TY - JOUR
T1 - Synthesis and crystal chemistry of mukhinite, V-analogue of clinozoisite on the join Ca 2 Al 3 Si 3 O 12 (OH)–Ca 2 Al 2 VSi 3 O 12 (OH)
AU - Nagashima, Mariko
AU - Nishio-Hamane, Daisuke
AU - Nakano, Nobuhiko
AU - Kawasaki, Toshisuke
N1 - Funding Information:
Acknowledgements Prof. Y. Osanai of Kyushu University is thanked for his permission to use the Raman spectrometer (JASCO NRS-3100), and Prof. M. Akasaka of Shimane University for his permission to use X-ray single-crystal diffractometer (Bruker SMART APEXII). One of the authors (M.N.) also thanks Prof. Y. Sampei for preliminary Raman spectroscopic study, Dr. K. Yoza for his advice of structural refinement, Mr. Y. Morifuku for technical assistance of high-pressure experiments, and Profs. T. Armbruster and M. Akasaka for their thoughtful revisions of an earlier version of this manuscript. We also thank the Editor Prof. M. Rieder, and the reviewers Prof. P. Bačik and Prof. P. Bonazzi for their constructive comments. The TEM session was performed at facilities of the Institute for Solid State Physics, University of Tokyo (project No. AG60). We gratefully acknowledge the financial supports of Grants-in-Aid for Scientific Research from the Japan Society for the Promotion of Science, nos. 285800296, 19H03748, and 17K05709.
Funding Information:
Prof. Y. Osanai of Kyushu University is thanked for his permission to use the Raman spectrometer (JASCO NRS-3100), and Prof. M. Akasaka of Shimane University for his permission to use X-ray single-crystal diffractometer (Bruker SMART APEXII). One of the authors (M.N.) also thanks Prof. Y. Sampei for preliminary Raman spectroscopic study, Dr. K. Yoza for his advice of structural refinement, Mr. Y. Morifuku for technical assistance of high-pressure experiments, and Profs. T. Armbruster and M. Akasaka for their thoughtful revisions of an earlier version of this manuscript. We also thank the Editor Prof. M. Rieder, and the reviewers Prof. P. Bačik and Prof. P. Bonazzi for their constructive comments. The TEM session was performed at facilities of the Institute for Solid State Physics, University of Tokyo (project No. AG60). We gratefully acknowledge the financial supports of Grants-in-Aid for Scientific Research from the Japan Society for the Promotion of Science, nos. 285800296, 19H03748, and 17K05709.
Publisher Copyright:
© 2018, Springer-Verlag GmbH Germany, part of Springer Nature.
PY - 2019/1/21
Y1 - 2019/1/21
N2 - This is the first report of the crystal structure of mukhinite, V-analogue clinozoisite, on the join Ca 2 Al 3 Si 3 O 12 (OH)–Ca 2 Al 2 V 3+ Si 3 O 12 (OH) synthesized at 1.5 GPa and 800 °C. The study was performed to clarify the distribution of V 3+ among structurally independent octahedral M1, M2, and M3 sites, and the effect of V 3+ on the crystal structure. Mukhinite and V 3+ -bearing clinozoisite in all run products are associated with zoisite, and also coexist with V-bearing phases such as vanadomalayaite, goldmanite, V-oxides, and unidentified Ca–Al-bearing vanadates. Mukhinite and V 3+ -bearing clinozoisite crystallized in the Run 20 product show a compositional gap between 0.33 and 0.74 V atoms per formula unit (apfu), and the V content attains 1.14 apfu. The coexistence of low V 3+ - and high V 3+ -clinozoisites indicates the presence of a miscibility gap at 1.5 GPa and 800 °C. Two mukhinite crystals with 0.75 and 0.83 V 3+ apfu were used for X-ray single-crystal structure analysis. The unit-cell parameters are a = 8.8995(2), b = 5.6299(1), c = 10.1532(2) Å, β = 115.327(1)°, and V = 459.81(2) Å 3 for the former, and a = 8.8999(1), b = 5.6357(1), c = 10.1499(1) Å, β = 115.306(1)°, and V = 460.24(2) Å 3 for the latter. The resulting V 3+ occupancies among the octahedral sites are M1 (Al 0.894(6) V 0.106 ) M2 (Al 0.976(6) V 0.024 ) M3 (V 0.621(6) Al 0.379 ) for the former and M1 (Al 0.868(4) V 0.132 ) M2 (Al 0.957(4) V 0.043 ) M3 (V 0.652(2) Al 0.348 ) for the latter. Site preference of V 3+ at the octahedral sites is M3 > M1 > M2 as that of Fe 3+ and Mn 3+ . The intracrystalline partition coefficient of V 3+ and Al 3+ between the M1 and M3 sites, K D = (V 3+ /Al) M1 /(V 3+ /Al) M3 , is 0.07–0.08, which is greater than those of Fe 3+ and Al 3+ (0.03–0.05) and of Mn 3+ and Al 3+ (0.04–0.06). Variations of the unit-cell parameters are strongly related to the variations of the M3−Oi and M1−Oi distances.
AB - This is the first report of the crystal structure of mukhinite, V-analogue clinozoisite, on the join Ca 2 Al 3 Si 3 O 12 (OH)–Ca 2 Al 2 V 3+ Si 3 O 12 (OH) synthesized at 1.5 GPa and 800 °C. The study was performed to clarify the distribution of V 3+ among structurally independent octahedral M1, M2, and M3 sites, and the effect of V 3+ on the crystal structure. Mukhinite and V 3+ -bearing clinozoisite in all run products are associated with zoisite, and also coexist with V-bearing phases such as vanadomalayaite, goldmanite, V-oxides, and unidentified Ca–Al-bearing vanadates. Mukhinite and V 3+ -bearing clinozoisite crystallized in the Run 20 product show a compositional gap between 0.33 and 0.74 V atoms per formula unit (apfu), and the V content attains 1.14 apfu. The coexistence of low V 3+ - and high V 3+ -clinozoisites indicates the presence of a miscibility gap at 1.5 GPa and 800 °C. Two mukhinite crystals with 0.75 and 0.83 V 3+ apfu were used for X-ray single-crystal structure analysis. The unit-cell parameters are a = 8.8995(2), b = 5.6299(1), c = 10.1532(2) Å, β = 115.327(1)°, and V = 459.81(2) Å 3 for the former, and a = 8.8999(1), b = 5.6357(1), c = 10.1499(1) Å, β = 115.306(1)°, and V = 460.24(2) Å 3 for the latter. The resulting V 3+ occupancies among the octahedral sites are M1 (Al 0.894(6) V 0.106 ) M2 (Al 0.976(6) V 0.024 ) M3 (V 0.621(6) Al 0.379 ) for the former and M1 (Al 0.868(4) V 0.132 ) M2 (Al 0.957(4) V 0.043 ) M3 (V 0.652(2) Al 0.348 ) for the latter. Site preference of V 3+ at the octahedral sites is M3 > M1 > M2 as that of Fe 3+ and Mn 3+ . The intracrystalline partition coefficient of V 3+ and Al 3+ between the M1 and M3 sites, K D = (V 3+ /Al) M1 /(V 3+ /Al) M3 , is 0.07–0.08, which is greater than those of Fe 3+ and Al 3+ (0.03–0.05) and of Mn 3+ and Al 3+ (0.04–0.06). Variations of the unit-cell parameters are strongly related to the variations of the M3−Oi and M1−Oi distances.
UR - http://www.scopus.com/inward/record.url?scp=85049856758&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85049856758&partnerID=8YFLogxK
U2 - 10.1007/s00269-018-0988-4
DO - 10.1007/s00269-018-0988-4
M3 - Article
AN - SCOPUS:85049856758
SN - 0342-1791
VL - 46
SP - 63
EP - 76
JO - Physics and Chemistry of Minerals
JF - Physics and Chemistry of Minerals
IS - 1
ER -