Description: 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

Description: 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 gm(-2)) into large mesocosms (52m(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 dissolved inorganic phosphorus (DIP), simulated wet deposition events were also a significant source of nitrate (NO3-) (net increases up to +9.8 mu M NO3- at 0.1m in 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 N-P 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, and taking into account the stimulation of the biological activity, a wet deposition event resulted in a strong increase in the NO3-/DIP ratio, from initially less than 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 strongly 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 contrasting 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 through changes in the nutrient stocks, and alters the NO3-/DIP ratio, leading to a switch in the nutrient limitation of the phytoplanktonic activity.

Description: 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 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 climatological 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.

Description: 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 biogeochemical 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 deposition 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.

Description: Microbial activity is a fundamental component of oceanic nutrient cycles. Photosynthetic microbes, collectively termed phytoplankton, are responsible for the vast majority of primary production in marine waters. The availability of nutrients in the upper ocean frequently limits the activity and abundance of these organisms. Experimental data have revealed two broad regimes of phytoplankton nutrient limitation in the modern upper ocean. Nitrogen availability tends to limit productivity throughout much of the surface low-latitude ocean, where the supply of nutrients from the subsurface is relatively slow. In contrast, iron often limits productivity where subsurface nutrient supply is enhanced, including within the main oceanic upwelling regions of the Southern Ocean and the eastern equatorial Pacific. Phosphorus, vitamins and micronutrients other than iron may also (co-)limit marine phytoplankton. The spatial patterns and importance of co-limitation, however, remain unclear. Variability in the stoichiometries of nutrient supply and biological demand are key determinants of oceanic nutrient limitation. Deciphering the mechanisms that underpin this variability, and the consequences for marine microbes, will be a challenge. But such knowledge will be crucial for accurately predicting the consequences of ongoing anthropogenic perturbations to oceanic nutrient biogeochemistry.

Description: The deposition of atmospheric dust is the main external source to the ocean for elements abundant in crustal rocks such as Mn, Al and Fe. Once deposited the residence time of these elements in surface waters differs according to their chemical speciation and biological ultilization. In the present work we examined the temporal changes (a daily cycle) in the concentrations within trace metal clean mesocosms after the input of simulated aeolian dust to surface waters of the northwestern Mediterranean. Two artificial deposition events were performed during the course of this experiment: each artificial Saharan dust fertilization to the mesocoms mimicked a wet deposition of 10 g m-2 and the changes in Mn, Fe and Al chemistry were followed over the following week. In this presentation we will present results from this mesocosm experiment focusing on the similarities and differences between these 3 elements. This trace metal dataset makes a significant contribution to enhance our knowledge about the release of trace metals from Saharan dust in a low nutrient low chlorophyll area and the subsequent processes of biouptake and scavenging

Description: The deposition of atmospheric dust is one of the main external source to the ocean for elements abundant in crustal rocks. Once deposited the residence time of these elements in surface waters differs according to their chemical speciation and biological ultilization. In the present work we examined the temporal changes in the concentrations of Iron, Maganese and Aluminium within large mesocosms after the seeding with simulated aeolian dust of surface waters of the northwestern Mediterranean. Two artificial deposition events were performed during the course of this experiment: for each artificial Saharan dust fertilization to the mesocoms the changes in Mn, Fe and Al chemistry were followed over the following week. In this presentation, we will present results from this mesocosm experiment focusing on the similarities and differences between these 3 elements. This trace metal dataset makes a significant contribution to enhance our knowledge about the release of trace metals from Saharan dust in a low nutrient low chlorophyll area and the subsequent processes of biouptake and scavenging.

Description: Mn forms a critical part of many redox enyzmes most notably for photosynthesis, where as part of Photosystem II it converts H2O to O2. Many marine organisms also contain Mn superoxide dismutases (SOD), that act as part of the intracellular defences against reactive oxygen species (ROS) and in particular rapidly convert superoxide (O2-) into O2 and H2O2. While laboratory studies have shown that the growth of marine phytoplankton is reduced for some species at the low Mn concentrations found in open ocean seawater, currently there is little evidence from fieldwork to suggest Mn limitation occurs, but this possibility remains, particularly for the Southern Ocean. The supply of Mn to the open ocean is predominantly via the deposition of aeolian dust and subsequent dissolution of Mn(II) from the particles. The released Mn(II) is slowly oxidized (via biota or chemically) to insoluble MnO2 which precipitates out of the water column. In the sunlit ocean, H2O2 can reduce MnO2 back to Mn(II) completing a redox cycle. New work by a number of groups suggest that transient Mn(III) species, intermediate in the cycling between Mn(II) and MnO2 may play an important role in both the Mn and Fe biogeochemical cycles in surface waters. In coastal waters Mn(II) can diffuse from reducing sediments with subsequent mixing into the photic zone. In this presentation we will present data for Mn concentrations, speciation and kinetic reactivity from two research cruises in the Tropical Atlantic (M83-1 and MSM17-04) and from a dust deposition experiment performed in trace metal clean mesocosms in the Mediterranean (DUNE2). We will use our combined dataset to determine the predominant source of Mn to shelf waters in the Mauritanian upwelling region and the adjacent open ocean in the Tropical Atlantic, which are impacted by both Saharan dust and potentially coastal sedimentary sources that are advected offshore by the upwelling waters. Finally we will examine the evidence for Mn(III) in the euphotic zone of the open ocean and the implications this had for Mn biogeochemical cycling in the ocean.