A simple and rapid procedure for on-site qualitative and quantitative analysis of organic matter from discharges of municipal wastewater in seawater has been developed. This method is based on the knowledge of the UV signal of both seawater and anthropogenic absorbing matter and on the mathematical deconvolution of the sample spectrum using reference spectra. The main application is the estimation of TOC at the direct outlet of the discharge. This quantitative application is obviously limited by the nature of organic compounds, but the UV estimation allowed us to have an overview of the composition and evolution of organic matter into the polluted area. The application of this procedure has been carried out to study the wastewater dilution into an area receiving urban discharges. Experiments showed satisfactory analytical features with a range of TOC values from 75 to 1500 μM C, and the comparison of the results with those obtained by reference method presented a reasonable correlation (r2 = 0.9636) in the marine discharge. The results have also allowed us to quickly estimate the plume evolution at the sea surface and in depth. This alternative method could be integrated in a portable device for on-site analysis and multiplication of measurements for relevant results, or in a continuous flow analyser. © 2006 Taylor & Francis.