ABSTRACT. Seven radiocarbon laboratories: Åbo/Aarhus, CIRCE, CIRCe, ETHZ, Poznań, RICH, and Milano-Bicocca performed separation of carbonaceous fractions suitable for

Absolute dating of mortars is crucial when trying to pin down construction phases of archaeological sites and historic stone buildings to a certain point in time or to confirm, but possibly also challenge, existing chronologies. To evaluate various sample preparation methods for radiocarbon (14C) dating of mortars as well as to compare different dating methods, i.e. 14C and optically stimulated luminescence (OSL), a mortar dating intercomparison study (MODIS) was set up, exploring existing limits and needs for further research. Four mortar samples were selected and distributed among the participating laboratories: one of which was expected not to present any problem related to the sample preparation methodologies for anthropogenic lime extraction, whereas all others addressed specific known sample preparation issues. Data obtained from the various mortar dating approaches are evaluated relative to the historical framework of the mortar samples and any deviation observed is contextualized to the composition and specific mineralogy of the sampled material.

A brief history of the nature, use and technology of binders in ancient constructions and buildings is outlined, including the apparent chronological discontinuities related to technological developments. The skilled and clever use of mineral resources is at the base of the technical achievements related to architectural activities, from simple adobe to high-performance modern concrete. It is argued that among pre-industrial binders the Roman pozzolanic mortars were highly optimized materials, skillfully prepared and very durable. Their innovative use in architecture is one of the keys of the successful expansion of the Roman Empire. The role of mineralogy and mineral reactions is emphasized in terms of: (1) the preparation and manufacturing of the binding materials; (2) the hardening process and the development of the physical properties of the binder; and (3) the archaeometric reconstruction of the ancient materials.

In order to radiocarbon (14C) date a building, several components of the mortar could be used, such as the mortar binder, the lime lumps, the charcoal particles and shell fragments eventually present among the aggregates. In particular, the mortar binder requires a purification treatment in order to separate it from other sources of carbon, which could change the 14C signature of the binder invalidating the dating process. Here, we present the application of the Cryo2Sonic method to 14C dating of the ancient building structures unearthed during excavation at the Padua Cathedral complex. The dated samples were pretreated by using Cryo2Sonic method and the improved Cryo2Sonic version 2.0, recently developed by introducing additional steps such as centrifugation of the mortar suspension and gravimetric sedimentation of the binder fractions. The Cryo2Sonic version 2.0 relies heavily on the characterization of the mortar and of the purified binder fractions, allowing the isolation of a reliable 14C datable mortar fraction. Through this new method, the 14C dating of different ancient structures excavated next to the Padua Cathedral allow to identify the first religious complex of the city of Padua (3rd–4th centuries AD).

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The mortar samples of the Castle of Cannero (Lake Maggiore, Italy) have been characterized and radiocarbon (14C) dated. The presence of LDH phases was identified. The hydraulic reaction was evaluated by a multi-analytical approach. Careful extraction, preparation and purification of the binder fraction have been performed. Contaminations due to LDH phases have been removed allowing reliable absolute dating of the structures. Non-hydraulic lime-based mortars represent only part of the binding materials found in archaeological and historical structures, and a new challenge is the application of 14C dating techniques on mortars that feature hydraulic reactions. This research work aims at 14C dating a series of Mg-rich hydraulic mortars from the Castle of Cannero (Lake Maggiore, Italy), from which both charcoals and mortar samples were collected. A multi-analytical approach employing X-ray powder diffraction (XRPD), optical microscopy (OM), and scanning electron microscopy/energy-dispersive microanalysis (SEM-EDS) was adopted in order to carefully characterize the samples. A wet gravimetric separation for the extraction of the fine fraction mainly composed by the mortar binder was carried out and the binder fraction was characterized by XRPD in order to investigate the presence of contaminants. The binding fractions are characterized by the widespread occurrence of hydrotalcite-type minerals, considered contaminants in 14C dating of mortars because of their capability to exchange carbonate anions even after the hardening process. A further purification treatment by thermal decomposition was performed before 14C dating by AMS. The obtained dates were consistent with archaeological expectations, confirming the potential of the developed purification methodology for hydraulic mortars dating.

Double-layer hydroxide minerals are part of a very interesting group of natural and synthetic compounds with trigonal or hexagonal symmetry and a flexible layered crystal structure. They are formed extremely frequently in geologic, industrial, and synthetic processes. The ease of formation is related to the possibility of accommodating divalent and trivalent cations in the structure, together with a range of anionic species. Some compounds of the group, namely those based on hydrotalcite chemistry, are invariably found as products of the pozzolanic reaction between lime and clays in ancient mortars and modern binders that serve as alternatives to Portland clinker. The present review wishes to relate the structural properties of hydrotalcitetype compounds to the crystal-chemical mechanisms taking place during long-term pozzolanic processes. The kinetics of CO 3 exchange between the hydroxide and the atmosphere has important negative consequences for the radiocarbon dating of ancient mortars.

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