Abstract: The availability of iron exerts an important influence on the
biological productivity of marine systems. Dissolved iron(III) speciation in
seawater is dominated by complexation with strong organic ligands which mediate
the biological availability and geochemical cycling of iron. Some of these chelators
are thought to be derived from intracellular material released via grazing or
cell lysis. Tetrapyrroles, for example, derived from chlorophyll pigments and
cytochrome enzyme systems, have been hypothesized to contribute significantly
to the ligands that bind iron in seawater, and to participate actively in biological
iron recycling. We propose to test this hypothesis and evaluate the role of
tetrapyrroles as iron complexing agents in seawater by looking at two important
aspects of this problem: (1) the potential for chlorophyll degradation products
to bind iron in seawater; and (2) the biological availability of iron-porphyrins.
This work will employ a combination of techniques (radiotracers, electrochemistry,
chromatography, spectroscopy, mass spectrometry) to elucidate the iron-binding
characteristics of model tetrapyrroles, the structural nature of iron-tetrapyrrole
association, and the biological availability of iron-tetrapyrrole complexes.
It is anticipated that the results of this work will be immediately relevant
to researchers studying the marine biogeochemistry of iron, by providing information
about the chemical speciation and reactivity of dissolved iron in seawater.
In addition this research is likely to elucidate some under-studied aspects
of tetrapryrrole diagenesis, with perhaps significant implications for the use
of metalloporphyrins as geochemical biomarkers.