The importance of the atmospheric deposition of biologically essential trace elements, especially iron, is widely recognized, as are the difficulties of accurately quantifying the rates of trace ...element wet and dry deposition and their fractional solubility. This paper summarizes some of the recent progress in this field, particularly that driven by the GEOTRACES, and other, international research programmes. The utility and limitations of models used to estimate atmospheric deposition flux, for example, from the surface ocean distribution of tracers such as dissolved aluminium, are discussed and a relatively new technique for quantifying atmospheric deposition using the short-lived radionuclide beryllium-7 is highlighted. It is proposed that this field will advance more rapidly by using a multi-tracer approach, and that aerosol deposition models should be ground-truthed against observed aerosol concentration data. It is also important to improve our understanding of the mechanisms and rates that control the fractional solubility of these tracers. Aerosol provenance and chemistry (humidity, acidity and organic ligand characteristics) play important roles in governing tracer solubility. Many of these factors are likely to be influenced by changes in atmospheric composition in the future. Intercalibration exercises for aerosol chemistry and fractional solubility are an essential component of the GEOTRACES programme.
This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element chemistry’.
A number of trace metals play essential roles in marine ecosystem structure and biological productivity. Until recently, it has been argued that phytoplankton access primarily dissolved iron, while ...particulate iron was considered a refractory material with little use biologically and limited interaction with the dissolved pool. In order to assess the transfer mechanisms between sediment-sourced particulate trace metals and the dissolved pool, we conducted a 14-month incubation that reacted resuspended sediments with natural seawater, both originating from the Kerguelen area (KEOPS cruises; Southern Ocean), in the dark, and at concentrations replicating natural conditions. Three types of sediments were investigated (named BioSi, BioSi + Ca, and Basalt), mostly composed of (i) biogenic silica (bSiO2), (ii) bSiO2 and calcite, and (iii) basaltic fragments, respectively. The release of dissolved silicon (dSi), iron (dFe) and manganese (dMn) was monitored regularly throughout the incubation, as well as living bacteria density and Fe organic ligands. Depending on the origin and composition of the sediment, unique dFe and dMn fluxes were observed, including a strong decoupling between dFe and dMn. The basaltic sediment released up to 1.09 ± 0.04 nmol L−1 of dFe and 0.28 ± 0.09 nmol L−1 of dMn, while the biogenic sediments released a higher 3.91 ± 0.04 nmol L−1 and 8.03 ± 0.42 nmol L−1 of dFe and dMn, respectively. Several factors influencing the release and removal of dFe and dMn were discernable at the temporal sampling resolution of the incubation, including the structural composition of the sediment, bacterial abundance, and the formation of manganese oxides. The regular sampling over short timescales and the extended sampling over one year proved to be critical to constrain the processes and exchanges that govern the contribution of the particulate to the dissolved pools. Overall, this incubation provides a strong basis for reassessing the role of resuspended sedimentary particles in the marine biogeochemical cycles of Fe and Mn. Indeed, we show that biogenic silica, calcite-rich and basaltic particles can contribute substantial dissolved Fe and Mn to the overlying water column. In the future, the global extent of this previously overlooked external metal source should be quantified through further process studies and biogeochemical models.
This article is part of a special issue entitled: “Cycles of trace elements and isotopes in the ocean – GEOTRACES and beyond” - edited by Tim M. Conway, Tristan Horner, Yves Plancherel, and Aridane G. González.
•Resuspended sedimentary particles contribute to a substantial flux of trace metals into the overlying oceanic water column•The release of dissolved Fe and Mn from resuspended sedimentary particles is decoupled through time•Biogenic silica and basaltic-rich particles are substantial sources of dissolved Fe•Calcite-rich particles are substantial sources of dissolved Mn
The identification of the mechanisms by which marine dissolved organic matter (DOM) is produced and regenerated is critical to develop robust prediction of ocean carbon cycling. Polysaccharides ...represent one of the main constituents of marine DOM and their degradation is mainly attributed to polysaccharidases derived from bacteria. Here, we report that marine viruses can depolymerize the exopolysaccharides (EPS) excreted by their hosts using five bacteriophages that infect the notable EPS producer, Cobetia marina DSMZ 4741. Degradation monitorings as assessed by gel electrophoresis and size exclusion chromatography showed that four out of five phages carry structural enzymes that depolymerize purified solution of Cobetia marina EPS. The depolymerization patterns suggest that these putative polysaccharidases are constitutive, endo-acting and functionally diverse. Viral adsorption kinetics indicate that the presence of these enzymes provides a significant advantage for phages to adsorb onto their hosts upon intense EPS production conditions. The experimental demonstration that marine phages can display polysaccharidases active on bacterial EPS lead us to question whether viruses could also contribute to the degradation of marine DOM and modify its bioavailability. Considering the prominence of phages in the ocean, such studies may unveil an important microbial process that affects the marine carbon cycle.
Seasonal progression of dissolved iron (DFe) concentrations in the upper water column was examined during four occupations in the Atlantic sector of the Southern Ocean. DFe inventories from euphotic ...and aphotic reservoirs decreased progressively from July to February, while dissolved inorganic nitrogen decreased from July to January with no significant change between January and February. Results suggest that between July and January, DFe loss from both euphotic and aphotic reservoirs was predominantly in support of phytoplankton growth (iron‐to‐carbon uptake ratio of 16 ± 3 μmol/mol), highlighting the importance of the “winter DFe reservoir” for biological uptake. During January to February, excess loss of DFe relative to dissolved inorganic nitrogen (iron‐to‐carbon uptake ratio of 44 ± 8 μmol/mol and aphotic DFe loss rate of 0.34 ± 0.06 μmol·m−2·day−1) suggests that scavenging is the dominant removal mechanism of DFe from the aphotic, while continued production is likely supported by recycled nutrients.
Plain Language Summary
Trace metal iron is one of the limiting nutrients for primary productivity in the Southern Ocean; however, the relative importance of seasonal iron supply and sinks remains poorly understood, due to sparse data coverage across the seasonal cycle and lack of high‐resolution dissolved iron (DFe) measurements. Here we present four “snapshots” of DFe measurements at a single station in the southeast Southern Atlantic Ocean (one in winter and three in late spring‐summer), to address the seasonal evolution of DFe and dissolved inorganic nitrogen (DIN) concentrations within the biologically active sunlit and subsurface reservoirs. We observed a seasonal depletion of DFe inventories from July to February, while DIN inventories decrease from July to January with no concomitant changes between January and February. This suggests that in addition to biological uptake in the sunlit layer, the observed decrease in DFe inventories below this (relative to DIN) is driven by aggregation and incorporation of iron particles into larger “marine snow” sinking particles, while nutrient recycling is driving the observed continuation of primary productivity during late summer. Our results provide insight into seasonal change of DFe availability in different reservoirs where interplay between removal and supply processes are controlling its distributions and bioavailability to support upper surface primary production.
Key Points
We report the first seasonal changes of the upper surface dissolved iron concentrations of four occupations from late winter to late summer
Euphotic zone dissolved iron decreases due to biological uptake, while aphotic iron decreases due to colloidal aggregation and scavenging
Recycling of nutrients might be responsible for sustaining the observed seasonal primary production in late January to early February
Distributions of total dissolvable iron (TDFe; unfiltered), dissolved iron (DFe; 0.2 μm filtered), and soluble iron (SFe; 0.02 μm filtered) were investigated during the BONUS‐GoodHope cruise in the ...Atlantic sector of the Southern Ocean (34°S/17°E–57°S/0°, February–March 2008). In the mixed layer, mean values of 0.43 ± 0.28 and 0.22 ± 0.18 nmol L−1 were measured for TDFe and DFe, respectively. In deeper waters, TDFe and DFe concentrations were 1.07 ± 0.68 and 0.52 ± 0.30 nmol L−1, respectively. DFe concentrations decreased from the north (subtropical waters) to the south (Weddell Sea Gyre). In the subtropical domain, dusts coming from Patagonia and southern Africa and inputs from the African continental margin may explain high DFe and TDFe concentrations in surface and intermediate waters. Results from numerical models gave support to these hypotheses. In the Antarctic Circumpolar Current domain, estimation of the median advective time of water masses suggests that sediment inputs from the Antarctic Peninsula, South America margin, and/or South Georgia Islands could be an important source of Fe. Except in the subtropical domain where 0.4–0.6 nmol L−1 of SFe were observed in the upper 1500 m, all stations exhibited values close to 0.1–0.2 nmol L−1 in surface and 0.3–0.5 nmol L−1 in deeper waters. For all stations, colloidal Fe (CFe) was a minor fraction of DFe in surface waters and increased with depth. Colloidal aggregation, sinking of CFe, and assimilation of SFe, followed by rapid exchange between the two fractions, are suspected to occur.
Dissolved Fe (dFe) concentrations were measured in the upper 1300 m of the water column in the vicinity of the Kerguelen Islands as part of the second KErguelen Ocean Plateau compared Study (KEOPS2). ...Concentrations ranged from 0.06 nmol L−1 in offshore, Southern Ocean waters to 3.82 nmol L−1 within Hillsborough Bay, on the north-eastern coast of the Kerguelen Islands. Direct island runoff, glacial melting and resuspended sediments were identified as important inputs of dFe that could potentially fertilise the northern part of the plateau. A significant deep dFe enrichment was observed over the plateau with dFe concentrations increasing up to 1.30 nmol L−1 close to the seafloor, probably due to sediment resuspension and pore water release. Biological uptake was shown to induce a significant decrease in dFe concentrations between two visits (28 days apart) at a station above the plateau. Our work also considered other processes and sources, such as lateral advection of enriched seawater, remineralisation processes, and the influence of the polar front (PF) as a vector for Fe transport. Overall, heterogeneous sources of Fe over and off the Kerguelen Plateau, in addition to strong variability in Fe supply by vertical or horizontal transport, may explain the high variability in dFe concentrations observed during this study.
Total dissolvable iron (TDFe) was measured in the water column above and in the surrounding of the Kerguelen Plateau (Indian sector of the Southern Ocean) during the KErguelen Ocean Plateau compared ...Study (KEOPS) cruise. TDFe concentrations ranged from 0.90 to 65.6 nmol L−1 above the plateau and from 0.34 to 2.23 nmol L−1 offshore of the plateau. Station C1 located south of the plateau, near Heard Island, exhibited very high values (329–770 nmol L−1). Apparent particulate iron (Feapp), calculated as the difference between the TDFe and the dissolved iron measured on board (DFe) represented 95±5% of the TDFe above the plateau, suggesting that particles and refractory colloids largely dominated the iron pool. This paper presents a budget of DFe and Feapp above the plateau. Lateral advection of water that had been in contact with the continental shelf of Heard Island seems to be the predominant source of Feapp and DFe above the plateau, with a supply of 9.7±3.6×106 and 8.3±11.6×103 mol d−1, respectively. The residence times of 1.7 and 48 days estimated for Feapp and DFe respectively, indicate a rapid turnover in the surface water. A comparison between Feapp and total particulate iron (TPFe) suggests that the total dissolved fraction is mainly constituted of small refractory colloids. This fraction does not seem to be a potential source of iron to the phytoplankton in our study. Finally, when taking into account the lateral supply of dissolved iron, the seasonal carbon sequestration efficiency was estimated at 154 000 mol C (mol Fe)−1, which is 4-fold lower than the previously estimated value in this area but still 18-fold higher than the one estimated during the other study of a natural iron fertilisation experiment, CROZEX.
Labile Fe(II) distributions were investigated in the Sub-Tropical South Atlantic and the Southern Ocean during the BONUS-GoodHope cruise from 34 to 57° S (February–March 2008). Concentrations ranged ...from below the detection limit (0.009 nM) to values as high as 0.125 nM. In the surface mixed layer, labile Fe(II) concentrations were always higher than the detection limit, with values higher than 0.060 nM south of 47° S, representing between 39 % and 63 % of dissolved Fe (DFe). Apparent biological production of Fe(II) was evidenced. At intermediate depth, local maxima were observed, with the highest values in the Sub-Tropical domain at around 200 m, and represented more than 70 % of DFe. Remineralization processes were likely responsible for those sub-surface maxima. Below 1500 m, concentrations were close to or below the detection limit, except at two stations (at the vicinity of the Agulhas ridge and in the north of the Weddell Sea Gyre) where values remained as high as ~0.030–0.050 nM. Hydrothermal or sediment inputs may provide Fe(II) to these deep waters. Fe(II) half life times (t1/2) at 4°C were measured in the upper and deep waters and ranged from 2.9 to 11.3 min, and from 10.0 to 72.3 min, respectively. Measured values compared quite well in the upper waters with theoretical values from two published models, but not in the deep waters. This may be due to the lack of knowledge for some parameters in the models and/or to organic complexation of Fe(II) that impact its oxidation rates. This study helped to considerably increase the Fe(II) data set in the Ocean and to better understand the Fe redox cycle.
We examined the effect of iron (Fe) and Fe-light (Fe-L) co-limitation on cellular silica (BSi), carbon (C) and nitrogen (N) in two marine diatoms, the small oceanic diatom Thalassiosira oceanica and ...the large coastal species Ditylum brightwellii. We showed that C and N per cell tend to decrease with increasing Fe limitation (i.e. decreasing growth rate), both under high light (HL) and low light (LL). We observed an increase (T. oceanica, LL), no change (T. oceanica, HL) and a decrease (D. brightwellii, HL and LL) in BSi per cell with increasing degree of limitation. The comparison with literature data showed that the trend in C and N per cell for other Fe limited diatoms was similar to ours. Interspecific differences in C and N quotas of Fe limited diatoms observed in the literature seem thus to be mostly due to variations in cell volume. On the contrary, there was no global trend in BSi per cell or per cell volume, which suggests that other interspecific differences than Fe-induced variations in cell volume influence the degree of silicification. The relative variations in C:N, Si:C and Si:N versus the relative variation in specific growth rate (i.e. μ:μmax) followed the same patterns for T. oceanica and D. brightwellii, whatever the irradiance level. However, the variations of C:N under Fe limitation reported in the literature for other diatoms are contrasted, which may thus be more related to growth conditions than to interspecific differences. As observed in other studies, Si:C and Si:N ratios increased by more than 2-fold between 100% and 40% of μmax. Under more severe limitation (HL and LL), we observed for the first time a decrease in these ratios. These results may have important biogeochemical implications on the understanding and the modelling of the oceanic biogeochemical cycles, e.g. carbon and silica export.
From 2008 to 2014, the MAREL-Iroise buoy, located in the Bay of Brest, collected high-frequency measurements of partial pressure of CO2 (pCO2) and ancillary hydrographic parameters, in conjunction ...with a comprehensive sampling regime of two additional carbonate system variables total alkalinity (AT), and dissolved inorganic carbon (DIC). Biological processes drive variations in AT and DIC throughout the year, except in winter, when primary production is negligible and large freshwater inputs occur. Annually, the Bay of Brest generally behaves as a source of CO2 to the atmosphere (0.14±0.20molCm−2yr−1), showing inter-annual variability significantly linked to annual net community production (NCP). The presence of a large community of benthic filter feeders leads to high levels of particulate organic matter (POM) and opal deposition during the spring diatom bloom. Over the following few months, benthic POM remineralisation reduces the spring CO2 deficit relative to the atmosphere, and remineralisation of biogenic silica supplies further late spring primary production. The result is an inverse spring NCP – air-sea CO2 flux relationship, whereby greater NCP in early spring results in lower fluxes of CO2 into the Bay in late spring. This recycling mechanism, or silicic acid pump, also links the spring and summer NCP values, which are both determined by the peak wintertime nutrient concentrations. The carbonate system is further affected by the benthic community in winter, when CaCO3 dissolution is evident from notable deviations in the ΔAT:ΔDIC ratio. This study highlights the necessity of individual study of coastal, temperate ecosystems and contributes to a better understanding of what determines coastal areas as sinks or sources of CO2 to the atmosphere.
•The Bay of Brest generally behaves as a source of CO2 to the atmosphere.•Inter-annual variability in air-sea CO2 exchange is linked to net community production.•Springtime net community production is determined by the winter, river dissolved silica supply.•Total alkalinity and dissolved inorganic carbon variability is driven by biology.
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