In situ measurements of micronutrient dynamics in open seawater show that complex dissociation rates may limit diatom growth

In this first in situ study of the dynamic availability of phytoplankton micronutrients, a SeaExplorer glider was combined with Diffusive Gradients in Thin Films and deployed in the Mediterranean Sea. On the basis of their labile metal complex pools, we discovered that Fe and Co can be potentially limiting and Cu co-limiting to diatom growth, contrary to the generally accepted view that phosphorus (phosphate) is the growth limiting element in the Mediterranean Sea. For flagellates and picoplankton, phosphorus remains the main element limiting growth. Our in situ measurements showed that organic complexes of Fe and Cu (>98% of total dissolved concentration), dissociate slower than inorganic complexes of Co, Cd and Ni (>99% of total dissolved concentration being free ions and inorganic complexes). This strengthens the potential growth limiting effect of Fe and Cu versus phosphate, which is present as a free ion and, thus, directly available for plankton.We acknowledge the skillful assistance of ALSEAMAR personnel for the preparation and the operation of SeaExplorer SEA010. We thank HERCULES Foundation (code: UABR/11/010) for funding of the High Resolution-ICPMS and SeaExplorer procurement sponsors DEME Group and Dr. G. Decadt. Support of this research from the Spanish Ministry MINECO (Project CTM2016-78798) is acknowledged