Abstract. The quality of near-surface groundwater reservoirs is controlled, but also threatened, by manifold surfacesubsurface interactions. Vulnerability studies typically evaluate the variable interplay of surface factors (land management, infiltration patterns) and subsurface factors (hydrostratigraphy, flow properties) in a thorough way, but disregard the resulting groundwater quality. Conversely, hydrogeochemical case studies that address the chemical evolution of groundwater often lack a comprehensive analysis of the structural buildup. In this study, we aim to reconstruct the actual spatial groundwater quality pattern from a synoptic analysis of the hydrostratigraphy, lithostratigraphy, pedology and land use in the Hainich Critical Zone Exploratory (Hainich CZE). This CZE represents a widely distributed yet scarcely described setting of thin-bedded mixed carbonatesiliciclastic strata in hillslope terrains. At the eastern Hainich low-mountain hillslope, bedrock is mainly formed by alternated marine sedimentary rocks of the Upper Muschelkalk (Middle Triassic) that partly host productive groundwater resources. Spatial patterns of the groundwater quality of a 5.4 km long well transect are derived by principal component analysis and hierarchical cluster analysis. Aquifer stratigraphy and geostructural links were deduced from lithological drill core analysis, mineralogical analysis, geophysical borehole logs and mapping data. Maps of preferential recharge zones and recharge potential were deduced from digital (soil) mapping, soil survey data and field measurements of soil hydraulic conductivities (K s ). By attributing spatially variable surface and subsurface conditions, we were able to reconstruct groundwater quality clusters that reflect the type of land management in their preferential recharge areas, aquifer hydraulic conditions and cross-formational exchange via caprock sinkholes or ascending flow. Generally, the aquifer configuration (spatial arrangement of strata, valley incision/outcrops) and related geostructural links (enhanced recharge areas, karst phenomena) control the role of surface factors (input quality and locations) vs. subsurface factors (water-rock interaction, cross-formational flow) for groundwater quality in the multi-layered aquifer system. Our investigation reveals general properties of alternating sequences in hillslope terrains that are prone to forming multilayered aquifer systems. This synoptic analysis is fundamental and indispensable for a mechanistic understanding of ecological functioning, sustainable resource management and protection.

Abstract. The quality of near surface groundwater reservoirs is to a large extent controlled by land use and the properties of the soils in the recharge areas. Studies on groundwater quality and vulnerability, therefore, call for a thorough and holistic analysis of the buildup and hydraulic properties of the full range of surface and subsurface compartments involved in the interactions of water with immobile surfaces of the soils and rocks. This study provides a comprehensive characterization of the soils senso stricto, the unsaturated zone, aquifer stratigraphy and hydrochemistry in a hillslope karst environment of a carbonate-rock subcatchment of the Hainich Critical Zone Exploratory (CZE). This CZE is located within the Upper Muschelkalk Formations in the Hainich low mountain range, Thuringia, central Germany. We investigated the soils, surface geology, land use types and the infiltration properties based on a field survey. Aquifer stratigraphy, lithology and structure were analyzed based on drill core analysis, mineralogical analysis and geophysical borehole logs. Hydrogeochemical data from 15 permanent monitoring wells along a 5.4 km long hillslope transect were analyzed for major and minor ions, total and dissolved organic and inorganic carbon during a 4 year monitoring period and were statistically evaluated. The geological succession of the interlayered and laterally continuous limestone (karst/) fracture aquifers and marlstone aquitards of the Upper Muschelkalk results in two main aquifer assemblages (HTL and HTU = Hainich transect lower/upper aquifer assemblage), which comprise ten previously undocumented individual aquifer storeys. The geologically inferred stratification of the subsurface was confirmed by principal component analysis and cluster analysis of groundwater chemistry. According to groundwater compositions within the HTL and HTU assemblages, there are 5 main clusters (2 in HTU and 3 in HTL). Soil properties are related to infiltration rates and the initial chemistry of recharge waters. The reconstructed recharge zones for the aquifer storeys are characterized by predominantly forest land use on "carbonate series" soils and cropland/pasture land use on "siliceous series" soils, the latter developed from quarternary aeolian loess and alluvial valley fills. Based on the local geological structure, aquifers in the lower positions of the litho/hydrostratigraphy (i.e. HTL) outcrop in higher slope positions, show greater catchment sizes and a greater limestone/marlstone-ratio. The latter leads to thin soils, low water retention potential and predominantly forest land use, resulting in presumably high groundwater recharge rates and little anthropogenic influence on groundwater quality. As the subsurface stratification enforces confined groundwater flow, intrastratal karstification and the resulting hydraulic conductivity increases (and groundwater residence time decreases) with increasing bed thickness and limestone/marlstone ratio towards the lower portions of the stratigraphic succession. By implication, aquifers in the upper litho/hydrostratigraphic positions (HTU) exhibit small and partly agriculturally managed catchments with thick soils, low infiltration potential and, based on thinly bedded aquifer/aquitard successions, low hydraulic conductivities and long groundwater residence times. All in all, the complex interplay of geological structure, lithology, soil group and land use type results in distinct hydrochemical, and presumably ecological conditions in the different aquifers.