Vibrational Spectroscopy 78 (2015) 39–48
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Vibrational Spectroscopy
journal homepage: www.elsevier.com/locate/vibspec
Spectroscopic analysis of pigments and inks in manuscripts. III.
Old-Slavonic manuscripts with multicolored rubication
Irena Nastova a , Orhideja Grup9
ce a, * , Biljana Min9
ceva-Šukarova a , Maja Kostadinovska b ,
c
Melih Ozcatal
a
b
c
Institute of Chemistry, Faculty of Natural Sciences and Mathematics, Ss Cyril and Methodius University, Skopje, Macedonia
Conservation and Restoration Laboratory, National and University Library “St. Clement of Ohrid, Skopje, Macedonia
Department of Material Science and Engineering, Faculty of Engineering and Architecture, Anadolu University, Eskişehir, Turkey
A R T I C L E I N F O
A B S T R A C T
Article history:
Received 14 January 2015
Received in revised form 17 March 2015
Accepted 19 March 2015
Available online 20 March 2015
Raman spectroscopy, FTIR spectroscopy and SEM-EDS were applied in characterization of pigments and
inks in five old-Slavonic manuscripts: Ki9cevo Four Gospel (16th century), Zrze Four Gospel (16th/beginning
of 17th century), Struga Four Gospel (beginning of 17th century), Kruševo Ochtoechos (second half of 15th
century) and Psalter with rituals (beginning of the 16th century). The illuminations used in the first four
manuscripts are in so called Balkan style characterized with interlaced rings and floral motifs, with rarely
seen, multicolored rubication text: in Ki9cevo and Zrze Four Gospel manuscripts are written in four colored
inks: black-brown, blue, red and purple-red while in Struga and Kruševo Ochtoechos manuscripts is blackbrown, blue and red inks. Psalter with rituals is a manuscript from the same period, with typical
rubication in red and was included in the study as standard form of manuscript. In addition to several
types of gall ink identified as brown-black ink used in the manuscripts, carbon black ink and logwood ink
were also identified. In colored inks, azurite or mixture of azurite and indigo were used as blue ink while
vermilion or mixture of vermilion and red lead was used as red ink. Another, purple-red ink of organic
nature was used as well. The pigments identified in ornaments are: azurite and indigo in blue colors,
orpiment as yellow pigment, vermilion, red lead and organic red pigment as reds, while green pigment
was identified as organo-Cu complex. Brown-black ink was used for framing the illuminations and
illuminated initial letters and pure gold for gilding. In spite of similar style and pigments, slight but
characteristic differences in pigments and inks used, suggest different scriptoria.
ã 2015 Elsevier B.V. All rights reserved.
Keywords:
Old-Slavonic manuscripts
Pigments
Inks
Micro-Raman spectroscopy
SEM-EDS
IR spectroscopy
1. Introduction
In the course of our study on pigments and inks in medieval
manuscripts, kept on the territory of Republic of Macedonia [1–4],
four 16–17th century old-Slavonic gospels have been analyzed. The
manuscript Kruševo Ochtoechos, dated second half of the 15th
century was also included in the study, due to the fact that first two
pages are later addition with illumination and multicolored
rubication. The manuscripts are written on paper, with old Cyrillic
alphabet, in old-Slavonic language and bear the names of the
places where they had been disclosed. The illuminations are
multicolored, in so called Balkan style, characterized with
interlaced rings and floral motifs [5,6], Figs. 1 and 2. Large,
elaborate multicolored capital letters in Balkan style are also
* Corresponding author. Tel: +389 70 340 220; fax: +389 23 226 687.
E-mail addresses: [email protected], [email protected] (O. Grup9
ce).
http://dx.doi.org/10.1016/j.vibspec.2015.03.005
0924-2031/ ã 2015 Elsevier B.V. All rights reserved.
present at the beginning of each chapter. The elaborate and
accurate execution of the ornaments in the Zrze Four Gospel
suggests that the scribes might have used some type of pattern/
stencils for the drawings while in the other manuscripts, the
illuminations are more of a free hand style.
The Ki9
cevo Four Gospel, Zrze Four Gospel, Struga Four Gospel and
Kruševo Ochtoechos were chosen for comparative analysis due to
their unusual, mutual characteristics in using multicolored inks for
rubication, untypical for the majority of the old-Slavonic and
Byzantine manuscripts, which mainly rely on rubication in red and/
or gold. The scriptoria where they were scribed are unknown.
Although, at that time, there have been well-established scriptoria
on this territory [5,6], common practice was that individual
churches actually had its own scribe activity for its own needs.
That is the reason why many of the old-Slavonic manuscripts are of
unknown provenance, as is the case of the title manuscripts.
However, unusual and quite rare mutual characteristic of multicolored rubication of analyzed manuscripts could suggest possible
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I. Nastova et al. / Vibrational Spectroscopy 78 (2015) 39–48
Fig. 1. Representative pages in the manuscript in S_FG (a and b), Z_FG (c and d), K_FG (e and f) and P_R (g and h).
Fig. 2. Representative pages in the manuscript K_O: (a) illumination, (b) glued page, (c) first page (d) 18th century “restoration” text.
I. Nastova et al. / Vibrational Spectroscopy 78 (2015) 39–48
mutual origin, the same scribe or scriptorium. To the best of our
knowledge, there are two more 16th/17th century manuscript with
multicolored rubication, again from the same geographical region,
(one disclosed in the village of Leunovo, Republic of Macedonia and
the other from Slep9
ce monastery, Republic of Macedonia (nowdays
kept at the Historical and Archival Church Institute in Sofia,
Bulgaria) that were not available for the study. It seems that this
characteristic of illumination existed dominantly in this region in
16th/17th century period and was locally developed. It is not clear
why this multicolored rubication appeared in particular period
(16th/17th century), was limited to small number of manuscripts
and then disappeared. It is also not known if this style was a
“practice” of an adventurous scribe in particular scriptorium or
practice of several related scriptoria. It certainly was not wide
spread activity. The fifth analyzed manuscript, Kruševo Ochtoechos,
is dated as 15th century text, however it is a composite manuscript,
with crude “restoration” from 18th century and with addition of the
two opening pages that are not dated. The illumination on the page
2 is with multicolored rubication that comply well with the scope of
this study.
An archaeometric analysis of pigments and inks in the
manuscripts was undertaken to offer insight into the similarities
and differences of the pigments used and thus suggest whether
they are of mutual origin or not. In addition, another book, Psalter
with rituals (dated as the beginning of 16th century) with
traditional, red rubication is studied. This manuscript, without
multicolored rubication, was chosen for comparison because it is a
typical form for old-Slavonic manuscripts, originating from similar
period, from the same region and with similar decoration as the
rest of the analyzed books but in red and black.
The manuscripts have been subjected to palaeographic and
linguistic studies and, based on the paper watermarks are dated
[7,8], but no archaeometric study has yet been performed on the
pigments and inks. In fact, archaeometric evidence on the oldSlavonic manuscripts, in general, is scarce in the literature [1]. Even
evidence on Byzantine and other orthodox manuscripts are scarce
[9–11]. The aim of this study was to identify the pigment palette
and inks that scribes used for decoration in Ki9
cevo, Zrze and Struga
Four Gospels, Kruševo Ochtoechos and Psalter with rituals illuminated manuscripts and consequently draw conclusions about
similarities and differences, which may help elucidate their
provenance. It will also add to the general knowledge about the
pigments use in old-Slavonic manuscripts. Having in mind that the
territory where the manuscripts were scribed was influenced, first
by the Byzantine culture, than in the 15–19th century by the
Ottoman culture, it could provide some information about the
possible know-how exchange and influences of other cultures.
The archaeometric analysis of valuable, old, fragile manuscripts
is followed by difficulties in keeping the integrity of the manuscript
and preventing any damage while performing the experiment.
However, the development of different analytical tools in the last
decades, offered possibilities for in situ characterization of the
cultural heritage objects [12], which relatively simplified the
process. Increased sensitivity of techniques and the need for
minute sampling only added to the increased activity in manuscript characterization. In addition to better possibilities of the
techniques, combination of two or three techniques provides more
substantial view on the characteristics of the analyzed object. In
this particular study, the main technique applied for nondestructive study of art object, was micro-Raman spectroscopy
[13,14] which is proven advantageous technique for non-destructive in situ analysis of art objects, allowing detection of pigments
and inks. Raman spectroscopy enabled fast and in situ analysis of
majority of pigments and inks used, except for the purple-red
organic pigment/ink and metallic pigments (gold). However, two
other techniques were applied for characterization of the used
41
pigments: ATR-FTIR was used in characterization of the organic
purple-red pigment/ink and gall inks while SEM-EDS was used in
analysis of the silver and gold pigment as well as an additional
technique for characterizing organic purple-red pigment/ink.
2. Experimental
2.1. Samples/sampling
Most of the pigments and inks in the studied medieval
manuscripts were analyzed in situ. In the case of the metallic
and purple-red pigments, samples were taken on cotton swabs.
2.2. Raman spectroscopy
Micro-Raman spectrometer LabRam 300 (Horiba Jobin-Yvon)
equipped with a He–Ne laser operating at 5 mW (on the sample)
and 632.8 nm was used for Raman analysis. An Olympus MPlanN
microscope with magnification 50 was used to focus the laser
onto the samples. The backscattered light was dispersed using
1800 lines/mm grating. The calibration was performed both by
Reghliegh line and Si standard at 520.7 cm-1. The spectral
resolution was 3–4 cm 1 with the wavenumber accuracy of
1 cm-1. The laser spot on the sample was 2 mm. To avoid any
damage to the manuscript, laser power was attenuated using
different neutral density filters (D = 0.3, D = 0.6, D = 1 and D = 2).
Acquisition time varied from 3 to 10 s, with 5–25 scans. Most of the
spectra were recorded in the 100–1800 cm 1. The LabSpec package
[15] was used for spectra acquisition and GRAMS 32 for spectra
manipulation [16]. All spectra were baseline corrected and filtered
if needed with LabSpec software [14] in order to remove the
background fluorescence and excessive noise. The obtained Raman
spectra were compared to the reference database and libraries of
pigments [16–19].
During the analysis, pages were held in place using weights, to
avoid loss of focus due to the vertical and horizontal vibrations. The
books with bound pages required a bit of cautiousness and
adjustment to keep the angle of the open book at 120 during the
measurements.
Raman spectroscopy was not suitable technique for the purplered organic pigment and purple-brownish ink due to the organic
nature of the pigments and as a consequence strong fluorescence
hindered detection of Raman bands.
2.3. ATR FTIR spectroscopy
Infrared spectra were recorded on the FT-IR PerkinElmer
2000 interferometer in the 4000–570 cm 1 region, with 64 scans
and resolution of 4 cm 1. ATR cell (Golden Gate) with sapphire
anvil was used for in situ measurements, or for samples on a cotton
swab. ATR-FTIR analysis allowed characterization of the purple-red
pigment used in illuminated books as well as characterization of
the purple-red ink.
2.4. SEM-EDX analysis
was applied for identification of the elemental composition of
metallic pigments that could not be identified by Raman spectroscopy and for additional characterization of green pigment, few inks
and organic pigments. In these cases, samples were taken by rubbing
a slightly wet cotton swab against the painted surface, which yielded
several micro-crystals being removed from the painted surface.
SEM-EDS analysis, for compositional characterisation, was carried
out on the surfaces without coating in the variable pressure
atmosphere. Pigments were examined using scanning electron
microscopy (SEM-Zeiss Supra 50VP) attached with energy dispersive
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I. Nastova et al. / Vibrational Spectroscopy 78 (2015) 39–48
X-ray spectrometer (EDX-Oxford, INCA). Analysis were routinely run
at 12 kV accelerating voltage, for 60 s in 8 mm working distance (WD)
with high accuracy mode and 30 mm aperture size.
brownish, blue) while the rest of the text begins with large,
illuminated initial letter (Fig. 1 a,b).
3.4. Kruševo Ochtoechos
3. Description of the books
Basic characteristics of the analyzed manuscripts, number of
analyzed folios of each manuscript and their corresponding
abbreviations are given in Table 1. Some additional information
regarding the content and principle features of the manuscripts are
presented below.
3.1. Struga four gospel
17th century (S_FG) comprises four illuminations in gold, red,
blue and green color. White paint is not used per se, white blank
spaces are left instead. Although they all comply with the Balkan
style illuminations, with intertwined rings and floral inserts, there
is pronounced variation in their overall shape. (Fig. 1a,b). The color
palette of illuminations is similar to the Z_FG and richer compared
to the other manuscripts (additional pigments are used), but the
execution is not very precise and is more of a free hand. The text is
written with brown-black inks with illuminated initial letters and
rubication in red and blue.
3.2. Zrze four gospel
16th/17th century (Z_FG) is by far the most richly decorated book
of the four. The book contains two, very elaborate illuminations, in
the form of large squares (Fig. 1c, d), decorated in golden, bright red,
purple red and blue color, with no blank white spaces left.
Illumination patterns are similar to the ones in K_FG but executed
with high precision. The text is written with brown-black inks with
colored rubication in red, blue and purple-red.
3.3. Ki9
cevo four gospel
16th/17th century (K_FG) comprises text decorated with
multicolored inks and with four illuminations. At the beginning
of each gospel, a headpiece in a form of a large, square, intertwined
arabesque in blue, yellow, red and purple-red is inserted (Fig. 1e, f).
The illuminations are very similar in pattern to the ones in Z_FG but
executed with less precision. Instead of golden pigment used in
Z_FG, yellow pigment is applied. Blank, uncolored spaces are left in
the arabesques, as part of the decoration (instead of white
pigment), similarly to the S_FG illuminations; however the last
illumination is apparently unfinished. The used colors are bright
red, blue, purple-red and yellow. The headpieces are followed by
one line rubication in large multicolored letters (red, purpleTable 1
Basic information for the analyzed manuscripts.
Manuscript
Analyzed folios
Abbrev.
Zrze Four Gospels
(End of 16th/beginning of 17th century)
Paper, 29,5 19 cm; ff 228/NUB Ms 157
Struga Four Gospels
(Beginning of 17th century)
Paper, 30 20 cm; ff 276/NUB Ms 42
Ki9
cevo Four Gospels
(End of 16th century)
Paper, 28 21 cm; ff 290/IAO M296
Kruševo ochtoechos
(Second half of 15th century)
Paper, 28 20 cm, ff.244
Psalter with rituals (mid 16th century)
Paper, 20,5 13,5 cm; ff 378/NUB Ms 19
59, 100, 173, 219
Z_FG
5, 82, 133, 214, 243
S_FG
2, 121, 128, 158, 192
K_FG
1, 2, 61, 114, 118, 200
K_O
1, 4, 114, 123, 377
P_15
second half of the 15th century (K_O) is composite unbound
manuscript with lose pages comprising a 15th century written text
with poor restoration interventions performed in the 18th century
(Fig. 2d). However, the first two pages (Fig. 2a, c) are later than 15th
century addition to the text and are glued on top of the existing
pages (Fig. 2b). They are not dated, but page 2 is with illumination
and multicolored rubication (Fig. 2a), similar to the one from S_FG.
The illumination is in three colors – blue and red, outlined with
black ink, while rubication is in blue and red. In the 15th century
text rubication is in red. At least four, distinct handwriting could be
identified, one in the main text from the 15th century, one from
restoration in 18th century and additional two, on each of the
opening pages (Fig. 2)
3.5. Psalter with rituals
First half of the 16th century (P_R) is with traditional red
rubication, brown-black inks and two illuminations (Fig. 1g, h).
One of the illuminations, although employs intertwined motifs is
in unusual form with uncolored parts while the other illumination
is left completely uncolored, suggesting that the book decoration is
not completely finished. The illuminated initial letters are not
colored as well. Two distinct handwritings are clearly observed,
suggesting two scribes scribed the text, with addition of a
signature ownership in a third ink.
4. Results and discussion
The results of the pigment study are shown in Table 2.
Discussion is carried out in a cumulative–comparative manner
within the color scheme, providing presentation of the results
without repetitions.
4.1. Ornaments
The decoration in all five decorated manuscripts is in a
traditional old-Slavonic style with color palette consistent with
the meaningful colors of the liturgy. Depending on the manuscript,
different combinations of red, blue, yellow, gold or green are used
(Figs. 1 and 2).
4.1.1. Yellow color
Yellow color is used in K_FG, S_FG and P_R while in Z_FG and
K_O yellow color is absent from the decoration. As a matter of fact,
yellow color could not be observed in S_FG as well since it is only
used as underlayer for the gold pigment and is noticeable only
under the microscope. Raman spectra of the yellow pigment
revealed that orpiment was used as yellow pigment in K_FG and
P_R, Fig. 3a. The underlayer (glue) for the golden pigment in S_FG
was orpiment as well. Having in mind that golden pigment was
used in decorations of Z_FG and S_FG at the places where yellow
pigment was used in K_FG and P_R, it seems that yellow pigment
used in these manuscripts was a substitute for gold, as cheaper
replacement. Since both manuscripts where yellow pigment was
used are Gospels and originate from the same period as the
Gospels decorated with gold, the difference in using yellow/gold
color might suggest that they were scribed in at least two
different scriptoria – one that could provide gold for the
manuscript decoration and the other that could not afford it.
I. Nastova et al. / Vibrational Spectroscopy 78 (2015) 39–48
43
Table 2
Identified pigments and inks in analyzed manuscripts.
Color
Z_FG
(End of 16th/beginning of 17th c.)
K_FG
(End of 16th/beginning of 17th c.)
S_FG
(Beginning of 17th c.)
P_R
(First half of 16th c.)
K_O
(Second half of 15th c.)
Illumination
Yellow
Gold
Bright-red
Purple-red
Blue
Green
Brown
n/a
Gold
Vermilion + red lead
Organic purple-red,vermilion + red lead
Indigo, azurite
n/a
Gall ink
Orpiment
n/a
Vermilion
n/a
Azurite
n/a
Gall ink
Orpiment
Gold
Vermilion
n/a
Indigo, azurite
Organo-Cu complex
Gall ink
Orpiment
n/a
Vermilion + red lead
Organic purple-red
Azurite
n/a
Gall ink
n/a
n/a
Vermilion
n/a
Azurite
n/a
Gall ink
Inks
Red
Purple-red
Blue
Brown/Black
Vermilion + Red lead
Madder
Indigo, azurite
Gall ink
Vermilion
Madder
Azurite
Gall ink
Vermilion
n/a
Indigo, azurite
Gall ink
Vermilion
n/a
n/a
Gall ink, carbon
Vermilion
Madder
4.1.2. Golden color
Golden pigment was observed in S_FG and Z_FG illuminations
only. The results from the SEM_EDS (Fig. 4) confirmed that pure
gold was used in S_FG and Z_FG. Naturally found gold usually
contain silver, pure gold is usually product of purification. This find
differs from the gold used in 11–14th century Byzantine manuscripts, where gold with different percentage of silver was
identified; suggesting purified gold was used in this case. As in
the case of Byzantine manuscripts [2], SEM-EDS did not identified
mercury or chlorides, suggesting that traditional methods of
purification through amalgamation and pulverization of gold
pigment with salt were not used. In the case of S_FG, as was already
stated, under the gold layer, a yellow underlayer of orpiment was
used. In our previous studies on Byzantine and old-Slavonic
manuscripts [1,2,4], under the gold pigments, we have identified a
pigment underlayer acting as a glue for the gold pigment. In all the
Byzantine manuscripts we have analyzed, the underlayer was
always red and exclusively vermilion, while in the old-Slavonic
manuscripts, realgar/pararealgar, orpiment or vermilion has been
identified. It seems that in the old-Slavonic manuscripts there was
no specific rule for the underlayer pigments so diverse pigments
were used. In the case of Z_FG, gold pigment was applied on the
paper without pigment underlayer. The application of gold
Gall ink, carbon, logwood
pigment directly on paper, without an pigment underlayer is
quite untypical for Byzantine and old-Slavonic manuscripts, but is
more-less a standard procedure in the Islamic/Ottoman manuscripts [3]. Since the Ottoman Empire ruled this region in the
15–20th century, and the manuscript is written in the 16th/17th
century, the know-how exchange and influence of the Ottoman
practice in applying gold without underlayer is quite feasible.
4.1.3. Red/purple-red color
Red color is dominant color in the illuminations of all five books
(Figs. 1 and 2, Table 2). In old-Slavonic manuscripts previously
analyzed [1], the most commonly used red pigment was vermilion.
Title manuscripts were not exception, vermilion (HgS) was
identified in all of the manuscripts. Still, while in K_FG, S_FG
and K_O pure vermilion was applied, in Z_FG and in P_R a mixture
of vermilion and red lead was used (Fig. 3b). There had been
obvious reason for the use of the vermilion and red lead mixture
since in Z_FG and K_FG: additional purple-red color was used for
decorations, so vermilion red hue had to be adjusted to emphasize
the contrast with the purple-red. To achieve that, scribe/s used
vermilion and red lead mixture, obtaining more of an orange-red
hue and obtaining nice contrast to the purple-red. It seems that
purple-red pigment was applied in the later stage of the
decoration, over the already painted vermilion-red lead mixture
since vermilion and red lead were detected in the Raman spectra of
the purple-redcolor as well. Raman spectroscopy did not yield
usable spectra of the purple-red pigment because of the intense
fluorescence under the laser light, suggesting organic nature of the
pigment. To obtain some insight into the nature of the purple-red
pigment, two additional techniques were applied: ATR-FTIR
spectroscopy and SEM-EDS (Fig. 5A, B). Purple-red pigment from
different manuscripts yielded infrared spectra of different quality;
Fig. 3. Raman spectra of: (a) orpiment in K_FG, (b) mixture of red lead and
vermilion in Z_FG, (c) mixture of indigo with azurite in Z_FG and (d) azurite in K_FG.
Fig. 4. Representative SEM-EDX spectrum of the gold pigment in S_FG.
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I. Nastova et al. / Vibrational Spectroscopy 78 (2015) 39–48
Fig. 5. K_O manuscript: (A) Representative FTIR spectra of the purple-red pigment (a) pigment and paper (b) clean paper (c) subtraction with enlarged section; (B)
Representative SEM-EDX spectrum of the purple-red pigment.
the infrared spectra of purple-red in K–O are shown on Fig. 5A.
Since ATR infrared spectra were recorded directly on the purplered letters, the resulting spectrum contained summed up bands of
the pigment and the paper (Fig. 5A (a)). Additionally, the IR
spectrum of the blank part of the page was recorded (Fig. 5A (b))
and resulting subtraction spectrum derived the IR spectrum of the
purple-red pigment (Fig. 5A (c)). Although the IR region between
1300 and 1700 cm 1 is obscured with additional IR bands of the
paper and mordant salts, the obtained subtraction spectrum
comply well with the IR spectrum of madder obtained for
Byzantine manuscripts [2] and with the literature data [20,21].
The SEM-EDS results are in agreement with the preparation
procedure for madder dye and showed the presence of the
characteristic ions (Al, K, S, Mg) [20,21] similar to the those
obtained for Byzantine manuscripts [2]. Based on the ATR-FTIR
spectrum and SEM-EDS results the purple-red pigment was
Attributed to madder Fig. 5. Madder root is easily grown in the
Balkans and is traditionally used for coloring. In the studies of
Svobodova et al. [22] the use of IR spectroscopy in identification of
madder is questioned, suggesting that IR spectra cannot distinguish between madder and kermes. Even in that case, with the
presumption that IR results could not be able to confirm, beyond
doubt, the use of madder in the purple-red paint, the other
pigment from alizarin family, kermes, is unlikely to have been
used. Although often found in the Arabic manuscripts [23,24],
kermes is not locally produced and used nor has ever been
identified in any of the pigment studies from this region. On the
other hand, madder root is easily grown in the Balkans and was
traditionally used (Easter eggs were colored with madder in this
region till the mid 20th century). The dye was called barzion, the
same name for the madder root dye used in Byzantine treatise [9].
Contrary to the richly decorated Byzantine gospel manuscripts
[2] where purple-red is a dominant red color with vermilion
(bright red) used only for accents, in old-Slavonic manuscripts
bright-red (vermilion) is a dominant color with accents in purplered. However, it should be noted that in more modest Byzantine
religious books [2], especially from the later period, bright-red
vermilion was a dominant color. It seems that purple-red mordant
dye had exclusive (divine) role and was used in more elaborate
gospels in the Byzantine manuscripts, while vermilion was readily
available and simpler to obtain, which made this pigment (in some
cases with addition of red lead) very popular red pigment applied
in all types of manuscripts. However, all three red pigments
(vermilion, red lead and madder) are widely used in both
old-Slavonic and Byzantine manuscripts.
4.1.4. Blue color
Blue color was used in the decorations of all five manuscripts. In
all cases azurite was identified as blue pigment. In Z_FG and S_FG
additional blue pigment was used – indigo (Table 2 and Fig. 3c,d).
Under the microscope the two blue pigments did not appear as
mixture of azurite and indigo, on the contrary, at places only indigo
was identified. It seems that in these two manuscripts originally
indigo was used. As indigo is a plant based pigment that easily fade,
at some latter period, azurite was applied, most probably, for
corrections of the faded blue color. In old-Slavonic manuscripts
modest blue pigments are used (azurite, indigo), contrary to the
Byzantine gospels (11–14th century) where abundance of
expensive lazurite was identified. However, in 18th century
post-Byzantine manuscript [2], similarly to the old-Slavonic
manuscripts, a mixture of indigo and azurite was identified as
blue pigment.
4.1.5. Green color
Green color was observed in the manuscript S_FG only. It was
not a mixture of blue and yellow pigment as often found in
Byzantine and sometimes in the old-Slavonic manuscripts [1,2,4].
The Raman spectrum of the green paint suggested a green pigment
I. Nastova et al. / Vibrational Spectroscopy 78 (2015) 39–48
45
Fig. 6. Green pigment in S_FG: (a) Raman spectrum and (b) SEM-EDX results.
of an organic nature, due to the intense band at around 2390 cm 1
and bands in the finger print region (1600–600 cm 1) (Fig. 6a). To
clarify the origin of the green pigment, SEM-EDS was performed.
The presence of Cu was confirmed, verifying that Cu based complex
was used as green pigment (Fig. 6b). However, the Raman spectra
of the Cu organo-complex pigment (Fig. 6a) obtained in this study
are more complex, richer with bands and differ from the Raman
spectra of green organo-complex found in the previously reported
studies of old-Slavonic and Islamic manuscripts [1,4]. The most
popular organic green pigment in the 16th/17th century was
verdigris, pigment obtained through reaction of copper with
vinegar [23–28]. Since various recipes [29,30] (addition of
carbonates, chlorides, ammonia) were used for obtaining this,
popular and widely used green pigment, its composition varies
[25] and can be related to different ratios of acetates, carbonates
even chlorides and ammonia. Accordingly, the Raman spectra of
obtained Cu-organo complex vary as well. The SEM-EDS results of
the sample from the green paint showed additional presence of
chlorides (compared to the previously analyzed green Cu-organo
complexes) (Fig. 6b). This find could suggest that the recipe
included ammonium or sodium chloride, for preparation of the
green pigment [29], which can result in copper complexes
containing ammonia and chloride. In addition to that, the
degradation of the pigment and binders due to age and/or
microbial attack [31,32] should be considered as well. Considering
the complexness of the 1600–800 cm 1 region, highest frequency
band (1605 cm 1) and the lowest (838 cm 1) and the number of
bands (Fig. 6a), it could suggest that mixture of a Cu-based pigment
and its degradation product is obtained.
The degradation product we considered possible was moolooite
(copper oxalate), a degradation product when microbial attack
occurs (frequencies at 1489,1450,921,833 cm 1) [21,32,33]. Although
the frequencies of the bands in the spectrum do not quite match to
those of the pure verdigris and pure moolooite, in cases of naturally
occurring mixture, the resulting spectrum should be dependent on
the different stages of degradation so differences are expected.
4.2.1. Brown/black inks
The main text in all the manuscripts was written with brown/
black ink with rubication in different color at the beginning of the
chapters. In general, the dark ink did not show pronounced fading
or corrosion to the support. As it was mentioned before, it was
noticeable that the text in P_R was written with two different
handwritings and with two different inks. Besides, there was a
signature in additional, third, ink so it was expected to identify
three different inks in P_R. Similarly, in K_O, four distinct
handwritings were identified in agreement with the text written
(or corrected) in three/four different periods.
In the manuscripts of Byzantine or old-Slavonic origin we have
analyzed, gall ink was an ink of choice, as it was in many other
regions [1,2,34–37] in Europe. The Raman analysis of the studied
manuscripts showed that the majority of black/brown inks in the
manuscripts were indeed iron gall ink (bands around 566, 1340,
1480/1490 and 1576 cm 1) (Table 2, Figs. 7 Fig. 8b,c). Change in the
color (darker, lighter, saturated) could be observed too. The overall
shape of the recorded spectra of gall inks are very similar and bear
strong characteristics of iron gall ink, however, there is slight shift
in the frequency of the characteristic iron gall Raman bands
appearing between 1480 and 1490 cm 1 (Figs. 7a,c and Fig. 8b,c).
The lowest frequency of this band (at 1480 cm 1) was found in
K_FG, in one of the gall inks in P_R (Fig. 7a) and K-O (8b); in Z_FG
and S_FG it appears around 1484 cm 1 (Figs. 7b), while in P_R and
K_O, the second type gall ink showed band at 1495 cm 1
(Figs. 7c, 8c). The reason for the slight shift in the frequencies
4.2. Inks
As it was already mentioned, the title manuscripts were chosen
for analysis due to the unusual multicolored rubication in the texts.
Traditionally, the religious texts are generally written with black/
brown ink, with emphasized parts in bright-red (as it is in the
manuscript P_R) and/or gold. In analyzed manuscripts, in S_FG and
K_O blue and bright-red color was used for rubication while in
Z_FG and K_FG bright-red, purple-red and blue were used
(Figs. 1 and 2). The colored letters are all framed in brown-black
ink. As seen from Table 2, the same pigments applied in the
illuminations were used for preparation of colored (red, purple-red
and blue) inks.
Fig. 7. Representative Raman spectra of gall inks from: (a) K_FG and P_R), (b) Z_FG
and S_FG, (c) P_R and (d) Carbon black ink from P_R.
46
I. Nastova et al. / Vibrational Spectroscopy 78 (2015) 39–48
of this most intensive Raman band could be found in the gall ink
preparation recipes. Namely, besides FeSO47H2O, gallic acid and
gum Arabic, medieval recipes suggest number of other components that could be included in preparation of historic ink [38].
Proportion of ink components and production methods could
affect the frequency position of the main gall ink Raman band.
SEM-EDX performed on analyzed inks identified additional cations
(Al, Mg, K, Ca) beside Fe-ions, which could affect the position of the
bands. In addition to that, as shown in literature [39,40], different
sources of tannic acid could be used, which again could lead to shift
of the band around 1485 cm 1. Based on the slight differences in
the frequencies of the most intensive band, appearing between
1480 and 1490 cm 1 (Figs. 7a–c; 8a,b) analyzed inks could be
classified into several variations of iron gall inks. Gall inks in
Byzantine manuscripts we have studied exhibited similar features
in the Raman spectra [2]. Based on the similarity of results
regarding analyzed inks in Byzantine and old-Slavonic manuscripts, it seems that several variations on iron gall ink recipes were
in use in orthodox (Byzantine and old-Slavonic) scriptoria,
resulting in several slightly different Raman spectra.
In K_O manuscript, scribed in 15th century; besides two distinct
types of iron gall ink (Fig. 8b,c), the third ink, used on the
illumination page was identified as logwood ink (Fig. 8a). This ink
is prepared from chips of Haematoxylum campechianum tree, the
main component being haematein. The wood was imported from
South Amerika and became available in Europe in 16th century. It
has been identified as ink in one post-Byzantine manuscript in our
previous study [2]; however in this case, the identification of
logwood ink was quite unexpected. The medieval monastic life was
quite solitude, separated from activities and novelties introduced
to secular, everyday life; besides this region was ruled by
Ottomans, who used carbon ink exclusively and is quite far from
trade routes of coastal areas where logwood ink would had been
readily available. The use of logwood on the manuscript confirms
that there must have been links and interaction between regional
local churches and Slavic monasteries on Mount Atos along the
Greek coast where logwood ink would have been available.
Unexpected as it was, the identification of logwood helped narrow
down the dating of the page to at least from 16th/17th century
onwards since logwood ink became available in that period, exactly
the period when the rest of multicolored rubication manuscripts
were scribed.
Additional type of black ink untypical for the region, carbon
black ink (Figs. 7 and 8d) was identified in P_R signature as well as
in the 18th century “restoration interventions” in K_O. Carbon
black as ink by itself is not standard ink used in orthodox
manuscripts; whenever carbon black was identified it was usually
in a mixture with iron gall ink [1]. However, the use of carbon black
in 18th century restoration in K_O and the signature (probably
from latter period) in P_R suggest the influence of Ottoman scribe
tradition, which used carbon black ink exclusively [3,23,24].
4.2.2. Red
Red ink was used in all the manuscripts. Except for Z_FG where
a mixture of vermilion and red lead was used, consistent with the
red mixture used in the illuminations of that book, in the other four
manuscripts, pure vermilion was used. Vermilion was a pigment
most commonly used whenever rubication was needed.
4.2.3. Purple-red inks
Purple-red ink was used in Z_FG and P_R, for capital letters or in
paragraphs, together with the other colored letters. In K_O purplered was used for capital letters in the 15th century text and in the
18th century restoration but not on the two first pages, where only
Fig. 8. Representative brown/black inks from K_O: (a) logwood, (b) iron gall ink in page 1, (c) iron gall ink in 15th century text, (d) carbon ink.
I. Nastova et al. / Vibrational Spectroscopy 78 (2015) 39–48
47
vermilion was used. As it was discussed in Section 4.1.3, the results
of the infrared spectra and SEM-EDS analysis were not conclusive
regarding the origin of the organic dye. However, due to traditional
use and availability of madder in this region, it is highly probable
that madder was used as purple-red ink (Fig. 3a, b).
identified, which is quite untypical ink for the region, but almost
exclusive ink in the Ottoman practice. In Z-FG the gold was applied
without pigment underlayer, again very untypical of the common
practice for the region but very typical of the Ottoman practice.
4.2.4. Blue ink
The blue ink was obtained using pigments consistent to the
pigments used in the illuminations e.g. azurite was used in K_FG,
while a mixture of azurite and indigo was detected in the blue
letters of S_FG and Z_FG.
Acknowledgement
5. Conclusion
An archaeometric analysis of pigments and inks in four 16/17th
century old-Slavonic manuscripts and one from the 15th century
characterized with multicolored rubication was undertaken to
offer insight into the similarities and differences of the pigments
used and thus suggest whether they are of mutual origin or not. As
shown in Table 2, the manuscripts pigment palette is limited, with
pigments widely available and well known since antiquity.
However, there are slight but pronounced differences in the
pigments used in each manuscript. Presence/absence of individual
pigment in the manuscripts (Table 2) suggests that most probably
different scribes in different scriptoria scribed the manuscripts.
Additional evidence is the difference in the Raman spectra of the
iron gall inks. Although Raman spectra show overall features of
iron gall ink, slight differences in the frequencies of the bands
could be noticed. It seems quite unlikely that in one and same
scriptorium, in similar time frame, different inks would be used. So,
based on the results of analysis (Table 2) although with unusual,
mutual characteristics and with similar pigment palette, it seems
that these manuscripts were scribed in different scriptoria, most
probably small, local church oriented scriptoria.
Old-Slavonic manuscripts are based on Byzantine manuscript
writing tradition, so the results were correlated to the results
obtained for the Byzantine manuscripts. Over all, the use of
pigments in both traditions is very similar, but not identical.
Byzantine manuscripts heavily rely on presence of both gold and
purple-red. Gold and purple red was used in Z-FG, which might
suggest that this manuscript was scribed in the region closer to the
Byzantine church influence, thus keeping the Byzantine tradition
the most. In S-FG gold was used as well but not the purple-red. In PR purple-red was used, but not the gold. It seems that Byzantine
influence was alive on this territory but more as a tradition not in a
strict, canonical way. Additional difference was the use of
underlayer under the gilding. In Byzantine manuscripts vermilion
is the pigment of choice used as underlayer, while in old-Slavonic
manuscripts wider variety of pigments is identified (vermilion,
orpiment, realgar-parapealgar). There is pronounced difference in
the use of green pigments as well. In the Byzantine manuscripts,
green color is obtained solely by mixing blue and yellow pigments,
while in old-Slavonic manuscripts wider palette of green pigments
was used – mixtures of blue and yellow, similar to the Byzantine
ones, as well as green pigments as Cu-organic pigment and
malachite. Regarding iron gall ink, in both traditions, similar
features were observed. The recorded Raman spectra of iron gall
ink in the analyzed samples of both Byzantine and old-Slavonic
manuscripts exhibit shift of the most prominent band in the region
1480–1495 cm-1, suggesting that in both traditions, variations of
iron gall inks were in practice. The identification of logwood in
K_O, on the other hand, suggest contacts of the regional churches
with the Slavic monasteries in coastal Greece, on Mount Atos.
Since the region was under Ottoman rule in that period, the
influence of Ottoman practice in manuscript scribing, in our
opinion, could be noticed too. In P_R and K_O, carbon black ink was
The financial Support of the Ministry of Education and Science
of Republic of Macedonia for the project No. 13-3571 is highly
appreciated. The help of Zorica Jakovlevska-Spirovska from
National and University Library “Sv. Kliment Ohridski and Ilinka
Janeva from National Archive-Ohrid in providing manuscripts is
acknowledged.
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