Evidence for the production of copper-complexing ligands by marine phytoplankton in the subarctic northeast Pacific

The availability and toxicity of copper (Cu) to marine phytoplankton involve complexation of Cu by dissolved organic ligands of uncertain origin and structure. As part of a GEOTRACES process study we used immobilized copper(II)-ion affinity chromatography (IMAC) to isolate and obtain information about the distribution and potential sources of Cu-complexing ligands along Line P in the subarctic northeast Pacific. Filtered seawater samples were collected from up to five stations during cruises in June 2016, June 2017, August 2017, and September 2018. Copper ligand concentrations were consistently higher at coastal station P4 than at other stations, particularly in surface waters. Ligand concentrations in the upper 40 m at station P26 increased between 2016 and 2018 following the 2014–2016 warming anomaly in the northeast Pacific, whereas an increase in ligand concentration from June to August 2017 coincided with seasonal increases in dissolved organic carbon (DOC) and net community production. At all stations, the depth of highest ligand concentration and maximum chlorophyll concentration coincided. A positive linear correlation between ligand and chlorophyll concentrations suggests that marine phytoplankton are a significant source of Cu ligands along Line P. The lower than expected ligand concentrations at station P26 in June 2016 are consistent with changes in phytoplankton ecology associated with the 2014–2016 warming anomaly. Comparing results from coastal and oceanic waters with those obtained previously in the Canadian Arctic suggests that terrigenous organic matter and marine humic substances contribute to the pool of Cu ligands captured by IMAC