Groundwater isoscapes in a montane headwater catchment show dominance of well-mixed storage

We conducted an integrated groundwater-surface water monitoring programme in a 3.2-km(2) experimental catchment in the Scottish Highlands by sampling all springs, seepages, and wells in six, spatially extensive synoptic surveys over a 2-year period. The catchment has been glaciated, with steep hillslopes and a flat valley bottom. There is around 70% glacial drift cover in lower areas. The solid geology, which outcrops at higher elevations, is granite and metamorphic schist. The springs and seepages generally occur at the contact between the solid geology and drift or at breaks of slopes in the valley bottom. Samples were analysed for stable isotopes, Gran alkalinity and electrical conductivity. Despite the surveys encompassing markedly different antecedent conditions, the isotopic composition of groundwater at each location exhibited limited temporal variability, resulting in a remarkable persistence of spatial patterns indicating well-mixed shallow, groundwater stores. Moreover, line-conditioned excess values derived from the isotope data indicated no evidence of fractionation affecting the groundwater, which suggests that most recharge occurs in winter. The alkalinity and electrical conductivity of groundwater reflected geological differences in the catchment, being highest where more weatherable calcareous rocks outcrop at higher altitudes in the catchment. Springs draining these areas also had the most variable isotope composition, which indicated that they have shorter residence times than the drift covered part of the catchment. The study showed that even in geologically heterogeneous upland catchments, groundwater can be characterized by a consistent isotopic composition, reflecting rapid mixing in the recharge zone. Our work, thus, emphasizes the critical role of groundwater in upland catchments and provides tracer data that can help constrain quantitative groundwater models.