Increased metabolic requirements for manganese and copper in iron-limited marine diatoms

Productivity in large areas of the world's oceans is limited by low concentrations of dissolved iron in surface waters. Phytoplankton have adapted to persist in these environments by reducing their requirements for iron (Fe) in key metabolic pathways, in some cases by replacing Fe-containing catalysts with their iron-free functional equivalents. This thesis examines the requirements and biochemical roles for copper (Cu) and manganese (Mn) in Fe-limited centric marine diatoms. A major finding of my research is that diatoms have elevated requirements for Mn and Cu when grown in Fe-deficient seawater. Iron deficiency induces oxidative stress and increases the cellular concentrations of toxic oxygen radicals and damage products in Thalassiosira pseudonana. The increased Mn-requirement is used, in part, to activate Mn-containing isoforms of the antioxidant enzyme superoxide dismutase. Cultures co-limited by Fe and Mn exhibit high levels of oxidative stress and an inefficient detoxification pathway that further reduces cell growth. Diatoms isolated from the metal poor open ocean require more Cu to divide than related species from metal-rich coastal waters. This pattern is in stark contrast to all other known nutritive trace metals. One part of the diatom Cu requirement that is independent of provenance is for efficient Fe transport. The additional Cu requirement of oceanic species appears to be due to the constitutive expression of a Cu-containing electron transport protein, possibly plastocyanin. Coastal species, which have higher Fe-requirements for growth, retain the Fe-containing functional homologue cytochrome c6. By employing metals other than Fe within photosynthesis and antioxidant pathways, marine diatoms are able to increase their fitness in Fe-deficient environments. However, Mn and Cu also occur in low concentrations in the open ocean and thus may co-limit growth of natural populations of phytoplankton. Metal enrichment experiments