Microstructural and compositional analysis of historical mortars is an active research field, not only to guarantee the use of compatible repair measures, but also to guide the design of novel efficient materials. Despite the crucial role of Roman mortars in building history, there is a significant lack of knowledge of their pore system in relation to building techniques and durability. From these premises, this research focuses on the structural mortars of the Realillo aqueduct (Archaeological Site of Baelo Claudia, Spain). This construction is especially interesting from a durability point of view, as in addition to being in a windy coastal area, the water-proof potential of the material is a major issue. Complementary experimental techniques (petrography, computed tomography, X-ray fluorescence, X-ray diffraction (micro and conventional), thermal analysis, pycnometry, physisorption, Hg porosimetry, and SEM-EDS) are applied within a multidisciplinary approach, including the Vitruvian guidelines and comparative analysis with coetaneous buildings. The size and shape of the pores and the porous volume distribution have been linked to hydraulicity, and to cohesion and weathering resistance. Total and open porosity can be related to waterproof worsening, and the entrapped air pores detected could indicate inadequate placement. The shrinkage cracks can be related to the sea sand aggregate. Thermal analysis and C-A-S-H gel indicate hydraulic phases, but with different hydraulicity levels. This variation could be related to the non-high-purity limestone and/or to the recipe. The differences in binder/aggregate ratios and petrographic classification confirm the distinct compositions. Non-standardized manufacturing or building stages could be related to compositional variations. This research has provided significant insights into durability and manufacturing issues by integrating a micro–macro pore structure study within multianalytical and interdisciplinary research. The method may be used as a complementary procedure to characterize historical mortars. As upgrading/degrading durability factors were obtained, a conservation campaign could be designed. In addition, knowledge about historical building techniques and materials has been enriched.
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