because vibrational ‘fingerprints’ can be measured from microscopic samples [106,
107]. Several developments of SERS techniques applied in the studies of textiles,
paintings, and archaeological objects presenting the importance of the appropriate
parameters and substrate selection were reported by Casadio et al. [11].
Additionally, the wide range of applications of the SERS technique in the identification of natural and some synthetic dyes in microscopic samples from objects of
artistic, historical, and archaeological significance recently was reported by Leona
[108].
New frontiers of the Raman spectroscopy in the cultural field came from the
application of the portable instruments and from coupling Raman with other analytical techniques. The introduction of the Raman imaging permits noninvasive
investigations of the composition and structure of a material and delivers the more
representative characterization of the samples than the point-by-point micro-Raman
analysis [109]. For example, Raman spectral imaging was successfully applied in
the analysis of materials from middle ages, like pigments from the ‘Last Judgment’
by Hieronymus Bosh, inks from Glagolitic, Greek, and Latin manuscripts, and
pigments widely used in modern and contemporary paints like ultramarine blue
(Na 6 Al 6 Si 6 O 24 S 4 ) [110]. Nowadays, in the studies of the artworks and archeological objects the Raman spectroscopy is usually combined with several elemental
and molecular techniques, for example, SEM-EDS [111], XRF [112], LA-ICP-MS
[113], XRD [114], µFTIR [115], FT-NIR [116], ATR FTIR [117], micro-ATR,
ESI-MS [118], and FORS [119].
16.2.1 Case Studies
16.2.1.1 Medieval Manuscripts
The Raman spectroscopy, due to its efficiency, became one of the most widely
applied techniques in the noninvasive analysis of the unique and precious illuminated manuscripts. Especially, the Medieval Hebrew manuscripts are rare objects
among European manuscripts collections, and due to religious reason, they are not
easily accessible for scientific studies. Very restrictive rules governing writing of
Hebrew manuscripts drastically limited materials that were available for the
preparation of inks and palette of pigments used in the illuminations. Due to religious constraints hampering access to the manuscripts, the available scientific data
on such materials is very limited [10, 120]. The Medieval Tanakh (Hebrew Bible)
was investigated [121, 122] at the Wroclaw University in the Cultural Heritage
Research Laboratory. The laboratory specializes in applications of Raman spectroscopy in the CH studies and was trusted with the access to Hebrew manuscript
from the collection of the Ossolinski National Institute in Wrocław (Poland). The
investigated manuscript consists of five volumes: Torah with the Aramaic translation, Book of Isaiah, Book of Judges, Book of Job, Book of Proverbs, Song of
Songs, Book of Ruth, Book of Lamentation, Ecclesiastes and Book of Esther. The
16 Spectroscopy in the Analysis of Artworks
491
107]. Several developments of SERS techniques applied in the studies of textiles,
paintings, and archaeological objects presenting the importance of the appropriate
parameters and substrate selection were reported by Casadio et al. [11].
Additionally, the wide range of applications of the SERS technique in the identification of natural and some synthetic dyes in microscopic samples from objects of
artistic, historical, and archaeological significance recently was reported by Leona
[108].
New frontiers of the Raman spectroscopy in the cultural field came from the
application of the portable instruments and from coupling Raman with other analytical techniques. The introduction of the Raman imaging permits noninvasive
investigations of the composition and structure of a material and delivers the more
representative characterization of the samples than the point-by-point micro-Raman
analysis [109]. For example, Raman spectral imaging was successfully applied in
the analysis of materials from middle ages, like pigments from the ‘Last Judgment’
by Hieronymus Bosh, inks from Glagolitic, Greek, and Latin manuscripts, and
pigments widely used in modern and contemporary paints like ultramarine blue
(Na 6 Al 6 Si 6 O 24 S 4 ) [110]. Nowadays, in the studies of the artworks and archeological objects the Raman spectroscopy is usually combined with several elemental
and molecular techniques, for example, SEM-EDS [111], XRF [112], LA-ICP-MS
[113], XRD [114], µFTIR [115], FT-NIR [116], ATR FTIR [117], micro-ATR,
ESI-MS [118], and FORS [119].
16.2.1 Case Studies
16.2.1.1 Medieval Manuscripts
The Raman spectroscopy, due to its efficiency, became one of the most widely
applied techniques in the noninvasive analysis of the unique and precious illuminated manuscripts. Especially, the Medieval Hebrew manuscripts are rare objects
among European manuscripts collections, and due to religious reason, they are not
easily accessible for scientific studies. Very restrictive rules governing writing of
Hebrew manuscripts drastically limited materials that were available for the
preparation of inks and palette of pigments used in the illuminations. Due to religious constraints hampering access to the manuscripts, the available scientific data
on such materials is very limited [10, 120]. The Medieval Tanakh (Hebrew Bible)
was investigated [121, 122] at the Wroclaw University in the Cultural Heritage
Research Laboratory. The laboratory specializes in applications of Raman spectroscopy in the CH studies and was trusted with the access to Hebrew manuscript
from the collection of the Ossolinski National Institute in Wrocław (Poland). The
investigated manuscript consists of five volumes: Torah with the Aramaic translation, Book of Isaiah, Book of Judges, Book of Job, Book of Proverbs, Song of
Songs, Book of Ruth, Book of Lamentation, Ecclesiastes and Book of Esther. The
16 Spectroscopy in the Analysis of Artworks
491