Copper-binding ligands in the NE Pacific
|Author(s)||Whitby Hannah1, Posacka Anna M.2, Maldonado Maria T.2, Van Den Berg Constant M. G.3|
|Affiliation(s)||1 : LEMAR, Technopole Brest Iroise, F-29280 Plouzane, France.
2 : Univ British Columbia, Vancouver, BC V6T 1Z4, Canada.
3 : Univ Liverpool, Liverpool L69 3GP, Merseyside, England.
|Source||Marine Chemistry (0304-4203) (Elsevier Science Bv), 2018-08 , Vol. 204 , P. 36-48|
|WOS© Times Cited||21|
|Keyword(s)||Copper speciation, Seawater, Thiols, Humic substances, Cathodic stripping voltammetry, Thiourea, Glutathione, Organic ligands|
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 previously considered.