Noble Gas Geochemistry

This study attempts to place constraints on groundwater residence times using helium isotopes and 14 C of a regional groundwater flow system – the Becancour River watershed – located midway between Montreal and Quebec City (Quebec, Canada). This densely populated region is one of the main targets for shale gas exploitation in Eastern Canada. For this reason, this watershed has been the focus of a detailed aquifer study to gain a better understanding of groundwater resources, both in terms of availability and quality. In the current study, noble gases were sampled and analyzed in twenty-eight wells from a Quaternary granular aquifer and a regional bedrock aquifer of Ordovician age. Tritium (3 H) and radiocarbon (A 14 C) activities were measured on selected wells. Helium isotopic ratios 3 He/ 4 He (R) normalized to that of the atmosphere (Ra = 1.386 × 10 −6) range from R/Ra = 0.039 ± 0.003 to 3.109 ± 0.065. The helium isotopic signatures point to the presence of three water bodies: 1) modern infiltration water with nearly atmospheric helium isotopic ratio and little post-bomb tritium recharging the shallower granular aquifer; 2) mid-50s tritium-rich water slightly mineralized; and 3) an older water component rich in terrigenic helium flowing in from the bedrock fractured aquifer. Uncorrected 14 C ages range from 15 ka to modern. 14 C is affected by several dead carbon reservoirs related to carbonate dissolution , cations exchange, oxidation of organic matter and methanogenesis. Adjusted 14 C ages calculated with NETPATH range from 7 ka to modern. Older 14 C ages correspond to the end of the regional reorganization of the hydrological system following deglaciation and isostatic rebound. Noble gas recharge paleotemperatures are 4–9 °C colder than the present temperatures, although no clear relation with ages has been found. The relationship between the helium isotopic ratios and 14 C ages suggests that the regional bedrock aquifer is affected by mixing between these three water sources. Calculated (U–Th)/ 4 He ages can be partially explained by in situ production of 4 He in the aquifer rock and the addition of a radiogenic helium source external to the aquifer. Calculated minimum helium fluxes of 1.0 × 10 −8 to 1.8 × 10 −7 cm 3 STP cm −2 yr −1 are tens to hundreds of times lower than the average continental crust flux of 3.3 × 10 −6 cm 3 STP cm −2 yr −1 , suggesting local sources, possibly from production of radiogenic helium in the shale gas formations underlying the studied aquifers. The occurrence of old groundwater in this aquifer system clearly limits the renewable resource and increases the risk of overexploitation in the case of increased use or in the case of pollution from different sources.

The Cheb Basin (Czech Republic) is characterized by emanations of magma-derived gases and repeated occurrences of mid-crustal earthquake swarms with small to intermediate magnitudes (M L < 4.5). Associated intense mantle degassing occurs at the Hartoušov Mofette, a representative site for the Cheb Basin. Here, we performed 14 sampling campaigns between June 2019 and March 2020. Gas samples of fluids ascending in two boreholes (F1, ∼28 m depth and F2, ∼108 m depth) and from a nearby natural mofette were analyzed for their chemical (CO 2 , N 2 , O 2 , Ar, He, CH 4 , and H 2) and isotope compositions (noble gases and CO 2). CO 2 concentrations were above 99.1% in most samples, while O 2 and N 2 were below 0.6%. He ranged from 19 to 34 µmol/mol and CH 4 was mostly below 12 µmol/mol. Isotope compositions of helium and carbon in CO 2 ranged from 5.39 to 5.86 R A and from −2.4 to −1.3 versus VPDB, respectively. Solubility differences of the investigated gases resulted in fluctuations of their chemical compositions. These differences were accompanied by observed changes of gas fluxes in the field and at the monitoring station for F1. Variations in solubilities and fluxes also impacted the chemical concentration of the gases and the δ 13 C values that were also likely influenced by Fischer-Tropsch type reactions. The combination of (a) the Bernard ratio, (b) CH 4 / 3 He distributions, (c) P-T conditions, (d) heat flow, and (e) the sedimentary regime led to the hypothesis that CH 4 may be of mixed biogenic and volcanic/geothermal origin with a noticeable atmospheric contribution. The drilling of a third borehole (F3) with a depth of ∼238 m in August 2019 has been crucial for providing insights into the complex system of Hartoušov Mofette.