Thermal treatment of the tourmaline Fe‑rich princivalleite Na(Mn2Al)Al6(Si6O18)(BO3)3(OH)3O

Natural Fe2+-rich princivalleite was thermally treated in the air at 700 °C to study crystal-chemical and color variations due to changes in oxidation states of Fe and Mn and atom ordering. Overall, the experimental data (electron microprobe, structural refinement, Mössbauer, infrared, and optical absorption spectroscopy) show that thermal treatment of princivalleite results in an almost total Fe2+ oxidation to Fe3+ and an oxidation of approximately one-third of Mn2+ to Mn3+ along with a minor degree of disorder of Al–Fe–Mn over the Y and Z sites. This process is accompanied by a significant deprotonation of the sample. The YFe and YMn oxidation from + 2 to + 3 yields in a decrease in a-parameter, whereas the increased content of ZFe3+ results in a minor increase in the c-parameter. Optical absorption spectroscopy shows that the faint blue (azure) color of untreated princivalleite is caused by the presence of Fe2+ and the absence of Ti4+. Thermal treatment in air (700 °C) changed the color to dark brown due to the progressive oxidation of Fe2+ to Fe3+ and Mn2+ to Mn3+, as demonstrated by the evolution of optical absorption bands caused by electron transitions in these 3d-cations. However, the most evident result of the thermal treatment of the Fe-rich princivalleite sample is the simultaneous presence of Fe2+, Fe3+, Mn2+, and Mn3+, with a Fe3+/ΣFe and Mn3+/ΣMn ratio of 0.92 and 0.25, respectively. This observation suggests that the oxidation process during the heating experiments was largely controlled by kinetic factors.