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Crystal chemistry of carbonates of rare earths and calcium

Research Project

Project/Area Number 13640488
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Petrology/Mineralogy/Science of ore deposit
Research Institutionthe National Science Museum

Principal Investigator

MIYAWAKI Ritsuro  National Science Museum, Dept of Geology, senior curator, 地学研究部, 室長 (80290865)

Project Period (FY) 2001 – 2004
Project Status Completed (Fiscal Year 2004)
Budget Amount *help
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2004: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 2003: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 2002: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 2001: ¥1,800,000 (Direct Cost: ¥1,800,000)
Keywordsrare earth elements / hydrous carbonate / rare earth mineral / crystal structure / kozoite / 結晶化学 / 木村石 / 炭酸塩 / 水酸バストネン石
Research Abstract

Kozoite-(Nd), Nd(CO_3)(OH), occurs in cavities and fissures of alkali olivine basalt exposed at Niikoba, Hizen-cho, Higashi Matsuura-gun, Saga Prefecture, Japan. The shape of aggregates of minute crystals of kozoite-(Nd) is usually platy, which corresponds to the crystal habit of lanthanite-(Nd), Nd_2(CO_3)_3・8H_2O. This occurrence mode suggests that kozoite-(Nd) is probably alteration products of lanthanite-(Nd) in the postmagmatic hydrothermal activity.
The alteration condition was examined with a chemical reagent of Nd_2(CO_3)_3・8H_2O [lanthanite-(Nd)] and sodium aqueous solutions under hydrothermal conditions. The powder of starting material, Nd_2(CO_3)_3・8H_2O, was sealed with sodium aqueous solution (0-0.5M NaHCO_3 or NaOH) in a Teflon vessel or a platinum capsule. The reaction containers were kept at 150,200,or 250℃. The reaction process was traced varying the reaction duration up to 7 days. The reaction products were filtered, washed with distilled water, and dried overnight at … More room temperature. They were characterized by XRD.
The starting material, Nd_2(CO_3)_3・8H_2O was decomposed within 30 minutes. A phase with the XRD pattern of Nd_2(CO_3)_3・2.5H_2O [ICDD #33-0932] was formed with the decomposition of Nd_2(CO_3)_3・8H_2O. Subsequently, kozoite-(Nd) and hydroxylbastnasite-(Nd), the polymorph of kozoite-(Nd), were crystallized. The higher reaction temperature and the higher pressure tend to promote the formation of hydroxylbastnashe-(Nd) instead of kozoite-(Nd). Actually, kozoite-(Nd) is the less dense polymorph in comparison to hydroxylbastnasite-(Nd). It is reasonable that kozoite-(Nd) with lower density crystallizes under lower pressure conditions. These trends indicate that kozoite-(Nd) may be formed relatively lower temperature and lower pressure. On the other hand, the yield of kozoite-(Nd) was reduced and hydroxylbastnasite-(Nd) was the dominant reaction product in the reaction runs using sodium solutions with higher concentration and in the runs with elongated reaction duration. These observations auggest that kozoite-(Nd) is a metastable phase in the present reaction system.
Rare earth carbonate hydroxides, RE(CO_3)OH, were hydrothermally synthesized from formic acid and hydroxide gels of La, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Y. A hexagonal phase with the bastnasite-type structure was obtained for RE=La, Ce, Nd and Sm. An orthorhombic phase wilh the kozoite-type structure was obtained for RE=Nd and Sm. In addition to these two major phases, another orthorhombic modification of the kozoite-type structure was obtained for RE=Eu, Gd, Tb, Dy, Ho, Er, Tm and Y. The latter phase has a lower symmetry (space group : P2_12_12_1) than the true kozoite-type structure (Pnma). A new tetragonal phase (space group : P4_2/nmc) was found for RE=Tm and Yb.
The crystal structures of RE(CO_3)OH were refined for Pnma (RE=Nd and Sm), P2_12_12_1(RE=Eu, Gd, Tb, Dy, Ho, Er, Tm and Y) and P4_2/nmc phases (RE=Tm and Yb) utilizing single crystal intensity data. The distinct feature of the difference among the three structures are the coordination numbers of the RE^<3+> ions : 10 for the Pnma phase,9 for the P2_12_12_1 phsase, and 8 for the P4_2/nmc phase. A systematic comparison of two orthorhombic structures revealed the following dynamic variation in the coordination environment about the RE^<3+> ions with ionic radii. Although the interatomic RE-O distances tend to decrease with the lanthanide contraction, exceptions were observed for two of the RE-O distances. The mutual close proximity of CO_3^<2-> anions caused by the lanthanide contraction led to repulsion between the CO_3^<2-> anions, which caused a decreases in the symmetry of configuration of CO_3^<2-> anions around the central RE^<3+> ion and some oxygen atoms of CO_3^<2-> became away from the first coordination shell of the RE^<3+> ions dueto the elongation of the RE-O distances.
The crystal structure of tetragonal RE(CO_3)OH show a characteristic feature distinct from those of orthorhombic phases. It consists of ladders of 8-coordinated RE^<3+> cation with CO_3^<2-> and OH^- anions arranged in a form of double cross. The powder XRD pattern of the tetragonal RE(CO_3)OH was identical with that of a synthetic material previously reported as RE_6(OH)_4(CO_3)_7[1] indicating that the latter formula is not adequate. Less

Report

(5 results)
  • 2004 Annual Research Report   Final Research Report Summary
  • 2003 Annual Research Report
  • 2002 Annual Research Report
  • 2001 Annual Research Report
  • Research Products

    (31 results)

All 2005 2004 2003 2002 Other

All Journal Article (24 results) Publications (7 results)

  • [Journal Article] The true structure of wonesite, an interlayer-deficient trioctahedral sodium mica.2005

    • Author(s)
      T.Kogure, R.Miyawaki, Y.Banno
    • Journal Title

      American Mineralogist 90

      Pages: 725-731

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] The true structure of wonesite, an interlayer-deficient trioctahedral sodium mica2005

    • Author(s)
      T.Kogure, R.Miyawaki, Y.Banno
    • Journal Title

      American Mineralogist 90

      Pages: 725-731

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Magnesiosadanagaite, a new member of the amphibole group from Kasuga-mura, Gifu Prefecture, central Japan2004

    • Author(s)
      Y.Banno, R.Miyawaki, S.Matsubara, K.Makino, M.Bunno, S.Yamada, T.Kamiya
    • Journal Title

      European Journal of Mineralogy 16

      Pages: 177-183

    • NAID

      130004646672

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Interlayer structure in aspidolite, the Na analogue of phlogopite2004

    • Author(s)
      T.Kogure, Y.Banno, R.Miyawaki
    • Journal Title

      European Journal of Mineralogy 16(6)

      Pages: 891-897

    • NAID

      10019865758

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Magnesiosadanagaite, a new member of the amphibole group from Kasuga-mura, Gifu Prefecture, central Japan.2004

    • Author(s)
      Y.Banno, R.Miyawaki, S.Matsubara, K.Makino, M.Bunno, S.Yamada, T.Kamiya
    • Journal Title

      European Journal of Mineralogy 16

      Pages: 177-183

    • NAID

      130004646672

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Interlayer structure in aspidolite, the Na analogue of phlogopite.2004

    • Author(s)
      T.Kogure, Y.Banno, R.Miyawaki
    • Journal Title

      European Journal of Mineralogy 16

      Pages: 891-897

    • NAID

      10019865758

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Tokyoite, Ba_2Mn^<3+>(VO_4)_2(OH), a new mineral from the Shiromaru mine, Okutama, Tokyo, Japan.2004

    • Author(s)
      S.Matsubara, R.Miyawaki, K.Yokoyama, M.Shimizu, H.Imai
    • Journal Title

      Journal of Mineralogical and Petrological Sciences 99

      Pages: 363-367

    • NAID

      10013710721

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] A Refinement of the Crystal Structure of synthetic Tengerite-(Y).2004

    • Author(s)
      R.Miyawaki, S.Matsubara
    • Journal Title

      Bull.Natn.Sci.Mus., Tokyo, Ser.C 30

      Pages: 1-4

    • NAID

      110004707982

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Magnesiosadanagaite, a new member of the amphibole group from Kasuga-mura, Gifu Prefecture, Central Japan2004

    • Author(s)
      Y.Banno, R.Miyawaki, S.Matsubara, K.Makino, M.Bunno, S.Yamada, T.Kamiya
    • Journal Title

      European Journal of Mineralogy 16

      Pages: 177-183

    • NAID

      130004646672

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Interlayer structure in aspidolite, the Na analogue of phlogopite2004

    • Author(s)
      T.Kogure, Y.Banno, R.Miyawaki
    • Journal Title

      European Journal of Mineralogy 16・6

      Pages: 891-897

    • NAID

      10019865758

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Tokyoite, Ba_2Mn^<3+>(VO_4)_2(OH), a new mineral from the Shiromaru mine, Okutama, Tokyo, Japan2004

    • Author(s)
      S.Matsubara, R.Miyawaki, K.Yokoyama, M.Shimizu, H.Imai
    • Journal Title

      Journal of Mineralogical and Petrological Sciences 99

      Pages: 363-367

    • NAID

      10013710721

    • Related Report
      2004 Annual Research Report
  • [Journal Article] A Refinement of the Crystal Structure of synthetic Tengerite-(Y)2004

    • Author(s)
      R.Miyawaki, S.Matsubara
    • Journal Title

      Bull.Natn.Sci.Mus.,Tokyo, Ser.C 30

      Pages: 1-4

    • NAID

      110004707982

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Kozoite-(La), La(CO_3)(OH), a new mineral from Mitsukoshi, Hizen-cho, Saga Prefecture, Japan2003

    • Author(s)
      R.Miyawaki, S.Matsubara, K.Yokoyama, S.Iwano, K.Hamasaki, I.Yukinori
    • Journal Title

      J.Mineral.Petrol.Sci. 98

      Pages: 137-141

    • NAID

      10011672268

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Watatsumiite, KNa_2LiMn_2V_2Si_8O_<24>, a new mineral from the Tanohata mine, Iwate Prefecture, Japan2003

    • Author(s)
      S.Matsubara, R.Miyawaki, M.Kurosawa, Y.Suzuki
    • Journal Title

      J.Mineral.Petrol.Sci. 98

      Pages: 142-150

    • NAID

      10011672276

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Crystal structure of protoanthophylite : A new mineral from the Takase ultramafic complex, Japan2003

    • Author(s)
      H.Konishi, T.L.Groy I.Dodony, R.Miyawaki, S.Matsubara, P.R.Buseck
    • Journal Title

      American Mineralogist 88

      Pages: 1718-1723

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Kozoite-(La), La(CO_3)(OH), a new mineral from Mitsukoshi, Hizen-cho, Saga Prefecture, Japan.2003

    • Author(s)
      R.Miyawaki, S.Matsubara, K.Yokoyama, S.Iwano, K.Hamasaki, I.Yukinori
    • Journal Title

      Journal of Mineralogical and Petrological Sciences 98

      Pages: 137-141

    • NAID

      10011672268

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] 「研究成果報告書概要(欧文)」より2003

    • Author(s)
      S.Matsubara, R.Miyawaki, M.Kurosawa, Y.Suzuki, S.Matsubara, R.Miyawaki, M.Kurosawa, Y.Suzuki
    • Journal Title

      Journal of Mineralogical and Petrological Sciences 98

      Pages: 142-150

    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Crystal structure of protoanthophyllite : A new mineral from the Takase ultramafic complex, Japan.2003

    • Author(s)
      H.Konishi, TL.Groy I.Dodony, R.Miyawaki, S.Matsubara, P.R.Buseck
    • Journal Title

      American Mineralogist 88

      Pages: 1718-1723

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] The crystal structure of rengeite, Sr4ZrTi_4(Si_2O_7)_2O_82002

    • Author(s)
      R.Miyawaki, S.Matsubara, H.Miyajima
    • Journal Title

      Journal of Mineralogical and Petrological Scicences 97(1)

      Pages: 7-12

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Matsubaraiite, Sr_4Ti_5Si_4O_<22>, a new mineral, the Sr-Tir analogue of perrierite in jadeitite from the Itoigawa-Ohmi district, Niigata Prefecture, Japan2002

    • Author(s)
      H.Miyajima, R.Miyawaki, K.Ito
    • Journal Title

      European Journal of Mineralogy 14(6)

      Pages: 1119-1128

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Potassicleakeite, a new amphibole from the Tanohata Mine, Iwate Prefecture, Japan2002

    • Author(s)
      S.Matsubara, R.Miyawaki, M.Kurosawa, Y.Suzuki
    • Journal Title

      J.Mineral.Petrol.Sci. 97

      Pages: 177-184

    • NAID

      130000254866

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] The crystal structure of rengeite, Sr4ZrTi_4(Si_2O_7)_2O_8.2002

    • Author(s)
      R.Miyawaki, S.Matsubara, H.Miyajima
    • Journal Title

      Journal of Mineralogical and Petrological Sciences 97

      Pages: 7-12

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Matsubaraiite, Sr_4Ti_5Si_4O_<22>, a new mineral, the Sr-Tir analogue of perrierite in jadeitite from the Itoigawa-Ohmi district, Niigata Prefecture, Japan.2002

    • Author(s)
      H.Miyajima, R.Miyawaki, K.Ito
    • Journal Title

      European Journal of Mineralogy 14

      Pages: 1119-1128

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Potassicleakeite, a new amphibole from me Tanohata Mine, Iwate Prefecture, Japan.2002

    • Author(s)
      S.Matsubara, R.Miyawaki, M.Kurosawa, Y.Suzuki
    • Journal Title

      Journal of Mineralogical and Petrological Sciences 97

      Pages: 177-184

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Publications] R.Miyawaki, S.Matsubara, K.Yokoyama, S.Iwano, K.Hamasaki, I.Yukinori: "Kozoite-(La),La(CO_3)(OH), a new mineral from Mitsukoshi, Hizen-cho, Saga Prefecture, Japan"J.Mineral.Petrol.Sci.. 98. 137-141 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] S.Matsubara, R.Miyawaki, M.Kurosawa, Y.Suzuki: "Watatsumiite, KNa_2LiMn_2V_2Si_8O_<24>, a new mineral from the Tanohata mine, Iwate Prefecture, Japan"J.Mineral.Petrol.Sci.. 98. 142-150 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Konishi, T.L.Groy, I.Dodony, R.Miyawaki, S.Matsubara, P.R.Buseck: "Crystal structure of protoanthophyllite : A new mineral from the Takase ultramafic complex, Japan"American Mineralogist. 88. 1718-1723 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Miyajima, R.Miyawaki, K.Ito: "Matsubaraiite, Sr_4Ti_5Si_4O_<22>, a new mineral, the Sr-Tir analogue of perrierite in jadeitite from the Itoigawa-Ohmi district, Niigata Prefecture, Japan"European Journal of Mineralogy. 14(6). 1119-1128 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] S.Matsubara, R.Miyawaki, M.Kurosawa, Y.Suzuki: "Potassicleakeite, a new amphibole from the Tanohata Mine, Iwate Prefecture, Japan"J. Mineral. Petrol. Sci.. 97. 177-184 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Ritsuro MIYAWAKI他: "The crystal structure of rengeite, Sr4ZrTi4(Si2O7)208"Journal of Mineralogical and Petrological Scicences. 97・1(印刷中). (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] 宮脇律郎他(分執) 日本分析化学会編: "改訂五版分析化学便覧"丸善. 806 (2002)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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