1.

Adsorption

Currently, adsorption is found to be a simple yet effective technique in industries for

wastewater treatment applications. The success of the technique is based on the
development of an efficient adsorbent (Wang & Peng, 2010).

2. Properties of Nitrate and Phosphate

The adsorption mechanism of the nitrate and phosphate ions onto adsorbents is dependent
on the physical chemical properties of N and P ions and their interaction with the adsorbent
surface. Some of the important characteristics of inorganic anions are brief in table below.

Table 1: Properties of nitrate and phosphate

Parameter Nitrate Phosphate

Molecular formula NO3- PO43-
Molar mass (g mol−1) 62.0049 94.97
Solubility in water 912.0 (25 °C) 88.0(25 °C)
(Na salts) (g L−1)
Charge Monovalent Trivalent
Ionic radius 3.0 -
(Rion) (×10−10 m)

3. Nanomaterials

The most significant properties about the nanomaterials as adsorbent is due to the large
surface to volume ratio and high chemical reactivity (Pradeep 2012). However modifying
its functionality and morphology helps to enhance the ability and reduce the drawbacks.
Characteristics of nanoparticles adsorbents for high efficient removal of ions from
wastewater are:

1. Must show relatively high sorption capacities and selectivity even to the low
concentration of pollutants
2. Presence of effective adsorption sites for anions in water
3. The sorbents could be infinitely recycled
4. The adsorbed pollutant could be removed from the surface of the nanoadsorbent
easily

The main aim in this review are to highlights recent advances in the development of novel
nanomaterials for removing nitrate and phosphate ions from water system. Based on
previous studies, there are four most widely functional materials for waste water which are
zerovalent metal-containing nanoparticles, nanoscale metal oxide materials, carbon based
nanomaterials and functionalized nanomaterials. These have a broad range of
physicochemical properties that make them particular attractive for water treatment.
3.1 Removal Using Nanoscale Zerovalent Materials

Nanoscale zerovalent is more selective than zerovalent due to greater surface area to volume
ratio (Wang and Zhang 1997). Besides, it also become of the latest discoveries because of
unique characteristics including high reactivity for the removal of targeted contaminants,
high mobility in porous media and low toxicity. These properties are the main tool when
designing this nanoparticles for water treatment (Yan et al., 2013). The common zerovalent
nanoparticles used in water remediation is nanoscale zero-valent iron as it is easy to prepare.

Based on previous studies, some materials have been developed as supporting material to
enhance the ability. This is because there are still some potential limitations like lacking in
durability, low mechanical strength (Cumbal et al., 2003) and quickly transformed to iron
oxides once exposed to the air (Nurmi et al., 2005). Despite of the fact that nanoscale
zerovalent has a decent capacity to remove phosphate and nitrate in wastewater, it is also
able to perform fast and simultaneous removal of different heavy metal ions. (Shaolin et al.,
2016). So, future research should to be completed to advance its structure and adsorption
productivity for chosen ions.

Table 2: Performance of Nanoscale Zero-valent Iron for the removal of nitrate, phosphate
and heavy metals

Adsorbent Target ions pH and Amount Adsorption Reference

time (min) taken (mg/L) capacity (mg/g)
Nanoscale Zero-valent Nitrate pH: 7 100 97 % (Hwang et al.,
Iron t: 90 2011)

Nanoscale Zero-valent Phosphate pH: 4 1-10 96–100 % (Almeelbi et al.,

Iron t: 30 2012)

Nanoscale Zero-valent pH: - 20 (Peng et al.,

Iron / graphene Nitrate t: 30 15.63 2015)

Nanoscale Zero-valent pH: 12 (Eljamal et al.,

Iron / copper chloride Phosphate t: 30 60 % 2016)

Nanoscale Zero-valent Uranium

pH: 5
Iron (V) 333 99.9 % (Li et al., 2015)
t: 24 h
Nanoscale Zero-valent pH: 5 (Zhang et al.,
Iron / kaolinite Lead t: 30 500 96% 2011)

Nanoscale Zero-valent Chromium pH: 3

Iron / bentonite (VI) t: - 20 99.5 % (Shi et al., 2011)
3.2 Removal Using Metal Oxides Nanomaterials

Metal oxides are the inorganic nanoparticles, which are broadly used for the removal of the
ions and heavy metals. They have also been widely adopted as adsorbent because these
metals possess high surface area and specific affinity for the adsorbate impurities and give
minimal environmental impact.

A lot of studies have been done using this metal like ferric oxides, magnesium oxides, zinc
oxides and zirconium oxides. Results obtained indicates that high removal efficiency of
metal oxides before and also after some modifications but it strongly dependent on pH,
temperature, adsorbent dose and the time (Gupta et al., 2015). For phosphate and nitrate,
Eljamal et al., (2016) reported MgO-biochar nanocomposites exhibits an excellent
adsorption ability these ions in aqueous solutions. Zeolite and lanthanum hydroxide also
have good phosphate uptake because La has high attraction to oxy donor leading to efficient
ion exchange. However, most of the available literature reports showed the high adsorption
capacity of metal ions by Fe3O4 magnetic nanoparticles. This happened due to the presence
of higher number of active sites and aqueous stability on the surface.

Table 3: Performance of metal oxides nanomaterial for the removal of nitrate, phosphate
and heavy metals

Adsorbent Target ions pH and Amount Adsorption Reference

time (min) taken (mg/L) capacity (mg/g)

Fe3O4/ZrO2/ Nitrate pH: 3 Nitrate: 100 Nitrate: 89 % (Jiang et al., 2013)

chitosan Phosphate t: 1440 Phosphate: 50 Phosphate: 27 %

Z-La(OH) Phosphate pH: 2 -10 500 71.94 % (Xie et al., 2014)

t: 24 h

Fe-Mg-La Phosphate pH: 6.4 100 48.3 % (Yu and Paul Chen,
t: 10 2015)

MgO- biochar Nitrate pH: Nitrate: 100 Nitrate: 94 % (Eljamal et al.,

Phosphate t: 3 Phosphate: 50 Phosphate:83.5% 2016)

Fe3O4 /carboxyl, 91 97 % (Gao et al., 2008)

As3+ pH: 8
amine and thiol-
Pb(II), pH: 8 Pb:100%,
(Engates and
TiO2 Cd(II) t: 120 0.5 Cd:99.9%
Shipley, 2011)
Ni(II) Ni:99.2 %
Fe3O4 / Polymer Zn (II) pH: 5.5 Zn: 85 %
modified Pb(II) t: 50 Pb: 97 % Ge et al. (2012)
Cu(II) Cu: 90%
ZnO / Ga Cr (VI) pH: 3 67.57 % (Ghilouf et al.,
2015)
Cu/ZnO Pb (II) pH: 7 1111.0 (Modwi et al., 2017)
composite t: 35
3.3 Removal Using Carbon-Based Nanomaterials

Carbon based nanomaterials such as activated carbon, carbon nanotubes, functionalized

carbon based materials, graphite and graphene are the most widely used materials in various
industries. Due to their non toxicity and high sorption capacity they became a promising
adsorbents for environmental (Bhatkhande et al., 2002)

Activated carbons have high porosity, high surface area and prepared from readily available
material like agricultural wastes (Mauter and Elimelech, 2008).

Previous studies showed carbon nanotubes have superior sorption capacity and effective
desorption compared to activated carbon (Rao et al., 2007).This is because of the unique
structural, electronic, semiconductor, as well as mechanical, chemical and physical
properties.

Besides, graphene also extensively used as adsorbent because of large surface area. It is
typically made of one or several atomics layered graphite’s and have special two-
dimensional structure and good mechanical, thermal properties.

Although, carbon based nanomaterials are used very efficiently and successfully in removal
of organic, inorganic and metal ions from wastewater, several problems still remains.
Therefore more studies should be continued in this field to keep improving the results.
.
Table 4: Performance of activated for the removal of nitrate, phosphate and heavy metals

Adsorbent Target ions pH and Amount Adsorption Reference

time (min) taken (mg/L) capacity (mg/g)

Activated carbon Cr (VI) pH: 10 5-20 99 Selvi et al., 2001)

t: 180
Activated Cu (II) pH: 3 - 6 0.1 - 10 3.46 (Pyrzynska and
Carbon (powder) Pb (II) Bystrzejewski,2010)
t: 45 min
Carbon Residue/ NO3- NO3- : 4 10 NO3- : 30.2 (Kilpimaa et al.,
ZnCl2 PO43 PO43-: 6 PO43- :11.2 2015)
t: 5 h
Activated carbon PO43 t: 3 h 5 51.62 % (Ouakouak et al.,
powder 2016)
Activated carbon NO3- pH: 6.5 100 62.61 % (Asl et al., 2016)
/ Clinoptilolite t: 60
Table 4: Performance of carbon nanotubes for the removal of nitrate, phosphate and heavy
metals

Adsorbent Target ions pH and Amount Adsorption Reference

time (min) taken (mg/L) capacity (mg/g)

Multiwall & Phenol, (Flores et al., 2017)

Nitrogen-Doped pyridine
CNT
Carbon nanotubes PO43- pH: 5.6 200 15.4 (Mahdavi et al.
(CNT) t: 180 ,2016)
Multiwalled Co (II) pH: 5 - 9 2 - 20 30 (Pyrzynska et al.,
CNT t: 180 2010)
Oxidized carbon Ni (II) pH: 2 - 12 1-5 Ni (II) : 0.03 (Gao et al., 2009)
nanotubes Cu (II) t: 180 Cu (II) : 0.04
Cd (II) Cd (II) : 0.01

Table 5: Performance of graphene for the removal of nitrate, phosphate and heavy metals

Adsorbent Target ions pH and Amount Adsorption Reference

time (min) taken (mg/L) capacity (mg/g)

Few-layered Co (II) pH: 6-9 Co (II): 106.3 (Zhao et al., 2011)

Graphene oxide Cd (II) Cd (II): 68.2

Graphene PO43- pH: 7 100 89.37 % (Vasudevan et al.,

t: - 2012)
EDTA-Reduced Pb (II) pH: 2-8.2 1-100 367 (Madarang et al.,
Graphene oxide t: 24 h 2012)
Graphene oxide / NO3- t: 8 h 5 90%, 83%, 81% (Motamedi et al.,
Fe , Ni, Co 2014)
Table 6: Performance of functionalized carbon nanomaterials for the removal of nitrate,
phosphate and heavy metals

Adsorbent Target pH and Amount Adsorption Reference

ions time (min) taken (mg/L) capacity (mg/g)

NO3- NO3- : <8 300 NO3-: 71 %

MCM-48
PO43- PO43-: 4-6 PO43-: 88 % (Saad et al., 2007)
silica
t: 10
Functionalized silica NO3- NO3- : 4 NO3- : 130 NO3- & PO43- : (Hamoudi et al.,
materials PO43 PO43-: 6 PO43 : 100 45 -57 2012)
(C3H6—NH) t:
Zr(IV) - NO3- pH: 3- 10 NO3- : 10 NO3- : 128 (Sowmya &
chitosan PO43 t: 60 PO43 : 1000 PO43 : 149 Meenakshi, 2014)
Nylon 6 nanofiber Heavy (Jabur et al.,2016)
membrane/chitosan metals

5. Surface Modification Technique of Adsorbent

Surface Modification

Physical
Chemical
 Heat treatment
 Protonantion
 Metal impregnation
 Surfactan modification
 Grafting
 Table 7: Modification of nanomaterials for the removal of nitrate and phosphate

ADSORBENT TARGET MODIFICATION CHANGES REFERENCE

ION
Functionalized Nitrate Synthesized  high adsorption performances (Belcemi et al.,
(C3H6—NH Phosphate Via Post-Synthesis in terms of anions removal, 2013)
mesoporous silica) Grafting capacities and distribution
coefficients
Carbon Residue Nitrate Chemical activation  increase pore size (Kilpimaa et
from biomass Phosphate (ZnCl2)  increase surface area al.,2014)
gasification

Nano sized Nitrate Doped on magnetic  increase loading of anions on (Nodeh et

lanthanum Phosphate graphene graphene surface al.,2016)
hydrous nanocomposite  high removal efficiencies
 great surface area
 great adsorption capacity

Chitosan Nitrate Zr(IV) loaded  Zr(IV) loaded onto cross- (Sowmya &
Phosphate - cross-linked linked makingpolymer selective Meenakshi,
chitosan beads towards the nitrate and phosphate 2014)
- Silica dissolution  Cross-linking agents
(glutaraldehyde) increase strength
dissolution enhance the surface
area

Hydrated Ferric  fibrous have high efficiency in

Oxide Ion Exchangers water treatment (extremely fast
Nanoparticles Phosphate (Hybrid Fibrous) sorption) (Xialei et
ligand sorption capacity greatly al.,2015)
increased by dispersing
nanoparticles within polymeric
anion exchangers

Sepiolite (complex Nitrate HCl  Increase adsorption capacity of (Ozfurk et al.,

magnesium Nitrate ion 2004)
silicate)