Chemosphere 283 (2021) 131176

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Biochar affects the fate of phosphorus in soil and water: A critical review
Larissa Ghodszad a, Adel Reyhanitabar a, Mohammad Reza Maghsoodi a,
Behnam Asgari Lajayer b, Scott X. Chang c, d, *
a
Department of Soil Science, Faculty of Agriculture, University of Tabriz, Tabriz, Iran
b
Health and Environment Research Center, Tabriz University of Medical Sciences, Tabriz, Iran
c
State Key Laboratory of Subtropical Silviculture, Zhejiang A&F University, Lin’an, 311300, Zhejiang, China
d
Department of Renewable Resources, University of Alberta, Edmonton, T6G 2E3, Canada

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

Handling editor: Patryk Oleszczuk Biochar is a promising novel material for managing phosphorus (P), a nutrient often limiting for primary pro­
duction but can also be a pollutant, in the environment. Reducing P input to the environment and finding cost-
Keywords: effective approaches to remediate P contamination are major challenges in P management. There is currently no
Eutrophication review that systematically summarizes biochar effects on soil P availability and its P removal potential from
Phosphorus dynamics
water systems. In this paper, we comprehensively reviewed biochar effects on soil P availability and P removal
Pollutant
from water systems and discussed the mechanisms involved. Biochar affects soil P cycling by altering P chemical
Pyrolysis
Soil fertility forms, changing soil P sorption and desorption capacities, and influencing microbial population size, enzyme
activities, mycorrhizal associations and microbial production of metal-chelating organic acids. The porous
structure, high specific surface area, and metal oxide and surface functional groups make biochars effective
materials for removing P from eutrophic water via ligand exchange, cation bridge, and P precipitation. Because
soil and biochar properties are widely variable, the effect of biochar on the fate of P in soil and water systems is
inconsistent among different studies. Knowledge gaps in the economic practicability of large-scale biochar
application, the longevity of biochar benefits, and the potential ecological risks of biochar application should be
addressed in future research.

1. Introduction of P in crop production systems is not sustainable, as currently much of

Phosphorus (P) is an essential macronutrient for plants, and P defi­
ciency is one of the main factors limiting plant growth and crop pro­
duction, as the majority of the world’s agricultural lands are deficient in
P (Wang et al., 2012). Annually, 15 million tons of P fertilizer is used to
meet plant P requirement, but only 5 to 30 percent of the applied P is
absorbed by crops, and the bioavailability of the remnant P is very low
due to sorption, precipitation, and microbial immobilization processes
(P fixation) that occur in the soil (Wang et al., 2012). Such behaviors of P
in the environment cause two problems: 1) the low bioavailability of the
applied P means that repeated application is required to meet crop P
requirement in intensively managed croplands, and 2) the repeated
application of P fertilizers causes accumulation of P in the soil,
increasing the risk of P loss through surface runoff and leaching to the
groundwater, resulting in the pollution of surface water, which can
cause eutrophication. A related problem is that the repeated application
the P fertilizer is produced from phosphate rock, which is a
non-renewable resource; the extraction of phosphate rock will eventu­
ally become non-economical as the resource is expected to be exhausted
by the end of this century (Streubel et al., 2012).
Organic matter can be applied to the soil to reduce soil P fixation and
increase soil P availability because organic matter and its decomposition
products (e.g., organic acids) occupy the surfaces of phosphate adsor­
bents in soils and prevent the formation of P precipitation (Du et al.,
2013). Adding animal manure and mulch, planting cover crops, and
returning plant residues to soil are methods recommended to increase
soil organic carbon (C) storage and improve soil P availability. However,
due to their low resistance to microbial degradation, the effect of these
types of organic matter added to the soil decreases or disappears after a
relatively short period of time (Moinet et al., 2018).
Over the last couple of decades, biochar has gained worldwide
attention as a novel material for environmental application. According

* Corresponding author. State Key Laboratory of Subtropical Silviculture, Zhejiang A&F University, Lin’an, 311300, Zhejiang, China.
E-mail addresses: larissaghodszad@ymail.com (L. Ghodszad), areyhani@tabrizu.ac.ir (A. Reyhanitabar), mr_maqsoodi@yahoo.com (M.R. Maghsoodi), h-asgari@
tabrizu.ac.ir (B. Asgari Lajayer), sxchang@ualberta.ca (S.X. Chang).

https://doi.org/10.1016/j.chemosphere.2021.131176
Received 19 November 2020; Received in revised form 12 April 2021; Accepted 8 June 2021
Available online 13 June 2021
0045-6535/© 2021 Elsevier Ltd. All rights reserved.
L. Ghodszad et al.
Table 1
Types of biochar production processes.
Process type Product (%)
Temperature (◦ C) Residence time (second)
Slow pyrolysis 100–1000 Long (7200–14,400)
350–800
Intermediate pyrolysis ~500 Moderate (10–20)
Fast pyrolysis 300–1000 Short (2)
400–600
Gasification ~900 Moderate (10–20)
700–1500
to the IBI (International Biochar Initiative) definition, biochar is a solid
material derived from the thermochemical conversion of feedstock in an
oxygen-limited environment. Generally, biochar is provided to meet the
following four goals: waste management, climate change mitigation,
energy generation, and improvement of soil properties (Tejerina, 2010).
The physical and chemical properties of biochars are strongly controlled
by factors such as the type of feedstock and pyrolysis condition (such as
pyrolysis temperature, heating rate, and residence time) used (Laird
et al., 2010). Biochar is a promising soil amendment, which is highly
resistant to microbial degradation, and an effective adsorbent for pol­
lutants in soil environments and aqueous solutions.
Many studies have examined the response of P availability to biochar
application in agricultural ecosystems; however, the majority of these
experiments involved a single biochar, pyrolysis condition, application
rate, or soil type, and contradictory results are often reported. Similarly,
the effectiveness of biochars for P removal from wastewater has been
variable among studies (Nobaharan et al., 2021). In addition, biochar’s
efficiency in removing P from wastewater can be low because of bio­
char’s negatively charged surfaces; modification methods have been
proposed to enhance biochar’s affinity for anionic pollutants such as
PO3−4 in water systems (Qu et al., 2020). To the best of our knowledge,
no systematic review has been conducted to synthesize the knowledge
on how biochar influences the biochemical cycle of P in the soil and P
removal from water systems. This review synthesizes recently published
data in this field, discusses mechanisms involved in biochar effects on
soil P availability and P removal from water systems, and provides
recommendations on areas for future research. With this background in
mind, this paper 1) discusses factors affecting biochar’s various physi­
cochemical properties, 2) assesses the effects of biochar on soil P
biochemical processes and soil P bioavailability, 3) reviews the sorption
of P by biochars and factors influencing P sorption, including biochar
modification methods to improve the effectiveness of biochars for P
sorption, and 4) recommends areas for future research, based on
knowledge gaps identified in this review, in biochar development for
application to meet agricultural and environmental management
objectives.
2. Biochar and factors affecting biochar properties
2.1. Biochar defined
Biochar is a porous, C-rich solid product from the pyrolysis of
biomass feedstocks in an oxygen-limited environment. The main pur­
pose of the thermochemical process of pyrolysis is to break up the
polymeric structure in the feedstock and convert polymeric compounds
into those with smaller molecular sizes (Kambo and Dutta, 2015). Bio­
char can be obtained from many different kinds of organic materials,
such as crop straw, rice husk, animal manure, wood waste, sewage
sludge, and other agricultural wastes (Dai et al., 2020). Biochar prop­
erties are governed by the feedstock type and pyrolysis conditions (py­
rolysis temperature, heating rate, and residence time), with the pyrolysis
temperature as one of the most important factors affecting biochar
properties. During the pyrolysis process, three phases of solid (biochar),
Chemosphere 283 (2021) 131176
Gas)Synthetic gas ( Liquid (Bio-oil) Solid (Biochar) Reference
35 30 35 Ok et al. (2015)
35 30 35 Tomczyk et al. (2020)
25 50 25 Ok et al. (2015)
~25–13 ~50–75 ~12–25 Ok et al. (2015)
13 75 12 Tomczyk et al. (2020)
85 5 10 Ok et al. (2015)
85 5 10 Tomczyk et al. (2020)
liquid (bio-oil), and gaseous (such as CO, CO2, CH4, and H2) products are
obtained (Yu et al., 2019). Depending on the pyrolysis temperature,
heating rate, and residence time, four types of pyrolysis, including slow,
intermediate, and fast pyrolysis, and gasification, are identified
(Table 1). The type of pyrolysis process used will affect biochar yield
(the conversion ratio of feedstock to biochar), which decreases with
increasing pyrolysis temperature (Ok et al., 2015). Also, the type, size
and lignin content of the feedstock affect biochar yield and properties
(Ok et al., 2015). Among the types of pyrolysis, slow pyrolysis has the
highest yield (25–35%), and it is also the main biochar production
process in which the feedstock is generally heated at 300–650 ◦ C for a
few minutes to several hours at a heating rate of 10–30 ◦ C min− 1 (Kambo
and Dutta, 2015). Various biochar pyrolysis methods can affect biochar
characteristics. For example, fast pyrolysis has been shown to result in
the production of biochars with higher cation exchange capacity (CEC)
than slow pyrolysis and gasification (Lee et al., 2010). Slow pyrolysis
produces biochars with lower mineral (compared to gasification) and
higher recalcitrant and fixed C (compared to fast pyrolysis) components
that are more suitable for C sequestration in soil (Ok et al., 2015). Wheat
straw-derived biochar obtained by slow pyrolysis can increase net ni­
trogen mineralization, whereas biochars produced through fast pyroly­
sis led to nitrogen immobilization (Bruun et al., 2012).
2.2. Physical properties of biochar
Porosity and specific surface area are the two most crucial physical
properties that strongly affect the function of biochar (bH. Li et al.,
2017). Biochars with high porosity and specific surface area provide
sites for nutrient adsorption and soil microbial colonization (Chandra
and Bhattacharya, 2019; Tan et al., 2018). These two properties mark­
edly vary with feedstock type and pyrolysis condition. The size of pores
in biochars is highly variable and includes nano- (0.09–2 nm), micro-
(<2 nm), meso- (2–50 nm), and macropores (>50 nm) (Ok et al., 2015).
Generally, biochars produced from solid waste and animal litter exhibit
lower surface areas as compared to those produced from wood-based
feedstocks and crop residues, even with higher pyrolysis temperatures,
due to the considerable variation in cellulose, lignin, and moisture
contents in different feedstock types (Tomczyk et al., 2020). Under the
same pyrolysis condition, wood-derived biochars have a higher surface
area compared to rice husk-derived biochars (Kizito et al., 2015).
Generally, high pyrolysis temperature promotes the production of bio­
chars that have high porosity and a strongly developed specific surface
area due to the dehydration process, increased micropores, decompo­
sition of organic matter (lignin and cellulose), and formation of vascular
bundles or channel structure (Li et al., 2013; Rafiq et al., 2016; Zhao
et al., 2017). However, at pyrolysis temperatures higher than 600 ◦ C
(depending on the feedstock type), biochar’s porous structure may be
blocked by tar or destroyed, leading to a decreased surface area
(Chandra and Bhattacharya, 2019; Ronsse et al., 2013; Tan et al., 2018).
2.3. Chemical properties of biochar
Biochar’s chemical properties also vary greatly with feedstock type
2
L. Ghodszad et al.
and pyrolysis condition. At the same pyrolysis temperature, biochars
produced from non-wood feedstocks (e.g., algae, manure, and corn
stovers) generally have a higher pH than those derived from wood
feedstock (Enders et al., 2012; Mukome et al., 2013). Moreover, biochars
produced from solid waste and animal litter show a lower C and volatile
matter content, and a higher CEC compared to biochars produced from
wood-based feedstock and crop residues, even at high pyrolysis tem­
peratures (Tomczyk et al., 2020). Generally, biochars produced at low
pyrolysis temperatures show high biochar yields and have higher dis­
solved and unstable organic C contents. In contrast, biochars produced
at high pyrolysis temperatures have high ash and C contents, high
alkalinity, C stability, and resistance to microbial degradation with low
CEC, low abundance of surface functional groups, and low O/C and H/C
ratios (S. Li et al., 2019; Wei et al., 2019; Zhao et al., 2017). Biochars
produced under high pyrolysis temperatures have more non-volatile
elements such as sodium, calcium, potassium, magnesium, and P than
those produced under low pyrolysis temperatures (Enders et al., 2012;
Wang et al., 2015).
Biochar can contain a significant amount of P, which often remains in
the char and not sublimated during pyrolysis up to 700 ◦ C. The amount
of P in biochar varies with the feedstock type. For example, biochars
produced from biosolids and manure have higher P contents than those
derived from wood-based biomass (Wang et al., 2014). Phosphorus
concentration in biochars is typically 2 to 3 times higher than that in raw
material due to the cleavage of organic P bonds and C sublimation
during pyrolysis (Gul et al., 2015), as the C contained in the feedstock is
lost faster than P during pyrolysis. The P concentration in biochar varies
from 0.13 to 42.79 g kg− 1 in 38 types of biochars produced from various
feedstock types and under various pyrolysis conditions (Gul et al.,
2015). The gradual release of P from biochar contributes to the increase
in soil available P. Phosphorus compounds in biochar encompass a
complex mixture of P species, including amorphous, semi-crystalline,
and crystalline components (whitlockite, dehydrated struvite, and hy­
droxyapatite) with organic components (Enders et al., 2017).
Fig. 1. Effect of biochar on soil physical, chemical, and microbiological properties (DeLuca et al., 2015; El-Naggar et al., 2019; Gao and DeLuca, 2016).
3
Chemosphere 283 (2021) 131176
3. Biochar effects on soil properties
The impact of biochar on soil properties has been widely studied
(Fig. 1); however, biochar effects on soil properties depend on the soil
and feedstock type, and the pyrolysis condition. Morphological char­
acteristics (e.g., large surface area and highly porous structure) of bio­
char can change soil hydrological and microclimatic properties, which
have been linked to changes in soil microbial community and nutrient
cycling processes (Thies et al., 2015). Biochars produced at low tem­
peratures increase soil CEC (Mukherjee et al., 2011), but have minimal
effects on soil pH in acidic soils, and could slightly reduce the pH in
alkaline soils (Laghari et al., 2015). Moreover, the application of bio­
chars produced at low temperatures can enhance the availability of ni­
trogen, P, and potassium in acidic soils with low fertility; however,
biochar addition to alkaline soils may decrease plant-available iron,
zinc, copper, and manganese concentrations (Gunes et al., 2014). On the
other hand, biochars produced at high temperatures can be efficient in
neutralizing soil acidity and improving soil nutrient retention (Dai et al.,
2017).
Although biochar application can be a useful strategy in increasing
agricultural productivity in different soils and cropping systems in
various climates, the benefits of biochar application are not always
positive or realized. Biochar application may also have negative effects
on soils and agroecosystems. For example, if the feedstock contains
heavy metals such as chromium and copper, these heavy metals will
remain in biochar and enter the soil system when biochar is applied.
However, when agricultural waste material is used for biochar produc­
tion, the risk of heavy metal contamination to the soil is low. In addition,
biochar may contain many volatile organic compounds, and some of
them, such as polycyclic aromatic hydrocarbons (PAHs), poly­
chlorinated dibenzodioxins (PCDDs), and polychlorinated biphenyl
(PCBs), are toxic (Hale et al., 2012; Hilber et al., 2012); however, the
effect of these volatile organic compounds on plant and microbial
growth is not fully understood. Therefore, it is necessary to study the
bioavailability of these compounds after biochar addition to soils.
L. Ghodszad et al. Chemosphere 283 (2021) 131176

4. Effects of biochar application on soil P
4.1. Soil P chemistry
When P fertilizers are applied to improve soil productivity, more
than 80% of the applied P becomes unavailability for plant uptake due to
sorption, precipitation, and microbial immobilization processes, which
can remove phosphate ions from the soil solution (Zhu et al., 2018).
Phosphate ions interact with soil constituents, mainly Fe and Al
oxy-hydroxides, carbonates, as well as silicate clays, to decrease P
availability in soils (Antoniadis et al., 2016). The chemical fixation of P
and low P availability in soils increase the need for repeated P fertilizer
application to meet the crop demand for P; rock phosphates and other
sources of P fertilizers are a non-renewable and dwindling resource. On
the other hand, repeated P fertilization and P accumulation in arable
soils can increase P runoff and leaching and increase the risk for
eutrophication in water bodies to occur (Xu et al., 2019). Hence, P
fertilization is considered a double-edged sword in intensively managed
terrestrial ecosystems (Tamburini et al., 2014).
Biochar can alter soil P chemistry by interaction with soil organic
and mineral components and by changing P chemical forms and the
soil’s P sorption and desorption capacity (Hong and Lu, 2018; Xu et al.,

Table 2
Biochar effects on soil P chemistry.
Feedstock Pyrolysis condition Application rate (% rates Result Reference
were based on w/w)

Mixed hardwood (primarily oak Slow pyrolysis (traditional kilns)
and hickory)
Pepperwood and peanut hull
A mixture of three biochars
(sawdust, elephant grass, and
sugar cane leaves)
Corn stover, Pandrosa pine wood Fast pyrolysis at 650 ◦ C, 18 min of 4%
residue, switchgrass
A mixture of Norway spruce and Pyrolysis at 550–600 ◦ C, for 10–15 0, 15 and 30 t ha−
Scots pine wood chips
Birchwood
Wheat straw
Maize straw
Mallee (Eucalyptus polybractea)
Sewage sludge
Hardwood and poultry litter
Coffee husk
Eucalyptus globulus
Pinewood nd wheat straw
Wood chip
Cow dung impregnated with
magnesium
Rice husk, bamboo, deciduous
tree leaves, reeds and rice
straw
Rice straw
Corn cob and rice husk
Wood chips
Ecoera: a commercial product
manufactured in Sweden
Maize stalk
0, 0.5, 1 and 2% The 2% addition decreased total dissolved P leaching by 69% in Laird et al.
soils amended with manure (2010a)
Pyrolysis at 600 ◦ C 2% Peanut hull biochar reduced phosphate in leachates by 20.6%. Yao et al. (2012)
However, pepperwood biochar increased phosphate release from
the soil
Fast pyrolysis between 450 and 26% Biochar decreased P sorption capacity by 55% in degraded Morales et al.
500 ◦ C with 8 s of residence time tropical mineral soils. The soil/biochar mixture had a common P (2013)
desorption curve but also buffered the soil solution around 0.2
mg L− 1
Biochar decreased P sorption and increased P availability in acidic Chintala et al.
residence time soils, with opposite results for calcareous soils, especially with (2014)
alkaline corn stover and switchgrass biochars
1
Biochar had a very low P sorption affinity and did not enhance P Soinne et al.
min sorption (2014)
Pyrolysis at 500 ◦ C 20 t ha− 1 Biochar increased P release compared to reference soils Kumari et al.
(2014)
Pyrolysis at 350–550 ◦ C 0, 1, 5 and 10% P sorption increased with increasing application rate in acidic soil Xu et al. (2014)
but slightly decreased in alkaline soil. P desorption increased at
all application rates
Pyrolysis at 400 ◦ C, 1.5-h residence 0, 2, 4 and 8% The 8% addition rate increased Olsen-P from 3 to 46 mg P kg− 1 in Zhai et al. (2015)
time acidic soil and from 13 to 137 mg P kg− 1 in alkaline soils
Pyrolysis at 720 ◦ C, 20 min of 5% Biochar addition increased the % P retention in acidic soil by Zhang et al.
residence time ~17% (2016)
300, 400, 500, 600 and 700 ◦ C for 3 1% Sewage sludge biochars produced at 500 and 700 ◦ C reduced the Yuan et al. (2016)
h leaching of phosphate from a Typic Plinthudult soil
Slow pyrolysis at 650–700 ◦ C for 1, 2 and 5% Biochar addition increased the maximum P retention capacity of Dari et al. (2016)
hardwood and at 700 ◦ C for poultry two acidic soils with increasing biochar application rate
litter, for 1 h
1
Pyrolysis at 350 and 500 ◦ C, Biochar produced at 500 ◦ C applied at 15 t ha− 1 increased P
0, 5, 10 and 15 t ha− Dume et al.
residence time of 3 h availability in acidic soil with low available P, but increased P (2017)
sorption and decreased P availability in a calcareous soil at higher
application rate and pyrolysis temperature
Pyrolysis at 450 C with a residence 0, 5, 10, 20 and 35%
◦
P sorption was lower in acidic soils treated with biochar. 35% Martínez et al.
time of 3 h biochar application rate increased cumulative desorption by 85% (2017)
Wood: gasification at 2% Straw biochar did not affect P sorption, whereas wood biochar Bornø et al.
1000–1200 ◦ C. Straw: pyrolysis at enhanced P sorption in soils with low and intermediate P sorption (2018)
700 ◦ C capacities yet decreased P sorption in acidic soils with high P
sorption capacities
Pyrolysis at 500 ◦ C 5% Biochar facilitated P retention in acidic soils but decreased it in Chen et al.
alkaline soils (2018a)
Pyrolysis at 600 C for 1 h
◦
1% Biochar lowered P loss from leaching by 89% and enhanced Chen et al.
available P content in the soil surface layer by 3.5-fold (2018b)
Slow pyrolysis at 450 ◦ C for 2 h 0, 1 and 2% Available P in biochar amended soils varies greatly with soil and Hong and Lu
biochar feedstock type. Application of rice straw biochar (2018)
produced at 450 ◦ C resulted in the highest available P
Pyrolysis at 600 ◦ C for 2 h 0, 1, 3 and 5% Within a certain range of P concentration in the sorption Liu et al. (2018)
equilibrium solution, the amount of P sorbed by the three acidic
soils derived from a granite parent material markedly reduced
with increasing biochar application rate
Pyrolysis at 300, 450 and 650 ◦ C 1% Biochars produced at 300 and 450 ◦ C decreased P sorption and Eduah et al.
enhanced P availability, especially in acidic soils, but might (2019)
enhance P retention in neutral and alkaline soils in a short-term,
reducing P de-sorbability
Pyrolysis at 500 C
◦
0, 2 and 4% Biochar decreased P sorption but enhanced P binding strength in a Amarakoon et al.
sandy loam soil (2019)
Slow pyrolysis at 600 ◦ C and then Applied as a 3-cm layer, Decreased P loss from medium- to high-P organic soils but was Riddle et al.
coated with magnesium (hydr)oxide 27 cm below the soil less useful in mineral soils (2019)
surface
Pyrolysis at 350 and 600 ◦ C, for 2 h 1% Biochars reduced available soil P through P adsorption Li et al. (2020a,
2020b, 2020c)

4
L. Ghodszad et al.
2014). Understanding the effect of biochar application on soil P reten­
tion and release can help improve P management to boost soil P
bioavailability while mitigating off-site P transport. However, results on
biochar effects on soil P chemistry have been inconsistent and are
dependent on the type of feedstock, pyrolysis condition, application rate
as well as the physical and chemical properties of the soil (Table 2).
Little research has been done to understand the mechanisms of biochar
effects on soil P chemistry. Generally, the mechanisms that can lead to
increased P availability in biochar treated soils are:
1. The biochar surface is often negatively charged and can directly
adsorb cations such as Ca2+, Al3+, Fe2+, and Fe3+, resulting in a
decrease in P sorption and precipitation (Xu et al., 2014).
2. Phosphorus precipitation reactions are strongly influenced by soil pH
because the activities of ions capable of precipitation with P (e.g.,
Ca2 +, Fe2 +, Fe3+ and Al3+) are pH-dependent. Therefore, biochar
can improve P availability by modifying soil pH and affecting the
activity of these cations (DeLuca et al., 2009; Gao et al., 2019).
3. Increased soil pH upon biochar addition can reduce P sorption in the
soil due to stronger anionic repulsion (Chen et al., 2018a).
4. Dissolved organic matter released from biochar in the form of
organic ligands can form organo-metal complexes with iron and
aluminum oxides. As a result, the effective amount of these oxides in
the soil is reduced, and subsequently, the adsorption of P on the
surfaces of these oxides is reduced (Liu et al., 2018).
5. Biochars are a source of available P in soils. The gradual release of P
from biochar can increase soil P availability. Therefore, biochar has
the potential to be used as a slow-release P fertilizer. For example,
poultry manure biochar can be a potential source of P and could
increase extractable P in Ultisols, Oxisols, and Entisols 100 days after
application (Mendes et al., 2015). However, the amount and form of
available P are dependent on biochar type (Zhang et al., 2016).
6. The higher labile organic C concentration in biochars produced
under low temperature can reduce P sorption in soils due to
competitive reactions between P and low molecular weight organic
acids and anions (Eduah et al., 2019; Schneider and Haderlein,
2016).
7. Biochars, particularly hydrophobic or charged (negatively/posi­
tively) biochars, can adsorb organic molecules (such as complex
proteins, phenolic acids and carbohydrates) that can act as chelates
of metal ions that otherwise precipitate P. In other words, organo-
biochar or organo-mineral-biochar complexes are created over
time, increasing P solubility and availability (Gao and DeLuca,
2016).
Increased P sorption and reduction of its availability upon biochar
addition to soils, on the other hand, have been documented and have
been attributed to the increased sorption sites, particularly with the
addition of biochars with high specific surface areas and with high basic
cation concentrations, especially those pyrolyzed at high temperatures;
such biochars can provide a large number of positive charges and basic
cations such as Ca2+ and Mg2+ to the soil that precipitates P ions as
calcium or magnesium phosphates (Chintala et al., 2014; Xu et al.,
2014). The contradictory effects of biochars on P behavior in different
soils emphasize the need to consider both soil and biochar properties
when biochar is applied as a soil amendment, especially when it is
intended to provide plant P requirements and to control eutrophication.
4.2. Soil biological processes and P availability
Organic P needs to be mineralized to inorganic forms to become
available for plants. Microbial activities, including enzyme activities,
are the most important determinants of P mineralization (Böhme et al.,
2005). Organic P hydrolysis is carried out by extracellular enzymes (i.e.,
phospholipase, phosphatase, and phytase) produced by soil microor­
ganisms and plant roots (Gul and Whalen, 2016). Biochars can directly
5
Chemosphere 283 (2021) 131176
(by providing food source) and indirectly (by altering the microenvi­
ronment) increase microbial populations by creating high internal sur­
face areas due to its pore structure and increase the capability to adsorb
organic matter, which provides a more diverse habitat for microbes
(Winsley, 2007). Moreover, increased soil water retention following
biochar application can increase microbial activities. Therefore, biochar
can alter soil P bioavailability by influencing microbial population size,
enzymatic activity, microbial production of metal-chelating organic
acids, and mycorrhizal associations (Gao et al., 2019), depending on the
soil property, biochar type, biochar application rate, and duration of
experimentation (Table 3). For example, the addition of biochar can
increase P mineralization by increasing microbial biomass by ~3 times
and phosphatase activity by ~19% 20 days after application of ~3.5 t
ha− 1 of biochar produced from a water hyacinth (Eichornia crassipes)
feedstock via slow pyrolysis at 300 ◦ C (Masto et al., 2013). Moreover,
the increase in soil pH following the addition of biochar, particularly
those with high alkalinity, is another possible mechanism that increases
alkaline phosphatase activities and, subsequently, P availability. For
instance, the addition of swine manure biochar produced at 400 ◦ C at a
rate of 1.5% to a clay loam and a silt loam soil increased alkaline
phosphomonoesterase activity by 28.5 and 95.1%, respectively, coin­
ciding with the increase of soil pH from 6.9 to 7.5 and 5.2 to 5.8,
respectively. However, acid phosphomonoesterase activities decreased
by 18.6 and 34.0% in the clay loam and silt loam soils, respectively,
upon the swine manure biochar addition at the same rate (Jin et al.,
2016).
Phosphate solubilizing bacteria, accounting for 1–50% of the total
microbial population, are a key biological contributor to enhance soil P
availability for plants. Biochar can improve P availability in the soil by
providing habitat and carbon supply to phosphate solubilizing bacteria,
which can solubilize the insoluble complexed P in the soil (Siddiqui
et al., 2016). The phosphate solubilizing bacteria, which excrete organic
acids (i.e., citric acid, lactic acid, gluconic acid, and oxalic acid), can
solubilize the insoluble P. These organic acids can directly dissolve the
phosphate mineral by anion exchange of PO3− 4 by acid anion or can
chelate Al3+ and Fe2+, and Fe3+ cations (Narula et al., 2000). For
example, a biochar produced at a lower temperature (400 ◦ C) was more
vulnerable to a phosphate solubilizing bacteria (Pseudomonas putida)
than that produced at a higher temperature (700 ◦ C), as P species in the
biochar produced at 400 ◦ C have a lower degree of polymerization and a
poorer crystal structure than those in the biochar produced at 700 ◦ C
(Qian et al., 2019). Application of a rice husk biochar produced at 400 ◦ C
increased the activities of phosphate solubilizing bacteria and led to
increasing phosphorous availability (Liu et al., 2017). In addition, a
combination of sewage sludge biochar and the phosphate-solubilizing
Penicillium aculeatum can increase plant biomass and P uptake by
wheat and thus increase the P fertilizer value of biochar (Efthymiou
et al., 2018). Holm oak-derived biochar produced at 480 ◦ C can also
increase rock phosphate solubilization by Aspergillus niger by increasing
organic acid production and alleviating fluoride toxicity (Mendes et al.,
2014).
Arbuscular mycorrhizal fungi (AMF) are one of the most important soil
microbial groups in terrestrial ecosystems. In exchange for sugars, AMF
benefits their hosts by improving plant-water relations, increasing access to
immobile nutrients, especially P, and enhancing resistance to pathogens
(Warnock et al., 2010). Moreover, with plants and fungi, both secreting
phosphate solubilizing organic acids and extracellular phosphatases can
enhance plant P uptake (Gul and Whalen, 2016). Biochar can enhance AMF
growth probably by providing a shelter or mineral nutrients contained in or
adsorbed on its surface (Ogawa and Okimori, 2010; Hammer et al., 2014).
The AMF hyphae can also access microsites within the biochar that are too
small (<10 mm) for most of the plant roots to enter and can mediate plant P
uptake from the biochar (Hammer et al., 2014). Results on the interaction
between biochar and AMF are inconsistent (Table 3), which demands more
detailed research, particularly in realistic soil environments, to better un­
derstand the underlying mechanisms.
L. Ghodszad et al. Chemosphere 283 (2021) 131176

Table 3
Biochar affects soil P bioavailability by altering soil biological activities.
Feedstock Pyrolysis condition Application rate Result Reference

Lodgepole pine wood Pyrolysis at 600 C for 1 h

◦
0, 0.5, 1, 2 and 4% Biochar application at 2 and 4% reduced arbuscular mycorrhizal fungi Warnock et al.
stock (w/w) (AMF) abundance in roots by 58 and 73%, respectively, but not in soils; (2010)
soil P availability was reduced by 28 and 34%, respectively
Peanut shell pellets Pyrolysis at 360, 400 and 10% (v/v) Biochar produced at 360 ◦ C enhanced P availability by 101% but reduced Warnock et al.
430 ◦ C, for 5 min AMF root colonization and extra-radical hyphal lengths by 74 and 95%, (2010)
respectively
Mango trunks and The feedstock was stacked, 0, 11.6, 23.2 and Field application of biochar at 23.2 and 116.1 t C ha− 1 enhanced P Warnock et al.
branches covered with soil and grass, and 116.1 t C ha− 1 availability by 163 and 208%, respectively, and reduced AMF abundance (2010)
ignited in soils by 43 and 77%, respectively
A mixture of spruce and 550 ◦ C for 12 h The higher nutrient content of the biochar enhances its fungal Hammer et al.
pine wood colonization. Hyphal surface contact with the produced biochar increases (2014)
P transfer to the host plant six-fold.
coniferous wood chips 500 ◦ C for 5 h 0 and 5% (v/v) P in the lettuce plant increased with AMF and biochar addition. Hammer et al.
(2015)
Birch wood 500 ◦ C 0.74% (w/w) AMF colonization of roots does not respond significantly to wood-derived Liu et al. (2017b)
biochar addition and plant P uptake decreased.
− 1
Wheat straw Pyrolysis between 350 and 0, 20 and 40 t ha Both 20 and 40 t h− 1 addition enhanced alkaline phosphatase activity but Chen et al. (2013)
550 ◦ C did not impact acid phosphatase activity
Eichornia biomass Pyrolysis at 300 ◦ C, 30 min of 0, 0.1, 0.3, 0.5, 1 Application at 2% increased alkaline phosphatase (22.8) and acid Masto et al.
residence time and 2% (w/w) phosphatase activities (32%) (2013)
Maize straw Pyrolysis at 400 ◦ C, and 1.5-h 0, 2, 4 and 8% (w/ Biochar decreased acid phosphomonoesterase activity in acidic soil and Zhai et al. (2015)
residence time w) alkaline phosphomonoesterase activity in an alkaline soil
Bamboo and rice straw Bamboo pyrolyzed at 750 ◦ C for 0, 1 and 5% (w/w) Biochars did not affect acid phosphatase activity Yang et al. (2016)
3 h and rice straw at 500 ◦ C for
30 min
Peanut shell Pyrolysis of acid-activated 0, 2.5, 5 and 10% The highest acid and alkaline phosphatase activities lasted up to 30 days Bhaduri et al.
peanut shell at 300 ◦ C for 2 h (w/w) of incubation with the lowest application rate (2.5%) (2016)
Salicornia bigelovii Pyrolysis at 350 ◦ C for 6 h 5% (w/w) Biochar increased alkaline phosphatase activities by 1.5-fold but only Al Marzooqi and
increased acid phosphatase activities on days 0 and 8 of the incubation Yousef (2017)
Rice husk Pyrolysis at 400 ◦ C for 0.5 h 0, 10, 20 and 40 t The 20 t ha− 1 treatment increased soil microbial biomass P and Liu et al. (2017a)
ha− 1 phosphatase activities the most
Wheat straw Pyrolysis at 450 ◦ C 0, 20, 40 and 60 t Alkaline phosphatase enzyme activities increased by 2–147% as a Cui et al. (2019)
ha− 1 function of increasing biochar addition rate
Moso bamboo chips Pyrolysis at 600 ◦ C 0, 20 and 40 t ha− 1 Addition at 40 t ha− 1 decreased acid phosphatase activity by 17% Peng et al. (2019)
Mentha arvensis Pyrolysis at 450 ◦ C 0, 2 and 4% (w/w) Biochar increased alkaline and acidic phosphatase activities, especially Nigam et al.
the former (2019)
Maize stalk Slow pyrolysis at 400 and 1% (w/w) Biochar enhanced alkaline phosphatase activity, with the effect greater in Khadem and
600 ◦ C, for 2 h sandy loam than in clayey soils. Increasing pyrolysis temperature Raiesi (2019)
negatively affected soil microbial activity and biomass, and subsequently,
the alkaline phosphatase activity
Rice straw Pyrolysis temperature 5% (w/w) Biochar addition decreased acid and neutral phosphatase activities Liu et al. (2019)
450–550 ◦ C, for 45 min
Rice husk Pyrolysis at 350 ◦ C 0, 3, 6 and 12 t Biochar increased alkaline phosphatase activity in the 0–0.10 m soil layer Oladele (2019)
ha− 1 after two years of field application, especially at 12 t ha− 1
Banana peel Pyrolysis at 350 C for 3 h
◦
0, 1 and 2% (w/w) Biochar increased alkaline phosphatase activity by 12 and 6% for the Sial et al. (2019)
application rates of 1% and 2%, respectively
Rice husk Pyrolysis at ~450 ◦ C for 3 h 0, 0.5, 2 and 8% Biochar (applied at 8%) markedly increased neutral phosphatase Wang et al.
(w/w) activities by 2.3-fold compared to the control (2019)
Rice straw Pyrolysis at 380–400 ◦ C with a 0, 1, 2 and 4% (w/ Biochar applied at 1, 2 and 4% decreased alkaline phosphatase activity by Mukherjee et al.
residence time of 2.5–3.0 min w) 19, 34 and 50%, respectively, compared to the control (2019)
A mixture Eucalyptus Pyrolysis temperature between 0, 1, 2, 3, 4 and 5% Alkaline phosphatase activities were decreased with an increasing biochar Silva et al. (2020)
urophylla and 350 and 400 ◦ C (v/v) application rate
E. saligna wood
Cornstalk Pyrolysis at 250, 550 and 0.1% (w/w) Biochar produced at 550 ◦ C increased the activity of phosphate- Tao et al. (2020b)
850 ◦ C for 2 h solubilizing bacteria

5. Removal of P from water systems
5.1. Biochar as an adsorbent
The increasing discharge of industrial, agricultural, and urban ef­
fluents into surface waters has caused P pollution, which may result in
eutrophication and damage to the receiving waters (Drizo et al., 1999).
The minimum phosphate threshold concentration for the induction of
eutrophication is 0.02 mg L− 1 (Yao et al., 2013a). Today, eutrophication
or enrichment of surface waters is a serious environmental crisis in the
world (Yin et al., 2017). Due to increasing population growth and ur­
banization, municipal, industrial and agricultural waste production has
also increased. Wastewater discharge and excessive use of pesticides and
fertilizers lead to the enrichment of water systems with nitrogen and P,
thereby intensify the eutrophication of water bodies. This disturbs
aquatic ecosystems, reduces biodiversity, and causes fish death, algal
growth, and economic loss. Therefore, it is essential to use appropriate
technology to eliminate these elements and prevent them from entering
aquatic systems. Different physical, chemical, and biological methods
have been used to control and remove these elements from aquatic
systems. Also, previous studies have recognized adsorption as a common
and widely used technique owing to its cost-efficient operation, high
removal efficiency, and minimal generation of secondary byproducts
(Tehrani et al., 2020). In general, the use of chemical methods has its
disadvantages due to the high consumption of chemicals and the pos­
sibility of creating new pollutants in the environment.
The disadvantages of biological methods can be the difficulty of
implementation, high microbial sensitivity to pH in aquatic systems, and
potentially high cost. Physical methods, such as electrodialysis, reverse
osmosis, and ion exchange for P removal, usually do not provide

6
L. Ghodszad et al.
Fig. 2. Mechanism of the formation of outer- and inner-sphere complexes of phosphate-metal on biochar surfaces (modified from Shepherd et al., 2017).
satisfactory results (Park et al., 2015). However, adsorbents such as
aluminum oxide, fly ash, zeolite, activated C, loess, and synthetic ma­
terials have been used to remove inorganic pollutants from aquatic
systems, where carbonaceous materials have shown to be effective. On
the other hand, methods that use adsorbents, such as activated C, ion
exchange resins, and zeolites, are costly and require expensive raw
materials (Kizito et al., 2015). Therefore, it is necessary to use affordable
adsorbents. In recent years, several studies have been conducted to
investigate biochar performance as P adsorbents in aquatic systems. In
these studies, biochars had different P sorption capacities depending on
the feedstock type and pyrolysis conditions. For instance, a study on the
phosphate sorption capacity of several biochar types produced at tem­
peratures of 400–450 and 600–650 ◦ C showed that, as pyrolysis tem­
perature increased, the phosphate sorption capacity of oak wood and
greenhouse waste biochars decreased, but the phosphate sorption ca­
pacity of municipal waste and press cake biochars increased (Takaya
et al., 2016). A number of studies used biochars as adsorbents from P
removal from aquatic systems and then used those biochars as a
slow-release P fertilizer in a soil application. In this regard, biochars
produced at 600 ◦ C from Mg-enriched tomato tissues are not only effi­
cient adsorbents for P removal from aqueous solutions but also a large
amount of P retained by the biochar was bioavailable, and the biochar
can be considered a slow-release P fertilizer (Yao et al., 2013a, 2013b,
2013b).
5.2. Mechanisms of P sorption by biochar
Phosphorus-biochar interactions are very complex, and our under­
standing of these interactions is still limited. Some studies suggest that
biochar can adsorb P from aqueous solutions. Some other research,
however, shows that biochars having higher available P do not adsorb P
from aqueous solutions (Schneider and Haderlein, 2016). Phosphorus
sorption by some biochars is accomplished through the interaction of P
with functional groups, involving metal cations, or through precipita­
tion reactions. Phosphate ions may also be adsorbed through ligand
exchange with hydroxyl and carboxyl groups on biochar surfaces
(Shepherd et al., 2017). However, ligand exchange occurs only with
metal complexes. Phosphate ion species (PO3− 2−
4 , HPO4 , H2PO4 ) may
−
7
Chemosphere 283 (2021) 131176
also react with biochar surfaces via hydrogen bonds and outer-sphere
electrostatic interactions involving cations. This type of phosphate
sorption by biochar is poor compared to inner-sphere chemical sorption
and precipitation reactions that may occur with minerals and are usually
not long-lived. The mechanism for the formation of outer- and
inner-sphere phosphate-metal complexes on biochar surfaces is pre­
sented in Fig. 2. The mechanism of phosphate sorption by hydroxyl
functional groups on the biochar surface is described in Fig. 3.
Inner-sphere complex formation is accomplished by ligand exchange,
but outer-sphere complex formation occurs through the formation of
cationic bridges without ligand exchange (Shepherd et al., 2017).
Factors affecting the sorption capacity of P are numerous, and in
general, they are related to the properties of biochars and the solution
where the reaction is occurring. These factors include biochar’s specific
surface area, the presence of metal oxides in biochar, and the pH of and
the presence of other ions in the aqueous solution (Yin et al., 2017).
5.3. Effects of biochar properties on phosphate sorption capacity
5.3.1. Biochar specific surface area
Biochar can be effectively used to remove P from aqueous solutions
such as wastewater via the sorption process. The porous structure and
the high specific surface area of biochar allow sorption reactions and
transfer of P from an aqueous solution to the biochar surface. The spe­
cific surface area of biochar is a function of the feedstock type and py­
rolysis temperature. As the pyrolysis temperature increases, the
biochar’s specific surface area increases due to the increased removal of
volatiles from the feedstock, forming more pores. However, extremely
high temperatures lead to the disintegration of portions of biochar
structure, blocking pores and reducing active sites. Several studies
investigated the impact of feedstock type on biochar’s specific surface
area. Under the same pyrolysis condition, biochars produced from wood
had higher specificity than those produced from rice husk (Kizito et al.,
2015). Among biochars produced from peanut shells, oak, bamboo, and
soybean stover under the same pyrolysis condition, biochars produced
from peanut shells had the highest specific surface area. Biochars pro­
duced from peanut shells, oak, bamboo, and soybean stover had a spe­
cific surface area of 328.96, 185.54, 110.52, and 247.09 m2 g− 1,
L. Ghodszad et al. Chemosphere 283 (2021) 131176

Fig. 3. Mechanism of phosphate sorption by hydroxyl groups on biochar: a) HPO2−

4 reacts with the water molecule to form H2PO4 and releases OH ion into the
− −

solution, b) H2PO−4 ion forming binuclear-bidentate bond with (Ox)FeOH groups on biochar surfaces, leading to the formation of phosphate-metal inner-sphere
complexes on biochar surfaces, and c) HPO2−
4 and H2PO4 ions release one and two OH ions, respectively, for the formation of inner-sphere complexes (modified
− −

from Shepherd et al., 2017).

respectively, with the highest phosphate sorption capacity in the peanut
shell biochar (Jung et al., 2015a). Moreover, the phosphate sorption
capacity of marine macroalgae biochars was positively correlated with
the biochar’s specific surface area (Jung and Ahn, 2016). Hence, the
specific surface area can be used as an index of biochar’s phosphate
sorption capacity.
5.3.2. Metal oxides on biochar surface
Biochars may contain different types of metal oxides such as calcium
oxide, magnesium oxide, iron oxide, aluminum hydroxide, and
lanthanum oxide. These compounds can be effective in increasing the
phosphate sorption capacity by allowing phosphate in the solution to be
deposited on the biochar surface through weak hydrogen bonding with
these metal oxides. Also, soluble phosphate can be precipitated with
biochar metal oxides via the formation of strong chemical bonds. The
phosphate sorption capacity is correlated with the amount of calcium
and magnesium present in biochars (Takaya et al., 2016). Phosphorus
ions can precipitate with free cations in the aqueous solution such as
Ca2+ and Mg2+ that are released from biochar or co-precipitate with
mixed mineral complexes (Al–Fe–Si–Ca) on biochar surfaces (Shepherd
et al., 2017). High pH, high Ca, Mg, Fe, and Al contents, the presence of
carbonates, especially calcite, explain the high P sorption capacity of a
pine wood-derived biochar (Bornø et al., 2018). Moreover, in Yao et al.
(2013a, 2013b, 2011a, 2011b), the amount of magnesium in biochar
produced from sugar beet tailings and tomato treated with magnesium
nanocomposites was 10 and 8%, respectively; the magnesium resulted in
high phosphate sorption capacities (73 and 88.5%, respectively) in these
biochars. The researchers described the effective removal of phosphate

8
L. Ghodszad et al.
from aqueous solutions by these biochars as a result of the presence of
magnesium nano-oxides, which were dispersed in large numbers on
biochar surfaces. Many factors affect the high phosphate sorption ca­
pacity of those biochars that had high magnesium nano-oxide content.
For example, the surfaces of metal oxides are hydroxylated and
depending on the pH of the aqueous solution, the electrical charge of
these surfaces can be positive or negative. The variation of charge of
magnesium oxide on the biochar surface can be described as follows
(Stumm and Schindler, 1987):
SMgO − OH+
2 ⇌SMgO − OH⇌SMgO − O
−
The pH at the point of zero-charge (pHpzc) of magnesium oxide is
about 12 (Yao et al., 2011a). If the pH of the aqueous solution is less than
the pHpzc, the magnesium oxide surface carries positive charges.
Otherwise, the magnesium oxide surface carries negative charges.
Magnesium oxide usually carries positive charges in most natural and
experimental aqueous solutions (most have pH < 12). Hence, phosphate
species are electrostatically adsorbed to the magnesium oxide surface
and form mono-, bi- and trinuclear complexes according to the following
reactions (Chernyakhovskii, 1985; Volceanov et al., 2002; Yao et al.,
2011a):
0.12 > pH > 9.21 mononuclear complex
SMgO − OH+ −
2 + H2 PO4 ⇌ ​ SMgO H2 PO4 + H2 O
5.21 > pH > 10.67 binuclear complex
( )
2−
2SMgO − OH+2 + HPO4 ⇌ SMgO 2 HPO4 + 2H2 O
10.67 > pH > 12 trinuclear complex
( )
3SMgO − OH+ 3−
2 + PO4 ⇌ SMgO 3 PO4 + 3H2 O
Also, some of the magnesium oxides can be dissolved and precipitate
as Mg3 (PO4)2 and MgHPO4 through chemical reactions between phos­
phate species and Mg2+ (Yao et al., 2011a).
5.4. Effect of aquatic system properties on biochar’s phosphate sorption
capacity
5.4.1. The pH in the aquatic system
The pH of the aqueous solution can affect phosphate adsorption by
changing the surface charge of the adsorbent and phosphate species in
the solution. For instance, the pHpzc of biochars produced at tempera­
tures above 400 ◦ C is higher than the pH of the aqueous solution,
resulting in electrostatic adsorption between biochars and phosphates.
Biochar produced at 200 ◦ C, for example, had a low phosphate sorption
capacity, and the surface charge of this biochar was near zero when the
pH of the initial solution was 7 (Jung et al., 2015a). In addition, biochars
with a lower zeta potential might not be suitable for phosphate
adsorption owing to their more negative surface charge (Trazzi et al.,
2016). Overall, the zeta potential of biochars becomes more negative
with increasing suspension pH, suggesting that the number of negative
charge increases and biochar becomes adverse to phosphate adsorption
owing to the competition of OH− and phosphate for sorption sites and
intensified the electrostatic repulsion between phosphate and the bio­
char (Yang et al., 2017). The fact that a high zeta potential means high
phosphate adsorption capacity has also been confirmed in the evalua­
tion of phosphate removal by several types of biochars, such as bamboo,
oak wood, soybean stover, peanut shell, and maize residue biochar
(Jung et al., 2015a; Yin et al., 2017). The four different phosphate
species, H3PO4, H2 PO−4 , and HPO2− 4 have pKa values of 2.12, 7.21, 12.67
in aqueous solutions (Jung et al., 2015a). Generally, the free energy of
sorption for H2PO−4 is lower than HPO2− 4 ; therefore, H2PO4 sorption by
−
9
Chemosphere 283 (2021) 131176
biochar would more readily occur. The phosphate sorption capacity
decreases at high pH values, as PO−4 3 is predominant at high pH and is
hard to be adsorbed. The OH− and PO3− 4 ions also compete for sorption
sites at high pH; this reduces the sorption of phosphate by biochar (Yin
et al., 2017).
5.4.2. Coexisting ions in aquatic systems
In natural aquatic systems, in addition to the target ion, other ions
can affect the rate of sorption of the target ion onto biochar surfaces. In
most studies, the coexistence of phosphate and other ions in aqueous
solutions has a negative effect on phosphate sorption on biochar sur­
faces. For instance, the phosphate sorption capacity of biochar in syn­
thetic solutions containing humic acidic, nitrate, chloride, bicarbonate,
and P decreased by up to 40% compared to solutions containing phos­
phate only (Yao et al., 2013a, 2013b, 2013b). In another study, biochar
produced from a mixture of several types of hardwoods absorbed 96 and
50% of phosphate in a pure phosphate solution and dairy effluent,
respectively, after 24 h (Sarkhot et al., 2013). In situations where the
underlying mechanisms of adsorption of coexisting ions on biochar
differ from that of phosphate, the coexisting ions may have no
remarkable effect on the adsorption of phosphate. For example, high
SO2−
4 and NO3 concentrations had no remarkable effect on the adsorp­
−
tion of phosphate on the surface of biochars impregnated with ferric
chloride (Yang et al., 2017); that was because phosphate adsorption
occurred in oxides and hydroxides through ligand exchange, which
formed inner-sphere complexes, while the adsorption of NO−3 and SO2− 4
was non-specifically adsorption and created the outer-sphere complexes,
which would not interfere with the adsorption of phosphate. However,
the presence of CO2-3 could reduce the removal efficiency of phosphate by
about 20.6%, because CO2− 3 could compete intensely with phosphate for
the adsorption sites on biochar.
Although biochar is recognized as an efficient and cost-effective
adsorbent for environmental remediation, modification of biochar sur­
faces can increase the P removal efficiency from aquatic systems
(Table 4). According to our review of the literature, most biochar
modification methods aimed to enhance biochar P sorption capacity by
increasing biochar porosity, surface area and sorption sites (Jack et al.,
2019), increasing the abundance of oxygen-containing and organic
functional groups (Fang et al., 2014; Wang et al., 2020), enhancing Ca,
Mg, Al, Fe and Mn nanoparticles/composites and generating nano-sized
crystalline structures (Jung et al., 2015b), changing biochar surface
charge and zeta potential from negative to positive (Park et al., 2015;
Yang et al., 2017), and increasing biochar anion exchange capacity
(Mosa et al., 2018).
6. Conclusions and recommendations for future research
We conclude that biochar interacts with biotic and abiotic compo­
nents of the soil and directly and indirectly modifies soil P biochemical
processes through altering P chemical forms, soil P sorption and
desorption capacities, microbial biomass, enzymatic activities, mycor­
rhizal associations, and microbial production of metal-chelating organic
acids. The P bioavailability in biochar treated soils is controlled by soil
and biochar properties that are affected by feedstock type, pyrolysis
condition, biochar application rate, and length of study. For improving
soil fertility, obtaining biochar that is optimized for enhancing P
bioavailability for plants is desirable. Application of biochar in the soil
increases soil CEC, changes soil pH, and releases organic ligands. These
changes increase the adsorption of cations such as calcium, iron and
aluminum, thereby reducing the adsorption of P and the precipitation of
P in the soil, which ultimately leads to an increase in available P. In
L. Ghodszad et al. Chemosphere 283 (2021) 131176

Table 4
Phosphate sorption from aqueous solutions through various modified biochars.
Feedstock type Pyrolysis Treatment method Result Reference
temperature (◦ C)

Corn straw 800 Biochar decorated by NaLa(CO3)2 via Modified biochar had excellent monolayer PO3−4 uptake from water Qu et al.
one-pot hydrothermal method (330.9 mg g− 1) over a wide pH range of 3.0–8.0 (2020)
Corn stover 500 Corn stover treated with FeSO4 Modified biochar possessed 11–12 times more P sorption capacity Bakshi et al.
(2021)
Wheat straw 600 Biochar impregnated by solutions The maximum sorption capacity of biochar impregnated with the Zheng et al.
containing MgCl2, AlCl3, or both mixture of MgCl2, AlCl3 was 93.54 times the capacity of raw biochar (2020)
Ground corn 300, 450, and 600 The feedstock was dipped in MgCl2 Modification of biochar increased the maximum P adsorption from Fang et al.
solution 225 to 239 mg g− 1 (2014)
Raw corn straw 200, 300, 400, Raw corn straw was immersed in a ferrous The total P removal efficiency was >99% with the modified biochar Liu et al.
500, 600, 700 sulfate (FeSO4. 7H2O) solution and an effluent total P concentration was <0.02 mg L− 1 (2015)
Waste activated 550 Biochar was modified by chemical co- FeCl3-impregnated biochar had much better phosphate adsorption Yang et al.
sludge precipitation of Fe3+/Fe2+ or FeCl3 capacity (111.0 mg g− 1) in all as-prepared samples (2017)
impregnation
Wheat straw 400, 500 and 600 Wheat straw was soaked with bismuth Bismuth impregnated biochar produced at 500 ◦ C had high adsorption Zhu et al.
oxide solution and hydrochloric acid capacity for arsenic, P, and chromium (2016)
Wheat straw 600 Biochar loaded with CaO2 nanoparticles The nano-CaO2/biochar composite was efficient for phosphate Li et al.
removal in a wide range of initial pH and temperature, and the (2020b)
maximum adsorption capacity was 213.2 ± 13.6 mg g− 1
Sludge 550 Biochar peroxidized with nitric acid and The P adsorption capacity of the modified biochar increased ~ 40 Li et al.
impregnation with ferrous times (2020c)
Walnut shell 600 Impregnated with solutions with different The maximum sorption capacity of treated biochar increased three- Tao et al.
molar Fe2+ to Mg2+ ratios fold (2020a)
Cornstalk 550 Feedstock impregnated with MgCl2 Synthesized MgO-biochar with enough MgO active site had a Zhu et al.
maximum phosphate sorption capacity of 60.95 mg P g− 1 (2020)
Oak chips 500 Biochar loaded by lanthanum La-loaded biochar had greater adsorption ability due to decreased Wang et al.
surface negative charge and increased La-composites such as LaOOH, (2016)
LaONO3, and La(OH)3
Poplar chips 550 Chips were impregnated with AlCl3 Al-modified biochar had a greater P sorption capacity. Biochars with Yin et al.
20% Al had the highest PO3− 4 adsorption capacity (2018)
Moso bamboo 400, 500 and 600 Impregnation with MgCl2 Mg-laden biochar had higher phosphate adsorption capacities. The Jiang et al.
(Phyllostachys maximum phosphate adsorption amount was 344, 357, and 370 mg (2018)
pubescens) g− 1 for biochar-Mg-400, biochar-Mg-500, and biochar-Mg-600,
respectively
Sugarcane harvest 550 The residue was impregnated with MgCl2 Mg introduction enhanced biochar’s affinity for PO3-
4 Li et al.
residue (2017a)
Bamboo 300, 450 and 600 Biochar modified by polyethyleneimine The P adsorption capacity of PEI-modified biochar was enhanced with Li et al.
(PEI) increasing pyrolysis temperature from 300 to 450 ◦ C, but not with (2019b)
600 ◦ C
Bamboo 600 Biochar functionalized with Mg–Al and Composite with 40% Mg–Al LDH had the highest PO3− 4 adsorption Wan et al.
Mg–Fe (3:1) layered double hydroxides with >95% PO3− 4 saturation achieved within 1 h (2017)
(LDH)
Cotton stalk 350 Granulation of biochar powder followed Both granulation and ferric oxide loading increased the surface area Ren et al.
by impregnation with ferric oxides and the adsorption capacity (from 0 to 0.963 mg P g− 1) (2015)
Carrot residue 200, 300, 400, Carrot powder was added to a MgCl2 Biochar produced at 400 ◦ C and impregnated with Mg had higher Pinto et al.
500 and 600 solution efficiencies for P removal from aqueous solutions (2019)
Hickory wood chips 600 The feedstock was immersed in an AlCl3 Engineered biochar effectively removed P from a secondary treated Zheng et al.
solution wastewater (2019)

addition, biochar can directly and indirectly affect microbial and
enzymatic activities and change P availability. In this regard, biochar
increases soil water retention, internal surfaces, and microbial popula­
tion and ultimately increases the activities of enzymes, including
phosphatases. In addition, biochar can be a source of P and increase P
supply. On the other hand, P precipitation with minerals in the biochar
and soil may occur.
In addition, biochar has the capacity to remove and recover P from
wastewater. Physicochemical reactions govern the P sorption capacity
from wastewater in various types of biochars. The P sorption from water
systems by biochar depends on the feedstock type and pyrolysis condi­
tion used for biochar production. Several mechanisms have been pro­
posed for P removal from water systems. Adsorption of P is through the
interaction of phosphate with biochar surface functional groups such as
carboxyl and hydroxyl through the formation of hydrogen bonds and
electrostatic interactions. Biochar can also adsorb P by ligand exchange
with metal complexes or cationic bridges. Properties such as pH and
coexisting ions in water systems also affect biochar’s P sorption capac­
ity. Increasing the pH and CO2− 3 concentration in the water system re­
duces the biochar P sorption capacity. Various modification methods
can be used to alter biochar surface properties, which can enhance
biochar’s P sorption capacities. To improve the efficiency of biochar for
P capture from aqueous solutions, factors such as biochar chemical
composition, biochar surface physical properties, pH, and coexisting
ions should be considered.
There are research gaps that need to be addressed in future research
regarding biochar application for P management: 1.) despite numerous
studies on soil P bioavailability changes upon biochar addition, the
underlying mechanisms remain poorly understood and should be further
studied; 2.) the economic feasibility of biochar application should be
part of future research. If biochar application is not economically viable,
such applications would not be sustainable. Strategies for reducing
biochar losses and cost of applications and enhancing its use efficiency
need to be developed; 3.) the longevity of biochar benefits on P cycling
and related soil fertility needs to be addressed in long-term field studies;
4.) interactions among biochar, soil, microorganisms and plants in
biochar-treated soils are complicated, and mechanistic understanding of
those interactions is still lacking. More research to understand those
interactions are urgently needed so that biochar applications are better
guided; 5.) the relative contribution of desorbed P from biochar or soil to
soil P availability could be studied using the 32P isotope technique. The
32
P isotope technique should help us to understand the mechanisms of P

10
L. Ghodszad et al.
sorption/desorption by soil constituents in the presence of biochar; 6.)
more research is required to develop low-cost modification methods to
increase the P sorption capacity of biochars and reuse such biochars as a
slow-release P fertilizer, and 7.) systematic studies on the potential
ecological risk of applied biochar in soil or water systems should be
conducted. For instance, the toxicity (e.g., heavy metals) and salinity
risk of biochar leachate of some biochars can have adverse effects on the
environment.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
We thank the editor and two anonymous reviewers whose
constructive comments improved the quality of an earlier version of this
manuscript.
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