Description: Highlights • Fe-binding ligands associated with primary productivity together with ligands from the Arctic Ocean are the main sources of Fe-binding ligands in surface waters of Fram Strait. • Fe-binding ligands are present in a high concentrations in front of the glacier terminus, but the ligands have a relatively low binding capacity, thus less reactive. • Low binding strength coupled with low competing strength of ligands result in a higher inorganic Fe concentration, causing Fe to precipitate or scavenged. Abstract There is a paucity of data on Fe-binding ligands in the Arctic Ocean. Here we investigate the distribution and chemical properties of natural Fe-binding ligands in Fram Strait and over the northeast Greenland shelf, shedding light on their potential sources and transport. Our results indicate that the main sources of organic ligands to surface waters of Fram Strait included primary productivity and supply from the Arctic Ocean. We calculated the mean total Fe-binding ligand concentration, [Lt], in Polar Surface Water from the western Fram Strait to be 1.65 ± 0.4 nM eq. Fe. This value is in between reported values for the Arctic and North Atlantic Oceans, confirming reports of north to south decreases in [Lt] from the Arctic Ocean. The differences between ligand sources in different biogeochemical provinces, resulted in distinctive ligand properties and distributions that are reflected in [Lt], binding strength (log KFe'L′) and competing strength (log αFe'L) of ligands. Higher [Lt] was present near the Nioghalvfjerdsfjorden (79 N) Glacier terminus and in the Westwind Trough (median of [Lt] = 2.17 nM eq. Fe; log KFe'L′ = 12.3; log αFe'L = 3.4) than in the Norske Trough (median of [Lt] = 1.89 nM eq. Fe; log KFe'L′= 12.8; log αFe'L = 3.8) and in Fram Strait (median of [Lt] = 1.38 nM eq. Fe; log KFe'L′ = 13; log αFe'L= 3.9). However, organic ligands near the 79 N Glacier terminus and in the Westwind Trough were weaker, and therefore less reactive than organic ligands in the Norske Trough and in Fram Strait. Our findings reveal the fundamental mechanism that underpin transport of dissolved-Fe (DFe) from the 79 N Glacier to Fram Strait, less reactive ligands will reduce Fe solubility. Accordingly, a portion of the glacial DFe will not be transported over the shelf into the ocean. The lower ligand binding strength in the outflow results in a higher inorganic Fe concentration, [Fe´], which is more prone to precipitation and/or scavenging than Fe complexed with stronger ligands. Ongoing changes in the Arctic and sub-Arctic Oceans will influence both terrestrially derived and in-situ produced Fe-binding ligands, and therefore will have consequences for Fe solubility and availability to microbial populations and Fe cycling in Fram Strait.

Description: 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.

Description: 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.

Description: 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.