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.

Safeguarding water resources for society and ecosystems requires a comprehensive understanding of hydrological fluxes within the Critical Zone, Earth's living skin where the atmosphere, hydrosphere, biosphere, and lithosphere meet. For decades, tracer‐aided mixing models have been used to track water flow paths through the Critical Zone, mapping the journey of water particles from atmospheric moisture to groundwater. Recent advances in novel tracer measurements and modeling methodologies offer new insights into hydrological partitioning within the Critical Zone, enabling improved quantification of water fluxes across scales ranging from microscopic to macroscopic. Advanced tracer‐aided modeling approaches enable more rigorous testing of assumptions and improved quantification of uncertainties. In this review, we (a) summarize state‐of‐the‐art tracer and modeling techniques, with an emphasis on stable water isotope tracers, (b) synthesize insights emerging from new approaches, and (c) highlight opportunities to apply these methods in interdisciplinary Critical Zone research.