Analyses for 81 Kr and noble gases on groundwater from the deepest aquifer system of the Baltic Artesian Basin (BAB) were performed to determine groundwater ages and uncover the flow dynamics of the system on a timescale of several hundred thousand years. We find that the system is controlled by mixing of three distinct water masses: Interglacial or recent meteoric water (δ 18 O ≈ −10.4‰) with a poorly evolved chemical and noble gas signature, glacial meltwater (δ 18 O ≤ −18 ‰) with elevated noble gas concentrations, and an old, high-salinity brine component (δ 18 O ≥ −4.5‰, ≥ 90 g Cl − /L) with strongly depleted atmospheric noble gas concentrations. The 81 Kr measurements are interpreted within this mixing framework to estimate the age of the endmembers. Deconvoluted 81 Kr ages range from 300 ka to 1.3 Ma for interglacial or recent meteoric water and glacial meltwater. For the brine component, ages exceed the dating range of the ATTA-3 instrument of 1.3 Ma. The radiogenic noble gas components 4 He* and 40 Ar* are less conclusive butalso support an age of > 1 Ma for the brine. Based on the chemical and noble gas concentrations and the dating results, we conclude that the brine originates from evaporated seawater that has been modified by later water-rock interaction. As the obtained tracer ages cover several glacial cycles, we discuss the impact of the glacial cycles on flow patterns in the studied aquifer system. Virbulis et al., 2013), the latter of which estimated the hydraulic age of groundwater in the CAS to be on the order of several hundreds of ka to 1 Ma. In the light of such long residence times, it is crucial to consider the effect of repeated glacial cycles on the long-term evolution of groundwater composition and flow. Sampling the deeper parts of the CAS on a regional scale for chemistry, noble gases, and multiple dating tracers ( 81 Kr, 85 Kr, 39 Ar, 14 C, 4 He, 40 Ar) allows us to elucidate the evolution of the brine, mixing proportions of the different groundwater components, and the flow dynamics over the last 1 Ma.
Identification of the barium occurrence and its origin is made on the basis of the groundwater chemistry study. High Ba content has been detected in the Cambrian-Vendian aquifer system in the coastal vicinity of the Gulf of Finland in Estonia and St Petersburg. The dissolution of Ba from witherite as the primary source was derived from the analysis of the aqueous solution equilibrium with Ba-related minerals. It is reflected in the chemical composition of groundwater and influenced by the galenitecalcite-fluorite polymetallic mineralization in Vendian sandstones. The dissolution and re-deposition of carbonates and baryte are confirmed by mineral saturation states for an aqueous solution and distribution of other species in the groundwater of the Cambrian-Vendian aquifer system in North Estonia.
The Viimsi peninsula is located north-east of Tallinn, capital of Estonia. The Cambrian-Vendian (Cm-V) aquifer system is a sole source of drinking water in the area. Historically, the groundwater exploitation has led to freshening of groundwater in the peninsula, but in recent years an increase in chloride concentrations and enrichment in δ18O values has been detected, but in recent years hydrochemical parameters indicate an increasing influence of a saline water source. The exact origin of this saline water has remained unclear. The aim of the current study is to elucidate whether the increase in Cl− concentrations is related to seawater intrusion or to the infiltration of saline water from the underlying crystalline basement. To identify the source of salinity, chemical composition of the groundwater and the isotope tracers (e.g., δ18O and radium isotopes) were studied in the Viimsi peninsula in the period from 1987 to 2018. Our results show that chemical composition of Cm-V groundwater in the peninsula is clearly controlled by three-component mixing between glacial palaeogroundwater, saline water from the underling crystalline basement and modern meteoric water. The concentrations of Ra are also significantly affected by the mixing, but the spatial variation of radium isotopes (226Ra and 228Ra) suggests the widespread occurrence of the U in the surrounding sedimentary sequence. Our hypothesis is that, in addition to U originating from the crystalline basement, some U could be associated with secondary U deposits in sedimentary rocks. The formation of these secondary U deposits could be related to glacial meltwater intrusion in the Pleistocene. Although the results suggest that the infiltration of saline groundwater from the underlying crystalline basement as the main source of salinity in the study area, the risk of seawater intrusion in the future cannot be ruled out. It needs to be highlighted that the present groundwater monitoring networks may not be precise enough to detect the potential seawater intrusion and subsequent changes in water quality of the Cm-V aquifer system in the Viimsi peninsula.
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