Imprint of chemical weathering and hydrothermalism on the Ge/Si ratio and Si isotope composition of rivers in a volcanic tropical island, Basse-Terre, Guadeloupe (French West Indies)

Abstract

A significant portion of the disproportionally high chemical weathering flux in volcanic island arcs may originate from hydrothermal fluid-rock interaction, thereby compromising the accurate estimate of atmospheric CO2 consumption rates. The objective of this study is to evaluate how the riverine Ge/Si ratio and Si isotopes, two well-established tracers of weathering, respond to hydrothermal inputs. The work took place in Basse-Terre, Guadeloupe, a tropical volcanic island with a dense river network, high chemical weathering fluxes and various hydrothermal surface manifestations. We characterized the Ge/Si ratio and δ30Si of 15 thermal springs, nine non-impacted (NI) rivers and 13 hydrothermally-impacted (HI) rivers. The soil solution from a highly weathered soil profile (Ferralsol) and a clayey-rock corresponding to the material exposed in an extinct hydrothermal system were also measured. A new purification method was successfully developed in order to allow the reliable measurement of Si isotopes in SO42−- and Cl−-rich thermal spring and HI river waters by mass spectrometry. Basse-Terre's thermal springs have variable Ge/Si ratios (0.05–21.03 μmol.mol−1) and δ30Si (0.71–1.50‰), but with no apparent relationship to the water compositional type. The Ge/Si ratio (0.15–2.57 μmol.mol−1) and Si isotope composition (0.26–1.21‰) values of the NI rivers reveal differences in the watersheds' weathering degree. Dissolution of Ge- and 28Si-rich secondary minerals explains the high Ge/Si and isotopically light composition of the northern NI rivers draining strongly weathered terranes. The Ge/Si ratio and δ30Si values measured for the NI and HI rivers overlap, implying that they cannot be used to diagnose hydrothermal contributions to river basins unambiguously. However, when combined with the Cl− and SO42− concentrations, the analysis of Ge and Si in the HI rivers suggests that water seeping through an extinct hydrothermal system produces SO4-rich drainages with distinctively lower Ge/Si ratios than those inferred for watersheds receiving thermal spring discharges associated with an active hydrothermal system. Overall, our results provide new constraints for applying and interpreting Ge/Si and Si isotope measurements to study weathering in volcanic environments.