A Combined X-ray Absorption and Mössbauer Spectroscopy Study on Fe Valence and Secondary Mineralogy in Granitoid Fracture Networks: Implications for Geological Disposal of Spent Nuclear Fuels.

Underground repository in crystalline bedrock is a widely accepted solution for long-term disposal of spent nuclear fuels. During future deglaciations, meltwater will intrude via bedrock fractures to the depths of future repositories where O2 left in the meltwater could corrode metal canisters and enhance the migration of redox-sensitive radionuclides. Since glacial meltwater is poor in reduced phases, the quantity and (bio)accessibility of minerogenic Fe(II) in bedrock fractures determine to what extent O2 in future meltwater can be consumed. Here, we determined Fe valence and mineralogy in secondary mineral assemblages sampled throughout the upper kilometer of fractured crystalline bedrock at two sites on the Baltic Shield, using X-ray absorption and Mössbauer spectroscopic techniques that were found to deliver matching results. The data point to extensive O2-consuming capacity of the bedrock fractures, because Fe(II)-rich phyllosilicates were abundant and secondary pyrite was dispersed deep into the bedrock with no overall increase in Fe(II) concentrations and Fe(II)/Fe(III) proportions with depth. The results imply that repeated Pleistocene deglaciations did not cause a measurable decrease in the Fe(II) pool. In surficial fractures, largely opened during glacial unloading, ferrihydrite and illite have formed abundantly via oxidative transformation of Fe(II)-rich phyllosilicates and recently exposed primary biotite/hornblende.