The Costa Rica upwelling dome (CRD; ϳ8.67ЊN and 90.6ЊW) was characterized chemically for cobalt and nickel abundances and speciation and biologically using cyanobacterial abundances and phylogeny. Total dissolved cobalt was 93 pmol L Ϫ1 at 90 m depth and decreased in surface waters to 45 pmol L Ϫ1 at 10 m. Cobalt was 40% labile at 90 m but was completely complexed by strong ligands at 10 m. A surface transect out of the dome showed decreasing total dissolved cobalt from 57 pmol L Ϫ1 to 12 pmol L Ϫ1 . Detection window studies showed that natural cobalt-ligand complexes have conditional stability constants greater than 10 16.8 and that competition with nickel did not release cobalt bound to organic complexes, consistent with natural cobalt ligands being Co(III) complexes. Synechococcus cell densities at the CRD are among the highest reported in nature, varying between 1.2 ϫ 10 6 and 3.7 ϫ 10 6 cells ml Ϫ1 . Phylogenetic analysis using the 16S-23S rDNA internally transcribed spacer showed the majority of clones were related to Synechococcus strain MIT S9220, while the remaining subset form a novel group within the marine Synechococcus lineage. In a bottle incubation experiment chlorophyll increased with cobalt and iron additions relative to each element alone and the unamended control treatment. Cobalt speciation analysis of incubation experiments revealed large quantities of strong cobalt-ligand complexes in the cobalt addition treatments (401 pmol L Ϫ1 ), whereas cobalt added to a 0.2-m filtered control remained predominantly labile (387 pmol L Ϫ1 ), demonstrating that the Synechococcus-dominated community is a source of strong cobalt ligands.Processes that influence the production of metal binding ligands in the surface ocean are not well understood. Many of the important biologically used metals (Fe, Cu, Zn, Co, and Cd) have a chemical speciation that is dominated by their complexation with strong organic ligands (e.g., Rue and Bruland 1995;Saito and Moffett 2001; Morel et al. and references therein;Morel et al. 2003). While the chemical structures of these metal-complexing ligands in the natural environment are currently unknown, their destruction by ultraviolet-irradiation provides evidence for their organic composition. Furthermore, conditional stability constants indicate these ligands are very strong, much stronger than most inorganic complexes (i.e., chloro or carbonate complexes).1 Corresponding author (mak@whoi.edu).
AcknowledgmentsWe are grateful to co-chief scientists Ken Bruland and Dave Hutchins for providing space aboard the cruise, helpful discussions, and ancillary data. Thanks to G. Smith, J. Conn, and L. M. Lessin for water samples and nutrient and chlorophyll analyses. Thanks to the captain and crew of the R/V Melville. We are indebted to J. Waterbury, E. Webb, and two anonymous reviewers' comments on the manuscript and to Val Franck for helpful discussions.