Journal of Cleaner Production 333 (2022) 130180

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Journal of Cleaner Production

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

Emerging approaches in lignocellulosic biomass pretreatment and

anaerobic bioprocesses for sustainable biofuels production
Ramesh Kumar a, Tae Hyun Kim b, **, Bikram Basak a, Swapnil M. Patil a, Hoo Hugo Kim a,
Yongtae Ahn c, Krishna Kumar Yadav d, Marina M.S. Cabral-Pinto e, Byong-Hun Jeon a, *
a
Department of Earth Resources & Environmental Engineering, Hanyang University, 222-Wangsimni-ro, Seongdong-gu, Seoul, 04763, Republic of Korea
b
Department of Materials Science and Chemical Engineering, Hanyang University, Ansan, Gyeonggi-do, 15588, Republic of Korea
c
Center for Environment, Health and Welfare Research, Korea Institute of Science and Technology (KIST), Hwarang-ro 14, Seongbuk-gu, Seoul, 02792, Republic of
Korea
d
Faculty of Science and Technology, Madhyanchal Professional University, Ratibad, Bhopal, 462044, India
e
Geobiotec Research Centre, Department of Geoscience, University of Aveiro, 3810-193, Aveiro, Portugal

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

Handling Editor: Cecilia Maria Villas Bôas de The development of advanced biofuels from waste organic matter, such as lignocellulosic biomass, is critical for
Almeida global sustainable waste management and to delay climate change by reducing greenhouse gas emissions via
partial replacement of fossil fuels. However, the inherent recalcitrance of lignocellulosic biomass due to the
Keywords: presence of inhibitory components, mainly lignin, limits the hydrolysis of its carbohydrate content, representing
Lignocellulosic biomass
a key hurdle augmenting biofuel production. Therefore, pretreatment of lignocellulosic biomass is crucial to
Biomass recalcitrance
promote its fragmentation, increase its surface area and solubility, and lower the cellulose crystallinity and lignin
Green pretreatment technologies
Omics technology content for sustainable biorefinery. Conventional pretreatment processes have several drawbacks, including high
Anaerobic bioprocesses operational costs, corrosion of equipment, and generation of toxic effluents and by-products. To offset the
Biofuels negative impacts of these limitations on biofuel production, here, we have discussed and critically compared
various eco-friendly approaches for the efficient conversion of biomass to ensure high yields of biofuels as a
commercial solution. Moreover, a range of microbes and enzymes have been highlighted that effectively utilize
lignocellulosic biomass to obtain energy and convert its complex polymeric structure into a biodegradable one,
facilitating its subsequent valorization. Furthermore, the importance of multi-omics approaches was discussed to
gain functional insights into the lignocellulolytic microbial communities and their interspecies symbiosis during
the hydrolysis of organic biomass. Finally, the limitations of previous studies, challenges, industrial perspectives,
and future outlooks for the development of economical, energy-saving, and eco-friendly strategies toward the
sustainable valorization of lignocellulosic biomass were summarized.

which is an attractive feedstock for anaerobic bioprocessing (Cheng

1. Introduction et al., 2020). This will help to meet the global energy demand, reduce
the dependence on fossil fuels, and reduce greenhouse gas (GHG)
The bioeconomy of the 21st century has encouraged the development emissions by 20–70%, thereby encouraging sustainable green growth
of novel economic models to curtail the utilization of natural resources (Xu et al., 2016).
for economic prosperity and ecological survival (Hassan et al., 2018; Biorefineries can be used to produce energy, value-added chemicals,
Kumar et al., 2020a). Global warming and climate change, environ­ bioplastics, and fuels using renewable and non-edible feedstocks, such as
mental deterioration, and consequent increase in pollution-related LCB and food waste biomass, to drive society towards a sustainable
health hazards are significant threats due to the ever-growing demand economy (Sriariyanun et al., 2021). However, numerous challenges,
and consumption of fossil fuels (Kazemi Shariat Panahi et al., 2019). such as the presence of inhibitory molecules and the structural
Intense efforts are being made to channelize sustainable energy from the complexity of LCB due to cross-linking between polysaccharides (cel­
largest renewable carbon source, the lignocellulosic biomass (LCB), lulose and hemicellulose) and phenolic polymers (lignin), critically

* Corresponding author.
** Corresponding author.
E-mail addresses: [email protected] (T.H. Kim), [email protected] (B.-H. Jeon).

https://doi.org/10.1016/j.jclepro.2021.130180
Received 17 September 2021; Received in revised form 6 December 2021; Accepted 17 December 2021
Available online 21 December 2021
0959-6526/© 2021 Elsevier Ltd. All rights reserved.
R. Kumar et al. Journal of Cleaner Production 333 (2022) 130180

Abbreviations LCC Lignin carbohydrate complex

LC-MS Liquid chromatography-mass spectrometry
ABE Acetone-butanol-ethanol LC-MS/MS Liquid chromatography-tandem mass spectrometry
AD Anaerobic digestion LPMOs Lytic polysaccharide monooxygenases
APSs Atmospheric plasma sources MWI Microwave irradiation
BSG Brewer’s spent grain NGS Next-generation sequencing
CAZymes Carbohydrate-active enzymes NIMS Nanostructure initiator mass spectrometry
CBP Consolidated bioprocessing OUT Operational taxonomic unit
CS Cornstalk PE Plasma electrolysis
DES Deep eutectic solvent PEF Pulse-electric field
DP Degree of polymerization PNS Purple non-sulfur
EB Electron beam PUL Polysaccharide utilization loci
EU European Union SC-CO2 Supercritical carbon dioxide
FTIR Fourier transform infrared SEM Scanning electron microscopy
GC-MS Gas chromatography-mass spectrometry SEP Steam explosion pretreatment
HTC Hydrothermal carbonization SHF Separate hydrolysis and fermentation
GHG Greenhouse gas SSCF Simultaneous saccharification and simultaneous
5-HMF 5-hydroxymethyl furfural saccharification and co-fermentation
IL Ionic liquid SSF Simultaneous saccharification and fermentation
iTRAQ isobaric tagging approach for relative and absolute TRS Total reducing sugar
quantification TVS Total volatile solids
LCA Life-cycle assessment MC1 Thermophilic microbial consortium
LCB Lignocellulosic biomass

reduce access to the carbohydrate content (55–75% w/w); therefore, it end products (Soares et al., 2020). Anaerobic digestion (AD) and dark
is necessary to develop effective anaerobic bioprocessing methods to­ fermentation are the most reliable and efficient processes for
wards a green environment and to boost the economy (Vu et al., 2020). waste-to-energy conversions (Basak et al., 2020a; Mulat et al., 2018);
Understanding the nature and chemical composition of feedstock and however, these complex processes involve various hydrolytic, fermen­
appropriate biological and non-biological (single or combinations of tative, syntrophic, and methanogenic archaea bacteria in an anoxic
physical, chemical, physicochemical methods) pretreatment technolo­ environment to form bio-methane/H2 from organic waste.
gies are necessary for the effective valorization of LCBs into biofuels Many pretreatment strategies have been practiced for decades to
(Saravanakumar and Kathiresan, 2014). improve the fermentability of biomass by altering its physical and
Economic assessments have shown that the pretreatment step of LCB chemical structure (Saha et al., 2016). However, techno-economic
is the most energy-intensive step and can account for 40% of the total feasibility, carbon footprints, slow process, and generation of several
processing cost, which often limits the commercial utilization of LCBs inhibitory by-products are the major concerns of the conventional pre­
for biofuel production. In addition, most of the physicochemical pre­ treatment processes for the subsequent valorization of LCB (Ab Rasid
treatment processes intended to improve the biodegradability of LCB et al., 2021; Vu et al., 2020). Considering these, the current article re­
simultaneously release inhibitory byproducts that adversely affect the views and critically analyzes the recent developments and optimizations
microbial growth and functions during anaerobic bioprocesses (Ravin­ from the perspective of sustainable valorization of LCB for biofuels
dran and Jaiswal, 2016). In this regard, cost-effective and eco-friendly production. Several emerging pretreatment processes, generation of
pretreatment with lignocellulolytic bacteria and fungi (primarily inhibitory by-products and their detoxification, and their effects on the
white-rot fungi) or their enzymes is an efficient biological process, valorization of LCB have been discussed here, which offer possible so­
which can be completed within a few hours to several days without lutions in biorefineries for higher productivity, substrate efficiency,
generating inhibitory compounds, resulting in a significant increase in reducing toxicity and waste generation, economical, and sustainable
the biofuel yield (up to 120%) (Zabed et al., 2019). However, a long manufacturing processes. Besides, accelerated degradation of LCB has
pretreatment time, relatively low hydrolysis rate, and considerable loss also been highlighted by using enzymatic machinery of ruminant
of fermentable sugars are some of the bottlenecks associated with the anaerobic, potent lignocellulolytic bacteria and fungi to enhance the
use of microbial pretreatment methods (Basak et al., 2020b). rate-limiting hydrolytic pathway for smooth conversion of LCB into
Various eco-friendly, efficient, and cost-effective pretreatment bioenergy.
methods, including the use of ultrasound, microwaves, supercritical A contemporary insight on ‘multi-omics’ approach has also been
carbon dioxide (SC–CO2), deep eutectic solvents (DESs), and ionic liq­ discussed for the first time to unravel the structural and functional un­
uids (ILs), are the emerging physicochemical pretreatment methods for derstandings into the lignocellulolytic microbes and microbial commu­
LCB valorization. These emerging technologies (biological and non- nities that can enhance LCB decomposition and improve the efficiency of
biological) can be used as commercially feasible green pretreatment biofuel production. Furthermore, the significant findings of previous
methods for the sustainable and efficient pretreatment of LCB (Rahmati studies on the production of bioenergy using a lignocellulosic substrate,
et al., 2020). Further, it is essential to identify the key microbial players with a specific focus on the relevant anaerobic bioprocesses, such as AD,
and the metabolic pathways involved in hydrolysis during biological photo/dark-fermentation, ethanol fermentation, and acetone-butanol-
pretreatment via a combination of ‘omics’ approaches, which will aid in ethanol (ABE) fermentation, were outlined. We performed a compre­
designing an improved microbial/enzymatic cocktail for effective LCB hensive literature survey on various methods for the pretreatment and
degradation (Alessi et al., 2018; Tsapekos et al., 2017). Biorefining of valorization of LCB and sustainable and economical treatment ap­
pretreated biomass via anaerobic bioprocesses involves fermentative proaches, emphasizing feasible concepts, desirable strategies, and
anaerobes (obligate or facultative) that produce hydrogen (H2), practical aspects for the commercial success of such anaerobic bio­
methane (CH4), ethanol, butanol, and acetone as one of their metabolic processes. The review articles published over the last five years in the

2
R. Kumar et al. Journal of Cleaner Production 333 (2022) 130180

relevant domain are tabulated and compared in Table 1 to validate the 2.2. Complexity of valorizing LCB in anaerobic bioprocessing
novelty of the present work.
The diversity of raw materials presents in the biomass, which in­
2. Structural complexity of LCB cludes various plant groups, their different chemical compositions, and
physical properties, make it difficult to scale up and commercialize pre-
2.1. Chemical and physical complexities of LCB processing at the industrial level to produce bioenergy. The effective use
of hemicellulose (which contributes 40–50% of the total carbohydrate
Cellulose constitutes the basic structure of LCB and imparts rigidity content) and cellulose is crucial to obtaining high yields and produc­
and ductility. This polymer includes repeated units (400–1400) of β-D- tivity during anaerobic bioprocesses. Although hemicellulose is sensitive
glucopyranose linked by β-(1–4) glycosidic bonds (Fig. 1), which are to water and acid treatment and is easily converted to monosaccharides,
mostly crystalline fibril structures embedded in LCB that confer resis­ its tight binding to cellulose via H-bonds and covalent linkage with
tance to biodegradation (Zeng et al., 2014). The degree of polymeriza­ lignin to form LCC affects its hydrolysis. It renders the LCB recalcitrant
tion (DP) of cellulose plays a crucial role in maintaining the rigid to hydrolysis and necessitates pretreatment to make the structure porous
structure of LCBs as long chains of cellulose contain many intermolec­ and alter the structural and compositional rigidity priors to its valori­
ular H-bonds in-between the ‘-OH’ group of C3 position and ‘O’ of zation (Dahiya et al., 2018). The total reducing sugar (TRS) yield from
glycosidic ring, which confer high resistance against its biodegradation. LCB can be enhanced from 10%–90% with an appropriate pretreatment
The accessibility and reactivity of the functional groups present in cel­ method following enzymatic saccharification (Zhang et al., 2012).
lulose molecules could be affected by an alternation of its crystalline and In general, depending on the severity of the process conditions, such
amorphous regions. The macromolecules in the amorphous structure of as the chemical pretreatments using various acids, pentoses present in
cellulose are irregular and wide apart, resulting in a lower density of 1.5 hemicellulose may be over-degraded to form furfural and organic acids,
g/cm3 compared to 1.588 g/cm3 in crystalline structure due to the which in turn inhibit microbial action during AD (Basak et al., 2020a). In
regular and compact arrangement of macromolecules (Bonechi et al., particular, phenolic compounds produced during the decomposition of
2017). lignin polymers display potent inhibitory or toxic properties against
Hemicellulose, a complex and branched heterogeneous polymer, is microorganisms, which makes biological conversion via saccharification
composed of pentoses (D-xylose, L-arabinose) and hexoses (D-glucose, and fermentation challenging task. Lignin also shows adverse effects by
D-mannose, D-galactose) (Chandel et al., 2018). In addition, a trace blocking enzyme accessibility to cellulose and non-specifically adsorb­
amount of L-rhamnose, D-glucuronic acid, and D-galacturonic acid are ing hydrolytic enzymes to its sticky surface results in non-productive
complexly linked to each other (Hendriks and Zeeman, 2009). However, binding of cellulolytic enzymes to LCC (dos Santos et al., 2019).
the chemical composition, DP, and branch-chain composition of hemi­ Therefore, removing or reducing the lignin content in LCB is necessary
cellulose differ according to the cell type and plant species. The main by selecting an appropriate and effective pretreatment method. More­
component of hemicellulose in grass species is glucuronoarabinoxylans, over, various intrinsic characteristics, such as dielectric properties,
while galactoglucomannan and glucuronoxylan are primarily present in number of hydroxyl groups, moisture content, and crystal­
softwood and hardwood along with other hemicelluloses (Scheller and line/amorphous region in the LCB, should be considered while designing
Ulvskov, 2010). Hemicelluloses in many species are acetylated xylan the parametric conditions. Adopting a strategy for maximal utilization of
and mannan units to various degrees at C2 or C3 position, especially in the monomeric sugars produced in LCB can overcome complexity and
dicot secondary walls and grasses have ferulic acid in xylans, which is valorize LCB in anaerobic bioprocessing.
covalently linked to p-coumaric acid of lignin (Ebringerová et al., 2005;
Hatfield et al., 2008). Hemicellulose has an amorphous structure with a 3. Emerging pretreatment technologies for LCB
DP of approximately 100–200 units lower than that of cellulose. Despite
its weak physical strength, it strongly limits cellulase activity (Barhoum Conventional pretreatment methods remain insufficient to meet the
et al., 2020). requirements for industrial-scale biofuel production due to their poor
Lignin is the second most widely distributed terrestrial biopolymer techno-economic and environmental sustainability. The emerging
after cellulose in biomass, used for binding and putting the fibers physicochemical and biological pretreatment methods have been dis­
together to give a compact and resistant plant cell structure (Boerjan cussed here while highlighting the current findings and recent in­
et al., 2003). It consists of three 4-hydroxycinnamyl alcohols repre­ novations to offset the inherent challenges to their applications in
senting basic aromatic moieties, such as p-hydroxyphenyl (H), guaiacyl commercial-scale biorefinery processes.
(G), and syringyl (S) which formed macromolecule through radical
oxidative polymerization (Tursi, 2019). The DP for the aromatic poly­ 3.1. Emerging non-biological pretreatment methods
mer varies from 450 to 550 units, which holds the hemicellulose and
cellulose fibers together in the plant cell wall and provides structural 3.1.1. Physicochemical pretreatment methods
rigidity (Zoghlami and Paes, 2019). Several G and S units with a small Several promising and non-classical technologies, including the use
number of H units are present in hardwood lignin, while G units pre­ of microwaves, ultrasound, radiation, steam explosion pretreatment
dominate the others in softwood lignin. Herbaceous lignin contains all (SEP), hydrothermal, and pulse-electric field (PEF), have been proposed
three types of monolignols in varying amounts (Zhao et al., 2012). as commercial solutions for LCB valorization (Fig. 2). Non-conventional
Lignin composition (i.e., the number of hydroxyl groups and S and G heating sources, such as microwave irradiation (MWI) operated under
units) and its content adversely affect the release of cellulose during the atmospheric or high pressure can exert effects at the molecular level and
hydrolysis of LCB. Hence, the elimination of lignin from LCB disrupts the dissipate uniformly and more rapidly, resulting in increased surface area
lignin carbohydrate complex (LCC), thereby enhancing the porosity, due to swelling, fragmentation, and internal chemical changes (decar­
surface area, and solubility of the biomass (Karimi and Taherzadeh, boxylation and dehydration) (Dai et al., 2017). However, the efficiency
2016; Kruyeniski et al., 2019). In addition to the three polymers of MWI depends on the dielectric properties of feedstocks, which reflect
described above, many other components are also included in the the capacity of the substrate to store electromagnetic energy and convert
biomass (referred to as extractives, presenting <10% w/w of the it into heat. High moisture and inorganic content in the carbon-rich
biomass), which prevent the penetration of microorganisms into the materials are better microwave energy absorbers and quickly achieve
plant (Mcdonough, 1983). the hydrothermal conditions required for the hydrolysis of LCB (Li et al.,
2016). However, MWI was ineffective on the plant fiber material under
low temperature (<100 ◦ C) (Chen et al., 2017). Additionally, high

3
R. Kumar et al. Journal of Cleaner Production 333 (2022) 130180

Table 1
Comparative analysis of selected review articles published over the last five years on the valorization of lignocellulosic biomass for biofuels production.
Ref. Highlights and Review coverage relevant to the sustainable valorization of LCB for biofuels production
strength of the review
Structural Biomass Generation of Multi-omics Anaerobic Sustainability
complexity of pretreatment inhibitors and approach bioprocesses for aspects
LCB methods their biofuels
detoxification production

Kumar and Sharma - Mainly discussed the N.C. - Physical, N.C. N.C. - Briefly N.C.
(2017) pretreatment chemical, mentioned the
methods for LCB physicochemical, biofuels and
and biological bioproducts
methods production
Chandel et al. (2018) - Commercialization N.C. - Enzymatic N.C. N.C. - General N.C.
of cellulosic ethanol hydrolysis biorefinery
and biochemical
products are
mentioned
- Biomass supply
chain, processing,
and product
recovery have been
presented
Hassan et al. (2018) - Discussed the N.C. - Physicochemical N.C. N.C. N.C. N.C.
limitation of pretreatment
conventional
pretreatment of LCB
- Focused on the green
approaches of
pretreatment
- Techno-economic
feasibility studies
are shown
Baruah et al. (2018) - Critically discussed - Covered - Physical, N.C. N.C. N.C. N.C.
the currently used chemical,
pretreatment physicochemical,
strategies with and biological
merits and demerits pretreatment
- Recovery of high- methods
value bio-polymeric
components from
LCB is mentioned
Kumari and Singh - Different N.C. - Conventional and N.C. N.C. - Briefly discuss N.C.
(2018) generations of emerging biofuels
biofuels and their pretreatment (biogas)
importance are methods production
shown
Hernández-Beltrán - Efficiency and - Covered - Conventional and N.C. N.C. - AD for biogas - Briefly covered
et al. (2019) limitations of emerging production environmental
various physicochemical aspects
pretreatment and biological
strategies are shown pretreatment
- Challenges and methods
opportunities to
increase biogas yield
from LCB are
reviewed
Galbe and Wallberg - Pretreatment of N.C. - Covered N.C. N.C. - Biorefinery of - LCA of LCB
(2019) different conventional LCB biorefinery
lignocellulosic pretreatment
materials are shown methods
- Mentioned the
techno-economic
feasibility studies of
LCB biorefinery
Tu and Hallett (2019) - Discussed the recent N.C. - Physical, N.C. N.C. N.C. N.C.
advances in chemical,
pretreatment physicochemical,
methods of LCB and biological
pretreatment
methods
Zabed et al. (2019) - Mechanism and - Briefly - Recent advances N.C. N.C. N.C. N.C.
factors affecting the covered in biological
biological pretreatment
pretreatment methods
methods are given
- Discussed the
limitation of
(continued on next page)

4
R. Kumar et al. Journal of Cleaner Production 333 (2022) 130180

Table 1 (continued )
Ref. Highlights and Review coverage relevant to the sustainable valorization of LCB for biofuels production
strength of the review
Structural Biomass Generation of Multi-omics Anaerobic Sustainability
complexity of pretreatment inhibitors and approach bioprocesses for aspects
LCB methods their biofuels
detoxification production

physicochemical
pretreatments
- 2G and 3G biofuels
production are
reviewed using LCB
and microalgae
Bhatia et al. (2020) - Technological - Covered - Recently - Covered N.C. N.C. N.C.
improvement, developed
challenges, and key physicochemical
parameters of pretreatment
pretreatment of LCB methods
are given
Rahmati et al. (2020) - Discussed the N.C. - Physical, N.C. N.C. N.C. N.C.
pretreatment and chemical,
fermentation of LCB physicochemical,
- Mainly focused on and biological
reaction mechanism pretreatments
and process methods
engineering
Kumar et al. (2020c) - Mechanisms, merits, - Covered - Physical, N.C. N.C. - Briefly - Economic
and demerits of chemical, discussed the aspects of
different physicochemical, different pretreatment
pretreatment and biological generations of
methods for pretreatment biofuels
biorefinery of LCB methods
are given
Haldar and Purkait - Insight of reaction - Covered - Emerging N.C. N.C. N.C. N.C.
(2021) mechanism, physicochemical
challenges, and pretreatment
perspectives of methods
emerging
pretreatment
methods are
discussed
Mankar et al. (2021) - Recent advances and - Covered - Conventional and N.C. N.C. N.C. N.C.
future perspectives emerging
of physical and physicochemical
chemical pretreatment
pretreatment methods
methods are
discussed
Beig et al. (2021) - Challenges and N.C. - Physical, N.C. N.C. N.C. - LCA of
innovative chemical, pretreatment
developments in LCB physicochemical, methods
pretreatment for and biological
biofuels production pretreatment
are critically methods
mentioned
Ab Rasid et al. (2021) - Recent advances and N.C. - Green chemical N.C. N.C. - AD for N.C.
future perspectives pretreatment methane,
in green methods bioethanol,
pretreatment and biobutanol
methods of LCB for fermentations
enhanced biofuels
production are
discussed
Mirmohamadsadeghi - LCB pretreatment - Covered N.C. - Covered - Phylogenetic - AD for biogas N.C.
et al. (2021) and AD studies production
improvement
mechanisms are
reviewed
- Microbial diversity
during AD is
discussed
Culaba et al. (2022) - Challenges and N.C. - Briefly covered N.C. N.C. - Briefly - CE concept in
future research pretreatment mentioned the smart
about innovative production of biorefinery
approaches, such as value-added
the use of artificial products from
intelligence in LCB
lignocellulosic
(continued on next page)

5
R. Kumar et al. Journal of Cleaner Production 333 (2022) 130180

Table 1 (continued )
Ref. Highlights and Review coverage relevant to the sustainable valorization of LCB for biofuels production
strength of the review
Structural Biomass Generation of Multi-omics Anaerobic Sustainability
complexity of pretreatment inhibitors and approach bioprocesses for aspects
LCB methods their biofuels
detoxification production

biorefinery, are
discussed
Ashokkumar et al. - Advanced - Covered - Conventional and N.C. N.C. - Briefly - Techno-
(2022) pretreatment emerging mentioned the economic
methods of LCB for physicochemical production of feasibility of
biofuels and and biological biofuels and biomass
bioproducts pretreatment value-added valorization
production are methods (briefly products
mentioned discussed)
Rodionova et al. - Comprehensively - Covered - Briefly Covered N.C. N.C. - Briefly N.C.
(2021) discussed the the physical, Covered bio-
lignocellulosic chemical, and H2, bioethanol,
biorefinery biological and bio-
- Biochemical pretreatment butanol
conversion and
engineering
perspective of LCB
biofuels are mentioned
Zhao et al. (2022) - Advances, key N.C. - Conventional and - Covered N.C. - Briefly N.C.
challenges, and emerging physical, mentioned
perspective LCB chemical, bioenergy
pretreatment for physicochemical, production in
bioenergy and biological general
production are pretreatment
discussed methods
Present study - Critically discussed - Covered in - Different - Inhibitors - Discussed - Different - Discussed
the emerging detail about emerging generations, genomics, anaerobic sustainability
pretreatment the physicochemical, their effect on transcriptomics, bioprocesses, aspects of
methods of LCB complexity chemical, and the proteomics, and such as light/ valorization of
- Sustainable of different biological valorization of metabolomics dark LCB
valorization of components pretreatment LCB, and fermentation,
pretreated LCB using of biomass methods detoxification AD,
anaerobic methods bioethanol,
bioprocesses is and ABE
reviewed fermentation

‘N.C. - Not covered’.

capital and operating costs, energy-intensive processes, and biomass wall structure by chain scission or cross-link formation, depolymeriza­
with high moisture and inorganic contents should be optimized before tion, and decrystallization of biomass (Schnabel et al., 2015). However,
implementing MWI on an industrial scale. Ultrasound pretreatment in additional methods, such as a steam explosion or alkali treatment along
the range of 20 kHz to 1 MHz has been used to produce oxidizing rad­ with EB, are required to effectively depolymerize LCB (Xiang et al.,
icals that attack and disrupt the linkages (α-O-4 and β-O-4) present in the 2017).
lignin of LCB, leading to the fragmentation, rupture, and destruction of Aqueous fractionation technologies include SEP (Pielhop et al.,
cells (Luo et al., 2013). 2016) and hydrothermal (Xiao et al., 2014) methods. Here, water is used
Ultrasound-assisted treatment results in the development of cavita­ at high temperatures (160–240 ◦ C) and pressure (0.7–4.8 MPa) for hy­
tion bubbles inside the LCB, which subsequently collapse after attaining drolysis and lignin separation, which renders the cellulose amenable to
the critical size owing to the development of high pressure (182.3 MPa) further enzymatic hydrolysis with a low effort for detoxification due to
and temperature (1726–4726 ◦ C). This leads to the splitting of the reduced generation of toxic compounds. Al Ramahi et al. (2021) re­
hemicellulose and cellulose structure, as well as fractionation in the ported hydrothermal carbonization (HTC) pretreatment of dried dairy
lignin polymers (Kumar and Sharma, 2017). The addition of ammonia sludge at 210 ◦ C for 30 min to improve the methane yield up to 192% by
(10 mL/g LCB) along with ultrasound treatment (400 W and 24 kHz) 30% increase in sludge biodegradability and an 18% reduction in
resulted in >58% delignification and >95% cellulose recovery from chemical oxygen demand through AD process. Further, the application
sugarcane bagasse at 80 ◦ C for 45 min (Ramadoss and Muthukumar, of HTC of AD digestate enhanced the total energy production by forming
2014). Thus, the synergistic approach reduced by-product formation, hydrochar of a high calorific valued (10.2 MJ/kg) product. These
operating temperature, pretreatment time, and cellulose crystallinity. methods do not require extra chemicals, thereby lowering the capital
Despite several advantages, to augment the bioconversion of LCB via and operating costs, although they corrode the equipment slightly
ultrasound processes at an industrial scale, various factors must be (Zhuang et al., 2016). Nevertheless, SEP and hydrothermal methods
critically comprehended and optimized, such as operating time, ultra­ have been successfully applied in semi-industrial projects on a pilot
sound frequency, solvents, type of feedstock, and bench-scale results scale, which indicates their potential for implementation at full indus­
(Mankar et al., 2021). trial scale (Larsen et al., 2008; Thomsen et al., 2008). The PEF is a
Radiations from different radioisotopes, such as Co-60 and Cs-137, non-thermal and energy-efficient method that can disrupt the LCB
can penetrate deeply and form free radicals to alter lignin structure, structure by applying voltage pulses of 0.1–80 kV/cm for a fraction of
reduce cellulose crystallinity, and enhance specific surface area (Hong time, facilitating the saccharification of porous biomass by hydrolytic
et al., 2014). Similarly, irradiation by an electron beam (EB) obtained enzymes (Hassan et al., 2018). However, high equipment cost,
from a linear accelerator produces free radicals and can disrupt the cell non-uniform effect, non-suitability for solid biomass, and operational

6
R. Kumar et al. Journal of Cleaner Production 333 (2022) 130180

Fig. 1. Structural complexities of lignocellulosic biomass consisting of cellulose, hemicellulose, and lignin.

and safety issues are significant limitations of PEF-based LCB pretreat­ However, the efficacy of SC-CO2 pretreatment heavily depends on the
ment (Kovacic et al., 2021). moisture content of the biomass because the CO2 and moisture generate
carbonic acids in situ, which promote hemicellulose hydrolysis due to
3.1.2. Emerging chemical pretreatment methods acidification of the reaction mixture (Escobar et al., 2020; Fockink et al.,
The idea of ‘green chemistry’ application in biorefineries for efficient 2018). The use of SC-CO2 does not cause equipment corrosion, as by
conversion of LCB to biofuels without using harsh and toxic chemicals mineral acids, during industrial-scale applications because the pH of the
has aroused increasing interest in researchers (Yiin et al., 2021). residual solution increases after depressurization of CO2 gas (Toscan
Recently, advances in chemistry have led to the development of greener et al., 2017).
and more sustainable alternatives, such as ILs, DESs, SC-CO2 explosion, Plasma pretreatment technology is another emerging efficient
and ozonolysis. ILs and DESs are the emerging, and tailor-made green method being considered for inducing physical and chemical structural
solvents whose physicochemical characteristics (viz. polarity, viscosity, changes in LCB using highly reactive ionized gases without generating
conductivity, hydrophobicity) can be tailored by adding various com­ polluting and toxic chemicals (Vanneste et al., 2017). Variants of plasma
binations of cationic and anionic constituents (Cao et al., 2017). ILs, pretreatment include atmospheric plasma sources (APSs) and plasma
such as [1-butyl, 3-methylimidazolium][hydrogen-SO4] and [1-butyl, electrolysis (PE), which employ low gas input and electricity to generate
3-methylimidazolium] [methyl-SO4] have been used to fractionate powerful oxidizing molecules, such as hydroxyl radicals, singlet oxygen,
LCB (Pinus sylvestris and Miscanthus giganteus) into lignin and hemicel­ and ozone to decompose/reduce the lignin content, increase the surface
lulose in hydrolysate and cellulose as solid biomass (Brandt et al., 2011). area, and reduce the crystallinity index by facilitating the severe colli­
High-purity cellulose can be recovered by adding an anti-solvent, such sion of active species over the surface of biomass (Gao et al., 2014).
as aqueous ethanol or acetone, while ILs can be recovered via ion ex­ However, initial moisture content of 50% was suitable for maximum
change, salting out, reverse osmosis or pervaporation. However, a few delignification and cellulose recovery by ozonolysis through APS and PE
limitations are associated with ILs; pyridinium and imidazolium salts, processes (Tian et al., 2013a). The methods mentioned above are
mainly used in ILs, are obtained from a petroleum source, are costly, energy-intensive, whereas a renewable energy source can make the
cause water pollution, and are non-biodegradable (Kumar et al., 2020b). processes eco-friendly and sustainable (Table 2). Furthermore, decon­
Unlike ILs, DESs are eco-friendly, cost-effective, highly tunable, and struction of lignocellulosic substrates into fermentable sugars becomes
soluble and render the LCBs amenable for better conversion to more effective when green pretreatment technologies (as discussed
value-added products (Chen and Mu, 2019). above) are performed in combination with integrated methods, as
Another advanced chemical pretreatment is ozonolysis, where shown in Table 3.
ozone, a powerful oxidizing agent, reacts specifically with the lignin of
LCB, causing up to 80% delignification, resulting in enhanced LCB di­ 3.1.3. Generation of inhibitory by-products and their detoxification
gestibility during the subsequent saccharification step (Rahmati et al., Pretreatment of LCB under thermal or thermochemical regimes re­
2020). However, the high operating cost of ozone generation and limi­ sults in better digestibility of lignocellulosic feedstocks, which also
tations related to scaling up are a few significant constraints related to generates toxic by-products (Basak et al., 2020a). In oxidative pre­
ozonolysis. In supercritical CO2 (SC–CO2) pretreatment performed treatment, hydrothermal pretreatment, and SEP, lignin undergoes
under high pressure (14–18 MPa) at mild temperatures (30–100 ◦ C), depolymerization to form phenolic compounds (e.g., vanillin and
CO2 molecules penetrate the crystalline structure of the LCB by forming syringaldehyde), whereas carbohydrates (cellulose and hemicellulose)
carbonic acid and increasing the surface area (Garver and Liu, 2014). transform into furanic compounds [furfural, levulinic acid,

7
R. Kumar et al. Journal of Cleaner Production 333 (2022) 130180

Fig. 2. Emerging physicochemical and chemical technologies used for the pretreatment of lignocellulosic biomass [adapted from Aguilar-Reynosa et al. (2017) with
permission from Elsevier, License No. 5181230680094; Omar and Amin (2016) with permission from Elsevier, License No. 5181230300318; Tian et al. (2020) with
permission from Elsevier, License No. 5181230946260; Xing et al. (2018) with permission from Elsevier, License No. 5181221467973; Liao et al. (2016) with
permission from Elsevier, License No. 5181651314593; Hernández-Beltrán et al. (2019); Yu et al. (2018); Salimi et al. (2016)].

5-hydroxymethyl furfural (5-HMF)] under harsh pretreatment condi­ Sporolactobacillus putidus, Clostridium acetobutylicum, Clostridium cellu­
tions (such as 60–75 min treatment with 4% HCl or 3.5% H2SO4 at losi) in the microbial consortium during dark fermentation may be
120–210 ◦ C) (Barakat et al., 2012; Panakkal et al., 2022). By-products suppressed by phenolic and furanic compounds, resulting in an overall
generated during LCB pretreatment negatively affect the fermentative low H2 production (Basak et al., 2020a; Quéméneur et al., 2012).
efficiency by altering the metabolic pathways and dynamics of the mi­ However, certain microorganisms, such as C. beijerinckii, can tolerate
crobial community involved in AD or fermentation. Weak acids (acetic, lignocellulosic inhibitors (phenolic compounds) and enhance their
formic, and levulinic acids), generated during the further breakdown of population from 70.7% to 85.8% during H2 production from LCB
5-HMF and furfural, can diffuse into microbial cells through lipoprotein (Quéméneur et al., 2012). Additionally, yeast cells can also sustain at
of the plasma membrane and cause cell lysis due to acidification of low concentrations (<1 g/L) of furfural and 5-HMF by metabolizing
cytosol (Mirmohamadsadeghi et al., 2021). Fermentation medium con­ them into relatively less harmful compounds, such as furfuryl alcohol
taining 5-HMF concentration <3 g/L does not show any toxic effect on and 2,5-bis-hydroxymethylfuran, respectively (Jonsson et al., 2013).
C. saccharoperbutylacetonicum during ABE fermentation. In contrast, Furfural, vanillin, and phenolic compound degrading fungal species
lignin-derived phenolic compounds inhibit the growth of microbial cells Byssochlamys nivea was identified after screening 44 fungal species for
even at low concentrations (<1 g/L) (Wang et al., 2019). These inhibi­ efficient detoxification of lignocellulosic inhibitors in less than 11 days
tory by-products can penetrate the microbial cells by a disintegrating (Zanellati et al., 2021).
cell membrane, limits cell growth by lag phase elongation, inhibit A variety of physical (heating and vaporizing) (Larsson et al., 1999),
glycolytic enzymes, and damage DNA depending upon their molecular chemical (NaOH, Ca(OH)2, NaBH4) (Monlau et al., 2015), adsorption
structure, weight, and hydrophobicity (Devi et al., 2021). The phenolic (activated carbon) (Mikulski and Kłosowski, 2020), liquid-liquid
compounds, 5-HMF, and furfural had more significant inhibitory effects extraction (ethyl acetate, trialkylamine) (Monlau et al., 2015), enzy­
on the microbes involved in dark fermentation than AD (Monlau et al., matic (laccase, peroxidase), and genetically modified microbe-based
2014). (Kannisto et al., 2015; Singh et al., 2019) processes can be used to
The growth of specific beneficial species (Clostridium beijerinckii, detoxify the slurries and hydrolysates after LCB pretreatment (Table 4).

8
R. Kumar et al. Journal of Cleaner Production 333 (2022) 130180

Table 2
Critical comparison of various emerging physicochemical technologies for the pretreatment of lignocellulosic biomass [adapted from Haldar and Purkait (2021) with
permission from Elsevier, License No. 5181210241494; Hassan et al. (2018) with permission from Elsevier, License No. 5182810299067; Yiin et al. (2021) with
permission from Elsevier, License No. 5182801386825].
Pretreatment methods and Impact on the degradation of Advantages Disadvantages Impact on Ref.
process conditions the lignocellulosic substrate production

Bio- bio-
CH4 ethanol
or H2

DESs (e.g., ChCl/Glycerol) - Disintegration of the - Green and cheap solvents - Low stability under high + + Zhang et al.
temperature: 40–110 ◦ C recalcitrance structure - Bio-degradable and bio- temperature (2016)
- Fractionation of compatible solvents - High viscosity
hemicellulose and partial - Easy to prepare - Hygroscopic properties
removal of lignin - Low energy requirement
ILs (e.g., Imidazolium-based - Partial dissolution of lignin - Tailor-made solvents - High operating cost due to + – Yoo et al.
complexes), temperature and hemicellulose - Low vapor pressure complex synthesis and (2017)
<100 ◦ C - Enhanced porosity and - Mild operating conditions purification
reduced crystallinity of - Efficient lignin recovery - Poor biodegradability
cellulose - Easy to recover and recycle - Inhibitory effect of enzymatic
- Thermally stable processing
- Industrial competitiveness
Supercritical fluids (e.g., SC- - Enhanced bioaccessibility - Green solvent - High utility and equipment + + Daza Serna
CO2), pressure: 7–25 MPa, for enzymatic - Minimal loss of sugars cost et al. (2016)
temperature: 200 ◦ C saccharification - Non-toxic and non- - High operating cost
- Reduced crystallinity of flammable - Not suitable for the
cellulose and removal of - Easy to recover lignocellulosic substrates with
lignin low moisture content
Hydrothermal, temperature: - Fractionation of biomass - No use of corrosive chemicals - High temperature and pressure + + He et al. (2015)
150–300 ◦ C, pressure: 0–6 components - Eco-friendly process are required
MPa, time: 10–240 min - Facilitation of enzymatic - Short processing time - Generate inhibitory by-
hydrolysis (131% increase products
in glucose yield)
Steam explosion, temperature: - Softening of lignin - Low capital investment - Less effective in softwood + + Pielhop et al.
184–235 ◦ C, pressure: - Reduced particle size - Moderate energy - Formation of inhibitors to (2016)
1.1–3.1 MPa - Disintegration of the requirement bioconversion
complex structure of LCB - Limited use of chemicals
- High sugar recovery - Eco-friendly process with
reduced generation of waste
Ozonization (O3 and ethanol), - Reaction with olefins to - No use of corrosive chemicals - Needs high ozone dosages for + + Mulakhudair
oxidizing potential (EO = form the ring structure and - Operation at ambient high biomass loadings et al. (2017)
+2.07 V), pH: 3, ozone dose: subsequent breakdown in temperature and pressure, - Economically unfeasible at
8 mg/L smaller compounds reduction in lignin content, industrial scale
- Enhance porosity and and the release of sugars - Needs high energy
biodegradability - Strong oxidant nature of O3 is - O3 is highly reactive, corrosive,
- Reduced lignin content effective and flammable
- No generation of toxic by-
products
MWI (needs H2O2, NaClO2) - Decreased crystallinity of - Short processing time - Microwave power is poorly + + Baruah et al.
cellulose - Easy to handle distributed (2018)
- Removal of lignin and - Quick heat transfer in - Uneven biomass heating
degradation of biomass - Inhibitors are generated in
hemicellulose - Environmentally benign severe conditions (high
process temperature and pressure)
- Selective, low residence time - High capital and operating
- Low/no inhibitors generated costs
at low temperature and
pressure
Ultrasound - Deconstruction of the - Highly efficient in sugar - Need high energy input + + Luo et al.
biomass for enhanced production - Less feasible in large-scale (2014)
enzymatic saccharification - Short pretreatment time application
- Reduced lignin content - Enhanced distribution of
biomass
CO2 laser pretreatment, solid to - Increased surface area of - No strong and toxic chemicals - High energy-demanding + + Tian et al.
liquid ratio: 21.3 mL/g, biomass are used process (2011)
power: 264.3 W, time: 67 min - Decreased crystallinity of - Short processing time - Consumes power during CO2
cellulose - Low/no lignocellulosic laser generation
- Enhanced enzymatic inhibitors are generated - High capital and operating cost
saccharification yield - Needs renewable energy
sources to make the process
sustainable
Plasma pretreatment, N2/air - Destruction of chemical - No need for strong chemicals - Requires high energy source + + Gao et al.
(wet and dry), argon, and bonds or linkages within the - Low/no conversion of lignin - Needs further investigation to (2014)
ozone gases which are ionized complex structure and/or sugars into inhibitors know the treatment
under high-voltage in- - Enhanced delignification - Short processing time mechanism involved between
between two electrodes - Reduced cellulose - Renewable energy sources the plasma-lignocellulose
crystallinity can increase sustainability interaction
- High equipment cost + +
(continued on next page)

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R. Kumar et al. Journal of Cleaner Production 333 (2022) 130180

Table 2 (continued )
Pretreatment methods and Impact on the degradation of Advantages Disadvantages Impact on Ref.
process conditions the lignocellulosic substrate production

Bio- bio-
CH4 ethanol
or H2

PEF, - Disruption of biological - Non-thermal and low energy - Unsuitable for solid biomass Kovacic et al.
Voltage pulses: 0.1–80 kV/ membrane requirement - Operational and safety issues (2021)
cm; time: 10− 2 s - Reduced crystallinity of - No strong chemicals are used - Non-uniform pretreatment
cellulose - Short processing time effect

‘+/− ’ signs indicate a positive and negative impact on production.

Table 3
Effects of integrated physicochemical pretreatment methods on the biodegradability of lignocellulosic biomass [adapted from Haldar and Purkait (2021) with
permission from Elsevier, License No. 5181220302245; Ong and Wu (2020) with permission from Elsevier, License No. 5181220518849].
Integrated Lignocellulosic Operating conditions Key findings Ref.
pretreatment substrates
methods

Ultrasound and Triarrhena Acid (HCl), 10% (w/v); Solid loadings, 10% (w/v); Lignin content reduced to 17.6%; Reducing Tao et al. (2017)
dilute acid lutarioparia temperature, 120 ◦ C; operating time, 1 h; sugars increased from 79.4% to 111.2%
ultrasonication for 30 min at 200 W and 20 kHz
Ultrasound and Rice straw Biomass loading, 20% (w/v); NaOH, 1% (w/w); Lignin content reduced to 4.6% Wu et al. (2017)
alkaline ultrasonication for 1 h at 300 W and 22 kHz
Ultrasound and Sunn hemp Biomass loading, 40% (w/v); H2O2, 2%; Lignin content reduced to 4.96% and Baksi et al. (2019)
alkaline H2O2 ultrasonication for 1 h at 130 W and 50 Hz at 50 ◦ C pretreatment time reduced to 80%
Ultrasonic and IL Rice straw Biomass loading, 20% (w/v); time, 15 min; Increase in delignification up to 19% and total Han et al. (2018)
ultrasonication for 1 h at 70 ◦ C reducing recovery up to 29%
Ultrasound and DES Oil palm frond Biomass loading, 10% (w/v); ChCl: urea (1:2); Lignin removal up to 36.4% and xylose Ong et al. (2019)
ultrasonication for 30 min at 70% amplitude recovery by 58%
Hybrid organic Spruce biomass Biomass loading, 1% (w/w) sulphuric acid; ethanol, Delignification up to 79.4%, enhanced Matsakas et al. (2019)
solvent and steam 50% (w/w); temperature, 200 ◦ C; 30 min cellulose content to 63.3%, saccharification
explosion yields 61% (w/w)
Hybrid pretreatment Corncob Biomass loading, 2% (w/v) hydrothermal Delignification up to 87%, recovery of 94% of Yu et al. (2018)
temperature, 130 ◦ C, 1.5 bar pressure and treatment total carbohydrates
time for 0.5–4 h in modified Fenton’s solution (0.007
mM FeCl3, 0.3 mM H2O2 and 2 mL 1:6 ratio of DMSO:
H2O solvent)
Microwave and Stillage of wheat Biomass loading, 5% (w/v) in sulphuric acid (0.2 M); Allowed cellulose hydrolysis yield up to 75% in Mikulski and Kłosowski
dilute acid and rye microwave at 0.372 MPa pressure for 15 min pretreated stillages (2020)
residence time at 300 W
Microwave and Corn cob Biomass loading, 10% (w/v); alkali NaOH (1.5 M) + Sugar yield enhanced up to 7-fold with the (Sewsynker-Sukai and
alkali salt different salts like Na3PO4˙12H2O, Na2CO3, and highest saccharification of 0.8 g/g of reducing Gueguim Kana, 2018)
CH3COONa; microwave at 700 W for 6 min sugars using 11.6% Na3PO4˙12H2O salt
Microwave and Brewer’s spent grain Biomass loadings, 10% (w/v) in hydrothermal; No strong chemical used, 82% of fermentable López-Linares et al.
hydrothermal temperature, 150–220 ◦ C; residence time, 2–10 min; sugars achieved at optimum condition, i.e., (2019)
method microwave at 50 Hz and 1000 W 193 ◦ C for 5 min, 60 kg of ABE fermentation per
ton of biomass
DES and Switch grass Biomass loading, 20% (w/v); hydrothermal Cellulose enriched to 72.6%, enzymatic Chen et al. (2018)
hydrothermal in temperature, 130 ◦ C; time, 30 min; ChCl: ethylene saccharification yielded 241 g/L reducing
acidic condition glycol (1:2) with 25% w/v; solid loading at sugars, i.e., 86% of glucose
temperature 130 ◦ C for 30 min
DES and microwave Switch grass, corn Biomass loading, 10% (w/v); microwave at 800 W for Delignification up to 85–87%, cellulose Chen and Wan (2018)
stover, miscanthus 45 s; ChCl: lactic acid, (1:2) enrichment up to 65–67%

However, most of these processes have limitations, such as the need for obtaining high yield and purity and the valuable final product (bio-­
chemical supplements, heat, loss of sugars, additional pretreatment methane/H2/ethanol/butanol) than subsequent detoxification steps
steps, and longer processing time (Basak et al., 2020a). Detoxication via (Mikulski and Kłosowski, 2020).
adsorption successfully reduces the toxic stress due to the high sorption
capacity of lignocellulosic inhibitors (furfural and 5-HMF) present in the
hydrolysate without disturbing the sugar concentration. For example, 3.2. Biological pretreatment
Monlau et al. (2015) successfully removed 5-HMF (94%) and furfural
(99%) using a pyrochar (4%, w/v) for 24 h in a synthetic medium. In recent years, biological pretreatment using lignocellulolytic bac­
Similarly, coconut shell activated carbon (2%, w/v) efficiently adsorbed teria and fungi (brown, white, and soft rot) has emerged as an alterna­
phenolic compounds and furaldehyde from hydrothermally pretreated tive, efficient, eco-friendly, and cost-effective approach for the
sugarcane bagasse hydrolysate, without affecting sugars. The detoxified pretreatment and depolymerization of lignocellulose without generating
hydrolysate produced 30% more glucose during saccharification, while inhibitory byproducts (Mustafa et al., 2016) (Table 5). The efficacy of a
yielding 14-fold enhanced alcoholic fermentation (Freitas et al., 2019). lignocellulose-degrading microorganism is not an absolute value and
Adoption of an appropriate LCB pretreatment method, under optimized varies mainly depending on the type as well as the structural and
conditions with low or no generation of toxic compounds and without chemical composition of the LCB. The appropriate selection of micro­
compromising the yield of fermentable sugars, is more effective for organisms based on the lignocellulosic composition of biomass can
render the process efficient, time-saving, and reduce substrate loss.

10
R. Kumar et al. Journal of Cleaner Production 333 (2022) 130180

Table 4
Critical comparison of some effective approaches to detoxify the lignocellulosic inhibitors from hydrolysates.
Biomass and Hydrolysate Detoxification process Inhibitors removal Pros and cons Biofuel production References
pretreatment composition
conditions

Switchgrass - Carbohydrates - Adsorption by - 50–60% removal Pros - Simultaneous saccharification Wang et al.
(P. virgatumis), (5.8 g/L; xylose, activated carbon of furfural and 5- - Cost-effective and fermentation (2019)
3 g/L acetic acid 10.4 g/L, total - Adsorbent loaded HMF process - ABE fermentation using
at temperature of carbohydrate, 20 5% (w/v), agitated at - 50% removal of - Easy to handle C. saccharoperbutylacetonicum N1-
170 ◦ C for 20 min g/L) 150 rpm at 60 ◦ C for phenolics - Easy to regenerate 4
- Inhibitory 6h - Detoxify by physical - 8.6 g/L butanol (0.16 g/g yield)
products (acetic adsorption on
acid, 4.9 g/L; 5- activated carbon
HMF, 0.5 g/L; Cons
furfural, 0.8 g/L; - Adsorption of
phenolics, 6.3 g/ carbohydrates
L) - Total carbohydrate
reduced by 11%
Olive tree clipping, - Carbohydrates - Sodium borohydride - 94–98% reduction Pros - Fermentation by Pichia stipitis CBS Peinado
75 mM oxalic acid (glucose, 16.6 g/L; as a reducing agent in furan - Mild reaction 6054 et al. (2019)
pretreatment at xylose, 15.1 g/L; - Used 0.03 mol/L for concentration conditions - 3.8 g/L ethanol (27% yield) at 63
150 ◦ C arabinose, 2.8 g/ 30 min at 6 pH - 40% reduction in - Reduce phenolic h
L; 2.87 g/L) phenolics content and furanic content
- Inhibitory - Positive effect on
products (acetic fermentation
acid; phenolic Cons
compounds, 3.18 - Furfural reduced to
g/L; furans, 0.96 furfuryl alcohol
g/L) causes toxicity to
yeast cells
- 1.3 and 4% loss of
glucose and xylose,
respectively
Cassava stem, - Carbohydrates - Liming by CaCO3 to - Furfural removal Pros - S. cerevisiae strain IAM4178 Tanaka et al.
20% (w/v) (glucose, 95 g/L) adjust pH up to 11 - Easy handling - intermittent yeast inoculation (2019)
loading, Inhibitors (furfural, - Adsorption by 10% - Completely produced 37.5 g/L ethanol
Two-step acid 0.95 g/L (w/v) activated removed furfural
pretreated (72%, carbon by agitating from hydrolysate
w/w H2SO4 added 1h - Activated carbon
1:1.25 ratio) can be reused
biomass stirred Cons
for 1 h and - Solid waste
autoclaved at (gypsum) formed
111 ◦ C for 1 h - Frequent pH change
- Glucose
concentration
reduced up to 27%
Hemicellulosic - Carbohydrate - Vacuum evaporation - 85.4% acetic acid Pros - Ethanol yield and productivity by Roque et al.
hydrolysate (glucose, 15.4 g/L; followed by liquid- removal - Less sugar loss S. stipitis 71.8% and 0.38 g/L/h, (2019)
(sugarcane xylose, 200.5 g/L; liquid extraction by - 69% phenolics (~5% glucose and respectively and by
bagasse), arabinose, 16.1 g/ methyl-isobutyl- removal 1% xylose) S. passalidarum, 82.2% and 0.91
Pretreated with L; cellobiose, 4.6 ketone - 100% removal of - 98.8% reducing g/L/h, respectively in 48 h
0.5% (v/v) H2SO4 g/L) formic acid, 5- sugars were
at 140 ◦ C for 15 - Inhibitory HMF, and furfural consumed by yeast
min products (acetic after detoxification
acid, 28 g/L; - 4.4-times increase
formic acid, 0.38 in ethanol yield
g/L; phenolics, after detoxification
12.4 g/L; 5-HMF, Cons
0.15 g/L; furfural, - High operating cost
0.12 g/L - high consumption
of solvent
- Additional solvent
recovery step is
required
Sugarcane bagasse, - Carbohydrates - Washing of - 72% reduction in Pros - 75% theoretical yield of ethanol Pinto et al.
15% (w/v) (glucose, 48.02 g/ hydrolysate phenolics - Soybean proteins (2021)
biomass loading, L; xylose, 18 g/L) - Addition of soybean prevent
Hydrothermal - Inhibitors protein during unproductive
pretreatment at (phenolics, 2.68 enzymatic adsorption of
195 ◦ C, 200 rpm g/L) saccharification cellulases on lignin
for 10 min - 18% enhanced
saccharification
after addition of
soybean proteins
Cons
(continued on next page)

11
R. Kumar et al. Journal of Cleaner Production 333 (2022) 130180

Table 4 (continued )
Biomass and Hydrolysate Detoxification process Inhibitors removal Pros and cons Biofuel production References
pretreatment composition
conditions

- Addition of soybean
protein delay the
hydrolysis process
in initial 12 h
a
Lodgepole pine - Carbohydrates - Addition of - Addition of Pros N.R. Zhai et al.
(P. contorta), (glucose, 55.4%; carbocation carbocation - No need for (2018)
woody biomass, xylose, 1.4%; scavengers scavengers additional
Acid (1%, w/w mannose, 2%) (hydroxybenzoic efficiently mitigate detoxification step
H2SO4) pretreated - Inhibitory acid, vanillic acid, the toxic effect of - Cellulose hydrolysis
at 180 ◦ C for 40 products (acid- and syringic acid) lignin-derived increased up to 50%
min followed by insoluble lignin, dissolved in acetone phenolics during by adding syringic
steam 44.6%; acid- (5%, w/w) saccharification acid
pretreatment at soluble lignin, - Scavengers agitated Cons
200 ◦ C for 5 min 1.1%) with biomass for 2 h - Steam pretreatment
is required after the
addition of
scavenger to the
acid pretreated
biomass
Wheat straw - Carbohydrates - Addition of 1 mM - Reducing the Pros N.R. Akimkulova
biomass (10%, w/ (glucose, 50.7%; MgCl2 negative charges - Weaken the et al. (2016)
v), xylose, 6.9%) over the surface of unproductive
Acid (0.5%, w/v - Inhibitory product lignin binding of cellulase
H2SO4) pretreated (lignin, 39.6%) - Reduces the to lignin
at 140 ◦ C stirred toxicity of lignin - Improved
at 300 rpm for 1h - Mg2+ block Ph-OH saccharification by
groups of lignin 19.3% at low
monomeric units enzyme loading (5
FPU/g solid)
Cons
- Metal ions may
interfere with the
saccharification
process
- Efficiency depends
upon pH, operating
time, and enzyme
loading
Sugarcane - Carbohydrates - Biodetoxification - Degrade 100% Pros N.R. Singh et al.
hydrolysate, (glucose, 7.74 g/L; using newly isolated furfural, 94% 5- - Cost-effective, (2017a)
Acid (1.25%, w/w xylose, 16.5 g/L) strain, Bordetella sp. HMF and 82% efficient, and eco-
H2SO4) pretreated - Inhibitory BTIITR from soil acetic acid in 16 h friendly process
biomass products (acetic - Lessen to inhibitors
autoclaved at acid, 3.3 g/L; 5- for smooth
121 ◦ C for 2 h HMF, 1.03 g/L; saccharification and
furfural, 0.42 g/L) fermentation
process
Cons
- Biodetoxification is
a slow process
Wood chip (poplar), - Carbohydrates - Ion-exchange resin - 96.7% of acid- Pros - 95.3% of total sugars are utilized Yu and
Steam (glucose, 3.5 g/L; IRA-400 (OH− ) soluble lignin was - IERs are chemically by S. cerevisiae in 72 h - Ethanol Christopher
pretreatment at xylose, 81.7 g/L; removed and mechanically concentration increased to 41.5 (2017)
170 ◦ C for 2 h, arabinose, 4.1 g/ - Significant stable g/L with a yield of 89.6%
liquid hydrolysate L) removal of acetic - Efficiently removed
is treated with 4% - Inhibitory acid (43.9%), phenolic
(w/v) H2SO4 products (acid- benzoic acid (95%) compounds
soluble lignin, 34 - Regeneration and
g/L; formic acid reuse make the IER
4.3 g/L; acetic cost-effective
acid, 21 g/L; Cons
benzoic acid, - Need acid/base for
0.022 g/L) regeneration
- Generates
wastewater during
washing and
regeneration
- 21% sugar (xylose)
lose
a
Not reported.

12
R. Kumar et al. Journal of Cleaner Production 333 (2022) 130180

Table 5
A comparison of various biological pretreatment strategies for lignocellulosic biomass.
Pretreatment Lignocellulosic Culture Pretreatment Impact of pretreatment on Impact of pretreatment Ref.
microorganisms/Enzyme feedstock technique incubation condition biomass on anaerobic bioprocess
preparations

Mixed microbial Sawdust waste Submerged X0/S0 = 12 mg/g; Reduction in TS (83.4), VS 25.6% higher biogas Ali et al. (2017)
consortium incubated at 30 ◦ C for (56.9%), cellulose (37.5%), yield after 28 d of AD
10 d hemicellulose (39.6%), and
lignin (56.7%)
Pleurotus pulmonarium Sugarcane top Solid-state Incubated at 28 ◦ C for Reduction in lignin 37.7% and 54% higher Kumari and Das
MTCC 1805 21 d (60.4%), hemicellulose yields of bioH2 and (2016)
(24.3%), and cellulose bioCH4, respectively
(5%); TS recovery was
81.7%
Citrobacter werkmanii Whole water hyacinth Submerged Incubated at 37 ◦ C Reduction in cellulose 23% increase in Barua et al. (2018)
VKVVG4 plant and stirred at 120 (30.8%) and hemicellulose cumulative biogas
rpm for 4 d (43%); overall production
solubilization of the
biomass, 33.3%
Aspergillus fumigatus Mixed fruit and Submerged X0/S0 = 2 × 105 Soluble carbohydrate 53% higher biohythane Basak et al. (2020b)
NITDGPKA3 vegetable wastes spores/g; incubated recovery was 362.84 mg/g; yield, which
at 30 ◦ C and stirred at reduction in hemicellulose corresponds to 47%
180 rpm for 5 d (62.7%), cellulose (53.6%), higher energy recovery
and lignin (8.8%)
Phlebia brevispora NRRL- Corn Stover Solid-state Moisture content Total sugar yield was 442 Bioethanol yield, 0.16 Saha et al. (2017)
13108 84%, incubated at mg/g; reduction in g/g pretreated biomass
28 ◦ C for 42 d hemicellulose (34.9%),
cellulose (15.1%), and
lignin (41.9%)
Mixed microbial Corn stover Submerged Incubated at 37 ◦ C for Degradation of cellulose Increased bioCH4 Zhao et al. (2019)
consortium 6d (35.6%), hemicellulose production by 62.8%;
(43.6%), and lignin increased activity of
(13.98%) Methanosaeta
Basidiomycete Irpex Corn stover, barley Solid-state Incubated at 30 ◦ C for Degradation of glucan, Bioethanol yield, García-Torreiro
lacteus straw, corncob, and 21 d xylan, and lignin were 18, 79–106 mg/g et al. (2016)
wheat straw 6.3, and 16.7% for wheat pretreated biomass
straw; 4, 32.8, and 29.3%
for corn stover; 17.1, 37.7,
and 4.3%; for corncob and
19, 20, 6.4%, for barley
straw
Gymnopus contrarius J2 Rice straw Submerged Moisture content Removal of lignin (41.9%), 74% increase in bioH2 Sheng et al. (2018)
65%, incubated at cellulose (22.9%), and yield
25 ◦ C in a static hemicellulose (22.7%);
condition for 21 d decrease of cellulose
crystallinity index by
46.2%
Pleurotus ostreatus DSM Rice straw Solid-state Moisture content 65, Removal of TS (13.2%) and Higher methane yield of Mustafa et al.
11191; Trichoderma 75, and 85%; degradation of 120% and 78.3% when (2016)
reesei QM9414 incubated at 28 ◦ C for hemicellulose (23.7%), pretreated with
30 d lignin (35.3%), and P. ostreatus and T. reesei,
cellulose (13.1%) with respectively
P. ostreatus pretreatment;
removal of TS (10.6%) and
degradation of
hemicellulose (23.3%),
lignin (23.6%), and
cellulose (20.1%) with
T. reesei pretreatment
Mixed microbial Corn straw Submerged Incubated at 30 ◦ C for Degradation of 131.6% higher methane Li et al. (2020)
consortium 14 d hemicellulose (44.4%), production compared to
cellulose (34.9%), and the control
lignin (39.2%)
Paecilomyces inflatus Surgical waste cotton Submerged Incubated at Degradation of Fermentation with Ramamoorthy et al.
ATCC 32919 and waste cardboard 28–30 ◦ C and 180 hemicellulose (76%) and Saccharomyces cerevisiae (2020)
rpm for 3 d lignin (25%); cellulose RW143 yielded 51.2 g/L
crystallinity index ethanol with 58.4%
decreased by 20.1% cellulose conversion
Flammulina velutipes Agropyron elongatum Submerged Moisture content 45, Maximum removal of 120% increased biogas Lalak et al. (2016)
(Tall wheatgrass) 60, 75%; incubation hemicellulose (29.1%), production with 134%
at 28 ◦ C for 28 d lignin (35.4%), and higher methane yield
cellulose (20.5%)
Celustar XL Sugar beet pulp silage Submerged Incubated at 50 ◦ C for Release of reducing sugar 27.9% enhancement in Ziemiński and
(Endoglucanase, and vinasse enzymatic 7d (87.3–92%) biogas yield Kowalska-Wentel
xylanase), Agropect hydrolysis (2015)
pomace (pectinase)
Corn stover Submerged
(continued on next page)

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R. Kumar et al. Journal of Cleaner Production 333 (2022) 130180

Table 5 (continued )
Pretreatment Lignocellulosic Culture Pretreatment Impact of pretreatment on Impact of pretreatment Ref.
microorganisms/Enzyme feedstock technique incubation condition biomass on anaerobic bioprocess
preparations

A mixture of laccase, Incubated at 30 ◦ C Degradation of lignin 17–25% increase in Schroyen et al.

manganese peroxidase, under continuous fraction and release of biomethane yields (2014)
and versatile peroxidase shaking for up to 24 h lignin-derived phenolic
compounds
Co-immobilization of Giant reed (Arundo Submerged Incubated at 30 ◦ C Reduction in cellulose Increased ethanol yield Kirupa Sankar et al.
laccase, cellulase, and donax), Energy cane and stirred at 150 crystallinity index by ranged from 52.1 to (2018)
β-glucosidase (Saccharum rpm for 60 h 5.7–18.4%; maximum TRS 63.4% for the
arundinaceum), Cattail ranged from 158 to 205 fermentation of varying
(Typha angustifolia), and mg/g of different biomass with
Morning glory (Ipomoea pretreated biomass S. cerevisiae
carnea)
Commercial enzymes Energy crops Miscanthus Submerged Incubated at 50 ◦ C Degradation of Higher cumulative Michalska et al.
Celluclast 1.5L giganteus and Sida enzymatic under shaking for 24 hemicellulose, cellulose, biogas production for (2015)
(Cellulase) and hermaphrodita hydrolysis h and lignin were 94.9, 74.5, M. giganteus (230.5
Novozyme 188 and 86.6%, respectively for dm3/kg TS) and
(Cellolbiase) Miscanthus giganteus; and S. hermaphrodita (223.7
86.9, 76.7, and 35.4%, dm3/kg TS)
respectively for Sida
hermaphrodita
Ultraflo® L (Novozymes, Corncob Solid-state Incubated at 50 mM Reduction in cellulose Up to 22.3% increase in Pérez-Rodríguez
Denmark), a cocktail of Na-phosphate buffer (43.3–57.5%) and neutral biogas production et al. (2017)
enzymes, including with solid: liquid detergent soluble
endo-1,3 (4)- 1:10 (w/v) at pH 6.0 compounds (41.7–43.5%)
β-glucanase, collateral for 3 h and stirred at
xylanase, cellobiase, 150 rpm at 40 ◦ C
and cellulase.

3.2.1. LCB pretreatment by fungi 3.2.2. LCB pretreatment by bacteria

Fungi have been extensively employed for hydrolyzing LCB with Employing lignocellulolytic bacteria can be a promising alternative
high lignin content. Several members of Basidiomycota, such as white to fungi for LCB pretreatment, as faster bacterial growth and metabolic
rot fungi, are superior lignin degraders owing to the presence of various rate allow a shorter pretreatment time. Several bacterial species
lignases, including lignin peroxidases, laccases, and manganese peroxi­ belonging to Actinobacteria, α-Proteobacteria, and γ-Proteobacteria can
dases (Zhao et al., 2019). In the last decade, several soft and brown-rot effectively degrade lignin under aerobic conditions (Bugg et al., 2011).
fungi, such as Aspergillus niger, Aspergillus fumigatus, Penicillium chrys­ Compared to white-rot fungi, bacteria are not regarded as potent de­
ogenum, Trichoderma ressei, Gloeophyllum trabeum, Coniophora puteana, graders of lignin (Baba et al., 2017; Rashid et al., 2017). Although
and Postia placenta have been used for hydrolyzing various LCBs to bacteria cannot degrade native lignin anaerobically, they can degrade
enhance the performance of anaerobic bioprocesses and improve the lignin fragments (Khan and Ahring, 2019). Several aerobic bacteria,
biofuel yield (Table 5). While soft and brown rot fungi can degrade LCB such as Pseudomonas sp., Bacillus sp., Sphingobium sp., and Rhodococcus
via their potent cellulolytic enzymes, they can only partially modify sp., can degrade lignin via oxidative reactions catalyzed by
lignin to access the polysaccharidic portion (Abdel-Hamid et al., 2013). lignin-degrading extracellular oxidative enzymes, such as heme perox­
White-rot fungi possess an extensive extracellular enzymatic ma­ idases (Ruiz-Dueñas and Martínez, 2009). Shi et al. (2017) described the
chinery that produces hydrolases that catalyze cellulose and hemicel­ degradation and bioconversion of Kraft lignin as the sole carbon source
lulose degradation. In addition, its ligninolytic system mediates lignin by the β-proteobacterium strain Cupriavidus basilensis B-8, which resul­
degradation, thereby increasing the overall bioavailability of the ted in 41.7% lignin removal in 7 d.
biomass for improved anaerobic bioprocessing (Table 5). Although Microaerobic pretreatment of LCB with a hydrolytic bacterial inoc­
white-rot fungi cannot utilize lignin as a sole carbon source, they are ulum under thermophilic conditions can accelerate lignocellulose hy­
capable of entirely mineralizing lignin present in LCB while consuming drolysis, reduce cellulose crystallinity, and improve biogas productivity
cellulose and hemicellulose as an energy and carbon source (ten Have in AD (Fu et al., 2015). Jaron et al. (2021) pre-digested the pasteurized
and Teunissen, 2001). However, the consequent loss of carbohydrates organic wastes (e.g., waste activated sludge and dairy manure) using a
could be minimized via selective degradation of target substrates, such hyperthermophilic bacterium, Caldicellulosiruptor bescii, at 75 ◦ C and pH
as hemicellulose and lignin, by a few species of white-rot fungi, leaving of 7–8, followed by AD at mesophilic condition (37–41 ◦ C) to get the
the cellulose fraction intact (Kainthola et al., 2021). For example, 2-fold increase in biogas production during the lab- and pilot-scale tests
Pleurotus ostreatus is the most efficient fungi in selectively degrading in comparison to control one. They suggested that 75–85% conversion of
lignin, with a high selectivity value (lignin/cellulose loss), compared to volatile solids into biogas containing 75% methane could be achieved
Phanerochaete chrysosporium, Ceriporiopsis subvermispora, and Trametes commercially using C. bescii pre-digested organic waste streams.
versicolor. However, these fungi also face a formidable challenge in Cellulolytic bacteria, such as Clostridium sp., Cellulomonas sp., Cit­
lignin degradation because of their large and stereo-irregular structures. robacter sp., Bacillus sp., and Streptomyces sp., have been increasingly
Despite the high lignocellulolytic activity of fungi in general, depending used in the pretreatment of lignocellulose during biogas production
on the fungal strain and biomass, fungal pretreatment may lead to sig­ (Table 5) (Sharma et al., 2019). Some rumen and soil cellulolytic bac­
nificant loss of soluble carbohydrates and an extensive pretreatment teria, such as Ruminococcus sp., C. thermocellum, C. cellulolyticum, and
period (Mustafa et al., 2016). To overcome these issues, fungal strains C. cellulovorans produce large multi-enzyme complexes containing cel­
with high lignin selectivity values and optimized process parameters lulases, hemicellulases, and other carbohydrate-active enzymes called
should be considered for the pretreatment or delignification of LCB. cellulosomes (Artzi et al., 2017) which can efficiently hydrolyze cellu­
lose and hemicellulose into fermentable soluble carbohydrates during
pretreatment.

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R. Kumar et al. Journal of Cleaner Production 333 (2022) 130180

3.2.3. LCB pretreatment by microbial consortia as these enzymes vary in their affinity to the inhibitors (Li and Zheng,
Synergistic actions of lignocellulolytic enzymes produced by 2017). A microbial cell has many sites on different enzymes, proteins,
different microorganisms in a mixed culture or consortium can enhance and other macromolecules where these inhibitors can act upon and harm
lignocellulose biodegradation and solubilization during pretreatment. microbial cells (Basak et al., 2020a). Studies also indicated that some of
The use of microbial consortia in lignocellulose pretreatment has several the lignocellulosic inhibitors could even have a stimulating impact on
advantages over the use of pure microbial culture: the higher hydrolytic the activity of certain lignocellulolytic enzymes. According to Tian et al.
capacity of the consortium results in maximum pretreatment efficiency (2013b), the addition of lignocellulosic inhibitors, such as ferulic acid,
in a relatively shorter time; no requirement to maintain optimum con­ p-coumaric acid, and salicylic acid, boosts the activity of cellulase
ditions for the pure culture; mixed consortia do not require aseptic against filter paper by 28.3, 15.1, and 10.1%, respectively. In enzymatic
conditions, thus minimizing the pretreatment cost (Wen et al., 2015). pretreatment, lignocellulolytic enzymes are also not affected by micro­
Therefore, the use of microbial consortia for LCB pretreatment has bial metabolic products, such as organic acids and alcohols, because of
emerged as a promising technological breakthrough. Several studies the absence of microbial metabolism that produces these products.
have successfully developed microbial consortia specialized for ligno­ Using a single enzyme (e.g., cellulase) for pretreatment may result in
cellulose degradation and pretreatment (Tabatabaei et al., 2020a). Most inefficient saccharification of lignocellulose and a longer pretreatment
of these studies have followed the principle of enriching the ligno­ time. However, physicochemical pretreatment followed by enzymatic
cellulolytic microorganisms from specific sources, such as cattle manure saccharification has often been used for better soluble carbohydrate
and rumen fluid (Baba et al., 2017; Takizawa et al., 2018), compost of yields (Pérez-Rodríguez et al., 2017). Alkaline (NaOH)-pretreated
straw and/or other lignocellulosic materials, forest soil, rotten wood biomass (Miscanthus giganteus and Sida hermaphrodita) followed by
(Zhang et al., 2021), termite gut (Lazuka et al., 2018). In designing the enzymatic hydrolysis using cellulase (Celluclast 1.5L) and cellobiase
microbial consortia, the primary aim of enrichment is to increase the (Novozyme 188) resulted in higher saccharification with 20 g/L glucose,
number of specific communities of microorganisms that produce and which subsequently yielded high methane in AD (Michalska et al.,
secrete potent lignocellulolytic enzyme systems, such as 2015).
carbohydrate-active enzymes (CAZymes) cellulosomes and laccase Additionally, mixtures of several enzymes ensure synergistic action
capable of degrading lignocellulose effectively. For example, a ligno­ on different lignocellulosic biomass components, leading to enhanced
cellulolytic microbial consortium enriched from wheat straw compost hydrolysis and solubilization of biomass. For example, co-immobilized
revealed the concoction of laccase producing white and brown rot fungi laccase, cellulase, and β-glucosidase used for LCB pretreatment
with cellulolytic members belonging to Firmicutes, Bacteroides, and decreased cellulose crystallinity and led to a high sugar yield of 205 mg/
Proteobacteria (Zhong et al., 2016). Baba et al. (2017) used the cattle g (Kirupa Sankar et al., 2018). Similarly, crude enzyme cocktails
rumen microflora to pretreat rapeseed biomass. They found that Rumi­ extracted from fungal or bacterial cultures acclimatized to lignocellulose
nococcus sp. dominated the microflora, which could significantly showed greater hydrolytic efficacy than pure enzymes.
degrade the lignocellulosic biomass. Dumond et al. (2021) applied Copper-dependent enzymes, such as lytic polysaccharide mono­
termite gut microbial consortium including Microcerotermes parvus, oxygenases (LPMOs), are designated as novel hydrolytic cocktails to
Termes hospes, Nasutitermes ephratae, and an unidentified species closely depolymerize LCB. Sepulchro et al. (2021) isolated and characterized
related to N. lujae, which could degrade lignin (up to 37%), hemicellu­ MtLPMO9A from Thermothelomyces thermophilus M77 which could be
lose (51%), and cellulose (41%) effectively. However, in-depth research efficiently activated in the presence of light and chlorophyllin for pho­
on this aspect is still limited, possibly due to difficulty in obtaining and tocatalysis of recalcitrant and crystalline cellulose by utilizing molecular
culturing termite gut microorganisms (Zhao et al., 2022). oxygen or hydroperoxide as co-substrate. This indicates that the pres­
Microbial consortia, including bacteria (Maki et al., 2014), fungi ence of a wide range of enzymes in the crude extracts, with ligninolytic
(Kalyani et al., 2013), and mixed bacterial and fungal (Fang et al., and cellulolytic activities, can degrade cellulose fibers, reduce their
2018), have been used in lignocellulose pretreatment over the last crystallinity, and enhance saccharification (Asgher et al., 2013). Despite
decade to increase bioconversion efficiencies. Fang et al. (2018) its advantages, enzymatic pretreatment has several drawbacks, such as a
employed a bacteria-fungal consortium for the selective degradation of lower delignification rate than chemical methods (Asgher et al., 2013),
lignin from tree trimmings, which resulted in high delignification after longer pretreatment time, and high hydraulic retention time (Zabed
16 d pretreatment, with a selectivity value of 2.78. Wen et al. (2015) et al., 2019). The overall performance of enzymatic pretreatment of
evaluated three microbial consortia for pretreating Napier grass, lignocellulose is yet to be evaluated thoroughly. A techno-economic
resulting in 1.32- to 1.49-fold higher methane production in AD than the analysis should be performed compared to established physicochem­
untreated control. A novel lignocellulose-degrading microbial con­ ical procedures for possible real-scale implementation.
sortium was isolated from rotten sawdust, significantly reduced cellu­
lose (37.5%), hemicelluloses (39.6%), and lignin (56.7%) content after 4. Integration of multi-omics approaches in effective utilization
10 d pretreatment, resulting in a 25.6% higher methane yield in AD (Ali of LCB
et al., 2017). Despite these encouraging results, using microbial con­
sortia in real-scale LCB pretreatment is associated with technological The multi-omics approach provides mechanistic insights into the
challenges, such as long-term maintenance of effective microorganisms intricate regulatory nexus that controls gene expression, alteration in
in the consortium, need for optimal conditions for synergistic enzyme protein structure, and composition of metabolites in an organism (de
activities, and loss of soluble carbohydrates and other substrates due to Figueiredo et al., 2021; Patil et al., 2020). Diverse meta-omics tech­
the diversity of microorganisms present in the consortium (Zabed et al., nologies, such as genomics, proteomics, transcriptomics, and metab­
2019). olomics, have improved the accuracy of identifying various microbial
populations, determining functional gene expression and protein in­
3.2.4. Enzymatic pretreatment of LCB teractions, and interpreting the metabolic pathways for an in-depth
Enzymatic pretreatment of LCB employs purified, semi-purified, or understanding of the LCB degradation (Aylward et al., 2012; Rose­
crude enzymes (oxidative and hydrolytic), which are principally pro­ warne et al., 2014). In addition, several meta-omics studies have
duced by bacteria and fungi (Table 5). Enzymatic pretreatment is revealed that members belonging to phyla Firmicutes and Bacteroidetes
gaining attention due to comparatively short reaction periods, low transcribe a diverse set of genes encoding cellulolytic glycosidic hy­
nutrient demand for enzymatic reactions, and more accessible process drolases and sugar transporters, which are ubiquitously involved in LCB
control. Moreover, most cellulolytic enzymes as free catalysts are less degradation (Hassa et al., 2018). Thus, the combined information fa­
sensitive to lignocellulosic inhibitors compared to whole microbial cells cilitates understanding metabolic pathway regulation and identifying

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R. Kumar et al. Journal of Cleaner Production 333 (2022) 130180

efficient organisms and key enzymes for the effective utilization of LCB. enzymes, and enrichment of potential bacterial strains to enhance the
conversion of lignocellulosic substrate into biofuel (Fig. 3a) (Mhuantong
4.1. Genomics et al., 2015). Moreover, 16S rRNA gene sequencing and metagenomics
have helped to identify the dominant LCB-degrading species and their
DNA sequencing using next-generation sequencing (NGS) and whole- diversity (Wei et al., 2015). Operational taxonomic unit (OTU) analysis
genome assembly offers crucial information for identifying functional is used to determine the specific microbial strains or communities that
genes and mapping proteins and mRNA sequences (Gruninger et al., are well adapted for degrading a particular lignocellulosic substrate
2019). Metagenomics is a powerful tool for studying unculturable mi­ (Campanaro et al., 2020). Moreover, sequence-based, and
croorganisms present in environmental samples (Rane et al., 2022). It function-based metagenomics studies have filled the gap between the
can be used to characterize microorganisms that grow on multiple sequence and functions of the genome, thereby linking metabolic ac­
substrates or under different environmental conditions (Mhuantong tivity with the corresponding microbial species. Metagenomic studies
et al., 2015). Using the metagenomic approach, identifying and isolating have also focused on screening biomass-degrading enzymes in the
microorganisms with beneficial traits, such as faster growth rate, higher CAZymes families to identify the efficient enzymes and analyze their
substrate utilization rate, high productivity, and resistance to toxic functional diversity (Abot et al., 2016). Mhuantong et al. (2015)
metabolites may become possible. Notably, the metagenomic approach analyzed the metagenome via DNA sequencing of the fosmid library of
has been applied to environmental samples and allowed identification of the microbial community inhabiting the ecological niche at the bagasse
functional gene loci, the discovery of diverse enzymes, including collection sites of sugar mills. Potential biomass-degrading microbial
uncharacterized enzymes, and functional domains specialized for spe­ communities and their lignocellulolytic enzymes were characterized
cific functions (Xia et al., 2016b). Functional metagenomics of the through shotgun pyrosequencing of the library. Furthermore, various
anaerobic consortium is used to predict polysaccharide utilization loci conserved genes responsible for LCB degradation were identified by
(PUL) (Tomazetto et al., 2020). comparing the microbial composition in different metagenomic data.
Metagenomic analysis of microbiota utilizing LCB can lead to strain
isolation, identification, characterization of carbohydrate-degrading

Fig. 3. Application of multi-omics approaches for the enhancing lignocellulosic biomass utilization; a) structural composition of lignocellulolytic microbial com­
munity based on 16S rRNA gene sequencing (Mhuantong et al., 2015), b) prediction of polysaccharide utilization loci (PUL) from the anaerobic consortium met­
agenome (Tomazetto et al., 2020), c) carbohydrate metabolites and predicted pathways in termite gut reconstructed using integrative omics data analysis (Calusinska
et al., 2020).

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R. Kumar et al. Journal of Cleaner Production 333 (2022) 130180

4.2. Transcriptomics metabolites produced during cellular processes (Roessner and Bowne,
2009; van der Werf et al., 2007). Metabolites generated during meta­
RNA sequencing provides a blueprint of expressed genes and changes bolic pathways can be detected by gas chromatography-mass spec­
in gene expression patterns under a set of metabolic conditions. An in- trometry (GC-MS) and/or liquid chromatography-mass spectrometry
depth study of the transcriptome will aid in determining the biological (LC-MS) (van der Werf et al., 2007). A high-throughput nanostructure
mechanisms used by bacterial species for degrading lignocellulose (Qi initiator mass spectrometry (NIMS) technique has been used in recent
et al., 2011). Transcriptomic analysis of the termite gut and soil metabolomic studies on microbial communities (Cheng et al., 2013;
microbiota grown on different lignocellulose substrates has offered new Northen et al., 2007). In targeted metabolomics approaches, the struc­
insights into the microbiota response to environmental conditions at a ture of lignocellulosic substrates has been analyzed along with the
functional level (Poretsky et al., 2009; Raychoudhury et al., 2013). Gene products and intermediates formed during microbial hydrolysis of LCB
ontology analysis provides essential information regarding genes whose (Klinke et al., 2004). Cellulose, hemicellulose, and lignin are hydrolyzed
expression is necessary for degrading LCB and genes required to detoxify into an array of products, such as D-glucose residues, xylose, mannose,
undesirable metabolites (Stewart et al., 2012). Multiple metagenomic galactose, arabinose, levulinic acid, furfural, furfuryl alcohol, 2-furan­
and metatranscriptomic studies have identified approximately 132 methanol acetate, HMF, and phenolic compounds, which can be iden­
families or subfamilies of CAZymes that actively participate in LCB tified using GC-MS (Zha et al., 2014). The targeted approach can be used
utilization. Metatranscriptomic analysis of CAZymes of rumen microbes to optimize pretreatment conditions, identify inhibitors and their char­
has confirmed the multi-fold enhancement in expression of genes acterization (Raj et al., 2007). The targeted metabolomics approach has
(transcription) involved in carbohydrate metabolism (Fig. 3b) (Huttner been used in various detoxification studies to optimize the fermentation
et al., 2017; Qi et al., 2011). process and increase the product yield (Alriksson et al., 2011).
Furthermore, the expression of members of CAZyme families such as Recent advancements in metabolomics techniques have allowed
GH5, GH6, GH9, and GH48 was upregulated in rumen anaerobes (Dai identification and characterization of the intracellular and extracellular
et al., 2015; Sollinger et al., 2018). The transcriptomic profile of Laeti­ metabolites and aided the interpretation of strain metabolic pathways to
porus sulphureus ATCC 52600 growing on sugarcane bagasse showed an understand their underlying mechanisms (Fig. 3c) (Calusinska et al.,
upregulated mRNA expression of genes encoding redox enzymes along 2020). The cellular responses of Clostridium acetobutylicum during LCB
with those of cellulases and hemicellulases (de Figueiredo et al., 2021). hydrolysis help to understand the inhibitory effects of phenol, fur­
An in-depth transcriptome study can reveal the functional genes aldehyde, and formic acid on carbohydrate metabolism and regulation
involved in lignocellulose degradation and changes in gene expression modules functioning in vivo (Liu et al., 2019a). The systematic analysis
patterns influenced by growth conditions. of the effects of these inhibitors can aid the optimization of fermentation
conditions and strain modifications.
4.3. Proteomics
5. LCB valorization via anaerobic bioprocesses
Although a comprehensive analysis of genomic and metagenomic
data can reveal the potential functional genes; this information often An innovative pretreatment method, along with efficient anaerobic
correlates poorly with protein expression or other strain phenotypes. For bioprocesses, results in maximum digestibility and subsequent valori­
instance, the functional genes identified by genomic and transcriptomic zation of LCB, which helps to overcome the challenges encountered in
data could not identify and correlate the concentration, function, and efficient biofuel production (Nkemka et al., 2015). High-valued
metabolic activity of expressed proteins (Xiao et al., 2017). The fermentative products of anaerobic bioprocesses, such as methane,
comprehensive metaproteomics approach provides a way to analyze hydrogen, ethanol, and biobutanol, can be obtained via photo and
functional proteins in microorganisms found in the natural environment dark-fermentation, AD, ethanol fermentation, and ABE fermentation
and study complex metabolic pathways in greater functional depth (Fig. 4).
(Bastida and Jehmlich, 2016).
Proteins expressed in biological systems can be measured using mass 5.1. Photo and dark fermentation
spectrometry (MS). Proteomics studies are used to evaluate changes in
protein abundance, protein isoforms, post-translational modifications, The sustainable production of bio-H2 from LCB is preferred and
enzyme activity, and their interactions in different environments. MS intensively studied due to its higher energy yield (142 kJ/g), use of clean
and MS/MS-based quantitative proteomic measurements can identify energy, more comprehensive industrial application, ease of control, easy
thousands of peptides or proteins present in the cellular environment conversion to electricity by a fuel cell, and operational safety (Basak
and can be used to characterize these proteins. Metaproteomic analysis et al., 2020a; Ndayisenga et al., 2021). Among the bio-H2 production
of Streptomyces sp. SSR-198 revealed that the proteins identified in its processes, photo-fermentation (light-dependent) or dark-fermentation
secretome consist of cellulases (30%), proteases (21%), other proteins (light-independent) offer a practical application for the conversion of
(32%), and hypothetical proteins (17%) (Singh et al., 2015). In targeted various organic wastes and carbohydrate enriched wastewater into
proteomics analysis of the Thermobifida fusca secretome, the isobaric bio-H2 under moderate operating conditions (Table 6) (Wang and Yin,
tagging approach for relative and absolute quantification (iTRAQ) was 2017). In photo-fermentation, light and organic acids act as the energy
used along with liquid chromatography-tandem mass spectrometry source and electron donor, respectively, and can be utilized by purple
(LC-MS/MS) to evaluate the effects of cellulose and lignin substrates on non-sulfur (PNS) to generate bio-H2 while catalyzing nitrogen fixation
changes in the abundance of proteins and its metabolic activities (Adav reactions using the nitrogenase (McKinlay, 2014). Microwave-assisted
et al., 2010). Identifying and characterizing a protein involved in the alkali pretreated rice straw (0.5% NaOH solution and 15 min micro­
de-polymerizing LCB, degradation of lignocellulose, and detoxifying wave at 2.45 GHz and 1000 W to maintain the temperature at 140 ◦ C)
metabolites will help design an efficient enzyme cocktail for the rapid was enzymatically hydrolyzed to get 69.3% reducing sugars and sub­
fermentation of LCB at an industrial scale (D’haeseleer et al., 2013). sequently used for bio-H2 production of 155 mL/g total volatile solids
(TVS) via dark fermentation. After fermentation, the residual nutrient
4.4. Metabolomics medium, mainly containing acetate and butyrate, was further utilized by
immobilized photo-fermentative synthetic bacteria to generate total
Metabolic studies aim to identify and characterize low molecular bio-H2 463 mL/g TVS, which is 43.2% of the theoretical yield (Cheng
weight substrates, intermediates, and end-products. In microbes, the et al., 2011). A few critical operating parameters, such as the pH, C/N
metabolomics approach can be used to study intra- and extracellular ratio, and light intensity, critically affect the metabolic pathways of

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R. Kumar et al. Journal of Cleaner Production 333 (2022) 130180

Fig. 4. Different anaerobic bioprocesses for the conversion of lignocellulosic substrates to biofuels [adapted from Monlau et al. (2013) with permission from Taylor &
Francis, License No. 5181250532546; Baruah et al. (2018)].

photo-fermentative microorganisms. A low C/N ratio and high pH inoculum was found to be most effective for mesophilic consortia (37 ◦ C)
(>7.6) of the medium can affect microbial growth and damage the with a relative abundance of Clostridiaceae to produce 0.8 mol H2/mol of
membrane of the microbial cells, resulting in microbial cluster forma­ xylose. Similarly, alkaline soaked (24 h treatment at pH 10) thermo­
tion. This leads to a decrease in the light conversion efficiency, which philic consortia (at 55 ◦ C), with a relative abundance of Clostridium and
further decreases the yield and productivity of bio-H2 (Keskin and Thermoanaerobacterium, may produce 1.2 mol H2/mol xylose by
Hallenbeck, 2012). Al-Mohammedawi et al. (2018) evaluated the opti­ repressing the growth of the Lactobacillaceae community (Dessì et al.,
mum pH (7.4), C/N ratio (27.5), and light intensity (126 W/m2) to 2018). However, bio-H2 producing microbiota is highly susceptible to
obtain the maximum bio-H2 productivity and potential of 41.7 and 960 lignocellulosic inhibitors due to their low diversity, sensitive nature,
mL/L, respectively, using Rhodobacter sphaeroides 158 DSM. short substrate retention duration, and a low ratio of inoculum to the
High bio-H2 productivity using pure culture or synthetic co-culture substrate (Basak et al., 2020a). Thus, a suitable combination of pre­
or acclimatized microbiome can be achieved via the dark fermentation treatment and inhibitor detoxification processes is necessary for the
of reducing sugars (Chang et al., 2018). In addition, a diverse microbial sustainable production of bio-H2 using inexpensive lignocellulosic
consortium is required to produce bio-H2 from lignocellulosic waste feedstocks via photo/dark-fermentation.
substrates, which makes the process economical as the system does not
require sterilization (Basak et al., 2020a). However, competitors of
bio-H2 producers (such as lactate-producing bacteria) or bio-H2 con­ 5.2. Anaerobic digestion
sumers (such as homoacetogens and hydrogenotrophic methanogens)
may grow in the reactor, resulting in a drastic reduction of the overall AD is the conversion of organic waste into valuable biogas via inti­
bio-H2 yield (Bundhoo and Mohee, 2016). Inoculum pretreatment by mate syntropy among the cellulolytic/hemicellulolytic microbes,
exposing mixed cultures to harsh environmental conditions (such as acidogenic or fermentative microbes, and methanogenic archaea bac­
temperature and pH shocks) to select H2-producing microbes, such as teria which are responsible for hydrolysis, acidogenesis, acetogenesis,
Bacillus, Clostridium, and Thermoanaerobacterium, which survives and methanogenesis. The anaerobic co-digestion (AcoD), integrated or
through endospore formation, can be a suitable strategy to sustain a high two-stage AD, and bioaugmentation have been identified as mainstream
bio-H2 yield (Galperin, 2013). For example, the acid pretreated biological strategies as AD for biogas production from LCB (Tabatabaei
et al., 2020b). The first step, hydrolysis, is the rate-determining step of

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R. Kumar et al. Journal of Cleaner Production 333 (2022) 130180

Table 6
Valorization of various pretreated lignocellulosic substrates by different anaerobic bioprocesses.
a
Pretreatment Feedstocks Operating conditions Composition of Yield of TRS after Yield and/or productivity of final Ref.
methods and composition before biomass after saccharification products of anaerobic
feedstocks pretreatment pretreatment bioprocesses

Photo/dark-fermentation
Combined Soluble-COD, HCl, 1% (w/w); Enhanced soluble- – Bio-H2 of 42.2 mL/g-dry grass by Yang and Wang
ultrasound and 272.8 mg/g-dry ultrasound treatment COD, 541 mg/g-dry thermal treatment at 100 ◦ C for (2019)
dilute HCl acid, biomass; at 260 W for 30 min biomass; 15 min in anaerobically digested
grass biomass carbohydrates, 86 and heated at 100 ◦ C carbohydrate, 289.7 sludge enriched with Clostridium
mg/g-dry biomass; for 30 min mg/g-dry biomass; sp.
CrI, 21 crystallinity index,
40.8
Fungal, rice straw C, 50.4%; H, Treated with edible C, 38.8%; H, 16.2%; – Maximum bio-H2 produced 126.1 Sheng et al.
28.7%; L, 19.9% fungus Gymnopus L, 11.6% mL/g-substrate by (2018)
contrarius J2 for 15 T. thermosaccharolyticum DD32
d at room
temperature
Ultrasound and – Ultrasound for 1.5 h – – Enhancement of average H2 Wang et al.
acid, Cornstalk at 25 kHz in the production rate (17.03 mL/gCS/h) (2012)
(CS) presence of acid (2% and specific H2 accumulation
H2SO4) (142.59 mL/gCS) of 6.1 and 9.3
times, respectively, in comparison
to the group without treatment
Ultrasound, palm – Ultrasound at 20 kHz – – Increased bio-H2 production from Budiman and
oil mill effluent and 70% amplitude 467 mL to 872.4 mL Wu (2016)
for 45 min
Anaerobic digestion
Steam explosion, C, 29.17%; H, Steam under pressure Hydrolysate in the – Loading rate of F/M, 0.7 g of Baeta et al.
coffee husk 28.96%; L, 17.67% at 120 ◦ C for 60 min liquid stage COD/g of VSinoculum to get the (2017)
contained 47.6% of yield of 144.96 mL CH4/g COD in
C; 57.1% of H; a batch reactor at 35 ◦ C for 25 d of
50.8% L in soluble fermentation
form
Hydrothermal, C, 44.2%; H, Pretreatment at Xylose, 18.4 g/L – Maximum production of 270 mL Ribeiro et al.
sugarcane 23.6%; L, 25.8%; 178.6 ◦ C for 43.6 min (80% of total CH4/g COD in continuous up-flow (2017)
bagasse extractives, 2.2%; at 0.24 g/mL solid sugars) from anaerobic sludge blanket reactor
ash, 1.4% loading rate hemicellulose at 20–30 ◦ C for 168 d of
degraded fermentation
hydrolysate
Hydrothermal, Temperature of Soluble COD, 12.6 g – Maximum production of 266 mL Ghimire et al.
Picea abies 140 ◦ C for 300 min CODs/L; arabinose, CH4/g COD in 103 d in batch 100 (2021)
(Norway spruce) 1.63 g/L; glucose, mL syringes at 55 ◦ C
1.55 g/L; xylose,
1.95 g/L; mannose,
5.11 g/L
Hydrothermal, C, 40.1%; H, Temperature of C, 48.5%; H, 11.3%; – Methane yield of 238.2 mL CH4/g Phuttaro et al.
Napier grass 32.3%; L, 10.2% 175 ◦ C and 113 psi for L, 14.7% VS in 42 d of batch study (2019)
(Pennisetum 15 min
purpureum)
Ultrasound and C, 36.4%, H, Dual-frequency – – Combined pretreatment enhanced Dong et al.
alkali (NaOH), 30.3%; L, 6.9%; TS, sonication, i.e., 57 56.5% biogas yield, 71.4% TS (2018)
corn stalk 90.3%; VS, 87.7% kHz and 20 kHz at 50 removal, 77.1% VS reduction, and
W and 2% NaOH for 19.7% net energy compared with
36 h of treatment time the untreated biomass
using 52 g of
feedstock
Ethanol fermentation
Alkaline C, 42%; H, 20%; L, NaOH, 0.5% (w/v); C, 58%; H, 22%; L, Biomass recovery, 20%; Ethanol yield of 71.8% in 72 h Sahoo et al.
hydrothermal, 19% H2SO4, 2% (w/v); 10% 696 mg/g TRS in 48 h (2017)
Brachiaria mutica autoclaved at 121 ◦ C (cellulase
(Para grass) for 1 h saccharification)
Ultrasound and Solid, 96.67%; C, Biomass loading, 10% Solid 93.47%, C, Maximum TRS 299.74 Ethanol yield of 81.9% Paramasivan
dilute acid, Typha 43.96%; L, 19.27%; (w/v); sulphuric acid, 68.73%; L, 17.53%; mg/g by enzymatic et al. (2021)
angustifolia ash, 3.39%; 1% (w/w); ash, 3.18%; saccharification
extractive ultrasound, power, extractive
(aqueous), 30.57% 70% and 24 kHz at (aqueous), 25.61%
60 ◦ C for 60 min
Alkaline hot-water C, 22.6%; H, NaOH 2%, 120 ◦ C for C, 22.6%; H, 21.9%; Biomass recovery, 30%; Ethanol yield of 95% Eliana et al.
treatment, 20.9%; L, 19.4% 1h L, 6.8% TRS, 146.9 mg/g in 45 h (2014)
Pennisetum (cellulase
purpureum saccharification)
(Elephant grass)
Plasma-assisted L, 19.2%; glucan, A dielectric barrier L, 9.5%; glucan, 47; Material loss of 1.6%, Ethanol yield of 53% Schultz-Jensen
ozonolysis, wheat 41.6%; xylan, 23%; discharge was used to xylan, 18; arabinan, enzymatic et al. (2011)
straw arabinan, 3.5%; convert air to ozone at 2; ash, 6 saccharification yielded
ash, 5.5% atmospheric pressure, 78% sugars after 48 h
(continued on next page)

19
R. Kumar et al. Journal of Cleaner Production 333 (2022) 130180

Table 6 (continued )
a
Pretreatment Feedstocks Operating conditions Composition of Yield of TRS after Yield and/or productivity of final Ref.
methods and composition before biomass after saccharification products of anaerobic
feedstocks pretreatment pretreatment bioprocesses

50% dry biomass

slurry was treated by
ozonolysis for 2 h
Microwave and C, 16%; H, 29.6%; Microwave at 300 W C, 89.2% Enzymatic Ethanol concentration of 20 g/L in Mikulski and
hydrothermal in L, 15.57% for 15 min under 0.37 saccharification in 24 h 48 h after detoxification of toxic Kłosowski
dilute acid MPa hydrothermal yielded TRS of 156 mg/ stress (HMF) with activated (2020)
solution, rye pressure in 0.2 M g carbon
stillages H2SO4 solution
ABE fermentation
Autohydrolysis, C, 34.85%; H, Biomass to liquid Xylose, 18.12 g/L; – Co-digestion of sorghum bagasse Mirfakhar et al.
sweet sorghum 37.32%; L, 27.36%; ration, 8% (w/v), glucose, 4.3 g/L; with sorghum grain powder by (2020)
bagasse ash, 1% 210 ◦ C for 60 min; xylo-oligomers, C. acetobutylicum NRRL B-591
pH, 3.4; activated 11.93 g/L; sweet produced butanol, 5 g/L; acetone,
charcoal, 2.4% (w/v) sorghum grain, 20 3 g/L; ethanol, 0.3 g/L
added to hydrolysate g/L
DESs, corn stover C, 31%; H, 20.1%; ChCl: formic acid C, 47.9%; H, 9.8%; Enzyme dosage 25 FPU/ Butanol, 5.63 g/L; yield, 0.17 g/g;
L, 25.4%; ash, 8.6% ratio 1:2 in acidic L, 27.9; ash, 7.1 g at 130 ◦ C for 3 h productivity, 0.12 g/L/h by
solution yielded 17 g/L of C. saccharobutylicum DSM 13864
glucose
Aqueous ammonia, Glucan 41.7%; acid Combined 5% Glucan, 61.4%; acid Enzymatic ABE fermentation yielded acetone Li et al. (2017)
dilute acid and insoluble L, NH3H2O at 140 ◦ C for insoluble L, 33.7% saccharification by (3.84 g/L), butanol (7.68 g/L),
oxidative 22.53% 1 h and biomass cellulase and xylanases and ethanol (0.6 g/L) in 120 h by
ammonolysis, loading, 1:10 (w/v) in at 50 ◦ C with substrate C. acetobutylicum
sugarcane a 0.5 L high pressure loading (2%, w/v)
bagasse reactor yielded glucose (29.6 g/
L) and xylose (1.16 g/L)
Steam explosion, C, 32–47%; H, Steam under the – Enzymatic hydrolysis of Highest ABE production, 2.07 g/L; Ranjan and
rice straw 19–27%; L, 5–24%; pressure of 0.103 MPa 1% acid hydrolyzed productivity, 0.017 g/L/h; yield, Moholkar
ash, 18.8% at 121 ◦ C for 30 min pretreated biomass at 41.4 g/kg raw rice straw by (2013)
60 ◦ C for 24 h yielded C. acetobutylicum MTCC 481 by
TRS 380 mg/g anaerobic fermentation for 120 h
Microwave and C, 17.9%; H, 28.7% Solid loading, 10% C, 26%; H, 77%; L, 70% glucose recovery Butanol, 8.3 g/L; yield; 46 kg/t López-Linares
hydrothermal, (xylan, 20.7% and (w/v); microwave- 43.3% in solid after enzymatic BSG using C. beijerinckii et al. (2019)
Brewer’s spent arabinose, 8%); L, hydrothermal at fraction; total hydrolysis
grain (BSG) 25.8% 192.7 ◦ C for 5.4 min sugars, 26 g/L;
biomass inhibitors, 2.2 g/L
are present in the
liquid fraction
a
C, cellulose; H, hemicellulose; L, lignin.

the LCB-based AD process and remains a bottleneck in the effective plants in Europe are AcoD-based with the prime substrate as animal
utilization and commercial application of LCB in large-scale biogas manure and agro-industrial along with municipal solid wastes used as
projects (Saha et al., 2019b; Shrestha et al., 2017). Biological pretreat­ co-substrate (Mata-Alvarez et al., 2014).
ment using hydrolytic microorganisms or consortia with strong lignin The application of acclimatized AD microbiota before adding sub­
degradation abilities can shorten the anaerobic fermentation time, strates in anaerobic two-stage co-digestion is beneficial to counteract the
enhance the bio-digestibility, and increase the bio-methanation rates system failures and instability, reduce the impact of inhibitory com­
(Tabatabaei et al., 2020a). In addition, an imbalance in the C/N ratio in pounds, achieve better substrate digestion, and higher gas productivity
the feedstock is another challenge for the anaerobic conversion of LCB to (Kang et al., 2021). Two-stage AD system consists of the acidogenic
biomethane (Saha et al., 2018). fermenter and methanogenic digester to provide optimal process con­
To overcome the substrate-inherent limitations, substrate-specific ditions, balance acidity and hydrogen level pressure for the smooth
pretreatment and/or substrate-focused AD optimization methods by growth of respective microbiota, and enhance energy recovery as bio­
adding complementary nutrients can prepare a more adaptable AD- hythane (H2 + CH4) from the organic feedstocks (Castellano-Hinojosa
microbiome for maximum AD performance (Kurade et al., 2019; Saha et al., 2018). The thermophilic microorganisms have shown high ac­
et al., 2019a). Blending of different organic matter, such as animal tivity in low pH and thermophilic conditions to produce volatile fatty
manure, pig urine, dairy manure, lipidic, municipal, and kitchen wastes acids, which inhibits the methanogens in the acid reactor. The next
with LCB during AcoD improved the methane yield by 4-fold as stage, i.e., methanogenic digester, provides mesophilic conditions and
compared to mono-digestion, mainly due to process stabilization as well neutral pH to bring efficacy and species diversity in methanogenic mi­
as element and nutrient balance (Hagos et al., 2017; Salama et al., croorganisms. Basak et al. (2020b) reported 47% (214.1 mL/g VSadded)
2019). Firmicutes, especially, Bacteroidetes, Actinobacteria, and Clos­ higher energy recovery as biohythane in two-stage AD using fungal
tridiales are observed as dominant phyla during AcoD (Mata-Alvarez (Aspergillus fumigatus) pretreated polysaccharide waste biomass.
et al., 2014). It offers several advantages, such as high pH stability, Bioaugmentation with engineered lignocellulolytic microbiomes, i.
diluting inhibitory compounds, and providing an effective starter inoc­ e., the addition of microbial consortium with potent lignocellulolytic
ulum for the new AD process. However, the operational difficulties in activities during AD, is a promising strategy to increase the digestion of
conventional single-stage co-digestion restrict the maximum conversion LCB for a higher yield of biomethane during the start-up period at a
of organic waste biomass into methane due to acidification of the reactor commercial scale (Tabatabaei et al., 2020b). Such a strategy helps to
by rapid formation of short and/or medium-chain fatty acids, resulting restore the reactor performance, enhancing the conversion rate of lipidic
in a decrease of pH beyond the critical level for methanogenic activity and LCB waste and reducing the lag phase during the start-up period of
(Kurade et al., 2020). Currently, only 10% of large-scale commercial the new system (Tale et al., 2015). The bioaugmented AD system has

20
R. Kumar et al. Journal of Cleaner Production 333 (2022) 130180

shown microbial communities with a large CAZyme secreting popula­ CBP represents an economical and ideal approach for second-
tion in Bacteroidetes and Firmicutes compared to the indigenous generation biofuel production by utilizing a broad spectrum of ligno­
microbiome in conventional AD (Basak et al., 2022). Enhanced sorghum cellulosic substrates without the addition of costly exogenous enzymes
biomass degradation (27%) and increased biomethane yield (20%) (Lugani et al., 2020). Developing pilot-scale and industrial-scale pro­
along with a stable AD-microbiome could be achieved using cellulolytic cesses using CBP in single vessel and temperature are much simpler than
and methanogenic consortia from natural sources, such as cow and goat SHF and SSF due to differences in the operating temperatures during
rumen content (Ozbayram et al., 2018). Applying natural microbial saccharification and fermentation steps (Agbor et al., 2014). However,
consortia in a newly designed bionic reactor based on the ruminant low ethanol tolerance (≤2%, v/v) of thermophilic microbes shows a
stomach produces 21.6 mL/g VS/day and 256.5 mL/g VS from corn significant obstacle in the industrial-scale application (Rastogi and
stover, as productivity and cumulative production of biogas, respec­ Shrivastava, 2017). Thus, a suitable CBP-enabling microorganism is a
tively (Table 6) (Zhang et al., 2014). major quest that limits the process technology design for large-scale
production of low-cost fuels compared to sequential step processes
5.3. Ethanol fermentation (SHF and SSF). The synthesis of robust engineered microorganisms using
synthetic biology, cell-surface engineering, and metabolic engineering
Bioethanol obtained from renewable biomass, especially LCB, is seems to be promising approaches to improve ethanol production
considered a promising alternative to fossil fuels to achieve sustainable through CBP (Kazemi Shariat Panahi et al., 2021; Lugani et al., 2020).
development goals by reducing the emissions of CO, hydrocarbons, and Yanase et al. (2010) genetically engineered a thermotolerant yeast strain
GHGs (Kumar et al., 2019). Therefore, bioethanol production has Kluyveromyces marxianus by co-displaying endoglucanase (from Tricho­
attracted global attention, such as the European Union (EU) has set a derma reesei) and β-glucosidase (from Aspergillus aculeatus) on the cell
target of 3.5% LCB-based bioethanol blended transport fuel by 2021 surface, which grew well at a temperature of 48 ◦ C and yielded 0.47 g/g
(Padella et al., 2019). However, compared to the sugar- or starch-based of carbohydrate. Such development of the recombinant yeast strain
bioethanol production processes, a more complicated and expensive shows a significant advancement towards the realization of CBP.
process consisting of four different steps: pretreatment, saccharification,
fermentation, and purification, is required to produce lignocellulosic 5.4. ABE fermentation
bioethanol (Haghighi Mood et al., 2013; Morales et al., 2021). More­
over, severe pretreatment conditions, including high temperature and The transformation of LCB through developing novel biorefinery
pressure, and the presence of concentrated acids or bases, lead to the designs and technologies for alternative biofuel and chemical produc­
production of toxic by-products that affect the microbial fermentation tion leads to chemical process sustainability, which has gained world­
process, resulting in a low yield of bioethanol (Yuan et al., 2021). wide attention. Butanol is one of the established alternative biofuels,
Ultrasound-assisted pretreatment under mildly acidic conditions can which can be produced via ABE fermentation technology (Mer­
delignify LCB (Saccharum arundinaceum) and expose the cellulose for amo-Hurtado et al., 2021). ABE fermentation is a strictly anaerobic
subsequent saccharification and fermentation, yielding up to 309 process completed in two phases: acidogenic and solventogenic phases.
mg/g-TRSs and 78% ethanol, respectively (Table 6) (Paramasivan et al., During the acidogenic phase, butyric and acetic acids, and gases (CO2
2021). and H2) are formed, accompanied by a drop in the pH of the medium. In
Consolidated bioprocessing (CBP) has been suggested as a fermen­ the solventogenic phase, the acids are re-assimilated to form ABE sol­
tation strategy for obtaining biofuels from pretreated LCB, where a vents along with pH restoration (Capilla et al., 2021). Widely known
combination of two or more microorganisms performs saccharification ABE bacteria from the class Clostridia can consume various carbon
and fermentation in a bioreactor (Mohapatra et al., 2020). In contrast, sources (such as sugars, whey, starch, cellulose, and hemicellulose) to
other approaches, such as separate hydrolysis and fermentation (SHF), produce second-generation biofuels (Zetty-Arenas et al., 2019). How­
simultaneous saccharification and fermentation (SSF), and simultaneous ever, the conversion of LCB to fermentable monomeric sugars via various
saccharification and co-fermentation (SSCF), need multi-steps for the physicochemical and biological methods is the rate-limiting step in
cellulose production, hydrolysis, and fermentation for ethanol produc­ obtaining inexpensive and sustainable feedstocks for ABE fermentation.
tion (Agbor et al., 2014). Based on the limitation of two-step processes in Autohydrolysis by water is an economical and eco-friendly pretreatment
SHF, integrated approaches, such as SSF and SSCF, saccharification and process to release the reducing sugars of hemicellulose from LCB, which
fermentation are conducted in a single reactor, thus allowing low can be an ideal feedstock for Clostridia for butanol fermentation without
operation cost and less inhibitor generation. But different process con­ generating inhibitors. Use of DESs (choline chloride: formic acid), an
ditions for an enzyme (for hydrolysis) and microorganism (for fermen­ effective and biocompatible pretreatment method, was proposed for the
tation) and faster conversion of hexoses than pentoses are critical issues pretreatment of corn stover biomass and released 17.0 g/L (99% yield)
related to SSF and SSCF processes (Vohra et al., 2014). The CBP glucose via enzymatic saccharification and subsequently produced 5.63
approach is lucrative for the bioprocessing of cellulosic biomass using g/L butanol with a yield of 0.17 g/g and productivity of 0.12 g/L/h using
the ingeniously designed microbial consortia, which has desirable as­ a novel strain C. saccharobutylicum DSM 13864 (Table 6) (Xu et al.,
pects related to higher stability, better operating functions, and 2016). C. acetobutylicum cannot ferment hemicellulose-derived sugars
enhanced productivity than using a single organism (Xia et al., 2016a). (mainly xylose) as the sole carbon source due to its carbon catabolite
In addition, synergistic labor division is possible among ingenious repression mechanism (Ren et al., 2010). To completely utilize LCB in
designated microbial consortia, either in cooperation or competitive ABE fermentation, different approaches, such as the co-fermentation
mode, to perform complex tasks, resulting in economic bioethanol with starch and the application of genetically modified microorgan­
production at approximately 41% lower cost than conventional methods isms (Ren et al., 2010), have been adopted to enhance butanol pro­
(Liu et al., 2019b). A moderate temperature (50–70 ◦ C) for the duction and butanol tolerance simultaneously.
saccharification of pretreated LCB is required during CBP to achieve the
efficient performance of cellulolytic enzymes. Therefore, 6. Sustainability aspects of valorization of LCB into biofuels
high-temperature resistant anaerobic thermophiles prefer microorgan­
isms over conventionally used yeast cells for CBP for biofuel production. The sustainability aspects of different methods used for the valori­
Furthermore, anaerobic thermophiles, such as Clostridium and Caldi­ zation of LCB can be judged by techno-economic evaluation, life-cycle
cellulosiruptor, can efficiently utilize monosaccharides (C6 and C5) and assessment (LCA), environmental impact assessment, and
are mainly resistant to inhibitors during fermentation (Singh et al., thermodynamic-based (emergy/energy/exergy) approaches (Soltanian
2017b). et al., 2020). The energy analysis provides information about energy

21
R. Kumar et al. Journal of Cleaner Production 333 (2022) 130180

efficiency considering only energy quantity. In contrast, exergy includes bottleneck in LCB bioprocessing is its pretreatment to make its recalci­
both, quality and quantity of energy flow in a system following the first trant structure readily biodegradable. Several studies have evaluated
and second law of thermodynamics (Aghbashlo et al., 2019). The exergy various biological and non-biological strategies for the effective pre­
analysis measures in terms of exergy destruction linked to economic loss treatment of LCB; however, the conventional processes still pose several
and resources degradation of the system under consideration, thus limitations. Therefore, apart from the fine-tuning of existing technolo­
making a good correlation with GHGs emission (Soltanian et al., 2019). gies, there is a need to develop novel pretreatment methods to improve
LCA could measure and quantify the environmental impacts of the final the sustainability and economic viability of biofuel production. Based on
product in the energy system, but difficult to evaluate environmental our extensive literature review, several critical aspects are summarized
consequences at the component level or intermediate products. These below that may be considered to overcome the current challenges for the
limitations can be fixed mainly by integrating LCA and economical with effective valorization of LCB.
exergy-based approaches, such as exergoenvironmental and exer­
goeconomic analysis tools, which provide vital information about hot i. In-depth understanding of various intrinsic properties of LCB,
spots of thermodynamic inadequacy, techno-economic feasibility, and including its dielectric properties, moisture content, presence of
impacts on the environment during each flow and an intermediate hydroxyl groups, crystalline/amorphous structures, and other
component of lignocellulosic biofuels production system (Aghbashlo features, such as the characteristics of lignin and its interactions
et al., 2021; Fallahi et al., 2021). with cellulose and hemicellulose, is necessary to ensure the se­
The environmental impact during biofuels production depends upon lection of the appropriate pretreatment method.
the types of feedstock and process conformation. For example, methanol ii. To overcome the challenges of low yield of fermentable carbo­
production using corn as a feedstock has shown a negative emission of hydrates, high energy consumption, discharge of polluting
0.99 kg CO2-eq/kg CH3OH in comparison to potential global warming wastewater, and release of inhibitory compounds, it is crucial to
value of 2.9 kg CO2-eq/kg CH3OH for coal-based production (Kajaste develop more advanced pretreatment methods. Few emerging
et al., 2018). O’Connor et al. (2020) demonstrated surplus energy of physicochemical pretreatment methods with mild/no use of
73–79% generated along with net reduction of CO2 ranging in-between chemicals, including microwave, ultrasound, DESs, irradiation,
2059 to 173,237 kg CO2-eq/yr through small-scale AD plants using ozonolysis, SC-CO2, and SEP show great potential for the efficient
livestock manure and municipal organic waste from Irish dairy farms valorization of LCB. However, these pretreatment methods have
with herd sizes greater than 100 cows. The utilization of specific pros and cons related to eco-friendliness and cost-
biomass-derived fuels results in zero net CO2 emissions due to the effectivity for the complete delignification or effective biomass
biogenic nature of CO2 emitted during their generation and consump­ utilization.
tion (Mandley et al., 2020). However, various factors, such as the iii. Microbial consortia used for anaerobic bioprocesses are vulner­
composition of the feedstock, pretreatment method enzymatic sacchar­ able to lignocellulosic inhibitors. Therefore, it is necessary to
ification or microbial hydrolysis, fermentation/AD process, and down­ detoxify these toxic compounds using cost-effective, technologi­
stream recovery, have significantly affected economic feasibility, cally sound, and highly efficient methods. Adsorption-based
envirosafety, and sustainability during lignocellulosic biofuels produc­ detoxification using porous, activated carbon may be one such
tion (Zabed et al., 2019). effective method to ensure the sustainable valorization of LCB via
The pretreatment process has been identified as a critical step in microbial fermentation.
impacting sustainable, economic, and environmentally benign biofuel iv. Biological pretreatment of LCB using cellulolytic bacteria,
production due to its chemical-dependent and energy-intensive nature including Bacteroidetes, Firmicutes (mainly Clostridia), and fungi
(da Silva et al., 2016). SEP was assessed as most exergy-efficient, low (especially white-rot fungi), exhibit great potential for hydro­
environment burden, and high index of sustainability approach for lyzing cellulose and hemicellulose; however, their involvement in
lignocellulosic ethanol production from sugarcane bagasse using SSF lignin biodegradation remains unclear. The lignocellulolytic mi­
process, followed by organosolv and dilute acid methods (Ojeda et al., crobial communities showing excellent capacities for LCB
2011). Hoang et al. (2021) evaluated microwave-based heating as faster biodegradation via their lignocellulolytic enzymatic machinery
and energy-efficient method that could reduce 10-fold in pretreatment can be further assessed using the combination of omics ap­
time while consuming 22.5-fold less energy than conventional heating. proaches to develop effective biological-based strategies to
The energy consumption was reduced from 560 kJ to 192 kJ by enhance the hydrolytic efficiency. Furthermore, bio-mimicking
switching the oil-bath technique to microwave-assisted pretreatment in the natural ecosystem, co-digestion, and natural microbial con­
IL-based (1-ethyl-3-methylimidazolium acetate) wood delignification sortia are potential alternatives for enhanced LCB
(Wang et al., 2013). The microbial pretreatment method was investi­ biodegradation.
gated as the highest exergy efficient process (90.9%) during oil-palm v. The efficacy of various anaerobic bioprocesses is debilitated due
processing due to relatively less energy and chemicals consumption to the low bioavailability of LCB for bioenergy conversion.
than SEP and organosolv processes (Ofori-Boateng and Lee, 2013). The Therefore, a comprehensive understanding of the recalcitrant
biochemical composition, especially the lignin content of LCB, has also nature of LCBs and their efficient pretreatment methods is the key
played a significant role in the exergy efficiency of pretreatment pro­ to improving the overall productivity, yield, and economics of
cesses (Ortiz and de Oliveira Jr, 2014). Further, downstream sacchari­ bioenergy production through various anaerobic bioprocesses.
fication and fermentation pretreated sugarcane bagasse using SSF
configuration outperformed the SHF approach in exergy efficiency Author credit statement
during bioethanol production (Ortiz and de Oliveira Jr, 2016). Overall,
future studies need to investigate on exergoeconomic and exergoenvir­ Ramesh Kumar: Conceptualization, Methodology, Funding acqui­
onmental aspects of various unexplored pretreatment methods to lower sition, Writing- Original Draft, Writing – review & editing, Tae Hyun
the LCB pretreatment cost while reducing the exergy destruction cost of Kim: Writing- Original Draft, Writing – review & editing, Supervision.
saccharification and/or fermentation subsystem (Soltanian et al., 2020). Bikram Basak: Writing- Original Draft, Writing – review & editing.
Swapnil M. Patil: Writing- Original Draft, Funding acquisition, Writing
7. Conclusions and future perspectives – review & editing, Hoo Hugo Kim: Writing- Original Draft, Writing –
review & editing. Yongtae Ahn: Writing – review & editing. Krishna
Bioenergy production from LCB via anaerobic bioprocesses is vital Kumar Yadav: Writing – review & editing. Marina M.S. Cabral-Pinto:
for the sustainable development of society. However, a critical Writing – review & editing. Byong-Hun Jeon: Conceptualization,

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R. Kumar et al. Journal of Cleaner Production 333 (2022) 130180

Resources, Supervision, Funding acquisition, Project administration, production: bacterial flora and enzyme activity analysis. J. Biosci. Bioeng. 123 (4),
489–496.
Writing – review & editing.
Baeta, B.E.L., Cordeiro, P.H.M., Passos, F., Gurgel, L.V.A., de Aquino, S.F., Fdz-
Polanco, F., 2017. Steam explosion pretreatment improved the biomethanization of
coffee husks. Bioresour. Technol. 245 (Pt A), 66–72.
Declaration of competing interest Baksi, S., Saha, S., Birgen, C., Sarkar, U., Preisig, H.A., Markussen, S., Wittgens, B.,
Wentzel, A., 2019. Valorization of Lignocellulosic Waste (Crotalaria juncea) Using
The authors declare that they have no known competing financial Alkaline Peroxide Pretreatment under different process conditions: an optimization
study on separation of lignin, cellulose, and hemicellulose. J. Nat. Fibers 16 (5),
interests or personal relationships that could have appeared to influence 662–676.
the work reported in this paper. Barakat, A., Monlau, F., Steyer, J.P., Carrere, H., 2012. Effect of lignin-derived and furan
compounds found in lignocellulosic hydrolysates on biomethane production.
Bioresour. Technol. 104, 90–99.
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This work was supported by the Mid-Career Research Program [grant volatile oils for the synthesis of nanoparticles and nanostructured materials.
Nanoscale 12 (45), 22845–22890.
number 2020R1A2C3004237] and the Creative and Challenging Barua, V.B., Goud, V.V., Kalamdhad, A.S., 2018. Microbial pretreatment of water
Research Program [grant numbers 2020R1I1A1A01072964 and hyacinth for enhanced hydrolysis followed by biogas production. Renew. Energy
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Recent trends in the pretreatment of lignocellulosic biomass for value-added
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