Bioresource Technology 97 (2006) 420–428

Effect of oxygen, ozone and hydrogen peroxide bleaching stages

on the contents and composition of extractives
of Eucalyptus globulus kraft pulps
Carmen S.R. Freire, Armando J.D. Silvestre *, Carlos Pascoal Neto, Dmitry V. Evtuguin
University of Aveiro, CICECO and Department of Chemistry, 3810-193 Aveiro, Portugal

Received 1 March 2004; received in revised form 5 January 2005; accepted 15 March 2005
Available online 21 April 2005

Abstract

The effects of oxygen (O), ozone (Z) and hydrogen peroxide (P) bleaching stages on the composition and total amount of Euca-
lyptus globulus kraft pulp lipophilic extractives was studied.
These bleaching stages led to the partial removal and to several oxidative transformations of fatty acids and sterols, the main
lipophilic extractives found in the unbleached pulp. Unsaturated extractives were found to be partially degraded while saturated
ones were, in general, stable. The oxygen and hydrogen peroxide bleaching stages were more effective than ozone in removing fatty
acids from pulp, by dissolution in the liquid phase. On the other hand, the ozone stage was more effective in the oxidative degra-
dation of sterols. Oxygen and hydrogen peroxide bleaching stages were also effective in sterols removal, but led to the formation of
sterol oxidation derivatives, previously shown to be involved in the formation of pitch that accumulates in the bleaching filtrates.

2005 Elsevier Ltd. All rights reserved.

Keywords: Eucalyptus globulus; Lipophilic extractives; TCF bleaching; GC–MS analysis

1. Introduction fatty acids (Silvestre et al., 1999; Freire et al., 2002a),

It is well known that wood extractives, even when
present in small amounts, may play an important role
in industrial wood processing for bleached pulp and
paper production. The lipophilic extractives, in particu-
lar, can be responsible for the formation of sticky depos-
its on the machinery, hindering normal operation of the
equipment or giving rise to dark spots in bleached pulp,
the so-called pitch (Back and Allen, 2000; del Rı́o et al.,
1998; Gutiérrez et al., 1998; Silvestre et al., 1999; Freire
et al., 2002a). In the case of ECF bleaching of Eucalyp-
tus globulus, pitch deposits were shown to be composed
mainly of fatty acids, including several a- and x-hydroxy-
*
Corresponding author. Tel.: +351 234 370 711; fax: +351 2343 70
084.
E-mail address: armsil@dq.ua.pt (A.J.D. Silvestre).
and several oxidation derivatives of b-sitosterol (Freire
et al., 2002a). The analysis of the lipophilic wood extrac-
tives in bleached pulps and filtrates is, therefore, an
important step in the study of the behaviour of wood
extractives during bleaching and, consequently, in the
resolution of the problems referred to above.
Totally chlorine free (TCF) bleaching processes have
been introduced, largely in response to environmental
restrictions and market demands for non-chlorine based
chemicals bleached pulps (Dence and Reeve, 1996).
These bleaching technologies employ oxygen based
bleaching agents such as molecular oxygen, ozone and
hydrogen peroxide. As far as E. globulus is concerned,
only a few studies on the behaviour of wood extractives
during TCF bleaching have been published (Gutiérrez
et al., 2001). In these works, only the analysis of the
extractives after a complete TCF bleaching sequence

0960-8524/$ - see front matter
2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2005.03.006
 C.S.R. Freire et al. / Bioresource Technology 97 (2006) 420–428
was studied and the effects of the single stages were not
considered. In previous publications the present authors
have reported the identification of several new E. globu-
lus wood components (Freire et al., 2002b), and the
occurrence of some of them in pitch deposits from
ECF mills (Silvestre et al., 1999; Freire et al., 2002a).
The identification of several oxidized derivatives of
wood extractives in such pitch deposits prompted a
more detailed study on the oxidation of lipophilic com-
ponents under ECF and TCF conditions, carried out
with model compounds (Freire et al., 2003).
In the present work, the lipophilic extracts of labora-
tory oxygen, ozone and hydrogen peroxide partially
bleached E. globulus kraft pulps (simulating O, Z, and
P stages) and also of the corresponding filtrates were
analysed by GC–MS in order to assess the fate of such
compounds during TCF bleaching stages. The effect of
these bleaching stages on the composition and total
amount of lipophilic extractives in the E. globulus pulp
is discussed.
2. Materials
2.1. Samples
E. globulus wood was selected from 12-year old trees
in a clone plantation (SMC-023) cultivated in the
Arouca region of Aveiro in Portugal.
Wood was debarked and then kraft pulped to a
kappa number of 17.6 in a laboratory reactor (MK
systems), using standard conditions (active alkali
18%, sulphidity 28%, temperature 160 C, time to tem-
perature 120 min, cooking time 60 min, liquor to wood
ratio 4).
The unbleached and partially washed E. globulus
Kraft pulp (consistency 8%, COD 26.5 Kg/tAD) was
then submitted to single stage delignification/bleaching
treatments with O2 (O), O3 (Z) and H2O2 (P) to kappa
numbers of 11.2, 9.0 and 11.8 respectively. The low de-
crease of kappa number is attributed to the high COD of
pulps which lead to high bleaching chemical consump-
tions in ‘‘non-bleaching’’ reactions (oxidation of dis-
solved organic matter in the liquid phase of the pulp);
however, COD was intentionally maintained high in
order to keep a relatively high concentration of lipophilic
extractives in order to facilitate the detection of their
degradation products in the bleached pulps. The bleach-
ing conditions were as follows; O: consistency 6.8%,
pH 13, heating time 20 min, 105 C, 90 min, NaOH
1.95%, total pressure 6 bar; Z: consistency 3.2%,
pH 2.5–3.0, 25 C, 30 min; the ozone was generated by
passing a constant flow of pure oxygen through the lab-
oratory ozone generator Fischer Model 502 (0.7 A) at
rate of 0.8 L/min (ozone rate was 42 mg/min, deter-
mined iodometrically) corresponding to a O3 charge of
421
4.2%; P: consistency 7.1%, pH 12, 70 C, 240 min,
NaOH 2.7%, H2O2 4.4%, EDTA 0.28%.
The unbleached pulp was separated from its liquid
fraction (carry-over) and partially bleached pulps were
separated from their bleaching filtrates by filtration.
Pulps and liquid fractions (carry-over and bleaching fil-
trates) were analysed individually as described below.
2.2. Extraction
Liquid filtrates (3 aliquots of 100 mL) were acidified
to pH 2 with 5% HCl and then sequentially extracted
with dichloromethane (3 · 100 mL) and ethyl acetate
(3 · 100 mL).
Three aliquots of around 20 g of each pulp were
Soxhlet extracted with dichloromethane (750 mL) for
16 h, followed by ethyl acetate (750 mL) for 16 h more.
The solvents were evaporated to dryness and the ex-
tracts were quantified gravimetrically. The results were
expressed as percent of the dry weight of the pulp. The
unbleached pulp was previously submitted to a beating
treatment (2000 rotations) in a PFI mill before solvent
extraction, in order to increase the extractives accessibil-
ity and thus the extraction yield (confirmed by results on
extraction yields before and after beating). The beating
treatment did not influence the extraction yields of
bleached or partially bleached pulps.
The extraction procedure using dichloromethane and
ethyl acetate was adopted, taking into consideration the
need to extract aqueous solutions. Although acetone is
normally used for pulp extractions, the same solvent se-
quence was used for pulps in order to facilitate compar-
ison of results. Dichloromethane together with ethyl
acetate gives lipophilic extractives contents quite similar
to those obtained by acetone extraction, as confirmed by
preliminary results in the present study, in good agree-
ment with results obtained for other species (Bergelin
et al., 2003). Additionally, the chromatograms from
the extracts obtained in the dichloromethane followed
by ethyl acetate extraction are simpler and easier to ana-
lyse than in the case of single extraction with acetone.
2.3. GC–MS analyses
Before GC–MS analysis, nearly 20 mg of each dried
extract were trimethylsilylated as described previously
(Freire et al., 2002b; Freire et al., 2003).
GC–MS analyses were performed using a Hewlett-
Packard gas chromatograph 5890 equipped with a mass
selective detector MSD series II, using helium as carrier
gas (35 cm/s), and with a DB-1 J&W capillary column
(30 m, 0.32 mm id, 0.25 lm film thickness). The
chromatographic conditions were as follows: initial
temperature: 80 C; temperature rise rate: 4 C/min;
final temperature, 285 C; injector temperature, 290 C;
transfer-line temperature, 290 C; split ratio, 1:100.
422 C.S.R. Freire et al. / Bioresource Technology 97 (2006) 420–428
In order to verify the presence of esterified structures
such as triglycerides, sterol esters and steryl glycosides,
the extracts were also analysed by GC–MS using short
length columns. These GC–MS analyses were performed
using a Trace gas chromatograph 2000 Series equipped
with a Finnigan Trace MS mass spectrometer, using
helium as carrier gas (35 cm/s), and a DB-1 J&W capil-
lary column (15 m, 0.32 mm id, 0.25 lm film thickness).
The chromatographic conditions were as follows (Freire
et al., 2002b): initial temperature: 100 C for 3 min; tem-
perature rise rate: 5 C/min; final temperature: 340 C
for 12 min; injector temperature: 320 C; transfer-line
temperature: 290 C; split ratio: 1:100.
Compounds were identified, as TMS derivatives, by
comparing their mass spectra with the GC–MS spectral
library, with data from literature and, in some cases, by
injection of standards.
For quantitative analysis, the GC–MS was calibrated
with pure reference compounds, representative of
the major lipophilic extractives components (hexadec-
anoic acid, 1-nonadecanol, 1-eicosanol, stigmasterol,
16-hydroxyhexadecanoic and 2-hydroxyoctadecanoic
acids), relative to pentanedioic acid (IS1) and 1-eicosa-
nol, 1-nonadecanol (IS2), the internal standards used.
The respective multiplication factors needed to obtain
correct quantification of the peak areas were calculated
as an average of 4 GC–MS runs.
2.4. Chemicals
16-Hydroxyhexadecanoic acid (97% purity), 1-non-
adecanol (98% purity) and b-sitosterol (99% purity) were
purchased from Fluka Chemie (Madrid, Spain); stig-
masterol (95% purity) was supplied by Sigma Chemicals
Co (Madrid, Spain); 2-hydroxyoctadecanoic acid was
ceded by Dr. Les West from Kraft Foods-USA. 5,6-
epoxy-24-ethylcholestane-3-ol (5,6-epoxy-b-sitosterol)
was prepared by reaction of b-sitosterol with m-chloro-
perbenzoic acid, while 24-ethylcholestane-3,5,6-triol was
obtained by cleavage of the 5,6-epoxy-b-sitosterol with
30% of perchloric acid in THF (Fieser and Fieser, 1967).
3. Results and discussion
3.1. Pulp extractives
The composition of the lipophilic extracts (dichloro-
methane + ethyl acetate) of Z, O and P partially
bleached pulps (Table 1, Fig. 1), from a qualitative point
of view, was, in general, similar to the corresponding ex-
tract of the unbleached pulp. The extracts were mainly
composed of long chain aliphatic acids, including sev-
eral a- and b-hydroxy fatty acids, sterols and long chain
aliphatic alcohols. The major compounds identified
were b-sitosterol, b-sitostanol, hexadecanoic, docos-
anoic, tetracosanoic and hexacosanoic acids. Minor
amounts of 22-hydroxydocosanoic, 24-hydroxytetracos-
anoic and 2-hydroxytetracosanoic acids were also
detected. The identification of these compounds in
bleached pulps is important because of their tendency
for pitch formation as reported for E. globulus ECF
bleached pulp mills (Silvestre et al., 1999; Freire et al.,
2002a).
Six b-sitosterol oxidation products, namely 24-ethyl-
6-cholestene-3,5-diol, 24-ethyl-5-cholestene-3,7-diol,
5,6-epoxy-24-ethylcholestane-3-ol (5,6-epoxysitosterol),
24-ethylcholestane-3,5,6-triol, 3-hydroxy-24-ethylcholes-
tane-6-one and 3-hydroxy-24-ethyl-5-cholestene-7-one
were identified in the O and P bleached pulps (Table 1,
Fig. 2). All these derivatives, apart from 5,6-epoxy-24-
ethylcholestane-3-ol, were also identified in Z bleached
pulp. These oxidised sterol derivatives were found in O
and P partially bleached pulps in small amounts (Table
1), in agreement with the results obtained in the reac-
tions of pure b-sitosterol with O2 and H2O2 (Freire
et al., 2003) where a low reaction extent was observed.
On the other hand, ozone was found to be more effective
in b-sitosterol oxidative degradation: a substantial de-
crease in b-sitosterol content was observed, but only a
small fraction of the degradation products was detected
in the pulp by GC–MS (Table 1), suggesting that ozone
promotes the conversion of b-sitosterol into higher oxi-
dation state derivatives, too polar to be analysed under
the GC–MS conditions used. Since the above mentioned
b-sitosterol oxidation products (Fig. 2) have already
been identified in pitch deposits from an Eucalyptus
globulus ECF bleached kraft pulp mill (Freire et al.,
2002a), it is likely that sterol derivatives in higher oxida-
tion states would also contribute to pitch formation,
and, therefore, the detailed nature of such a fraction
and its impact deserve further investigation.
In addition, 24-ethylcholestane-3-one was also identi-
fied in small amounts in the Z bleached pulp (Table 1,
Fig. 2). Its detection was quite difficult because it
co-elutes with b-sitosterol. This compound was recently
reported to be the main oxidation product formed
during reaction of pure b-sitostanol with ozone (Freire
et al., 2003).
Sitosteryl 3-b-D-glucopyranoside, identified in E.
globulus wood and kraft pulp (Gutiérrez and del Rı́o,
2001; Freire et al., 2004), and some steryl esters were still
identified in minor amounts in pulp after bleaching with
ozone, oxygen and hydrogen peroxide, as confirmed by
the analysis of the dichloromethane extracts by GC–MS
with short columns (results not shown). The resistance
of steryl esters to hydrolysis and/or oxidative degrada-
tion during hydrogen peroxide bleaching has already
been reported (Gutiérrez et al., 2001; Gutiérrez and del
Rı́o, 2001). However, the resistance of steryl esters dur-
ing Z and O bleaching may only be related to the acces-
sibility of these compounds in the fibre structure, since
 C.S.R. Freire et al. / Bioresource Technology 97 (2006) 420–428 423

Table 1
Lipophilic components (mg compound/kg of dry pulp, sum of dichloromethane and ethyl acetate extracts contribution) of O, P and Z partially
bleached pulps
Compound Unbleached pulp O pulp P pulp Z pulp
Glycerol 6.23 11.3 10.6 8.4
1-Dodecanol 1.77 1.28
Dodecanoic acid 1.06
2,6-Dimethoxyhydroquinone 3.20
1-Tetradecanol 1.51 1.74
Tetradecanoic acid 3.23 1.75 1.96
Pentadecanoic acid 2.03 0.913 0.599 1.51
1-Hexadecanol 11.7 2.79 2.91 4.25
Hexadecenoic acid 4.68
Hexadecanoic acid 21.5 16.4 18.06 24.6
1-Heptadecanol 3.84
Z-9-octadecen-1-ol 13.0 3.19 5.95 5.38
Heptadecanoic acid 9.51 2.23 3.54 4.68
1-Octadecanol 14.1 3.01 6.43 4.95
Linoleic acid 6.61 1.28 3.56 2.75
Oleic acid 7.52 2.97 3.31 4.18
2-Hydroxyhexadecanoic acid 0.45
Octadecanoic acid 11.1 5.83 9.09 10.1
Nonadecanoic acid 1.26 1.34
1-Eicosanol 0.571 1.77
Eicosanoic acid 7.34 4.06 6.24 5.85
Heneicosanoic acid 4.42 3.65 5.63 4.20
1-Docosanol 5.41 4.06 8.92 4.90
2-Hydroxyeicosanoic acid 0.87
Docosanoic acid 40.2 33.1 33.0 40.2
2-Hydroxyheneicosanoic acid 0.84
Tricosanoic acid 8.76 6.92 4.47 8.53
1-Tetracosanol 2.74 1.26 3.13 1.51
2-Hydroxydocosanoic acid 5.42 5.29 5.38 7.77
Squalene Tr 0.901 1.54 Tr
Tetracosanoic acid 56.0 60.9 48.3 70.9
2-Hydroxytricosanoic acid 4.10 4.69 4.50 5.97
Pentacosanoic acid 10.3 6.03 8.60 7.60
1-Hexacosanol 1.99 1.07 1.10 1.58
22-Hydroxydocosanoic acid 38.0 17.5 24.2 26.4
2-Hydroxytetracosanoic acid 9.75 14.1 9.56 15.3
Hexacosanoic acid 62.3 75.3 57.6 76.4
23-Hydroxytricosanoic acid 1.23 0.882
2-Hydroxypentacosanoic acid 4.14 4.83 2.36 4.77
Heptacosanoic acid 3.96 1.96 3.51 3.40
1-Octacosanol 9.88 2.35 10.1 3.82
24-Hydroxytetracosanoic acid 32.7 40.1 30.6 33.9
2-Hydroxyhexacosanoic acid 2.35 5.30 6.38
Campesterol 8.69
Octacosanoic acid 16.0 22.4 10.7 18.9
Stigmasterol 11.7
25-Hydroxypentacosanoic acid 1.37 1.53 1.58
24-Ethyl-6-cholestene-3,5-diol 21.4 7.9 5.21 15.2
b-Sitosterol 468.8 401.2 410.6 381.8
b-Sitostanol 95.5 61.5 89.0 83.6
1-Triacontanol 4.64 0.984 3.61
Cycloartenol 8.29 9.50 11.8 5.55
26-Hydroxyhexacosanoic acid 29.9 23.1 11.7 14.3
24-Ethyl-5-cholestene-3,7-diol 10.5 7.50 4.82 10.6
Triacontanoic acid 0.62 2.47 1.93 1.25
24-Methylenecycloartanol 21.4 11.7 12.1 11.9
5,6-Epoxy-24-ethylcholestane-3-ol 1.90 0.912
Citostradienol 24.1 8.25 11.4 11.2
24-Ethylcholestane-3,5,6-triol 2.30 0.830 3.87
3-Hydroxy-24-ethylcholestane-6-one 1.40 0.421 1.84
3-Hydroxy-24-ethyl-5-cholestene-7-one 0.951 Tr Tr
(continued on next page)
424 C.S.R. Freire et al. / Bioresource Technology 97 (2006) 420–428
Table 1 (continued)
Compound Unbleached pulp
Total identified 1156.05
Total unidentified (and others) 29.05
Total 1185.1
Fig. 1. Major families of compounds (FA: fatty acids, LCAA: long chain aliphatic alcohols and ST: sterols) identified in the unbleached pulp and Z,
O and P bleached pulps (sum of dichloromethane and ethyl acetate contributions).
they were found to undergo complete hydrolysis and
some oxidative degradation in experiments with
model compounds (Freire et al., 2003). Nilvebrant and
Byström (1995) reported that steryl glycosides were
quite resistant during O stages and almost complete de-
graded during P and Z bleaching stages. Consequently,
the resistance of sitosteryl 3-b-D-glucopyranoside during
P and Z bleaching of E. globulus pulp reported here can
only be assigned to its low accessibility in the fibre struc-
ture as observed in some cases for steryl esters. It is
worth noting that the experiments reported in this paper
refer to single bleaching stages, applied to unbleached
pulp. So, the possibility that the extent of degradation
of such compounds would be higher if P and Z stages
were applied later in a bleaching sequence cannot be
ruled out.
From a quantitative point of view, all the lipophilic
extractives families present in Z, O and P partially
bleached pulps were found in lower amounts than in
the unbleached pulp (Fig. 1), due to their oxidative de-
gradation and/or removal with bleaching filtrates. The
Z bleached pulp contained around 3%, 63% and 22%
less fatty acids, long chain aliphatic alcohols and sterols,
respectively, than the unbleached pulp. The decrease of
sterols in the pulp during the Z stage is related essen-
tially to their oxidative degradation, as described above,
since they were found in very small amounts in the cor-
responding bleaching filtrate, as described below. Never-
O pulp P pulp Z pulp
909.5 918.0 965.1
25.0 61.6 471.1
934.5 979.6 1436.2
theless, the percentage of degradation of b-sitosterol
observed here was lower than that observed in model
compound experiments (Freire et al., 2003), almost cer-
tainly because in this early bleaching stage ozone was
being primarily consumed in delignification reactions
and oxidation of the carry over compounds, rather than
in extractives degradation. The alkaline oxygen and
hydrogen peroxide bleaching removed fatty acids in
amounts of 13% and 25%, respectively. Sterols and
long chain aliphatic alcohols were also removed during
the alkaline bleaching stages: 23% and 73% in the O
bleaching and 18% and 34% in the P bleaching,
respectively.
3.2. Bleaching filtrates composition
The filtrates obtained from pulp bleaching with oxy-
gen, hydrogen peroxide and ozone were also extracted
with dichloromethane and ethyl acetate, and the
corresponding extracts analysed by GC–MS, after
derivatization.
The compositions of the bleaching filtrates were quite
different from that of the unbleached pulp liquid carry-
over (Fig. 3). The dichloromethane extracts of the alka-
line O and P bleaching filtrates (Table 2) were mainly
composed of phenolic compounds, mostly brought for-
ward with the liquid carry-over of the unbleached pulp
but also formed by lignin degradation during bleaching,
 C.S.R. Freire et al. / Bioresource Technology 97 (2006) 420–428 425

and sterols in these filtrates when compared with the

unbleached pulp carry-over confirms their removal from
pulp during the alkaline bleaching stages (Table 1). In
contrast, the amounts of long chain aliphatic compo-
HO
OH
HO OH
nents and sterols in the dichloromethane extract of the
24-Ethyl-6-cholestene-3,5-diol
24-Ethyl-5-cholestene-3,7-diol acidic Z filtrate (Fig. 3, Table 2) were very small. This
(7-Hydroxy-β-sitosterol)
is consistent with the small decrease of fatty acids ob-
served in the corresponding pulp (Table 1) and with
the significant decrease of sterols in pulp, associated
with their oxidative degradation.
The derivatives of b-sitosterol identified in O and P
HO HO
O OH
OH
bleached E. globulus pulps, namely 24-ethyl-6-choles-
5,6-Epoxy-24-ethylcholestane-3-ol tene-3,5-diol, 24-ethyl-5-cholestene-3,7-diol 5,6-epoxy-
(5,6-Epoxy-β-sitosterol) 24-Ethylcholestane-3,5,6-triol
24-ethylcholestane-3-ol (5,6-epoxysitosterol), 24-ethyl-
cholestane-3,5,6-triol, 3-hydroxy-24-ethylcholestane-
6-one and 3-hydroxy-24-ethyl-5-cholestene-7-one, were
also identified in the corresponding bleaching filtrates
(Table 2). However, these compounds were not detected
HO HO
O
O in the ozone bleaching filtrate, mainly because they were
3-Hydroxy-24-ethylcholestane-6-one 3-Hydroxy-24-ethyl-5-cholestene-7-one found to be minor oxidation products of b-sitosterol
during ozone bleaching.
Several aliphatic acids, namely hexanoic, heptanoic,
octanoic, nonanoic, octanedioic and azelaic (nonane-
dioic) acids were detected in the alkaline O bleaching
filtrate (Table 2). These acids have been identified as
the main oxidation products of oleic and linoleic acids
O
formed in O bleaching experiments with model com-
24-Ethylcholestane-3-one pounds (Freire et al., 2003). Azelaic, nonanoic and 9-
oxononanoic acids were identified in trace amounts in
Fig. 2. Structures of the main sterol derivatives identified in O, Z and
the P bleaching filtrate; these are the main oxidation
P partially bleached pulps and corresponding filtrates.
products of oleic and linoleic acids identified under P
bleaching conditions, and the low conversion yield is
and long chain aliphatic acids and alcohols and sterols. also consistent with previous model compound experi-
The increase in the amounts of long chain aliphatic acids ments (Freire et al., 2003). The main oxidation products

Fig. 3. Abundances of the major families of compounds identified in the unbleached pulp liquid and Z, O and P bleaching filtrates (sum of
dichloromethane and ethyl acetate contributions).
426 C.S.R. Freire et al. / Bioresource Technology 97 (2006) 420–428

Table 2
Lipophilic components (dichloromethane extract, in mg/L filtrate) of O, P, Z bleaching filtrates
Compound Unbleached pulp carry-over O filtrate P filtrate Z filtrate
Lactic acid 0.288 0.366 0.186 0.049
Hexanoic acid 0.066
Hydroxyacetic acid 0.149 0.033
4-Oxopentanoic acid 0.231 0.051
2-Hydroxybutanoic acid 0.659 0.581 0.363
3-Hydroxypropanoic acid 0.338
2-Methoxyphenol 0.135
Heptanoic acid 0.086
Benzoic acid 0.119 0.114
2-Tiophenocarboxylic acid 0.058 0.037
Isomer of 9 0.104 0.106
Octanoic acid 0.023
Methyltiophenecarboxylic acid 0.061
4-Hydroxybenzaldeyde 0.125 0.063
Nonanoic acid 0.064 0.080
2-Hydroxyheptanoic acid 0.092
Decanoic acid 0.057
Vanillin 1.73 7.18 1.95
Acetovanillone 0.924 1.33 0.684
Dodecanoic acid 0.386 0.446 0.719
Syringaldehyde 4.90 13.4 3.67 0.021
2,6-Dimethoxy-hydroquinone 0.229 0.022
Homovanillyl alcohol 0.083
Acetovanillone (enolic form) 0.059 0.202 0.109
Acetosyringone 5.12 2.41 1.63 0.039
Vanillic acid 1.68 3.76 3.46
1-Tetradecanol 0.079
Azelaic acid 0.123 0.293 0.344
3-Vanillylpropanol 0.138
Propiosyringone 0.228 0.136
Acetosyringone (enolic form) 0.900 0.581 0.537 0.022
Syringic acid 4.72 0.913 3.26 0.077
1-Guaiacy-2-hydroxyethanone 0.235
Pentadecanoic acid 0.058 0.118 0.165
Guaiacylglyoxylic acid 0.165 0.083
1-Hexadecanol 0.237 0.146 0.180 0.057
3-Guaiacyl-2-hydroxypropanoic acid 0.210
Hexadecenoic acid 0.777 0.159
Hexadecanoic acid 0.659 1.09 2.03 0.163
Ferulic acid 0.107 0.187
Syringylglyoxylic acid 0.239 0.906 0.264
3-Hydroxy-1-(4-hydroxy-3,5-dimethoxyphenil)-1-propenone 0.161 0.349 0.201
Z-9-octadecen1-ol 0.398 0.238 0.259 0.098
Heptadecanoic acid 0.320 0.195 0.224 0.070
2-Hydroxy-2-methyl-3-syringylpropanoic acid 0.174
1-Octadecanol 0.278 0.188 0.184 0.069
Linoleic acid 0.602 1.13 1.84
Oleic acid 0.355 0.761 1.41 0.078
2-Hydroxyhexadecanoic acid 0.319 0.071
Octadecanoic acid 0.250 0.477 0.610 0.061
Benzenetricarboxylic acid 0.106
Oxosyringylalcanoic acid n.i. 0.203 0.450 0.130
Oxosyringylalcanoic acid n.i. 0.318 0.404
Eicosanoic acid 0.061 0.151 0.391 0.011
Heneicosanoic acid 0.160 0.287
1-Docosanol 0.120 0.214
Docosanoic acid 0.086 0.882 1.74 Tr
2-Hydroxiheneicosanoic acid 0.155
Tricosanoic acid 0.251 0.451
1-Tetracosanol 0.104
2-Hydroxydocosanoic acid 0.279 0.566
Squalene derivative 0.163 0.454
 C.S.R. Freire et al. / Bioresource Technology 97 (2006) 420–428 427

Table 2 (continued)
Compound Unbleached pulp carry-over O filtrate P filtrate Z filtrate
Tetracosanoic acid 0.108 1.25 2.58 0.022
11-Disyringylethane 0.469
2-Hydroxytricosanoic acid 0.250
Pentacosanoic acid 0.645
1-Hexacosanol 0.173
22-Hydroxydocosanoic acid 0.812 0.715
2-Hydroxytetracosanoic acid 0.413 1.16
Hexacosanoic acid 1.18 2.79 0.013
Docosanodioc acid 0.222
23-Hydroxytricosanoic acid 0.149
2-Hydroxypentacosanoic acid 0.175 0.443
1-Octacosanol 0.145 0.134 0.020
24-Hydroxytetracosanoic acid 0.821 0.723
2-Hydroxyhexacosanoic acid 0.110 0.371
Octacosanoic acid 0.500
Stigmasterol Tr 0.510
25-Hydroxypentacosanoic acid 0.131
2-Hydroxyheptaccosanoic acid 0.131
24-Ethyl-6-cholestene-3,5-diol Tr 0.283 0.237
Ellagic acid 0.170
b-Sitosterol 0.867 7.70 8.41 0.094
b-Sitostanol 2.22 2.77 0.022
26-Hydroxyhexacosanoic acid 0.360 0.397
1-Triacontanol 0.013 0.031
Cycloartenol 0.087 1.29
24-Ethyl-5-cholestene-3,7-diol Tr 0.275 0.222
Medioresinol 0.354
24-Methylenecycloartanol 0.438 1.35
5,6-Epoxy-24-ethylcholestane-3-ol 0.0102 0.007
Citoestradienol 0.350 1.71
24-Ethylcholestane-3,5,6-triol 0.0122 0.011
Syringaresinol 1.94
3-Hydroxy-24-ethylcholestane-6-one 0.0074 0.012
3-Hydroxy-24-ethyl-5-cholestene-7-one Tr Tr
Total identified 31.35 59.1 58.2 1.04
Total unidentified (phenolic compounds n.i.) 5.35 7.2 (3.0) 6.1 (1.9) 0.16
Total 36.7 66.3 64.3 1.20

of oleic and linoleic acids during Z bleaching, namely 9-
oxononanoic and azelaic acids (Freire et al., 2003; Nie-
melä et al., 1999), were also identified in the ethyl acetate
extract of the Z bleaching filtrate studied here. Finally,
x- and a-hydroxyfatty acids, detected in the unbleached,
O, Z and P bleached pulps, were also identified in the
dichloromethane extract of the corresponding alkaline
bleaching filtrates.
Sitosteryl 3-b-D-glucopyranoside was also identified
in all bleaching filtrates, while steryl esters were not de-
tected. This could be due to the fact that steryl esters are
much less abundant in the unbleached pulp and more
lipophilic than the sitosteryl glucopyranoside, being
preferentially retained in pulp.
The ethyl acetate extracts of these bleaching filtrates
were quite similar, being composed mainly of short
chain aliphatic hydroxyacids formed by the alkaline
degradation of carbohydrates during pulping and alka-
line bleaching. In fact, in the O and P bleaching filtrates
a great increase in the amount of these compounds
(Fig. 3) was observed showing the degradation of carbo-
hydrates during these bleaching stages.
4. Conclusions
The oxygen, hydrogen peroxide and ozone bleaching
stages of Eucalyptus globulus kraft pulps led to the par-
tial removal and to oxidative transformations of the
main lipophilic extractives families found in unbleached
pulps, fatty acids and sterols. In general, unsaturated
compounds were partially degraded while saturated
ones were stable.
Oxygen and hydrogen peroxide stages are more effec-
tive than ozone in fatty acids removal from pulp, as ex-
pected from the alkaline nature of the corresponding
aqueous bleaching media. However, fatty acids or their
oxidation products accumulated in the bleaching fil-
trates and, in an industrial situation, unless filtrates were
purged, could contribute to pitch formation. On the
428 C.S.R. Freire et al. / Bioresource Technology 97 (2006) 420–428
other hand, although a low removal of unsaturated ster-
ols under ozone bleaching was observed, because of
ozone consumption in delignification reactions under
the conditions of the experiment, this bleaching agent
was shown to be effective in the extensive oxidation of
this group of compounds. Therefore the use of a Z treat-
ment in the later stages of bleaching sequences, where
most delignification has already occurred and extrac-
tives are more accessible, may contribute to a reduction
in the amounts of these compounds and the problems
associated with the recirculation of filtrates and pitch
deposition in bleached kraft pulp mills.
Oxygen and hydrogen peroxide were also effective in
sterols removal. However, with these bleaching chemi-
cals, sterol oxidation derivatives, previously shown to
be involved in pitch formation, accumulated in the
bleaching filtrates.
Acknowledgements
Thanks are due to FCT and ESF for the awarding of
a Ph.D. grant within the Community Support Frame-
work III, to C. S. R. Freire, and to the Forest and Paper
Research Institute RAIZ for supplying the E. globulus
wood and for the making facilities available for the kraft
pulping essays.
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