Longitudinal Profiles of Stream Chemistry in Headwater Catchments in Germany

Headwater streams account for 70% or more of total stream length in most catchments, making it crucial to better understand the processes and controlling factors governing streamflow generation as well as water quality. In this context, stream water chemistry longitudinal profiles can provide valuable insights. This study examines longitudinal stream chemistry profiles across six headwater catchments in three mid-mountain ranges in Germany: The Ore Mountains (catchments OM 1 and OM 2), Black Forest (BF 1 and BF 2), and Sauerland (SL 1 and SL 2).

Three to four snapshot sampling campaigns were conducted per catchment across different seasons and catchment wetness conditions. During the campaigns, water samples were collected from 22 stream monitoring points in the Ore Mountains catchments, 14 in the Black Forest, and 14 in Sauerland, and the samples were analyzed for major cations, anions, and dissolved organic carbon. Subsequently, the longitudinal profiles observed were grouped into spatial and temporal patterns.

In the Ore Mountains, solute concentrations were generally stable over time. However, the spatial patterns varied between the two neighbouring catchments (OM 1 and OM 2). OM 2 exhibited chemostatic longitudinal profiles for most solutes, while OM 1 showed pronounced spatial variability in solutes such as nitrate, dissolved organic carbon (DOC), chloride, and sodium. This variability is usually linked to monitoring points located near springs, tributaries, and drainage systems. However, some spikes in ion concentrations along the stream were not linked to these obvious inflows, thus potentially indicating hotspots for groundwater inflow. The Sauerland catchments showed elevated concentrations of DOC, magnesium, calcium, and sodium in July 2023, a period associated with lower streamflow. An increase in concentration from upstream to downstream was here seen in both streams for solutes like calcium and sodium, during all snapshot campaigns. However, other solutes, like nitrate and sulfate, showed different longitudinal patterns and notable shifts in solute concentration during the snapshot campaigns in SL 2. The shifts in patterns indicate a dependency on time-variant factors like seasonal changes in water input, and land use practices. BF 1 catchment in the Black Forest showed a decreasing pattern in DOC, from upstream to downstream, while the neighbouring catchment BF 2 showed a chemostatic trend. These trends could be influenced by the land use changes within the catchments. Notable increased nitrate concentrations were seen along reaches adjacent to grassland areas and at sampling points near tile drains in OM 1, BF 1, SL 1, and SL 2.

Overall, solute spatial and temporal patterns were stream-specific, with no universal behaviour observed across all catchments. This variability likely results from the interplay of factors such as geology, soils, land use, stream morphology, and climate. High-resolution spatial sampling enabled the identification of point sources and hotspots of groundwater inflow which could be missed by sparse sampling. These findings enhance our understanding of the processes regulating water quality and flow in headwater systems, providing a basis for better management of these systems.