Coupled modelling has been performed using geochemical/transport codes and radiolysis models to describe the chemical evolution of the waste forms “high-level waste glass” and “spent nuclear fuel” together with its waste package and engineered barrier surroundings. Near field processes considered include container corrosion, hydrogen generation, mass transfer for radionuclides and other waste matrix components in corrosion products and buffer materials, geochemistry of near field solution chemistry, sorption of radionuclides on surface sites in the nano-sized pore space of near field materials and the radiolytic decomposition of pore water. The rate limiting steps in waste form dissolution and secondary phase formation mechanism and the associated radionuclide mobilisation chemistry (solubility, solid solution formation, speciation, redox stability) are strongly influenced by the near field constraints.