The chemical speciation analysis of chromium in one of the most important South American Estuary was performed for the first time. Samples were collected in Patos Lagoon Estuary (Brazil) and were analysed by adsorptive cathodic stripping voltammetry, with the following analytical figures of merit: limit of detection, 0.1 nmol L(-1); precision RSD = 3%, n = 7; linearity, from limit of quantitation up to 20 nmol L(-1); and accuracy of 99.8%, expressed as recovery. No labile chromium forms were identified in samples, beside industries and a city were near the study area. It is pointed out a reverse correlation between total and non-active chromium and salinity, which could be explained by biogeochemical processes.