Nonstoichiometric hydrogen contents in common rock-forming hydroxyl silicates

Mathematics – Logic

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H + and Fe 3+ have been analyzed in conjunction with electron microprobe studies of over 500 petrologically well-constrained rock-forming Fe-bearing hydroxyl silicates. H + and Fe 3+ vary widely in the minerals studied. In most cases, biotite, muscovite, and chlorite are deficient in H + relative to the generally assumed stoichiometries. Results indicate that oxysubstitution (or deprotonation) involving only H + and Fe 3+ exchange is rare, although the related substitution of H + mineral (Fe, Mg) 2+ mineral (Fe 3+ , A1 3+ , , etc.) mincral + is extremely common. In biotites from metapelites in western Maine, this relationship can be expressed quantitatively as H + = -1.120 ± 0.302 × (6 - 4 Si 4+ + 6 Fe 3+ + 6 A1 3+ + 6 Ti 4+ × 2)× + 4.9006 ± 0.2547 6 A1 3+ + 6 Ti 4+ × 2)× + 4.9006 ± 0.2547 for a 24-oxygen formula unit. Similar equations will be developed for other hydroxyl phases. This mechanism accounts for the great majority of R 3+ and R 4+ substitution (apart from the Tshermak substitution), reducing or eliminating the need to invoke vacancies for charge balance and should also be considered in formulation of site substitution models, geothermobarometry and any other applications dependent on full characterization of mineral compositions.

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