The management of stormwater pollution has placed particular emphasis on the first flush phenomenon. However, definition and current methods of analyses of the phenomena contain serious limitations, the most important being their inability to capture a possible impact of the event size (total event volume) on the first flush. This paper presents the development of a novel approach in defining and assessing the first flush that should overcome these problems. The phenomenon is present in a catchment if the decrease in pollution concentration with the absolute cumulative volume of runoff from the catchment is statistically significant. Using data from seven diverse catchments around Melbourne, Australia, changes in pollutant concentrations for Total Suspended Solids (TSS) and Total Nitrogen (TN) were calculated over the absolute cumulative runoff and aggregated from a collection of different storm events. Due to the discrete nature of the water quality data, each concentration was calculated as a flow-weighted average at 2 mm runoff volume increments. The aggregated concentrations recorded in each increment (termed as a 'slice' of runoff) were statistically compared to each other across the absolute cumulative runoff volume. A first flush is then defined as the volume at which concentrations reach the 'background concentration' (i.e. the statistically significant minimum). Initial results clearly highlight first flush and background concentrations in all but one catchment supporting the validity of this new approach. Future work will need to address factors, which will help assess the first flush's magnitude and volume. Sensitivity testing and correlation with catchment characteristics should also be undertaken.