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.

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Multivariate statistical methodsprincipal component analysis (PCA) and hierarchical cluster analysis (HCA)are applied to identify geochemically distinct groundwater groups in the territory of Latvia. The main processes observed to be responsible for groundwater chemical composition are carbonate and gypsum dissolution, fresh and saltwater mixing and ion exchange. On the basis of major ion concentrations, eight clusters (C1-C8) are identified. C6 is interpreted as recharge water not in equilibrium with most sediment forming minerals. Water table aquifers affected by diffuse agricultural influences are found in C3. Groundwater in C4 reflects brine or seawater admixture and gypsum dissolution in C5. C7 and C2 belong to typical bicarbonate groundwater resulting from calcite and dolomite weathering. Extremely low Cl À and SO 4 2À are observed in C8 and described as preindustrial groundwater or a solely carbonate weathering result. Finally, C1 seems to be a poorly defined subgroup resulting from mixing between other groups. This research demonstrates the validity of applying multivariate statistical methods (PCA and HCA) on major ion chemistry to distribute characteristic trace elements in each cluster even when incomplete records of trace elements are present. Key words | groundwater chemistry, hierarchical cluster analysis, principal component analysis, trace elements Riga region. A noticeable increase of salinity in fresh groundwater around the city of Riga has been observed (Levins ). Coastal groundwater aquifers sometimes are affected by seawater intrusion, in particular if large cities are using them 799

A new data set of δ(2)H and δ(18)O in the groundwater from the central part of the Baltic Artesian Basin is presented. The hydrogeological section is subdivided into stagnation, slow exchange and active exchange zones. Na-Ca-Cl brine found at the deepest part - the stagnation zone - is characterized by δ(18)O values above -5 ‰ and δ(2)H values approaching -40 ‰ with respect to Vienna Standard Mean Ocean Water. The slow exchange zone where waters of mostly intermediate salinity reside is characterized by δ(18)O values around -11.7 ‰ and δ(2)H values around -85.3 ‰. Mean δ(18)O and δ(2)H values of the fresh groundwater in the active water exchange zone are -11.1 and -79.9 ‰, respectively. Characteristically, the groundwater in the active and slow exchange zone is isotopically more depleted compared with the precipitation values observed, and the depletion increases with depth down to the level where strongly enriched brines are encountered.

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