Journal of Paper Conservation

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Stabilization of Verdigris
Application of Research in Conservation Practice

Christa Hofmann, Andreas Hartl, Kyujin Ahn, Kristina Druceikaite, Ute

Henniges & Antje Potthast

To cite this article: Christa Hofmann, Andreas Hartl, Kyujin Ahn, Kristina Druceikaite, Ute
Henniges & Antje Potthast (2016) Stabilization of Verdigris, Journal of Paper Conservation, 17:3-4,
88-99, DOI: 10.1080/18680860.2016.1247515

To link to this article: https://doi.org/10.1080/18680860.2016.1247515

Published online: 26 Apr 2017.

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Stabilization of Verdigris:
Application of Research in Conservation Practice

Christa Hofmann*, Andreas Hartl, Kyujin Ahn, Kristina Druceikaite,

Ute Henniges, Antje Potthast

The results of a research project on verdigris on paper have been applied in the conservation of a celestial
atlas and a series of printed books with images of cities in Renaissance time. Paper degraded by verdigris
was chemically stabilized by applying a solution of benzotriazole, a copper complexing agent, in ethanol by
brush from the verso. Tears and brittle areas were mechanically stabilized with pre-coated Japanese tissue
papers. The copper ion content and the effect of complexation were monitored with self-prepared copper ion
indicator papers. Paper samples with different concentrations of benzotriazole were light-aged to evaluate
the effect of yellowing.
Keywords: Verdigris, Pre-coated Japanese tissue paper, Complexation of copper, Copper ion indicator papers

Introduction by verdigris. Finished in 2012, the project elicited

Verdigris, a collective term for copper acetate with
different compositions, is one of several copper green
pigments. Verdigris is produced by reactions of met-
allic copper with acetic acid in the presence of
oxygen. Initially blue-green, the colour turns green
with ageing. As an easily available pigment, verdigris
has been frequently used as green pigment on paper:
in manuscripts, in printed books, on maps, prints,
and drawings. Verdigris was applied in thick layers
or in a diluted form to colour drawings and printed
maps. Organic colourants were frequently added to
temper the blue-green colour to yellow-green tones
or to achieve dark-green shades as described in
many manuals for painters (Boltz von Ruffach,
1913; Clarke, 2011). Depending on the support, the
sizing and the manner of application, the green
colour can penetrate to the verso of the paper.
Coloured areas may turn brown, on recto and verso.
Copper ions can cause degradation of the paper
support (Banik & Ponahlo, 1982; Henniges et al.,
2005): the paper becomes brittle and breaks easily.
For example in coloured prints from the atlas
Harmonia macrocosmica by Andreas Cellarius brown
discolouration is visible on recto and verso of areas
which were initially green (Figure 1). Turning the
pages in this atlas has caused tears and losses in
embrittled areas.
The aim of a previous research project was to find
methods to stabilize verdigris on paper: to chemically
stabilize copper ions which cause deterioration of cel-
lulose, and to mechanically stabilize paper damaged
promising results for methods of chemical and mech-
anical stabilization. During the last 3 years, the
results were applied in the conservation of manu-
scripts, an incunabula, an atlas and a series of early
printed books with coloured prints at the Austrian
National Library. In the treatment of manuscripts
with coloured drawings and of the incunabula
Peregrinatio in terram sanctam with coloured wood-
cuts brittle areas and losses were reinforced with
pre-coated Japanese tissue papers. In the conserva-
tion of the atlas Harmonia macrocosmica and three
volumes of Civitates orbis terrarum methods of
chemical and mechanical stabilization were applied.
The decision-making process and the treatment of
these last two case studies will be presented in this
paper. The presentation includes the application of
copper ion indicator papers and the results of a
light ageing test.
Background: results of the verdigris project
In the previous research project, samples were prepared
by applying synthetic copper acetate (Kremer) in gum
arabic (Kremer) to handmade gelatine-sized rag paper
(Gangolf Ulbricht) in thick and thin layers of paint as
can be seen in Figure 2. The samples were pre-aged
by light to induce degradation of cellulose before treat-
ment and to render the paint layer less water sensitive.
For the evaluation of the chemical treatments, the pre-
aged samples were treated with different solutions of
de-acidification, antioxidant, and complexing agents,

© IADA / International Association of Book and Paper Conservators 2017

88 DOI 10.1080/18680860.2016.1247515 Journal of Paper Conservation 2016 VOL. 17 NOS. 3–4

applied by airbrush on a suction table or by brush from
the verso of the sample. The treated samples were sub-
mitted to accelerated ageing at increased levels of temp-
erature and relative humidity. An additional set of
samples was light-aged. Figure 2 shows samples
treated with a 0.5% solution of benzotriazole by air-
brush after treatment, after post-light ageing and after
FIGURE 2 Verdigris samples sprayed with a 0.5% solution
of BTA, from left to right: after treatment, after post-light
ageing, after post-thermal ageing.
C. Hofmann et al. Stabilization of verdigris
FIGURE 1 Harmonia
macrocosmica (ÖNB
BAG 265.697-E),
printed map on which a
former green
colouration has turned
brown.
post-thermal ageing. After post-ageing, the cellulose
was analysed by gel permeation chromatography
(Potthast et al., 2003) to assess the effect of the
treatments on cellulose, on molecular weight and car-
bonyl group content. For mechanical stabilization,
Japanese tissue papers were coated with different
adhesives and adhesive mixtures. The pre-coated
papers were activated with water or ethanol and
applied to the samples recto and verso. After ageing,
the effect of the pre-coated papers on the samples was
visually assessed and compared.
A detailed description of the experimental and the
results of the verdigris project can be found in Ahn
et al. (2014; 2015) and Hofmann et al. (2015).
Summarizing the main outcome, 3% of benzotriazole,
BTA (Merck), in ethanol 96% (Australco) was found
to be promising to slow down copper-induced cellu-
lose degradation, depending on the conditions of the
samples and the application methods (in Ahn et al.,
2015; Figure 4: change in the total carbonyl group
content of all the samples vs. chain scission after hot
and humid ageing; Figure 5: change in the total carbo-
nyl group content of all the samples vs. chain scission
after light ageing for 330 h). BTA is a strong complex-
ing agent for copper that has been used in industry and
in metal conservation (Sease, 1978; Madsen, 1985).
Faerber (2007) first introduced BTA to paper conser-
vation. A substantial drawback of BTA to be used uni-
versally for copper-containing paper objects was that
light ageing caused discolouration of BTA on rag
paper.
Journal of Paper Conservation 2016 VOL. 17 NOS. 3–4 89
C. Hofmann et al. Stabilization of Verdigris
Pre-coated Japanese tissue papers (Pataki, 2009;
Titus et al., 2009) proved to stabilize rag paper
mechanically without inducing further damage after
light and thermal ageing (Hofmann et al., 2015).
When applied on the recto of coloured areas, thin
papers, 2–3.7 g m−2, with a matte adhesive coating,
only compromise the visual appearance moderately.
Japanese papers of 5–8 g m−2 can be used to
support the verso of strongly degraded rag papers.
Homogeneous and matte films can be achieved by
brushing dilute adhesives on a silicone mat.
Activation of pre-coated papers with the sponge-
blotter-system, developed by Jacobi et al. (2011)
reduces the risk of migration of copper ions.
Migration test papers for iron (Jacobi et al., 2011;
Belhadji et al., 2014) and copper ions help to control
and adjust treatment methods. In the study at the
Austrian National Library, Japanese tissue papers
coated with gelatine, Klucel® G in ethanol, wheat
starch paste, and methylcellulose as well as combi-
nations of these adhesives proved to provide sufficient
support for rag paper. A coating with Klucel® G in
ethanol, which can be activated with ethanol, offers
a non-aqueous alternative. By blending adhesives,
properties of the coating can be adjusted. When gela-
tine and Klucel® G are mixed the gloss of gelatine can
be reduced. After thermal and after light ageing the
adhesive coatings showed only minor colour change.
Experimental
Preparation of copper ion indicator paper
Copper ions indicator papers were used to detect
copper ions in the objects of the following case study
and to monitor treatments. These indicator papers
were prepared based on the publication of Hulthe
(1970). According to Hulthe, a nearly circular, uni-
formly coloured, yellow spot appears if more than
1 ppm of copper ion is present. The reagent paper con-
tains sodium chloride, hydroquinone for the reduction
of copper II to copper I ions and bathocuproine, a
colour indicator for copper ions. Whatman No. 1 is
dipped in a 0.2 mol L−1 sodium chloride solution
and left to dry overnight. A solution with equal
parts of acetone and chloroform is prepared, which
contains 0.15 g bathocuproine per 100 mL solution
and 0.2 g hydroquinone per 100 mL solution.
1.5 mL ethanol is added to the solution. The
Whatman papers doped with sodium chloride are
dipped into this solution, taken out and left to dry at
least 48 h for all solvents to evaporate.
To detect copper ions, strips of the indicator paper
are humidified with one drop of de-ionized water.
Excess water is blotted off and the paper strips are
90 Journal of Paper Conservation 2016 VOL. 17
put on areas with green colouration under the light
pressure of the fingertip. Gloves are worn to avoid con-
tamination of the paper. The verso of the area tested is
supported by a piece of blotter and a sheet of polyester
film. In the presence of copper ions, the indicator
paper turns yellow to orange depending on the quan-
tity of copper ions. The colour is judged after drying.
Light ageing
To evaluate the effect of different concentrations of
BTA on the colour of paper under light, test samples
were prepared for light ageing to aid in the decision-
making process for possible future treatments. These
additional tests were done after the treatment of the
described books had been completed and were
inspired by the discussion after the presentation at
the XIIIth IADA congress in Berlin. Whatman No.
1 and Ulbricht rag paper were cut to 60 × 160 mm
pieces. BTA was applied by brush on 40 × 160 mm of
the paper in the following concentrations: 0.5, 1, 1.5,
2, 2.5, and 3%. The Whatman and Ulbricht papers
were light aged with 10 cycles of four hours in the
dark at (30 ± 2)°C followed by 12 hours with an
irradiation of 1.10 W m−2 (monitored at 420 nm)
with a black panel temperature of 65°C in a Q-Lab
Xe-1 tester. The instrument used in this experiment
does not allow controlling the relative humidity. Due
to the increased temperatures, relative humidities
below 30% were established.
Case studies: Harmonia macrocosmica and
Civitates orbis terrarum
History and condition
Harmonia macrocosmica by Andreas Cellarius is an
atlas with images of planetary systems and celestial
maps incorporating Antique and Renaissance knowl-
edge (Van Gent, 2006). The book conserved was
printed in 1708 in Amsterdam and had been part of
the private library of Emperor Franz I (ÖNB BAG
265.697-E/FKB 34–007a). The atlas had been
rebound in the nineteenth century.
The rag paper measures 0.20–0.25 mm in thickness
and is in an overall good condition. One measurement
with a Merck pH indicator strip revealed a surface pH
of 4.7. The illumination in green colour was applied
diluted or in thicker layers with a high proportion of
binding media. Most green-coloured areas have
turned brown on recto and verso (Figure 1). In some
cases, brown discolouration has been transferred to
the adjacent page. In the part of the map, which has
been attached to the guard, the green colour is some-
times protected by the glue of the guard and has
NOS. 3–4

preserved its original colour. Especially areas that are
exposed to more mechanical stress, when the pages are
turned, have smaller and larger tears due to the
embrittlement and the loss of flexibility of the cellu-
lose. The severity of paper degradation, the visual
appearance of the pigment and copper ion tests (see
below) led to the assumption that verdigris was used
for green colouration.
Civitates orbis terrarium by Georg Braun and Franz
Hogenberg is a five-volume book assembling over 450
descriptions and images from cities of the world in
Renaissance time (Füssl, 2011). Figure 3 shows the
image of Tigurum (Zurich). The volumes appeared in
sequence from 1572 to 1618 in Cologne. The Latin
edition in the Department of Manuscripts and Rare
Books of the Austrian National Library dates from
1582 onwards. At some point, the volumes seemed
to have been exposed to high humidity since water
stains and mould spots were observed. All volumes
are in their original leather bindings. The five
volumes have been stored in the baroque hall of the
Prunksaal (ÖNB HAD 47.Dd.6.Alt-Rara).
In volume I–IV, the prints depicting cities are
coloured. The paper quality differs from volume to
volume: the paper is generally yellowed and shows
signs of negligent production in thin areas, folds, and
FIGURE 3 Civitates orbis terrarum (ÖNB HAD 47.Dd.6.Alt-Rara), Vol. III: coloured print of Tigurum (Zurich).
C. Hofmann et al. Stabilization of verdigris
metal impurities. The thickness of the paper in volume
II measures between 0.18 and 0.23 mm. One measure-
ment in volume II in a yellowed area on the margin
yielded a surface pH of 4.2. Many but not all green
areas have changed to brown. The brown discolouration
has migrated to the verso (Figure 4). On some pages
degraded green colour has led to brown off-prints on
adjacent pages. The degradation caused by copper-con-
taining pigments is especially pronounced in volumes II
and III. In volume III, tears and losses can be found in
browned areas that are exposed to more mechanical
stress when the book is opened and read.
Discolouration and degradation together with copper
ion tests led to the assumption that most of the green
areas were painted with verdigris. White crystals found
in volume III were identified as alum by FT-IR analysis
(data not shown). It is assumed that the degradation of
the paper caused by copper ions was facilitated by
poor quality paper, the presence of alum and/or at
some point the influence of high humidity.
Detection of copper ions with copper ion
indicator paper
The Hulthe-indicator papers, described above, were
applied to confirm the presence of copper in green
Journal of Paper Conservation 2016 VOL. 17 NOS. 3–4 91
C. Hofmann et al. Stabilization of Verdigris
FIGURE 4 Civitates orbis terrarum (ÖNB HAD 47.Dd.6.Alt-Rara), Vol. III: brown discolouration migrating from the recto of the
coloured prints.
colouration and in colouration that has turned brown.
They were used to decide if free copper ions from ver-
digris are present. When applied on Harmonia
Macrocosmica and Civitates orbis terrarum Volume
III, the copper ion indicator paper showed a pro-
nounced orange colour reaction on these areas on
the recto. Volumes I, II, and IV of Civitates orbis ter-
rarum are in better condition than volume III. The
colour change on the indicator papers ranged from
an overall orange reaction to spots of orange.
Decision-making process
The atlas by Andreas Cellarius was not accessible to
the public due to its present condition. Volumes II
and III of the description of cities by Georg Braun
were endangered by their use in the reading room.
Volumes I–IV showed disfiguring brown discolour-
ation. The curators brought the books to the attention
of the Conservation Department. The aim of a conser-
vation treatment was to stabilize the objects in their
current condition, to prevent further damage and to
allow restricted use of the books.
The five volumes of Civtates orbis terrarum are in
their original sixteenth century leather bindings. The
bindings had to be preserved and treatments of
92 Journal of Paper Conservation 2016 VOL. 17
verdigris had to be done in the bound books.
Harmonia macrocosmica was rebound in a half-
leather binding in the nineteenth century. The
volume from the private library of Franz I is not com-
plete. Unbinding of the book was discussed as a treat-
ment option at the beginning of the decision-making
process. As the binding is in good condition and the
history of the object should be preserved, this option
was disregarded as too invasive.
Areas deteriorated by verdigris in Harmonia macro-
cosmica and in volume III of Civitates orbis terrarum
showed tears and losses especially where the mechan-
ical stress of opening the book and turning the pages
was more pronounced. In the conservation of both
books, it was necessary to mechanically stabilize
areas of verdigris on paper as a minimal treatment.
The research results dealing with the pre-coated
Japanese papers showed that these papers could be
applied locally without causing migration of copper
ions. For the coating of the Japanese tissue papers,
good adhesion with sufficient flexibility when the
pages of the book are turned is necessary. The verdi-
gris project evaluated different coating options with
respect to their flexibility and adhesion. Papers
coated with gelatine had shown good adhesion in com-
bination with good flexibility of the mending paper.
NOS. 3–4

The gelatine coating exhibited gloss after drying. The
gloss of gelatine can be reduced by using the support
of a silicon mat for the coating. The addition of
Klucel® G in water or ethanol further reduced the
gloss of the adhesive layer. Therefore it was decided
to use a mixture of gelatine 2.5% and Klucel® G
2.5% in water in the ratio 3:1 (w/w).
The chemical stabilization in the conservation of
the two objects was intensely discussed. The pros
and cons of the application of BTA from our previous
study were considered: BTA was promising to stabilize
the copper-containing paper and to reduce migration
of copper ions when it was applied properly. The
application of tetrabutylammonium bromide, TBAB
(Maitland, 2009; Tse et al., 2012; Malešič et al.,
2015) was not considered because in our study the
antioxidant effect was less pronounced and less
reliable than the complexing effect with BTA after
ageing. As de-acidification treatments, aqueous and
non-aqueous, did not enhance stabilization of cellu-
lose in our previous study, they were not considered
as a treatment step. BTA has the disadvantage that
it can cause yellow discolouration of the paper and
the green paint after light ageing. There is no long-
term experience with BTA in paper conservation;
the action of BTA on paper has not been researched
sufficiently yet. Tests of bringing dry Whatman
papers impregnated with BTA in contact with verdi-
gris samples (Faerber, 2007), under weight and
under vacuum, did not show any positive potential
in pre-tests. Therefore, it was decided to locally
apply a BTA solution in ethanol to verdigris that
had brown discolouration on the verso in both
cases, aiming to stabilize strongly degraded areas
and to prevent further deterioration of less degraded
areas.
The reason why it was decided to apply BTA
directly onto the historic paper despite of the poten-
tial discolouration was that the colour change would
not be pronounced since the green areas already
showed a more or less strong colour shift from
green to brown. It was assumed that additional yel-
lowing by BTA would be limited. In addition,
natural ageing has yellowed the paper itself in the
books of Civitates orbis terrarum. To avoid further
colour changes of the surrounding paper, the appli-
cation should be strictly limited to areas coloured
with verdigris. A 3% solution was chosen because
it clearly stabilized cellulose after thermal and light
ageing. The results of the 0.5% solution were less
convincing in our previous study. We decided to
use a 3% solution because we wanted to be sure
that copper ions are complexed on papers and
paint layers of varying thickness when applied
from the verso. Due to the known potential of dis-
colouration of BTA after light ageing, but not after
C. Hofmann et al. Stabilization of verdigris
hot and humid ageing, it was decided with the cura-
tors that the exposure to light should be limited after
conservation. Access to the books was to be
restricted after the treatment. Both objects will not
be exhibited.
Treatment
The description of the treatments focuses on the appli-
cation of BTA and reinforcement with coated papers.
After dry cleaning of the objects, the treatment contin-
ued with chemical stabilization, which was followed by
mechanical stabilization. With strips of copper ion
indicator papers (6–8 mm) the copper ions in the
green colouration in Harmonia macrocosmica and
Civitates orbis terrarum, Vol. I–IV, were detected
prior to treatment. The complexation of copper ions
was checked with the indicator papers after the appli-
cation of BTA (Figure 5). As BTA is harmful to
health, the treatment was performed under a fume
hood with protective garments.
In Harmonia Macrocosmica, the 3% solution of
BTA (Merck) in ethanol 96% (Australco) was
applied with a synthetic brush (da Vinci No. 4) to
the verso of areas with discoloured verdigris. Pre-
tests with copper ion indicator papers on Harmonia
macrocosmica showed that a onetime application
with 3% BTA from the verso was sufficient to
complex the copper ions present. Multiple appli-
cations lead to the formation of white crystals, which
could be brushed off. The solution was carefully
applied on the browned parts while it was avoided to
spread solution in areas without verdigris. In
Civitates orbis terrarum, BTA had to be applied to
larger areas. Fine (daVinci No. 4, 6, 8) and broad syn-
thetic brushes (daVinci 16, 18) were used depending on
the size of the area. During treatment in the fume
FIGURE 5 Civitates orbis terrarum, Vol. II, print of Danzig,
detail with copper ion indicator paper, before (lower paper)
and after (upper paper) treatment with BTA.
Journal of Paper Conservation 2016 VOL. 17 NOS. 3–4 93
C. Hofmann et al. Stabilization of Verdigris

hood, book wedges supported the book. After each

application, the solution was left to evaporate before
the page was turned.
When the stabilization with BTA had been com-
pleted, tears, losses, and brittle areas in Harmonia
macrocosmica and Civitates orbis terrarum were
mechanically stabilized. On verdigris, only pre-
coated Japanese tissue papers were applied. In
Harmonia macrocosmica Paper Nao RK0 5 g m−2
was chosen for reinforcement of local tears and
small areas. Paper Nao RK1 8 g m−2 was used for
large browned and brittle areas (Figure 6). On some
pages, it was necessary to secure a tear also from the
recto. In these cases, Paper Nao RK00 3.7 g m−2
and Römerturm, KR4C 4 g m−2, cream, were used
(Figure 7). In Civitates orbis terrarum, Vol. II and
III, RK1 and RK0 were used on the verso of verdigris
depending on the degree of support necessary and the
size of the area. Browned paper with printed text was
reinforced with RK00 or KR4C cream. On the recto
of images, tears close to the guard had to be secured
from verso and recto with RK00 or KR4C cream.
FIGURE 7 Stabilization of a tear from the recto with pre-
Cream tissue papers or tinted tissue papers are less
coated Japanese tissue paper (KR4C) in Harmonia
obvious when used over text or colouration, especially macrocosmica.
on browned verdigris. The choice of RK00 and KR4C
depended on the colour of the area to be reinforced.
Pre-coated tissue papers with less than 3.7 g m−2 are
more difficult to handle and seemed too thin to reinforce a tear close to the guard. The reinforcements
should offer protection when the pages of the books
are turned.
The Japanese tissue papers were coated with a
mixture of three parts gelatine (Gelita®,
Photographic gelatine, type B, 264 Bloom,
Kleindorfer Gelatine Restaurierung 1) 2.5% and
one part Klucel® G (Kleindorfer) 2.5% in water, w/
w. The adhesive mixture was applied on a self-pre-
pared silicone mat (Hofmann et al., 2015). A 5 mm
silicone replica (Elastosil® M 4641 A/B) was pro-
duced from the rough surface of a cutting support
(Boesner) or a matte glass plate. The tissue paper
was placed on the silicone mat and stretched out.
With a soft synthetic brush (da Vinci® 60 mm), the
adhesive mixture was brushed on the tissue paper
starting from the middle until the paper was evenly
saturated. The adhesive was left to slowly air dry.
The tissue papers with the dry adhesive coating
could be easily peeled off the silicon mat. On the
dry pre-coated paper, strips can be cut to support
tears. Larger pieces can be cut following the form
of an area that needs support. A template of polyester
film can be used to cut irregular forms. For the stabil-
ization of large areas like on maps in Harmonia
Macrocosmica, the pre-coated Japanese papers were
FIGURE 6 Reinforcement of brittle paper from the verso applied in pieces following the form of a large
with pieces of pre-coated Japanese tissue paper (RK1) in
browned area (Figure 6). The pre-coated papers
Harmonia macrocosmica.
were activated by the sandwich system (Jacobi

94 Journal of Paper Conservation 2016 VOL. 17 NOS. 3–4


et al., 2011) which consists of a kitchen cloth sponge
(10 × 10 cm) humidified with water and a blotting
paper on top (Figure 8). The cut Japanese papers
were smoothed out, adhesive layer face down, on
the humid blotting paper with a soft synthetic brush
(da Vinci®, No. 12). With a pair of tweezers, the acti-
vated Japanese paper strip or piece was transferred to
the verso of the verdigris. The paper strip is laid on
the verso and put in contact with a Surobake brush
(Paper Nao). The reinforcement was dried under
blotting paper and the weight of lead snakes.
During treatment, book wedges supported the books.
Results
Treatment and copper indicator paper
The BTA solution could be applied locally by brush
in the bound book without the use of a vacuum or
high pressure. The use of ethanol prevented defor-
mation of the paper and mechanical stress to the
degraded paper areas. The local application did not
lead to tears on the border of brittle and intact
paper. After one time application of a 3% BTA sol-
ution from the verso, the copper indicator paper
showed no or a light yellow reaction compared to a
strong orange reaction before the treatment.
Visually no colour changes after treatment could be
observed in the different green and brown hues in
Harmonia macrocosmica and in Civitates orbis ter-
rarum. Pictures of details of prints were taken
before and after treatment. Figure 9(a) shows a
C. Hofmann et al. Stabilization of verdigris
detail of the image of Danzig in volume II of
Civitates orbis terrarum before and Figure 9(b) after
treatment with BTA. The copper ion indicator
papers were used to monitor migration of free
copper ions again 2 years after the treatment. The
reaction was similar to the test in 2013. According
to the copper ion indicator paper, the BTA-copper
complex seems to be stable. The pre-coated
Japanese tissue papers could be used not only to
reinforce tears but also to support larger areas of
paper degraded by verdigris. The mixture of gelatine
and Klucel® G offered sufficient adhesive power.
Two years after the treatment, the reinforcements
are stable. The activated coated papers dried
quickly and did not deform very brittle paper. On
very dark areas, cream-coloured tissue papers like
KR4C proved to be less jarring than thin white
papers.
Light ageing
The light ageing was performed with five concen-
trations (1–3%) of BTA applied on Whatman filter
paper and sized rag paper. The discolouration of the
areas brushed with BTA clearly increased with the
strength of the concentration applied. Figure 10
shows on the left the Whatman samples and on the
right the rag paper samples, from top to bottom:
untreated control, 0.5, 1, 1.5, 2, 2.5, and 3% BTA.
The left part of each sample was exposed to light. In
the present experiment, any concentration above 1%
leads to clear signs of yellowing after the light ageing
conditions applied; at 3% the BTA covered area is
FIGURE 8 Materials
for the activation of pre-
coated papers.
Journal of Paper Conservation 2016 VOL. 17 NOS. 3–4 95
C. Hofmann et al. Stabilization of Verdigris
FIGURE 9 Civitates orbis terrarum, Vol. II, detail of Danzig, (a) before treatment; (b) after treatment with 3% BTA from the verso.
intensely coloured. This observation holds true for
both, Whatman and rag paper, despite of their differ-
ent paper shades, i.e. bright white in the case of
Whatman and off-white in the case of rag paper. In
conclusion, after application of BTA contact with
light should carefully be avoided. While low concen-
trations, for example 0.5 or 1% are somewhat safer,
FIGURE 10 Whatman (left) and rag paper (right) samples
after light ageing, from top to bottom: untreated control, 0.5,
1, 1.5, 2, 2.5, and 3% BTA; the left side of each sample was
exposed to light.
96 Journal of Paper Conservation 2016 VOL. 17
higher concentrations will clearly feature a stronger
impact on the colour of unaged paper. The shift in
colour depends on the initial colour of paper and
different papers may feature deviating sensitivities
towards colour changes upon BTA application.
Conclusion
The condition of verdigris depends on the composition
of the pigment, the mode of application and the paper
support. On many paper objects colouration with ver-
digris is stable. When verdigris has discoloured on
recto and verso, non-bleeding copper ion indicator
papers can help to evaluate if copper ions are
present and by the intensity of the colour, estimation
on the amount of copper ions present is also possible.
This information helps with the decision if chemical
stabilization of verdigris is necessary. Additives to ver-
digris can also cause colour change. Solutions of BTA
in ethanol are an option to complex copper ions on
paper. They can be easily prepared in a conservation
studio with due health precautions. The solution can
be applied by brush from the verso without causing
mechanical degradation on degraded paper. The
mode of application and a possible immediate colour
change has always to be pre-tested in a small area.
Penetration of the solution and hence complexation
depends on the paper support, the size and the thick-
ness of the colour layer. Copper ion indicator papers
can help to judge the effect of complexation. The
application of BTA can lead to yellowing of paper
under light. The reduction of the concentration
diminishes the risk of yellowing. The intensity of the
yellow discolouration will be perceived the more, the
brighter the paper it was applied on, is initially. In
the decision process, the need for chemical
NOS. 3–4

stabilization has to be balanced against the risk of yel-
lowing under light and the degree of discolouration of
verdigris and aged paper. Further research on the
action, possible modifications and the long-term
effect of BTA on paper is necessary.
Pre-coating of Japanese tissue papers, allows the use
of water-soluble adhesives on water sensitive media
and mobile metal ions. The treatment of Harmonia
macrocosmica and Civitates orbis terrarum showed
that the pre-coated tissue papers offer good support
even for large areas and do not cause mechanical defor-
mation of very brittle paper. Very thin and cream-
coloured papers appear discreet on colours or text.
The pre-coated Japanese tissue papers have found
wide application in the Conservation Department of
the Austrian National Library not only for verdigris
but also for the stabilization of iron gall ink.
Acknowledgements
The verdigris research project was supported by the
forMuse-programme of the Austrian Federal Ministry
of Science, Research and Economy. The project
joined the research efforts of the Conservation
Department of the Austrian National Library and the
Division of Chemistry of Renewable Resources at the
Department of Chemistry of the University of
Natural Resources and Life Sciences Vienna. Light
ageing was done at the Institute of Wood Technology
and Renewable Materials at the Department of
Material Sciences and Process Engineering at the
University of Natural Resources and Life Sciences,
Vienna. We would like to thank Mr Gerhard
Emsenhuber for his support with the light ageing
chamber and Prof. Wolfgang Gindl-Altmutter, head
of Institute, for kindly allowing the use of the
chamber. Colleagues in the Conservation
Department, the Collection of Manuscripts and Rare
Books and the Pictures Archive and Graphic
Collection at the Austrian National Library supported
the work presented with their expertise and their advice.
Suppliers
Australco, Bahnstraße 16, 2104 Spillern, Austria, Tel.:
+43 2266 81107-0, www.australco.at. (Ethanol
PRIMA 96%)
Farben Wolf, Margaretenstraße 124, 1050 Vienna,
Austria, Tel.: +43 1 544 83 75,
www.farbenwolf.at. (Silicone resin ELASTOSIL
M 4641 A/B, RTV-2)
Gabi Kleindorfer, Aster Str. 9, Kapfing, 84186 Vilsheim,
Germany, Tel.: +49 8706-1094, www.gmw-shop.de.
C. Hofmann et al. Stabilization of verdigris
(photographic gelatine type Restauration 1, Klucel
G, book supports, lead snakes)
Kremer Pigmente, Hauptstr. 41-47, 88317 Aichstetten,
Germany, Tel.: +49 7565-91448, www.kremer-
pigmente.de. (verdigris [Grünspan synthetisch]
No. 91448)
Paper Nao, 4-37-28 Hakusan Bunkyo-ku, Tokyo 112-
0001 Japan, Fax: 03-3944-4699,
www.papernao.com. (RK00, RK0, RK1,
Surokami bake No. 10 and 9)
Practice in Conservation, Email: eliza@practice-in-
conservation.com. (Dutch Fe-Migration Mending
Test)
Putrich & Sohn, Vordere Zollamtstraße 11, 1030
Vienna, Austria, Tel.: +43 1 715 11 76-0,
www.putrich.at. (blotting paper Canson 250 g m−2)
Römerturm, Alfred-Nobel Str. 19, 50226 Frechen,
Germany, www.roemerturm.de. (KR4C)
Sigma-Aldrich, Marchettigasse 7/2, 1060 Vienna,
Austria, Tel.: +43 1 605 81 10, www.sigmaaldrich
.com/austria. (bathocuproine Nor. 140910)
Gangolf Ulbricht, Mariannenplatz 2, 10997 Berlin,
Germany. Tel.: +49 30 615 81 55, Email:
gangolf.ulbricht@p-soft.de. (custom made rag
paper)
VWR, Graumanngasse 7, 1150 Wien, Austria, Tel.:
+43-1-97002-0, http://at.vwr.com. (1-H-
Benzotriazole zur Synthese, Merck Art. 8.22315-
1000, hydroquinone, acetone, chloroform,
Merck indicator strips pH 4.0-7.0, Merck Art.
9542)
References
Ahn, K., Hartl, A., Hofmann, C., Henniges, U. &
Potthast, A. 2014. Investigation of the
Stabilization of Verdigris-Containing Rag Paper
by Wet Chemical Treatments. Heritage Science, 2
(12). http://www.heritagesciencejournal.com/
content/2/1/12.
Ahn, K., Hofmann, C., Horsky, M. & Potthast, A.
2015. How Copper Corrosion can be Retarded –
New Ways Investigating A Chronic Problem for
Cellulose in Paper. Carbohydrate Polymers,
134:136–143.
Banik, G. & Ponahlo, J. 1982. Some Aspects of
Degradation Phenomena of Paper Caused by
Green Copper-Containing Pigments. The Paper
Conservator, 7:3–7.
Belhadi, O., Phan Tan Luu, C., Jacobi, E.,
Meslet-Struyve, S., Vez, S., Reissland, B. &
Rouchon, V. 2014. The Dutch Fe-Migration
Mending Test. Journal of Paper Conservation, 15
(1): 9–15.
Journal of Paper Conservation 2016 VOL. 17 NOS. 3–4 97
C. Hofmann et al. Stabilization of Verdigris
Boltz von Ruffach, V. 1913. Illuminierbuch – Wie man
allerlei Farben bereiten, mischen und auftragen
soll. In: E. Berger ed. Sammlung Maltechnischer
Schriften Band IV. München: Georg
D. W. Callwey, pp. 74–76, 103–105.
Clarke, M. 2011. Mediaeval Painteŕs Materials and
Techniques: The Monpellier Liber Diversarum
Artium. London: Archetype Publications, pp.
112–115.
Faerber, I. 2007. Kupferfraß auf Papier.
PapierRestaurierung, 8(1):21–29.
Füssl, S. 2011. Städte der Welt: 363 Kupferstiche
revolutionieren das Weltbild. Köln: Taschen Verlag.
Henniges, U., Schröter, K. & Potthast, A. 2005.
Tapeten und Kupferfraß. Berlin: Berliner
Wissenschafts Verlag, pp. 17–26.
Hofmann, C., Hartl, A., Ahn, K., Faerber, I.,
Henniges, U. & Potthast, A. 2015. Studies on the
Conservation of Verdigris on Paper. Restaurator,
36(2): 147–182.
Hulthe, P. 1970. A Bathcuproine Reagent-Paper for
the Rapid Semi-Quantitative Determination of
Copper in the 1 to 70 ppm Range. The Analyst,
95:351–355.
Jacobi, E., Reissland, B., Phan, C., Luu, T., van
Velzen, B. & Ligterink F. 2011. Rendering the
Invisible Visible: Preventing Solvent-Induced
Migration During Local Repairs on Iron Gall
Ink. Journal of Paper Conservation, 12
(2):25–38.
Madsen, H.B. 1985. Benzotriazole: A Perspective. In:
Corrosion Inhibitors in Conservation. London: The
United Kingdom Institute for Conservation, pp.
19–20.
Maitland, C. 2009. Where Archival and Fine Art
Conservation Meet: Antioxidant and
Deacidification Treatment of Corrosive Copper
Wallpapers and Copper Containing Iron Gall
Inks. In: J. Hinz ed. AIC, The Book and Paper
Group Annual, Vol. 28. Washington, DC: Edwards
Brothers Inc., pp. 37–46.
Malešič, J., Kolar, J. & Anders, M. 2015. Evaluation
of Treatments of Stabilization of Verdigris and
Malachite Containing Paper Documents.
Restaurator, 36(4):283–305.
Pataki, A. 2009. Remoistenable Tissue Preparation
and its Practical Aspects. Restaurator, 30
(1):51–69.
Potthast, A., Röhrling, J., Rosenau, T., Borgards, A.,
Sixta, H. & Kosma, P. 2003. A Novel Method for
the Determination of Carbonyl Groups in
Cellulosics by Fluorescence
Labeling. 3. Monitoring Oxidative Processes.
Biomacromolecules, 4:743–749.
Sease, C. 1978. Benzotriazole: A Review for
Conservators. Studies in Conservation, 23:76–85.
98 Journal of Paper Conservation 2016 VOL. 17
Titus, S., Schneller, R., Huhsmann, E., Hähner, U. &
Banik, G. 2009. Stabilising Local Areas of Loss in
Iron Gall Ink Copy Documents from the Savigny
Estate. Restaurator, 30(1):16–50.
Tse, S., Trojan-Bedynski, M. & St-Jacques, D. 2012.
Treatment Considerations for the Haggadah
Prayer Book: Evaluation of Two Antioxidants for
Treatment of Copper-Containing Inks and
Colorants. In: R. Wolcott, ed. The Book and Paper
Group Annual 31. Washington, DC: Edwards
Brothers Inc., pp. 87–97.
Van Gent, R.H. 2006. The Finest Atlas of the Heavens:
Andreas Cellarius, Harmonia Macrocosmica of
1660. Köln: Taschen Verlag.
Die Stabilisierung von Verdigris
Bei der Konservierung eines Himmelsatlas und einer
Serie von Druckschriften mit Städteansichten aus der
Zeit der Renaissance wurden die Ergebnisse eines
Forschungsprojektes zu Grünspan auf Papier
angewandt. Papier, das durch Grünspan beschädigt
war, wurde durch das Auftragen von Benzotriazol,
einem Komplexbildner für Kupfer, in Ethanol mit
dem Pinsel chemisch stabilisiert. Risse und brüchige
Stellen wurden mit beschichtetem Japanpapier
mechanisch stabilisiert. Der Kupferionengehalt und
der Effekt der Komplexierung wurden mit selbst
hergestellten Kupferindikatorpapieren überprüft.
Papierproben mit verschiedenen Konzentrationen von
Benzotriazole wurden am Licht gealtert, um die
Vergilbung zu bewerten.
Authors
Christa Hofmann graduated from the conservation
programme at the Academy of Fine Arts in Vienna
specializing in paper conservation. She worked as a
fellow at the Conservation Analytical Laboratory of
the Smithsonian Institution and received further
training in photo conservation during internships in
the USA and France. She is working as paper and
photograph conservator at the Austrian National
Library, where she has been Head of Conservation
since 2003.
Austrian National Library, Institute of
Conservation, Josefsplatz 1, 1015 Vienna, Austria.
Tel.: +431 53410-322,
christa.hofmann@onb.ac.at,
https://www.onb.ac.at/forschung/institut-fuer-
restaurierung/
Andreas Hartl studied paper conservation as well as
conservation of modern and contemporary art at the
Academy of Fine Arts Vienna. From 2011 to
NOS. 3–4

November 2014, he was working at the Austrian
National Library in Vienna. Currently, he is part-
time employed at the graphic collection of the
Academy of Fine Arts Vienna and is working as a
conservator in private practice.
Austrian National Library – Institute of Con-
servation, Josefsplatz 1, 1010 Vienna, Austria.
hartl@papiermoderne.at
Kyujin Ahn gained an MSc in conservation science at
De Montfort University in Leicester, UK, in 2000.
From 2001 to 2003, she took a Mellon fellowship at
Los Angeles County Museum of Art after an
internship at Victoria and Albert Museum and was
employed at Samsung Museum of Art, Leeum in
Seoul, Korea, until 2008. In 2013, she received her
PhD under Prof. Potthast at the University of
Natural Resources and Life Sciences, Vienna
(BOKU Wien) and worked as a postdoctoral
researcher till 2016, March. Currently, she works as
a conservation scientist at the Archival Preservation
and Restoration Center, National Archives of
Korea.
University of Natural Resources and Life Sciences –
Department of Chemistry, Division of Chemistry of
Renewable Resources, Muthgasse 18, 1190 Vienna,
Austria.
Tel.: +431-47654-77412.
kyujinahn@korea.kr.
Kristina Druceikaite gained an MSc in chemistry at
Vilnius University, Vilnius, Lithuania, in 2014. In
2013, she took an internship at University of
Natural Resources and Life Sciences, Vienna
(BOKU). From 2014 to 2015, she was working in
Vilnius University, Heritage Collections and
Research Centre, Department of Restauration
as a chemist. Currently, she is working as a
junior researcher at a biotech company called
‘Ferentis’.
University of Natural Resources and Life Sciences –
Department of Chemistry, Division of Chemistry of
Renewable Resources, Muthgasse 18, 1190 Vienna,
Austria.
Tel.: +431-47654-77412.
druceikaite@gmail.com
C. Hofmann et al. Stabilization of verdigris
Ute Henniges received a PhD in 2008 from the
University of Natural Resources and Life Sciences,
Vienna (BOKU) and is a trained paper conservator.
From 1999 to 2003, she studied conservation of paper-
based cultural heritage at the Academy of Art and
Design in Stuttgart (Germany). In 2002/2003, she
received a grant from the Landesstiftung Baden-
Württemberg for the Universitat Politècnica de
Catalunya in Terrassa (Spain). From 2003 to 2005, she
was employed at PAL Preservation Academy GmbH
Leipzig as a paper conservator. Since 2008, she works
as a researcher at the Department of Chemistry,
University of Natural Resources and Life Sciences,
Vienna (BOKU).
University of Natural Resources and Life Sciences –
Department of Chemistry, Division of Chemistry of
Renewable Resources, Muthgasse 18, 1190 Vienna,
Austria.
Tel.: +431-47654-77414,
ute.henniges@boku.ac.at,
http://www.chemie.boku.ac.at/wpf/arbeitsgrup
pen/wissenschaft-in-der-papierrestaurierung-ute-
henniges/.
Antje Potthast received a PhD in chemistry from the
Dresden University of Technology and was visiting
scientist at North Carolina State University in Raleigh
(U.S.A.). Since 1998, she is affiliated with the
University of Natural Resources and Life Sciences,
BOKU, Vienna where she finished her habilitation
(venia docendi) in ‘Wood Chemistry’ in 2003.
Currently, she is Associate Professor at the University
of Natural Resources and Life Sciences (BOKU) in
Vienna (Austria) and heads the group of biopolymer
and paper analytics. Together with Thomas Rosenau,
she leads the Christian-Doppler-Laboratory ‘Modern
cellulose chemistry and analytics’.
University of Natural Resources and Life Sciences –
Department of Chemistry, Division of Chemistry of
Renewable Resources, Muthgasse 18, 1190 Vienna,
Austria.
Tel.: +431-47654-77412,
antjepotthast@boku.ac.at,
http://www.chemie.boku.ac.at/wpf/arbeitsgrup
pen/biopolymer-und-papieranalytik-antje-pot
thast/.
*Corresponding author: Christa Hofmann
Journal of Paper Conservation 2016 VOL. 17 NOS. 3–4 99