Predicting soil-water partition coefficients for Hg(II) from soil properties

Abstract

The metal adsorption characteristics for fifteen Taiwan soils by Hg(II), were evaluated using pH as the major variable. The soil samples were thoroughly characterized for their physical chemical properties and composition, particularly organic matter and metal oxides. The adsorption of Hg(II) increased with increasing pH between pH 2.5 and 5.5, whereas the adsorption significantly decreased above around pH 5.5. Below pH 5.5, greater adsorption was found for soils with a higher organic matter content at constant pH and metal concentration. To better understand the mechanism of adsorption, the experimental results for Hg (II) were tested in a partition coefficient model to relate the adsorption of the Hg(II) by the different soils with soil components: organic matter, iron oxide, aluminium oxide and manganese oxide. This model was not successful when applied to measurements at the differing natural soil pHs because of the importance of pH. At pH greater than 5.5 the model fails because of the complexation of Hg by the dissolved organic matter. However, partition coefficients obtained from experimental data were highly correlated with those calculated for a partition coefficient between mercury and organic matter alone at lower pH. Normalization of the partition coefficients, Kd, for the organic matter content of the soils, Kom, greatly improved the correlation between the partition coefficient and pH under pH 5.5 (R2 increased from 0.484 to 0.716). This suggests that the surficial adsorption sites are principally due to organic matter for pH less than 5.5. For the 24-hour equilibration period employed, diffusion of Hg through this superficial organic matter coating to underlying sorptive materials, including metal oxides, is not important in the partitioning of Hg. At pH above 5, a decrease of mercury adsorption with increasing solution pH was also found. This result may be explained in part by the complexation of mercury by soil dissolved organic matter whose concentration increased with increasing pH.