Hydrogen isotopes in volcanic plumes: Tracers for remote temperature sensing of fumaroles

In high-temperature volcanic fumaroles (>400 °C), the isotopic composition of molecular hydrogen (H₂) reaches equilibrium with that of the fumarolic H₂O. In this study, we used this hydrogen isotope exchange equilibrium of fumarolic H₂ as a tracer for the remote temperature at volcanic fumaroles. In this remote sensing, we deduced the hydrogen isotopic composition (δD value) of fumarolic H₂ from those in the volcanic plume. To ascertain that we can estimate the δD value of fumarolic H₂ from those in a volcanic plume, we estimated the values in three fumaroles with outlet temperatures of 630 °C (Tarumae), 203 °C (Kuju), and 107 °C (E-san). For this we measured the concentration and δD value of H₂ in each volcanic plume, along with those determined directly at each fumarole. The average and maximum mixing ratios of fumarolic H₂ within a plume’s total H₂ were 97% and 99% (at Tarumae), 89% and 96% (at Kuju), and 97% and 99% (at E-san). We found a linear relationship between the depletion in the δD values of H₂, with the reciprocal of H₂ concentration. Furthermore, the estimated end-member δD value for each H₂-enriched component (−260 ± 30‰ vs. VSMOW in Tarumae, −509 ± 23‰ in Kuju, and −437 ± 14‰ in E-san) coincided well with those observed at each fumarole (−247.0 ± 0.6‰ in Tarumae, −527.7 ± 10.1‰ in Kuju, and −432.1 ± 2.5‰ in E-san). Moreover, the calculated isotopic temperatures at the fumaroles agreed to within 20 °C with the observed outlet temperature at Tarumae and Kuju. We deduced that the δD value of the fumarolic H₂ was quenched within the volcanic plume. This enabled us to remotely estimate these in the fumarole, and thus the outlet temperature of fumaroles, at least for those having the outlet temperatures more than 400 °C. By applying this methodology to the volcanic plume emitted from the Crater 1 of Mt. Naka-dake (the volcano Aso) where direct measurement on fumaroles was impractical, we estimated that the δD value of the fumarolic H₂ to be −172 ± 16‰ and the outlet temperature to be 868 ± 97 °C. The remote temperature sensing using hydrogen isotopes developed in this study is widely applicable to many volcanic systems.