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Determination of Lignin, Cellulose, and Hemicellulose in Plant Materials by FTIR

Spectroscopy

Article in Journal of Analytical Chemistry · June 2023

DOI: 10.1134/S1061934823040093

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ISSN 1061-9348, Journal of Analytical Chemistry, 2023, Vol. 78, No. 6, pp. 718–727. © Pleiades Publishing, Ltd., 2023.
Russian Text © The Author(s), 2023, published in Zhurnal Analiticheskoi Khimii, 2023, Vol. 78, No. 6, pp. 496–506.

ARTICLES

Determination of Lignin, Cellulose, and Hemicellulose

in Plant Materials by FTIR Spectroscopy
S. G. Kostryukova, *, H. B. Matyakubova, Yu. Yu. Masterovaa, A. Sh. Kozlova, M. K. Pryanichnikovaa,
A. A. Pynenkova, and N. A. Khluchinaa
a National Research Mordovian State University,
Saransk, 430005 Russia
*e-mail: [email protected]
Received March 9, 2022; revised November 6, 2022; accepted November 10, 2022

Abstract—A procedure for determining concentrations of lignin, cellulose, and hemicellulose in plant mate-
rials using Fourier-transform IR spectroscopy in the middle spectral region was developed and tested. The
procedure is based on the use of calibration functions reflecting the dependence of the intensity of analytical
absorption bands on the concentration of lignin (1512 cm–1) and cellulose (1450 cm–1) in model samples; for
hemicellulose, indirect correlations were used. The model samples were ternary mixtures consisting of lignin,
bacterial cellulose, and hemicellulose in various proportions. The proposed method was tested on a wide
range of plant biomass samples; it demonstrated adequate precision (RSD no more than 4%). The accuracy
of the procedure for determining the main components of plant biomass (lignin, cellulose, and hemicellu-
lose) was demonstrated using the standard addition method.

Keywords: Fourier-transform IR spectroscopy, absorption band, plant biomass, lignin, cellulose, hemicellu-
lose
DOI: 10.1134/S1061934823040093

Plant wastes possess a unique potential for the pro- the condensation and precipitation of lignin
duction of renewable energy and valuable chemicals during the cooking of sulfate pulp [11, 12]. As Fourier-
and in the nearest future can contribute to solving transform IR (FTIR) spectroscopy is characterized by
problems associated with the use of traditional fossil rapidity and ease of sample preparation and does
fuels. The development and implementation of tech- not require large amount of test samples, it was suc-
nologies for the chemical and biotechnological pro- cessfully used in the analysis of archaeological
cessing of plant biomass into biofuels and chemicals is wood [13–15]. Infrared spectra help to distinguish
currently an urgent task. In this context, data on the wood species [16] and to determine the place of their
initial composition of plant biomass is critical for pre- growth [17].
dicting the efficiency of any processing method. Most Interest in this topic in other countries is currently
“wet” analytical methods for the determination of cel- rather high; for example, review [18] summarizes the
lulose, hemicellulose, and lignin are based on their advances in using IR spectroscopy to study plant bio-
separation, followed by isolation [1, 2]. However, mass. Three methods of Fourier-transform IR spec-
these methods are destructive and laborious, require troscopy (attenuated total reflection (ATR), diffuse
significant amounts of materials, generate a large reflecttion, and transmission) were compared in [19].
amount of chemical wastes, and do not always give In recent years, the use of near-infrared spectroscopy
reliable results [1–4]. It is desirable to create simple (NIRS) for the qualitative and quantitative analysis of
and rapid spectroscopic methods for determining plant materials has attracted increasing interest [20],
these components, among which IR spectroscopy is but this method requires more complex mathematical
the most available and attractive [5]. processing because of the overlapping and low inten-
The use of IR spectroscopy, for example, for ana- sity of analytical bands. Javier-Astete et al. [21]
lyzing wood, began in the second half of the 20th cen- described the use of FTIR spectroscopy for identifying
tury under the leadership of Karklin [6, 7] and is con- chemical differences between the apical and basal
tinued at present. In Russia, similar studies are con- woods of two species of Amazonian trees, which are in
ducted by the Derkacheva group. For example, an IR demand in the forest industry. Infrared spectra were
spectroscopy procedure was developed to determine obtained from 150 samples of each tree species aged
lignin in paper [8] and sulfate pulp [9, 10] and to assess 1.8 years. The results indicated significant differences

718
 DETERMINATION OF LIGNIN, CELLULOSE, AND HEMICELLULOSE 719

between the apical and basal stems in terms of the cel- collect wood samples, Haglof age drills (d = 5.15 mm,
lulose, hemicellulose, holocellulose, and lignin con- l = 100 mm) were used to drill radial cores. Wood sam-
centrations. Fourier-transform IR spectroscopy is ples were drilled perpendicularly to the longitudinal
conveniently used to assess the quality of raw materials axis of the trunk at a height of about 1 m from the
used in the production of wood pellets [22], determine ground. Agricultural wastes, in particular, barley straw
the chemical composition of logging waste, and pre- (Kazansky 6/4 variety), wheat straw (Saratovskaya
dict its thermochemical properties [23]. Popescu et al. 36 variety), oat straw (Pobeda variety), corn stalks and
[24] studied combined effects of the chemical (with cobs (Sterling variety), and stalks and sunflower seed
tricine and bicine) and thermal treatment of wood shells (Yenisei variety), were provided by local agricul-
using infrared spectroscopy and chemometric meth- tural producers. Walnut shells (Chandler variety),
ods (principal component analysis and hierarchical peanut shells (Virginia variety), pistachios (Uzun vari-
cluster analysis). Fourier-transform IR spectroscopy ety), hazelnuts (Kuban variety), almonds (Monterey
can serve as an effective tool for detecting differences variety), and pine nuts were obtained from nuts pur-
in chemical compositions between juvenile and chased at a farm market. Coconut (Indonesia) was
mature pine wood: partial least-squares regression purchased in a supermarket. Reed straw was collected
models built from standardized IR spectra ensured in the floodplain of the Insar River in late autumn. All
high accuracy in predicting the concentration of lig- samples were first dried at 60°C for 12 h in a thermo-
nin, cellulose, and extractives [25]. In [26], marker ventilated oven and then ground to a fraction of 50 μm
regions were determined in the IR spectra of some tex- using a Retsch ZM 200 ultracentrifugal mill. Before all
tile plants that can be used in sorting raw materials. studies, the samples were dried to a constant weight in
The ATR method was applied to study the processes of an oven at 105°C for 12 h.
the aging of fibreboards under thermal exposure and
irradiation [27], under the conditions of the alkaline Fourier-transform IR spectroscopy. To analyze
extraction of wood [28], upon treatment with ozone plant materials, we selected the transmission method
[29], and during the cultivation of the fungus Gano- using a KBr tablet instead of the ATR method,
derma lucidum for 1 to 5 years [30]. because it is more convenient to prepare artificial mix-
tures from reference substances in order to obtain a
Thus, the simplicity of sample preparation, the calibration dependence. In addition, the ATR method
availability of equipment, and a variety of methods is based on the principle of surface reflection and is
make FTIR spectroscopy an indispensable tool for more suitable for the analysis of samples with all com-
studying lignocellulosic materials, which can be used ponents uniformly distributed in the matrix. Plant bio-
to rapidly obtain qualitative and quantitative data. mass has a complex 3D structure; therefore, the KBr
The goal of this work was to develop and test an tablet method gives more representative information.
FTIR spectroscopy procedure for determining lignin, In particular, FTIR transmission spectroscopy, pro-
cellulose, and hemicellulose using pressed KBr tab- vided that the particle size is less than 100 μm, gives
lets. Various samples of wood and agricultural waste better spectra than the ATR or diffuse reflection
were used as test samples, 24 samples in total. The method [19, 35]. When the condition of equal masses
concentrations of lignin, cellulose, and hemicellulose, of one and the same sample and KBr is fulfilled, one
determined by IR spectroscopy, were compared with can obtain tablets of equal thickness, yielding repro-
the published data [31, 32]. ducible IR spectra. Spectra of ternary mixtures and
plant materials were recorded at room temperature
with maintaining equal concentrations of a test mate-
EXPERIMENTAL rial (0.5 wt %) and equal thickness of each tablet
Reference compounds. Bacterial cellulose, kraft lig- (0.55 mm), so that the results of analyses are supsect to
nin, and hemicellulose were used to obtain a calibra- the law the Bouguer–Lambert–Beer law and corre-
tion dependence. Bacterial cellulose was obtained in a sponded to the linear section of the calibration func-
static culture medium using Komagataeibacter sucro- tion. The tablets were obtained using KBr containing
fermentans H110 [33], hemicellulose was 0.1 wt % Pb(SCN)2 as of an internal standard. A solid
obtained from birch wood flour according to the pro- mixture consisting of KBr, Pb(SCN)2, and a test sam-
cedure [34], and kraft lignin and lead thiocyanate were ple or reference compounds was ground in a tungsten
purchased from Sigma-Aldrich (Germany). All com- carbide grinding container of a Herzog HP-M 100
pounds used as reference samples were preliminarily semiautomatic vibratory mill for 30 s. Then, tablets
dried at 105°C for 12 h and stored in a desiccator over were pressed from 200 mg of the resulting powder, and
anhydrous CaCl2. their IR spectra were recorded. The tablets were
pressed using a Lab Tools press at a pressure of up to
Plant materials. Various samples of wood and agri- 20 MPa.
cultural wastes were used as test samples, 24 samples
in total. Wood samples were collected from living trees Fourier-transform IR spectra were recorded on an
growing in the forest park area of the city of Saransk. Infra LUM FT-08 IR Fourier-transform spectrometer
Preference was given to trees aged 40–60 years. To in the spectral region 400–4000 cm–1 with a resolution

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 78 No. 6 2023

720 KOSTRYUKOV et al.

of 4 cm–1, using Bessel apodization with an accumula-

3348.83

1033.97
1060.98
tion time of 60 s at an ambient temperature of 18 to 1.2 (a)

1269.32
1512.38
25°C, normal atmospheric pressure, and air humidity 1.1

1219.16
1.0

1462.22
no more than 80%. The peak areas were calculated

2932.16
0.9

1427.5
1601.11
using the SpectraLUM software, version 2.0.1.295. 0.8
0.7
Ash concentration in the reference compounds and 0.6

1705.28
samples of plant biomass was determined by a proce- 0.5
0.4

559.42
dure similar to that of GOST R 56881-2016 [36] with 0.3
the difference that four repetitions were performed for 0.2
0.1
each sample. 0
–0.1

RESULTS AND DISCUSSION 3800 3400 3000 2600 2200 1880 1400 1000 600

1060.98
The FTIR spectra of cellulose, hemicellulose, and

1033.97
lignin, used as reference compounds, are shown in 1.3

3348.83
1.2 (b)

1111.13
Fig. 1. A detailed description of the main absorption 1.1

1165.15
bands of cellulose, hemicellulose, and lignin is given 1.0
in Table 1 [37]. 0.9
0.8

2897.43

1373.48
Absorbance
The spectra of each component at equal concen- 0.7

667.45
0.6

617.3
1631.98

559.42
trations of KBr and tablet thicknesses show noticeable 0.5

1535.52
differences in the intensity and position of some 0.4
absorption bands. We took the absorption band at 0.3
0.2
1512 cm–1 (area integrated between 1490 and 0.1
1530 cm–1), which is mainly due to the skeletal vibra- 0
tions of the aromatic ring, to determine lignin. This 3800 3400 3000 2600 2200 1880 1400 1000 600
selection seems appropriate, because cellulose and

1045.55
hemicellulose do not have absorption bands in this
3364.26
region. Cellulose was determined using the absorption

1604.97
1.1 (c)
band at 1450 cm–1 (area integrated between 1405 and

1412.06
1.0
1480 cm–1), which is mainly assigned to the scissor 0.9
0.8
2928.3

vibrations of the methylene group and bending in-

1319.47
0.7
plane vibrations of the OH group. This selection was

1261.6
0.6
made by analogy with the data [38]. The absorption 0.5
band at 2072 cm–1 (area integrated between 2050 and 0.4

652.02
0.3
2084 cm–1), belonging to the Pb(SCN)2 internal stan- 0.2
dard, was used to normalize the integrated areas of the 0.1
analytical bands selected for quantitative analysis. 0
As for hemicellulose, it structurally differs from 3800 3400 3000 2600 2200 1880 1400 1000 600
cellulose by the presence of acetyl and carboxyl Wavenumber, cm–1
groups. However, the absorption bands of these
groups overlap with the bands of bending vibrations of Fig. 1. IR spectra of (a) lignin, (b) bacterial cellulose,
crystallization water [37], which is not removed from and (c) hemicellulose in tablets with KBr (200 mg with
the sample upon drying. The amount of bound water 0.5 wt % substance).
was determined by thermogravimetry using Netzsch
TG 209 F1 Libra thermomicrobalances as the loss of
sample weight (%) upon heating to 150°C; the analysis spectra of cellulose and hemicellulose differ a little due
conditions were heating from 100 to 200°C at a rate of to structural similarity; therefore, indirect correlations
10 K/min. The amount of bound water was 3.3% for between different amounts of each component in ter-
lignin, 1.1% for bacterial cellulose, and 7.1% for hemi- nary mixtures were used to determine hemicellulose.
cellulose. The amount of crystallization water in the In particular, the ratios of lignin/(cellulose + hemicel-
samples of plant materials did not exceed 5%. Thus, lulose) to the amount of lignin and cellulose/(hemi-
the total amount of water in the ternary mixtures was cellulose + lignin) to the amount of cellulose were
approximately equal to the amount of water in the considered.
plant materials, so no correction for the presence of To develop a model, the ash concentration of each
water was applied. The spectrum of hemicellulose had reference substance (cellulose, hemicellulose, and lig-
a broad absorption band in the region 1750–1510 cm–1, nin) was preliminarily determined to take into account
so we could use the absorption bands of C=O or only the actual amount of a polymer. Rather high ash
COOH groups as analytical ones. Otherwise, the concentrations were detected for lignin (12.5 wt %)

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 78 No. 6 2023

 DETERMINATION OF LIGNIN, CELLULOSE, AND HEMICELLULOSE 721

Table 1. Absorption bands of lignin, bacterial cellulose, and hemicellulose [37]

Absorption
Lignin Bacterial cellulose Hemicellulose
band, cm–1

3700–3100 O–H stretching vibrations

3000–2750 Symmetric and asymmetric C–H stretching vibrations in CH, CH2, and CH3 groups

1770–1700 C=O stretching vibrations No bands C=O stretching vibrations in acetyl

in carbonyl and carboxyl groups fragments

1675–1655 C=O stretching vibrations No bands

in p-substituted aromatic ketones

1650–1615 Bending vibrations of crystallization water

1605–1490 C–C stretching skeletal vibrations of No bands Asymmetric stretching vibrations

the aromatic ring; C=O stretching of the carboxylate anion
vibrations

1470–1460 Asymmetric C–H bending vibra- No bands Scissor symmetric C–H bending
tions in CH2 and CH3 groups vibrations in CH2 groups

1450–1400 C–C stretching skeletal vibrations of O–H bending in-plane vibrations; Symmetric stretching vibrations of
the aromatic ring, combined with C–H scissor vibrations in CH2 the carboxylate anion; symmetrical
asymmetric C–H in-plane bending groups bending vibrations C–H in CH2
vibrations in OCH3 groups groups

1380–1370 No bands C–H and O–H bending vibrations C–H bending vibrations in CH3
groups of acyl fragments

1370–1350 Symmetrical bending vibrations No bands O–H in-plane bending vibrations

C–H in CH3 groups; O–H in-plane
bending vibrations in phenols

1335–1200 Skeletal vibrations of the syringyl C–H bending vibrations; deformation fan vibrations C–H in CH2 groups;
and condensed guaiacyl ring; O–H in-plane bending vibrations
stretching asymmetric vibrations
CAr–O–C; C–O stretching vibra- Symmetrical stretching vibrations of C–O–C bending vibrations between
tions in phenols the glycosidic bond acyl groups and carbohydrate frag-
ments

1170–1150 C–H in-plane bending vibrations Asymmetric stretching vibrations of Asymmetric stretching vibrations of
of the aromatic ring; C–O stretching the C–O–C bridge between gluco- the C–O–C bridge between xylopy-
vibrations pyranose units ranose units

1145–1000 C–H in-plane bending vibrations of Stretching vibrations of the glucopy- Stretching vibrations of the xylopy-
the syringyl and guaiacyl rings ranose ring ranose ring

C–O stretching vibrations in alcohol groups; symmetric and asymmetric C–O–C stretching vibrations

925–750 Out-of-plane C–H bending vibra- Various vibrations of the glucopyra- Various vibrations of the xylopyra-
tions of the aromatic ring nose ring nose ring

700–400 No bands Out-of-plane bending vibrations of hydroxyl groups

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 78 No. 6 2023

 Table 2. Compositions of ternary mixtures of reference substances corrected for ash concentration, areas of analytical absorption bands, and their normalized values
722

(n = 5, P = 0.95)

Lignin, Cellulose,
Lignin, Cellulose, Hemice- Lignin, RSD, Cellulose, RSD, Pb(SCN)2, RSD, S ± Δ (S RSD, S ± Δ (S RSD,
Sample 1 1490–1530/ 2 1405–1480/
% % S
llulose, % 1490–1530 ± Δ % S1405–1480 ± Δ % S2050–2080 ± Δ % % %
S2050–2080) S2050–2080)

1 55 15 30 2.6 ± 0.1 3 2.81 ± 0.07 2 1.18 ± 0.04 3 2.21 ± 0.05 2 2.38 ± 0.09 3

2 45 20 35 2.05 ± 0.08 3 3.12 ± 0.08 2 1.11 ± 0.04 3 1.85 ± 0.05 2 2.81 ± 0.07 2

3 40 35 20 2.01 ± 0.07 3 4.37 ± 0.11 2 1.27 ± 0.05 3 1.58 ± 0.06 3 3.44 ± 0.09 2

4 35 40 25 1.64 ± 0.04 2 4.49 ± 0.11 2 1.25 ± 0.05 3 1.31 ± 0.03 2 3.59 ± 0.09 2
KOSTRYUKOV et al.

5 35 40 35 1.55 ± 0.06 3 4.18 ± 0.10 2 1.17 ± 0.03 2 1.32 ± 0.03 2 3.57 ± 0.09 2

6 30 65 5 1.35 ± 0.03 2 5.76 ± 0.14 2 1.21 ± 0.03 2 1.12 ± 0.03 2 4.76 ± 0.12 2

JOURNAL OF ANALYTICAL CHEMISTRY

7 30 60 10 1.49 ± 0.06 3 5.69 ± 0.14 2 1.26 ± 0.05 3 1.18 ± 0.03 2 4.52 ± 0.11 2

Vol. 78
8 25 60 15 1.28 ± 0.03 2 5.91 ± 0.15 2 1.31 ± 0.05 3 0.98 ± 0.02 2 4.51 ± 0.11 2

No. 6
9 15 60 25 0.78 ± 0.03 3 5.71 ± 0.14 2 1.26 ± 0.05 3 0.62 ± 0.02 2 4.53 ± 0.11 2

2023
 DETERMINATION OF LIGNIN, CELLULOSE, AND HEMICELLULOSE 723

Table 3. Parameters for the indirect determination of hemicellulose concentration (n = 5, P = 0.95)

ωlignin ωcellulose
Sample X 1 = S1 RSD, % X2 = S2 RSD, %
ωcellulose + ωhemicellulose ωlignin + ωhemicellulose
1 1.22 2.21 ± 0.05 2 0.18 2.38 ± 0.09 3
2 0.82 1.85 ± 0.07 3 0.25 2.81 ± 0.07 2
3 0.73 1.58 ± 0.06 3 0.58 3.44 ± 0.09 2
4 0.54 1.31 ± 0.03 2 0.67 3.59 ± 0.09 2
5 0.47 1.32 ± 0.03 2 0.57 3.57 ± 0.09 2
6 0.43 1.12 ± 0.03 2 1.86 4.76 ± 0.12 2
7 0.43 1.18 ± 0.03 2 1.50 4.52 ± 0.11 2
8 0.33 0.98 ± 0.02 2 1.50 4.51 ± 0.11 2
9 0.18 0.62 ± 0.02 2 1.50 4.53 ± 0.11 2

and hemicellulose (16.8 wt %), and a low ash concen- ln X 1 = (1.4833 ± 0.0652 ) ln S1 – (1.0501 ± 0.0278) ,
tration was revealed for bacterial cellulose (0.4 wt %). (3)
n = 5, P = 0.95, r = 0.9933,
According to the procedures described in the
Experimental section, several ash-corrected ternary ln X 2 = (3.4857 ± 0.1269 ) ln S2 – ( 4.8673 ± 0.1685) ,
mixtures of reference substances were prepared (sam- n = 5, P = 0.95, r = 0.9954. (4)
ples 1–10, Table 2). To decrease errors, the IR spectra
of each sample were measured five times and then The concentration of hemicellulose was calculated
averaged. For the absorption bands under consider- by Eqs. (5) and (6) derived from Eqs. (3) and (4),
ation, we estimated integrated areas and plotted the respectively,
dependence of these values on the concentrations of
ωlignin
lignin and cellulose. The peak areas were calculated ωhemicellulose = – ωcellulose, (5)
using baseline correction. The compositions of refer- X1
ence ternary mixtures, integral intensities, and their
ωcellulose
normalized values are given in Table 2. ωhemicellulose = – ωlignin . (6)
X2
Calibration functions for the determination of cel-
lulose and lignin in ternary mixtures of cellulose– Using Eqs. (1), (2), (5), and (6), we determined the
hemicellulose–lignin were linear dependences limits of quantification for lignin, cellulose, and hemi-
between the concentration of lignin or cellulose and cellulose. For this purpose, ternary mixtures were pre-
the values of S1 or S2 (Eqs. (1) and (2)); the correlation pared to contain from 1 to 10 wt % of each component,
coefficient was 0.9947 for Eq. (1) and 0.9977 for while the remainder of a mixture consisted of the
Eq. (2). remaining components in equal proportions. The
limit of detection was found to be >3% for lignin, >8%
S1 + 0.0504 for cellulose, and >9% for hemicellulose. Then, using
ωlignin = , (1) Eqs. (1), (2), (5), and (6), we calculated the concen-
0.0407 trations of lignin, cellulose, and hemicellulose in plant
S2 − 1.7926 materials (Table 4); and the published data are also
ωcellulose = . (2) given in the table for comparison. The data on the
0.0455 composition of plant materials, calculated from the IR
Hemicellulose was determined in ternary mixtures spectra, generally correspond to the values given in
using indirect correlations. In particular, we consid- [31, 32]. A comparison of the results obtained for
ered the dependence of the ratio of lignin concentra- hemicellulose using Eqs. (5) and (6) indicates that the
tion to the total concentration of cellulose and hemi- ternary mixture model gives reasonable values for
cellulose (X1) on the parameter S1 or the dependence hemicellulose concentration in most plant biomass
of the ratio of cellulose concentration to the total con- samples, except for oat, wheat, and barley straw, corn
centration of hemicellulose and lignin (X2) on the stalks, sunflower, and shells of some nuts. This phe-
parameter S2 (Table 3). nomenon can be explained by a difference between the
real composition of these biomass samples and the
These dependences most closely correspond to composition of ternary mixtures because of the pres-
power functions presented as linear dependences ence of other components in them, such as extractives
using the substitution of variables: Eq. (3) (model 1) and proteins, which were not taken into account in this
and Eq. (4) (model 2). study.

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 78 No. 6 2023

 Table 4. Concentrations (%) of lignin, cellulose, and hemicellulose in lignocellulosic biomass samples, calculated from IR spectra and reported in the literature
724

(n = 5, P = 0.95)
Lignin Cellulose Hemicellulose
Sample published published published
IR RSD, % IR RSD, % IR (1) RSD, % IR (2) RSD, %
data data data

Spruce wood [31] 26.6 ± 1.3 4 27.9 46.1 ± 1.1 2 45.5 28.35 ± 0.7 2 26.3 ± 1.0 3 22.9
Pine wood [31] 19.10 ± 0.95 4 20.0 47.0 ± 1.2 2 42.0–50.0 38.4 ± 1.4 3 32.8 ± 1.2 3 24.0–27.0
Larch wood [31] 29.8 ± 1.5 4 28.5 48.0 ± 1.8 3 47.5 22.1 ± 0.8 3 20.8 ± 0.8 3 24.5
Aspen wood [31] 20.3 ± 1.0 4 19.5 51.1 ± 1.3 2 52.7 32.5 ± 1.6 4 26.9 ± 1.0 3 21.7
Poplar wood [31] 31.0 ± 1.2 3 29.1 38.0 ± 1.4 3 39.8 30.6 ± 1.1 3 33.5 ± 1.3 3 14.8
Beech wood [31] 23.7 ± 1.2 4 21.0 39.1 ± 1.5 3 40.0 39.55 ± 2.0 4 39.1 ± 1.0 2 23.0
Oak wood [31] 32.5 ± 1.2 3 35.4 44.1 ± 1.6 3 43.2 22.7 ± 0.8 3 23.0 ± 0.9 3 21.9
Willow wood [31] 17.9 ± 0.7 3 16.9–18.9 43.0 ± 1.6 3 42.4–45.3 44.0 ± 1.6 3 39.1 ± 1.5 3 20.6–22.9
Cherry wood [31] 19.6 ± 0.7 3 18.0 46.1 ± 1.7 3 46.0 38.6 ± 1.4 3 33.4 ± 1.2 3 29.0
Barley straw [31] 10.1 ± 0.5 4 6.3–13.1 41.0 ± 2.0 4 36.0–43.0 50.1 ± 2.5 4 49.7 ± 1.9 3 24.0–33.0
Wheat straw [31] 13.3 ± 0.5 3 12.0–16.0 37.1 ± 1.4 3 35.0–39.0 54.6 ± 2.0 3 52.7 ± 2.0 3 23.0–30.0
Oat straw [32] 14.7 ± 0.7 4 10.0–15.0 32.95 ± 1.6 4 31.0–35.0 57.7 ± 2.9 4 58.3 ± 2.9 4 20.0–26.0
Corn stalks [32] 12.0 ± 0.5 3 7.0–18.4 38.0 ± 1.4 3 35.0–39.6 54.0 ± 2.0 3 52.45 ± 1.95 3 16.8–35.0
KOSTRYUKOV et al.

Corn cobs [32] 7.7 ± 0.4 4 6.1–15.9 39.95 ± 1.5 3 33.7–41.2 46.1 ± 2.3 4 53.7 ± 2.7 4 31.9–36.0
Sunflower stems [32] 9.1 ± 0.3 3 7.7–13.4 41.0 ± 1.5 3 34.1–42.1 48.7 ± 1.8 3 50.6 ± 1.9 3 5.18–9.71
Sunflower seed shell [32] 23.5 ± 1.2 4 20–25 48.0 ± 1.2 2 45–55 30.9 ± 1.5 4 27.1 ± 1.4 4 23–28
Walnut shell [31] 52.1 ± 1.9 3 53.5 24.0 ± 0.9 3 23.3 24.3 ± 0.9 3 34.8 ± 1.3 3 20.4

JOURNAL OF ANALYTICAL CHEMISTRY

Peanut shell [32] 28.6 ± 1.1 3 28.0 38.0 ± 1.4 3 37.0 33.8 ± 1.3 3 35.9 ± 1.3 3 18.7
Pistachio shell [31] 30.0 ± 1.1 3 29.4 15.9 ± 0.8 4 15.2 54 ± 2 3 51.5 ± 1.9 3 38.2
Hazelnut shell [32] 39.25 ± 1.95 4 38.0 30.1 ± 1.5 4 30.0 29.1 ± 1.4 4 38.8 ± 1.9 4 23

Vol. 78
Almond shell [31] 35.4 ± 1.3 3 36.0 27.1 ± 1.0 3 27.0 36.3 ± 1.4 3 47.7 ± 1.8 3 30
Pine nut shell [31] 37.6 ± 1.9 4 38.0 32.1 ± 1.6 4 31.0 28.9 ± 1.4 4 37.0 ± 1.8 4 25

No. 6
Coconut shell [32] 31.0 ± 0.8 2 29.0 37.1 ± 1.4 3 36.0 31.5 ± 0.8 2 34.9 ± 0.9 2 25
Reed straw [32] 9.1 ± 0.5 4 8.7 50.0 ± 1.9 3 49.4 39.8 ± 2.0 4 39.3 ± 2.0 4 31.5

2023
* Data for comparison are taken from works, references to which are given after the name of the sample.
 DETERMINATION OF LIGNIN, CELLULOSE, AND HEMICELLULOSE 725

Table 5. Concentrations of lignin, cellulose, and hemicellulose, calculated and found by the standard addition method in
samples of lignocellulosic biomass (n = 5, P = 0.95)
Lignin (+20%) Cellulose (+20%) Hemicellulose (+20%)
Sample (80%) RSD, % RSD, % RSD, %
calculated found calculated found calculated found
Spruce wood 41.3 41.6 ± 0.5 1 56.7 56.8 ± 0.7 1 42.7 43.1 ± 0.5 1
Pine wood 35.3 35.3 ± 0.4 1 57.6 57.8 ± 0.7 1 50.7 51.0 ± 0.6 1
Larch wood 43.8 43.7 ± 0.5 1 58.4 58.4 ± 0.7 1 37.7 37.9 ± 0.5 1
Aspen wood 36.2 36.5 ± 0.9 2 60.9 61.0 ± 0.8 1 46.0 47.0 ± 0.6 1
Poplar wood 44.8 44.6 ± 0.5 1 50.4 50.8 ± 0.6 1 44.5 44.8 ± 0.6 1
Beech wood 39.0 39.0 ± 0.5 1 51.3 51.6 ± 0.6 1 51.6 51.4 ± 1.3 2
Oak wood 46.0 46.1 ± 1.2 2 55.3 55.6 ± 0.7 1 38.1 38.5 ± 1.0 2
Willow wood 34.3 34.2 ± 0.4 1 54.4 54.9 ± 0.7 1 55.2 55.5 ± 0.7 1
Cherry wood 35.7 35.6 ± 0.9 2 56.9 57.1 ± 0.7 1 50.9 51.1 ± 1.3 2
Barley straw 28.1 28.0 ± 0.4 1 52.8 53.1 ± 0.7 1 60.1 59.9 ± 0.7 1
Wheat straw 30.6 30.8 ± 0.8 2 49.7 49.9 ± 0.6 1 63.7 63.6 ± 1.6 2
Oat straw 31.8 32.0 ± 0.4 1 46.4 46.4 ± 1.2 2 66.2 66.3 ± 1.7 2
Corn stalks 29.2 29.7 ± 0.4 1 50.4 50.5 ± 1.3 2 63.2 63.8 ± 0.8 1
Corn cobs 26.1 26.4 ± 0.7 2 52.0 52.1 ± 0.7 1 56.9 57.0 ± 1.4 2
Sunflower stems 27.3 27.6 ± 0.3 1 52.8 52.6 ± 0.7 1 59.0 59.2 ± 0.7 1
Sunflower seed shell 38.8 38.6 ± 0.5 1 58.4 58.9 ± 0.7 1 44.7 44.3 ± 0.5 1
Walnut shell 61.7 61.6 ± 0.8 1 39.2 39.4 ± 0.5 1 39.5 40.0 ± 0.5 1
Peanut shell 42.85 42.4 ± 1.1 2 50.4 50.8 ± 0.6 1 47.0 47.1 ± 0.6 1
Pistachio shell 44.0 44.2 ± 0.6 1 32.7 32.9 ± 0.4 1 63.2 63.4 ± 0.8 1
Hazelnut shell 51.4 51.0 ± 0.6 1 44.1 44.3 ± 1.1 2 43.3 43.7 ± 0.5 1
Almond shell 48.3 48.6 ± 0.6 1 41.6 41.8 ± 1.0 2 49.0 48.9 ± 1.2 2
Pine nut shell 50.0 49.9 ± 1.2 2 45.7 45.6 ± 0.6 1 43.1 43.9 ± 1.1 2
Coconut shell 44.8 45.6 ± 0.6 1 49.7 50.0 ± 1.2 2 45.2 45.5 ± 1.1 2
Reed straw 27.3 28.7 ± 0.4 1 60.0 60.5 ± 1.5 2 51.8 52.0 ± 0.7 1

The relative standard deviation of the results of Equation (5) was used to determine hemicellulose.
analyses of all samples does not exceed 4%; therefore, The data in Table 5 indicate the good accuracy of the
we can state that the developed procedure is character- developed procedure for the determination of lignin,
ized by good measurement reproducibility. cellulose, and hemicellulose in plant materials.
The accuracy of the proposed procedure for the
determination of lignin, cellulose, and hemicellulose CONCLUSIONS
was evaluated by the standard addition method. We Thus, concentrations of lignin, cellulose, and
prepared samples consisting of 80 wt % of a plant hemicellulose can be determined in plant materials
material with additions of 20 wt % of lignin, cellulose, from calibration equations obtained for ternary mix-
or hemicellulose. Three independently prepared sam- tures composed of lignin, cellulose, and hemicellu-
ples of identical compositions were analyzed. Table 5 lose, using FTIR spectroscopy with pressed KBr tab-
presents the calculated and found concentrations of lets, under the conditions of equal degrees of grinding
lignin, cellulose, and hemicellulose in these samples. of the tablet material and weighing accuracies. The

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726 KOSTRYUKOV et al.

accuracy of the developed procedure was verified by 15. Pozhidaev, V.M., Sergeeva, Y.E., Malakhov, S.N., and
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