Carbon isotopes and geochemical processes in CO2-rich cold mineral water, N-Portugal(Article)

This paper summarizes a new outlook on the conceptual model of Melgaço-Messegães CO2-rich cold (≈18 °C) mineral water systems, issuing in N of Portugal, based on their isotopic (2H, 3H, 13C, 14C and 18O) and geochemical features. Stable isotopes indicate the meteoric origin of these CO2-rich mineral waters. Based on the isotopic fractionation with the altitude, a recharge altitude between 513 up to 740 m a.s.l. was estimated, corroborating the tritium results. The lowest 3H content (0 TU) is found in the groundwater samples with the highest mineralization. The mineral waters circulation are mainly related to a granitic and granodioritic environment inducing two different groundwater types (Ca/Na-HCO3 and Na/Ca-HCO3), indicating different underground flow paths. Calcium dissolution is controlled by hydrolysis of rock-matrix silicate minerals (e.g. Ca-plagioclases) and not associated to anthropogenic sources. The shallow dilute groundwaters exhibit signatures of anthropogenic origins (e.g. NO3) and higher Na/Ca ratios. The stable isotopes together with the geochemistry provided no indication of mixing between the regional shallow cold dilute groundwater and mineral water systems. The heavy isotopic signatures identified in the δ13C data (δ13C = 4.7 ‰, performed on the total dissolved inorganic carbon (TDIC) of CO2-rich mineral waters) could be derived from a deep-seated (upper mantle) source or associated to methanogenesis (CH4 source). The negligible 14C content (≈2 pmC) determined in the TDIC of the mineral waters, corroborates the hypothesis of a mantle-derived carbon source to the mineral groundwater systems or dissolution of carbonate layers at depth. © 2013 Springer-Verlag Berlin Heidelberg.