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Journal of Cleaner Production 270 (2020) 122462

Contents lists available at ScienceDirect

Journal of Cleaner Production


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

A comprehensive review of engineered biochar: Production,


characteristics, and environmental applications
Hamed Kazemi Shariat Panahi a, b, c, Mona Dehhaghi a, b, c, Yong Sik Ok d,
Abdul-Sattar Nizami e, Benyamin Khoshnevisan f, Solange I. Mussatto g,
Mortaza Aghbashlo h, ***, Meisam Tabatabaei a, c, i, j, *, Su Shiung Lam a, k, **
a
Henan Province Engineering Research Center for Forest Biomass Value-added Products, School of Forestry, Henan Agricultural University, Zhengzhou,
450002, China
b
Faculty of Medicine and Health Sciences, Macquarie University, NSW, Australia
c
Biofuel Research Team (BR Team), Karaj, Iran
d
Korea Biochar Research Center, O-Jeong Eco-Resilience Institute (OJERI) & Division of Environmental Science and Ecological Engineering, Korea University,
Seoul, 02841, Republic of Korea
e
Sustainable Development Study Center, Government College University, Lahore, Pakistan
f
Key Laboratory of Non-point Source Pollution Control, Ministry of Agriculture, Institute of Agricultural Resources and Regional Planning, Chinese Academy
of Agricultural Sciences, Beijing, 100081, China
g
Novo Nordisk Foundation Center for Biosustainability, Technical University of Denmark, Kemitorvet, Building 220, 2800, Kongens Lyngby, Denmark
h
Department of Mechanical Engineering of Agricultural Machinery, Faculty of Agricultural Engineering and Technology, College of Agriculture and Natural
Resources, University of Tehran, Karaj, Iran
i
Faculty of Plantation and Agrotechnology, Universiti Teknologi MARA (UiTM), 40450 Shah Alam, Selangor, Malaysia
j
Microbial Biotechnology Department, Agricultural Biotechnology Research Institute of Iran (ABRII), AREEO, Karaj, Iran
k
Pyrolysis Technology Research Group, Institute of Tropical Aquaculture and Fisheries (AKUATROP) & Institute of Tropical Biodiversity and Sustainable
Development (Bio-D Tropika), Universiti Malaysia Terengganu, 21030, Kuala Nerus, Terengganu, Malaysia

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

Article history: A sustainable management of environment and agriculture is crucial to protect soil, water, and air during
Received 2 March 2020 intensified agriculture practices as well as huge industrial and transportation activities. A promising tool
Received in revised form to address these challenges could be the application of biochar, a carbonaceous product of biomass
20 May 2020
pyrolysis. The efficiency of biochar could be improved through physical, chemical and microbial pro-
Accepted 22 May 2020
cedures. Engineered biochar could then be applied for various applications ranging from sustainable
Available online 1 June 2020
agriculture to pollution remediation and catalytic reactions. Biochar engineering allows achieving bio-
Handling Editor: Prof. Jiri Jaromir Klemes char properties which are optimum for specific applications and/or under specific conditions. This would
lead to harnessing the favorable features of biochar and to enhance its efficiency while simultaneously
Keywords: minimizing the existing tradeoffs. This review covers the production and applications of engineered
Charcoal biochar by summarizing great deals of research and knowledge on the field. Unlike previous reviews,
Green and sustainable remediation herein biochar physical and chemical properties and the factors affecting them (i.e., biomass nature and
Functional group pyrolysis conditions) have been discussed in detail. Moreover, the contributions of each physical and
Designer biochar
chemical activation/modification method to improving biochar characteristics with respect to environ-
Physical and chemical characteristics
mental applications have been specifically scrutinized. By providing the state-of-the-art knowledge
Environmental management
about engineered biochar production, properties, and applications, this review aims to help research in
this field for identification of the culprits that must be addressed in future experiments.
© 2020 Elsevier Ltd. All rights reserved.

* Corresponding author. Henan Province Engineering Research Center for Forest Biomass Value-added Products, School of Forestry, Henan Agricultural University,
Zhengzhou, 450002, China.
*** Corresponding author.
** Corresponding author. Henan Province Engineering Research Center for Forest Biomass Value-added Products, School of Forestry, Henan Agricultural University,
Zhengzhou, 450002, China.
E-mail addresses: maghbashlo@ut.ac.ir (M. Aghbashlo), meisam_tab@yahoo.com, meisam_tabatabaei@uitm.edu.my (M. Tabatabaei), lam@umt.edu.my (S.S. Lam).

https://doi.org/10.1016/j.jclepro.2020.122462
0959-6526/© 2020 Elsevier Ltd. All rights reserved.
2 H. Kazemi Shariat Panahi et al. / Journal of Cleaner Production 270 (2020) 122462

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Biochar: general characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. Physical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1.1. Nano- and macro-porosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1.2. Particle-size distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1.3. Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1.4. Mechanical strength . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.2. Chemical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.2.1. Microchemical characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.2.2. Organo-chemical characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3. Engineering biochar production techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.1. Physical techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.1.1. Ball milling modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.1.2. Gas/steam activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.1.3. Microwave modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.1.4. Magnetic biochar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.2. Chemical techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.2.1. Oxidizing modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.2.2. Chemical impregnation/coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
3.2.3. Clay-coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.3. Biological techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4. Biochar for sustainable environmental management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.1. Sustainable agriculture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.1.1. Soil nutritional properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.1.2. Soil biological properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
4.1.3. Greenhouse gases emission . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
4.2. Pollution remediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.2.1. Inorganic contaminants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.2.2. Organic contaminants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
5. Conclusions and future prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

1. Introduction product not only traps CO2 but could also be used in sustainable
agriculture, pollution remediation, catalytic reactions, and energy
One of the main challenges in today’s industrial world is the production. In 2010, it was estimated that biochar could mitigate
huge emission of greenhouse gases (Aghbashlo et al., 2019a), which 1.8 billion metric tons of CO2, corresponding to 12% of anthropo-
has significant adverse effects on the environment including air genic greenhouse gas emissions.
pollution (Kazemi Shariat Panahi et al., 2019b) and climate change It is worth mentioning that activated carbon and biochar should
(Tabatabaei et al., 2019b). It is obvious that industrialization is not be confused with each other. The major difference between
necessary for human to sustain and thrive, for example, alleviating these two lies in the type of materials used as feedstock. More
the need for intense transportation and agriculture (i.e., food pro- specifically, biochar is only produced from biomass whereas acti-
duction) (Rajaeifar et al., 2019). Therefore, any effort targeting at vated carbon could be produced from biomass as well as other
slowing down the industrialization process remains unfruitful, and carbonaceous substances such as tar pitch or coal. To a lesser
at most, only provides temporary reliefs. In contrast, replacing the extent, they can also be distinguished according to their environ-
polluting compounds/products with less/non-polluting alterna- mental applications. Biochar is typically applied for soil amend-
tives could be successful only if the new products have political and ment to improve soil physical, chemical, and biological properties.
economic feasibilities (Soltanian et al., 2020). For example, exerting In contrast, the typical application of activated carbon is for
political and economic pressures by oil companies on demotivating pollution remediation. The production of biochar and activated
the application of biofuels are the two main challenges, impeding carbon is relatively similar, i.e., through pyrolysis. However, acti-
their rapid public acceptance of these ecofriendly green fuels vated carbon can also be produced through chemical activation
(Kazemi Shariat Panahi et al., 2019c). (such as acid, base, or salt activation) or steam/air activation of C
Another solution for minimizing the negative consequences of feedstocks. It is worth mentioning that both mentioned processes,
modern lifestyle could be through various strategies concentrating i.e., chemical and physical activations can also be used for engi-
on recycling as much wastes as possible into value-added products neering biochar after its production through pyrolysis.
for strategic applications such as biogas and electricity (Shirzad Biochar engineering allows achieving biochar properties which
et al., 2019) and biofertilizer (Aghbashlo et al., 2019c). An appro- are optimum for specific applications and/or under specific condi-
priate example for this approach is the mitigation of C through tions. This would lead to harnessing the favorable features of bio-
biochar production from pyrolysis of cheap and easily available C- char and to enhance its efficiency while simultaneously minimizing
rich residues (i.e., lignocellulose) left from intense agriculture. This the existing tradeoffs. For instance, in case of soil amendment, not
H. Kazemi Shariat Panahi et al. / Journal of Cleaner Production 270 (2020) 122462 3

all biochars are suitable for increasing plant productivity. More modification techniques), and environmental application of engi-
specifically, in hard soils, porous biochar is more appreciated for neered biochar in this review have been summarized in Fig. 1.
enhancing the growth of plant root. Addition of inappropriate In the present work, only a brief discussion on the applications
biochar into soil could even increase soil greenhouse gases emis- of engineered biochar for sustainable environmental management
sion capacity, decrease soil nutrients content, and dysregulate soil has been provided as there are already a handful of good reviews
biological properties (See Section 4.1). With respect to pollution published specifically dealing with each of these applications
remediation, the type and availability of functional groups on the (Table 1). Biochar applications related to energy management have
surface of biochar is critical to specifically remove target analytes as been reviewed elsewhere (Lee et al., 2018; Xiu et al., 2017). In
well as to its adsorption capacity (See Section 4.2). Finally, engi- contrast, the main emphasis of the current review is on biochar
neering of pore size distribution in biochar allows its more efficient physical and chemical characteristics including the factors affecting
environmental applications. For example, biochar pore size must be them. The physical and chemical modification/activation methods
larger than the compound that is intended to be remediated while used for engineering biochar along with the conferred improve-
an abundant number of large macropores is appreciated for ments (e.g., surface area, porosity, active site, and functional
improving soil water holding capacity as plant roots cannot over- groups) have also been scrutinized. The novelty of the present re-
come the capillary forces holding water in micropores (Weber and view against the previously published ones has been clarified in
Quicker, 2018). In case of energy application, for example in blast Table 1.
furnace, fuel biochar must show high mechanical strength enough
to tolerate the weight of the iron ore. An appropriate mechanical 2. Biochar: general characteristics
strength is also required for appropriate handling, storage, and
transport of biochar (Weber and Quicker, 2018). 2.1. Physical properties
Pyrolysis is a thermochemical process (Aghbashlo et al., 2019b)
applying heat (typically, 300e700  C) in the limited amount of O2 The physical properties of biochar directly depend on the
under atmospheric pressure (Tabatabaei et al., 2019d). Through this biomass nature and pyrolysis conditions (including biomass pre-
process, various chemical species (i.e., non-condensable pyrogas, treatment and handling). More specifically, attrition, cracks for-
biocrude oil, and biochar) can be obtained, the amount of which mation, and microstructural rearrangement occur during different
being dependent on reaction temperature, heating rate, and resi- pyrolysis processes, altering the biomass’s original structures at
dence time (Kazemi Shariat Panahi et al., 2019d). Furthermore, the various degrees (Downie et al., 2009). As the pyrolysis process
products characteristics could be improved by incorporation of continues, feedstock mass is reduced (i.e., volatile organics are
catalyst, alternative heating methods (e.g., microwave), specific released), resulting in disproportional amount of volume decrease
carrier gas (e.g., H2 for hydropyrolysis), and other process condi- or biomass shrinkage. At the end of pyrolysis step, C and mineral
tions such as vacuum (Kazemi Shariat Panahi et al., 2019d). skeletons resembling the basic structure and porosity of the orig-
Typically, any successful pyrolysis system uses a heat source for inal biomass are formed. This physical modification has been
increasing the biomass temperature, triggering the volatiles release confirmed by the identification of plant cellular structures within
and char formation (i.e., charcoal and biochar). The primary py- coals and woods-derived biochar, contributing to most of the bio-
rolysis initiates autocatalytic secondary reactions by condensing char macroporosity (Downie et al., 2009). The macropores could be,
hot volatiles in the cooler un-pyrolyzed parts of biomass, leading to in turn, converted into meso and micropores (Fukuyama et al.,
tar formation (Kazemi Shariat Panahi et al., 2019d). Both of these 2001; Zabaniotou et al., 2008).
reactions simultaneously and competitively continue while process Overall, biomass pretreatment, reaction temperature, heating
parameters (i.e., temperature, pressure, and/or reaction time) may rate, reactor type and dimension, the carrier/purge gas flow rate,
trigger further reactions including thermal decomposition, dehy- residence time, pressure, and biochar post-modification methods
dration, radicals recombination, water gas shift reactions, and are the main operating parameters shaping the physical structure
reforming (Kazemi Shariat Panahi et al., 2019d). It is worth of biochar produced via pyrolysis. For example, fast pyrolysis of
mentioning that the feedstock characteristics could also affect the biomass delivers biochar with low surface area. An ideal biochar
ratio of the pyrolysis products. For example, wet biomass with physical structure could be developed by increasing reaction tem-
42e62% moisture content enhances the biochar formation at peratures up to a point that any further temperature elevation
elevated pressures. Similarly, the biochar yield is higher from py- triggers deformation. According to Downie et al. (2009), biochar
rolysis of spruce wood, pine wood, or other high-lignin biomass formed at 400  C had high aromatic hydrocarbon contents and
(Liu et al., 2015). Biochar formation could also be impacted by the were highly disorganized in amorphous mass. As the reaction
presence of some inorganic species (especially, the alkali and temperature decreases, conjugated aromatic C sheets that are ar-
alkaline earth metals) in biomass. More specifically, autocatalytic ranged turbostratically grow. Finally, the biochar resembles a
process could be induced by catalyzing the volatiles secondary graphitic structure with order in the third dimension at tempera-
cracking in the presence of some inorganic species (e.g., Ca, K, and tures 2500  C. More specifically, the decrease in reaction temper-
Mg), leading to the formation of more gaseous compounds, ature decreases the formation of structured regular spacing
including H2, CH4, CO, CO2, and C2H4 (Liu et al., 2015). Therefore, between the planes, increases the interplanar distances, and re-
higher amount of biochar is cracked and lower biochar yield is duces the molecular organization (Downie et al., 2009).
delivered. Like pyrolysis process conditions, the physical characteristics of
The present review scrutinizes the general (physical and the biomass also directly depend on the biomass chemical com-
chemical) characteristics of biochar and compares various tech- positions. The thermal decomposition of organic materials starts at
niques that have been used to produce engineered biochar >120  C. More specifically, hemicellulose, cellulose, and lignin
including physical, chemical, and biological techniques. Addition- decompose at 200e260  C, 240e350  C, and 280e500  C, respec-
ally, the applications of engineered biochar for (i) sustainable tively (Downie et al., 2009). Therefore, the reactivity and physical
environmental management as nutrient stabilizer, soil fertilizer, structure modification degrees are impacted by the ratios of these
and soil greenhouse gases emission reducers, and (ii) remediation components during pyrolysis process. On the other hand, the bio-
of organic and inorganic pollutants have briefly been discussed. char physical structure could also be impacted by the ash ratio (i.e.,
The discussed characteristics, production (i.e., activation and inorganic components) through ash sintering of fusion under
4 H. Kazemi Shariat Panahi et al. / Journal of Cleaner Production 270 (2020) 122462

Fig. 1. Characteristics, production (i.e., activation and modification techniques), and environmental applications of engineered biochar.

Table 1
Comparison of the present review article and some top review papers published previously on engineered biochars.

Review Biochar production Factors affecting biochar Biochar characteristics Engineered biochar Engineered biochar
method/s characteristics production techniques applications

General Physical Chemical Physical Chemical Biological Agriculture Remediation Other

This Study 7 ✓** ✓* ✓** ✓** ✓** ✓** ✓* ✓** ✓* 7


(Liu et al., 2015)a ✓** ✓* ✓* ✓* ✓* ✓** ✓** 7 7 7 ✓**
Dai et al. (2019) 7 7 7 7 7 7 7 7 7 ✓** ✓*
Rajapaksha et al. 7 7 7 7 7 ✓** ✓** 7 7 7 7
(2016)
Jiang et al. (2020) 7 7 7 7 7 7 7 7 ✓** 7 7
Xu et al. (2012) 7 7 ✓* 7 7 7 7 7 ✓* ✓* 7
Mohan et al. (2014) ✓* 7 7 7 7 7 7 7 7 ✓**a 7
Wang et al. (2017a) 7 7 7 7 7 ✓** ✓** ✓* ✓* ✓* ✓*
Palansooriya et al. 7 7 7 7 7 7 7 7 ✓**b 7 7
(2019b)

✓**Comprehensively discussed.
✓*Briefly discussed.
7 Not discussed.
a
Referred to reference.
b
Specific on one topic (e.g., water remediation or microbial responses).

pyrolysis process (Downie et al., 2009). greater structural organization in biochar molecule (Downie et al.,
2009). Moreover, volatile content of feedstock is released at higher
2.1.1. Nano- and macro-porosity pyrolysis temperatures and creates more pores (Shaaban et al.,
One of the most important physical properties of any produced 2014). Slow pyrolysis increases the porosity of woody biochar
biochar is pore-size distribution, well determining its industrial through slow decomposition of the lignin content (Weber and
application potentials. Macropores, mesopores, and micropores Quicker, 2018). Typically, specific surface area of the biochar
(i.e., pores with internal diameter of >50 nm, 2e50 nm, and <2 nm, rapidly enlarges when pyrolysis temperature exceeds a certain
respectively) constitute the total pore volume of the biochar value (for example 400  C), resulting in the thermal condensation
(Rouquerol et al., 2013). Among them, micropores are the main of organic matters and formation of micropores (Li et al., 2019c).
contributor to the biochar surface area and efficiently adsorb When pyrolyzed at higher temperatures, feedstocks that contain
minute molecules (e.g., solvents and gases). On the other hand, aromatic lignin core, as well as aliphatic alkyls and ester groups
mesopores are significant in many liquid-solid adsorption pro- generate biochars with higher surface areas (Tomczyk et al., 2020).
cesses (Downie et al., 2009). Eventually, the growth in specific surface area becomes insignifi-
Micropore volume could be improved through extending cant at temperatures higher than 800e1000  C (especially, for slow
biomass pyrolyzing at higher reaction temperatures, providing the heating rates), and at temperatures >850  C, the shrinkage of solid
required activation energies and time for reaction completion, i.e., matrix leads to decreased porosity. It should be noted that the wall
H. Kazemi Shariat Panahi et al. / Journal of Cleaner Production 270 (2020) 122462 5

between two adjacent micropores could also be destroyed at high structure packing) of biochar is higher than that of the original
temperatures under some conditions (Zhang et al., 2004). The pores biomass as the result of the volatile and condensable compounds
enlargement reduces the micropore volume, but increases the total release and formation of graphitic crystallites (Downie et al., 2009).
biochar pore volume. Another factor deciding the micropore vol- Solid density of biochar increases with increasing the pyrolysis
ume is heating rate. At high heating rate the biomass undergoes temperature (independent of the heating rate), hence causing
melting which forms macropores, while low heating rate enriches higher shrinkage of solid matrix and the degree of carbonization
micropores volume in the produced biochar (Cetin et al., 2004). (Brown et al., 2006). In contrast, biochar has lower bulk density
Macropores act as feeder pores that transport adsorbed sub- (typically, ranging 0.3e0.43 g/cm3) due to biomass drying and
stances into meso and micro-pores (Downie et al., 2009). Macro- carbonization, compared to the wood precursor. However, bulk
pores volume is very important for assessing biochar potentials for density of biochar (activated carbon) could be as high as 0.50 g/cm3
sustainable agriculture (e.g., hydrology, aeration, roots movement, and 0.75 g/cm3 for gas adsorption and decolorization applications,
and as niche for soil microorganisms) (Fig. 2, Fig. 7) (Palansooriya respectively (Downie et al., 2009).
et al., 2019b) (See Section 4.1). Compared to micropores, macro- The residual porosity and turbostratic structure within most
pores have lower surface area but higher pore volumes. biochars reduce their solid densities to ~1.47e1.7 g/cm (Brown
et al., 2006; Downie et al., 2009). The formation of high-density
2.1.2. Particle-size distribution turbostratic carbon fiber (from transformation of low-density un-
The rigidity of the biomass against shrinkage and attrition organized ones) is strengthen by increasing reaction temperature
during pyrolysis process determined the biochar particle size. (regardless of heating rate) and time (Kercher and Nagle, 2002). The
Generally, the particle sizes of the produced biochar are smaller availability of micropores within biochar increases its density,
than those of the un-pyrolyzed biomass. However, agglomeration compared to macro- and mesopores (Downie et al., 2009). It should
may occur during pyrolysis process, leading to the formation of be noted that there is no strong correlation between pyrolysis
biochar with larger particle sizes than the starting biomass (Cetin temperature and biochar bulk density. Typically, the higher the
et al., 2004). Post-mechanical stresses (e.g., during handling) may bulk density of the feedstock used, the higher the bulk density of
also occur, crumbling biochar that is more susceptible than the the produced biochar would be (Byrne and Nagle, 1997).
original biomass. Biochar particles with smaller size distributions
could be obtained through slow pyrolysis with a heating rate of 2.1.4. Mechanical strength
5e30  C/min. Particle size has inverse correlation with reaction Biochar solid density and its level of aromaticity and crystal-
temperature. For example, it has been observed that the tendency linity determine its mechanical strength. In another word, the
for formation of smaller size particles in biochar is increased by mechanical stability directly correlates with density, and hence,
increasing reaction temperature from 450  C to 700  C (Downie inversely with the porosity. The assessment of mechanical strength
et al., 2009). This could be attributed to the increased vulnera- of pyrolyzed biochar was a topic of only few studies (Das et al.,
bility to attrition due to reduced tensile strength in biomass/ 2015; Zickler et al., 2006). Compared to the virgin wood, mono-
biochar. lithic carbonized wood biochar has lower stiffness (37%) and higher
Overall, to enhance the mass- and heat-transfer during pyrolysis strength (28%) (Byrne and Nagle, 1997). According to these studies,
reactions, smaller biomass particles are required when higher both reduced moduli and hardness of woody biochar continuously
heating rates (e.g., 500-105  C/s) are applied. Therefore, the increase with increases in temperature, finally reaching a plateau at
resulting biochar will be very fine. In contrast, slow pyrolysis (lower temperatures between 700 and 2000  C. Any further increases in
heating rates and longer residence time) provides larger biochar pyrolysis temperature would negatively affect these properties in
particles. Apart from reaction temperature and residence time, the generated biochar. Kumar et al. (1999) reported that both
higher pyrolysis pressure could render the formation of biochar compressive and impact strengths of biochar derived from euca-
with larger particle sizes. Under pressurized pyrolysis, melting and lyptus and acacia showed an early decrease in response to tem-
subsequent particles fusion are more pronounced, triggering perature elevation (up to 600  C) followed by an improvement
swelling and the formation of particle clusters (Cetin et al., 2004). thereafter. However, eucalyptus-derived biochar had a better me-
chanical strength than acacia-derived biochar. They also mentioned
2.1.3. Density that slow pyrolysis process (heating rate, 4  C/min) would increase
Apparent or bulk density and solid density could be considered compressive strength, compared to rapid process (30  C/min). This
with respect to determination of biochar physical properties. can be attributed to the fact that rapid heating rate leaves cracks in
Typically, an increase in bulk density accompanies with a decrease the solid structure of biochar by rapid release of volatile matter and
in solid density. In general, solid density (i.e., the degree of C water evaporation. This explanation also justifies why pyrolysis of

Fig. 2. Biochar macroporosity under scanning electron microscope: A) slow pyrolyzed wood-derived biochar; and B) slow pyrolyzed poultry-manure-derived biochar. Source:
(Amonette and Joseph, 2009a; Downie et al., 2009). "Copyright© Johannes Lehmann and Stephen Joseph, 2009”. Courtesy of Johannes Lehmann and Stephen Joseph.
6 H. Kazemi Shariat Panahi et al. / Journal of Cleaner Production 270 (2020) 122462

biomass containing lower moisture contents develops biochars their organization, and exhibited electrochemical properties and
with higher mechanical strengths, compared to their high- functional groups on the biochar surface, all of which are formed
moisture counterparts (Weber and Quicker, 2018). In addition to through thermal decomposition of biomass under sub-
moisture content, the orientation and nanocomposite properties of stoichiometric O2 condition (Amonette and Joseph, 2009b). More
biomass (high density and high lignin content) can also determine specifically, the pyrolysis of dried biomass (e.g., lignocelluloses)
the mechanical strength of biochar as these properties are almost triggered by the hemolytic cleavage of covalent bonds (in the
not affected during the pyrolysis process (Weber and Quicker, biomass being thermally decomposed), releases plenty of free
2018). Therefore, lignocellulose-derived honey-comb structure radicals from inorganics impurities and structural O within biomass
and microfibril angle of the cellulose in parent feedstock would be (Amonette and Joseph, 2009b). During the initial pyrolysis stages,
retained to some extent in the resultant biochar. Compared to the free radicals may be produced from low atmospheric O2 levels
parent biomass, a higher mechanical strength, but lower anisotropy (Amonette and Joseph, 2009b). The process continues by the for-
and compressive strength are expected in biochar due to higher mation of carboxyl and carbonyl groups and their subsequent
molecular order (Downie et al., 2009). cleavage into CO2 and CO (Shafizadeh, 1982).
Mechanical strength is important in biochar quality determi- At the end of the pyrolysis process, biochar residue is formed
nation for withstanding tear and wear stresses during environ- from recombination of free radical fragments with each other and
mental applications. On this basis, the harder biomass containing with the substrate in different ways (Amonette and Joseph, 2009b).
low ash and high lignin contents, such as fruit stones/pits (e.g., date, As the reaction temperature is elevated (500e600  C), the pro-
olive, apricot) and nut shells (e.g., walnut, macadamia, hazelnut, portion of the entrained free radicals (measured by electron para-
and almond), are more appreciated for biochar production with magnetic resonance spectroscopy) in biochar reaches its maximum
excellent mechanical properties (Aygün et al., 2003). In a more for a given residence time, leading to pyrophoric biochar formation
recent study (Das et al., 2015), structure-mechanics properties of (Feng et al., 2004). It is worth mentioning that the yield of biochar
seven waste-derived biochars under different pyrolysis conditions produced at 300e600  C mainly depends on the degradation (i.e.,
were investigated. Accordingly, the value of hardness and modulus dehydration and fission reactions) and volatilization rates
increased at high pyrolysis temperature (500  C) and longer resi- (increased by mass- and heat-transfer) of anhydrosugars (such as
dence time (60 min). Intriguingly, pyrolysis temperature was found levoglucosan) present in the tar (Amonette and Joseph, 2009b).
as a more dominant determinant in the biochar mechanical prop- Beyond this temperature, the dominating product will be gas which
erties than residence time. minimizes the biocrude oil, tar, and biochar productions (Kazemi
Shariat Panahi et al., 2019d). Biomass carbonization during pyrol-
2.2. Chemical properties ysis step delivers biochar with high C content (>90%) through
removing most of S, N, H, and O contents from the parent biomass.
Any pyrolysis process could chemically manifest the biomass to
form biochar with diverse properties. The properties of biochar are 2.2.1.1. Solid phases and their distribution. Carbon-based phases.
mainly determined by feedstock type and pyrolysis temperature. In The thermal decomposition of lignocellulosic biomass under py-
fact, biochar properties and functions can be predicted with the rolysis triggers four regions of changes including dehydration, py-
help of data synthesis technique (Li et al., 2019c). Typically, with the rolysis, graphene nucleation and carbonization with transition
increase in the pyrolysis temperature, biochar yield exponentially temperatures of 250  C, 350  C, and 600  C (2  C/min heating rate)
decreases whereas alkalinity (pH) of biochar shows a linear in- under near-atmospheric pressure (Paris et al., 2005). More specif-
crease (rate, 0.5e1.4/100  C) (Li et al., 2019c). The elevation of pH is ically, dehydration (with slight depolymerization) of cellulosic
attributed to the thermal decomposition of hydroxyl bonds and content of biomass occurs at <250  C with little mass loss in
other weak bonds within the biochar structure under high tem- biomass (about 3 wt% at 150  C). At this stage, a progressive gain in
peratures. In contrast, cation exchange capacity of biochar shows an C concentration is started when biomass is heated above 150  C.
inverse relationship with pyrolysis temperature due to the removal Compared to original biomass, the 13C-NMR spectral intensity of
of acidic functional groups (Li et al., 2019c). Generally, biosolids- biochar produced at 200  C showed weaker signal intensity asso-
derived biochars have the highest cation exchange capacity ciated to hemicellulose and cellulose structures (O-alkyl C and di-
because biosolids are rich in minerals (e.g., P, Mg, Ca, Na, and K) O-alkyl C), but stronger signals related to lignin (aryl C and O-aryl
which promote the formation of O-containing functional groups on C) were recorded (Knicker et al., 2005). From signal intensities, it
the surface of biochar during pyrolysis (Agrafioti et al., 2013). Unlike was found that a transformation of O-alkyl to aryl C structures is
ash content, the volatile matter content of biochar is linearly induced in biochar produced at 250  C.
reduced with increasing pyrolysis temperature. The formation of The onset of the second region (250e350  C) coincides with
ash is due to the left-over inorganic minerals following the decrease in hydrogen-to-carbon (H-to-C) ratio due to progressive
decomposition of H, O, and C in the biomass (Li et al., 2019c). Re- higher loss in O and H than C (Baldock and Smernik, 2002). The
ductions in these elements are attributed to the destruction of reduction in H-to-C ratios could indicate the formation of struc-
hydroxyl, azanide, and other weakly-bonded groups in response to tures with unsaturated C (e.g., aromatic rings). In this region of
increases in temperature. However, C content (except some volatile changes (i.e., second region), cellulose is completely depolymerized
C) decreases very slowly, leading to higher C proportions in the (pyrolyzed), volatilizing biomass (with significant mass loss) and
produced biochar under higher pyrolysis temperatures (Li et al., forming amorphous C matrix. Up to 81 wt% reduction in starting
2019c). biomass could be observed during a pyrolysis at 300  C (Baldock
In this section, the chemical complexity of biochar is further and Smernik, 2002).
discussed by considering microscopic and molecular, and organo- Amorphous C starts transforming into aromatic C and poly-
chemical properties. aromatic graphene sheets at ~330  C and >350  C (third region),
respectively. Higher temperatures (i.e., >600  C, fourth region)
2.2.1. Microchemical characteristics remove most of the remaining non-C atoms via carbonization
Microchemical characteristics of biochar could affect its super- (Amonette and Joseph, 2009b). Moreover, the graphene sheets
ficial sorption properties. These characteristics significantly depend continue growing laterally, while their thickness and number of
on the nature and composition of solid phases, the entrapped oils, graphene packets remain constant, at the expense of amorphous C
H. Kazemi Shariat Panahi et al. / Journal of Cleaner Production 270 (2020) 122462 7

phase and ultimately coalescing, i.e., intersect with adjacent start vaporizing during thermal decomposition of the biomass (Yu
packets to develop electrical continuity throughout biochar et al., 2005). Similarly, N associated with different organic mole-
(Amonette and Joseph, 2009b). As the result of this transformation, cules is vaporized at low temperatures (Schnitzer et al., 2007b). In
microporosity improves due to the formation of voids in biochar contrast, S and P are bonded with complex organic compounds in
structure (i.e., aligned graphene packets are denser than amor- the biomass cells, showing good stability at low temperatures.
phous C). An intimate solid mixture of graphene packets and Compared to Cl and K ions, some biomass cell wall entrapped ions,
amorphous C primarily forms the backbone of carbonized biochars such as Ca (also bound to organic acids) and Si (as opal phytolithys
synthesized at higher pyrolysis reaction temperatures (Cohen-Ofri and silica), are released during thermal decomposition at much
et al., 2007). higher temperature (Fig. 3) (Bourke, 2007). Magnesium is associ-
The mass loss in biomass during volatilization (due to dehy- ated with organic molecules (through covalent and ionic bonds),
dration and pyrolysis) mainly link to compositional loss in O, H, allowing its vaporization only at high reaction temperatures
and, to lesser extent, C. These elements could be lost in the form of (Amonette and Joseph, 2009b). Some organic and inorganic ele-
H2O (at initial stages by dehydration reactions), hydrocarbons, ments (e.g., Mn and Fe) in the biomass are not eliminated during
gases (i.e., CO2, CO, and H2), and tarry vapors (Antal and Grønli, pyrolysis, passing therefore, to the biochar residue. Potassium could
2003). Typically, the C content improves from 40 to 50 wt% in be distributed on some biochar matrix, intercalating between
starting biomass to 70e80 wt% in the produced biochar, following graphene sheets or forming phenoxides. Like K, Ca could also form
the pyrolysis at 250e600  C. As already mentioned, the C content of phenoxides throughout the biochar matrix (Wornat et al., 1995).
biochar could reach to >90 wt% through carbonization (excluding Other mineral elements could be present in the biochar forming
chars containing high mineral ash) (Antal and Grønli, 2003). different minerals in minor phases. They may include amorphous
Entrained minerals. The fate for biomass inorganic content silica, anhydrite (CaSO4), calcium phosphates [Ca3(PO4)2], calcite
could be volatilization, entrainment in biochar (Fig. 3), or retention (CaCO3), garnet [Ca3Al2(SiO4)(OH)8], gonnardite [(Na, Ca)2(Si,
as discrete mineral phases (Wornat et al., 1995). The distribution Al)5O10*3H2O], hydroxyapatite [Ca10(PO4)6(OH)2], quartz (SiO2),
and amount of minerals entrained in biochar is controlled by sylvite (KCl), and various hydroxides, oxides and nitrates of Zn, Mg,
biomass and pyrolysis process conditions. Typically, woody Mn, Ca, Fe, Al, and Ti (Fig. 3). The existence of some of these min-
biomass (i.e., forest residues, scrap wood, and sawmill residues) erals may complicate the biochar production (e.g., amorphous silica
contain <1 wt% ash contents (Fig. 3A). In contrast, high ash contents forms phytoliths, protecting plant C content against degradation)
(up to 24 wt%) could be delivered by grain, straw, and grass husks, (Parr and Sullivan, 2005; Smith and White, 2004) or their appli-
which are rich in silica contents (Raveendran et al., 1995). As cations (e.g., crystalline silica in some biochar is a lung carcinogen)
already mentioned, the loss of H, O, and C in biomass during py- (Ndirangu et al., 2019).
rolysis concentrates the mineral content in the biochar, for example Overall, inherent minerals of biomass can significantly affect
chicken litter- and bone-derived biochars may contain up to 45 wt% biochar properties through interaction with its organic contents
(Koutcheiko et al., 2007) and 84 wt% mineral contents (Purevsuren during the pyrolysis process (Nan et al., 2018). Accordingly, removal
et al., 2004), respectively. It has been suggested that biochar yield is of these minerals prior to the pyrolysis process could increase the
independent of biomass mineral-ash content unless a solid catalyst optimum pyrolysis temperature (370 vs. 330  C) for the biomass
is added, i.e., a higher biochar yield could be expected from biomass conversion into biochar, compared to pristine biomass with
containing higher mineral-ash content in the presence of solid inherent minerals. Surprisingly, up to 30.1% more C content of
catalyst (Amonette and Joseph, 2009b). biomass could be sequestrated into biochar in the absence of
Mineral ash in biochar could also be controlled by pyrolysis biomass inherent minerals while at the same time, lower amounts
process conditions, particularly reaction temperature, and partial of low-molecular-weight organic compounds would be emitted
pressure of CO2, steam and O2 (Bridgwater and Boocock, 2006). At during pyrolysis (Nan et al., 2018). The removal of biomass minerals
relatively low temperatures, highly mobile ions such as Cl and K prior to pyrolysis strengthened biochar C skeleton by promoting

Fig. 3. Scanning electron microscope micrographs and associated energy-dispersive X-ray spectroscopy spectra for minerals embedded on engineered biochars’ surfaces. A)
Minerals on surface of poplar-wood-derived biochar, including 1) amorphous SiO2, 2) trace dehydroxylated silicates, 3) CaHPO4 and Ca10(PO4), and 4) CaCO3 and CaO; and B)
minerals on surface of maize-cob-derived biochar, 5) Na2S, 6) Na2CO3 and Na2O, 7) ZnS, and 8) KCl. Source: (Amonette and Joseph, 2009b). "Copyright© Johannes Lehmann and
Stephen Joseph, 2009”. Courtesy of Johannes Lehmann and Stephen Joseph.
8 H. Kazemi Shariat Panahi et al. / Journal of Cleaner Production 270 (2020) 122462

aromatization level, i.e., the formation of C¼C and/or C-C bond/s in and (ii) electron donors such as O(C¼O)R, OR, NH2, or OH that
the expense of O-containing functional groups. It is worth contain a or p electrons (Amonette and Joseph, 2009b). On this
mentioning that the existence of some mineral acids (e.g., H3PO4) basis, carbonyls and phenols are weak acidic groups whereas
could be beneficial to synthesizing biochars with specific environ- carboxyl groups are strong Brønsted acids. On the other hand,
mental applications. For example, H3PO4 improves C retention and pyrones and chromenes are basic functional groups (Amonette and
micropores formation via the insertion of P-O-P into the C lattice. Joseph, 2009b). Both basic and acidic sites may be present on the
Such a swollen and amorphous biochar has been shown to possess biochar pores and outer surfaces within micrometers of each other.
a higher adsorption capacity for Pb, compared to its pristine This phenomenon could be attributed to the large diversity in
counterpart (Zhao et al., 2017). Therefore, the type and amount of mineral composition and content on biochar surfaces (Fig. 3)
minerals in biomass must be optimized according to the intended (Amonette and Joseph, 2009b). Oxides minerals could form
environmental application of biochar. amphoteric sites on biochar surfaces, showing charge changes with
Associated biocrude oils. At reaction temperatures less than pH modifications, i.e., positively and negatively charged surfaces at
500  C, some of the tarry and oily vapors that have not been acidic and alkaline conditions, respectively. Similar behavior to
recovered as biocrude oil from the gas stream in a condensation oxides is expected from carbonate minerals due to the presence of
tower, may condense in biochar pores, forming a multi-phase the O in the carbonate anion (Amonette and Joseph, 2009b). In
substance (Schnitzer et al., 2007a, contrast, a diverse behavior is observed from sulfide minerals upon
2007b,bib_Schnitzer_et_al_2007a,bib_Schnitzer_et_al_2007b). Ac- their exposure to aqueous solutions. More accurately, seven elec-
cording to Schnitzer et al. (2007a, 2007b), six compound classes, trons are eventually released from superficial located S atom on
including (i) N-hetrocyclics, (ii) substituted furans, (iii) phenol and biochar when oxidized by water or other dissolved oxidants
substituted phenols, (iv) benzene and substituted benzenes, (v) (Rimstidt and Vaughan, 2003). This phenomenon leads to signifi-
carbocylics, and (vi) aliphatics may be present as the organic cant variations in surface charge ranging from positive to negative
molecules from the residual biocrude oils on biochars’ surface. Al- that is controlled by the S oxidation state (Essington, 2015). It is
kanes (n-C7-19), alkenes (n-C7:1-19:1), and ethyl- and methyl- worth mentioning that high mineral-ash content may allow heavy
substituted pteridine, pyrozines, pyrimidine, pyridines and pyr- metals incorporation in functional groups (Fig. 8).
roles are some prominent N-heterocyclics that exist in biocrude oil A range of different S- and N-based functional groups may also
and may left adhering on the biochar surface/pores (Amonette and be detected in biochar, especially those derived from sewage sludge
Joseph, 2009b). The concentration of alkali and alkaline earth and manures (Leng et al., 2019). More specifically, the occurrence of
metallic species in biochar increases in the pyrolysis systems with N-functional groups (predominantly, pyridinic nitrogen oxides, and
poor biocrude oil separation efficiencies. Biochar can absorb up to quaternary, pyrrolic and pyridinic nitrogen) on biochar surface is
27% and 43% of Mg and Ca contents of biocrude oil (Zhang et al., primarily linked to biomass protein content that has been modified
2017). Overall, the adsorption of biocrude oil or its components through thermal decomposition (i.e., dehydration, dehydrogena-
by biochar could modify the physico-chemical properties of the tion, and deamination) (Leng et al., 2019). Through 13C- and 15N-
produced biochar. Such a biochar may or may not be appropriate NMR of charring peat, it was found that both heterocyclic and ar-
for some applications. For instance, biochar overloaded by alkali omatic N-containing structures could directly be formed by heat
and alkaline earth metals could serve as catalyst in some industries (i.e., temperature-dependent) (Almendros et al., 2003). Therefore,
or could be used to amend soil deficient in these elements. The biochar N-functional groups could be engineered through modifi-
presence of biocrude oil-derived compounds such as butenolide cation and optimization of biomass composition, pyrolysis process
and sesquiterpenes could improve the biochar environmental (particularly, reaction temperature), and N-doping technique. Like
application. These two biocrude oil-derived compounds are N, S content of the biomass is also significantly determined by
respectively vital for some plants germination and microorganisms temperature. On this basis, sulfates and sulfonates are more
growth whereas other biocrude oil-derived compounds such as so- abundant in biochars produced at lower temperature whereas
called smoke vinegar may have biocidal activities (Amonette and sulfidic and thiophenic functional groups are dominant at higher
Joseph, 2009b). reaction temperatures (Koutcheiko et al., 2007). It is also possible
The incorporation of biocrude oil-derived compounds may that S transforms into an insoluble form (e.g., K2S and CaS) in the
decrease the efficiency of the biochar. In fact, the adsorption of biochar matrix. Sulfur may substitute O in surface oxides or bond to
heavy organic compounds, particularly aromatics with two or more unsaturated sites in the biochar (Knudsen et al., 2004). The exis-
fused rings from biocrude oil could significantly decrease the ca- tence of O-containing groups on biochar surface could be ascribed
pacity of biochar for environmental (water and soil) pollution to biochar reaction with atmospheric O2 and/or its oxidization with
remediation. Aromatics with fused rings in biocrude oil may also other gases (e.g., CO2, NO, and O3) or solutions (Amonette and
decrease biochar porosity through porosity-selective effect. When Joseph, 2009b). Similarly, pyrone groups on the biochar surface
lower amounts of biocrude oil are present, these negative effects could be due to the adsorption of molecular oxygen (O2_-) or its
may also be triggered by single aromatic structures. Nevertheless, dissociate adsorption (O2or O) (Swiatkowski et al., 2004).
the extent of aromatic adsorption by biochar depends on functional Overall, reaction temperature, heating rate, gas composition in
groups and hydrophobicity of biochar (Zhang et al., 2017). the vicinity of the charring particle, biomass composition, and any
post-modification method (See Section 3.2) may control the rela-
2.2.1.2. Surface chemistry. The biochar heterogeneous composition tive concentrations of each of the biochar functional groups
provides rich and varied surface chemistry, exhibiting various basic, (Amonette and Joseph, 2009b).
acidic, hydrophobic, and hydrophilic properties based on the py-
rolysis and feedstock conditions. Heteroatoms such as S, P, N, O and 2.2.2. Organo-chemical characteristics
H are associated with aromatic rings, forming various functional Some organo-chemical characteristics of biochars have been
groups on the graphene sheets’ surfaces (Brennan et al., 2001). The already discussed in previous section (i.e., Section 2.2.1). In general,
electronegative differences between the C atoms and heteroatoms the H-to-C ratio drops from ~1.5 in lignocellulosic biomass to 0.5,
cause surface chemical heterogeneity. The functional groups on following pyrolysis at temperatures higher than 400  C (Graetz and
biochar surface could be classified into (i) electron acceptors such Skjemstad, 2003). This H-to-C ratio reduction could be attributed to
as NO2, (C¼O)H, or (C¼O)OH groups that contain empty orbitals, elemental (N, O, H, and C) concentration changes during biomass
H. Kazemi Shariat Panahi et al. / Journal of Cleaner Production 270 (2020) 122462 9

thermal decomposition. Typically, O-to-C and H-to-C ratios 3.1.1. Ball milling modification
(indicative of the degree of aromaticity and maturation) in biochar The properties of biochar (i.e., particle size and specific surface
reduce at high reaction temperatures and/or extended residence area) for adsorbing inorganic and organic ions could be engineered
time (Almendros et al., 2003; Baldock and Smernik, 2002). H-to-C through its grinding via physical ball milling (Cai et al., 2016; Lyu
ratio in biochar could reveal some information about bonding ar- et al., 2018a). For example, the surface area of a corn-stover-based
rangements in analyzed biochar. On this basis, burnt peat showed a biochar could be improved more than 3.2 times, reaching 194 m2/
H-to-C ratio equal to 1.3 when most of its C content was either g, through optimized planetary ball mill process (Peterson et al.,
connected through a hydroxyl group or directly bonded to a proton 2012). In addition to micropores and surface area, the functional
(Knicker et al., 2005). If H-to-C ratio drops to 0.4e0.6, it indicates groups within biochar could be modified in the presence of
that on average every second to third C is connected to a proton appropriate chemical during ball milling, a process known as
(Knicker et al., 2005). The more graphitic-like structure of the chemical ball milling (Wang et al., 2017a). Compared to pristine
compounds, the lower H-to-C ratio will be (e.g., <0.1 in lignite and biochar, ball milled biochar displayed higher affinity for Ni and
soot). methylene blue removals (Lyu et al., 2018a). Through ball milling,
Besides the pyrolysis and biomass conditions, the chemical nano-sized biochar could be produced with comparable perfor-
composition (such as H-to-C and O-to-C ratios) of biochar could be mance to those of carbon nanotubes and activated carbon with
engineered through chemical treatment. For example, nitric acid- respect to organic and inorganic contaminants removal (Shan et al.,
treated biochars have lower H-to-C but higher O-to-C ratios 2016). However, it should also be noted that the biochar dis-
(Trompowsky et al., 2005). Artificial aging of the biochar through persibility in water has direct relationship with the intensity of ball
heat-incubation treatment showed a reduction in organic contents mill process, restricting ball milled biochar application in soil and
that correlated well with temperature rise (Cheng et al., 2008). In water remediation. More specifically, the lower size biochar parti-
contrast, organic contents were enriched as the temperature was cles will either move downward in the saturated sandy soil or are
increased (up to certain points) when biochar was aged at O- prone to erosion by wind or water (i.e., surface run-off). If ball
reduced environment. Typically, biochar contains [500 mg/g milled biochar is used for contaminants (such as pesticides)
organic contents; however, the organic content in grass- and remediation, there will be a risk for subsequent contamination of
manure-based biochars may be less than 500 mg/g (Knicker et al., groundwater upon possible erosion (Wang et al., 2017a). This
2005). constraint can be overcome in future studies by developing
Overall, the biomass pyrolysis at >350  C produces low H-to-C methods for stabilizing grinded biochar.
ratios biochars containing alkyl C, and O-alkyl C with dominated
aromatic (aryl) C. Higher temperature (>500  C) and prolonged 3.1.2. Gas/steam activation
residence time further enriches aryl C structures at the expense of The positive properties of the biochar could be almost double
removing plant-characteristics functional group C structures (e.g., through its activation by gas/steam, i.e., air, CO2, water vapor, etc.
O-alkyl C), leading to greater mass loss and very low H-to-C ratios. With respect to agriculture, this method delivers biochar with
higher nutrient retention, which could be taken up by plants
(Borchard et al., 2012). This improvement could be attributed to the
3. Engineering biochar production techniques
development of activated carbon during which process
(700e1100  C) the porosity formation in biochar is induced, its
Any specific environmental application uses biochar with spe-
surface area improved, and its surface reactivity degree increased
cific adsorption properties. In other word, biochar could be engi-
substantially (Fig. 4C) (Wang et al., 2017a). This activation method
neered to suit better for intended environmental application by
also removes products of incomplete combustion and other im-
modification of its physico-chemical properties such as specific
purities from biochar. On the other hand, steam activation de-
surface area, surface functional groups, and pore structures. This
creases the availability of functional groups on the surface of the
engineering could be conducted through various techniques
biochar (Fig. 4C). For example, carboxylic acid, that is labile to this
ranging from physical or chemical to biological methods.
process, will be degraded, resulting in production of less oxidized
Fig. 4 depicts three activation methods that are used for
biochar. As the carboxyl group acts as a binding site for heavy
upgrading biochar properties and compares the improvements
metals (Pourret and Houben, 2018; Uchimiya et al., 2012), it is ex-
achieved to the original properties of pristine biochar. In Fig. 5,
pected that the metal remediation is negatively impacted by gas/
some biochar modification methods are presented.
steam activation. Like carboxyl group, phenolic group is also sus-
ceptible to this process, resulting in the formation of less polar
3.1. Physical techniques biochar.
Overall, gas/steam activation could be used as a preliminary
Pore structure improvement and oxygenic functional groups treatment for extending the biochar surface area prior to a second
induction could be economically achieved by physically modified technique aiming at positively modifying biochar functional
biochar with no impurities added. Ball milling, gas or steam acti- groups.
vation, microwave, and magnetic modifications are some of the
most applied physical methods for biochar properties improve- 3.1.3. Microwave modification
ment. The physically modified biochar displayed higher adsorption Microwave is an electromagnetic base irradiation (frequencies
capacity for organic pollutants, nutrient elements, and heavy metal of 0.03e300 GHz, wavelengths of 0.01e1 m) that could be effi-
elements due to improved specific surface area with more abun- ciently (with respect to time and energy) applied with ease of
dant mesopores and micropores (Wang et al., 2017a). The appli- control (Tabatabaei et al., 2019a). The microwave-pyrolysis could be
cation of clean and easily controlled agents makes physical conducted at low reaction temperature of around 200e300  C with
methods safer and results in cheaper biochars which are free of biochar yield of more than 60 wt%. When polar molecules are
impurities, compared to chemical ones. subjected to microwave irradiation, polarization (i.e., dipole
Table 2 summarizes some physical activation and modification orientation) occurs, displacing electrons surrounding atoms or
techniques commonly used for engineering biochar with enhanced nuclei trillion times per second. Rotating molecules rub against
properties. each other producing heat (Yek et al., 2020). In addition to friction,
10 H. Kazemi Shariat Panahi et al. / Journal of Cleaner Production 270 (2020) 122462

Fig. 4. A comparison between different activation methods for engineering biochar with respect to sorption characteristics. A) Pristine biochar; B) acid-treated biochar; C) gas/
steam-activated biochar; and D) alkali-treated biochar. Adopted from (Sizmur et al., 2017). With permission from Elsevier. Copyright©2017.

Maxwell-Wagner and conduction are the other two mechanisms wastewater treatment. Delayed separation of biochar that has
for thermal energy generation during microwave irradiation adsorbed various contaminants from water will induce secondary
(Tabatabaei et al., 2019a). The application of microwaves in pyrol- pollution, preventing the regeneration and recycling of the biochar
ysis is relatively a novel methodology for speeding up the process. (Nguyen et al., 2013). An efficient solution would be the combina-
Moreover, pyrolysis through microwave irradiation does not tion of biochar with a suitable magnetic medium such as zero-
require the biomass shredding step nor drying (Bhaskar and valent iron (Fe0), CoFe2O4, gamma-Fe2O3, and Fe3O4 (Fig. 5B).
Pandey, 2015). Through this strategy, a uniform thermal energy Through this strategy, the engineered biochar could be collected
could be internally transferred within the biomass directed to- from aqueous solution by imposing a magnetic force. The incor-
wards the reactants’ functional groups. The resultant biochar would poration of Fe oxides in biochar improves its cation exchange and
have larger surface area (a Brunauer-Emmett-Teller, BET, up to its metal binding capacities (i.e., higher surface area and functional
450e800 m2/g) as well as more functional groups, compared to groups availability) (Fig. 8). However, magnetic impregnation di-
unmodified biochar (Wang et al., 2017a). If this engineered biochar minishes phenol sorption probably by enhancing C oxidation.
is used as an agent in sustainable environmental management, it The successful encapsulation may require an appropriate
could improve soil water holding capacity as well as cation ex- coupling reagent to prevent falling out of magnetic nanoparticles
change capacity (Fig. 7). from the biochar matrix. Accordingly, the surface encapsulation of
Fe3O4 particles on biochar is promised by incorporation of the
3.1.4. Magnetic biochar amino-terminated 3-Triethoxysilylpropylamine as a coupling re-
The main constraint on the way of application of grinded bio- agent, efficiently linking the magnetic nanoparticles with biochar
char in water purification is its minute particle size and small (Zhou et al., 2018). It should be noted that functional modification
density, making its separation from water complicated after the (See Section 3.2.2) is commonly applied in conjunction with
H. Kazemi Shariat Panahi et al. / Journal of Cleaner Production 270 (2020) 122462 11

Fig. 5. A comparison between different modification methods for engineering biochar with respect to sorption characteristics. A) Pristine biochar; chemical impregnation/coating
by B) metal oxides, C) clay minerals, D) organic compounds such as amino groups, polyethylenimine, chitosan or graphene oxide and E) carbon nanotubes; and F) microbial
modification.

Table 2
Effects of some physical modification techniques on biochar properties.

Technique Enhanced properties Negative effect/disadvantage Ref.

Ball milling - Particle size -Increased dispersibility in water (Lyu et al., 2018a; Peterson et al.,
modification - Specific surface area -Vulnerability to surface runoff 2012)
-Contaminating ground water upon biochar erosion
Gas/steam - Porosity -Reduced availability of surface functional groups (e.g., carboxylic (Borchard et al., 2012; Chang et al.,
activation - Surface area acid, phenolic) 2000)
- Nutrient retention - Formation of less polar biochar
-Biochar purity - Lowered metal remediation efficiency
Microwave - Biochar production yield (i.e., >60 wt -Low process reproducibility due to difficulty of controlling power and (Wan et al., 2009; Zhao et al.,
modification %) temperature 2010)
- Biochar production speed
- Surface area
- Functional groups availability
- Cation exchange capacity
Magnetic biochar - Separation characteristics - Diminished sorption of phenol (due to enhanced C oxidation) (Trakal et al., 2016; Zhou et al.,
- Cation exchange and metal binding - Often requires coupling reagent 2018)
capacities - Loss in biochar surface area and partial blockage of pores by
magnetic medium

magnetic modification of biochar to compensate for any loss in (between the positively charged metal cation and negatively
biochar surface area due to the blockage of biochar pores by mag- charged carboxyl anion), and complexation (Fig. 8) (Yu et al., 2017b;
netic medium. Through this strategy, the functional groups are Zhou et al., 2018).
enriched in biochar which in turn improve its adsorption selectivity
and capacity to desired chemical species (i.e., heavy metals). Amino
and amide, carboxyl, hydroxyl, sulfhydryl, and sulfonyl are some 3.2. Chemical techniques
functional groups containing some coordinate atoms (e.g., N, O, or
S) that can chelate with metal ions (Fig. 5) (Zhou et al., 2018). Chemical-based techniques involve the activation of biomass/
Among them, carboxyl group render a strong affinity to coordinate biochar in the presence of chemicals and inert gas. More specif-
with metal ions due to ion exchange, electrostatic interaction ically, acids or bases could be used for oxidation of biochar,
improving micropores, surface area, cation exchange capacity, and
12 H. Kazemi Shariat Panahi et al. / Journal of Cleaner Production 270 (2020) 122462

Fig. 6. The motivation for biochar application in sustainable environmental management.

Fig. 7. Biochar impact on soil nutrient leaching: 1) porous biochar particles improve water retention by adsorbing it and reducing its mobility; 2) weathered biochar improves soil
aggregation by binding to other soil particles; 3) and 4) to a lesser extent, fresh biochar sorbs hydrophobic organic nutrients; 5) the weathered biochar also increases soil cation
exchange capacity due to increase in biochar surface charge; and 6) consequently soil biota is enriched. Source: (Major et al., 2009). "Copyright© Johannes Lehmann and Stephen
Joseph, 2009”. Courtesy of Johannes Lehmann and Stephen Joseph.

functional groups availability of biochar (Fig. 4B, D). Alternatively, scaffold for supporting the materials deposition. The outcome of
biochar could be impregnated with clays, carbonaceous and such strategy is the production of completely new biochar surface
organic compounds (e.g., amino groups, polyethylenimine, chito- functional groups.
san, carbon nanotubes, and graphene oxide), metal oxides, and
(functional) nanoparticles to synthesize composite (Fig. 5BeD, F).
3.2.1. Oxidizing modification
Typically, this modification type uses high-surface-area biochar as
This technique could either be used for chemical modification of
H. Kazemi Shariat Panahi et al. / Journal of Cleaner Production 270 (2020) 122462 13

Fig. 8. Heavy metal removal mechanisms by engineered biochar activated/modified different methods (Wang et al., 2019). With permission from Elsevier. Copyright©2019. License
Number: 4741561425430.

biomass prior to pyrolysis (also known as in-situ modification) or D). More specifically, acid-treatment results in more carboxyl
biochar modification after pyrolysis (also known as post- groups on biochar (Fig. 4B), which is appropriate for better
modification). Chemical modification in the presence of appro- adsorption of Cu, Pb, Zn (Uchimiya et al., 2012), sulfamethazine
priate oxidant efficiently enhances the sorption capacity and heavy (Vithanage et al., 2015), Cd and oxytetracycline (Aghababaei et al.,
metals uptake of biochar (Table 3). These improvements could be 2017). In contrast, alkaline-treatment results in more surface
attributed to the induced affinity of carbonyl (negatively charged graphite C and/or aromatic functional groups (e.g., hydroxyl groups)
groups) in biochar for binding with positively charged metals, (Fig. 4D) while increasing surface electrostatic attraction, p-p
particularly following acid-treatment (Fig. 4B, D) (Wang et al., interaction, surface precipitation, and/or surface complexation that
2017a). Acids (e.g., H2SO4, H3PO4, HCl, HNO3, and H2O2), alkali are better for As, Cd, tannic acid, and chloramphenicol (Fig. 8).
(e.g., KOH and NaOH) and other oxidizing agents (e.g., metal salts For application as supercapacitors, biochar powder must be first
such as KMnO4, and iron chloride hexahydrate) are some of the activated in the presence of a strong base such as KOH and inert
chemicals that have been already applied in chemical-based tech- atmosphere at high temperatures (~960  C) for several hours. The
niques for engineering biochar to obtain desirable properties mixture is then subjected to chemical washing and lengthy drying
(Table 3). It is worth mentioning that the careful selection of steps to develop porous nanostructures with optimal pore-size
appropriate oxidizing agent could be translated into the production distribution over a large surface area (Gupta et al., 2015; Jiang
of more recalcitrant carboxyl-rich biochar that are appreciable for et al., 2013). However, the economic feasibility of such process is
long-term remediation of heavy metals from soil and water relatively low; significantly impeding biochar supercapacitors
(Uchimiya et al., 2012). Generally, a larger surface area could be production. Biochar treatment by oxygen plasma is a more recent
expected in alkali-treated biochar, compared to pristine or acid- technique for its rapid and cost-efficient activation at temperatures
treated ones. The surge in surface area could be attributed to the lower than 150  C. Within the plasma chamber, a controlled flow
biochar demineralization during acid or alkali treatment (Fig. 4B, rate of the reactive gas (O2) is introduced which is ionized to O* and

Table 3
Effects of some oxidants on engineered biochar properties.

Chemical Enhanced properties Other improvement Ref.


reagent

Various - Availability of surface carboxyl groups - Induced Sorption capacity and heavy (Mahmoud et al., 2012;
acids - Mineral composition tailoring metals uptake Vithanage et al., 2015)
- Oxygen-containing functional groups - Environmental persistency (half-life)
Various - Surface graphite C and/or aromatic functional groups Surface area (Ding et al., 2016; Jin et al., 2014)
alkalines - Increasing surface electrostatic attraction, p-p interaction, surface
precipitation, and/or surface complexation
Oxygen - Pore size distribution and surface area (generation of biochar supercapacitor -
plasma production)
14 H. Kazemi Shariat Panahi et al. / Journal of Cleaner Production 270 (2020) 122462

Oþ, and in turn, plasma under a strong electromagnetic field pyrolysis could enhance the thermal cracking of volatile organic
generated by excitation radio frequency antenna. The process is compounds and their subsequent conversion into syngas (i.e., H2
conducted at desired temperature under vacuum for efficient ion and CO) due to the direct reaction with CO2 (Cho et al., 2017). It is
implantation of samples (hold on a plate below the antenna), worth mentioning that syngas evolved during biochar production
modifying the sample surface properties (e.g., pore size distribution could be used for the production of various value-added green fuels
and surface area). Gupta et al. (2015) enhanced the supercapacitor such as butanol, methanol, and CH4 (Kazemi Shariat Panahi et al.,
characteristics (171.4 F/g) of yellow pine biochar by 5-min oxygen 2019c); therefore, significantly improving the economic feasibility
plasma activation. Compared to pristine and conventional base- of the process. Moreover, the presence of Co and CO2 showed a
activated biochars, 185% and 72.3% improvements in capacitance synergistic effect on extending biochar surface area to 599 m2/g
were observed. The effects of some oxidizing agents on engineered (~100 times greater than that formed in N2 environment) as well as
biochar properties are summarized in Table 3. syngas production (compared to absence of Co impregnation) (Cho
et al., 2017).
3.2.2. Chemical impregnation/coating He et al. (2018) immersed corn straw into FeCl3*6H2O solution,
Biochar surface area could be expanded by incorporation of and the oven dried biomass was subjected to slow pyrolysis
different nanoparticles or metal oxides onto the biochar through (600  C, 60 min). Accordingly, a greater thermal stability, more
various chemical impregnation/coating techniques at different functional groups, and larger surface area were observed in the
pyrolysis steps (i.e., in-situ or post-modifications) (Fig. 5B). The engineered biochar. The improvement allowed up to 400-time
advantages of biochar application and nanotechnology could be higher As(V) adsorption efficiency through electrostatic attraction
combined through the production of biochar-based nano- and precipitation mechanisms (Fig. 8), compared to pristine bio-
composites. Briefly, this win-win solution for both water remedi- char (6.80 mg/g vs. 17 mg/g). Recently, MgCl2-pretreated corncob
ation and C sequestration could benefit from abundant and cheap was pyrolyzed to develop MgO-coated biochar with a calculated
biomass, cost-efficient production process, efficient chemical/ MgO content of 29.9% w/w (Shen et al., 2019). The surface area of
physical surface characteristics, and high functionalities (Lehmann the engineered biochar was extended by about 380 times, reaching
and Joseph, 2015; Tan et al., 2016). Biochar-based nanoparticles 26.56 m2/g, compared to pristine biochar. The Pb removal efficiency
could be fabricated in three forms (i) nano-metal oxide/hydroxide- from aqueous solution was also enhanced by 3.2 times. This
biochar composites, (ii) functional nanoparticles-coated biochar, improvement was mainly attributed to the adsorption of Pb on
and (iii) magnetic biochar composites. The resulting composites biochar surface (through cation-p interaction) and its precipitation
will substantially improve in terms of pore properties (i.e., volume, by MgO coating (Fig. 8) (Shen et al., 2019). Unlike pristine biochar,
size, and distribution), surface area, catalytic degradation ability the MgO-coated corncob biochar could remediate Pb from soil,
(e.g., simultaneous adsorption and degradation of contaminant), reducing its content by about 51% (from 10.63 to 5.24 mg/L) (Shen
surface active sites availability, functional groups, and even their et al., 2019).
separation from aqueous solutions. Overall, foreign particles Target element enrichment by bioaccumulation. Biomass could
impregnation onto pristine biochars is a promising approach for be enriched with specific (target) chemical elements during its
expanding and enhancing the environmental applications of bio- cultivation. Then, the accumulated metal element could be trans-
char if biological and environmental concerns of nanoparticles have formed into hydroxide/nano-metal oxide following pyrolysis.
carefully been identified and appropriately addressed. Through this strategy, engineered biochars presenting MgO and
Mg(OH)2 nanoparticles in the surface were developed for efficient
3.2.2.1. Nano-metal oxide/hydroxide-biochar composites. remediation of aqueous phosphate. The starting biomass was
Nano-metal oxide/hydroxide-biochar composites could be pro- delivered from irrigated tomato plants with 25 mM Mg enrichment
duced via three different techniques, including (i) biomass pre- solution (Hoagland solution) twice a week (Yao et al., 2013b).
treatment by metal salt, (ii) target element enrichment by Currently, many industries consume considerable amounts of
bioaccumulation, and (iii) post-pyrolysis metal oxide nanoparticles nanoparticles in their products/process, posing environment into
insertion. risk. Therefore, an innovative solution may be the remediation of
Biomass pretreatment by metal salt. Metal salts or other suit- nanoparticles-contaminated soil and wastewater by suitable
able chemical reagents are used for pretreating biomass prior to hyperaccumulator plant (Dehhaghi et al., 2019b). The plant could
pyrolysis. The immersion of biomass into metal salts solution leads be subsequently converted into value-added engineered biochar
to the metal ions attachment into the interior or onto the surface of through the above-mentioned strategy. However, the full potential
the biomass. The pyrolysis of this metal ions impregnated biomass of this strategy relies on comprehensive research on the impact of
induces the transformation of the attached metal ions into metal accumulation of different chemical species (e.g., Al, Ca, Fe, and Mn)
hydroxide or nano-metal oxide, developing biochar-based nano- on the biochar physiochemical properties.
composites (Tan et al., 2016). Some of the common metal salts for Post-pyrolysis metal oxide nanoparticles insertion. Heat
this purpose are AlCl3 (transformation into Al2O3/AlOOH) (Zhang treatment, evaporative method, direct hydrolysis, and conventional
and Gao, 2013), CaCl2 (transformation into CaO) (Fang et al., 2015; wet impregnation are the most widely applied techniques for post-
Liu et al., 2016), CoCl2 and Co(NO3)2 (transformation into CoO and pyrolysis metal oxide nanoparticles insertion. These techniques
CO3O) (Cho et al., 2017; Wang et al., 2012), FeCl3 (He et al., 2018), have successfully been employed by different researchers for en-
KMnO4 (transformation into MnOx), MgCl2 (transformation into gineering biochar in the presence of metal oxides. For example,
MgO) (Fang et al., 2015; Zhang et al., 2012a), MnCl2 (transformation micro/nano-MnOx porous biochar composite was synthesized,
into MnO), and Zn(NO3)2 and ZnCl2 (transformation into ZnO) (Gan following the heat treatment of KMnO4-biochar mixture (Song
et al., 2015). The presence of these metal hydroxides or nano-metal et al., 2014). The resulting composite could efficiently adsorb
oxides on the surface of biochar increases the biochar surface area Cu2þ (160 mg/g, ~8.2-time higher than pristine biochar) on O-
as well as its reactive area and sites for efficient adsorption of containing functional groups and MnOx mainly through forming
inorganic and organic contaminants, and heavy metals (Tan et al., inner-sphere complexes. Wang et al. (2015a) engineered a biochar
2016). In an innovative research (Cho et al., 2017), CoCl2-impreg- for remediating Pb(II) with removal yield of 98.9% (~15.5-time
nated lignin was pyrolyzed in CO2 environment to form Co/lignin higher than pristine biochar) by loading amorphous hydrous
biochar for catalytic degradation of bromate (BrO 3 ). The CO2-aided MnO on biochar through conventional wet impregnation
H. Kazemi Shariat Panahi et al. / Journal of Cleaner Production 270 (2020) 122462 15

technique. Improvements in the removal efficiency of fabricated Post-pyrolysis functional nanoparticles impregnation. Chito-
MnO-biochar could be attributed to the decrease in pH at the point san (Zhang et al., 2015), hydrogel (Karakoyun et al., 2011), Mg/Al
of zero charge (pHPZC) and increase in surface hydroxyls and elec- (Tan et al., 2016), ZnS nanocrystals (Yan et al., 2014), LDHs, and Fe0
trostatic interactions (Fig. 8). In another study, an evaporative (Devi and Saroha, 2015; Yan et al., 2015) are some of the most
method was used for amendment of biochar with iron oxides in the common functional nanoparticles that have successfully been
presence of Fe(NO3)3.9H2O, delivering up to 2.5 order of magnitude deposited on the C surface within the biochar matrix through post-
higher surface area than iron-oxide-amended sand (Cope et al., pyrolysis functional nanoparticles impregnation technique.
2014). Qian et al. (2013) used AlCl3 solution as immersion solu- Through this technique, appropriate active sites for selective
tion for production of 0.6 M Al(III)-modified crop (peanut, soybean, sorption of desired contaminants from aqueous solutions could be
and rice) straw-derived biochars. As the result of this direct introduced on the biochar matrix. Despite partial biochar pore
impregnation modification, biochars’ surface negative charges blockage by functional nanoparticles coating, the resulting biochar
changed into positive in acidic environment and the biochars’ zeta has a superior over that of the pristine one due to the favorable
potential-pH curves shifted into a positive-value direction. The properties of functional nanoparticles (Tan et al., 2016). For
engineered biochars were granted an enhanced sorption of arse- example, post-pyrolysis impregnation of chitosan nanoparticles
nate [445e667 mmol As(V)/kg biochar at pH 5], owing to the reduces the biochar surface area, but enhances the metal ions (e.g.,
electrostatic attraction between the heavy metal and the Cd2þ, Cu2þ, and Pb2þ) adsorption performance by forming amine
positively-charged surfaces on the biochars (Fig. 8) (Qian et al., functional groups on the biochar surface (Wei et al., 2018b). This
2013). engineered biochar was prepared in three steps; (i) paper mill
sludge pyrolysis at 700  C, (ii) addition of the produced biochar into
3.2.2.2. Functional nanoparticles-coating. Synthesis of functional cetyltrimethylammonium bromide solution (0.1e0.8%, CTMB), fol-
nanoparticles-coated biochar could be either through in-situ or lowed by impregnation of Fe0 on biochar-CTMB complex
post-modifications. Through this strategy, various kinds of func- (1000 rpm, 30 min) to form Fe0 magnetic biochar composite (ZVI-
tional nanoparticles such as graphene, carbon nanotubes, chitosan, MBC), and (iii) NiCl2.6H2O doping on filtered, distilled-water
graphitic C3N4, graphene oxide, Fe0 nanoparticles, layered double washed, and oven dried (at 95  C) solid ZVI-MBC residues to form
hydroxides (LDHs), and ZnS nanocrystals could be economically Ni-ZVI-MBC (dip-coating technique) (Devi and Saroha, 2015). This
coated onto the biochar surface (Fig. 5D, F). The resulting functional engineered biochar showed a characteristic pentachlorophenol
nanoparticles-coated biochar displays superb capabilities for removal mechanism (simultaneous adsorption and dechlorina-
various contaminants removal, owing to the combined advantages tion), delivering higher remediating performance (i.e., adsorption
of functional nanoparticles and biochar matrix. More specifically, efficiency and rate). The improvement could be attributed to the
thermal stability, porosity, surface area, and surface functional catalytic action of Ni, that prevented the accumulation of the
groups are significantly improved in biochar (Tan et al., 2016). A pentachlorophenol on the surface of the engineered biochar
characteristic simultaneous adsorption and degradation of organic through its degradation (i.e., dechlorination), following its adsorp-
contaminants could be obtained through dispersion of appropriate tion. Polymerization technique could be used for the conversion of
oxidative/reductive and catalytic nanoparticles (e.g., graphitic C3N4 the exhausted engineered biochar into bricks with negligible
and Fe0) on biochar surface. pentachlorophenol and heavy metal leaching and good compres-
Precoating biomass with functional nanoparticles. First, the sive strength (Devi and Saroha, 2015).
desired functional nanoparticles are suspended in deionized water Yan et al. (2014) boosted the Pb2þ adsorption capacity (up to 10-
and homogenized by sonication. Then, biomass is immersed into time, reaching ~367.7 mg/g) in magnetic biochar by its decoration
this solution and subsequently dried in oven prior to pyrolysis. with ZnS nanocrystals in a polyol solution. The engineered mag-
Through this strategy, Zhang et al. (2012b) pyrolyzed graphene-/ netic biochar/ZnS composites; therefore, possessed high Pb2þ
pyrene-derivative-treated biomass into a biochar with graphene removal capacity and excellent superparamagnetic properties (i.e.,
skin . The engineered graphene-coated biochar showed a signifi- easy separation). In another study, a peanut shell-derived biochar
cant methylene blue adsorption. In another study, graphene was was modified through post-pyrolysis MnO nanoparticles impreg-
linked onto the biochar surface by p-p interactions via slow py- nation for efficient sequestration of Cd2þ and Pb2þ at different pH
rolysis, forming a graphene/biochar composite (Fig. 5F) with high (ranging 3e7) with minimized Mn leaching at acidic pH (Wan et al.,
Hg and phenanthrene removal efficiencies. Compared to pristine 2018). The engineered biochar was recyclable and captured the
biochar, the engineered one had more functional groups, larger mentioned target heavy metals through specific inner-sphere
surface area, and greater thermal stability (Tang et al., 2015). complexation. Prior to preferable sorption through the Donnan
Biochar could also be modified by carbon nanotube via pre- membrane effect, Cd2þ and Pb2þ permeated into the biochar pore
coating biomass with functional nanoparticles (i.e., dip-coating). channels and were pre-enriched due to the inducing effect of fixed
For instance, bagasse or hickory biomass was dip-coated in car- negatively charged O-containing groups on the engineered biochar
bon nanotube suspensions in the presence of an appropriate (Wan et al., 2018). Recently, Mortazavian et al. (2019) impregnated
dispersion aiding compound (i.e., sodium dodecylbenzenesulfo- Fe0 nanoparticles on the heat-treated (300  C, ambient air) pine
nate) (Inyang et al., 2015). The process continued by slow pyro- tree-derived commercial biochar, forming biochar/Fe0 nano-
lyzing the pretreated biomass at 600  C in a N2 environment. Up to particles composite. The hydrophilicity and the O-containing
86% and 71% sulfapyridine and Pb could be simultaneously functional groups availability in heat treated biochar increased by
(without competition) removed by the engineered biochars, increasing the heating time. The composite could remove organic
respectively (Inyang et al., 2015). Hybride multi-walled carbon contaminant, particularly trichloroethylene (88% removal effi-
nanotube-coated biochars were also synthesized by dip-coating ciency in 20 min) and p-nitrosodimethylaniline (Mortazavian et al.,
same types of biomass into carboxyl-functionalized carbon nano- 2019).
tube suspension, allowing better methylene blue sorption via Overall, post-pyrolysis functional nanoparticles impregnation
electrostatic attraction (Inyang et al., 2014). The improvement in technique could significantly improve the removal performances of
the dye removal could be attributed to the larger pore volumes engineered biochar, masking its shortcoming of partial blockage of
(0.14e0.22 cc/g) and surface areas (351e390 m2/g), and greater biochar pores. However, for maximum exploitation, research spe-
thermal stabilities. cifically targeting at minimizing the negative impact of post-
16 H. Kazemi Shariat Panahi et al. / Journal of Cleaner Production 270 (2020) 122462

pyrolysis functional nanoparticles impregnation technique on sur- contaminant) at the same time (Frankel et al., 2016). Dalahmeh
face area must be conducted. et al. (2018) investigated biochar eligibility as suitable scaffold for
microbial biofilm and compared it to conventional sand-active
3.2.3. Clay-coating biofilm. The adsorption and biodegradation performances of
The application of clay minerals in industry is gaining attention these two biofilm scaffolds were investigated at an onsite sewage
due to some significant physico-chemical characteristics treatment facility degrading pharmaceutically active compounds
(Rahimzadeh et al., 2018), including high surface area, particle size (i.e., caffeine, carbamazepine, ranitidine, and metoprolol). It was
and shape, and surface chemistry (Yao et al., 2014). More specif- found that filter made up of biochar-active-biofilm could efficiently
ically, organic and inorganic pollutants (e.g., dyes and heavy metals) adsorb and degrade >98% carbamazepine, compared to only 7%
could be efficiently adsorbed by clay minerals. Bentonite and other removal obtained by sand-active-biofilm after 154 d incubation.
montmorillonite are low-cost adsorbents that have been already The performances relating to other three pharmaceutically active
applied for eutrophication and pollution management compounds were relatively same in both scaffolds (Dalahmeh et al.,
(Rahimzadeh et al., 2018). Another most studied clay mineral is 2018).
kaolinite (with surface exchange sites), a layered silicate mineral The residues from anaerobic digestion (AD) of biomass could be
containing one tetrahedral sheet linked through O atoms to efficiently used for the production of engineered biochar due to
alumina octahedral sheet (Yao et al., 2014). Montmorillonite is also more suitable pH values and redox potential. In fact, the biochar
a mineral with negatively charged expandable layered silicates, produced from AD-treated biomass has higher quality in terms of
consisting of one octahedral and two tetrahedral units establishing surface area, anion exchange capacity, surface charge (i.e., more
a 10-A -thick platelet (Yao et al., 2014). negatively charged), pH (i.e., more alkaline), and cation exchange
Unlike physical modifications, chemical-based techniques also capacity, compared to pristine biochar (Yao et al., 2018). Generally,
allow the engineering of biochar mineral compositions. Clay- this biologically activated biochar could be efficiently applied as ion
biochar composite could be produced through either in-situ or exchangers in environmental remediation purposes for seques-
post-modifications techniques. Apparently, the first attempt on tering both negatively and positively charged ions including heavy
synthesis of such composites dates to 2014 in which three types of metals and phosphate. The incorporation of such process could
biomass were pretreated by kaolinite and montmorillonite sus- remarkably increase the environmental and economic feasibilities
pensions prior to pyrolysis (600  C, N2 environment, and 60 min) of biochar production through production of biogas (Dehhaghi
(Yao et al., 2014). Accordingly, the dye (i.e., methylene blue) et al., 2019b; Tabatabaei et al., 2019c) and biofertilizer (Shirzad
adsorption capability of the engineered biochars increased about et al., 2019).
five times, compared to pristine ones, due to electrostatic attraction
and ion exchange with biochar and clay, respectively. The engi- 4. Biochar for sustainable environmental management
neered biochars showed a stable dye adsorption capacity of
~7.9 mg/g, following recycling and reusing (Yao et al., 2014). With respect to sustainable environmental management, bio-
The versatility of clay-coating technique was also exploited by char could be efficiently utilized in two complementary and usually
Takaya et al. (2016) for phosphate recovery from wastewaters by synergistic objectives, viz., sustainable agriculture and pollution
Mg-impregnated biochar (Fig. 5C). Accordingly, the phosphate remediation (Fig. 6). In addition, the production of biochar could
adsorption capacity of biochar derived from oak wood increased up greatly contribute to climate change mitigation (Fig. 6). There are
to ~31.6-33-5 times, reaching 70.3%. The modification involved some good papers that have specifically addressed each application
biochar treatment with iron chloride hexahydrate in the presence of engineered biochar, e.g., in remediation (Dai et al., 2019; Mohan
of MgCl2.6H2O and subjecting it to another pyrolysis (600  C, 10  C/ et al., 2014) or in sustainable agriculture (Jiang et al., 2020;
min heating rate, 5 mL/min N2, and 60 min). Palansooriya et al., 2019b). Therefore, the current review article
only discusses the mentioned applications briefly.
3.3. Biological techniques
4.1. Sustainable agriculture
Microorganisms possess different metabolic pathways
(Mohammadipanah and Dehhaghi, 2017; Wink et al., 2017), Biochar is gaining attention as a promising soil amendment for
allowing them to assimilate broad range of organic compounds sustainable agriculture, enhancing soil fertility through valorizing
(including contaminants and wastes) into usually safer metabolites soil enzyme dynamics and nutrient. The biochar impact on soil
(Dehhaghi et al., 2019a, 2019b) and even value-added products could be direct (i.e., nutrient-rich biochar amendment) or indirect
(Dehhaghi et al., 2018; Sajedi et al., 2018), particularly therapeutic (i.e., modification of soil physiochemical properties such as soil
lead compounds (Dehhaghi et al., 2020 ; Dehhaghi et al., 2019c, organic matter, soil aeration, water infiltration, soil hydration, and
2019d). Thanks to their microscopic size, they can penetrate minute water-holding capacity) (Fig. 7). The implementation of biochar
pores and develop a biofilm, which is a rigid structure able to could affect microorganisms (i.e., source of soil enzyme) or
prevent them from washing out. Microorganisms could biochemi- nutrient-leaching effect (i.e., improvement of macro and micro-
cally modify inert biochar through colonization and biofilms gen- nutrient retention). This section discusses various ways by which
eration on its high surface area (Fig. 5E). This post-modification biochar could contribute in improving soil quality or minimizing
technique allows engineering biochar with desirable properties. the environmental burden of intense agriculture to procure the
More specifically, a simultaneous adsorption of organic contami- desired environmental and economic advantages, a so-called sus-
nants and their degradation by biochar scaffold and inoculated tainable agriculture.
microorganisms could be observed, respectively. It should be noted
that some microorganisms are superb bio-adsorbent of a number of 4.1.1. Soil nutritional properties
heavy metals (Hamedi et al., 2015b; Mohammadipanah et al., Analyzing 153 published articles through a meta-analysis study
2015). On this basis, the colonization of a microbial consortium based on 1254 paired combinations showed that the combined
sourced from process water oil sands mining operations on biochar effects of soil conditions and biochar properties on plant growth
allowed the removal and degradation of naphthenic acids (an can vary from () 31.8%e974% (Dai et al., 2020). With respect to
organic contaminant) while adsorbing heavy metals (inorganic biochar, contents of organic C, ash and N, cation exchange capacity,
H. Kazemi Shariat Panahi et al. / Journal of Cleaner Production 270 (2020) 122462 17

pH, and bulk density are the key determinants. Biochar produced of basic biochar to acidic soils can significantly increase the pH,
from biomass pyrolysis can potentially enhance soil fertility, in- improving the nutrient bioavailability. In other words, basic biochar
crease soil C storage, and contribute in aggregate formation (El- can neutralize soil acidity and increase the soil quality and crop
Naggar et al., 2018; Marousek et al., 2019). Soil organic C (SOC) is productivity through enhancing the alkaline nutrients availability
considered as the main component of soil organic matter and used for plants (Cornelissen et al., 2018; Raboin et al., 2016). A recent
as an important soil health indicator. On this basis, high SOC con- large meta-analysis study showed that an average of 9% increase in
tents are associated with improved nutrients and water availability, soil pH was obtained in the biochar-amended soils (Dai et al., 2020).
resulting in higher soil fertility and crops productivity. In addition, A positive correlation was found between plant productivity and
SOC can increase soil structural stability through improving the the extent of biochar-amendment of soil, especially in acidic soils
aggregate formations that provide sufficient aeration required for (Jeffery et al., 2011). The increased plant productivity in alkaline soil
plant growth (Stott et al., 2018). Compared to total C content, total which was amended with biochar could be attributed to the
organic C content and its composition in biochar are more impor- improvement of cation exchange capacity, electron conductivity,
tant in terms of plant productivity improvement. Therefore, biochar and soil nutrients contents (Liu et al., 2019; Zheng et al., 2018).
intended for long-term soil C storage should possess specific These improvements were observed even with highly alkaline
characteristics such as high content of aromatic compounds and C biochars that were used for amendment purposes (Dai et al., 2020).
matter with low O-to-C ratios (Nguyen et al., 2009; Spokas, 2010). A meta-analysis conducted by Jeffery et al. (2011) showed that the
In better word, pyrolysis process should be performed at high most favorable effects of biochar amendment on crop productivity
temperature (500-700  C) to support the conversion of biomass was obtained in soils with medium or coarse texture (13 and 10%
into a high-content aromatic biochar with an O-to-C ratio similar to improvement, respectively) and acidic or neutral pH (14 and 13%
charcoal (i.e., 0.2e0.4) (Baldock and Smernik, 2002; Hammes et al., improvements, respectively). These improvements are mainly
2006). Generally, raising pyrolysis temperature promotes the attributed to higher nutrients availability and water holding ca-
degradation of easily decomposable materials, increasing the bio- pacity of the treated soil. In contrast, treatment of alkaline soils
char total nutrient content as well as pH and specific surface area with acidic/neutral biochar can reduce the soil pH, enhancing the
(See Section 2). However, to obtain biochar with specific nutrients, solubility and availability of some nutrients such as K and trace
pyrolysis conditions (especially, reaction temperature) should elements. On this basis, oxidizing pristine biochar with HCl or py-
carefully be controlled (See Section 2.2.1). Through this strategy, for rolyzing switchgrass at low temperatures (i.e., 350  C) are recom-
example, a N-rich biochar could be delivered by a pyrolysis process mended for rehabilitation of calcareous saline-sodic soil (Sadegh-
adjusted at 300-400  C. This could be attributed to the stability of Zadeh et al., 2018). Typically, the effect of biochar on soil pH
heterocyclic N-containing structures in this temperature range, reduction is weak, and hence, a significant improvement in alkaline
allowing their existence following pyrolysis (Cantrell et al., 2012). soil with respect to nutrient bioavailability might not be achieved
Biochar stability in soil also depends on its volatile matter/fixed C (Lentz and Ippolito, 2012).
ratio with an optimum of 0.5e1.0 (Amonette et al., 2009). When In addition to the pH, biochar with high surface area can in-
added to nutrient-deficient tropical soils, biochar derived from the crease the soil cation exchange capacity, particularly in sandy soils.
nutrients-rich feedstock (i.e., biosolids and manures) are more Up to 19.4% increase in cation exchange capacity of soil can be
effective inducers of plant productivity than those synthesized expected by biochar amendment, calculated from meta-analysis of
from structure-based feedstock (i.e., straw and wood) (Dai et al., 14 studies with 85 pairs of data (Dai et al., 2020). The effect of such
2020). Cares must be taken not to consume feedstocks containing modification is a reduction in the soil nutrients (e.g., Na, K, Mg, and
environmentally persistent free radicals to produce biochar. The Ca) leaching, and therefore, an increase in the soil nutrients avail-
presence of these compounds significantly inhibits seed germina- ability for plants (Fig. 7) (Laird et al., 2010). However, the exact
tion, and root and shoot growth through damaging plasma mem- extent of the improvement in the plant productivity depends on
branes (Liao et al., 2014; Odinga et al., 2020). the initial properties of soil (e.g., cation exchange capacity, humic
In general, biochar can restore the fertility of degraded and low materials content, and pH) which also explains the inconsistency
nutrient soils, and subsequently improves the crop productivity observed in the level of the improvements observed in the plant
with few exceptions. Soil fertility is related to various factors such productivity by different studies. Aged biochars are better soil
as nutrient cycling, pH, soil N content, microbial population, cation cation exchange capacity enhancer than fresh biochars. On this
exchange capacity, water retention, and C sequestration (Fig. 7). As basis, it has been demonstrated that 15 month-aged biochar
already mentioned, the nutrients content as well as their absorp- increased cation exchange capacity from 26.2 mmolc/kg (obtained
tion capacity of biochar could significantly affect soil nutrients from treating soil with fresh biochar) to 173 mmolckg1 (Mukherjee
level. In addition to soil nutrient supplementation, the improve in et al., 2014). This higher improvement may be associated with
crop productivity due to biochar amendment of soil could be biochar surface oxidation and formation of more O-containing
attributed to better plants nutrient usage through enhancing nu- functional groups (See Sections 2.2.1.2 and 3.2.1). It is worth
trients retention and decreasing their leaching. As one may expect, mentioning that the impacts of natural aging of biochar in soil on
the reports of biochar application for crop productivity improve- biochar’s properties cannot be artificially stimulated accurately. A
ment in low nutrient soils are more common than those of fertile meta-analysis of 42 studies quantitatively compared the effects of
and healthy ones (Hussain et al., 2017; Laghari et al., 2015). As an freeze-thaw biochar aging, chemical (i.e., oxidation) biochar aging,
example, it has been indicated that eucalyptus-derived biochar and natural field biochar aging on biochar properties (Li et al.,
could significantly increase sorghum (Sorghum bicolor L. Moench) 2019a). Accordingly, freeze-thaw aging methodology is only
productivity up to 18e22%, compared to the control (Laghari et al., appropriate to understand the impacts of changes in biochar
2015). In another study it was found that addition of biochar to a porosity but provides little in terms of element compositions.
poor-nutrient soil in the North China Plain enhanced the maize Compared to natural process, chemically aged biochars are superior
grain yield by 10.7%, compared to the soil treated with commercial in terms of surface oxidation in the expense of exogenous elements
fertilizer (Zheng et al., 2017). importation from oxidants into biochar. In contrast, natural field
One of the most important modifications of soil physico- aging delivers biochars with significantly higher levels of interior
chemical properties by biochar amendment is soil pH optimiza- oxidation (Li et al., 2019a). Biochar type is another important factor
tion, allowing higher crop productivity. More specifically, addition that can affect biochar performance with respect to soil cation
18 H. Kazemi Shariat Panahi et al. / Journal of Cleaner Production 270 (2020) 122462

exchange capacity. El-Naggar et al. (2019) reported that the treat- be observed. However, on the downside, the amended biochar in
ment of sandy soils with three types of biochars, i.e., amursilver- long-term could trigger a biochar negative priming effect and
grass residue, paddy straw, and umbrella tree wood respectively subsequently inhibit native soil organic content mineralization
increased cation exchange capacity by 57%, 67%, and 90%. However, (Ventura et al., 2019; Zimmerman and Ouyang, 2019). The
only paddy straw biochar could enhance cation exchange capacity amendment of biochar can increase average soil available P and K
in the sandy loam soil. by up to 32.4% and 48.3%, respectively. For soil enrichment with P
Another field of interest is biochar application for increasing N and K, sewage sludge or animal manure may be used as biochar
dynamics and retention. It has been well-documented that biochar feedstock (Zheng et al., 2013b). Potassium-deficient soils may be
can increase soil N content, decrease its leaching, and recover N improved by using giant reed biochar pyrolyzed at high-
fertilizer (Mia et al., 2019; Zhao et al., 2013). Biomass compositions temperatures (i.e., 600  C) (Zheng et al., 2013b). Recently, Glaser
and pyrolysis condition are the two critical factors affecting the and Lehr (2019) calculated the effects of biochar amendment on
biochar impacts on soil N content. In general, biochar can adsorb soil P availability. Unlike the previous studies, they found a signif-
some inorganic N-containing compounds such as ammonia and icant improvement in P availability (as high as 4.6 times) following
nitrate and decreasing N loss by gradually releasing them to plant biochar amendment, regardless of the feedstock that was converted
roots (Haider et al., 2017; Solaiman and Anawar, 2015). This ca- into biochar. However, they also emphasized that improvement in
pacity depends on biochar surface properties, including cation soil P availability could only be achieved if biochar were pyrolyzed
exchange capacity, acidic functional groups, and surface area. To at temperatures <600  C and applied at high rates of >10 t/ha.
improve the biochar efficiency on decreasing N loss from soil, Moreover, soil pH was found as the main determinant of biochar-
various modifications could be considered. For example, ultrasonic induced soil P availability. No significant improvement was
treatment can improve biochar physicochemical characteristics observed when biochar was added to alkaline soils (pH, >7.5) while
and adsorption capacity (Feng et al., 2019). It has been documented it increased soil P availability in neutral (pH, 6.5e7.5) and acid (pH,
that combination of chemical and ultrasonic treatments can in- <6.5) soils by up to 2.4 and 5.1 times, respectively (Glaser and Lehr,
crease biochar capacity for NHþ 4 -N absorption by 20%, compared to 2019). Overall, it could be concluded that the application of engi-
the pristine biochar (Chen et al., 2017). The increased adsorption neered biochar as a slow-release P fertilizer could prevent P run-off
capacity of modified biochar is potentially associated with alter- and eutrophication while providing this limiting nutrient for seed
ation in its surface physico-chemical features, particularly germination and plant growth.
increasing O-containing functional groups availability. The Regardless of soil type, the presence of biochar may improve soil
amounts of NO þ
3 -N and NH4 -N in soils, and C-to-N ratios of soil and water holding capacity by about 10% on average (Dai et al., 2020). A
biochar are the indicators to predict the degree of N retention or its meta-analysis study (37 articles) revealed that by using biochar, the
recycling (Nguyen et al., 2017). Generally, biochar shows a higher permanent wilting point, field capacity, and available water content
affinity for NHþ 
4 -N (372e2102 mg/g) than NO3 -N (171e533 mg/g) of soils were improved on average by 16.7%, 20.4, and 28.5%,
because biochar surface is negatively charged (Zheng et al., 2013a). respectively (Edeh et al., 2020). Accordingly, the main determinants
The C-to-N ratios of less than 20 indicates the possible minerali- on these biochar-induced improvements (independent of soil type)
zation of N in biochar-amended soil by microbes whereas those of were specific surface area, particle size, and porosity of the biochar.
higher than 20 probably result in N immobilization (Nguyen et al., Therefore, biochar could be introduced into sand or low-silt soils to
2017). The mineralization process reduces the availability of N for improve water holding capacity and reduce Ksat of soils; two pa-
plants and may hence lead to lower plant productivity. The meta- rameters required for sustainable management of water. For this
analysis of 56 studies (1080 pairs of data) published in purpose, biochar application rates of 30e70 t/ha is optimum for
2010e2015 revealed that decreases in soil inorganic N (95% of coarse texture soils (Edeh et al., 2020). With respect to clay soils,
cases) were obtained within a year after biochar amendment the amendment by biochar reduces run-off by improving Ksat.
(Nguyen et al., 2017). On average, biochar reduced about ()10% However, water management is more significantly enhanced when
and ()11% of soil NO 
3 -N and NO3 -N, respectively (Nguyen et al., biochar is added to coarse-texture soils, compared to their clay type
2017). In addition to residence time of biochar in soil, soil pH, fer- counterparts.
tilizer type, biochar application rate, pyrolysis temperature, and
biochar surface properties are the other significant determinants of 4.1.2. Soil biological properties
soil N change dynamics. Therefore, to minimize the negative effects Soil microorganisms play significant roles in biogeochemical
on plants due to decreased N, biochar must be applied at least a cycles, decomposing organic matter, suppression of pathogens,
month before plants cultivation. Alternatively, organic fertilizers plants growth promoting, and soil health. Several studies have
must be applied to decrease the absorption of soil inorganic N by implicated that biochar can affect soil microbial structure and di-
biochar. The soil N flux is also affected by biochar-induced N fixa- versity (Table 4). Biochar can change the physico-chemical prop-
tion (See Section 4.1.2), nitrification, and/or denitrification pro- erties of soil which could affect the microbial community in soil. In
cesses (See Section 4.1.3.3). addition, highly porous structure of biochar provides a microenvi-
Like N, biochar amendment can improve the C concentration ronment for microbial colonization and growth in soil (Awad et al.,
(average, 47.6%) in low nutrient soils while at the same time could 2018; Quilliam et al., 2013). On the other hand, biochar may have
be used as a C sequestration tool to decrease the CO2 content in the neutral or negative effects on soil microbial community. For
atmosphere. Ultimately, these features improves the soil fertility as example, Elzobair et al. (2016) reported that soil amendment by
well as the crops productivity (El-Naggar et al., 2015). Compared to biochar had no significant effect on microbial colonization, struc-
other organic soil additives such as compost and manure, biochar ture, diversity, and enzymatic activities. In another study, biochar
possesses more stable C component owing to its long C half-lives amendment (0.5e5.0 wt%) decreased the total phospholipid fatty
ranging from 102-107 years (depends on biomass pyrolysis tem- acid content and bacterial population in the soil. However, its
perature) (Sa nchez-García et al., 2019). This higher C stability could amendment at low ratio (0.5% w/w) could induce the activity of
be ascribed to biochar’s high condensed aromatic structures (Awad microbial extracellular enzymes such as b-glucosidase, b-D-cello-
et al., 2013; Purakayastha et al., 2015). In the first few days-months biosidase, and N-acetyl-b-glucosaminidase (Wang et al., 2015b).
of biochar amendment, a positive priming effect increasing the rate This neutral to negative effects could be explained by the fact that
of soil organic content mineralization (decomposition) rate could biochar impact on soil microbial population highly depends on soil
H. Kazemi Shariat Panahi et al. / Journal of Cleaner Production 270 (2020) 122462 19

Table 4
Effects of biochar amendments on soil microbial community.

Biomass/Pyrolysis Amendment Soil type Microbial responses Ref.


temperature rate

Wheat straw/350-550  C 0e3% Slightly acidic - Increase in bacterial gene abundance and decrease in fungal gene abundance. Chen et al.
- Increase in dehydrogenase and alkaline phosphatase activities (2013)
Corn straws/500  C 0.5% Sandy loam - Increase in microbial biomass, particularly Gram-positive bacteria Lu et al.
(2014)

Maize straw/450 C 0e5% Fluvo-aquic - Bacteria abundance was decreased with increasing biochar application rate. Wang et al.
- Increasing soil microbial enzyme activities at 0.5% biochar. (2015b)
Sugar maple or White 5 t/ha Shallow sandy or - No significant effect on microbial community in first year. Noyce et al.
spruce sawdust/400  C sandy loam - A decreased fungi/bacteria ratio in the presence of maple biochar after 2 yr. (2015)
Hardwood/600  C 22.4 mg/ha Aridisol - No effect on microbial biomass, community structure, and enzyme activities. Elzobair
et al. (2016)

Cotton straw/450 C Up to 4.5 t/ Drip-irrigated desert - Increase in soil microbial biomass C (32%), soil microbial biomass N (58%), and basal Liao et al.
ha soil respiration (13%). (2016)
- Increase in b-glucosidase and cellobiohydrolase activities.
- Promoted growth of Gram positive and Gram-negative bacteria.
Oak pellet/550  C Up to 20% Weld silt loam - Increase in soil microbial biomass. Jiang et al.
- Increase in abundance of signature PLFAsa of Gram-negative bacteria and actinobacteria. (2016)
Maize straw/400  C 0-50 t/ha Silt loam - No significant effect on the absolute and proportional abundances of Gram positive/Gram Luo et al.
negative bacteria and protozoa. (2017a)
- Increase in absolute and proportional abundances of fungi and the fungi-to-bacteria ratio.
Rice straw/300-700  C 3% Anaerobic paddy - Decrease in denitrifying bacteria abundance and increase in iron-reducing bacteria. Wang et al.
(2017b)
Rice straw/550  C 2250, Yellow-brown, - Decrease in the proportions of Actinobacteria and Ascomycota. Gao et al.
4500 kg/ha tobacco-planting soil - Increase in proportions of the Proteobacteria, Acidobacteria, and Basidiomycota. (2017)
Raw rice husk/500  C 2% River sediment - Decrease in bacterial abundance and diversity. Liu et al.
(2018b)
Wheat straw/350e550  C 20 and 40 t/ Sandy loam - Increase in microbial biomass C. Li et al.
ha - Decrease in soil basal respiration rates. (2018b)
- No significant changes in b-glucosidase activity.
Moso bamboo chips/ 20 and 40 t/ Ferrosols - Increase in microbial biomass C (22.3%) at 20 t/ha of biochar. Li et al.
600  C ha - Decrease in microbial biomass C (17.5%) at 40 t/ha of biochar. (2018a)
- Increase in the relative abundance of Gemmatimonadetes and Thaumarchaeota.
- Decrease in the relative abundance of Acidobacteria and Chloroflexi.
Whole-tree residue/550  C 100 kg/ha Ferrosols - Increase in bacterial diversity. Nguyen
- Increase in the abundance of nitrifiers and pyrogenic C-decomposing bacteria. et al. (2018)
China fir branches/550  C 1 or 3% Mountain acidic red - Increase in the abundance of Gram-positive bacteria and actinomycetes. Li et al.
loam (2019e)
Maize straw/500  C 1% Agricultural field - Increase in activity of dehydrogenase. Li et al.
- Inhibition of urease activity. (2019d)
- Increase in the abundance of Gram-positive bacteria.
Rice hull/400  C Up to 45 t/ha Tobacco lands - Increase in the relative abundances of potential beneficial bacteria such as Aeromicrobium, Chen et al.
Bacillus, Burkholderia, Bradyrhizobium, and Chlorochromatium. (2020)
- Decrease in the relative abundances of denitrifying bacteria.
Leaf or woodchip/300 or 1 or 3% Forest - Increase in the abundance of Burkholderia-Paraburkholderia, Planctomyces, Sphingomonas Zhou et al.
600  C and Singulisphaera. (2020)
a
Phospholipid fatty acid.

and biochar types, and biochar application rates. On this basis, for influences the microbial growth and diversity in the soil. Biomass
example, noticeable changes in soil microbial community can only compositions, pyrolysis conditions, and in-situ and post-
be observed when the biochar application rates are sufficiently modifications methods significantly control biochar surface area
high to modify the soil properties such as pH, nutrients content, (See Sections 2 and 3). For example, soybean stover-derived biochar
and water holding capacity (Li et al., 2019f). The mentioned (300  C and 700  C) displayed 5.61 m2/g and 420.33 m2/g of surface
physico-chemical parameters are considered as the most important areas, respectively. Changing biomass type to pine needles deliv-
factors influencing the diversity and population of soil microor- ered biochars with slightly lowered respective surface areas of
ganisms (Palansooriya et al., 2019a). 4.09 m2/g and 390.52 m2/g under similar pyrolyzing conditions
In general, modifications in soil physico-chemical characteristics (Ahmad et al., 2016). Like porosity, water holding capacity of bio-
control the soil microorganisms’ growth. The high surface area and char increases with its surface area which could also be translated
porous structure of biochar is important for soil microbial hosting. into higher growth of soil microorganisms (Mohamed et al., 2016;
Temperature of pyrolysis and type of feedstock are the two Wong et al., 2017).
important factors affecting the biochar porosity (See Section 2.1.1). Biochar application has been implicated to significantly affect
The enhanced macropores formation at higher pyrolysis reaction microbial biomass content (Luo et al., 2017b). For instance, it has
temperature provides suitable habitat for bacteria and fungi, pro- been reported that biochar amendment at 10e20 t/ha into P-
tecting them against undesirable environmental conditions (See limited forest soil increased bacterial/fungal ratio while decreasing
Section 2.1.1). The deposition of the water molecules and soluble Gram-negative/Gram-positive bacteria ratio (Mitchell et al., 2015).
nutrients such as sugars, ketones, aldehydes, and acids into biochar The addition of oak and grass biochar can significantly increase the
macropores provides vital substances for microbial growth (See abundance of actinobacteria (i.e. Gram-positive bacteria) compared
Section 2.1.1). to other soil microbial group (Khodadad et al., 2011). Growth
Surface area of biochar is another important factor that stimulation of actinobacteria in the presence of biochar might be
20 H. Kazemi Shariat Panahi et al. / Journal of Cleaner Production 270 (2020) 122462

closely related to their high ability in pyrogenic C metabolism and physico-chemical properties (Li et al., 2018b).
high growth rate in C-rich soils. Diverse bacterial and fungal re-
sponses to biochar amendments might be associated with their 4.1.3.1. CO2 emission. Alteration in physico-chemical characteristics
ecological features and physiological characteristics. More specif- of the soil after biochar application has significant effects on soil
ically, bacteria and fungi are significantly different in terms of CO2 emissions. The degree of this effect in forest soils varies among
nutrient demands, growth rate, and resistance to environmental the different investigations. For example, sugar maple biochar
stresses. Compared to fungi, bacteria are more sensitive to the lack could enhance CO2 emission from forest soils (Mitchell et al., 2015),
of C source; therefore, high C content in biochar can strongly pro- whereas up to 31.5% decrease in CO2 flux from pine forest soils was
mote their growth (Ameloot et al., 2013). In general, fungal hyphae observed in the presence of unspecified biochar (Sun and Lu, 2014).
are larger than bacteria, inhibiting them from colonization in bio- Biochar application rate could also be important in CO2 emission
char pores. Moreover, soil pH generally increases after biochar from soil. For example, biochar amendment at high application
addition, making the environment more favorable for bacterial rates (10%) increased CO2 emission more significantly, compared to
growth rather than fungi. Soil inorganic N could be modified by low biochar application (1%) (Johnson et al., 2017). There are also
biochar application through impacting N2-fixing bacteria. This studies providing evidence that biochar application had no signif-
phenomenon biologically increases soil N flux through the con- icant effects on CO2 emission from forest soils (Sackett et al., 2015;
version of atmospheric N2 into NH3 by both symbiotic (e.g., Zhou et al., 2017). These variations in biochar effects might be
rhizobia) and free-living (e.g., Azospirillum and Azotobacter spp.) associated with biochar and soil types, biochar application rates,
bacteria. The enrichment of free-living bacteria is due to the bio- incubation time, and vegetation.
char’s anoxia pores whereas the increase in nodulation of rhizobia Overall, the effects of biochar application on CO2 flux can be
is stimulated through the adsorption of soil N by biochar, the explained by four processes; (i) biochar application can influence
release of Ca, P, K, Mo, and B, and higher retention of signaling the mineralization of soil organic C pool through “priming effects”,
molecules (e.g., nod factors) (Biederman and Harpole, 2013; causing an increase in CO2 emission; (ii) biochar can alter the soil
Nguyen et al., 2017). Therefore, the origin of biochar must be CO2 emission through adsorbing CO2 molecules on its surface; (iii)
considered before soil applications. For example, soft wood-derived biochar can affect the physico-chemical characteristics of soil,
biochar significantly boosts N fixation in Alder plant by consider- which indirectly change CO2 emission; and (iv) biochar application
ably decreasing soil N (Robertson et al., 2012). can significantly affect soil microbial activities and diversity that
Soil microorganisms are a rich source of numerous hydrolytic are involved in CO2 metabolism. The stability and the rate of
extracellular and intracellular enzymes (Mohammadipanah et al., turnover of biochar in soil determine CO2 emission from soil. 14C- or
13
2015), which have significant roles in biochemical processes C-labelling technique is a promising approach for tracing biochar
(Hamedi et al., 2015b). These enzymes are also considered as bio- turnover and its subsequent transformation into different products.
indicator of soil quality as they directly reflect the microbial ac- This approach can also determine the contribution of biochar to the
tivity (Ahmad et al., 2012; Das and Varma, 2010). Biochar amend- total CO2 emission from soil by differentiating it from the back-
ments can restore degraded soils by improving soil enzyme activity. ground of other CO2 sources from soil (Kuzyakov et al., 2014; Wang
For instance, biochar amendment could increase the activity of et al., 2016). A meta-analysis of the biochar stability in soil inves-
some microbial enzymes such as b-glucosidase, b-D-cellobiosidase, tigated 128 observations from 24 studies that applied 14C- or 13C-
and a-glucosidase (Wang et al., 2015b), which are involved in labelling technique (Wang et al., 2016). Accordingly, the biochar
nutrient cycling (Kazemi Shariat Panahi et al., 2019a, b). However, decomposition rate reduces with retention time in soil (i.e., the
this effect seems to be dependent on biochar amendment rate. For duration of the experiments) while its decomposition rate in-
example, the addition of maize biochar at 0.5 wt% increased the creases logarithmically. Surprisingly, the mean residence times
enzymes activity, while at higher rates (1.0e5.0 wt%) the activity required for the decomposition of the recalcitrant (97% of total C)
decreased (Wang et al., 2015b). As revealed by Teutscherova et al. and labile (3% of total C) C contents of biochar were estimated at
(2018), biochar alleviated Al toxicity in low-nutrient soil, which 556 yr and 108 d, respectively (Wang et al., 2016). However, the
followed by increase in activity of dehydrogenases. On the other exact retention time for C decomposition mainly depends on soil
hand, the activity of some hydrolytic enzymes such as b-glucosi- clay content, biochar feedstock, and pyrolysis temperature.
dase, b-glucosaminidase, and phosphatase significantly decreased
for biochar-amended Acrisol (Teutscherova et al., 2018). The 4.1.3.2. Soil methane emission. A change in CH4 emission from soils
decreased enzyme activity might be related to the inactivation of could be expected following biochar amendment. The effect could
hydrolytic enzymes through their adsorption on the biochar sur- be either suppressive such as CH4 flux from waterlogged rice
face. Due to sophisticated nature of enzyme-solid phase in- paddies (Liu et al., 2011b) or inductive such as CH4 emission from
teractions, drawing a conclusion about biochar impact on enzyme aerobic and forest soils (Karhu et al., 2011). The increasing CH4
activities is difficult. Overall, the impacts of biochar on soil enzymes mechanisms following biochar amendment could be through five
can be classified as direct (i.e., microbial enzyme synthesis) and processes (Brassard et al., 2016), including (i) increasing the soil C
indirect (i.e., adsorption on biochar surface) effects. Hydrolytic content, which could be assimilated into CH4 by methanogens (i.e.,
enzymes are also produced by soil-borne pathogenic microorgan- archaea and bacteria); (ii) suppressing CH4 oxidation by meth-
isms, disrupting plant growth (i.e., degrading plant cell wall). These anotrophic activity; (iii) increasing CH4 emission due to off-gassing
harmful enzymes could be adsorbed by biochar, protecting the from surface and/or pores desorption; (iv) increasing soil pH that
plants from cell wall degradation (Jaiswal et al., 2018). affects methanogens and methanotrophs activities; and (v)
enhancing CH4 production and emission by providing anaerobic
4.1.3. Greenhouse gases emission microsites in soil. It is worth mentioning that methanotrophs could
Carbon dioxide can migrate from soil to the atmosphere through be suppressed by fresh biochar due to existence of inhibitory
a process, known as “soil respiration” or “soil CO2 emission”. Like compounds such as some metals and organics. Alternatively, fresh
CO2, CH4 and nitrous oxide (NO2) are considered as the main biochar may substitute CH4 substrate as energy source in meth-
greenhouse gasses but with greater global warming potentials per anotrophs by some other sorbed organic compounds. Both pro-
unit mass. The emission of greenhouse gasses from soil could be cesses result in higher CH4 emission for fresh-biochar-amended
impacted by biochar amendments due to modifications in soil soil.
H. Kazemi Shariat Panahi et al. / Journal of Cleaner Production 270 (2020) 122462 21

Compared to emission enhancing effect, the CH4 suppression average in biochar-amended soils (Liu et al., 2018a). Such increases
from soil by biochar amendment is far less common. One possible were commonly observed in studies where biochar was applied at
suppressive mechanism is through enriching methanotrophs as a high application rates (>40 t/ha), highly alkaline biochar was used
result of improved soil aeration. At the same time, biochar could (manure- or straw-derived biochar), or treated soils has low buff-
also induce the growth of methanogens through increasing dis- ering capacities (clay texture, organic C of 10 g/kg, and pH of 5).
solved organic C content in soil. However, at certain conditions (i.e., There are also some reports highlighting positive or non-
higher soil aeration), methanotrops population overwhelm that of significant effects of biochar application on N2O emission. For
the methanogens. Overall, suppressive CH4 emission mechanisms instance, Hawthorne et al. (2017) found that biochar application at
could be achieved through (i) enhancing CH4 uptake by adsorbing it rate of 10% to forest soil greatly increased N2O emission, while no
on biochar surface and/or increasing CH4 diffusion through the soil, significant effect was reported after application of lower rate (1%) of
and (ii) providing a suitable condition for CH4-oxidizing soil bac- biochar. Overall, the impact of biochar amendment on N2O emis-
teria by reducing soil density and increasing porosity. In fact, bio- sion is complex and significantly depends on biochar chemical
char application increases aeration and porosity, providing an oxic composition and pH, and soil physico-chemical properties. Soil
condition that in association with higher added C substrate and amended with biochar containing high N and low C (5 g/kg)
enhanced CH4 uptake will result in more CH4 oxidation, production, contents (e.g., pine chip or walnut shell biochar, manure-derived
and emission (Brassard et al., 2016). biochar, or those pyrolyzed at the temperatures less than 350  C),
Overall, through a meta-analysis study, it was observed that as well as high ash content significantly increases N2O emissions.
biochar amendment in acidic soils that experience periods of This increase could also be affected by the original soil N content (N
flooding could potentially decrease CH4 emissions (Jeffery et al., fertilizers) (Van Zwieten et al., 2014; Zheng et al., 2012). Typically,
2016). In contrast, biochar may weaken the CH4 sink strength of soil N2O emission either decreased or remained unaffected by
soils, particularly alkaline or neutral ones that do not have flooding biochar containing C-to-N ratios of greater than 30 (Cayuela et al.,
periods. Therefore, water management and soil pH considerations 2014; Verhoeven and Six, 2014). Like C-to-N ratio, the higher the
must be done prior to biochar application if CH4 mitigation is pH of the biochar, the lower the N2O emission from soil will be. This
intended. Soil CH4 flux is also under control of soil N availability. On is especially true in biochars with high pH (i.e., >9). More specif-
a rate dependent basis, the addition of large amounts of NHþ 4 -rich ically, there is a lower proportion of biochar with pH less than 9
fertilizers into soil results in a higher emissions of CH4 from soil. (particularly, 7e9) that is associated with either increased or no
This higher emission is attributed to the fact that NHþ 4 competi- effect on N2O emissions (Brassard et al., 2016). Soil moisture con-
tively binds to CH4-binding site on biochar, releasing more CH4 dition, determined by the percentage of water filled pore space
(Bedard and Knowles, 1989). On the other hand, low amounts of N (WFPS), controls N2O emission (WFPS <80%) or mitigation (WFPS
fertilizer could boost CH4 oxidation by enriching methanotrophes >80%) (Bateman and Baggs, 2005). Biochar can improve WFPS and
(Bodelier et al., 2000; Nazaries et al., 2013). On this basis, a typical N2O mitigation by (i) enriching N2O-reducing bacteria, (ii) creating
application of N fertilizer up to 100e140 kg N/ha stimulates CH4 and maintaining anaerobic microsites owing to biochar hydrophilic
oxidation whereas further increase in N fertilizer inhibits CH4 property and its combination with soil micro-aggregates, and (iii)
mitigation in soil (Jeffery et al., 2016). facilitating the electron transfer to denitrifying microorganisms
due to biochar matrix (acting as electronic conductor) and the ex-
4.1.3.3. Soil N2O emission. Biochar has been shown to reduce N2O istence of quinone-hydroquinone functional groups (induction of
emission from many farmland soils and forest environments (He electron shuttle) on the surface of biochar (Liu et al., 2018a; Sun
et al., 2016; Xiao et al., 2016). Sun and Lu (2014) reported that the et al., 2017).
application of biochar at 30 t/ha to forest soil reduced N2O emission
by 25.5%. Furthermore, Xiao et al. (2016) found that biochar 4.2. Pollution remediation
application (5 t/ha) to a Chinese chestnut forest could significantly
decrease cumulative total N2O flux by 20.5%. A recent meta-analysis Biochar is a promising sorbent for various organic and inorganic
using the data compiled across 208 peer-reviewed studies showed pollutants in soil and water due to its high adsorption capacity and
that biochar reduces the emissions of N2O by 32% on average, and porous structure. These characteristics could specifically be engi-
reaching the maximum value at biochar addition rate of >40 t/ha neered for removal of a specific environmental pollutant.
(Liu et al., 2018a). There are two fundamental mechanisms under-
lying the decreased soil N2O emission. First, biochar amendment 4.2.1. Inorganic contaminants
increases soil aeration and O content, prohibiting soil denitrifica- Biochar has exhibited a great potential to remove contaminants,
tion process by denitrifying bacteria, which occurs in O2-limited particularly heavy metals from wastewaters due to its high surface
condition. Second, biochar has high adsorption capacity that can area and microporous structure (Fig. 8). However, high contami-
adsorb NHþ 
4 and NO3 . This process increases plants growth, im- nant concentrations in aqueous solution could not sufficiently be
mobilizes N compounds, and may decrease NH3 volatilization, treated by pristine biochar. Moreover, the application of grinded
reducing inorganic N pool for N2O-producing microorganisms via biochar (i.e., engineered through ball milling process) causes diffi-
denitrification process (Clough et al., 2013; Van Zwieten et al., culties in the biochar separation step due to its small particle size
2010). It should be noted that increase in soil pH and NHþ 4 avail- and density (See Sections 3.1.1 and 3.1.4). To overcome these limi-
ability induces soil NH3 ventilation by shifting the equilibrium from tations, several investigations have been focused on the production
NHþ 4 towards NH3 (Pan et al., 2016). The addition of biochar to soil of engineered biochar with improved surface properties. In recent
can have a double-edged sword effects on NH3 ventilation. Upon years, engineered biochar have been designed to remove various
biochar amendment, NH4 availability is decreased by its adsorption types of contaminants with larger surface area, improved func-
by the O-containing groups on the surface of biochar (Kastner et al., tional groups, increased surface-active sites, and ease of separation
2009). Alternatively, biochar may mediate NH3 formation by (Table 5).
increasing soil pH due to the release of alkaline minerals (e.g., hy- Different types of physico-chemically engineered biochars have
droxides, oxides, and carbonates of Al, Ca, Fe, Mg, Mn and Zn) (Liu been developed for enhancing heavy metals removal (Table 5). A
et al., 2018a). Through a meta-analysis study, it was understood detailed explanation of such modification methods with respect to
that the volatilization of NH3 may be increased by up to 19% on heavy metals removal has been provided in Section 3. For example,
22 H. Kazemi Shariat Panahi et al. / Journal of Cleaner Production 270 (2020) 122462

biochar covered with MnOx ultrafine particles showed higher the adsorption is pH dependent. Typically, high aqueous pH values
sorption capacity to adsorb Pb(II), Cu(II), and Cd(II) (Gan et al., decrease the phosphate adsorption in biochar with negatively
2015). The MnOx-loaded biochar possessed more O-containing charged surface. Recently, Han et al. (2020) studied the effect of P
groups (i.e. hydroxyl groups, phenolic hydroxyl and carboxyl on the remediation of Cd by biochar. For this purpose, biochar-
functional groups) on its surface, providing more adsorption sites supported nanoscale Fe0 composite was engineered and applied
for heavy metals. Ding et al. (2016) found that NaOH-modified for Cd removal from the sediments in the Ulansuhai River where
biochar had greater capacity to adsorb (2.6e5.8 times) heavy serious eutrophication problems were faced. Interestingly, effective
metals than pristine biochar. Alkali-modification increased biochar immobilization of Cd by this engineered biochar through adsorp-
surface area which could, in turn, enhance porosity by increasing tion and precipitation mechanisms was induced by P in overlying
NaOH-C matrix interactions. In addition, alkali-modification water. In fact, this biochar could remediate labile fractions of Cd and
enhanced cation exchange capacity, which might be associated aqueous phase P.
with increase in O-containing functional groups. In some cases, biochar modification can provide more capacity
Various heavy metal removal mechanisms by activated/modi- for inorganic contaminants removal, compared to the pristine ones.
fied engineered biochars are illustrated in Fig. 8. Biochar can For example, only 10% of phosphate could be removed by pristine
remove nitrate, phosphate, and ammonia from natural ecosystem, biochar, compared to 66.7% by MgO-loaded biochar. The enhanced
hence preventing eutrophication, i.e., the excessive growth of adsorption could be attributed to high affinity of MgO for phos-
photosynthetic organisms in response to high inorganic nutrients phate in aqueous environment (Yao, 2013). More discussion on the
content in aqueous environment. The eutrophication risks of waste biochar engineering method for phosphate removals could be
streams containing P can be minimized by the application of found in Sections 3.2.1 and 3.2.2. Mg-loaded biochars also display
engineered biochar decorated with LDHs. To achieve this, biomass high adsorption capacities for P (>100 mg/g) through its precipi-
is pyrolyzed in the presence of some metal hydroxides such as Ni/ tation and surface deposition of P on Mg (Yao et al., 2013a). The
Fe, Mg/Al, and Zn/Al. However, biochar itself may also release some adsorbed P remains bioavailable, allowing the formulation of slow-
amounts of nitrate or phosphate to the environment. Generally, the release P fertilizers. When Mg-impregnated biochars are intro-
adsorption of inorganic contaminants by biochar depends on bio- duced into agricultural soils, the leaching of P could be reduced by
char surface properties, contaminant type, and pH. Yang et al. 89.25% while at the same time P availability of the surface layer soil
(2019b) found that corn-stalk-Zn/Al-LDH has fast Elovich kinetics was increased by 3.5 folds (compared to the soil without biochar)
(5,925 mg/g/h) and superior P adsorption capacity (152.1 mg/g), but (Chen et al., 2018a).

Table 5
Engineered biochars applications for inorganic contaminants removal.

Biochar/Pyrolysis Type of Effect on contaminant removal Mechanism Ref.


temperature contaminant

Fe/Ca-rich biochar/270- As(V) and Adsorption capacities of 22.8 and 41.6 mg/g - Yoon et al.
720  C Cd(II) for As(V) and Cd(II), respectively. (2017)
Fe-Hichory chips As(V) Maximum As(V) adsorption capacity of Chemisorption mechanism Hu et al.

biochar/600 C 2.16 mg/g, compared to insignificant (2015)
adsorption by pristine biochar
a-FeOOH-nanorods- Cu(II) Increased adsorption of coppera Increased biochar surface area and pore volume Yang et al.
impregnated Biochar/ (adsorption capacity, 144.7 mg/g) (2018)
800  C
Fe3O4ealginate Cu(II) Three times higher than that of the Coordination and ion exchange were the major mechanisms for Cu(II) Yu et al.
modified biochar magnetic biochar, Maximum Cu(II) removal by this engineered biochar. (2017a)
microspheres/800  C adsorption capacity of 40.42 mg/g
CeO2-MoS2 hybrid Pb(II) Enhanced Pb(II) adsorptiona (˃99% removal Improved lectrostatic attraction, CpePb(II) bond interaction, and Li et al.
biochar/600  C efficiency, 6 h) complexation combined processes (2019b)
Magnetic Pb(II) Outstanding Pb(II) adsorption capacity of Multiple interaction mechanisms involved the O-containing groups Yang et al.
electrochemical 113 mg/g and fast kinetics of 0.054 g/mg/h.(complexation with CeO and OeH) and Fe3þ species (FeeOePb bond) (2019a)
Fe3O4/biochar/600  C on the engineered biochar surface.
Biochar-Zn/Al-LDH P Elovich kinetics and P adsorption capacity Interlayer anion exchange and surface complexation Yang et al.
composite/ of 5,925 mg/g/h and 152.1 mg/g, (2019b)
respectively.
Mg-Al and Mg-Fe PO3-
4 Enhanced PO3 4 removal by >95%
a
Interlayer anion exchange and surface adsorption Wan et al.
layered double (2017)
hydroxides biochar/
600  C
Cow dung-derived PO3-
4 Increased PO3
4 adsorption capacity to Precipitation reaction between P salts and Mg compounds Chen et al.
biochar/700  C 345 mg/ga (2018b)
Phosphogypsum- PO3-
4 102.4 mg/g PO3
4 adsorption capacity Electrostatic adsorption, surface precipitation, and ligand exchange Wang et al.
treated biochar/300- (2020)
600  C
Fe3O4-Douglas fir PO3-
4 ~90 mg/g of PO3
4 from water Magnetic removal Karunanayake
biochar/~900  C et al. (2019)
La-biochar/400-600  C PO3-
4 High PO3
4 adsorption capacity of Adsorption on the La-biochar through ligand exchange, complexation, Xu et al. (2019)
36.06 mg P/g and electrostatic interaction.
Cu-biochar composite/ Re(VII) Maximum Re(VII) adsorption capacity of Hybrid mechanism of adsorption Hu et al.
350e500  C 20.91 mg/g, 3e12 times higher than (2018)
pristine biochar
Biochar-supported nano NO
3 High capacity for NO3 removal (75e97%) Magnetite enhanced the reactivity of Fe(0) for nitrate removal Wei et al.
zero-valent iron (2018a)
a
Compared to pristine biochar.
H. Kazemi Shariat Panahi et al. / Journal of Cleaner Production 270 (2020) 122462 23

Biochar engineered by using ball milling has also attracted some removal of antibiotics from wastewaters/agricultural drainage is
levels of attention for water purification. Through this method, very important to avoid emergence of drug-resistant pathogens
micro-nano-engineered nitrogenous cow bone biochar (pyrolyzed (Mohammadipanah et al., 2016) and to prevent new threats to
at 600  C) was developed which was capable of removing 165.7, human and animal health (Dehhaghi and Mohammadipanah, 2017;
287.6, and 558.9 mg/g of Cd(II), Cu(II), and Pb from water, respec- Panahi et al., 2016). In addition, it should also be highlighted that
tively (Xiao et al., 2020). In another study, the removal of ammo- the degradation of these compounds does not necessarily render
nium from water was improved by more than three folds through them harmless. For instance, biological degradation of furazolidone
ball milling bamboo biochar, compared to pristine biochar (7.0 vs. may result in the formation of carcinogenic metabolites such as
22.9 mg/g) (Qin et al., 2019). ß-hydroxyethylhydrazine and 3-amino-2-oxazolidone (Lewkowski
Like water medium, heavy metals can be remediated from soil et al., 2019). This further signifies the importance of biochar
medium using engineered biochar. Calcium-based magnetic bio- application in eliminating them through the adsorption
char, for example, decreases the bioavailability of Cd and As in soil mechanism.
by transforming these metals into stable fractions (Wu et al., 2020). Biochar engineering increases its efficiency in the removal of
Following the addition of this porous biochar, both pH and cation pesticides. In a successful field trial, steam activated (800  C for
exchange capacity of the soil increased, leading to Cd remediation. 45 min) almond shell biochar that was slowly pyrolyzed at 650  C
Moreover, bi-dentate chelate and ternary surface complexes were for 1 h under N2 was used for the removal of dibromo-
formed on iron oxide surface (Wu et al., 2020). Thiol-modified chloropropane from well waters (Klasson et al., 2013). The engi-
biochar has also been used for remediation of Pb2þ and Cd2þ neered biochar showed a favorable adsorption capacity (up to
polluted soil with the corresponding maximum adsorption capac- 102 mg/g) for this soil fumigant pesticide due to the improved
ities of 61.4 mg/g and 45.1 mg/g (Fan et al., 2020). The engineered biochar surface area (up to 344 m2/g). With respect to color/dye
biochar was produced through esterification with ß-mercaptoe- removal from water, for example, slow pyrolyzed (at 1000  C) acid-
thanol and reduced the available Cd and Pb in soil by 39.2% and treated Kenaf (Hibiscus cannabinus) biochar efficiently trapped
11.1% after a 28-d incubation (Fan et al., 2020). Biochar amendment methylene blue (22.7 mg/g at 50  C and pH 6e7) in its honeycomb
into soil may indirectly remediate heavy metals by enriching mi- pore network (mesoporous with average pore diameter of 3 nm)
croorganisms that have the capability to remediate heavy metals (Mahmoud et al., 2012). This engineered biochar showed a higher
(Hamedi et al., 2015a, 2015b). surface area, higher O content, and almost double fixed C content,
compared to the pristine control. Biochar can also be used for the
4.2.2. Organic contaminants removal of solvents from water. Trichloroethylene, for example, has
In addition to inorganic pollutants, biochar has potential for been removed from water using biochars derived from soybean
removing hazardous organic compounds such as dyes, antibiotics, stover (Mohan et al., 2014). The adsorption capacities of these
pesticides, oils, phenolics, polynuclear aromatics and persistent biochar were dependent on pyrolysis temperature. In fact, biochar
organic pollutants. Generally, the adsorption of organic compounds produced at the highest temperature (700  C) showed the highest
on biochar depends on the contaminant type and biochar surface adsorption capacity for trichloroethylene (32.02 mg/g) (Mohan
properties. Accordingly, the adsorption mechanisms for organic et al., 2014).
contaminants removal can be classified as pore-filling, p-p inter- Biochar can be used in the development of hybrid techniques for
action, electrostatic attraction, cation exchange, hydrophobic in- water purification, such as biochar-augmented biofilters, perme-
teractions, complexes adsorption, and partition uncarbonized able reactive barriers, and biochar-based membrane filtration
fraction (Dai et al., 2019; Wang et al., 2017b). Engineered biochar (Palansooriya et al., 2020). In 2018, a novel chem-bio hybrid system
has been extensively used to remove organic contaminants. One was constructed using wheat straw biochar-supported nano Fe-S
example is the enhancement of levofloxacin adsorption by cerium composite and Corynebacterium variabile HRJ4. This biologically
trichloride-treated biochar (Yi et al., 2018). Cerium treatment could engineered biochar could efficiently remove and degrade trichlo-
be associated with increasing the O-containing functional groups roethylene from water while showing a higher stability and smaller
on the surface of biochar. Moreover, CeO2 had mesoporous struc- hydrodynamic diameter, compared to the pristine biochar (Lyu
ture, thereby could improve the adsorption capacity of biochar (Yi et al., 2018b). An inorganic-organic hybrid system could be con-
et al., 2018). Furthermore, Alghazwi et al. (2019) found that ball- structed through decoration of soft wood biochar composite (py-
milled biochars had higher sorption capacity (three-fold increase) rolyzed at 700  C) with TiO2. Compared to the pristine biochar and
for galaxolide, compared to the pristine biochar. In addition to the TiO2 alone, the photocatalytic degradation efficiency of phenol by
improvement of biochar surface area and pore size, the surface the engineered biochar was significantly improved, i.e., reaching
polarity was also increased due to higher availability of O-con- 64.1% under UV light and 33.6% under visible light (Lisowski et al.,
taining functional groups. The presence of these groups facilitates 2017). Overall, engineering biochars through hybridization tech-
organic contaminants sorption through H2 binding and complex- niques could greatly improve their removal capacity of contami-
ation between organic compound and biochar (Liu et al., 2011a). nants from water.
Engineered biochars are also efficient for the removal of bio-
logical contaminants from water. For example, engineering wood 5. Conclusions and future prospects
biochar through H2SO4 oxidation and the consequent increase in
biochar surface area (234.7 m2/g, almost double the area of the A promising way for addressing current environmental issues is
pristine biochar) improved the retention of Escherichia coli from the application of powerful remediating compounds such as bio-
stormwater (Lau et al., 2017). Recently, the properties of pristine char. This carbonaceous compound could efficiently mitigate CO2
biochar produced from pyrolyzed banana pseudostem biomass at (i.e., by consuming biomass during pyrolysis) while at the same
600  C was significantly improved by Fe3O4 coating (Gurav et al., time allows sustainable environmental management. More spe-
2020). This engineered biochar showed superparamagnetic prop- cifically, biochar could have significant impact on soil biological and
erties and very high surface area and was efficiently used for nutritional properties, and greenhouse gases emission; or be used
removal of the antibiotic furazolidone from wastewater. More in pollution remediation. To most effectively exploit biochar's
specifically, up to 37.86 mg furazolidone/g of biochar was adsorbed favorable properties while minimizing the environmental burdens
through chemisorption mechanisms. It should be noted that the associated with its application, the physico-chemical properties of
24 H. Kazemi Shariat Panahi et al. / Journal of Cleaner Production 270 (2020) 122462

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