Multi-methodical study of the Ti, Fe2+ and Fe3+ distribution in chevkinite-subgroup minerals: X-ray diffraction, neutron diffraction, 57Fe Mössbauer spectroscopy and electron-microprobe analyses
Source abstract
Abstract
Three non-metamict chevkinite-subgroup minerals, space group P21/a, from Cape Ashizuri, Japan, (No. 1), Tangir Valley, Diamar District, Pakistan (No. 2) and Haramosh Mts., Skardu district, Pakistan, (No. 3) were studied by crystal chemical techniques. Powder X-ray diffraction and transmission electron microscopic observations confirmed well crystalline samples. Electron-microprobe analyses indicated the general composition [(REE, Ca)4Fe2+(Fe2+, Fe3+, Ti)2Ti2(Si2O7)2O8] known for chevkinite-(Ce). Site scattering values determined by single-crystal X-ray structure refinements suggested assignment of subordinate Nb to the octahedral M3 and M4 sites, minor Th to M1 for the Ashizuri sample and minor Mg to M1 for both samples from Pakistan. Neutron time-of-flight powder diffraction studies were applied to determine the Ti/Fe distribution among octahedral sites for all samples and Mossbauer spectroscopy served for the Fe valence assignment at the four octahedral sites. Combined results gave the simplified formulas with Ce as dominant REE: No. 1 A(REE,Ca)4M1(Fe2+,Ti)M2(Ti,Fe3+)2M3,M4(Ti,Fe2+,Nb)2(Si2O7)2O8, No. 2 A(REE,Ca)4M1(Fe2+,Fe3+,Mg)M2(Ti,Fe3+)2M3,M4(Ti,Fe2+)2(Si2O7)2O8 and No. 3 A(REE,Ca)4M1(Fe3+,Fe2+,Mg,Ti)M2(Ti,Fe3+)2M3,M4(Ti,Fe2+)2(Si2O7)2O8. The dominant iron valence at M1 of the Haramosh sample (No. 3) is ferric whereas for samples Nos. 1 and 2 iron is ferrous. The structure of chevkinite-subgroup minerals consists of octahedral layers (M2, M3 and M4) alternating with an intermediate layer containing disilicate groups, REE polyhedra and strongly distorted M1 octahedra. Increased O atomic displacement parameters within the intermediate layers indicate disorder and/or strain to fit the extension of the embracing octahedral layers. A statistical analysis of chevkinite-subgroup structures (space groups P21/a, C2/m and P21/m) indicates a positive correlation between bond length and M1 bond angle variance. A negative correlation is found between bond length and the disilicate bending angle Si–O–Si, varying between ca. 160° and 175°. Outliers of this trend are delhuyarite-(Ce) Ce4Mg(Fe3+2W)□(Si2O7)2O6(OH)2, mainly due to octahedral W6+ and vacancies in the octahedral layers associated with OH groups, and synthetic Nd end-members with strong bonds between Nd and the intersecting O of the disilicate group. The observed trends reflect the main mechanisms in the intermediate layer to adopt to the size of the embracing rigid octahedral layers formed by M2, M3 and M4 octahedra.
Source: openaire · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: Geological and Geochemical Analysis · Crystal Structures and Properties · High-pressure geophysics and materials
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (62)
Show source-provided references
1. Akasaka M, Shinno I (1992) Mössbauer spectroscopy and its recent application to silicate mineralogy. J Miner Soc Japan 21:3–20 (In Japanese with English abstract)
2. Amthauer G, Rossman GR (1984) Mixed valence of iron in minerals with cation clusters. Phys Chem Miner 11:37–5110.1007/BF00309374 ↗
3. Anders E, Grevesse N (1989) Abundances of the elements: meteoritic and solar. Geochim Cosmochim Acta 53:197–21410.1016/0016-7037(89)90286-X ↗
4. Bagiński B, Macdonald R (2013) The chevkinite group: underestimated accessory phases from a wide range of parageneses. Mineralogia 44:99–11410.2478/mipo-2013-0006 ↗
5. Baur H (1974) The geometry of polyhedral distortions. Predictive relationships for the phosphate group. Acta Crystallogr B 30:1195–121510.1107/S0567740874004560 ↗
6. Belkin HE, Macdonald R, Grew ES (2009) Chevkinite-group minerals from granulite-facies metamorphic rocks and associated pegmatites of East Antarctica and South India. Miner Mag 73:149–16410.1180/minmag.2009.073.1.149 ↗
7. Bender FK, Raza HA (1995) Geology of Pakistan. Gebrüder Borntraeger Verlagsbuchhandlung, Stuttgart
8. Brown ID, Altermatt D (1985) Bond-valence parameters obtained from a systematic analysis of the inorganic crystal structure database. Acta Crystallogr B 41:244–24710.1107/S0108768185002063 ↗
9. Bruker AXS Inc (1999) SMART and SAINT–Plus. Versions 6.01. Bruker AXS Inc., Madison
10. Burg JP, Jagoutz O, Hamid D, Hussain S (2006) Precollision tilt of crustal blocks in rifted island arcs: structural evidence from the Kohistan Arc. Tectonics 25:TC500510.1029/2005TC001835 ↗
11. Calvo C, Faggiani R (1974) A re-investigation of the crystal structures of chevkinite and perrierite. Am Miner 59:1277–1285
12. Chukanov NV, Aksenov S, Rastsvetaeva RK, Belakovskiy DI, Göttlicher J, Britvin SN, Möckel S (2012) Christofschäferite-(Ce), (Ce, La, Ca)4Mn2+(Ti, Fe3+)3(Fe3+, Fe2+, Ti)(Si2O7)2O8—a new chevkinite-group mineral from the Eifel area, Germany. New Data Miner 47:33–42
13. Gottardi G (1960) The crystal structure of perrierite. Am Miner 45:1–14
14. Hattori T, Sano-Furukawa A, Arima H, Komatsu K, Yamada A, Inamura Y, Nakatani T, Seto Y, Nagai T, Utsumi W, Iitaka T, Kagi H, Katayama Y, Inoue T, Otomo T, Suzuya K, Iamiyama T, Arai M, Yagi T (2015) Design and performance of high-pressure PLANET beamline at pulsed neutron source at J-PARC. Nucl Instrum Methods Phys Res A780:55–6710.1016/j.nima.2015.01.059 ↗
15. Holtstam D, Bindi L, Hålenius U, Andersson UB (2017) Delhuyarite-(Ce)—Ce4Mg(Fe3+2W)□(Si2O7)2O6(OH)2—a new mineral of the chevkinite group, from the Nya Bastnäs Fe-Cu-REE deposit, Sweden. Eur J Miner 29:897–90510.1127/ejm/2017/0029-2635 ↗
16. Imaoka T (1994) Chevkinite in syenite from Cape Ashizuri, Shikoku Island, Japan. N Jb Miner Monats H8:358–36610.1127/njmm/1994/1994/358 ↗
17. Ishihara S, Hoshino M (2013) Zircon and REE-rich alkaline plutonic rocks intruded into the accretionary prism at the Cape Ashizuri, Shikoku Island, Japan. Bull Geol Surv Jp 64:1–2410.9795/bullgsj.64.1 ↗
18. Ito J (1967) A study of chevkinite and perrierite. Am Miner 52:1094–1104
19. Ito J, Arem E (1971) Chevkinite and perrierite: synthesis, crystal growth and polymorphism. Am Miner 56:307–319
20. Jagoutz OE, Müntener O, Ulmer P, Pettke T, Burg J-P, Dawood H, Hussain S (2007) Petrology and mineral chemistry of lower crustal intrusions: the Chilas Complex, Kohistan (NW Pakistan). J Petrol 48:1895–195310.1093/petrology/egm044 ↗
21. Khan MA, Jan MQ, Windley BF, Tarney J, Thirlwall MF (1989) The Chilas mafic-ultramafic igneous complex; the root of the Kohistan island arc in the Himalaya of the northern Pakistan. In: Malinconico LL Jr, Lillie RJ (eds) Tectonics of the Western Himalayas, 232nd edn. Geological Society of America, Washington, pp 75–9410.1130/SPE232-p75 ↗
22. Liu Y, Ma C (2015) Monazite, chevkinite-perrierite and xenotime in Martian breccia meteorite NWA7034. IN: 46th lunar and planetary science conference 2015, p 1287
23. Liu Y, Ma C, Beckett J, Guan Y (2015) Rare-earth minerals in the Martian meteorite NWA7034/7533: evidence for fluid-rock interaction in the Martian crust. In: 78th annual meeting of the meteoritical society, p 505110.1016/j.epsl.2016.06.041 ↗
24. Liu Y, Ma C, Beckett JR, Chen Y, Guan Y (2016) Rare-earth-element minerals in Martian breccia meteorites NWA7034 and 7533: implications for fluid-rock interaction in the Martian crust. Earth Planet Sci Lett 451:252–26210.1016/j.epsl.2016.06.041 ↗
25. Liziero F (2008a) Studio cristallochimico e strutturale di chevkiniti-(Ce) non metamittiche. Universita’ degli studi di Padova, Padua, p 117
26. Liziero F (2008b) Crystal chemistry and structure of non-metamict chevkinite-(Ce). Plinius 34:90–91
27. Li Z, Jin M, Liu M, Liu X (1992) Iron distribution in chevkinite. Hyperfine Interact 70:1057–106010.1007/BF02397511 ↗
28. Li G, Yang G, Ma Z, Shi N, Xiong M, Fan H, Sheng G (2005) Crystal structure of natural non-metamict Ti- and Fe2+-rich chevkinite-(Ce). Acta Geol Sinica 79:325–33110.1111/j.1755-6724.2005.tb00896.x ↗
29. Longerich HP, Jackson SE, Günther D (1996) Laser ablation inductively coupled plasma mass spectrometric transient signal data acquisition and analyte concentration calculation. J Anal Atom Spectr 11:899–90410.1039/JA9961100899 ↗
30. Macdonald R, Belkin HE (2002) Compositional variation in minerals of the chevkinite group. Miner Mag 66:1075–109810.1180/0026461026660078 ↗
31. Macdonald R, Belkin HE, Wall F, Bagiński B (2009) Compositional variation in the chevkinite group: new data from igneous and metamorphic rocks. Miner Mag 73:777–79610.1180/minmag.2009.073.5.777 ↗
32. Macdonald R, Bagiński B, Belkin HE, Stachowicz M (2019) Composition, paragenesis, and alteration of the chevkinite group of minerals. Am Miner 104:348–36910.2138/am-2019-6772 ↗
33. Momma K, Izumi F (2011) VESTA3 for three-dimensional visualization of crystal, volumetric and morphology data. J Appl Crystallogr 44:1257–127610.1107/S0021889811038970 ↗
34. Momma K, Tsutusmi Y, Sano T, Miyawaki R, Shigeoka M, Yokoyama K (2016) Chevkinite-bearing tuffs from the Boso and Noto Peninsulas in Central Japan and from Primorye, Far East Russia. Mem Natl Mus Nat Sci Tokyo 51:89–98
35. Muhling JR, Suvorova AA, Rasmussen B (2014) The occurrence and composition of chevkinite-(Ce) and perrierite-(Ce) in tholeiitic intrusive rocks and lunar mare basalt. Am Miner 99:1911–192110.2138/am-2014-4690 ↗
36. Murakami N, Imaoka T, Uozumi S (1989) Ring complex of Cape of Ashizuri, and its mode of emplacement, Kochi Prefecture, Southwest Japan. Assoc Geol Collab Jpn Monogr 36:115–142 (in Japanese with English abstract)
37. Nagashima M, Imaoka T, Nakashima K (2011) Crystal chemistry of Ti-rich ferriallanite-(Ce) from Cape Ashizuri, Shikoku Island, Japan. Am Miner 96:1870–187710.2138/am.2011.3830 ↗
38. Noritake F (2019) Revisiting the nature of Si–O–Si bridging. J Comput Chem Jpn Int Edn 5:1–8
39. Noritake F, Kawamura K (2015) The nature of Si-O-Si bonding via molecular orbital calculations. J Comp Chem Japan 14:124–13010.2477/jccj.2015-0009 ↗
40. Oishi-Tomiyasu R, Yonemura M, Morishima T (2012) Application of matrix decomposition algorithms for singular matrices to the Pawley method in Z-Rietveld. J Appl Crystallogr 45:299–30810.1107/S0021889812003998 ↗
41. Oishi R, Yonemura M, Nishimaki Y, Torii S, Hoshikawa A, Ishigaki T, Morishima T, Mori K, Kamiyama T (2009) Rietveld analysis software for J-PARC. Nucl Instrum Methods Phys Res A 600:94–9610.1016/j.nima.2008.11.056 ↗
42. Peng Z, Pan Z (1964) The crystal structure of chevkinite. Sci Sinica 13:1539–1545 (in Russian)
43. Popov VA, Pautov LA, Sokolova E, Hawthorne FC, McCammon C, Bazhenova LF (2001) Polyakovite-(Ce), (REE, Ca)4(Mg, Fe2+)(Cr3+, Fe3+)2(Ti, Nb) 22, a new metamict mineral species from the Ilmen Mountains, Southern Urals, Russia: Mineral description and crystal chemistry. Can Miner 39:1095–110410.2113/gscanmin.39.4.1095 ↗
44. Robinson K, Gibbs GV, Ribbe PH (1971) Quadratic elongation: a quantitative measure of distortion in coordination polyhedra. Science 172:567–57010.1126/science.172.3983.567 ↗
45. Schaltegger U, Zeilinger G, Frank M, Burg JP (2002) Multiple mantle sources during island arc magmatism: U-Pb and Hf isotopic evidence from the Kohistan arc complex, Pakistan. Terra Nova 14:461–46810.1046/j.1365-3121.2002.00432.x ↗
46. Sears VF (1992) Neutron scattering lengths and cross sections. Neutron News 3:26–3710.1080/10448639208218770 ↗
47. Shah MY (2017) Mineral potential in Diamer District. Pamir Times, Kabul, p 24
48. Sheldrick GM (1996) SADABS. University of Göttingen, Germany
49. Sheldrick GM (2015) Crystal structure refinement with SHELX. Acta Crystallogr C 71:3–810.1107/S2053229614024218 ↗
50. Shen G, Yang G, Xu J (2005) Maoniupingite-(Ce): a new rare-earth mineral from the Maoniuping rare-earth deposit in Mianning, Sichuan, China. Sedim Geol Tethyan Geol 25:210–216 (in Chinese with English abstract)
51. Shibata K (1968) K-Ar age determinations on granitic and metamorphic rocks in Japan. Rept Geol Surv Jpn 227:73
52. Shinjoe H, Orihashi Y, Sumii T (2010) U-Pb zircon ages of syenitic and granitic rocks in the Ashizuri igneous complex, western Shikoku: constraint for the origin of forearc alkaline magmatism. Geochem J 44:275–28310.2343/geochemj.1.0070 ↗
53. Sokolova E, Hawthorne FC, Della Ventura G, Kartashov PM (2004) Chevkinite-(Ce): crystal structure and the effect of moderate radiation-induced damage on site-occupancy refinement. Can Miner 42:1013–102510.2113/gscanmin.42.4.1013 ↗
54. Song R, Ding K, Li Z (1999) Site occupancies of iron in saimaite and chevkinite. Chin Sci Bull 44:2274–227610.1007/BF02885938 ↗
55. Stachowicz M, Bagiński B, Macdonald R, Kartashov PM, Oziębło A, Woźniak K (2014) Structure of Sr-Zr-bearing perrierite-(Ce) from the Burpala Massif, Russia. Miner Mag 78:1647–165910.1180/minmag.2014.078.7.08 ↗
56. Stachowicz M, Bagiński B, Welch MD, Kartashov PM, Macdonald R, Balcerzak J, Tyczkowski J, Woźniak K (2019a) Cation ordering, valence states, and symmetry breaking in the crystal-chemically complex mineral chevkinite-(Ce): X-ray diffraction and photoelectron spectroscopy studies and mechanisms of Nb enrichment. Am Miner 104:595–60210.2138/am-2019-6457 ↗
57. Stachowicz M, Welch MD, Bagiński B, Kartashov PM, Macdonald R, Woźniak K (2019b) Cation ordering valence states, and symmetry breaking in the crystal-chemically complex mineral chevkinite-(Ce): recrystallization, transformation, and metamict states in chevkinite. Am Miner 102:1481–148610.2138/am-2019-6458 ↗
58. Xu J, Yang G, Li G, Wu Z, Shen G (2008) Dingdaohengite-(Ce) from the Bayan Obo REE-Nb-Fe mine, China: both a true polymorph of perrierite-(Ce) and a titanic analog at the C1 site of chevkinite subgroup. Am Mineral 93:740–74410.2138/am.2008.2543 ↗
59. Yang Z, Fleck M, Smith M, Tao K, Song R, Zhang P (2002) The crystal structure of natural Fe-rich chevkinite. Eur J Miner 14:969–97510.1127/0935-1221/2002/0014-0969 ↗
60. Yang Z, Li H, Liu M, Pertlik F (2007) Crystal chemistry of iron in non-metamict chevkinite-(Ce): valence state and site occupation proportions. J Rare Earths 25:238–24210.1016/S1002-0721(07)60080-5 ↗
61. Yang Z, Pertlik F, Fleck M (2008) Hydroxyl groups in nonmetamict chevkinite-(Ce): a crystal chemical discussion. J Rare Earths 26:609–61310.1016/S1002-0721(08)60147-7 ↗
62. Young RA (1993) Introduction to the Rietveld method. In: Young RA (ed) The Rietveld Method. Oxford Science Publications, Oxford, pp 1–3810.1093/oso/9780198555773.001.0001 ↗