The composition of dissolved organic carbon (DOC) in stormflow from urban areas has been greatly altered, both directly and indirectly, by human activities and there is concern that there may be public health issues associated with DOC, which has unknown composition from different sources within urban watersheds. This study evaluated changes in the concentration and composition of DOC in stormflow in the Santa Ana River and its tributaries between 1995 and 2004 using a simplified approach based on the differences in the optical properties of DOC and using operationally defined differences in molecular weight and solubility. The data show changes in the composition of DOC in stormflow during the rainy season and differences associated with runoff from different parts of the basin, including extensive upland areas burned prior to the 2004 rainy season. Samples were collected from the Santa Ana River, which drains similar to 6950 km(2) of the densely populated coastal area of southern California, during 23 stormflows between 1995 and 2004. Dissolved organic carbon (DOC) concentrations during the first stormflows of the 'winter' (November to March) rainy season increased rapidly with streamflow and were positively correlated with increased faecal indicator bacteria concentrations. DOC concentrations were not correlated with streamflow or with other constituents during stormflows later in the rainy season and DOC had increasing UV absorbance per unit carbon as the rainy season progressed. DOC concentrations in stormflow from an urban drain tributary to the river also increased during stormflow and were greater than concentrations in the river. DOC concentrations in stormflow from a tributary stream, draining urban and agricultural land that contained more than 320 000 animals, mostly dairy cows, were higher than concentrations in stormflow from the river and from the urban drain. Fires that burned large areas of the basin before the 2004 rainy season did not increase DOC concentrations in the river during stormflow after the fires - possibly because the large watershed of the river damped the effect of the fires. However, the fires increased the hydrophobic neutral organic carbon fraction of DOC in stormflow from the urban drain and the tributary stream.
