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Isotopically (delta C-13 and delta O-18) heavy volcanic plumes from Central Andean volcanoes : a field study
Abstract
Stable isotopes of carbon and oxygen in volcanic gases are key tracers of volatile transfer between Earth's interior and atmosphere. Although important, these data are available for few volcanoes because they have traditionally been difficult to obtain and are usually measured on gas samples collected from fumaroles. We present new field measurements of bulk plume composition and stable isotopes (delta(CCO2)-C-13 and delta(OH2O+)-O-18 CO2) carried out at three northern Chilean volcanoes using MultiGAS and isotope ratio infrared spectroscopy. Carbon and oxygen in magmatic gas plumes of Lastarria and Isluga volcanoes have delta C-13 in CO2 of + 0.76% to + 0.77% (VPDB), similar to slab carbonate; and delta O-18 in the H2O + CO2 system ranging from + 12.2% to + 20.7% (VSMOW), suggesting significant contributions from altered slab pore water and carbonate. The hydrothermal plume at Tacora has lower delta(CCO2)-C-13 of -3.2% and delta(OH2O)-O-18+ CO2 of + 7.0%, reflecting various scrubbing, kinetic fractionation, and contamination processes. We show the isotopic characterization of volcanic gases in the field to be a practical complement to traditional sampling methods, with the potential to remove sampling bias that is a risk when only a few samples from accessible fumaroles are used to characterize a given volcano's volatile output. Our results indicate that there is a previously unrecognized, relatively heavy isotopic signature to bulk volcanic gas plumes in the Central Andes, which can be attributed to a strong influence from components of the subducting slab, but may also reflect some local crustal contamination. The techniques we describe open new avenues for quantifying the roles that subduction zones and arc volcanoes play in the global carbon cycle.
Studying spatial and temporal trends in volcanic gas compositions and fluxes is crucial both to volcano monitoring and to constrain the origin and recycling efficiency of volatiles at active convergent margins. New volcanic gas compositions and volatile fluxes are here reported for Nevado del Ruiz, Galeras, and Purace, three of the most persistently degassing volcanoes located in the Colombian Arc Segment of the Northern Volcanic Zone. At Nevado del Ruiz, from 2014 to 2017, plume emissions showed an average molar CO2/ST ratio of 3.9 ± 1.6 (ST is total sulfur, S). Contemporary, fumarolic chemistry at Galeras progressively shifted toward low‐temperature, S‐depleted fumarolic gas discharges with an average CO2/ST ratio in excess of 10 (6.0–46.0, 2014–2017). This shift in volcanic gas compositions was accompanied by a concurrent decrease in SO2 emissions, confirmed on 21 March 2017 by high‐resolution ultraviolet camera‐based SO2 fluxes of ~2.5 kg/s (~213 t/day). For comparison, SO2 emissions remained high at Nevado del Ruiz (weighted average of 8 kg/s) between 2014 and 2017, while Puracé maintained rather low emission levels (<1 kg/s of SO2, CO2/SO2 ≈ 14). We here estimate carbon dioxide fluxes for Nevado del Ruiz, Galeras, and Puracé of ~23, 30, and 1 kg/s, respectively. These, combined with recent CO2 flux estimates for Nevado del Huila of ~10 kg/s (~860 t/day), imply that this arc segment contributes about 50% to the total subaerial CO2 budget of the Andean Volcanic Belt. Furthermore, our work highlights the northward increase in carbon‐rich sediment input into the mantle wedge via slab fluids and melts that is reflected in magmatic CO2/ST values far higher than those reported for Southern Volcanic Zone and Central Volcanic Zone volcanoes. We estimate that about 20% (~1.3 Mt C/year) of the C being subducted (~6.19 Mt C/year) gets resurfaced through subaerial volcanic gas emissions in Colombia (Nevado del Ruiz ~0.7 Mt C/year). As global volcanic volatile fluxes continue to be quantified and refined, the contribution from this arc segment should not be underestimated.
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