Modeling the Effect of pH and Salinity on Biogeochemical Reactions and Metal Behavior in Sediment

A mathematical model is developed to investigate the effect of pH and salinity fluctuation on biogeochemical reactions and metals' behavior in sediments. The model includes one-dimensional vertical advective and diffusive transport of species, serial reductions of electron acceptors, and precipitation/dissolution of species, acid–base chemistry, and metal sorption to sediments. The model was tested using data obtained from laboratory microcosm experiments which exposed metal (Cd, Zn) contaminated sediment to alternating fresh and salty overlying water. The model successfully reproduces the contrasting metal's release behavior and the vertical profiles of pH, Cl^?, SO₄ ^2?, Mn and Fe in porewater and the acid volatile sulfides (AVS) and simultaneously extracted metals (SEM) in sediments. The model showed that FeOOH_(s) was the dominant sorption phase controlling the solubility of the metals at the surficial sediments while AVS controlled the solubility of the metals in anoxic sediments. The model also showed that the release of the metals to overlying water was controlled by the oxidation of metal sulfides in a very thin layer of oxic sediments (2–3 mm). The proposed model can be useful in managing metal contaminated sediments where pH and salinity are fluctuating by assessing the underlying biogeochemical processes and metals' behavior.