Irregular discharges of polluted stormwater into drainage systems during base flow (no rainfall) result in acute ecological impacts within fluvial and estuarine environments. In this study, metal and TSS concentrations were significantly more variable during business hours of weekdays (i.e. high-business activity) than weekends/public holidays (i.e. low-business activity) within three highly-urbanised catchments of Sydney estuary (Australia), as determined by analysing multivariate dispersion (PERMDISP). Concentrations of TSS and all metals analysed (Al, Ca, Cu, Fe, Mg, Pb and Zn) were also significantly greater during high- than low-business periods within at least one of the three catchments. In no case were concentrations significantly higher during low- than high-business periods. This pattern of contamination supports the hypothesis that commercial and industrial sources are major contributors of irregular discharges of contamination to Sydney estuary. Irregular discharges and consequential ecological impacts may be effectively reduced in this environment by focussing management efforts on these activities.