Gas geochemistry of Sierra Negra volcano, Galapagos hot spot

We report chemical and isotopic compositions of gases from the Mina Azufral fumarolic field of Sierra Negra volcano, Isabela Island, Galápagos, collected in 2004 and compare our data with the data by Giggenbach (unpublished) collected in 1990 and Goff et al. (2000) collected in 1995. New results include the noble gas elemental and isotope abundances and nitrogen isotope ratios for the discharges. Maximum fumarole temperatures and ratios of major components (C/S/Cl/N) changed very little between 1995 and 2004, but the water fraction varied significantly over this period (39 mol% in 1990; 77% in 1995 and 52% in 2004). Carbon and helium isotopic compositions were stable (-3 to -4‰ and 16-18Ra, respectively), and water isotopic composition showed a notable negative oxygen shift from the local meteoric water value depending on the relative water content and thus controlled by the H2O-CO2 oxygen isotope fractionation. In terms of the noble gas abundances and isotopic ratios, heavy noble gases (Kr and Xe) are mainly of the atmospheric origin. Ne isotopic ratios also show strong meteoric signatures, but fall along the 20Ne/22Ne - 21Ne/22Ne air-deep mantle mixing trend for Fernandina glasses (Kurz et al., 2009). 40Ar/36Ar ratios up to 400 show a notable contribution of radiogenic Ar, and 40Ar*/4He ~ 0.3 ratios are consistent with un-degassed upper mantle values. Despite the high He/Ne ratios in gases collected in 2004, and only trace air contamination attributable to sampling, the nitrogen isotope ratios (~ -1 ‰) show a high fraction of the air-saturated water in the volcanic vapor. The chemical composition of the parent magmatic gas is difficult to characterise due to significant interaction between magmatic and hydrothermal system fluids beneath the Sierra Negra caldera. Never-the-less, some important indicators can be estimated: CO2/3He ≈ 3.5x10^9; N2/He <30; CO2/N2 >500. The last value is much higher than the accepted value of ~ 100 for the upper mantle.