Tracing effects of decalcification on solute sources in a shallow groundwater aquifer, NW Germany

Summaryδ87Sr values and Ca/Sr ratios were employed to quantify solute inputs from atmospheric and lithogenic sources to a catchment in NW Germany. The aquifer consists primarily of unconsolidated Pleistocene eolian and fluviatile deposits predominated by >90% quartz sand. Accessory minerals include feldspar, glauconite, and mica, as well as disperse calcium carbonate in deeper levels. Decalcification of near-surface sediment induces groundwater pH values up to 4.4 that lead to enhanced silicate weathering. Consequently, low mineralized Ca–Na–Cl- and Ca–Cl-groundwater types are common in shallow depths, while in deeper located calcareous sediment Ca–HCO3-type groundwater prevails. δ87Sr values and Ca/Sr ratios of the dissolved pool range from 7.3 to −2.6 and 88 to 493, respectively. Positive δ87Sr values and low Ca/Sr ratios indicate enhanced feldspar dissolution in shallow depths of less than 20 m below soil surface (BSS), while equilibrium with calcite governs negative δ87Sr values and elevated Ca/Sr ratios in deep groundwater (>30 m BSS). Both positive and negative δ87Sr values are evolved in intermediate depths (20–30 m BSS). For groundwater that is undersaturated with respect to calcite, atmospheric supplies range from 4% to 20%, while feldspar-weathering accounts for 8–26% and calcium carbonate for 62–90% of dissolved Sr2+. In contrast, more than 95% of Sr2+ is derived by calcium carbonate and less than 5% by feldspar dissolution in Ca–HCO3-type groundwater. The surprisingly high content of carbonate-derived Sr2+ in groundwater of the decalcified portion of the aquifer may account for considerable contributions from Ca-containing fertilizers. Complementary tritium analyses show that equilibrium with calcite is restricted to old groundwater sources.