CE-SSCP indicate a temporal evolution of the structure of the total (16S rRNA gene) and active (16S rRNA transcripts) bacterial community, and Saharan dust deposition had a noticeable structuring effect on the active bacterial community. Combining results from 16S rRNA gene clone libraries and CE-SSCP indicates that the relative contribution of Alteromonas macleodii to the active bacterial community was enhanced 2-fold following dust addition. The 2 operational taxonomic units (OTUs) Thiothrix and Alteromonas, belonging to Gammaproteobacteria, and the Bacteroidetes OTU NS5-1 were specific to the clone libraries from the dust-amended mesocosms or more abundant in these than in the control ones. CARD-FISH analyses, however, indicate that these OTUs had overall low abundances (1 to 5% of total DAPI-counts). Despite the pronounced temporal trend observed during the experimental period, dust deposition had a small, but noticeable structuring effect on the heterotrophic bacterial community that was detectable only at the OTU level at 99% similarity of the 16S rRNA gene.

Intense Saharan dust deposition occurs over large oligotrophic areas in the Mediterranean Sea and in the Tropical Atlantic, and its impact on the biogeochemical functioning of such oligotrophic ecosystems needs to be understood. However, due to the logistical difficulties of investigating in situ natural dust events, and due to the inherent limitations of microcosm laboratory experiments, new experimental approaches need to be developed. In this paper, we present a new experimental setup based on large, clean mesocoms deployed in the frame of the DUNE (a DUst experiment in a low-Nutrient, low-chlorophyll Ecosystem) project. We demonstrate that these tools are highly relevant and provide a powerful new strategy to in situ studies of the response of an oligotrophic ecosystem to chemical forcing by atmospheric deposition of African dust. First, we describe how to cope with the large amount of dust aerosol needed to conduct the seeding experiments by producing an analogue from soil collected in a source area and by performing subsequent appropriate physico-chemical treatments in the laboratory, including an eventual processing by simulated cloud water. The comparison of the physico-chemical characteristics of produced dust analogues with the literature confirms that our experimental simulations are representative of dust, aging during atmospheric transport, and subsequent deposition to the Mediterranean. Second, we demonstrate the feasibility in coastal areas to installing, in situ, a series of large (6 × 52 m³) mesocosms without perturbing the local ecosystem. The setup, containing no metallic parts and with the least possible induced perturbation during the sampling sequence, provides an approach for working with the required conditions for biogeochemical studies in oligotrophic environments, where nutrient and micronutrients are at nano- or subnano-molar levels. Two, distinct "seeding experiments" were conducted by deploying three mesocosms serving as controls (CONTROLS-Meso = no addition) and three mesocosms seeded with the same amount of Saharan dust (DUST-Meso = 10 g m^-2 of sprayed dust). A large panel of biogeochemical parameters was measured at 0.1 m, at 5 m and 10 m in all of the mesocosms and at a selected site outside the mesocosms before seeding and at regular intervals afterward. Statistical analyses of the results show that data from three mesocosms that received the same treatment are highly reproducible (variability < 30%) and that there is no significant difference between data obtained from CONTROLS-Meso and data obtained outside the mesocosms. This paper demonstrates that the methodology developed in the DUNE project is suitable to quantifying and parameterizing the impact of atmospheric chemical forcing in a low-nutrient, low-chlorophyll (LNLC) ecosystem. Such large mesocosms can be considered as 1-D ecosystems so that the parameterization obtained from these experiments can be integrated into ecosystem models.

Dissolution of wind blown dust is a major source of iron, manganese and other trace nutrients in the ocean. Kinetic and thermodynamic values for the release of metals from dust are needed for computer models which incorporate dust as part of their ocean system. Here we investigate both the thermodynamic and kinetics parameters involved in the dissolution of metals from dust in seawater. We added dust from the Sahara and the Western United States in five different concentrations (0.01-5.0 mg/L) representative of those concentrations found in seawater after dust events, to open-ocean Pacific seawater. Sub-sampling of the reaction vessels took place on days 1, 2, 4, 7, 14, and 35 for the kinetic study. Results show different apparent thermodynamic constants for manganese (Mn) and iron (Fe). The final Mn concentrations are proportional to the added dust concentration. Fe concentrations reach a maximum of less than 2 nM, independent of the quantity and type of dust added. The Fe dissolution kinetics are faster than our sampling resolution. The first order rate constant for the dissolution of Mn from the Western US and Sahara dusts were 0.94 +/- 0.04 nmol Mn/day mg Dust, and 0.22 +/- 0.01 nmol Mn/day mg Dust respectively. We conclude that, Mn concentrations are limited by available Mn on the dust surface, while Fe concentrations are limited by the ligand concentrations in the seawater, which ultimately are determined by the biological community. (C) 2008 Elsevier B.V. All rights reserved.

In much of the world's low-nutrient low-chlorophyll (LNLC) oceans, including the Mediterranean Sea, surface dissolved inorganic phosphorus (DIP) is below the detection limit of conventional techniques. Although dust deposition has been generally recognized as a major source of P to the Mediterranean Sea, the lack of DIP data at nanomolar levels has so far precluded a quantification of this effect. This work reports the first one-year time series of surface nanomolar DIP in the Mediterranean Sea. Moreover, by combining nanomolar DIP data from two field studies (the above cited time-series and an experimental addition of Saharan dust to large mesocosms) and one in vitro dust dissolution experiment, we show that dust pulses may indeed provoke transient increases in DIP concentration (up to 80 nM) in P-starved surface waters of this LNLC region. Citation: Pulido-Villena, E., V. Rerolle, and C. Guieu (2010), Transient fertilizing effect of dust in P-deficient LNLC surface ocean, Geophys. Res. Lett., 37, L01603, doi: 10.1029/2009GL041415.

Abstract. Simultaneous measurements of atmospheric deposition and of sinking particles at 200 and 1000 m depth, were performed in the Ligurian Sea (North-Western Mediterranean) between 2003 and 2007, along with phytoplanktonic activity derived from satellite images. Atmospheric deposition of Saharan dust particles was very irregular and confirmed the importance of sporadic high magnitude events over the annual average (11.4 g m−2 yr−1 for the 4 years). The average marine total mass flux was 31 g m−2 yr−1, the larger fraction being the lithogenic one (~37%). The marine total mass flux displayed a seasonal pattern with a maximum in winter, occurring before the onset of the spring bloom. The highest POC fluxes did not occur during the spring bloom nor could they be directly related to any noticeable increase in the surface phytoplanktonic biomass. Over the 4 years of the study, the strongest POC fluxes were concomitant with large increases of the lithogenic marine flux, which had originated from either recent Saharan fallout events (February 2004 and August 2005), from "old" Saharan dust "stored" in the upper water column layer (March 2003 and February 2005), or alternatively from lithogenic material originating from Ligurian riverine flooding (December 2003, Arno, Roya and Var rivers). Those associated export fluxes defined as "lithogenic events", are believed to result from a combination of forcing (winter mixing or Saharan events, in particular extreme ones), biological (zooplankton) activity, and also organic-mineral aggregation inducing a ballast effect. By fertilising the surface layer, mixed Saharan dust events were shown to be able to induce "lithogenic events" during the stratification period. These events would be more efficient in transferring POC to the deeper layers than the spring bloom itself. The extreme Saharan event of February 2004 exported ~45% of the total annual POC, compared to an average of ~25% for the bloom period. This emphasises the role played by these "lithogenic events", and in particular those that are induced by the more extreme Saharan events, in the carbon export efficiency in the North-western Mediterranean Sea.

Soil dust deposition is recognized as a major source of iron to the open ocean at global and regional scales. However, the processes that control the speciation and cycle of iron in the surface ocean after dust deposition are poorly documented mainly due to the logistical difficulties to investigate in-situ, natural dust events. The development of clean mesocosms in the frame of the DUNE project (a DUst experiment in a low Nutrient low chlorophyll Ecosystem) was a unique opportunity to investigate these processes at the unexplored scale of one dust deposition event. During the DUNE-1-P mesocosm seeding experiment, iron stocks (dissolved and particulate concentrations in the water column) and fluxes (export of particulate iron in sediment traps) were followed during 8 days after an artificial dust seeding mimicking a wet deposition of 10 g m −2. The addition of dust at the surface of the mesocosms was immediately followed by a decrease of dissolved iron [dFe] concentration in the 0-10 m water column. This decrease was likely due to dFe scavenging on settling dust particles and mineral organic aggregates. The scavenging ratio of dissolved iron on dust particles averaged 0.37 ± 0.12 nmol mg −1. Batch dissolution experiments conducted in parallel to the mesocosm experiment showed a increase (up to 600 %) in dust iron dissolution capacity in dust-fertilized waters compared to control conditions. This study gives evidences of complex and unexpected effects of dust deposition on surface ocean biogeo-chemistry: (1) large dust deposition events may be a sink for surface ocean dissolved iron and (2) successive dust deposi-tion events may induce different biogeochemical responses in the surface ocean.

Climate change is projected to significantly alter the delivery (stratification, boundary currents, aridification of landmasses, glacial melt) of iron to the Southern Ocean. We report the most comprehensive suite of biogeochemical iron budgets to date for three contrasting sites in subantarctic and polar frontal waters south of Australia. Distinct regional environments were responsible for differences in the mode and strength of iron supply mechanisms, with higher iron stocks and fluxes observed in surface northern subantarctic waters, where atmospheric iron fluxes were greater. Subsurface waters southeast of Tasmania were also enriched with particulate iron, manganese and aluminum, indicative of a strong advective source from shelf sediments. Subantarctic phytoplankton blooms are thus driven by both seasonal iron supply from southward advection of subtropical waters and by wind-blown dust deposition, resulting in a strong decoupling of iron and nutrient cycles. We discuss the broader global significance our iron budgets for other ocean regions sensitive to climate-driven changes in iron supply.

[1] The bacterial response to dust pulses was investigated in the Mediterranean Sea through a combined field and experimental study. During the stratification period, characterized by a nutrient-starved mixed layer isolated from the depth, a Saharan dust event (2.6 gm(-2)) induced a 1.5-fold increase in bacterial abundance (BA) and a 2-fold increase in bacterial respiration (BR). Experimental dust additions (equivalent to fluxes of 5 and 20 g m(-2)) to bacteria natural assemblages also stimulated BA (between 2- and 4-fold increases) and BR (between 1.5- and 3-fold increases). Pooling the in situ and experimental data, linear relationships were obtained between dust concentration and BA (r(2) = 0.86; p < 0.01) and BR (r(2) = 0.89; p < 0.001). The dust-induced bacterial bloom resulted in a C mineralization of 0.5 g m(-2), which may represent up to 70% of bioavailable DOC annually exported to the depth in the Mediterranean. These results demonstrate that heterotrophic bacteria may play a much larger role in the connections between dust and the ocean carbon cycle than previously recognized and highlight the need for a more accurate understanding of how dust pulses may affect C export in the oligotrophic ocean.

Dissolved iron (DFe) distributions (<0.2 µm) were determined in the upper water column (0–400 m) of the south eastern tropical and subtropical Pacific, in October–November 2004. Data were collected along a transect extending from the Marquesas Islands to the Chilean coast with most of the stations located in the south Pacific gyre. The concentrations of DFe presented large variability with highest values observed at both extremities of the transect. In the Chilean upwelling, DFe concentrations ranged between 1.2–3.9 nM. These high values result from inputs from the continental margin and are likely maintained by anoxic conditions in the water corresponding to the Oxygen Minimum Zone (OMZ). In subsurface waters near the Marquesas, that were also associated with the extension of the OMZ, DFe concentrations varied between 0.15–0.41 nM. Vertical transport of this water by mesoscale activity eastward of the archipelago may explain the dissymmetric east-west distribution of chlorophyll-<i>a</i> evidenced by satellite images. Using the new tracer Fe*=DFe-<i>r</i>_Fe:P (PO₄^3-) we show that DFe was in deficit compared to PO₄^3- resulting from the remineralisation of organic matter. This suggests that the Marquesas islands and the surrounding plateau are not a significant source of DFe. In the gyre, DFe concentrations in the upper 350 m water column were around 0.1 nM and the ferricline was located well below the nitracline. These low concentrations reflect the low input of DFe from the atmosphere, from the ventilation of the upper thermocline with water containing low DFe, and from the low biological activity within this ultra oligotrophic gyre.

Aerosol concentrations in the Southern Hemisphere are largely undersampled. This study presents a chemical and physical description of dust particles collected on board research vessels in the southeast Pacific (SEPS) and the Southern Ocean (SOKS). Concentrations of dust were 6.1 ± 2.4 ng m À3 for SEPS and 13.0 ± 6.3 ng m À3 for SOKS. Dust fluxes, derived from those concentrations, were 9.9 ± 3.7 mg m À2 d À1 for SEPS and 38 ± 14 mg m À2 d À1 for SOKS and are shown to be representative of actual fluxes in those areas. Dust and iron deposition are up to 2 orders of magnitude lower than former predictions. A map of dust deposition on the Southern Hemisphere is proposed by incorporating those in situ measurements into a dust model. This study confirms that dust deposition is not the dominant source of iron to the large high-nutrient low-chlorophyll Southern Ocean.

Iron is an essential nutrient involved in a variety of biological processes in the ocean, including photosynthesis, respiration and dinitrogen fixation. Atmospheric deposition of aerosols is recognized as the main source of iron for the surface ocean. In high nutrient, low chlorophyll areas, it is now clearly established that iron limits phytoplankton productivity but its biogeochemical role in low nutrient, low chlorophyll environments has been poorly studied. We investigated this question in the unexplored southeast Pacific, arguably the most oligotrophic area of the global ocean. Situated far from any continental aerosol source, the atmospheric iron flux to this province is amongst the lowest of the world ocean. Here we report that, despite low dissolved iron concentrations (~0.1 nmol l^-1) across the whole gyre (3 stations located in the center and at the western and the eastern edges), primary productivity are only limited by iron availability at the border of the gyre, but not in the center. The seasonal stability of the gyre has apparently allowed for the development of populations acclimated to these extreme oligotrophic conditions. Moreover, despite clear evidence of nitrogen limitation in the central gyre, we were unable to measure dinitrogen fixation in our experiments, even after iron and/or phosphate additions, and cyanobacterial nif H gene abundances were extremely low compared to the North Pacific Gyre. The South Pacific gyre is therefore unique with respect to the physiological status of its phytoplankton populations.

A better comprehension of atmospheric iron dissolution in seawater would be a key advance in understanding the atmospheric supply of iron to the ocean and its role on marine biogeochemistry. So far, different studies have demonstrated that dissolution of atmospheric iron depends on physical and chemical properties of the particles, which can be modified during their transport from the source. Here, based on a one-year time-series in the Western Mediterranean Sea, we show that dissolution of iron from a Saharan desert dust sample in seawater follows the seasonal trend of the dissolved organic carbon (DOC) variability in the surface layer. As part of the DOC pool, the role of iron binding ligands, probably derived from bacteria activity, has also been investigated. The dust iron dissolution rates are found to be linearly dependent on iron binding ligands and dissolved organic carbon concentrations (r 2 > 0.65, p < 0.01, n = 9).

ChArMEx is a new regional project on tropospheric chemistry and aerosols in the Mediterranean proposed by the French community, calling for international cooperation. ChArMEx proposes an integrated modelling and observational approach to study budgets of species, chemical and dynamical processes, intense events, trends, and impacts. The objectives include an assessment of the recent past, present and future states of the atmospheric chemistry and of related impacts on air quality, regional climate and marine biogeochemistry. The experimental strategy includes long-term monitoring, 2 years of enhanced surface observations, and summer intensive campaigns with research aircrafts and drifting balloons to study the aging of continental air masses over the basin when pollutants and desert dusts are at their maximum and likely impact the regional climate. Focus is presently put on the western basin. Synergies are built with other Mediterranean projects on the hydrological cycle (HyMEx) and marine ecosystems (MERMEX).

The role of potential factors limiting bacterial growth was investigated along vertical and longitudinal gradients across the South Eastern Pacific Gyre. The effects of glucose, nitrate, ammonium and phosphate additions on heterotrophic bacterial production (using leucine technique) were studied in parallel in unfiltered seawater samples incubated under natural daily irradiance. The enrichments realized on the subsurface showed three types of responses. From 141° W (Marquesas plateau) to approx 125° W, bacteria were not bottom-up controlled, as confirmed by the huge potential of growth in non-enriched seawater (median of enhancement factor×39 in 24 h). Within the Gyre (125° W–95° W), nitrogen alone stimulated leucine incorporation rates (median×4.2), but rapidly labile carbon (glucose) became a second limiting factor (median×37) when the two elements were added. Finally from the border of the gyre to the Chilean upwelling (95° W–73° W), labile carbon was the only factor stimulating heterotrophic bacterial production. Interaction between phytoplankton and heterotrophic bacterial communities and the direct versus indirect effect of iron and macronutrients on bacterial production were also investigated in four selected sites: two sites on the vicinity of the Marquesas plateau, the centre of the gyre and the Eastern border of the gyre. Both phytoplankton and heterotrophic bacteria were limited by availability of nitrogen within the gyre, but not by iron. Iron limited phytoplankton at Marquesas plateau and at the eastern border of the gyre. However 48 h enrichment experiments were not sufficient to show any clear limitation of heterotrophic bacteria within Marquesas plateau and showed a limitation of these organisms by labile carbon in the eastern border of the Gyre.

Dissolved iron (DFe) distributions (<0.2 µm) were determined in the upper water column (0–400 m) of the south eastern tropical and subtropical Pacific, in October–November 2004. Data were collected along a transect extending from the Marquesas Islands to the Chilean coast with most of the stations located in the south Pacific gyre. The concentrations of DFe presented large variability with highest values observed at both extremities of the transect. In the Chilean upwelling, DFe concentrations ranged between 1.2–3.9 nM. These high values result from inputs from the continental margin and are likely maintained by anoxic conditions in the water corresponding to the Oxygen Minimum Zone (OMZ). In subsurface waters near the Marquesas, that were also associated with the extension of the OMZ, DFe concentrations varied between 0.15–0.41 nM. Vertical transport of this water by mesoscale activity eastward of the archipelago may explain the dissymmetric east-west distribution of chlorophyll a evidenced by satellite images. Using the new tracer Fe*=DFe–r_Fe:P (PO₄^3-) we show that DFe was in deficit compared to PO₄^3- resulting from the remineralisation of organic matter. This suggests that the Marquesas islands and the surrounding plateau are not a significant source of DFe. In the gyre, DFe concentrations in the upper 350 m water column were around 0.1 nM and the ferricline was located well below the nitracline. These low concentrations reflect the low input of DFe from the atmosphere, from the ventilation of the upper thermocline with water containing low DFe, and from the low biological activity within in this ultra oligotrophic gyre.

Iron is an essential nutrient involved in a variety of biological processes in the ocean, including photosynthesis, respiration and nitrogen fixation. Atmospheric deposition of aerosols is recognized as the main source of iron for the surface ocean. In high nutrient, low chlorophyll areas, it is now clearly established that iron limits phytoplankton productivity but its biogeochemical role in low nutrient, low chlorophyll environments has been poorly studied. We investigated this question in the unexplored southeast Pacific, arguably the most oligotrophic area of the global ocean. Situated far from any continental aerosol source, the atmospheric iron flux to this province is amongst the lowest of the world ocean. Here we report that, despite low dissolved iron concentrations (~0.1 nmol l^-1) measured across the whole gyre (3 stations situated in the center, the western and the eastern edge), photosynthesis and primary productivity are only limited by iron availability at the border of the gyre, but not in the center. The seasonal stability of the gyre has apparently allowed for the development of populations acclimated to these extreme oligotrophic conditions. Moreover, despite clear evidence of nitrogen limitation in the central gyre, we were unable to measure nitrogen fixation in our experiments, even after iron and/or phosphate additions, and cyanobacterial <i>nifH</i> gene abundances were extremely low compared to the North Pacific Gyre. The South Pacific gyre is therefore unique with respect to the physiological status of its phytoplankton populations.

The role of potential factors limiting bacterial growth was investigated along vertical and longitudinal gradients across the South Eastern Pacific Gyre. The effects of glucose, nitrate, ammonium and phosphate additions on heterotrophic bacterial production (using leucine technique) were studied in parallel in unfiltered seawater samples incubated under natural daily irradiance. Longitudinally, the enrichments realized on the subsurface showed three types of responses. From the Marquesas plateau (8° W to approx 125° W), bacteria were not bottom-up controlled, as confirmed by the huge potential of growth in non-enriched seawater (43±24 times in 24 h). Within the Gyre (125° W–95° W), nitrogen alone stimulated leucine incorporation rates by a factor of 5.6±3.6, but rapidly labile carbon (glucose) became a second limiting factor (enhancement factor 49±32 when the two elements were added). Finally from the border of the gyre to the Chilean upwelling (95° W–73° W), labile carbon was the only factor stimulating heterotrophic bacterial production. Interaction between phytoplankton and heterotrophic bacterial communities and the direct versus indirect effect of iron and macronutrients on bacterial production were also investigated in four selected sites: two sites on the vicinity of the Marquesas plateau, the centre of the gyre and the Eastern border of the gyre. Both phytoplankton and heterotrophic bacteria were limited by availability of nitrogen within the gyre, but not by iron. While iron limited phytoplankton at Marquesas plateau and at the eastern border of the gyre, heterotrophic bacteria were only limited by availability of labile DOC in those environments.

A 1-year survey of simultaneous measurements of total atmospheric deposition and dissolved iron concentrations in surface waters (0-40 m) was performed in the northwestern Mediterranean Sea, an area with a marked seasonal hydrological regime. The total atmospheric iron flux was 1118 mg m(-2) (i.e., 20.4 mmol m(-2)). By using aluminium as a crustal marker the deposition was mainly attributed to Saharan dust deposition. Dissolved iron flux was estimated to be 42 mmol m(-2) yr(-1), of which 44% was anthropogenic in origin and 56% was of Saharan origin. Dissolved iron profiles revealed four typical situations throughout the year: (1) a winter situation with homogenous dissolved iron concentrations ranging from 0.8 to 0.9 nmol L-1, (2) a spring situation with uniformly low concentrations ranging from 0.2 to 0.5 nmol L-1, (3) a summer situation with enriched surface waters up to 1.2 nmol L-1, and (4) an autumnal situation with homogenous concentrations ranging from 0.9 to 1.1 nmol L-1. The results demonstrate that the iron enrichment in the mixed layer observed during the stratified period was of the same order of magnitude as the cumulative atmospheric inputs for the same period. The seasonal variability of dissolved iron (DFe) concentrations in surface waters was driven by a combination of factors, including aeolian Fe deposition, nature of aerosols, vertical mixing, phytoplankton uptake, and particle scavenging. Iron distribution can have a clear biogeochemical effect on the autotrophic communities: The low Fe: P ratio observed during the bloom indicates a possible iron limitation for phytoplankton, and the dissolved iron enrichment during summer is certainly at the origin of the development of diazotrophs populations in the system.

During 48 hour stations during the three Programme Océan Multidisciplinaire Méso Echelle (POMME) cruises in 2001 (late winter, spring, and late summer) at different locations within the region studied (38°-45°N, 15°-21°W), drifting sediment traps were deployed at 200 m and 400 m. Fluxes increased from late winter (POMME 1) to spring (POMME 2), with highest values in the North Atlantic gyre (109.1, 20.1, and 3.5 mg m À2 d À1 for mass, C, and N, respectively) and decreased during POMME 3 to reach threshold values (19.1 ± 6.0, 4.4 ± 1.1, and 0.7 ± 0.2 mg m À2 d À1 , respectively). Lipid class tracers and their fatty acid composition analyzed by gaseous chromatography were used to assess the quality and quantity of organic matter fluxes. Wide seasonal variability was observed in biogenic lipid fluxes (0.42 ± 0.19 and 0.39 ± 0.13 mg m À2 d À1 , 1.78 ± 1.08 and 0.69 ± 0.56 mg m À2 d À1 , and 0.71 ± 0.14 and 0.45 mg m À2 d À1 on average at 200 m and 400 m during late winter, spring, and late summer, respectively) in relation with the development of the spring phytoplankton bloom. In a northern persistent anticyclonic eddy a major export of algal matter occurred through zooplankton activity. In contrast with this pattern, the southernmost anticyclonic eddy exhibited the lowest particle fluxes in relation to the low productivity and the high bacterial carbon demand prevailing in the surface waters. In the main cyclonic structure (C4) and the saddle zone (during POMME 2) the pattern of lipid biotracers reflected the permanence of a zooplankton community and likely advective transfer of matter between 43.5°N and 42°N through subsurface water circulation.

In the framework of the Programme Océan Multidisciplinaire Méso Echelle (POMME) experiment, a 1.5 year record (February 2001–June 2002) of downward particle flux at 400 m and 1000 m was measured by sediment traps at four moorings located in the northeast Atlantic between 39°–43°N and 17°–19°W. Thorium-230 was used to estimate sediment trap efficiency, revealing values ranging from 18.5 to 55%. The lowest trapping efficiency was observed for the trap having experienced the highest currents. Significant interannual variability between 2001 and 2002 was clearly linked to the differences observed in the mixed layer depth. At some sites, particulate organic carbon (POC) export was higher (up to a factor of 1.6) during summer than during the spring event. This could be related to the occurrence of short wind events that deepened the thermocline along with the presence of anticyclonic eddies, yielding an input of new nutrients. The average percentage of POC exported compared to the primary production of organic carbon in the surface waters ranged between 1.3 and 5.0%, with higher export efficiency during the spring. Finally, although the area was shown to present a relatively high mesoscale activity that might impact the geochemistry, POC export was rather homogeneous over the POMME area: 4.9 ± 1.6 gC m−2 yr−1 were exported below 1000 m between February 2001 and February 2002. Therefore a large fraction of the new production may be exported through convection and mode water circulation rather than by particle settling.

While the Mediterranean region is typified by frequent summer fires, the 2003 heat wave that hit Europe, and France in particular, made this season longer causing devastating fires. Aerosol sampling performed in the French Riviera between August and September 2003 indicated that iron concentrations in 2003 were significantly higher than in previous years. Continuous pyrogenic emissions are suspected to be the cause of high Fe concentrations. When these particles were dissolved in seawater, 2% of the total iron content was found in solution. This amount could be significant for the water column on a regional scale. Indeed, these fires might explain the observed dissolved iron enrichment of the surface mixed layer (+0.4 nM) measured in the Ligurian Sea during August. In contrast to a locally significant effect, pyrogenic inputs have little impact on the global Fe budget since they represent at most 10% of desert dust inputs.

The effect of atmospheric inputs on phytoplanktonic dynamics was investigated in the Mediterranean Sea during the season characterized by a stratified water column, low primary productivity, and low concentrations of nutrients ([nitrate] < 50 nmol L-1; [phosphate] = 20 nmol L-1; [silicate] = 0.7 mu mol L-1). We report here data obtained during microcosm enrichment experiments performed on the natural assemblage using different combinations of realistic additions (Saharan dust, Fe, Fe + phosphate, and anthropogenic particles). Saharan dust and Fe + phosphate treatments significantly stimulated primary production. Anthropogenic particles and Fe + phosphate treatments increased the chlorophyll a concentrations, enhancing mainly the small cells (pico- and nanophytoplankton). The autotrophic community structure was significantly altered; for example, Fe and Fe + phosphate additions benefited prokaryotic populations, indicating possible nitrogen fixation. The colimitation of both phosphate and Fe was removed by these additions. Results emphasized the effect of Fe, although the ambient concentration was close to I nmol L-1. The addition of dust benefited eukaryotic populations, which indicates that the dust was a possible source of nitrogen. An abiotic dissolution experiment of macronutrients attached to dust confirmed this hypothesis. The dissolution of Fe attached to the dust (0.23-0.61%) and to the anthropogenic particles (0.86-1.85%) was consistent with previous studies conducted under abiotic conditions. This result suggests that the possible enhancement of the dissolution processes caused by biological activity might have been balanced by Fe consumption by the biota and its adsorption on both mineral and organic particles.

[ 1] The biogenic (BSi) and lithogenic (LSi) silica export fluxes were investigated in the northeast Atlantic (38 degrees - 45 degrees N, 16 degrees - 22 degrees W) as part of the Programme Ocean Multidisciplinaire Meso Echelle (POMME) program in 2001 - 2002. They were measured at four stations located on both sides of a frontal zone (40 degrees - 42 degrees N) by means of permanent moorings of sediment traps deployed at 400 and 1000 m depth. Averaged over the area, the annual BSi fluxes ( corrected from Th-230 trapping efficiencies) ranged between 0.240 mmol m(-2) d(-1) at 400 m to 0.316 mmol m(-2) d(-1) at 1000 m. The bulk annual BSi fluxes are comparable to bulk BSi export fluxes recorded for oligotrophic areas. The annual export flux of LSi ( range 0.029 mmol m(-2) d(-1) at 400 m to 0.054 mmol m(-2) d(-1) at 1000 m) was lower than BSi and accounted for 10% of the total silica export flux. Results show a strong coupling between the two siliceous particulate fractions, which is interpreted as reflecting LSi scavenging by BSi and limitation of BSi production in surface water by lithogenic ( trace metals) inputs. BSi export was maximum at the beginning of the productive season during the spring bloom. However, annual BSi export fluxes in 2001 were quite higher at 400 m in the southern area ( e. g., 0.249 - 0.288 at the southeast station versus 0.211 mmol BSi m(-2) d(-1) at the northeast station) contradictory to the classical south-north surface production increase. We suggest an advective lateral transport within the upper 400 m of siliceous particles from the northern, more productive area to the southern region.

Because of recent findings that Fe is a limiting factor for phytoplankton activity even at relatively high dissolved iron (DFe) concentrations, the potential importance of Fe limitation was revisited in the northeast Atlantic Ocean (39-458N, 17-218W). We report data gathered during deck incubation experiments performed at three stations in February-March 2001 with surface seawater containing DFe concentrations of ;0.40 nmol L21. At all stations, Fe addition enhanced phytoplankton growth. Fe limitation was moderate and occurred simultaneously with limitation by major nutrients. This was clearly demonstrated for diatoms that were colimited by orthosilicic acid. Micro-, nano-, and picoplankton benefited from Fe enrichment. Experiments performed with the trihydroxamate siderophore desferrioxamine mesylate B (DFOB) indicated that Fe reserves exist within the cells, especially within the larger cells. This reserve could result from luxurious storage of Fe by colimited cells during episodic atmospheric deposition of Saharan dust. Simulating concentrations of dust resulting from aerosol deposition in well-stratified surface waters, we determined that the solubility of Saharan dust was very low (,0.1% w/w) but the amount of DFe released in seawater was sufficient to relieve the Fe limitation of the ambient phytoplankton community.

In vitro dissolution experiments were conducted in seawater in order to quantify the partitioning between dissolved and particulate phases of iron associated to Saharan dust and urban particles. The percentage of iron released was very low (0.05 to 2.2%) depending on the particulate load, the aerosol source and the contact time. This percentage decreased with the amount of particles introduced following a power law, indicating that the process could be modeled. Indeed, these dissolution processes were a function of the lability of iron in relation to the particle source, the particle size and adsorption processes. According to these experiments, the dissolved iron induced in a 10 m mixed layer by Saharan events of various magnitudes ranges from 0.07 to 1 nM. Since these concentrations are in agreement with the natural iron requirements for the phytoplankton, such inputs can profoundly influence the primary production, especially in oligotrophic conditions.

The behavior of dissolved cadmium (Cd) in the Danube estuary was investigated through field sampling and mixing experiments using Danube River water and Black Sea water. The experiments were performed by mixing these two end-member waters in various proportions, with the addition of stable or radioactive Cd to the freshwater Danube end-member prior to the mixing. The release of Cd that resulted in maximum concentrations under field conditions was well simulated by mixing experiments. The experimental results were modeled assuming that the release of Cd was the sum of the contribution of physical effects resulting from dilution effects and the contribution of chemical effects resulting from dissolved Cd-complex formation (and isotopic exchange when concerned). In the absence of dissolved Cd-complexing ligands, the release of Cd due to the dilution of the particulate phase during mixing could explain part of the maximum concentrations observed in field conditions. Kinetic effects were established by comparing the theoretical and measured contribution of chemical effects resulting from dissolved Cd-complex formation. The non-equilibrium state observed during the mixing experiment suggested the presence of particulate labile Cd that was not easily mobilized. All these features supported the hypothesis that Cd released in estuaries is controlled both by the dilution of the particulate phase and by kinetic competitive complexation between particulate ligands (covering a large spectrum of nature and strength) and dissolved ligands. (C) 2002 Elsevier Science Ltd. All rights reserved.

A Saharan soil, considered as a proxy for Saharan aerosols, was used to perform radio-labelled phosphate adsorption experiments using ³³PO₄^3-: leached particles were exposed to poisoned western Mediterranean seawater for varying lengths of time. The measured adsorption capacity of Saharan dust for phosphate was 0.13 µmol.g^-1. Considering this value and an annual Saharan dust deposition of 12.5 t.km^-2.yr^-1, we show that Saharan particles do not represent a significant sink for seawater phosphate in the western Mediterranean Sea. This result is in agreement with that determined from a similar approach conducted in the eastern basin. As a consequence, the unusual N/P ratio measured in the whole Mediterranean Sea (up to 29) can not be explained by the adsorption process of seawater phosphate onto Saharan dust.

A Saharan soil, considered as a proxy for Saharan aerosols, was used to perform a series of dissolution experiments: various amounts of Saharan soil were exposed to ultra pure water and seawater for varying lengths of time. The concentration of phosphate released was proportional to the amount of dust introduced. In the case of Saharan events associated with a significant amount of rain, the main dissolution of phosphorus will occur in the air column; for Saharan events associated with only few drops of rainwater, the main dissolution will occur in the surface seawater. The Saharan dust represent a source of phosphate to the surface water and may play a role in biological activity especially during the oligotrophic period. In the western Mediterranean in oligotrophic conditions, biological production is P-limited and the atmosphere becomes the main pathway of nutrients to the surface mixed layer. At the scale of the oligotrophic season, the input of "Saharan DIP" are negligible compared to the new production integrated over the productive layer. At the event time scale, the production induced by "Saharan DIP" can represent up to 15% of the integrated new production, and up to 14% of the total primary production in the mixed surface layer. These inputs of atmospheric DIP would promote fixation of atmospheric N2 that, in return, may enhance the new production in the surface layer.

During the PROSOPE cruise (Sept. 1999) in the Mediterranean Sea, dissolved iron concentrations in seawater and iron and aluminium concentrations in aerosols collected on board were investigated. Concentrations in aerosols were about two times higher in the Tyrrhenian Sea than in the west (Alboran Sea). This was in good agreement with the observed increase in dissolved iron concentrations in the surface waters from West to East. Depth profiles were characterised by a maximum in the surface mixed layer. Using an in vitro experiment, iron released from Saharan dust during the season characterized by a stratified water column and a low primary productivity was estimated: it resulted in an accumulation of 0.5-0.8 nM dissolved iron, in good agreement with the observed iron enrichment in the surface water (0.8 nM). This study confirms the significance of atmospheric input of Saharan origin on the iron cycle in the Mediterranean Sea.

Trace metal concentrations were measured in the Danube River at different locations along the three main branches of the delta. Results from a systematic delta survey in 1997 and those from the 1995 cruise indicate that the ranges of the total dissolved concentrations in the river end-member are: A1 = 211-445 nM, Cd = 224-302 pM, Co = 266-390 pM, Cu = 61-120 nM, Fe = 21-156 nM, Mn = 26-55 nM, Pb = 145-220 pM and Zn = 11-41 nM. The particulate concentrations were found to be: A1 = 5.5-6.7%, Cd = 1.1-2.4 ppm, Co = 16-19 ppm, Cu = 201-1092 ppm, Fe = 3.7-4.0%, Mn = 1286-2290 ppm, Ni = 66-77 ppm, Pb = 58-65 ppm and Zn = 212-224 ppm. The concentrations measured in 1997 confirm that the total dissolved concentrations in the Danube River are low and do not give any evidence of contamination, except for Cu. The particulate concentrations of Al, Ni, Cd, Co and Mn are very similar in the Danube and in uncontaminated world rivers. Pb is found to be enriched by a factor of 3 and Cu by a factor of 14. This enrichment may be due to some mining activity occurring upstream and within the Danube delta area. The evolution of the total dissolved metal concentration (Cd, Cu, Fe, Mn and Zn) along the salinity gradient established in 1997 for the Chilia and Sulina branches confirmed the low reactivity of dissolved trace metals. The only exception being an addition of manganese in front of the Chilia branch. This excess may be attributed to the occurrence of highly labile particulate manganese originating from a local source within the Chilia branch, probably from mining waste. The comparison between field data for winter and spring conditions do not show any significant difference for Cd, Mn and Zn. The comparison with results from the in vitro mixing of river and seawater seems to indicate that the processes involved in the addition of Cd and Zn are inorganic. In winter, the total dissolved iron concentrations were found to be pH-dependent, whereas in spring, due to the beginning of photosynthetic activity, the pH increased within the estuary, and the lower concentrations of Fe observed (down to around 10 nM) can be considered as an indirect consequence of the biological activity. The Cu distribution was found to be conservative in winter; in spring, the river concentrations are reduced by a factor of 1.4, which could have resulted from biological uptake by freshwater phytoplankton species. The distribution also seemed to show a slight removal of Cu, similar to the one observed for silica, suggesting that some uptake took place in the low salinity area. (C) 2002 Elsevier Science Ltd. All rights reserved.

Two types of samples were used to chemically characterize the Saharan end-member: fine fractions of surface soil samples collected in Northern Africa and particulate phases of typical Saharan rains. Since the concentrations measured in the particulate phase of the Saharan rains were corrected from the dissolution losses in rainwater, these particles were considered to be representative of the transported Saharan dust before being blended into rainwater. Al, Fe, P, and Pb were analyzed: except for lead, the chemical composition of the transported Saharan dust was more homogeneous than the composition of individual soils. As confirmed by the air mass back trajectories, the higher level of homogeneity of the aerosol is partly due to the fact that a dust event affects a large area of the Saharan desert, and the composition of the particles reflects the average composition of the eroded areas. Pb concentration in the transported dust reflected an anthropogenic fraction. By using Pb/Al measurements from the soils it was shown that a typical Saharan rain event with no mixing with air masses from Europe appears to be very rare in the Mediterranean environment. The following values are proposed to characterize the Saharan dust end-member: Al (%) = 7.09 ± 0.79; Fe (%) = 4.45 ± 0.49; P (%) = 0.082 ± 0.011; Pb (ppm) = 24 ± 9. This study suggests that the [element/Al or Fe)] ratio is also useful to characterize the Saharan end-member as they are very homogeneous for the two sample types. Saharan dust represents a potential source of nutrients (P, Fe) for the Mediterranean water. Indeed, it accounts for ∼30–40% of the total atmospheric flux of phosphorus in the western Mediterranean, and it governs the biogeochemical cycle of iron being the main source of dissolved iron in the western Mediterranean waters.

Measurements of dissolved and leachable particulate trace metals (Mn, Fe, Co, Pb, Cd, Zn, Cu and Ni) and total particulate Mn and Fe were made on seawater samples collected from the northwestern Black Sea during the EROS 2000 expedition conducted in July-August 1995. The investigation concentrated on waters of the shelf and shelf edge, but included one deeper water (1440 m) station. In the oxic layer of the deep station, the suspended particulate fractions of Mn and Fe were a major part of the total metal mass, consistent with the presence of the ``Fine Particle Layer'' which forms on the shelf and spreads all over the Black Sea with intensities decreasing from the coast. Dissolved and total particulate concentrations were, respectively, Mn, 0.69-9.6, 1.2-29; Fe, 0.79-3.03, 2.3-7.4 nM. Dissolved Cu and Ni concentrations were relatively high (1-8 and 8-12 nM, respectively), and did not show any depletion in surface oxic waters, possibly as a result of strong organic complexation. Dissolved Pb concentrations (100-200 pM) were higher than were generally found on the shelf. This was attributed to atmospheric inputs combined with less efficient scavenging of metals in these low SPM waters. The distribution of dissolved Co closely resembled that of dissolved Mn reflecting coupling through oxidation of Mn. Concentrations of dissolved Cd and Zn were low in surface water (0.07-0.09 and 0.9-2.0 nM, respectively), and increases in concentrations with depth were sharply reversed around the top of the redoxcline. For most metals (Mn, Fe, Co, Pb, Cu, Cd, Zn) dissolved concentrations were low in the anoxic layers as a result of solubility by formation of, or association with, solid sulphide phases. Dissolved Ni was not affected by sulphide precipitation. At most of the shelf stations there were clear enhancements of dissolved Mn and Fe in the deepest waters, consistent with other evidence that significant benthic fluxes of these metals arise through the redox conditions in the region of the sediment-water interface. In the shelf water column, dissolved Mn and Fe concentrations ranged between 1.2 and 1350 and between 0.4 and 181 nM, respectively; the highest concentrations were found near the bottom. Particulate concentrations of Mn and Fe were high, implying high oxidation rates of Mn(II) and Fe(II) and/or high supply rates from rivers. Total particulate concentrations of Mn and Fe were 0.7-1050 and 2.3-2650 nM, respectively; the highest concentrations were found ill surface and bottom waters. The distributions of particulate Mn and Fe were consistent with the isopyenal transport or Mn and Fe oxyhydroxides from the shelf by the coastal circulation. Distributions of other trace metals (Co, Pb, Cu, Ni, Cd, Zn) were considerably influenced by riverine inputs. Relatively high dissolved and available particulate metal concentrations were generally found in surface waters at stations directly influenced by the Danube River. Some trace metals (Co, Ni, Cd and Zn) were influenced by Mn and Fe cycling and increases in their dissolved concentrations occurred at a number of stations near the sediment-water interface. Dissolved and available particulate metal concentrations (nM) at stations oil the shelf were, respectively: 0.171-1.80, 0.003-0.437 (Co); 0.014-0.614, 0.010-1.48 (Pb); 7.6-28.8, 0.048-3.75 (Cu); 11.0-17.5, 0.018-2.10 (Ni); 0.033-0.161, 0.003-0.063 (Cd); 1.01 8.33, 0.135 7.58 (Zn). (C) 2001 Elsevier Science Ltd. All rights reserved.

This paper presents inputs and output fluxes of dissolved metals (As, Cd, Co, Cu, Fe, Mn, Ni, Ph and Zn) into and out the Western Mediterranean. These flux estimates are based on the most recently published concentrations and fluxes for the atmosphere, the rivers and the straits, Comparison of the different sources shows the predominance of the inputs through the straits over other sources. The river input is smaller than the atmospheric input except for As. For all elements except Fe, output flux and input flux are balanced; iron budget indicates transfer from the dissolved to the particulate phase. (C) 2001 Elsevier Science Ltd. All rights reserved.

The total atmospheric deposition on the north-western coast of Corsica (Pirio) was sampled for 2 years and concentration of Al, Cd, Cu, Fe, Mn, Ni, Pb and Zn were measured during that time period. The sampling station was chosen for its isolation from any local and regional contamination sources. The year-to-year variability of the total atmospheric deposition was found to be high (up to a factor of 2). Using Al as the crustal reference indicates that Pb, Cd and Zn are mainly associated with anthropogenic aerosols (> 85%) and Fe with crustal aerosols (> 70 %). However, our results indicate that the Saharan dust is a potential source of «natural» lead especially in the case of a major input of dust to the north-western Mediterranean. In order to determine the spatio-temporal variability of the trace metals over the north-western Mediterranean Sea, the observed fluxes are compared to those previously found in the past decade using the same methodology. The comparison indicates a relative homogeneity of Cu and Ni fluxes over the north-western Mediterranean and over the past decade. The decrease found in Al and Fe since 1985 (by a factor of 4 to 6) can be related to the decrease of the Saharan dust fallout. The limitation in the use of lead additives in gasoline could result in a decrease of the European atmospheric lead emissions of about a factor of 6 since 1985 and in a maximum decrease of the total atmospheric flux of 12 when taking into account the natural interannual variability of atmospheric deposition in this region. So the recorded decrease in the lead atmospheric flux since 1985 (~a factor of 30) reveals a slight local contamination at the previous Corsican station. In the case of Cd and Zn, there is a decrease by a factor of 30 and 23 respectively between the data obtained at La Tour du Valat (7/88-6/89) and those at Pirio (3/96-3/97); such a decrease cannot be the consequence of neither a reduction of emissions at the European scale (the factor being at most 4), nor the distance to the emissions sources. Hence, we confirm that Zn and Cd fluxes at la Tour du Valat and Zn fluxes at Cap Ferrat were not representative of a long-range transport to the Mediterranean but the result of a local/regional contamination. The large decrease observed for anthropogenic metals (Cd, Zn and Pb) results from a combination of the actual diminution of the concentrations due to the reduction of the emissions and the occurrence of local/regional contamination for some elements at some sampling sites.

Trace metal concentrations were measured in the Danube River estuary and in the shelf area of the north-western Black Sea. Total dissolved concentrations (<0.45 mu M) of the freshwater in the river end-member were found to be: Cd = 117 pM, Pb=81 pM, Co = 266 pM, Zn = 6 nM, Mn = 19 nM, Ni = 15 nM, Cu = 36 nM, Al = 384 nM and Fe = 20 nM. These concentrations are surprisingly low for an area where serious contamination has been suspected. This is particularly true of Cd, Pb and Zn, which are generally anthropogenic in polluted regions. The observed low concentrations, in particular for Fe, Mn, Co and Al can be attributable to the precipitation of hydrated oxides as a consequence of high pH of the Danube River. Concentrations of metals in the particulate fraction are similar to those in other major rivers of the world. The evolution of the total dissolved trace metal concentrations in the surface waters within the salinity gradient suggests: (1) no noticeable exchange between the particulate and the dissolved fraction for Cu, Ni and Zn; and (2) evidence for a low solid to liquid exchange for the other metals (Cd, Fe, Mn, Co and Pb) which brings about a two-fold increase in their concentrations from lower to higher salinity. Another source of dissolved material is suspected at around salinity 15. This source may be from localized-patches in the sediment where specific redox conditions may induce a vertical flux of dissolved metals: the bottom waters above these patches are characterized by a diminution of the dissolved O-2 and high concentrations of metals. The colloidal fraction (between 10 kD and 0.45 mu m) was established on a limited number of samples for Cd, Cu, Mn and Fe and was found to be significant: 40% of Cu, 40% of Cd, similar to 50% of Mn and 60% of Fe of the so-called dissolved phase are actually associated with colloidal material. It represents at least 40% of the total dissolved concentration in the fresh water and in the mixing zone. This proportion decreases linearly with salinity for Cd and Cu. Fe is mostly in colloidal form with a maximum (similar to 80%) between salinity 5 and 10. The surface distribution of the total dissolved metals throughout the study area show a limited influence of the Danube on the concentrations observed for the `open sea' (salinity = 18). Most of the riverine flux seems to follow the general circulation to the south-west area. These `open Black Sea' concentrations are the same order of magnitude as average surface concentrations in the Mediterranean Sea. (C) 1998 Academic Press.

Concentrations of trace elements (Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn) were determined for aerosols, dry deposition, precipitation and total deposition samples collected from five stations on islands and in the coastal zone of the northwestern Mediterranean. Average concentrations of metals are very homogeneous over the sampled area, in particular at the three coastal sites. Cd and Pb are almost entirely of man-made origin, even in Saharan aerosols. For the other metals, the non-crustal fraction is lower in Saharan aerosols than in European aerosols, but there is an important man-made component in the Saharan aerosol, even for metals such as Fe and Cr. This confirms the results of Chester et al. (1992) who concluded that Mediterranean aerosols have a European background upon which are superimposed Saharan inputs. Dry deposition represents an important fraction of the total deposition. Partitioning of total atmospheric deposition between the dissolved and the particulate phases shows that Al, Fe and Cr originating from the atmosphere are mostly in a particulate form in the surface waters. For the other metals studied, the dissolved fraction represents more than 30% of the total input, and for Cd it is almost 100%. Extrapolation shows that more than 50% of the dissolved metals input to the northwestern Mediterranean originates from the atmosphere. Atmospheric input entirely dominates the total external input of pollution-derived elements, such as Pb and Cd. The dissolved input of atmospheric origin is also very important (> 80%) for elements of terrigeneous origin such as Al. (C) 1997 Elsevier Science Ltd.

Freshwater concentrations confirm the pristine character of the Lena River environment as already pointed-out in a previous study with a limited set of data (Martin et al., 1993). Total dissolved concentrations of the freshwater are 13.8 ± 1.6 nM, Cu, 4.4 ± 0.1 nM, Ni, 0.054 ± 0.047 nM, Cd, 642 ± 208 nM, Fe, 0.2–0.3 nM Pb and 1.2 ± 1.0 nM, Zn. For Zn and Pb, a simple mixing of the Lena River waters with the Arctic waters is observed. Relationships with salinity suggest that for Cu, Ni and Cd, there is a mobilization of the dissolved fraction from the suspended matter, with an increase of the dissolved concentration of 1.5, 3 and 6 times, respectively. For Fe, the total dissolved concentrations follow an exponential decrease in the mixing zone and 80% of the total “dissolved” Fe is removed from the solution. For Cu, Ni, Cd and Fe, the riverine end-members are 20 nM, 12 nM, 0.3 nM and 47 nM, respectively. When considering the input of total dissolved metals to the Arctic Ocean, the fraction attributed to the freshwaters from the Arctic rivers appears to be small (4% of the input of dissolved metal to the Arctic Ocean for Cd, 27% for Cu, 11 % for Ni and 2% for Zn). Metal concentrations in the Laptev Sea and Arctic Ocean are very similar, indicating a generally homogeneous distribution in the areas sampled.

The atmospheric input is established for almost forty trace and major elements at a coastal site on the North-Western Mediterranean. Comparison with the Rhône River input at the scale of the Gulf of Lions shows that the total atmospheric input dominates for elements of anthropogenic origin such as Cd, Pb, Sb and Zn. Dissolved input of atmospheric origin is very important for these elements and for those of terrigenous origin (Al and Fe). In the coastal zone, both dissolved external sources (atmosphere and Rhône River) can explain the high Mediterranean Surface waters concentrations. Atmospheric input becomes rapidly the predominant factor, while the riverine influence being negligible in the few tens' kilometers outside the river mouth.

This study assesses the significance of the atmospheric input of trace metals as compared to the Rhône river input into the Northern part of the Western Mediterranean directly influenced by this river. For most dissolved metals, atmospheric input is higher than dissolved riverine inputs. Atmospheric particulate input increases rapidly as one moves seaward from the river mouth. It shows the predominance of dissolved over particulate fractions in rain for all studied trace metals, except iron. Dry and wet fallout are equivalent for Co, Cu, Mn, Ni, and Pb; in the case of Al, Cd, and Fe, dry fallout is predominant. However, total atmospheric input of particulate metals (scavenged by the wet fallout and deposited as dry fallout) represents at least 70% of total atmospheric fallout.