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Microchemical Journal 88 (2008) 186 193

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Analysis of lignin from archaeological waterlogged wood by direct exposure

mass spectrometry (DE-MS) and PCA evaluation of mass spectral data
F. Modugno a,, E. Ribechini a , M. Calderisi a , G. Giachi b , M.P. Colombini a
a

Dipartimento di Chimica e Chimica Industriale, Universit di Pisa, Via Risorgimento 35, I-56126 Pisa, Italy
Soprintendenza ai Beni Archeologici per la Toscana, Laboratorio di Analisi-Centro di Restauro, Largo del Boschetto 3, I-50135 Firenze, Italy
Received 3 August 2007; accepted 21 November 2007
Available online 8 January 2008

Abstract
The chemical characterisation of waterlogged archaeological wood is of fundamental importance to understand the degradation processes
undergone by wooden objects and consequently to develop suitable consolidation and conservation procedures. Lignin extracted from archaeological
waterlogged wood samples was characterized using direct exposure electron ionisation mass spectrometry (DE-MS). DE-MS achieves a mass
spectral fingerprint of the sample in a few minutes, avoiding any chemical pre-treatment and requiring only few micrograms of material.
Mass spectral data were put in relation to the chemical composition of lignin and evaluated by means of principal component analysis (PCA). The
preliminary results, presented in this study, demonstrate the feasibility and the potential of DE-MS as a reproducible and rapid screening method for
archaeological waterlogged wood samples.
2007 Elsevier B.V. All rights reserved.
Keywords: Archaeological waterlogged wood; Lignin; Direct exposure electron ionisation mass spectrometry (DE-MS); Principal component analysis (PCA)

1. Introduction
The recovery, consolidation and preservation of waterlogged
wooden artefacts, such as shipwrecks and archaeological objects
recovered from underwater environments, is a particularly arduous conservation problem. Under favourable conditions of low
temperature and low oxygen availability, wood artefacts can
survive underwater in a surprisingly good state. Nevertheless, it
has been shown that some species of anaerobic bacteria can
slowly degrade waterlogged wood even under near anoxic
conditions, mainly by eroding the polysaccharides as a source of
nutrients. This leads to the formation of pores and cavities filled
with water, and transforms the wood into a soft and fragile
structure which is likely to collapse when drying [14]. Due to the
almost complete loss of cellulosic components, the chemical
characterisation of lignin is of primary importance in the
diagnosis and conservation of waterlogged wood artefacts.
Corresponding author. Tel.: +39 050 2219303.
E-mail address: frances@dcci.unipi.it (F. Modugno).
0026-265X/$ - see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.microc.2007.11.010

Lignin, a cross-linked poly-phenolic macromolecule (molecular

mass over 10,000), is insoluble in solvents and does not contain
either chains of repeating units or easily hydrolysable bonds [5].
These chemicalphysical properties make the chemical analysis
of lignin extremely complex. Infrared spectroscopy [6,7], thermogravimetric methods [8], solid state 13C-NMR [9,10] and
pyrolysis-gas chromatography based procedures [1014] have
been adopted to deal with this problem in degraded or aged wood.
The use of pyrolysis gas chromatographic techniques in combination with mass spectrometry has proven to be of particular
interest in the study of macromolecules such as lignin, cellulose
and hemicellulose. In particular, Py-GC/MS provides useful data
on the chemical structure of wood components, and has been used
for studying cellulose and lignin and also for investigating decay
processes in archaeological wood [10,12].
During pyrolysis, the macromolecules are depolymerised by
heat and the pyrolysis products can be identified by mass spectrometry, after gas chromatographic separation. Especially in the
case of lignin, pyrolysis produces a variety of phenolic products,
which consist of guaiacyl and syringyl structural units with an

F. Modugno et al. / Microchemical Journal 88 (2008) 186193

aliphatic side chain in position 4 of the aromatic ring [15]. It is

assumed that pyrolysis products represent, to a greater or lesser
degree, the structural units that make up the macromolecule.
The aim of this study was to use a direct in-source Py-mass
spectrometric technique, namely direct exposure electron ionisation mass spectrometry (DE-MS), to characterise archaeological waterlogged wood and lignin extracted from archaeological
artefacts, in order to explore the potential of this technique to
retrieve chemical information on archaeological wood materials
and to evaluate decay processes.
In DE-MS the sample undergoes a resistively controlled
heating on a rhenium filament within the ion source of the mass-

187

spectrometer. The sample components are desorbed or, in the case

of macromolecules, pyrolysed over the heating range, and are
ionised and analysed as a function of time. DE-MS requires very
small amounts of untreated sample (in the order of micrograms), it
can be performed rapidly (a few minutes for analysis and data
acquisition), and its sensitivity has been shown to be suitable for
identifying materials in the archaeometric field, with specific
applications in the analysis of wood-derived materials such as
terpenic resins [16,17]. Direct and rapid analytical methods that
avoid sample pre-treatment are particularly welcome in the
cultural heritage field, where the availability of sample is often
limited and contamination must be avoided.

Fig. 1. DE mass spectra of a) lignin extracted from archaeological wood IS, identified as Pinaceae, and b) lignin extracted from spruce sound wood.

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F. Modugno et al. / Microchemical Journal 88 (2008) 186193

The few applications of in-source pyrolysis-mass spectrometry

(direct temperature resolved mass spectrometry, DTMS) to wood
and lignin described in the literature [18,19], have highlighted that
it is possible to relate mass spectral data to the chemical composition of lignin and of wood in sediments [18]. Although
directly combining pyrolysis with mass spectrometry does not
offer the detailed chemical information accomplished by Py-GC/
MS, it nevertheless achieves a mass spectral fingerprint of the
samples within a few minutes. The application of pattern analysis
based on principal components (PCA) enables the mass profiles
obtained for the various samples to be compared quantitatively in
an easily readable manner. It also highlights similarities and
differences between samples. Moreover, the examination of
loading plots permits the differences to be correlated to specific
chemical features. This analytical approach is suitable for fast
screening even a large number of samples. It thus has great
potential, when applied to wood artefacts of large dimensions,
such as shipwrecks, where it can be used to monitor the state of
conservation of the wood in various regions of the timbers.
This first application of DE-MS to archaeological wood
shows that it is a fast fingerprint tool that is able to discriminate
between hardwood and softwood archaeological wood, and is
sensitive to differences in the chemical structure of lignin.

Unsupervised pattern recognition analysis of DE-MS mass

spectral data corresponding to the mass range 50500 m/z was
performed by principal component analysis (PCA, Nipals algorithm) on the covariance matrix of centered data, after row
normalisation of the full 501000 spectra. The region 50500 m/z
was selected because it contains all the pyrolysis fragments
corresponding to lignin monomers and dimers. The software used
was XLSTAT 6.0 (Addinsoft, Paris, France).

2. Materials and methods

3. Results and discussion

2.1. Samples

All the samples examined showed the presence of a single

peak in the total ion current (TIC) profile. The peaks show a
variable degree of broadness and in some cases the presence of

The lignin was prepared and donated by Professor M. Orlandi

of the Department of Environmental and Earth Sciences of the
University of Milano Bicocca (Milan, Italy). Lignin extraction
and isolation was carried out using a recently published procedure [9], based on a modification of the milled wood method
developed by Holmbom et al. [20]. The lignin samples were
derived from archaeological wood samples of different ages and
origins:
- two samples from bollards excavated in the Site of Ancient
Pisa Ships (Pisa, Italy), provided by the Archaeological
Superintendence of Tuscany: D (Ulmus sp), SR (hardwood,
unknown species). The archaeological artefacts from the site
are dated to a period between the 4th century BC to the 2nd
century AD;
- a wooden piece from a shipwreck found under shallow waters
(0.5 m deep) in Tantura Lagoon (Haifa, Israel) and dated 8
9th century AD, provided by the Institute of Maritime Studies
of the University of Haifa: sample IS. Previous analysis had
identified the wood as a conifer, probably from the Pinaceae
family [10];
- a wooden piece from the shipwreck Epave du Grand
Conglou recovered near Marseille (France) and dated 2nd
century BC, provided by Prof. I.D. Donato (Department of
Chemistry of the University of Palermo, Italy): B44. The
wood was identified as oak (Quercus sp.).
Recent lignin from spruce (soft wood) and birch (hard wood)
extracted with the same procedure was used as references.

2.2. DE-MS
Samples were analysed by depositing a few particles of
powder directly on the direct exposure probe filament by means
of a capillary. Each sample was analysed in duplicate.
The instrumentation (Thermo Electron Corporation, USA)
was made up of a Direct Probe Controller and a Direct Exposure
Probe (rhenium filament, current programmed mode 0 mA to
1000 mA in 2 s then 1000 mA for 60 s), coupled with a Polaris Q
ion trap external ionisation mass spectrometer (electron impact
ionisation 70 eV). The source temperature was at 230 C. The
mass spectrometer was scanned over an m/z range of 501000.
2.3. Data analysis

Table 1
Attribution of m/z peaks observed in archaeological lignin DE mass spectra
m/z

Derivation

Type of monomer G:
guaiacyl S: siringyl

124
138
150
137

Guaiacol (M+) coniferylalcohol (M+-C3H4OH)

Methylguaiacol (M+)
Vinylguaiacol (M+)
Ethyguaiacol (M+ -CH3), Propylguaiacol
(M+ -CH2CH3), Coniferylalcohol (M+-C2H2OH)
Propenylguaiacol (M+)
Acetylguaiacol (M+-CH3), Vanillin (M+-H),
Propylguaiacol (M-CH3)
Vanillin (M+)
Syringol (M+)
Methylsyringol (M+)
Ethylsyringol (M+-CH3), Propylsyringol
(M+-CH2CH3), Sinapylalcohol (M+-C2H2OH)
Propenyl-3-one-guaiacol (M+),
prop-2-enalguaiacol (M+)
Vinylsyringol (M+)
Propenylsyringol (M+)
Acetylsyringol (M+-CH3)
Propenalsiryngol (M+)
Sinapylalcohol (M+)
Stilbene-type dimer (M+)
Stilbene-type dimer (M+)
Stilbene-type dimer (M+)
-resinol type dimer (M+)
-resinol type dimer (M+)
-resinol type dimer (M+)

G
G
G
G

164
151
152
154
168
167
178
180
194
181
208
210
272
303
332
358
388
418

G
G

S
S
S
G
S
S
S
S
S
GG dimer
GS dimer
SS dimer
GG dimer
GS dimer
SS dimer

F. Modugno et al. / Microchemical Journal 88 (2008) 186193

shoulders. This is probably due to the polymeric nature of lignin

and the degree of the polymerization of lignin samples collected
from the various species of wood.
The mass spectrum is obtained by time-integration of the
main peak in the total ion current (TIC) profile. The mass
spectra show high complexity, as expected in the direct mass
spectrometric analysis of the complex mixture of products
formed in the pyrolysis of lignin.
The mass spectra of lignin sample IS from the shipwreck from
Israel (softwood) is shown in Fig. 1a and compared with the
mass spectra of the reference spruce lignin (Fig. 1b). Both the
spectra are characterised by the occurrence of peaks indicative of
a guaiacyl lignin: m/z 124, corresponding to the molecular peak

189

of guaiacol (2-methoxy-phenol); m/z 137 ([guaiacol + CH2]+),

which could derive from several compounds formed in the
pyrolysis of guaiacyl lignin including ethylguaiacol, propylguaiacol and coniferyl alcohol, by the loss of a methyl radical, an
ethyl radical and a C2H2OH. radical respectively; m/z 151
(guaiacol + CH2CH2+); m/z 152, corresponding to the molecular
ion of vanillin. The peak at m/z 272 corresponds to the molecular
peak of a guaiacyl-guaiacyl dimer compound with a stilbene
structure (3,3'-dihydroxy-4,4'-dimethoxy-stilbene).
Table 1 lists the fragments identified and the most probable
attribution, based on the mass spectra of guaiacyl and siringyl
compounds determined by Py-GC/MS [10] and available from
the literature [18].

Fig. 2. DE mass spectra of a) lignin extracted from archaeological wood SR , unknown specie, and b) lignin extracted from sound birch wood.

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F. Modugno et al. / Microchemical Journal 88 (2008) 186193

Fig. 3. DE mass spectra of lignin extracted from archaeological wood B44, identified as Quercus sp.

As can be seen in Figs. 2, 3 and 4, the mass spectra of birch

lignin (hardwood) and of samples SR, B44 and D show the
presence of peaks characteristic of guaiacyl-syringyl lignin at
m/z 124, 137, 151 deriving from guaiacyl monomers, and at m/z
167, 181, 208, 210 deriving from syringyl monomers. In
particular, the peaks at m/z 167 (syringol + CH2+) and at m/z 181
(syringol + CH2CH2+) correspond to the main ion fragments
deriving from sinapyl alcohol and alkylsyringol compounds,
while the peak at m/z 210 corresponds to the molecular ion of

sinapyl alcohol. In the mass spectra of sample D (Fig. 4), the

occurrence of peaks at m/z 196 and at m/z 153 is significant.
These peaks could derive from the demethylation reaction of
alkylsyringyl monomeric units. This reaction leads to the formation of corresponding catechol derivatives, whose fragmentation should form ion fragments at m/z 196 and at m/z 153. In
fact, the peaks at m/z 196 and at m/z 153 correspond to a loss of
14 uma from peaks at m/z 210 and m/z 167, respectively. Due to
the fact that demethylation of alkylsyringyl units is a recognized

Fig. 4. DE mass spectra of lignin extracted from archaeological wood D, identified as Ulmus sp.

F. Modugno et al. / Microchemical Journal 88 (2008) 186193

Fig. 5. PCA score plot of PC1 and PC2 of DE mass spectral data, accounting for
78.5% of total variance. IS: conifer lignin from a 89th century AD shipwreck
recovered near Haifa (Israel); B44: oak lignin from a 2nd century BC shipwreck
recovered near Marseille (France); D: elm lignin from a bollard pertinent to the
Site of Ancient Pisa Ships (Pisa, Italy); SR: D: hardwood lignin from a bollard
pertinent to the Roman Harbour of san Rossore (Pisa, Italy); spruce: reference
spruce lignin; birch: reference birch lignin.

decay index for lignin [12], the occurrence of peaks relative to

lignin demethylation products can be considered as a way to
establish the degree of degradation.
The ratio between the relative abundance of peak at m/z 167,
the most abundant from syringyl monomers, and that of peak at
m/z 137, deriving from guaiacyl monomers, can be considered
as a rough indication of the S/G ratio for the lignin sample. As
can be seen from the mass spectra, softwood samples do not
contain a peak at m/z 167, while hardwood samples show
variability in this ratio depending on the species of wood. In the
lignin mass spectra, m/z fragments deriving from residual
cellulose and hemicellulose are not evident, demonstrating the
efficiency of the extraction and purification procedure adopted
to obtain lignin. In particular, if polysaccharides had been present in not negligible amounts, on the basis of the literature [19]
and of the analysis of reference cellulose, the following m/z
fragments would have been observed: 65, 73, 85, 79, 97, 127.
In all the mass spectra obtained for hardwood and softwood
lignin, in addition to the peaks deriving from the guaiacyl and
siringyl monomer structures, peaks attributable to ion fragments
deriving from dimeric structures of the lignin macromolecule
were observed. Amongst these, the most abundant was at m/z
272, which corresponds to the molecular ion of the GG dimer
dihydroxydimethoxy-stilbene. In samples from hardwood species, peaks at m/z 302 and m/z 332 attributable to the homologue
SG and SS dimers, were also observed. Moreover, the series of
peaks at m/z 358, 388 and 418, which differ by 30 Da (OCH3), can
be attributed to GG, GS and SS dimers with - resinol type
structures [18].
Due to the complexity of the mass spectra obtained in the direct
Py-MS analysis of lignin, principal component analysis (PCA) was

191

used as a pattern recognition technique to quantitatively compare

the mass spectra obtained and to highlight differences and
similarities between samples and correlations between variables.
The DE mass spectra obtained from the archaeological lignin
examined and those from the two reference lignin extracted from
wood were compared by means of PCA. The data matrix was
constituted by the mass spectra of the samples (in replicates) in
the range m/z 50500, where the intensities of each m/z
fragment was expressed as percentage of the sum of the
intensities of all the m/z fragments in the spectra (row
normalisation). The data matrix was column-centered and the
covariance matrix was used for PCA. Fig. 5 shows the scatter
plot corresponding to the first two PCs, accounting for 78.5% of
the total variance. The following couples of similar samples can
be highlighted: spruce lignin and IS, birch lignin and DD1, and
SR and B44.
The loading plot of PC1 (Fig. 6) on the basis of the loadings
shows that this axis of variance concerns the ratio between
syringyl and guaiacyl markers. The PC1+ is indicative of syringyl
units and the PC1- of guaiacyl units. Actually, the two softwood
samples, spruce and IS, scored lowest on PC1, because they
contained only guaiacyl lignin, and they were well differentiated
from the hardwood samples. The archaeological sample D1 was
similar to the modern birch lignin, at an intermediate guaiacyl/
syringyl ratio, while the archaeological samples B44 and SR
formed a separate cluster with high syringyl content.
The scores of the samples on the PC3/PC1 map, shown in
Fig. 7, enhance the differences between archaeological (PC3+)
and modern lignin (PC3).
It seems that PC2 and PC3 might be indicative of the degree
of conservation, in fact the reconstructed mass spectra of PC2
and PC3 show that both the axes have significant loadings for
m/z 196 and m/z 153, which can be attributed to the fragmentation catechol derivatives formed by the demethylation of
the alkylsyringyl units. Peaks at m/z 153 and 196 are well
evident in the mass spectra of sample D. Moreover, PC3 showed
a positive loading for m/z 110, corresponding to the molecular
mass of catechol, which is also considered as a lignin degradation marker [12]. Neverthless, conclusions cannot be
drawn from PC3 values because this PC3 has a low significance
(only 9% of total variance) and in fact shows a non negligible
variability between replicated samples. The analysis of a higher
number of samples and the comparison of DE-MS data with PyGC/MS data will permit to better evaluate the role of the formation of catechols in the degradation processes affecting lignin
in waterlogged environment [21].
The results show that the differences in the mass spectra are
related not only to the difference between guaiacyl lignin
(spruce and IS) and guaiacyl/siringyl lignin (other samples), but
also to the ratio between guaiacyl and syringyl components and
to the degree of demethylation undergone by lignin monomers
in the course of degradation.
4. Conclusions
This preliminary study has highlighted that DE-MS is a fast
fingerprint tool which is able to discriminate between hardwood

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F. Modugno et al. / Microchemical Journal 88 (2008) 186193

Fig. 6. Loading plots of the first three PCs.

and softwood archaeological wood and which is sensitive to

differences in the chemical structure of lignin. The mass spectra
obtained can be quantitatively evaluated and compared by
means of principal component analysis, and this method would

seem to be suitable for studying degradation processes in lignin

contained in archaeological wood.
Further comparative investigations are in progress. They involve a larger number of archaeological and reference samples,

F. Modugno et al. / Microchemical Journal 88 (2008) 186193

Fig. 7. PCA score plot of PC1 and PC3 of DE mass spectral data, accounting for
72.2% of total variance. IS: conifer lignin from a 89th century AD shipwreck
recovered near Haifa (Israel); B44: oak lignin from a 2nd century BC shipwreck
recovered near Marseille (France); D: elm lignin from a bollard pertinent to the
Roman Harbour of San Rossore (Pisa, Italy); SR: hardwood lignin from a
bollard pertinent to the Roman Harbour of San Rossore (Pisa, Italy); spruce:
reference spruce lignin; birch: reference birch lignin.

the aim being to establish the value of this technique in determining the extent of degradation of lignin.
Acknowledgments
The authors wish to thank Dr. Y. Kahanov (University of
Haifa, Israel), Prof. I. Donato (University of Palermo) for
having provided the archaeological samples, and Prof. M.
Orlandi (University of Milano Bicocca) for having extracted
lignin from archaeological woods. Economic support was from
the Italian MIUR findings (PRIN Cofin05).
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