8806 Ind. Eng. Chem. Res.

2007, 46, 8806-8812

Adsorptive Removal of Phosphate and Nitrate Anions from Aqueous Solutions

Using Ammonium-Functionalized Mesoporous Silica
Safia Hamoudi,* Rabih Saad, and Khaled Belkacemi
Department of Soil Sciences and Agri-Food Engineering; UniVersité LaVal, Québec, Canada, G1K 7P4

Adsorption of nitrate and monovalent phosphate anions from aqueous solutions on ammonium-functionalized
mesoporous MCM-48 silica was investigated. The adsorbent was prepared via a post-synthesis grafting method,
using aminopropyltriethoxysilane, 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 effects of pH, temperature, initial concentration of anions, and adsorbent loading on both anions
adsorption were examined. At ambient temperature, the removal of nitrate was maximum at pH <8, whereas
phosphate removal was maximized at 4 < pH < 6. At a given initial concentration, the percentage anions
removal increased as the adsorbent loading increased. For instance, maximum removals of 71% and 88%
were obtained for nitrate and phosphate solutions, respectively, using an adsorbent loading of 10 g/L. The
results also showed that the adsorption capacity decreased as the temperature increased. The adsorption
isotherms were approached by the standard adsorption model equations. Based on a model discrimination
study, only the Freundlich model resulted in physicochemically sound adsorption enthalpies and entropies
for both anions. Desorption 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.

1. Introduction the tethering of organic functional groups has attracted much

Water pollution that is due to the excessive presence of
nutrients (i.e., nitrogen and phosphorus) is a serious environ-
mental worldwide problem, because both species are implicated
in the eutrophication of receiving surface waters.1 Agricultural
over-application of natural and synthetic fertilizers, aquaculture,
municipal wastewaters, and the detergent manufacturing and
mineral processing industries are the main sources of nutrients
release into the aquatic environment.2 Eutrophication is the
abundance of aquatic plants, growth of algae, and depletion of
dissolved oxygen.3 Furthermore, the presence of nitrate ions in
drinking water is a potential public health hazard, including
infant methaemoglobinaemia (“blue baby” syndrome).4,5
Several physicochemical and biological processes have been
investigated for the removal of dissolved nutrients in water and
wastewaters. Among them, adsorption methods are promising,
because they allow simple and economical operation, resulting
in less sludge production and disposal problems. Therefore,
several materials such as fly ash and cement, surfactant-modified
zeolites, alunite, polymeric ion exchangers, and agricultural
residues have been investigated as adsorbents for the removal
of phosphate and/or nitrate anions.6-10 However, these materials
exhibited insufficient adsorption and regeneration capacities, as
well as poor selectivity and limited surface area. Therefore, there
is an imperative need to develop novel adsorbents with high
surface areas and open pore structures for enhanced rate
adsorption and increased adsorption capacity.
During the last two decades, the so-called mesostructured
materials have received much attention from the scientific
community. Several strategies were proposed to assign specific
properties to these materials for their adequate use in a variety
of applications such as catalysis, adsorption, and chemical
sensing.11 Among these strategies, surface functionalization via
* To whom correspondence should be addressed. Tel.: (418) 656
2131, ext. 8460. Fax: (418) 656 3723. E-mail address: safia.hamoudi@
sga.ulaval.ca.
10.1021/ie070195k CCC: $37.00 © 2007 American Chemical Society
Published on Web 11/07/2007
attention, because it allows one to introduce several function-
alities onto the internal pore surfaces through post-synthesis
grafting and co-condensation. The grafting method consists of
reacting a suitable organosilane with a previously synthesized
mesoporous material, using an appropriate solvent under reflux
conditions.11,12 Thus, the surface silanol groups react with the
organosilane to form a layer of covalently coupled surface
functional groups. Co-condensation involves the hydrolytic con-
densation of an organosilane with conventional silica sources
such as tetraethyl orthosilicate (TEOS).11,13 Specifically, meso-
porous silicas functionalized with amine functional groups have
been applied as adsorbents for heavy-metal cations, such as
cobalt, copper, and zinc cations,12 as well as for chromate and
arsenate oxyanions.13
The present work is intended to study the adsorption of nitrate
and monobasic phosphate anions, from synthetic aqueous
solutions using surface-modified MCM-48 material as an
adsorbent. The objectives pursued are (i) synthesis and char-
acterization of the adsorbent, (ii) experimental investigation of
the effect of operating conditions, and (iii) modeling of the
isotherms data.
2. Experimental Section
2.1. Materials and Adsorbent Synthesis. Tetraethyl ortho-
silicate (TEOS), 3-aminopropyltriethoxysilane (APTES), cetyl-
trimethylammonium bromide (CTAB), and sodium nitrate
(NaNO3) were purchased from Aldrich. Sodium orthophosphate
(NaH2PO4) was obtained from BDH, Inc. Deionized water was
used in the preparation of the adsorption solutions and the
mesoporous silica synthesis gels.
MCM-48 material was prepared according to the synthesis
procedure described by Schumacher et al.14 After calcination
at 540 °C, MCM-48 material was functionalized with amino
groups via post-synthesis grafting with a molar ratio of APTES
in the silica framework fixed to 10%. The post-synthesis grafting
procedure schematized in Figure 1 consisted of refluxing 10 g

Figure 1. Schematic representation of the MCM-48 surface functional-
ization.
(160 mmol SiO2) of calcined and dehydrated pure silica MCM-
48 material in 250 mL of dry toluene containing 16 mmol of
APTES under vigorous stirring at 383 k for 10 h.15 The obtained
material (MCM-48-NH2) was collected by filtration, washed
with isopropanol, and dried at 373 K. It then was acidified to
convert the amino groups to ammonium moieties.13,16 Thus, 1
g of each material was stirred in 1 L of 0.1 M HCl for 6 h at
ambient temperature. The acidified material (MCM-48-NH3+)
was then recovered by filtration and dried at room temperature
overnight, before its use as an adsorbent. Furthermore, blank
pure silica material was also subjected to the acidification
procedure and its adsorption performance was evaluated for
nitrate and phosphate removal.
2.2. Materials Characterization. Nitrogen adsorption-
desorption analyses were performed at 77 K using a Quantach-
rome Autosorb 1 volumetric analyzer. Prior to analysis, the
materials were degassed at 200 °C for 4 h for the pure silica
materials and 120 °C for 12 h for the organically functionalized
materials. The specific surface area (SBET) was determined from
the linear part of the Brunauer-Emmett-Teller (BET) plot
(P/P0 ) 0.05-0.20). The pore size distributions were calculated
from the desorption branch, using the Horvath-Kawazoe (HK)17
and Barrett-Joyner-Hallenda (BJH)18 methods for the mi-
croporous (pore size <2.0 nm)and mesoporous (pore size >2.0
nm) materials, respectively. The total pore volume was evaluated
from the adsorbed amount at a relative pressure of ∼0.99.
Powder X-ray diffraction (XRD) data of the synthesized
materials were collected on a Rigaku D-Max-Ultima III dif-
fractometer, using nickel-filtered Cu KR radiation (wavelength
λ ) 1.5406 Å). Powder XRD diffraction patterns were obtained
between 0.75° and 10° 2θ with a scan speed of 1° 2θ/min.
Elemental analysis was performed using a LECO CHN-600
apparatus.
2.3. Adsorption Experiments and Anions Analysis. The
adsorption capability of the synthesized adsorbent material
toward nitrate and phosphate anions was investigated separately,
using aqueous solutions of NaNO3 and NaH2PO4. Adsorption
was performed batchwise in Erlenmeyer flasks mounted on a
temperature-regulated platform stirrer under the following
conditions: temperature, 5-45 °C; adsorbent loading, 1-10 g/L;
anion initial concentration, 0.1-0.7 g/L; and pH 2-10. Pre-
liminary adsorption tests with sampling intervals of 2 min
showed that equilibrium was attained within 10 min. Thus, for
all the adsorption tests presented thereafter, the stirring was
continued for 60 min before aliquots of the solutions were
withdrawn, filtered with a microsyringe (0.2 µm) and analyzed
for nitrate or phosphate anions using an ion chromatograph (ICS
Ind. Eng. Chem. Res., Vol. 46, No. 25, 2007 8807
2500, Dionex) that was equipped with an electrochemical
detector, an IonPac AS18 (4 × 250 mm) column, and an
online eluent generator. The unit was operated isocratically at
1 mL/min using a 35 mM KOH solution as a mobile phase.
The data processing was performed using Chromeleon software
(from Dionex).
The adsorption experiments were performed in duplicate or
triplicate and analyzed twice.
The percentage removal (Re) of anions was calculated as
Ci - Ce
Re ) × 100 (1)
Ci
The amount of anions retained in the adsorbent phase (in units
of mg/g) at equilibrium was calculated using
V
Qe ) (Ci - Ce) × (2)
m
Consecutive adsorption-desorption cycles were also per-
formed to study the regenerability and stability of MCM48-
NH3+. Hence, after contacting a fresh adsorbent with nitrate or
phosphate solutions (300 mg/L), it was separated by filtration,
washed, dried at room temperature, and weighed. The anion-
loaded sample then was stirred in a 0.01 M NaOH solution for
1 h with a loading of 5 g adsorbent/L, to strip the nitrate or
phosphate anions. After filtration and washing with deionized
water, the solid was dried at room temperature and weighed. It
was then acidified in HCl solution, as described previously.
These steps represent the first adsorption-desorption cycle,
which was followed by four other cycles using the same
adsorbent batch.
3. Results and Discussion
3.1. Adsorbent Characterization. Results of the nitrogen
sorption analysis of the synthesized materials are presented in
Figures 2a and 2b and Table 1. Nitrogen adsorption-desorption
isotherm of the pure silica MCM-48 is a typical reversible type
IV isotherm, having an S-shape that is characteristic of
mesoporous materials. The MCM-48-NH2 showed an isotherm
with an adsorption step being shifted toward lower relative
pressures. The BET surface area decreased from 1400 m2/g for
the pure silica material to 890 m2/g for the MCM-48-NH2. The
corresponding pore sizes were 2.2 and 1.9 nm and the pore
volumes were 1.04 and 0.66 cm3/g for the MCM-48 and MCM-
48-NH2, respectively. The decrease in the textural properties
was previously reported to accompany the surface modification
of mesoporous materials with organic functional groups and was
attributed to the occupation of the pore framework by the
functional groups protruding into the internal pores surface.11
Furthermore, MCM-48 samples functionalized according to
organosilane/pure silica molar ratios of 15% and 20% exhibited
surface areas in the same order of magnitude as the 10%
material, but the pore sizes and total pore volumes were
significantly lower (i.e., 1.6 and 1.5 nm and 0.5 and 0.44 cm3/g
for the 15% and 20% materials, respectively). Thus, to prevent
complete pore blockage and a drastic decrease in pore volume,
which may affect the adsorbent performances, the organosilane/
pure silica molar ratio was voluntarily fixed to 10% during the
synthesis of MCM-48-NH2. Furthermore, elemental analysis
performed on the amine- and ammonium-functionalized MCM-
48 revealed that 90% of the propylamine groups initially
contacted with the calcined MCM-48 material were effectively
8808 Ind. Eng. Chem. Res., Vol. 46, No. 25, 2007

Figure 3. Powder X-ray diffraction (XRD) patterns for MCM-48 materials.

Figure 2. (a) Nitrogen adsorption-desorption isotherms of MCM-48

materials and (b) corresponding pore size distributions.

Table 1. Textural Properties of Calcined and Functionalized

MCM48
d211 BET pore total pore Figure 4. Effect of pH on nitrate and phosphate anions adsorption on
spacing surface diameter volume MCM-48-NH3+ at 25 °C (initial anion concentration, 300 mg/L; adsorbent
adsorbent (nm) area (m2/g) (nm) (cm3/g) loading, 5 g/L). Lines show trends.
calcined MCM-48 3.25 1400 2.2 1.04
MCM-48-NH2 3.24 890 1.9 0.66 exchanger where the Cl- anions are exchanged by the nitrate
MCM-48-NH3+ 3.10 750 1.2 0.39 or phosphate anions in solution. In such cases, pH may have
an important effect on solution species and adsorbent surface
grafted on the silica surface. Therefore, the actual amount of charge. The effect of pH is illustrated in Figure 4. In the case
grafted propylamine groups was 1.55 mmol/g MCM-48 material. of nitrate anions, the equilibrium anion uptake was almost
Moreover, nitrogen adsorption performed on the MCM-48- unaffected by the pH within the pH range of 2-8. At pH >8,
NH3+ revealed a subsequent decrease in its textural properties. with the increasing basicity of the adsorption medium, the
This may be attributed to the progressive pore filling of the equilibrium anion uptake was negatively affected by the pH.
material by the counteranion Cl-, which balances the positive As for phosphate anions, the pH dependency profile denoted
charge formed by the protonation during reaction with HCl an optimal zone in the pH range of 4-6. According to the
solution. titration curve of H3PO4 with NaOH,19 phosphate anions occur
Powder XRD patterns are depicted in Figure 3. Both MCM- either as monovalent H2PO4-, divalent HPO42-, or trivalent
48 and MCM-48-NH2, as well as MCM-48-NH3+, exhibited PO43- forms, depending on the solution pH (pK1 ) 2.2, pK2 )
XRD patterns typical of cubic Ia3d mesophase with character- 7.2, pK3 ) 12.4). Therefore, a pH range of 4-6 corresponds to
istic Bragg peaks at ∼2.8° and 3.0° 2θ attributed to the (211) the occurrence of monobasic phosphate anions (H2PO4-).
and (220) diffraction lines, respectively. This indicates that the Furthermore, pH influences the charge of the grafted propyl-
modified materials retained the ordered cubic structure, although amine groups on the mesoporous silica walls. Indeed, the pKa
the MCM-48-NH3+ diffractogram denoted a slight shift toward value for propylamine groups grafted on different mesoporous
higher values for the two main peaks, thus confirming the silica materials, as well as on amorphous silica gels, was
shrinking in the pore diameters, in agreement with the nitrogen evaluated to be ∼9,16,20 while the pKa value of propylamine is
adsorption data. 10.6.21 Hence, when pH < pKa, the amino groups are charged
3.2. Adsorption Tests. 3.2.1. Effect of pH. The MCM-48- positively upon protonation, which leads to ammonium moieties
NH3+ adsorbent exhibiting surface propyl-ammonium groups, capable of attracting anionic species by electrostatic forces. In
together with their Cl- counter-anions acts as an anion contrast, when pH > pKa, the alkyl-ammonium species are

Figure 5. Effect of anion initial concentration and adsorbent loading on
the adsorption for (a) the nitrate and (b) the phosphate at 25 °C. Lines
show trends. Bars show standard deviations on measurements.
deprotonated and recover their free amine form, unable to exert
any electrostatic effect toward anionic species present in
solution.
3.2.2. Effect of the Initial Anion Concentration and
Adsorbent Loading. As mentioned in the Experimental Section,
calcined MCM-48 was acidified under the same conditions as
the MCM-48-NH2 material to probe its adsorption performances
in the removal of nitrate and phosphate anions from water.
Tested separately using 130 mg/L nitrate solutions and 100 mg/L
phosphate solutions for an adsorbent loading of 2 g/L, the
obtained anion removals were 0.7% ( 0.4% and 1.8% ( 1.1%,
respectively. Because the blank material failed to adsorb both
nitrate and phosphate anions significantly, it was concluded that
the adsorption occurred at the surface propyl ammonium
functional sites of the MCM-48-NH3+ adsorbent.
The effect of the initial anion concentration on nitrate and
phosphate adsorption on MCM-48-NH3+ in the range of 100-
700 mg/L, using an adsorbent loading in the range of 2-10
g/L at ambient temperature is depicted in Figures 5a and 5b for
nitrate and phosphate anions, respectively.
For all the adsorbent loadings investigated, an increase in
the initial concentration of either nitrate or phosphate from 100
mg/L to 700 mg/L translated in a decrease in the percentage
uptake. The nitrate and phosphate adsorption from their respec-
tive solutions was significantly influenced by the adsorbent
loading. For instance, the percentage adsorption of nitrate
increases from 38% (19 mg/g) to 71% (7 mg/g) by increasing
the adsorbent loading from 2 g/L to 10 g/L, at an initial
concentration of 100 mg/L. At an initial concentration of 700
mg/L nitrate, the percentage removal increases from 7% (25
mg/g) to 30% (20 mg/g) by increasing the adsorbent loading
from 2 g/L to 10 g/L. Generally, the same tendency was
Ind. Eng. Chem. Res., Vol. 46, No. 25, 2007 8809
Figure 6. Experimental and theoretical adsorption isotherms on MCM-
48-NH3+ for (a) the nitrate anion and (b) the phosphate anion with 5 g/L
adsorbent loading. Solid lines represent the Langmuir model (denoted as
“L” in the figure). For the sake of clarity, dotted lines are shown only for
isotherms at 5 and 45 °C; these dotted lines refer to the Freundlich (“F”),
Langmuir-Freundlich (“LF”), and Redlich-Peterson (“RP”) models.
observed for phosphate anions as depicted in Figure 5b. This is
attributed to the fact that, at higher adsorbent loadings, because
of increased surface area, more adsorption sites are available,
leading to a higher removal of nitrate or phosphate anions. The
results showed also that the uptakes per unit mass of the
adsorbent (Qe) were higher at lower adsorbent loadings. This
may be attributed to the fact that, at higher adsorbent loadings,
some of the adsorption sites remain unsaturated during the
adsorption process. However, it is worthy of mention that, even
if the initial concentrations were intentionally varied to up to
700 mg/L for phosphate and nitrate, typical actual effluents
heavily charged with nutrient compounds stemming for instance
from agricultural pig farms contain, at most, 200 mg/L dissolved
mineral and organic phosphorus species and 2 mg/L nitrate.22,23
In the case of aquaculture wastewaters, the concentrations of
phosphate and nitrate are ∼80 mg/L and ∼20 mg/L, respec-
tively.24 This makes the proposed adsorbent adequate for the
treatment of such wastewaters.
3.2.3. Adsorption Isotherms. 3.2.3.1. Experimental Ad-
sorption Isotherms. The adsorption isotherm studies are
conducted to investigate the effect of temperature on the
adsorption of nitrate and phosphate anions on MCM-48-NH3+
and to determine the maximum adsorption capacities. Hence,
the adsorption isotherms for nitrate and phosphate anions on
MCM-48-NH3+ at different temperatures are depicted in Figures
6a and 6b. As the figure shows, by increasing the temperature,
the equilibrium uptake for both anions decreased, indicating the
8810 Ind. Eng. Chem. Res., Vol. 46, No. 25, 2007

exothermic character of the adsorption process. Maximum Table 2. Model Isotherm Constants for Nitrate and Phosphate
adsorption capacities of ∼43 mg/g (0.7 mmol/g) and 46 (0.5 Adsorption on MCM-48-NH3+
mmol/g) were obtained at the lowest temperature investigated Langmuir Constants Langmuir-Freundlich Constants
(5 °C) for nitrate and phosphate anions, respectively. Compari- temperature temperature
son of the obtained capacities to the amount of grafted (K) Kad Qmax Ω (K) Kad Qmax n Ω
propylamine groups on the MCM-48 silica surface (1.55 mmol/ Nitrate Nitrate
g) indicates that, at most, only 45% of the grafted groups were 278 0.012 51.8 2.0 278 0.012 52.2 1.02 1.9
involved in the adsorption process. This may be attributed to 288 0.011 44.6 2.5 288 0.006 41.6 0.84 2.2
the incomplete protonation of the propylamine groups grafted 298 0.011 39.4 2.5 298 0.003 35.1 0.72 1.3
308 0.012 34.8 3.9 308 0.001 30.2 0.58 2.2
on the mesoporous silica material, as previously reported by 318 0.009 32.0 2.7 318 0.001 27.4 0.63 1.4
Walcarius and co-workers,16,20 who observed a ratio of 40%:
60% between propylamine and propylammonium grafted species Phosphate Phosphate
278 0.043 47.8 3.7 278 0.090 54.5 1.45 1.5
on amorphous silica gels, as well as on three different meso- 288 0.029 44.6 2.3 288 0.052 48.6 1.27 1.4
porous silicas (i.e., MCM-41, MCM-48, and SBA-15). Further- 298 0.027 40.8 1.7 298 0.045 43.4 1.20 1.2
more, in the presence of water, aminopropyl-functionalized silica 308 0.019 39.7 1.7 308 0.009 37.5 0.82 1.1
materials undergo proton transfer from silanol to amine surface 318 0.018 36.5 2.0 318 0.007 34.1 0.78 1.4
groups, leading to the formation of zwitterion-like moieties Freundlich Constants Redlich-Peterson Constants
(≡SiO-, +H3N≡), as proposed first by Golub et al.25 and later
temperature temperature
by Walcarius and co-workers.16,20 Because these zwitterion-like (K) KF n Ω (K) a Kad n Ω
surface moieties are already charge balanced, they do not
Nitrate Nitrate
represent ion exchange sites for the anionic species investigated,
278 2.77 4.9 5.5 278 0.011 0.60 0.99 1.9
thus diminishing the effective adsorption capacity. 288 2.92 4.6 6.1 288 0.003 0.39 0.84 1.7
3.2.3.2. Adsorption Isotherms Modeling. To date, thermo- 298 3.03 4.4 5.9 298 0.002 0.35 0.85 1.1
dynamic parameters such as the enthalpy and entropy of 308 3.32 4.7 6.9 308 0.001 0.27 0.69 0.7
adsorption of dissolved nitrate and phosphate anions onto the 318 2.91 3.1 5.2 318 0.000 0.24 0.86 1.7
present mesoporous adsorbent (MCM-48-NH3+) were not Phosphate Phosphate
reported in the open literature; therefore, it is proposed in this 278 4.40 12.1 5.5 278 0.117 3.18 1.11 2.0
section to estimate these parameters based on known adsorption 288 3.99 9.4 4.9 288 0.058 1.66 1.08 1.5
298 4.11 8.8 4.7 298 0.034 1.32 1.05 1.4
models. The adsorption isotherms data at different temperatures 308 3.72 7.0 5.9 308 0.015 0.59 0.90 0.7
were restricted to the Langmuir, Freundlich, Langmuir- 318 3.71 6.3 5.5 318 0.007 0.51 0.89 1.3
Freundlich, and Redlich-Peterson isotherm models, which are
represented by the following equations: experimental data and the different models predicted isotherms
for nitrate and phosphate anions. The estimated isotherm
KadQmaxCe parameters are summarized in Table 2. Clearly, the Langmuir-
Langmuir equation: Qe ) (3)
1 + KadCe Freundlich and Redlich-Peterson models, which are character-
ized by three parameters, resulted in the lowest residues, which
Freundlich equation: Qe ) KFCe1/n (4) suggests the numerical adequacy of these models. The enthalpies
and entropies of adsorption that are reported in Table 3 were
KadQmaxCe1/n evaluated from the temperature dependence of the adsorption
Langmuir-Freundlich equation: Qe ) (5) constants according to the van’t Hoff law. As observed, the neg-
1 + KadCe1/n
ative enthalpies obtained for all the models considered confirm
aCe the exothermicity of the adsorption process investigated. En-
Redlich-Peterson equation: Qe ) (6) thalpies and entropies evaluated from the Langmuir-Freundlich
1 + KadCen and Redlich-Peterson models seemed to be excessively high.
In contrast, energies determined from the Langmuir and
The isotherm constants were determined by optimization, Freundlich constants were determined to be reasonably com-
using the Quasi-Newton constrained optimization method run- parable with those scarcely reported in the literature for nitrate
ning a mixed quadratic and cubic line search procedure (Matlab and phosphate anion adsorption. For instance, Sahai determined
software, from MathWorks Inc.) to solve a least-squares enthalpies of -5 and -8 kJ/mol and entropies of -75 and -92
problem, minimizing the quadratic criterion :2 J/(mol K) for the adsorption of NO3- and H2PO4- anions,
respectively, on R-silica.26
min 2 ) ∑ (Qe - Qe)2 (7) Discrimination between the four models was based on the
a, Qmax, Kad, n > 0 goodness of fit (2 or Ω) and the physicochemical significance
of the parameter estimates, according to the following Boudart
where the bars represent the experimental quantities. criteria:27
The relative mean deviation to the experimental data (Ω) is
∆S < 0 (9a)
calculated as
10 e -∆S e 12.2 - 0.0014∆H

x( )
(9b)
2
Qe - Qe Therefore, the ultimate model to be soundly retained must fulfill
Ω) ∑ (8) both conditions (eqs 7 or 8 and 9) simultaneously. Among the
Qe four models evaluated in the present investigation, only the
Freundlich model fulfilled these conditions and was thus
The model predicted isotherms are also presented in Figures retained, although it presented the less-satisfactory fit to the
6a and 6b. Reasonable agreement was obtained between the experimental data. This model, which is the most popular for a
 Ind. Eng. Chem. Res., Vol. 46, No. 25, 2007 8811

Table 3. Enthalpies and Entropies of Adsorption for Nitrate and Phosphate Anions on MCM-48-NH3+ for Various Models
Nitrate Anion Phosphate Anion
enthalpy, -∆H entropy, -∆S Boudart criteria enthalpy, -∆H entropy, -∆S Boudart criteria
model (kJ/mol) (J/(mol K)) fulfillment? (kJ/mol) (J/(mol K)) fulfillment?
Langmuir 2.5 45.7 no 16.1 84.4 no
Freundlich 8.4 16.6 yes 11.8 21.6 yes
Langmuir-Freundlich 70.6 291.9 no 51.6 202.5 no
Redlich-Peterson 62.4 260.4 no 51.2 202.3 no

Table 4. Regeneration of the Adsorbenta

single solute system, is known to be adequate to describe
adsorption data obtained for concentrations within the interme- NO3- H2PO4-
diate range.28 For instance, it is reported that this model exhibits % amount % amount
some discrepancies toward experimental data for dilute solutions cycle removal adsorbed (mg/g) removal adsorbed (mg/g)
attributed to its weak description of the Henry’s law.28 On the 1 46.0 ( 3.7 27.6 ( 2.2 59.0 ( 6.1 35.4 ( 3.7
other hand, the Freundlich model was also reported to well 2 41.5 ( 8.7 24.9 ( 5.2 60.6 ( 3.3 36.4 ( 1.9
describe equilibrium adsorption data obtained for adsorbents 3 40.5 ( 4.0 24.3 ( 2.4 52.5 ( 3.5 31.5 ( 2.1
4 40.0 ( 9.4 24.0 ( 5.6 57.5 ( 5.4 34.5 ( 3.2
that have heterogeneous surfaces consisting of sites with 5 43.3 ( 4.7 26.0 ( 2.8 56.6 ( 1.8 33.4 ( 1.0
different adsorption potentials.28 In contrast, the Langmuir a Operating conditions: nitrate or phosphate initial concentration, 300
model, which was originally developed to describe the chemi-
mg/L; adsorbent loading, 5 g/L; temperature, 25 °C; adsorption time, 60
sorption equilibrium of gases, is intended to describe homoge- min.
neous surfaces and monolayer adsorption.29 In the case of the
MCM-48-NH3+ adsorbent, the surface heterogeneity may be desorption, making the adsorbent very suitable for the design
related to the grafting procedure, which uses the silanol groups of a continuous sorption process.
distributed randomly on the internal and external surfaces, as
well as on pore apertures of mesostructured silica material. 4. Conclusion
Silanol groups are classified into three different types, i.e., single
(≡SiOH), geminal (dSi(OH)2), and hydrogen-bonded hydroxyl A mesoporous silica functionalized with ammonium groups
groups.11 Only single and geminal groups are involved in the (MCM-48-NH3+) was synthesized and proved to be an effective
grafting.11 high-capacity adsorbent for the removal of NO3- and H2PO4-
3.2.4. Desorption and Regeneration. Because the success anions from aqueous solutions. The adsorption was influenced
and adequacy of adsorption are dependent on the possibility by pH, initial anion concentration, adsorbent loading, and
of, on one hand, desorbing the target nutrient species for their temperature. The removal of nitrates was optimal at pH <8,
eventual recovery and reuse as valuable fertilizers and, on the whereas, for phosphates, the adsorption was optimal in the pH
other hand, reusing the adsorbent for economic and environ- interval of 4-6. Maximal removals of 70% and 88% were
mental motivations, the desorption and adsorbent recycling obtained for the nitrate and phosphate, respectively. Classical
possibility have been investigated. Therefore, Figure 7 shows isotherm models described the experimental data adequately.
the desorption kinetics, relative to the spent adsorbents used However, based on a model discrimination study, using the
for nitrate and phosphate adsorption. As observed, the desorption goodness of fit and Boudart physicochemical criteria applied
was rapid and complete for both anions within 10 min. This to the energy data, only the Freundlich model was retained,
leads to the conclusion that the adsorption of anions on MCM- despite its less-satisfactory fit to the experimental data. Fur-
48-NH3+ is completely reversible. On the other hand, consecu- thermore, the desorption was rapid and completely achieved
tive adsorption-desorption cycles data are shown in Table 4. within 10 min for both anions, using 0.01 M NaOH. Recycling
As clearly demonstrated, no significant loss of adsorbent tests showed that no significant loss of adsorbent capacity was
capacity was observed during five cycles of adsorption- observed during five adsorption-desorption cycles.

Notation
a ) constant in the Redlich-Peterson isotherm equation; a )
KadQmax
Ci ) initial concentration of the anions in solution (mg/L)
Ce ) equilibrium concentration of the anions in solution (mg/L
or mol/m3)
∆H ) adsorption enthalpy (kJ/mol)
∆S ) adsorption entropy (J/(mol K))
Kad ) adsorption equilibrium constant (m3/mol)
KF ) Freundlich adsorption constants (m3/mol)n
m ) adsorbent weight (g)
Qe ) amount of anions retained on the adsorbent phase at
equilibrium (mg/g or mol/kg)
Qmax ) adsorbent maximum adsorption capacity (mg/g or mol/
kg)
R ) gas constant (J/(mol K))
Re ) anions removal (%)
Figure 7. Desorption kinetics of nitrate and phosphate anions at 25 °C in T ) temperature (K)
0.01 M NaOH solution. Adsorbent loading ) 5 g/L. Lines show trends. V ) solution volume (L)
8812 Ind. Eng. Chem. Res., Vol. 46, No. 25, 2007
Greek Symbols
2) quadratic criterion
Ω ) relative mean deviation to the experimental data
Acknowledgment
Funding provided by the Natural Sciences and Engineering
Research Council of Canada (NSERC) and the Canada Founda-
tion for Innovation (CFI) is gratefully acknowledged.
Literature Cited
(1) Jorgensen, S. E.; Williams, W. D. Water Quality: The Impact of
Eutrophication; United Nations Environment Program, 2001.
(2) Viessman, W., Jr.; Hammer, M. J. Water Supply and Pollution
Control; Prentice Hall: Upper Saddle River, NJ, 2005.
(3) Levine, S. N.; Schindler, D. W. Phosphorus, Nitrogen and Carbon
Dynamics of Experimental Lake 303 during Recovery from Eutrophication.
Can. J. Fish. Aquat. Sci. 1989, 46, 2.
(4) World Health Organization: Guidelines for Drinking-water Quality.
http://www.who.int/water_sanitation_health/dwq/gdwq0506.pdf.
(5) Murphy, A. P. Chemical Removal of Nitrate from Water. Nature
1991, 350, 223.
(6) Agyei, N. M.; Strydom, C. A.; Potgieter, J. H. The Removal of
Phosphate Ions from Aqueous Solution by Fly Ash, Slag, Ordinary Portland
Cement and Related Blends. Cem. Concr. Res. 2002, 32, 1889.
(7) Li, Z. H.; Bowman, R. S. Retention of Inorganic Oxyanions by
Organo-kaolinite. Water Res. 2001, 35, 3771.
(8) Ozacar, M. Adsorption of Phosphate from Aqueous Solution onto
Alunite. Chemosphere 2003, 51, 321.
(9) Zhao, D. Y.; Sengupta, A. K. Ultimate Removal of Phosphate from
Wastewater Using a New Class of Polymeric Ion Exchangers. Water. Res.
1998, 32, 1613.
(10) Orlando, U. S.; Baes, A. U.; Nishijima, W.; Okada, M. Preparation
of Agricultural Residue Anion Exchangers and its Nitrate Maximum
Adsorption Capacity. Chemosphere 2002, 48, 1041.
(11) Sayari, A.; Hamoudi, S. Periodic Mesoporous Silica-based Organic-
Inorganic Nanocomposite Materials. Chem. Mater. 2001, 13, 3151.
(12) Stein, A.; Melde, B. J.; Schroden, R. C. Hybrid Inorganic-Organic
Mesoporous SilicatessNanoscopic Reactors Coming of Age. AdV. Mater.
2000, 12, 1403.
(13) Yoshitake, H.; Yokoi, T.; Tatsumi, T. Adsorption of Chromate and
Arsenate by Amino-functionalized MCM-41 and SBA-1. Chem. Mater.
2002, 14, 4603-4610.
(14) Schumacher, K.; Grün, M.; Unger, K. K. Novel Synthesis of
Spherical MCM-48. Microporous Mesoporous Mater. 1999, 27, 201.
(15) Yokoi, T.; Yoshitake, H.; Tatsumi, T. Synthesis of Amino-
functionalized MCM-41 via Direct Co-condensation and Post-synthesis
Grafting Methods Using Mono-, Di- and Tri-amino-organoalkoxysilanes.
J. Mater. Chem. 2004, 14, 951.
(16) Walkarius, A.; Etienne, M.; Lebeau, B. Rate of Access to the
Binding Sites in Organically Modified Silicates. 2. Ordered Mesoporous
Silicas Grafted with Amine or Thiol Groups. Chem. Mater. 2003, 15, 2161.
(17) Horvath, G.; Kawazoe, K. Method for the Calculation of Effective
Pore Size Distribution in Molecular Sieve Carbon. J. Chem. Eng. Jpn. 1983,
16, 470.
(18) Barrett, E. P.; Joyner, L. G.; Halenda, P. P. The Determination of
Pore Volume and Area Distributions in Porous Substances. 1. Computations
from Nitrogen Isotherms. J. Am. Chem. Soc. 1951, 73, 373.
(19) Yoshida, H.; Galinada, W. A. Equilibria for Adsorption of
Phosphates on OH-type Strongly Basic Ion Exchanger. AIChE J. 2002, 48,
2193.
(20) Walcarius, A.; Etienne, M.; Bessière, J. Rate of Access to the
Binding Sites in Organically Modified Silicates. 1. Amorphous Silica Gels
Grafted with Amine or Thiol Groups. Chem. Mater. 2002, 14, 2757.
(21) Harris, D.C. QuantitatiVe Chemical Analysis, Second Edition; W.
H. Freeman and Company: New York, 1987; pp 729-738.
(22) Bortone, G.; Gemelli, S.; Rambaldi, A.; Tilche, A. Nitrification,
Denitrification and Biological Phosphate Removal in Sequencing Batch
Reactors Treating Piggery Wastewater. Wat. Sci. Technol. 1992, 26, 977.
(23) Navaratnasamy, M.; Feddes, J. J. R.; Leonard, J. J. Reusing Liquid
Manure as a Possible Source of Drinking Water for Pigs. Can. Biosyst.
Eng. 2004, 46, 2.67.
(24) Kioussis, D. R.; Wheaton, F. W.; Kofinas, P. Reactive Nitrogen
and Phosphorus Removal from Aquaculture Wastewater Effluents Using
Polymer Hydrogels. Aquat. Eng. 2000, 23, 315.
(25) Golub, A. A.; Zubenko, A. I.; Zhmud, B.V. Gamma-APTES
Modified Silica Gels: The Structure of the Surface Layer. J. Colloid
Interface Sci. 1996, 179, 482.
(26) Sahai, N. Estimating Adsorption Enthalpies and Affinity Sequences
of Monovalent Electrolyte Ions on Oxide Surfaces in Aqueous Solution.
Geochim. Cosmochim. Acta 2000, 64, 3629.
(27) Boudart, M.; Mears, D.; Vannice, M. A. In Congres International
Chimie Industrielle. Ind. Chim. Belge 1967, 32, 281.
(28) Rouquerol, F.; Rouquerol, J.; Sing, K. Adsorption by Powders and
Porous Solids: Principles, Methodology and Applications; Academic
Press: New York, 1999.
(29) Myers, D. Surfaces, Interfaces and Colloids: Principles and
Applications; Wiley: New York, 1999.
ReceiVed for reView February 2, 2007
ReVised manuscript receiVed August 16, 2007
Accepted September 11, 2007
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