Environmental Chemistry Letters (2023) 21:497–524

https://doi.org/10.1007/s10311-022-01519-5

REVIEWPAPER

Phosphorus adsorption by functionalized biochar: a review

Dan Luo1 · Luyao Wang1 · Hongyan Nan1 · Yijun Cao1 · Hui Wang2 · Thakur Vijay Kumar3 · Chongqing Wang1

Received: 28 June 2022 / Accepted: 12 September 2022 / Published online: 1 October 2022
© The Author(s), under exclusive licence to Springer Nature Switzerland AG 2022

Abstract
Phosphorus is essential element for agricultural production, yet phosphorus ore resources are non-renewable and become
depleted. Moreover, phosphate release from wastewater treatment plants and from inefficient crop fertilization induces pol-
lution such as water eutrophication. Therefore, phosphorus recovery from wastewater is promising alternative source of
agricultural phosphorus. Biochar can be used to adsorb phosphorus due to their porous structure, large surface area, abundant
surface groups, and high mineral content of biochars. Biochar can be functionalized to improve their adsorption performance.
Here, we review phosphorus recovery by functionalized biochar, with focus on biochar preparation and modification, fac-
tors influencing the efficiency of adsorption, adsorption mechanisms, and biochars as slow-release fertilizers. We discuss
mechanisms for Mg-, Ca- and Fe-rich biochars.

Keywords Biochar · Phosphorus recovery · Adsorption mechanism · Slow-release fertilizer

Introduction situation have a more significant impact on food produc-

Phosphorus is an essential element for the basic life activi-
ties of living organisms and limits productive activities at
the base of ecosystems (Tonini et al. 2019). Humans are
faced with two interrelated problems: the decreasing supply
of phosphate resources and eutrophication due to phosphate
loss in water systems. Phosphate ores are non-renewable and
disposable mineral resources (Wu et al. 2021). The move-
ment of phosphorus in nature is linear and difficult to circu-
late spontaneously in nature (Jupp et al. 2021). After being
used by organisms, phosphorus in nature enters the environ-
ment with the metabolism and death of organisms and is
eventually lost in seafloor sediments (Ohtake and Tsuneda
2019; Sun et al. 2018).
Currently, 71.95% of the world's phosphorus resources
are in Morocco, and most countries depend on phospho-
rus imports (Wu et al. 2021). Changes in the international
* Chongqing Wang
cqwang1990@zzu.edu.cn; zilangwang@126.com
1
School of Chemical Engineering, Zhengzhou University,
Zhengzhou 450001, China
2
School of Chemistry and Chemical Engineering, Central
South University, Changsha 410083, Hunan, China
3
Biorefining and Advanced Materials Research Center, SRUC​,
Edinburgh EH9 3JG, UK
tion in phosphorus-importing countries (Table S1) (Antunes
et al. 2018). Moreover, there are problems in the exploitation
of China's phosphorus rock, such as rapid resource consump-
tion, insufficient resources, low level of mineral exploitation,
and environmental pollution (Cui et al. 2019). From this
perspective, phosphorus resources recovery is imperative,
favoring the decline of phosphorus resource exploitation and
pollution reduction (Han et al. 2021).
The phosphorus enrichment causes eutrophication of
water bodies, inducing environmental pollution and eco-
nomic losses (Elser and Bennett 2011; Shaddel et al. 2020).
While phosphorus resources are facing a shortage, a large
amount of phosphorus is released into the environment every
year in the world (Ohtake and Tsuneda 2019; Roy 2017).
Phosphorus enrichment occurs derived from both point
sources, such as industrial effluents and municipal sewage,
and non-point sources, such as agricultural runoff. Phospho-
rus emissions from agricultural non-point sources in China
accounts for 67.20% of total pollution emissions (Fig. S1).
Similarly, phosphorus fertilizer in Italy accounts for 71%
of the total phosphorus load. Agricultural runoff is also a
major contributor to eutrophication pollution in lakes and
streams in the USA (Marella et al. 2022). According to the
2020 China State of the Environment Bulletin, 29.1% of 110
lakes in China are eutrophic. There are three strategies to
solve non-point source phosphorus loss: source reduction,

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process interception, and phosphorus recycle. Phosphorus
release derived from agricultural non-point source is one of
important pathways of environmental problems. Therefore,
for non-point source phosphorus pollution, developing effec-
tive techniques to recover phosphorus resources is necessary
(Yu et al. 2020).
Proposing green, cheap, and effective methods is crucial
to recover phosphorus resources from wastewater. Various
techniques have been investigated to deal with this problem,
including biological processes, chemical precipitation, ion
exchange, and adsorption (Huang et al. 2020; Yang et al.
2020). Adsorption is a promising method due to the inherent
features. Biochar is a solid material with high carbon content
prepared by thermochemical conversion of biomass (Xiang
et al. 2020). Biochar can be prepared from various raw
materials, including agricultural wastes, forestry processing
wastes, and sewage sludge (Panwar et al. 2019). The prepara-
tion of biochar is simple, generally including pre-treatment,
thermochemical processes, and post-modification (Li et al.
2020a). The past decade has witnessed a sharp increase
in biochar-related researches (Fig. S2). Biochar is widely
studied for various applications such as soil improvement
(O'Connor et al. 2018; Qian et al. 2021), carbon sequestra-
tion (Shalini et al. 2021; Sheng and Zhu 2018), catalysis
(Kumari et al. 2021; Wang et al. 2021a), wastewater treat-
ment (Wang et al. 2021b; Kang et al. 2022), and energy
production and storage (Bhatia et al. 2021; Senthil and Lee
Fig. 1  Density distribution maps showing occurrences of keywords
of publications related to biochar between 2007 and 2021. Based on
keywords perspective, there are many studies on biochar adsorption,
13
Environmental Chemistry Letters (2023) 21:497–524
2021). This can be verified by keywords of related publica-
tions shown in Fig. 1. Biochar has unique characteristics
such as high carbon content, high cation exchange capacity,
large surface area, porous structure, and abundant surface
groups (Wang and Wang 2019), enabling biochar as promis-
ing adsorbent.
Biochar has considerable potential as adsorbent for recov-
ering phosphorus from wastewater (Wang and Wang 2019).
Biochar has abundant active sites for phosphorus adsorp-
tion due to the porous structure, abundant surface groups,
and high content of mineral components (Mohan et al.
2014; Wang et al. 2020a). Recently, numerous studies have
been reported on using biochar as phosphorus adsorbents.
Research advances have been obtained from several perspec-
tives. First, various modifications are proposed for obtaining
functional biochar with excellent adsorption performance
(Wang et al. 2017; Yi et al. 2019). The loading metals such
as Mg (Jiang et al. 2019), Ca (Liu et al. 2019), Fe (Wang
et al. 2020b), La (Dai et al. 2014), and Bi (Zhu et al. 2016) is
an important and effective strategy. Second, extensive stud-
ies are implemented to explore the adsorption mechanism of
phosphorus onto biochar-based materials, including interac-
tions of electrostatic attraction, ion exchange, complexation,
and chemical precipitation (Deng et al. 2021). Additionally,
studies reveal that phosphorus-rich biochar can be used as
a soil amendment or a slow-release phosphorus fertilizer
to promote crop growth (Chu et al. 2021). More than 80%
mechanism research, wastewater purification, and pyrolysis is the
most widely used method for biochar preparation
Environmental Chemistry Letters (2023) 21:497–524
of the phosphorus loss with surface runoff is in the form of
particles, and fertilization has a great impact on the distribu-
tion and enrichment of phosphorus in soil aggregate (Mitran
et al. 2018; Yang et al. 2021). The input of biochar improves
soil quality, enhances water retention capacity, increases soil
organic matter, and ameliorates microbial communities, and
may help reduce phosphorus loss along runoff (Chen et al.
2018a; Fang et al. 2020; Wang et al. 2021c; Hansen et al.
2016).
Several reviews on phosphorus recovery have been pub-
lished. Sun et al. (2018) reported a review on phosphorus
recovery and reuse for applications in agriculture and envi-
ronment. Günther et al. (2018) summarized phosphorus
recovery for fertilizer production. Masrura et al. (2021)
reviewed the sustainable utilization of biochar for resource
recovery from human urine. Wang et al. (2022a) reported
slow-release of fertilizers derived from biochar for sustain-
able agriculture. To the best of our knowledge, no review
is reported focusing on phosphorus recovery using biochar.
Considering research advances and better understanding,
providing a review paper on the topic is essential. The
objectives of this review include: (i) the preparation and
modification of biochar-based phosphorus adsorbents; (ii)
the performance of phosphorus adsorption and the process
factors; (iii) the adsorption mechanisms of phosphorus onto
biochar; (iv) the potential application of phosphorus-rich
biochar as slow-release fertilizers.
Preparation and modification of biochars
Preparation methods
Biochar is a highly aromatic and carbon-rich solid mate-
rial prepared from biomass with porous structure (Liu et al.
2019). There is a wide range of biomass sources for the prep-
aration of biochar. The biomass sources are classified into
three major categories: plant-derived, animal-derived, and
sludge-based (Wang 2021). Biochar can be prepared by gasi-
fication, combustion, pyrolysis, hydrothermal carbonization,
etc. (Tripathi et al. 2016). Combustion is the oldest known
method for producing biochar. Although combustion can be
employed for any type of biomass, combustion is feasible if
the moisture content in the biomass is less than 50% (Goyal
et al. 2008). Combustion suffers from adverse environmen-
tal impacts and high energy losses for biochar preparation.
Hydrothermal carbonation is defined as the thermochemical
process of conversion of organic matter in water at moder-
ate temperatures (180–260 °C) and autogenous pressures
(Gascó et al. 2018). Compared to pyrolysis, hydrothermal
carbonization requires lower energy, and hydrothermal car-
bonization is more suitable to treat the material with high-
water content (Chen et al. 2020). The product generated by
499
hydrothermal carbonization is also known as hydrochar,
and hydrochar retains more oxygen functional groups and
relatively lower surface area compared to pyrolytic biochar
(Jian et al. 2018; Wang et al. 2020c). Gasification is a ther-
mochemical process that produces biosynthesis gas consist-
ing of CO, C ­ O2, and H
­ 2. Gasification is an effective method
of producing hydrogen from biomass with biochar as by-
products (Lv et al. 2007; Neves et al. 2011; Tripathi et al.
2016). Few gasification processes have the primary purpose
of preparing biochar, and biochar production is intentionally
limited to increase syngas yield (You et al. 2017).
Similar to the gasification process, the products of the
pyrolysis process also contain biogas, bio-oil, and biochar.
Currently, biochar is usually produced by pyrolysis. The
main product of fast pyrolysis is bio-oil, and the most effi-
cient method of biochar production is slow pyrolysis (Mohan
et al. 2014; Tomczyk et al. 2020). Biochar production
obtained by pyrolysis is influenced by biomass feedstocks,
heating rate, residence time, and pyrolysis temperature. The
parameters of pyrolysis process change the properties of bio-
char, such as pore structure, surface area, functional groups,
and zeta potential (Sun et al. 2014). Pyrolysis temperature is
the most important factor, followed by heating rate, nitrogen
flow rate, and residence time (Li et al. 2021a). For biochar
prepared from wood, 650 °C was the effective temperature
for forming biochar structure, 750 °C was the key tempera-
ture for creating porous structure, and a longer pyrolysis
time (> 60 min) increased the pore volume without affect-
ing the yield (He et al. 2021). Changes in pyrolysis condi-
tions affected the oxygenated groups on biochar surface (de
Mendonça et al. 2017). Compared with traditional pyrolysis,
microwave pyrolysis is more controllable and has the charac-
teristics of high energy efficiency and cost-effectiveness (Yu
et al. 2007). Pyrolysis process for biochar production has the
advantages of simple operation, low cost, and environmental
friendliness.
Additionally, the flash carbonization and torrefaction pro-
cess can also be used to prepare biochar (Wang and Wang
2019). Unlike pyrolysis and gasification, flash carbonization
does not produce bio-oil. Torrefaction produces a relatively
low O/C biochar, and biomass is partially oxidized and has
poor adsorption properties (Benavente and Fullana 2015).
In addition to the above preparation methods, novel methods
have been reported for biochar production in recent years.
Biochar prepared by the template method has a larger sur-
face area and total pore volume than biochar prepared by
direct pyrolysis (Zheng et al. 2021). The basic steps of the
template method are: (i) filling of precursors in the pores of
the template materials; (ii) polymerization of the precursors
in the template; (iii) carbonization; (iv) removal of the tem-
plate to obtain carbon product. The most prominent feature
of the template method is good structural controllability (Xi
et al. 2020). In combination with conventional pyrolysis, the
13
500
template method is more like an optimized and controlled
pyrolysis method with an additional biomass pre-treatment.
Moreover, the pyrolysis process can be optimized using a
fluidized bed, which effectively enhances the carbonization
step of biochar preparation, significantly reducing the car-
bonization time (Sun et al. 2016).
Biochar‑based phosphorus adsorbents
Due to its unique properties, biochar can be a promising
phosphorus adsorbent. The porous structure, surface area,
and surface functional groups are essential characteristics
of biochar adsorbents (Xiang et al. 2020). Biochar has been
reported as adsorbents for phosphorus recovery from water,
and the adsorption performance of biochar is closely related
to the physicochemical properties (Dai et al. 2020). As
shown in Table 1, the elemental composition and other phys-
icochemical properties of biochar rely on the biomass feed-
stocks and preparation methods. To obtain better phosphorus
adsorption performance, modification of pristine biochar
for functionalization has become a hot research topic (Wan
et al. 2017). Functional biochar performs better than pristine
biochar for environmental management, soil remediation,
and energy storage (Jiao et al. 2021; Yao et al. 2013a). The
preparation of functional biochar is divided into three stages:
pre-treatment, thermochemical process, and post-treatment
(Fig. 2). As thermochemical processes have been described
above, this section mainly discusses pre-treatment and post-
treatment for preparation of functional biochar.
Pre‑treatment
Pre-treatment refers to the treatment of raw feedstocks
to regulate the desired properties. Typical pre-treatment
includes washing, drying, crushing, and enrichment of
target elements. Washing and drying are mainly removing
contaminants and moisture from biomass feedstocks. Crush-
ing is conducted to obtain particles with desired particle
size. Growing or dipping with specific solutions can enrich
target elements in biomass. Yao et al. (2013a) fabricated
biochar by pyrolysis of Mg-enriched tomato plant tissues
cultured in magnesium-containing solutions. Mg-biochar
composites showed better phosphorus adsorption in aqueous
solutions than biochar prepared from normal tomato plant
tissues (Yao et al. 2013a, 2013b). Anaerobic digestion or
bacterial conversion of biomass feedstocks improved bio-
char's physicochemical properties and phosphorus adsorp-
tion performance. Biochar produced from anaerobically
digested dairy fibers recovered about 30% phosphorus from
wastewater in fifteen days (Streubel et al. 2012). Biochar
obtained from anaerobic digestion of sugar beet tailings was
a promising adsorbent to recover phosphorus from water
with a maximum adsorption capacity of 133.085 mg/kg (Yao
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Environmental Chemistry Letters (2023) 21:497–524
et al. 2011a). Anaerobic treatment significantly increased
the surface area, oxygenated functional groups, and mineral
composition of biochar (Tao et al. 2021). In addition to bac-
terial digestion and anaerobic fermentation, transabdomi-
nal digestion was investigated for biochar preparation. For
transabdominal transformation, the irregular folds, particle
aggregation surface, and pore structure, as the pyrolysis tem-
perature increased, generated more potential adsorption sites
(Tao et al. 2019). Modification by microbial or biological
treatment has the advantages of low cost and environmental
friendliness, but the process and results of the transformation
are uncertain (Wang et al. 2017).
Post‑treatment
Post-treatment refers to various physicochemical treatments
of biochar to obtain phosphorus adsorbents with excellent
properties. Steam activation and ball milling are the most
widely physical modifications (Wang et al. 2017). These
methods improve the adsorption capacity of modified bio-
char for heavy metal, nutrients, and organic pollutants by
increasing the surface area and forming more microporous
and mesopores (Lyu et al. 2018; Panwar and Pawar 2020).
Ball milling is a simple post-treatment method that reduces
particle size and increases the surface area of the particles
(Shan et al. 2016). Ball milling increases the external and
internal surface area for higher temperature biochar, while
ball milling enlarges the external surface area of lower tem-
perature biochar. In addition, ball milling also introduces
oxygen-containing functional groups (e.g., carboxyl and
hydroxyl) to biochar surface (Lyu et al. 2018; Wang et al.
2017). The use of ball milling to synthesize nano-biochar
materials is gaining attention for low cost and eco-friendly
nature (Kumar et al. 2020). Ball mill is an effective way
to prepare nano-biochar, nanoparticles have oxidation and
excellent adsorption ability (Li et al. 2021b). However,
reducing biochar particle size may cause potential risks to
groundwater, and the fine and light biochar particles are eas-
ily lost and difficult to be recycled for real application.
Steam activation effectively increases the surface area and
the internal pores (mainly micropores) of the biochar (Fungo
et al. 2014; He et al. 2021; Rajapaksha et al. 2015). The
tar produced during the carbonization process can partially
block the internal pores of the biochar, and steam activation
is effective in producing activated biochar with highly devel-
oped pores (Ioannidou and Zabaniotou 2007; Panwar and
Pawar 2020). Steam activation increases the pore size of bio-
char but has little effect on other properties (Azargohar and
Dalai 2008). Biochar prepared by a microwave steam activa-
tion process promoted lead adsorption, and the adsorption
capacity was comparable to commercial activated carbon
(Kwak et al. 2019; Lam et al. 2020). Steam activation mainly
uses water vapor, and other gases can also be employed for
 Table 1  Physicochemical properties of biochars prepared by various methods
Feedstocks Preparation Temperature Surface area Pore volume Mineral com- pH C H O N References
(°C) ­(m2/g) ­(cm3/g) position (wt.%)

Waste palm Microwave 700 110.80 0.070 – 8.00 51.0 ± 9.0 7.00 ± 2.40 39.0 ± 11.5 3.00 ± 0.10 Lam et al. (2020)
shell Steam activation
Banana straw MgCl2 soaking 430 6.6839 0.028 Mg 190.62 * 8.94 34.66 4.81 20.31 0.85 Jiang et al. (2019)
Sugarcane MgCl2 soaking 700 1440.4 1.574 Mg 602.30 * 9.60 45.01 – – – Fang et al. (2020)
bagasse
Oilseed rape Co-pyrolysis of 700 144.59 0.069 – 11.93 17.30 0.60 – 0.25 Wang et al.
coal gangue (2021c)
Hickory wood Slow pyrolysis 600 401.0 – – 8.40 81.81 2.17 14.03 0.73 Sun et al. (2014)
Hickory wood Hydrothermal 200 2.5 – – 6.00 55.30 6.13 39.84 0.25 Sun et al. (2014)
carbonization
Environmental Chemistry Letters (2023) 21:497–524

Batatas Soft-template- 800 286.3 0.249 – – 91.50 – 6.50 2.01 Zheng et al.
assisted hydro- (2021)
thermal route
Bagasse Slow pyrolysis 600 59.0 0.002 – 9.20 – – – – Lyu et al. (2018)
Bagasse Ball milling 600 364.0 0.125 – 6.90 – – – – Lyu et al. (2018)
Burcucumber Slow pyrolysis 700 2.31 0.008 – 12.32 ± 0.03 69.41 1.31 24.45 4.61 Rajapaksha et al.
(2015)
Burcucumber Steam activation 700 7.10 0.038 – 11.72 ± 0.01 50.55 1.66 44.88 2.54 Rajapaksha et al.
(2015)
Canola Slow pyrolysis 700 4.20 – – 10.93 78.7 1.37 14.28 1.71 Kwak et al.
(2019)
Canola Steam activation 106.00 – – 10.24 77.62 1.34 7.02 1.12 Kwak et al.
(2019)
Waste palm – – 1148.92 0.560 – – 76.0 ± 3.9 3.0 ± 0.4 19.0 ± 4.4 2.0 ± 0.1 Lam et al. (2020)
shell
Waste palm Steam activation 700 539.80 0.250 – – 81.0 ± 0.8 3.6 ± 0.1 14.0 ± 0.9 0.70 Lam et al. (2020)
shell
Rice straw Steam activation 700 105.21 0.062 – – – – – – Sakhiya et al.
(2021)
Rice straw CH3COOK 700 255.88 0.183 – – – – – – Sakhiya et al.
solution soak- (2021)
ing
Sugar beet tail- Slow pyrolysis 600 2.60 – – 9.45 50.78 2.08 36.70 1.83 Yao et al. (2011b)
ings
Sugar beet tail- Anaerobically 600 335.00 – – 9.95 30.81 1.38 39.87 2.74 Yao et al. (2011b)
ings digestion
Waste activated Co-precipitation 550 156.78 1.018 – – – – – – Yang et al. (2018)
sludge of ­Fe2+/Fe3+
under nitrogen

13
501

atmosphere
 Table 1  (continued)
502

Feedstocks Preparation Temperature Surface area Pore volume Mineral com- pH C H O N References
(°C) ­(m2/g) ­(cm3/g) position (wt.%)

13
Waste activated Co-precipitation 550 226.015 1.096 – – – – – – Yang et al. (2018)
sludge of ­Fe2+/Fe3+
under air
atmosphere
Waste activated Impregnation 550 254.400 0.889 – – – – – – Yang et al. (2018)
sludge with ferric
chloride under
air atmosphere
Sedimentation Slow pyrolysis 700 53.550 ± 2.590 0.135 ± 0.012 Ca 0.65 ± 0.01 7.54 ± 0.03 – – – – Antunes et al.
sludge (2018)
Sedimentation Ca(OH)2 mixing 700 54.40 ± 0.750 0.142 ± 0.003 Ca 11.52 ± 0.05 10.22 ± 0.02 – – – – Antunes et al.
sludge and pyrolysis (2018)
Japonica Slow pyrolysis 600 79.950 0.044 Ca 6.15 11.62 53.25 1.11 9.32 1.30 Jung et al. (2016)
and encapsu- Mg 2.61
lated with cal-
cium alginate
beads
Japonica Slow pyrolysis 800 45.460 0.031 Ca 6.15 12.59 60.51 0.74 4.89 1.13 Jung et al. (2016)
and encapsu- Mg 2.61
lated with cal-
cium alginate
beads
Japonica Slow pyrolysis 600 – – Ca 7.77 11.45 28.30 – – 5.65 Jung et al. (2016)
Mg 3.38
Crab shell Slow pyrolysis 600 52.130 0.048 Ca 27.38 – 19.20 1.28 – 2.01 Dai et al. (2017)
Mg 1.11
Crab shell Slow pyrolysis 900 48.440 0.048 Ca 36.14 – 9.08 0.89 – < 1.0 Dai et al. (2017)
Mg 1.50
Poultry manure Slow pyrolysis 350 – – Mg 2.26 8.30 36.3 2.50 37.5 2.60 Novais et al.
(2018)
Poultry manure Slow pyrolysis 650 – – Mg 2.36 10.00 32.6 2.70 26.8 1.40 Novais et al.
(2018)
Sugar cane Slow pyrolysis 350 – – Mg 1.16 8.80 60.8 3.30 53.4 1.80 Novais et al.
straw (2018)
Sugar cane Slow pyrolysis 650 – – Mg 1.28 9.20 68.2 0.80 62.3 1.70 Novais et al.
straw (2018)
Oak chips La(NO3)3 soak- 450 45.790 – – 11.08 40.46 1.39 – 0.42 Wang et al.
ing and slow (2016)
pyrolysis
Environmental Chemistry Letters (2023) 21:497–524
 Table 1  (continued)
Feedstocks Preparation Temperature Surface area Pore volume Mineral com- pH C H O N References
(°C) ­(m2/g) ­(cm3/g) position (wt.%)

Oak chips Slow pyrolysis 450 90.310 – – 9.27 77.43 3.17 – 0.17 Wang et al.
(2016)
Sheep manure Slow pyrolysis 800 195.970 0.110 – – – – – – Feng et al. (2021)
Sheep manure Oyster shells 800 5.090 0.040 Ca 17.15 – 17.53 – 22.67 0.62 Feng et al. (2021)
mixing and
slow pyrolysis
Sheep manure LaCl3 solution 800 12.040 0.060 La 10.84 – 10.32 – 22.24 0.99 Feng et al. (2021)
soaking and
slow pyrolysis
Wheat straw Bi2O3 solution 500 190.400 0.095 – – – – – – Zhu et al. (2016)
soaking and
Environmental Chemistry Letters (2023) 21:497–524

slow pyrolysis
Wheat straw Slow pyrolysis 500 124.440 0.080 – – – – – – Zhu et al. (2016)
C.korshinskii Slow pyrolysis 600 133.490 0.090 – – 68.43 – 31.57 – Cui et al. (2020)
C.korshinskii Iron plating and 600 89.370 0.050 Fe 11.01 – 54.52 – 34.47 – Cui et al. (2020)
slow pyrolysis
C.korshinskii Iron and alu- 600 233.290 0.130 Fe 7.03 – 39.44 – 38.18 – Cui et al. (2020)
minum plating Al 15.35
and slow
pyrolysis
Sewage sludge Slow pyrolysis 550 18.500 0.058 Ca 35.5 ± 1.03 6.9 – – – – Melia et al.
Al 19.8 ± 0.09 (2019)
Sewage sludge Slow pyrolysis 550 and 800 109.000 0.085 – – – – – – Melia et al.
under ­CO2 (2019)
atmosphere
Cotton stalks Slow pyrolysis 350 49.710 0.038 – – – – – – Ren et al. (2015)
Cotton stalks Slow pyrolysis 350 69.950 0.045 – – – – – – Ren et al. (2015)
and then iron
oxide coating
Corn cob AlCl3 soak- 450 85.813 0.1126 Al 0.115 42.79 4.554 33.51 0.33 Deng et al. (2021)
ing and slow
pyrolysis
Corn cob MgCl2 soaking 450 77.000 0.271 Mg 18.52 29.18 3.911 51.03 0.19 Deng et al. (2021)
and slow
pyrolysis
Sludge Slow pyrolysis 300 1.850 – – 6.96 – – – – Wang et al.
(2020b)

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 504 Environmental Chemistry Letters (2023) 21:497–524

steam activation (Wang et al. 2017). ­CO2 as an activation

gas is clean and easy to control during the activation process
(Zhang et al. 2004). At the same pyrolysis temperature, the
Wang et al.
References

(2020b)
O/C ratio of steam-activated biochar was higher than that of
­CO2-activated biochar (Xu et al. 2021).
Besides physical modifications, chemical methods can
change the properties of biochar in a more definite direc-
tion (Ahmed et al. 2016). Chemical modifications can
modify properties such as surface area, surface groups, and
N

adsorption selectivity of biochar (Li et al. 2021c; Panwar

et al. 2019). Treatment of biochar employing acid or alkali
impregnation is simple and effective methods. Sulfuric acid-
O

activated cucumber plant biochar had a high surface area,

–

250 times higher than that of inactivated biochar (Vithan-

age et al. 2015). Using phosphoric acid to modify biochar
increased the content of oxygen-containing groups (Peng
H

et al. 2017). The modification of biochar with cysteine could

enhance hydrophilicity, increase surface functional groups,
and improve adsorption capacity (Li et al. 2021d). Chemical
C

modification with NaOH produced biochar with high surface

area and microporous volume (Lillo-Ródenas et al. 2001;
Wang et al. 2018a). In general, alkali-modified biochar has a
5.70

large surface area, positively charged surface, and abundant

pH

oxygen-containing groups, which facilitates electrostatic

position (wt.%)

attraction and ligand exchange for the adsorption of nega-

Mineral com-

tively charged phosphorus (Ding et al. 2016; Eduah et al.,

2020). Additionally, sufficient washing of modified biochar
is essential, and inadequate washing after KOH treatment
–

strongly impeded the adsorption performance (Wongrod

et al. 2018).
Pore volume

In addition to acid or alkali modifications, the loading of

­(cm3/g)

metal elements is also an effective post-treatment method.

Iron-modified biochar can be fabricated by loading zero-
–

valent iron, iron oxides, iron compounds and compos-

ites (Wang and Wang 2018; Cui et al. 2020; Huang et al.
Surface area

2022; Sun et al. 2021). Zero-valent iron nanoparticles loaded

biochar removed 95% of phosphate in 30 min (Yuan et al.
­(m2/g)
4.890

2020). Fe-containing biochar prepared by iron impregna-

tion removed more than 85% of total phosphorus from arti-
ficial wastewater (Min et al. 2020). The magnetic property
Temperature

of ­Fe3O4/biochar composite made ­Fe3O4/biochar composite

easy to recycle, and the adsorption capacity was 20 times
(°C)
300

higher than that of biochar (Yang et al. 2018). Due to low

cost and simple preparation, this iron-modified biochar can
Fenton reagent
Dewatering of

be used as an efficient phosphorus adsorbent (Xiao et al.

sludge with
Preparation

pyrolysis
and slow

2019).
Other metals such as calcium and magnesium are also
employed to improve the phosphorus adsorption of bio-
Table 1  (continued)

char. The phosphorus removal capacity of calcium-rich

*The unit is mg/g

biochar was proportional to the calcium content, and the

Feedstocks

leaching rate of heavy metals from the calcium-loaded

biochar significantly declined (Antunes et al., 2018; Jung
Sludge

et al. 2016). The calcium-rich crab shell biochar increased

13
Environmental Chemistry Letters (2023) 21:497–524 505

Fig. 2  Preparation of biochar

phosphorus adsorbents. Bio-
chars can be prepared from a
wide range of biomass sources,
such as sludge sources, plant
sources and animal sources.
Biomass after pre-treatment,
thermal treatment and post
treatment will be purposefully
prepared to meet the demand of
biochar. Redrawn with permis-
sion of Elsevier from Xiang
et al. (2020)

the phosphorus removal from 26% to over 90% (Dai et al.
2017). Adsorption of phosphorus by magnesium-rich bio-
char is closely related to the loading of Mg on biochar
(Jiang et al. 2019). Biochar made by pyrolysis sugarcane
straw and chicken manure soaked in magnesium solu-
tion showed good performance of phosphorus adsorption
(Novais et al. 2018). Researchers also prepared Mg/Ca
modified biochar to achieve a better adsorption capacity
of 129.79 mg P/g (Fang et al. 2020).
Due to their unique properties, rare metals are proposed
to modify biochar for phosphorus adsorption. Lanthanum-
modified biochar can attenuate the effect of co-existing ani-
ons on phosphorus adsorption (Dai et al. 2014). The maxi-
mum adsorption capacity of lanthanum-modified biochar
prepared from municipal sludge was 93.91 mg/g (Li et al.
2020b). Xu et al. (2019) reported the adsorption capacity
of 36.06 mg P/g using lanthanum-modified biochar. Bio-
char with a Ca/La ratio of 1:1 prepared by co-precipitation

13
506
and pyrolysis reached a maximum adsorption capacity of
88.34 mg/g (Feng et al. 2021). The adsorption capacities of
the lanthanum-modified biochar differ significantly in dif-
ferent studies, but all researches prove that the lanthanum
loading on biochar improves the selectivity of phosphorus
adsorption (Li et al. 2020b; Wang et al. 2016; Zhao et al.
2021). The bismuth-modified biochar is also worth mention-
ing due to the excellent adsorption capacity for phosphorus,
and the formed bismuth phosphate can be used as poten-
tial photocatalyst (Zhu et al. 2016). Besides the physical or
chemical methods, an innovative biological post-treatment
method involved covering biochar surface with bacterial bio-
films cultured in food wastes, which reduced the surface area
of biochar, increased the average pore size, and improved
adsorption performance (Xing et al. 2021). Biochar adsor-
bent is a viable option for converting various waste biomass
into value-added products.
There are various methods to prepare functional biochar.
The choice of modification methods depends on the raw
material and application field. In order to obtain efficient
biochar-based phosphorus adsorbents, the loading of met-
als is better than other methods. Metals can be loaded on
biochar in various ways, including impregnation, biologi-
cal enrichment, and co-pyrolysis. The methods employed
for biochar preparation exhibit inherent features, and more
efforts are required to develop novel strategies for fabricating
efficient biochar-based adsorbents. Attention should be paid
to the cost, process complexity, and environmental impact
of the developed methods. For example, the used acid and
alkali solutions in the modification process should be dis-
posed properly, and the leaching risk of metal ions should
be considered.
Factors controlling phosphorus adsorption
Phosphorus adsorption can be influenced by various process
factors such as solution pH, adsorbent dosage, co-existing
ions, and reaction temperature. Examining the impacts of
process factors to evaluate the adsorption performance of
biochar is essential, and the design of optimal process factors
is imperative for real application. The results of phosphorus
adsorption from different studies are listed in Table 2. The
chapter outlines the effect of these factors on phosphorus
adsorption.
Solution pH
The pH of the solution has a significant effect on the adsorp-
tion capacity of biochar. Solution pH influences phosphorus
species and the surface characteristic of adsorbents, thus
affecting the dominant adsorption mechanism (Hou et al.
2020; Yao et al. 2013b). The surface charge, functional
13
Environmental Chemistry Letters (2023) 21:497–524
groups, and loaded metals of biochar can be significantly
influenced by solution pH. Biochar contains various func-
tional groups, and the surface groups such as carboxylate
and hydroxyl change with the variation of solution pH. The
groups are protonated and positively charged at low pH,
while the deprotonation of surface groups occurs with an
increase of solution pH. When pH is lower than the point of
zero charge, the positively charged surface of biochar favors
the adsorption of anionic phosphorus species through elec-
trostatic repulsion.
The phosphorus species at different pH can be shown
in Fig. S3, and various forms of phosphorus can be seen.
When the pH of the solution was between 3.0 and 6.0, the
dominant species of phosphorus in the solution was ­H2PO4−,
which was easily bound to La. As shown in Fig. 3a, with the
increased pH, the dominant species changed, and phospho-
rus adsorption decreased (Li et al. 2020b). A similar sce-
nario was reported for phosphorus adsorption on La-coated
biochar (Wang et al. 2016). For phosphorus adsorption using
core–shell γ-Al2O3/Fe3O4 biochar, the impact of pH exhib-
ited a volcanic trend with an optimum adsorption pH = 5.0
(Cui et al. 2020). The adsorption capacity of Ca-La modified
biochar increased with increasing solution pH (Feng et al.
2021). Above studies demonstrate that pH changes have dif-
ferent impacts on phosphorus adsorption. Low pH induces
the protonation of surface groups and metal leaching. The
former favors the adsorption of phosphorus anions, and the
latter is adverse to the adsorption process.
Adsorbent dosage
Phosphorus adsorption highly depends on the adsorbent dos-
age. When the phosphorus concentration is designed, the
addition of more adsorbent generally results in large phos-
phorus adsorption, but this increase is limited for excessive
adsorbent. In Fig. 3b, using coal gangue-biochar composites
as the adsorbent, the phosphorus removal increased with
increasing the adsorbent dosage when the adsorbent dosage
was low (Wang et al. 2021c). As the adsorbent increases, the
available adsorption sites increase, facilitating the phospho-
rus adsorption. When the adsorbent is sufficient, phospho-
rus in the solution can be effectively removed. The partition
coefficient defined as Equation S1 can be an indicator to
evaluate the adsorption performance of adsorbents. The high
value of partition coefficient indicates high adsorption abil-
ity, especially for low concentration adsorbate. Zhu et al.
(2016) reported that the partitioning coefficient of bismuth-
immersed biochar increased with the increase of the amount
of adsorbent, indicating that the biochar surface was not uni-
form. When the adsorbent dosage exceeded a specific value,
the phosphorus removal no longer increased. This situation
is ascribed to agglomeration of biochar particles and reduced
phosphorus concentration. The fine biochar particles will
Environmental Chemistry Letters (2023) 21:497–524 507

Table 2  Adsorption performance of phosphorus by biochar-based adsorbents

Biochar precur- Adsorbents Adsorption pH Temperature P concen- Adsorbent Co-existing ion References
sor capacity (°C) tration dosage
(mg/g) (mg/L) (g/L)

Sugarcane Mg modified 129.79 2.0 23 ± 2 1282.14 10.0 – Fang et al. (2020)

bagasse biochar
Thalia dealbata Fe-modified 15.86 10.0 25 40 12.5 – Xiao et al. (2019)
Thalia deal-
bata derived
biochar
Sedimentation Calcium-rich 147.06 4.5 ± 0.1 22 ± 2 1500 10.0 – Antunes et al.
sludge biochar (2018)
Sedimentation Pristine biochar 14.08 4.0 22 ± 2 1500 10.0 – Antunes et al.
sludge (2018)
Rice straw Lanthanum 61.57 4.5 25.0 40 1.0 – Dai et al. (2014)
doped hydro-
char
C.korshinskii Core–shell 205.70 5.0 25.0 50 1.0 F−, ­Cl−, ­NO3−, Cui et al. (2020)
γ-Al2O3/Fe3O4 ­SO42−
biochar
Sludge Iron-rich sludge 1.84 5.5 25.0 46 15.0 Cl−, ­NO3−, Wang et al.
biochar ­HCO3− (2020b)
Poplar tree Dolomite car- 207.00 5.83 25.0 25 1.25 – Li et al. (2018)
wood sawdust bon compos-
ites
Oilseed rape Coal gangue- 7.90 4.0 25.0 50 12.5 NO3−, ­CO32−, Wang et al.
straw biochar ­Cl−, ­SO42− (2021c)
composites
Corn cob Pristine biochar 6.50 2.8 22 ± 0.5 100 16.7 – Eduah et al.
(2020)
Waste activated Iron-modified 110.00 2.0 22 ± 0.5 20 2.0 SO42−, ­NO3−, Yang et al. (2018)
sludge biochar ­CO32−
L. Japonica, Calcium- 157.70 6.0 30.0 1000 1.0 – Jung et al. (2016)
alginate beads
granular
biochar
Oka chips Lanthanum 46.37 3.0 45.0 1000 2.0 – Wang et al.
loaded biochar (2016)
Dewatered sew- Lanthanum- 93.91 5.4 23 ± 0.5 50 0.5 Cl−, ­NO3−, Li et al. (2020b)
age sludge coated biochar ­SO42−,
­HCO3−,
­CH3COO−
Sheep manure Biochar-based 47.83 11.0 25 ± 0.5 50 1.0 CO32−, ­Cl−, Feng et al. (2021)
Ca composite ­NO3−, ­SO42−
Sheep manure Biochar-based 49.67 10.0 25 ± 0.5 50 1.0 CO32−, ­Cl−, Feng et al. (2021)
La composite ­NO3−, ­SO42−
Corn-cob Mg modified 56.12 11.0 25.0 50 2.0 – Deng et al. (2021)
biochar
Corn-cob Al modified 44.79 6.0 25.0 50 2.0 – Deng et al. (2021)
biochar
Sugarcane har- Magnesium 121.25 3.0 23.0 ± 0.2 20 2.5 – Li et al. (2016)
vest residue oxide
Decorated mag-
netic biochar

13
508
Fig. 3  Effect of process factors on phosphorus adsorption: a solution
pH, reprinted with permission of Elsevier from (Li et al. 2020b); b
biochar dosage, reprinted with permission of Elsevier from (Wang
et al. 2021c); c reaction time, reprinted with permission of Elsevier
from (Wang et al. 2016); d initial phosphorus concentration, reprinted
agglomerate for excessive adsorbent, which may reduce the
adsorption capacity due to the decrease in the available sur-
face area of the adsorbent. From the point of view of the
economics of practical applications, the optimal dosage of
biochar for phosphorus adsorption should be determined.
Adsorption time
The adsorption time should also be considered for phospho-
rus adsorption. In general, the adsorption capacity increases
with adsorption time in the beginning, and then reaches a
constant value after reaching adsorption equilibrium. Fig-
ure 3c shows the rapid increase of phosphorus adsorption
within 13 min, and then the adsorption equilibrium reaches
(Wang et al. 2021c). After a period of adsorption, the
active sites of biochar adsorbents are mostly occupied, and
the phosphate concentration in the water is reduced, mak-
ing phosphate challenging to collide with the active sites
of the adsorbents. The time required to reach equilibrium
adsorption can be an important indicator to evaluate the
performance of biochar adsorbents, and rapid adsorption
is favorable for practical application. Adsorption kinetics
closely related to adsorption time provides insights into
adsorption process. Yang et al. (2018) considered that the
adsorption rate and fitted kinetic model provided supporting
evidence for judging the adsorption mechanism. In addition,
13
Environmental Chemistry Letters (2023) 21:497–524
with permission of EDP Sciences from (Xiao et al. 2019); e reaction
temperature, reprinted with permission of Elsevier from (Wang et al.
2016); f co-existing anions, reprinted with permission of Elsevier
from (Cui et al. 2020)
according to the relationship between the adsorbed phospho-
rus and the time square root (­ t0.5), whether the diffusion of
the inner surface of the particle is the main factor of adsorp-
tion can be explored.
Initial phosphorus concentration
In natural wastewater, the phosphorus concentration varies
with sources and time. To examine the efficiency of biochar-
based adsorbents, the initial phosphorus concentration should
be examined. Figure 3d exhibits that the initial concentration
significantly influences phosphorus adsorption. An increase
in the initial phosphorus concentration caused a decrease in
the phosphorus removal and an increase in adsorption capac-
ity (Wang et al. 2016). Additionally, phosphorus species are
changes due to the potential effect of phosphorus concentration
on pH. Taking orthophosphate adsorption as an example, the
ionization of phosphoric acid can be shown as Equations S2-4.
The adsorption process of biochar after surface protonation can
be depicted as Equations S5-6. After a decline in phosphorus
concentration due to biochar adsorption, the amount of ionized
­H+ in water changes and induces hydroxyl protonation/depro-
tonation on biochar surface. This will affect the electrostatic
attraction between phosphorus species and biochar surface.
The maximum adsorption capacity is related to the initial
phosphorus concentration, and may be biased for different
Environmental Chemistry Letters (2023) 21:497–524
biochar due to the difference in phosphorus concentration.
To judge the performance of biochar adsorbents based on
adsorption capacity only is not objective. Researchers have
proposed the partition coefficient to evaluate the phosphorus
adsorption efficiency (Cui et al. 2020; Huang et al. 2020).
The smaller the partition coefficient value, the more phos-
phorus remains in the solution.
Temperature
From a thermodynamic point of view, high temperature
promotes the diffusion process. The enhanced movement
of adsorbent particles and phosphorus molecules increases
the collision probability, thus promoting adsorption. The
adsorption capacity increased with an increase in tem-
perature and increased more rapidly when the temperature
exceeded 35 °C (Fig. 3e) (Wang et al. 2016). For treating
actual wastewater, the effect of temperature on phospho-
rus release should be considered from sediments. Studies
have shown that elevated temperature promoted phospho-
rus released from sediments in wastewater (Gibbons and
Bridgeman 2020). This will directly affect the phospho-
rus concentration in water and indirectly affect the whole
adsorption process. Additionally, adsorption temperature is
closely related to operating costs. High temperature signifies
high energy requirement and cost, and thus high adsorp-
tion efficiency at low temperature is favorable for the actual
application.
Co‑existing ions
There are various ions in natural wastewater, and co-exist-
ing ions should be considered for the adsorption process.
Phosphorus adsorption is influenced by co-existing ani-
ons in solution, which compete with phosphorus species
for adsorption sites. The presence of C ­ l−, ­F−, ­SO42−, and
−
­HCO3 had negative impacts on phosphorus adsorption
(Fig. 3f) (Cui et al. 2020; Huang et al. 2020). Lanthanum-
modified biochar was effective in excluding the interference
of co-existing anions (Feng et al. 2021; Xu et al. 2019). A
high adsorption capacity was obtained with pH ranging from
3.0 to 6.0, and co-existing ­Cl−, ­NO3−, ­SO42−, ­HCO3−, and
citric acid had little effect on phosphorus adsorption (Feng
et al. 2021). However, lanthanum has a potential risk of
environmental contamination and lanthanum modification
requires a relatively high cost. For phosphorus adsorption,
improving the performance of biochar-based adsorbents to
exclude the interference of co-existing anions in the solution
is crucial.
Phosphorus adsorption by biochar-based adsorbents is
significantly influenced by process factors. The adsorption
data related to process factors provide guidance of device
design and practical application of proposed process. Most
509
of current researches are based on simulated wastewater,
and tests of real wastewater containing phosphorus should
be implemented to provide more reliable data. Additionally,
the adsorption data can be examined by mathematical mod-
els such as kinetic models, isotherms, and thermodynamic
models.
Adsorption kinetics, isotherms,
and thermodynamics
Adsorption kinetics
Adsorption is the process of adsorbate transfer from the bulk
solution to the surface of adsorbents. Adsorption kinetics,
adsorption mechanism, and adsorption equilibrium are not
independent but interrelated. The large-scale application of
biochar to phosphorus adsorption from wastewater requires
a clear understanding of the diffusion mechanism and sur-
face reactions in the adsorption process (Tong et al. 2019;
Ambaye et al. 2021). To describe the adsorption process
more clearly, researchers have established several mathemat-
ical models to examine adsorption kinetics. The adsorption
process can be divided into diffusion control adsorption and
reaction control adsorption based on kinetic studies. Various
kinetic models that can be employed to study phosphorus
adsorption are listed in Table S2.
The liquid film diffusion kinetic model and the inner dif-
fusion kinetic model are relevant. For phosphorus in solu-
tion, diffusion into the biochar pore involves the following
steps: (i) diffusion in the bulk solution, (ii) diffusion in the
liquid film on the surface of biochar adsorbents, and (iii)
diffusion in the pore water, also known as internal diffu-
sion. For the solid–liquid system, the liquid extends on the
adsorbent surface to form a relatively stationary film layer,
and phosphorus must pass through this film layer before
reaching the solid surface. If film diffusion is the rate-lim-
iting step, the adsorption rate is driven by a concentration
gradient. In the well-mixed reaction system, the concen-
tration gradient of the liquid film is almost negligible, so
film diffusion is usually not a control step (Benjamin and
Lawler, 2013). If the diffusion stage in the particle is the
control step of the adsorption process, and the kinetic model
of intraparticle diffusion is used to evaluate this (Plazinski
and Rudzinski 2009). The intraparticle diffusion model is
based the assumptions: the negligible liquid film diffusion
resistance, the random diffusion direction, and the constant
diffusion coefficient. Cui et al. (2020) prepared core–shell
γ-Al2O3/Fe3O4 biochar, and the fitting between the experi-
mental data and the internal diffusion kinetic model showed
a three-segment line formula, indicating that the adsorption
process could be described by film diffusion and subsequent
particle diffusion. For phosphorus adsorption by bismuth
13
510
impregnated biochar, the fitting of kinetic model manifested
correlation coefficient between 0.920 and 0.941, showing
that diffusion model was not the only limiting step (Zhu
et al. 2016). According to the phosphorus adsorption rate,
adsorption can be mainly divided into two steps: (i) transfer
from the bulk solution to the external surface of biochar
adsorbents driven by the initial phosphate gradient; (ii) dif-
fusion process within the particle, in which phosphate mol-
ecules are transported from the external surface to the pores
of biochar.
Another situation is the “adsorption reaction”, where the
binding of phosphorus to the adsorption sites of biochar.
Kinetic models associated with reaction control assume neg-
ligible diffusion rates and focus on the last step of adsorp-
tion (Gupta and Bhattacharyya 2011). Rate-limiting kinetic
methods are more suitable for binding to adsorption sites by
ion exchange or sharing electron pairs by covalent or ionic
bonds (Ho and McKay 1998). The adsorption process obey-
ing the pseudo-first-order kinetics is usually considered as
the physical adsorption. He et al. (2017) prepared pristine
biochar for phosphorus adsorption, and the experimental data
were consistent with a pseudo-first-order kinetic model, indi-
cating that phosphorus adsorption by pristine biochar was
dominant by physical adsorption. The pseudo-second-order
kinetics assumes that the adsorption process is controlled
by a chemical mechanism, and there is electron sharing or
electron transfer between phosphorus species and the adsor-
bent surface. The process of phosphorus adsorption by ferric
oxide/biochar conformed to the pseudo-second-order kinetic
model (He et al. 2017), indicating the controlled mechanism
of chemical adsorption. Kinetic models provide useful infor-
mation about diffusion or reaction rates. Data fit using kinetic
models is necessary, but only the mechanical extrapolation
information is not enough. To better understand the adsorp-
tion behavior and reveal the adsorption mechanism, combin-
ing adsorption kinetic with other analysis to study the adsorp-
tion process may be necessary (Tong et al. 2019).
Adsorption isotherms
The adsorption isotherm is the relationship between the
equilibrium concentration of adsorbates in two phases at a
certain temperature and pH (Lowell and Shields, 1991). The
adsorption isotherm provides the key information to explain
how phosphorus interacts with the adsorbents during the
adsorption process, and characterize the surface properties
and adsorption capacity of biochar-based adsorbents Stud-
ies on adsorption isotherms are essential for better under-
standing of adsorption mechanism and the proper design
of adsorption systems (Ayawei et al. 2017). Researchers
have proposed a variety of isotherm models to study the
adsorption equilibrium, including single-parameter models
(Henry model), two-parameter models (Langmuir model
13
Environmental Chemistry Letters (2023) 21:497–524
and Freundlich model, etc.), three-parameter models (Sips
model and Toth model, etc.), and multi-parameter models
(Table S3). Among them, Langmuir isotherm and Freundlich
isotherm are commonly used in phosphorus adsorption.
Langmuir isotherm makes several ideal assumptions,
such as the homogeneous surface of adsorbents, monolayer
adsorption, dynamic equilibrium of adsorption, and no
interaction between adsorbed molecules. Langmuir iso-
therm explains the surface coverage by balancing the rela-
tive rate of adsorption and desorption (Ayawei et al. 2017).
The parameter Ke of Langmuir model is a constant related
to adsorption capacity. The parameter RL , a dimensionless
constant, is the separation factor. RL is used to describe
the difficulty of the adsorption process: difficult adsorp-
tion ( RL > 1); linear adsorption ( RL = 1); easy adsorption
(0 < RL < 1); irreversible adsorption ( RL = 0) (Wang and
Guo 2020). The good fitting of Langmuir model ­(R2 > 0.93)
indicated uniform monolayer adsorption of phosphorus onto
calcium-flour biochar, and the easy adsorption was verified
by Langmuir parameter (0< RL < 1) (Wang et al. 2018b).
Yao et al. (2013a) prepared magnesium-rich tomato biochar
for phosphorus adsorption, and the linear fitting of experi-
mental data using the Langmuir–Freundlich isotherm proved
that the process was controlled by multiple mechanisms.
Additionally, Langmuir model can calculate the maximum
adsorption capacity, which is helpful to evaluate the adsorp-
tion ability of different biochar-based adsorbents.
Freundlich model is the mathematical model used to
describe non-ideal and reversible adsorption (Ezzati 2020).
Freundlich model is an empirical model that assumes mul-
tilayer adsorption on the adsorbent surface, the surface het-
erogeneity, and the exponential distribution of active sites
and their energies (Ayawei et al. 2015). The characteristic
parameter n of Freundlich model is an important parameter.
When n is between 2 and 10, the adsorption process is easy
to occur, and while the adsorption is difficult when n < 0.5.
He et al. (2017) prepared ferric oxide/biochar for phosphorus
adsorption. The Langmuir–Freundlich model better matched
the experimental data at 298 K and 308 K, while the Fre-
undlich model better fitted the experimental data at 318 K.
This was because the hydroxyl ions on the surface of fer-
ric oxide/biochar reacted with phosphorus species faster at
higher temperature.
Adsorption thermodynamics
Like isotherms, thermodynamics plays an important role
in characterizing the adsorption equilibrium and mecha-
nism. The important thermodynamic parameters include
Gibbs free energy, enthalpy change, and entropy change,
and their mathematical relationship is shown in Eqs. 1 and
2. In this section, the isosteric heat of adsorption, enthalpy
change of adsorption, and free energy change of adsorption
Environmental Chemistry Letters (2023) 21:497–524
are described, which provide additional insights into the
adsorption mechanism of phosphorus onto biochar-based
adsorbents.
ΔG = ΔH − TΔS (1)
ΔG = −RTlnKC (2)
where ΔG is the Gibbs free energy (kJ/mol); ΔH is the
enthalpy change (kJ/mol); ΔS is the entropy change (J/mol
K); R is the ideal gas constant, 8.314 J/(mol·K); T is tem-
perature (K); KC represents the dimensionless equilibrium
constant, which can be derived from the constants in Lang-
muir, Freundlich, and other isotherm models.
Isosteric heat of adsorption is used for quantitative gas
phase adsorption and later for liquid phase adsorption
(Myers 2002). The adsorption interactions include chemi-
cal bond, hydrogen bond, electron donor–acceptor interac-
tion, conjugation π-π interaction, electrostatic force, van der
Waals force, etc. The adsorption interactions can be roughly
judged by the isosteric heat of adsorption (Vonopen et al.
1991). To discuss surface heterogeneity and identified
adsorption mechanism on magnesium ferrite/biochar mag-
netic composites, the Clausius–Clapeyron equation based on
Sips parameters was used to calculate the isosteric heat of
adsorption (Jung et al. 2017). In general, the isosteric heat of
adsorption below 80 kJ/mol indicates a physical adsorption
process (Tun and Chen, 2021; Sircar et al. 1999). Jung et al.
(2017) reported that there was a continuous increase in the
isosteric heat from 36.02 to 76.10 kJ/mol with the increased
adsorption amount. This indicated that magnesium ferrite/
biochar magnetic composites had a heterogeneous surface,
and phosphorus adsorption was the physical adsorption pro-
cess. The most widely used method to calculate the enthalpy
change of adsorption is based on the Van’t Hoff equation
at constant pressure. A change in enthalpy means a change
in the energy of the adsorption process, and the positive
enthalpy change indicates an endothermic process while a
negative value implies an exothermic process. Typically,
physical adsorption occurs when the enthalpy change is less
than 40 kJ/mol, and chemisorption occurs when the enthalpy
changes in 50–200 kJ/mol (Wang et al. 2021d). Entropy
change reveals the change of disorder of phosphorus species
binding to biochar surface, and a positive value indicates the
increase of interface disorder. For phosphorus adsorption
at pH 5.5, the enthalpy change and entropy change were
10.00 kJ/mol and 93.73 J/mol K, respectively (Karunanithi
et al. 2017). Thermodynamic analysis indicated that the
phosphorus adsorption by soybean stover-derived biochar
was physical adsorption and an endothermic process.
Gibbs free energy variation represents the possibility
and feasibility of the adsorption process. Gibbs free energy
reflects the balance of different interactions influencing
511
adsorption (Tong et al. 2019). The negative value implies
the spontaneous adsorption process, and large absolute
value indicates that the adsorption process has good feasi-
bility. Calculating the Gibbs free energy based on the data
of adsorption isotherm is relatively simple (Al-Ghouti and
Da'ana 2020). Analysis of multiple contributions from dif-
ferent mechanisms requires molecular dynamics simulations
and thermodynamic studies (Tong et al. 2019). The Gibbs
free energy of phosphate adsorption on the eupatorium ade-
nophorum biochar was 6.66 kJ/mol (15 °C), 6.13 kJ/mol
(25 °C), and 5.56 kJ/mol (35 °C), suggesting more favorable
adsorption with the increase in temperature (Cheng et al.
2021). The negative value of Gibbs free energy for phos-
phorus adsorption on Mg-modified corn biochar indicated
the spontaneous behavior of the adsorption process (Fang
et al. 2014).
Adsorption mechanisms
Understanding the underlying mechanism of phosphorus
adsorption is necessary to improve the adsorption capac-
ity of biochar-based adsorbents. The adsorption behavior
depends on biochar's properties such as surface groups,
porous structure, mineral components, and loaded active
components. The adsorption mechanism involves several
interactions such as physical adsorption, surface precipita-
tion, complexation, electrostatic attraction, and ion exchange
(Dai et al. 2020). Fig. 4 shows various interactions involved
in phosphorus adsorption onto biochar-based adsorbents
(Wang et al. 2022a). The mechanism is discussed in this sec-
tion from the perspective of the metal-modified adsorbents.
Mg‑rich biochar
Mg-loaded biochar is extensively studied as phosphorus
adsorbents. The adsorption mechanism associated with
Mg-rich biochar has been well revealed. The adsorption
mechanism of phosphorus from Mg-rich biochar derived
from tomato tissues was reported (Yao et al. 2013a). Clus-
ters of Mg-phosphorus nanocrystals on biochar surface
were observed after adsorption (Fig. 5a). X-ray diffraction
analysis revealed the appearance of magnesium hydrogen
phosphate and magnesium dihydrogen phosphate on the
adsorbed biochar (Fig. 5b and 5c), manifesting the suc-
cessful adsorption of phosphorus through magnesium-
phosphorus crystals. X-ray photoelectron spectroscopy
confirmed the precipitation of phosphorus on the biochar.
A dramatic reduction in the Mg hydroxylated compound
after adsorption formed the Mg-P precipitation with phos-
phate ions (Fig. 5d and 5e). The pH of the solution was
­ PO42− and
5.2 to 7.9, and phosphorus was in the form of H
−
­HPO4 . Although MgO and Mg(OH)2 had low solubility,
13
512
Fig. 4  Adsorption mechanisms
of biochar-based phosphorus
adsorbent. The adsorption
mechanisms involves elec-
trostatic attraction, compl-
exation, ligand exchange, anion
exchange, precipitation, and
physical adsorption. Redrawn
with permission of Elsevier
from (Wang et al. 2022a)
the presence of phosphate anions promoted their dissolu-
tion forming insoluble salts (­ MgHPO4 and Mg(H2PO4)2).
The process could be described by Equation S7-11. The low
surface energy of biochar surface facilitated the nucleation
growth of phosphate salt precipitates on the surface. The
role of hydrogen bonding in the adsorption of phosphorus
on biochar should not be overlooked. The high content of
phosphate analogs (64%) was attributed to hydrogen bond-
ing (Fig. 5f). Mg(OH)2 and the precipitates generated in the
adsorption, such as M ­ gHPO4 and Mg(H2PO4)2, adsorbed
additional phosphorus analogs through hydrogen bonding.
The process of phosphorus analog adsorption by biochar
through magnesium phosphate could be described by Equa-
tions S12-13.
The role of functional groups on biochar surfaces in phos-
phorus adsorption was revealed (Jiang et al. 2019). Infrared
spectra showed that all characteristic peaks broadened and
weakened after adsorption. The anthraquinone or aromatic
ring was replaced by -(OH)2 at 3416–3430 ­cm−1, and the
absorption peaks at 1039–1088 ­cm−1 and 608–631 ­cm−1
disappeared due to the phosphorus adsorption by hydroxyl
groups and phenols on biochar surface. Fang and col-
leagues studied demonstrated the role of hydroxyl groups in
the adsorption of phosphorus (Fig. 5g) (Fang et al. 2020).
The peak at 3400 ­cm−1 ascribed to -OH group was signifi-
cantly weakened, which indicated deprotonation of hydroxyl
13
Environmental Chemistry Letters (2023) 21:497–524
groups during the adsorption of phosphate. In addition, an
apparent newly formed peak at 1100 ­cm−1 was detected,
which was attributed to hydrogen phosphate (-HPO4). The
carboxyl and phenolic hydroxyl groups on the biochar sur-
face were consumed during the adsorption process. The
phosphorus in the wastewater was not adsorbed in the form
of pure phosphate crystals. Ligand exchange in the presence
of ­NH4+ has been reported. ­Mg2(OH)3Cl·4H2O on the sur-
face of banana straw biochar could exchange ligands with
total phosphorus in water to form ­MgNH4PO4·6H2O during
the adsorption process (Jiang et al. 2019).
Electrostatic attraction has been reported in other stud-
ies on Mg-modified biochar (Luo et al. 2021; Yao et al.
2013b). Nanoscale Mg(OH)2 and MgO particles appeared
on the surface of Mg-modified biochar, which are the main
adsorption sites of phosphorus. X-ray diffraction showed
that the MgO diffraction peaks weakened, and new peaks
of ­MgHPO4 and ­Mg3(PO4)2 appeared on biochar surface
(Fig. 5h) (Chen et al. 2018b). ­Mg2+ released from the bio-
char was co-precipitated with ­PO43− or H ­ PO42− and was
promoted by electrostatic attraction. The situation is a little
more complex for natural wastewater, where metal ions are
also involved in the adsorption process. Phosphorus recov-
ery from the acid extract of incinerated sewage sludge ash
was studied using Mg-modified biochar (Fang et al. 2020).
The co-precipitation of phosphorus with Mg, Ca, Fe, and
Environmental Chemistry Letters (2023) 21:497–524
Fig. 5  a Scanning electron microscope image of biochar after phos-
phorus adsorption, reprinted with permission of ACS publications
from (Yao et al. 2013a); b X-ray diffraction of biochar before phos-
phorus adsorption, reprinted with permission of Elsevier from (Yao
et al. 2013b); c after phosphorus adsorption, reprinted with permis-
sion of ACS publications from (Yao et al. 2013a); d X-ray photoelec-
tron spectra of the Mg 1 s spectra of the biochar before phosphorus
adsorption, reprinted with permission of Elsevier from (Yao et al.
2013b); e X-ray photoelectron spectra of the Mg 1 s spectra of the
Al occurred assisted by electrostatic attraction (Fig. 5i).
Mg-modified biochar generally has a positive charge, and
an electrostatic attraction to the phosphate to form mono-
nuclear or polynuclear complexes when the solution pH is
less than the ­pHPZC (Kosmulski 2009).
In summary, chemical precipitation and electrostatic
attraction play a more important role in phosphorus adsorp-
tion by Mg-modified biochar. The main reasons for the
excellent adsorption performance may be: (i) the positive
charge on the surface of the modified biochar is conducive
to electrostatic attraction; (ii) Mg co-precipitates with phos-
phorus in water, inducing surface precipitation of P analogs
513
biochar after phosphorus adsorption, reprinted with permission of
ACS publications from (Yao et al. 2013a); f X-ray photoelectron
spectra of P 2p3/2 after phosphorus adsorption, reprinted with per-
mission of ACS publications from (Yao et al. 2013a); g infrared spec-
­ gCl2 (Fang et al. 2020); h X-ray dif-
tra of the biochar modified by M
fraction of the cow dung-derived biochar, reprinted with permission
of Elsevier from (Chen et al. 2018b); i X-ray diffraction of the biochar
modified by ­MgCl2, reprinted with permission of Elsevier from (Fang
et al. 2020)
in water through hydrogen bonding; (iii) the abundant
functional groups after modification increase the surface
hydroxyl protonation and facilitates the exchange of ligands
with phosphorus.
Ca‑rich biochar
Similar to Mg, Ca is another alkali earth metal widely
used for biochar modification. Ca-rich biochar was used
as phosphorus adsorbent and found that -OH was involved
in the chemisorption process (Liu et al. 2019). X-ray dif-
fraction analysis showed the characteristic peaks of CaO
13
514
and Ca(OH)2 disappeared, and the diffraction peaks of
­Ca5(PO4)3(OH) appeared after phosphate adsorption. Com-
bined with other analysis, the dominant mechanism was
revealed as the combination of C ­ a2+ and O­ H− with phos-
phate to produce ­Ca5(PO4)3(OH) precipitates. Antunes
et al. (2018) also reported the precipitation mechanism of
phosphorus adsorption onto Ca-doped biochar. Ca-modified
biochar had preferential adsorption for phosphorus due to
the reaction of Ca(OH)2 and P ­ O43− to form hydroxyapatite
­(Ca5(PO4)3(OH)) crystals (Wang et al. 2018b). The involved
reactions can be shown as Equations S14-16.
Fe‑rich biochar
Due to the low toxicity and natural abundance, iron is also
used for biochar modification (Wang et al. 2021e; Qian
et al. 2021; Han et al. 2021). ­H2PO4− is the predominant
phosphorus species in neutral waters (pH around 7.0). The
ligand exchange between ­OH− and ­H2PO4− formed surface
complexes with Fe is the primary mechanism for Fe-based
biochar (Yuan et al. 2020). Yang et al. (2018) prepared Fe-
modified biochar by impregnation waste-activated sludge
biochar with F­ eCl3. The amorphous hematite and amorphous
hydroxide were determined in the biochar, and these iron
oxides and metal hydroxyl groups acted as active adsorption
sites for phosphate adsorption (Ren et al. 2015). Fe-modified
biochar had a high zeta potential, which favored electrostatic
attraction. Infrared spectra analysis indicated that the -OH
group was replaced by ­H2PO4− and ligand exchange played
an important role in phosphate adsorption (Equation S17).
Other elements‑rich biochar
Bimetals modification is proposed to enhance the adsorption
capacity of biochar, and Mg/Ca is a common combination.
The MgO-CaO/biochar composites showed the contribution
of phosphate crystal deposition and electrostatic attraction
to phosphate adsorption and the involvement of π-π interac-
tions in humate adsorption (Li et al. 2018). The presence
of MgO and CaO particles on the surface provided high
pH (9.5–10) as active sites for phosphate mineral growth
and induced phosphate precipitation. The adsorption perfor-
mance and adsorption mechanism of Mg and Al modified
biochar were comparatively studied by Deng et al. (2021).
The dominant mechanism of phosphorus adsorption was dif-
ferent for Mg-modified biochar and Al-modified biochar.
Phosphorus adsorption by Mg-rich biochar relied mainly
on electrostatic attraction and reprecipitation of phosphorus
analogs through hydrogen bonding. In contrast, the adsorp-
tion mechanism of phosphorus by Al-modified biochar
mainly involved complex formation, cation bridging, chemi-
cal co-precipitation, and electrostatic attraction.
13
Environmental Chemistry Letters (2023) 21:497–524
Due to rare metals’ unique properties, rare metals are
employed to modify biochar to improve phosphorus adsorp-
tion. Lanthanum-modified biochar had good selectivity for
phosphorus adsorption (Dai et al. 2014). La-modified hydro-
char was insensitive to the co-existing anions. During the
adsorption process, electrostatic attraction was not domi-
nant mechanism at constant solution pH. The adsorption
mechanism was influenced by pH. When the initial solution
pH was about 2.5, ion exchange and electrostatic attraction
occurred. In a wide pH range (above 4.5), Lewis acid–base
interaction to form complexes was the dominant mechanism
for phosphorus adsorption. As to high pH, biochar surface
was negatively charged due to deprotonation, and electro-
static repulsion limited phosphorus adsorption. Li et al.
(2020b) also studied phosphorus adsorption by La-modified
biochar. When the solution pH was below 6.99 (the p­ Hpzc
of La-modified biochar), the positively charged biochar
adsorbed phosphorus through electrostatic attraction, and
ligand exchange played an important role. The adsorption
mechanism can be shown as Equations S18-21. In addition,
a study on biochar-based Ca-La alloy composites showed
that the primary adsorption mechanism was complexation
(Feng et al. 2021).
Phosphorus adsorption by Bi-modified biochar showed
the formation of bismuth phosphate (Zhu et al. 2016). Bi-
modified biochar had a good photocatalytic effect on meth-
ylene blue and was beneficial to the removal of methylene
blue from wastewater. For Bi-modified biochar, chemical
precipitation played a role in the phosphorus adsorption
process. X-ray diffraction analysis showed that new crystal
peaks ascribed to bismuth phosphate appeared after adsorp-
tion. The adsorption process involved loading bismuth atoms
on the surface of the activated carbon as adsorption sites,
followed by hydroxylation under acidic conditions. The
hydroxylated bismuth adsorbed phosphate groups to form
water-insoluble ­BiPO4 precipitates.
In summary, electrostatic attraction plays a vital role in
phosphorus adsorption, as metal oxides have a solid abil-
ity to adsorb negatively charged phosphorus species. A
hydroxylation process on biochar surface makes the surface
positively or negatively charged depending on the solution
pH (Ahmed et al. 2016; Wang et al. 2017; Wang and Wang
2019). The electrostatic repulsion hindered the attachment of
phosphate anions to the negatively charged biochar (Zhang
et al. 2018). Determining the zeta potential on the adsorbent
surface is essential for examining electrostatic attractions.
Mechanisms including ion exchange, surface complexation,
and electrostatic attraction are highly influenced by solution
pH. Surface precipitation is usually crucial in phosphorus
adsorption by Ca- and Mg-rich biochar. These mechanisms
do not occur individually, and they interact with each other
and take place simultaneously in the adsorption process.
Environmental Chemistry Letters (2023) 21:497–524
Phosphorus‑loaded biochar as slow‑release
fertilizers
Since agricultural lands are usually monocultures with
simple ecological structures and poor resistance to dis-
turbance, minor disturbances to cultivated lands cause
environmental problems. Disturbance even cause soil
degradation, the decomposition of soil organic matter, the
deterioration of soil microbial communities, and the loss
of soil biodiversity (Rhodes 2017). Chemical fertilizers are
widely used to improve crop production. However, most
conventional chemical fertilizers are highly water-solu-
ble, leading to low fertilizer efficiency. Over-fertilization
even leads to problems such as soil salinization, water
eutrophication, exacerbating soil degradation, and causing
waste of resources (Savci 2012). Additionally, the fertiliz-
ers requirement of crop growth is rough "S" shaped, and
the nutrient requirement varies according to the growth
stage (Shepherd et al. 2016). To improve the utilization
efficiency of fertilizers and reduce environmental threats,
researchers have proposed the concept of slow-release
fertilizers/controlled-release fertilizers. Biochar-based
slow-release fertilizers have attracted increasing attention
in recent years (Wang et al. 2022a).
Biochar‑based slow‑release fertilizers
Slow-release fertilizers are fertilizers that are designed
to control the release of nutrients, realize the continuous
nutrient supply of plants, and improve nutrient use effi-
ciency (Ehis-Eriakha et al. 2021). Biochar with porous
structure and large surface is an excellent carrier of nutri-
ents such as nitrogen, phosphorus, and potassium (Wang
et al. 2022a). Biochar can be used as a soil amendment
to alleviate land degradation. The addition of biochar to
soil improves soil quality, water retention capacity, soil
organic matter, carbon fixation, and microbial commu-
nities (Wang et al. 2020d; Yang et al. 2021; Zhao et al.
2016). Biochar-based slow-release fertilizer can be pre-
pared by various methods, such as impregnation, granula-
tion, co-pyrolysis, and encapsulation (Rashid et al. 2021;
Marcińczyk and Oleszczuk 2022). Different preparation
methods have their advantages and disadvantages (Fig. S4)
(Wang et al. 2022a). For example, the use of co-pyrolysis
to produce biochar-based slow-release fertilizers has sig-
nificant advantages such as simple synthesis, high phos-
phorus load, and good sustained release performance
(Rombel et al. 2021). Zhao et al. (2016) synthesized bio-
char-based phosphate fertilizers by co-cracking method,
which was produced by pyrolysis of a mixture of plant-
based biomass, calcium triple superphosphate, and bone
515
meal. The biochar-based phosphate fertilizer significantly
enhanced the ability of biochar to stabilize metals in soil
and improved the char retention rate (from 53.5–55.0% to
68.4–74.7%).
With the deepening understanding of biochar-based
slow-release fertilizer and nanotechnology, researchers have
explored the possibility of biochar-based slow-release fer-
tilizer at the nanoscale (Ramadan and Abd-Elsalam 2020).
The conversion of fertilizer to nanoparticle has been shown
to improve fertilizer’s efficacy (Le et al. 2021). Control of
the structural organization and surface chemistry of materi-
als at the nanoscale is possible, which means that materials
can be regulated to achieve desired application. Therefore,
nanotechnology has great application prospects in the prepa-
ration of slow-release fertilizers. The size of biochar can be
adjusted by increasing the pyrolysis temperature and grind-
ing time. Mechanical grinding is the most used technique to
fabricate nano biochar. The difference between nano biochar
and bulk biochar is reflected in the physical and chemical
properties and structural changes (Tan et al. 2016). Nano-
biochar has small volume, larger surface area, higher car-
bon skeleton, and extremely rich surface groups, providing a
platform for the attachment of microorganisms and nutrients.
Biochar-based nanoscale fertilizer can utilize the porous
structure to provide available macro- and micro-nutrients
for crops and soil on a sustained-release basis (Lateef et al.
2019). The preparation of biochar-based nanoscale fertilizer
derived from wheat straw was reported, and the excellent
performance of slow-release fertilizer in environmental pro-
tection and plant growth promotion was verified (Khan et al.
2021). The prepared γ-FeOOH@BC nanomaterial effec-
tively controlled the release of nutrients in the pH-neutral
soil and could automatically assemble herbicides and ferti-
lizers already present in the soil (Wang et al. 2022b). The
nanoscale slow-release fertilizers associated with biochar
have a broad prospect in the future. However, the small parti-
cle size of nanoscale slow-release fertilizer may have the risk
of micron or nanometer dust during large-scale use, which
needs to be paid attention and solved (Rajput et al. 2022).
The application of biochar-based slow-release fertilizer
will affect the migration of phosphorus in soil, which pro-
vides a solution to the loss of phosphorus due to leaching.
The superabsorbent materials have hydrophilic functional
groups and a three-dimensional cross-linking network of
hydrogen bonds, exhibiting excellent water retention abil-
ity and retention ability of nutrients in soil (Flanagan et al.
2003). The application of superabsorbent polymers in
slow-release fertilizer is beneficial to nutrients and water
retention. The coated biochar-based slow-release fertilizer
showed strong hydrophilicity with contact angle of 40.25°.
Korsmeyer-Peppas model was used to accurately describe
phosphorus release in slow-release fertilizers, which indi-
cated that the coating and polymer matrix could delay
13
516
the diffusion of phosphorus, in which the chemical bonds
formed between phosphorus and copolymer played an
important role (An et al. 2021). For superabsorbent hydrogel
biochar materials, hydrogels can also act as physical barriers
to hinder the diffusion of nutrients from the polymerization
network (Wen et al. 2017). For the inherent phosphorus in
soil, superabsorbent biochar can also alleviate the loss to
a certain extent. Hosseini et al. (2021) reported that phos-
phorus in soil mainly existed in the form of colloids, and
superabsorbent materials were beneficial to alleviate the
loss of colloidal phosphorus in soil. Das and Ghosh (2022)
pointed out that superabsorbent biochar accumulated large
amounts of water, and then slowly discharged the adsorbed
water when the soil moisture declined. Nutrients could be
gradually discharged with water as a supplementary nutri-
ent pool. In addition, the humic acid superabsorbent biochar
mixture could increase soil available phosphorus content,
which was beneficial to the improvement of soil quality (Li
et al. 2020c).
Phosphorus adsorbents as slow‑release fertilizers
Many studies have confirmed the potential of biochar-
based phosphate fertilizers in applications. Biochar has
been proven to be effective in phosphorus adsorption. The
interaction between adsorbed phosphorus and biochar lat-
tices is not strong enough, and there is still potential for
phosphorus release into the environment (Shepherd et al.
2016). Shepherd et al. (2016) confirmed the potential of
biochar recovered phosphorus through theoretical calcula-
tions. Plant growth experiments demonstrated that biochar
significantly contributed to seed germination and improved
crop height and fresh weight (Li et al. 2018; Wang et al.
Fig. 6  A phosphorus cycle route based on biochar when used as a
slow-release fertilizer. After being mined, phosphate ores are used by
human activities (daily life, industrial production, agricultural pro-
duction, etc.), and phosphorus is partly released into water. Biochar
13
Environmental Chemistry Letters (2023) 21:497–524
2020b; Yao et al. 2013a). An et al. (2020) reported using
bentonite-modified biochar after phosphorus adsorption as
controlled release fertilizer, and established a phosphorus
release kinetic model to quantitatively and precisely regulate
phosphorus release to meet the needs of plant growth. Phos-
phorus-adsorbed biochar as slow-release fertilizers helps
establish sustainable phosphorus circulation routes (Fig. 6).
The concept of bond order has been used to explain the
potential for phosphorus release. M ­ gHPO4 and ­Mg3(PO4)2
formed after phosphorus adsorption on biochar surface
tend to be converted to more stable phosphorus analogs and
MgO (Fig. 7a) (Chen et al. 2018b). This indicates that after
adsorption of phosphorus, biochar can be slow-release fer-
tilizers to improve the soil while promoting crop growth (Li
et al. 2016; Liu et al. 2019; Yao et al. 2013a). The adsorp-
tion of phosphorus from wastewater is also an effective
strategy to enhance biochar efficiency from agronomic and
economic perspectives. Phosphorus recovery from sewage
addresses the eutrophication problem and favors the decline
in the exploitation of phosphorus rock resources (Yang et al.
2020). Yao et al. (2013a) used phosphorus-adsorbed biochar
as a slow-release fertilizer. Biochar had a stable phosphorus
release capacity (Fig. 7b, c). Phosphorus release kinetics
showed that equilibrium release was reached at 30 h. This
release was repeatable when the new solution was intro-
duced into the system (simulating plant growth conditions).
The amount of phosphorus released was approximately
the same in eleven consecutive experiments. Biochar con-
tinuously and effectively provided nutrients to plants and
promoted plant growth (Fig. 7d-f). The result was consist-
ent with the study reported by Zheng et al. (2019). Bio-
char loaded with colloidal and nanosized AlOOH crystal-
line flakes was fabricated to recover phosphorus and then
can recover phosphorus from water body, and adsorbed biochar can
be used as a slow-release fertilizer. Biochar participation provides a
feasible way to construct a benign phosphorus cycle
Environmental Chemistry Letters (2023) 21:497–524
Fig. 7  a Bond order of the compounds and sketch of the desorption
process of phosphorus on biochar surface, reprinted with permission
of Elsevier from (Chen et al. 2018b); b desorption kinetics of phos-
phorous-loaded biochar; c the behavior of phosphorus release from
phosphate-containing biochar; d comparison of shoot length between
used as a slow-release fertilizer. Phosphorus-containing
biochar significantly promoted cowpea seed germination
and early seedling growth. There is sufficient evidence to
517
phosphorus biochar and control group, reprinted with permission of
ACS publications from (Yao et al. 2013a); e seed germination and
growth in different media, reprinted with permission of Elsevier from
(Zheng et al. 2019); f statistical results of plant growth, reprinted with
permission of Elsevier from (Wang et al. 2021c)
prove that reclaimed phosphorus by biochar can be applied
to soil as a slow-release fertilizer to improve soil quality and
productivity.
13
518
There are special requirements for applying phosphorous-
rich biochar as fertilizers: (i) the release rate of phospho-
rus in biochar; (ii) the availability of phosphorus for plant
growth; (iii) the potential adverse effects of biochar-based
fertilizers; (iv) the preparation cost of biochar-based fertiliz-
ers. When applying biochar-based fertilizers, the type of soil
and the target crop should be considered. Both the utilization
rate and release rate of phosphorus is of crucial concern.
Ca-P had a much lower bioavailability than Fe–P and Al-P
(Müller-Stöver et al. 2018; Sun et al. 2018). Additionally, the
coating of biochar-based slow-release fertilizers is mostly
slow or non-degradable materials (Fertahi et al. 2021). The
accumulation and potential threat to the soil of polymers
used in coatings requires special consideration. Finally, the
potential environmental risk of colloids and hazardous ele-
ments, depending on biomass feedstocks and the method of
biochar preparation, also needs to be assessed.
Perspective
Improvement of modification methods
Current researches mainly focus on biochar modification to
improve phosphorus adsorption performance. Metal loading
is considered an effective method of biochar modification.
Mg-modification is promising for fabricating biochar-based
adsorbents. Additionally, the application of bentonite, cel-
lulose and other green materials to biochar-based adsorbents
requires more attention. The metal toxicity to soil should be
considered for further researches due to the leaching risk of
metals. Moreover, biochar functionalization in a low-cost
and effective manner should take into account the charac-
teristics of biomass feedstocks.
Practical treatment of biochar adsorption
Most of the studies on phosphorus adsorption by func-
tional biochar are conducted under laboratory conditions.
Researches on real wastewater and pilot experiments are
rarely reported. For industrial practice, we need to consider
process cost and device differences. Biochar is subjected
to multiple processes such as grinding, washing, and dry-
ing for laboratory experiments, which means additional
energy and resource consumption in industrial applications.
The simulated wastewater is mostly used in the laboratory,
and the situation of real wastewater is more complex. The
experimental data, especially process parameters, are not
reliable to guidance industrial application. Studying adsorp-
tion under realistic wastewater can be of value in terms of
translating the lab-scale research to pilot-scale studies. For
the phosphorus recovery of wastewater by biochar, future
13
Environmental Chemistry Letters (2023) 21:497–524
research should gradually shift from the laboratory tests to
the pilot scale.
Better understanding of adsorption mechanism
The widely recognized mechanisms of phosphorus adsorp-
tion on biochar include electrostatic attraction, ion exchange,
surface complexation, etc. Future studies should provide
more experimental evidence to reveal the adsorption mecha-
nism. The kinetic models, adsorption isotherms, and thermo-
dynamic analysis provides insights into adsorption mecha-
nism, but the evidence is not fully persuasive. Extensive
studies on the change of biochar before and after adsorption
should be conducted by multiple techniques such as X-ray
diffraction, X-ray photoelectron spectroscopy, scanning
electron microscope, and infrared spectroscopy. Theoretical
calculations are helpful to reveal the mechanism of phospho-
rus adsorption onto biochar surface. Great efforts should be
performed to quantitatively analyze the adsorption mecha-
nism. Additionally, the better understanding of adsorption
mechanism offers beneficial guidance for design of effective
biochar-based adsorbents.
Phosphorus‑adsorbed biochar as slow‑release
fertilizers
After phosphorus adsorption from wastewater, phosphorus-
rich biochar has the potential to be slow-release fertilizers.
Future researches should focus on exploring the release
mechanism of phosphorus-rich biochar as slow-release fer-
tilizer. The rapid development of nanotechnology brings
opportunities to biochar-based slow-release fertilizers.
Technological progress in nano-enabled slow-release ferti-
lizer looks promising for future sustainable crop practices.
Moreover, the combination of superabsorbent, biochar and
phosphorous nutrient in one system is highly valuable for
improving soil quality and increasing fertilizer efficiency.
Finally, the researches related to phosphorus-adsorbed bio-
char as slow-release fertilizers are still in infancy, and the
fate and potential risks of biochar-based fertilizers should
be paid more attention.
Conclusion
The continuous loss of phosphorus resources and envi-
ronmental pollution promote the demand of phosphorus
resource recovery. This review highlights the role of biochar
in phosphorus recovery. Biochar shows great potential in
phosphorus recycle. Various waste biomasses provide abun-
dant sources of biochar materials. Functional biochar can
be fabricated by different thermochemical processes associ-
ated with modification methods. The properties of biochar
Environmental Chemistry Letters (2023) 21:497–524
offer an excellent platform for preparation of efficient phos-
phorus adsorbents. Phosphorus recovery using functional
biochar gives a solution to solve phosphorus loss and envi-
ronmental pollution. Research advances have been obtained
on the effect of process factors in adsorption process and
the adsorption mechanism of phosphorus. Using biochar to
establish a virtuous cycle of phosphorus is feasible. Cur-
rent knowledge suggests good application prospects of using
biochar to recover phosphorus. Although using phosphorus-
adsorbed biochar as slow-release fertilizers is in infancy, the
application as potential slow-release fertilizers is foreseeable
to establish a virtuous phosphorus cycle.
Supplementary Information The online version contains supplemen-
tary material available at https://d​ oi.o​ rg/1​ 0.1​ 007/s​ 10311-0​ 22-0​ 1519-5.
Author contributions All authors contributed to the study conception
and design. Material preparation, data collection and analysis were
performed by DL, LW, and CW. The first draft of the manuscript was
written by DL and CW and all authors commented on previous versions
of the manuscript.
Funding This work was supported by the National Key Research and
Development Project (2020YFC1908802).
Availability of data and materials Not applicable.
Code availability Not applicable.
Declarations
Conflict of interest The authors have no relevant financial or non-fi-
nancial interests to disclose.
Ethics approval Not applicable.
Consent to participate Not applicable.
Consent for publication All authors read the manuscript and approved
for publication.
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