This paper demonstrates the application of a low-cost and rapid natural fluorescence technique for tracing and quantifying the transport of pollutants from livestock farming through a small headwater catchment. Fluorescence intensities of Dissolved Organic Matter (DOM) present in different pollutant sources and drainage waters in the Den Brook catchment (Devon, UK) were monitored through storm events occurring between January 2007 and June 2008. Contrasting fluorescence signals from different sources confirmed the technique's usefulness as a tracer of pollutants from livestock farming. Changes in fluorescence intensities of drainage waters throughout storm events were used to assess the dynamics of key pollutant sources. The farmyard area of the catchment studied was shown to contribute polluted runoff at the onset of storm events in response to only small amounts of rain, when flows in the Den Brook first-order channel were low. The application of slurry to a field within the catchment did not elevate the fluorescence of drainage waters during storm events suggesting that when slurry is applied to undrained fields the fluorescent DOM may become quickly adsorbed onto soil particles and/or immobilised through bacterial breakdown. Fluorescence intensities of drainage waters were successfully combined with discharge data in a two component mixing model to estimate pollutant fluxes from key sources during the January 2007 storm event. The farmyard was shown to be the dominant source of tryptophan-like material, contributing 61-81% of the total event flux at the catchment outlet. High spatial and temporal resolution measurements of fluorescence, possibly using novel in-situ fluorimeters, may thus have great potential in quickly identifying and quantifying the presence, dynamics and sources of pollutants from livestock farming in catchments.