Modelling heavy metals in estuarine environments is extremely complex for various reasons; one of the primary complicating factors is that metals exist in two phases, dissolved and particulate bound. Dynamic changes in water chemistry, and in particular salinity, affect the partitioning of metals between the two phases and hence make it difficult to determine the fractions of each phase. A relatively simple approach was developed to relate variations in partition coefficient for Pb to salinity fluctuations in the Mersey Estuary. The functional relationship developed between partition coefficient and salinity departs from the traditional exponential type curve, providing a more realistic relationship.A numerical model was then developed for predicting the transport and distribution of Pb about the Mersey Estuary. The model couples transport of metals throughout the water along with incorporating the chemical processes controlling how lead is fractioned between dissolved and particulate phases through the newly developed partition coefficient relationship. Model predictions of dissolved Pb along the longitudinal axis of the estuary were compared with measurements of Pb for two events: very good correlation was obtained between the model results and the data. The approach is compared with approaches adopted by other researchers. Also results are presented for the determination of partition coefficients for a second metal, Ni, using the Author's approach. These results are used to support the approach developed by the Authors. (C) 2008 Civil-Comp Ltd. and Elsevier Ltd. All rights reserved.