Analytical investigation on the writing ink of Codex 99 from Manizola collection

Margarida Nunes, Victoria Corregidor, Luís C. Alves, Maria Fernanda Olival, Ofélia Sequeira, Hermínia Maria Vilar, Ana Manhita, Ana Claro, Teresa Ferreira

Research output: Contribution to conferencePosterpeer-review


Written in the first half of the 17th century by the Jesuit Father António Pessoa, “Orthographia Pratica de Varias Letras”, Codex 99 of Manizola collection, encompasses different pedagogical topics as orthography, alphabets, arithmetic’s, and even, recipes of iron gall ink (IGI) to be used on paper or parchment. This Codex is nowadays preserved in the Public Library of Évora but most of its prior custody and usage is unknown. The book was probably used in a pedagogical context, whether teaching or mission. Father António was also a missionary in Tangier and a member of various Jesuit houses in Portugal, where probably he produced it.
From a conservation point of view, the book represents an interesting case study since the use of IGI led to different results: while the first half of the book is very well preserved, the second part presents dramatic degradation patterns such as yellowing, loss of paper strength and fragmentation on the inked areas. To prepare this ink, iron was used as green vitriol (ferrous sulfate) and sometimes salts of other metals like copper and zinc were added to adjust the final hue of the ink. Gum Arabic, the most frequently used binder, was added to increase the viscosity, facilitating the flow of the ink [1]. The ink’s colour could vary from blue to dark violet, and after deposition onto the substrate, it turned to different hues of brown or black as a result of oxidation. Although it was first thought as a long-lasting ink, its degradation effects were rapidly brought to light. Oxidation and acid hydrolysis of cellulose are among the main degradation mechanisms that this polymer may undergo, due to variation of relative humidity and temperature and the presence of transition metal ions, among others [2]. Using microscopic and spectroscopic techniques, namely, micro-Fourier transform infrared spectroscopy (µ-FTIR), micro-Raman spectroscopy and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (VP-SEM/EDS), a selection of samples from the Codex was analyzed to gather information on the surface morphology and the chemical composition of the ink and the support, and the observed pathologies. Particle Induced X-ray emission (PIXE) was used to try to establish differences in the ink composition from different pages of the book. High-performance liquid chromatography with diode array and mass spectrometry detection (HPLC-DAD-MS) was carried out for tannins’ identification. Preliminary results showed that different inks were used and conservation work, not documented, to the best of our knowledge, was probably performed on the manuscript.
[1] Remazeilles, C; Rouchon, V.; Calligaro, T.; Pichon, L. Restaurador 2005, 26, 118-133.
[2] Hosoya, T; Bacher, M.; Pottash, A.; Elder, T.; Rosenau, T. Cellulose 2018, 25, 3797-3814.
Original languageEnglish
Number of pages1
Publication statusPublished - Nov 2020
EventAnalítica 2020: 10º Encontro da Divisão de Química Analítica - Lisboa, Portugal
Duration: 26 Oct 202028 Oct 2020


ConferenceAnalítica 2020
Internet address


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  • Best poster award

    Nunes, M. (Recipient), Corregidor, V. (Recipient), C. Alves, L. (Recipient), Olival, M. F. (Recipient), Vilar, H. V. (Recipient), Sequeira, O. (Recipient), Manhita, A. (Recipient), Claro, Ana (Recipient) & Ferreira, T. (Recipient), 2020

    Prize: Prize (including medals and awards)

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