Crystal chemistry of volcanic allanites indicative of naturally induced oxidation-dehydrogenation     

Mihoko Hoshino  Mitsuyoshi Kimata  Craig A. Chesner  Norimasa Nishida  Masahiro Shimizu  Takeshi Akasaka 《Mineralogy and Petrology》2010,99(1-2):133-141

The crystal chemistry of volcanic allanites from both the Youngest Toba Tuff (YTT), Sumatra, Indonesia and SK100 volcanic ash beds (SK100-VAB), Niigata, Japan has been examined by electron microprobe analysis (EMPA), Fourier-transform infrared spectroscopic analysis (FTIR), and single-crystal structure analysis. In the FTIR study, based on the Diamond ATR accessory, YTT and SK100- VAB allanites were observed to have different OH contents, respectively: the former has 0.64 wt% H₂O (OH: 0.40 apfu.), while the latter has 1.65 wt% H₂O (OH: 1.00 apfu.). The crystal structures of these two allanites have been refined to individual R indices (3.64 and 4.25) based on 1350 observed reflections (|Fo| > 4sig|Fo|) measured using a single-crystal diffractometer with MoKα X-radiation. The OH-poor YTT allanite has a shorter b axis, a longer c axis, and larger β value than the relatively OH-rich SK100-VAB one. The bond valence sums of O4 (accepter oxygen for H atom) and O10 (donor oxygen for H atom) are 1.962 and 1.709 v.u. for YTT allanite (valence sum: 3.671 v.u.) and 1.754 and 1.271 v.u. for SK100-VAB one (valence sum: 3.025 v.u.). The difference from the ideal total bond valence value (4.00 v.u.) of O4 and O10 in YTT allanite (0.33 v.u.) is smaller than that in SK100-VAB (0.98 v.u.). These difference values are also broadly consistent with the corresponding differences in OH content between the YTT (OH: 0.40 apfu.) and SK100-VAB allanites (OH: 1.00 apfu.) determined by FTIR- ATR. Chemical analyses, FTIR-ATR and crystal structure refinement of YTT and SK100-VAB allanites yielded the following crystal chemical formula: YTT: (Ca_0.83Mn²⁺ _0.06Fe²⁺ _0.11)(La_0.24Ce_0.32Pr_0.04Nd_0.11Sm_0.02Th_0.04Ca_0.21)(Al_0.73Fe³⁺ _0.19Ti_0.08)(Al_0.89Fe³⁺ _0.11)(Fe²⁺ _0.22Fe³⁺ _0.62Mg_0.16)(SiO₄)Si₂O₇O_1.6(OH)_0.4, SK100-VAB: (Ca_0.81Fe²⁺ _0.13Mn²⁺ _0.06)(La_0.22Ce_0.34Pr_0.05Nd_0.13Sm_0.02Th_0.02Ca_0.22)(Al_0.76Fe³⁺ _0.19Ti_0.05)Al_1.00(Fe²⁺ _0.73Fe³⁺ _0.17Mg_0.10)(Si_0.96Al_0.04O₄)Si₂O₇O(OH). Therefore, it is concluded that welding of the Youngest Toba Tuff caused the following post-crystallization changes to occur in YTT allanite: oxidation of Fe²⁺ to Fe³⁺, release of H₂, and the concomitant replacement of OH^? by O^2?. These oxidation and dehydrogenation processes advanced during the welding to thereby produce oxyallanite. Oxyallanite had been reported only in laboratory studies where it was produced by heating natural allanite. Our report on natural oxyallanite suggests that it may be present in other welded silicic volcanic rocks as well.  相似文献   

Organic matters and acid‐sulfate alteration in Itomuka mercury mine,Hokkaido, Japan: Implications for the transportation and deposition mechanisms of Hg     

Takuya Echigo  Mitsuyoshi Kimata  Masahiro Shimizu 《Resource Geology》2020,70(2):204-213

In order to examine the transportation and deposition mechanisms of Hg, we investigated the ore and hydrothermal alteration minerals and solid organic matters from Itomuka mercury mine located in the eastern part of central Hokkaido. In addition to the ore minerals, native mercury and cinnabar, quartz, marcasite, alunite, kaolinite, and minor amounts of pyrite and smectite were identified in the Hg ore by powder X‐ray diffraction (XRD) analysis. This mineral assemblage of acid sulfate alteration was likely developed under the conditions of low temperature (≤100°C) and low pH (≤2) in the steam‐heated environment. The H₂SO₄ was produced above the water table by the oxidation of H₂S separated from deep, near‐neutral fluids by boiling. The dominance of native mercury over cinnabar in Hg ore indicates that the greater part of mineralized Hg was transported as Hg⁰ in aqueous solution and vapor with low sulfur fugacity. The solid organic matters found in the Hg ore were analyzed with SEM‐EDS, micro‐XRD, and micro‐Fourier transform infrared (FTIR) spectroscopy, and these results suggest that the organic matters contributed to keeping the low fO₂ of the Hg‐bearing fluid and transportation of Hg as Hg⁰ in S‐poor condition. Because the solubility of Hg in acidic fluid is low, neutral to alkaline fluid seems to have leached Hg from the basement sedimentary rocks of Hidaka Group which also supplied the organic matters to the fluid. The oxidation and cooling of Hg‐bearing solution and vapor triggered the deposition of liquid Hg as a primary phase.  相似文献   

Magma intrusion and discharge process at the initial stage of the 2000 activity of Miyakejima, Central Japan, inferred from tilt and GPS data   总被引：2，自引：0，他引：2  

Hideki Ueda  Eisuke Fujita  Motoo Ukawa  Eiji Yamamoto  Meilano Irwan  Fumiaki Kimata 《Geophysical Journal International》2005,161(3):891-906

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Single-crystal X-ray diffraction and spectroscopic studies on humboldtine and lindbergite: weak Jahn–Teller effect of Fe<Superscript>2+</Superscript> ion     

Takuya Echigo  Mitsuyoshi Kimata 《Physics and Chemistry of Minerals》2008,35(8):467-475

The single-crystal of humboldtine [Fe²⁺(C₂O₄) · 2H₂O] was first synthesized and the crystal structure has been refined. Single-crystal X-ray diffraction data were collected using an imaging-plate diffractometer system and graphite-monochromatized MoKα radiation. The crystal structure of humboldtine was refined to an agreement index (R1) of 3.22% calculated for 595 unique observed reflections. The mineral crystallizes in the monoclinic system, space group C2/c, with unit cell dimensions of a = 12.011 (11), b = 5.557 (5), c = 9.920 (9) Å, β = 128.53 (3)?, V = 518.0 (8) Å³, and Z = 4. In this crystal structure, the alternation of oxalate anions [(C₂O₄)^2?] and Fe²⁺ ions forms one-dimensional chain structure parallel to [010]; water molecules (H₂O)⁰ create hydrogen bonds to link the chains, where (H₂O)⁰ is essentially part of the crystal structure. The water molecules with the two lone electron pairs (LEPs) on their oxygen atom are tied obliquely to the chains, because the one lone electron pair is considered to participate in the chemical bonds with Fe²⁺ ions. Humboldtine including hydrogen bonds is isotypic with lindbergite [Mn²⁺(C₂O₄) · 2H₂O]. The donor–acceptor separations of the hydrogen bonds in humboldtine are slightly shorter than those in lindbergite, which suggests that the hydrogen bonds in the former are stronger than those in the latter. The infrared and Raman spectra of single-crystals of humboldtine and lindbergite confirmed the differences in hydrogen-bond geometry. In addition, Fe²⁺–O stretching band of humboldtine was split and broadened in the observed Raman spectrum, owing to the Jahn–Teller effect of Fe²⁺ ion. These interpretations were also discussed in terms of bond-valence theory.  相似文献