Progressive drying of the hydrothermal system of La Soufrière de Guadeloupe (French West Indies) revealed by multi-year monitoring of chlorine isotopic composition of fumarolic HCl

Abstract

Closed-conduit volcanoes develop hydrothermal aquifers where infiltrating waters dissolve magmatic gases such as SO₂, HCl, and HF. The extent of this “scrubbing effect” is traditionally tracked using CO₂/SO₂ or CO₂/S_Total, but these ratios can also be modified by secondary processes. Given the high solubility of gaseous HCl_(g) into aqueous water, we assess here chlorine isotopic compositions (δ³⁷Cl) in fumarolic HCl_(g) as a potential quantitative index of scrubbing.

We present three years and a half (January 2018 to May 2021) of δ³⁷Cl and chlorine concentrations [Cl] data from fumarolic gases at La Soufrière de Guadeloupe, alongside traditional geochemical tracers in volcanology. Our data show strong negative correlation between δ³⁷Cl and [Cl] values, suggesting variable extents of HCl dissolution into the hydrothermal aquifer through time. High δ³⁷Cl values associated to low [Cl] indicate intense ³⁵Cl loss into the aquifer, while low δ³⁷Cl values with high [Cl] likely reflect more pristine magmatic signatures with minimal extents of scrubbing.

The observed δ³⁷Cl–[Cl] trends suggest Cl isotopic fractionation factors between gas and liquid Δ_g-l varying between +2.5 and +5 ‰. These values are higher than expected at equilibrium, suggesting kinetic fractionations likely resulting from rapid gas flow (preventing isotopic equilibration with liquid water). The fact that comparable δ³⁷Cl–[Cl] trends are found at Poás (Costa Rica) and Vulcano (Italy) suggests that such kinetic fractionations during HCl scrubbing may be widespread.

Comparisons between δ³⁷Cl and CO₂/CH₄ ratios and the modeled groundwater level within the dome suggest that variations in scrubbing at La Soufrière are primarily driven by varying magmatic inputs. The progressive decrease in δ³⁷Cl, associated with increasing [Cl] from 2019 to 2021, likely reflects long-term aquifer drying, predating the observed rise in fumarolic temperatures above 150 °C in mid-2023.