Iron corrosion in an anoxic soil: Comparison between thermodynamic modelling and ferrous archaeological artefacts characterised along with the local in situ geochemical conditions

Graphical abstract: Eh/pH diagram based on the in situ conditions measured on the archaeological site of Glinet (France, 16th century). Display Omitted Research highlights: → Long-term corrosion behaviour of ferrous archaeological artefacts in anoxic media. → Use of thermodynamic modelling to correlate the corrosion products to the environmental data. → Thermodynamic data for carbonate phases from the rosasite group (chukanovite). - Abstract: This article is part of an ongoing study on the long-term corrosion behaviour of ferrous archaeological artefacts. The aim of this study is to correlate the corrosion products formed on ancient artefacts in an anoxic medium to the environmental data using thermodynamic modelling. For this purpose, measurement campaigns have been conducted on the archaeological site of Glinet (16th century, High Normandy (Seine-Maritime), France) where the evolution of the pore water chemistry has been recorded for a period of one year. Three evolution steps have been distinguished after the oxidizing perturbation which was induced by the piezometers installation. The first step was related to an oxidizing environment in which pore water was in equilibrium with a Fe(III) precipitated phase: ferrihydrite (FeOOH.0.4 H2O). The second step was considered as an intermediate step and Fe speciation had evolved; equilibrium was achieved between ferrihydrite and a Fe(II) carbonate phase: siderite (Fe(II)CO3). The last step of the evolution was related to a reducing stage where pore water was in equilibrium with magnetite (Fe3(II,III)O4) and with chukanovite (Fe2(II)(OH)2CO3). As these phases were present in the corrosion layers formed on the archaeological samples, it is possible to conclude that the thermodynamic approach was helpful in developing a better understanding of the effect of geochemical conditions on the composition and mineralogy of the corrosion products formed on archaeological artefacts. This work could be used as a reference for further corrosion studies, especially on long-term corrosion processes applied to nuclear waste disposal.