Journal of Water Process Engineering 49 (2022) 103159

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Journal of Water Process Engineering

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

A comprehensive review on technological advances of adsorption for

removing nitrate and phosphate from waste water
E. Priya a, Surendra Kumar b, Chhavi Verma d, Sudipta Sarkar a, c, *, Pradip K. Maji a, d, *
a
Centre for Nanotechnology, Indian Institute of Technology Roorkee, Roorkee 247667, Uttarakhand, India
b
Department of Botany, Jai Narain Vyas University, Jodhpur 342001, Rajasthan, India
c
Department of Civil Engineering, Indian Institute of Technology Roorkee, Roorkee 247667, Uttarakhand, India
d
Department of Polymer & Process Engineering, Indian Institute of Technology Roorkee, Saharanpur Campus, Saharanpur 247001, Uttar Pradesh, India

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

Keywords: Nitrate and phosphate contamination in water sources is considered a major problem globally. The excessive
Adsorption discharge of nitrate and phosphate is responsible for the most widespread contamination in an aquatic system,
Nitrate causes eutrophication to harm the ecosystem, and severe threats to people’s health. So the removal and recovery
Phosphate
of these nitrate and phosphate are esteemed as one of the interventions to prevent the water bodies’ eutrophi­
Co-sorbents
Water purification
cation by application of numerous methods. Adsorption is a low-cost, efficient, environmentally friendly, and
Sorption capacity universal method utilized to remove nitrate and phosphate from wastewater. Here we review adsorption as an
effective method for removing nitrate and phosphate from an aqueous solution, even with a low effluent con­
centration in the water medium. The major points are the following: first, this review compiles the data reported
in the various literature about nitrate and phosphate removal through adsorption using different adsorbents like
carbon base, clay base, zeolite base, chitosan, agricultural waste, cellulose nanocrystal, cellulose nanofibre, metal
hydroxide, and biochar base. Second, the adsorption capacity, preparation, and modification method of adsor­
bents, the effect of temperature, and pH of using such adsorbents for removing nitrate and phosphate have also
been discussed. Third, a discussion of some high-performance adsorbents for the removal of nitrate and phos­
phate is proposed; this is a key novelty of this review work. Moreover, the future outlook and upcoming nitrate
and phosphate removal and recovery challenges are presented.

1. Introduction these sectors, domestic wastewater is the primary source of discharge of

The development of human civilization has always been associated
with deleterious effects on the environment, especially in water [1].
However, current day water pollution is considered a major problem
globally. Though 70 % of the earth’s surface is full of water, the acces­
sibility of freshwater is a crucial problem across the world. The growing
utilization of limited fresh water resources needs an efficient wastewater
treatment system. Clean water is necessary for human beings and other
life systems [2]. Water pollution is caused by the discharge of inorganic
and organic contaminants such as nitrate, phosphate, heavy metal ions,
toxic metalloids, and synthetic organic chemicals (Fig. 1) [3]. The
release of anionic pollutants such as phosphate, nitrite, and nitrate
(which has nutrient value) into natural water bodies like rivers, lakes,
and oceans leads to severe degradation in water quality [4]. Domestic
and industrial wastewater is the main source of these nutrients. Among
these nutrients into the aquatic water bodies. It was found that the
higher concentrations of NO−3 (nitrate), NO−2 (nitrite), and PO3−
4 (phos­
phate) present in wastewater discharge from treatment plants [5].
Generally, the aquatic ecosystem cannot exhaust all the nutrients
available in the wastewater discharged from treatment industries,
leading to eutrophication problems [6]. Phosphate and nitrogen are
known as plant growth nutrients, excess of which, when present in
surface water, cause algal bloom, which ultimately leads to eutrophi­
cation problems. Eutrophication is the slow aging of the water body,
resulting in the abundant development of aquatic plants, declining dis­
solved oxygen, becoming toxic to water inhabitants, and disturbing the
ecological balance [7]. Nitrate and phosphate are the plant nutrients
needed for their growth and thus vital for modern agriculture, which are
crucial elements for the growth of living organisms and are used in
agriculture as fertilizer [8]. The maximum yield of crop production is

* Corresponding authors.
E-mail addresses: sudipta.sarkar@ce.iitr.ac.in (S. Sarkar), pradip@pe.iitr.ac.in (P.K. Maji).

https://doi.org/10.1016/j.jwpe.2022.103159
Received 28 May 2022; Received in revised form 3 September 2022; Accepted 13 September 2022
Available online 21 September 2022
2214-7144/© 2022 Elsevier Ltd. All rights reserved.
E. Priya et al. Journal of Water Process Engineering 49 (2022) 103159

gained by using conventional fertilizers, which disturbs global pop­ wastewater and reduce their concentration to an acceptable level
ulations and suffers from a leaching load of nitrate and phosphate. The specified by the effluents standard guidelines before the treated waste­
increase in NO−3 concentration is due to the numerous types of human water is discharged into water bodies. Fig. 2 represents the number of
action, primarily by using nitrogen fertilizers in agriculture, mainly in articles published yearly in Science Direct (access date: 11 July 2022,
the form of urea [9]. However, the utilization range of nitrogen fertilizer time: 12:30 pm) for the few years on the topic of phosphorous and ni­
is only 30–50 % remaining washed out due to its high water solubility trogen in water and wastewater; the number has grown exponentially,
[10,11]. Nitrogen in the form of nitrate does not bind to the soil signifying the importance of the occurrence and removal of nitrate and
immediately due to its higher water solubility predominating the phosphate in water and wastewater.
leaching over adsorption in the land. It leads to an increase in nitrate
pollution in ground and surface water sources [12]. The various sources
of nitrate contamination are industrial wastes discharged in an unsafe 1.1. Technologies for the removal of nitrate and phosphate from
manner, urban and agricultural runoff, landfill leachate, disposal of wastewater
untreated sewage and leakage from septic systems, and animal manure
[13]. In aquatic environments, the main source of phosphate pollution is Various techniques have been developed and used to remove nitrate
fertilizers used on agricultural land, effluent from the food processing and phosphate from wastewater. They largely include (i) chemical
industry, and household wastewater. This phosphate is readily available precipitation [21], (ii) reverse osmosis [22], (iii) biological processes
in a form that can be used in aquatic systems, directly leading to algae
growth and promoting eutrophication. The discharge of effluents con­
taining nitrate and phosphate in excessive amounts into the aquatic
environment increases the possibility of eutrophication [14]. Thus, in
natural water ecosystem, enrichment of water with nitrate and phos­
phate is a global environmental issue.
To prevent the eutrophication problem, the recommended release
concentration of nutrients in the water stream is 2.6 mg/L PO3− 4 , <11
mg/L NO−3 , and 0.03 mg/L NO−2 [15]. Some researchers have specified
that for the growth of algae, even 0.02 mg/L phosphate concentration in
a water system is sufficient [15,16]. Several environmental governing
organizations, including the United States Environmental Protection
Agency (USEPA), have fixed a maximum pollutant level of 10 mg/L of
nitrate in drinking water and has recommended a maximum concen­
tration of phosphate in drinking water as 50 μg/L [17,18]. Besides
eutrophication, the increase in NO−3 concentration in drinking water
leads to serious health problems like blue-baby syndrome (methemo­
globinemia). Sometimes it allows conversion into nitrosamine, affecting
infants mainly [19]. Recent works have revealed that additional nitrate
in drinking water is responsible for various cancers, infectious diseases,
and diabetes. It also acts as a precursor of carcinogens [20]. Therefore, it Fig. 2. Numbers of published articles about nitrate and phosphate from 1998 to
is essential to remove nitrate and phosphate from contaminated water or May 2022 based on science direct database.

Fig. 1. The diversified sources of phosphate and nitrate pollution.

2
E. Priya et al.
[23], (iv) coagulation-flocculation [24] and (v) adsorption [25]. Of all
these techniques, chemical precipitation is the most widely used method
of phosphate removal by precipitation as salts of metals like (Fe(II), Fe
(III), Al(III), and Ca(II)). This method often produces treated effluent
concentrations below 1.0 mg/L as P [26]. Metal ions, when added to the
contaminated water or wastewater, combine with phosphate to form
insoluble precipitates of metal phosphate, which can be easily separated
from water using gravity separations or filtration processes [27].
Reverse osmosis is a membrane-based non-selective separation process
applied to treat a wide variety of industrial effluents, which removes all
the impurities present in the water or wastewater, including the non-
target species [28]. The reverse osmosis process uses a semipermeable
membrane, which needs a driving force to overcome the osmotic barrier
and also to push the fluid through the membrane; thus, it is an energy
intensive process [29]. Biological processes have been used for the
removal of both phosphorus and nitrogen from the contaminated water.
The biological nitrogen removal consists of two consecutive steps —
nitrification and denitrification. In nitrification process the organic-
bound nitrogen and ammoniacal nitrogen are converted by the mi­
crobes into nitrate. In denitrification process, nitrate is reduced into
gaseous nitrogen. Denitrification is an essential process of the nitrogen
cycle, and it is potentially more complicated. This method specifies that
the nitrate reduction into nitrogen in the lack of oxygen condition
(anoxic condition) is the primary fundamental of biological denitrifi­
cation [30]. On the other hand biological phosphate removal process is
carried out by a special group of microorganisms known as phosphate
accumulating organisms (PAOs) which when exposed to alternate
anaerobic and anaerobic conditions, tend to uptake phosphate during
the aerobic conditions. In order to remove phosphate from the polluted
water, these phosphate-rich microorganisms are isolated from the
effluent. Biological phosphate and nitrogen removal processes have
several disadvantages, such as requirements of high energy, sensitivity
to environmental conditions, and the possibility of the generation of
toxic nitrite ions. Coagulation and flocculation followed by sedimenta­
tion/filtration are conventional techniques in the wastewater industry to
remove suspended solids. Salts of two commonly used metal ions - alum
and ferric chloride. The metal ions destabilize particles through the
chemical reaction between coagulants and colloids [31]. The metal
hydroxides bind to the phosphate ions via inner sphere complexation
due to Lewis acid-base interaction and precipitate. These currently
available technologies have their limitations. They are not quite effec­
tive, more expensive and are responsible for generating several by-
products. Nevertheless, these methodologies do not solve the problems
associated with excessive nitrate and phosphate present in the envi­
ronment. Adsorption and ion-exchange processes hold promise for being
the appropriate technologies for the selective removal of phosphate and
nitrate from the contaminated water.
1.2. Removal of nutrients from wastewater by adsorption process
The adsorption process is considered to be an effective method in
wastewater treatment because of its simplicity of design, convenient use,
easy-to-operate nature, and no requirement for any special care [32].
This technology is applicable for the elimination of diverse kinds of
organic contaminants and inorganic species, including anions, such as
fluoride [33], nitrate [34], bromate [35], perchlorate [36], and phos­
phate [37] from water by the use of several different types of adsorbent
materials. Adsorption is a surface-based process in which ions, atoms, or
molecules are attached to the adsorbent’s surface. As adsorption being a
surface phenomenon, the adsorbent, and its physicochemical qualities
significantly influence the sorptive removal of the contaminants. An
excellent adsorbent should have the following characteristics: high
selectivity, low cost, long life, and high adsorption capacity. Adsorbents
differ in terms of pore size, active surface area, surface functional group,
pore sizes and their distribution, etc. Porous adsorbents are classified
into three major categories based on their pore size: macropores >50
3
Journal of Water Process Engineering 49 (2022) 103159
nm, mesopores between 2 and 50 nm, and micropores <2 nm. To
selectively remove nitrate and phosphate from an aqueous solution,
many commercial adsorbents have been used, such as activated carbon,
zeolites, chitosan, cellulose-based adsorbents, modified agricultural
waste-based adsorbents, and biochar. Adsorbents with distinct surface
physicochemical qualities, pore structure, and surface functional groups
play essential roles in nitrate and phosphate adsorption [38]. As shown
in Fig. 3, this adsorption process can occur between adsorbent and
adsorbate molecules through a physical (weak van der Waals forces of
attraction is known as physisorption) and chemical process (adsorption
occurs through chemical bonding is called chemisorption). Usually, it is
a reversible process. The process for the release of the adsorbate species
upon the exhaustion of the available sites on the adsorbent is called
desorption [39]. The process of desorption is important when the same
adsorbent is reused over many number of cycles. Nitrate and phosphate
removal through adsorption can take place via various mechanisms like
electrostatic interactions, ion exchange, surface complexation (inner-
sphere and outer-sphere), hydrogen bonding, precipitation, and ligand
exchange [40]. When the contaminants get electrostatically adsorbed
onto surfaces with opposite charges, the interaction is known as an
electrostatic attraction [41,42]. Thus, in such an adsorption process, a
protonated surface would electrostatically attract negatively charged
species or anions such as negatively charged phosphate species (H2PO−4 ,
HPO2− 3−
4 , PO4 ) and nitrate ions NO3 [43–46]. In the ion exchange
−
mechanism, an exchange of ions occurs between the solution and solid/
porous ion exchanger. Modifying the surfaces of the adsorbents with
primary, secondary, tertiary, and quaternary ammonium functional
groups plays an important role in the adsorption of nitrate and phos­
phate ions by an ion-exchange mechanism [47–50]. Removal using
surface complexation is essentially based on two mechanisms: inner-
sphere complexation and outer-sphere complexation mechanism. In
the outer-sphere complexation mechanism, electron transfer occurs
between chemical species which remain separate before, after, and
during the electron transfer that do not form any intermediate, and no
bonds are formed or broken. In the inner-sphere complexation mecha­
nism, electron transfer occurs between complexes via a bridging ligand
and through the formation of a covalent bond [43,44,51–55]. In ligand
exchange, ligands are basically ion or natural molecules. The formation
of a coordinate covalent bond occurs due to donating the electrons pair
to metal atoms. Several reports indicated that ligand exchange could be
created by inner-sphere complexes and electrostatic attraction between
positively charged metal and metal oxide surfaces and negatively
charged phosphate ions [54,56]. The electrostatic attraction occurs be­
tween the negatively charged ions, such as N−2 and O−2 and protonated
hydrogen ion is known as hydrogen bond. Through this interaction, the
hydrogen atom loses its electron to neighboring atoms that have an
equal probability of forming a hydrogen bond. The hydroxyl ion (OH) is
a good example, where one positive charge of hydrogen is attracted by
the negative charge of O2 to make the unit of OH. This unit of OH, due to
its net negative, is responsible for forming a component of the phosphate
crystal structures [41,42]. The hydrogen bond is weaker than stronger
bonds like covalent and ionic bonds, but it is stronger than the van der
walls interaction [49]. The precipitation technique is also referred to as
aqueous precipitation or chemical precipitation. Studies have been re­
ported that the Mg2+ and Ca2+ are used for the precipitation of phos­
phate complex [43,44,52,57–60]. The possible mechanism of the
adsorption process is explained in Fig. 4. Further, the potential advan­
tage of the adsorption technology is the ability to achieve a higher
accumulation of nitrate and phosphate onto the adsorbent leading to
lower nitrate and phosphate concentration levels in the treated effluent
[61].
The synthesis of cost-effective adsorbents has been the focus of the
fast-growing research interests in this field. Various types of materials
from diverse origins have been employed to selectively remove phos­
phate and nitrate from water by the adsorption process, as will be dis­
cussed in the following sections of this article. However, no overview of
E. Priya et al. Journal of Water Process Engineering 49 (2022) 103159

Fig. 3. The conventional methods of the adsorption process.

Fig. 4. Schematic diagram displaying the possible adsorption mechanisms of nitrate and phosphate.

the adsorption potentials of the different adsorbent materials studied so
far for nitrate and phosphate removal has been published. The present
review article focuses on the most recent literature studies on the syn­
thesis and utilization of various types of adsorbents to remove and
recover nitrate and phosphate from wastewater. Fig. 5 provides a sum­
mary of various types of adsorbents so far used for the purpose. The key
concepts, including kinetic models, applicable adsorption isotherm
models, and adsorption capacities, a source of up-to-date literature, have
been presented in this article, and the results have been discussed. A
summary of the sorption efficiency and mechanism for different sorbents
for nitrate and phosphate removal and recovery from aqueous solution
has been represented in Table 1 and Table 2. This study will help
enhance and update the knowledge of researchers working on the
removal of phosphate and nitrate from wastewater.

4
 E. Priya et al.
Various absorbents used for nitrate and phosphate removal

Nitrate Phosphate

Carbon-based Natural sorbent Biosorbent Agricultural Cellulose based Zeolite Agricultural Biochar Metal Chitosan Cellulose
adsorbents (Chitosan) waste based adsorbents Based waste based based hydroxide based based
adsorbents adsorbents adsorbents adsorbents adsorbents adsorbents
Clay Zeolite
Surfactant
- modified
Impregnated
Activated Modified Surfactant Wheat straw
Chitosan Agricultural corn ZSM-5 SP-Zr-La
carbon CPTMS/CNC Ca-biochar Metal MIL-
clay modified based cob and coconut zeolite (Fe+3) 101(Al/Fe)
mineral BEA- type hybrid bio- copra beads with oxide/
with of zeolite composites lanthanum Agro waste hydroxide
HDTMA material Natural Rice husk Modified nano- M-IACBs
RS2/ Chemically Cell-g-
cellulose h magnetic -particles
Na2CO3 modified biochar E/PEI
adsorbents biochar
APTS- from sugarcane Synthetic
5

2M HCl zeolite Chitosan- bagasse zeolite with Seagrass

activated Fe3+ fly ash CTAB Chitosan/
Lignite
complex Cell-g-E/PEI modified Lanthanu Fe(OH)3@
GAC with Ethiopian Modified CaO- biochar IONP m CNFs
ZnCl2 bentonite brewer’s spent RS-PA hydrogel
Surfactant grain (MBSG) Lanthanum beads
modified Chitosan incorporated
Modified Natural Lanthanum Magnetic
nano composites ternary
clay Onion peel Ws-N-Zr modified iron oxide
granular zeolite with PVA (hydro)
activate minerals dust platanus ball nano-
(SMZN) and PEG oxides nano- La-BC-5
carbon (NC) fiber biochar -particle
composite
(MALZ) (La-TC)
St+@UiO-66
Nanocrystal-line
Local clay Nano cellulose
Rice husk
activated chitosan/
carbon clinoptilolite Fe-Zeolite-A

Journal of Water Process Engineering 49 (2022) 103159

Modified wheat
(Nono-
straw
CS/Clino)
ZEO@AZ
Pine sawdust

Mn-Zr-Fe
modified
natural
zeolites

Fig. 5. List of various sorbents used for the removal of nitrate and phosphate from water.
E. Priya et al. Journal of Water Process Engineering 49 (2022) 103159

Table. 1
Summary of sorption efficiency and different parameters for the removal of nitrate by various types of adsorbents.
Adsorbent Amount Conc. range Contact Temperature pH Adsorption mechanism Reference
adsorbed time

Carbon-based adsorbents
• AC-CTABr from dates stems 83.33 mg/g 100–600 – 25 ◦ C 5.8 The activated carbon (AC) impregnated with CTABr [68]
mg/L solution introduced ammonium group CTA+ onto
the activated carbon surface, responsible for the
electrostatic interaction between nitrate ions and
CTA+.
• RS2/Na2CO3 8.2 mg/g 50 mg/L 24 h 25 ◦ C 8.0 Ion exchange interaction occurs between the [69]
functional group and nitrate ions
• Lignite modified GAC with 4.4 mg/g 50 to 150 30 min 25 ± 2 C ◦
5.0 Nitrate adsorption on LGAC5 was a physical [71]
ZnCl2 mg/L adsorption process.
• Granular activated carbon 43.1 mg/g 10–50 mg/ 60 min 25 ± 1 ◦ C 4.0 Nitrate adsorption onto MGAC follows a [72]
modified with Fenton L heterogeneous (multilayer) mechanism.
reagents
• Rice husk-activated carbon 93.5 mg/g 100–200 4h Room 4.0 The adsorption mechanism was based on [73]
• Carbon prepared from 79.5 mg/g mg/L temperature electrostatic interaction
primary sludge of wastewater
treatment of paper industry
Clay-based adsorbents
• H-B-4CEC 14.76 mg/g 100 mg/L 17 h Room 5.4 Compared with unmodified clay minerals, modified [76]
temperature clay minerals with HDTMA had better adsorption
capacities towards nitrate ions it was due to
surfactant cations that can attract and
electrostatically hold anionic contaminants.
• 2 M HCl activated Ethiopian 5.0 mg/g 250–500 – 30 ◦ C 5.0 Bentonite is a metal oxide adsorbent containing [77]
bentonite mg/L different metal oxide in the structure through
activation, hydroxylated surfaces of these oxides
develop a charge on the surface. The interaction
between nitrate ion and metal oxide was modeled by
assuming ligand exchange reactions
• Adsorbent A1 5.1 mg/g 100 mg/L 2h Room 2 to 4 Adsorption nitrate due to the electrostatic [79]
temperature interaction
• Natural clay mineral (NC) 244.06 mg/g 300 mg/L 180 min 20 ◦ C 5.1 The strong electrostatic interaction between the [78]
positively charged surface sites of the adsorbent and
the nitrate ions.
Zeolite based adsorbents
• BEA-type nanocrystals 19 mg/g 0.8–24.2 24 h Room 5.5 The adsorption capacity due to the presence of a [84]
• BEA-type nanosponges 83 mg/g mmol.L− 1 temperature more positive charge in the surface-modified zeolite
with HDTMA+Br− at pH 5.5 led to the electrostatic
attraction between surface-modified zeolite and
nitrate ions.
• APTS-zeolite 12.54 mg/g 50 mg/L 4h 30 ◦ C 3.0 The APTS-zeolite, NH2 groups on the surface need [85]
an H+ ion to convert NH2 into NH+ 4 to remove
nitrate, which was possible on acidic conditions.
Under the acidic condition, the positively charged
surface group of adsorbent attract the nitrate ions.
• SMZNC 810 (±50) 0.8–40.5 – Room 6.0 The nitrate adsorption capacity was higher at pH 6 [86]
mmol⋅kg− 1 mmol⋅L− 1 temperature for these three modified materials. Further lower
• SMZNS 1941 (±100) pH, in the range of 4–6, led to a decrease the nitrate
mmol⋅kg− 1 removal due to an increase of the H3O+ a
• SMZNSp 2125 (±100) concentration that led to the formation of another
mmol⋅kg− 1 form of nitrate, which is the HNO3 form that could
limit the surface exchange between Br− and Cl−
species and NO−3 . In addition, a slight decreased in
the nitrate removal capacity was also noticed once
being in the basic medium range. This could be
explained by the presence of OH− species in such
medium and its competition with NO−3 in
contaminated water.
Chitosan-based adsorbents
• Chitosan/bentonite (ChBT) 35.68 mg/g 200 mg/L 180 min 40 ◦ C 6.0 Adsorption of nitrate by chitosan/bentonite [88]
• Chitosan/titanium oxide 43.62 mg/g biocomposites was generally electrostatic
(ChTi) interaction.
• Chitosan/alumina (ChAl) 43.62 mg/g
• Nano-CS/Clino@ PEHA 277.77 mg/g 100 to 300 30 min 25 ◦ C 4.0 After the chemical modification, the material [89]
mg/L showed an increased adsorption capacity, and it was
due to the strong electrostatic attraction between
the positively charged adsorbent sites (such as
amine and a hydroxyl group) towards the nitrate
ions.
• Chitosan-Fe3+complex 8.35 mg/g 50 mg/L 1.5 h 25 ◦ C 5.9 ± Nitrate adsorption was mainly attributed to ion [91]
0.2 exchange and electrostatic attraction.
• PEG/chitosan 50.68 mg/g 10 mg/L 40 min Room 3.0 The adsorption of nitrate onto PEG/chitosan and [90]
• PVA/chitosan 35 mg/g temperature PVA/chitosan was mainly due to strong electrostatic
(continued on next page)

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E. Priya et al. Journal of Water Process Engineering 49 (2022) 103159

Table. 1 (continued )
Adsorbent Amount Conc. range Contact Temperature pH Adsorption mechanism Reference
adsorbed time

interaction between the positively charged

adsorbent sites and the nitrate anion.
Agricultural waste-based
adsorbents
• Corn cob 49.9 mg/g 20 mg/L 24 h 25 ◦ C 6.5 The adsorption occurred through the electrostatic [92]
• Coconut copra 59.0 mg/g attraction between positive surface charges on the
adsorbent and negative charges on the anions by
outer-sphere surface complexation (non-specific
adsorption).
• Modified biochar of sugarcane 28.21 mg/g 50 mg/L 60 min 22 ◦ C 3.0 Nitrate adsorption efficiency was higher under [93]
bagasse acidic pH than basic pH due to the electrostatic
attraction occurring between nitrate ions and the
modified biochar surface.
• Modified brewers’ spent grain 14.4 mg/g 30 mg/L 120 min 25 ◦ C 3 to 8 The mechanism based on electrostatic interaction [94]
(MBSG)
• Onion peel dust 5.93 mg/g 100 mg/L 10 min 40 ◦ C 12 The nitrate adsorption was favorable when the [95]
surface of OPD is negative, and it is only possible
due to hydrogen bonding between surface adsorbed
hydroxyl ions and NO−3 ions.
• Nanocrystalline cellulose 8.33 mg/g 100 mg/L 100 min Room 6.0 Electrostatic interaction [96]
temperature
• Modified wheat straw 8.5 mg/g 20 mg/L 10 min 25 ◦ C 7.0 – [97]
• Pine sawdust 32.8 mg/g 50 mg/L 4h 40 ◦ C 5.8–7.0 The incorporated triethylamine functional group [98]
was responsible for the nitrate adsorption
• Modified hazelnut shell 26.5 mg/g 30 mg/L 60 min 25 ◦ C 4.0–10 The adsorption mechanism was based on [99]
electrostatic interaction
Cellulose based adsorbents
• CPTMS/CNC 30 mg/g 20 mg/L 10 min 25 ◦ C 7.0 – [102]
• Natural cellulosic adsorbents 96.5 % 5 mg/L 10 min 25 ◦ C 6.6 The mechanism was based on electrostatic [103]
removal interaction
• Cell-g-E/PEI 158.3 mg/g 100–250 4h 30 ◦ C 4.5 The electrostatic interaction between nitrate and [104]
mg/L adsorbent surface
The adsorbent used for the
nitrate removal by co-removal
mechanism
• MG@La 138.88 mg/g 20 mg/L 5 to180 20 to 40 ◦ C 4 to 8 Nitrate adsorption was based on electrostatic [53]
min interaction
• HA520E-Fe hybrid material 56.85 mg/g 100 mg/L – 25 ◦ C 3 Adsorption of nitrate ions through the ion exchange [105]
mechanism
• Nanocomposite HFO@TPR Reduced from 50 mg/L 12 h 25 C
◦
7.2 Adsorption via an ion exchange mechanism [106]
18 to <10 mg/
g
• RH 700 (rice husk) 95.42 mg/g 100 mg/L 12 h – – Adsorption through the ion exchange mechanism [107]
• Amine-functionalized walnut 24.8 mg/g 30 mg/L 1h 298 K 3.0–0.9 Adsorption was based on electrostatic and hydrogen [108]
shells (ACWNS) bond
• Amine cross-linked tea waste 136.43 mg/g 1000 mg/g 60 min 25 ◦ C 6.0 Adsorption was based on electrostatic and ion [109]
(ACTW) exchange
• Cellulose nanofibres aerogels 79.65 % 100 mg/L 60 min 25 ◦ C 6 Electrostatic interaction [110]
removal

2. Nitrate removal through the adsorption process 2.1. The carbon-based adsorbents used for nitrate removal

Nitrogen deposition in the environment from geogenic and anthro­
pogenic sources raises nitrate concentrations in water bodies. House­
holds, animals, fertilizer manufacturers, the food industry, and other
industries generate large volumes of organic, inorganic, and biologically
bound nitrogen and sewage waste rich in inorganic nitrogen compounds
[62]. These elevated nitrogen concentrations are much higher than what
the environment can eliminate and assimilate. Due to its high solubility
and stability, nitrate has a low tendency to getting removed via
adsorption and precipitation; therefore, it is hard to eliminate this ion
from water using conventional water treatment technologies [63]. The
various adsorbents with outstanding characteristics to adsorb nitrates
from water by adsorption process have been produced by various re­
searchers. In order to get the best removal rates, it is vital to use the
proper material for the removal of particular types of anions. In the
subsequent sub-sections, we discuss in detail the capabilities of different
materials used so far for the removal of nitrate from contaminated
water.
Activated carbon (AC), commonly known as a universal adsorbent in
powder or granular form, is widely used to remove several types of water
pollutants, particularly organic pollutants. However, AC shows weak
adsorption capacity towards anionic pollutants, and only limited studies
have investigated the adsorption potential of NO−3 of AC [64–67]. A
surfactant-altered activated carbon (AC-CTABr) was used to remove
anionic compounds, mainly nitrate, from water systems [68]. The
surfactant-altered activated carbon AC-CTABr was prepared through the
chemical activation of date stem, followed by saturation with CTABr
solution, which led to the addition of an ammonium-based functional
group (CTA+) onto the activated carbon surface. Experimental results
revealed that the kinetics of adsorption was quite fast, so that the
equilibrium was obtained within 5 min of contact time between the
nitrate solution and the adsorbents (AC and AC-CTABr) and the
maximum capacity was found to be 83.33 mg/g [68]. The AC-CTABr
was more efficient for the sorption of NO−3 than bare AC because of
the presence of ammonium group CTA+ on the surface. The results
suggested that NO−3 removal increased from 14 % in AC to 60 % in the

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E. Priya et al. Journal of Water Process Engineering 49 (2022) 103159

Table. 2
Summary of sorption efficiency and different parameters for the removal of phosphate by various types of adsorbents.
Adsorbent Amount Conc. Contact Temperature pH Adsorption mechanism Reference
adsorbed range time

Zeolite based adsorbents

• La-ZB 106.2 mg/g 200 mg/L 180 min Room 6.0 Based on the inner-sphere surface complexation [114]
temperature mechanism
• La-P1 58.2 mg/g 12.5 to 24 h 25 ◦ C 5.3 The phosphate species were adsorbed onto zeolites by [115]
• La-A 44.0 mg/g 200 mg/L electrostatic forces and with the involvement of the
• La-CLP 24.6 mg/g ion-exchange mechanism
• MALZ 80.8 mg/g 500 mg/L 180 min 25 ◦ C 6.6 The phosphate was removed by the ligand exchange [116]
mechanism and the formation of LaPO4⋅xH2O
• Fe-Zeolite-A 18.75 mg/g 4.725 mg/ 10 min – 5.0 The mechanism was based on ligand exchange, [117]
L electrostatic, and diffusion.
• ZEO@AZ 24.96 mg/g 50 mg/L 24 h 25 ◦ C <6 The mechanism was based on inner sphere complex [118]
formation
• Mn-Zr-Fe-modified natural 20.9 mg/g 10 mg/L 24 h 25 ◦ C 2.0–6.0 Electrostatic attraction and ligand exchange [119]
zeolites
Agricultural waste-based
adsorbents
• HFO@St+ 27.81 mg/g 5 to 60 24 h Room 6.0 The nano-sized hydrous Fe(III) oxides (HFO) were [120]
• HFO@St+ 40.19 mg/g mg/L temperature 3.2 based on the mechanism of inner-sphere complex
formation.
• Activated rice husk ash 89 % 10 mg/L 24 h 25 ◦ C 6 The presence of polar groups on the surface increases [121]
(ARHA) the cation exchange capacity of the adsorbents. The
presence of crystalline silica and the Si–O–Si group
was responsible for the adsorption of phosphate ions.
• Seagrass residues of 3.3 mg/g 100 mg/L 24 h – – – [122]
Posidonia oceanica
• RS-PA 71.94 mg/g 400 mg/L 90 min 25 ◦ C 7.0 The incorporated triethylamine functional group was [123]
responsible for the selective adsorption of phosphate
• WS-N-Zr 31.9 mg/g 20 mg/L 24 h 25 ◦ C 2.0–7.0 Adsorption of phosphate was based on two distinct [124]
processes: ion exchange by the quaternary
ammonium group of wheat straw and specific inner-
sphere complexation by impregnated HZO
nanoparticles.
• St+@UiO-66 69.3 mg/g 3 mg/L 24 h 25 ◦ C 4.5 The adsorption was based on inner sphere [125]
complexation was created by forming Zr–O–P
coordination bonds between adsorbents and
phosphate ions.
Biochar based adsorbents
• Ca-biochar 197 mg/g 100 mg/L 24 h 25 ◦ C 3.1to 7.0 The primary mechanisms assigned to ligand exchange [127]
and chemical precipitation
• La10-MC 101.16 mg/g 100–400 24 h 30 ± 1 ◦ C 2.0 to The mechanism was based on electrostatic [128]
mg/L 5.0 interaction, inner-sphere complexation, and ligand
exchange.
• CaO-biochar 231 mg/g 5 to 200 24 h 25 ◦ C 5 to 11 The chemical interactions between the phosphate and [129]
mg/L the active constituent in the adsorbent (CaO and Ca
(OH)2) was the main adsorption mechanism of
phosphate
• La-TC 148.11 mg/g 30–100 24 h 25 ◦ C 6.0 The adsorption mechanism of La-TC to phosphate, [130]
mg/L including electrostatic adsorption, ligand exchange,
and complexation mechanisms.
Metal hydroxide
• Metal (Fe+3) oxide/ 70 mg/g 10 mg/L 180 min Room 7.5 Phosphate adsorption was mainly based on the inner- [134]
hydroxide nanoparticles temperature sphere surface complexation
• CTAB modified IONP 5.03 mg/g 10 to 60 100 min 25 ◦ C 1.6 to 9 CTAB-modified IONP was mainly associated with [135]
mg/L inner-sphere complexing mechanism and
electrostatic attraction.
• Magnetic iron oxide 10.85 mg/g 2 to 20 24 h 15 to 45 ◦ C 2.0 to The adsorption of phosphate ions to iron (hydr)oxide [136]
nanoparticle mg/L 6.0 surfaces was based on a ligand exchange mechanism.
Chitosan-based adsorbents
• MIL-101(Al)-CS 49.8 mg/g 30 mg/g 12 h 25 ◦ C 3.0–10 A mechanism was based on ligand exchange and [138]
• MIL-101(Fe)-CS 46.8 mg/g electrostatic interaction
• M-IACBs 18.5 mg/g 0.1–120 24 h 25 ◦ C 4.0 A mechanism was based on electrostatic and inner [139]
mg/g sphere complex formation
• Chitosan/lanthanum 107.7 mg/g 50 mg/g 24 h 25 ◦ C 4.0 A mechanism was based on electrostatic and ion [140]
hydrogel beads exchange.
• La-BC-5 23.52 mg/g 50 mg/g 30 min 25 C◦
3.0 Electrostatic interaction, precipitation, and [141]
complexation.
Cellulose-based adsorbents
• SP-Zr-La 23.5 mg/g 30 mg/L 1200 25 ◦ C 3 The mechanism was based on inner sphere complex [142]
min formation
• Cell-g-E/PEI 111.7 mg/g 100 mg/L 180 min 30 ◦ C 4.5 Adsorption was based on ion exchange [143]
• Fe(OH)3@CNFs 142.86 mg/g 10 mg/L 24 h 25 ◦ C 4.5 Ligand exchange and electrostatic attraction [144]

(continued on next page)

8
E. Priya et al. Journal of Water Process Engineering 49 (2022) 103159

Table. 2 (continued )
Adsorbent Amount Conc. Contact Temperature pH Adsorption mechanism Reference
adsorbed range time

The adsorbent used for the

phosphate removal by co-
removal mechanism
• MG@La 116.28 mg/g 20 mg/L 5 to180 20 to 40 ◦ C 4 to 8 Adsorbent shows high affinity towards phosphate [53]
min ions by forming inner-phase and outer-sphere
complex through electrostatic interaction.
• HA520E-Fe hybrid material 12.8 mg/g 15.33 mg/ 72 h 25 ◦ C 7 The phosphate adsorption through Lewis acid based [105]
L (LAB) interactions
• Nanocomposite HFO@TPR Reduced from 10 mg/L 12 h 25 ◦ C 7.2 Adsorption through inner-sphere complex formation [106]
2.5 to <0.2
mg/g
• RH 300(rice husk) 47.18 mg/g 50 mg/L 12 h – – Adsorption was based on ion exchange [107]
• Amine-functionalized 78.7 mg/g 30 mg/L 1h 298 K 3.0–10.0 Adsorption was based on electrostatic and hydrogen [108]
walnut shells (ACWNS) bonding
• Amine cross-linked tea waste 98.72 mg/g 300 mg/L 60 min 25 ◦ C 6.0 Adsorption was based on electrostatic and ion [109]
(ACTW) exchange
• Cellulose nanofibres aerogel 98.18 % 100 mg/L 60 min 25 ◦ C 6.0 Electrostatic interaction [110]

case of AC-CTABr. The introduction of a positively charged functional
group on AC led to electrostatic interaction between CTA+ and nitrate
ions and was responsible for the enhanced adsorption of nitrate. When
the pH value rises from 2 to 3, nitrate sorption ability enhances about 50
to 60 mg/g. Moreover, the sorption ability was reduced to 52 and 48
mg/g, respectively. Once the pH value was below 3 or above 10, results
indicate a weakening in the electrostatic interaction between adsorbent
and nitrate ions. The nitrate adsorption efficiency was independent of
the solution pH in the pH range from 3 to 10. This study reveals that the
unmodified activated carbon does not have a good capacity to absorb
nitrate anion and modification with CTABr has enhanced the sorption
efficiency of activated carbon [68].
In a study by Hassan et al., the removal of NO−3 by utilizing activated
carbon obtained from rice straw (ARSC) was evaluated. ARSC was pre­
pared by heating rice straw at 650 ◦ C for 1 h in an electric furnace and
mixing with Na2CO3. ARSC showed a maximum uptake capacity of 8.2
mg/g [69]. Further, in another study, modification of granular activated
carbon (GAC) with a mixture of ZnCl2, CaCl2, and MgCl2 was done to
impart capability for the adsorption of nitrate [70]. In this case, the
adsorption capacity was sensitive to the variation of pH; when the pH
rose from 4 to 7, the sorption efficiency of nitrate increased by 72.2 %.
The kinetic study fitted well with the pseudo-second-order kinetic model
and Langmuir model.
The sorption capacity of NO−3 was examined from wastewater by
utilizing lignite granular activated carbon (LGAC) modified with ZnCl2
[71]. The chemical saturation ratio of ZnCl2:LGAC varies from 1:1 to 1:3,
and the activation temperature range from 400 to 600 ◦ C. Experimental
results reveal that at 500 ◦ C, the volatile matter was released gradually
during carbonization creating extra pores responsible for the maximum
adsorption of nitrate from wastewater. Further increasing carbonization
temperature from 500 to 600 ◦ C led to a reduction in adsorption of NO−3
due to sintering effects at higher temperatures. An LGAC to ZnCl2 ratio
of 2:1 showed a better nitrate adsorption capacity than the unmodified
LGAC, with an adsorption capacity of 4.4 mg/g at pH 5. The surface
charge studies of LGAC revealed a point of zero charge (pHpzc) at pH 5.9.
So at pH < pHpzc the surface was positively charged, and led to an
optimal adsorption capability, and at pH > pHpzc the surface was
negatively charged, leading to reduced NO−3 adsorption capacity
because of the presence of an excess of competing hydroxyl ions on the
surface of the adsorbent, creating an electrostatic repulsion between the
surface of the adsorbent and NO−3 ions [71].
The adsorption efficiency of commercial GAC with Fenton reagents
(Fe2+ and H2O2) by chemical activation approach for NO−3 removal has
been studied by Ahmadi et al. [72]. The Fenton oxidation process per­
formed by the reaction between catalysts (Fe2+/Fe3+) and hydrogen
peroxide as an oxidant (H2O2) has been a widely used process. The
adsorption capacity for the GAC in this case was reported as 43.1 mg
NO−3 /g adsorbent. The experimental data were best fitted by pseudo-
second-order kinetics and Freundlich isotherm models [72].
In this study, research has grown to utilize the novel applications of
activated carbon to remove particular contaminants from wastewater
and also order to raise the adsorption capacity. Activated carbon ab­
sorbents attained from pyrolysis of rice husk and sludge of paper in­
dustry wastewater treatment were utilized by Shahmoradi et al. for the
removal of NO−3 ions from wastewater [73]. The NO−3 adsorption ability
was more in rice husk than paper-industry sludge. The adsorption ca­
pacity of the rice husk and sludge obtained from the paper industry was
found to be 93.5 and 79.5 NO−3 /g adsorbent, respectively. As the results
of this literature show surface modified carbon-based adsorbents have
increased sorption capacity compared to unmodified adsorbents
showing inadequate sorption capacity toward nitrate ions [73]. Surface-
modified activated carbon offered large surface area, porous
morphology, inexpensive, and readily available and viable alternative
material for the enhanced capability toward the removal of nitrate ions.
The changes in surface physiochemical characterization because of the
modification of the materials have basically enhanced the surface
reactivity towards the nitrate ions.
2.2. The clay-based adsorbents used for nitrate removal
Clay minerals are commonly utilized in various applications for the
removal of environmental contaminants [74]. Clay minerals have a high
specific surface area, layered structure, chemical, mechanical stability,
swelling capacity, and high cation exchange capacity utilized to remove
different types of contaminants from water [75]. The intercalation of
cationic surfactants with clay minerals modifies the surface properties
and dramatically increases the anions’ adsorption capacity. Such surface
quality modification helps in anionic pollutant removal by the clay
minerals [76]. Bentonite, kaolinite, and halloysite are chosen as orga­
noclays, and it was found that unmodified organoclays do not adsorb
NO−3 from the contaminated water. These unmodified clay materials
showed weak sorption capacities towards NO−3 ions in solution and the
only halloysite were identified to remove 0.54 mg/g NO−3 ions. Further,
various dosages of hexadecyltrimethylammonium bromide (HDTMA)
were added to investigate the enhancement of the organoclay minerals.
Fig. 6 illustrates a schematic mechanism of clay minerals surface
chemical modifications that enable the adsorbent to remove nitrate
through adsorption. Modification of clay materials with surfactant
hexadecyltrimethylammonium bromide (HDTMA) in 2 and 4 cation
exchange capacity (CEC) showed improved adsorption capacity for
bentonites as compared to other clay materials. Modification of ben­
tonites with HDTMA in 2 CEC and 4 CEC was represented as H-B-2CEC
and H-B-4CEC even though other organoclays are represented as H-K-
2CEC, H-K-4CEC, H-H-2CEC, and H-H-4CEC, respectively. The sorption

9
E. Priya et al.
Fig. 6. Schematic of mechanisms of clay minerals’ surface chemical modifications and nitrate adsorption on QLD-bentonite, kaolinite, halloysite, and organo­
clays [75,76].
capacity of different organoclays is determined by utilizing a 100 mg/L
nitrate solution. Modification of bentonite with HDTMA showed a
greater result among other organoclays materials. H-B-4CEC and H-B-
2CEC can take out 14.76 mg/g and 12.83 mg/g NO−3 ions, respectively.
Other modified kaolinite and halloysite with HDTMA showed poor
adsorption of NO−3 as compared to H-B samples (H-H-4CEC, H-H-2CEC,
and H-K-2CEC removed 1.93, 1.78, and 1.54 mg/g nitrate ions from the
solution, respectively). Compared to unmodified clay minerals, modi­
fied clay minerals with HDTMA have demonstrated better adsorption
capacities toward nitrate ions [76].
Bekele et al. prepared acid-activated bentonite clay modified with 2
M HCl to determine the adsorbent capacity of NO−3 removal from
aqueous solutions [77]. The acid activation was used to increase the
number of active sites on the activated clay mineral. Acid-activated
bentonite clay modified by HCl showed good NO−3 removal capacity,
>80 %, and the experimental data well fitted into the Langmuir model.
The maximum adsorbent capacity of 2 M HCl activated bentonite
clay was 5.0 mg/g for nitrate using an adsorbent dose 2.0 g, initial ni­
trate concentration of 250 mg/g, at pH 5 and temperature 30 ◦ C [77].
Natural clay materials from a dam situated in Morocco (Agadir city)
acted as a very effective low-cost adsorbent for nitrate removal from the
contaminated water [78]. The greater sorption ability was observed at
low pH because of the strong electrostatic interaction between the
positively charged surface sites of the adsorbent and the nitrate ions.
Nitrate removal capacity decreased when the pH rose from 2 to 10. It
was demonstrated that after pH 6, the adsorbent surface became nega­
tively charged, leading to repulsion between the negatively charged sites
on the adsorbent and the nitrate anions. The adsorption capacity of ni­
trate was enhanced by increasing the adsorbent dosage from 0.2 g/L is
9.84 %, to 1 g/L is 72.97 %, due to the presence of more adsorbent
surface area. At natural pH (pH = 5.1) the removal of nitrate was 71.89
%. The maximum nitrate adsorption capacity was 244.06 mg/g at 20 ◦ C
[78]. Clay is an abundant, naturally occurring material with excellent
physicochemical stability and structural and surface properties. Labo­
ratory experiments were carried out to examine the adsorption capacity
of local clay (greenish clay (A1) rich in free silica (quartz)) without
chemical modification utilized for the removal of nitrate from water
through the process of adsorption [79]. Under the optimal condition,
nitrate adsorption ability was 5.1 mg/g for a dosage of 0.4 g of adsorbent
10
Journal of Water Process Engineering 49 (2022) 103159
in 20 mL of nitrate solution with a 100 mg/L concentration. Freundlich’s
model showed the best correlation for the adsorption process [79]. Clays
and clay minerals are non-toxic and cost-effective materials with a high
surface area. The role of clays and clay minerals in nitrate removal from
wastewater resources can achieve higher removal rates with suitable
modifications to existing systems. Most clay and clay minerals are uti­
lized to remove cationic pollutants; still, they can be equally effective for
anionic contaminants removal depending on the modification process
they have undergone or the materials they were mixed with. As a result,
clay-based materials and natural clays could remove the nitrates based
on the modification and then release the nitrate in a slow-release
manner into the soil would be a great selection for the circular econ­
omy and sustainable development.
2.3. Zeolite-based adsorbents for nitrate removal from water
Zeolites are a group of hydrated aluminosilicate minerals usually
present in a natural environment and utilized as an effective and cheap
adsorbent for eliminating contaminants from wastewater and act as
cationic exchangers (CEC) [80]. Researchers have used modified zeolitic
materials for the adsorption of nitrate and other contaminants such as
arsenate, chromate, phosphate, and fluoride from wastewater
[33,81–83]. Surfactant-modified BEA-type of zeolites was synthesized as
nanocrystals, nanosponges, and conventional microcrystals. In this
study, external surfaces of the zeolites were modified with a cationic
surfactant (HDTMA+Br− ) to obtain surface-modified zeolites such as
SMZNC, SMZNS, and SMZMC for nitrate adsorption [84]. The maximum
nitrate removal capacities observed in surface-modified zeolite nano­
crystals and nanosponges were 83 mg/g and 19 mg/g at pH 5.5,
respectively. The high adsorption capacity was due to the presence of a
high concentration of positively charged functional groups in the
surface-modified zeolite with HDTMA+Br− at pH 5.5. At the same time,
reducing the pH to the acidic region led to a decrease in nitrate
adsorption capacity due to the leaching of trivalent aluminum atoms
from the zeolite framework bound with NO−3 ions. Further, the surface-
modified microcrystal adsorption capacity was found to be 0.22 mg/g in
optimal conditions. Their decreased adsorption capacity is due to a low
modification rate with HDTMA+Br− on the external surface of micro­
crystals. In another study, nitrate sorption on zeolites (especially
E. Priya et al.
clinoptilolite) was studied at room temperature, employing batch ex­
periments only [85]. A natural zeolite was ball-milled to obtain zeolite
nanoparticles which were chemically modified by 3-aminopropyl trie­
thoxysilane (APTS), which led to the development of NH2 groups on the
zeolite surface. The APTS-zeolite having NH2 groups on the surface
needed an H+ ion to convert − NH2 into − NH+ 3 which are capable of
nitrate removal, making this phenomenon possible only in acidic con­
ditions. Further, increasing pH led to an increase of OH− ions, thereby
reducing the nitrate removal capability and acting as a competitive
anion for nitrate removal. The maximum nitrate uptake was 12.54 mg/g
at pH 3.
ZSM-5 (MFI-type) nanosheets (NS), nanosponges (NSp), and nano­
crystals (NC) were developed by various processes. To obtain surfactant-
modified nano zeolites (SMZN) as nanosheets, nanosponges, and nano­
crystals, their external surface is modified with cationic surfactant
(HDTMA+Br− : hexadecyltrimethylammonium bromide) to obtain
higher external surface areas and smaller crystal sizes. The MFI-type
zeolites were also modified using the same cationic surfactant to pro­
duce a low external surface area and large crystal size (SMZMC) in
comparison to the SMZN to test the nitrate removal capability in this
investigation [86]. As shown in Fig. 7, the number of adsorbed
HDTMA+Br− on the surface of the zeolites increased as the particle sizes
became smaller (which means an increase of the specific surface areas) i.
e., SMZNSp > SMZNS > SMZNC > SMZMC. The ultra-fast nitrate removal
on the three altered zeolite materials is 5.3, 4.1, and 2.5 % from the total
initial nitrate concentration for SMZNSp, SMZNS, and SMZNC,
Fig. 7. Schematic representation of the surface modification and characteristics of MFI-type NS and NSp in order to obtain the SMZNS and SMZNSp materials [86].
11
Journal of Water Process Engineering 49 (2022) 103159
respectively, within the starting 2 min interaction period before reach­
ing the equilibrium. The maximum removal nitrate capacity at pH 6 was
found to be 810 (±50), 1941 (±100), 2125 (±100) mmol kg− 1 for
SMZNC, SMZNS, and SMZNSp, respectively. The maximum removal ni­
trate capacity at pH 6 was found to be 810 (±50), 1941 (±100), and
2125 (±100) mmol kg− 1 for the SMZNC, SMZNS, and SMZNSp, respec­
tively. At lower pH, the presence of more acidic conditions increases the
H3O+ concentration leads to the formation of another form of nitrate
(HNO3) that may reduce the adsorption capacity. Besides, at higher pH,
a decrease in the nitrate removal capacity has occurred to the presence
of hydroxyl ions and their competition with NO−3 binding with the
adsorbent site [86]. Zeolite-based composites demonstrated various
advantages over raw zeolites for the adsorption of pollutants such as
nitrate from water. The advantages of zeolite-based composites included
fast adsorption, higher sorption ability, better reusability, high selec­
tivity, and fast adsorption. In the past few years, the utilization of
zeolite-based composites in the forms of zeolite/polymer and zeolite/
inorganic composites has been augmented for the sorption of nitrate
from wastewater. The main sorption mechanisms based on zeolite-based
composites are ion exchange, electrostatic interaction, chelation, surface
adsorption, complexation, and diffusion. The trace concentration of
toxic material and contaminants present in drinking water removed by
selective mechanism by zeolite based composite should be developed in
future. The development of cost effective zeolite-based composite
should be considered for practical application on actual wastewater
treatment at a large scale.
E. Priya et al.
2.4. Chitosan-based adsorbents for nitrate removal from wastewater
In current years, the chitosan-based adsorbent method has become
an economically valuable and eco-friendly alternative treatment tech­
nology in the wastewater industry. The exciting features of this bio-
sorbent are utilized in various research and industries. In this light,
chitosan is used as an adsorbent; it helps remove the toxic pollutants
from water selectively and is also used to remove various organic and
inorganic pollutants. Chitosan is the N-deacetylated chitin, which is
found in algae and fungi cell walls, the exoskeletons of insects, crusta­
ceans, and mollusks; chitin is the second most abundant biopolymer
after cellulose in nature [87]. Different types of crosslinked chitosan-
based hybrid biocomposite materials, like chitosan/bentonite (ChBT),
chitosan/titanium oxide (ChTi), and chitosan/alumina (ChAl), were
tested for their NO−3 ions removal capacity [88]. The maximum
adsorption capacity was attained at pH 6. Further, decreasing the pH
leads to more protons accessible to protonate the chitosan amine func­
tional group, which reduces the nitrate ions’ adsorption capacity to­
wards the adsorption sites. The adsorption capacity of ChAl, ChTi, and
ChBT was recorded 45.38, 43.62, and 35.68 mg/g as nitrate, respec­
tively. The adsorption capacity was pH-sensitive, and it was demon­
strated that the best adsorption capacity was obtained around pH 6; for
other pH values the capacity diminished. At above pH 6, the number of
hydroxyl ions increases, and adsorbent sites become more negatively
charged, leading to a reduction of adsorption capacity through repels the
NO−3 ions in aqueous solution, and when the pH > pHpzc, the chitosan
surface will become negatively charged, reducing nitrate ions’ adsorp­
tion capacity because of electrostatic repulsive action. The optimal
temperature range of nitrate adsorption capacity from aqueous solution
through chitosan bio-composites was achieved at 303–313 K. Fatemeh
et al. also reported that the nano chitosan/clinoptilolite (Nano-CS/
Clino) composite was able to remove nitrate removal satisfactorily from
an aqueous solution [89]. The functionalization of Nano-CS/Clino was
accomplished with pentaethylenehexamine (Nano-CS/Clino@ PEHA)
and was activated by hydrochloric acid (Nano-CS/Clino@H). The
maximum adsorption capacity of prepared Nano-CS/Clino@PEHA,
Fig. 8. Represent the mechanism for the effect of pH on PEG/chitosan composite and PVA/chitosan composite [90].
12
Journal of Water Process Engineering 49 (2022) 103159
Nano-CS/Clino@H, Nano-CS/Clino composites were 277.77, 227.27,
and 185.18 mg/g as nitrate, respectively. The analyses indicate that
kinetic and equilibrium data for the adsorption of NO−3 were expertly
fitted to the pseudo-second-order kinetics and Freundlich isotherm
model.
In another study, two different types of chitosan composites were
prepared for the purpose of nitrate removal — polyvinyl alcohol (PVA)/
chitosan and polyethylene glycol (PEG)/chitosan [90]. The suitability of
the prepared composites for removing nitrate from the water was
evaluated under various experimental conditions, including the effects
of interaction time, pH of the solution, and adsorbent dosage. The nitrate
adsorption capacities of PVA/chitosan and PEG/chitosan were found to
be 35.03 and 50.68 mg/g, respectively. Compared to PVA/chitosan, the
prepared PEG/chitosan has more adsorption capacity. Fig. 8 illustrates a
schematic of how the composites were prepared and their mechanism of
nitrate adsorption at acidic pH [90].
The high chemical stability of granular chitosan-Fe3+complex with
good environmental adaptation was made by the precipitation process
[91]. Highly chemically stable granular chitosan-Fe3+ complex proved
to be a good adsorber of nitrate and demonstrated a maximum adsorp­
tion capacity of 8.35 mg/g based on the Langmuir-Freundlich model. It
was also observed that the adsorption capacity was not dependent on
solution pH, and significant adsorption occurred in the removal of NO−3
efficiency >80 % in between the pH range of 3.0–10.0. Besides, the pH
range of 3.0–10.0 chitosan-Fe3+ complex showed buffer capacity.
Further, an increase in pH beyond 10.0 led to a sharp decrease in NO−3
removal efficiency due to competition between OH− and NO−3 ions for
the adsorption sites. Hence, the free amine groups of chitosan could not
be protonated in an alkaline medium, which did not facilitate electro­
static attraction between adsorbent and adsorbate. However, the ther­
modynamic study showed that nitrate adsorption on granular chitosan-
Fe3+complex was spontaneous and exothermic. Chitosan-based com­
posite adsorbent materials are becoming an attractive approach for the
adsorptive recovery of nitrates due to the fact that they are abundant in
nature, environmentally friendly, and biodegradable. The chitosan
surface modification will help overcome the low adsorption capacity
E. Priya et al.
and low surface area available with the parent material by providing
more number of active sorption sites for binding nitrate ions with better
adsorption kinetics and decent reusability.
2.5. The agricultural waste-based adsorbents for the removal of nitrate
from wastewater
Cost-effective adsorbents made from various agricultural waste ma­
terials can well be a good alternative material for water and wastewater
treatment remediation. Various naturally present materials were suc­
cessfully utilized for the removal of nitrate from wastewater. The agri­
cultural wastes-based adsorbents utilized to recover nitrate from the
wastewater were investigated in the study by Kalaruban et al. [92] who
investigated the feasibility of using waste materials such as corn cob and
coconut copra after surface modification is done by grafting amine
groups. The reaction with dimethylamine and epichlorohydrin in the
presence of N,N-dimethylformamide (DMF), and pyridine led to the
incorporation of amino and epoxy groups on corn cob and coconut
copra. It was found that the incorporation of the amino group into corn
cob and coconut copra increased during the reaction with the occur­
rence of the presence of a catalyst (pyridine). The maximum NO−3
exchangeability and capacity of the developed exchangers were 59.0
and 49.9 mg/g, respectively for coconut copra, and corn cob. The pro­
posed synthetic process was found useful in an amine-grafted corn cob
and coconut copra, resulting in a higher yield and NO−3 removal capacity
at pH 6.5.
NO−3 uptake from wastewater using chemically altered biochar
(developed from sugarcane bagasse) was studied by Divband et al. [93].
The biochar was crosslinked with dimethylamine and epichlorohydrin.
It was observed that under low pH, higher nitrate adsorption efficiency
was observed, which is due to the electrostatic attraction between the
modified biochar surface and nitrate ions. In the case of a mixed ion
solution of co-existing ions (phosphate, chloride, sulfate, and carbon­
ate), the removal capacity was compromised. The experimental data
best fitted with the Langmuir isotherm and pseudo-second-order kinetic
model. The maximum nitrate adsorption efficiency of the biochar was
28.21 mg/g.
In another study by Stjepanovi et al. [94], waste lignocellulosic
material, namely brewer’s spent grain (BSG) was altered by epichloro­
hydrin in the presence of ethylenediamine, and the batch experimental
study was conducted to measure the adsorption kinetics. The nitrate
adsorption capacity of modified BSG (MBSG) was 22.65 mg/g for model
nitrate solution, 18.22 mg/g for model wastewater, and 14.4 mg/g for
real wastewater effluent produced from the dairy industry. Desorption
results revealed that the maximum amount of the adsorbed nitrate ions
could be desorbed from altered brewer’s spent grain (BSG) using 0.1 M
NaOH solution.
The nitrate removal was evaluated using onion peel dust (OPD) [95].
The result reveals that the maximum adsorption capacity of nitrate was
5.93 mg/g by using onion peel dust (OPD) at pH 12. The equilibrium
data fitted well with the Langmuir adsorption isotherm. The active
functional groups on the onion peel dust (OPD) were identified by
Fourier transform infrared (FTIR) before and after the removal of NO−3
and the result has revealed that several active functional groups exist on
the surface for the adsorption of NO−3 ions. Besides, the adsorbed NO−3
ions could be desorbed from onion peel dust (OPD) using a 0.1 M NaOH
solution. Therefore, the results of this study suggested that onion peel
dust could be another substitute adsorbent for nitrate removal from an
aqueous medium. The nitrate removal from wastewater by utilizing
nanocrystalline cellulose (NCC) extracted by the acid hydrolysis of
bagasse was studied [96]. Nanocrystalline cellulose was obtained in
diameter and length of <14.7 and 500 nm, respectively. The
morphology of adsorbent material was characterized by various tech­
niques such as atomic force microscopy (AFM) and dynamic light scat­
tering (DLS). AFM image analysis and DLS results showed that the
dimensions of the extracted cellulose crystals are in the nanoscale range.
13
Journal of Water Process Engineering 49 (2022) 103159
The results indicated that the maximum nitrate removal capacity was
8.33 mg/g [96].
Wheat straw was treated with 3-chloropropyltrimethoxysilane
(CPTMS) and (1,4-diazabicyclo[2.2.2]octane) (DABCO), and batch
tests were performed in order to determine the ideal conditions for ni­
trate removal by modified wheat straw (MWS) [97]. It was observed that
85 % of the nitrate was eliminated with an MWS dose 2 g/L, initial ni­
trate concentration 20 mg/L, contact period 10 min, initial solution pH
− 7, and temperature 25 ◦ C. Sulfate had the largest inhibitory impact as
competing anion, followed by phosphate, chloride, and bicarbonate. The
adsorption process was exothermic, viable, and spontaneous, according
to thermodynamic analyses. According to the findings of this investi­
gation, the MWS needed the simplest operating parameters for nitrate
removal [97]. Anni et al. studied nitrate adsorption by a chemically
modified pine sawdust used as anion exchange resin. The pine sawdust
was chemically modified by treating it with N,N-dimethylformamide,
epichlorohydrin, ethylenediamine, and triethylamine. The inserted
triethylamine functional group was responsible for nitrate ion exchange.
Under the temperature setting of 40 ◦ C, chemically modified pine
sawdust had a maximum adsorption capacity of 32.8 mg/g. As the
temperature rose, the adsorption capacity decreased. The nitrate
adsorption on the material is based on monolayer adsorption, suggesting
that the adsorption is best suited to the Redlich-Peterson and Langmuir
models. Further thermodynamic investigations show that nitrate
adsorption was exothermic and spontaneous [98]. In another work,
hazelnut shells as new adsorbents were studied for removing nitrate
from wastewater. N,N-dimethylformamide, epichlorohydrin, ethyl­
enediamine, and triethylamine were used for the modification of the
hazelnut shell. Rapid nitrate adsorption took place before reaching
equilibrium within <60 min, and the modified material showed a
maximum adsorption capacity of 26.51 mg/g. The electrostatic inter­
action between nitrate and the added triethylamine functional group
drove the adsorption process. The adsorption conformed well with both
the Langmuir and Freundlich adsorption isotherms. The pseudo-second-
order well fitted the kinetics data [99]. Domestic and international
studies have found that agricultural waste is a good choice to deal with
environmental pollution due to its biocompatibility, cost-effectiveness,
easy availability, and suitable modification of this material leads to se­
lective adsorption towards the nitrate ions. Agricultural waste’s porous
structure consists of hydroxyl, carboxyl, and other active groups, and
these functional groups are responsible for the modification process that
leads to the adsorption of nitrate ions.
2.6. Cellulose-based adsorbents for nitrate removal
Natural polymer cellulose has been widely employed in wastewater
treatment in recent years. To reduce future environmental issues in
wastewater treatment, the ideal chemical feedstock used to synthesize
the adsorbents should be environmentally friendly (i.e. non-toxic). The
most common organic biopolymer on the planet is cellulose, which
meets a variety of criteria that match the profile of a very safe and
efficient adsorbent. Furthermore, cellulosic materials may be trans­
formed into cellulose nanocrystals and nanofibers by chemical treat­
ment or mechanical, which offer superior properties to microscale
native cellulose, particularly in water purification applications [100].
Cellulose is made of repeating units of glucose and β-D-anhy­
droglucopyranose units, which are linked together by β-(1–4)-glycosidic
bonds [101]. 3-chloropropyl trimethoxysilane (CPTMS) was employed
to modify cellulose nanocrystals for imparting capability for nitrate
adsorption. Under optimal pH 7, the adsorption capability of the syn­
thesized CPTMS/CNC adsorbent material was 30 mg/g. These synthe­
sized materials did not require pH adjustment during the process and
demonstrated 86.5 % adsorption capacity in <10 min. The Pseudo-
second-order kinetic model fitted the kinetic adsorption data well.
Freundlich isotherm model fitted the equilibrium adsorption data [102].
Chong et al. used natural cellulose powder for nitrate adsorption from
E. Priya et al. Journal of Water Process Engineering 49 (2022) 103159

aquaculture effluents. The absorption of nitrate by naturally occurring converted into orthophosphates through the biological oxidation pro­
cellulose adsorbent was examined using a different range of parameters, cess [112]. Orthophosphate can be found in various forms, such as
including adsorbent dosages of 5.0 mg and 40.0 mg, starting concen­ H3PO4, H2PO−4 , HPO2− 3−
4 or PO4 depending on the pH (Fig. 9) [111] and
trations of 5.0 mg/L and 30.0 mg/L, temperatures of 25 ◦ C and 45 ◦ C, following the dissociation constants: pK1 = 2.15, pK2 = 7.20, and pK3
contact times of 10 min and 60 min, and an optimum pH of 6.6. The = 12.35. H2PO−4 and HPO2− 4 are the most abundant forms of dissolved
results of batch studies revealed that the best nitrate removal was ob­ phosphate present in most water bodies [105]. Numerous techniques
tained at 5.0 mg of dosage, 5.0 mg/L of initial concentration, 10 min, have been employed for phosphate removal from contaminated water.
and 25 ◦ C of temperature, when 96.50 % removal was recorded. The However, adsorption is one of the most successful techniques employed
mechanism of adsorption is based on electrostatic interaction [103]. In so far to remove various forms of phosphate ions present in contami­
another study, a cellulose grafted epichlorohydrin (Cell-g-E) copolymer nated water. Further, researchers have focused on utilizing various types
was synthesized and functionalized with polyethylenimine (Cell-g-E/ of adsorbent material to remove phosphate, and their mechanism for
PEI) to remove nitrate from an aqueous solution [104]. The adsorbent phosphate removal are explained in the following section.
material reached its maximum adsorption capacity at pH 4.5 and
increasing the pH resulted in electrostatic repulsion. The process relies
3.1. Removal of phosphate from wastewater through zeolite-based
on electrostatic interaction between the nitrate and adsorbent surface,
adsorbents
which is mediated by cellulose with the specific integrated functional
group. The experiments demonstrated that the Pseudo-second-order
The zeolites are eco-friendly and cost-effective materials that have
kinetic model well fitted the kinetic rate data, showing the coexistence
well-organized porous structures with high surface area contributing to
of chemisorption and physisorption-like mechanisms, with film diffu­
several active binding sites, which are helpful for the selective adsorp­
sion acting as the rate-limiting step in the adsorption process. The
tion of pollutants from wastewater [113]. Impregnated ZSM-5 zeolite
Freundlich isotherm, which suggests a multilayer adsorption process,
beads (ZB) with lanthanum (La) were investigated for phosphate re­
was shown to be the best-fit adsorption isotherm when comparing the
covery from wastewater [114]. Lanthanum was incorporated into ZSM-5
two and three variable isotherms. According to thermodynamic
zeolite beads (ZB) using lanthanum nitrate solution (LA-ZB). Zeolite has
research, the adsorption process is spontaneous and exothermic, which
a specific surface area and porous structure, which offers an active
is advantageous for strengthening the adsorption mechanism [104].
binding site for lanthanum. Impregnated ZSM-5 zeolite beads with
Cellulose-based products provide a productive, affordable, and effective
lanthanum (La-ZB)-based adsorbents deliver selective coordination
option for the treatment of wastewater. These cellulose-based adsor­
adsorption sites for phosphate. The maximum phosphate sorption ca­
bents, which successfully remove nitrate from the aqueous solution,
pacity by La-ZB and ZSM-5 was 106.2 and 59.8 mg/g, respectively. The
could be used for various purposes.
mechanism of adsorption followed monolayer sorption conforming to
Langmuir isotherm, and the kinetics followed pseudo-second-order re­
3. Phosphate removal from wastewater
action kinetics. At pH 6, phosphate removal capacity was maximum for
both zeolite beads (ZSM-5) and La-ZB. Increasing the pH 3 to 6 resulted
Phosphate is present naturally in soil and occurs in different forms.
in an increase in phosphate adsorption due to the presence of more
Agricultural pollution and municipal sectors are major sources of
deprotonated species of phosphate (HPO2− 4 ) ions that readily coordi­
phosphate contamination to surface water bodies. Orthophosphates are
nated with lanthanum through lewis acid-base interaction. Further, at
mainly generated by man-influenced sources like untreated and
pH >7 adsorbents surface became negatively charged which led to
partially treated sewage from the industrial sector and runoff from
electrostatic repulsion, thereby reducing the phosphate removal ca­
agricultural fields. These phosphates exist in three different forms in
pacity. Desorption was done using NaOH solution, and hence, the
water and wastewater: condensed phosphate, organic phosphate, and
adsorbent was recyclable with capability to remove and recover the
orthophosphate. Each compound contains phosphorus in various
target ions from wastewater.
chemical arrangements [111]. More complex forms of phosphorus are
Synthetic zeolites produced from fly ash and incorporated with

Fig. 9. Relative proportion (mole fractions) of orthophosphate species at 25 ◦ C [111].

14
E. Priya et al.
lanthanum (La) were used to recover phosphate from an aqueous solu­
tion [115]. The adsorption capacities of zeolites obtained from fly ashes
La-P1 (16.0 wt% of La) and La-A (9.5 wt% of La) towards phosphate
were related to that of natural zeolite-clinoptilolite, altered with La (La-
CLP having 4.8 wt% of lanthanum) in the study. The results indicated
that the adsorbents were positively charged at pH 5 to 7, responsible for
selective adsorption of phosphate ions. Imposition of the alkaline envi­
ronmental condition increased hydroxyl ion concentration, so adsorbent
sites become more negative, which reduces phosphate binding to the
adsorbents due to the lack of binding sites. Between La-modified zeolites
and unmodified zeolite form, a modified form led to a significant
improvement in their phosphate adsorption capacity. The maximum
phosphate sorption capacity of La-P1, La-A, and La-CLP were 58.2 mg/g,
44.0 mg/g, 24.6 mg/g, respectively. The La-P1 showed the highest
phosphate adsorption capacity as it contained the highest percentage of
lanthanum. The experimental data fitted well with the Langmuir
isotherm model, and the thermodynamic study indicated that phosphate
sorption was an endothermic and spontaneous process.
Zeolite loaded with La-incorporated ternary (hydro) oxides nano­
composite (MALZ) was prepared by a coprecipitation method using LA,
Mg, Al to recover phosphate from an aqueous solution [116]. The
multimetal oxides had better physiochemical properties as compared to
single metal oxides. The results of X-ray diffraction (XRD) and scanning
electron microscopy (SEM) indicated that the MALZ had an amorphous
surface with Mg, La, and Al homogeneously dispersed on the outer
surface of the zeolite. La-incorporated ternary (hydro) oxides nano­
composite (having 12.5 wt% of lanthanum) showed a maximum phos­
phate adsorption capacity of 80.8 mg/g at pH 6.6. In this case,
phosphate was removed by the ligand exchange mechanism and also by
the formation of solid phases of LaPO4⋅xH2O [116].
In another study, Fe-Zeolite-A adsorbents were prepared by adding
ferric iron using ammonium iron citrate as the source of Fe3+ to the
zeolite-A structure for the removal of phosphate. During the modifica­
tion procedure, initially, zeolite-A was synthesized in a hydrothermal
reactor using the SOL-Gel technique, and then iron particles were
incorporated into the material. EDX study showed that Fe was present in
a Fe-Zeolite-A material along with Na, Al, and Si. Through a variety of
interactions, Fe3+, Al3+, and Na+ in the Fe-Zeolite-A took part in the
phosphate adsorption and desorption of phosphate ions. The sorption
process was reversible as Fe3+demonstrated a ligand exchange mecha­
nism with the phosphate anions. Other possible metal ion interactions
included electrostatic attraction by Fe3+, precipitation, and hydrogen
bonding by Al3+. Fe-loaded zeolite demonstrated a maximum phosphate
adsorption capability of 18.15 mg/g. The Langmuir-Freundlich isotherm
model matched the adsorption data well [117].
In a work by Ying et al., the metal oxide is used to modify zeolite for
phosphate adsorption. The adsorbent material (ZEO@AZ) impregnated
with ZrO2 in-situ exhibits good reusability and effective adsorption ca­
pabilities. ZrO2 contains an acidic and basic bifunctional site exhibiting
considerable phosphate adsorption. In order to exchange the phosphate
ions in the target solution, these Zr species hydrolyze a large number of
hydroxyl ions and water molecules through the ligand exchange process.
The material’s maximal adsorption capacity is 24.96 mg/g, and
adsorption data fit well with Langmuir and Pseudo-second-order ki­
netics. Furthermore, material adsorption capability significantly de­
pends on solution pH and stays effective and constant at pH < 6. The
mechanism is dependent on the inner-sphere complex formation [118].
In another study, green synthesis techniques were adopted to create
Mn–Fe, Zr–Fe, and Mn–Zr–Fe modified natural zeolites (MNZs).
These modified natural zeolites (MNZs) were utilized to remove phos­
phate from the contaminated aqueous solution. Zr–Fe, Mn–Fe, and
Mn–Zr–Fe modified zeolites had adsorption capacities of 8.8, 11.8,
and 20.9 mg/g, respectively. The Langmuir isotherm and pseudo-
second-order kinetics model fitted well with the adsorption data.
Phosphate ion adsorption onto modified zeolites was aided by both
electrostatic attraction and ligand exchange. It was revealed that the
15
Journal of Water Process Engineering 49 (2022) 103159
modified zeolites had a high capacity for regeneration. The newly
developed unique adsorbents had a wide variety of potential applica­
tions, including the removal of phosphorus from eutrophic water [119].
Lanthanum and other metals integrated with zeolite material have
recently attracted much attention for phosphate adsorption from
wastewater due to its environmentally friendly nature, increased
adsorption capacity, higher removal rate, and wide operating pH range.
Although there are several techniques for modifying the zeolites, the
most appropriate method should be chosen based on the specific con­
taminants. Furthermore, due to the huge number of coordination sites,
lanthanum and other metal-incorporated zeolites may have strong
selectivity towards phosphate ions in the medium, even at low con­
centrations. As a result, adding lanthanum and other metals to zeolites
promotes advancements in both adsorption kinetics and capture
capacity.
3.2. Agricultural waste used for phosphate removal from wastewater
Bio-derived material-based adsorbents have good properties, such as
effectiveness, economically valuable, and biodegradable. The efficient
removal of phosphate by chemically modified agricultural waste
biomass (HFO@St+) from wastewater was examined [120]. This
experimental study proposed a new nanocomposite (HFO@St+) that was
derived from aminated wheat straw (St+) and was saturated with nano-
sized hydrous Fe(III) oxides (HFO). TEM and SEM determined the
morphological characters, and the BET results revealed that the iron
oxide nanoparticles had an average size of 20–30 nm. The optimal
phosphate sorption was detected over a wide range of pH from 2.0 to
7.0. The nano-sized hydrous Fe(III) oxides (HFO) were based on the
mechanism of inner-sphere complex formation. At lower pH, the in­
crease in H+ concentration facilitates the favorable reaction for phos­
phate adsorption on nano-sized hydrous Fe(III) oxides. At increasing pH,
the increasing OH− (hydroxyl ions) leads to competition between the
adsorption site of phosphate and hydroxyl ions, reducing the phosphate
adsorption. Binary exchange reactions were carried out on aminated
wheat straw (St+) before or after the loading of HFO using a test solution
containing a variable molar ratio of phosphate and nitrate. Results
indicated that the adsorption capacity of HFO@St+ showed a higher
affinity to phosphate over nitrate. The maximum phosphate adsorption
capacities were 27.81 mg/g and 40.19 mg/g, respectively, under pH 6.0
and 3.2.
Phosphate removal from the wastewater by activated agro-waste rice
husk ash (ARHA) was investigated in another study by Suman et al.
[121]. The experimental data revealed that rice husk ash chemically
modified with 1 N HCl boosted phosphate adsorption efficiency and
indicated a maximum removal of up to 89 % of phosphate at pH 6. The
experimental data best fitted the Pseudo-second-order model and
Langmuir isotherms. The effect of temperature and pH played a critical
role in phosphate adsorption. While increasing pH above 6 produces
more hydroxyl ions, creating competition between phosphate and
adsorbent sites. Temperature above 30 ◦ C showed a reduction in the
adsorption capacity by weakening the sorptive forces between the active
sites on the adsorbent and the adsorbate.
In another study thermally treated seagrass residues of Posidonia
oceanica for phosphate adsorption from synthetic and real wastewater
[122]. The results indicated that the adsorption kinetics showed that the
thermally treated seagrass adsorption performance followed Pseudo-
first-order and the Freundlich isotherm. The phosphate adsorption ca­
pacity of seagrass residues of Posidonia oceanica in real wastewater is 3.3
mg/g and showed 81 % of adsorption rate by use of an adsorbent dose
30 g/L and phosphate concentration was 100 mg/L. In the synthetic
aqueous solution, phosphate adsorbent capacity was 99 % using an
adsorbent dose 20 g/L, and the initial phosphate concentration was 100
mg/L without competitive inorganic ions. Rice straw is a common
agricultural waste product with a significant presence of hydroxyl group
modified with a triethylamine functional group, which was responsible
E. Priya et al.
for the demonstration of selective phosphate adsorption (RS-PA) [123].
The prepared RS-PA (rice straw-based phosphate adsorbent) had a
maximum adsorption capacity of 71.94 mg/g, and the phosphate
adsorption was exothermic. Total phosphate removal was attained when
the starting phosphate content was 50 mg/L, and a dosage of 10 g/L RS-
PA removed 99 % of phosphate within 10 min. The Langmuir isotherm
and Pseudo-second-order kinetic models provided the best fit [123]. Hui
et al. employed quaternary-aminated wheat straw immobilized with
zirconium oxide nanoparticles (Ws-N-Zr) for phosphate removal in their
investigation. Three distinct samples were used to calculate the
adsorption capacities: Ws (wheat straw), Ws-N (containing quaternary
ammonia functional group), and Ws-N-Zr (both quarternary and hy­
droxyl zirconium oxide nanoparticle). It was discovered that Ws had an
almost negligible adsorption capability because the hydroxyl group in
Ws could not be exploited as an active phosphate adsorption site. The
adsorption of phosphate by Ws-N, which had an adsorption capacity of
19.5 mg/g, was due to electrostatic interaction between phosphate and
quaternary ammonia groups. The hybrid Ws-N-Zr material had a
maximum phosphate adsorption capability of 31.9 mg/g. Ws-N-Zr per­
formed better than other adsorbents because there was additional
interaction between the impregnated hydrated zirconium oxide (HZO)
nanoparticles and the phosphate ions. Langmuir’s adsorption model
fitted well with the adsorption data. Two independent mechanisms
allowed the new adsorbent Ws-N-Zr to successfully collect phosphate
ions without any Zr(IV) leaching under pH 2–7: specific inner-sphere
complexation by incorporated HZO nanoparticles and nonspecific ion
exchange by wheat straw’s quaternary ammonium groups [124].
In-situ hydrothermal synthesis was used in another study to create
modified wheat straws. The material was first modified using N,N-
dimethylformamide, epichlorohydrin, ethylenediamine, and triethyl­
amine to provide a positive charge to the surface. Furthermore, UiO-66
nanoparticles were integrated onto the surface and inner pores of wheat
straw. Following these changes, it was discovered that the adsorption
site was more active due to the impregnation of UiO-66 nanoparticles on
positively charged wheat straw. According to the findings, the St+@UiO-
66 exhibited the strongest phosphate ion selectivity. The increased ef­
ficiency of St+@UiO-66 can be attributed to its bifunctional structure,
selective adsorption by impregnated UiO-66 nanoparticles, and the
Donnan membrane effect exerted by the immobilized quaternary
ammonium groups, which provided phosphate enrichment from
aqueous solution. The pH of the aqueous solution is critical for phos­
phate ion adsorption. The best adsorption occurred when the pH range
was between 2.0 and 5.5. Increasing the pH led to an increase in the
quantity of OH− ions, which led to an electrostatic repulsive force be­
tween the adsorption site and the phosphate ions. According to the FTIR
and XPS spectra, the inner sphere complexation formed through
Zr–O–P coordination bonds, which also suggested that phosphate ions
replaced the surface hydroxyl groups of UiO-66. The maximum
adsorption capacity of modified wheat straw material was 69.3 mg/g,
and kinetics data fitted well with the Pseudo-second-order model [125].
Agricultural waste-based adsorbent for sorption of the phosphate ions is
dependent on the surface modification, and adsorption capacity is also
based on the surface functionalization of the material. These adsorbents
can be directly used as fertilizer in the agricultural field after recovering
the phosphate ions, and more research needs to be focused on this field.
3.3. Removal of phosphate from wastewater by biochar-based adsorbents
Nowadays, biochar has received much attention for potential use in
the wastewater treatment process. Biochar is produced through green
and eco-friendly methods, which has an excellent capacity to be used as
an adsorbent to eliminate phosphate from wastewater [126]. Treatment
with Ca(OH)2 based rice straw produced a black liquor-derived calcium-
activated biochar (Ca-biochar) that acted as a good adsorbent for
removal of phosphate in aqueous solution and actual wastewater, and
their removal capacity was investigated in this study [127]. The
16
Journal of Water Process Engineering 49 (2022) 103159
adsorption process was correlated with Pseudo-second-order kinetics
and the Langmuir model with primary mechanisms assigned to ligand
exchange and chemical precipitation. The maximum adsorption capac­
ity by Ca-biochar was 197 mg/g. Further, an examination of actual
wastewater was carried out in this study. The experimental data
revealed that the actual wastewater containing 3.78 mg/L P in the initial
stage at pH 7.6 after the adsorption process contained only 0.102 mg/L
and 0.021 mg/L when Ca-biochar adsorbent concentration of 0.1 g/L
and 0.2 g/L, respectively were used as adsorbents. Desorption was done
using NaOH solution, and thus it acted as a recyclable adsorbent to
recover phosphate from the aqueous solution. Ca-biochar adsorbents
had mesoporous structures mainly containing elements like O, Ca, H,
and C, which are eco-friendly and bio-compatible. Therefore, the
phosphate-containing Ca-biochar may find use as phosphate-rich fer­
tilizer in the soil. Mechanism of synthesis and use of black liquor-derived
calcium-activated biochar is provided in Fig. 10.
Biochar synthesized from pineapple’s peel waste, and decorated with
magnetic Fe2O3 and lanthanum hydroxides was used for phosphate
removal. The modified magnetic biochar (MC) and La(OH)3-modified
magnetic biochar (Lax-MC) were investigated in a phosphate adsorption
study [128] (Fig. 11). The batch of La(OH)3-modified magnetic biochar
adsorbents were prepared and named La0.63-MC, La1.25-MC, La2.5-
MC, La5-MC, La10-MC, and La15-MC. Results reveal that La10-MC
showed better adsorption capacity than other adsorbent materials,
with higher phosphate adsorption capacity of up to 101.16 mg/g. The
influences of coexisting anions such as CO2− 2−
3 , NO3 , SO4 , HCO3 , and Cl
− − −
showed no significant effect on phosphate removal. The La10-MC
adsorbent showed higher selective adsorption and recyclability, and
their mechanism of action was based on electrostatic interaction, inner-
sphere complexation, and ligand exchange. The resultant data of
adsorption isotherms were fitted well by the Langmuir isotherm, and the
pseudo-second-order model signified kinetics.
The CaO-biochar composite materials were synthesized by ball
milling and pyrolysis methods using eggshell and rice straw. The batch
experimental studies were carried out to determine the phosphate
adsorption capacity [129]. CaO-biochar composites showed good per­
formance for phosphate adsorption from wastewater between pH values
from 5 to 11 and the maximum phosphate adsorption capacity of 231
mg P/g. The experimental data fitted with the Langmuir isotherm model
and pseudo-second-order kinetics. The thermodynamic study indicated
that phosphate sorption was a spontaneous and endothermic process.
CaO-biochar composite can be applied as fertilizer after phosphate re­
covery and may act as a slow-release fertilizer for the soil.
Lanthanum-modified Platanus ball fiber biochar (La-TC) was devel­
oped from biochar of Platanus ball fiber treated with lanthanum nitrate
hexahydrate. The study aims to examine the phosphate adsorption ef­
ficiency of La-TC adsorbent [130]. The maximum sorption efficiency of
phosphate on La-TC was 148.11 mg/g at an initial pH of 6.0, the dosage
of 0.4 g/L, and the contact time of 20 min at 35 ◦ C. Adsorption kinetics
showed that the La-TC adsorption performance followed the pseudo
second order and Elovich models and fitted well with the Langmuir
isotherm model [130]. Modified biochar material showed an improved
adsorption capacity and more number of active surface functional
groups over other materials of a similar category, for phosphate
adsorption. Biochar-based adsorbent materials gained much interest as a
promising agent for environmental applications and agriculture with
great properties, including high surface area, porosity, and incorporated
functional groups for nutrient recovery from wastewater.
3.4. Removal of phosphate from wastewater by metal hydroxides
Excessive phosphate discharge into the water system leads to
eutrophication responsible for the global environmental problem [131].
Phosphate removal from an aqueous solution by utilizing metal (Fe3+)
oxide/hydroxide nanoparticles has been studied widely. The researcher
has found that metal (Fe3+) oxide/hydroxide nanoparticles have a
E. Priya et al. Journal of Water Process Engineering 49 (2022) 103159

Fig. 10. Schematic representation of the mechanism of Black liquor-derived calcium-activated biochar [127].

Fig. 11. Schematic representation of the mechanism of La(OH)3-modified magnetic pineapple biochar [128].

higher affinity towards phosphate ions than other contaminants present
in wastewater [132]. There is no universal method available to recover
phosphate from municipal and industrial wastewater. Physiochemical
activated sludge and biological nutrient removal are the most commonly
used methods to remove phosphate from municipal and industrial
wastewater. Compared to these methods, adsorption is one of the most
effective beneficial and economically low-cost methods to remove
phosphate [133]. In one such study (Fe3+) oxide/hydroxide
nanoparticles-based agglomerates (AggFe) were used for phosphate
removal from an aqueous solution [134]. A series of batch experimental
studies were carried out to determine the sorption capacity of phosphate
removal. Experimental conditions maintained during the studies were
initial phosphate concentration is 10 ppm, the adsorbent concentration
(iron (Fe3+) oxide/hydroxide nanoparticles-based agglomerates) from
50 to 180 ppm, pH values vary from 7 to 9, and presence of various
competition inorganic ions: NO−3 , SO2−4 , HCO3 , Na , Ca
− + 2+
and Cl− .
These competing inorganic ions did not show any significant influence
on phosphate recovery except HCO−3 ions. Adsorbent enhances the
adsorption capacity towards phosphate in comparison to HCO−3 ion,
even though increasing the concentration of adsorbent results in the
incorporation of additional adsorption sites on the surface of AggFe.
Further, the morphological characterization is determined through

17
E. Priya et al.
transmission electron microscopy (TEM); the result indicated that the
nanoparticle with an average size of 50 nm. The sorption efficiency of
the AggFe adsorbent was about 70 mg P/g at optimum pH of 7.5. The
experimental results were well fitted with pseudo-second-order reaction
kinetics and the Langmuir isotherm model.
In another study, phosphate removal capacity was evaluated using
iron oxide nanoparticles (IONP) [135]. Iron oxide nanoparticles were
synthesized from leaf extract of eucalyptus with CTAB surfactant. The
phosphate removal efficiency was determined using CTAB-modified
iron oxide nanoparticles and related to unmodified iron oxide nano­
particles, CTAB, ELE (eucalyptus leaf extract), and material made
without ELE. Compared to unmodified materials, CTAB-modified IONP
showed better results because CTAB-modified IONP had dual adsorption
properties, including electrostatic interaction or ligand exchange
mechanism due to the presence of hydroxyl group and protonated CTA+
layer capping on the external surface site of adsorbent responsible for
the higher sorption capacity. Higher temperature favored the sorption
capacity of phosphate (P) in CTAB-modified IONP. The maximum
adsorption capacity of CTAB-modified IONP was 5.64 mg/g, 7.94 mg/g,
and 9.41 mg/g at 288 K, 298 K, and 308 K, respectively. It indicates the
adsorption process of phosphate-depend on endothermic reaction. Ac­
cording to the results, CTAB-modified IONP follows the Langmuir
isotherm and the pseudo-second-order kinetics and increasing the
starting phosphate concentration from 10 to 60 mg/L resulted in a
greater adsorption capacity from 4.26 to 17.87 mg/g.
The phosphate removal using magnetic iron oxide nanoparticles was
studied using a batch experimental study [136]. Phosphate adsorption
depended on the ligand exchange mechanism; under this mechanism,
phosphate ions can replace hydroxyl ions on the surface of iron hy­
droxide (the inner-sphere complex formation), leading to the covalent
bond between phosphate ions and iron hydroxide. The adsorption ki­
netics was stable at acidic pH (2.0 to 6.0); further increasing pH led the
alkaline condition to generate more hydroxyl ions. The thermodynamic
result indicates that the adsorption process is endothermic. The
maximum adsorption capacity was found to be 5.03 mg/g. The
adsorption data of magnetic iron oxide nanoparticles fitted well with the
Freundlich and Redlich-Peterson isotherms and Pseudo-second-order
adsorption kinetics [136]. Iron (hydr)oxides are low-priced, eco-
friendly materials for phosphate sorption. Synthesizing iron hydroxide
in the form of the nano dimension shows a better performance towards
the phosphate ions. The mechanism responsible for phosphate removal
capacity is ligand exchange and the formation of inner-sphere com­
plexes (Lewis acid-base interaction) by the utilization of iron hydroxide.
Fig. 12. Adsorption mechanism of MIL-101(Al/Fe) [138].
18
Journal of Water Process Engineering 49 (2022) 103159
3.5. Chitosan adsorbents used for phosphate removal
Chitosan has been used in various industries, including wastewater
treatment, the environment, medicine, and pharmaceuticals, for
different application purposes. Chitosan is a nontoxic, biocompatible,
biodegradable, hydrophilic, and highly reactive material. Additionally,
the chitosan linear polyamine structure has many free amine groups
available for crosslinking and modifications responsible for phosphate
adsorption [137]. The elimination of the phosphate, metal-organic
framework has received much attention in recent years. So Zhang
et al. synthesized chitosan-based adsorbents integrated with MIL-101
(Al/Fe) for phosphate removal [138]. The materials were created
using the in-situ growing process. The MIL-101(Al)-CS and MIL-101(Fe)-
CS adsorbents sustain strong phosphate adsorption throughout a broad
pH range of 3–11. This result indicated that ligand exchange takes place
between adsorbents and phosphate. The adsorption capacity of MIL-101
(Al)-CS was greater than that of MIL-101(Fe)-CS. This finding might be
implied that the binding affinity of the MOF metal atom in adsorbents
with the O atom of phosphate differs (Al > Fe). The phosphate adsorp­
tion process was based on electrostatic, and ligand exchange mecha­
nisms (Fig. 12). The isotherm and adsorption kinetics investigations
revealed that monolayer adsorption and chemisorption are the primary
processes of phosphate adsorption. MIL-101(Fe)-CS and MIL-101(Al)-CS
had greater sorption capacities of 46.8 mg/g and 49.8 mg/g, respec­
tively. These results demonstrated that the MOFs-chitosan adsorbents
act as potential adsorbents for phosphate removal [138].
In another study, iron-loaded magnetic alginate-chitosan double-gel
interpenetrated porous beads (M-IACBs) adsorbent was produced for
phosphate removal. Chitosan and sodium alginate, two long-chain linear
polysaccharides, were combined to create a two-layer network that
improves the stability of the adsorbent. The synthesized material had a
maximum adsorption capability of 18.5 mg/g. The observations on
adsorption well fitted with the Langmuir isotherm and pseudo-second-
order kinetics. The adsorption capacity was steady between pH 2 and
7. Further, increased pH led to an electrostatic repulsive force between
the adsorbent material and the phosphate. The synthesized M-adsorbent
IACB’s material works in two different ways. (1) When phosphate ions
enter the adsorbent surface, they are quickly adsorbed via electrostatic
contact to form outer-sphere complexes. (2) Through an electron donor-
acceptor interaction, integrated iron form a coordination bond with the
phosphate’s oxygen atom, replacing OH− to create a stable inner-sphere
complex [139]. Furthermore, chitosan/lanthanum hydrogel beads were
used in this work to remove phosphate from an aqueous solution. This
adsorbent substance eliminated phosphate across a wide pH range of
2–7. This material had a maximum adsorption capacity of 107.7 mg/g
E. Priya et al.
and followed the Langmuir isotherm model. The interaction of phos­
phate ions with adsorbent material was based on ion exchange and
electrostatic interaction [140]. In order to remove phosphate from an
aqueous solution, Xiaohui et al. created an inexpensive, ecologically
acceptable adsorbent using chitosan and bentonite that was doped with
lanthanum (La-BC-5) [141]. The material’s optimum adsorption ca­
pacity was 23.52 mg/g. The mechanism of adsorption was based on
electrostatic contact, simultaneous precipitation, and complexation. The
pH value was thought to impact the phosphate adsorption process
significantly. Under acidic pH conditions, the developed composite
material showed high adsorption capability. As the pH rises, the
adsorbent surface becomes more negatively charged, and hydroxyl ions
compete with phosphate in alkaline conditions. Adsorption followed the
Freundlich isotherm model [141]. Adsorbents based on chitosan are
becoming a popular alternative for the adsorptive removal of phos­
phates from aqueous solutions. The modification of this material pro­
vides a more binding site for phosphate adsorption.
3.6. Cellulose-based adsorbents for phosphate removal
In the wastewater sector, the cellulose-based adsorbent approach has
developed as a cost-effective and environmentally acceptable alterna­
tive treatment technology for phosphate removal. In this aspect, cellu­
lose is used as an adsorbent; it assists in the selective removal of
phosphate pollutants from water and is subject to additional specialized
modification. SP-Zr-La composite was used for phosphate adsorption
from an aqueous solution [142]. In order to incorporate zirconium (Zr)
and lanthanum (La) hydroxides and create the SP-Zr-La composite,
shaddock peels (SP), a highly carboxylated biomaterial, was employed
as the host material. The SP-Zr-La composite demonstrated the presence
of certain rods or amorphous nanoparticles that were anchored inside
the SP and exerted more readily accessible interface contacts towards
the phosphate ions. These nanoparticles ranged in size from 20 to 150
nm. The adsorption capacity of phosphate by SP-Zr-La increased as the
temperature rose from 2 to 3, exhibited an adsorption capacity of 21.4 to
23.5 mg/g, and after that, progressively decreased by 7.2 mg/g at pH
11.0, and under this condition, it’s indicated that the presence of hy­
droxyl ions led to declines in the adsorption capacity. The adsorption
process’s mechanism was based on forming inner-sphere complexes.
After ten cycles with a 10 % NaOH solution, the recovery capabilities
were still at or above 90 %.
Anirudhan et al. developed a cellulose-grafted epichlorohydrin-
functionalized polyethylenimine graft copolymer for phosphate removal
(Cell-g-E/PEI). Cellulose was combined with polyethylenimine,
epichlorohydrin, N,N′ -methylene bisacrylamide (MBA), a crosslinking
agent, and azetobis-isobutyronitrile (AIBN), an initiator to produce an
adsorbent material. The adsorbent containing the amine functional
group was responsible for phosphate adsorption, with a maximum
adsorption capacity of 111.7 mg/g at pH 4.5 and reached equilibrium at
adsorption capacity in 3 h. It was demonstrated that the Pseudo-second-
order kinetic model well represents the kinetic rate and agrees with the
Freundlich isotherm, which suggests multilayer adsorption onto adsor­
bent (Cell-g-E/PEI). The mechanism of adsorption is anion exchange
[143].
In another study, ferric hydroxide-coated cellulose nanofibres (Fe
(OH)3@CNFs) were used for phosphate adsorption. The maximal
phosphate sorption capacity of Fe(OH)3@CNFs was determined to be
142.86 mg/g. The adsorbent-phosphate interaction was based on the
inner-sphere complexation of phosphate on ferric hydroxide via ligand
exchange and electrostatic attraction. Phosphate adsorption followed
the Langmuir isotherm and pseudo-second-order models. In addition,
competing ions like chloride, sulfate, and nitrate caused the least
amount of interference to the adsorption process [144]. Besides, these
various functionalized cellulose adsorbents have excellent phosphate
ion adsorption potential. Furthermore, cellulose-based materials have
many good properties, such as low energy consumption, a wide range of
19
Journal of Water Process Engineering 49 (2022) 103159
sources, environmental protection, economic feasibility, and renewable,
and have a very broad application promise in wastewater treatment.
4. Adsorbents used for nitrate and phosphate co-removal from
wastewater
Recently increased research interest has been focused on the
adsorption of nitrate (N) and phosphate (P) from wastewater. Re­
searchers have been utilizing various types of adsorbents for recovery
purposes, showing different physicochemical properties for nitrate and
phosphate adsorption from an aqueous solution [26]. In a study by
Nodeh et al., nitrate and phosphate ions were removed from the water
using nanosized lanthanum hydrous doped on magnetic graphene
nanocomposite (MG@La) [53]. FTIR, XRD, and FESEM were used to
determine the surface and physicochemical properties of the adsorbent.
FT-IR spectra results indicated that most lanthanum ions found as hy­
droxide form with a high density of positive ions (La3+(OH− )3). The
synthesized metal hydroxide adsorbents showed a high affinity towards
phosphate ions by forming inner-phase and outer-sphere complexes
through electrostatic interaction. So the mechanism of phosphate and
nitrate on MG@La was mainly based on electrostatic interaction. The
maximum adsorption was obtained under a wide range of pH from 4 to 8
for nitrate and phosphate. The maximum adsorption efficiency of
MG@La for phosphate was 116.28 mg/g, whereas it was 138.88 mg/g
for nitrate ions. The experimental data were well fitted to Pseudo second
order and the Langmuir model isotherm.
Zr/CTAB/BAC was prepared by bamboo activated carbon (BAC)
functionalized by zirconia chloride octahydrate (ZrOCl2⋅8H2O), and
cetyltrimethylammonium bromide (CTAB) was utilized for removal of
phosphate and nitrate [145]. The modification of bamboo activation
was done with the steam activation method. When the dosage of Zr/
CTAB/BAC was in the range of 0.1 g–1.0 g, the removal efficiency of
phosphate in simulated wastewater was between 59.32 % and 99.42 %,
and the removal efficiency of nitrate was between 34.08 % and 93.70 %.
Adsorption isotherm showed that the modified BAC (Zr/CTAB/BAC)
adsorbent performance followed the Langmuir model for phosphate and
the Freundlich model for nitrate. Further, the mechanism of phosphate
and nitrate was based on chemical adsorption. The thermodynamic data
showed that the adsorption process is spontaneous and endothermic.
After four times regeneration of adsorption and desorption experiments,
Zr/CTAB/BAC had a high removal effect (70 %) on phosphate and ni­
trate in the water. Therefore, it can be effectively used as an adsorbent to
remove anion salts in sewage.
The novel hybrid polymeric anion exchanger impregnated with hy­
drated Fe(III) oxide (HFO) nanoparticles (HA520E-Fe) was synthesized
and utilized for the co-removal of nitrate and phosphate [105]. The
synthesized HA520E-Fe hybrid material had dual functional groups;
triethylamine, which was selective for nitrate ions through the ion ex­
change mechanism, and HFO nanoparticles, which were selective for
phosphate adsorption through Lewis acid-based (LAB) interactions.
During loading HFO nanoparticles in the resin, an ethanol medium was
utilized to reduce the repulsion between Fe3+ ions and triethylamine
functional groups, called the Donnan exclusion effect. Ethanol medium
was basically increasing HFO formation inside the parent anion ex­
change resin. The sorption efficiency of nitrate on HA520E-Fe was be­
tween 56.85 and 60.37 mg/g at the pH range of 3 to 11, and the
maximum phosphate uptake recorded was 12.18 mg as P/g of adsorbent.
The phosphate adsorption data were better fitted with the Freundlich
model than the Langmuir.
The bifunctional nanocomposite HFO@ TPR was synthesized by
incorporating HFO nanoparticles inside a triethylamine-functionalized
polystyrene resin (TPR) used for the adsorption of nitrate and phos­
phate [106]. As shown in Fig. 13, nanocomposite HFO@ TPR had two
different active sites for binding of both nitrate and phosphate.
The results indicated that triethylamine-functionalized polystyrene
resin showed selective adsorption for nitrate via ion exchange, and
E. Priya et al.
Fig. 13. Schematic illustration of HFO@TPR and its possible mechanism for nitrate and phosphate interaction [106].
incorporated iron hydroxide nanoparticles showed specific interaction
with phosphate through inner-sphere complex formation. The experi­
mental data fitted to both Pseudo-first-order and second-order kinetics.
The maximum adsorption capacity of nanocomposite HFO@ TPR for
nitrate was reduced from 18 to <10 mg N/L. In contrast, it was reduced
from 2.5 to <0.2 mg P/L for phosphate [106].
The biochar was generated from sawdust and rice husk used for the
removal of nitrate and phosphate from the aqueous solution. The bio­
char was created by pyrolyzing sawdust and rice straw at different
temperatures like 700 ◦ C and 300 ◦ C. As a result, four distinct biochar
samples were created: SD 700 (derived from sawdust 700 ◦ C), SD 300
(derived from sawdust 300 ◦ C), RH 700 (derived from rice husk 700 ◦ C),
and RH 300 (derived from rice husk 300 ◦ C). The results of kinetics data
showed that adsorption capacity increased sharply for up to 3 h. The
maximum adsorption capacity within 3 h demonstrated that there are
more active sites for nitrate adsorption on biochar surfaces. RH 700 had
a greater nitrate adsorption capacity of 95.42 mg/g after 12 h when
compared to other synthetic materials. RH 300 had a greater phosphate
absorption capacity, measuring 47.18 mg/g. Furthermore, synthesized
biochar demonstrated greater nitrate adsorption at higher temperatures,
while phosphate adsorption at lower temperatures. Ion exchange was
the basis for the nitrate and phosphate adsorption process. This result
employs loaded nitrogen and phosphate biochar as nutritional sources
for plant development [107].
Furthermore, amine-functionalized walnut shells (ACWNS) were
used for nitrate and phosphate adsorption. In order to modify, N,N-
dimethylformamide, epichlorohydrin, ethylenediamine, and triethyl­
amine were used. The inserted triethylamine functional groups were in
charge of nitrate and phosphate ions adsorption via electrostatic inter­
action and hydrogen bonding. The highest adsorption capacity of
ACWNS for nitrate and phosphate were 82.2 and 35.7 mg/g, respec­
tively. Notably, nitrate adsorption was based on the Langmuir model for
nitrate and the Freundlich model for phosphate adsorption. The Pseudo-
second-order kinetic model fitted well with nitrate and phosphate, and
adsorption was exothermic and spontaneous for both ions [108].
Huanhuan et al. created the tea waste biosorbent (ACTW) and
removed phosphate and nitrate from the aqueous solution using amine
crosslinking. N,N-dimethylformamide, epichlorohydrin, ethylenedi­
amine, and triethylamine were used to modify. The synthesized material
exhibited greater adsorption capacity against a broad pH 3–10 range.
For phosphate ions, the maximal adsorption efficiency of ACTW was
98.72 mg/g, while for nitrate ions, it was 136.43 mg/g. According to
these studies, the removal of phosphate and nitrate ions by ACTW may
be accomplished by electrostatic attraction and ion exchange. These
findings suggested that ACTW may be used as a unique biowaste ma­
terial for removing phosphorus and nitrogen from eutrophic water. The
20
Journal of Water Process Engineering 49 (2022) 103159
adsorption was well fitted with the Langmuir isotherm model [109].
Fatemeh et al. developed a cellulose nanofibres aerogel to remove
nitrate and phosphate from aquaculture effluent [110]. In order to
create cellulose nanofibres aerogel adsorbents, cellulose nanofibres
were first made from sugarcane bagasse. These nanofibres were then
combined with the ecologically friendly cross-linker carboxymethyl
cellulose and citric acid. The adsorption capacity of the synthesized
material for nitrate was 79.65 mg/L and for phosphate was 98.18 mg/L.
The findings showed that the CNF aerogels could operate as an effective
adsorbent for the reduction and removal of nitrate and phosphate
because they had a high porosity, high low density, and specific surface
area, fitted well with Langmuir adsorption models and Temkin and the
pseudo-second-order kinetics model. The simultaneous removal of the
phosphate and nitrate ions-based adsorbent-based material needs to be
further focused on in the future. If synthesizing adsorbent materials have
a specific functional group with biodegradable nature, the adsorbed
nutrient and phosphate can directly be applied to the agricultural land as
fertilizer for plant growth.
5. The major anions that impede the adsorption of nitrate and
phosphate
Along with nitrate and phosphate, wastewater typically contains a
number of other coexisting ions that may compete for adsorbent active
adsorption sites. Major anion competitors with nitrate and phosphate
include HCO−3 , Cl− and SO2− 4 . The presence of these competing anions
lowers the nitrate and phosphate adsorption capacity. The physico­
chemical properties of competing anions, as well as their interaction
with the adsorbent surface, have a significant influence on the adsorp­
tion process [146]. Mahmoud et al. discovered that the existence of
phosphate, sulfate, bicarbonate, and chloride reduced the adsorption
capacity of modified granular activated carbon. The largest reduction
efficiency was shown to be nitrate with sulfate, followed by chloride and
phosphate, with no significant change in the presence of bicarbonate
[147]. The chitosan composites were used to remove nitrates. The
adsorption ability of these biosorbents was tested in the presence of
anions such as sulfate, chloride, bicarbonate, and fluoride. The results
suggested that sulfate had the most adverse effects, followed by bicar­
bonate, fluoride, and the presence of chloride, which had a slightly
negative effect. This might be because the sulfate ion had a greater ionic
charge than the nitrate ion. These competing anions attach to the
adsorption site, resulting in electrostatic repulsive interactions between
the biosorbents and nitrate ions, reducing adsorption capacity. Because
nitrate adsorption involves electrostatic interaction rather than selective
adsorption, other ions in the water compete with it [148]. According to
Yanhui et al., the presence of sulfate, chloride, and bicarbonate ions with
E. Priya et al.
a surfactant-modified zeolite (SMZ) lowered the adsorption capability of
nitrate [149]. Furthermore, amine grafted agricultural waste was used
in this work to remove nitrate ions [150]. Adsorption capacity was
determined by the presence of co-existing ions such as sulfate, phos­
phate, and chloride, which showed that adsorption capacity drops
sharply in the presence of sulfate and declines slightly in the presence of
chloride and phosphate [150]. Besides, it is noted that using various
kinds of adsorbent material to remove nitrate with the presence of
competing ions shows that sulfate is more competitive with nitrate than
other anions because the valency of sulfate ion is two than other ions.
Yinhai et al. revealed that anions such as bicarbonate, sulfate,
chloride, and nitrate deteriorate the phosphate adsorption in
lanthanum-incorporated porous zeolite was utilized for phosphate
adsorption. The findings showed that chloride and nitrate have minimal
effect on phosphate adsorption. When the sulfate concentration was
raised, the removal efficiency dropped from 98.9 to 94.6 %. This
property indicated that multivalent anion adsorption was easier than
monovalent anion adsorption. However, increasing the bicarbonate
content reduced phosphate adsorption by 18 %. It is caused by the
electrostatic repulsive force between deprotonated hydroxyl ions and
highly charged phosphate ions due to the high pH (due to bicarbonate
ions) [151]. Hu et al. studied phosphate adsorption in Ce(III) impreg­
nated crosslinked chitosan with co-existing ions such as sulfate, chlo­
ride, bicarbonate, and nitrate. The results revealed that sulfate had a
greater interfering impact than chloride and the presence of bicarbonate
drastically decreased the phosphate ion adsorption capability [152].
Further, Zhang et al. discovered phosphate adsorption onto metal oxide
and metal hydroxide doped with activated carbon in the presence of
anion (chloride, sulfate, nitrate, fluoride, and carbonate). It was
discovered that increasing competing ions in the range of 0–0.1 mol/L
had a notable influence on phosphate adsorption. Carbonate had the
biggest impact on phosphate among these five anions. Through a
bidentate inner-sphere interaction, the carbonate anions were con­
nected to the active metal sites [153]. Yao et al. discovered that anions
such as chloride, nitrate, and bicarbonate compete with phosphate,
reducing phosphate adsorption. This impact was highest when the three
competing ions were combined together in a solution. Each anion
independently decreased phosphate adsorption by <20 %, but by over
40 % when anions were combined [154]. Ying et al. investigated the
phosphate selectivity of ZEO@AZ in the presence of various concen­
trations of competing ions (50 to 800 mg/L) such as chloride, nitrate,
sulfate, and bicarbonate. The results suggested that the nitrate and
chloride in the solution have little or no influence on phosphate. As the
concentration of coexisting ions increased from 50 to 800 mg/L, sulfate
and bicarbonate greatly influence phosphate adsorption in an aqueous
solution. These findings showed that nitrate and chloride interact with
phosphate via weak interactions by forming outer-sphere complexes. At
the same time, sulfate and bicarbonate can produce both outer and inner
sphere complexation with adsorbent [118]. Therefore, in the medium
utilizing different adsorbent materials, bicarbonate has the greatest
impact on phosphate adsorption, followed by sulfate, chloride, and
nitrate.
6. Conclusions and outlook
The development of industrialization causes exudes of several types
of contaminants to water sources. Lately, the increase of toxic anionic
contaminants, specifically nitrate and phosphates, in water sources
certainly disses the ecological system and creates severe problems.
Moreover, the adsorption process is one of the most promising methods
utilized to remove the various contaminant from wastewater. This is due
to its unparalleled benefits, which include being cost-effective, time-
consuming, easy to handle etc. In addition, this review gathers a list of
several materials that have been utilized as adsorbents for nitrate and
phosphate removal by the adsorption process and their varied adsorp­
tion capacities based on the modification and functional group present
21
Journal of Water Process Engineering 49 (2022) 103159
on the surface sites. The nitrate adsorption is mainly based on the ion
exchange or electrostatic interaction between the positively charged
functional group of surface sites and negatively charged nitrate ions.
Besides, the adsorption of phosphate depends on the ligand exchange
mechanism. In this mechanism, phosphate ions can replace hydroxyl
ions on the surface of the adsorbent functional group (the inner-sphere
complex formation), leading to the covalent bond between phosphate
ions and the adsorbent functional group.
In this review synthesized nanocomposite Nano-CS/Clino modified
by pentaethylenehexamine showed a higher adsorption capacity of ni­
trate. For phosphate, CaO-biochar composites were prepared by mixed
ball milling, and pyrolysis of agricultural wastes eggshell and rice straw
showed better phosphate adsorption capacity as compared to other
adsorbents. The MG@La adsorbent showed better adsorption for both
nitrate and phosphate from the water. Consequently, selecting appro­
priate adsorbents for the effective removal of nitrate and phosphate is a
complicated task. In laboratory conditions, a particular sorbent shows
good adsorption capacity for nitrate and phosphate, but they may fail in
actual wastewater conditions.
Herein, we tried to display a better understanding of how various
types of adsorbent materials and their surface modification are used to
remove nitrate and phosphate from water sources efficiently. Further, it
should be noted that the whole world is facing a huge problem with
nitrate and phosphate in wastewater. So it is very much necessary to
remove and reduce the nitrate and phosphate concentration from
wastewater. Further, it has been noted that most research experimental
methods are carried out by assessing a very high initial concentration of
nitrate and phosphate in the batch system, which is not a practical
condition. Thus, the adsorbent’s capacity must be tested in a continuous-
flow column system to determine the operating parameters required for
designing real-life adsorption columns used in wastewater industries.
The adsorbent’s efficiency should be tested using real-life wastewater
for successful practical application. Compared to individual removal of
nitrate or phosphate, co-removal mechanism for N and P needs to be
focused on in the future because wastewater contains both nitrate and
phosphate. The application of nitrate and phosphate recovery at full
scale currently occurs in a few countries, so implementing this large-
scale research needs to be focused on other countries also. So further
research needs to focus on environmentally friendly adsorbents with
higher efficiency, and effective modification techniques need to be
synthesized. Subsequently, the cost-benefit assessment of adsorbed
materials should be considered for use on a large scale and real waste­
water treatment. To conclude, the environmentally safe disposal of ni­
trate and phosphate adsorbents needs to be synthesized. It would be
worthwhile to investigate the agricultural-based adsorbent because,
after the recovery, adsorbent material can directly be applied to the soil
as fertilizer.
Declaration of competing interest
None.
Data availability
No data was used for the research described in the article.
Acknowledgments
This project has been supported by Department of Science and
Technology, Government of India under the project grant No. DST/TDT/
AGRO-39/2020. The author, Mrs. E. Priya, also acknowledges the
Council of Scientific and Industrial Research, Government of India, for
fellowship support under the grant No. 09/143(0971)/2019-EMR-l.
E. Priya et al. Journal of Water Process Engineering 49 (2022) 103159

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