Graphite in the Bishop Tuff and its effect on postcaldera oxygen fugacity

Several cubic kilometers of Paleozoic graphite-bearing argillitic country rocks are present as lithic fragments in Bishop Tuff ignimbrite and fallout. The lithics were entrained by the 650 km³ of rhyolite magma that vented during the 5- to 6-day-long, caldera-forming eruption at Long Valley, California. The caldera is floored by a 350 km² roof plate that collapsed during the eruption and consists in large part of the Paleozoic strata that provided the abundant hornfelsed metapelitic lithic clasts in the tuff. Graphite has been identified by Raman spectroscopy, electron-dispersive spectroscopy, and X-ray diffraction as an irregularly dispersed component in the small fraction of Bishop Tuff pumice that is dark-colored. Carbon concentration has been determined in pumice, lithics, and wall rocks. Values of δ¹³C range from –21‰ to –29‰ Vienna Peedee Belemnite (VPDB) for pumice, lithics, and argillitic wall rocks, reflecting the biogenic origin of the reduced carbon in oxygen-limited black Paleozoic marine mudrocks. Carbonate contents, measured separately, are negligible in fresh pumice and lithics. Microprobe analyses of titanomagnetite-ilmenite pairs show that oxygen-fugacity values of numerous batches of postcaldera Early Rhyolite (750–640 ka; ~100 km³) are up to one log unit more reduced than those of the temperature–oxygen fugacity (T-fO₂) array of the Bishop Tuff (767 ka), despite similar major-element compositions and Fe-Ti–oxide temperature ranges. All of the many batches of Early Rhyolite, which erupted episodically over an interval of ~125,000 years, yield the reduced fO₂ values, indicating that reaction with graphite lowered magmatic fO₂ after the caldera-forming eruption but before the first eruption of Early Rhyolite. It is inferred that reaction of postcaldera rhyolite magma with the reduced carbon in a great mass of subsided roof rocks lowered its fO₂. It is suggested that comparable effects could have attended caldera collapse of other magma chambers hosted in continental sedimentary rocks.