Dissolved helium isotope ratios in ground-waters: a new technique based on gas-water re-equilibration and its application to Stromboli volcanic system

Here, a new technique for the determination of dissolved He isotope ratios in ground-waters is presented. This method is based on the extraction and subsequent equilibrium of dissolved gases in an added “host” gas phase. Ultra pure N2 is placed in glass flasks (250 cc), containing water samples, that were hermetically sealed after their collection. After shaking in an ultrasonic bath for 10 min, an aliquot of the separated gas phase was removed from the flask for MS analysis. 3He/4He ratios are measured by using a modified double collector mass spectrometer (VG 5400-TFT). Helium and Ne concentrations are calculated by comparing the partial pressures of masses 4 and 20 of the samples with those of the air-standard measured by a quadrupole mass spectrometer (QMS;VG Quartz). Using He and Ne equilibrium partitioning coefficients, it is possible to calculate the amount of gas originally dissolved in the water. The technique was tested on both air-saturated waters (ASW) and thermal waters from Stromboli (Aeolian Islands, South Italy), the results of which confirmed good reproducibility (≌5%) and accuracy (≌3%) of the data. The method was then applied to three thermal water samples collected from the same volcanic area and the results compared with those of a fumarolic and a soil gas. The isotope ratios for dissolved He gave values of 4.06–4.23 Ra, which are significantly higher than those previously reported in the literature (3.0, 3.5 and 2.9 Ra) and that measured at the fumarole (3.09 Ra), suggesting a newer and higher isotopic signature for the volcanic system. The proposed method appears to be a useful tool in the determination of 3He/4He ratios in ground-water systems, especially when free gases are not available or are dangerous to collect.