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Defining hydrochemical evolution of streamflow through flowpath dynamics in Kawakami headwater catchment, Central Japan

The hydrochemical behaviour of catchments is often investigated by inferring stream chemistry through identification of source areas involved in hydrograph separation analysis, yet its dynamic evolution of hydrologic pathways has received little attention. Intensive hydrometric and hydrochemical measurements were performed during two different storms on March 29, 2001 and August 21–22, 2001 to define hydrochemical evolution under the dynamic of flow pathways in a 5·2 ha first‐order drainage of the Kawakami experimental basin (KEB), Central Japan, a forested headwater catchment with various soil depths (1·8 to 5 m) overlying late Neogene of volcanic bedrocks. The hydraulic potential distribution and flow lines data showed that the change in flow direction, which was controlled by rainfall amount and antecedent wetness of the soil profile, agreed well with the hydrochemical change across the slope segment during the storm. Hydrograph separation predicted by end‐member mixing analysis (EMMA) using Ca2+ and SiO2 showed that near surface riparian, hillslope soil water and deep riparian groundwater were important in stream flow generation. The evidence of decrease in solutes concentration at a depth of 1 m in the hillslope and 0·6 m in the near surface riparian during peak storm suggested a flushing of high solutes concentration. Most of the solutes accumulated in the deep riparian groundwater zone, which was due to prominent downward flow and agreed well with the residence time. The distinct flow pathways and chemistry between the near surface riparian and deep riparian groundwater zones and the linkage hillslope aquifer and near surface riparian reservoir, which controls rapid flow and solutes flushing during the storm event, are in conflict with the typical assumption that the whole riparian zone resets flow pathways and chemical signature of hillslope soil water, as has been reported in a previous study. Copyright © 2005 John Wiley & Sons, Ltd.