Evidences of strong sources of DFe and DMn in Ryder Bay, Western Antarctic Peninsula.
ABSTRACT: The spatial distribution, biogeochemical cycling and external sources of dissolved iron and dissolved manganese (DFe and DMn) were investigated in Ryder Bay, a small coastal embayment of the West Antarctic Peninsula, during Austral summer (2013 and 2014). Dissolved concentrations were measured throughout the water column at 11 stations within Ryder Bay. The concentration ranges of DFe and DMn were large, between 0.58 and 32.7?nM, and between 0.18 and 26.2?nM, respectively, exhibiting strong gradients from the surface to the bottom. Surface concentrations of DFe and DMn were higher than concentrations reported for the Southern Ocean and coastal Antarctic waters, and extremely high concentrations were detected in deep water. Glacial meltwater and shallow sediments are likely to be the main sources of DFe and DMn in the euphotic zone, while lateral advection associated with local sediment resuspension and vertical mixing are significant sources for intermediate and deep waters. During summer, vertical mixing of intermediate and deep waters and sediment resuspension occurring from Marguerite Trough to Ryder Bay are thought to be amplified by a series of overflows at the sills, enhancing the input of Fe and Mn from bottom sediment and increasing their concentrations up to the euphotic layer.This article is part of the theme issue 'The marine system of the West Antarctic Peninsula: status and strategy for progress in a region of rapid change'.
Project description:Iron (Fe) is an essential micronutrient for marine microbial organisms, and low supply controls productivity in large parts of the world's ocean. The high latitude North Atlantic is seasonally Fe limited, but Fe distributions and source strengths are poorly constrained. Surface ocean dissolved Fe (DFe) concentrations were low in the study region (<0.1?nM) in summer 2010, with significant perturbations during spring 2010 in the Iceland Basin as a result of an eruption of the Eyjafjallajökull volcano (up to 2.5?nM DFe near Iceland) with biogeochemical consequences. Deep water concentrations in the vicinity of the Reykjanes Ridge system were influenced by pronounced sediment resuspension, with indications for additional inputs by hydrothermal vents, with subsequent lateral transport of Fe and manganese plumes of up to 250-300?km. Particulate Fe formed the dominant pool, as evidenced by 4-17 fold higher total dissolvable Fe compared with DFe concentrations, and a dynamic exchange between the fractions appeared to buffer deep water DFe. Here we show that Fe supply associated with deep winter mixing (up to 103 nmol m-2 d-1) was at least ca. 4-10 times higher than atmospheric deposition, diffusive fluxes at the base of the summer mixed layer, and horizontal surface ocean fluxes.
Project description: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.
Project description:Dissolved iron (DFe) concentrations in oxygen minimum zones (OMZs) of Eastern Boundary Upwelling Systems are enhanced as a result of high supply rates from anoxic sediments. However, pronounced variations in DFe concentrations in anoxic coastal waters of the Peruvian OMZ indicate that there are factors in addition to dissolved oxygen concentrations (O2) that control Fe cycling. Our study demonstrates that sediment-derived reduced Fe (Fe(II)) forms the main DFe fraction in the anoxic/euxinic water column off Peru, which is responsible for DFe accumulations of up to 200 nmol L-1. Lowest DFe values were observed in anoxic shelf waters in the presence of nitrate and nitrite. This reflects oxidation of sediment-sourced Fe(II) associated with nitrate/nitrite reduction and subsequent removal as particulate Fe(III) oxyhydroxides. Unexpectedly, the highest DFe levels were observed in waters with elevated concentrations of hydrogen sulfide (up to 4?µmol L-1) and correspondingly depleted nitrate/nitrite concentrations (<0.18?µmol L-1). Under these conditions, Fe removal was reduced through stabilization of Fe(II) as aqueous iron sulfide (FeSaqu) which comprises complexes (e.g., FeSH+) and clusters (e.g., Fe2S2|4H2O). Sulfidic events on the Peruvian shelf consequently enhance Fe availability, and may increase in frequency in future due to projected expansion and intensification of OMZs.
Project description:The impacts of large-scale, episodic sediment resuspension on the cycling of polychlorinated biphenyl congeners (PCBs) were examined using a spatially coordinated air and water sampling strategy conducted in southern Lake Michigan in the late winters of 1998, 1999, and 2000. We found no significant temporal changes in gas phase, dissolved phase, or suspended sediment PCB concentrations despite large-scale seasonal storms occurring before and after sampling campaigns. Only gas phase and suspended sediment PCBs varied spatially. Higher total suspended material (TSM) concentrations and fraction organic carbon (foc ) were measured at sampling stations located in the near-shore region of southern Lake Michigan than at open-water sampling stations. Gas phase concentrations (?PCBg) were higher in the west (0.436 ± 0.200 ng/m(3), n = 11) and south (0.408 ± 0.286 ng/m(3), n = 5) than the east (0.214 ± 0.082 ng/m(3), n = 10) and central (0.253 ± 0.145 ng/m(3), n = 8) regions of southern Lake Michigan. Dissolved phase concentrations (?PCBd) averaged 0.18 ± 0.024 ng/L (n = 52); suspended sediment concentrations (?PCBs) accounted for between 4% and 72% (23 ± 4%, n = 52) of the total ?PCB concentrations (?PCBT = ?PCBd + ?PCBs). Despite no consistent temporal variations in both dissolved phase or suspended sediment ?PCB concentrations, there were temporal and spatial variations in the distribution shift between phases that can be linked to sediment resuspension, not a state of equilibrium. Specifically, our analysis suggests sediment resuspension results in preferential sorption of heavier, more chlorinated PCB congeners.
Project description:Mesoscale eddies are ubiquitous in the iron-limited Southern Ocean, controlling ocean-atmosphere exchange processes, however their influence on phytoplankton productivity remains unknown. Here we probed the biogeochemical cycling of iron (Fe) in a cold-core eddy. In-eddy surface dissolved Fe (dFe) concentrations and phytoplankton productivity were exceedingly low relative to external waters. In-eddy phytoplankton Fe-to-carbon uptake ratios were elevated 2-6 fold, indicating upregulated intracellular Fe acquisition resulting in a dFe residence time of ~1 day. Heavy dFe isotope values were measured for in-eddy surface waters highlighting extensive trafficking of dFe by cells. Below the euphotic zone, dFe isotope values were lighter and coincident with peaks in recycled nutrients and cell abundance, indicating enhanced microbially-mediated Fe recycling. Our measurements show that the isolated nature of Southern Ocean eddies can produce distinctly different Fe biogeochemistry compared to surrounding waters with cells upregulating iron uptake and using recycling processes to sustain themselves.
Project description:Shelf sediments underlying temperate and oxic waters of the Celtic Sea (NW European Shelf) were found to have shallow oxygen penetrations depths from late spring to late summer (2.2-5.8 mm below seafloor) with the shallowest during/after the spring-bloom (mid-April to mid-May) when the organic carbon content was highest. Sediment porewater dissolved iron (dFe, <0.15 µm) mainly (>85%) consisted of Fe(II) and gradually increased from 0.4 to 15 ?M at the sediment surface to ~100-170 µM at about 6 cm depth. During the late spring this Fe(II) was found to be mainly present as soluble Fe(II) (>85% sFe, <0.02 µm). Sub-surface dFe(II) maxima were enriched in light isotopes (?56Fe -2.0 to -1.5‰), which is attributed to dissimilatory iron reduction (DIR) during the bacterial decomposition of organic matter. As porewater Fe(II) was oxidised to insoluble Fe(III) in the surface sediment layer, residual Fe(II) was further enriched in light isotopes (down to -3.0‰). Ferrozine-reactive Fe(II) was found in surface porewaters and in overlying core top waters, and was highest in the late spring period. Shipboard experiments showed that depletion of bottom water oxygen in late spring can lead to a substantial release of Fe(II). Reoxygenation of bottom water caused this Fe(II) to be rapidly lost from solution, but residual dFe(II) and dFe(III) remained (12 and 33 nM) after >7 h. Iron(II) oxidation experiments in core top and bottom waters also showed removal from solution but at rates up to 5-times slower than predicted from theoretical reaction kinetics. These data imply the presence of ligands capable of complexing Fe(II) and supressing oxidation. The lower oxidation rate allows more time for the diffusion of Fe(II) from the sediments into the overlying water column. Modelling indicates significant diffusive fluxes of Fe(II) (on the order of 23-31 µmol m-2 day-1) are possible during late spring when oxygen penetration depths are shallow, and pore water Fe(II) concentrations are highest. In the water column this stabilised Fe(II) will gradually be oxidised and become part of the dFe(III) pool. Thus oxic continental shelves can supply dFe to the water column, which is enhanced during a small period of the year after phytoplankton bloom events when organic matter is transferred to the seafloor. This input is based on conservative assumptions for solute exchange (diffusion-reaction), whereas (bio)physical advection and resuspension events are likely to accelerate these solute exchanges in shelf-seas.
Project description:Biogenic dimethylsulfide (DMS) is a significant contributor to sulfur flux from the oceans to the atmosphere, and the most significant source of aerosol non sea-salt sulfate (NSS-SO42-), a key regulator of global climate. Here we present the longest running time-series of DMS-water (DMSW) concentrations in the world, obtained at the Rothera Time-Series (RaTS) station in Ryder Bay, West Antarctic Peninsula (WAP). We demonstrate the first ever evaluation of interseasonal and interannual variability in DMSW and associated flux to the atmosphere from the Antarctic coastal zone and determine the scale and importance of the region as a significant source of DMS. Impacts of climate modes such as El Niňo/Southern Oscillation are evaluated. Maximum DMSW concentrations occurred annually in January and were primarily associated with sea-ice break-up. These concentrations resulted in extremely high (up to 968 µmol m-2 d-1) DMS flux over short timescales, which are not parameterised in global-scale DMS climatologies. Calculated DMS flux stayed above the aerosol nucleation threshold of 2.5 µmol m-2 d-1 for 60% of the year. Overall, using flux determinations from this study, the total flux of DMS-sulfur from the Austral Polar Province (APLR) was 1.1 Tg sulfur yr-1, more than double the figure suggested by the most recent DMS climatologies.
Project description:Palmer Deep (PD) is one of several regional hotspots of biological productivity along the inner shelf of the West Antarctic Peninsula. The proximity of hotspots to shelf-crossing deep troughs has led to the 'canyon hypothesis', which proposes that circumpolar deep water flowing shoreward along the canyons is upwelled on the inner shelf, carrying nutrients including iron (Fe) to surface waters, maintaining phytoplankton blooms. We present here full-depth profiles of dissolved and particulate Fe and manganese (Mn) from eight stations around PD, sampled in January and early February of 2015 and 2016, allowing the first detailed evaluation of Fe sources to the area's euphotic zone. We show that upwelling of deep water does not control Fe flux to the surface; instead, shallow sediment-sourced Fe inputs are transported horizontally from surrounding coastlines, creating strong vertical gradients of dissolved Fe within the upper 100?m that supply this limiting nutrient to the local ecosystem. The supply of bioavailable Fe is, therefore, not significantly related to the canyon transport of deep water. Near shore time-series samples reveal that local glacial meltwater appears to be an important Mn source but, surprisingly, is not a large direct Fe input to this biological hotspot.This article is part of the theme issue 'The marine system of the West Antarctic Peninsula: status and strategy for progress in a region of rapid change'.
Project description:Both industrial effluent discharge and the resuspension of contaminated marine sediments are important sources of trace metals in seawater which potentially affect marine ecosystems. The aim of this study was to evaluate the impact of the industrial wastewaters having acidic pH (2-3) and containing trace metals on microbial diversity in the coastal ecosystem of the Gulf of Gabès (Tunisia, southern Mediterranean Sea) subjected to resuspension events of marine sediments. Four trace elements (As, Cd, U, and V) were monitored during 10-day sediment resuspension experiments. The highest enrichment in the seawater dissolved phase was observed for Cd followed by U, V, and As. Cd remobilization was improved by indigenous microbial community, while U release was mainly abiotic. Acidic effluent addition impacted both trace metal distribution and microbial diversity, particularly that of the abundant phylum Bacteroidetes. Members of the order Saprospirales were enriched from sediment in natural seawater (initial pH > 8), while the family Flavobacteriaceae was favored by acidified seawater (initial pH < 8). Some Flavobacteriaceae members were identified as dominant species in both initial sediment and experiments with acidic wastewater, in which their relative abundance increased with increasing dissolved Cd levels. It could be therefore possible to consider them as bioindicators of metal pollution and/or acidification in marine ecosystems.
Project description:A field, laboratory, and modeling study of As in groundwater discharging to Waquoit Bay, MA, shed light on coupled control of chemistry and hydrology on reactive transport of As in a coastal aquifer. Dissolved Fe(III) and As(III) in a reducing groundwater plume bracketed by an upper and a lower redox interface are oxidized as water flows toward the bay. This results in precipitation of Fe(III) oxides, along with oxidation and adsorption of As to sediment at the redox interfaces where concentrations of sedimentary HCl-leachable Fe (80-90% Fe(III)) are 734 +/- 232 mg kg(-1) and sedimentary phosphate-extractable As (90-100% As(VI) are 316 +/- 111 microg kg(-1) and are linearly correlated. Batch adsorption of As(III) onto orange, brown, and gray sediments follows Langmuir isotherms and can be fitted by a surface complexation model (SCM) assuming a diffuse layer for ferrihydrite. The sorption capacity and distribution coefficient for As increase with decreasing sediment Fe(II)/Fe. To allow accumulation of the amount of sediment As, similar hydrogeochemical conditions would have been operating for thousands of years at Waquoit Bay. The SCM simulated the observed dissolved As concentration better than a parametric approach based on Kd. Site-specific isotherms should be established for Kd- or SCM-based models.