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https://doi.org/10.1007/s00226-018-1057-3
ORIGINAL
Abstract
The effect of heat treatment and the presence of some molybdenum catalysts on
the amount of extractives in Populus nigra, Larix decidua, Paulownia tomentosa,
Castanea sativa and Quercus frainetto wood were studied. There are an increase
in the amount of lignin and extractives and a decrease in the amount of holocel-
lulose following thermo-treatment, in the treatment temperature range. Autoclave
treatment of wood with water in the presence of some molybdenum catalysts can
increase the amount of extracts, but it reduces solubility. Soxhlet extraction of wood
with ethanol/toluene mixture in the presence of H3PMo12O40 increases the amount
of extractives and their solubility in chloroform, while in the presence of MoO3 only
the solubility of extractives increases. GC–MS analysis of insoluble fraction showed
the presence of myo-inositol and some simple carbohydrates, mainly ribose, xylose
and glucose. GC–MS analysis of soluble fraction showed the presence of long-chain
acids and fatty acid esters of 10–20 carbon atoms, mainly decanoic acid, hexadeca-
noic acid and octadecanoic acid, which can be a source of fatty acids for biodiesel
production.
* Marisabel Mecca
marisabelmecca@libero.it
1
Department of Science, University of Basilicata, Viale dell’Ateneo Lucano 10, 85100 Potenza,
Italy
2
School of Agricultural Forestry, Food, and Environmental Science, University of Basilicata,
Viale dell’Ateneo Lucano 10, 85100 Potenza, Italy
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Wood Science and Technology
Introduction
Heat treatment of wood is getting more and more popular over the last several
years, and it is one of the environmentally friendly methods to protect and to
extend the service life of wood. It is known that thermal modification enhances
overall dimensional stability and biological durability of wood along with chang-
ing its colour without using chemicals (Esteves and Pereira 2009). However, heat
treatment adversely influences mechanical properties of wood including compres-
sion strength, bending strength and hardness due to modification of the chemical
structure of its main components, namely hemicelluloses, cellulose, lignin and
extractives (Cademartori et al. 2013).
Although many studies have been carried out on the improvement of the over-
all properties of wood, there has been a recently increasing interest in the char-
acterization of the thermal degradation of treated wood products (Jones 2015;
Todaro et al. 2015), which could be related to both increased demand for heat-
treated wood and newly developed environmental management policies (ISO
14040 2006; ISO 14044 2006). The thermal decomposition process of wood and
wood products is based on a series of complex reactions influenced by many fac-
tors, such as the heating rate, temperature, exposure time, pressure, moisture,
composition of biomass material and the size of particles.
Extractives are responsible for the colour, smell and durability of the wood
(Rowell et al. 2012). Furthermore, extractives can represent a source of valuable
fine chemicals such as fatty acids, terpenes and phenols. Therefore, the extrac-
tives can be used in chemical industry, in cosmetic industry or for their biological
antioxidant properties in pharmaceutical and nutraceutical industry.
Recently, several efforts have been reported relating to the lignin degradation
to obtain fine chemicals (Rinaldi et al. 2016).
While the use of oxidant catalysts in the lignin depolymerization is the object
of widespread research (Li et al. 2015; Mukherjee et al. 2016), the possible use
of these catalysts to induce oxidative depolymerization of wood, increasing the
amount of low molecular mass chemical compounds that can be obtained from
wood, has not been studied until now.
On the basis of these results, the possible use of some oxidants of Mo(VI) to
induce chemical degradation of wood was tested. The selection of this type of
oxidant species is due to the intention, on the one hand, to re-evaluate the work of
an ancient chemist, Francesco Mauro (chemist able to synthesize several Mo(V)
and Mo(VI) derivatives, born in Basilicata, and coworker of Stanislao Canizzaro)
(D’Auria et al. 2014), and on the other hand, on the basis of the green properties
of this type of catalyst (Podgors’ek et al. 2009).
Therefore, because extractives are the key constituents that provide the dura-
bility of wood, in this contribution, the objectives were to evaluate the effect of
heat treatment on extraction yield, the chemical composition and on the quality
of the extractives, to demonstrate that available new procedures could be used
to obtain wood degradation in order to (1) increase the amount of recoverable
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extractives, and (2) show that wood can be a source of valuable fatty acids for the
production of biodiesel (Mecca et al. 2017).
For this purpose, Populus nigra L., Larix deciduas Mill., Paulownia tomen-
tosa Steud., Castanea sativa Mill. and Quercus frainetto Ten. untreated wood and
thermo-treated wood were used.
Populus nigra is a geographically widespread tree species of which stands are
found in large parts of Europe and Asia. The species is a typical pioneer species par-
ticularly in riverine areas. It is dioecious, heliophilous and characterized by an effi-
cient dissemination of both seeds and pollen, but also by its good ability to naturally
undergo vegetative propagation. It is a species of both social and economic interest.
In poplar breeding programs it plays a central role: 63% of the poplar cultivars from
the international register descend from this species, mainly as interspecific hybrids.
In addition to wood production, it is used as a windbreak for the protection of agri-
cultural land and for ornamental and landscaping purposes (Frison et al. 1995).
Larix decidua, a deciduous conifer endemic to Europe, is an industrially impor-
tant tree, characterized by a strong, water-resistant and durable wood but also flex-
ible in thin strips. The heartwood is particularly weatherproof and, therefore, mainly
used as construction timber. Due to its high resin content and difficult machinabil-
ity, its use for furniture production is limited (Pferschy-Wenzig et al. 2008). At pre-
sent, larch sawdust is mainly used for the production of pellet fuels, and it contains
phenolic compounds, such as lignans and flavonols (mainly dihydroquercetin and
dihydrokaempferol) (Salem et al. 2016). Barks and branches are waste material of
the timber industry with important, but also partially underexplored, supplies of bio-
logically active compounds; this material can be considered a good source of anti-
oxidants and phytoconstituents with possible use in cosmetic or nutraceutical prod-
ucts; furthermore, several conifer barks contain phytoconstituents, such as tannins,
terpenes and polyphenols (Bianchi et al. 2015).
Paulownia tomentosa is a plant species belonging to the Paulowniaceae family,
which includes 17 species of trees, all endemic to the South and East Asia. Paulow-
nia wood, a light-coloured hardwood, has been revered for centuries by Japanese
craftsmen because of its workability and beauty. In the Japanese tradition, Paulow-
nia was used to build kotos (Japanese harps) because of the wood’s superior acous-
tical quality, and it is now also used as timber and biomass, and in Chinese agro-
forestry systems because it grows fast, its wood is light but strong, its flowers are
rich in nectar, and its leaves make good fodder for farm animals. Paulownia wood
also resists splitting and deformation in the drying process and can retain nails and
screws without splitting (Kaygin et al. 2009). Fast developing programs for planting
and growing Paulownia, with the help of financial support, are performed in Italy.
Presently, they are the sources for the fast supply of high-quality timber and energy.
Castanea sativa, or sweet chestnut, is a plant species in the family Fagaceae,
native to Europe and Asia Minor. Castanea sativa heartwood is one of the most
durable wood species in Europe. Due to its good durability, the wood is frequently
used for utility poles and posts and other outdoor applications, both in and above
ground. In addition, this wood is used for manufacturing furniture, barrels and con-
structions, notably in southern Europe (Dieste et al. 2012). One of the reasons for
the good durability is the presence of extractives, predominantly tannins. Chestnut
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trees are a rich source of tannins, which were used in the past for the production of
some medicines, leather production, as well as playing a part in the flavouring of
various types of alcoholic beverages (Gironi and Piemonte 2011).
Quercus is one of the most important woody genera due to its large number of
species, including trees and shrubs in Turkey. Oak belongs to the family Fagaceae,
its botanical name is Quercus frainetto, and it is known by many common names
across the globe such as Hungarian oak and Italian oak. These trees are also tolerant
to different environmental and climatic conditions and contribute to erosion control.
It is often used for firewood, and because of the rather high durability of its wood,
Quercus frainetto wood sometimes has been used as construction material in civil
engineering and mining. It is less suited for the manufacture of barrels and furniture
(Bartha et al. 1998).
Thermo-treatment of wood has been used in order to obtain a wood that is more
resistant to outdoor conditions, changing the decay resistance and the dimensional
stability; indeed, thermo-treated wood generally shows a decreased wettability.
Materials and methods
Paulownia tomentosa, Populus nigra and Larix decidua boards free of defect for
each species were supplied by a local manufactures located at Calitri (Avellino prov-
ince, Campania Region, Italy).
Castanea sativa and Quercus frainetto boards were obtained from a natural high
forest located in Calvello municipality (Potenza province, Basilicata Region, Italy).
A total of eight sawn boards for each species (Populus nigra, Larix decidua,
Paulownia tomentosa, Castanea sativa and Quercus frainetto) with dimensions of
30 mm × 180 mm × 1500 mm (thickness × width × length), having a moisture content
of 20%, were used for the experiments.
The thermo-vacuum plant facility used for the test, following the description of
Ferrari et al. (2013b), was a semi-industrial prototype with an internal diameter of
1.7 m, modified to perform thermo-vacuum treatments at high temperature (up to
250 °C). The cylinder walls were heated by diathermic oil circulating between dou-
ble layers of steel.
The samples were dried to a moisture content of 0% in the same cylinder prior
to the thermo-vacuum treatments. The drying process of the samples having an ini-
tial moisture content of 20% was carried out at 100 °C and a pressure not exceed-
ing 25,000 Pa, corresponding to a water boiling temperature of 65 °C (Ferrari et al.
2013b).
In the next step, samples of the abovementioned species were exposed to the
thermo-vacuum treatment. Each thermo-vacuum treatment consisted of a heating
phase that started at a temperature of 100 °C and reached a maximum air tempera-
ture of 190 °C followed by a thermal treatment phase with a different constant air
temperature for 2 h: 170 °C for Castanea sativa, 200 °C for Populus nigra and Larix
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decidua, 180 and 200 °C for Quercus frainetto, and 180 °C, 200 °C and 210 °C for
Paulownia tomentosa.
Three-hour cooling phase decreased the temperature of the samples to 100 °C.
The heating rate of the air was 12 °C/h. The temperature variation of the diathermic
oil, air and wood samples was measured using thermocouples. The reason for the
different treatment is that each type of wood is associated with one specific type of
treatment because of the different nature of hardwood and softwood (Ferrari et al.
2013a).
Soxhlet extraction
The samples of wood obtained in “Sample preparation and heat treatment” section
were dried at 105 °C overnight. Then, it was ground through a 40-mesh screen using
a Wiley mill.
The obtained material (1.0 g) was put into an extraction thimble, which was
placed into a Soxhlet extraction apparatus. The sample was extracted with 300 ml of
1:2 ethanol/toluene mixture (v/v) for 7 h. After this period, the solvent was evapo-
rated in vacuo (D’Auria et al. 2017).
Lignin content
The remaining sawdust was transferred to a 50-ml beaker, a cold H 2SO4 solution
(72%) (15 ml) was added, and the mixture was frequently stirred for 2 h at room
temperature.
The mixture was then diluted to 3% (w/w) with 560 ml of distilled water, heated
under reflux for 4 h, filtered and washed with 500 ml of water. The residue was dried
at 105 °C to a constant mass. The holocellulose content was determined by differ-
ence between the residue amount after extraction and the lignin content (Mohareb
et al. 2012).
Autoclave extraction
A sample of wood (10 g) was put into an airtight glass jar with 50 ml of distilled
water and placed into the autoclave (Vapor Matic 770) for 20 min, at a tempera-
ture of 120 °C and a pressure of 1 bar for the extraction. The sample was filtered
and frozen at a temperature of − 28 °C. Then, it was lyophilized to remove water
(D’Auria et al. 2017). The obtained mixture was fractionated as follows: the mixture
was treated with chloroform (20 ml) and filtered, the solvent was evaporated, and
the residue was chromatographed using thin layer chromatography on silica gel in
the presence of a fluorescent indicator and using a hexane/ethyl acetate mixture. The
different bands revealed by UV irradiation were scraped off and eluted with ethyl
acetate. The solvent was evaporated, and the residue was analysed as described in
“Gas chromatographic–mass spectrometric analyses” section. The chloroform-insol-
uble fraction was treated as described in “Derivatization” section.
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The sample (10 g) was put into an airtight glass jar with 50 ml of distilled water
and 1 g of the catalysts MoO3/SiO2 or H3PMo12O40, and then it was placed into the
autoclave (Vapor Matic 770) for 20 min at a temperature of 120 °C and a pressure
of 1 bar. Then, the sample was filtered, frozen at a temperature of − 28 °C and lyo-
philized to remove water, while for Soxhlet extraction, the sample (1.0 g) was put
into an extraction thimble with 0.1 g of the catalysts M
oO3/SiO2 or H 3PMo12O40,
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and then it was placed into a Soxhlet extraction apparatus. The sample was extracted
with 300 ml of 1:2 ethanol/toluene mixture (v/v) for 7 h. After this period, the sol-
vent was evaporated in vacuo.
Derivatization
Analyses of all the extractives obtained using all the procedures previously described
were accomplished with an HP 6890 Plus gas chromatograph equipped with a Phe-
nomenex Zebron ZB-5 MS capillary column (30 m × 0.25 mm i.d. × 0.25 μm FT)
(Agilent, Milan, Italy). An HP 5973 mass selective detector (Agilent) was utilized
with helium at 0.8 ml/min as the carrier gas. A split injector was maintained at
250 °C and the detector at 230 °C. The oven was held at 80 °C for 2 min, then grad-
ually warmed, 8 °C/min, up to 250 °C and held for 10 min. Tentative identification
of aroma components was based on mass spectra and Wiley 6 and NITS 98 library
comparison.
Results and discussion
Populus nigra, Larix decidua, Paulownia tomentosa, Castanea sativa and Quercus
frainetto samples were used in this study. Samples of these woods were thermo-
treated as described in “Materials and methods” section, and the amount of extrac-
tives, lignin and holocellulose was determined.
Heat treatment of wood changes its chemical composition by degrading cell wall
compounds and extractives. The chemical changes due to heating depend on the
duration and temperature of the treatment, the temperature being the main factor
(Bourgois et al. 1989). For low temperatures, the wood dries, beginning with the loss
of free water and finishing with bound water, whereas at high temperatures the car-
bonization processes start with the formation of CO2 and other pyrolysis products.
The histograms in Fig. 1 (where the controls are shown in white and the thermo-
treated samples in black) show that the holocellulose content of the treated samples
decreased compared to those of the untreated wood. In contrast, the lignin content
of the samples is relatively higher in the treated samples than in the untreated sam-
ples. This trend was observed for all samples, except for Populus nigra heat-treated
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Wood Science and Technology
(a) % HOLOCELLULOSE
Control
Treated
64.8
61.6 60.8
56.7
53.7 54.5
51.1 51.9
50.3
45.5 45.7
42.1
36.2
% LIGNIN 54.5
(b)
48.1
45.1 45.2
39.6 40.4
39.0 39.5
37.7 37.6
32.7 31.9
27.8
at 200 °C and Paulownia tomentosa thermally treated at 180 °C, where an oppo-
site pattern was observed: the content of holocellulose increased and the content of
lignin decreased.
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% EXTRACTIVES
(a) Control
Treated
15.7
15.3
10.2
9.4
8.5 8.6
7.9
7.4 7.3
5.7
3.7 3.4
2.9
% EXTRACTIVES
(b) 7.6
5.3
4.8
4.2
3.3
1.6 1.6
1.4 1.4
0.9 1.0 0.9
0.5
Fig. 2 Amount of extractives by Soxhlet (a) and autoclave (b) extraction of the samples
When the extraction was performed in an autoclave using water, the content
of the extractives increased by 3.40% for Castanea s., by 0.20% for Larix d., by
1.10% for Populus n., and by 0.14%, 0.59% and 0.07% for Paulownia t. at 180 °C,
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Wood Science and Technology
200 °C and 210 °C, respectively, but the amount of the extractives decreased by
0.50% and 2.00% for Quercus f. at 180 °C and 200 °C, respectively, compared to
those of untreated wood. As reported below, the composition of water extractives
mainly depends on the presence of pentoses and hexoses. It is reasonable that in
thermo-treated species where the cellulose amount increases, the fraction that can be
extracted in water increases.
In addition, the possible effect of oxidants of Mo(VI) to induce degradation of
wood during the autoclave and Soxhlet extraction was tested. The effect of the pres-
ence of 10% of a polyoxometalate compound, such as H3PMo12O40 and that of silica-
supported MoO3, was tested in particular for Castanea sativa at 170 °C. The results
are reported in Fig. 3. Clearly, the presence of the Mo(VI) derivatives induced an
extensive degradation of wood, thereby allowing an increased recovery of extrac-
tives. In particular, in Soxhlet H
3PMo12O40 increased the amount of extractives by
3.4% and by 8.2% in the autoclave. MoO3 reduced the amount of extractives by 0.9%
in Soxhlet, but increased the extraction yield by 1.2% in the autoclave. Furthermore,
the obtained extractives were fractionated considering the capability of the com-
ponents to be soluble in chloroform (dielectric constant 4.81, able to dissolve apo-
lar and medium polar compounds). In the case of the present samples, in Soxhlet
extraction in the presence of H 3PMo14O40 the solubility of the extracts increased by
9.2%, while it was reduced by 1.5% when the extraction was performed in the auto-
clave. These results can be explained by considering the different effects of the oxi-
dant on lignin and cellulose. The polyoxometalated compound induced a selective
degradation of lignin and cellulose inducing an increase in the amount of extractives
12.4
8.8
7.6
3.2
2.7
1.2
0.3
Control H3PMo12O40 MoO3 Control H3PMo12O40 MoO3
Fig. 3 Amount of extractives and solubility of Castanea sativa at 170 °C by Soxhlet (white) and auto-
clave (grey) extraction in the presence of the Mo polyoxometalate derivative
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Wood Science and Technology
both in Soxhlet and in autoclave extraction processes. However, the autoclave treat-
ment allows the selective extraction of polar components of the extracts, with the
consequent reduction in the chloroform-soluble fraction. When the Soxhlet extrac-
tion was performed in the presence of MoO3, the oxidant was not able to oxidize
wood, and the treatment induced only an oxidation process of the extractives that
are reduced. The oxidation occurred mainly on the polar fraction of the extractives,
and then, the solubility in chloroform increased by 12.3%. When the extraction was
performed in the autoclave, MoO3 was able to induce an oxidative depolymerization
of wood with the consequent increase in the extractives amount. However, it reduces
the solubility in chloroform by 2.4% considering that, in water, the extraction occurs
mainly on polar compounds.
The main compounds of the chloroform-soluble fraction of the extractives were
determined on the basis of their mass spectra. These compounds were obtained with
an overall chemical yield of 31–44% (w/w), based on the different species of wood.
From the GC–MS analysis, the main compounds of the soluble extractives are long-
chain acids and fatty acids or esters of fatty acids from 10 to 20 carbon atoms, spe-
cially n-hexadecanoic acid, 9-octadecenoic acid and 9,12-octadecadienoic acid. On
the contrary, using wood of conifers, tall oil obtained in the kraft pulp production
contains large amounts of fatty acids (Rowe 1989) (see Supplementary Material).
The main compounds of the insoluble fraction of extractives were determined
after acetylation of the mixture. Sugars, in particular glucopyranose pentaacetate
and glucitol hexaacetate, were recovered. Furthermore, a polyhydroxylated com-
pound, myo-inositol hexaacetate, was determined in the mixture. The overall chem-
ical yields were in the range of 11–63% (w/w), based on the different species of
wood.
There also appeared new compounds in the thermo-treated samples resulting
from the degradation of cell wall structural components: apocynin (a, S1) in Cas-
tanea sativa at 170 °C and Populus nigra at 200 °C, with anti-arthritic (Hart et al.
1990) and anti-asthmatic (Stefanska and Pawliczak 2008) properties, aspidinol (b,
S2) in Quercus frainetto at 200 °C, that is an anti-parasite (Bosman et al. 2004),
sinapaldehyde (c, S3) in Quercus frainetto at 180 °C and Populus nigra at 200 °C,
used as a flavouring agent, and it also is a cyclooxygenase inhibitor (Setzer 2011),
and fenozan (d, S4) and asarinin (e, S5) in Paulownia tomentosa at 180 °C, 200 °C
and 210 °C, which are both antioxidants, vasodilators and antithrombotic agents
(Bespalov et al. 2016; Yasuda et al. 2012; Mordi et al. 2016) (Fig. 4 and S1, S2, S3,
S4, S5 in Supplementary Material).
Conclusion
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Wood Science and Technology
(d) (e)
thermally treated at 180 °C, where an opposite pattern was observed: the content
of holocellulose increased, and the content of lignin decreased.
In this research, the possible effect of oxidants of Mo(VI) to induce degrada-
tion of wood during the autoclave and Soxhlet extraction was tested particularly
for Castanea sativa wood thermo-treated at 170 °C. As a general statement, the
polyoxometalated compound induced a selective degradation of lignin and cellu-
lose. It increased the extractives amount both in Soxhlet and in autoclave extrac-
tion processes, with a greater activity on heat-treated wood.
About autoclave and Soxhlet treatment of the samples in the presence of some
molybdenum catalysts, in Soxhlet extraction both catalysts increased solubility,
but only H 3PMo12O40 increased the extraction yields, while in the autoclave both
catalysts increased the yields of extractives, but they reduced solubility. Clearly,
in these conditions, the presence of the oxidants induced a selective degradation
of cellulose increasing the amount of chloroform-insoluble carbohydrates.
The effect of the oxidants seems to induce mainly the oxidative fission of cel-
lular membranes. The use of a molybdenum catalyst depended on the evidences
that molybdenum can act as catalyst in Fenton-like reactions. However, molybde-
num compounds have not been used for this purpose until now.
The organic solvent-soluble fraction was composed of 31–44% by long-chain
acid and fatty acid esters, while the water-soluble fraction of the extractives and
the insoluble fraction of extractives can be a source of simple carbohydrates.
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Wood Science and Technology
In conclusion, the heat treatment and the use of molybdenum catalysts increased
fatty acid esters which have a possible use in biodiesel synthesis. Furthermore, the
increased amount of carbohydrates allowed to obtaining valuable amounts of bio-
logically active compounds.
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