DOCSLIB.ORG

Presented !O the University of Manitoba Llasters of Sc I

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Presented !O the University of Manitoba Llasters of Sc I Copper Oxysal!s: The Jahn-TeIIer Effect And Its StructuraL lmplications by Raymond K. Eby A thesis presented !o the University of Manitoba in fuIf i Llment of the thesis requirement for lhe degree of llasters of Sc i ence in Deparlment of Geologica). Sc i ences llinnipeg, Man i toba (c) naymond K. Eby, 1988 Permission has been granteal L'aut.origatíon a êtê accordêe to the Natlonal Llbrary of å ta Bibliothèque nationale Canada to nícrofi lm thís du Canada de ¡nicrof ilmer the6is and to lend or sell cette thèse et de prêter ou copies of the fi lm. de vendre des exenplalres du fllm. The author (copyríght owner ) Lr auteur (tltulaíre du droit, hae re6erved other d'auteur) ae réserve Iea publ icat íon rfghtB, and autrea droits de publ lcat ion; nelther the thesís nor nf Ia thèse ní de longa extensive extracCa from it. extraits de ce1le-ci ne may be printed or otherwíse doivent être inprímês ou reproduced nithout hle/her autrement repro¿lults 6ana gon vrritten pernission. autorleatlon êcrite. rsBN 0-315-47941-8 COPPER OXYSALTS: THE JAHN-TELLER IFFECT AND ITS STRUCTURAL IMPLICATIONS BY RAYMOND K. EBY A thesis submitted to the Faculty of Graduate Studies of the University of Manitoba in partial fulfìllment of the requirenìeuts of the degree of MASTER OF SCIENCE o 1988 Permission has beeu granted to the LIBRARY OF THE UNIVER- SITY OF MANITOBA to lend or sell copies of this thesis. to the NATIONAL LIBRARY OF CANADA to microfilnr this thesis and to lend or sell copies of the film, and UNIVERSITY MICROFI LMS to publish an abstract of this thesis. The author reserves other publication rights, and neither the thesis no¡ extensive ext¡acts from it may be printed or other- wise reproduced without the author's wrilteir pernrissio:r. I hereby declare that I am the soLe author of this thesis. I authorize lhe University of Mânitoba to Lend this thesis !o other institutions or individuals for the purpose of scholarly research. Raymond K. Eby I further authorize the University of Manitoba to reproduce this thesis by photocopying.or by other means, in total or in pait, at the request of other institutions or individuals for lhe purpose of scholarly research. Raymond K. Eby - tl - The University of Manitoba requires the signatures of aIl persons using or pholocopying this thesis. Please sign below, and give address and date. ÀCKNOtlLEIN'EI{ENTS I l¡ish to thank the Natural Sciences and Engineering Research CounciL for their generosity in supporting my studies financiali.y. I also thank my advisor - Dr. Frank C. Hawthorne - for his inspirational. advice involving this thesis, I am also greatful to Dr. Fred Wicks and Dr. Ànthony Secco for giving their valuabLe time and effort to heLp make this thesis a coherent piece. - IV - ÀBSTRÀCT Copper oxysalts are a common class of minerals thal have been considered structurally anamalous. Some copper oxysalt structures have non-Cu analogues, bu! many do not, and the reasons for this have been unclear. The unique coordination environment of Cu2* is responsible for the anomalous character of Cu oxysalts. À regular octahedral coordination is unstable around Cu2* because of its degenerate de orbitat state. Spontaneous electronic relaxation (octahedral distortion) lifts the degeneracy, making distorted Cu-octahedra stable in structures. This is the Jahn-TeIler effect. By considering the complete coordination of Cu2*, the topology of Cu2* oxysalt structures is readily interpreted, and similarities to non-Cu oxysalts becorne eviden!. Nunerous studies have deaLt with only the local coordination environment of Cuz', but this study also deals with the long range structural effects of octahedral distortions e.g. ho¡+ distorled octahedra fit into strucLures, and the geometricaL/chenical consequences. Bond-valence analysis and mathematical simulation of crystal structures (using ÐLS) rtere used to study the structural effects of octahedral distortions. The Jahn-TelIer distortion provides a geonetrically flexible coordination environment for Cu2*, resul!ing in a wide variety of bond-valence distrÍbutions. This ftexibility creates the potential for polymerization styles not possible t¡ith un-distorted M2*-octahedra. Structural analyses show lwo fundanental structure types: 1) structures that cân be constructed from regular coordination poJ.yhedra, the arrangement of which can distort and accomodate the Jahn-Te11er distortion; and 2) structures that can onLy be constructed from very distorted coordination polyhedra. Isostructuralisrn is often possible in TYPE I structures, because of their geometrically flexible arrangements, Isostructuralism is not presen! in TYPE iI structures. Jahn-TelLer distortions are often coupled through structural symmetry by poJ.ymerization of Cu2*-octahedra. The resulting periodic electronic relaxations (PER) occur as waveforms commensurate with transLational symmeLry. Polymerization sLyIes control the type of waveform produced. Thus Cu2* oxysalts can be understood by anal.ysis of the local ocLahedral distortions and their influence on the long-range of structures. v1 CONTENTS ÀCKNOIILEDGEI,IENTS lv ÀBSTRÀCT chapter Þaqe I. iNTRODUCTION Cu2 t Oxysa I t s The Jahn-Teller Effect: Introductory Remarks Purpose of Thesi s Data Base Procedures: Experimental & Descriptive Bond-VaLence Theory: Bac kg round II. X-RÀY STRUCruRE REFINE}TENTS 13 Exper imental Methods 13 Data Collection . 13 Struclure Refinement . 15 Mineral Structure Ref inements 16 cornetite 16 Clinoclase ,..21 Euchroi !e . 26 Li rocon i te 28 III. À STRUCruRÀL CLÀSSIFICÀTION OF CUz+ OXYSÀIT I.IINERÂLS 36 Classi f icat ion Criteria 36 Isolated Polyhedra and Finite clusters 39 Inf inite Polyhedral Chains 43 Corner-Shar ing Cha ins 43 Octahedral Chains Edge-Sharing with 3*'T-groups 46 Edge-Sharing Cha ins 49 Cuo6-chains v¡i lhout. Te t rahedra : 49 CuO6-chains Flanked by Corner-Sharing Tetrahedra: 49 Inf inite Polyhedral Sheets ' 54 Edge-Sharing Cu-octahedral Sheets . 54 Fully Occupied Sheets: 54 Mixed Polyhedral Shee t s 64 Corner Sharing Sheets: 64 Edge-Sharing Sheels: 67 Structures of Polyhedral F ramewor k s 13 Calegory .\: Frameworks of Chains 't3 Corner-Sharíng Chains : 75 Edqe-Sharing Square Pyramidal Cuz*: . 78 - vt1 complex Edge-sharing 5*6M Linked to sing).e 3*aT: 80 Edge-Sha r i ng 6M-chains: 85 Category B: Frame!¡orks of sheets 98 Cu-Octahedral Sheets, Partially Occupied: 98 FuIIy Occupied Cu-Octahedral Sheets: 107 Complex Sheets of Mixed Polyhedra: . 107 Category C: Complex Octahedral Frameworks 117 ZeoI i te-Like Frameworks: 11'l Spinel-Type Frameworks: 121 Octahedral Diners and Trimers: 123 Summary 128 IV. THE IIÀHN-TELLER EFFECT ÀND LOCÀL CU2. ENVIRONI.EI'IT . 129 A DeLaiLed Explanation of the Jahn-TelLer Effect 129 The Coordinations of Cu?* 136 Octahedral Coordinati ons 139 Square Pyramids 0 Trigonal Bipyrarnids 156 Sguare Planar Cu2* 164 Unusual Cuz* Coordinations 166 Summary 167 V. BOND-VÀLENCE FEÀTT'RES OF CU2+ OXYSÀET STRUCN'RES 168 Bond-Valence Di str ibut ions 168 0c tahedra I Variations 168 Polymerization Features . .... 170 Sunnary 180 vI . DiSTÀNCE LEAST-SoUÀRES MODELLING OF CU2* oXYSÀLT STRUCnRES 181 The DLS Method . 181 Àpplication to Cu2* Oxysalt Structures 183 The General Problem 183 The MeLhod of Ànalysis 184 DLS Modeling of Rel-ated Slructure Types 189 The Olivenile croup . 189 The Kieserite Structure Group . 195 The Chalcomenile - Teinile Slructure 200 The Kröhnkite croup . 203 ÐLS Refinement of Unique Structure Types . 210 Lanmerile 210 Lindgreni te ; 211 Cha lc ocyan i te 214 Summary 21'l VII. THE ROLES OF CU2+ IN THE LONG NÀNGE STRUCN'RE OF OXYSÀLTS 219 À Geometrical Classification of Cuz' Oxysalt l.linerals 219 Long Range Àdaptation of Cu2- DisLortions in Structures 226 Periodic Electronic Relaxat.ions as waveforms 226 zíg-7,a9 Octahedral Chains 227 corrugated octahedral Sheets 230 v11¡ commensurate Modulation of Mixed-Type Polyhedral Layers 236 FinaL Summary . 238 REFERENCES 242 ÀÞÞend i x paqe À. STRUCI'I'RE FÀCTORS OF X-RÀY REFINEHENTS 251 cornet ite 252 CI inoclase 260 Euchroi te 269 Li roconi !e 276 B. DLS PROGRÀM OUTPUT 284 The 0liveni te Group 285 The Ke i seri te Group 293 The Chalcomeni te/Tei nite Struclure 296 The Kröhnk i !e Group 298 Lindgreni te & Chalcocyanite 303 !x L]ST OF TÀBLES pÊg!. cu2* Oxysalt Minerals Studied 6 Pertinent Data for cornetite . 17 Atomic (fractional) & Thermal ParaÍìeters for cornetite 18 Selected Bond Lengths (Â) of Cornetite . 19 Selected Bond Àngles (o) for Cornelile . , 20 Bond-Valences for Cornetite ..,,21 Pertinent Data for Clinocl.ase , 22 Àtomic (fractional) & Thermal Parameters for Clinoclase 23 Selected Bond Lengths (Â) of Clinoclase . , 24 Selected Bond Àngles (o) for Ctinoclase . 25 Bond-Valences for Clinoclase . .",..25 Pertinent Datä for Euchroite , 26 Àtornic (fracLional) 6, ThermaL Paraneters for Euchroite , , . 28 Selecled Bond Lengths (Â) of Euchroite . , 29 Selected Bond ÀngJ.es (o) for Euchroite 30 Bond-vaLences for Euchroile 31 Pertinen! Data for tiroconite . 32 Àtomic (fractional) & Thermal Parameters for Liroconite . 33 Selected Bond Lengths (Â) of Liroconite . 34 Selected Bond Angles (o) for Liroconite 35 Bond-Valences for Liroconite . 35 Shading Scheme For Polyhedral Drawings 38 3,2, Isolated Polyhedra and Finite Cluslers 39 3.3. Infinite Polyhedral Chains . ,44 3.4, ¡nfinite Polyhedral Sheets . 55 3.5. Polyhedral Framework Categories 73 3.6. caLegory À: Polyhedral Frameworks of Chains . , . 14 3.7. Bond-Valences for Àzurite 101 3.8. Category B: Frameworks of Sheels 102 3.9, Category c: Complex Octahedral Frameworks 118 4.1, Geornetrical Parameters for Cuztoe octahedra 140 4,2. Parameters for Five Coordinate Cu-Polyhedra 157 4.3. Square Planar CuO¿ . 164 4.4. Unusual Cu2t Coordinations . 156 6.1. CetI Dimensions of the Olivenite Group . 190 6.2. Atomic Dislance Violations in the Idealized 0Iivenite croup . 193 6.3. Bond-valence Tables for the Idealized Olivenite Group 194 6,4.
Load more

Recommended publications
  • Mineral Processing
    Mineral Processing Foundations of theory and practice of minerallurgy 1st English edition JAN DRZYMALA, C. Eng., Ph.D., D.Sc. Member of the Polish Mineral Processing Society Wroclaw University of Technology 2007 Translation: J. Drzymala, A. Swatek Reviewer: A. Luszczkiewicz Published as supplied by the author ©Copyright by Jan Drzymala, Wroclaw 2007 Computer typesetting: Danuta Szyszka Cover design: Danuta Szyszka Cover photo: Sebastian Bożek Oficyna Wydawnicza Politechniki Wrocławskiej Wybrzeze Wyspianskiego 27 50-370 Wroclaw Any part of this publication can be used in any form by any means provided that the usage is acknowledged by the citation: Drzymala, J., Mineral Processing, Foundations of theory and practice of minerallurgy, Oficyna Wydawnicza PWr., 2007, www.ig.pwr.wroc.pl/minproc ISBN 978-83-7493-362-9 Contents Introduction ....................................................................................................................9 Part I Introduction to mineral processing .....................................................................13 1. From the Big Bang to mineral processing................................................................14 1.1. The formation of matter ...................................................................................14 1.2. Elementary particles.........................................................................................16 1.3. Molecules .........................................................................................................18 1.4. Solids................................................................................................................19
    [Show full text]
  • Euchlorine Knacu3o(SO4)3 C 2001-2005 Mineral Data Publishing, Version 1
    Euchlorine KNaCu3O(SO4)3 c 2001-2005 Mineral Data Publishing, version 1 Crystal Data: Monoclinic. Point Group: 2/m. As crystals, tabular on {001}, with rectangular outline, to 2 mm; typically as an incrustation. Physical Properties: Cleavage: In two directions. Hardness = n.d. D(meas.) = 3.27 D(calc.) = 3.28 Soluble in H2O. Optical Properties: Semitransparent. Color: Emerald-green; emerald-green in transmitted light. Optical Class: Biaxial (+). Pleochroism: X = pale grass-green; Y = grass-green; Z = bright yellow-green. α = 1.580 β = 1.605 γ = 1.644 2V(meas.) = Moderately large. Cell Data: Space Group: C2/a. a = 18.41(5) b = 9.43(3) c = 14.21(5) β = 113.7(3)◦ Z=8 X-ray Powder Pattern: Vesuvius, Italy. 8.44 (100), 2.816 (47), 2.544 (45), 2.843 (40), 2.852 (37), 3.475 (30), 3.237 (25) Chemistry: (1) (2) SO3 41.41 43.13 Al2O3 0.06 CuO 43.69 42.85 MgO 0.17 CaO 0.07 Na2O 6.35 5.56 K2O 8.25 8.46 Total [100.00] 100.00 (1) Vesuvius, Italy; by electron microprobe, average of seven analyses, recalculated to 100% 2− from an original total of 101.86%, (SO4) shown present by IR; corresponds to K1.01Na1.18 Mg0.02Ca0.01Cu3.15O1.27(SO4)3. (2) KNaCu3O(SO4)3. Occurrence: A rare sublimate around volcanic fumaroles. Association: Dolerophanite, eriochalcite, chalcocyanite, melanothallite (Vesuvius, Italy); stoiberite, fingerite, ziesite, th´enardite,mcbirneyite (Izalco volcano, El Salvador); eriochalcite, melanothallite, fedotovite, vergasovaite, chalcocyanite, dolerophanite, tenorite, cuprian anglesite, gold (Tolbachik volcano, Russia).
    [Show full text]
  • JOURNAL the Russell Society
    JOURNAL OF The Russell Society Volume 20, 2017 www.russellsoc.org JOURNAL OF THE RUSSELL SOCIETY The journal of British Isles topographical mineralogy EDITOR Dr Malcolm Southwood 7 Campbell Court, Warrandyte, Victoria 3113, Australia. ([email protected]) JOURNAL MANAGER Frank Ince 78 Leconfield Road, Loughborough, Leicestershire, LE11 3SQ. EDITORIAL BOARD R.E. Bevins, Cardiff, U.K. M.T. Price, OUMNH, Oxford, U.K. R.S.W. Braithwaite, Manchester, U.K. M.S. Rumsey, NHM, London, U.K. A. Dyer, Hoddlesden, Darwen, U.K. R.E. Starkey, Bromsgrove, U.K. N.J. Elton, St Austell, U.K. P.A. Williams, Kingswood, Australia. I.R. Plimer, Kensington Gardens, S. Australia. Aims and Scope: The Journal publishes refereed articles by both amateur and professional mineralogists dealing with all aspects of mineralogy relating to the British Isles. Contributions are welcome from both members and non-members of the Russell Society. Notes for contributors can be found at the back of this issue, on the Society website (www.russellsoc.org) or obtained from the Editor or Journal Manager. Subscription rates: The Journal is free to members of the Russell Society. The non-member subscription rates for this volume are: UK £13 (including P&P) and Overseas £15 (including P&P). Enquiries should be made to the Journal Manager at the above address. Back numbers of the Journal may also be ordered through the Journal Manager. The Russell Society: named after the eminent amateur mineralogist Sir Arthur Russell (1878–1964), is a society of amateur and professional mineralogists which encourages the study, recording and conservation of mineralogical sites and material.
    [Show full text]
  • Demesmaekerite Pb2cu5(UO2)2(Se O3)6(OH)6 • 2H2O C 2001-2005 Mineral Data Publishing, Version 1
    4+ Demesmaekerite Pb2Cu5(UO2)2(Se O3)6(OH)6 • 2H2O c 2001-2005 Mineral Data Publishing, version 1 Crystal Data: Triclinic. Point Group: 1. Crystals are elongated along [001] and flattened on {100} or {010}, with dominant {100} and {010}, secondary faces typically striated k [101], to 1 cm; in radial aggregates. Physical Properties: Hardness = 3–4 D(meas.) = 5.28(4) D(calc.) = 5.42 Radioactive. Optical Properties: Translucent to opaque. Color: Bottle-green to pale olive-green, becoming brownish green with dehydration. Optical Class: Biaxial (+). Pleochroism: X 0 = yellow-green; Y 0 = brown. α = 1.835(5) (α 0) β = n.d. γ = 1.910(5) (γ 0) 2V(meas.) = n.d. Cell Data: Space Group: P 1. a = 11.955(5) b = 10.039(4) c = 5.639(2) α =89.78(4)◦ β = 100.36(4)◦ γ =91.34(4)◦ Z=1 X-ray Powder Pattern: Musonoi mine, Congo. 2.97 (FFF), 5.42 (FF), 5.89 (F), 3.34 (F), 5.14 (mF), 4.72 (mF), 4.67 (mF) Chemistry: (1) (2) SeO2 30.9 30.65 UO3 27.6 26.34 PbO 19.4 20.55 CuO 18.2 18.31 H2O 4.2 4.15 Total 100.3 100.00 (1) Musonoi mine, Congo; H2O by the Penfield method; corresponds to Pb1.87Cu4.93(UO2)2.08 • • (SeO3)6(OH)6.04 2H2O. (2) Pb2Cu5(UO2)2(SeO3)6(OH)6 2H2O. Occurrence: Rare in the lower oxidized portions of a selenium-bearing Cu–Co deposit. Association: Cuprosklodowskite, kasolite, guilleminite, derriksite, chalcomenite, malachite, selenian digenite.
    [Show full text]
  • Vibrational Spectroscopic Study of the Uranyl Selenite Mineral Derriksite
    Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 473–477 Contents lists available at ScienceDirect Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy journal homepage: www.elsevier.com/locate/saa Vibrational spectroscopic study of the uranyl selenite mineral derriksite Cu4UO2(SeO3)2(OH)6ÁH2O ⇑ Ray L. Frost a, , JirˇíCˇejka b, Ricardo Scholz c, Andrés López a, Frederick L. Theiss a, Yunfei Xi a a School of Chemistry, Physics and Mechanical Engineering, Science and Engineering Faculty, Queensland University of Technology, GPO Box 2434, Brisbane Queensland 4001, Australia b National Museum, Václavské námeˇstí 68, CZ-115 79 Praha 1, Czech Republic c Geology Department, School of Mines, Federal University of Ouro Preto, Campus Morro do Cruzeiro, Ouro Preto, MG 35400-00, Brazil highlights graphical abstract We have studied the mineral derriksite Cu4UO2(SeO3)2(OH)6ÁH2O. A comparison was made with the other uranyl selenites. Namely demesmaekerite, marthozite, larisaite, haynesite and piretite. Approximate U–O bond lengths in uranyl and O–HÁÁÁO hydrogen bond lengths were calculated. article info abstract Article history: Raman spectrum of the mineral derriksite Cu4UO2(SeO3)2(OH)6ÁH2O was studied and complemented by Received 20 May 2013 the infrared spectrum of this mineral. Both spectra were interpreted and partly compared with the spec- Received in revised form 29 July 2013 tra of demesmaekerite, marthozite, larisaite, haynesite and piretite. Observed Raman and infrared bands Accepted 2 August 2013 were attributed to the (UO )2+, (SeO )2À, (OH)À and H O vibrations. The presence of symmetrically dis- Available online 22 August 2013 2 3 2 tinct hydrogen bonded molecule of water of crystallization and hydrogen bonded symmetrically distinct hydroxyl ions was inferred from the spectra in the derriksite unit cell.
    [Show full text]
  • Mineral Index
    Mineral Index Abhurite T.73, T.355 Anandite-Zlvl, T.116, T.455 Actinolite T.115, T.475 Anandite-20r T.116, T.45S Adamite T.73,T.405, T.60S Ancylite-(Ce) T.74,T.35S Adelite T.115, T.40S Andalusite (VoU, T.52,T.22S), T.27S, T.60S Aegirine T.73, T.30S Andesine (VoU, T.58, T.22S), T.41S Aenigmatite T.115, T.46S Andorite T.74, T.31S Aerugite (VoU, T.64, T.22S), T.34S Andradite T.74, T.36S Agrellite T.115, T.47S Andremeyerite T.116, T.41S Aikinite T.73,T.27S, T.60S Andrewsite T.116, T.465 Akatoreite T.73, T.54S, T.615 Angelellite T.74,T.59S Akermanite T.73, T.33S Ankerite T.74,T.305 Aktashite T.73, T.36S Annite T.146, T.44S Albite T.73,T.30S, T.60S Anorthite T.74,T.415 Aleksite T.73, T.35S Anorthoclase T.74,T.30S, T.60S Alforsite T.73, T.325 Anthoinite T.74, T.31S Allactite T.73, T.38S Anthophyllite T.74, T.47S, T.61S Allanite-(Ce) T.146, T.51S Antigorite T.74,T.375, 60S Allanite-(La) T.115, T.44S Antlerite T.74, T.32S, T.60S Allanite-(Y) T.146, T.51S Apatite T.75, T.32S, T.60S Alleghanyite T.73, T.36S Aphthitalite T.75,T.42S, T.60 Allophane T.115, T.59S Apuanite T.75,T.34S Alluaudite T.115, T.45S Archerite T.75,T.31S Almandine T.73, T.36S Arctite T.146, T.53S Alstonite T.73,T.315 Arcubisite T.75, T.31S Althausite T.73,T.40S Ardaite T.75,T.39S Alumino-barroisite T.166, T.57S Ardennite T.166, T.55S Alumino-ferra-hornblende T.166, T.57S Arfvedsonite T.146, T.55S, T.61S Alumino-katophorite T.166, T.57S Argentojarosite T.116, T.45S Alumino-magnesio-hornblende T.159,T.555 Argentotennantite T.75,T.47S Alumino-taramite T.166, T.57S Argyrodite (VoU,
    [Show full text]
  • Oxidizing-Type Fumaroles of the Tolbachik Volcano, a Mineralogical and Geochemical Unique
    Russian Geology and Geophysics © 2020, V.S. Sobolev IGM, Siberian Branch of the RAS Vol. 61, No. 5-6, pp. 675–688, 2020 DOI:10.15372/RGG2019167 Geologiya i Geofizika Oxidizing-Type Fumaroles of the Tolbachik Volcano, a Mineralogical and Geochemical Unique I.V. Pekova,b, , A.A. Agakhanovс, N.V. Zubkovaa, N.N. Koshlyakovaa, N.V. Shchipalkinaa, F.D. Sandalova, V.O. Yapaskurta, A.G. Turchkovaa, E.G. Sidorovd a Lomonosov Moscow State University, Leninskie Gory 1, Moscow, 119991, Russia b Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences, ul. Kosygina 19, Moscow, 119991, Russia c Fersman Mineralogical Museum, Leninskii pr. 18/2, Moscow, 119071, Russia d Institute of Volcanology and Seismology, Far Eastern Branch of the Russian Academy of Sciences, bul. Piipa 9, Petropavlovsk-Kamchatsky, 683006, Russia Received 1 July 2019; accepted 28 August 2019 Abstract—We overview recent data on the mineralogy of oxidizing-type fumaroles of the Tolbachik Volcano (Kamchatka, Russia), with the main focus on the chemical specifics of the minerals. The active fumarole fields of Tolbachik are the most prominent mineral- forming exhalative system of this type in the world. About 350 mineral species, including 123 minerals first discovered here, are reliably identified in the Tolbachik fumaroles. The species diversity and the specifics of this mineralization are due to the unique combination of the physicochemical conditions and mechanisms of its formation: high temperatures, atmospheric pressure, superhigh oxygen fugacity, gas transport of most of chemical elements, and direct deposition of many high-temperature minerals from volcanic gases with a specific geo- chemical composition, including strong enrichment in alkaline metals and chalcophile (“ore”) elements.
    [Show full text]
  • Crystal Chemistry and Structural Complexity of Natural and Synthetic Uranyl Selenites
    Review Crystal Chemistry and Structural Complexity of Natural and Synthetic Uranyl Selenites Vladislav V. Gurzhiy 1,*, Ivan V. Kuporev 1, Vadim M. Kovrugin 1, Mikhail N. Murashko 1, Anatoly V. Kasatkin 2 and Jakub Plášil 3 1 Institute of Earth Sciences, St. Petersburg State University, University Emb. 7/9, St. Petersburg, 199034, Russian Federation; [email protected] (I.V.K.); [email protected] (V.M.K.); [email protected] (M.N.M.) 2 Fersman Mineralogical Museum of the Russian Academy of Sciences, Leninskiy pr. 18, 2, Moscow, 119071, Russian Federation; [email protected] 3 Institute of Physics, The Academy of Sciences of the Czech Republic, v.v.i., Na Slovance 2, Praha 8, 18221, Czech Republic; [email protected] * Correspondence: [email protected], [email protected] Received: 10 November 2019; Accepted: 28 November 2019; Published: 30 November 2019 Abstract: Comparison of the natural and synthetic phases allows an overview to be made and even an understanding of the crystal growth processes and mechanisms of the particular crystal structure formation. Thus, in this work, we review the crystal chemistry of the family of uranyl selenite compounds, paying special attention to the pathways of synthesis and topological analysis of the known crystal structures. Comparison of the isotypic natural and synthetic uranyl-bearing compounds suggests that uranyl selenite mineral formation requires heating, which most likely can be attributed to the radioactive decay. Structural complexity studies revealed that the majority of synthetic compounds have the topological symmetry of uranyl selenite building blocks equal to the structural symmetry, which means that the highest symmetry of uranyl complexes is preserved regardless of the interstitial filling of the structures.
    [Show full text]
  • A New Mineral Species from the Tolbachik Volcano, Kamchatka Peninsula, Russia
    921 The Canadian Mineralogist Vol. 45, pp. 921-927 (2007) DOI : 10.2113/gscanmin.45.4.921 PAUFLERITE, ␤-VO(SO4), A NEW MINERAL SPECIES FROM THE TOLBACHIK VOLCANO, KAMCHATKA PENINSULA, RUSSIA Sergey V. KRIVOVICHEV§ Department of Crystallography, St. Petersburg State University, University Emb. 7/9, St. Petersburg, 199034, Russia Lidiya P. VERGASOVA Institute of Volcanology, Russian Academy of Sciences, Bulvar Piypa 9, Petropavlovsk-Kamchatskiy, 683006, Russia Sergey N. BRITVIN Department of Mineral Deposits, St. Petersburg State University, University Emb. 7/9, St. Petersburg, 199034, Russia Stanislav K. FILATOV Department of Crystallography, St. Petersburg State University, University Emb. 7/9, St. Petersburg, 199034, Russia Volker KAHLENBERG Institut für Mineralogie und Petrographie, Leopold-Franzens-Universität Innsbruck, Innrain 52, A–6020 Innsbruck, Austria Vladimir V. ANANIEV Institute of Volcanology, Russian Academy of Sciences, Bulvar Piypa 9, Petropavlovsk-Kamchatskiy, 683006, Russia Abstract Paufl erite, ␤-VO(SO4), is a new mineral species from the fumaroles of the Great Fissure Tolbachik eruption (GFTE), Kamchatka Peninsula, Russia. It was found in 1977 in the fi rst cinder cone of the North breach of the GFTE. The mineral occurs as light green prismatic crystals up to 0.1 mm in length, associated with shcherbinaite (V2O5), an unknown Tl–Bi sulfate and fi nely crystalline Mg, Al, Fe and Na sulfates. Paufl erite is light green with a white streak and vitreous luster; the mineral is transparent and non-fl uorescent. The Mohs hardness is 3–4. Paufl erite is brittle, and without visible cleavage. The density is 3.36(4) (measured) and 3.294 g/cm3 (calculated). The mineral is biaxial, optically positive, ␣ 1.731(4), ␤ 1.778(2), ␥ 1.845(4), with 2Vmeas ≈ 90°, and 2Vcalc equal to 83°.
    [Show full text]
  • Alt I5LNER&S
    4r>.'44~' ¶4,' Alt I5LNER&SI 4t *vX,it8a.rsAt s 4"5' r K4Wsx ,4 'fv, '' 54,4 'T~~~~~~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~~~~~' 4>i4^ 44 4 r 44,4 >s0 s;)r i; X+9;s tSiX,.<t;.W.FE0''¾'"',f,,v-;, s sHteS<T^ 4~~~~~~~~~~~~~~~~~~~~'44'" 4444 ;,t,4 ~~~~~~~~~' "e'(' 4 if~~~~~~~~~~0~44'~"" , ",4' IN:A.S~~ ~ ~ C~ f'"f4444.444"Z'.4;4 4 p~~~~~~~~~~~~~~~~~~~44'1s-*o=4-4444's0zs*;.-<<<t4 4 4 A'.~~~44~~444) O 4t4t '44,~~~~~~~~~~i'$'" a k -~~~~~~44,44.~~~~~~~~~~~~~~~~~~44-444444,445.44~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~.V 4X~~~~~~~~~~~~~~4'44 44 444444444.44. AQ~~ ~ ~~~~, ''4'''t :i2>#ZU '~f"44444' i~~'4~~~k AM 44 2'tC>K""9N 44444444~~~~~~~~~~~,4'4 4444~~~~IT fpw~~ ~ ~ ~ ~ ~ ~ 'V~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ Ae, ~~~~~~~~~~~~~~~~~~~~~~2 '4 '~~~~~~~~~~4 40~~~~~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ' 4' N.~~..Fg ~ 4F.~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ " ~ ~ ~ 4 ~~~ 44zl "'444~~474'~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ ~ ~ ~ &~1k 't-4,~~~~~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ :"'".'"~~~~~~~~~~~~~~~~~"4 ~~ 444"~~~~~~~~~'44*#"44~~~~~~~~~~4 44~~~~~'f"~~~~~4~~~'yw~~~~4'5'# 44'7'j ~4 y~~~~~~~~~~~~~~~~~~~~~~~~~~~~~""'4 1L IJ;*p*44 *~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~44~~~~~~~~~~~~~~~~~~~~1 q A ~~~~~ 4~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~W~~k* A SYSTEMATIC CLASSIFICATION OF NONSILICATE MINERALS JAMES A. FERRAIOLO Department of Mineral Sciences American Museum of Natural History BULLETIN OF THE AMERICAN MUSEUM OF NATURAL HISTORY VOLUME 172: ARTICLE 1 NEW YORK: 1982 BULLETIN OF THE AMERICAN MUSEUM OF NATURAL HISTORY Volume 172, article l, pages 1-237,
    [Show full text]
  • Shin-Skinner January 2018 Edition
    Page 1 The Shin-Skinner News Vol 57, No 1; January 2018 Che-Hanna Rock & Mineral Club, Inc. P.O. Box 142, Sayre PA 18840-0142 PURPOSE: The club was organized in 1962 in Sayre, PA OFFICERS to assemble for the purpose of studying and collecting rock, President: Bob McGuire [email protected] mineral, fossil, and shell specimens, and to develop skills in Vice-Pres: Ted Rieth [email protected] the lapidary arts. We are members of the Eastern Acting Secretary: JoAnn McGuire [email protected] Federation of Mineralogical & Lapidary Societies (EFMLS) Treasurer & member chair: Trish Benish and the American Federation of Mineralogical Societies [email protected] (AFMS). Immed. Past Pres. Inga Wells [email protected] DUES are payable to the treasurer BY January 1st of each year. After that date membership will be terminated. Make BOARD meetings are held at 6PM on odd-numbered checks payable to Che-Hanna Rock & Mineral Club, Inc. as months unless special meetings are called by the follows: $12.00 for Family; $8.00 for Subscribing Patron; president. $8.00 for Individual and Junior members (under age 17) not BOARD MEMBERS: covered by a family membership. Bruce Benish, Jeff Benish, Mary Walter MEETINGS are held at the Sayre High School (on Lockhart APPOINTED Street) at 7:00 PM in the cafeteria, the 2nd Wednesday Programs: Ted Rieth [email protected] each month, except JUNE, JULY, AUGUST, and Publicity: Hazel Remaley 570-888-7544 DECEMBER. Those meetings and events (and any [email protected] changes) will be announced in this newsletter, with location Editor: David Dick and schedule, as well as on our website [email protected] chehannarocks.com.
    [Show full text]
  • Crystal Chemistry and Structural Complexity of Natural and Synthetic Uranyl Selenites
    crystals Review Crystal Chemistry and Structural Complexity of Natural and Synthetic Uranyl Selenites Vladislav V. Gurzhiy 1,* , Ivan V. Kuporev 1, Vadim M. Kovrugin 1, Mikhail N. Murashko 1, Anatoly V. Kasatkin 2 and Jakub Plášil 3 1 Institute of Earth Sciences, St. Petersburg State University, University Emb. 7/9, St. Petersburg 199034, Russian; [email protected] (I.V.K.); [email protected] (V.M.K.); [email protected] (M.N.M.) 2 Fersman Mineralogical Museum of the Russian Academy of Sciences, Leninskiy pr. 18, 2, Moscow 119071, Russian; [email protected] 3 Institute of Physics, The Academy of Sciences of the Czech Republic, v.v.i., Na Slovance 2, 18221 Praha 8, Czech Republic; [email protected] * Correspondence: [email protected] or [email protected] Received: 10 November 2019; Accepted: 28 November 2019; Published: 30 November 2019 Abstract: Comparison of the natural and synthetic phases allows an overview to be made and even an understanding of the crystal growth processes and mechanisms of the particular crystal structure formation. Thus, in this work, we review the crystal chemistry of the family of uranyl selenite compounds, paying special attention to the pathways of synthesis and topological analysis of the known crystal structures. Comparison of the isotypic natural and synthetic uranyl-bearing compounds suggests that uranyl selenite mineral formation requires heating, which most likely can be attributed to the radioactive decay. Structural complexity studies revealed that the majority of synthetic compounds have the topological symmetry of uranyl selenite building blocks equal to the structural symmetry, which means that the highest symmetry of uranyl complexes is preserved regardless of the interstitial filling of the structures.
    [Show full text]