The time-dependent oxidation and carburization behaviour of two type 316H austenitic stainless steels with varying Mn content and differing average austenite grain size of 142 μm in ‘Low Mn’ (0.98 wt.% Mn) and 81 μm in ‘High Mn’ (1.52 wt.% Mn), were assessed at 550 °C and 600 °C in the presence of simulated reactor primary gas coolant containing 500 vppm H 2 O, 100 vppm H 2 , 300 vppm CH 4 and 1 vol.% CO, balanced with CO 2 . Rupture and spallation of the initial protective chromia layer occurs in the ‘High Mn’ steel after 2000 h at 550 ºC, and leads to the formation of a magnetite/spinel oxide layer that reaches 75% surface coverage only after 8000 h. In contrast, ‘Low Mn’ steel reaches ~ 85% coverage after only 1000 h at the same temperature. The development of an inner carburized layer occurs gradually in both steels once the duplex oxide layer is forming. The differences in steel behaviour are reduced at 600 °C, where both oxidation and carburization are significantly accelerated. Only 0.02 wt.% carbon remains in solid solution in the austenite lattice in the carburized layer, the excess carbon atoms precipitating out in the form of Cr-rich M 23 C 6 particles, present both inter- and intragranularly. The experimental values of the activation energy for carburization suggest that diffusion of substitutional solutes as the rate-limiting mechanism of the process. Previously observed carburization depths of ≥ 200 μm in ex-service austenitic stainless steels, may be achieved by preconditioning 316H steel in simulated reactor gas coolant for ≥ 6000 h at 600 ºC.