RES³T - Rossendorf Expert System for Surface and Sorption Thermodynamics

A surface complexation model of Se(IV) sorption on biotite with one type of strong sorption sites and two types of weak sorption sites were developed based on experimental data obtained from titration, sorption edge and sorption isotherm experiments. Titration data was collected using a batch-wise manner together with backtitration to calibrate the effect of mineral dissolution in 0.01 M KClO₄ background electrolytes from pH 3 to 11 in an inert atmosphere glovebox. Further calibrations of the titration curve include proton exchange and cation exchange in which the calculations of cation occupancies on biotite surfaces were taken into account. The sorption edge measurements were determined by measuring the sorption of 10⁻⁹ M total Se with a radioactive Se-75 tracer on converted biotite in 0.01 M KClO₄ solution from pH 3 to 11. Se sorption was observed to be strongly dependent on pH. Surface complexation modelling was performed by deriving a set of optimized parameters that can fit titration, sorption edge and sorption isotherm (at pH ~7.7) experimental data. A CASTEP code implemented into Materials Studio was used to calculate the site densities and site types on the biotite surfaces. Weak sorption sites with site densities of 3.2 sites/nm² and 1.4 sites/nm² were derived from the codes and used in the sorption model. A computer code that coupled PHREEQC with Python was developed for the fitting and optimizing processes. The model was validated by sorption data at pH ~9.5. The results show that the model can provide quantitative predicts of Se(IV) sorption in groundwater conditions of a deep geological repository and help improve the performance assessments by giving more convincing estimates of the release of radionuclides towards aquifers and biosphere.