Invitation to the Defense of Salvatore Caterino

The Examination Panel is made up of: Sigrid Eyb-Green (chair), Katja Sterflinger (supervisor), Dubravka Jembrih-Simbürger (member of the curriula commission), and Radko Tiňo (external appraiser, Slovak University of Technologies).

Abstract

Iron-gall inks (IGI) were among the most widespread writing materials in antiquity. Their extensive geographical distribution and centuries-long use—documented in Europe from at least the 12th to the 19th century—led to the development of numerous preparation recipes. Variations in raw materials, their provenance, ingredient ratios, and preparation protocols have resulted in a wide chemical diversity of IGI found in historical manuscripts. Unfortunately, many of these manuscripts now suffer from severe deterioration, largely caused by degradation processes initiated by the inks themselves. This vulnerability has prompted extensive scientific research into IGI chemistry, degradation mechanisms, and strategies for preservation.

This thesis investigates the variability of IGI with a particular focus on how key factors (pH, the nature of polyphenolic ligands, iron concentration, and the interaction between ink and parchment) affect the structure and degradation behavior of iron–polyphenolic complexes. Beyond the chemical aspects, a central objective was also the evaluation of proper methodologies. The accurate experimental design adopted throughout this research proved fundamental in ensuring both the reliability and the statistical robustness of the results. Indeed, one of the main outcomes of this work is the demonstration that IGI chemistry, and in particular the in-depth study of degradation processes, can only be meaningfully approached through rigorous and carefully planned methodologies. Such an approach must either explicitly account for the inherent variability of IGI or guarantee strict control of the key factors that determine the formation and stability of iron–polyphenolic complexes. The intrinsic chemical variability of IGI, as explored in this thesis, was shown to have a decisive impact not only on the type and extent of degradation phenomena occurring within the inks themselves but also on the synergistic processes triggered when inks interact with their supports, such as parchment. To address these questions, a multi-analytical strategy was applied: Raman spectroscopy, Electron Paramagnetic Resonance (EPR), and Fourier Transform Infrared spectroscopy (FTIR) were used to investigate both the structure and degradation pathways of iron–polyphenolic complexes, while Micro Hot Table (MHT) thermal microscopy provided insights into the physical effects of ink-induced degradation on parchment. This integrated approach highlights the importance of methodology as both a scientific tool and a conceptual framework, allowing not only the elucidation of degradation mechanisms but also a deeper understanding of how IGI chemistry, parchment properties, and environmental factors (specifically, relative humidity and UV exposure) converge to determine the long-term stability of manuscripts.

Short biography

I am a junior (doctoral) researcher working at the intersection of chemistry and cultural heritage. I graduated in Sciences and Technology for Cultural Heritage at Ca’ Foscari University of Venice, with a specific focus on iron-gall inks in historical manuscripts. My interest in this field began in 2020 through an archaeometric project based on Raman spectroscopy, applied to laboratory-prepared model inks at the CSIC in Madrid. Since then, I have steadily developed my expertise in iron–polyphenolic systems, investigating their structure, variability, and degradation behavior.

Over time, my research has expanded to include other techniques such as NMR and EPR, with particular attention to the methodological challenges associated with these chemically complex materials. This work led to the publication of a review on iron-gall ink chemistry and laid the groundwork for my PhD, which I began in November 2022 within an FWF-funded project. My doctoral research focuses on the controlled study of iron–polyphenolic complexes and their role in ink-induced degradation processes.

During my PhD, I have presented my research at international conferences and engaged closely with conservation-restoration practice, reinforcing my commitment to bridging fundamental chemical research and practical applications. My work has resulted in several publications and contributes to a more systematic understanding of iron-gall ink chemistry and its implications for manuscript preservation.

The thesis defense will be in English and will take place at the Academy at Augasse 2-6, room D 1.17.15 as well as online via Zoom.

Zoom-Link: https://akbild-ac-at.zoom.us/j/63218384842?pwd=3FDQZubAXExLwzZzpSb3zlH9obshGg.1

We are looking forward to welcoming you.