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Variation of iron redox kinetics and its relation with molecular composition of standard humic substances at circumneutral pH.

ABSTRACT: Oxidation and reduction kinetics of iron (Fe) and proportion of steady-state Fe(II) concentration relative to total dissolved Fe (steady-state Fe(II) fraction) were investigated in the presence of various types of standard humic substances (HS) with particular emphasis on the photochemical and thermal reduction of Fe(III) and oxidation of Fe(II) by dissolved oxygen (O2) and hydrogen peroxide (H2O2) at circumneutral pH (pH 7-8). Rates of Fe(III) reduction were spectrophotometrically determined by a ferrozine method under the simulated sunlight and dark conditions, whereas rates of Fe(II) oxidation were examined in air-saturated solution using luminol chemiluminescence technique. The reduction and oxidation rate constants were determined to substantially vary depending on the type of HS. For example, the first-order rate constants varied by up to 10-fold for photochemical reduction and 7-fold for thermal reduction. The degree of variation in Fe(II) oxidation was larger for the H2O2-mediated reaction compared to the O2-mediated reaction (e.g., 15- and 3-fold changes for the former and latter reactions, respectively, at pH 8). The steady-state Fe(II) fraction under the simulated sunlight indicated that the Fe(II) fraction varies by up to 12-fold. The correlation analysis indicated that variation of Fe(II) oxidation is significantly associated with aliphatic content of HS, suggesting that Fe(II) complexation by aliphatic components accelerates Fe(II) oxidation. The reduction rate constant and steady-state Fe(II) fractions in the presence of sunlight had relatively strong positive relations with free radical content of HS, possibly due to the reductive property of radical semiquinone in HS. Overall, the findings in this study indicated that the Fe reduction and oxidation kinetics and resultant Fe(II) formation are substantially influenced by chemical properties of HS.

SUBMITTER: Lee YP

PROVIDER: S-EPMC5409151 | biostudies-literature | 2017

REPOSITORIES: biostudies-literature

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Variation of iron redox kinetics and its relation with molecular composition of standard humic substances at circumneutral pH.

Lee Ying Ping YP Fujii Manabu M Kikuchi Tetsuro T Terao Koumei K Yoshimura Chihiro C

PloS one 20170428 4

Oxidation and reduction kinetics of iron (Fe) and proportion of steady-state Fe(II) concentration relative to total dissolved Fe (steady-state Fe(II) fraction) were investigated in the presence of various types of standard humic substances (HS) with particular emphasis on the photochemical and thermal reduction of Fe(III) and oxidation of Fe(II) by dissolved oxygen (O2) and hydrogen peroxide (H2O2) at circumneutral pH (pH 7-8). Rates of Fe(III) reduction were spectrophotometrically determined by ...[more]

PMID: 28453538

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Project description:Fe(II)-oxidizing microorganisms and Fe(III)-reducing microorganisms, which drive the biogeochemical Fe cycle on the Earth's surface, are phylogenetically and ecologically diverse. However, no single organism capable of aerobic Fe(II) oxidation and anaerobic Fe(III) reduction at circumneutral pH have been reported so far. Here, we report a novel neutrophilic Fe(II)-oxidizing Rhodoferax bacterium, strain MIZ03, isolated from an iron-rich wetland in Japan. Our cultivation experiments demonstrate that MIZ03 represents a much more versatile metabolism for energy acquisition than previously recognized in the genus Rhodoferax. MIZ03 can grow chemolithoautotrophically at circumneutral pH by oxidation of Fe(II), H2, or thiosulfate as the sole electron donor under (micro)aerobic conditions (i.e., using O2 as the sole electron acceptor). In addition, it can reduce Fe(III) or nitrate under anaerobic conditions. Thus, this is the first report demonstrating the presence of a single bacterium capable of both Fe(II) oxidation and Fe(III) reduction at circumneutral pH. The observed physiology was consistent with its 4.9-Mbp complete genome encoding key genes for iron oxidation/reduction (foxEY and mtrABC), for nitrate reduction (narGHI), for thiosulfate oxidation (soxABCDXYZ), and for carbon fixation via the Calvin cycle. Our metagenomic survey suggests that there are more Rhodoferax members capable of Fe(II) oxidation and Fe(III) reduction. Such bifunctional Rhodoferax may have an ecological advantage in suboxic/anoxic environments at circumneutral pH by recycling of Fe as the electron donor and acceptor. IMPORTANCE The biogeochemical cycle of iron (Fe) via reactions of oxidation, reduction, precipitation, and dissolution is involved in the cycle of other ecologically relevant elements, such as C, N, P, S, As, Co, Ni, and Pb. The Fe cycle on the Earth's surface is driven by a variety of Fe(II)-oxidizing microorganisms and Fe(III)-reducing microorganisms. Here, we discovered a novel bacterium, Rhodoferax sp. strain MIZ03, capable of both Fe(II) oxidation and Fe(III) reduction at circumneutral pH, and we report its physiological characteristics and complete genome sequence. The unexpected capability of this bacterium provides novel insights into the Fe cycle in the environment. Moreover, this bacterium will help to better understand the molecular mechanisms of microbial Fe redox cycling as a model organism.

Dataset Information

Variation of iron redox kinetics and its relation with molecular composition of standard humic substances at circumneutral pH.

Publications

Variation of iron redox kinetics and its relation with molecular composition of standard humic substances at circumneutral pH.

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