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Environmental contextCopper released by deep-sea hydrothermal vents has been recognised to be partly stabilised against precipitation by its complexation with strong Cu binding ligands. Yet, the sources and nature of these compounds in such environments are still not fully understood. This study shows that the Cu ligands detected are hydrothermally sourced and could be mainly inorganic sulfur species. AbstractThe apparent speciation of Cu in the early buoyant plume of two black smokers (Aisics and Y3) from the hydrothermal vent field Lucky Strike (Mid-Atlantic Ridge) was investigated using competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-AdCSV). We have assessed the apparent Cu-binding ligand concentration ([L]) and the corresponding conditional stability constant (log K) for 24 samples. At the smoker Aisics, [L] ranged from 18.2 to 2970nM. Log K-CuL ranged from 12.4 to 13.4. At Y3, the binding capacity of natural ligands was from 32.5 to 1020nM, with Log K-CuL ranging from 12.5 to 13.1. Total dissolved Cu ranged from 7.0 to 770nM and from 12.7 to 409nM at Aisics and Y3, respectively. Our results show that the amount of ligand L increases with dissolved Mn (dMn) concentrations, suggesting a hydrothermal origin of the Cu-binding ligands detected. In addition, such high concentrations of Cu-binding ligands can only be explained by an additional abiotic source differing from organic processes. Based on the massive in situ concentrations of free sulfides (up to 300 mu M) and on the striking similarities between our log K-CuL and the log K-Cu(HS) previously published, we infer that the Cu-binding ligands could be predominantly inorganic sulfur species in the early buoyant plume of the two vent sites studied.

In this study, we report the distributions of total dissolvable cadmium and particulate cadmium from 27 stations in southern Moroccan coastal waters (22°N–30°N), which is part of the North-West African upwelling system. These distributions were predominantly controlled by upwelling of the North Atlantic Central Waters (NACWs) and uptake by primary production. Atmospheric inputs and phosphogypsum slurry inputs from the phosphate industry at Jorf Lasfar (33°N), recently estimated as an important source of dissolved cadmium (240 t Cd yr−1), are at best of minor importance for the studied waters. Our study provides new insights into the mechanisms fractionating cadmium from phosphate. In the upper 30 m, the anomalies observed in terms of Cd:P ratios in both the particulate and total dissolvable fractions were related to an overall preferential uptake of phosphate. We show that the type of phytoplanktonic assemblage (diatoms versus dinoflagellates) is also a determinant of the fractionation intensity. In subsurface waters (30–60 m), a clear preferential release of P (versus Cd) was observed indicating that remineralization in Oxygen Minimum Zones is a key process in sequestering Cd.