Factors controlling sulfur concentrations in volcanic apatite

Apatite crystals from two types of samples were analyzed by electron microprobe for 15 major and trace elements: (1) apatite in H2O- and S-saturated experimental charges of the 1982 El Chicho??n trachyandesite and (2) apatite in volcanic rocks erupted from 20 volcanoes. The SO3 contents of the experimental apatite increase with increasing oxygen fugacity (fo2), from ???0.04 wt% in reduced charges buffered by fayalite-magnetite-quartz (FMQ), to 1.0-2.6 wt% in oxidized charges buffered by manganosite-hausmanite (MNH) or magnetite-hematite (MTH). The SO3 contents of MNH- and MTH-buffered apatite also generally increase with increasing pressure from 2 to 4 kbar and decreasing temperature from 950 to 800??C. The partition coefficient for SO3 between apatite and oxidized melt increases with decreasing temperature but appears to be independent of pressure. Apatites in volcanic rocks show a wide range of SO3 contents (<0.04 to 0.63 wt%). Our sample set includes one group known to contain primary anhydrite and a second group inferred to have been free of primary anhydrite. No systematic differences in apatite S contents are observed between these two groups. Our study was initiated to define the factors controlling S contents in apatite and to evaluate the hypothesis that high S contents in apatite could be characteristic of S-rich anhydrite-bearing magmas such as those erupted from El Chicho??n in 1982 and Pinatubo in 1991. This hypothesis is shown to be invalid, probably chiefly a consequence of the slow intra-crystaline diffusion that limits re-equilibration between early formed apatite and the evolving silicate melt. Contributing factors include early crystallization of most apatite over a relatively small temperature interval, common late-stage magmatic enrichment of S, progressive oxidation during magmatic evolution, and strong controls on S contents in apatite exerted fo2, temperature, and pressure.