Major and trace element compositions (including REE) of mineral, thermal, mine and surface waters in SW Germany and implications for water-rock interaction

The near-surface water cycle in a geologically complex area comprises very different sources including meteoric, metamorphic and magmatic ones. Fluids from these sources can react with sedimentary, magmatic and/or metamorphic rocks at various depths. The current study reports a large number of major, minor and trace element analyses of meteoric, mineral, thermal and mine waters from a geologically well-known and variable area of about 200 × 150. km in SW Germany. The geology of this area comprises a Variscan granitic and gneissic basement overlain in parts by Triassic and Jurassic shales, sandstones and limestones. In both the basement and the sedimentary rocks, hydrothermal mineralization occurs (including Pb, Cu, As, Zn, U, Co and many others) which were mined in former times. Mineral waters, thermal waters and meteoric waters flowing through abandoned mines (mine waters) are distributed throughout the area, although the mine waters concentrate in and around the Schwarzwald. The present analyses show, that the major element composition of a particular water is determined by the type of surrounding rock (e.g., crystalline or sedimentary rocks) and the depth from which the water originates. For waters from crystalline rocks it is the origin of the water that determines whether the sample is Na-Cl dominant (deeper origin) or Ca-HCO₃ dominant (shallow origin). In contrast, compositions of waters from sedimentary rocks are determined by the availability of easily soluble minerals like calcite (Ca-HCO₃ dominant), halite (Na-Cl dominant) or gypsum (Ca-SO₄ dominant). Major element data alone cannot, therefore, be used to trace the origin of a water. However, the combination of major element composition with trace element data can provide further information with respect to flow paths and fluid-rock interaction processes. Accordingly, trace element analyses showed, that:-Ce anomalies can be used as an indicator for the origin of a water. Whereas surface waters have negative or strongly negative Ce anomalies, waters originating from greater depths show no or only weak negative Ce anomalies.-Eu anomalies can be used to differentiate between host rocks. Waters from gneisses display positive Eu anomalies, whereas waters from granites have negative ones. Waters from sedimentary rocks do not display any Eu anomalies.-Rb and Cs can also be indicators for the rock with which the fluid interacted: Rb and Cs correlate positively in most waters with Rb/Cs ratios of ∼2, which suggests that these waters are in equilibrium with the clay minerals in the rocks. Rb/Cs ratios >5 indicate reaction of a water with existing clay minerals, whereas Rb/Cs ratios <2 are probably related to host rock alteration and clay mineral formation. The chemical compositions of carbonate precipitates from thermal waters indicate that rare earth elements (REEs), Rb and Cs concentrations in the minerals are controlled by the incorporation of clay particles that adsorb these elements.