Experimental evidence for partial Fe2+ disorder at the Y and Z sites of tourmaline; a combined EMP, SREF, MS, IR and OAS study of schorl

An experimental study of an Al-rich schorl sample from Cruzeiro mine (Minas Gerais, Brazil) was carried out using electron microprobe analysis, structural refinement and Mossbauer, infrared and optical absorption spectroscopy in order to explore the disordering of Fe2+ over the Y and Z sites of the tourmaline structure.A structural formula was obtained by merging chemical and structural data. The cation distribution at the two non-equivalent octahedrally coordinated sites (Y and Z) was obtained by two different optimization procedures which, minimizing the residuals between observed and calculated data, converged to the formula: X(Na0.65∎0.32Ca0.02K0.01)Σ1.00 Y(Fe2+1.65 Al1.15Fe3+0.06Mn2+0.05 Zn0.05Ti4+0.04)Σ3.00 Z(Al5.52Fe2+0.30 Mg0.18)Σ6.00[T(Si5.87Al0.13)Σ6.00O18]( BBO3)3 V(OH)3 W[(OH)0.34F0.28O0.38]Σ1.00.This result shows a partial disordering of Fe2+ over the Y and Z sites which explains adequately the mean atomic number observed for the Z site (13.5±0.1). Such a disordering is also in line with the shoulder recorded in the Mossbauer spectrum (fitted by a doublet with isomer shift of 1.00 mm/s and quadrupole splitting of 1.38 mm/s) as well as with the asymmetric bands recorded in the optical absorption spectrum at ∼9000 and 14,500 cm-1 (modelled by four Gaussian bands, centred at 7677 and 9418 cm-1, and 13,154 and 14,994 cm-1, respectively).The high degree of consistency in the results obtained using the different methods suggests that the controversy over Fe2+ order can be ascribed to the failure to detect small amounts of Fe2+ at Z (typically