RESUMEN
Iron (Fe) is the fourth most abundant element in the Earth's crust where ferrous Fe [Fe(II)] and ferric Fe [Fe(III)] can be used by archaea for energy conservation. In these archaea-Fe interactions, Fe(III) serves as terminal electron acceptor for anaerobic respiration by a variety of archaea, while Fe(II) serves as electron donor and/or energy sources for archaeal growth. As no Fe is incorporated into the archaeal cells, these redox reactions are referred to as dissimilatory Fe(III) reduction and Fe(II) oxidation, respectively. Dissimilatory Fe(III)-reducing archaea (FeRA) and Fe(II)-oxidizing archaea (FeOA) are widespread on Earth where they play crucial roles in biogeochemical cycling of not only Fe, but also carbon and sulfur. To reduce extracellular Fe(III) (oxyhydr)oxides, some FeRA transfer electrons directly to the Fe(III) (oxyhydr)oxides most likely via multiheme c-type cytochromes (c-Cyts). These multiheme c-Cyts may form the pathways similar to those found in bacteria for transferring electrons from the quinone/quinol pool in the cytoplasmic membrane to the Fe(III) (oxyhydr)oxides external to the archaeal cells. Use of multiheme c-Cyts for extracellular Fe(III) reduction by both Domains of Archaea and Bacteria emphasizes an ancient mechanism of extracellular electron transfer, which is well conserved. Other FeRA, however, reduce Fe(III) (oxyhydr)oxides indirectly via electron shuttles. Similarly, it is proposed that FeOA use pathways to oxidize Fe(II) on the surface of the cytoplasmic membrane and then to transfer the released electrons across the cytoplasmic membrane inward to the O2 and NAD+ in the cytoplasm. In this review, we focus on the latest understandings of the molecular mechanisms used by FeRA and FeOA for Fe(III) reduction and Fe(II) oxidation, respectively.
RESUMEN
A microbially facilitated approach was developed to degrade 2, 2', 4, 4'-tetrabrominated diphenyl ether (BDE-47). This approach consisted of biological production of Fe(II) and H2O2 by the dissimilatory metal-reducing bacterium Shewanella oneidensis MR-1 during the repetitive anoxic/oxic cycles and abiotic production of hydroxyl radical (HOâ) with the biologically produced Fe(II) and H2O2 via Fenton reaction. Under the condition tested, BDE-47 did not inhibit the growth of S. oneidensis MR-1. Water soluble Fe(III)-citrate and the solid minerals ferrihydrite [Fe(III)2O3â¢0.5H2O] and goethite [Fe(III)OOH] were tested in this study. Under anoxic condition, the amounts of Fe(II) produced by S. oneidensis MR-1 varied among the Fe(III)s tested, which decreased in the order of Fe(III)-citrate > ferrihydrite > goethite. Under subsequent oxic condition, H2O2 was produced via O2 reduction by S. oneidensis MR-1. The amounts of H2O2 detected also varied, which decreased in the order of the reactions with Fe(III)-citrate > goethite > ferrihydrite. S. oneidensis MR-1 maintained its ability to produce Fe(II) and H2O2 for up to seven anoxic/oxic cycles. At each end of anoxic/oxic cycle, HOâ was detected. The amount of HOâ produced decreased in the order of the reactions with ferrihydrite > goethite > Fe(III)-citrate, which was opposite to that of H2O2 detected. Compared to the controls without HOâ, the amounts of BDE-47 in the reactions with HOâ decreased. The more HOâ in the reaction, the less amount of BDE-47 detected. Furthermore, no BDE-47 degradation was observed when HOâ was scavenged or ferrihydrite was either omitted or replaced by nitrate. Finally, identification of degradation products, such as hydroxylated BDE-47 and trisBDE, dibromophenol and monobromophenol, suggested that OH-addition and Br-substitution by HOâ were the main mechanisms for degrading BDE-47. Collectively, all these results demonstrated for the first time that the Fenton reaction driven by S. oneidensis MR-1 degraded BDE-47 effectively.
