ALBERT

Beschreibung: This paper reports a physicochemical study (thermodynamic and kinetic data) describing the ability of Rubus ulmifolius biomass (dead leaves) for metal uptake. The toxicity of aluminum is a major problem for crops in acidic soils and therefore, aluminum has been selected. The results obtained indicate that dead R. ulmifolius leaves uptake up to 10000mg/kg on its surface in less than 60min. This suggests that R. ulmifolius can be an excellent component with adsorbent properties for aquatic environments and in particular for amendments to be used in acidic soils in order to control aluminum levels, thus its toxicity. The results obtained have been critically analyzed and compared with literature on aluminum bioaccumulation. The application of a pseudo-second order kinetic equation, not previously used in toxicity studies, is discussed. Moreover, a good linear correlation between stability constants for Al3+ complexes with several defined ligands and the Langmuir affinity constants obtained from the corresponding adsorption isotherm has been found. Therefore, in addition to its ethno-botanical relevance, applications of R. ulmifolius as a detoxifier for aluminum in a simulated acidic gastrointestinal fluid, as phytostabilization agent in amendments or in natural attenuation cycles or as biomass for wastewater treatment containing aluminum, are suggested.

Beschreibung: Competitive ligand exchange – adsorptive cathodic stripping voltammetry (CLE-AdCSV) is a widely used technique to determine dissolved iron (Fe) speciation in seawater, and involves competition for Fe of a known added ligand (AL) with natural organic ligands. Three different ALs were used, 2-(2-thiazolylazo)-p-cresol (TAC), salicylaldoxime (SA) and 1-nitroso-2-napthol (NN). The total ligand concentrations ([L t ]) and conditional stability constants (log K ′ Fe’L ) obtained using the different ALs are compared. The comparison was done on seawater samples from Fram Strait and northeast Greenland shelf region, including the Norske Trough, Nioghalvfjerdsfjorden (79N) Glacier front and Westwind Trough. Data interpretation using a one-ligand model resulted in [L t ] SA (2.72 ± 0.99 nM eq Fe) > [L t ] TAC (1.77 ± 0.57 nM eq Fe) > [L t ] NN (1.57 ± 0.58 nM eq Fe); with the mean of log K ′ Fe’L being the highest for TAC (log ′ K Fe’L(TAC) = 12.8 ± 0.5), followed by SA (log K ′ Fe’L(SA) = 10.9 ± 0.4) and NN (log K ′ Fe’L(NN) = 10.1 ± 0.6). These differences are only partly explained by the detection windows employed, and are probably due to uncertainties propagated from the calibration and the heterogeneity of the natural organic ligands. An almost constant ratio of [L t ] TAC /[L t ] SA = 0.5 – 0.6 was obtained in samples over the shelf, potentially related to contributions of humic acid-type ligands. In contrast, in Fram Strait [L t ] TAC /[L t ] SA varied considerably from 0.6 to 1, indicating the influence of other ligand types, which seemed to be detected to a different extent by the TAC and SA methods. Our results show that even though the SA, TAC and NN methods have different detection windows, the results of the one ligand model captured a similar trend in [L t ], increasing from Fram Strait to the Norske Trough to the Westwind Trough. Application of a two-ligand model confirms a previous suggestion that in Polar Surface Water and in water masses over the shelf, two ligand groups existed, a relatively strong and relatively weak ligand group. The relatively weak ligand group contributed less to the total complexation capacity, hence it could only keep part of Fe released from the 79N Glacier in the dissolved phase.

Beschreibung: Around the Greenlandic and Antarctic coastlines, sediment plumes associated with glaciers are significant sources of lithogenic material to the ocean. These plumes contain elevated concentrations of a range of trace metals, especially in particle bound phases, but it is not clear how these particles affect dissolved (〈0.2 µm) metal distributions in the ocean. Here we show, using transects in 8 glacier fjords, trends in the distribution of dissolved iron, cobalt, nickel and copper (dFe, dCo, dNi, dCu). Following rapid dFe loss close to glacier outflows, dFe concentrations in particular showed strong similarities between different fjords. Similar dFe concentrations were also observed between seasons/years when Nuup Kangerlua (SW Greenland) was revisited in spring, mid- and late-summer. Dissolved Cu, dCo and dNi concentrations were more variable and showed different gradients with salinity depending on the fjord, season and year. The lack of consistent trends for dCu and dNi largely reflects less pronounced differences contrasting the concentration of inflowing shelf waters with fresher glacially-modified waters. Particles also made only small contributions to total dissolvable Cu (dCu constituted 83 ± 28% of total dissolvable Cu) and Ni (dNi constituted 86 ± 28% of total dissolvable Ni) within glacier plumes. For comparison, dFe was a lower fraction of total dissolvable Fe; 3.5 ± 4.8%. High concentrations of total dissolvable Fe in some inner-fjord environments, up to 77 µM in Ameralik (SW Greenland), may drive enhanced removal of scavenged type elements, such as Co. Further variability may have been driven by local bedrock mineralogy, which could explain high concentrations of dNi (25–29 nM) and dCo (6–7 nM) in one coastal region of west Greenland (Kangaatsiaq). Our results suggest that dissolved trace element distributions in glacier fjords are influenced by a range of factors including: freshwater concentrations, local geology, drawdown by scavenging and primary production, saline inflow, and sediment dynamics. Considering the lack of apparent seasonality in dFe concentrations, we suggest that fluxes of some trace elements may scale proportionately to fjord overturning rather than directly to freshwater discharge flux.

Beschreibung: Concentrations of the toxic element lead (Pb) are elevated in seawater due to historical emissions. While anthropogenic atmospheric emissions are the dominant source of dissolved Pb (dPb) to the Atlantic Ocean, evidence is emerging of a natural source associated with subglacial discharge into the ocean but this has yet to be constrained around Greenland. Here, we show subglacial discharge from the cavity underneath Nioghalvfjerdsbræ floating ice tongue, is a previously unrecognized source of dPb to the NE Greenland Shelf. Contrasting cavity-inflowing and cavity-outflowing waters, we constrain the associated net-dPb flux as 2.2 ± 1.4 Mg·yr−1, of which ∼90% originates from dissolution of glacial bedrock and cavity sediments. We propose that the retreat of the floating ice tongue, the ongoing retreat of many glaciers on Greenland, associated shifts in sediment dynamics, and enhanced meltwater discharges into shelf waters may result in pronounced changes, possibly increases, in net-dPb fluxes to coastal waters. Key Points - Helium and neon show strong evidence for a subglacial source of Pb discharging onto the NE Greenland Shelf - Contrasting inflowing and outflowing waters beneath the floating ice tongue of Nioghalvfjerdsbræ shows a 2-3-fold dPb enrichment - The dissolved Pb flux from Nioghalvfjerdsbræ (2.2 ± 1.4 Mg·yr−1) is comparable to small Arctic rivers, with ∼90% of a sedimentary origin

Beschreibung: We present high-resolution profiles of dissolved, labile and total particulate trace metals (TMs) on the Northeast Greenland shelf from GEOTRACES cruise GN05 in August 2016. Combined with radium isotopes, stable oxygen isotopes, and noble gas measurements, elemental distributions suggest that TM dynamics were mainly regulated by the mixing between North Atlantic-derived Intermediate Water, enriched in labile particulate TMs (LpTMs), and Arctic surface waters, enriched in Siberian shelf-derived dissolved TMs (dTMs; Co, Cu, Fe, Mn, and Ni) carried by the Transpolar Drift. These two distinct sources were delineated by salinity-dependent variations of dTM and LpTM concentrations and the proportion of dTMs relative to the total dissolved and labile particulate ratios. Locally produced meltwater from the Nioghalvfjerdsbræ (79NG) glacier cavity, distinguished from other freshwater sources using helium excess, contributed a large pool of dTMs to the shelf inventory. Localized peaks in labile and total particulate Cd, Co, Fe, Mn, Ni, Cu, Al, V, and Ti in the cavity outflow, however, were not directly contributed by submarine melting. Instead, these particulate TMs were mainly supplied by the re-suspension of cavity sediment particles. Currently, Arctic Ocean outflows are the most important source of dFe, dCu and dNi on the shelf, while LpTMs and up to 60% of dMn and dCo are mainly supplied by subglacial discharge from the 79NG cavity. Therefore, changes in the cavity-overturning dynamics of 79NG induced by glacial retreat, and alterations in the transport of Siberian shelf-derived materials with the Transport Drift may shift the shelf dTM-LpTM stoichiometry in the future. Key Points The overall dissolved and particulate trace metal dynamics were mainly regulated by the mixing with Arctic surface waters Resuspension of cavity sediments is a major localized source of labile and total particulate Cd, Co, Fe, Mn, Ni, Cu, Al, V, and Ti Whilst dissolved and particulate trace metals are mostly coupled on the Greenland shelf, cavity outflow decouples both phases

Beschreibung: 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.