Distribution of copper-binding ligands in Fram Strait and influences from the Greenland Shelf (GEOTRACES GN05)

The Fram Strait represents the major gateway of Arctic Ocean waters towards the Nordic Seas and North Atlantic Ocean and is a key region to study the impact of climate change on biogeochemical cycles. In the region, information about trace metal speciation, such as copper, is scarce. This manuscript presents the concentrations and conditional stability constants of copper-binding ligands (L_Cu and log K^cond_Cu2+L) in the water column of Fram Strait and the Greenland shelf (GEOTRACES cruise GN05). Cu-binding ligands were analysed by Competitive Ligand Exchange-Adsorptive Cathodic Stripping Voltammetry (CLE-ACSV) using salicylaldoxime (SA) as competitive ligand. Based on water masses and the hydrodynamic influences, three provinces were considered (coast, shelf, and Fram Strait) and differences were observed between regions and water masses. The strongest variability was observed in surface waters, with increasing L_Cu concentrations (mean values: Fram Strait = 2.6 ± 1.0 nM; shelf = 5.2 ± 1.3 nM; coast = 6.4 ± 0.8 nM) and decreasing log K^cond_Cu2+L values (mean values: Fram Strait = 15.7 ± 0.3; shelf = 15.2 ± 0.3; coast = 14.8 ± 0.3) towards the west. The surface L_Cu concentrations obtained above the Greenland shelf indicate a supply from the coastal environment to the Polar Surface Water (PSW) which is an addition to the ligand exported from the central Arctic to Fram Strait. The significant differences (in terms of L_Cu and log K^cond_Cu2+L) between shelf and coastal samples were explained considering the processes which modify ligand concentrations and binding strengths, such as biological activity in sea-ice, phytoplankton bloom in surface waters, bacterial degradation, and meltwater discharge from 79NG glacier terminus. Overall, the ligand concentration exceeded those of dissolved Cu (dCu) and kept the free copper (Cu²⁺) concentrations at femtomolar levels (0.13-21.13 fM). This indicates that Cu²⁺ toxicity limits were not reached and dCu levels were stabilized in surface waters by organic complexes, which favoured its transport to the Nordic Seas and North Atlantic Ocean and the development of microorganism.