Macronutrients and trace metals are incorporated into phytoplankton during growth and regenerated back into the water column when phytoplankton decay, a process that contributes to the distributions of dissolved trace metals and macronutrients in depth profiles. To study this, we incubated mixed Gulf of Mexico phytoplankton assemblages and monocultures of the diatom Pseudo-nitzschia dolorosa and the dinoflagellate Karenia brevis in the dark. Over 6 months, macronutrients (phosphate, silicic acid, nitrate + nitrite, nitrite, ammonium), chlorophyll-a, particulate organic carbon and nitrogen, and prokaryotes were monitored alongside dissolved manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), cadmium (Cd), and lead (Pb). Results were compared to depth profiles to evaluate the role of regeneration in trace metal cycling. In contrast to water-column distributions, silicic acid and phosphate were closely coupled in experiments containing diatoms, indicating a shared regeneration pathway. Nitrification and nitrifying prokaryotes were only observed near the end of a subset of the experiments. Of the trace metals, Cd was most tightly coupled with phosphate. Regeneration of Mn was followed by rapid drawdown, consistent with Mn-oxide formation. Iron (Fe), Cu, and Pb typically remained low until Mn was depleted, suggesting either scavenging to Mn-oxides or otherwise delayed regeneration of these elements. Cobalt (Co) and Ni were largely conservative, but behaved like nutrients in the experiment using more offshore water low in Cd and Zn. Although experimental conditions were limited in their representation of the water column, these incubations provide novel insight into macronutrient and trace metal regeneration in the oceans. At the base of the marine food web, phytoplankton require the macronutrients carbon (C), nitrogen (N), and phosphorous (P) to build cellular organic matter, and, for diatoms, silicon (Si) to build frustules (Redfield 1934; Brzezinski 1985). Phytoplankton also assimilate a suite of trace metals into their cells, including manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), cadmium (Cd), and lead (Pb) (

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Dissolved organic matter (DOM) is a distinct component of Earth’s hydrosphere and provides a link between the biogeochemical cycles of carbon, nutrients, and trace metals (TMs). Binding of TMs to DOM is thought to result in a TM pool with DOM-like biogeochemistry. Here, we determined elemental stoichiometries of aluminum, iron, copper, nickel, zinc, cobalt, and manganese associated with a fraction of the DOM pool isolated by solid-phase extraction at ambient pH (DOM SPE-amb ) from the Amazon plume. We found that the rank order of TM stoichiometry within the DOM SPE-amb fraction was underpinned by the chemical periodicity of the TM. Furthermore, the removal of the TM SPE-amb pool at low salinity was related to the chemical hardness of the TM ion. Thus, the biogeochemistry of TMs bound to the DOM SPE-amb component in the Amazon plume was determined by the chemical nature of the TM and not by that of the DOM SPE-amb .

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