ABSTRACT Gypsum-bearing rocks and mortars were often used to build historical masonries. In many cases, the restoration of such buildings with unsuitable binders resulted in severe damages of the masonry due to the formation and swelling of hydrous sulfate minerals. Here, we have studied an extreme case of damage, which occurred due to inappropriate restoration of the historical city wall in Mühlhausen (Thuringia, Germany). To understand the causes for the fatal wall degradation, we collected samples from the wall interior during its deconstruction and analyzed them by thermal analysis, X-ray diffraction, and LA-ICP-MS. The investigations reveal the formation of concentric reaction zones of secondary ettringite and gypsum, which occur particularly around emplaced anchors at the contact between injected cement and gypsum-bearing masonry materials. The swelling in ettringite reaction rings produced concentric cracks around anchors, in which gypsum precipitated from sulfate-bearing solutions. This process of swelling, cracking, and precipitation repeated in periods of water entry and resulted in the formation of multiple laminated gypsum layers in a transition zone. We conclude that the fatal damage of the city wall of Mühlhausen is primarily due to ettringite formation, because gypsum precipitated in empty cracks, likely exerting no extensional forces on the masonry structure.
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