Dissolution of silica and the development of concentration profiles in freshwater sediments

The dissolution of silica and diffusion of reactive dissolved Si in the porewaters of river sediments are investigated using sediments of different physical and chemical properties. Three sediments are considered: (a) from sectioned cores taken from a river-bed, (b) fine organic-rich surface sediment (<5 cm depth) installed in a fluvarium channel and, (c) coarse river sediment of low organic matter content also installed in a fluvarium channel. Dissolution rates of silica are measured at 10°C using batches of suspended material. The derived dissolution rate constants show large differences between the sediments. The river bed-sediment cores had vertical concentration profiles of dissolved Si that are consistent with the diffusion and dissolution of biogenic silica. Experiments in a fluvarium channel enabled Si fluxes to be calculated from a mass-balance of the overlying solution. The results are consistent with the attainment of a steady-state concentration profile of dissolved Si in the sediment. There are no discernible effects of water velocity over the sediment between 5 and 11 cm s^?1. However, at 20 cm s^?1, the flux increases as a result of either entrainment of fine particles at the surface or advective effects in the surface sediment. A fluvarium experiment with the fine sediment (<125 μm) over 61 days, produced a concentration profile with the highest concentration of 1025 μmol dm^?3 at a depth of 4–5 cm in the sediment. A FORTRAN program is used to model the results of the increase in dissolved Si in the overlying water and development of a concentration profile in the porewater. This leads to a sediment diffusion coefficient of 1.21×10^?9 m² s^?1 at 8.8°C at the beginning of the experiment and rate constant k=13.1×10^?7 s^?1 at pH=7.82 and average temperature of 7.6°C for the entire experiment. Fluxes measured at the sediment–surface interface and calculated assuming steady-state profiles had developed are typically 0.01–0.04 μmol m^?2 (of river bed) s^?1. The approach enables the efflux of dissolved Si from bottom-sediments to be estimated from dissolution rates measured using suspensions of bed-sediment.