France. In the next year, the advantages of the application of the Raman spectroscopy in the analysis of the pigments and dyes were presented by the multidisciplinary group of the researches [38, 39]. In the beginning of the nineties,
several research groups [21] started various studies with the application of Raman
spectroscopy in the field of art and archaeology. Edwards et al. published the first
scientific study on the biodegradation of the Renaissance frescos identifying calcium oxalate as the main compound in the incrustation with other organic compounds of the lichen metabolism [40] and characterizing the mono- and dihydrate
forms of the oxalate compounds [41]. Year later, paper concerning the biodegraded
cave art [42] and the research of the biodegraded archaeological materials originated from the mummified skin of Otzi the Alpine Iceman dating from 5200 BC
[43] were published. Just a few months later, Clack et al. published in England the
study of the illuminations in the unique medieval manuscripts [44] and characterization of the historically important dyes [45]. He continued the research of art
objects with the use of the Raman spectroscopy, which resulted 3 years later in
publishing the first review highlighting the advantages of this technique in the
noninvasive investigations of manuscripts [45]. In the next years, he published
study of Persian [46], German [47], and Latin [48] illuminated manuscripts.
Simultaneously, French researcher carried out investigation of the blue pigments
used by French artist in nineteenth century [49] and systematically developed the
application of Raman spectroscopy in the study of works of art, forensic science
[50] and study on the past technology for manufacturing the archaeological blue
(Egyptian Blue) and green pigments [51]. The study of the marbles from Carrara in
the Certosa of Pavia revealed that the inorganic pigment Pb 3 O 4 is responsible for
the presence of the red stains on the marble instead of previously assumed bacterial
strain identified as Micrococcus roseus [52]. The comprehensive study of works
assigned to the Italian Renaissance Master—Tintoretto—showed that the yellowish
shade over not protected areas of the realgar (As 4 S 4 ) was wrongly assumed as an
orpiment (As 2 S 3 ). The nonprotected realgar exposed to the sunlight developed into
a yellow material, identified by the Raman microspectroscopy as a pararealgar—the
light-induced polymorph of the realgar [53].
The great potential of the Raman spectroscopy in the analysis of the minerals,
liquid, and solid inclusion in minerals as well in the analysis of ceramics was
reported by Colomban in 1979. Investigations of the archaeological ceramics were
initiated by the Italian groups in the middle of nineties [54, 55]; further progress in
the study of the ancient and archaeological ceramic was made at the beginning of
the twentieth century [56]. Colomban et al. [57] with other researchers studied
selected porcelain representative for the Imperial Manufacture and now the
Manufacture Nationale de Sevres: French soft paste (‘pate tendre’ or ‘frit ware’),
English-like (bone China), the latest soft pastes made from glass (silica-rich soft
paste, Vogt soft paste), and ancient hard and new hard pastes. They revealed that
the presence of a strong beta-wollastonite and/or tricalcium phosphate peak allows
to differentiate a soft-paste body from a hard-paste body in Raman spectra.
Colomban et al. [49] continued the study of porcelain from Sevres Factory and
successfully identified and differentiated the ancient and modern European
16 Spectroscopy in the Analysis of Artworks
487
several research groups [21] started various studies with the application of Raman
spectroscopy in the field of art and archaeology. Edwards et al. published the first
scientific study on the biodegradation of the Renaissance frescos identifying calcium oxalate as the main compound in the incrustation with other organic compounds of the lichen metabolism [40] and characterizing the mono- and dihydrate
forms of the oxalate compounds [41]. Year later, paper concerning the biodegraded
cave art [42] and the research of the biodegraded archaeological materials originated from the mummified skin of Otzi the Alpine Iceman dating from 5200 BC
[43] were published. Just a few months later, Clack et al. published in England the
study of the illuminations in the unique medieval manuscripts [44] and characterization of the historically important dyes [45]. He continued the research of art
objects with the use of the Raman spectroscopy, which resulted 3 years later in
publishing the first review highlighting the advantages of this technique in the
noninvasive investigations of manuscripts [45]. In the next years, he published
study of Persian [46], German [47], and Latin [48] illuminated manuscripts.
Simultaneously, French researcher carried out investigation of the blue pigments
used by French artist in nineteenth century [49] and systematically developed the
application of Raman spectroscopy in the study of works of art, forensic science
[50] and study on the past technology for manufacturing the archaeological blue
(Egyptian Blue) and green pigments [51]. The study of the marbles from Carrara in
the Certosa of Pavia revealed that the inorganic pigment Pb 3 O 4 is responsible for
the presence of the red stains on the marble instead of previously assumed bacterial
strain identified as Micrococcus roseus [52]. The comprehensive study of works
assigned to the Italian Renaissance Master—Tintoretto—showed that the yellowish
shade over not protected areas of the realgar (As 4 S 4 ) was wrongly assumed as an
orpiment (As 2 S 3 ). The nonprotected realgar exposed to the sunlight developed into
a yellow material, identified by the Raman microspectroscopy as a pararealgar—the
light-induced polymorph of the realgar [53].
The great potential of the Raman spectroscopy in the analysis of the minerals,
liquid, and solid inclusion in minerals as well in the analysis of ceramics was
reported by Colomban in 1979. Investigations of the archaeological ceramics were
initiated by the Italian groups in the middle of nineties [54, 55]; further progress in
the study of the ancient and archaeological ceramic was made at the beginning of
the twentieth century [56]. Colomban et al. [57] with other researchers studied
selected porcelain representative for the Imperial Manufacture and now the
Manufacture Nationale de Sevres: French soft paste (‘pate tendre’ or ‘frit ware’),
English-like (bone China), the latest soft pastes made from glass (silica-rich soft
paste, Vogt soft paste), and ancient hard and new hard pastes. They revealed that
the presence of a strong beta-wollastonite and/or tricalcium phosphate peak allows
to differentiate a soft-paste body from a hard-paste body in Raman spectra.
Colomban et al. [49] continued the study of porcelain from Sevres Factory and
successfully identified and differentiated the ancient and modern European
16 Spectroscopy in the Analysis of Artworks
487