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.
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
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