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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 (−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.

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.

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.

The surface ocean receives important amounts of organic carbon from atmospheric deposition. The degree of bioavailability of this source of organic carbon will determine its impact on the marine carbon cycle. In this study, the potential availability of dissolved organic carbon (DOC) leached from both desert dust and anthropogenic aerosols to marine heterotrophic bacteria was investigated. The experimental design was based on 16 d incubations, in the dark, of a marine bacterial inoculum into artificial seawater amended with water-soluble Saharan dust (D treatment) and anthropogenic (A treatment) aerosols, so that the initial DOC concentration was similar between treatments. Glucose-amended (G) and non-amended (control) treatments were run in parallel. Over the incubation period, an increase in bacterial abundance (BA) and bacterial production (BP) was observed first in the G treatment, followed then by the D and finally A treatments, with bacterial growth rates significantly higher in the G and D treatments than the A treatment. Following this growth, maxima of BP reached were similar in the D (879 ± 64 ng C L−1 h−1; n=3) and G (648 ± 156 ng C L−1 h−1; n=3) treatments and were significantly higher than in the A treatment (124 ng C L−1 h−1; n=2). The DOC consumed over the incubation period was similar in the A (9 µM; n=2) and D (9 ± 2 µM; n=3) treatments and was significantly lower than in the G treatment (22 ± 3 µM; n=3). Nevertheless, the bacterial growth efficiency (BGE) in the D treatment (14.2 ± 5.5 %; n=3) compared well with the G treatment (7.6 ± 2 %; n=3), suggesting that the metabolic use of the labile DOC fraction in both conditions was energetically equivalent. In contrast, the BGE in the A treatment was lower (1.7 %; n=2), suggesting that most of the used labile DOC was catabolized. The results obtained in this study highlight the potential of aerosol organic matter to sustain the metabolism of marine heterotrophs and stress the need to include this external source of organic carbon in biogeochemical models for a better constraining of the carbon budget.

In spring, the Mediterranean Sea, a well-stratified low-nutrient–low-chlorophyll region, receives atmospheric deposition by both desert dust from the Sahara and airborne particles from anthropogenic sources. Such deposition translates into a supply of new nutrients and trace metals for the surface waters that likely impact biogeochemical cycles. However, the relative impacts of the processes involved are still far from being assessed in situ. After summarizing the knowledge on dust deposition and its impact on the Mediterranean Sea biogeochemistry, we present in this context the objectives and strategy of the PEACETIME project and cruise. Atmospheric and marine in situ observations and process studies have been conducted in contrasted areas encountering different atmospheric deposition context, including a dust deposition event that our dedicated “fast-action” strategy allowed us to catch. Process studies also include artificial dust seeding experiments conducted on board in large tanks in three ecoregions of the open waters of the Mediterranean Sea for the first time. This paper summarizes the work performed at sea and the type of data acquired in the atmosphere, at the air–sea interface and in the water column. An overview of the results presented in papers of this special issue (and in some others published elsewhere) is presented.

Modelling of mineral dust is often done using one single mean species. But for biogeochemical studies, it could be useful to access to a more detailed information on differentiated mineral species and the associated chemical composition. Differentiating between mineral species would also induce different optical properties and densities and then different radiative impact, transport and deposition. In this study, the mineralogical differentiation is implemented in the CHIMERE regional chemistry-transport model, by using global databases. The results show that this implementation does not change the results much in terms of aerosol optical depth, surface concentrations and deposition fluxes. But the information on mineralogy, with a high spatial (a few kilometres) and temporal (1 h) resolution, is now available and is ready to be used for future biogeochemical studies.

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.

Trace element deposition from desert dust has important impacts on ocean primary productivity, the quantification of which could be useful in determining the magnitude and sign of the biogeochemical feedback on radiative forcing. However, the impact of elemental deposition to remote ocean regions is not well understood and is not currently included in global climate models. In this study, emission inventories for eight elements primarily of soil origin, Mg, P, Ca, Mn, Fe, K, Al, and Si are determined based on a global mineral data set and a soil data set. The resulting elemental fractions are used to drive the desert dust model in the Community Earth System Model (CESM) in order to simulate the elemental concentrations of atmospheric dust. Spatial variability of mineral dust elemental fractions is evident on a global scale, particularly for Ca. Simulations of global variations in the Ca / Al ratio, which typically range from around 0.1 to 5.0 in soils, are consistent with observations, suggesting that this ratio is a good signature for dust source regions. The simulated variable fractions of chemical elements are sufficiently different; estimates of deposition should include elemental variations, especially for Ca, Al and Fe. The model results have been evaluated with observations of elemental aerosol concentrations from desert regions and dust events in non-dust regions, providing insights into uncertainties in the modeling approach. The ratios between modeled and observed elemental fractions range from 0.7 to 1.6, except for Mg and Mn (3.4 and 3.5, respectively). Using the soil database improves the correspondence of the spatial heterogeneity in the modeling of several elements (Ca, Al and Fe) compared to observations. Total and soluble dust element fluxes to different ocean basins and ice sheet regions have been estimated, based on the model results. The annual inputs of soluble Mg, P, Ca, Mn, Fe and K associated with dust using the mineral data set are 0.30 Tg, 16.89 Gg, 1.32 Tg, 22.84 Gg, 0.068 Tg, and 0.15 Tg to global oceans and ice sheets.

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 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

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.

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 refine the "ballast hypothesis". In the framework of the DUNE (a DUst experiment in a low-Nutrient, low-chlorophyll Ecosystem) 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 than 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. On the scale of a dust-deposition event, we estimated that 42–50% of POC fluxes were strictly associated with lithogenic particles (through aggregation and most probably sorption processes). 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.

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.