OH in zoned amphiboles of eclogite from the western Tianshan, NW-China

Chemically-zoned amphibole porphyroblast grains in an eclogite (sample ws24-7) from the western Tianshan (NW-China) have been analyzed by electron microprobe (EMP), micro Fourier-transform infrared (micro-FTIR) and micro-Raman spectroscopy in the OH-stretching region. The EMP data reveal zoned amphibole compositions clustering around two predominant compositions: a glaucophane end-member (^BNa₂ ^CM²⁺₃ M³⁺₂ ^TSi₈(OH)₂) in the cores, whereas the mantle to rim of the samples has an intermediate amphibole composition (^A_0.5^BCa_1.5Na_0.5 ^CM²⁺_4.5 M_0.5^{3+ T}Si_7.5Al_0.5(OH)₂) (A = Na and/or K; M²⁺ = Mg and Fe²⁺; M³⁺ = Fe³⁺ and/or Al) between winchite (and ferro-winchite) and katophorite (and Mg-katophorite). Furthermore, we observed complicated FTIR and Raman spectra with OH-stretching absorption bands varying systematically from core to rim. The FTIR/Raman spectra of the core amphibole show three lower-frequency components (at 3,633, 3,649-3,651 and 3,660-3,663 cm^-1) which can be attributed to a local O(3)-H dipole surrounded by ^M(1)M(3)Mg₃, ^M(1)M(3)Mg₂Fe²⁺ and ^M(1)M(3) Fe²⁺₃, respectively, an empty A site and ^TSi₈ environments. On the other hand, bands at higher frequencies (3,672-3,673, 3,691-3,697 and 3,708 cm^-1) are observable in the rims of the amphiboles, and they indicate the presence of an occupied A site. The FTIR and Raman data from the OH-stretching region allow us to calculate the site occupancy of the A, M(1)-M(3), T sites with confidence when combined with EPM data. By contrast M(2)- and M(4) site occupancies are more difficult to evaluate. We use these samples to highlight on the opportunities and limitations of FTIR OH-stretching spectroscopy applied to natural high pressure amphibole phases. The much more detailed cation site occupancy of the zoned amphibole from the western Tianshan have been obtained by comparing data from micro-chemical and FTIR and/or Raman in the OH-stretching data. We find the following characteristic substitutions Si(T-site) (Mg, Fe)[M(1)-M(3)-site] → Al(T-site) Al[M(1)-M(3)-site] (tschermakite), Ca(M4-site)□ (A-site) → Na(M4-site) Na + K(A-site) (richterite), and Ca(M4-site) (Mg, Fe) [M(1)-M(3)-site] → Na(M4-site) Al[M(1)-M(3)-site] (glaucophane) from the configurations observed during metamorphism.