A New Era in Ceramic Archaeometry: A Comprehensive Multimodal Methodological Workflow

Abstract

This study establishes a comprehensive, sequential multimodal workflow for archaeometric analysis of medieval ceramics, integrating seven measurement techniques to characterize elemental, crystalline, amorphous, microstructural, structural, and chemical-state properties of the material, while preserving artefact integrity. Therefore, (i) X-ray fluorescence establishes baseline major (Si, Al, Fe, Ca, K, Na) and trace (Cr, Mn, Zr) profiles for paste discrimination; (ii) X-ray diffraction identifies kaliophilite/oligoclase phases (~ 800–900°C firing); (iii) Fourier transform infrared resolves amorphous networks (Si–O–Si 950–1100 cm^-1); (iv) Raman spectroscopy detects microscale oxide impurities (anatase TiO₂ lattice modes at 110–160 cm^-1, ZrO₂, Al₂O₃ corundum M–O stretching modes at 440–465 cm^-1) and lattice defects, revealing heavy mineral tempers (rutile sands) and refractory phases undetectable by bulk diffraction analysis or the broad spectral envelopes of infrared spectroscopy; (v) scanning electron microscope with energy dispersive spectroscopy quantifies temper distributions; (vi) X-ray computed tomography reveals 3D void networks, and (vii) X-ray absorption near-edge structure constrains speciation of Fe²⁺/Fe³⁺, Ca carbonate–silicates, and K-feldspars. This standardized framework enables precise reconstruction of provenance, fluxing strategies, pyrotechnology, and post-firing alterations, beyond the limitations of single- and dual-technique approaches, providing a reproducible protocol for heritage science.