ferrihydrite and anthraquinone-2-6-disulfonate

The effects of electron shuttles (biochar/anthraquinone-2,6-disulphonate (AQDS)) on the process of the Shewanella oneidensis MR-1-induced As(V)-adsorbed ferrihydrite reduction were studied. The results showed that biochar could stimulate Fe(Ⅱ) and As release during the ferrihydrite bioreduction. After the addition of biochar, more dissolved organic matter (DOM) can be consumed as an electron donor to promote the metabolism of microorganisms by the fluorescence excitation-emission matrix spectra analysis. After microbial treatment, cyclic voltammetry (CV) showed that a unique cathodic peak and a distinct anodic peak appeared, which may represent the reduction of Fe(OH)

Topics: Adsorption; Anthraquinones; Arsenic; Charcoal; Ferric Compounds; Oxidation-Reduction; Shewanella

Iron oxides and humic substances (humics) have substantial effects on biochemical processes, such as methanogenesis, due to their redox reactivity and ubiquitous presence. This study aimed to investigate how methanogenesis is affected by the common occurrence of these compounds, which has not been considered to date. The experiment was conducted with anoxic paddy soil microcosms receiving a humics surrogate compound (anthraquinone-2,6-disulfonate, AQDS) and three iron(III) oxides (ferrihydrite, hematite, and magnetite) differing in crystallinity and conductivity. Ferrihydrite suppressed methanogenesis, whereas AQDS, hematite, and magnetite facilitated methanogenesis. CH4 production in co-occurring ferrihydrite + AQDS, hematite + AQDS, and magnetite + AQDS cultures was 4.1, 1.3, and 0.9 times greater than the corresponding cultures without AQDS, respectively. Syntrophic cooperation between Geobacter and Methanosarcina occurred in the methanogenesis-facilitated cultures. Experimental results suggested that the conductive characteristics of iron(III) oxides was an important factor determining the methanogenic response to the co-occurrence of iron(III) oxides and humics in anaerobic paddy soil. This work indicated that the type of iron(III) oxides may significantly affect carbon cycling under anoxic conditions in natural wetlands.

Topics: Anthraquinones; China; Ferric Compounds; Ferrosoferric Oxide; Geobacter; Humic Substances; Methanosarcina; Oryza; Oxidation-Reduction; Soil; Soil Microbiology

To determine whether biologically mediated Fe(III) reduction is possible under alkaline conditions in systems of relevance to geological disposal of radioactive wastes, a series of microcosm experiments was set up using hyperalkaline sediments (pH ~11.8) surrounding a legacy lime working site in Buxton, United Kingdom. The microcosms were incubated for 28 days and held at pH 10. There was clear evidence for anoxic microbial activity, with consumption of lactate (added as an electron donor) concomitant with the reduction of Fe(III) as ferrihydrite (added as the electron acceptor). The products of microbial Fe(III) reduction were black and magnetic, and a range of analyses, including X-ray diffraction, transmission electron microscopy, X-ray absorption spectroscopy, and X-ray magnetic circular dichroism confirmed the extensive formation of biomagnetite in this system. The addition of soluble exogenous and endogenous electron shuttles such as the humic analogue anthraquinone-2,6-disulfonate and riboflavin increased both the initial rate and the final extent of Fe(III) reduction in comparison to the nonamended experiments. In addition, a soluble humic acid (Aldrich) also increased both the rate and the extent of Fe(III) reduction. These results show that microbial Fe(III) reduction can occur in conditions relevant to a geological disposal facility containing cement-based wasteforms that has evolved into a high pH environment over prolonged periods of time (>100,000 years). The potential impact of such processes on the biogeochemistry of a geological disposal facility is discussed, including possible coupling to the redox conditions and solubility of key radionuclides.

Topics: Anaerobiosis; Anthraquinones; Bacteroidetes; Base Sequence; Circular Dichroism; Cloning, Molecular; England; Ferric Compounds; Ferrosoferric Oxide; Geologic Sediments; Hydrogen-Ion Concentration; Kinetics; Lactic Acid; Microscopy, Electron, Transmission; Molecular Sequence Data; Oxidation-Reduction; Radioactive Waste; Refuse Disposal; Riboflavin; RNA, Ribosomal, 16S; Sequence Analysis, DNA; X-Ray Absorption Spectroscopy; X-Ray Diffraction

Flavins are secreted by the dissimilatory iron-reducing bacterium Shewanella and can function as endogenous electron transfer mediators. To assess the potential importance of flavins in Fe(III) bioreduction, we investigated the redox reaction kinetics of reduced flavin mononucleotide (i.e., FMNH(2)) and reduced riboflavin (i.e., RBFH(2)) with ferrihydrite and lepidocrocite. The organic reductants rapidly reduced and dissolved ferrihydrite and lepidocrocite in the pH range 4-8. The rate constant k for 2-line ferrihydrite reductive dissolution by FMNH(2) was 87.5 ± 3.5 M(-1)·s(-1) at pH 7.0 in batch reactors, and k was similar for RBFH(2). For lepidocrocite, k was 500 ± 61 M(-1)·s(-1) for FMNH(2) and 236 ± 22 M(-1)·s(-1) for RBFH(2). The surface area normalized initial reaction rates (r(a)) were between 0.08 and 77 μmol·m(-2)·s(-1) for various conditions in stopped-flow experiments. Initial rates (r(o)) were first-order with respect to iron(III) oxide concentration, and r(a) increased with decreasing pH. Poorly crystalline 2-line ferrihydrite yielded the highest r(a), followed by more crystalline 6-line ferrihydrite and crystalline lepidocrocite. Compared to a previous whole-cell study with Shewanella oneidensis strain MR-1, our findings suggest that the reduction of electron transfer mediators by the Mtr (i.e., metal-reducing) pathway coupled to lactate oxidation is rate limiting, rather than heterogeneous electron transfer to the iron(III) oxide.

Topics: Anthraquinones; Ferric Compounds; Flavin Mononucleotide; Oxidation-Reduction; Riboflavin; Shewanella

The potential of microbial mediated iron plaque reduction, and associated arsenic (As) mobility were examined by iron reducing bacteria enriched from As contaminated paddy soil. To our knowledge, this is the first time to report the impact of microbial iron plaque reduction on As mobility. Iron reduction occurred during the inoculation of iron reducing enrichment culture in the treatments with iron plaque and ferrihydrite as the electron acceptors, respectively. The Fe(II) concentration with the treatment of anthraquinone-2, 6-disulfonic acid (AQDS) and iron reducing bacteria increased much faster than the control. Arsenic released from iron plaque with the iron reduction, and a significant correlation between Fe(II) and total As in culture was observed. However, compared with control, the increasing rate of As was inhibited by iron reducing bacteria especially in the presence of AQDS. In addition, the concentrations of As(III) and As(V) in abiotic treatments were higher than those in the biotic treatments at day 30. These results indicated that both microbial and chemical reductions of iron plaque caused As release from iron plaque to aqueous phase, however, microbial iron reduction induced the formation of more crystalline iron minerals, leading to As sequestration. In addition, the presence of AQDS in solution can accelerate the iron reduction, the As release from iron plaque and subsequently the As retention in the crystalline iron mineral. Thus, our results suggested that it is possible to remediate As contaminated soils by utilizing iron reducing bacteria and AQDS.

Topics: Anthraquinones; Arsenic; Bacteria; Biodegradation, Environmental; Ferric Compounds; Oryza; Plant Roots; Soil; Soil Microbiology; Soil Pollutants

Batch studies were conducted to explore differences in the transformation pathways of 2,4,6-trinitrotoluene (TNT) reduction by a Gram-positive fermenting bacterium (Cellulomonas sp. strain ES6) in the presence and absence of ferrihydrite and the electron shuttle anthraquinone-2,6-disulfonate (AQDS). Strain ES6 was capable of TNT and ferrihydrite reduction with increased reduction rates in the presence of AQDS. Hydroxylaminodinitrotoluenes, 2,4-dihydroxylamino-6-nitrotoluene (2,4-DHANT), and tetranitroazoxytoluenes were the major metabolites observed in ferrihydrite- and AQDS-free systems in the presence of pure cell cultures. Ferrihydrite enhanced the production of amino derivatives because of reactions with microbially produced surface-associated Fe(ll). The presence of AQDS in the absence of ferrihydrite promoted the fast initial formation of arylhydroxylamines such as 2,4-DHANT. However, unlike in pure cell systems, these arylhydroxylamines were transformed into several unidentified polar products. When both microbially reduced ferrihydrite and AQDS were present simultaneously, the reduction of TNT was more rapid and complete via pathways thatwould have been difficult to infer solely from single component studies. This study demonstrates the complexity of TNT degradation patterns in model systems where the interactions among bacteria, Fe minerals, and organic matter have a pronounced effect on the degradation pathway of TNT.

Topics: Anthraquinones; Biodegradation, Environmental; Cellulomonas; Culture Media; Environment; Fermentation; Ferric Compounds; Gram-Positive Bacteria; Hydroxylamines; Iron; Models, Chemical; Oxygen; Sucrose; Time Factors; Trinitrotoluene; Waste Disposal, Fluid; Water; Water Microbiology; Water Purification

Iron-reducing bacteria can transfer electrons to ferric iron oxides which are barely soluble at neutral pH, and electron-shuttling compounds or chelators are discussed to be involved in this process. Experiments using semipermeable membranes for separation of ferric iron-reducing bacteria from ferric iron oxides do not provide conclusive results in this respect. Here, we used ferrihydrite embedded in 1% agar to check for electron-shuttling compounds in pure and in enrichment cultures. Geobacter sulfurreducens reduced spatially distant ferrihydrite only in the presence of anthraquinone-2,6-disulfonate, a small molecule known to shuttle electrons between the bacterial cell and ferrihydrite. However, indications for the production and excretion of electron-shuttling compounds or chelators were found in ferrihydrite-containing agar dilution cultures that were inoculated with ferric iron-reducing enrichment cultures.

Topics: Anthraquinones; Cytochrome c Group; Deltaproteobacteria; Electron Transport; Ferric Compounds; Ferritins; Iron; Oxidation-Reduction

The quinol form (AHDS) of 9,10-anthraquinone-2,6-disulfonate (AQDS) was used as a titrant to determine bioavailability of Fe(III) in pure iron minerals and several soils. AHDS oxidation to AQDS was coupled to Fe(III) reduction to Fe(ll) in biological media consisting of trace salts and vitamins, providing estimates of bioavailability consistentwith the biogeochemical mechanisms and conditions that control Fe(III) availability to iron-reducing bacteria. Iron(III) oxide sources were synthetic oxides (amorphous and crystalline) and three soils separated into two size fractions each (0-500 and 500-1000 microm). This titration gave a measurement of the amount of Fe(III) available to dissimilatory iron-reducing bacteria and was compared to hydroxylamine reduction, oxalate extraction, and biological reduction by Shewanella alga BrY. The advantage of AHDS titration over existing chemical techniques is that it can be performed at normal soil pH and ionic strength, and it allows for distinction of iron(III) oxides rendered unavailable by sorption of Fe(II) or by other pH-dependent geochemical processes. This approach also allows distinction of Fe(III) present in micropores that is not directly available to bacteria but bioavailable in the presence of an electron shuttle capable of transporting electrons into the micropores.

Topics: Anthraquinones; Ferric Compounds; Ferritins; Iron Compounds; Minerals; Models, Chemical; Oxidation-Reduction; Shewanella; Soil