G Model

ARTICLE IN PRESS

JAAP-3446; No. of Pages 10

Journal of Analytical and Applied Pyrolysis xxx (2015) xxxxxx

Contents lists available at ScienceDirect

Journal of Analytical and Applied Pyrolysis

journal homepage: www.elsevier.com/locate/jaap

Slow pyrolysis of different Brazilian waste biomasses as sources of soil

conditioners and energy, and for environmental protection
Marta Eliane Doumer a , Gregorio Guadalupe Carbajal Arzaga b , Dimas Agostinho da Silva c ,
Carlos I. Yamamoto d , Etelvino Henrique Novotny e , Jandyson Machado Santos f ,
Luana Oliveira dos Santos f , Alberto Wisniewski Jr. f , Jailson Bittencourt de Andrade g ,
Antonio Salvio Mangrich a,f,g,
a

Department of Chemistry, Federal University of Paran UFPR, 81531-990 Curitiba, PR, Brazil
Department of Chemistry, University of Guadalajara, Marcelino Garca Barragn 1421, CP 44430 Guadalajara, Jalisco, Mexico
c
Department of Forestry Engineering and Technology, Federal University of Paran UFPR, 80210-170 Curitiba, PR, Brazil
d
Department of Chemical Engineering, Automotive Fuel Analysis Laboratory (LACAUT), Federal University of Paran UFPR, 81530-990 Curitiba, PR, Brazil
e
Embrapa Soils, Rua Jardim Botnico 1024, 22460-000 Rio de Janeiro, RJ, Brazil
f
Department of Chemistry, Federal University of Sergipe UFS, 49100-000 So Cristvo, SE, Brazil
g
National Institute of Science and Technology: Energy & Environment, 40170-290 Salvador, BA, Brazil
b

a r t i c l e

i n f o

Article history:
Received 10 November 2014
Received in revised form 9 March 2015
Accepted 12 March 2015
Available online xxx
Keywords:
Slow pyrolysis
Chemical composition
Waste biomass
Functional groups
Biochar
Bio-oil

a b s t r a c t
This paper explores the viability of producing energy and agricultural soil conditioners with biochars
and bio-oils from the pyrolysis of biomasses that in some cases are potential environmental pollutants.
This approach addresses the need to develop sustainable production systems that minimize pollution
and soil degradation, and meet the demand for renewable fuels. Large volumes of biomass from different
sources are available in Brazil, including Eucalyptus crop residues (CE), castor meal (CM), coconut pericarp
(CP), sugarcane bagasse (SB), and water hyacinth (WH). CM char and SB bio-oil are good prospects for
energy generation. Characterization using DRIFT, 13 C NMR, and van Krevelen diagrams indicated that after
carbonization, aromatic structures were predominant in the biochars produced from the CP, CE, and SB
biomasses, while aliphatic groups were abundant in the biochars from CM and WH. Analysis using EPR
showed that unpaired electrons were preferentially located on carbon atoms in the case of the CP, CE,
and SB biochars, with EPR g values around 2.0030, while the CM and WH biochars presented g values
around 2.0035, indicating that the unpaired electrons were closer to oxygen atoms. In terms of bio-oil
chemical composition, the most abundant compounds were 3-pyridinol and furans (WH), phenols (CP),
and hexadecanoic, octadecanoic, 9,12-octadecenoic (z,z), 3-docosenoic, and 5-docosenoic acids (present
only in the CM bio-oil). The bio-oils from SB and CE were quite similar and the main compound was 1,2,6hexanetriol. The biomass sources studied produced reasonable amounts of bio-oil, and could compete as
suitable raw materials for biofuel production.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Biomass can be converted into fuel and chemical feedstock
by thermochemical pyrolysis routes (gasication, liquefaction and
solid charring) [1]. Pyrolysis is usually divided into three modes:
fast, intermediate, and slow. The mode and the conditions of pyrolysis can inuence the relative proportions of the gas, liquid, and

Corresponding author at: Department of Chemistry, Federal University of Paran

UFPR, 81531-990, Curitiba, PR, Brazil. Tel.: +55 4133613182; fax: +55 4133613006.
E-mail address: asmangrich@gmail.com (A.S. Mangrich).

solid products obtained. Slow pyrolysis uses a low heating rate,

with a long vapor residence time, and is used to maximize the
yield of solid products (biochar) [2]. The liquid fraction (bio-oil)
contains organic compounds such as alkanes, aromatic hydrocarbons, phenol derivatives, and small amounts of ketones, esters,
ethers, sugars, amines, and alcohols [3]. These liquid products,
obtained under optimum conditions, can be utilized as synthetic
fuels or raw materials in the chemical industry. The caloric
energy content of bio-oil is close to that of petroleum [1,4,5].
The solid fraction, a charcoal-like product called biochar, is carbon rich (6590%), with oxygen-containing functional groups on
the surface and aromatic structures [6] that provide resistance

http://dx.doi.org/10.1016/j.jaap.2015.03.006
0165-2370/ 2015 Elsevier B.V. All rights reserved.

Please cite this article in press as: M.E. Doumer, et al., Slow pyrolysis of different Brazilian waste biomasses as sources of soil conditioners
and energy, and for environmental protection, J. Anal. Appl. Pyrol. (2015), http://dx.doi.org/10.1016/j.jaap.2015.03.006

G Model
JAAP-3446; No. of Pages 10
2

ARTICLE IN PRESS
M.E. Doumer et al. / Journal of Analytical and Applied Pyrolysis xxx (2015) xxxxxx

Fig. 1. Raw biomass, biochars, and pyrolysis setup used. (a) Biomass (left) and resulting biochar (right) of the materials: water hyacinth (WH), sugarcane bagasse (SB),
castor meal (CM), coconut pericarp (CP), and Eucalyptus crop residues (CE); (b) borosilicate reactor loaded with biochar; (c) reactor inside the electrically heated furnace; (d)
schematic diagram of the reactor arrangement; (e) photograph of the equipment used.

to biological degradation [7]. Biochar has shown potential as a

natural fertilizer [814] and as a solid biofuel [8,15]. The indigenous Amazonian peoples prepared biochar by pyrolyzing (charring)
plant debris, producing the substance known as Terra Preta de
ndios. Biochar contains both refractory and labile portions [13], and
can be produced from various waste biomass sources, including
woody biomasses [2,6,1618], municipal waste [19], and agricultural residues [1,9,10,1215]. According to the International
Biochar Initiative (IBI), it is estimated that by the year 2050 about
80% of all crop and forestry residues may be converted to biochar
for use as soil conditioners and for energy production [11]. Currently, lignocellulosic wastes are not fully utilized in Brazil, with
some being burned and reduced to ash and CO2 , increasing greenhouse gas (GHG) emissions, without energy recovery [20]. In this
context, value can be added to biomass by using it for energy
production, as an excellent alternative to fossil fuels [21], as well
as to produce soil conditioners [13], taking advantage of the fact
that waste biomass is low-cost, renewable, and available in large
quantities.
Several studies have demonstrated that the quality and chemical
composition of biochar depend on the feedstock and the production conditions [13,16,17,22]. However, few detailed studies have
been carried out in Brazil using biomass wastes such as those considered here. In this work, we studied biomass derived from water
hyacinth (WH), an aquatic plant widely utilized to clean wastewater in ponds, which if not frequently removed can cover the entire
water surface and hinder the process. This biomass is abundant
in Brazil, it is estimated that the annual WH generation from the

Brazilian Paraguay river oodplain reach about 0.8 to 2.4 107 t of

dry biomass [23]. Another biomass is Eucalyptus crop residue (CE)
from planted forests, which if left in the environment can contaminate the soil surface and fresh waters, due to its action as a reducing
agent [24]. Currently planted area of Eucalyptus forests is 5.4 million
hectares, in Brazil [25]. Sugarcane bagasse (SB) from the sugar and
alcohol industries is also abundant in Brazil and is used to produce
thermal electricity. In Brazil, 700 million tons of sugarcane were
produced in 2014 [26]. Castor meal (CM), which is available from
the Brazilian biodiesel industry [27], is known to be highly toxic
to animals. In 2014, Brazilian production of castor berries was of
37.900 t [26]. Green coconut pericarp (CP), from coconut processing industries and the consumption of coconut water [28], which
is very common on Brazilian beaches, can pose a substantial risk
to public health. Coconut pericarp halves are concave and retain
rainwater, enabling the development of Aedes aegypti, the mosquito
that transmits dengue fever, chikungunya, and yellow fever, among
other viruses, mainly in countries with tropical climates [29,30]
such as Brazil, where around two billion of the fruit are produced
every year [26].
For the reasons described above, it was decided to study slow
pyrolysis processes, using the biomasses CE, CM, CP, SB, and
WH to produce biochar, bio-oil, and syngas. The solid products
obtained were characterized using physicochemical and spectroscopic methods in order to determine their suitability for use
as biofuels or soil conditioners. The composition of the bio-oil
was investigated using gas chromatography/mass spectrometry (GC/MS) in order to relate the chemical structures to the

Please cite this article in press as: M.E. Doumer, et al., Slow pyrolysis of different Brazilian waste biomasses as sources of soil conditioners
and energy, and for environmental protection, J. Anal. Appl. Pyrol. (2015), http://dx.doi.org/10.1016/j.jaap.2015.03.006

G Model
JAAP-3446; No. of Pages 10

ARTICLE IN PRESS
M.E. Doumer et al. / Journal of Analytical and Applied Pyrolysis xxx (2015) xxxxxx

characteristics of the products and their potential for use as biofuels

or feedstocks for the chemical industry.
2. Materials and experimental procedures
2.1. Biomass and pyrolysis
The biomass sources were water hyacinth (WH), sugarcane
bagasse (SB), castor meal (CM), coconut pericarp (CP), and Eucalyptus crop residues (CE). The sugarcane bagasse was provided by
the sugar and alcohol company Melhoramentos S.A. (Brazil). The
castor bean (Ricinus communis L.) residues from the biodiesel industry were collected in the form of castor meal and the mesh size
was 2 mm. The triturated coconut pericarp was from trees (Cocos
Nucifera) grown in Bahia State (Brazil). The Eucalyptus crop residue
from the species Eucalyptus grandis and Eucalyptus saligna was provided by Granfor (Brazil) and was ground to a mesh size of 5 mm
using a hammer mill. The water hyacinth (Eichhornia crassipes) was
obtained from wastewater stabilization ponds in the municipality
of So Cristovo (Sergipe State, Brazil) and received in mesh size
0.85 mm. All the biomass samples were air-dried before pyrolysis.
The pyrolysis reactions were conducted in a laboratory-scale
reactor, with heating from room temperature up to 350 C at a rate
of 5 C min1 , giving a maximum time of 70 min in the reactor. The
pyrolysis experiments were performed using a 2 L internal volume
borosilicate reactor (internal diameter 15 cm, height 34 cm) loaded
with the biomass (300 g of SB, 300 g of WH, 550 g of CM, 350 g of CE,
or 300 g of CP). The reactor was externally heated by an electric furnace equipped with temperature control. A diagram of the system
is shown in Fig. 1. The pyrolysis vapors were transferred through a
water condenser at 20 C to separate the condensable (bio-oil) and
non-condensable gases.
After each test, biochar and bio-oil were collected from the
reactor and the condenser system, respectively, to measure the
mass yield and remove aliquots for detailed analyses. The pyrolysis
experiments were repeated at least three times. The mass yield of
gases was calculated by difference. The bio-oil was separated into
organic and aqueous fractions using aqueous NaHCO3 solution (5%,
w/v), with a 1:2 (v/v) ratio of bio-oil to sodium bicarbonate solution, and the organic fraction was stored in stoppered glass asks
for subsequent analysis.
2.2. Characterization of biomass, biochar, and bio-oil samples
Characterization of the biomass, biochar, and bio-oil samples
was performed using a range of analytical and physicochemical methods. Measurement of the caloric values of the samples
followed ASTM Method D240-50 and employed an IKA Model
C 7000 calorimeter. In the case of the bio-oil, only the organic
fraction was measured. The proximate analysis of the biomass
and biochar samples was conducted according to the ASTM
standard procedures for ash (ASTM D 1762-84), volatile matter
(ASTM D 1762-84), and xed carbon (FC) (by difference). Bio-oil
solutions (100 mg mL1 ) in tetrahydrofuran (THF) were derivatized using N,O-bis(trimethylsilyl) triuoroacetamide (BSTFA) in
a ratio of 1:1, and then analyzed by GC/MS using a Shimadzu
Model QP5050A instrument. An RTX-5SilMS capillary column was
used (5% diphenyl, 95% dimethylpolysiloxane; 30 m 0.25 mm ID,
0.25 m), and 1 L aliquots of sample were injected in splitless
mode. Helium (99.999%) was used as the carrier gas, at a ow rate of
1.2 mL min1 . The column temperature program was 50 C (5 min),
followed by a ramp at 10 C min1 to 310 C (14 min). The injector
and transfer line temperatures were 300 C. The mass spectrometer was operated at 70 eV in electron impact (EI) mode. The mass
spectrometer was operated in scan mode in the range 40550 Da.

Table 1
Higher heating values (HHV, MJ kg1 ) of the biomass, biochar, and oil samples (as
received).
Material

HHV (MJ/kg)

Biomass
CE
CM
CP
SB
WH

18.85 0.14
21.25 0.04
23.46 0.07
17.27 0.49
14.36 0.21

Biochar
CE
CM
CP
SB
WH

25.32 0.17
22.74 0.84
25.97 0.58
24.35 0.45
17.24 0.13

Bio-oil
CE
CM
CP
SB
WH

27.49 0.03
27.69 0.17
30.23 0.03
22.66 0.15
29.52 1.24

Mid-infrared spectra of the solid samples were acquired with a

Fourier transform infrared spectroscopy (DRIFT) instrument (Excalibur FTS 3500 52 GX, Bio-Rad).
Electron paramagnetic resonance (EPR) analysis of the biochar
samples was conducted at room temperature (300 K), using a
Bruker EMX spectrometer operated in the X-band (9.5 GHz)
with modulation frequency of 100 kHz. For the full EPR spectra
(B = 5000 G), the operational conditions were a sweep eld of
5000 G, center eld of 3300 G, microwave power of 20 mW, and
modulation amplitude of 5 G. The organic free radicals (OFR) were
analyzed using the g-factor region close to 2.0, with the OFR signal near the center of the sweep eld of 50 G, microwave power
of 0.2 mW, and modulation amplitude of 1 G. The EPR data were
treated with the aid of Win-EPR software, and a weak pitch
reference material (g = 2.0028) was supplied by Bruker. The OFR
were quantied using the approximation: intensity x B2 . The resonance parameters were obtained by mathematical treatment with
the Win-EPR software, and the electron spin concentration was
determined by comparison with that of the reference material.
Solid-state 13 C NMR analyses were performed at a resonance
frequency of 100.6 MHz, using a Varian Inova 400 spectrometer
(Varian, Palo Alto, CA, USA). Thermogravimetric (TG) and differential thermal gravimetric (DTG) analyses were performed with
20 mg of sample, using a Mettler-Toledo TG/SDTA 851e thermoanalyzer, under an air atmosphere, at a heating rate of 20 C min1
in the range 251000 C. The moisture contents were calculated
from the loss of weight at 105 C.
3. Results and discussion
3.1. Pyrolysis yields
The average pyrolysis yields of biochar, bio-oil, and noncondensable gases are presented in Fig. 2. As a rst observation,
the maximum production of solid, liquid, or gaseous products was
identied in terms of the type of biomass that provided the highest yield. In the case of solid biochar, CM provided the highest
yield (74.09%), while generating the smallest amounts of liquid and
gaseous products. The highest yield of liquid products (sum of the
oil and water fractions) was achieved with SB (40.97%), and the
maximum production of bio-gas (20.48%) was obtained with CP.
The bio-oil derived from Eucalyptus (CE) showed a higher yield
in the aqueous fraction, which represented 78.54% of the total liquid product of pyrolysis. The highest organic fraction percentage

Please cite this article in press as: M.E. Doumer, et al., Slow pyrolysis of different Brazilian waste biomasses as sources of soil conditioners
and energy, and for environmental protection, J. Anal. Appl. Pyrol. (2015), http://dx.doi.org/10.1016/j.jaap.2015.03.006

G Model
JAAP-3446; No. of Pages 10

ARTICLE IN PRESS
M.E. Doumer et al. / Journal of Analytical and Applied Pyrolysis xxx (2015) xxxxxx

Table 2
Chemical analysis of the biomasses and biochars in terms of the amounts (wt.%, dry
basis) of xed carbon, ash, and volatile matter.
Material

Fig. 2. Mass yields of pyrolysis products from CE, CM, CP, SB, and WH.

(37.69%) in the liquid product was obtained for SB. In previous work,
a similar yield of 32.34% of bio-oil was obtained from giant Miscanthus at 400 C [31], while Wright et al. [32] reported that the
aqueous phase of the bio-oil can account for more than 70%, with
30% being suitable for use as a biofuel. The biomass sources studied here therefore produced comparable and satisfactory amounts
of bio-oil, and could compete as suitable raw materials for biofuel
production or for use as chemical industry feedstocks.
3.2. Higher heating value
The higher heating values (HHV) of the samples of biomass,
biochar, and bio-oil are given in Table 1.
For the biomasses, the highest HHV value (23.46 MJ kg1 ) was
obtained for CP, and the lowest value (14.36 MJ kg1 ) was found
for WH. The HHV values for biochar and bio-oil (organic fraction)
were higher than for the corresponding biomasses. The higher HHV
of biochar was due to the formation of xed carbon, and substantial increments were observed for SB (from 17.27 to 24.35 MJ kg1 )
and CE (from 18.85 to 25.32 MJ kg1 ), reecting improvement in
the quality of these materials for use as fuel. The highest HHV
were obtained for CP, with values of 25.97 and 30.23 MJ kg1 for
biochar and bio-oil, respectively. The HHV values for CP bio-oil
(30.23 MJ kg1 ) and SB bio-oil (22.66 MJ kg1 ) were in agreement
with those reported by Mantilla et al. [21] for empty palm fruit
(34.91 MJ kg1 ) and sugarcane bagasse (25.22 MJ kg1 ).
According to Bridgwater [33], the mean caloric value of bio-oil
is close to 17 MJ kg1 , which is equivalent to 40% of the caloric
value of fuel oil (43 MJ kg1 ). Therefore, the bio-oils obtained from
the ve biomass sources in this study are good candidates for use as
fuel sources, because the measured caloric values reached around
70% of that of fuel oil.
3.3. Proximate and ultimate analyses
The results of the chemical analyses of the biomasses and
biochars are given in Table 2.
Chemical analysis of the biomass samples showed that the contents of volatile materials ranged from 65.15 to 83.03%, with the
lowest and highest values for WH and SB, respectively. The low
volatiles content of WH was possibly due to the high percentage of
ash (17.40%). The ash contents of the remaining biomasses ranged
from 2.05% (CE) to 8.57% (CM).
The lowest and highest xed carbon contents of the biomass
samples were found for SB and CP, respectively, in agreement with

Fixed carbon
wt.%

Ash
wt.%

Volatile matter
wt.%

Moisture
wt.%

CE
CM
CP
SB
WH

Biomass
18.61 1.14
20.91 0.18
28.57 0.42
12.97 0.58
17.43 0.27

2.05 0.42
8.57 0.42
2.43 0.09
4.00 0.18
17.40 0.18

79.20 1.35
70.52 0.58
68.99 0.46
83.03 0.67
65.15 0.36

4.0
3.0
4.6
6.3
8.0

CE
CM
CP
SB
WH

Biochar
58.26 0.90
27.13 1.08
64.39 0.09
50.44 0.16
31.58 0.26

4.37 0.18
10.35 0.20
5.22 0.18
5.50 0.13
30.54 0.48

37.36 0.71
62.52 0.88
30.39 0.11
44.05 0.30
37.87 0.41

the HHV results since a higher content of xed carbon in the fuel
should be reected in a higher caloric value.
Compared to the raw materials, the biochars showed increased
contents of volatile matter and xed carbon. The levels of volatile
matter in the samples of biochar were indicative of incomplete carbonization and suggested that volatile compounds were formed
during the thermal degradation process. The ash contents of the
biochars were also higher than found for the biomasses, as expected
due to the mineral material remaining after carbonization. These
ndings are in agreement with the results obtained by zcimen
and Ersoy-Mericboyu [1], who studied waste biomass from the food
processing industry.
Table 3 presents the elemental analyses of the biomasses. The
lowest and highest contents of C were found for WH (33.59%) and
CP (47.59%), respectively. The C contents in SB, CE, and CM were
similar to the value obtained for CP. In terms of H and N, the highest contents were found for CM and CE. After pyrolysis, the highest
C contents of the biochars were found for CE, SB, and CP (between
63 and 68%). The highest percentages of H and N were obtained for
CM. Carbonization caused the C contents of the biochars to increase,
relative to the values for the biomasses, while the percentages of
O and H decreased. According to Al-Wabel et al. [34], the loss of
hydrogen can be attributed to the effect of temperature in breaking
the weakest bonds in the biomass structure, producing materials
that are more carbonaceous. The same authors found enrichment in
N content, compared to the original raw material, after carbonization of coconut pericarp, and a similar effect was observed in this
study, with the exception of CM. This can be explained by the incorporation of N into complex structures that are heat-resistant and
involatile [13]. The high N content of biochar could be an advantage, because it could be used to provide nutrients to the soil and
increase crop yields [35].

Table 3
Elemental contents (%C, %H, %N, and %O) of the biomasses and their respective
biochars.
Element CE

CM

CP

SB

WH

(%)
C
H
N
Oa

Biomass
46.82 0.91
6.33 0.04
0.16 0.03
44.65 0.49

46.79 0.17
7.19 0.04
8.52 0.04
28.92 0.49

47.59 0.41
5.82 0.09
0.78 0.02
43.38 0.38

45.52 0.22
6.26 0.01
0.24 0.03
43.83 0.38

33.59 0.37
5.81 0.09
2.11 0.01
41.07 0.98

C
H
N
Oa

Biochar
68.15 0.92
4.09 0.06
0.50 0.03
22.85 0.71

54.42 0.73
6.05 0.06
7.01 0.38
22.14 1.10

63.99 1.98
4.00 0.11
0.97 0.03
25.47 1.55

65.02 0.93
4.19 0.08
0.55 0.01
24.72 0.88

45.53 1.19
3.53 0.04
3.93 0.03
16.44 1.25

Calculated by difference.

Please cite this article in press as: M.E. Doumer, et al., Slow pyrolysis of different Brazilian waste biomasses as sources of soil conditioners
and energy, and for environmental protection, J. Anal. Appl. Pyrol. (2015), http://dx.doi.org/10.1016/j.jaap.2015.03.006

G Model
JAAP-3446; No. of Pages 10

ARTICLE IN PRESS
M.E. Doumer et al. / Journal of Analytical and Applied Pyrolysis xxx (2015) xxxxxx

Table 4
Relative composition of bio-oil by GC/MS.
Chemical compound

Molecular formula

WH

CP

CM

SB

CE

1-Methylbutoxy TMS
3-Methylbutanoic acid TMS
Pentanoic acid TMS
5-Methyl-furfural
2-Methyl-butanol TMS
1,2-Ethanediol TMS
Furan-2-ol TMS
3,6-Dioxy-2,7-disilaoctane TMS/2,2,4,7,7-pentamethyl TMS
2-Pyridinol TMS
Hexanoic acid TMS
Phenol TMS
2-Hydroxy-propanoic acid TMS
2-Hydroxy-acetic acid TMS
Inosose, 2-desoxy-, o-methyloxime, tetrakis-o- TMS
Methyl-hexanoic acid TMS
2-Hydroxy-butanoic acid TMS
3-Pyridinol TMS
2-Methyl phenol TMS (Guaiacol)
3-Methylcyclopent-1-en-1-ol TMS
4-Pyridinol TMS
2-Pyrrolidinone TMS
Tetrahydro-3-furanmethanol TMS
4-Methylphenyl ether TMS
3-Methyl-3-hydroxy-butanoic acid TMS
Heptanoic acid TMS
3-Methylphenyl ether TMS
d-Xylo-hexonic acid,3-deoxy; g-lactone TMS
5-(1,2-dihydroxyethyl)-4-hydroxydihydrofuran-2(3H)-one
3-Hydroxy-6-methylpyridine1 TMS
2,4-Hexadienoic acid TMS
Acetic acid, bis[(trimethylsilyl) oxyl] ester TMS
2-Methoxyphenol TMS (Guaiacol)
4-Hydroxy-butanoic acid TMS
Benzoic acid ester TMS
3,7-Dioxa-2,8-disilanonane, 2,2,8,8-tetramethyl-5-(TMS) oxy]
1,2-Benzenediol bis(TMS) ether (Catechols)
3-Methyl-4-hydroxybutyrate 2 TMS
Cyclohexene, 3-(3-methyl)-hexyl TMS
Pentanedioic acid, ester bis TMS
Butanoic acid, 2,4-bis[(trimethylsilyl) oxy]- ester TMS
3-Methyl-2-nitro-benzeneethanol TMS
1,2,6-Hexanetriol TMS
2-Ethyl-1,3- propane TMS
Undecenoic acid TMS
3-Hydroxybenzoic acid TMS
Levoglucosan TMS
Hexadecanoic acid, ester TMS
9,12-Octadecadienoic acid (Z,Z) ester TMS
9,12-Octadecadienoic acid (Z,Z) ester TMS
9-Octadecenoic acid TMS
Octadecanoic acid TMS
3-Docosenoic acid ester TMS
5-Docosenoic acid ester TMS

C8 H20 SiO
C8 H18 O2 Si
C8 H18 O2 Si
C6 H6 O2
C8 H20 OSi
C8 H22 O2 Si2
C7 H12 O2 Si
C9 H24 O2 Si2
C8 H13 NOSi
C9 H20 O2 Si
C9 H14 SiO
C9 H22 Si2 O3
C8 H20 Si2 O3
C19 H45 NO5
C10 H22 O2 Si
C10 H24 O3 Si
C8 H13 NOSi
C10 H16 OSi
C9 H18 OSi
C8 H13 NOSi
C7 H15 NOSi
C8 H18 SiO2
C10 H16 OSi
C10 H24 O3 Si
C10 H22 O2 Si
C9 H14 OSi

4.17
0.55

1.72
4.24
3.97
0.70

0.29
3.93
1.81
0.74

0.30
13.07

1.36

3.70

0.53

0.64
0.58
1.00
1.65
0.35
0.32

27.00
2.09
4.76

0.14
1.12
0.34

2.19
1.42

0.18

0.11
0.13

0.55
0.77

0.28
0.40
2.32

0.23

2.91

0.64

1.43

0.27
0.18

0.24

3.14
1.37
0.14
0.32

1.11
1.04
4.36
0.27

0.48

2.07

1.37
0.44
0.14
0.22

0.23

2.13
1.78
0.37
0.45

0.46
0.77
3.56
0.73

0.23

1.95

3.08

0.19

C15 H34 O5 Si3

C9 H15 NOSi
C12 H22 SiO2
C11 H28 O4 Si
C10 H16 O2 Si
C10 H24 O3 Si2
C10 H14 O2 Si
C12 H32 O3 Si3
C12 H22 O2 Si2
C11 H26 O3 Si
C16 H32 OSi
C11 H24 O4 Si
C13 H32 Si3 O4
C11 H17 NO3 Si
C15 H38 O3 Si3
C11 H28 O2 Si2
C14 H28 O2 Si
C13 H22 O3 Si2
C15 H34 O5 Si3
C19 H40 O2 Si
C21 H40 O2 Si
C21 H42 O2 Si
C21 H42 O2 Si
C21 H44 O2 Si
C25 H50 O2 Si
C25 H50 O2 Si

0.97

1.62

0.94
1.81
0.46
5.95
5.93
0.52
3.42

0.48

4.76
1.60

6.20

0.19
0.86

2.20
0.84
0.55
1.05
17.3
0.34
3.22

0.75

6.27
1.04

1.64
0.44

0.25

1.17

1.33
5.34

1.13

0.26
0.22

0.26

2.11
0.39
1.16
0.41
0.18
0.67
4.74
0.25
2.10
0.27
0.57
0.51
12.10
2.56

5.57

0.14

2.57
0.47
1.67
0.73

0.61
5.84
0.47
7.60
0.21
0.55
2.55
14.70
0.96

2.95

Van Krevelen diagrams illustrating the differences in the elemental compositions of the biomasses and biochars are shown in
Fig. 3 (a) and (b), respectively. After pyrolysis, the contents of H
and O decrease, because the biochar becomes carbon-rich [31], as
observed in this study. The decrease in the O/C molar ratio during
carbonization is associated with dehydration reactions and results
in a less hydrophilic surface of biochar [31], while the decrease in
the H/C molar ratio is indicative of the formation of aromatic compounds [34]. The highest N/C and O/C molar ratios were observed
for the CM biochar, indicating a substantial presence of nitrogen and
oxygen functions. The CM biochar also presented the highest H/C
molar ratio, indicating that the material was aliphatic [36]. Therefore, the CM and WH biomasses may have shown higher aliphatic
contents due to the smaller particle size and less free space inside
the reactor, which might have affected the thermal gradients in the
system. The low H/C molar ratio for the CE biochar was suggestive

Relative area (%)

4.78

0.13
4.24
2.13
6.71
7.21
3.51
12.20
2.57

of the presence of aromatic compounds. In all cases, the H/C molar

ratios for the biomasses exceeded 1.4, which is characteristic of
lignocellulosic materials [15].
3.4. Composition of the bio-oils
GC/MS analysis was used to obtain information concerning the
nature of the organic compounds present in the liquid products
of pyrolysis (Table 4). Between 50 and 80% of the relative chemical composition of the bio-oils produced could be identied from
investigation of the presence of around 160 compounds in their
silylated forms.
The most abundant product in the WH bio-oil was 3-pyridinol,
with a relative percentage of up to 13%. Nitrogen compounds could
be produced after the pyrolysis of peptides or the decomposition
and condensation of amino acids [37]. It should be noted that the

Please cite this article in press as: M.E. Doumer, et al., Slow pyrolysis of different Brazilian waste biomasses as sources of soil conditioners
and energy, and for environmental protection, J. Anal. Appl. Pyrol. (2015), http://dx.doi.org/10.1016/j.jaap.2015.03.006

G Model
JAAP-3446; No. of Pages 10
6

ARTICLE IN PRESS
M.E. Doumer et al. / Journal of Analytical and Applied Pyrolysis xxx (2015) xxxxxx

presence of such compounds in bio-oil could be a disadvantage

for its use as fuel, due to NOx emissions during combustion [38].
Furan compounds were another signicant group in the WH bio-oil
(8.6%). Furan derivatives are formed during primary decomposition of hemicellulose at temperatures above 400 C [38]. The major
anhydrosaccharide compound in the WH bio-oil was levoglucosan
(6.2%), which is formed from cellulose degradation at temperatures between 300 and 400 C [38]. These results were in agreement
with the amounts of hemicelluloses and cellulose in the feedstock
(40%) and the low content of lignin (6.5%) [39].
Phenols were the main organic compounds in the CP biooil, which could be attributed to the high lignin content (up to
25%) of green coconut shells [40]. These compounds are formed
during the decomposition of lignin macromolecules at temperatures above 350 C, and include catechols (benzenediols), guaiacols
(methoxyphenols), and alkyl-phenols [38]. Organic compounds
such as hexadecanoic, octadecanoic, 9,12-octadecenoic (z,z),
3-docosenoic, and 5-docosenoic acids were only present in the CM
bio-oil. During biodiesel production, these oils remain in the raw
material after the extraction procedure. Hydrocarbons in bio-oil
originate from the carbohydrate and lipid groups in the biomasses
[37]. The presence in bio-oils of phenols and long chain fatty acid
methyl esters (FAME) could improve their HHV [21].
The bio-oils derived from SB and CE were quite similar, with
yields of up to 12% of 1,2,6-hexanetriol as the major constituent,
which was probably produced by the weak cleavage of hexose
molecules such as glucose and mannose from cellulose and hemicelluloses.

Table 5
EPR spin densities (spin g1 ) and g values obtained for the biochar samples.
Biochar

spin g1

CE
CM
CP
SB
WH

2.40 1018
2.79 1017
7.35 1018
1.51 1018
1.67 1017

2.0030
2.0034
2.0031
2.0030
2.0035

3.5. DRIFT spectroscopy

The biomasses and biochars were characterized by infrared
spectroscopy (Fig. 4). The main signals detected included bands
between 2850 and 3000 cm1 , corresponding to symmetric and
antisymmetric stretching vibrations of aliphatic CH2 and CH3
moieties [1,8,9,34]. Peaks between 1050 and 1350 cm1 corresponded to C O stretching and O H deformation in phenols,
ethers, esters, and primary, secondary, and tertiary alcohols [8].
Peaks between 630 and 850 cm1 corresponded to aromatic C H
bending vibration, due to the presence of adjacent aromatic hydrogens in biochars [1,8]. The spectra of the biomasses showed some
differences, compared to the biochars, in the region centered at
1602 cm1 , where the bands attributed to C C and C N from
lignin and protein appear [9,15,34], with higher signals for the
biochars (see the magnication in Fig. 4). The broad band at around
3440 cm1 , related to O H stretching of cellulose and proteins in
the biomasses, disappeared completely after carbonization. The
lignin structures of biomass produce a strong absorption at around
1060 cm1 , due to C O C vibrations in ethers [15,41], which are
decomposed by pyrolysis; this band was absent in the spectra for
all the chars. All the biomass samples showed an absorption peak at
around 1739 cm1 , related to the C O stretching mode of ester and
aldehyde groups [42]; the intensity of this signal decreased after
pyrolysis, while the intensity of the band at 1700 cm1 increased
for all the biochars (see the magnication in Fig. 4). This feature
has been observed previously during the pyrolysis of lignin, and
was attributed to the formation of aromatics containing carbonyl
groups [42,43]. This nding, in addition to the increased intensity of the 1602 cm1 band related to aromatic C C vibrations,
conrmed the formation of polycyclic aromatic compounds [9,34],
in agreement with the lower H/C ratios identied from the elemental analysis (Section 3.3), conrming that the structures became
more aromatic after pyrolysis of the biomasses. The WH biomass
and biochar showed different behavior, with absorption bands at
3050 cm1 characteristic of aromatic C H stretching, with less
conjugation among the aromatic rings. The spectra for the CM
biomass and biochar showed greater intensity of peaks corresponding to aliphatic groups (at 2930 and 2857 cm1 ), compared to the
other biochars, revealing a higher content of linear structures. The
presence of a high content of aliphatic structures remaining after
pyrolysis was in agreement with the 1739 cm1 band observed for
the CM char, indicating the presence of linear carbonyl structures,
possibly from fatty acids remaining after the biodiesel production
process.

3.6. EPR spectroscopy

Fig. 3. Van Krevelen diagrams for the biomasses (a) and biochars (b).

The EPR spectra of all the biochars showed sharp absorption

lines at around g = 2.003 (Fig. 5). The CE, CP, and SB biochars presented EPR g-factors of 2.0031 and 2.0030 (Table 5), suggesting
that the unpaired electrons were nearest to carbon atoms, whereas
the WH and CM biochars presented g-factors of 2.0035 and 2.0034,
respectively, which are typical of free radicals near to heteroatoms
in organic structures, as occurs in ortho-semiquinones [44].

Please cite this article in press as: M.E. Doumer, et al., Slow pyrolysis of different Brazilian waste biomasses as sources of soil conditioners
and energy, and for environmental protection, J. Anal. Appl. Pyrol. (2015), http://dx.doi.org/10.1016/j.jaap.2015.03.006

G Model
JAAP-3446; No. of Pages 10

ARTICLE IN PRESS
M.E. Doumer et al. / Journal of Analytical and Applied Pyrolysis xxx (2015) xxxxxx

Fig. 4. DRIFT spectra obtained for the different biomasses (dashed lines) and their corresponding biochars (bold lines).

The areas of the absorption curves were used to determine the

concentrations of the free radicals listed in Table 5. The highest spin
densities were observed for CP, followed by CE. This was due to the
high amount of polyphenol structures, which are directly related
to the number of free radicals (the greater the number of spins,
the greater the number of phenolic groups) [44], although considering the EPR g values of this kind of free radical (around 2.0030),
the unpaired electrons were near carbon atoms. The organic free
radicals present in biochars might enhance the reactivity of these
materials in soil [45]. The OFR concentrations listed in Table 5 correspond to the areas of the curves due to OFR absorption. The higher
spin densities observed for CP, CE, and SB were in agreement with
the 13 C NMR spectra (see below) that showed that these samples
produced the most intense absorbance related to the presence of

aromatic structures (Fig. 7). They were also in agreement with the
higher aromatic compound contents of these materials, inferred
from the van Krevelen plots (Fig. 3). In addition, high spin densities
are also associated with high levels of polyphenol structures, which
directly affect the number and stability of OFR, due to the presence of a greater number of phenolic groups in ortho- and parapositions [44]. These phenolic groups produced during pyrolysis,
as evidenced by the shift of the FTIR band from 1739 to 1700 cm1
(described above, Section 3.5), could be responsible for the oxidation capacity of biochars, which is required in order to sustain the
enzymatic reduction of N2 O to N2 .
In addition to the intense free radical signal, the SB sample presented an intense wide EPR line between 2700 and 3700 gauss,
caused by trivalent iron in concentrated domains [46]. The same
band appeared with less intensity in the other samples, with the
exception of the CP sample, for which this absorption signal was
absent. Samples CM, WH, and CE (almost imperceptible) also exhibited six lines centered at the g = 2.0 region of the spectra, attributed
to the hyperne structure (A 90 G) of Mn (II) ions (S = 5/2) in outer
sphere complexes, which is typical of reducing environments [46].
The spectra for the CM and WH samples also showed a line near
1500 gauss (g = 4), corresponding to Fe (III) in diluted domains [46].

3.7. Thermogravimetric (TG and DTG) analysis

Fig. 5. EPR spectra obtained for the biochars using a magnetic eld of 5000 gauss at
room temperature (300 K).

The pyrolysis proles shown by both TG and DTG curves for

the biomasses SB, WH, CE, and CP were similar, while the CM
biomass showed a distinct DTG curve (Fig. 6). For all the biomass
samples, the rst weight loss indicated in the DTG curve ended
at 130 C, and could be attributed to the release of water. The
next events occurred at 200300 C and 300400 C, corresponding to the degradation of hemicelluloses and cellulose, respectively
[17]. The prole exhibited by CM during the decomposition of cellulose showed the presence of two large peaks of loss mass, at
345 and 373 C, instead of the single peak presented by the other
biomasses.

Please cite this article in press as: M.E. Doumer, et al., Slow pyrolysis of different Brazilian waste biomasses as sources of soil conditioners
and energy, and for environmental protection, J. Anal. Appl. Pyrol. (2015), http://dx.doi.org/10.1016/j.jaap.2015.03.006

G Model

ARTICLE IN PRESS

JAAP-3446; No. of Pages 10

-0,004

SB
310 oC

-0,006
-0,008

20
-0,010

360 oC
0

40

-0.004

20
0

100

200

-0,004

CE

-0,006

40

-0,008

355 oC
300

400

500

600

700

Residual Mass (%)

900 1000

800

-0,010
900 1000

-0,001
-0,002

CM

60

-0,003
40
-0,004

345 oC 373 oC

20
0

100

200

300

400

500

600

700

800

-0,005
900 1000

Temperature ( C)

0,000

100

-0,001

80 oC

CP

-0,002
-0,003

60

270 oC

-0,004

40
-0,005

325 oC
0

800

100 oC

80

20

700

0,000

Temperature ( C)

80

600

-0,002

80

200

500

100

Residual Mass (%)

Residual Mass (%)

Mass Loss Rate (wt.%/ C)

0,000

100

400

85 oC

300

Temperature ( C)

100

20

-0.005

330 oC

Temperature ( C)

300 oC

-0.003

270 oC

100 200 300 400 500 600 700 800 900 1000

60

-0.002

WH

60

Mass Loss Rate (wt.%/ C)

75 oC

100

200

300

400

500

600

700

800

-0,006
900 1000

40

-0.001

80

Mass Loss Rate (wt.%/ C)

60

o
Mass Loss Rate (wt.%/ C)

-0,002

0.000

100

Residual Mass (%)

Residual Mass (%)

60 oC

80

0,000

100

Mass Loss Rate (wt.%/ C)

M.E. Doumer et al. / Journal of Analytical and Applied Pyrolysis xxx (2015) xxxxxx

Temperature ( C)
Fig. 6. Thermogravimetric and differential thermal analyses of the ve biomasses.

The decomposition of lignin occurs slowly throughout the entire

temperature range of the analysis (from ambient temperature up to
900 C) [47]. The reactions at 100 C, mainly involve the removal of
moisture. At higher temperatures, the biomass DTG proles show
cellulose decomposition, reected in an intense peak in 300350 C
range, and peaks at 275 and 365 C, corresponding to the degradation of hemicelluloses and lignin, respectively [47].

3.8. CP/MAS 13 C NMR

CP/MAS13 C NMR analysis was used to investigate the chemical
structures of the biochars (Fig. 7). The assignment of the resonance
absorptions was based on previous studies of a variety of biomass
samples including pine cone, soybean cake, corn stalk, and peanut
shell [15], as well as pitch pine [17] and Miscanthus [48].

Please cite this article in press as: M.E. Doumer, et al., Slow pyrolysis of different Brazilian waste biomasses as sources of soil conditioners
and energy, and for environmental protection, J. Anal. Appl. Pyrol. (2015), http://dx.doi.org/10.1016/j.jaap.2015.03.006

G Model
JAAP-3446; No. of Pages 10

ARTICLE IN PRESS
M.E. Doumer et al. / Journal of Analytical and Applied Pyrolysis xxx (2015) xxxxxx

studied produced reasonable amounts of bio-oil, and could compete as suitable raw materials for biofuel production or as
feedstocks for the chemical industry. These biochars could also
be used as soil conditioners, due to their stability and chemical
composition.
Acknowledgments
This work was supported by CNPq, CAPES, INCT E&A, and FUNPAR (Foundation of the Federal University of Paran UFPR). The
authors are indebted to LAMIR (Laboratory of Analysis of Minerals
and Rocks UFPR) for providing the TG/DTG analyses.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jaap.2015.03.006.

Fig. 7.

13

C NMR spectra of the ve biochars.

The spectra of all the chars exhibited peaks at 050 ppm and
150 ppm, corresponding to aliphatic carbons and phenolic groups,
respectively.
A number of differences between the biochars were observed:
peaks for carbohydrates in the 50100 ppm range were only
present in the spectra for the CE and CM biochar samples (the
same samples for which linear structures with carbonyl groups
were detected by DRIFT spectroscopy, even after pyrolysis). For
CM, signals between 72 and 75 ppm, and at 105 ppm, were related
to resonances of carbons in cellulose and hemicelluloses. The CP
biochar presented a clear peak at 150 ppm, indicating that residual
carbohydrates and lignin remained in the biochar after pyrolysis,
and this char also showed a signal at 173 ppm from the carboxyl
groups present in hemicelluloses and probably also in phenolic
groups (as indicated by the DRIFT spectrum). The higher content
of phenolic groups in the CP sample probably explained the stabilization of the free radicals found by EPR spectroscopy (Table 5).
A signal at 130 ppm, related to aromatic carbons, was present
in the spectra for all the samples, and its high intensity could
be explained by the formation of more stable aromatic compounds from carbohydrates (cellulose and hemicelluloses) during
the pyrolysis process. A peak at 29 ppm, corresponding to methyl
carbons of acetyl groups in hemicelluloses, was most intense for
the CM and WH chars, indicating a signicant presence of these
compounds. A signal at 56 ppm, reecting metxy groups of lignin,
was observed for the CE biochar, indicating incomplete carbonization. The presence of cellulose in the biochars could be explained
by the fact that cellulose tolerates higher temperatures, compared
to hemicelluloses.
4. Conclusions
A range of characterization methods were used to analyze the
pyrolysis products of different biomasses abundantly available in
Brazil. Correlations between the data obtained by the different
techniques enabled an understanding of the physicochemical features of the products. Pyrolysis of biomass produced bio-oil with
up to 70% of the caloric value of fuel oil. The biomasses CP, CE,
and SB appeared to be suitable for producing biochars with low ash
contents and high caloric values. These biochars exhibited high
contents of xed and elemental carbon, and the OFR spin density
was located close to carbon atoms. Aromatic structures were predominant in the CP, CE, and SB biochars, while aliphatic groups
were abundant in the CM and WH biochars. The biomass sources

References
[1] D. zcimen, A. Ersoy-Mericboyu, Characterization of biochar and bio-oil
samples obtained from carbonization of various biomass materials, Renew.
Energy 35 (2010) 13191324.
[2] W. Kwapinski, C.M.P. Byrne, E. Kryachko, P. Wolfram, C. Adley, J.J. Leahy, et al.,
Biochar from biomass and waste, Waste Biomass Valorization 1 (2010)
177189.
[3] Q. Lu, W.-Z. Li, X.-F. Zhu, Overview of fuel properties of biomass fast pyrolysis
oils, Energy Convers. Manage. 50 (2009) 13761383.
[4] A.V. Bridgwater, Renewable fuels and chemicals by thermal processing of
biomass, Chem. Eng. J. 91 (2003) 87102.
[5] H.F. Gercel, Bio-oil production from Onopordum acanthium L. by slow
pyrolysis, J. Anal. Appl. Pyrolysis 92 (2011) 233238.
[6] W.A.W.A.K. Ghani, A. Mohd, G. da Silva, R.T. Bachmann, Y.H. Tauq-Yap, U.
Rashid, et al., Biochar production from waste rubber-wood-sawdust and its
potential use in C sequestration: Chemical and physical characterization, Ind.
Crops Prod. 44 (2013) 1824.
[7] A. McBeath, R. Smernik, E. Krull, J. Lehmann, The inuence of feedstock and
production temperature on biochar carbon chemistry: a solid-state 13 C NMR
study, Biomass Bioenergy 60 (2014) 121129.
[8] D. Angn, Effect of pyrolysis temperature and heating rate on biochar obtained
from pyrolysis of safower seed press cake, Bioresour. Technol. 128 (2012)
593597.
[9] M. Ahmad, S.L. Soo, X. Dou, D. Mohan, J. Sung, J.E. Yang, et al., Effects of
pyrolysis temperature on soybean stover- and peanut shell-derived biochar
properties and TCE adsorption in water, Bioresour. Technol. 118 (2012)
536544.
[10] T.-Y. Jiang, J. Jiang, R.-K. Xu, Z. Li, Adsorption of Pb(II) on variable charge soils
amended with rice-straw derived biochar, Chemosphere 89 (2012) 249256.

[11] D. Koodynska,
R. Wnetrzak,
J.J. Leahy, M.H.B. Hayes, W. Kwapinski, Z.
Hubicki, Kinetic and adsorptive characterization of biochar in metal ions
removal, Chem. Eng. J. 197 (2012) 295305.
[12] L. Sun, S. Wan, W. Luo, Biochars prepared from anaerobic digestion residue,
palm bark, and Eucalyptus for adsorption of cationic methylene blue dye:
characterization, equilibrium, and kinetic studies, Bioresour. Technol. 140
(2013) 406413.
[13] J. Gaskin, C. Steiner, K. Harris, K. Das, B. Bibens, Effect of low-temperature
pyrolysis conditions on biochar for agricultural use, Trans. ASABE 51 (2008)
20612069.
[14] M. Carrier, A. Hardie, . Uras, J. Gorgens, J.H. Knoetze, Production of char from
vacuum pyrolysis of South-African sugar cane bagasse and its characterization
as activated carbon and biochar, J. Anal. Appl. Pyrolysis 96 (2012) 2432.
[15] E. Apaydn-Varol, E. Ptn, Preparation and characterization of pyrolytic chars
from different biomass samples, J. Anal. Appl. Pyrolysis 98 (2012) 2936.
[16] K. Kim, T. Kim, S. Lee, D. Choi, H. Yeo, Comparison of physicochemical features
of biooils and biochars produced from various woody biomasses by fast
pyrolysis, Renewable Energy 50 (2013) 188195.
[17] K.H. Kim, J. Kim, T. Cho, J.W. Choi, Inuence of pyrolysis temperature on
physicochemical properties of biochar obtained from the fast pyrolysis of
pitch pine (Pinus rigida), Bioresour. Technol. 118 (2012) 158162.
[18] L. Zhao, X. Cao, Heterogeneity of biochar properties as a function of feedstock
sources and production temperatures, J. Hazard. Mater. 257 (2013) 19.
[19] P.J. Mitchell, T.S.L. Dalley, R.J. Helleur, Preliminary laboratory production and
characterization of biochars from lignocellulosic municipal waste, J. Anal.
Appl. Pyrolysis 99 (2013) 7178.
[20] L. McAllister, Sustainable consumption governance in the Amazon, Environ.
Law Rep. News Anal. 1595 (2008) 1087310881.
[21] S.V. Mantilla, Comparative study of bio-oil production from sugarcane
bagasse and palm empty fruit bunch: yield optimization and bio-oil
characterization, J. Anal. Appl. Pyrolysis 108 (2014) 284294.

Please cite this article in press as: M.E. Doumer, et al., Slow pyrolysis of different Brazilian waste biomasses as sources of soil conditioners
and energy, and for environmental protection, J. Anal. Appl. Pyrol. (2015), http://dx.doi.org/10.1016/j.jaap.2015.03.006

G Model
JAAP-3446; No. of Pages 10
10

ARTICLE IN PRESS
M.E. Doumer et al. / Journal of Analytical and Applied Pyrolysis xxx (2015) xxxxxx

[22] J. Lehmann, M.C. Rillig, J. Thies, C.A. Masiello, W.C. Hockaday, D. Crowley,
Biochar effects on soil biota A review, Soil Biol. Biochem. 43 (2011)
18121836.
[23] I. Bergier, S.M. Salis, C.H.B. Miranda, E. Ortega, C.A. Luengo, Biofuel production
from water hyacinth in the Pantanal wetland, Ecohydrol. Hydrobiol. 12 (2012)
7784.
[24] R.S. Gabor, K. Eilers, D.M. McKnight, N. Fierer, S.P. Anderson, From the litter
layer to the saprolite: chemical changes in water-soluble soil organic matter
and their correlation to microbial community composition, Soil Biol. Biochem.
68 (2014) 166176.
[25] IB, Brazilian Industry of trees, (2014).
http://www.bracelpa.org.br/shared/iba 2014 pt.pdf (accessed 12.17.14).
[26] IBGE, Systematic Survey of Agricultural Production. Brazilian Institute of
Geography and Statistics, (2014). http://www.ibge.gov.br (accessed 12.17.14).
[27] Z.M. Magriotis, M.Z. Carvalho, F.P. de Sales, F.C. Alves, R.F. Resende, A.A. Saczk,
Castor bean (Ricinus communis L.) presscake from biodiesel production: an
efcient low cost adsorbent for removal of textile dyes, J. Environ. Chem. Eng.
2 (2014) 17311740.
[28] P. Okafor, P. Okon, Adsorption capacity of coconut (Cocos nucifera L.) shell for
lead copper cadmium and arsenic from aqueous solutions, Int. J. Electrochem.
Sci. 7 (2012) 1235412369.
[29] S. Banerjee, G. Aditya, G.K. Saha, Household disposables as breeding habitats
of dengue vectors: linking wastes and public health, Waste Manage. 33 (2013)
233239.
[30] C. Zettel, P. Kaufman, Featured Creatures Yellow Fever Mosquito, Univ.
Florida. (2008).
http://entnemdept.u.edu/creatures/aquatic/aedes aegypti.htm (acessed
January 2015).
[31] Y. Lee, P. Eum, C. Ryu, Y. Park, J. Jung, Characteristics of biochar produced from
slow pyrolysis of Geodae-Uksae 1, Bioresour. Technol. 130 (2013) 345350.
[32] M.M. Wright, D.E. Daugaard, J.A. Satrio, R.C. Brown, Techno-economic analysis
of biomass fast pyrolysis to transportation fuels, Fuel 89 (2010) S2S10.
[33] A.V. Bridgwater, Review of fast pyrolysis of biomass and product upgrading,
Biomass Bioenergy 38 (2012) 6894.
[34] M.I. Al-Wabel, A. Al-Omran, A.H. El-Naggar, M. Nadeem, A.R.A. Usman,
Pyrolysis temperature induced changes in characteristics and chemical
composition of biochar produced from conocarpus wastes, Bioresour.
Technol. 131 (2013) 374379.
[35] A. Sanna, S. Li, R. Linforth, K.A. Smart, J.M. Andrsen, Bio-oil and bio-char from
low temperature pyrolysis of spent grains using activated alumina, Bioresour.
Technol. 102 (2011) 1069510703.

[36] P. Fu, W. Yi, X. Bai, Z. Li, S. Hu, J. Xiang, Effect of temperature on gas
composition and char structural features of pyrolyzed agricultural residues,
Bioresour. Technol. 102 (2011) 82118219.
[37] S. Wang, Q. Wang, X. Jiang, X. Han, H. Ji, Compositional analysis of bio-oil
derived from pyrolysis of seaweed, Energy Convers. Manage. 68 (2013)
273280.
[38] J. Alvarez, G. Lopez, M. Amutio, J. Bilbao, M. Olazar, Bio-oil production from
rice husk fast pyrolysis in a conical spouted bed reactor, Fuel 128 (2014)
162169.
[39] M.Y. Harun, A.B. Dayang Radiah, Z. Zainal Abidin, R. Yunus, Effect of physical
pretreatment on dilute acid hydrolysis of water hyacinth (Eichhornia
crassipes), Bioresour. Technol. 102 (2011) 51935199.
[40] F. Goncalves, H. Ruiz, C. Nogueira, Comparison of delignied coconuts waste
and cactus for fuel-ethanol production by the simultaneous and
semi-simultaneous saccharication and fermentation, Fuel 131 (2014) 6676.
[41] K. Lammers, G. Arbuckle-Keil, J. Dighton, FT-IR study of the changes in
carbohydrate chemistry of three New Jersey pine barrens leaf litters during
simulated control burning, Soil Biol. Biochem. 41 (2009) 340347.
Molecular characterization of
[42] J. Kaal, A. Martnez Cortizas, O. Reyes, M. Solino,
Ulex europaeus biochar obtained from laboratory heat treatment
experimentsA pyrolysisGC/MS study, J. Anal. Appl. Pyrolysis 95 (2012)
205212.
[43] R.K. Sharma, J.B. Wooten, V.L. Baliga, X. Lin, W. Geoffrey Chan, M.R. Hajaligol,
Characterization of chars from pyrolysis of lignin, Fuel 83 (2004) 14691482.
[44] C. Maia, A. Mangrich, C. Budziak, J. Dos Santos, Spectroscopic and chemical
characterization of humic structures through composting advance of
sawdust/paper mill sludge, in: 11th IHSS Conf., Boston, USA, 2002, pp.
359361.
[45] S.D. Joseph, M. Camps-Arbestain, Y. Lin, P. Munroe, C.H. Chia, J. Hook, et al., An
investigation into the reactions of biochar in soil, Soil Res. 48 (2010) 501515.
[46] T. Weber, T. Allard, M.F. Benedetti, Iron speciation in interaction with organic
matter: modelling and experimental approach, J. Geochem. Explor. 88 (2006)
166171.
[47] H. Yang, R. Yan, H. Chen, D.H. Lee, C. Zheng, Characteristics of hemicellulose,
cellulose and lignin pyrolysis, Fuel 86 (2007) 17811788.
[48] F. Melligan, K. Dussan, R. Auccaise, E.H. Novotny, J.J. Leahy, M.H.B. Hayes,
et al., Characterisation of the products from pyrolysis of residues after acid
hydrolysis of Miscanthus, Bioresour. Technol. 108 (2012) 258263.

Please cite this article in press as: M.E. Doumer, et al., Slow pyrolysis of different Brazilian waste biomasses as sources of soil conditioners
and energy, and for environmental protection, J. Anal. Appl. Pyrol. (2015), http://dx.doi.org/10.1016/j.jaap.2015.03.006