Osman Et Al. (2021)
Osman Et Al. (2021)
https://doi.org/10.1007/s10311-021-01273-0
REVIEW
Received: 6 May 2021 / Accepted: 9 July 2021 / Published online: 23 July 2021
© The Author(s) 2021
Abstract
The global energy demand is projected to rise by almost 28% by 2040 compared to current levels. Biomass is a promising
energy source for producing either solid or liquid fuels. Biofuels are alternatives to fossil fuels to reduce anthropogenic
greenhouse gas emissions. Nonetheless, policy decisions for biofuels should be based on evidence that biofuels are produced
in a sustainable manner. To this end, life cycle assessment (LCA) provides information on environmental impacts associated
with biofuel production chains. Here, we review advances in biomass conversion to biofuels and their environmental impact
by life cycle assessment. Processes are gasification, combustion, pyrolysis, enzymatic hydrolysis routes and fermentation.
Thermochemical processes are classified into low temperature, below 300 °C, and high temperature, higher than 300 °C,
i.e. gasification, combustion and pyrolysis. Pyrolysis is promising because it operates at a relatively lower temperature of
up to 500 °C, compared to gasification, which operates at 800–1300 °C. We focus on 1) the drawbacks and advantages
of the thermochemical and biochemical conversion routes of biomass into various fuels and the possibility of integrating
these routes for better process efficiency; 2) methodological approaches and key findings from 40 LCA studies on biomass
to biofuel conversion pathways published from 2019 to 2021; and 3) bibliometric trends and knowledge gaps in biomass
conversion into biofuels using thermochemical and biochemical routes. The integration of hydrothermal and biochemical
routes is promising for the circular economy.
Introduction
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4076                                                                                     Environmental Chemistry Letters (2021) 19:4075–4118
utilisation to produce fuel and chemicals is required (Bharti           as shown in Fig. 1. There are unprecedented challenges with
et al. 2021). Biomass is classified as non-lignocellulosic or           the integration of thermochemical and biochemical routes.
lignocellulosic in nature and exists in various forms such as           For instance, the catalysts or solvent utilisation of the ther-
woody, herbaceous, aquatic debris, farming manure and by-               mal routes may result in poisoning or kill the microorganism
products and other forms (Osman et al. 2019; Kaloudas et al.            or generate various inhibitors that can affect the biological
2021). Various technologies are used to convert biomass into            progress routes. Furthermore, this integration may lead to
fuel or chemicals, such as gasification, combustion, pyroly-            additional costs.
sis, enzymatic hydrolysis routes and the fermentation pro-                 Identifying sources of biofuels such as biodiesel and
cesses (Abou Rjeily et al. 2021; Peng et al. 2020).                     biochar can potentially reduce the environmental impacts
    A recent review discussed integrating hydrothermal and              of fossil fuels (Balajii and Niju 2019; Gunarathne et al.
biochemical routes in biomass utilisation from a circular bio-          2019). Biofuels can also counter the increasing use of fossil
economy approach (Song et al. 2021). The thermochemical                 resources and prevent pressure on non-renewable sources
methods usually involve a high energy intake along with sol-            (Peng et al. 2020; Hassan et al. 2020). However, it is impor-
vent or catalyst addition. Meanwhile, the biochemical route             tant to use practical, scientific and robust tools to evaluate
has a lengthy cycle period and is less efficient in breaking            the real benefits of using biofuels over conventional energy
down recalcitrant biomass materials. Thus, combining those              sources (Chamkalani et al. 2020; Kargbo et al. 2021). Life
two routes can be promising by incorporating the benefits of            cycle assessment (LCA) has been identified as a compre-
both methods in biofuel processing. They proposed a sche-               hensive evaluation approach (Astrup et al. 2015) to measure
matic route where hydrothermal routes are being used in the             environmental impacts over the entire production chain of
pretreatment stage to prepare the appropriate biomass feed-             biofuels (Collotta et al. 2019).
stock for the following biological routes to improve the over-             Therefore, this review aims to critically evaluate exist-
all process efficiency and final product yields and vice versa,         ing biomass to biofuel pathways and associated studies
Fig. 1  Integration of hydrothermal and biochemical routes in biomass   ical route or vice versa by thermochemical pretreatment for the fol-
utilisation from a circular economy approach. Firstly, the biomass is   lowing biochemical route and eventually producing biofuel or chemi-
pretreated using a biochemical process for the following thermochem-    cals
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Environmental Chemistry Letters (2021) 19:4075–4118                                                                       4077
which evaluated environmental impacts for the entire life         sectors comprising heat, power and transport fuel (Kargbo
cycle. The main objectives were to: (1) critically review         et al. 2021; Wang et al. 2020a). For this purpose, two
recent advances in biofuel production processes, (2) ana-         grouped distinct routes, namely thermochemical and bio-
lyse existing LCA studies and highlight key methodological        chemical, are currently used. Thermochemical methods use
approaches and present critical findings.                         the whole biomass in the presence of a heat source and con-
                                                                  trollable oxygen atmosphere to modify it to different energy
                                                                  forms.
Bibliometric analysis                                                In contrast, biochemical methods employ enzymes, bac-
                                                                  teria or other engineered organisms to transform it to liquid
Bibliometric research methodology: TOPIC: ‘biomass                fuels such as drop-in-biofuels (Shen and Yoshikawa 2013;
pyrolysis’ OR TOPIC: ‘biomass gasification’ OR TOPIC:             Singh et al. 2016). During the past decades, the biomass-
‘biomass combustion’ OR TOPIC: ‘biomass hydrothermal              derived fuel synthesis process has upgraded from the first-
liquefaction’ OR TOPIC: ‘biomass torrefaction’ OR TOPIC:          generation biofuel to fourth-generation biofuel, passing by
‘biomass fermentation’ OR TOPIC: ‘anaerobic digestion’            second and third generations. Food crops, inedible biomass,
AND TOPIC: ‘biomass into fuels’ AND TOPIC: (‘thermo-              macro/microalgal biomass and genetically bioengineered
chemical’ OR ‘thermo-chemical’) AND TOPIC: ‘biochemi-             algal and microbial systems-based biofuels are examples for
cal’. The document type selected in the bibliographic search      the first, second, third and fourth generations, respectively
was articles, the timespan: All years.                            (Martin 2010; Adelabu et al. 2019; Aro, 2016; Ben-Iwo
   It is a complex process to assess the sustainability of bio-   et al. 2016). Innumerable biomass-based fuels, chemicals
fuels. This is because the use of energy crops can cause          and organic compounds such as methane, ethane, propane,
the transformation of natural and agricultural land for the       butane, ethylene, methanol, ethanol, butanol, dimethyl
cultivation of these crops. Moreover, various technical path-     ether, ammonia, acetic acid, formaldehyde, gasoline, diesel,
ways range from biological to thermochemical conversion           wax, paraffin, bio-jet fuels and others have been produced
processes, all involving range of products and co-products.       throughout different biomass to liquid routes and presently
Therefore, it is imperative to conduct the LCA of the biofuel     available in the markets throughout the world (Demirbas and
production chain. This study provides an overview of LCA          Demirbas, 2010).
approaches by recent studies. Keywords: ‘biomass’, ‘bio-
fuel’, ‘life cycle assessment’, ‘environmental impact assess-     Thermochemical conversion methods
ment’, were used for literature search in the Web of Sci-
ence database. Forty most complete studies published from         Thermochemically, diverse technologies including direct
2019–2021 were selected for analysis in the present study.        combustion, torrefaction, hydrothermal liquefaction, pyroly-
                                                                  sis and gasification have been implemented to produce liquid
                                                                  fuels from biomass, as shown in Fig. 2. Practically, the bio-
Biomass conversion technologies                                   mass is decomposed in controllable operational conditions to
                                                                  produce solid, liquid and gas (syngas), which need a supple-
Harnessing various renewable energy resources is consid-          mentary catalytic promotion process to produce liquid fuels
ered affordable, reliable and sustainable solutions for their     called drop-in biofuel. One of its most important features is
excessive availability, such as agriculture wastes, domestic      its capabilities to utilise any biomass type as a biomaterial
wastes, forest residues, industrial wastes and human excreta.     feedstock, unlike biochemical conversion methods (Raheem
Among them, biomass is the most significant contributor           et al. 2015).
with 9% (~ 51 EJ) of the global overall primary energy sup-           The thermal-based processes are also classified into low-
ply, out of which about 55% is traditionally used in daily        temperature, which typically operate at < 300 °C, such as
living activities such as heating and cooking, especially in      torrefaction, hydrothermal carbonisation and high-temper-
developing countries (Chan et al. 2019). Slade et al. (2014)      ature that operate at > 300 °C, such as gasification, combus-
revealed the possibility of biomass, wastes and energy crops      tion and pyrolysis biomass conversion methods (Quereshi
for sharing up to ~ 100 EJ in the world energy supply (Slade      et al. 2021). The direct combustion (flaming or smoulder-
et al. 2014).                                                     ing) of biomass to produce energy usually operates in the
   Economically, biomass combustion is not the best strat-        temperature range of 1000–2000 °C in the presence of air.
egy to utilise biomass because of causing severe environ-         However, there are emissions associated with such processes
mental damage as well as not recovery of the total energy         as NOx and pollutants (Osman 2020). Hence, gasification
stored in the substrates (Ullah et al. 2015). In this context,    which typically operates at 800–1300 °C is seen as a poten-
biomass conversion into solid, liquid and gaseous forms is        tial substitute to produce energy and chemicals as well. The
deemed an efficient and green energy supplier for various         synthesis gas produced from the gasification process can
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Fig. 2  Thermochemical conversion of biomass, including hydro-           cessing plants into liquid biofuels for energy purposes or for the pro-
thermal liquefaction, pyrolysis, torrefaction, gasification and direct   duction of value-added chemicals
combustion processes. Different types of biomass are treated in pro-
be used for electricity production, as well as the conversion               In waste-to-energy facilities, biomass can be separately
into liquid fuel via the Fischer–Tropsch route. Interestingly,           burned or combined in co-firing with coal to produce steam,
pyrolysis is considered a promising route requiring a lower              used later in electricity generation. The net electricity effi-
temperature of up to 500 °C compared to the gasification                 cacy generated from coal/biomass in co-firing power plant
process.                                                                 system varied from 36 up to 44% based on as-used strategy
                                                                         and biomass specifications (quantity and quality). Despite
Direct combustion                                                        the present feasibility of 20% of co-firing as energy basis
                                                                         in addition to a theoretical achievability of 50%, only less
 Biomass utilisation as fuel was closely linked with the                 than 5% and sometimes surpasses to 10% of biomass con-
 beginning of human civilisation. Moreover, it is the high-              tribution continuously. It has been estimated that only 10%
 est contributor source of clean energy globally (Mladenović             of biomass usage in co-firing systems in power plants can
 et al. 2018). Biomass combustion is described as a group                decline the release of C
                                                                                                 O2 to the atmosphere from 45 to 450
 of chemical reactions involving carbon dioxide and water                million tonnes/year by 2035 (Sahu et al. 2014). Considering
 formation resulting from the transformation of carbon and               the physicochemical properties of fuel and its required vol-
 hydrogen, respectively, by oxidation reactions. Improper                ume to air for avoiding any troubles in the fuel-to-air ratio,
 oxygen quality can result in incomplete combustion associ-              excessive air can be forwarded to the reaction to control
 ated with release of atmospheric polluters (i.e. CO, NOX,              the temperature of the burning system and ensure complete
SO2 and particulate matter) (Yang et al. 2020). Nowadays,               combustion (Vicente and Alves, 2018). Majorly, combus-
 the usage of effective fabricated combustion systems such               tion physicochemical features of biomass can be catego-
 as combustion control systems that simultaneously use con-              rised into macroscopic and microscopic. Comprehensively,
 ventional and alternative biomass resources has become a                macroscopic features are provided by macroscopic analyses
 predominant feature industrially.                                       such as proximate analysis such as moisture tenor, sulphur,
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Environmental Chemistry Letters (2021) 19:4075–4118                                                                               4079
particle magnitude, calorific value, bulk density, fixed car-       Table 2  Physicochemical characteristics of biomass and coal-based
bon and ash fusion. This is coupled with ultimate analysis          fuels (Demirbas, 2004)
such as C, H, N, O and S %, whereas microscopic analyses            Property                          Biomass                  Coal
include chemical, thermal and mineral data (Khodaei et al.
                                                                    Particle size (mm)                3                        100
2015).
                                                                    Fuel density                      500                      1300
   Main combustion reactions are as follows: (1) drying
                                                                    Carbon content*                   43–54                    65–85
out of biomass, (2) pyrolysis, (3) pre-combustion reaction,
                                                                    Oxygen content*                   35–45                    2–15
(4) primary combustion, (5) secondary combustion and (6)
                                                                    Sulphur content*                  Max 0.5                  0.5–7.5
effluent stack gas. Parameters that influence the combus-
                                                                    AL2O3 content*                    2.4–9.5                  15–25
tion process include biomass magnitude, specific gravity,
                                                                    SiO2 content*                     23–49                    40–60
moisture tenor, ash percentage, elemental composition and
                                                                    K2O content*                      4–48                     2–6
anatomical structure as lignin, cellulose and hemicellulose.
                                                                    Fe2O3 content*                    1.5–8.5                  8–18
Different researchers highlighted that about 95–97% of the
                                                                    Ignition temperature              418–426                  490–595
global bioenergy production is based on direct biomass com-
                                                                    Heating value                     14–21                    23–28
bustion (Fouilland et al. 2010; Zhang et al. 2010). Given the
massive quantity of ash produced from coal burning (∼780            *(wet % of dry fuel)
million tonnes), a less quantity of biomass ash (∼ 480 mil-
lion tonnes/year) was assumed to be generated coincided
with the burning of 7 billion tonnes of biomass (Vassilev              As a solid fuel, fossil-based fuels are still dominating this
et al. 2013; Izquierdo and Querol, 2012). Retrofitting invest-      sector for power generation and heat. However, biomass uti-
ment cost characterised to various power plants was USD             lisation in the co-combustion along with fossil-based fuel
430–500/kW, USD 760–900/kW and USD 3000–4000/kW                     is seen as a cost-effective and interesting option (Variny
for co-feed plants and separate feed plants indirect co-fir-        et al. 2021). Co-combustion of those two feedstocks offers
ing, respectively. These investigated costs were totally more       higher power generation than biomass alone, and biomass
minuscule than the specified outlays of 100% biomass power          ash is acting as a sulphur capture and mitigates the sulphur
generations facilities (Sahu et al. 2014). Table 1 presents         oxide emissions. On the other hand, some challenges arise
the energy content in MJ/kg for several kinds of biomass,           when mixing fossil-based coal with biomass, leading to
whereas Table 2 displays the differences in the physicochem-        higher corrosion, slagging and fouling due to the high alkali
ical characteristics of biomass and coal-based fuels.               contents within the biomass. In fact, the projected gradual
Data sourced from: Sami et al. 2001; Demirbas 2001; Demirbas 2005; Atimtay 2010; Haykiri-Acma 2003; Borjesson 1996; Raveendran and
Ganesh 1996; Erol et al. 2010; Friedl et al. 2005
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4080                                                                              Environmental Chemistry Letters (2021) 19:4075–4118
shutdown of fossil-based power plants will limit this co-             Commercially, the torrefaction process is a potential
combustion approach. Technologies such as gasification and        scenario to be applied in various applications. Salapa et al.
pyrolysis should be the main focus, to be competitive and         revealed the high adsorption capacity of torrefied barley
fully available in the near future.                               straw of 11.65 mg/g at operating parameters of 220 °C and
                                                                  20 min (Salapa et al. 2018). Other researchers evaluated the
                                                                  torrefaction process’s impacts at different contact periods
Torrefaction                                                      (i.e. 20, 40 and 60 min) and temperature (160–260 °C) on
                                                                  ethanol generation based on rice straw. They found out that
Torrefaction is an endothermic pretreatment pathway that          the best yield of 351 mg/g was obtained at operating param-
mainly proceeded at temperatures ranging from 200 to              eters of 220 °C and 40 min.
300 °C and a non-accelerated heating rate of less than 50 °C/         Additionally, they confirmed that the torrefied biomass
min in an oxygen-free atmosphere. This process is used for        enhanced the yield of ethanol production at a value of
upgrading the solid biomass to produce a torrefied prod-          50.67% compared with the untreated one (Chiaramonti et al.
uct used later as a suitable alternate to coal (Cahyanti et al.   2011; Sheikh et al. 2013). An enhancement in the ethanol
2020). Three transformational reactions, including: vola-         production yield is based on torrefied sugarcane bagasse and
tilisation, polymerisation and carbonisation, occur during        waste jute caddies by 19.34 and 20.28%, respectively, com-
the torrefaction process. The process efficacy is influenced      pared with the untreated biomass (Chaluvadi et al. 2019).
by temperature, reaction time, particle magnitude, carrier            Igalavithana et al. demonstrated that torrefied product
gas type and flow, catalyst and performance index (Chen           could be positively utilised in soil improvement because it
et al. 2021). This strategy significantly improves the phys-      increases air space, water retention efficiency, plant pros-
icochemical properties of utilised biomass such as hydro-         perity, microbial community and enzymes activity (Igala-
phobicity, grindability, mass/energy density, ignitability,       vithana et al. 2017). Ogura et al. observed an increase in
moisture expelling and homogeneity (Chen and Kuo 2011).           the growth of the J. curcas when it was exposed to varied
    Commonly, the torrefied product is termed bio-coal or         ratios of 250 °C torrefied biomass of 1, 3 and 5% (Ogura
green coal and biochar when used as fuel and soil amend-          et al. 2016). The feasibility of using torrefaction condensate
ment. Based on the mode of operation, the torrefaction pro-       in plant safeguarding pathways (pest repellent, insecticide
cess can be practically classified into dry, wet and steam        and herbicide) was confirmed considering its minimum
modes (Barskov et al. 2019). In dry torrefaction, biomaterial     amounts of polycyclic aromatic hydrocarbons and phenolic
feedstock can be torrefied in non-oxidative; for example,         compounds. Comparing the as-generated condensate result-
nitrogen and carbon dioxide are carrier gases or oxidative        ing from different biomass feedstocks such as pine bark,
mediums such as air, flue gases and other streams with vari-      forest residue, wheat straw and willow biomass, the con-
ous oxygen concentrations at working temperatures ranging         densate based on willow had the best pesticide performance
from 200 to 300 °C. Attributing to oxygen presence, the           (Hagner et al. 2020). Table 3 presents more details about the
oxidative scenario has a better reaction rate than the other      physicochemical properties of numerous biomass after the
non-oxidative scenario and minimises the reaction time            torrefaction process.
(Thanapal et al. 2014; Lynam et al. 2011).
    Contrarily, in the wet torrefaction, the biomass is torre-    Hydrothermal liquefaction
fied in a wet environment, typically water and dilute acids
at 180–260 °C and 5–240 min for surrounding temperature           Hydrothermal liquefaction is defined as a thermochemical
and holding time, respectively, and the produced solid is         pathway at which the lignocellulosic feedstock, whether wet
termed as hydrochar. Under these subcritical conditions,          or dry, is effectively decomposed into renewable liquid fuel
physicochemical properties of water such as density, dif-         (Guo et al. 2015). Based on the mode of operation, it can
fusivity, dielectric constant and viscosity alter and improve     be divided into two main subclasses: (1) indirect liquefac-
the biomass degradation process, which further upgrades           tion and (2) solvent liquefaction (Mika et al. 2018). In the
the torrefaction process (Bach and Skreiberg 2016; Balat          first scenario, biomass or its liquefied products are first con-
et al. 2008).                                                     verted into syngas followed by a subsequent fuel synthesis
    Besides the two mentioned routes, steam torrefaction          (i.e. alcohols and alkanes). In contrast, in the second, direct
by introducing steam with elevated temperature and pres-          conversion of biomass into liquid fuel occurs by the action of
sure is conducted to torrefy the biomass at 200–260 °C and        proton solvents such as water, alcohols, phenols, sulpholane
5–10 min for environmental temperature and contact period,        and ionic liquid. Solvent liquefaction has the priority to be
respectively. The subsequently accelerated venting of the         implemented over the other scenario because of its remark-
pressure will allow steam to bulge the biomass and split it       able merits, moderate operational conditions and higher
with minor loss in the feedstock.                                 yield of products (Gollakota et al. 2018).
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Environmental Chemistry Letters (2021) 19:4075–4118                                                                                      4081
Cotton stalk           16.48–34.01           53.62–75.44            4.79–9.88     0.25–0.83 0.06–0.14 18.68–25.43        Chen et al. (2014a),
Corn stalk             18.41–41.19           35.30–69.32            9.18–20.52    0.18–0.85 0.06–0.15 18.26–23.61         Chen et al.
                                                                                                                          (2014b), Chen
                                                                                                                          et al. (2014c)
Rice straw             17–48                 44.5–79.6              6–8           0.24–0.81 0.09–0.16 19.0–28.6          Nam and Capareda
                                                                                                                          (2015)
Oil palm fibre         5–25                  3–48                   6–7           0.22–0.62 0.02–0.10 11.13–23.98        Chen et al. (2013)
Cryptomeria            12–25                 5–54                   0             0.23–0.63 0.02–0.09 21.94–28.81
 japonica
Coconut fibre          2–27                  2–40                   0.5–3         0.22–0.55   0.02–0.09   11.86–26.46
Eucalyptus             15–28                 10–61                  0             0.28–0.64   0.02–0.09   20.59–26.28
Bamboo                 25.05–47.03           48.05–70.20            1.43–1.95     0.34–0.63   0.07–0.10   21.02–27.26    Chen et al. (2012a),
Rice husk sugar cane   22.27–41.17           33.33–61.88            13.18–23.11   0.32–0.70   0.06–0.10   17.68–21.48     Chen et al.
 bagasse Madagas-                                                                                                         (2012b)
 car almond
Oil palm               32.58–43.67           39.60–53.76            9.97–13.52    0.29–0.54   0.06–0.08   20.61–23.54
Reed canary grass      13.3–21.3             70.5–80.3              6.4–8.3       0.67–0.74   0.11–0.13   20.0–21.8      Bridgeman et al.
Wheat straw            15.6–38               51.8–77                7.4–10.2      0.48–0.72   0.10–0.12   19.8–22.6       (2008)
Olive tree pruning     20.4                  74.5                   2.4           0.89        0.16        N/A            Martin-Lara et al.
                                                                                                                          (2017)
Olive trimmings        16.54–32.57           55.96–77.65            3.87–7.87     0.18–0.70   0.08–0.12   19.6–28.4      Martin-Lara et al.
Olive pulp             19.98–50.40           41.99–77.22            1.50–6.67     0.24–0.72   0.08–0.12   20–26.8         (2017), Volpe
                                                                                                                          et al. (2015)
Orange peel waste      38.9–62.2             37.8–61.1              3.3–5.6       0.24–0.65   0.06–0.10   21.45–28.74
Lemon peel waste       35.7–61.8             38.2–64.3              3.5–6.3       0.22–0.68   0.06–0.10   21.09–28.75
Jatropha seed          13.5–35.5             55.5–79.8              6.25–7.60     0.29–0.49   1.14–1.50   21.8–23.8      Hsu et al. (2018)
  residue
    The main process parameters that directly influence the               viscosity as well as dielectric constant and weakening of
hydrothermal liquefaction process include biomass composi-                water hydrogen bonds consequently enhance the solubil-
tion, particle size, pressure, temperature, heating rate, resi-           ity of hydrophobic organic compounds associated with an
dence time, feed/solvent ratio and presence of the catalyst               improvement in the catalytic activity of acid–base reac-
and reducing gas. Generally, the hydrothermal liquefaction                tions. This results in biomass conversion into four main
process operates at mild operational parameters of tempera-               fractions: bio-crude fuel (liquid), water-soluble products,
ture in the temperature range of 250–500 °C and pressure of               solid residue and gases.
5–35 MPa and contact periods of 5–60 min. These processes                     Moreover, hydrothermal liquefaction is regarded as lesser
are conducted in the presence of solvents such as sub/super-              energy consumption and a higher efficiency strategy than
critical water, organic solvents and mixed solvents such as               pyrolysis because of the better physicochemical properties.
the combination of water + organic solvent (Yang et al. 2019;             The produced bio-crude from the hydrothermal liquefaction
Akalın et al. 2017).                                                      process has an oxygen content of 10–20 wt.% and a heating
    The utilisation of water as a solvent has numerous                    value of 30–35 MJ/kg, which is typically higher than those
advantages over conventional organic solvents due to its                  obtained from the conventional pyrolysis process (Guo et al.
natural occurrence in biomass and eco-friendliness. On                    2019). During the hydrothermal liquefaction process, the
the contrary of water state at ambient conditions, the                    oxygen contained in the biomass is partially eliminated by
compressed water in a liquid state at the following criti-                dehydration, decarboxylation and decarbonylation reactions
cal conditions of temperature and pressure of 374 °C and                  associated with producing CO, CO2 and H2O. Despite its
22.064 MPa, respectively, generates higher ionic products                 higher quality, the higher oxygen content produces a highly
(i.e. H3O+ and OH−) ions. Proximity to the mentioned crit-              sticky and acidic bio-crude product with a low heating value.
ical conditions, the physicochemical properties of water                  Distinctly, its quality enormously varies depending on the
such as density, viscosity, dielectric constant, polarity and             operational parameters and biomaterial feedstock composi-
permittivity change (Arun et al. 2021). Decrease in the                   tion (Scarsella et al. 2020).
                                                                                                                                 13
4082                                                                                      Environmental Chemistry Letters (2021) 19:4075–4118
    Hence, the importance of downstream upgrading treat-                 coffee grounds of approximately 15 and 17.4% for lipids and
ment such as catalytic cracking and hydrotreating for the                proteins, respectively, were liquefied to output crude bio-oil
obtained bio-crude cannot be ignored for further utilisation             under N2 atmosphere at (200–300 °C) and (5–25 min). The
as a transportation drop-in fuel. In situ upgrading using vari-          highest yield of acetone-recovered bio-crude oil (47.3 wt%)
ous acidic or alkaline homogenous catalysts such as HCl,                 was obtained at 275 °C and 10 min with an estimated higher
H3PO4, K2CO3, Na2CO3, NaOH, KOH and Ca(OH)2 and                       heating value of 31.0 MJ/kg−1, better than that of spent cof-
 heterogeneous catalysts has been studied in detail (Perkins             fee grounds of 20.2 MJ/kg (Yang et al. 2016). Xiu et al. per-
 et al. 2019). Despite its cost and energy-saving nature, it has         formed a study on swine manure composed of < 1%, 17.1%,
 some disadvantages, such as operating at high pressure that             22.3% and ∼35% for lignin, crude protein, ash content and
 results in the necessity of (1) solid/water slurries reliable           saccharide, respectively. They successfully liquefied into
 pumping, (2) suitable unit metallurgy to avoid the potentially          bio-crude oil under N2 atmosphere at a temperature range
 corrosive nature of slurries at the operational parameters              of 260–340 °C and a contact period of 15 min with a yield
 of elevated pressures and mild temperatures and (3) usage               of 24.2 wt.% and higher heating value of 36.05 MJ/kg (Xiu
 of heat exchangers with high surface areas to overcome                  et al. 2010). Table 4 presents the proximate as well as ulti-
 the problem of low heat transfer coefficients (Beims et al.             mate investigations of crude bio-oil prepared from several
 2020). Li et al. (2017) liquefied wheat straw biomass at a              biomaterials through the hydrothermal liquefaction process.
 pre-adjusted temperature of 270 °C for 120 min, and the
 resulting oil was forwarded for manufacturing of bio-polyols            Pyrolysis
 and polyurethane foams (Li et al. 2017).
    Crude oil originated from liquefaction of bark biomass               Pyrolysis is counted as one of the most as-used thermo-
 was directed to produce bio-based phenol–formaldehyde                   chemical scenarios to degrade the carbonaceous biomass,
 formable resole as reported by Li et al. (Li et al. 2016). Spent        such as cellulose, hemicellulose and lignin (Aravind et al.
Table 4  Proximate and ultimate analyses of bio-crude oil prepared from several biomass through hydrothermal liquefaction process. Where,
the higher heating value is abbreviated as HHV
Feedstock                      Elemental composition of product spe- Physicochemical properties of the prod-   References
                               cies after Hydrothermal liquefaction  ucts
                               C (%)   H (%) N (%) O (%) S (%) Ash %             Moisture % HHV Yield %
Spirulina algae                68.9    8.9    6.5     14.9    0.86   –           –            33.2    32.6     Vardon et al. (2011
Anaerobic sludge               66.6    9.2    4.3     18.9    0.97   –           –            32.0    9.4
Cladophora glomerata           26.8    3.53   2.14    20.48   0.22   36.5       9.1           10.29   –        Plis et al. (2015)
Nannochloropsis gaditana       40.3    5.97   6.30    14.49   0.37   28.3       4.1           18.53   –
Almeriansis                    73.2    9.3    5.1     0.8     11.7   35.8      20.0           –       42.6     López Barreiro et al. (2015)
Gaditana                       74.2    9.3    4.0     0.6     11.8   36.2      12.4           –       50.8
Swine manure                   71      8.9    4.1     0.21    14.2   35          –            –       61       Toor et al. (2011)
Algae Dunaliella tertiolecta   63.55   7.66   3.71    –       25.8   30.7        –            –       25.8
Porphyridium                   66–83   5–11   0–12    0–1     8–27   22.8–36.9   –            –       5–25
A.esculenta                    73.8    8      3.8     14      0.8    –           –            33.8    17.8     Anastasakis and Ross (2015)
L.digitata                     70.5    7.8    4.0     17      0.7    –           –            32      17.6
L.Saccharina                   31.3    3.7    2.4     26.3    0.7    24.2       9.2           12      –
Fucus vesiculosus              32.88   4.77   2.53    35.63   2.44   11.8        –            15.0    –        Ross et al. (2008)
Laminaria hyperborea           34.97   5.31   1.12    35.09   2.06   11.2        –            16.54   –
Miscanthus                     46.32   5.58   0.56    41.79   0.2    2.1         –            19.08   –
A.azuera                       40.82   5.56   0.63    52.99   –      10.61      6.03          52.99   –        Aysu et al. (2016)
Nannochloropsis Oceana         77.6    4.9    3.4     –       0.3    –           –            37.70   54.2     Caporgno et al. (2016)
Aspen wood                     75.2    8.2    0.5     15.8    0.3    0.48       3.8           34.3    –        Pedersen et al. (2016)
Arthrospira platensis          74.5    10.2   6.8     7.5     1.0    –           –            38.65   30       Lavanya et al. (2016)
Tetraselmis                    71.4    9.5    5.7     12.3    1.1    –           –            35.58   29
Nannochloropsis Salina         55.16   6.87   2.73    33.97   1.27   2.48       4.95          25.40   –        Toor et al. (2013)
Seaweed meal                   43.99   5.95   5.21    36.13   1.02   7.7        7.92          18.35   –        Ferrera–Lorenzo et al. (2014)
Laurel algae                   48.97   6.38   3.02    41.63   –      10.53      9.95          19.77   –        Ertas and Alma (2010)
13
Environmental Chemistry Letters (2021) 19:4075–4118                                                                               4083
2020). This results in the generation of solid, liquid and gas        The primary product is liquid oil (Bridgwater, 2012a). Ultra-
biofuels in an oxygen-free atmosphere via endothermic reac-           fast or flash pyrolysis is a highly accelerated pyrolysis at a
tion (Perkins et al. 2018). The yield of the pyrolytic products       high heating rate with major gas and oil products. The oper-
is influenced by factors, including feedstock composition             ating conditions are as follows temperature (medium–high
such as structure and complexity. This is also coupled with           (700 – 1000 °C), shortest residence time and fastest heating
pyrolysis impacting factors such as particle size, tempera-           rate. Yields of outputs are: (1) liquid condensate (10 – 20%),
ture, heating rate, residence time, inert gas type, inert gas         (2) gases (60 – 80%) and (3) char (10 – 15%) (Priharto et al.
flow, catalyst type and others (Azizi et al. 2018).                   2020).
   Complex reactions such as dehydration, decarboxylation,               Catalytic pyrolysis is a process in which catalysts such as
decarbonylation, hydrogenation, isomerisation, aromatisa-             natural zeolite, Cu/Al2O3, Co/Mo/Z, Zeolite-ß, Fe2O3 and
tion, depolymerisation and charring are involved in the ther-         Ni-CaO-C are used to decrease the reaction operating tem-
mal decomposition process of biomass. Typically, pyrolysis            perature and increase the selectivity towards desired prod-
of biomass undergoes the following steps: (1) transfer of             ucts. This process is used to optimise the biomass conversion
heat from its source to biomass to initiate the reaction, (2)         into liquid fuels with improved physicochemical properties
elevated pyrolysis temperature of primary vapours con-                (Cai et al. 2019; Chai et al. 2020). Catalytic co-pyrolysis
tributes to volatiles and char formation, (3) because of the          of biomass and plastic waste showed promising results in
influx of hot vapours to the biomass, heat migration contin-          upgrading the oil quality by removing oxygen from the
ues between unpyrolysed fuel and hot volatiles, (4) volatiles         biomass and producing more aromatics and olefins (Wang
condensation associated with secondary reactions leads to             et al. 2020b). This is due to the high hydrogen and carbon
tar formation and (5) autocatalytic secondary pyrolysis reac-         contents within the plastic waste and consequently acting as
tions take place in conjugation with primary pyrolytic reac-          a hydrogen donor in the catalytic co-pyrolysis process and
tion (Dabros et al. 2018).                                            thus eliminates the oxygenated compounds. This approach
   The impact of different pyrolysis operational parameters           is seen as a sustainable, efficient and economical approach
occurs at different stages such as dehydration, decomposi-            to upgrading the bio-oil quality, along with extending the
tion and reforming. With elevated heating rate, minimum               catalyst’s lifetime.
vapour contact periods and a surrounding temperature of                  Microwave-assisted pyrolysis is a new thermochemi-
500 °C, liquid yields can be maximised (Chintala, 2018).              cal process that transforms biomaterial feedstock into liq-
These conditions directly prohibit (1) thermal or catalytic           uid oil using microwave input heat energy. In contrast to
cracking of the primary decomposition products due to char            the conventional process, microwave-assisted pyrolysis is
presence to lesser non-condensable gas molecules as well              a more effective and controllable technique. CO2-assisted
as (2) their polymerisation to char (Kasmuri et al. 2017).            pyrolysis is a process by which C  O2 is delivered as a reactive
Table 5 presents different working modes of the pyrolysis             medium instead of inert N2 in utilising the pyrolysis process
process. Other pyrolysis types such as catalytic and assisted         and enhancing the syngas yield and declines the produced
microwave, carbon dioxide, additives, solar and hydro-pyrol-          oil but also decreases the greenhouse gas emissions (Kwon
ysis can be performed to upgrade the product’s yields.                et al. 2019).
   Slow pyrolysis is a process in which organic materi-                  Additive–assisted pyrolysis is a type of pyrolysis at which
als are slowly heated at a low heating rate between 5 and             metal salts such as sodium, potassium and calcium salts and
50 °C min-1 and the longest residence time above 10 s in the          inorganic additives (zeolites, biochar) are added and thus
absence of oxygen, typically producing about 80% of car-              having some advantages over conventional pyrolysis. It has
bon as the main product (Antoniou and Zabaniotou, 2013).              a great potential to decrease the required operating tempera-
Fast pyrolysis is a strategy by which organic materials are           ture, cracking time and solid residue yield, in addition, to
quickly heated at faster heating rates of > 103 °C s−1 and           increase the cracking efficacy of wastes and improves the
shorter contact periods of up to 3 s without air existence.           quality of pyrolysis products (Wang et al. 2019a).
Table 5  Different working          Mode of action    Working tem-      Residence time (seconds)     Yields (wt. %)
modes of the pyrolysis process                        perature (°C)
(Bulushev and Ross, 2011)                                                                            Char      Liquid             Gas
                                                                                                                           13
4084                                                                                 Environmental Chemistry Letters (2021) 19:4075–4118
   Solar pyrolysis is a process in which solar renewable              decomposition stage and secondary cracking of vapours.
energy can be introduced as thermal input sources rather              Bio-oil is formed by subjecting the heavier molecules con-
than electrical energy that maximise biofuel production and           densable gases to subsequent cooling and condensation pro-
reduce CO2 emissions. Hydropyrolysis is a particular type of         cesses, while the lower molecules non-condensable gases
pyrolysis at which biomaterial feedstock is decomposed with           (i.e. CO and CO2) are not condensed during the cooling
the assistance of high pressurised hydrogen. Using the men-           stage.
tioned technique above, a higher yield of hydrocarbons with
improved structures can be attained (Marcilla et al. 2013).
   Pyrolysis products can be categorised as solid, liquid and         Gasification
gases that can be exploited to generate chemicals, energy,
electricity and transportation fuels. Proximate and ulti-             Gasification is a process by which carbonaceous materials
mate analyses are beneficial to characterise the obtained             are thermochemically converted into valuable gases, com-
products. Char, pyrolytic char or biochar, is the produced            monly referred to as synthesis gases in the presence of a
solid, chemically not pure carbon, and contains carbon as             gasifying agent such as air, oxygen, steam, C  O2 or a combi-
the main constituent, hydrogen, nitrogen, ash and some                nation of them at a temperature above 700 °C. Primarily, the
volatiles. The highly porous char is used in several appli-           produced gas consists of CO, H   2, CO2 and C
                                                                                                                     H4 (Shahabud-
cations as adsorbent and soil amendment for wastewater                din et al. 2020). Generally, the gasification process com-
treatment and enhancement of crop yields. Bio-oil (tar)               prises four main steps: (1) heating or drying (100–200 °C)
is a dark brown, sticky liquid produced from the thermal              to decrease its moisture content, (2) pyrolysis, (3) oxida-
degradation of biomass. Typically, it consists of more than           tion or partial combustion and (4) gasification. Firstly, the
400 chemical compounds (i.e. aldehydes, alcohols, amines,             moisture content (30–60%) of the biomass is vaporised at
acids, esters, ethers, ketones, phenol derivatives, ketones,          about 200 °C. Then, pyrolysis includes the decomposition
guaiacols, furans, oligomers, syringols and sugars) (Hen-             of different biomass, including cellulose, hemicellulose and
rich et al. 2016). Considering its low carbon, nitrogen and           lignin, into solid residues and volatiles occurs (Thomson
sulphur content, CO, S OX and NOx emissions are low, hence           et al. 2020). Oxidation or partial combustion is the third
preparing bio-oil and conventional fuels.                             stage in which the resultant volatiles and char residues are
   Table 6 displays a comparison between the properties               oxidised to CO, CO2 and H    2O with gasifying agent assis-
of prepared bio-oil (after water removal) and conventional            tance beyond 700 °C (exothermic reaction).
liquid fuels. Concurrently, Table 7 shows physiochemical                 By the action of CO2 or steam as gasifying agents, car-
properties of as-formed bio-oil resulting from the pyroly-            bon and volatile compounds react with them in terms of
sis of several biomaterials feedstocks without applying               reduction reaction to produce syngas at a temperature over
any upgrading strategy as well as comparing it with other             800 °C in an endothermic reaction (Situmorang et al. 2020;
conventional fuels, respectively. Both condensable and                Hanchate et al. 2021). Briefly, simultaneous exothermic
non-condensable gases are generated throughout the first              and endothermic reactions are included in the gasification
                                                                      process, and the first previously mentioned reactions are
                                                                      considered as heat suppliers for the endothermic one. Main
Table 6  Comparison of bio-oil properties with conventional fuels     reactions involved in the gasification include carbon reaction
(Bridgwater, 2012b)                                                   such as primary or secondary steam reforming, hydrogasi-
Property                   Bio-oil Diesel      Heating oil Gasoline   fication, oxidation, shift reaction, mechanisation and steam
                                                                      reaction.
pH                         2.0–3.0   –       –            –
                                                                         The efficiency of the gasification process is impacted by
Viscosity at 40 °C (cP)    40–100    2.4     1.8–3.4      0.37–0.44
                                                                      different operational parameters such as feedstock composi-
Density at 15 °C (kg/m3)   1200      820–950 865          737
                                                                      tion, moisture content, ash content, granulometry, pressure,
Heating value (MJ/kg)      18–20     42      45.5         44
                                                                      temperature, gasifier’s type, gasifying agents, equivalence
Pour point (°C)            − 15      − 29    −6           − 60
                                                                      ratio and steam to biomass ratio (Díaz González and Pacheco
Flash point (°C)           48–55     42      38           40
                                                                      Sandoval 2020). Basically, the gasifier’s selection: fixed or
Solids (wt%)               0.2–1.0   –       –            –
                                                                      moving bed (dry ash/slagging), fluidised bed (circulating,
Ash                        < 0.02            < 0.01
                                                                      bubbling) and entrained flow (upflow, downflow), is con-
Carbon                     42–47     87.4    86.4         84.9
                                                                      trolled by several factors, for instance, feedstock composi-
Hydrogen                   6–8       12.1    12.7         14.76
                                                                      tion, gasifying agent and product requirements (Mehrpooya
Oxygen                     46–51     –       0.04         –
                                                                      et al. 2018). Syngas chemical composition and its heating
Nitrogen                   < 0.1     392 ppm 0.006        0.08
                                                                      values vary based on the as-used gasification method, as
Sulphur                    < 0.02    1.39    0.2–0.7      –
                                                                      presented in Table 8.
13
     Table 7  Physiochemical properties of bio-oil produced from different biomasses without using any upgrading technique. Where, the higher heating value is abbreviated as HHV
     Biomass             Reactor type          Operating     Bio-oil elemental analysis     Bio-oil fuel properties                                                      References
                                               temperature   (wt.%)
                                               (°C)
                                                             C%      N%     O%       H%     pH     Density (g/ml)     Viscosity   Water con-    HHV       Acid value
                                                                                                                                  tent (wt.%)   (MJ/kg)   (mg of KOH/
                                                                                                                                                          g)
     Saccharina          Fluidised bed         300           60.15   5.77   16.48    7.74   5.9     –                 –            1.76         28.63     –              Choi et al. (2017)
     Japonica
     Corn stover         Fixed bed             400           –        –       –       –     2.67   1.25               2.6b          –           15.3      –              Sundaram et al. (2016)
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     Table 8  Composition of syngas from several biomass types and operating parameters, where N.A is abbreviated for not available
     Biomass type      Operating parameters                                                                     Syngas Composition (% v/v)                                Lower heating
                                                                                                                                                                          value
                       Temperature      Steam: biomass Gasification         Gasifying agent Equivalence         CO               CO2          CH4          H2             (MJ/Nm3)
                       (°C)                            reactor                              ratio
     Bamboo            400–600          –                 Fluidised bed     Air               0.4               23.5–30.6%       59–63% m/m 4–5% m/m       6.6–8.1% m/m   1.6–1.9
                                                                                                                  m/m
     Bamboo            400–600          0:1, 1:1          Fluidised bed     Air & air–steam 0.4                 23.5–30.6%       N.A          N.A          6.6–8.16% m/m N.A
                                                                                                                  m/m (air);                                 (air);10.9–
                                                                                                                  36.1–40.3%                                 16.5% m/m
                                                                                                                  m/m                                      (air–steam)
                                                                                                                (air–steam)
     Empty Fruit       700–1000         –                 Fluidised bed     Air               0.15–0.35         21–36            10–65        5–14         10–38          7.5–15.5
       Bunch
     Empty Fruit       850              –                 Fluidised bed     Air               0.15–0.35         32–45            16.6–36      12–15        18.3–27.4      12.3–15.3
       Bunch
     α–cellulose       800              0–1.5             Fluidised bed     Air–steam         0.27              6.5–11.2         26.3–27.7    2.2–3.7      13.5–18.5      6.5–7.6
     Palm oil wastes   800              0.67–2.67         Fixed bed         Steam             –                 14–33            14–26        3–6          47–58          8.7–12
     Pine sawdust      700–900          2.7               Fluidised bed     Air–steam         0.22              35–43            18–20        6–10         21–39          7.4–8.6
     Palm oil wastes   750–900          1.3               Fixed bed         Steam             –                 15–25            20–25        4–5          48–60          9.1–11.2
     Olive kernel      950              –                 Fixed bed         Air               0.14–0.42         15–20% w/w       40–55% w/w   10–12% w/w   20–30% w/w     8.8–10.4
     Data sourced from Ahmad et al. (2016), Lv et al. 2004), Luo et al. (2009), Mohammed et al. 2011), Skoulou et al. (2008)
                                                                                                                                                                                          Environmental Chemistry Letters (2021) 19:4075–4118
Environmental Chemistry Letters (2021) 19:4075–4118                                                                          4087
    Other gasification types such as plasma, supercritical          and organic solvents, and (4) biological or combination of
and microwave have been operated to improve gasification            them (Haghighi Mood et al. 2013). Secondly, pretreated
yields. In plasma gasification, an intense plasma thermal           biomass is decomposed into monomers by the action of
process is used to catalyse and ionise the organic compounds        acid/enzymatic hydrolysis. Lastly, the intermediate mono-
in biomass and gas, respectively, into syngas with slag using       mers are converted into alcohols using yeast/bacteria (Liu
a plasma torch powered by an electric arc (over 2500 °C).           et al. 2015).
Supercritical water gasification is a type of gasification typi-       Based on the consolidation degree of the mentioned
cally performed in the presence of a vast amount of water           stages, ethanol production can be configured into four
for the generation of H   2 and C  H4 (Rodriguez Correa and       routes: (1) separate hydrolysis and fermentation, (2)
Kruse, 2018). The process yield is very high, mainly affected       simultaneous saccharification and fermentation, (3)
by different parameters such as temperature, catalyst and           simultaneous saccharification and co-fermentation and
biomass/water ratio.                                                (4) consolidated bioprocessing. In separate hydrolysis and
    Microwave gasification is a compelling scenario for trans-      fermentation scenarios, enzyme generation, hydrolysis,
forming biomass. This technique’s benefits over the tradi-          hexose and pentose fermentation are employed in separate
tional methods include uniform distribution of temperature,         OR individual reactors. Despite execution of hydrolysis
efficacy for large particle handling and higher heating values      in addition to fermentation at their optimised conditions,
(Chen et al. 2015). Different technologies such as scrubbers        accumulation of cellobiose and glucose enzymes during
(i.e. spray, dynamic wet, cyclonic, impactor, venture and           hydrolysis process negatively prohibits the efficiencies of
electrostatic) and filters (fabric bag, fibrous ceramic, metallic   cellulases (Margeot et al. 2009).
foam and granular bed) have been used to clean up the syn-             In the simultaneous saccharification and fermentation
gas from different contaminants and hence improve its qual-         scenario, cellulose hydrolysis and hexose fermentation
ity for numerous applications. A list of global biofuel-based       simultaneously run at the same reactor that overcomes
facilities comprising its manufacturer, country, starting-up        cellulase inhibition because of instant consumption of
year, feedstock composition, downstream products and as-            sugars by fermenting microorganisms (Hahn-Hägerdal
used technology is shown in Table 9.                                et al. 2007). In the simultaneous saccharification and co-
                                                                    fermentation scenario, two genetically modified strains
Biochemical conversion methods                                      of Saccharomyces cerevisiae and Zymomonas mobilis are
                                                                    used to co-ferment glucose and xylose in the same reac-
Biochemical conversion pathways such as anaerobic diges-            tor. In the consolidated bioprocessing scenario, only one
tion and fermentation can be employed to generate various           microorganism is simultaneously utilised for hydrolysis
biofuels from waste biomass, as shown in Fig. 3. Biochemi-          and fermentation, which decreases the operation cost and
cal conversion methods have numerous merits, including              enhances the process efficacy (Lin and Tanaka, 2006).
high product selectivity, high product yield and flexibility           Different modes of fermentation can be briefly viewed
to be operated at ambient temperature and pressure condi-           as follows: photo-fermentation is a fermentative trans-
tions (Singh et al. 2016). Ethanol and bio-hydrogen can be          formation of organic substrate to produce bio-hydrogen
produced from the fermentable biomass via alcoholic fer-            driven by miscellaneous groups of photosynthetic bacteria.
mentation and dark fermentation/photo-biological routes,            This is occurring throughout a set of biochemical reac-
respectively, whereas biogas can be produced anaerobic              tions in three steps like anaerobic conversion. The dif-
digestion as follows (Osman et al. 2020).                           ference between photo-fermentation and dark fermenta-
                                                                    tion is its proceeding in the presence and absence of light,
Fermentation                                                        respectively.
                                                                       Alcoholic fermentation is another type of fermentation
Fermentation is a process by which biological activities            driven by yeast by which sugars are transformed into cel-
are utilised conjugated with air existence known as aerobic         lular energy associated with the generation of ethanol and
fermentation or without air called anaerobic fermentation           carbon dioxide. Considering its occurrence in the absence
(Karimi et al. 2021). Bioconversion of biomass to biofuel           of oxygen, it can be categorised as an anaerobic integration
comprises of sequential stages: pretreatment, hydrolysis            process. Heterotrophic algae or yeast can transform sugars
(acid/enzymatic) and fermentation (Alvira et al. 2010).             into lipids inwards their cells associated with using suitable
   The pretreatment step aims to damage the cell wall as            solvents to break down the cells (Łukajtis et al. 2018). The
well as exhibit cellulose and hemicellulose for subsequent          resultant lipids can be further purified and improved to liq-
hydrolysis. It can be classified into four main categories,         uid forms of transport fuels by hydro-treated vegetable oil
including: (1) physical, e.g. grinding, (2) physicochemi-           diesel scenario, whereas genetically modified bacteria con-
cal, e.g. wet oxidation, (3) chemical, e.g. oxidising agents        sume sugars and consequently produce short-chain gaseous
                                                                                                                       13
     Table 9  Second-generation biofuel plants, including manufacturer, country, starting up a year, feedstock composition, downstream products and as-used technology
                                                                                                                                                                                                    4088
     Company/Institute/University Starting-Up Year Feedstock composition               Downstream products             As-used Technology             TRL-scale                    Country
     name
13
     Lahti Energia Oy               1998              Wood waste                       Renewable diesel                Circulating Fluidised Bed      TRL 9 commercial             Finland
                                                                                       (HVO) (70 MWth)                  gasifier
     CHP Agnion Biomasse            2001              Wood waste (80,000 t/year)       Synthetic natural gas (32.5     Agnion Heatpipe-Reformer       TRL 4–5 pilot                Germany
     Heizkraftwerk Pfaffenhofen                                                          MWth)
     CHOREN Industries GmbH         2003              Dry wood chips from recy-        Fischer–Tropsch liquids (53     Not available                  TRL 4–5 pilot                Germany
                                                        cled wood and                    t/year)
                                                      residual forestry wood
     Vienna University of           2005              Syngas from FICFB gasifier       Fischer–Tropsch liquids         Not available                  TRL 4–5 pilot                Austria
      Technology/BIOENERGY                              (5 m3/h)                        (5 kg/day)
      2020 +
     West Biofuels                  2007              Clean wood, waste wood (5        Fischer–Tropsch liquids         Dual fluidised bed thermal     TRL 6–7 demonstration        United States
                                                        t/day)                                                         reforming
     Bio SNG Guessin                2008              Syngas from gasifier (350        Synthetic natural gas (576 t/   Not available                  TRL 6–7 demonstration        Austria
                                                        m3/year)                       year)
     TUBITAK MRC—ENERGY 2009                          biomass                          Synthetic natural gas           Downdraft fixed bed gasifier   TRL 4–5 pilot                Turkey
      INSTITUTE—TURKEY                                                                  (0.2 MW)
     Greasoline GmbH    2011                          Bio-based oils and fats, resi-   Diesel type hydrocarbons (2     Catalytic cracking of bio-     TRL 4–5 pilot                Germany
                                                       dues of plant oil process-       t/year)                         based oils + fats primarily
                                                       ing, free fatty acids used                                       produces diesel fuel-range
                                                       bio-based oils and fats (3                                       hydrocarbons
                                                       t/year)
     BioTfueL-consortium            2012              Forest waste, straw, green     Fischer–Tropsch liquids (60 Not available                        TRL 4–5 pilot                France
                                                       waste, dedicated crops          t/year),
                                                                                     jet fuel component
     TUBITAK                        2013              Combination of hazelnut        Fischer–Tropsch liquids (250 Pressurised fluidised bed           TRL 4–5 pilot                Turkey
                                                       shell, olive cake, wood chip    t/year)                      gasifier
                                                       and lignite blends (0.2 t/h)
     Goteborg Energi AB             2014              Forest residues, wood pellets, Synthetic natural gas (11,200 Repotec indirect gasification      Demonstration                Sweden
                                                       branches and treetops           t/year)                      technology and Haldor
                                                                                                                    Topsoe fixed bed methana-
                                                                                                                    tion
     BioMCN                         2017              Wood chips                     Methanol (413,000 t/year)     Not available                      TRL 8 first-of-a-kind        Netherlands
     Go Green Fuels Ltd             2018              Refuse derived fuel and        Synthetic natural gas (1500   Not available                      TRL 8 first-of-a-kind com-   United Kingdom
                                                       waste wood (7500 t/year)        t/year)                                                         mercial demo
     ECN                            2019              Not available                  Synthetic natural gas         Not available                      TRL 6–7                      Netherlands
                                                                                       (300 MW)                                                       demonstration
     Red Rock Biofuels              2019              Not available                  Diesel type hydrocarbons      Not available                      TRL 8 first-of-a-kind com-   United States
                                                                                     (1 t/year)                                                        mercial demo
     Fulcrum BioEnergy Sierra       2019              Waste (20,000 t/year)          Fischer–Tropsch liquids       Not available                      TRL 9 commercial             United States
      Biofuels Plant                                                                 (314,913 t/year)
                                                                                                                                                                                                    Environmental Chemistry Letters (2021) 19:4075–4118
  Environmental Chemistry Letters (2021) 19:4075–4118                                                                                                                                                                    4089
TRL 6–7
                                                                                                                                                               Anaerobic digestion
                       As-used Technology
Greenfield Ethanol)
                                                                                                                                                                                                                   13
4090                                                                                     Environmental Chemistry Letters (2021) 19:4075–4118
Fig. 3  Biochemical conversion route of biomass utilisation into bio-   turn, along with hydrogen, could be converted into liquid fuel. The
fuel, including fermentation and anaerobic digestion processes. Two     other route is the fermentation process, where the biomass is firstly
types of digestion: aerobic digestion, which produces carbon dioxide    pretreated and then followed by enzymatic hydrolysis and fermenta-
and fertiliser, while anaerobic digestion produces biogas which in      tion, and finally, the production of liquid biofuel
   Commonly, an anaerobic digestion scenario comprises                   produce methane (biogas) by two sets of methanogens: ace-
four consecutive steps, including hydrolysis, acidogenesis,              toclastic and hydrogen utilising organisms (Matheri et al.
acetogenesis and methanogenesis, catalysed by different                  2018; Ganesh Saratale et al. 2018). The first group (ace-
microorganisms, whereas hydrolysis is deemed as the rate-                toclastic methanogens) convert acetate into methane and
determining step.                                                        carbon dioxide, while the other ones (hydrogen-utilising
   Hydrolysis is the first stage of anaerobic digestion at               methanogens) generate methane by applying hydrogen and
which complex biopolymers (i.e. carbohydrates, lipids,                   carbon dioxide as electrons donor and acceptor, respectively.
proteins, polysaccharide and nucleic acid) are converted                     Several enhancement techniques as pretreatment steps
into simple soluble compounds (i.e. amino acid, fatty acids,             such as: (1) physical, e.g. milling, (2) chemical, e.g. ionic
monomers, sugar, purines and pyrimidine) by the action of                liquid and surfactant, thermophysical, e.g. microwave irra-
enzymes (i.e. amylases, lipases and proteases) produced                  diation, (3) thermochemical, e.g. supercritical CO2, ammo-
from hydrolytic bacteria (Sawatdeenarunat et al. 2015).                 nia fibre explosion and ammonia fibre percolation, and
   Secondly, acidogenesis is the second stage of anaerobic              (4) biological (microbial and enzymatic) can precede to
digestion at which the simplified amino acids, sugar, fatty             enhance anaerobic digestion process (Gautam et al. 2020).
acids and monomers are converted into intermediate bio-                 To upgrade the quality of biogas (impurities removing),
molecules (i.e. alcohols, volatile fatty acids, propionic and           an additional cleaning step can be added to capture C        O 2,
butyric acids) by fermentative bacteria.                                H2S and water vapours and avoid mechanical and chemical
   Acetogenesis is the third step at which the mentioned                 appliances throughout its utilisation. Different materials (i.e.
acidogenesis products serve as a substrate to produce acetate            silica gel) can be used to tackle H2S and water vapours.
by homoacetogens bacteria. Methanogenesis is the last step                   In contrast, other techniques (i.e. water scrubbing, organic
at which both acetate and carbon dioxide are directed to                scrubbing, membrane separation, cryogenic technology and
13
Environmental Chemistry Letters (2021) 19:4075–4118                                                                          4091
pressure swing adsorption) can be delivered to sequester          residence time (Li et al. 2021). Where steam and oxygen
CO2 from the product and subsequently elevate its calorific      (95% vol.) are commonly the gasification agents, the heat
 value (Nag et al. 2019). The raw biogas can be used for          required for the gasification is supplied by biochar com-
 producing electrical energy, whereas the improved biogas         bustion. The gasification gas usually has a low content of
 can be directly inserted into the natural gas grid or utilised   light hydrocarbon and high-water content; thus, an in situ
 as fuels for vehicles. From the economic point of view,          reformer with steam is used to convert them into carbon
 two substrates can be simultaneously mixed (anaerobic co-        monoxide and hydrogen, followed by cooling of the high-
 digestion) to overcome the disadvantages of mono-digestion       temperature reformer effluent gas before subjecting it to gas
 and enhances its feasibility. Numerous types of reactors,        composition adjustment (compression and sulphur removal
 including submerged packed beds, fluidised beds and other        steps). This is then followed by the water gas shift reaction
 types, have been employed for the anaerobic digestion treat-     process, where steam is introduced into the unit to increase
 ment process of wastewater with high biochemical oxygen          the hydrogen to carbon monoxide ratio to 2, and then, car-
 demand (Paudel et al. 2017).                                     bon dioxide is removed before the methanol synthesis stage.
                                                                  Finally, the compressed synthesis gas is pre-heated before
                                                                  entering the methanol reactor, where carbon monoxide
Production of liquid biofuel such                                 hydrogenation produces bio-methanol.
as methanol and bio‑oil from biomass                                 Interestingly, bio-methanol derived from biomass feed-
                                                                  stocks can be used to produce light olefins of 230 million
Historically, more than a hundred years ago, Giacomo Cia-         tonnes demand worldwide (Li et al. 2021). Ethylene, pro-
mician mentioned in his manuscript entitled ‘Photochem-           pylene and butylene as light olefins are commercially pro-
istry of the Future’ about the urgent need for the sustain-       duced from petroleum-based hydrocarbon via steam crack-
able transfer from non-renewable to renewable sources             ing, where currently, biomass into olefins route gains interest
(Sharma et al. 2020; Qasim et al. 2020). In 2017, the global      through bio-methanol, dimethyl ether or Fischer–Tropsch
energy consumption was rated at 13.5 billion tons of oil          process.
(∼656 exajoules) by a yearly growth rate of 1.7%. Relat-             Bio-methanol can produce biodiesel via the transesteri-
edly, an increase in the uncontrolled population has directly     fication process, where triglycerides/ lipids are transformed
deepened the negative effects of the ascending pressure on        into fatty acid methyl ester using a catalyst and alcohol,
non-renewable resources globally (Pradhan et al. 2018).           mainly methanol (Al-Mawali et al. 2021; Al-Muhtaseb
Considering the new United Nations reports, it has been           et al. 2021; Hazrat et al. 2021). There is also a non-catalytic
stated that with an introduction of approximately 83 mil-         route for microalgal biodiesel production via subcritical and
lion people to our globe per year, the current global popula-     supercritical methanol (Karpagam et al. 2021).
tion of 7.6 billion is anticipated to increase to 8.6, 9.8, and      As a type of biomass, algae recently showed some merits
11.2 billion by 2030, 2050 and 2100, respectively. Based          in producing biofuels, such as high lipid productivity, carbon
on the United States Energy Administration (EIA) estima-          dioxide capture, high growth rate, limited land requirement
tions, the global energy requirement is increasing annually       and high production yields (Sekar et al. 2021; Peter et al.
and projected to rise by almost 28% in 2040 (∼739 quadril-        2021). Then again, there are still challenges, such as the
lions Btus) (Sharma et al. 2020). Majorly, high pressure on       post-processing of algae and the cultivation process. Besides
energy consumption originates from countries with robust          the biofuels mentioned earlier, microalgae can produce bio-
economic growth. A total enhancement in energy consump-           oil via different processes, most commonly pyrolysis and
tion has been investigated by non-OECD (Organisation for          others such as gasification and liquefaction as thermochemi-
Economic Co-operation and Development) countries (∼473            cal routes. Pyrolysis is preferred herein due to its simplicity,
quadrillions Btus) by 2040, compared with its counterpart of      speed, better yields, along with operating conditions.
Organisation of the Petroleum Exporting Countries (∼266              Bio-oil is the main pyrolytic product in fast and flash
quadrillions Btus) (Kumar et al. 2020).                           pyrolysis, along with biochar and gaseous products (Xiao
   The main route of biomass into liquid fuel ‘drop-in’ is        et al. 2021). However, when applying bio-oil directly in
through the gasification process. On a small scale, woody         petroleum (gasoline and diesel), engines will not produce
biomass gasification outperforms combustion and pyroly-           sufficient heat due to its low calorific value, a high number
sis in terms of technological and economic impacts, while         of oxygenated compounds (> 300) and high water content
pyrolysis has been identified as the best large-scale method      (20–40 wt.%), which is negligible in hydrocarbon fuels
for upgrading woody biomass (Solarte-Toro et al. 2021).           (gasoline and diesel) (Gupta et al. 2021). Furthermore, due
The biomass into liquid fuel such as bio-methanol starts          to its high viscosity and the presence of acidic compounds,
with biomass gasification under low pressure using down-          it will provide a flow barrier when it passes into injectors
draft gasifier owing to its low tar formation along with long     and engines, resulting in engine corrosion. Besides, crude
                                                                                                                       13
4092                                                                             Environmental Chemistry Letters (2021) 19:4075–4118
bio-oil will generate coking complications in the combus-        range of biomass feedstocks, geographical span, biofuels
tion stage due to the presence of a high number of solid         produced, life cycle tools and inventories used. Even if the
particles. Therefore, upgrading the bio-oil via the integrated   geographical span or biomass feedstock considered was sim-
refinery is crucial for its commercialisation and producing      ilar, no two studies were identified as identical to each other.
value-added chemicals, char utilisation and gasoline grade       This demonstrates that LCA practitioners and decision-mak-
fuel. The bio-oil upgrading process starts with moisture         ers would need to identify the routes towards environmental
separation either by distillation (fractional or azeotropic),    sustainability and energy efficiency while paying heed to the
using catalysts, additional pyrolysis or biomass pretreatment    specific processes modelled in the studies.
techniques (demineralisation and torrefaction). This is fol-
lowed by value-added chemicals extraction from the aqueous
phase (acids, ketones, alcohols, ethers and esters) to improve   Goal and scope definition
the overall economics of the process. Some chemicals could
also be extracted from the organic phase. The final organic      Goal and scope definition includes defining specific pur-
residue of the bio-oil is then upgraded into a transportation    pose, aim and objectives for conducting LCA. This stage is
fuel via various techniques such as deoxygenation, emulsifi-     imperative to understand overall results and LCA findings. It
cation, hydrocracking, esterification, catalytic cracking and    incorporates defining functional unit and respective system
heavy fuel blending.                                             boundaries. Functional units are quantified description of
   However, there are challenges associated with the upgrad-     the performance requirements that the product system fulfils
ing routes for bio-oil, mentioned above, as they are still not   and are linked with functions of the product rather than with
commercialised due to the high cost of the catalyst, short       physical products. It was observed that about 32% of the
catalyst life and complex operating conditions (high-pres-       reviewed studies used ‘units of bioenergy in J or kWh’ as
sure, special reactor requirements). Furthermore, extracting     the functional unit, while about 22% recorded LCA results
the chemicals in their low concentration is expensive and        for ‘amount of biofuels produced’ such as in kg (Fig. 4).
will require more investigation on the low-cost solvent, cata-      The system boundaries included in the LCA studies
lyst and process optimisation, primarily as the physicochem-     control what processes will be considered for computing
ical characteristics of the bio-oil rely on the catalyst used.   environmental impacts. Figure 5 shows the generalised three
The catalyst minimises the heteroatom content of the bio-        crucial phases for biofuel production: (1) Phase 1 includes
oil and increases the hydrogen-to-carbon ratio (H/C). This       biomass cultivation, fertiliser application, impacts of ferti-
consequently lowers the harmful emissions of N       OX, SOX   liser on soil, carbon emissions from land use, use of mar-
and increases the calorific value of the bio-oil (Nagappan       ginal and/or forest land, transportation of produced biomass
et al. 2021). Selling the biochar produced during pyrolysis      to the production system, (2) Phase 2 incorporates chemical,
can also increase the overall economics, which can be used       thermal, biochemical, thermochemical processes for con-
in the carbon sequestration, adsorption of the contaminants,     version of biomass to biofuels and related environmental
soil amendments and catalytic supports in bio-oil upgrading      impacts due to chemicals, electricity and energy procure-
that enhances the circular bioeconomy of the process (Fawzy      ment, upgradation of biofuels for final purpose, and (3)
et al. 2021).                                                    Phase 3 involves environmental impacts due to co-products
                                                                 management and emissions due to biofuel use.
                                                                    The system boundaries included in the LCA studies var-
Life cycle assessment of biomass to biofuel                      ied for processes and systems considered. It was observed
conversion processes                                             that about 90% of the reviewed studies considered Phase
                                                                 1, Phase 2, while only 25% of the studies included Phase 3
Life cycle assessment is recognised as an effective frame-       (Fig. 6). This highlights a paucity of research in the biofuel
work for assessing impacts on natural environment, humans        LCA field containing a holistic approach and includes all the
and natural resources for processes, products and systems.       phases of the biofuel production chain. Even where the stud-
It provides evidence-based data to policymakers to make          ies focused on Phase 3, they primarily dealt with anaerobic
long-term strategic decisions and improve environmental          digestion. Most of the studies focused on specific processes
sustainability. The four main stages defined by ISO 14,040       of the biofuel production chain, focusing on critical areas
and IS0 14,044 for conducting LCA are: (1) goal and scope        of concern rather than evaluating the overall impacts of the
definition, (2) life cycle inventory analysis, (3) environ-      entire production chain. Interestingly, use of biofuels has
mental impacts assessment and (4) life cycle interpretation      increasingly been recognised as a measure to reduce green-
(Lewandowski et al. 2000).                                       house gas emissions; however, very few studies addressed
   Herein, we analysed 40 LCA studies published from 2019        the use phase of biofuels and compared them to conventional
to 2021 on biofuels (Table 10). These studies covered a wide     sources.
13
     Table 10  Characteristics of life cycle assessment research analysed in the present study
     Reference                Region                  Functional unit          Feedstock             Process                  Product               LCA tools     Database
     Aberilla et al. (2019)   Southeast Asia          1 kWh of electricity     Rice and coconut      Comparison of: Com- Electricity                GaBi 7.3      Ecoinvent 3.1
                                                        produced                residues              bustion
                                                                                                     Anaerobic digestion
                                                                                                     Gasification
     Amezcua-Allieri et al. Southern Mexico           1 MJ of energy pro-      Sugarcane bagasse     Boiler              Bioenergy                  n/i           Ecoinvent
      (2019)                                            duced
     Ardolino and Arena     EU-27                     1 MW of biomethane       Biowaste            Comparison of:             Biomethane            SimaPro 8.2   n/i
      (2019)                                                                                         Anaerobic digestion
                                                                                                     with
                                                                                                   Gasification
     Bacenetti (2019)         North Italy             1 ha of vineyard       Pruning residues from Combustion for use in      Heat and Cold         n/i           Ecoinvent 3.5
                                                                              grapevine cultiva-     boiler followed by
                                                                              tion                 Chiller
                                                                                                                                                                                         Environmental Chemistry Letters (2021) 19:4075–4118
     Banerjee et al. (2019)   India                   Mass of CO2 equiva- Microalgal biomass      Comparison of Trans-       Biodiesel             GaBi 7        n/i
                                                        lent released per MJ                         esterification (Fe2O3
                                                        of fuel produced                             catalyst with HCl
                                                                                                     catalyst)
     Chung et al. (2019)      n/i                     1000 kg of biodiesel   Waste cooking oil     Transesterification        Biodiesel             openLCA 1.8   Agribalyse and NEEDS
                                                        produced per day                             (waste chicken egg-
                                                                                                     shell derived CaO
                                                                                                     catalyst)
     Dasan et al. (2019)      n/i                     100,000 kg of dry      Microalgal biomass    Lipid extraction           Biodiesel             n/i           n/i
                                                        algae biomass for     from                   followed by lipid
                                                        340 days of yearly   Chlorella vulgaris      recovery and trans-
                                                        operation                                    esterification
     Derose et al. (2019)     n/i                     Mass of CO2 equiva- algae harvested from Comparison of:                Biodiesel             n/i           GREET
                                                        lent released per MJ  an algal turf scrub- Biochemical process-
                                                        of fuel produced      ber                    ing with
                                                                                                   Thermochemical
                                                                                                     processing
     Di Fulvio et al. (2019) EU-27 + United           Biodiversity loss per  Biomass from land     n/i                        Biofuel               GISa          GLOBIOM
                              Kingdom                   ha of land use for                                                                                        model
                                                        spatially explicit
                                                        LCA
     Dupuis et al. (2019)     East England, United    Mass of CO2 equiva- Lignocellulosic         n/i                        High octane biodiesel n/i           DNDC and STAMINA
                               Kingdom                  lent released per     Biomass from Mis-                                                                    models
                                                        unit of delivered     canthus and Wheat
                                                        feedstock
     Zhu et al. (2019)        Hubei province,         1 MJ of electricity    Cotton straw          Combustion                 Electricity           n/i           Water footprint
                               China                    output                                                                                                      databaseb
     Wang et al. (2019b)      China                   1 kg hydrogen          Biomass and water     Gasification               Hydrogen              n/i           n/i
13
                                                                                                                                                                                         4093
     Table 10  (continued)
                                                                                                                                                                                            4094
Reference Region Functional unit Feedstock Process Product LCA tools Database
13
     Wagner et al. (2019)    Germany                1 GJ of electricity    Miscanthus              Anaerobic diges-        Electricity           n/i                  Ecoinvent 3.4 and
                                                                                                    tion followed by                                                   KTBL
                                                                                                    combined heat and
                                                                                                    power generation
     Timonen et al. (2019)   Southern Finland       g CO2 eq per MJ of    Pig slurry              Anaerobic digestion     Heat and              SimaPro              LIPASTO
                                                      energy produced                                                      electricity
                                                      and kg C
                                                              O2 eq per
                                                      kg of
                                                    nitrogen (N) in
                                                      digestate
     Tanzer et al. (2019)    Brazil and Sweden      1 GJ of fuel           Agroforestry residues   Comparison of: Gasi-    Marine fuels          CMLCA 5.2            Ecoinvent 2.2
                                                                                                    fication
                                                                                                   Fast pyrolysis hydro-
                                                                                                    treatment
                                                                                                   Hydrothermal lique-
                                                                                                    faction
     Quispe et al. (2019)    Peruvian north coast   1 MJ of energy from    Rice husk               Combustion              Electricity           n/i                  Ecoinvent 3.1
                                                      rice husk
     Krzyżaniak et al.       Poland                 1 Mg of dry biomass    Poplar                  n/i                     Biofuel               SimaPro              Ecoinvent
      (2019)
     Im-Orb and Arporn-      n/i                    kg CO2 eq per kg of   Rice straw              Integrated biomass      Methanol              LCSoft version 6.1   ASPEN Plus
      wichanop, (2020)                               biofuel produced                                pyrolysis,                                  Aspen Engineering
                                                                                                   gasification, and                              8.4
                                                                                                     methanol synthesis
     Jeswani et al. (2020)   United Kingdom         1 MWh of heat          Woodchips from          Boiler                  Heat                  GaBi 4.4             Ecoinvent
                                                                            forestry and sawmill
                                                                            waste
     Lan et al. (2020)       Southeast United       1 MJ of biofuel pro-   Blended feedstock:    Fast pyrolysis fol-       Gasoline and diesel   n/i                  GREET 1.8
                              States                  duced                 switchgrass and       lowed by combus-                                                    Ecoinvent
                                                                            pine residues         tion
     Lask et al. (2020)      Southwest Germany      1 kWh of electricity   Perennial wild plant  Anaerobic digestion       Electricity           openLCA              Ecoinvent
                                                      produced              mixtures and                                                         1.8.0
                                                                           maize silage
     Mendecka et al.         Italy                  Treatment and          Olive pomace          Hydrothermal car-         Bioenergy             n/i                  European Reference
      (2020)                                          upgrade of 1 kg of                          bonisation                                                          Life Cycle Database
                                                      biomass                                                                                                          and Ecoinvent 3.2
     Reaño, (2020)           Southeast Asia         1 kg of biofuel pro-   Rice husk               Comparison of:          Bio-hydrogen          openLCA 1.10         Ecoinvent 3.5
                                                      duced                                        Alkali water elec-
                                                                                                    trolysis
                                                                                                   Gasification
                                                                                                   Dark fermentation
                                                                                                                                                                                            Environmental Chemistry Letters (2021) 19:4075–4118
     Table 10  (continued)
     Reference                Region                Functional unit          Feedstock              Process                  Product                 LCA tools       Database
     Spatari et al. (2020)    United States         1 kg of bio-oil          Forest residues        Comparison of:           Biodiesel               ASPEN Plus      GaBi 9 LCA
                                                                                                    Fast pyrolysis                                   GaBi 9
                                                                                                    Catalytic fast pyroly-
                                                                                                     sis
     Thengane et al. (2020) California, United      1 MJ of torrefied rice   Rice husk              Torrefaction             Torrefied rice husk     openLCA 1.8.0   Ecoinvent 3.4
                             States                   husk pellets                                                            pellets
     Ubando et al. (2020)   Taiwan                  1 kg of torrefied        Microalgal biomass     Torrefaction             Torrefied microalgal    Simapro 8.5.2   Simapro 8.5.2 LCA
                                                      microalgal biomass      from Chlorella                                  biomass
                                                                              vulgaris
     Nilsson et al. (2020)    Sweden                1 ha of land under       Perennial grass        n/i                      Bioenergy               GISa            DNDC agricultural
                                                      cultivation                                                                                                     model
     Aristizábal-Marulanda Colombia                 1 MJ of energy           Coffee cut stems       Comparison of:           Ethanol and electric-   SimaPro 8.3     Ecoinvent 3
      et al. (2021)                                                                                 Enzymatic hydrolysis      ity + steam
                                                                                                                                                                                             Environmental Chemistry Letters (2021) 19:4075–4118
                                                                                                     followed by gasifi-
                                                                                                     cation system
                                                                                                    Gasification only
                                                                                                     system
     Brassard et al. (2021)   Metropolitan France   1000 kg of dry bio-      Primary forestry       Pyrolysis                Bio-oil,                Simapro 9.0     Ecoinvent 3
                                                     mass                     residues                                       biochar) and gaseous
                                                                                                                               (non-condensable
                                                                                                                               gases)
     Cusenza et al. (2021)    Sicily, Italy         1 kWh of electricity     Residual biomasses:    Anaerobic digestion      Electricity and heat    n/i             Ecoinvent 3
                                                      feed into the grid       olive pomace,
                                                                               chicken and bovine
                                                                             manure, whey, citrus
                                                                               processing waste,
                                                                               and Hedysarum
                                                                               coronarium
                                                                             silage
     Da Silva et al. (2021)   Region state of Rio   1 kg of methanol         Rice straw             Gasification             Methanol                Aspen Plus      Aspen Plus
                               Grande do Sul,
                               Brazil
     Fu et al. (2021)         Dongying, Shandong    1 kg of ethanol          Sweet sorghum          Combustion               Ethanol                 GISa            Harmonised world soil
                               province, China
     Martillo Aseffe et al.   Ecuador (Los Rios     1 ton of seed-corn       Corncob                Comparison of:           Electricity             SimaPro 8       SimaPro 8 LCA
      (2021)                   and Guayas)            produced                                      Combustion
                                                                                                    Gasification
     Schonhoff et al.         Germany               100 GJ thermal           Sida hermaphrodita     Comparison of:           chips, pellets and bri- GaBi 9.2        Ecoinvent 3.5
      (2021)                                         energy                                         Chopping                   quettes as carriers
                                                                                                    Pelletisation              of Thermal energy
                                                                                                    Splitting
13
                                                                                                                                                                                             4095
     Table 10  (continued)
                                                                                                                                                                                           4096
Reference Region Functional unit Feedstock Process Product LCA tools Database
13
     Schmidt Rivera et al.     United Kingdom         1 tonne of spent cof-   Spent coffee grounds   Comparison of:           Biodiesel,            GaBi 8.7               Ecoinvent 3.3
      (2020)                                            fee grounds treated                          Incineration             compost
                                                                                                     Landfilling,
                                                                                                     Anaerobic digestion,
                                                                                                       Composting fol-
                                                                                                       lowed by
                                                                                                     direct application to
                                                                                                       land
     Al-Mawali et al.          Gulf cooperation       1000 kg of biodiesel    Waste date seeds       Esterification using a   Biodiesel             SimaPro                SimaPro LCA
      (2021)                   council countries                                                       magnetic catalyst
     Yang et al. (2021)        China                  1 ton of crop residues Crop residues           Slow pyrolysis           Biofuel and biochar   GaBi 8.7               PRC 2019c
     Saranya and               Karnataka, India       Biomass achievable in Microalgal biomass       Comparison of:           Biodiesel             OpenLCA 1.10.3         Ecoinvent 3.6
      Ramachandra,                                      1 ha area                                    Acid catalysis
      (2020)                                                                                         Biocatalysis
     Bora et al. (2020)        United States          1000 kg of wet poul-    Poultry litter         Comparison of:           Biofuel and biochar   n/i                    Ecoinvent 3
                                                       try litter                                    Direct land use
                                                                                                     Pyrolysis
                                                                                                     Gasification
                                                                                                     Hydrothermal pro-
                                                                                                       cessing
     Al-Muhtaseb et al.        Pakistan               1000 kg of biodiesel    Waste loquat seeds     Transesterification      Biodiesel             SimaPro                SimaPro LCA
      (2021)                                                                                           using a CaO/CeO2
                                                                                                       catalyst
     n/i: Not included, EU-27: The European Union; GREET: Greenhouse Gases, Regulated Emissions, and Energy Use in Transportation
     a
         GIS: Some life cycle assessment (LCA) studies analysed environmental impacts of land use for biofuel production and thus used geographic information systems software
     b
         Water footprint database: Data sourced from the water footprint assessment manual
     c
         PRC 2019: Data sourced from the national development and reform commission of the People’s Republic of China (PRC)
                                                                                                                                                                                           Environmental Chemistry Letters (2021) 19:4075–4118
Environmental Chemistry Letters (2021) 19:4075–4118                                                                                                                          4097
Fig. 4  Types of functional units                                                                 Types of functional units considered in the reviewed
used in the life cycle assessment                                                                                        studies
                                                                                       35
studies reviewed in the present
work (N = 40)
                                                                                       30
                                                               % of studies reviewed
                                                                                       25
20
15
10
                                                                                       0
                                                                                            Bioenergy        Biofuel     Biomass         Biomass       Land use      Other
                                                                                            produced        produced     produced         used
Fig. 5 General system boundary for conducting life cycle assessment of conversion of biomass feedstocks to biofuels
Fig. 6  Phases of system bound-                                                               Phases of system boundary considered in the reviewed
ary considered for conduct-
                                                              100
                                                                                                                    studies
ing life cycle assessment of
converting biomass feedstocks                                 90
                                      % of studies reviewed
                                                                                                                                                                     13
4098                                                                               Environmental Chemistry Letters (2021) 19:4075–4118
Life cycle inventory analysis                                      of reactive substances injurious to human health and ecosys-
                                                                   tems. Acidification measured in kg SO2 equivalent is caused
Inventory analysis involves quantifying all the inputs and         by the emission of acidifying substances. Land use calcu-
outputs for the processes considered in the system bound-          lated in m2 is categorised as the transformation of urban
ary of the LCA. This includes raw material requirements,           land, agricultural land and natural land such as forests. Water
energy input, emissions to air, wastewater production, solid       depletion (m3) is the use of water for the entire production
waste generation, emissions to land and others. It should be       chain of biofuels. Particulate matter formation expressed
noted that more the systems involved in the system bound-          as PM2.5 equivalent and/or PM10 equivalent relates to the
ary, greater would be the need for data for inventory analy-       emission of PM 2.5 (particulate matter with ≤ 2.5 µm in
sis, which also is explained in Fig. 6 with only some studies      diameter) and/or PM10 (particulate matter with ≤ 10 µm in
considering all the phases of biofuel production.                  diameter). Eutrophication consists of the effect of releas-
   Table 10 shows databases for conducting inventory analy-        ing an excessive amount of nutrients reported as kg P       O4
sis, used in the reviewed studies such as SimaPro LCA data-        equivalent. Ionising radiation (kg U235 equivalent) transfers
bases, Ecoinvent, GREET (Greenhouse Gases, Regulated               energy into the body tissue and may thereby interfere with
Emissions, and Energy Use in Transportation). Some LCA             the structure of molecules (Table 11).
studies also used agricultural models for considering the             Finally, human toxicity is recorded as kg 1,4 dichloroben-
impacts of land use on overall environmental sustainability,       zene equivalent or cumulative toxic units. Human toxicity
such as GLOBIOM, DNDC and STAMINA (Di Fulvio et al.                (carcinogens) is an index that corresponds to potential harm
2019; Dupuis et al. 2019; Nilsson et al. 2020).                    of a unit of cancer-causing chemical released into the envi-
                                                                   ronment and is based on both the inherent toxicity of a com-
Environmental impacts assessment                                   pound and its potential dose. Human toxicity (non-carcino-
                                                                   gens) index is associated with non-carcinogenic chemicals
Mid‑point indicators                                               release, doses and exposure.
In this stage of LCA, key environmental impacts are quan-          Endpoint indicators
tified and distributed in various environmental categories
depending upon the functional unit, system boundary, mod-          The mid-point categories are aggregated to present results
elled systems and need of the decision-makers. Some studies        as endpoint categories. It is argued that the environmental
computed net energy ratio to evaluate the usability of biofu-      impacts should be presented as mid-point categories to pre-
els as energy sources (Al-Mawali et al. 2021; Al-Muhtaseb          vent oversimplification or misinterpretation of environmen-
et al. 2021; Dasan et al. 2019; Im-Orb and Arpornwichanop          tal impacts (Kalbar et al. 2017). Nevertheless, some studies
2020; Reaño 2020; Saranya and Ramachandra 2020), which             did not present detailed mid-point indicator impacts but only
is defined as the ratio of output energy to input energy for the   endpoint indicators (Amezcua-Allieri et al. 2019; Martillo
overall process (Pleanjai and Gheewala 2009).                      Aseffe et al. 2021; Bora et al. 2020).
    Mid-point categories used for expressing life cycle               The endpoint categories used in reviewed studies were:
environmental impacts were: global warming potential               (1) human health (disability-adjusted life year) is related
(100 years), which includes greenhouse emissions is gen-           to the impacts of environmental degradation that results in
erally expressed as kg CO2 equivalent for a time horizon          an increase in and duration of loss of life years due to ill
of 100 years. Some studies also considered greenhouse gas          health, disability or early death, and (2) ecosystem quality
emissions for a temporal scale of 20 years, in accordance          (species × year) is linked to the impact of global warming
with the life span of infrastructure (Aberilla et al. 2019;        potential, ozone layer depletion, acidification, ecotoxicity,
Cusenza et al. 2021). Abiotic depletion reported as kg Sb          eutrophication and indicates biodiversity loss. It is recorded
equivalent corresponds to the depletion of fossil fuels, min-      as local species loss integrated over time, and (3) resources
erals, clay and peat. Abiotic depletion (fossil fuels, recorded    are related to the depletion of raw materials and energy
as MJ) is linked to the depletion of fossil deposits. Ozone        sources expressed generally in US dollars ($), representing
layer depletion (kg trichlorofluoromethane equivalent) is          the extra costs involved for future mineral and fossil resource
typically accounted for a time scale of 40 years.                  extraction (Al-Muhtaseb et al. 2021).
    Ecotoxicity potential evaluated in kg 1,4 dichlorobenzene
equivalent or cumulative toxic units is calculated in three        Uncertainty, scenario and sensitivity analysis
separate categories, which examine damage to terrestrial,
freshwater and marine sources for the entire production pro-       Life cycle assessment (LCA) studies are models which
cess. Photochemical oxidation recorded in kg non-methane           are simplified versions of the real-world system and thus
volatile organic compounds equivalent refers to emissions          are inherently uncertain (Wang and Shen 2013). These
13
     Table 11  Environmental impacts and main findings recorded in the life cycle assessment case studies analysed
     Reference                             Environmental impacts considered                                              Findings
     Aberilla et al. (2019)                Global warming (20 years), ozone layer depletion, particulate matter forma- The study compared anaerobic digestion, combustion and gasification for
                                            tion, photochemical oxidant formation, freshwater eutrophication, marine      rice and coconut residues in South East Asia to produce 1 kWh of electric-
                                            eutrophication, terrestrial acidification, freshwater ecotoxicity, marine     ity as the end product. It was observed that anaerobic digestion was the
                                            ecotoxicity, terrestrial ecotoxicity, fossil depletion, mineral depletion,    best option for 14 out of 18 impacts (the remaining four impacts categories
                                            water depletion, agricultural land occupation, natural land transformation,   were: global warming, photochemical oxidant formation, particulate matter
                                            urban land occupation, human toxicity, ionising radiation                     formation and terrestrial ecotoxicity potentials)
                                           potentials                                                                    Global warming potential for anaerobic digestion = 100 kg CO2 eq
                                                                                                                         Global warming potential for gasification and combustion = -30 to 30 kg C  O2
                                                                                                                          eq
                                                                                                                         Ozone layer depletion for anaerobic digestion = − 36 µg CFC-11 eq
                                                                                                                         Ozone layer depletion for gasification and combustion = − 1 µg CFC-11 eq
                                                                                                                         Human toxicity (carcinogens) for anaerobic digestion = − 74 g 1,4 DB eq
                                                                                                                                                                                                          Environmental Chemistry Letters (2021) 19:4075–4118
13
                                                                                                                                                                                                          4099
     Table 11  (continued)
                                                                                                                                                                                              4100
13
     Chung et al. (2019)       Global warming, ozone layer depletion, eutrophication, terrestrial acidifica- The highest environmental impacts were observed during transesterification
                                tion, ecotoxicity, fossil depletion, minerals depletion, land use, human       of the entire biodiesel production process. The transesterification pro-
                                toxicity(carcinogens), ionising radiation, respiratory inorganics and          cess contributed a 1010 MJ surplus on fuel consumption due to the high
                                respiratory organics potentials                                                demand of electrical energy for 1000 kg of biodiesel produced
     Dasan et al. (2019)       Net energy ratio and global warming potential (10,000 years)                  This study assessed the impact of different microalgae cultivation systems on
                                                                                                               biomass productivity. The net energy ratio was below 1 for all microalgae
                                                                                                               cultivation systems (open pond, tubular, bubble column photo-bioreactors)
     Derose et al. (2019)      Global warming potential                                                      Biochemical and thermochemical pathways were compared for bioenergy
                                                                                                               production (1 MJ of fuel produced)
                                                                                                             Global warming potential for biochemical pathway = 111.2 g CO2 eq
                                                                                                             Global warming potential for thermochemical pathway = − 2 g CO2 eq
     Di Fulvio et al. (2019)   Biodiversity loss                                                             Increased cultivation of perennial crops for bioenergy production could be an
                                                                                                               option for climate change mitigation. However, it could negatively impact
                                                                                                               biodiversity through loss of species habitats in EU-27 and the UK
     Dupuis et al. (2019)      Global warming potential per unit of delivered feedstock (100 years)          Perennial energy crops rather than wheat husk should be considered biofuel
                                                                                                               in East England based on the life cycle assessment of the use of wheat husk
                                                                                                               and energy crops
     Zhu et al. (2019)         Water footprint in L per MJ of bioenergy                                      The total life cycle water use intensity for using cotton straw as a bioenergy
                                                                                                               source via combustion was 11.708 L/MJ, lower than bio-oil power genera-
                                                                                                               tion, however, much greater than other renewable energy sources (such as
                                                                                                               geothermal, solar photovoltaic and wind power). The study also noted that
                                                                                                               biomass agricultural production accounted for 84.61% of the total water
                                                                                                               use
     Wang et al. (2019b)       Global warming potential                                                      An increase in gasification temperature and decrease in biomass slurry con-
                                                                                                               centration and pressure could decrease global warming potential
     Wagner et al. (2019)      Global warming, agricultural land occupation, freshwater ecotoxicity,         This study noted that marginal German electricity mix, when substituted by
                                human toxicity, marine ecotoxicity potential, freshwater eutrophication        miscanthus-based biogas, can lead to net benefits in the impact categories
                                and marine eutrophication potentials                                           of global warming potential, human toxicity, marine ecotoxicity, freshwater
                                                                                                               ecotoxicity and freshwater eutrophication. This was observed even when
                                                                                                               the biomass is transported over longer distances, biomass yields are lower,
                                                                                                               or a lower heat utilisation rate is applied
     Timonen et al. (2019)     Global warming potential                                                      The study compared the use of pig slurry with grass and pig slurry with food
                                                                                                               waste as feedstocks for anaerobic digestion
                                                                                                             The highest global warming potential was observed when pig slurry and
                                                                                                               grass from uncultivated fields were used for anaerobic digestion. This
                                                                                                               could be due to due to prominent N    2O emissions from grasslands, while
                                                                                                               the lowest level of global warming potential was in the scenario, which
                                                                                                               involved the digestion of pig slurry and side streams from the food industry
                                                                                                               due to avoided emissions from co-feedstock procurement (covered storage
                                                                                                               and zero emissions to produce food industry sludge as waste)
                                                                                                                                                                                              Environmental Chemistry Letters (2021) 19:4075–4118
     Table 11  (continued)
     Reference               Environmental impacts considered                                          Findings
     Tanzer et al. (2019)    Global warming potential (100 years), NOx and SO2 emissions             All biofuel systems of agroforestry residues have substantially lower life
                                                                                                        cycle environmental impacts compared to heavy fuel oil (HFO, marine fuel
                                                                                                        reference)
                                                                                                       Global warming potential for biofuels = − 30 to 40 kg CO2 eq/GJ
                                                                                                       Global warming potential for HFO reference = 90 kg C
                                                                                                                                                           O2 eq/GJ
                                                                                                       SO2 emissions all biofuels < 0.3 kg SO2/GJ
                                                                                                       SO2 emissions for HFO reference = 2.5 kg SO2/GJ
                                                                                                       NOX emissions from biofuels ≈ HFO reference = 1.6 kg NOX/GJ
     Quispe et al. (2019)    Global warming (100 years), acidification potential, eutrophication and   For generating 457 MJ of bioenergy from fuels considered, the results
                              water depletion potentials                                                obtained are summarised below
                                                                                                                                                                                        Environmental Chemistry Letters (2021) 19:4075–4118
                                                                                                       For rice husk, with yield = 9.5 t/ha and dryer efficiency as 0.7:
                                                                                                       Global warming potential = 1.96 kg CO2 eq
                                                                                                       Water depletion potential = 2.3 m3
                                                                                                       Eutrophication potential = 12.5 g PO4 eq
                                                                                                       Acidification potential = 50.3 g S
                                                                                                                                         O2 eq
                                                                                                       For coal system:
                                                                                                       Global warming potential = 61 kg CO2 eq,
                                                                                                       Water depletion = 23 m3
                                                                                                       Eutrophication potential = 63 g PO4 eq
                                                                                                       Acidification potential = 462 g S
                                                                                                                                        O2 eq
                                                                                                       The study concluded that if all rice husk available in Peru were used for dry-
                                                                                                        ing processes instead of coal, it could mitigate around 708,540 metric tons
                                                                                                        of CO2 eq per year
13
                                                                                                                                                                                        4101
     Table 11  (continued)
                                                                                                                                                                                                     4102
13
     Krzyżaniak et al. (2019)          Global warming, particulate matter formation, terrestrial acidification,     This study compared poplar production (1 tonne of dry matter) as lignocel-
                                        freshwater eutrophication, human toxicity, freshwater ecotoxicity, fossil    lulosic feedstock for use in bioenergy systems considering four fertilisation
                                        depletion potentials                                                         systems: unfertilised, mineral, lignin and lignin + mineral, and observed the
                                                                                                                     following results
                                                                                                                    Global warming potential for lignin + mineral fertilisation system = −20 kg
                                                                                                                     CO2 eq
                                                                                                                    Global warming potential for unfertilised system = 20 kg C
                                                                                                                                                                              O2 eq
                                                                                                                    Particulate matter formation potential for lignin + mineral fertilisation sys-
                                                                                                                     tem = 0.3 kg PM10 eq
                                                                                                                    Particulate matter formation potential for unfertilised system = 0.3 kg PM10
                                                                                                                     eq
                                                                                                                    Terrestrial acidification potential for lignin + mineral fertilisation sys-
                                                                                                                     tem = 0.7 kg SO2 eq
                                                                                                                    Terrestrial acidification potential for unfertilised system = 0.3 kg SO2 eq
                                                                                                                    Freshwater eutrophication potential for lignin + mineral fertilisation sys-
                                                                                                                     tem = 0.01 kg P eq
                                                                                                                    Freshwater eutrophication potential for unfertilised system = 0.3 kg P eq
                                                                                                                    Human toxicity potential for lignin + mineral fertilisation system = 9 kg 1,4
                                                                                                                     DB eq
                                                                                                                    Human toxicity potential for unfertilised system = 19 kg 1,4 DB eq
                                                                                                                    The study concluded that fertilised systems could cause negative environ-
                                                                                                                     mental impacts for poplar production in Poland
     Im-Orb and Arpornwichanop (2020) Net energy ratio and                                                          The study analysed the life cycle impacts of methanol production. The
                                      potential environmental impact                                                 impact categories considered global warming, ozone layer depletion,
                                                                                                                     acidification, eutrophication, photochemical oxidant formation, ecotoxicity,
                                                                                                                     respiration effects, human toxicity (non-carcinogens) and human toxic-
                                                                                                                     ity (carcinogens) were all merged as potential environmental impact. The
                                                                                                                     highest net energy ratio achieved was 0.612. The lowest PEI/kg methanol
                                                                                                                     was observed as 0.18
                                                                                                                                                                                                     Environmental Chemistry Letters (2021) 19:4075–4118
     Table 11  (continued)
     Reference                Environmental impacts considered                                               Findings
     Jeswani et al. (2020)    Global warming, abiotic depletion, abiotic depletion for fossil fuels, acidifi- The study compared the use of biomass for boiler compared to fossil
                               cation, eutrophication, freshwater ecotoxicity, human                           resources (i.e. natural gas, oil and electricity). The findings demonstrated
                                                                                                               that heat from biomass boilers had lower impacts than from the coal and oil
                                                                                                               equivalents in all categories (except terrestrial ecotoxicity potential). Some
                                                                                                               of the environmental impacts observed for the production of 1MWh of heat
                                                                                                               are summarised below
                              toxicity, marine ecotoxicity, ozone layer depletion, photochemical oxidant     Global warming potential during biomass use = 14.7 kg CO2 eq
                                formation and terrestrial ecotoxicity potentials
                                                                                                             Global warming potential during use of fossil resources = 233.9–468.4 kg
                                                                                                              CO2 eq
                                                                                                             Terrestrial ecotoxicity potential during biomass use = 0.6 kg DB eq
                                                                                                                                                                                                Environmental Chemistry Letters (2021) 19:4075–4118
13
                                                                                                                                                                                                4103
     Table 11  (continued)
                                                                                                                                                                                                           4104
13
     Spatari et al. (2020)                 Global warming potential (100 years)                                          For 1 MJ of biodiesel produced:
                                                                                                                         Global warming potential for catalytic pyrolysis = − 80 g CO2 eq
                                                                                                                         Global warming potential for fast pyrolysis = 20 g CO2 eq
     Thengane et al. (2020)                Global warming potential                                                      Global warming potential = 6.04 ton C O2 eq/ton torrefied rice husk for severe
                                                                                                                          torrefaction
     Ubando et al. (2020)                  Global warming, water depletion, fossil resource scarcity, mineral resource   Global warming potential was observed as 12.72 C    O2 eq for the entire
                                            scarcity, land use, human toxicity(carcinogens), human toxicity (non-car-     process from cultivation to torrefaction. For all other categories, only
                                            cinogens), marine ecotoxicity, freshwater toxicity, terrestrial ecotoxicity,  normalised results as % were recorded
                                            marine eutrophication, freshwater eutrophication, terrestrial acidification,
                                            ozone layer depletion, particulate matter formation, ionising radiation
                                            potentials
     Nilsson et al. (2020)                 Global warming (100 years) and eutrophication potentials                      The mean global warming potential was 1170 ± 460 and 1200 ± 460 kg CO2
                                                                                                                          eq/ha year for a 140 and 200 kg N/ha fertilisation rate. The eutrophication
                                                                                                                          potential was observed as 11 ± 6.1 kg N-eq/ha to use 1 ha of land to pro-
                                                                                                                          duce perennial grass as a biofuel source in five different sites in Sweden.
                                                                                                                          The variation between sites highlights the use of temporal and spatial data
                                                                                                                          for assessing whole life cycle impacts
     Aristizábal-Marulanda et al. (2021)   Global warming, ozone layer depletion, terrestrial acidification, freshwater The study compared the use of coffee-cut stems for ethanol production
                                            eutrophication, human toxicity, photochemical oxidant formation, par-         concerning the production of electricity and steam. Lesser environmental
                                            ticulate matter formation, freshwater ecotoxicity, water depletion, fossil    impacts were observed for the latter. Some of the findings for both 1 MJ of
                                            depletion and agricultural land occupation potentials                         ethanol and 1 MJ of electricity and steam are:
                                                                                                                         Global warming potential for 1 MJ of ethanol = 1.37 kg CO2 eq
                                                                                                                         Global warming potential for 1 MJ of electricity and steam = 0.27 kg CO2 eq
                                                                                                                         Ozone layer depletion potential for 1 MJ of ethanol = 2.5 × 10–8 kg CFC-
                                                                                                                          11 eq
                                                                                                                         Ozone layer depletion potential for 1 MJ of electricity and
                                                                                                                          steam = 0.7 × 10–8 kg CFC-11 eq
                                                                                                                         Fossil depletion potential for 1 MJ of ethanol = 0.05 kg oil eq
                                                                                                                         Fossil depletion potential for 1 MJ of electricity and steam = 0.01 kg oil eq
                                                                                                                                                                                                           Environmental Chemistry Letters (2021) 19:4075–4118
     Table 11  (continued)
     Reference                Environmental impacts considered                                                Findings
     Brassard et al. (2021)   Global warming (100 years), ozone layer depletion, human toxicity (car-         This study compared the use of primary forestry residues for pyrolysis to the
                               cinogens), freshwater eutrophication, mineral resource use, terrestrial,        business-as-usual of no use and concluded that pyrolysis could result in
                               freshwater acidification, water scarcity, photochemical ozone forma-            better environmental impacts in nine out of a total of 16 categories. Some
                               tion, human toxicity (non-carcinogens), respiratory inorganics, marine          results recorded for the use of 1000 kg of feedstock are given below
                               eutrophication, terrestrial eutrophication, freshwater ecotoxicity, ionising
                               radiation, resource use (energy carriers), land use potentials                 Global warming potential = 906 kg CO2 eq during pyrolysis
                                                                                                              Global warming potential = 1750 kg CO2 eq during no use
                                                                                                              Ozone layer depletion potential = 3 × 10–5 kg CFC-11 eq during pyrolysis
                                                                                                              Ozone layer depletion potential = 2 × 10–5 kg CFC-11 eq during no use
                                                                                                              Mineral resource use potential = 1.5 × 10–3 kg Sb eq during pyrolysis
                                                                                                              Mineral resource use potential = 2.5 × 10–4 kg Sb eq during no use
                                                                                                                                                                                              Environmental Chemistry Letters (2021) 19:4075–4118
13
                                                                                                                                                                                              4105
     Table 11  (continued)
                                                                                                                                                                                                   4106
13
     Martillo Aseffe et al. (2021)   Global warming potential                                                     The study analysed the use of corncob for electricity production through
                                                                                                                   gasification and combustion and its impacts on the seed-corn supply chain.
                                                                                                                   It concluded that if waste-to-energy scenarios are included with the agri-
                                                                                                                   business sector, it could reduce environmental impacts
                                     and                                                                          Global warming potential = 913 kg CO2 eq/t seed-corn through combustion
                                     Endpoint indicators: human health, ecosystem quality, resource depletion      Global warming potential = 797 kg CO2 eq/t seed-corn through gasification
     Schonhoff et al. (2021)         Global warming (including biogenic carbon), global warming (exclud-           The study concluded that different production and processing pathways for
                                       ing biogenic carbon), acidification, freshwater eutrophication, terrestrial  Sida hermaphrodita biomass did not significantly differ in the overall envi-
                                       eutrophication, marine eutrophication, human toxicity (carcinogens),         ronmental impacts. Moreover, when comparing Sida hermaphrodita bio-
                                       human toxicity (non-carcinogens), land use, particulate matter formation,    mass was performed with alternative biomasses like wood or Miscanthus;
                                       water depletion, freshwater ecotoxicity, ionising radiation, photochemical   in most cases (except Miscanthus and mixed logs), beneficial properties of
                                       zone formation, abiotic depletion potentials                                 Sida hermaphrodita biomass were observed
                                                                                                                   For 100 GJ of thermal energy from Sida hermaphrodita biomass, some of
                                                                                                                    the environmental impacts recorded were:
                                                                                                                   Global warming potential (including biogenic carbon) ≈ 12,000 kg C     O2 eq
                                                                                                                   Global warming potential (excluding biogenic carbon) ≈ 1500 kg C     O2 eq
                                                                                                                   Ozone layer depletion potential ≈ 10 × 10–5 kg CFC-11 eq
                                                                                                                   Abiotic depletion potential ≈ 0.15 kg Sb eq during pyrolysis
                                                                                                                   Human toxicity(carcinogens) = 14 to 19 × 10–5 cumulative toxicity units
                                                                                                                   Human toxicity(non-carcinogens) ≈ 10.5 × 10–4 cumulative toxicity units
     Schmidt Rivera et al. (2020)    Global warming, primary                                                       The study compared waste treatment cases for spent coffee grounds. It
                                                                                                                    concluded that overall, incineration (with electricity and heat recovery)
                                                                                                                    showed the least environmental impacts compared to landfilling, biodiesel
                                                                                                                    production and composting, followed by the spreading of compost on
                                                                                                                    land. It showed that use for waste as an energy source should follow not
                                                                                                                    only waste hierarchy but also life cycle assessment. Some of the impacts
                                                                                                                    recorded for incineration (with electricity and heat recovery—best case)
                                                                                                                    and biodiesel production using 1 tonne of spent coffee grounds are below
                                     energy demand, fossil depletion, metal depletion, particulate matter forma- Global warming potential for biodiesel production = 31 kg CO2 eq
                                       tion, stratospheric ozone depletion, photochemical oxidant
                                     (ecosystems), photochemical oxidant (humans) formation, freshwater            Global warming potential for incineration = 525 kg CO2 eq
                                       eutrophication, marine eutrophication, terrestrial acidification, human
                                       toxicity (carcinogens), human toxicity (non-carcinogens), freshwater
                                       ecotoxicity, marine ecotoxicity and terrestrial ecotoxicity potentials
                                                                                                                   Ozone layer depletion for biodiesel production = 0.25 g CFC-11 eq
                                                                                                                   Ozone layer depletion for incineration = 0.18 g CFC-11 eq
                                                                                                                   Human toxicity (non-carcinogens) for biodiesel production = 357 kg 1,4 DB
                                                                                                                    eq
                                                                                                                   Human toxicity (non-carcinogens) for incineration = 5 kg 1,4 DB eq
                                                                                                                                                                                                   Environmental Chemistry Letters (2021) 19:4075–4118
     Table 11  (continued)
     Reference                         Environmental impacts considered                                               Findings
     Al-Mawali et al. (2021)           Net energy ratio and                                                           The study conducted LCA to analyse the transformation of waste date seed
                                                                                                                       oil to biodiesel via esterification. It concluded that it is environmentally
                                                                                                                       feasible to produce biodiesel from waste-derived feedstocks
                                       Global warming (100 years), ozone layer depletion, abiotic depletion (fossil Net energy ratio = 2.17
                                        fuels)
                                       abiotic depletion, human toxicity, freshwater ecotoxicity, marine ecotoxic-    Global warming potential = 1.11 kg C
                                                                                                                                                          O2 eq/kg of biodiesel produced
                                         ity
                                       terrestrial ecotoxicity, photochemical oxidant formation, acidification, and   Abiotic depletion potential = 2 × 10–5 kg Sb eq/kg of biodiesel produced
                                         eutrophication potentials
                                                                                                                      Abiotic depletion (fossil fuels) potential = 19 MJ/kg of biodiesel produced
                                                                                                                      Human toxicity potential = 0.6 kg 1,4 DB eq/kg of biodiesel produced
                                                                                                                                                                                                      Environmental Chemistry Letters (2021) 19:4075–4118
     Yang et al. (2021)                Global warming (100 years), ozone layer depletion, abiotic depletion,          The study used LCA to evaluate the potential of biochar for carbon seques-
                                        human toxicity, freshwater ecotoxicity, marine ecotoxicity                      tration produced using crop residue in China. The carbon sequestration
                                                                                                                        potential of a country-level biochar system was estimated at 500 × 1012 kg
                                                                                                                       CO2 eq for a year. This accounts for 4.50% of the total greenhouse gas
                                                                                                                        emissions from China, which could be mitigated by use of biochar
                                       terrestrial ecotoxicity, photochemical oxidant formation, acidification, and   Global warming potential = -5 × 1014 kg CO2 eq/kg of biochar
                                         eutrophication potentials
                                                                                                                      Abiotic depletion potential = 4.5 × 107 kg Sb eq/kg of biochar
     Saranya and Ramachandra, (2020)   Net energy ratio and                                                           The study compared acid catalysis and biocatalysis for the use of microalgal
                                                                                                                       biomass feedstocks (produced in 1 ha of land—FU) for biodiesel produc-
                                                                                                                       tion. The study concluded that biocatalysis was the best route to use with
                                                                                                                       the following impacts
                                       Global warming (100 years), abiotic depletion, abiotic depletion (fossil       Net energy ratio = 18.8
                                        fuels)
                                       photochemical oxidant formation, acidification, and eutrophication poten-      Global warming potential = 2000 – 3000 kg CO2 eq/FU
                                        tials
                                                                                                                      Abiotic depletion potential = 0.004 kg Sb eq/FU
     Bora et al. (2020)                Endpoint indicators: global warming potential, human health, ecosystem         This study computed 15 mid-point indicators for thermochemical conversion
                                        quality, resource depletion                                                    of poultry litter to fuel and biochar in the USA. However, the results were
                                                                                                                       aggregated to present endpoint indicators for 1000 kg of poultry litter (FU)
                                                                                                                      Global warming potential of thermochemical conversion = 659 to 1192 kg
                                                                                                                       CO2 eq/FU
                                                                                                                      Global warming potential for spreading on fields = 1410 kg CO2 eq/ FU
13
                                                                                                                                                                                                      4107
  4108                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                            Environmental Chemistry Letters (2021) 19:4075–4118
                                                                                                                                                                                                                                                                                                                                                                                                                                                                                           CFC-11: Trichlorofluoromethane; DB: dichlorobenzene; EU-27: The European Union; eq: Equivalent; FU: Functional unit; HFO: Heavy fuel oil; LCA: Life cycle assessment; NER: Net energy
                                                           The study conducted LCA to analyse the transformation of waste date seed
                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                   judgement, linguistic imprecision, variability in space
                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                                   Interpretation of results
                        Environmental impacts considered
     13
Environmental Chemistry Letters (2021) 19:4075–4118                                                                          4109
(Pleanjai and Gheewala 2009), recorded net energy ratio > 1,       only one study identified that highlighted that for spent cof-
showing the importance of biofuels as energy sources.              fee grounds, incineration is a better route compared to bio-
    Generally recognised contentious issue to produce bio-         fuel production (Schmidt Rivera et al. 2020).
fuels was land use which could occur due to natural land,             Finally, focusing on the comparison of biological and
agricultural and urban land transformation. This was high-         thermochemical pathways, in general, it was observed in the
lighted by the fact that 7% of the studies used land use as        comparative studies that thermochemical processes showed
a functional unit (Fig. 5); furthermore, about 15% of the          lesser environmental impacts compared to biological pro-
reviewed studies analysed impacts on land use (Aberilla            cesses for the same biomass and geographical and temporal
et al. 2019; Chung et al. 2019; Ubando et al. 2020; Aris-          span (Ardolino and Arena 2019; Derose et al. 2019). Even in
tizábal-Marulanda et al. 2021; Brassard et al. 2021; Schon-        Aberilla et al. (2019), which showed higher environmental
hoff et al. 2021). It was also noted that the use of perennial     impacts in the thermochemical process, the greenhouse gas
energy crops is an interesting approach towards mitigation of      emissions for gasification were lower than that of anaerobic
greenhouse gas emissions; however, it could result in loss of      digestion for rice and coconut residues.
biodiversity for the European Union and UK (EU-27 + UK)
(Di Fulvio et al. 2019) (Table 11).
    Other studies focused on water depletion and concluded         Bibliometric analysis
that while producing biofuels can mitigate greenhouse gas
emissions, it is also necessary to compute water depletion         Figure 8a, b depicts the bibliometric analysis mapping origi-
during crop production and biomass processing (Aberilla            nated from the Web of Science core collection for the net-
et al. 2019; Quispe et al. 2019; Ubando et al. 2020; Aris-         work visualisation and density visualisation, respectively.
tizábal-Marulanda et al. 2021; Schonhoff et al. 2021). In          Firstly, the data were exported 500 entries at a time of 9947
fact, Zhu et al. (2019) concluded that water depletion for         results and then were fed into the VOSviewer software that
biofuel production from cotton straws was lower than bio-          plotted the data. The type of analysis used herein was co-
oil power generation, however, much greater than observed          occurrence, and all keywords were included, as well as
for other renewable sources of energy (such as geothermal,         the fractional counting method. We observed direct clus-
solar photovoltaic and wind power). Most of the water use          ters connecting identifiable keywords to broad topics such
occurred due to biomass agricultural production, accounting        as thermochemical, biochemical and processes associated
for 84.6% of the total water use.                                  with those two routes (gasification, pyrolysis, hydrothermal
    The impacts on land use and water depletion due to energy      liquefaction, combustion, torrefaction, anaerobic digestion
crop production show that waste-derived feedstocks could           and fermentation). This enabled the visualisation of most
provide more sustainable energy sources. Waste-to-energy           of the significant keywords in publications in the period of
applications for biomass could mitigate the use of land, fer-      1970–2021 that were associated with the thermochemical
tilisers and water for agriculture of energy crops. This is also   and biochemical conversion routes of biomass.
in accordance with zero-waste hierarchy for management of             It is evident from Fig. 8a, b that keywords that have seen
waste biomass (Refuse/ redesign > Reduce > Reuse > Recy-           a significant increase in popularity and, as a result, progress
cle > Material and chemicals recovery > Residuals man-             in keyword research such as biomass gasification, pyrolysis
agement > Unacceptable, e.g. landfilling of non-stabilised         and combustion as they part of the thermochemical route in
waste/energy recovery) (Simon, 2019). In fact, there was           biomass conversion. In addition, other correlated keywords
                                                                                                                       13
4110   Environmental Chemistry Letters (2021) 19:4075–4118
13
 Environmental Chemistry Letters (2021) 19:4075–4118                                                                                      4111
◂Fig. 8  Bibliometric mapping of biomass conversion processes into    microorganism or generate various inhibitors that can affect
 biofuels a network visualisation and b density visualisation maps.   the biological progress routes. Furthermore, this integration
 The bibliometric mapping was performed between 1970 and 2021
                                                                      may lead to additional costs.
                                                                         Moreover, to understand the recent advances in evaluat-
 have shown in the bibliometric mapping, such as hydrogen             ing environmental impacts due to biofuel production, we
 production, catalysts and fuel performance. This signifies           conducted an intensive critical review of 40 life cycle assess-
 that the process of thermochemical conversion is at a very           ment (LCA) studies published from the years 2019–2021,
 mature stage in terms of research and development, as dem-           including methods and findings. The important methods and
 onstrated by the prominence of publication keywords over             key findings observed were:
 the last 51 years. Because of its higher productivity, eco-
 nomic viability and existing infrastructure compatibility            1. Only eight studies included all three phases of biofuel
 resources, it is ultimately readily available and easily scaled         production (which includes biomass cultivation, biofuel
 up for the industrial sector.                                           production process and biofuel use and end-of-life man-
    Although gasification appears to be most researched in               agement phase).
 the thermochemical route, this could be down to the fact             2. Waste-derived feedstocks could provide more sustain-
 that gasification technology has existed longer than coun-              able energy sources by mitigating impacts on land use
 terpart technologies, apart from combustion. This also does             and water depletion incurred during the production of
 not indicate that it is the most efficient thermochemical               energy crops.
 technology in process efficiency and product quality. For            3. Focusing on thermochemical and biological processes
 example, when using gasification, there is a need to remove             for the same biomass feedstock and geographical and
 the hydrogen sulphide and clean the synthesis gas produced              temporal span, thermochemical processes caused lesser
 and other requirements.                                                 greenhouse gas emissions compared to biological path-
    On the other hand, the biochemical conversion route is               ways.
 less favourable since it suffers from certain limitations, such
 as its time-consuming process and low product yield and                 This review has suggested interesting new avenues for
 product inhabitation. Biochemical conversion keywords are            evaluation of environmental impacts of the biofuel produc-
 shown in Fig. 8a, b, such as ethanol production, bio-hydro-          tion chain and key outcomes from a range of biofuel produc-
 gen and others.                                                      tion processes. Based on the bibliometric mapping (network
                                                                      and density visualisation maps) from the Web of Science
                                                                      core collection, we have identified that the thermochemical
 Conclusion                                                           conversion route of biomass is more researched and far out-
                                                                      weighed and understood than the biochemical counterpart
 Biomass as an affordable, reliable and sustainable energy            route of research outputs. This indicates that the biochemical
 source contributes 9% (~ 51 EJ) of the global overall primary        route suffers from specific gaps in the research, as shown
 energy supply. Thermochemical and biochemical technolo-              from the lack of impact in the bibliometric mapping analy-
 gies are the two main routes employed to convert biomass             sis, thus opening doors for a scope for further research in
 into biofuels. The former route includes hydrothermal lique-         this area.
 faction, pyrolysis, torrefaction, gasification and combustion
 processes, while the latter route consists of fermentation and
 anaerobic digestion processes.                                       Funding The authors would like to thank OQ Oman for their generous
                                                                      financial support (project code: CR/DVC/SERC/19/01). The authors
    Herein, we critically reviewed each individual route along
                                                                      would also like to acknowledge the support of the Sustainable Energy
 with the integration between hydrothermal and biochemi-              Research Centre at Sultan Qaboos University. Ahmed Osman and
 cal routes of biomass utilisation from a bioeconomy per-             David Rooney wish to acknowledge the support of The Bryden Centre
 spective. Both routes have drawbacks: the former method              project (Project ID VA5048). The Bryden Centre project is supported
                                                                      by the European Union’s INTERREG VA Programme, managed by the
 usually involves a high energy intake along with solvent or
                                                                      Special EU Programmes Body (SEUPB). Neha Mehta acknowledges
 catalyst addition. In contrast, the latter route has a lengthy       funding from the Centre for Advanced Sustainable Energy, Belfast,
 cycle period and is less efficient in breaking down recalci-         UK.
 trant biomass materials. Thus, combining those two routes
 can be promising by incorporating the benefits of both meth-         Declarations
 ods in biofuel processing. However, there are outstanding
 challenges associated with integration between those two             Conflict of interest The authors declare no conflict of interest.
 routes. For instance, the catalysts or solvent utilisation of the
 thermochemical route can result in poisoning or killing the
                                                                                                                                  13
4112                                                                                                   Environmental Chemistry Letters (2021) 19:4075–4118
Ethical approval The views and opinions expressed in this review do                Anastasakis K, Ross AB (2015) Hydrothermal liquefaction of four
not necessarily reflect those of the European Commission or the Spe-                     brown macro-algae commonly found on the UK coasts: an
cial EU Programmes Body (SEUPB).                                                         energetic analysis of the process and comparison with bio-
                                                                                         chemical conversion methods. Fuel 139:546–553. https://doi.
                                                                                         org/10.1016/j.fuel.2014.09.006
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bution 4.0 International License, which permits use, sharing, adapta-                    ronmentally attractive used tyres pyrolysis with energy and
tion, distribution and reproduction in any medium or format, as long                     material recovery. Renew Sustain Energy Rev 20:539–558.
as you give appropriate credit to the original author(s) and the source,                 https://doi.org/10.1016/j.rser.2012.12.005
provide a link to the Creative Commons licence, and indicate if changes            Aravind S et al (2020) Conversion of green algal biomass into bioen-
were made. The images or other third party material in this article are                  ergy by pyrolysis. A Review Environmental Chemistry Letters
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