Biomass and Bioenergy 129 (2019) 105335

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Biomass and Bioenergy

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

Research paper

Torrefaction of wheat-barley straw: Composition and toxicity of torrefaction T

condensates
Katarzyna Jagodzińskaa,∗,1, Michał Czerepb, Edyta Kudlekc, Mateusz Wnukowskib,
Weihong Yangd
a
Silesian University of Technology, Institute of Power Engineering and Turbomachinery, Konarskiego 20, Gliwice, Poland
b
Wroclaw University of Science and Technology, Department of Boilers, Combustion and Energy Processes, Wybrzeże St, Wyspiańskiego 27, Wroclaw, Poland
c
Silesian University of Technology, Institute of Water and Wastewater Engineering, Konarskiego 18, Gliwice, Poland
d
KTH Royal Institute of Technology, Department of Material Sciences and Engineering, Brinellvägen 23, Stockholm, Sweden

ARTICLE INFO ABSTRACT

Keywords: Until now, few studies on the valorisation of torrefaction condensable volatiles (condensates) have been per-
Biomass formed. The composition and toxicity of torrefaction condensable volatiles determine their possible applications.
Condensable volatiles Therefore, a study on the composition of wheat-barley straw torrefaction condensates, combined with toxicity
Toxicity tests tests, was performed. This analysis was mainly aimed at the utilisation of these condensates as an anaerobic
Phenols
digestion substrate. The torrefaction process was performed in a batch-scale reactor at temperatures from 240 °C
Furans
to 320 °C. The condensates were analysed using GC/MS, and quantitative analysis was based on the calibration
curves (external standard method). Toxicity tests were performed for vascular plants (Lemna sp. Growth
Inhibition Test), saltwater bacteria (Microtox® bioassay) and freshwater crustaceans (Daphtoxkit F magna®
survival bioassay). The condensates were classified as highly toxic for the tested organisms. Compounds that are
inhibitory and/or toxic to anaerobic bacteria were detected in the samples, e.g. furfural, guaiacol, palmitic acid
and oleic acid. Taking into account the condensates’ high toxicity for the tested organisms and the presence of
anaerobic digestion process inhibitors, there is a significant likelihood that prior detoxification of the con-
densates is necessary before they can be utilised as anaerobic digestion substrates.

1. Introduction they have a similar or lower energy density in comparison to those

Barley and wheat are two of the most widely grown crop species
worldwide, and the European Union is the leading global producer of
them. Due to their extensive availability, the residues from their pre-
paration represent a high-potential source of heat and energy. However,
their bulk density is relatively low (loose wheat straw – 40–82 kg/m3,
depending on the source [1,2]), and this makes their handling and
transport relatively expensive. Furthermore, this type of biomass is char-
acterised by a strongly heterogeneous composition, high moisture content
and relatively low calorific value. Pelletising combined with the torre-
faction of the residues constitute an efficient way to overcome these lim-
itations and thereby to increase their competitiveness with the other types
of biomass commonly used in the energy and heat production sector.
Pelletising previously torrefied biomass is difficult due to the in-
sufficient durability and low mass density of the obtained pellets [3] –
made of raw biomass [4]. Moreover, the pelletisation of biochar is
connected with higher friction in a press channel of a pellet mill,
causing a higher pelletising pressure and thereby an increased energy
uptake or even press channel blockages, which may result in fire [5].
Subjecting pelletised biomass to the torrefaction process can mitigate
all of those drawbacks. According to Shang et al. [6], pelletised and
subsequently torrefied Scots pine does not show any springback effect
or disintegration at torrefaction temperatures up to 270 °C.
Torrefaction has been a subject of research for roughtly 15 years. Its
main objective is to obtain fuel characterised by a high energy density
combined with high hydrophobicity and a low moisture content;
therefore, the majority of recent studies have focused on detailed
analyses of the changes in the feedstock chemical and physical prop-
erties during the process [7–9]. In parallel, gas (torgas) with con-
densable volatiles is produced as well. It is usually burnt with another

Corresponding author. KTH Royal Institute of Technology, Department of Material Sciences and Engineering, Brinellvägen 23, Stockholm, Sweden.
∗

E-mail addresses: kjag@kth.se (K. Jagodzińska), michal.czerep@pwr.edu.pl (M. Czerep), edyta.kudlek@polsl.pl (E. Kudlek),
mateusz.wnukowski@pwr.edu.pl (M. Wnukowski), weihong@kth.se (W. Yang).
1
Present address: KTH Royal Institute of Technology, Department of Material Sciences and Engineering, Brinellvägen 23, Stockholm, Sweden.

https://doi.org/10.1016/j.biombioe.2019.105335
Received 5 April 2019; Received in revised form 6 August 2019; Accepted 12 August 2019
Available online 23 August 2019
0961-9534/ © 2019 Elsevier Ltd. All rights reserved.
K. Jagodzińska, et al.
fuel (e.g., natural gas), and the produced flue gas is used to either heat a
torrefaction agent or as a torrefaction agent itself [10]. Condensable
volatile content, however, can result in the clogging of the gas feed
lines, so a cooling (condensation) stage is often used to avoid that.
Those condensable volatiles (condensates) released during torre-
faction have been extensively studied as well. The previous studies were
mainly performed in fixed-bed reactors with sample masses in the range
of 2.5–40 g and temperatures in the range of 220–300 °C [11–14]. Some
of the research was also performed using TGA coupled with GC-MS
[15]. The previous studies’ outcomes clearly show the tendency for the
formation of the main group of compounds (e.g., acids, ketones, alde-
hydes, alcohols, furans, and phenols). Thành et al. [14] also performed
the quantification of the main compounds (e.g., acetic acid, methanol,
furfural, phenol, and syringol), thereby greatly contributing to the un-
derstanding of the volatile formation during torrefaction.
Currently, those condensable volatiles are generally combusted
back to increase the energy efficiency of the installation or are treated
as a hazardous waste, as they are highly corrosive to the combusting
equipment. Thus far, a few studies have focused on the valorisation of
the obtained torrefaction condensates, mainly from woody biomass
[16]. The condensates have been used as fertilisers but also as herbi-
cides, insecticides, fungicides, coagulating agents in a rubber produc-
tion process or a source of valuable chemicals. This knowledge gap can
be filled by the extensive research on pyrolysis oil utilisation, including
their broad characterisation [17,18], although only partially, because
pyrolysis oils significantly differ from torrefaction condensates. Con-
sequently, those studies can only provide some guidelines for torre-
faction liquid applications.
Doddapaneni et al. [19] proposed a new method of torrefaction
condensate utilisation as a substrate for an anaerobic digestion process
(AD). However, the condensates are acknowledged to contain phenols,
furans and aldehydes (e.g., furfural, guaiacol and 5-hydro-
xymethylfural), which are inhibitors to microbes [20,21]. Conse-
quently, a torrefaction system combined with condensate detoxification
was proposed. The detoxification was carried out in a glass adsorption
column filled with torrefied biomass (biochar) as an absorber. After the
detoxification, the condensate was used as an anaerobic digestion
substrate, and the biochar previously used as an absorber was pelletised
and used as a fuel. Such integration of the processes improves the
system economic efficiency and reduces the quantity of hazardous
wastes produced during the torrefaction itself. Tests were performed on
pine wood chips as a commonly used biomass in industrial applications
(e.g., paper production). A techno-economic analysis of the installation
[22] showed that the system is highly sensitive to the feedstock price;
therefore, the reduction of that price improves the competitiveness of
the torrefied wood pellets in relation to raw wood pellets. Using agri-
cultural residues instead of wood may further decrease the torrefied
pellet price, thereby increasing the economic feasibility of the system.
During anaerobic digestion (AD), microorganisms convert most of
the substrate's carbon into biogas (mainly methane and carbon dioxide)
and the leftover digestate can be used as an agricultural fertiliser. Since
the presence of phenols in the digestate can be inhibitory for the ac-
tivity of ammonia-oxidising bacteria in the soil [23], the AD should be
conducted in such a way to limit their concentration in the digestates,
mainly by adjusting the feedstock and process temperature. The dif-
ferent phenolic compounds are characterised by different levels of
toxicity [24], and the differences in the degree to which they are fer-
mentable are mostly related to their concentration, nature and type of
microorganism being exposed to them [25]. In addition, phenolic
compounds increase the fungicidal efficiency of wood biomass vinegar
in comparison to its main compounds - acetic acid and formic acid [26].
Therefore, it may be concluded that phenolic compounds play a leading
role in determining the method of condensate utilisation.
Up to now, few studies have been performed on the valorisation of
the condensates obtained during agricultural residue torrefaction.
Therefore, the main objective of this study is to determine the toxicity
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Biomass and Bioenergy 129 (2019) 105335
of the torrefaction condensates as a method for the preliminary as-
sessment of their further application, aiming mainly at their utilisation
as an anaerobic digestion substrate. The impact of the torrefaction
temperature on the condensate composition and toxicity was de-
termined as well. A special emphasis was put on phenolic compounds.
Taking into account their wide availability, wheat-barley straw pellets
were chosen as the biomass torrefied within the study.
2. Materials and methods
2.1. Feedstock properties
The tests were performed on the pelletised wheat-barley straw re-
sidues commercially used in Germany (wheat/barley volume ratio: 95/
5; size of pellets: ϕ15 mm; length = 29–30 mm; no binding agent). The
feedstock properties are shown in Table A1 in the Supplementary ma-
terial - it is characterised by relatively high ash and chlorine contents.
The biomass was analysed by an external lab (Zakłady Pomiarowo -
Badawcze Energetyki „ENERGOPOMIAR” Sp. z o. o., Gliwice, Poland) –
the total contents of C, H, N, and S in the fuel were determined ac-
cording to EN 15407:2011 using IR and TCD methods, the Cl content
was measured using IC (EN 15408:2011), and the Na and K contents
were determined using a Thermo iCAP 6500 Due ICP Spectrometer. The
O content was calculated as the difference between 100% and the sum
of the contents of the other elements. The total Hg content (organic and
inorganic) was determined according to EPA Method 7473:2007 (AAS
method with amalgamate technique). The LHV was determined using a
bomb calorimeter, and the Vdaf content was determined using ther-
mogravimetric analysis.
2.2. Torrefaction process
Fig. 1 shows a flow chart presenting the main stages carried out
within the study.
A TG analysis and trial tests were performed to choose the tem-
perature range (240–320°C) and sample holding time at the final tem-
perature (75 min). After that time, the torgas yield significantly de-
creased, indicating the end of the carbonisation process. Cheng et al.
[11] performed tests at temperatures equal to or higher than 225 °C in a
reactor of similar design and determined the residence time in the re-
actor to be 2 h – this time was correspondingly extended within this
study due to the higher mass of the samples.
The mass of the feedstock sample was 2 kg for each test.
Torrefaction tests were performed in a lab-scale batch reactor (Fig. 2)
with a heating mantle made of three ceramic insulated band heaters.
The heaters were regulated by a programmable logic controller (PLC)
coupled with a type K thermocouple mounted into a ceramic layer of
one of the band heaters. A random order of experiments was introduced
to ensure avoidance of consecutive run errors.
The sample was introduced into the hot reactor in a stainless-steel
mesh basket (ϕ = 300 mm; height = 450 mm; aperture = 0.5 mm).
Afterwards, the reactor was closed, and the sample was manually mixed
by a two-bladed centrifugal stirrer. The sample temperature was mea-
sured by a type K thermocouple coupled with a digital thermometer.
The thermocouple immersion was regulated, and thus the temperature
along the thickness of the sample layer was measured.
During the first stage of heating of the sample (when the O2 content
was higher than 2% in the produced gas), the reactor was flushed with
nitrogen to purge the air from the system. Torgas spewed out through
two stub pipes: one connected to a flare mounted on the top of the
reactor and supplied with natural gas and air, and the second connected
to a sampling path – a set of impingers immersed in a cooling bath
(propylene glycol; 0.5 °C), a conditioner and a gas analyser. Trial tests
have shown that most of the volatiles are polar compounds, so water
was chosen as a solvent. According to Refs. [27,28], in the torrefaction
process, two impingers are enough for the volatile capture with
K. Jagodzińska, et al.
Fig. 1. Flow chart presenting the main stages of the study.
sufficient efficiency; that is why two impingers were used during the
tests, each with 100 cm3 of demineralised water.
At the end of every experiment, the contents of the impingers
(condensable volatiles) were mixed together, and the volume and mass
of the samples were measured. The samples were stirred and heated to
the ambient temperature, and afterwards the solutions were filtered
down, thereby separating the water-soluble (WS) compounds, herein
referred to as condensates, and the water-insoluble (liquid gel - LG)
compounds to determine their yields.
After each test, the biochar was collected and weighted. The volume
rate of torgas was not determined, and therefore the gas yield was
calculated as the difference between the initial feedstock mass and the
sum of the other yields.
The condensates were analysed using an Agilent 7820 gas chro-
matograph coupled to an Agilent 5977B MSD mass spectrometer.
Samples of 0.5 μl were introduced into the GC injector (250 °C;
split = 20), and helium was used as the carrier gas (1.5 ml/min). The
Fig. 2. The general scheme of the test rig (CB – cooling bath; DT – digital thermometer; TC – thermocouple).
3
Biomass and Bioenergy 129 (2019) 105335
GC was equipped with a Stabilwax-DA column (30 m × 0.32 mm x
0.25 μm; Restek), and the temperature profile was as follows: holding at
50 °C for 5 min, then increasing at 10 °C/min to 200 °C and holding for
20 min. Compound identification was automatically performed by
comparing the mass spectra with the NIST-14 MS library (minimum
match factor = 80%). The MS scanning range was m/z 10–450 with a
frequency of 1.7 scans/sec. The gain factor and EM Volts were 0.5 and
1348.5, respectively, and the MS source and quadrupole temperatures
were 230 °C and 150 °C, respectively.
On the basis of the MS qualitative analysis, part of the major com-
pounds detected during the GC/MS analysis were subjected to a
quantitative analysis based on the calibration curves for each com-
pound, according to an external standard method [29]. The curves were
created by determining four points of known compound concentration
in an isopropanol-compound solution; five repetitions for each point
were performed. The isopropanol and reference substances (acetic an-
hydride, 2-methoxyphenol, 4-ethyl-2-methoxyphenol, 4-ethylphenol, 4-
K. Jagodzińska, et al.
Fig. 3. Biochar, condensable and gas mass yields in dry-ash free state based on
initial feedstock mass; WS – water-soluble compounds, LG – liquid gel.
ethenyl-2-methoxyphenol, 4-methylphenol, and phenol) used for the
calibration were of a chromatographic grade (Sigma Aldrich, Poland,
with the exception of phenol, purchased from Chempur, Poland). The
use of external standards proved the MS qualitative analyses on the
base of the retention time and three selected ions (the three highest
from the mass spectrum with one being the target ion and the rest
qualifiers). Table A2 in the Supplementary material presents the
quantified compounds with the corresponding ions used for the quan-
titative analysis.
2.3. Toxicity tests
After filtering down the liquid gel (LG) and thus separating the
water-soluble phase (condensate), each condensate sample was sub-
jected to toxicity tests to assess their impact on the environment. The
results of the saltwater bacteria (Allivibrio fisheri) Microtox® bioassay
were compared to the results of the acute bioassays (with bacteria,
microcrustaceans, and fish), and a good correlation between their re-
sults was found [30]. Therefore, that test was chosen as a part of the
analysis within the study. The toxicological evaluation was extended
with two additional assays to broaden their scope to different trophic
levels: the Lemna sp. Growth Inhibition Test (GIT), where the test or-
ganisms were vascular plants (Lemna minor), and the Daphtoxkit F
magna® survival bioassay, where the test organisms were freshwater
crustaceans (Daphnia magna).
The tests were performed for the non-diluted sample and afterwards
for the condensate-deionised water solutions for as long as measurable
results were obtained. The Lemna sp. Growth Inhibition Test and the
Daphtoxkit F magna® survival bioassay gave measurable results for the
dilution ratio of 1:1000, whereas the Microtox® bioassay gave mea-
surable results for the dilution ratio of 1:100. However, the Microtox®
bioassay was also performed for the dilution ratio of 1:1000 for a
comparison of the results.
The Lemna sp. Growth Inhibition Test was performed according to
OECD Guideline 221. The test plants from our own breeding were used.
The bioassay was conducted at temperature of 25 ± 1 °C with constant
exposure to 6000 lux light. The test results were compared to a control
sample.
The enzymatic Microtox® bioassay, with Allivibrio fisheri as indicator
organisms, was performed according to the Screening Tests procedure
of the MicrotoxOmni system in a Microtox Model 500 analyser (Modern
Water, Warsaw, Poland). Over last 25 years, this test has been re-
cognised as reliable bioassay for environmental risk assessment among
many international regulation bodies (e.g. OECD, Swedish
Environmental Protection Agency, American Society for Testing and
Materials [31]). The bacteria are characterised by sensitivity to a wide
4
Biomass and Bioenergy 129 (2019) 105335
spectrum of organic and inorganic toxins. The test result is shown as a
change in the tests organisms' bioluminescence in comparison to that in
a 2% NaCl solution (a control sample). The change is related to the
inhibition of the bacterial metabolic processes. The exposure times
were 5 and 15 min. No initial preparation of the samples was necessary,
as their pH was in the range recommended by the analyser's manu-
facturer (pH ≈ 6.0–8.0).
In addition, the EC50 value was estimated based on the Microtox®
bioassay calculation program (Basic Test procedure). The value is de-
fined as the toxic compound concentration that reduces the light in-
tensity (harmful effect on bacteria life processes) by 50% compared to
the control sample. The Basic Test is a procedure that measures the
acute toxicity of the initial sample and their dilutions in duplicate. The
EC50 values were interpreted from the chart of % effect vs concentration
drawn by the program software.
The Daphtoxkit F magna® survival bioassay (Tigret, Warsaw,
Poland) was performed according to OECD Guideline 202, ISO 6341
and ASTM E1440-91. The number of dead organisms was evaluated
after 24 h and 48 h.
3. Results and discussion
3.1. Product yields
The changes in the biochar (B) and condensable volatile (the sum of
water-soluble compounds and liquid) yields are not linear (Fig. 3). With
the temperature increase from 240 °C to 260 °C, the yield increases by
two times; afterwards, the increase is not so significant, and mainly the
gas (G) yield increases as the result of the biochar yield decrease. This
non-linear change is connected with secondary reactions and the
cracking of the condensable volatiles into low molecular weight organic
compounds [12]. However, the general tendency shows that with the
temperature increase, the B yield decreases in favour of the C and G
yields, which coincides with the available literature data [32–34].
The liquid gel (LG) volume increased with the temperature as well,
and at 320 °C, it was approximately 15%vol. of the total C yield due to
the enhanced formation of non-polar compounds (e.g., phenols, ben-
zene derivatives and other heterocyclic compounds).
The exact yield values are shown in Table A3 in the Supplementary
material.
3.2. Condensate composition
The condensate (water-soluble phase of condensable volatiles)
composition was determined using GC-MS. A list of all detected com-
pounds can be found in Tables 2–5 at the end of the manuscript. The
chromatograms are shown in the Supplementary material (Figure A1-
A5).
The detected compounds were divided into 8 main groups (Table A4
in the Supplementary material; Fig. 4). The peaks with unidentifiable
hydrocarbons, due to missing spectral or chromatographic data, or
mixed hydrocarbons are marked as Un (unknown). Alkanes (including
halo- and cycloalkanes), e.g., chloromethane, 3-ethyl-2-hydro-
xycyclopent-2-en-1-one, benzene derivatives (1,2,3-trimethoxy-5-me-
thylbenzene) and other heterocyclic compounds (3-hydroxy-2-methyl-
pyran-4-one; maltol) were detected in the analysed samples as well.
However, the area% of those groups is in the range of 0–0.32; therefore,
there are not mentioned further.
Moving on to the result analysis, wheat straw contains 30–45%
cellulose, 17–32% hemicellulose and 16–23% lignin, whereas barley
straw's contents are 35–45%, 30–50% and 8–20%, respectively [35].
Consequently, hemicellulose can be assumed to be the main compound
of the analysed feedstock, followed by cellulose and lignin. However,
cellulose is characterised by a higher thermal stability than hemi-
cellulose or lignin [36], and thus mostly hemicellulose and lignin de-
composition products can be found in the torrefaction condensates.
K. Jagodzińska, et al.
Fig. 4. Composition of WS (relative peak area distribution - area%).
Moreover, during palletisation, the lignin softens [37] and becomes
easier to decompose, which is reflected in the condensates composition
as well.
Fig. 4 shows the relative peak area distributions (area%) of the
groups of species identified in the condensables. They mainly include
acids, ketones, phenols, furans, esters and aldehydes. The complexity of
the condensate composition increases with the torrefaction tempera-
ture.
The identified groups are in line with the available literature data
[11,13,15], as the thermal depolymerisation of hemicellulose, lignin,
and cellulose, to some extent, results in pyrans, phenols and anhy-
drosugars formation. In parallel, competing reactions (e.g., ring scis-
sion, side-chain splitting, rearrangement) occur, resulting in their de-
composition to low-molecular-weight oxygenates, such as acids,
ketones, aldehydes, alcohols, and furans [36].
Acids, ketones and alcohols dominate in the analysed temperature
range. Their changes with the temperature are not obvious. The main
acid is acetic acid, derived from the disassociation of the acetyl func-
tional group in xylan. The content of acetic acid in the analysed con-
densates varied between 5.12 kg/m3 and 33.84 kg/m3, with a general
increasing tendency with the torrefaction temperature and a maximum
at 300 °C. The domination of acetic acid over the other compounds
coincides with previous studies on wheat straw torrefaction [13,14]. On
the other hand, González Martínez [15] shows a methanol content
higher than that of acetic acid during wheat straw torrefaction, whereas
Bridgeman et al. [38] shows acetaldehyde and formaldehyde as the
dominant compounds during the torrefaction of reed canary grass
(characterised by a similar composition to that of wheat straw). This
shows that even a slight difference in the feedstock composition can
significantly influence the condensate composition.
Propan-2-one is a dominant ketone, derived from hexose-containing
polysaccharides (β-glucan, arabinogalactan, galactomannan, gluco-
mannan, xyloglucan) [39]. On the other hand, Thành et al. [14] show
1-hydroxypropan-2-one as the main ketone in torrefaction condensates,
which is a result of the hexose-containing polysaccharide decomposi-
tion as well.
Playne and Smith and Hayward and Lau [40,41] indicated that the
following components are toxic for anaerobic bacteria, inter alia:
components belonging to the groups of alcohols (C5–C12; e.g., hexanol,
octanol), ketones (C5–C8; pentan-3-one, hepta-4-one), benzene and
benzene derivatives (e.g., nitrobenzene, methyl benzene), isoamyl
acetate, di-isopropyl and tetrachloromethane. None of those com-
pounds were detected in the analysed samples, similarly to in previous
studies [13–15,38].
A low content (area% in the range of 0.3–3.9) of long-chain fatty
acids (LCFAs) was detected – (Z)-octadec-13-enoic acid was found at
the torrefaction temperature range of 260–300 °C, whereas n-
5
Biomass and Bioenergy 129 (2019) 105335
hexadecenoic acid (palmitic acid), octadecanoic acid (stearic acid),
octa-9,12-dienoic acid and trace levels of (Z)-octadec-9-enoic acid
(oleic acid) were detected at the torrefaction temperature of 240 °C. The
LCFA content increased with the decreasing temperature, and at 320 °C,
no LCFAs were detected. LCFAs are considered to have an inhibitory
effect on the anaerobic digestion process, which is connected with their
adsorption on the methanogen cells walls and interference with their
protective or transport functions interference [42]. None of the pre-
vious studies on wheat straw torrefaction show LCFAs in the con-
densates [13–15,38], which may be a result of the GC-MS analysis
technique used.
A low pyridines (pyridine and meta-substituted pyridine deriva-
tives) content was detected in all condensates, with the maximum at the
torrefaction temperature of 300 °C (area% of 0.54%). Pyridine was
detected in the temperature range of 280–300 °C and 3-methoxypyr-
idine at 280 °C, whereas pyridin-3-ol was detected in all samples and
was the main compound of the pyridine group. Meta-substituted pyr-
idine derivatives are characterised by low toxicity, and pyridine deri-
vatives with –OH are less toxic than those with a methyl group [43];
therefore, the detected pyridines are not suspected to have an inhibitory
impact on the anaerobic digestion process. None of the previous studies
on wheat straw torrefaction show pyridine and pyridine derivatives in
the condensates [13–15,38], whereas those compounds can be found in
condensates from wood, sewage sludge and municipal solid waste tor-
refaction [28,44,45].
The ester group, formed by esterification of the acids and alcohols
contained in the condensates, is mainly composed of methyl esters
(methyl formate, methyl acetate, methyl propanoate, and methyl furan-
2-carboxylate). Esters were also found in the condensates analysed
within the previous studies on wheat straw torrefaction [14,15]. Con-
trary to those studies, though, no anhydrosugars (e.g., levoglucose-
none) were detected. It is likely that their decomposition occurred in
the reactor, before reaching the condenser.
Furans, especially furfural and its derivatives, are known to be in-
hibitory for the anaerobic digestion microorganisms [22]. Conse-
quently, their presence may negatively impact the condensates’ appli-
cation as anaerobic digestion substrates. Fig. 4 shows that the content of
the furan group is non-negligible.
Fig. 5 shows the furan group composition, which changes with the
temperature. They are mainly in the form of furan-2-ylmethanol (fur-
furyl alcohol), whose content has its local minimum at the torrefaction
temperature of 280 °C. This is in line with Martínez et al. [46], who
observed a local minimum of the furfuryl alcohol formation during
wheat straw torrefaction at 270–275 °C. Furan-2-carbaldehyde (fur-
fural) can also be observed at lower torrefaction temperatures
(240–280 °C), which is also in line with the previous study of Martínez
et al. [46], who observed that furfural was produced in significant
amounts at temperatures lower than 300 °C as a result of cellulose and
hemicellulose decomposition. Moreover, the formation of 1-(furan-2-yl)
ethenone (2-acetylfuran), likely by the acylation of furans, is enhanced
by the temperature increase. Consequently, at higher temperatures, the
yield of other furans, such as oxolane and its derivatives, increase as a
result of the further thermal recompositing.
Phenols were detected in all analysed samples, and their yield was
stable in the torrefaction temperature range of 240–300 °C and in-
creased at 320 °C (Fig. 4). This increase is a consequence of the lignin
decomposition, which occurs to a large extent at temperatures higher
than 300 °C [5].
Fig. 6a shows that 2-methoxy-4-vinylphenol (guiacol) was identified
in all of the analysed samples. It is a result of arabinoxylan decom-
position - the arabinoxylan in the barley and wheat cell walls is cross-
linked to ferulic acid (lignin-like compound), which decomposes to
form guiacol [39]. Therefore, the progressive hemicellulose decom-
position is reflected by the guiacol and guiacol derivatives dominating
in all the analysed samples.
Summarising, the increase in the phenol yield at 320 °C in parallel
K. Jagodzińska, et al. Biomass and Bioenergy 129 (2019) 105335

Fig. 5. Furans composition in condensates (relative peak area distribution - area%) with the errors marked in red. (For interpretation of the references to colour in
this figure legend, the reader is referred to the Web version of this article.)

Fig. 6. a Phenols composition in condensates (relative peak area distribution - area%) with the errors marked in red. Fig. 6b The results of the quantitative analysis of
the main detected phenols (the measurement errors do not exceed 2.5%). (For interpretation of the references to colour in this figure legend, the reader is referred to
the Web version of this article.)

6
K. Jagodzińska, et al.
with the decreases in the yields of guiacol and guiacol-derived com-
pounds in favour of other phenols (mainly 4-ethylphenol) suggest the
formation of phenols derived from lignin decomposition. At lower
temperatures, on the other hand, the phenolic compound formation is
mainly connected to the hemicellulose decomposition.
Fig. 6b shows the results of the quantitative analysis of the main
phenolics detected in the condensates. A constant increase in the
guiacol concentration until 300 °C and a decrease at 320 °C is shown.
The same tendency can be seen for phenol, which confirms the for-
mation of other phenols at temperatures higher than 300 °C by direct
reaction or the re-composition of previously formed phenolics. This
confirms that at higher torrefaction temperatures (> 300 °C), the de-
composition of lignin plays a major role in the formation of the phe-
nolics. The exact values of the compound concentrations can be found
in the Supplementary material (Table A5).
Traces of 4-methylphenol (p-Cresol) have been detected in samples
as well, with no clear relationship between its concentration in a sample
and the torrefaction temperature (Fig. 6b).
3.3. Toxicity tests
The Lemna sp. Growth Inhibition Test, the Microtox® enzymatic
bioassay and the Daphtoxkit F magna® survival bioassay were per-
formed for the analysed samples. Tests were performed for sample-
demineralised water solutions with 1:100 (only Microtox® bioassay)
and 1:1000 ratios (all tests). The numerical results of the tests can be
found in the Supplementary material (Table A6).
The toxicity classification used in this study is based on the mag-
nitude of the observed effect in the indicator organisms, following
Werle and Dudziak [47]. According to those classification guidelines,
water solutions with toxicological effects in the range of 50.1–75% are
characterised as toxic, and those in the range of 75.1–100% are char-
acterised as highly toxic. Consequently, Fig. 7 shows the results of the
Microtox® and Daphtoxkit F magna® bioassays for the 1:1000 dilution
ratio with the limit of 75.1% marked as a red line. The measurement
error does not exceed 5%.
Fig. 7 does not show the Lemna sp. Growth Inhibition Test results
because the analysed samples caused the inhibition of the plant growth
and afterwards its necrosis (toxicological effect equal to 100%).
Therefore, all samples were classified as highly toxic. Consequently, it
can be concluded that the introduction of those samples into the en-
vironment in an unchanged form will have an adverse effect on vascular
plants.
Fig. 7. The results of toxicity tests with the errors marked in red (legend: the test name, the exposure time, the sample dilution ratio). (For interpretation of the
references to colour in this figure legend, the reader is referred to the Web version of this article.)
7
Biomass and Bioenergy 129 (2019) 105335
The results of the Microtox® bioassay for the samples with a 1:100
dilution ratio were higher than 96% for every sample, and thus they
were classified as highly toxic. For comparison reasons, those results are
not included in Fig. 7; only the results for the 1:1000 dilution ratio are
shown. Obviously, the 1:1000 dilution causes lower toxicological ef-
fects; notwithstanding that, all of the condensates should be considered
toxic (240 °C) or highly toxic (260–320 °C) due to the toxicological ef-
fect being close to or higher than 75%. The exposure time (5 and
15 min) does not show a significant impact on the ecotoxicological ef-
fect of the sample.
The tendencies observed within the Daphtoxkit F magna® survival
bioassay for 24 h are correlated with the results of the Microtox®
bioassay – all of the samples should be characterised as toxic (240 °C) or
highly toxic (260–320 °C). However, the sensitivity of the indicator
organisms is slightly lower than those in the Microtox® bioassay. The
exposure time of 48 h resulted in a 100% ecotoxicological effect, re-
gardless of the temperature.
An increasing tendency of the toxicological effect with the tem-
perature can be seen (Fig. 7). This occurs until the torrefaction tem-
perature reaches 300 °C, and then a decrease can be observed at 320 °C
to the values lower than those for 280 °C. This phenomenon occurs
despite the increases in the phenol and furan yields (Fig. 4), which are
considered as the main toxic compounds in torrefaction condensates.
This leads to the conclusion that the condensate acute toxicity is the
result of a synergistic effect of the wide spectrum of compounds, and it
is hard to assess their toxicity on the basis of only the furans and
phenols contents.
The results of the Microtox® bioassay were also used to determine
the half-maximal effective concentration, EC50, shown in Table 1. The
values are expressed in ppm (μg/ml) as is common in the thematic
literature; a lower value means a higher toxicity. The tendencies follow
the results of two bioassays shown in Fig. 7 – the condensate at the
torrefaction temperature of 240 °C is characterised by the lowest acute
toxicity, and the condensates at 280 °C and 300 °C by the highest acute
toxicity, and the decrease in the condensate toxicity at 320 °C can be
seen as well.
However, samples with an EC50 value equal to or greater than
100 ppm are commonly considered to be non-toxic because of the very
slight possibility of finding those pollutants in an aqueous environment
due to their very low concentration [48]. Ruiz et al. [30] studied pes-
ticides, and many of them (e.g., chlormequat or paraquat) appeared to
be non-toxic as well, despite the fact that they are considered toxic and
are on the Environmental Protection Agency (EPA) list of extremely
K. Jagodzińska, et al. Biomass and Bioenergy 129 (2019) 105335

Table 1 of mixed hydrocarbons and thus improving the identification of the

The EC50 values determined on the basis of the Microtox® bioassay results. compounds.
Temperature (sample) EC50(15) Unit The last limitation concerns the lack of previous studies on the
torrefaction condensate toxicity. Therefore, there is a lack of a theore-
240 °C 1958 ± 183 ppm tical foundation for the research methodology and a lack of data to refer
260 °C 1704 ± 142 ppm
to as well.
280 °C 1544 ± 149 ppm
300 °C 1507 ± 129 ppm
320 °C 1593 ± 171 ppm
4. Conclusions

hazardous substances. Notwithstanding that, the study was mainly
aimed at using the condensates as an anaerobic digestion substrate
directly, when their concentration will exceed the value of EC50 by
several times. Therefore, despite the discrepancy between the results of
the toxicity tests and EC50, an unambiguous statement of the con-
densate toxicity is upheld. It is very likely that the condensates con-
stitute an environmental risk, which eliminates them from direct use as
an anaerobic digestion substrate or fertiliser without prior detoxifica-
tion.
3.4. Limitations of the study
As with the majority of studies, the design of the current study is
subject to limitations. There are two major limitations in this study that
could be addressed in future research, and the third one identifies the
need for further development in the area of study.
The first is the lack of gas flow measurement, which did not allow
calculating the mass balance for the process. However, it does not have
any impact on the process itself because the leaking of the experiment
set-up was controlled on-line by monitoring the oxygen content in the
torgas. Despite that, in further studies, a gas flow meter should be in-
stalled in the experimental set-up to allow us to fully evaluate the
process performance.
The second limitation concerns the GC-MS analysis, which resulted
in a relatively high content of unknown compounds (unidentifiable
hydrocarbons) in the condensates at the torrefaction temperature of
240 °C. In further studies, the initial fractionation (separation) of the
compounds in the samples should be performed to reduce the number
The analysis of the torrefaction condensable volatile (condensate)
toxicological effects has been performed as a preliminary assessment for
their further utilisation, aiming at their utilisation as an anaerobic di-
gestion substrate. Special emphasis has been put on the phenol com-
pounds recognised as playing the main role in the toxicity of the con-
densates.
The higher the temperature, the more differentiated the composi-
tion of the condensates. In the analysed range of the temperature, acids,
aldehydes and ketones dominate.
No compounds from the alcohol, ketone, pyridine and benzene
derivative groups, considered to be toxic for anaerobic bacteria, were
detected in the analysed samples. However, long-chain fatty acids (in-
hibitors of the anaerobic digestion process) were detected in all sam-
ples.
The detected phenolic compounds are the result of hemicellulose
(guiacol and guiacol-derived compounds) and lignin (other phenols,
such as 4-ethylphenol) decomposition. The yield of phenols increases at
higher temperature (320 °C), as the decomposition of lignin plays a
major role in their formation.
There is a discrepancy between the toxicity classification used
within the toxicity assays and the EC50 values. Despite that, the ana-
lysed condensates, regardless of the torrefaction temperature, con-
stitute an environmental risk and therefore can be considered as toxic.
Their toxicity is the result of a synergistic effect of the compounds in the
condensates. Consequently, the assessment of the condensate's toxicity
only on the basis of the furans and phenols contents is unlikely to be
accurate.
The likelihood of excluding the condensates' utilisation as an

Table 2
The results of the GC-MS analysis (relative peak area distribution -%area); group abbreviation: Fu – furans, Ph – phenols, Pyr – pyridines, Es – esters, Alc – alcohols,
Ad – aldehydes, K – ketones, Ac – acids, A – alkanes, Oth – other heterocyclic compounds, Ben – benzene derivatives.
No. Group Compound (IUPAC name) Condensate (torrefaction temperature)/area%

320 °C 300 °C 280 °C 260 °C 240 °C

1 Ad CH3CHO Acetaldehyde 2.22 1.37 2.17 2.14 2.11

2 A CH3Cl Chloromethane 0.05
3 Alc CH4O (CH3OH) Methanol 11.09 6.23 7.70 8.51 7.88
4 Es C2H4O2 (HCOOCH3) Methyl formate 0.05 0.05 0.03
5 Ac CH3COOH Acetic acid 24.92 24.90 25.79 17.62
6.74 5.84
7 K C3H6O2 (CH3C(O)CH2OH) 1-Hydroxypropan-2-one 15.62 11.08 9.76 10.18 6.81
8 Es C3H6O2 (CH3COOCH3) Methyl acetate 8.87 4.98 7.69 6.76 6.07
9 Es C3H6O3 Methyl 2-hydroxyacetate 0.42 0.42 0.21 0.21 0.07
10 Ad C3H6O (CH3CH2CHO) Propanal 0.62 0.40 0.65 0.61 0.46
11 Ac CH3CH2COOH Propanoic acid 4.44 2.91 3.04 3.16 1.87
12 Alc C3H8O ((CH3)2CHOH) Propan-2-ol 0.98
13 K C3H6O (CH3COCH3) Propan-2-one 2.90 2.33 2.85 2.73 2.50
14 Ad C4H8O (CH3CH2CH2CHO) Butanal 0.03
15 Ac C4H8O2 (CH3CH2CH2COOH) Butanoic acid 1.01 0.75 0.59 0.47 0.26
16 K C4H6O2 (CH3COCOCH3) Butane-2,3-dione 7.65 4.92 6.63
17 Ac C4H6O2 But-2-enoic acid 0.03
18 K C4H8O (CH3COCH2CH3) Butan-2-one 2.39 1.54 2.22 1.59
19 K C4H8O2 1-Hydroxybutan-2-one 5.86 4.26 4.17 4.62 3.02
20 K C4H8O2 (CH3CH(OH)C(O)CH3) 3-Hydroxybutan-2-one 1.25 0.96 1.02 1.06 0.56
21 Es C4H3O3 Methyl 2-hydroxypropanoate 0.85 0.70 0.58 0.58 0.32
22 Es C4H8O2 (C2H5COOCH3) Methyl propanoate 1.18 2.20
0.57 0.42 0.29
23 Fu C4H8O ((CH2)3CH2O) Oxolane 0.06

8
K. Jagodzińska, et al. Biomass and Bioenergy 129 (2019) 105335

Table 3
The results of the GC-MS analysis (relative peak area distribution -%area) (cont.); group abbreviation: Fu – furans, Ph – phenols, Pyr – pyridines, Es – esters, Alc –
alcohols, Ad – aldehydes, K – ketones, Ac – acids, A – alkanes, Oth – other heterocyclic compounds, Ben – benzene derivatives.
No. Group Compound (IUPAC name) Sample (temperature)/area%

320 °C 300 °C 280 °C 260 °C 240 °C

24 Fu C4H6O2 ((CH2)3CH2O) Oxolan-2-one 1.04 0.92 0.53 0.41 0.25

25 K C5H8O Cyclopentanone 0.13 0.06
26 K C5H6O2 Cyclopentane-1,2-dione 0.40 0.54 0.23 0.25 0.08
27 K C5H6O Cyclopent-2-en-1-one 1.21 0.70 0.54 0.47 0.28
28 Fu C4H3OCHO Furan-2-carbaldehyde 2.51 2.95 1.74
29 Fu C5H6O2 Furan-2-ylmethanol 4.22 3.31 2.74 3.10 2.03
30 Ad C5H10O 2-Methylbutanal 0.24 0.11 0.10
31 Ad C5H10O ((CH3)2CHCH2CHO) 3-Methylbutanal 0.22 0.18
32 Fu C5H10O2 2-Methyloxolan-2-ol 0.09 0.11
33 Ac C5H10O2 3-Methylbutanoic acid 0.07
34 Ad C5H10O Pentanal 1.12 0.95 0.35 0.32 0.68
35 Alc C5H12O (CH3CH2CHOHCH2CH3) Pentan-3-ol 0.04
36 Pyr C5H5N Pyridine 0.19 0.08
37 Pyr C5H5NO Pyridin-3-ol 0.43 0.35 0.22 0.20 0.33
38 Fu C6H6O2 1-(Furan-2-yl)ethanone 1.95 1.02 0.99 0.76 0.56
39 Fu C6H8O2 2,4-Dimethyl-2H-furan-5-one 0.03
40 A C6H8O2 2-Hydroxy-3-methylcyclopent-2-en-1-one 0.67 0.67 0.33 0.27 0.14
41 Oth C6H6O3 3-Hydroxy-2-methylpyran-4-one (maltol) 0.32 0.14 0.12 0.05
42 Fu C6H6O3 Methyl furan-2-carboxylate 0.38 0.29 0.30 0.14
43 Fu C6H6O3 Methyl furan-3-carboxylate 0.31
44 Es C6H12O3 Methyl 2-hydroxy-2-methylbutanoate 1.25 0.92 0.92 0.97 0.49
45 K C6H8O 2-Methylcyclopent-2-en-1-one 0.20 0.18 0.13 0.04
46 Fu C6H6O2 5-Methylfuran-2-carbaldehyde 0.12

Table 4
The results of the GC-MS analysis (relative peak area distribution -%area) (cont.); group abbreviation: Fu – furans, Ph – phenols, Pyr – pyridines, Es – esters, Alc –
alcohols, Ad – aldehydes, K – ketones, Ac – acids, A – alkanes, Oth – other heterocyclic compounds, Ben – benzene derivatives.
No. Group Compound (IUPAC name) Sample (temperature)/area%

320 °C 300 °C 280 °C 260 °C 240 °C

47 Ac C6H14O3 2-Methylpropanoyl 2-methylpropanoate 5.54

48 Pyr C6H7NO 3-Methoxypyridine 0.08
49 Ac C6H12O2 3-Methylpentanoic acid 0.04
50 Ph C6H5OH Phenol 1.17 0.94 0.81 0.71 0.44
51 Ac (CH3CH2CH2CO)2O Butanoic acid, anhydride 3.94 2.80 2.16 1.77 1.55
9.95 6.25 5.55 3.53
52 K C8H14O 4,5-Dimethylhex-4-en-3-one 0.32 0.26 0.30 0.14
53 Ph C8H10O3 2,6-Dimethoxyphenol (syringol) 1.50 1.16 1.11 0.96 0.83
54 Ph C8H10O 4-Ethylphenol 0.20
55 A C7H10O2 3-Ethyl-2-hydroxycyclopent-2-en-1-one 0.14 0.12 0.12
0.18 0.06
56 Fu C7H8O3 Furan-2-ylmethyl acetate 0.13 0.06
57 Ph C7H8O2 2-Methoxyphenol (guaiacol) 3.57 2.36 2.48 2.35 1.62
58 Ph C8H10O2 2-Methoxy-4-methylphenol (creosol) 0.12 0.08 0.03
59 Ph C9H12O2 4-Ethyl-2-methoxyphenol 0.82 0.57 0.67 0.62 0.44
60 Ph C9H10O2 4-Ethenyl-2-methoxyphenol 0.20 0.13 0.14
61 Ph C9H10O2 1-(4-Hydroxy-2-methylphenyl)ethanone 0.12
62 Ph C10H12O2 2-Methoxy-4-[(E)-prop-1-enyl]phenol (isoeugenol) 0.05
63 Ben C10H14O3 1,2,3-Trimethoxy-5-methylbenzene 0.09 0.07
64 Ac C16H30O3 2-Ethylhexanoyl 2-ethylhexanoate 0.06 0.05 0.04
65 K C10H12O3 1-(4-Hydroxy-3-methoxyphenyl)propan-2-one 0.30 0.32 0.22 0.23
66 Ac C16H32O2 n-Hexadecanoic acid 3.97
67 Ac C18H36O2 (CH3(CH2)16COOH) Octadecanoic acid 0.84

Table 5
The results of the GC-MS analysis (relative peak area distribution -%area) (cont.); group abbreviation: Fu – furans, Ph – phenols, Pyr – pyridines, Es – esters, Alc –
alcohols, Ad – aldehydes, K – ketones, Ac – acids, A – alkanes, Oth – other heterocyclic compounds, Ben – benzene derivatives.
No. Group Compound (IUPAC name) Sample (temperature)/area%

320 °C 300 °C 280 °C 260 °C 240 °C

68 Ac C18H32O2 Octadeca-9,12-dienoic acid 1.26

69 Ac C18H34O2 (Z)-Octadec-13-enoic acid 1.07 0.28 0.29

9
K. Jagodzińska, et al.
anaerobic digestion substrate is high, due to their high acute toxicity
and containing the toxicity or/and inhibitory characteristic for anae-
robic bacteria. Therefore, further studies following two paths shall be
considered: I – the evaluation of the possibility of the condensate de-
toxification and later utilisation as an anaerobic digestion substrate and
II – the evaluation of the condensates’ performance as pesticides.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.biombioe.2019.105335.
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