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On the role of tannins and iron in the Bogolan or mud cloth dyeing process

Article in Textile Research Journal · November 2012

DOI: 10.1177/0040517512452955

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Original article
Textile Research Journal
82(18) 1888–1896

On the role of tannins and iron in the ! The Author(s) 2012

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Bogolan or mud cloth dyeing process DOI: 10.1177/0040517512452955
trj.sagepub.com

Mukta V Limaye1,2, Zoltán Bacsik1, Christina Schütz1,2,

Aı̈ssata Dembelé3, Mama Pléa3, Linnéa Andersson1,
German Salazar-Alvarez1,2 and Lennart Bergström1

Abstract
We have investigated the chemistry of the Bogolan or mud cloth dyeing process, a traditional technique of coloring
cotton cloths deeply rooted in Mali. Textiles produced by the traditional Bogolan process, using tannin-rich plant extract
and iron-rich clay-based mud, were compared using infrared (IR) spectroscopy, scanning electron microscopy (SEM) and
X-ray absorption near-edge spectroscopy (XANES) with cotton fibers that were impregnated with tannin and iron salt
solutions. IR spectroscopy in both reflective mode on the cloth and cotton and in transmission mode on single fibers,
together with SEM, showed that gallic and tannic acid adsorb and precipitate onto the cotton fiber surface. IR
spectroscopy and comparison with tannin and iron solution-impregnated cotton showed that the black color of the
traditional Bogolan cloth is dominated by the formation of iron-tannin complexes. The presence of iron in the Bogolan
cloth was confirmed using XANES data, supporting the notion that iron has been transferred from the iron-rich
clay-based mud to the cloth. The chemistry of Bogolan cloth is not only historically and culturally significant and of
importance in textile conservation, but may also inspire future research on sustainable dyeing and processing techniques
based on natural products.

Keywords
Bogolan dyeing, tannins, clay, cotton, mud cloth

Bogolan or mud cloth is a traditional, handmade
African textile indigenous to the Bamana Tribe of
Mali, where it has been produced and worn for
generations.1,2 Bogolan is also known as bogolanfini,
bogo meaning ‘‘mud’’, lan meaning ‘‘with’’ and fini
meaning ‘‘cloth’’.3 Bogolan is unique both in technique
and in style, which has made the cloth appealing also in
recent times.1,4
The Bogolan dyeing follows a specific and unique
procedure that utilizes natural products: textile, plants
(rich in tannins) and clay-based mud (rich in iron).3,5
The mud, which contains organic matter, is collected
from still ponds or parts of the Niger river and stored in
covered jars for up to a year prior to use. The textile
consists of white cotton strips that are stitched together
into a cloth of desired shape and size. Leaves and
branches from the evergreen tree known as African
birch or n’gallama (Anogeissus leiocarpa) are mashed
and soaked in water for 24 hours or boiled for a
few minutes. The textile is impregnated with this
brown-colored leaf extract and dried in the sun. The
process is repeated until the textile acquires a deep
yellow color, which stems from some of the extracts
released by the soaking or boiling of the leaves.
Patterns are then drawn with a pointy object on the
impregnated cloth using the blackish clay-based mud
paste. After drying in the sun, the patterned textile is
1
Department of Materials and Environmental Chemistry, Stockholm
University, Sweden
2
Wallenberg Wood Science Center, Royal Institute of Technology,
Sweden
3
Laboratoire de Physico-Chimie des Matériaux, FAST, Université de
Bamako, Mali
Corresponding author:
Lennart Bergström, Department of Materials and Environmental
Chemistry, Arrhenius Laboratory, Stockholm University, SE-106 91
Stockholm, Sweden.
Email: lennart.bergstrom@mmk.su.se
Limaye et al.
washed with water to remove any excess mud, leaving
black or brown designs on a yellow background.6
This process can be repeated several times to obtain
increasingly darker shades of color. Finally, the
yellow background is bleached using a solution of
millet bran, caustic soda and ground peanuts to
render it white. This process yields a dyed cloth
that has a high fastness and retains its dark color for
a long time.
There are only a few reports describing the Bogolan
dyeing process in more detail, primarily from handi-
craft or artistic viewpoints.1–5 Donne7 was the first to
investigate this ‘‘cumbersome’’ process from a chemical
perspective, succeeding in identifying the importance of
the tannins and iron oxide to produce the brown or
black color. Recently, Blanchart et al.6 presented a
thorough investigation of two of the main components
in the Bogolan dyeing process: Balengué clay and
n’gallama leaves, showing that the Balengué clay is
iron rich and that the n’gallama leaves are rich in
tannins, primarily ellagic, gallic acid (GA) and tannic
acid (TA).
Useful information on how black pigments can form
through reactions between iron salts and tannins can be
obtained from the numerous studies on iron-gall
inks,8–17 which was the dominating writing inks used
in Europe since the 12th century until the introduction
of synthetic inks in the late 19th century. Iron-gall inks
were generally prepared by mixing iron(II) sulfate with
a solution of fermented oak galls, which are rich in GA,
and gum Arabic, which provides the desired rheology
and also acts as a binder. It is interesting to note that
iron-gall inks tend to slowly become darker after appli-
cation, an effect that has been connected to the oxida-
tion of the iron ion from the Fe2+ to the Fe3+
state.11,12 Unfortunately, iron-gall inks can result in a
degradation of the paper or vellum (skin) they are
applied to, a challenge that has motivated many studies
on, for example, paper degradation.11–14 Although the
acidity of the ink and a possible excess of Fe2+ ions has
been identified as possible causes for the degradation of
iron-gall ink documents,12 the mechanisms are complex
and many ancient documents do not show any signs of
damage or degradation by the iron-gall inks.
This study aims to elucidate the chemistry of the
Bogolan dyeing process by characterizing both cloth
dyed using the traditional process and cotton treated
with only some of the main components, that is, GA
and TA, and Fe(II) or Fe(III) solutions, which is
referred to as model Bogolan cotton. The traditional
and the model textiles have been characterized by a
combination of infrared (IR) spectroscopy, scanning
electron microscopy (SEM) and X-ray absorption
near-edge spectroscopy (XANES). The interaction
between the tannins and the cellulose and the formation
1889
of color pigments on the cotton fibers has been demon-
strated. The oxidation state and the transfer of iron
from iron-rich clay-based mud to the cotton cloth are
discussed based on the XANES data.
Experimental details
Materials
Traditional Bogolan or mud cloth, n’gallama leaves
and Balengué clay were obtained from Mali, Africa.
The cloth was prepared in Mali using the traditional
Bogolan dyeing process described earlier by treating a
hand-woven textile with n’gallama leaves and Balengué
clay-based mud.
Layered cotton was used as obtained. GA (C7H6O5),
TA (C76H52O46), FeCl36H2O, FeCl24H2O and
FeSO47H2O were purchased from Sigma Aldrich and
used as received.
Cotton fibers were treated with GA and TA. A small
piece (around 1 cm3) of cotton was soaked for 5 min-
utes in an aqueous solution containing concentrations
of 0.005 M and 0.001 M of GA and TA, respectively
(M ¼ mol/dm3). The treated cotton (hereafter referred
to as acid-treated cotton) was dried under ambient con-
ditions. For the sake of comparison, cotton fibers were
also treated with n’gallama leaf extract. The GA and
TA-treated cotton were impregnated with different iron
solutions (FeCl3/FeCl2/FeSO4) of concentration
0.025 M and 0.005 M, respectively, and then dried
under ambient conditions. The acid and iron salt solu-
tion-treated cotton are referred to as model Bogolan
cotton.
Characterization
A Varian 610-IR Fourier transform infrared (FTIR)
spectrometer was used to probe the molecular inter-
actions of the starting materials and the dyed cotton
and Bogolan cloth. The FTIR spectrometer was
equipped with an attenuated total reflection (ATR)
accessory (Specac) with a single-reflection diamond
ATR element. Measurements were normally performed
by accumulating 64 scans in the spectral region of
4000–390 cm1 with a spectral resolution of 4 cm1.
IR spectra of the black and white regions of traditional
Bogolan cloth were obtained by pressing the cloth
against the diamond ATR element without destruction
of the cloth. IR spectra of the model Bogolan cotton
were also obtained following this procedure, together
with a technique where a single fiber (around 3–5 mm
long and 10 mm diameter) was extracted from the
traditional and model Bogolan cloth and placed in a
diamond anvil cell. Approximately a 60  60 mm2
area can be investigated using a diamond anvil cell.
1890
The fiber section was examined by setting the aperture
of a Varian 610-IR microscope in transmission mode
(see Supplementary data Figure S1).
The morphological analysis was performed using a
JEOL 7000 field emission gun scanning electron micro-
scope. The samples were prepared by placing some
fibers from the acid-treated and model Bogolan
cotton on aluminum stubs using carbon double-sided
tape and coating with a thin layer of amorphous
carbon. The secondary electron images were recorded
using accelerating voltage of 1 kV and with a medium
probe current.
Room temperature Fe K-edge X-ray absorption
near-edge spectra (XANES) were recorded at the Max
lab beamline I811 in Lund, Sweden. The intensity of the
X-ray beam with a sample spot size of 0.5  0.5 mm2
was measured with three ionization chambers. A metal-
lic Fe foil was used as a reference during acquisition.
The data were recorded in transmission mode and
fluorescence mode. The Bogolan sample for XANES
measurements was prepared by scraping off a small
amount (a few micrograms) of fibers from the surface
of the black section of a traditional Bogolan cloth. The
sample was glued onto Kapton tape and mounted in
between the first and second ionization chambers and
positioned at 45 with respect to the incident photon
beam. The reference metallic Fe foil was inserted in
between the second and third ionization chambers.
The absorption spectra were recorded in the range
of  150 eV with respect of the Fe K-edge (7112 eV).
The data were acquired with a varying step size, that
is, for the range (150 to 50 eV) a step size of 5 eV
was used, whereas for the ranges (50 to 30 eV) and (30
to 150 eV) step sizes of 0.25 eV and of 1 eV were used,
respectively. The acquisition time for the XANES data
was 45 min for each spectrum. The short measure-
ment time and sufficiently large spot size makes
photon-induced changes unlikely.12,17
Results and discussion
We have characterized traditional Bogolan cloth and
model Bogolan cotton by a combination of IR spec-
troscopy, SEM and XANES. Figure 1 exemplifies the
distinct dark patterns on a white background that are
typical for a traditional Bogolan cloth. The IR spec-
trum recorded from a black region of the textile
(Figure 2) shows the typical bands (in the regions
1200–900 cm1, 1500–1200 cm1 and 790–580 cm1)
for cotton and an intense broad band in the range of
1760–1500 cm1. Tannins, such as GA or TA, have the
characteristic carbonyl (C ¼ O) band around 1700 cm1
and aromatic ring C ¼ C stretching around
1600 cm1.18,19 Impregnation of tannins on the cotton
results in superimposition and broadening of the
Textile Research Journal 82(18)
Figure 1. Photograph of traditional Bogolan or mud cloth
displaying the typical black and white patterns.
bands.19 The spectrum of the bleached, white part of
the textile looks similar to that of untreated cotton. The
carbonyl band of the bleached part is less intense com-
pared to the black part, indicating that most of the
tannins have been removed. However, features still pre-
sent in the 1760–1500 cm1 region suggest that some
tannins remain. The distinct and narrow OH bands at
3620 and 3700 cm1 characteristic for the Balengué clay
are present in both the dark and white (bleached)
regions of the traditionally dyed Bogolan cloth.
Interestingly, spectroscopic analysis carried out on
historic manuscripts written using iron-gall inks
also showed an intense broad carbonyl band in the
1750–1500 cm1 region compared to pure cellulose.14,20
This similarity between the two processes may already
suggest a similar chemistry of iron-gall inks and
Bogolan dyeing.
We have also used another sampling technique that
allows IR spectra to be obtained from single fibers of
the traditional Bogolan cloth. Placing a single cotton
fiber in a diamond anvil cell yields a well-defined, suf-
ficiently thin section of the fiber (see Supplementary
data Figure S1) that allowed IR spectra to be retrieved
in the transmission mode. The measurements on the
single fiber shown in Figure 3 confirm the features
observed from the ATR-measurements shown in
Figure 2, with a prominent contribution from the
cotton and intense absorption bands related to
carbonyl groups on the black fiber. The absence of dis-
tinct and narrow OH bands at 3620 and 3700 cm1
indicates that the contribution from the clay is less pro-
nounced in the single fiber measurements.
Figure 4 shows the IR spectra of the n’gallama leaf
and the cotton treated with n’gallama extract. The spec-
trum of a leaf native to Mali shows typical bands of
cellulose, which of course relates to the matrix of the
Limaye et al. 1891

Figure 2. Infrared (IR) spectra of cotton retrieved from the (a) black section and (b) white (bleached) section of a traditional
Bogolan or mud cloth. The IR spectra of untreated cotton and Balengué clay are shown in (c) and (d), respectively. The inset figure
display the respective sampling areas of the black and white regions of the traditional Bogolan cloth.

Figure 3. Transmission infrared spectra of single fibers of (a)
untreated cotton, (b) cotton treated with n’gallama leaf extract,
(c) the white (bleached) part of the traditional Bogolan cloth and
(d) the black part of the traditional Bogolan cloth.
leaf. In addition, we can also identify intense bands for
-CH2- fragments at 2920 and 2851 cm1, characteristic
for long chain alkanes, a C ¼ O band at 1723 cm1, and
a C ¼ C aromatic ring stretching at 1600 cm1 typical
Figure 4. Infrared spectra of (a) n’gallama leaf, (b) untreated
cotton and (c) cotton treated with n’gallama leaf extract.
for the tannins present in these leaves.21 The cotton
treated with solutions of n’gallama leaf extract shows
a C ¼ O and C ¼ C stretching region that is nearly iden-
tical to the n’gallama leaf, indicating that the tannins
from the leaves are dissolved and attached to the sur-
face of the cotton. The very broad band between 3300
1892 Textile Research Journal 82(18)

Figure 5. Photographs of cotton treated with (a) gallic acid (GA) and FeCl3, (b) GA and FeCl2, (c) GA and FeSO4, (d) tannic acid
(TA) and FeCl3, (e) TA and FeCl2 and (f) TA and FeSO4.

Figure 6. Scanning electron microscopy images of (a) and (b) cotton treated with gallic acid (GA) and (c) and (d) cotton treated with
GA and FeSO4. The inset shows a magnified region of (d). The images were modified using GIMP 2 software.
Limaye et al. 1893

Figure 7. Infrared spectra of (a) cotton, (b) cotton treated with gallic acid (GA) (cotton+GA), (c) the difference spectrum
((cotton+GA)–cotton) and (d) GA. The magnified region of the spectra between 1800 and 1500 cm1 is shown on the top right-hand
side. Infrared spectra of (e) cotton, (f) cotton treated with tannic acid (TA) (cotton+TA), (g) the difference spectrum
((cotton+TA)–cotton) and (h) TA. The magnified region of the spectra between 1800 and 1500 cm1 is shown on the bottom
right-hand side.

and 2500 cm1 can be attributed to H-bonded OH
groups.
We have treated cotton with two different tannins –
GA and TA – which are found in n’gallama leaves and
n’gallama leaf extract (Figure S2 in Supplementary
data). Subsequently, we have treated the cotton with
iron solutions to elucidate the chemistry of the
Bogolan dying process in detail. Figure 5 shows that
the treatment with GA and Fe(II) salt solutions
produces a deep black color of the treated cotton,
whereas combination with Fe(III) salt solution
produces less intense brown or gray colors.
Interestingly, the color of the cotton impregnated
with TA displays much smaller differences in blackness
after reaction with Fe(II) or Fe(III) salt solutions.
The SEM images of the cotton fibers shown in
Figure 6 show that treatment with GA results in the for-
mation of small particles on the fiber surface. The par-
ticles have an angular shape and the size is of the order
of a few micrometers. The microscopic images of the
cotton fibers impregnated with GA (0.005 M) and
FeSO4 (0.025 M) also show the presence of some
1894 Textile Research Journal 82(18)

Figure 8. Infrared spectra of (a) cotton treated with gallic acid (GA) and (b) cotton treated with GA and FeSO4. The magnified
region of the spectra between 1800 and 1500 cm1 is shown on the top right-hand side. Infrared spectra of (c) cotton treated with
tannic acid (TA) and (d) cotton treated with TA and FeSO4. The magnified region of the spectra between 1800 and 1500 cm1 is
shown on the bottom right-hand side.

particles (Figure 6(c)), suggesting that the formation of
GA precipitates during the first step of the dying
process, which is important for the subsequent in situ
formation of the iron-gall pigments on the cotton
fibers.
The concentrations of GA and TA used to impreg-
nate the cotton were adjusted (0.005 M and 0.001 M,
respectively) for the interpretation of the IR spectra.
When acid is in excess (0.070 M GA and 0.025 M
TA), the bands observed in the IR spectra of the
acid-treated cotton samples are dominated by the free
acid (Supplementary data Figure S3). The concentra-
tions of the acids were adjusted in order to observe the
changes in the carbonyl region, which corresponds only
to the acid molecules adsorbed on the cotton. Figure 7
shows IR spectra of cotton treated with dilute (0.005 M
GA and 0.001 M TA) solutions of acids. Detailed assig-
nation of the bands in the GA spectrum can be found
elsewhere;18 here we have concentrated on the carbonyl
stretching region. The untreated cotton has a carbonyl
band at 1637 cm1 (Figure 7(a)) and pure GA shows a
characteristic carbonyl band at 1698 cm1 and C ¼ C
aromatic ring stretching at 1610 cm1 (Figure 7(d)).
The GA-treated cotton shows a broad band in the
region 1711–1576 cm1 (Figure 7(b)), indicating that
the treatment of GA with cotton causes superimpos-
ition and broadening of the bands. The difference spec-
trum obtained by subtracting the contribution of
Limaye et al. 1895

unmodified cotton from the spectrum of cotton treated

with GA is a convenient way to visualize differences
between the two spectra. Indeed, the similarity between
the difference spectra (Figure 7(c)) and the spectrum of
the pure GA (Figure 7(d)) confirms that GA adsorbs
onto the cotton fibers. It can also be observed that the
C ¼ O band present at 1698 cm1 in pure GA was
shifted to 1686 cm1 in the difference spectrum. The
explanation for the shift is not straightforward, but
suggests that the carbonyl group of the acid (at least
partially) interacts with the cellulose. A possible explan-
ation for the shift can be the participation of the car-
bonyl group in hydrogen bonding with functional
groups on the cotton surface. Unfortunately, it is not
possible to identify conclusively the changes in the OH
stretching region from the complex difference spectra.
The IR spectrum of the cotton treated with TA is
shown in Figure 7(f). The TA-treated cotton sample
shows two absorption bands at 1610 and 1706 cm1,
which correspond to the aromatic ring C ¼ C stretching
and carbonyl (C ¼ O) stretching, respectively, of TA.19
The shift of the C ¼ O band present at 1696 cm1 in
pure TA (Figure 7(h)) to 1706 cm1 in the difference
spectrum (Figure 7(g)) suggests that the carbonyl
group of the TA (at least partially) interacts with the
cellulose.
The IR spectra of the model Bogolan cotton first
impregnated with GA or TA and then treated with
FeSO4 are shown in Figure 8. The spectra of model
Bogolan cotton treated with both acids and all three
iron salts are shown in the Supplementary data Figure 9. Fe K-edge X-ray absorption near-edge spectroscopy
Figure S4. The broad band in the carbonyl region, spectra of (a) Fe foil, (b) traditional Bogolan cloth and (c)
which is characteristic for the cotton treated with GA Balengué clay.
or TA (see Figure 7), becomes broader after treatment
with FeSO4. The intensity of the carbonyl band for small shoulder is observed at 7147 eV, which indicates
the FeSO4-treated samples also increases compared the presence of iron oxides or iron oxyhydroxides.24,25
to the acid-treated samples, using the most intense This corresponds well with previous observations,6
band of the cotton in the 1200–900 cm1 region as an which suggested that Balengué clay contains akaganeite
internal reference. The similarity between the broad, (b-FeOOH). The Fe K-edge XANES data clearly
intense carbonyl band found in the model Bogolan shows that the Bogolan cloth also contains iron. This
cotton samples and the traditional Bogolan cloth, and observation suggests that the iron originally present in
the previously studied iron tannates22 and iron gall- the clay is transferred at least partially to the cloth
ates23 indicates the presence of these species on the sur- during the process of dyeing, as no other material
face of the treated cotton. However, a detailed analysis except the clay contains iron. The XANES data
of the IR spectra is not possible, as the iron complex shows that the transfer of iron occurs without change
has a similar spectrum in the carbonyl region to that of of oxidation state.
the adsorbed acids on the surface of the cotton.
XANES is a sensitive tool for the determination of
the oxidation state of iron. Figure 9 shows the Fe
Conclusions
K-edge XANES spectra of Bogolan cloth, Balengué We have studied the chemistry of the traditional
clay and Fe reference foil. The Bogolan cloth and Bogolan or mud cloth and the interaction between
Balengué clay display a pre-edge (1 s ! 3 d transition) cotton, tannins and iron salts. Studies on cotton fibers
at 7115 eV, which is characteristic of Fe(III). An edge treated with GA and TA and iron solutions by mainly
(1 s ! 4 p transition) is observed at 7133.7 eV for both IR spectroscopy showed that the GA and TA adsorb
the Bogolan cloth and Balengué clay. In the clay, a on the cotton surface. The IR measurement of a single
1896
fiber is a promising technique to characterize small
quantities of samples and it show similar features
observed from the ATR measurements. The similarity
of the IR spectra for the black regions of the traditional
Bogolan cloth and cotton treated with tannins and iron
solution suggests that the dying process is dominated
by the formation of iron-tannin complexes. SEM con-
firmed the formation of precipitates on the cotton fibers
after treatment with GA and FeSO4. The unusually
high color fastness of old Bogolan cloth suggests that
the iron originally present in the clay is transferred to
the cloth where it interacts with tannins, resulting in
dark pigments strongly bound to the cotton fiber
surfaces.
Acknowledgements
The Knut and Alice Wallenberg Foundation and Max lab,
Lund, Sweden, are acknowledged for the electron microscopy
facilities at Stockholm University and the allocation of beam
time, respectively. We also thank Katarina Norén and Tom
Willhammar for assistance and support during the XANES
experiments and taking photos of the Bogolan samples
respectively.
Funding
The work was supported by Wallenberg Wood Science Center
(WWSC). MP and AD were supported by the International
Science Programme, Uppsala University.
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