DOCSLIB.ORG

Biotransformation of Two-Line Silica-Ferrihydrite by a Dissimilatory Fe(III)-Reducing Bacterium: Formation of Carbonate Green Rust in the Presence of Phosphate

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Biotransformation of Two-Line Silica-Ferrihydrite by a Dissimilatory Fe(III)-Reducing Bacterium: Formation of Carbonate Green Rust in the Presence of Phosphate University of Nebraska - Lincoln DigitalCommons@University of Nebraska - Lincoln US Department of Energy Publications U.S. Department of Energy 2004 Biotransformation of two-line silica-ferrihydrite by a dissimilatory Fe(III)-reducing bacterium: Formation of carbonate green rust in the presence of phosphate Ravi K. Kukkadapu Pacific Northwest National Laboratory, [email protected] John M. Zachara Pacific Northwest National Laboratory James K. Fredrickson Pacific Northwest National Laboratory, [email protected] David W. Kennedy Pacific Northwest National Laboratory Follow this and additional works at: https://digitalcommons.unl.edu/usdoepub Part of the Bioresource and Agricultural Engineering Commons Kukkadapu, Ravi K.; Zachara, John M.; Fredrickson, James K.; and Kennedy, David W., "Biotransformation of two-line silica-ferrihydrite by a dissimilatory Fe(III)-reducing bacterium: Formation of carbonate green rust in the presence of phosphate" (2004). US Department of Energy Publications. 157. https://digitalcommons.unl.edu/usdoepub/157 This Article is brought to you for free and open access by the U.S. Department of Energy at DigitalCommons@University of Nebraska - Lincoln. It has been accepted for inclusion in US Department of Energy Publications by an authorized administrator of DigitalCommons@University of Nebraska - Lincoln. Geochimica et Cosmochimica Acta, Vol. 68, No. 13, pp. 2799–2814, 2004 Copyright © 2004 Elsevier Ltd Pergamon Printed in the USA. All rights reserved 0016-7037/04 $30.00 ϩ .00 doi:10.1016/j.gca.2003.12.024 Biotransformation of two-line silica-ferrihydrite by a dissimilatory Fe(III)-reducing bacterium: Formation of carbonate green rust in the presence of phosphate RAVI K. KUKKADAPU,* JOHN M. ZACHARA,JAMES K. FREDRICKSON, and DAVID W. KENNEDY Pacific Northwest National Laboratory, Richland, WA 99352, USA (Received November 1, 2002; accepted in revised form December 22, 2003) Abstract—The reductive biotransformation of two Si-ferrihydrite coprecipitates (1 and 5 mole % Si) by Shewanella putrefaciens, strain CN32, was investigated in 1,4-piperazinediethanesulfonic acid-buffered media (pH ϳ7) with lactate as the electron donor. Anthraquinone-2,6-disulfonate, an electron shuttle, was present in the 3Ϫ media. Experiments were performed without and with PO4 (P) (1 to 20 mmol/L) in media containing 50 mmol/L 4Ϫ Fe. Our objectives were to define the combined effects of SiO4 (Si) and P on the bioreducibility and biominer- alization of ferrihydrites under anoxic conditions. Iron reduction was measured as a function of time, solids were characterized by powder X-ray diffraction and Mo¨ssbauer spectroscopy, and aqueous solutions were analyzed for Si, P, ClϪ and inorganic carbon. Both of the ferrihydrites were rapidly reduced regardless of the Si and P content. Si concentration had no effect on the reduction rate or mineralization products. Magnetite was formed in the 2Ϫ II III xϩ 2Ϫ absence of P whereas carbonate green rust GR(CO3 ) ([Fe (6Ϫx)Fe x(OH)12] (CO3 )0.5x · yH2O) and vivianite 2Ϫ [Fe3(PO4)2 ·8H2O], were formed when P was present. GR(CO3 ) dominated as a mineral product in samples with Ͻ 2Ϫ 4 mmol/L P. The Fe(II)/Fe(III) ratio of GR(CO3 ) varied with P concentration; the ratio was 2 in 1 mmol/L P and approached 1 with 4- and 10 mmol/L P. Green rust appeared to form by solid-state transformation of ferrihydrite. Media P and Si concentration dictated the mechanism of transformation. In the 1 mole % Si coprecipitate with 1 mmol/L P, an intermediate Fe(II)/Fe(III) phase with structural Fe(II) slowly transformed to GR with time. In contrast, when ferrihydrite contained more Si (5 mole %) and/or contained higher P (4 mmol/L), sorbed Fe(II) and residual ferrihydrite together transformed to GR. Despite similar chemistries, P was shown to have a profound effect on extent of ferrihydrite reduction and biotransformations while that of Si was minimal. Copyright © 2004 Elsevier Ltd 1. INTRODUCTION under specific conditions (Fredrickson et al., 1998). Fe(II) flux rate and magnitude at the ferrihydrite surface and the presence Green rusts (GRs) are mixed valence, layered Fe(II)/Fe(III)- of sorbed/coprecipitated ions are important factors influencing hydroxides that belong to the sjo¨grenite-pyroaurite mineral the nature of the biomineralization products (Zachara et al., class (Taylor, 1973). These compounds have an ideal compo- 2002). Medium composition and electron donor and acceptor sition of [FeII FeIII (OH) ]xϩ[(Ax/n)·yH O]xϪ, where Ax/n (6Ϫx) x 12 2 concentrations are also important. In a 1,4-piperazinediethane- is an n-valent interlayer anion (e.g., ClϪ,CO2Ϫ,PO3Ϫ,SO2Ϫ). 3 4 4 sulfonic acid (PIPES)-buffered medium with 4 mmol/L P (a They are found in hydromorphic soils and are potential con- ligand with strong affinity for ferrihydrite surfaces) and 0.1 taminant reductants, anion exchangers, and metal cation sor- mmol/L anthraquinone-2,6-disulfonate (AQDS) (an electron bents in anoxic soils and sediments (Hansen et al., 1996; Ϫ shuttle), a carbonate GR [GR(CO2 ] in association with vivi- Myneni et al., 1997; Erbs et al., 1999; Lee et al., 2000; Loyaux- 3 anite was the primary mineral product formed in an anoxic Lawniczak et al., 2000; Refait et al., 2000; Williams and suspension with S. putrefaciens (CN32) (Fredrickson et al., Scherer, 2001; Bond and Fendorf, 2003). Recently, a bluish- Ϫ 1998). A phosphate GR [GR(PO3 ], however, was identified as gray colored GR mineral termed fougerite with Fe(II)/Fe(III) of 4 a major product of the bioreduction of ferrihydrite by S. putre- ϳ1 was isolated from forest soils of Brittany (Trolard et al., ϩ faciens in similar medium (with and without dissolved Ni2 ) 1997). Various synthetic procedures have been developed for but without AQDS (Parmar et al., 2001). GR that are believed to mimic those operative in the environ- Although, GR has been observed as a product in the labo- ment including: i) the controlled oxidation of ferrous hydroxide Ϫ 2Ϫ 2Ϫ ratory transformation of Fe(III) oxides by iron reducing bacte- in the presence of Cl ,SO4 , and CO3 (Ge´nin et al., 1998), ϩ ria, the specific range of chemical and biologic conditions that and ii) the solid-state transformation of ferrihydrite by Fe2 (aq) promote GR formation has not been established. Two out of (Mann et al., 1989; Hansen et al., 1994). three reports of biogenic GR formation (Fredrickson et al., Dissimilatory Fe(III)-reducing bacteria (DIRB) catalyze the 1998; Parmar et al., 2001) observed that P was requisite for its reduction of Fe(III) to Fe(II) in anoxic soils, sediments, and genesis. However, the specific mechanistic role of P in promot- groundwater (Lovley and Phillips, 1986). A variety of biomin- ing GR formation is unknown. Under identical conditions, but eralization products result from the interaction of DIRB with poorly crystalline two-line ferrihydrite, including green rusts in the absence of P, magnetite is the predominant bacterial transformation product of ferrihydrite (Fredrickson et al., 1998). Magnetite is thermodynamically more stable than GR * Author to whom correspondence should be addressed, at Pacific (Ge´nin et al., 1998), but P apparently impedes magnetite for- Northwest National Laboratory, P.O. Box 999, MSIN K8-96, Richland, mation (Couling and Mann, 1985; Fredrickson et al., 1998). In WA 99352 ([email protected]). contrast, GR was found as a primary anoxic transformation 2799 2800 R. K. Kukkadapu et al. product of lepidocrocite by S. putrefaciens strain CIP in the dissolved in concentrated HCl and analyzed for Si and Fe by induc- absence of P (Ona-Nguema et al., 2002). This latter study used tively coupled plasma-mass spectroscopy (ICP-MS, Hewlett Packard ϩ a different buffer (bicarbonate), electron donor (formate), and 4500). The ICP-determined Si/(Si Fe) mole fractions of the two Si-ferrihydrites respectively were 0.013 and 0.048. These will be re- higher organism concentrations (10x) than the former studies. ferred to as 0.01- and 0.05-Si-ferrihydrites. Whether one of these factors or the organism itself was most influential in GR formation was not established. Lepidocrocite 2.2. Bacteria and Media is the primary oxidation product of GR (Karim, 1986), imply- Anoxic suspensions of S. putrefaciens strain CN32 were prepared ing structural or kinetic relationships between the two mineral and suspended in a 30 mmol/L PIPES buffered-medium (pH ϳ7) as phases. The only common requirement noted above in the reported previously (Fredrickson et al., 2001). Media components biogenesis of GR from ferrihydrite appears to be the presence included (in mmol/L): lactate, 27 (electron donor); AQDS, 0.09 (elec- of excess electron donor. tron shuttle); NH4Cl, 25.5; KCl, 1.2; CaCl20·8H2O, 0.7; and varying amounts of phosphate (NaH PO ), 0 or 1, 4, 10, and 20. The medium Natural ferrihydrites contain Si (up to 9 mole %), and sig- 2 4 composition was similar to our previous study (Fredrickson et al., nificant amounts of organic matter (Carlson and Schwertmann, 1998) where biogenic GR was observed, except that the current media 1981; Fox, 1989; Fortin et al., 1993; Tessier et al., 1996; Perret lacked trace minerals that included sulfate salts. Sulfate, a potential et al., 2000). Coreacted Si affects the recrystallization of ferri- anion for GR, was excluded to prevent sulfate-GR formation. hydrite to crystalline oxides such as goethite and hematite and Both 0.01- and 0.05-Si-ferrihydrites (ϳ50 mmol/L Fe), which were “aged” for 1 and 3 months, were incubated in the PIPES buffered- may influence its reductive transformation by DIRB. Silicate media (30 mmol/L) containing 2–4 ϫ 108 cells/mL. The headspace anions, like P, have a strong affinity for ferrihydrite (Carlson atmosphere of the tubes was O2-free N2.
Load more

Recommended publications
  • Products of Hexavalent Chromium Reduction by Green Rust Sodium Sulfate and Associated Reaction Mechanisms
    Article Products of Hexavalent Chromium Reduction by Green Rust Sodium Sulfate and Associated Reaction Mechanisms Andrew N. Thomas 1,*, Elisabeth Eiche 1, Jörg Göttlicher 2, Ralph Steininger 2, Liane G. Benning 3,4 , Helen M. Freeman 3,† , Knud Dideriksen 5 and Thomas Neumann 6 1 Institute for Applied Geosciences, Karlsruhe Institute of Technology, Adenauerring 20b, Building 50.40, 76135 Karlsruhe, Germany; [email protected] 2 Institute for Synchrotron Radiation, Karlsruhe Institute of Technology, Herman-von-Helmholtz Platz 1, 76344 Eggenstein-Leopoldshafen, Germany; [email protected] (J.G.); [email protected] (R.S.) 3 GFZ German Research Center for Geosciences, Telegrafenberg, 14473 Potsdam, Germany; [email protected] (L.G.B.); [email protected] (H.M.F.) 4 Department of Earth Sciences, Free University of Berlin, 12249 Berlin, Germany 5 Nano-Science Center, Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 Copenhagen, Denmark; [email protected] 6 Department of Applied Geosciences, Technical University of Berlin, Ernst-Reuter-Platz 1, 10587 Berlin, Germany; [email protected] * Correspondence: [email protected] † Current address: School of Chemical and Process Engineering, University of Leeds, Leeds LS29JT, UK. Received: 28 September 2018; Accepted: 25 October 2018; Published: 29 October 2018 Abstract: The efficacy of in vitro Cr(VI) reduction by green rust sulfate suggests that this mineral is potentially useful for remediation of Cr-contaminated groundwater. Previous investigations studied this reaction but did not sufficiently characterize the intermediates and end products at 2− chromate (CrO4 ) concentrations typical of contaminant plumes, hindering identification of the dominant reaction mechanisms under these conditions.
    [Show full text]
  • The Formation of Green Rust Induced by Tropical River Biofilm Components Frederic Jorand, Asfaw Zegeye, Jaafar Ghanbaja, Mustapha Abdelmoula
    The formation of green rust induced by tropical river biofilm components Frederic Jorand, Asfaw Zegeye, Jaafar Ghanbaja, Mustapha Abdelmoula To cite this version: Frederic Jorand, Asfaw Zegeye, Jaafar Ghanbaja, Mustapha Abdelmoula. The formation of green rust induced by tropical river biofilm components. Science of the Total Environment, Elsevier, 2011, 409 (13), pp.2586-2596. 10.1016/j.scitotenv.2011.03.030. hal-00721559 HAL Id: hal-00721559 https://hal.archives-ouvertes.fr/hal-00721559 Submitted on 27 Jul 2012 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. The formation of green rust induced by tropical river biofilm components Running title: Green rust from ferruginous biofilms 5 Frédéric Jorand, Asfaw Zegeye, Jaafar Ghanbaja, Mustapha Abdelmoula Accepted in Science of the Total Environment 10 IF JCR 2009 (ISI Web) = 2.905 Abstract 15 In the Sinnamary Estuary (French Guiana), a dense red biofilm grows on flooded surfaces. In order to characterize the iron oxides in this biofilm and to establish the nature of secondary minerals formed after anaerobic incubation, we conducted solid analysis and performed batch incubations. Elemental analysis indicated a major amount of iron as inorganic compartment along with organic matter.
    [Show full text]
  • Identification of Jarosite and Other Major Mineral Fe Phases in Acidic
    Revista Mexicana de Ciencias Geológicas ISSN: 1026-8774 ISSN: 2007-2902 [email protected] Universidad Nacional Autónoma de México México Identification of jarosite and other major mineral Fe phases in acidic environments affected by mining-metallurgy using X-ray Absorption Spectroscopy: With special emphasis on the August 2014 Cananea acid spill Escobar-Quiroz, Ingrid Nayeli; Villalobos-Peñalosa, Mario; Pi-Puig, Teresa; Martín Romero, Francisco; Aguilar-Carrillo de Albornoz, Javier Identification of jarosite and other major mineral Fe phases in acidic environments affected by mining-metallurgy using X-ray Absorption Spectroscopy: With special emphasis on the August 2014 Cananea acid spill Revista Mexicana de Ciencias Geológicas, vol. 36, no. 2, 2019 Universidad Nacional Autónoma de México, México Available in: http://www.redalyc.org/articulo.oa?id=57265251007 PDF generated from XML JATS4R by Redalyc Project academic non-profit, developed under the open access initiative Ingrid Nayeli Escobar-Quiroz, et al. Identification of jarosite and other major mineral Fe phases ... Articles Identification of jarosite and other major mineral Fe phases in acidic environments affected by mining-metallurgy using X-ray Absorption Spectroscopy: With special emphasis on the August 2014 Cananea acid spill Ingrid Nayeli Escobar-Quiroz 13* Redalyc: http://www.redalyc.org/articulo.oa?id=57265251007 Universidad Nacional Autónoma de México, México [email protected] Mario Villalobos-Peñalosa 1 Universidad Nacional Autónoma de México, México Teresa Pi-Puig 1 Universidad Nacional Autónoma de México, México Francisco Martín Romero 1 Universidad Nacional Autónoma de México, México Javier Aguilar-Carrillo de Albornoz 2 Universidad Autónoma de San Luis Potosí, México Received: 23 July 2018 Accepted: 14 March 2019 Abstract: e sulfuric acid spill into the Sonora river, enriched in iron and copper ions from the Buenavista del Cobre mine (Cananea), gave way to the formation of various solid iron (Fe) phases.
    [Show full text]
  • NICKEL INCORPORATION in Fe(II, III) HYDROXYSULFATE GREEN RUST: EFFECT on CRYSTAL LATTICE SPACING and OXIDATION PRODUCTS(1)
    NICKEL INCORPORATION IN Fe (II, III) HYDROXYSULFATE GREEN RUST: EFFECT... 1115 NICKEL INCORPORATION IN Fe(II, III) HYDROXYSULFATE GREEN RUST: EFFECT ON CRYSTAL LATTICE SPACING AND OXIDATION PRODUCTS(1) Lucia Helena Garófalo Chaves(2), Joan Elizabeth Curry(3), David Andrew Stone(4), Michael D. Carducci(5) & Jon Chorover(6) SUMMARY Ni(II)-Fe(II)-Fe(III) layered double hydroxides (LDH) or Ni-containing sulfate green rust (GR2) samples were prepared from Ni(II), Fe(II) and Fe(III) sulfate salts and analyzed with X ray diffraction. Nickel is readily incorporated in the GR2 structure and forms a solid solution between GR2 and a Ni(II)-Fe(III) LDH. There is a correlation between the unit cell a-value and the fraction of Ni(II) incorporated into the Ni(II)-GR2 structure. Since there is strong evidence that the divalent/trivalent cation ratio in GR2 is fixed at 2, it is possible in principle to determine the extent of divalent cation substitution for Fe(II) in GR2 from the unit cell a-value. Oxidation forms a mixture of minerals but the LDH structure is retained if at least 20 % of the divalent cations in the initial solution are Ni(II). It appears that Ni(II) is incorporated in a stable LDH structure. This may be important for two reasons, first for understanding the formation of LDHs, which are anion exchangers, in the natural environment. Secondly, this is important for understanding the fate of transition metals in the environment, particularly in the presence of reduced Fe compounds. Index terms: isomorphous substitution, layered double hydroxide, LDH, X ray diffraction (1) Received for publication in february 2008 and aproved in july 2009.
    [Show full text]
  • Green Rust: the Simple Organizing ‘Seed’ of All Life?
    life Review Green Rust: The Simple Organizing ‘Seed’ of All Life? Michael J. Russell Planetary Chemistry and Astrobiology, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA 91109-8099, USA; [email protected] Received: 6 June 2018; Accepted: 14 August 2018; Published: 27 August 2018 Abstract: Korenaga and coworkers presented evidence to suggest that the Earth’s mantle was dry and water filled the ocean to twice its present volume 4.3 billion years ago. Carbon dioxide was constantly exhaled during the mafic to ultramafic volcanic activity associated with magmatic plumes that produced the thick, dense, and relatively stable oceanic crust. In that setting, two distinct and major types of sub-marine hydrothermal vents were active: ~400 ◦C acidic springs, whose effluents bore vast quantities of iron into the ocean, and ~120 ◦C, highly alkaline, and reduced vents exhaling from the cooler, serpentinizing crust some distance from the heads of the plumes. When encountering the alkaline effluents, the iron from the plume head vents precipitated out, forming mounds likely surrounded by voluminous exhalative deposits similar to the banded iron formations known from the Archean. These mounds and the surrounding sediments, comprised micro or nano-crysts of the variable valence FeII/FeIII oxyhydroxide known as green rust. The precipitation of green rust, along with subsidiary iron sulfides and minor concentrations of nickel, cobalt, and molybdenum in the environment at the alkaline springs, may have established both the key bio-syntonic disequilibria and the means to properly make use of them—the elements needed to effect the essential inanimate-to-animate transitions that launched life.
    [Show full text]
  • Hydroxysulphate Green Rust Synthesized by Precipitation and Coprecipitation Revista Brasileira De Ciência Do Solo, Vol
    Revista Brasileira de Ciência do Solo ISSN: 0100-0683 [email protected] Sociedade Brasileira de Ciência do Solo Brasil Garófalo Chaves, Lucia Helena; Curry, Joan Elizabeth; Stone, David Andrew; Chorover, Jon Fate of nickel ion in (II-III) hydroxysulphate green rust synthesized by precipitation and coprecipitation Revista Brasileira de Ciência do Solo, vol. 31, núm. 4, agosto, 2007, pp. 813-818 Sociedade Brasileira de Ciência do Solo Viçosa, Brasil Available in: http://www.redalyc.org/articulo.oa?id=180214056021 How to cite Complete issue Scientific Information System More information about this article Network of Scientific Journals from Latin America, the Caribbean, Spain and Portugal Journal's homepage in redalyc.org Non-profit academic project, developed under the open access initiative FATE OF NICKEL ION IN (II-III) HYDROXYSULPHATE GREEN RUST SYNTHESIZED BY... 813 FATE OF NICKEL ION IN (II-III) HYDROXYSULPHATE GREEN RUST SYNTHESIZED BY PRECIPITATION AND COPRECIPITATION(1) Lucia Helena Garófalo Chaves(2), Joan Elizabeth Curry(3), David Andrew Stone(4) & Jon Chorover(5) SUMMARY In order to investigate the efficiency of sulfate green rust (GR2) to remove Ni from solution, GR2 samples were synthesized under controlled laboratory conditions. Some GR2 samples were synthesized from Fe(II) and Fe(III) sulfate salts by precipitation. Other samples were prepared by coprecipitation, of Ni(II), Fe(II) and Fe(III) sulfate salts, i.e., in the presence of Ni. In another sample, Ni(II) sulfate salt was added to pre-formed GR2. After an initial X-ray diffraction (XRD) characterization all samples were exposed to ambient air in order to understand the role of Ni in the transformation of the GR2 samples.
    [Show full text]
  • Removal of Arsenate and Arsenite in Equimolar Ferrous And
    Article Removal of Arsenate and Arsenite in Equimolar Ferrous and Ferric Sulfate Solutions through Mineral Coprecipitation: Formation of Sulfate Green Rust, Goethite, and Lepidocrocite Chunming Su * and Richard T. Wilkin Groundwater Characterization and Remediation Division, Center for Environmental Solutions and Emergency Response, Office of Research and Development, United States Environmental Protection Agency, 919 Kerr Research Drive, Ada, OK 74820, USA; [email protected] * Correspondence: [email protected] Received: 24 September 2020; Accepted: 14 November 2020; Published: 23 November 2020 Abstract: An improved understanding of in situ mineralization in the presence of dissolved arsenic and both ferrous and ferric iron is necessary because it is an important geochemical process in the fate and transformation of arsenic and iron in groundwater systems. This work aimed at evaluating mineral phases that could form and the related transformation of arsenic species during coprecipitation. We conducted batch tests to precipitate ferrous (133 mM) and ferric (133 mM) ions in sulfate (533 mM) solutions spiked with As (0–100 mM As(V) or As(III)) and titrated with solid NaOH (400 mM). Goethite and lepidocrocite were formed at 0.5–5 mM As(V) or As(III). Only lepidocrocite formed at 10 mM As(III). Only goethite formed in the absence of added As(V) or As(III). Iron (II, III) hydroxysulfate green rust (sulfate green rust or SGR) was formed at 50 mM As(III) at an equilibrium pH of 6.34. X-ray analysis indicated that amorphous solid products were formed at 10–100 mM As(V) or 100 mM As(III).
    [Show full text]
  • {Replace with the Title of Your Dissertation}
    Characterization and Formation of High-Chroma Features in Loamy Soils of Southern Minnesota A Dissertation SUBMITTED TO THE FACULTY OF UNIVERSITY OF MINNESOTA BY Douglas Wayne Pribyl IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY James C. Bell, Adviser December 2012 © Douglas Wayne Pribyl 2012 Acknowledgements Many people both inside and outside the University of Minnesota have helped make this dissertation possible. The Department of Soil, Water, and Climate has supported me in many ways not least of which was the office staff, who were always ready with a friendly greeting, and willing and able to solve any problem: Karen Mellem, Kari Jarcho, Jenny Brand, and Marjorie Bonse. I especially want to thank my adviser, Jay Bell, for his continuous enthusiasm and encouragement. Ed Nater, together with Jay Bell, is responsible for introducing me to soil genesis and enabling me to pursue the interest they created. The rest of my committee, Paul Bloom and Carrie Jennings, have provided inspiration and motivation. Terry Cooper and John Lamb imparted wisdom and confidence in ways that only the best teachers can. I am profoundly grateful to have been their teaching assistant. Parts of this work were carried out in the Characterization Facility, University of Minnesota, which receives partial support from NSF through the MRSEC program. A special thanks to the staff who trained, listened, suggested, and encouraged: Bob Hafner, Ozan Ugurlu, Jinping Dong, John Nelson, Alice Ressler, Maria Torija Juana, Fang Zhou, and Nicholas Seaton. My earliest microscopy imaging and analysis work was with Gib Ahlstrand at the Biological Imaging Center, now part of the University Imaging Centers at the University of Minnesota.
    [Show full text]
  • Effects of Fe(III) Oxide Mineralogy and Phosphate on Fe(II) Secondary Mineral Formation During Microbial Iron Reduction
    minerals Article Effects of Fe(III) Oxide Mineralogy and Phosphate on Fe(II) Secondary Mineral Formation during Microbial Iron Reduction Edward J. O’Loughlin 1,* , Maxim I. Boyanov 1,2 , Christopher A. Gorski 3,†, Michelle M. Scherer 3 and Kenneth M. Kemner 1 1 Biosciences Division, Argonne National Laboratory, Lemont, IL 60439-4843, USA; [email protected] (M.I.B.); [email protected] (K.M.K.) 2 Institute of Chemical Engineering, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria 3 Department of Civil and Environmental Engineering, University of Iowa, Iowa City, IA 52242-1527, USA; [email protected] (C.A.G.); [email protected] (M.M.S.) * Correspondence: [email protected]; Tel.: +1-630-252-9902 † Present address: Department of Civil and Environmental Engineering, The Pennsylvania State University, University Park, State College, PA 16802-7304, USA. Abstract: The bioreduction of Fe(III) oxides by dissimilatory iron-reducing bacteria may result in the formation of a suite of Fe(II)-bearing secondary minerals, including magnetite (a mixed Fe(II)/Fe(III) oxide), siderite (Fe(II) carbonate), vivianite (Fe(II) phosphate), chukanovite (ferrous hydroxy car- bonate), and green rusts (mixed Fe(II)/Fe(III) hydroxides). In an effort to better understand the factors controlling the formation of specific Fe(II)-bearing secondary minerals, we examined the effects of Fe(III) oxide mineralogy, phosphate concentration, and the availability of an electron shuttle (9,10-anthraquinone-2,6-disulfonate, AQDS) on the bioreduction of a series of Fe(III) oxides (akaganeite, feroxyhyte, ferric green rust, ferrihydrite, goethite, hematite, and lepidocrocite) by Shewanella putrefaciens CN32, and the resulting formation of secondary minerals, as determined by Citation: O’Loughlin, E.J.; Boyanov, X-ray diffraction, Mössbauer spectroscopy, and scanning electron microscopy.
    [Show full text]
  • Further Insights Into the Fe(Ii) Reduction of 2-Line Ferrihydrite: A
    Nanoscale Advances View Article Online PAPER View Journal | View Issue Further insights into the Fe(II) reduction of 2-line ferrihydrite: a semi in situ and in situ TEM study† Cite this: Nanoscale Adv., 2020, 2, 4938 Mario Alberto Gomez, ‡*ab Ruonan Jiang,a Miao Song,‡c Dongsheng Li, *c Alan Scott Lea, d Xu Ma,e Haibo Wang,a Xiuling Yin,e Shaofeng Wang e and Yongfeng Jiae The biotic or abiotic reduction of nano-crystalline 2-line ferrihydrite (2-line FH) into more thermodynamically stable phases such as lepidocrocite-LP, goethite-GT, magnetite-MG, and hematite- HT plays an important role in the geochemical cycling of elements and nutrients in aqueous systems. In our study, we employed the use of in situ liquid cell (LC) and semi in situ analysis in an environmental TEM to gain further insights at the micro/nano-scale into the reaction mechanisms by which Fe(II)(aq) catalyzes 2-line FH. We visually observed for the first time the following intermediate steps: (1) formation of round and wire-shaped precursor nano-particles arising only from Fe(II)(aq), (2) two distinct dissolution mechanisms for 2 line-FH (i.e. reduction of size and density as well as breakage through smaller nano- Creative Commons Attribution 3.0 Unported Licence. particles), (3) lack of complete dissolution of 2-line FH (i.e. “induction-period”), (4) an amorphous phase growth (“reactive-FH/labile Fe(III) phase”) on 2 line-FH, (5) deposition of amorphous nano-particles on the surface of 2 line-FH and (6) assemblage of elongated crystalline lamellae to form tabular LP crystals.
    [Show full text]
  • Oxidation Modes and Thermodynamics of Feii-III Oxyhydroxycarbonate Green Rust: Dissolution-Precipitation Versus In-Situ Deproton
    Oxidation modes and thermodynamics of FeII-III oxyhydroxycarbonate green rust: dissolution-precipitation versus in-situ deprotonation; about the fougerite mineral Christian Ruby, Mustapha Abdelmoula, Sebastien Naille, Aurélien Renard, Varsha Khare, Georges Ona-Nguema, Guillaume Morin, Jean Marie Robert Génin To cite this version: Christian Ruby, Mustapha Abdelmoula, Sebastien Naille, Aurélien Renard, Varsha Khare, et al.. Oxidation modes and thermodynamics of FeII-III oxyhydroxycarbonate green rust: dissolution- precipitation versus in-situ deprotonation; about the fougerite mineral. Geochimica et Cosmochimica Acta, Elsevier, 2009, 74, pp.953-966. 10.1016/j.gca.2009.10.030. hal-00522806 HAL Id: hal-00522806 https://hal.archives-ouvertes.fr/hal-00522806 Submitted on 1 Oct 2010 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Oxidation modes and thermodynamics of FeII-III oxyhydroxycarbonate green rust: dissolution-precipitation versus in-situ deprotonation; about the fougerite mineral a a a a Christian Ruby , Mustapha Abdelmoula , Sébastien Naille
    [Show full text]
  • Magnetite and Green Rust
    Magnetite and Green Rust: Synthesis, Properties, and Environmental Applications of Mixed-Valent Iron Minerals Muhammad Usman, J M Byrne, A Chaudhary, S Orsetti, Khalil Hanna, C Ruby, A Kappler, S B Haderlein To cite this version: Muhammad Usman, J M Byrne, A Chaudhary, S Orsetti, Khalil Hanna, et al.. Magnetite and Green Rust: Synthesis, Properties, and Environmental Applications of Mixed-Valent Iron Minerals. Chemical Reviews, American Chemical Society, 2018, 118 (7), pp.3251-3304. 10.1021/acs.chemrev.7b00224. hal-01771511 HAL Id: hal-01771511 https://hal-univ-rennes1.archives-ouvertes.fr/hal-01771511 Submitted on 29 May 2018 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Magnetite and green rust: synthesis, properties and environmental applications of mixed-valent iron minerals M. Usman1, 2*, J. M. Byrne3, A. Chaudhary1,4, S. Orsetti1, K. Hanna5, C. Ruby6, A. Kappler3, S. B. Haderlein1 1 Environmental Mineralogy, Center for Applied Geosciences, University of Tübingen, 72074 Tübingen, Germany 2 Institute of Soil and Environmental Sciences, University of Agriculture, Faisalabad– 38040, Pakistan 3 Geomicrobiology, Center for Applied Geosciences, University of Tübingen, 72074 Tübingen, Germany 4 Department of Environmental Science and Engineering, Government College University Faisalabad, Pakistan 5 Univ Rennes, École Nationale Supérieure de Chimie de Rennes, CNRS, ISCR – UMR6226, F-35000 Rennes, France 6 Laboratoire de Chimie Physique et Microbiologie pour l’Environnement, UMR 7564 CNRS-Université de Lorraine, 54600 Villers-Lès-Nancy, France * Corresponding author: M.
    [Show full text]