Carrier and dilution effects of CO2 on thoron emissions from a zeolitized tuff exposed to subvolcanic temperatures.

Radon (222Rn) and thoron (220Rn) are two isotopes belonging to the noble gas radon (sensu lato) that is frequently employed for the geochemical surveillance of active volcanoes. Temperature gradients operating at subvolcanic conditions may induce chemical and structural modifications in rock-forming minerals and their related 222Rn-220Rn emissions. Additionally, CO2 fluxes may also contribute enormously to the transport of radionuclides through the microcracks and pores of subvolcanic rocks. In view of these articulated phenomena, we have experimentally quantified the changes of 220Rn signal caused by dehydration of a zeolitized tuff exposed to variable CO2 fluxes. Results indicate that, at low CO2 fluxes, water molecules and hydroxyl groups adsorbed on the glassy surface of macro- and micropores are physically removed by an intermolecular proton transfer mechanism, leading to an increase of the 220Rn signal. By contrast, at high CO2 fluxes, 220Rn emissions dramatically decrease because of the strong dilution capacity of CO2 that overprints the advective effect of carrier fluids. We conclude that the sign and magnitude of radon (sensu lato) changes observed in volcanic settings depend on the flux rate of carrier fluids and the rival effects between advective transport and radionuclide dilution.

Deep versus shallow sources of CO2 and Rn from a multi-parametric approach: the case of the Nisyros caldera (Aegean Arc, Greece).

Estimating the quantity of CO2 diffusively emitted from the Earth's surface has important implications for volcanic surveillance and global atmospheric CO2 budgets. However, the identification and quantification of non-hydrothermal contributions to CO2 release can be ambiguous. Here, we describe a multi-parametric approach employed at the Nisyros caldera, Aegean Arc, Greece, to assess the relative influence of deep and shallow gases released from the soil. In April 2019, we measured diffuse soil surface CO2 fluxes, together with their carbon isotope compositions, and at a depth of 80 cm, the CO2 concentration, soil temperature, and the activities of radon and thoron. The contributions of deep CO2 and biogenic CO2 fluxes were distinguished on the basis of their carbon isotope compositions. A Principal Component Analysis (PCA), performed on the measured parameters, effectively discriminates between a deep- and a shallow degassing component. The total CO2 output estimated from a relatively small testing area was two times higher with respect to that observed in a previous survey (October 2018). The difference is ascribed to variation in the soil biogenic CO2 production, that was high in April 2019 (a wet period) and low or absent in October 2018 (a dry period). Accounting for seasonal biogenic activity is therefore critical in monitoring and quantifying CO2 emissions in volcanic areas, because they can partially- or completely overwhelm the volcanic-hydrothermal signal.