Research Article

pubs.acs.org/journal/ascecg

Profiles of Volatile Organic Compounds in Biochar: Insights into

Process Conditions and Quality Assessment
Michele Ghidotti,*,† Daniele Fabbri,† and Andreas Hornung‡
†
Interdepartmental Centre for Industrial Research “Energy and Environment” and CIRSA, University of Bologna, via S. Alberto 163,
I-48123 Ravenna, Italy
‡
Fraunhofer Institute for Environmental, Safety, and Energy Technology UMSICHT, Institute Branch Sulzbach-Rosenberg, An der
Maxhütte 1, 92237 Sulzbach-Rosenberg, Germany
*
S Supporting Information
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ABSTRACT: Sustainable application of biochar to soil requires

careful consideration of sorbed mobile compounds that can be
released into the environment and their relationship with bulk
Downloaded via NAGOYA UNIV on June 26, 2018 at 21:35:57 (UTC).

chemical properties. Seven biochars were produced by pyrolysis

of corn stalk from 350 to 650 °C, and residual volatile organic
compounds (VOCs) were investigated by head space solid-
phase microextraction and gas chromatography−mass spectrom-
etry. Over 80 compounds were detected in poorly carbonized
biochars, including thermal degradation products of lignin (2-
methoxyphenols), cellulose and hemicellulose (1,4:3,6-dianhy-
dro-β-D-glucopyranose, C1−C3 furans and furanones, C1−C2
cyclopentenones), lipids (aromatic and C2−C8 aliphatic acids),
and proteins (aromatic nitriles, amides). The presence of
potentially harmful compounds, such as benzene, toluene,
ethylbenzene, xylenes, phenols, volatile fatty acids, and polycyclic aromatic hydrocarbons, highlights the importance of
controlling the biochar production process. Statistically significant decreasing trends emerged between the quantity of all VOC
classes and the increasing carbonization degree estimated by the hydrogen to carbon (H/C) ratios and volatile matter content.
Biochars with H/C < 0.70 (pyrolysis temperature >400 °C) did not release VOCs at ambient temperatures (25, 50 °C). VOCs
fingerprinting can contribute to the evaluation of biochar quality. The samples with the highest levels of VOCs did not inhibit the
germination of cress seeds (40 g L−1 water suspensions) indicating that biochar contamination is not necessarily associated with
adverse effects.
KEYWORDS: Char, Biomass, Volatilome, Solid-phase microextraction, Solventless, Green analytical chemistry

■ INTRODUCTION
Biochar is the solid carbonaceous material produced by the
exert adverse effects on plants11−13 and microorganisms.14−16
Smith et al.14 evidenced that biochar water-soluble organic
pyrolysis of biomass for a variety of applications in the agro/ compounds resulted in toxic to freshwater blue-green algae.
environmental field.1 The wide range of feedstocks that can be Contaminated biochar showed phytotoxicity on cress seeds
thermally converted, including animal (poultry litter, residues (germination tests), while noncontaminated biochar produced
from anaerobic digestion) as well as vegetable based materials under the same conditions did not present any negative
(agricultural residues, energy crops), and the different effects.12 Biochar labile substances can have a priming effect on
technologies currently under optimization for biochar produc- soil biota17 and the potential to influence the fate of soil organic
tion highly influence its physical and chemical properties.2,3 matter18 and pyrogenic black carbon cycle.19 Moreover, if large
The increasing interest in finding suitable biochar applications amounts of biochar are produced for soil application, the
(e.g., soil amendment, greenhouse gas mitigation, feed additive, presence of harmful compounds, such as monoaromatic
new materials, remediation of polluted areas)4,5 led to a hydrocarbons (benzene, toluene, ethylbenzene, xylenes:
comprehensive investigation on its chemical characteristics to BTEX), polyaromatic hydrocarbons (PAHs), and heavy metals,
determine its quality prior to large scale use.6,7 Standardization has to be monitored for health and safety concerns during its
of analytical methods for biochar testing is under investigation handling and storage and to prevent impacts on plants11,15,20 or
with conventional and nonconventional techniques, and other organisms.21 Spokas et al.22 qualitatively investigated
standard parameters for its quality/safety were proposed.8−10
During pyrolysis condensable gases could be retained onto the Received: August 5, 2016
biochar porous structure, and these compounds could have a Revised: October 25, 2016
certain degree of mobility. Their release in air or water could Published: October 28, 2016

© 2016 American Chemical Society 510 DOI: 10.1021/acssuschemeng.6b01869

ACS Sustainable Chem. Eng. 2017, 5, 510−517
ACS Sustainable Chemistry & Engineering Research Article

volatile organic compounds (VOCs) released by 77 biochars 1000 mL/min nitrogen flow. During pyrolysis the actual temperature
produced from different processes and different temperatures in the reactor was measured with a thermocouple. For each pyrolysis
with traditional head space gas chromatography−mass batch about 15 g of biomass was processed. The char produced was
spectrometry (HS)-GC-MS instrumentation. Differences in allowed to cool in the reactor under nitrogen flow, collected, and, after
homogenization, stored in the freezer. The syntheses of biochar were
the amounts of VOCs (total ion current) from similar performed in triplicate, with relative standard deviation (RSD) of the
feedstocks (oak hardwood), pyrolysis units, and temperatures yields for each pyrolysis condition less than 2%. Biochar samples
were found as well as VOCs profiles of corn stover biochar obtained at a given pyrolysis temperature XXX °C were grouped,
produced at similar conditions but from different units. The top homogenized, and stored in closed vials at −25 °C before analysis; the
ten most frequently observed compounds were acetone, resulting sample was named as CSXXX.
benzene, methylethyl ketone, toluene, methyl acetate, propanal, Biochar Characterization. Elemental analysis of biochar samples
octanal, 2,3-butadiene, pentanal, and 3-methyl butanal.22 The was performed with a Thermo Scientific FLASH 2000 Series CHNS/
overall trend associated with an increase in pyrolysis temper- O Elemental Analyzer. TGA of thermosequence biochar samples was
ature within the same unit was a net decrease in total sorbed performed with a Mettler Toledo TGA/DSC. Between 5 and 10 mg of
biochar were placed in alumina pans. TGA analyses were performed
VOCs with an increasing proportion of aromatic compounds. with nitrogen purge gas (50 mL/min) and the following temperature
Buss et al.12 studied softwood biochar produced at 550 °C that program: 25 °C for 2 min, 25−110 °C at 25 °C/min, 110 °C for 10
were contaminated with pyrolysis gases during process min (segment A); 110−900 °C at 25 °C/min, 900 °C for 10 min
operation. Even after 4 weeks of storage, contaminated biochar (segment B); 900 °C for 20 min in air at 50 mL/min (segment C). A
released a small quantity of vapors inhibiting germination, but blank curve of an empty pan was acquired for baseline correction
the chemical nature of the contamination was only hypothe- during the evaluation of the biochar samples. Proximate analysis was
sized. Further studies led Buss et al.20 to conclude that VOCs conducted from the weight loss curve of each sample. Moisture
posed a greater concern for plant growth than PAHs. EBC content was calculated from the weight loss during segment A, while
guidelines for biochar quality indicate that the VOCs are very the volatile matter (VM) and fixed carbon (FC) from segments B and
C, respectively. The ash content was calculated from the residual
important for the determination of biochar quality, but no weight after fixed carbon oxidation (segment C). Analyses were
quantitative information or thresholds was given.8 The report performed in triplicate. Data were normalized by sample weight and
cites the qualitative study conducted by Spokas et al.22 and expressed in % dry basis.
concluded proposing the assessment of total VOCs by HS-SPME Procedure. One gram of biochar was exactly weighed in
thermogravimetric analysis (TGA). IBI proposed the same 20 mL HS vials and spiked with 1 μL (weighed at ±0.01 mg) of
determination of VOCs as advanced analysis optional for methanol containing o-eugenol as surrogate pyrolysis product (1.00
biochar quality.9 Solid phase microextraction (SPME) is a mg/mL). Sealed vials were placed on a heating plate at 150 °C where
powerful solventless technique for the analysis of trace only the bottom part containing biochar was in contact with the
components in complex matrices by GC-MS, that integrates heated surface. The Car-PDMS fiber was placed in the HS where the
temperature was about 40 °C. Temperatures were constantly
several analytical steps (sampling, extraction, preconcentration,
measured by means of a PSC-MS Plus Portable Hand-held infrared
and sample introduction for instrumental analysis).23 The thermometer. The exposure time was fixed at 30 min according to
potential of SPME for the analysis of mobile organic Becker et al.25 and Spokas et al.22 Preliminary experiments during
compounds was described in the characterization of poultry method development showed that Car-PDMS fiber gave a better
litter biochar where the technique enabled the detection of alkyl performance in terms of signal intensity compared to polyacrylate and
phenols, small hydrocarbons, alkyl aromatics, small PAHs, and polyethylene glycol SPME fibers; increasing the exposure time more
nitrogen containing compounds.11 However, the effect of than 30 min did not significantly increase the GC signal. The HS-
biochar characteristics on the qualitative and quantitative SPME procedure was also applied to calibration solutions and CS
distribution of VOCs determined by HS-SPME has not been biochar samples heated at different temperatures (25, 50, 100, 150 °C)
during sampling.
investigated yet. In this study, a method based on HS-SPME-
GC-MS Conditions. After fiber exposure, the Car-PDMS was
GC-MS was developed in order to understand the pattern of inserted into the split/splitless injector of an Agilent 5977 gas
VOCs retained or formed in biochar during pyrolysis of chromatograph equipped with a straight SPME liner. Analytes were
biomass and how they relate to process conditions and biochar thermally desorbed at 250 °C for 10 min, and separation was
bulk properties. The method was tested on seven biochars performed with a DB-FFAP polar column (30 m length, 0.25 mm i.d,
obtained from the pyrolysis of a typical lignocellulosic biomass, 0.25 μm film thickness). The starting GC oven temperature was set to
corn stalk, at increasing pyrolysis temperatures (350−650 °C). 36 °C (5 min) and increased to 250 °C (10 °C/min). Detection was
The purpose of this study was the detailed characterization of made with a quadrupole mass spectrometer Agilent 7820A operating
the mobile organic compounds that could be volatilized from under electron ionization at 70 eV with acquisition at 1 scan/s in the
biochar, potentially affecting its environmental performance, m/z 29 and 450 range. Mass spectra were acquired in full scan mode
properly adjusting the electron multiplier voltage. Identification was
and the correlation of the VOCs species with biochar based on library mass spectra matching (NIST) and literature data.
carbonization degree. Second, the potential of HS-SPME data Quantification was made from the peak area integrated by extracting
for the evaluation of biochar quality for sustainable applications characteristic ions from total ion current.
was discussed. Quantification and Statistical Analysis. The quantity of each

■
analyte released by biochar and captured by the SPME fiber in the HS
MATERIALS AND METHODS of test vials (20 mL) was expressed in terms of normalized peak area
NA. NA was calculated from the peak areas of the analyte (Aanalyte) and
Chemicals. 2-Allyl-6-methoxy phenol (o-eugenol) and methanol the internal standard (Ais), the quantity of added internal standard
were purchased from Sigma-Aldrich. SPME fiber holder and (μgis of methanol), and the analyzed biochar using the following eq
Carboxen-polydimethylsiloxane (Car-PDMS) fiber were purchased (eq 1):
by Supelco.
Biochars. Pelletized corn stalks were pyrolyzed in a bench-scale A analyte μg is
horizontal quartz reactor24 at different temperatures (350, 400, 450, NA =
A is g biochar
500, 550, 600, and 650 °C) with fixed residence time of 20 min and (1)

511 DOI: 10.1021/acssuschemeng.6b01869

ACS Sustainable Chem. Eng. 2017, 5, 510−517
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Table 1. Elemental Composition (% d.w.) and Atomic Molar Ratios of Corn Stalk (CS) Biochar Samplesa
biochars N RSD C RSD H RSD O H/C O/C C/N
CS350 1.2 2.1 55 0.43 3.7 1.2 13 0.80 0.17 56
CS400 1.0 2.9 54 1.1 3.2 1.2 9.6 0.71 0.13 61
CS450 1.0 2.2 56 1.3 2.7 0.2 7.1 0.59 0.095 63
CS500 0.92 3.6 56 1.7 2.3 5.4 5.5 0.49 0.074 70
CS550 0.87 5.3 55 5.5 2.0 6.3 5.6 0.44 0.078 73
CS600 0.84 5.0 55 2.2 1.6 1.6 3.9 0.36 0.053 77
CS650 0.69 12 54 7.0 1.4 9.0 5.1 0.32 0.071 91
a
Mean values and %RSD (n = 3). Oxygen content by difference.

This approach was considered adequate for the purposes of this temperature with enhanced elimination of volatile compounds
study intended to compare the relative behavior of different biochar and polycondensation, aromatization, and defunctionalization
samples produced from the same feedstock. The linearity of the HS- of the carbonaceous matrix.27−30 H/C and O/C atomic molar
SPME method was tested on o-eugenol. Ordinary least-squares
ratios were proposed as an index of biochar carbonization
regression computed on the peak area of o-eugenol in the calibration
range of 108−0.108 ng (12 data points) resulted in the following linear degree or its degree of aromaticity.31 H/C values were
model (y = ax + b): y = 4.43E06x − 4.56E06, where x and y are the preferred in this study given that O/C values may not be
amount of internal standard and its peak area, respectively. 95% adequate for biochars with high ash content.2 The trend of H/
confidence intervals for a and b were [4.34E06;5.55E06] and C was demonstrated to be statistically significant with the
[9.42E06;8.38E05], respectively, while the standard errors were Jonckheere-Terpstra statistics (P < 0.01). FC increased with the
5.43E04 and 2.94E06. R2 and Pearson correlation coefficient (r) decreasing H/C of the biochars, with correlation coefficients of
were both 0.999. Average S/N values for 0.1 ng level was 50 (n = 3, 4% 0.83 (P < 0.05) indicating a good correlation between different
RSD) indicating that under the selected conditions VOCs at the subng parameters representative of the carbonization degree, while the
level could be detected in the HS of biochar. All the analyses were
conducted in triplicate; data were reported as mean values ±1 standard VM progressively decreased with the decreasing H/C (r = 0.97,
deviation (SD) or % relative standard deviation (RSD). Blanks were P < 0.01).
performed to ascertain the absence of cross-contamination. The RSD Qualitative Analysis: Biochar Volatilome. Thermose-
of methanol peak area (Ais) from triplicate analyses of each biochar quence biochars evolved a variety of organic compounds in the
was <10%. Ordinary least-squares regression was computed with the HS that were detected by SPME GC-MS. A typical chromato-
software PAST (Paleontological Statistic vers. 2.16); while Pearson gram obtained from the HS-SPME of the biochar sample
product moment correlation coefficients (r, with P level of CS350 (H/C 0.80) is presented in Figure 1. In total 88
significance) were calculated with the software SigmaPlot vers.12.0. compounds were tentatively identified belonging to several
Kruskal−Wallis, and Jonckheere-Terpstra statistics were performed
with the NSM3 package of R according to Hollander et al.26
compounds classes (Tables S1 and S2). The initial part of the
Germination Tests. Seed germination tests on cress (Lepidium chromatogram presented an intense and poorly resolved
sativum L.) were conducted with CS350 and CS400 biochars in water sequence of peaks formed by volatile compounds, principally
suspensions at 40 g/L (4 replicates) according to Rombolà et al.11 C3−C4 oxygenated compounds, for example propanaldehyde,

■
butanaldehyde, butan-2-one, methyl acetate. Some of these
RESULTS AND DISCUSSION compounds were also detected in previous studies with
different biochars.11,22,32,33 Blank analyses confirmed that
Biochar Characteristics. The elemental composition of these compounds were not present in reagents and glassware
biochar samples produced in this study is reported in Table 1.
utilized in the analytical procedure; however, it cannot be
The hydrogen and oxygen content decreased with increasing
excluded that biochar might adsorb volatile compounds from
pyrolysis temperature, and accordingly the values of H/C and
the ambient air and release them under HS conditions even
O/C atomic molar ratios decreased (from 0.80 to 0.32 and
though precautions were made to limit contact with air. The
from 0.17 to 0.07 from 350 to 650 °C, respectively). The
attention in this study was focused to C≥5 compounds that
content of nitrogen also decreased with increasing pyrolysis
eluted later in the chromatogram and were structurally related
temperature. Proximate analysis of biochar samples is reported
to the original biopolymers composing the original plant
in Table 2. The FC and ash content tended to increase with the
biomass or indicative of their charring intensity (Figure 1).
pyrolysis temperature while the VM decreased. These trends
Typical thermal degradation products of lignin (2-methox-
were typically observed in thermosequence biochars due to the
yphenol, i.e. guaiacol, and its alkylated derivatives) and
more severe thermal decomposition of biopolymers at higher
holocellulose (e.g., 1,4:3,6-dianhydro-β-D-glucopyranose, C1−
C3 furans and furanones, C1−C2 cyclopentenones and
Table 2. Proximate Analysis of Corn Stalk Thermosequencea
pyranones) could be identified in CS350 (Figure
biochars VM %RSD FC %RSD ash %RSD 1).31,34,35Aromatic (benzoic and benzeneacetic) and short
CS350 33 1.4 43 1.0 24 3.6 chain (up to C8) aliphatic acids principally in the form of
CS400 26 0.67 45 2.1 28 3.8 methyl esters were identified. Apparently, methylation of
CS450 21 2.3 49 1.2 30 2.9 carboxylic groups could take place during sampling. Lipids
CS500 20 0.46 49 3.3 31 4.9 could be the source of these acids. These compounds were
CS550 18 3.0 50 2.6 32 4.5 detected in HS and aqueous extracts of biochar from poultry
CS600 16 4.3 50 0.87 34 2.0 litter where they could play a role in the inhibition to plant seed
CS650 15 2.9 51 1.7 35 3.2 germination.11Aromatic compounds not directly related to the
structure of original biomolecules but indicative of their
a
Data are reported as % on dry basis with %RSD (n = 3). carbonization were detected in almost all biochar samples.
512 DOI: 10.1021/acssuschemeng.6b01869
ACS Sustainable Chem. Eng. 2017, 5, 510−517
ACS Sustainable Chemistry & Engineering Research Article

Figure 1. Total ion current chromatogram from HS-SPME-GC-MS analysis of corn stalk biochar produced at 350 °C. The pattern of the most
relevant VOCs was reported in the expanded chromatogram between 10 and 22 min.

These compounds included monoaromatic (benzenes, biphen- biochars under fixed conditions rather than absolute concen-
yls, indanes) and polycyclic aromatic hydrocarbons (PAHs), trations. The aim was to evaluate the dependence of emitted
benzonitrile, and benzofurans.31,34 Benzene, toluene, C2- VOCs on the carbonization degree of biochars produced with
benzenes, naphthalene, benzonitrile, and benzofurans were the same feedstock and pyrolysis apparatus. Pearson product-
released from all the samples including the highly carbonized moment correlation coefficient (r) showed statistically
biochars of the thermosequence (CS600 and CS650). significant (P < 0.05) correlation (r = 0.95) of VOCs vs H/C
Interestingly, these aromatics compounds were proposed as trend. Similarly, total VOCs and VM were strongly correlated
molecular indicators of charring in analytical pyrolysis (Figure 2, r > 0.9, P < 0.05). The strong correlation with
studies.31,34,35The ratio of alkylated/nonalkylated analogues indexes of the degree of charring and aromaticity (H/C, VM)
(e.g., benzene/toluene, naphthalene/methylnaphthalene) was indicated that highly carbonized biochars should be produced
found to decrease with decreasing H/C ratios. Similarly, the in order to reduce the risk of VOCs emission. Notably, the
degree of alkylation of VOCs released by biochars tended to molecular pattern of the volatilome of biochars produced at
diminish with charring intensity. While C1−C2 benzenes were different temperatures was different. This was evidenced in
observed in all thermosequence biochars, C3, C4, and C5
benzenes were not detected for biochar with H/C lower than
0.44, 0.49, and 0.7, respectively. Alkyl substituted benzenes are
well-known harmful compounds,36 and their presence in
biochar could pose direct issues on its safety during handling
and storage. The number of products detected by GC-MS after
HS-SPME decreased with an increasing charring degree
expressed by the H/C ratio of biochars, from 88 in CS350 to
15 in CS650. For instance, the large group of phenols (phenol,
methyl phenols, and C2−C4 phenols) and guaiacols (guaiacol
and its C1−C2 derivatives) released from CS350 was restricted
to only phenol, 4-methylphenol, guaiacol, and 4-methylguaiacol
in biochar with a higher carbonization degree. For the purpose
of investigating the relationship between the degree of charring
and the presence of mobile compounds, a quantitative
approach was applied and discussed in the next section.
Relationship with Biochar Properties. The quantity of
VOCs, expressed as normalized areas (NA), was reported in Figure 2. Correlation between the normalized area (NA) of VOCs
Tables S1 and S2. These values were meant to estimate the (HS-SPME-GC-MS) and the VM measured by TGA of cornstalk
magnitude of VOCs that could be released in air from different biochars. Mean values and SD from three replicates.

513 DOI: 10.1021/acssuschemeng.6b01869

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Figure 3. Box plots of the normalized areas (NA) of major (A) and minor (B) VOCs compound classes vs H/C of corn stalk biochars and pyrolysis
temperature. The tops and bottoms of each “box” reported the 25th and 75th percentiles of the samples, respectively, while the whiskers were drawn
from the ends of the interquartile ranges to the furthest observations within the whisker length.

Figure 3 showing the quantity of the different chemical families with H/C of 0.49 and 0.44. In this range of temperature there
as a function of H/C values, for the most abundant (Figure 3A) could be a cyclic rearrangement of their smaller linear
and less abundant (Figure 3B) compounds. Aldehydes and precursors. Aromatic aldehydes like furaldehyde and benzalde-
ketones (mostly benzaldehydes and furaldehydes) were the hyde were identified in all thermosequence biochars. Cyclo-
most abundant family in weakly charred biochars (around pentenones, lactones, and alkyl and aryl furans are representa-
30%), but their quantity decreased sharply with decreasing H/ tives of thermal degradation of holocellulose.24,31 Their signal
C becoming negligible in biochars with H/C < 0.59. Aromatics was strongly suppressed in biochars with H/C < 0.49. C1−C3
(principally benzene, toluene, and C2-benzenes) and phenols cyclopentenones were not found at H/C lower than 0.59.
were the principal class of VOCs in all the biochars. Their Volatile aldehydes and ketones could also originate from
contributions to total VOCs of slightly carbonized biochar were pyrolysis of holocellulose.34 C3−C4 alkyl aldehydes and
20 and 14%, respectively. In all other corn stalk biochars (H/C substituted derivatives of benzaldehyde were detected only in
0.71−0.32) aromatics were the most abundant compounds. biochars with H/C < 0.59. Incomplete degradation of cellulose
Interestingly, aliphatic as well as aromatic (benzoic acid) acids at low pyrolysis temperature (0.80 < H/C < 0.59) could be
represented a significant class of compounds featuring biochar evidenced by the presence of 1,4:3,6-dianhydro-β-D-glucopyr-
volatilomes (25% for CS350). These compounds were detected anose. The Kruskal−Wallis test was applied to determine
principally as methyl ester derivatives probably from biochar- differences of VOCs concentrations in biochars with increasing
catalyzed methylation. Traces of cyclic ketones like cyclo- carbonization degree. Results evidenced statistically significant
pentanone and cyclohexanone were detected only in biochars differences (1% level of significance) on the medians of all
514 DOI: 10.1021/acssuschemeng.6b01869
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VOCs compound classes except alkyl amides. The level of

significance of alcohols was 5%. The Jonckheere-Terpstra
statistic was also performed to test the alternative hypothesis of
an increasing trend in the medians of VOCs with the increasing
H/C. The outcome evidenced statistically significant differ-
ences (1% level of significance) for all compound classes. These
results were in accordance with those of Pearson product-
moment correlation coefficients and confirmed the relevant
effect of the carbonization degree on the volatiles released by
biochar. Quantitative analysis highlighted differences in VOCs
relative abundance (Tables S1 and S2), but all corn stalk
biochars had toluene, acetic acid methyl ester, and phenol
among the most abundant compounds. The presence of
aromatic compounds, volatile fatty acids, and phenols in
biochar could be therefore a crucial marker for its safety and
quality for environmental applications. The %RSD calculated
on total VOCs concentrations in triplicate analysis were 17, 18,
27, 23, 31, 34, and 14% for corn stalk biochars with H/C of Figure 4. Mass chromatograms at m/z 122 from cornstalk biochar
0.80, 0.71, 0.59, 0.49, 0.44, 0.36, and 0.32, respectively. (CS350) heated at different temperatures (25, 50, 100, and 150 °C)
Considering the complexity of the matrix and the number of during HS-SPME.
compound identified, %RSD values were acceptable and
demonstrated the suitability of the HS-SPME method for the Evaluation of the HS-SPME-GC-MS Method for
analysis of VOCs in biochar. A rough estimation of the Biochar Quality Assessment. The presence of trace VOCs
concentrations could be accomplished by utilizing for all the in biochar was investigated with a green analytical method
compounds the response factor of the surrogate pyrolysis based on SPME. SPME application to biochar was seldom
product o-eugenol. VOCs concentrations progressively de- reported.32,33 Clough et al. applied the technique using DVB/
creased with the increasing carbonization degree from about 6 CAR/PDMS fiber exposed at 40 °C for 40 min, but only α,β-
to 0.09 μg/gbiochar. These values are within the range pinene and acetaldehyde were identified.33 Higashikawa et al.
conservatively estimated in biochars (pg-μg/gbiochar) through selected DVB/CAR/PDMS fiber (20 °C and 20 min fiber
direct HS-GC-MS analysis and could be sufficient to affect the exposure) to quantitatively detect model VOCs in complex
soil microbiome.22 environmental matrices and showed that the biochar-matrix
VOCs Emissions at Ambient Temperatures. The effect reduced method performance due to high affinity for the spiked
of biochar temperature on the pattern of evolved compounds compounds.32 In the present study, several compound classes
detectable by HS-SPME was investigated at 25, 50, 100 °C (the with different polarities and representative of biomass
results at 150 °C were described in the previous section). The thermochemical degradation products were detected, corrobo-
lowest value was chosen in order to verify if biochar could rating the preliminary results obtained in a previous work.11
release volatile compounds at ambient temperature, while 50 More recently, it was shown that the composition of pyrolysis
°C approximated a possible condition achieved in terrestrial vapors provided by SPME with Car-PDMS fiber was similar to
soils during warm periods. The value of 100 °C was tested by that of the bio-oil analyzed by direct GC-MS.24 This similarity
Becker et al.25 As expected, temperature greatly affected the confirms the suitability of the Car-PDMS fiber for the detection
pattern and intensity of GC traces. As an example, the mass of biomass pyrolysis products. The ability of the methods to
chromatograms relative to the ions m/z 122 in the elution detect molecular markers of feedstock and carbonization could
region of interest indicative of alkyl aromatics, alkyl aldehydes, allow the control of the occurrence of biochar contamination
and lignin phenols are shown in Figure 4 for different from vapor recondensation during pyrolysis.14,37 The potential
temperatures. GC peaks were barely detected at 25 and 50 release of these compounds in air or pore water can affect
°C; they could be revealed at 100 °C and became intense at biochar performance in soils and its sustainability. It was shown
150 °C. This latter temperature was selected in the procedure. that VOCs and water-soluble organic compounds in biochar
Concerning the possibility of VOCs emission at ambient can affect soil and aquatic micro-organism communities.14,16,38
temperatures, quantitative results (Table S3) showed that To the end of assessing the potential inhibitory effects of
VOCs could be detected only in CS350 and CS400 biochars biochars with the highest levels of VOCs, germination tests on
with low carbonization degree (H/C 0.80 and 0.71). The most cress seeds were performed on samples CS350 and CS400. The
abundant compounds were aldehydes like propanal, furfural, average germination rate of CS350 and CS400 (96 ± 2% for
benzaldehyde, and formic and acetic acids. The possible both biochars) was similar to that of the control (97 ± 1%).
correlation of such compound classes, especially organic acids These results were consistent with a previous study on similar
and phenols with the environmental performance of biochar, biochars,11 indicating that a high VOC content is not
was highlighted,11,12and their presence could be a useful proxy necessarily associated with observable toxicity, at least on the
to discriminate biochar quality. Biochars with H/C < 0.71 did germination of cress seeds. However, the importance of mobile
not exhibit detectable compounds in HS at 25 and 50 °C. The organic compounds in biochar quality assessment emerges
threshold value of 0.70 for H/C was considered as a quality considering the similarity between some VOCs molecules
parameter for biochar.8,9 Similarly, the results of this study presented in this study and volatile WSOC that showed toxicity
suggest that sufficiently carbonized biochars (H/C < 0.70) on aquatic organisms.14 The composition and quantity of
obtainable at relatively high pyrolysis temperatures (>400 °C) biochar VOCs was dependent on chemical characteristics, as
are not prone to evolve VOCs at normal conditions. VOCs decreased with increasing carbonization degrees, while
515 DOI: 10.1021/acssuschemeng.6b01869
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the molecular pattern shifted from the prevalence of oxy- (6) Singh, B.; Singh, B. P.; Cowie, A. L. Characterisation and
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(11) Rombolà, A. G.; Marisi, G.; Torri, C.; Fabbri, D.; Buscaroli, A.;
Ghidotti, M.; Hornung, A. Relationships between Chemical Character-
ASSOCIATED CONTENT istics and Phytotoxicity of Biochar from Poultry Litter Pyrolysis. J.
* Supporting Information
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The Supporting Information is available free of charge on the (12) Buss, W.; Mašek, O. Mobile organic compounds in biochar - A
ACS Publications website at DOI: 10.1021/acssusche- potential source ofcontamination - Phytotoxic effects on cress seed
(Lepidiumsativum) germination. J. Environ. Manage. 2014, 137, 111−
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chemistry and growth of Koeleria macrantha in the ponderosa pine/
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AUTHOR INFORMATION (14) Smith, C. R.; Hatcher, P. G.; Kumar, S.; Lee, J. W. Investigation
Corresponding Author into the Sources of Biochar Water-Soluble Organic Compounds and
Their Potential Toxicity on Aquatic Microorganisms. ACS Sustainable
*Phone: +39 0544 937344. E-mail: michele.ghidotti2@unibo.it.
Chem. Eng. 2016, 4 (5), 2550−2558.
Notes (15) Kołtowski, M.; Oleszczuk, P. Toxicity of biochars after
The authors declare no competing financial interest. polycyclic aromatic hydrocarbons removal by thermal treatment.

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Ecol. Eng. 2015, 75, 79−85.
ACKNOWLEDGMENTS (16) Smith, C. R.; Buzan, E. M.; Lee, J. W. Potential impact of
biochar water-extractable substances on environmental sustainability.
This study was performed within the collaboration agreement ACS Sustainable Chem. Eng. 2013, 1 (1), 118−126.
between the University of Bologna and Fraunhofer Institute for (17) Zimmerman, A. R.; Gao, B.; Ahn, M. Y. Positive and negative
Environmental, Safety and Energy Technology (UMSICHT), carbon mineralization priming effects among a variety of biochar-
Germany. We would like to thank Dr. Ondřej Mašek of the UK amended soils. Soil Biol. Biochem. 2011, 43 (6), 1169−1179.
Biochar Research Centre (UKBRC), University of Edinburgh, (18) Rombolà, A. G.; Meredith, W.; Snape, C. E.; Baronti, S.;
for the use of thermogravimetric analyser. Genesio, L.; Vaccari, F. P.; Miglietta, F.; Fabbri, D. Fate of Soil

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Organic Carbon and Polycyclic Aromatic Hydrocarbons in a Vineyard
Soil Treated with Biochar. Environ. Sci. Technol. 2015, 49 (18),
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