Mercury in the Black Sea:New Insights From Measurements and Numerical Modeling

Redox conditions and organic matter control marine methylmercury (MeHg) production. The Black Sea is the world's largest and deepest anoxic basin and is thus ideal to study Hg species along the extended redox gradient. Here we present new dissolved Hg and MeHg data from the 2013 GEOTRACES MEDBlack cruise (GN04_leg2) that we integrated into a numerical 1-D model, to track the fate and dynamics of Hg and MeHg. Contrary to a previous study, our new data show highest MeHg concentrations in the permanently anoxic waters. Observed MeHg/Hg percentage (range 9-57%) in the anoxic waters is comparable to other subsurface maxima in oxic open-ocean waters. With the modeling we tested for various Hg methylation and demethylation scenarios along the redox gradient. The results show that Hg methylation must occur in the anoxic waters. The model was then used to simulate the time evolution (1850-2050) of Hg species in the Black Sea. Our findings quantify (1) inputs and outputs of Hg-T (similar to 31 and similar to 28 kmol yr(-1)) and MeHgT (similar to 5 and similar to 4 kmol yr(-1)) to the basin, (2) the extent of net demethylation occurring in oxic (similar to 1 kmol yr(-1)) and suboxic water (similar to 6 kmol yr(-1)), (3) and the net Hg methylation in the anoxic waters of the Black Sea (similar to 11 kmol yr(-1)). The model was also used to estimate the amount of anthropogenic Hg (85-93%) in the Black Sea

Fe-binding organic ligands in coastal and frontal regions of the western Antarctic Peninsula

Organic ligands are a key factor determining the availability of dissolved iron (DFe) in the high-nutrient low-chlorophyll (HNLC) areas of the Southern Ocean. In this study, organic speciation of Fe is investigated along a natural gradient of the western Antarctic Peninsula, from an ice-covered shelf to the open ocean. An electrochemical approach, competitive ligand exchange – adsorptive cathodic stripping voltammetry (CLE-AdCSV), was applied. Our results indicated that organic ligands in the surface water on the shelf are associated with ice-algal exudates, possibly combined with melting of sea ice. Organic ligands in the deeper shelf water are supplied via the resuspension of slope or shelf sediments. Further offshore, organic ligands are most likely related to the development of phytoplankton blooms in open ocean waters. On the shelf, total ligand concentrations ([Lt]) were between 1.2 and 6.4 nM eq. Fe. The organic ligands offshore ranged between 1.0 and 3.0 nM eq. Fe. The southern boundary of the Antarctic Circumpolar Current (SB ACC) separated the organic ligands on the shelf from bloom-associated ligands offshore. Overall, organic ligand concentrations always exceeded DFe concentrations (excess ligand concentration, [L′] = 0.8–5.0 nM eq. Fe). The [L′] made up to 80 % of [Lt], suggesting that any additional Fe input can be stabilized in the dissolved form via organic complexation. The denser modified Circumpolar Deep Water (mCDW) on the shelf showed the highest complexation capacity of Fe (αFe'L; the product of [L′] and conditional binding strength of ligands, KFe'Lcond). Since Fe is also supplied by shelf sediments and glacial discharge, the high complexation capacity over the shelf can keep Fe dissolved and available for local primary productivity later in the season upon sea-ice melting.</p

Effects of Iron and Light Availability on Phytoplankton Photosynthetic Properties in the Ross Sea

Waters of the Southern Ocean are characterized by high macronutrient concentrations but limited availability of trace metals and light, often making it difficult for phytoplankton to achieve maximum growth rates. One strategy employed by Southern Ocean phytoplankton in culture to cope with low light and low dissolved iron (DFe) is to enhance light absorption by increasing their antenna size rather than the number of reaction centers, thereby reducing their Fe demand. Here we provide physiological evidence that natural populations of Southern Ocean phytoplankton employ a similar photoacclimation strategy to cope with low ambient DFe concentrations. During a research cruise to the Ross Sea in 2013-2014, we conducted 4 bioassay experiments in which we manipulated light and DFe concentrations and measured changes in phytoplankton biomass, growth rate, photosynthetic parameters, fluorescence parameters, and pigment composition. Phytoplankton responded strongly to DFe additions, exhibiting significantly higher biomass, growth rates, and photosynthetic competency. At low light, the maximum photosynthetic rate (P*max) was significantly reduced and the photosynthetic efficiency (α*) was unchanged compared to the high light treatment, regardless of phytoplankton species composition or DFe concentration. Our data suggest that Southern Ocean phytoplankton have evolved an Fe-saving strategy whereby they photoacclimate to low light by increasing their photosynthetic unit size, rather than photosynthetic unit number, even when DFe is available. It appears this Fe-saving strategy is characteristic of both Phaeocystis antarctica and diatoms, suggesting that it is a common adaptation among phytoplankton taxa that grow under Fe limitation in the Southern Ocean

Estimating the Benthic Efflux of Dissolved Iron on the Ross Sea Continental Shelf

Continental margin sediments provide a potentially large but poorly constrained source of dissolved iron (dFe) to the upper ocean. The Ross Sea continental shelf is one region where this benthic supply is thought to play a key role in regulating the magnitude of seasonal primary production. Here we present data collected during austral summer 2012 that reveal contrasting low surface (0.08 +/- 0.07 nM) and elevated near-seafloor (0.74 +/- 0.47 nM) dFe concentrations. Combining these observations with results from a high-resolution physical circulation model, we estimate dFe efflux of 5.8 x 10(7) mol yr(-1) from the deeper portions (\u3e400m) of the Ross Sea continental shelf; more than sufficient to account for the inferred winter reserve dFe inventory at the onset of the growing season. In addition, elevated dFe concentrations observed over shallower bathymetry suggest that such features provide additional inputs of dFe to the euphotic zone throughout the year

Dissolved Cd, Co, Cu, Fe, Mn, Ni and Zn in the Arctic Ocean

During the Polarstern (PS94) expedition, summer 2015, part of the international GEOTRACES program, sources and sinks of dissolved (D) Cd, Co, Cu, Fe, Mn, Ni and Zn were studied in the central Arctic Ocean. In the Polar Surface Water in which the TransPolar Drift (TPD) is situated, salinity and δ18O derived fractions indicated a distinct riverine source for silicate DCo, DCu, DFe, DMn and DNi. Linear relationships between DMn and the meteoric fraction depended on source distance, likely due to Mn-precipitation during transport. In the upper 50 m of the Makarov Basin, outside the TPD core, DCo, DMn, DNi, DCd and DCu were enriched by Pacific waters, whereas DFe seemed diluted. DCo, DFe, DMn and DZn were relatively high in the Barents Sea and led to enrichment of Atlantic water flowing into the Nansen Basin. Deep concentrations of all metals were significantly lower in the Makarov Basin compared to the Nansen and Amundsen, the Eurasian, Basins. The Gakkel ridge hydrothermal input and higher continental slope convection are explanations for higher metal concentrations in the Eurasian Basins. Although scavenging rates are lower in the Makarov Basin compared to the Eurasian Basins, the residence time is longer and therefore scavenging can decrease the dissolved concentrations with time. This study provides a baseline to assess future change, and additionally identifies processes driving trace metal distributions. Our results underline the importance of fluvial input as well as shelf sources and internal cycling, notably scavenging, for the distribution of bio-active metals in the Arctic Ocean

Climatically sensitive transfer of iron to maritime Antarctic ecosystems by surface runoff

Iron supplied by glacial weathering results in pronounced hotspots of biological production in an otherwise iron-limited Southern Ocean Ecosystem. However, glacial iron inputs are thought to be dominated by icebergs. Here we show that surface runoff from three island groups of the maritime Antarctic exports more filterable (<0.45 μm) iron (6–81 kg km−2 a−1) than icebergs (0.0–1.2 kg km−2 a−1). Glacier-fed streams also export more acid-soluble iron (27.0–18,500 kg km−2 a−1) associated with suspended sediment than icebergs (0–241 kg km−2 a−1). Significant fluxes of filterable and sediment-derived iron (1–10 Gg a−1 and 100–1,000 Gg a−1, respectively) are therefore likely to be delivered by runoff from the Antarctic continent. Although estuarine removal processes will greatly reduce their availability to coastal ecosystems, our results clearly indicate that riverine iron fluxes need to be accounted for as the volume of Antarctic melt increases in response to 21st century climate change

Tracking Changes in Bioavailable Fe Within High-Nitrate Low-Chlorophyll Oceanic Waters: A First Estimate Using a Heterotrophic Bacterial Bioreporter

It is conventional knowledge that heterotrophic bacteria play a key role in the biogeochemical cycling of oceanic carbon. However, only recently has their role in marine iron ( Fe) biogeochemical cycles been examined. Research during this past decade has demonstrated an inextricable link between Fe chemistry and the biota, as \u3e99% of Fe in marine systems is complexed to organic chelates of unknown but obviously biotic origin. Here we present a novel approach to assess and compare Fe bioavailability in low Fe HNLC waters using a bioluminescent bacterial reporter that quantitatively responds to the concentration of bioavailable Fe by producing light. Originally tested in freshwater environments, this study presents the first characterization of this halotolerant reporter organism in a defined seawater medium and then subsequently in marine surface waters. Laboratory characterizations demonstrate that this reporter displays a dose-dependent response to Fe availability in our defined marine medium. Field tests were performed during the 10-day mesoscale FeCycle experiment ( February 2003) in the Pacific sub-Antarctic high-nitrate low-chlorophyll region. Data from both biogeochemical measures and bioreporter assays are provided which describe how the bioreporter detected changes in Fe bioavailability that occurred during a natural shift in ambient dissolved Fe concentrations (similar to 40 pM). Our data explore the use of heterotrophic bioluminescent reporters as a comparable tool for marine ecosystems and demonstrate the potential utility of this tool in elucidating the relationship between Fe bioavailability and Fe chemistry in complex marine systems

Biolabile ferrous iron bearing nanoparticles in glacial sediments

Glaciers and ice sheets are a significant source of nanoparticulate Fe, which is potentially important in sustaining the high productivity observed in the near-coastal regions proximal to terrestrial ice cover. However, the bioavailability of particulate iron is poorly understood, despite its importance in the ocean Fe inventory. We combined high-resolution imaging and spectroscopy to investigate the abundance, morphology and valence state of particulate iron in glacial sediments. Our results document the widespread occurrence of amorphous and Fe(II)-rich and Fe(II)-bearing nanoparticles in Arctic glacial meltwaters and iceberg debris, compared to Fe(III)-rich dominated particulates in an aeolian dust sample. Fe(II) is thought to be highly biolabile in marine environments. Our work shows that glacially derived Fe is more labile than previously assumed, and consequently that glaciers and ice sheets are therefore able to export potentially bioavailable Fe(II)-containing nanoparticulate material to downstream ecosystems, including those in a marine setting. Our findings provide further evidence that Greenland Ice Sheet meltwaters may provide biolabile particulate Fe that may fuel the large summer phytoplankton bloom in the Labrador Sea, and that Fe(II)-rich particulates from a region of very high productivity downstream of a polar ice sheet may be glacial in origin

Arctic – Atlantic exchange of the dissolved micronutrients Iron, Manganese, Cobalt, Nickel, Copper and Zinc with a focus on Fram Strait

The Arctic Ocean is considered a source of micronutrients to the Nordic Seas and the North Atlantic Ocean through the gateway of Fram Strait. However, there is a paucity of trace element data from across the Arctic Ocean gateways, and so it remains unclear how Arctic and North Atlantic exchange shapes micronutrient availability in the two ocean basins. In 2015 and 2016, GEOTRACES cruises sampled the Barents Sea Opening (GN04, 2015) and Fram Strait (GN05, 2016) for dissolved iron (dFe), manganese (dMn), cobalt (dCo), nickel (dNi), copper (dCu) and zinc (dZn). Together with the most recent synopsis of Arctic-Atlantic volume fluxes, the observed trace element distributions suggest that Fram Strait is the most important gateway for Arctic-Atlantic dissolved micronutrient exchange as a consequence of Intermediate and Deep Water transport. Combining fluxes from Fram Strait and the Barents Sea Opening with estimates for Davis Strait (GN02, 2015) suggests an annual net southward flux of 2.7 ± 2.4 Gg·a-1 dFe, 0.3 ± 0.3 Gg·a-1 dCo, 15.0 ± 12.5 Gg·a-1 dNi and 14.2 ± 6.9 Gg·a-1 dCu from the Arctic towards the North Atlantic Ocean. Arctic-Atlantic exchange of dMn and dZn were more balanced, with a net southbound flux of 2.8 ± 4.7 Gg·a-1 dMn and a net northbound flux of 3.0 ± 7.3 Gg·a-1 dZn. Our results suggest that ongoing changes to shelf inputs and sea ice dynamics in the Arctic, especially in Siberian shelf regions, affect micronutrient availability in Fram Strait and the high latitude North Atlantic Ocean