Carbon Concentration Excursions in Apatite Phenocrysts from the Cerro Galan Ignimbrite: A SIMS View into the Transient pre-Eruptive Volatile History of a Supervolcano

In nearly all igneous rock compositions, apatite is the most abundant mineral that regularly incorporates significant quantities of volatile elements into its structure, making it a potentially useful tool for exploring magmatic processing of volatiles (as well as REEs, Sr, Nd, and Pb isotopes, all of which are typically abundant in apatite). We have developed an analytical protocol that permits measurement of C, H, F, S, and Cl in ~8μm diameter regions of apatite using the Cameca 6f SIMS. A primary Cs+ beam (4-10 nA) is used in conjunction with electron gun charge-compensation to sputter negative ions from polished sections and unpolished crystal faces mounted in volatile-free indium mounts. We operated at mass resolving powers sufficient to separate all potential interferences (such as ^{31}PH and 16O2 from ^{32}S, and 17O from 16OH). Quantifying the SIMS data requires a set of standards that are 1) homogeneous at the few-micron scale; and 2) well-calibrated with multiple, reliable, independent volatile content measurements. Using values combed from the literature and other unpublished sources, we have assembled a set of apatite standards, none of which are proven to meet either criteria. Nevertheless, these materials allow us to create calibration curves for all of the volatile elements listed above. Traverses across polished basal sections of apatite phenocrysts from the ~1000 km3 Cerro Galan ignimbrite, Argentina (courtesy of C. Schirnick) yield the following results: Apatites are fluorine-rich, and contain significant and reproducible intracrystalline variations in C, H, S, and Cl. Positive carbon concentration excursions (up to 360 ppm) are factors of 2-7 greater than apatite baseline concentrations (40-60 ppm), the largest of which correlate with position in different grains. In the majority of the traverses, these carbon excursions also correlate spatially with 25-30% increases in sulfur concentration. We suggest that these dramatic increases in carbon and sulfur concentrations record a transient increase in magmatic SO4^{2- } and CO2 activities, perhaps the result of an underplating/recharge event, followed by a return to baseline magma chemistry. Hydrogen-poor rims are observed in all studied crystals, and are accompanied by chlorine-impoverished rims in a majority of the traverses, perhaps recording the pre- or syn-eruption exsolution of a vapor phase enriched in H and Cl.