An experimental study on K and Na incorporation in dravitic tourmaline and insight into the origin of diamondiferous tourmaline from the Kokchetav Massif, Kazakhstan

Abstract

Tourmaline was synthesized in the system MgO–Al2O3–B2O3–SiO2–KCl–NaCl–H2O from an oxide mixture and excess fluid at 500–700 °C and 0.2–4.0 GPa to investigate the effect of pressure, temperature, and fluid composition on the relative incorporation of Na and K in dravitic tourmaline. Incorporation of K at the X-site increases with pressure, temperature, and KCl concentration; a maximum of 0.71 K pfu (leaving 0.29 X-vacant sites pfu) was incorporated into K-dravite synthesized at 4.0 GPa, 700 °C from a 4.78 m KCl, Na-free fluid. In contrast, Na incorporation depends predominately on fluid composition, rather than pressure or temperature; dravite with the highest Na content of 1.00 Na pfu was synthesized at 0.4 GPa and 700 °C from a 3.87 m NaCl and 1.08 m KCl fluid. All synthesized crystals are zoned, and the dominant solid solution in the Na- and K-bearing system is between magnesio-foitite [□(Mg2Al)Al6Si6O18(BO3)3(OH)3OH] and dravite [NaMg3Al6Si6O18(BO3)3(OH)3(OH)], with the dravitic component increasing with the concentration of Na in the fluid. In the K-bearing, Na-free system, the dominant solid solution is between magnesio-foitite and K-dravite [KMg3Al6Si6O18(BO3)3(OH)3(OH)], with the K-dravitic component increasing with pressure, temperature, and the concentration of K in the fluid. The unit-cell volume of tourmaline increases with K incorporation from 1555.1(3) to 1588.1(2) A3, reflecting the incorporation of the relatively large K+ ion. Comparison of our results to the compositional data for maruyamaite (K-dominant tourmaline) from the ultrahigh-pressure rocks of the Kokchetav Massif in Kazakhstan suggests that the latter was formed in a K-rich, Na-poor environment at ultrahigh-pressure conditions near the diamond-stability field.