Metal quotas of plankton in the equatorial Pacific Ocean

The micronutrient metals Mn, Fe, Co, Ni and Zn are required for phytoplankton growth, and their availability influences ocean productivity and biogeochemistry. Here we report the first direct measurements of these metals in phytoplankton and protozoa from the equatorial Pacific Ocean. Cells representing 4 functional groups (diatoms, autotrophic flagellates, heterotrophic flagellates and autotrophic picoplankton) were collected from the surface mixed layer using trace-metal clean techniques during transects across the equator at 110 degrees W and along the equator between 110 degrees W and 140 degrees W. Metal quotas were determined for individual cells with synchrotron x-ray fluorescence microscopy, and cellular stoichiometries were calculated relative to measured P and S. as well as to C calculated from biovolume. Bulk particulate (> 3 mu m) metal concentrations were also determined at 3 stations using inductively coupled plasma mass spectrometry for comparison to single-cell stoichiometries. Phosphorus-normalized Mn, Fe, Ni and Zn ratios were significantly higher in diatoms than other cell types, while Co stoichiometries were highest in autotrophic flagellates. The magnitude of these effects ranged from approximately 2-fold for Mn in diatoms and autotrophic flagellates to nearly an order of magnitude for Fe in diatoms and picoplankton. Variations in S-normalized metal stoichiometries were also significant but of lower magnitude (1.4 to 6-fold). Cobalt and Mn quotas were 1.6 and 3-fold higher in autotrophic than heterotrophic flagellates. Autotrophic picoplankton were relatively enriched in Ni but depleted in Zn, matching expectations based on known uses of these metals in prokaryotes and eukaryotes. Significant spatial variability in metal stoichiometries was also observed. At two stations deviations in Fe stoichiometries reflected features in the dissolved Fe distribution. At these same stations, high Ni stoichiometries in autotrophic flagellates were correlated with elevated ammonium and depressed nitrate concentrations. The spatial effects may have resulted from the passage of tropical instability waves along the equator. Comparison of bulk and single-cell results show similar Mn:P ratios at 2 of 3 stations, but Fe:P and Ni:P were systematically higher in bulk material and Co:P was lower. These results suggest an overrepresentation of diatoms or diatom-based detritus in the bulk fraction. Taken together, the analyses present a generalized stoichiometry of Fe approximate to Zn > Mn approximate to Ni > Co in the plankton. Diatom Fe quotas exceeded minimum subsistence levels, characteristic of cells growing actively on oxidized N sources. This study demonstrates the substantial biogeochemical insight that can be gained from studies of metal quotas in individual functional groups. (C) 2010 Elsevier Ltd. All rights reserved.