DOCSLIB.ORG

Magnetite and Green Rust

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text

Load more

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. Usman manuscript Research Fellow (Alexander von Humboldt-Foundation) Environmental Mineralogy, Center for Applied Geosciences, University of Tübingen Hölderlinstr. 12, 72074 Tübingen, Germany Email: [email protected] or: [email protected] Phone No.: +49 70 71 29 78 924 Fax: +49 70 71 29 50 59 Accepted 1 Abstract Mixed-valent iron [Fe(II)-Fe(III)] minerals such as magnetite and green rust have received a significant amount of attention over recent decades, especially in the environmental sciences. These mineral phases are intrinsic and essential parts of biogeochemical cycling of metals and organic carbon and play an important role regarding the mobility, toxicity, and redox transformation of organic and inorganic pollutants. The formation pathways, mineral properties, and applications of magnetite and green rust are currently active areas of research in geochemistry, environmental mineralogy, geomicrobiology, material sciences, environmental engineering, and environmental remediation. These aspects ultimately dictate the reactivity of magnetite and green rust in the environment, which has important consequences for the application of these mineral phases, for example in remediation strategies. In this review we discuss the properties, occurrence, formation by biotic as well as abiotic pathways, characterization techniques, and environmental applications of magnetite and green rust in the environment. The aim is to present a detailed overview of the key aspects related to these mineral phases which can be used as an important resource for researchers working in a diverse range of fields dealing with mixed- valent iron minerals. manuscript Accepted 2 Contents 1. Introduction 4 2. Properties of mixed-valent iron minerals 7 2.1. Structural properties 7 2.2. Fe(II): Fe(III) ratio 12 2.3. Redox Potential 15 2.4. Magnetic properties 18 2.5. Thermodynamic properties 22 3. Occurrence of mixed-valent iron minerals in the environment 23 3.1. Natural environments 23 3.2. Corrosion products in engineered systems 26 4. Synthesis of mixed-valent iron minerals 28 4.1. Abiotic synthesis of mixed-valent iron minerals 28 4.1.1. Co-precipitation of dissolved Fe(II) and Fe(III) species 28 4.1.2. Partial oxidation of hydroxylated dissolved Fe(II) and (Fe(II)aq, Fe(OH)2) mixture 31 4.1.3. Chemical or electrochemical oxidation of zero-valent iron 33 4.1.4. Interaction of Fe(II) with Fe(III) (oxyhydr)oxides 37 4.2. Synthesis of mixed-valent iron minerals by microbial activity 45 4.2.1. Synthesis by bacterial Fe(III) reduction 45 4.2.2. Synthesis of mixed-valent iron minerals by bacterial Fe(II) oxidation 50 4.2.3. Magnetotactic bacteria 55 5. Identification and quantification techniques 60 5.1. X–ray diffraction 60 5.2. Mössbauer spectroscopy 64 5.3. Vibrational spectroscopy manuscript70 5.4. Synchrotron X-ray absorption 73 5.5. Transmission electron microscopy and scanning electron microscopy 78 5.6. Magnetic measurements 81 6. Application of mixed-valent iron minerals for environmental remediation 86 6.1. Sorption of contaminants 86 6.1.1. Inorganic compounds 88 6.1.2. Organic compounds 91 6.2. Reductive transformation of inorganic and organic contaminants 99 6.3. Use of mixed-valent iron minerals to promote advanced oxidation processes 111 7. Conclusions and outlook 126 Acknowledgments 128 Biography 129 References 131 Table of content graphic 167 Accepted 3 1. Introduction Iron (Fe) is the fourth most abundant element in the earth crust with an average mass concentration of 5.6% and is the second most abundant metal after aluminum.1 Fe exists in almost all aquatic and terrestrial environments. Fe is commonly found to form together with O, and/or OH either oxides, hydroxides or oxide-hydroxides which are collectively referred to as ‘iron oxides’ in this review article. There are 16 known iron oxides (Table 1) having different crystal structure, chemical composition and, Fe valence state.2 Iron oxides are categorized into three different groups based on Fe oxidation state including: (i) ferric oxides bearing only trivalent Fe(III), including ferrihydrite, goethite, hematite, lepidocrocite etc., (ii) very rare ferrous oxides containing exclusively divalent Fe(II), with only examples of Fe(II)O and Fe(II)(OH)2, and (iii) mixed-valent iron oxides containing both Fe(III) and Fe(II) in their structure which include magnetite and green rust (GR). Iron predominantly exists as Fe(III) oxides especially near the surfacemanuscript of Earth’s crust due to the presence of oxygen. However, under appropriate redox conditions in aquatic or terrestrial environments, Fe(III) oxides can serve as electron acceptors for microbial respiration or react with Fe(II) or other reductants to form mixed-valent Fe minerals such as magnetite and GR which are the focus of this review. Magnetite [Fe(II)Fe(III)2O4], a black ferromagnetic mineral, is a member of the spinel group of minerals while GRs are layered double hydroxides.3 GRs appear in intense bluish green colors. AcceptedStructurally, GRs contain both Fe(II) and Fe(III) cations in brucite-like layers along with intercalated anions. Most common types of GRs are hydroxysulfate GR 2– 2– – [GR(SO4 )], hydroxycarbonate GR [GR(CO3 )], and hydroxychloride GR [GR(Cl )] 2– 2– according to the type of intercalated anions, i.e., sulfate (SO4 ), carbonate (CO3 ), or 4 chloride (Cl–), respectively. A detailed description of structural properties of both magnetite and GR is presented in the section 2 of this review. Table 1: Overview of iron oxides. Reproduced with permission from Ref. 2. Copyright 2003 Wiley-VCH Verlag GmbH & Co. KGaA. Oxide-hydroxides and hydroxides Oxides Goethite α-FeOOH Hematite α-Fe2O3 Lepidocrocite γ-FeOOH Magnetite Fe3O4 Akaganéite β-FeOOH Maghemite γ-Fe2O3 [Fe(II)Fe(III)2O4) Schwertmannite Fe16O16(OH)y(SO4)z•nH2O β-Fe2O3 δ-FeOOH -Fe2O3 Feroxyhyte δ'-FeOOH Wüstite FeO High pressure FeOOH Ferrihydrite Fe5HO8• 4H2O Bernalite Fe(OH)3 Fe(OH)2 – – – 2– Green rusts Fe(III)xFe(II)y (OH)3x+2y–z(A )z ; A = Cl ; 1/2 SO4 Mixed-valent Fe minerals are amongst the most reactive iron compounds due to their role in biogeochemical cycling of trace elements,manuscript their ability to affect the mobility, redox transformation, and toxicity of various organic and inorganic pollutants, and their use in various environmental remediation strategies. A large amount of research concerning mixed-valent iron oxides has been carried out in recent decades, but despite the immense amount of collected research data, no comprehensive review of this topic has been published. Our review article is intended to compile the research data related to all aspects of mixed-valent Fe minerals (magnetite and GR) including their characteristics, presence, formation, and role in the environment. AcceptedOnly narrow aspects of this wide research field were reviewed so far. For example, a very recent review article by Su C.4 describes the environmental applications of engineered magnetite nanoparticles and its hybrid composites. Munoz et al.,5 in 2015, reviewed various methods to form magnetite-based catalysts followed by their 5 efficiency to improve Fenton oxidation for treatment of industrial wastewater. In 2013, Tang et al.6 presented a comprehensive review of various factors to be considered for sustainable environmental application of magnetic nano-materials like magnetite, maghemite, and zero-valent iron (Fe0). Another review article in 2012 discussed the catalytic role of various
Recommended publications
  • Coulsonite Fev2o4—A Rare Vanadium Spinel Group Mineral in Metamorphosed Massive Sulfide Ores of the Kola Region, Russia

    Coulsonite Fev2o4—A Rare Vanadium Spinel Group Mineral in Metamorphosed Massive Sulfide Ores of the Kola Region, Russia

    minerals Article Coulsonite FeV2O4—A Rare Vanadium Spinel Group Mineral in Metamorphosed Massive Sulfide Ores of the Kola Region, Russia Alena A. Kompanchenko Geological Institute of the Federal Research Centre “Kola Science Centre of the Russian Academy of Sciences”, 14 Fersman Street, 184209 Apatity, Russia; [email protected]; Tel.: +7-921-048-8782 Received: 24 August 2020; Accepted: 21 September 2020; Published: 24 September 2020 Abstract: This work presents new data on a rare vanadium spinel group mineral, i.e., coulsonite FeV2O4 established in massive sulfide ores of the Bragino occurrence in the Kola region, Russia. Coulsonite in massive sulfide ores of the Bragino occurrence is one of the most common vanadium minerals. Three varieties of coulsonite were established based on its chemical composition, some physical properties, and mineral association: coulsonite-I, coulsonite-II, and coulsonite-III. Coulsonite-I forms octahedral crystal clusters of up to 500 µm, and has a uniformly high content of 2 Cr2O3 (20–30 wt.%), ZnO (up to 4.5 wt.%), and MnO (2.8 wt.%), high microhardness (743 kg/mm ) and coefficient of reflection. Coulsonite-II was found in relics of quartz–albite veins in association with other vanadium minerals. Its features are a thin tabular shape and enrichment in TiO2 of up to 18 wt.%. Coulsonite-III is the most common variety in massive sulfide ores of the Bragino occurrence. Coulsonite-III forms octahedral crystals of up to 150 µm, crystal clusters, and intergrowths with V-bearing ilmenite, W-V-bearing rutile, Sc-V-bearing senaite, etc. Chemical composition of coulsonite-III is characterized by wide variation of the major compounds—Fe, V, Cr.
  • Chromite Crystal Structure and Chemistry Applied As an Exploration Tool

    Chromite Crystal Structure and Chemistry Applied As an Exploration Tool

    Western University Scholarship@Western Electronic Thesis and Dissertation Repository February 2015 Chromite Crystal Structure and Chemistry applied as an Exploration Tool Patrick H.M. Shepherd The University of Western Ontario Supervisor Dr. Roberta L. Flemming The University of Western Ontario Graduate Program in Geology A thesis submitted in partial fulfillment of the equirr ements for the degree in Master of Science © Patrick H.M. Shepherd 2015 Follow this and additional works at: https://ir.lib.uwo.ca/etd Part of the Geology Commons Recommended Citation Shepherd, Patrick H.M., "Chromite Crystal Structure and Chemistry applied as an Exploration Tool" (2015). Electronic Thesis and Dissertation Repository. 2685. https://ir.lib.uwo.ca/etd/2685 This Dissertation/Thesis is brought to you for free and open access by Scholarship@Western. It has been accepted for inclusion in Electronic Thesis and Dissertation Repository by an authorized administrator of Scholarship@Western. For more information, please contact [email protected]. Western University Scholarship@Western University of Western Ontario - Electronic Thesis and Dissertation Repository Chromite Crystal Structure and Chemistry Applied as an Exploration Tool Patrick H.M. Shepherd Supervisor Roberta Flemming The University of Western Ontario Follow this and additional works at: http://ir.lib.uwo.ca/etd Part of the Geology Commons This Thesis is brought to you for free and open access by Scholarship@Western. It has been accepted for inclusion in University of Western Ontario - Electronic Thesis and Dissertation Repository by an authorized administrator of Scholarship@Western. For more information, please contact [email protected]. Chromite Crystal Structure and Chemistry Applied as an Exploration Tool (Thesis format: Integrated Article) by Patrick H.M.
  • Products of Hexavalent Chromium Reduction by Green Rust Sodium Sulfate and Associated Reaction Mechanisms

    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.
  • Reduction of Ferric Green Rust by Shewanella Putrefaciens F

    Reduction of Ferric Green Rust by Shewanella Putrefaciens F

    Reduction of ferric green rust by Shewanella putrefaciens F. Jorand, A. Zegeye, F. Landry, C. Ruby To cite this version: F. Jorand, A. Zegeye, F. Landry, C. Ruby. Reduction of ferric green rust by Shewanella putrefaciens. Letters in Applied Microbiology, Wiley, 2007, 45 (5), pp.515-521. 10.1111/j.1472-765X.2007.02225.x. hal-03210484 HAL Id: hal-03210484 https://hal.archives-ouvertes.fr/hal-03210484 Submitted on 28 Apr 2021 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. Distributed under a Creative Commons Attribution| 4.0 International License Letters in Applied Microbiology ISSN 0266-8254 ORIGINAL ARTICLE Reduction of ferric green rust by Shewanella putrefaciens F. Jorand, A. Zegeye, F. Landry and C. Ruby Laboratoire de Chimie Physique et Microbiologie pour l’Environnement (LCPME), UMR 7564 CNRS-UHP, rue de Vandœuvre, Villers-le` s-Nancy, France Keywords Abstract biomineralization, green rust, iron reduction, Shewanella. Aims: To reduce carbonated ferric green rust (GR*) using an iron respiring bacterium and obtain its reduced homologue, the mixed FeII–FeIII carbonated Correspondence green rust (GR). Fre´ de´ ric Jorand, Laboratoire de Chimie Methods and Results: The GR* was chemically synthesized by oxidation of the Physique et Microbiologie pour GR and was incubated with Shewanella putrefaciens cells at a defined [FeIII] ⁄ l’Environnement (LCPME), UMR 7564 [cell] ratio.
  • Phase Transition of Electrooxidized Fe3o4 to Γ and Α-Fe2o3 Nanoparticles Using Sintering Treatment I

    Phase Transition of Electrooxidized Fe3o4 to Γ and Α-Fe2o3 Nanoparticles Using Sintering Treatment I

    Vol. 125 (2014) ACTA PHYSICA POLONICA A No. 5 Phase Transition of Electrooxidized Fe3O4 to γ and α-Fe2O3 Nanoparticles Using Sintering Treatment I. Kazeminezhad∗ and S. Mosivand Physics Department, Faculty of Science, Shahid Chamran University, Ahvaz, Iran (Received June 4, 2013; in nal form January 1, 2014) In this work, electrosynthesis of Fe3O4 nanoparticles was carried out potentiostatically in an aqueous solution of C4H12NCl which acts as supporting electrolyte and electrostatic stabilizer. γ-Fe2O3 nanoparticles were synthesized by controlling oxidation of the electrooxidized Fe3O4 nanoparticles at dierent temperature. Finally the phase transition to α-Fe2O3 nanoparticles was performed at high temperatures using sintering treatment. The synthesized particles were characterized using X-ray diraction, Fourier transformation, infrared scanning electron microscopy with energy dispersive X-ray analysis, and vibrating sample magnetometry. Based on the X-ray diraction results, ◦ ◦ the transition from Fe3O4 to cubic and tetragonal γ-Fe2O3 was performed at 200 C and 650 C, respectively. Furthermore, phase transition from metastable γ-Fe2O3 to stable α-Fe2O3 with rhombohedral crystal structure was ◦ approved at 800 C. The existence of the stabilizer molecules at the surface of Fe3O4 nanoparticles was conrmed by Fourier transformation infrared spectroscopy. According to scanning electron microscopy images, the average particles size was observed around 50 nm for electrooxidized Fe3O4 and γ-Fe2O3 nanoparticles prepared at sintering temperature lower than 900 ◦C, however by raising sintering temperature above 900 ◦C the mean particles size increases. Energy dispersive X-ray point analysis revealed that the nanoparticles are almost pure and composed of Fe and O elements. According to the vibrating sample magnetometry results, saturation magnetization, coercivity eld, and remnant magnetization decrease by phase transition from Fe3O4 to Fe2O3.
  • Spinel Group Minerals in Metamorphosed Ultramafic Rocks from Río De Las Tunas Belt, Central Andes, Argentina

    Spinel Group Minerals in Metamorphosed Ultramafic Rocks from Río De Las Tunas Belt, Central Andes, Argentina

    Geologica Acta, Vol.11, Nº 2, June 2013, 133-148 DOI: 10.1344/105.000001836 Available online at www.geologica-acta.com Spinel group minerals in metamorphosed ultramafic rocks from Río de Las Tunas belt, Central Andes, Argentina 1 1 2 M.F. GARGIULO E.A. BJERG A. MOGESSIE 1 INGEOSUR (Universidad Nacional del Sur – CONICET) San Juan 670, B8000ICN Bahía Blanca, Argentina Gargiulo E-mail: [email protected]; [email protected] Bjerg E-mail: [email protected] 2 Institut für Erdwissenschaften, Bereich Mineralogie und Petrologie, Karl-Franzens Universität Graz Universitätsplatz 2, 8010 Graz, Austria E-mail: [email protected] ABS TRACT In the Río de Las Tunas belt, Central Andes of Argentina, spinel group minerals occur in metaperidotites and in reaction zones developed at the boundary between metaperidotite bodies and their country-rocks. They comprise two types: i) Reddish-brown crystals with compositional zonation characterized by a ferritchromite core surrounded by an inner rim of Cr-magnetite and an outer rim of almost pure magnetite. ii) Green crystals chemically homogeneous with spinel (s.s.) and/or pleonaste compositions. The mineral paragenesis Fo+Srp+Cln+Tr+Fe-Chr and Fo+Cln+Tr+Tlc±Ath+Fe-Chr observed in the samples indicate lower and middle grade amphibolite facies metamorphic conditions. Nonetheless, the paragenesis (green)Spl+En+Fo±Di indicates that granulite facies conditions were also reached at a few localities. Cr-magnetite and magnetite rims in zoned reddish-brown crystals and magnetite rims around green-spinel/pleonaste grains are attributed to a later serpentinization process during retrograde metamorphism.
  • Corrosion of Carbon Steel in Marine Environments: Role of the Corrosion Product Layer

    Corrosion of Carbon Steel in Marine Environments: Role of the Corrosion Product Layer

    corrosion and materials degradation Review Corrosion of Carbon Steel in Marine Environments: Role of the Corrosion Product Layer Philippe Refait 1,*, Anne-Marie Grolleau 2, Marc Jeannin 1, Celine Rémazeilles 1 and René Sabot 1 1 Laboratoire des Sciences de l’Ingénieur pour l’Environnement (LaSIE), UMR 7356 CNRS-La Rochelle Université, Av. Michel Crépeau, CEDEX 01, F-17042 La Rochelle, France; [email protected] (M.J.); [email protected] (C.R.); [email protected] (R.S.) 2 Naval Group Research, BP 440, CEDEX 50104 Cherbourg-Octeville, France; [email protected] * Correspondence: [email protected]; Tel.: +33-5-46-45-82-27 Received: 5 May 2020; Accepted: 30 May 2020; Published: 3 June 2020 Abstract: This article presents a synthesis of recent studies focused on the corrosion product layers forming on carbon steel in natural seawater and the link between the composition of these layers and the corrosion mechanisms. Additional new experimental results are also presented to enlighten some important points. First, the composition and stratification of the layers produced by uniform corrosion are described. A focus is made on the mechanism of formation of the sulfate green rust because this compound is the first solid phase to precipitate from the dissolved species produced by the corrosion of the steel surface. Secondly, localized corrosion processes are discussed. In any case, they involve galvanic couplings between anodic and cathodic zones of the metal surface and are often associated with heterogeneous corrosion product layers. The variations of the composition of these layers with the anodic/cathodic character of the underlying metal surface, and in particular the changes in magnetite content, are thoroughly described and analyzed to enlighten the self-sustaining ability of the process.
  • Characterization of Formation and Oxidation of Green Rust (Cl )

    Characterization of Formation and Oxidation of Green Rust (Cl )

    ISIJ International, Vol. 49 (2009), No. 11, pp. 1730–1735 (Characterization of Formation and Oxidation of Green Rust (Cl؊ Suspension Futoshi NAGATA, Katsuya INOUE, Kozo SHINODA and Shigeru SUZUKI Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2–1–1 Katahira, Aoba-ku, Sendai 980-8577 Japan. E-mail: [email protected] (Received on April 30, 2009; accepted on July 3, 2009) Green rust (GR) containing both ferrous (Fe(II)) and ferric (Fe(III)) ions is formed in an aqueous solution with a relatively low electrochemical potential. In this study, in order to understand the formation and oxida- tion of GR, a suspension of GR containing chloride ions (GR(ClϪ)) was synthesized and subsequently oxi- dized by injecting nitrogen gas containing oxygen under different conditions. X-ray diffraction (XRD) meas- urements were performed for identifying the solid particles formed under different conditions. The results show that the GR(ClϪ) suspension was formed from specific concentrations of hydroxyl, ferrous, and ferric ions. The pH values and oxidation-reduction potential (ORP) of the aqueous solution were measured during oxidation of the GR(ClϪ) suspension. It was observed that because of oxygen injection, GR(ClϪ) was trans- formed into iron oxides such as a-FeOOH, g-FeOOH, and Fe3O4. These iron oxide and oxyhydroxide species formed by oxidation were dependent on the oxidation conditions such as temperature. This sug- gested that conditions of aqueous solution are crucial for the transformation of GR(ClϪ) into different iron oxides and oxyhydroxides. KEY WORDS: oxidation; reduction; green rust; iron oxyhydroxide; copper; X-ray diffraction; X-ray absorption spectroscopy.
  • Surface Charge and Growth of Sulphate and Carbonate Green Rust in Aqueous Media

    Surface Charge and Growth of Sulphate and Carbonate Green Rust in Aqueous Media

    Available online at www.sciencedirect.com Geochimica et Cosmochimica Acta 108 (2013) 141–153 www.elsevier.com/locate/gca Surface charge and growth of sulphate and carbonate green rust in aqueous media Romain Guilbaud a,⇑,1, Maggie L. White b, Simon W. Poulton a,1 a School of Civil Engineering and Geosciences, Newcastle University, Newcastle Upon Tyne NE1 7RU, UK b School of Chemical Engineering and Advanced Materials, Newcastle University, Newcastle Upon Tyne NE1 7RU, UK Received 16 March 2012; accepted in revised form 16 January 2013; available online 8 February 2013 Abstract We report the first determination of the point of zero charge of sulphated and carbonated green rust particles. Green rust has been recognised as a prevalent mineral in environments such as hydromorphic soils, groundwaters and anoxic Fe(II)-rich water bodies, and the evolution of its net surface charge with pH has direct implications for the uptake of contaminants, met- als and nutrients in such settings. We find that the surface of both sulphated and carbonated green rust is positively charged at pH < 8.3, whereas it is negatively charged at pH > 8.3. Thus, alkaline settings will promote enhanced adsorption of metallic cations. However, the behaviour of ionic species surrounding green rust is more complicated than that predicted by simple pH-dependent adsorption, as our experiments suggest that green rust likely grows via dissolution–reprecipitation during Ost- wald-ripening. This implies that adsorbed species are potentially subject to repetitive steps of release into solution, re-adsorp- tion and co-precipitation during particle growth. The growth rate of green rust particles is highest within the first 50 min of aging, and appears to decrease towards an asymptote after 200 min, suggesting that particle growth controls on the uptake of dissolved species will be most important during the early steps of green rust growth.
  • 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

    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.
  • The Oxidation of Carbonate Green Rust Into Ferric Phases:Solid-State Reaction Or Transformation Via Solution

    The Oxidation of Carbonate Green Rust Into Ferric Phases:Solid-State Reaction Or Transformation Via Solution

    Geochimica et Cosmochimica Acta, Vol. 68, No. 17, pp. 3497–3507, 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.2004.02.019 The oxidation of carbonate green rust into ferric phases:solid-state reaction or transformation via solution 1, 2 1 LUDOVIC LEGRAND, *LEO´ MAZEROLLES, and ANNIE CHAUSSE´ 1Laboratoire Analyse et Environnement, UMR 8587, CEA-CNRS-Universite´ d’Evry Val d’Essonne, Rue du pe`re Jarland, F-91025 Evry France 2Centre d’Etudes de Chimie Me´tallurgique, CNRS, F-94407 Vitry sur Seine France (Received February 28, 2003; accepted in revised form February 18, 2004) 2Ϫ ϭ Abstract—The oxidation of carbonate green rust, GR(CO3 ), in NaHCO3 solutions at T 25°C has been 2Ϫ investigated through electrochemical techniques, FTIR, XRD, TEM and SEM. The used GR(CO3 ) samples were made of either suspended solid in solution or a thin electrochemically formed layer on the surface of an iron disc. Depending on experimental conditions, oxidation occurs, with or without major modifications of the 2Ϫ GR(CO3 ) structure, suggesting the existence of two pathways: solid-state oxidation (SSO) leading to a ferric oxyhydroxycarbonate as the end product, and a dissolution-oxidation-precipitation (DOP) mechanism leading to ferric oxihydroxides such as lepidocrocite, goethite, or ferrihydrite. A formula was proposed for this ferric III oxyhydroxycarbonate, Fe6 O(2ϩx)(OH)(12-2x)(H2O)x(CO3), assuming that the solid-state oxidation reaction is associated to a deprotonation of the water molecules within the interlayers, or of the hydroxyl groups in the Fe(O,H) octahedra layers.
  • Identification of Jarosite and Other Major Mineral Fe Phases in Acidic

    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.