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Fe 2+ - and Mn 2+ -rich tourmalines were used to test whether Fe 2+  and Mn 2+  substitute on the Z site of tourmaline to a detectable degree. Fe-rich tourmaline from a pegmatite from Lower Austria was characterized by crystal-structure refinement, chemical analyses, and Mössbauer and optical spectroscopy. The sample has large amounts of Fe 2+  (~2.3 apfu), and substantial amounts of Fe 3+  (~1.0 apfu). On basis of the collected data, the structural refinement and the spectroscopic data, an initial formula was determined by assigning the entire amount of Fe 3+  (no delocalized electrons) and Ti 4+  to the Z site and the amount of Fe 2+  and Fe 3+  from delocalized electrons to the Y-Z ED doublet (delocalized electrons between Y-Z and Y-Y):  X  (Na 0.9 Ca 0.1 )  Y (Fe 2+  2.0 Al 0.4 Mn 2+  0.3 Fe 3+  0.2 )  Z (Al 4.8 Fe 3+  0.8 Fe 2+  0.2 Ti 4+  0.1 )  T (Si 5.9 Al 0.1 )O 18  (BO 3 ) 3  V (OH) 3  W [O 0.5 F 0.3 (OH) 0.2 ] with a = 16.039(1) and c = 7.254(1) Å. This formula is consistent with lack of Fe 2+  at the Z site, apart from that occupancy connected with delocalization of a hopping electron.

Limitations of Fe 2+ and Mn 2+ site occupancy in tourmaline: Evidence from Fe 2+ - and Mn 2+ -rich tourmaline