porcelains by Raman macro- and microspectroscopy [58]. Simultaneously, several
other studies focused on the archeological ceramics were published. The Neolithic
pottery found on the bank of the River Danube was analyzed by Colomban et al.
[59], who identified the yellow-to-red decor present on the external faces of pottery
as made of ocher, a mixture of hematite, quartz, and phyllosilicates. Red deposit,
found on some internal surfaces of a pottery, consists of cinnabar (HgS) with some
quartz and phyllosilicates. Following, many studies of various archaeological
findings were published, for example, study of material collected from the wall of
an ancient Celtic vitrified fort [60], ceremonial polished ‘greenstone’ axe heads
from Mesoamerica [61], and the mineral species jadeite from Guatemala [62]. In the
following years, studies focused on the analysis of the Iberian ceramics [63],
archaeological ceramics from the fourteenth and seventeenth centuries from Parma
[64], ceramics from the period between the end of the mid-seventh century and the
first half of the fourth century BC were reported, as well as brief overview about
identification of enameled pottery, glass artifacts and associated pigments [65],
application and problems of the use of micro-Raman spectroscopy in the study of
ancient ceramics [66], pre-Roman ceramics excavated near the suburbs of Canosa
(Puglia, Italy) [67], and ancient ceramics from Ebla (Syria) [68].
One of the first scientific investigations focused on better understanding of the
techniques used in wall paintings, and their deterioration was published by Edwards
[69]. The next research focused on painting techniques used in wall paintings
elucidated the misinterpretation of ancient recipes. The term ‘minium’ was used for
both, cinnabar (HgS) and red lead (Pb 3 O 4 ) pigments, in antiquity. In Roman times,
the term minium was reserved for mercury(II) sulfide (HgS) but was applied
increasingly to lead tetroxide (Pb 3 O 4 ) by the Renaissance. The differentiation of the
components of this mixture was possible by application of Raman spectroscopy
[70, 71]. Another interesting mixture of pigments was found in the medieval
frescoes in Spain. The mixed iron red with cinnabar was applied to impart the red
color in the wall paintings in the church, but pure cinnabar was being used for only
the most important biblical figures [72]. Investigations of the Italian wall paintings
were started by the group from Parma (Italy) which applied the micro-Raman
spectroscopy combined with gas chromatography and ultraviolet fluorescence
photography to study some wall paintings in the S. Giovanni Evangelista Abbey in
Parma, Italy. The micro-Raman spectroscopy determined the palette used by two
painters of the sixteenth century: Parmigianino and Michelangelo Anselmi, leading
to the identification of different white, yellow, red, brown, green, blue, and black
pigments [73] and binding media [74]. The study of Italian historical wall paintings
was continued by Baraldi et al. who used the Raman spectroscopy combined with
other analytical methods to carry out the analytical characterization of Roman
painted plasters from the ‘Domus farini’ in Modena [75]. In 2007, the first results of
scientific examination focused on characterization of pigments present in paint
samples collected from the south and east wall decorations of the fifteenth-century
Thubchen Lakhang monastery located in Nepal were published. The first results of
the micro-Raman analyses identified that azurite was used alone and sometimes in
combination with lazurite, red ocher, malachite, brochantite, which may represent
488
T. Łojewski and B. Łydżba-Kopczyńska
other studies focused on the archeological ceramics were published. The Neolithic
pottery found on the bank of the River Danube was analyzed by Colomban et al.
[59], who identified the yellow-to-red decor present on the external faces of pottery
as made of ocher, a mixture of hematite, quartz, and phyllosilicates. Red deposit,
found on some internal surfaces of a pottery, consists of cinnabar (HgS) with some
quartz and phyllosilicates. Following, many studies of various archaeological
findings were published, for example, study of material collected from the wall of
an ancient Celtic vitrified fort [60], ceremonial polished ‘greenstone’ axe heads
from Mesoamerica [61], and the mineral species jadeite from Guatemala [62]. In the
following years, studies focused on the analysis of the Iberian ceramics [63],
archaeological ceramics from the fourteenth and seventeenth centuries from Parma
[64], ceramics from the period between the end of the mid-seventh century and the
first half of the fourth century BC were reported, as well as brief overview about
identification of enameled pottery, glass artifacts and associated pigments [65],
application and problems of the use of micro-Raman spectroscopy in the study of
ancient ceramics [66], pre-Roman ceramics excavated near the suburbs of Canosa
(Puglia, Italy) [67], and ancient ceramics from Ebla (Syria) [68].
One of the first scientific investigations focused on better understanding of the
techniques used in wall paintings, and their deterioration was published by Edwards
[69]. The next research focused on painting techniques used in wall paintings
elucidated the misinterpretation of ancient recipes. The term ‘minium’ was used for
both, cinnabar (HgS) and red lead (Pb 3 O 4 ) pigments, in antiquity. In Roman times,
the term minium was reserved for mercury(II) sulfide (HgS) but was applied
increasingly to lead tetroxide (Pb 3 O 4 ) by the Renaissance. The differentiation of the
components of this mixture was possible by application of Raman spectroscopy
[70, 71]. Another interesting mixture of pigments was found in the medieval
frescoes in Spain. The mixed iron red with cinnabar was applied to impart the red
color in the wall paintings in the church, but pure cinnabar was being used for only
the most important biblical figures [72]. Investigations of the Italian wall paintings
were started by the group from Parma (Italy) which applied the micro-Raman
spectroscopy combined with gas chromatography and ultraviolet fluorescence
photography to study some wall paintings in the S. Giovanni Evangelista Abbey in
Parma, Italy. The micro-Raman spectroscopy determined the palette used by two
painters of the sixteenth century: Parmigianino and Michelangelo Anselmi, leading
to the identification of different white, yellow, red, brown, green, blue, and black
pigments [73] and binding media [74]. The study of Italian historical wall paintings
was continued by Baraldi et al. who used the Raman spectroscopy combined with
other analytical methods to carry out the analytical characterization of Roman
painted plasters from the ‘Domus farini’ in Modena [75]. In 2007, the first results of
scientific examination focused on characterization of pigments present in paint
samples collected from the south and east wall decorations of the fifteenth-century
Thubchen Lakhang monastery located in Nepal were published. The first results of
the micro-Raman analyses identified that azurite was used alone and sometimes in
combination with lazurite, red ocher, malachite, brochantite, which may represent
488
T. Łojewski and B. Łydżba-Kopczyńska