Color and Ink Characterization of the Ottoman Diplomatics Dating from the 13th to the 20th Century
Ömer KANTOĞLU*, Ece ERGUN, Rıdvan KIRMAZ, Yakup KALAYCI, Abdullah ZARARSIZ and Önder BAYIR
ABSTRACT
This study investigates the colors and inks used in the diplomatics o f the Ottoman Empire dating
from the 13th to 20th century. Elemental and spectroscopic analyses were carried out on more
than 150 diplomatics using the p-XRF, Raman and FTIR spectroscopies, but 10 o f them were
chosen representative for each century. In addition to the characterization o f color and ink, the
common or rare use o f different colors and inks through ages is discussed. The results o f the
analysis o f the Ottoman diplomatics revealed that minium, vermilion, red ochre and cochineal
comprised the red color; lapis lazuli (ultramarine blue), azurite (blue verditer), Prussian blue
and smalt were used as the blue color; malachite and green earth provided the green color;
massicot was used as the yellow color; yellow lead constituted the orange color; and basic lead
carbonate and zinc oxide were the source o f the white color have been determined in the
diplomatics o f the Ottoman Empire. All the illuminations were ornamented with gold to
demonstrate the power o f Empire and also Emperor. The text script o f the diplomatics were
written in black, red and gold inks using iron gall- and carbon-based black ink (carbon
black/soot), cochineal (red ink) and gold.
KEYWORDS
p-XRF, Raman, FTIR, color, ink, diplomatic
Corresponding author: Ömer Kantoğlu,TAEA, Sarayköy Nuclear Research and Training Center, Kahramankazan 06983, Ankara, Turkey, E-mail: omer.kantoglu@taek.gov.tr
http://orcid.org/0000-0002-0403-5425
Ece Ergun, Rıdvan Kırmaz, Yakup Kalaycı, Abdullah Zararsız, TAEA, Sarayköy Nuclear Research and Training Center, Kahramankazan 06983, Ankara, Turkey,
E-mail: ece.ergun@taek.gov.tr, ridvan.kirmaz@taek.gov.tr, yakup.kalayci@taek.gov.tr, abdullah.zararsiz@taek.gov.tr
Önder Bayır,State o f Archives, Directorate o f the Ottoman Archive, Kağıthane 34400, Istanbul,Turkey, E -mail: onderbayir2@gmail.com
l.Introduction
The Ottoman Archives held in Istanbul, Turkey comprise one o f the most valuable and richest
collections o f diplomatics, manuscripts, illuminated codices and documents on parchment and
paper in the world. It contains more than 100 million o f documents on the history o f Balkans
and Mid Europe, Near and Middle East, North Africa and Caucasus concerning their customs
and traditions, national and international relationships and problems, title deed, endowment
deed, title o f privilege, ... etc. Among the treasures o f the collection, there are so many stylistic
documents. This embellishment in the manuscripts, valuable books and diplomatics are defined
as illumination and are called “tezhib” in traditional Turkish-Islamic art. The word has the
literal meaning o f “ornamenting with gold” . However, tezhib does not only use gold; through
the ages, the process is also undertaken using vegetable dyes, metal oxides, earth-based color
dyes and powdered stones with techniques that are applied are usually based on the composition
o f gold and paint (Özen 2003).
Ferman is one o f the most important documents in the fields o f diplomacy, law, charitable
donations and foundations, history and economics in the Ottoman period. It is ordinarily
imprinted with the sultan's “Tuğra” and is the sign o f sultan’s sovereignty. The document can
be gilded and contain a diversity o f colors and motifs or it may be plain and ungilded.
In the early years o f the Ottomans, the tuğra was drawn in black ink; then, during the reign
o f Mehmed II the Conqueror (1451-1481), it was delineated in gold. Under Beyazid II (1481
1512) the son o f Mehmed II, the fields o f the ellipse in the tuğra were decorated with
illumination. The prominent features o f the ornamentation were the application o f a gold wash,
and this came to be designated as the classical style o f illumination. At the end o f the 17th
century and beginning o f the 18th century, under western influence, the classical style was
Besides illumination, calligraphy (called “hat” in Turkish-Islamic art) was also o f great
importance in the ferman (Anonymous, 2003). Scripts were generally written in black but
sometimes, red ink and rarely green ink were used. Carbon based black and iron gall ink were
generally used for the black ink by calligraphers. Carbon-based black ink can be prepared by
three different techniques. The first method consists o f burning organic materials like linseed
oil, resin or tar, second is the collection o f lamp soot, and the third is burning o f animal bones
or ivory. Ottoman calligraphers mostly collected lamp or candle soot or burnt linseed oil, resin
or tar to prepare the carbon based black ink, but not burnt the bone or ivory for the sacred
concern. Burning these materials produced soot containing pure carbon and oxidized materials.
W hen properly produced, the soot could contain up to 80% carbon particles, which was mixed
with water and gum to keep the carbon in suspension. A good quality carbon ink has a blue-
black appearance. Such an ink will not discolor with age, but can easily smudge with high
humidity and is easy to remove from a document (Schopen 2004). Iron gall ink was also used
and was produced by mixing o f iron dusts with tannic acid extracted from Aleppo gall together
with a gum arabic solution. Some trace amount o f transition metals like Cu, Mn, Cd, Co, Cr
may also contain in the iron gall ink as accidental by-products o f historic mining technology.
However, iron gall ink used by the Ottomans iron gall ink is prepared in two different methods.
One is as described above, the other is the adding o f a vitriol mostly CuSO4 to iron gall ink for
turning the color o f ink solution to a brilliant black. It is called as iron gall ink-vitriol and is also
used by Persian calligraphers. Even in Persia, iron gall ink is also prepared by adding alum
(Rifat 1938; Zekrgoo 2014).
It is sometimes difficult to differentiate between aged carbon ink and iron gall ink. Although
most iron gall inks turn brown over time, color alone does not identify an aged iron gall ink
since poor quality carbon inks contain a high proportion o f tarry material, which also produces
pale. In contrast, some iron gall ink on parchment, even after centuries, can appear as a deep
black and can easily be mistaken for a carbon ink. To distinguish iron gall ink from carbon ink
or other inks; e.g., bister or sepia, a quantitative test such as micro X-Ray fluorescence
spectroscopy (p-XRF) is a useful method to reveal the presence o f iron in an ink line, and thus
determining the source o f the ink. In last two decades, conservators also use a rapid
identification test method using bathophenanthroline test papers (Yazır 1989; Roldan 2014;
Neevel 2005).
In most o f the ferman, it is said that some parts o f scripts were written in red ink, which is
a Carmine dye made from carminic acid, extracted from the body and eggs o f the female
Cochineal beetle (Gettens 1966). According to some sources, Armenian cochineal and Ararat
kermes insects are used as well (Fuller 1986). The harvested cochineal insects are killed by
immersion in hot water, steam, or baking in an oven. They are then dried and crushed.
Gypsophila, pokeweed (Phytolacca americana) is boiled; then, the crushed cochineal is added
and the boiling continues. The resultant brilliant red solution is filtered and then have been used
as red ink since antiquity (Kütükoğlu, 1994). In spite o f basic production procedures are the
same, some differences are observed in the ingredients o f the cochineal red ink over centuries
(Özen 2003; Rifat, 1938; Bell 1997; IRUG; HR Aldrich; CAMEO; Sujuta and Raja 2014;
Cardon 2010).
Since the foundation o f the Ottoman Empire (AD 1300), most o f the documents have been
contaminated by the biological deterioration agent(s), such as fungi, bacteria and insects in
addition to natural degradation. Therefore, a rapid decontamination and conservation method
is necessary to preserve the Ottoman archive collection. The successful applications o f radiation
technology on the decontamination o f fungi, bacteria and insect from foods, cereals, disposable
medical items and items o f cultural heritage encourage its usage (Woods and Pikaev 1994;
the materials o f interest in order to select the appropriate conservation technique(s),
equipment(s) and material(s). But, non-destructive analysis is mandatory for testing the
valuable archival materials. In this regard, the mobile p-XRF, FTIR and Raman systems are the
most suitable methods to fulfill the requirements since materials are not damaged or altered by
these techniques (Kriznar et al. 2012; Miliani et al. 2010). It is important to note that performing
the analysis outside the archive was not possible since the loan o f the documents is not
permitted. Therefore, portable elemental and spectroscopic systems were transported to the
archive and all analysis was carried in the archive storages. In this study, the basic information
concerning the types o f colors and inks used in diplomatics dated from the 13 th to the 20th
centuries were identified by using those o f techniques.
2.Materials and Methods
2.1. Diplomatics
Ten diplomatics from the 13th to the 20th century were selected in more than 150 examined
diplomatics. The diplomatics were written on burnished paper produced from cotton, cotton-
linen or rag. The diplomatics labeled as EV.VKF.19-17, AE.SMRD.I-11, EV.VKF.19-1, MFB-
2, MFB-950, MFB-18, MFB-935, AE.SABH.I-19701, MFB-445 and MFB-650 were chosen as
samples o f the mostly used colors in diplomatics from the foundation o f the Ottoman Empire.
Attention was paid to select at least one significant example from each century. A digital image
o f each o f the diplomatics is presented in Figs. 1 - 4.
2.2. p-XRF Analysis
The Mobile Bruker ARTAX p-XRF 800 system was employed in the determination o f the
elemental composition o f colors and inks used in the diplomatics. This system allows the
camera with sample illumination and a laser spot. The system is operated by a Peltier cooled
silicon drift detector (SDD) with 150 eV resolution and a Mo X-ray tube. During the analysis,
samples were exposed to X-Ray for 60 second under 1 mA and 50 keV voltage. ARTAX is
suitable for multi-element analysis o f Al (13) to U (92) and offers a spatial resolution down to
70 pm. The direct measurement o f light elements from Al (13) to Ar (18) can be undertaken
under helium purging; however, since their quantifications are limited, during the analysis, the
use o f helium purging was not preferred and the light elements from Al (13) to Ar (18) were
not identified. Thin ink layers on paper were very heterogeneous and did not allow reproducible
point measurements; therefore, the line scans o f 10 measurements each were acquired.
2.3. FTIR analysis
The handheld FTIR system o f A2 Technologies ExoScan with ATR accessory was used in the
color and ink analysis. Spectra were acquired with A2 MicroLab PC software for the data
acquisition; then, Thermo Omnic software was used for the data mining. Spectra were recorded
with the 4 cm-1 spectral resolution between 650 and 4000 cm-1 spectral range. During the
application, most o f the time, the color spectra was overlapped by the characteristic bands o f
cellulose, which has high intense and broad band between 900 and 1200 cm-1, and most o f the
color characteristics bands were under this broad band; thus, direct interpretation was
impossible. For this reason, the subtraction method was used in the evaluations. In this method,
the reference spectra o f known species are subtracted from acquired spectra. The final spectra
obtained by this method was searched in internal libraries to find similarities with the most
matched spectra as well as comparing them in terms o f the characteristic band assignments.
2.4. Raman Analysis
In Raman spectroscopic analysis, the handheld Bruker Bravo Raman spectrometer controlled
This system has dual laser excitation (785 nm -1064 nm -Duo LASER™-) and a large spectral
range (300 - 3200 cm-1) with a spectral resolution o f 10 cm-1. W hile the laser o f 1064 nm
eliminates the fluorescence effect as well as exciting colors with low efficiency, the laser of
785 nm excites colors, and this helps in the acquisition o f spectra. The dual laser at different
wavelengths enables for a Raman spectrum in all basic modes o f scattering to be acquired. It
minimizes fluorescence effect and enables for spatial compression o f the spectrum (Cooper et
al. 2014). On the other hand, it uses Sequential Shifted Excitation (SSE TM) a florescence
mitigation that enables to measure materials with handheld Raman system. In Raman spectral
analysis, cellulose bands also overlapped with the color spectra. M ost o f the colors were
acquired together with cellulose; therefore, the cellulose bands were not included in the
interpretation o f the Raman spectra. The subtraction method was also conducted in the Raman
spectra evaluations.
3.Results and Discussions
Since all the diplomatics under investigation had gold ornaments either in splashed or wash
form, the presence o f gold is not included in the further discussions on the evaluation o f the
elemental composition o f the diplomatics.
3.1. EV.VKF-19-17
In early years o f the Ottoman Empire, diplomatics were not illuminated. A plain font in black
ink was the general writing style used in the calligraphy o f diplomatics. In this regard, the
diplomatic o f EV.VKF-19-17 (Fig. 1) issued in 1300 by an unknown calligrapher is the earliest
and unique example o f the diplomatics in the Ottoman archives from the period o f Osman
Ghazi, the founder o f the Ottoman Empire. Therefore, the preservation and characterization of
examined by p-XRF, FTIR and Raman spectroscopy. In the p-XRF spectra, Fe, Cu and Ca were
determined with Fe and Cu being the major components o f the ink and Ca being a minor element
(Table 1). This composition was the typical o f iron gall ink containing vitriol. The FTIR and
Raman analyses were also conducted to support the elemental analysis result; however, the spot
size (around 5 mm) o f both instruments was larger than the thickness o f calligraphic letters (less
than 1 mm). In addition, the analyzed black script did not show a neat spectrum, probably
because o f a lack o f ink or the impossibility o f extracting the information from the cellulose
fiber. In fact, the ink was often so deeply impregnated into the fibers that it was very difficult
for any signal to be observed apart from those in the supporting paper. Therefore, meaningful
spectra was not acquired for ink rather than cellulose spectra. However, as noted from p-XRF
analysis, the elemental composition o f black iron gall-vitriol ink on the diplomatic and the
ingredients o f the iron gall overlapped. In addition, there was no deterioration or disintegration
on paper because o f the acid hydrolysis o f Fe and Cu content. It was assumed to be the
balancaed iron gall ink usage. All iron and copper ions were probably bound with tannic acid
forming the sufficient amount o f chelating agents. Therefore, there was no free Fe and Cu ions
to react with cellulose for acid hydrolysis (Neevel 1995; Potthast 2008).
3.2. AE.SMRD.1. 11
This diplomatic issued on July 05, 1369 for Sultan Murat I was written in black ink without a
m otif inscription. As a result o f p-XRF elemental analysis presented in Table 1, Fe, Cu and Ca
were determined and it was found that the black ink was iron gall (Table 2). In addition, the
FTIR spectral bands at 1319 and 1643 cm-1 o f the scripts were the characteristic bands o f iron
gall (Fig. 5a) (Boyatzis et al. 2016). However, in the literature, it is stated that such an ink would
discolor through the ages although if the paper surface is sized with animal products namely
egg yolk or collagen extract, it can retain a deep black color even after centuries. In the case of
surveyed by FTIR and Raman spectroscopy. As can be seen from the digital image o f this
diplomatic in Fig. 1, the discoloration o f ink from black to brown is clear. This discoloration
was probably due to the unbalanced metallo-gallate ration o f iron gall ink (Neevel 1995;
Potthast et al. 2008). In addition, influence o f the deterioration products o f organic gall
compounds on the ink corrosion may also take part o f the browning o f the iron gall ink (Krekel
1999). In this context, discoloration on the diplomatic paper surface was attributed to the iron
gall ink changing from black to brown over time. Both visual and analytical analysis results
pronoun the use o f iron gall in the diplomatic.
3.3. EV.VKF-19-1
The diplomatic issued for Sultan Murat II on Dec 10, 1440 (Fig. 2) was written in black ink.
Table 1 shows the Fe, Cu and Ca acquired from the p-XRF spectra o f black ink and that their
quantities were the same as the background paper. The Raman bands elucidated at 1360 and
1590 cm-1 due to the sp3 and sp2 hybridized forms o f carbon was an indication o f a carbon-
based black ink shown in Fig. 6a (Edwards and Chalmers 2005). It may also be bone or ivory
black ink containing PO4-3 content. But phosphorus (P) w asn’t detected by p-XRF elemental
analysis. In addition, there was no PO4-3 characteristic band at 961 cm-1 in Raman spectra.
Therefore, the black ink in the text was assumed to be carbon-based. From the FTIR and Raman
spectroscopic analysis, the round pattern elements o f blue and green colors were found to be
azurite and malachite, respectively. The elemental composition o f the blue and green colors
was matched with the spectroscopic results. In the p-XRF o f the green color, Cu was the major
component, Pb and Au were minor, and Fe were in trace amounts. Fe was sourced from paper.
But Pb in the elemental spectra o f green color was a contamination o f basic white lead used for
tinting or white color. For the blue color, Cu was major whereas Fe was minor. At the end of
the elemental and spectroscopic analyses, blue color was found to be azurite (Fig. 6b) and green
they observed a sharp Raman signal o f malachite at 1492 cm-1, which is absent in Fig 6c (Bell
et al. 1997). However, in their analysis 514 nm laser was used, whereas in ours was 785 nm. It
was supposed that the reason o f the absence o f signal at 1492 cm-1 was the differences in laser
energy.
3.4. MFB-2
In the p-XRF analysis o f the diplomatics issued on Feb 21, 1575 for Sultan Selim II (Fig. 2),
Pb and Fe for red color were identified with Pb being the major amount, and Fe being present
in trace amounts. Regarding the p-XRF results, the red color was presumed to be minium
(Pb3O4). On the other hand, none o f elements were traced for the blue color, but this was
probably due to the limitation o f the light element analysis in p-XRF system. The red and blue
colors were characterized as minium (Fig. 6d) and lapis lazuli (Fig. 5e and 6e) by their FTIR
and Raman spectra, respectively. The bands at 454 and 531 cm-1 o f FTIR and at 311, 387, 477
and 544 cm-1 o f Raman for minium and at 696 and 1010 cm-1 (arising from stretching modes in
tetrahedral Si-O units) o f FTIR and at 410, 548 (attributed the S3- ion), 822 and 1096 cm-1 of
Raman for lapis lazuli confirmed that those colors were minium and lapis lazuli, respectively.
The black ink in the diplomatic was also investigated; however, except for a trace amount o f
Pb with background elements, none o f the other elements were observed. In the Raman analysis
o f the black ink, the bands at 1360 and 1590 cm-1 o f carbon-based black ink were found. All
the colors and inks surveyed on the diplomatic o f MFB-2 are summarized in Table 2.
3.5. MFB-950
Diplomatic MFB-950 (Fig. 3) was issued on July 13, 1608 for Sultan Ahmed I. In the p-XRF analysis, a trace amount o f Pb, Au, Zn, Fe, Ca and K elements were detected related to blue color. However, these elements were not sufficient to definitively assign them to being the source o f a blue color. These trace amounts o f elements were observed from the paper background and the contamination o f red color. After the FTIR analysis was conducted, the
blue color was found to be lapis lazuli by the bands at 696 and 1010 cm-1 o f FTIR. It was correlated by Raman bands at 410, 548, 822 and 1096 cm-1. Whereas chemical composition of natural lapis lazuli is (Na,Ca)s(AlSiO4)6(SO4,S,Cl)2, synthetic ultramarine blue (French ultramarine) is N a6-10Al6Si6O24S2-4. In natural mineral lapis lazuli, the proportion o f aluminum (Al), silicon (Si), and oxygen (O) being fixed in an aluminasilicate, the other elements presents as cation and anions are variable. Depending on the production process and the nature and color properties are varied (Roy 1993). Both presence o f a broad band in FTIR spectra between 3000 3700 cm-1 and absence o f the band at 373 cm-1 in Raman spectra indicate synthetic form o f lapis lazuli (ultramarine blue). However broad band is absent in natural lapis lazuli. The blue color o f MFB-950 identified as lapis lazuli was attributed to natural lapis lazuli by the absence o f broad band o f 3000-3700 cm-1 in FTIR spectra and o f band 373 cm-1 in Raman spectra. After this analysis, the elemental composition o f the red color in the scroll was determined and found to be Hg, Cu, Fe and Ca. Apart from Hg, all elements were o f minor content; thus, the red color was assumed to be vermilion (HgS). The Raman spectra o f the red color on the scrolls were well fitted to the vermilion reference spectra (Fig. 6f), as well as the appearance of characteristics bands for this color at 342 cm-1 for Raman. The band at 1054 cm-1 in Fig 6f, was the only related band with the basic lead carbonate used for tinting agent. Rest o f the unassigned bands may be related to the other contaminants in color and paper based ingredients. Therefore, unassigned bands in Figs 5-7 must be kept out from the color considerations. The black color on the diplomatic was also investigated with Pb, Ag, Br, Cu and Fe being the elemental components. In addition, it was found that the black color in the tuğra was ornamented with red and blue flower motifs. The red and blue colors in the motifs were forecasted to be minium and azurite, respectively. In the Raman analysis o f the black/gray area on the tuğra, combined spectral bands o f minium and azurite, which were the source o f Pb and Cu in elemental analysis were observed at the bands 311, 387, 477 and 544 cm-1 for minium and at the band 410 cm-1 for azurite. There was a main grayish color that remained from the admixture o f ink and AgBr. It is thought that AgBr was added as a glossing (shining) agent. In some Persian manuscripts silver was used as glossing agent whether it was leaf or powdered form (Zekrgoo 2017). Silver bromide is a Raman inactive compound. Therefore, there was no other signal contribution to the spectra that was obtained. In the characterization studies o f ink by p-XRF, Fe, Cu and Ca were determined as the elemental composition o f the black ink. These results refer directly to a typical indicator o f iron gall. The analysis results o f the diplomatic concerning the assigned colors and ink are given in Table 2.
3.6. MFB-18
Diplomatic MFB-18 (Fig. 3) was prepared under the command o f Sultan M ustapha II on Aug 26, 1700 and several colors including blue, green and red were identified in this document. Except the trace amount o f Pb in the red color, the remainder seemed to be organic in the p- XRF analysis. However, it might contain some light elements, which could be outside o f the detection range o f the mobile p-XRF system. Cu (major), Au (trace) were identified in the green color. Gold was assumed to be contamination from the gold in the tuğra. In the blue color, a rarely observed elemental composition among the examined diplomatics in the Ottoman Archive was detected with Co, As and Fe being the major elements and Pb and Bi being the minor elements. This p-XRF pattern refers to smalt, which first appeared on a wall painting (ca. 1000-1200 C.E.) in Khara Khoto, Central Asia, and in the Kariye Mosque (1325-1453 C.E.) (Gettens and Stout 1958; Muhlethaler and Thissen 1969; W allert et al. 1995). In the production o f smalt, cobalt ore is processed with quartz. Therefore, in addition to Co as well as K and Si, it contains As (mostly higher than Co), Ni, Bi, Fe Mg and Al that indicates the origin o f Co ore or silica source. Therefore, the detection o f As and Bi in blue color w asn’t a sign o f other color (Robinet and Spring 2011). The trace o f white color was also detected, but it was not used directly but as tinting material with other colors. The major component o f the white color was Pb. This result indicates that the white color could be basic lead carbonate (PbCO3.Pb(OH)2) (Fig. 7a). The FTIR and Raman spectroscopic analyses were conducted to identify the chemical structure o f those o f the predicted color structures. The intense bands o f 462 cm-1 were detected for the Raman spectra o f blue color which was the characteristic band o f the smalt (Fig. 7b). Those bands were compared with the reference library spectra and matched with a high quality yield. In the FTIR and Raman spectra o f the green color, the FTIR spectral bands at 1047, 1096, 1389 and 1508 cm-1 revealed carbonate whereas the Raman spectra bands at 348, 430, 508 and 532 cm-1 revealed a basic copper carbonate o f malachite. The bands at 1377 and 1462 cm-1 of the FTIR spectra belonged to cochineal, which was the origin o f the red color (Fig. 5b). Cochineal may contain several ingredients depending o f the desired tones o f red color and change its characteristic FTIR spectra due to the dominant character o f other ingredients. There are several published, released in web pages or library recorded spectra for cochineal. However, most o f them demonstrate different FTIR bands due to its ingredient variations (Özen 2003; Rifat 1953; Kütükoğlu 1994; Bell et al. 1997; IRUG; HR Aldrich; CAMEO). But FTIR spectra collected from MFB-18 and MFB-935 was well fitted with the reference library spectra o f “HR Aldrich FTIR Collection Edition I-II” released by Aldrich Chemical Company. In the visual
examination o f the diplomatic, a trace o f black ink was also observed, but the p-XRF analysis o f this ink revealed that there were no different elements (Fe and Zn) than in the paper background. This result was attributed to the presence o f carbon-based black ink. Regarding the color and ink analysis used in the illuminations and scripts, the elemental composition is presented in Table 1.
3.7. MFB-935
In diplomatic MFB-935 (Fig. 3) dated June 10, 1741 issued for Sultan Mahmud I, two different
red colors were observed visually, and special attention was paid to these points using the p-
XRF system. The red color on the rose illumination contains Zn, Ca, Mn, Fe and K, but none
o f them was a major element that could be assigned to a color. It appeared to be organic or
containing some light elements, but it could not be detected through the p-XRF system used.
In the second red color point above the shafts on the red claret, Fe, Ca, Zn and K were detected.
In this case, Fe was the major element, which pointed to the source being red ochre. The analysis
o f the green color was also conducted in two different points, one on the tuğra and the other on
the leaves in the diplomatic. The green color in tuğra contained Cu (major), Fe, Ca and Zn
whereas the green color on leaves contained Ca (major), Pb, K, Fe and Zn. Malachite and green
earth was considered to be the colors, respectively. But, it needs to be identified by FTIR and
Raman. In addition, Cu (major), Zn, Fe, Mn, Pb and K (minor) were found on the blue
background o f tuğra. W hen the elements o f Ca, Fe, Cu, Zn and K in paper background were
excluded, the thicker script in the frame and thinner script on the diplomatic written in black
was considered to be organic. It was presumed that the ink used in the writing o f script was a
carbon-based black ink. Then the mobile FTIR and Raman spectroscopic techniques were
utilized to determine the exact chemical composition o f the colors. Bands 3441, 561 and 479
cm-1 o f the FTIR spectra and bands 401, 487 and 600 cm-1 o f the Raman spectra acquired from
red color point above shafts on a background red claret revealed red ochre (Fig. 7c), which was
color to be cochineal by the characteristic bands at 1462 and 1377 cm-1. The bands at 1047,
1096, 1389 and 1508 cm-1 for FTIR and 348, 430, 508 and 532 cm-1 for the Raman spectra were
collected from green colors in the tuğra. Bands at 980, 1610, 3580 and 3610 cm-1 for the FTIR
spectra and at 582 and 609 cm-1 for the Raman spectra o f the green color on the leaves were
also obtained. After the interpretation and the comparison with the reference spectra in the
spectral library, both green colors were found to be malachite and green earth (Fig. 7d) applied
to the tuğra and leaves, respectively. The eye-catching blue color on the tuğra was found to be
azurite (Table 2). This color was distinguished from the FTIR bands at 456, 837, 952, 1415,
1465 and 3425 cm-1 and the Raman band at 410 cm-1. In the diplomatic, in the |i-XRF or FTIR
analysis, the excess content o f the Zn element in the colors was attributed to zinc oxide having
been used to tint the color.
3.8. AE.SABH.1.19701
This diplomatic was issued on Aug 24, 1784 for Sultan Abdulhamid I (Fig. 4). The m otif of
ornamentation was called Tree o f Life and the dominant color in the document was red. But,
the color was darkened or lightened, according to the desired color tone in overall the
ornamentation o f Tree o f Life by tinting with white color. In the elemental analysis o f color on
the document, rich content o f Zn was observed besides the major element o f colorant. Then,
the use o f white zinc oxide was determined in the document by FTIR analysis. The presence of
zinc oxide in the tinted colors was proved by the characteristic FTIR bands o f 679, 1028, 1382
and 1467 cm-1 shown at Fig. 5c (HR Industrial). Thus, it was presumed that the color contrast
was dependent on the Zn content. In visual examination, it was suspected for the use o f two
different red colors. They were in light and dark red colors at the Life o f Tree. One was on the
tuğra looked like pink. The other was used in a sequential order with blue and orange on the
border at both right and left sides o f the Tree o f Life. In both red color analysis points, the major
colors, vibration bands at 454 and 531 cm-1 and scattering bands at 477 and 544 cm-1 were
obtained. Therefore, both red colors were accepted to be lead (IV) oxides (Pb3O4) which were
also complied with the reference FTIR and Raman spectra. In addition to red color, the
application o f several color splashes such as orange and blue were observed in the
ornamentation o f tezhib on both sides o f the Tree o f Life. For the blue color, Fe was major,
whereas there were trace amounts o f Cu and Pb in the elemental composition spectrum o f this
color. The distinct FTIR peak at 2088 cm-1 o f the cyanide group revealed that the blue color
was Prussian blue (iron ferrocyanide) (Fig. 5d). For the orange color, Pb was a major and Zn
was a trace component. The orange color was characterized by the Raman shift values o f 311,
387, 477 and 544 cm-1. In comparison o f the g-XRF results with the FTIR and Raman results,
these three colors were found to be minium, Prussian blue and lead (IV) oxide for the red, blue
and orange colors, respectively. As is known, color o f minium varies from red to orange
depending o f the production process. When the black ink was subjected to the g-XRF analysis,
an organic material spectra was observed and was attributed to a carbon-based black ink. A
summary o f the color and ink contents o f the diplomatic is presented in Table 1.
3.9. MFB-445
This diplomatic was issued on Jan 19, 1787 for Sultan Abdulhamid I (Fig. 4). In the elemental
analysis o f the red colors, Pb and Ca were found as major and Au in trace quantity. Cu (major),
Au, Pb and Mn (trace) were detected in the analysis carried out on the green color (Table 1). In
addition, two blue colors were observed in the diplomatic as a light blue on the floral bouquet
and a dark blue on the ground. The major components o f the light blue color were found to be
Pb and Fe whereas those o f the dark blue color components were Cu. It was presumed that
Prussian blue and azurite were used for the light and dark blue color on Tree o f Life
illumination. Some pink color was also observed on the diplomatic, but it was identical with
tinted with white basic lead carbonate. The black ink was also examined by |i-XRF, but there
was no indication o f inorganic ink, and it was assumed that it was carbon-based black ink.
To determine the chemical composition o f the colors o f interest in this diplomatic, analyses
using FTIR and Raman was performed. The findings were as follows; 454 and 531 cm-1 of
FTIR and 311, 387, 477 and 544 cm-1 o f Raman bands for the red color on bouquet; 1261, 1633
and 2088 cm-1 o f FTIR and 336 and 397 cm-1 o f Raman bands for the light blue color on
bouquet; 451, 494, 769, 837, 852, 1415, a doublet o f 1464-1494 and 3422 cm-1 o f FTIR and
410 cm-1 o f Raman bands for the dark blue color on ground o f tuğra and 429, 523, 571, 820,
871, 1047, 1389, 1508, 3310 and 3404 cm-1 o f FTIR and 348, 430, 508 and 532 cm-1 o f Raman
bands for the green color on the ground o f tuğra. After compiling the ^-XRF, FTIR and Raman
results, the red, light and dark blue, and green colors were characterized as minium, Prussian
blue (Fig. 7e), azurite and malachite, respectively. In the dark blue color on the ground of tuğra,
a trace o f red ochre and smalt was also observed by ^-XRF, FTIR and Raman spectroscopy;
however, the dominant color was azurite. The presence of the carbonate ion precursor band at
1410 cm-1 o f the FTIR spectra demonstrated that basic lead carbonate was used as tinting agent
in the illuminations o f MFB-445. The color palette o f diplomatic MFB-445 is presented in
Table 2.
3.10. MFB-650
Diplomatic MFB-650 (Fig. 4) was written on May 12, 1803 for Sultan Selim III. In the
elemental analysis of the red colors, Fe was found in major and Cu, Pb, K and Ca were in minor
quantities. In the dark red on the ground o f the tuğra, a mixture o f Fe, Cu and Pb containing
color was used. In both red illuminations o f the diplomatic, minor content o f Cu, Pb, Ca and K
was observed. Cu source was azurite and malachite contaminations from the nearby
tinting agent and appeared in p-XRF spectra as Pb. Both Ca and K were from the paper
background. Blue color was observed on the diplomatic as dark ground on the tuğra and blue
on the crest. The major component o f the blue color was found to be Cu whereas the minor
components were Au, Fe, Pb, Ca and K (Table 1). It was presumed that azurite was used for
blue color, and white basic lead carbonate was used as a tinting agent as in most o f the
diplomatic. Black ink was also examined by p-XRF, but there was no indication o f an inorganic
ink; thus, it was assumed to be a carbon-based black ink.
The chemical composition o f the colors on the diplomatic was investigated on the dark red
tuğra by FTIR and Raman spectroscopies. The bands at 454, 531, 1261, 1633 and 2088 cm-1 of
FTIR and 311, 336, 387, 397, 477 and 544 cm-1 o f Raman were detected at the dark red color.
According to the results o f elemental and spectroscopic analysis, dark red color was thought to
be obtained from a mixture o f colors. The bands at 454 and 531 cm-1 o f FTIR and 311, 387,
477 and 544 cm-1 o f Raman were belong to the minium, and the bands at 1261, 1633 and 2088
cm-1 o f FTIR and 336 and 397 cm-1 o f Raman were belong to the Prussian blue. Regarding this
result, it was considered that Prussian blue was added to minium to darken the red color o f the
tuğra. Red ochre was characterized on the rose leaf by the bands o f 3441, 561 and 479 cm-1 of
FTIR and 401, 487 and 600 cm-1 o f Raman. The blue color on the crest was discriminated by
the characteristic bands o f azurite at 456, 837, 952, 1415 and 1465 cm-1 o f FTIR and at 410 cm-
1 o f Raman. In MFB-650, an interesting mixture o f the green color had been prepared to
illuminate the green motifs. In FTIR analysis, strong bands at 1019 cm-1 (green earth) and 1406
cm-1 (basic lead carbonate) and weak bands at 1096 and 1389 cm-1 (malachite) were interpreted.
At the same analysis point, Strong Raman signals at 582, 609 cm-1 (green earth) and 1054 cm-
1 (basic lead carbonate), very weak Raman signal at 430 cm-1 (malachite) were obtained as well.
A high proportion o f green earth had been mixed with a trace amount o f malachite and a large
that malachite was used as the contrast and shadow in the green earth color. As was common
practice at the time, basic lead carbonate was preferred as a tinting agent. The yellow on the
frame lines was found to be massicot using the p-XRF and Raman data (Fig. 7f). The orange
leaf on the diplomatic was characterized by the presence o f Pb (major), Cu and Ca by the p-
XRF system. This orange color was also characterized with distinct bands at 454 and 531 cm-1
o f FTIR and 311, 387, 477 and 544 cm-1 o f Raman and found to be minium. All the colors used
in the illumination were presented in Table 2. It was observed that two types o f ink were used
in the diplomatic. Some part o f illumination was ornamented by black lines colored with
carbon-based black ink. However, for the text, iron gall was used for the black ink.
3.11 Frequency of Color Utilization in the Ottoman Diplomatics
In the context o f the reign periods o f the Ottoman Empire, although several studies have been
undertaken on the color and ink used in documents through various periods, until the present
day, there has not been a study covering documents written since the foundation o f Ottoman
Empire (Tanevska et al. 2014; Bruni et al. 2001; Duran et al. 2009; Burgio et al. 2008; Kural
Özgörüş et al. 2017; Derman 2011). For this reason, the current work is the first investigation
o f diplomatics from all centuries since the foundation o f the Ottoman Empire in the 13 th century.
In this article, the results o f ten diplomatics with at least one document from each century were
summarized to demonstrate the color usage. Although the color analysis results o f the remaining
diplomatics and manuscripts (more than 150) were not included in the results o f the diplomatics
in Fig. 1 - 4, they are considered to contribute to the demonstration o f the rich palette o f valuable
and costly colors used in the Ottoman diplomatics between the 13 th and the 20th century.
Minium, lapis lazuli and malachite were the common colors that were used over the centuries.
In some specific periods (from the 18th to the 19th century), orpiment and cochineal were often
used. Iron gall and iron gall-vitriol inks were used frequently in the first centuries o f the
results revealed that cochineal red ink was used after seventeenth century and it was even used
as a red color in the drawing o f tuğra in a certain period. Carbon-based black ink was also
commonly used in the Ottoman diplomatics, and in some o f the applications o f carbon ink, after
writing, very tiny flakes o f gold or titanium (imported from Vienna) were perfused to allow
quickly drying the ink and brighten the script (Derman 2012).
The main text in the diplomatics was written in black ink (iron gall and carbon-based black),
but in some o f the diplomatics, red ink was used to emphasize specific elements o f the text and
was found to be cochineal. The red ocher for red ink was also identified as an uncommon
practice within the 150 diplomatics examined except a couple o f diplomatics. Prussian blue was
also used for blue ink. But it was also an uncommon practice as in red ink and it was not detected
except 2 or 3 diplomatics. In addition, in some o f the diplomatics investigated within 150
diplomatics, green ink was also identified as cennino (a mixture o f lapis lazuli and orpiment)
and vergaut (a mixture o f indigo and orpiment). In some o f the diplomatics, these mixtures were
also used as green ink as well as color in the text scripts.
4.Conclusion
In this study, the use o f colors and inks in the Ottoman diplomatics was investigated. Ten
representative documents were selected from more than 150 diplomatics from the foundation
o f the Ottoman Empire to the 20th century. In these ten diplomatics, minium, vermilion, red
ochre, cochineal, lapis lazuli (ultramarine blue), azurite (blue verditer), Prussian blue, smalt,
malachite, green earth, massicot, yellow lead, basic lead carbonate and zinc oxide were used
for colorizing the diplomatic’s motifs. However, in addition to those o f colors investigated at
the ten diplomatics, several colors such as cerulean blue, cobalt blue, indigo, verdigris, emerald
green, Scheele’s green, chromium (III) oxide, orpiment, chrome yellow, yellow ochre, limonite,
were identified in all investigated diplomatics (in more than 150 diplomatics) as well. In the
scripts, the use o f iron gall, carbon-based black and cochineal inks was observed. Besides
cochineal, calligraphers also occasionally used vermilion as red ink. Minium, vermilion, lapis
lazuli, malachite and basic lead carbonate colors were used frequently through all the eight
centuries. In a period o f time, during the 18th and the 19th centuries, a mixture o f orpiment and
lapis lazuli /indigo was often used as an alternative to verdigris.
Acknowledgement
The authors wish to express their gratitude to Turkish Atomic Energy Authority for supporting this work through TAEK [A4.H5.P10] project and also to General Directorate o f State Archives to allow us the spectroscopic analysis on the original diplomatics.
References
Adamo, M., Magaudda, G., Tata. A.: Radiation Technology fo r Cultural Heritage Restoration. Restaurator 25 (2004):159-170.
Anonymous : Ottoman Fermans, 1-20. Ankara, Turkey: General Directorate o f the State Archives2003.
Arias, T.E., Montes, A.L., Bueno, A.G., Benito, A.D., Garcia., R.B.: A Study About Colourants
in the Arabic Manuscripts Collection o f the Sacromonte Abbey, Granada, Spain.
Restaurator 28 (2008):76-106.
Bell, I.M., Clark, R.J.H., Gibbs, P.J.: Raman Spectroscopic Library o f Natural and Synthetic
Pigments (pre-1850 AD). Spectrochimica Acta Part A 53 (1997):2159-2179.
Boyatzis, C.S., Velivasaki, G., Malea. E.: A Study o f Deterioration o f A ged Parchment M arked
with Laboratory Iron Gall Inks using FTIR-ATR andM icro Hot Table. Heritage Science
4(13) (2016):1-17.
Bruni, S., Cariati, F., Casadio, F., Guglielmi. V.: Micro-Raman Identification o f the Pallete o f
a Precious XVI century Illuminated Persian Codex. Journal o f Cultural Heritage 4
(2001):291-296.
Burgio, L., Clark, R.J.H., Muralha, V.S.F., Stanley. T.: Pigment Analysis by Raman
Microscopy o f the N onfigurative Illumination in 16th-18th-century Islamic Manuscripts. Journal o f Raman Spectroscopy 39 (2008):1482-1493.
Cardon, D.: Natural Dyes, Our Global Heritage o f Colors. Textile Society o f America Symposium Proceedings. (2010): 12.
Cooper, J.B., Marshall, S., Jones, R., Abdelkader, M., Wise, K.L.: Spatially compressed dual
wavelength excitation Raman spectrometer. Applied Optics 53 (2014):3333-3340.
Derman, M.U.: Surname ’nin Resimlendirmesine Dair Bir Belge/A Document Concerning the
Illustration o f Surname, Ed. Yasa Yaman, Z., Bağcı, S., Tradiation, Identity, Synthesis: Cultural Crossing and Art, 95-103. Ankara: Hacettepe Üniversitesi Yayınları 2011.
Derman. M.U.: Mürekkep. TDV İslam Ansiklopedisi, cilt 32, 47. Istanbul: Türkiye Diyanet Vakfı 2012.
Duran, A., Perez-Rodriguea, J.L., Espejo, T., Franquelo, M.L., Castaing, J., Walter. P.:
Characterization o f Illuminated manuscripts by laboratory-made Portable XRD and micro-XRD systems. Analytical Bioanalytical Chemistry 395 (2009):1997-2004.
Edwards, H.G.M., Chalmers, J.M.: Raman Spectroscopy in Archaeology and A rt History, Cambridge, UK: Royal Chemical Society 2005.
Fuller, R.L.: Artists Pigments, A handbook o f their history and characteristics, Vol. 1, 255-283. National Gallery o f Art, Washington DC, London: Archetype Publications 1986.
http://www.irug.org/search-spectral-database
HR Aldrich FTIR Collection Edition I-II database, Sigma-Aldrich Comp.
HR Industrial Coatings Database, Sigma-Aldrich Comp.
http://cameo.mfa.org/wiki/Cochineal
Gettens, R.J., Stout. G.L.: A Monument o f Byzantine Wall Painting: The M ethod o f
Construction. Studies in Conservation 3 (1958):107-18.
Gettens, R.J., Stout. G.L.: Painting Materials, A Short Encyclopedia, New York, USA: Dover Publications, Inc 1966.
Kantoğlu, Ö., Ergun, E., Özmen, D., Doğan Halkman, H.B.: A Biological Survey on the
Ottoman Archive Papers and Determination o f D1 0 Value. Radiation Physics and Chemistry 144 (2018):204-210.
Krekel, C.: Chemistry o f Historical Iron Gall Inks. International Journal o f Forensic Document Examiners 5 (1999):54-58.
Kriznar, A., Munoz, M.V., Respaldiza, M.A., Vega., M.: Materials Applied in Bernardo
M artorell’s Painting Analysed by Portable XRF. ArcheoSciences 36 (2012):37-45.
Kural Özgörüş, N., Ünlü, C.H., Grupce, O., Bakan, F., Sezen, M.: Analysis o f Deterioration
Phenomena in a Koran by Nineteenth Century Ottoman Calligrapher Mehmet Şevki.
Restaurator 38 (4) (2017): 331-354.
Kütükoğlu. M.S.: Osmanlı Belgelerinin Dili, İstanbul, Turkey: Kubbealtı Neşriyatı 1994.
Miliani, C., Rosi, F., Brunetti, B.G., Sgamellotti. A.: In Situ Noninvasive Study o f Artworks:
The MOLAB Multitechnique Approach. Account Chemistry Research 43 (6) (2010):
Muhlethaler, B., Thissen. J.: Smalt. Studies in Conservation 14 (1969):47-61.
Neevel, J.: Phytate: A Potential Conservation Agentfor The Treatment o f Ink Corrosion Caused
by Iron Gall Inks. Restaurator 16 (1995):143.
Neevel, J, Reissland, B.: Bathophenanthroline Indicator Paper: Development a New Test fo r
Iron Ions. Papier Restaurierung 6 (1) (2005):28-36.
Özen., M.E.: Türk Tezhip Sanatı / Turkish A rt o f Illumination, Istanbul, Turkey: Gözen Yayınları 2003.
Potthast, A., Henniges, U., Banik, G.: Iron Gall Ink-Induced Corrosion o f Cellulose: Ageing,
Degradation and Stabilization. Part 1: M odel Paper Studies. Cellulose 15 (2008):849-
859.
Rifat. K.M.: Gülzar-ı Savab, 84-86. Istanbul, Turkey: Güzel Sanatlar Akademisi Neşriyatı 1938.
Robinet, l., Spring, M., Pages-Camagna, S., Vantelon, D., Trcera, N.: Investigation o f the
Discoloration o f Smalt Pigment in Historic paintings by Micro-X-ray Absorption Spectroscopy at the Co K-edge. Analytical Chemistry 83 (2011):5145-5152.
Roldan, M.L., Centeno, S.A., Rizzo, A.: An improved methodology fo r characterization and
identification o f sepia in work o f art by normal Raman and SERS, complemented by FTIR, Py-GC/MS, andXRF. Journal o f Raman Spectroscopy 45 (2014): 1160-1171.
Roy, A.: Artists Pigments, A handbook o f their history and characteristics, Vol. 2, 37-61. National Gallery o f Art, Washington DC, London: Archetype Publications 1993.
Schopen, A.: Tinten und Tuschen des Arabisch-Islamischen Mittelalters, 198-205. Göttingen, Germany:Vandenhoeck & Ruprecht 2004.
Sujata, S., Raja, A. S. M.: Natural Dyes: Sources, Chemistry, Application and Sustainability
Issues. Muthu, S. S. (ed.), Roadmap to Sustainable Textiles and Clothing, Textile Science and Clothing Technology 37-80. Singapore: Springer Science+Business Media
2014.
Tanevska, V., Nastova, I., Sukarova, B.M., Grupce, O., Özçatal, M., Kavcic, M., Jakovlevska- Spirovska. Z.: Spectroscopic Analysis o f Pigments and Inks in Manuscripts: II. Islamic
illuminated manuscripts (16th-18th century). Vibrational Spectroscopy 73 (2014):127-
Wallert, A., Hermens, E., Peek. M.: Historical Painting Techniques, M aterials and Studio
Practice, Lawrance, Kansas, USA:Allen Press Inc 1995.
Woods, R.J., Pikaev. A.: Applied Radiation Chemistry, New York, USA: A Wiley Interscience Publications, John W iley & Sons, Inc 1994.
Yazır. M.B.: Kalem Güzeli, II, Istanbul, Turkey,183-184 1989.
Zekrgoo, S: Methods o f Creating, Testing and Identifying Traditional Black Persian Inks. Restaurator-International Journal for the Preservation of Library and Archival Material 35 (29 (2014):133-158.
Zekrgoo, S., Nel, P., Sloggett, R.: Peacock Ink: Investigation into the Constituents o f the most
p rized ink o f Persia. Restaurator-International Journal for the Preservation of Library
Figure Captions
Figure 1. Digital images o f EV.VKF-19-17 (A.D. 1300) and AE.SMRD.1.11 (A.D.1369) the Ottoman diplomatics.
Figure 2. Digital images o f EV.VKF-19-1 (A.D.1440) and MFB-2 (A.D.1575) the Ottoman diplomatics.
Figure 3. Digital images o f MFB-950 (A.D.1608), MFB-18 (A.D.1700) and MFB-935 (A.D.1741) the Ottoman diplomatics.
Figure 4. Digital images o f AE.SABH.1.19701 (A.D.1784), MFB-445 (A.D.1787) and MFB- 650 (A.D.1803) the Ottoman diplomatics.
Figure 5. FTIR spectra o f iron gall ink (a), cochineal ink (b), zinc oxide (c), Prussian blue (d), lapis lazuli (e) colors acquired from diplomatics.
Figure 6. Raman spectra o f carbon based black ink (a), azurite (b), malachite (c), minium (d), lapis lazuli (e), vermilion (f) colors as acquired from diplomatics.
Figure 7. Raman spectra o f basic lead carbonate (a), smalt (b), red ochre (c), green earth (d), Prussian blue (e), massicot (f) colors acquired from diplomatics.
E V . V K F - 1 9 - 1 7
A E . S M R D . 1 . 1 1
Figure 1. Digital images o f EV.VKF-19-17 (A D . 1300) and AE.SMRD.1.11 (A.D.1369) the Ottoman diplomatics.
Figure 2. Digital images o f EV.VKF-19-1 (A.D.1440) and MFB-2 (A.D.1575) the Ottoman diplomatics.
M F B -9 5 0
M F B -1 8
M F B -9 3 5
Figure 3. Digital images o f MFB-950 (A.D.1608), MFB-18 (A.D.1700) and MFB-935 (A.D.1741) the Ottoman diplomatics.
Figure 4. Digital images o f AE.SABH.1.19701 (A.D.1784), MFB-445 (A.D.1787) and MFB- 650 (A.D.1803) the Ottoman diplomatics.
Figure 5. FTIR spectra o f iron gall ink (a), cochineal ink (b), zinc oxide (c), Prussian blue (d), lapis lazuli (e) colors acquired from diplomatics.
Figure 6. Raman spectra o f carbon based black ink (a), azurite (b), malachite (c), minium (d), lapis lazuli (e), vermilion (f) colors as acquired from diplomatics.
Figure 7. Raman spectra o f basic lead carbonate (a), smalt (b), red ochre (c), green earth (d), Prussian blue (e), massicot (f) colors acquired from diplomatics.
Table Captions
Table 1. Elemental composition o f colors used in representative the Ottoman diplomatics determined by p-XRF.
Table 2. Colors and inks used in the representative the Ottoman diplomatics determined by p- XRF, FTIR, Raman spectroscopies.
Table 1.
Elemental composition o f colors used in representative the Ottoman diplomatics determined by p-XRF.Red Green Blue Yellow Orange Brown Violet Black White Background
EV.VKF-19-17 Fe, Ca, Cu Fe, Zn
AE.SM RD.1. 11 Fe, Cu, Ca Fe, Cu, Zn
EV.VKF-19-1 Cu, Pb, Au, Fe, Cu Pb, Fe, Cu Pb Fe, Cu, Zn
Fe
M FB-2 Pb, Fe Org C black, Pb Fe, Cu, Ca
MFB-950 Cu, Hg, Fe, Pb, Au, Fe, Cu, Ca (i) Au, Fe, Ca,
Ca, Pb Fe, Ca, K Pb, Ag, Br (p) K
MFB-18 Pb, Org Cu, Au Co, As, Fe,
Pb, Bi
C black, Fe, Zn Pb Fe, Zn
MFB-935 Zn, Ca, Mn, Fe, K Cu, Zn, K, Pb, Fe Cu, Zn, Au, Fe, Mn, Pb, K
Zn, Ca, Fe, Org, Cu, Mn, K
Zn Ca, Fe, Cu,
Zn, K
AE.SABH.1. 19701 Zn, Fe, Pb, Fe, Pb, Cu Zn, Pb Pb Pb, Fe, Zn Fe, Zn
Org
MFB-445 Pb, Au, Ca Cu, Ca, Mn, Pb, Fe, Ca, Pb, Ca, Zn, Fe, K, Pb Zn, Ca, Au
Fe, Ca Fe, Zn, Au, Pb Mn, Cu, Co Ca, Au Cu
MFB-650 Cu, Fe, Ca,
K, Pb
Cu, Fe, Ca, K, Cu, Fe, Au, Pb, Ca, K
Pb, Cu, Fe, Pb, Cu, Ca Mn, K, Ca
Fe, Mn, Ca, K Pb Fe, Ca, K
Org: organic; p: pigment; i: ink; bold: major
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