2017/07/01 by Marie D. Jackson, Sean R. Mulcahy, Heng Chen +4 · 3 citations
Chemistry · Earth and Planetary Sciences · Engineering · Materials Science · #Analcime #Building materials and conservation #Calcium Carbonate Crystallization and Inhibition #Carbonation #Cement #Chemistry #Composite material #Concrete and Cement Materials Research #Gehlenite #Geochemistry #Geology #Materials science #Metallurgy #Mineralogy #Tobermorite #Zeolite
paper · pdf · doi:10.2138/am-2017-5993ccby
openalex publication_date 2017/07/01 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/01
Pozzolanic reaction of volcanic ash with hydrated lime is thought to dominate the cementing fabric and durability of 2000-year-old Roman harbor concrete. Pliny the Elder, however, in first century CE emphasized rock-like cementitious processes involving volcanic ash ( pulvis ) “that as soon as it comes into contact with the waves of the sea and is submerged becomes a single stone mass ( fierem unum lapidem ), impregnable to the waves and every day stronger” ( Naturalis Historia 35.166). Pozzolanic crystallization of Al-tobermorite, a rare, hydrothermal, calcium-silicate-hydrate mineral with cation exchange capabilities, has been previously recognized in relict lime clasts of the concrete. Synchrotron-based X-ray microdiffraction maps of cementitious microstructures in Baianus Sinus and Portus Neronis submarine breakwaters and a Portus Cosanus subaerial pier now reveal that Al-tobermorite also occurs in the leached perimeters of feldspar fragments, zeolitized pumice vesicles, and in situ phillipsite fabrics in relict pores. Production of alkaline pore fluids through dissolution-precipitation, cation-exchange and/or carbonation reactions with Campi Flegrei ash components, similar to processes in altered trachytic and basaltic tuffs, created multiple pathways to post-pozzolanic phillipsite and Al-tobermorite crystallization at ambient seawater and surface temperatures. Long-term chemical resilience of the concrete evidently relied on water-rock interactions, as Pliny the Elder inferred. Raman spectroscopic analyses of Baianus Sinus Al-tobermorite in diverse microstructural environments indicate a cross-linked structure with Al 3+ substitution for Si 4+ in Q 3 tetrahedral sites, and suggest coupled [Al 3+ +Na + ] substitution and potential for cation exchange. The mineral fabrics provide a geoarchaeological prototype for developing cementitious processes through low-temperature rock-fluid interactions, subsequent to an initial phase of reaction with lime that defines the activity of natural pozzolans. These processes have relevance to carbonation reactions in storage reservoirs for CO 2 in pyroclastic rocks, production of alkali-activated mineral cements in maritime concretes, and regenerative cementitious resilience in waste encapsulations using natural volcanic pozzolans.