A fractured roman glass block altered for 1800 years in seawater: Analogy with nuclear waste glass in a deep geological repository

Fractured archaeological glass blocks altered 1800 years in seawater are investigated because of their morphological analogy with vitrified nuclear waste. They provide an opportunity for understanding glass alteration in variable confined media (cracks), by studying an actual ancient system in a known stable natural environment. Characterization of the crack network from two-dimensional trace maps (length, alteration thickness, orientation) allows us to determine the three-dimensional geometric parameters (crack density, fracture ratio) and the percentage of alteration, using stereological relations. This methodology could be applied to nuclear glass. From a representative archaeological glass block, we showed that the surface developed by the cracks is 86 ± 27 times greater than the geometric surface but the volumetric alteration is 12.2 ± 4.1%, which is only 12 times greater than the volumetric alteration of the block periphery (about 1 vol%). This unexpected low value is explained by the large variation of the alteration thicknesses in the different types of cracks in relation with their location in the block. The alteration thickness is usually smaller in the internal zone than in the border zone. The alteration layers resulted from three main mechanisms (interdiffusion, glass dissolution, and secondary phase precipitation) leading to two different alteration products (a sodium-depleted layer and mainly a Mg-smectite). Geometric parameters such as the glass surface area/solution volume ratio and transport parameters (renewal of the alteration solution) strongly affected the glass dissolution kinetics. The confined conditions and the diffusive transport of reactive species favor low alteration kinetics. The precipitation of secondary phases also results in sealing of the cracks. Consequently, although it is not known if subcritical crack growth occurred, internal cracks account for only a minor contribution to the overall alteration. These results improve our understanding of alteration in cracks for assessing the predominant physical and chemical parameters that must be considered in long-term nuclear glass modeling