International Biodeterioration & Biodegradation 52 (2003) 151 – 160

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FTIR studies of the changes in wood chemistry following decay

by brown-rot and white-rot fungi
K.K. Pandeya;∗ , A.J. Pitmanb
a Institute of Wood Science and Technology, 18th Cross Malleswaram, Bangalore 560003, India
b Forest Products Research Centre, Buckinghamshire Chilterns University College, High Wycombe, UK
Received 19 November 2002; accepted 8 March 2003

Abstract

A Fourier transform infrared (FTIR) spectroscopic study of changes in chemistry of Scots pine (Pinus sylvestris L.) sapwood and beech
(Fagus sylvatica L.) decayed by Coniophora puteana ((Schumacher) Karsten), Coriolus versicolor ((L.) Quelet) and Phanerochaete
chrysosporium (Burdsall) is presented. Wood was exposed to fungi for di7erent durations up to 12 weeks, with decay assessed through
weight loss and FTIR. The relative changes in intensities of spectral bands associated with lignin and carbohydrates as a result of decay
were determined after di7erent exposure periods. In wood decayed by C. puteana there was a progressive increase in lignin content
relative to carbohydrate evident from increases in the relative height of lignin associated bands (at 1596, 1505, 1330, 1230 and 1122 cm−1
in beech and 1596, 1511, 1268 and 1220 cm−1 in pine) and a corresponding decrease in the intensities of carbohydrate bands (at 1738,
1375, 1158 and 898 cm−1 ). At higher weight losses, spectra for wood decayed by C. puteana have many similarities with that of Klason
lignin isolated from wood. In contrast, wood decayed by P.chrysosporium showed selective type decay with a reduction in peak heights
associated with lignin relative to carbohydrates. Although weight losses in samples exposed to C. versicolor were high (45.5% and 39.8%
for beech and Scots pine, respectively, after 12 weeks) simultaneous decay resulted in little change in the relative intensities of the lignin
and carbohydrate bands, with only a slight preference for lignin.
? 2003 Elsevier Ltd. All rights reserved.

Keywords: Wood decay; Wood chemistry; White-rot; Brown-rot; FTIR

1. Introduction Brown-rot fungi selectively decay structural carbohy-

drates, with limited lignin degradation resulting in this com-
Several types of fungal wood decay are recognised in- ponent becoming elevated in brown-rotted wood. Changes
cluding white-rot, brown-rot and soft-rot (Blanchette, 1995; in wood chemistry following brown-rot decay have been
Worrall et al., 1997). Changes in wood chemistry resulting investigated (Perez et al., 1993; Davis et al., 1994a, b; Kim
from these decay types have been studied directly using and Newman, 1995; Worrall et al., 1997; Enoki et al., 1998).
gravimetric analysis (Worrall et al., 1997; Enoki et al., White-rot fungi decay all structural cell wall constituents,
1998; Blanchette, 1995; Perez et al., 1993), FTIR (Faix although the rate at which they do this di7ers. Selective
et al., 1991; Korner et al., 1990, 1992; Perez et al., 1993; (or preferential) white-rots decay hemicellulose and lignin
Ferraz et al., 2000) and NMR spectroscopy (Davis et al., Erst, resulting in deEbrillation through dissolution of the
1994a, b; Kim and Newman, 1995). More recently, Vane middle lamella. In contrast, non-selective (or simultaneous)
(2002) employed pyrolysis GC-MS and thermochemol- white-rots remove lignin and structural carbohydrates at a
ysis to study white-rot decay in spruce. Decay has also similar rate, resulting in homogeneous cell wall decay. The
been studied indirectly through examination of changes in inFuence of white-rot decay on wood chemistry has been
the cell wall following decay using microscopy (Daniel, investigated by various methods (Blanchette et al., 1985;
1994; Anagnost, 1998). Perez et al., 1993; Davis et al., 1994a, b; Blanchette, 1995;
Worrall et al., 1997; Enoki et al., 1998).
∗ Corresponding author. Tel.: +91-80-3346811; fax: +91-80-3340529. FTIR is a useful technique for studying wood decay
E-mail address: [email protected] (K.K. Pandey). chemistry, since minimal sample preparation is required

0964-8305/03/$ - see front matter ? 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0964-8305(03)00052-0
152 K.K. Pandey, A.J. Pitman / International Biodeterioration & Biodegradation 52 (2003) 151 – 160

and very small quantities of wood can be analysed (a few weeks. At 2-week intervals six pine and beech samples
milligrams) when compared to conventional gravimetric were removed, mycelium removed from their surfaces and
techniques where several grams are required. FTIR has they were oven-dried to constant weight. The weight losses
previously been used to characterise the chemistry of wood (WL ) of individual samples were calculated (Eq. (1)), and
(Faix, 1992; Owen and Thomas, 1989; Pandey, 1999) and used to calculate mean percentage weight losses.
determine lignin content in pulp, paper and wood (Schultz
%WL = [(Wo − Wf )=Wo ] ∗ 100; (1)
et al., 1985; Berben et al., 1987; Rodrigues et al., 1998).
It has also been used for analysing chemical changes that where, Wo is oven dry weight of sample prior to exposure
occur in wood during weathering, decay and chemical treat- and Wf is the oven dry weight following exposure to fungus.
ments, its use for this having been recently reviewed by Additional Scots pine sapwood and beech samples
Moore and Owen (2001). (10 × 10 × 2 mm) were exposed to P. chrysosporium us-
Fungal decay of wood has been studied using FTIR (Faix ing the methods described above, although blocks were not
et al., 1991; Korner et al., 1990, 1992; Chen, 1992; Perez pre-extracted and were exposed for 6 and 12 weeks only.
et al., 1993; Ferraz et al., 2000). Faix et al. (1991) used FTIR spectra of decayed samples and undecayed con-
this technique to monitor changes in beech wood decayed trols were measured by direct transmittance using the KBr
by white-rot fungi. Korner et al. (1990, 1992) investigated pellet technique. Spectra were recorded using a Nicolet
the e7ects of brown-rot decay (by Fomitopsis pinicola and Impact 400 FTIR spectrometer equipped with a DTGS de-
Coniophora puteana) on the chemistry of Scots pine. Chen tector. Wood was removed from the sample surfaces using
(1992) studied fungal decay resistance of loblolly pine mod- a double-sided razor and mixed with potassium bromide
iEed with 1,6 diisocyanatohexane. More recently, Ferraz et (for IR spectroscopy, MERCK) to about 0.5 –1% concen-
al. (2000) used FTIR-DRIFT spectroscopy to characterise tration. The sample for FTIR analysis was taken from one
changes in wood of Pinus radiata and Eucalyptus globu- sample block whose weight loss reFected the average for
lus decayed by white and brown-rot fungi. However, most that species exposed for that duration. All the spectra were
published work describes qualitative changes in the FTIR measured at a spectral resolution of 4 cm−1 and 100 scans
spectra following decay over long exposure periods. Infor- were taken per sample.
mation on relative changes in lignin/carbohydrate compo- Peak height and area was measured using OMNIC soft-
sition of wood decayed for shorter exposure periods and ware version 1.2a (Nicolet Instrument Corporation, USA).
changes over time is scant. First, a baseline was constructed by connecting the lowest
In this paper, we present a detailed FTIR spectroscopic data points on either side of the peak. A vertical line from
analysis of the chemical changes occurring in a softwood the top of the peak to this baseline gave peak height. The
(Pinus sylvestris L. sapwood) and a hardwood (Fagus area between the baseline and the top of the peak represents
sylvatica L.) decayed by the brown-rot C. puteana, the the peak area. Peak height and area values for lignin as-
non-selective white-rot C. versicolor and the selective sociated bands were ratioed against carbohydrate reference
white-rot P. chrysosporium. Samples were decayed to dif- peaks to provide relative changes in the composition of the
ferent levels (determined by weight loss) through exposing structural components relative to each other. The assignment
samples to fungi for di7erent periods from 2 to 12 weeks. of bands to structural components (as determined by other
Relative changes in the intensity of lignin/carbohydrate researchers) is provided in the results.
characteristic bands were determined. Studies of the changes Klason lignin was isolated from undecayed beech and
in wood chemistry of these wood species decayed by Scots pine samples according to methods given in TAPPI
C. puteana and C. versicolor over such exposure intervals standard T 222 om-88 and analysed as for decayed wood
has been carried out. Also an FTIR study of these species samples.
decayed by P. chrysosporium is undertaken for the Erst
time.
3. Results and discussion

2. Materials and methods 3.1. Weight loss data

Scots pine sapwood and beech blocks (50 × 10 × 3 mm) The mean percentage weight losses for samples exposed
were extracted with ethanol: toluene (1 : 2, v/v) for 6 h, to C. puteana and C. versicolor for di7erent exposure peri-
oven-dried at 60 ± 5◦ C (to constant weight) and then ods are given in Table 1. Mean weight losses in beech and
weighed. Samples were sterilised by autoclaving (121◦ C Scots pine decayed by C. puteana were 64.3% and 61.4%,
for 15 min) and exposed to C. puteana (FPRL 11E) and respectively, after 12 weeks. The extent of decay was greater
C. versicolor (MD-227) in Petri dishes containing 3% in Scots pine decayed by C. puteana in the initial stages
malt extract agar, pre-inoculated 1 week prior to the test. (after 2 weeks). Mean weight losses for beech and Scots
Samples were supported on sterile plastic mesh, and were pine decayed by C. versicolor were 45.5% and 39.8%, re-
incubated at 25◦ C and 65% relative humidity for 2–12 spectively, after 12 weeks. The extent of decay was greater
 K.K. Pandey, A.J. Pitman / International Biodeterioration & Biodegradation 52 (2003) 151 – 160 153

Table 1
Average weight losses and ratios of the intensity of the lignin associated band with carbohydrate bands for decayed samples

Exposure Wood Fungus Average weight Relative intensitiesa of aromatic skeletal vibration (Ia )b
(weeks) species loss (%) against typical bands for carbohydrates
Ia =I1738 Ia =I1375 Ia =I1158 Ia =I898

0 Beech Control — 0.45 1.38 1.73 2.24

(0.25) (1.40) (2.19) (3.15)
Pine Control — 1.54 2.91 2.59 4.42
(0.82) (2.65) (3.10) (5.04)

2 Beech C. puteana 3:09 ± 1:2 0.48 1.62 2.28 2.64

(0.29) (1.67) (2.59) (3.63)
Pine C. puteana 15:8 ± 6:4 1.78 3.89 2.69 9.70
(0.85) (3.74) (3.83) (12.68)

4 Beech C. puteana 18:8 ± 10:0 0.65 2.49 2.64 5.69

(0.34) (2.72) (4.16) (7.89)
C. versicolor 5:27 ± 1:8 0.40 1.22 1.13 1.99
(0.19) (1.15) (1.07) 2.36
Pine C. puteana 30:8 ± 2:9 2.07 4.77 3.60 11.07
(1.03) (4.69) (5.24) (12.69)
C. versicolor 6:22 ± 1:3 1.21 2.11 1.48 4.38
(0.53) (1.75) (1.40) (4.69)

6 Beech C. puteana 28:3 ± 10:6 0.72 2.94 3.47 7.56

(0.41) (3.71) (6.50) (12.03)
C. versicolor 25:52 ± 4:8 0.38 1.03 0.97 1.85
(0.19) (0.97) (0.93) (2.45)
Pine C. puteana 40:8 ± 3:3 2.70 5.89 4.97 16.59
(1.36) (6.04) (6.92) (19.84)
C. versicolor 13:96 ± 3:1 1.54 2.61 1.79 4.26
(0.71) (2.33) (1.85) (4.50)

8 Beech C. puteana 38:9 ± 5:9 0.95 4.51 5.02 17.19

(0.55) (6.03) (12.93) (32.39)
C. versicolor 40:20 ± 2:8 0.36 0.91 0.81 1.65
(0.16) (0.83) (0.78) (2.19)
Pine C. puteana 52:3 ± 1:9 3.29 7.50 6.05 —
(1.66) (7.59) (9.49)
C. versicolor 23:28 ± 5:3 1.40 2.85 2.16 3.89
(0.61) (2.36) (2.09) (4.01)

10 Beech C. puteana 49:8 ± 9:5 0.99 4.38 6.42 —

(0.57) (6.27) (12.75)
C. versicolor 40:85 ± 2:7 0.36 0.94 0.84 1.69
(0.19) (0.90) (0.84) (2.30)
Pine C. puteana 54:3 ± 3:9 3.11 6.28 5.30 —
(1.52) (6.35) (7.79)
C. versicolor 30:75 ± 3:4 1.42 2.10 1.50 3.34
(0.74) (1.93) (1.44) (3.71)

12 Beech C. puteana 64:3 ± 0:8 1.32 6.29 — —

(0.75) (8.58)
C. versicolor 45:53 ± 3:8 0.40 1.06 0.91 1.89
(0.19) (0.96) (0.86) (2.38)
Pine C. puteana 61:4 ± 6:4 4.26 11.27 — —
(2.07) (11.22)
C. versicolor 39:87 ± 3:8 1.23 1.93 1.47 3.86
(0.61) (1.74) (1.37) (4.49)
a Quantities
given in the parentheses correspond to values calculated from band area measurements. The values above the parentheses are ratios
based on peak heights.
b Beech 1505 cm −1 ; Scots Pine 1511 cm −1 .
154 K.K. Pandey, A.J. Pitman / International Biodeterioration & Biodegradation 52 (2003) 151 – 160

Fig. 1. FTIR spectra of undecayed Scots pine (sapwood) and beech.

in beech decayed by C. versicolor in the initial stages (see The relative intensities of bands at 1511, 1425, and
Table 1). Mean weight losses for beech and pine blocks af- 1268 cm−1 are higher in the Scots pine, whereas bands at
ter 12 weeks exposure to P. chrysosporium were 54.2% and 1738, 1462, 1330 and 1244 cm−1 are stronger in beech.
45.5%, respectively. The higher xylan content in beech (a hardwood) than pine
results in a stronger carbonyl band at 1738 cm−1 , whereas
3.2. FTIR studies the higher lignin content of Scot pine (a softwood) than
beech is seen in a stronger aromatic band at 1511 cm−1 .
3.2.1. Undecayed wood (controls)
FTIR spectra of undecayed Scots pine sapwood and beech
are shown in Fig. 1. A strong hydrogen bonded (O–H) 3.2.2. Wood decayed by C. puteana
stretching absorption is seen at 3400 cm−1 (1) and a promi- FTIR spectra of beech and Scots pine exposed to
nent C–H stretching absorption around 2997 cm−1 (2). In C. puteana for 2–12 weeks are shown in Figs. 2a and b and
addition, there are many well-deEned peaks in the Enger- 3a and b, respectively. SigniEcant changes in IR spectra
print region between 1800 and 600 cm−1 . The peaks in the can be seen at very early stages of decay in both species.
Engerprint are assigned (Harrington et al., 1964; Hergert, In the case of beech (Fig. 2a and b), the intensities of
1971; Schultz and Glasser, 1986; Faix, 1992; Collier et al., carbohydrate bands at 1738, 1375, 1158 and 898 cm−1 de-
1992; Pandey and Theagarajan, 1997): 1738=1734 cm−1 crease with exposure time to the fungus, with those at 1158
(3) for unconjugated C = O in xylans (hemicellulose), and 898 cm−1 almost absent after 12 weeks exposure. In
1650 cm−1 (4) for absorbed O–H and conjugated C–O, contrast, intensities of absorption bands resulting from lignin
1596 cm−1 (5) and 1505=1511 cm−1 (6) for aromatic at 1596, 1505, 1462, 1425, 1330, 1244 and 1122 cm−1 in-
skeletal in lignin, 1462 cm−1 (7) and 1425 cm−1 (8) for crease as decay progresses. A shoulder at 1268 cm−1 , which
C–H deformation in lignin and carbohydrates, 1375 cm−1 was not observed in the spectrum of undecayed beech, de-
(9) for C–H deformation in cellulose and hemicellulose, velops in the band at 1230 cm−1 . It has been shown that
1330=1320 cm−1 (10) for C–H vibration in cellulose and the guaiacyl type (softwood lignin) absorbs near 1268 and
Cl –O vibration in syringyl derivatives, 1268 cm−1 (11) for 1230 cm−1 and that the syringyl type (the major type of
guaiacyl ring breathing, C–O stretch in lignin and for C–O hardwood lignin) absorbs only at 1230 cm−1 (Sarkanen
linkage in guiacyl aromatic methoxyl groups, 1244 cm−1 et al., 1967). Although hardwood lignin also contains gua-
(12) for syringyl ring and C–O stretch in lignin and iacyl moities, the absorption band at 1268 cm−1 may have
xylan, 1158 cm−1 (13) for C–O–C vibration in cellulose been suppressed by a strong absorption at 1230 cm−1 . The
and hemicellulose, 1122 cm−1 (14) for aromatic skeletal and appearance of the 1268 cm−1 band in decayed beech may
C–O stretch, 1048 cm−1 (15) for C–O stretch in cellulose be mainly due to decrease in the intensity of 1230 cm−1
and hemicellulose and 898 cm−1 (16) for C–H deformation band resulting from xylan degradation, since this band
in cellulose. results partially from the C–O in xylan.
 K.K. Pandey, A.J. Pitman / International Biodeterioration & Biodegradation 52 (2003) 151 – 160 155

Fig. 2. (a) FTIR spectra of beech samples at various degrees of decay by C. puteana: (a) undecayed wood; (b) decayed for 2 weeks; (c) decayed for 4
weeks; (d) decayed for 6 weeks; (e) decayed for 8 weeks; (f) decayed for 12 weeks and (g) decayed for 12 weeks (b) FTIR spectra of (a) undecayed
beech; (b) beech decayed for 12 weeks; and (c) Klason lignin isolated from undecayed beech.
156 K.K. Pandey, A.J. Pitman / International Biodeterioration & Biodegradation 52 (2003) 151 – 160

Fig. 3. (a) FTIR spectra of Scots pine samples with various degrees of decay by C. puteana: (a) undecayed wood; (b) decayed for 2 weeks; (c) decayed
for 4 weeks; (d) decayed for 6 weeks; (e) decayed for 8 weeks; (f) decayed for 10 weeks and (g) decayed for 12 weeks. (b) FTIR spectra of (a)
undecayed Scots pine; (b) Scots pine decayed for 12 weeks and (c) Klason lignin isolated from undecayed Scots pine.
 K.K. Pandey, A.J. Pitman / International Biodeterioration & Biodegradation 52 (2003) 151 – 160 157

The spectra for undecayed beech, beech decayed for decay. Values of I1462 =I1511 and I1425 =I1511 for pine decrease
12 weeks and Klason lignin isolated from beech are shown from 0.36 to 0.35 and 0.30 to 0.25 respectively, whereas
in Fig. 2b. The peaks with the maximum intensities in for beech I1462 =I1505 and I1425 =I1505 ratio changes from 0.88
Fig. 2b have been normalised at the same value. It can to 0.80 and from 0.56 to 0.46, respectively, after 12 weeks
be observed that the spectrum for beech decayed for decay. This small decrease may be due to xylan decay rather
12 weeks has many similarities with the lignin spectrum (i.e. than demethylation of lignin, since both of peaks have a
increased intensities of bands at 1596, 1505, 1462, 1268, contribution from carbohydrates.
1230 and 1122 cm−1 . The presence of band at 1738 cm−1 Infrared spectroscopy has earlier been used to determine
in wood decayed for 12 week is due to residual xylan. Since the lignin content in pulp and paper and wood (Schultz et al.,
the weight loss after 12 weeks exposure for beech and pine 1985; Berben et al., 1987; Rodrigues et al., 1998). Attempts
is 64.3 and 61.4%, respectively, some of the hemicellulose have been made to correlate FTIR measurements with lignin
fraction still remains in these decayed samples. content determined by the Klason method and/or the acetyl
In the case of Scots pine (Fig. 3a and b) the intensi- bromide method. The 1505 cm−1 peak is often taken as
ties of carbohydrate bands at 1734, 1375, 1320, 1158, 1060 a reference for lignin, while the 1738, 1158 or 898 cm−1
and 898 cm−1 decrease and carbohydrate bands at 1320, peaks as polysaccharide references. Rodrigues et al. (1998)
1158 and 898 cm−1 are almost absent after 12 weeks of de- used FTIR spectroscopy to quantitatively determine lignin
cay. However, intensities of absorption bands at 1596, 1511, in Eucalyptus globulus using carbohydrate peaks at 1158
1462, 1425, 1268, and 1030 cm−1 increase signiEcantly and and 898 cm−1 as references against lignin peaks at 1505
well-resolved lignin bands at 1220 and 1140 cm−1 develop and 1330 cm−1 . They concluded that the best calibration Et
in decayed Scots pine. Normalised spectra for undecayed was obtained by taking a ratio of peak heights at 1505 and
Scots pine, that decayed for 12 weeks, and that of Klason 1158 cm−1 for lignin and carbohydrates, respectively.
lignin isolated from Scots pine are shown in Fig. 3b for The average relative intensities of lignin peaks at
comparison. This shows that after 12 weeks, there are many 1505 cm−1 (for beech) and 1511 cm−1 (for Scots pine)
similarities between the spectrum of decayed wood and that against carbohydrate peaks at 1738/1734, 1375, 1158 and
of Klason lignin as for beech, indicating selective removal 898 cm−1 calculated using peak heights and areas are sum-
of the carbohydrate fraction. marised in Table 1. It is important to mention that most of the
The most obvious di7erence between beech and Scots bands in the Enger print region have contributions from all
pine decayed by C. puteana is an increase in the inten- the wood constituents and careful interpretation of IR data
sity of bands at 1330 and 1122 cm−1 in beech (see Fig. is needed. Therefore, we have used the 1505=1511 cm−1
2b) when compared to Scots pine (Fig. 3b). In beech, the peak as a lignin reference since it arises purely due to aro-
band at 1122 cm−1 arises from C–H in plane deformation matic skeletal vibration (C = C) in lignin. All carbohydrate
in the syringyl monomer (lignin) (Faix, 1992), the relative peaks listed in Table 1 have no signiEcant contribution from
proportion of which increases as decay occurs. This study lignin (Harrington et al., 1964). The method of baseline
shows the band at 1330 cm−1 in beech results from the construction and peak height for 1738, 1505 and 1377 cm−1
C–O vibration in syringyl unit and not from C–H in cel- bands measurement is shown in Fig. 4. The base lines for
lulose, since it increases as the carbohydrate is selectively measuring the intensities of the bands at 1738, 1505, 1375,
removed. 1158, and 898 cm−1 for beech were constructed between
The decrease in the intensity at 1060 cm−1 accompanied 1700 and 1805, 1488 and 1544, 1350 and 1400, 1148 and
by the increase at 1030 cm−1 and development of a band 1180, and 876 and 911 cm−1 , respectively. Similarly base
at 1140 cm−1 in Scots pine decayed for 12 weeks is at- lines for measuring peak height and area under the bands
tributable to an increase in the guaiacyl lignin relative to at 1734, 1511, 1375, 1158 and 898 cm−1 for Scots pine
carbohydrate components (C–H deformation in the guaiacyl were constructed between 1700 and 1786, 1490 and 1538,
unit, with C–O deformation in primary alcohol). 1350 and 1397, 1148 and 1178 and 872 and 910 cm−1 , re-
The increase in the intensity of the 1650 cm−1 (4) band spectively. From Table 1 the ratio of lignin to carbohydrate
after 2 and 4 weeks exposure in both species results from increases for both species as decay progresses.
an increase of carbonyl moieties as decay initiates.
Lignin is chemically altered during the brown-rot decay
process (Davis et al., 1994a, b). An NMR study of decay 3.2.3. Wood decayed by C. versicolor
of spruce by a brown-rot (Postia placenta) shows loss of Fig. 5a and b show FTIR spectra for beech and Scots pine
methoxy groups, whereas the decay of birch by the same samples decayed for di7erent durations by C. versicolor.
brown-rot species has been reported to cause cleavage of The relative intensities of various component bands are sum-
lignin -O-4 linkages rather than demethylation of lignin marised in Table 1. There is little change in the relative inten-
(Davis et al., 1994a, b). We have calculated the ratios of the sities of structural wood components decayed by this fungus
heights of lignin peaks at 1505/1511 against peaks at 1462 (1505 cm−1 (for beech) and 1511 cm−1 bands (for pine)
and 1425 cm−1 (due to C–H, deformation of methyl and against carbohydrate bands) although high weight losses
methylene). There is only a small decrease in the ratio after were recorded. This results from C. versicolor decaying
158 K.K. Pandey, A.J. Pitman / International Biodeterioration & Biodegradation 52 (2003) 151 – 160

Fig. 4. Measurement of peak heights of 1738, 1505 and 1375 cm−1 for beech.

Fig. 5. (a) FTIR spectra of beech samples with various degrees of decay by C. versicolor: (a) undecayed wood; (b) decayed for 2 weeks; (c) decayed
for 4 weeks; (d) decayed for 6 weeks; (e) decayed for 8 weeks; (f) decayed for 10 weeks and (g) decayed for 12 weeks. (b) FTIR spectra of pine
samples with various degrees of decay by C. versicolor: (a) undecayed wood; (b) decayed for 4 weeks; (c) decayed for 6 weeks; (d) decayed for
8 weeks; (e) decayed for 10 weeks and (f) decayed for 12 weeks.
 K.K. Pandey, A.J. Pitman / International Biodeterioration & Biodegradation 52 (2003) 151 – 160 159

the structural components (lignin and carbohydrates)

simultaneously. Some decrease in the relative intensities
of lignin bands at 1505 cm−1 (for beech) and 1511 cm−1
(for Scots pine) accompanied by increase in the intensity at
1650 cm−1 was seen, resulting in a slight reduction in the
lignin to carbohydrate ratio (Table 1) indicating a slight pref-
erence for lignin. The decrease in the lignin/carbohydrate
ratio is less for 1738 cm−1 band when compared to other
carbohydrate bands, indicating C. versicolor has preferen-
tially decayed the hemicellulose fraction over cellulose.
Faix et al. (1993) studied chemical changes in beech
wood decayed by the white-rots, Trametes (Coriolus)
versicolor, Pleurotus ostreatus and Lentinus edodes. After
14 weeks of decay, sample weight losses were 51%, 27% and
24%, respectively. Although substantial weight losses were
recorded, the complex band between 1200 and 900 cm−1 ,
due mainly to polysaccharides and the hemicellulose band
at 1740 cm−1 showed only small changes. However, decay
resulted in increased intensity of the 1646 cm−1 band (due
to conjugated carbonyl groups originating from lignin)
while the aromatic skeletal vibration band at 1596 and
1506 cm−1 decreased in intensity. It was shown that the
quotients calculated from the band intensities 1596/1646
and 1506=1646 cm−1 were inversely proportional to
the degree of degradation indicating selective nature of
T. Versicolor, since lignin removed while little change in
structural carbohydrates was noticed. However, when Faix
et al. (1993) compared lignin content determined by FTIR
with other methods, it was found to overestimate lignin loss
for white-rots. This highlights the importance of calibrating
FTIR data with that obtained via other methods for accu-
rate quantitative determination of the lignin component in
wood. Fig. 6. FTIR spectra of (a) undecayed beech; (b) beech decayed for 6
weeks by P. chrysosporium; (c) undecayed pine and (d) pine decayed for
Perez et al. (1993) also reported a reduction in lignin 6 weeks by P. chrysosporium.
content of Fagus sylvatica wood by C. versicolor after
12 months decay and observed reduction in intensity of
lignin associated bands at 1600 and 1510 cm−1 . In 13 C NMR intensity of carbonyl absorption band at 1738 cm−1 also in-
studies of decay of paper birch and blue spruce by C. versi- dicates decay of xylan (hemicellulose) by P. chrysosporium.
color (Davis et al., 1994a, b), it was found that this fungus
decayed lignin and carbohydrate components of wood si- 4. Conclusions
multaneously as for this study, supporting Endings of other
workers that the same fungus can cause both simultaneous FTIR spectroscopy was used to examine qualitative and
and selective decay in same species of wood (Blanchette, quantitative changes in lignin and carbohydrate components
1995). relative to one another in wood decayed by a brown-rot
and white-rots. C. puteana removed structural carbohy-
drate components selectively (with reduction of bands at
3.2.4. Wood decayed by P. chrysosporium 1738, 1375, 1158 and 898 cm−1 ) leaving elevated levels
FTIR spectra of beech and Scots pine samples decayed by of the syringyl moiety in beech and guiaicyl moiety in
P. chrysosporium for 6 weeks are shown in Fig. 6. Decay of pine. This results in an increase in the lignin:carbohydrate
beech results in decrease in intensity of lignin bands at 1505, peak area ratio as decay proceeded. In wood decayed by
1245 and 1122 cm−1 and the carbonyl band due to xylan the selective white-rot P. chrysosporium, the lignin content
at 1738 cm−1 . Similarly, in Scots pine intensities of lignin decreased as decay progressed, as did the xylan content. In
bands at 1511, 1268 cm−1 and xylan bands at 1734 cm−1 the simultaneous white-rot C. versicolor, lignin and carbo-
decrease in decayed wood. The spectra indicate preferential hydrate reduction occurred at a similar rate, with a slight
decay of lignin fraction over total carbohydrate component preference for lignin reFected in a small reduction in the
by P. chrysosporium. However, a signiEcant decrease in the lignin:carbohydrate peak area ratio as decay progressed.
160 K.K. Pandey, A.J. Pitman / International Biodeterioration & Biodegradation 52 (2003) 151 – 160

Acknowledgements wood by DRIFT spectroscopy and multivariate analysis. Bioresource

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