Octahedral M3 Research Articles

Low-temperature infrared spectrum and atomic-scale structure of hydrous defects in diopside

Abstract. Hydrous defects in diopside (CaMgSi2O6) play an important role in the water budget of the Earth's mantle. Related OH-stretching modes lead to a variety of infrared absorption bands observed in natural or experimental samples. In the present study, we report new low-temperature infrared spectra of reference natural diopside samples in the OH-stretching range. In parallel, the structure and vibrational properties of a series of OH-bearing defects in diopside are theoretically determined at the density functional theory level. The infrared spectra make it possible to resolve additional bands in the region above 3600 cm−1 and reveal that their anharmonic behavior differs from that of the bands at lower frequency. A comparison of theoretical results with experimental data makes it possible to propose atomic-scale geometries corresponding to observed OH-stretching bands. It confirms that the bands observed at 3620–3651 cm−1 are related to M3+ ions substituted for Si in tetrahedral sites, while the 3420 cm−1 band is associated with the Na+ for Ca2+ substitution. In both cases, H+ incorporation compensates the charge deficit due to the heterovalent substitution. The other major mechanism of water incorporation in diopside relates to the charge compensation of cationic vacancies, among which Ca vacancies play a central role. The 3357 cm−1 band corresponds to doubly protonated Ca vacancies in pure diopside. In experimental diopside-bearing trivalent cations, the bands at 3432–3460 cm−1 correspond to singly protonated Ca vacancies with a nearby octahedral M3+ ion, while the 3310 cm−1 band likely involves a more remote charge compensation by M3+ ions. More complex defects associating Ca vacancies with tetrahedral M3+ and octahedral Ti4+ ions are proposed for the bands observed between 3500 and 3600 cm−1 in natural diopside. The Fe2+ for Mg2+ and Fe2+ for Ca2+ substitutions are also found to affect nearby OH-bearing defects, causing a shift and broadening of OH stretching bands in chemically more complex diopside samples.

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

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.

A crystal-chemical investigation of clinozoisite synthesized along the join Ca2Al3Si3O12(OH)-Ca2Al2CrSi3O12(OH)

Cr 3+ -bearing clinozoisite along the join Ca 2 Al 3 Si 3 O 12 (OH)-Ca 2 Al 2 Cr 3+ Si 3 O 12 (OH) was synthesized using cold-seal pressure vessels at P H 2 O = 0.35 to 0.40 GPa and T = 500 °C and a piston-cylinder apparatus at P H 2 O = 0.8 to 1.5 GPa and T = 500 to 800 °C. Gel-starting materials of Ca 2 Al 3– q Cr 3+ q Si 3 O 12.5 composition with q = 1.00, 0.75, 0.50, and 0.25 were employed to maximize the yields of clinozoisite. Mass fractions of clinozoisite in the experimental products with q = 0.50, 0.75, and 1 were about 70 to 90% along with lesser amounts of eskolaite, garnet, and quartz. Clinozoisite crystallized from the gel with q = 0.25 was associated only with zoisite. The crystal structures of clinozoisite in four runs, containing 0.28, 0.49, 0.50, and 0.62 Cr apfu were refined using X-ray powder diffraction data and the Rietveld method. The amount of Cr 3+ at the octahedral M3 and M1 sites ranged from 0.37(1)–0.16(1) to 0.25(1)–0.12(1) apfu, respectively. Corresponding K D = (Cr 3+ /Al) M1 /(Cr 3+ /Al) M3 values range between 0.57 and 0.73. The M2 site contained only Al. The K D values, and published results for intracrystal-line partitioning in epidote and piemontite, show that the preference of Cr 3+ for M1 is stronger than that of Fe 3+ and Mn 3+ in spite of the fact that most Cr 3+ is partitioned into M3. Unit-cell parameters of clinozoisite increase with increasing Cr 3+ . Variations in macroscopic unit-cell parameters can be related to variations in the local M3-O i and M1-O i distances.

Über kristallines Chrom(III)hydroxid. I

AbstractWhen hydroxide ions are added to a solution of Cr(H2O)63+ ions at low temperature a well crystallized chromium hydroxide hydrate is formed, corresponding to the formula [Cr(OH)3‐(H2O)3]∞. Its structure is the inverse of bayerite type, two thirds of the octahedral M3+ positions being vacant. It loses water easily and turns into a totally amorphous hydroxide of variable water content. An amorphous hydroxide is also obtained when solutions are alkalized at higher temperatures or when aged solutions (containing polynuclear complexes) are used.