DOCSLIB.ORG

Iron Hydroxides in Soils: a Review of Publications Yu

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Iron Hydroxides in Soils: a Review of Publications Yu ISSN 10642293, Eurasian Soil Science, 2010, Vol. 43, No. 11, pp. 1244–1254. © Pleiades Publishing, Ltd., 2010. Original Russian Text © Yu.N. Vodyanitskii, 2010, published in Pochvovedenie, 2010, No. 11, pp. 1341–1352. SOIL CHEMISTRY Iron Hydroxides in Soils: A Review of Publications Yu. N. Vodyanitskii Dokuchaev Soil Science Institute, Russian Academy of Agricultural Sciences, per. Pyzhevskii 7, Moscow, 119017 Russia Email: [email protected] Received December 15, 2008 Abstract—Iron hydroxides are subdivided into thermodynamically unstable (ferrihydrite, feroxyhyte, and lepidocrocite) and stable (goethite) minerals. Hydroxides are formed either from Fe3+ (as ferrihydrite) or Fe2+ (as feroxyhyte and lepidocrocite). The high amount of feroxyhyte in ferromanganic concretions is proved, which points to the leading role of variable redox conditions in the synthesis of hydroxides. The struc ture of iron hydroxides is stabilized by inorganic elements, i.e., ferrihydrite, by silicon; feroxyhyte, by man ganese; lepidocrocite, by phosphorus; and goethite, by aluminum. Ferrihydrite and feroxyhyte are formed with the participation of biota, whereas the abiotic formation of lepidocrocite and goethite is possible. The iron hydroxidogenesis is more pronounced in podzolic soils than in chernozems, and it is more pronounced in iron–manganic nodules than in the fine earth. Upon the dissolution of iron hydroxides, iron isotopes are fractioned with lightweight 54Fe atoms being dissolved more readily. Unstable hydroxides are transformed into stable (hydr)oxides, i.e., feroxyhyte is spontaneously converted to goethite, and ferrihydrite, to hematite or goethite. DOI: 10.1134/S1064229310110074 INTRODUCTION Ferrihydrite Oxides and hydroxides predominate among the Properties. The chemical formula of ferrihydrite nonsilicate iron compounds in soils [5, 11, 24]. Min remained uncertain for a long time. The chemical erals of other classes, i.e., carbonates, sulfides, and composition of mineral samples depends to a great extent on the size of the domains composing them, sulfates, are met much more rarely. Iron hydroxides which range from 2 to 6 nm. Anions on the particles' form a sequence of minerals differing in their thermo – surface are represented by ОН groups and Н2О mole dynamic stability; they are ferrihydrite Fe2О3 ⋅ ⋅ δ cules bound to them, which changes the O : OH : Н2О 2FеООН 2.5Н2О, feroxyhyte FеООН, lepidocrocite ratio in them depending on the particles' volume. This γFеООН, and goethite αFеООН. All hydroxides are is the reason for the discrepancy in the chemical for classified as thermodynamically unstable, except for mulas of the mineral suggested by different authors. goethite, which possesses the minimal free Gibbs Russell [51], who was the first to discover the struc energy. The unstable iron hydroxides bear important tural hydroxyl groups, suggested the following formula soil information. First, these recently formed minerals for ferrihydrite: Fe2О3 ⋅ 2FеООН ⋅ 2.5Н2О.Next, Egg attest to the current iron oxidogenesis. With time, fer leton and Fitzpatrick [29] revealed that the alteration oxyhyte may be spontaneously transformed into goet in the total composition of ferrihydrite samples does hite, and ferrihydrite may be converted either into not influence the composition of an elementary cell of hematite or goethite. Second, their presence testifies the mineral, which is close to the composition of the to the activity of heterotrophic oxidizing microbes in cells in polymorphic FeOOH modifications. The later the soil [2]. These microorganisms are active upon a investigations performed by Drits and coauthors [13, low concentration of iron in the solution and upon a 45] showed that the actual ferrihydrite represents a low concentration of organic acids [14]. The chemical heterogenic mixture of three components, i.e., the precipitation of iron accompanied by goethite and structurally ordered and defect ferrihydrites, as well as lepidocrocite formation proceeds without the partici ultradispersed hematite with the size of the coherent pation of microorganisms and upon a high enough scattering domains being about 2 nm. The finest activity of iron [8]. Sometimes, goethite and lepi hematite particles operate as seeds or nuclei for a new docrocite particles are formed biogenically. phase. This explains the possible solidphase transfor mation of ferrihydrite to hematite under natural con The objective of this work is to systematize the evi ditions. Dehydration, which develops in soils and dence concerning the structure; properties; and the weathering crusts upon the temperature rise and arid conditions of formation, dissolution, and distribution ization, is the condition for the rearrangement of the of iron hydroxides in soils. anion ferrihydrite package into a hematite package. 1244 IRON HYDROXIDES IN SOILS: A REVIEW OF PUBLICATIONS 1245 The value of the free energy of the ferrihydrite for Both anions and cations affect the ferrihydrite crys mation ΔG0 is equal to –695.8 kJ/mol. The standard tallization. The influence of anions is most compre redox potential of ferrihydrite is Ео = 1.06 V. The den hensively studied by the example of phosphates [33]. sity is equal to 3.96 g/cm3 [24, 56]. Crystals form The phosphate impact was estimated by the value of aggregates 100–300 nm in size. Ferrihydrite is well dis the P : Fe atomic ratio. With the growing P : Fe ratio, solved by acidic ammonium oxalate even in the dark. the degree of the ferrihydrite solubility by oxalate (i.e., All natural ferrihydrites produce an additional strip in the Feox : Fetot ratio) increases. That means that the the infrared spectra in the area of 1000–1100 cm–1 due ferrihydrite crystallization slows down even at a small to the Si–O bond. Fe–O–Fe bonds are partially share of phosphates in the system, i.e., upon the P : Fe destroyed in the hydroxide, and various Fe–O–Si bonds ratio <2%. The pH influence upon a low rate of phos are formed instead of them with Fe partially replacing Si phate was the same as in the absence of phosphate: the in a tetrahedral Si–ferrihydrite lattice [50]. growing pH increases the ferrihydrite crystallization The identification of ferrihydrite in soils with xray degree. diffractometry is based on the maximal reflection Ferrihydrite fixes cations of many heavy metals. (110) with d = 0.252–0.256 nm. However, this reflec This process attracts the attention of soil scientists tion interval coincides with the maximal reflection involved in soil conservation. The codeposition of iron (100) produced by feroxyhyte δFеООН [11]. As a and heavy metals is believed to be the most significant matter of fact, ferrihydrite was earlier studied in the mechanism favoring the removal of heavy metals from soils by xray diffractometry. As a result, the reflection the solution. This codeposition lowers the toxicity and with d = 0.252–0.256 nm was unambiguously assigned biological availability of the heavy metals in the soil. to ferrihydrite. The huge volume of Xray investiga Being codeposited with iron, Сd2+, Cu2+, Pb2+, and tions performed under the guidance of Schwertmann Zn2+ enter the xray amorphous particles of iron showed that this reflection was very often met in the hydroxides [46]. With time, the heavy metals are fixed diffraction patterns of clay soil fractions [24, 56]. This as a result of the transformation of low crystallized fact was interpreted as the wide spreading of ferrihy hydroxide to its well crystallized form. The participa drite in soils. However, now it appears invalid to treat tion of Cu2+ in the lattice of crystallized hydroxide is this reflection as sure evidence of ferrihydrite’s pres proved. At pH 7, the codeposited Cd and Pb become ence in soils. Consequently, transmitting electron less soluble after the ferrihydrite transformation into microscopy with electron microdiffraction permitting goethite. In this case, Cd enters the hydroxide lattice us to reliably distinguish ferrihydrite and feroxyhyte is and, therefore, is fixed more firmly than Pb upon the the best method of ferrihydrite identification in soils. hydroxide ageing. Upon applying this method, the adopted rules of elec Cations of heavy metals slow down the transforma tron microdiffraction should be followed, in particu tion of ferrihydrite at a high atomic ratio of Me : Fe. lar, the analysis of no less than 20–30 particles. The The codeposition with iron of such heavy metals as best results may be obtained from the analysis of the Cu, Co, or Mn brakes the ferrihydrite transformation hydroxide composition in iron–manganic concre into better crystallized phases. The effect of slowing tions, in which the amount of these minerals reaches down the transformation is presented by the following whole percents and seven tens of percents sometimes. succession: Cu ӷ Co ӷ Mn [46]. Formation. Ferrihydrite originates from the hydrol Transformations. Ferrihydrite is a predecessor of ysis of chloride and nitrate Fe(III) salts, and this dif other more stable iron (hydr)oxides, above all, hema fers it from other thermodynamically unstable iron tite and goethite. Numerous experiments were per hydroxides (lepidocrocite and feroxyhyte) that are formed concerning ferrihydrite crystallization in labo formed from Fe(II) salts. As a result of this genetic dif ratories. The origin of the final products is found to be ference, the prevalence of either ferrihydrite or controlled by such factors as the pH, the temperature, hydroxides produced from Fе(ОН)2 in soils may point and the quantity and composition of the foreign ions. to different redox and pH conditions in the period of The influence of the pH and temperature is rather their synthesis. well studied. At pH 6, ferrihydrite mainly produces Ferrihydrite is formed both upon the organic and hematite upon lacking protons, and it produces goet inorganic catalysis of Fe(II) oxidation. In the latter hite at pH 5. As was shown recently by Schwertmann case, the role of silicic acid in the hydrolytic polymer and coauthors [55], a temperature increase from 4° to ization of Fe(III) is important, as it prevents the for 25°С favors goethite formation from ferrihydrite.
Load more

Recommended publications
  • Xrd and Tem Studies on Nanophase Manganese
    Clays and Clay Minerals, Vol. 64, No. 5, 488–501, 2016. 1 1 2 2 3 XRD AND TEM STUDIES ON NANOPHASE MANGANESE OXIDES IN 3 4 FRESHWATER FERROMANGANESE NODULES FROM GREEN BAY, 4 5 5 6 LAKE MICHIGAN 6 7 7 8 8 S EUNGYEOL L EE AND H UIFANG X U* 9 9 NASA Astrobiology Institute, Department of Geoscience, University of Wisconsin Madison, Madison, 10 À 10 1215 West Dayton Street, A352 Weeks Hall, Wisconsin 53706 11 11 12 12 13 Abstract—Freshwater ferromanganese nodules (FFN) from Green Bay, Lake Michigan have been 13 14 investigated by X-ray powder diffraction (XRD), micro X-ray fluorescence (XRF), scanning electron 14 microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and scanning 15 transmission electron microscopy (STEM). The samples can be divided into three types: Mn-rich 15 16 nodules, Fe-Mn nodules, and Fe-rich nodules. The manganese-bearing phases are todorokite, birnessite, 16 17 and buserite. The iron-bearing phases are feroxyhyte, goethite, 2-line ferrihydrite, and proto-goethite 17 18 (intermediate phase between feroxyhyte and goethite). The XRD patterns from a nodule cross section 18 19 suggest the transformation of birnessite to todorokite. The TEM-EDS spectra show that todorokite is 19 associated with Ba, Co, Ni, and Zn; birnessite is associated with Ca and Na; and buserite is associated with 20 2+ +2 3+ 20 Ca. The todorokite has an average chemical formula of Ba0.28(Zn0.14Co0.05 21 2+ 4+ 3+ 3+ 3+ 2+ 21 Ni0.02)(Mn4.99Mn0.82Fe0.12Co0.05Ni0.02)O12·nH2O.
    [Show full text]
  • Sorptive Interaction of Oxyanions with Iron Oxides: a Review
    Pol. J. Environ. Stud. Vol. 22, No. 1 (2013), 7-24 Review Sorptive Interaction of Oxyanions with Iron Oxides: A Review Haleemat Iyabode Adegoke1*, Folahan Amoo Adekola1, Olalekan Siyanbola Fatoki2, Bhekumusa Jabulani Ximba2 1Department of Chemistry, University of Ilorin P.M.B. 1515, Ilorin, Nigeria 2Department of Chemistry, Faculty of Applied Sciences, Cape Peninsula University of Technology, P.O. Box 652, Cape Town, South Africa Received: 5 December 2011 Accepted: 24 July 2012 Abstract Iron oxides are a group of minerals composed of Fe together with O and/or OH. They have high points of zero charge, making them positively charged over most soil pH ranges. Iron oxides also have relatively high surface areas and a high density of surface functional groups for ligand exchange reactions. In recent time, many studies have been undertaken on the use of iron oxides to remove harmful oxyanions such as chromate, arsenate, phosphate, and vanadate, etc., from aqueous solutions and contaminated waters via surface adsorp- tion on the iron oxide surface structure. This review article provides an overview of synthesis methods, char- acterization, and sorption behaviours of different iron oxides with various oxyanions. The influence of ther- modynamic and kinetic parameters on the adsorption process is appraised. Keywords: oxyanions, iron oxides, adsorption, isotherm, points of zero charge Introduction Iron oxides have been used as catalysts in the chemical industry [9, 10], and a potential photoanode for possible Iron oxides are a group of minerals composed of iron electrochemical cells [11, 12]. In medical applications, and oxygen and/or hydroxide. They are widespread in nanoparticle magnetic and superparamagnetic iron oxides nature and are found in soils and rocks, lakes and rivers, on have been used for drug delivery in the treatment of cancer the seafloor, in air, and in organisms.
    [Show full text]
  • Mineralogy of Cobalt-Rich Ferromanganese Crusts from the Perth Abyssal Plain (E Indian Ocean)
    Article Mineralogy of Cobalt-Rich Ferromanganese Crusts from the Perth Abyssal Plain (E Indian Ocean) Łukasz Maciąg 1,*, Dominik Zawadzki 1, Gabriela A. Kozub-Budzyń 2, Adam Piestrzyński 2, Ryszard A. Kotliński 1 and Rafał J. Wróbel 3 1 Faculty of Geosciences, Institute of Marine and Coastal Sciences, University of Szczecin, Mickiewicza 16A, 70383 Szczecin, Poland; [email protected] (Ł.M); [email protected] (D.Z.); [email protected] (R.A.K.) 2 Faculty of Geology, Geophysics and Environmental Protection, Department of Economic Geology, AGH University of Science and Technology, Mickiewicza 30, 30059 Kraków, Poland; [email protected] (G.A.K.-B.); [email protected] (A.P.) 3 Faculty of Chemical Technology and Engineering, West Pomeranian University of Technology Szczecin, Pułaskiego 10, 70322 Szczecin, Poland; [email protected] * Correspondence: [email protected]; Tel.: +48-91-444-2371 Received: 26 December 2018; Accepted: 27 January 2019; Published: 29 January 2019 Abstract: Mineralogy of phosphatized and zeolitized hydrogenous cobalt-rich ferromanganese crusts from Dirck Hartog Ridge (DHR), the Perth Abyssal Plain (PAP), formed on an altered basaltic substrate, is described. Detail studies of crusts were conducted using optical transmitted light microscopy, X-ray Powder Diffraction (XRD) and Energy Dispersive X-ray Fluorescence (EDXRF), Differential Thermal Analysis (DTA) and Electron Probe Microanalysis (EPMA). The major Fe-Mn mineral phases that form DHR crusts are low-crystalline vernadite, asbolane and a feroxyhyte-ferrihydrite mixture. Accessory minerals are Ca-hydroxyapatite, zeolites (Na-phillipsite, chabazite, heulandite-clinoptilolite), glauconite and several clay minerals (Fe-smectite, nontronite, celadonite) are identified in the basalt-crust border zone.
    [Show full text]
  • Accumulation of Platinum Group Elements in Hydrogenous Fe–Mn Crust and Nodules from the Southern Atlantic Ocean
    minerals Article Accumulation of Platinum Group Elements in Hydrogenous Fe–Mn Crust and Nodules from the Southern Atlantic Ocean Evgeniya D. Berezhnaya 1,*, Alexander V. Dubinin 1, Maria N. Rimskaya-Korsakova 1 and Timur H. Safin 1,2 1 Shirshov Institute of Oceanology, Russian Academy of Sciences, 36, Nahimovskiy prt., 117997 Moscow, Russia; [email protected] (A.V.D.); [email protected] (M.N.R.-K.); timursafi[email protected] (T.H.S.) 2 Institute of Chemistry and Problems of Sustainable Development, D. Mendeleev University of Chemical Technology of Russia, 9, Miusskya Sq., 125047 Moscow, Russia * Correspondence: [email protected]; Tel.: +7-4991-245-949 Received: 27 May 2018; Accepted: 25 June 2018; Published: 28 June 2018 Abstract: Distribution of platinum group elements (Ru, Pd, Pt, and Ir) and gold in hydrogenous ferromanganese deposits from the southern part of the Atlantic Ocean has been studied. The presented samples were the surface and buried Fe–Mn hydrogenous nodules, biomorphous nodules containing predatory fish teeth in their nuclei, and crusts. Platinum content varied from 47 to 247 ng/g, Ru from 5 to 26 ng/g, Pd from 1.1 to 2.8 ng/g, Ir from 1.2 to 4.6 ng/g, and Au from less than 0.2 to 1.2 ng/g. In the studied Fe–Mn crusts and nodules, Pt, Ir, and Ru are significantly correlated with some redox-sensitive trace metals (Co, Ce, and Tl). Similar to cobalt and cerium behaviour, ruthenium, platinum, and iridium are scavenged from seawater by suspended ferromanganese oxyhydroxides. The most likely mechanism of Platinum Group Elements (PGE) accumulation can be sorption and oxidation on δ-MnO2 surfaces.
    [Show full text]
  • Helium and Argon Isotopes in the Fe-Mn Polymetallic Crusts and Nodules from the South China Sea: Constraints on Their Genetic Sources and Origins
    minerals Article Helium and Argon Isotopes in the Fe-Mn Polymetallic Crusts and Nodules from the South China Sea: Constraints on Their Genetic Sources and Origins Yao Guan 1 , Yingzhi Ren 2, Xiaoming Sun 1,2,3,*, Zhenglian Xiao 2 and Zhengxing Guo 2 1 School of Earth Sciences and Engineering, Sun Yat-sen University, Guangzhou 510275, China; [email protected] 2 School of Marine Sciences, Sun Yat-sen University, Guangzhou 510006, China; [email protected] (Y.R.); [email protected] (Z.X.); [email protected] (Z.G.) 3 Guangdong Provincial Key Laboratory of Marine Resources and Coastal Engineering, Guangzhou 510006, China * Correspondence: [email protected]; Tel./Fax: +86-20-84110968 Received: 17 August 2018; Accepted: 8 October 2018; Published: 22 October 2018 Abstract: In this study, the He and Ar isotope compositions were measured for the Fe-Mn polymetallic crusts and nodules from the South China Sea (SCS), using the high temperature bulk melting method and noble gases isotope mass spectrometry. The He and Ar of the SCS crusts/nodules exist mainly in the Fe-Mn mineral crystal lattice and terrigenous clastic mineral particles. The results show that 3 the He concentrations and R/RA values of the SCS crusts are generally higher than those of the SCS nodules, while 4He and 40Ar concentrations of the SCS crusts are lower than those of the SCS nodules. Comparison with the Pacific crusts and nodules, the SCS Fe-Mn crusts/nodules have 3 3 4 lower He concentrations and He/ He ratios (R/RA, 0.19 to 1.08) than those of the Pacific Fe-Mn crusts/nodules, while the 40Ar/36Ar ratios of the SCS samples are significantly higher than those of the Pacific counterparts.
    [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]
  • Study on Nanophase Iron Oxyhydroxides in Freshwater Ferromanganese Nodules from Green Bay, Lake Michigan, with Implications for the Adsorption of As and Heavy Metals
    American Mineralogist, Volume 101, pages 1986–1995, 2016 SPECIAL COLLECTION: NANOMINERALS AND MINERAL NANOPARTICLES Study on nanophase iron oxyhydroxides in freshwater ferromanganese nodules from Green Bay, Lake Michigan, with implications for the adsorption of As and heavy metals SEUNGYEOL LEE1, ZHIZHANG SHEN1, AND HUIFANG XU1,* 1NASA Astrobiology Institute, Department of Geoscience, University of Wisconsin-Madison, Madison, Wisconsin 53706, U.S.A. ABSTRACT Nanophase Fe-oxyhydroxides in freshwater ferromanganese nodules (FFN) from Green Bay, Lake Michigan, and adsorbed arsenate have been investigated by X-ray powder diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), Z-contrast imaging, and ab initio calculations using the density functional theory (DFT). The samples from northern Green Bay can be divided into two types: Fe-Mn nodules and Fe-rich nodules. The manganese-bearing phases are todorokite, birnessite, and buserite. The iron-bearing phases are feroxyhyte, nanophase goethite, two-line ferrihydrite, and nanophase FeOOH with guyanaite structure. Z-contrast images of the Fe-oxyhydroxides show ordered FeOOH nano-domains with guyanaite structure intergrown with nanophase goethite. The FeOOH nanophase is a precursor to the goethite. Henceforth, we will refer to it as “proto-goethite.” DFT calculations indicate that goethite is more stable than proto-goethite. Our results suggest that ordering between Fe and vacancies in octahedral sites result in the transforma- tion from feroxyhyte to goethite through a proto-goethite intermediate phase. Combining Z-contrast 3– images and TEM-EDS reveals that arsenate (AsO4 ) tetrahedra are preferentially adsorbed on the proto-goethite (001) surface via tridentate adsorption. Our study directly shows the atomic positions of Fe-oxyhydroxides with associated trace elements.
    [Show full text]
  • The Structure of Nano Sized Poorly-Crystalline Iron Oxy-Hydroxides
    Università degli Studi di Cagliari PhD Thesis DOTTORATO DI RICERCA Corso di Dottorato in Scienze e Tecnologie Chimiche Ciclo XXVII Settore scientifico disciplinare di afferenza CHIM/02 Matteo Sestu The structure of nano sized poorly-crystalline iron oxy-hydroxides Coordinatore Dottorato: Prof. Mariano Casu Relatore: Dott. Gabriele Navarra A.A. 2013 – 2014 The structure of nano sized poorly-crystalline iron oxy-hydroxides Matteo Sestu Dipartimento di Scienze Chimiche e Geologiche Universita' degli Studi di Cagliari A thesis for the degree of Doctor of Philosophy 03 13 2015 The structure of nano sized poorly-crystalline iron oxy-hydroxides |||{ Author: Matteo Sestu Supervisor: Gabriele Navarra Matteo Sestu gratefully acknowledges Sardinia Regional Government for the financial support of his PhD scholarship (P.O.R. Sardegna F.S.E. Operational Programme of the Regione Autonoma della Sardegna, European Social Fund 2007-2013 - Axis IV Human Resources, Objective l.3, Line of Activity l.3.1.) Ai miei genitori "Nature is a language, can't you read?" Ask, The Smiths Acknowledgements I would like to acknowledge • Gabriele Navarra, for our long fruitful scientific cohabitation • Maria, Danilo, Claudia and all the people that "went through" the Functional Materials Team • Erika, who shares with me the PhD experience • Anna, Gavin and Andrea for their precious scientific, and espe- cially human, contribution • The Elettra MCX and XAFS Teams • Alex, for being so kind. I hope that our collaboration will con- tinue in the future • All the colleagues of the Sala Dottorandi and all the colleagues that in these years shared lunches and laughs with me • Francesco, Bruno and all my colleagues in Kent.
    [Show full text]
  • Subsea Mineral Resources
    Subsea Mineral Resources U.S. GEOLOGICAL SURVEY BULLETIN 1689-A Chapter A Subsea Mineral Resources By V. E. McKELVEY US. GEOLOGICAL SURVEY BULLETIN 1689 MINERAL AND PETROLEUM RESOURCES OF THE OCEAN DEPARTMENT OF THE INTERIOR DONALD PAUL MODEL, Secretary U.S. GEOLOGICAL SURVEY Dallas L. Peck, Director UNITED STATES GOVERNMENT PRINTING OFFICE: 1986 For sale by the Books and Open-File Reports Section, U.S. Geological Survey, Federal Center, Box 25425, Denver, CO 80225 Library of Congress Cataloging-in-Publication Data McKelvey, V. E. (Vincent Ellis), 1916- Subsea mineral resources. (U.S. Geological Survey bulletin ; 1689-A) Bibliography: p. 95 Supt. of Docs, no.: I 19.3:1689-A 1. Marine mineral resources. I. Title. II. Series. QE75.B9 no. 1689-A 557.3s 86-600199 [TN264] [553'.09162] CONTENTS Abstract 1 Introduction 2 Concepts of reserves and resources 3 Definitions 4 Classification 4 Summary 7 Geology of the continental margins and ocean basins 7 Continental margins 7 Deep-ocean basins 8 Plate tectonic processes in the origin of subsea geologic provinces 9 Subsea minerals in relation to the continent-ocean framework 9 Marine placers 9 Placer minerals 10 Geologic environments favorable for the formation of placers 10 Placers in the marine environment 11 World distribution of marine placer deposits 12 Guides to prospecting for offshore placers 13 Offshore sand, gravel, and calcium carbonate deposits 13 Sand and gravel 17 Shell 18 Other offshore sources of calcium carbonate 19 Precious coral 20 Phosphorite and guano 21 Mineralogy and goechemistry
    [Show full text]
  • REVISION 1 Study on Nanophase Iron Oxyhydroxides in Freshwater
    1 REVISION 1 2 3 Study on nanophase iron oxyhydroxides in freshwater ferromanganese nodules 4 from Green Bay, Lake Michigan 5 Seungyeol Lee, Zhizhang Shen, and Huifang Xu* 6 NASA Astrobiology Institute, Department of Geoscience, University of Wisconsin–Madison, 7 Madison, Wisconsin 53706 8 9 10 11 12 13 * Corresponding author: 14 Prof. Huifang Xu, 15 Department of Geoscience, 16 University of Wisconsin-Madison 17 1215 West Dayton Street, A352 Weeks Hall 18 Madison, Wisconsin 53706 19 Tel: 1-608-265-5887 20 Fax: 1-608-262-0693 21 Email: [email protected] 22 23 ABSTRACT 24 Nanophase Fe-oxyhydroxides in freshwater ferromanganese nodules (FFN) from Green 25 Bay, Lake Michigan and adsorbed arsenate have been investigated by X-ray powder 26 diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), Z-contrast 27 imaging, and ab-initio calculations using the density functional theory (DFT). The samples 28 from northern Green Bay can be divided into two types: Fe-Mn nodules and Fe-rich nodules. 29 The manganese-bearing phases are todorokite, birnessite, and buserite. The iron-bearing 30 phases are feroxyhyte, nanophase goethite, 2-line ferrihydrite, and nanophase FeOOH with 31 guyanaite structure. Z-contrast images of the Fe-oxyhydroxides show ordered FeOOH nano- 32 domains with guyanaite structure intergrown with nanophase goethite. The FeOOH 33 nanophase is a precursor to the goethite. Henceforth, we will refer to it as “proto-goethite”. 34 DFT calculations indicate that goethite is more stable than proto-goethite. Our results suggest 35 that ordering between Fe and vacancies in octahedral sites result in the transformation from 36 feroxyhyte to goethite through a proto-goethite intermediate phase.
    [Show full text]
  • Back Matter (PDF)
    Index abyssal hills and ridge deposits, Peru Basin, 154 Krivoy Rog basin, 73 abyssal nodules, Pacific, 126, 132, 140, 187 Orissa, 119, 120 abyssal plain deposits, Pacific, 124, 125, 190, 192 Pacific, 132, 192, 193 accretion rate Peru Basin, 168, 169 of nodules, Peru basin, 153, 167, 174 Astarte, ferromanganese deposits on, 223,225 see also growth rates; sedimentation rates asymmetric growth of nodules, 173, 174 acidic fluids, leaching by, Kato Nevrokopi, 278, 279 asymmetric rhythms, 73 acidic soil, effects of, 14, 23 atmosphere, 5 14, 17, 19, 29, 33, 34, 36 acmite, 330 climate and, 84 active tectonic environment deposits, 5 early, 91 Pacific, 124, 125, 129 evolution, 10-13 northwest, 180, 183, 195-6 manganese depositon and, 15 South, 140 primitive, Archaean, 11, 100-1 adsorption capacity, 319, 320, 321 atmospheric inputs to oceans, 31 adsorption of metals see metal adsorption on manganese oxides Ba-Mn-Mg micas, 329 adsorption series, 312, 315, 322, 324 Bababudan Group, 91, 92 Aitutaki-Jarvis Transect, manganese nodules, 145-9, back-arc deposits, 7 125, 180, 181, 183, 195, 196, 199 166 bacteria activity, Hokkaido, 286, 287 Akan-Yunotaki deposits, 283, 284, 286-7, 288, 289, bacterial oxidation, 34, 221 290, 291,292, 293, 295, 296, 297, 298 Baltic Sea, 70, 71, 73, 74, 213-18, 227 alabandite, 7 ferromanganese concretions, 214, 218-31 Albian, Late, deposits, 21-2 pollution, 214, 227, 230 algae banded iron formations, 14, 16, 17, 18, 61 Hokkaido, 291,293, 295 Archaean, 100 oxidation of ferrous iron by, 29, 34 Dharwar Craton, 92, 95, 98 alkali
    [Show full text]
  • Thirtieth List of New Mineral Names
    MINERALOGICAL MAGAZINE, DECEMBER I978, VOL. 42, PP. 521-32 Thirtieth list of new mineral names M. H. HEY British Museum (Natural History), Cromwell Road, London, SW7 THis list of 19o names includes x Io names of valid or Alumolyndochite. S. A. Gorzhevskaya, G. A. Sido- probably valid new species, most of which have been renko, and A. I. Ginzburg, I974. Abstr. Zap. 105, approved by the I.M.A. Commission on New Minerals 76 (A~oMOAHHAOKnX). Unnecessary name for and Mineral Names, together with 6 new systematic aluminian lyndochite. names substituted for trivial names by the I.M.A. Sub- committee on nomenclature of the pyrochlore group and Antimonwesterveldite. Zap. 105, no.' 5, contents. 3I end-member names provided by the LM.A. Subcom- Erroneous transliteration of eypb~ma~era~t mittee on amphiboles; the rest include xo errors of BeeTepses~rr, antimonian westerveldite. spelling or transliteration, IO unnecessary names for Areherite. P. J. Bridge, t977. M.M. 41, 33. Tetra- varieties or polytypes, 8 synonyms, 4 species of doubtful gonal crystals of (K,NH4)H2PO4 occur in the validity, 5 artificial products, 3 trade names for gem- Petrogale Cave, near Madura Motel (3 I~ 54' S, stones, a hypothetical polytype, a group name, and a rock i27 ~ o' E), Western Australia. Formed from bat name. guano. Sp. gr. 2.23, 09 r513, e r47o. Named for As in the last three lists, certain contractions for the names of frequently cited periodicals are used: A.M., Am. M. Archer. [M.A. 77-218r; A.M. 63, 593.] Mineral; C.M., Can.
    [Show full text]