Modelling the diffusive transport and remobilisation of Cs-137 in sediments: The effects of sorption kinetics and reversibility

In determining the mobility of ions in sediments it is important to take account of the solid phase sorption and speciation. Measurements were made of activity depth profiles of Cs-137 from fallout from Nuclear Weapons Testing and from the Chernobyl accident in two lake sediments. The fraction of Cs-137 in the aqueous, exchangeably sorbed and ''fixed'' phases was determined at each depth interval. A model was developed to simulate the transport of Cs-137 in these sediments, taking account of changes in sorption properties as the concentration of the competing ammonium ion changes with depth, as well as transfers of activity to less-exchangeable sites on the solids. The model simulations give reasonable agreement with experimental data, and the fitted rate constant for slow transfers to less-exchangeable sites (T-1/2 = 50-125 d) is in agreement with independent measurements. The modelling gave evidence for a reverse reaction from less-exchangeable to exchangeable sites with a half-life of order 10 y. Model results were compared with those generated by a physical mixing model and the standard molecular diffusion model assuming equilibrium sorption to the solid phase. Estimates were made of the remobilisation of Chernobyl Cs-137 from these sediments to the water column: predicted rates vary from around 3% of the inventory per year 2 years after the fallout event to 0.04% per year 30 years after the fallout.