Article

pubs.acs.org/EF

Characterization of Bio-oils from Dierent Pyrolysis Process Steps

and Biomass Using High-Resolution Mass Spectrometry
Patrcia V. Abdelnur,*, Boniek G. Vaz, Jose D. Rocha, Marlon B. B. de Almeida,
Marco Antonio G. Teixeira, and Rosana C. L. Pereira

National Center for Agroenergy Research, Brazilian Enterprise for Agricultural Research (EMBRAPA), Parque Estacao Biologica,
PqEB s/n, Avenida W3 Norte, 70770-901 Braslia, Federal District, Brazil

Chemistry Institute, Federal University of Goias, Campus Samambaia, 74001-970 Goiania, Goias, Brazil

Cenpes, Petrobras, Avenida Horacio Macedo, 950, Cidade Universitaria, Ilha do Fundao, 21941-915 Rio de Janeiro, Rio de Janeiro,
Brazil
S Supporting Information
*

ABSTRACT: Next-generation biofuels have been widely investigated because they have particular advantages compared to rstgeneration biofuels. Pyrolysis is an example of a thermochemical route extensively used in oil and coal industries worldwide to
produce these biofuels. Strategies for low-cost upgrading are among the biggest challenges facing the adoption of bio-oils in the
development of commercial biofuels. Specic biomass sources could be the best option for generating bio-oil with the required
properties. For this, it is necessary to understand the composition of these biomasses and their bio-oils. Here, we analyzed bio-oil
samples from the fast pyrolysis of dierent biomasses collected during two dierent steps of the process by direct-infusion highresolution mass spectrometry. First, a comparative study of two common high-resolution mass spectrometers, quadrupole timeof-ight mass spectrometry (Q-TOF MS) and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), was
performed to validate the methodology and to investigate the dierences in mass discrimination and resolution. FT-ICR MS
showed the best performance because of its unsurpassed resolution and accuracy. We apply the common petroleomics tools to
interpret the mass spectra obtained. The FT-ICR MS analysis reveals that bio-oils are dominated by Ox species. The class prole
of bio-oils was strongly aected by the biomass and steps of the pyrolysis process.

INTRODUCTION
Much has been invested worldwide in the generation of a
renewable chain of fuels based on biomass derivatives, which
has been called next-generation biofuels. These have particular
advantages compared to rst-generation biofuels; they are nonfood materials and could provide a real reduction in greenhouse
gas emissions. Biomass-based fuels could be generated from
lignocellulosic biomass, such as woody crops, agricultural
residues, and wastes. Some examples of these advanced biofuels
are algae biodiesel, butanol, cellulosic ethanol, hydrotreated
vegetable oil, biomass to liquid diesel, and biosynthetic gas.1
The main technologies described that produce these biofuels
are based on biochemical and thermochemical routes. Pyrolysis
is an example of a thermochemical route extensively used in oil
and coal industries worldwide. Its application in biomass
conversion is still innovative with pilot- and demonstrative-scale
projects. Variations in technology and operation conditions can
make changes in the process of pyrolysis. Torrefaction, also
known as a mild form of pyrolysis, occurs at temperatures in
the range of 250300 C, producing mainly torreed
biomasses and low yields of acidic pyrolignous extracts as
condensable liquids.2 Slow pyrolysis, also known as carbonization, aims to produce high yields of charcoal yet is able to
produce signicant amounts of tar if an appropriated
condensation system is connected to the furnace. In Brazil,
10 million metric tons of charcoal is produced yearly, to be
used mainly as a bioreductor in steel and iron alloy production.3
2013 American Chemical Society

Fast pyrolysis produces higher bio-oil (BO) yields compared to

conventional pyrolysis because of the high heating rates, low
residence times, and small particle sizes of the applied
feedstock. In this study, samples were collected via a fast
pyrolysis pilot plant in a 1020 kg/h1 capacity.4
Dierent biomass sources could be a good option for
generating BOs with specic properties. BO is the condensable
product fraction originating from biomass fast pyrolysis,
exhibiting some interesting features: it is liquid, presents higher
energy density than the original material, and is easy to pump
and transport over large distances. However, BO has to be
upgraded to reach suitable fuel properties. Strategies for lowcost upgrading are among the biggest challenges facing the
adoption of pyrolysis BO in the development of commercial
biofuels.
A considerable number of studies have been performed
investigating BO properties and chemical compositions to
verify their potential as biofuel.59 The most common
technique used to identify BO samples is gas chromatographymass spectrometry (GCMS). However, this technique
is limited to identifying small-chain and nonpolar compounds,
usually requiring one-step derivatization to analyze polar
compounds. Only lightweight compounds in BO can be
Received: May 1, 2013
Revised: September 26, 2013
Published: September 30, 2013
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Figure 1. Biomass fast pyrolysis pilot plant (PPR 10), with 10 kg/h capacity, for (7) BO and (9) LFBO sample reservoir.
(Rio de Janeiro, Brazil) and used without further purication.
Ammonium hydroxide was obtained from Sigma-Aldrich (Rio de
Janeiro, Brazil).
BO samples originating from the fast pyrolysis process of dierent
biomass samples (eucalyptus, eucalyptus bark, cellulosic mud, water
hyacinth, and pine) were analyzed. Eucalyptus samples were collected
from a pulp and paper plant. These samples are representative of the
industrial process and are produced in large amounts in Brazil.
Eucalyptus bark was collected from a debarking process before
chipping the trunks. Primary cellulosic mud was collected at the end of
the pulping process during ltration and purication of pulp. Water
hyacinth was collected under Brazilian Environment Institute
(IBAMA) rules from the Paraguay River near Corumba in the state
of Mato Grosso do Sul.25 Pine wood biomass sample was supplied by
BTG (Enschede, Netherlands).
General Experimental Procedures. Fast Pyrolysis Technology
and BO Production. The pilot plant shown in Figure 1 is a circulating
uidized-bed reactor, with a capacity of 10 kg/h, located at the
Bioware Company (Campinas, Brazil), where the pyrolysis runs were
carried out. Some changes in the feed capacity are expected because of
the bulk density variation of feedstock. Pretreated biomasses with a
moisture content in the range of 1012 wt % and particle sizes from 2
to 4 mm were fed from a silo (3) directly into the free board of the
reactor (2), which was preheated and previously loaded with ne sand
particles as a bed in the case of thermal pyrolysis, whereas alternatively,
a reactive catalyst bed could have been used. A conned feed screw
(3a) located at the bottom of the silo kept a regular preset feeding rate.
Air was used as the uidization agent. A blower (1) supplied the air
ow, which passed through a heater (2) and nally fed in the reactor.
The process is autothermal, once the air burned about 10% of the
biomass to supply heat for the process. The reaction temperature
ranged from 450 to 500 C. As a result, the biomass was converted
into biochar, vapor, and gas mixture. Volatile products left the reactor,
dragging the ner char particles, which were separated by means of
two insulated cyclones in series (5). A biochar reservoir (8) retained
the biochar from the cyclones until it cooled to room temperature.
After the cyclones, a two-stage recovering (condensation) system (6)
separated pyrolysis liquids into two fractions. The rst stage was an
indirect cooler with water, and the second stage was a centrifugal
device (condenser). The gases entered in the rst stage at 200250 C
and left at 8090 C. A stream rich in water and water-soluble
compounds LBOF was condensed and collected in a tank (9). The
uncondensed vapors entered in the second stage (centrifugal device),
where aerosol drops coalesced and the BO was collected at 4050 C.

analyzed by GCMS analysis, owing to the low injector

temperature in GC. However, some polar compounds, such
acids and alcohols, can be identied, which is dependent upon
the chromatographic column used in GC separation.1012 MS
has been shown to be a powerful technique for detecting polar
compounds using an electrospray ionization source (ESIMS).
Direct-infusion mass spectrometry (DIMS) analysis has been
widely used to detect and identify many chemical compounds
in dierent matrices, such as food, 13,14 fuels, 15 and
biofuels.1619 Some advantages of this technique are minimal
sample preparation steps, faster analyses, and a wider range of
compounds detected at the same injection. Smith and Lee20
have analyzed BOs using laser desorption ionizationmass
spectrometry (LDIMS) and have detected a complex nature
of them compared to non-phenolic compounds. Recently, ESI
MS has been used to detect a wide range of compounds
(phenolics and sugarics) in BOs produced from red oak,21
pine pellets, and peanut hull22 biomasses.
In the present study, BO samples originating from the
pyrolysis of dierent biomasses were analyzed by DIMS using
quadrupole time-of-ight mass spectrometry (Q-TOF MS).
However, a considerable amount of compounds was detected,
and the spectrum was quite similar to that generated for
petroleum samples (showing a Gaussian shape of m/z ions),
conrming the high complexity of BO samples. Afterward, the
BO samples were analyzed through ultrahigh-resolution mass
spectrometry (UHRMS), using Fourier transform ion cyclotron
resonance mass spectrometry (FT-ICR MS),11,12 which has
evaluated precision for petroleomic experiments as measured
by repeatability and reproducibility.23 Petroleomic tools were
used to characterize each sample according to their oxygen and
carbon classes and double-bond equivalents (DBEs).5,11,24
Additionally, samples collected in two dierent steps of the
fast pyrolysis process of each biomass [BO and light bio-oil
fraction (LBOF)] were analyzed by DIMS. A dierent
spectrum prole was obtained for each step of the process,
inferring a specic chemical composition for each step.

EXPERIMENTAL SECTION

Chemical Reagents and Samples. High-performance liquid

chromatography (HPLC)-grade methanol was purchased from Merck
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Figure 2. ESI()MS spectrum using Q-TOF MS of (a) BO and (b) LBOF from the fast pyrolysis process of water hyacinth biomass.
Pyrolysis gases exited on the top of centrifugal device and owed to
a combustion chamber to be burned (10). Optionally, the combustion
gases could recirculate to the system from a gas distributor plate to
serve as a uidization agent and as a source of heating for the reactor
bed (not shown in Figure 1). The plant operated at atmospheric
pressure. Operational conditions were monitored and controlled using
sensors distributed throughout the system, which was connected to a
computer for data acquisition (1115). Further information about
biomass fast pyrolysis in Brazil is described elsewhere.26,27
For each biomass processed, two samples were collected in dierent
steps of the pyrolysis process, BO and LBOF, and both were analyzed
by MS. BO is the oil fraction with a low water content, and LBOF is
the aqueous phase with a high water content and contains watersoluble compounds.27
BO and LBOF samples from eucalyptus, eucalyptus bark, cellulosic
mud, and water hyacinth were produced at the Bioware Company
(Campinas, Brazil), whereas BO from pine biomass was supplied by
BTG (Enschede, Netherlands)28 via Petrobras (Rio de Janeiro, Brazil).
MS Analysis. A standard solution (SS) of each BO and LBOF
sample was prepared, dissolving 10 mg of BO in 10 mL of MeOH.
Then, consecutive dilutions were performed to determine an ideal
concentration for each analyzer because they have dierent
sensitivities. The best conditions established were 0.1 mg/mL for QTOF MS analysis and 0.05 mg/mL for FT-ICR MS analysis, with both
solutions containing 0.2% ammonium hydroxide in methanol.
Q-TOF MS Analysis. ESIMS analyses were performed in the
negative-ion mode in Q-TOF MS (Waters, Manchester, U.K.), with
the following conditions: capillary voltage, 1.4 kV; gas pressure, 0.3 psi;
cone voltage, 35 V; extractor voltage, 4 V; source temperature, 100 C;
and desolvation temperature, 100 C.
Aliquots of 100 L of SS were transferred to a ask containing 900
L of methanol with a 0.2% ammonium hydroxide solution. After
shaking for 30 s using a vortex and 5 min of centrifugation, 100 L of
this solution was diluted to 1 mL of the total volume with methanol
containing a 0.2% ammonium hydroxide solution. This resulting
solution was then directly infused into the mass spectrometer.
All of the ESI()Q-TOF MS data were analyzed using the
MassLynx 3.5 software (Waters, Manchester, U.K.). Mass spectra were
accumulated over 60 s to generate nal data ranging from m/z 50 to
1000.
FT-ICR MS Analysis. Aliquots of 100 L of SS were transferred to a
ask containing 900 L of methanol with a 0.2% ammonium
hydroxide solution. After shaking for 30 s using a vortex and 5 min

of centrifugation, 500 L of this solution was taken and diluted to 1

mL of the total volume with methanol containing a 0.2% ammonium
hydroxide solution and injected using a micro-ESI. Solvents and
additives were of HPLC grade, purchased from Sigma-Aldrich, and
used as received. General ESI conditions were as follows: capillary
voltage, 3.10 kV; ow rate, 5 L min1; tube lens voltage, 39 V; and
capillary voltage, 100 V.
Ultrahigh-resolution MS was performed with a Thermo Scientic
7.2 T ESIFT-ICR MS LTQ-FT ULTRA (Thermo Scientic,
Bremen, Germany). A scan range of m/z 2001000 was used, and
100 microscans were collected in each run. The average resolving
power (Rp) was 400 000 at m/z 400, where Rp was calculated as m/m
50%, that is, by the m/z value divided by the peak width at 50% peak
height. Time-domain data (ion cyclotron resonance signal or transient
signal) were acquired for 700 ms. Microscans were co-added using
Xcalibur 2.0 software (Thermo Scientic, Bremen, Germany). The
molecular weight distribution for each sample was rst veried by
LTQ analysis to ensure the validity of the molecular weight
distribution based on FT-ICR MS.
ESI()FT-ICR MS data were analyzed using the Composer
software (Sierra Analytics, Modesto, CA). In addition to external
calibration, an internal recalibration was applied to the peak list (using
Composer software) prior to nal peak assignment. A set of theoretical
homologues series for a specic heteroatom class (most abundant class
for each ion mode) was selected as an internal calibrant because of
their presence in all samples, low errors, and high average peak
intensities. Similar tools used for petroleum analysis, such as class
distribution, DBE versus carbon number, and van Krevelen diagrams,
were used to process these highly complex spectra.

RESULTS AND DISCUSSION

BO Analysis Using Q-TOF MS. Figure 2 shows ESI()

mass spectra of BO and LBOF of water hyacinth, which were
collected from dierent steps of the pyrolysis process. Note that
the mass spectra of these two samples are dierent, revealing
dierences in their chemical composition because of the
chemical fractionation that occurred in the process. The BO
samples were collected at the end of the process and contained
many more compounds, including heavy compounds, such as
O-containing compounds (Figure 2a), and the LBOF samples,
collected at the beginning of the process, contained more
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Figure 3. (a) ESI()MS spectrum of eucalyptus BO using Q-TOF MS. Mass-to-charge (m/z) ratio from 351.00 to 351.40 using (b) Q-TOF MS
(resolution of 5000) and (c) FT-ICR MS (resolution of 400 000).

light compounds, such as acids and sugar-derivative

compounds (Figure 2b).
The highest ion intensity detected in negative mode, m/z
255 (Figure 2a), in the BO sample refers to the saturated fatty
acid palmitic acid (C16:0; C16H32O2);29 however, the highest
ion intensity detected in the LBOF, m/z 161, was attributed to
the sugar compound levoglucosan (C6H10O5) (Figure 2b).
The high abundance of sugar-derivative compounds in the
LBOF samples was also observed for the other biomass samples
submitted to fast pyrolysis (see Figure 1S of the Supporting
Information). This occurs because the hot product vapors
meet, as a rst step, a quench stream (water + LBOF recycled),
which further condensates water and light compounds. This
fraction contained more light compounds, such as acids and
polyhydroxilated compounds, which indicate derivatives of the
conversion of sugar structures (Figure 2b).
Comparing BO samples from dierent biomass sources and
processes under dierent stages of development, it was clearly
noticed that each one has a specic ngerprinting MS
spectrum. BO from water hyacinth has more fatty acid
compounds, whereas BO from eucalyptus bark contains a
triterpenoid acid (C30H46O3)30 as the highest ion intensity
detected. BOs from eucalyptus, cellulosic mud, and pine
presented similar chemical composition proles, with levoglucosan having the highest detectable ion intensity.
Q-TOF MS versus FT-ICR MS. Because of the high
chemical composition complexity of these samples, we use
UHRMS, using ESIFT-ICR MS, as a tool that has the power
to broadly characterize these samples at a molecular level. The
results obtained when applying both analytical approaches were
compared: Q-TOF MS (resolution of 5000) and FT-ICR MS
(resolution of 400 000).
To illustrate the dierences in the amount and quality of
information obtained by each analyzer, Figure 3 shows the
mass-scale-expanded segment at m/z 351 from the mass
spectrum of eucalyptus BO obtained from Q-TOF MS and FT-

ICR MS. This mass scale-expanded segment in the FT-ICR

mass spectrum demonstrates baseline separation of six dierent
compounds, whereas only one compound had been observed in
the Q-TOF mass spectrum. Resolution of all of those doublets
requires a mass resolving power (m/m 50% at m/z 351)
greater than 17 000 if the two closely spaced ion peaks have
similar magnitudes. An even higher resolving power is required
if their abundances are dierent. Such an ultrahigh resolving
power is easily achieved by FT-ICR MS or other UHRMSs,
such as Orbitrap or ultrahigh-resolution TOF MS.
This infers that Q-TOF MS does not have enough resolution
to separate compounds with the same nominal mass. For a
detailed and complete chemical composition characterization of
BO and LBOF samples, they should be analyzed using
UHRMS. However, Q-TOF MS could be a good option for
pyrolysis process evaluation during development and optimization, detecting major compounds in BO and LBOF
samples, with the advantage of being a more robust and cheaper
instrument.
Another important and signicant dierence among the two
mass spectrometers is mass discrimination; some instrumentation and/or experimental conditions have a higher sensitivity
for low mass ions versus high mass ions or vice versa. Hence,
the experimental conditions were carefully optimized to
minimize mass discrimination for the mass range of interest.
Additionally, ion source conditions and ion guide voltages were
optimized to reduce aggregation and minimize fragmentation.
Despite having performed all of these settings, the FT-ICR MS
data showed mass discrimination against very low mass ions,
especially those below m/z 140 (see Figure 2S of the
Supporting Information). However, the ions detected by FTICR MS and Q-TOF MS show similar relative abundance.
In the FT-ICR MS, the ion ight time between the
quadrupole and the ICR aects the transmission of high mass
ions versus low mass ions. The ion ight time determines how
long the ICR cell has the gate open for the ion injection, during
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water hyacinth, with O2 as the most abundant class; the other

BOs have the most abundant class with 46 oxygens,
accounting for 1220% of the identied peaks, corroborating
with previous results reported by Jarvis et al.22 and Smith et
al.21
To verify the dierences between the chemical compositions
of the BO samples, two BO samples from water hyacinth and
eucalyptus biomasses were selected and a detailed inspection of
their composition was performed.
The oxygen class distribution was completely dierent for
each BO analyzed (see Figure 3S of the Supporting
Information). BO from eucalyptus contains more oxygen
compounds compared to that from water hyacinth. This could
be explained considering the thermal chemical conversion of
hemicellulose, cellulose, and lignin as reported by Yang et al.32
The pyrolysis of hemicellulose occurred quickly, with the
weight loss of hemicellulose mainly happening at 220315 C
and that of cellulose happening at 315400 C. However,
lignin was more dicult to decompose, because its weight loss
happened in a wide temperature range of 160900 C and the
generated solid residue was very high (40 wt %). Because water
hyacinth has a lower lignin content compared to eucalyptus, it
is expected that its conversions mainly in H2, CO, CO2, H2O,
and some oxygenated compounds are those represented in
Figure 3S of the Supporting Information. On the other hand,
because eucalyptus has a higher lignin content, its conversion
not is totally complete, with a high amount of oxygenated
compounds remaining in the nal product, mainly ligninderivative compounds.25
Figure 5 shows water hyacinth and eucalyptus BO negativeion ESI isoabudance-countoured diagrams of DBE versus
carbon for three Ox heteroatom classes (O4, O6, and O8). The
oxygen classes for both oils span dierent compositional spaces
with number and DBE. Water hyacinth BO contains more O4
compounds, from C8 to C22, and DBE 515. However,
eucalyptus BO contains more O6 and O8 compounds, from C6
to C30, and DBE 218. In general, the lower oxygen
heteroatom classes (O1O6) have lower DBE values of 16,
whereas the high oxygen heteroatom classes (O7 or higher)
have higher DBE values (>7). This means that, in such
compounds, an increase in DBE and carbon number is

which trapping of injected ions occurs through the high

magnetic eld inside the cell. If sucient time is not given,
some high mass ions might not have arrived at the cell. In
contrast, if the gate is open too long, some low mass ions will
be lost. The eect of the ion ight time on mass discrimination
is notorious in FT-ICR, and typically, there is no good way of
eciently trapping ions in a very wide mass range.31 The mass
spectra acquisition conditions were set to reach the best way to
avoid the mass discrimination.
Chemical Characterization of BO by FT-ICR MS. FTICR MS has been shown to be an ideal tool for the deep
chemical composition characterization of BO samples,
especially for its unparalleled ability to simultaneously resolve
and identify thousands of peaks in complex mixtures at the level
of molecular formula assignment.22 To demonstrate the high
mass accuracy obtained, tables of assignment molecular
formulas for the some Ox class identied in the eucalyptus
BO is include in Tables 1S5S of the Supporting Information.
In addition, petroleomic-like tools are necessary to process
these highly complex matrixes. The rst data process performed
was the characterization of BO samples according to their
oxygen classes using the Composer software (Figure 4). Each

Figure 4. Oxygen class distribution for each BO analyzed by ESI()

MS using FT-ICR MS.

BO sample has a dierent prole of oxygen compounds, which

is directly related to the biomass used in the fast pyrolysis
process. The chemical composition analysis showed several
heteroatom classes consisting of 212 oxygens, except for

Figure 5. DBE versus carbon number diagrams to (a) water hyacinth BO and (b) eucalyptus BO.
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accompanied by a high oxygen content. Jarvis et al.22 reported a

similar trend for pine pellet BO.
Chemical Characterization of BO and LBOF Samples.
Another data process was performed to compare samples
collected in two dierent steps of the fast pyrolysis process (BO
and LBOF) using the same biomass. The samples obtained
from the same biomass used for FT-ICR MS characterization
were selected to compare the results.
Water hyacinth BO contains a majority of O 2 O 5
compounds, whereas LBOF samples are concentrated in O2
O8 compounds (Figure 6a). The high oxygen composition in

for highly acidic to weakly acidic species in BO is more

asymmetric than that for petroleum and because a few highly
abundant, very acidic species dominate the broadband mass
spectra.22
With these results, it was possible to conclude that the
chemical composition of the samples is dependent upon the
process conditions on the step of the process that they are
collected and is strongly aected by the biomass used in the
process.
van Krevelen Diagrams of BO and LBOF Samples. A
chemical composition data analysis was performed using the
van Krevelen diagram, a graph where each derivative compound
class is detected in a specic region of the diagram.
The van Krevelen diagram is obtained by plotting the ratios
H/C versus O/C. Each region of the diagram refers to a
specic class of compounds, such as lipid-, lignin-, and
condensed aromatic-derivative compounds,33 which easily and
clearly make the major classes of compounds in a sample
observable. The diagrams were plotted to BO samples from
water hyacinth (Figure 8a), pine (Figure 8b), eucalyptus
(Figure 8c), cellulosic mud (Figure 8d), and eucalyptus bark
(Figure 8e). In Figure 8, the blue dots mean compounds
detected in high relative abundance.
Water hyacinth BO samples are concentrated in lipidderivative compounds as fatty acids (palmitic acid), whereas
cellulosic mud BO contains lipid- and lignin-derivative
compounds. Eucalyptus BO contains a lot of lignin-, cellulose-,
and hemicellulose-derivative compounds. Levoglucosan
(C6H10O5) is the most intense sugar in this sample. Pine BO
contains more cellulose- and hemicellulose-derivative compounds. Eucalyptus bark BO has a high concentration of
triterpenoid acid (C30H46O3).
Each biomass submitted to the pyrolysis process directly
infers the chemical composition of BO. Some of them contain
more sugar-derivative compounds, and others have more ligninderivative compounds, depending upon biomass processed.
BO composition is aected by biomass composition but
could be also impacted by dierent vapor residence times34 or
catalytic eect of the sand used in the dierent uidized beds.
In this study, pine and eucalyptus BOs were produced by two
dierent setups. Therefore, the chemical composition of these
samples could be aected by the biomass and also the pyrolysis
process.
The same approach was used to compare the BO and LBOF
compositions from water hyacinth and eucalyptus. A clear
separation between BO and LBOF from water hyacinth was
noted, as mentioned before. BO contains more lipid-derivative
compounds, whereas LBOF has lipid-derivative compounds
and also cellulose- and hemicellulose-derivative compounds
(Figure 9).
Eucalyptus BO and LBOF have lignin-, cellulose-, and
hemicellulose-derivative compounds. However, most celluloseand hemicellulose-derivative compounds were extracted in the
LBOF sample. This infers that the separation method worked
for both BO and LBOF samples; however, because eucalyptus
BO presented a high concentration of levoglucosan, the
separation was not clear using oxygen class (Figure 6) and
carbon class distribution (Figure 7) graphs.

Figure 6. Oxygen class distribution graph of BO and LBOF of (a)

water hyacinth and (b) eucalyptus.

LBOF indicates the presence of high concentrations of

derivatives of the conversion of sugar structures. This occurs,
as was previously explained, because there is a quenching of the
temperature at the rst step of the fast pyrolysis process, which
condenses the water, and furthermore, water-soluble compounds, such as sugar-derivative compounds (high oxygen
composition), are extracted at this part of the process, where
LBOF samples are collected. On the other hand, eucalyptus BO
and LBOF samples could not be clearly distinguished in the
oxygen class composition graph (Figure 6b), which infers that
the separation process at the pyrolysis process was not ecient
for this biomass under the tested conditions.
Further data processing was performed for these samples,
generating carbon distribution graphs for BO and LBOF from
water hyacinth and eucalyptus biomasses (Figure 7). Of note,
water hyacinth BO had more heavy compounds with a higher
number of carbon molecules (Figure 7a). On the other hand,
LBOF presented more light compounds, containing a lower
number of carbon molecules in the structure (Figure 7b). Once
again, it is possible to infer that the separation process was not
ecient for the eucalyptus biomass because many compounds,
including heavy compounds with high numbers of carbon, were
detected in the LBOF sample collected at the beginning of the
process. There was no Gaussian shape to the total carbon
number distribution graph because the abundance distribution

CONCLUSION
DIMS has been successfully used for analyses of BO
composition. UHRMS, using FT-ICR MS, has shown to be
an essential tool for an unequivocal characterization of BO and
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Figure 7. Carbon distribution graph of BO and LBOF of (a) water hyacinth and (b) eucalyptus.

Figure 8. van Krevelen diagrams of the BO samples from (a) water hyacinth, (b) pine, (c) eucalyptus, (d) cellulosic mud, and (e) eucalyptus bark.

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Figure 9. van Krevelen diagrams of the BO and LBOF to (a) water hyacinth and (b) eucalyptus.

1S), O4 compounds (Table 2S), O6 compounds (Table 3S), O8

compounds (Table 4S), and O10 compounds (Table 5S). This
material is available free of charge via the Internet at http://
pubs.acs.org.

LBOF samples, because compounds with the same nominal

mass were present in the samples. Otherwise, a pre-separation
step should be performed before Q-TOF MS analysis. In
addition, Q-TOF MS could be a good option for pyrolysis
process evaluation, because it is a more robust and cheaper
instrument.
The chemical composition of BO and LBOF samples is
strongly aected by the biomass type and process conditions.
Each biomass submitted to the pyrolysis process directly aects
the chemical composition of BO. Some of them contain more
sugar-derivative compounds, and others have more lignin- and/
or lipid-derivative compounds. BO produced through fast
pyrolysis of water hyacinth has more lipid-derivative compounds; eucalyptus bark has more triterpenoid acid compounds; and eucalyptus, pine, and cellulosic mud have more
cellulosic- and lignin-derivative compounds. These characteristics seem to be directly related to the biomass composition
and are under investigation.
The analysis of the two product samples collected from
dierent steps of the pyrolysis process, BO and LBOF, revealed
dierent spectrum proles for each sample. Samples collected
at the rst step of condensation, LBOF, contain more sugarderivative compounds because of the quenching of vapors,
which results in water condensation and extraction of watersoluble compounds.

AUTHOR INFORMATION

Corresponding Author

*Telephone: +55-61-3448-2340. Fax: +55-61-3448-1589. Email: patricia.abdelnur@embrapa.br.

Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
The authors thank EMBRAPA and Petrobras for permission to
publish this work and for the nancial support.

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ASSOCIATED CONTENT

S Supporting Information
*

ESI()MS spectrum using Q-TOF of (a) BO and (b) LBOF

from fast pyrolysis of dierent biomasses (Figure 1S), typical
mass spectrum of a eucalyptus BO acquired in Q-TOF MS and
FT-ICR MS (Figure 2S), oxygen class distribution for (a) water
hyacinth BO and (b) eucalyptus BO (Figure 3S), and estimated
molecular formulas for the measured m/z values from ESI()
FT-ICR MS eucalyptus BO results for O2 compounds (Table
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