Copper-binding ligands in the NE Pacific

• Published in: Marine Chemistry
• Main Authors: Whitby, Hannah, Posacka, Anna M., Maldonado, Maria T., Berg, Constant M. G., van Den
• Other Authors: Laboratoire des Sciences de l'Environnement Marin (LEMAR) (LEMAR), Institut de Recherche pour le Développement (IRD)-Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER)-Université de Brest (UBO)-Institut Universitaire Européen de la Mer (IUEM), Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Université de Brest (UBO)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), University of British Columbia (UBC), University of Liverpool
• Format: Article in Journal/Newspaper
• Language: English
• Published: HAL CCSD 2018
• Subjects: ACL; marine-phytoplankton; Seawater; Glutathione; Thiols; sub-arctic pacific; Copper speciation; Thiourea; humic substances; complexing ligands; dissolved organic-matter; Cathodic stripping voltammetry; estuarine waters; methylosinus-trichosporium ob3b; northeast pacific; Organic ligands; san-francisco bay; [SDE.BE]Environmental Sciences/Biodiversity and Ecology; [SDU.OCEAN]Sciences of the Universe [physics]/Ocean; Atmosphere; Arctic; Pacific; Phytoplankton
• Online Access: https://hal.science/hal-02651794; https://hal.science/hal-02651794/document; https://hal.science/hal-02651794/file/Whitby_etal_MC_2018.pdf; https://doi.org/10.1016/j.marchem.2018.05.008

WOS:000443668500004 International audience Copper distribution and speciation were determined at stations P4 and P26 along Line P as part of a GEOTRACES Process Study in the Northeast Pacific, at depths between 10 and 1400 m. Two ligand classes (L-1 and L-2) were detected at both stations: the stronger L-1 ligand pool with log K'(cu2+)(L1) 15.0-16.5 and the weaker L-2 ligand pool with log K'(cu2)(+L2) 11.6-13.6. The L-1 class bound on average 94% of dCu, with the ratio between L-1 and dCu constant and close to unity (1.15 = [L-1]:[dCu]). The concentrations of total ligands exceeded those of dCu at all depths, buffering Cu2+ concentrations ([Cu2+]) to femtomolar levels (i.e. pCu 14.1-15.7). Measurements using cathodic stripping voltammetry also identified natural copper-responsive peaks, which were attributed to thiourea- and glutathione-like thiols (TU and GSH, respectively), and Cu-binding humic substances (HScu). Concentrations of TU, GSH and HScu were determined by standard addition of model compounds in an attempt to identify Cu-binding ligands. HScu concentrations were generally higher at P26 than at P4, consistent with a marine origin of the humic material. Overall, HScu contributed to 1-27% of the total L concentration (L-T) and when combined with the two thiols contributed to up to 32% of L-T. This suggests other ligand types are responsible for the majority of dCu complexation in these waters, such as other thiols. Some potential candidates for detected, but unidentified, thiols are cysteine, 3-mercaptopropionic acid and 2-mercaptoethanol, all of which bind Cu. Significant correlation between the concentrations of TU-like thiols and L-1, along with the high log K'(cu)(2+)(L1) values, tentatively suggest that the electrochemical TU-type peak could be part of a larger, unidentified, high-affinity Cu compound, such as a methanobactin or porphyrin, with a stronger binding capability than typical thiols. This could imply that chalkophores may play a greater role in oceanic dCu complexation than ...