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Physico-chemical characteristics of leaf litter biomass to delineate the

chemistries involved in biofuel production

Article  in  Journal of the Taiwan Institute of Chemical Engineers · March 2016

DOI: 10.1016/j.jtice.2016.02.011

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 Journal of the Taiwan Institute of Chemical Engineers 62 (2016) 239–246

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Journal of the Taiwan Institute of Chemical Engineers

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

Physico-chemical characteristics of leaf litter biomass to delineate the

chemistries involved in biofuel production
Nadeem Akhtar a, Dinesh Goyal a,∗, Arun Goyal b
a
Department of Biotechnology, Thapar University, Patiala, 147 004 Punjab, India
b
Department of Biotechnology, Indian Institute of Technology Guwahati, Guwahati, 781 039 Assam, India

a r t i c l e i n f o a b s t r a c t

Article history: Increase in energy demand across the world has put immense pressure on utilization of widely avail-
Received 10 September 2015 able lignocellulosic agricultural waste biomass and forest residues. Physico-chemical characteristics of leaf
Revised 2 January 2016
litter from largely grown tree species such as Mangifera indica, Populus deltoides and Polyalthia longifo-
Accepted 2 February 2016
lia were evaluated for possible use in biorefinery. Physical and chemical properties of these leaf litter
Available online 16 March 2016
biomasses were examined using bomb calorimetry, SEM, XRD, TGA, CHNSO analysis, FTIR and solid state
13
Keywords: C CP/MAS NMR spectroscopy. Low ash content (3.70 wt%), high volatile matter (76.05 wt%) and cellu-
Biofuel lose (37.75 wt%) was observed from leaf litter biomass of P. deltoides. SEM of leaf litter biomass revealed
Mangifera indica compacted surface morphology of M. indica, however a fibrillar structure was observed in P. deltoides and
Populus deltoides P. longifolia. Maximum crystallinity index (CrI) was observed in leaf litter biomass of M. indica (23.13%)
Polyalthia longifolia followed by P. longifolia (20.94%) and P. deltoides (20.93%). The calorific values of all biomasses were in
the range of 18.37 to 19.32 MJ/kg. Delineation of these physico-chemical characteristics together per se
shows that leaf litter biomass can also act as a potential feedstock for biofuel production.
© 2016 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction tree plantation sites can be collected and used as a promising feed-
stock for biofuel production to mitigate energy crisis.
Considering world energy demand and its security, attention is Lignocellulosic biomass refers to plant derived organic mat-
being focused on inexpensive renewable lignocellulosic substrates ter, composed of cellulose, hemicellulose, lignin, pectins, extrac-
for biofuel production. These energy resources are an alternatives tives, glycosylated proteins and several other inorganic mate-
to fossils fuel and their derivatives, and have become a high prior- rials. Cellulose is a linear condensation polymer consisting of
ity for chemical industries [1]. To solve the global warming prob- D-anhydroglucopyranose joined by β -1, 4-glycosidic bonds with a
lem and ensure sustainable development of the economy, it is nec- degree of polymerization from 100 to 20,0 0 0 [6]. Hemicellulose,
essary to increase the use of renewable biomass resources [2], as a complex carbohydrate, is comprised of pentoses (e.g. xylose and
they lack the environmental risk and capital investment associated arabinose), hexoses (e.g. mannose, glucose and galactose) and sugar
with fossil fuels. The available biomass of the world is 220 billion acids. The most abundant polymer after cellulose and hemicel-
oven dry tones (ODT) per year or 4500 EJ (1018 J) [3]. India meets lulose is lignin, which consists of three different phenylpropane
70% of its energy requirement using fuel woods and in the process units (p-coumaryl, coniferyl and sinapyl alcohol) [7]. The cellu-
about 50 million tones of wood are removed from forests every lose, hemicellulose and lignin content of such biomasses fall in the
year [4]. Substantial portion of cellulosic and hemicellulosic com- range of 30–50%, 15–35% and 10–20%, respectively [8,9]. The ac-
ponent of leafy biomass can be readily hydrolyzed into fermentable cessibility of cellulose which is embedded in hemicelluloses-lignin
sugars by action of different hydrolytic enzymes, which is further matrix and highly crystalline nature of the cellulose are two main
biotransformed into ethanol [5]. Therefore, leaf litter biomass from factors responsible for increasing the cost associated with process-
ing of lignocellulosic biomass [10]. Determining relative quantities
of cellulose, hemicellulose and lignin in lignocellulosic feedstock
is often required in studies involving fractionation [11], fermenta-
Abbreviations: CrI, crystallinity index; CP/MAS NMR, cross polarizing magic an- tion [12], or other modification [13]. Besides biofuel, lignocellulosic
gle spinning nuclear magnetic resonance; FTIR, fourier transform infrared; SEM,
biomass can be a source of other bio-based products such as lev-
scanning electron microscopy; TGA, thermal gravimetric analysis; XRD, X-ray
diffraction. ulinic acid, furfural and hydroxy methyl furfural [14].
∗
Corresponding author. Tel.: +91 175 2393314; fax: +91 175 2393011. Chemical and molecular characteristics of lignocellulosic feed-
E-mail address: dgoyal@thapar.edu (D. Goyal). stock vary with geo-climatic conditions and taxonomic rank too.

http://dx.doi.org/10.1016/j.jtice.2016.02.011
1876-1070/© 2016 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
240 N. Akhtar et al. / Journal of the Taiwan Institute of Chemical Engineers 62 (2016) 239–246

Table 1 cess of heating and cooling was repeated until constant weight was
Botanical nomenclature of biomass samples source.
obtained.
Common name Family Genus Scientific name
2.2.3. Volatile matter and fixed carbon
Mango Anacardiaceae Mangifera Mangifera indica
The volatile matter in the leaf litter biomass was determined
Poplar Salicaceae Populus Populus deltoides
Ashoka Annonaceae Polyalthia Polyalthia longifolia
by the procedure given in ASTM D 3175-07 [23]. A biomass sam-
ple (1.0 g) was taken in a covered crucible and placed in a muf-
fle furnace regulated at 950 ± 10 °C for 7 min to obtain rapid heat-
ing. Then the crucible was removed from the furnace and placed
The primary obstacle impeding the widespread production of
in a desiccator. The loss of weight was interpreted as the volatile
bioenergy from biomass lies in the availability of low-cost tech-
matter in the biomass. Fixed carbon was the resultant of the sum-
nology to overcome recalcitrant nature of lignin. To make cellulose
mation of percentage moisture, ash, and volatile matter subtracted
more accessible for hydrolytic enzymes, lignin component must be
from 100.
separated [15], which primarily depends upon the degree of poly-
merization, crystallinity, structural composition and surface area 2.2.4. Calorific value
[16]. Knowing accurately the physico-chemical composition of lig- The calorific value of all biomass samples was determined in
nocellulosic biomass is gaining importance in assessing its poten- a static bomb calorimeter; BCM 211059, using the procedure de-
tial for biomass to biofuel conversion [1,11,17]. scribed in NREL protocol [24]. Each biomass sample was mixed
The current investigation is based on evaluation of physico- thoroughly in the sample bottle and was made into a pellet, tak-
chemical characteristics of different leaf litter biomasses from ing care that the heavies and lights (fluff) were distributed well in
largely grown tree species such as Mangifera indica, Populus del- the sample. Samples (1.0 g) in the form of pellet was measured out
toides and Polyalthia longifolia to evaluate their potential as feed- and put into pre-weighed crucibles. A cotton thread was attached
stock for bio-energy production. to a platinum ignition wire and placed in contact with the pellet.
Distilled water (1 ml) was poured into the bomb and then filled
2. Material and methods with oxygen to a consistent pressure between 20 and 30 atm (2.03
and 3.04 MPa). The calorimeter was placed in an isothermal jacket
2.1. Collection of biomass samples with an air gap separation of 10 mm between all surfaces. The
electrical energy for ignition, discharged through a platinum wire
Leaf litter biomass samples from largely grown trees such as M. of ∼40 V, was calculated using the change in potential across a
indica, P. deltoides and P. longifolia were collected from soil surface 1256 or 2900 mF capacitor. The bomb calorimeter was submerged
in early spring (March 2014) from Thapar University campus, Pa- in a calorimeter cane filled with distilled water. The jacket of the
tiala, Punjab (India), located at 30°19 48"N, 76°24 0"E and 310 m calorimeter was maintained at constant temperature by circulating
above the sea level. The detailed nomenclature of the source of water at 25° C.
biomasses is represented in Table 1. The air dried biomass sam-
ples were ground using mechanical blender and sieved to get ho- 2.2.5. Scanning electron microscopy (SEM)
mogeneous powder (diameter of particle < 0.5 mm) (Supplemen- The physical appearance of biomass samples were observed
tary material, Plate 1). Sieved biomass samples were stored in air by SEM. The samples were coated to provide conductivity with
tight containers at room temperature for characterization studies. gold using gold sputter at a voltage of 10–15 kV. Images were
The general outline of the biomass characterization is presented in taken using SEM (Model: JEOL JSM-6510 LV, USA) at different
Fig. 1. magnifications.

2.2. Physical characterization 2.2.6. X-ray diffraction (XRD) analysis

Crystallinity of the powdered biomass samples was analyzed at
2.2.1. Moisture content room temperature in the scanning angle of 5–50° at the scan speed
Moisture content plays a key role in the selection of a suitable of 5°/min using a PANalytical X’Pert PRO diffractometer (Nether-
substrate for bioenergy application due to hydrophilic properties. lands) with Ni-filter, operated at 45 kV and 40 mA with λ (Cu
Adsorption of moisture may lead to a decrease in the energy den- Kα ) = 1.5406 Å. The crystallinity index (CrI) of the biomass samples
sity of the biomass [18]. Comparative low moisture content feed- were determined as described by Segal et al. [25] as follows:
stock (<15%) is preferred when using a thermal conversion process, CrI = [(I002 − Iam )/I002 ] × 100
while bio-conversion can utilize biomass with a high moisture con-
Where I002 is the intensity for the crystalline portion of biomass
tent [19]. The moisture content of the biomass was determined us-
(i.e. cellulose) at about 2θ of 21–23°, and Iam is the peak for
ing the procedure given in ASTM 3173-87 [20].
the amorphous portion (i.e. cellulose, hemicellulose, and lignin) at
about 2θ of 16–18° in most literatures [1,2,17,26].
2.2.2. Ash content
Ash, the incombustible solid mineral matter present in the 2.2.7. Thermal gravimetric analysis (TGA)
biomass, mainly contains oxides of silica (SiO), Aluminium (AlO), To understand the devolatilization characteristics, TGA of
Iron (FeO), calcium (CaO) and Magnesium (MgO). The cations biomass samples were performed using a Mettler Toledo instru-
present in ash retards the enzymatic saccharification of biomass ment (Model: TGA/SDTA 851e). The devolatilizations of biomasses
samples to glucose and other fermentable sugars [21]. Therefore it were studied from 20 to 700 °C with a heating rate of 10 °C/min
is prerequisite to analyze the biomass for ash content before us- with a purge gas (nitrogen) flow rate of 60 ml/min.
ing it as a feedstock for biofuel production. Determination of ash
content in biomass samples were adopted as per the protocol de- 2.3. Chemical characterization of biomasses
scribed in ASTM D 3174-04 [22]. Oven dried biomass sample (1.0 g)
was taken in oven dried moisture free crucibles and placed in muf- 2.3.1. CHNSO analysis
fle furnace maintained at 575 ± 10 °C for 4 h. Crucibles were re- The basic elements of any biomass such as carbon (C), hydro-
moved from the furnace and placed in a dessicator and the pro- gen (H), nitrogen (N), sulphur (S) and oxygen (O), were analyzed
 N. Akhtar et al. / Journal of the Taiwan Institute of Chemical Engineers 62 (2016) 239–246 241

Fig. 1. Scheme for characterization of biomass samples.

Table 2
Proximate, ultimate and calorific value of biomass.

Biomass Proximate analysis (wt%) Ultimate analysis (wt%) Calorific Value

(MJ/kg)
§ ¥
Ash Volatile matter Fixed carbon Moisture C H N S O

M. indica 9.46 ± 0.60a 75.01 ± 4.77a 7.71 ± 0.40b 7.57 ± 0.47b 39.32 ± 2.40b 5.25 ± 0.20b 0.28 ± 0.01b 0.10 ± 0.008a 55.05 ± 3.95a 18.37 ± 0.46b
P. deltoides 3.70 ± 0.28c 76.05 ± 6.25a 11.23 ± 0.78a 8.32 ± 0.70a 40.68 ± 3.08b 4.81 ± 0.49c 1.40 ± 0.03a 0.02 ± 0.002b 53.09 ± 2.55a 18.50 ± 0.45b
P. longifolia 8.67 ± 0.65b 75.34 ± 4.18a 7.66 ± 0.71b 7.34 ± 0.69b 44.78 ± 2.39a 5.55 ± 0.15a 1.48 ± 0.09a 0.09 ± 0.004a 48.10 ± 2.50b 19.32 ± 0.73a

Values are mean ± SD (n = 3), bearing different letters in same column are significant at P < 0.05.
§
Percent of fixed carbon calculated from difference of moisture, ash and volatile matter content.
¥
Percent O calculated from the difference of C, H, N and S.

in a PerkinElmer Elementar CHNSO analyzer. The sample (1.0 mg) were spun at a rate of 10 kHz using 4 mm zirconia (ZnO2 ) rotor
was used in a tin boat assortment at 900 °C in an oxygen atmo- with CP pulse programme. Typically 18,0 0 0 transients were accu-
sphere to determine the percentage composition of C, H, N and S. mulated in the time domain with a contact time of 1 ms and a re-
The percentage of O was determined by means of difference. cycle delay of 3 s. Tetramethylsilane (TMS) was used as an external
standard for the calibration of the 13 C chemical shift.
2.3.2. Determination of extractives and compositional analysis
For determination of extractives, biomass samples (5 g) were 2.3.5. Statistical analysis
extracted using a Soxhlet extraction apparatus through cotton cel- All the experiments were performed in triplicate and the data
lulose extraction thimbles (external length 94 mm and inner diam- were analyzed by analysis of variance (ANOVA) using GraphPad
eter 33 mm) as per the NREL protocol [24]. The heating mantle was Prism (5.0) software followed by the Tukey’s honestly significant
adjusted to provide a minimum of 6–10 siphon cycles per hour. difference test. Results were expressed as mean ± S.D. (n = 3).
Three stages of extraction; n-hexane, ethanol and distilled water
were performed and each extraction operation was executed for 3. Results and discussion
6 h. The solvent in each extract was removed in a rotary evapora-
tor under reduced pressure. In the first step the extraction of n- 3.1. Determination of proximate, ultimate and calorific values
hexane soluble compounds was carried out to separate the class
of compounds such as non-polar lipids, hydrocarbon compounds, The proximate and ultimate composition along with calorific
terpenoids etc. The raffinated biomass of the first step was ex- value of leaf litter biomasses from Mango, Poplar and Ashoka are
tracted with ethanol to separate compounds such as chlorophyll, shown in Table 2. The percentage of ash in Mango, Poplar and
polar waxes, sterol and other minor constituents. The final raffinate Ashoka leaf litters were found to be 9.46, 3.70 and 8.67%, respec-
biomass was extracted with distilled water to separate inorganic tively. Moisture content of these biomass samples were found in
materials and non-structural carbohydrates [1]. Raffinate biomass the range of 7.34–8.32%. Similar results were observed for wheat
was subjected to cellulose, hemicelluloses and lignin estimation by straw, barley straw, flax straw and timothy grass and reported
TAPPI protocol [27]. in the range of 5.0–7.9% for moisture and 1.1–9.8% for ash con-
tent by Naik et al. [1]. Biomass of Areca catechu, Ziziphus rugosa
2.3.3. Fourier transform infrared (FTIR) spectroscopy and Albizia lucida showed moisture content of 6.6, 5.2 and 5.8%
Accurate predictions of the chemical composition of biomass and ash content of 2.9, 1.3 and 1.5%, respectively [17]. Greater
samples were obtained by FTIR spectroscopy using a Nicolet Instru- amount of ash was observed with Mango and Ashoka leaf lit-
ment (Model: MAGNA 550, USA). The biomass sample (10 mg) was ter biomasses, accounted them less suitable than Poplar leaf litter
mixed with 200 mg of KBr and the mixture was compressed for biomass for bioethanol production as ash cannot be converted into
preparation of pellets. Each spectrum was the average of 64 scans energy. Feedstock with low moisture content (<15%) is preferred
with a total scan time of 15 s in the IR range of 40 0–40 0 0 cm−1 . using thermal conversion process, while conversion using biolog-
ical means require relatively high moisture for submerged and
2.3.4. Solid state 13 C CP/MAS NMR spectroscopy solid state fermentation. In biomass fuel, chemical energy is stored
Solid state 13 C CP/MAS NMR spectroscopy is an important tool mainly in the form of fixed carbon and volatile matter, which can
to analyze the structural features of lignocellulosic biomass. The be released via direct or indirect combustion. High volatile matter
spectra of biomass samples were obtained at 75.475 MHz using and low ash content were observed with Poplar leaf litter biomass,
a Bruker AV-300 FT NMR spectrometer (Germany). Dried samples may be considered as promising substrate for biofuel production.
242 N. Akhtar et al. / Journal of the Taiwan Institute of Chemical Engineers 62 (2016) 239–246

Table 3
Peak at crystalline and amorphous region and CrI of different biomass samples.

Biomass Crystalline portion peak Amorphous portion peak CrI (%)

at 2 θ angle at 2 θ angle

M. indica 22.89° 18.45° 23.13

P. deltoides 22.82° 18.62° 20.93
P. longifolia 22.30° 18.49° 20.94

CHNSO analysis of biomass samples showed no marked differ-

ence (Table 2). Leaf litter biomass samples contained C, H, N, S and
O in the range of 39.32–44.78%, 4.81–5.55%, 0.28–1.48%, 0.02–0.10%
and 48.10–55.05%, respectively. Results of ultimate analysis were
in good agreement with the earlier results reported by Naik et al.
[1] and Sasmal et al. [17] with different biomass samples. Nitrogen
and S generates oxides as gaseous emissions (NOx, SOx) on com-
bustion, therefore does not contribute to the total heating value
of biomass. In contrast to conventional fuels, biofuels demonstrate
relatively low proportions of C, as compared to the total proportion
of O and H, deteriorating fuel energy value due to lower energy
contained in C =O and C–H bonds over C–C bonds [28]. Calorific
value of Ashoka leaf litter biomass was found greater (19.32 MJ/kg)
as compared to Poplar (18.50 MJ/kg) and Mango (18.37 MJ/kg) leaf
litter biomasses. High calorific value of wheat straw (20.3 MJ/kg),
pinewood (19.6 MJ/kg) [1], Z. rugosa (21.24 MJ/kg) and A. lucida
(20.35 MJ/kg) [17] makes these biomass types more efficient for
production of bio-energy than the litters we studied.

3.2. Scanning electron microscopy (SEM)

Scanning electron micrographs of native biomass fractions ex-

hibited different surface structure with intact morphology. Distinct
surface structures were observed with micrographs (Fig. 2) of dif-
ferent leaf litter biomasses from Mango, Poplar and Ashoka, prob-
ably due to taxonomic differences. More compact structure was
seen with the micrograph of Mango leaf litter (Fig. 2a). However,
comparatively less compact and fibrillar structure was observed
with leaf litter biomasses of Poplar (Fig. 2b) and Ashoka (Fig. 2c).
Rigid and compact structure is generally observed due to encap-
sulation of cellulosic fibers by lignin-hemicellulose matrix, which
hinders accessibility of cellulose to hydrolytic enzymes for conver-
sion processes.

3.3. X-ray diffraction (XRD) analysis

The XRD analysis of leaf litter biomass samples are presented in

Fig. 3. The peaks for crystalline and amorphous cellulose were ob-
served near 2θ angles of 18° and 22°, respectively (Table 3, Fig. 3)
Fig. 2. Scanning electron micrograph of leaf litter biomass samples from (a) Mango,
for leaf litter biomasses from Mango, Poplar and Ashoka. CrI of (b) Poplar and (c) Ashoka (Magnification: 1,0 0 0X).
these samples was found in the range of 21–23% in the native
state. High crystallinity hinders enzymatic hydrolysis of lignocel-
lulosic biomass. Amorphous cellulose is readily accessed by cellu- 3.4. Thermal gravimetric analysis (TGA)
lases as compared to crystalline microfibrils [29] and it is widely
accepted that the decrease in crystallinity increases the digestibil- The behavior of different biomass samples during devolatiliza-
ity of lignocelluloses [30,31]. On the contrary, more crystalline lig- tion were quite different (Fig. 4.). The onset temperature of de-
nocelluloses have been reported to show more digestibility [2,32]. volatilization was in the range of 200–250 °C, which corresponded
Similar peaks for crystalline and amorphous cellulose were also to weight loss (∼10%) with respect to the final weight loss. The
observed with different biomass samples [1,17,26,32]. Crystallinity main weight loss ends at 310–350 °C for all biomasses and then
depends on relative amounts of crystalline and amorphous compo- followed by a slow and continuous weight loss. The former step
nent of cellulosic microfibrils [29]. However, determining true crys- was due to the primary devolatilization, whereas the later was
tallinity of cellulose is ambiguous, as crystallinity depends upon attributed to the degradation of heavier chemical structures in
the entire material including hemicelluloses, lignin and the nature the solid matrix [33]. The weight loss during devolatilization can
of bonds between them too. Therefore, further study between ma- be explained as follows: the weight loss at temperature less
jor chemical classes and their interactions is necessary to justify than 100 °C was for loss of easily volatilized compounds, 100–
the diffractographic studies. 130 °C for loss of water, 130–250 °C for loss of volatile compounds,
 N. Akhtar et al. / Journal of the Taiwan Institute of Chemical Engineers 62 (2016) 239–246 243

Table 4
Extractives (g) from 100 g of biomass samples.

Biomass Hexane extract Ethanol extract Water extract Cellulose Hemicellulose Lignin

M. indica 9.65 ± 0.55b 8.68 ± 0.55b 13.39 ± 0.92a 31.23 ± 1.71b 28.02 ± 3.02b 10.56 ± 0.79b
P. deltoides 8.60 ± 0.54c 9.79 ± 0.52a 9.95 ± 0.73b 37.75 ± 4.21a 21.85 ± 1.55c 11.95 ± 0.80a
P. longifolia 10.59 ± 0.81a 10.26 ± 0.66a 8.84 ± 0.53c 26.65 ± 1.64c 32.04 ± 2.19a 10.63 ± 1.18b

Values are mean ± SD (n = 3), bearing different letters in same column are significant at P < 0.05.

litter biomasses may be attributed to high mannose or lignin con-

tent [1]. Similar devolatization patterns were observed with differ-
ent feedstocks such as rice straw, wheat straw, barley straw, flax
straw, pine wood [1], Tamarix ramosissima [2], A. catechu, A. lucida
and Z. rugosa [17], characterized for biofuel production.

3.5. Biomass extractives

The yield of hexane, ethanol and water extracts along with cel-
lulose, hemicelluloses and lignin content of different biomass sam-
ples are presented in Table 4. In terms of total extract, leaf lit-
ter biomass of Mango has maximum extractives (31.72 wt%) fol-
lowed by Ashoka (29.69 wt%) and Poplar (28.34 wt%). Among three
leaf litter biomass studied, Poplar showed greater cellulose con-
tent (37.75 wt%) followed by Mango (31.23 wt%) and Ashoka (26.65
wt%), however, hemicellulose content was in the range of 22–32%.
Comparable range of cellulose (29–39%) and hemicelllulose (26–
34%) content was observed in wheat straw, barley straw, flax straw,
trimothy straw and pinewood [1]. However, greater cellulose (45–
53%) with less hemicelllulose (6–28%) content was observed with
the biomasses of A. catechu, A. lucida, Z. rugosa [17]. Cellulosic and
hemicellulosic component of these biomasses could be used as po-
tential substrate for enzymatic hydrolysis to obtain fermentable
Fig. 3. X-ray diffractograph of leaf litter biomass samples from (a) Mango, (b)
sugar for bioethanol production.
Poplar and (c) Ashoka.

3.6. Fourier transform infrared (FTIR) spectroscopy

Fourier transform infrared (FTIR) spectroscopy analysis was car-

ried out to detect changes in functional groups of different biomass
samples. The obtain FTIR spectrum is represented in Fig. 5 and
assigned fingerprints are summarised in Table 5 based on litera-
ture values [1,2,17,34,35]. The main characteristics were attributed
to different chemical groups present in cellulose, hemicellulose
and lignin components of biomasses. The greater percent trans-
mittance was observed for leaf litter biomass of Poplar followed
by Ashoka and Mango in the range 360 0–30 0 0 cm−1 . This range
represents the hydrogen bonded stretching bands of OH groups, ei-
ther from the glucoside linkages of cellulose or the hydroxyphenyl,
guaiacyl and syringyl groups of lignin [36]. Lignocellulosic biomass
most likely consisted of alkene, esters, aromatics, ketone and alco-
hol, with different oxygen-containing functional groups. The wave
number 140 0–90 0 cm−1 is designated to vibrations of a variety
of bonds such as C–H, C–O, C–N and P–O [37]. Absorption for
wave number in between 1450 and 10 0 0 cm−1 corresponds to a
large family of esters formed between quinic acid and one to four
residues of certain trans-cinnamic acids, most commonly caffeic,
Fig. 4. Thermogravimetric analysis of leaf litter biomass samples from (a) Mango, p-coumaric and ferulic [38], contributing to majority of observed
(b) Poplar and (c) Ashoka. bands. The readily visible peak at 1635 cm−1 was observed in all
three types of biomass samples, and is generally attributed to C=O
stretching of hemicelluloses and deformation vibrations of H–O–H
250–350 °C for loss of hemicellulose, 350–500 °C for loss of cel- in absorbed water [2]. The prominent peak near 1043 cm−1 cor-
lulose, lignin and > 500 °C for lignin. A sharp decline beyond responded to C–O stretching vibration in cellulose and hemicellu-
500 °C was observed with Mango leaf litter biomass, which gener- loses, advocated that all leaf litter biomass samples are rich source
ally shows more cellulose and hemicelluloses content, whereas the of cellulose and hemicellulose and can be used as a promising
slow rate of devolatilization pattern with Ashoka and Poplar leaf feedstock in biorefinery.
244 N. Akhtar et al. / Journal of the Taiwan Institute of Chemical Engineers 62 (2016) 239–246

Table 5
Assignment of FTIR bands of functional groups in different leaf litter biomass.

Name of characteristic group Wavenumber (cm−1 )

O–H stretching in cellulose and lignin 360 0–30 0 0

C–H stretching of aliphatic structure 2960–2850
C=O stretching of hemicelluloses 1750–1630
C–H deformation in cellulose and hemicellulose 1384–1346
Syringyl ring breathing and C–O stretching out of lignin and xylan ∼1232
C–O stretching vibration in cellulose and hemicelluloses ∼1043

Table 6
13
Signal assignments for chemical shifts obtained from solid state C CP/MAS NMR spec-
troscopy of different leaf litter biomass.

Chemical shift (ppm) Assignments

173 Carboxyl group of hemicelluloses

104 Anomeric carbon (C1) of cellulose
83 C4 of amorphous cellulose and hemicelluloses
72 C2, C3, C5 of cellulose, OCα H2 carbon of lignin
63 C6 of crystalline cellulose
32 Methoxyl (–OCH3 ) and methylene (–CH2 ) groups in lignin
23 CH3 in acetyl group of hemicelluloses

Fig. 6. Solid state 13 C CP/MAS NMR spectra of leaf litter biomass samples from (a)
Mango, (b) Poplar and (c) Ashoka.
Fig. 5. FTIR spectra of leaf litter biomass samples from (a) Mango, (b) Poplar and
(c) Ashoka.

content of hemicellulose. The conclusions drawn from NMR spec-

3.7. Solid state 13 C CP/MAS NMR spectroscopy tra (Fig. 5) support the result obtained from chemical analysis
of biomasses for cellulose and hemicellulose content (Table 4).
Solid state 13 C CP/MAS NMR spectra provide characteristic Presence of cellulose and hemicelluloses content of these biomass
chemical shift values ascribed to cellulose, hemicellulose and samples recommend their use as feedstock for bio-energy gen-
lignin, represented in Fig. 6. Signal assignments for various eration. Intense peaks assigned in the region of 50–120 ppm are
biomass samples have been assigned based on the literature attributed mostly to cellulose carbon, contributions from hemicel-
[39–41] and summarised in Table 6. The prominent peak at lulose along with some lignin signals. However, signals from lignin
72 ppm along with peaks at 104, 83 and 63 ppm render a clue for are generally concentrated between 10 0 and 20 0 ppm. An aliphatic
the presence of carbohydrates in Mango, Poplar and Ashoka leaf region for lignin lies from 0 to 95 ppm whereas, an aromatic region
litter biomass samples. A prominent peak at 23 ppm was typically falls in between 100 and 160 ppm [42]. Chemical shift deflection
observed with biomass samples of Ashoka, advocating for a greater for C4 and C6 carbon in the anhydroglucose unit rely upon the cel-
 N. Akhtar et al. / Journal of the Taiwan Institute of Chemical Engineers 62 (2016) 239–246 245

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