Karim 2021

Critical Reviews in Environmental Science and
Technology
ISSN: (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/best20
Enrichment of primary macronutrients in biochar

for sustainable agriculture: A review
Adnan Asad Karim, Manish Kumar, Ekta Singh, Aman Kumar, Sunil Kumar,
Arati Ray & Nabin Kumar Dhal
To cite this article: Adnan Asad Karim, Manish Kumar, Ekta Singh, Aman Kumar, Sunil Kumar,
Arati Ray & Nabin Kumar Dhal (2021): Enrichment of primary macronutrients in biochar for
sustainable agriculture: A review, Critical Reviews in Environmental Science and Technology, DOI:
10.1080/10643389.2020.1859271
To link to this article: https://doi.org/10.1080/10643389.2020.1859271
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CRITICAL REVIEWS IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY
https://doi.org/10.1080/10643389.2020.1859271
Enrichment of primary macronutrients in biochar for

sustainable agriculture: A review
Adnan Asad Karima, Manish Kumara, Ekta Singhb, Aman Kumarb,
Sunil Kumarb, Arati Raya, and Nabin Kumar Dhala
a
Environment and Sustainability Department, CSIR-Institute of Minerals and Materials
Technology, Bhubaneswar, India; bTechnology Development Centre, CSIR-National Environmental
Engineering Research Institute (CSIR-NEERI), Nagpur, India
ABSTRACT
Macronutrient-enriched biochars
have potential for nutrient recy-
cling from waste, enhance soil
fertility, reduce consumption of
fertilizers, and thereby promoting
sustainable agriculture. The focus
of the recent research studies has
been on exploring different
methods for production of mac-
ronutrients (nitrogen [N], phos-
phorus [P], and potassium [K])
enriched biochar fertilizers. There
is now an urgent need to comprehend the work carried out on biochar fertilizers for a
proper scientific understanding and advancement. This review provides crucial informa-
tion about nutrients enriched biochars production and the underlying mechanisms
toward its use in agriculture. The production methods, nutrient characteristics, potential
major challenges and future perspectives of using these nutrients enriched biochars
have also been dealt in the present review. Among primary macronutrients, the main
focus of nutrients enriched biochar are on N and P. Total N, P, and K enriched up to
10%, 15.32%, 25.85% in biochar through controlled (primarily temperature) pyrolysis
and utilization of specific feedstock. Although total macronutrients content in nutrients
enriched biochar were thoroughly studied, but the bio-labile and plant available frac-
tions of these nutrients are yet to be extensively researched. Nutrients transformation
in biochars revealed about comparatively higher bio-available K fraction due to forma-
tion of water soluble kalicinite (KHCO3) minerals. The efficacy of biochars toward soil
fertility and plant growth was widely studied (mainly as pot experiments) and there
results varied. Overall, the prospects of nutrients enriched biochars toward sustainable
agriculture has gained momentum with time and further engineered biochars hold
great potential to cater for specific soil-plant-environment system.
KEYWORDS Agriculture; biochar fertilizers; macronutrients; soil fertility; waste
CONTACT Manish Kumar manish@immt.res.in; Adnan Asad Karim md.karime@gmail.com Environment

and Sustainability Department, CSIR-Institute of Minerals and Materials Technology, Bhubaneswar, Odisha
751013, India.
Adnan Asad Karim and Manish Kumar are the joint first authors.
Supplemental data for this article can be accessed at publisher’s website.
ß 2021 Taylor & Francis Group, LLC
2 A. A. KARIM ET AL.
1. Introduction
Sustainable agriculture seeks development and implementation of different
agricultural management strategies to alleviate detrimental effects of inten-
sified land use. In recent years, extensive research focused on efficient util-
ization of various natural and synthetic fertilizers for the sustainable
agriculture. These fertilizers are extensively utilized to enhance the soil fer-
tility and crop productivity (Semida et al., 2019). Synthetic fertilizers con-
tains nutrients (nitrogen-N, phosphorus-P, potassium-K) in high quantity
and water soluble forms, therefore widely used in soils compared to man-
ures, and organic fertilizers (Olsen, 1978; Vanlauwe et al., 2010). However,
continuous and overuse of synthetic fertilizers (specifically superphosphate)
resulted in accumulation of toxic heavy metals (Cu, Zn, Cd, Pb, As, and
Mn) in soils and crops, posing health risks to humans (Gimeno-Garcia
et al., 1996; Kelepertzis, 2014; Lin et al. 2019; Modaibsb & Al-Sewailem,
1999). Therefore, intensive farming practices with sole dependency on con-
ventional fertilizers are generally unfavorable and costly for soil quality and
ecosystem (Ding et al., 2016; Karer et al., 2015). The use of eco-friendly
approach to improve fertility of the soil is therefore imperative (Inyang
et al., 2016; Ok et al., 2015).
Biochars application in soil received growing interest over past two deca-
des for sustainable agriculture by improving fertility, productivity (Peiris
et al. 2019) along with numerous advantages like waste management, and
climate change mitigation (Awad et al., 2018; El-Naggar et al., 2019).
Biochars are carbonaceous solid material produced through thermo-chem-
ical conversion of organic substances in presence of limited oxygen for soil
application (Kumar, Singh, Singh, et al., 2020; Lehmann & Joseph, 2015).
Application of biochar are widely studied, but its efficacy is not always
positive and showed variation depending on characteristics along with soil-
environmental conditions (El-Naggar et al., 2019; Kumar, Singh, Khapre,
et al., 2020; Purakayastha et al., 2019; Singh et al., 2020). Characteristic of
biochars are mainly influenced by chemical composition of feedstock and
production conditions. Biochars produced from hardwood wastes like euca-
lyptus, pine bark and sawdust possess higher alkaline pH, carbon (C) con-
tent, and aromaticity; whereas, ash content and nutrients like N, P, K, and
calcium (Ca) are lesser (Domingues et al., 2017). Biochars produced from
crop residues (Prakongkep et al., 2015; Wang, Hu, et al., 2013) and animal
manures (Cantrell et al., 2012) were contrastingly alkaline with higher
nutrients, but with lesser C content and aromaticity. In relation to pH
value, acidic and neutral biochars were also reported (Chan & Xu, 2012).
Low temperature (250–350 C) biochars of Birch (Betula spp.) (Hagner
et al., 2016), Pecan shell and Switchgrass (Novak et al., 2009) bear acidic
pH (5–6), whereas Eucalyptus deglupta (Rondon et al., 2007) derived
CRITICAL REVIEWS IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY 3
biochar showed neutral pH (7.0–7.5). When pyrolysis temperature

increased from 300 to 800 C, C content in biochars increased in contrast
to hydrogen and oxygen (Kookana et al., 2011). The porous structure of
biochars augment beneficial soil microorganism (e.g., mycorrhizae and bac-
teria) population due to their protective habitat (Atkinson et al., 2010;
Spokas et al., 2012) which helps in nutrients transformation and dynamics.
Biochars having less C and high ash content improved plant productivity
in sandy and acidic soils due to biochar induced liming effect, improved
soil physical structure and nutrient use efficiency (Dai et al., 2020).
Biochars derived from less C/N ratio feedstocks (like animal manure) were
more efficient in improving P availability in soils (Gao et al., 2019). Earlier
studies revealed about combined application of fertilizers (inorganic/organic
amendments) with biochar lead to improve crop yield (Ye et al., 2020). As
an alternative to fertilizers, several researchers focused on nutrients rich
biochar production and application for improving soil fertility and product-
ivity (Chan & Xu, 2012; Ippolito et al., 2015). Application of nutrients rich
biochars could be more useful for degraded and/or macronutrients def-
icit soils.
To better comprehend the ongoing research on nutrients rich biochar
fertilizer, relevant literatures were reviewed to gauge research progress and
to identify the knowledge gaps for highlighting future research directions.
Earlier published reviews (El-Naggar et al., 2018, 2019) on biochars
included summary of its nutrients value with emphasis for potential fertil-
izer application. However, a review exclusively on the primary macronu-
trients (NPK) enrichment in biochars not yet reported properly and in
view of that covered as overarching theme of the current review article.
The specific goals of present review article are as follows:
1. Co-relation between the various production processes and enrichment

of primary macronutrients in biochars to determine suitable feedstocks,
process conditions, limitations and gaps
2. Mechanisms responsible for enrichment and transformation of primary
macronutrients forms in biochars is outlined and specified to under-
stand the nutrients release dynamics in soils
3. Specifying the contrasting research findings, shortcomings and associ-
ated negative outcomes based on diversified characteristics and perform-
ance biochars in soils
4. Discussion about biochars production and application in view of farm-
ers’ socio-economic aspects and scenario
5. Environmental concerns associated with the biochars application in soil
like potentially toxic constituents etc.
6. Future research directions regarding the best possible ways to produce
different types of nutrients enriched improved biochars as fertilizer
2. Production of nutrients enriched biochar-based fertilizer and

underlying transformation mechanisms
2.1. Methods for nutrients enriched biochar-based fertilizer production
Biochars fertilizer contains plant nutrients with potential to improve soil
fertility for better plant growth, development and productivty. Different
methods were documented regarding production of nutrients rich biochar
fertilizer. These methods (Figure 1) broadly classified into three categories:
(1) direct treatment, (2) pre-treatment, and (3) post-treatment.
2.1.1. Direct treatment method

The direct treatment method involves direct thermo-chemical conversion
of nutrient rich feedstocks into biochar fertilizer. Table S1 present charac-
teristics of biochar fertilizers produced from different nutrient rich feed-
stocks, which has potential for soil application. Almost all research studies
reported that, feedstocks inherently rich in nutrients undergo slow pyrolysis
leading to nutrients enrichment in biochar. Pyrolysis temperature were
dominant factor for nutrient enrichment in biochars due to varied volatil-
ization temperature of nutrients. For N enrichment in biochar, relatively
lower temperature range 300–400 C were more appropriate, whereas ele-
vated temperature of around 700 C was suitable for P and K (Biederman
& Harpole, 2013; Chan & Xu, 2012). Several biomass feedstocks such as
poultry litter, swine manure, anaerobic digestate, bone-meal, algae were
explored to produce nutrient rich biochars. In subsequent paragraphs,
Figure 1. Schema of different methods for production of biochars fertilizer.

pyrolytic methods to produce primarily N-P-K, P, and K enriched biochars

are discussed in detail.
Production of macronutrients rich biochars from human manure
(300–700 C), swine manure (400–800 C), poultry manure/litter
(400–600 C) constituted (in %) total N (2.4–4.8, 1.6–3.2, and 2.0–2.8), P
(5.4–8.1, 6.1–7.7, and 4.0–5.8) and K (1.9–2.6, 2.7–3.1, and 3.8–5.8) (Liu
et al., 2014; Subedi, Taupe, Ikoyi, et al., 2016; Tsai et al., 2012). Chlorella-
based microalgal residue (generated from cell disruption and dehydration
process) biochar contained remarkable high N (>10%) at 400 C and its
value decreased with increase in temperature (Chang et al., 2015). Lou et al.
(2017) studied spent mushroom substrate compost derived biochars rich in
total calcium (15.17–17.76%), K (3.16–4.45%), N (4.1–4.7%), and P
(1.19–3.42%). In contrast to above mentioned N, P and K containing bio-
chars, wastewater sludge biochars retained 1.2–3.3% N along with
4.47–6.17% sulfur (S), and 3.47–5.35% Ca (Hossain et al., 2011).
Bio-fermentation waste (Escherichia coli bacterial biomass) produced P
rich (8.4%) biochars at 600 C, which also contained about 8.6% N (Kim
et al., 2018). Zwetsloot et al. (2016) revealed production of P rich biochars
from bone waste at 350 C (12.71%) and 750 C (15.32%). Ma and
Matsunaka (2013) study about dairy cattle carcasses (mixture of skin, meat,
and bone) biochars (450 C) showed total P 10.8%. Yuan et al. (2015) also
highlighted about higher P in biochars produced from sewage sludge at
higher pyrolysis temperature (at 300 C-3.88% and at 700 C-4.92%),
whereas N showed reverse trend (6.1% at 300 C and 0.9% at 700 C).
K enriched biochars production from banana peduncle biomass waste
was reported by Karim et al. (2017). In place of widely explored slow pyr-
olysis method, thermal plasma fast processing with regulated temperature
varying processing time (3–9 min) were developed. Maximum total K con-
tent 25.85% in biochar was achieved at 7 min under argon plasma pyrolysis.
Roberts et al. (2015) reported about K enriched biochars from six different
species of seaweeds (brown seaweeds: Saccharina, Undaria and Sargassum;
red seaweeds: Gracilaria, Kappaphycus and Eucheuma) produced at 450 C
pyrolysis temperature. Biochars derived from red seaweeds contained rela-
tively higher total K (5.12–16.3%) than the brown seaweeds that also
retains total P up to 5.19%.
The average values of total NPK contents in biochars fertilizer of differ-
ent feedstocks are shown in Figure 2. Among different feedstocks, algal
waste derived biochars contains relatively very high total N with relatively
lower total C/N ratio of 3.79–8.78 (Zhou et al., 2019). However, organic C/
N were not extensively reported for biochars, which could have indicated
actual potential bio-availability of N in soils. Bone waste was found to be a
more suitable feedstock for the production of P rich biochars. Banana
Figure 2. Average values (calculated from Table S1 data) of total N, P, and K content (as elem-
ental %) in biochar fertilizer derived from various feedstocks.
peduncle was the better feedstock for K rich biochars production. Biochars
derived from bio-fermentation waste were rich in both N and P nutrients.
Cattle carcasses could be suitable feedstock for the production of biochar
rich in multiple macronutrients (NPK). However, a major knowledge gap
is total bio-available fraction of NPK in biochars are rarely studied and not
known properly. Few studies investigated about P and reported less water
soluble fraction compared to total content in biochars, which could be due
to its fixed chemical form and trapping in the particles (Song & Guo,
2012). Therefore, it is crucial that both total content and bio-available frac-
tion should be reported by researchers for nutrient rich biochars to identify
its actual potential for soil application.
2.1.2. Pre-treatment method

In pre-treatment method, the biomass is treated with nutrient rich materi-
als (e.g., nutrient rich minerals, chemical fertilizers and fertilizer industry
waste, animal waste) prior to thermo-chemical processing (high pyrolysis
temperature about 600 C) for production of biochar fertilizers (Joseph
et al., 2013). Research studies on pretreatment method are very limited.
Zhao et al. (2016) evaluated the influence of mixing phosphate fertilizers
(bone meal and triple super phosphate) with sawdust and switch grass bio-
mass on characteristics of biochars produced through slow pyrolysis
(600 C). The biochars contained high amount of P along with high C
retention and enhanced heavy metal stabilization in soils. During pyrolysis,
Ca(H2PO4)2 (present in triple super phosphate) transformed to Ca2P2O7,
which reacts with biomass C to form C–P and C–O–PO3. These reactions
helped in improving the C and P retention in biochars, and its application
as slow P release fertilizer. Mixture of banana peduncle biomass and phos-
phogypsum was treated through thermal plasma processing for 7 min for
production of K-S rich biochars. The biochars contained high contents of
K (4.2–12.7%) and S (13.3–17.8%), along with reduced bioavailable frac-
tions of toxic contaminants like fluoride, cadmium, lead etc. K and S were
mainly present as potassium sulfate (highly water soluble) in biochars,
which indicates the fast release of K and S from biochars for enhanced
plant uptake in soils (Karim, Kumar, Mohapatra, & Singh, 2019). Biochar
fertilizers were produced through thermal treatment of K rich banana ped-
uncle biomass and P rich effluent sludge mixture (Karim, Kumar,
Mohapatra, Singh, & Panda, 2019). Biochars produced through plasma
processing (1200–1500 C) contained more total P (11.81%) and K (21.9%)
contents in comparison to slow pyrolysis performed at 700 C (4.2% P,
11.5% K). It was due to the comparatively elevated temperature during
plasma processing. Bioavailable P fractions were 0.6 and 0.56% in biochars
produced via plasma processing and slow pyrolysis respectively. Overall, all
above studies demonstrated that pre-treatment method could be a suitable
way for the production of designer biochar fertilizers such as biochars
enriched in multiple macro/micro nutrients for application in specific soil-
plant systems.
2.1.3. Post-treatment method

In post-treatment method, biochars were treated with a nutrient rich source
(e.g., wastewater, waste gases) at ambient conditions or temperature regu-
lated conditions to prepare nutrient enriched biochar fertilizers (Joseph
et al., 2013). Research studies have been focused on the utilization of bio-
chars as the low-cost sorbent for nutrient recovery from wastewater
(Antunes et al., 2017; Gai et al., 2014; Kizito et al., 2015; Shepherd et al.,
2017; Zhang & Wang, 2016). Post saturation, the nutrient loaded biochar
were proposed to be used as fertilizers in soils. It can help in reducing
nutrient pollution and eutrophication along with promoting
nutrients cycling.
Biochars produced (300–600 C) from various feedstocks were evaluated
for nutrient (Phosphate and Ammonium) sorption from liquid wastes and
presented in Table S2. Diverse feedstocks used for biochars were anaerobic
digestate sewage sludge, bamboo, corn waste, cotton stalks waste, grapevine
cane, greenhouse waste, hardwood shavings, municipal waste, oak wood,
saw dust, rice husk, corn straw, wheat straw, peanut shells, water treatment
sludge, sugar beet tailings, wood waste, and Thalia dealbata. The liquid
wastes used as nutrient rich sources for sorption were included urine, swine
manure anaerobic digestate liquid/slurry, biogas fermentation liquid, and

wastewater. Several researchers also evaluated pyrolysis of feedstock/biomass
pretreated with Magnesium (Mg) solutions to produce Mg rich biochars for
enhancement of its phosphate adsorption capacity (Cui et al., 2016; Fang
et al., 2015; Yao et al., 2011a, 2013). Among biochars, Hardwood shavings
biochar (300 C) exhibited lowest sorption capacity both for ammonium
(5.3 mg/g) and phosphate (0.24 mg/g) (Sarkhot et al., 2013). Municipal waste
biochar showed relatively highest ammonium sorption capacity (137.3 mg/g)
(Takaya et al., 2016). Biochar produced at pyrolysis temperature of 450 C
was more suitable for higher ammonium sorption capacity, further increase
in pyrolysis temperature to 650 C decreased its sorption capacity.
Ammonium adsorption capacity of biochars was found to be highly depend-
ent on the reactions with oxygen functional groups, CEC, compared to sur-
face adsorption (physisorption) (Mukherjee et al., 2011; Takaya et al., 2016).
During sorption process, MgO and P2O5 present in biochars are released as
Mg2þ and PO43 into solutions, which combines (at pH range 7–11) with
NH4þ to form Struvite (MgNH4PO4) precipitation (Equations (1) and (2)).
MgO þ 2NH4 þ þ H2 O ! Mg2þ þ 2NH3 :H2 O (1)
Mg2þ þ NH4 þ þ PO3
4 þ 6H2 O ! MgNH4 PO4 :6H2 O (2)
The availability of more polar functional groups (ACOOH, AOH, CAO)
in low temperature (300 C) biochars is responsible for urea sorption (from
human urine) capacity, whereas high temperature biochars (500–600 C)
showed better adsorption capacity, if urea concentration gradient is high
(above 4000 mg/L in urine) due to diffusion of urea in the biochars with
high surface area. The plant germination experiments further indicated that
exhausted biochar could be used for improving soil productivity (Zhang
et al., 2015). In a study (Zhang et al., 2017), S rich biochar (Sulfachar) was
prepared by using biochar for capturing toxic hydrogen sulfide gas from
biogas emissions stream, which generated during anaerobic digestion of
organic waste. The Sulfachar collected large amount (36.5%) of S in both
elemental and sulfate form. In addition, adsorbed S was in plant available
form and Sulfachar treated soils showed increase in the uptake of S and
other nutrients in corn plant.
Non woody biomass and high pyrolysis temperature (600–800 C) were
found more favorable showing high adsorption capacity for phosphate.
Corn waste biochars have higher (225 mg/g) phosphate sorption capacity
(Fang et al., 2014). After modifying corncob biochars by enriching Ca-Mg,
the sorption capacity increased up to 326.62 mg/g (Fang et al., 2015).
Montmorillonite (Chen et al., 2017) and ocher (Shepherd et al., 2016) min-
erals were used with biomass to produce biochar composites to provide
various surface-active sites for effective adsorption. Adsorption of
phosphate mainly occurred through electrostatic attraction and bonding

with metal cations like Ca2þ, Mg2þ, and Fe3þ present in biochars (Chen
et al. 2017; Fang et al., 2014, 2015; Takaya et al., 2016; Veni et al., 2017)
and ion exchange with hydroxyl groups oxygen rich functional groups (car-
bonyl, carboxyl, hydroxyl, and methoxyl) present in biochar surfaces
(Sarkhot et al., 2013). Precipitation and retention of phosphate as brushite
(CaHPO3) mineral form also identified in biochars (Marshall et al., 2017).
The presence of Mg nanocrystals and/or MgO nanoparticles on biochar’s
surface could further enhanced its phosphate sorption capacity by provid-
ing more active sites and P precipitation as magnesium phosphates (Yao
et al., 2011a, 2013). Presence of Ca in biochar does not have a prominent
effect on phosphate sorption through precipitation as calcium phosphate. It
could be due to the calcium existence as less water-soluble calcite mineral
and entrapment inside the biochar structures, which limited the release of
Ca from biochars into solution due to chemical precipitation (Cao &
Harris, 2010; Yao et al., 2011b). Desorption experiment revealed 97% of
phosphate recovery from biochars mostly as calcium phosphate by modify-
ing solution pH 4 (Marshall et al., 2017). Phosphate effectively desorbed
from biochar in both acidic (75–88%) and neutral pH (57–78%), which
indicated reversible sorption process (Kizito et al. 2017). In pot culture
experiments, the post-sorption biochar exhibited improved P content in
soil and plant (Marshall et al., 2017). P was present in bioavailable form in
biochars. Due to this, post-sorption biochar also improved the germination
and growth of grass seedlings (Yao et al., 2013).
Nutrient binding capabilities of the specific biochar type are highly
influenced by its properties, including pH, surface area and ion-exchange
capacities (Ding et al., 2016). The mechanisms for biochars binding cap-
acity of polar and non-polar compounds are mainly due to hydrophobic
bonding, a-a electrons donor interactions as a result of fused structures
and the weak H bonding (Conte et al., 2013). The process of sorption
and desorption of nutrients in biochars controls its release in soil solu-
tion and bioavailability. The nutrient (especially adsorbed nutrients)
release from biochar through desorption process is heavily affected by
soil type, feedstocks, process of formation and biochar application rates.
The soil pH, organic matter, and activity of cations (Al3þ, Fe3þ and
Ca2þ) that interact with nutrients (phosphate and nitrate) in biochar
also influences their bioavailability in soils (Xu et al., 2014). The phys-
ical characteristics, organo-mineral complexes and various interactions
between biochar and soil also have a strong impact on the dynamic of
release and maintenance of nutrients. Nutrient binding and its release
are mainly due to the following mechanisms (Schmidt et al., 2017; Xiao
& Pignatello, 2016):
1. Ionic bonding i.e. direct positive ion bonding, micro sites negative
charge, surface functional groups or precipitated metal or pyrolytic
oxides tars
2. Water bridges between dissolved ion hydraulic shells and systems, like
oxygen-generated organic groups on biochar surfaces
3. Covalent bonding/chemical bonding involves sharing of electron pairs
among ions on the biochar
4. Physical entrapment (minerals entering the pore spaces)
5. Intra-molecular hydrogen bonds between the electron rich proton
acceptors and donors on the surface of biochar
6. Van-der-Waals interactions between the hydrophobic characteristics of
an organic molecules and the organic poly-aromatic components of
the biochar
2.2. Nutrients transformation mechanisms in biochar fertilizer production

During pyrolytic decomposition of biomass constituents, nutrient enrich-
ment in biochars mainly takes place because of the formation of thermally
resistant form and volatilization of other compounds (Domingues et al.,
2017). Minerals form of nutrients in biochars mainly determined its avail-
ability to plants. In addition, the occurrence of nutrients on the surface
and inside the biochar particles can also influence its plant availability
(Keiluweit et al., 2010). In previous studies, researchers have mainly studied
the nutrients (NPK) transformation during biochar production through dir-
ect treatment method, explained in subsequent sub-sections. Studies related
to nutrients transformation in biochar produced through pre-treatment and
post-treatment methods are scarce.
2.2.1. N transformation
Several studies had documented the mechanisms for transformation of N
species from biomass to biochars, which was influenced by biomass com-
position, pyrolysis atmosphere, and temperature. Loss of N from biomass
feedstock mainly initiated at pyrolysis temperature of 150 C, due to the
degradation of hemicellulose and cellulose fractions. The degradation fur-
ther intensified gradually with the rise in temperature from 250 to 500 C,
which causes major loss of nutrients due to volatilization (Tian et al.,
2017). Transformation of N due to the pyrolysis and its dominant forms
present in the biochar fertilizers is shown in Figure 3. Tian et al. (2014)
examined the N speciation in sewage sludge biochars produced at
150–800 C through pyrolysis. Raw sludge mainly consisted of proteins,
pyridinic, pyrrolic, and amine forms of N. The pyrolysis of sludge pro-
duced biochar mainly rich in heterocyclic-N derived from pyrrolic and
Figure 3. N species transformation due to pyrolysis and its dominant forms present in the bio-
char fertilizers.
pyridinic N of raw sludge. In addition, the sludge biochars contained

amine, nitrile, and other organic N compounds. Transformation of N
forms also studied from rice straw and its biochars (Liu, Tan, Zhang, et al.,
2018). Rice straw found to be dominantly composed of proteins (70%) and
remaining N are present as alkaloids, amines, and ammonium. In its bio-
char, pyrolysis process changed the N species to organic (25–44% pyrrole,
12–23% pyridine, 4–12% amino, and below 10% nitrile), and inorganic
forms (NH4þ, NO3, and NO2). Liu, Tan, and Ye (2018) investigated the
N speciation and transformation in wheat straw biochars produced at dif-
ferent pyrolysis temperature ranged 300–800 C using isotope tracer and
XPS analysis. This study concluded that the wheat straw and its biochars
produced at temperature range 300–500 C contained similar N compounds
i.e., alkaloid, free amino acid, protein, and NH4þ. However, gradual trans-
formation of these N species formed additional N compounds mainly
amino, pyridine, pyrrole, quaternary N, NH4þ, NO2, and NO3 in bio-
chars. A study by Tian et al. (2017) concluded retention of N is relatively
higher in the CO2 atmosphere than N2 because it can inhibit the formation
of volatile species such as NO, NH3, HCN compounds etc. Thus, the CO2
atmosphere and lower pyrolysis temperature (Preferably around 300 C)
generally favored the preparation of N enriched biochar.
2.2.2. P transformation
During pyrolysis of biomass, organic P (phosphate monoesters, mostly
phytic acid) compounds transformed into inorganic P oxides and metal
(Ca, Mg, Fe) phosphates (Dai et al., 2016). The volatilization of P mostly
started above 250 C, thereafter increase in pyrolysis temperature caused
changes in the proportion of organic, inorganic, and volatile P compounds.

The enriched P fraction in biochar mainly constitutes of inorganic P frac-
tion due to the thermal transformation of organic P into inorganic com-
pounds. Conversion of organic P species into inorganic species is
comparatively higher in N2 presence than CO2. Above 700 C pyrolysis
temperature, inorganic P mostly transformed into volatile species leading to
its loss from biochar (Tian et al., 2017).
Several researchers investigated the speciation and transformation of P
during pyrolysis in sewage sludge biochars. Huang and Tang (2015)
observed the raw sludge predominantly contained orthophosphate and
long-chained poly-phosphate. The pyrolysis transformed these P species
into relatively less extractable forms i.e. pyro-phosphate and short-chained
poly-phosphate in biochar. The extractability of P substantially reduced
with increased pyrolysis temperature (250–600 C) to produce biochars.
Another study by Qian and Jiang (2014) explained the impact of fast pyr-
olysis temperature range (400–800 C) and gaseous conditions (N2, CO2,
and air) on P content in sewage sludge biochar. They found that pyrolysis
temperature predominantly affects the formation of P-species in biochars
and not the gaseous atmosphere. Moreover, they elucidated (based on XRD
and solid-state 31P NMR) the pathway for formation of varied P species in
sewage sludge biochars. P mainly presents as organic and inorganic P
(orthophosphate and pyro-phosphate) in sewage sludge. However, among
them, orthophosphate constitutes major proportion (75%) of sewage sludge.
The formation of pyrophosphates in biochars is dominant around
400–600 C pyrolysis temperature due to dehydration of M2(HPO4)x (or
M(H2PO4)x) present in sludge. In contrast, pyro-phosphates formation
largely declined and metal (Ca, Mg) phosphates or P bearing minerals
(Stanfieldite-Ca4(Mg, Fe)5(PO4)6) dominated at elevated temperature
around 700–800 C. This study used sequential extraction process that
includes NaHCO3, NaOH and HCl extractants to predict the availability of
different P forms. The soluble orthophosphate, pyro-phosphate and weakly
bound forms of P extracted in the solution using NaHCO3. Adsorbed phos-
phate anions on positively charge metals Al/Fe and some insoluble metal
phosphate compounds extracted in the NaOH solution. Whereas, insoluble
Ca/Mg phosphate compounds, P bearing minerals and P trapped in the lat-
tice of minerals mostly extracted using HCl solution. As the pyrolysis tem-
perature rises, the water-soluble P transformed into NaHCO3-P, NaOH-P
and HCl-P with decreasing solubility. P speciation in biochars produced
from two different types of sewage sludge samples under varied thermal
processing conditions was investigated (Steckenmesser et al., 2017). First
sample was sewage sludge formed through precipitation method (using
iron chloride) for treatment of industrial wastewater. Second sample is the
sewage sludge formed by use of biological precipitation method for rural

wastewater treatment and post-stabilization using aluminum sulfate. Both
sewage sludge samples were thermally treated at low temperature ranged
400–500 C. Mineralogical analysis (using XRD) of biological sludge not
exhibited any presence of crystalline P compounds, which could be due to
organic polyphosphates and amorphous P compounds as major constitu-
ents. Vivianite (Fe3(PO4)2.8H2O) and lipscombite (Fe3(PO4)2(OH)2) miner-
als were evident in industrial sewage sludge. The evaluation of total P
fractionation showed that the chemical sludge contains 41.5% Fe-P (NaOH
extract), 20% Al-P (NH4F extract), 17% Ca-P (H2SO4 extract), and 2.5%
water-soluble extract. On the other hand, biological sludge constitutes of
47.5% Al-P, 17% Fe-P, 11% Ca-P, and 3.3% water soluble P.
The P transformation in poultry litter biochars produced through slow
pyrolysis (300–600 C) was researched by Li et al. (2018). Raw poultry litter
comprised of organic (phospholipids, phytates, and nucleic acids) and inor-
ganic P species i.e. CaHPO4, Ca3(PO4)2, and Ca8H2(PO4)65H2O. Pyrolysis
specifically above 400 C drastically declined the organic forms of P in bio-
chars due to its decomposition and subsequent transformation into inor-
ganic forms. Initially, organic P (water-soluble and NaOH extractable
fraction) converted to inorganic pyro-phosphates and other poly-phos-
phates, which further at higher pyrolysis temperature changed dominantly
to orthophosphates. The poly-phosphates to orthophosphates conversion
were facilitated by availability of metal ions at higher pyrolysis temperature.
The low labile and water-insoluble hydroxyapatite and oxyapatite minerals
(HCl extractable) formed in biochars. In addition, surface precipitates and
complexes of P on calcium carbonate and Fe/Al oxides (NaHCO3 and
NaOH extractable), which are moderately labile are marginally present in
biochars. These changes in P speciation due to pyrolysis transformed the
readily labile and water-soluble P fraction in poultry litter to less labile and
mobile fractions in biochars, which could be beneficial to restrict its loss
through leaching and run off, and thus enhancing its plant availability.
Transformation of P in biochars derived from peanut husk, wheat and
maize straw through slow pyrolysis (300–600 C) was studied by Xu,
Zhang, Shao, and Sun (2016). Water-soluble P forms are dominant in bio-
chars produced at low temperature (up to 400 C), which are transformed
into more labile form (400 to 600 C) and ultimately to stable form with
increasing pyrolysis temperature (600 to 800 C). During pyrolysis, above
200 C organic P (ortho-monoester) fractions changed into inorganic
forms (Ortho and Pyro-phosphate). Sodium pyro-phosphate (Na4P2O7) and
monetite (CaHPO4) were major species present in biochars, whose propor-
tions increased with pyrolysis temperature. The other stable minor forms
of P in biochars as detected by Solid state 31P NMR are Crandallite
Figure 4. P species transformation due to pyrolysis and its dominant forms present in the bio-
char fertilizers.
(CaAl3(OH)5(PO4)2), Wavellite (Al3(OH)3(PO4)25H2O), Hydroxyapatite

[Ca5(PO4)3OH], Sodium pyro-phosphates [Na2H2P2O7], Tri-sodium di-
phosphate [Na3HP2O7], Senegalite [Al2(OH)3(PO4)H2O], Variscite
(AlPO42H2O), Di-calcium phosphate dihydrate (CaHPO42H2O).
The variations in P speciation in biochars produced from solid manure
digestate of biogas plant 300–1050 C pyrolysis temperature and its effect
on P availability in soils were investigated (Bruun et al., 2017). P was dom-
inantly present as calcium phosphates in the solid digestate. The elevated
pyrolysis temperature transformed the less thermally stable forms such as
struvite and magnesium phosphates into high thermally stable apatite with
increased crystallinity even at above 1050 C. A study on biochar derived
from bone meal also revealed that with increase in pyrolysis temperature
the organic P transformed into crystalline calcium phosphates (Zwetsloot
et al., 2015). Research work undertaken by Uchimiya and Hiradate (2014)
on biochar produced from plant and manure also concluded that increase
in pyrolysis temperature gradually converts the organic phytate phosphate
into pyro-phosphate and finally to orthophosphate at further elevated tem-
peratures. On basis of above studies, scheme of P species transformation
due to pyrolysis and its dominant forms present in the biochar fertilizers is
presented in Figure 4.
2.2.3. K transformation
The transformation of K compounds into biochars initiated above 250 C
pyrolysis temperature. The water-soluble fraction of K usually transformed
into organic compounds up to 500 C; whereas between 500 to 700 C,
silicate and volatile compounds such as K2SO4, KOH, and KCl dominated
in biochars. Furthermore, increase in temperature above 700 C leads to
loss of K from biochars through decomposition and volatilization of K-
minerals (Tian et al., 2017). Non-woody plant wastes mainly constitute of
K containing minerals specifically kalicinite and sylvite, present both on the
surface and inside voids of biochar particles. Prakongkep et al. (2015)
reported the minerals form of nutrients in biochars, produced through
slow pyrolysis from different tropical plant wastes i.e. corncob, lemon peel,
soybean cake, bamboo wood, eucalyptus wood, coconut shell, coconut fiber,
rice husk, sugar palm fiber, oil palm fruit, coffee waste, tamarind wood,
and durian shell. Most of these biochars predominantly contain calcite
(CaCO3) and kalicinite (KHCO3) minerals. Other nutrients containing min-
erals were also present in biochars such as sylvite (KCl), archerite
(KH2PO4), struvite (KMgPO4. 6H2O), chlorocalcite (KCaCl3) and pyroco-
proite (K2MgP2O7). Kalicinite is highly water-soluble mineral and thus con-
tain P in plant available form. Karim et al. (2017) also reported the
formation of kalicinite mineral in banana peduncle biochars. Formation of
Kalicinite in biochars might be through following mechanism. K mainly
exists in biomass as a dissolved salt in ionic form. Biomass pyrolysis above
400 C mainly forms KOH and KO2 due to H2O presence in volatiles/bio-
oil (Cao et al., 2016). Subsequently, KO2 may react with C or CO to form
K2CO3, which reacts with H2O molecules and CO2 to form KHCO3 (kali-
cinite mineral). Possible reactions that lead to formation of KHCO3 during
biomass pyrolysis are as follows (Equations (3)–(7)).
2K þ 2H2 O ! 2KOH þ H2 (3)
2KOH þ 2K ! 2K2 O þ H2 ðabove 400 CÞ (4)
4KO2 þ 3C ! 2K2 CO3 þ CO2 (5)
2KO2 þ CO ! K2 CO3 þ O2 (6)
K2 CO3 þ H2 O þ CO2 ! 2KHCO3 (7)
Presence of above-mentioned minerals and their dominance in biochars

strictly depends on the composition of biomass feedstocks (Figure 5).
These K-minerals are highly water-soluble and thus highlight the potential
of biochars as K-fertilizer substitute for synthetic chemical fertilizers.
Among biochars, durian shell, fruit peel, and fiber waste biochars were
relatively richer in K minerals, which indicate its more applicability as K-
fertilizers. Overall, application of these K rich biochar fertilizers could be
appropriate for sustainable organic agriculture.
Figure 5. K species transformation due to pyrolysis and its dominant forms present in the bio-
char fertilizers.
2.3. Nutrient binding mechanisms and its release

When applied to the soil, the total amount of nutrients present in biochars
necessarily does not indicate the actual amount that is released (Camps-
Arbestain et al., 2015; Singh et al., 2017). Compared to the original feed-
stock, nutrients (particularly N) in biochar are usually less bio-available.
El-Naggar et al. (2015) reported that out of 15.6% N in the original feed-
stock, only 4.5% N was retained in biochar. Higher total C/N ratio in bio-
char material leads to N immobilization and reduced bioavailability in soils
(Arif et al., 2017; Riaz et al., 2017), which could be the reason that biochar
has not contributed to improve the N crop budget (Hangs et al., 2016;
Nguyen et al., 2017).
For agricultural systems, biochars could also be a valuable method specific-
ally for P recycling. As total P amounts of animal manure produced annually
surpass world P fertilizer output, the thermochemical conversion of manure
into biochar could be a viable alternative to mineral P fertilizers (Steinfeld,
2006). P recycling from organic residues/wastes has environmental advantages
(e.g., water bodies protection) and can also provide a continuous P source for
soils (Dai et al., 2016; Manolikaki et al., 2016; Wang et al., 2015). However, the
water soluble fractions of P in biochars are reduced compared to raw biomass
due to the bonding of P to multivalent metal cations during pyrolysis (Dai
et al., 2016; Wu et al., 2012). Generally, P amount in wood-derived biochars
are very less and not bioavailable in soils, thus not suitable as a P fertilizer.
Whereas, P-rich biomass (e.g., animal manures) derived biochars contains
higher P and showed increase in its bio-availability in soils. Therefore, these
biochars could be suitable as P fertilizer (Glaser & Lehr, 2019).
K mainly exists in plant available forms in almost all biochars, which was
due to its presence as water-soluble minerals (Ippolito et al., 2015). Although
above said biochars possessed high total N/P/K contents, the availability of
nutrients for plants depends on its chemical speciation, and need further
detailed research. Nutrients released from the biochar into the solution
depends strongly on the feedstock (Nelson et al., 2011). Furthermore, the
release of nutrient varies based on the sorption capacity of the element.
Leaching trials to study the release of nutrients from hardwood biochar car-
ried out by Angst and Sohi, (2013) reported a progressive K supply over the
growing season compared to rapid release of K. Therefore, while managing
plant nutrient supply through biochar application, the difference in the release
patterns of each of the nutrient and plant type needs proper consideration.
Application of above discussed macro-nutrients rich biochars could be
more appropriate for degraded and/or macronutrients deficit soils. For
instance, calcareous soils in arid zones have common issues of low
nutrients (specifically P) availability and organic matter (Abbaszadeh-
Dahaji et al., 2020; Bityutskii et al., 2017; Kumari et al., 2018). The decline
in organic matter adversely impacts the supply of nutrients in soil (Naeem
et al., 2017). Post biochar applications, the soil total N, available P and K
has been increased to 1.2–1.4 g/kg, 1.70–2.65 mg/kg, and 1.52–2.59 mg/kg,
respectively. The highest increase in availability of NPK in soil reported
with 2% biochar application rate. The findings also showed that pyrolysis
temperature increased the P/K availability in soils (Karimi et al., 2020).
3. Potential of biochars fertilizer for soil application

Relevant research studies are explained herewith that investigated the
potential of nutrients rich biochars (pyrolytic temperature 300–550 C) for
soil nutrients replenishment and improved plant growth (Table 1).
Limitation of these studies were high non-uniformity, and execution
through lab scale greenhouse pot experiments with different biochars and
soil-plant systems. Nutrient rich biochars showed mixed results and no spe-
cific trend about the influence of pyrolytic temperature and feedstocks on
efficacy of biochars for improving nutrient availability in soils and plant
growth was observed. Animal manures and sewage sludge derived nutrient
enriched biochars application in soils were commonly studied. Application
of NPK enriched poultry litter biochars increased the total N concentration
in sub-tropical acidic soil and foliar N in macadamia orchard plant leaves.
It also improved the P availability in that soil (Bai et al., 2015). Zolfi-
Bavariani et al. (2016) also reported enhanced P availability in calcareous
soil after application of poultry manure biochar. Treatment of clay loam
soil with poultry manure biochar increased the dry weight, P and K content
of lettuce (Lactuca sativa) and corn (Zea mays L.) (Gunes et al., 2015).
Abbasi and Anwar, (2015) research showed poultry manure biochars appli-
cation significantly increased N uptake, growth and biomass yield of wheat
(Triticum aestivum L.) in loam soil. The post-harvest examination of soil
also showed improvement in its total N content and C/N ratio than con-
trol. Application of nutrient rich cow manure biochar in sandy soil
increased the pH, water use efficiency, hydraulic conductivity, bio-available
P, and total N along with significant improvement of maize grain yield
(Uzoma et al. 2011). Subedi, Taupe, Pelissetti, et al. (2016) reported treat-
ment of manure (poultry litter and swine manure) biochars in silt loam
and sandy soils showed significant increase in yield, shoot matter dry
weight along with enhanced uptake of NPK nutrients in ryegrass plant.
However, in another study application of swine solid biochars in Mollisol
and Entisol soils showed negative impact i.e. increased in the loss of dis-
solved P and K (Novak et al., 2014).
Wastewater sludge biochar treatment of chromo-sol soil significantly
enhanced the N and P availability and increased the yield of cherry toma-
toes (Hossain et al., 2010). Application of sewage sludge biochar in tropical
clay soil significantly improved nutrient availability, uptake and growth of
maize plants (Gwenzi et al., 2016). Sewage sludge biochars also increased N
and P availability in oxisol soil and improved the growth of radish
(Raphanus sativus L.) plant (Sousa & Figueiredo, 2016). Song et al. (2014)
reported application of sewage sludge biochar in acidic soil improved
growth, dry matter, and yield of garlic (Allium sativum L.). This study
reported the heavy metal (Cu and Zn) accumulation in bulbs and roots of
garlic plants, which underscores that application of sewage/wastewater
sludge biochars for agriculture could pose risk for human health.
Application of P rich biochars produced from cattle carcasses and its appli-
cation to acidic soil significantly improved P availability leading to better
growth and dry matter of corn (Zea mays L.) plant (Ma & Matsunaka,
2013). Incorporation of K enriched biochars (prepared by treating biochars
with anaerobically digestate slurry) with slow release fertilizer slowed down
the leachability of K, but showed lower lettuce yield than commercial slow
release fertilizer (Oh et al., 2014). The decrease yield was probably due to
elevated pH of soil after biochar treatment. Research studies extrapolated
the application rate for biochars to be very high (up to 270 t/ha), which
seems to be less practically feasible keeping in view the regular requirement
of at least twice amount of dried feedstock, high production cost and other
negative effects like possibility for inducing long term alkalinity and limit-
ing nutrient availability in soils. Therefore, future nutrient enriched biochar
research is essential to focus more on high availability feedstock (e.g., for-
estry waste, crop residues), identify practically feasible application methods,
application in appropriate soil type (e.g., degraded, mine contaminated, and
forest soil) and plants (e.g., forestry and horticultural).
Table 1. Effect of nutrients enriched biochars fertilizer on soil fertility and plant growth.
Pyrolysis Quantitative detail on change “from
Biochars temperature Soil type Plant Type of study Biochar dose control to biochar treatment” References
riPoultry manure biochar 300 C Clay loam Lettuce (Lactuca Greenhouse pot 10 g/kg soil (25 t/ha) Lettuce: 1.63 g/kg P to 5.32 g/kg; 43.57 g/ Gunes
sativa) and Corn experiment kg K to 75.09 g/kg; increased lettuce et al. (2015)
(Zea mays L.) plant dry weight from 31.6 to 445.5 g
Corn: P 0.97 to 2.93 g/kg; K 52.65 to
66.56 g/kg; corn dry weight from 1023
to 1374 g
Poultry manure biochar 300 C Calcareous soil Pot 150 days 2% Soil: enhanced the availability of P from Zolfi-Bavariani
incubation 3.54 to 125 mg/kg in soil et al. (2016)
experiment
Biochars (water- 300 C Decomposed Lettuce Greenhouse pot 67.5 mg/ha Soil: increase available P (P2O5) 20.97 to Oh et al. (2014)
treatment sludge) granite soil (Lactuca sativa) experiment 71.75 mg/kg; Increase potassium from
(WS) treated with (sand at 91.8%) 0.02 to 0.15 cmol/kg; increase plant
anaerobically yield from l 2.28 to 34.22 t/ha
digestate slurry
Sewage sludge biochar 300 C Oxisol Radish (Raphanus Green house pot 50 g/kg Soil: increase P from 0.39 to 100.31 mg/kg; Sousa and
sativus L.) experiment 35 days increase K from 18 to 34.25 mg/kg; Figueiredo
increase Nitrate from 7.32 to 41.91 mg/ (2016)
kg; increase plant dry weight from 0.2
to 3 g/pot
Sewage sludge biochar 300 C Tropical Maize (Zea mays L.) 49 days pot 15 t/ha Increased total dry biomass weight from Gwenzi
clay soil experiments 20 to 80 g/pot et al. (2016)

Poultry litter biochar 400 C Silt loam and Ryegrass (Lolium 150 days Pot (1.5 kg) Seeds were sown (0.2 g/ Silt loam soil: increased plant shoot dry Subedi, Taupe,
sandy soils multiflorum L.) experiments in pot given the seed weight from around 13 to 18 g/pot Ikoyi, et al.
controlled chamber. rate of 10 g m2 ) Sandy soil: increase plant shoot dry (2016)
weight from 6 to 9 g/pot
Swine manure biochar 400 C Silt loam and Ryegrass (Lolium 150 days pot (1.5 kg) Seeds were sown (0.2 g/ Silt loam soil: increased plant shoot dry Subedi, Taupe,
sandy soils multiflorum L.) experiments in pot given the seed weight from around 13 to 16 g/pot Pelissetti,
controlled chamber rate of 10 g m2 Sandy soil: increased plant shoot dry et al. (2016)
weight from 6 to 8 g/pot
Swine solid biochars 400 C Mollisol 25-day laboratory 3.84 g/kg (ca.10 t/ha) Entisol: cumulative DP % loss increase Novak et al. (2014)
and incubation pot experiments from 1.44 to 6.03; cumulative DK% loss
entisol from increase from 6.10 to 34.19
Mollisol: cumulative DP % loss increase
from 0.30 to 0.61; cumulative DK %
loss decrease from 0.88 to 0.74
Cattle Carcasses 450 C Acidic soil Maize (Zea mays L.) 40 days pot plant 1.6 g biochar/2.4 kg Biochar improved dry matter of plant Ma and Matsunaka
biochar growth experiments in soil pot 25.6 g/pot compared to 22.0 g/pot for (2013)
CRITICAL REVIEWS IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY
glasshouse superphosphate; increased P plant

uptake to 38.6 g/pot than 36.9 g/pot
for superphospate
450 C 270 t/ha Song et al. (2014)
19
(continued)
20
Table 1. Continued.
Pyrolysis Quantitative detail on change “from
Biochars temperature Soil type Plant Type of study Biochar dose control to biochar treatment” References
Sewage sludge Local Slightly Garlic (Allium 40 days pot Compared to control, biochar increase
biochars acidic (6.3 pH) sativum L.) experiments 30% dry matter yield of garlic
soil of Sanghai,
China
Poultry manure 500 C Loam soil Wheat (Triticum Greenhouse pot 30 t/ha Increase in dry matter yield of wheat from Abbasi and
biochar aestivum L.) experiment upto 11.7 to 27.0 g/pot, grain yield increase Anwar (2015)
plant maturity from 7.9 to 18.9 g/pot
A. A. KARIM ET AL.
Poultry litter 500 C Subtropical Macadamia Finding of 5-year 40 kg per tree; 10 t/ha Increased soil TN from 0.45% to 0.55%, Bai et al. (2015)
biochar acidic soil (Macadamia integrifolia L.) field study dry weight slightly high foliar N (1.34%) in biochar
treated than control 1.29%
Cow manure 500 C Sandy soil Maize (Zea mays L.) 85 days greenhouse 15 t/ha Increased maize grain yield by 150 % as Uzoma et al. (2011)
biochar pot experiments compared with the control; increased N
from 0.45 to 1.50 g/kg in soil
Sewage sludge 500 C Tropical clay soil Maize (Zea mays L.) 49 days pot 7.5 t/ha Maize growth increased by 42 % and total Gwenzi et al. (2016
biochar experiments biomass by 270% compared to control

Wastewater 550 C Chromosol Cherry tomato Glasshouse pot 10 t/ha Biochar treatment produced 64% greater Hossain et al. (2010)
sludge biochar (Lycopersicon experiments (16 wks) yield compared to control treatment
esculentum)
3.1. Contradictory findings related to biochar application in soil

Several biochars studies have reported conflicting findings that illustrate
positive, negative or neutral impacts on the soil quality (Beiyuan et al.,
2017; Yang et al., 2019). Biochar derived from various feedstocks showed
different potential toward improving fertility of sandy and sandy loam soils
(El-Naggar et al., 2018), where rice straw biochar significantly increased the
content of N, available P, exchangeable cations, and CO2 efflux compared
to the wood and grass biochar. The results strongly depend on the type of
biochar produced from five different feedstocks (Alburquerque et al., 2014).
Authors also stated that soils treated with wheat straw and pine wood chip
biochar had a greater field potential than soils treated with other kinds of
biochar. The contrasting findings of such studies can be partly due to fac-
tors like the soil type and experimental arrangement. However, the differ-
ence in composition of each type of biochar is one of the key reasons of
contrasting results (El-Naggar et al., 2019; Rajapaksha et al., 2019). Any
biochar generated using a specified production process (e.g., pyrolysis, gas-
ification, hydrothermal carbonization), at a specified temperature and with
or without any modifications will produce a unique biochar (Igalavithana
et al., 2017; Yoo et al. 2018). Without specifying production conditions and
biochar composition it would be very problematic to generalize the func-
tion of biochar on different usages. Some papers have shown variations in
properties of biochar and soil functions on the basis of type of feedstock
and the production condition (Agegnehu et al., 2017; Ding et al., 2016;
Igalavithana et al., 2017). The application of biochar can increase the avail-
ability of soil water (Ma et al., 2016), water holding capacity (Mohamed
et al., 2016), soil aeration (Cayuela et al., 2013), soil organic C content (El-
Naggar et al., 2019), soil microbial biomass and activity (Igalavithana et al.,
2017), enzymatic activity (Awad et al., 2018), and nutrient retention and
availability, which results in fewer fertilizer needs and reduces the leaching
of nutrients (El-Naggar et al., 2019). However, some studies reported
reduce nutrient availability (Karer et al., 2013 Hussain et al., 2017) and
decrease in crop productivity following biochar application (Schmidt et al.,
2015), which could be related to a decrease in plant nutrient uptake or
mineralization of soil C (Ippolito et al. 2012). Biochar produced at high
pyrolytic temperatures (around 600 C), for example, may adsorb plant
nutrients, thereby limiting plant uptake. Moreover, the negative priming
effect (PE) induced by biochar nutrient adsorption may also lead to reduc-
tion in the availability of nutrients for plant uptake in low organic carbon
soils (Kuppusamy et al., 2016).
Biochar application for amelioration of saline/sodic soils has also been
studied, which reported contrasting results. Some studies confirmed the bio-
char application reduced the exchangeable sodium percentage (ESP) and
Sodium Adsorption ratio (SAR) in saline and sodic soils (Amini et al., 2016;
Luo et al., 2017; Sun et al., 2016; Wu et al., 2014). The different mechanisms
responsible for that could be biochar application releases exchangeable Ca to
replace Na in soil solution, organic C in biochar increases the surface charge
density leading to comparatively more Ca adsorption in soil colloids than Na,
enhancement in soil porosity due to biochar may increase the Na leaching
and decrease its concentration from soil solution (Dahlawi et al., 2018).
Generally, salt affected soils are low in NPK, which could be due to reasons:
(1) enhanced organic matter solubility increases the mineralized nutrients
leaching and loss, and (2) salinity and sodicity negatively impacts the benefi-
cial microbial population, which consequently reduced the nutrient trans-
formation and limits phyto-availability (Dahlawi et al., 2018). Biochar
application in saline and sodic soils had showed the improvement in macro-
nutrients contents (Akhtar et al., 2015; Kim et al., 2016; Lashari et al., 2013,
2015; Lin et al., 2015). This could be done by the biochar through directly
supplying the macronutrients, neutralizing pH, improving organic C content,
and indirectly supporting the growth of beneficial microbial population like
N2 fixing bacteria and phosphate solubilizing bacteria (Lashari et al, 2013).
Several research studies had also reported that biochar application could nega-
tively impact the soil by increasing ESP and SAR, as some biochars (depend-
ing on feedstocks like poultry litter) also contains considerable amount of Na
(Fernandes et al., 2019). Furthermore, several studies also reported that bio-
char application limits the nutrient bio-availability in saline and sodic soils
due to biochar induced alkalinity and nutrients (P) precipitation (Xu, Zhang,
Sun, & Shao, 2016). In this context, either biochar with less Na and high Ca/
K or biochar mixed with Ca/K rich mineral could be more suitable for appli-
cation in salt affected soils (Dahlawi et al., 2018; Lin et al., 2015). Overall,
almost all biochar research works underscores that the positive and negative
impacts of biochars application are mainly related to biomass feedstock prop-
erties, pyrolysis condition, biochar dose, and soil characteristics.
3.2. Socio-economic aspects of biochar fertilizers

In recent decades, technological advancement has provided many useful
soil productivity and ecosystem resource management techniques essential
for sustainable agriculture. But, these have rarely been discussed with pro-
ducers and perhaps other agricultural specialists, farmers and technicians
who are actually in need of some advancements (Scherr & McNeely, 2008).
This appears specifically true for biochar-based fertilizer. So, knowledge of
the socio-economic aspects of biochar production, logistics and recognition
by farmers are essential, if biochar to be adopted in agricultural practice.
While biochars have many technological advantages, it is of limited use if
its application (how and when) not properly demonstrated and people/
farmers are unaware. Local development and distribution of crop residue
derived biochars are more sustainable than large-scale processing for farm-
ers. Farmers on-farm easy and convenient ways to turn crop residues or
any other waste biomass into biochar should practice and therefore trans-
port of biomass to any other locations are not required. However, it is dif-
ficult to convert diverse biomass into biochar by specific, low cost single
pyrolysis reactor design, as the complexity of biomass characteristics (types,
values, size, shape, density, etc.) produces several different biochars.
Modern biochar processing is an acquired know-how. Biochar products
and innovations in market as patents are released at a high price, and are
not available to farmers. In many developed and poor countries, therefore,
the industrial approach to biochar development will not be a viable choice.
Farmers should be encouraged in their fields to use biochar on a trial
basis, and experimental results with controls should be compared. Plants
grow rapidly in case of chemical fertilizer while plant grow slowly with bio-
char. Also, with 10% increase in yield, the cost of biochar fertilizers reduces
to half than that of conventional fertilizers. While farmers during field
studies are satisfied with the biochar application performance, the high cost
of biochar technology makes it difficult for its practical implementation on
a large scale (Reddy, 2014).
Biochar costs are related directly to feedstock costs, collection, transpor-
tation costs, methods of processing and co-products value (Filiberto &
Gaunt, 2013). Life cycle and economic assessment performed for biochar
by Homagain et al. (2016) reported that the total biochar production cost
includes 12% for feedstock collection, 9% for transportation cost, 36% cost
for the pyrolysis production system and 14% for land application. The feed-
stock collection depends on its availability in bulk volume and proximity
with the location of pyrolysis system. Forestry wood and agricultural (e.g.,
corncob, rice straw) wastes could be considered as high availability feed-
stock, as it can be collected in bulk from point sources and transported eas-
ily to nearby located pyrolysis system. Whereas, animal wastes (poultry/
swine manures and bone wastes) could be low available feedstock, as for
acquiring it in sufficient quantity (e.g., to produce 50 tons of biochar for
land application) they need to collected from several non-point sources
located at very large distances (within 300 km or above). Low availability
feedstock collection costs about $134,053/year, and high feedstock availabil-
ity costs $113,945/year. For low and high feedstock availability, the trans-
portation costs were $97,962/year and $83,268/year, respectively (Homagain
et al., 2016). Cost of biochars derived from green waste and waste wood
biochars are within $150 and $260/ton (Shackley et al., 2011). Biochar cost
produced from bagasse is between $50 and $200/ton (Van Zwieten et al.,
2008). The reports by United States (US) initiative assigned $500/ton broad
cost for biochar (US Biochar Initiative, 2013). Taking into account the costs
of input and use, together with the rates of biochar soil addition, an esti-
mated biochar amendment cost was $6,317/ha (Filiberto & Gaunt, 2013).
The costs of poultry litter and wastewater sludge biochars and other waste
biochars could be considerably lower, since it will prevent/remove the dis-
posal costs and pollution problems associated with those raw wastes. In
contrast to many conventional fertilizers, biochar is also projected to offer
lasting soil benefits, and is not necessary to be added to soil every year.
Here again lies a cost benefit of using biochar fertilizers over conventional/
synthetic fertilizers (Filiberto & Gaunt, 2013). This provides an important
context in which biochar applications are economically viable.
4. Environmental concerns and challenges of biochar application in soil

Some of the environmental impacts and challenges related to biochar appli-
cation in soils are discussed below:
1. C sequestration through conversion of biomass to biochar is suggested

as one of the ways of reducing global warming and climate change
(IPCC, 2014; Wang, Zheng, et al., 2013). Woolf et al. (2010) reported
biochar and its soil storage would help reduce current anthropogenic
CO2 emissions by up to 12%. By reducing usage of N fertilizer, biochar
could also minimize indirect greenhouse gas (GHG) emissions (Brassard
et al., 2016). However, all biochars are not the same and equally effi-
cient. For C sequestration, biochar should be prepared from specific
feedstock and through appropriate pyrolysis conditions (e.g., high tem-
perature) to contain higher recalcitrant and stable C. In addition, bio-
char should be produced in reactors generating few or no GHG.
2. Biochar application has been studied to treat and remediate infertile
and contaminated soils (Mandal, Sarkar, Bolan, et al., 2017; Mandal,
Sarkar, Igalavithana, et al., 2017; Xu, Lin, et al., 2018; Xu, Seshadri,
et al., 2018; Yang et al., 2018, 2019). It has been found beneficial in
immobilizing soil pollutants (Stefaniuk et al., 2017), however, several
studies also reported that some biochar products increased the availabil-
ity of harmful organic compounds, which represents a potential threat
to human health. Therefore, the content of organic toxicants in the bio-
char and their eco-toxicological impact on soil flora and fauna needs to
be evaluated (Kookana et al., 2011).
3. Biochar contains toxic Polycyclic Aromatic Hydrocarbons (PAHs),
whose concentrations and type varied based on production conditions
like residence time, temperature, slow or rapid pyrolysis (Garcia-Perez
et al., 2008; Jose et al., 2016; Wang et al., 2017). Thus, biochar organiza-
tions such as the International Biochar Initiative (IBI) and European
Biochar Foundation have set a threshold PAHs value of 6–20 mg/kg and
12 mg/kg dry matter for basic grade and premium grade biochar,
respectively (EBC, 2013; IBI, 2012). Special care and further studies are
necessary for determining the suitable process conditions to produce
nutrient rich biochar with permissible PAHs value for its application to
agricultural soils.
4. Application of raw sewage sludge in soil is highly restricted due to the
presence of pathogens and toxic (heavy metals) contaminants. Due to
its high nutrient content and abundant availability, sewage/wastewater
sludge has been one of the most frequently used feedstocks for the pro-
duction of nutrient rich biochar fertilizers. Nearly all research studies in
literature (Khanmohammadi et al., 2015; Yuan et al., 2015) have empha-
sized that sewage sludge pyrolysis enriches the total heavy metals in bio-
chars. However, regarding the bio-available/leachable fractions of heavy
metals in sewage sludge biochars, both positive and negative results
were reported. Yuan et al. (2015) reported a decrease in the leachable
fraction of As, Cd, Cr, Cu, Pb, Ni, Zn and the bio-available fraction of
Cu, Fe, Mn, Zn in biochars of sewage sludge compared to raw sewage
sludge. Khanmohammadi et al. (2015) also reported a reduction in the
bio-available sewage sludge biochar fraction of Cu, Fe, Pb, Mn, Ni and
Zn. Khan et al. (2013) reported a decrease in As, Co, Cr, Ni, and Pb
bio-availability, but not Cd, Cu, and Zn. They also reported reduction
of As, Cr, Co, Cu, Ni, and Pb bioaccumulation but not of Cd and Zn.
Previous studies also document the presence of organic contaminants,
such as PAHs, in sludge-derived biochars rich in nutrients (Khan et al.,
2015; Waqas et al., 2015). Wang et al. (2019) highlighted about the
human health risks related to biochar associated PAH and suggested to
regulate the dose of application below 20 t/ha to manage the problem.
The toxic content in biochar and their transfer/accumulation to biota
can be restricted depending upon soil and biochar characteristics
(Malev et al., 2016). Toxic contaminants could be regulated within the
permissible limit by moderating methods and processes of biochar pro-
duction (Hale et al., 2012). Further extensive studies are needed to
know about biochar toxicants bioavailability, bio-magnification and risk
to the environment.
5. The retention of toxic contaminants in biochar fertilizers is dependent
on their chemical forms, which could be restricted by selecting proper
production conditions. Catalysts/additives (e.g., KCl) could be used with
biomass during pyrolysis to volatilize the heavy metals, or to use silica
to form silicate metals to significantly reduce their leaching capacity and
bio-availability in biochars. The effect of these additives on biochar

characteristics must be investigated, as it can also adversely affect the
availability of nutrients by influencing the surface area, porosity or fix-
ing K as silicates. Detailed, in-depth mechanistic study of heavy metals
retention, enrichment, and vaporization during sewage sludge pyrolysis
is highly essential to minimize its toxic content in biochars.
6. Biochar produced by high temperature gasification could not be suitable
for agriculture application. As, gasification of biomass at high tempera-
ture will produce a completely inert biochar and its application may
cause immobilization of nutrients in soils.
5. Future perspectives
1. Biochar fertilizers rich in P/K are generally low in N and have a higher
C/N ratio, which highlighted that the N will not be bio-available for
plant uptake. For improving crop productivity, the co-use of N fertil-
izers or compost with those biochar fertilizers is suggested in the soils.
Another method that could be explored is the post-treatment of P/K
rich biochar such as using it as a sorbent to recover N species from
wastewater and waste gases (e.g., biogas), which will enhance its N con-
tent and achieving the proper C/N ratio (below 30) for its bio-availabil-
ity in soils.
2. Current research aims mainly toward enrichment of single macronutri-
ent specifically N, P and K. But, for practical application of a single
nutrient (e.g., P) enriched biochar fertilizer, additional fertilizer (e.g., N
and K) must be applied along with it. Research on production of bio-
char complex (rich in multiple macronutrients) fertilizer is highly desir-
able to minimize the additional need of chemical fertilizer/compost for
plant growth. Production of designer biochar enriched in specific
nutrients as per the requirement of a particular soil-plant system should
also be investigated in future.
3. Biochar fertilizers containing P in form of Ca-P/Mg-P/Fe-P are not
highly soluble in water and are slowly available for plant uptake. The P
solubilizing bacteria such as Pseudomonas and Rhizobium (Rodrıguez &
Fraga, 1999) could be integrated in biochars porous structure to
enhance the availability of phosphate in soils for plant use. Likewise,
different microbes such as K and S solubilizing bacteria could possibly
be loaded in biochars for increasing the bio-availability of the nutrients
as per the requirement.
4. For controlled release of nutrients in the soil, it is recommended for
encapsulating the biochar with bio-polymers like latex, starch, cellulose,
chitosan etc. (Zhou et al. 2015). It will help in improving the nutrient
use efficiency for precision agriculture. Biochar coating with waterborne

polyacrylate material decreased its rate of bio-degradation, which indi-
cates the controlled nutrient slow release for long time. In addition, the
coating material does not showed significant harmful effect on soil
microbial community diversity, and thus potentially environmental
friendly (Zhou et al., 2015). Biochar based slow release fertilizer pre-
pared by coating with water borne co-polymers (Polyvinyl alcohol and
polyvinylpyrrolidone). This biochar demonstrated an effective release
behavior for urea (Chen et al., 2017).
5. The incorporation of nanomaterials like nano clays and metal nanopar-
ticles in biochar fertilizer may also be done to increase its surface area
and functionality. This will enhance the capacity of the biochar for
retaining nutrients back in the soil for a longer time period, thereby
allowing slower release of nutrients in soils for a much better
plant growth. So, this would help in extending the bio-availability of
nutrients for longer time and minimize the unwanted loss of nutrients
through leaching.
6. Biochars (especially sewage sludge and manure derived) also contain
considerable amount of essential plant nutrients such as Ca, Mg, Fe, Zn,
Cu, Mn (Figueredo et al., 2017; Prasad et al., 2019). However, informa-
tion about their enrichment in biochar and their bio-availability in dif-
ferent soil system are highly scarce (Bornø et al., 2019). Future studies
could be focused on long-term field trials for assessing the heavy metals
leachability and plant uptake after biochar application in different soils
and environment conditions (e.g., various seasons-summer, winter, and
rainy). This will help to predict the risk of large scale biochar applica-
tion toward environment and human health.
7. The use of biochar fertilizers has been found to reduce the bioavailabil-
ity of micronutrients (Cu, Mn, Zn) in soils, which will cause deficiencies
and limited plant growth (Karimi et al., 2020). Thus, future studies are
necessary to overcome that limitation. For example, studies for evaluat-
ing utilization of other micronutrients materials along with biochars for
agriculture.
8. As the application of biochar is a relatively new agricultural practice,
most of the research studies have been undertaken at lab scale with dif-
ferent biochars and soils. Therefore, long term field studies are highly
essential to validate lab-scale experimental findings about detailed mech-
anism and possible negative impacts of biochar fertilizers application in
soils to reach an appropriate conclusion. It is essential to study and
determine the quantity that needs to be applied in soil. Furthermore,
there is inadequate information about the sustainability of its use in
agriculture.
6. Conclusions
Nutrients rich biochar fertilizers with desired characteristics can be pro-
duced by selecting specific feedstocks and applying appropriate production
methods. Nutrient enrichment in biochars predominantly related to charac-
teristics of feedstocks. All the three classified methods i.e. direct pyrolysis,
pre-pyrolysis and post-pyrolysis showed possibility for biochars fertilizer
production. Unlike pre- and post-treatment methods, direct pyrolysis of
nutrients rich feedstocks (cattle carcasses, bio-fermentation waste) produced
N-P-K enriched biochar fertilizers without additional treatments. For N
enrichment in biochar, low temperature pyrolysis condition i.e. 300–400 C
were suitable; in contrast it was reported to be relatively higher (about
700 C) for P and K enriched biochars. Enriched biochar fertilizers
improved fertility in diverse soils (sandy, silt-loam, clay loam, acidic soil)
and aided plant growth (e.g., maize, lettuce, rye grass etc.), which depends
on factors like total and bioavailable nutrient contents, soil properties, and
plant species. Also, long term studies to evaluate the holistic effects of bio-
char application on soil health (including soil biota) vis-a-vis plant prod-
uctivity are needed. As nutrient enriched biochars produced from
contaminated feedstocks like sewage-sludge contained toxic constituents
like heavy metals etc., therefore study about its alternative utilization like
mine reclamation and revegetation etc. should be explored. In view of con-
tinuous availability of diverse wastes and specific agro-ecological require-
ments, decentralized production of nutrients enriched biochars has brighter
scope to contribute for sustainable agriculture and socio-economic
development.
Acknowledgments
All the authors express sincere thanks to all the reviewers and editor for valuable guidance,
which helped in improving the content and quality of the manuscript. Authors also
acknowledge the support of Prof. S. Basu, Director, CSIR-IMMT, Bhubaneswar. Manish
Kumar would like to highlight the financial support provided by CSIR (OLP-86 and MLP-
75) and DST, Government of India [(DST/TDT/WM/2019/51 (g))] as GAP-335 projects
related to biochars theme at CSIR-IMMT.
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Critical Reviews in Environmental Science and

ISSN: (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/best20

Enrichment of primary macronutrients in biochar

To link to this article: https://doi.org/10.1080/10643389.2020.1859271

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Enrichment of primary macronutrients in biochar for

KEYWORDS Agriculture; biochar fertilizers; macronutrients; soil fertility; waste

CONTACT Manish Kumar manish@immt.res.in; Adnan Asad Karim md.karime@gmail.com Environment

biochar showed neutral pH (7.0–7.5). When pyrolysis temperature

1. Co-relation between the various production processes and enrichment

2. Production of nutrients enriched biochar-based fertilizer and

2.1.1. Direct treatment method

Figure 1. Schema of different methods for production of biochars fertilizer.

pyrolytic methods to produce primarily N-P-K, P, and K enriched biochars

2.1.2. Pre-treatment method

2.1.3. Post-treatment method

manure anaerobic digestate liquid/slurry, biogas fermentation liquid, and

phosphate mainly occurred through electrostatic attraction and bonding

2.2. Nutrients transformation mechanisms in biochar fertilizer production

pyridinic N of raw sludge. In addition, the sludge biochars contained

changes in the proportion of organic, inorganic, and volatile P compounds.

sewage sludge formed by use of biological precipitation method for rural

(CaAl3(OH)5(PO4)2), Wavellite (Al3(OH)3(PO4)25H2O), Hydroxyapatite

2K þ 2H2 O ! 2KOH þ H2 (3)

2KOH þ 2K ! 2K2 O þ H2 ðabove 400 CÞ (4)

4KO2 þ 3C ! 2K2 CO3 þ CO2 (5)

2KO2 þ CO ! K2 CO3 þ O2 (6)

K2 CO3 þ H2 O þ CO2 ! 2KHCO3 (7)

Presence of above-mentioned minerals and their dominance in biochars

2.3. Nutrient binding mechanisms and its release

3. Potential of biochars fertilizer for soil application

glasshouse superphosphate; increased P plant

3.1. Contradictory findings related to biochar application in soil

3.2. Socio-economic aspects of biochar fertilizers

4. Environmental concerns and challenges of biochar application in soil

1. C sequestration through conversion of biomass to biochar is suggested

bio-availability in biochars. The effect of these additives on biochar

use efficiency for precision agriculture. Biochar coating with waterborne

growth–promoting rhizobacteria and Fe-EDTA. Journal of Soil Science and Plant

Bornø, M. L., M€ uller-St€

application. Journal of Analytical and Applied Pyrolysis, 123, 165–172. https://doi.org/10.

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