Periodic Reporting for period 2 - ARIAH (Chemical speciation of A Revolution In Art History)
Reporting period: 2024-11-01 to 2025-10-31
The ARIAH (Chemical Speciation of A Revolution In Art History) project sought to unravel the intricate molecular and nanoscale composition of Renaissance mixed-media paints, which combined egg- and oil-based binders. This material innovation marked a transformative period in art history and enabled masterpieces by artists such as Leonardo da Vinci and Sandro Botticelli. However, the chemical and structural properties of these paints had remained insufficiently understood, limiting the ability to fully explore the interaction between material advances and artistic techniques.
ARIAH integrated advanced analytical methods, including x-ray Raman scattering (XRS), scanning transmission x-ray microscopy (STXM), deep-UV photoluminescence microscopy, and atomic force microscopy infrared spectroscopy (AFM-IR), alongside mass spectrometry. These state-of-the-art techniques established new standards for the study of heritage materials and provided unprecedented insights into the chemistry and nanostructure of mixed-media paints. The findings drove innovation in the preservation of cultural heritage while deepening understanding of the technological and artistic processes that shaped Renaissance masterpieces.
This interdisciplinary project bridged physical chemistry and art history to contextualize scientific findings within broader cultural and historical narratives. By illuminating the relationship between material properties, artistic practices, and social influences, ARIAH enriched the appreciation of Renaissance art and provided a holistic framework for studying cultural heritage. The results promised lasting impacts on the preservation, interpretation, and celebration of one of the most pivotal artistic epochs in history.
ARIAH integrated advanced analytical methods, including x-ray Raman scattering (XRS), scanning transmission x-ray microscopy (STXM), deep-UV photoluminescence microscopy, and atomic force microscopy infrared spectroscopy (AFM-IR), alongside mass spectrometry. These state-of-the-art techniques established new standards for the study of heritage materials and provided unprecedented insights into the chemistry and nanostructure of mixed-media paints. The findings drove innovation in the preservation of cultural heritage while deepening understanding of the technological and artistic processes that shaped Renaissance masterpieces.
This interdisciplinary project bridged physical chemistry and art history to contextualize scientific findings within broader cultural and historical narratives. By illuminating the relationship between material properties, artistic practices, and social influences, ARIAH enriched the appreciation of Renaissance art and provided a holistic framework for studying cultural heritage. The results promised lasting impacts on the preservation, interpretation, and celebration of one of the most pivotal artistic epochs in history.
Cutting-edge spectroscopic and imaging techniques revealed the molecular interactions and material behaviors that characterized these complex paint systems, substantially advancing knowledge of Renaissance art materials and their preservation.
High-resolution X-ray Raman scattering (XRS) proved instrumental in elucidating the chemical composition of mixed-media paints, enabling clear differentiation between tempera grassa and protein-coated oil paints. Model paints prepared using historically accurate methods yielded detailed carbon speciation data collected at large-scale facilities worldwide, including ESRF (France) and SSRL (United States). Key achievements included the identification of functional group transitions, mitigation of radiation damage, and the establishment of XRS as a foundational analytical tool for the study of historical paints. The implementation of cryogenic setups further enhanced analytical precision and ensured the reliability of the results.
Complementary techniques, including scanning transmission X-ray microscopy (STXM) and advanced photoluminescence methods, provided nanoscale insights into paint layer heterogeneity. STXM analyses conducted at the SOLEIL synchrotron facility revealed pronounced chemical heterogeneity in tempera paints, uncovering oxidative processes and complex binder–pigment interactions. A dedicated Python-based pipeline was developed to process and classify spectral datasets, significantly improving analytical robustness. In parallel, deep-UV photoluminescence and multispectral luminescence microscopy enabled the spatial mapping of proteinaceous and lipid components, offering valuable insights into historical paint preparation methods. Atomic force microscopy–infrared spectroscopy (AFM-IR) further enriched understanding of paint microstructure by revealing nanoscale features such as preferential functional group orientation relative to pigment particles and the subsequent formation of lead carboxylates. Together, these advanced methodologies provided a comprehensive framework for investigating the chemical and structural organization of Renaissance paints and laid the groundwork for future research in cultural heritage preservation.
Among the historical samples analyzed using deep-UV photoluminescence, particular attention was given to a microsample taken from Madonna of the Carnation by Leonardo da Vinci (c. 1475, Bavarian State Painting Collection). Initial analyses revealed preserved chemical signatures consistent with proteinaceous materials within this oil painting, underscoring the complexity of Leonardo’s material practice. To validate these findings and examine the paint structure at higher spatial resolution, AFM-IR was employed, revealing nanoscale protein signatures localized around pigment particles and embedded within the oil binder. These results provided direct molecular-level evidence that Leonardo da Vinci prepared his paints using protein-treated pigments dispersed in an oil-based medium.
This discovery was highly significant, as it confirmed the deliberate use of mixed-media paint formulations during the transitional period from tempera to oil painting in the late fifteenth century. It offered rare insight into Leonardo’s workshop practices and demonstrated that complex protein–oil systems were intentionally engineered, likely to modulate paint properties such as stability, handling, and drying behavior.
High-resolution X-ray Raman scattering (XRS) proved instrumental in elucidating the chemical composition of mixed-media paints, enabling clear differentiation between tempera grassa and protein-coated oil paints. Model paints prepared using historically accurate methods yielded detailed carbon speciation data collected at large-scale facilities worldwide, including ESRF (France) and SSRL (United States). Key achievements included the identification of functional group transitions, mitigation of radiation damage, and the establishment of XRS as a foundational analytical tool for the study of historical paints. The implementation of cryogenic setups further enhanced analytical precision and ensured the reliability of the results.
Complementary techniques, including scanning transmission X-ray microscopy (STXM) and advanced photoluminescence methods, provided nanoscale insights into paint layer heterogeneity. STXM analyses conducted at the SOLEIL synchrotron facility revealed pronounced chemical heterogeneity in tempera paints, uncovering oxidative processes and complex binder–pigment interactions. A dedicated Python-based pipeline was developed to process and classify spectral datasets, significantly improving analytical robustness. In parallel, deep-UV photoluminescence and multispectral luminescence microscopy enabled the spatial mapping of proteinaceous and lipid components, offering valuable insights into historical paint preparation methods. Atomic force microscopy–infrared spectroscopy (AFM-IR) further enriched understanding of paint microstructure by revealing nanoscale features such as preferential functional group orientation relative to pigment particles and the subsequent formation of lead carboxylates. Together, these advanced methodologies provided a comprehensive framework for investigating the chemical and structural organization of Renaissance paints and laid the groundwork for future research in cultural heritage preservation.
Among the historical samples analyzed using deep-UV photoluminescence, particular attention was given to a microsample taken from Madonna of the Carnation by Leonardo da Vinci (c. 1475, Bavarian State Painting Collection). Initial analyses revealed preserved chemical signatures consistent with proteinaceous materials within this oil painting, underscoring the complexity of Leonardo’s material practice. To validate these findings and examine the paint structure at higher spatial resolution, AFM-IR was employed, revealing nanoscale protein signatures localized around pigment particles and embedded within the oil binder. These results provided direct molecular-level evidence that Leonardo da Vinci prepared his paints using protein-treated pigments dispersed in an oil-based medium.
This discovery was highly significant, as it confirmed the deliberate use of mixed-media paint formulations during the transitional period from tempera to oil painting in the late fifteenth century. It offered rare insight into Leonardo’s workshop practices and demonstrated that complex protein–oil systems were intentionally engineered, likely to modulate paint properties such as stability, handling, and drying behavior.
The ARIAH project made transformative contributions to the study of Renaissance mixed-media paints by revealing their nanoscale chemical composition and structural organization. Through the use of advanced analytical techniques such as X-ray Raman scattering (XRS), scanning transmission X-ray microscopy (STXM), deep-UV photoluminescence, and atomic force microscopy–infrared spectroscopy (AFM-IR), the project significantly advanced scientific understanding of historical painting materials while establishing innovative methodologies for their analysis and preservation. These findings addressed critical gaps in knowledge surrounding the transition from tempera to oil painting, elucidating the complex interplay between binders, pigments, and preparation techniques that underpinned iconic Renaissance artworks.
A central discovery of the project emerged from the analysis of a microsample taken from Madonna of the Carnation by Leonardo da Vinci. Deep-UV photoluminescence and AFM-IR analyses revealed, at the nanoscale, preserved proteinaceous materials intimately associated with pigment particles and embedded within an oil-based binder. This direct molecular evidence demonstrated that Leonardo deliberately employed protein-treated pigments within oil paint, confirming the intentional use of mixed-media formulations during the late fifteenth-century transition from tempera to oil painting. These results provided rare insight into Leonardo’s workshop practices and highlighted sophisticated material engineering aimed at controlling paint stability, handling, and drying behavior.
Key outcomes of the ARIAH project included the development of advanced analytical protocols for the investigation of mixed-media paints. XRS delivered detailed molecular speciation of organic components, STXM exposed nanoscale chemical heterogeneities within Renaissance paint layers, and deep-UV photoluminescence enabled submicrometer mapping of protein and oil distributions. AFM-IR further revealed nanoscale heterogeneity and interactions within organic binders in both historical and model paint systems. Collectively, these methodological advances enhanced understanding of complex heritage materials and fostered interdisciplinary collaboration among scientists, conservators, and art historians.
By deepening insight into the material innovations behind masterpieces by artists such as Leonardo da Vinci and Sandro Botticelli, ARIAH strengthened appreciation of Renaissance art while contributing significantly to heritage science. The project’s methodologies demonstrated relevance beyond cultural heritage, with implications for paint technology and materials research. Future directions included validating the findings across a broader corpus of historical samples, developing noninvasive analytical protocols, and expanding international collaborations to extend the reach and impact of these discoveries.
A central discovery of the project emerged from the analysis of a microsample taken from Madonna of the Carnation by Leonardo da Vinci. Deep-UV photoluminescence and AFM-IR analyses revealed, at the nanoscale, preserved proteinaceous materials intimately associated with pigment particles and embedded within an oil-based binder. This direct molecular evidence demonstrated that Leonardo deliberately employed protein-treated pigments within oil paint, confirming the intentional use of mixed-media formulations during the late fifteenth-century transition from tempera to oil painting. These results provided rare insight into Leonardo’s workshop practices and highlighted sophisticated material engineering aimed at controlling paint stability, handling, and drying behavior.
Key outcomes of the ARIAH project included the development of advanced analytical protocols for the investigation of mixed-media paints. XRS delivered detailed molecular speciation of organic components, STXM exposed nanoscale chemical heterogeneities within Renaissance paint layers, and deep-UV photoluminescence enabled submicrometer mapping of protein and oil distributions. AFM-IR further revealed nanoscale heterogeneity and interactions within organic binders in both historical and model paint systems. Collectively, these methodological advances enhanced understanding of complex heritage materials and fostered interdisciplinary collaboration among scientists, conservators, and art historians.
By deepening insight into the material innovations behind masterpieces by artists such as Leonardo da Vinci and Sandro Botticelli, ARIAH strengthened appreciation of Renaissance art while contributing significantly to heritage science. The project’s methodologies demonstrated relevance beyond cultural heritage, with implications for paint technology and materials research. Future directions included validating the findings across a broader corpus of historical samples, developing noninvasive analytical protocols, and expanding international collaborations to extend the reach and impact of these discoveries.