Coupled substitutions in the tourmaline group

Statistical analysis of 136 natural tourmaline compositions from the literature reveals the presence and extent of coupled substitutions involving several cations and structural sites. In schorls and dravites these are a dehydroxylation type substitution (1) (OH)^–+R²⁺ = R³⁺+O^2– and an alkali-defect type substitution (2) R⁺+R²⁺ = R³⁺+, Al³⁺ being the predominant R³⁺ action. Substitution (1) which represents solid solution towards a proton-deficient end-member, R⁺ R ₃ ³⁺ R ₆ ³⁺ (BO₃)₃ Si₆O₁₈O₃(OH), accounts for three times as much of the observed compositional variability as does (2) which represents substitution toward a hypothetical alkali-free end-member, (R ₂ ²⁺ R³⁺) R ₆ ³⁺ (BO₃)₃Si₆O₁₈(OH)₄. The occurrence of both of these substituions produces intermediates between end-member schorl/ dravite, R⁺ R ₃ ²⁺ R ₆ ³⁺ (BO₃)₃Si₆O₁₈(OH)₄, and a new series within the tourmaline group, R _1–x ⁺ R ₃ ³⁺ R ₆ ³⁺ (BO₃)₃Si₆O₁₈O_3–x (OH)_1+x.In addition to dehydroxylation type, 2(OH)^–+Li⁺ = R³⁺+20^2–, and possibly alkali-defect type, 2R⁺+Li⁺ = R³⁺+2, substitutions, a third type Li⁺+O^2– = (OH)^–+, occurs in the elbaites giving rise to Li-poor, proton-rich species. All three substitutions serve to reduce the Li-content of natural elbaite which, as a result, does not attain the composition of the ideal end-member, Na(Li_1.5Al_1.5)Al₆(BO₃)₃Si₆O₁₈(OH)₄. Substitution from elbaite and schorl/dravite toward R _1–x ⁺ R ₃ ³⁺ R ₆ ³⁺ (BO₃)₃Si₆O₁₈O_3–x(OH)_1+x is very extensive and may be complete.Substitution toward R _1–x ⁺ R ₃ ³⁺ R ₆ ³⁺ (BO₃)₃Si₆O₁₈O_3–x(OH)_1+x results in improved local charge balance. The mean deviation from oxygen charge saturation is at a maximum in end-member schorl, dravite and elbaite. Substitutions (1) and (2) progressively decrease but substitution (1) does so more effectively, which may explain its predominance in nature. However, alkali-defective end-members appear to be unstable regardless of . Substitution (3) in the elbaites cannot be discussed on the basis of charge balance considerations at present due to the lack of structural information on proton-rich species.