Caratterizzazione di materiali scrittori da libri di grande valore storicoartistico mediante spettroscopia FT-IR e micro-raman
10.6092/issn.1973-9494/4740
SummaryThis work describes the application of Fourier-Transform Infrared and Raman spectroscopic techniques for the characterization of cellulose paper samples and inks used on ancient writing materials. These samples from books of high historical and artistic interest were provided by the Public Library of Syracuse.The ancient paper showed a characteristic pattern of carbonyl groups, whose vibration modes were observed in FTIR spectra. The spectra of ancient paper samples were compared to each other and to modern paper in order to highlight differences in conservation state between new and old papers. The paper aging process is related to the presence of acid substances and oxidative agents that result in cellulose hydrolysis leading to the shortening of its chain along with changes in the amount of the crystalline form. This hydrolysis causes changes in hydrogen bonds and consequently change the CCH, COH, OCH and HCH bending vibrations mode. In this work, the FTIR and Raman spectra of inks used on ancient paper and parchment samples were also discussed. RiassuntoQuesto lavoro descrive l’applicazione delle tecniche spettroscopiche infrarosse in trasformata di Fourier e Raman per la caratterizzazione di campioni di carta di cellulosa e inchiostri utilizzati su antichi materiali scrittori. Questi campioni provenienti da libri di notevole interesse storico e artistico sono stati forniti dalla Biblioteca Comunale di Siracusa.La carta antica ha mostrato un modello caratteristico di gruppi carbonilici, le cui modalità di vibrazione sono state osservate in spettri FTIR. Gli spettri dei campioni di carta antica sono stati confrontati tra loro e con quelli della carta moderna al fine di evidenziare le differenze tra lo stato di conservazione della carta nuova e vecchia. Il processo di invecchiamento della carta è legato alla presenza di sostanze acide e agenti ossidanti che provocano l’idrolisi di cellulosa che porta all’accorciamento della sua catena con cambiamenti nellaquantità della forma cristallina. Questa idrolisi provoca cambiamenti nei legami a idrogeno che influenzano i modi vibrazioni di bending di CCH, COH, OCH e HCH.In questo lavoro sono stati anche discussi gli spettri FTIR e Raman di inchiostri usati su campioni di carta e pergamena antica. RésuméCe travail décrit l’application des techniques de spectroscopie infrarouge à transformée de Fourier et Raman pour la caractérisation d’échantillons de papier cellulose et d’encre qui ont été utilisés dans des manuscrits anciens. Ces échantillons proviennent de livres d’un très grand intérêt historique et artistique, qui nous ont été fournis par la bibliothèque de Syracuse (Biblioteca Comunale di Siracusa).Le papier ancien présentait un modèle caractéristique de groupes carbonyles, dont les modalités vibratoires ont été observées dans des spectres FTIR. Les spectres des échantillons de papier ancien ont été comparés entre eux et avec ceux du papier moderne, afin de faire ressortir les différences entre l’état de conservation du papier ancien et nouveau. Le processus de vieillissement du papier est lié à la présence de substances acides et d’agents oxydants qui provoquent l’hydrolyse de la cellulose et par conséquent le raccourcissement de sa chaîne et des changements dans la quantité de cellulose cristalline. Cette hydrolyse provoque des changements dans les liaisons hydrogène quià leur tour influencent les modes vibratoires de bending de CCH, COH, OCH et HCH.Ce travail discute également des spectres FTIR et Raman des encres utilisés surdes échantillons de papier et de papier parchemin ancien. ZusammenfassungDieses Werk beschreibt die Anwendung der Fourier-Transform-Ramanspektroskopie zur Charakterisierung von Zellulosepapierproben und auf antiken Schriftstücken verwendeten Tinten. Diese aus Büchern von beachtlichem historischem und künstlerischem Interesse stammenden Proben wurden von der Stadtbibliothek von Syrakus zur Verfügung gestellt.Das antike Papier zeigte ein charakteristisches Modell von Carbonylgruppen, deren Schwingungsverhalten in FT-IR-Spektren beobachtet wurde. Die Spektren der antiken Papierproben wurden untereinander und mit Proben modernen Papiers verglichen, um die Unterschiede zwischen den Konservierungszuständen neuen und alten Papiers festzustellen.Der Alterungsprozess von Papier ist mit dem Vorhandensein saurer Stoffe undOxydantien verbunden, die eine Hydrolyse der Zellulose und somit die Verkürzung ihrer Molekülkette hervorrufen, so dass mengenmäßige Veränderungen der Kristallform eintreten.Diese Hydrolyse bewirkt Veränderungen in den Bindungen mit dem Wasserstoff, welche das Bending - Schwingungsverhalten von CCH, COH, OCH und HCH beeinflussen.In diesem Werk werden auch die FTIR- und Raman-Spektren der Tinten besprochen, die auf antiken Papier- und Pergamentproben verwendet wurden. ResumenEste trabajo describe la aplicación de técnicas de espectroscopía de infrarrojo con transformada de Fourier y Raman para caracterizar muestras de papel de celulosa y tintas empleadas sobre antiguos materiales de escritura. Dichas muestras, provenientes de libros de destacado interés histórico y artístico, han sido proporcionadas por la Biblioteca Municipal de Siracusa.El papel antiguo ha mostrado un modelo característico de los grupos carbonilos,cuyas modalidades de vibración se han observado en espectros FTIR. Los espectros de las muestras de papel antiguo se han comparado entre sí y con los del papel moderno para evidenciar las diferencias entre el estado de conservación del papel nuevo y el viejo. El proceso de envejecimiento del papel está relacionado con la existencia de sustancias ácidas y agentes oxidantes que provocan la hidrólisis de la celulosa. Este fenómeno comporta el acortamiento de la cadena, con modificaciones en la cantidad de la forma cristalina, y provoca cambios en los enlaces de hidrógeno que influyen enlos modos de las vibraciones de deformación de CCH, COH, OCH y HCH.En este trabajo, asimismo, se acomete una discusión sobre los espectros FTIR yRaman de tintas empleadas sobre muestras de papel y pergamino antiguo. 简介本文介绍了傅里叶变换红外光谱和拉曼光谱技术的应用:检测纤维纸张样品，以及古代书写材料上墨水样本的特性。这些样品均取自具有极高历史和艺术价值的书籍，书籍由Siracusa (锡拉库萨市) 政图书馆提供。根据FTIR光谱测定观察得到的震动方式显示，古代纸张中具有碳基结构特性。古代纸张样本的光谱相互比较后，还与现代纸张光谱进行了比较，以得出新旧纸张保存状态的差异。纸张的老化过程与其中酸性物质和氧化剂相关，这些物质促成纤维素的水解，进而使碳链缩短、晶体结构数量变化。这些水解反应造成氢键连接方式的变化，进而影响CCH，COH，OCH和HCH弯曲振动的模式。此外在这项测试中，同样还进行了样本纸张和羊皮纸上墨水FTIR和拉曼光谱的分析。 РезюмеОбъектом этой работы является применение методов ИК рамановской спек-троскопии с Фурье-преобразованием для определения характеристик образцов целлюлозной бумаги и чернил, использованных в старинных материалах для письма. Данные образцы, полученные из книг, представляющих значительную историческую и художественную ценность, были предоставлены городской би-блиотекой г. Сиракуза.В старинной бумаге была обнаружена характерная модель карбонильныхгрупп, способы колебания которых были изучены в ИК-спектрах с Фурье-преобра-зованием. Для выявления разницы между состоянием хранения новой и старой бумаги спектры образцов старинной бумаги были сопоставлены друг с другом и со спектрами, полученными от современной бумаги. Процесс старения бумаги связан с наличием кислотных веществ и окисляющих агентов, вызывающих ги-дролиз целлюлозы. Это приводит к сокращению ее цепи и к количественным из-менениям кристаллической формы. Гидролиз вызывает изменение водородных связей, оказывающих влияние на изгибное колебание CCH, COH, OCH и HCH.В данной работе также изучены ИК-спектры с Фурье-преобразованием и Ра-ман-спектры чернил, используемых на образцах старинной бумаги и пергамента
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Zelica Minniti
Conservation Science in Cultural Heritage
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Characterization of writing materials of books of great historical-artistic value by FT-IR and micro-raman spectroscopy
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2015-02-24
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Zelica Minniti
2014/12/20
10.6092/issn.1973-9494/4740
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1973-9494
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BELL I.M., CLARK R. J. H., GIBBS P. J., 1997, Raman Spectroscopic Library of Natural and Synthetic Pigments (pre- 1850 AD), Spectrochimica Acta Part A, 53, pp. 2159
Characterization of writing materials of books of great historical-artistic value by FT-IR and micro-raman spectroscopy
https://conservation-science.unibo.it/article/download/4740/4221
14
C    HARACTERIZATION OF WRITING MATERIALS OF BOOKS
     OF GREAT HISTORICAL-ARTISTIC VALUE BY FT-IR AND
     MICRO-RAMAN SPECTROSCOPY




   Vito Librando•, Zelica Minniti
   Dipartimento di chimica
   Università degli Studi di Catania, Italy


   Keywords: spectroscopy, infrared, Raman, cellulose, ink

   1. Introduction

   1.1 State of the art

    Due to its non-destructive approach, infrared spectroscopy represents great poten-
tial for the characterization of the surface of different materials [1]. Many authors have
applied this spectroscopic technique to paper characterization. Calvini and colleagues
(2006) studied the composition of old and modern Japanese papers [2]. Hon (1986)
demonstrated the effectiveness of FTIR in analyzing and determining acid impurities
distributed on the surface of paper documents produced from 1790 to 1983 [1]. In one
study by Mossini (1990), some naturally aged papers were subjected to FTIR analysis




                                                                                                  CONSERVATION SCIENCE IN CULTURAL HERITAGE
[3]. In a study by Zotti and colleagues (2008) the main surface components of bio-
deteriorated papers from the XVIII century were characterized by FTIR spectroscopy;
the author also referred to the presence of gelatin, wood pulp, calcium carbonate,
gypsum, hemicelluloses and glue in the composition of the paper, as indicated by the
characteristic FTIR absorption bands [4].
    Raman spectroscopy has been applied to different types of artworks too. On paper
artifacts, the presence of additives in the cellulose can be detected; Raman analysis
of a map from the XVII century showed that gypsum was used as an additive in the
cellulose [5]. Bicchieri and colleagues (2006) examined degraded papers using sev-
eral non-destructive spectroscopic techniques, including Raman spectroscopy [6]. The
cellulose subjected to accelerated hydrothermal ageing gives rise to a characteristic
pattern of carbonyl groups; their vibrational modes were observed in Raman spectra
by Lojewska and colleagues (2007) [7].

   1.2 Paper structure

   Paper mainly consists of bonded cellulose fibres that are linear polymers of glucose
monomers linked by β-1.4-glycosidic bonds [8]. All chemical reactions occur at the lev-
el of the hemiacetal bond (glycosidic linkage) and/or hydroxyl groups. Cellulose chains


• Corresponding author: vlibrando@unict.it

                                                                                             39
                                                                                                              are held together by strong intramolecular hydrogen bonds. 80% of these chains are
                                                                                                              ordered (crystalline forms), the remainder of the chains, are unordered (amorphous
                                                                                                              form) [9]. In addition to cellulose fibres, paper contains hemicellulose (wood polyoses),
                                                                                                              lignin and a certain amount of additives. The presence of acidic substances results
                                                                                                              in the hydrolysis of cellulose that appears in the shortening of its chain, along with a
                                                                                                              reduction in content of the crystalline form [10-11]. Progressive fragmentation of the
                                                                                                              chains makes the paper brittle, leading to increased oxidation and yellowing.
                                                                                                                  As a consequence of the aging process, oxidized groups (carbonyl and carboxyl
                                                                                                              groups) are formed on the cellulose chains. As there is a synergy between hydrolysis
                                                                                                              and oxidation, study of the alterations is very difficult [12].
V. Librando, Z. Minniti - Characterization of writing materials of books of great historical-artistic value




                                                                                                                 1.3 Ink composition.

                                                                                                                 Inks can be described as liquid, semi-liquid or solid preparations, which can be used
                                                                                                              to draw graphic signs on a support. The aging of inks is one of the major causes for
                                                                                                              corrosion of paper, the mechanism of which depends on the nature of the components
                                                                                                              and their interaction with paper. Different inks age differently: the literature focuses in
                                                                                                              particular on iron gall ink, which has been shown to be the principal cause of paper
                                                                                                              penetration. This is either due to the acid hydrolysis of cellulose (caused by an excess
                                                                                                              of sulphuric acid in the ink recipe) or to iron (II) ion oxidation reactions (caused by
                                                                                                              an excess of iron ions) [13-14]. Conversely, carbon black inks are stable due to their
                                                                                                              chemical inertia, but become more opaque with age. Other modern synthetic inks do
                                                                                                              not cause paper corrosion, but they are very photosensitive [15].

                                                                                                                 1.4 Aim of the work.

                                                                                                                 In this work, FTIR and Raman spectroscopic techniques were used to characterize
                                                                                                              the cellulose on paper samples from books of great historical and artistic value and to
                                                                                                              identify inks on ancient samples of paper and parchment.

                                                                                                                 2. Experimental section.

                                                                                                                 2.1 Methods.

                                                                                                                  In order to characterize samples of the papers and the inks used on them, the two
                                                                                                              spectroscopic methods were used on both printed and non-printed areas of the pages
                                                                                                              of the books.
                                                                                                                  The spectroscopic analyses were carried out at ambient temperature and humid-
                                                                                                              ity; the spectra were acquired on a Thermo-Nicolet 6700 FTIR spectrometer with an
                                                                                                              Attenuated Total Reflectance (ATR) sampling tool (Diamond Crystal window). FTIR
                                                                                                              spectral analyses were performed at a resolution of 4 cm-1 in the range of 4000–550
                                                                                                              cm-1 by iterating 32 scans for each analysis; the Raman spectra were recorded on a
                                                                                                              Thermo Dispersive Raman DXR spectrometer equipped with a 780 nm excitation laser
                                                                                                              and full range grating coupled to a micro-probe (CCD detector). 10x, 50x and 100x
                                                                                                              magnifying lenses are mounted on the head of the micro-probe. Neutral density filters
                                                                                                              implemented in the system were used to attenuate the laser power on the samples
                                                                                                              (between 1 and 14 mW).



                                                                                                         40
  2.2 Samples.

   The samples, provided by the Public Library of Syracuse (Italy), come from the fol-
lowing books:
   • book A - Histoire naturelle, générale et particulière, Volume 13, published in Paris
     in 17891;
   • book B - Tractatus in Quinque Ecclesiae Praecepta, published in Lyon in 16262.
   • Some fragments of paper and parchment belonging to the following books were
     also analysed;
   • book C - Augustini Eugubini In psalmum XVIII et CXXXVIII interpretatio. Epistola
     Erasmi Roterodami ad Augustinum Eugubinum. Augustini Eugubini ad Erasmum
     responsio, super his quae ab eo dicta sunt super Pentateuchum, published in
     Lyon in 15333;
   • book D - Officia Propria Sanctorum Jussu Syracusarum Episcopi, published in
     Syracuse in 1794.
   These fragments were found glued to the back plates of the listed books. Gluing
paper fragments from old books was a common practice used to reinforce book cov-
ers. For this reason, these fragments are not datable, but they were also characterized
and the findings discussed.

  3. Results and discussion.

  3.1 Paper characterization.

   The FTIR analysis carried out on samples of paper from the three ancient books, A,
B and C, show absorption bands typical of calcium stearate (shoulders at 2835* and
1541* cm-1) and the presence of gypsum (peaks at 661** and 595** cm-1) (Figure 1)




                                                                                                 CONSERVATION SCIENCE IN CULTURAL HERITAGE
[16]. The most interesting peaks are observed at frequencies of 1425 and 1316 cm-1
and two smaller ones at 1335 and 1370 cm-1, these bands are very sensitive to the ag-
ing process of paper (Table 1) [17-23]. The rearrangement in hydrogen bonds due to
oxidative reactions, causes changes in the vibrational pattern of these bands (Figure
1): the band at 1425 cm-1 which is mainly due to H-C-H and O-H-C in plane bending vi-
brations [17-23] gains intensity with the accelerated aging of cellulose, while the band
at 1316 cm-1, due to C-O-H and H-C-C bending vibrations, loses its intensity. Smaller
changes in intensity are observed for the 1335 and 1370 cm-1 bands that are similar to
the 1316 cm-1 band, assigned to the bending vibrations of C-O-H and H-C-C [17-23].




                                                                                            41
V. Librando, Z. Minniti - Characterization of writing materials of books of great historical-artistic value




                                                                                                                  Figure 1. FTIR spectra of paper samples from books A, B and C. The bands at 1425, 1316,
                                                                                                                  1335 and 1370 cm-1 are very sensitive to the paper aging process.
                                                                                                                  *bands due to calcium stearate;
                                                                                                                  **
                                                                                                                     bands due to gypsum.




                                                                                                                 These changes in vibrational pattern are less marked in the ancient paper samples
                                                                                                              analysed. In fact, comparing the spectra of paper samples from book A (yr.1789) and
                                                                                                              book B (yr.1626), with recently produced paper (P-yr.2010) or with one from the last
                                                                                                              century (P-yr.1955) (16), the oldest samples show a much less marked degree of oxi-
                                                                                                              dation (Figure 2).




                                                                                                              Figure 2. FTIR spectra of paper samples from ancient books A (yr.1769) and B (yr.1626) compared
                                                                                                              with recently produced paper (P-yr.2010) and with that produced last century (P-yr.1955): the
                                                                                                              band at 1425 cm-1 gains intensity with accelerated aging of cellulose, while the 1316 cm-1 band
                                                                                                              lowers its intensity


                                                                                                         42
    It is very difficult at this point to clearly interpret the data. However, it seems more
likely that hydrolysis of the glycosidic bonds at this level of “destruction” causes chang-
es in polymer structure mainly by forcing rearrangement in hydrogen bonding (chang-
ing from a crystalline to an amorphous form) which in turn changes the pattern of the
CCH, COH, OCH and HCH bending vibration mode.

   3.2 Characterization of the ink

   Spectroscopic analysis revealed important information about the type of ink used in
the samples from books A and B. In both samples there are the typical oxalate absorp-
tion bands at 1637 and 1315 cm-1 but, without more specific analyses, it is difficult to
state whether these signals come from the degradation of the ink or are typical of an
iron-tannin complex. The weak peak at 821 cm-1 in both samples suggests the pres-
ence of iron(II) oxalate [24] (Figure 3).




Figure 3. FTIR ink spectra from books A and B: the grey regions are very sensitive to the presence        CONSERVATION SCIENCE IN CULTURAL HERITAGE
of oxalate, sulphate and carboxylic groups


    One of the main problems of FTIR analysis is the presence of hidden bands, due to
other components (e.g., calcium oxalate, iron-oxycellulose complexes, copper oxalate,
aluminium oxalate) that absorb at approximately the same frequencies as iron oxalates
and modify both the shape and the relative heights of the main peaks. The signal at
about 1100 cm-1 indicates the presence of sulphates, but the uncertainty regarding the
nature of the sulphates (i.e. calcium, iron or sodium sulphate) makes it difficult to per-
form a thorough analysis of degraded iron gall inks [25]. By comparing the spectrum
of the ink with the respective paper one, it is possible to note the increase in intensity
of the characteristic absorption bands due to the stretching vibrations in SO42– (strong
in the range between 1120-1040 cm-1 and 645-570 cm-1, and weak at 976 cm-1) and in
CO-OH (strong between 1700-1650 cm-1 and 1350-1340 cm-1 and medium between
950 and 825 cm-1) [26] (Figures 4-5).


                                                                                                     43
V. Librando, Z. Minniti - Characterization of writing materials of books of great historical-artistic value




                                                                                                              Figure 4. Ink sample from book A: comparison between the ink FTIR spectrum and the respective
                                                                                                              paper one, it is possible to notice the increase in intensity of the characteristic SO42– absorption
                                                                                                              bands (in the 1120-1040 and 645-570 cm-1 ranges); in the circles the oxalate and carboxylic
                                                                                                              groups bands (in the 1700-1650 and 1350-1340 cm-1 regions) typical of metal-gall inks




                                                                                                              Figure 5. Ink sample from book B: comparison between the ink FTIR spectrum and respective
                                                                                                              paper one, it is possible to notice the increase in intensity of the characteristic SO42- absorption
                                                                                                              bands (in the 1120-1040 and 645-570 cm-1 ranges); in the circles the oxalate and carboxylic
                                                                                                              groups bands (in the 1700-1650 and 1350-1340 cm-1 regions) typical of metal-gall inks



                                                                                                         44
   It is likely that they are metal gall inks. Through Raman analyses it was possible to
characterise the red and black inks found on a sample of very deteriorated paper from
book C (Figures 6-7). In particular, the strongest peak in the Raman spectrum at 244
cm-1 (Figure 6) is typical of vermilion red ink (HgS, mercury sulphide of a natural min-
eral) [27]. The Raman absorption bands of black ink in the 1350-1380 and 1580-1600
cm-1 range, are typical of amorphous carbon, known as “lampblack” or carbon black,
which has been used since ancient times. In the spectrum of the paper fragment from
book C, two bands are located at 1365 and 1578 cm-1 (Figure 7) [28-29].




Figure 6. Red ink on fragments from book C; characteristic Raman spectrum of vermilion (251




                                                                                                   CONSERVATION SCIENCE IN CULTURAL HERITAGE
cm-1 absorption band of mercury sulphide HgS)




Figure 7. Black ink on fragments from book C; characteristic Raman spectrum of Lamp black
(1575 and 1365 cm-1 absorption bands of amorphous carbon)


                                                                                              45
                                                                                                                  Raman analysis also made it possible to characterize the ink found on the samples of
                                                                                                              parchment fragments from book D (Figure 8). In particular the very strong band at 1474 cm-1
                                                                                                              is typical of iron gall ink and the broad band at about 580 cm-1 may be related to the presence
                                                                                                              of metal salts. The absorption bands around 1334 and 1588 cm-1 are probably due to the
                                                                                                              presence of a certain amount of amorphous carbon in the ink mixture. At times amorphous
                                                                                                              carbon (carbon black) was added to a metal gall ink (which was transparent immediately af-
                                                                                                              ter preparation) in order to make it immediately usable. The other absorption bands are prob-
                                                                                                              ably independent of the ink composition and may be related to organic iron complexes [27].
V. Librando, Z. Minniti - Characterization of writing materials of books of great historical-artistic value




                                                                                                              Figure 8. Black ink on fragments from book D: in the circles the typical absorption bands of iron-
                                                                                                              gall inks; *absorption bands probably due to the presence of amorphous carbon in the ink mixture.
                                                                                                              In the box the standard spectra of iron-gall and lamp-black inks


                                                                                                                 4. Conclusion.

                                                                                                                  In this study, FTIR and Raman techniques applied on original writing materials gave
                                                                                                              important information about paper composition and conservation state and enabled
                                                                                                              the type of ink used on them to be identified. Several samples of ancient paper were
                                                                                                              compared with each other and with modern paper samples in order to highlight differ-
                                                                                                              ences between the more recent and the older paper. Analysis of the old paper revealed
                                                                                                              the presence of additives in lesser quantities than in present-day paper or that of the
                                                                                                              last century. Furthermore, the amount of amorphous cellulose in the ancient paper is
                                                                                                              lower than that in the samples of contemporary paper. These facts can be explained
                                                                                                              by the significantly higher quality of the materials constituting the older paper. Since
                                                                                                              ancient paper is essentially made of long chain cellulose derived from cotton rags used
                                                                                                              in old mills, it has better withstood the attacks of external agents and has been affected
                                                                                                              less by hydrolysis and oxidation processes.
                                                                                                                  The identification of metal-gall inks or organic inks from books A and B was rather
                                                                                                              difficult, since the ink absorption bands were covered by the cellulose band: indeed,
                                                                                                              cellulose is the main component of the sample and only small discrepancies were ob-
                                                                                                              served between the spectra of the inked paper and the spectra of the uninked paper


                                                                                                         46
area. The interpretation of these small discrepancies measured on these ancient sam-
ples remains difficult due to the degradation processes in the ink and paper.
   Raman spectroscopy has proved to be a very sensitive instrument for the identifica-
tion of inks on parchment and paper samples. This technique allowed us to identify
the red and black inks from paper fragments belonging to book C (as shown by the
characteristic Raman spectrum of vermilion and lamp black) and the black ink on frag-
ments belonging to book D. The spectrum of this black ink, in particular, showed a very
strong band at 1474 cm-1 typical of iron-gall ink, and two absorption bands around 1334
and 1588 cm-1 that are probably due to the presence of a certain amount of amorphous
carbon in the ink mixture.

    Acknowledgements

  The authors wish to thank the MIUR (Ministry for Education, University and Re-
search), PRIN 2009, for the financial support.


    Notes

1
    Georges Louis Leclerc de Buffon (Montbard, 1707-Paris, 1788) was an eighteenth-
    century French naturalist. Buffon developed his interest in natural history after being
    appointed by Louis XV in 1739 as director of the Jardin du Roi (Royal Gardens and
    Natural History Collections) in Paris. He was ambitious and produced a collection
    of books about natural history (animals, plants, and minerals). In 1749 he published
    (along with a set of co-workers) the first three volumes of his famous Histoire na-
    turelle, générale et particulière that ultimately comprised thirty-six volumes pub-
    lished over a period of fifty years. The Histoire Naturelle was an enormous success




                                                                                                    CONSERVATION SCIENCE IN CULTURAL HERITAGE
    and became one of the most widely read books of the century. Buffon also included
    a number of theoretical essays in his Histoire Naturelle that were historically impor-
    tant for the theory about the evolution of life and on the concept of species.

2
    The Jesuit, Tommaso Tamburino (Caltanissetta, 1591 – Palermo, 1675) was a dom-
    inant figure in the production of Italian casuistry which had developed in Sicily in the
    seventeenth century following that of Spain (School of Salamanca). Tamburino’s
    works, thanks to the efforts of the Jesuits, spread throughout Europe from the mid-
    seventeenth century. His writings on moral theology, collected in “Opera Omnia”,
    were published several times in Italy and abroad and were used as reference books
    in Europe for a century, even after his death.

3
    Agostino Steuco (in Latin Steuchus or Eugubinus) (Gubbio, 1497 – Venezia, 1548),
    an Italian humanist, Old Testament scholar, a counter reformation polemicist and
    antiquarian, was born in Gubbio, in Umbria. Over several years (1529-33) Steu-
    co wrote a series of controversial works against Luther and Erasmus, the latter of
    whom he accused of helping to foment the Protestant revolt against the Church.
    These works show Steuco’s staunch support of the traditions and practices of the
    church, including a strident defence of papal authority. Part of his output during this
    period included an important set of annotations on the Pentateuch.



                                                                                               47
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                                                                                                                 Biographical Notes

                                                                                                                  Vito Librando has a degree in Chemistry, he is Full Professor of Environmental
                                                                                                              Chemistry and Cultural Heritage at Catania University and he has been Professor
                                                                                                              of Chemistry of Cultural Heritage, Restoration Chemistry, Laboratory of Chemistry of
                                                                                                              Cultural Heritage, both in three-year and magisterial degree courses of “Science and
                                                                                                              Technology of Restoration.”
                                                                                                                  He has been involved in the study of organic inhibitors of the crystallization of mix-
                                                                                                              tures of salts in stone materials, as well as in FT-IR mapping and Raman micro-spec-
                                                                                                              troscopy applied to the Cultural Heritage. He has coordinated national and interna-
                                                                                                              tional research projects, such as Strategic Projects of the NRC, MIUR, INTAS and the
V. Librando, Z. Minniti - Characterization of writing materials of books of great historical-artistic value




                                                                                                              Sicilian Region.
                                                                                                                  He is the author of 110 publications in international scientific journals, mainly in the
                                                                                                              field of Chemistry of Cultural Heritage and Environmental Chemistry.

                                                                                                                 Zelica Minniti graduated in Biological Science at Catania University in 2004. She
                                                                                                              did a doctorate in Chemical Science at Catania University with a thesis on advanced
                                                                                                              characterization methods of organic materials of environmental and historical-artistic
                                                                                                              relevance through Micro-FTIR Mapping and Raman Microscopy. She has taken part
                                                                                                              in different environmental chemistry research projects in partnership with different or-
                                                                                                              ganizations such as: ARPA Sicilia, Consorzio Catania Ricerche e Consorzio COMETA.
                                                                                                              She is currently working for the research center “CRAM3RA” directed by Prof. Vito
                                                                                                              Librando.




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