CHAPTER 1: INTRODUCTION
Chemically modi?ed polymeric adsorbents are resins with functional groups such as phenolic
hydroxyl, acetyl, sulfonic group or amino group, grafted on hyper cross linked polymers
(Alexandratos & Natesan 1999), (Cai et al. 2005). Among these, aminated hyper cross linked
polymers display a unique advantage in adsorption of aromatic sulphonates (Pan et al. 2005)
phenol derivatives (Pan, Zhang, Wei & Ren 2008), and phenolic acids (Wang, Zhang, Zhao, Xia,
& Chen 2005) due to the presence of electrostatic interactions, hydrogen bonding interaction or
?–? interaction between adsorbents and adsorbents.
Polystyrene particles have excellent chemical and physical properties that make them not easy to
be degraded and damaged. Therefore polystyrene based adsorbents are usually used repeatedly.
Unmodified particles are not suitable to adsorb substances from aqueous solutions because the
surface is hydrophobic and lack of selective groups (Wang et al. 2005). However their
hydrophobicity and selectivity is increased after modification.
Nitrate is the most widely available contaminant in ground and surface waters (Liu et al 2005).
Excess of nitrate in drinking water results from anthropogenic sources, for example, over
fertilization in agriculture, cattle discharge, untreated sewage, leakage from septic systems,
infiltration of landfill leachate, and industrial waste water (Nuhoglu et al. 2005), (Hell et al.
1998), (Samatya et al. 2006), (Nataraj et. al 2006). Out of these, synthetic fertilizers are the
major contributors of nitrate pollution (Rupert 2008).
Nitrate concentration above the maximum permissible limit in drinking water is injurious to
human health. Nitrate exposure can lead to several health issues such as increased infant
mortality, birth defects, abdominal pain, diarrhoea, vomiting, diabetes, hypertension, respiratory
tract infections, and changes in the immune system (Majumdar & Guptar 2002), (Kross et al.
1992), (Fewtrell 2004), (Greener & Shannon 2005), (Ward, et al. 2005).
Numerous technologies are available for removal of nitrate from water. These include reverse
osmosis, electro dialysis, biological denitrification, and ion exchange methods. In case of reverse
osmosis (RO) water passes through a semipermeable membrane, and nitrate and other ions are
rejected because their size is greater than the membrane pore size.
Biological denitrification is widely practiced for the treatment of municipal and industrial
wastewater but is less commonly used in drinking water applications (Hu et al. 2001)
Ion exchange is a process in which the target ion gets exchanged with a loosely adsorbed ion on
a resin. Ion exchange is also like a reversible chemical process in which ions from an insoluble
permanent solid medium (the ion exchanger is usually a resin) are exchanged for ions in a
solution (Baes et al. 2002). This process is widely adopted for nitrate removal because of its
simplicity, effectiveness, and relatively low cost (Baes et al. 2002). Adsorption has proved to be
a relatively cheaper option which is readily applicable (Gupta & Ali 2000).
There are several methods that can be used to determine the concentration of nitrate ions and
amongst them ion selective method is the most versatile. The nitrate electrode contains an
internal reference solution in contact with a porous plastic organophilic membrane which acts as
selective nitrate exchanger (Qingshan et al. 1999). When the membrane is exposed to nitrates
present in water, a potential, E is developed across the membrane which is measured against a
constant reference electrode potential , E0 .The magnitude of E depends on the concentration of
nitrates present (Alexiades, & Mitrakas 1990).
1.1 Justification of the study
Conventional methods (example use of activated carbon) of removing nitrates are expensive. The
methods are also ineffective when the ions are present in high concentration (Somdutta et al.
2012). Use amino alkylated polystyrene will be of benefit because the particles have excellent
chemical and physical properties that make them not easy to be degraded and damaged.
Therefore polystyrene based adsorbents are used repeatedly. The amino alkylated polystyrene
has a large adsorption capacity.
1.2 Statement of the problem
Nitrate contamination in groundwater has become an ever increasing and serious environmental
threat since 1970s (Jeong, Kim, & Park 2012). The excessive application of fertilizers in
agriculture causes the infiltration of large quantities of this ion into underground and surface
water (Zhou et al 2007). Nitrate, due to its high water solubility (Thomson 2001), is the most
widespread groundwater contaminant in the world, imposing a serious threat to drinking water
supplies and promoting eutrophication.
Elevated levels of nitrate in drinking water can cause many health problems such as gastric
cancer, which results from the reduction of nitrate to nitrosamines in the stomach (Zheng &
Wang 2010). In addition, methemoglobinemia or blue baby syndrome, a serious health risk,
occurs when nitrate is converted to nitrite, which then reacts with the haemoglobin to cause
blueness of the skin of new born infants (Chatterjee & Woo 2009). After ingestion of plants or
water high in NO3? acute poisoning may occur within 30 minutes to 4 hours in cattle. Thus, the
problem occurs very quickly and often the cattle are observed to be normal one day and dead the
next day (Romano & Zeng 2009).
Ward et al. (2005) reviewed the epidemiologic evidence for the linkages between drinking water
NO3? and the risk of specific cancers, adverse reproductive outcomes, and other health outcomes
in the context of the current regulatory limit for nitrate in drinking water. Nitrate contaminated
water supplies have also been linked to outbreaks of infectious diseases in humans (Lin 1996).
Literature survey reveals that NO3? ion also causes diabetes and is a precursor of carcinogen
(Kostraba 1992), (Wolfe & Patz 2002).
Conventional method have several disadvantages such as only limited to certain concentrations,
generation of large amount of toxic sludge and the capital costs are much too high to be
economical. Adsorption based on the interaction between sorbent and adsorbent, offers the
advantage such as low operating cost, and high efficiency of removing low concentration ions
from water. In this study amino alkylated polystyrene has been chosen to be the adsorbent for the
removal of nitrate from water as it is a very cheap option and also reduces pollution by
1.3 Research questions
The following questions will be answered by the end of the research.
? What are the adsorption properties of amino alkylated polystyrene?
? What are the optimum conditions for the removal of nitrates from water using amino
? Which suitable isotherm best fits the adsorption of nitrate ions onto amino alkylated
The aims of the project were;
? To assess the performance of amino alkylated polystyrene in the adsorption of nitrate
ions from water.
? To determine the adsorption properties of amino alkylated polystyrene.
The objectives of the study were
? To prepare amino alkylated polystyrene
? To characterise nitrated polystyrene, aminated polystyrene and amino alkylated
? To identify the optimum conditions in the removal nitrate ions from water using amino
? To determine the isotherm that best fits the adsorption of nitrate ions.
? To identify the adsorption properties of amino alkylated polystyrene
The limitations of the study were failure to characterize the fuctionalized polystyrene by SEM,
BET, XRD and elemental analysis.
CHAPTER 2: LITERATURE REVIEW
This section outlines the information on research that has been carried out with respect to the
research problem at hand. The analytical methods of analysis are also reviewed.
All living organisms require the nutrient nitrogen for the growth and metabolism. Nitrogen is a
component of nucleic acids and other cell components. Nitrates are essential nutrients for plants
protein synthesis and play a critical role in nitrogen cycle. The findings from (Wang & Li 2004)
show that nitrogen mainly contributes in protein and chlorophyll formation.
Nitrate is a well-known contaminant of ground and stream water. It is an important
environmental and human health analyte, and thus its detection and quantification are considered
to be essential. The heavy utilization of artificial fertilizers and the uncontrolled discharges of
raw sewage have been known to cause the penetration of large nitrate quantities into the ground
and surface waters (Shrimali & Singh, 2001).
The most important environmental problems caused by nitrogen compounds are eutrophication
of water supplies and infectious disease (Guo et al. 2001), (Chiban et al. 2012).
In order to protect public health from the adverse effects of high nitrate intake, World Health
Organisation (WHO) set the standard as 50 mg/L to regulate the nitrate concentration in drinking
water (WHO 2001).
Polymeric adsorbents have attracted increasing attention over as an alternative to activated
carbon in industrial effluent treatment mainly due to their favourable physicochemical stability,
large adsorption capacity, good selectivity and structural diversity (Zhang et al. 2007). To obtain
large adsorption capacity and better selectivity for a specific anion, chemical modification of
ordinary polymeric resins is adopted by introducing functional groups onto the matrix of the
resin (Huang, Liu, Luo & Xu 2007). In particular introduction of amino and hydroxyl groups as
hydrogen bonding acceptors or donors onto the matrices of the resin will develop a series of
hydrogen bonding polymeric resins (Pan et al. 2003), (Ming et al. 2006).
2.1 Functionalization of polystyrene
Polystyrene is fuctionalized through various methods of nitration, amination and alkylation to
produce polynitrostyrene, polyaminostyrene and amino alkylated polystyrene.
2.1.1 Nitration of polystyrene
There are several methods that can be used nitration of polystyrene and they include direct
nitration with a concentrated nitric acid and sulphuric acid mixture, nitration in carbon
tetrachloride with acetyl nitrate, nitration in N, N?-dimethyl formamide with a concentrated nitric
acid and sulphuric acid mixture and nitration in 3-nitrotoluene with a concentrated nitric acid and
sulphuric acid mixture. Philippides et al. (1993) reported that reported that the first three methods
give products with low degrees of substitution and lead to a broadening of the molecular weight
distribution, but that method last gives poly (4-nitrostyrene) with minimal effect on the breadth
of the molecular weight distribution.
Philippides et al. (1993) has reported the effect of nitrating medium on the nitration of
polystyrene in which polystyrene is nitrated in anhydrous mixture of nitric acid and sulphuric
acid. Degree of substitution varies from one to two nitro groups per benzene ring and increases
with increasing time, temperature and concentration of nitric acid in the nitrating medium. The
effect of polar and nonpolar solvents on nitration are examined by nitrating the polymer in
fuming nitric acid or with a mixture of nitric acid and sulphuric acid in presence of dimethyl
formamide and carbon tetrachloride.
Dimethyl formamide increases the reaction rate with fuming nitric acid but decreases the
nitration rate in nitrating mixtures. Carbon tetrachloride decreases the nitration rate in fuming
nitric acid but increases the nitration rate in nitrating mixtures. The results are explained in terms
of mechanism of formation Of NO2+ in various nitrating media. Degradation of polymer is less in
the presence of organic solvents than in concentrated acids.
Shyaa (2012) indicates that nitration involves formation of a very strong electrophile, the
nitronium ion which is linear. This occurs following the interaction of two very strong acids,
sulphuric acid and nitric acid. Sulphuric acid is strong and it protonates the nitric acid on the OH
group such that a water molecule can leave. Benzene attacks the positively charged atom of the
electrophile, where one of the N=O is broken at the same time. This is followed by rapid loss of
a proton to generate the aromaticity. The equation 2.1 shows generation of the electrophile NO2+.
HNO3 + H2SO4 ? NO2+ + OSO3H- + H20 equation 2.1
Figure 2.1 Nitration of polystyrene
Concentrated sulphuric acid acts a catalyst. Nitration of polystyrene results in monomer
disubstituted product depending on the conditions of the nitration experiment, but the nitration in
ortho-position is slow and does not occur in this reaction due to steric hindrance.
2.1.2 Amination of nitrated polystyrene
Several methods different methods for the direct amination of nitrobenzene have been reported
(Stern & Cheng 1993). The most useful of these with respect to synthetic utility is vicarious
nucleophilic substitution for hydrogen (VNS). This class of reaction has been shown to be useful
for the introduction of carbon, oxygen and amine nucleophiles into nitro arenes but demands the
positioning of a good leaving group ? to the nucleophilic center which is eliminated during the
decomposition of the proposed ? complex intermediate. These methods generate reasonable
yields of nitroaninilines.
By contrast a more direct and automatically efficient route for the production of aromatic amines
would be via the direct displacement of hydrogen from nitrobenzene using amides as
nucleophiles. Aminolysis of the resulting aromatic amide would produce the corresponding
Amination of polynitrostryrene can also be carried out by reductive methods of the nitro group
(Abadie et al. 2006). Metals such as tin and iron are used to reduce the nitro groups.
Polyaminostyrene are synthetically important compounds that acts as precursors to the synthesis
of many interesting molecule and can be readily synthesized from polynitrostyrene compound
via reduction methods. Tin powder in concentrated HCl in ethanol gives a yield of 67% .This
process has been considered as effective method for the synthesis of polyaminostyrene. However
notable disadvantages to these methods include high reaction temperatures and relatively long
Figure 2.2 Amination of nitrated polystyrene
2.1.3 Alkylation of aminated polystyrene
One of the most frequently used procedures for the preparation of tertiary amines is the N-
alkylation of primary and secondary amines with alkyl halides in the presence of a base such as
KOH potassium, sodium amide, CsOH, (Salvatore 2002) thallium(I) ethoxide, CsF / Celite
(Hayat 2001) and Hünig’s base (Moore 2005). Other methods for N-alkylation include the
displacement of methanesulfonates, p-toluenesulfonates or p-nitrobenzene sulphonates by
amines on solid supports (Olsen 2003).
Tertiary amines on solid supports have also been synthesised by a variety of other protocols
(Lober 2004). Some other methods, such as a Mannich-type reaction (Tremblay-
Morin 2004) reductive and catalytic amination, (Sajiki et al. 2004) metal initiated amination of
alkenes, alkynes and aryl halides, (Okano et al. 2003) deamination of quaternary hydrazinium
halides and reduction of N-tosylamidines, have been devised for alkylation.
Unsymmetrical tertiary amines have been obtained in a single step through the CuCl/B(OMe)3
catalysed reaction of primary amines, alkyl halides and ?-chlorine-substituted allylsilanes.
Synthesis of tertiary amines using a palladium-catalysed nucleophilic substitution of benzylic
esters and secondary amines has been reported (Kuwano et al. 2003).
Figure 2.3 Alkylation of aminated polystyrene
2.2 Application of functionalized polystyrene
Functionalized polystyrene has many applications in the field of Chemistry. Some of the most
significant applications include use as a stationary phase in chromatography and as an adsorbent
for removal of organic and inorganic compounds in aqueous media.
2.2.1 Application as stationary phase in chromatography
The majority of stationary phases currently used for separation of ionic compounds are based on
organic polymers and silica gel. In contrast to stationary phases prepared on silica gel, organic
polymers show higher stability towards extreme pH conditions. The silica-based anion
exchangers (Matsushita, Tada, Baba ; Osako 1983), (Vydac 1991) can be operated only in pH
range between 2.0–9.5 while polymeric ion exchangers are stable across the entire pH range.
Thus, styrene/divinylbenzene (PS/DVB) copolymers (Weiss ; Jensen 2003), (Gawdzik, Matynia
; Osypiuk 1998) polyvinyl and polymethacrylate resin are the most important organic polymers
used as materials in the manufacturing process for polymer-based anion exchangers.
Bocian, Kosobucki ; Gawdzik (2011) described the synthesis and properties of the multilayered
stationary phases, which contain quaternary amine functional groups for the analysis of anions
by ion chromatography. They worked on the separation of an inorganic anions sample (F–, Cl?,
NO2? Br?, NO3?, additionally HPO42? and SO42?).
2.2.2 Application as an adsorbent for removal of organic and inorganic compounds from
Zhang et al. (2008) did a comparative investigation for uptake of dissolved organic matter
(DOM). They did their investigation on refractory dissolved organic matter (DOM) from land?ll
leachate treatment plant with high dissolved organic carbon (DOC) content. An aminated
polymeric adsorbent NDA-8 with tertiary amino groups was synthesized, which exhibited high
adsorption capacity to the DOM (raw water after coagulation). In their findings resin NDA-8
performed better in the uptake of the DOM than resin DAX-8 and A100 which are commercial
Electrostatic attraction was considered as the decisive interaction between the adsorbent and
adsorbate. Special attention was paid to the correlation between porous structure and adsorption
capacity. The mesopore of NDA-8 played a crucial role during uptake of the DOM. In general,
resin in chloride form performed a higher removal rate of DOC. According to the column
adsorption test, total adsorption capacity of NDA-8 was calculated to 52.28 mg DOC/mL wet
resin. 0.2 mol/L sodium hydroxide solution could regenerate the adsorbent e?ciently.
Zhang et al. (2009) worked on removal of aromatic sulphonates from aqueous solution by
aminated polymeric sorbents. They worked on sorption of aromatic sulphonates onto two
aminated polystyrene sorbents with different pore structures M-101 and D-301 was investigated
for optimization of their potential in application in chemical waste water treatment.
Sodium benzene BS, sodium 2 naphthalene sulphonate 2- NS and disodium 2,6 naphthalene
disulphonate 2,6 NDS were selected as reference solutes and sodium disulphate was used as a
competitive inorganic salt. Sorption selectivity of both sorbents was dependent upon the
concentration levels of aromatic sulphonates in solution coexisting with sodium sulphate at high
levels. Their findings showed that both sorbents exhibited different characters. D-301 presented
more favourable sorption for the solutes at relatively high levels (higher than 5 mM 0.7 mM for
2-NS and 0.05 mM for 2.6 NS, while M-101emoved aromatic sulfonates more completely when
the solute concentration was kept at relatively low levels.
2.3 Characterization of functionalized polystyrene adsorbent.
The functionalized polystyrene is characterized using various techniques which include FTIR,
XRD, BET and SEM.
FTIR is one of the most widely used tools for the detection of functional groups in pure
compounds and mixtures and for compound comparison. Infrared study is related to the
vibrational motion of atoms or molecules.
This study is mainly used for structure elucidation in organic and inorganic compounds. These
compounds absorb electromagnetic energy in the infrared region of the spectrum. IR radiation
does not have sufficient energy to cause the excitation of electrons. However, it causes atoms or
group of atoms to vibrate faster about the bonds, which connect them. The compounds absorb
energy from a particular region since the vibrations are quantized. The position of a particular
absorption band is specified by a particular wave number (Tourintio et al, 1998).
Shyaa (2012) worked on synthesis, characterization and thermal study of polyimides derived
from polystyrene. Infrared (FTIR) spectra and thermo gravimetric analysis (TGA) were used to
characterize polymers. The chemical structure of poly(4nitro styrene) was analysed by FTIR
analysis which confirmed the nitration of polystyrene.
There finding were as the vibration band at 3107 cm-1 attributed for aromatic C-H stretching, the
band at 2854 cm-1 for aliphatic C-H stretching, 1597, 1518 cm-1 for asymmetric (ArNO2) N=O
stretching, 1390 cm-1 for symmetric stretching N=O, 1329 cm-1 for C-N stretching. The
polyaminostyrene was analysed by FT-IR, there were two bands, the asymmetrical N- H stretch
and symmetrical N-H stretch, located at 3323, 3215 cm-1. The N-H bending vibration for primary
amines was observed in the region 1618, 1583 cm-1. The C-N stretching vibration for aromatic
amines was observed in the region 1315 -1273 cm-1.
Sun et al. (2014) determined the microstructure and mechanical properties of aminated
polystyrene spheres / epoxy polymer blends. In their research polystyrene spheres were chosen
as soft fillers to toughen epoxy polymer. In order to weaken the aggregation of polystyrene
spheres in epoxy matrix caused by phase separation, amination treatment was firstly done on
them. They reported that FTIR was employed to distinguish the difference between native
polystyrene spheres and aminated polystyrene spheres.
The FTIR test displayed a spectral profile characterized by the presence of specific bands related
to polystyrene. Their findings were, at 3024cm-1 (-CH aromatic) and 2847 cm-1 (-CH2), 1600 cm-
1 (-C-C) aromatic, 1492-1451 cm-1 (-C6H5 in plane), 1200-1100 cm-1 (=C-H aromatic, out of
plane) 900-600cm-1 (=C-H aromatic in plane). Compared with the FTIR spectra of polystyrene
sphere, new peaks at 3420 cm-1, 3323 cm-1, 3215 cm-1 and 1613 cm-1 were observed on that of
aminated polystyrene spheres. There were typical peaks of N-H stretching and bending modes in
primary amines (Covolan et al. 2000). The disappeared peak 1830 cm –1 indicated that the amine
substitution reaction occurs on the para orienting of the polystyrene.
Figure 2.4 Comparison of FTIR spectrum for aminated polystyrene and polystyrene (Covolan et
X-ray powder diffraction (XRD) is a rapid analytical technique primarily used for phase
identification of a crystalline material and can provide information on unit cell dimensions. The
analysed material is finely ground, homogenized, and average bulk composition is determined.
X-ray powder diffraction is most widely used for the identification of unknown crystalline
materials. Determination of unknown solids is critical to studies in geology, environmental
science, material science, engineering and biology. Other applications include, characterization
of crystalline materials, identification of fine grained minerals such as clays and mixed layer
clays that are difficult to determine and optically determination of unit cell dimensions
measurement of sample purity (Khondker1 ; Lakhani 2015).
XRD technique offers the following advantages its powerful and rapid ( 1, the
adsorption is not favourable, the adsorption connections become weak and the adsorption
capacity decreases. The value of 1/n was less than one (Table 4.2), this revealed favourable
adsorption conditions. The correlation coefficient value was 0.9806 which is less than the
Langmuir value. Therefore, adsorption does not fit well to Freundlich isotherm . These findings
were in line with those of (Gammoudi ; Srasra 2012) who worked on nitrate sorption by
Table 4.2 Freundlich parameters for adsorption of nitrate ions onto AAP
KF N 1/n R2
18.373 1.862891 0.5368 0.9806
Fig 4.9 Freundlich isotherm linear plot for the adsorption of nitrate ions
4.3.3 Temkin isotherm
A plot of qe againist ?n C? is shown in figure 4.10. The plot gives constants B and KT
from the slope and the intercept respectively. The data did not show a good fit to the
Temkin isotherm model compared to the Langmuir isotherm, based on the fact that the R2
value was 0.933. The same results were obtained by (Liao et al. 2010) using carbonate
hydroxyapatite extracted from egg shell as an as an adsorbent. The adsorption parameters
for this study are given in table 4.3.
y = 0.5368x + 1.2642
R² = 0.9806
Table 4.3.Temkin parameters for adsorption of nitrate ions on AAP
B KT R2
25.27 1.4586 0.9333
Fig 4.10 Temkin isotherm linear plot for the adsorption of nitrate ions.
4.4 Results for characterization of functionalized polystyrene by FTIR
4.4.1 Results for characterization of polystyrene by FTIR
The chemical structure of polystyrene was analyzed by FT-IR analysis in figure 4.11.The
y = 25.27x + 9.5396
R² = 0.933
FTIR, spectra displayed a spectral profile characterized by presence of specific peaks at
3023 cm-1, (-CH aromatic) and 2918 and 2840 cm-1 (-CH2), 1600 cm-1 (-C-C) aromatic,
1491 cm-1 (C6H5 in plane), 1451 cm-1 (-C6H5 in plane), 1100 cm-1 (=CH aromatic, out of
plane) 694 cm-1 (-CH- aromatic. These results are in line with the findings of (Covolan et
Figure 4.11 FTIR spectrum of pure polystyrene
4.4.2 Results for characterization of nitrated polystyrene by FTIR
The chemical structure of polynitrostyrene was analyzed by FT-IR analysis which
confirmed the nitration of polystyrene as shown in figure 4.12. The new peaks at 1518
cm-1 for asymmetric (C6H5NO2) N=O stretching, 1342 cm-1 for symmetric stretching
N=O, and 1200 cm-1 for C-N stretching. These results were in line with those of (Shyaa
Figure 4.12 FTIR spectrum for nitrated polystyrene
4.4.3 Results for characterization of aminated polystyrene by FTIR
The polyaminostyrene FTIR spectrum is shown figure 4.13. There is a broad band at 3340 cm-1
which is typical of the N-H stretching in primary amines. The N-H bending vibration for primary
amines is observed at 1602 cm-1.
Figure 4.13 FTIR spectrum for aminated polystyrene
4.4.4 Results for characterization of amino alkylated polystyrene
The FTIR for amino alkylated polystyrene is shown in figure 4.14. The peak at 1056 cm-1 is
responsible for the C-N (N-CH3) stretch in amino alkylated polystyrene. The peak around 3000
cm-1 is for the –CH3 group. Tetiary amines do not show any bond in the region 3300 -3000 cm-1
since they do not have an N-H (Xiong ; Yao 2009).
Figure 4.14 FTIR spectrum of amino alkylated polystyrene
CHAPTER 5: CONCLUSION AND RECOMMENDATIONS
This study investigated the adsorption characteristics and suitability of AAP as potential
adsorbent for the removal of nitrate from aqueous solutions using batch technique. The results
showed that this clay could be used as potential sorbent and it was highly effective as low cost
adsorbent for the removal of nitrates ions from aqueous solutions. The batch study parameters,
pH of solution, mass of adsorbent, initial solution concentration, contact time and temperature
were found to be effective on the adsorption processes. The adsorption equilibrium was attained
within 3 hours.. The percentage removal was found to decrease with increase in pH. The increase
in adsorbent dosage increased the percent removal of nitrate due to the increase in adsorbent
surface area in adsorbent dosage. The equilibrium data fitted well the Langmuir isotherm
equation and this adsorbent showed large uptake capacity of nitrate Q max,exp = 81 mg/g). AAP
adsorbent proved to be a highly efficient adsorbent for remediation of nitrate contaminated water
owing to its exceptional uptake capacity as well as high selectivity for this anionic contaminant.
The recommendations for this study are
? Various anions beside nitrate ions should also be analysed to maximise the use of the
? Studies on application of the beads on real environmental samples are required
? Use of the adsorbent as a anion preconcetration method is also required
Abadie, M. J. M., Voytekunas V. Y. ; Rusanov, A. L. (2006) State of the Art organic matrices
for high-performance composites. Polymer Journal, 15, (1), 65-77.
Ahmaruzzaman, M. ;. Sharma, D.K. (2005) Adsorption of phenols from wastewater. Journal of
Colloid and Interface Science, 287, (1), 14-24.
Aksu, Z. ; Kabasakal, E. (2004) Batch adsorption of 2,4-dichlorophenoxyacetic acid (2,4-D)
from aqueous solution by granular activated carbon. Separation and Purification Technology, 35,
Alexandratos, S. D., Natesan, S.,(1999) Ion selective polymer-supported reagents: the principle
of bifunctionality. European Polymer Journal, 35(3) 431–436.
Alexiades, C.A. ; Mitrakas, M.G. (1990) A New IonicStrengthAdjustor for Nitrate Analysis in
Waters, Soils and Plants Using Ion-Selective Electrode. Mikrochim Acta, 1, 7-16.
Arief, V. O., Trilestari K., Sunarso, J., Indraswati N. ; Ismadji, S. (2008) Recent progress on
biosorption of heavy metals from liquids using low cost biosorbents: Characterization,
biosorption parameters and mechanism studies: a review. Clean, 36, 937-962.
Arló, L.A., Beretta, A. ; Perdomo, C.H. 2015 A Quick Test Based on Cataldo’s Method to
Determine Nitrate in Fresh Tissue Extracts. Journal of Plant Nutrition 38 (1), 1- 1.
Auta, M. & Hameed, B.H. (2011) Preparation of waste tea activated carbon using potassium
acetate as an activating agent for adsorption of Acid Blue 25 dye. Chemical Engineering
Babel, S. & Kurniawan, T.A (2003) Various treatment technologies to remove arsenic and
carbon for the removal of copper, zinc, chromium and mercury from contaminated groundwater:
an overview. Journal of Hazard Mater, 166, 433-440.
Badea, M., Amine, A., Palleschi, G., Moscone, D., Volpe, G. & Curulli, A. (2001) New
electrochemical sensors for detection of nitrites and nitrates. Journal of Electroanalytical
Chemistry 50, (9), 66–72.
Baes, B.U., Jung, Y.H., Han, W.W. & Shin, H.S. (2002) Improved Brine Recycling during
Nitrate Removal Using Ion Exchange. Water Research, 36, 3330-3340.
Bhatnagar, A. & Sillanpaa M. A. (2011) Review of emerging adsorbents for nitrate removal from
water. Chemical Engineering Journal. 168, (2), 493-504.
Bocian, M., Jackowska, S., Kosobucki, P. & Gawdzik, B. (2011) Functionalized polymeric
stationary phases for ion chromatography. Journal of chromatography, 34, (6), 601–608.
Cai, J. G., Li, A. M, Shi, H. Y., Fei, Z. H., Long, C. & Zhang, Q. X. (2005) Equilibrium and
kinetic studies on the adsorption of aniline compounds from aqueous phase onto bifunctional
polymeric adsorbent with sulfonic groups. Chemosphere, 61, (4), 502–509.
Chatterjee, S & Woo, S.H. (2009) The Removal of Nitrate from Aqueous Solutions by Chitosan
Hydrogel Beads. Journal of Hazardous Materials, 164, 1012-1018.
Chen, Y. N., Chai, L. Y. & Shu Y. D. (2008) Study of arsenic (V) adsorption on bone char from
aqueous solution. Journal of Hazardous materials, 160, 168-172.
Cheremisinoff, P. N. & Morresi, A.C. (1978) Carbon adsorption Handbook. Borought Green, 1-
Chiban, M., Soudani, A., Sinan F. & Persin M. (2011) Single, binary and multi-component
adsorption of some anions and actions on Cedulis plant particles. Colloids Surface B, 82, 267-
Chingakham, B. Singh, V. K., Akshaya K., Samal, A. & Bhisma K. P. (2007) Aqueous-Mediated
N-Alkylation of Amines. Journal of Organic Chemistry, 8, 1369–1377
Chou, S., Chung, J. & Hwang, D. (2003) A High Performance Liquid Chromatography Method
for Determining Nitrate and Nitrite Levels in Vegetables. Journal of Food and Drug Analysis,
11, (3), 233-238.
Covolan, V. L., Antone, S., Ruggeri, G. & Chiellini, E. (2000) Preparation of aminated
polystyrene latexes by dispersion polymerization, Macromolecules 33, (18), 6685-92
Dabrowski, A. (2001) Adsorption from theory to practice. Advances in Colloid and Interface
Science, 93, 135-224.
Dayananda, B. P. & Revanasiddappa H. D. (2007) Determination of nitrites by the formation of
biazo dye. Chemical papers, 61, (6) 446-451.
Elmoubarki, R., Mahjoubi, F.Z., Tounsadi, H., Moustadraf, J., Abdennouri, M., Zouhri, A.,
ElAlbani, A. & Barka, N. (2015) Adsorption of Textile Dyes on Raw and Decanted Moroccan
Clays: Kinetics, Equilibrium and Thermodynamics. Water Resources and Industry, 9, 16-29.
Febrianto, J., Kosasih, A. N., Sunarso, J., Ju, Y., Indraswati, N. & Ismadji, S. (2009)
Equilibrium and kinetic studies in adsorption of heavy metals using biosorbent: A summary of
recent studies. Journal of Hazardous Materials, 162, (2-3), 616-645.
Fewtrell, L. (2004) Drinking water nitrate, methemoglobinemia, and global burden of disease: a
discussion. Environmental Health Perspectives, 14, (112), 1371–1374.
Frant, M. S. (1994) History of the Early Commercialization of Ion-Selective Electrodes. Analyst,
Freundlich, H. (1906) Adsorption in solutions. Zeitschrift Physical Chemistry, 57, 385-470.
Gammoudi, S., Srasra, N. F. & Srasra, E. (2012) Nitrate Sorption by Organosmectites.
Engineering Geology, 124, 119-129.
Gawdzik, B. & Matynia, T.O. (1998) Porous copolymer of the methacrylic ester of
dihydroxydiphenylmethane diglycidyl ether and divinylbenzene as an HPLC packing. Journal of
Chromatographia, 47, 509–514.
Greer, R. & Shannon, M. (2005) Infant methemoglobinemia: the role of dietary nitrate in food
and water. Pediatrics, 116, (3), 784–786.
Guo, H. C., Liu, L., Huang, S. H., Fuller, S. A. & Yim, Y. (2001) System dynamics approach for
regional environmental planning and management: A study for the Lake Erhai Basin. Journal of
Environmental Management, 61, (1), 93-111.
Gupta, V. & Ali, I. (2000) Utilisation of Bagasse fly ash (a sugary industry waste) for removal of
copper, and zinc from wastewater. Separation and purification Technology, 8, 131-140.
Haghseresht, F., Nouri, S. &. Lu, G. Q. M. (2003) Effects of carbon surface chemistry and
solution pH on the adsorption of binary aromatic solutes. Carbon, 41, (5), 881-892.
Han, R., Lu, L., Zou, W., Daotong, W., Shi, J. & Jiujun, Y. (2006) Removal of copper(II) and
lead(II) from aqueous solution by manganese oxide coated sand. Journal of Hazardous
Material, 137, (1) 480-488
Hayat, A., Rahman, M. I., Choudhary, K. M., Khan, W., Schumann, E. & Bayer, E (2001) N-
alkylation of anilines, carboxamides and several nitrogen heterocycles using CsF-celite/alkyl
halides/CH3CN combination. Tetrahedron, 57, (50) 9951.
Hell, F., Lahnsteiner, J., Frischherz, H & Baumgartner, G. (1998) Experience with full-scale
electrodialysis for nitrate and hardness removal, Desalination,117, (1–3), 173–180.
Hoda, N., Bayram, E. & Ayranci, E. (2006) Kinetic and Equilibrium Studies on the Removal of
Acid Dyes from Aqueous Solutions by Adsorption onto Activated Carbon Cloth. Journal of
Hazardous Materials, 137, (1), 344-351.
Horita, K. & Satake, M. (1997) Column preconcentration analysis spectrophotometric
determination of nitrate and nitrite by a diazotization–coupling reaction. Analyst, 122 (12) 1569-
Hu, H. Y., Goto, N. & Fujie, K. (2001) Effect of pH on the Reduction of Nitrite in Water by
Metallic Iron. Water Research, 35, (11), 2789-2793.
Huang, J., Huanh, K., Liu, Q. & Luo, M. (2007) Adsorption properties of tea polyphenols onto
three polymeric adsorbents with amide group, Journal of Colloid Interface Science, 315 (2) 407-
Islam, M. & Patel, R. (2011) Physicochemical Characterization and Adsorption Behaviour of
Ca/Al Chloride Hydrotalcite Like Compound towards Removal of Nitrate. Journal of Hazardous
Materials, 190, 659-668.
Jeong, J. Y., Kim, H. K., Kim, J. H. & Park, J.Y. (2012) Electrochemical Removal of Nitrate
Using ZVI Packed Bed Bipolar Electrolytic Cell. Chemosphere, 89, (2), 172-178.
Jiang, C. Cooper, S. Ouki, Comparison of Modified Montmorillonite Adsorbents. Part I:
Preparation, Characterization and Phenol Adsorption. Chemosphere,Chemosphere 47 (7) (2002),
Khondker, A. & Lakhani, S. (2015) X-Ray Diffraction: A Comprehensive Explanation for
Multipurpose Research International. Journal of Interdisciplinary Research and Innovations,
3, (1), 60-64.
Kostraba, T.N., Gay, E.C., Rewers, M. & Hamman, R.F. (1992) Nitrate Levels in Community
Drinking Waters and Risk of IDDM, An Ecological Analysis. Diabetes Care, 15, 1505-1508.
Kross, B. C., Ayebo, A. D. & Fuortes, L. J. (1992) Methemoglobinemia: nitrate toxicity in
rural America. American Family Physician, 46, (1), 183–188.
Kumar, P.S. & Kirthika, K. (2009) Equilibrium and kinetic study of adsorption of nickel from
aqueous solution onto bael tree leaf powder. Journal of Engineering Science and Technology, 4,
Kumar, U. & Bandyopadhyay, M. (2006) Sorption of cadmium from aqueous solution using
pretreated rice husk. Bioresource Technology, 97, 104-109.
Kuwano, R., Kondo, R. & Matsuyama, Y. (2003) The Chemistry of Amidines and Imidates.
Journal American Chemical Society, 125, (40), 12104-12105.
Langmuir, I. (1918) The adsorption of gases on plane surfaces of glass, mica and platinum.
Journal of the American Chemical Society, 40, (9), 1361-1403.
Lata, H., Garg, V. K. & Gupta, R. K. (2007) Removal of Sources of a basic dye from aqueous
solution by adsorption waste. Dyes and Pigments, 74, (3), 653-658.
Lawal, O. S., Sanni, A. R., Ajayi, I. & Rabiu, O., (2010) Equilibrium thermodynamic and
kinetic studies for the biosorption of aqueous lead (II) ions onto the seed husk of Calophyllum
inophyllum. Journal of Harzadous Materials, 177, 829-835.
Lawal, O., Sanni, A, R., Ajayi, I. & Rabiu, O. O. (2010) Equilibria thermodynamic and kinetic
studies for the biosorption of aqeous (II) ions with onto the seed husk of Calophyllum
inophylum. Journal of Hazardous Material, 177, 829-835.
Li, A .M., Zhang, Q. X., Wu., H. S., Zhai, Z, C., Liu, F. Q. & Fei, Z. H. (2004) A new amine-
modi?ed hypercrosslinked polymeric adsorbent for removing phenolic compounds from aqueous
solutions. Adsorption Science & Technology, 22,(10), 807–819.
Liao, D., Xu, X. & Yan., (2008) Kinetic studies for biosorption of lead and copper ions by
Penicillium simplicissimum immobilized with within loofa sponge. Journal of Hazardous
Material, 159, 610-615
Lin, S.H. & Wu, C.L. (1996) Removal of Nitrogenous Compounds from Aqueous Solution by
Ozonation and Ion Exchange. Water Research, 30, 1851-1857
Liu, A. Ming, J. & Ankumah, R. O. (2005) Nitrate contamination in private wells in rural
Alabama, United States. Science of the Total Environment, 346, (1–3), 112–120.
Lober, S. & Gmeiner, P. (2004) An efficient and operationally convenient general synthesis of
tertiary amines by direct alkylation of secondary amines with alkyl halides in the presence of
Huenig’s base. Tetrahedron, 60, 8699 – 8792.
Majumdar, D. ; Gupta, N. (2000) Nitrate pollution of groundwater and associated human health
disorders. Indian Journal of Environmental Health, 42, (1), 28–39.
Matsushita, S., Tada., Y, Baba, N. ; Osako, K. (1983) Functionalized anion exchange stationary
phase for separation of anionic compounds. Journal of Chromatography 259, 459–464.
Merusi, C., Corradini, C., Cavazza, A., Borromei, C. ; Salvadeo, P. (2010) Determination of
nitrates, nitrites and oxalates in food products by capillary electrophoresis with pH-dependent
electroosmotic flow reversal. Food Chemistry, 120, 615-620.
Ming, Z.W., Long, C. J., Cai, P.R. ; Zin, X. Q. (2006) Synergistic adsorption of phenol from
aqueous solution onto polymeric adsorbents. Journal of Hazardous Material, 128, 123-129.
Monser, L. ; Adhoum, N. (2002) Modified activated carbon for the removal of copper, zinc,
chromium and cyanide from wastewater. Separation and Purification Technology, 26, (2-3) 137-
Moore, J. L., Taylor, S., Soloshonok, V. ; Arkivoc, A. (2005) The synthesis of amines with
alkylhalides. Organic Letters (6) 287-289.
Moussavi, G. ; Khosravi, R. (2011) The Removal of Cationic Dyes from Aqueous Solutions by
Adsorption onto Pistachio Hull Waste. Chemical Engineering Research and Design, 89, 2182-
Nataraj, S. K., Hosamani, K. M. ; Aminabhavi, T. M. (2006) Electrodialytic removal of nitrates
and hardness from simulated mixtures using ion-exchange membranes. Journal of Applied
Polymer Science, 99, (4), 1788–1794.
Nuhoglu, A., Pekdemir, T., Yildiz, E., Keskinler, B., ; Akay, G. (2002) Drinking water
denitrification by a membrane bio-reactor. Water Research, 36, (5), 1155–1166,
Okano, K., Tokuyama, H. ; Fukuyama, T. (2003) Synthesis of secondary arylamines through
copper-mediated intermolecular aryl amination. Organic Letters, 5, (26), 4987-4990
Olsen, C. A., Witt, M., Joraszewski, J. W. ; Franzyk, H. (2003) Solid-phase polyamine
synthesis using piperazine and piperidine building blocks. Organic Letters, 5, (26), 4183-4185
Orion Research, Inc. (1997). http://www.orionres.com/
Pan B C, Zhang Q, Meng F W, Li X T, Zhang X, Zheng J Z et al., 2005. Sorption enhancement
of aromatic sulfonates onto an aminated hyper-cross-linked polymer. Environmental Science ;
Technology, 39(9): 3308–3313
Pan, B.C., Xiong, Y., Su, Q., Li, A. M. ; Chen, A.L. (2003) Role of amination of polymeric
adsorbent on phenol adsorption from aqueous solutions. Chemosphere, 51, 953-962.
Pan, Bi., Zhang Q., Pan Bi., Zhang W., Du W., ; Ren H. (2008) Removal of aromatic sulfonates
from aqueous media by aminated by polymeric sorbents. Microporous and Mesoporous
Materials, 116, 63-69.
Perez, O. R., Gabiola, X. ; Hurtado, J.M. (2013) Sequential Potentiometric determination of
Nitrate and Chloride in Vegetables, Chemistry Journal 3, (3), 81-85.
Philippides. A., Budd, P., M. P. ; Colin, P. (1993) The nitration of polystyrene. International
Journal of Scientific ; Engineering Research, 34, (16) 3509-3513.
Qingshan, Y., Sándor, B., ; George, H. (1999) Microstructure of ion selective plasticized PVC
membranes studied by small angle neutron scattering. Analytical Chemistry 71, (19), 4313-4320.
Rassaf, T., Kleinbangard, P. ; Kelm, M.(2006) The Larginine nitric oxide pathway: Avenue
for a multiple level approach to assess vascular function’, Biological Chemistry 387, (10-
Rijn, J. V., Tal, Y. & Schreier, H. J. (2006) Denitrification in recirculating systems: theory and
applications. Aquaculture Engineering, 34, (3), 364-376.
Romano, N. & Zeng, C. (2009) Evaluating the Newly Proposed Protocol of Incorporated
Potassium in Nitrate Toxicity Experiments at Different Salinities: A Case Study with the Tiger
Prawn, Penaeus monodon, Juveniles. Aquaculture, 289, 304-309.
Rupert, M. G. (2008) Decadal-scale changes of nitrate in ground water of the United States,
Journal of Environmental Quality, 37 (5), S240–S248.
Sajiki, H., Ikawa, T., & Hirota, K., (2004) Catalytic hydrogenation in organic synthesis Organic
Letters, 6, (26), 4977 -4980.
Salvatore, R. N., Nagle, A. S. & Jung K. W. (2002) Cesium Effect in Direct N-Alkylation of
Amines. Journal Organic Chemistry, 67, (3), 674. 674-683.
Samatya, S., Kabay, N., Yuksel, U., Mand. A. & Yuksel, M. (2006) Removal of nitrate from
aqueous solution by nitrate selective ion exchange resins, Reactive and Functional Polymers,
66, (11), 1206–1214.
Shrimali, M. & Singh, K. P. (2001) New methods of nitrate removal from water. Environmental
Pollution. 112, 351-359.
Shyaa, A, A. (2012) Synthesis, Characterization and Thermal Study of Polyimides Derived from
Polystyrene. Journal of University of Anbar for Pure Science, 6, (1), 21-27.
Somdutta, S., Ujjaini, S., Sourav, M. & Sudeshna, S. (2012) Trranscient behaviour of packed
column of water hyacinth stem for the removal of hexavalent chromium. Desallination, 297, 48
Stern, M. K., & Cheng, B. K. (1993) Amination of Nitrobenzene via Nucleophilic Aromatic
Substitution for Hydrogen: Direct Formation of Aromatic Amide Bonds, Journal of Organic
Chemistry. 58, 6883-6888.
Sun, T., Zhanjun, W., Qin, Z., Xin, L., Zhi, W. & Hongyu, F. (2014) Microstructure and
mechanical properties of aminated polystyrene spheres/epoxy polymer blends. Composites:Part
A, 66, 58-64
Thomson, T.S. (2001) Nitrate Concentration in Private Rural Drinking Water Supplies in
Saskatchewan Canada. Bulletin of Environmental Contamination and Toxicology, 66, 64-70.
Tourintio, F.A., Depeyrot, J., Da Silva, G.J & Lara MC.L. (1998). Protective measurement and
quantum reality. Journal of Physics, 28, 413-420
Tremblay-Morin, S., Raeppel, F. & Gaudett, T. (2004) The use of potassium alkynyl
trifluoroborates in Petasis borono-Mannich reaction. Tetrahedron Letters, 45, (17) 3471-3478
Tsai, W.T., Chang, Y. M., Lai, C. W. & Lo, C.C. (2005) Adsorption of Basic Dyes in Aqueous
Solution by Clay Adsorbent from Regenerated Bleaching Earth. Applied Clay Science, 29, 149-
Vera, Z., Zoltan P., Stefar, A., (2002) Determination of nitrate and nitrite by high-performance
liquid chromatography in human plasma. Journal of chromatography 780, (1), 193-197.
Vimonses, V., Lei, S., Jin, B., Chow, C.W.K. & Saint, C. (2009) Adsorption of Congo Red by
Three Australian Kaolins. Applied Clay Science, 43, 465-472.
Vydac HPLC columns and separation materials. The separation groups, Hesperia, 1990–1991,
pp. 20–23 (15)
Wang, G. F., Satake, M. & Horita, K. (1998) Spectrophotometric determination of nitrate and
nitrite in water and some fruit samples using column preconcentration. Talanta, 46, (4), 671-678.
Wang, X. J, Zhang, Q. X., Zhao, J. F., Xia, S. Q. & Chen, L. (2005) Adsorption of phenolic acids
on a new type of amino modi?ed polystyrene. Acta Polymerica Sinica, 1, 93–97
Wang, Y., Gao B. Y., Yue W. W. & Yue, Q. Y. (2007) Adsorption kinetics of nitrate from
aqueous solutions onto modified wheat residue. Colloid and Surfaces A, 308, (3), 1-5.
Wang, Z. & Li, S. (2004) Effects of Nitrogen and Phosphorus Fertilization on Plant Growth and
Nitrate Accumulation in Vegetables. Journal of Plant Nutrition, 27,(3), 539-556.
Ward, M. H., Dekok, T. M. & Levallois, P. (2005) Workgroup report: drinking water nitrate
and health recent findings and research needs. Environmental Health Perspectives, 113, (11)
Ward, M. H., Dekok, T. M., Levallois, P., Brender, J., Gulis, G., Nolan, B.T. & Van Derslice, J.
(2005) Drinking-Water Nitrate and Health Recent Findings and Research Needs. Environmental
Health Perspectives, 113, 1607-1614.
Weiss, J. & Jensen, D. (2003) Novel ion chromatographic stationary phases for the analysis of
complex matrices. Analalytical and Bioanalytical Chemisty, 375, 81–98.
WHO, Guidelines for drinking water quality. Fluoride,World Health Organization, 2001.
(http://www.who.int/water sanitation 1th/GDWQ/ Chemicals/?uoridefull/html).
Wolfe, A. H. & Patz, J. A. (2002) Reactive Nitrogen and Human Health: Acute and Long-Term
Implications. A Journal of the Human Environment, 31, 120-125.
Xiong, C. & Yao, C. (2009) Synthesis, characterization and application of triethylenetetramine
modified polystyrene resin in removal of mercury, cadmium and lead from aqueous solutions,
Chemical Engineering Journal, 155, (3), 844–850.
Yadla, S.V., Sridevei, V. & Chandana, M.V.V. (2012) Adsorption performance of fly ash for the
removal of lead. International Journal of Engineering Research & Technology, 1, (7), 143-149
Zhang, L., Du, Q., Pan, B. & Hong, C. (2009) Adsorption egilibrium and heat of phenolonto
aminated polymeric resins from aqueous solution. Colloid and Surfaces, 346, 34-38.
Zhang, L., LI, A., Wang, J., Lu Y. & Zhou Y. (2009) A novel aminated polymeric adsorbent for
removing refractory dissolved organic matter from land?ll leachate treatment plant. Journal of
Environmental Sciences, 21, 1089–1095.
Zhang, W.M., Xu, Z. W., Pan, B.C., Zhang, Q. J., Du, W. & Zheng, K. (2007) Adsorption
enhancement of laterally interacting phenol/ aniline mixtures onto non polar adsorbents,
Chemosphere, 66, 2044-2049.
Zheng, Y. & Wang, A. (2010) Nitrate Adsorption Using Poly(dimethyl diallyl ammonium
chloride)/polyacrylamide hydrogel. Journal of Chemical & Engineering Data, 55, 3494-3500.
Zhou, M., Fu, W., Gu, H. and Lei, L. (2007) Nitrate Removal from Groundwater by a Novel
Three-Dimensional Eletrode Biofilm Reactor. Electrochimica Acta, 52, 6052-6059