Abstract. Carbon steel is a potential canister material for the disposal of high-level radioactive waste in deep geological repositories in clays and clay rocks. Bentonite is considered as a potential backfill material for those multi-barrier systems. To predict the long-term performance and for safety assessment the knowledge of canister corrosion behavior is important. The corrosion products formed and mineralogically altered bentonite at the canister/bentonite interface can potentially provide an additional barrier against radionuclide migration. In-situ corrosion experiments were performed at the Mont Terri underground research laboratory. Coupons of carbon steel were embedded in Volclay MX-80 bentonite with controlled densities, installed in a borehole under simulated repository and anaerobic conditions and exposed to natural Opalinus clay porewater for a period up to 5.5 years (Smart et al., 2017). In the present study, the bentonite layer at the canister/bentonite interface was characterized by complementary microscopic and spectroscopic techniques (XPS, SEM-EDX, µXANES) under anoxic conditions. The interface revealed reddish-brown staining up to 2 mm depth into the bentonite in the zone adjacent to the steel in all three obtained samples. The XPS analysis revealed formation of sulfides at the interface consisting of iron and other trace metals present in the steel. The SEM-EDX analyses of the interface (embedded cross-cut with steel removed) showed different degrees of calcium enrichment in the bentonite adjacent to the metal for various samples. The µXRF analysis performed on the bentonite at the interface showed a scarce or distinct calcium-enriched rim up to 100 µm into the bentonite and iron-enriched rim depending on the sample (one sample in Fig. 1), while µXANES analysis revealed formation of iron silicate compounds in the reacted reddish-brown zone. The iron appears to displace calcium from the interlayer sites in montmorillonite. The calcium then precipitates at the interface as calcite. The extent of this process seems to be strongly related to the bentonite density. The steel coupon was removed prior to embedding, with the location marked as resin in Fig. 1. A line scan from the edge towards the bulk bentonite did not indicate any systematic gradient in the Fe2+/3+ ratio. The formation of mixed Fe2+/3+ silicate compounds appears to be heterogeneous. This work contributes to an increasing understanding of steel corrosion mechanisms in clay, which can improve the robustness of canister lifetime predictions.