Chemical Engineering Journal 168 (2011) 493–504

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Chemical Engineering Journal

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Review

A review of emerging adsorbents for nitrate removal from water

Amit Bhatnagar a,∗ , Mika Sillanpää b
a
LSRE–Laboratory of Separation and Reaction Engineering, Departamento de Engenharia Química, Faculdade de Engenharia da Universidade do Porto (FEUP),
Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
b
Faculty of Technology, Lappeenranta University of Technology, Patteristonkatu 1, FI-50100, Mikkeli, Finland

a r t i c l e i n f o a b s t r a c t

Article history: Nitrate, due to its high water solubility, is possibly the most widespread groundwater contaminant in
Received 21 November 2010 the world, imposing a serious threat to human health and contributing to eutrophication. Among several
Received in revised form 23 January 2011 treatment technologies applied for nitrate removal, adsorption has been explored widely and offers
Accepted 26 January 2011
satisfactory results especially with mineral-based and/or surface modified adsorbents. In this review, an
extensive list of various sorbents from the literature has been compiled and their adsorption capacities
Keywords:
for nitrate removal as available in the literature are presented along with highlighting and discussing the
Water treatment
key advancement on the preparation of novel adsorbents tested for nitrate removal.
Anions
Nitrate removal © 2011 Elsevier B.V. All rights reserved.
Adsorbents
Sorption capacities

1. Introduction ication [6,7]. The presence of elevated concentrations of NO3 − in

In many parts of the world, groundwater serves as the sole
source of drinking water in rural communities and urban areas.
However, in recent years, increased industrial and agricultural
activities have resulted in the generation of toxic pollutants such
as inorganic anions, metal ions, synthetic organic chemicals which
have increased public concern about the quality of groundwaters.
Inorganic anions are of great importance since these are toxic and
harmful to humans and animals at very low concentrations (ppb).
As there are usually no organoleptic changes in drinking water
due to the presence of trace levels of toxic inorganic anions, it
is therefore possible that some of them may remain undetected,
thereby increasing the possible health risks [1]. A number of inor-
ganic anions have been found in potentially harmful concentrations
in numerous drinking water sources [1–4]. Of these, nitrate (NO3 − )
is of prime concern on a global scale. Nitrate is a naturally occur-
ring ion in the nitrogen cycle that is the stable form of N for
oxygenated systems. It can be reduced by microbial action into
nitrite (NO2 − ) or other forms. The NO2 − ion contains N in a rel-
atively unstable oxidation state. Chemical and biological processes
can further reduce nitrite to various compounds or oxidize it to
NO3 − .
Nitrate, due to its high water solubility [5], is possibly the most
widespread groundwater contaminant in the world, imposing a
serious threat to drinking water supplies and promoting eutroph-
∗ Corresponding author.
E-mail addresses: amit b10@yahoo.co.in, dr.amit10@gmail.com (A. Bhatnagar).
potable water has become a serious concern worldwide over the
recent decades [8–12]. The increase in NO3 − levels can be linked
to several kinds of human activities especially the intensive use
of fertilizers in agriculture, which have led to the higher NO3 −
contamination of ground and surface water sources [13]. Nitrate
does not readily bind to the soil causing it to be highly susceptible
to leaching. Point and non-point sources of NO3 − contamination
include agricultural and urban runoff, disposal of untreated sani-
tary and industrial wastes in unsafe manner, leakage from septic
systems, landfill leachate, animal manure, NOx air stripping waste
from air pollution control devices.
High NO3 − concentrations in drinking water sources can lead
to a potential risk to environment and public health. High NO3 −
concentrations are known to stimulate heavy algal growth thus
promoting the eutrophication in water bodies. After ingestion of
plants or water high in NO3 − , acute poisoning may occur within
30 min to 4 h in cattle. Thus, the problem occurs quickly and often
the cattle are observed to be normal one day and found dead the
next day [14]. An early symptom is salivation followed by frequent
urination. Soon after, the cattle exhibit difficult breathing, increased
respiratory rate, and dark brown or “chocolate” colored blood and
mucous membranes [15]. The animals then become weak, reluctant
to move, and have convulsions before they die [15]. If pregnant cat-
tle receive a dose that is not quite deadly, they may abort soon after
recovering [15].
In humans, increasing NO3 − concentrations in drinking water
causes two adverse health effects: induction of “blue-baby syn-
drome” (methemoglobinemia), especially in infants, and the
potential formation of carcinogenic nitrosamines [6,7]. Recent

1385-8947/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2011.01.103
494 A. Bhatnagar, M. Sillanpää / Chemical Engineering Journal 168 (2011) 493–504
Fig. 1. Comparison of some nitrate removal technologies.
studies [16 and references therein] have shown that excess NO3 −
in drinking water may also be responsible for causing diverse kinds
of cancers in humans. Ward et al. [17] 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 [18].
Literature survey revealed that NO3 − ion also causes diabetes [19]
and is a precursor of carcinogen.
Keeping with the view that serious health problems are asso-
ciated with excess NO3 − concentrations in drinking water, various
environmental regulatory agencies including the U.S. Environmen-
tal Protection Agency (U.S. EPA) have set a maximum contaminant
level (MCL) of 10 mg/L of NO3 − in drinking water [20]. Nitrate
contaminated water must be treated properly to meet applicable
regulations.
2. Technologies for the removal of nitrate from water
The most commonly used treatment methods to remove/reduce
NO3 − include chemical denitrification using zero-valent iron (Fe0 )
[21–25], zero-valent magnesium (Mg0 ) [26], ion exchange (IX)
[27–29], reverse osmosis (RO) [30], electrodialysis (ED) [31], cat-
alytic denitrification [32] and biological denitrification [33]. World
Health Organization (WHO) has suggested biological denitrifica-
tion and IX as nitrate removal methods, while IX, RO, and ED
are approved by US EPA as Best Available Technologies (BAT) to
treat NO3 − contaminated water [34,35]. However, current available
technologies for NO3 − removal have their own strength and limi-
tations and are found to be expensive, less effective and generate
additional by-products. Nevertheless, these traditional technolo-
gies do not solve the problem related to the excess of NO3 − in
the environment; in turn, they generate NO3 − concentrated waste
streams that pose a disposal problem due to the high saline con-
tent [33,36]. BATs are relatively expensive [31] and moreover, cause
process complexity to be used in in situ application for direct decon-
tamination of groundwater [37].
Zero-valent iron (ZVI) has been extensively studied for its ability
to reduce different contaminants including NO3 − in groundwater
[21,38–42]. However, this technology has some limitations as dis-
cussed by various researchers in different articles. For example,
Cheng et al. [21] reported that the main disadvantages of NO3 −
reduction using ZVI are ammonium production and the pH con-
trol requirement (by initial pH reduction or use of buffer). When
applying ZVI in an in situ remediation technique for NO3 − removal,
these disadvantages are more critical [43]. Furthermore, biological
denitrification processes are difficult to apply to inorganic wastew-
ater treatment because additional organic substrates are required
to serve as electron donors [44]. Fig. 1 presents an overview of some
of the technologies used for NO3 − removal from water [45,46].
3. Removal of nitrate from water using adsorption process
Adsorption process is generally considered better in water treat-
ment because of convenience, ease of operation and simplicity of
design. Further, this process can remove/minimize different types
of organic and inorganic pollutants from the water or wastewa-
ter [47–59] and thus it has a wider applicability in water pollution
control [60]. Adsorption technology has been found successful in
removing different types of inorganic anions, e.g., fluoride [61–63],
nitrate [64–66], bromate [67–69], perchlorate [70–72], from waters
by using various materials as adsorbents. It should be noted here
that selection of appropriate material for the removal of specific
types of anions is important to achieve optimum removal rates.
Various conventional and non-conventional materials from dif-
ferent origins have been assessed for the removal of NO3 − from
water, as will be discussed in the following sections in this paper.
However, no overview of the sorption potentials of the various con-
ventional and non-conventional adsorbents examined so far for
nitrate removal has been published.
 A. Bhatnagar, M. Sillanpää / Chemical Engineering Journal 168 (2011) 493–504
This review focuses on the potential of various adsorbents for
NO3 − removal from water and wastewater. A summary of rele-
vant published data (in terms of adsorption capacities, applicable
adsorption isotherm models and kinetic models) with some of the
latest important findings, and a source of up-to-date literature is
presented and the results have been discussed. For information
pertaining to detailed experimental methodology and conditions,
readers are referred to the full articles listed in the References.
3.1. Removal of nitrate from water by carbon based adsorbents
Activated carbon is generally considered as a universal adsor-
bent for the removal of diverse types of aquatic pollutants
especially organic pollutants. However, it shows poor adsorption
towards anionic pollutants. Only a few studies are available report-
ing the sorption of NO3 − by activated carbon. Afkhami et al. [73]
studied the effects of functional groups on the adsorption of NO3 −
and NO2 − by carbon cloth. The carbon cloths were chemically
etched in 4 M H2 SO4 solution after deionization cleaning proce-
dure and used for the adsorption of NO3 − and NO2 − from water
samples at nearly neutral (pH ∼ 7) solutions. It was suggested [73]
that treatment of carbon cloth with acid produced positive sites
on the carbon cloth, by protonation of surface –OH groups caused
an increase in electrostatic adsorption of anions. The dramatic
increase in the adsorption of anions by treatment of C-cloth with
acid was attributed to the strong electrostatic interaction between
the negative charge of anions and positive charge of the surface. The
adsorption capacity of acid treated carbon cloth for NO3 − and NO2 −
was 2.03 and 1.01 mmol/g, respectively. These values were much
higher than those obtained for distilled water treated carbon cloth
(0.38 and 0.05 mmol/g for NO3 − and NO2 − , respectively). The effect
of competing ions was found to be negligible on the adsorption.
Powdered activated carbon (PAC) and carbon nanotubes (CNTs)
were used for the removal of NO3 − from aqueous solution [74]. The
NO3 − adsorption capacity of CNTs was found to be higher than PAC
and decreased above pH 5. The equilibration time for maximum
NO3 − uptake was 60 min. Adsorption capacity of the PAC and CNTs
was found to be 10 and 25 mmol NO3 − /g adsorbent, respectively.
Commercial granular activated carbon (GAC) (produced from
coconut shells by steam activation) was chemically activated with
ZnCl2 and examined for NO3 − removal [75]. The optimal condi-
tions were selected by studying the influence of process variables
such as chemical ratio and activation temperature. Experimental
results reveal that chemical weight ratio of 200% and activation
temperature of 500 ◦ C was found to be optimum for the maximum
removal of nitrate from water. The lower adsorption of NO3 − with
GAC prepared at 400 ◦ C carbonization temperature was attributed
to the inadequacy of heat energy generated at low carbonization
temperature for any substantial evolution of volatile matters essen-
tial for pore development. Furthermore, at 500 ◦ C, more volatile
matters were released progressively during carbonization, thereby
resulting in the development of some new pores, and hence the
adsorption of NO3 − increased progressively. The decrease in the
adsorption of NO3 − with further increase in carbonization tempera-
ture to 600 ◦ C might be due to a sintering effect at high temperature,
followed by shrinkage of the char, and realignment of the carbon
structure, which resulted in reduced pore areas as well as volume.
The comparison between untreated and ZnCl2 treated GAC indi-
cated that treatment with ZnCl2 had significantly improved the
adsorption efficacy of untreated GAC. The adsorption capacity of
untreated and ZnCl2 treated coconut GACs were found to be 1.7 and
10.2 mg/g, respectively. The higher uptake of NO3 − in ZnCl2 treated
GAC was attributed to the increased microporosity and formation
of zinc oxide in macro- and mesopores in ZnCl2 treated GAC, which
resulted in the enhanced NO3 − adsorption. The adsorption behav-
ior of NO3 − was investigated from aqueous solution using activated
495
carbon (AC) prepared from coconut shells and charcoal (CB) pre-
pared from bamboo [76]. The maximum removal of NO3 − by the
prepared adsorbents occurred at equilibrium pH 2–4, and was fit-
ted well with Langmuir model. The adsorption capacity for AC and
CB were reported as 2.66 × 10−1 mmol/g and 1.04 × 10−1 mmol/g,
respectively.
The adsorption effectiveness of bamboo powder charcoal (BPC)
in removing NO3 − from water has been investigated [77]. The BPC
was prepared by heating the bamboo powder in an electric furnace
at 900 ◦ C for 1 h. The calculated uptake values of BPC and com-
mercial activated carbon (CAC) at 10 ◦ C were 1.25 and 1.09 mg/g,
respectively. The results show that the adsorption effectiveness of
BPC for NO3 − was higher than that of CAC regardless of the concen-
tration of NO3 − (0–10 mg/L), and temperature (10–20 ◦ C).
The adsorption of NO3 − including other inorganic anions
(bromate, chlorate, chloride, iodate, perchlorate, sulfate, and (di-
hydrogen) phosphate) was studied using activated carbon F400 at
pH 4 and concentration range from 0.1 to 1.0 mM [78]. The adsorp-
tion density of 0.29 mmol/g was observed for nitrate. Among all the
anions studied, only nitrate showed competitive adsorption with
perchlorate. It was suggested that perchlorate and nitrate prefer the
same surface sites in the adsorption process. Iron oxide-dispersed
activated carbon fibers were also used for NO3 − adsorption [79].
As revealed from the literature, surface modification of carbon-
based sorbents has found to increase sorption when compared to
adsorbents without surface modification.
3.2. Removal of nitrate from water by clay adsorbents
Clays are hydrous aluminosilicates broadly defined as those
minerals that make up the colloid fraction (<2 ␮m) of soils, sedi-
ments, rocks and water [80] and may be composed of mixtures of
fine grained clay minerals and clay-sized crystals of other miner-
als such as quartz, carbonate and metal oxides [81]. Clays play an
important role in the environment by acting as a natural scavenger
of pollutants by taking up cations and anions either through ion
exchange or adsorption or both [81]. Calcium bentonite was modi-
fied by acid thermoactivation with HCl (2N) and H2 SO4 (2N and 4N),
and investigated for NO3 − removal from aqueous solutions [82].
Calcium montmorrillonite activated by HCl showed better NO3 −
removal capacity, up to 22.28%. It was explained that an ionic inter-
change took place between chlorine (due to the hydrochloric acid
treatment) and nitrate ions. The ionic exchange was also confirmed
by the presence of KCl in the clay residue. The Brunauer-Emmet-
Teller (BET) area measurements showed no direct relation between
the surface area and the nitrate removal capacity. Nitrates adsorp-
tion in clays was further confirmed by using infrared spectroscopy.
Xi et al. [83] prepared the surfactant modified clay minerals and
evaluated them for NO3 − adsorption. It was found that untreated
Queensland (QLD) bentonite did not remove NO3 − from the solu-
tion, and kaolinite also showed similar behavior for NO3 − removal.
However, halloysite was found to remove ca. 0.54 mg NO3 − per
gram of clay. As all these untreated clays showed poor adsorp-
tion capacities for nitrate ions, these clays were modified with
nonfunctional surfactant hexadecyltrimethylammonium bromide
(HDTMA) in 2 or 4 cation exchange capacity (CEC) and the removal
capacities of these materials were found to greatly improve. Among
all these organoclays, HDTMA modified QLD-bentonite showed the
best result: H-B-2CEC and H-B-4CEC could remove 12.83 mg and
14.76 mg NO3 − /g of organoclay, respectively. But HDTMA modified
kaolinite and halloysite were found to remove less NO3 − compared
to H-B samples (e.g., H-K-2CEC, H-H-2CEC and H-H-4CEC removed
1.54, 1.78 and 1.93 mg NO3 − /g of clay, respectively). When the con-
centration of HDTMA was increased to 4 CEC, the removal capacity
was increased to 4.87 mg/g on H-K-4CEC. It was explained by the
fact that the CEC of QLD-bentonite (66.67 meq/100 g) was higher
496 A. Bhatnagar, M. Sillanpää / Chemical Engineering Journal 168 (2011) 493–504
than that of kaolinite and halloysite (9.78 and 10 meq/100 g, respec-
tively). Therefore, after modification with HDTMA, more surfactant
molecules were exchanged and attached on the surface of QLD
bentonite than that of other two clays.
3.3. Removal of nitrate from water by layered-double
hydroxides/hydrotalcite-like compounds/hydroxyapetite as
adsorbents
Hydrotalcite-like compounds, also known as layered double
hydroxides (LDHs), constitute an important class of inorganic mate-
rials with desirable properties to remove anionic pollutants from
water [15]. Zn-Al-Cl LDH was synthesized by co-precipitation
method and was characterized using various instrumental tech-
niques [15]. It was further tested towards NO3 − removal from
water. The removal of NO3 − was found to be 85.5% under neu-
tral conditions, using 0.3 g of LDH in 100 mL of NO3 − solution
having initial concentration of 10 mg/L. Adsorption kinetic study
revealed that the adsorption process followed first order kinetics.
Adsorption data were fitted to Langmuir isotherm. The Langmuir
sorption capacity was found to be 40.26 mg/g. The percentage
removal was found to decrease gradually with increase in pH and
the optimum pH was found to be 6. The presence of competitive
anions reduced the NO3 − adsorption in the order of carbon-
ate > phosphate > chloride > sulfate. The Zn-Al-Cl LDH exhibited low
desorption and poor regeneration.
LDHs with different kinds of metal ions (Mg-Al, Co-Fe, Ni-Fe,
and Mg-Fe) in the brucite layers were prepared by Tezuka et al.
[84] and their anion exchange properties were studied by measure-
ments of distribution coefficient (Kd ) and ion exchange capacity.
The basal spacing of LDHs varied depending on the kind of metal
ions in the brucite layer. A relatively high Kd value for NO3 − ions
was observed on Ni-Fe type LDHs, and a markedly high Kd value
for the hydrothermally-treated Ni-Fe type LDHs (Ni-Fe (HT)), pre-
pared at 120 ◦ C. These high Kd values correlated with the basal
spacing of 0.81 nm observed for this sample, where the inter-
layer distance (0.33 nm) is suitable for the stable fixing of NO3 −
ions (ionic size = 0.33 nm). A chemical analysis study showed a
Cl− /NO3 − ion-exchange mechanism for NO3 − adsorption on Ni-
Fe (HT). The NO3 − uptake by Ni-Fe (HT) was nearly constant
(NO3 /Fe = 0.7) over a pH range between 5 and 10, which was also
supported by the adsorption mechanism of Cl− /NO3 − ion exchange.
The Ni-Fe (HT) could remove NO3 − ions from seawater effectively
(NO3 − uptake = 168 ␮mol/g) even though seawater consisted large
amount of coexisting anions (2.3 mM of carbonate ions, 14 mM of
sulfate ions, 550 mM of chloride ions, etc.).
The selective adsorptive properties of Ni-Fe layered double
hydroxide (LDH (Ni-Fe)), containing Ni and Fe metal atoms in each
layer were studied for NO3 − removal from seawater [85]. LDH (Ni-
Fe) with Cl− in the interlayers was synthesized by co-precipitation
at constant pH. It showed a higher Kd for NO3 − than for other
anions (HPO4 2− and SO4 2− ). The prepared LDH (Ni-Fe) was also
studied for its potential for NO3 − removal by batch method using
NO3 − enriched seawater (NO3 − concentration: 40 ␮mol/dm3 ). The
equilibrium was achieved in 4 h with adsorption data following
the Freundlich model. The maximum NO3 − uptake was found to
be 0.33 mmol/g when LDH (Ni-Fe) (0.10 g) was added to NO3 −
enriched seawater (1 dm3 ), corresponding to the removal of 83% of
the NO3 − from seawater. The pH dependence of NO3 − adsorption
showed a maximum NO3 − uptake at around pH 8. Dissolutions of Ni
and Fe from LDH (Ni-Fe) was less than 0.6% for Ni and less than 0.1%
for Fe at pH 8, indicating that LDH (Ni-Fe) was sufficiently stable in
seawater.
The sorption of NO3 − on calcined hydrotalcite-type compounds
at 550 ◦ C (HT550), 650 ◦ C (HT650), and 850 ◦ C (HT850) from water
at 25 ◦ C has been studied by Socías-Viciana et al. [86]. The influence
of the temperature was also investigated for the sample calcined at
850 ◦ C by studying the sorption process at 10 and 40 ◦ C. The exper-
imental sorption data were fitted to the Langmuir model. Sorption
capacities of the samples ranged from 61.7 g/kg (HT550 at 25 ◦ C) to
147.0 g/kg (HT850 at 40 ◦ C). The values for the removal efficiency
ranged from 70.5% for HT550 at 25 ◦ C to 99.5% for HT850 at 40 ◦ C.
The sorption experiments showed that at higher calcination tem-
perature (850 ◦ C), the removal of NO3 − was greater. The increase
in the temperature from 10 to 40 ◦ C for sample HT850 also tended
to increase the sorption of NO3 − from 63.3 g/kg to 147 g/kg and the
corresponding removal efficiency ranged from 71.5 to 99.5%. The
variation of amount adsorbed of NO3 − and removal efficiency with
the heat treatment applied to the hydrotalcite seemed to be related
to the sorption mechanisms of the NO3 − ions; i.e., related to the
access by the NO3 − anions to the recovered layered structure of the
calcined hydrotalcite once rehydrated, by occupying the locations
of the carbonate anions initially present in the synthesized sample
(HT). It was noted that for the calcined samples, and according to
the characterization data discussed by the authors, a change in the
hydrotalcite structure was observed, mainly due to the loss of CO2
and the formation of amorphous Mg1−x Alx O1+x/2 mixed oxide. The
re-hydration of this mixed oxide lead to the incorporation of NO3 −
in the interlayer space, so the sample recovered its original struc-
ture. As the calcination temperature increased to 850 ◦ C, a greater
loss of CO2 occurred, thus increasing the amount of NO3 − adsorbed.
The adsorption of NO3 − by various layered double hydroxides
(LDHs), such as Mg-Al and Zn-Al, was investigated by Hosni et al.
[87]. The samples were identified as [MII 3P10], where M represents
the divalent cation used to prepare the materials. For example,
Mg3P10 stands for the precipitate prepared with Mg2+ as the diva-
lent cation and Mg/Al molar ratio of 3, at pH 10. The nature and
content of divalent cations in LDHs showed a strong influence on
the adsorption process. Calcined Mg-Al LDH with an Mg/Al molar
ratio of 3.0 showed higher adsorption capacity compared to other
calcined LDHs. The sorption capacity of Mg3P10-500 (activated by
heating at 500 ◦ C) was found to be 35 mg/g, and that of Zn3P10-500
was 20 mg/g. This difference in sorption capacity was explained
by the fact that the nature of the divalent cation in LDH has a
strong influence on the adsorption process. The removal of NO3 −
was found to take place via an adsorption process followed by a
reconstruction of the calcined material. Authors concluded that
the quantity of NO3 − removed (35 mg/g), which corresponds to
56 meq/100 g, was small and it was explained by the fact that
the CO3 2− coming from the dissolution of atmospheric CO2 dis-
placed NO3 − . The carbonate is attributed to their divalent character,
their relative small ionic radius, and the strong hydrogen bond that
occurred between NO3 − and the brucite-like sheets.
A laboratory study was conducted to investigate the ability of
Mg-Al-Cl hydrotalcite-like compound for the removal of NO3 − from
synthetic NO3 − solution [88]. The removal of NO3 − was 87.6% under
neutral condition, using 0.3 g of adsorbent in 100 mL of nitrate
solution having an initial concentration of 10 mg/L. The percent-
age removal was found to gradually decrease (from 87.6% to 69.9%)
with an increase in pH (from 6 to 12) and the optimum pH for
removal of nitrate was 6. The equilibrium was established within
40 min. The effect of other anions was also studied and it was found
that the anions reduced the NO3 − adsorption in the order of car-
bonate > phosphate > chloride > sulfate. A regeneration study of the
material with 1–4% NaCl was also carried out and it was found
that the Mg-Al-Cl hydrotalcite could not be easily regenerated and
reused. The percentage regeneration was <2%. It was therefore con-
cluded that once HTlc-nitrate is formed, it is difficult to regenerate.
The efficiency of hydroxyapatite (HAP) for NO3 − removal from syn-
thetic NO3 − solution was studied by the same workers [89]. The
results of pH study revealed that there was an increase in the per-
centage removal for increase in pH from 2 to 6 but further increase
 A. Bhatnagar, M. Sillanpää / Chemical Engineering Journal 168 (2011) 493–504
in pH beyond 6, no increase in removal was observed. The effect
of competing anions reduced the NO3 − adsorption in the order
of chloride > carbonate > sulfate > phosphate. It was suggested that
OH− ions were exchanged by NO3 − ions.
3.4. Removal of nitrate from water by zeolite adsorbents
Natural zeolites are hydrated aluminosilicate minerals of a
porous structure with valuable physicochemical properties [90].
Zeolites have been widely used as adsorbents in separation and
purification processes and remain a promising technique in envi-
ronmental cleaning processes [90]. Besides their natural form,
surface modified zeolites have also been tested for the removal of
water pollutants. Surface modifications of natural zeolite were per-
formed by coating it with a chitosan layer [91]. The chitosan coated
zeolite (Ch-Z) was protonated with either sulfuric or hydrochlo-
ric acid and tested for its suitability to capture NO3 − from water
at 20 and 4 ◦ C. It was found that protonation with hydrochloric
acid resulted a higher maximum NO3 − exchange capacity when
compared to sulfuric acid. The surface characterization of the Ch-Z
was performed using scanning electron microscopy (SEM), Fourier
transform infrared spectrometry (FTIR), thermogravimetric analy-
sis (TGA) and nitrogen adsorption tests. The results of these tests
showed evidence of chitosan coating onto zeolite particles. Ch-Z has
a comparable ion exchange capacity to other weak anion exchang-
ers with a NO3 − ion exchange capacity of 0.74 mmol NO3 − /g
(protonated with HCl).
Nitrate adsorption kinetics were determined in batch-wise
experiments on a nonfunctional surfactant-modified zeolite
(SMZ), prepared by treatment of a clinoptilolite sample by
HDTMABr (HDTMA+ being the hexadecyltrimethylammonium
cation) [92]. The influence of various parameters, namely ini-
tial NO3 − concentration (0.08–8.06 mmol/L), liquid/solid weight
ratio (L/S = 5–50 mL/g) and presence of Cl− , SO4 2− and HCO3 −
competing anions (at the same equimolar concentration equal to
1.61 mmol/L) were studied. The equilibrium time for NO3 − uptake
was short (0.5–1 h), with a maximal removal value (Rmax. ) at equi-
librium. Rmax. was found to decrease significantly to 58% and 40%,
respectively, for higher concentrations (4.83 and 8.06 mmol/L). The
final removal rate was ≥80%, with liquid/solid weight ratios ≤10,
initial NO3 − concentrations in the range 0.08–2.42 mmol/L (corre-
sponding to 5–150 mg/L). The sorption equilibrium data were in
good agreement with the Langmuir isotherm model. On the other
hand, the Rmax. value decreased with the increase in adsorbent
mass. Under the studied experimental conditions, the presence
of competing anions did not change the NO3 − Rmax. value, but
slowed down the exchange kinetics and the increasing affinity
order towards the SMZ was found as follows: Cl−  HCO3 − #
SO4 2− < NO3 − . Other studies have also examined the feasibility
of zeolites for nitrate removal from water [93,94]. Experimental
results [93] showed that shallow-well water (with NO3 − concen-
tration of 74–288 mg/L), after 1 h. mixing with 5 g of 0.315 mm
particle-sized zeolite and after 30 min. sedimentation, NO3 − con-
centration stayed the same without any reduction. However, the
same shallow-well water (with 1–10 mg/L ammonium ion con-
centration) mixed with 5 g of 0.315–0.63 mm particle-sized zeolite
showed ammonium ion removal efficiency of 72–86%, revealing
that zeolite particles were not found suitable for NO3 − sorption
from water solutions, but 0.315–0.63 mm particle-sized zeolite
could be a useful sorbent for NH4 + removal from water. Hexade-
cyltrimethyl ammonium bromide (HDTMABr) surfactant modified
zeolite (SMZ) were prepared by Masukume et al. [94] and evalu-
ated as a potential adsorption media for NO3 − removal from water.
It was found that surfactant modification of zeolite resulted in a
significant increase in the adsorption capacity (∼11.5 mg/g) of the
adsorbent.
497
Surfactant modified zeolites with different coverage types were
prepared by loading the cetylpyridinium bromide (CPB) onto the
surface of the natural zeolites (NZ) [95]. The adsorption behavior
of NO3 − on SMZ was investigated. NZ and SMZ with monolayer
CPB coverage were found inefficient for the removal of NO3 − from
aqueous solution. However, SMZ with patchy bilayer or bilayer CPB
coverage was efficient in NO3 − removal, and the NO3 − adsorp-
tion capacity of SMZ increased with its CPB loading. Based on
the Langmuir isotherm model, the predicted maximum monolayer
NO3 − adsorption capacity for SMZ7 (SMZ sample with CPB loading
amounts of 409 mmol/(kg NZ)) was found to be 9.36 mg/g. Anionic
exchange and electrostatic attraction were the main mechanisms
responsible for the adsorption of NO3 − onto SMZ7. The presence
of chloride, sulfate or bicarbonate ions in solution slightly reduced
the NO3 − adsorption efficiency for CPB modified zeolite.
3.5. Removal of nitrate from water by chitosan adsorbents
Chitin and chitosan-derivatives have gained wide attention as
effective biosorbents due to low cost and high contents of amino
and hydroxyl functional groups which show significant adsorp-
tion potential for the removal of various aquatic pollutants [96].
Chitosan hydrobeads were prepared by Chatterjee and Woo [97]
and examined for the adsorption of NO3 − . The maximum adsorp-
tion capacity was 92.1 mg/g at 30 ◦ C. Intraparticle diffusion was
suggested to play a significant role at the initial stage of the adsorp-
tion process. Nitrate adsorption was found to increase with a
decrease in the pH of the solution which was explained by the
fact that a decrease in the pH of the solution resulted in more
protons being available to protonate the chitosan amine group.
This resulted in an enhancement of NO3 − adsorption by the chi-
tosan beads due to increased electrostatic interactions between the
negatively charged NO3 − group and the positively charged amine
group. Above pH 6.4, an appreciable amount of NO3 − adsorption
by chitosan beads indicated the involvement of physical forces.
The equilibrium adsorption capacity decreased by increasing the
temperature from 30 to 50 ◦ C which was explained due to either
the damage of active binding sites of the adsorbent or increasing
tendency to desorb NO3 − ions from the interface to the solution.
However, increase in temperature from 20 to 30 ◦ C reduced the
nitrate adsorption, which was attributed to an increase of the
mobility of the NO3 − ions and a swelling effect within the internal
structure of chitosan beads. Desorption of NO3 − from the loaded
beads was accomplished by increasing the pH of the solution to the
alkaline range, and a desorption ratio of 87% was achieved around
pH 12.0.
The same authors [98] also reported the adsorption of NO3 −
onto chitosan beads modified via crosslinking with epichlorohy-
drin (ECH) and surface conditioning with sodium bisulfate. The
maximum adsorption capacity was found at a cross-linking ratio
of 0.4 and a conditioning concentration of 0.1 mM NaHSO4 . It
was reported that ECH mainly cross-links chitosan beads using
the –OH group of chitosan and did not interact with the cationic
amine groups of chitosan during the cross-linking. The maximum
value for the equilibrium adsorption capacity of cross-linked chi-
tosan beads was found at a 0.4 cross-linking ratio, and further
increase in this ratio slightly reduced the uptake value. Thus, an
increase in the cross-linking ratio did not reduce the available
adsorption sites but increased the steric hindrance for diffusion
through the chitosan beads. The conditioning of chitosan beads
with NaHSO4 increased its equilibrium adsorption capacity because
the amine groups of chitosan were protonated by the H+ pro-
duced from the dissociation of NaHSO4 during conditioning. The
maximum adsorption capacity was 104.0 mg/g for the conditioned
cross-linked chitosan beads at pH 5, while it was 90.7 mg/g for
normal chitosan beads. The NO3 − adsorption was found to be
498 A. Bhatnagar, M. Sillanpää / Chemical Engineering Journal 168 (2011) 493–504
strongly pH dependent, and the maximum NO3 − removal was
found at pH 3. The high adsorption capacities in acidic solu-
tions (pH 3–5) were due to the strong electrostatic interactions
between adsorption sites and NO3 − . The mean adsorption energies
obtained from the Dubinin-Radushkevich (D-R) model indicated
that physical electrostatic forces were involved in the adsorption
process. The feasibility of NO3 − removal by cross-linked chitosan
gel beads was also investigated by Jaafari et al. [99–100]. Pro-
tonated cross-linked chitosan gel beads were prepared [99] and
examined for NO3 − removal. The sorption capacity was found
to be dependent on pH and was maximal at pH of between 3
and 5. Chloride and sulfate did not show interference but fluo-
ride slightly lowered the NO3 − sorption. Increasing pH to 12 with
NaOH allowed desorption of NO3 − without losing the effectiveness
of the sorbent. The same workers extended their study to simu-
late and design the operation of a fixed bed adsorber [100]. It was
reported by the authors that daily water required for 5–10 people
could be produced with an adsorber of 0.2 m diameter and 1.5 m
length.
3.6. Removal of nitrate from water by agricultural wastes as
adsorbents
The use of agricultural waste materials is an attractive option
as it combines the reuse of waste materials in the remediation of
water and wastewaters. Different agricultural wastes have been
studied for the removal of NO3 − from aqueous solutions. Orlando
et al. [101] investigated the feasibility of lignocellulosic agricultural
waste materials (LCM), sugarcane bagasse (BG) and rice hull (RH)
after converting them into weak base anion exchangers and further
evaluated their potential for NO3 − removal from water. Pure cellu-
lose (PC) and pure alkaline lignin (PL) were also used as reference
materials to elucidate possible reactivity in LCM. Epoxy and amino
groups were introduced into BG, RH, PC and PL substrates after
the reaction with epichlorohydrin and dimethylamine in the pres-
ence of pyridine and an organic solvent N,N-dimethylformamide
(DMF). It was found that amino group incorporation into cellulose
decreased with the presence of water in the reaction mixture and
increased with the reaction time and presence of a catalyst (pyri-
dine). The highest maximum NO3 − exchange capacity and yields
of the prepared exchangers was obtained from PL (1.8 mmol/g and
412.5%), followed by BG (1.41 mmol/g and 300%), PC (1.34 mmol/g
and 166%) and RH (1.32 mmol/g and 180%). The proposed synthetic
procedure was found effective in modifying PL, PC and LCM result-
ing in a higher yield and NO3 − removal capacity.
Anionic sorbent using wheat straw was prepared and examined
for NO3 − removal from aqueous solution by Wang et al. [102]. The
oven-dried and sieved (150–250 ␮m) raw wheat straw (RWS) was
crosslinked with epichlorohydrin and dimethylamine. The results
indicated that the yield of the prepared anionic sorbent, the total
exchange capacity, and the maximum adsorption capacity were
350%, 2.57 mEq/g, and 2.08 mmol/g, respectively. In the presence of
a mixed ion solution, the preferential adsorption of the anions was
in the following order, SO4 2− > H2 PO4 − > NO3 − > NO2 − . The capac-
ity of NO3 − adsorption was reduced by 50%. Desorption and reuse
experiments showed that about 90% of the adsorbed NO3 − ions
could be desorbed from modified wheat straw (MWS) anionic sor-
bent using 30 mL of 0.1 M NaOH.
In another study [103], the raw wheat residue (RWR) was
modified by epichlorohydrin in the presence of pyridine and the
adsorption kinetics were investigated in batch experiments. The
significant increase in the zeta potential (from −35 mV to 40 mV)
and total exchange capacity (TEC) (from 0.25 mEq/g to 2.57 mEq/g)
of modified wheat residue (MWR) was observed after chemical
treatment which greatly enhanced the anion adsorption capacity.
The results showed that the MWR had greater anion adsorbing
capacity. The maximum adsorption capacity of RWR and MWR
were 0.02 mmol/g and 2.08 mmol/g, respectively.
Almond shell activated carbon impregnated by Zn◦ and ZnSO4
were used as adsorbent with a particle size of 10–20 mesh for
NO3 − removal by Rezaee et al. [104]. Experimental data showed
that modified activated carbon by Zn◦ and ZnSO4 was more effec-
tive than virgin almond activated carbon for NO3 − removal. It was
postulated that after modification of activated carbon, macrop-
ores were filled by Zn◦ and ZnSO4 and micropores were formed.
Furthermore, zinc present at carbon surface as ZnO increased pos-
itive charge of activated carbon which resulted increased NO3 −
adsorption. The maximum NO3 − removal was 64–80% and 5–42%
for modified activated carbon and virgin activated carbon, respec-
tively. Maximum removal was ca. 16–17 mg NO3 − per g activated
carbon for impregnated activated carbon.
The effectiveness of wheat straw charcoal (WSC) and mustard
straw charcoal (MSC) as adsorbents for the removal of NO3 − -N from
water has been investigated [105]. Wheat straw charcoal and mus-
tard straw charcoal were prepared by taking clean and air dried
(for 24 h) straw which was sieved (sieve size was ASTM—7–10) and
were heated in a muffle furnace at 300 ◦ C for 1 h and 30 min. Then
the charcoal was washed by using double distilled water to remove
any color due to the presence of carbon particles. Commercial acti-
vated carbon (CAC) from Eureka Forbes Limited was used as a
standard for comparison. The calculated values of amount adsorbed
of WSC, MSC and CAC at 15 ◦ C were 1.10, 1.30 and 1.22 mg/g,
respectively, which showed that the adsorption effectiveness of
MSC was higher than that of WSC and CAC used in this experi-
ment.
The nitrate removal was evaluated using a fixed-bed column
packed with amine-crosslinked wheat straw (AC-WS) [106]. Solid-
state 13 C NMR and zeta potential analysis validated the existence
of crosslinked amine groups in AC-WS. Raman shift of the nitrate
peaks suggested the electrostatic attraction between the adsorbed
ions and positively charged amine sites. The column sorption
capacity of the AC-WS for nitrate was 87.27 mg/g in comparison
with the raw WS of 0.57 mg/g. Nitrate sorption in column was
affected by bed height, influent nitrate concentration, flow rate and
pH, and of all these, influent pH demonstrated significant effect on
the performance of the column. HCl solution (0.1 mol/L) demon-
strated its high desorption rate for the regeneration of AC-WS. In
addition, the sorption-desorption process indicated the excellent
regeneration capacity of AC-WS with little loss (5.2%) in its initial
sorption capacity when repeatedly used.
A new inorganic/sugar beet pulp composite material was pre-
pared from sugar beet pulp (SBP) after loading with zirconium(IV)
ions [107]. The prepared anion exchanger material was exam-
ined for its ability to remove sulfate and NO3 − from water. The
effect of contact time, anions concentration, temperature, and pH
on the adsorption capacity of Zr(IV)-loaded SBP was studied. The
maximum adsorption capacity of Zr(IV)-loaded SBP was about
114 mg/g and 63 mg/g for sulfate and NO3 − , respectively. In addi-
tion, the effect of the regeneration of the Zr-loaded SBP after anion
removal was also studied. The results of anion adsorption tests and
energy dispersed X-ray (EDX)-SEM showed that zirconium ions
were strongly bound to the carboxylate groups of SBP constituents,
especially pectins, and were not leached as a result of regeneration.
Activated carbon was prepared from sugar beet bagasse by
chemical activation using ZnCl2 and the prepared activated car-
bon was used to remove NO3 − from aqueous solutions [108]. The
maximum specific surface area of the activated carbon was about
1826 m2 /g at 700 ◦ C and at an impregnation ratio of 3:1. It was
discussed by the authors that increasing the carbonization temper-
ature increased the evolution of volatile matters from the precursor,
leading to the increase in the pore development, and creating new
pores. Maximum removal (41.2%) was achieved at pH 3. The maxi-
 A. Bhatnagar, M. Sillanpää / Chemical Engineering Journal 168 (2011) 493–504
mum adsorption capacity increased from 9.14 to 27.55 mg/g as the
temperature increased from 25 to 45 ◦ C.
Kinetic and thermodynamic studies were carried out for the
adsorption of NO3 − from aqueous solutions onto modified beet
residue and for desorption from the sorbent to the solution in batch
experiments [109]. The beet residue was modified by epichlorohy-
drin in the presence of pyridine. The experiments were conducted
in the presence and absence of ultrasound. It was found that
more than 90% of NO3 − was removed in <2 min from the solu-
tion. Results indicated that the adsorption of NO3 − in the presence
of ultrasound was higher at lower temperature (10 ◦ C) and it was
lower at higher temperatures with respect to the control method
(without ultrasound). The maximum capacity was higher in con-
trol method (57.12–85.9 mg/g) than in the presence of ultrasound
(48.4–86.16 mg/g). This behavior could be explained by the acous-
tic cavitation (formation, growth, and collapse of the cavity). The
critical conditions produced during the cavitation could reduce the
sorbed species from the sorbent and lead to the lower amount of
NO3 − uptake. In the case of desorption study, the amount of des-
orption was higher in the presence of ultrasound than in its absence
at different applied temperatures.
3.7. Removal of nitrate from water by industrial wastes as
adsorbents
Only a few industrial wastes have been tested as adsorbents
for NO3 − removal. Cengeloglu et al. [110] reported the removal of
NO3 − from aqueous solution by using the original (water washed
and dried) and activated (water washed and HCl treated) red mud.
The NO3 − adsorption capacity of activated red mud was found to
be higher than that of the original form and decreased above pH
7. Adsorption capacity of the original and activated red mud was
found to be 1.859 and 5.858 mmol NO3 − /g red mud, respectively.
The increase in sorption capacity in red mud after acid treatment
was attributed to the leaching out of the sodalite compounds dur-
ing acid treatment, which are expected to hinder the adsorption
Fig. 2. List of different adsorbents used for the removal of nitrate from water.
499
by blocking the available adsorption sites for nitrate in untreated
red mud. The equilibrium time of nitrate sorption was 60 min. The
mechanism for NO3 − removal was explained by considering the
chemical nature of red mud and the interaction between metal
oxides surface and NO3 − ions. Other industrial wastes (e.g., slag, fly
ash) have been examined with other adsorbents and their results
have been discussed under Section 3.8.
3.8. Removal of nitrate from water by miscellaneous adsorbents
Sepiolite activated by HCl, slag and powdered activated carbon
were tested as adsorbents for NO3 − removal [111]. The equilib-
rium time was found to be 30, 45, 5 min for sepiolite, powdered
activated carbon and activated sepiolite, respectively. The most
effective pH for nitrate removal was 2 for powdered activated car-
bon, however, pH did not affect nitrate removal significantly for
other adsorbents. Sepiolite activated by HCl showed the highest
potential (38.16 mg/g) for NO3 − removal which was explained due
to increase in surface area after activation as the proton (H+ ) of the
acids was replaced by part of the Mg2+ ions located in the octa-
hedral sheet during acid activation. Furthermore, more carbonates
in sepiolite were partially decomposed leading to new pores and
fresh surfaces.
In order to increase the positive charge on the surface, sepiolite
was modified by treatment with nonfunctional surfactant dode-
cylethyldimethylammonium (DEDMA) bromide [112]. After mod-
ification, it was found that maximum NO3 − adsorption occurred at
pH 2.0. The results indicated that the surfactant-modified sepiolite
was more effective (453 mmol/kg) than the unmodified sepiolite
(408 mmol/kg) for NO3 − removal. Dried chinese reed (Miscant-
hus sinensis), a fast growing plant, was used as a model biomass
for the development of anion exchangers using a quaternization
agent, N-(3-chloro-2-hydroxypropyl)trimethylammonium chlo-
ride (CHMAC), and a cross-linking agent, epichlorohydrin by
Namasivayam et al. [113]. The adsorption capacity of the cross-
linked and quaternized chinese reed for NO3 − was found to be
500 A. Bhatnagar, M. Sillanpää / Chemical Engineering Journal 168 (2011) 493–504

Table 1
Adsorption capacities and other parameters for the removal of nitrate by different sorbents.

S. no. Adsorbent Amount adsorbed Concentration range Contact time Temperature pH Ref.
◦
1. H2 SO4 treated carbon cloth 2.03 mmol/g 115 mg/L 60 min 25 C ∼7.0 [73]
2. Powdered activated carbon 10 mmol/g – 60 min 25 ◦ C <5.0 [74]
3. Carbon nanotubes 25 mmol/g – 60 min 25 ◦ C <5.0 [74]
4. Untreated coconut granular activated 1.7 mg/g 5–200 mg/L 2h 25 ◦ C 5.5 [75]
carbon
5. ZnCl2 treated coconut granular 10.2 mg/g 5–200 mg/L 2h 25 ◦ C 5.5 [75]
activated carbon
6. Coconut shell activated carbon 2.66 × 10−1 mmol/g – – 303 K 2–4 [76]
7. Bamboo charcoal 1.04 × 10−1 mmol/g – – 303 K 2–4 [76]
8. Bamboo powder charcoal 1.25 mg/g 0–10 mg/L 120 h 10 ◦ C – [77]
9. Halloysite 0.54 mg/g 100 mg/L 17 h Room temperature 5.4 [83]
10. HDTMA modified QLD-bentonite 12.83–14.76 mg/g 100 mg/L 17 h Room temperature 5.4 [83]
11. Calcined hydrotalcite-type compounds 61.7–147.0 g/kg 12.7–236 mg/L 24 h 25 ◦ C – [86]
12. Layered double hydroxides 20–35 mg/g 0–1000 mg/L 4h 21 ◦ C ∼8.5 [87]
13. Chitosan coated zeolite 0.6–0.74 mmol/g 10–3100 mg/L 72 h 4 ◦ C and 20 ◦ C – [91]
14. Chitosan hydrobeads 92.1 mg/g 1–1000 mg/L 1440 min 30 ◦ C 5.0 [97]
15. Chitosan beads 90.7 mg/g 25–1000 mg/L 24 h 30 ◦ C 5.0 [98]
16. Conditioned cross-linked chitosan 104.0 mg/g 25–1000 mg/L 24 h 30 ◦ C 5.0 [98]
beads
17. Pure alkaline lignin 1.8 mmol/g 1–30 mg/L 48 h 30 ◦ C – [101]
18. Sugarcane bagasse 1.41 mmol/g 1–30 mg/L 48 h 30 ◦ C – [101]
19. Pure cellulose 1.34 mmol/g 1–30 mg/L 48 h 30 ◦ C – [101]
20. Rice hull 1.32 mmol/g 1–30 mg/L 48 h 30 ◦ C – [101]
21. Raw wheat residue 0.02 mmol/g 50–500 mg/L 150 min 23 ± 2 ◦ C 6.8 [103]
22. Modified wheat residue 2.08 mmol/g 50–500 mg/L 150 min 23 ± 2 ◦ C 6.8 [103]
23. Impregnated almond shell activated 16–17 mg/g 10–50 mg/L 120 min 20 ◦ C 6.2 [104]
carbon
24. Wheat straw charcoal 1.10 mg/g 0–25 mg/L 10 min 15 ◦ C – [105]
25. Mustard straw charcoal 1.30 mg/g 0–25 mg/L 10 min 15 ◦ C – [105]
26. Commercial activated carbon 1.22 mg/g 0–25 mg/L 10 min 15 ◦ C – [105]
27. Zr(IV)-loaded sugar beet pulp 63 mg/g – 24 h 25 ◦ C 6.0 [107]
28. Chemically modified sugar beet 9.14–27.55 mg/g 10–200 mg/L – 25–45 ◦ C 6.58 [108]
bagasse
29. Original and activated red mud 1.859 and 5.858 mmol/g 5–250 mg/L 60 min Room temperature 6.0 [110]
30. Sepiolite activated by HCl 38.16 mg/g 100 mg/L 5 min – – [111]
31. Unmodified sepiolite 408 mmol/kg – – – – [112]
32. Surfactant-modified sepiolite 453 mmol/kg – – – 2.0 [112]
33. Cross-linked and quaternized chinese 7.55 mg/g 10–40 mg/dm3 10 min 25 ◦ C 5.8 [113]
reed
34. Ammonium-functionalized 46.0 mg/g 100–700 mg/L 60 min 5 ◦C <8.0 [114]
mesostructured silica

7.55 mg of anion per g of the anion exchanger. The pH effect and
desorption studies confirm that removal of NO3 − occurred through
ion exchange on the quaternized biomass. The presence of sul-
fate, fluoride, phosphate, and perchlorate considerably lowered the
uptake of nitrate.
Adsorption of NO3 − and monovalent phosphate anions from
aqueous solutions on ammonium-functionalized mesoporous
MCM-48 silica was investigated [114]. The adsorbent was prepared
via a post-synthesis grafting method, using aminopropyltri-
ethoxysilane, followed by acidification in HCl solution to convert
the attached surface amino groups to ammonium moieties. The
adsorbent was determined to be effective for the removal of
both anions. The removal of NO3 − was maximum at pH <8,
whereas phosphate removal was maximized at 4 < pH < 6. Max-
imum removal of 71% and 88% was obtained for NO3 − and
phosphate, respectively, using an adsorbent dose of 10 g/L. Des-
orption of both anions was rapidly achieved within 10 min, using
0.01 M NaOH. Regeneration tests showed that the adsorbent
retained its capacity after five adsorption–desorption cycles.
Ammonium-functionalized MCM-41, MCM-48 and SBA-15
mesoporous silica materials were synthesized via post-synthesis
grafting [115] and their efficiency to remove NO3 − and phos-
phate anions in aqueous solutions was investigated. The adsorbents
showed high adsorption capacities reaching 46.5 mg NO3 − /g and
55.9 mg H2 PO4 − /g under the operating conditions explored. The
mesoporous silica functionalized via post-synthesis grafting meth-

Table 2
Kinetic studies of nitrate on different adsorbents.

S. no. Adsorbent Applicable kinetic model Reference

1. Carbon cloth First-order [73]

2. Untreated coconut granular activated carbon Pseudo-second-order [75]
3. ZnCl2 treated coconut granular activated carbon Pseudo-second-order [75]
4. Chitosan hydrobeads Pseudo-second-order [97]
5. Modified wheat straw First-order [102]
6. Raw wheat residue Pseudo-second-order [103]
7. Modified wheat residue Pseudo-second-order [103]
8. Zr(IV)-loaded sugar beet pulp Pseudo-first-order [107]
9. Chemically modified sugar beet bagasse Pseudo-second-order [108]
10. Modified beet residue Pseudo-second-order [109]
11. HCl activated sepiolite Second-order [111]
 A. Bhatnagar, M. Sillanpää / Chemical Engineering Journal 168 (2011) 493–504 501

Table 3
Adsorption isotherm studies of nitrate on different adsorbents.

S. no. Adsorbent Applicable isotherm model Reference

1. Carbon cloth Langmuir [73]

2. Powdered activated carbon Freundlich [74]
3. Carbon nanotubes Freundlich [74]
4. Untreated coconut granular activated carbon Langmuir [75]
5. ZnCl2 treated coconut granular activated carbon Langmuir [75]
6. Bamboo powder charcoal Langmuir [77]
7. Calcined hydrotalcite-type compounds Langmuir [86]
8. Layered double hydroxides Langmuir [87]
9. Chitosan hydrobeads Langmuir [97]
10. Chitosan beads Langmuir [98]
11. Conditioned cross-linked chitosan beads Langmuir [98]
12. Pure alkaline lignin Langmuir [101]
13. Sugarcane bagasse Langmuir [101]
14. Pure cellulose Langmuir [101]
15. Rice hull Langmuir [101]
16. Modified wheat straw Freundlich [102]
17. Raw wheat residue Freundlich [103]
18. Modified wheat residue Freundlich [103]
19. Wheat straw charcoal Langmuir [105]
20. Mustard straw charcoal Langmuir [105]
21. Commercial activated carbon Langmuir [105]
22. Zr(IV)-loaded sugar beet pulp Langmuir [107]
23. Chemically modified sugar beet bagasse Langmuir [108]
24. Modified beet residue Langmuir [109]
25. Original and activated red mud Langmuir [110]
26. HCl activated sepiolite Freundlich [111]

ods exhibited higher performances in terms of percentage pollutant
removal and adsorption capacities.
Nitrate removal from paper mill industry wastewater was
studied [116] with fly-ash, raw and heat-activated sepiolite as
adsorbents. Equilibrium time was found to be 1 h for both adsor-
bents. It was observed that pH played an important role in the
NO3 − adsorption process, both ionizing the compounds and mod-
ifying sorbent surfaces. It was noticed that heat-activated sepiolite
was more effective than raw sepiolite and fly-ash to remove
NO3 − .
Six species of trees in the Cedar and Bald Cypress families
were selected and samples of heartwood, sapwood and bark were
obtained [117]. The wood samples were pretreated with a weak
acid solution (pH 3) and distilled water (control). During the
experiment, liquid absorbed, tannin leaching, tissue density and
sorption of NO3 − from solution data were recorded. Samples that
proved most effective for NO3 − removal were also evaluated for
re-release of sorbed NO3 − back into water. Nitrate removal from
water solutions were most effective with incense cedar bark (22%
removal/water pre-treatment, 28% removal/acid pre-treatment)

Table 4
Thermodynamic studies of nitrate sorption on different adsorbents.

Adsorbent Temperature (◦ C) G (kJ/mol) H (kJ/mol) S (kJ/mol·K) Reference

Zn/Al chloride layered double 20 −0.987 to −1.789 13.832 to 16.392 0.0672 to 0.07346 [15]
hydroxide 25 −1.560 to −2.294
30 −2.133 to −2.798
35 −2.706 to −3.303
40 −3.280 to −3.808
45 −3.853 to −4.313
50 −4.426 to −4.817

ZnCl2 treated coconut granular activated carbon 10 −4.01 −32.33 [75]

25 −3.05 −13.16 −33.93
45 −2.75 −32.4

Thermally activated Mg/Al chloride hydrotalcite-like 20 −0.987 to −1.789 10.361 to 12.912 0.055 to 0.069 [88]
compound 25 −1.560 to −2.294
30 −2.133 to −2.798
35 −2.706 to −3.303
40 −3.280 to −3.808
45 −3.853 to −4.313
50 −4.426 to −4817

Surfactant modified zeolite 15 −19.6 [95]

25 −19.9 −13.7 20.5
35 −20.0

Chitosan hydrobeads 20 −16.343 47.92 [97]

30 −17.006 −2.302 48.53
40 −17.313 47.96
50 −17.846 48.12

Sugar beet bagasse carbon 25 −20.75 [108]

35 −24.18 133.62 0.516
45 −31.15
502 A. Bhatnagar, M. Sillanpää / Chemical Engineering Journal 168 (2011) 493–504
and Port-Orford cedar bark (33% removal/water pretreatment, 30%
removal/acid pre-treatment).
The NO3 − adsorption onto a cement paste, a cured mixture of
cement and water, has been observed and is well described by
a linear isotherm with the coefficient of 43.6 L/kg [118]. Cement
paste column was used by Park et al. [119] to remove some anions
including NO3 − . Recently, the feasibility of nano-alumina for NO3 −
removal from aqueous solutions has been explored [120]. The max-
imum sorption capacity of nano-alumina for NO3 − removal was
found to be ca. 4.0 mg/g. Maximum NO3 − removal occurred at equi-
librium pH ∼ 4.4. Nitrate sorption was affected by the presence of
chloride, sulfate and carbonate anions.
Fig. 2 summarises various sorbents which have been used so
far for the removal of nitrate. Furthermore, a summary of adsorp-
tion capacities of various adsorbents for nitrate removal from
water has been presented in Table 1. A perusal of Table 1 reveals
that hydrotalcite-type compounds/layered double hydroxides and
chemically modified adsorbents have been found promising for
enhanced removal of nitrate from water. Tables 2–4 represent
kinetic studies, adsorption isotherms and thermodynamic stud-
ies of nitrate sorption onto various adsorbents. In most studies,
pseudo-second-order kinetic model was found to fit well with the
data. Furthermore, nitrate sorption by various adsorbents is char-
acterized by Freundlich and Langmuir isotherm models. Negative
Gibbs free energy change (G) indicates the feasibility and spon-
taneous nature of the adsorption process, while positive enthalpy
change (H) represents endothermic nature of an adsorption. In
some cases, negative values of enthalpy change were reported
indicating the exothermic nature of the process. Positive entropy
change (S) denotes the affinity of the adsorbents and increas-
ing randomness at solid–solution interface during the sorption of
nitrate on active sites of the adsorbents, while negative value of
entropy change in some cases indicates that degree of freedom
decreases at solid/liquid interface during the adsorption.
4. Conclusions and future perspectives
Nitrate is ubiquitous in the environment, leading to human
exposure and causing potential impact on human health and pro-
moting ecological disturbances such as eutrophication. Among
several water treatment technologies for removing NO3 − , adsorp-
tion has been widely explored. This review compiles a list of
several materials which have been explored as adsorbents for NO3 −
removal. Double layered hydroxides/hydrotalcite-type compounds
and modified chitosan show higher uptake of NO3 − compared to
other conventional adsorbents. Agricultural wastes, after surface
modification, have also been explored for NO3 − removal and, in
some cases, these wastes show an appreciable potential for NO3 −
removal. However, during chemical treatment of adsorbent, one
should not ignore the cost factor. Low production cost with higher
removal efficiency would make the process economical and effi-
cient. More research is needed to properly optimize the conditions.
As revealed from the literature reviewed, only a few industrial
wastes have been examined for NO3 − removal, however, these can
serve as potential sorbents for NO3 − sorption as they are gener-
ally characterized by positive surface charge thereby increasing the
sorption of negatively charged NO3 − anion.
Selection of a suitable adsorbent media for NO3 − removal from
water generally depends on several factors including, (1) the range
of initial NO3 − concentrations, (2) other competing ions and their
concentration in water, (3) optimization of adsorbent dose, (4)
adjustment of pH in water, and (5) proper operation and main-
tenance. Therefore, selection of a suitable adsorbent for effective
NO3 − removal is a complex task. A particular sorbent which shows
higher uptake of NO3 − in the laboratory, may fail in field condi-
tions. Thus, the selection of the appropriate technology/sorbent
media can be tedious. Besides these, some other issues, such
as assessment of efficacy of sorbents for NO3 − removal under
multi-component pollutants, mechanistic modeling to correctly
understand the sorption mechanisms, investigation of these mate-
rials with real industrial effluents, and continuous flow studies
should also be conducted in detail. Last but not the least, it would be
worthwhile to investigate the reusability of the spent adsorbents
as only a few studies are available in literature. More research is
needed in the field of regeneration and finally for the environmen-
tally safe disposal of NO3 − -laden adsorbents.
Acknowledgments
We wish to thank all the anonymous reviewers whose com-
ments/suggestions have significantly improved the quality of
this manuscript. Amit Bhatnagar acknowledges his post-doctoral
scholarship (FCT-DFRH-SFRH/BPD/62889/2009) supported by the
Portuguese Foundation for Science and Technology (FCT).
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