Cobalt, manganese, and iron near the Hawaiian Islands: A potential concentrating mechanism for cobalt within a cyclonic eddy and implications for the hybrid-type trace metals

The vertical distributions of cobalt, iron, and manganese in the water column were studied during the E-Flux Program (E-Flux II and III), which focused on the biogeochemistry of cold-core cyclonic eddies that form in the lee of the Hawaiian Islands. During E-Flux II (January 2005) and E-Flux III (March 2005), 17 stations were sampled for cobalt (n=147), all of which demonstrated nutrient-like depletion in surface waters. During E-Flux III, two depth profiles collected from within a mesoscale cold-core eddy, Cyclone Opal, revealed small distinct maxima in cobalt at ∼100 m depth and a larger inventory of cobalt within the eddy. We hypothesize that this was due to a cobalt concentrating effect within the eddy, where upwelled cobalt was subsequently associated with sinking particulate organic carbon (POC) via biological activity and was released at a depth coincident with nearly complete POC remineralization [Benitez-Nelson, C., Bidigare, R.R., Dickey, T.D., Landry, M.R., Leonard, C.L., Brown, S.L., Nencioli, F., Rii, Y.M., Maiti, K., Becker, J.W., Bibby, T.S., Black, W., Cai, W.J., Carlson, C.A., Chen, F., Kuwahara, V.S., Mahaffey, C., McAndrew, P.M., Quay, P.D., Rappe, M.S., Selph, K.E., Simmons, M.P., Yang, E.J., 2007. Mesoscale eddies drive increased silica export in the subtropical Pacific Ocean. Science 316, 1017–1020]. There is also evidence for the formation of a correlation between cobalt and soluble reactive phosphorus during E-Flux III relative to the E-Flux II cruise that we suggest is due to increased productivity, implying a minimum threshold of primary production below which cobalt–phosphate coupling does not occur. Dissolved iron was measured in E-Flux II and found in somewhat elevated concentrations (∼0.5 nM) in surface waters relative to the iron depleted waters of the surrounding Pacific [Fitzwater, S.E., Coale, K.H., Gordon, M.R., Johnson, K.S., Ondrusek, M.E., 1996. Iron deficiency and phytoplankton growth in the equatorial Pacific. Deep-Sea Research II 43 (4–6), 995–1015], possibly due to island effects associated with the iron-rich volcanic soil from the Hawaiian Islands and/or anthropogenic inputs. Distinct depth maxima in total dissolved cobalt were observed at 400–600 m depth, suggestive of the release of metals from the shelf area of comparable depth that surrounds these islands.