: The identification and characterization of pigments and inks in historical manuscripts and artworks plays a crucial role in understanding artistic techniques, material composition, provenance, and authenticity. In this study, non-invasive in-situ analytical techniques, principal component analysis and supervised chemometric modeling are employed to investigate selected manuscripts dated between the 14th and 18th centuries and preserved at the University Library of Cagliari (BUCA). Micro-Raman spectroscopy provides molecular and structural information on pigment composition and degradation processes, while fiber optic reflectance spectroscopy (FORS) and colorimetric measurements allow the characterization of chromatic properties and their correlation with specific materials. Luminescence spectroscopy was further used to support pigment identification through emission features under UV excitation. Additionally, Principal Component Analysis (PCA) was applied to the Raman datasets to explore patterns and similarities among pigments and inks, whereas FORS, luminescence spectroscopy, and colorimetric measurements provided complementary information for material characterization. Building on this exploratory approach, supervised chemometric models based on Soft Independent Modeling of Class Analogy (SIMCA) and Linear Discriminant Analysis (LDA) were evaluated as a preliminary, proof-of-concept framework for comparing the spectral profiles of pigments and inks across manuscripts, and for illustrating a possible future approach to provenance screening. These methods offer a preliminary framework for distinguishing among the manuscripts examined and for flagging anomalous samples, pending validation on a larger, independent dataset. The integration of these techniques within a compact and portable system demonstrates its effectiveness for non-destructive cultural heritage diagnostics. In this work, a preliminary exploratory analysis illustrates the potential for future combination of Raman, FORS, luminescence, and colorimetric information within integrated chemometric workflows, providing a proof-of-concept basis for more extensively validated approaches to authenticity screening and provenance studies. This multi-analytical approach contributes to the development of a systematic methodology for pigment identification and characterization and offers new insights into the historical, artistic, and material context of the manuscripts investigated.
Integrated spectroscopic characterization and exploratory Raman-based chemometric analysis of pigments and inks in historical manuscripts and early printed books from the university library of Cagliari
Porcu, Stefania
;Pruna, Giulia;Minnai, Lorenzo;Cappellini, Giancarlo;Chiriu, Daniele
2026-01-01
Abstract
: The identification and characterization of pigments and inks in historical manuscripts and artworks plays a crucial role in understanding artistic techniques, material composition, provenance, and authenticity. In this study, non-invasive in-situ analytical techniques, principal component analysis and supervised chemometric modeling are employed to investigate selected manuscripts dated between the 14th and 18th centuries and preserved at the University Library of Cagliari (BUCA). Micro-Raman spectroscopy provides molecular and structural information on pigment composition and degradation processes, while fiber optic reflectance spectroscopy (FORS) and colorimetric measurements allow the characterization of chromatic properties and their correlation with specific materials. Luminescence spectroscopy was further used to support pigment identification through emission features under UV excitation. Additionally, Principal Component Analysis (PCA) was applied to the Raman datasets to explore patterns and similarities among pigments and inks, whereas FORS, luminescence spectroscopy, and colorimetric measurements provided complementary information for material characterization. Building on this exploratory approach, supervised chemometric models based on Soft Independent Modeling of Class Analogy (SIMCA) and Linear Discriminant Analysis (LDA) were evaluated as a preliminary, proof-of-concept framework for comparing the spectral profiles of pigments and inks across manuscripts, and for illustrating a possible future approach to provenance screening. These methods offer a preliminary framework for distinguishing among the manuscripts examined and for flagging anomalous samples, pending validation on a larger, independent dataset. The integration of these techniques within a compact and portable system demonstrates its effectiveness for non-destructive cultural heritage diagnostics. In this work, a preliminary exploratory analysis illustrates the potential for future combination of Raman, FORS, luminescence, and colorimetric information within integrated chemometric workflows, providing a proof-of-concept basis for more extensively validated approaches to authenticity screening and provenance studies. This multi-analytical approach contributes to the development of a systematic methodology for pigment identification and characterization and offers new insights into the historical, artistic, and material context of the manuscripts investigated.
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