Experimental investigation of F, Cl, and OH partitioning between apatite and Fe-rich basaltic melt at 1.0-1.2 GPa and 950-1000 °C

Apatite-melt partitioning experiments were conducted in a piston-cylinder press at 1.0–1.2 GPa and 950–1000 °C using an Fe-rich basaltic starting composition and an oxygen fugacity within the range of ΔIW-1 to ΔIW+2. Each experiment had a unique F:Cl:OH ratio to assess the partitioning as a function of the volatile content of apatite and melt. The quenched melt and apatite were analyzed by electron probe microanalysis and secondary ion mass spectrometry techniques. The mineral-melt partition coefficients (D values) determined in this study are as follows: DF^Ap-Melt = 4.4–19, DCl^Ap-Melt = 1.1–5, DOH^Ap-Melt = 0.07–0.24. This large range in values indicates that a linear relationship does not exist between the concentrations of F, Cl, or OH in apatite and F, Cl, or OH in melt, respectively. This non-Nernstian behavior is a direct consequence of F, Cl, and OH being essential structural constituents in apatite and minor to trace components in the melt. Therefore mineral-melt D values for F, Cl, and OH in apatite should not be used to directly determine the volatile abundances of coexisting silicate melts. However, the apatite-melt D values for F, Cl, and OH are necessarily interdependent given that F, Cl, and OH all mix on the same crystallographic site in apatite. Consequently, we examined the ratio of D values (exchange coefficients) for each volatile pair (OH-F, Cl-F, and OH-Cl) and observed that they display much less variability: K_dCl-F^Ap-Melt = 0.21 ± 0.03, K_dOH-F^Ap-Melt= 0.014 ± 0.002, and K_dOH-Cl^Ap-Melt= 0.06 ± 0.02. However, variations with apatite composition, specifically when mole fractions of F in the apatite X-site were low (X_F < 0.18), were observed and warrant additional study. To implement the exchange coefficient to determine the H₂O content of a silicate melt at the time of apatite crystallization (apatite-based melt hygrometry), the H₂O abundance of the apatite, an apatite-melt exchange K_d that includes OH (either OH-F or OH-Cl), and the abundance of F or Cl in the apatite and F or Cl in the melt at the time of apatite crystallization are needed (F if using the OH-F K_d and Cl if using the OH-Cl K_d). To determine the H₂O content of the parental melt, the F or Cl abundance of the parental melt is needed in place of the F or Cl abundance of the melt at the time of apatite crystallization. Importantly, however, exchange coefficients may vary as a function of temperature, pressure, melt composition, apatite composition, and/or oxygen fugacity, so the combined effects of these parameters must be investigated further before exchange coefficients are applied broadly to determine volatile abundances of coexisting melt from apatite volatile abundances.