Application of hierarchical cluster analysis and principal component analysis to identify compositional trends of brine in crystalline basements and sedimentary basins

The present study identifies distinct geochemical signatures of deep brines originating from crystalline basements and sedimentary basins. A corresponding conceptual hydrogeochemical model is developed outlining the evolution of crystalline and sedimentary brines. The combined application of Hierarchical Cluster Analysis and Principal Component Analysis allowed the identification of evolutionary trends of groundwater towards crystalline and sedimentary brines. Using 308 brine samples from the existing literature, eight chemical species were considered in the analysis: sodium, magnesium, potassium, calcium, strontium, chlorine, sulphate, and bromine, from which two salinity evolution pathways towards common Ca-Cl brines were derived: (1) the evolution of crystalline brines, which evolved from recharge water to brine through hydration of silicates, is described by the linear equation Ca = -1610 + 0.4*Cl; and (2) the evolution of sedimentary brines, which evolved from recharge water to brine through dissolution and precipitation of halite, is described by the linear equation Cl/Br = 103 + Na/Br. We also discuss differences in water isotopes, and in lithium and boron concentrations which directly reflect various temperature-dependent processes that control the evolution of sedimentary and crystalline brines. This leads to development of a discriminatory graphical tool using B/Br and Li/Br ratios, with crystalline brines having B/Br and Li/Br ratios below 0.01 and sedimentary brines above 0.01. Our results improve our understanding of deep crustal brine evolution through brine-rock interaction.