Molecular determination of marine iron ligands by mass spectrometry
Boiteau, Rene M.
MetadataShow full item record
Marine microbes produce a wide variety of metal binding organic ligands that regulate the solubility and availability of biologically important metals such as iron, copper, cobalt, and zinc. In marine environments where the availability of iron limits microbial growth and carbon fixation rates, the ability to access organically bound iron confers a competitive advantage. Thus, the compounds that microbes produced to acquire iron play an important role in biogeochemical carbon and metal cycling. However, the source, abundance, and identity of these compounds are poorly understood. To investigate these processes, sensitive methodologies were developed to gain a compound-specific window into marine iron speciation by combining trace metal clean sample collection and chromatography with inductively coupled plasma mass spectrometry (LCICPMS) and electrospray ionization mass spectrometry (LC-ESIMS). Coupled with isotope pattern assisted search algorithms, these tools provide a means to quantify and isolate specific iron binding ligands from seawater and marine cultures, identify them based on their mass and fragmentation spectra, and investigate their metal binding kinetics. Using these techniques, we investigated the distribution and diversity of marine iron binding ligands. In cultures, LC-ICPMS-ESIMS was used to identify new members of siderophore classes produced by marine cyanobacteria and heterotrophic bacteria, including synechobactins and marinobactins. Applications to natural seawater samples from the Pacific Ocean revealed a wide diversity of both known and novel metal compounds that are linked to specific nutrient regimes. Ferrioxamines B, E, and G were identified in productive coastal waters near California and Peru, in oligotrophic waters of the North and South Pacific Gyre, and in association with zooplankton grazers. Siderophore concentrations were up to five-fold higher in iron-deficient offshore waters (9pM) and were dominated by amphibactins, amphiphilic siderophores that partition into cell membranes. Furthermore, synechobactins were detected within nepheloid layers along the continental shelf. These siderophores reflect adaptations that impact dissolved iron bioavailability and thus have important consequences for marine ecosystem community structures and primary productivity. The ability to map and characterize these compounds has opened new opportunities to better understand mechanisms that link metals with the microbes that use them.
Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution February 2016
Suggested CitationThesis: Boiteau, Rene M., "Molecular determination of marine iron ligands by mass spectrometry", 2016-02, DOI:10.1575/1912/7837, https://hdl.handle.net/1912/7837
Showing items related by title, author, creator and subject.
Barth, John A. (Massachusetts Institute of Technology and Woods Hole Oceanographic Institution, 1987-10)A two-layer shallow water equation model is used to investigate the linear stability of a coastal upwelling front. The model features a surface front near a coastal boundary and bottom topography which is an arbitrary ...
Sanford, Lawrence P. (Massachusetts Institute of Technology and Woods Hole Oceanographic Institution, 1984-08)Intermittent, shoreward propagating packets of high frequency first mode internal waves are common on the continental shelf when the water column is stratified and may induce large fluctuations in near bottom velocity. ...
Nadakuditi, Rajesh Rao (Massachusetts Institute of Technology and Woods Hole Oceanographic Institution, 2007-02)The first part of the dissertation investigates the application of the theory of large random matrices to high-dimensional inference problems when the samples are drawn from a multivariate normal distribution. A longstanding ...