To examine the pathways that form Mn(III) and Mn(IV) in the Mn(II)-oxidizing bacterial strains Pseudomonas putida GB-1 and MnB1, and to test whether the siderophore pyoverdine (PVD) inhibits Mn(IV)O2 formation, cultures were subjected to various protocols at known concentrations of iron and PVD. Depending on growth conditions, P. putida produced one of two oxidized Mn species - either soluble PVD-Mn(III) complex or insoluble Mn(IV)O2 minerals - but not both simultaneously. PVD-Mn(III) was present, and MnO2 precipitation was inhibited, both in iron-limited cultures that had synthesized 26-50 μM PVD and in iron-replete (non-PVD-producing) cultures that were supplemented with 10-550 μM purified PVD. PVD-Mn(III) arose by predominantly ligand-mediated air oxidation of Mn(II) in the presence of PVD, based on the following evidence: (a) yields and rates of this reaction were similar in sterile media and in cultures, and (b) GB-1 mutants deficient in enzymatic Mn oxidation produced PVD-Mn(III) as efficiently as wild type. Only wild type, however, could degrade PVD-Mn(III), a process linked to the production of both MnO2 and an altered PVD with absorbance and fluorescence spectra markedly different from those of either PVD or PVD-Mn(III). Two conditions, the presence of bioavailable iron and the absence of PVD at concentrations exceeding those of Mn, both had to be satisfied for MnO2 to appear. These results suggest that P. putida cultures produce soluble Mn(III) or MnO2 by different and mutually inhibitory pathways: enzymatic catalysis yielding MnO2 under iron sufficiency or PVD-promoted oxidation yielding PVD-Mn(III) under iron limitation. Since PVD-producing Pseudomonas species are environmentally prevalent Mn oxidizers, these data predict influences of iron (via PVD-Mn(III) versus MnO2) on the global oxidation/reduction cycling of various pollutants, recalcitrant organic matter, and elements such as C, S, N, Cr, U, and Mn.
ASJC Scopus subject areas
- Geochemistry and Petrology