Spectrochimica Acta Part B 62 (2007) 669 – 676

www.elsevier.com/locate/sab

Non-destructive analysis for the investigation of decomposition phenomena

of historical manuscripts and prints ☆
Werner Faubel b , Susanne Staub a , Rolf Simon a,⁎, Stefan Heissler a ,
Andrea Pataki c , Gerhard Banik c
a
Institute for Synchrotron Radiation, Forschungszentrum Karlsruhe, Postfach 3640, 76021 Karlsruhe, Germany
b
Institute for Technical Chemistry, Water-and Geotechnology Division, Forschungszentrum Karlsruhe, Postfach 3640, 76021 Karlsruhe, Germany
c
State Academy of Art and Design Stuttgart, Department of Book and Paper Conservation , Höhenstr. 16, 70736 Fellbach, Germany
Received 1 December 2005; accepted 17 March 2007
Available online 31 March 2007

Abstract

As a contribution to the increasing efforts to preserve cultural heritage, historical books as well as illuminated manuscripts endangered by
corrosive writing and printing materials or destructive coloring matters, non-destructive analytical methods are highly desirable enabling an in-situ
examination of the surface status of an object. The development and application of a novel combination of non-destructive analytic methods based
on (a) synchrotron radiation induced micro-X-ray fluorescence (SR-μXRF) and (b) Fourier transform infrared (FTIR) microscope allows to
investigate the state as well as the effectiveness of conservation procedures for historical manuscripts. Examples of measurements include (1) an
iron gall ink manuscript of a historical memo on legal land description of the year 1769, (2) an original hand colored herbal of the years 1536/38
from the Senckenbergische Bibliothek, Frankfurt, and (3) the incunabula Johannes von Saaz: “Der Ackermann aus Boehmen” fated from 1463 and
printed by Albrecht Pfister, Bamberg, owned by the Herzog August Bibliothek, Wolfenbuettel.
© 2007 Elsevier B.V. All rights reserved.

Keywords: SR-μXRF; Synchrotron radiation induced micro-X-ray fluorescence; Application in arts; FTIR microscope; Iron gall ink manuscripts; Hand colored
herbals; Incunabula

1. Introduction acceptable and it can even subsequently lead to further damage. In

A major problem in preservation of cultural heritage is the
damage to manuscripts, paper, parchment, books, and other
valuable documents of earlier centuries. Damage is caused by the
effect of aggressive atmospheres, by humidity and temperature, by
alterations of paper constituents, and by added materials such as
ink and later hand coloring with pigments or dyes. In order to
assess damage to such documents, it has been necessary to take at
least micro-samples of support to allow analysis. However, the
damage to precious documents caused by sampling is hardly
☆
This paper was presented at the “18th International Congress on X-ray Optics
and Microanalysis” (ICXOM-18) held in Frascati, Rome (Italy) 25-30 September
2005, and is published in the Special Issue of Spectrochimica Acta Part B dedicated
to that Conference.
⁎ Corresponding author.
E-mail address: Rolf.Simon@iss.fzk.de (R. Simon).
0584-8547/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.sab.2007.03.029
many cases, the size of a micro-sample is not sufficient to carry out
classical evaluation procedures.
The goal of this work was to develop a consistent set of
analytical techniques for the non-destructive measurement of the
condition of paper and parchment books. Moreover, the analysis
should be spot-specific so that gradients of alterations may be
established, such as for instance in the vicinity of a paper
degradation inducing ink line. It is mandatory that these analytical
methods be non-destructive, with preference even contact-free.
Their applicability in the evaluation of the durability characteristics
of paper or the condition of paper artefacts must be assessed.
The capability to assess the condition of paper-based objects of
cultural value with the help of non-destructive analysis is of great
significance in providing a basis for developing a balanced
conservation policy. Indeed, existing standard testing procedures
find their origin in industry, they involve large samples and will
simply not be applied in conservation practice.
670 W. Faubel et al. / Spectrochimica Acta Part B 62 (2007) 669–676
In order to reach the main objective, we evaluate in our
laboratory the applicability of the following techniques.
Synchrotron radiation induced X-ray fluorescence microprobe
analysis (SR-μXRF) with the ability of multi-elemental detection
and quantitative ultra trace element analysis has become a very
popular tool for non-destructive analysis of valuable artefacts [1].
The method allows elemental imaging with micron resolution in
two dimensions and recently, first archeometric applications using
depth profiling were reported [2].
Fourier transform infrared (FTIR) microscopy will be used to
test how far the presence, and eventual chemical condition, of
individual products or product groups can be screened in the
complex paper matrix (cellulose, lignin, sulphate, fillers, and
pigments) [3,4].
At present, the condition of paper must be determined by tests
and analyses performed on samples taken from the document.
Although every effort is made to minimize the sample size
required, the ideal condition of strict non-destructive sampling has
not been attained. It is not hard to imagine therefore that paper
documents of the highest importance for cultural heritage, such as
18th and 19th centuries manuscripts of J.S. Bach and Charles
Dickens, which are seriously threatened, will ever be properly
analyzed. The classical analytical methods used are SEM/EDX
(scanning electron microscopy/energy dispersive X-ray micro-
analysis), ESCA (electron spectroscopy for chemical analysis),
XRD (X-ray diffraction, eventually on a micro-scale: μXRD), and
FTIR (Fourier transform infrared spectroscopy). A range of
chromatographical separation methods are used, such as IC (ion
chromatography), SEC (size exclusion chromatography) and GC
(gas chromatography), often coupled to MS (mass spectrometry),
normalized pH measurements, such as ISO 6588 and ASTM
D778, and several mechanical tests. Each of these methods gives
only partial results, referring to paper condition. Many of them
must be combined for a global condition evaluation [5–7].
Our special focus in this paper will be to report on novel
results using a variety of analytical techniques, like the
synchrotron radiation induced micro-X-ray fluorescence spec-
trometry (SR-μXRF) at the synchrotron radiation source ANKA
(Angströmquelle Karlsruhe) and the FTIR Microscopy. In a
previous publication we have already reported the FT Raman
mapping and the laser excited photothermal imaging on
investigations of the possibilities to soften brittle and horny
parchment with regards to urea as a softening agent for the
conservation of the Erfurt Bible of the Staatsbibilothek zu
Berlin-Preussischer Kulturbesitz [8].
2. Analytical techniques
2.1. Micro-X-ray fluorescence spectrometry (SR-μXRF)
This technique is based on measuring the element specific
emitted X-ray fluorescence radiation which follows ionization
by excitation with high energy photons. It allows qualitative and
quantitative determination of the elemental composition of the
sample. By scanning of a sample through a confined beam
information about the spatial distribution of each element is
obtained additionally [1].
Fig. 1. Relative detection limits of a biological standard reference material (NIST
SRM 1577b) 20 μm beam, excitation energy: 21 keV, measuring time: 1000 s.
The XRF results on historical iron gall ink manuscripts as well
as early prints described in this paper have been obtained at the
synchrotron radiation facility ANKA, a 2.5-GeV second generation
storage ring. The ANKA X-ray microprobe fluorescence station
enables the identification and semi-quantitative determination of
trace amounts of chemical elements in archaeometric samples with
high sensitivity. As excitation source either white beam (2.5–
35 keV) or monochromatic beam (multilayer monochromator, 2.5–
30 keV) can be used. Thus, trace elements can be specifically
excited and disturbing elements faded out. The entire set-up is
situated in a vacuum chamber, which allows detecting lighter
elements such as sodium and magnesium. Thereby the range of
detectable elements reaches from sodium beyond uranium.
As optical systems for creating X-ray micro-beams mono- and
poly-capillaries as well as novel X-ray refractive lenses based on
SU-8 polymer photo resist are used [9] yielding beam sizes down
to 1.5 μm × 3 μm [10].
Samples are positioned and scanned by three translational
stages (Micos) driven by stepper motors with sub-μm resolution.
The emitted fluorescence radiation is detected by a 30-mm2
energy dispersive Si(Li) detector (Oxford) with a digital signal
processor (Gresham). The energy resolution of the system is
135 eV (FWHM) at 5.9 keV (Mn-Kα).
Relative detection limits of SR-μXRF were determined by
measurements of certified standard reference materials. Fig. 1
represents typical detection limits obtained with 20 × 20 μm2
excitation beam size in an organic matrix (NIST SRM 1577
bovine liver). With an excitation energy of 21 keV and a
measuring time of 1000 seconds relative detection limits of 5 to
100 ppb for elements with Z = 26 (iron) to Z = 42 (molybdenum)
were achieved. In general sensitivity depends on sample depth
and environment conditions such as air or vacuum.
3. Fourier transform infrared microscopy
The FTIR microscope data reported here were obtained at room
temperature by the use of a Bruker IFS 66S spectrometer in a rapid
scan mode, with an IR Scope II. The intensity modulation of the IR
 W. Faubel et al. / Spectrochimica Acta Part B 62 (2007) 669–676
Fig. 2. Experimental set-up employing a special manuscript holder for SR-
μXRF analysis.
beam was produced by path difference modulation via a Michelson
interferometer. Typically 256 scans at a resolution of 8 cm− 1 were
used to collect the spectra from 600 to 4000 cm− 1 range. The rapid
scan spectra were modulated with a mirror speed (optical-path-
difference velocity, OPD) of 0.101 cm/s, leading to a modulation
frequency of 404 Hz at 4000 cm− 1 and 60.6 Hz at 600 cm− 1.
The FTIR technique has been tested on previous analysis
applied on samples from ancient manuscripts, as well as in
laboratory ink samples [3]. Results for ancient manuscripts
indicate a correlation between the cellulose oxidation, in acidic
and corroded ink samples, tested by the increasing band at
1720 cm− 1. This is not a clear band, it is a shoulder near the water
absorption belonging to the C-O bond, which can be explained by
hydrolysis and oxidation of cellulose. This is associated with
reduction in the −OH band at 3430 cm− 1.
This technique is useful in small samples with a size of 10 μm or
less and allows acquisition of spectra from single fibres. Cellulose
crystallinity changes during aging of paper, so variations in
intensities and shifts of the individual bands at 3350 cm− 1,
3418 cm− 1, 3466 cm− 1 in different spectra can be assessed. FTIR
can be also used for cellulose crystallinity (CI) determination. The
infrared crystallinity index has been already developed in the
1960s by Nelson and O'Connor [11] and bases on the absorption
ratio of two bands in the infrared spectrum of cellulose,
1372 cm− 1/2900 cm− 1. Nelson and O'Connor [11] found that
the band at 2900 cm− 1 (C-H and CH2 stretching) is relatively
invariant while the absorption band at 1372 cm− 1 (C-H bending) is
quite sensitive to changes in crystallinity.
4. Results
4.1. Analysis of historical iron gall ink manuscripts
Iron gall ink is from ancient times one of the most used inks. It
consists of vitriol (iron sulphate Fe(II)SO4) extracts of oak gall, an
extraction medium (as water, wine, or vinegar), and gum arabic as
dispersing and binding medium [12]. By exposure to atmospheric
oxygen, a black ferric gallate complex (Fe(III)) is formed. Vitriol is
671
contaminated in varying percentages with salts mostly present as
sulphates of copper, manganese, aluminium, or zinc. These
contaminants are characteristic for historic iron gall inks [13].
The deterioration of paper by iron gall ink so-called iron-gall ink
corrosion is known since a long time. Besides ink corrosion –
corrosion of excess vitriol (Fe(II)SO4) to iron oxides and sulfuric
acid and other transition metal ions present, especially copper, can
deteriorate the paper carrier by corrosion – iron and copper ions
catalyse oxidation processes of cellulose. Therefore, the investiga-
tion on degradation products is of great interest, in order to allow the
development of special restoration procedures needed to stabilize
the deteriorated artifacts [14]. As we emphasized above contactless,
non-destructive techniques like SR-μXRF have to be employed.
As an example for an iron gall ink manuscript we analyzed a
historical memo on legal land description (Stuehlingen/Baden-
Wuerttemberg, private owner) of the year 1769 script with SR-
μXRF at ANKA.
To make contactless, absolute non-destructive analysis
possible, a special sample holder for manuscripts was con-
structed of polymethyl methacrylate (PMMA). PMMA contains
only the elements H, C, and O which are in general not dete-
rmined by SR-μXRF, and it is scarcely contaminated by other
elements. Thereby the manuscript can be fixed directly on the
sample holder and no material is present (Fig. 2) which might
produce interfering peaks.
FTIR microscope reflection analyses (beam spot size:
40 μm) of this iron gall ink manuscript have shown differences
on the used inks. Due to the different state of degradation of
cellulose (paper) differences in the intensities of C-H bonds
(∼3000 and 1400 cm− 1) and O-H bonds (∼ 3500 cm− 1) are
evident [3] (Fig. 3).
SR-μXRF measurements using a 20-μm beam confirmed
this result. As shown in Fig. 4 (right top) the iron gall inks used
are contaminated by manganese, copper, and zinc.
As characteristics of iron gall inks the peak areas of manganese,
copper, and zinc in each measured SR-μXRF spectrum of this
manuscript of the 18th century were determined and alluded to the
respective iron content.
Fig. 3. Original iron gall ink manuscript on legal land description of the year
1769; FTIR micro-reflectance spectra (Bruker IFS 66/S with attached IR scope
II, resolution 4 wavenumbers, measuring time 5 min) measured on iron gall ink
in line 4 and 11 (according to Fig. 4).
672 W. Faubel et al. / Spectrochimica Acta Part B 62 (2007) 669–676

Fig. 4. Photo of the manuscript; right top: representative SR-μXRF spectra (21.5 keV excitation energy, 20 μm capillary, measuring time: 500 s) of the iron gall ink and
paper; right bottom: zinc to copper ratio of iron gall ink in different lines of the manuscript.

From the analytical results it is apparent that the zinc to [4]. The goal of the analytical investigations is to identify the
copper ratio of the iron gall inks investigated show differences composition of the green coloration and further to confirm the
(Fig. 4, right bottom). The ink in line 4 and 5 is not identical assumption of a copper contamination within the brown
with the ink that has been applied in line 10 and 11, which can discolored areas. The results should facilitate the selection of
be deduced from the significant lower zinc and copper content a suitable restoration technique.
of the letter. The conclusion can be drawn that the writer Colorations were analyzed by SR-μXRF in order to identify
changed the ink during the document draft. From a conservation the elemental composition of the pigments with the aim of a
point of view it is evident that as higher the copper content of better understanding of the materials used and the choice of
the ink is, the higher is the possibility that ink corrosion occurs. conservation treatments. A special sample holder for this book
according to its dimensions which restricts the aperture angle to
4.2. Analysis of a historical hand-colored herbal 150° was drafted and constructed. This exclusive sample holder
allows the positioning of one single sheet for SR-μXRF
As an example of an early printed book, an original hand-
colored herbal “Herbarium imagines vivae/Imaginum Her-
barum Pars II” of the year 1536/38 from the Senckenbergische
Bibliothek, Frankfurt, was analyzed. This Herbarium is a
German print of the 16th century. Herbs and plants are printed
by woodcut with letterpress and were later hand-colored. The
herbal consists of two different parts one dating form 1536, the
other from 1538. It is the only copy in German, Austrian, or
Swiss public libraries with the original Renaissance binding.
The book suffered water damage in the past which caused
tide lines and especially discoloration within the green colored
areas. It is well known that the green colors which have been in
use at that time are mostly copper based pigments. Often
verdigris, i.e., several modifications of copper acetate have been
used. These pigments show sensitivity towards water or
humidity especially the artificial “pigment” verdigris which to
Fig. 5. “Herbarium imagines vivae/Imaginum Herbarum Pars II” (1538/1536)
some extent is water soluble. The migration of copper ions into Senckenbergische Bibliothek, Frankfurt (Inv.Nr.4Q.203.2066). Left: special book
the paper carrier causes oxidative decomposition of cellulose sample holder for SR-μXRF analysis; right: exemplary one single sheet (fol.4r)
and leads to paper embrittlement and deep brown discoloration positioned for SR-μXRF analysis.
 W. Faubel et al. / Spectrochimica Acta Part B 62 (2007) 669–676 673

Fig. 6. “Herbarium imagines vivae” (1538) Senckenbergische Bibliothek, Frankfurt (Inv.Nr.4Q.203.2066). Left: detail photo of plant Gackauchlauch (fol.4r); right:
representative SR-μXRF spectrum (excitation energy: 21.5 keV) of the green illumination.

analysis, without impairment of serviceability of the original
Renaissance binding (Fig. 5). The SR-μXRF spectra of green
colorations show high concentrations of copper (green pigment)
and further potassium, calcium, manganese, iron, rubidium, and
strontium which may be interpreted as contaminants of the
paper support (Fig. 6). Comparison of copper distribution in the
herbal and an original cover sheet of the same but uncolored book
confirms the assumption of the migration of copper ions into the
paper support, as a result of water damage. The water damage is
presumably responsible for contaminations of the green illumina-
tion with sulphur and mercury. They origin in red illuminations
with vermilion (HgS) (Fig. 7) as comparison with reference
materials and pigments showed. The green pigment of the
illumination was identified as verdigris, for the reason that
among the green copper containing pigments used for illumination
of printed books at the period the object was created, the only one
that shows a considerable solubility in water is verdigris, which is
copper acetate in different crystalline modifications. It is well
known that free copper (II) ions are effective oxidations catalysts
that cause decomposition of cellulose. This type of deterioration of
paper artefacts is called copper pigment corrosion. Corresponding
SR-μXRF spectra of a hand-colored and uncolored cover sheet of
the second part of the herbal (Fig. 8) are shown in Fig. 9.
Comparison of copper distribution provides further evidence for
pigment migration due to water damage. The results suggest that
the embrittlement of the paper and the brown discolorations are
resulting from the oxidative decomposition of paper by copper
(II)–ions. The analytical results allow the conservator to design a
suitable conservation, which on the one hand inhibits the progress
of the decomposition reaction and stabilizes the already affected
paper support, which both must be based on a non-aqueous
intervention [15].
4.3. Analysis of papers of an incunabula (dated before 1500)
Several historical papers of incunabula “Johannes von Saaz:
Der Ackermann aus Böhmen” dated from 1463 and printed by
Albrecht Pfister, Bamberg, were analyzed. The object is owned
by the Herzog August Bibliothek Wolfenbüttel. Incunabula
(Latin: incunabula = cradle) are early printed books dated before
1500, when the printing technique was still in its infancy. The
support papers of the object suffered from a special type of
damage as there are small holes in the areas of letters, which is
an unknown destruction phenomenon. It was suggested that
these losses may also be the result of metal catalyzed
degradation reactions of cellulose. Fig. 10 shows a detail of
the printed text and these holes in the paper.
Measured red colorants of letter and red line seem to be
vermilion as reference measurements have shown. One observes
significantly more lead in the red letter as in the red line. This can
be explained by abrasion during the printing process.
The areas around the holes in the paper were analyzed. In
some cases higher concentrations of zinc have been detected.
Further investigations of two fragments with leavings of

Fig. 7. “Herbarium imagines vivae” (1538) Senckenbergische Bibliothek, Frankfurt (Inv. Nr. 4Q.203.2066). Left: detail photo of plant “Johans Treublin” (fol. 21 v);
right: representative SR-μXRF spectrum (excitation energy: 21.5 keV) of the red illumination.
674 W. Faubel et al. / Spectrochimica Acta Part B 62 (2007) 669–676
Fig. 8. Cover sheet of the second part of the herbal “Imaginum Herbarum Pars
II” (1536). Left: uncolored cover sheet woodcut with letterpress (private owner);
right: the same but hand-colored cover sheet, Senckenbergische Bibliothek,
Frankfurt (Inv.Nr.4Q.203.2066).
printing ink, which were detached from Pfister prints during
restoration at the Herzog August Bibliothek Wolfenbüttel, show
reproducible higher copper concentrations. For comparison and
statistical purposes additional sheets of “Johannes von Saaz:
Der Ackermann aus Böhmen” and other papers of incunabula
printed by Albrecht Pfister as well as other papers of incunabula
of the 15th century from another printer were analyzed.
Comparison of the nickel/lead to copper/lead ratio of these
analyses is shown in Fig. 11.
Copper to lead ratios of 0.5 to 2 were found from SR-μXRF
analyses of the papers of incunabula “Johannes von Saaz: Der
Ackermann aus Böhmen” (1463) and “Ulrich Boner: Der
Edelstein” (1461) from Albrecht Pfister, Bamberg. These results
correlate with former analyses of the Gutenberg Bible which
reported an unusually high copper and lead content of Gutenberg's
ink [16–18]. Employing X-ray fluorescence analyses induced by
white synchrotron radiation on a page of the Gutenberg Bible,
Mommsen et al.[19] found Cu/Pb = 1.0± 0.5 recto, ±0.4 verso and
Ni/Pb = 0.007 ± 0.0035 recto, ±0.002 verso. Therefore, the sort of
ink Gutenberg used for the recto and verso side of the 42-line Bible
sheet can be assumed to be the same.
Fig. 9. Representative SR-μXRF spectra from the uncolored (blue) and hand-
colored (red) cover sheet of the second part of the herbal “Imaginum Herbarum
Pars II” (1536). Excitation energy: 16.5 keV (blue)/21.5 keV (red), measurement
time: 200 s.
Fig. 10. Johannes von Saaz: “Der Ackermann aus Böhmen” printed by Albrecht
Pfister, Bamberg (1463) (fol.13r), Herzog August Bibliothek Wolfenbüttel. Left:
detail in transmitted light.
For further reference we analyzed also the well-preserved
“Biblia latina” from the printer Berthold Ruppel, Basel, by SR-
μXRF analyses at ANKA and found also in this specimen elevated
copper to lead ratios. Until now high metal concentrations have
been detected only for the very early years of printing. These
results and the fact that the Biblia Latina is without any damage
lead us to the conclusion, that small holes may not be the result
from metal catalyzed degradation reactions of cellulose.
Additionally, to the SR-μXRF Cu/Pb analysis of different
papers of incunabula of the 15th century, FTIR microscope
reference analysis has been performed to identify a blue spot in the
“Ulrich Bonner: Der Edelstein” (1461) from Albrecht Pfister,
Bamberg. Using the FTIR microscope in the reflectance mode, we
could show that the blue pigments consist of azurite (Fig. 12).
According to the literature azurite is composed of basic carbonate of
copper, 2CuCO3Cu(OH)2. Generally, the following fundamental
vibrations of the carbonate groups have been reported for the pure
azurite powder: 1490, 1415, 1090, 837, and 817 cm− 1, while OH
out-of-plane bending modes produce strong bands at 3425 and
952 cm− 1[20]. For the structure of azurite it is reported that it
5
crystallized in the space group C2h , with Z =2. The structure
contains two types of Cu atoms, both in distorted square planar co-
ordination to two hydroxyl groups and two carbonate oxygens. The
infrared spectra in the region 5000–600 cm− 1 of azurite is readily
interpreted in terms of carbonate ions in sites of low symmetry, and
the of the OH groups present, while those in 500–60 cm− 1 are
Fig. 11. Analysis of different papers of incunabula of the 15th century from
Albrecht Pfister, Bamberg, and other printers as B. Ruppel, Basel, from the same
period.
 W. Faubel et al. / Spectrochimica Acta Part B 62 (2007) 669–676
Fig. 12. FTIR microscope analysis of a blue pigment in the incunabula of
“Ulrich Boner: Der Edelstein” (1461) from Albrecht Pfister, Bamberg.
found to correspond well to the vibrations of CuO2(OH)2 for
azurite. The fundamental vibrations of the carbonate group in
azurite and the incunabula are all observed, as is to be expected
from the C1 site symmetry of the carbonate ion, and the suggested
assignments for the combination frequencies agree well with
observation. The splitting of the out-of-plane bending mode ν2
(range 837–817 cm− 1) is typical for carbonates, just as the ν3 mode
(range 1490–1415 cm− 1) can be assigned to CO23− [21].
Fig. 12 shows a very good agreement of the IR bands,
discussed above, for the blue pigment (“Ulrich Boner: Der
Edelstein”) and the azurite standard which has been prepared by
fixing the azurite with gum arabic on an adequate paper support.
5. Conclusion
In context to the description of writing and print substrates
contact-less and non-destructive analytical techniques become
more and more important for the investigation of the composition
of existing painting and writing materials in art and design. These
analytical methods are of special interest for probing of
decomposition phenomena and paper artefacts. Metals influence
the catalytic deterioration of the paper, especially iron and copper
are well known as effective oxidation catalysts causing the
decomposition of cellulose. In this work, we analyzed historical
iron gall ink on paper, green copper pigments in a historical hand-
colored herbal and additionally, some sheets of an incunabula,
under the suspicion that the observed deterioration phenomena
for the incunabula has been caused by the influence of copper
ions occurring in printing ink. Using X-ray micro-fluorescence
(SR-μXRF) and Fourier transform infrared microscopy it was
possible to identify the elemental composition of the pigments and
to characterize the decomposition phenomena of writing and print
substrates. Especially, the SR-μXRF shows the advantage
compared to other analytical techniques, like PIXE, to be an ultra
trace analytical, which enables us even to investigate trace
concentrations of accompanying elements in ink, printing inks or
pigments, adequately. Thus, it was possible to identify two different
types of iron gall inks, with two different concentration ratios of
copper and zinc, on the same sheet of a historical manuscript.
For the water affected herbal, the comparison of the copper
distribution and an original cover sheet of the same but uncolored
book confirms the assumption of decomposition phenomena due
675
to the migration of copper ions out of the illuminated area. The
results suggest that the embrittlement of the paper and the
brownish discoloration are resulting from the oxidative decompo-
sition of paper by copper(II)–ions, the so called “copper-pigment
corrosion”. Thus, this analytical result allows the restorer to select
adequate options for the elaboration of a conservation treatment,
which requires in this case the treatment with antioxidant and
neutralizing chemicals in non-aqueous media.
The SR-μXRF elemental analysis of an incunabula with a
remarkable number of holes in the peripheral area of the printing
paint, allows us to exclude that this special damage was effected by
the contamination of the printing ink with copper because no
migration of copper of the printing ink was found in the affected
area. Also by this result the restorer is enabled to choose the
adequate method of treatment.
Acknowledgments
The authors thank the Senckenbergische Bibliothek, Frankfurt
am Main, for providing “Herbarium imagines vivae/Imaginum
Herbarum Pars II” (Inv. Nr. 4Q.203.2066), 1538/1536.
Furthermore, the authors thank the Herzog August Bib-
liothek Wolfenbüttel for providing papers of incunabula from
Albrecht Pfister for analysis.
We thank the Bibliothek der Universität Mannheim for
cooperation and Ch. Frieh and D. Erbe for technical support.
Thankfully one of the authors (S.Staub) has been funded by
the European Community: contract G6RD-2000-0345.
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