Multivariate statistical methods – principal 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⁻ and SO₄²⁻ are observed in C8 and described as pre-industrial 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.

Estimated natural background levels (NBLs) are needed to assess groundwater chemical status according to the EU Groundwater Directive. They are commonly derived for different substances by applying statistical methodologies. Due to the complexity of the sea water intrusion process, some of those methods do not always provide appropriate assessment of chloride NBLs. This paper analyzes the applicability of different NBL estimation methods in five EU coastal aquifers with significant differences in available datasets and hydrogeological settings. A sensitivity analysis of results to different constraints was performed to remove samples with anthropogenic impacts. A novel statistical approach combining different methods to identify the range of chloride NBLs is proposed. In all pilots the estimated NBLs were below 85 mg/L and fitted well with previous studies and expert judgment, except Campina del Faro aquifer (the maximum being 167.5 mg/L). Although this approach is more time consuming, it provides a more robust solution.

A new data set of δ²H and δ¹⁸O 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 δ¹⁸O values above −5 ‰ and δ²H 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 δ¹⁸O values around −11.7 ‰ and δ²H values around −85.3 ‰. Mean δ¹⁸O and δ²H 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.

Groundwater pollution by agrochemicals such as nitrogen fertilizers can cause complex biogeochemical transformations to take place in groundwater-dependent ecosystems. To explore the interaction between nitrogen load and groundwater-dependent, spring-fed ecosystems, a study was conducted in Latvia in an area of suspected high nitrate (NO₃⁻) vulnerability due to its geological settings. A map of NO₃⁻vulnerability along the margins of the carbonate aquifer in Latvia is presented. The map is based on a conceptual model that was developed during an extensive case study involving hydrological, hydrochemical, and habitat investigation of springs discharging from a karst aquifer and spring-fed ecosystems. Areas that should be prime targets for restricting fertilizer application are highlighted on the map. Although the case study revealed increased nitrogen pollution (up to 51 mg L⁻¹, standard deviation of 9 mg L⁻¹, in the springs discharging from the karst aquifer), no clear evidence of adverse effects due to NO₃⁻pollution on the groundwater-dependent ecosystems using biotic indicators was found, highlighting the resilience of spring-fed ecosystems against high nitrogen inputs. In the case study, downstream groundwater-dependent ecosystems retained 70% of the reactive nitrogen during the vegetation season, but only a small proportion during the cold season. Thus, NO₃⁻pollution can be partly mitigated by restoring wetlands along valley slopes where natural groundwater discharge takes place. The conceptual model developed for groundwater NO₃⁻vulnerability is applicable to other areas in the Baltic region and other places with similar climatic and geological conditions.