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Bioresource Technology 101 (2010) 38083815

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Bioresource Technology
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Review

Proximate analysis, backwards stepwise regression between gross caloric


value, ultimate and chemical analysis of wood
C. Telmo a,*, J. Lousada b, N. Moreira b
a
University of Trs-os-Montes and Alto Douro (UTAD), Forestry Department, Quinta dos Prados Apartado, 1013-5001-801 Vila Real, Portugal
b
CITAB, Centre for the Research and Technology of Agro-Environment and Biological Sciences, UTAD, Quinta dos Prados Apartado, 1013-5001-801 Vila Real, Portugal

a r t i c l e i n f o a b s t r a c t

Article history: The gross caloric value (GCV), proximate, ultimate and chemical analysis of debark wood in Portugal
Received 1 October 2009 were studied, for future utilization in wood pellets industry and the results compared with CEN/TS
Received in revised form 4 January 2010 14961. The relationship between GCV, ultimate and chemical analysis were determined by multiple
Accepted 11 January 2010
regression stepwise backward. The treatment between hardwoodssoftwoods did not result in signicant
Available online 1 February 2010
statistical differences for proximate, ultimate and chemical analysis. Signicant statistical differences
were found in carbon for National (hardwoodssoftwoods) and (National-tropical) hardwoods in volatile
Keywords:
matter, xed carbon, carbon and oxygen and also for chemical analysis in National (hardwoodssoft-
Heating value
Proximate analysis
woods) for F and (National-tropical) hardwoods for Br. GCV was highly positively related to C (0.79***)
Ultimate analysis and negatively to O ( 0.71***). The nal independent variables of the model were (C, O, S, Zn, Ni, Br) with
Chemical analysis R2 = 0.86; F = 27.68***. The hydrogen did not contribute statistically to the energy content.
Wood 2010 Elsevier Ltd. All rights reserved.

1. Introduction mination of major elements (Na, K, Ca, Mg, Fe and P), minor ele-
ments (Mn, Zn, Ni, Cr, Cd and Cu) and three halogens (F, Cl and Br).
According to the National Forest Inventory 2006, the Portuguese The wood fuel properties gross caloric value (GCV), proximate,
forest area is occupied mainly by Quercus suber 736700 ha, Pinus ultimate and chemical analysis determined according to the Euro-
pinaster 710600 ha and Eucalyptus globulus 646700 ha. However, pean Committee for standardization (CEN/TS). The determination
only the two last species have potential to be used for energy in of the GCV, vary within a species and between species, generally
large-scale because Q. suber it is only used in the cork industry softwood species have higher carbon content and heating values
and is a protect species. The E. globulus used primary for paper than hardwood species. According to (CEN/TS 14961, 2005) the
industry is now having a great competition from the pellets indus- typical value of GCV for softwoods in dry basis is 20.5 MJ/kg and
try that uses this species in the sawdust mixtures. There are no for hardwoods 20.2 MJ/kg. The proximate analysis of wood without
studies about proportion and potentially of these species and the bark in dry basis is 0.3% to ash (CEN/TS 14961, 2005). The quantity
others referred in this paper in Portugal that is why the importance of volatiles in biomass fuels is high and usually varies between 76
of our study, to known these species better. However there is re- and 86 wt.% dry basis (d.b.) in woody biomass (Van loo and Koppe-
search studies in other countries to others softwoods and hard- jan, 2002) and 15% to 25% xed according to same literature, but
woods with similar properties like (Baernthalera et al., 2006; not dened in CEN/TS 14961 (2005). The ultimate analysis of soft-
Brunner et al., 1998; Brunner et al., 2002; Faaij et al., 1997; Lind wood species is generally 51% carbon, 6.3% hydrogen, 42% oxygen,
et al., 1998; Nordin, 1994; Obernberger and Biedermann, 1998; 0.1% nitrogen, 0.02% sulfur and 0.01% on a dry ash free basis. In
Obernberger, 1999). hardwoods the C content is 49%, H 6.2%, O 44%, N 0.1%, S 0.02%
An analysis programme of biomass fuels has been carried out and Cl 0.01%. The range of content for softwoods species in C is
within the framework of CEBIO (Competence Network for Bioener- (4754%), H (5.67.0%), O (4044%), N (<0.10.5%), S (<0.01
gy) and the University of Tras-Os-Montes and Alto Douro. 0.05%) and Cl (<0.010.03%). The range of content for hardwoods
The parameters tested within the framework of this analysis species in C is (4852%), H (5.96.5%), O (4145%), N (<0.10.5%),
programme Tables 1 and 3, were gross caloric value, ash content, S (<0.010.05%) and Cl (<0.010.03%) (CEN/TS 14961, 2005).
volatile matter, xed carbon, the contents of C, H, O, N and S deter- The chemical analysis which includes (major, minor and halo-
gens elements in mg/kg in a dry basis), are as follow. The typical
values in softwoods for major elements contents in (mg/kg) are
Al (100), Ca (900), Fe (25) K (400), Mg (150), Mn (147), Na (20)
* Corresponding author. Tel.: +351 914 165 175; fax: +351 259 350 859.
E-mail address: telmimore@hotmail.com (C. Telmo). and P (60). The typical values in softwoods for minor elements

0960-8524/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2010.01.021
C. Telmo et al. / Bioresource Technology 101 (2010) 38083815 3809

Table 1
Mean of gross caloric value (Mj/kg), proximate and ultimate analysis of wood (wt.% in dry basis).

Species GCV ASH VM FC C H O N S


Pinus pinaster 20.1 0.2 85.8 14.1 48.4 6.0 45.3 0.1 0.00
Pseudotsuga menziesii 19.7 0.4 83.9 15.7 47.6 5.9 45.8 0.2 0.01
Cedrus atlantica 20.3 0.4 82.9 16.7 50.3 5.6 43.6 0.2 0.00
Castanea sativa 18.7 0.1 79.6 20.3 47.1 4.9 47.7 0.2 0.02
Eucalyptus globulus 17.6 0.5 86.3 13.3 46.2 5.8 47.2 0.2 0.02
Fagus sylvatica 19.1 0.5 85.7 13.9 46.7 5.9 46.8 0.2 0.02
Quercus robur 18.7 0.3 81.7 18.0 47.2 5.5 46.8 0.2 0.01
Fraxinus angustifolia 19.2 0.4 84.9 14.7 47.7 6.1 45.6 0.2 0.04
Prunus avium 18.3 0.1 84.9 15.0 48.6 5.8 45.3 0.2 0.05
Salix babilonica 18.2 2.4 80.8 16.8 47.2 5.6 44.4 0.4 0.00
Populus euro-americana 18.8 0.5 87.1 12.4 47.8 6.0 45.4 0.2 0.03
Acer pseudoplatanus 18.6 1.0 85.1 13.9 46.8 5.8 46.1 0.2 0.06
Chlorophora excelsa 20.3 2.8 74.7 22.5 50.7 6.0 40.4 0.2 0.00
Entandrophragma cylindricum 19.0 1.0 81.7 17.3 47.8 5.8 45.1 0.3 0.01
Gossweilerodendron balsamiferum 20.4 0.4 83.8 15.8 50.4 6.2 42.5 0.5 0.01
Bowdichia nitida 20.7 0.1 81.8 18.2 52.3 6.1 41.3 0.2 0.03
Hymenaea courbaril 19.2 0.7 81.7 17.6 48.3 5.7 45.1 0.2 0.04

Table 2
Mean, SD in brackets, test comparison of means of proximate and ultimate analysis by type of wood (wt.% in d. basis). Note: mean values with the same letter are not signicantly
different for p<0.05 by TukeyKramer test.

Species (treatment) Ash VM FC C H O N S


Hardwoods (H) (1) 0.8 a 82.8 a 16.4 a 48.2 a 5.8 a 45.0 a 0.2 a 0.02 a
(0.8) (3.2) (2.8) (1.8) (0.3) (2.2) (0.1) (0.02)
Softwoods (S) 0.3 a 84.2 a 15.5 a 48.8 a 5.8 a 44.9 a 0.2 a 0.01 a
(0.1) (1.3) (1.2) (1.4) (0.2) (1.2) (0.0) (0.01)
H. National (HN) (2) 0.6 a 84.0 a 15.4 a 47.3 a 5.7 a 46.2 a 0.2 a 0.03 a
(0.7) (2.6) (2.4) (0.7) (0.3) (1.0) (0.1) (0.02)
S. National (SN) 0.3 a 84.2 a 15.5 a 48.8 b 5.8 a 44.9 a 0.2 a 0.01.a
(0.1) (1.3) (1.2) (1.4) (0.2) (1.2) (0.0) (0.01)
H. National (HN) (3) 0.6 a 84.0 a 15.4 a 47.3 a 5.7 a 46.2 a 0.2 a 0.03.a
(0.7) (2.6) (2.4) (0.7) (0.3) (1.0) (0.1) (0.02)
H. Tropical (HT) 1.0 a 80.7 b 18.3 b 49.9 b 5.9 a 42.9 b 0.3 a 0.02.a
(1.0) (3.3) (2.4) (1.9) (0.2) (2.2) (0.1) (0.02)

contents in (mg/kg) are Cd (0.10), Cr (1.0), Cu (2.0), Ni (0.5) and Zn fur. Elemental analysis can be used to describe biomass fuels,
(10). The typical values for major elements contents in hardwoods determine their caloric values (Friedl et al., 2005) and their ex-
in (mg/kg) are Al (20), Ca (1200), Fe (25) K (800), Mg (200), Mn pected impact on the environment. An example of that is the S con-
(83), Na (50) and P (100) (CEN/TS 14961, 2005). tent in woods whose importance does not result especially from
The typical values in hardwoods for minor elements contents in SO2 and SO3 emissions but from is role in the corrosion processes.
(mg/kg) are Cd (0.10), Cr (1.0), Cu (2.0), Ni (0.5) and Zn (10). The A higher concentration of S can cause sulphation and leads to Cl re-
typical variation on major elements contents in softwoods (mg/ lease. It can cause corrosion by FeCl2 and ZnCl2 in the boilers. The
kg) is Al (30400), Ca (5001000), Fe (10100) K (200500), Mg SO2 emissions are not signicant for wood combustion because
(100200), Mn (no value), Na (1050) and P (50100). The typical their low S content, but can be relevant for agricultural residues,
variation on major elements contents in hardwoods (mg/kg) is Al grasses and straw.
(1050), Ca (80020000), Fe (10100) K (5001500), Mg (100 The method used is described in Section 2, in total 17 samples of
400), Mn (no value), Na (10200) and P (50200) (CEN/TS 14961, debarked wood were obtained within the framework of the analy-
2005). sis programme. The objectives of the work were to get an overview
The minor elements had the same typical value and the same about the gross caloric value, proximate and ultimate analysis
typical variation in hardwoods and softwoods, the typical variation and the chemical composition of debark wood in Portugal, for fu-
for minor elements contents (mg/kg) is Cd (<0.050.50), Cr (0.2 ture utilization in wood pellets industry. The variations of these
10.0), Cu (0.510.0), Ni (<0.110.0), Zn (5100) (CEN/TS 14961, properties among the species and between softwoods, National
2005). hardwoods and tropical hardwoods, using TurkeyKramer test, as
While major elements are of key relevance regarding ash melt- well as a comparison between the analyses results achieved and
ing, deposit and slag formation as well as corrosion, minor ele- the limiting values dened in the CEN Technical Standards and
ments are of special importance for particulate emissions as is Specications for Solid biofuels. Finally, the determination of the
the environmental assessment of the ashes produced and their relationship between gross caloric value, ultimate and chemical
subsequent utilization. analysis by multiple regression stepwise backward.
The thermal utilization of solid biofuels is inuenced by the
kind of solid biofuel used, its physical characteristics and its chem-
ical composition (Directive 2000/76/EC, 2000). 2. Methods
The caloric value of wood can be related to it chemical compo-
sition (Fengel and Wegener, 1983). Major elements contributing to All measurements and analyses were performed by us in the
the caloric value are carbon, hydrogen, nitrogen, oxygen and sul- Chemical Department of the University of Tras-Os-Montes and Alto
3810 C. Telmo et al. / Bioresource Technology 101 (2010) 38083815

Douro. The gross caloric values were measured in the Mechanical ballast are mixed, and a small aliquot dose is then used for further
Department. The contents of the elements (C, S and N) were conversion of the gases. The remaining aliquot that has been re-
determined in the to-chemical and food composition labora- duced is measured by the thermal conductivity cell for Nitrogen,
tory, in UTAD. The element (H) was done in Lisbon in a Leco in a Leco FP-528. Two determinations per sample were performed
laboratory. according to CEN/TS 15104 (2005) to the (C, N) and according to
CEN/TS 15289 (2006) to (S) determination.
2.1. Determination of gross caloric value
2.9. Determination of total content of (H)
The gross caloric value at constant volume in dry basis was
determined according to (CEN/TS 14918, 2005). The samples The Leco TruSpec TRSCHNC was used to determine Hydrogen,
weights ranging from 0.5 to 0.6 g to avoid invalid combustion, they however it can analyze carbon and nitrogen. The system is based
were combusted in a Parr 6300 automated isoperibol calorimeter. on the Dumas method of combustion, there are three phases dur-
There were three replications for each sample. ing an analysis cycle: purge, burn, and analyze. In the sample-drop
purge phase, the encapsulated sample is placed in the loading
2.2. Determination of ash content head, sealed, and purged of any atmospheric gases that have en-
tered during sample loading. The ballast volume (zero volume at
The ash content was determined by burning 1 g of oven-dried this point) and gas lines are also purged. During the burn phase,
sample in a platinum crucible in a mufe furnace model (Lenton the sample is dropped into the primary furnace (950 C) and
Thermal Designs EF 11/8B) at 550 25 C. All analyses were done ushed with pure oxygen for very rapid combustion. The products
in duplicate and the results were expressed on a dry weight basis of combustion are passed through the after-burner furnace, fur-
according to CEN/TS 14775 (2004). nace lter, pre-cooler, and thermoelectric cooler before collecting
in the ballast volume. In the analyze phase, the combustion gases
2.3. Determination of volatile matter in the ballast become homogeneous by means of passive mixing.
A series of infrared detectors then measure the evolved gases for
The volatile matter was determined by burning 1 g of oven- carbon and hydrogen. In addition, a 3 cc aliquot is captured in a
dried sample in a fused silica crucible with lid in a mufe furnace loop before the ballast piston is forced down to evacuate the bal-
model (Lenton Thermal Designs EF 11/8B) at 900 10 C. All anal- last. An optimized detector was used for Hydrogen. The nal result
yses were done in duplicate and the results were expressed on a was displayed as weight percentage, according to CEN/TS 15104
dry weight basis according to (CEN/TS 15148, 2005). (2005).

2.4. Fixed carbon


2.10. Determination of total content of (O)
The xed carbon content was obtained by subtracting from
The oxygen content was obtained by subtracting from 100% the
100% the sum of volatile matter and ash contents in percentage.
sum of (C, H, N, S and ash) contents in percentage.
The mean, standard deviation and a test comparison means (Tu-
2.5. Determination of Major elements (Na, K, Ca, Mg, Mn, Fe, Zn and P)
keyKramer) were done for proximate, ultimate and chemical
analysis by type of wood in dry basis. The correlation coefcient
Heat the sample (550 C) according to the procedure described
matrix was determined for the GCV, ultimate and chemical analy-
in CEN/TS 14775 (2004) to obtain ash.
sis. A backward stepwise multiple regression was employed be-
Digestion: Resistance heating 220 C, digestion with HNO3
tween the dependent variable (GCV) and the independent
(65%), HF (40%), H3BO3 (4%), according to CEN/TS 15290 (2006).
variables (ultimate analysis and chemical analysis of wood in dry
Detection: With ame atomic adsorption spectrometry (FAAS).
basis).
2.6. Determination of Minor elements (Ni, Cr, Cd and Cu)
3. Results and discussion
Digestion: Resistance heating 220 C, digestion with HNO3
(65%), HF (40), H3BO3 (4%), according to CEN/TS 15297 (2006). Table 1 shows the mean of gross caloric value, proximate and
Detection: Graphite furnace atomic absorption spectroscopy (GF- ultimate analysis of seventeen wood species. Ash content (Ad), vol-
AAS). atile matter (Vd) and xed carbon (FC) are considered as proximate
analysis and they were determined on weight percent in dry basis
2.7. Determination of (F, Cl and Br) (wt.% in dry basis). Carbon (C), hydrogen (H), oxygen (O), nitrogen
(N) and sulfur (S) contents are considered as ultimate analysis.
Digestion: Bomb combustion in oxygen; absorption in NaOH They also were determined using weight percent in dry basis
(0.05 M). (wt.% in dry basis).
Detection: High-performance liquid chromatography (HPLC). The gross caloric value ranges from 17.6 MJ/kg in E. globulus to
Cl determined according to CEN/TS 15289 (2006). 20.7 MJ/kg in Bowdichia nitida. These ranging values of the GCV,
were on the typical variation for softwoods, had a lower value in
2.8. Determination of total content of (C, S and N) National hardwoods, and were almost in the limits for tropical
hardwoods, according to CEN/TS 14961 (2005) typical variations.
The Simultaneous determination of Sulfur/Carbon was done in a The data of this Technical Specication were obtained from a com-
Leco SC-144DR using direct combustion and infrared detection. In bination of research work mainly from Sweden, Finland, Denmark
nitrogen determination the sample is dropped into a hot furnace and Germany. These values describe properties that can be ex-
and ushed with pure oxygen for very rapid combustion, and pected in Europe in general, however they were compared to trop-
formed By-products of combustion (CO2, H2O, NOx and N2). Then ical hardwoods values too. It can be seen that ash content ranged
pass through the furnace lter and thermoelectric cooler for subse- from 0.1% in (Castanea sativa, Prunus avium, B. nitida) to 2.8%
quent collection in a ballast apparatus. These collected gases in the weight in dry basis in Chlorophora excelsa. The majority of the spe-
C. Telmo et al. / Bioresource Technology 101 (2010) 38083815 3811

cies were in the typical variation for typical value of ash, usually 0.1 wt% (d.b.) and can therefore be of relevance for straw, cereals,
tropical species have much higher ash content comparing with grasses and fruit residues. The Cl content in wood is generally very
temperate forest species, but not always. Volatile matter is in the low.
range of 74.7% in C. excelsa and 87.1% in Populus euro-americana. The S contained in solid biofuels forms gaseous SO2, sometimes
Fixed carbon is in the range of 12.4%in P. euro-americana and SO3, alkali, alkali-sulphates. The efciency of S xation in ashes de-
22.5% in C. excelsa. Ultimate analysis is very important in order pends on the concentration of Ca in the fuel. According to (Obern-
to determine the theoretical airfuel ratio in thermo-conversion berger, 2003), emission problems are expected at S concentrations
systems, to calculate the heating values and also to have knowl- above 0.2 wt%.
edge of the pollution potential. This study showed that the major Table 2 shows the mean, standard deviation, TukeyKramer test
elemental constituents of biomass are carbon, oxygen, and hydro- for ash content, volatile matter, xed carbon (proximate analysis),
gen. The elemental contents of (C, H, O, N and S) listed in Table 1 carbon, hydrogen, oxygen, nitrogen, and sulfur content (Ultimate
show clearly that these biomass fuels contain higher proportion analysis) of wood wt.% in dry basis. Treatment (1) between all
of carbon content compared with hydrogen and oxygen which in- hardwoods and softwoods showed that hardwoods had a higher
creased the energy value. With the exception of C. sativa, E. globulus content of ash, xed carbon, oxygen and sulfur content. They had
and Fagus sylvatica were the oxygen content is higher than carbon the same average content in hydrogen and nitrogen. Softwoods
content. The weight fraction of carbon ranged from 46.2% in E. glob- had higher volatile matter and carbon content. The study of differ-
ulus to 52.3% in B. nitida, hydrogen from 4.9% in C. sativa to 6.2% in ent wood species did not result in signicant statistical differences
Gossweilerodendron cylindrica, oxygen from 40.4% in C. excelsa to for treatment (1).
47.7% in C. sativa. The measured values of these three components Treatment (2) between National hardwoods and National soft-
are in the range reported by CEN/TS 14961 (2005) for softwoods, woods showed a higher content of ash, oxygen and sulfur in the
tropical hardwoods and had a lower value in some National hard- National hardwoods and also the same content of nitrogen of soft-
woods. The Nitrogen content ranged from 0.1% in P. pinaster to 0.5% woods. The volatile matter, xed carbon, carbon and hydrogen
in Gossweilerodendron cylindrica, sulfur ranged from 0.00% in P. pin- content were higher in softwoods. In the treatment (2) signicant
aster to 0.06% in Acer pseudoplatanus. A very low nitrogen and sul- statistical differences were found in carbon content
fur content was reported in this study for the majority of the In treatment (3), National hardwoods versus tropical hard-
species with exception of the sulfur content in A. pseudoplatanus woods the higher content of volatile matter, oxygen and sulfur
higher than the typical variation (0.010.05%). Coniferous and content occurs in National hardwoods. There is a difference in
deciduous wood has the lowest N content according to CEN/TS the average content of nitrogen between these two types of woods.
335 (2003). Tropical hardwoods had a higher content of ash, xed carbon,
Low chlorine content ranging from 0.00% in almost all the spe- carbon, hydrogen, and nitrogen content, the treatment (3) result
cies to 0.01% in (F. sylvatica, Quercus robur, P. euro-americana, Gos- in signicant statistical differences for volatile matter, xed car-
sweilerodendron balsamiferum). The values of Cl are in the typical bon, carbon and oxygen content.
variation limits (<0.010.03%), (CEN/TS 14961). The lower content The standard deviation for xed carbon, hydrogen and oxygen,
of nitrogen and sulfur in biomass fuels is especially important for was higher in hardwoods (H) with a variation from 0.3% in hydro-
environment protection. The concentrations of N, S and Cl in differ- gen to 2.8% in xed carbon. The standard deviation for nitrogen
ent species are of major importance because they cause gaseous content of hardwoods, National hardwoods and tropical hard-
emissions (NOx, SO2, HCl). Recent investigations have show that woods was the same with a value of 0.1%. The tropical hardwoods
one of the main environmental impacts of solid biofuels combus- standard deviation was higher for ash, volatile matter, carbon and
tion is caused by NOx emissions (Nussbaumer, 2002). The NOx oxygen content with a variation from 1.0% (ash) to 3.3% (volatile
emissions thus increase with increasing fuel N content (Obernber- matter).
ger et al., 1995; Leckner, 1993). The main effect of Cl are the corro- Table 3 shows the chemical composition of the wood (major,
sive effect of chloride salts and HCl on metal parts in the furnace minor and three halogens elements). The major elements in bio-
and boiler (Riedl and Obernberger, 1996; Salmenoja and Makela, mass, such as Na, K, Ca, Mg, Fe and P, are especially important
2000) HCl and particulate (KCl, NaCl, ZnCl2 and PbCl2) emissions. for any thermochemical conversion process. The Table 3 shows
According to (Obernberger, 2003), Cl induced corrosion and HCl some clear differences among the wood species. According to
emission problems are to be expected at fuel concentrations above CEN/TS 14961 (2005), the concentration of Na in P. pinaster

Table 3
Mean of chemical composition of wood (mg/kg) in dry basis.

Species Na K Ca Mg Mn Fe Zn Ni Cr Cd Cu F Cl Br P
Pinus pinaster 98.5 492.0 1.0 58.5 72.0 49.0 31.0 1.5250 0.4646 0.0030 0.2957 0.9 23.0 0.0 5.7
Pseudotsuga menziesii 34.0 815.0 67.0 20.5 43.0 19.5 9.0 0.8715 0.2440 0.0186 0.5770 0.4 32.7 0.0 73.2
Cedrus atlantica 58.5 495.0 98.0 13.0 22.5 23.5 24.5 1.7925 0.9290 0.0109 0.4584 0.3 28.1 0.1 3.3
Castanea sativa 91.5 174.5 44.0 12.0 38.0 131.0 24.5 1.9325 0.9305 0.0006 0.7635 1.2 1.2 0.0 2.4
Eucalyptus globulus 19.5 3100.0 106.5 83.5 34.5 53.0 80.0 0.3270 0.6160 0.0169 0.4452 0.9 11.7 0.0 1285.6
Fagus sylvatica 152.0 1590.0 148.0 40.5 260.0 38.5 32.5 1.7335 0.4535 0.0593 0.5050 1.2 75.8 0.0 12.5
Quercus robur 61.0 720.0 68.5 11.0 29.0 80.5 18.0 1.1260 0.4432 0.0030 0.2489 0.9 85.2 0.0 9.5
Fraxinus angustifolia 45.0 800.0 111.5 10.0 2.5 11.0 1.0 0.8395 0.1195 0.0056 0.3654 1.0 41.8 0.0 3.6
Prunus avium 58.5 275.0 425.0 111.5 25.5 26.0 16.5 0.9705 0.3924 0.0005 0.1672 0.8 32.0 0.0 2.8
Salix babilonica 600.0 12850.0 3650.0 3.0 170.0 40.5 135.0 0.5105 0.8340 0.2083 1.2385 1.1 37.5 0.0 488.1
Populus euro-americana 418.0 650.0 126.0 40.5 37.5 19.5 46.5 1.0045 0.1525 0.0315 0.0557 1.4 54.5 0.0 10.9
Acer pseudoplatanus 56.5 1610.0 175.0 67.5 1.5 19.5 1.0 0.1168 0.1899 0.0003 0.6465 1.8 17.4 0.0 2074.2
Chlorophora excelsa 48.0 3780.0 4750.0 480.0 5.5 32.0 13.5 0.7825 0.2901 0.0010 0.2008 1.4 10.1 0.9 4.5
Entandrophragma cylindricum 34.0 1495.0 236.5 58.5 3.0 23.5 29.0 1.1785 0.5425 0.0003 0.2958 1.6 10.8 0.8 8.4
Gossweilerodendron balsamiferum 70.5 93.0 143.5 41.5 115.0 57.5 20.5 0.7185 1.1150 0.0243 0.9360 3.3 78.8 0.0 0.5
Bowdichia nitida 43.0 127.5 30.5 501.0 1.5 47.0 12.5 1.9935 0.8810 0.0008 0.4493 0.4 28.3 0.0 4.0
Hymenaea courbaril 60.0 1155.0 123.5 5.5 41.5 42.5 41.0 1.1175 0.4669 0.0001 0.1376 2.2 2.9 0.0 16.7
3812 C. Telmo et al. / Bioresource Technology 101 (2010) 38083815

(98.5 mg/kg) was higher than the typical value and typical varia- use of willows for heavy metal phytoremediation suggests that
tion for softwoods. Also P. euro-americana with 418.0 mg/kg had there is great variation in the ability of different Salix species and
the double value than the typical variation, and Salix babilonica species hybrids to take up metals (Landberg and Greger, 2002; Pul-
with 600.0 mg/kg had the triple value. Relatively to K concentra- ford et al., 2002; Vyslouzilova et al., 2003). It is highly likely that
tion was observed a high variation between species whose minor there is genetic variation among Salix clones in their ability to oc-
value was observed in the G. balsamiferum (93 mg/kg) and the cupy different types of contaminated soils and promote remedia-
highest value in the S. babilonica (12850 mg/kg). Pseudotsuga men- tion. Likewise, clones display varying rates of transpiration (Weih
ziesii, E. globulus had almost the double of the content in K allowed and Nordh, 2002), which is an important trait for hydrologic con-
by this technical specication. This element is a major obstacle for trol of contaminated groundwater.
an efcient utilization of these three woods as fuel for heating and Salix spp was shown as shoot accumulators of Cd and Zn in
power production. comparison with other wet species (Stoltz and Greger, 2002). Cd
Generally low values of Ca where obtain, normally in hard- competes with Zn forming protein complexes, soil Zn induces dis-
woods with the exception of the Chlorophora. (4750.0 mg/kg) and sociation of Cd sorbed onto the binding site as a result of competi-
Salix (3650 mg/kg) however with values inside the typical variation tion for these sites increasing the Cd.
for hardwoods (80020000 mg/kg) (CEN/TS 14961, 2005). The B. Table 4 shows the mean, standard deviation, TukeyKramer test
nitida, Q. robur and A. pseudoplatanus had the highest values of of chemical analysis by type of wood wt.% in dry basis. Treatment
Mg, Fe and P. The. Mg concentration in the majority of the species (1) between all hardwoods and softwoods showed that hardwoods
is lower than the typical values and variations, with the exception had a higher content of the major elements (Na, K, Ca, Mg, Fe, P)
of C. excelsa and B. nitida that were upper than the typical variation and the minor elements (Mn, Zn and Cu). The softwoods had the
(100400 mg/kg). A very low concentration of P was found, only E. high percentage of the minor elements (Ni, Cr and Cd). The halo-
globulus, S. babilonica and A. pseudoplatanus had a higher value than gens (F, Br) and (Cl) are higher in hardwoods. The standard devia-
the typical variation (50200 mg/kg). tion in hardwoods had the highest values for (K, Ca and P) because
From literature is known that the content of most of the minor of the great variability in concentrations among the different wood
elements (Mn, Zn, Ni, Cr, Cd and Cu) is higher in agricultural bio- species. However the study did not resulted in signicant statisti-
mass than in forestry biomass, elements in roots, leaves, and bark cal differences for treatment (1).
are much higher than in other parts of the trees. The Mn concentra- Treatment (2) between National hardwoods and National soft-
tions were lower compared with the typical values for almost all woods showed higher concentrations of the major elements (Na,
the species with exception of the F. sylvatica, S. babilonica, G. bals- K, Ca, Mg, Fe and P) and the minor elements (Mn, Zn and Cu) in
amiferum (260.0, 170.0, 115 mg/kg). For the other minor elements hardwoods. The softwoods had higher value of the minor elements
(Zn, Ni, Cr, Cd and Cu), values are within normal with the exception (Ni, Cr and Cd). The halogen (F) and the (Cl) was higher in hard-
of the concentration of Zn and Cd in S. babilonica with (135.0 mg/ woods and softwoods had more (Br) concentration. The standard
kg) and (0.208 mg/kg) higher than the typical variation (5 deviation in National hardwoods had the highest values for (K,
100 mg/kg) to Zn and Typical value 0.10 and variation of Cd Ca and P) because of the great variability in concentrations among
(<0.050.50 (CEN/TS 14961, 2005). The phytoremediation of me- the different wood species. However, only signicant statistical dif-
tal-contaminated soils offers a low-cost method for soil remedia- ferences were found for (F) concentrations. In treatment (3), Na-
tion and several reviews are available (Raskin et al., 1994; Salt tional hardwoods versus tropical hardwoods showed higher
et al., 1996; Cunningham et al., 1995; Cunningham and Ow, concentrations of the major elements (Na, K, Fe and P) and the
1996; Raskin., 1996; Moffat, 1995; Chaney et al., 1995; Salt et al., minor elements (Mn, Zn, Cd and Cu) in National hardwoods. Trop-
1998; Wenzel et al., 1999). Some extracted metals may be recycled ical hardwoods had higher concentrations of major elements (Ca,
for value as Se or Hg. Mg) and minor elements (Ni, Cr). The halogens (F, Br) were higher
Willows (Salix spp) used to accumulate heavy metals from the in Tropical hardwoods and (Cl) higher in National hardwoods. The
soil can be burned in power plants, the heavy metals are concen- standard deviation in National hardwoods had the highest values
trated in the ash for proper disposal. With their rapid growth for (K, P) and in tropical hardwoods in the concentrations of (Ca).
and short rotations, they can take up excess nitrogen and phospho- However, only signicant statistical differences were found for
rus runoff from agricultural activities (Adegbidi et al., 2001). The (Br) concentrations.

Table 4
Mean, SD in brackets, test comparison means of chemical analysis (mg/kg) by type of wood in dry basis. Note mean values with the same letter are not signicantly different For
p < 0.05 by TukeyKramer test.

Species (treatment) Na K Ca Mg Mn Fe Zn Ni Cr Cd Cu F Cl Br P
Hardwoods (H) (1) 125.54a 2030.00a 724.18a 104.71a 54.64a 44.43a 33.68a 1.03a 0.53a 0.03a 0.46a 1.37a 34.86a 0.12a 280.26a
(169.2) (3301.9) (1491.4) (166.6) (76.1) (30.9) (35.6) (0.6) (0.3) (0.6) (0.3) (0.7) (28.9) (0.3) (626.0)
Softwoods (S) 63.67a 600.67a 55.33a 30.67a 45.83a 30.67a 21.50a 1.40a 0.55a 0.01a 0.44a 0.53a 27.93a 0.03a 27.40a
(32.6) (185.6) (49.5) (24.4) (24.9) (16.0) (11.3) (0.5) (0.35) (0.0) (0.1) (0.3) (4.9) (0.1) (39.7)
H. National (2) 166.89a 2418.83a 539.39a 42.17a 66.50a 46.61a 39.44a 0.95a 0.46a 0.04a 0.49a 1.14 39.68a 0.00a 432.18a
(HN) b
(202.6) (4013.8) (1171.7) (38.1) (88.2) (38.0) (43.4) (0.6) (0.3) (0.1) (0.4) (0.3) (28.3) (0.0) (751.1)
S. National (SN) 63.67a 600.67a 55.33a 30.67a 45.83a 30.67a 21.50a 1.40a 0.55a 0.01a 0.44a 0.53 27.93a 0.03a 27.40a
b
(32.6) (185.6) (49.5) (24.4) (24.9) (16.0) (11.3) (0.5) (0.4) (0.0) (0.1) (0.3) (4.9) (0.1) (39.7)
H. National (3) 166.89a 2418.83a 539.39a 42.17a 66.50a 46.61a 39.44a 0.95 0.46a 0.04a 0.49a 1.14a 39.68a 0.00 432.18a
(HN) b
(202.6) (4013.8) (1171.7) (38.1) (88.2) (38.0) (43.4) (0.6) (0.3) (0.1) (0.4) (0.3) (28.3) (0.0) (751.1)
H. Tropical (HT) 51.10a 1330.10a 1056.80a 217.30a 33.30a 40.50a 23.30a 1.16a 0.66a 0.01a 0.40a 1.78a 26.18a 0.34 6.82a
b
(14.4) (1503.0) (2065.9) (250.2) (48.6) (13.2) (11.9) (0.5) (0.3) (0.0) (0.3) (1.1) (30.9) (0.5) (6.2)
C. Telmo et al. / Bioresource Technology 101 (2010) 38083815 3813

Table 5 contains the correlation coefcients. GCV was found to

0.13
0.12
0.41
0.46

0.02

0.25
0.16
0.08

0.65
0.17
0.01
0.01
be strictly related positively to C (0.79***) and secondary to Mg, Ni,

0.28

0.16
0.08

0.24

0.27
0.42

1.00
0.08

0.10
H (0.47**, 0.46**, 0.38*, respectively). GCV was negatively highly

P
related to O ( 0.71***) and secondary to Zn, P, S, K ( 0.47**,

0.45

0.13
0.28
0.20

0.33
0.19
0.36

0.12
0.17
0.26
0.06
0.46**, 0.36* and 0.35*).

0.46
0.25

0.05

0.55
0.23

0.10

0.11

0.11

1.00
Br
H was negatively related to Fe and. C was positively highly re-
lated to Mg and related to H, and negatively to O. N was positively

0.22
0.16

0.05
0.02
0.02

0.17

0.07
highly related to Cu and F as well as secondary related to Cr, Cd, K

0.32
0.27
0.04

0.22

0.22
0.12
0.15
0.50
0.06

1.00
0.01
0.03
and negatively to O and Ni. There was no correlation between N

Cl
and Ca. Cl was positively related to Mn. K was highly related to

0.14
Cd, Zn, Ca and to a lesser extent to Mn and N, while was negatively

0.36
0.17

0.01
0.02

0.01
0.63
0.18

0.18
0.09
0.03

0.16
0.04
0.06

0.02

0.20
1.00
0.10
associated with Ni. S was positively correlated to P and negatively

F
correlated to Cr, Br and Ca
Table 6 represents the multiple regression stepwise backward

0.29

0.18
0.22

0.21
0.10
0.07

0.64

0.44
0.27
0.47
0.22
0.56
0.39
0.00

0.58
0.67
1.00
developed using GCV as output dependent variable and ultimate

Cu
analysis (C, H, O, N and S) and chemical analysis (Na, K, Ca, Mg,
Mn, Fe, Zn, Ni, Cr, Cd, Cu, F, Cl, Br and P) as input independent vari-

0.23
0.30
0.23

0.22
0.01
0.07

0.06
0.30

0.43

0.83
0.65
0.86

0.23
0.50
0.90

1.00
ables. Backward elimination, which involves starting with all can-

Cd
didate variables and testing them one by one for statistical
signicance, deleting any that are not signicant. That means

0.46
0.25
0.31

0.02
0.49

0.38
0.24
0.54
0.38

0.13

0.30
0.26

0.04
0.06

1.00
deleting the minor signicance t values of the variables statisti-

Cr
cally not signicant. Entering all the variables in the model the
determination coefcient was 0.968.

0.27
0.37

0.25
0.29
0.07

0.31
0.41
0.16

0.37
0.36

0.16

1.00
0.46

0.10
The statistical parameters associated with the nal step of the

Ni
multiple regression which represents the best explanatory inde-
pendent variables, were as followed: R2 = 0.86; F = 27.68***. The -

0.29
0.16
0.32

0.23
0.47
Correlation coefcient matrix for the GCV (Mj/kg), ultimate analysis (wt.% in dry basis) and chemical analysis of wood (mg/kg) in dry basis.

0.27
0.12

0.46
0.39
0.83

1.00
0.75

0.09
nal six independent variables of the model were (C, O, S, Zn, Ni and
Zn
Br). The oxygen and zinc, were revealed as greater relative weight,
in the sense negative explaining of the gross caloric value varia-

0.25
0.69
0.12

0.11
0.11

0.07
0.08
0.07
0.28
0.01

0.10
1.00
tion (52.4%).The carbon was the variable with the 3rd weight on
Fe

the regression and explains 16.6% of GCV, however, was the rst
variable with the greatest positive weight. The nickel with (9.6%)
0.31
0.26

0.29
0.10

0.33
0.16

0.12
0.02

0.48

1.00
0.40
and bromine (10.6%) contribute positively to the change of the
Mn

GCV. However, sulfur with (10.8%) contributes negatively to the


variation. The regression suggests that the energy content is a
0.73

0.05
0.22
0.03
0.33

0.02
0.68

0.44
0.47

function of carbon, nickel and bromine. The presence of oxygen, 1.00


Mg

sulfur and zinc lower the energy content. The model had excluded
(H, N, Na, K, Ca, Mn, Cr, Cd, Cu and P) content and (Mg, Mn, F and
0.35
0.52
0.26
0.18
0.02

0.73
0.41

1.00
0.04

Cl) content were forced to excluded. An interesting nding is that


Ca

hydrogen did not contribute statistically to the energy content and


sulfur and oxygen contributes negatively. This nding contradicts
0.29
0.22

0.10
0.35

0.10

the results of Dulong (Selvig and Gibson, 1945), Steuer (Wilson,


0.35

0.72
1.00
K

1979; Buckley and Domalski, 1998) and ScheurerKestner (Wilson,


1979; Buckley and Domalski, 1998).
0.14
0.21
0.06
0.30

They found that hydrogen was one of the parameters that have
0.26
0.02

1.00
Na

higher inuence in gross caloric value along with carbon, oxygen


and sulfur, which contributed positively to the energy content.
0.24
0.18
0.36

The coefcients in the original Dulong formula make certain


0.26

1.00

Correlation signicance level for r > 0.34*, r > 0.44**, r > 0.54***.
0.06

assumptions about the heat released from each of the elements.


S

Carbon is assumed to be amorphous rather than the standard state


0.39

of graphite (Wilson, 1979; Buckley and Domalski, 1998). All the


0.27

1.00
0.23
0.10
N

oxygen in the sample is assumed to be bound in the form of water


such that a portion of the total hydrogen is bound to the oxygen
0.46
0.91
0.71

and is not available for combustion. The equation also assumes


1.00

that the oxygen in the carbon dioxide comes solely from the com-
O

bustion air.
0.34
0.38

1.00
H

4. Conclusion
0.79
1.00
C

The chemical properties of the different woods affect their ther-


GCV
1.00

mal behavior. Wood contains usually relatively low amounts of N,


S and Cl. With the exception of Chlorophora these species are also
characterised by low ash content, with low concentrations of major
Table 5

GCV

Mn
Mg
Na

Cu
Cd

elements, exception the Na, K, Mg and P. The Potassium is a major


Zn
Ca

Ni
Fe

Br
Cr

Cl
H

N
O

K
C

P
S

obstacle for an efcient utilization of these woods in thermal heat-


3814 C. Telmo et al. / Bioresource Technology 101 (2010) 38083815

Table 6
Multiple regression analysis between the dependent variable GCV (Mj/kg) and the independent variables, ultimate analysis (wt.% in dry basis) and chemical analysis of wood (mg/
kg) in dry basis.

STEP C H O N S Na K Ca Mg Mn Fe Zn Ni Cr Cd Cu F Cl Br P R2
1 18.7 2.2 20.5 3.0 7.5 0.1 2.6 1.7 4.8 3.0 5.8 4.7 4.5 2.4 0.2 1.3 5.3 1.4 8.8 1.6 0.968
2 18.7 2.2 20.6 3.0 7.5 0.1 2.5 1.8 4.8 2.9 5.8 4.7 4.5 2.4 __ 1.3 5.3 1.4 8.8 1.7 0.968
3 18.9 2.2 20.9 3.0 7.4 __ 2.5 1.9 4.8 2.8 5.7 4.8 4.3 2.5 __ 1.2 5.2 1.4 8.7 1.7 0.968
4 16.6 1.8 17.1 2.9 8.6 __ 2.6 __ 5.5 3.7 7.1 5.1 5.7 2.5 __ 1.4 6.6 1.5 9.8 1.4 0.967
5 17.9 1.5 18.2 2.3 8.5 __ 1.5 __ 5.0 3.6 6.7 6.3 5.9 3.3 __ __ 6.2 1.7 10.2 1.1 0.966
6 15.8 1.4 15.5 2.6 9.5 __ __ __ 5.8 3.9 7.5 7.3 6.2 3.3 __ __ 7.3 1.9 10.8 1.2 0.966
7 17.9 __ 18.8 3.0 8.6 __ __ __ 4.1 3.8 6.0 7.8 6.6 4.0 __ __ 6.4 1.8 10.2 0.9 0.965
8 17.3 __ 19.2 2.8 9.3 __ __ __ 3.8 3.9 6.0 7.8 7.7 3.2 __ __ 6.7 1.8 10.4 __ 0.963
9 14.0 __ 17.7 1.3 11.9 __ __ __ 4.2 3.9 6.3 8.3 9.2 __ __ __ 7.9 3.2 12.1 __ 0.957
10 14.9 __ 17.8 __ 11.5 __ __ __ 4.2 4.3 6.4 8.3 9.9 __ __ __ 7.3 3.3 12.0 __ 0.955
11 17.0 __ 24.6 __ 10.2 __ __ __ * 3.5 4.6 9.9 10.0 __ __ __ 5.4 3.6 11.3 __ 0.942
12 12.5 __ 23.6 __ 12.5 __ __ __ * __ 5.4 13.5 9.2 __ __ __ 5.4 5.9 12.1 __ 0.933
13 17.3 __ 30.3 __ 10.3 __ __ __ * __ * 14.3 8.2 __ __ __ 3.3 4.7 11.6 __ 0.900
14 17.9 __ 32.6 __ 10.6 __ __ __ * __ * 15.4 7.5 __ __ __ * 4.2 11.8 __ 0.881
15 16.6 __ 35.4 __ 10.8 __ __ __ * __ * 17.0 9.6 __ __ __ * * 10.6 __ 0.860

(a) The values under de independent variables are the standard coefcients (beta) and represents the proportion of which variable contribution in the variation of the
dependent variable, expressed in the regression in a positive or negative ( ) way.
(b) The symbol (__) indicates that the independent variable is not signicant for p > 0.05, whereby was eliminated.
(c) The symbol (*) represents that this variable was forced to excluded.

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