The goal of the study was to characterize the limestone that was used extensively in the ancient city of Pella (Macedonia, Greece), the birthplace of Alexander the Great. An on-site examination of the building material was carried out to record the types of damage and to select sampling areas. A variation in the nature of the stone and the degree of deterioration, even between the stones that comprise a specific monument structure, was observed, with water absorption and biological colonization being the main factors resulting in the deterioration of the stone. A comprehensive microanalysis and testing scheme was conducted to fully characterize the mineralogical, chemical, mechanical and thermal properties of the stones collected from various areas of the archaeological site. Optical microscopy, XRD and SEM–EDX were used to investigate the chemical composition and the structure of the stone samples. Finally, other properties, such as porosity, specific gravity and water absorption, were measured. Surface alterations, material degradation and biological deterioration were observed in most samples. The results obtained using XRD showed that the dominant mineral phase of the limestone is calcite, with quartz and clay minerals also detected in traces. The microscopic examination of the samples showed that the main natural stone at the archaeological site is a marly limestone. Thermographical measurements showed that the decay of the stones due to ambient temperature variation and corresponding contraction/expansion phenomena may be relatively limited, as the stone exhibited a low thermal diffusivity. Moreover, high porosity values (12.06–21.09%) and low compressive strength (11.3–27.7 MPa) were recorded, indicating the vulnerability of the stone and the need to take conservation measures.

Superhydrophobic materials have clear potential for mitigating rain/humidity-induced damage to cultural heritage. In the present study, the wetting properties of Paraloid B72 were tailored to achieve superhydrophobicity by incorporating modified calcium carbonate (CaCO₃) nanoparticles (NPs). B72 is a well-established conservation product while CaCO₃ is chemically compatible with calcareous materials commonly found in cultural heritage buildings and objects. Initially, the wettabilities of CaCO₃ NPs, functionalised with caproic (C6), caprylic (C8), lauric (C12), myristic (C14), palmitic (C16), and stearic (C18) acid, were evaluated by measuring water contact angles (CAs) on NP pellets. For NPs with short hydrocarbon chains, CA increased with chain length, from 66.3° for CaCO₃-C6 to 118.0° for CaCO₃-C12 NPs. For NPs with longer chains, CA remained stable and around 118°. Based on these results, CaCO₃-C12 NPs were selected for further investigation and subjected to transmission electron microscopy analysis, which revealed chain-like agglomerates of aggregated nanocrystallites (5–10 nm) forming 40–150 nm polycrystalline NPs. Scanning transmission electron microscopy combined with elemental mapping revealed a homogeneous distribution of Ca, C, and O within the NPs. Next, CaCO₃-C12 NPs were dispersed in B72 solutions and sprayed onto limestone, which was employed as a model calcite-rich substrate. At optimal NP concentration, the resulting composite coating exhibited superhydrophobicity (CA > 150°), while it induced minimal colour alteration to limestone and effective resistance to capillary water absorption. The fluorine-free coating also demonstrated good durability against UV exposure, drop impact, salt attack, freeze–thaw cycles, tape peeling, drop pH variations, and thermal treatment.