Urban run-off from a catchment in Dunedin, New Zealand was sampled and chemically characterised (iron (Fe), lead (Pb), copper (Cu), zinc (Zn) in total and <0.4 (im fractions, suspended solids, nitrogen (N), phosphorus (P), dissolved organic carbon, major ions, pH) during base flows, and storm flows from five rainfall events. Fe and Pb were found to be predominantly particle-associated (>0.4 μm) and their concentrations increased significantly at the beginning of storm run-off. In contrast, the majority of Cu and Zn was found in the <0.4μm fraction before rainfall events but during the initial period of storm flows a significant proportion of Cu and Zn was also present in the >0.4 μm fraction. The results indicate that Cu and Zn may be more bio-available, and more difficult to remove by storm-water treatment, than Pb. The pH level and the concentration of major ions (Ca +2 , Na + , Mg +2 , K + ), dissolved reactive phosphorus, and nitrate generally decreased during storm flows as a result of dilution by rainwater. Concentrations of total N and P often increased during the initial period of storm run-off, which was likely because of wash-off of particulate plant material.