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Use of Non-Thermal Plasma in Lignocellulosic Materials - A Smart Alternative

This review discusses the use of non-thermal plasma (NTP) as an environmentally friendly pre-treatment method for lignocellulosic materials, which are rich in cellulose, hemicellulose, and lignin. NTP offers a sustainable alternative to conventional chemical pre-treatments that can harm the environment, enabling the extraction of value-added products like biofuels and renewable chemicals. The document highlights the effectiveness of NTP in breaking down complex biomass structures and its growing application in various fields.
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0% found this document useful (0 votes)
32 views9 pages

Use of Non-Thermal Plasma in Lignocellulosic Materials - A Smart Alternative

This review discusses the use of non-thermal plasma (NTP) as an environmentally friendly pre-treatment method for lignocellulosic materials, which are rich in cellulose, hemicellulose, and lignin. NTP offers a sustainable alternative to conventional chemical pre-treatments that can harm the environment, enabling the extraction of value-added products like biofuels and renewable chemicals. The document highlights the effectiveness of NTP in breaking down complex biomass structures and its growing application in various fields.
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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Trends in Food Science & Technology 109 (2021) 365–373

Contents lists available at ScienceDirect

Trends in Food Science & Technology


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

Use of non-thermal plasma in lignocellulosic materials: A smart alternative


Gabriela N. Pereira a, Karina Cesca a, Anelise Leal Vieira Cubas b, Débora de Oliveira a, *
a
Department of Chemical and Food Engineering, Federal University of Santa Catarina (UFSC), Florianópolis, Santa Catarina, Brazil
b
Environmental Science Master’s Program, University of Southern Santa Catarina (Unisul), Palhoça, SC, Brazil

A R T I C L E I N F O A B S T R A C T

Keywords: Background: Lignocellulosic materials are mainly composed of cellulose, hemicellulose, and lignin. They have
Dielectric barrier discharge (DBD) been extensively used in recent years to obtain new value-added products, such as xylitol, vanillin, activated
Hemicellulose carbon, oligosaccharides, biofuels, among others.
Lignocellulosic materials
Scope and approach: Biomass needs a pre-treatment to promote the breaking of the bonds that link the rigid
Biomass
Xylose
macrostructures. The most common conventional pre-treatments are chemical. However, they cause significant
Lignin damage to the environment since they either use toxic chemicals or produce waste, causing disposal problem.
Non-thermal plasma is considered an environmentally friendly technique and is increasingly explored as a
method of treatment and/or pre-treatment of lignocellulosic materials.
Key findings and conclusions: In this review, we cover the main topics related to the use of non-thermal plasma
technology (NTP) as a clean technology for the treatment of different lignocellulosic materials. We also address
the main works on the subject and the main effects of this promising technology on different biomass. In addition
to the main characterization techniques, we could find that it is possible to use this technique as an effective pre-
treatment for future obtaining value-added products from different residues discarded in large quantities. Then,
the main contribution of this review is to critically show the efficiency of this technology as an innovative and
promising way to the treatment of different lignocellulosic residues.

1. Introduction are not environmentally friendly, leading to the formation of numerous


undesirable compounds, such as aliphatic acids, formaldehyde, and
In the last few years, there has been a great effort to value agro- others (Ravindran & Jaiswal, 2016). This reason encouraged the
industrial wastes and their respective reuse. In this sense, lignocellu­ replacement of conventional unsustainable pre-treatments (for example,
losic materials have been highly considered, making possible to obtain chemical and physical-chemical ones) with sustainable pre-treatments
several value-added products such as biofuels, renewable chemicals, and called “green” (for example, biological pre-treatments) (Saha, Qureshi,
renewable materials (Lopes et al., 2016). Lignocellulosic materials are Kennedy, & Cotta, 2016).
the most abundant organic materials in the biosphere, representing 60% Biological pre-treatments, using microorganisms, are considered
of plant biomass. They are composed of lignin (10%–30%), hemicellu­ sustainable. However, they require an extensive treatment period, low
lose (15%–35%) and cellulose (30%–50%), the composition of which yield, and consumption of carbohydrates by the organisms, being
depends on the raw material in question, age and vegetative stage considered one of the main challenges of this technique (Saha et al.,
(Biswas, Persad, & Bisaria, 2014a). In the conversion of lignocellulosic 2016). Enzymatic hydrolysis is also a promising way because it does not
biomass into biofuels or other products, a pre-treatment step is neces­ generate effluents (ecologically correct), but exclusively enzymatic
sary, taking a fundamental role in the economics of processes. Therefore, depolymerization has low efficiency due to the high natural recalci­
energy-efficient and cost-effective pre-treatment methods are required trance to material, due to the complexity of the chemical interactions
to make the process sustainable and economically viable (Wright et al., between cellulose, hemicellulose and lignin in the plant cell wall (Otieno
2018). & Ahring, 2012). These obstacles encouraged the investigation of other
Conventional pre-treatments require large amounts of energy and pre-treatments for lignocellulosic biomass. One of the not so

* Corresponding author. Universidade Federal de Santa Catarina (UFSC), Departamento Engenharia Química e Engenharia de Alimentos (EQA) – Campus Trindade,
Cx. Postal 476, 88010-970, Florianópolis, SC, Brazil.
E-mail address: [email protected] (D. de Oliveira).

https://doi.org/10.1016/j.tifs.2021.01.047
Received 14 May 2020; Received in revised form 27 September 2020; Accepted 18 January 2021
Available online 23 January 2021
0924-2244/© 2021 Elsevier Ltd. All rights reserved.
G.N. Pereira et al. Trends in Food Science & Technology 109 (2021) 365–373

conventional technologies that are in an increasing application, in the barrier layer and the coolant for the discharge (Ravindran et al., 2019).
pre-treatment of raw materials, is the use of non-thermal plasma (Rav­ Other configurations of the NTP reactor are the dielectric discharge of a
indran et al., 2019). This method has been explored over the last years plane, consisting of a Perspex glass and two steel plates, where studies
and has excellent potential in the most diverse applications, as in the used this plasma configuration in the deconstruction of lignocellulosic
treatment of mammalian cells (Kalghatgi et al., 2011), degradation of material (Lim & Zulkifli, 2018). Plasma configurations of weakly ionized
pharmaceuticals in wastewater (Krishna et al., 2016), treatment of oxygen have also been tested for lignocellulosic materials (Praveen
biofilms (Gupta & Ayan, 2019), treatment of water and sewage (Cubas et al., 2016). In general, it is known that the electrical discharge plasma
et al., 2019; Hashim et al., 2016), aid in the degradation of p-nitrophenol in contact with water, by generating many types of reactive species and
in water (Shang, Li, Wang, et al., 2019), degradation of dye in water molecular species, in addition to UV irradiation and shock waves, is
degradation of dye in water (Jo, Moon, & Mok, 2015), pre-treatment of capable of efficiently destroying recalcitrant organic compounds,
lignocellulosic waste (Miranda et al., 2019; Ravindran et al., 2019), mainly due to its efficient generation of the strongest electron radical
among others. oxidant OH (Shang, Li, & Morent, 2019). The most common discharge
In the non-thermal plasma technique, plasma is produced using a regimes for the generation of NTP in the laboratory are: corona
dielectric barrier (DBD) discharge, to improve a later stage of access of discharge, dielectric barrier discharge (DBD), spark discharge (from
the enzyme complex to the lignocellulosic matrix (Kriegseis, Möller, English spark discharge), streamer, light discharge (from English glow
Grundmann, & Tropea, 2011). This method has proved to be interesting, discharge) etc. (Jiang et al., 2014; H.; Zhang, Ma, Qiu, Tang, & Du,
as the process can be carried out at atmospheric pressure and use at­ 2017), these being characterized by an energetic electron temperature
mospheric air as exhaust gas, making the cost of the operational process much higher than that of bulk gas molecules. In this review, we will only
and maintenance low due to the absence of a vacuum chamber (Žigon, address the non-thermal plasma technology as it is a technology that
Petrič, & Dahle, 2018). This technology can be considered a promising does not use high temperatures.
substitute for conventional and aggressive techniques aiming to obtain
value-added products, such as biofuels, renewable chemicals, and 2.1. Non-thermal plasma (NTP)
renewable materials from different lignocellulosic materials.
In this context, the present review aims to present the main concepts Non-thermal plasma (NTP) is a partial electrical discharge initiated
and mechanisms of action of non-thermal plasma in different materials, at sufficient voltages. Partial electrical discharges cause the electron
in addition to the main characterization techniques used so far. It is temperature to be higher than the temperature of the surrounding gas
worth noting that this is the first review exposing the primary studies of molecules. Electrons interact with gas molecules to generate active
the use of this promising and eco-friendly technique in residual biomass, radicals, reactive species and, ions, which have higher levels of energy,
particularly for lignocellulosic materials. increasing the rate of reactions (Wu, Hong, Ouyang, Cho, & Ruzic,
2013). Plasma is technologically generated by electric or electromag­
2. Plasma netic fields and is generally indicated as discharge plasma (Carlsson &
Strom, 1991). These dielectric barrier discharges can be generated in
The concept of plasma emerged in 1879, when William Crooks used many configurations (Wolf, 2012). It generally consists of metallic
and defined it as the fourth state of matter. It was only in 1928 that the conductive electrodes, mainly refrigerated, connected to a high voltage
term “plasma” was used by the American chemist Irving Langmuir source of alternating polarity (Král et al., 2015). An electric field with
(Kalia, Thakur, Celli, Kiechel, & Schauer, 2013). Plasma is a diversified sufficient field forces is generated by applying a high voltage to the
and unique medium for modifying the surface of plant fibers, as it space between the electrode and the material, where the electrical break
contains a mixture of reactive species such as free radicals, electrons, occurs (Wolf, 2012) and a stable plasma state is formed (Zanini et al.,
and massive particles, being defined as a gaseous environment 2008). The total charge is approximately zero, that is, the number of
composed of charged and neutral species with a total density zero load. electrons is equal to the sum of the positive and negative ions multiplied
The transformations of the physical states of matter happen with the by their respective costs (Esteves Magalhães & Ferreira de Souza, 2002).
gain of energy (Fig. 1). Therefore, plasma is a partially or fully ionized The positive electrode accelerates free electrons. After impact, they
gas made up of electrons, ions, excited and neutral molecules, reactive dissociate gas molecules producing ionization and fragmentation. Ions
species, and photons (Fridman, 2008; Jiang et al., 2014). and electrons continue to collide with other atoms and gas molecules
Plasma is classified according to the temperature, density and, en­ and promote an avalanche of electrons (Wagner et al., 2003).
ergy level of the species that make it up (Fridman, 2008). Thus, we can Fig. 2 shows different types of plasmas. In 2.1 shows a schematic
consider high-temperature plasma or thermal plasma that with tem­ drawing of a liquid plasma reactor, with (1) sample port (2) electrodes
peratures above 3000 K and low temperature or non-thermal plasma (3) Teflon cover (4) glass chamber (5) grounded metal plate (6) inlet gas
that with temperatures below 1000 K (Gao, Uner, Thimsen, & Foston, (7) gas inlet (7) gas outlet. In (b), there is the plasma discharge, in which
2018). In the literature, there are different configurations of plasmas the yellowish color of the discharge is due to the sodium environment
used in lignocellulosic materials. Dielectric barrier plasmas, for inside the reactor and in (c) there is a schematic drawing showing the
example, employ a conventionally coaxial electrode configuration. The distance between the plasma discharge and the surface of the liquid in
high voltage electrode is sealed in a quartz tube, submerged in the the reactor. In 2.2, Weakly ionized oxygen plasma. In 2.3 Plane to plane
treated liquids, so that the liquid serves as an additional dielectric dielectric barrier discharge reactor, consisting of a Perspex glass and two
steel plates and in 2.4 Plasma enhanced fluid bed reactor (PEFBR).

2.2. Non-thermal plasma: an overview of potential applications

The growing number of publications that use non-thermal plasma


(Fig. 3) highlights the importance of this technology, which has
increased in recent years. These surveys show an average advance of
approximately 17 times more publications related to the topic in 2019
(376 documents) when compared to the 2000s (22 papers), generating a
total of about 2930 article documents in that period, when using the
Fig. 1. Illustration of the physical transformation of the state of matter with words "nonthermal plasma "or" non-thermal plasma ". This interest is
energy gain. due to the NTP technology, as it presents characteristics such as clean

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G.N. Pereira et al. Trends in Food Science & Technology 109 (2021) 365–373

Fig. 2. Schematic drawing of the plasma-liquid reactor. Source: Miranda et al. (2019).

others. Among the documents found in this review, we will use the eight
main articles on the topic “use of NTP in lignocellulosic materials”,
because despite the amount of work has increased over the years, only a
small number of studies are focused on this use.
Some research studies have investigated the effects of plasma
application on different lignocellulosic materials, such as bunches of
empty palm fruits (Lim & Zulkifli, 2018), coffee grain spent (Ravindran,
Jaiswal, Abu-Ghannam, & Jaiswal, 2017), lignocellulosic natural coir
fibers (Praveen et al., 2016), spent brewery grain (Ravindran et al.,
2019), sugar cane bagasse (Miranda et al., 2019) to verify its effec­
tiveness as a pre-treatment to obtain value-added products.

2.3. Use of non-thermal plasma in lignocellulosic materials

Lignocellulosic materials are found in almost all materials derived


from plants, from wood, grass to agricultural waste and municipal solid
waste (S. Yang, 2007). Examples of these materials are Switchgrass,
Hardwood (hybrid poplar), Softwood (pine), Corncob, Rice straw,
Fig. 3. Number of publications related to non-thermal plasma between the
years 2000 and 2019. Source: Scopus, Web of Science and Science Direct, key- Bagasse, among others (Hamelinck, Van Hooijdonk, & Faaij, 2005).
word “non-thermal plasma” OR “nonthermal plasma”. Nowadays, these materials as being wheat straw, rice straw, cane
bagasse, corn cobs, among others are used, for example, for the pro­
duction of lignin-modifying enzymes. Many significant efforts are
technology, with an enormous advantage to the drastic reduction of
devoted to converting these lignocellulosic products into value-added
pollutants and a corresponding reduction of costs in the treatment of
products others, including too compounds, fine chemicals, animal
effluents, in addition to being easy to handle.
feed, cellulose and paper, biofuels. (Bilal, Asgher, Iqbal, Hu, & Zhang,
Plasma has potential applications in several research areas, with
2017). The composition of the lignocellulosic material in the residues
works for example that include the use of NTP technology in fabrics,
may change depending on the genotype and environmental conditions.
where this technique helps in improving the ability to print on fabrics
This type of content is generally composed of a large fraction of cellulose
(Morent et al., 2008). In the treatment of water and wastewater (Hashim
(40–50%), followed by hemicellulose (25–30%) and lignin (15–25%)
et al., 2016), in the treatment of mammalian cells, proving the inter­
(Biswas, Persad, & Bisaria, 2014b). A representation of the structures of
action of plasma with cells at the molecular level (Kalghatgi et al.,
the cell wall of lignocellulosic materials and their chemical structures is
2011), in the degradation of pharmaceuticals in wastewater (Krishna
presented in Fig. 4.
et al., 2016), in the treatment of biofilms, where the promising nature of
The main component of lignocellulosic materials is cellulose, a
technology to eradicate biofilms in the medical field is clearly shown
polysaccharide formed by glucose molecules joined by β-1,4-glycosidic
(Gupta & Ayan, 2019), in the decomposition of volatile organic com­
bonds. These fibrils are joined to each other through hemicellulose.
pounds (VOCs) (Schmidt, Jõgi, Hołub, & Brandenburg, 2015), use of
Hemicellulose is the second most abundant polysaccharide in plants (W.
cold-atmospheric plasma in oncology (Dubuc et al., 2018), among
Yang et al., 2015). Hemicellulose molecules are present by several

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G.N. Pereira et al. Trends in Food Science & Technology 109 (2021) 365–373

Fig. 4. Representation of the structures that form the plant cell wall.

polymers consisting of pentoses (D-xylose and D-arabinose) and hexoses of the LCMs. One aspect that must be emphasized when dealing with
(D-mannose, D-glucose, and D-galactose) with xylose as the most abun­ non-thermal plasma, is that despite its numerous advantages, it can
dant sugar (Kumar, Singh, & Singh, 2008). Also, uronic acids (D-glu­ consume electrical energy. In this sense, several homogeneous and
curonic, D-galacturonic, and methylgalacturonic acids) may also be heterogeneous catalysts are used for the catalysis of ozone and hydrogen
present in branched chains (Limayem & Ricke, 2012). Hemicellulose peroxide and to cooperate with UV effect to improve the degradation of
polymers are often interconnected by covalent and hydrogen bonds. pollutants in water, for example. A range of homogeneous (Fe2+, Fe3+)
Lignin is a heterogeneous amorphous polymer, insoluble in water, and and heterogeneous (non-doped metal oxides) catalysts obviously im­
composed of three aromatic alcohols, also called monolignols, corre­ proves pollutant degradation compared to plasma alone (Shang, Li, &
sponding to propyl phenol units: p-coumaric alcohol, coniferyl alcohol Morent, 2019).
and synaphyl alcohol (Anwar, Gulfraz, & Irshad, 2014). Table 1 shows the different types of lignocellulosic raw materials that
Non-thermal plasma can assist as a pre-treatment of biomass, the have been pre-treated with non-thermal plasma.
central aspect when using this technology is the delignification of Among the biomasses explored with the plasma technique to date we
lignocellulosic material. With this, portions of lignin, cellulose, and have the wheat straw (Schultz-Jensen, Kádár, Thomsen, Bindslev, &
hemicellulose can be obtained separately, each of which is a source of Leipold, 2011), coffee grain spent (Ravindran et al., 2017), lignocellu­
value-added products. Lignin, for example, can be used to get products losic natural coir fibers (Praveen et al., 2016), waste bunches of empty
of commercial value such as activated carbon (Hayashi, Kazehaya, palm fruit (Lim & Zulkifli, 2018), used grains from brewing industries
Muroyama, & Watkinson, 2000) and vanillin (which applied in the (Ravindran et al., 2019), grasses (Gao et al., 2018), grass (Wright et al.,
production of herbicides, antifoaming agents, and antimicrobial agents 2018) and also the sugarcane bagasse (Miranda et al., 2019). Some more
(Walton, Mayer, & Narbad, 2003)). The delignified part, that is, rich in recalcitrant biomasses were investigated, for example, sawdust was used
cellulose and hemicellulose, can be also used to obtain products with as one of the raw materials in a study, but the intention was the plasma
added value. Hemicellulose is a source of xylose, from which xylitol liquefaction of lignocellulosic biomass in order to obtain maximum
comes, which is used as a sweetener (Wölnerhanssen, Meyer-gerspach, energy yield and not with focus in a pre-treatment to assess the structure
& Islam, 2019), in addition to dental use (Joseph, 2017) and furfural, after using plasma (Mei et al., 2020).
used in the manufacture of plastics, solvents) (Mamman et al., 2008), These are some of the few studies that used lignocellulosic materials
soil improvers (Chun’ai Dai, Liu, Girisuta, & Heeres, 2010), cellulose can and sought to evaluate the efficiency of non-thermal plasma technology
also be used to obtain second-generation ethanol (bioethanol) (J. Zhang, as a different pre-treatment method, since it has the advantages of not
Liu, Kou, Zhang, & Tan, 2019) and pharmaceutical applications (Kul­ being toxic, non-polluting, with proven efficacy in lignin extraction,
karni & Dixit, 2011). which is one of the problems faced in other conventional pre-treatment
The non-thermal plasma technique has the advantage of attacking methods tested for these materials.
the lignin of the lignocellulosic material (Miranda et al., 2019). This is a When compared to pretreatment with conventional steam blast,
very important aspect when, for example, the final product of interest some studies reported that the efficiency of 90% enzymatic hydrolysis
are xylo-oligosaccharides, where the portion of interest is hemicellulose was achieved in 24 h, but due to the high temperature achieved in the
(Vázquez, Alonso, Domínguez, & Parajó, 2000). Hydrothermal treat­ process, some sugars were degraded (Grous, Converse, & Grethlein,
ment has the disadvantages of forming inhibitors depending on the 1986). Studies with alkaline hydrolysis in beer residue reached 75 g/l of
severity of the process and solubilizing hemicellulose (Nanda, Moham­ reducing sugar after enzymatic hydrolysis. This study involved the use of
mad, Reddy, Kozinski, & Dalai, 2014), which depending on the desired concentrated alkalis to digest lignin fibers. The alkaline treatment was
final product, would not be ideal. preceded by the removal of hemicellulose with sulfuric acid (Liguori
Therefore, this NTP technology becomes extremely interesting, for et al., 2015). A thermomechanical pretreatment was developed for
use in the pre-treatment phase of the most varied raw materials, seeing brewing waste by Pierre et al. (2011) where a DIC reactor was used,
the amount of products that can be obtained from the different portions where Using a variety of processing pressures, the researchers were able

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G.N. Pereira et al. Trends in Food Science & Technology 109 (2021) 365–373

Table 1 among others. Ozone, for example, is a powerful oxidizer, with an


Use of non-thermal plasma in different lignocellulosic materials. oxidation potential of 2.08 V that can cleave carbon double bonds that
Raw material Why the plasma was Main results Authors are abundant in lignin, whereas hydronium ions are the basis for
used? determining the pH of aqueous solutions (García-Cubero,
Wheat straw Potential for the Extent of plasma Schultz-Jensen González-Benito, Indacoechea, Coca, & Bolado, 2009). In fact, the
production of lignin removal over et al. (2011) higher its concentration, in contrast to the concentration of hydroxyl
bioethanol by time, thereby ions, the more acidic the solution is, and the lower the concentration of
fermentation reducing hydronium ions in favor of the concentration of hydroxyl ions, the more
recalcitrance
Lignocellulosic Investigations of Changes in surface Praveen et al.
alkaline (basic) is the solution. These species react with chemical
natural coir plasma induced topography have (2016) structures of nearby lignocellulosic materials to effectively disintegrate
fibers effects on the been confirmed certain parts of these chemical structures. The ozone molecule, typically
surface properties after treatment generated in abundance in air plasmas, can specifically attack the lignin
with plasma
of the treated material (Fig. 5), leaving cellulose and hemicellulose
Coffee spent Evaluation of Conservation of a Ravindran et al.
waste different techniques large part of the (2017) intact, which is the direct degradation (Ravindran et al., 2019). Besides,
such as pre- hemicellulose it is also possible to carry out the indirect degradation of the lignocel­
treatment fraction along with lulosic matrix through UV light and shock waves (Bruggeman, Degroote,
the removal of acid- Leys, & Vierendeels, 2007). These chemical species (O3) produce UV
insoluble lignin
Empty fruit Investigatation of Changes in residue Lim and Zulkifli
light between the liquid plasma interfaces and, consequently, photo­
bunches NTP effects on morphology, (2018) chemical reactions could take part in the activation of hydrogen
surface reactivity, increased surface peroxide environment breaking the form of O and OH.
morphology, reactivity, changes Oxygen (O) and hydroxyl groups (OH), being proton acceptors when
changes in in lignin structure
in a plasma reactor, cause the chemical interaction between the Brønsted
associated
functional groups bases, resulting from air discharge and the lignin structure of the
and chemical bonds, lignocellulosic biomass to occur, which causes deprotonation of lignin.
chemical Deprotonated lignin molecules are soluble at pH higher than 7 due to the
elimination interaction of the binding (Wright et al., 2018). During plasma treat­
reactivity and
ment, the buffered solution has an amphoteric behavior, that is, it can
surface morphology
Switchgrass Evaluation of the Significant Gao et al. behave as an acid or as a base, depending on the other reagent present,
(grasses) deconstruction of hydrocarbon yield, (2018) using hydrolysis of the bicarbonate ion to restore pH and provides pH
lignocellulosic where the biomass balance during all plasma treatments, as described in Equations (1) and
biomass carbon generated
(2) with reversible reactions.
methane
Miscanthus grass Efficacy of plasma Reactive species Wright et al. HCO−3 + H2 O ↔ CO2−3 + H3 O+ (1)
as an alternative produced by (2018)
pre-treatment plasma attacked
method for biofuel biomass and HCO−3 + H2 O ↔ H2 CO3 + OH − (2)
production released lignin in
the solution
Miranda et al. (2019), using plasma technology combined with pH
Wasted grain Improve the Increased Ravindran et al. buffered solution (pH 12) had a positive effect on the lignin solubiliza­
brewer subsequent step of efficiency in (2019) tion (about 58.5%), which helped in enzymatic hydrolysis and provided
enzymatic enzymatic a high solubilization yield of acetyl groups present in the hemicelluloses
hydrolysis for hydrolysis by
(Miranda et al., 2019).
bioethanol removing
production lignocellulose The initial pH of the solution exposed to the plasma plays an essential
recalcitrance role in the process of degradation of the chemical structures that make
Sugarcane Evaluation of Positive effect on Miranda et al.
bagasse biomass lignin (2019)
delignification solubilization,
efficiency caused by which contributed
plasma treatment to the enzymatic
hydrolysis process
and favored a high
carbohydrate
solubilization yield

to obtain a maximum glucose yield of 24 g per 100 g of waste. The


reducing sugar produced by the new dielectric barrier discharge plasma
was comparable to the values obtained for different pretreatment stra­
tegies (Ravindran et al., 2019).
According to Table 1, we can see that the central studies to date are
related to the use of lignocellulosic materials for later production of
biofuels. Much can still be explored due to the extensive list of high
added value products that can be obtained from different fractions from
biomass (cellulose, hemicellulose, and lignin).

2.4. Effects of using non-thermal plasma as pre-treatment on LCMs

Atmospheric pressure plasma is a source of highly reactive species, Fig. 5. Schematic drawing of the air environment in the plasma forming ozone,
such as ozone (O3), hydroxyl radical (OH), hydronium ions (H3O+), which helps in the cleavage of double bonds of lignocellulosic materials.

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G.N. Pereira et al. Trends in Food Science & Technology 109 (2021) 365–373

up the lignocellulosic material. Direct reactions (O3 attacking lignin) are oxidizing potential.
prevalent in acidic environments (low pHs) and are efficient processes The reaction of the hydroxyl radical contributes more to the change
for compounds with functional groups, aromatic (phenolic) systems, or in pH (to some extent, pH < 8), which increases the efficiency of lignin
with double bonds (as is the case with lignin in LCMs) (Sarangapani, Lu, removal (Sarangapani et al., 2018). However, at pH values higher than
Behan, Bourke, & Cullen, 2018). When the nitrogen atmosphere is used 8.5, the formation of HO−2 occurs, which can eliminate a certain per­
for the formation of NTP, important reactive nitrogenous species (RNS) centage of OH radicals, consequently reducing the efficiency of the
are formed (Cadorin et al., 2015). When air (N2 + O2) is used to form the pre-treatment process (Ravindran et al., 2019).
NTP, reactive oxygen species (ROS) and reactive nitrogen species (RNS) Another aspect in relation to the use of ozone as a pre-treatment is
are formed (Jiang et al., 2014). From the secondary nitrogen and oxygen that although it is widely reported to not produce inhibitory/toxic
species, other species are produced according to Eqs. (Crema, Piazza products that can affect fermentation enzymes or bacteria, the nature of
Borges, Micke, & Debacher, 2020): the degradation products depends on the type of biomass and the
products of plasma dissolved in the pre-treatment liquid. Ozonation
H2 O2 + NO−2 + H3 O+ → ​ ONOOH + H2 O2 (3)
studies of wheat straw showed that among the inhibitory compounds
produced, significant increases in the concentrations of oxalic acid and
ONOOH + H2 O ↔ ONOO− + H3 O+ (4)
acetovanilone were observed (Schultz-Jensen et al., 2011).
ONOOH→HNO3 (5)
2.5. Main changes observed in LCMs after using the NTP technique
However, some studies indicate that a low pH environment leads to
reduced efficiency of plasma-induced lignin. This is attributed to the Several changes occur in the structure of a lignocellulosic material
formation and accumulation of strong acids, such as nitric acids, nitrous after applying a pre-treatment technique, it is no difference with plasma.
acid and other carboxylic acids (Su, Ito, Kim, Takashima, & Mizuno, These changes can be observed by different techniques such as Fourier
2002). Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy
At higher pH, indirect oxidation through O3 and H2O2 predominates (SEM), Differential Scanning Calorimeter (DSC), and Atomic Force Mi­
and results in the formation of OH radicals (Lukes, Appleton, & Locke, croscopy (AFM) (Fig. 6). These techniques can be addressed together to
2004). In the pH range between 6.5 and 8.5, for example, the radicals O3 analyze better the changes that have occurred.
and OH predominate in the disintegration process of the lignocellulosic Fourier Transform Infrared Spectroscopy (FTIR), for example, is a
matrix, with the oxidative capacity of O3 interrupting the carbon double qualitative technique that indicates compositional changes in biomass
bonds present in the aromatic rings (Grabowski, Van Veldhuizen, based on the presence or absence of functional groups belonging to
Pemen, & Rutgers, 2007). This probably leads to better lignin removal cellulose, hemicellulose, and lignin (Ravindran et al., 2019). Physical
efficiencies in the pH range between 6.5 and 8.5, in which the oxidation methods such as FTIR have also been used to characterize natural con­
potential of the OH radical (2.80 V) is significantly greater than that of stituents of biomass, such as lignin, extractives, hemicellulose, methoxy,
O3 (2.08 V). Secondary species (OH, NO−2 , NO−3 , H2O2, HNO3, H3O+) are and aromatic hydroxyl groups, among others (Lu et al., 2017). Charac­
also responsible for decreasing the pH and increasing the conductivity of teristic peaks usually related to lignocellulosic raw materials in this
the medium (Cubas et al., 2019). This is due to the dissociation of water technique are related to glycosidic bonds, double bonds between car­
that occurs under the plasma, which leads to acidification of the medium bons, aryl-alkyl ether (C–O–C) bonds, where a decrease in the peak after
and formation of oxidizing species. Depending on the radical formed, plasma use, indicates changes in main structure material (Ravindran
there is an increase in conductivity with the plasma treatment time and et al., 2019). This decrease was observed in beer residue after
this increase results from the production of ions, demonstrating that the pre-treatment with plasma (Ravindran et al., 2019). Changes in the
active ions were generated due to the activation of the plasma. That is, syringil and guaiacyl components of lignin and in the carboxyl and
these consequences occur depending on the radical formed and its carbonyl groups were also verified by this technique in empty fruit

Fig. 6. Schematic drawing of the Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR), Differential Scanning Calorimeter (DSC),
and Atomic Force Microscopy (AFM) analyzes, which can be performed before and after pre-treatment using non-thermal plasma for evaluation purposes of the
structure in the pre and post treatment.

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clusters of sprayed palm trees, before and after plasma treatment (Lim & the exposure of the material in a liquid next to the plasma, because the
Zulkifli, 2018), where the decrease in absorbance at the syringil and contact of the lignocellulosic material with water causes the swelling of
guaiac peaks was verified. By the same technique (FTIR), the conser­ the material to occur, increasing the surface area, which allows a greater
vation of hemicellulose in spent coffee beans was observed after the use penetration of reactive species in the material. This fact was also verified
of plasma. This was verified by the peak value before and after the in Michantus grass (Wright et al., 2018), and proves the importance of
remain the same (Ravindran et al., 2017). using plasma in a liquid medium.
Another technique that assesses changes caused by pre-treatments in Fig. 7 presents an example of images that can be obtained by the SEM
the physical properties of biomass is Differential Scanning Calorimeter and AFM techniques of sugarcane bagasse to highlight the images
(DSC), being a non-specific diagnostic tool to obtain in a single step the captured by these two different techniques for the same raw material.
entire pattern of phase transitions that occur during a temperature scan
(Brys, 2016). Changes of this nature were observed in brewery residue, 3. Conclusions and future perspectives
after treatment with NTP, with a decrease in melting temperature from
361.05 ◦ C to 309.9 ◦ C (Ravindran et al., 2019). As lignin has specific The growing concern with the final destination of lignocellulosic
characteristics due to its high degree of association between its macro­ residues (LCMs) has increasingly attracted the attention of researchers in
molecules, it decomposes at higher temperatures due to its compacted making possible to transform this type of material into products that can
and interconnected propane units in a complex amorphous matrix add value until they reach the consumer. These materials have high
(Pishnamazi, Iqbal, Shirazian, Walker, & Collins, 2019).Consequently, recalcitrance due to the chemical composition, therefore the need for
that treatment with NTP altered the structure of lignin, decreasing its pre-treatment steps that help to reduce resistance.
stability, and consequently decreasing its melting temperature. Many alternatives are tested; however, it is known of a large amount
Scanning Electron Microscopy (SEM), on the other hand, is a tech­ of toxic residues and solvents that are used in conventional techniques.
nique that aims to obtain information about the morphology and surface In this line of reasoning, it appears that in recent times there has been a
roughness of lignocellulosic materials (Okenwa et al., 2020). After significant advance in research involving the use of non-thermal plasma
plasma treatment in biomass of empty palm fruit clusters, changes in the (NTP), as evidenced by the increase in the number of publications. In
raw material surface morphology were observed (Lim & Zulkifli, 2018). addition, this technique has proved, by means of few studies, to be
These changes may have occurred because NTP induces lignin exposure effective when used as a pre-treatment in lignocellulosic materials.
and crystalline portions of cellulose (Xie, Tang, Jiang, Breedveld, & Understanding the modes of action of NTP specifically in LCMs is of
Hess, 2015). Some “flaws” were observed in the sugar cane bagasse after utmost interest because through different characterization techniques
2 h of treatment, which the authors stated would be an effect of the such as SEM, FTIR and DSC, the main changes caused in biomass can be
plasma on the fibers of the material, with the removal of the layers that proven when using this technique. The NTP technique is considered
covered the fibers (this layer, with a glue-like structure, composed of adequate, non-polluting, and non-toxic, which makes it attractive and a
fibril structures connected by a xyloglucan) (Fig. 7 (b) and (c)) (Miranda tendency to be further explored.
et al., 2019). The biomass of Mischantus grass, treated under different Based on the few studies found in the literature using NTP in ligno­
operating conditions (2 and 4 h) of plasma, was analyzed by SEM. Minor cellulosic materials, an important direction in the future would be the
structural damage, probably to the lignin structure, was observed after 2 use of this technique as a pre-treatment in LCMs, focused on a larger
h of dry pre-treatment, and after 4 h of treatment, it presented more range of value-added products, after the total separation of cellulose,
significant localized damage (Wright et al., 2018). In coconut lignocel­ hemicellulose, and lignin. An up-and-coming trend is the branch of
lulosic fibers, after 10 s of exposure to plasma, changes in morphology biorefinery, where all extracted parts (cellulose, hemicellulose and
were observed for technical SEM, as the surface appeared to be etched lignin) could be used separately. For example, by concentrating the
by reactive oxygen species and became softer (Praveen et al., 2016). amount of hemicellulose in the biomass, the use of specific enzymes such
Another technique that has the function of detecting morphological as xylanases could be efficient in obtaining xylooligosaccharides, which
changes resulting from the pre-treatment is the Atomic Force Micro­ are xylose oligomers with prebiotic properties, which are increasingly
scopy (AFM). This technique provides three-dimensional images of the attracting interest in the food area. The liquid part (rich in lignin) can be
surface (García, 2002). AFM analysis of coconut lignocellulosic fibers for explored when isolated from black liquor to obtain various products of
example, allowed to observe differences in surface topography and commercial interest, such as activated carbon, vanillin, phenols, ben­
viscoelastic properties at the nanoscale (Praveen et al., 2016). Taken zene, fertilizers, polymers, among others. Cellulose, on the other hand,
together, the SEM and AFM analysis confirmed that the plasma had a enriches this biorefinery chain in obtaining biofuels, which has been
marked effect on the pretreated sugarcane bagasse biomass, removing seen in some studies so far.
the layers that covered the fibers of the material. The effect of plasma on Therefore, knowing that the pre-treatment stage is one of the most
the liquid was not limited to the sample surface, but also changed the important stages of a process, it is necessary to search for a practical and
volume of sugarcane bagasse, a fact has proven after enzymatic hydro­ economical method, with the minimum or nonexistent use of chemicals
lysis (Fig. 7(d)) (Miranda et al., 2019). The fact of the change in the and that preserves the maximum amount of cellulose and hemicellulose.
volume of the structures of lignocellulosic materials, is due to the fact of With this, it is suggested that NTP technology be further explored, as it

Fig. 7. (a) Cane bagasse in nature; (b) and (c) SEM images of cane fibers after plasma pre-treatment and (d) AFM image of the cane fiber structure after plasma
treatment, which shows the structure of cellulose and microfibrils bound by xyloglucans. Source: Miranda et al. (2019).

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Declaration of competing interest Hashim, S. A., Samsudin, F. N. D. binti, Wong, C. S., Abu Bakar, K., Yap, S. L., Mohd,
et al. (2016). Non-thermal plasma for air and water remediation. Archives of
All of authors declare that they have no conflict of interest. Biochemistry and Biophysics, 605, 34–40. https://doi.org/10.1016/j.abb.2016.03.032
Hayashi, J., Kazehaya, A., Muroyama, K., & Watkinson, A. P. (2000). Preparation of
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Acknowledgments https://doi.org/10.1016/S0008-6223(00)00027-0
Jiang, B., Zheng, J., Qiu, S., Wu, M., Zhang, Q., Yan, Z., et al. (2014). Review on
electrical discharge plasma technology for wastewater remediation. In Chemical
The authors acknowledge the financial support of Conselho Nacional engineering journal (Vol. 236, pp. 348–368). https://doi.org/10.1016/j.
de Desenvolvimento Científico e Tecnológico (CNPq). The authors are cej.2013.09.090
also grateful to CAPES-PRINT, Project numbers 88887.310560/2018-00 Jo, J. O., Moon, S. H., & Mok, Y. S. (2015). Non-thermal plasma degradation of dye using
an underwater dielectric barrier discharge created inside a porous hydrophobic
and 88887.310727/2018-00.
ceramic tube. Coloration Technology, 131(2), 73–80. https://doi.org/10.1111/
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