Multi-analytical characterization of an unusual epidote-supergroup mineral from Malmkärra, Sweden: Toward the new (OH)-analog of dollaseite-(Ce) Available to Purchase

A study of a skarn sample from the Malmkärra iron mines, Norberg, Västmanland (Sweden), revealed the occurrence of a peculiar epidote-supergroup mineral. It was examined using electron microprobe, single-crystal X-ray diffraction, Mössbauer, and Fourier-transform infrared spectroscopy (FTIR) techniques. Structure refinements combined with electron microprobe data indicate the following cation populations: $A1=Ca0.96REE0.033+Mn0.01$⁠; $A2=REE0.993+Ca0.01$⁠; $M1=Mg0.40Al0.32Fe0.263+Fe0.022+$⁠; $M2=Al0.98Fe0.023+$⁠; $M3=Mg0.72Fe0.172+Fe0.113+$⁠; T1,2,3 = Si_2.93Al_0.07, accounting for a total positive charge of 24.64. The presence of Fe²⁺ is confirmed by Mössbauer data. The remarkable number of divalent cations at both M1 and M3 (>1 pfu, per formula unit) demands more than one monovalent anion pfu in the structure. As the mineral lacks fluorine, charge neutrality must be achieved through additional H⁺ (about 0.4 apfu). Only one independent hydrogen atom is located within the structure, with O10 as donor and O4 as acceptor, as in other epidote-supergroup minerals. Nonetheless, another O-O distance is suitable for a hydrogen bond, namely O10-O2. Although the existence of the additional OH group was not directly proved by vibrational spectroscopy, FTIR data provided information related to this potential O10-O2 bridge. In the IR spectrum acquired, several bands are observed in the OH-stretching region, and a secondary peak at 2140 cm⁻¹ could be assigned to the bending mode of the O10-H···O2 group. To shed light on this puzzling observation, one single crystal was subjected to annealing experiments at temperatures from 500 to 700 °C, in 50 °C steps, while a second one underwent a heat treatment at 700 °C. After the heat treatment, the IR spectrum showed a decreased intensity of all observed bands, in agreement with a dehydrogenation occurring at high temperatures. Although the structural position of the second hydrogen is still uncertain, it is reasonable to describe the composition of the epidote-supergroup mineral from Malmkärra as a solid solution between dissakisite-(Ce) (32%), ferriallanite-(Ce) (28%), and a yet undescribed end-member (40%), the (OH)-analog of dollaseite-(Ce), ideally CaREE³⁺Mg₂AlSi₃O₁₁(OH)₂.