|Lischeid, G; Bittersohl, J: Tracing biogeochemical processes in stream water and groundwater using nonlinear statistics, Journal of Hydrology, 357, 11-28 (2008), doi:10.1016/j.jhydrol.2008.03.013
Stream water and groundwater solute concentration are subject to a multitude of biogeochemical processes that act at different scales and are often characterized by non-linear relationships and feedback loops. Different multivariate statistical methods were applied to investigate the interplay of different processes. The data set from the Lehstenbach catchment in South Germany comprised 2641 stream water and groundwater samples from 38 different sites in the catchment, where 13 different solutes had been determined. According to the correlation dimension analysis, the number of dominant processes was four. The first four components determined via principal component analysis comprised 88% of the total variance, whereas the non-linear isometric feature mapping explained 92% with the first four components. These components were ascribed to prevailing biogeochemical processes and were used to investigate spatial and temporal patterns. Redox processes and contamination by road salt explained 35% of the variance each. Another 13% were ascribed to near-surface runoff in the acidified topsoil, and 9% to the impact of contaminated filter gravel in some of the groundwater wells. The redox component exhibited clear seasonal patterns at most stream water and groundwater sampling sites, with the most reduced conditions in late summer, immediately before the onset of re-wetting. There was clear evidence that redox processes, especially denitrification, play an important role even in the oxic aquifer. During discharge peaks, stream water exhibited higher values of the near-surface runoff component. However, the associated lower values of the redox component pointed to near-surface runoff in the riparian wetlands as the predominating runoff generation process rather than to a contribution of upslope soil water. A series of major rain storms in fall 1998 altered groundwater and stream water solute concentration for months: stream water and groundwater became more oxic and more acidified, and showed a higher impact of road salt contamination at some sites. Overall, the spatial and temporal patterns of the predominating components gave a consistent picture and helped considerably to better understand the interplay between biogeochemical and hydrological processes. The chosen approach is a promising tool for investigating apparently complex hydrological and biogeochemical systems.