Combined use of spot samples and continuous integrated sampling in a study of storm runoff from a lowland catchment in the south of England

We have used two different sampling techniques to study the geochemical response of a small lowland rural catchment to episodic storm runoff. The first method involves traditional daily spot sampling and has been used to develop a standard end-member mixing analysis (EMMA) of the relative contributions of ground water flow and surface runoff to the total stream flow. The second method utilizes a continuous sampling device, powered by an osmotic pump, to produce an integrated 24-h sample of the stream flow. When combined with the EMMA results from the spot samples, analyses of the integrated samples reveal the presence of a third component that makes a significant contribution to the dissolved NO3, Ca and K export from the catchment during the rising limb of the hydrographic profile of a storm event following a prolonged dry period. The storm occurred in the middle of the night, so that the response of the stream chemistry was not captured by the daily samples. We hypothesize that this third component is derived from the flushing of stored soil water that contains the geochemical signature of decaying vegetation.