FN Archimer Export Format PT J TI Cu transport and complexation by the marine diatom Phaeodactylum tricornutum: Implications for trace metal complexation kinetics in the surface ocean BT AF González-Dávila, Melchor Maldonado, Maria T. González, Aridane G. Guo, Jian González-Santana, David Martel, Antera Santana-Casiano, J. Magdalena AS 1:1;2:2;3:1;4:2;5:1;6:3;7:1; FF 1:;2:;3:;4:;5:;6:;7:; C1 Instituto de Oceanografía y Cambio Global, IOCAG, Universidad de Las Palmas de Gran Canaria, ULPGC, Spain Department of Earth, Ocean, and Atmospheric Sciences, University of British Columbia Vancouver, BC, Canada Banco Español de Algas, Instituto de Oceanografía y Cambio Global, IOCAG, Universidad de Las Palmas de Gran Canaria, ULPGC, Spain C2 UNIV LAS PALMAS GRAN CANARIA, SPAIN UNIV BRITISH COLUMBIA, CANADA UNIV LAS PALMAS GRAN CANARIA, SPAIN IF 9.8 TC 0 UR https://archimer.ifremer.fr/doc/00877/98859/108557.pdf https://archimer.ifremer.fr/doc/00877/98859/109296.docx LA English DT Article DE ;Copper;adsorption kinetics;Cu transport;complexation;diatoms;Phaeodactylum tricornutum;Cu uptake AB Elucidating whether dissolved Cu uptake is kinetically or thermodynamically controlled, and the effects of speciation on Cu transport by phytoplankton will allow better modeling of the fate and impact of dissolved Cu in the ocean. To address these questions, we performed Cu physiological and physicochemical experiments using the model diatom, Phaeodactylum tricornutum, grown in natural North Atlantic seawater (0.44 nM Cu). Using competitive ligand equilibration-cathodic stripping voltammetry (CLE-CSV), we measured two organic ligand types released by P. tricornutum to bind Cu (L1 and L2) at concentrations of ~0.35 nM L1 and 1.3 nM L2. We also established the presence of two putative Cu-binding sites at the cell surface of P. tricornutum (S1 and S2) with log K differing by ~5 orders of magnitude (i.e., 12.9 vs. 8.1) and cell surface densities by 9-fold. Only the high-affinity binding sites, S1, exhibit reductase activity. Using voltammetric kinetic measurements and a theoretical kinetic model, we calculated the forward and dissociation rate constants of L1 and S1. Complementary 67Cu uptake experiments identified a high- and a low-affinity Cu uptake system in P. tricornutum, with half-saturation constant (Km) of 154 nM and 2.63 μM dissolved Cu, respectively. In the P. tricornutum genome, we identified a putative high-affinity Cu transporter (PtCTR49224) and a putative ZIP-like, low-affinity Cu transporter (PtZIP49400). PtCTR49224 has high homology to Homo sapiens hCTR1, which depending on the accessibility to extracellular reducing agents, the hCTR1 itself is involved in the reduction of Cu2+ to Cu+ before internalization. We combined these physiological and physicochemical data to calculate the rate constants for the internalization of Cu, and established that while the high-affinity Cu uptake system (S1) is borderline between a kinetically or thermodynamically controlled system, the low-affinity Cu transporters, S2, is thermodynamically-controlled. We revised the inverse relationship between the concentrations of inorganic complexes of essential metals (i.e., Ni, Fe, Co, Zn, Cd, Mn and Cu) in the mixed layer and the formation rate constant of metal transporters in phytoplankton, highlighting the link between the chemical properties of phytoplankton metal transporters and the availability and speciation of trace metals in the surface ocean. PY 2024 PD APR SO Science of The Total Environment SN 0048-9697 PU Elsevier BV VL 919 DI 10.1016/j.scitotenv.2024.170752 ID 98859 ER EF