Chemosphere 306 (2022) 135310

Contents lists available at ScienceDirect

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

From waste to fertilizer: Nutrient recovery from wastewater by pristine and

engineered biochars
Marta Marcińczyk a, Yong Sik Ok b, Patryk Oleszczuk a, *
a
Department of Radiochemistry and Environmental Chemistry, Faculty of Chemistry, Maria Curie-Skłodowska University, 3 Maria Curie-Skłodowska Square, 20-031
Lublin, Poland
b
Korea Biochar Research Center, APRU Sustainable Waste Management Program & Division of Environmental Science and Ecological Engineering, Korea University,
Seoul 02841, Republic of Korea

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Wastewater is the valuable sources of

nutrients.
• New knowledge on the biochar use to
recover nutrients from wastewater was
discussed.
• Nutrient adsorption is determine by:
biochar’s properties and solution’s pH.
• Potential of biochar as a slow-release
fertilizer was presented.
• The use of biochar-based fertilizer can
be economically and agriculturally
viable.

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

Handling Editor: Y Yeomin Yoon Biochar application for the recovery of nutrients from wastewater is a sustainable method based on a circular
economy. Wastewater, food wastewater, and stormwater are valuable sources of nutrients (i.e., PO3− 4 , NO3 , and
−

Keywords: NH+ 4 ). The unique properties of biochar, such as its large specific surface area, pH buffering capacity, and ion-
Biochar exchange ability, make it a cost-effective and environmentally friendly adsorbent. Biochar engineering im­
Wastewater
proves biochar properties and provide targeted adsorbents. The biochar-based fertilizers can be a sustainable
Fertilizer
alternative to traditional fertilization. The aim of the study was to compare the potential of pristine and engi­
Circular economy
Nutrients recovery neered biochars to recover nutrients from wastewater and to determine the factors which may affect this process.
Engineered biochar can be used as a selective adsorbent from multicomponent solutions. Adsorption on engi­
neered biochar can be also regulated by additional mechanisms: surface precipitation and ligand/ion exchange.
Metal modification (e.g. Mg, Fe) enhances PO3− 4 and NO3 adsorption capacity, and thus may provide the extra
−

plant macro-/micronutrients. The desorption mechanism, which is the basis for nutrient release are strongly pH
depended. The use of biochar-based fertilizer can have economic and agricultural benefits when using waste
materials and reducing pyrolysis energy costs.

* Corresponding author.
E-mail address: patryk.oleszczuk@mail.umcs.pl (P. Oleszczuk).

https://doi.org/10.1016/j.chemosphere.2022.135310
Received 25 April 2022; Received in revised form 8 June 2022; Accepted 9 June 2022
Available online 14 June 2022
0045-6535/© 2022 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
M. Marcińczyk et al.
1. Introduction
Natural resources, such as soil and mineral deposits, are depleted to
meet the needs of the growing population. It is estimated that phos­
phorus (P) reserves will be depleted during the next 50–100 years, with
the P demand gradually increasing by 2.5% per year (Xu et al., 2018).
Inappropriate and excessive use of fertilizers causes their accumulation
in the soil (Jie et al., 2002), which leads to their degradation. Accidental
loss of nutrients from nitrogen fertilizers results in elevated concentra­
tions of greenhouse gases as a result of N2O emissions, groundwater
pollution, and eutrophication of surface waters (Coskun et al., 2017).
Therefore, it is important to identify, evaluate, and implement a sus­
tainable strategy to ensure safety in the fertilizer market. An important
part of the newest growth strategy (e.g., the European Green Deal
(EGD)) is circular economy, which is an economic model focused on
resource efficiency (Klein et al., 2022) that includes the perspectives of
both raw material management and waste management (UE COM no.
398, 2014). One of the possibilities consistent with the circular economy
is the use of biochar as both a fertilizer and an adsorbent for nutrient
recovery. Biochar has a long agricultural history (Kookana et al., 2011)
as the main factor leading to high fertility in the Terra Preta de Índio
(Amazonian dark earth). This unique soil has a significantly high
nutrient content, especially P and N. Biochar contributes to the
improvement of soil properties (Agbede and Oyewumi, 2022; L. Ye et al.,
2020a), carbon sequestration, reduction of greenhouse gas emissions,
and removal of organic and heavy metal pollutants (Krasucka et al.,
2021; Song et al., 2020; Su et al., 2021). The use of nutrients contained
in different waste streams to produce fertilizers is strongly recom­
mended by the circular economy (Smol, 2021). Agriculture, forestry,
and fish waste, household waste, and wastewater are only a few exam­
ples of nutrient-rich wastes that can be used for fertilizer purposes.
These materials provide valuable nutrients for plant growth, including
N, P, K, Ca, and Mg. However, the use of waste is not only affected by the
presence of elements that are valuable for plants but also by the presence
of pollutants such as Pb, Hg, and Zn (Qasem et al., 2021). Therefore,
there is a need to search for sorbents that effectively recover nutrients
from waste as well as reduce the penetration of harmful substances into
the environment. Moreover, biochar seems to be an excellent tool to
fulfill the 17 Sustainable Development Goals (SDGs) of the United Na­
tions, especially SDG15 (protecting life on land) and SDG2 (promoting
sustainable agriculture). Several conventional methods are used to
recover nutrients from wastewater, including biochemical degradation,
chemical precipitation, flocculation/coagulation, and artificial wetlands
(Chrispim et al., 2019; Santos and Pires, 2018). These methods usually
remove valuable nutrients from wastewater, with high operational and
maintenance costs and massive waste production (Wang and Wang,
2019). The efficient techniques for P recovery from wastewater are the
Integrated Fixed-Film Activated Sludge Systems with Enhanced Bio­
logical Phosphorus removal (IFAS-EBPR) and struvite precipitation
(Bashar et al., 2018). Removal of nitrogen (N) from sewage is based on
physical (membrane processes, filtration, adsorption, stripping) or bio­
logical methods (Bio-electrochemical systems) (Beckinghausen et al.,
2020). The costs of wastewater treatment are largely determined by
energy prices, e.g. IFAS-EBPR: 60 € P kg− 1 (Stávková and Maroušek,
2021) and vacuum stripping 470 US $ t− 1 (Beckinghausen et al., 2020).
Adsorption using biochar is seems to be cost-effective, user-friendly, and
efficient method for removing nutrients from wastewater. Therefore, the
aim of this study was to collect existing data on the possible applications
of biochar to recover nutrients from wastewater and present its potential
for use as a slow/control-release fertilizer. Special attention was directed
to the sources of nutrient-rich wastewater and their use for fertilizer
purposes. This paper broadly discusses the adsorption and desorption
processes of macro- and micronutrients using biochar and engineered
biochars (EngBCs). The green entrepreneurship, i.e., cooperation be­
tween scientists and practitioners, should be the basis for developing
new techniques and practice (Muo and Azeez, 2019). The research
2
Chemosphere 306 (2022) 135310
discussed in the paper may contribute to the development of application
methods for the recovery of nutrients.
2. Biochar
Biochar is a solid material produced by the carbonization of biomass
(Mohan et al., 2014). Biomass resources, such as agricultural residue,
food processing waste, solid waste, animal waste, and municipal sludge,
are thermally decomposed under oxygen-limited conditions through
pyrolysis (Lee et al., 2019). Biochar has unique properties such as a large
specific surface area, pH buffering capacity, and ion-exchange ability,
and is perceived as a cost-effective, environmentally friendly, and effi­
cient multifunctional adsorbent (Huang et al., 2020a). Furthermore,
biochar has been shown to have a positive effect on many physico­
chemical and biological soil properties by improving ion exchange
properties, increasing soil pH, and enhancing water-holding capacity
(Ye et al., 2020b). As a soil amendment, biochar can be used as a fer­
tilizer to bind toxic contaminants, such as heavy metals (Song et al.,
2020), and stimulate soil microbial activity (El-Naggar et al., 2018). The
biomass type, pretreatment method, and pyrolysis conditions (temper­
ature, duration, and carrier gas) affect the physicochemical properties of
biochar (Cao et al., 2013). Biochar prepared from manure is usually
richer in nutrients, has a higher pH, and is characterized by a higher
specific surface area than biochar obtained from highly cellulosic feed­
stock such as wood (Ghodake et al., 2021). Biochars produced at high
temperatures (>550 ◦ C) are generally characterized by a larger specific
surface area and higher pH but have lower nutrient content than bio­
chars produced at lower temperatures (<550 ◦ C) (Ippolito et al., 2020).
Pristine biochar has some limitations as an efficient fertilizer owing to its
physicochemical properties, such as a negatively charged surface, low
specific surface area, and lack of acidic functional groups (Kavitha et al.,
2018; Takaya et al., 2016), which limits its utilization in reducing the
leaching of anionic nutrients (NO3- and PO43-) from soils. However,
engineered biochars or biochar composites can be a good replacement
for pristine biochar because these biochars have the potential for various
applications in the soil (as pristine biochar), but more importantly, may
contain nutrients and slowly release them from the matrix, thereby
improving their functionality Wang et al., 2022). Engineered biochar or
biochar composites are the form of pristine biochar modified with ma­
terials such as metals, nanomaterials, microorganisms, and hydroxides
(Wang et al., 2021) (Fig. 1). The development of EngBCs has gained
significant attention recently, and numerous reports have shown the
efficient removal of heavy metals, toxic dyes, and contaminants from
municipal wastewater and industrial effluent (Kun Luo et al., 2021;
Yaashikaa et al., 2019).
3. Nutrient sources
Phosphorus is a non-renewable resource; the conversion of N to
fertilizer using the Haber–Bosch process is energy intensive and nutrient
losses cause environmental eutrophication (Lim and Welty, 2018).
Therefore, the recovery of nutrients from wastewater has attracted
considerable attention. The potential sources of macro- (N, P, K, Ca, Mg,
and Na) and micronutrients (Cu, Fe, Mn, and Zn) that can be used for
fertilization are municipal, industrial, and agricultural waste and
wastewater. Wastewater is considered a source of nutrients because of
its high concentration and high production. The global wastewater
production is estimated to be 359.4 × 109 m3 yr− 1, of which 63% is
collected and 52% is treated using various methods (Jones et al., 2021).
Moreover, 48% of global wastewater production is released into the
environment untreated (Jones et al., 2021). The total recovery of P from
wastewater would fulfill 15–20% of the global demand for this element
(Jing et al., 2019). The main types of wastewater are domes­
tic/municipal (gray or black), industrial, and stormwater runoff (Dia­
z-Elsayed et al., 2019). Municipal wastewater (particularly black water)
is an excellent source of N and P (Yu et al., 2020). Human urine can also
M. Marcińczyk et al.
Fig. 1. Biochar modification methods.
serve as a source of nutrients (Jena et al., 2021). Urine constitutes less
than 1% of the total wastewater (Pathy et al., 2021) but approximately
80% of the N, 50% of the P, and 70% of the K in municipal wastewater is
from urine (Wilsenach et al., 2003). Food wastewater, produced during
the processing of food as a result of dehydration or anaerobic degrada­
tion, is also rich in nutrients (Thant Zin and Kim, 2021). The use of
biowaste composting provides essential nutrients at high concentrations
(Antonangelo et al., 2020; Oldfield et al., 2018). Stormwater also con­
tains nutrients in various forms including soluble ions (NH+
4 , NO3 , NO2 ,
− −
3−
and PO4 ), precipitates (with metals or carbonates), colloids, and par­
ticulate matter (particles larger than 0.45 μm) (Tondera et al., 2018).
However, it should be noted that only nutrients recovered from stable
sources (e.g. municipal, fermentation residues) can be an alternative to
traditional sources (Maroušek and Gavurová, 2022; H. Yang et al.,
2020). The use of waste as a source of nutrients may face one technical
(legislative constraints), economic (high transportation and storage
costs) and practical (large volumes) barriers (Vaneeckhaute et al.,
2017).
In the past decade, many review studies have included detailed in­
formation on nutrient recovery from wastewater (Fig. 2). Microalgae-
based wastewater treatment processes (Li et al., 2019), anaerobic
Fig. 2. Nutrient recovery from wastewater.
3
Chemosphere 306 (2022) 135310
digestion (Santos and Pires, 2018) and membrane hybrids are effective
processes with high operational costs and difficult technical feasibility
(Ye et al., 2020). The present review focuses on the implementation of
wastewater nutrient recovery using adsorption on biochar and engi­
neered biochar and biochar composites. Biochar has the potential to
recover nutrients from wastewater but can also be an additional source
of macro- and micronutrients, which can significantly increase its
fertilization properties (Marcińczyk and Oleszczuk, 2022). The appli­
cation of nutrient-loaded biochar in agricultural fields can also act as a
slow/control-release fertilizer.
4. Nutrients adsorption using pristine biochar and modified
biochar
Adsorption techniques are considered promising for recovering nu­
trients from wastewater. The simplicity of the procedure, cost-
effectiveness of sorbents, and economics (Loganathan et al., 2014)
indicate the advantages of this technique (Fig. 2). The sorption method
is relatively more effective at low concentrations; post-treatment pro­
cedures are often not required, and no sludge is produced during or after
the process (Bhatnagar and Sillanpää, 2011). The high cost of sorbent
M. Marcińczyk et al.
regeneration may affect the practicality of adsorption methods.
Furthermore, sorbents are usually characterized by a low selectivity for
coexisting ions. Adsorption techniques are sensitive to pH and temper­
ature (Fidel et al., 2018). The use of waste-produced biochar reduces the
costs of adsorption techniques and also provides selective, engineered
sorbents (Panwar and Pawar, 2022).
4.1. Ammonium adsorption using pristine biochar
Ammonium ions are the main form of N (NH−4 N) in water. Yang et al.
(2018) determined the ability of biochars produced at 300 ◦ C (PS300)
and 500 ◦ C (PS500) from pine sawdust and at 550 ◦ C from wheat straw
(WS550) to adsorb NH−4 N ions from wastewater. PS300 was character­
ized by the highest affinity for NH−4 N ions, adsorbing NH−4 N ions at a
level of 5.38 mg g− 1. Significantly lower adsorption values were
observed for PS550 (3.37 mg g− 1) and WS550 (2.08 mg g− 1). The au­
thors demonstrated that the adsorption of NH−4 N primarily occurs based
on chemical bonds and electrostatic interactions between the negatively
charged biochar surface and positively charged NH−4 N (Yang et al.,
2018). The higher H/C ratio indicates relatively lower aromatic struc­
ture (higher organic carbon content) and may suggest higher adsorption
sites potentially available for adsorption of nutrients. Additionally the
high O/C indicates the oxygen-containing functional groups and
hydrophilic/polar character of biochars (Gai et al., 2014; Lou et al.,
2016). The higher values of H/C and O/C, which characterize PS300,
indicate the presence of numerous functional groups on the surface of
the biochar and its low carbonization (Yang et al., 2018), which resulted
in the highest Qmax (maximum adsorption capacity) values for NH−4 N
(Yang et al., 2018). Similar conclusions were drawn by Hu et al. (2020),
who investigated the possibility of removing NH−4 N from aqueous so­
lutions using biochars produced from fruit skin (orange, pineapple, and
pitaya) at 300, 400, 500, and 600 ◦ C. The study found higher adsorption
values for the biochars produced at lower temperatures compared to
those produced at higher temperatures, regardless of the type of feed­
stock used. The highest adsorption capacity (5.60 mg g− 1) was deter­
mined for the biochar prepared from pineapple peel (300 ◦ C; H/C =
0.06; O/C = 0.29). Xu et al. (2019) suggested that biochar characterized
by high H/C content is more effective for the adsorption of inorganic
pollutants and high O/C ratio (represents high hydrophilicity and po­
larity) is recommended to the adsorption of polar soluble pollutants such
as ammonium. Furthermore, the study (Hu et al., 2020) showed that the
pH of the solution had a significant effect on NH−4 N adsorption. Kizito
et al. (2015) demonstrated that the adsorption efficiency of NH−4 N had
the lowest values in low pH ranges (3–4), increasing in the pH range
(4–8). When the pH exceeded 8, the adsorption decreased again. The
authors explained the behavior of NH−4 N ions through the fact that at
low pH values, some functional groups (COO- and OH-) adopt a positive
charge as a result of protonation, which leads to the repulsion of posi­
tively charged NH−4 N ions from the biochar matrix (Gong et al., 2019).
Moreover, in a low pH solution, there is a high concentration of H+ ions
that compete with NH−4 N ions for active sites on the biochar surface
(Tang et al., 2019). At a high pH (>8), NH−4 N ions are converted to NH3,
which substantially reduces the adsorption of these ions because the
electrostatic interaction mechanism is no longer efficient (Tang et al.,
2019). It was also noted that with increasing biochar mass, in the range
of 0.1–1 g, the amount of adsorbed NH−4 N increased, which is a result of
a higher number of available adsorption sites (Tang et al., 2019).
Nonetheless, the application of biochar rates exceeding 1 g no longer
increased the adsorption of NH−4 N and could even decrease it (Tang
et al., 2019). This was because of the aggregation of biochar particles
and the decrease in available active sites on the adsorbent. The
adsorption of NH−4 N ions also increased with a decrease in biochar
particle size (Tang et al., 2019). The Qmax determined for NH−4 N for
different biochars can adopt a wide range of values (Table S1), which
predominantly depends on the type of biochar used. The pyrolysis
temperature plays the important role in biochar’s physicochemical
4
Chemosphere 306 (2022) 135310
parameters such as atomic ratios H/C and O/C. High temperature
removes H- and O-containing functional groups, increases the aroma­
ticity and decreases polarity of biochars compered to low temperature
pyrolysis conditions (<500 ◦ C).
4.2. Ammonium adsorption using engineered biochar
Pristine biochar has a limited ability to bind nutrients and hence the
recently growing interest in EngBCs, which after appropriate modifica­
tion, achieve an even greater ability to adsorb NH−4 N ions (Thant Zin and
Kim, 2021). EngBCs can be used to remove NH−4 N from water/waste­
water; however, after adsorption they can be used as fertilizer as a
source of NH−4 N in soil. Modifications of biochar increase its cation ex­
change capacity (CEC) and introduce additional functional groups
(Zhang et al., 2020), which have a notable impact on the mechanisms
responsible for NH−4 N adsorption. Natural clay minerals, such as mont­
morillonite (Mt) and bentonite, are characterized by a higher specific
surface area, significant CEC, and adsorption capacity relative to bio­
chars. Because of this capacity, these minerals have been used to
fabricate biochar composites (Chen et al., 2017). Clay minerals are
formed by tetrahedral layers of silica, in which water molecules and
metal cations occur (Ismadji et al., 2016). Chen et al. (2017)
co-pyrolyzed bamboo powder and Mt. The pyrolysis process was carried
out in the temperature range of 300–500 ◦ C, in a N atmosphere. The
montmorillonite-biochar (MtBC) composites obtained were tested for
their efficiency in removing NH−4 N. The adsorption of NH−4 N on the
MtBC was 12.5 mg g− 1, which was more than five times higher than that
on unmodified biochar. This positive effect of NH−4 N adsorption was
achieved owing to the interaction of NH−4 N with the functional groups
present on the surface of Mt and the binding (intercalation) of ions in the
interlayer spaces of Mt. In another study conducted using bentonite as a
component of a biochar composite, the adsorption of NH−4 N was found
to be at a level of 23.7 mg g− 1. For comparison, the adsorption of the
same ions on the biochar or bentonite was 9.49 and 12.4 mg g− 1,
respectively (Ismadji et al., 2016). A higher specific surface area and
more developed porous structure of the bentonite-biochar composite
were the factors determining its higher adsorption capacity compared to
that of bentonite or biochar alone. The mechanism of binding NH−4 N is
based on van der Waals interactions and ion exchange with the metal
cations present in the interlayer spaces of bentonite (Ismadji et al.,
2016).
Another biochar modification method involves the use of oxidants
(acids and H2O2), which are designed to increase the percentage of ox­
ygen functional groups (Han et al., 2021). Specific oxidants provide
advantages and disadvantages. For example, H2O2 minimizes the pos­
sibility of accompanying reactions such as precipitation or complexa­
tion, which may occur when acids are applied (H2SO4, HNO3) (Wang
et al., 2015a, 2015b). In a study, Wang et al. (2020) used H2O2 to modify
biochar produced from peanut shells at a temperature of 500 ◦ C. In this
way, an increase in sorption affinity was achieved toward NH−4 N from
24.6 mg g− 1 for the pristine biochar to 123.3 mg g− 1 for the H2O2-mo­
dified biochar. This enhanced adsorption was linked to a change in the
surface properties of the biochar because of H2O2 modification. Nitro­
gen, located in functional groups on the biochar surface, initially having
pyrrolic character, changing to pyridine after adsorption of NH−4 N,
which indicated that chemical adsorption predominantly occurred (π-π
bonds and hydrogen bonds). Another method for increasing the biochar
adsorption capacity for NH−4 N is neutralization of the acidic surface.
Because the affinity of alkali metal ions for the functional groups of
biochar is generally lower than that for H+ ions, they can be more easily
replaced with NH−4 N (Han et al., 2021). In a study by Wang et al. (2015a,
2015b), maple wood-derived biochar was oxidized using H2O2. The
determined adsorption of NH−4 N ions on the modified biochar increased
from 1.77 mg g− 1 in pH 3.69–5.44 mg g− 1 after pH neutralization to 7.
Modification of biochar with HCl or H2SO4 (Wang et al., 2020) also
increases its adsorption capacity for NH−4 N, which in such cases can
M. Marcińczyk et al.
reach Qmax values of 100 mg g− 1 and 120 mg g − 1, respectively. It was
suggested (Wang et al., 2020) that biochar with high porous structure
(high SBET) effectively adsorb nitrogen ions and exhibit the fast
adsorption rates. Alkali treatment (NaOH) of biochar also increases the
negative charges on it surfaces and enhances the ammonium adsorption.
Liu et al. (2016) reported that NH4–N adsorption by modified (1 M
NaOH) biochars produced from peanut shells, corncobs, or cotton stalks
was respectively 1.3–1.7-2.5-times higher than on pristine biochars. In
addition modified biochars demonstrated extremely good NH4–N
adsorption ability at high temperature (50 ◦ C), indicating that it can be
used in high temperature environment for ammonium removal. Biochar
modifications for NH−4 N adsorption applications can also be based on the
impregnation of biochar with MgO. Gong et al. (2017) impregnated
biochar prepared from Phragmites australis using MgCl2, which increased
its adsorption capacity from approximately 1 to 30 mg g− 1 NH−4 N. The
main mechanism responsible for NH−4 N adsorption using Mg-coated
biochar was ion exchange between Mg2+ and NH+ 4 . The literature data
included in the table clearly indicate that biochar modification affects
the NH−4 N adsorption capacity.
4.3. Nitrate adsorption using pristine biochar
Apart from NH−4 N, NO−3 anions are nitrogen-containing ions (NO−3 N)
that occur most frequently in aqueous solutions. The electrostatic
repulsion between the negatively charged biochar surface and NO−3 N
can be an obstacle to the adsorption of these ions by biochar (Zhang
et al., 2020). Nonetheless, research has shown that adsorption of NO−3 N
using biochars is possible. Alsewaileh et al. (2019) compared NO−3 N
adsorption on biochars produced from date palms at temperatures of
300 and 700 ◦ C. The biochar produced at 700 ◦ C exhibited twice the
adsorption (7.73 mg g− 1) of that generated at 300 ◦ C. The better
adsorption capacities of biochars produced at higher temperatures are
usually due to their higher specific surface area (Alsewaileh et al., 2019)
and thus, a higher number of active sites are capable of adsorbing NO−3 N.
Moreover, with increasing pyrolysis temperature, the number of
oxygen-containing functional groups and thus the electrostatic repulsion
between the biochar and NO−3 N ion can become weaker (Alsewaileh
et al., 2019). In such cases, the adsorption of negatively charged NO−3 N is
possible based on covalent and electrostatic interactions. Solution pH
also plays an important role in the adsorption of NO−3 N by biochars
(Fidel et al., 2018). At low pH (<7), H+ ions can accumulate on the
biochar surface; thus, the number of positively charged active sites in­
creases, which also results in increased adsorption of negatively charged
NO−3 N ions. At pH (>7), there is competition between OH− anions and
NO−3 N, which reduces the adsorption. Research has revealed that the
feedstock used to produce biochar plays an essential role in the
adsorption of NO−3 N. Zhao et al. (2017) compared the NO−3 N adsorption
capacity of biochar produced from corncobs, peanut shells, and corn
waste at a temperature of 600 ◦ C. These authors found that corncob
biochar was the most efficient for NO−3 N adsorption. The maximum
sorption capacity determined for this biochar was 14.5 mg g− 1 NO−3 N,
which was approximately nine times higher than those determined for
the other biochars. Hafshejani et al. (2016) also found a similar
maximum sorption capacity value of 11.6 mg g− 1 for sugarcane bagasse
biochar produced at 300 ◦ C. Nonetheless, the majority of studies have
reported either marginal or no adsorption of NO−3 N on pristine biochar.
When studying NO−3 N adsorption on mustard straw (300 ◦ C) and wheat
straw (300 ◦ C) biochar as well as on commercial activated carbon,
Mishra and Patel (2009)obtained very low adsorption values, which
were as follows: 1.3 mg g− 1, 1.1 mg g− 1, and 1.22 mg g− 1, respectively
(Mishra and Patel, 2009). Investigating adsorption of NO−3 N using
wheat-straw, corn-straw, and peanut-shell biochars produced at
different temperatures (400, 500, 600, and 700 ◦ C), Gai et al. (2014)
observed no adsorption. A study conducted by Hale et al. (2013) also
demonstrated marginal adsorption of NO−3 N on biochars derived from
cacao shells and corncob (300–350 ◦ C). Yang et al. (2017) studied
5
Chemosphere 306 (2022) 135310
adsorption of NO−3 N on biochars produced at different temperatures
(200, 350, 500, and 700 ◦ C) from feedstocks with a high content of
lignin and cellulose. The composition of the biopolymers in the feed­
stock may determine biochar properties such as their surface area and
pores size distribution, and thus their sorption characteristics. Higher
adsorption was observed for the lignin biochars produced at higher
temperatures. However, the adsorption levels achieved in these exper­
iments were very low, ranging from 0.029 to 0.580 mg g− 1.
4.4. Nitrate adsorption using engineered biochar
Biochar modifications aimed at improving NO−3 N adsorption are
designed to reduce the electrostatic repulsion between NO−3 ions and the
negatively charged biochar surface (Zhang et al., 2020). One method for
engineering biochar to increase its NO−3 N adsorption capacity is Al
modification (Yin et al., 2018a,b). As a result of this type of modifica­
tion, Yin et al. (2018a,b) obtained NO−3 N adsorption capacity that was
five times higher (89.6 mg g− 1) than that of pristine biochar. The authors
used pre-pyrolysis modification, during which the initial feedstock,
which consisted of poplar pieces, was impregnated with an AlCl3 solu­
tion, dried, and pyrolyzed at a temperature of 550 ◦ C in a N atmosphere.
The main reason for the substantial increase in adsorption was the
development of the specific surface area and a change in the charge of
the Al-coated biochar surface to become positive, which attracted
negatively charged NO−3 . Yin et al. (2018a,b) investigated NO−3 N
adsorption on Al- and Mg-modified biochar composites. The Al-coated
biochar, for which the maximum adsorption capacity (40.6 mg g− 1)
was 8 and 2.5 times higher than for the pristine biochar and for the
Mg-coated biochar, respectively, proved to be the most efficient. When
modifying biochar produced from peanut shells at a temperature of
600 ◦ C with MgCl2, Zhang et al. (2012) found the maximum NO−3 N
adsorption capacity to be 95 mg g− 1. In an aqueous environment, MgO
on the biochar surface adopts a positive charge and can therefore effi­
ciently combine with negatively charged NO−3 N (Yao et al., 2011). When
modifying biochar derived from Conocarpus green waste (600 ◦ C) with
MgCl2, Usman et al. (2016) did not achieve high adsorption values as in
the studies cited previously. Although the techniques used managed to
increase the biochar adsorption capacity by nearly three times (Usman
et al., 2016), it was not at a satisfactory level at 0.8 mg g− 1.
Lanthanum is another metal that has been used to modify biochar to
increase its adsorption capacity for NO−3 N. Owing to the La modification
of biochar derived from oak sawdust (600 ◦ C), Wang et al. (2015a,
2015b) obtained an almost 12-fold increase in NO−3 N adsorption of 100
mg g− 1. The significant increase in adsorption was attributed to an in­
crease in basic functional groups on the modified biochar, which facil­
itated chemisorption. The O/C (0.23) and (O + N)/C (0.24) ratios in
La-biochars (600 ◦ C) were both higher than those of pristine biochar
(600 ◦ C) (O/C = 0.15 and (O + N)/C = 0.16) and confirmed the higher
content of basic functional groups. Research has shown that modifica­
tion using concentrated HCl also causes an increase in the biochar
adsorption capacity for NO−3 ions (Chintala et al., 2013). Using
HCl-modified biochar from Ponderosa pine wood (650 ◦ C), Chintala et al.
(2013) found the adsorption capacity to increase from 2.58 mg g− 1 to
9.74 mg N g− 1. Chemical modification may be provided also with using
N, N-dimethylformamide (Hafshejani et al., 2016). During this modifi­
cation the additional positively charged functional groups are intro­
duced to biochars which enhance NO3–N adsorption (over 2 times)
compared to pristine biochar (Table S2). However, the presence of
co-existing ions (e.g., phosphate, carbonate, sulfate or chloride) may
reduce the NH4–N adoption capacity. Multivalent anion with higher
charge density was adsorbed more favorable than monovalent anion.
Another modification method contributing to the enhanced NO−3 N
adsorption by biochar is the use of clay minerals. Viglašová et al. (2018)
proposed the synthesis of bamboo-based MtBC composites. The feed­
stock was combined with Mt suspension, dried, and pyrolyzed at 460 ◦ C.
Owing to the addition of Mt to biochar, a two-fold increase in NO−3 N
M. Marcińczyk et al.
adsorption was obtained at a level of 9 mg g− 1 (Yu et al., 2020). The
adsorption of NO−3 N on clay mineral composites is based on complex
mechanisms that combine electrostatic interactions, ionic bonding, and
ion exchange (Viglašová et al., 2018). When comparing the biochar
modification methods in terms of biochar applications for NO−3 N
adsorption, it should be noted that the methods based on Al or Mg
addition are more beneficial because they do not cause a significant
increase in adsorption relative to the initial biochar; however, they also
sorb NO−3 N several times better than the biochars modified using other
methods (Table S2). Generally, NO3–N adsorption is determined by
presence the basic functional groups (high N content and (O + N)/C
ratios), electrostatic interaction (outer-sphere complexation mecha­
nism) or high surface area (Yang et al., 2017).
4.5. Phosphate adsorption using pristine biochar
Phosphate ions, which are another macronutrient essential for plant
growth (Yang et al., 2020), are best assimilated by plants as H2PO−4 and
HPO2− 4 . Depending on the pH of the environment, inorganic forms of P
occur as H2PO−4 , HPO2− 3−
4 , and PO4 (PO4 P) ions (Zhang et al., 2020).
−
Similar to the case of NO−3 N ions, the adsorption of PO−4 P on pristine
biochar is usually inhibited owing to the electrostatic repulsion of anions
by the negatively charged biochar surface. Phosphorus adsorption on
biochar is dependent on the concentration and availability of cations in
its inorganic fraction. Thus, biochars with low ash content exhibit a low
ability to bind P because they contain small amounts of metals (Shep­
herd et al., 2017). Furthermore, the mechanisms of P binding by bio­
chars are related to an ash fraction rather than a functional carbon
group. As reported by Hale et al. (2013), cacao shell and corncob bio­
chars with an ash content of 8–17% adsorbed PO−4 P in low amounts of
0.022–0.748 mg g− 1. Jung et al. (2015) suggested that Mg and Ca
contents in biochars are of key importance for PO−4 P sorption by bio­
chars, particularly the Mg/P and Ca/P ratios. The authors observed that
the biochars tested (prepared from soybean stover, bamboo wood, and
maize residue), with low Mg/P (<1.5) and Ca/P (<5.0) ratios, poorly
adsorbed PO−4 P, and caused the release of P from the biochar. A con­
trasting relationship was observed in peanut shell biochar, which was
characterized using higher Mg/P (3.46) and Ca/P (47.60) ratios and
adsorbed PO−4 P at a level of 6.79 mg g− 1. Kizito et al. (2017) compared
the adsorption of PO−4 P from digested liquid swine manure onto biochar
obtained from wood, corncobs, rice husks, and sawdust. Adsorption of
PO−4 P did not differ significantly between the feedstocks and ranged
from 8.1 to 12.0 mg g− 1. The authors suggested that the main adsorption
mechanism was based on the Ca–P precipitation reaction. They also
suggested that the presence of other ions, such as Na+ or K+, in the
digested swine manure (from which PO4–P was adsorbed) could have
contributed to the protonation of the negatively charged biochar surface
and the formation of a local positive charge, which facilitated the
adsorption of negative PO−4 P on the biochar surface. PO−4 P adsorption
was also found to be dependent on the pyrolysis temperature at which
the biochar was produced (Fang et al., 2014; Peng et al., 2012; Trazzi
et al., 2016) (Table S3). The higher the pyrolysis temperature is, the
higher the PO−4 P adsorption values.
4.6. Phosphate adsorption using engineered biochar
As indicated for the previously discussed ions, biochar modification
using metals may be a solution for enhanced efficiency in removing
PO−4 P (Zhang et al., 2021). Wang et al. (2021) proposed a solution for
the problem of low adsorption on pristine biochar. Biochars produced
from oilseed rape straw (700 ◦ C) were modified with coal gangue.
Owing to this modification, adsorption of 7.9 mg g− 1 PO−4 P was ach­
ieved, which was nearly five times higher than that on the pristine
biochar. The authors explained the process of adsorption on this com­
posite based on the mechanisms of ion exchange, surface precipitation,
and electrostatic attraction. Modifications may also involve the
6
Chemosphere 306 (2022) 135310
introduction of additional metals e.g., Mg or Fe, which increase the
content of the mineral fraction; largely participates in the binding of P.
Zhang et al. (2021) modified sludge biochars with Mg and Mg–Fe. The
adsorption of PO−4 P on the Mg-biochar composite was 142.3 mg g− 1, and
lower values were determined for the Mg–Fe biochar (35.4 mg g− 1);
however, both results were much higher than those for the pristine
biochar (2.3 mg g− 1). The authors suggested that the process of PO−4 P
adsorption on the composites is complex and involves a range of
mechanisms, such as protonation, electrostatic attraction, surface
inner-sphere complexation, and precipitation. The impregnation of
Mg-biochar seems to be an effective method to increase PO−4 P adsorp­
tion, which was also confirmed in a study by Shin et al. (2020). The
modification of biochar from ground coffee bean waste with Mg resulted
in an adsorption of 56 mg g− 1. Xiao et al. (2020) also indicated that
Mg-coated biochar composites were efficient for PO−4 P removal.
Nevertheless, the values obtained were significantly lower (21.8 mg g− 1)
than those presented in previous studies but almost 14 times higher than
that of the pristine biochar. Modification proposed by Peng et al. (2021)
involved the formation of Mg/Al layered double hydroxides (LDHs),
composed of both positively and negatively charged layers, and water
filling the interlayer spacing on the surface of the biochar (corn straw,
950 ◦ C). The adsorption of PO−4 P on the obtained composite was found
to be 286.2 mg g− 1. Yang et al. (2019) also confirmed the high efficiency
of Mg/Al LDH biochar composites for PO−4 P adsorption. The adsorption
of PO−4 P using the produced biochar composite (corn stalk, 600 ◦ C) was
152 mg g− 1. The high results for PO−4 P adsorption on the BC-LDHs
composites can be explained by the good dispersion of colloidal LDH
flakes in the aqueous solution, which increased the number of active
sites and enabled efficient adsorption on the composites. Huang et al.
(2020b) modified biochar with lanthanum and chitosan, achieving
PO−4 P adsorption at 109 mg g− 1. The adsorption mechanism was based
on electrostatic interactions, but Lewis acid-base interactions and ligand
exchange also played a significant role. Particularly, very high PO−4 P
adsorption results were obtained by Novais et al. (2018) for biochars
derived from poultry manure (350 ◦ C) and sugarcane straw (350 ◦ C) and
doped with Al. Doping with Al was performed after pyrolysis as a result
of the saturation of the biochars with an AlCl3 solution (biochar mass:
solution of 1:1000). The Al-doped biochars prepared from poultry
manure and sugarcane straw were characterized by very high PO−4 P
adsorptions of 701.65 mg g− 1 and 758.96 mg g− 1, respectively. The
authors suggested that the use of Al allows the negatively charged bio­
char surface to be coated with Al3+ cations and hydrolysis products of its
salts, thus generating a positive surface charge that facilitates the
binding of the negatively charged ions. The negative charge of biochar’s
surface can be also eliminated by biochar treatment using ZnCl2 (Park
et al., 2015). The maximum PO−4 P adsorption capacity was enhanced
after Zn activation to 15.46 mg kg− 1, whereas pristine biochar release P
(− 12.38 mg kg− 1). These examples (Table S3) show how large differ­
ences in PO−4 P adsorption can be obtained using various biochar modi­
fications. Compared with adsorption on pristine biochar, adsorption on
engineered biochar can be more than 1000 times higher (Novais et al.,
2018). The utilization of metals to fabricate biochar composites forms a
bridge that enables the adsorption of anions on the negatively charged
biochar surface. However, when selecting a modification method, effi­
ciency as well as the possibility of safe environmental application must
be considered. This particularly applies to modification with Al, which
exhibits toxicity that can disturb plant growth and soil microbiological
processes (Shetty et al., 2021), when this type of composite is considered
for use as a secondary fertilizer with controlled release of PO4. Wang
et al. (2021) proposed a different solution for the problem of low
adsorption on pristine biochar. Oilseed rape straw biochar (700 ◦ C) was
modified with coal gangue. Owing to the modification used, an
adsorption of 7.9 mg g− 1 PO−4 P was achieved, which was nearly five
times higher than that of the pristine biochar. The authors explained the
process of adsorption on this composite based on the mechanisms of ion
exchange, surface precipitation, and electrostatic attraction (Table 1).
M. Marcińczyk et al.
Table 1
Mechanism of NH4–N, NO3–N and PO4–P adsorption/desorption on/from biochar.
4.7. Combined adsorption
In addition to these discussed possibilities of recovering single ions as
nutrients, it is also possible to simultaneously adsorb N and P ions on
biochar composites. An example is the use of Mg-modified biochar to
recover PO−4 P and NH−4 N from aqueous solutions based on the precipi­
tation reaction (Equation (1)):
Mg2+ + NH4+ + HPO2−4 + 6 H2 O→MgNH4 PO4 *6H2 O + H + (1)
Struvite (MgNH4PO4∙6H2O) obtained from this reaction covers the
biochar surface (Thant Zin and Kim, 2021) and can also be a source of N,
P, and Mg. Therefore, such materials can act as slow-release compound
fertilizers. Xu et al. (2018) proposed the use of MgO-coated wood waste
biochar for the simultaneous recovery of N and P from urea. The
adsorption of N and P was 47.5 mg g− 1 and 116 mg g− 1, respectively.
Gong et al. (2017) used Mg-coated biochar obtained from P. australis for
the simultaneous removal of PO−4 P and NO−3 N from water. The authors
found the sorption to be 100 mg g− 1 for PO−4 P and 30 mg g− 1 for NH−4 N.
Chandra et al. (2020) and Yin et al. (2018a,b) compared the adsorption
of NH−4 N, PO−4 P, and NO−3 N from eutrophic water onto biochar using
single- and three-component systems. The authors found no differences
in the levels of NH−4 N and PO−4 P adsorption between these systems.
Nonetheless, they observed a 50% decrease in NO−3 N adsorption in the
three-component system. The absence of differences in NH−4 N and PO−4 P
desorption indicates a lack of competition between these ions, which is
due to their binding/interaction with different active sites. The reduced
adsorption of NO−3 N may result from the greater affinity of PO−4 P for the
proposed functional groups, because of which the active sites are
occupied by competitive ions. The generation of adsorbents with the
ability to simultaneously bind nutrients is of particular interest for the
treatment of water contaminated with many nutrients, such as eutrophic
water or wastewater.
7
Chemosphere 306 (2022) 135310
5. Nutrient desorption from pristine biochar and modified
biochar
In the fabrication of biochar-based slow-release fertilizers, the pre­
viously described methods for enriching biochars with nutrients are
important as are the processes of desorption of these nutrients, which
enable essential elements to be transferred to the soil and subsequently
assimilated by the plants. The following section presents information
regarding the efficiency of nutrient desorption from biochar, desorption
mechanisms, and factors affecting desorption.
5.1. Ammonium desorption
Yin et al. (2020) used biochars produced from sewage sludge and
walnut shells at a temperature of 600 ◦ C to evaluate NH−4 N adsorp­
tion/desorption processes. In their study, the authors investigated the
effect of pH on NH−4 N desorption from biochar. The desorption of NH−4 N
gradually decreased with increasing solution pH from 2.0 to 11.5. The
maximum NH−4 N desorption of 2.2% was achieved at a pH of 2. The
authors suggested (Yin et al., 2020) that NH−4 N desorption primarily
occurred based on ion exchange, which was confirmed by its greatest
intensity at low pH values (pH = 2). Desorption was also observed to
increase slightly in a strongly alkaline environment because the OH−
ions present in this environment electrostatically attracted NH−4 N.
Desorption of NH−4 N occurred in two stages, with the first lasting 4 h and
being the most intensive. Aghoghovwia et al. (2020) determined the
NH−4 N desorption from biochars obtained from various feedstocks,
including grape pip biochar, grape skin biochar, pine wood biochar, and
rubber tire biochar, using 2 M KCl. Desorption solutions are commonly
used to determine mineral nitrogen in soils (Aghoghovwia et al., 2020).
Within the first 24 h, depending on the feedstock used to produce the
biochars, desorption ranged as 53–60% of the initially adsorbed NH−4 N
(0.6–9.4 mg g− 1). The authors suggest that because adsorption was
based on electrostatic and van der Waals interactions, desorption was
possible through ion exchange with K+ ions (Aghoghovwia et al., 2020).
The weakest binding and hence the highest desorption, were obtained
M. Marcińczyk et al.
for the grape pip biochar (60.3%) and rubber tire biochar (58.4%). The
adsorption of NH−4 N on these biochars mainly resulted from electrostatic
interactions because a net negative charge and the presence of carboxyl
groups were observed; therefore, NH−4 N could be easily desorbed by K+
ions (Table 1). Gong et al. (2019) investigated NH−4 N desorption from
biochar prepared from rice straw at temperatures of 300, 400, 600, and
800 ◦ C. The range of NH−4 N desorption was dependent on the biochar
production temperature to the greatest extent, which determined its
physicochemical properties. Desorption of NH−4 N was highest for the
biochar produced at 800 ◦ C (60.2%), while desorption from BC600,
which had most efficiently adsorbed NH−4 N (15.61 mg g− 1), occurred at
46.2%. Nutrients physically adsorbed on the biochar surface are des­
orbed easily, whereas the opposite phenomenon is observed in the case
of chemical adsorption. Adsorption on biochars produced at high tem­
peratures usually occurs through physical sorption, which explains the
higher desorption from these biochars (Gong et al., 2019). Wang et al.
(2015a, 2015b) studied NH−4 N desorption from maple wood biochar
(500 ◦ C) in aqueous and KCl solutions. The authors reported that less
than 27% of the initially adsorbed NH−4 N was desorbed in water within
24 h, whereas the use of KCl solution for extraction allowed 99%
desorption to be achieved. Desorption to the KCl solution was dependent
on pH, and as suggested by the authors, at pH above 7, the NH−4 N ions
were converted to volatile NH3, resulting in incomplete recovery of
NH−4 N. A recent study by Vendra Singh et al. (2020) also reported high
levels of urea desorption from biochar. The authors indicated that within
72 h rice straw biochar prepared at 450 ◦ C desorbed almost 98% of urea
from the water. The desorption process was dependent on urea
adsorption and diffusion, as well as on surface parameters, such as the
porous structure, because a microporous structure favors the storage and
retention of nutrients in biochars. Chen et al. (2017) studied NH−4 N
desorption from a composite of biochar (bamboo powder, 300–500 ◦ C)
with Mt. Weak interactions of NH−4 N with the biochar, based on van der
Waals interactions and surface adsorption, allowed the adsorbate to be
leached evenly and easily, with the obtained desorption results ranging
as 0.30–4.92% of the initial adsorbed amount. Desorption of NH−4 N from
biochar (maple wood, 550 ◦ C) modified with 30% H2O2 was determined
by Wang et al. (2015a, 2015b) in two stages. A sample was first
extracted with water and then with KCl solution. NH−4 N desorption in
the water was very low, accounting for less than 27% of the adsorbed
NH−4 N for the biochar with an unadjusted pH and less than 16% for the
biochar with an adjusted pH (=7). At a low pH, KCl application allowed
the adsorption of NH−4 N to recover almost completely. However, this
was not possible at pH greater than 7, as explained by the authors (Wang
Fig. 3. Biochar-based fertilizer obtained through adsorption from contaminated wastes.
8
Chemosphere 306 (2022) 135310
et al., 2015a, 2015b), which was associated with N losses as a result of
the release of gaseous NH3. The higher the level of biochar oxidation
achieved by increasing the H2O2 concentration and biochar contact
time, the lower the NH−4 N desorption from the biochar. As shown in the
above examples, desorption of NH−4 N from biochar occurs gradually, but
in most cases, maximum NH−4 N is released from the biochar matrix
relatively quickly (from 24 to 72 h), which limits the use of biochar as a
slow/control-release fertilizer. The NH−4 N desorption process can be
controlled to some degree by the selection of substrates, pH, and
appropriate modifications. Under environmental conditions, controlling
pH or moisture content can be difficult. However, the presented studies
demonstrate the potential of reusing biochars that were initially used to
remove NH−4 N from water and subsequently as fertilizer. Nevertheless, a
range of studies on the desorption kinetics and environmental processes
that may impact the release of NH−4 N are required. NH−4 N is bound by
biochars with little strength, which creates the risk that NH−4 N will be
quickly released after the application of this type of fertilizer to soils
(Fig. 3). Therefore, the direct application of secondary biochar is in
question; currently, biochar will probably require additional treatments
that will increase the strength of interaction with the matrix, due to
which NH−4 N will be leached more slowly and in a more controlled
manner. One should not exclude the direct application of secondary
biochars to soils; however, this requires additional studies using
different feedstocks and more complex biochars, wherein bonding will
be stronger, which will provide gradual release of NH−4 N.
5.2. Nitrate desorption
Most studies have shown that desorption of NO−3 N from pristine
biochar is marginal or reaches very low values (Aghoghovwia et al.,
2020; Hale et al., 2013). Using KCl as an extractant, Aghoghovwia et al.
(2020) determined the desorption of NO−3 N from biochar prepared from
plant waste (grape pip, grape skin, and pine wood) and rubber tires to
range 0.01–0.23%, depending on the type of biochar. According to these
authors (Aghoghovwia et al., 2020), biochar catalyzes the reactions of
nitrogen compounds owing to the transfer of electrons in the aromatic
structure of the biochar, which causes the formation of nitrogen forms
other than NO−3 N. The biochar reduced NO−3 N, probably to nitrites or
gaseous forms, which resulted in reduced desorption. Hale et al. (2013)
observed no desorption of NO−3 N from cacao shell biochar produced at a
temperature of 350 ◦ C. Chintala et al. (2013) observed that the
desorption of NO−3 N was significantly dependent on the solution pH and
amount of previously adsorbed NO−3 N. In addition, biochar activation
M. Marcińczyk et al.
significantly affects desorption (Chintala et al., 2013). Biochars pre­
pared from Pinus ponderosa L. wood chips and Panicum virgatum L. at
650 ◦ C were activated using HCl. A study (Chintala et al., 2013) revealed
that the desorption of NO−3 N from activated biochars was clearly higher
than that from nonactivated biochars. Desorption from activated Pinus
ponderosa-derived biochar was nearly 75%, whereas that from
non-activated biochar was 65%. The authors observed that the desorp­
tion of NO−3 N was higher at pH 9 than at pH 4. Increased desorption at a
high pH can be associated with the formation of a negative charge on the
biochar surface, which acts repulsively on negatively charged NO−3 N.
Moreover, a higher concentration of OH− ions at a high pH can cause the
displacement of NO−3 N from the sorption sites. Gong et al. (2019) found
that biochar production temperature plays an important role in the
desorption of NO−3 N from biochars. The authors compared the desorp­
tion of NO−3 N from rice straw biochars produced at 300, 400, 600, and
800 ◦ C. As previously mentioned, physical adsorption predominantly
occurs on biochars produced at higher temperatures (>600 ◦ C), which is
a process that weakly binds NO−3 N ions, and thus, such adsorbed nu­
trients are desorbed more easily. Comparing NO−3 N desorption from the
biochars prepared at two extreme temperatures, 300 ◦ C and 800 ◦ C,
Gong et al. (2019) found desorption to be nearly twice that of the bio­
char produced at a temperature of 800 ◦ C (64% of the initially adsorbed
NO−3 N). The present study demonstrates that desorption of NO−3 N from
biochars can be substantially lower than that of NH+ 4 , and that it is
strongly dependent on the pH of the desorbing solution. This may cause
problems when trying to obtain secondary controlled-release fertilizers,
especially compound fertilizers. Adjustment of the relevant parameters
that consider the desorption of different ions may require additional
research that would include biochars produced at different temperatures
and their modifications.
5.3. Phosphorus desorption
Studies have also been conducted on PO−4 P ions. Yin et al. (2020)
investigated the desorption of PO4–P ions from biochar produced from
municipal sewage sludge and walnut shells at a temperature of 600 ◦ C.
Desorption of PO4–P was clearly dependent on the initial PO−4 P con­
centration used in the adsorption process, which is understandable
because it determines the amount of desorbed nutrients. This also in­
dicates that desorption depends on the amount of adsorbed nutrients,
which can form the basis for preparing fertilizers with a specific amount
of released nutrients. The highest desorption level was achieved at pH 2,
where 7.58% of the initially adsorbed PO−4 P was desorbed from the
biochar within 24 h. However, the authors (Yin et al., 2020) observed
that with the adsorption of a lower amount of PO−4 P (14.2 mg g− 1),
desorption was not proportionate, at only 2.1%. These differences in
desorption were linked to the easier desorption of nutrients from the
successive adsorption layers and the large difference between the con­
centration of the adsorbed ions and the aqueous solution used as a
desorbate. Moreover, PO−4 P formed on the biochar surface were spar­
ingly soluble in neutral solution; hence, after the application of such
biochar in soil, their biological availability can also be limited. With
increasing pH, the amount of PO−4 P desorbed from the biochar decreased
because of the poor solubility of PO−4 P in a basic environment and
electrostatic repulsion between OH− and PO−4 P, which did not promote
the leaching of these ions into the solution. Trazzi et al. (2016) also
investigated the effect of the initial PO−4 P concentration and biochar
production conditions on PO4–P desorption. Biochar was prepared from
sugarcane and Miscanthus at 300, 500, and 700 ◦ C. The authors found
that PO−4 P desorption was dependent on the initial concentration of the
solution used for adsorption and the biochar pyrolysis temperature.
Desorption from sugarcane biochar (700 ◦ C) ranged as 22.4–45.6% for
initial solution concentrations of 25 and 400 ppm. With increasing py­
rolysis temperature ranging as 300–700 ◦ C, a 3–12% increase in
desorption was observed. Shin et al. (2020) studied the effect of different
extractants on the range of PO4–P desorption from Mg-biochar
9
Chemosphere 306 (2022) 135310
composites produced using biochar from ground coffee bean waste py­
rolyzed at a temperature of 500 ◦ C. The authors used pre-pyrolysis
modification and impregnated ground coffee bean waste with MgCl2
solution. Desorption of PO4–P occurred at the same rate in both water
and the 2% citric acid solution. The Mg-biochar composite released
approximately 70% of the initially adsorbed PO4–P within 12 h. At the
same time, desorption in 2% citric acid resulted in the release of 90% of
adsorbed PO4–P. The obtained results show that an acidic environment
(2% citric acid, pH 2.5) was more beneficial for the desorption of PO4–P,
which was associated with the higher solubility of Mg–P (Mg3(PO4)2),
MgHPO4) at acidic pH. The desorption of PO4–P is strongly dependent
on the pH of the desorbing solution, which limits soil environmental
conditions, but also on pyrolysis conditions or the initial concentration
used in the adsorption, which makes it possible to design biochar ad­
sorbents and adjust their properties to the soil requirements.
6. Economic evaluation
The production costs of biochar depend on many factors i.e., feed­
stock used, production automation, energy costs and logistics, and range
from 30 to 800 € t− 1 (Maroušek and Trakal, 2022). The energy balance
of biochar can be regulated by the choice of pyrolysis conditions, e.g., at
temperature below 500 ◦ C hemicellulose and lignin decomposition is an
exothermic reaction and cellulose is an endothermic reaction, while at
higher temperatures the opposit trend occurs (Kwapinski, 2019). The
biochar production costs seem to be lower compared to synthetic fer­
tilizer prices. According to the World Bank (April 2022) the price of
nitrogen fertilizers (urea) is as high as 925 US $ t-1 and phosphorus
fertilizers 954 US $ t-1. It is estimated that such high prices of fertilizers
will remain or even increase due to high canning of energy resources
(coal, natural gas) and disturbances in the supply chain of raw materials
(phosphorus, ammonia, sulfur). The nutrient losses from synthetic fer­
tilizers can be as high as 50% (Dimkpa et al., 2020), which results in low
utilization of fertilizers and an increase in the costs of agricultural pro­
duction. On the other hand significant changes are achieved in crop
productivity when high biochar (pristine) rates, ranging 2.5–20 ton
ha− 1, are applied to soil (Joseph et al., 2013). Enriching biochar with
nutrients can lower this dosage level. Moreover, a one-time application
of biochar can provide fertilization for several seasons, reducing agri­
cultural and energy costs (Shaviv, 2001). However, attention should also
be paid to the fact that some of the physicochemical properties of bio­
chars (water-binding capacity, porosity, specific area) have changed due
to aging in soil (Maroušek and Trakal, 2022). Furthermore, the final cost
of secondary biochar is related to the cost of modifying factor e.g., metal
salts (Maroušek and Gavurová, 2022). The growing production of
wastewater (Jones et al., 2021) not only has an adverse impact on the
environment (e.g., eutrophication), but also requires the large financial
outlays (Muga and Mihelcic, 2008). Additionally, the average fee for
biowaste landfilling in the EU is currently about 30 € t− 1 (Favoino and
Giavini, n.d.). Biochar-based fertilizer production can be profitable
segment if: 1) waste are used for biochar production; 2) pyrolysis pro­
cess involve waste heat and; 3) the obtained biochar is rich in nutrients
(from waste); 4) biochar-based fertilizers are used for targeted fertil­
ization (Stávková and Maroušek, 2021). Nevertheless, further studies
are required to evaluate the economic and agricultural profitability of
using biochar-based fertilizers.
7. Conclusions and recommendations for further research
Utilization of the characteristic properties of biochar, that is, high
specific surface area, porosity, and the presence of various functional
groups, allows us to obtain an excellent matrix for recovering nutrients
from wastewater. Biochar adsorption processes have an advantage over
other methods, especially because of the simplicity of the procedure and
cost-effective and eco-friendly adsorbent. The main mechanisms that
determine adsorption on pristine biochar are electrostatic adsorption,
M. Marcińczyk et al.
physical adsorption, and surface adsorption on macro- and micropores.
The maximum adsorption capacity strongly depends on the biochar type
(i.e., biochar feedstock and pyrolysis temperature). Pristine biochar has
some limitations (for example, negatively charged surface, low specific
surface area, and lack of acidic functional groups); therefore, it is rec­
ommended to modify biochar. Metal modification (e.g., Mg, Al, Fe, Zn),
acid-base treatment, H2O2 modification or combining biochars with
minerals (e.g., bentonite, montmorillonite) effectively enhanced the
adsorptive properties of biochar. Engineered biochar exhibits selective
adsorption, which is important for adsorption from multicomponent
solutions. Adsorption on EngBCs depends on additional mechanisms,
particularly ligand and ion exchange, hydrogen bonding, and surface
precipitation. Desorption processes are strongly influenced by biochar
type, pH, and type of desorbing solution. Electrostatic interaction and
ion exchange are the main mechanism effected desorption processes.
Direct application is difficult on an agriculture scale and may impose
restrictions in the secondary biochar application. Future research should
focus on a better understanding of the desorption kinetics and envi­
ronmental processes that may impact the release of nutrients in the soil.
Direct application of secondary biochar to soil can cause unwanted
phenomena, such as the uncontrolled loss of nutrients, providing a lower
utilization rate and higher application costs. Furthermore, nutrient high
concentration in soil manifested as specific toxicity may cause plant
stress. Nutrients released to the soil too quickly from the secondary
biochar will not be fully assimilated by the plants, and an excess of
nutrients can lead to groundwater contamination, and eutrophication of
surface waters. The direct application of secondary biochars to soils
should not be ruled out; however, additional studies are required using
different feedstocks and more complex biochars in which bonding will
be stronger, which will provide gradual nutrient release. Evaluation of
the economic benefits of secondary biochar application requires further
analyses.
Credir author statement
Marta Marcińczyk: Writing – original draft, Yong Sik Ok: Review and
editing, Patryk Oleszczuk: Conceptualization, Writing – original draft,
Review and editing, Supervision.
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.
Data availability
No data was used for the research described in the article.
Acknowledgments
This work was supported by the National Science Center (Poland)
under the SHENG 1 grant [grant number UMO-2018/30/Q/ST10/
00060].
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.chemosphere.2022.135310.
References
Agbede, T.M., Oyewumi, A., 2022. Benefits of biochar, poultry manure and
biochar–poultry manure for improvement of soil properties and sweet potato
productivity in degraded tropical agricultural soils. Resour. Environ. Sustain. 7,
100051. https://doi.org/10.1016/j.resenv.2022.100051.
10
Chemosphere 306 (2022) 135310
Aghoghovwia, M.P., Hardie, A.G., Rozanov, A.B., 2020. Characterisation, adsorption and
desorption of ammonium and nitrate of biochar derived from different feedstocks.
Environ. Technol. 43 (5), 774–787. https://doi.org/10.1080/
09593330.2020.1804466, 0(0).
Alsewaileh, A.S., Usman, A.R., Al-Wabel, M.I., 2019. Effects of pyrolysis temperature on
nitrate-nitrogen (NO3− -N) and bromate (BrO3− ) adsorption onto date palm
biochar. J. Environ. Manag. 237, 289–296. https://doi.org/10.1016/j.
jenvman.2019.02.045.
Antonangelo, J.A., Sun, X., Zhang, H., 2020. The roles of co-composted biochar (COMBI)
in improving soil quality, crop productivity, and toxic metal amelioration.
J. Environ. Manag. 277, 111443. https://doi.org/10.1016/j.jenvman.2020.111443.
Bashar, R., Gungor, K., Karthikeyan, K.G., Barak, P., 2018. Cost effectiveness of
phosphorus removal processes in municipal wastewater treatment. Chemosphere
197, 280–290. https://doi.org/10.1016/j.chemosphere.2017.12.169.
Beckinghausen, A., Odlare, M., Thorin, E., Schwede, S., 2020. From removal to recovery:
an evaluation of nitrogen recovery techniques from wastewater. Appl. Energy 263,
114616. https://doi.org/10.1016/j.apenergy.2020.114616.
Bhatnagar, A., Sillanpää, M., 2011. A review of emerging adsorbents for nitrate removal
from water. Chem. Eng. J. 168 (2), 493–504. https://doi.org/10.1016/j.
cej.2011.01.103.
Cao, X., Ro, K.S., Libra, J.A., Kammann, C.I., Lima, I., Berge, N., Li, L., Li, Y., Chen, N.,
Yang, J., Deng, B., Mao, J., 2013. Effects of biomass types and carbonization
conditions on the chemical characteristics of hydrochars. J. Agric. Food Chem. 61
(39), 9401–9411. https://doi.org/10.1021/jf402345k.
Chandra, S., Medha, I., Bhattacharya, J., 2020. Potassium-iron rice straw biochar
composite for sorption of nitrate, phosphate, and ammonium ions in soil for timely
and controlled release. Sci. Total Environ. 712, 136337. https://doi.org/10.1016/j.
scitotenv.2019.136337.
Chen, L., Chen, X.L., Zhou, C.H., Yang, H.M., Ji, S.F., Tong, D.S., Zhong, Z.K., Yu, W.H.,
Chu, M.Q., 2017. Environmental-friendly montmorillonite-biochar composites:
facile production and tunable adsorption-release of ammonium and phosphate.
J. Clean. Prod. 156, 648–659. https://doi.org/10.1016/j.jclepro.2017.04.050.
Chintala, R., Mollinedo, J., Schumacher, T.E., Papiernik, S.K., Malo, D.D., Clay, D.E.,
Kumar, S., Gulbrandson, D.W., 2013. Nitrate sorption and desorption in biochars
from fast pyrolysis. Microporous Mesoporous Mater. 179, 250–257. https://doi.org/
10.1016/j.micromeso.2013.05.023.
Chrispim, M.C., Scholz, M., Nolasco, M.A., 2019. Phosphorus recovery from municipal
wastewater treatment: critical review of challenges and opportunities for developing
countries. J. Environ. Manag. 248, 109268. https://doi.org/10.1016/j.
jenvman.2019.109268.
Coskun, D., Britto, D.T., Shi, W., Kronzucker, H.J., 2017. Nitrogen transformations in
modern agriculture and the role of biological nitrification inhibition. Nature Plants
3, 17074. https://doi.org/10.1038/nplants.2017.74.
Diaz-Elsayed, N., Rezaei, N., Guo, T., Mohebbi, S., Zhang, Q., 2019. Wastewater-based
resource recovery technologies across scale: a review. Resour. Conserv. Recycl. 145,
94–112. https://doi.org/10.1016/j.resconrec.2018.12.035.
Dimkpa, C.O., Fugice, J., Singh, U., Lewis, T.D., 2020. Development of fertilizers for
enhanced nitrogen use efficiency – trends and perspectives. Sci. Total Environ. 731,
139113. https://doi.org/10.1016/j.scitotenv.2020.139113.
El-Naggar, A., Lee, S.S., Awad, Y.M., Yang, X., Ryu, C., Rizwan, M., Rinklebe, J.,
Tsang, D.C.W., Ok, Y.S., 2018. Influence of soil properties and feedstocks on biochar
potential for carbon mineralization and improvement of infertile soils. Geoderma
332, 100–108. https://doi.org/10.1016/j.geoderma.2018.06.017.
Fang, C., Zhang, T., Li, P., Jiang, R., Wang, Y., 2014. Application of magnesium modified
corn biochar for phosphorus removal and recovery from swine wastewater. Int. J.
Environ. Res. Publ. Health 11 (9), 9217–9237. https://doi.org/10.3390/
ijerph110909217.
Favoino, E., & Giavini, M. (n.d.). This Report Was Commissioned by the Bio-Based
Industries Consortium (BIC). 50.
Fidel, R.B., Laird, D.A., Spokas, K.A., 2018. Sorption of ammonium and nitrate to
biochars is electrostatic and pH-dependent. Sci. Rep. 8 (1), 17627. https://doi.org/
10.1038/s41598-018-35534-w.
Gai, X., Wang, H., Liu, J., Zhai, L., Liu, S., Ren, T., Liu, H., 2014. Effects of feedstock and
pyrolysis temperature on biochar adsorption of ammonium and nitrate. PLoS One 9
(12), e113888. https://doi.org/10.1371/journal.pone.0113888.
Ghodake, G.S., Shinde, S.K., Kadam, A.A., Saratale, R.G., Saratale, G.D., Kumar, M.,
Palem, R.R., Al-Shwaiman, H.A., Elgorban, A.M., Syed, A., Kim, D.-Y., 2021. Review
on biomass feedstocks, pyrolysis mechanism and physicochemical properties of
biochar: state-of-the-art framework to speed up vision of circular bioeconomy.
J. Clean. Prod. 297, 126645. https://doi.org/10.1016/j.jclepro.2021.126645.
Gong, Y.-P., Ni, Z.-Y., Xiong, Z.-Z., Cheng, L.-H., Xu, X.-H., 2017. Phosphate and
ammonium adsorption of the modified biochar based on Phragmites australis after
phytoremediation. Environ. Sci. Pollut. Control Ser. 24 (9), 8326–8335. https://doi.
org/10.1007/s11356-017-8499-2.
Gong, H., Tan, Z., Zhang, L., Huang, Q., 2019. Preparation of biochar with high
absorbability and its nutrient adsorption–desorption behaviour. Sci. Total Environ.
694, 133728. https://doi.org/10.1016/j.scitotenv.2019.133728.
Hafshejani, L.D., Hooshmand, A., Naseri, A.A., Mohammadi, A.S., Abbasi, F.,
Bhatnagar, A., 2016. Removal of nitrate from aqueous solution by modified
sugarcane bagasse biochar. Ecol. Eng. 95, 101–111. https://doi.org/10.1016/j.
ecoleng.2016.06.035.
Hale, S.E., Alling, V., Martinsen, V., Mulder, J., Breedveld, G.D., Cornelissen, G., 2013.
The sorption and desorption of phosphate-P, ammonium-N and nitrate-N in cacao
shell and corn cob biochars. Chemosphere 91 (11), 1612–1619. https://doi.org/
10.1016/j.chemosphere.2012.12.057.
M. Marcińczyk et al.
Han, B., Butterly, C., Zhang, W., He, J., Chen, D., 2021. Adsorbent materials for
ammonium and ammonia removal: a review. J. Clean. Prod. 283, 124611. https://
doi.org/10.1016/j.jclepro.2020.124611.
Hu, X., Zhang, X., Ngo, H.H., Guo, W., Wen, H., Li, C., Zhang, Y., Ma, C., 2020.
Comparison study on the ammonium adsorption of the biochars derived from
different kinds of fruit peel. Sci. Total Environ. 707, 135544. https://doi.org/
10.1016/j.scitotenv.2019.135544.
Huang, Y., Lee, X., Grattieri, M., Yuan, M., Cai, R., Macazo, F.C., Minteer, S.D., 2020a.
Modified biochar for phosphate adsorption in environmentally relevant conditions.
Chem. Eng. J. 380, 122375. https://doi.org/10.1016/j.cej.2019.122375.
Huang, Y., Lee, X., Grattieri, M., Yuan, M., Cai, R., Macazo, F.C., Minteer, S.D., 2020b.
Modified biochar for phosphate adsorption in environmentally relevant conditions.
Chem. Eng. J. 380, 122375. https://doi.org/10.1016/j.cej.2019.122375.
Ippolito, J.A., Cui, L., Kammann, C., Wrage-Mönnig, N., Estavillo, J.M., Fuertes-
Mendizabal, T., Cayuela, M.L., Sigua, G., Novak, J., Spokas, K., Borchard, N., 2020.
Feedstock choice, pyrolysis temperature and type influence biochar characteristics: a
comprehensive meta-data analysis review. Biochar 2 (4), 421–438. https://doi.org/
10.1007/s42773-020-00067-x.
Ismadji, S., Tong, D.S., Soetaredjo, F.E., Ayucitra, A., Yu, W.H., Zhou, C.H., 2016.
Bentonite hydrochar composite for removal of ammonium from Koi fish tank. Appl.
Clay Sci. 119, 146–154. https://doi.org/10.1016/j.clay.2015.08.022.
Jena, J., Das, T., Sarkar, U., 2021. Explicating proficiency of waste biomass-derived
biochar for reclaiming phosphate from source-separated urine and its application as
a phosphate biofertilizer. J. Environ. Chem. Eng. 9 (1), 104648. https://doi.org/
10.1016/j.jece.2020.104648.
Jie, C., Jing-zhang, C., Man-zhi, T., Zi-tong, G., 2002. Soil degradation: a global problem
endangering sustainable development. J. Geogr. Sci. 12 (2), 243–252. https://doi.
org/10.1007/BF02837480.
Jing, H.-P., Li, Y., Wang, X., Zhao, J., Xia, S., 2019. Simultaneous recovery of phosphate,
ammonium and humic acid from wastewater using a biochar supported Mg(OH)2/
bentonite composite. Environ. Sci.: Water Res. Technol. 5 (5), 931–943. https://doi.
org/10.1039/C8EW00952J.
Jones, E.R., van Vliet, M.T.H., Qadir, M., Bierkens, M.F.P., 2021. Country-level and
gridded estimates of wastewater production, collection, treatment and reuse. Earth
Syst. Sci. Data 13 (2), 237–254. https://doi.org/10.5194/essd-13-237-2021.
Joseph, S., Graber, E.R., Chia, C., Munroe, P., Donne, S., Thomas, T., Nielsen, S.,
Marjo, C., Rutlidge, H., Pan, G.X., Li, L., Taylor, P., Rawal, A., Hook, J., 2013.
Shifting paradigms: development of high-efficiency biochar fertilizers based on
nano-structures and soluble components. Carbon Manag. 4 (3), 323–343. https://
doi.org/10.4155/cmt.13.23.
Jung, K.-W., Hwang, M.-J., Ahn, K.-H., Ok, Y.-S., 2015. Kinetic study on phosphate
removal from aqueous solution by biochar derived from peanut shell as renewable
adsorptive media. Int. J. Environ. Sci. Technol. 12 (10), 3363–3372. https://doi.org/
10.1007/s13762-015-0766-5.
Kavitha, B., Reddy, P.V.L., Kim, B., Lee, S.S., Pandey, S.K., Kim, K.-H., 2018. Benefits and
limitations of biochar amendment in agricultural soils: a review. J. Environ. Manag.
227, 146–154. https://doi.org/10.1016/j.jenvman.2018.08.082.
Kizito, S., Wu, S., Kipkemoi Kirui, W., Lei, M., Lu, Q., Bah, H., Dong, R., 2015. Evaluation
of slow pyrolyzed wood and rice husks biochar for adsorption of ammonium
nitrogen from piggery manure anaerobic digestate slurry. Sci. Total Environ. 505,
102–112. https://doi.org/10.1016/j.scitotenv.2014.09.096.
Kizito, S., Luo, H., Wu, S., Ajmal, Z., Lv, T., Dong, R., 2017. Phosphate recovery from
liquid fraction of anaerobic digestate using four slow pyrolyzed biochars: dynamics
of adsorption, desorption and regeneration. J. Environ. Manag. 201, 260–267.
https://doi.org/10.1016/j.jenvman.2017.06.057.
Klein, N., Ramos, T.B., Deutz, P., 2022. Advancing the circular economy in public sector
organisations: employees’ perspectives on practices. Circ. Econ. Sustain. 2, 759–781.
https://doi.org/10.1007/s43615-021-00044-x.
Kookana, R.S., Sarmah, A.K., Van Zwieten, L., Krull, E., Singh, B., 2011. Chapter three -
biochar application to soil: agronomic and environmental benefits and unintended
consequences. In: Sparks, D.L. (Ed.), Advances in Agronomy, vol. 112. Academic
Press, pp. 103–143. https://doi.org/10.1016/B978-0-12-385538-1.00003-2.
Krasucka, P., Pan, B., Sik Ok, Y., Mohan, D., Sarkar, B., Oleszczuk, P., 2021. Engineered
biochar – a sustainable solution for the removal of antibiotics from water. Chem.
Eng. J. 405, 126926. https://doi.org/10.1016/j.cej.2020.126926.
Kwapinski, W., 2019. 2—char production technology. In: Jeguirim, M., Limousy, L.
(Eds.), Char and Carbon Materials Derived from Biomass. Elsevier, pp. 39–68.
https://doi.org/10.1016/B978-0-12-814893-8.00002-X.
Lee, J., Sarmah, A.K., Kwon, E.E., 2019. Chapter 1—production and formation of
biochar. In: Ok, Y.S., Tsang, D.C.W., Bolan, N., Novak, J.M. (Eds.), Biochar from
Biomass and Waste. Elsevier, pp. 3–18. https://doi.org/10.1016/B978-0-12-811729-
3.00001-7.
Li, K., Liu, Q., Fang, F., Luo, R., Lu, Q., Zhou, W., Huo, S., Cheng, P., Liu, J., Addy, M.,
Chen, P., Chen, D., Ruan, R., 2019. Microalgae-based wastewater treatment for
nutrients recovery: a review. Bioresour. Technol. 291, 121934. https://doi.org/
10.1016/j.biortech.2019.121934.
Lim, T.C., Welty, C., 2018. Assessing variability and uncertainty in green infrastructure
planning using a high-resolution surface-subsurface hydrological model and site-
monitored flow data. Front. Built Environ. 4. https://www.frontiersin.org/art
icle/10.3389/fbuil.2018.00071.
Liu, Z., Xue, Y., Gao, F., Cheng, X., Yang, K., 2016. Removal of ammonium from aqueous
solutions using alkali-modified biochars. Chem. Speciat. Bioavailab. 28 (1–4),
26–32. https://doi.org/10.1080/09542299.2016.1142833.
Loganathan, P., Vigneswaran, S., Kandasamy, J., Bolan, N.S., 2014. Removal and
recovery of phosphate from water using sorption. Crit. Rev. Environ. Sci. Technol. 44
(8), 847–907. https://doi.org/10.1080/10643389.2012.741311.
11
Chemosphere 306 (2022) 135310
Lou, K., Rajapaksha, A.U., Ok, Y.S., Chang, S.X., 2016. Sorption of copper(II) from
synthetic oil sands process-affected water (OSPW) by pine sawdust biochars: effects
of pyrolysis temperature and steam activation. J. Soils Sediments 16 (8), 2081–2089.
https://doi.org/10.1007/s11368-016-1382-9.
Luo, Kun, Pang, Ya, Wang, Dongbo, Li, Xue, Wang, Liping, Lei, Min, Huang, Qi, Yang, Qi,
2021. A critical review on the application of biochar in environmental pollution
remediation: role of persistent free radicals (PFRs). J. Environ. Sci. (China) 108,
201–216. https://doi.org/10.1016/j.jes.2021.02.021.
Marcińczyk, M., Oleszczuk, P., 2022. Biochar and engineered biochar as slow- and
controlled-release fertilizers. J. Clean. Prod. 339, 130685. https://doi.org/10.1016/
j.jclepro.2022.130685.
Maroušek, J., Gavurová, B., 2022. Recovering phosphorous from biogas fermentation
residues indicates promising economic results. Chemosphere 291 (Pt 1), 133008.
https://doi.org/10.1016/j.chemosphere.2021.133008.
Maroušek, J., Trakal, L., 2022. Techno-economic analysis reveals the untapped potential
of wood biochar. Chemosphere 291, 133000. https://doi.org/10.1016/j.
chemosphere.2021.133000.
Mishra, P.C., Patel, R.K., 2009. Use of agricultural waste for the removal of nitrate-
nitrogen from aqueous medium. J. Environ. Manag. 90 (1), 519–522. https://doi.
org/10.1016/j.jenvman.2007.12.003.
Mohan, D., Sarswat, A., Ok, Y.S., Pittman, C.U., 2014. Organic and inorganic
contaminants removal from water with biochar, a renewable, low cost and
sustainable adsorbent – a critical review. Bioresour. Technol. 160, 191–202. https://
doi.org/10.1016/j.biortech.2014.01.120.
Muga, H.E., Mihelcic, J.R., 2008. Sustainability of wastewater treatment technologies.
J. Environ. Manag. 88 (3), 437–447. https://doi.org/10.1016/j.
jenvman.2007.03.008.
Muo, I., Azeez, A., 2019. Green entrepreneurship: literature review and agenda for future
research. https://doi.org/10.2478/ijek-2019-0007.
Novais, S.V., Zenero, M.D.O., Barreto, M.S.C., Montes, C.R., Cerri, C.E.P., 2018.
Phosphorus removal from eutrophic water using modified biochar. Sci. Total
Environ. 633, 825–835. https://doi.org/10.1016/j.scitotenv.2018.03.246.
Oldfield, T.L., Sikirica, N., Mondini, C., López, G., Kuikman, P.J., Holden, N.M., 2018.
Biochar, compost and biochar-compost blend as options to recover nutrients and
sequester carbon. J. Environ. Manag. 218, 465–476. https://doi.org/10.1016/j.
jenvman.2018.04.061.
Panwar, N.L., Pawar, A., 2022. Influence of activation conditions on the physicochemical
properties of activated biochar: a review. Biomass Convers. Biorefin. 12 (3),
925–947. https://doi.org/10.1007/s13399-020-00870-3.
Park, J.H., Ok, Y.S., Kim, S.H., Cho, J.S., Heo, J.S., Delaune, R.D., Seo, D.C., 2015.
Evaluation of phosphorus adsorption capacity of sesame straw biochar on aqueous
solution: influence of activation methods and pyrolysis temperatures. Environ.
Geochem. Health 37 (6), 969–983. https://doi.org/10.1007/s10653-015-9709-9.
Pathy, A., Ray, J., Paramasivan, B., 2021. Challenges and opportunities of nutrient
recovery from human urine using biochar for fertilizer applications. J. Clean. Prod.
304, 127019 https://doi.org/10.1016/j.jclepro.2021.127019.
Peng, F., He, P.-W., Luo, Y., Lu, X., Liang, Y., Fu, J., 2012. Adsorption of phosphate by
biomass char deriving from fast pyrolysis of biomass waste. Clean: Soil, Air, Water
40 (5), 493–498. https://doi.org/10.1002/clen.201100469.
Peng, Y., Sun, Y., Hanif, A., Shang, J., Shen, Z., Hou, D., Zhou, Y., Chen, Q., Ok, Y.S.,
Tsang, D.C.W., 2021. Design and fabrication of exfoliated Mg/Al layered double
hydroxides on biochar support. J. Clean. Prod. 289, 125142. https://doi.org/
10.1016/j.jclepro.2020.125142.
Qasem, N.A.A., Mohammed, R.H., Lawal, D.U., 2021. Removal of heavy metal ions from
wastewater: a comprehensive and critical review. NPJ Clean Water 4 (1), 1–15.
https://doi.org/10.1038/s41545-021-00127-0.
Santos, F.M., Pires, J.C.M., 2018. Nutrient recovery from wastewaters by microalgae and
its potential application as bio-char. Bioresour. Technol. 267, 725–731. https://doi.
org/10.1016/j.biortech.2018.07.119.
Shaviv, A., 2001. Advances in controlled-release fertilizers. In: Advances in Agronomy,
vol. 71. Academic Press, pp. 1–49. https://doi.org/10.1016/S0065-2113(01)71011-
5.
Shepherd, J.G., Joseph, S., Sohi, S.P., Heal, K.V., 2017. Biochar and enhanced phosphate
capture: mapping mechanisms to functional properties. Chemosphere 179, 57–74.
https://doi.org/10.1016/j.chemosphere.2017.02.123.
Shetty, R., Vidya, C.S.-N., Prakash, N.B., Lux, A., Vaculík, M., 2021. Aluminum toxicity in
plants and its possible mitigation in acid soils by biochar: a review. Sci. Total
Environ. 765, 142744. https://doi.org/10.1016/j.scitotenv.2020.142744.
Shin, H., Tiwari, D., Kim, D.-J., 2020. Phosphate adsorption/desorption kinetics and P
bioavailability of Mg-biochar from ground coffee waste. J. Water Proc. Eng. 37,
101484. https://doi.org/10.1016/j.jwpe.2020.101484.
Smol, M., 2021. Transition to circular economy in the fertilizer sector—analysis of
recommended directions and end-users’ perception of waste-based products in
Poland. Energies 14 (14), 4312. https://doi.org/10.3390/en14144312.
Song, S., Arora, S., Laserna, A.K.C., Shen, Y., Thian, B.W.Y., Cheong, J.C., Tan, J.K.N.,
Chiam, Z., Fong, S.L., Ghosh, S., Ok, Y.S., Li, S.F.Y., Tan, H.T.W., Dai, Y., Wang, C.-
H., 2020. Biochar for urban agriculture: impacts on soil chemical characteristics and
on Brassica rapa growth, nutrient content and metabolism over multiple growth
cycles. Sci. Total Environ. 727, 138742. https://doi.org/10.1016/j.
scitotenv.2020.138742.
Stávková, J., Maroušek, J., 2021. Novel sorbent shows promising financial results on P
recovery from sludge water. Chemosphere 276, 130097. https://doi.org/10.1016/j.
chemosphere.2021.130097.
Su, J., Weng, X., Luo, Z., Huang, H., Wang, W., 2021. Impact of biochar on soil
properties, pore water properties, and available cadmium. Bull. Environ. Contam.
Toxicol. 107 (3), 544–552. https://doi.org/10.1007/s00128-021-03259-8.
M. Marcińczyk et al.
Takaya, C.A., Fletcher, L.A., Singh, S., Anyikude, K.U., Ross, A.B., 2016. Phosphate and
ammonium sorption capacity of biochar and hydrochar from different wastes.
Chemosphere 145, 518–527. https://doi.org/10.1016/j.chemosphere.2015.11.052.
Tang, Y., Alam, M.S., Konhauser, K.O., Alessi, D.S., Xu, S., Tian, W., Liu, Y., 2019.
Influence of pyrolysis temperature on production of digested sludge biochar and its
application for ammonium removal from municipal wastewater. J. Clean. Prod. 209,
927–936. https://doi.org/10.1016/j.jclepro.2018.10.268.
Tondera, K., Blecken, G., Tournebize, J., Mander, Ü., Tanner, C., 2018. Nutrient removal
from variable stormwater flows, pp. 31–55. https://doi.org/10.1007/978-3-319-
70013-7_3.
Trazzi, P.A., Leahy, J.J., Hayes, M.H.B., Kwapinski, W., 2016. Adsorption and desorption
of phosphate on biochars. J. Environ. Chem. Eng. 4 (1), 37–46. https://doi.org/
10.1016/j.jece.2015.11.005.
Usman, A.R.A., Ahmad, M., El-Mahrouky, M., Al-Omran, A., Ok, Y.S., Sallam, A. Sh, El-
Naggar, A.H., Al-Wabel, M.I., 2016. Chemically modified biochar produced from
conocarpus waste increases NO3 removal from aqueous solutions. Environ.
Geochem. Health 38 (2), 511–521. https://doi.org/10.1007/s10653-015-9736-6.
Vaneeckhaute, C., Lebuf, V., Michels, E., Belia, E., Vanrolleghem, P.A., Tack, F.M.G.,
Meers, E., 2017. Nutrient recovery from digestate: systematic technology review and
product classification. Waste Biomass Valorizat. 8 (1), 21–40.
Vendra Singh, S., Chaturvedi, S., Dhyani, V.C., Kasivelu, G., 2020. Pyrolysis temperature
influences the characteristics of rice straw and husk biochar and sorption/desorption
behaviour of their biourea composite. Bioresour. Technol. 314, 123674. https://doi.
org/10.1016/j.biortech.2020.123674.
Viglašová, E., Galamboš, M., Danková, Z., Krivosudský, L., Lengauer, C.L., Hood-
Nowotny, R., Soja, G., Rompel, A., Matík, M., Briančin, J., 2018. Production,
characterization and adsorption studies of bamboo-based biochar/montmorillonite
composite for nitrate removal. Waste Manag. 79, 385–394. https://doi.org/
10.1016/j.wasman.2018.08.005.
Wang, L., Ok, Y.S., Tsang, D.C.W., Alessi, D.S., Rinklebe, J., Mašek, O., Bolan, N.S.,
Hou, D., 2022. Biochar composites: emerging trends, field successes and
sustainability implications. Soil Use Manag. 38 (1), 14–38. https://doi.org/10.1111/
sum.12731.
Wang, J., Wang, S., 2019. Preparation, modification and environmental application of
biochar: a review. J. Clean. Prod. 227, 1002–1022. https://doi.org/10.1016/j.
jclepro.2019.04.282.
Wang, B., Lehmann, J., Hanley, K., Hestrin, R., Enders, A., 2015a. Adsorption and
desorption of ammonium by maple wood biochar as a function of oxidation and pH.
Chemosphere 138, 120–126. https://doi.org/10.1016/j.chemosphere.2015.05.062.
Wang, Z., Guo, H., Shen, F., Yang, G., Zhang, Y., Zeng, Y., Wang, L., Xiao, H., Deng, S.,
2015b. Biochar produced from oak sawdust by Lanthanum (La)-involved pyrolysis
for adsorption of ammonium (NH4+), nitrate (NO3− ), and phosphate (PO43− ).
Chemosphere 119, 646–653. https://doi.org/10.1016/j.chemosphere.2014.07.084.
Wang, Z., Li, J., Zhang, G., Zhi, Y., Yang, D., Lai, X., Ren, T., 2020. Characterization of
acid-aged biochar and its ammonium adsorption in an aqueous solution. Materials
13 (10), 2270. https://doi.org/10.3390/ma13102270.
Wang, B., Ma, Y., Lee, X., Wu, P., Liu, F., Zhang, X., Li, L., Chen, M., 2021.
Environmental-friendly coal gangue-biochar composites reclaiming phosphate from
water as a slow-release fertilizer. Sci. Total Environ. 758, 143664. https://doi.org/
10.1016/j.scitotenv.2020.143664.
Wilsenach, J.A., Maurer, M., Larsen, T.A., van Loosdrecht, M.C.M., 2003. From waste
treatment to integrated resource management. Water Sci. Technol. 48 (1), 1–9.
https://doi.org/10.2166/wst.2003.0002.
Xiao, R., Zhang, H., Tu, Z., Li, R., Li, S., Xu, Z., Zhang, Z., 2020. Enhanced removal of
phosphate and ammonium by MgO-biochar composites with NH3⋅H2O hydrolysis
pretreatment. Environ. Sci. Pollut. Control Ser. 27 (7), 7493–7503. https://doi.org/
10.1007/s11356-019-07355-5.
Xu, K., Lin, F., Dou, X., Zheng, M., Tan, W., Wang, C., 2018. Recovery of ammonium and
phosphate from urine as value-added fertilizer using wood waste biochar loaded
with magnesium oxides. J. Clean. Prod. 187, 205–214. https://doi.org/10.1016/j.
jclepro.2018.03.206.
Xu, D., Cao, J., Li, Y., Howard, A., Yu, K., 2019. Effect of pyrolysis temperature on
characteristics of biochars derived from different feedstocks: a case study on
ammonium adsorption capacity. Waste Manag. 87, 652–660. https://doi.org/
10.1016/j.wasman.2019.02.049.
12
Chemosphere 306 (2022) 135310
Yaashikaa, P.R., Senthil Kumar, P., Varjani, S.J., Saravanan, A., 2019. Advances in
production and application of biochar from lignocellulosic feedstocks for
remediation of environmental pollutants. Bioresour. Technol. 292, 122030. https://
doi.org/10.1016/j.biortech.2019.122030.
Yang, J., Li, H., Zhang, D., Wu, M., Pan, B., 2017. Limited role of biochars in nitrogen
fixation through nitrate adsorption. Sci. Total Environ. 592, 758–765. https://doi.
org/10.1016/j.scitotenv.2016.10.182.
Yang, H.I., Lou, K., Rajapaksha, A.U., Ok, Y.S., Anyia, A.O., Chang, S.X., 2018.
Adsorption of ammonium in aqueous solutions by pine sawdust and wheat straw
biochars. Environ. Sci. Pollut. Control Ser. 25 (26), 25638–25647. https://doi.org/
10.1007/s11356-017-8551-2.
Yang, F., Zhang, S., Sun, Y., Tsang, D.C.W., Cheng, K., Ok, Y.S., 2019. Assembling
biochar with various layered double hydroxides for enhancement of phosphorus
recovery. J. Hazard Mater. 365, 665–673. https://doi.org/10.1016/j.
jhazmat.2018.11.047.
Yang, H., Ye, S., Zeng, Z., Zeng, G., Tan, X., Xiao, R., Wang, J., Song, B., Du, L., Qin, M.,
Yang, Y., Xu, F., 2020. Utilization of biochar for resource recovery from water: a
review. Chem. Eng. J. 397, 125502. https://doi.org/10.1016/j.cej.2020.125502.
Yao, Y., Gao, B., Inyang, M., Zimmerman, A.R., Cao, X., Pullammanappallil, P., Yang, L.,
2011. Removal of phosphate from aqueous solution by biochar derived from
anaerobically digested sugar beet tailings. J. Hazard Mater. 190 (1), 501–507.
https://doi.org/10.1016/j.jhazmat.2011.03.083.
Ye, Y., Ngo, H.H., Guo, W., Chang, S.W., Nguyen, D.D., Zhang, X., Zhang, J., Liang, S.,
2020. Nutrient recovery from wastewater: from technology to economy. Bioresour.
Technol. Rep. 11, 100425. https://doi.org/10.1016/j.biteb.2020.100425.
Ye, L., Camps-Arbestain, M., Shen, Q., Lehmann, J., Singh, B., Sabir, M., 2020a. Biochar
effects on crop yields with and without fertilizer: a meta-analysis of field studies
using separate controls. Soil Use Manag. 36 (1), 2–18. https://doi.org/10.1111/
sum.12546.
Ye, L., Camps-Arbestain, M., Shen, Q., Lehmann, J., Singh, B., Sabir, M., 2020b. Biochar
effects on crop yields with and without fertilizer: a meta-analysis of field studies
using separate controls. Soil Use Manag. 36 (1), 2–18. https://doi.org/10.1111/
sum.12546.
Yin, Q., Ren, H., Wang, R., Zhao, Z., 2018a. Evaluation of nitrate and phosphate
adsorption on Al-modified biochar: influence of Al content. Sci. Total Environ.
631–632, 895–903. https://doi.org/10.1016/j.scitotenv.2018.03.091.
Yin, Q., Wang, R., Zhao, Z., 2018b. Application of Mg–Al-modified biochar for
simultaneous removal of ammonium, nitrate, and phosphate from eutrophic water.
J. Clean. Prod. 176, 230–240. https://doi.org/10.1016/j.jclepro.2017.12.117.
Yin, Q., Liu, M., Li, Y., 2020. Desorption characteristics of phosphate and ammonium
from sludge-based biochar. Environ. Technol. 1–11. https://doi.org/10.1080/
09593330.2020.1858179, 0(0).
Yu, J., Hu, H., Wu, X., Zhou, T., Liu, Y., Ruan, R., Zheng, H., 2020. Coupling of biochar-
mediated absorption and algal-bacterial system to enhance nutrients recovery from
swine wastewater. Sci. Total Environ. 701, 134935. https://doi.org/10.1016/j.
scitotenv.2019.134935.
Zhang, M., Gao, B., Yao, Y., Xue, Y., Inyang, M., 2012. Synthesis of porous MgO-biochar
nanocomposites for removal of phosphate and nitrate from aqueous solutions. Chem.
Eng. J. 210, 26–32. https://doi.org/10.1016/j.cej.2012.08.052.
Zhang, M., Song, G., Gelardi, D.L., Huang, L., Khan, E., Mašek, O., Parikh, S.J., Ok, Y.S.,
2020. Evaluating biochar and its modifications for the removal of ammonium,
nitrate, and phosphate in water. Water Res. 186, 116303. https://doi.org/10.1016/j.
watres.2020.116303.
Zhang, M., Yang, J., Wang, H., Lv, Q., Xue, J., 2021. Enhanced removal of phosphate
from aqueous solution using Mg/Fe modified biochar derived from excess activated
sludge: removal mechanism and environmental risk. Environ. Sci. Pollut. Control
Ser. 28 (13), 16282–16297. https://doi.org/10.1007/s11356-020-12180-2.
Zhao, H., Xue, Y., Long, L., Hu, X., 2017. Adsorption of nitrate onto biochar derived from
agricultural residuals. Water Sci. Technol. 77 (2), 548–554. https://doi.org/
10.2166/wst.2017.568.
Zin, M.M.Thant, Kim, D.-J., 2021. Simultaneous recovery of phosphorus and nitrogen
from sewage sludge ash and food wastewater as struvite by Mg-biochar. J. Hazard
Mater. 403, 123704. https://doi.org/10.1016/j.jhazmat.2020.123704.