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  • 1
    In: Marine Chemistry, Elsevier BV, Vol. 224 ( 2020-08), p. 103815-
    Materialart: Online-Ressource
    ISSN: 0304-4203
    Sprache: Englisch
    Verlag: Elsevier BV
    Publikationsdatum: 2020
    ZDB Id: 184352-7
    ZDB Id: 1497339-X
    Standort Signatur Einschränkungen Verfügbarkeit
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  • 2
    Online-Ressource
    Online-Ressource
    Frontiers Media SA ; 2021
    In:  Frontiers in Marine Science Vol. 7 ( 2021-1-21)
    In: Frontiers in Marine Science, Frontiers Media SA, Vol. 7 ( 2021-1-21)
    Kurzfassung: 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) & gt; [L t ] TAC (1.77 ± 0.57 nM eq Fe) & gt; [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.
    Materialart: Online-Ressource
    ISSN: 2296-7745
    Sprache: Unbekannt
    Verlag: Frontiers Media SA
    Publikationsdatum: 2021
    ZDB Id: 2757748-X
    Standort Signatur Einschränkungen Verfügbarkeit
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  • 3
    In: Biogeosciences, Copernicus GmbH, Vol. 18, No. 15 ( 2021-08-11), p. 4587-4601
    Kurzfassung: Abstract. 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.
    Materialart: Online-Ressource
    ISSN: 1726-4189
    Sprache: Englisch
    Verlag: Copernicus GmbH
    Publikationsdatum: 2021
    ZDB Id: 2158181-2
    Standort Signatur Einschränkungen Verfügbarkeit
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  • 4
    Online-Ressource
    Online-Ressource
    Royal Society of Chemistry (RSC) ; 2016
    In:  Journal of Materials Chemistry A Vol. 4, No. 32 ( 2016), p. 12425-12433
    In: Journal of Materials Chemistry A, Royal Society of Chemistry (RSC), Vol. 4, No. 32 ( 2016), p. 12425-12433
    Materialart: Online-Ressource
    ISSN: 2050-7488 , 2050-7496
    Sprache: Englisch
    Verlag: Royal Society of Chemistry (RSC)
    Publikationsdatum: 2016
    ZDB Id: 2702232-8
    Standort Signatur Einschränkungen Verfügbarkeit
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  • 5
    Online-Ressource
    Online-Ressource
    Royal Society of Chemistry (RSC) ; 2018
    In:  Journal of Materials Chemistry A Vol. 6, No. 39 ( 2018), p. 19266-19266
    In: Journal of Materials Chemistry A, Royal Society of Chemistry (RSC), Vol. 6, No. 39 ( 2018), p. 19266-19266
    Materialart: Online-Ressource
    ISSN: 2050-7488 , 2050-7496
    Sprache: Englisch
    Verlag: Royal Society of Chemistry (RSC)
    Publikationsdatum: 2018
    ZDB Id: 2702232-8
    Standort Signatur Einschränkungen Verfügbarkeit
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  • 6
    In: Biogeosciences, Copernicus GmbH, Vol. 18, No. 19 ( 2021-09-30), p. 5265-5289
    Kurzfassung: Abstract. Competitive ligand exchange–adsorptive cathodic stripping voltammetry (CLE-AdCSV) is used to determine the conditional concentration ([L]) and the conditional binding strength (logKcond) of dissolved organic Fe-binding ligands, which together influence the solubility of Fe in seawater. Electrochemical applications of Fe speciation measurements vary predominantly in the choice of the added competing ligand. Although different applications show the same trends, [L] and logKcond differ between the applications. In this study, binding of two added ligands in three different common applications to three known types of natural binding ligands is compared. The applications are (1) salicylaldoxime (SA) at 25 µM (SA25) and short waiting time, (2) SA at 5 µM (SA5), and (3) 2-(2-thiazolylazo)-ρ-cresol (TAC) at 10 µM, the latter two with overnight equilibration. The three applications were calibrated under the same conditions, although having different pH values, resulting in the detection window centers (D) DTAC 〉 DSA25 ≥ SA5 (as logD values with respect to Fe3+: 12.3 〉 11.2 ≥ 11). For the model ligands, there is no common trend in the results of logKcond. The values have a considerable spread, which indicates that the error in logKcond is large. The ligand concentrations of the nonhumic model ligands are overestimated by SA25, which we attribute to the lack of equilibrium between Fe-SA species in the SA25 application. The application TAC more often underestimated the ligand concentrations and the application SA5 over- and underestimated the ligand concentration. The extent of overestimation and underestimation differed per model ligand, and the three applications showed the same trend between the nonhumic model ligands, especially for SA5 and SA25. The estimated ligand concentrations for the humic and fulvic acids differed approximately 2-fold between TAC and SA5 and another factor of 2 between SA5 and SA25. The use of SA above 5 µM suffers from the formation of the species Fe(SA)x (x〉1) that is not electro-active as already suggested by Abualhaija and van den Berg (2014). Moreover, we found that the reaction between the electro-active and non-electro-active species is probably irreversible. This undermines the assumption of the CLE principle, causes overestimation of [L] and could result in a false distinction into more than one ligand group. For future electrochemical work it is recommended to take the above limitations of the applications into account. Overall, the uncertainties arising from the CLE-AdCSV approach mean we need to search for new ways to determine the organic complexation of Fe in seawater.
    Materialart: Online-Ressource
    ISSN: 1726-4189
    Sprache: Englisch
    Verlag: Copernicus GmbH
    Publikationsdatum: 2021
    ZDB Id: 2158181-2
    Standort Signatur Einschränkungen Verfügbarkeit
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  • 7
    In: Nature Communications, Springer Science and Business Media LLC, Vol. 12, No. 1 ( 2021-05-24)
    Kurzfassung: Approximately half of the freshwater discharged from the Greenland and Antarctic Ice Sheets enters the ocean subsurface as a result of basal ice melt, or runoff draining via the grounding line of a deep ice shelf or marine-terminating glacier. Around Antarctica and parts of northern Greenland, this freshwater then experiences prolonged residence times in large cavities beneath floating ice tongues. Due to the inaccessibility of these cavities, it is unclear how they moderate the freshwater associated supply of nutrients such as iron (Fe) to the ocean. Here, we show that subglacial dissolved Fe export from Nioghalvfjerdsbrae (the ‘79°N Glacier’) is decoupled from particulate inputs including freshwater Fe supply, likely due to the prolonged ~162-day residence time of Atlantic water beneath Greenland’s largest floating ice-tongue. Our findings indicate that the overturning rate and particle-dissolved phase exchanges in ice cavities exert a dominant control on subglacial nutrient supply to shelf regions.
    Materialart: Online-Ressource
    ISSN: 2041-1723
    Sprache: Englisch
    Verlag: Springer Science and Business Media LLC
    Publikationsdatum: 2021
    ZDB Id: 2553671-0
    Standort Signatur Einschränkungen Verfügbarkeit
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